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| author | nfenwick <nfenwick@pglaf.org> | 2025-02-16 11:21:20 -0800 |
|---|---|---|
| committer | nfenwick <nfenwick@pglaf.org> | 2025-02-16 11:21:20 -0800 |
| commit | 0acc48572d38f314e60a112a861a6b10968a2876 (patch) | |
| tree | 7a0ba89cc482f84b0384f0365f48a572b92a3f85 /75389-h | |
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font-size: 0.9em;} +.footnote .label {position: absolute; right: 84%; text-align: right;} +.fnanchor { + vertical-align: super; + font-size: .8em; + text-decoration: + none; +} + +.transnote {background-color: #E6E6FA; + color: black; + font-size:smaller; + padding:0.5em; + margin-bottom:5em; + font-family:sans-serif, serif; } + +.ws2 {display: inline; margin-left: 0em; padding-left: 2em;} +.ws3 {display: inline; margin-left: 0em; padding-left: 3em;} +.ws4 {display: inline; margin-left: 0em; padding-left: 4em;} +.ws5 {display: inline; margin-left: 0em; padding-left: 5em;} +.ws6 {display: inline; margin-left: 0em; padding-left: 6em;} +.ws7 {display: inline; margin-left: 0em; padding-left: 7em;} +.ws8 {display: inline; margin-left: 0em; padding-left: 8em;} +.ws10 {display: inline; margin-left: 0em; padding-left: 10em;} + + </style> + </head> +<body> +<div style='text-align:center'>*** START OF THE PROJECT GUTENBERG EBOOK 75389 ***</div> + +<hr class="chap x-ebookmaker-drop"> + +<h1><span class="fs_80">PRINCIPLES AND PRACTICE<br> OF</span><br>AGRICULTURAL ANALYSIS.</h1> + +<hr class="r60"> +<p class="center">A MANUAL FOR THE EXAMINATION OF SOILS,<br> +FERTILIZERS, AND AGRICULTURAL PRODUCTS.</p> + +<hr class="r60"> +<p class="center">FOR THE USE OF ANALYSTS, TEACHERS, AND<br> +STUDENTS OF AGRICULTURAL CHEMISTRY.</p> + +<p class="f120 spa2 spb1">VOLUME III.</p> + +<p class="f120 spb2"><b>AGRICULTURAL PRODUCTS.</b></p> + +<p class="f120"><b>BY HARVEY W. WILEY,</b></p> +<p class="f90"><span class="smcap">Chemist of the U. S. Department of Agriculture.</span>.</p> + +<hr class="r60"> +<p class="center">EASTON, PA.<br><span class="smcap">Chemical Publishing Co.</span><br> +1897.</p> + +<p class="center">COPYRIGHT, 1897,<br><span class="smcap">By Harvey W. Wiley</span>.</p> + +<hr class="chap x-ebookmaker-drop"> + +<div class="chapter"> +<p class="f150"><b>PREFACE TO VOLUME THIRD.</b></p> +</div> + +<p>The concluding volume of the Principles and Practice of Agricultural +Analysis has been written in harmony with the plan adopted at the +commencement of the first volume. In it an effort has been made to +place the analyst or student <i>en rapport</i> with all the best +methods of studying the composition of agricultural products. During +the progress of the work the author has frequently been asked why +some special method in each case has not been designated as the +proper one to be used. To do this would be a radical departure from +the fundamental idea of the work; <i>viz.</i>, to rely on the good +judgment and experience of the chemist. It is not likely that the +author’s judgment in such matters is better than that of the analyst +using the book, and, except for beginning students pursuing a course +of laboratory instruction, a biased judgment is little better than +none at all. For student’s work in the laboratory or classroom it is +probable that a volume of selected methods based on the present work +may be prepared later on, but this possible future need has not been +allowed to change the purpose of the author as expressed in the preface +of the second volume “to present to the busy worker a broad view of a +great subject.” For the courtesy and patience of the publishers, for +the uniformly commendatory notices of the reviewers of volumes one and +two, and for the personal encouraging expressions of his professional +brethren the author is sincerely grateful. He finds in this cordial +reception of his book a grateful compensation for long years of +labor. The plates of the first edition of the three volumes have been +destroyed in order to insure a re-writing of the second edition when it +shall be demanded, in order to keep it abreast of the rapid progress in +the field of agricultural chemical analysis.</p> + +<p><span class="smcap">Washington, D. C.</span>,<br> +  Beginning of January, 1897.</p> + +<hr class="chap x-ebookmaker-drop"> + +<div class="chapter"> +<p><span class="pagenum"><a id="Page_iv"></a>[Pg iv]</span></p> +<p class="f150"><b>TABLE OF CONTENTS OF<br> VOLUME THIRD.</b></p> +</div> + +<div class="blockquot"> +<p class="f120 spa1"><b>PART FIRST.</b></p> +<p class="f110">SAMPLING, DRYING, INCINERATION<br> AND EXTRACTIONS.</p> + +<p class="neg-indent"><i>Introduction</i>, <a href="#Page_1">pp. 1-3</a>.—Methods +of study; Scope of the work; Limitations of work; General manipulations.</p> + +<p class="neg-indent"><i>Methods of Sampling</i>, <a href="#Page_3">pp. 3-13</a>.—Vegetable +substances; Animal substances; Preserving samples; Collecting samples; +Grinding samples; Grinding apparatus.</p> + +<p class="neg-indent"><i>Drying Organic Bodies</i>, <a href="#Page_13">pp. 13-36</a>.—Volatile +bodies; Drying ovens; Air baths; Drying in vacuum; Electric drying +ovens; Steam coil apparatus; Drying in hydrogen; Drying in tubes; +Drying viscous liquids; General principles of drying.</p> + +<p class="neg-indent"><i>Incineration</i>, <a href="#Page_36">pp. 36-40</a>.—Principles +of incineration; Products of combustion; Purpose and conduct of +incineration; German ash method; Courtonne’s muffle.</p> + +<p class="neg-indent"><i>Extraction of Organic Bodies</i>, +<a href="#Page_40">pp. 40-57</a>.—Object of extraction; Solvents; +Methods of extraction; Extraction by digestion; Extraction by +percolation; Apparatus for extraction; Knorr’s extraction apparatus; +Soxhlet’s extraction apparatus; Compact extraction apparatus; Recovery +of solvents; Authorities cited in Part First.</p> + +<p class="f120 spa1"><b>PART SECOND.</b></p> +<p class="f110">SUGARS AND STARCHES.</p> + +<p class="neg-indent"><i>Introduction</i>, <a href="#Page_58">pp. 58-62</a>.—Carbohydrates; +Nomenclature; Preparation of pure sugar; Classification of methods of analysis.</p> + +<p class="neg-indent"><i>Analysis by Density of Solution</i>, +<a href="#Page_63">pp. 63-72</a>.—Principles of the method; +Pyknometers; Calculating volume of pyknometers; Hydrostatic balance; +Areometric method; Correction for temperature; Brix hydrometer; +Comparison of brix and baumé degrees; Errors due to impurities.</p> + +<p class="neg-indent"><i>Estimation of Sugars with Polarized Light</i>, +<a href="#Page_74">pp. 74-120</a>.—Optical properties of sugars; +Polarized light; Nicol prism; Polariscope; Kinds of polariscopes; +Character of light; Description of polarizing instruments: +Laurent polariscope; Polariscope lamps; <span class="pagenum"><a +id="Page_v"></a>[Pg v]</span> Soleil-Ventzke polariscope; Half Shadow +polariscope; Triple field polariscope; Setting the polariscope; +Control observation tube; Quartz plates; Correcting quartz plates; +Application of quartz plates; Sugar flasks; Preparing sugar solutions +for polarization; Alumina cream; Errors due to lead solutions; Double +polarization; Mercuric compounds; Bone-black; Inversion of sugar; +Clerget’s method; Influence of strength of solution; Calculation of +results; Method of Lindet; Use of invertase; Activity of invertase; +Inversion by yeast; Determination of sucrose; Determination of +raffinose; Specific rotatory power; Calculating specific rotatory +power; Variations in specific rotatory power; Gyrodynatic data; Birotation.</p> + +<p class="neg-indent"><i>Chemical Methods of Estimating Sugar</i>, +<a href="#Page_120">pp. 120-149</a>.—General principles; Classification +of methods; Reduction of mercuric salts; Sachsse’s solution; Volumetric +copper methods; Action of copper solution on dextrose; Fehling’s +solution; List of copper solutions; Volumetric laboratory method; +Filtering tubes; Correction of errors; Permanganate process; Modified +permanganate method; Specific gravity of cuprous oxid; Soldaini’s +process; Relation of reducing sugar to quantity of suboxid; Factors for +different sugars; Pavy’s process; Peska’s process; Method of Allein and +Gaud; Method of Gerrard; Sidersky’s modification; Titration of excess +of copper.</p> + +<p class="neg-indent"><i>Gravimetric Copper Methods</i>, +<a href="#Page_149">pp. 149-170</a>.—General principles; Laboratory +copper method; Halle method; Allihn’s method; Meissl’s method; +Determination of invert sugar; Estimation of milk sugar; Determination +of maltose; Preparation of levulose; Estimation of levulose.</p> + +<p class="neg-indent"><i>Miscellaneous Methods of Sugar Analysis</i>, +<a href="#Page_171">pp. 171-196</a>; Phenylhydrazin; Molecular weights +of carbohydrates; Birotation; Estimation of pentosans; Determination of +furfurol; Method of Tollens; Method of Stone; Method of Chalmot; Method +of Krug; Precipitation with pyrogalol; Precipitation with phloroglucin; +Fermentation methods; Estimating alcohol; Estimating carbon dioxid; +Precipitation with earthy bases; Barium saccharate; Strontium +saccharate; Calcium saccharate; Qualitive tests; Optical tests; +Cobaltous nitrate test; The Dextrose group; Tests for levulose; Tests +for galactose; Tests for invert sugar; Compounds with phenylhydrazin; +Detection of sugars by means of furfurol; Bacterial action on sugars.</p> + +<p class="neg-indent"><i>Determination of Starch</i>, +<a href="#Page_196">pp. 196-226</a>.—Constitution of starch; +Separation of starch; Methods of separation; Separation with diastase; +Separation in an autoclave; Principles of analysis; Estimation of +water; Estimation of ash; Estimation of nitrogen; Hydrolysis with +acids; Factors for calculation; Polarization of starch; Solution at +high pressure; Method of Hibbard; Precipitation with barium hydroxid; +Disturbing bodies in starch determinations; Colorimetric estimation of +starch; Fixation of iodin; Identification of starches; Vogel’s table; +Muter’s table; Blyth’s classification; Preparation of starches for +the microscope; Mounting in canada balsam; Description of typical +starches; Authorities cited in Part Second. +<span class="pagenum"><a id="Page_vi"></a>[Pg vi]</span></p> + +<p class="f120 spa1"><b>PART THIRD.</b></p> +<p class="f110">SEPARATION AND DETERMINATION<br> +OF CARBOHYDRATES IN CRUDE OR<br> MANUFACTURED AGRICULTURAL PRODUCTS.</p> + +<p class="neg-indent"><i>Sugars in Vegetable Juices</i>, +<a href="#Page_227">pp. 227-253</a>.—Introduction; Sugar in the sap of +trees; Sugar in sugar canes; Weighing pipettes; Gravimeter; Reducing +sugars in juices; Preservation of juices; Direct estimation of sugar; +Cutting or shredding canes; Methods of analysis; Drying and extracting; +Examination of bagasse; Fiber in canes; Sugar beets; Estimation of +sugar in sugar beets; Machines for pulping beets; Instantaneous +diffusion; Pellet’s process; Alcohol digestion; Extraction with +alcohol; Determination of sugar in mother beets; Determination of +sugars without weighing; Continuous observation tube.</p> + +<p class="neg-indent"><i>Analysis of Sirups and Massecuites</i>, +<a href="#Page_254">pp. 254-264</a>.—Specific gravity; Determination +of water; Determination of ash; Determination of reducing sugars; +Estimation of minute quantities of invert sugar; Soldaini’s gravimetric +method; Weighing the copper as oxid; Analyses for factory control.</p> + +<p class="neg-indent"><i>Separation of Carbohydrates in Mixtures</i>, +<a href="#Page_264">pp. 264-292</a>.—Occurrence of sugars; Optical +methods; Optical neutrality of invert sugar; Separation of sucrose +and invert sugar; Separation of sucrose and raffinose; Determination +of levulose; Formula for calculating levulose; Separation of sucrose +from dextrose; Estimation of lactose in milk; Error due to volume of +precipitate; Separation of sucrose, levulose and dextrose; Sieben’s +method; Wiechmann’s method; Copper carbonate method; Winter’s process; +Separation with lead oxid; Analysis of commercial glucose and grape +sugar; Fermentation method; Oxidation method; Removal of dextrose by +copper acetate; Separation of dextrin with alcohol.</p> + +<p class="neg-indent"><i>Carbohydrates in Milk</i>, +<a href="#Page_293">pp. 293-298</a>.—Copper tartrate method; The +official method; The copper cyanid process; Separation of sugars in +evaporated milks; Method of Bigelow and McElroy.</p> + +<p class="neg-indent"><i>Separation and Determination of Starch and +Fiber</i>, <a href="#Page_298">pp. 298-306</a>.—Occurrence; +Separation of starch; Dry amyliferous bodies; Indirect method of +determining water; Removal of oils and sugars; Preparation of diastase; +Estimation of starch in potatoes; Constitution of cellulose; Fiber +in cellulose; Official method; Separation of cellulose: Solubility +of cellulose; Qualitive reactions for cellulose; Rare carbohydrates; +Authorities cited in Part Third. +<span class="pagenum"><a id="Page_vii"></a>[Pg vii]</span></p> + +<p class="f120 spa1"><b>PART FOURTH.</b></p> +<p class="f110">FATS AND OILS.</p> + +<p class="neg-indent"><i>General Principles</i>, +<a href="#Page_309">pp. 309-316</a>.—Nomenclature; Composition; +Principal glycerids; Presses for extraction; Solvents; Freeing extracts +of petroleum; Freeing fats of moisture; Sampling and drying for +analysis; Estimation of water.</p> + +<p class="neg-indent"><i>Physical Properties of Fats and Oils</i>, +<a href="#Page_317">pp. 317-350</a>.—Specific gravity; Balance +for determining specific gravity; Expression of specific gravity; +Coefficient of expansion of oils; Densities of common fats and oils; +Melting point; Determination in capillary tube; Determination by +spheroidal state; Solidifying point; Temperature of crystallization; +Refractive power; Refractive index; Abbe’s refractometer; Pulfrich’s +refractometer; Refractive indices of common oils; Oleorefractometer; +Butyrorefractometer; Range of application of the butyrorefractometer; +Viscosity; Torsion viscosimeter; Microscopic appearance; Preparation +of fat crystals; Observation of fat crystals with polarized light; +Spectroscopic examination of oils; Critical temperature; Polarization; +Turbidity temperature.</p> + +<p class="neg-indent"><i>Chemical Properties of Fats and Oils</i>, +<a href="#Page_351">pp. 351-406</a>.—Solubility in alcohol; Coloration +produced by oxidants; Nitric acid coloration; Phosphomolybdic acid +coloration; Picric acid coloration; Silver nitrate coloration; Stannic +bromid coloration; Auric chlorid coloration; Thermal reactions; Heat +of sulfuric saponification; Maumené’s process; Method of Richmond; +Relative maumené figure; Heat of bromination; Method of Hehner and +Mitchell; Author’s method; Haloid addition numbers; Hübl number; +Character of chemical reaction; Solution in carbon tetrachlorid; +Estimation of the iodin number; Use of iodin monochlorid; Preservation +of the hübl reagent; Bromin addition number; Method of Hehner; +Halogen absorption by fat acids; Saponification; Saponification +in an open dish; Saponification under pressure; Saponification in +the cold; Saponification value; Saponification equivalent; Acetyl +value; Determination of volatile fat acids; Removal of the alcohol; +Determination of soluble and insoluble fat acids; Formulas for +calculation; Determination of free fat acids; Identification of oils +and fats; Nature of fat acids; Separation of glycerids; Separation +with lime; Separation with lead salts; Separation of arachidic acid; +Detection of peanut oil; Bechi’s test; Milliau’s test; Detection of +sesamé oil; Sulfur chlorid reaction; Detection of cholesterin and +phytosterin; Absorption of oxygen; Elaidin reactions; Authorities cited +in Part Fourth.</p> + +<p class="f120 spa1"><b>PART FIFTH.</b></p> +<p class="f110">SEPARATION AND ESTIMATION OF BODIES<br> CONTAINING NITROGEN.</p> + +<p class="neg-indent"><i>Introduction and Definitions</i>, +<a href="#Page_410">pp. 410-418</a>.—Nature of nitrogenous bodies; +Classification of proteids; Albuminoids; Other forms of nitrogen; +Occurrence of nitrates.</p> + +<p class="neg-indent"><i>Qualitive Tests for Nitrogenous Bodies</i>, +<a href="#Page_418">pp. 418-422</a>.—Nitric acid; Amid +nitrogen; Ammoniacal nitrogen; Proteid <span class="pagenum"><a +id="Page_viii"></a>[Pg viii]</span> nitrogen; Qualitive tests for +albumni; Qualitive tests for peptones and albuminates; Action of +polarized light on albumins; Alkaloidal nitrogen.</p> + +<p class="neg-indent"><i>Estimation of Nitrogenous Bodies in Agricultural +Products</i>, <a href="#Page_423">pp. 423-432</a>.—Total nitrogen; +Ammoniacal nitrogen; Amid nitrogen; Sachsse’s method; Preparation of +asparagin; Estimation of asparagin and glutamin; Cholin and betain; +Lecithin; Factors for calculating results; Estimation of alkaloidal +nitrogen.</p> + +<p class="neg-indent"><i>Separation of Proteid Bodies in Vegetable +Products</i>, <a href="#Page_432">pp. 432-448</a>.—Preliminary +treatment; Character of proteids; Separation of gluten; Extraction with +water; Action of water on composition of proteids; Extraction with +dilute salt solution; Separation of bodies soluble in water; Separation +of the globulins; Proteids soluble in dilute alcohol; Solvent action of +acids and alkalies; Method of extraction; Methods of drying separated +proteids; Determination of ash; Determination of carbon and hydrogen; +Estimation of nitrogen; Determination of sulfur; Dialysis.</p> + +<p class="neg-indent"><i>Separation and Estimation of Nitrogenous +Bodies in Animal Products</i>, <a href="#Page_448">pp. 448-462</a>.—Preparation +of sample; Extraction of muscular tissues; Composition of meat extracts; +Analysis of meat extracts; Use of phosphotungstic acid; Separation of +albumoses and peptones; Estimation of gelatin; Estimation of nitrogen +in flesh bases; Treatment of residue insoluble in alcohol; Pancreas +peptone; Albumose peptone; Authorities cited in Part Fifth.</p> + +<p class="f120 spa1"><b>PART SIXTH.</b></p> +<p class="f110">DAIRY PRODUCTS.</p> + +<p class="neg-indent"><i>Milk</i>, <a href="#Page_464">pp. 464-512</a>.—Composition +of milk; Alterability of milk; Effects of boiling on milk; +Micro-organisms of milk; Sampling milk; Scovell’s milk sampler; +Preserving milk for analysis; Freezing point; Electric conductivity; +Viscosity; Acidity and alkalinity; Determination of acidity; Opacity; +Creamometry; Specific gravity; Lactometry; Quévenne lactometer; +Lactometer of the New York Board of Health; Density of sour milk; +Density of milk serum; Total solids; Formulas for calculating total +solids; Determination of ash; Estimation of fat; Fat globules; Number +of fat globules; Counting globules; Classification of methods of +analysis; Dry extraction methods; Official methods; Variations of +extraction methods; Gypsum method; Estimation of fat in malted milk; +Comparison of fat methods; Wet extraction methods; Solution in acid; +Solution in alkali; Method of Short; Method of Thörner; Liebermann’s +method; Densimetric methods; Areometric methods; Lactobutyrometer; +Volumetric methods of fat analysis; Method of Patrick; The lactocrite; +Modification of Lindström; Babcock’s method; Method of Leffmann and +Beam; Method of Gerber; Proteid bodies in milk; Estimation of total +<span class="pagenum"><a id="Page_ix"></a>[Pg ix]</span> +proteid matter; Copper sulfate as a reagent; Precipitation by ammonium +sulfate; Precipitation by tannic acid; Separation of casein from +albumin; Estimation of casein; Factors for calculation; Separation of +casein; Separation of casein with carbon dioxid; Separation of albumin; +Separation of globulin; Precipitants of milk proteids; Precipitation +by dialysis; Carbohydrates in milk; Dextrinoid body in milk; Amyloid +bodies in milk.</p> + +<p class="neg-indent"><i>Butter</i>, <a href="#Page_512">pp. 512-523</a>.—General +principles of analysis; Appearance of melted butter; Microscopic examination; +Refractive power; Estimation of water, fat, casein, ash and salt; +Volatile and soluble acids; Relative proportion of glycerids; +Saponification value; Reichert number; Reichert-Meissl method; +Elimination of sulfurous acid; Errors due to poor glass; Molecular +weight of butter; Substitutes for and adulterants of butter; Butter colors.</p> + +<p class="neg-indent"><i>Cheese and Koumiss</i>, +<a href="#Page_524">pp. 524-536</a>.—Composition of cheese; Manufacture +of cheese; Official methods of analysis; Process of Mueller; Separation +of fat from cheese; Filled cheese; Separation of nitrogenous bodies; +Preparation of koumiss; Determination of carbon dioxid; Acidity; +Estimation of alcohol; Proteids in koumiss; Separation by porous +porcelain; Separation by precipitation with alum; Separation with +mercury salts; Determination of water and ash; Composition of koumiss; +Authorities cited in Part Sixth.</p> + +<p class="f120 spa1"><b>PART SEVENTH.</b></p> +<p class="f110">MISCELLANEOUS AGRICULTURAL PRODUCTS.</p> + +<p class="neg-indent"><i>Cereals and Cereal Foods</i>, +<a href="#Page_541">pp. 541-545</a>.— Classification; General methods +of analysis; Composition and analysis of bread; Determination of alum +in bread; Chemical changes produced by baking.</p> + +<p class="neg-indent"><i>Fodders, Grasses, and Ensilage</i>, +<a href="#Page_545">pp. 545-547</a>.—General principles of analysis; +Organic acids in ensilage; Changes due to fermentation; Alcohol in +ensilage; Comparative values of dry fodder and ensilage.</p> + +<p class="neg-indent"><i>Flesh Products</i>, +<a href="#Page_547">pp. 547-555</a>.—Names of meats; Sampling; General +methods of analysis; Examination of nitrogenous bodies; Fractional +analysis of meats; Starch in meats; Detection of horse flesh.</p> + +<p class="neg-indent"><i>Methods of Digestion</i>, +<a href="#Page_555">pp. 555-564</a>.—Artificial digestion; Amylolytic +ferments; Aliphalytic ferments; Proteolytic ferments; Pepsin and +pancreatin; Digestion in pancreas extract; Artificial digestion of +cheese; Natural digestion; Digestibility of pentosans.</p> + +<p class="neg-indent"><i>Preserved Meats</i>, +<a href="#Page_565">pp. 565-566</a>.—Methods of examination; Estimation +of fat; Meat preservatives.</p> + +<p class="neg-indent"><i>Determination of Nutritive Values</i>, +<a href="#Page_566">pp. 566-576</a>.—Nutritive value of foods; +Comparative value of food constituents; Nutritive ratio; Calorimetric +analysis of foods; Combustion in oxygen; Bomb calorimeter; Manipulation +and calculation; Computing the calories of combustion; Calorimetric +equivalents; Distinction between butter and oleomargarin. +<span class="pagenum"><a id="Page_x"></a>[Pg x]</span></p> + +<p class="neg-indent"><i>Fruits, Melons and Vegetables</i>, +<a href="#Page_577">pp. 577-582</a>.— Preparation of samples; +Separation of carbohydrates; Examination of the fresh matter; +Examination of fruit and vegetable juices; Separation of pectin; +Determination of free acid; Composition of fruits; Composition of ash +of fruits; Dried fruits; Zinc in evaporated fruits; Composition of +melons.</p> + +<p class="neg-indent"><i>Tea and Coffee</i>, +<a href="#Page_582">pp. 582-588</a>.—Special points in analysis; +Estimation of caffein; Iodin method; Spencer’s method; Separation +of chlorophyll; Determination of proteid nitrogen; Carbohydrates of +coffee; Estimation of galactan; Revised factors for pentosans; Use of +roentgen rays.</p> + +<p class="neg-indent"><i>Tannins and Allied Bodies</i>, +<a href="#Page_588">pp. 588-596</a>.— Occurrence and composition; +Detection and estimation; Precipitation with metallic salts; The +gelatin method; The hide powder method; Permanganate gelatin method; +Permanganate hide powder method; Preparation of infusion.</p> + +<p class="neg-indent"><i>Tobacco</i>, <a href="#Page_596">pp. 596-610</a>.—Fermented +and unfermented tobacco; Acid and basic constituents; Composition of ash; +Composition of tobacco; Estimation of water; Estimation of nitric acid; +Estimation of sulfuric and hydrochloric acids; Estimation of oxalic, +malic and citric acids; Estimation of acetic acid; Estimation of pectic +acid; Estimation of tannic acid; Estimation of starch and sugar; +Estimation of ammonia; Estimation of nicotin; Polarization method of +Popovici; Estimation of amid nitrogen; Fractional extraction; Burning +qualities; Artificial smoker.</p> + +<p class="neg-indent"><i>Fermented Beverages</i>, +<a href="#Page_610">pp. 610-641</a>.— Description; Important +constituents; Specific gravity; Determination of alcohol; Distilling +apparatus; Specific gravity of the distillate; Hydrostatic plummet; +Calculating results; Table giving percentage of alcohol by weight +and volume; Determination of percentage of alcohol by means of vapor +temperature; Improved ebullioscope; Indirect determination of extract; +Determination of total acids; Determination in a vacuum; Estimation +of water; Total acidity; Volatile acids; Tartaric acid; Tartaric, +malic and succinic acids; Polarizing bodies in fermented beverages; +Reducing sugars; Polarization of wines and beers; Application of +analytical methods; Estimation of carbohydrates; Determination of +glycerol; Coloring matters; Determination of ash; Determination of +potash; Sulfurous acid; Salicylic acid; Detection of gum and dextrin; +Determination of nitrogen; Substitutes for hops; Bouquet of fermented +and distilled liquors; Authorities cited in Part Seventh; +<a href="#Page_645">Index</a>.</p> +</div> + +<hr class="chap x-ebookmaker-drop"> + +<div class="chapter"> +<p><span class="pagenum"><a id="Page_xi"></a>[Pg xi]</span></p> +<p class="f120"><b>ILLUSTRATIONS TO<br> VOLUME THIRD.</b></p> +</div> + +<table class="spb1"> + <tbody><tr> + <td class="tdr fs_90" colspan="6">Page.</td> + </tr><tr> + <td class="tdl">Figure</td> + <td class="tdr">1.</td> + <td class="tdl_wsp" colspan="3">Mill for grinding dry samples</td> + <td class="tdr"><a href="#FIG_1">7</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">2.</td> + <td class="tdl_wsp" colspan="3">Comminutor for green samples</td> + <td class="tdr"><a href="#FIG_2">9</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">3.</td> + <td class="tdl_wsp" colspan="3">Rasp for sugar beets</td> + <td class="tdr"><a href="#FIG_3">10</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">4.</td> + <td class="tdl_wsp" colspan="3">Dreef grinding apparatus</td> + <td class="tdr"><a href="#FIG_4">11</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">5.</td> + <td class="tdl_wsp" colspan="3">Water jacket drying oven</td> + <td class="tdr"><a href="#FIG_5">14</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">6.</td> + <td class="tdl_wsp" colspan="3">Thermostat for Steam-Bath</td> + <td class="tdr"><a href="#FIG_6">15</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">7.</td> + <td class="tdl_wsp" colspan="3">Spencer’s drying oven</td> + <td class="tdr"><a href="#FIG_7">17</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">8.</td> + <td class="tdl_wsp" colspan="3">Electric vacuum drying oven</td> + <td class="tdr"><a href="#FIG_8">19</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">9.</td> + <td class="tdl_wsp" colspan="3">Steam coil drying oven</td> + <td class="tdr"><a href="#FIG_9">21</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">10.</td> + <td class="tdl_wsp" colspan="3">Carr’s vacuum drying oven</td> + <td class="tdr"><a href="#FIG_10A">22</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">10.</td> + <td class="tdl_wsp" colspan="3">(Bis.) vacuum oven open</td> + <td class="tdr"><a href="#FIG_10B">23</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">11.</td> + <td class="tdl_wsp" colspan="3">Apparatus for drying in a current of hydrogen</td> + <td class="tdr"><a href="#FIG_11">25</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">12.</td> + <td class="tdl_wsp" colspan="3">Caldwell’s hydrogen drying apparatus</td> + <td class="tdr"><a href="#FIG_12">27</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">13.</td> + <td class="tdl_wsp" colspan="3">Liebig’s ente</td> + <td class="tdr"><a href="#FIG_13">28</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">14.</td> + <td class="tdl_wsp" colspan="3">Drying apparatus used at the Halle Station</td> + <td class="tdr"><a href="#FIG_14">29</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">15.</td> + <td class="tdl_wsp" colspan="3">Wrampelmayer’s oven</td> + <td class="tdr"><a href="#FIG_15">30</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">16.</td> + <td class="tdl_wsp" colspan="3">Ulsch drying oven</td> + <td class="tdr"><a href="#FIG_16">31</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">17.</td> + <td class="tdl_wsp" colspan="3">Courtoune muffle</td> + <td class="tdr"><a href="#FIG_17">39</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">18.</td> + <td class="tdl_wsp" colspan="3">Knorr’s extraction apparatus</td> + <td class="tdr"><a href="#FIG_18">45</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">19.</td> + <td class="tdl_wsp" colspan="3">Extraction flask</td> + <td class="tdr"><a href="#FIG_19">46</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">20.</td> + <td class="tdl_wsp" colspan="3">Extraction tube</td> + <td class="tdr"><a href="#FIG_20">46</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">21.</td> + <td class="tdl_wsp" colspan="3">Extraction siphon tube</td> + <td class="tdr"><a href="#FIG_21">46</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">22.</td> + <td class="tdl_wsp" colspan="3">Soxhlet extraction apparatus</td> + <td class="tdr"><a href="#FIG_22">48</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">23.</td> + <td class="tdl_wsp" colspan="3">Compact condensing apparatus</td> + <td class="tdr"><a href="#FIG_23">49</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">24.</td> + <td class="tdl_wsp" colspan="3">Improved compact extraction apparatus</td> + <td class="tdr"><a href="#FIG_24">51</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">25.</td> + <td class="tdl_wsp" colspan="3">Knorr’s apparatus for recovering solvents</td> + <td class="tdr"><a href="#FIG_25">54</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">26.</td> + <td class="tdl_wsp" colspan="3">Apparatus for recovering solvents from open dishes</td> + <td class="tdr"><a href="#FIG_26">55</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">27.</td> + <td class="tdl_wsp" colspan="3">Common forms of pyknometers</td> + <td class="tdr"><a href="#FIG_27">63</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">28.</td> + <td class="tdl_wsp" colspan="3">Bath for pyknometers</td> + <td class="tdr"><a href="#FIG_28">66</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">29.</td> + <td class="tdl_wsp" colspan="3">Aereometers, pyknometers and hydrostatic balance</td> + <td class="tdr"><a href="#FIG_29">68</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">30.</td> + <td class="tdl_wsp" colspan="3">Hydrostatic balance</td> + <td class="tdr"><a href="#FIG_30">69</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">31.</td> + <td class="tdl_wsp" colspan="3">Course of rays of light in a nicol</td> + <td class="tdr"><a href="#FIG_31">77</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">32.</td> + <td class="tdl_wsp" colspan="3">Theory of the nicol</td> + <td class="tdr"><a href="#FIG_32">78</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">33.</td> + <td class="tdl_wsp" colspan="3">Laurent lamp</td> + <td class="tdr"><a href="#FIG_33">83</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">34.</td> + <td class="tdl_wsp" colspan="3">Lamp for producing constant monochromatic flame</td> + <td class="tdr"><a href="#FIG_34">85</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">35.</td> + <td class="tdl_wsp" colspan="3">Field of vision of a Laurent polariscope</td> + <td class="tdr"><a href="#FIG_35">86</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">36.</td> + <td class="tdl_wsp" colspan="3">Laurent polariscope</td> + <td class="tdr"><a href="#FIG_36">88</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">37.</td> + <td class="tdl_wsp" colspan="3">Tint polariscope</td> + <td class="tdr"><a href="#FIG_37">89</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">38.</td> + <td class="tdl_wsp" colspan="3">Double compensating shadow polariscope</td> + <td class="tdr"><a href="#FIG_38">91</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">39.</td> + <td class="tdl_wsp" colspan="3">Triple shadow polariscope</td> + <td class="tdr"><a href="#FIG_39">92</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">40.</td> + <td class="tdl_wsp" colspan="3">Apparatus for producing a triple shadow</td> + <td class="tdr"><a href="#FIG_40">92</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">41.</td> + <td class="tdl_wsp" colspan="3">Control observation tube</td> + <td class="tdr"><a href="#FIG_41">95</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">42.</td> + <td class="tdl_wsp" colspan="3">Apparatus for the volumetric estimation</td> + <td class="tdr"> </td> + </tr><tr> + <td class="tdc"> </td> + <td class="tdr"> </td> + <td class="tdl_ws2" colspan="3">of reducing sugars</td> + <td class="tdr"><a href="#FIG_42">131</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">43.</td> + <td class="tdl_wsp" colspan="3">Apparatus for the electrolytic deposition of copper</td> + <td class="tdr"><a href="#FIG_43">151</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">44.</td> + <td class="tdl_wsp" colspan="3">Apparatus for filtering copper suboxid</td> + <td class="tdr"><a href="#FIG_44">154</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">45.</td> + <td class="tdl_wsp" colspan="3">Apparatus for reducing copper suboxid</td> + <td class="tdr"><a href="#FIG_45">154</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">46.</td> + <td class="tdl_wsp" colspan="3">Distilling apparatus for pentoses</td> + <td class="tdr"><a href="#FIG_46">179</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">47.</td> + <td class="tdl_wsp" colspan="3">Autoclave for starch analysis</td> + <td class="tdr"><a href="#FIG_47A">199</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">47.</td> + <td class="tdl_wsp bb" colspan="3">(Bis). Maercker’s hydrolyzing apparatus for starch</td> + <td class="tdr bb"><a href="#FIG_47B">204</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">48.</td> + <td class="tdl_ws2"><a href="#FIG_48">Maranta starch</a></td> + <td class="tdl">× 350</td> + <td class="tdl bb" rowspan="14">to face</td> + <td class="tdr bb" rowspan="14">220</td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">49.</td> + <td class="tdl_ws2"><a href="#FIG_49">Potato starch</a></td> + <td class="tdl">× 350</td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">50.</td> + <td class="tdl_ws2"><a href="#FIG_50">Ginger starch</a></td> + <td class="tdl">× 350</td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">51.</td> + <td class="tdl_ws2"><a href="#FIG_51">Sago starch</a></td> + <td class="tdl">× 350</td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">52.</td> + <td class="tdl_ws2"><a href="#FIG_52">Pea starch</a></td> + <td class="tdl">× 350</td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">53.</td> + <td class="tdl_ws2"><a href="#FIG_53">Bean starch</a></td> + <td class="tdl">× 350</td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">54.</td> + <td class="tdl_ws2"><a href="#FIG_54">Wheat starch</a></td> + <td class="tdl">× 350</td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">55.</td> + <td class="tdl_ws2"><a href="#FIG_55">Barley starch</a></td> + <td class="tdl">× 350</td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">56.</td> + <td class="tdl_ws2"><a href="#FIG_56">Rye starch</a></td> + <td class="tdl">× 350</td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">57.</td> + <td class="tdl_ws2"><a href="#FIG_57">Oat starch</a></td> + <td class="tdl">× 350</td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">58.</td> + <td class="tdl_ws2"><a href="#FIG_58">Indian corn starch</a></td> + <td class="tdl">× 350</td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">59.</td> + <td class="tdl_ws2"><a href="#FIG_59">Rice starch</a></td> + <td class="tdl">× 350</td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">60.</td> + <td class="tdl_ws2"><a href="#FIG_60">Cassava starch</a></td> + <td class="tdl">× 150</td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">61.</td> + <td class="tdl_ws2 bb"><a href="#FIG_61">Indian corn starch</a></td> + <td class="tdl bb">× 150 + <span class="pagenum"><a id="Page_xii"></a>[Pg xii]</span></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">62.</td> + <td class="tdl_wsp" colspan="3">Laboratory cane mill</td> + <td class="tdr"><a href="#FIG_62">230</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">63.</td> + <td class="tdl_wsp" colspan="3">Weighing pipette</td> + <td class="tdr"><a href="#FIG_63">231</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">64.</td> + <td class="tdl_wsp" colspan="3">Gird’s gravimeter</td> + <td class="tdr"><a href="#FIG_64">233</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">65.</td> + <td class="tdl_wsp" colspan="3">Machine for cutting canes</td> + <td class="tdr"><a href="#FIG_65">236</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">66.</td> + <td class="tdl_wsp" colspan="3">Cane cutting mill</td> + <td class="tdr"><a href="#FIG_66">237</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">67.</td> + <td class="tdl_wsp" colspan="3">Apparatus for pulping beets</td> + <td class="tdr"><a href="#FIG_67">243</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">68.</td> + <td class="tdl_wsp" colspan="3">Apparatus for cold diffusion</td> + <td class="tdr"><a href="#FIG_68">245</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">69.</td> + <td class="tdl_wsp" colspan="3">Sickel-Soxhlet extractor</td> + <td class="tdr"><a href="#FIG_69">247</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">70.</td> + <td class="tdl_wsp" colspan="3">Scheibler’s extraction tube</td> + <td class="tdr"><a href="#FIG_70">248</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">71.</td> + <td class="tdl_wsp" colspan="3">Battery for alcoholic digestion</td> + <td class="tdr"><a href="#FIG_71">250</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">72.</td> + <td class="tdl_wsp" colspan="3">Rasp for sampling mother beets</td> + <td class="tdr"><a href="#FIG_72">251</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">73.</td> + <td class="tdl_wsp" colspan="3">Hand press for beet analysis</td> + <td class="tdr"><a href="#FIG_73">251</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">74.</td> + <td class="tdl_wsp" colspan="3">Perforating rasp</td> + <td class="tdr"><a href="#FIG_74">252</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">75.</td> + <td class="tdl_wsp" colspan="3">Tube for continuous observation</td> + <td class="tdr"><a href="#FIG_75A">253</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">75.</td> + <td class="tdl_wsp" colspan="3">(Bis). Chandler and Rickett’s Polariscope</td> + <td class="tdr"><a href="#FIG_75B">266</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">76.</td> + <td class="tdl_wsp" colspan="3">Apparatus for polarimetric observations</td> + <td class="tdr"> </td> + </tr><tr> + <td class="tdc"> </td> + <td class="tdr"> </td> + <td class="tdl_ws2" colspan="3">at low temperatures</td> + <td class="tdr"><a href="#FIG_76">267</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">77.</td> + <td class="tdl_wsp" colspan="3">Construction of desiccating tube</td> + <td class="tdr"><a href="#FIG_77">268</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">78.</td> + <td class="tdl_wsp" colspan="3">Apparatus for polarizing at high temperatures</td> + <td class="tdr"><a href="#FIG_78">269</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">79.</td> + <td class="tdl_wsp" colspan="3">Oil press</td> + <td class="tdr"><a href="#FIG_79">312</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">80.</td> + <td class="tdl_wsp" colspan="3">Apparatus for fractional distillation</td> + <td class="tdr"> </td> + </tr><tr> + <td class="tdc"> </td> + <td class="tdr"> </td> + <td class="tdl_ws2" colspan="3">of petroleum ether</td> + <td class="tdr"><a href="#FIG_80">314</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">81.</td> + <td class="tdl_wsp" colspan="3">Section showing construction of a funnel</td> + <td class="tdr"> </td> + </tr><tr> + <td class="tdc"> </td> + <td class="tdr"> </td> + <td class="tdl_ws2" colspan="3">for hot filtration</td> + <td class="tdr"><a href="#FIG_81">316</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">82.</td> + <td class="tdl_wsp" colspan="3">Balance and Westphal sinker</td> + <td class="tdr"><a href="#FIG_82">318</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">83.</td> + <td class="tdl_wsp" colspan="3">Melting point tubes</td> + <td class="tdr"><a href="#FIG_83">322</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">84.</td> + <td class="tdl_wsp" colspan="3">Apparatus for the determination of melting point</td> + <td class="tdr"><a href="#FIG_84">324</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">85.</td> + <td class="tdl_wsp" colspan="3">Apparatus for determining crystallizing point</td> + <td class="tdr"><a href="#FIG_85">327</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">86.</td> + <td class="tdl_wsp" colspan="3">Abbe’s refractometer</td> + <td class="tdr"><a href="#FIG_86">329</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">87.</td> + <td class="tdl_wsp" colspan="3">Charging position of refractometer</td> + <td class="tdr"><a href="#FIG_87">330</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">88.</td> + <td class="tdl_wsp" colspan="3">Prism of Pulfrich’s refractometer</td> + <td class="tdr"><a href="#FIG_88">331</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">89.</td> + <td class="tdl_wsp" colspan="3">Pulfrich’s new refractometer</td> + <td class="tdr"><a href="#FIG_89">332</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">90.</td> + <td class="tdl_wsp" colspan="3">Heating apparatus for Pulfrich’s refractometer</td> + <td class="tdr"><a href="#FIG_90">333</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">91.</td> + <td class="tdl_wsp" colspan="3">Spectrometer attachment</td> + <td class="tdr"><a href="#FIG_91">333</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">92.</td> + <td class="tdl_wsp" colspan="3">Oleorefractometer</td> + <td class="tdr"><a href="#FIG_92">335</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">93.</td> + <td class="tdl_wsp" colspan="3">Section showing construction of oleorefractometer</td> + <td class="tdr"><a href="#FIG_93">335</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">94.</td> + <td class="tdl_wsp" colspan="3">Butyrorefractometer</td> + <td class="tdr"><a href="#FIG_94">339</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">95.</td> + <td class="tdl_wsp bb" colspan="3">Doolittle’s viscosimeter</td> + <td class="tdr bb"><a href="#FIG_95">343</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">96.</td> + <td class="tdl_ws2"><a href="#FIG_96">Lard crystals</a></td> + <td class="tdl">× 65</td> + <td class="tdl bb" rowspan="2">to face</td> + <td class="tdr bb" rowspan="2">348</td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">97.</td> + <td class="tdl_ws2 bb"><a href="#FIG_97">Refined lard crystals</a></td> + <td class="tdl bb">× 65</td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">98.</td> + <td class="tdl_wsp" colspan="3">Apparatus for determining rise of temperature</td> + <td class="tdr"> </td> + </tr><tr> + <td class="tdc"> </td> + <td class="tdr"> </td> + <td class="tdl_ws2" colspan="3">with sulfuric acid</td> + <td class="tdr"><a href="#FIG_98">358</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">99.</td> + <td class="tdl_wsp" colspan="3">Apparatus for determining heat of bromination</td> + <td class="tdr"><a href="#FIG_99">362</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">100.</td> + <td class="tdl_wsp" colspan="3">Olein tube</td> + <td class="tdr"><a href="#FIG_100">374</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">101.</td> + <td class="tdl_wsp" colspan="3">Apparatus for saponifying under pressure</td> + <td class="tdr"><a href="#FIG_101">380</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">102.</td> + <td class="tdl_wsp" colspan="3">Apparatus for the distillation of volatile acids</td> + <td class="tdr"><a href="#FIG_102">388</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">103.</td> + <td class="tdl_wsp" colspan="3">Apparatus for amid nitrogen</td> + <td class="tdr"><a href="#FIG_103">425</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">104.</td> + <td class="tdl_wsp" colspan="3">Sachsse’s eudiometer</td> + <td class="tdr"><a href="#FIG_104">425</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">105.</td> + <td class="tdl_wsp" colspan="3">Dialyzing apparatus</td> + <td class="tdr"><a href="#FIG_105">447</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">106.</td> + <td class="tdl_wsp" colspan="3">Scovell’s milk sampling tube</td> + <td class="tdr"><a href="#FIG_106">470</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">107.</td> + <td class="tdl_wsp" colspan="3">Lactoscope, lactometer, and creamometer</td> + <td class="tdr"><a href="#FIG_107">474</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">108.</td> + <td class="tdl_wsp" colspan="3">Areometric fat apparatus</td> + <td class="tdr"><a href="#FIG_108">493</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">109.</td> + <td class="tdl_wsp" colspan="3">Babcock’s butyrometer and acid measure</td> + <td class="tdr"><a href="#FIG_109">500</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">110.</td> + <td class="tdl_wsp" colspan="3">Gerber’s butyrometers</td> + <td class="tdr"><a href="#FIG_110">502</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">111.</td> + <td class="tdl_wsp" colspan="3">Gerber’s centrifugal</td> + <td class="tdr"><a href="#FIG_111">503</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">112.</td> + <td class="tdl_wsp" colspan="3">Thermometer for butyrorefractometer</td> + <td class="tdr"><a href="#FIG_112">515</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">113.</td> + <td class="tdl_wsp" colspan="3">Apparatus for determining carbon dioxid in koumiss</td> + <td class="tdr"><a href="#FIG_113">533</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">114.</td> + <td class="tdl_wsp" colspan="3">Cuts of mutton</td> + <td class="tdr"><a href="#FIG_114">548</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">115.</td> + <td class="tdl_wsp" colspan="3">Cuts of beef</td> + <td class="tdr"><a href="#FIG_115">548</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">116.</td> + <td class="tdl_wsp" colspan="3">Cuts of pork</td> + <td class="tdr"><a href="#FIG_116">548</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">117.</td> + <td class="tdl_wsp" colspan="3">Bath for artificial digestion</td> + <td class="tdr"><a href="#FIG_117">559</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">118.</td> + <td class="tdl_wsp" colspan="3">Bag for collecting feces</td> + <td class="tdr"><a href="#FIG_118">563</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">119.</td> + <td class="tdl_wsp" colspan="3">Fecal bag attachment</td> + <td class="tdr"><a href="#FIG_119">563</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">120.</td> + <td class="tdl_wsp" colspan="3">Hempel and Atwater’s calorimeter</td> + <td class="tdr"><a href="#FIG_120">570</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">121.</td> + <td class="tdl_wsp" colspan="3">Apparatus for acetic acid</td> + <td class="tdr"><a href="#FIG_121">603</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">122.</td> + <td class="tdl_wsp" colspan="3">Apparatus for smoking</td> + <td class="tdr"><a href="#FIG_122">610</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">123.</td> + <td class="tdl_wsp" colspan="3">Metal distilling apparatus</td> + <td class="tdr"><a href="#FIG_123">613</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">124.</td> + <td class="tdl_wsp" colspan="3">Distilling apparatus</td> + <td class="tdr"><a href="#FIG_124">614</a></td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdr">125.</td> + <td class="tdl_wsp" colspan="3">Improved ebullioscope</td> + <td class="tdr"><a href="#FIG_125">623</a></td> + </tr> + </tbody> +</table> + +<hr class="chap x-ebookmaker-drop"> + +<div class="chapter"> +<p><span class="pagenum"><a id="Page_1"></a>[Pg 1]</span></p> +<p class="f150"><b>VOLUME THIRD.</b></p> +<p class="f120"><b>AGRICULTURAL PRODUCTS.</b></p> +<hr class="chap x-ebookmaker-drop"> + +<h2 class="nobreak">PART FIRST.<br> +<span class="h_subtitle">SAMPLING, DRYING, INCINERATION<br>AND EXTRACTIONS.</span></h2> +</div> + +<p><b>1. Introduction.</b>—The analyst may approach the examination of +agricultural products from various directions. In the first place +he may desire to know their proximate and ultimate constitution +irrespective of their relations to the soil or to the food of man and +beast. Secondly, his study of these products may have reference solely +to the determination of the more valuable plant foods which they have +extracted from the soil and air. Lastly, he may approach his task from +a hygienic or economic standpoint for the purposes of determining the +wholesomeness or the nutritive and economic values of the products +of the field, orchard, or garden. In each case the object of the investigation +will have a considerable influence on the method of the examination.</p> + +<p>It will be the purpose of the present volume to discuss fully the +principles of all the standard processes of analysis and the best +practice thereof, to the end that the investigator or analyst, whatever +may be the design of his work, may find satisfactory directions for +prosecuting it. As in the previous volumes, it should be understood +that these pages are written largely for the teacher and the analyst +already skilled in the principles of analytical chemistry. Much is +therefore left to the individual judgment and experience of the worker, +to whom it is hoped a judicious choice of approved processes may be +made possible.</p> + +<p><b>2. Scope Of the Work.</b>—Under the term agricultural products +is included a large number of classes of bodies of most different +constitution. In general they are the products of vegetable and animal +<span class="pagenum"><a id="Page_2"></a>[Pg 2]</span> +metabolism. First of all come the vegetable products, fruits, grains +and grasses. These may be presented in their natural state, as cereals, +green fruits and fodders, or after a certain preparation, as starches, +sugars and flours. They may also be met with in even more advanced +stages of change, as cooked foods, alcohols and secondary organic +acids, such as vinegar. In general, by the term agricultural products +is meant not only the direct products of the farm, orchard and forest, +but also the modified products thereof and the results of manufacture +applied to the raw materials. Thus, not only the grain and straw of +wheat are proper materials for agricultural analysis, but also flour +and bran, bread and cakes made therefrom. In the case of maize and +barley, the manufactured products may extend much further, for not only +do we find starch and malt, but also alcohol and beer falling within +the scope of our work. In respect of animal products, the agricultural +analyst may be called on to investigate the subject of leather and +tanning; to determine the composition of meat, milk and butter; to +pass upon the character of lard, oleomargarine, and, in general, to +determine as fully as possible the course of animal food in all its +changes between the field, the packing house and the kitchen.</p> + +<p><b>3. Limitations of Work.</b>—It is evident from the preceding +paragraph, that in order to keep the magnitude of this volume within +the limits fixed for a single volume the text must be rigidly confined +to the fundamental principles and practice of agricultural analysis. +The interesting region of pharmacy and allied branches, in respect of +plant analysis, can find no description here, and in those branches +of technical chemistry, where the materials of elaboration are the +products of the field only a superficial view can be given. The main +purpose and motive of this volume must relate closely to the more +purely agricultural processes.</p> + +<p><b>4. General Manipulations.</b>—There are certain analytical +operations which are more or less of a general nature, that is, they +are of general application without reference to the character of the +material at hand. Among these may be mentioned the determination of +<span class="pagenum"><a id="Page_3"></a>[Pg 3]</span> +moisture and of ash, and the estimation of matters soluble in ether, +alcohol and other solvents. These processes will be first described. +Preliminary to these analytical steps it is of the utmost importance +that the material be properly prepared for examination. In general, +this is accomplished by drying the samples until they can be ground +or crushed to a fine powder, the attrition being continued until +all the particles are made to pass a sieve of a given fineness. The +best sieve for this purpose is one having circular apertures half a +millimeter in diameter. Some products, both vegetable and animal, +require to be reduced to as fine a state as possible without drying. +In such instances, passing the product through a sieve is obviously +impracticable. Special grinding and disintegrating machines are made +for these purposes and they will be described further on.</p> + +<p>There are some agricultural products which have to be prepared for +examination in special ways and these methods will be given in +connection with the processes for analyzing the bodies referred +to. Nearly all the bodies, however, with which the analyst will be +concerned, can be prepared for examination by the general methods about +to be described.</p> + +<p id="P_5"><b>5. Preparation of the Sample.</b> (<i>a</i>) <i>Vegetable +Substances.</i>—For all processes of analysis not executed on the +fresh sample, substances of a vegetable nature should, if in a fresh +state, be dried as rapidly as possible to prevent fermentative changes. +It is often of interest to determine the percentage of moisture in +the fresh sample. For this purpose a representative portion of the +sample should be rapidly reduced to as fine a condition as possible. +To accomplish this it should be passed through a shredding machine, +or cut by scissors or a knife into fine pieces. A few grams of the +shredded material are dried in a flat-bottomed dish at progressively +increasing temperatures, beginning at about 60° and ending at from 100° +to 110°. The latter temperature should be continued for only a short +time. The principle of this process is based upon the fact that if the +temperature be raised too high at first, some of the moisture in the +interior cells of the vegetable substance can be occluded by the too +rapid desiccation of the exterior layers which would take place at a +high temperature. The special processes for determining moisture will +be given in another place. +<span class="pagenum"><a id="Page_4"></a>[Pg 4]</span></p> + +<p>The rest of the sample should be partly dried at a lower temperature +or air-dried. In the case of fodders and most cattle foods the samples +come to the analyst in a naturally air-dried state. When grasses are +harvested at a time near their maturity they are sun-dried in the +meadows before placing in the stack or barn. Such sun-dried samples are +already in a state fit for grinding. Green grasses and fodders should +be dried in the sun, or in a bath at a low temperature from 50° to +60° until all danger of fermentative action is over, and then air- or +sun-dried in the usual way.</p> + +<p>Seeds and cereals usually reach the analyst in a condition suited to +grinding without further preliminary preparation. Fruits and vegetables +present greater difficulties. Containing larger quantities of water, +and often considerable amounts of sugar, they are dried with greater +difficulty. The principles which should guide all processes of drying +are those already mentioned, <i>viz.</i>, to secure a sufficient degree +of desiccation to permit of fine grinding and at a temperature high +enough to prevent fermentative action, and yet not sufficiently high to +cause any marked changes in the constituents of the vegetable organism.</p> + +<p>(<i>b</i>) <i>Animal Substances.</i>—The difficulties connected with +the preliminary treatment of animal substances are far greater than +those just mentioned. Such samples are composed of widely differing +tissues, blood, bone, tendon, muscle and adipose matters, and all the +complex components of the animal organism are to be considered. The +whole animal may be presented for analysis, in which case the different +parts composing it should be separated and weighed as exactly as +possible. Where only definite parts are to be examined it is best to +separate the muscle, bone, and fat as well as may be, before attempting +to reduce the whole to a fine powder. The soft portions of the sample +are to be ground as finely as possible in a meat or sausage cutter. +The bones are crushed in some appropriate manner, and thus prepared +for further examination. Where the flesh and softer portions are to be +dried and finely ground, the presence of fat often renders the process +almost impossible. In such cases the fat must be at least partially +<span class="pagenum"><a id="Page_5"></a>[Pg 5]</span> +removed by petroleum or other solvent. In practically fat-free samples +the material, after grinding in a meat cutter, can be partially dried +at low temperatures from 60° to 75°, and afterwards ground in much the +same manner as is practiced with vegetable substances.</p> + +<p>As is the case with the preliminary treatment of vegetable matters, +it is impossible to give any general directions of universal +applicability. The tact and experience of the analyst in all these +cases are better than any dicta of the books. In some instances, as +will appear further on, definite directions for given substances can be +given, but in all cases the general principles of procedure are on the +lines already indicated.</p> + +<p><b>6. Preserving Samples.</b>—In most cases, as is indicated in the +foregoing paragraphs, the sample may be dried before grinding to such a +degree as to prevent danger from fermentation or decay. The fine-ground +samples are usually preserved in glass-stoppered bottles, carefully +marked or numbered. In some cases it is advisable to sterilize the +bottles after stoppering, by subjecting them to a temperature of 100° +for some time. In the case of cereals assurance should be had that the +samples do not contain the eggs of any of the pests that often destroy +these products. As a rule, samples should be kept for a time after the +completion of the analytical work, and this is especially true in all +cases where there is any prospect of dispute or litigation. In general +it may be said, that samples should be destroyed only when they are +spoiled, or when storage room is exhausted.</p> + +<p><b>7. Collecting Samples.</b>—When possible, the analyst should be +his own collector. There is often as much danger from data obtained +on non-representative samples as from imperfect manipulation. When +personal supervision is not possible, the sample when received, +should be accompanied by an intelligible description of the method of +taking it, and of what it represents. In all cases the object of the +examination must be kept steadily in view. Where comparisons are to be +made the methods of collecting must be rigidly the same.</p> + +<p>The processes of analysis, as conducted with agricultural products, are +tedious and difficult. The absolutely definite conditions that attend +the analysis of mineral substances, are mostly lacking. The simple +<span class="pagenum"><a id="Page_6"></a>[Pg 6]</span> +determinations of carbon, hydrogen, nitrogen and sulfur, which are +required in the usual processes of organic analysis, are simplicity +itself when compared with the operations which have to be performed +on agricultural products to determine their character and their value +as food and raiment. We have to do here with matters on which the +sustenance, health and prosperity of the human race are more intimately +concerned than with any other of the sciences. This fact also +emphasizes the necessity for care in collecting the materials on which +the work is to be performed.</p> + +<p><b>8. Grinding Samples.</b>—In order to properly conduct the processes +of agricultural analysis it is important to have the sample finely +ground. This arises both from the fact that such a sample is apt +to contain an average content of the various complex substances of +which the material under examination is composed, and because the +analytical processes can be conducted with greater success upon the +finely divided matter. In mineral analysis it is customary to grind the +sample to an impalpable powder in an agate mortar. With agricultural +products, however, such a degree of fineness is difficult to attain, +and moreover, is not necessary. There is a great difference of opinion +among analysts respecting the degree of fineness desirable. In some +cases we must be content with a sample which will pass a sieve with a +millimeter mesh; in fact it may be found impossible, on account of the +stickiness of the material, to sift it at all. In such cases a thorough +trituration, so as to form a homogeneous mass will have to be accepted +as sufficient. Where bodies can be reduced to a powder however, it +is best to pass them through a sieve with circular perforations half +a millimeter in diameter. A finer degree of subdivision than this is +rarely necessary.</p> + +<p><b>9. The Grinding Apparatus.</b>—The simplest form of apparatus for +reducing samples for analysis to a condition suited to passing a fine +sieve is a mortar. Where only a few samples are to be prepared and in +small quantities, it will not be necessary to provide anything further. +After the sample is well disintegrated it is poured on the sieve and +all that can pass is shaken or brushed through. The sieve is provided +with a receptacle, into which it fits closely, to avoid loss of any +particles which may be reduced to a dust. The top of the sieve, when +<span class="pagenum"><a id="Page_7"></a>[Pg 7]</span> +shaken, may also be covered if there be any tendency to loss from dust. +Any residue failing to pass the sieve is returned to the mortar and +the process thus repeated until all the material has been secured in +the receiver. The particles more difficult of pulverization are often +different in structure from the more easily pulverized portions, and +the sifted matter must always be carefully mixed before the subsample +is taken for examination. Often the materials, or portions thereof, +will contain particles tough and resistant to the pestle, but the +operator must have patience and persistence, for it is highly necessary +to accurate work that the whole sample be reduced to proper size.</p> + +<div class="figcenter smcap"> + <img id="FIG_1" src="images/fig1.jpg" alt="" width="600" height="406" > + <p class="center spb1">Figure 1. Mill for Grinding Dry Samples.</p> +</div> + +<p>Where many samples are to be prepared, or in large quantities, mills +should take the place of mortars. For properly air-dried vegetable +substances, some form of mill used in grinding drugs may be employed. +Grinding surfaces of chilled corrugated steel are to be preferred. +The essential features of such a mill are that it be made of the best +material, properly tempered, and that the parts be easily separated +for convenience in cleaning. The grinding surfaces must also be so +constructed and adjusted as to secure the proper degree of fineness. In +<span class="pagenum"><a id="Page_8"></a>[Pg 8]</span> +<a href="#FIG_1">fig. 1</a> is shown a mill of rather simple construction, +which has long been in satisfactory use in this laboratory. Small mills may +be operated by hand power, but when they are to be used constantly +steam power should be provided. In addition to the removal of nearly +all the moisture by air-drying there are many oleaginous seeds which +cannot be finely ground until their oil has been removed. For this +purpose the grinding surfaces of the mill are opened so that the seeds +are only coarsely broken in passing through. The fragments are then +digested with light petroleum in a large flask, furnished with a reflux +condenser. After digestion the fragments are again passed through the +mill adjusted to break them into finer particles.</p> + +<p>The alternate grinding and digestion are thus continued until the +pulverization is complete. On a small specially prepared sample the +total content of oil is separately determined.</p> + +<p>Fresh animal tissues are best prepared for preliminary treatment by +passing through a sausage mill. The partially homogeneous mass thus +secured should be dried at a low temperature and reground as finely as +possible. Where much fat is present it may be necessary to extract it +as mentioned above, in the case of oleaginous seeds. In such cases both +the moisture and fat in the original material should be determined on +small specially prepared samples with as great accuracy as possible. +Bones, hoofs, horns, hair and hides present special difficulties in +preparation, which the analyst will have to overcome with such skill +and ingenuity as he may possess.</p> + +<p>The analyst will find many specially prepared animal foods already in +a fairly homogeneous form, such as potted and canned meats, infant +and invalid foods, and the like. Even with these substances, however, +a preliminary grinding and mixing will be found of advantage before +undertaking the analytical work. Many cases will arise which are +apparently entirely without the classification given above. But even in +such instances the analyst should not be without resources. Frequently +some dry inert substance may be mixed with the material in definite +quantities, whereby it is rendered more easily prepared. Perhaps no +case will be presented where persistent and judicious efforts to secure +a fairly homogeneous sample for analysis will be wholly unavailing. +<span class="pagenum"><a id="Page_9"></a>[Pg 9]</span></p> + +<div class="figcenter smcap"> + <img id="FIG_2" src="images/fig2.jpg" alt="" width="600" height="456" > + <p class="center spb1">Figure 2. Comminutor for Green Samples.</p> +</div> + +<p>In the case of green vegetable matters which require to be reduced +rapidly to a fine state of subdivision in order to secure even a fairly +good sample some special provision must be made. This is the case +with stalks of maize and sugar cane, root crops, such as potatoes and +beets, and green fodders, such as clover and grasses. The chopping of +these bodies into fine fodders by hand is slow and often impracticable. +The particles rapidly lose moisture and it is important to secure +them promptly as in the preparation of beet pulp for polarization. +For general use we have found the apparatus shown in <a href="#FIG_2">fig. 2</a> +quite satisfactory in this laboratory. It consists of a series of staggered +circular saws carried on an axis and geared to be driven at a high +velocity, in the case mentioned, 1,400 revolutions per minute. The +green material is fed against the revolving saws by the toothed +gear-work shown, and is thus reduced to a very fine pulp, which is +received in the box below. Stalks of maize, green fodders, sugar canes, +beets and other fresh vegetable matters are by this process reduced +to a fine homogeneous pulp, suited for sampling and for analytical +<span class="pagenum"><a id="Page_10"></a>[Pg 10]</span> +operations. Such pulped material can also be spread in a fine layer +and dried rapidly at a low temperature, thus avoiding danger of +fermentative changes when it is desired to secure the materials in a +dry condition or to preserve them for future examination. Samples of +sorghum cane, thus pulped and dried, have been preserved for many years +with their sugar content unchanged.</p> + +<div class="figcenter smcap"> + <img id="FIG_3" src="images/fig3.jpg" alt="" width="400" height="378" > + <p class="center spb1">Figure 3. Rasp for Sugar Beets.</p> +</div> + +<p>Such a machine is also useful in preparing vegetable matter for the +separation of its juices in presses. Samples of sugar cane, sugar +beets, apples and other bodies of like nature can thus be prepared to +secure their juices for chemical examination. Such an apparatus we +have found is fully as useful and indispensable in an agricultural +laboratory as a drug mill for air-dried materials.</p> + +<p>It is often desirable in the preparation of roots for sugar analysis +to secure them in a completely disintegrated state, that is with the +cellular tissues practically all broken. Such a pulped material can +be treated with water and the sugar juices it contains thus at once +distributed to all parts of the liquid mass. The operation is known +as instantaneous diffusion. The pulp of the vegetable matter is thus +introduced into the measuring flask along with the juices and the +content of sugar can be easily determined. Several forms of apparatus +have been devised for this purpose, one of which is shown in <a href="#FIG_3">fig. 3</a>. +This process, originally devised by Pellet, has come into quite general +<span class="pagenum"><a id="Page_11"></a>[Pg 11]</span> +use in the determination of the sugar content of +beets.<a id="FNanchor_1" href="#Footnote_1" class="fnanchor">[1]</a> +It is observed that it can be applied to other tubers, such as the +turnip, potato, artichoke, etc. It is desirable, therefore, that an +agricultural laboratory be equipped with at least three kinds of +grinding machines; <i>viz.</i>, first, the common drug mill used for +grinding seeds, air-dried fodders, and the like; second, a pulping +machine like the system of staggered saws above described for the +purpose of reducing green vegetable matter to a fine state of +subdivision, or one like the pellet rasp for tubers; third, a mill for +general use such as is employed for making sausages from soft animal tissues.</p> + +<div class="figcenter smcap"> + <img id="FIG_4" src="images/fig4.jpg" alt="" width="400" height="410" > + <p class="center spb1">Figure 4. Dreef Grinding Apparatus.</p> +</div> + +<p><b>10. Grinding Apparatus at Halle Station.</b>—The machine used at +the Halle station for grinding samples for analysis is shown in +<a href="#FIG_4">Fig. 4</a>.<a id="FNanchor_2" href="#Footnote_2" class="fnanchor">[2]</a> +It is so adjusted as to have both the upper and lower grinding +surfaces in motion. The power is transmitted through the pulley D, +which is fixed to an axis carrying also the inner grinding attachment +B. Through C₂, C₃, C₄, and C₁, the reverse motion is transmitted to +the outer grinder A. By means of the lever E the two grinding surfaces +can be separated when the mill is to be cleaned. The dree mill above +described is especially useful for grinding malt, dry brewers’ grains, +cereals for starch determinations and similar dry bodies. It is not +<span class="pagenum"><a id="Page_12"></a>[Pg 12]</span> +suited to grinding oily seeds and moist samples. These, according to +the Halle methods, are rubbed up in a mortar until of a size suited to +analysis, and samples such as moist residues, wet cereals, mashes, beet +cuttings, silage, etc., are dried before grinding. If it be desired to +avoid the loss of acids which may have been formed during fermentation, +about ten grams of magnesia should be thoroughly incorporated with each +kilogram of the material before drying.</p> + +<p><b>11. Preliminary Treatment of Fish.</b>—The method used by Atwater +in preparing fish for analysis is given below.<a id="FNanchor_3" href="#Footnote_3" class="fnanchor">[3]</a> +The same process may also be found applicable in the preparation of +other animal tissues. The specimens, when received at the laboratory, +are at once weighed. The flesh is then separated from the refuse and +both are weighed. There is always a slight loss in the separation, +due to evaporation and to slimy and fatty matters and small fragments +of the tissues which adhere to the hands and the utensils employed in +preparing the sample. Perfect separation of the flesh from the other +parts of the fish is difficult, but the loss resulting from imperfect +separation is small. The skin of the fish, although it has considerable +nutritive value, should be separated with the other refuse.</p> + +<p>The partial drying of the flesh for securing samples for analytical +work is accomplished by chopping it as finely as possible and +subjecting from fifty to one hundred grams of it for a day to a +temperature of 96° in an atmosphere of hydrogen. After cooling and +allowing to stand in the open air for twelve hours, the sample is again +weighed, and then ground to a fine powder and made to pass a sieve +with a half millimeter mesh. If the samples be very fat they cannot +be ground to pass so fine a sieve. In such a case a coarser sieve may +be used or the sample reduced to as fine and homogeneous a state as +possible, and bottled without sifting.</p> + +<p>The reason for drying in hydrogen is to prevent oxidation of the fats. +As will be seen further on, however, such bodies can be quickly and +accurately dried at low temperatures in a vacuum, and thus all danger +of oxidation be avoided. In fact, the preliminary drying of all animal +and vegetable tissues, where oxidation is to be feared, can be safely +accomplished in a partial vacuum by methods to be described in another +<span class="pagenum"><a id="Page_13"></a>[Pg 13]</span> +place. In order to be able to calculate the data of the analysis to the +original fresh state of the substance, a portion of the fresh material +should have its water quantitively determined as accurately as possible.</p> + +<h3>DRYING ORGANIC BODIES.</h3> + +<p><b>12. Volatile Bodies.</b>—In agricultural analysis it becomes +necessary to determine the percentage of bodies present in any given +sample which is volatile at any fixed temperature. The temperature +reached by boiling water is the one which is usually selected. It +is true that this temperature varies with the altitude and within +somewhat narrow limits at the same altitude, due to variations in +barometric pressure. As the air pressure to which any given body is +subjected, however, is a factor in the determination of its volatile +contents, it will be seen that within the altitudes at which chemical +laboratories are found, the variations in volatile content will not +be important. This arises from the fact that while water boils at a +lower temperature, as the height above the sea level increases, the +corresponding diminished air pressure permits a more ready escape of +volatile matter. As a consequence, a body dried to constant weight at +sea level, where the temperature of boiling water is 100°, will show +the same percentage of volatile matter as if dried at an altitude where +water boils at 99°. When, therefore, it is desirable to determine the +volatile matter in a sample approximately at 100°, it is better to +direct that it be done in a space surrounded by steam at the natural +pressure rather than at exactly 100°, a temperature somewhat difficult +to constantly maintain. However, where it is directed or desired to +dry to constant weight exactly at 100°, it can be accomplished by +means of an air-bath or by a water-jacketed-bath under pressure, or to +which enough solid matter is added to raise the boiling-point to 100°. +It is not often, however, that it is worth while to make any special +efforts to secure a temperature of 100°. When bodies are to be dried at +temperatures above 100°, such as 105°, 110°, and so on, an air-bath is +the most convenient means of securing the desired end. The different +kinds of apparatus to be employed will be described in succeeding paragraphs.</p> + +<p><b>13. Drying at the Temperature of Boiling Water.</b>—The best +<span class="pagenum"><a id="Page_14"></a>[Pg 14]</span> +apparatus for this process is so constructed as to have an interior +space entirely surrounded with boiling water or steam, with the +exception of the door by which entrance is gained thereto. The metal +parts of the apparatus are constructed of copper, and to keep a +constant level of water and avoid the danger of evaporating all the +liquid, it is advisable to have a reflux condenser attached to the +apparatus. It is also well to secure entrance to the interior drying +oven, not only by the door, but also by small circular openings, which +serve both to hold a thermometer and to permit of the aspiration of a +slow stream of dry air through the apparatus during the progress of +desiccation. The gaseous bodies formed by the volatilization of the +water and other matters are thus carried out of the drying box and the +process thereby accelerated. The bath should be heated by a burner so +arranged as to distribute the flame as evenly as possible over the +base. A single lamp, while it will boil the water in the center, will +not keep it at the boiling-point on the sides. The temperature of the +interior of the bath will not therefore reach 100°. The interior of the +oven should be coated with a non-detachable carbon paint to promote +the radiation of the heat from its walls, as well as to protect the +parts from oxidation where acid fumes are produced during desiccation. +Instead of a reflux condenser a constant water level may be maintained +in the bath by means of a mariotte bottle or other similar device.</p> + +<div class="figcenter smcap"> + <img id="FIG_5" src="images/fig5.jpg" alt="" width="400" height="599" > + <p class="center spb1">Figure 5. Water-jacketed Drying Oven.</p> +</div> + +<p><span class="pagenum"><a id="Page_15"></a>[Pg 15]</span> +When a bath of this kind is arranged for use with a partial vacuum, it +should be made cylindrical in shape, with conical ends, as shown in +<a href="#FIG_5">fig. 5</a>, in order to bear well the pressure to +which it is subjected. Among the many forms of steam-baths offered, +the analyst will have but little difficulty in selecting one suited to +his work. To avoid radiation the exterior of the apparatus should be +covered with a non-conducting material.</p> + +<div class="figcenter smcap"> + <img id="FIG_6" src="images/fig6.jpg" alt="" width="600" height="455" > + <p class="center spb1">Figure 6. Thermostat for Steam-Bath.</p> +</div> + +<p><b>14. Drying In a Closed Water Oven.</b>—When it is desired to keep +the temperature of a drying oven exactly at 100° instead of at the +heat of boiling water, a closed water oven with a thermostat is to +be employed. The oven should be so constructed as to secure a free +circulation of the water about the inner space. Since as a rule the +water between the walls of the apparatus will be subjected to a slight +pressure, these walls should be made strong, or the cylindrical form +of apparatus should be used. The thermostat used by the Halle Station +is shown in <a href="#FIG_6">Fig. 6</a>.<a id="FNanchor_4" href="#Footnote_4" class="fnanchor">[4]</a> +A <b>⋃</b> shaped tube, with a bulb on one arm and a lateral smaller +tube sealed on the other, is partly filled with mercury and connected +by rubber tubes on the right with the gas supply, and on the left with +the burner. The end carrying the bulb is connected + +<span class="pagenum"><a id="Page_16"></a>[Pg 16]</span> +directly by a rubber and metal tube with the water space of the oven. +This device is provided with a valve which is left open until the +temperature of the drying space reaches about 95°. The tube conducting +the gas is held in the long arm of the <b>⋃</b> by means of a cork +through which it passes air-tight and yet is loose enough to permit of +its being moved. Its lower end is provided with a long ▲ shaped slit. +When the valve leading to the water space is closed and the water +reaches the boiling point, the pressure of the vapor depresses the +mercury in the bulb arm of the <b>⋃</b> and raises it in the other. As +the mercury rises it closes the wider opening of the ▲ shaped slit, +thus diminishing the flow of gas to the burner. By moving the gas entry +tube up or down a position is easily found in which the temperature of +the drying space, as shown by the thermometer, is kept accurately and +constantly at 100°.</p> + +<p>In a bath arranged in this way a steam condenser is not necessary. +Since, however, in laboratories which are not at a higher altitude than +1,000 feet the boiling-point of water is nearly 100°, it does not seem +necessary to go to so much trouble to secure the exact temperature +named. There could be no practical difference in the percentage of +moisture determined at 100°, and at the boiling-point of water at a +temperature not more than 1° lower.</p> + +<p><b>15. Drying in an Air-Bath.</b>—In drying a substance in a medium of +hot air surrounded by steam, as has been described, the process is, in +reality, one of drying in air. The apparatus usually meant by the term +air-bath, however, has its drying space heated directly by a lamp, or +indirectly by a stratum of hot air occupying the place of steam in the +oven already described. The simplest form of the apparatus is a metal +box, usually copper, heated from below by a lamp. In the jacketed forms +the currents of hot air produced directly or indirectly by the lamp +are conducted around the inner drying oven, thus securing a more even +temperature. The bodies to be dried are held on perforated metal or +asbestos shelves in appropriate dishes, and the temperature to which +they are subjected is determined by a thermometer, the bulb of which is +brought as near as possible to the contents of the dish. One advantage +<span class="pagenum"><a id="Page_17"></a>[Pg 17]</span> +of the air-bath is in being able to secure almost any desired +temperature from that of the room to one of 150° or even higher. Its +chief disadvantage lies in the difficulty of securing and maintaining +an even temperature throughout all parts of the apparatus. Radiation +from the sides of the drying oven should be prevented by a covering of +asbestos or other non-combustible and non-conducting substance. The +burner employed should be a broad one and give as even a distribution +of the heat as possible over the bottom of the apparatus.</p> + +<div class="figcenter smcap"> + <img id="FIG_7" src="images/fig7.jpg" alt="" width="500" height="417" > + <p class="center spb1">Figure 7. Spencer’s Drying Oven.</p> +</div> + +<p><b>16. Spencer’s Air-Drying Oven.</b>—In order to secure an even +distribution of the heat in the desiccating space of the oven, Spencer +has devised an apparatus, <a href="#FIG_7">shown in the figure</a>, in which +the temperature is maintained evenly throughout the apparatus by means of a +fan.<a id="FNanchor_5" href="#Footnote_5" class="fnanchor">[5]</a> +The oven has a double bottom, the space between the two bottoms being +filled with air. The sides are also double, the space between being +filled with plaster. The fan is driven by a toy engine connected with +<span class="pagenum"><a id="Page_18"></a>[Pg 18]</span> +the compressed air service or other convenient method. Thermometers +placed in different parts of the apparatus, while in use, show a +rigidly even heat at all points so long as the fan is kept in motion. +The actual temperature desired can be controlled by a gas regulator. +This form of apparatus is well suited to drying a large number of +samples at once. Portions of liquids and viscous masses may also be +dried by enclosing them in bulbs and connecting with a vacuum.</p> + +<p>Spencer’s oven can also be used to advantage in drying viscous +liquids in a partial vacuum. For this purpose the flask A, <a href="#FIG_7">Fig. 7</a>, +containing the substance is made with a round bottom to resist the +atmospheric pressure. Its capacity is conveniently from 150 to 200 +cubic centimeters. It is closed with a rubber stopper carrying a trap, +H Hʹ, to keep the evaporated water from falling back. The details of +the construction of the trap H are shown at the right of the <a href="#FIG_7">figure</a>. +The vapors enter at the lateral orifice, just above the bulb, while the +condensed water falls back into the bulb instead of into the flask A. A +series of flasks can be used at once connected through the stopcocks +G with the circular tube E leading to the vacuum. A water pump easily +exhausts the apparatus, maintaining a vacuum of about twenty-seven +inches. The hot air in the oven is kept in motion by the fan B, thus +ensuring an even temperature in every part. The flask A may be partly +filled with sand or pumice stone before the addition of the samples +to be dried, and the weight of water lost is determined by weighing +A before and after desiccation. If it be desired to introduce a slow +current of dry air or some inert gas into A, it is easily accomplished +by passing a small tube, connected with the dry air or gas supply, +through the rubber stopper and extending it into the flask as far as +possible without coming into contact with the contents.</p> + +<p><b>17. Drying Under Diminished Air Pressure.</b>—The temperature at +which any given body loses its volatile products is conditioned largely +by the pressure to which it is subjected. At an air pressure of 760 +millimeters of mercury, water boils at 100° but it is volatilized at +all temperatures. As the pressure diminishes the temperature at which a +body loses water at a given rate falls. This is a fact of importance to +be considered in drying many agricultural products. This is especially +<span class="pagenum"><a id="Page_19"></a>[Pg 19]</span> +true of those containing oils and sugars, nearly the whole number. +Invert sugar especially is apt to suffer profound changes at a +temperature of 100°, the levulose it contains undergoing partial +decomposition. Oils are prone to oxidation and partial decomposition at +high temperatures in the presence of oxygen.</p> + +<p>In drying in a partial vacuum therefore a double advantage is secured, +that of a lower temperature of desiccation and in presence of less +oxygen. It is not necessary to have a complete vacuum. There are few +organic products which cannot be completely deprived of their volatile +matters at a temperature of from 70° to 80° in a partial vacuum in +which the air pressure has been diminished to about one-quarter of its +normal force.</p> + +<div class="figcenter smcap"> + <img id="FIG_8" src="images/fig8.jpg" alt="" width="500" height="483" > + <p class="center spb1">Figure 8. Electric Vacuum Drying Oven.</p> +</div> + +<p><b>18. Electric Drying-Bath.</b>—The heat of an electric current can +be conveniently used for drying in a partial vacuum by means of the +<span class="pagenum"><a id="Page_20"></a>[Pg 20]</span> +simple device illustrated in <a href="#FIG_8">Fig. 8</a>. In ordering +a heater of this kind the voltage of the current should be stated. The +current in use in this laboratory has a voltage of about 120, and is +installed on the three wire principle. It is well to use a rheostat +with the heater in order to control the temperature within the bell +jar. The ground rim of the bell jar rests on a rubber disk placed on a +thick ground glass or a metal plate, making an air-tight connection. A +disk of asbestos serves to separate the heater from the dish containing +the sample, in order to avoid too high a temperature.</p> + +<p><b>19. Steam Coil Apparatus.</b>—For drying at the temperature of +superheated steam, it is convenient to use an apparatus furnished with +layers or coils of steam pipes. The drying may be accomplished either +in the air or in a vacuum. In this laboratory a large drying oven, +having three shelves of brass steam-tubes and sides of non-conducting +material, is employed with great advantage. The series of heating +pipes is so arranged as to be used one at a time or collectively. Each +series is furnished with a separate steam valve, and is provided with +a trap to control the escape of the condensed vapors. In the bottom of +the apparatus are apertures through which air can enter, which after +passing through the interior of the oven escapes through a ventilator +at the top. With a pressure of forty pounds of steam to the square inch +and a free circulation of air, the temperature on the first shelf of +the apparatus is about 98°; on the second from 103° to 104°, and on +the third about 100°. The vessels containing the bodies to be dried +are not placed directly on the brass steam pipes, but the latter are +first covered with thick perforated paper or asbestos. For drying +large numbers of samples, or large quantities of one sample, such an +apparatus is almost indispensable to an agricultural laboratory.</p> + +<div class="figcenter smcap"> + <img id="FIG_9" src="images/fig9.jpg" alt="" width="400" height="601" > + <p class="center spb1">Figure 9. Steam Coil Drying Oven.</p> +</div> + +<p>A smaller apparatus is shown in <a href="#FIG_9">Fig. 9</a>. The heating part +G is made of a small brass tube arranged near the bottom in a horizontal coil and +continued about the sides in a perpendicular coil. Bodies placed on the +horizontal shelf are thus entirely surrounded by the heating surfaces +except at the top.<a id="FNanchor_6" href="#Footnote_6" class="fnanchor">[6]</a> +The steam pipe S is connected with the supply by the usual method, and +the escape of the condensation is controlled either by a valve or trap +<span class="pagenum"><a id="Page_21"></a>[Pg 21]</span> +in the usual way. The whole apparatus is covered by a bell jar B, +resting on a heavy cast-iron plate P, through which also the ends of +the brass coil pass. The upper surface of the iron plate may be planed, +or a planed groove may be cut into it, to secure the edge of the bell +jar. When the air is to be exhausted from the apparatus, a rubber +<span class="pagenum"><a id="Page_22"></a>[Pg 22]</span> +washer should be placed under the rim of the bell jar. The latter piece +of apparatus may either be closed, as shown in the <a href="#FIG_9">figure</a>, +by a rubber stopper, or it is better, though not shown, to have a stopper with +three holes. One tube passes just through the stopper and is connected +with the vacuum; the second passes to the bottom of the apparatus and +serves to introduce a slow stream of dry air or of an inert gas during +the desiccation. The third hole is for a thermometer. When no movement +of the residual gas in the apparatus is secured, a dish containing +strong sulfuric acid S’ is placed on the iron plate and under the +horizontal coil, as is shown in the <a href="#FIG_9">figure</a>. The sulfuric acid +so placed does not reach the boiling-point of water, and serves to absorb the +aqueous vapors from the residual air in the bell jar. By controlling +<span class="pagenum"><a id="Page_23"></a>[Pg 23]</span> +the steam supply the desiccation of a sample can be secured in +the apparatus at any desired temperature within the limit of the +temperature of steam at the pressure used. Where no steam service is at +hand a strong glass flask may be used as a boiler, in which case the +trap end of the coil must be left open. The vacuum may be supplied by +an air or bunsen pump. When a vacuum is not used an atmosphere of dry +hydrogen may be supplied through H.</p> + +<div class="figcenter smcap"> + <img id="FIG_10A" src="images/fig10.jpg" alt="" width="400" height="425" > + <p class="center spb1">Figure 10. Carr’s Vacuum Drying Oven.</p> + + <img id="FIG_10B" src="images/fig10_2.jpg" alt="" width="400" height="468" > + <p class="center spb1">Figure 10. (Bis) Vacuum Oven Open.</p> +</div> + +<p id="P_20"><b>20. Carr’s Vacuum Oven.</b>—A convenient drying oven has been +devised in this laboratory by Carr.<a id="FNanchor_7" href="#Footnote_7" class="fnanchor">[7]</a> +<span class="pagenum"><a id="Page_24"></a>[Pg 24]</span> +It is made of a large tube, preferably of brass. The tube may be from +six to nine inches in diameter and from twelve to fifteen inches long. +One end is closed air-tight by a brass end-piece attached by a screw, +or brazed. The other end is detachable and is made air-tight by ground +surfaces and a soft washer. In the <a href="#FIG_10A">figure</a> this +movable end-piece is shown attached by screw-nuts, but experience has +shown that these are not necessary. On the upper longitudinal surfaces +are apertures for the insertion of a vacuum gauge and for attachment to +a vacuum apparatus.</p> + +<p>In the <a href="#FIG_10A">figure</a> the thermometer and aperture +for introducing dry air or an inert gas are shown in the movable end +disk, but they would be more conveniently placed in the fixed end. The +oven is heated below by a gas burner, which conveniently should be as +long as the oven. The heat is not allowed to strike the brass cylinder +directly, but the latter is protected by a piece of asbestos paper.</p> + +<p>The temperature inside of the oven can be easily kept practically +constant by means of a gas regulator, not shown in the figure, or +by a little attention to the lamp. For a vacuum of twenty inches a +temperature of about 80° should be maintained. When the vacuum is more +complete a lower temperature can be employed. This apparatus is simple +in construction, strong, cheap, and highly satisfactory in use.</p> + +<p><b>21. Drying in Hydrogen.</b>—In some of the processes of +agricultural analysis it becomes important to dry the sample in +hydrogen or other inert gas. This may be accomplished by introducing +the dry gas desired into some form of the apparatus already described. +The drying may either be accomplished in an atmosphere of hydrogen +practically at rest or in a more limited quantity of the gas in motion. +The latter method is to be preferred by reason of its greater rapidity. +The analyst has at his command many forms of apparatus designed for the +purpose mentioned above. It will be sufficient here to describe only +two, devised particularly for agricultural purposes.</p> + +<p>The first one of these, designed by the author, was intended especially +for drying the samples of fodders for analysis according to the methods +of the Association of Agricultural +Chemists.<a id="FNanchor_8" href="#Footnote_8" class="fnanchor">[8]</a></p> + +<div class="figcenter smcap"> + <img id="FIG_11" src="images/fig11.jpg" alt="" width="500" height="478" > + <p class="center spb1">Figure 11. Apparatus for Drying in a<br> Current of Hydrogen.</p> +</div> + +<p>For the purpose of drying materials contained in flasks and tubes in a +<span class="pagenum"><a id="Page_25"></a>[Pg 25]</span> +current of hydrogen the apparatus shown in <a href="#FIG_11">Fig. 11</a> is +used. This apparatus consists of a circular box, B, conveniently made of +galvanized iron, having a movable cover, S, fitted for the introduction +of steam into the interior of the apparatus. Condensed steam escapes at +W. A stream of perfectly pure and dry hydrogen enters at H, passes up +through the material to be dried, down through the bulb V, containing +sulfuric acid, and follows the direction of the arrows through the rest +of the apparatus. The stream of hydrogen is thus completely dried by +passing through bulbs containing sulfuric acid, on the way from one +<span class="pagenum"><a id="Page_26"></a>[Pg 26]</span> +piece of the apparatus to the other. A, represents a flask such as is +used, with the extraction apparatus described. The apparatus which we +have used will hold eight tubes or flasks at a time, and thus a single +stream of hydrogen is made to do duty eight times in drying eight +separate samples. The great advantage of the apparatus is in the fact +that the stream of hydrogen must pass over and through the substance +to be dried. In order to prevent any sulfuric acid from being carried +forward into the next tube the bulb K, above the sulfuric acid, may be +filled with solid pieces of soda or potash.</p> + +<p>This apparatus has been in use for a long time and no accidents from +sulfuric acid being carried forward have occurred, and there is no +danger, provided the stream of hydrogen is kept running at a slow +rate. If, however, by any accident the stream of hydrogen should be +admitted with great rapidity, particles of the sulfuric acid might be +carried forward and spoil the next sample. To avoid any such accident +as this the proposal to introduce the potash bulb has been made. The +apparatus works with perfect satisfaction, and it is believed that when +properly adjusted check weighings can be made by weighing the bulbs, +showing their increase in weight, which will give the volatile matter, +and weighing the flasks or tubes, which will show the loss of weight. +The only chance for error in weighing the bulbs is that some of the +volatile matter may be material which is not dissolved in sulfuric +acid, and is thus carried on and out of the apparatus. The blackening +of the sulfuric acid in the bulbs, in the drying of all forms of +organic matter, shows that the loss in weight of such bodies is not +due to water alone, but also to organic volatile substances, which are +capable of being decomposed by the sulfuric acid, thus blackening it.</p> + +<p><b>22. Caldwell’s Hydrogen Drying-Bath.</b>—An excellent device for +drying in hydrogen has been described by Caldwell.<a id="FNanchor_9" href="#Footnote_9" class="fnanchor">[9]</a> +A vessel of copper or other suitable material serves to hold the tubes +containing the samples to be dried. It should be about twenty-four +centimeters long, fifteen high, and eight wide. This vessel is +contained in another made of the same material and of the dimensions +shown in the <a href="#FIG_12">figure</a>. On one side the edge of this +<span class="pagenum"><a id="Page_27"></a>[Pg 27]</span> +containing vessel may not be more than one centimeter high and the bath +should rest against it. The other side is made higher to form a support +for the drying tubes as indicated.</p> + +<div class="figcenter smcap"> + <img id="FIG_12" src="images/fig12.jpg" alt="" width="400" height="441" > + <p class="center spb1">Figure 12. Caldwell’s Hydrogen Drying Apparatus.</p> +</div> + +<p>The tube containing the substance <i>a d</i> is made of glass and may +be closed by the ground stoppers <i>c b</i> or the tube stoppers <i>e +f</i>. At <i>a</i> it carries a perforated platinum disk for holding +the filtering felt. The tube should be about thirteen centimeters long +and have an internal diameter of about twenty millimeters. With its +stoppers it should weigh only a little over thirty grams. The asbestos +felt should not be thick enough to prevent the free passage of gas. +Passing diagonally through the bath are metal tubes, preferably made of +copper, and of such a size as just to receive the glass drying tubes. +If these be a little loose they should be made tight by wrapping them +with a narrow coil of paper at either end of the tubular receptacle. +The entrance of cold air between the glass tube and its metal holder is +thus prevented, and the glass tube is held firmly in position. The glass +<span class="pagenum"><a id="Page_28"></a>[Pg 28]</span> +tube should be weighed with its two solid stoppers. Afterwards the +sample, about two grams, is placed on the asbestos felt and the +stoppers replaced and the whole reweighed. The exact weight of the +sample is thus obtained. The solid stoppers are then removed and the +tube stoppers inserted. The lower end of the tube is then connected +with the supply of dry hydrogen. The upper tube stopper is connected +by a rubber tube with a small bottle containing sulfuric acid through +which the escaping hydrogen is made to bubble. A double purpose is thus +secured; moisture is kept from entering the drying tube and the rate +at which the hydrogen is passing is easily noted. After the drying is +completed the solid stoppers are again inserted, the tube cooled in a +desiccator and weighed. The loss of weight is entered as water. The +tube containing the sample can afterwards be put into an extractor and +treated with ether or petroleum in the manner hereafter described. This +apparatus requires more hydrogen than the one previously described, +but it is rather simple in construction, is easily controlled, and has +given satisfactory results.</p> + +<div class="figcenter smcap"> + <img id="FIG_13" src="images/fig13.jpg" alt="" width="400" height="204" > + <p class="center spb1">Figure 13. Liebig’s Ente.</p> +</div> + +<p><b>23. Drying in Liebig’s Tubes.</b>—In drying samples, especially of +fodders, the method practiced at the Halle Station is to place them +in drying tubes, the form of which is shown in <a href="#FIG_13">Fig. 13</a>. +A stream of illuminating gas, previously dried by passing over sulfuric acid and +calcium chlorid, is directed through the tubes.<a id="FNanchor_10" href="#Footnote_10" class="fnanchor">[10]</a> +Many of these tubes can be used at once, arranged as shown in <a href="#FIG_14">Fig. 14</a>. +When the air is all driven out the stream of gas can be ignited so as +to regulate the flow properly by the size of the flame. The tubes are +held in drying ovens, as shown in the <a href="#FIG_14">figure</a>, the temperature +of which should be kept at 105°-107°. The drying should be continued for eight +or ten hours. At the end of this time the gas in the tube is to be +expelled by a stream of dry air and the tubes cooled in a desiccator +and weighed. There are few advantages in this method not possessed by +the processes already described. The samples, moreover, are not left +in a condition for further examination, either by incineration or extraction. +<span class="pagenum"><a id="Page_29"></a>[Pg 29]</span></p> + +<div class="figcenter smcap"> + <img id="FIG_14" src="images/fig14.jpg" alt="" width="600" height="372" > + <p class="center spb1">Figure 14. Drying Apparatus used at the Halle Station.</p> +</div> + +<p><span class="pagenum"><a id="Page_30"></a>[Pg 30]</span> +<b>24. Wrampelmayer’s Drying Oven.</b>—The apparatus used at the +Wageningen Station, in Holland, for drying agricultural samples, +was devised by Wrampelmayer and is shown in <a href="#FIG_15">Fig. 15</a>. +The oven is so constructed as to permit of drying in a stream of inert gas. +Illuminating gas is let into the drying space of the oven through the +tube A B. At B the entering gas is heated by the same lamp which boils +the liquid in the water space of the apparatus. The hot gas is dried in +the calcium chlorid tube c and then passes into the oven at D. At E it +leaves the apparatus and is thence conducted to the lamp F, used for +heating the bath. The lamp should be closed by a wire gauze diaphragm +to prevent any possible explosion by reason of any admixture with the +air in the oven. The condensation of the aqueous vapors is effected by +means of the condenser G. In the drying space is a small shelf holder, +which, by means of the hook H, can be removed from the apparatus. The +drying space is closed from the upper part of the apparatus, which +contains no water by the cover J, resting on a support K. This rim is +covered with a rubber gasket L, by means of which the cover J can be +fastened with a bayonet latch air-tight. This fastening is shown at N. +Being closed in this way the part of the cylindrical oven above the +cover may be left entirely open. Instead of the rather elaborate method +of closing the bath, some simple and equally effective device might be +used. The cover J is best made with double metallic walls enclosing an +asbestos packing.</p> + +<div class="figcenter smcap"> + <img id="FIG_15" src="images/fig15.jpg" alt="" width="400" height="545" > + <p class="center spb1">Figure 15. Wrampelmayer’s Oven.</p> +</div> + +<p><span class="pagenum"><a id="Page_31"></a>[Pg 31]</span> +It is evident that this oven could be used with an atmosphere of carbon +dioxid or of air, provided the gas for heating were derived from a +separate source and the tube between E and F broken. In a drying oven +designed by the author, the movable top is made with double walls and +the space between is joined to the steam chamber by means of a flexible +metallic tube, thus entirely surrounding the drying space with steam.</p> + +<p><b>25. The Ulsch Drying Oven.</b>—A convenient drying oven is +described by Ulsch which varies from the ordinary form of a +water-jacketed drying apparatus in having a series of drying tubes +inserted in the water-steam space.</p> + +<div class="figcenter smcap"> + <img id="FIG_16" src="images/fig16.jpg" alt="" width="500" height="438" > + <p class="center spb1">Figure 16. Ulsch Drying Oven.</p> +</div> + +<p>The arrangement of the oven is shown in the accompanying <a href="#FIG_16">figure</a>. +The water space is filled only to about one-third of its height. When the +heat is applied the cock <i>c</i> is left open until the steam has +<span class="pagenum"><a id="Page_32"></a>[Pg 32]</span> +driven out all the air. It is then closed and the temperature of the +bath is then regulated by the manometer <i>e</i>, connected with the +bath by <i>d</i>. The bottom of the manometer cylinder contains enough +mercury to always keep sealed the end of the manometer tube. The rest +of the space is filled with water. At the top the manometer tube is +expanded into a small bulb which serves as a gas regulator, as shown +in the <a href="#FIG_16">figure</a>. The gas is admitted also by a +small hole above the mercury in the bulb, so that when the end of +the gas inlet tube is sealed enough gas still passes through to keep +the lamp burning. With a mercury pressure of thirty centimeters the +temperature of the bath will be about 105°. The walls of the bath +should be made strong enough to bear the pressure corresponding to this +degree. The drying can be accomplished either in the cubical drying +box <i>a</i> or in the drying tubes made of thin copper and disposed +as shown in the <a href="#FIG_16">figure</a>. The natural draft is +shown by the arrows. The substance is held in boats placed in the tube +as indicated. The air in traversing the tube is brought almost to +the temperature of the water-steam space in which the tube lies. The +natural current of hot air can easily be replaced by a stream of dry +illuminating or other inert gas.</p> + +<p id="P_26"><b>26. Drying Viscous Liquids.</b>—In the case of cane juices, milk, +and similar substances, the paper coil method may be used.<a id="FNanchor_11" href="#Footnote_11" class="fnanchor">[11]</a> +The manipulation is conducted as follows: A strip of filtering paper from +five to eight centimeters wide and forty centimeters in length, is +rolled into a loose coil and dried at the temperature of boiling water +for two hours, placed in a dry glass-stoppered weighing tube, cooled +in a desiccator and weighed. The stoppered weighing tube prevents the +absorption of hygroscopic moisture. About three cubic centimeters of +the viscous or semi-viscous liquid are placed in a flat dish covered +by a plate of thin glass and weighed. The coil is then placed on end +in the dish, and the greater part of the liquid is at once absorbed. +The proportions between the coil and the amount of liquid should be +such that the coil will not be saturated more than two-thirds of its +length. It is then removed and placed dry end down in a steam-bath +and dried two hours. The dish, covered by the same plate of glass, is +again weighed, the loss in weight representing the quantity of liquid +<span class="pagenum"><a id="Page_33"></a>[Pg 33]</span> +absorbed by the coil. After drying for the time specified the coil +is again placed in the hot weighing tube, cooled and its weight +ascertained. The increase represents the solid matter in the sample +taken. This method has been somewhat modified by Josse, who directs +that it be conducted as follows:<a id="FNanchor_12" href="#Footnote_12" class="fnanchor">[12]</a> +Filter-paper is cut into strips from one to two centimeters wide and +three meters long. The strips are crimped so they will not lie too +closely together and then wrapped into coils. These coils can absorb +about ten cubic centimeters of liquid. One of them is placed in a flat +dish about two centimeters high and seven in diameter, and dried as +described, covered, cooled and weighed. There are next placed in the +dish and weighed one or two grams of the massecuite, molasses, etc., +which are to be dried and the dish again weighed and the total weight +of the matter added, determined by deducting the weight of the dish and +cover. About eight cubic centimeters of water are added, the material +dissolved with gentle warming, the coil placed in the dish, and the +whole dried for two hours. The cover is then replaced and the whole +cooled in a desiccator and weighed. The increase in weight represents +the dry matter in the sample taken.</p> + +<p>The above method of solution of a viscous sample in order to divide +it evenly for desiccation is based on the principle of the method +first proposed by the author and Broadbent for drying honeys and other +viscous liquids.<a id="FNanchor_13" href="#Footnote_13" class="fnanchor">[13]</a> +In this process the sample of honey, molasses, or other viscous liquid +is weighed in a flat dish, dissolved in eighty per cent alcohol, and +then a weighed quantity of pure dry sand added, sufficient to fill +the dish three-quarters full. The alcoholic solution of the viscous +liquid is evenly distributed throughout the mass of sand by capillary +attraction, and thus easily and rapidly dried when placed on the bath.</p> + +<p>Pumice stone, on account of its great porosity, is also an excellent +medium for the distribution of a viscous liquid in aiding the process +of desiccation. The method has been worked out in great detail in +this laboratory by Carr and Sanborn,<a id="FNanchor_14" href="#Footnote_14" class="fnanchor">[14]</a> +and most excellent results obtained. Round aluminum dishes two +centimeters high and from eight to ten centimeters in diameter are +conveniently used for this process. The pumice stone is dried and +broken into fragments the size of a pea before use. +<span class="pagenum"><a id="Page_34"></a>[Pg 34]</span></p> + +<p><b>27. General Principles of Drying Samples.</b>—It would be a +needless waste of space to go into further details of devices for +desiccation. A sufficient number has been given to fully illustrate all +the principles involved. In general, it may be said that drying in the +open air at a temperature not exceeding that of boiling water can be +safely practiced with the majority of samples. For instance, we have +found practically no change in this laboratory in the composition of +cereals dried in the air and in an inert gas. The desiccation should +in all cases be accomplished as speedily as possible. To this end the +atmosphere in contact with the sample should be dry and kept in motion. +An oven surrounded by boiling water and steam is to be preferred to +one heated by air. Constancy of temperature is quite as important as +its degree and this steadiness is most easily secured by steam at +atmospheric pressure. Where higher temperatures than 100° are desired +the steam must be under pressure, or the boiling-point of the water may +be raised by adding salt or other soluble matters. A bath of paraffin +or calcium chlorid may also be used or a sand or air-bath may be +employed. The analyst must not forget, however, that inorganic matters +are prone to change at temperatures above 100°, even in an inert +atmosphere, and higher temperatures must be used with extreme caution.</p> + +<p>Drying in partial vacuum and in a slowly changing atmosphere may +be practiced with all bodies and must be employed with some. The +simple form of apparatus already described will be found useful for +this purpose. At a vacuum of twenty inches or more, even unstable +organic agricultural products are in little danger of oxidation. In +the introduction of a dry gas, therefore, air will be found as a +rule entirely satisfactory. In the smaller form of vacuum apparatus +described, however, there is no objection to the employment of hydrogen +or of carbon dioxid. The gas entering the apparatus should be dried by +passing over calcium chlorid or by bubbling through sulfuric acid. In +this laboratory the vacuum is provided by an air-pump connected with a +large exhaust cylinder. This cylinder is connected by a system of pipes +to all the working desks. The chief objection to this system is the +<span class="pagenum"><a id="Page_35"></a>[Pg 35]</span> +unsteadiness of the pressure. When only a few are using the vacuum +apparatus for filtering or other purposes the vacuum will stand at +about twenty inches. When no one is using it the vacuum will rise to +twenty-eight or twenty-nine inches. At other times, when in general +use, it may fall to fifteen inches. Where a constant vacuum is desired +for drying, therefore, it is advisable to connect the apparatus with a +special aspirator which will give a pressure practically constant.</p> + +<p>The dishes containing the sample should be low and flat, exposing as +large a surface as possible. For viscous liquids it will be found +advisable to previously fill the dishes with pumice stone or other +inert absorbent material to increase the surface exposed.</p> + +<p>The special methods of drying milk, sirup, honeys, and like bodies, +will be described in the paragraphs devoted to these substances.</p> + +<p>In drying agricultural products, not only water but all other matters +volatile at the temperature employed are expelled. It is only necessary +to conduct the products of volatilization through sulfuric acid to +demonstrate the fact that organic bodies are given off. In the case +mentioned the sulfuric acid will be speedily changed to a brown and +even black color by these bodies. It is incontestable, however, that +in most cases the essential oils and other volatile matters thus +escaping are not large in quantity and could not appreciably affect +the percentage composition of the sample. In such cases the whole of +the loss on drying is entered in the note book as water. There are +evidently many products, however, where a considerable percentage of +the volatile products is not water. The percentage of essential oils, +which have a lower boiling-point than water, can be determined in a +separate sample and this deducted from the total loss on drying will +give the water.</p> + +<p>Simple as it seems, the determination of water in agricultural products +often presents peculiar difficulties and taxes to the utmost the +patience and skill of the analyst. Having set forth the substantial +principles of the process and indicated its more important methods, +there is left for the worker in the laboratory the choice of processes +<span class="pagenum"><a id="Page_36"></a>[Pg 36]</span> +already described, or, in special cases, the device of new ones and +adaption of old ones to meet the requirements of necessity.</p> + +<h3>INCINERATION.</h3> + +<p id="P_28"><b>28. Determination of Ash.</b>—The principle to be kept in view in +the preparation of the ash of agricultural products is to conduct the +incineration at as low a temperature as possible to secure a complete +combustion. The danger of too high a temperature is two-fold. In the +first place some of the mineral constituents constantly present in the +ash, notably, some of the salts of potassium and sodium are volatile +at high temperatures and thus escape detection. In the second place, +some parts of the ash are rather easily fusible and in the melted state +occlude particles of unburned organic matter, and thus protect them +from complete oxidation. Both of these dangers are avoided, and an ash +practically free of carbon obtained, by conducting the combustion at +the lowest possible temperature capable of securing the oxidation of +the carbonaceous matter.</p> + +<p><b>29. Products Of Combustion.</b>—The most important product of +combustion, from the present point of view, is the mineral residue +obtained. The organic matter of the sample undergoes decomposition +in various ways, depending chiefly on its nature. Complex volatile +compounds are formed first largely of an acid nature. The residual +carbon is oxidized to carbon dioxid and the hydrogen to water. The +relative proportions of these bodies formed, in any given case, depend +on the conditions of combustion. With a low temperature and a slow +supply of oxygen, the proportion of volatile organic compounds is +increased. At a high temperature, and in a surplus of oxygen, the +proportions of water and carbon dioxid are greater. At the present +time, however, our attention is to be directed exclusively to the +mineral residue; the organic products of combustion belonging to the +domain of organic chemistry. As has already been intimated, the ash of +agricultural samples consists of the mineral matters derived from the +tissues, together with any accidental mineral impurities which may be +present, some unburned carbon, and the sulfur, phosphorus, chlorin, +nitrogen, etc., existing previously in combination with the mineral +bases. The organic sulfur and phosphorus may also undergo complete or +<span class="pagenum"><a id="Page_37"></a>[Pg 37]</span> +partial oxidation during incineration and be found in the ash. Unless +special precautions be taken, however, a portion of the organic +sulfur and phosphorus may escape as volatile compounds during the +combustion.<a id="FNanchor_15" href="#Footnote_15" class="fnanchor">[15]</a> +The organic nitrogen is probably completely lost, at most, only traces +of it being oxidized during the combustion in such a way as to combine +with a mineral base. The rare mineral elements that are taken up by +plants will also be found in the ash. Here the analyst would look for +copper, boron, zinc, manganese, and the other elements which, when +existing in the soil, are apt to be found in the tissues of the plants, +not, perhaps, as organic or essential compounds, but as concomitants +of the other mineral foods absorbed by growing vegetation. This fact +is often of importance in toxicological and hygienic examinations of +foods. For instance, traces of copper or of boron in the ash of a +prescribed food would not be evidence of the use of copper or borax +salts as preservatives unless it could be shown that the soil on which +the food in question was grown was free of these bodies.</p> + +<p>This fact manifestly applies only to those cases where mere traces +of these rare bodies are in question. The presence of considerable +quantities of them, enough to be inimical to health, could only be +attributed to artificial means.</p> + +<p><b>30. Purpose and Conduct of Incineration.</b>—In burning a sample +of an agricultural product the analyst may desire to secure either a +large sample of ash for analytical purposes as already described or to +determine the actual percentage of ash. The first purpose is secured +in many ways. In the preparation of ash for manurial purposes, for +instance, little care is exercised either to prevent volatilization of +mineral matters or to avoid the occurrence of a considerable quantity +of carbon in the sample. With this operation we have, at present, +nothing whatever to do. In preparing a sample of ash for chemical +analysis it is important, where a sufficient quantity of the sample can +be obtained, to use as large a quantity of it as convenient. While it +is true that very good results may be secured on very small samples, +it is always advisable to have a good supply of the material at hand. +Since the materials burned have only from one to three per cent of ash, +a kilogram of them will supply only from ten to thirty grams. To supply +<span class="pagenum"><a id="Page_38"></a>[Pg 38]</span> +all needful quantities of material and replace the losses due to +accident, whenever possible at least twenty grams of the ash should +be prepared. The combustion can be carried on in platinum dishes with +all bodies free of metallic oxids capable of injuring the platinum. +Otherwise porcelain or clay dishes may be employed. As a rule the +combustion is best conducted in a muffle at a low red heat. With +substances very rich in fusible ash, as for instance the cereals, it is +advisable to first char them, extract the greater part of the ash with +water, and afterwards burn the residual carbon. The aqueous extract can +then be added to the residue of combustion and evaporated to dryness at +the temperature of boiling water. During the combustion the contents +of the dish should not be disturbed until the carbon is as completely +burned out as possible. The naturally porous condition in which the +mass is left during the burning is best suited to the entire oxidation +of the carbon. At the end however, it may become necessary to bring +the superficial particles of unburned carbon into direct contact with +the bottom of the dish by stirring its contents. In most instances +very good results may be obtained by burning the ash in an open dish +without the aid of a muffle. In this case a lamp should be used with +diffuse flame covering as evenly as possible the bottom of the dish and +thus securing a uniform temperature. The carbon, when once in active +combustion, will as a rule be consumed, and an ash reasonably pure be +obtained.</p> + +<p>The second purpose held in view by the analyst is to determine the +actual content of ash in a sample. For this purpose only a small +quantity of the material should be used, generally from two to ten +grams. The combustion should be conducted in flat-bottomed, shallow +dishes, and at a low temperature. In many cases the residue, after +determining the moisture, can be at once subjected to incineration, +and thus an important saving of time be secured. A muffle, with gentle +draft, will be found most useful for securing a white ash. The term, +white ash, is sometimes a deceptive one. In samples containing iron or +manganese, the ash may be practically free of carbon and yet be highly +colored. The point at which the combustion is to be considered as +<span class="pagenum"><a id="Page_39"></a>[Pg 39]</span> +finished therefore should be at the time the carbon has disappeared +rather than when no coloration exists. In general the methods of +incineration are the same for all substances, but some cases may arise +in which special processes must be employed. Some analysts prefer to +saturate the substance before incineration with sulfuric acid, securing +thus a sulfated ash. This is practiced especially with molasses. In +such cases the ash obtained is free of carbon dioxid and roughly the +difference in weight is compensated for by deducting one-tenth of +the weight of the ash when comparison is to be made with ordinary +carbonated ash. Naturally this process could not be used when sulfuric +acid is to be determined in the product.</p> + +<div class="figleft smcap"> + <img id="FIG_17" src="images/fig17.jpg" alt="" width="200" height="329" > + <p class="center spb1">Figure 17. Courtoune Muffle.</p> +</div> + +<p><b>31. German Ash Method.</b>—The method pursued at the Halle Station +for securing the percentage of ash in a sample is as follows:<a id="FNanchor_16" href="#Footnote_16" class="fnanchor">[16]</a> +Five grams of the air-dried sample are incinerated in a platinum dish and +the ash ignited until it has assumed a white, or at least a bright +gray tint. As soon as combustible gases are emitted at the beginning +of the incineration they are ignited and allowed to burn as long as +possible. It is advisable to hasten the oxidation by stirring the mass +with a piece of platinum wire. If the ash should become agglomerated, +as sometimes happens with rich food materials, it must be separated by +attrition. The ash, when cooled on a desiccator, is to be weighed. When +great exactness is required, it is advised, as set forth in a former +<span class="pagenum"><a id="Page_40"></a>[Pg 40]</span> +paragraph, to first carbonize the mass and then extract the soluble +ash with hot water before completing the oxidation. When the latter is +complete and the dish cooled the aqueous extract is added, evaporated +to dryness and the incineration completed.</p> + +<p><b>32. Courtonne’s Muffle.</b>—The ordinary arrangement of a muffle, +as in assaying, may be conveniently used in incineration. A special +muffle arrangement has been prepared by Courtonne which not only +permits of the burning of a large number of samples at once, but also +effects a considerable saving in gas. The muffle as shown in <a href="#FIG_17">Fig. 17</a>, +is made in two stages, and the floor projects in front of the furnace, +forming a convenient hearth. The incineration is commenced on the upper +stage, where the temperature is low, and finished on the lower one at a +higher heat. The furnace is so arranged as to permit the flame of the +burning gas to entirely surround the muffle. The draft and temperature +within the muffle are controlled by the fire-clay door shown resting on +the table.</p> + +<h3>TREATMENT WITH SOLVENTS.</h3> + +<p id="P_33"><b>33. Object Of Treatment.</b>—The next step, in the analytical +work, after sampling, drying, and incinerating, is the treatment of +the sample with solvents. The object of this work is to separate +the material under examination into distinct classes of bodies +distinguished from each other by their solubilities. It is not the +purpose of this section to describe the various bodies which may +be separated in this way, especially from vegetable products. For +this description the reader may consult the standard works on plant +analysis.<a id="FNanchor_17" href="#Footnote_17" class="fnanchor">[17]</a></p> + +<p>The chief object of a strictly agricultural examination of a field or +garden product is to determine its food value. This purpose can be +accomplished without entering into a minute separation of nearly allied +bodies. For example, in the case of carbohydrates it will be sufficient +as a rule, to separate them into four classes. In the first class will +be found those soluble in water as the ordinary sugars. In the second +group will be found those which, while not easily soluble in water, are +readily rendered so by treatment with certain ferments or by hydrolysis +with an acid. The starches are types of this class. In the third place +<span class="pagenum"><a id="Page_41"></a>[Pg 41]</span> +are found those bodies which resist the usual processes of hydrolysis +either with an acid or alkali, and therefore remain in the residue as +fiber. Cellulose is a type of these bodies. In the fourth class are +included those bodies which on hydrolysis with an acid yield furfurol +on distillation, and therefore belong to the type containing five atoms +of carbon or some multiple thereof in their molecule. For ordinary +agricultural purpose the separation is not even as complete as is +represented above.</p> + +<p>What is true of the carbohydrates applies equally well to the fats and +to other groups. Especially in the analysis of cereals and of cattle +foods, the treatment with solvents is confined to the use in successive +order of ether or petroleum, alcohol, dilute acids, and alkalies, the +latter at a boiling temperature. The general method of treatment with +these solvents will be the subject of the following paragraphs.</p> + +<p><b>34. Extraction of the Fats and Oils.</b>—Two solvents are in +general use for the extraction of fats and oils; <i>viz.</i>, ethylic +ether and a light petroleum. The former is the more common reagent. +Before use it should be made as pure as possible by washing first +with water, afterwards removing the water by lime or calcium chlorid, +and then completing the drying by treatment with metallic sodium. +The petroleum spirit used should be purified by several fractional +distillations until it has nearly a constant boiling-point of from 45° +to 50°. The detailed methods of preparing these reagents will be given +in another place. For rigid scientific determinations the petroleum +is to be preferred to the ether. It is equally as good a solvent +for fats and oils and is almost inert in respect to other vegetable +constituents. Ether, on the other hand, dissolves chlorophyll and its +partial oxidation products, resins, alkaloids and the like. The extract +obtained by ether is therefore less likely to be a pure fat than that +secured by petroleum. For purposes of comparison, however, the ether +should be employed, inasmuch as it has been used almost exclusively in +analytical operations in the past.</p> + +<p><b>35. Methods Of Extraction.</b>—The simplest method for +accomplishing the extraction of fat from a sample consists in treating +<span class="pagenum"><a id="Page_42"></a>[Pg 42]</span> +it with successive portions of the solvent in an open dish or a closed +flask. This process is actually employed in some analytical operations, +as, for instance, in the determination of fat in milk. Experience has +shown, however, that a portion of the substance soluble, for instance, +in ether, passes very slowly into solution, so that a treatment such as +that just described would have to be long continued to secure maximum +results. The quantity of solvent required would thus become very large +and in the case of ether would entail a great expense. For the greater +number of analytical operations, therefore, some device is employed for +using the same solvent continually. The methods of extraction therefore +fall into two general classes; <i>viz.</i>, extraction by digestion +and extraction by percolation. This classification holds good also for +other solvents besides ether and petroleum. In general, the principles +and practice of extraction described for ether may serve equally well +for alcohol, acetone and other common solvents.</p> + +<p><b>36. Extraction by Digestion.</b>—In the use of ether or petroleum +the sample is covered with an excess of the solvent and allowed to +remain for some time in contact therewith. The soluble portions of the +sample diffuse into the reagent. The speed of diffusion is promoted +by stirring the mixtures. The operation may be conducted in an open +dish or a flask. Inasmuch as the residue is, as a rule, to be dried +and weighed, an open dish is to be preferred. To avoid loss of reagent +and to prevent filling a working room with very dangerous gases, the +temperature of digestion should be kept below the boiling-point of the +solvent. The greater part of the soluble matter will be extracted with +three or four successive applications of the reagent, but, as intimated +above, the last portions of the soluble material are extracted with +difficulty by this process. In pouring off the solvent care must be +exercised to avoid loss of particles of the sample suspended therein. +To this end it is best to pour the solvent through a filter. For the +extraction of large quantities of material for the purpose of securing +the extract for future examination, or simply to remove it, the +digestion process is usually employed. This excess of solvent required +is easily recovered by subsequent distillation and used again. The +method is rarely used for the quantitive estimation of the extract, the +<span class="pagenum"><a id="Page_43"></a>[Pg 43]</span> +process of continuous percolation being more convenient and more exact.</p> + +<p><b>37. Extraction by Percolation.</b>—In this method the solvent +employed is poured on the top of the material to be extracted and +allowed to pass through it usually by gravitation alone, sometimes with +the help of a filter-pump. The principle of the process is essentially +that of washing precipitates.</p> + +<p>Two distinct forms of apparatus are in use for this process. In +the first kind the solvent is poured over the material and after +percolation is secured by distillation in another apparatus. In the +second kind the solvent is secured after percolation in a flask where +it is at once subjected to distillation. The vapors of the solvent +are conducted by appropriate means to a condenser placed above the +sample. After condensation the solvent is returned to the upper part of +the sample. The percolation thus becomes continuous and a very small +quantity of the solvent may thus be made to extract a comparatively +large amount of material. This process is particularly applicable +to the quantitive determination of the extract. After distillation +and drying the latter may be weighed in the flask in which it was +received or the sample may be dried and weighed in the vessel in which +it is held both before and after extraction. One great advantage of +the continuous extraction method lies in the fact that when it is +once properly started it goes on without further attention from the +analyst save an occasional examination of the flow of water through +the condenser and of the rate of the distillation. For this reason the +process may be continued for many hours without any notable loss of +time. The vapor of the solvent in passing to the condenser may pass +through a tube out of contact with the material to be extracted or it +may pass directly around the tube holding the sample. In the former +case the advantage is secured of conducting the extraction at a higher +temperature, but there is danger of boiling the solvent in contact with +the material and thus permitting the loss of a portion of the sample.</p> + +<p><b>38. Apparatus Used for Extractions.</b>—For extraction by +digestion, as has already been said, an open dish may be used. When +large quantities of material are under treatment, heavy flasks, holding +<span class="pagenum"><a id="Page_44"></a>[Pg 44]</span> +from five to ten liters, will be found convenient. In these cases a +condenser can be attached to the flask and the extraction conducted +at the boiling temperature of the solvent. During the process of +extraction it is advisable to shake the flask frequently. By proceeding +in this way the greater part of the solvent matter will be removed +after three or four successive treatments.</p> + +<p>In extraction by percolation various forms of apparatus are employed. +The ordinary percolators of the manufacturing pharmacist may be used +for the larger operations, while the more elaborate forms of continuous +extractors will be found most convenient for quantitive work. In each +case the analyst must choose that process and form of apparatus best +suited to the purpose in view. In the next paragraphs will be described +some of the more common forms of apparatus in use.</p> + +<p id="P_39"><b>39. Knorr’s Extraction Apparatus.</b>—The apparatus which has been +chiefly used in this laboratory for the past few years is shown in +the accompanying <a href="#FIG_18">figure</a>.<a id="FNanchor_18" href="#Footnote_18" class="fnanchor">[18]</a> +The principle of the construction of the apparatus lies in the complete +suppression of stoppers and in sealing the only joint of the device +with mercury.</p> + +<p>The construction and operation of the apparatus will be understood by a +brief description of its parts.</p> + +<p>A is the flask containing the solvent, W a steam bath made by cutting +off the top of a bottle, inverting it and conducting the steam into one +of the tubes shown in the stopper while the condensed water runs out of +the other. The top of the bath is covered with a number of concentric +copper rings, so that the opening may be made of any desirable size. B +represents the condenser, which is a long glass tube on which a number +of bulbs has been blown, and which is attached to the hood for holding +the material to be extracted, as represented at Bʹ, making a solid +glass union. Before joining the tube at Bʹ the rubber stopper which is +to hold it into the outside condenser of B is slipped on, or the rubber +stopper may be cut into its center and slipped over the tube after the +union is made. In case alcohol is to be used for the solvent, requiring +a higher temperature, the flask holding the solvent is placed entirely +within the steam-bath, as represented at Aʹ. +<span class="pagenum"><a id="Page_45"></a>[Pg 45]</span></p> + +<div class="figcenter smcap"> + <img id="FIG_18" src="images/fig18.jpg" alt="" width="400" height="670" > + <p class="center spb1">Figure 18. Knorr’s Extraction Apparatus.</p> +</div> + +<p><span class="pagenum"><a id="Page_46"></a>[Pg 46]</span></p> + +<div class="figcenter smcap"> + <img id="FIG_19" src="images/fig19.jpg" alt="" width="600" height="316" > + <p class="center spb1">Figure 19. Extraction Flask.</p> +</div> + +<div class="figcontainer smcap"> + <div class="figsub"> + <img id="FIG_20" src="images/fig20.jpg" alt="" width="210" height="386" > + <p class="center">Figure 20.<br> Extraction Tube.</p> + </div> + <div class="figsub"> + <img id="FIG_21" src="images/fig21.jpg" alt="" width="200" height="383" > + <p class="center">Figure 21.<br> Extraction Siphon Tube.</p> + </div> +</div> + +<p>A more detailed description of the different parts of the apparatus +can be seen by consulting Figs. <a href="#FIG_19">19</a>, <a href="#FIG_20">20</a>, +and <a href="#FIG_21">21</a>. In A, <a href="#FIG_19">Fig. 19</a>, is +represented a section of the flask which holds the solvent, showing how +the sides of the hood containing the matters to be extracted pass over +<span class="pagenum"><a id="Page_47"></a>[Pg 47]</span> +the neck of the flask, and showing at S a small siphon inserted in the +space between the neck of the flask and the walls of the hood for the +purpose of removing any solvent that may accumulate in this space. +A view of the flask itself is shown at Aʹ. It is made by taking an +ordinary flask, softening it about the neck and pressing the neck in +so as to form a cup, as indicated at Aʹ, to hold the mercury which +seals the union of the flask with the condenser. The flask is held in +position by passing a rubber band below it, which is attached to two +glass nipples, <i>b</i>, blown onto the containing vessel, as shown in +<a href="#FIG_18">Fig. 18</a>. The material to be extracted may be contained in an ordinary +tube, as shown in <a href="#FIG_20">Fig. 20</a>, which may be made from a test tube drawn +out, as indicated in the figure, having a perforated platinum disk +sealed in at D. The containing tube rests upon the edges of the flask +containing the solvent by means of nipples shown at <i>t</i>. If a +siphon tube is to be used, one of the most convenient forms is shown in +<a href="#FIG_21">Fig. 21</a>, in which the siphon lies entirely within +the extracting tube, thus being protected from breakage. By means of +this apparatus the extractions can be carried on with a very small +quantity of solvent, there being scarcely any leakage, even with the +most volatile solvents, such as ether and petroleum. The apparatus is +always ready for use, no corks are to be extracted, and no ground glass +joints to be fitted.</p> + +<p id="P_40"><b>40. Soxhlet’s Extraction Apparatus.</b>—A form of continuous +extraction apparatus has been proposed by Soxhlet which permits the +passage of the vapors of the solvent into the condenser by a separate +tube and the return of the condensed solvent after having stood in +contact with the sample, to the evaporating flask by a siphon. The +advantage of this process lies in freeing the sample entirely from the +rise of temperature due to contact with the vapors of the solvent, and +in the second place in the complete saturation of the sample with the +solvent before siphoning. The sample is conveniently held in a cylinder +of extracted filter-paper open above and closed below. This is placed +in the large tube between the evaporating flask and the condenser. The +sample should not fill the paper holder, and if disposed to float in +the solvent, should be held down with a plug of asbestos fiber or of +glass wool. The extract may be transferred, by dissolving in the +<span class="pagenum"><a id="Page_48"></a>[Pg 48]</span> +solvent, from the flask to a drying dish, or it may be dried and +weighed in the flask where first received.</p> + +<div class="figleft smcap"> + <img id="FIG_22" src="images/fig22.jpg" alt="" width="100" height="411" > + <p class="center spb1">Figure 22.<br> Soxhlet<br> Extraction<br> Apparatus.</p> +</div> + +<p>There are many forms of apparatus of this kind, one of which is shown +in <a href="#FIG_22">Fig. 22</a>, but a more extended description of +them is not necessary. The disadvantages of this process as compared +with Knorr’s, are quite apparent. The connections with the evaporating +flask and condenser are made with cork stoppers, which must be +previously thoroughly extracted with ether and alcohol. These corks +soon become dry and hard and difficult to use. The joints are likely +to leak, and grave dangers of explosion arise from the vapors of the +solvents escaping into the working room. Moreover, it is an advantage +to have the sample warmed by the vapors of the solvent during the +progress of the extraction, provided the liquid in direct contact with +the sample does not boil with sufficient vigor to cause loss.</p> + +<p>The use of extraction apparatus with ground glass joints is also +unsatisfactory. By reason of unequal expansion and contraction these +joints often are not tight. They are also liable to break and thus +bring danger and loss of time.</p> + +<p><b>41. Compact Extraction Apparatus.</b>—In order to bring the +extraction apparatus into a more compact form, the following described +device has been successfully used in this laboratory.<a id="FNanchor_19" href="#Footnote_19" class="fnanchor">[19]</a> +The condenser employed is made of metal and is found entirely within +the tube holding the solvent.</p> + +<p>This form of condenser is shown in <a href="#FIG_23">Fig. 23</a>, in which +the tube E serves to introduce the cold water to the bottom of the condensing +device. The tube D serves to carry away the waste water. The tube F serves +for the introduction of the solvent by means of a small funnel. When +the solvent is introduced and has boiled for a short time, the tube +F should be closed. In each of the double conical sections of the +condenser a circular disk B is found, which causes the water flowing +from A upward to pass against the metallic surfaces of the condenser. +<span class="pagenum"><a id="Page_49"></a>[Pg 49]</span></p> + +<p>A section of the double conical condenser is shown in the upper right +hand corner. It is provided with two small hooks <i>hh</i>, soldered on +the lower surface, by means of which the crucible G can be hung with a +platinum wire. The condenser is best made smooth and circular in form.</p> + +<p>The crucible G, which holds the material to be extracted, can be made +of platinum, but for sake of economy also of porcelain. The bottom +of the porcelain crucible is left open excepting a small shelf, as +indicated, which supports a perforated disk of platinum on which an +asbestos film is placed.</p> + +<div class="figcenter smcap"> + <img id="FIG_23" src="images/fig23.jpg" alt="" width="400" height="643" > + <p class="center spb1">Figure 23. Compact Condensing Apparatus.</p> +</div> + +<p>The whole apparatus is of such size as to be easily contained in the +large test-tube T.</p> + +<p><span class="pagenum"><a id="Page_50"></a>[Pg 50]</span> +The mouth of the test-tube is ground so as to fit as smoothly as +possible to the ground-brass plate of the metallic condenser P.</p> + +<p>In case it is desired to weigh the extract it may be done directly by +weighing it in the test-tube T after drying in the usual way at the +end of the extraction; or a glass flask H, made to fit freely into the +test-tube, may be used, in which case a little mercury is poured into +the bottom of the tube to seal the space between H and T. To prevent +spirting of the substance in H, or projecting any of the extracted +material without or against the bottom of the crucible G, the funnel +represented by the dotted lines in the right hand section may be used.</p> + +<p>Heat may be applied to the test-tube either by hot water, or steam, or +by a bunsen, which permits of the flame being turned down to minimum +proportions without danger of burning back. When the test-tube alone +is used it is advisable to first put into it some fragments of pumice +stone, particles of platinum foil, or a spoonful of shot, to prevent +bumping of the liquid when the lamp is used as the source of heat.</p> + +<p>Any air which the apparatus contains is pushed out through F when the +boiling begins, the tube F not being closed until the vapor of the +liquid has reached its maximum height. With cold water in the condenser +the vapor of ether very rarely reaches above the lower compartment and +the vapor of alcohol rarely above the second.</p> + +<p>When the plate P is accurately turned so as to fit the ground surface +of the mouth of T, it is found that ten cubic centimeters of anhydrous +ether or alcohol are sufficient to make a complete extraction, and +there is not much loss of solvent in six hours. The thickness of the +asbestos film in G, or its fineness, is so adjusted as to prevent too +rapid filtration so that the solvent may just cover the material to +be extracted, or, after the material is placed in a crucible, a plug +of extracted glass wool may be placed above it for the purpose of +distributing the solvent evenly over the surface of the material to be +extracted and of preventing the escape of fine particles. +<span class="pagenum"><a id="Page_51"></a>[Pg 51]</span></p> + +<div class="figcenter smcap"> + <img id="FIG_24" src="images/fig24.jpg" alt="" width="600" height="409" > + <p class="center spb1">Figure 24. Improved Compact Extraction Apparatus.</p> +</div> + +<p>In very warm weather the apparatus may be arranged as shown in <a href="#FIG_24">figure 24</a>. +The bath for holding the extraction tubes is made in two parts, +K and Kʹ. The bath K has a false bottom shown in the dotted line O, +perforated to receive the ends of the extraction tubes and which holds +them in place and prevents them from touching the true bottom, where +they might be unequally heated by the lamp. The upper bath Kʹ has a +<span class="pagenum"><a id="Page_52"></a>[Pg 52]</span> +perforated bottom, partly closed with rubber-cloth diaphragms Gʹ Nʹ Hʹ. +The extraction tubes passing through this bath, water-tight, permit +broken ice or ice-water to be held about their tops, and thus secure +a complete condensation of the vapors of the solvent which in warm +weather might escape the metal condenser. In practice care must be +taken to avoid enveloping too much of the upper part of the extraction +tube with the ice-water, otherwise the vapors of the solvent will be +chiefly condensed on the sides of the extraction tube and will not be +returned through the sample. It is not often that the upper bath is +needed, and then only with ether, never with alcohol. This apparatus +has proved especially useful with alcohol, using, as suggested, +glycerol in the bath. The details of its further construction and +arrangement are shown in the <a href="#FIG_24">figure</a>. The extraction tubes +are most conveniently arranged in a battery of four, one current of cold water +passing in at A and out at B, serving for all. The bath is supported +on legs long enough to allow the lamp plenty of room. The details of +the condenser M are shown in Bʹ, Aʹ, T, Fʹ, and Lʹ. Instead of a gooch +Lʹ for holding the sample a glass tube R, with a perforated platinum +disk Q, may be used. The water line in the bath is shown by W. This +apparatus may be made very cheaply and without greatly impairing its +efficiency by using a plain concentric condenser and leaving off the +upper bath Kʹ.</p> + +<p><b>42. Solvents Employed.</b>—It has already been intimated that the +chief solvents employed in the extraction of agricultural samples are +ether or petroleum and aqueous alcohol. The ether used should be free +of alcohol and water, the petroleum should be subjected to fractional +distillation to free it of the parts of very high and very low +boiling points, and the alcohol as a rule should contain about twenty +per cent of water.</p> + +<p>There are many instances, however, where other solvents should be used. +The use of aqueous alcohol is sometimes preceded by that of alcohol of +greater strength or practically free of water. For the extraction of +soluble carbohydrates (sugars) cold or tepid water is employed, the +temperature of which is not allowed to rise high enough to act upon +starch granules. For the solution of the starch itself an acid solvent +<span class="pagenum"><a id="Page_53"></a>[Pg 53]</span> +is used at a boiling temperature, whereby the starch molecules undergo +hydrolysis and form dextrin or soluble sugars (maltose, dextrose). By +this process also the carbohydrates, whose molecules contain five, or +some multiple thereof, atoms of carbon form soluble sugars of which +xylose and arabinose are types. The solvent action of acids followed +by treatment with dilute alkalies at a boiling temperature, completes +practically the solution of all the carbohydrate bodies, save cellulose +and nearly related compounds. The starch carbohydrates are further +dissolved by the action of certain ferments such as diastase.</p> + +<p>Dilute solutions of mineral salts exert a specific solvent action on +certain nitrogenous compounds and serve to help separate the albuminoid +bodies into definite groups.</p> + +<p>Under the proper headings the uses of these principal solvents will be +described, but a complete discussion of their action, especially on +samples of a vegetable origin, should be looked for in works on plant +analysis.<a id="FNanchor_20" href="#Footnote_20" class="fnanchor">[20]</a></p> + +<p>The application of acids and alkalies for the extraction of +carbohydrates, insoluble in water and alcohol, will be described, +in the paragraphs devoted to the analysis of fodders and cereals. +The extraction of these matters, made soluble by ferments, will be +discussed in the pages devoted to starch and artificial digestion. +It is thus seen that the general preliminary treatment of a sample +preparatory to specific methods of examination is confined to drying, +extraction with ether and alcohol, and incineration.</p> + +<p id="P_43"><b>43. Recovery of the Solvent.</b>—In using such solvents as ether, +chloroform, and others of high value, it is desirable often to recover +the solvent. Various forms of apparatus are employed for this purpose, +arranged in such a way as both to secure the solvent and to leave the +residue in an accessible condition, or in a form suited to weighing +in quantitive work. When the extractions are made according to the +improved method of Knorr, the flask containing the extract may be at +once connected with the apparatus shown in <a href="#FIG_25">figure 25</a>.<a id="FNanchor_21" href="#Footnote_21" class="fnanchor">[21]</a> +A represents the flask containing the solvent to be recovered, W the +steam-bath, B the condenser sealed by mercury, M and R the flask +receiving the products of condensation. It will be found economical +to save ether, alcohol, and chloroform even when only a few cubic +centimeters remain after the extraction is complete. In the <a href="#FIG_25">figure</a> +the neck of the flask A is represented as narrower than it really is. +The open end of the connecting tube, which is sealed on A by mercury, +should be the same size as the tube connecting with the condenser in +the extraction apparatus. +<span class="pagenum"><a id="Page_54"></a>[Pg 54]</span></p> + +<div class="figcenter smcap"> + <img id="FIG_25" src="images/fig25.jpg" alt="" width="400" height="707" > + <p class="center spb1">Figure 25.—Knorr’s Apparatus for<br> Receiving Solvents.</p> +</div> + +<p><span class="pagenum"><a id="Page_55"></a>[Pg 55]</span></p> + +<div class="figcenter smcap"> + <img id="FIG_26" src="images/fig26.jpg" alt="" width="500" height="545" > + <p class="center spb1">Figure 26. Apparatus for Recovering Solvents<br> from Open Dishes.</p> +</div> + +<p>It often happens that materials which are dissolved by the ordinary +<span class="pagenum"><a id="Page_56"></a>[Pg 56]</span> +solvents in use are to be collected in open dishes in order that +their properties may be studied. At the same time large quantities +of solvents must be used, and it is desirable to have some method of +recovering them. The device shown in <a href="#FIG_26">Fig. 26</a> has been found to work +excellently well for this purpose.<a id="FNanchor_22" href="#Footnote_22" class="fnanchor">[22]</a> +It consists of a steam-bath, W, and a bottle, B, with the bottom +cut off, resting on an iron dish, P, containing a small quantity of +mercury, enough to seal the bottom of the bottle. The dish containing +the solvent is placed on the mercury, and the bottle placed down over +it, forming a tight joint. On the application of steam the solvent +escapes into the condenser, C, and is collected as a liquid in the +flask A. In very volatile solvents the flask A may be surrounded with +ice, or ice-cold water passed through the condenser. When an additional +quantity of the solvent is to be added to the dish for the purpose of +evaporating it is poured into the funnel F, and the stopcock H opened, +which allows the material to run into the dish in B without removing +the bottle. In this way many liters of the solvent may be evaporated +in any one dish, and the total amount of extract obtained together. At +the last the bottle B is removed, and the extract which is found in the +dish is ready for further operations.</p> + +<h3>AUTHORITIES CITED IN PART FIRST.</h3> + +<div class="footnotes"> +<div class="footnote"><p class="no-indent"> +<a id="Footnote_1" href="#FNanchor_1" class="label">[1]</a> +Sidersky: Traité d’Analyse des Matières Sucrées, p. 311.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_2" href="#FNanchor_2" class="label">[2]</a> +Die Agricultur-Chemische Versuchs-Station, Halle a/S., S. 34. +(Read Dreef instead of Dree.)</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_3" href="#FNanchor_3" class="label">[3]</a> +Report of Commissioner of Fish and Fisheries, 1888, p.686.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_4" href="#FNanchor_4" class="label">[4]</a> +Vid. op. cit. 2, p. 14.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_5" href="#FNanchor_5" class="label">[5]</a> +Journal of the American Chemical Society, Vol. 15, p. 83.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_6" href="#FNanchor_6" class="label">[6]</a> +Chemical Division, U. S. Department of Agriculture, +Bulletin No. 28, p. 101.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_7" href="#FNanchor_7" class="label">[7]</a> +Not yet described in any publication. Presented at 12th annual meeting +of the Association of Agricultural Chemists, Aug. 7th, 1895.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_8" href="#FNanchor_8" class="label">[8]</a> +Vid. op. cit. 6, p. 100.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_9" href="#FNanchor_9" class="label">[9]</a> +Cornell University Agricultural Experiment Station, Bulletin 12.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_10" href="#FNanchor_10" class="label">[10]</a> +(bis. p. 28). Vid. op. cit. 2, p. 15.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_11" href="#FNanchor_11" class="label">[11]</a> +Bulletin No. 13, Chemical Division, U. S. Department of Agriculture, +Part First pp. 85-6.</p> +</div> + +<p class="no-indent"><span class="pagenum"><a id="Page_57"></a>[Pg 57]</span></p> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_12" href="#FNanchor_12" class="label">[12]</a> +Bulletin de 1’ Association des Chimistes de Sucrerie, 1893, p. 656.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_13" href="#FNanchor_13" class="label">[13]</a> +Chemical News, Vol. 52, p. 280.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_14" href="#FNanchor_14" class="label">[14]</a> +Presented to 12th Annual Convention of the Association of +Official Agricultural Chemists, Sept. 7th, 1895.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_15" href="#FNanchor_15" class="label">[15]</a> +Vid. Volume First, p. 411.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_16" href="#FNanchor_16" class="label">[16]</a> +Vid. op. cit. 2, p. 17.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_17" href="#FNanchor_17" class="label">[17]</a> +Dragendorff, Plant Analysis.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_18" href="#FNanchor_18" class="label">[18]</a> +Vid. op. cit. 6, p. 96.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_19" href="#FNanchor_19" class="label">[19]</a> +Journal of Analytical and Applied Chemistry, Vol. 7, p. 65, +and Journal of the American Chemical Society, March 1893.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_20" href="#FNanchor_20" class="label">[20]</a> +Vid. op. cit. 16.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_21" href="#FNanchor_21" class="label">[21]</a> +Vid. op. cit. 6, p. 99.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_22" href="#FNanchor_22" class="label">[22]</a> +Vid. op. cit. 6, p. 103.</p> +</div></div> + +<hr class="chap x-ebookmaker-drop"> + +<div class="chapter"> +<p><span class="pagenum"><a id="Page_58"></a>[Pg 58]</span></p> + +<h2 class="nobreak">PART SECOND.<br> +<span class="h_subtitle">SUGARS AND STARCHES.</span></h2> +</div> + +<p><b>44. Introduction.</b>—Carbohydrates, of which sugars and starches +are the chief representatives, form the great mass of the results of +vegetable metabolism. The first functions of the chlorophyll cells of +the young plant are the condensation of carbon dioxid and water. The +simplest form of the condensation is formaldehyd, <b>CH₂O</b>. There is no +convincing evidence, however, that this is the product resulting from +the functional activity of the chlorophyll cells. The first evidence +of the condensation is found in more complex molecules; <i>viz.</i>, +those having six atoms of carbon. It is not the purpose of this work to +discuss the physiology of this process, but the interested student can +easily find access to the literature of the subject.<a id="FNanchor_23" href="#Footnote_23" class="fnanchor">[23]</a> +When a sample of a vegetable nature reaches the analyst he finds by +far the largest part of its substance composed of these products of +condensation of the carbon dioxid and water. The sugars, starches, +pentosans, lignoses, and celluloses all have this common origin. Of +many air-dried plants these bodies form more than eighty per cent.</p> + +<p>In green plants the sugars exist chiefly in the sap. In plants cut +green and quickly dried by artificial means the sugars are found +in a solid state. They also exist in the solid state naturally in +certain sacchariferous seeds. Many sugar-bearing plants when allowed +to dry spontaneously lose all or the greater part of their sugar by +fermentation. This is true of sugar cane, sorghum, maize stalks, and +the like. The starches are found deposited chiefly in tubers, roots or +seeds. In the potato the starch is in the tuber, in cassava the tuber +holding the starch is also a root, in maize, rice and other cereals +the starch is in the seeds. The wood-fibers; <i>viz.</i>, pentosans, +lignose, cellulose, etc., form the framework and support of the plant +structure. Of all these carbohydrate bodies the most important as foods +<span class="pagenum"><a id="Page_59"></a>[Pg 59]</span> +are the sugars and starches, but a certain degree of digestibility +cannot be denied to other carbohydrate bodies with the possible +exception of pure cellulose. In the following paragraphs the general +principles of determining the sugars and starches will be given and +afterwards the special processes of extracting these bodies from +vegetable substances preparatory to quantitive determination.</p> + +<p><b>45. Nomenclature.</b>—In speaking of sugars it has been thought +best to retain for the present the old nomenclature in order to avoid +confusion. The terms dextrose, levulose, sucrose, etc., will therefore +be given their commonly accepted significations.</p> + +<p>A more scientific nomenclature has recently been proposed by Fischer, +in which glucose is used as the equivalent of dextrose and fructose +as the proper name for levulose. All sugars are further classified +by Fischer into groups according to the number of carbon atoms found +in the molecule. We have thus trioses, tetroses, pentoses, hexoses, +etc. Such a sugar as sucrose is called hexobiose by reason of the fact +that it appears to be formed of two molecules of hexose sugars. For a +similar reason raffinose would belong to the hexotriose group.<a id="FNanchor_24" href="#Footnote_24" class="fnanchor">[24]</a></p> + +<p>Again, the two great classes of sugars as determined by the structure +of the molecule are termed aldoses and ketoses according to their +relationship to the aldehyd or ketone bodies.</p> + +<p>Since sugars may be optically twinned, that is composed of equal +molecules of right and left-handed polarizing matter it may happen that +apparently the same body may deflect the plane of polarization to the +right, to the left, or show perfect neutrality.</p> + +<p>Natural sugars, as a rule, are optically active, but synthetic sugars +being optically twinned are apt to be neutral to polarized light.</p> + +<p>To designate the original optical properties of the body therefore +the symbols <i>d</i>, <i>l</i>, and <i>i</i>, meaning dextrogyratory, +levogyratory, and inactive, respectively, are prefixed to the name. +Thus we may have <i>d</i>, <i>l</i>, or <i>i</i> glucose, <i>d</i>, +<i>l</i>, or <i>i</i> fructose, and so on.</p> + +<p>The sugars that are of interest here belong altogether to the pentose +and hexose groups; <i>viz.</i>, <b>C₅H₁₀O₅</b> and <b>C₆H₁₂O₆</b>, respectively. +Of the hexobioses, sucrose, maltose, and lactose are the most important, +<span class="pagenum"><a id="Page_60"></a>[Pg 60]</span> +and of the hexotrioses, raffinose. In this manual, unless otherwise +stated, the term dextrose corresponds to <i>d</i> glucose, and levulose +to <i>d</i> fructose. In this connection, however, it should be noted +that the levulose of nature, or that which is formed by the hydrolysis +of inulin or sucrose is not identical in its optical properties with +the <i>l</i> fructose of Fischer.</p> + +<p><b>46. Preparation of Pure Sugar.</b>—In using the polariscope or in +testing solutions for the chemical analysis of samples, the analyst +will be required to keep always on hand some pure sugar. Several +methods of preparing pure sugar have been proposed. The finest +granulated sugar of commerce is almost pure. In securing samples for +examination those should be selected which have had a minimum treatment +with bluing in manufacture. The best quality of granulated sugar when +pulverized, washed with ninety-five per cent and then with absolute +alcohol and dried over sulfuric acid at a temperature not exceeding 50° +will be found nearly pure. Such a sugar will, as a rule, not contain +more than one-tenth per cent of impurities, and can be safely used for +all analytical purposes. It is assumed in the above that the granulated +sugar is made from sugar cane.</p> + +<p>Granulated beet sugars may contain raffinose and so may show a +polarization in excess of 100. This sugar may be purified by dissolving +seventy parts by weight in thirty parts of water. The sugar is +precipitated by adding slowly an equal volume of ninety-six per cent +alcohol with constant stirring, the temperature of the mixture being +kept at 60°. While still warm the supernatant liquor is decanted +and the precipitated sugar washed by decantation several times with +strong warm alcohol. The sugar, on a filter, is finally washed with +absolute alcohol and dried in a thin layer over sulfuric acid at from +35° to 40°. By this process any raffinose which the sugar may have +contained is completely removed by the warm alcohol. Since beet sugar +is gradually coming into use in this country it is safer to follow the +above method with all samples.<a id="FNanchor_25" href="#Footnote_25" class="fnanchor">[25]</a> +In former times it was customary to prepare pure sugar from the whitest +crystals of rock candy. These crystals are powdered, dissolved in +water, filtered, precipitated with alcohol, washed and dried in the +manner described above. +<span class="pagenum"><a id="Page_61"></a>[Pg 61]</span></p> + +<p><b>47. Classification of Methods.</b>—In the quantitive determination +of pure sugar the various processes employed may all be grouped +into three classes. In the first class are included all those which +deduce the percentage of sugar present from the specific gravity of +its aqueous solution. The accuracy of this process depends on the +purity of the material, the proper control of the temperature, and +the reliability of the instruments employed. The results are obtained +either directly from the scale of the instruments employed or are +calculated from the arbitrary or specific gravity numbers observed. It +is evident that any impurity in the solution would serve to introduce +an error of a magnitude depending on the percentage of impurity and +the deviation of the density from that of sugar. The different classes +of sugars, having different densities in solution, give also different +readings on the instruments employed. It is evident, therefore, that a +series of tables of percentages corresponding to the specific gravities +of the solutions of different sugars would be necessary for exact work. +Practically, however, the sugar which is most abundant, <i>viz.</i>, +sucrose, may be taken as a representative of the others and for rapid +control work the densimetric method is highly useful.</p> + +<p>In the second class of methods are grouped all those processes which +depend upon the property of sugar solutions to rotate the plane of +polarized light. Natural sugars all have this property and if their +solutions be found neutral to polarized light it is because they +contain sugars of opposite polarizing powers of equal intensity. Some +sugars turn the polarized plane to the right and others to the left, +and the degree of rotation in each case depends, at equal temperatures +and densities of the solutions, on the percentages of sugars present. +In order that the optical examination of a sugar may give correct +results the solution must be of a known density and free of other +bodies capable of affecting the plane of polarized light. In the +following paragraphs an attempt will be made to give in sufficient +detail the methods of practice of these different processes in so far +as they are of interest to the agricultural analyst. The number of +variations, however, in these processes is so great as to make the +attempt to fully discuss them here impracticable. The searcher for +<span class="pagenum"><a id="Page_62"></a>[Pg 62]</span> +additional details should consult the standard works on sugar +analysis.<a id="FNanchor_26" href="#Footnote_26" class="fnanchor">[26]</a></p> + +<p>In the third class of methods are included those which are of a +chemical nature based either on the reducing power which sugar +solutions exercise on certain metallic salts, upon the formation of +certain crystalline and insoluble compounds with other bodies or +upon fermentation. Under proper conditions solutions of sugar reduce +solutions of certain metallic salts, throwing out either the metal +itself or a low oxid thereof. In alkaline solutions of mercury and +copper, sugars exercise a reducing action, throwing out in the one case +metallic mercury and in the other cuprous oxid. With phenylhydrazin, +sugars form definite crystalline compounds, quite insoluble, which +can be collected, dried and weighed. There is a large number of other +chemical reactions with sugars such as their union with the earthy +bases, color reactions with alkalies, oxidation products with acids, +and so on, which are of great use qualitively and in technological +processes, but these are of little value in quantitive determinations.</p> + +<h3>THE DETERMINATION OF THE PERCENTAGE OF<br> +SUGAR BY THE DENSITY OF ITS SOLUTION.</h3> + +<p id="P_48"><b>48. Principles of the Method.</b>—This method of analysis is +applied almost exclusively to the examination of one kind of sugar, +<i>viz.</i>, the common sugar of commerce. This sugar is derived +chiefly from sugar cane and sugar beets and is known chemically as +sucrose or saccharose. The method is accurate only when applied to +solutions of pure sucrose which contain no other bodies. It is evident +however, that other bodies in solution can be determined by the same +process, so that the principle of the method is broadly applicable to +the analyses of any body whatever in a liquid state or in solution. +Gases, liquids and solids, in solution, can all be determined by +densimetric methods.</p> + +<p>Broadly stated the principle of the method consists in determining the +specific gravity of the liquid or solution, and thereafter taking the +percentage of the body in solution from the corresponding specific +gravity in a table. These tables are carefully prepared by gravimetric +<span class="pagenum"><a id="Page_63"></a>[Pg 63]</span> +determinations of the bodies in solution of known densities, varying by +small amounts and calculation of the percentages for the intervening +increments or decrements of density. This tabulation is accomplished at +definite temperatures and the process of analysis secured thereby is +rapid and accurate, with pure or nearly pure solutions.</p> + +<p><b>49. Determination of Density.</b>—While not strictly correct from +a physical point of view, the terms density and specific gravity are +here used synonymously and refer to a direct comparison of the weights +of equal volumes of pure water and of the solution in question, at the +temperature named. When not otherwise stated, the temperature of the +solution is assumed to be 15°.5.</p> + +<div class="figcenter smcap"> + <img id="FIG_27" src="images/fig27.jpg" alt="" width="500" height="594" > + <p class="center spb1">Figure 27. Common Forms of Pyknometers.</p> +</div> + +<p>The simplest method of determining the density of a solution is to +get the weight of a definite volume thereof. This is conveniently +accomplished by the use of a pyknometer. A pyknometer is any vessel +<span class="pagenum"><a id="Page_64"></a>[Pg 64]</span> +capable of holding a definite volume of a liquid in a form suited +to weighing. It may be a simple flask with a narrow neck distinctly +marked, or a flask with a ground perforated stopper, which, when +inserted, secures always the same volume of liquid contents. A very +common form of pyknometer is one in which the central stopper carries a +thermometer and the constancy of volume is secured by a side tubulure +of very small or even capillary dimensions, which is closed by a ground +glass cap.</p> + +<p>The apparatus may not even be of flask form, but assume a quite +different shape as in Sprengel’s tube. Pyknometers are often made to +hold an even number of cubic centimeters, but the only advantage of +this is in the ease of calculation which it secures. As a rule, it +will be found necessary to calibrate even these, and then the apparent +advantage will be easily lost. A flask which is graduated to hold fifty +cubic centimeters, may, in a few years, change its volume at least +slightly, due to molecular changes in the glass. Some of the different +forms of pyknometers are shown in the accompanying figures.</p> + +<p>In use the pyknometer should be filled with pure water of the desired +temperature and weighed. From the total weight the tare of the flask +and stopper, weighed clean and dry, is to be deducted. The remainder +is the weight of the volume of water of the temperature noted, which +the pyknometer holds. The weight of the solution under examination is +taken in the same way and at the same temperature, and thus a direct +comparison between the two liquids is secured.</p> + +<table class="spb1 fs_90"> + <tbody><tr> + <td class="tdl"><i>Example.</i>—Let the weight of the pyknometer be  </td> + <td class="tdr">15.2985</td> + <td class="tdl_wsp">grams.</td> + </tr><tr> + <td class="tdl_ws2">and its weight with pure water at 15°.5 be</td> + <td class="tdr">26.9327</td> + <td class="tdc">”</td> + </tr><tr> + <td class="tdl_ws1">Then the weight of water is</td> + <td class="tdr">11.6342</td> + <td class="tdc">”</td> + </tr><tr> + <td class="tdl_ws1">The weight filled with the sugar solution is</td> + <td class="tdr">28.3263</td> + <td class="tdc">”</td> + </tr><tr> + <td class="tdl_ws1">Then the weight of the sugar solution is</td> + <td class="tdr">13.0278</td> + <td class="tdc">”</td> + </tr> + </tbody> +</table> + +<p>The specific gravity of the sugar solution is therefore, 13.0278 ÷ +11.6342 = 1.1198.</p> + +<p>For strictly accurate results the weight must be corrected for the +volume of air displaced, or in other words, be reduced to weights in +vacuo. This however is unnecessary for the ordinary operations of +agricultural analysis. +<span class="pagenum"><a id="Page_65"></a>[Pg 65]</span></p> + +<p>If the volume of the pyknometer be desired, it can be calculated from +the weight of pure water which it holds, one cubic centimeter of pure +water weighing one gram at 4°.</p> + +<p>The weights of one cubic centimeter of water at each degree of +temperature from 1° to 40°, are given in the following table:</p> + +<p class="f120 spb1"><b><span class="smcap">Table Showing Weights of One<br> +Cubic Centimeter of Pure Water<br> at Temperatures Varying from<br> 1° To 40°.</span></b></p> + +<table class="spb1"> + <thead><tr> + <th class="tdc bb"> Temperature. </th> + <th class="tdc bb">Weight,<br> Gram.</th> + <th class="tdc bb"> Temperature. </th> + <th class="tdc bb">Weight,<br> Gram.</th> + </tr></thead> + <tbody><tr> + <td class="tdc"> 0°</td> + <td class="tdc">0.999871</td> + <td class="tdc">21°</td> + <td class="tdc">0.998047</td> + </tr><tr> + <td class="tdc"> 1°</td> + <td class="tdc">0.999928</td> + <td class="tdc">22°</td> + <td class="tdc">0.997826</td> + </tr><tr> + <td class="tdc"> 2°</td> + <td class="tdc">0.999969</td> + <td class="tdc">23°</td> + <td class="tdc">0.997601</td> + </tr><tr> + <td class="tdc"> 3°</td> + <td class="tdc">0.999991</td> + <td class="tdc">24°</td> + <td class="tdc">0.997367</td> + </tr><tr> + <td class="tdc"> 4°</td> + <td class="tdc">1.000000</td> + <td class="tdc">25°</td> + <td class="tdc">0.997120</td> + </tr><tr> + <td class="tdc"> 5°</td> + <td class="tdc">0.999990</td> + <td class="tdc">26°</td> + <td class="tdc">0.996866</td> + </tr><tr> + <td class="tdc"> 6°</td> + <td class="tdc">0.999970</td> + <td class="tdc">27°</td> + <td class="tdc">0.996603</td> + </tr><tr> + <td class="tdc"> 7°</td> + <td class="tdc">0.999933</td> + <td class="tdc">28°</td> + <td class="tdc">0.998331</td> + </tr><tr> + <td class="tdc"> 8°</td> + <td class="tdc">0.999886</td> + <td class="tdc">29°</td> + <td class="tdc">0.995051</td> + </tr><tr> + <td class="tdc"> 9°</td> + <td class="tdc">0.999824</td> + <td class="tdc">30°</td> + <td class="tdc">0.995765</td> + </tr><tr> + <td class="tdc">10°</td> + <td class="tdc">0.999747</td> + <td class="tdc">31°</td> + <td class="tdc">0.995401</td> + </tr><tr> + <td class="tdc">11°</td> + <td class="tdc">0.999655</td> + <td class="tdc">32°</td> + <td class="tdc">0.995087</td> + </tr><tr> + <td class="tdc">12°</td> + <td class="tdc">0.999549</td> + <td class="tdc">33°</td> + <td class="tdc">0.994765</td> + </tr><tr> + <td class="tdc">13°</td> + <td class="tdc">0.999430</td> + <td class="tdc">34°</td> + <td class="tdc">0.994436</td> + </tr><tr> + <td class="tdc">14°</td> + <td class="tdc">0.999299</td> + <td class="tdc">35°</td> + <td class="tdc">0.994098</td> + </tr><tr> + <td class="tdc">15°</td> + <td class="tdc">0.999160</td> + <td class="tdc">36°</td> + <td class="tdc">0.993720</td> + </tr><tr> + <td class="tdc">16°</td> + <td class="tdc">0.999002</td> + <td class="tdc">37°</td> + <td class="tdc">0.993370</td> + </tr><tr> + <td class="tdc">17°</td> + <td class="tdc">0.998841</td> + <td class="tdc">38°</td> + <td class="tdc">0.993030</td> + </tr><tr> + <td class="tdc">18°</td> + <td class="tdc">0.998654</td> + <td class="tdc">39°</td> + <td class="tdc">0.992680</td> + </tr><tr> + <td class="tdc">19°</td> + <td class="tdc">0.998460</td> + <td class="tdc">40°</td> + <td class="tdc">0.992330</td> + </tr><tr> + <td class="tdc">20°</td> + <td class="tdc">0.998259</td> + <td class="tdc"> </td> + <td class="tdc"> </td> + </tr> + </tbody> +</table> + +<p>From the table and the weight of water found, the volume of the +pyknometer is easily calculated.</p> + +<p><i>Example.</i>—Let the weight of water found be 11.72892 grams, and +the temperature 20°. Then the volume of the flask is equal to 11.72892 +÷ 0.998259, <i>viz.</i>, 11.95 cubic centimeters.</p> + +<p><b>50. Use of Pyknometer at High Temperatures.</b>—It is often found +desirable to determine the density of a liquid at temperatures above +that of the laboratory, <i>e. g.</i>, at the boiling-point of water. +This is easily accomplished by following the directions given below:</p> + +<p><i>Weight of Flask.</i>—Use a small pyknometer of from twenty-five to +thirty cubic centimeters capacity. The stopper should be beveled to a +<span class="pagenum"><a id="Page_66"></a>[Pg 66]</span> +fine edge on top and the lower end should be slightly concave to +avoid any trapping of air. The flask is to be thoroughly washed with +hot water, alcohol and ether, and then dried for some time at 100°. +After cooling in a desiccator the weight of the flask and stopper is +accurately determined.<a id="FNanchor_27" href="#Footnote_27" class="fnanchor">[27]</a></p> + +<div class="figcenter smcap"> + <img id="FIG_28" src="images/fig28.jpg" alt="" width="400" height="509" > + <p class="center spb1">Figure 28. Bath for Pyknometers.</p> +</div> + +<p><span class="pagenum"><a id="Page_67"></a>[Pg 67]</span> +<i>Weight of Water.</i>—The flask in an appropriate holder, <a href="#FIG_28">Fig. 28</a>, +conveniently made of galvanized iron, is filled with freshly boiled and +hot distilled water and placed in a bath of pure, very hot distilled +water, in such a way that it is entirely surrounded by the liquid with +the exception of the top.</p> + +<p>The water of the bath is kept in brisk ebullition for thirty minutes, +any evaporation from the flask being replaced by the addition of +boiling distilled water. The stopper should be kept for a few minutes +before use in hot distilled water and is then inserted, the flask +removed, wiped dry, and, after it is nearly cooled to room temperature, +placed in the balance and weighed when balance temperature is reached. +A convenient size of holder will enable the analyst to use eight or ten +flasks at once. The temperature at which water boils in each locality +may also be determined; but unless at very high altitudes, or on days +of unusual barometric disturbance the variations will not be great, and +will not appreciably affect the results.</p> + +<p id="P_51"><b>51. Alternate Method of Estimating the Weight of Water in +Flasks.</b>—Formulas for calculating the volume <i>V</i>, in cubic +centimeters, of a glass vessel from the weight <i>P</i> of water at the +temperature <i>t</i> contained therein, and the volume <i>Vʹ</i> at any +other temperature <i>t’</i> are given by Landolt and Börnstein.<a id="FNanchor_28" href="#Footnote_28" class="fnanchor">[28]</a> +They are as follows:</p> + +<table class="spb1 fs_120"> + <tbody><tr> + <td class="tdl" rowspan="2"><i>V</i> = <i>P</i> </td> + <td class="tdc bb"><i>p</i></td> + </tr><tr> + <td class="tdc"><i>d</i></td> + </tr> + </tbody> +</table> + +<table class="spb1 fs_120"> + <tbody><tr> + <td class="tdl" rowspan="2"><i>Vʹ</i> = <i>P</i> </td> + <td class="tdc bb"><i>p</i></td> + <td class="tdl" rowspan="2"> [1 + <i>γ</i> (<i>tʹ</i>- <i>t</i>)];</td> + </tr><tr> + <td class="tdc"><i>d</i></td> + </tr> + </tbody> +</table> + +<p class="no-indent">in which <i>p</i> = weight (in brass weights) of +one cubic centimeter <b>H₂O</b> in vacuo. This is so nearly one gram that +it will not affect the result in the fifth place of decimals and may +therefore be disregarded. Hence the formula stands:</p> + +<table class="spb1 fs_120"> + <tbody><tr> + <td class="tdl" rowspan="2"><i>Vʹ</i> = <i>P</i> </td> + <td class="tdc bb">1</td> + <td class="tdl" rowspan="2"> [1 + <i>γ</i> (<i>tʹ</i>- <i>t</i>)]</td> + </tr><tr> + <td class="tdc"><i>d</i></td> + </tr> + </tbody> +</table> + +<p><i>d</i> = density of water at temperature <i>t</i>.</p> + +<p><i>γ</i> = 0.000025, the cubical expansion coefficient of glass.</p> + +<p>From this volume the weight of the water may be readily obtained by +referring to tables 13, 14 and 15<i>a</i> in Landolt and Börnstein’s book. +<span class="pagenum"><a id="Page_68"></a>[Pg 68]</span></p> + +<p><b>52. Example Showing Determination of Specific Gravity of a +Fat.</b>—The flask is emptied of its water, rinsed with alcohol and +ether, and dried again for a few minutes at 100°. It is then filled +with the dry, hot, fresh-filtered fat, which should be entirely free +from air bubbles.</p> + +<p>The stoppered flask is then replaced in the water-bath, kept for thirty +minutes at the temperature of boiling water, removed, and treated as +above. The weight of fat having been determined, the specific gravity +is obtained by dividing it by the weight of water previously found.</p> + +<table class="spb1"> + <tbody><tr> + <td class="tdc fs_110" colspan="2"><i>Example.</i></td> + </tr><tr> + <td class="tdr" colspan="2">Grams.</td> + </tr><tr> + <td class="tdl">Weight of flask, dry</td> + <td class="tdr">10.0197</td> + </tr><tr> + <td class="tdl">Weight of flask, plus water</td> + <td class="tdr">37.3412</td> + </tr><tr> + <td class="tdl">Weight of water</td> + <td class="tdr">27.3215</td> + </tr><tr> + <td class="tdl">Weight of flask, plus fat</td> + <td class="tdr">34.6111</td> + </tr><tr> + <td class="tdl">Weight of fat</td> + <td class="tdr">24.5914</td> + </tr><tr> + <td class="tdl">Specific gravity = 24.5914 ÷ 27.3215 = </td> + <td class="tdr">0.90008.</td> + </tr> + </tbody> +</table> + +<p>The weight of the flask dry and empty and the weight of water at 99° to +100° contained therein may be used constantly if great care be taken in +handling and cleaning the apparatus.</p> + +<table class="spb2"> + <tbody><tr> + <td class="tdc fs_110" colspan="2"><i>Example</i>.</td> + </tr><tr> + <td class="tdr" colspan="2">Grams.</td> + </tr><tr> + <td class="tdl">Weight of flask, dry and empty</td> + <td class="tdr">10.0028</td> + </tr><tr> + <td class="tdl">Weight of flask after three weeks’ use </td> + <td class="tdr">10.0030</td> + </tr> + </tbody> +</table> + +<div class="figcenter smcap"> + <img id="FIG_29" src="images/fig29.jpg" alt="" width="600" height="171" > + <p class="center spb1">Figure 29. Aereometers, Pyknometers, and + Hydrostatic Balance.</p> +</div> + +<p id="P_53"><b>53. Determination of Density by the Hydrostatic Balance.</b>—While +the pyknometer is useful in control work and in fixing standards of +comparison, it is not used extensively in practical work. Quicker +methods of determination are desired in such work, and these are +found in the use of other forms of apparatus. A convenient method of +operation consists in determining the weight of a sinker, whose exact +<span class="pagenum"><a id="Page_69"></a>[Pg 69]</span> +weights in air and in pure water of a definite temperature, have been +previously determined. The instrument devised by Mohr and modified by +Westphal, is based upon that principle, and is extensively used in +practical work. The construction of this apparatus and also that of the +pyknometers and areometers is shown in the illustrations, figures +<a href="#FIG_29">29</a> and <a href="#FIG_30">30</a>.</p> + +<div class="figcenter smcap"> + <img id="FIG_30" src="images/fig30.jpg" alt="" width="500" height="498" > + <p class="center spb1">Figure 30. Hydrostatic Balance.</p> +</div> + +<p>The weight of the sinker is so adjusted that the index of the balance +arm marks zero when the sinker is wholly immersed in pure water at the +standard temperature. The density of a solution of sugar at the same +temperature, is then determined by placing the rider-weights on the +<span class="pagenum"><a id="Page_70"></a>[Pg 70]</span> +divided arm of the balance, until the index again marks zero. The +density can then be read directly from the position of the weights in +the arm of the balance or calculated therefrom.</p> + +<p><b>54. The Areometric Method.</b>—The most rapid method of determining +the density of a solution and the one in most common use, is based +on the distance to which a heavy bulb with a slender graduated stem +will sink therein. An instrument of this kind is called an areometer. +Many forms of this instrument are employed but they all depend on the +same principle and differ only in the manner of graduation. The one of +widest application has the stem graduated in such a manner as to give +directly the specific gravity of the solution in which it is placed.</p> + +<p>Others are made with a special graduation giving directly the +percentage of solid matter in the solution. These instruments can be +used only for the special purposes for which they are constructed. +Other forms are provided with an arbitrary graduation, the numbers +of which by appropriate tables can be converted into expressions of +specific gravity or of per cents of dissolved matters. It is not +practicable to give here, a discussion of the principles of the +construction of areometers.<a id="FNanchor_29" href="#Footnote_29" class="fnanchor">[29]</a> +The two which are commonly used, are the baumé hydrometer and the +balling or brix spindle.</p> + +<p>In the baumé instrument the zero of the scale is fixed at the point +marked by the surface of distilled water at 15°, and the point to which +it sinks in pure monohydrated sulfuric acid at the same temperature is +marked 66, corresponding to a specific gravity of 1.8427.</p> + +<p>The specific gravity corresponding to any degree of the scale, may be +calculated in the absence of a table giving it, by the following formula</p> + +<table class="spb1 fs_120"> + <tbody><tr> + <td class="tdl" rowspan="2"><i>P</i> = </td> + <td class="tdc bb">144.3</td> + <td class="tdl_wsp" rowspan="2">.</td> + </tr><tr> + <td class="tdc">144.3 - <i>d</i></td> + </tr> + </tbody> +</table> + +<p>In this formula <i>P</i> is the density and <i>d</i> the degree of the +scale.<a id="FNanchor_30" href="#Footnote_30" class="fnanchor">[30]</a> +In former times the baumé instruments were graduated with a solution +of common salt and a different formula was employed for calculating +specific gravity, but these older instruments are no longer in common +use.</p> + +<p>The following table shows the specific gravities of solutions +corresponding to baumé degrees from 1° to 75° consecutively<a id="FNanchor_31" href="#Footnote_31" class="fnanchor">[31]</a>:</p> + +<p><span class="pagenum"><a id="Page_71"></a>[Pg 71]</span></p> + +<table class="spb1"> + <thead><tr> + <th class="tdc">Degree<br>baumé</th> + <th class="tdc"> Specific <br>gravity</th> + <th class="tdc">Degree<br>baumé</th> + <th class="tdc"> Specific <br>gravity</th> + <th class="tdc">Degree<br>baumé</th> + <th class="tdc"> Specific <br>gravity</th> + <th class="tdc">Degree<br>baumé</th> + <th class="tdc"> Specific <br>gravity</th> + </tr></thead> + <tbody><tr> + <td class="tdc"> 0</td> <td class="tdc">1.0000</td> + <td class="tdc">19</td> <td class="tdc">1.1516</td> + <td class="tdc">38</td> <td class="tdc">1.3574</td> + <td class="tdc">57</td> <td class="tdc">1.6527</td> + </tr><tr> + <td class="tdc"> 1</td> <td class="tdc">1.0069</td> + <td class="tdc">20</td> <td class="tdc">1.1608</td> + <td class="tdc">39</td> <td class="tdc">1.3703</td> + <td class="tdc">58</td> <td class="tdc">1.6719</td> + </tr><tr> + <td class="tdc"> 2</td> <td class="tdc">1.0140</td> + <td class="tdc">21</td> <td class="tdc">1.1702</td> + <td class="tdc">40</td> <td class="tdc">1.3834</td> + <td class="tdc">59</td> <td class="tdc">1.6915</td> + </tr><tr> + <td class="tdc"> 3</td> <td class="tdc">1.0212</td> + <td class="tdc">22</td> <td class="tdc">1.1798</td> + <td class="tdc">41</td> <td class="tdc">1.3968</td> + <td class="tdc">60</td> <td class="tdc">1.7115</td> + </tr><tr> + <td class="tdc"> 4</td> <td class="tdc">1.0285</td> + <td class="tdc">23</td> <td class="tdc">1.1895</td> + <td class="tdc">42</td> <td class="tdc">1.4104</td> + <td class="tdc">61</td> <td class="tdc">1.7321</td> + </tr><tr> + <td class="tdc"> 5</td> <td class="tdc">1.0358</td> + <td class="tdc">24</td> <td class="tdc">1.1994</td> + <td class="tdc">43</td> <td class="tdc">1.4244</td> + <td class="tdc">62</td> <td class="tdc">1.7531</td> + </tr><tr> + <td class="tdc"> 6</td> <td class="tdc">1.0433</td> + <td class="tdc">25</td> <td class="tdc">1.2095</td> + <td class="tdc">44</td> <td class="tdc">1.4386</td> + <td class="tdc">63</td> <td class="tdc">1.7748</td> + </tr><tr> + <td class="tdc"> 7</td> <td class="tdc">1.0509</td> + <td class="tdc">26</td> <td class="tdc">1.2197</td> + <td class="tdc">45</td> <td class="tdc">1.4530</td> + <td class="tdc">64</td> <td class="tdc">1.7968</td> + </tr><tr> + <td class="tdc"> 8</td> <td class="tdc">1.0586</td> + <td class="tdc">27</td> <td class="tdc">1.2301</td> + <td class="tdc">46</td> <td class="tdc">1.4678</td> + <td class="tdc">65</td> <td class="tdc">1.8194</td> + </tr><tr> + <td class="tdc"> 9</td> <td class="tdc">1.0665</td> + <td class="tdc">28</td> <td class="tdc">1.2407</td> + <td class="tdc">47</td> <td class="tdc">1.4829</td> + <td class="tdc">66</td> <td class="tdc">1.8427</td> + </tr><tr> + <td class="tdc">10</td> <td class="tdc">1.0744</td> + <td class="tdc">29</td> <td class="tdc">1.2514</td> + <td class="tdc">48</td> <td class="tdc">1.4983</td> + <td class="tdc">67</td> <td class="tdc">1.8665</td> + </tr><tr> + <td class="tdc">11</td> <td class="tdc">1.0825</td> + <td class="tdc">30</td> <td class="tdc">1.2624</td> + <td class="tdc">49</td> <td class="tdc">1.5140</td> + <td class="tdc">68</td> <td class="tdc">1.8909</td> + </tr><tr> + <td class="tdc">12</td> <td class="tdc">1.0906</td> + <td class="tdc">31</td> <td class="tdc">1.2735</td> + <td class="tdc">50</td> <td class="tdc">1.5301</td> + <td class="tdc">69</td> <td class="tdc">1.9161</td> + </tr><tr> + <td class="tdc">13</td> <td class="tdc">1.0989</td> + <td class="tdc">32</td> <td class="tdc">1.2849</td> + <td class="tdc">51</td> <td class="tdc">1.5465</td> + <td class="tdc">70</td> <td class="tdc">1.9418</td> + </tr><tr> + <td class="tdc">14</td> <td class="tdc">1.1074</td> + <td class="tdc">33</td> <td class="tdc">1.2964</td> + <td class="tdc">52</td> <td class="tdc">1.5632</td> + <td class="tdc">71</td> <td class="tdc">1.9683</td> + </tr><tr> + <td class="tdc">15</td> <td class="tdc">1.1159</td> + <td class="tdc">34</td> <td class="tdc">1.3081</td> + <td class="tdc">53</td> <td class="tdc">1.5802</td> + <td class="tdc">72</td> <td class="tdc">1.9955</td> + </tr><tr> + <td class="tdc">16</td> <td class="tdc">1.1246</td> + <td class="tdc">35</td> <td class="tdc">1.3201</td> + <td class="tdc">54</td> <td class="tdc">1.5978</td> + <td class="tdc">73</td> <td class="tdc">2.0235</td> + </tr><tr> + <td class="tdc">17</td> <td class="tdc">1.1335</td> + <td class="tdc">36</td> <td class="tdc">1.3323</td> + <td class="tdc">55</td> <td class="tdc">1.6157</td> + <td class="tdc">74</td> <td class="tdc">2.0523</td> + </tr><tr> + <td class="tdc">18</td> <td class="tdc">1.1424</td> + <td class="tdc">37</td> <td class="tdc">1.3447</td> + <td class="tdc">56</td> <td class="tdc">1.6340</td> + <td class="tdc">75</td> <td class="tdc">2.0819</td> + </tr> + </tbody> +</table> + +<p><b>55. Correction for Temperature.</b>—The baumé hydrometer should be +used at the temperature for which it is graduated, usually 15°. In this +country the mean temperature of our working rooms is above 15°. The +liquid in the hydrometer flask should therefore be cooled to a trifle +below 15°, or kept in a bath exactly at 15° while the observation is +made. When this is not convenient, the observation may be made at any +temperature, and the reading corrected as follows: When the temperature +is above 15° multiply the difference between the observed temperature +and fifteen, by 0.0471 and add the product to the observed reading of +the baumé hydrometer; when the temperature on the other hand, is below +fifteen, the corresponding product is subtracted.<a id="FNanchor_32" href="#Footnote_32" class="fnanchor">[32]</a></p> + +<p><b>56. The Balling or Brix Hydrometer.</b>—The object of the balling +or brix instrument is to give in direct percentages the solid matter +in solution. It is evident that for this purpose the instrument must +be graduated for a particular kind of material, since ten per cent of +sugar in solution, might have a very different specific gravity from a +similar quantity of another body. Instruments of this kind graduated +for pure sugar, find a large use in technical sugar analysis. To attain +<span class="pagenum"><a id="Page_72"></a>[Pg 72]</span> +a greater accuracy and avoid an instrument with too long a stem, the +brix hydrometers are made in sets. A convenient arrangement is to have +a set of three graduated as follows; one from 0° to 30°, one from 25° +to 50°, and one from 45° to 85°. When the percentage of solid matter +dissolved is over seventy the readings of the scale are not very reliable.</p> + +<p><b>57. Correction for Temperature.</b>—The brix as the baumé scale is +graduated at a fixed temperature. This temperature is usually 17°.5. +The following table shows the corrections to be applied to the scale +reading when made at any other temperature:<a id="FNanchor_33" href="#Footnote_33" class="fnanchor">[33]</a></p> + +<p class="f120 spa1"><b><span class="smcap">Per Cent of Sugar in Solution.</span></b></p> + +<table class="spb1"> + <tbody><tr> + <td class="tdl"> </td> + <td class="tdc"> 0.</td> <td class="tdc"> 5.</td> + <td class="tdc">10.</td> <td class="tdc">15.</td> + <td class="tdc">20.</td> <td class="tdc">25.</td> + <td class="tdc">30.</td> <td class="tdc">35.</td> + <td class="tdc">40.</td> <td class="tdc">50.</td> + <td class="tdc">60.</td> <td class="tdc">70.</td> + <td class="tdc">75.</td> + </tr><tr> + <td class="tdl">Temp.</td> + <td class="tdc fs_110" colspan="13"><i>To be subtracted from the degree read.</i></td> + </tr><tr> + <td class="tdl_wsp">0°</td> + <td class="tdc"> 0.17 </td> <td class="tdc bl"> 0.30 </td> + <td class="tdc bl"> 0.41 </td> <td class="tdc bl"> 0.52 </td> + <td class="tdc bl"> 0.62 </td> <td class="tdc bl"> 0.72 </td> + <td class="tdc bl"> 0.82 </td> <td class="tdc bl"> 0.92 </td> + <td class="tdc bl"> 0.98 </td> <td class="tdc bl"> 1.11 </td> + <td class="tdc bl"> 1.22 </td> <td class="tdc bl"> 1.25 </td> + <td class="tdc bl"> 1.29 </td> + </tr><tr> + <td class="tdl_wsp">5°</td> + <td class="tdc">0.23</td> <td class="tdc bl">0.30</td> + <td class="tdc bl">0.37</td> <td class="tdc bl">0.44</td> + <td class="tdc bl">0.52</td> <td class="tdc bl">0.59</td> + <td class="tdc bl">0.65</td> <td class="tdc bl">0.72</td> + <td class="tdc bl">0.75</td> <td class="tdc bl">0.80</td> + <td class="tdc bl">0.88</td> <td class="tdc bl">0.91</td> + <td class="tdc bl">0.94</td> + </tr><tr> + <td class="tdl">10°</td> + <td class="tdc">0.20</td> <td class="tdc bl">0.26</td> + <td class="tdc bl">0.29</td> <td class="tdc bl">0.33</td> + <td class="tdc bl">0.36</td> <td class="tdc bl">0.39</td> + <td class="tdc bl">0.42</td> <td class="tdc bl">0.45</td> + <td class="tdc bl">0.48</td> <td class="tdc bl">0.50</td> + <td class="tdc bl">0.54</td> <td class="tdc bl">0.58</td> + <td class="tdc bl">0.61</td> + </tr><tr> + <td class="tdl">11°</td> + <td class="tdc">0.18</td> <td class="tdc bl">0.23</td> + <td class="tdc bl">0.26</td> <td class="tdc bl">0.28</td> + <td class="tdc bl">0.31</td> <td class="tdc bl">0.34</td> + <td class="tdc bl">0.36</td> <td class="tdc bl">0.39</td> + <td class="tdc bl">0.41</td> <td class="tdc bl">0.43</td> + <td class="tdc bl">0.47</td> <td class="tdc bl">0.50</td> + <td class="tdc bl">0.53</td> + </tr><tr> + <td class="tdl bb">12°</td> + <td class="tdc bb">0.16</td> <td class="tdc bl bb">0.20</td> + <td class="tdc bl bb">0.22</td> <td class="tdc bl bb">0.24</td> + <td class="tdc bl bb">0.26</td> <td class="tdc bl bb">0.29</td> + <td class="tdc bl bb">0.31</td> <td class="tdc bl bb">0.33</td> + <td class="tdc bl bb">0.34</td> <td class="tdc bl bb">0.36</td> + <td class="tdc bl bb">0.40</td> <td class="tdc bl bb">0.42</td> + <td class="tdc bl bb">0.46</td> + </tr><tr> + <td class="tdl">13°</td> + <td class="tdc">0.14</td> <td class="tdc bl">0.18</td> + <td class="tdc bl">0.19</td> <td class="tdc bl">0.21</td> + <td class="tdc bl">0.22</td> <td class="tdc bl">0.24</td> + <td class="tdc bl">0.26</td> <td class="tdc bl">0.27</td> + <td class="tdc bl">0.28</td> <td class="tdc bl">0.29</td> + <td class="tdc bl">0.33</td> <td class="tdc bl">0.35</td> + <td class="tdc bl">0.39</td> + </tr><tr> + <td class="tdl">14°</td> + <td class="tdc">0.12</td> <td class="tdc bl">0.15</td> + <td class="tdc bl">0.16</td> <td class="tdc bl">0.17</td> + <td class="tdc bl">0.18</td> <td class="tdc bl">0.19</td> + <td class="tdc bl">0.21</td> <td class="tdc bl">0.22</td> + <td class="tdc bl">0.22</td> <td class="tdc bl">0.23</td> + <td class="tdc bl">0.26</td> <td class="tdc bl">0.28</td> + <td class="tdc bl">0.32</td> + </tr><tr> + <td class="tdl">15°</td> + <td class="tdc">0.09</td> <td class="tdc bl">0.11</td> + <td class="tdc bl">0.12</td> <td class="tdc bl">0.14</td> + <td class="tdc bl">0.14</td> <td class="tdc bl">0.15</td> + <td class="tdc bl">0.16</td> <td class="tdc bl">0.16</td> + <td class="tdc bl">0.17</td> <td class="tdc bl">0.17</td> + <td class="tdc bl">0.19</td> <td class="tdc bl">0.21</td> + <td class="tdc bl">0.25</td> + </tr><tr> + <td class="tdl">16°</td> + <td class="tdc">0.06</td> <td class="tdc bl">0.07</td> + <td class="tdc bl">0.08</td> <td class="tdc bl">0.09</td> + <td class="tdc bl">0.10</td> <td class="tdc bl">0.10</td> + <td class="tdc bl">0.11</td> <td class="tdc bl">0.12</td> + <td class="tdc bl">0.12</td> <td class="tdc bl">0.12</td> + <td class="tdc bl">0.14</td> <td class="tdc bl">0.16</td> + <td class="tdc bl">0.18</td> + </tr><tr> + <td class="tdl">17°</td> + <td class="tdc">0.02</td> <td class="tdc bl">0.02</td> + <td class="tdc bl">0.03</td> <td class="tdc bl">0.03</td> + <td class="tdc bl">0.03</td> <td class="tdc bl">0.04</td> + <td class="tdc bl">0.04</td> <td class="tdc bl">0.04</td> + <td class="tdc bl">0.04</td> <td class="tdc bl">0.04</td> + <td class="tdc bl">0.05</td> <td class="tdc bl">0.05</td> + <td class="tdc bl">0.06</td> + </tr><tr> + <td class="tdl"> </td> + <td class="tdc fs_110" colspan="13"><i>To be added to the degree read.</i></td> + </tr><tr> + <td class="tdl">18°</td> + <td class="tdc">0.02</td> <td class="tdc bl">0.03</td> + <td class="tdc bl">0.03</td> <td class="tdc bl">0.03</td> + <td class="tdc bl">0.03</td> <td class="tdc bl">0.03</td> + <td class="tdc bl">0.03</td> <td class="tdc bl">0.03</td> + <td class="tdc bl">0.03</td> <td class="tdc bl">0.03</td> + <td class="tdc bl">0.03</td> <td class="tdc bl">0.03</td> + <td class="tdc bl">0.02</td> + </tr><tr> + <td class="tdl">19°</td> + <td class="tdc">0.06</td> <td class="tdc bl">0.08</td> + <td class="tdc bl">0.08</td> <td class="tdc bl">0.09</td> + <td class="tdc bl">0.09</td> <td class="tdc bl">0.10</td> + <td class="tdc bl">0.10</td> <td class="tdc bl">0.10</td> + <td class="tdc bl">0.10</td> <td class="tdc bl">0.10</td> + <td class="tdc bl">0.10</td> <td class="tdc bl">0.08</td> + <td class="tdc bl">0.06</td> + </tr><tr> + <td class="tdl">20°</td> + <td class="tdc">0.11</td> <td class="tdc bl">0.14</td> + <td class="tdc bl">0.15</td> <td class="tdc bl">0.17</td> + <td class="tdc bl">0.17</td> <td class="tdc bl">0.18</td> + <td class="tdc bl">0.18</td> <td class="tdc bl">0.18</td> + <td class="tdc bl">0.19</td> <td class="tdc bl">0.19</td> + <td class="tdc bl">0.18</td> <td class="tdc bl">0.15</td> + <td class="tdc bl">0.11</td> + </tr><tr> + <td class="tdl">21°</td> + <td class="tdc">0.16</td> <td class="tdc bl">0.20</td> + <td class="tdc bl">0.22</td> <td class="tdc bl">0.24</td> + <td class="tdc bl">0.24</td> <td class="tdc bl">0.25</td> + <td class="tdc bl">0.25</td> <td class="tdc bl">0.25</td> + <td class="tdc bl">0.26</td> <td class="tdc bl">0.26</td> + <td class="tdc bl">0.25</td> <td class="tdc bl">0.22</td> + <td class="tdc bl">0.18</td> + </tr><tr> + <td class="tdl">22°</td> + <td class="tdc">0.21</td> <td class="tdc bl">0.26</td> + <td class="tdc bl">0.28</td> <td class="tdc bl">0.31</td> + <td class="tdc bl">0.31</td> <td class="tdc bl">0.32</td> + <td class="tdc bl">0.32</td> <td class="tdc bl">0.32</td> + <td class="tdc bl">0.33</td> <td class="tdc bl">0.34</td> + <td class="tdc bl">0.32</td> <td class="tdc bl">0.29</td> + <td class="tdc bl">0.25</td> + </tr><tr> + <td class="tdl">23°</td> + <td class="tdc">0.27</td> <td class="tdc bl">0.32</td> + <td class="tdc bl">0.35</td> <td class="tdc bl">0.37</td> + <td class="tdc bl">0.38</td> <td class="tdc bl">0.39</td> + <td class="tdc bl">0.39</td> <td class="tdc bl">0.39</td> + <td class="tdc bl">0.40</td> <td class="tdc bl">0.42</td> + <td class="tdc bl">0.39</td> <td class="tdc bl">0.36</td> + <td class="tdc bl">0.33</td> + </tr><tr> + <td class="tdl">24°</td> + <td class="tdc">0.32</td> <td class="tdc bl">0.38</td> + <td class="tdc bl">0.41</td> <td class="tdc bl">0.43</td> + <td class="tdc bl">0.44</td> <td class="tdc bl">0.46</td> + <td class="tdc bl">0.46</td> <td class="tdc bl">0.47</td> + <td class="tdc bl">0.47</td> <td class="tdc bl">0.50</td> + <td class="tdc bl">0.46</td> <td class="tdc bl">0.43</td> + <td class="tdc bl">0.40</td> + </tr><tr> + <td class="tdl bb">25°</td> + <td class="tdc bb">0.37</td> <td class="tdc bl bb">0.44</td> + <td class="tdc bl bb">0.47</td> <td class="tdc bl bb">0.49</td> + <td class="tdc bl bb">0.51</td> <td class="tdc bl bb">0.53</td> + <td class="tdc bl bb">0.54</td> <td class="tdc bl bb">0.55</td> + <td class="tdc bl bb">0.55</td> <td class="tdc bl bb">0.58</td> + <td class="tdc bl bb">0.54</td> <td class="tdc bl bb">0.51</td> + <td class="tdc bl bb">0.48</td> + </tr><tr> + <td class="tdl">26°</td> + <td class="tdc">0.43</td> <td class="tdc bl">0.50</td> + <td class="tdc bl">0.54</td> <td class="tdc bl">0.56</td> + <td class="tdc bl">0.58</td> <td class="tdc bl">0.60</td> + <td class="tdc bl">0.61</td> <td class="tdc bl">0.62</td> + <td class="tdc bl">0.62</td> <td class="tdc bl">0.66</td> + <td class="tdc bl">0.62</td> <td class="tdc bl">0.58</td> + <td class="tdc bl">0.55</td> + </tr><tr> + <td class="tdl">27°</td> + <td class="tdc">0.49</td> <td class="tdc bl">0.57</td> + <td class="tdc bl">0.61</td> <td class="tdc bl">0.63</td> + <td class="tdc bl">0.65</td> <td class="tdc bl">0.68</td> + <td class="tdc bl">0.68</td> <td class="tdc bl">0.69</td> + <td class="tdc bl">0.70</td> <td class="tdc bl">0.74</td> + <td class="tdc bl">0.70</td> <td class="tdc bl">0.65</td> + <td class="tdc bl">0.62</td> + </tr><tr> + <td class="tdl">28°</td> + <td class="tdc">0.56</td> <td class="tdc bl">0.64</td> + <td class="tdc bl">0.68</td> <td class="tdc bl">0.70</td> + <td class="tdc bl">0.72</td> <td class="tdc bl">0.76</td> + <td class="tdc bl">0.76</td> <td class="tdc bl">0.78</td> + <td class="tdc bl">0.78</td> <td class="tdc bl">0.82</td> + <td class="tdc bl">0.78</td> <td class="tdc bl">0.72</td> + <td class="tdc bl">0.70</td> + </tr><tr> + <td class="tdl">29°</td> + <td class="tdc">0.63</td> <td class="tdc bl">0.71</td> + <td class="tdc bl">0.75</td> <td class="tdc bl">0.78</td> + <td class="tdc bl">0.79</td> <td class="tdc bl">0.84</td> + <td class="tdc bl">0.84</td> <td class="tdc bl">0.86</td> + <td class="tdc bl">0.86</td> <td class="tdc bl">0.90</td> + <td class="tdc bl">0.88</td> <td class="tdc bl">0.80</td> + <td class="tdc bl">0.78</td> + </tr><tr> + <td class="tdl">30°</td> + <td class="tdc">0.70</td> <td class="tdc bl">0.78</td> + <td class="tdc bl">0.82</td> <td class="tdc bl">0.87</td> + <td class="tdc bl">0.87</td> <td class="tdc bl">0.92</td> + <td class="tdc bl">0.92</td> <td class="tdc bl">0.94</td> + <td class="tdc bl">0.94</td> <td class="tdc bl">0.98</td> + <td class="tdc bl">0.94</td> <td class="tdc bl">0.88</td> + <td class="tdc bl">0.86</td> + </tr><tr> + <td class="tdl">35°</td> + <td class="tdc">1.10</td> <td class="tdc bl">1.17</td> + <td class="tdc bl">1.22</td> <td class="tdc bl">1.24</td> + <td class="tdc bl">1.30</td> <td class="tdc bl">1.32</td> + <td class="tdc bl">1.33</td> <td class="tdc bl">1.35</td> + <td class="tdc bl">1.36</td> <td class="tdc bl">1.39</td> + <td class="tdc bl">1.34</td> <td class="tdc bl">1.27</td> + <td class="tdc bl">1.25</td> + </tr><tr> + <td class="tdl">40°</td> + <td class="tdc">1.50</td> <td class="tdc bl">1.61</td> + <td class="tdc bl">1.67</td> <td class="tdc bl">1.71</td> + <td class="tdc bl">1.73</td> <td class="tdc bl">1.79</td> + <td class="tdc bl">1.79</td> <td class="tdc bl">1.80</td> + <td class="tdc bl">1.82</td> <td class="tdc bl">1.83</td> + <td class="tdc bl">1.78</td> <td class="tdc bl">1.69</td> + <td class="tdc bl">1.65</td> + </tr><tr> + <td class="tdl">50°</td> <td class="tdc">—</td> + <td class="tdc bl">2.65</td> <td class="tdc bl">2.71</td> + <td class="tdc bl">2.74</td> <td class="tdc bl">2.78</td> + <td class="tdc bl">2.80</td> <td class="tdc bl">2.80</td> + <td class="tdc bl">2.80</td> <td class="tdc bl">2.80</td> + <td class="tdc bl">2.79</td> <td class="tdc bl">2.70</td> + <td class="tdc bl">2.56</td> <td class="tdc bl">2.51</td> + </tr><tr> + <td class="tdl">60°</td> + <td class="tdc">—</td> <td class="tdc bl">3.87</td> + <td class="tdc bl">3.88</td> <td class="tdc bl">3.88</td> + <td class="tdc bl">3.88</td> <td class="tdc bl">3.88</td> + <td class="tdc bl">3.88</td> <td class="tdc bl">3.88</td> + <td class="tdc bl">3.90</td> <td class="tdc bl">3.82</td> + <td class="tdc bl">3.70</td> <td class="tdc bl">3.43</td> + <td class="tdc bl">3.41</td> + </tr><tr> + <td class="tdl">70°</td> + <td class="tdc">—</td> <td class="tdc bl">—</td> + <td class="tdc bl">5.18</td> <td class="tdc bl">5.20</td> + <td class="tdc bl">5.14</td> <td class="tdc bl">5.13</td> + <td class="tdc bl">5.10</td> <td class="tdc bl">5.08</td> + <td class="tdc bl">5.06</td> <td class="tdc bl">4.90</td> + <td class="tdc bl">4.72</td> <td class="tdc bl">4.47</td> + <td class="tdc bl">4.35</td> + </tr><tr> + <td class="tdl">80°</td> + <td class="tdc">—</td> <td class="tdc bl">—</td> + <td class="tdc bl">6.62</td> <td class="tdc bl">6.59</td> + <td class="tdc bl">6.54</td> <td class="tdc bl">6.16</td> + <td class="tdc bl">6.38</td> <td class="tdc bl">6.30</td> + <td class="tdc bl">6.26</td> <td class="tdc bl">6.06</td> + <td class="tdc bl">5.82</td> <td class="tdc bl">5.50</td> + <td class="tdc bl">5.33</td> + </tr> + </tbody> +</table> + +<p><span class="pagenum"><a id="Page_73"></a>[Pg 73]</span> +According to observations of Gerlach, the correction for temperature +varies with the concentration of the solution and the range of +temperature as shown in the table.</p> + +<p id="P_58"><b>58. Comparison of Brix and Baumé Degrees.</b>—The following table +shows the degree baumé and the specific gravity of a sugar solution +for each degree brix (per cent of sugar in solution) from zero to +ninety-five:<a id="FNanchor_34" href="#Footnote_34" class="fnanchor">[34]</a></p> + +<table class="spb1"> + <thead><tr> + <th class="tdc bb">Degree<br>brix.</th> + <th class="tdc bb"> Degree <br>baumé.</th> + <th class="tdc bb"> Specific <br>gravity</th> + <th class="tdc bl bb"> Degree <br>brix.</th> + <th class="tdc bb">Degree<br>baumé.</th> + <th class="tdc bb"> Specific <br>gravity</th> + </tr></thead> + <tbody><tr> + <td class="tdc"> 1.0</td> <td class="tdc"> 0.6</td> + <td class="tdc">1.00388</td> + <td class="tdc bl">37.0</td> <td class="tdc">20.7</td> + <td class="tdc">1.16413</td> + </tr><tr> + <td class="tdc"> 2.0</td> <td class="tdc"> 1.1</td> + <td class="tdc">1.00779</td> + <td class="tdc bl">38.0</td> <td class="tdc">21.2</td> + <td class="tdc">1.16920</td> + </tr><tr> + <td class="tdc"> 3.0</td> <td class="tdc"> 1.7</td> + <td class="tdc">1.01173</td> + <td class="tdc bl">39.0</td> <td class="tdc">21.8</td> + <td class="tdc">1.17430</td> + </tr><tr> + <td class="tdc"> 4.0</td> <td class="tdc"> 2.3</td> + <td class="tdc">1.01570</td> + <td class="tdc bl">40.0</td> <td class="tdc">22.3</td> + <td class="tdc">1.17943</td> + </tr><tr> + <td class="tdc"> 5.0</td> <td class="tdc"> 2.8</td> + <td class="tdc">1.01970</td> + <td class="tdc bl">41.0</td> <td class="tdc">22.9</td> + <td class="tdc">1.18460</td> + </tr><tr> + <td class="tdc"> 6.0</td> <td class="tdc"> 3.4</td> + <td class="tdc">1.02373</td> + <td class="tdc bl">42.0</td> <td class="tdc">23.4</td> + <td class="tdc">1.18981</td> + </tr><tr> + <td class="tdc"> 7.0</td> <td class="tdc"> 4.0</td> + <td class="tdc">1.02779</td> + <td class="tdc bl">43.0</td> <td class="tdc">24.0</td> + <td class="tdc">1.19505</td> + </tr><tr> + <td class="tdc"> 8.0</td> <td class="tdc"> 4.5</td> + <td class="tdc">1.03187</td> + <td class="tdc bl">44.0</td> <td class="tdc">24.5</td> + <td class="tdc">1.20033</td> + </tr><tr> + <td class="tdc"> 9.0</td> <td class="tdc"> 5.1</td> + <td class="tdc">1.03599</td> + <td class="tdc bl">45.0</td> <td class="tdc">25.0</td> + <td class="tdc">1.20565</td> + </tr><tr> + <td class="tdc">10.0</td> <td class="tdc"> 5.7</td> + <td class="tdc">1.04014</td> + <td class="tdc bl">46.0</td> <td class="tdc">25.6</td> + <td class="tdc">1.21100</td> + </tr><tr> + <td class="tdc">11.0</td> <td class="tdc"> 6.2</td> + <td class="tdc">1.04431</td> + <td class="tdc bl">47.0</td> <td class="tdc">26.1</td> + <td class="tdc">1.21639</td> + </tr><tr> + <td class="tdc">12.0</td> <td class="tdc"> 6.8</td> + <td class="tdc">1.04852</td> + <td class="tdc bl">48.0</td> <td class="tdc">26.6</td> + <td class="tdc">1.22182</td> + </tr><tr> + <td class="tdc">13.0</td> <td class="tdc"> 7.4</td> + <td class="tdc">1.05276</td> + <td class="tdc bl">49.0</td> <td class="tdc">27.2</td> + <td class="tdc">1.22128</td> + </tr><tr> + <td class="tdc">14.0</td> <td class="tdc"> 7.9</td> + <td class="tdc">1.05703</td> + <td class="tdc bl">50.0</td> <td class="tdc">27.7</td> + <td class="tdc">1.23278</td> + </tr><tr> + <td class="tdc">15.0</td> <td class="tdc"> 8.5</td> + <td class="tdc">1.06133</td> + <td class="tdc bl">51.0</td> <td class="tdc">28.2</td> + <td class="tdc">1.23832</td> + </tr><tr> + <td class="tdc">16.0</td> <td class="tdc"> 9.0</td> + <td class="tdc">1.06566</td> + <td class="tdc bl">52.0</td> <td class="tdc">28.8</td> + <td class="tdc">1.24390</td> + </tr><tr> + <td class="tdc">17.0</td> <td class="tdc"> 9.6</td> + <td class="tdc">1.07002</td> + <td class="tdc bl">53.0</td> <td class="tdc">29.3</td> + <td class="tdc">1.24951</td> + </tr><tr> + <td class="tdc">18.0</td> <td class="tdc">10.1</td> + <td class="tdc">1.07441</td> + <td class="tdc bl">54.0</td> <td class="tdc">29.8</td> + <td class="tdc">1.25517</td> + </tr><tr> + <td class="tdc">19.0</td> <td class="tdc">10.7</td> + <td class="tdc">1.07884</td> + <td class="tdc bl">55.0</td> <td class="tdc">30.4</td> + <td class="tdc">1.26086</td> + </tr><tr> + <td class="tdc">20.0</td> <td class="tdc">11.3</td> + <td class="tdc">1.08329</td> + <td class="tdc bl">56.0</td> <td class="tdc">30.9</td> + <td class="tdc">1.26658</td> + </tr><tr> + <td class="tdc">21.0</td> <td class="tdc">11.8</td> + <td class="tdc">1.08778</td> + <td class="tdc bl">57.0</td> <td class="tdc">31.4</td> + <td class="tdc">1.27235</td> + </tr><tr> + <td class="tdc">22.0</td> <td class="tdc">12.4</td> + <td class="tdc">1.09231</td> + <td class="tdc bl">58.0</td> <td class="tdc">31.9</td> + <td class="tdc">1.27816</td> + </tr><tr> + <td class="tdc">23.0</td> <td class="tdc">13.0</td> + <td class="tdc">1.09686</td> + <td class="tdc bl">59.0</td> <td class="tdc">32.5</td> + <td class="tdc">1.28400</td> + </tr><tr> + <td class="tdc">24.0</td> <td class="tdc">13.5</td> + <td class="tdc">1.10145</td> + <td class="tdc bl">60.0</td> <td class="tdc">33.0</td> + <td class="tdc">1.28989</td> + </tr><tr> + <td class="tdc">25.0</td> <td class="tdc">14.1</td> + <td class="tdc">1.10607</td> + <td class="tdc bl">61.0</td> <td class="tdc">33.5</td> + <td class="tdc">1.29581</td> + </tr><tr> + <td class="tdc">26.0</td> <td class="tdc">14.6</td> + <td class="tdc">1.11072</td> + <td class="tdc bl">62.0</td> <td class="tdc">34.0</td> + <td class="tdc">1.30177</td> + </tr><tr> + <td class="tdc">27.0</td> <td class="tdc">15.2</td> + <td class="tdc">1.11541</td> + <td class="tdc bl">63.0</td> <td class="tdc">34.5</td> + <td class="tdc">1.30177</td> + </tr><tr> + <td class="tdc">28.0</td> <td class="tdc">15.7</td> + <td class="tdc">1.12013</td> + <td class="tdc bl">64.0</td> <td class="tdc">35.1</td> + <td class="tdc">1.31381</td> + </tr><tr> + <td class="tdc">29.0</td> <td class="tdc">16.3</td> + <td class="tdc">1.12488</td> + <td class="tdc bl">65.0</td> <td class="tdc">35.6</td> + <td class="tdc">1.31989</td> + </tr><tr> + <td class="tdc">30.0</td> <td class="tdc">16.8</td> + <td class="tdc">1.12967</td> + <td class="tdc bl">66.0</td> <td class="tdc">36.1</td> + <td class="tdc">1.32601</td> + </tr><tr> + <td class="tdc">31.0</td> <td class="tdc">17.4</td> + <td class="tdc">1.13449</td> + <td class="tdc bl">67.0</td> <td class="tdc">36.6</td> + <td class="tdc">1.33217</td> + </tr><tr> + <td class="tdc">32.0</td> <td class="tdc">18.0</td> + <td class="tdc">1.13934</td> + <td class="tdc bl">68.0</td> <td class="tdc">37.1</td> + <td class="tdc">1.33836</td> + </tr><tr> + <td class="tdc">33.0</td> <td class="tdc">18.5</td> + <td class="tdc">1.14423</td> + <td class="tdc bl">69.0</td> <td class="tdc">37.6</td> + <td class="tdc">1.34460</td> + </tr><tr> + <td class="tdc">34.0</td> <td class="tdc">19.1</td> + <td class="tdc">1.14915</td> + <td class="tdc bl">70.0</td> <td class="tdc">38.1</td> + <td class="tdc">1.35088</td> + </tr><tr> + <td class="tdc">35.0</td> <td class="tdc">19.6</td> + <td class="tdc">1.15411</td> + <td class="tdc bl">71.0</td> <td class="tdc">38.6</td> + <td class="tdc">1.35720</td> + </tr><tr> + <td class="tdc">36.0</td> <td class="tdc">20.1</td> + <td class="tdc">1.15911</td> + <td class="tdc bl">72.0</td> <td class="tdc">39.1</td> + <td class="tdc">1.36355 + <span class="pagenum"><a id="Page_74"></a>[Pg 74]</span></td> + </tr><tr> + <td class="tdc" colspan="3"> </td> + <td class="tdc bl" colspan="3"> </td> + </tr><tr> + <td class="tdc">73.0</td> <td class="tdc">39.6</td> + <td class="tdc">1.36995</td> + <td class="tdc bl">85.0</td> <td class="tdc">45.5</td> + <td class="tdc">1.44986</td> + </tr><tr> + <td class="tdc">74.0</td> <td class="tdc">40.1</td> + <td class="tdc">1.37639</td> + <td class="tdc bl">86.0</td> <td class="tdc">46.0</td> + <td class="tdc">1.45678</td> + </tr><tr> + <td class="tdc">75.0</td> <td class="tdc">40.6</td> + <td class="tdc">1.38287</td> + <td class="tdc bl">87.0</td> <td class="tdc">46.5</td> + <td class="tdc">1.46374</td> + </tr><tr> + <td class="tdc">76.0</td> <td class="tdc">41.1</td> + <td class="tdc">1.38939</td> + <td class="tdc bl">88.0</td> <td class="tdc">47.0</td> + <td class="tdc">1.47074</td> + </tr><tr> + <td class="tdc">77.0</td> <td class="tdc">41.6</td> + <td class="tdc">1.39595</td> + <td class="tdc bl">89.0</td> <td class="tdc">47.5</td> + <td class="tdc">1.47778</td> + </tr><tr> + <td class="tdc">78.0</td> <td class="tdc">42.1</td> + <td class="tdc">1.40254</td> + <td class="tdc bl">90.0</td> <td class="tdc">49.9</td> + <td class="tdc">1.48486</td> + </tr><tr> + <td class="tdc">79.0</td> <td class="tdc">42.6</td> + <td class="tdc">1.40918</td> + <td class="tdc bl">91.0</td> <td class="tdc">48.4</td> + <td class="tdc">1.49199</td> + </tr><tr> + <td class="tdc">80.0</td> <td class="tdc">43.1</td> + <td class="tdc">1.41586</td> + <td class="tdc bl">92.0</td> <td class="tdc">48.9</td> + <td class="tdc">1.49915</td> + </tr><tr> + <td class="tdc">81.0</td> <td class="tdc">43.6</td> + <td class="tdc">1.42258</td> + <td class="tdc bl">93.0</td> <td class="tdc">49.3</td> + <td class="tdc">1.50635</td> + </tr><tr> + <td class="tdc">82.0</td> <td class="tdc">44.1</td> + <td class="tdc">1.42934</td> + <td class="tdc bl">94.0</td> <td class="tdc">49.8</td> + <td class="tdc">1.51359</td> + </tr><tr> + <td class="tdc">83.0</td> <td class="tdc">44.6</td> + <td class="tdc">1.43614</td> + <td class="tdc bl">95.0</td> <td class="tdc">50.3</td> + <td class="tdc">1.52087</td> + </tr><tr> + <td class="tdc">84.0</td> <td class="tdc">45.1</td> + <td class="tdc">1.44298</td> + <td class="tdc bl"> </td> <td class="tdc"> </td> + <td class="tdc"> </td> + </tr> + </tbody> +</table> + +<p><b>59. Error Due to Impurities.</b>—The fact that equal per cents +of solid bodies in solution affect the specific gravity in different +degrees has already been noted. The specific gravities of the solutions +of the common sugars, however, are so nearly the same for equal per +cents of solid matter in solution as to render the use of a brix +hydrometer quite general for technical purpose. For the mineral salts +which often occur in sugar solutions the case is quite different. A +twenty per cent solution of cane sugar at 17°.5 has a specific gravity +1.08329 and of dextrose 1.08310, practically identical. But a solution +of calcium acetate of similar strength has a specific gravity of +1.0874; of sodium sulfate 1.0807, and of potassium nitrate 1.1359. +This latter number would correspond to a sugar content of nearly +twenty-seven per cent. The brix scale can, therefore, be regarded as +giving only approximately the percentage of solid matter in sugar +solutions and, while useful in technical work, should never be relied +upon for exact analytical data.</p> + +<h3>THE DETERMINATION OF SUGAR<br> WITH POLARIZED LIGHT.</h3> + +<p><b>60. Optical Properties of Natural Sugars.</b>—The solutions of all +natural sugars have the property of deflecting the plane of polarized +light and the degree of deflection corresponds to the quantity of sugar +in solution. By measuring the amplitude of the rotation produced the +percentage of sugar in the solution can be determined. In order to +secure accuracy in the determinations it is necessary that only one +kind of sugar be present, or, if more than one, that the quantities of +all but one be determined by other means, and the disturbances produced +<span class="pagenum"><a id="Page_75"></a>[Pg 75]</span> +thereby in the total rotation be properly arranged. In point of fact +the process in practice is applied chiefly to cane and milk sugars, +both of which occur in nature in an approximately pure state. The +process is also useful in determining cane sugar when mixed with +other kinds, by reason of the fact that this sugar after hydrolysis +by treatment with a weak acid for a long or a strong acid for a short +time, definitely changes its rotating power. Since, by the same +treatment, the rotating power of other sugars which may be present is +only slightly altered, the total disturbance produced is approximately +due to the inversion of the cane sugar.</p> + +<p>Dextrose and maltose arising from the hydrolysis of starch may also +be determined with a fair degree of accuracy by their deportment +with polarized light. When a solution of natural sugars shows +negative results when examined with polarized light, it is due to an +admixture of two or more sugars of opposite polarizing powers in such +proportions as to produce neutrality. This condition often occurs +in the examination of honeys or in submitting artificial sugars to +polarimetric observations. In the latter case the neutrality is caused +by the tendency manifested by artificially produced sugars to form twin +compounds of optically opposite qualities.</p> + +<p>The instrument used for measuring the degree of deflection produced in +a plane of polarized light is called a polariscope, polarimeter, or +optical saccharimeter. For a theoretical discussion of the principles +of polarization and the application of these principles in the +construction of polariscopes, the reader is referred to the standard +works on optics and the construction of optical instruments.<a id="FNanchor_35" href="#Footnote_35" class="fnanchor">[35]</a> +For the purposes of this work a description of the instruments commonly +employed and the methods of using them will be sufficient.</p> + +<p><b>61. Polarized Light.</b>—When a ray of light has been repeatedly +reflected from bright surfaces or when it passes through certain +crystalline bodies it acquires peculiar properties and is said to be +polarized.</p> + +<p>Polarization is therefore a term applied to a phenomenon of light, in +which the vibrations of the ether are supposed to be restricted to a +<span class="pagenum"><a id="Page_76"></a>[Pg 76]</span> +particular form of an ellipse whose axes remain fixed in direction. If +the ellipse become a straight line it is called plane polarization. +This well-known phenomenon is most easily produced by a nicol prism, +consisting of a cut crystal of calcium carbonate (Iceland spar). This +rhombohedral crystal, the natural ends of which form angles of 71° and +109°, respectively, with the opposite edges of its principal section, +is prepared as follows:</p> + +<p>The ends of the crystals are ground until the angles just mentioned +become 68° and 112°. The crystal is then divided diagonally at right +angles with the planes of the ends and with the principal section, and +after the new surfaces are polished they are joined again by canada +balsam. The principal section of this prism passes through the shorter +diagonal of the two rhombic ends. If now a ray of light fall on one +of the ends of this prism, parallel with the edge of its longer side, +it suffers double refraction, and each ray is plane polarized, the +one at right angles with the other. That part of the entering ray of +light which is most refracted is called the ordinary and the other the +extraordinary ray. The refractive index of the film of balsam being +intermediate between those of the rays, permits the total reflection of +the ordinary ray, which, passing to the blackened sides of the prism, +is absorbed. The extraordinary ray passes the film of balsam without +deviation and emerges from the prism in a direction parallel with the +incident ray, having, however, only half of its luminous intensity.</p> + +<p>Two such prisms, properly mounted, furnish the essential parts of a +polarizing apparatus. They are called the polarizer and the analyzer, +respectively.</p> + +<p>If now the plane of vibration in each prism be regarded as coincident +with its principal section, the following phenomena are observed: +If the prisms are so placed that the principal sections lie in the +prolongation of the same plane, then the extraordinary polarized ray +from the polarizer passes into the analyzer, which practically may +be regarded in this position as a continuation of the same prism. +It happens, therefore, that the extraordinary polarized ray passes +through the analyzer exactly as it did through the polarizer, and is +not reflected by the film of balsam, but emerges from the analyzer in +<span class="pagenum"><a id="Page_77"></a>[Pg 77]</span> +seemingly the same condition as from the polarizer. If now the analyzer +be rotated 180°, bringing the principal section again in the same +plane, the same phenomenon is observed. But if the rotation be in +either direction only 90°, then the polarized ray from the first prism, +incident on the second, deports itself exactly as the ordinary ray, +and on meeting the film of balsam is totally reflected. The field of +vision, therefore, is perfectly dark.</p> + +<p>In all other inclinations of the planes of the principal sections of +the two prisms the ray incident in the analyzer is separated into +two, an ordinary and extraordinary, varying in luminous intensity in +proportion to the square of the cosine of the angle of the two planes.</p> + +<div class="figleft smcap"> + <img id="FIG_31" src="images/fig31.jpg" alt="" width="200" height="531" > + <p class="center spb1">Figure 31. Course<br> of Rays of Light<br> In a Nicol.</p> +</div> + +<p>Thus, by gradually turning the analyzer, the field of vision passes +slowly from maximum luminosity to complete obscurity. The expression +crossed nicols refers to the latter condition of the field of vision.</p> + +<p><b>62. Description of the Prism.</b>—In a nicol made as described +above, <a href="#FIG_31">Fig. 31</a>, suppose a ray of light parallel with the longer +side of the prism be incident to the end <i>a</i> <i>b</i> at <i>m</i>. By the +double refracting power of the spar the ray is divided into two, which +traverse the first half of the prism. The two rays are polarized at +right angles to one another. The less refracted ray when it strikes the +film of Canada balsam passes through it without interference. The more +refracted ray strikes the balsam at <i>o</i> at such an angle as to be +totally reflected and made to pass out of the prism in the direction +<span class="pagenum"><a id="Page_78"></a>[Pg 78]</span> +<i>o r</i>. If the prism be blackened at the surface the ray will be +entirely absorbed. The other ray passes on through the other half of +the prism and emerges in the direction of <i>qs</i>. It is evident that +the emergent light from a nicol has only half the illuminating power +possessed by the immergent rays.</p> + +<p>The polarized plane of light from the nicol just described may be +regarded as passing also into a second nicol of essentially the same +construction as the first.</p> + +<p>This second nicol, called the analyzer, is so constructed as to revolve +freely about its longitudinal axis, and is attached to a graduated +circle in such a way that the degree of rotation can be accurately +read. If the planes of polarization of the two nicols are coincident +when prolonged, the ray of light passing from the first nicol will pass +through the second practically unchanged in character or intensity. If, +however, the analyzing nicol be turned until the plane of polarization +is at right angles to that of the polarizer the immergent ray will +suffer refraction in such a manner as to be totally reflected when +reaching the film of balsam and will be thus entirely lost. In making +a complete revolution of the analyzer, therefore, two positions of +maximum intensity of light and two of darkness will be observed. In +intermediate positions the ray immergent to the analyzer will be +separated as in the first instance into two rays <i>g p</i> varying +intensities, one of which will be always totally reflected.</p> + +<div class="figright smcap"> + <img id="FIG_32" src="images/fig32.jpg" alt="" width="200" height="431" > + <p class="center spb1">Figure 32. Theory of<br> the Nicol.</p> +</div> + +<p>In <a href="#FIG_32">Fig. 32</a> is given a more detailed illustration of the +action of the rays of light. The film of balsam is represented as enlarged and of +the thickness <i>bb</i>. Draw the perpendiculars represented by the dotted +lines <i>n</i>₁ <i>n</i>ʹ₁, <i>n</i>₂ <i>n</i>ʹ₂, <i>n</i>₃ <i>n</i>ʹ₃ +and <i>n</i>₄ <i>n</i>ʹ₄. In passing into the prism at <i>m</i> both +<span class="pagenum"><a id="Page_79"></a>[Pg 79]</span> +refracted rays are bent towards the normal <i>m n</i>ʹ₁. The degree of +deflection depends on the refractive index of the two rays 1.52 and +1.66 respectively. The refractive index of the extraordinary ray in +calcspar being 1.52, and in Canada balsam 1.54, it suffers but little +disturbance in passing from one to the other. On the other hand the +balsam, being considerably less refractive for the ordinary ray than +the calcspar, causes that ray to diverge outwards from the normal +<i>o n</i>ʹ₂, and to such a degree as to suffer total reflection. The +critical angle, that is the angle at which a ray issuing from a more +refractive into a less refractive medium, emerges just parallel to the +bounding surfaces, depends on the relative index of refraction. In the +case under consideration the ratio for balsam and spar is 1.54/1.66 = +0.928 = sin 68°. Therefore the limiting value of <i>m o</i> <i>n</i>₃ +so that <i>m o</i> may just emerge in the direction <i>od</i> is 68°. +If now <i>mo</i> were parallel to <i>o d</i> the angle <i>m o n</i>, +would be just 68°, being opposite <i>b a d</i>. which has been ground +to 68° in the construction of the prism. But in passing into the prism, +<i>m o</i> is refracted so that the angle <i>m o n</i>₃ is greater +than <i>b a d</i>. It is therefore always certain that by grinding +<i>b a d</i> to 68° the ordinary ray <i>m o</i> will be with certainty +entirely thrown out in every case. In respect of the analyzing nicol +the following additional observations will be found useful. In all +uniaxial crystals there are two directions at right angles to each +other, one of greatest and one of least resistance to the propagation +of luminous vibrations. These planes are in the direction of the +principal axis and at right angles thereto. Only light vibrating in +these two directions can be transmitted through calcspar; and all +incident light propagated by vibrations in a plane at any other angle +to the principal section is resolved into two such component rays. But +the velocities of transmission in the two directions are unequal, that +is, the refractive index of the spar for the two rays is different. If +the analyzing nicol be so adjusted as to receive the emergent light +from the polarizer when the corresponding planes of the two prisms are +coincident when extended, the emergent extraordinary ray falling into +a plane of the same resistance as that it had just left is propagated +through the second nicol with the same velocity that it passed the +<span class="pagenum"><a id="Page_80"></a>[Pg 80]</span> +first one. It is therefore similarly refracted. If, however, the +two prisms be so arranged that corresponding planes cross then the +extraordinary ray falls into a plane which it traverses with greater +velocity than it had before and is accordingly refracted and takes the +course which ends in total reflection at the film of balsam. No light +therefore can pass through the prism in that position. If any other +substance, as for instance a solution of sugar, capable of rotating +a plane of polarized light, be interposed between the two nicols the +effect produced is the same as if the analyzer had been turned to a +corresponding degree. When the analyzer is turned to that degree the +corresponding planes again coincide and the light passes. This is the +principle on which the construction of all polarizing instruments is +based.<a id="FNanchor_36" href="#Footnote_36" class="fnanchor">[36]</a></p> + +<p><b>63. The Polariscope.</b>—A polariscope for the examination of +solutions of sugar consists essentially of a prism for polarizing +the light, called a nicol, a tube of definite length for holding the +sugar solution, a second nicol made movable on its axis for adjustment +to the degree of rotation and a graduated arc for measuring it. +Instead of having the second nicol movable, many instruments have an +adjusting wedge of quartz of opposite polarizing power to the sugar, +by means of which the displacement produced on the polarized plane is +corrected. A graduated scale and vernier serve to measure the movement +of the wedges and give in certain conditions the desired reading of +the percentage of sugar present. Among the multitude of instruments +which have been devised for analytical purposes, only three will be +found in common use, and the scope of this volume will not allow space +for a description of a greater number. For a practical discussion +of the principles of polarization and their application to optical +saccharimetry, the reader may conveniently refer to the excellent +manuals of Sidersky, Tucker, Landolt, and Wiechmann.<a id="FNanchor_37" href="#Footnote_37" class="fnanchor">[37]</a></p> + +<p><b>64. Kinds of Polariscopes.</b>—The simplest form of a polarizing +apparatus consists of two nicol prisms, one of which, <i>viz.</i>, the +analyzer, is capable of rotation about its long axis. The prolongation +of this axis is continuous with that of the other prism, <i>viz.</i>, +the polarizer. The two prisms are sufficiently removed from each other +to allow of the interposition of the polarizing body whose rotatory +power is to be measured. +<span class="pagenum"><a id="Page_81"></a>[Pg 81]</span></p> + +<p>For purposes of description three kinds of polarimeters may be +mentioned.</p> + +<p>1. <i>Instruments in which the deviation of the plane of polarization +is measured by turning the analyzer about its axis.</i></p> + +<p>Instruments of this kind conform to the simple type first mentioned, +and are <i>coeteris paribus</i> the best. The Laurent, Wild, +Landolt-Lippich, etc., belong to this class.</p> + +<p>2. <i>Instruments in which both nicols are fixed and the direction of +the plane of polarized light corrected by the interposition of a wedge +of a solid polarizing body.</i></p> + +<p>Belonging to this class are the apparatus of Soleil, Duboscq, +Scheibler, and the compensating apparatus of Schmidt and Haensch.</p> + +<p>3. <i>Apparatus in which the analyzer is set at a constant angle with +the polarizer, and the compensation secured by varying the length or +concentration of the interposed polarizing liquid.</i></p> + +<p>The apparatus of Trannin belongs to this class.</p> + +<p><b>65. Appearance of Field of Vision.</b>—Polarimeters are also +classified in respect of the appearance of the field of vision.</p> + +<p>1. <i>Tint Instruments.</i>—The field of vision in these instruments +in every position of the nicols, except that on which the plane of +vibration of the polarized light is coincident with the three principal +sections, is composed of two semi-disks of different colors.</p> + +<p>2. <i>Shadow Instruments.</i>—The field of vision in this class of +polarimeters in all except neutral positions, is composed of two +semi-disks, one dark and one yellow. As the neutral position is +approximated the two disks gradually assume a light yellow color, and +when neutrality is reached they appear to be equally colored.</p> + +<p>The Laurent, Schmidt and Haensch shadow and Landolt-Lippich +instruments, are of this class.</p> + +<p>3. <i>Striated Instruments.</i>—In this class the field of vision is +striated. The lines may be tinted as in Wild’s polaristrobometer or +black, as in the Duboscq and Trannin instruments. The neutral position +is indicated either by the disappearance of the striae (Wild) or by the +phenomenon of their becoming continuous. (Duboscq, Trannin.) +<span class="pagenum"><a id="Page_82"></a>[Pg 82]</span></p> + +<p><b>66. Character of Light Used.</b>—Polariscopes may be further +divided into two classes, based on the kind of light employed.</p> + +<p>1. <i>Instruments which Use Ordinary White Light.</i>—(Oil lamp, etc.) +Scheibler, Schmidt and Haensch.</p> + +<p>2. <i>Instruments Employing Monochromatic Light.</i>—(Sodium flame, +etc.) Laurent, Landolt-Lippich, etc.</p> + +<p><b>67. Interchangeable Instruments.</b>—Some of the instruments in +common use are arranged to be used either with ordinary lamp or gas +light, or with a monochromatic flame. Laurent’s polarimeter is one of +this kind. The compensating instruments also may have the field of +vision arranged for tints or shadows. Theoretically the best instrument +would be one in which the light is purely monochromatic, the field of +vision a shadow, and the compensation secured by the rotation of the +second nicol.</p> + +<p>The accuracy of an instrument depends, however, on the skill and care +with which it is constructed and used. With quartz wedges properly +ground and mounted, and with ordinary white light, polariscopes may be +obtained which give readings as accurate as can be desired.</p> + +<p>Since many persons are more or less affected with color-blindness, the +shadow are to be preferred to the tint fields of vision.</p> + +<p>For practical use in sugar analysis the white light is much more +convenient than the monochromatic light.</p> + +<p>For purposes of general investigation the polarimeters built on +the model of the laurent are to be preferred to all others. Such +instruments are not only provided with a scale which shows the +percentage of sucrose in a solution, but also with a scale and vernier +by means of which the angular rotation which the plane of vibration has +suffered, can be accurately measured in more than one-quarter of the circle.</p> + +<h3>DESCRIPTION OF POLARIZING INSTRUMENTS.</h3> + +<p><b>68. Rotation Instruments.</b>—This instrument has already been +described as one in which the extent of deviation in the plane of +polarized light caused by the intervention of an optically active +substance is measured by rotating one of the nicols about its axis and +measuring the degree of this rotation by a vernier on a graduated arc. +<span class="pagenum"><a id="Page_83"></a>[Pg 83]</span></p> + +<p>In Germany these instruments are called <i>polaristrobometers</i>, +and in France <i>polarimètrés</i>. In England and this country the +term <i>polariscope</i> or <i>polarimeter</i> is applied without +discrimination to all kinds of optical saccharimeters.</p> + +<p>The polariscope of Mitscherlich was one of the earliest in use. It has +now been entirely superseded by more modern and accurate instruments.</p> + +<p><b>69. The Laurent Instrument.</b>—A polariscope adapted by Laurent +to the use of monochromatic yellow light is almost exclusively used in +France and to a considerable extent in this country. In case a worker +is confined to the use of a single instrument, the one just mentioned +is to be recommended as the best suited to general work. It has the +second nicol, called the analyzer, movable and the degree of rotation +produced is secured in angular terms directly on a divided circle. The +scale is graduated both in angular measurements and in per cents of +sugar for a definite degree of concentration of the solution and length +of observation tube. The normal solution in the laurent instrument +contains 16.19 grams of pure sugar in 100 true cubic centimeters, and +the length of the observation tube is 200 millimeters. Both the angular +rotation and the direct percentage of sugar can be read at the same +time. Great accuracy can be secured by making the readings in each +of the four quadrants. The light is rendered yellow monochromatic by +bringing into the flames of a double bunsen, spoons made of platinum +wire, which carry fragments of fused sodium chlorid.</p> + +<div class="figcenter smcap"> + <img id="FIG_33" src="images/fig33.jpg" alt="" width="500" height="558" > + <p class="center spb1">Figure 33. Laurent Lamp.</p> +</div> + +<p><b>70. The Laurent Burner.</b>—The theory of the illumination of the +laurent burner is illustrated by the accompanying <a href="#FIG_33">Fig. 33</a>. +The lamp consists essentially of two bunsens, surmounted by a chimney.<a id="FNanchor_38" href="#Footnote_38" class="fnanchor">[38]</a> +A curved spoon made of platinum gauze serves to hold the fused particles +<span class="pagenum"><a id="Page_84"></a>[Pg 84]</span> +of sodium chlorid which are used to produce the yellow light. The spoon +is shown at G, held by the arm F, fastened by the key P. The interior +intense flame B B is surrounded by an exterior less highly colored +flame A A. It is important that the optical axis of the polariscope +be directed accurately upon the disk B, which is the most intense +part of the illumination. The point of the spoon carrying the salt +should be coincident with the prolongation of the lamp TT, so that it +just strikes the edge of the blue flame. Care should be taken not to +press the spoons into the interior of the flame as by so doing the +intensity of the illumination is very much diminished. Great care must +be observed in the position of the spoon G, and the platinum arm F +being flexible, the operator with a little patience, will be enabled +to properly place the spoon by bending it. Moreover, if the spoon be +pressed too far into the flame, the melted particles of salt collecting +in the bottom of G may drop into the lamp and occlude the orifices +through which the gas enters. The light of the yellow flame produced by +the lamp may be further purified by passing through a prism filled with +a solution of potassium dichromate, or better, a homogeneous disk cut +from a crystal of that salt.</p> + +<p>Since the flame produced by the above device is not perfectly constant, +being more intense at the moment of introducing a fresh portion of +the fused salt, the author has used a lamp designed to furnish an +absolutely constant flame.<a id="FNanchor_39" href="#Footnote_39" class="fnanchor">[39]</a> +This device which is shown in <a href="#FIG_34">Fig. 34</a>, is +based on the principle of adding constantly a fresh portion of the +salt to the flame. The flame is thus kept perfectly uniform in its +intensity.</p> + +<p>The lamp consists essentially of two wheels with platinum gauze +perimeters and platinum wire spokes, driven by a clock-work D, and +mounted by the supports AAʹ as shown in the <a href="#FIG_34">figure</a>. +The sodium salt, chlorid or bromid, in dilute solution, is placed in the porcelain +crucibles F, supported by BBʹ as indicated in the figure, to such a +depth that the rims of the platinum wheels dip beneath the surface as +they revolve. The salt is volatilized by the lamp E. By means of the +crossed bands the wheels are made to revolve in opposite directions as +indicated by the arrows. The solution of the salt which is taken up by +<span class="pagenum"><a id="Page_85"></a>[Pg 85]</span> +the platinum net-work of the rim of the wheel, thus has time to become +perfectly dry before it enters the flame and the sputtering which +a moist salt would produce is avoided. At every instant, by this +arrangement, a minute fresh portion of salt is introduced into the +flame with the result of making a perfectly uniform light which can +be used for hours without any perceptible variation. The mechanism of +the apparatus is so simple that no further description is necessary. +The polariscope should be so directed toward the flame as to bring +into the field of vision its most luminous part. The platinum wheels +are adjustable and should be so arranged as to produce between them an +unbroken yellow flame. The wheels are eight centimeters in diameter and +are driven at a rate to make one revolution in from six to ten minutes.</p> + +<div class="figcenter smcap"> + <img id="FIG_34" src="images/fig34.jpg" alt="" width="600" height="487" > + <p class="center spb1">Figure 34. Lamp for Producing Constant<br> Monochromatic Flame.</p> +</div> + +<p><span class="pagenum"><a id="Page_86"></a>[Pg 86]</span> +<b>71. Construction of Laurent’s Apparatus.</b>—The shadow polariscope +invented by Laurent is constructed as follows: The polarizer is a +special nicol which is not fixed in its position, but is so arranged +as to be turned through a small arc about its axis. By this device, +the quantity of light passing through it can be regulated, and the +apparatus is thus useful with colored solutions which are not easily +cleared by any of the common bleaching agents. The greater the quantity +of light admitted, however, the less delicate is the reading of the +shadow produced. The plane of polarized light emergent from this prism, +falls on a disk of glass half covered by a thin lamina of quartz which +thus divides the field of vision into halves. It is this semi-disk of +quartz which is the distinguishing feature of the apparatus.<a id="FNanchor_40" href="#Footnote_40" class="fnanchor">[40]</a> +The polarized light thus passes without hindrance the half field of vision +which is covered by the glass only, but can not pass the quartz plate +unless its axis is set in a certain way. The field of vision may be +thus half dark, or both halves may be equally illuminated or equally +dark according to the position of the nicol analyzer which is freely +movable about its axis and carries a vernier and reading glass over +a graduated circle. The field of vision in the laurent may have any +of the following forms.<a id="FNanchor_41" href="#Footnote_41" class="fnanchor">[41]</a> +Let the polarizer be first so adjusted that the plane of polarization +of the transmitted pencil of light is parallel to the axis of the plate +lying in the direction A B. The two halves of the field of vision will +then appear equally illuminated in every position of the analyzer. But +if the polarizing nicol be inclined to AB at an angle a, the plane of +polarization of the rays passing through the quartz plate will undergo +deviation through an equal angle in the opposite direction.</p> + +<div class="figcenter smcap"> + <img id="FIG_35" src="images/fig35.jpg" alt="" width="600" height="188" > + <p class="center spb1">Figure 35. Field of Vision of a Laurent Polariscope.</p> +</div> + +<p><span class="pagenum"><a id="Page_87"></a>[Pg 87]</span> +It happens from this, that when in the uncovered half of the field, the +plane of polarization has the direction AC, in the other half it will +have the direction ACʹ. When the analyzer is rotated, if its plane of +polarization lie in the direction cc, the rays polarized parallel to AC +will be completely extinguished and the corresponding half of the field +will be dark. The opposite happens when the plane of polarization lies +in the direction of cʹcʹ. When one-half of the field is thus obscured, +the other suffers only a partial diminution in the intensity of its +illumination. When the middle position bb is reached in the rotation of +the analyzer, the illumination of the two halves is uniform, and this +is the point at which the zero of the scale is reached. The slightest +rotation of the analyzer to the right or left of this neutral point +will cause a shadow to appear on one of the halves of the field, which +by an oscillatory movement of the analyzer, seems to leap from side to +side. The smaller the angle <i>a</i> or BAC, the more delicate will be +the shading and the more accurate the observation. This angle being +adjustable by the mechanism already described, should be made as small +as will permit the admission of the quantity of light requisite for +accurate observation.</p> + +<p>The various pieces composing the polariscope are arranged in the +following positions, beginning on the right of <a href="#FIG_36">Fig. 36</a>, +and passing to the left, where the observer is seated.<a id="FNanchor_42" href="#Footnote_42" class="fnanchor">[42]</a></p> + +<p>1. The lamp VV, TT, AA, or the wheel burner:</p> + +<p>2. The lens B for condensing the rays and rendering them parallel:</p> + +<p>3. The tube I, blackened inside to carry the lens:</p> + +<p>4. A thin lamina E, cut from a crystal of potassium bichromate, serving +to render the sodium light more monochromatic: When the saccharine +liquids under examination are colored the crystal of bichromate is +removed before the observation is made.</p> + +<p>5. The polarizer R, which is rotatable through a small angle by the +lever K:</p> + +<p>6. The lever JK for rotating the tube containing the polarizer: This is +operated by the rod X extending to the left.</p> + +<p>7. Diaphragm D, half covered with a lamina of quartz. +<span class="pagenum"><a id="Page_88"></a>[Pg 88]</span></p> + +<p>8. Trough L for holding the observation tube: In the large instrument +shown in the <a href="#FIG_36">figure</a>, it is more than half a meter in +length and arranged to hold an observation tube 500 millimeters long.</p> + +<p>9. Disk C, carrying divided circle and arbitrary sugar scale:</p> + +<p>10. Mirror M, to throw the light of the lamp on the vernier of the scale:</p> + +<div class="figcenter smcap"> + <img id="FIG_36" src="images/fig36.jpg" alt="" width="600" height="367" > + <p class="center spb1">Figure 36. Laurent Polariscope.</p> +</div> + +<p>11. Reading glass N, carried on the same radius as the mirror and used +to magnify and read the scale:</p> + +<p>12. Device F, to regulate the zero of the instrument:</p> + +<p>13. Tube H, carrying a nicol analyzer and ocular O for defining the +field of vision: This tube is rotated by the radial arm G, carrying the +mirror and reading glass.</p> + +<p><b>72 Manipulation.</b>—The lamp having been adjusted, the instrument, +in a dark room, is so directed that the most luminous spot of the flame +is in the line of vision. An observation tube filled with water is +placed in the trough and the zero of the vernier is placed accurately +on the zero of the scale. The even tint of the field of vision is then +secured by adjusting the apparatus by the device number 12.</p> + +<p><b>73 The Soleil-Ventzke Polariscope.</b>—A form of polariscope giving +a colored field of vision was in use in this country almost exclusively +until within ten years, and is still largely employed. There are many +<span class="pagenum"><a id="Page_89"></a>[Pg 89]</span> +forms of tint instruments, but the one almost exclusively used here +is that mentioned. A full description of their construction and +manipulation is given by Tucker.<a id="FNanchor_43" href="#Footnote_43" class="fnanchor">[43]</a> +By the introduction of a third rotating nicol in front of the lens +next to the lamp, the sensitive tint at which the reading is made +can be kept at a maximum delicacy. These instruments are capable of +rendering very reliable service, especially in the hands of those who +have a delicate perception of color. They are inferior, however, to the +shadow instruments in delicacy, and are more trying to the eye of the +observer. The shadow instruments therefore, especially those making +use of an ordinary kerosene lamp, have practically driven the tint +polariscopes out of use.</p> + +<p>The general arrangement of a tint instrument as modified by Scheibler +is shown in <a href="#FIG_37">Fig. 37</a>.</p> + +<div class="figcenter smcap"> + <img id="FIG_37" src="images/fig37.jpg" alt="" width="600" height="289" > + <p class="center spb1">Figure 37. Tint Polariscope.</p> +</div> + +<p>Beginning on the right of the figures, its optical parts are as +follows: A is a nicol which, with the quartz plate B, forms the +apparatus for producing the light rose neutral tint. The proper +degree of rotation of these two parts is secured by means of the +button L attached to the rod carrying the ratchet wheel as shown. The +polarizing nicol is at C, and D is a quartz disk, one-half of which is +right-handed and the other left-handed. At G is another quartz plate +belonging to the analyzing part of the apparatus. This, together with +the fixed quartz wedge F, and the movable quartz wedge E, constitute +the compensating apparatus of the instrument whereby the deviation +produced in the plane of polarized light by the solution in the tube is +restored.</p> + +<p>Next to the compensating apparatus is the analyzing nicol which in this +<span class="pagenum"><a id="Page_90"></a>[Pg 90]</span> +instrument is fixed in a certain place, <i>viz.</i>, the zero of the +scale. The analyzer and the telescope for observing the field of vision +are carried in the tube HJ. The movable quartz wedge has a scale which +is read with a telescope K, provided with a mirror inclined at an angle +of 45°, just over the scale and serving to illuminate it. The quartz +wedges are also provided with a movement by which the zero point of +the scale can be adjusted. A kerosene lamp with two flat wicks is the +best source of illumination and the instrument should be used in a dark +room and the light of the lamp, save that which passes through the +polariscope, be suppressed by a shade. The sensitive or transition tint +is produced by that position of the regulating apparatus which gives +a field of view of such a nature that a given small movement of the +quartz compensating wedge gives the greatest contrast in color between +the halves of the field of vision. For most eyes a faint rose-purple +tint, as nearly colorless as possible, possesses this quality. A slight +movement of the quartz wedge by means of the screw head M will, with +this tint, produce on one side a faint green and on the other a pink +color, which are in strong contrast. The neutral point is reached by so +adjusting the quartz wedge as to give to both halves of the field the +same faint rose-purple tint.</p> + +<p><b>74. The Shadow Polariscope for Lamp Light.</b>—This form of +instrument is now in general use for saccharimetric purposes. It +possesses on the one hand, the advantages of those instruments using +monochromatic light, and on the other, the ease of manipulation +possessed by the tint polariscopes. It differs from the tint instrument +in dispensing with the nicol and quartz plate used to regulate +the sensitive tint, and in having its polarizing nicol peculiarly +constructed in harmony with the optical principles of the jellet-corny +prism. The more improved forms of the apparatus have a double quartz +wedge compensation. The two wedges are of opposite optical properties, +and serve to make the observations more accurate by mutual correction. +The optical arrangement of the different parts of such a polariscope is +shown in the following <a href="#FIG_38">figure</a>.</p> + +<p>The lenses for concentrating the rays of light and rendering them +<span class="pagenum"><a id="Page_91"></a>[Pg 91]</span> +parallel are contained in the tube N. At O is placed the modified +polarizing nicol. The two compensating quartz wedges are moved by the +milled screw-heads EG. The rest of the optical apparatus is arranged +as described under the tint polariscope. For practical purposes, only +one of the wedges is employed, but for all accurate work the readings +should be made with both wedges and thus every possible source of error +eliminated.</p> + +<div class="figcenter smcap"> + <img id="FIG_38" src="images/fig38.jpg" alt="" width="600" height="310" > + <p class="center spb1">Figure 38. Double Compensating Shadow Polariscope.</p> +</div> + +<p id="P_75"><b>75. The Triple Shadow Instrument.</b>—When properly made, all +the instruments which have been mentioned, are capable of giving +accurate results if used in harmony with the directions given. In the +use of polariscopes having colored fields of vision a delicate sense +of distinguishing between related tints is necessary to good work. +Color-blind observers could not successfully use such apparatus. In +the shadow instruments it is only necessary to distinguish between the +halves of a field of vision unequally illuminated and to reduce this +inequality to zero. A neutral field is thus secured of one intensity +of illumination and of only one color, usually yellow. Such a field of +vision permits of the easy discrimination between the intensity of the +coloration of its two halves, and is consequently not trying to the eye +of the observer, and allows of great accuracy of discrimination. This +field of vision has lately been still further improved by dividing it +into three parts instead of two. An instrument of this kind, <a href="#FIG_39">Fig. 39</a>, +in use in this laboratory, permits a delicacy of reading not possessed +by any other instrument used for sugar analysis, and approaching that +<span class="pagenum"><a id="Page_92"></a>[Pg 92]</span> +of the standard Landolt-Lippich apparatus, used by us for research +work and for determining the rotation of quartz plates and testing the +accuracy of other polariscopes.</p> + +<div class="figcenter smcap"> + <img id="FIG_39" src="images/fig39.jpg" alt="" width="600" height="259" > + <p class="center spb1">Figure 39. Triple Shadow Polariscope.</p> +</div> + +<p>The triple shadow is secured by interposing in front of the polarizing +nicol two small nicols as indicated in <a href="#FIG_40">Fig. 40</a>. +The end views in different positions of the polarizer are shown in the +lower part of the diagrams.</p> + +<div class="figcenter smcap"> + <img id="FIG_40" src="images/fig40.jpg" alt="" width="500" height="458" > + <p class="center spb1">Figure 40. Apparatus for Producing a Triple Shadow.</p> +</div> + +<p>Instead of the comparison of the intensity of the illumination being +made on the halves of the field of vision it is made by comparing +the segments of the halves with a central band, which also changes in +intensity synchronously with the two segments, but in an opposite direction.</p> + +<h3>THE ANALYTICAL PROCESS.</h3> + +<p><b>76. General Principles.</b>—Having described the instruments +chiefly employed in the optical examination of sugar solutions, the next +<span class="pagenum"><a id="Page_93"></a>[Pg 93]</span> +step is to apply them to the analytical work. A common set of +directions for use will be found applicable to all instruments +with such modifications only as are required by peculiarities of +construction. With the best made instruments it is always advisable +to have some method of controlling the accuracy of the observation. +The simplest way of doing this is to test the apparatus by standard +quartz plates. These plates are made from right-handed polarizing +quartz crystal ground into plates of definite thickness and accurately +tested by standard instruments. Theoretically such quartz plates +deflect the plane of polarized light in a degree proportionate to +their thickness, but practically some small deviations from the rule +are found. With a source of light of the same tint, and at a constant +temperature, such plates become a safe test for the accuracy of the +graduation of polariscopes. They are more convenient for use than pure +sugar solutions of known strength which are the final standards in +all disputed cases. These quartz plates are conveniently mounted in +tubes of the same size as those holding the sugar solution, and thus +fit accurately into the trough of the polariscope, the optical axis +of which passes through their center. The quartz plate when used for +setting the scale of a polariscope should be placed always in the same +position. In some plates slight differences of reading may be noticed +on rotating the tubes holding them. Theoretically, such differences +should not exist, but in practice they are sometimes found. The temperature +of observation should also be noted, and if not that at which the value +of the plate was fixed a proper correction should be made.</p> + +<p><b>77. Setting the Polariscope.</b>—While mention has been made of +several forms of apparatus in the preceding paragraphs, those in common +use are limited to a very small number. In this country quite a number +of color instruments may still be found, together with a few laurents, +and a constantly increasing number of shadow instruments for use with +lamp light. The following description of setting the polariscope is +especially adapted to the last named instrument, but the principles of +adjustment are equally applicable to all.</p> + +<p>The scale of the instrument is first so adjusted by means of the +adjusting screws provided with each instrument, as to bring the zero of +<span class="pagenum"><a id="Page_94"></a>[Pg 94]</span> +the vernier and that of the scale exactly together. The telescope or +ocular is then adjusted until the sharp line separating the halves of +the field of vision is brought into focus. This being accomplished an +observation tube filled with pure water is placed in the apparatus +and the telescope again adjusted to bring the dividing line of the +field into focus. The beginner especially, should repeatedly study +this adjustment and be impressed with the fact that only in a sharply +defined field are practical observations of any worth. The importance +of having all the lenses perfect and all the cover glasses without a +flaw may be fully appreciated when it is remembered that the polarized +ray, already deprived of half its original luminous power, must pass +through several centimeters of crystallized calcium carbonate, and +half a dozen disks of glass and quartz, and as many lenses before +reaching the eye of the observer. Only with the greatest care and +neatness is it possible to secure the required degree of illumination. +The zero point having been well studied and accurately adjusted, the +scale of the instrument may be tried with a series of quartz plates of +known polarizing power at the temperature of the observation. In the +apparatus with double quartz wedge compensation, it will be noticed +that the marks on one scale are black and on the other red. The +black is the working and the red the control scale. To operate this +instrument, the red scale is placed exactly at the zero point. The +black scale is also placed at zero, and if the field of vision is not +neutral, it is made so by the micrometer screw with which the black +scale is provided. In a right-handed solution, the red scale is left +at zero and the black one moved to the right until neutrality in the +field of vision is reached and the reading is taken. The observation +tube containing the sugar solution is taken out and the red scale +moved until the field of vision is again neutral and the reading of +the red scale taken. The two readings should agree. Any failure in the +agreement shows some fault either in adjusting the apparatus or in its +construction, or some error in manipulation.</p> + +<p>The double compensating shadow instruments are more readily tested +for accuracy in all parts of the scale than those of any other +<span class="pagenum"><a id="Page_95"></a>[Pg 95]</span> +construction. The two compensating wedges are cut with the greatest +care, one from a left-handed and the other from a right-handed +perfectly homogeneous quartz crystal. Since faults in these wedges are +due either to lack of parallelism of surface, or of perpendicularity +to the optical axis of the crystal, and since these faults of +crystallization or construction must be in a very limited degree common +they would not coincide once in many thousand times in the two wedges. +This is easily shown by the theory of probabilities. If, therefore, the +two readings made at any point, should not agree, it must be due either +to a fault in one of the wedges, or to a fault in reading or a lack of +adjustment, as has been mentioned. In such cases the readings should be +retaken and the errors are usually easily discovered.</p> + +<p><b>78. Control Observation Tube.</b>—Instead of using quartz plates of +known values for testing the accuracy of the scale, an observation tube +may be used, the length of which can be varied at the pleasure of the observer.</p> + +<p>The construction of a tube of this kind is shown in <a href="#FIG_40">Fig. 40</a>. +The tube B is movable telescopically in A by means of the ratchet wheel +shown. It is closed at D water-tight by a glass disk. The tube B fits +as accurately into A as is possible to permit of free movement, and +any liquid which may infilter between its outer surface and the inner +surface of A is prevented from gaining exit by the washer C, which +fits both tubes water-tight. The ratchet which moves B in A carries +a millimeter scale and vernier N whereby the exact thickness of the +liquid solution between the surfaces of the glass disks D and E can be +always determined.</p> + +<div class="figcenter smcap"> + <img id="FIG_41" src="images/fig41.jpg" alt="" width="600" height="313" > + <p class="center spb1">Figure 41. Control Observation Tube.</p> +</div> + +<p><span class="pagenum"><a id="Page_96"></a>[Pg 96]</span> +By this device the length of liquid under observation can be accurately +read to a tenth of a millimeter. The cover glass E is held in position +by any one of the devices in common use for this purpose in the case in +question, by a bayonet fastening. The funnel T, communicating directly +with the interior of A, serves to hold the solution, there being always +enough of it to fill the tube when D is removed to the maximum distance +from C, which is usually a little more than 200 millimeters.</p> + +<p>Let the control tube be adjusted to 200 millimeters and filled with a +solution of pure sugar, which reads 100 per cent or degrees in a 200 +millimeter tube. Since the degree of rotation is, other things being +equal, proportional to the length of the column of polarizing solution, +it follows that if the tube B be moved inward until the distance +between D and C is 100 millimeters, the scale should read 50° or per +cent. By adjusting the length of the distance between B and C it is +easily seen that every part of the scale can be accurately tested.</p> + +<p>The tube should be filled by removing the funnel and closing the +orifice with a screw cap which comes with the apparatus. The cap E +is then removed and the tube filled in the ordinary manner. This +precaution is practiced to avoid carrying air bubbles into the tube +when filled directly through the funnel. With a little care, however, +this danger may be avoided, or should air bubbles enter they can be +easily removed by inclining the tube.</p> + +<p>In case the solution used be not strictly pure it may still be employed +for testing the scale. Suppose, for instance, that a solution made up +in the usual way, has been made from a sample containing only 99.4 per +cent of sugar. Then in order to have this solution read 100° on the scale +the tube should be set at 201.2 millimeters, according to the formula</p> + +<table class="spb1 fs_110"> + <tbody><tr> + <td class="tdl" rowspan="2"> </td> + <td class="tdc bb">200 × 100</td> + <td class="tdl_wsp" rowspan="2">= 201.2.</td> + </tr><tr> + <td class="tdc">99.4</td> + </tr> + </tbody> +</table> + +<p>By a similar calculation the position of the tube for reading any +desired degree on the scale can be determined. The importance of +controlling all parts of the scale in compensating instruments is +emphasized by the fact that a variation of only 0.016 millimeter in the +thickness of the compensating wedge will cause a change of one degree +in the reading of the instrument.</p> + +<p><b>79. Setting the Polariscope with Quartz Plates.</b>—Pure sugar is +<span class="pagenum"><a id="Page_97"></a>[Pg 97]</span> +not always at the command of the analyst, and it is more convenient +practically to adjust the instrument by means of quartz plates, the +sugar values of which have been previously tested for the character +of the light used. Assuming the homogeneity of a plate of quartz, the +degree of deflection which it imparts to a plane of polarized light +depends on the quality of the light, the thickness of the plate, and +the temperature.</p> + +<p>In respect of the quality of light, red polarized rays are least, and +violet most deflected. The degree of rotation produced with any ray, +at a given temperature, is directly proportional to the thickness of +the plate. Temperature affects the rotating power of a quartz plate +in a degree highly significant from a scientific point of view and +not wholly negligible for practical purposes. The rotating power of a +quartz plate increases with the temperature and the variation may be +determined by the formula given below:<a id="FNanchor_44" href="#Footnote_44" class="fnanchor">[44]</a></p> + +<p>The formula is applicable for temperatures between 0° and 100°. Its +values are expressed in degrees of angular measure which can be +converted into degrees of the sugar scale by appropriate factors:</p> + +<p class="fs_110"><i>Formula.— a</i>ᵗ = <i>a</i>°(1 + 0.000146<i>t</i>);</p> + +<p class="no-indent">in which <i>a</i>° = polarization in angular degrees at 0°, +<i>t</i> the temperature of observation and <i>a</i>ᵗ the rotation desired.</p> + +<p><i>Example.</i>—A quartz plate which has an angular rotation of 33° at +0° will have a rotation at 20° of 33°.09834.</p> + +<p class="fs_110"><i>a</i>ᵗ = 33(1 + 0.000146 × 20) = 33.09834.</p> + +<p>Since in instruments using the ventzke scale one degree of the sugar +scale is equal to 0.3467 degree angular measure, the sugar value of the +quartz plate mentioned is equal to 95.47 percent; 33.09834 ÷ 0.3467 = 95.47.</p> + +<p>The sugar value of this plate at 0° is 95.18 per cent; 33 ÷ 0.3467 = 95.18.</p> + +<p><b>80. Tables for Correcting Quartz Plates.</b>—Instead of calculating +the variation in quartz plates for each temperature of observation, it +is recommended by the Bureau of Internal Revenue of the Treasury, to +use control quartz plates the values of which at any given temperature, +are found on a card which accompanies each one.<a id="FNanchor_45" href="#Footnote_45" class="fnanchor">[45]</a> +The variations given, are from temperatures between 10° and 35°. Three control +<span class="pagenum"><a id="Page_98"></a>[Pg 98]</span> +plates are provided with each instrument used by the Bureau, for polarimetric +work in the custom houses, or in ascertaining bounties to be paid on +the production of domestic sugars. For example, the case of a sugar +which polarizes 80°.5 may be cited. One of the control plates nearest +to this number, is found to have at the temperature of observation, a +polarization of 91°.4, the reading being made in each case at 25°. On +consulting the card which accompanies the control plate, it is seen +that its value at the temperature mentioned, is 91°.7. The reading of +the instrument is therefore too low by three-tenths of a degree, and +this quantity should be added to the observed polarization, making it +80°.8. In this method of correcting the reading for temperature, it is +assumed that the compensating wedges of the instrument, are free of +error at the points of observation. The plates used for the purpose +above, are all standardized in the office of weights and measures of +the Coast and Geodetic Survey, before delivery to the analysts.</p> + +<p><b>81. Applicability of Quartz Plates.</b>—Quartz plates which are +correctly set for one instrument or kind of light, should be equally +accurate for the sugar scales of all instruments, using the same sugar +factor. In other words a quartz plate which reads 99° on a scheibler +color polariscope, should give the same reading on the sugar scale of a +shadow compensating or a monochromatic direct reading apparatus using +26.048 grams of sugar.</p> + +<p>The most useful quartz plates for sugar analysis, are those which give +the readings at points between 80° and 96°, which cover the limits of +ordinary commercial sugars. For molasses the plates should read from +45° to 55°. For sugar juices of the cane and beet, the most convenient +graduation would be from 10° to 20°, but plates of this value would be +too thin for practical work and are not in use. When quartz plates are +to be used for control purposes, they should be purchased from reliable +manufacturers, or better, tested directly against pure sugar solutions +by the observer.</p> + +<p>In practice we have found quartz plates as a rule, true to their +markings.</p> + +<p><b>82. The Sugar Flask.</b>—Sugar solutions are prepared for +polarization in flasks graduated to hold fifty or one hundred cubic +<span class="pagenum"><a id="Page_99"></a>[Pg 99]</span> +centimeters. For scientific work a flask is marked to hold 100 grams of +distilled water at 4°. The weights are all to be reduced to a vacuum +standard. One flask having been marked in this way, others may be +compared directly therewith by means of pure mercury. For this purpose +the flasks must be perfectly dry and the mercury pure, leaving no stain +on the sides of the flask. The glass must also be strong enough to +undergo no change in shape from the weight of mercury used.</p> + +<p>For sugar work the true 100 gram flask is not usually employed, but +one graduated by weighing at 17°.5. These flasks are graduated by +first weighing them perfectly dry, filling with distilled water and +again weighing fifty and fifty-five, or 100 and 110 grams of water at +the temperature named. Since the volume of water at 17°.5 is greater +than at 4° the sugar flask in ordinary use has a greater volume by +about 0.25 cubic centimeter than the true flask. The observer should +always secure a statement from the dealer in respect of the volume +of the flask used in testing the scale of the polariscope purchased. +In the graduation of a flask in true cubic centimeters, when brass +weights are used it will be necessary to correct the weight of each +gram of water by adding to it one milligram, which is almost exactly +the weight of the volume of air displaced by one gram of water in the +circumstances named. If the flask be first counterbalanced and it be +desired to mark it at 100 cubic centimeters the sum of the weights +placed in the opposite pan should be 100 - 0.100 = 99.900 grams. While +this is not a rigidly exact correction it will be sufficient for all +practical purposes. A liter of dry air weighs 1.29366 grams; and 100 +cubic centimeters of water would therefore displace 0.129 gram of air. +But the brass weights also displace a volume of air which when deducted +reduces the correction to be made for the water to nearly the one +named. For convenience in inverting sugar solutions the flasks used in +practical work are graduated at fifty and fifty-five and 100 and 110 +cubic centimeters respectively.</p> + +<p id="P_83"><b>83. Preparing Sugar Solutions for Polarization.</b>—If sugar +samples were always pure the percentage of sugar in a given solution +could be directly determined by immediate polarization. Such cases, +<span class="pagenum"><a id="Page_100"></a>[Pg 100]</span> +however, are rarely met in practice. In the majority of cases the +sample is not only to be brought into solution but is also to be +decolorized and rendered limpid by some one of the methods to be +described. A perfectly limpid liquid is of the highest importance to +secure correct observations. With a cloudy solution the field of vision +is obscured, the dividing line of the two halves, or the double line +in the triple field, becomes blurred or invisible and the intensity +of illumination is diminished. A colored liquid which is bright is +far more easy to polarize than a colorless liquid which is turbid. In +fact, it is only rarely in sugar work that samples will be found which +require any special decolorizing treatment other than that which is +received in applying the reagents which serve to make the solutions +limpid. In the following paragraphs the approved methods of clarifying +sugar solutions preparatory to observation in the polariscope will be +described.</p> + +<p id="P_84"><b>84. Alumina Cream.</b>—The hydrate of alumina, commonly known as +alumina cream, is always to be preferred as a clarifying agent in all +cases where it can be successfully applied.<a id="FNanchor_46" href="#Footnote_46" class="fnanchor">[46]</a> +It is a substance that acts wholly in a mechanical way and therefore +leaves the sugars in solution unchanged, carrying out only suspended +matters. In the preparation of this reagent a solution of alum is +treated with ammonia in slight excess, the aluminum hydroxid produced +washed on a filter or by decantation until neutral in reaction. The +hydroxid is suspended in pure water in proportions to produce a creamy +liquid. Although apparently very bulky, the actual space occupied by +the amount of dry hydroxid added in a few cubic centimeters is so small +as to produce no disturbing effect of importance on the volume of the +sugar solution. The cream thus prepared is shaken just before using and +from one to five cubic centimeters of it, according to the degree of +turbidity of the saccharine solution, are added before the volume in +the flask is completed to the mark. After filling the flask to the mark +the ball of the thumb is placed over the mouth and the contents well +shaken and allowed to stand for a few moments before filtering.</p> + +<p>The alumina cream is well suited to use with solutions of commercial +sugars of not too low a grade and of most honeys and high grade sirups. +<span class="pagenum"><a id="Page_101"></a>[Pg 101]</span> +It is usually not powerful enough to clarify beet and cane juices, +molasses and massecuites.</p> + +<p><b>85. Basic Lead Acetate.</b>—A solution of basic lead acetate is an +invaluable aid to the sugar analyst in the preparation of samples for +polarimetric observation. It acts as a clarifying agent by throwing +out of solution certain organic compounds and by uniting with the +organic acids in solution forms an additional quantity of precipitate, +and these precipitates act also mechanically in removing suspended +matters from solution. The action of this reagent is therefore much +more vigorous than that of alumina cream. Coloring matters are often +precipitated and removed by treatment with lead acetate. It happens +therefore that there are few samples of saccharine bodies whose +solutions cannot be sufficiently clarified by lead acetate to permit of +polarimetric observation.</p> + +<p>The reagent is most frequently employed of the following +strength:<a id="FNanchor_47" href="#Footnote_47" class="fnanchor">[47]</a> +Boil for half an hour in one and a half liters of water 464 grams of +lead acetate and 264 grams of litharge with frequent stirring. When +cool, dilute with water to two liters, allow to stand until clear, and +decant the solution. The specific gravity of this solution is about 1.267.</p> + +<p>In a solution of basic lead acetate of unknown strength the percentage +of lead acetate may be determined from its specific gravity by the +following table:<a id="FNanchor_48" href="#Footnote_48" class="fnanchor">[48]</a></p> + +<p class="f120 spa1"><b><span class="smcap">Percentage of Lead Acetate +Corresponding<br> to Different Specific Gravities at 15°.</span></b></p> + +<table class="spb1"> + <thead><tr> + <th class="tdc bb"> Specific <br>gravity.</th> + <th class="tdc bb"> Percentage of <br> lead acetate.</th> + <th class="tdc bb"> Specific <br>gravity.</th> + <th class="tdc bb"> Percentage of <br> lead acetate.</th> + </tr></thead> + <tbody><tr> + <td class="tdc">1.0127</td> + <td class="tdc"> 2</td> + <td class="tdc">1.2040</td> + <td class="tdc">28</td> + </tr><tr> + <td class="tdc">1.0255</td> + <td class="tdc"> 4</td> + <td class="tdc">1.2211</td> + <td class="tdc">30</td> + </tr><tr> + <td class="tdc">1.0386</td> + <td class="tdc"> 6</td> + <td class="tdc">1.2395</td> + <td class="tdc">32</td> + </tr><tr> + <td class="tdc">1.0520</td> + <td class="tdc"> 8</td> + <td class="tdc">1.2579</td> + <td class="tdc">34</td> + </tr><tr> + <td class="tdc">1.0654</td> + <td class="tdc">10</td> + <td class="tdc">1.2768</td> + <td class="tdc">36</td> + </tr><tr> + <td class="tdc">1.0796</td> + <td class="tdc">12</td> + <td class="tdc">1.2966</td> + <td class="tdc">38</td> + </tr><tr> + <td class="tdc">1.0939</td> + <td class="tdc">14</td> + <td class="tdc">1.3163</td> + <td class="tdc">40</td> + </tr><tr> + <td class="tdc">1.1084</td> + <td class="tdc">16</td> + <td class="tdc">1.3376</td> + <td class="tdc">42</td> + </tr><tr> + <td class="tdc">1.1234</td> + <td class="tdc">18</td> + <td class="tdc">1.3588</td> + <td class="tdc">44</td> + </tr><tr> + <td class="tdc">1.1384</td> + <td class="tdc">20</td> + <td class="tdc">1.3810</td> + <td class="tdc">46</td> + </tr><tr> + <td class="tdc">1.1544</td> + <td class="tdc">22</td> + <td class="tdc">1.4041</td> + <td class="tdc">48</td> + </tr><tr> + <td class="tdc">1.1704</td> + <td class="tdc">24</td> + <td class="tdc">1.4271</td> + <td class="tdc">50</td> + </tr><tr> + <td class="tdc">1.1869</td> + <td class="tdc">26</td> + <td class="tdc"> </td> + <td class="tdc"> </td> + </tr> + </tbody> +</table> + +<p id="P_86"><span class="pagenum"><a id="Page_102"></a>[Pg 102]</span> +<b>86. Errors Due to use of Lead Solutions.</b>—In the use of lead +solutions there is danger of errors intruding into the results of +the work. These errors are due to various sources. Lead subacetate +solution, when used with low grade products, or sugar juices, or sirups +from beets and canes, precipitates albuminous matters and also the +organic acids present. The bulk occupied by these combined precipitates +is often of considerable magnitude, so that on completing the volume in +the flask the actual sugar solution present is less than indicated. The +resulting condensation tends to give too high a polarimetric reading. +With purer samples this error is of no consequence, but especially with +low grade sirups and molasses it is a disturbing factor, which must be +considered.</p> + +<p>One of the best methods of correcting it has been proposed by +Scheibler.<a id="FNanchor_49" href="#Footnote_49" class="fnanchor">[49]</a> +To 100 cubic centimeters of a solution of the sample, +ten of lead solution are added, and after shaking and filtering +the polarimetric reading is taken. Another quantity of 100 cubic +centimeters of the solution with ten of lead is diluted to 220 cubic +centimeters, shaken, filtered, and polarized. Double the second +reading, subtract it from the first, multiply the difference by 2.2, +and deduct the product from the first reading. The remainder is the +correct polarization.</p> + +<p>The process just described is for the usual work with beet juices and +sirups. For cane juices measured by the graduated pipette, hereafter to +be described, and for weighed samples of molasses and massecuites, the +following method of calculation is pursued.<a id="FNanchor_50" href="#Footnote_50" class="fnanchor">[50]</a> +To the sample dissolved in water, add a measured portion of the lead +subacetate solution, make its volume 100 cubic centimeters and observe +the polarimetric reading. Prepare a second solution in the same way +and make the volume double that of the first and again take the +polarimetric reading. Multiply the second reading by two, subtract the +product from the first reading and multiply the remainder by two, and +subtract the product from the first reading.</p> + +<table class="spb1"> + <tbody><tr> + <td class="tdl_top" rowspan="5"><i>Example.</i>—</td> + <td class="tdl">First polarization</td> + <td class="tdc"> </td> + <td class="tdl_ws1">30.0</td> + </tr><tr> + <td class="tdl">Second polarization</td> + <td class="tdc"> </td> + <td class="tdl_ws1">14.9</td> + </tr><tr> + <td class="tdl">Then 30 - (2 × 14.9 = 29.8)</td> + <td class="tdl_wsp">=  0.2</td> + <td class="tdc"> </td> + </tr><tr> + <td class="tdl_ws2">0.2 × 2</td> + <td class="tdl_wsp">=  0.4</td> + <td class="tdc"> </td> + </tr><tr> + <td class="tdl">and 30 - 0.4</td> + <td class="tdl_wsp">= 29.6</td> + <td class="tdc"> </td> + </tr> + </tbody> +</table> + +<p><span class="pagenum"><a id="Page_103"></a>[Pg 103]</span> +The corrected reading therefore shows that the sample contained 29.6 +per cent of sugar.</p> + +<p id="P_87"><b>87. Error Due to Action of Lead Subacetate on Levulose.</b>—In the +use of lead subacetate solution not only is there danger of error due +to the causes just described, but also to a more serious one, arising +from the chemical interaction of the clarifying agent and levulose.<a id="FNanchor_51" href="#Footnote_51" class="fnanchor">[51]</a></p> + +<p>Lead subacetate forms a chemical union with levulose and the resulting +compound has a different rotatory power from the left-handed sugar in +an uncombined state. By adding a sufficient quantity of subacetate +solution, the left-handed rotation of levulose may be greatly +diminished if not entirely destroyed. In this case the dextrose, which +with levulose forms inverted sugar, serves to increase the apparent +right rotation due to the sucrose in solution. The reading of the +scale is therefore higher than would be given by the sucrose alone. +If the lead subacetate could be added in just the proportion to make +the invert sugar neutral to polarized light, its use would render the +analysis more accurate; but such a case could only arise accidentally. +To correct the error, after clarification, the compound of levulose and +lead may be decomposed by the addition of acetic acid according to the +method of Spencer. In this case the true content of sucrose can only be +obtained by the method of inversion proposed by Clerget, which will be +described in another paragraph.</p> + +<p id="P_88"><b>88. Clarification with Mercuric Compounds.</b>—Where the disturbing +bodies in a solution are chiefly of an albuminoid nature, one of the +best methods of securing clarification is by the use of a solution +containing an acid mercuric compound.<a id="FNanchor_52" href="#Footnote_52" class="fnanchor">[52]</a> +In the case of milk this method is to be preferred to all others. +Albuminoid bodies themselves, have the property of deflecting the plane +of polarization, as a rule, to the left, and therefore, should be +completely removed from solutions containing right-handed sugars such +as lactose. For this purpose the mercuric compound is more efficient +than any other. It is prepared and used as follows.<a id="FNanchor_53" href="#Footnote_53" class="fnanchor">[53]</a> +Dissolve mercury in double its weight of strong nitric acid and dilute +the solution with an equal volume of water. One cubic centimeter of +this solution is sufficient to clarify fifty times its volume of milk. +<span class="pagenum"><a id="Page_104"></a>[Pg 104]</span></p> + +<p><b>89. Decolorization by Means of Bone-Black.</b>—Where the means +already described fail to make a solution sufficiently colorless to +permit of the passage of a ray of polarized light, recourse should be +had to a decolorizing agent. The most efficient of these is bone-black. +For laboratory work it is finely ground and should be dry if added to +an already measured solution. When moist it should be added to the +flask before the volume is completed, and a correction made for the +volume of the dry char employed. Bone-black has the power of absorbing +a certain quantity of sugar, and for this reason as little of it +should be employed as is sufficient to secure the end in view. If not +more than one gram of the char be used for 100 cubic centimeters of +solution, the error is not important commercially. The error may be +avoided by placing the char on the filter and rejecting the first half +of the filtered solution. The char becomes saturated with the first +portion of the solution, and does not absorb any sugar from the second. +This method, however, does not secure so complete a decolorization as +is effected by adding the black directly to the solution and allowing +to stand for some time with frequent shaking.</p> + +<p><b>90. Remarks on Analytical Process.</b>—Since large weights of sugar +are taken for polarization, a balance which will weigh accurately to +one milligram may be used. In commercial work the weighing is made in a +counterpoised dish with a prominent lip, by means of which the sample +can be directed into the mouth of the flask after partial solution. +Where the air in the working room is still, an uncovered balance is +most convenient. With a little practice the analyst will be able to +dissolve and transfer the sample from the dish to the flask without +danger of loss. The source of light used in polarizing should be in +another room, and admitted by a circular opening in the partition. In a +close polarizing room, which results from the darkening of the windows, +the temperature will rapidly rise if a lamp be present, endangering +notably the accuracy of the work, and also interfering with the comfort +of the observer. The greatest neatness must be practiced in all stages +of the work, and especially the trough of the polariscope must be kept +from injury which may arise from the leaking of the observation tubes. +<span class="pagenum"><a id="Page_105"></a>[Pg 105]</span> +Dust and dirt of all kinds must be carefully excluded from the lenses, +prisms, wedges and plates of the instrument.</p> + +<p id="P_91"><b>91. Determination of Sucrose by Inversion.</b>—In the foregoing +paragraphs directions have been given for the estimation of sugar +(sucrose) by its optical properties. It has been assumed so far, that +no other disturbing bodies have been present, save those which could be +removed by the clarifying agents described. The case is different when +two or more sugars are present, each of which has a specific relation +to polarized light. In such cases some method must be used for the +optical determination of sucrose, which is independent of the influence +of the other polarizing bodies, or else recourse must be had to other +methods of analysis. The conversion of the sucrose present into invert +sugar by the action of an acid or a ferment, affords an opportunity for +the estimation of sucrose in mixed sugars, by purely optical methods. +This process rests upon the principle that by the action of a dilute +acid for a short time, or of a ferment for a long time, the sucrose +is completely changed, while other sugars present are not sensibly +affected. Neither of these assumptions is rigidly correct but each is +practically applicable.</p> + +<p>The sucrose by this process of hydrolysis is converted into an equal +mixture of levulose and dextrose. The former, at room temperatures, has +the higher specific rotating power, and the deflection of the plane of +polarization in a solution of inverted sugar is therefore to the left. +The levorotatory power of invert sugar varies with the temperature, +and this arises from the optical properties of the levulose. The +influence of temperature on the rotating power of other sugars, is not +imperceptible in all cases, but in practice is negligible.</p> + +<p>This method of analysis is invaluable in control work in factories, +in the customs and in agricultural laboratories. Since the rotating +power of levulose diminishes as the temperature rises, an accurate +thermometric observation must accompany each polarimetric reading. At +about 88° the rotatory powers of dextrose and levulose are equal, and a +solution of pure invert sugar examined at that degree, is found to be +neutral to polarized light.</p> + +<p id="P_92"><b>92. Clerget’s Method of Inversion.</b>—The classical method of +<span class="pagenum"><a id="Page_106"></a>[Pg 106]</span> +Clerget for the determination of cane sugar by double polarization +before and after inversion, was first described in a memoir presented +to the Society of Encouragement for National Industry on the 14th of +October, 1846. The following description of the original method is +taken from a reprint of the proceedings of that Society, dated Nov. 1846:</p> + +<p>Clerget points out first the observation of Mitscherlich regarding +the influence of temperature on the rotatory power of invert sugar, +and calls attention to the detailed experiments he has made which +resulted in the determination of the laws of the variation. From these +studies he was able to construct a table of corrections, applicable in +the analysis of all saccharine substances in which the cane sugar is +polarized before and after inversion. The basis of the law rests upon +the observation that a solution of pure sugar, polarizing 100° on the +sugar scale, before inversion, will polarize 44° to the left after +inversion at a temperature of zero. The quantity of sugar operated upon +by Clerget amounted to 16.471 grams in 100 cubic centimeters of liquid. +On the instrument employed by him this quantity of sugar in 100 cubic +centimeters gave a reading of 100° to the right on the sugar scale +when contained in a tube twenty centimeters in length. The process of +inversion carried on by Clerget is as follows:</p> + +<p>The sugar solution is placed in a flask, marked on the neck at 100 +and 110 cubic centimeters; or if smaller quantities are used, in a +flask marked on the neck at fifty and fifty-five cubic centimeters. +The flask is filled with the sugar solution to the first mark and then +a sufficient quantity of strong hydrochloric acid added to bring the +volume of the liquid to the second mark. The mouth of the flask is then +closed with the thumb and its contents thoroughly mixed by shaking. +A thermometer is placed in the flask which is set in a water-bath in +such a way that the water comes just above the level of the liquid +in the neck of the flask. The water is heated in such a manner as to +bring the temperature of the contents of the flask, as determined +by the thermometer, exactly to 68° and at such a rate as to require +fifteen minutes to reach this result. At the end of fifteen minutes the +<span class="pagenum"><a id="Page_107"></a>[Pg 107]</span> +temperature having reached 68° the flask is removed and placed at +once in another water-bath at the temperature of the room, to which +temperature the contents of the flask are cooled as rapidly as +possible. To make the polarimetric observation a tube twenty-two +centimeters in length is filled with the inverted sugar solution by +means of a tubulure in its center, which serves not only the purpose of +filling the tube but also afterwards to carry the thermometer, by means +of which the temperature of observation can be taken. If the sugar +solution be turbid, or contain any lead chlorid due to the previous use +of basic lead acetate in clarification, it should be filtered before +being introduced into the observation tube. This tube being one-tenth +longer than the original compensates for the dilution caused by the +addition of the hydrochloric acid in inversion.</p> + +<p>When reading, the bulb of the thermometer should be withdrawn far +enough to permit the free passage of the ray of light and the exact +temperature of the solution noted.</p> + +<p>The above outline of Clerget’s method of inversion is given in order +that the analyst may compare it with any of the variations which he may +find in other works. The chief points to which attention is called, +are, first, the fact that only a little over sixteen grams of sugar are +used for ten cubic centimeters of strong hydrochloric acid, and second, +that the time of heating is exactly fifteen minutes, during which time +the contents of the flask should be raised from room temperature to +exactly 68°.</p> + +<p>From the above it is seen that the process of Clerget, as originally +described, can be applied directly to all instruments, using +approximately sixteen grams of sugar in 100 cubic centimeters. +Experience has also shown that even when larger quantities of sugar +are employed, as for instance, approximately twenty-six grams, +the inversion is effected with practical completeness in the same +circumstances. It is advised, therefore, that in all analytical +processes, in which cane sugar is to be determined by the process of +inversion with an acid, the original directions of Clerget be followed +as strictly as possible. Experience has shown that no one of the +variations proposed for Clerget’s original method has any practical +advantage and the analyst is especially cautioned against those methods +<span class="pagenum"><a id="Page_108"></a>[Pg 108]</span> +of inversion in which the temperature is continued at 68° for fifteen +minutes or in which it is allowed to go above that degree.</p> + +<p><b>93. Influence of Strength of Solution and Time of Heating on the +Inversion of Sucrose.</b>—As has been intimated, the strength of a +sugar solution and the time of heating with hydrochloric acid are +factors that must be considered in determining a formula for the +calculation of sucrose by inversion. The Clerget formula holds good +only for the conditions specified and these conditions must be rigidly +adhered to in order to secure the proper results. This matter has been +thoroughly studied by Bornträger, who also gives a nearly complete +bibliography of the subject.<a id="FNanchor_54" href="#Footnote_54" class="fnanchor">[54]</a> +As a result of his investigations it seems well established that the +original Clerget formula is practically correct for the conditions +indicated, Bornträger modifying it only by substituting in the formula +143.66 for 144. This is so nearly the same as the Clerget factor +that it is not advisable to substitute it therefor. If, however, +the inverted sugar solution be diluted to double its volume before +polarization the factor proposed by Landolt, <i>viz.</i>, 142.4, gives +more nearly accurate results. If the hydrochloric acid be neutralized +before polarization by an alkaline body, the character of the salt +which is formed also influences, to a greater or less extent, the +specific rotatory power of the solution. Hydrochloric acid itself also +influences the rotation to a certain degree.<a id="FNanchor_55" href="#Footnote_55" class="fnanchor">[55]</a></p> + +<p id="P_94"><b>94. Calculation of Results.</b>—The percentage of sucrose in +a solution which has been polarized before and after inversion is +calculated by an appropriate formula from the data obtained or is taken +directly from tables. These tables are too long to insert here, and in +point of fact the calculation can be made from the formula almost as +quickly as the result can be taken from a table.</p> + +<p>Two factors are commonly used in the calculations, one based on +the supposition that a sugar solution polarizing 100° to the right +will, after inversion, give a reading of 44° to the left, at zero +temperature. In the second formula in common use the polarization to +the left in the circumstances mentioned above is assumed to be 42.4, a +number reached by Landolt after a long series of experiments.<a id="FNanchor_56" href="#Footnote_56" class="fnanchor">[56]</a> +The principle of the calculation of the percentage of sucrose is based upon +<span class="pagenum"><a id="Page_109"></a>[Pg 109]</span> +the original observation of Clerget to the effect that the algebraic +difference of the two readings, divided by 144, less half of the +temperature, will give the percentage of sucrose desired. The formula +by which this is obtained is</p> + +<table class="spb1 fs_110"> + <tbody><tr> + <td class="tdl" rowspan="2"><i>S</i> = </td> + <td class="tdc bb" colspan="2"><i>a</i> - <i>b</i></td> + <td class="tdl_wsp" rowspan="2">.</td> + </tr><tr> + <td class="tdl"><i>K</i> -</td> + <td class="tdl bb"> <i>t</i> </td> + </tr><tr> + <td class="tdl"> </td> + <td class="tdl"> </td> + <td class="tdc">2</td> + <td class="tdl"> </td> + </tr> + </tbody> +</table> + +<p>In this formula <i>a</i> is the polarization on the sugar scale before +inversion, <i>b</i> the polarization after inversion, <i>K</i> the +constant representing the algebraic difference of the two polarizations +of pure sugar at 0° and <i>t</i> the temperature of the observation. +To <i>K</i> may be assigned the values 144 or 142.4, the one in more +common use. In case the polarization, after inversion, is to the +left, which is more commonly the case, the sum of the two readings +is taken for <i>a</i> - (-<i>b</i>) = <i>a</i> + <i>b</i>; when both +polarizations are to the right or left the difference is taken. S is +the percentage of sucrose desired.</p> + +<table class="spb1 fs_110"> + <tbody><tr> + <td class="tdl_top" rowspan="3"><i>Example.—</i></td> + <td class="tdl">Let the polarization before inversion be</td> + <td class="tdr_wsp">  +95</td> + </tr><tr> + <td class="tdl_ws2">and after inversion</td> + <td class="tdr_wsp">-26</td> + </tr><tr> + <td class="tdl_ws2">and the temperature</td> + <td class="tdr">20°</td> + </tr> + </tbody> +</table> + +<table class="spb1 fs_110"> + <tbody><tr> + <td class="tdl" rowspan="2">Then <i>S</i> = </td> + <td class="tdc bb">95 + 26</td> + <td class="tdl_wsp" rowspan="2">= 121 ÷ 134 = 90.6.</td> + </tr><tr> + <td class="tdc">144 - 10</td> + </tr> + </tbody> +</table> + +<p class="fs_110">Substituting the value 142.4 for <i>K</i>, the result of the +calculation is 91.4.</p> + +<p>In high grade sugars, therefore, the difference in the results secured +by taking the two values of <i>K</i> amounts to about 1 per cent of +sucrose.</p> + +<p>For a further discussion of the theory and practice of inversion the +reader is referred to the articles of Herles, Herzfeld, and Wohl.<a id="FNanchor_57" href="#Footnote_57" class="fnanchor">[57]</a></p> + +<p id="P_95"><b>95. Method Of Lindet.</b>—Courtonne recommends the method of Lindet +for securing the inversion instead of the method of Clerget.<a id="FNanchor_58" href="#Footnote_58" class="fnanchor">[58]</a> +Modified by Courtonne, the method is as follows:</p> + +<p>Make two or three times the normal weight of sugar dissolved in water +to a volume of 200 or 300 cubic centimeters, as the case may be. After +thoroughly mixing proceed as follows:</p> + +<p><i>First, to Obtain the Polarization Direct.</i>—Place fifty or 100 +cubic centimeters of the prepared solution in a flask marked at fifty +and fifty-five or at 100 and 110 cubic centimeters, add a sufficient +quantity of lead acetate to secure a complete clarification, make the +<span class="pagenum"><a id="Page_110"></a>[Pg 110]</span> +volume to fifty-five or 110 cubic centimeters, shake thoroughly, +filter, and polarize in a 220 millimeter tube.</p> + +<p><i>Second, to Obtain the Rotation after Inversion.</i>—Place twenty +cubic centimeters of the original solution, in a flask marked at +fifty cubic centimeters, containing five grams of powdered zinc. The +flask should be placed in boiling water. Add, little by little so as +to avoid a too rapid evolution of hydrogen, ten cubic centimeters of +hydrochloric acid made of equal parts of the strongest acid and water. +After the operation is terminated, cool to the temperature of the room, +make the volume to fifty cubic centimeters, polarize, and determine +the rotation. The volume occupied by the zinc which is not dissolved, +will be about one-half cubic centimeter, hence the deviation should be +multiplied by the factor 2.475 in order to get the true deviation which +would have been produced by the pure liquor. We have then:</p> + +<ul class="index"> +<li class="isub2"><i>A</i> = the deviation direct.</li> +<li class="isub2"><i>B</i> = the deviation after inversion.</li> +<li class="isub2"><i>C</i> = the algebraic difference of the deviations.</li> +</ul> + +<p>The amount of sucrose, therefore, would be calculated by the formula of +Creydt,<a id="FNanchor_59" href="#Footnote_59" class="fnanchor">[59]</a></p> + +<table class="spb1 fs_110"> + <tbody><tr> + <td class="tdl" rowspan="2"><i>X</i> = </td> + <td class="tdc bb"><i>C</i> - 0.493<i>A</i></td> + <td class="tdl_wsp" rowspan="2"> ;</td> + </tr><tr> + <td class="tdc">0.827</td> + </tr> + </tbody> +</table> + +<p class="no-indent">for raffinose the formula would be</p> + +<table class="spb1 fs_110"> + <tbody><tr> + <td class="tdl" rowspan="2"><i>Y</i> = </td> + <td class="tdc bb"><i>A</i> - <i>S</i></td> + <td class="tdl_wsp" rowspan="2"> ;</td> + </tr><tr> + <td class="tdc">1.57</td> + </tr> + </tbody> +</table> + +<p>in which <i>S</i> is the deviation due to the sucrose present. The +solutions inverted in the manner described are absolutely colorless. +There is no need of employing bone-black to secure the saccharimetric +reading nor does it present any uncertainty. It is thought by Courtonne +that this method will soon take the place of the method of Clerget on +account of the advantages above mentioned. The method will be somewhat +improved by adopting the following suggestions:</p> + +<p>1. Instead of allowing any arbitrary number for the volume of the +undissolved zinc, decant the liquid, after inversion, into another +flask and wash repeatedly with hot water until all trace of sugar is +removed from the flask in which the inversion took place.</p> + +<p>2. Instead of polarizing in a 200 millimeter tube make the observation +in a 500 millimeter tube, which will permit of the reading being made +without any correction whatever. +<span class="pagenum"><a id="Page_111"></a>[Pg 111]</span></p> + +<p><b>96. Inversion by Means of Invertase.</b>—Instead of using acids +for the inversion of cane sugar the hydrolysis can be easily effected +by means of a ferment derived from yeast. A complete history of the +literature and characteristics of this ferment, together with a study +of its properties and the various methods of preparing it, has been +given by O’Sullivan and Tompson.<a id="FNanchor_60" href="#Footnote_60" class="fnanchor">[60]</a> +In the preparation of invertase, the method found most effective is the +following:</p> + +<p>The yeast is allowed to liquify for at least a month in a fairly warm +room without stirring. At the end of this time the surface is removed +and any supernatant liquid poured away. The lower sedimentary part is +thrown on a quick-acting filter and allowed to drain for two days. +To the filtrate, alcohol of specific gravity 0.87 is gradually added +to the extent of one and a half times its volume, with continued and +vigorous stirring. The process of adding the alcohol and stirring +should require about half an hour, after which the mixture is allowed +to stand for twenty-four hours to allow the precipitated invertase +to settle. The supernatant liquid is poured away and the precipitate +washed several times on successive days by decantation with alcohol of +0.92 specific gravity. When the washings become nearly colorless the +precipitate is thrown on a filter, allowed to drain, and immediately +removed and mixed with a large bulk of alcohol of 0.92 specific +gravity. The precipitate is again collected, mixed thoroughly with its +own bulk of water, and some alcohol of 0.97 specific gravity, allowed +to stand for a few hours and thrown on a filter. The filtrate contains +the invertase.</p> + +<p><b>97. Determination of Activity of Invertase.</b>—The activity of a +solution of invertase, prepared as above, is measured by the number +of minutes required for it to reduce to zero the optical power of a +solution of 100 times its weight of cane sugar at a temperature of +15°.5. In order to facilitate the action of the invertase, a trace of +sulfuric acid is added to the solution. The manipulation is as follows:</p> + +<p>Fifty grams of sucrose are dissolved in water and made to a volume of +nearly a quarter of a liter and placed in a bath maintained at 15°.5. +Half a gram of the invertase is added, the time noted, the solution +immediately made up to a quarter of a liter and well shaken. The +<span class="pagenum"><a id="Page_112"></a>[Pg 112]</span> +contents of the flask are poured rapidly into five beakers; the actual +quantity in each beaker is not necessarily the same. To each of these +beakers, in succession, are added the following amounts of decinormal +sulfuric acid, <i>viz.</i>, one-tenth, three-tenths, six-tenths, one, +and one and four-tenths cubic centimeters. After an hour a small +quantity of the solution is taken from beaker No. 3 and the reaction +of the invertase stopped by adding a few drops of strong potassium +hydroxid and the time of adding this reagent noted. This solution is +then read in the polariscope and the percentage of sugar inverted is +calculated from the formula <b>C₁₂H₂₂O₁₁ + H₂O = C₆H₁₂O₆ + C₆H₁₂O₆.</b></p> + +<p>The calculation of the amount of cane sugar inverted is based on the +formula,</p> + +<p class="f110">(38.4 - <i>d</i>) ÷ 0.518 = <i>p</i>.</p> + +<p class="no-indent">In this formula <i>d</i> equals the divisions +of the sugar scale read on the polariscope; <i>p</i> the percentage +of cane sugar inverted; 38.4 the reading on the sugar scale of the +original sugar solution and 51.8 the total number of divisions of the +cane sugar scale that the polariscope reading would fall through if all +the sugar were inverted. The observation tubes used in the polarization +are only 100 millimeters in length. After stopping the action of the +invertase with potassium hydroxid the solution is allowed to stand +for some time before polarization inasmuch as the dextrose formed +appears to assume the state of birotation and some time is required +for it to reach its normal rotatory power. If the invertase be used +in the alcoholic solution a sufficient quantity should be added to be +equivalent to 0.01 of the sucrose present. The time which the contents +of beaker No. 3 will take to reach optical activity is calculated in a +manner described by O’Sullivan and Tompson, but too long to be inserted +here.<a id="FNanchor_61" href="#Footnote_61" class="fnanchor">[61]</a> +The five beakers mentioned above are examined in succession and the +amount of sulfuric acid best suited to the maximum inversion thus +determined. This quantity is then used in subsequent hydrolyses with +the given sample of invertase.</p> + +<p>The action of invertase on sucrose is very rapid at the first and +becomes very much slower towards the end. At a temperature of 15°.5 it +is advisable to let the solution stand for forty-eight hours in order +to be sure that complete inversion has taken place. For this reason the +<span class="pagenum"><a id="Page_113"></a>[Pg 113]</span> +method by inversion by means of invertase is one of no great practical +importance, but it may often be useful to the analyst when the +employment of an acid is inadmissible.</p> + +<p><b>98. Inversion by Yeast.</b>—Owing to the difficulty of preparing +invertase, O’Sullivan and Thompson<a id="FNanchor_62" href="#Footnote_62" class="fnanchor">[62]</a> +propose to use yeast as the hydrolytic agent, as first suggested by +Kjeldahl. It is shown that in the use of yeast it is not necessary +to employ thymol or any other antiseptic. The method of procedure is +as follows: The cane sugar solution of usual strength should not be +alkaline, but, if possible, should be exactly neutral. If there be any +ferment suspected, the temperature should be momentarily raised to 80° +to destroy its activity. The polariscopic reading of the solution is +then taken at 15°.5 and the amount of copper reduced by the solution +should also be determined.</p> + +<p>Fifty cubic centimeters of the solution are poured into a beaker and +raised to a temperature of 55° in a constant temperature bath. Some +brewers yeast amounting to about one-tenth of the total amount of sugar +to be inverted, pressed in a towel, is thrown into the hot solution and +the whole stirred until mixture is complete. The solution is left for +four hours in the water-bath, at the end of this time it is cooled to +15°.5, a little freshly precipitated aluminum hydroxid added, and the +volume made to 100 cubic centimeters. A portion of this solution is +filtered and its polariscopic reading observed. The solution is then +left till the next day, when another polariscopic reading is taken in +order to prove that inversion is complete. The copper reducing power is +also determined. The method of calculating the results is the same as +when invertase is used. The following formulas are employed.</p> + +<p><i>a</i> = the number of divisions indicated by the polariscopic +reading for a 200 millimeter tube:</p> + +<p><i>aʹ</i> = the same number after inversion:</p> + +<p><i>m</i> = the number of the divisions of the polariscopic scale which +200 millimeters of the sugar solution containing one gram of cane sugar +per 100, alter at 15°.5 on being inverted: In the case of the ventzke +polarimeter scale, one gram of cane sugar in 100 cubic centimeters, +<span class="pagenum"><a id="Page_114"></a>[Pg 114]</span> +indicates +3.84 divisions and after inversion it gives -1.34 div. In +experiments of this kind, therefore, <i>m</i> = 5.18.</p> + +<p><i>P</i> = the weight of cane sugar present in 100 cubic centimeters of +the original solution:</p> + +<p>The formula employed then is</p> + +<table class="spb1 fs_110"> + <tbody><tr> + <td class="tdl" rowspan="2"><i>P</i> = </td> + <td class="tdc bb"><i>a</i> - 2<i>a</i>ʹ</td> + <td class="tdl_wsp" rowspan="2"> .</td> + </tr><tr> + <td class="tdc"><i>m</i></td> + </tr> + </tbody> +</table> + +<p>For the copper reduction data the following are used:</p> + +<p><i>G</i> = the weight of 100 cubic centimeters of the original solution:</p> + +<p><i>Gʹ;</i> = the same for the inverted solution: Allowance must be made +here both for the dilution and for the 5 per cent increase of the +inverted sugar, but the latter number is so small that it need not be +calculated accurately.</p> + +<p><i>w</i> = the weight of the original solution used for the estimation:</p> + +<p><i>wʹ</i> = the same factor for the inverted solution:</p> + +<p><i>k</i> = the weight of cupric oxid reduced by <i>w</i>:</p> + +<p><i>kʹ</i> = the same factor for <i>wʹ</i>:</p> + +<p><i>p</i> = the weight of cane sugar present in 100 cubic centimeters of +the original solution: The formula to be employed then is</p> + +<table class="spb1 fs_110"> + <tbody><tr> + <td class="tdl_top" rowspan="2"><i>p</i> = 0.4308 + <img src="images/cbl-2.jpg" alt="" width="10" height="36" > 2 </td> + <td class="tdc bb"><i>Gʹ kʹ</i></td> + <td class="tdl" rowspan="2"> - </td> + <td class="tdc bb"><i>G k</i></td> + <td class="tdl_wsp" rowspan="2"><img src="images/cbr-2.jpg" alt="" width="10" height="36" > .</td> + </tr><tr> + <td class="tdc"><i>wʹ</i></td> + <td class="tdc"><i>w</i></td> + </tr> + </tbody> +</table> + +<p>This method has been applied to the estimation of cane sugar in +molasses, apple juices and other substances. It is recommended by the +authors as a simple and accurate means of estimating sucrose in all +solutions containing it. The methods of making the copper reductions +will be given hereafter.</p> + +<p><b>99. Application of the Process.</b>—In practice the process of +inversion is used chiefly in the analysis of molasses and low grade +massecuites. In approximately pure sugars the direct polarization is +sufficiently accurate for all practical purposes. In molasses resulting +from the manufacture of beet sugar are often found considerable +quantities of raffinose, and the inversion process has been adapted to +that character of samples. In molasses, in sugar cane factories, the +disturbing factors are chiefly invert sugars and gums. The processes +used for molasses will be given in another paragraph. In certain +determinations of lactose the process of inversion is also practiced, +but in this case the lactose is converted into dextrose and galactose, +<span class="pagenum"><a id="Page_115"></a>[Pg 115]</span> +and the factors of calculation are altogether different. The process +has also been adapted by McElroy and Bigelow to the determination of +sucrose in presence of lactose, and this method will be described +further on. In general the process of inversion is applicable to the +determination of sucrose in all mixtures of other optically active +bodies, which are not affected by the methods of inversion employed.</p> + +<p id="P_100"><b>100. Determination of Sucrose and Raffinose.</b>—Raffinose +is a sugar which often occurs in beets, and is found chiefly in the +molasses after the chief part of the sucrose has been removed by +crystallization. It is also found in many seeds, notably in those of +the cotton plant. In a pure solution of sucrose and raffinose, both +sugars may be determined by the inversion method of Creydt.<a id="FNanchor_63" href="#Footnote_63" class="fnanchor">[63]</a> +The inversion is effected by means of hydrochloric acid in the manner +described by Clerget. The following formulas are calculated for a +temperature of observation of 20°, and the readings should be made as +near that temperature as possible.</p> + +<table class="spb1 fs_110"> + <tbody><tr> + <td class="tdl" rowspan="2">(1)<span class="ws5"><i>S</i> = </span></td> + <td class="tdc bb"><i>C</i> - 0.493<i>A</i></td> + </tr><tr> + <td class="tdc">0.827</td> + </tr> + </tbody> +</table> + +<table class="spb1 fs_110"> + <tbody><tr> + <td class="tdl" rowspan="2">(2) <i>R</i> = </td> + <td class="tdc bb"><i>A</i> - <i>S</i></td> + <td class="tdl" rowspan="2">= 1.017<i>A</i> - </td> + <td class="tdc bb">6</td> + </tr><tr> + <td class="tdc">1.57</td> + <td class="tdc">1.298</td> + </tr> + </tbody> +</table> + +<p>In these formulas <i>S</i> and <i>R</i> are the respective per cents +of sucrose and raffinose desired, <i>A</i> the polarization in sugar +degrees before inversion, <i>B</i> the polarization after inversion +read at 20°, and <i>C</i> is the algebraic difference between <i>A</i> +and <i>B</i>. It must be understood that these formulas are applicable +only to a solution containing no other optically active substances, +save sucrose and raffinose.</p> + +<p><b>101. Specific Rotatory Power.</b>—In order to compare among +themselves the rotations produced on a plane of polarized light by +different optically active bodies in solution, it is convenient to +refer them all to an assumed standard. The degree of rotation which +the body would show in this condition, is found by calculation, since, +in reality, the conditions assumed are never found in practice. In +the case of sugars and other optically active bodies, the standard of +comparison is called the specific rotatory power. This factor in any +<span class="pagenum"><a id="Page_116"></a>[Pg 116]</span> +given case, is the angular rotation which would be produced by any +given substance in a pure anhydrous state if it were one decimeter in +length and of a specific gravity equal to water. These are conditions +which evidently do not exist in the case of sugars, since crystalline +sugar particles have no polarizing power, and it would be impossible +to pass a ray of light through an amorphous sugar column of the length +specified. The specific rotatory power is therefore to be regarded as a +purely theoretical factor, calculated from the actual data obtained by +the examination of the solution of any given substance. If the length +of the observation tube in decimeters be represented by <i>l</i>, the +percentage of the polarizing body in 100 grams by <i>p</i>, and the +specific gravity of the solution by <i>d</i>, and the observed angle of +rotation by <i>a</i>, then the factor is calculated from the formula:</p> + +<table class="spb1 fs_110"> + <tbody><tr> + <td class="tdl" rowspan="2">[<i>a</i>]<span class="fs_70"><sub><b>Dj</b></sub></span> = </td> + <td class="tdc bb"><i>a</i>. 100</td> + <td class="tdl" rowspan="2"> .</td> + </tr><tr> + <td class="tdc"><i>p</i>. <i>d</i>. <i>l</i>.</td> + </tr> + </tbody> +</table> + +<p>The symbols Dj refer to the character of light employed, D indicating +the monochromatic sodium flame, and j the transition tint from white light.</p> + +<p>If the weight of the polarizing body <i>c</i> be given or known for 100 +cubic centimeters of the solution the formula becomes</p> + +<table class="spb1 fs_110"> + <tbody><tr> + <td class="tdl" rowspan="2">[<i>a</i>]<span class="fs_70"><sub><b>Dj</b></sub></span> = </td> + <td class="tdc bb"><i>a</i>. 100</td> + <td class="tdl" rowspan="2"> .</td> + </tr><tr> + <td class="tdc"><i>c</i>. <i>l</i>.</td> + </tr> + </tbody> +</table> + +<p>The latter formula is the one easier of application since it is only +necessary in applying it to dissolve a given weight of the active body +in an appropriate solvent and to complete the volume of the solution +exactly to 100 cubic centimeters. It is therefore unnecessary in this +case to determine the specific gravity.</p> + +<p><b>102. Formulas for Calculating Specific Rotatory Power.</b>—In order +to determine the specific rotatory power (gyrodynat<a id="FNanchor_64" href="#Footnote_64" class="fnanchor">[64]</a>) +of a given substance it is necessary to know the specific gravity and percentage +composition or concentration of its solution, and to examine it with +monochromatic polarized light in an instrument by which the angular +rotation can be measured. The gyrodynat of any body changes with its +degree of concentration, in some cases with the temperature, and always +with the color of the light. With the red rays the gyrodynat is least +<span class="pagenum"><a id="Page_117"></a>[Pg 117]</span> +and itprogressively increases as the violet end of the spectrum is +approached. In practice the yellow ray of the spectrum has been found +most convenient for use, and in the case of sugars the gyrodynat is +always expressed either in terms of this ray or if made with color +compensating instruments in terms of the sensitive or transition tint. +In the one case the symbol used is (<i>a</i>)<sub>D</sub> and in the other +(<i>a</i>)<sub>j</sub>. From this statement it follows that (<i>a</i>)<span class="fs_70"><span class="fs_80"><sub><b>D</b></sub></span></span> +is always numerically less than (<i>a</i>)<sub>j</sub>. Unless otherwise specified +the gyrodynat of a body is to be considered as determined by yellow +monochromatic light, and therefore corresponds to + <i>a</i><span class="fs_80"><sub><b>D</b></sub></span>.<a id="FNanchor_65" href="#Footnote_65" class="fnanchor">[65]</a></p> + +<p><b>103. Variations in Specific Rotatory Power.</b>—The gyrodynat of +any optically active body varies with the nature of the solvent, the +strength of the solution, and the temperature.<a id="FNanchor_66" href="#Footnote_66" class="fnanchor">[66]</a></p> + +<p>Since water is the only solvent of importance in determining the +gyrodynat of sugars it will not be necessary here to discuss the +influence of the nature of the solvent. In respect of the strength of +the solution it has been established that in the case of cane sugar the +gyrodynat decreases while with dextrose it increases with the degree +of concentration. The influence of temperature on the gyrodynat of +common sugars is not of great importance save in the case of levulose, +where it is the most important factor, the gyrodynat rapidly increasing +as the temperature falls. It is of course understood that the above +remarks do not apply to the increase or decrease in the volume of a +solution at changed temperatures. This influence of temperature is +universally proportional to the change of volume in all cases, and +this volumetric change is completely eliminated when the polarizations +are made at the temperatures at which the solutions are completed to +standard volumes.</p> + +<p><b>104. Gyrodynatic Data for Common Sugars.</b>—In the case of cane +sugar the gyrodynat for twenty-five grams of sugar in 100 grams of +solution at 20° is [<i>a</i>]<span class="fs_80"><sub><b>D</b></sub></span> = 66°.37. +This is about the degree of concentration of the solutions employed in the shadow +lamplight polariscopes. For seventeen grams of sugar in 100 grams of solution the +number is [<i>a</i>]<span class="fs_80"><sub><b>D</b></sub></span> = 66°.49. +This is approximately the degree of concentration for the laurent instrument. +<span class="pagenum"><a id="Page_118"></a>[Pg 118]</span></p> + +<p>For any degree of concentration according to Tollens the gyrodynat +may be computed by the following formula: [<i>a</i>]<span class="fs_80"><sub><b>D</b></sub></span> += 66°.386 + 0.015035<i>p</i> - 0.0003986<i>p</i>², in which <i>p</i> is the number +of grams of sugar in 100 grams of the solution.<a id="FNanchor_67" href="#Footnote_67" class="fnanchor">[67]</a> +In the table constructed by Schmitt the data obtained are as follows:</p> + +<table class="spb1 spa1"> + <thead><tr> + <th class="tdc bb bt" colspan="2">In 100 parts by weight <br> of solution.</th> + <th class="tdc bl bt">Specific<br> gravity</th> + <th class="tdc_bott bl bt"> Concentration </th> + <th class="tdc bl bt">Rotation <i>a</i><br> for 100 mm. </th> + <th class="tdc_bott bl bt">[<i>a</i>]<span class="fs_80"><sub><b>D</b></sub></span>.</th> + </tr><tr> + <th class="tdc bb">Sugar <i>p</i>.</th> + <th class="tdc bb bl">Water <i>q</i>.</th> + <th class="tdc bb bl"> at 20° C.<i>d</i>. </th> + <th class="tdc bb bl"><i>c</i> = <i>pd</i>.</th> + <th class="tdc bb bl">at 20° C.</th> + <th class="tdc bb bl"> </th> + </tr></thead> + <tbody><tr> + <td class="tdc">64.9775</td> + <td class="tdc bl">35.0225</td> + <td class="tdc bl">1.31650</td> + <td class="tdc bl">85.5432</td> + <td class="tdc bl">56°.134</td> + <td class="tdc bl"> 65°.620 </td> + </tr><tr> + <td class="tdc">54.9643</td> + <td class="tdc bl">45.0357</td> + <td class="tdc bl">1.25732</td> + <td class="tdc bl">69.1076</td> + <td class="tdc bl">45°.533</td> + <td class="tdc bl">65°.919</td> + </tr><tr> + <td class="tdc">39.9777</td> + <td class="tdc bl">60.0223</td> + <td class="tdc bl">1.17664</td> + <td class="tdc bl">47.0392</td> + <td class="tdc bl">31°.174</td> + <td class="tdc bl">66°.272</td> + </tr><tr> + <td class="tdc">25.0019</td> + <td class="tdc bl">74.9981</td> + <td class="tdc bl">1.10367</td> + <td class="tdc bl">27.5938</td> + <td class="tdc bl">18°.335</td> + <td class="tdc bl">66°.441</td> + </tr><tr> + <td class="tdc">16.9926</td> + <td class="tdc bl">83.0074</td> + <td class="tdc bl">1.06777</td> + <td class="tdc bl">18.1442</td> + <td class="tdc bl">12°.064</td> + <td class="tdc bl">66°.488</td> + </tr><tr> + <td class="tdc"> 9.9997</td> + <td class="tdc bl">90.0003</td> + <td class="tdc bl">1.03820</td> + <td class="tdc bl">10.3817</td> + <td class="tdc bl"> 6°.912</td> + <td class="tdc bl">66°.574</td> + </tr><tr> + <td class="tdc"> 4.9975</td> + <td class="tdc bl">95.0025</td> + <td class="tdc bl">1.01787</td> + <td class="tdc bl"> 5.0868</td> + <td class="tdc bl"> 3°.388</td> + <td class="tdc bl">66°.609</td> + </tr><tr> + <td class="tdc bb"> 1.9986</td> + <td class="tdc bl bb">98.0014</td> + <td class="tdc bl bb">1.00607</td> + <td class="tdc bl bb"> 2.0107</td> + <td class="tdc bl bb"> 1°.343</td> + <td class="tdc bl bb">66°.802</td> + </tr> + </tbody> +</table> + +<p><b>105. Bi-Rotation.</b>—Some sugars in fresh solution show a +gyrodynat much higher than the normal, sometimes lower. The former +phenomenon is called bi- the latter semi-rotation. Dextrose shows +birotation in a marked degree, also maltose and lactose. After +standing for a few hours, or immediately on boiling, solutions of these +sugars assume their normal state of rotation. The addition of a small +quantity of ammonia also causes the birotation to disappear.<a id="FNanchor_68" href="#Footnote_68" class="fnanchor">[68]</a> +This phenomenon is doubtless due to a certain molecular taxis, which remains +after solution is apparently complete. The groups of molecules thus +held in place have a certain rotatory power of their own and this is +superadded to that of the normal solution. After a time, under the +stress of the action of the solvent, these groups are broken up and the +solution then assumes its normal condition.</p> + +<p><b>106. Gyrodynat of Dextrose.</b>—The gyrodynat of dextrose, as has +already been mentioned, increases with the degree of concentration, +thus showing a property directly opposite that of sucrose.</p> + +<p>The general formula for the anhydrous sugar is [<i>a</i>]<span class="fs_80"><sub><b>D</b></sub></span> = 52.°718 ++ 0.017087<i>p</i> + 0.0004271<i>p</i>². In this formula <i>p</i> +represents the grams of dextrose in 100 grams of the solution. In a ten +per cent solution the gyrodynat of dextrose is therefore nearly exactly +[<i>a</i>]<span class="fs_80"><sub><b>D</b></sub></span>20° = 53°. +As calculated by Tollens the gyrodynats corresponding to several +degrees of concentration are shown in the following table: +<span class="pagenum"><a id="Page_119"></a>[Pg 119]</span></p> + +<table class="spb1"> + <thead><tr> + <th class="tdc bb"><i>p</i> = grams in 100<br> grams of solution. </th> + <th class="tdc"> </th> + <th class="tdc bb"> [<i>a</i>]<span class="fs_80"><sub><b>D</b></sub></span>20° + calculated for <br> anhydrous dextrose.</th> + </tr></thead> + <tbody><tr> + <td class="tdc"> 7.6819</td> + <td class="tdc" rowspan="12">   </td> + <td class="tdc">52°.89</td> + </tr><tr> + <td class="tdc"> 9.2994</td> + <td class="tdc">52°.94</td> + </tr><tr> + <td class="tdc"> 9.3712</td> + <td class="tdc">52°.94</td> + </tr><tr> + <td class="tdc">10.0614</td> + <td class="tdc">52°.96</td> + </tr><tr> + <td class="tdc">10.6279</td> + <td class="tdc">52°.98</td> + </tr><tr> + <td class="tdc">12.9508</td> + <td class="tdc">53°.05</td> + </tr><tr> + <td class="tdc">18.6211</td> + <td class="tdc">53°.25</td> + </tr><tr> + <td class="tdc">31.6139</td> + <td class="tdc">53°.83</td> + </tr><tr> + <td class="tdc">40.7432</td> + <td class="tdc">54°.34</td> + </tr><tr> + <td class="tdc">43.9883</td> + <td class="tdc">54°.54</td> + </tr><tr> + <td class="tdc">53.0231</td> + <td class="tdc">55°.17</td> + </tr><tr> + <td class="tdc">82.6111</td> + <td class="tdc">57°.80</td> + </tr> + </tbody> +</table> + +<p id="P_107"><b>107. Gyrodynats of Other Sugars.</b>—Of the other sugars it will be +sufficient to mention only levulose, maltose, lactose, and raffinose. +For complete tables of gyrodynatic powers the standard books on +carbohydrates may be consulted.<a id="FNanchor_69" href="#Footnote_69" class="fnanchor">[69]</a></p> + +<p>The gyrodynat of levulose is not definitely established. At 14° the +number is nearly expressed by [<i>a</i>]<span class="fs_80"><sub><b>D</b></sub></span>14° = -93°.7.</p> + +<p>Invert sugar, which should consist of exactly equal molecules of +dextrose and levulose, has a gyrodynat expressed by the formula +[<i>a</i>]<span class="fs_80"><sub><b>D</b></sub></span>0° = -27°.9, +with a concentration equivalent to 17.21 grams of sugar in 100 cubic +centimeters. The gyrodynat decreases with increase of temperature, +according to the formula [<i>a</i>]<span class="fs_80"><sub><b>D</b></sub></span><i>t</i>° += - (27°.9 - 0.32<i>t</i>°). According to this formula the solution is +neutral to polarized light at 87°.2, and this corresponds closely to +the data of experiment.</p> + +<p>Maltose, in a ten per cent solution at 20°, shows a gyrodynat of +[<i>a</i>]<span class="fs_80"><sub><b>D</b></sub></span>20° = 138°.3.</p> + +<p>The general formula for other degrees of concentration is +[<i>a</i>]<span class="fs_80"><sub><b>D</b></sub></span> = 140°.375 - 0.01837<i>p</i> - 0.095<i>t</i>, +in which <i>p</i> represents the number of grams in 100 grams of the solution +and <i>t</i> the temperature of observation.</p> + +<p>In the case of lactose [<i>a</i>]<span class="fs_80"><sub><b>D</b></sub></span> = 52°.53, +and this number does not appear to be greatly influenced by the degree of concentration; but +is somewhat diminished by a rising temperature.</p> + +<p>The gyrodynat of raffinose in a ten per cent solution is +[<i>a</i>]<span class="fs_80"><sub><b>D</b></sub></span> = 104°.5. +<span class="pagenum"><a id="Page_120"></a>[Pg 120]</span></p> + +<h3>CHEMICAL METHODS OF<br> ESTIMATING SUGARS.</h3> + +<p><b>108. General Principles.</b>—The methods for the chemical +estimation of sugars in common use depend on the reducing actions +exerted on certain metallic salts, whereby the metal itself or some +oxid thereof, is obtained. The reaction is either volumetric or +the resulting oxid or metal may be weighed. The common method is, +therefore, resolved into two distinct processes, and each of these +is carried out in several ways. Not all sugars have the faculty of +exerting a reducing action on highly oxidized metallic salts and the +most common of them all, <i>viz.</i>, sucrose is practically without +action. This sugar, however, by simple hydrolysis, becomes reducing, +but the two components into which it is resolved by hydrolytic action +do not reduce metallic salts in the same proportion. Moreover, in all +cases the reducing power of a sugar solution is largely dependent on +its degree of concentration, and this factor must always be taken into +consideration. Salts of copper and mercury are most usually selected to +measure the reducing power of a sugar and in point of fact copper salts +are almost universally used. Copper sulfate and carbonate are the salts +usually employed, and of these the sulfate far more frequently, but +after conversion into tartrate. Practically, therefore, the study of +the reducing action of sugar as an analytical method will be confined +almost exclusively to the determination of its action on copper +tartrate.</p> + +<p>Direct gravimetric methods are also practiced to a limited extent in +the determination of sugars as in the use of the formation of sucrates +of the alkaline earths and of the combinations which certain sugars +form with phenylhydrazin. Within a few years this last named reaction +has assumed a marked degree of importance as an analytical method. +The most practical treatment of this section, therefore, for the +limited space which can be given it, will be the study of the reducing +action of sugars, both from a volumetric and gravimetric point of +view, followed by a description of the best approved methods of the +direct precipitation of sugars by such reagents as barium hydroxid and +phenylhydrazin. +<span class="pagenum"><a id="Page_121"></a>[Pg 121]</span></p> + +<h3>VOLUMETRIC METHODS.</h3> + +<p><b>109. Classification.</b>—Among the volumetric methods will be given +those which are in common use or such as have been approved by the +practice of analysts. Since the use of mercuric salts is now practiced +to a limited extent, only a brief study of that process will be +attempted. With the copper methods a somewhat extended description will +be given of those depending on the use of copper sulfate, and a briefer +account of the copper carbonate process.</p> + +<p>In the copper sulfate method two distinct divisions must be noted, +<i>viz.</i>, first an indirect process depending first upon the +reduction of the copper to a suboxid, the subsequent action of this +body on iron salts, measured finally by titration with potassium +permanganate; and second, a direct process determined either by the +disappearance of the blue color from the copper solution, or by the +absence of copper from a drop of the solution withdrawn and tested +with potassium ferrocyanid. This last mentioned reaction is one which +is found in common use. The volumetric methods are not, as a rule, +as accurate as the gravimetric, depending on weighing the resultant +metal, but they are far more rapid and well suited to technical control +determinations.</p> + +<p><b>110. Reduction of Mercuric Salts.</b>—The method of determining +sugar by its action on mercuric salts, is due to Knapp.<a id="FNanchor_70" href="#Footnote_70" class="fnanchor">[70]</a> +The method is based on the observation that dextrose and other allied +sugars, will reduce an alkaline solution of mercuric cyanid, and that +the mercury will appear in a metallic state.</p> + +<p>The mercuric liquor is prepared by adding to a solution of ten grams of +mercuric cyanid, 100 cubic centimeters of a solution of caustic soda of +1.145 specific gravity, and making the volume to one liter with water. +The solution of sugar to be titrated, should be as nearly as possible +of one per cent strength.</p> + +<p>To 100 cubic centimeters of the boiling solution, the sugar solution is +added in small portions from a burette and in such a way as to keep the +whole mass in gentle ebullition.</p> + +<p>To determine when all the mercuric salt has been decomposed, a drop of +the clear boiling liquid is removed and brought into contact with a +drop of stannous chlorid solution on a white surface. A brownish black +<span class="pagenum"><a id="Page_122"></a>[Pg 122]</span> +coloration or precipitate will indicate that the mercury is not all +precipitated. Fresh portions of the sugar must then be added, until no +further indication of the presence of mercury is noted. The approximate +quantity of sugar solution required to precipitate the mercury having +thus been determined, the process is repeated by adding rapidly, nearly +the quantity of sugar solution required, and then only a few drops at a +time, until the reduction is complete.</p> + +<p>One hundred cubic centimeters of the mercuric cyanid solution prepared +as directed above, will be completely reduced by</p> + +<table class="spb1"> + <tbody><tr> + <td class="tdl">202</td> + <td class="tdl_wsp">milligrams</td> + <td class="tdl_wsp">of</td> + <td class="tdl_wsp">dextrose,</td> + </tr><tr> + <td class="tdl">200</td> + <td class="tdc">”</td> + <td class="tdc">”</td> + <td class="tdl_wsp">invert sugar,</td> + </tr><tr> + <td class="tdl">198</td> + <td class="tdc">”</td> + <td class="tdc">”</td> + <td class="tdl_wsp">levulose,</td> + </tr><tr> + <td class="tdl">308</td> + <td class="tdc">”</td> + <td class="tdc">”</td> + <td class="tdl_wsp">maltose,</td> + </tr><tr> + <td class="tdl">311</td> + <td class="tdc">”</td> + <td class="tdc">”</td> + <td class="tdl_wsp">lactose.</td> + </tr> + </tbody> +</table> + +<p>By reason of the unpleasant odor of the boiling mercuric cyanid when +in presence of a reducing agent, the process should be conducted in a +well ventilated fume chamber. With a little practice the process is +capable of rapid execution, and gives reasonably accurate results.</p> + +<p><b>111. Sachsse’s Solution.</b>—The solution of mercuric salts +proposed by Sachsse, is made by dissolving eighteen grams of mercuric +iodid in twenty-five cubic centimeters of an aqueous solution of +potassium iodid. To this solution are added 200 cubic centimeters of +potash lye, containing eighty grams of caustic potash. After mixing the +solution, the volume is completed to one liter. The sugar solutions +used to reduce this mixture, should be more dilute than those employed +with the mercuric cyanid, and should not be over one-half per cent in +strength. The end of the reduction is determined as already described. +After a preliminary trial, nearly all the sugar necessary to complete +reduction, should be added at once, and the end of the reduction then +determined by the addition of successive small quantities. One hundred +cubic centimeters of the mercuric iodid solution prepared as directed +above, require the following quantities of sugar to effect a complete +reduction:</p> + +<table class="spb1"> + <tbody><tr> + <td class="tdl">325</td> + <td class="tdl_wsp">milligrams</td> + <td class="tdl_wsp">of</td> + <td class="tdl_wsp">dextrose,</td> + </tr><tr> + <td class="tdl">269</td> + <td class="tdc">”</td> + <td class="tdc">”</td> + <td class="tdl_wsp">invert sugar,</td> + </tr><tr> + <td class="tdl">213</td> + <td class="tdc">”</td> + <td class="tdc">”</td> + <td class="tdl_wsp">levulose,</td> + </tr><tr> + <td class="tdl">491</td> + <td class="tdc">”</td> + <td class="tdc">”</td> + <td class="tdl_wsp">maltose,</td> + </tr><tr> + <td class="tdl">387</td> + <td class="tdc">”</td> + <td class="tdc">”</td> + <td class="tdl_wsp">lactose.</td> + </tr> + </tbody> +</table> + +<p><span class="pagenum"><a id="Page_123"></a>[Pg 123]</span> +By reason of the great difference between the reducing power of +dextrose and levulose in this solution, it has been used in combination +with the copper reduction method, to be described, to determine the +relative proportion of dextrose and levulose in a +mixture.<a id="FNanchor_71" href="#Footnote_71" class="fnanchor">[71]</a></p> + +<p>It is now known that copper solutions require slightly different +quantities of dextrose, levulose, or invert sugar to effect complete +reduction, but the variations are not great and in the calculation +above mentioned, it may be assumed that these differences do not exist.</p> + +<p>Instead of using stannous chlorid as an indicator, the end of the +reaction may be determined as follows: A disk of filtering paper is +placed over a small beaker containing some ammonium sulfid. A drop of +the clear hot solution is placed on this disk, and if salts of mercury +be still present a dark stain will be produced; or a drop of the +ammonium sulfid may be brought near the moist spot formed by the drop +of mercury salt. An alkaline solution of zinc oxid may also be used.</p> + +<p>The methods depending on the use of mercuric salts have, of late, been +supplanted by better processes, and space will not be given here to +their further discussion.</p> + +<p><b>112. The Volumetric Copper Methods.</b>—The general principle on +which these methods depend, is found in the fact that certain sugars, +notably, dextrose, (glucose), levulose, (fructose), maltose and +lactose, have the property of reducing an alkaline solution of copper +to a lower state of combination, in which the copper is separated as +cuprous oxid. The end of the reaction is either determined by the +disappearance of the blue color of the solution, or by the reaction +produced by a drop of the hot filtered solution, when placed in contact +with a drop of potassium ferrocyanid acidified with acetic.</p> + +<p>The copper salt which is found to give the most delicate and reliable +reaction, is the tartrate. The number of volumetric processes proposed +and which are in use, is very great, and an attempt even to enumerate +all of these can not be made in this volume. A few of the most reliable +and best attested methods will be given, representing if possible, the +best practice in this and other countries. The rate of reduction of the +<span class="pagenum"><a id="Page_124"></a>[Pg 124]</span> +copper salt to suboxid, is influenced by the rate of mixing with +the sugar solutions, the temperature, the composition of the copper +solution and the strength of the sugar solution.</p> + +<p>The degree of reduction is also modified by the rate at which the +sugar solution is added, and by the degree and duration of heating, +and all these variables together, make the volumetric methods somewhat +difficult and their data, to a certain extent, discordant. By reason, +however, of the ease with which they are applied and the speed of their +execution, they are invaluable for approximately correct work and for +use in technical control.</p> + +<p id="P_113"><b>113. Historical.</b>—It is not the purpose in this paragraph +to trace the development of the copper reduction method for the +determination of reducing sugars, but only to refer to the beginning of +the exact analytical application of it.</p> + +<p>Peligot, as early as 1844, made a report to the Society for the +Encouragement of National Industry on methods proposed by Barreswil +and Fromherz for the quantitive estimation of sugar by means of copper +solution.<a id="FNanchor_72" href="#Footnote_72" class="fnanchor">[72]</a> +These methods were based on the property of certain sugars to reduce alkaline +copper solution to a state of cuprous oxid first announced by +Trommer.<a id="FNanchor_73" href="#Footnote_73" class="fnanchor">[73]</a> +This was followed by a paper by Falck on the quantitive determination of +sugar in urine.<a id="FNanchor_74" href="#Footnote_74" class="fnanchor">[74]</a></p> + +<p>In 1848 the methods, which have been proposed, were critically examined +by Fehling, and from the date of his paper the determination of sugar +by the copper method may be regarded as resting on a scientific +basis.<a id="FNanchor_75" href="#Footnote_75" class="fnanchor">[75]</a></p> + +<p>Since the date mentioned the principal improvements in the process +have been in changing the composition of the copper solution in order +to render it more stable, which has been accomplished by varying the +proportions of copper sulfate, alkali and tartaric acid. For the better +keeping of the solution the method of preserving the copper sulfate and +the alkaline tartrates in separate flasks and only mixing them at the +time of use has been found very efficacious.<a id="FNanchor_76" href="#Footnote_76" class="fnanchor">[76]</a> +For testing for the end of the reaction by means of an acetic acid +solution of potassium ferrocyanid the filtering tube suggested by the +author, the use of which will be described further on, has proved quite +<span class="pagenum"><a id="Page_125"></a>[Pg 125]</span> +useful. Pavy has suggested that by the addition of ammonia to the copper +solution the precipitated suboxid may be kept in solution and the end of +the reaction thus easily distinguished by the disappearance of the blue +color.<a id="FNanchor_77" href="#Footnote_77" class="fnanchor">[77]</a> +Allen has improved on this method by covering the hot mixture with a layer +of paraffin oil whereby any oxidation of the suboxid is prevented.<a id="FNanchor_78" href="#Footnote_78" class="fnanchor">[78]</a></p> + +<p>The introduction and development of the gravimetric process depending +on securing the reduced copper oxid in a metallic state as developed by +Allihn, Soxhlet, and others, completes the resumé of this brief sketch +of the rise and development of the process.</p> + +<p><b>114. Action of Alkaline Copper Solution on Dextrose.</b>—The +action to which dextrose and other reducing sugars are subjected in +the presence of a hot alkaline copper solution is two-fold in its +nature. In the first place there is an oxidation of the sugar which is +transformed into tartronic, formic and oxalic acids, the two latter in +very small quantities. At the same time another part of the sugar is +attacked directly by the alkali and changed to complex products among +which have been detected lactic, oxyphenic and oxalic acids, also two +bodies isomeric with dioxyphenolpropionic acid. When the sugar is in +large excess melassic and glucic acids have also been detected. The +glucic acid may be regarded as being formed by simple dehydration but +becomes at once resolved into pyrocatechin and gluconic acid according +to the reaction <b>C₁₂H₁₈O₉ = C₆H₆O₂ + C₅H₁₂O₇</b>. The gluconic acid also is +decomposed and gives birth to lactic and glyceric acids according to +the formula <b>C₆H₁₂O₇ = C₃H₆O₃ + C₃H₆O₄</b>. The glyceric acid also in the +presence of a base is changed into lactic and oxalic acids. Between +lactic acid and pyrocatechin, existing in a free state, there is +produced a double reciprocal etherification in virtue of which there +arise two ethers isomeric with hydrocaffeic acid, <b>C₉H₁₀O₄</b>. One of these +bodies is an acid and corresponds to the constitution</p> + +<ul class="index fs_110"> +<li class="isub6">CH₃</li> +<li class="isub5">  /</li> +<li class="isub5"> O ── CH</li> +<li class="isub5">/  \</li> +<li class="isub3">C₆H₄ <span class="ws2">CO₂H (2)</span></li> +<li class="isub5">\</li> +<li class="isub5">OH (2)</li> +</ul> + +<p class="no-indent">and the other is of an alcoholic nature corresponding to the formula +<span class="pagenum"><a id="Page_126"></a>[Pg 126]</span></p> + +<ul class="index fs_110"> +<li class="isub5"> CO₂ ── CHOH ── CH₃ (1)</li> +<li class="isub5">/</li> +<li class="isub3">C₆H₄</li> +<li class="isub5">\</li> +<li class="isub5">OH₂ (2)</li> +</ul> + +<p>Of all these products only oxyphenic and lactic acids and their ethers +and oxalic acid remain unchanged and they can be isolated. All the +others are transformed in an acid state and they can only be detected +by operating in the presence of metallic oxids capable of precipitating +them at the time of their formation.<a id="FNanchor_79" href="#Footnote_79" class="fnanchor">[79]</a></p> + +<p><b>115. Fehling’s Solution.</b>—The copper solution which has been +most used in the determination of reducing sugars is the one proposed +by Fehling as a working modification of the original reagent used by +Trommer.<a id="FNanchor_80" href="#Footnote_80" class="fnanchor">[80]</a></p> + +<p>Following is the formula for the preparation of the fehling solution:</p> + +<table class="spb1"> + <tbody><tr> + <td class="tdl">Pure crystallized copper sulfate CuSO₄.5H₂O,  </td> + <td class="tdr_wsp">34.64</td> + <td class="tdr">grams:</td> + </tr><tr> + <td class="tdl">Potassium tartrate,</td> + <td class="tdr_wsp">150.00</td> + <td class="tdc">”</td> + </tr><tr> + <td class="tdl">Sodium hydroxid,</td> + <td class="tdr_wsp">90.00</td> + <td class="tdc">”</td> + </tr> + </tbody> +</table> + +<p>The copper sulfate is dissolved in water and the potassium tartrate in +the aqueous solution of the sodium hydroxid which should have a volume +of about 700 cubic centimeters. The two solutions are mixed and the +volume completed to a liter. Each cubic centimeter of this solution +will be reduced by five milligrams of dextrose, equivalent to four and +a half milligrams of sucrose.</p> + +<p>The reaction which takes place is represented by the following +molecular proportions:</p> + +<table class="spb1"> + <tbody><tr> + <td class="tdl">C₆H₁₂O₆</td> + <td class="tdc_top" rowspan="3">  =</td> + <td class="tdl">  10CuSO₄.5H₂O</td> + </tr><tr> + <td class="tdl">Dextrose.</td> + <td class="tdl">  Copper sulfate.  </td> + </tr><tr> + <td class="tdc">180</td> + <td class="tdc">2494</td> + </tr> + </tbody> +</table> + +<p>Fehling’s solution is delicate in its reactions but does not keep well, +depositing cuprous oxid on standing especially in a warm place exposed +to light. The fehling liquor was soon modified in its constitution by +substituting 173 grams of the double sodium and potassium tartrate for +the neutral potassium tartrate first used, and, in fact, the original +fehling reagent contained forty grams of copper sulfate instead of the +<span class="pagenum"><a id="Page_127"></a>[Pg 127]</span> +quantity mentioned above. Other proportions of the ingredients are also +given by many authors as fehling solution.</p> + +<p><b>116. Comparison of Copper Solutions for Oxidizing Sugars.</b>—For +the convenience of analysts there is given below a tabular comparison +of the different forms of fehling liquor which have been proposed +for oxidizing sugars. The table is based on a similar one prepared +by Tollens and Rodewald, amended and completed by Horton.<a id="FNanchor_81" href="#Footnote_81" class="fnanchor">[81]</a> The +solutions are arranged alphabetically according to authors’ names:</p> + +<div class="blockquot"> +<p class="no-indent">1. <i>Allihn</i>:</p> + +<p>34.6 grams copper sulfate, solution made up to half a liter; 173 +grams potassium-sodium tartrate; 125 grams potassium hydroxid +(equivalent to 89.2 grams sodium hydroxid) solution made up to +half a liter.</p> + +<p class="no-indent">2. <i>A. H. Allen</i>:</p> + +<p>34.64 grams copper sulfate, solution made up to 500 cubic +centimeters; 180 grams potassium-sodium tartrate; 70 grams sodium +hydroxid (not less than 97° NaOH), solution made up to half a +liter.</p> + +<p class="no-indent">3. <i>Bödeker</i>:</p> + +<p>34.65 grams copper sulfate; 173 grams potassium-sodium tartrate; +480 cubic centimeters sodium hydroxid solution, 1.14 specific +gravity; 67.3 grams sodium hydroxid; fill to one liter; 0.180 gram +grape sugar reduces according to Bödeker, 36.1 cubic centimeters +of the copper solution = 0.397 gram copper oxid. The same quantity +of milk sugar reduces, however, only twenty-seven cubic +centimeters copper solution = 0.298 copper oxid.</p> + +<p class="no-indent">4. <i>Boussingault</i>:</p> + +<p>40 grams copper sulfate; 160 grams potassium tartrate; 130 grams +sodium hydroxid.</p> + +<p class="no-indent">5. <i>Dietzsch</i>:</p> + +<p>34.65 grams copper sulfate; 150 grams potassium-sodium tartrate; +250 grams sodium hydroxid solution, 1.20 specific gravity; 150 +grams glycerol.</p> + +<p class="no-indent">6. <i>Fleischer</i>:</p> + +<p>69.278 grams copper sulfate dissolved in about half a liter of +water, add to this 200 grams tartaric acid; fill to one liter with +concentrated sodium hydroxid solution; twenty cubic centimeters +copper solution = forty cubic centimeters sugar solution, that +contain in every cubic centimeter five milligrams grape sugar.</p> + +<p class="no-indent">7. <i>Fehling</i>:</p> + +<p>40 grams copper sulfate; 160 grams di-potassium tartrate = 600-700 +cubic centimeters sodium hydroxid solution, 1.12 specific gravity, +or from 54.6 to 63.7 grams sodium hydroxid, fill to 1154.4 cubic + +<span class="pagenum"><a id="Page_128"></a>[Pg 128]</span> + +centimeters.</p> + +<p class="no-indent">8. <i>Gorup-Besanez</i>:</p> + +<p>34.65 grams copper sulfate; 173 grams potassium-sodium tartrate; +480 cubic centimeters sodium hydroxid solution, 1.14 specific +gravity; equal 67.3 sodium hydroxid. Fill to one liter.</p> + +<p class="no-indent">9. <i>Grimaux</i>:</p> + +<p>40 grams copper sulfate; 160 grams potassium-sodium tartrate; +600-700 cubic centimeters sodium hydroxid solution, 1.20 specific +gravity, equal to 92.5-107.9 grams sodium hydroxid. Fill to +1154.4 cubic centimeters. Ten cubic centimeters of this solution +are completely decolorized by 0.050 gram glucose.</p> + +<p class="no-indent">10. <i>Holdefleis</i>:</p> + +<p>34.632 grams copper sulfate in one liter of water; 125 grams +potassium hydroxid, equivalent to 89.2 grams sodium hydroxid; 173 +grams potassium-sodium tartrate. Fill to one liter.</p> + +<p class="no-indent">11. <i>Hoppe-Seyler</i>:</p> + +<p>34.65 grams copper sulfate; 173 grams potassium-sodium tartrate; +600-700 cubic centimeters sodium hydroxid solution, 1.12 specific +gravity; equal to 63.0-73.5 grams potassium hydroxid. Fill to +one liter. One cubic centimeter is reduced by exactly 0.005 gram +grape sugar.</p> + +<p class="no-indent">12. <i>Krocker</i>:</p> + +<p>6.28 grams copper sulfate; 34.6 grams potassium-sodium tartrate; +100 cubic centimeters sodium hydroxid solution, 1.14 specific +gravity. Fill to 200 cubic centimeters. In 100 cubic centimeters +of this solution is contained 0.314 gram copper sulfate, which is +reduced by 0.050 grape sugar.</p> + +<p class="no-indent">13. <i>Liebermann</i>:</p> + +<p>4 grams copper sulfate; 20 grams potassium-sodium tartrate; 70 +grams sodium hydroxid solution, 1.12 specific gravity. Fill to +115.5 cubic centimeters.</p> + +<p class="no-indent">14. <i>Löwe</i>:</p> + +<p>15 grams copper sulfate; 60 grams glycerol; 80 cubic centimeters +sodium hydroxid, 1.34 specific gravity; 160 cubic centimeters +water. Fill to half a liter.</p> + +<p class="no-indent">15. <i>Mohr</i>:</p> + +<p>34.64 copper sulfate; 150 grams di-potassium tartrate; 600-700 +cubic centimeters sodium hydroxid solution, 1.12 specific +gravity, equal to 70.5-82.3 grams sodium hydroxid. Fill to one +liter.</p> + +<p class="no-indent">16. <i>Märcker</i>:</p> + +<p>35 grams copper sulfate, solution made up to one liter: 175 +grams potassium-sodium tartrate; 125 grams potassium hydroxid, +equivalent to 89.2 grams sodium hydroxid, solution made up to one +liter.</p> + +<p class="no-indent">17. <i>Maumenè</i>:</p> + +<p>375 grams copper sulfate; 188 grams potassium-sodium tartrate; +<span class="pagenum"><a id="Page_129"></a>[Pg 129]</span></p> + +<p>166 grams potassium hydroxid. Fill to nine liters.</p> + +<p class="no-indent">18. <i>Monier</i>:</p> + +<p>40 grams copper sulfate; 3 grams stannic chlorid; 80 grams cream +of tartar; 130 grams sodium hydroxid. Fill to one liter.</p> + +<p class="no-indent">19. <i>Neubauer and Vogel</i>:</p> + +<p>34.639 grams copper sulfate; 173 grams potassium-sodium tartrate; +500-600 grams sodium hydroxid solution, 1.12 specific gravity. +Fill to one liter.</p> + +<p class="no-indent">20. <i>Pasteur</i>:</p> + +<p>40 grams copper sulfate; 105 grams tartaric acid; 80 grams +potassium hydroxid; 130 grams sodium hydroxid.</p> + +<p class="no-indent">21. <i>Possoz</i>:</p> + +<p>40 grams copper sulfate; 300 grams potassium-sodium tartrate; +29 grams sodium hydroxid; 159 grams sodium bicarbonate, allow +to stand six months before use. Fill to one liter. One cubic +centimeter equals 0.0577 gram dextrose. One cubic centimeter +equals 0.0548 gram cane sugar.</p> + +<p class="no-indent">22. <i>Rüth</i>:</p> + +<p>34.64 grams copper sulfate; 143 grams potassium-sodium tartrate; +600-700 cubic centimeters sodium hydroxid solution, 1.12 specific +gravity. Fill to one liter.</p> + +<p class="no-indent">23. <i>Rodewald and Tollens</i>:</p> + +<p>34.639 grams copper sulfate, solution made up to half a liter; +173 grams potassium-sodium tartrate; 60 grams sodium hydroxid, +solution made up to half a liter.</p> + +<p class="no-indent">24. <i>Schorlemmer</i>:</p> + +<p>34.64 grams copper sulfate; 200 grams potassium-sodium tartrate; +600-700 cubic centimeters sodium hydroxid solution, 1.20 specific +gravity. Fill to one liter.</p> + +<p class="no-indent">25. <i>Soxhlet</i>:</p> + +<p>34.639 grams copper sulfate, solution made up to half a liter. +173 grams potassium-sodium tartrate; 51.6 grams sodium hydroxid, +solution made up to half a liter.</p> + +<p class="no-indent">26. <i>Soldaini</i>:</p> + +<p>3.464 grams copper sulfate; 297 grams potassium bicarbonate. Fill +to one liter.</p> + +<p class="no-indent">27. <i>Violette</i>:</p> + +<p>34.64 grams copper sulfate; 187.0 potassium-sodium tartrate; 78.0 +sodium hydroxid made up to one liter. Ten cubic centimeters equal +0.050 gram dextrose. Ten cubic centimeters equal 0.0475 gram cane +sugar.</p> +</div> + +<p id="P_117"><b>117. Volumetric Method used in this Laboratory.</b>—The alkaline +copper solution preferred in this laboratory has the composition +<span class="pagenum"><a id="Page_130"></a>[Pg 130]</span> +proposed by Violette. The copper sulfate and alkaline tartrate +solutions are kept in separate vessels and mixed in proper proportions +immediately before use, and diluted with about three volumes of water. +The reduction is accomplished in a long test tube at least twenty-five +centimeters in length, and from thirty-five to forty millimeters in diameter.</p> + +<p>The sugar solution employed should contain approximately one per cent +of reducing sugar. If it should have a greater content it should be +reduced with water to approximately the one named. If it have a less +content, it should be evaporated in a vacuum at a low temperature +until it reaches the strength mentioned above. A preliminary test +will indicate almost the exact quantity of the sugar solution to be +added to secure a complete reduction of the copper. This having been +determined the whole quantity should be added at once to the boiling +copper solution, the test tube held in the open flame of a lamp +giving a large circular flame and the contents of the tube kept in +brisk ebullition for just two minutes. The lamp is withdrawn and the +precipitated suboxid allowed to settle. If a distinct blue color remain +an additional quantity of the sugar solution is added and again boiled +for two minutes. When the blue coloration is no longer distinct, the +presence or absence of copper is determined by aspirating a drop or +two of the hot solution with the apparatus described below. This clear +filtered liquor is then brought into contact with a drop of potassium +ferrocyanid solution acidulated with acetic. The production of a brown +precipitate or color indicates that some copper is still present, +in which case an additional quantity of the sugar solution is added +and the operation continued as described above until after the last +addition of sugar solution no coloration is produced.</p> + +<p><b>118. The Filtering Tube.</b>—The filtering tube used in the above +operation is made of a long piece of narrow glass tubing with thick +walls. The length of the tube should be from forty to forty-five +centimeters. One end of the tube being softened in the flame is pressed +against a block of wood so as to form a flange. Over this flange is +tied a piece of fine linen.<a id="FNanchor_82" href="#Footnote_82" class="fnanchor">[82]</a></p> + +<p>Instead of using a linen diaphragm the tube is greatly improved, as +suggested by Knorr, by sealing into the end of the tube while hot a +<span class="pagenum"><a id="Page_131"></a>[Pg 131]</span> +perforated platinum disk. Before using, the tube is dipped into a +vessel containing some suspended asbestos felt and by aspiration a thin +felt of asbestos is formed over the outer surface of the platinum disk. +By inverting the tube the water which has entered during aspiration is +removed. The tube thus prepared is dipped into the boiling solution in +the test tube above described and aspiration continued until a drop of +the liquor has entered the tube. It is then removed from the boiling +solution, the asbestos felt wiped off with a clean towel, and the drop +of liquor in the tube blown through the openings in the platinum disk +and brought into contact with a drop of potassium ferrocyanid in the +usual way. In this way a drop of the liquor is secured without any danger +of a reoxidation of the copper which may sometimes take place on cooling.</p> + +<div class="figcenter smcap"> + <img id="FIG_42" src="images/fig42.jpg" alt="" width="600" height="278" > + <p class="center spb1">Figure 42. Apparatus for the Volumetric Estimation<br> + of Reducing Sugars.</p> +</div> + +<p>The careful analyst by working in this way with the volumetric method +is able to secure highly accurate results. The apparatus used is shown +in the accompanying illustration.</p> + +<p><b>119. Suppression of the Error Caused by the Action of the Alkali +on Reducing Sugars.</b>—Three methods are proposed by Gaud for +correcting or suppressing the error due to the action of the alkali +upon reducing sugars. In the first place, the common method followed +may be employed, depending upon the use of an alkaline copper solution +of known composition and the employment of a reducing sugar solution of +a strength varying between one-half and one per cent. The error which +is introduced into such a reaction is a constant one and the solution +<span class="pagenum"><a id="Page_132"></a>[Pg 132]</span> +having been tested once for all against pure sugar is capable of giving +fairly accurate results.</p> + +<p>In the second place, a table may be constructed in which the error is +determined for sugar solutions for varying strengths, <i>viz.</i>, from +one-tenth of one per cent to ten per cent. If <i>y</i> represent the +error and <i>x</i> the exact percentage of reducing sugar present then +the correction may be made by the following formula;</p> + +<p class="f110"><i>y</i> = - 0.00004801<i>x</i> + 0.02876359<i>x</i>².</p> + +<p>In order to use this formula in practice the percentage of reducing +sugar obtained by the actual analysis must be introduced and may +be represented by θ. The formula for correction then becomes +0.02876<i>x</i>² - 1.000048<i>x</i> + θ = 0; whence the value of +<i>x</i> is easily computed.</p> + +<p>In the third place, the error may be eliminated by substituting for an +alkali which acts upon the glucose one which does not, <i>viz.</i>, +ammonia. At the temperature of boiling water ammonia does not have any +decomposing effect upon reducing sugars. It is important, however, +that the reduction take place in an inert atmosphere in order to +avoid the oxidation of the dissolved cuprous oxid and the temperature +need not be carried beyond 80°. The end of the reaction can be easily +distinguished in this case by the disappearance of the blue color. When +one reaction is finished the copper may be completely reoxidized by +conducting through it a current of air or oxygen for half an hour, when +an additional quantity of ammonia may be added to supply any that may +have evaporated, and a new reduction accomplished with exactly the same +quantity of copper as was used in the first. The solution used by Gaud +contains 36.65 grams of crystallized copper sulfate dissolved in water +and the volume completed to one liter with ordinary aqueous +ammonia.<a id="FNanchor_83" href="#Footnote_83" class="fnanchor">[83]</a></p> + +<p><b>120. Permanganate Process for the Estimation of Reducing +Sugars.</b>—Dextrose, invert sugar, and other reducing sugars can also +be determined with a fair degree of accuracy by an indirect volumetric +process, in which a standard solution of potassium permanganate is used +as the final reagent.<a id="FNanchor_84" href="#Footnote_84" class="fnanchor">[84]</a> +The principle of the process is based upon the observation that two molecules +<span class="pagenum"><a id="Page_133"></a>[Pg 133]</span> +of dextrose reduce from an alkaline cupric tartrate solution five +molecules of cuprous oxid. The five molecules of cuprous oxid thus +precipitated when added to an acid solution of ferric sulfate, will +change five molecules of the ferric sulfate to ten molecules of ferrous +sulfate. The reaction is illustrated by the following equation:</p> + +<table class="spb1"> + <tbody><tr> + <td class="tdc"><img src="images/cbl-3.jpg" alt="" width="16" height="57" ></td> + <td class="tdc">5Cu₂O<br>715 parts</td> + <td class="tdc"><img src="images/cbr-3.jpg" alt="" width="16" height="57" ></td> + <td class="tdc"> + </td> + <td class="tdc"><img src="images/cbl-3.jpg" alt="" width="16" height="57" ></td> + <td class="tdc">5Fe₂(SO₄)₃<br>2000 parts</td> + <td class="tdc"><img src="images/cbr-3.jpg" alt="" width="16" height="57" ></td> + <td class="tdc"> + </td> + <td class="tdc"><img src="images/cbl-3.jpg" alt="" width="16" height="57" ></td> + <td class="tdc">5H₂SO₄<br>490 parts</td> + <td class="tdc"><img src="images/cbr-3.jpg" alt="" width="16" height="57" ></td> + <td class="tdc"> <span class="fs_120">=</span> </td> + <td class="tdc"><img src="images/cbl-3.jpg" alt="" width="16" height="57" ></td> + <td class="tdc">10CuSO₄<br>1595 parts</td> + <td class="tdc"><img src="images/cbr-3.jpg" alt="" width="16" height="57" ></td> + </tr> + </tbody> +</table> + +<table class="spb1"> + <tbody><tr> + <td class="tdc"> + </td> + <td class="tdc"><img src="images/cbl-3.jpg" alt="" width="16" height="57" ></td> + <td class="tdc">10FeSO₄<br>1520 parts</td> + <td class="tdc"><img src="images/cbr-3.jpg" alt="" width="16" height="57" ></td> + <td class="tdc"> + </td> + <td class="tdc"><img src="images/cbl-3.jpg" alt="" width="16" height="57" ></td> + <td class="tdc">5H₂O<br>90 parts</td> + <td class="tdc"><img src="images/cbr-3.jpg" alt="" width="16" height="57" ></td> + </tr> + </tbody> +</table> + +<p>The ten molecules of ferrous sulfate formed as indicated in the above +reaction, are reoxidized to ferric sulfate by a set solution of +potassium permanganate. This reaction is illustrated by the equation +given below:</p> + +<table class="spb1"> + <tbody><tr> + <td class="tdc"><img src="images/cbl-3.jpg" alt="" width="16" height="57" ></td> + <td class="tdc">10FeSO₄<br>1520 parts</td> + <td class="tdc"><img src="images/cbr-3.jpg" alt="" width="16" height="57" ></td> + <td class="tdc"> + </td> + <td class="tdc"><img src="images/cbl-3.jpg" alt="" width="16" height="57" ></td> + <td class="tdc">K₂Mn₂O₈<br>316.2 parts</td> + <td class="tdc"><img src="images/cbr-3.jpg" alt="" width="16" height="57" ></td> + <td class="tdc"> + </td> + <td class="tdc"><img src="images/cbl-3.jpg" alt="" width="16" height="57" ></td> + <td class="tdc">5H₂SO₄<br>784 parts</td> + <td class="tdc"><img src="images/cbr-3.jpg" alt="" width="16" height="57" ></td> + <td class="tdc"> <span class="fs_120">=</span> </td> + <td class="tdc"><img src="images/cbl-3.jpg" alt="" width="16" height="57" ></td> + <td class="tdc">5Fe₂(SO₄)₂<br>2000 parts</td> + <td class="tdc"><img src="images/cbr-3.jpg" alt="" width="16" height="57" ></td> + </tr> + </tbody> +</table> + +<table class="spb1"> + <tbody><tr> + <td class="tdc">+ </td> + <td class="tdc"><img src="images/cbl-3.jpg" alt="" width="16" height="57" ></td> + <td class="tdc">2MnSO₄<br>302 parts</td> + <td class="tdc"><img src="images/cbr-3.jpg" alt="" width="16" height="57" ></td> + <td class="tdc"> + </td> + <td class="tdc"><img src="images/cbl-3.jpg" alt="" width="16" height="57" ></td> + <td class="tdc">K₂SO₄<br>174.2 parts</td> + <td class="tdc"><img src="images/cbr-3.jpg" alt="" width="16" height="57" ></td> + <td class="tdc"> + </td> + <td class="tdc"><img src="images/cbl-3.jpg" alt="" width="16" height="57" ></td> + <td class="tdc">8H₂O<br>144 parts</td> + <td class="tdc"><img src="images/cbr-3.jpg" alt="" width="16" height="57" ></td> + </tr> + </tbody> +</table> + + +<p>By the study of the above equations it is seen that two molecules +of dextrose or other similar reducing sugar, are equivalent +to one molecule of potassium permanganate, as is shown by the +following equations:</p> + +<table class="spb1"> + <tbody><tr> + <td class="tdc"><img src="images/cbl-3.jpg" alt="" width="16" height="57" ></td> + <td class="tdc">2C₆H₁₂O₆<br>360 parts</td> + <td class="tdc"><img src="images/cbr-3.jpg" alt="" width="16" height="57" ></td> + <td class="tdc"> = </td> + + <td class="tdc"><img src="images/cbl-3.jpg" alt="" width="16" height="57" ></td> + <td class="tdc">5Cu₂O<br>715 parts</td> + <td class="tdc"><img src="images/cbr-3.jpg" alt="" width="16" height="57" ></td> + <td class="tdc"> = </td> + + <td class="tdc"><img src="images/cbl-3.jpg" alt="" width="16" height="57" ></td> + <td class="tdc">10FeSO₄<br>1520 parts</td> + <td class="tdc"><img src="images/cbr-3.jpg" alt="" width="16" height="57" ></td> + <td class="tdc"> = </td> + + <td class="tdc"><img src="images/cbl-3.jpg" alt="" width="16" height="57" ></td> + <td class="tdc">K₂Mn₂O₈<br>316.2 parts</td> + <td class="tdc"><img src="images/cbr-3.jpg" alt="" width="16" height="57" ></td> + </tr> + </tbody> +</table> + +<p>It is thus seen that 316.2 parts by weight of potassium permanganate +are equivalent to 360 parts by weight of dextrose; or one part of +permanganate corresponds to 1.1385 parts by weight of dextrose. If, +therefore, the amount of permanganate required in the above reaction to +restore the iron to the ferric condition, be multiplied by the factor +mentioned above, the quotient will represent in weight the amount of +dextrose which enters into the reaction. The standard solution of +potassium permanganate should contain 4.392 grams of the salt in a +liter. One cubic centimeter of this solution is equivalent to five +milligrams of dextrose.</p> + +<p><b>121. Manipulation.</b>—The saccharine solution whose strength is to +be determined should contain approximately about one per cent of sugar. +<span class="pagenum"><a id="Page_134"></a>[Pg 134]</span> +Of this solution ten cubic centimeters are placed in a porcelain dish +together with a considerable excess of fehling solution. When no +sucrose is present, the mixture may be heated to the temperature of +boiling water and kept at that temperature for a few minutes until +all the reducing sugar is oxidized. There should be enough of the +copper solution used to maintain a strong blue coloration at the end +of the reaction. A greater uniformity of results will be secured by +using in all cases a considerable excess of the copper solution. When +sucrose or other non-reducing sugars are present, the temperature of +the reaction should not be allowed to exceed 80° and the heating may +be continued somewhat longer. At this temperature the copper solution +is absolutely without action on sucrose. The precipitated suboxid is +allowed to settle, the supernatant liquid poured off through a filter +and the suboxid washed thoroughly a number of times by decantation with +hot water, the washings being poured through the filter. This process +of washing is greatly facilitated by decanting the supernatant liquid +from the porcelain dish first into a beaker and from this into a third +beaker and so on until no suboxid is carried off. Finally the wash +water is poured through a filter-paper bringing as little as possible +of the suboxid onto the paper. The suboxid on the filter-paper and in +the beakers is next dissolved in a solution of ferric sulfate made +strongly acid with sulfuric; or in a sulfuric acid solution of ammonia +ferric sulfate which is more easily obtained free from impurities than +the ferric sulfate. When all is dissolved from the beakers the solution +is poured upon the suboxid which still remains in the porcelain dish. +When the solution is complete it is washed into a half liter flask and +all the vessels which contain the suboxid are also thoroughly washed +and the wash waters added to the same flask. The whole is rendered +strongly acid with sulfuric and made up to a volume of half a liter.</p> + +<p>The process carried out as directed, when tested against pure sugar, +gives good results, not varying from the actual content of the sugar +by more than one-tenth per cent below or three-tenths above the true +content. The distinct pink coloration imparted to the solution by the +permanganate solution as soon as the iron is all oxidized to the ferric +state marks sharply the end of the reaction. In this respect this +<span class="pagenum"><a id="Page_135"></a>[Pg 135]</span> +process is very much to be preferred to the usual volumetric processes +depending upon the coloration produced with potassium ferrocyanid +by a copper salt for distinguishing the end of the reaction. It is +less convenient than the ordinary volumetric process by reason of the +somewhat tedious method of washing the precipitated cuprous oxid. When +a large number of analyses is to be made, however, the whole can be +washed with no more expenditure of time than is required for a single +sample. One analyst can, in this way, easily attend to fifty or a +hundred determinations at a time.</p> + +<p>In the application of the permanganate method to the analysis of the +juices of sugar cane and sorghum it is directed to take 100 cubic +centimeters of the expressed juice and clarify by the addition of +twenty-five cubic centimeters of basic lead acetate, diluted with +water, containing enough of the lead acetate, however, to produce a +complete clarification. It is not necessary to remove the excess of +lead from the filtrate before the determination. Ten cubic centimeters +of the filtrate correspond to eight cubic centimeters of the original +juice. For percentage calculation the specific gravity of the original +juice must be known. Before the addition of the alkaline copper +solution, from fifty to seventy-five cubic centimeters of water should +be added to the clarified sugar juice and the amount of fehling +solution used in each case should be from fifty to seventy-five cubic +centimeters. The heating at 75° should be continued for half an hour +in order to insure complete reduction and oxidation of the sugar. The +sucrose can also be estimated in the same juices by inverting five +cubic centimeters of the clarified juice with five cubic centimeters +of dilute hydrochloric acid, by heating for an hour at a temperature +not above 90°. Before adding the acid for inversion, about 100 cubic +centimeters of water should be poured over the five cubic centimeters +of sugar solution. The washing of the suboxid and the estimation of the +amount reduced are accomplished in the manner above described.</p> + +<p>This method has been extensively used in this laboratory and with very +satisfactory results. The only practical objection which can be urged +to it is in the time required for filtering. This fault is easily +remedied by adopting the method of filtering through asbestos felt +described in the next paragraph. +<span class="pagenum"><a id="Page_136"></a>[Pg 136]</span></p> + +<p>For the sake of uniformity, however, the copper solution should +be boiled for a few minutes before the addition of the sugar in +order to expel all oxygen, the sugar solutions should be made with +recently boiled water and the precipitation of the suboxid should be +accomplished by heating for just thirty minutes at 75°. At the end of +this time an equal volume of cold, recently boiled, water should be +added and the filtration at once accomplished.</p> + +<p><b>122. Modified Permanganate Method.</b>—The permanganate method +as used by Ewell, in this laboratory, is conducted as follows: After +the precipitate is obtained, according to the directions given in the +methods described, it is thoroughly washed with hot, recently boiled +water, on a gooch. The asbestos, with as much of the precipitate as +possible, is transferred to the beaker in which the precipitation was +made, beaten up with from twenty-five to thirty cubic centimeters +of hot, recently boiled water, and from fifty to seventy-five cubic +centimeters of a saturated solution of ferric sulfate in twenty-five +per cent sulfuric acid are added to the beaker and then poured through +the crucible to dissolve the cuprous oxid remaining therein. If the +precipitate be first beaten up with water as directed, so that no +large lumps of it remain, there is no difficulty in dissolving the +oxid in the ferric salt; while if any lumps of the oxid be allowed to +remain there is great difficulty. After the solution is obtained, it is +titrated with a solution of potassium permanganate of such a strength +that each cubic centimeter is equivalent to 0.01 gram of copper.</p> + +<p>In triplicate determinations made by this method the precipitates +obtained required after solution in the ferric salt, 28.7, 28.9, 28.6 +cubic centimeters of potassium permanganate solution, respectively. +For the quantities taken this was equivalent to an average percentage +of reducing sugars of 4.19. The percentage obtained by the gravimetric +method was 4.26.</p> + +<p>The method seems to be sufficiently accurate for all ordinary purposes +and is extremely rapid.</p> + +<p>The permanganate solution used should be standardized by means +of metallic iron, but in ordinary work it is also recommended to +standardize by check determinations of reducing sugars in the same +sample by the gravimetric method. +<span class="pagenum"><a id="Page_137"></a>[Pg 137]</span></p> + +<p><b>123. Determination of Reducing Sugar by the Specific Gravity of +the Cuprous Oxid.</b>—Gaud proposes to determine the percentage of +reducing sugar from the specific gravity of the cuprous oxid. The +manipulation is carried out as follows:</p> + +<p>In a porcelain dish are placed fifty cubic centimeters of the alkaline +copper solution and an equal quantity of water and the mixture +maintained in ebullition for two or three minutes. The dish is then +placed on a boiling water-bath and twenty-five cubic centimeters of a +reducing sugar of approximately one per cent strength added at once. +The reduction is thus secured at a temperature below 100°, which is an +important consideration in securing the minimum decomposing effect of +the alkali upon the sugar. The dish is kept upon the water-bath for +about ten minutes when the reduction is complete and the supernatant +liquor should still be intensely blue. The precipitate is washed by +decantation with boiling water, taking care to avoid the loss of any +of the cuprous oxid. The washing is continued until the wash waters +are neutral to phenolphthalein. The cuprous oxid is then washed into a +pyknometer of from twenty to twenty-five cubic centimeters capacity, +the exact content of which has been previously determined at zero. It +is filled with boiling water, the stopper inserted, and after cooling +the flask is weighed. Let <i>P</i> be the weight of the pyknometer plus +the liquid and the precipitate, the total volume of which is equal to +the capacity of the flask at the temperature at which it was filled, +that is <i>V</i>ₜ = <i>V</i>₀ [1 + 3β(<i>t</i>-<i>t</i>₀)].</p> + +<p>This formula is essentially that given in paragraph <b><a href="#P_51">51</a></b>, for +calculating the volume of a pyknometer at any temperature, substituting +for 3β, γ the cubical expansion of glass, <i>viz</i>., 0.000025.</p> + +<p>The specific gravity of the dry cuprous oxid is Δ = 5.881 and let the +specific gravity of water at the temperature of filling, which can be +taken from any of the tables of the density of water, be <i>d</i>. +The total weight <i>p</i> of the precipitated suboxid may then be +calculated by the following formula:</p> + +<table class="spb1 fs_110"> + <tbody><tr> + <td class="tdl" rowspan="2"><i>P</i> = </td> + <td class="tdc bb" colspan="2"><i>P</i>-<i>V</i>ₜ <i>d</i></td> + <td class="tdl_wsp" rowspan="2">.</td> + </tr><tr> + <td class="tdl">1 -</td> + <td class="tdl bb"> <i>d</i></td> + </tr><tr> + <td class="tdl"> </td> + <td class="tdl"> </td> + <td class="tdc">Δ</td> + <td class="tdl"> </td> + </tr> + </tbody> +</table> + +<p>The density of water at 99°, which is about the mean temperature of +<span class="pagenum"><a id="Page_138"></a>[Pg 138]</span> +boiling water for laboratories in general, is 0.95934, and this may be +taken as the weight of one cubic centimeter for purposes of calculation +in the formula above.</p> + +<p>In order to obtain exact results, it is important that the weight +<i>P</i> be reduced to a vacuum. The weight of cuprous oxid not varying +proportionally to the weight of reducing sugar, it is necessary to +prepare a table showing the principal numerical values of the two, in +order to be able to calculate easily all the possible values, either +directly from the table or by appropriate interpolations. Following are +the chief values which are necessary for the calculation:</p> + +<table class="spb1"> + <thead><tr> + <th class="tdc"> Milligrams <br>cuprous oxid.</th> + <th class="tdc"> Milligrams <br>dextrose.</th> + <th class="tdc"> Milligrams <br>cuprous oxid.</th> + <th class="tdc"> Milligrams <br>dextrose.</th> + </tr></thead> + <tbody><tr> + <td class="tdc">10</td> + <td class="tdc"> 5.413</td> + <td class="tdc">100</td> + <td class="tdc"> 46.221</td> + </tr><tr> + <td class="tdc">20</td> + <td class="tdc"> 9.761</td> + <td class="tdc">200</td> + <td class="tdc"> 91.047</td> + </tr><tr> + <td class="tdc">30</td> + <td class="tdc">14.197</td> + <td class="tdc">300</td> + <td class="tdc">138.842</td> + </tr><tr> + <td class="tdc">50</td> + <td class="tdc">23.036</td> + <td class="tdc">400</td> + <td class="tdc">188.928</td> + </tr> + </tbody> +</table> + +<p>It is claimed by the author that the above method is both simple and +rapid and can be applied with an error of not more than one-thousandth +if the corrections for temperature and pressure be rigorously +applied.<a id="FNanchor_85" href="#Footnote_85" class="fnanchor">[85]</a></p> + +<p id="P_124"><b>124. The Copper Carbonate Process.</b>—While the copper solutions +which have been mentioned in previous paragraphs have only a slight +action on sucrose and dextrin yet on prolonged boiling even these +bodies show a reducing effect due probably to a preliminary change in +the sugar molecules whereby products analogous to dextrose or invert +sugar are formed. In order to secure a reagent, to which the sugar not +reducing alkaline copper solutions might be more resistant Soldaini has +proposed to employ a liquor containing the copper as carbonate instead +of as tartrate.<a id="FNanchor_86" href="#Footnote_86" class="fnanchor">[86]</a> +This solution is prepared by adding to a solution of forty grams of +copper sulfate one of equal strength of sodium carbonate. The resulting +copper carbonate and hydroxid are collected on a filter, washed with +cold water, and dried. The reaction which takes place is represented by +the following formula:</p> + +<p class="f110">2CuSO₄ + 2Na₂CO₃ + H₂O =<br> +<span class="ws8">CuCO₃ + CuO₂H₂ + 2Na₂SO₄ + CO₂.</span></p> + +<p>The dry precipitate obtained, which will weigh about fifteen grams, is +<span class="pagenum"><a id="Page_139"></a>[Pg 139]</span> +placed in a large flask with about 420 grams of potassium bicarbonate +and 1400 cubic centimeters of water. The contents of the flask are +heated on a steam-bath for several hours with occasional stirring +until the evolution of carbon dioxid has ceased. During this time the +liquid is kept at the same volume by the addition of water, or by +attaching a reflux condenser to the flask. The potassium and copper +compounds at the end of this time will be found dissolved and the +resulting liquor will have a deep blue color. After filtration the +solution is boiled for a few minutes and cooled to room temperature. +The volume is then completed to two liters. A more direct method of +preparing the solution, and one quite as effective, consists in adding +the solution of the copper sulfate directly to the hot solution of +potassium bicarbonate and heating and shaking the mixture until the +copper carbonate formed is dissolved. After filtering the volume is +made as above. The proportions of reagents employed are placed by +Preuss at 15.8 grams of crystallized copper sulfate and 594 grams of +potassium bicarbonate.<a id="FNanchor_87" href="#Footnote_87" class="fnanchor">[87]</a> +The soldaini reagent is extremely sensitive and is capable of detecting +as little as half a milligram of invert sugar. The presence of sucrose +makes the reagent more delicate, and it is especially useful in +determining the invert sugar arising during the progress of manufacture +by the action of heat and melassigenic bodies on sucrose.</p> + +<p><b>125. The Analytical Process.</b>—As in the case of fehling solution +a great many methods of conducting the analysis with the soldaini +reagent have been proposed. The general principle of all these +processes is the one already described for the alkaline copper tartrate +solution, <i>viz.</i>, the addition of the reducing sugar solution to +the boiling reagent, and the determination of the end of the reaction +by the disappearance of the copper.<a id="FNanchor_88" href="#Footnote_88" class="fnanchor">[88]</a></p> + +<p>Practically, however, these methods have had no general application, +and the use of the soldaini reagent has been confined chiefly to the +determination of invert sugar in presence of a large excess of sucrose. +For this purpose the sugar solution is not added until the blue color +of the reagent has been destroyed, but on the other hand, the reagent +has been used in excess, and the cuprous oxid formed collected and +<span class="pagenum"><a id="Page_140"></a>[Pg 140]</span> +weighed as metallic copper. The weight of the metallic copper found, +multiplied by the factor 0.3546, gives the weight of invert sugar in +the volume of the sugar solution used. According to Preuss, the factor +is not a constant one, but varies with the quantity of invert sugar +present, as is seen in the formula <i>y</i> = 2.2868 + 3.3<i>x</i> + +0.0041<i>x</i>², in which <i>x</i> = the invert sugar, and <i>y</i> the +metallic copper.<a id="FNanchor_89" href="#Footnote_89" class="fnanchor">[89]</a></p> + +<p><b>126. Tenth Normal Copper Carbonate Solution.</b>—In the study of +some of the solutions of copper carbonate, proposed for practical +work, Ettore Soldaini was impressed with the difficulty of dissolving +so large a quantity of carbonate in the solvent employed.<a id="FNanchor_90" href="#Footnote_90" class="fnanchor">[90]</a> +The solution recommended by Bodenbender and Scheller,<a id="FNanchor_91" href="#Footnote_91" class="fnanchor">[91]</a> +in which forty grams of the crystallized copper sulfate were used, +failed to disclose an equivalent amount of copper in the reagent ready +for use. For this reason a tenth-normal copper solution is prepared by +Soldaini containing the equivalent of 3.464 grams of copper sulfate +in one liter. The reagent is easily prepared by adding slowly the +dissolved or finely powdered copper salt to a solution of 297 grams +of potassium bicarbonate, and after complete solution of the copper +carbonate formed, completing the volume to one liter. With this reagent +as little as one-quarter of a milligram of reducing sugar can be easily +detected. For the quantitive estimation of sugar a solution of the +above strength is to be preferred to the other forms of the soldaini +reagent by reason of the ease of direct comparison with standard +fehling solutions.</p> + +<p>The analytical process is conducted with the tenth-normal solution, +prepared by Soldaini and described above, as follows: Place 100 cubic +centimeters of the reagent in each of several porcelain dishes heat +to boiling, and add little by little the sugar solution to one dish +until the blue color has disappeared. Having thus determined nearly the +exact quantity of sugar solution required for the copper in 100 cubic +centimeters of the reagent the whole of the sugar solution is added at +once, varying slightly the amounts added to each dish. The boiling is +continued for fifteen minutes, and the contents of the dishes poured +on filters. That filtrate which contains neither copper nor sugar +represents the exact quantity of sugar solution which contained fifty +milligrams of dextrose. +<span class="pagenum"><a id="Page_141"></a>[Pg 141]</span></p> + +<p><b>127. Relation of Reducing Sugar to Quantity of Copper Suboxid +Obtained.</b>—The relation of the quantity of copper reduced to +the amount of sugar oxidized by the copper carbonate solution has +been determined by Ost, and the utility of the process thereby +increased.<a id="FNanchor_92" href="#Footnote_92" class="fnanchor">[92]</a> +The solution used should have the following composition: 23.5 grams +of crystallized copper sulfate, 250 grams of potassium carbonate, and +100 grams of potassium bicarbonate in one liter. Without an indicator +the end reaction is distinctly marked by the passage of the blue color +into a colorless solution. Ost affirms that this solution is preferable +to any form of fehling liquor because it can be kept indefinitely +unchanged; it attacks sucrose far less strongly, and an equal quantity +of sugar precipitates nearly double the quantity of copper. The boiling +requires a longer time, as a rule ten minutes, but this is a matter of +no importance, when the other advantages are taken into consideration. +The relations of the different sugars to the quantity of copper +precipitated are given in the table in the next paragraph.</p> + +<p id="P_128"><b>128. Factor for Different Sugars.</b>—For pure dextrose the +relation between sugar and copper reduced has been determined by +Ost, and the data are given in the table below. The data were +obtained by adding to fifty cubic centimeters of the copper solution +twenty-five cubic centimeters of sugar solutions of varying strength +and collecting, washing, and reducing the cuprous oxid obtained in a +current of hydrogen in a glass tube by the method described further on.</p> + +<p>The boiling in all cases was continued, just ten minutes, although a +slight variation from the standard time did not produce so great a +difference as with fehling reagent. In the case of dextrose, when fifty +milligrams were used with fifty cubic centimeters of the solution, +the milligrams of copper obtained after six, ten and twenty minutes’ +boiling were 164.6, 165.5, and 166.9 respectively.<a id="FNanchor_93" href="#Footnote_93" class="fnanchor">[93]</a></p> + +<p>The data differ considerably from those obtained by Herzfeld, but +in his experiments the boiling was continued only for five minutes, +<span class="pagenum"><a id="Page_142"></a>[Pg 142]</span> +and this is not long enough to secure the proper reduction of the +copper.<a id="FNanchor_94" href="#Footnote_94" class="fnanchor">[94]</a></p> + +<p class="f120 spa1"><b><span class="smcap">Table Showing the Quantity of Copper<br> +Reduced by Different Sugars.</span></b></p> + +<table class="spb1"> + <thead><tr> + <th class="tdc bb">Copper.<br> Milligrams </th> + <th class="tdc bb">Invert Sugar.<br> Milligrams </th> + <th class="tdc bb">Dextrose.<br> Milligrams </th> + <th class="tdc bb">Levulose.<br> Milligrams </th> + <th class="tdc bb">Galactose.<br> Milligrams </th> + <th class="tdc bb">Arabinose.<br> Milligrams</th> + </tr></thead> + <tbody><tr> + <td class="tdc"> 50</td> + <td class="tdc">15.2</td> + <td class="tdc">15.6</td> + <td class="tdc">14.7</td> + <td class="tdc">17.4</td> + <td class="tdc">17.0</td> + </tr><tr> + <td class="tdc"> 55</td> + <td class="tdc">16.6</td> + <td class="tdc">17.0</td> + <td class="tdc">16.1</td> + <td class="tdc">19.1</td> + <td class="tdc">18.6</td> + </tr><tr> + <td class="tdc"> 60</td> + <td class="tdc">18.0</td> + <td class="tdc">18.5</td> + <td class="tdc">17.5</td> + <td class="tdc">20.8</td> + <td class="tdc">20.3</td> + </tr><tr> + <td class="tdc"> 65</td> + <td class="tdc">19.4</td> + <td class="tdc">19.9</td> + <td class="tdc">18.9</td> + <td class="tdc">22.5</td> + <td class="tdc">21.9</td> + </tr><tr> + <td class="tdc"> 70</td> + <td class="tdc">20.8</td> + <td class="tdc">21.4</td> + <td class="tdc">20.3</td> + <td class="tdc">24.2</td> + <td class="tdc">23.5</td> + </tr><tr> + <td class="tdc"> 75</td> + <td class="tdc">22.3</td> + <td class="tdc">22.9</td> + <td class="tdc">21.7</td> + <td class="tdc">25.9</td> + <td class="tdc">25.1</td> + </tr><tr> + <td class="tdc"> 80</td> + <td class="tdc">23.7</td> + <td class="tdc">24.4</td> + <td class="tdc">23.0</td> + <td class="tdc">27.7</td> + <td class="tdc">26.7</td> + </tr><tr> + <td class="tdc"> 85</td> + <td class="tdc">25.2</td> + <td class="tdc">25.8</td> + <td class="tdc">24.3</td> + <td class="tdc">29.3</td> + <td class="tdc">28.3</td> + </tr><tr> + <td class="tdc"> 90</td> + <td class="tdc">26.6</td> + <td class="tdc">27.3</td> + <td class="tdc">25.7</td> + <td class="tdc">31.1</td> + <td class="tdc">29.9</td> + </tr><tr> + <td class="tdc bb"> 95</td> + <td class="tdc bb">28.1</td> + <td class="tdc bb">28.8</td> + <td class="tdc bb">27.1</td> + <td class="tdc bb">32.8</td> + <td class="tdc bb">31.5</td> + </tr><tr> + <td class="tdc">100</td> + <td class="tdc">29.5</td> + <td class="tdc">30.3</td> + <td class="tdc">28.5</td> + <td class="tdc">34.5</td> + <td class="tdc">33.1</td> + </tr><tr> + <td class="tdc">105</td> + <td class="tdc">31.0</td> + <td class="tdc">31.8</td> + <td class="tdc">29.9</td> + <td class="tdc">36.2</td> + <td class="tdc">34.7</td> + </tr><tr> + <td class="tdc">110</td> + <td class="tdc">32.4</td> + <td class="tdc">33.3</td> + <td class="tdc">31.2</td> + <td class="tdc">38.0</td> + <td class="tdc">36.3</td> + </tr><tr> + <td class="tdc">115</td> + <td class="tdc">33.9</td> + <td class="tdc">34.8</td> + <td class="tdc">32.6</td> + <td class="tdc">39.7</td> + <td class="tdc">37.9</td> + </tr><tr> + <td class="tdc">120</td> + <td class="tdc">35.3</td> + <td class="tdc">36.3</td> + <td class="tdc">34.0</td> + <td class="tdc">41.4</td> + <td class="tdc">39.5</td> + </tr><tr> + <td class="tdc">125</td> + <td class="tdc">36.8</td> + <td class="tdc">37.8</td> + <td class="tdc">35.4</td> + <td class="tdc">43.1</td> + <td class="tdc">41.1</td> + </tr><tr> + <td class="tdc">130</td> + <td class="tdc">38.2</td> + <td class="tdc">39.3</td> + <td class="tdc">36.8</td> + <td class="tdc">44.8</td> + <td class="tdc">42.8</td> + </tr><tr> + <td class="tdc">135</td> + <td class="tdc">39.7</td> + <td class="tdc">40.8</td> + <td class="tdc">38.2</td> + <td class="tdc">46.5</td> + <td class="tdc">44.4</td> + </tr><tr> + <td class="tdc">140</td> + <td class="tdc">41.1</td> + <td class="tdc">42.3</td> + <td class="tdc">39.6</td> + <td class="tdc">48.3</td> + <td class="tdc">46.0</td> + </tr><tr> + <td class="tdc bb">145</td> + <td class="tdc bb">42.6</td> + <td class="tdc bb">43.8</td> + <td class="tdc bb">41.0</td> + <td class="tdc bb">50.0</td> + <td class="tdc bb">47.6</td> + </tr><tr> + <td class="tdc">150</td> + <td class="tdc">44.0</td> + <td class="tdc">45.3</td> + <td class="tdc">42.5</td> + <td class="tdc">51.8</td> + <td class="tdc">49.3</td> + </tr><tr> + <td class="tdc">155</td> + <td class="tdc">45.5</td> + <td class="tdc">46.8</td> + <td class="tdc">43.9</td> + <td class="tdc">53.6</td> + <td class="tdc">50.9</td> + </tr><tr> + <td class="tdc">160</td> + <td class="tdc">47.0</td> + <td class="tdc">48.3</td> + <td class="tdc">45.3</td> + <td class="tdc">55.4</td> + <td class="tdc">52.6</td> + </tr><tr> + <td class="tdc">165</td> + <td class="tdc">48.5</td> + <td class="tdc">49.8</td> + <td class="tdc">46.7</td> + <td class="tdc">57.2</td> + <td class="tdc">54.3</td> + </tr><tr> + <td class="tdc">170</td> + <td class="tdc">50.0</td> + <td class="tdc">51.4</td> + <td class="tdc">48.1</td> + <td class="tdc">59.0</td> + <td class="tdc">55.9</td> + </tr><tr> + <td class="tdc">175</td> + <td class="tdc">51.5</td> + <td class="tdc">52.9</td> + <td class="tdc">49.5</td> + <td class="tdc">60.8</td> + <td class="tdc">57.5</td> + </tr><tr> + <td class="tdc">180</td> + <td class="tdc">53.0</td> + <td class="tdc">54.5</td> + <td class="tdc">51.0</td> + <td class="tdc">62.7</td> + <td class="tdc">59.2</td> + </tr><tr> + <td class="tdc">185</td> + <td class="tdc">54.5</td> + <td class="tdc">56.0</td> + <td class="tdc">52.5</td> + <td class="tdc">64.5</td> + <td class="tdc">60.9</td> + </tr><tr> + <td class="tdc">190</td> + <td class="tdc">56.0</td> + <td class="tdc">57.6</td> + <td class="tdc">54.0</td> + <td class="tdc">66.4</td> + <td class="tdc">62.7</td> + </tr><tr> + <td class="tdc bb">195</td> + <td class="tdc bb">57.5</td> + <td class="tdc bb">59.2</td> + <td class="tdc bb">55.5</td> + <td class="tdc bb">68.3</td> + <td class="tdc bb">64.4</td> + </tr><tr> + <td class="tdc">200</td> + <td class="tdc">59.1</td> + <td class="tdc">60.8</td> + <td class="tdc">57.0</td> + <td class="tdc">70.3</td> + <td class="tdc">66.2</td> + </tr><tr> + <td class="tdc">205</td> + <td class="tdc">60.7</td> + <td class="tdc">62.4</td> + <td class="tdc">58.6</td> + <td class="tdc">72.3</td> + <td class="tdc">68.0</td> + </tr><tr> + <td class="tdc">210</td> + <td class="tdc">62.4</td> + <td class="tdc">64.1</td> + <td class="tdc">60.2</td> + <td class="tdc">74.3</td> + <td class="tdc">69.8</td> + </tr><tr> + <td class="tdc">215</td> + <td class="tdc">64.1</td> + <td class="tdc">65.8</td> + <td class="tdc">61.8</td> + <td class="tdc">76.3</td> + <td class="tdc">71.6</td> + </tr><tr> + <td class="tdc">220</td> + <td class="tdc">65.8</td> + <td class="tdc">67.5</td> + <td class="tdc">63.5</td> + <td class="tdc">78.3</td> + <td class="tdc">73.5</td> + </tr><tr> + <td class="tdc">225</td> + <td class="tdc">67.5</td> + <td class="tdc">69.2</td> + <td class="tdc">65.2</td> + <td class="tdc">80.3</td> + <td class="tdc">75.4</td> + </tr><tr> + <td class="tdc">230</td> + <td class="tdc">69.3</td> + <td class="tdc">70.9</td> + <td class="tdc">66.9</td> + <td class="tdc">82.4</td> + <td class="tdc">77.3</td> + </tr><tr> + <td class="tdc">235</td> + <td class="tdc">71.1</td> + <td class="tdc">72.7</td> + <td class="tdc">68.7</td> + <td class="tdc">84.5</td> + <td class="tdc">79.3</td> + </tr><tr> + <td class="tdc">240</td> + <td class="tdc">72.9</td> + <td class="tdc">74.5</td> + <td class="tdc">70.6</td> + <td class="tdc">86.6</td> + <td class="tdc">81.3</td> + </tr><tr> + <td class="tdc bb">245</td> + <td class="tdc bb">74.8</td> + <td class="tdc bb">76.4</td> + <td class="tdc bb">72.5</td> + <td class="tdc bb">88.9</td> + <td class="tdc bb">83.4</td> + </tr><tr> + <td class="tdc">250</td> + <td class="tdc">76.7</td> + <td class="tdc">78.4</td> + <td class="tdc">74.4</td> + <td class="tdc">91.2</td> + <td class="tdc">85.5</td> + </tr><tr> + <td class="tdc">255</td> + <td class="tdc">78.6</td> + <td class="tdc">80.5</td> + <td class="tdc">76.5</td> + <td class="tdc">93.5</td> + <td class="tdc">87.6</td> + </tr><tr> + <td class="tdc">260</td> + <td class="tdc">80.5</td> + <td class="tdc">82.8</td> + <td class="tdc">78.8</td> + <td class="tdc">95.9</td> + <td class="tdc">89.8</td> + </tr><tr> + <td class="tdc">265</td> + <td class="tdc">82.5</td> + <td class="tdc">85.1</td> + <td class="tdc">81.1</td> + <td class="tdc">98.3</td> + <td class="tdc">92.2</td> + </tr><tr> + <td class="tdc">270</td> + <td class="tdc">84.7</td> + <td class="tdc">87.5</td> + <td class="tdc">83.5</td> + <td class="tdc">100.7 </td> + <td class="tdc">94.6</td> + </tr><tr> + <td class="tdc">275</td> + <td class="tdc">87.1</td> + <td class="tdc">89.9</td> + <td class="tdc">85.9</td> + <td class="tdc">103.3 </td> + <td class="tdc">97.1</td> + </tr><tr> + <td class="tdc">280</td> + <td class="tdc">89.7</td> + <td class="tdc">92.4</td> + <td class="tdc">88.6</td> + <td class="tdc">106.1 </td> + <td class="tdc">99.6</td> + </tr><tr> + <td class="tdc">285</td> + <td class="tdc">92.3</td> + <td class="tdc">94.9</td> + <td class="tdc">91.3</td> + <td class="tdc">109.0 </td> + <td class="tdc">102.3 </td> + </tr><tr> + <td class="tdc">290</td> + <td class="tdc">95.1</td> + <td class="tdc">97.6</td> + <td class="tdc">94.2</td> + <td class="tdc">112.0 </td> + <td class="tdc">105.1 </td> + </tr><tr> + <td class="tdc">295</td> + <td class="tdc">98.0</td> + <td class="tdc">100.4 </td> + <td class="tdc">97.2</td> + <td class="tdc">115.1 </td> + <td class="tdc">107.9 </td> + </tr><tr> + <td class="tdc">298</td> + <td class="tdc">100.0 </td> + <td class="tdc">102.5 </td> + <td class="tdc">99.0</td> + <td class="tdc">117.0 </td> + <td class="tdc">109.5 </td> + </tr> + </tbody> +</table> +<p class="spa2"><span class="pagenum"><a id="Page_143"></a>[Pg 143]</span></p> + +<h3>VOLUMETRIC METHODS<br> BASED UPON THE USE OF AN<br> AMMONIACAL COPPER SOLUTION.</h3> + +<p><b>129. Pavy’s Process.</b>—The well-known solubility of cuprous oxid +in ammonia led Pavy to adopt a copper reagent containing ammonia in the +volumetric determination of reducing sugars.<a id="FNanchor_95" href="#Footnote_95" class="fnanchor">[95]</a> In Pavy’s process an +alkaline copper solution is employed made up in the usual way, to which +a sufficient quantity of ammonia is added to hold in solution all the +copper when precipitated as cuprous oxid. The solution used by Pavy has +the following composition: One liter contains</p> + +<table class="spb2"> + <tbody><tr> + <td class="tdl">Crystallized copper sulfate  </td> + <td class="tdr">34.65</td> + <td class="tdl_wsp">grams</td> + </tr><tr> + <td class="tdl">Potassium-sodium tartrate</td> + <td class="tdr">173.00</td> + <td class="tdc">”</td> + </tr><tr> + <td class="tdl">Caustic potash</td> + <td class="tdr">160.00</td> + <td class="tdc">”</td> + </tr> + </tbody> +</table> + +<p>For use 120 cubic centimeters of the above reagent are mixed with 300 +of ammonia of specific gravity 0.88, and the volume completed to one +liter with distilled water. Twenty cubic centimeters of this reagent +are equivalent to ten milligrams of dextrose or invert sugar when added +in a one per cent solution.</p> + +<p>In the use of ammoniacal copper solution, care must be taken that +all the liquids employed be entirely free of oxygen and that the +contents of the flask in which the reduction takes place be in some way +excluded from contact with the air. Pavy secured this by conducting +the reduction in a flask closed with a stopper carrying two holes; +one of these served for the introduction of the burette carrying the +sugar solution and the other carried a tube dipping into a water seal +by means of a slit rubber tube, which would permit of the exit of the +vapors of steam and ammonia, but prevent the regurgitation of the water +into the flask.</p> + +<p>The complete decoloration of the copper solution marks the end of the +reaction. The usual precautions in regard to the length of the time of +boiling must be observed.</p> + +<p>It is easy to see that in the Pavy process the quantity of ammonia in +the solution is rapidly diminished during the boiling and this has led +to the suggestion of other methods to exclude the air. Among these have +been recommended the introduction of a current of hydrogen or carbon +dioxid. One of the best methods of procedure is that proposed by Allen, +<span class="pagenum"><a id="Page_144"></a>[Pg 144]</span> +who recommends covering the copper solution by a layer of paraffin oil +(kerosene).<a id="FNanchor_96" href="#Footnote_96" class="fnanchor">[96]</a></p> + +<p><b>130. Process Of Peska.</b>—Peska has also independently made use of +Allen’s method of covering the solutions with a layer of paraffin oil +and finds it reliable.<a id="FNanchor_97" href="#Footnote_97" class="fnanchor">[97]</a> +The copper reagent employed by him has the following composition:</p> + +<table class="spb2"> + <tbody><tr> + <td class="tdl">Crystallized copper sulfate</td> + <td class="tdr">6.927</td> + <td class="tdl_wsp">grams</td> + </tr><tr> + <td class="tdl">Ammonia, twenty-five per cent strength  </td> + <td class="tdr">160.00 </td> + <td class="tdl_wsp">cc.</td> + </tr> + </tbody> +</table> + +<p>The copper sulfate is dissolved in water, the ammonia added, and +the volume completed to half a liter with distilled water. A second +solution containing half a liter is made by dissolving 34.5 grams +of potassium-sodium tartrate and ten grams of sodium hydroxid and +completing the cool solution to half a liter with distilled water. +In all cases the water used in making up the above solutions must be +freshly boiled to exclude the air.</p> + +<p>For the titration, fifty cubic centimeters of each of the above +solutions are taken, mixed and covered with a layer of paraffin oil +half a centimeter in depth. The reduction is not accomplished at a +boiling temperature, but at from 80° to 85°. The manipulation is +conducted as follows:</p> + +<p>The mixed solutions are placed in a beaker, covered with oil, and +heated to 80°. The temperature is measured by a thermometer which also +serves as a stirring rod. The sugar solution is run down the sides +of the beaker from a burette of such a shape as to be protected from +the heat. After each addition of the sugar solution the mixture is +carefully stirred, keeping the temperature at from 80° to 85°. The +first titration is made to determine approximately the quantity of +sugar solution necessary to decolorize the copper. This done, the +actual titration is accomplished by adding at once the total amount +of sugar solution necessary to decolorize, less about one cubic +centimeter. Any sugar solution adhering to the side of the beaker +is washed down by distilled water, the contents of the beaker well +stirred, and the temperature kept at 85° for two minutes. The rest of +the sugar solution is then added in quantities of one-tenth of a cubic +centimeter until the decoloration is completed. The total time of the +final titration should not exceed five minutes. The sugar solution +should be as nearly as possible of one per cent strength. If a lower +<span class="pagenum"><a id="Page_145"></a>[Pg 145]</span> +degree of strength be employed a larger quantity of the sugar is +necessary to reduce a given quantity of copper.</p> + +<p>In the case of dextrose, when a one per cent solution is used, eight +and two-tenths cubic centimeters, corresponding to 80.2 milligrams of +dextrose, are required to reduce 100 cubic centimeters of the mixed +reagent. On the other hand, when the sugar solution is diluted to +one-tenth of a per cent strength 82.1 milligrams are required.</p> + +<p>With invert sugar slightly larger quantities are necessary, the +reducing power being as 94.9 to 100 as compared with dextrose. With +a one per cent strength of invert sugar it is found that eighty-four +milligrams are required to reduce 100 cubic centimeters of the mixed +reagent and when the strength of the invert sugar is reduced to +one-tenth per cent 87.03 milligrams are required.</p> + +<p><b>131. Method Of Allein and Gaud.</b>—Allein and Gaud have proposed a +further modification of the ammonia process which consists essentially +in the suppression of rochelle salt and fixed caustic alkali and the +entire substitution therefor of ammonia. Ammonia acts with much less +vigor upon sugars than the caustic alkalies, and it is therefore +claimed that the decomposition of the sugar due to the alkali is +reduced to a minimum when ammonia is employed.<a id="FNanchor_98" href="#Footnote_98" class="fnanchor">[98]</a> +The copper solution is made as follows:</p> + +<p>Dissolve 8.7916 grams of electrolytic copper in ninety-three grams +of concentrated sulfuric acid diluted with an equal volume of water. +Complete the resulting solution to one liter with concentrated ammonia. +Ten cubic centimeters of this solution are equal to fifty grams of +dextrose.</p> + +<p>It is recommended that the reduction be accomplished in an atmosphere +of hydrogen, but it is apparent that the use of kerosene is permissible +in this case, and on account of its greater simplicity it is to be +recommended as the best means of excluding the oxygen. The reduction is +accomplished at a temperature of about 80°.</p> + +<p>It is also proposed to reoxidize the copper by substituting a current +of air for the hydrogen at the end of the reaction, and thus use the +same copper a number of times. The danger of loss of ammonia, and the +<span class="pagenum"><a id="Page_146"></a>[Pg 146]</span> +difficulty of determining when the oxidation is complete, render this +regeneration of the reagent undesirable.</p> + +<p><b>132. Method of Gerrard.</b>—The method of Gerrard does not depend +upon the use of ammonia, but the principle involved is the same, +<i>viz.</i>, the holding of the separated cuprous oxid in solution +and the determination of the end of the reaction by the disappearance +of the blue color. As first proposed by Gerrard, the copper sulfate +solution is made of double the strength usually employed and to each +100 cubic centimeters thereof, before use, three and three-tenths +grams of potassium cyanid are added. This is sufficient to hold the +precipitated cuprous oxid in solution.<a id="FNanchor_99" href="#Footnote_99" class="fnanchor">[99]</a></p> + +<p>The original method of Gerrard is found difficult of execution and the +author, in conjunction with Allen, has lately modified it and reduced +it to a practical working basis.<a id="FNanchor_100" href="#Footnote_100" class="fnanchor">[100]</a></p> + +<p>In the new method the ordinary fehling solution is employed and it +is prepared for use in the following way: Ten cubic centimeters of +the fehling solution, or half that quantity of each of the component +parts kept in separate bottles, are placed in a porcelain dish with +forty cubic centimeters of water and brought to the boiling-point. To +the boiling liquid is added, from a pipette, a five per cent solution +of potassium cyanid until the blue color just disappears, or only a +very faint tint of blue remains, avoiding any excess of the cyanid. A +second portion of the fehling solution equal to that first employed +is added, and to the boiling mixture the solution of sugar is added, +from a burette, until the blue color disappears. The contents of the +dish should be kept boiling during the addition of the sugar solution. +The volume used will contain fifty milligrams of dextrose. The sugar +solution should be of such a strength as to contain no more than half a +per cent of reducing sugar.</p> + +<p>The principle of the preparation of the solution may be stated as +follows: If to a solution of copper sulfate, potassium be added until +the blue color disappears, a double cyanid of copper and potassium +cyanid is formed according to the following reaction:</p> + +<p class="f110">CuSO₄ + 4KCN = Cu(CN)₂.2KCN + K₂SO₄.</p> + +<p class="no-indent">This double cyanid is a salt of considerable +stability. It is not decomposed by alkalies, hydrogen or ammonium, +<span class="pagenum"><a id="Page_147"></a>[Pg 147]</span> +sulfid. With mineral acids it gives a whitish, curdy precipitate. With +fehling solution the same double cyanid is formed as that described +above. If, however, fehling solution be present in excess of the amount +necessary to form the double cyanid of copper, this excess can be used +in the oxidation of reducing sugar and the colorless condition of the +solution will be restored as soon as the excess of the fehling is +destroyed. The double cyanid holds in solution the cuprous oxid formed +and thus complete decoloration is secured.</p> + +<p><b>133. Sidersky’s Modification of Soldaini’s Process.</b>—In all +cases where the sugar solutions are not too highly colored, Sidersky +finds that the method of reduction in a large test tube, as practiced +by Violette, is applicable with the copper carbonate solution.<a id="FNanchor_101" href="#Footnote_101" class="fnanchor">[101]</a> +For more exact work it is preferred to determine the quantity of copper +reduced by an indirect volumetric method. The sugar solution, properly +clarified and the lead removed if subacetates have been used, is made +of such a volume as to contain less than one per cent of reducing +sugars. In a flask or large test tube are placed 100 cubic centimeters +of the copper solution, which is boiled for a short time and the sugar +solution added, little by little, from a pipette, at such a rate as +not to stop the ebullition. The boiling is continued for five minutes +after the last addition of the sugar. The vessel is taken from the +flame and 100 cubic centimeters of cold water added, the whole brought +on an asbestos felt and the cuprous oxid washed with hot water until +the alkaline reaction has disappeared. The residual cuprous oxid +is dissolved in a measured quantity of set sulfuric acid, semi- or +fifth-normal, a few particles of potassium chlorate added, and the +mixture boiled to convert any cuprous into cupric sulfate. The reaction +is represented by the following formula:</p> + +<p class="f110">3Cu₂O + 6H₂SO₄ + KClO₃ = 6CuSO₄ + KCl + 6H₂O.</p> + +<p>The residual sulfuric acid is titrated with a set alkali in excess, +ammonia being preferred.</p> + +<p>The solution of ammonia is made by diluting 200 cubic centimeters of +commercial aqua ammonia with 800 of water. Its strength is determined +by adding a little copper sulfate solution as indicator and then the +set solution of sulfuric acid until the blue color disappears. The +<span class="pagenum"><a id="Page_148"></a>[Pg 148]</span> +copper sulfate secured from the cuprous sulfate as described above +is cooled, and a quantity of the ammonia, equal to twenty-five cubic +centimeters of the set sulfuric acid, added. The excess of the +ammonia is then determined by titration with the sulfuric acid, the +disappearance of the blue color being the indication of the end of the +reaction. The number of cubic centimeters of the set sulfuric acid +required to saturate the ammonia represents the equivalent of cuprous +oxid originally present. One cubic centimeter of normal sulfuric acid +is equivalent to 0.0317 gram of metallic copper.</p> + +<p>To determine the weight of invert sugar oxidized, multiply the weight +of copper, calculated as above described, by the factor 0.3546.<a id="FNanchor_102" href="#Footnote_102" class="fnanchor">[102]</a> +For a general application of this method of analysis the relative +quantities of copper reduced by different quantities of sugar must be +taken into consideration.</p> + +<p>While, as has already been stated, the copper carbonate process has +heretofore been applied chiefly to the detection of invert sugar, it +has merits which justify the expectation that it may some time supplant +the fehling liquor both for volumetric and gravimetric work. Large +volumes of the reagent can be prepared at once and without danger of +subsequent change. The action of the reagent on the hexobioses and +trioses is far less vigorous than that of the alkaline copper tartrate, +and the end reactions for volumetric work are, at least, as easily +determined in the one case as the other.</p> + +<p><b>134. Method Depending on Titration of Excess of Copper.</b>—Instead +of measuring the quantity of copper reduced, either by its +disappearance or by reducing the cuprous oxid to a metallic state, +Politis has proposed a method of analysis depending on the titration of +the residual copper.<a id="FNanchor_103" href="#Footnote_103" class="fnanchor">[103]</a> +The reagents employed are:</p> + +<div class="blockquot"> +<p>(1) A copper solution containing 24.95 grams of crystallized copper +sulfate, 140 grams of sodium and potassium tartrate, and twenty-five +grams of sodium hydroxid in one liter:</p> + +<p>(2) A solution of sodium thiosulfate containing 24.8 grams of the salt +in one liter:</p> + +<p>(3) A solution of potassium iodid containing 12.7 grams of iodin in one +liter.</p> +</div> + +<p><span class="pagenum"><a id="Page_149"></a>[Pg 149]</span> +The reaction is represented by the formula</p> + +<p class="f110">2CuCl₂ + 4KI = Cu₂I₂ + 4KCl + I₂.</p> + +<p>The analytical process is carried out as follows: In a 100 cubic +centimeter flask are boiled fifty cubic centimeters of the copper +solution, ten cubic centimeters of about one-tenth per cent reducing +sugar solution are added, the boiling continued for five minutes, +the flask filled to the mark with boiling water and its contents +filtered. Fifty cubic centimeters of the hot filtrate are cooled, +slightly acidified, potassium iodid solution added in slight excess; +and the iodin set free determined by titration with sodium thiosulfate. +The quantity of iodin obtained corresponds to the unreduced copper +remaining after treatment with the reducing sugar. The number of cubic +centimeters of thiosulfate used subtracted from twenty-five will give +the number of cubic centimeters of the copper solution which would be +reduced by five cubic centimeters of the sugar solution used.</p> + +<p class="blockquot"><i>Example.</i>—In the proportions given above it +was found that eleven cubic centimeters of thiosulfate were required +to saturate the iodin set free. Then 25 - 11 = 14 cubic centimeters +of copper solution reduced by five cubic centimeters of the sugar +solution. Since one cubic centimeter of the copper solution is reduced +by 0.0036 gram of dextrose the total dextrose in the five cubic +centimeters = 0.0036 × 5 = 0.0180 gram.</p> + +<p>The above method does not seem to have any practical advantage over +those based on noting the disappearance of the copper and is given only +to illustrate the principle of the process. While the titration of the +iodin by sodium thiosulfate is easily accomplished in the absence of +organic matter, it becomes difficult, as shown by Ewell, when organic +matters are present, as they always are in the oxidation of a sugar +solution. Ewell has therefore proposed to determine the residual copper +by a standard solution of potassium cyanid, but the method has not yet +been developed.<a id="FNanchor_104" href="#Footnote_104" class="fnanchor">[104]</a></p> + +<h3>GRAVIMETRIC COPPER METHODS.</h3> + +<p><b>135. General Principles.</b>—In the preceding pages the principles +of the volumetric methods of sugar analysis by means of alkaline copper +<span class="pagenum"><a id="Page_150"></a>[Pg 150]</span> +solution have been set forth. They depend either on the total +decomposition of the copper solution employed by the reducing sugar, +or else on the collection and titration of the cuprous oxid formed in +the reaction. In the gravimetric methods the general principle of the +process rests upon the collection of the cuprous oxid formed and its +reduction to metallic copper, the weight of which serves as a starting +point in the calculations of the weight of reducing sugar, which has +been oxidized in the solution.</p> + +<p>The factors which affect the weight of copper obtained are essentially +those which influence the results in the volumetric method. The +composition of the copper solution, the temperature at which the +reduction is accomplished, the time of heating, the strength of the +sugar solution and the details of the manipulation, all affect more or +less the quantity of copper obtained. As in the volumetric method also, +the kind of reducing sugar must be taken in consideration, dextrose, +levulose, invert sugar, maltose and other sugars having each a definite +factor for reduction in given conditions. It follows, therefore, that +only those results are of value which are obtained under definite +conditions, rigidly controlled.</p> + +<p id="P_136"><b>136. Gravimetric Methods of the Department of Agriculture +Laboratory.</b>—The process used in this laboratory is based +essentially on the methods of Maercker, Behrend, Morgen, Meissl, Hiller +and Allihn.<a id="FNanchor_105" href="#Footnote_105" class="fnanchor">[105]</a> +Where dextrose alone is present, the table of factors proposed by +Allihn is used and also the copper solution corresponding thereto.</p> + +<p class="spb1">For pure invert sugar, the tables and solutions of +Meissl are used. For invert sugar in the presence of sucrose, the table +and process proposed by Hiller are used. +<span class="pagenum"><a id="Page_151"></a>[Pg 151]</span></p> + +<div class="figcenter smcap"> + <img id="FIG_43" src="images/fig43.jpg" alt="" width="600" height="357" > + <p class="center spb1">Figure 43. Apparatus for the Electrolytic + Deposition of Copper.</p> +</div> + +<p><span class="pagenum"><a id="Page_152"></a>[Pg 152]</span> +The reduction of the copper solution and the electrolytic deposition of +the copper are accomplished as follows:</p> + +<p>The copper and alkali solutions are kept in separate bottles. After +mixing the equivalent volume of the two solutions in a beaker, heat is +applied and the mixture boiled. To the boiling liquid the proper volume +of the cold sugar solution is added. This must always be less than the +amount required for complete reduction. The solution is again brought +into ebullition and kept boiling exactly two minutes. A two-minute +sand glass is conveniently used to determine the time of boiling. At +the end of this time an equal volume of freshly boiled cold water is +added, and the supernatant liquor at once passed through a gooch under +pressure. The residual cuprous oxid is covered with boiling water and +washed by decantation until the wash water is no longer alkaline. It +is more convenient to wash in such a way that, at the end, the greater +part of the cuprous oxid is in the gooch. The felt and cuprous oxid are +then returned to the beaker in which the reduction is made. The gooch +is moistened with nitric acid to dissolve any adhering oxid and then +is washed into the beaker. Enough nitric acid is added to bring all +the oxid into solution, an excess being avoided, and a small amount +of water added. The mixture is again passed under pressure through +a gooch having a thin felt, to remove the asbestos and the filtrate +collected in a flask of about 150 cubic centimeters capacity. The +washing is continued until the gooch is free of copper, when the volume +of the filtrate should be about 100 cubic centimeters. The liquid is +transferred to a platinum dish holding about 175 cubic centimeters and +the flask washed with about twenty-five cubic centimeters of water. +From three to five cubic centimeters of strong sulfuric acid are added +and the copper deposited by an electric current.</p> + +<p><b>137. Precipitating the Copper.</b>—When no more nitric acid is used +than indicated in the previous paragraph, it will not be necessary +to remove it by evaporation. The platinum dishes containing the +solutions of the cuprous oxid are arranged as shown in the <a href="#FIG_43">figure</a> +for the precipitation of the copper by the electric current. Each of the +supporting stands has its base covered with sheet-copper, on which the +platinum dishes rest. The uprights are made of heavy glass rods and +carry the supports for the platinum cylinders which dip into the copper +solutions. The current used is from the city service and is brought +in through the lamp shown at the right of the <a href="#FIG_43">figure</a>. +This current has a voltage of about 120. After passing the lamp it is conducted +through the regulator shown at the right, a glass tube closed below by +a stopper carrying a piece of platinum foil, and above by one holding +a glass tube, in the lower end of which is sealed a piece of sheet +<span class="pagenum"><a id="Page_153"></a>[Pg 153]</span> +platinum connected, through the glass tube, with the lamp. The +regulating tube contains dilute sulfuric acid. The strength of current +desired is secured by adjusting the movable pole. A battery of this +kind easily secures the precipitation of sixteen samples at once, but +only twelve are shown in the <a href="#FIG_43">figure</a>. The practice here +is to start the operation at the time of leaving the laboratory in the afternoon. +The next morning the deposition of the copper will be found complete. +The wiring of the apparatus is shown in the figure. The wire from the +regulator is connected with the base of the first stand, and thence +passes through the horizontal support to the base of the second, and so +on. The return to the lamp is accomplished by means of the upper wire. +This plan of arranging the apparatus has been used for two years, and +with perfect satisfaction.</p> + +<p>Where a street current is not available, the following directions +may be followed: Use four gravity cells, such as are employed in +telegraphic work, for generating the current. This will be strong +enough for one sample and by working longer for two. Connect the +platinum dish with the zinc pole of the battery. The current is allowed +to pass until all the copper is deposited. Where a larger number of +samples is to be treated at once, the size of the battery must be +correspondingly increased.</p> + +<p><b>138. Method Used at the Halle Station.</b>—The method used at the +Halle station is the same as that originally described by Maercker +for dextrose.<a id="FNanchor_106" href="#Footnote_106" class="fnanchor">[106]</a> +The copper solution employed is the same as in the allihn method, +<i>viz.</i>, 34.64 grams of copper sulfate in 500 cubic centimeters, +and 173 grams of rochelle salt and 125 grams of potassium hydroxid in +the same quantity of water. In a porcelain dish are placed thirty cubic +centimeters of copper solution and an equal quantity of the alkali, +sixty cubic centimeters of water added and the mixture boiled. To the +solution, in lively ebullition, are added twenty-five cubic centimeters +of the dextrose solution to be examined which must not contain more +than one per cent of sugar. The mixture is again boiled and the +separated cuprous oxid immediately poured into the filter and washed +with hot water, until the disappearance of an alkaline reaction. For +<span class="pagenum"><a id="Page_154"></a>[Pg 154]</span> +filtering, a glass tube is employed, provided with a platinum disk, +and resembling in every respect similar tubes used for the extraction +of substances with ether and alcohol. The arrangement of the filtering +apparatus is shown in <a href="#FIG_44">Fig. 44</a>. In the Halle method it is +recommended that the tubes be prepared by introducing a platinum cone in place +of the platinum disk and filling it with asbestos felt, pressing the felt +tightly against the sides of the glass tube and making the asbestos +fully one centimeter in thickness. This is a much less convenient +<span class="pagenum"><a id="Page_155"></a>[Pg 155]</span> +method of working than the one described above. After filtration and +washing, the cuprous oxid is washed with ether and alcohol and dried +for an hour at 110°, and finally reduced to metallic copper in a stream +of pure dry hydrogen, heat being applied by means of a small flame. The +apparatus for the reduction of the cuprous oxid is shown in <a href="#FIG_45">Fig. 45</a>. +The metallic copper, after cooling and weighing, is dissolved in nitric +acid, the tube washed with water, ether and alcohol, and again dried, +when it is ready for use a second time. The percentage of dextrose is +calculated from the milligrams of copper found by Allihn’s table.</p> + +<div class="figcenter smcap"> + <img id="FIG_44" src="images/fig44.jpg" alt="" width="500" height="434" > + <p class="center">Figure 44. Apparatus for Filtering Copper Suboxid.</p> + <img id="FIG_45" src="images/fig45.jpg" alt="" width="500" height="438" > + <p class="center spb1">Figure 45. Apparatus for Reducing Copper Suboxid.</p> +</div> + +<p><b>139. Tables for Use in the Gravimetric Determination of Reducing +Sugars.</b>—The value of a table for computing the percentage of a +reducing sugar present in a solution, is based on the accuracy with +which the directions for the determination are followed. The solution +must be of the proper strength and made in the way directed. The degree +of dilution prescribed must be scrupulously preserved and the methods +of boiling during reduction and washing the reduced copper, followed. +The quantity of copper obtained by the use of different alkaline copper +solutions and of sugar solutions of a strength different from that +allowed by the fixed limits, is not a safe factor for computation. +It must be understood, therefore, that in the use of the tables the +directions which are given are to be followed in every particular.</p> + +<p id="P_140"><b>140. Allihn’s Gravimetric Method for the Determination of +Dextrose.</b>—<i>Reagents</i>:</p> + +<table class="spb1"> + <tbody><tr> + <td class="tdr_top">I.</td> + <td class="tdl_top bb"> 34.639 grams of CuSO₄.5H₂O,</td> + <td class="tdl_wsp bb">dissolved in water and diluted<br> to half a liter:</td> + </tr><tr> + <td class="tdr">II.</td> + <td class="tdl_wsp">173 grams of rochelle salts</td> + <td class="tdc">dissolved in water and diluted</td> + </tr><tr> + <td class="tdr"> </td> + <td class="tdl_wsp">125 grams of KOH,</td> + <td class="tdl_wsp">to half a liter.</td> + </tr> + </tbody> +</table> + +<p><i>Manipulation</i>: Place thirty cubic centimeters of the copper +solution (I), thirty cubic centimeters of the alkaline tartrate +solution (II), and sixty cubic centimeters of water in a beaker and +heat to boiling. Add twenty-five cubic centimeters of the solution +of the material to be examined, which must be so prepared as not to +contain more than one per cent of dextrose, and boil for two minutes. +<span class="pagenum"><a id="Page_156"></a>[Pg 156]</span> +Filter immediately after adding an equal volume of recently boiled cold +water and obtain the weight of copper by one of the gravimetric methods +given. The corresponding weight of dextrose is found by the following table:</p> + +<p class="f120"><b><span class="smcap">Allihn’s Table for the<br> +Determination of Dextrose.</span></b></p> + +<ul class="index fs_110"> +<li class="isub3"><b>(A)</b> = Milligrams of copper.</li> +<li class="isub3"><b>(B)</b> = Milligrams of dextrose.</li> +</ul> + +<table class="spb1"> + <thead><tr class="fs_110"> + <th class="tdc"> (A) </th> <th class="tdc"> (B) </th> + <th class="tdc"> (A) </th> <th class="tdc"> (B) </th> + <th class="tdc"> (A) </th> <th class="tdc"> (B) </th> + <th class="tdc"> (A) </th> <th class="tdc"> (B) </th> + <th class="tdc"> (A) </th> <th class="tdc"> (B) </th> + </tr></thead> + <tbody><tr> + <td class="tdc">10</td> <td class="tdc"> 6.1</td> + <td class="tdc">46</td> <td class="tdc">23.9</td> + <td class="tdc"> 82</td> <td class="tdc">41.8</td> + <td class="tdc">118</td> <td class="tdc">60.1</td> + <td class="tdc">154</td> <td class="tdc">78.6</td> + </tr><tr> + <td class="tdc">11</td> <td class="tdc"> 6.6</td> + <td class="tdc">47</td> <td class="tdc">24.4</td> + <td class="tdc"> 83</td> <td class="tdc">42.3</td> + <td class="tdc">119</td> <td class="tdc">60.6</td> + <td class="tdc">155</td> <td class="tdc">79.1</td> + </tr><tr> + <td class="tdc">12</td> <td class="tdc"> 7.1</td> + <td class="tdc">48</td> <td class="tdc">24.9</td> + <td class="tdc"> 84</td> <td class="tdc">42.8</td> + <td class="tdc">120</td> <td class="tdc">61.1</td> + <td class="tdc">156</td> <td class="tdc">79.6</td> + </tr><tr> + <td class="tdc">13</td> <td class="tdc"> 7.6</td> + <td class="tdc">49</td> <td class="tdc">25.4</td> + <td class="tdc"> 85</td> <td class="tdc">43.4</td> + <td class="tdc">121</td> <td class="tdc">61.6</td> + <td class="tdc">157</td> <td class="tdc">80.1</td> + </tr><tr> + <td class="tdc">14</td> <td class="tdc"> 8.1</td> + <td class="tdc">50</td> <td class="tdc">25.9</td> + <td class="tdc"> 86</td> <td class="tdc">43.9</td> + <td class="tdc">122</td> <td class="tdc">62.1</td> + <td class="tdc">158</td> <td class="tdc">80.7</td> + </tr><tr> + <td class="tdc">15</td> <td class="tdc"> 8.6</td> + <td class="tdc">51</td> <td class="tdc">26.4</td> + <td class="tdc"> 87</td> <td class="tdc">44.4</td> + <td class="tdc">123</td> <td class="tdc">62.6</td> + <td class="tdc">159</td> <td class="tdc">81.2</td> + </tr><tr> + <td class="tdc">16</td> <td class="tdc"> 9.0</td> + <td class="tdc">52</td> <td class="tdc">26.9</td> + <td class="tdc"> 88</td> <td class="tdc">44.9</td> + <td class="tdc">124</td> <td class="tdc">63.1</td> + <td class="tdc">160</td> <td class="tdc">81.7</td> + </tr><tr> + <td class="tdc">17</td> <td class="tdc"> 9.5</td> + <td class="tdc">53</td> <td class="tdc">27.4</td> + <td class="tdc"> 89</td> <td class="tdc">45.4</td> + <td class="tdc">125</td> <td class="tdc">63.7</td> + <td class="tdc">161</td> <td class="tdc">82.2</td> + </tr><tr> + <td class="tdc">18</td> <td class="tdc">10.0</td> + <td class="tdc">54</td> <td class="tdc">27.9</td> + <td class="tdc"> 90</td> <td class="tdc">45.9</td> + <td class="tdc">126</td> <td class="tdc">64.2</td> + <td class="tdc">162</td> <td class="tdc">82.7</td> + </tr><tr> + <td class="tdc bb">19</td> <td class="tdc bb">10.5</td> + <td class="tdc bb">55</td> <td class="tdc bb">28.4</td> + <td class="tdc bb"> 91</td> <td class="tdc bb">46.4</td> + <td class="tdc bb">127</td> <td class="tdc bb">64.7</td> + <td class="tdc bb">163</td> <td class="tdc bb">83.3</td> + </tr><tr> + <td class="tdc">20</td> <td class="tdc">11.0</td> + <td class="tdc">56</td> <td class="tdc">28.8</td> + <td class="tdc"> 92</td> <td class="tdc">46.9</td> + <td class="tdc">128</td> <td class="tdc">65.2</td> + <td class="tdc">164</td> <td class="tdc">83.8</td> + </tr><tr> + <td class="tdc">21</td> <td class="tdc">11.5</td> + <td class="tdc">57</td> <td class="tdc">29.3</td> + <td class="tdc"> 93</td> <td class="tdc">47.4</td> + <td class="tdc">129</td> <td class="tdc">65.7</td> + <td class="tdc">165</td> <td class="tdc">84.3</td> + </tr><tr> + <td class="tdc">22</td> <td class="tdc">12.0</td> + <td class="tdc">58</td> <td class="tdc">29.8</td> + <td class="tdc"> 94</td> <td class="tdc">47.9</td> + <td class="tdc">130</td> <td class="tdc">66.2</td> + <td class="tdc">166</td> <td class="tdc">84.8</td> + </tr><tr> + <td class="tdc">23</td> <td class="tdc">12.5</td> + <td class="tdc">59</td> <td class="tdc">30.3</td> + <td class="tdc"> 95</td> <td class="tdc">48.4</td> + <td class="tdc">131</td> <td class="tdc">66.7</td> + <td class="tdc">167</td> <td class="tdc">85.3</td> + </tr><tr> + <td class="tdc">24</td> <td class="tdc">13.0</td> + <td class="tdc">60</td> <td class="tdc">30.8</td> + <td class="tdc"> 96</td> <td class="tdc">48.9</td> + <td class="tdc">132</td> <td class="tdc">67.2</td> + <td class="tdc">168</td> <td class="tdc">85.9</td> + </tr><tr> + <td class="tdc">25</td> <td class="tdc">13.5</td> + <td class="tdc">61</td> <td class="tdc">31.3</td> + <td class="tdc"> 97</td> <td class="tdc">49.4</td> + <td class="tdc">133</td> <td class="tdc">67.7</td> + <td class="tdc">169</td> <td class="tdc">86.4</td> + </tr><tr> + <td class="tdc">26</td> <td class="tdc">14.0</td> + <td class="tdc">62</td> <td class="tdc">31.8</td> + <td class="tdc"> 98</td> <td class="tdc">49.9</td> + <td class="tdc">134</td> <td class="tdc">68.2</td> + <td class="tdc">170</td> <td class="tdc">86.9</td> + </tr><tr> + <td class="tdc">27</td> <td class="tdc">14.5</td> + <td class="tdc">63</td> <td class="tdc">32.3</td> + <td class="tdc"> 99</td> <td class="tdc">50.4</td> + <td class="tdc">135</td> <td class="tdc">68.8</td> + <td class="tdc">171</td> <td class="tdc">87.4</td> + </tr><tr> + <td class="tdc">28</td> <td class="tdc">15.0</td> + <td class="tdc">64</td> <td class="tdc">32.8</td> + <td class="tdc">100</td> <td class="tdc">50.9</td> + <td class="tdc">136</td> <td class="tdc">69.3</td> + <td class="tdc">172</td> <td class="tdc">87.9</td> + </tr><tr> + <td class="tdc bb">29</td> <td class="tdc bb">15.5</td> + <td class="tdc bb">65</td> <td class="tdc bb">33.3</td> + <td class="tdc bb">101</td> <td class="tdc bb">51.4</td> + <td class="tdc bb">137</td> <td class="tdc bb">69.8</td> + <td class="tdc bb">173</td> <td class="tdc bb">88.5</td> + </tr><tr> + <td class="tdc">30</td> <td class="tdc">16.0</td> + <td class="tdc">66</td> <td class="tdc">33.8</td> + <td class="tdc">102</td> <td class="tdc">51.9</td> + <td class="tdc">138</td> <td class="tdc">70.3</td> + <td class="tdc">174</td> <td class="tdc">89.0</td> + </tr><tr> + <td class="tdc">31</td> <td class="tdc">16.5</td> + <td class="tdc">67</td> <td class="tdc">34.3</td> + <td class="tdc">103</td> <td class="tdc">52.4</td> + <td class="tdc">139</td> <td class="tdc">70.8</td> + <td class="tdc">175</td> <td class="tdc">89.5</td> + </tr><tr> + <td class="tdc">32</td> <td class="tdc">17.0</td> + <td class="tdc">68</td> <td class="tdc">34.8</td> + <td class="tdc">104</td> <td class="tdc">52.9</td> + <td class="tdc">140</td> <td class="tdc">71.3</td> + <td class="tdc">176</td> <td class="tdc">90.0</td> + </tr><tr> + <td class="tdc">33</td> <td class="tdc">17.5</td> + <td class="tdc">69</td> <td class="tdc">35.3</td> + <td class="tdc">105</td> <td class="tdc">53.5</td> + <td class="tdc">141</td> <td class="tdc">71.8</td> + <td class="tdc">177</td> <td class="tdc">90.5</td> + </tr><tr> + <td class="tdc">34</td> <td class="tdc">18.0</td> + <td class="tdc">70</td> <td class="tdc">35.8</td> + <td class="tdc">106</td> <td class="tdc">54.0</td> + <td class="tdc">142</td> <td class="tdc">72.3</td> + <td class="tdc">178</td> <td class="tdc">91.1</td> + </tr><tr> + <td class="tdc">35</td> <td class="tdc">18.5</td> + <td class="tdc">71</td> <td class="tdc">36.3</td> + <td class="tdc">107</td> <td class="tdc">54.5</td> + <td class="tdc">143</td> <td class="tdc">72.9</td> + <td class="tdc">179</td> <td class="tdc">91.6</td> + </tr><tr> + <td class="tdc">36</td> <td class="tdc">18.9</td> + <td class="tdc">72</td> <td class="tdc">36.8</td> + <td class="tdc">108</td> <td class="tdc">55.0</td> + <td class="tdc">144</td> <td class="tdc">73.4</td> + <td class="tdc">180</td> <td class="tdc">92.1</td> + </tr><tr> + <td class="tdc">37</td> <td class="tdc">19.4</td> + <td class="tdc">73</td> <td class="tdc">37.3</td> + <td class="tdc">109</td> <td class="tdc">55.5</td> + <td class="tdc">145</td> <td class="tdc">73.9</td> + <td class="tdc">181</td> <td class="tdc">92.6</td> + </tr><tr> + <td class="tdc">38</td> <td class="tdc">19.9</td> + <td class="tdc">74</td> <td class="tdc">37.8</td> + <td class="tdc">110</td> <td class="tdc">56.0</td> + <td class="tdc">146</td> <td class="tdc">74.4</td> + <td class="tdc">182</td> <td class="tdc">93.1</td> + </tr><tr> + <td class="tdc bb">39</td> <td class="tdc bb">20.4</td> + <td class="tdc bb">75</td> <td class="tdc bb">38.3</td> + <td class="tdc bb">111</td> <td class="tdc bb">56.5</td> + <td class="tdc bb">147</td> <td class="tdc bb">74.9</td> + <td class="tdc bb">183</td> <td class="tdc bb">93.7</td> + </tr><tr> + <td class="tdc">40</td> <td class="tdc">20.9</td> + <td class="tdc">76</td> <td class="tdc">38.8</td> + <td class="tdc">112</td> <td class="tdc">57.0</td> + <td class="tdc">148</td> <td class="tdc">75.5</td> + <td class="tdc">184</td> <td class="tdc">94.2</td> + </tr><tr> + <td class="tdc">41</td> <td class="tdc">21.4</td> + <td class="tdc">77</td> <td class="tdc">39.3</td> + <td class="tdc">113</td> <td class="tdc">57.5</td> + <td class="tdc">149</td> <td class="tdc">76.0</td> + <td class="tdc">185</td> <td class="tdc">94.7</td> + </tr><tr> + <td class="tdc">42</td> <td class="tdc">21.9</td> + <td class="tdc">78</td> <td class="tdc">39.8</td> + <td class="tdc">114</td> <td class="tdc">58.0</td> + <td class="tdc">150</td> <td class="tdc">76.5</td> + <td class="tdc">186</td> <td class="tdc">95.2</td> + </tr><tr> + <td class="tdc">43</td> <td class="tdc">22.4</td> + <td class="tdc">79</td> <td class="tdc">40.3</td> + <td class="tdc">115</td> <td class="tdc">58.6</td> + <td class="tdc">151</td> <td class="tdc">77.0</td> + <td class="tdc">187</td> <td class="tdc">95.7</td> + </tr><tr> + <td class="tdc">44</td> <td class="tdc">22.9</td> + <td class="tdc">80</td> <td class="tdc">40.8</td> + <td class="tdc">116</td> <td class="tdc">59.1</td> + <td class="tdc">152</td> <td class="tdc">77.5</td> + <td class="tdc">188</td> <td class="tdc">96.3</td> + </tr><tr> + <td class="tdc">45</td> <td class="tdc">23.4</td> + <td class="tdc">81</td> <td class="tdc">41.3</td> + <td class="tdc">117</td> <td class="tdc">59.6</td> + <td class="tdc">153</td> <td class="tdc">78.1</td> + <td class="tdc">189</td> <td class="tdc">96.8</td> + </tr><tr> + <td class="tdc" colspan="10"> <span class="pagenum"><a id="Page_157"></a>[Pg 157]</span></td> + </tr><tr class="f110"> + <td class="tdc"> <b>(A)</b> </td> <td class="tdc"> <b>(B)</b> </td> + <td class="tdc"> <b>(A)</b> </td> <td class="tdc"> <b>(B)</b> </td> + <td class="tdc"> <b>(A)</b> </td> <td class="tdc"> <b>(B)</b> </td> + <td class="tdc"> <b>(A)</b> </td> <td class="tdc"> <b>(B)</b> </td> + <td class="tdc"> <b>(A)</b> </td> <td class="tdc"> <b>(B)</b> </td> + </tr><tr> + <td class="tdc">190</td> <td class="tdc"> 97.3</td> + <td class="tdc">233</td> <td class="tdc">120.1</td> + <td class="tdc">276</td> <td class="tdc">143.3</td> + <td class="tdc">319</td> <td class="tdc">167.0</td> + <td class="tdc">362</td> <td class="tdc">191.1</td> + </tr><tr> + <td class="tdc">191</td> <td class="tdc"> 97.8</td> + <td class="tdc">234</td> <td class="tdc">120.7</td> + <td class="tdc">277</td> <td class="tdc">143.9</td> + <td class="tdc">320</td> <td class="tdc">167.5</td> + <td class="tdc">363</td> <td class="tdc">191.7</td> + </tr><tr> + <td class="tdc">192</td> <td class="tdc"> 98.4</td> + <td class="tdc">235</td> <td class="tdc">121.2</td> + <td class="tdc">278</td> <td class="tdc">144.4</td> + <td class="tdc">321</td> <td class="tdc">168.1</td> + <td class="tdc">364</td> <td class="tdc">192.3</td> + </tr><tr> + <td class="tdc">193</td> <td class="tdc"> 98.9</td> + <td class="tdc">236</td> <td class="tdc">121.7</td> + <td class="tdc">279</td> <td class="tdc">145.0</td> + <td class="tdc">322</td> <td class="tdc">168.6</td> + <td class="tdc">365</td> <td class="tdc">192.9</td> + </tr><tr> + <td class="tdc">194</td> <td class="tdc"> 99.4</td> + <td class="tdc">237</td> <td class="tdc">122.3</td> + <td class="tdc">280</td> <td class="tdc">145.5</td> + <td class="tdc">323</td> <td class="tdc">169.2</td> + <td class="tdc">366</td> <td class="tdc">193.4</td> + </tr><tr> + <td class="tdc">195</td> <td class="tdc">100.0</td> + <td class="tdc">238</td> <td class="tdc">122.8</td> + <td class="tdc">281</td> <td class="tdc">146.1</td> + <td class="tdc">324</td> <td class="tdc">169.7</td> + <td class="tdc">367</td> <td class="tdc">194.0</td> + </tr><tr> + <td class="tdc">196</td> <td class="tdc">100.5</td> + <td class="tdc">239</td> <td class="tdc">123.4</td> + <td class="tdc">282</td> <td class="tdc">146.6</td> + <td class="tdc">325</td> <td class="tdc">170.3</td> + <td class="tdc">368</td> <td class="tdc">194.6</td> + </tr><tr> + <td class="tdc">197</td> <td class="tdc">101.0</td> + <td class="tdc">240</td> <td class="tdc">123.9</td> + <td class="tdc">283</td> <td class="tdc">147.2</td> + <td class="tdc">326</td> <td class="tdc">170.9</td> + <td class="tdc">369</td> <td class="tdc">195.1</td> + </tr><tr> + <td class="tdc">198</td> <td class="tdc">101.5</td> + <td class="tdc">241</td> <td class="tdc">124.4</td> + <td class="tdc">284</td> <td class="tdc">147.7</td> + <td class="tdc">327</td> <td class="tdc">171.4</td> + <td class="tdc">370</td> <td class="tdc">195.7</td> + </tr><tr> + <td class="tdc bb">199</td> <td class="tdc bb">102.0</td> + <td class="tdc bb">242</td> <td class="tdc bb">125.0</td> + <td class="tdc bb">285</td> <td class="tdc bb">148.3</td> + <td class="tdc bb">328</td> <td class="tdc bb">172.0</td> + <td class="tdc bb">371</td> <td class="tdc bb">196.3</td> + </tr><tr> + <td class="tdc">200</td> <td class="tdc">102.6</td> + <td class="tdc">243</td> <td class="tdc">125.5</td> + <td class="tdc">286</td> <td class="tdc">148.8</td> + <td class="tdc">329</td> <td class="tdc">172.5</td> + <td class="tdc">372</td> <td class="tdc">196.8</td> + </tr><tr> + <td class="tdc">201</td> <td class="tdc">103.1</td> + <td class="tdc">244</td> <td class="tdc">126.0</td> + <td class="tdc">287</td> <td class="tdc">149.5</td> + <td class="tdc">330</td> <td class="tdc">173.1</td> + <td class="tdc">373</td> <td class="tdc">197.4</td> + </tr><tr> + <td class="tdc">202</td> <td class="tdc">103.7</td> + <td class="tdc">245</td> <td class="tdc">126.6</td> + <td class="tdc">288</td> <td class="tdc">149.4</td> + <td class="tdc">331</td> <td class="tdc">173.7</td> + <td class="tdc">374</td> <td class="tdc">198.0</td> + </tr><tr> + <td class="tdc">203</td> <td class="tdc">104.2</td> + <td class="tdc">246</td> <td class="tdc">127.1</td> + <td class="tdc">289</td> <td class="tdc">150.9</td> + <td class="tdc">332</td> <td class="tdc">174.2</td> + <td class="tdc">375</td> <td class="tdc">198.6</td> + </tr><tr> + <td class="tdc">204</td> <td class="tdc">104.7</td> + <td class="tdc">247</td> <td class="tdc">127.6</td> + <td class="tdc">290</td> <td class="tdc">151.0</td> + <td class="tdc">333</td> <td class="tdc">174.8</td> + <td class="tdc">376</td> <td class="tdc">199.1</td> + </tr><tr> + <td class="tdc">205</td> <td class="tdc">105.3</td> + <td class="tdc">248</td> <td class="tdc">128.1</td> + <td class="tdc">291</td> <td class="tdc">151.6</td> + <td class="tdc">334</td> <td class="tdc">175.3</td> + <td class="tdc">377</td> <td class="tdc">199.7</td> + </tr><tr> + <td class="tdc">206</td> <td class="tdc">105.8</td> + <td class="tdc">249</td> <td class="tdc">128.7</td> + <td class="tdc">292</td> <td class="tdc">152.1</td> + <td class="tdc">335</td> <td class="tdc">175.9</td> + <td class="tdc">378</td> <td class="tdc">200.3</td> + </tr><tr> + <td class="tdc">207</td> <td class="tdc">106.3</td> + <td class="tdc">250</td> <td class="tdc">129.2</td> + <td class="tdc">293</td> <td class="tdc">152.7</td> + <td class="tdc">336</td> <td class="tdc">176.5</td> + <td class="tdc">379</td> <td class="tdc">200.8</td> + </tr><tr> + <td class="tdc">208</td> <td class="tdc">106.8</td> + <td class="tdc">251</td> <td class="tdc">129.7</td> + <td class="tdc">294</td> <td class="tdc">153.2</td> + <td class="tdc">337</td> <td class="tdc">177.0</td> + <td class="tdc">380</td> <td class="tdc">201.4</td> + </tr><tr> + <td class="tdc">209</td> <td class="tdc">107.4</td> + <td class="tdc">252</td> <td class="tdc">130.3</td> + <td class="tdc">295</td> <td class="tdc">153.8</td> + <td class="tdc">338</td> <td class="tdc">177.6</td> + <td class="tdc">381</td> <td class="tdc">202.0</td> + </tr><tr> + <td class="tdc">210</td> <td class="tdc">107.9</td> + <td class="tdc">253</td> <td class="tdc">130.8</td> + <td class="tdc">296</td> <td class="tdc">154.3</td> + <td class="tdc">339</td> <td class="tdc">178.1</td> + <td class="tdc">382</td> <td class="tdc">202.5</td> + </tr><tr> + <td class="tdc">211</td> <td class="tdc">108.4</td> + <td class="tdc">254</td> <td class="tdc">131.4</td> + <td class="tdc">297</td> <td class="tdc">154.9</td> + <td class="tdc">340</td> <td class="tdc">178.7</td> + <td class="tdc">383</td> <td class="tdc">203.1</td> + </tr><tr> + <td class="tdc">212</td> <td class="tdc">109.0</td> + <td class="tdc">255</td> <td class="tdc">131.9</td> + <td class="tdc">298</td> <td class="tdc">155.4</td> + <td class="tdc">341</td> <td class="tdc">179.3</td> + <td class="tdc">384</td> <td class="tdc">203.7</td> + </tr><tr> + <td class="tdc">213</td> <td class="tdc">109.5</td> + <td class="tdc">256</td> <td class="tdc">132.4</td> + <td class="tdc">299</td> <td class="tdc">156.0</td> + <td class="tdc">342</td> <td class="tdc">179.8</td> + <td class="tdc">385</td> <td class="tdc">204.3</td> + </tr><tr> + <td class="tdc">214</td> <td class="tdc">110.0</td> + <td class="tdc">257</td> <td class="tdc">133.0</td> + <td class="tdc">300</td> <td class="tdc">156.5</td> + <td class="tdc">343</td> <td class="tdc">180.4</td> + <td class="tdc">386</td> <td class="tdc">204.8</td> + </tr><tr> + <td class="tdc">215</td> <td class="tdc">110.6</td> + <td class="tdc">258</td> <td class="tdc">133.5</td> + <td class="tdc">301</td> <td class="tdc">157.1</td> + <td class="tdc">344</td> <td class="tdc">180.9</td> + <td class="tdc">387</td> <td class="tdc">205.4</td> + </tr><tr> + <td class="tdc">216</td> <td class="tdc">111.1</td> + <td class="tdc">259</td> <td class="tdc">134.1</td> + <td class="tdc">302</td> <td class="tdc">157.6</td> + <td class="tdc">345</td> <td class="tdc">181.5</td> + <td class="tdc">388</td> <td class="tdc">206.0</td> + </tr><tr> + <td class="tdc">217</td> <td class="tdc">111.6</td> + <td class="tdc">260</td> <td class="tdc">134.6</td> + <td class="tdc">303</td> <td class="tdc">158.2</td> + <td class="tdc">346</td> <td class="tdc">182.1</td> + <td class="tdc">389</td> <td class="tdc">206.5</td> + </tr><tr> + <td class="tdc">218</td> <td class="tdc">112.1</td> + <td class="tdc">261</td> <td class="tdc">135.1</td> + <td class="tdc">304</td> <td class="tdc">158.7</td> + <td class="tdc">347</td> <td class="tdc">182.6</td> + <td class="tdc">390</td> <td class="tdc">207.1</td> + </tr><tr> + <td class="tdc bb">219</td> <td class="tdc bb">112.7</td> + <td class="tdc bb">262</td> <td class="tdc bb">135.7</td> + <td class="tdc bb">305</td> <td class="tdc bb">159.3</td> + <td class="tdc bb">348</td> <td class="tdc bb">183.2</td> + <td class="tdc bb">391</td> <td class="tdc bb">207.7</td> + </tr><tr> + <td class="tdc">220</td> <td class="tdc">113.2</td> + <td class="tdc">263</td> <td class="tdc">136.2</td> + <td class="tdc">306</td> <td class="tdc">159.8</td> + <td class="tdc">349</td> <td class="tdc">183.7</td> + <td class="tdc">392</td> <td class="tdc">208.3</td> + </tr><tr> + <td class="tdc">221</td> <td class="tdc">113.7</td> + <td class="tdc">264</td> <td class="tdc">136.8</td> + <td class="tdc">307</td> <td class="tdc">160.4</td> + <td class="tdc">350</td> <td class="tdc">184.3</td> + <td class="tdc">393</td> <td class="tdc">208.8</td> + </tr><tr> + <td class="tdc">222</td> <td class="tdc">114.3</td> + <td class="tdc">265</td> <td class="tdc">137.3</td> + <td class="tdc">308</td> <td class="tdc">160.9</td> + <td class="tdc">351</td> <td class="tdc">184.9</td> + <td class="tdc">394</td> <td class="tdc">209.4</td> + </tr><tr> + <td class="tdc">223</td> <td class="tdc">114.8</td> + <td class="tdc">266</td> <td class="tdc">137.8</td> + <td class="tdc">309</td> <td class="tdc">161.5</td> + <td class="tdc">352</td> <td class="tdc">185.4</td> + <td class="tdc">395</td> <td class="tdc">210.0</td> + </tr><tr> + <td class="tdc">224</td> <td class="tdc">115.3</td> + <td class="tdc">267</td> <td class="tdc">138.4</td> + <td class="tdc">310</td> <td class="tdc">162.0</td> + <td class="tdc">353</td> <td class="tdc">186.0</td> + <td class="tdc">396</td> <td class="tdc">210.6</td> + </tr><tr> + <td class="tdc">225</td> <td class="tdc">115.9</td> + <td class="tdc">268</td> <td class="tdc">138.9</td> + <td class="tdc">311</td> <td class="tdc">162.6</td> + <td class="tdc">354</td> <td class="tdc">186.6</td> + <td class="tdc">397</td> <td class="tdc">211.2</td> + </tr><tr> + <td class="tdc">226</td> <td class="tdc">116.4</td> + <td class="tdc">269</td> <td class="tdc">139.5</td> + <td class="tdc">312</td> <td class="tdc">163.1</td> + <td class="tdc">355</td> <td class="tdc">187.2</td> + <td class="tdc">398</td> <td class="tdc">211.7</td> + </tr><tr> + <td class="tdc">227</td> <td class="tdc">116.9</td> + <td class="tdc">270</td> <td class="tdc">140.0</td> + <td class="tdc">313</td> <td class="tdc">163.7</td> + <td class="tdc">356</td> <td class="tdc">187.7</td> + <td class="tdc">399</td> <td class="tdc">212.3</td> + </tr><tr> + <td class="tdc">228</td> <td class="tdc">117.4</td> + <td class="tdc">271</td> <td class="tdc">140.6</td> + <td class="tdc">314</td> <td class="tdc">164.2</td> + <td class="tdc">357</td> <td class="tdc">188.3</td> + <td class="tdc">400</td> <td class="tdc">212.9</td> + </tr><tr> + <td class="tdc">229</td> <td class="tdc">118.0</td> + <td class="tdc">272</td> <td class="tdc">141.1</td> + <td class="tdc">315</td> <td class="tdc">164.8</td> + <td class="tdc">358</td> <td class="tdc">188.9</td> + <td class="tdc">401</td> <td class="tdc">213.5</td> + </tr><tr> + <td class="tdc">230</td> <td class="tdc">118.5</td> + <td class="tdc">273</td> <td class="tdc">141.7</td> + <td class="tdc">316</td> <td class="tdc">165.3</td> + <td class="tdc">359</td> <td class="tdc">189.4</td> + <td class="tdc">402</td> <td class="tdc">214.1</td> + </tr><tr> + <td class="tdc">231</td> <td class="tdc">119.0</td> + <td class="tdc">274</td> <td class="tdc">142.2</td> + <td class="tdc">317</td> <td class="tdc">165.9</td> + <td class="tdc">360</td> <td class="tdc">190.0</td> + <td class="tdc">403</td> <td class="tdc">214.6</td> + </tr><tr> + <td class="tdc">232</td> <td class="tdc">119.6</td> + <td class="tdc">275</td> <td class="tdc">142.8</td> + <td class="tdc">318</td> <td class="tdc">166.4</td> + <td class="tdc">361</td> <td class="tdc">190.6</td> + <td class="tdc">404</td> <td class="tdc">215.2</td> + </tr><tr> + <td class="tdc" colspan="10"> <span class="pagenum"><a id="Page_158"></a>[Pg 158]</span></td> + </tr><tr class="f110"> + <td class="tdc"> <b>(A)</b> </td> <td class="tdc"> <b>(B)</b> </td> + <td class="tdc"> <b>(A)</b> </td> <td class="tdc"> <b>(B)</b> </td> + <td class="tdc"> <b>(A)</b> </td> <td class="tdc"> <b>(B)</b> </td> + <td class="tdc"> <b>(A)</b> </td> <td class="tdc"> <b>(B)</b> </td> + <td class="tdc"> <b>(A)</b> </td> <td class="tdc"> <b>(B)</b> </td> + </tr><tr> + <td class="tdc">405</td> <td class="tdc">215.8</td> + <td class="tdc">417</td> <td class="tdc">222.8</td> + <td class="tdc">429</td> <td class="tdc">229.8</td> + <td class="tdc">441</td> <td class="tdc">236.9</td> + <td class="tdc">453</td> <td class="tdc">244.0</td> + </tr><tr> + <td class="tdc">406</td> <td class="tdc">216.4</td> + <td class="tdc">418</td> <td class="tdc">223.3</td> + <td class="tdc">430</td> <td class="tdc">230.4</td> + <td class="tdc">442</td> <td class="tdc">237.5</td> + <td class="tdc">454</td> <td class="tdc">244.6</td> + </tr><tr> + <td class="tdc">407</td> <td class="tdc">217.0</td> + <td class="tdc">419</td> <td class="tdc">223.9</td> + <td class="tdc">431</td> <td class="tdc">231.0</td> + <td class="tdc">443</td> <td class="tdc">238.1</td> + <td class="tdc">455</td> <td class="tdc">245.2</td> + </tr><tr> + <td class="tdc">408</td> <td class="tdc">217.5</td> + <td class="tdc">420</td> <td class="tdc">224.5</td> + <td class="tdc">432</td> <td class="tdc">231.6</td> + <td class="tdc">444</td> <td class="tdc">238.7</td> + <td class="tdc">456</td> <td class="tdc">245.7</td> + </tr><tr> + <td class="tdc">409</td> <td class="tdc">218.1</td> + <td class="tdc">421</td> <td class="tdc">225.1</td> + <td class="tdc">433</td> <td class="tdc">232.2</td> + <td class="tdc">445</td> <td class="tdc">239.3</td> + <td class="tdc">457</td> <td class="tdc">246.3</td> + </tr><tr> + <td class="tdc">410</td> <td class="tdc">218.7</td> + <td class="tdc">422</td> <td class="tdc">225.7</td> + <td class="tdc">434</td> <td class="tdc">232.8</td> + <td class="tdc">446</td> <td class="tdc">239.8</td> + <td class="tdc">458</td> <td class="tdc">246.9</td> + </tr><tr> + <td class="tdc">411</td> <td class="tdc">219.3</td> + <td class="tdc">423</td> <td class="tdc">226.3</td> + <td class="tdc">435</td> <td class="tdc">233.4</td> + <td class="tdc">447</td> <td class="tdc">240.4</td> + <td class="tdc">459</td> <td class="tdc">247.5</td> + </tr><tr> + <td class="tdc">412</td> <td class="tdc">219.9</td> + <td class="tdc">424</td> <td class="tdc">226.9</td> + <td class="tdc">436</td> <td class="tdc">233.9</td> + <td class="tdc">448</td> <td class="tdc">241.0</td> + <td class="tdc">460</td> <td class="tdc">248.1</td> + </tr><tr> + <td class="tdc">413</td> <td class="tdc">220.4</td> + <td class="tdc">425</td> <td class="tdc">227.5</td> + <td class="tdc">437</td> <td class="tdc">234.5</td> + <td class="tdc">449</td> <td class="tdc">241.6</td> + <td class="tdc">461</td> <td class="tdc">248.7</td> + </tr><tr> + <td class="tdc">414</td> <td class="tdc">221.0</td> + <td class="tdc">426</td> <td class="tdc">228.0</td> + <td class="tdc">438</td> <td class="tdc">235.1</td> + <td class="tdc">450</td> <td class="tdc">242.2</td> + <td class="tdc">462</td> <td class="tdc">249.3</td> + </tr><tr> + <td class="tdc">415</td> <td class="tdc">221.6</td> + <td class="tdc">427</td> <td class="tdc">228.6</td> + <td class="tdc">439</td> <td class="tdc">235.7</td> + <td class="tdc">451</td> <td class="tdc">242.8</td> + <td class="tdc">463</td> <td class="tdc">249.9</td> + </tr><tr> + <td class="tdc">416</td> <td class="tdc">222.2</td> + <td class="tdc">428</td> <td class="tdc">229.2</td> + <td class="tdc">440</td> <td class="tdc">236.3</td> + <td class="tdc">452</td> <td class="tdc">243.4</td> + <td class="tdc"> </td> <td class="tdc"> </td> + </tr> + </tbody> +</table> + +<p id="P_141"><b>141. Meissl’s Table for Invert Sugar.</b>—Invert sugar is usually +the product of the hydrolysis of sucrose. The following table is to +be used when the hydrolysis is complete, <i>i</i>. <i>e</i>., when no +sucrose is left in the solution. The solution of copper sulfate and of +the alkaline tartrate are made up as follows: 34.64 grams of copper +sulfate in half a liter, and 173 grams of rochelle salt and 51.6 grams +sodium hydroxid in the same volume. The quantity of sugar solution +used must not contain more than 245 nor less than ninety milligrams of +invert sugar.</p> + +<p>In the determination twenty-five cubic centimeters of the copper +solution and an equal volume of the alkaline tartrate are mixed and +boiled, the proper amount of sugar solution added to secure a quantity +of invertose within the limits named, the volume completed to 100 +cubic centimeters with boiling water, and the mixture kept in lively +ebullition for two minutes. An equal volume of recently boiled cold +water is added and the cuprous oxid at once separated by filtration on +asbestos under pressure, and washed free of alkali with boiling water. +The metallic copper is secured by one of the methods already described. +<span class="pagenum"><a id="Page_159"></a>[Pg 159]</span></p> + +<p class="f120"><b><span class="smcap">Table for Invert Sugar by Meissl and + Wien.</span></b><a id="FNanchor_107" href="#Footnote_107" class="fnanchor">[107]</a></p> + +<ul class="index fs_110"> +<li class="isub3"><b>(A)</b> = Milligrams of copper.</li> +<li class="isub3"><b>(B)</b> = Milligrams of invert sugar.</li> +</ul> + +<table class="spb1"> + <thead><tr class="fs_110"> + <th class="tdc"> (A) </th> <th class="tdc"> (B) </th> + <th class="tdc"> (A) </th> <th class="tdc"> (B) </th> + <th class="tdc"> (A) </th> <th class="tdc"> (B) </th> + <th class="tdc"> (A) </th> <th class="tdc"> (B) </th> + </tr></thead> + <tbody><tr> + <td class="tdc"> 90</td> <td class="tdc">46.9</td> + <td class="tdc">133</td> <td class="tdc">69.7</td> + <td class="tdc">176</td> <td class="tdc"> 93.0</td> + <td class="tdc">219</td> <td class="tdc">117.0</td> + </tr><tr> + <td class="tdc"> 91</td> <td class="tdc">47.4</td> + <td class="tdc">134</td> <td class="tdc">70.3</td> + <td class="tdc">177</td> <td class="tdc"> 93.5</td> + <td class="tdc">220</td> <td class="tdc">117.5</td> + </tr><tr> + <td class="tdc"> 92</td> <td class="tdc">47.9</td> + <td class="tdc">135</td> <td class="tdc">70.8</td> + <td class="tdc">178</td> <td class="tdc"> 94.1</td> + <td class="tdc">221</td> <td class="tdc">118.1</td> + </tr><tr> + <td class="tdc"> 93</td> <td class="tdc">48.4</td> + <td class="tdc">136</td> <td class="tdc">71.3</td> + <td class="tdc">179</td> <td class="tdc"> 94.6</td> + <td class="tdc">222</td> <td class="tdc">118.7</td> + </tr><tr> + <td class="tdc"> 94</td> <td class="tdc">48.9</td> + <td class="tdc">137</td> <td class="tdc">71.9</td> + <td class="tdc">180</td> <td class="tdc"> 95.2</td> + <td class="tdc">223</td> <td class="tdc">119.2</td> + </tr><tr> + <td class="tdc"> 95</td> <td class="tdc">49.5</td> + <td class="tdc">138</td> <td class="tdc">72.4</td> + <td class="tdc">181</td> <td class="tdc"> 95.7</td> + <td class="tdc">224</td> <td class="tdc">119.8</td> + </tr><tr> + <td class="tdc"> 96</td> <td class="tdc">50.0</td> + <td class="tdc">139</td> <td class="tdc">72.9</td> + <td class="tdc">182</td> <td class="tdc"> 96.2</td> + <td class="tdc">225</td> <td class="tdc">120.4</td> + </tr><tr> + <td class="tdc"> 97</td> <td class="tdc">50.5</td> + <td class="tdc">140</td> <td class="tdc">73.5</td> + <td class="tdc">183</td> <td class="tdc"> 96.8</td> + <td class="tdc">226</td> <td class="tdc">120.9</td> + </tr><tr> + <td class="tdc"> 98</td> <td class="tdc">51.1</td> + <td class="tdc">141</td> <td class="tdc">74.0</td> + <td class="tdc">184</td> <td class="tdc"> 97.3</td> + <td class="tdc">227</td> <td class="tdc">121.5</td> + </tr><tr> + <td class="tdc"> 99</td> <td class="tdc">51.6</td> + <td class="tdc">142</td> <td class="tdc">74.5</td> + <td class="tdc">185</td> <td class="tdc"> 97.8</td> + <td class="tdc">228</td> <td class="tdc">122.1</td> + </tr><tr> + <td class="tdc">100</td> <td class="tdc">52.1</td> + <td class="tdc">143</td> <td class="tdc">75.1</td> + <td class="tdc">186</td> <td class="tdc"> 98.4</td> + <td class="tdc">229</td> <td class="tdc">122.6</td> + </tr><tr> + <td class="tdc">101</td> <td class="tdc">52.7</td> + <td class="tdc">144</td> <td class="tdc">75.6</td> + <td class="tdc">187</td> <td class="tdc"> 99.0</td> + <td class="tdc">230</td> <td class="tdc">123.2</td> + </tr><tr> + <td class="tdc">102</td> <td class="tdc">53.2</td> + <td class="tdc">145</td> <td class="tdc">76.1</td> + <td class="tdc">188</td> <td class="tdc"> 99.5</td> + <td class="tdc">231</td> <td class="tdc">123.8</td> + </tr><tr> + <td class="tdc">103</td> <td class="tdc">53.7</td> + <td class="tdc">146</td> <td class="tdc">76.7</td> + <td class="tdc">189</td> <td class="tdc">100.1</td> + <td class="tdc">232</td> <td class="tdc">124.3</td> + </tr><tr> + <td class="tdc">104</td> <td class="tdc">54.3</td> + <td class="tdc">147</td> <td class="tdc">77.2</td> + <td class="tdc">190</td> <td class="tdc">100.6</td> + <td class="tdc">233</td> <td class="tdc">124.9</td> + </tr><tr> + <td class="tdc">105</td> <td class="tdc">54.8</td> + <td class="tdc">148</td> <td class="tdc">77.8</td> + <td class="tdc">191</td> <td class="tdc">101.2</td> + <td class="tdc">234</td> <td class="tdc">125.5</td> + </tr><tr> + <td class="tdc">106</td> <td class="tdc">55.3</td> + <td class="tdc">149</td> <td class="tdc">78.3</td> + <td class="tdc">192</td> <td class="tdc">101.7</td> + <td class="tdc">235</td> <td class="tdc">126.0</td> + </tr><tr> + <td class="tdc">107</td> <td class="tdc">55.9</td> + <td class="tdc">150</td> <td class="tdc">78.9</td> + <td class="tdc">193</td> <td class="tdc">102.3</td> + <td class="tdc">236</td> <td class="tdc">126.6</td> + </tr><tr> + <td class="tdc">108</td> <td class="tdc">56.4</td> + <td class="tdc">151</td> <td class="tdc">79.4</td> + <td class="tdc">194</td> <td class="tdc">102.9</td> + <td class="tdc">237</td> <td class="tdc">127.2</td> + </tr><tr class="bb"> + <td class="tdc">109</td> <td class="tdc">56.9</td> + <td class="tdc">152</td> <td class="tdc">80.0</td> + <td class="tdc">195</td> <td class="tdc">103.4</td> + <td class="tdc">238</td> <td class="tdc">127.8</td> + </tr><tr> + <td class="tdc">110</td> <td class="tdc">57.5</td> + <td class="tdc">153</td> <td class="tdc">80.5</td> + <td class="tdc">196</td> <td class="tdc">104.0</td> + <td class="tdc">239</td> <td class="tdc">128.3</td> + </tr><tr> + <td class="tdc">111</td> <td class="tdc">58.0</td> + <td class="tdc">154</td> <td class="tdc">81.0</td> + <td class="tdc">197</td> <td class="tdc">104.6</td> + <td class="tdc">240</td> <td class="tdc">128.9</td> + </tr><tr> + <td class="tdc">112</td> <td class="tdc">58.5</td> + <td class="tdc">155</td> <td class="tdc">81.6</td> + <td class="tdc">198</td> <td class="tdc">105.1</td> + <td class="tdc">241</td> <td class="tdc">129.5</td> + </tr><tr> + <td class="tdc">113</td> <td class="tdc">59.1</td> + <td class="tdc">156</td> <td class="tdc">82.1</td> + <td class="tdc">199</td> <td class="tdc">105.7</td> + <td class="tdc">242</td> <td class="tdc">130.0</td> + </tr><tr> + <td class="tdc">114</td> <td class="tdc">59.6</td> + <td class="tdc">157</td> <td class="tdc">82.7</td> + <td class="tdc">200</td> <td class="tdc">106.3</td> + <td class="tdc">243</td> <td class="tdc">130.6</td> + </tr><tr> + <td class="tdc">115</td> <td class="tdc">60.1</td> + <td class="tdc">158</td> <td class="tdc">83.2</td> + <td class="tdc">201</td> <td class="tdc">106.8</td> + <td class="tdc">244</td> <td class="tdc">131.2</td> + </tr><tr> + <td class="tdc">116</td> <td class="tdc">60.7</td> + <td class="tdc">159</td> <td class="tdc">83.8</td> + <td class="tdc">202</td> <td class="tdc">107.4</td> + <td class="tdc">245</td> <td class="tdc">131.8</td> + </tr><tr> + <td class="tdc">117</td> <td class="tdc">61.2</td> + <td class="tdc">160</td> <td class="tdc">84.3</td> + <td class="tdc">203</td> <td class="tdc">107.9</td> + <td class="tdc">246</td> <td class="tdc">132.3</td> + </tr><tr> + <td class="tdc">118</td> <td class="tdc">61.7</td> + <td class="tdc">161</td> <td class="tdc">84.8</td> + <td class="tdc">204</td> <td class="tdc">108.5</td> + <td class="tdc">247</td> <td class="tdc">132.9</td> + </tr><tr> + <td class="tdc">119</td> <td class="tdc">62.3</td> + <td class="tdc">162</td> <td class="tdc">85.4</td> + <td class="tdc">205</td> <td class="tdc">109.1</td> + <td class="tdc">248</td> <td class="tdc">133.5</td> + </tr><tr> + <td class="tdc">120</td> <td class="tdc">62.8</td> + <td class="tdc">163</td> <td class="tdc">85.9</td> + <td class="tdc">206</td> <td class="tdc">109.6</td> + <td class="tdc">249</td> <td class="tdc">134.1</td> + </tr><tr> + <td class="tdc">121</td> <td class="tdc">63.3</td> + <td class="tdc">164</td> <td class="tdc">86.5</td> + <td class="tdc">207</td> <td class="tdc">110.2</td> + <td class="tdc">250</td> <td class="tdc">134.6</td> + </tr><tr> + <td class="tdc">122</td> <td class="tdc">63.9</td> + <td class="tdc">165</td> <td class="tdc">87.0</td> + <td class="tdc">208</td> <td class="tdc">110.8</td> + <td class="tdc">251</td> <td class="tdc">135.2</td> + </tr><tr> + <td class="tdc">123</td> <td class="tdc">64.4</td> + <td class="tdc">166</td> <td class="tdc">87.6</td> + <td class="tdc">209</td> <td class="tdc">111.3</td> + <td class="tdc">252</td> <td class="tdc">135.8</td> + </tr><tr> + <td class="tdc">124</td> <td class="tdc">64.9</td> + <td class="tdc">167</td> <td class="tdc">88.1</td> + <td class="tdc">210</td> <td class="tdc">111.9</td> + <td class="tdc">253</td> <td class="tdc">136.3</td> + </tr><tr> + <td class="tdc">125</td> <td class="tdc">65.5</td> + <td class="tdc">168</td> <td class="tdc">88.6</td> + <td class="tdc">211</td> <td class="tdc">112.5</td> + <td class="tdc">254</td> <td class="tdc">136.9</td> + </tr><tr> + <td class="tdc">126</td> <td class="tdc">66.0</td> + <td class="tdc">169</td> <td class="tdc">89.2</td> + <td class="tdc">212</td> <td class="tdc">113.0</td> + <td class="tdc">255</td> <td class="tdc">137.5</td> + </tr><tr> + <td class="tdc">127</td> <td class="tdc">66.5</td> + <td class="tdc">170</td> <td class="tdc">89.7</td> + <td class="tdc">213</td> <td class="tdc">113.6</td> + <td class="tdc">256</td> <td class="tdc">138.1</td> + </tr><tr> + <td class="tdc">128</td> <td class="tdc">67.1</td> + <td class="tdc">171</td> <td class="tdc">90.3</td> + <td class="tdc">214</td> <td class="tdc">114.2</td> + <td class="tdc">257</td> <td class="tdc">138.6</td> + </tr><tr> + <td class="tdc">129</td> <td class="tdc">67.6</td> + <td class="tdc">172</td> <td class="tdc">90.8</td> + <td class="tdc">215</td> <td class="tdc">114.7</td> + <td class="tdc">258</td> <td class="tdc">139.2</td> + </tr><tr> + <td class="tdc">130</td> <td class="tdc">68.1</td> + <td class="tdc">173</td> <td class="tdc">91.4</td> + <td class="tdc">216</td> <td class="tdc">115.3</td> + <td class="tdc">259</td> <td class="tdc">139.8</td> + </tr><tr> + <td class="tdc">131</td> <td class="tdc">68.7</td> + <td class="tdc">174</td> <td class="tdc">91.9</td> + <td class="tdc">217</td> <td class="tdc">115.8</td> + <td class="tdc">260</td> <td class="tdc">140.4</td> + </tr><tr> + <td class="tdc">132</td> <td class="tdc">69.2</td> + <td class="tdc">175</td> <td class="tdc">92.4</td> + <td class="tdc">218</td> <td class="tdc">116.4</td> + <td class="tdc">261</td> <td class="tdc">140.9</td> + </tr><tr> + <td class="tdc" colspan="8"> <span class="pagenum"><a id="Page_160"></a>[Pg 160]</span></td> + </tr><tr class="f110"> + <td class="tdc"> <b>(A)</b> </td> <td class="tdc"> <b>(B)</b> </td> + <td class="tdc"> <b>(A)</b> </td> <td class="tdc"> <b>(B)</b> </td> + <td class="tdc"> <b>(A)</b> </td> <td class="tdc"> <b>(B)</b> </td> + <td class="tdc"> <b>(A)</b> </td> <td class="tdc"> <b>(B)</b> </td> + </tr><tr> + <td class="tdc">262</td> <td class="tdc">141.5</td> + <td class="tdc">305</td> <td class="tdc">166.8</td> + <td class="tdc">348</td> <td class="tdc">192.6</td> + <td class="tdc">391</td> <td class="tdc">219.3</td> + </tr><tr> + <td class="tdc">263</td> <td class="tdc">142.1</td> + <td class="tdc">306</td> <td class="tdc">167.3</td> + <td class="tdc">349</td> <td class="tdc">193.2</td> + <td class="tdc">392</td> <td class="tdc">219.9</td> + </tr><tr> + <td class="tdc">264</td> <td class="tdc">142.7</td> + <td class="tdc">307</td> <td class="tdc">167.9</td> + <td class="tdc">350</td> <td class="tdc">193.8</td> + <td class="tdc">393</td> <td class="tdc">220.5</td> + </tr><tr> + <td class="tdc">265</td> <td class="tdc">143.2</td> + <td class="tdc">308</td> <td class="tdc">168.5</td> + <td class="tdc">351</td> <td class="tdc">194.4</td> + <td class="tdc">394</td> <td class="tdc">221.2</td> + </tr><tr> + <td class="tdc">266</td> <td class="tdc">143.8</td> + <td class="tdc">309</td> <td class="tdc">169.1</td> + <td class="tdc">352</td> <td class="tdc">195.0</td> + <td class="tdc">395</td> <td class="tdc">221.8</td> + </tr><tr> + <td class="tdc">267</td> <td class="tdc">144.4</td> + <td class="tdc">310</td> <td class="tdc">169.7</td> + <td class="tdc">353</td> <td class="tdc">195.6</td> + <td class="tdc">396</td> <td class="tdc">222.4</td> + </tr><tr> + <td class="tdc">268</td> <td class="tdc">144.9</td> + <td class="tdc">311</td> <td class="tdc">170.3</td> + <td class="tdc">354</td> <td class="tdc">196.2</td> + <td class="tdc">397</td> <td class="tdc">223.1</td> + </tr><tr> + <td class="tdc">269</td> <td class="tdc">145.5</td> + <td class="tdc">312</td> <td class="tdc">170.9</td> + <td class="tdc">355</td> <td class="tdc">196.8</td> + <td class="tdc">398</td> <td class="tdc">223.7</td> + </tr><tr> + <td class="tdc">270</td> <td class="tdc">146.1</td> + <td class="tdc">313</td> <td class="tdc">171.5</td> + <td class="tdc">356</td> <td class="tdc">197.4</td> + <td class="tdc">399</td> <td class="tdc">224.3</td> + </tr><tr> + <td class="tdc">271</td> <td class="tdc">146.7</td> + <td class="tdc">314</td> <td class="tdc">172.1</td> + <td class="tdc">357</td> <td class="tdc">198.0</td> + <td class="tdc">400</td> <td class="tdc">224.9</td> + </tr><tr> + <td class="tdc">272</td> <td class="tdc">147.2</td> + <td class="tdc">315</td> <td class="tdc">172.7</td> + <td class="tdc">358</td> <td class="tdc">198.6</td> + <td class="tdc">401</td> <td class="tdc">225.7</td> + </tr><tr> + <td class="tdc">273</td> <td class="tdc">147.8</td> + <td class="tdc">316</td> <td class="tdc">173.3</td> + <td class="tdc">359</td> <td class="tdc">199.2</td> + <td class="tdc">402</td> <td class="tdc">226.4</td> + </tr><tr> + <td class="tdc">274</td> <td class="tdc">148.4</td> + <td class="tdc">317</td> <td class="tdc">173.9</td> + <td class="tdc">360</td> <td class="tdc">199.8</td> + <td class="tdc">403</td> <td class="tdc">227.1</td> + </tr><tr> + <td class="tdc">275</td> <td class="tdc">149.0</td> + <td class="tdc">318</td> <td class="tdc">174.5</td> + <td class="tdc">361</td> <td class="tdc">200.4</td> + <td class="tdc">404</td> <td class="tdc">227.8</td> + </tr><tr> + <td class="tdc">276</td> <td class="tdc">149.5</td> + <td class="tdc">319</td> <td class="tdc">175.1</td> + <td class="tdc">362</td> <td class="tdc">201.1</td> + <td class="tdc">405</td> <td class="tdc">228.6</td> + </tr><tr> + <td class="tdc">277</td> <td class="tdc">150.1</td> + <td class="tdc">320</td> <td class="tdc">175.6</td> + <td class="tdc">363</td> <td class="tdc">201.7</td> + <td class="tdc">406</td> <td class="tdc">229.3</td> + </tr><tr> + <td class="tdc">278</td> <td class="tdc">150.7</td> + <td class="tdc">321</td> <td class="tdc">176.2</td> + <td class="tdc">364</td> <td class="tdc">202.3</td> + <td class="tdc">407</td> <td class="tdc">230.0</td> + </tr><tr class="bb"> + <td class="tdc">279</td> <td class="tdc">151.3</td> + <td class="tdc">322</td> <td class="tdc">176.8</td> + <td class="tdc">365</td> <td class="tdc">203.0</td> + <td class="tdc">408</td> <td class="tdc">230.7</td> + </tr><tr> + <td class="tdc">280</td> <td class="tdc">151.9</td> + <td class="tdc">323</td> <td class="tdc">177.4</td> + <td class="tdc">366</td> <td class="tdc">203.6</td> + <td class="tdc">409</td> <td class="tdc">231.4</td> + </tr><tr> + <td class="tdc">281</td> <td class="tdc">152.5</td> + <td class="tdc">324</td> <td class="tdc">178.0</td> + <td class="tdc">367</td> <td class="tdc">204.2</td> + <td class="tdc">410</td> <td class="tdc">232.1</td> + </tr><tr> + <td class="tdc">282</td> <td class="tdc">153.1</td> + <td class="tdc">325</td> <td class="tdc">178.6</td> + <td class="tdc">368</td> <td class="tdc">204.8</td> + <td class="tdc">411</td> <td class="tdc">232.8</td> + </tr><tr> + <td class="tdc">283</td> <td class="tdc">153.7</td> + <td class="tdc">326</td> <td class="tdc">179.2</td> + <td class="tdc">369</td> <td class="tdc">205.5</td> + <td class="tdc">412</td> <td class="tdc">233.5</td> + </tr><tr> + <td class="tdc">284</td> <td class="tdc">154.3</td> + <td class="tdc">327</td> <td class="tdc">178.8</td> + <td class="tdc">370</td> <td class="tdc">206.1</td> + <td class="tdc">413</td> <td class="tdc">234.3</td> + </tr><tr> + <td class="tdc">285</td> <td class="tdc">154.9</td> + <td class="tdc">328</td> <td class="tdc">180.4</td> + <td class="tdc">371</td> <td class="tdc">206.7</td> + <td class="tdc">414</td> <td class="tdc">235.0</td> + </tr><tr> + <td class="tdc">286</td> <td class="tdc">155.5</td> + <td class="tdc">329</td> <td class="tdc">181.0</td> + <td class="tdc">372</td> <td class="tdc">207.3</td> + <td class="tdc">415</td> <td class="tdc">235.7</td> + </tr><tr> + <td class="tdc">287</td> <td class="tdc">156.1</td> + <td class="tdc">330</td> <td class="tdc">181.6</td> + <td class="tdc">373</td> <td class="tdc">208.0</td> + <td class="tdc">416</td> <td class="tdc">236.4</td> + </tr><tr> + <td class="tdc">288</td> <td class="tdc">156.7</td> + <td class="tdc">331</td> <td class="tdc">182.2</td> + <td class="tdc">374</td> <td class="tdc">208.6</td> + <td class="tdc">417</td> <td class="tdc">237.1</td> + </tr><tr> + <td class="tdc">289</td> <td class="tdc">157.2</td> + <td class="tdc">332</td> <td class="tdc">182.8</td> + <td class="tdc">375</td> <td class="tdc">209.2</td> + <td class="tdc">418</td> <td class="tdc">237.8</td> + </tr><tr> + <td class="tdc">290</td> <td class="tdc">157.8</td> + <td class="tdc">333</td> <td class="tdc">183.5</td> + <td class="tdc">376</td> <td class="tdc">209.9</td> + <td class="tdc">419</td> <td class="tdc">238.5</td> + </tr><tr> + <td class="tdc">291</td> <td class="tdc">158.4</td> + <td class="tdc">334</td> <td class="tdc">184.1</td> + <td class="tdc">377</td> <td class="tdc">210.5</td> + <td class="tdc">420</td> <td class="tdc">239.2</td> + </tr><tr> + <td class="tdc">292</td> <td class="tdc">159.0</td> + <td class="tdc">335</td> <td class="tdc">184.7</td> + <td class="tdc">378</td> <td class="tdc">211.1</td> + <td class="tdc">421</td> <td class="tdc">239.9</td> + </tr><tr> + <td class="tdc">293</td> <td class="tdc">159.6</td> + <td class="tdc">336</td> <td class="tdc">185.4</td> + <td class="tdc">379</td> <td class="tdc">211.7</td> + <td class="tdc">422</td> <td class="tdc">240.6</td> + </tr><tr> + <td class="tdc">294</td> <td class="tdc">160.2</td> + <td class="tdc">337</td> <td class="tdc">186.0</td> + <td class="tdc">380</td> <td class="tdc">212.4</td> + <td class="tdc">423</td> <td class="tdc">241.3</td> + </tr><tr> + <td class="tdc">295</td> <td class="tdc">160.8</td> + <td class="tdc">338</td> <td class="tdc">186.6</td> + <td class="tdc">381</td> <td class="tdc">213.0</td> + <td class="tdc">424</td> <td class="tdc">242.0</td> + </tr><tr> + <td class="tdc">296</td> <td class="tdc">161.4</td> + <td class="tdc">339</td> <td class="tdc">187.2</td> + <td class="tdc">382</td> <td class="tdc">213.6</td> + <td class="tdc">425</td> <td class="tdc">242.7</td> + </tr><tr> + <td class="tdc">297</td> <td class="tdc">162.0</td> + <td class="tdc">340</td> <td class="tdc">187.8</td> + <td class="tdc">383</td> <td class="tdc">214.3</td> + <td class="tdc">426</td> <td class="tdc">243.4</td> + </tr><tr> + <td class="tdc">298</td> <td class="tdc">162.6</td> + <td class="tdc">341</td> <td class="tdc">188.4</td> + <td class="tdc">384</td> <td class="tdc">214.9</td> + <td class="tdc">427</td> <td class="tdc">244.1</td> + </tr><tr> + <td class="tdc">299</td> <td class="tdc">163.2</td> + <td class="tdc">342</td> <td class="tdc">189.0</td> + <td class="tdc">385</td> <td class="tdc">215.5</td> + <td class="tdc">428</td> <td class="tdc">244.9</td> + </tr><tr> + <td class="tdc">300</td> <td class="tdc">163.8</td> + <td class="tdc">343</td> <td class="tdc">189.6</td> + <td class="tdc">386</td> <td class="tdc">216.1</td> + <td class="tdc">429</td> <td class="tdc">245.6</td> + </tr><tr> + <td class="tdc">301</td> <td class="tdc">164.4</td> + <td class="tdc">344</td> <td class="tdc">190.2</td> + <td class="tdc">387</td> <td class="tdc">216.8</td> + <td class="tdc">430</td> <td class="tdc">246.3</td> + </tr><tr> + <td class="tdc">302</td> <td class="tdc">165.0</td> + <td class="tdc">345</td> <td class="tdc">190.8</td> + <td class="tdc">388</td> <td class="tdc">217.4</td> + <td class="tdc"> </td> <td class="tdc"> </td> + </tr><tr> + <td class="tdc">303</td> <td class="tdc">165.6</td> + <td class="tdc">346</td> <td class="tdc">191.4</td> + <td class="tdc">389</td> <td class="tdc">218.0</td> + <td class="tdc"> </td> <td class="tdc"> </td> + </tr><tr class="bb"> + <td class="tdc">304</td> <td class="tdc">166.2</td> + <td class="tdc">347</td> <td class="tdc">192.0</td> + <td class="tdc">390</td> <td class="tdc">218.7</td> + <td class="tdc"> </td> <td class="tdc"> </td> + </tr> + </tbody> +</table> + +<p id="P_142"><span class="pagenum"><a id="Page_161"></a>[Pg 161]</span> +<b>142. Table for the Determination of Invert Sugar (Reducing Sugars) +in the Presence of Sucrose.</b>—The method adopted by the Association +of Official Agricultural Chemists is essentially that proposed by +Meissl and Hiller.<a id="FNanchor_108" href="#Footnote_108" class="fnanchor">[108]</a> +Prepare a solution of the material to be examined in such a manner +that it contains twenty grams of the mixed sugars in one hundred cubic +centimeters, after clarification and the removal of the excess of lead. +Prepare a series of solutions in large test tubes by adding one, two, +three, four, five etc. cubic centimeters of this solution to each tube +successively. Add five cubic centimeters of the mixed copper reagent +to each, heat to boiling, boil two minutes and filter. Note the volume +of sugar solution which gives the filtrate lightest in tint, but still +distinctly blue. Place twenty times this volume of the sugar solution +in a 100 cubic centimeter flask, dilute to the mark, and mix well. Use +fifty cubic centimeters of the solution for the determination, which is +conducted as already described, until the weight of copper is obtained. +For the calculation of the results use the following formulas and table +of factors of Meissl and Hiller:<a id="FNanchor_109" href="#Footnote_109" class="fnanchor">[109]</a></p> + +<table class="spb1"> + <tbody><tr> + <td class="tdr_wsp">Let Cu =</td> + <td class="tdl">the weight of the copper obtained;</td> + </tr><tr> + <td class="tdr_wsp">P =</td> + <td class="tdl">the polarization of the sample;</td> + </tr><tr> + <td class="tdr_wsp">W =</td> + <td class="tdl">the weight of the sample in the fifty cubic</td> + </tr><tr> + <td class="tdr_wsp"> </td> + <td class="tdl_ws1">centimeters of the solution used for determination;</td> + </tr><tr> + <td class="tdr_wsp">F =</td> + <td class="tdl">the factor obtained from the table for conversion</td> + </tr><tr> + <td class="tdr_wsp"> </td> + <td class="tdl_ws1">of copper to invert sugar;</td> + </tr><tr> + <td class="tdr_wsp u"> Cu </td> + <td class="tdl" rowspan="2">= approximate absolute weight of invert sugar = Z;</td> + </tr><tr> + <td class="tdr_ws1">2</td> + </tr><tr> + <td class="tdr_ws1">100 </td> + <td class="tdl"> </td> + </tr><tr> + <td class="tdr_wsp">Z × —— = </td> + <td class="tdl">approximate per cent of invert sugar = <i>y</i>;</td> + </tr><tr> + <td class="tdr_ws1">W </td> + <td class="tdl"> </td> + </tr><tr> + <td class="tdr_wsp u"> 100P </td> + <td class="tdl" rowspan="2">= R, relative number for sucrose;</td> + </tr><tr> + <td class="tdr_ws1">P + <i>y</i></td> + </tr><tr> + <td class="tdr_wsp">100 - R =</td> + <td class="tdl">I, relative number for invert sugar;</td> + </tr><tr> + <td class="tdr_wsp u"> Cu </td> + <td class="tdl" rowspan="2">= per cent of invert sugar.</td> + </tr><tr> + <td class="tdr_ws1">W</td> + </tr> + </tbody> +</table> + +<p>Z indicates the vertical column, and the ratio of R to I, the +horizontal column of the table, which are to be used for the purpose of +finding the factor (F) for calculating copper to invert sugar. +<span class="pagenum"><a id="Page_162"></a>[Pg 162]</span></p> + +<p><i>Example</i>:—The polarization of a sugar is 86.4, and 3.256 grams +of it (W) are equivalent to 0.290 gram of copper. Then:</p> + +<table class="spb1 fs_105"> + <tbody><tr> + <td class="tdc bb">Cu</td> + <td class="tdl" rowspan="2"> = </td> + <td class="tdc bb">0.290</td> + <td class="tdl" rowspan="2"> = 0.145 = Z</td> + </tr><tr> + <td class="tdc">2</td> + <td class="tdc">2</td> + </tr> + </tbody> +</table> + +<table class="spb1 fs_105"> + <tbody><tr> + <td class="tdl" rowspan="2">Z × </td> + <td class="tdc bb">100</td> + <td class="tdl" rowspan="2"> = 0.145 × </td> + <td class="tdc bb">100</td> + <td class="tdl" rowspan="2"> = 4.45 = <i>y</i></td> + </tr><tr> + <td class="tdc">W</td> + <td class="tdc">3.256</td> + </tr> + </tbody> +</table> + +<table class="spb1 fs_105"> + <tbody><tr> + <td class="tdc bb">100P</td> + <td class="tdl" rowspan="2"> = </td> + <td class="tdc bb">8640</td> + <td class="tdl" rowspan="2"> = 95.1 = R</td> + </tr><tr> + <td class="tdc">P + <i>y</i></td> + <td class="tdc">86.4 + 4.45</td> + </tr> + </tbody> +</table> + +<p class="f105">100 - R = 100 - 95.1 = 4.9 = I</p> + +<p class="f105">R : I = 95.1 : 4.9</p> + +<p>By consulting the table it will be seen that the vertical column headed +I = 150 is nearest to Z, 145, the horizontal column headed 95: 5 is +nearest to the ratio of R to I, 95.1: 4.9. Where these columns meet we +find the factor 51.2, which enters into the final calculation:</p> + +<table class="spb1 fs_105"> + <tbody><tr> + <td class="tdc bb">CuF</td> + <td class="tdl" rowspan="2"> = </td> + <td class="tdc bb">.290 × 51.2</td> + <td class="tdl" rowspan="2"> = 4.56 the true per cent of invert sugar.</td> + </tr><tr> + <td class="tdc">W</td> + <td class="tdc">3.256</td> + </tr> + </tbody> +</table> + +<p class="f120"><b><span class="smcap">Meissl and Hiller’s Factors for the Determination of<br> +More Than One Per Cent of Invert Sugar.</span></b></p> + +<table class="spb1"> + <thead><tr class="fs_110"> + <th class="tdc br bb" rowspan="2">Ratio of<br>sucrose<br>to invert<br>sugar =</th> + <th class="tdc bb" colspan="7">Approximate absolute weight of invert sugar = <i>Z</i>.</th> + </tr><tr class="bb"> + <th class="tdc">I = 200</th> + <th class="tdc bl">I = 175</th> + <th class="tdc bl">I = 150</th> + <th class="tdc bl">I = 125</th> + <th class="tdc bl">I = 100</th> + <th class="tdc bl">I = 75</th> + <th class="tdc bl">I = 50</th> + </tr></thead> + <tbody><tr class="bb"> + <td class="tdc">R : I.</td> <td class="tdc bl">mg.</td> + <td class="tdc bl">mg.</td> <td class="tdc bl">mg.</td> + <td class="tdc bl">mg.</td> <td class="tdc bl">mg.</td> + <td class="tdc bl">mg.</td> <td class="tdc bl">mg.</td> + </tr><tr> + <td class="tdc">  0 : 100</td> <td class="tdc">56.4</td> + <td class="tdc">55.4</td> <td class="tdc">54.5</td> + <td class="tdc">53.8</td> <td class="tdc">53.2</td> + <td class="tdc">53.0</td> <td class="tdc">53.0</td> + </tr><tr> + <td class="tdc">10 : 90</td> <td class="tdc">56.3</td> + <td class="tdc">55.3</td> <td class="tdc">54.4</td> + <td class="tdc">53.8</td> <td class="tdc">53.2</td> + <td class="tdc">52.9</td> <td class="tdc">52.9</td> + </tr><tr> + <td class="tdc">20 : 80</td> <td class="tdc">56.2</td> + <td class="tdc">55.2</td> <td class="tdc">54.3</td> + <td class="tdc">53.7</td> <td class="tdc">53.2</td> + <td class="tdc">52.7</td> <td class="tdc">52.7</td> + </tr><tr> + <td class="tdc">30 : 70</td> <td class="tdc">56.1</td> + <td class="tdc">55.1</td> <td class="tdc">54.2</td> + <td class="tdc">53.7</td> <td class="tdc">53.2</td> + <td class="tdc">52.6</td> <td class="tdc">52.6</td> + </tr><tr> + <td class="tdc">40 : 60</td> <td class="tdc">55.9</td> + <td class="tdc">55.0</td> <td class="tdc">54.1</td> + <td class="tdc">53.6</td> <td class="tdc">53.1</td> + <td class="tdc">52.5</td> <td class="tdc">52.4</td> + </tr><tr> + <td class="tdc">50 : 50</td> <td class="tdc">55.7</td> + <td class="tdc">54.9</td> <td class="tdc">54.0</td> + <td class="tdc">53.5</td> <td class="tdc">53.1</td> + <td class="tdc">52.3</td> <td class="tdc">52.2</td> + </tr><tr> + <td class="tdc">60 : 40</td> <td class="tdc">55.6</td> + <td class="tdc">54.7</td> <td class="tdc">53.8</td> + <td class="tdc">53.2</td> <td class="tdc">52.8</td> + <td class="tdc">52.1</td> <td class="tdc">51.9</td> + </tr><tr> + <td class="tdc">70 : 30</td> <td class="tdc">55.5</td> + <td class="tdc">54.5</td> <td class="tdc">53.5</td> + <td class="tdc">52.9</td> <td class="tdc">52.5</td> + <td class="tdc">51.9</td> <td class="tdc">51.6</td> + </tr><tr> + <td class="tdc">80 : 20</td> <td class="tdc">55.4</td> + <td class="tdc">54.3</td> <td class="tdc">53.3</td> + <td class="tdc">52.7</td> <td class="tdc">52.2</td> + <td class="tdc">51.7</td> <td class="tdc">51.3</td> + </tr><tr> + <td class="tdc">90 : 10</td> <td class="tdc">54.6</td> + <td class="tdc">53.6</td> <td class="tdc">53.1</td> + <td class="tdc">52.6</td> <td class="tdc">52.1</td> + <td class="tdc">51.6</td> <td class="tdc">51.2</td> + </tr><tr> + <td class="tdc">91 : 9 </td> <td class="tdc">54.1</td> + <td class="tdc">53.6</td> <td class="tdc">52.6</td> + <td class="tdc">52.1</td> <td class="tdc">51.6</td> + <td class="tdc">51.2</td> <td class="tdc">50.7</td> + </tr><tr> + <td class="tdc">92 : 8 </td> <td class="tdc">53.6</td> + <td class="tdc">53.1</td> <td class="tdc">52.1</td> + <td class="tdc">51.6</td> <td class="tdc">51.2</td> + <td class="tdc">50.7</td> <td class="tdc">50.3</td> + </tr><tr> + <td class="tdc">93 : 7 </td> <td class="tdc">53.6</td> + <td class="tdc">53.1</td> <td class="tdc">52.1</td> + <td class="tdc">51.2</td> <td class="tdc">50.7</td> + <td class="tdc">50.3</td> <td class="tdc">49.8</td> + </tr><tr> + <td class="tdc">94 : 6 </td> <td class="tdc">53.1</td> + <td class="tdc">52.6</td> <td class="tdc">51.6</td> + <td class="tdc">50.7</td> <td class="tdc">50.3</td> + <td class="tdc">49.8</td> <td class="tdc">48.9</td> + </tr><tr> + <td class="tdc">95 : 5 </td> <td class="tdc">52.6</td> + <td class="tdc">52.1</td> <td class="tdc">51.2</td> + <td class="tdc">50.3</td> <td class="tdc">49.4</td> + <td class="tdc">48.9</td> <td class="tdc">48.5</td> + </tr><tr> + <td class="tdc">96 : 4 </td> <td class="tdc">52.1</td> + <td class="tdc">51.2</td> <td class="tdc">50.7</td> + <td class="tdc">49.8</td> <td class="tdc">48.9</td> + <td class="tdc">47.7</td> <td class="tdc">46.9</td> + </tr><tr> + <td class="tdc">97 : 3 </td> <td class="tdc">50.7</td> + <td class="tdc">50.3</td> <td class="tdc">49.8</td> + <td class="tdc">48.9</td> <td class="tdc">47.7</td> + <td class="tdc">46.2</td> <td class="tdc">45.1</td> + </tr><tr> + <td class="tdc">98 : 2 </td> <td class="tdc">49.9</td> + <td class="tdc">48.9</td> <td class="tdc">48.5</td> + <td class="tdc">47.3</td> <td class="tdc">45.8</td> + <td class="tdc">43.3</td> <td class="tdc">40.0</td> + </tr><tr class="bb"> + <td class="tdc">99 : 1 </td> <td class="tdc">47.7</td> + <td class="tdc">47.3</td> <td class="tdc">46.5</td> + <td class="tdc">45.1</td> <td class="tdc">43.3</td> + <td class="tdc">41.2</td> <td class="tdc">38.1</td> + </tr> + </tbody> +</table> + +<p id="P_143"><span class="pagenum"><a id="Page_163"></a>[Pg 163]</span> +<b>143. Table for the Estimation of Milk Sugar.</b>—The solutions to +be used for this table are the same as those employed in the preceding +table for the estimation of invert sugar. The milk sugar is supposed to +be in a pure form in solution before beginning the analysis. The method +to be employed for milk will be given in the part devoted to dairy products.</p> + +<p>In the conduct of the work twenty-five cubic centimeters of the copper +solution are mixed with an equal quantity of the alkaline tartrate +mixture, and from twenty to one hundred cubic centimeters of the sugar +solution added, according to its concentration. This solution should +not contain less than seventy nor more than 306 milligrams of lactose. +The volume is completed to 150 cubic centimeters with boiling water and +kept in lively ebullition for six minutes. The rest of the operation is +conducted in the manner already described. From the weight of copper +obtained the quantity of milk sugar is determined by inspecting the +table. It is recommended to use such a weight of milk sugar as will +give about 200 milligrams of copper.</p> + +<p id="MILK_SUGAR" class="f120 spa1"><b><span class="smcap">Table for Determining Milk Sugar.</span></b></p> + +<ul class="index fs_110"> +<li class="isub3"><b>(A)</b> = Milligrams of copper.</li> +<li class="isub3"><b>(B)</b> = Milligrams of milk sugar.</li> +</ul> + +<table class="spb1"> + <thead><tr class="fs_110"> + <th class="tdc"> (A) </th> <th class="tdc"> (B) </th> + <th class="tdc"> (A) </th> <th class="tdc"> (B) </th> + <th class="tdc"> (A) </th> <th class="tdc"> (B) </th> + <th class="tdc"> (A) </th> <th class="tdc"> (B) </th> + </tr></thead> + <tbody><tr> + <td class="tdc">100</td> <td class="tdc"> 71.6</td> + <td class="tdc">120</td> <td class="tdc"> 86.4</td> + <td class="tdc">140</td> <td class="tdc">101.3</td> + <td class="tdc">160</td> <td class="tdc">116.4</td> + </tr><tr> + <td class="tdc">101</td> <td class="tdc"> 72.4</td> + <td class="tdc">121</td> <td class="tdc"> 87.2</td> + <td class="tdc">141</td> <td class="tdc">102.0</td> + <td class="tdc">161</td> <td class="tdc">117.1</td> + </tr><tr> + <td class="tdc">102</td> <td class="tdc"> 73.1</td> + <td class="tdc">122</td> <td class="tdc"> 87.9</td> + <td class="tdc">142</td> <td class="tdc">102.8</td> + <td class="tdc">162</td> <td class="tdc">117.9</td> + </tr><tr> + <td class="tdc">103</td> <td class="tdc"> 73.8</td> + <td class="tdc">123</td> <td class="tdc"> 88.7</td> + <td class="tdc">143</td> <td class="tdc">103.5</td> + <td class="tdc">163</td> <td class="tdc">118.6</td> + </tr><tr> + <td class="tdc">104</td> <td class="tdc"> 74.6</td> + <td class="tdc">124</td> <td class="tdc"> 89.4</td> + <td class="tdc">144</td> <td class="tdc">104.3</td> + <td class="tdc">164</td> <td class="tdc">119.4</td> + </tr><tr> + <td class="tdc">105</td> <td class="tdc"> 75.3</td> + <td class="tdc">125</td> <td class="tdc"> 90.1</td> + <td class="tdc">145</td> <td class="tdc">105.1</td> + <td class="tdc">165</td> <td class="tdc">120.2</td> + </tr><tr> + <td class="tdc">106</td> <td class="tdc"> 76.1</td> + <td class="tdc">126</td> <td class="tdc"> 90.9</td> + <td class="tdc">146</td> <td class="tdc">105.8</td> + <td class="tdc">166</td> <td class="tdc">120.9</td> + </tr><tr> + <td class="tdc">107</td> <td class="tdc"> 76.8</td> + <td class="tdc">127</td> <td class="tdc"> 91.6</td> + <td class="tdc">147</td> <td class="tdc">106.6</td> + <td class="tdc">167</td> <td class="tdc">121.7</td> + </tr><tr> + <td class="tdc">108</td> <td class="tdc"> 77.6</td> + <td class="tdc">128</td> <td class="tdc"> 92.4</td> + <td class="tdc">148</td> <td class="tdc">107.3</td> + <td class="tdc">168</td> <td class="tdc">122.4</td> + </tr><tr class="bb"> + <td class="tdc">109</td> <td class="tdc"> 78.3</td> + <td class="tdc">129</td> <td class="tdc"> 93.1</td> + <td class="tdc">149</td> <td class="tdc">108.1</td> + <td class="tdc">169</td> <td class="tdc">123.2</td> + </tr><tr> + <td class="tdc">110</td> <td class="tdc"> 79.0</td> + <td class="tdc">130</td> <td class="tdc"> 93.8</td> + <td class="tdc">150</td> <td class="tdc">108.8</td> + <td class="tdc">170</td> <td class="tdc">123.9</td> + </tr><tr> + <td class="tdc">111</td> <td class="tdc"> 79.8</td> + <td class="tdc">131</td> <td class="tdc"> 94.6</td> + <td class="tdc">151</td> <td class="tdc">109.6</td> + <td class="tdc">171</td> <td class="tdc">124.7</td> + </tr><tr> + <td class="tdc">112</td> <td class="tdc"> 80.5</td> + <td class="tdc">132</td> <td class="tdc"> 95.3</td> + <td class="tdc">152</td> <td class="tdc">110.3</td> + <td class="tdc">172</td> <td class="tdc">125.5</td> + </tr><tr> + <td class="tdc">113</td> <td class="tdc"> 81.3</td> + <td class="tdc">133</td> <td class="tdc"> 96.1</td> + <td class="tdc">153</td> <td class="tdc">111.1</td> + <td class="tdc">173</td> <td class="tdc">126.2</td> + </tr><tr> + <td class="tdc">114</td> <td class="tdc"> 82.0</td> + <td class="tdc">134</td> <td class="tdc"> 96.9</td> + <td class="tdc">154</td> <td class="tdc">111.9</td> + <td class="tdc">174</td> <td class="tdc">127.0</td> + </tr><tr> + <td class="tdc">115</td> <td class="tdc"> 82.7</td> + <td class="tdc">135</td> <td class="tdc"> 97.6</td> + <td class="tdc">155</td> <td class="tdc">112.6</td> + <td class="tdc">175</td> <td class="tdc">127.8</td> + </tr><tr> + <td class="tdc">116</td> <td class="tdc"> 83.5</td> + <td class="tdc">136</td> <td class="tdc"> 98.3</td> + <td class="tdc">156</td> <td class="tdc">113.4</td> + <td class="tdc">176</td> <td class="tdc">128.5</td> + </tr><tr> + <td class="tdc">117</td> <td class="tdc"> 84.2</td> + <td class="tdc">137</td> <td class="tdc"> 99.1</td> + <td class="tdc">157</td> <td class="tdc">114.1</td> + <td class="tdc">177</td> <td class="tdc">129.3</td> + </tr><tr> + <td class="tdc">118</td> <td class="tdc"> 85.0</td> + <td class="tdc">138</td> <td class="tdc"> 99.8</td> + <td class="tdc">158</td> <td class="tdc">114.9</td> + <td class="tdc">178</td> <td class="tdc">130.1</td> + </tr><tr> + <td class="tdc">119</td> <td class="tdc"> 85.7</td> + <td class="tdc">139</td> <td class="tdc">100.5</td> + <td class="tdc">159</td> <td class="tdc">115.6</td> + <td class="tdc">179</td> <td class="tdc">130.8</td> + </tr><tr> + <td class="tdc" colspan="8"> <span class="pagenum"><a id="Page_164"></a>[Pg 164]</span></td> + </tr><tr class="f110"> + <td class="tdc"> <b>(A)</b> </td> <td class="tdc"> <b>(B)</b> </td> + <td class="tdc"> <b>(A)</b> </td> <td class="tdc"> <b>(B)</b> </td> + <td class="tdc"> <b>(A)</b> </td> <td class="tdc"> <b>(B)</b> </td> + <td class="tdc"> <b>(A)</b> </td> <td class="tdc"> <b>(B)</b> </td> + </tr><tr> + <td class="tdc">180</td> <td class="tdc">131.6</td> + <td class="tdc">223</td> <td class="tdc">164.2</td> + <td class="tdc">266</td> <td class="tdc">197.2</td> + <td class="tdc">309</td> <td class="tdc">231.4</td> + </tr><tr> + <td class="tdc">181</td> <td class="tdc">132.4</td> + <td class="tdc">224</td> <td class="tdc">164.9</td> + <td class="tdc">267</td> <td class="tdc">198.0</td> + <td class="tdc">310</td> <td class="tdc">232.2</td> + </tr><tr> + <td class="tdc">182</td> <td class="tdc">133.1</td> + <td class="tdc">225</td> <td class="tdc">165.7</td> + <td class="tdc">268</td> <td class="tdc">198.8</td> + <td class="tdc">311</td> <td class="tdc">232.9</td> + </tr><tr> + <td class="tdc">183</td> <td class="tdc">133.9</td> + <td class="tdc">226</td> <td class="tdc">166.4</td> + <td class="tdc">269</td> <td class="tdc">199.5</td> + <td class="tdc">312</td> <td class="tdc">233.7</td> + </tr><tr> + <td class="tdc">184</td> <td class="tdc">134.7</td> + <td class="tdc">227</td> <td class="tdc">167.2</td> + <td class="tdc">270</td> <td class="tdc">200.3</td> + <td class="tdc">313</td> <td class="tdc">234.5</td> + </tr><tr> + <td class="tdc">185</td> <td class="tdc">135.4</td> + <td class="tdc">228</td> <td class="tdc">167.9</td> + <td class="tdc">271</td> <td class="tdc">201.1</td> + <td class="tdc">314</td> <td class="tdc">235.3</td> + </tr><tr> + <td class="tdc">186</td> <td class="tdc">136.2</td> + <td class="tdc">229</td> <td class="tdc">168.6</td> + <td class="tdc">272</td> <td class="tdc">201.9</td> + <td class="tdc">315</td> <td class="tdc">236.1</td> + </tr><tr> + <td class="tdc">187</td> <td class="tdc">137.0</td> + <td class="tdc">230</td> <td class="tdc">169.4</td> + <td class="tdc">273</td> <td class="tdc">202.7</td> + <td class="tdc">316</td> <td class="tdc">236.8</td> + </tr><tr> + <td class="tdc">188</td> <td class="tdc">137.7</td> + <td class="tdc">231</td> <td class="tdc">170.1</td> + <td class="tdc">274</td> <td class="tdc">203.5</td> + <td class="tdc">317</td> <td class="tdc">237.6</td> + </tr><tr> + <td class="tdc">189</td> <td class="tdc">138.5</td> + <td class="tdc">232</td> <td class="tdc">170.9</td> + <td class="tdc">275</td> <td class="tdc">204.3</td> + <td class="tdc">318</td> <td class="tdc">238.4</td> + </tr><tr> + <td class="tdc">190</td> <td class="tdc">139.3</td> + <td class="tdc">233</td> <td class="tdc">171.6</td> + <td class="tdc">276</td> <td class="tdc">205.1</td> + <td class="tdc">319</td> <td class="tdc">239.2</td> + </tr><tr> + <td class="tdc">191</td> <td class="tdc">140.0</td> + <td class="tdc">234</td> <td class="tdc">172.4</td> + <td class="tdc">277</td> <td class="tdc">205.9</td> + <td class="tdc">320</td> <td class="tdc">240.0</td> + </tr><tr> + <td class="tdc">192</td> <td class="tdc">140.8</td> + <td class="tdc">235</td> <td class="tdc">173.1</td> + <td class="tdc">278</td> <td class="tdc">206.7</td> + <td class="tdc">321</td> <td class="tdc">240.7</td> + </tr><tr> + <td class="tdc">193</td> <td class="tdc">141.6</td> + <td class="tdc">236</td> <td class="tdc">173.9</td> + <td class="tdc">279</td> <td class="tdc">207.5</td> + <td class="tdc">322</td> <td class="tdc">241.5</td> + </tr><tr> + <td class="tdc">194</td> <td class="tdc">142.3</td> + <td class="tdc">237</td> <td class="tdc">174.6</td> + <td class="tdc">280</td> <td class="tdc">208.3</td> + <td class="tdc">323</td> <td class="tdc">242.3</td> + </tr><tr> + <td class="tdc">195</td> <td class="tdc">143.1</td> + <td class="tdc">238</td> <td class="tdc">175.4</td> + <td class="tdc">281</td> <td class="tdc">209.1</td> + <td class="tdc">324</td> <td class="tdc">243.1</td> + </tr><tr> + <td class="tdc">196</td> <td class="tdc">143.9</td> + <td class="tdc">239</td> <td class="tdc">176.2</td> + <td class="tdc">282</td> <td class="tdc">209.9</td> + <td class="tdc">325</td> <td class="tdc">243.9</td> + </tr><tr> + <td class="tdc">197</td> <td class="tdc">144.6</td> + <td class="tdc">240</td> <td class="tdc">176.9</td> + <td class="tdc">283</td> <td class="tdc">210.7</td> + <td class="tdc">326</td> <td class="tdc">244.6</td> + </tr><tr> + <td class="tdc">198</td> <td class="tdc">145.4</td> + <td class="tdc">241</td> <td class="tdc">177.7</td> + <td class="tdc">284</td> <td class="tdc">211.5</td> + <td class="tdc">327</td> <td class="tdc">245.4</td> + </tr><tr class="bb"> + <td class="tdc">199</td> <td class="tdc">146.2</td> + <td class="tdc">242</td> <td class="tdc">178.5</td> + <td class="tdc">285</td> <td class="tdc">212.3</td> + <td class="tdc">328</td> <td class="tdc">246.2</td> + </tr><tr> + <td class="tdc">200</td> <td class="tdc">146.9</td> + <td class="tdc">243</td> <td class="tdc">179.3</td> + <td class="tdc">286</td> <td class="tdc">213.1</td> + <td class="tdc">329</td> <td class="tdc">247.0</td> + </tr><tr> + <td class="tdc">201</td> <td class="tdc">147.7</td> + <td class="tdc">244</td> <td class="tdc">180.1</td> + <td class="tdc">287</td> <td class="tdc">213.9</td> + <td class="tdc">330</td> <td class="tdc">247.7</td> + </tr><tr> + <td class="tdc">202</td> <td class="tdc">148.5</td> + <td class="tdc">245</td> <td class="tdc">180.8</td> + <td class="tdc">288</td> <td class="tdc">214.7</td> + <td class="tdc">331</td> <td class="tdc">248.5</td> + </tr><tr> + <td class="tdc">203</td> <td class="tdc">149.2</td> + <td class="tdc">246</td> <td class="tdc">181.6</td> + <td class="tdc">289</td> <td class="tdc">215.5</td> + <td class="tdc">332</td> <td class="tdc">249.2</td> + </tr><tr> + <td class="tdc">204</td> <td class="tdc">150.0</td> + <td class="tdc">247</td> <td class="tdc">182.4</td> + <td class="tdc">290</td> <td class="tdc">216.3</td> + <td class="tdc">333</td> <td class="tdc">250.0</td> + </tr><tr> + <td class="tdc">205</td> <td class="tdc">150.7</td> + <td class="tdc">248</td> <td class="tdc">183.2</td> + <td class="tdc">291</td> <td class="tdc">217.1</td> + <td class="tdc">334</td> <td class="tdc">250.8</td> + </tr><tr> + <td class="tdc">206</td> <td class="tdc">151.5</td> + <td class="tdc">249</td> <td class="tdc">184.0</td> + <td class="tdc">292</td> <td class="tdc">217.9</td> + <td class="tdc">335</td> <td class="tdc">251.6</td> + </tr><tr> + <td class="tdc">207</td> <td class="tdc">152.2</td> + <td class="tdc">250</td> <td class="tdc">184.8</td> + <td class="tdc">293</td> <td class="tdc">218.7</td> + <td class="tdc">336</td> <td class="tdc">252.5</td> + </tr><tr> + <td class="tdc">208</td> <td class="tdc">153.0</td> + <td class="tdc">251</td> <td class="tdc">185.5</td> + <td class="tdc">294</td> <td class="tdc">219.5</td> + <td class="tdc">337</td> <td class="tdc">253.3</td> + </tr><tr> + <td class="tdc">209</td> <td class="tdc">153.7</td> + <td class="tdc">252</td> <td class="tdc">186.3</td> + <td class="tdc">295</td> <td class="tdc">220.3</td> + <td class="tdc">338</td> <td class="tdc">254.1</td> + </tr><tr> + <td class="tdc">210</td> <td class="tdc">154.5</td> + <td class="tdc">253</td> <td class="tdc">187.1</td> + <td class="tdc">296</td> <td class="tdc">221.1</td> + <td class="tdc">339</td> <td class="tdc">254.9</td> + </tr><tr> + <td class="tdc">211</td> <td class="tdc">155.2</td> + <td class="tdc">254</td> <td class="tdc">187.9</td> + <td class="tdc">297</td> <td class="tdc">221.9</td> + <td class="tdc">340</td> <td class="tdc">255.7</td> + </tr><tr> + <td class="tdc">212</td> <td class="tdc">156.0</td> + <td class="tdc">255</td> <td class="tdc">188.7</td> + <td class="tdc">298</td> <td class="tdc">222.7</td> + <td class="tdc">341</td> <td class="tdc">256.5</td> + </tr><tr> + <td class="tdc">213</td> <td class="tdc">156.7</td> + <td class="tdc">256</td> <td class="tdc">189.4</td> + <td class="tdc">299</td> <td class="tdc">223.5</td> + <td class="tdc">342</td> <td class="tdc">257.4</td> + </tr><tr> + <td class="tdc">214</td> <td class="tdc">157.5</td> + <td class="tdc">257</td> <td class="tdc">190.2</td> + <td class="tdc">300</td> <td class="tdc">224.4</td> + <td class="tdc">343</td> <td class="tdc">258.2</td> + </tr><tr> + <td class="tdc">215</td> <td class="tdc">158.2</td> + <td class="tdc">258</td> <td class="tdc">191.0</td> + <td class="tdc">301</td> <td class="tdc">225.2</td> + <td class="tdc">344</td> <td class="tdc">259.0</td> + </tr><tr> + <td class="tdc">216</td> <td class="tdc">159.0</td> + <td class="tdc">259</td> <td class="tdc">191.8</td> + <td class="tdc">302</td> <td class="tdc">225.9</td> + <td class="tdc">345</td> <td class="tdc">259.8</td> + </tr><tr> + <td class="tdc">217</td> <td class="tdc">159.7</td> + <td class="tdc">260</td> <td class="tdc">192.5</td> + <td class="tdc">303</td> <td class="tdc">226.7</td> + <td class="tdc">346</td> <td class="tdc">260.6</td> + </tr><tr> + <td class="tdc">218</td> <td class="tdc">160.4</td> + <td class="tdc">261</td> <td class="tdc">193.3</td> + <td class="tdc">304</td> <td class="tdc">227.5</td> + <td class="tdc">347</td> <td class="tdc">261.4</td> + </tr><tr> + <td class="tdc">219</td> <td class="tdc">161.2</td> + <td class="tdc">262</td> <td class="tdc">194.1</td> + <td class="tdc">305</td> <td class="tdc">228.3</td> + <td class="tdc">348</td> <td class="tdc">262.3</td> + </tr><tr> + <td class="tdc">220</td> <td class="tdc">161.9</td> + <td class="tdc">263</td> <td class="tdc">194.9</td> + <td class="tdc">306</td> <td class="tdc">229.1</td> + <td class="tdc">349</td> <td class="tdc">263.1</td> + </tr><tr> + <td class="tdc">221</td> <td class="tdc">162.7</td> + <td class="tdc">264</td> <td class="tdc">195.7</td> + <td class="tdc">307</td> <td class="tdc">229.8</td> + <td class="tdc">350</td> <td class="tdc">263.9</td> + </tr><tr> + <td class="tdc">222</td> <td class="tdc">163.4</td> + <td class="tdc">265</td> <td class="tdc">196.4</td> + <td class="tdc">308</td> <td class="tdc">230.6</td> + <td class="tdc">351</td> <td class="tdc">264.7</td> + </tr><tr> + <td class="tdc" colspan="8"> <span class="pagenum"><a id="Page_165"></a>[Pg 165]</span></td> + </tr><tr class="f110"> + <td class="tdc"> <b>(A)</b> </td> <td class="tdc"> <b>(B)</b> </td> + <td class="tdc"> <b>(A)</b> </td> <td class="tdc"> <b>(B)</b> </td> + <td class="tdc"> <b>(A)</b> </td> <td class="tdc"> <b>(B)</b> </td> + <td class="tdc"> <b>(A)</b> </td> <td class="tdc"> <b>(B)</b> </td> + </tr><tr> + <td class="tdc">352</td> <td class="tdc">265.5</td> + <td class="tdc">365</td> <td class="tdc">276.2</td> + <td class="tdc">377</td> <td class="tdc">286.5</td> + <td class="tdc">389</td> <td class="tdc">296.8</td> + </tr><tr> + <td class="tdc">353</td> <td class="tdc">266.3</td> + <td class="tdc">366</td> <td class="tdc">277.1</td> + <td class="tdc">378</td> <td class="tdc">287.4</td> + <td class="tdc">390</td> <td class="tdc">297.7</td> + </tr><tr> + <td class="tdc">354</td> <td class="tdc">267.2</td> + <td class="tdc">367</td> <td class="tdc">277.9</td> + <td class="tdc">379</td> <td class="tdc">288.2</td> + <td class="tdc">391</td> <td class="tdc">298.5</td> + </tr><tr> + <td class="tdc">355</td> <td class="tdc">268.0</td> + <td class="tdc">368</td> <td class="tdc">278.8</td> + <td class="tdc">380</td> <td class="tdc">289.1</td> + <td class="tdc">392</td> <td class="tdc">299.4</td> + </tr><tr> + <td class="tdc">356</td> <td class="tdc">268.8</td> + <td class="tdc">369</td> <td class="tdc">279.6</td> + <td class="tdc">381</td> <td class="tdc">289.9</td> + <td class="tdc">393</td> <td class="tdc">300.3</td> + </tr><tr> + <td class="tdc">357</td> <td class="tdc">269.6</td> + <td class="tdc">370</td> <td class="tdc">280.5</td> + <td class="tdc">382</td> <td class="tdc">290.8</td> + <td class="tdc">394</td> <td class="tdc">301.1</td> + </tr><tr> + <td class="tdc">358</td> <td class="tdc">270.4</td> + <td class="tdc">371</td> <td class="tdc">281.4</td> + <td class="tdc">383</td> <td class="tdc">291.7</td> + <td class="tdc">395</td> <td class="tdc">302.0</td> + </tr><tr> + <td class="tdc">359</td> <td class="tdc">271.2</td> + <td class="tdc">372</td> <td class="tdc">282.2</td> + <td class="tdc">384</td> <td class="tdc">292.5</td> + <td class="tdc">396</td> <td class="tdc">302.8</td> + </tr><tr> + <td class="tdc">360</td> <td class="tdc">272.1</td> + <td class="tdc">373</td> <td class="tdc">283.1</td> + <td class="tdc">385</td> <td class="tdc">293.4</td> + <td class="tdc">397</td> <td class="tdc">303.7</td> + </tr><tr> + <td class="tdc">361</td> <td class="tdc">272.9</td> + <td class="tdc">374</td> <td class="tdc">283.9</td> + <td class="tdc">386</td> <td class="tdc">294.2</td> + <td class="tdc">398</td> <td class="tdc">304.6</td> + </tr><tr> + <td class="tdc">362</td> <td class="tdc">273.7</td> + <td class="tdc">375</td> <td class="tdc">284.8</td> + <td class="tdc">387</td> <td class="tdc">295.1</td> + <td class="tdc">399</td> <td class="tdc">305.4</td> + </tr><tr> + <td class="tdc">363</td> <td class="tdc">274.5</td> + <td class="tdc">376</td> <td class="tdc">285.7</td> + <td class="tdc">388</td> <td class="tdc">296.0</td> + <td class="tdc">400</td> <td class="tdc">306.3</td> + </tr><tr> + <td class="tdc bb">364</td> <td class="tdc bb">275.3</td> + <td class="tdc bb" colspan="6"> </td> + </tr> + </tbody> +</table> + +<p><b>144. Table for the Determination of Maltose.</b>—The copper and +alkaline solutions employed for the oxidation of maltose are the same +as those used for invert and milk sugars.</p> + +<p>In the manipulation twenty-five cubic centimeters each of the copper +and alkali solutions are mixed and boiled and an equal volume of the +maltose solution added, which should not contain more than one per +cent of the sugar. The boiling is continued for four minutes, an equal +volume of cold recently boiled water added, the cuprous oxid separated +by filtration and the metallic copper obtained in the manner already +described. The weight of maltose oxidized is then ascertained from the table.</p> + +<ul class="index"> +<li class="isub2"><i>Example.</i> Weight of impure maltose taken, ten grams to a liter:</li> +<li class="isub6">Quantity used, twenty-five cubic centimeters:</li> +<li class="isub6">Weight of copper obtained 268 milligrams:</li> +<li class="isub6">Weight of maltose oxidized 237 milligrams:</li> +<li class="isub6">Weight of impure maltose taken 250 milligrams:</li> +<li class="isub6">Percentage of maltose in sample 94.8.</li> +</ul> + +<p class="f120 spa1"><b><span class="smcap">Table for Maltose.</span></b></p> + +<ul class="index fs_110"> +<li class="isub3"><b>(A)</b> = Milligrams of copper.</li> +<li class="isub3"><b>(B)</b> = Milligrams of maltose.</li> +</ul> + +<table class="spb1"> + <thead><tr class="fs_110"> + <th class="tdc"> (A) </th> <th class="tdc"> (B) </th> + <th class="tdc"> (A) </th> <th class="tdc"> (B) </th> + <th class="tdc"> (A) </th> <th class="tdc"> (B) </th> + <th class="tdc"> (A) </th> <th class="tdc"> (B) </th> + </tr></thead> + <tbody><tr> + <td class="tdc"> 30</td> <td class="tdc"> 25.3</td> + <td class="tdc"> 35</td> <td class="tdc"> 29.6</td> + <td class="tdc"> 40</td> <td class="tdc"> 33.9</td> + <td class="tdc"> 45</td> <td class="tdc"> 38.3</td> + </tr><tr> + <td class="tdc"> 31</td> <td class="tdc"> 26.1</td> + <td class="tdc"> 36</td> <td class="tdc"> 30.5</td> + <td class="tdc"> 41</td> <td class="tdc"> 34.8</td> + <td class="tdc"> 46</td> <td class="tdc"> 39.1</td> + </tr><tr> + <td class="tdc"> 32</td> <td class="tdc"> 27.0</td> + <td class="tdc"> 37</td> <td class="tdc"> 31.3</td> + <td class="tdc"> 42</td> <td class="tdc"> 35.7</td> + <td class="tdc"> 47</td> <td class="tdc"> 40.0</td> + </tr><tr> + <td class="tdc"> 33</td> <td class="tdc"> 27.9</td> + <td class="tdc"> 38</td> <td class="tdc"> 32.2</td> + <td class="tdc"> 43</td> <td class="tdc"> 36.5</td> + <td class="tdc"> 48</td> <td class="tdc"> 40.9</td> + </tr><tr> + <td class="tdc"> 34</td> <td class="tdc"> 28.7</td> + <td class="tdc"> 39</td> <td class="tdc"> 33.1</td> + <td class="tdc"> 44</td> <td class="tdc"> 37.4</td> + <td class="tdc"> 49</td> <td class="tdc"> 41.8</td> + </tr><tr> + <td class="tdc" colspan="8"> <span class="pagenum"><a id="Page_166"></a>[Pg 166]</span></td> + </tr><tr class="f110"> + <td class="tdc"> <b>(A)</b> </td> <td class="tdc"> <b>(B)</b> </td> + <td class="tdc"> <b>(A)</b> </td> <td class="tdc"> <b>(B)</b> </td> + <td class="tdc"> <b>(A)</b> </td> <td class="tdc"> <b>(B)</b> </td> + <td class="tdc"> <b>(A)</b> </td> <td class="tdc"> <b>(B)</b> </td> + </tr><tr> + <td class="tdc"> 50</td> <td class="tdc"> 42.6</td> + <td class="tdc"> 94</td> <td class="tdc"> 81.2</td> + <td class="tdc">138</td> <td class="tdc">120.6</td> + <td class="tdc">182</td> <td class="tdc">160.1</td> + </tr><tr> + <td class="tdc"> 51</td> <td class="tdc"> 43.5</td> + <td class="tdc"> 95</td> <td class="tdc"> 82.1</td> + <td class="tdc">139</td> <td class="tdc">121.5</td> + <td class="tdc">183</td> <td class="tdc">160.9</td> + </tr><tr> + <td class="tdc"> 52</td> <td class="tdc"> 44.4</td> + <td class="tdc"> 96</td> <td class="tdc"> 83.0</td> + <td class="tdc">140</td> <td class="tdc">122.4</td> + <td class="tdc">184</td> <td class="tdc">161.8</td> + </tr><tr> + <td class="tdc"> 53</td> <td class="tdc"> 45.2</td> + <td class="tdc"> 97</td> <td class="tdc"> 83.9</td> + <td class="tdc">141</td> <td class="tdc">123.3</td> + <td class="tdc">185</td> <td class="tdc">162.7</td> + </tr><tr> + <td class="tdc"> 54</td> <td class="tdc"> 46.1</td> + <td class="tdc"> 98</td> <td class="tdc"> 84.8</td> + <td class="tdc">142</td> <td class="tdc">124.2</td> + <td class="tdc">186</td> <td class="tdc">163.6</td> + </tr><tr> + <td class="tdc"> 55</td> <td class="tdc"> 47.0</td> + <td class="tdc"> 99</td> <td class="tdc"> 85.7</td> + <td class="tdc">143</td> <td class="tdc">125.1</td> + <td class="tdc">187</td> <td class="tdc">164.5</td> + </tr><tr> + <td class="tdc"> 56</td> <td class="tdc"> 47.8</td> + <td class="tdc">100</td> <td class="tdc"> 86.6</td> + <td class="tdc">144</td> <td class="tdc">126.0</td> + <td class="tdc">188</td> <td class="tdc">165.4</td> + </tr><tr> + <td class="tdc"> 57</td> <td class="tdc"> 48.7</td> + <td class="tdc">101</td> <td class="tdc"> 87.5</td> + <td class="tdc">145</td> <td class="tdc">126.9</td> + <td class="tdc">189</td> <td class="tdc">166.3</td> + </tr><tr> + <td class="tdc"> 58</td> <td class="tdc"> 49.6</td> + <td class="tdc">102</td> <td class="tdc"> 88.4</td> + <td class="tdc">146</td> <td class="tdc">127.8</td> + <td class="tdc">190</td> <td class="tdc">167.2</td> + </tr><tr class="bb"> + <td class="tdc"> 59</td> <td class="tdc"> 50.4</td> + <td class="tdc">103</td> <td class="tdc"> 89.2</td> + <td class="tdc">147</td> <td class="tdc">128.7</td> + <td class="tdc">191</td> <td class="tdc">168.1</td> + </tr><tr> + <td class="tdc"> 60</td> <td class="tdc"> 51.3</td> + <td class="tdc">104</td> <td class="tdc"> 90.1</td> + <td class="tdc">148</td> <td class="tdc">129.6 </td> + <td class="tdc">192</td> <td class="tdc">169.0</td> + </tr><tr> + <td class="tdc"> 61</td> <td class="tdc"> 52.2</td> + <td class="tdc">105</td> <td class="tdc"> 91.0</td> + <td class="tdc">149</td> <td class="tdc">130.5</td> + <td class="tdc">193</td> <td class="tdc">169.8</td> + </tr><tr> + <td class="tdc"> 62</td> <td class="tdc"> 53.1</td> + <td class="tdc">106</td> <td class="tdc"> 91.9</td> + <td class="tdc">150</td> <td class="tdc">131.4</td> + <td class="tdc">194</td> <td class="tdc">170.7</td> + </tr><tr> + <td class="tdc"> 63</td> <td class="tdc"> 53.9</td> + <td class="tdc">107</td> <td class="tdc"> 92.8</td> + <td class="tdc">151</td> <td class="tdc">132.3</td> + <td class="tdc">195</td> <td class="tdc">171.6</td> + </tr><tr> + <td class="tdc"> 64</td> <td class="tdc"> 54.8</td> + <td class="tdc">108</td> <td class="tdc"> 93.7</td> + <td class="tdc">152</td> <td class="tdc">133.2</td> + <td class="tdc">196</td> <td class="tdc">172.5</td> + </tr><tr> + <td class="tdc"> 65</td> <td class="tdc"> 55.7</td> + <td class="tdc">109</td> <td class="tdc"> 94.6</td> + <td class="tdc">153</td> <td class="tdc">134.1</td> + <td class="tdc">197</td> <td class="tdc">173.4</td> + </tr><tr> + <td class="tdc"> 66</td> <td class="tdc"> 56.6</td> + <td class="tdc">110</td> <td class="tdc"> 95.5</td> + <td class="tdc">154</td> <td class="tdc">135.0</td> + <td class="tdc">198</td> <td class="tdc">174.3</td> + </tr><tr> + <td class="tdc"> 67</td> <td class="tdc"> 57.4</td> + <td class="tdc">111</td> <td class="tdc"> 96.4</td> + <td class="tdc">155</td> <td class="tdc">135.9</td> + <td class="tdc">199</td> <td class="tdc">175.2</td> + </tr><tr> + <td class="tdc"> 68</td> <td class="tdc"> 58.3</td> + <td class="tdc">112</td> <td class="tdc"> 97.3</td> + <td class="tdc">156</td> <td class="tdc">136.8</td> + <td class="tdc">200</td> <td class="tdc">176.1</td> + </tr><tr> + <td class="tdc"> 69</td> <td class="tdc"> 59.2</td> + <td class="tdc">113</td> <td class="tdc"> 98.1</td> + <td class="tdc">157</td> <td class="tdc">137.7</td> + <td class="tdc">201</td> <td class="tdc">177.0</td> + </tr><tr> + <td class="tdc"> 70</td> <td class="tdc"> 60.1</td> + <td class="tdc">114</td> <td class="tdc"> 99.0</td> + <td class="tdc">158</td> <td class="tdc">138.6</td> + <td class="tdc">202</td> <td class="tdc">177.9</td> + </tr><tr> + <td class="tdc"> 71</td> <td class="tdc"> 61.0</td> + <td class="tdc">115</td> <td class="tdc"> 99.9</td> + <td class="tdc">159</td> <td class="tdc">139.5</td> + <td class="tdc">203</td> <td class="tdc">178.7</td> + </tr><tr> + <td class="tdc"> 72</td> <td class="tdc"> 61.8</td> + <td class="tdc">116</td> <td class="tdc">100.8</td> + <td class="tdc">160</td> <td class="tdc">140.4</td> + <td class="tdc">204</td> <td class="tdc">179.6</td> + </tr><tr> + <td class="tdc"> 73</td> <td class="tdc"> 62.7</td> + <td class="tdc">117</td> <td class="tdc">101.7</td> + <td class="tdc">161</td> <td class="tdc">141.3</td> + <td class="tdc">205</td> <td class="tdc">180.5</td> + </tr><tr> + <td class="tdc"> 74</td> <td class="tdc"> 63.6</td> + <td class="tdc">118</td> <td class="tdc">102.6</td> + <td class="tdc">162</td> <td class="tdc">142.2</td> + <td class="tdc">206</td> <td class="tdc">181.4</td> + </tr><tr> + <td class="tdc"> 75</td> <td class="tdc"> 64.5</td> + <td class="tdc">119</td> <td class="tdc">103.5</td> + <td class="tdc">163</td> <td class="tdc">143.1</td> + <td class="tdc">207</td> <td class="tdc">182.3</td> + </tr><tr> + <td class="tdc"> 76</td> <td class="tdc"> 65.4</td> + <td class="tdc">120</td> <td class="tdc">104.4</td> + <td class="tdc">164</td> <td class="tdc">144.0</td> + <td class="tdc">208</td> <td class="tdc">183.2</td> + </tr><tr> + <td class="tdc"> 77</td> <td class="tdc"> 66.2</td> + <td class="tdc">121</td> <td class="tdc">105.3</td> + <td class="tdc">165</td> <td class="tdc">144.9</td> + <td class="tdc">209</td> <td class="tdc">184.1</td> + </tr><tr> + <td class="tdc"> 78</td> <td class="tdc"> 67.1</td> + <td class="tdc">122</td> <td class="tdc">106.2</td> + <td class="tdc">166</td> <td class="tdc">145.8</td> + <td class="tdc">210</td> <td class="tdc">185.0</td> + </tr><tr class="bb"> + <td class="tdc"> 79</td> <td class="tdc"> 68.0</td> + <td class="tdc">123</td> <td class="tdc">107.1</td> + <td class="tdc">167</td> <td class="tdc">146.7</td> + <td class="tdc">211</td> <td class="tdc">185.9</td> + </tr><tr> + <td class="tdc"> 80</td> <td class="tdc"> 68.9</td> + <td class="tdc">124</td> <td class="tdc">108.0</td> + <td class="tdc">168</td> <td class="tdc">147.6</td> + <td class="tdc">212</td> <td class="tdc">186.8</td> + </tr><tr> + <td class="tdc"> 81</td> <td class="tdc"> 69.7</td> + <td class="tdc">125</td> <td class="tdc">108.9</td> + <td class="tdc">169</td> <td class="tdc">148.5</td> + <td class="tdc">213</td> <td class="tdc">187.7</td> + </tr><tr> + <td class="tdc"> 82</td> <td class="tdc"> 70.6</td> + <td class="tdc">126</td> <td class="tdc">109.8</td> + <td class="tdc">170</td> <td class="tdc">149.4</td> + <td class="tdc">214</td> <td class="tdc">188.6</td> + </tr><tr> + <td class="tdc"> 83</td> <td class="tdc"> 71.5</td> + <td class="tdc">127</td> <td class="tdc">110.7</td> + <td class="tdc">171</td> <td class="tdc">150.3</td> + <td class="tdc">215</td> <td class="tdc">189.5</td> + </tr><tr> + <td class="tdc"> 84</td> <td class="tdc"> 72.4</td> + <td class="tdc">128</td> <td class="tdc">111.6</td> + <td class="tdc">172</td> <td class="tdc">151.2</td> + <td class="tdc">216</td> <td class="tdc">190.4</td> + </tr><tr> + <td class="tdc"> 85</td> <td class="tdc"> 73.2</td> + <td class="tdc">129</td> <td class="tdc">112.5</td> + <td class="tdc">173</td> <td class="tdc">152.0</td> + <td class="tdc">217</td> <td class="tdc">191.2</td> + </tr><tr> + <td class="tdc"> 86</td> <td class="tdc"> 74.1</td> + <td class="tdc">130</td> <td class="tdc">113.4</td> + <td class="tdc">174</td> <td class="tdc">152.9</td> + <td class="tdc">218</td> <td class="tdc">192.1</td> + </tr><tr> + <td class="tdc"> 87</td> <td class="tdc"> 75.0</td> + <td class="tdc">131</td> <td class="tdc">114.3</td> + <td class="tdc">175</td> <td class="tdc">153.8</td> + <td class="tdc">219</td> <td class="tdc">193.0</td> + </tr><tr> + <td class="tdc"> 88</td> <td class="tdc"> 75.9</td> + <td class="tdc">132</td> <td class="tdc">115.2</td> + <td class="tdc">176</td> <td class="tdc">154.7</td> + <td class="tdc">220</td> <td class="tdc">193.9</td> + </tr><tr> + <td class="tdc"> 89</td> <td class="tdc"> 76.8</td> + <td class="tdc">133</td> <td class="tdc">116.1</td> + <td class="tdc">177</td> <td class="tdc">155.6</td> + <td class="tdc">221</td> <td class="tdc">194.8</td> + </tr><tr> + <td class="tdc"> 90</td> <td class="tdc"> 77.7</td> + <td class="tdc">134</td> <td class="tdc">117.0</td> + <td class="tdc">178</td> <td class="tdc">156.5</td> + <td class="tdc">222</td> <td class="tdc">195.7</td> + </tr><tr> + <td class="tdc"> 91</td> <td class="tdc"> 78.6</td> + <td class="tdc">135</td> <td class="tdc">117.9</td> + <td class="tdc">179</td> <td class="tdc">157.4</td> + <td class="tdc">223</td> <td class="tdc">196.6</td> + </tr><tr> + <td class="tdc"> 92</td> <td class="tdc"> 79.5</td> + <td class="tdc">136</td> <td class="tdc">118.8</td> + <td class="tdc">180</td> <td class="tdc">158.3</td> + <td class="tdc">224</td> <td class="tdc">197.5</td> + </tr><tr> + <td class="tdc"> 93</td> <td class="tdc"> 80.3</td> + <td class="tdc">137</td> <td class="tdc">119.7</td> + <td class="tdc">181</td> <td class="tdc">159.2</td> + <td class="tdc">225</td> <td class="tdc">198.4</td> + </tr><tr> + <td class="tdc" colspan="8"> <span class="pagenum"><a id="Page_167"></a>[Pg 167]</span></td> + </tr><tr class="f110"> + <td class="tdc"> <b>(A)</b> </td> <td class="tdc"> <b>(B)</b> </td> + <td class="tdc"> <b>(A)</b> </td> <td class="tdc"> <b>(B)</b> </td> + <td class="tdc"> <b>(A)</b> </td> <td class="tdc"> <b>(B)</b> </td> + <td class="tdc"> <b>(A)</b> </td> <td class="tdc"> <b>(B)</b> </td> + </tr><tr> + <td class="tdc">226</td> <td class="tdc">199.3</td> + <td class="tdc">245</td> <td class="tdc">216.3</td> + <td class="tdc">264</td> <td class="tdc">233.4</td> + <td class="tdc">283</td> <td class="tdc">250.4</td> + </tr><tr> + <td class="tdc">227</td> <td class="tdc">200.2</td> + <td class="tdc">246</td> <td class="tdc">217.2</td> + <td class="tdc">265</td> <td class="tdc">234.3</td> + <td class="tdc">284</td> <td class="tdc">251.3</td> + </tr><tr> + <td class="tdc">228</td> <td class="tdc">201.1</td> + <td class="tdc">247</td> <td class="tdc">218.1</td> + <td class="tdc">266</td> <td class="tdc">235.2</td> + <td class="tdc">285</td> <td class="tdc">252.2</td> + </tr><tr> + <td class="tdc">229</td> <td class="tdc">202.0</td> + <td class="tdc">248</td> <td class="tdc">219.0</td> + <td class="tdc">267</td> <td class="tdc">236.1</td> + <td class="tdc">286</td> <td class="tdc">253.1</td> + </tr><tr> + <td class="tdc">230</td> <td class="tdc">202.9</td> + <td class="tdc">249</td> <td class="tdc">219.9</td> + <td class="tdc">268</td> <td class="tdc">237.0</td> + <td class="tdc">287</td> <td class="tdc">254.0</td> + </tr><tr> + <td class="tdc">231</td> <td class="tdc">203.8</td> + <td class="tdc">250</td> <td class="tdc">220.8</td> + <td class="tdc">269</td> <td class="tdc">237.9</td> + <td class="tdc">288</td> <td class="tdc">254.9</td> + </tr><tr> + <td class="tdc">232</td> <td class="tdc">204.7</td> + <td class="tdc">251</td> <td class="tdc">221.7</td> + <td class="tdc">270</td> <td class="tdc">238.8</td> + <td class="tdc">289</td> <td class="tdc">255.8</td> + </tr><tr> + <td class="tdc">233</td> <td class="tdc">205.6</td> + <td class="tdc">252</td> <td class="tdc">222.6</td> + <td class="tdc">271</td> <td class="tdc">239.7</td> + <td class="tdc">290</td> <td class="tdc">256.6</td> + </tr><tr> + <td class="tdc">234</td> <td class="tdc">206.5</td> + <td class="tdc">253</td> <td class="tdc">223.5</td> + <td class="tdc">272</td> <td class="tdc">240.6</td> + <td class="tdc">291</td> <td class="tdc">257.5</td> + </tr><tr class="bb"> + <td class="tdc">235</td> <td class="tdc">207.4</td> + <td class="tdc">254</td> <td class="tdc">224.4</td> + <td class="tdc">273</td> <td class="tdc">241.5</td> + <td class="tdc">292</td> <td class="tdc">258.4</td> + </tr><tr> + <td class="tdc">236</td> <td class="tdc">208.3</td> + <td class="tdc">255</td> <td class="tdc">225.3</td> + <td class="tdc">274</td> <td class="tdc">242.4</td> + <td class="tdc">293</td> <td class="tdc">259.3</td> + </tr><tr> + <td class="tdc">237</td> <td class="tdc">209.1</td> + <td class="tdc">256</td> <td class="tdc">226.2</td> + <td class="tdc">275</td> <td class="tdc">243.3</td> + <td class="tdc">294</td> <td class="tdc">260.2</td> + </tr><tr> + <td class="tdc">238</td> <td class="tdc">210.0</td> + <td class="tdc">257</td> <td class="tdc">227.1</td> + <td class="tdc">276</td> <td class="tdc">244.2</td> + <td class="tdc">295</td> <td class="tdc">261.1</td> + </tr><tr> + <td class="tdc">239</td> <td class="tdc">210.9</td> + <td class="tdc">258</td> <td class="tdc">228.0</td> + <td class="tdc">277</td> <td class="tdc">245.1</td> + <td class="tdc">296</td> <td class="tdc">262.0</td> + </tr><tr> + <td class="tdc">240</td> <td class="tdc">211.8</td> + <td class="tdc">259</td> <td class="tdc">228.9</td> + <td class="tdc">278</td> <td class="tdc">246.0</td> + <td class="tdc">297</td> <td class="tdc">262.8</td> + </tr><tr> + <td class="tdc">241</td> <td class="tdc">212.7</td> + <td class="tdc">260</td> <td class="tdc">229.8</td> + <td class="tdc">279</td> <td class="tdc">246.9</td> + <td class="tdc">298</td> <td class="tdc">263.7</td> + </tr><tr> + <td class="tdc">242</td> <td class="tdc">213.6</td> + <td class="tdc">261</td> <td class="tdc">230.7</td> + <td class="tdc">280</td> <td class="tdc">247.8</td> + <td class="tdc">299</td> <td class="tdc">264.6</td> + </tr><tr> + <td class="tdc">243</td> <td class="tdc">214.5</td> + <td class="tdc">262</td> <td class="tdc">231.6</td> + <td class="tdc">281</td> <td class="tdc">248.7</td> + <td class="tdc">300</td> <td class="tdc">265.5</td> + </tr><tr class="bb"> + <td class="tdc">244</td> <td class="tdc">215.4</td> + <td class="tdc">263</td> <td class="tdc">232.5</td> + <td class="tdc">282</td> <td class="tdc">249.6</td> + <td class="tdc"> </td> <td class="tdc"> </td> + </tr> + </tbody> +</table> + +<p><b>145. Preparation of Levulose.</b>—It is not often that +levulose, unmixed with other reducing sugars, is brought to the +attention of the analyst. It probably does not exist in the unmixed +state in any agricultural product. The easiest method of preparing it +is by the hydrolysis of inulin. A nearly pure levulose has also lately +been placed on the market under the name of diabetin. It is prepared +from invert sugar.</p> + +<p>Inulin is prepared from dahlia bulbs by boiling the pulp with water +and a trace of calcium carbonate. The extract is concentrated to +a sirup and subjected to a freezing temperature to promote the +crystallization of the inulin. The separated product is subjected to +the above operations several times until it is pure and colorless. It +is then washed with alcohol and ether and is reduced to a fine powder. +Before the repeated treatment with water it is advisable to clarify +the solution with lead subacetate. The lead is afterwards removed by +hydrogen sulfid and the resultant acetic acid neutralized with calcium +carbonate.</p> + +<p>By the action of hot dilute acids inulin is rapidly converted into +levulose.</p> + +<p>Levulose may also be prepared from invert sugar, but in this case it +<span class="pagenum"><a id="Page_168"></a>[Pg 168]</span> +is difficult to free it from traces of dextrose. The most successful +method consists in forming a lime compound with the invert sugar and +separating the lime levulosate and dextrosate by their difference +in solubility. The levulose salt is much less soluble than the +corresponding compound of dextrose. In the manufacture of levulose +from beet molasses, the latter is dissolved in six times its weight of +water and inverted with a quantity of hydrochloric acid, proportioned +to the quantity of ash present in the sample. After inversion the +mixture is cooled to zero and the levulose precipitated by adding +fine-ground lime. The dextrose and coloring matters in these conditions +are not thrown down. The precipitated lime levulosate is separated by +filtration and washed with ice-cold water. The lime salt is afterwards +beaten to a cream with water and decomposed by carbon dioxid. The +levulose, after filtration, is concentrated to the crystallizing +point.<a id="FNanchor_110" href="#Footnote_110" class="fnanchor">[110]</a></p> + +<p><b>146. Estimation of Levulose.</b>—Levulose, when free of any +admixture with other reducing sugars, may be determined by the copper +method with the use of the subjoined table, prepared by Lehmann.<a id="FNanchor_111" href="#Footnote_111" class="fnanchor">[111]</a> +The copper solution is the same as that used for invert sugar, +<i>viz.</i>, 69.278 grams of pure copper sulfate in one liter. The +alkali solution is prepared by dissolving 346 grams of rochelle salt +and 250 grams of sodium hydroxid in water and completing the volume to +one liter.</p> + +<p><i>Manipulation.</i>—Twenty-five cubic centimeters of each solution +are mixed with fifty of water and boiled. To the boiling mixture +twenty-five cubic centimeters of the levulose solution are added, which +must not contain more than one per cent of the sugar. The boiling is +then continued for fifteen minutes, and the cuprous oxid collected, +washed and reduced to the metallic state in the usual way. The quantity +of levulose is then determined by inspection from the table given +below. Other methods of determining levulose in mixtures will be given +further on. +<span class="pagenum"><a id="Page_169"></a>[Pg 169]</span></p> + +<p class="f120 spa1"><b><span class="smcap">Table for the Estimation of Levulose.</span></b></p> + +<ul class="index fs_110"> +<li class="isub3"><b>(A)</b> = Milligrams of copper.</li> +<li class="isub3"><b>(B)</b> = Milligrams of levulose.</li> +</ul> + +<table class="spb1"> + <thead><tr class="fs_110"> + <th class="tdc"> (A) </th> <th class="tdc"> (B) </th> + <th class="tdc"> (A) </th> <th class="tdc"> (B) </th> + <th class="tdc"> (A) </th> <th class="tdc"> (B) </th> + <th class="tdc"> (A) </th> <th class="tdc"> (B) </th> + </tr></thead> + <tbody><tr> + <td class="tdc"> 20</td> <td class="tdc">  7.15</td> + <td class="tdc"> 62</td> <td class="tdc"> 31.66</td> + <td class="tdc">104</td> <td class="tdc"> 56.85</td> + <td class="tdc">146</td> <td class="tdc"> 82.81</td> + </tr><tr> + <td class="tdc"> 21</td> <td class="tdc">  7.78</td> + <td class="tdc"> 63</td> <td class="tdc"> 32.25</td> + <td class="tdc">105</td> <td class="tdc"> 57.46</td> + <td class="tdc">147</td> <td class="tdc"> 83.43</td> + </tr><tr> + <td class="tdc"> 22</td> <td class="tdc">  8.41</td> + <td class="tdc"> 64</td> <td class="tdc"> 32.84</td> + <td class="tdc">106</td> <td class="tdc"> 58.07</td> + <td class="tdc">148</td> <td class="tdc"> 84.06</td> + </tr><tr> + <td class="tdc"> 23</td> <td class="tdc">  9.04</td> + <td class="tdc"> 65</td> <td class="tdc"> 33.43</td> + <td class="tdc">107</td> <td class="tdc"> 58.68</td> + <td class="tdc">149</td> <td class="tdc"> 84.68</td> + </tr><tr> + <td class="tdc"> 24</td> <td class="tdc">  9.67</td> + <td class="tdc"> 66</td> <td class="tdc"> 34.02</td> + <td class="tdc">108</td> <td class="tdc"> 59.30</td> + <td class="tdc">150</td> <td class="tdc"> 85.31</td> + </tr><tr> + <td class="tdc"> 25</td> <td class="tdc"> 10.30</td> + <td class="tdc"> 67</td> <td class="tdc"> 34.62</td> + <td class="tdc">109</td> <td class="tdc"> 59.91</td> + <td class="tdc">151</td> <td class="tdc"> 85.93</td> + </tr><tr> + <td class="tdc"> 26</td> <td class="tdc"> 10.81</td> + <td class="tdc"> 68</td> <td class="tdc"> 35.21</td> + <td class="tdc">110</td> <td class="tdc"> 60.52</td> + <td class="tdc">152</td> <td class="tdc"> 86.55</td> + </tr><tr> + <td class="tdc"> 27</td> <td class="tdc"> 11.33</td> + <td class="tdc"> 69</td> <td class="tdc"> 35.81</td> + <td class="tdc">111</td> <td class="tdc"> 61.13</td> + <td class="tdc">153</td> <td class="tdc"> 87.16</td> + </tr><tr> + <td class="tdc"> 28</td> <td class="tdc"> 11.84</td> + <td class="tdc"> 70</td> <td class="tdc"> 36.40</td> + <td class="tdc">112</td> <td class="tdc"> 61.74</td> + <td class="tdc">154</td> <td class="tdc"> 87.88</td> + </tr><tr> + <td class="tdc"> 29</td> <td class="tdc"> 12.36</td> + <td class="tdc"> 71</td> <td class="tdc"> 37.00</td> + <td class="tdc">113</td> <td class="tdc"> 62.36</td> + <td class="tdc">155</td> <td class="tdc"> 88.40</td> + </tr><tr> + <td class="tdc"> 30</td> <td class="tdc"> 12.87</td> + <td class="tdc"> 72</td> <td class="tdc"> 37.59</td> + <td class="tdc">114</td> <td class="tdc"> 62.97</td> + <td class="tdc">156</td> <td class="tdc"> 89.05</td> + </tr><tr> + <td class="tdc"> 31</td> <td class="tdc"> 13.46</td> + <td class="tdc"> 73</td> <td class="tdc"> 38.19</td> + <td class="tdc">115</td> <td class="tdc"> 63.58</td> + <td class="tdc">157</td> <td class="tdc"> 89.69</td> + </tr><tr> + <td class="tdc"> 32</td> <td class="tdc"> 14.05</td> + <td class="tdc"> 74</td> <td class="tdc"> 38.78</td> + <td class="tdc">116</td> <td class="tdc"> 64.21</td> + <td class="tdc">158</td> <td class="tdc"> 90.34</td> + </tr><tr> + <td class="tdc"> 33</td> <td class="tdc"> 14.64</td> + <td class="tdc"> 75</td> <td class="tdc"> 39.38</td> + <td class="tdc">117</td> <td class="tdc"> 64.84</td> + <td class="tdc">159</td> <td class="tdc"> 90.98</td> + </tr><tr> + <td class="tdc"> 34</td> <td class="tdc"> 15.23</td> + <td class="tdc"> 76</td> <td class="tdc"> 39.98</td> + <td class="tdc">118</td> <td class="tdc"> 65.46</td> + <td class="tdc">160</td> <td class="tdc"> 91.63</td> + </tr><tr> + <td class="tdc"> 35</td> <td class="tdc"> 15.82</td> + <td class="tdc"> 77</td> <td class="tdc"> 40.58</td> + <td class="tdc">119</td> <td class="tdc"> 66.09</td> + <td class="tdc">161</td> <td class="tdc"> 92.26</td> + </tr><tr> + <td class="tdc"> 36</td> <td class="tdc"> 16.40</td> + <td class="tdc"> 78</td> <td class="tdc"> 41.17</td> + <td class="tdc">120</td> <td class="tdc"> 66.72</td> + <td class="tdc">162</td> <td class="tdc"> 92.90</td> + </tr><tr> + <td class="tdc"> 37</td> <td class="tdc"> 16.99</td> + <td class="tdc"> 79</td> <td class="tdc"> 41.77</td> + <td class="tdc">121</td> <td class="tdc"> 67.32</td> + <td class="tdc">163</td> <td class="tdc"> 93.53</td> + </tr><tr> + <td class="tdc"> 38</td> <td class="tdc"> 17.57</td> + <td class="tdc"> 80</td> <td class="tdc"> 42.37</td> + <td class="tdc">122</td> <td class="tdc"> 67.92</td> + <td class="tdc">164</td> <td class="tdc"> 94.17</td> + </tr><tr> + <td class="tdc"> 39</td> <td class="tdc"> 18.16</td> + <td class="tdc"> 81</td> <td class="tdc"> 42.97</td> + <td class="tdc">123</td> <td class="tdc"> 68.53</td> + <td class="tdc">165</td> <td class="tdc"> 94.80</td> + </tr><tr> + <td class="tdc"> 40</td> <td class="tdc"> 18.74</td> + <td class="tdc"> 82</td> <td class="tdc"> 43.57</td> + <td class="tdc">124</td> <td class="tdc"> 69.13</td> + <td class="tdc">166</td> <td class="tdc"> 95.44</td> + </tr><tr> + <td class="tdc"> 41</td> <td class="tdc"> 19.32</td> + <td class="tdc"> 83</td> <td class="tdc"> 44.16</td> + <td class="tdc">125</td> <td class="tdc"> 69.73</td> + <td class="tdc">167</td> <td class="tdc"> 96.08</td> + </tr><tr> + <td class="tdc"> 42</td> <td class="tdc"> 19.91</td> + <td class="tdc"> 84</td> <td class="tdc"> 44.76</td> + <td class="tdc">126</td> <td class="tdc"> 70.35</td> + <td class="tdc">168</td> <td class="tdc"> 96.77</td> + </tr><tr> + <td class="tdc"> 43</td> <td class="tdc"> 20.49</td> + <td class="tdc"> 85</td> <td class="tdc"> 45.36</td> + <td class="tdc">127</td> <td class="tdc"> 70.96</td> + <td class="tdc">169</td> <td class="tdc"> 97.33</td> + </tr><tr> + <td class="tdc"> 44</td> <td class="tdc"> 21.08</td> + <td class="tdc"> 86</td> <td class="tdc"> 45.96</td> + <td class="tdc">128</td> <td class="tdc"> 71.58</td> + <td class="tdc">170</td> <td class="tdc"> 97.99</td> + </tr><tr> + <td class="tdc"> 45</td> <td class="tdc"> 21.66</td> + <td class="tdc"> 87</td> <td class="tdc"> 46.57</td> + <td class="tdc">129</td> <td class="tdc"> 72.19</td> + <td class="tdc">171</td> <td class="tdc"> 98.63</td> + </tr><tr> + <td class="tdc"> 46</td> <td class="tdc"> 22.25</td> + <td class="tdc"> 88</td> <td class="tdc"> 47.17</td> + <td class="tdc">130</td> <td class="tdc"> 72.81</td> + <td class="tdc">172</td> <td class="tdc"> 99.27</td> + </tr><tr> + <td class="tdc"> 47</td> <td class="tdc"> 22.83</td> + <td class="tdc"> 89</td> <td class="tdc"> 47.78</td> + <td class="tdc">131</td> <td class="tdc"> 73.43</td> + <td class="tdc">173</td> <td class="tdc"> 99.90</td> + </tr><tr> + <td class="tdc"> 48</td> <td class="tdc"> 23.42</td> + <td class="tdc"> 90</td> <td class="tdc"> 48.38</td> + <td class="tdc">132</td> <td class="tdc"> 74.05</td> + <td class="tdc">174</td> <td class="tdc">100.54</td> + </tr><tr> + <td class="tdc"> 49</td> <td class="tdc"> 24.00</td> + <td class="tdc"> 91</td> <td class="tdc"> 48.98</td> + <td class="tdc">133</td> <td class="tdc"> 74.67</td> + <td class="tdc">175</td> <td class="tdc">101.18</td> + </tr><tr> + <td class="tdc"> 50</td> <td class="tdc"> 24.59</td> + <td class="tdc"> 92</td> <td class="tdc"> 49.58</td> + <td class="tdc">134</td> <td class="tdc"> 75.29</td> + <td class="tdc">176</td> <td class="tdc">101.82</td> + </tr><tr> + <td class="tdc"> 51</td> <td class="tdc"> 25.18</td> + <td class="tdc"> 93</td> <td class="tdc"> 50.18</td> + <td class="tdc">135</td> <td class="tdc"> 75.91</td> + <td class="tdc">177</td> <td class="tdc">102.46</td> + </tr><tr> + <td class="tdc"> 52</td> <td class="tdc"> 25.76</td> + <td class="tdc"> 94</td> <td class="tdc"> 50.78</td> + <td class="tdc">136</td> <td class="tdc"> 76.53</td> + <td class="tdc">178</td> <td class="tdc">103.11</td> + </tr><tr> + <td class="tdc"> 53</td> <td class="tdc"> 26.35</td> + <td class="tdc"> 95</td> <td class="tdc"> 51.38</td> + <td class="tdc">137</td> <td class="tdc"> 77.15</td> + <td class="tdc">179</td> <td class="tdc">103.75</td> + </tr><tr> + <td class="tdc"> 54</td> <td class="tdc"> 26.93</td> + <td class="tdc"> 96</td> <td class="tdc"> 51.98</td> + <td class="tdc">138</td> <td class="tdc"> 77.77</td> + <td class="tdc">180</td> <td class="tdc">104.39</td> + </tr><tr> + <td class="tdc"> 55</td> <td class="tdc"> 27.52</td> + <td class="tdc"> 97</td> <td class="tdc"> 52.58</td> + <td class="tdc">139</td> <td class="tdc"> 78.39</td> + <td class="tdc">181</td> <td class="tdc">105.04</td> + </tr><tr> + <td class="tdc"> 56</td> <td class="tdc"> 28.11</td> + <td class="tdc"> 98</td> <td class="tdc"> 53.19</td> + <td class="tdc">140</td> <td class="tdc"> 79.01</td> + <td class="tdc">182</td> <td class="tdc">105.68</td> + </tr><tr> + <td class="tdc"> 57</td> <td class="tdc"> 28.70</td> + <td class="tdc"> 99</td> <td class="tdc"> 53.79</td> + <td class="tdc">141</td> <td class="tdc"> 79.64</td> + <td class="tdc">183</td> <td class="tdc">106.33</td> + </tr><tr> + <td class="tdc"> 58</td> <td class="tdc"> 29.30</td> + <td class="tdc">100</td> <td class="tdc"> 54.39</td> + <td class="tdc">142</td> <td class="tdc"> 80.28</td> + <td class="tdc">184</td> <td class="tdc">106.97</td> + </tr><tr> + <td class="tdc"> 59</td> <td class="tdc"> 29.89</td> + <td class="tdc">101</td> <td class="tdc"> 55.00</td> + <td class="tdc">143</td> <td class="tdc"> 80.91</td> + <td class="tdc">185</td> <td class="tdc">107.62</td> + </tr><tr> + <td class="tdc"> 60</td> <td class="tdc"> 30.48</td> + <td class="tdc">102</td> <td class="tdc"> 55.62</td> + <td class="tdc">144</td> <td class="tdc"> 81.55</td> + <td class="tdc">186</td> <td class="tdc">108.27</td> + </tr><tr> + <td class="tdc"> 61</td> <td class="tdc"> 31.07</td> + <td class="tdc">103</td> <td class="tdc"> 56.23</td> + <td class="tdc">145</td> <td class="tdc"> 82.18</td> + <td class="tdc">187</td> <td class="tdc">108.92</td> + </tr><tr> + <td class="tdc" colspan="8"> <span class="pagenum"><a id="Page_170"></a>[Pg 170]</span></td> + </tr><tr class="f110"> + <td class="tdc"> <b>(A)</b> </td> <td class="tdc"> <b>(B)</b> </td> + <td class="tdc"> <b>(A)</b> </td> <td class="tdc"> <b>(B)</b> </td> + <td class="tdc"> <b>(A)</b> </td> <td class="tdc"> <b>(B)</b> </td> + <td class="tdc"> <b>(A)</b> </td> <td class="tdc"> <b>(B)</b> </td> + </tr><tr> + <td class="tdc">188</td> <td class="tdc">109.56</td> + <td class="tdc">232</td> <td class="tdc">138.57</td> + <td class="tdc">276</td> <td class="tdc">168.68</td> + <td class="tdc">320</td> <td class="tdc">199.97</td> + </tr><tr> + <td class="tdc">189</td> <td class="tdc">110.21</td> + <td class="tdc">233</td> <td class="tdc">139.25</td> + <td class="tdc">277</td> <td class="tdc">169.37</td> + <td class="tdc">321</td> <td class="tdc">200.71</td> + </tr><tr> + <td class="tdc">190</td> <td class="tdc">110.86</td> + <td class="tdc">234</td> <td class="tdc">139.18</td> + <td class="tdc">278</td> <td class="tdc">170.06</td> + <td class="tdc">322</td> <td class="tdc">201.44</td> + </tr><tr> + <td class="tdc">191</td> <td class="tdc">111.50</td> + <td class="tdc">235</td> <td class="tdc">140.59</td> + <td class="tdc">279</td> <td class="tdc">170.75</td> + <td class="tdc">323</td> <td class="tdc">202.18</td> + </tr><tr> + <td class="tdc">192</td> <td class="tdc">112.14</td> + <td class="tdc">236</td> <td class="tdc">141.27</td> + <td class="tdc">280</td> <td class="tdc">171.44</td> + <td class="tdc">324</td> <td class="tdc">202.91</td> + </tr><tr> + <td class="tdc">193</td> <td class="tdc">112.78</td> + <td class="tdc">237</td> <td class="tdc">141.94</td> + <td class="tdc">281</td> <td class="tdc">172.14</td> + <td class="tdc">325</td> <td class="tdc">203.65</td> + </tr><tr> + <td class="tdc">194</td> <td class="tdc">113.42</td> + <td class="tdc">238</td> <td class="tdc">142.62</td> + <td class="tdc">282</td> <td class="tdc">172.85</td> + <td class="tdc">326</td> <td class="tdc">204.39</td> + </tr><tr> + <td class="tdc">195</td> <td class="tdc">114.06</td> + <td class="tdc">239</td> <td class="tdc">143.29</td> + <td class="tdc">283</td> <td class="tdc">173.55</td> + <td class="tdc">327</td> <td class="tdc">205.13</td> + </tr><tr> + <td class="tdc">196</td> <td class="tdc">114.72</td> + <td class="tdc">240</td> <td class="tdc">143.97</td> + <td class="tdc">284</td> <td class="tdc">174.26</td> + <td class="tdc">328</td> <td class="tdc">205.88</td> + </tr><tr> + <td class="tdc">197</td> <td class="tdc">115.38</td> + <td class="tdc">241</td> <td class="tdc">144.65</td> + <td class="tdc">285</td> <td class="tdc">174.96</td> + <td class="tdc">329</td> <td class="tdc">206.62</td> + </tr><tr> + <td class="tdc">198</td> <td class="tdc">116.04</td> + <td class="tdc">242</td> <td class="tdc">145.32</td> + <td class="tdc">286</td> <td class="tdc">175.67</td> + <td class="tdc">330</td> <td class="tdc">207.36</td> + </tr><tr class="bb"> + <td class="tdc">199</td> <td class="tdc">116.70</td> + <td class="tdc">243</td> <td class="tdc">146.00</td> + <td class="tdc">287</td> <td class="tdc">176.39</td> + <td class="tdc">331</td> <td class="tdc">208.10</td> + </tr><tr> + <td class="tdc">200</td> <td class="tdc">117.36</td> + <td class="tdc">244</td> <td class="tdc">146.67</td> + <td class="tdc">288</td> <td class="tdc">177.10</td> + <td class="tdc">332</td> <td class="tdc">208.83</td> + </tr><tr> + <td class="tdc">201</td> <td class="tdc">118.02</td> + <td class="tdc">245</td> <td class="tdc">147.35</td> + <td class="tdc">289</td> <td class="tdc">177.82</td> + <td class="tdc">333</td> <td class="tdc">209.57</td> + </tr><tr> + <td class="tdc">202</td> <td class="tdc">118.68</td> + <td class="tdc">246</td> <td class="tdc">148.03</td> + <td class="tdc">290</td> <td class="tdc">178.53</td> + <td class="tdc">334</td> <td class="tdc">210.30</td> + </tr><tr> + <td class="tdc">203</td> <td class="tdc">119.33</td> + <td class="tdc">247</td> <td class="tdc">148.71</td> + <td class="tdc">291</td> <td class="tdc">179.24</td> + <td class="tdc">335</td> <td class="tdc">211.04</td> + </tr><tr> + <td class="tdc">204</td> <td class="tdc">119.99</td> + <td class="tdc">248</td> <td class="tdc">149.40</td> + <td class="tdc">292</td> <td class="tdc">179.95</td> + <td class="tdc">336</td> <td class="tdc">211.78</td> + </tr><tr> + <td class="tdc">205</td> <td class="tdc">120.65</td> + <td class="tdc">249</td> <td class="tdc">150.08</td> + <td class="tdc">293</td> <td class="tdc">180.65</td> + <td class="tdc">337</td> <td class="tdc">212.52</td> + </tr><tr> + <td class="tdc">206</td> <td class="tdc">121.30</td> + <td class="tdc">250</td> <td class="tdc">150.76</td> + <td class="tdc">294</td> <td class="tdc">181.63</td> + <td class="tdc">338</td> <td class="tdc">213.25</td> + </tr><tr> + <td class="tdc">207</td> <td class="tdc">121.96</td> + <td class="tdc">251</td> <td class="tdc">151.44</td> + <td class="tdc">295</td> <td class="tdc">182.07</td> + <td class="tdc">339</td> <td class="tdc">213.99</td> + </tr><tr> + <td class="tdc">208</td> <td class="tdc">122.61</td> + <td class="tdc">252</td> <td class="tdc">152.12</td> + <td class="tdc">296</td> <td class="tdc">182.78</td> + <td class="tdc">340</td> <td class="tdc">214.73</td> + </tr><tr> + <td class="tdc">209</td> <td class="tdc">123.27</td> + <td class="tdc">253</td> <td class="tdc">152.81</td> + <td class="tdc">297</td> <td class="tdc">183.49</td> + <td class="tdc">341</td> <td class="tdc">215.48</td> + </tr><tr> + <td class="tdc">210</td> <td class="tdc">123.92</td> + <td class="tdc">254</td> <td class="tdc">153.49</td> + <td class="tdc">298</td> <td class="tdc">184.21</td> + <td class="tdc">342</td> <td class="tdc">216.23</td> + </tr><tr> + <td class="tdc">211</td> <td class="tdc">124.58</td> + <td class="tdc">255</td> <td class="tdc">154.17</td> + <td class="tdc">299</td> <td class="tdc">184.92</td> + <td class="tdc">343</td> <td class="tdc">216.97</td> + </tr><tr> + <td class="tdc">212</td> <td class="tdc">125.24</td> + <td class="tdc">256</td> <td class="tdc">154.91</td> + <td class="tdc">300</td> <td class="tdc">185.63</td> + <td class="tdc">344</td> <td class="tdc">217.72</td> + </tr><tr> + <td class="tdc">213</td> <td class="tdc">125.90</td> + <td class="tdc">257</td> <td class="tdc">155.65</td> + <td class="tdc">301</td> <td class="tdc">186.35</td> + <td class="tdc">345</td> <td class="tdc">218.47</td> + </tr><tr> + <td class="tdc">214</td> <td class="tdc">126.56</td> + <td class="tdc">258</td> <td class="tdc">156.40</td> + <td class="tdc">302</td> <td class="tdc">187.06</td> + <td class="tdc">346</td> <td class="tdc">219.21</td> + </tr><tr> + <td class="tdc">215</td> <td class="tdc">127.22</td> + <td class="tdc">259</td> <td class="tdc">157.14</td> + <td class="tdc">303</td> <td class="tdc">187.78</td> + <td class="tdc">347</td> <td class="tdc">219.97</td> + </tr><tr> + <td class="tdc">216</td> <td class="tdc">127.85</td> + <td class="tdc">260</td> <td class="tdc">157.88</td> + <td class="tdc">304</td> <td class="tdc">188.49</td> + <td class="tdc">348</td> <td class="tdc">220.71</td> + </tr><tr> + <td class="tdc">217</td> <td class="tdc">128.48</td> + <td class="tdc">261</td> <td class="tdc">158.49</td> + <td class="tdc">305</td> <td class="tdc">189.21</td> + <td class="tdc">349</td> <td class="tdc">221.46</td> + </tr><tr> + <td class="tdc">218</td> <td class="tdc">129.10</td> + <td class="tdc">262</td> <td class="tdc">159.09</td> + <td class="tdc">306</td> <td class="tdc">189.93</td> + <td class="tdc">350</td> <td class="tdc">222.21</td> + </tr><tr class="bb"> + <td class="tdc">219</td> <td class="tdc">129.73</td> + <td class="tdc">263</td> <td class="tdc">159.70</td> + <td class="tdc">307</td> <td class="tdc">190.65</td> + <td class="tdc">351</td> <td class="tdc">222.96</td> + </tr><tr> + <td class="tdc">220</td> <td class="tdc">130.36</td> + <td class="tdc">264</td> <td class="tdc">160.30</td> + <td class="tdc">308</td> <td class="tdc">191.37</td> + <td class="tdc">352</td> <td class="tdc">223.72</td> + </tr><tr> + <td class="tdc">221</td> <td class="tdc">131.07</td> + <td class="tdc">265</td> <td class="tdc">160.91</td> + <td class="tdc">309</td> <td class="tdc">192.09</td> + <td class="tdc">353</td> <td class="tdc">224.47</td> + </tr><tr> + <td class="tdc">222</td> <td class="tdc">131.77</td> + <td class="tdc">266</td> <td class="tdc">161.63</td> + <td class="tdc">310</td> <td class="tdc">192.81</td> + <td class="tdc">354</td> <td class="tdc">225.23</td> + </tr><tr> + <td class="tdc">223</td> <td class="tdc">132.48</td> + <td class="tdc">267</td> <td class="tdc">162.35</td> + <td class="tdc">311</td> <td class="tdc">193.53</td> + <td class="tdc">355</td> <td class="tdc">225.98</td> + </tr><tr> + <td class="tdc">224</td> <td class="tdc">133.18</td> + <td class="tdc">268</td> <td class="tdc">163.07</td> + <td class="tdc">312</td> <td class="tdc">194.25</td> + <td class="tdc">356</td> <td class="tdc">226.74</td> + </tr><tr> + <td class="tdc">225</td> <td class="tdc">133.89</td> + <td class="tdc">269</td> <td class="tdc">163.79</td> + <td class="tdc">313</td> <td class="tdc">194.97</td> + <td class="tdc">357</td> <td class="tdc">227.49</td> + </tr><tr> + <td class="tdc">226</td> <td class="tdc">134.56</td> + <td class="tdc">270</td> <td class="tdc">164.51</td> + <td class="tdc">314</td> <td class="tdc">195.69</td> + <td class="tdc">358</td> <td class="tdc">228.25</td> + </tr><tr> + <td class="tdc">227</td> <td class="tdc">135.23</td> + <td class="tdc">271</td> <td class="tdc">165.21</td> + <td class="tdc">315</td> <td class="tdc">196.41</td> + <td class="tdc">359</td> <td class="tdc">229.00</td> + </tr><tr> + <td class="tdc">228</td> <td class="tdc">135.89</td> + <td class="tdc">272</td> <td class="tdc">165.90</td> + <td class="tdc">316</td> <td class="tdc">197.12</td> + <td class="tdc">360</td> <td class="tdc">229.76</td> + </tr><tr> + <td class="tdc">229</td> <td class="tdc">136.89</td> + <td class="tdc">273</td> <td class="tdc">166.60</td> + <td class="tdc">317</td> <td class="tdc">197.83</td> + <td class="tdc">361</td> <td class="tdc">230.52</td> + </tr><tr> + <td class="tdc">230</td> <td class="tdc">137.23</td> + <td class="tdc">274</td> <td class="tdc">167.29</td> + <td class="tdc">318</td> <td class="tdc">198.55</td> + <td class="tdc">362</td> <td class="tdc">231.28</td> + </tr><tr> + <td class="tdc">231</td> <td class="tdc">137.90</td> + <td class="tdc">275</td> <td class="tdc">167.99</td> + <td class="tdc">319</td> <td class="tdc">199.26</td> + <td class="tdc">363</td> <td class="tdc">232.05</td> + </tr><tr> + <td class="tdc" colspan="8"> <span class="pagenum"><a id="Page_171"></a>[Pg 171]</span></td> + </tr><tr class="f110"> + <td class="tdc"> <b>(A)</b> </td> <td class="tdc"> <b>(B)</b> </td> + <td class="tdc"> <b>(A)</b> </td> <td class="tdc"> <b>(B)</b> </td> + <td class="tdc"> <b>(A)</b> </td> <td class="tdc"> <b>(B)</b> </td> + <td class="tdc"> <b>(A)</b> </td> <td class="tdc"> <b>(B)</b> </td> + </tr><tr> + <td class="tdc">364</td> <td class="tdc">232.81</td> + <td class="tdc">370</td> <td class="tdc">237.39</td> + <td class="tdc">376</td> <td class="tdc">241.87</td> + <td class="tdc">382</td> <td class="tdc">246.25</td> + </tr><tr> + <td class="tdc">365</td> <td class="tdc">233.57</td> + <td class="tdc">371</td> <td class="tdc">238.16</td> + <td class="tdc">377</td> <td class="tdc">242.51</td> + <td class="tdc">383</td> <td class="tdc">247.17</td> + </tr><tr> + <td class="tdc">366</td> <td class="tdc">234.33</td> + <td class="tdc">372</td> <td class="tdc">238.93</td> + <td class="tdc">378</td> <td class="tdc">243.15</td> + <td class="tdc">384</td> <td class="tdc">248.08</td> + </tr><tr> + <td class="tdc">367</td> <td class="tdc">235.10</td> + <td class="tdc">373</td> <td class="tdc">239.69</td> + <td class="tdc">379</td> <td class="tdc">243.79</td> + <td class="tdc">385</td> <td class="tdc">248.99</td> + </tr><tr> + <td class="tdc">368</td> <td class="tdc">235.86</td> + <td class="tdc">374</td> <td class="tdc">240.46</td> + <td class="tdc">380</td> <td class="tdc">244.43</td> + <td class="tdc"> </td> <td class="tdc"> </td> + </tr><tr class="bb"> + <td class="tdc">369</td> <td class="tdc">236.63</td> + <td class="tdc">375</td> <td class="tdc">241.23</td> + <td class="tdc">381</td> <td class="tdc">245.34</td> + <td class="tdc"> </td> <td class="tdc"> </td> + </tr> + </tbody> +</table> + +<p id="P_147"><b>147. Precipitation of Sugars with Phenylhydrazin</b>.—The +combination of phenylhydrazin with aldehyds and ketones was first +studied by Fischer, and the near relationship of these bodies to sugar +soon led to the investigation of the compounds formed thereby with +this reagent.<a id="FNanchor_112" href="#Footnote_112" class="fnanchor">[112]</a> +Reducing sugars form with phenylhydrazin insoluble crystalline bodies, +to which the name osazones has been given. The reaction which takes +place is a double one and is represented by the following formulas:</p> + +<ul class="index"> +<li class="isub1">Dextrose. Phenylhydrazin. Dextrose-phenylhydrazone.</li> +<li class="isub1">C₆H₁₂O₆ + C₆H₅NH.NH₂ = C₆H₁₂O₅.N.NHC₆H₅ + H₂O</li> +<li class="isub3">and C₆H₁₂O₅.N.NHC₆H₅ + C₆H₅NH.NH₂ =</li> +<li class="isub10">Phenyldextrosazone.</li> +<li class="isub10">C₆H₁₀O₄(N.NHC₆H₅)₂ + 2H₂O.</li> +</ul> + +<p>The dextrosazone is commonly called glucosazone. The osazones formed +with the commonly occurring reducing sugars are crystalline, stable, +insoluble bodies which can be easily separated from any attending +impurities and identified by their melting points. Glucosazone melts at +205°, lactosazone at 200° and maltosazone at 206°.</p> + +<p>The osazones are precipitated in the following way: The reducing sugar, +in about ten per cent solution, is treated with an excess of the +acetate of phenylhydrazin in acetic acid and warmed to from 75° to 85°. +In a short time the separation is complete and the yellow precipitate +formed is washed, dried and weighed. The sugar can be recovered from +the osazone by decomposing it with strong hydrochloric acid by means +of which the phenylhydrazin is displaced and a body, osone, is formed, +which by treatment with zinc dust and acetic acid, is reduced to the +<span class="pagenum"><a id="Page_172"></a>[Pg 172]</span> +original sugar. The reactions which take place are represented by the +following equations:<a id="FNanchor_113" href="#Footnote_113" class="fnanchor">[113]</a></p> + +<ul class="index"> +<li class="isub14">Glucososone.</li> +<li class="isub1">C₆H₁₀O₄(N.NH.C₆H₅)₂ + 2H₂O = C₆H₁₀O₆ + 2C₆H₅N₂H₂</li> +<li class="isub1"> </li> +<li class="isub10"> Dextrose (Glucose).</li> +<li class="isub4">C₆H₁₀O₆ + H₂ = C₆H₁₂O₆.</li> +</ul> + +<p>For the complete precipitation of dextrose as osazone Lintner and +Kröber show that the solution of dextrose should not contain more than +one gram in 100 cubic centimeters. Twenty cubic centimeters containing +0.2 gram dextrose should be used for the precipitation.<a id="FNanchor_114" href="#Footnote_114" class="fnanchor">[114]</a> +To this solution should be added one gram of phenylhydrazin and one gram of +fifty per cent acetic acid. The solution is then to be warmed for about +two hours and the precipitate washed with from sixty to eighty cubic +centimeters of hot water and dried for three hours at 105°. One part +of the osazone is equivalent to one part of dextrose when maltose and +dextrin are absent. When these are present the proportion is one part +of osazone to 1.04 of dextrose. Where levulose is precipitated instead +of dextrose 1.43 parts of the osazone are equal to one part of the sugar.</p> + +<p>Sucrose is scarcely at all precipitated as osazone until inverted.</p> + +<p>After inversion and precipitation as above, 1.33 parts osazone are +equal to one part of sucrose.</p> + +<p>The reaction with phenylhydrazin has not been much used for quantitive +estimations of sugars, but it has been found especially useful in +identifying and separating reducing sugars. It is altogether probable, +however, that in the near future phenylhydrazin will become a common +reagent for sugar work.</p> + +<p>Maquenne has studied the action of phenylhydrazin on sugars and +considers that this reaction offers the only known means of +precipitating these bodies from solutions where they are found mixed +with other substances.<a id="FNanchor_115" href="#Footnote_115" class="fnanchor">[115]</a> +The osazones, which are thus obtained, are usually very slightly +soluble in the ordinary reagents, for which reason it is easy to obtain +them pure when there is at the disposition of the analyst a sufficient +quantity of the material. But if the sugar to be studied is rare and +if it contain, moreover, several distinct reducing bodies, the task +is more delicate. It is easy then to confound several osazones which +have almost identical points of fusion; for example, glucosazone with +<span class="pagenum"><a id="Page_173"></a>[Pg 173]</span> +galactosazone. Finally, it becomes impossible by the employment of +phenylhydrazin to distinguish glucose, dextrose or mannose from +levulose alone or mixed with its isomers. Indeed, these three sugars +give, with the acetate of phenylhydrazin the same phenylglucosazone +which melts at about 205°. It is noticed that the weights of osazones +which are precipitated when different sugars are heated for the +same time with the same quantity of the phenylhydrazin, vary within +extremely wide limits. It is constant for each kind of sugar if the +conditions under which the precipitation is made are rigorously the +same. There is then, in the weight of the osazones produced, a new +characteristic of particular value. The following numbers have been +obtained by heating for one hour at 100°, one gram of sugar with 100 +cubic centimeters of water and five cubic centimeters of a solution +containing forty grams of phenylhydrazin and forty grams of acetic acid +per hundred. After cooling the liquid, the osazones are received upon +a weighed filter, washed with 100 cubic centimeters of water, dried at +110° and weighed. The weights of osazones obtained are given in the +following table:</p> + +<table class="spb1"> + <tbody><tr> + <td class="tdl" colspan="2">Character of the sugar.</td> + <td class="tdc" rowspan="11">   </td> + <td class="tdc">Weight of the<br> osazones. </td> + </tr><tr> + <td class="tdl" colspan="2"> </td> + <td class="tdc">gram.</td> + </tr><tr> + <td class="tdl">Sorbine,</td> + <td class="tdl_wsp">crystallized</td> + <td class="tdc">0.82</td> + </tr><tr> + <td class="tdl">Levulose</td> + <td class="tdc">”</td> + <td class="tdc">0.70</td> + </tr><tr> + <td class="tdl">Xylose</td> + <td class="tdc">”</td> + <td class="tdc">0.40</td> + </tr><tr> + <td class="tdl">Glucose,</td> + <td class="tdl_wsp">anhydrous</td> + <td class="tdc">0.32</td> + </tr><tr> + <td class="tdl">Arabinose,</td> + <td class="tdl_wsp">crystallized</td> + <td class="tdc">0.27</td> + </tr><tr> + <td class="tdl">Galactose</td> + <td class="tdc">”</td> + <td class="tdc">0.23</td> + </tr><tr> + <td class="tdl">Rhamnose</td> + <td class="tdc">”</td> + <td class="tdc">0.15</td> + </tr><tr> + <td class="tdl">Lactose</td> + <td class="tdc">”</td> + <td class="tdc">0.11</td> + </tr><tr> + <td class="tdl">Maltose</td> + <td class="tdc">”</td> + <td class="tdc">0.11</td> + </tr> + </tbody> +</table> + +<p>With solutions twice as dilute as those above, the relative conditions +are still more sensible, and the different sugars arrange themselves in +the same order, with the exception of levulose, which shows a slight +advantage over sorbine and acquires the first rank. From the above +determinations, it is shown that levulose and sorbine give vastly +greater quantities of osazones, under given conditions, than the other +reducing sugars. It would be easy, therefore, to distinguish them by +this reaction and to recognize their presence also even in very complex +mixtures, where the polarimetric examination alone would furnish only +uncertain indications. +<span class="pagenum"><a id="Page_174"></a>[Pg 174]</span></p> + +<p>It is remarkable that these two sugars are the only ones among the +isomers or the homologues of dextrose, actually known, which possess +the functions of an acetone. They are not, however, easily confounded, +since the glucosazone forms beautiful needles which are ordinarily +visible to the naked eye, while the sorbinosazone is still oily and +when heated never gives perfectly distinct crystals.</p> + +<p>This method also enables us to distinguish between dextrose and +galactose, of which the osazone is well crystallized and melts at +almost the same temperature as the phenylglucosazone. Finally, it +is observed that the reducing sugars give less of osazones than the +sugars which are not capable of hydrolysis, and consequently differ +in their inversion products. It is specially noticed in this study of +the polyglucoses (bioses, trioses), that this new method of employing +the phenylhydrazin appears very advantageous. It is sufficient to +compare the weights of the osazones to that which is given under the +same conditions by a known glucose, in order to have a very certain +verification of the probabilities of the result of the chemical or +optical examination of the mixture which is under study. All the +polyglucoses which have been examined from this point of view give +very decided results. The numbers which follow have reference to one +gram of sugar completely inverted by dilute sulfuric acid, dissolved +in 100 cubic centimeters of water, and treated with two grams of +phenylhydrazin, the same quantity of acetic acid, and five grams of +crystallized sodium acetate. All these solutions have been compared +with the artificial mixtures and corresponding glucoses, with the same +quantities of the same reagents. The following are the results of the +examination:</p> + +<table class="spb1"> + <tbody><tr> + <td class="tdl"> </td> + <td class="tdl_ws1">Character of the sugar.</td> + <td class="tdc">Weight of the<br> osazones. </td> + </tr><tr> + <td class="tdl bb" colspan="2"> </td> + <td class="tdc bb">gram.</td> + </tr><tr> + <td class="tdl bb" rowspan="2">1</td> + <td class="tdl_ws1">Saccharose, ordinary</td> + <td class="tdc">0.71</td> + </tr><tr> + <td class="tdl_ws1 bb">Glucose and levulose (.526 g each)</td> + <td class="tdc bb">0.73</td> + </tr><tr> + <td class="tdl bb" rowspan="2">2</td> + <td class="tdl_ws1">Maltose</td> + <td class="tdc">0.55</td> + </tr><tr> + <td class="tdl_ws1 bb">Glucose (1.052 g)</td> + <td class="tdc bb">0.58</td> + </tr><tr> + <td class="tdl bb" rowspan="2">3</td> + <td class="tdl_ws1">Raffinose, crystallized</td> + <td class="tdc">0.48</td> + </tr><tr> + <td class="tdl_ws1 bb">Levulose, glucose and galactose (.333 g each)</td> + <td class="tdc bb">0.53</td> + </tr><tr> + <td class="tdl bb" rowspan="2">4</td> + <td class="tdl_ws1">Lactose, crystallized</td> + <td class="tdc">0.38</td> + </tr><tr> + <td class="tdl_ws1 bb">Glucose and galactose (.500 g each)</td> + <td class="tdc bb">0.39</td> + </tr> + </tbody> +</table> + +<p>It is noticed that the agreement for each saccharose is as satisfactory +<span class="pagenum"><a id="Page_175"></a>[Pg 175]</span> +as possible. Numbers obtained with the products of inversion are always +a little low by reason of the destructive action of sulfuric acid, +and in particular, upon levulose. This is, moreover, quite sensible +when the product has to be heated for a long time with sulfuric acid +in order to secure a complete inversion. It is evident from the +data cited from the papers of Fischer, Maquenne, and others, that +the determination of sugars by this method is not a very difficult +analytical process and may, in the near future, become of great +practical importance.</p> + +<p><b>148. Molecular Weights of Carbohydrates.</b>—In the examination of +carbohydrates the determination of the molecular weights is often of +the highest analytical value.</p> + +<p>The uncertainty in respect of the true molecular weights of the +carbohydrates is gradually disappearing by reason of the insight into +the composition of these bodies, which recently discovered physical +relations have permitted.</p> + +<p>Raoult, many years ago,<a id="FNanchor_116" href="#Footnote_116" class="fnanchor">[116]</a> +proposed a method of determining molecular weights which is +particularly applicable to carbohydrates soluble in water.</p> + +<p>The principle of Raoult’s discovery may be stated as follows: The +depression of the freezing point of a liquid, caused by the presence of +a dissolved liquid or solid, is proportionate to the absolute amount of +substance dissolved and inversely proportionate to its molecular weight.</p> + +<p>The following formulas may be used in computing results:</p> + +<div class="blockquot"> +<p><i>C</i> = observed depression of freezing point:</p> + +<p><i>P</i> = weight of anhydrous substance in 100 grams:</p> + +<table class="spb1"> + <tbody><tr> + <td class="tdl bb"> <i>C</i> </td> + <td class="tdl" rowspan="2">= <i>A</i> = depression produced by one gram substance in 100 grams:</td> + </tr><tr> + <td class="tdc"><i>P</i></td> + </tr> + </tbody> +</table> + +<p><i>K</i> = depression produced by dissolving in 100 cubic centimeters +a number of grams of the substance corresponding to its +molecular weight:</p> + +<p><i>M</i> = molecular weight:</p> + +<table class="spb1"> + <tbody><tr> + <td class="tdl" rowspan="2">Then we have, <i>K</i> = </td> + <td class="tdc bb"><i>C</i></td> + <td class="tdl" rowspan="2"> × <i>M</i>.</td> + </tr><tr> + <td class="tdc"><i>P</i></td> + </tr> + </tbody> +</table> + +<p><i>K</i> is a quantity varying with the nature of the solvent but with +the same solvent remaining sensibly constant for numerous groups of compounds. +<span class="pagenum"><a id="Page_176"></a>[Pg 176]</span></p> + +<p>The value of</p> + +<table class="spb1"> + <tbody><tr> + <td class="tdl" rowspan="2">A <span class="fs_200">(</span> </td> + <td class="tdc bb"><i>C</i></td> + <td class="tdl" rowspan="2"> <span class="fs_200">)</span></td> + </tr><tr> + <td class="tdc"><i>P</i></td> + </tr> + </tbody> +</table> + +<p class="no-indent">can be determined by experiment. The molecular +weight can therefore be calculated from the formula</p> + +<table class="spb1"> + <tbody><tr> + <td class="tdl" rowspan="2"><i>M</i> = </td> + <td class="tdc bb"><i>K</i></td> + </tr><tr> + <td class="tdc"><i>A</i></td> + </tr> + </tbody> +</table> + +<p class="spb1">With organic compounds in water the value of <i>K</i> +is almost constant.</p> +</div> + +<p>Brown and Morris<a id="FNanchor_117" href="#Footnote_117" class="fnanchor">[117]</a> +report results of their work in extending Raoult’s investigations of +the molecular weight of the carbohydrates. The process is carried on as +follows:</p> + +<p>A solution of the carbohydrate is prepared containing a known weight +of the substance in 100 cubic centimeters of water. About 120 cubic +centimeters of the solution are introduced into a thin beaker of about +400 capacity. This beaker is closed with a stopper with three holes. +Through one of these a glass rod for stirring the solution is inserted. +The second perforation carries a delicate thermometer graduated to +0°.05. The temperature is read with a telescope. The beaker is placed +in a mixture of ice and brine at a temperature from 2° to 3° below +the freezing point of the solution. The solution is cooled until its +temperature is from 0°.5 to 1° below the point of congelation. Through +the third aperture in the stopper a small lump of ice taken from a +frozen portion of the same solution, is dropped, causing at once the +freezing process to begin. The liquid is briskly stirred and as the +congelation goes on the temperature rises and finally becomes constant. +The reading is then taken. The depression in the freezing point, +controlled by the strength of the solution, should never be more than +from 1° to 2°.</p> + +<p>The molecular weights may also be determined by the boiling points of +their solutions as indicated by the author,<a id="FNanchor_118" href="#Footnote_118" class="fnanchor">[118]</a> +Beckmann,<a id="FNanchor_119" href="#Footnote_119" class="fnanchor">[119]</a> +Hite, Orndorff and Cameron.<a id="FNanchor_120" href="#Footnote_120" class="fnanchor">[120]</a></p> + +<p>The method applied to some of the more important carbohydrates gave the +following results:</p> + +<table class="spb1"> + <tbody><tr> + <td class="tdc smcap" colspan="2"><b>Dextrose.</b></td> + </tr><tr> + <td class="tdl">Calculated for C₆H₁₂O₆.</td> + <td class="tdc">Found.</td> + </tr><tr> + <td class="tdc"><i>M</i> = 180</td> + <td class="tdr"><i>M</i> = 180.2</td> + </tr><tr> + <td class="tdc smcap" colspan="2"> <br><b>Sucrose.</b></td> + </tr><tr> + <td class="tdl">Calculated for C₁₂H₂₂O₁₁.</td> + <td class="tdc">Found.</td> + </tr><tr> + <td class="tdc"><i>M</i> = 342</td> + <td class="tdr"><i>M</i> = 337.5 + <span class="pagenum"><a id="Page_177"></a>[Pg 177]</span></td> + </tr><tr> + <td class="tdc smcap" colspan="2"> <br><b>Invertose (Dextrose and Levulose).</b></td> + </tr><tr> + <td class="tdl">Calculated for C₆H₁₂O₆</td> + <td class="tdc">Found.</td> + </tr><tr> + <td class="tdc"><i>M</i> = 180</td> + <td class="tdr"><i>M</i> = 174.3</td> + </tr><tr> + <td class="tdc smcap" colspan="2"> <br><b>Maltose.</b></td> + </tr><tr> + <td class="tdl">Calculated for C₁₂H₂₂O₁₁.</td> + <td class="tdc">Found.</td> + </tr><tr> + <td class="tdc"><i>M</i> = 342</td> + <td class="tdr"><i>M</i> = 322</td> + </tr><tr> + <td class="tdc smcap" colspan="2"> <br><b>Lactose.</b></td> + </tr><tr> + <td class="tdl">Calculated for C₁₂H₂₂O₁₁.</td> + <td class="tdc">Found.</td> + </tr><tr> + <td class="tdc"><i>M</i> = 342</td> + <td class="tdr"><i>M</i> = 345</td> + </tr><tr> + <td class="tdc smcap" colspan="2"> <br><b>Arabinose.</b></td> + </tr><tr> + <td class="tdl">Calculated for C₅H₁₀O₅.</td> + <td class="tdc">Found.</td> + </tr><tr> + <td class="tdc"><i>M</i> = 150</td> + <td class="tdr"><i>M</i> = 150.3</td> + </tr><tr> + <td class="tdc smcap" colspan="2"> <br><b>Raffinose.</b></td> + </tr><tr> + <td class="tdl">Calculated for C₁₈H₃₂O₁₆.5H₂O.</td> + <td class="tdc">Found.</td> + </tr><tr> + <td class="tdc"><i>M</i> = 594</td> + <td class="tdr"><i>M</i> = 528</td> + </tr> + </tbody> +</table> + +<p><b>149. Birotation.</b>—As is well known, dextrose exhibits in fresh +solutions the phenomenon of birotation. The authors supposed that +this phenomenon might have some relation to the size of the molecule. +They, therefore, determined the molecular volume of freshly dissolved +dextrose by the method of Raoult and found <i>M</i> = 180. The high +rotatory power of recently dissolved dextrose is therefore not due to +any variation in the size of its molecule.</p> + +<p>The mathematical theory of birotation is given by Müller as +follows.<a id="FNanchor_121" href="#Footnote_121" class="fnanchor">[121]</a> +In proportion as the unstable modification <i>A</i> is +transformed into the stable modification <i>B</i>, the rotation will +vary. Let ρ = the specific rotatory power of <i>B</i> and <i>a</i>ρ = +that of <i>A</i>, both in the anhydrous state. Let now <i>p</i> grams +of the substance be dissolved in <i>V</i> cubic centimeters of solvent +and observed in a tube <i>l</i> decimeters in length. The time from +making the solution is represented by θ. The angle of rotation α is +read at the time θ. Let <i>x</i> = the mass of <i>A</i>, and <i>y</i> = +that of <i>B</i>, and the equation is derived.</p> + +<table class="spb1 fs_105"> + <tbody><tr> + <td class="tdl" rowspan="2">α = </td> + <td class="tdc bb"><i>a ρ xl</i></td> + <td class="tdl" rowspan="2"> + </td> + <td class="tdc bb">ρ<i>yl</i></td> + </tr><tr> + <td class="tdc"><i>V</i></td> + <td class="tdc"><i>V</i></td> + </tr> + </tbody> +</table> + +<p class="center fs_105">But <i>x</i> + <i>y</i> = <i>p</i></p> + +<table class="spb1 fs_105"> + <tbody><tr> + <td class="tdl" rowspan="2"> whence α = + <span class="fs_150">[</span>(<i>a</i> - 1)<i>x</i> + <i>p</i><span class="fs_150">]</span></td> + <td class="tdc bb">ρ<i>l</i></td> + </tr><tr> + <td class="tdc"><i>V</i></td> + </tr> + </tbody> +</table> + +<p>If now there be introduced into the calculation the final angle +of rotation α<sub>n</sub>, which can be determined with great exactness; +we have</p> + +<table class="spb1 fs_105"> + <tbody><tr> + <td class="tdl" rowspan="2">α<sub>n</sub> = </td> + <td class="tdc bb"><i>p ρ l</i></td> + </tr><tr> + <td class="tdc"><i>V</i></td> + </tr> + </tbody> +</table> + +<table class="spb1 fs_105"> + <tbody><tr> + <td class="tdl" rowspan="2">and consequently α = α<sub>n</sub><span class="fs_200">[</span>1 +</td> + <td class="tdc bb">(<i>a</i> - 1)<i>x</i></td> + <td class="tdl" rowspan="2"><span class="fs_200">]</span>.</td> + </tr><tr> + <td class="tdc"><i>p</i></td> + </tr> + </tbody> +</table> +<table class="spb1 fs_105"> + <tbody><tr> + <td class="tdl" rowspan="2">whence </td> + <td class="tdc bb">(<i>a</i> - 1)<i>x</i></td> + <td class="tdl" rowspan="2"> = </td> + <td class="tdc bb">α</td> + <td class="tdl" rowspan="2"> - 1.</td> + </tr><tr> + <td class="tdc"><i>p</i></td> + <td class="tdc">α<sub>n</sub></td> + </tr> + </tbody> +</table> + +<p><span class="pagenum"><a id="Page_178"></a>[Pg 178]</span> +This equation gives the quantity <i>x</i> of the unstable matter which +is transformed into the stable modification in the time θ.</p> + +<p>It must be admitted that the quantity <i>dx</i> which is changed +during the infinitely small time <i>d</i>θ is proportional to the +mass <i>x</i> which still exists at the moment θ, whence <i>dx</i> = +-Cʹ<i>xd</i>θ where Cʹ represents a constant positive factor. From this +is derived the equation</p> + +<table class="spb1 fs_105"> + <tbody><tr> + <td class="tdc bb"><i>dx</i></td> + <td class="tdl" rowspan="2"> = - Cʹ<i>d</i>θ.</td> + </tr><tr> + <td class="tdc"><i>x</i></td> + </tr> + </tbody> +</table> + +<p>Integrating and calling <i>x</i> the quantity of matter changed to the +stable form at the moment θ, corresponding to a rotation α₀, we have</p> + +<table class="spb1 fs_105"> + <tbody><tr> + <td class="tdl" rowspan="2">Cʹ = </td> + <td class="tdc bb">1</td> + <td class="tdl" rowspan="2"> log. nap. </td> + <td class="tdc bb"><i>x</i>₀</td> + <td class="tdl" rowspan="2"> ,</td> + </tr><tr> + <td class="tdc">θ - θ₀</td> + <td class="tdc"><i>x</i></td> + </tr> + </tbody> +</table> + +<p class="no-indent">and taking into consideration the equation given +above, and substituting common for superior logarithms we get</p> + +<table class="spb1 fs_105"> + <tbody><tr> + <td class="tdl" rowspan="2">C = </td> + <td class="tdc bb">1</td> + <td class="tdl" rowspan="2"> log. </td> + <td class="tdc bb">α₀ - αₙ</td> + <td class="tdl" rowspan="2"> .</td> + </tr><tr> + <td class="tdc">θ - θ₀</td> + <td class="tdc">α - αₙ</td> + </tr> + </tbody> +</table> + +<p>Experience has shown that such a constant C really exists, and +its value can be easily calculated from the data of Parcus and +Tollens.<a id="FNanchor_122" href="#Footnote_122" class="fnanchor">[122]</a> +The mean value of C from these data is 0.0301 for +arabinose; 0.0201 for xylose; 0.0393 for rhamnose; 0.0202 for fucose; +0.00927 for galactose; 0.00405 for lactose; 0.00524 for maltose, and +for dextrose, 0.00348 at 11° to 13° and 0.00398 from 13° to 15°. The +constant C as is well known, increases as the temperature is raised.</p> + +<p>The constant C, at a given temperature, measures the progress of the +phenomenon of the change from the unstable to the stable state. It will +be noticed that among the sugars possessing multirotation properties the +pentoses possess a much higher speed of transformation than the others.</p> + +<p id="P_150"><b>150. Estimation of Pentose Sugars and Pentosans as +Furfurol.</b>—The production of furfurol by distilling carbohydrates +with an acid has already been mentioned. Tollens and his associates +have shown that with pentose sugars, and carbohydrate bodies yielding +them, the production of furfurol is quantitive. +<span class="pagenum"><a id="Page_179"></a>[Pg 179]</span></p> + +<p>The production and estimation of furfurol have been systematically +studied by Krug, to whose paper the reader is referred for the complete +literature of the subject.<a id="FNanchor_123" href="#Footnote_123" class="fnanchor">[123]</a> +The essential principles of the operation are based on the conversion +of the pentoses into furfurol by distilling with a strong acid, and the +subsequent precipitation and estimation of the furfurol formed in the +first part of the reaction.</p> + +<p>The best method of conducting the distillation is as follows:</p> + +<p>Five grams of the pentose substance are placed in a flask of about a +quarter liter capacity, with 100 cubic centimeters of hydrochloric acid +of 1.06 specific gravity. The arrangement of the apparatus is shown in +<a href="#FIG_46">Fig. 46</a>. The flame of the lamp is so regulated as +to secure about two cubic centimeters of distillate per minute.</p> + +<div class="center smcap"> + <img id="FIG_46" src="images/fig46.jpg" alt="" width="600" height="369" > + <p class="center spb1">Figure 46. Distilling Apparatus for Pentoses.</p> +</div> + +<p>The distillate is received in a graduated cylinder and as soon +as thirty cubic centimeters are collected, an equal quantity of +hydrochloric acid, of the strength noted, is added to the distilling +flask, allowing it to flow in slowly so as not to stop the ebullition. +The process is continued until a drop of the distillate gives no +sensible reaction for furfurol when tested with anilin acetate. The +test is applied as follows: Place a drop of the distillate on a piece +<span class="pagenum"><a id="Page_180"></a>[Pg 180]</span> +of filter paper moistened with anilin acetate. The presence of furfurol +will be disclosed by the production of a brilliant red color. Usually +about three hours are consumed in the distillation, during which time a +little less than 400 cubic centimeters of distillate is obtained. The +distillate is neutralized with solid sodium carbonate and, in order +to have always the same quantity of common salt present, 10.2 grams +of sodium chlorid are added for each fifty cubic centimeters of water +necessary to make the total volume to half a liter.<a id="FNanchor_124" href="#Footnote_124" class="fnanchor">[124]</a></p> + +<p>The reactions with pentosans probably consist in first splitting up of +the molecule into a pentose and the subsequent conversion of the latter +into furfurol according to the following equations:</p> + +<div class="blockquot"> +<p class="center"> (C₅H₈O₄)ₙ + (H₂O)ₙ = (C₅H₁₀O₅)ₙ<br> +Pentosan.  Water.<span class="ws2">Pentose.</span></p> + +<p>and</p> + +<p class="center">(C₅H₁₀O₅)ₙ = (C₅H₄O₂)ₙ + (3H₂O)ₙ.<br> +Pentose.  Furfurol.<span class="ws2">Water.</span></p> +</div> + +<p><b>151. Determination of Furfurol.</b>—The quantity of furfurol +obtained by the process mentioned above may be determined in several ways.</p> + +<p><i>As Furfuramid.</i>—When ammonia is added to a saturated solution +of furfurol, furfuramid, (C₅H₄O)₃N₂, is formed. In order to secure the +precipitate it is necessary that the furfurol be highly concentrated +and this can only be accomplished by a tedious fractional distillation. +This method, therefore, has little practical value.</p> + +<p><i>As Furfurolhydrazone.</i>—Furfurol is precipitated almost +quantitively, even from dilute solutions, by phenylhydrazin. The +reaction is represented by the equation:</p> + +<table class="spb1"> + <tbody><tr> + <td class="tdc">C₆H₈N₂</td> + <td class="tdl_wsp">+</td> + <td class="tdl_wsp">C₅H₄O₂</td> + <td class="tdl_wsp">=</td> + <td class="tdc">C₁₁H₁₀N₂O</td> + <td class="tdl_wsp">+</td> + <td class="tdc">H₂O.</td> + </tr><tr> + <td class="tdl">Phenylhydrazin.</td> + <td class="tdl_wsp"> </td> + <td class="tdl_wsp">Furfurol.</td> + <td class="tdl_wsp"> </td> + <td class="tdl_wsp">Furfurolhydrazone.</td> + <td class="tdl_wsp"> </td> + <td class="tdl_wsp">Water.</td> + </tr> + </tbody> +</table> + +<p><b>152. Volumetric Methods.</b>—Tollens and Günther have proposed +a volumetric method which is carried out as follows:<a id="FNanchor_125" href="#Footnote_125" class="fnanchor">[125]</a> +The distillation is accomplished in the manner described. The distillate +is placed in a large beaker, neutralized with sodium carbonate and +acidified with a few drops of acetic. Phenylhydrazin solution of known +strength is run in until a drop of the liquid, after thorough mixing, +<span class="pagenum"><a id="Page_181"></a>[Pg 181]</span> +shows no reaction for furfurol with anilin acetate. The reagent is +prepared by dissolving five grams of pure phenylhydrazin and three +of glacial acetic acid in distilled water, and diluting to 100 cubic +centimeters. The solution is set by dissolving from two-tenths to +three-tenths gram of pure furfurol in half a liter of water and +titrating with the phenylhydrazin as indicated above. The quantity of +the pentose used has a great influence on the result.</p> + +<p>With nearly a gram of arabinose about fifty per cent of furfurol were +obtained while when nearly five grams were used only about forty-six +per cent of furfurol were found. With xylose a similar variation was +found, the percentage of furfurol, decreasing as the quantity of +pentose increased. The method, therefore, gives only approximately +accurate results.</p> + +<p><b>153. Method of Stone.</b>—Another volumetric method proposed by +Stone is based on the detection of an excess of phenylhydrazin by its +reducing action on the fehling reagent.<a id="FNanchor_126" href="#Footnote_126" class="fnanchor">[126]</a> +A standard solution of phenylhydrazin is prepared by dissolving one +gram of the hydrochlorate and three grams of sodium acetate in water +and completing the volume of the liquor to 100 cubic centimeters. This +solution contains 1.494 milligrams of phenylhydrazin in each cubic +centimeter, theoretically equivalent to 1.328 milligrams of furfurol. +The reagent is set by titrating against a known weight of furfurol. +Pure furfurol may be prepared by treating the crude article with +sulfuric acid and potassium dichromate, and subjecting the product to +fractional distillation. The distillate is treated with ammonia and +the furfuramid formed is purified by recrystallizing from alcohol and +drying over sulfuric acid. One gram of this furfuramid is dissolved in +dilute acetic acid and the volume completed to one liter with +water.<a id="FNanchor_127" href="#Footnote_127" class="fnanchor">[127]</a> +The phenylhydrazin solution being unstable, is to be prepared at the time of use.</p> + +<p>The titration is conducted as follows: Twenty-five cubic centimeters of +the distillate obtained from a pentose body, by the method described +above, are diluted with an equal volume of water, a certain quantity +of the phenylhydrazin solution added to the mixture from a burette and +the whole heated quickly to boiling. The flask is rapidly cooled and a +portion of its contents poured on a filter. The filtrate should have a +<span class="pagenum"><a id="Page_182"></a>[Pg 182]</span> +pale yellow color and be perfectly clear. If it become turbid on +standing, it should be refiltered. Two cubic centimeters of the clear +filtrate are boiled with double the quantity of the fehling reagent. +If phenylhydrazin be present, the color of the mixture will change +from blue to green. By repeating the work, with varying quantities of +phenylhydrazin, a point will soon be reached showing the end of the +reaction in a manner entirely analogous to that observed in volumetric +sugar analysis.</p> + +<p>In practice the volumetric methods have given place to the more exact +gravimetric methods described below.</p> + +<p id="P_154"><b>154. Gravimetric Methods.</b>—The distillation is carried on and +the volume of the distillate completed to half a liter as described +above. Chalmot and Tollens then proceed as follows:<a id="FNanchor_128" href="#Footnote_128" class="fnanchor">[128]</a> +Ten cubic centimeters of a solution of phenylhydrazin acetate, +containing in 100 cubic centimeters twelve grams of the phenylhydrazin +and seven and a half grams of glacial acetic acid dissolved and +filtered, are added to the distillate and the mixture stirred with an +appropriate mechanism for half an hour. The furfurolhydrazone at the +end of this time will have separated as small reddish-brown crystals. +The mixture is then thrown onto an asbestos filter and the liquid +separated with suction. The suction should be very gradually applied +so as not to clog the felt. The precipitate adhering to the beaker +is washed into the filter with 100 cubic centimeters of water. The +precipitate is dried at about 60° and weighed. As a check the hydrazone +may be dissolved in hot alcohol, the filter well washed, dried and +again weighed. To obtain the weight of furfurol the weight of hydrazone +found is multiplied by 0.516 and 0.025 added to compensate for the +amount which was held in solution or removed by washing. Less than one +per cent of pentose can not be determined by this method since that +amount is equalled by the known losses during the manipulation.</p> + +<p><i>Factor.</i>—To convert the furfurol found into pentoses, the +following factors are used:</p> + +<table class="spb1"> + <tbody><tr> + <td class="tdl">Per cent furfurol<br>obtained from five<br> grams of pentoses. </td> + <td class="tdc">Multiply for<br> arabinose by. </td> + <td class="tdc"> Multiply for <br>xylose by.</td> + <td class="tdc">Multiply for<br> penta-glucoses by.</td> + </tr><tr> + <td class="tdc" colspan="4"> </td> + </tr><tr> + <td class="tdl">2.5 per cent or less</td> + <td class="tdc">1.90</td> + <td class="tdc">1.70</td> + <td class="tdc">1.67</td> + </tr><tr> + <td class="tdl">5.0 ” ” ” more</td> + <td class="tdc">2.04</td> + <td class="tdc">1.90</td> + <td class="tdc">1.92</td> + </tr> + </tbody> +</table> + +<p id="P_155"><span class="pagenum"><a id="Page_183"></a>[Pg 183]</span> +<b>155. Method Of Krug.</b>—In conducting the determination of +furfurol, according to the method of Chalmont and Tollens just noticed, +Krug observed that the filtrate, after standing for some time, yielded +a second precipitate of furfurol hydrazone. Great difficulty was also +experienced in collecting the precipitate upon the filter on account +of the persistency with which it stuck to the sides of the vessel +in which the precipitation took place.<a id="FNanchor_129" href="#Footnote_129" class="fnanchor">[129]</a> +In order to avoid these two objections, Krug modified the method as +described below and this modified method is now exclusively used in +this laboratory.</p> + +<p>After the precipitation of the furfurol hydrazone, it is stirred +vigorously, by means of an appropriate mechanical stirrer, for at +least half an hour and then allowed to rest for twenty-four hours. On +filtering after that length of time the filtrate remains perfectly +clear and no further precipitation takes place. After the filtration is +complete and the beaker and filtering tube well washed, no attempt is +made to detach the part of the filtrate adhering to the beaker but the +whole of the precipitate, both that upon the filter and that adhering +to the sides of the beaker, is dissolved in strong alcohol, from thirty +to forty cubic centimeters being used. The alcoholic solution is +collected in a small weighed flask, the alcohol evaporated at a gentle +heat and the last traces of water removed by heating to 60° and blowing +a current of dry air through the flask. After weighing the precipitate +of furfurol hydrazone, obtained as above, the calculation of the weight +of pentose bodies is accomplished by means of the usual factors.</p> + +<p><b>156. Precipitation of Furfurol with Pyrogalol.</b>—Furfurol is +thrown out of solution in combination with certain phenol bodies by +heating together in an acid solution. Hotter has proposed a method +for the determination of furfurol based on the above fact.<a id="FNanchor_130" href="#Footnote_130" class="fnanchor">[130]</a> +The furfurol is obtained by distillation in the manner already described +and hydrochloric acid is added if necessary to secure twelve per cent +of that body in a given volume. The furfurol is thrown out of an +aliquot portion by heating with an excess of pyrogalol in closed tubes +for about two hours at 110°. The reaction takes place in two stages, +represented by the following equations: +<span class="pagenum"><a id="Page_184"></a>[Pg 184]</span></p> + +<div class="blockquot"> +<p class="f105">C₅H₄O₂  + C₆H₆O₃ = C₁₁H₁₀O₅<br>and<br> +2C₁₁H₁₀O₅ = C₂₂H₁₈O₉ + H₂O.</p> +</div> + +<p>The aliquot part of the distillate used should not contain more than +one-tenth of a gram of furfurol. The precipitate formed in this way is +collected on an asbestos felt, dried at 103° and weighed. The weight +obtained divided by 1.974 gives the corresponding amount of furfurol. +There is some difficulty experienced in loosening the precipitate from +the sides of the tubes in which the heating takes place, but this +defect can be overcome by heating in covered beakers in an autoclave.</p> + +<p id="P_157"><b>157. Precipitation with Phloroglucin.</b>—Instead of using +pyrogalol for the precipitating reagent phloroglucin may be employed. +The method of procedure proposed by Councler for this purpose is given +below.<a id="FNanchor_131" href="#Footnote_131" class="fnanchor">[131]</a> +The furfurol is prepared by distillation in the usual way. The volume +of the distillate obtained is completed to half a liter with twelve per +cent hydrochloric acid, and an aliquot portion, varying in volume with +the percentage of furfurol is withdrawn for precipitation. This portion +is placed in a glass-stoppered flask with about twice the quantity of +finely powdered phloroglucin necessary to combine with the furfurol +present. The contents of the flask are well shaken and allowed to stand +fifteen hours. The precipitate is collected on an asbestos filter, washed +free of chlorin, dried at the temperature of boiling water and weighed.</p> + +<p>The theoretical quantity of precipitate corresponding to one part +of furfurol, <i>viz.</i>, 2.22 parts, is never obtained since the +precipitate is not wholly insoluble in water. The actual proportions +between the precipitate and the original furfurol vary with the amount +of precipitate obtained.</p> + +<p>When the weight of the precipitate is 200 milligrams and over, 2.12 +parts correspond to one part of furfurol. When the weight of the +precipitate varies from fifty to 100 milligrams, the ratio is as 2.05:1 +and when only about twenty-five milligrams of precipitate are obtained +the ratio is as 1.98:1.</p> + +<p>The quantity of pentose bodies corresponding to the furfurol is +calculated from the factors given by Tollens in a preceding paragraph. +<span class="pagenum"><a id="Page_185"></a>[Pg 185]</span></p> + +<p>The reaction which takes place with furfurol and phloroglucin is simply +a condensation of the reagents with the separation of water. It is very +nearly represented by the following formula:</p> + +<table class="spb1"> + <tbody><tr> + <td class="tdc">2C₅H₄O₂</td> + <td class="tdl_wsp">+</td> + <td class="tdc">C₆H₆O₃</td> + <td class="tdl_wsp">=</td> + <td class="tdc">C₁₆H₁₂O₆</td> + <td class="tdl_wsp">+</td> + <td class="tdc">H₂O.</td> + </tr><tr> + <td class="tdl">Furfurol.</td> + <td class="tdl_wsp"> </td> + <td class="tdl_wsp">Phloroglucin</td> + <td class="tdl_wsp"> </td> + <td class="tdc">Condensation<br>product.</td> + <td class="tdl_wsp"> </td> + <td class="tdl_wsp">Water.</td> + </tr> + </tbody> +</table> + +<p>It has been shown by Welbel and Zeisel,<a id="FNanchor_132" href="#Footnote_132" class="fnanchor">[132]</a> +that in the presence of twelve per cent of hydrochloric acid +phloroglucin itself is condensed into dark insoluble compounds. When +three molecules of furfurol and two molecules of phloroglucin are +present, the bodies are both condensed and separated by continued +action. When from one and a quarter to three parts of phloroglucin by +weight are used to one part of furfurol, the weight of the precipitate +obtained under constant conditions may serve sufficiently well for +the calculation of the furfurol. The precipitates contain chlorin, +which they give up even in the cold, to water. For these reasons the +analytical data obtained by the method of Councler, given above, are +apt to be misleading. It is probable also that similar conditions +may to a certain extent prevail in the separation of furfurol with +phenylhydrazin, and further investigation in this direction is +desirable. For the present the very best method that can be recommended +for the estimation of pentoses and pentosans is the conversion thereof +into furfurol and the separation of the compound with phenylhydrazin +acetate.</p> + +<p><b>158. Estimation of Sugars by Fermentation.</b>—When a solution +of a hexose sugar is subjected to the action of certain ferments a +decomposition of the molecule takes place with the production of carbon +dioxid and various alcohols and organic acids. Under the action of +the ferment of yeast <i>Saccharomyces cerevisiae</i> the sugar yields +theoretically only carbon dioxid and ethyl alcohol, as represented by +the equation:</p> + +<p class="f105">C₆H₁₂O₆ = 2C₂H₆O + 2CO₂.</p> + +<p>The theoretical quantities of alcohol and carbon dioxid obtained +according to this equation are 51.11 percent of alcohol and 48.89 per +cent of carbon dioxid.</p> + +<p>When the yeast ferment acts on cane sugar the latter first suffers +inversion, and the molecules of dextrose and levulose produced are +<span class="pagenum"><a id="Page_186"></a>[Pg 186]</span> +subsequently converted into alcohol and carbon dioxid as represented +below:</p> + +<p class="f105">C₁₂H₂₂O₁₁ + H₂O = 2C₆H₁₂O₆<br> +2C₆H₁₂O₆ = 4C₂H₆O + 4CO₂.</p> + +<p>Cane sugar, plus the water of hydrolysis, will yield theoretically 53.8 +per cent of alcohol and 51.5 per cent of carbon dioxid.</p> + +<p>In practice the theoretical proportions of alcohol and carbon dioxid +are not obtained because of the difficulty of excluding other +fermentative action, resulting in the formation especially of succinic +acid and glycerol. Moreover, a part of the sugar is consumed by the +yeast cells to secure their proper growth and development. In all +only about ninety-five per cent of the sugar can be safely assumed as +entering into the production of alcohol. About 48.5 per cent of alcohol +are all that may be expected of the weight of dextrose or invert sugar +used. Only sugars containing three molecules of carbon or some multiple +thereof are fermentable. Thus the trioses, hexoses, nonoses, etc., are +susceptible of fermentation, while the tetroses, pentoses, etc., are +not.</p> + +<p><b>159. Estimating Alcohol.</b>—In the determination of sugar by +fermentation, a rather dilute solution not exceeding ten per cent +should be used. A quantity of pure yeast, equivalent to four or five +per cent of the sugar used, is added, and the contents of the vessel, +after being well shaken, exposed to a temperature of from 25° to 30° +until the fermentation has ceased, which will be usually in from +twenty-four to thirty-six hours. The alcohol is then determined in the +residue by the methods given hereafter.</p> + +<p>The weight of the alcohol obtained multiplied by 100 and divided by +48.5, will give the weight of the hexose reducing sugar which has been +fermented. Ninety-five parts of sucrose will give 100 parts of invert +sugar.</p> + +<p><i>Example.</i>—Let the weight of alcohol obtained be 0.625 gram. Then +0.625 × 100 ÷ 48.5 = 1.289 grams, the weight of the hexose, which has +been fermented; 1.289 grams of dextrose or levulose correspond to 1.225 +of sucrose.</p> + +<p><b>160. Estimating Carbon Dioxid.</b>—The sugar may also be determined +by estimating the amount of carbon dioxid produced during the +<span class="pagenum"><a id="Page_187"></a>[Pg 187]</span> +fermentation. For this purpose the mixture of sugar solution and yeast, +prepared as above mentioned, is placed in a flask whose stopper carries +two tubes, one of which introduces air free of carbon dioxid into the +contents of the flask, and the other conducts the evolved carbon dioxid +into the absorption bulbs. In passing to the absorption bulbs the +carbon dioxid is freed of moisture by passing through another set of +bulbs filled with strong sulfuric acid. During the fermentation, the +carbon dioxid is forced through the bulbs by the pressure produced, or +better, a slow current of air is aspirated through the whole apparatus. +The aspiration is continued after the fermentation, has ceased, until +all the carbon dioxid is expelled. Towards the end, the contents of +the flask may be heated to near the boiling-point. The increase of +the weight of the potash bulbs will give the weight of carbon dioxid +obtained. A hexose reducing sugar will yield about 46.5 per cent of its +weight of carbon dioxid. The calculation is made as suggested for the +alcohol process.</p> + +<p>The fermentation process has little practical value save in determining +sucrose in presence of lactose, as will be described in another place.</p> + +<p><b>161. Precipitation of Sugars in Combination with the Earthy +Bases.</b>—The sugars combine in varying proportions with the oxids +and hydroxids of calcium, strontium and barium. Sucrose especially, +furnishes definite crystalline aggregates with these bases in such +a way as to form the groundwork of several technical processes in +the separation of that substance from its normally and abnormally +associated compounds. These processes have little use as analytical +methods, but are of great value, as mentioned, from a technical point +of view.</p> + +<p><b>162. Barium Saccharate.</b>—This compound is formed by mixing +the aqueous solutions of barium hydroxid and sugar. The saccharate +separates in bright crystalline plates or needles from the warm +solution, as <b>C₁₂H₂₂O₁₁BaO</b>. One part of this precipitate is soluble in +about forty-five parts of water, both at 15° and 100°.</p> + +<p><b>163. Strontium Saccharates.</b>—Both the mono- and distrontium +saccharates are known, <i>viz.</i>, <b>C₁₂H₂₂O₁₁SrO + 5H₂O</b> and +<b>C₁₂H₂₂O₁₁2SrO</b>.</p> + +<p><span class="pagenum"><a id="Page_188"></a>[Pg 188]</span> +The monosalt may be easily secured by adding a few of its crystals to a +mixture of sugar and strontium hydroxid solutions.</p> + +<p>The disaccharate is precipitated as a granular substance when from two +to three molecules of strontium hydroxid are added to a boiling sugar +solution. The reaction is extensively used in separating the sugar from +beet molasses.</p> + +<p><b>164. Calcium Saccharates.</b>—Three calcium saccharates are known +in which one molecule of sugar is combined with one, two and three +molecules of lime respectively.</p> + +<p>The monosaccharate is obtained by mixing the sugar and lime in the +proper proportion and precipitating by adding alcohol.</p> + +<p>The precipitate is partly granular and partly jelly-like, and is +soluble in cold water. The dicalcium compound is obtained in the same +way and has similar properties. Both, on boiling, with water, form the +trisaccharate and free sugar.</p> + +<p>The tricalcium saccharate is the most important of these compounds, and +may be obtained directly by mixing freshly burned and finely ground +lime <b>(CaO)</b> with a very cold dilute solution of sugar.</p> + +<p>The compound crystallizes with three or four molecules of water. +When precipitated as described above, however, it has a granular, +nearly amorphous structure, and the process is frequently used in the +separation of sugar from beet molasses.</p> + +<p>In the laboratory but little success has been had in using even the +barium hydroxid as a chemical reagent, and therefore the reactions +mentioned above are of little value for analytical purposes. In +separating sugar from vegetable fibers and seeds, however, the +treatment with strontium hydroxid is especially valuable the sugar +being subsequently recovered in a free state by breaking up the +saccharate with carbon dioxid. The technical use of these reactions +also is of great importance in the beet sugar industry.</p> + +<p><b>165. Qualitive Tests for the Different Sugars.</b>—The analyst will +often be aided in examining an unknown substance by the application +of qualitive tests, which will disclose to him the nature of the +saccharine bodies with which he has to deal.</p> + +<p><b>166. Optical Test for Sucrose.</b>—The simplest test for the +presence of sucrose is made with the polariscope. A small quantity of +<span class="pagenum"><a id="Page_189"></a>[Pg 189]</span> +the sample under examination is dissolved in water, clarified by any of +the usual methods, best with alumina cream, and polarized. A portion of +the liquor is diluted with one-tenth its volume of strong hydrochloric +acid and heated to just 68°, consuming about fifteen minutes time in +the operation. The mixture is quickly cooled and again polarized in +a tube one-tenth longer than before used; or the same tube may be +used and the observed reading of the scale increased by one-tenth. +If sucrose be present the second reading will be much lower than the +first, or may even be to the left.</p> + +<p><b>167. Cobaltous Nitrate Test for Sucrose.</b>—Sucrose in solution +may be distinguished from other sugars by the amethyst violet color +which it imparts to a solution of cobaltous nitrate. This reaction was +first described by Reich, in 1856, but has only lately been worked out +in detail. The test is applied as follows:</p> + +<p>To about fifteen cubic centimeters of the sugar solution add five cubic +centimeters of a five per cent solution of cobaltous nitrate. After +thoroughly mixing the two solutions, add two cubic centimeters of a +fifty per cent solution of sodium hydroxid. Pure sucrose gives by this +treatment an amethyst violet color, which is permanent. Pure dextrose +gives a turquoise blue color which soon passes into a light green. When +the two sugars are mixed the coloration produced by the sucrose is the +predominant one, and one part of sucrose in nine parts of dextrose can +be distinguished. If the sucrose be mixed with impurities such as gum +arabic or dextrin, they should be precipitated by alcohol or basic lead +acetate, before the application of the test. Dextrin may be thrown +out by treatment of the solution with barium hydroxid and ammoniacal +lead acetate. The reaction may also be applied to the detection of +cane sugar in wines, after they are thoroughly decolorized by means of +lead acetate and bone-black. The presence of added sucrose to milk, +either in the fresh or condensed state, may also be detected after the +disturbing matters are thrown out with lead acetate. The presence of +sucrose in honey may also be detected by this process. The reaction +has been tried in this laboratory with very satisfactory results. The +amethyst violet coloration with sucrose is practically permanent. On +<span class="pagenum"><a id="Page_190"></a>[Pg 190]</span> +boiling the color is made slightly bluish, but is restored to the +original tint on cooling. Dextrose gives at first a fine blue color +which in the course of two hours passes into a pale green. A slight +flocculent precipitate is noticed in the tube containing the dextrose. +Maltose and lactose act very much as dextrose, but in the end do not +give so fine a green color. If the solutions containing dextrose, +lactose and maltose be boiled, the original color is destroyed and a +yellow-green color takes its place. The reaction is one which promises +to be of considerable practical value to analysts, as it may be applied +for the qualitive detection of sucrose in seeds and other vegetable +products.<a id="FNanchor_133" href="#Footnote_133" class="fnanchor">[133]</a></p> + +<p><b>168. The Dextrose Group.</b>—In case the carbohydrate in question +shows a right-handed rotation and the absence of sucrose is established +by the polariscopic observation described above, the presence of the +dextrose group may be determined by the following +test.<a id="FNanchor_134" href="#Footnote_134" class="fnanchor">[134]</a></p> + +<p>Five grams of the carbohydrate are oxidized by boiling with from twenty +to thirty cubic centimeters of nitric acid of 1.15 specific gravity, +and then at gentle heat evaporated to dryness with stirring. If much +mucic acid be present, as will be the case if the original matter +contained lactose some water is added and the mixture well stirred, +and again evaporated to dryness to expel all nitric acid. The residue +should be of a brown color. The mass is again mixed with a little +water and the acid reaction neutralized by rubbing with fine-ground +potassium carbonate. The carbonate should be added in slight excess and +acetic acid added to the alkaline mixture, which is concentrated by +evaporation and allowed to stand a few days. At the end of this time +potassium saccharate has formed and is separated from the mother liquid +by pouring on a porous porcelain plate. The residue is collected, +dissolved in a little water and again allowed to crystallize, when it +is collected on a porous plate, as before, and washed by means of an +atomizer with a little aqueous spray until it is pure white and free of +any oxalic acid. The residual acid potassium saccharate may be weighed +after drying and then converted into the silver salt. The potash salt +for this purpose is dissolved in water, neutralized with ammonia and +precipitated with a solution of silver nitrate. The precipitate is well +<span class="pagenum"><a id="Page_191"></a>[Pg 191]</span> +stirred, collected on a gooch and washed and dried in a dark place. +It contains 50.94 percent of silver. All sugars which contain the +dextrose group yield silver saccharate when treated as above described. +Inulin, sorbose, arabinose and galactose yield no saccharic acid under +this treatment, and thus it is shown that they contain no dextrose +group. Milk sugar, maltose, the dextrins, raffinose and sucrose yield +saccharic acid when treated as above and therefore all contain the +dextrose group.</p> + +<p><b>169. Levulose.</b>—The levulose group of sugars, wherever it +occurs, when oxidized with nitric acid, gives rise to tartaric, +racemic, glycolic and oxalic acids, which are not characteristic, +being produced also by the oxidation of other carbohydrates. A more +distinguishing test is afforded by the color reactions produced with +resorcin.<a id="FNanchor_135" href="#Footnote_135" class="fnanchor">[135]</a> +The reagent is prepared by dissolving half a gram of resorcin in thirty +cubic centimeters each of water and strong hydrochloric acid. To the +sugar solution under examination an equal volume of strong hydrochloric +acid is added, and then a few drops of the reagent. The mixture is +gently warmed, and in the presence of levulose develops a fire-red +color. Dextrose, lactose, mannose and the pentoses do not give the +coloration, but it is produced by sorbose in a striking degree, and +also by sucrose and raffinose since these sugars contain the levulose +group.</p> + +<p><b>170. Galactose.</b>—The galactose which arises from the hydrolysis +of milk sugar is readily recognized by the mucic acid which it gives +on oxidation with nitric acid.<a id="FNanchor_136" href="#Footnote_136" class="fnanchor">[136]</a> +The analytical work is conducted as follows: The body containing +galactose or galactan is placed in a beaker with about sixty cubic +centimeters of nitric acid of 1.15 specific gravity for each five grams +of the sample used. The beaker is placed on a steam-bath and heated, +with frequent stirring, until two-thirds of the nitric acid have been +evaporated. The residual mixture is allowed to stand over night and +the following morning is treated with ten cubic centimeters of water, +allowed to stand for twenty-four hours, filtered through a gooch, and +the collected matter washed with twenty-five cubic centimeters of +water, dried at 100° and weighed. The mucic acid collected in this way +<span class="pagenum"><a id="Page_192"></a>[Pg 192]</span> +will amount to about thirty-seven per cent of the milk sugar or +seventy-five per cent of the galactose oxidized. Raffinose yields under +similar treatment, about twenty-three per cent of mucic acid, which +proves that the galactose group is contained in that sugar. Raffinose, +therefore, is composed of one molecule each of dextrose, levulose, and +galactose.</p> + +<p id="P_171"><b>171. Invert Sugar.</b>—The presence of a trace of invert sugar +accompanying sucrose can be determined by Soldaini’s solution, +paragraph <b><a href="#P_124">124</a></b>, or by boiling with methyl blue.<a id="FNanchor_137" href="#Footnote_137" class="fnanchor">[137]</a> +Methyl blue is the hydrochlorate of an ammonium base, which, under the influence +of a reducing agent, loses two atoms of hydrogen and becomes a colorless +compound. The test for invert sugar is made as follows: The reagent +is prepared by dissolving one gram of methyl blue in water. If the +sugar solution is not clear, twenty grams of the sugar are dissolved +in water clarified by lead subacetate, the volume completed to 100 +cubic centimeters, and the solid matters separated by filtration. The +filtrate is made slightly alkaline with sodium carbonate to remove the +lead. A few drops of soda lye solution are then added and the mixture +thrown on a filter. To twenty-five cubic centimeters of the filtrate a +drop of the methyl blue solution is added, and a portion of the liquor +heated in a test tube over the naked flame. If, after boiling for one +minute, the coloration disappear, the sample contains at least 0.01 +per cent of invert sugar; if the solution remain blue it contains none +at all or less than 0.01 per cent. The test may also be made with the +dilute copper carbonate solution of Ost described further on.</p> + +<p id="P_172"><b>172. Compounds with Phenylhydrazin.</b>—Many sugars may also be +qualitively distinguished by the character of their compounds with +phenylhydrazin. In general, it may be said that those sugars which +reduce fehling solution form definite crystalline compounds with the +reagent named. If a moderately dilute hot solution of a reducing sugar +be brought into contact with phenylhydrazin acetate, a crystalline +osazone is separated. The reaction takes place between one molecule of +the sugar and two molecules of the hydrazin compound, according to the +following formula:</p> + +<p class="f105">C₆H₁₂O₆ + 2C₆H₅N₂H₃ = C₁₈H₂₂N₄O₄ + 2H₂O + H₂.</p> + +<p><span class="pagenum"><a id="Page_193"></a>[Pg 193]</span> +The hydrogen does not escape but combines in the nascent state with the +excess of phenylhydrazin to form anilin and ammonia.</p> + +<p>The precipitation is accomplished as follows:</p> + +<p>One part by weight of the sugar, two parts of phenylhydrazin +hydrochlorate, and three parts of sodium acetate are dissolved in +twenty parts of water and gradually heated on the water-bath.</p> + +<p>The osazone slowly separates in a crystalline form and it is freed from +the mother liquor by filtration, and purified by solution in alcohol +and recrystallization. The crystals are composed of yellow needles, +which are difficultly soluble in water and more easily in hot alcohol. +The crystals are not decomposed by a dilute acid but are destroyed by +the action of strong acids.</p> + +<p><i>Dextrosazone.</i>—The crystals melt at from 204° to 205°, reduce +fehling liquor, and dissolved in glacial acetic acid are slightly left +rotating.</p> + +<p><i>Levulosazone.</i>—This body has the same properties as the dextrose +compound.</p> + +<p><i>Maltosazone.</i>—This substance melts at 206° with decomposition. +It is left rotating. Its structure is represented by the formula +<b>C₂₄H₃₂N₄O₉</b>.</p> + +<p><i>Galactosazone.</i>—This substance, <b>C₁₈H₂₂N₄O₄</b>, has the same +centesimal composition as the corresponding bodies produced from +dextrose and levulose. It is distinguished from these compounds, +however, by its low melting point, <i>viz.</i>, 193°.</p> + +<p>The above comprise all the phenylosazones which are important from +the present point of view. Sucrose, by inversion, furnishes a mixture +of dextros- and levulosazones when treated with phenylhydrazin, while +starch and dextrin yield the dextros- or maltosazone when hydrolyzed. +Lactose yields a mixture of dextros- and galactosazones when hydrolyzed +and treated as above described.</p> + +<p>The reactions with phenylhydrazin are approximately quantitive and it +is possible that methods of exact determination may be based on them in +the near future.<a id="FNanchor_138" href="#Footnote_138" class="fnanchor">[138]</a></p> + +<p><b>173. Other Qualitive Tests for Sugars.</b>—The analyst may +sometimes desire a more extended test of qualitive reactions than those +<span class="pagenum"><a id="Page_194"></a>[Pg 194]</span> +given above. The changes of color noticed on heating with alkalies may +often be of advantage in discriminating between different sugars. The +formation of definite compounds with the earthy and other mineral bases +may also be used for qualitive determinations. One of the most delicate +qualitive tests is found in the production of furfurol and this will be +described in the following paragraphs.</p> + +<p><b>174. Detection of Sugars and Other Carbohydrates by Means of +Furfurol.</b>—The production of furfurol (furfuraldehyd) as noted in +paragraph <b><a href="#P_150">150</a></b>, is also used quantitively for the determination +of pentose sugars and pentosans.</p> + +<p>Furfurol was first obtained from bran (<i>furfur</i>), whence its name, +by treating this substance with sulfuric acid, diluted with three +volumes of water, and subjecting the mixture to distillation. Its +percentage composition is represented by the symbol <b>C₅H₄O₂</b>, and its +characteristics as an aldehyd by the molecular structure <b>C₄H₃O,C-HO</b>.</p> + +<p>Carbohydrates in general, when treated as described above for bran, +yield furfurol, but only in a moderate quantity, with the exception of +the pentoses.</p> + +<p>Mylius has shown<a id="FNanchor_139" href="#Footnote_139" class="fnanchor">[139]</a> +that Pettenkofer’s reaction for choleic acid is due to the furfurol +arising from the cane sugar employed, which, with the gall acid, +produces the beautiful red-blue colors characteristic of the +reaction.</p> + +<p>Von Udránszky<a id="FNanchor_140" href="#Footnote_140" class="fnanchor">[140]</a> +describes methods for detecting traces of carbohydrates by the +furfurol reaction, which admit of extreme delicacy. The solution of +furfurol in water, at first proposed by Mylius, is to be used and +it should not contain more than two and two-tenths per cent, while +a solution containing five-tenths per cent furfurol is found to be +most convenient. The furfurol, before using, should be purified by +distillation, and, as a rule, only a single drop of the solution used +for the color reaction.</p> + +<p>The furfurol reaction proposed by Schiff<a id="FNanchor_141" href="#Footnote_141" class="fnanchor">[141]</a> +appears to be well suited for the detection of carbohydrates. +It is made as follows:</p> + +<p>Xylidin is mixed with an equal volume of glacial acetic acid and the +solution treated with some alcohol. Strips of filter paper are then +dipped in the solution and dried. When these strips of prepared paper +are brought in contact with the most minute portion of furfurol, +<span class="pagenum"><a id="Page_195"></a>[Pg 195]</span> +furoxylidin is formed, <b>C₄H₃OCH(C₈H₈NH₂)₂</b>, producing a beautiful red +color. In practice, a small portion of the substance, supposed to +contain a carbohydrate, is placed in a test tube and heated with a +slight excess of concentrated sulfuric acid. The prepared paper is then +placed over the mouth of the test tube so as to be brought into contact +with the escaping vapors of furfurol.</p> + +<p>The furfurol reaction with α-naphthol for some purposes, especially +the detection of sugar in urine, is more delicate than the one just +described. This reaction was first described by Molisch<a id="FNanchor_142" href="#Footnote_142" class="fnanchor">[142]</a>, +who, however, did not understand its real nature.</p> + +<p>The process is carried on as follows: The dilute solution should +contain not to exceed from 0.05 to one-tenth per cent of carbohydrates. +If stronger, it should be diluted. Place one drop of the liquid in a +test tube with two drops of fifteen per cent alcoholic solution of +α-naphthol, add carefully one-half cubic centimeter of concentrated +sulfuric acid, allowing it to flow under the mixture. The appearance +of a violet ring over a greenish fringe indicates the presence of a +carbohydrate. If the substance under examination contain more than a +trace of nitrogenous matter, this must be removed before the tests +above described are applied.</p> + +<p>If the liquids be mixed by shaking when the violet ring is seen, a +carmine tint with a trace of blue is produced. If this be examined with +a spectroscope, a small absorption band will be found between D and E, +and from F outward the whole spectrum will be observed. One drop of +dextrose solution containing 0.05 per cent of sugar gives a distinct +reaction by this process. It can be used, therefore, to detect the +presence of as little as 0.028 milligram of grape sugar. This test has +been found exceedingly delicate in this laboratory, and sufficiently +satisfactory without the spectroscopic adjunct.</p> + +<p>The furfurol reaction is useful in detecting the presence of minute +traces of carbohydrates but is of little value in discriminating +between the different classes of these bodies.</p> + +<p>It is not practical here to go into greater detail in the description +of qualitive reactions. The analyst, desiring further information, +should consult the standard works on sugar chemistry. +<a id="FNanchor_143" href="#Footnote_143" class="fnanchor">[143]</a></p> + +<p><span class="pagenum"><a id="Page_196"></a>[Pg 196]</span> +<b>175. Detection of Sugars by Bacterial Action.</b>—Many forms of +bacteria manifest a selective action towards sugars and this property +may in the future become the basis of a qualitive and even quantitive +test for sugars and other carbohydrates. Our present knowledge of the +subject is due almost exclusively to the researches of Smith, conducted +at the Department of Agriculture.<a id="FNanchor_144" href="#Footnote_144" class="fnanchor">[144]</a> +Dextrose is the sugar first and most vigorously attacked by bacterial +action, and by proper precautions the whole of the dextrose may be +removed from mixtures with sucrose and lactose.</p> + +<p>The development of other forms of micro-organisms which will have the +faculty of attacking other and special forms of carbohydrates is to be +looked for with confident assurance of success.</p> + +<h3>DETERMINATION OF STARCH.</h3> + +<p><b>176. Constitution of Starch.</b>—The molecule of starch is without +doubt formed by the condensation of a large number of hexose bodies. +On account of its great insolubility its molecular weight has not been +determined with any degree of accuracy. Its formula may be expressed +either as <b>(C₆H₁₀O₅)ₙ</b> or <b>(C₁₂H₂₀O₁₀)ₙ</b>. It is insoluble in cold water +and other common solvents and does not pass into solution in any reagent +without undergoing a change of structure. In hot water it forms a paste +and when heated under pressure with water it undergoes a partial change +and becomes soluble. Heated with acids or subjected to the action of +certain ferments it suffers hydrolysis and is transformed into dextrin, +maltose and dextrose. In analytical work an attempt is usually made to +transform the starch entirely into dextrose, the quantity of which is +then determined by some of the processes already given. All starches +possess the property of giving an intensely blue color with iodin and +this reaction serves to detect the most minute quantity of the material.</p> + +<p>Starch grains derived from different sources are distinguished by +differences in size and appearance. In most cases a careful examination +of the starch particles will reveal their origin.<a id="FNanchor_145" href="#Footnote_145" class="fnanchor">[145]</a> +The greatest part of the cereal grains is composed of starch, the +percentage ranging from sixty to eighty. Rice has the greatest +<span class="pagenum"><a id="Page_197"></a>[Pg 197]</span> +percentage of starch in its composition of any substance. Certain +root crops are also rich in starch, such as the potato, artichoke and +cassava. Starch appears as one of the first products of vegetable +metabolism, according to some authorities, preceding the formation +of sugars. By reason of its greater complexity, however, it is more +probable that the production of simple sugars precedes the formation of +the more complex molecule. Starch granules are probably used as a food +by the plant in the building of more complex structures and the excess +of this food is stored in the seeds and in tubers.</p> + +<p><b>177. Separation of Starch Particles.</b>—Advantage is taken of the +insolubility of the starch particles to secure their separation from +the other vegetable structures with which they are associated. The +substances containing starch are reduced to a pulp as fine as possible, +and this pulp being placed in a fine cloth the starch particles are +washed through the cloth with water. The milky filtrate carrying the +starch is collected in an appropriate holder and, after some time, the +particles subside. They may then be collected and dried. While this +process is the one used commercially in the manufacture of starch, it +can only give approximate data respecting the actual quantity of starch +in a given weight of the sample. It is not quite possible by this +method to get all the starch separated from the rest of the vegetable +matter, and particles of foreign substances, such as cellulose and +albuminoid matters, may pass through the filter cloth and be found +with the deposited granules. It follows from this that the quantitive +determination of the starch in a given sample by any direct method is +only approximately exact.</p> + +<p><b>178. Methods of Separation.</b>—Hot acids cannot be safely employed +to dissolve starch from its natural concomitants because other +carbohydrate bodies become soluble under similar conditions. In such +cases the natural sugars which are present should be removed by cold +water and the starch dissolved from the residue by a diastatic ferment. +Instead of this the sugars may be determined in a separate portion +of the pulped material and the starch, together with the sugars, determined, +and the quantity of sugar found deducted from the final result. +<span class="pagenum"><a id="Page_198"></a>[Pg 198]</span></p> + +<p>In these cases the final determinations are made on the sugars, after +inverting the sucrose, and proceeding as directed for invert sugars +in paragraph <b><a href="#P_141">141</a></b>. The starch, after separation with diastase, +is converted into dextrose by one of the methods to be given and the +resulting dextrose determined by one of the approved methods.</p> + +<p id="P_179"><b>179. Separation with Diastase.</b>—Diastase or malt extract at +a temperature of about 65° rapidly renders starch soluble. Cereals, +potato meal and other starch-holding bodies are dried, first at a low +temperature, and extracted with ether or petroleum to remove fat. The +material is then rubbed up with water, boiled, cooled to 65°, and +treated with malt extract (diastase) prepared as given below. One +kilogram of ground green malt is mixed with one liter of glycerol +and an equal quantity of water, and allowed to stand, with frequent +shaking, for eight days. After that time the mixture is filtered, +first through a small filter press and afterwards through paper. In +case no filter press is at hand the mixture may be pressed in a bag +and the liquor obtained, filtered. Malt extract obtained in this way +will keep its diastatic properties for a long time. In its use, blank +determinations must be made of the dextrose produced by treating equal +portions of it with hydrochloric acid. For three grams of starchy +material twenty-five cubic centimeters of the malt solution should be +used and the mixture kept at 65° for two hours.<a id="FNanchor_146" href="#Footnote_146" class="fnanchor">[146]</a></p> + +<p><b>180. Method in Use at the Halle Station.</b>—The method of +separating starch from cereals, potatoes and other starch-holding +materials, employed at the Halle station, is essentially the same as +already described.<a id="FNanchor_147" href="#Footnote_147" class="fnanchor">[147]</a></p> + +<p>The malt extract used is prepared immediately beforehand, inasmuch +as no preservative is added to it. It can be quickly prepared by +digesting, for a short time at not above 50°, 100 grams of finely +ground dried malt with one liter of water and separating the extract by +filtration. This extract will keep only a few hours.</p> + +<p>The material in which the starch is to be determined is dried and +extracted with ether. From two to four grams of the extracted material, +<span class="pagenum"><a id="Page_199"></a>[Pg 199]</span> +according to the amount of starch which it contains, are boiled for +half an hour with 100 cubic centimeters of water, cooled to 65°, +treated with ten cubic centimeters of malt extract and kept at the +temperature named for half an hour. It is then again boiled for fifteen +minutes, cooled to the temperature mentioned and again treated with +malt extract as above. Two treatments with malt extract are usually +sufficient to bring all the starch into solution. Finally it is again +boiled and the volume completed to 250 cubic centimeters and thrown +upon a filter. Two hundred cubic centimeters of the filtrate are +converted into dextrose by boiling with hydrochloric acid, and the rest +of the analysis is conducted in the usual manner. The dextrose value of +the quantity of malt extract used must be determined upon a separate +portion thereof, and the quantity of dextrose found deducted from the +total amount obtained in the analysis.</p> + +<div class="figleft smcap"> + <img id="FIG_47A" src="images/fig47.jpg" alt="" width="200" height="366" > + <p class="center spb1">Figure 47.<br> Autoclave for<br> Starch Analysis.</p> +</div> + +<p id="P_181"><b>181. Separation by Hydrolysis with Water at High +Temperatures.</b>—Instead of dissolving the starch with diastase, it +may be brought into solution by heating with water under pressure. The +former method employed of heating in sealed flasks has been entirely +superceded by heating in an autoclave. The materials are best held in +metal beakers furnished with a cover which prevents loss from boiling +if the pressure should be removed too rapidly after the completion +of the operation. The autoclave is a strong metal vessel capable of +resisting the pressure of several atmospheres. It is furnished with a +pressure gauge C and a safety valve D, as shown in the <a href="#FIG_47A">figure</a>. +The top is securely screwed on by means of a wrench, shown at the right hand +<span class="pagenum"><a id="Page_200"></a>[Pg 200]</span> +side. In the <a href="#FIG_47A">figure</a> a portion of the case is +represented cut away to show the arrangement of the metal beakers +inside.</p> + +<p>In the method of Reinke, as practiced at the Halle station, and in +this laboratory, about three grams of the starchy substance are placed +in each of the metal beakers with twenty-five cubic centimeters of +a one per cent lactic acid solution and thirty cubic centimeters of +water. The contents of the beaker are thoroughly mixed and they are +then heated for two and a half hours in the autoclave, at a pressure +of three and a half atmospheres. The addition of the lactic acid is +for the purpose of protecting any sugar which may be present from +decomposition at the high pressure and temperature employed. After +the completion of the heating, the autoclave is allowed to cool, the +cover is removed and the beakers taken out and their contents washed +with hot water into quarter liter flasks. After cooling, the volume +is completed with cold water, and after standing for half an hour, +with frequent shaking, the contents of the flasks are filtered and +200 cubic centimeters of the filtrate in each case converted into +dextrose with hydrochloric acid in the usual way. In order to obtain +agreeing results, it is highly necessary that the substance before +treatment should be ground to a fine powder. The addition of the lactic +acid, as practiced in the reinke method, tends to give somewhat high +results, due probably to the hydrolytic action of the acid on the +fiber present. When starchy bodies are heated in the autoclave for the +determination of their starch by polarimetric methods, or for ordinary +determinations, the use of lactic acid should be omitted.</p> + +<p><i>Example.</i>—The following data indicate the methods of calculation +to be followed in the determination of the percentage of starch in the +material by diastatic hydrolysis: Three grams of a barley were inverted +by diastase, as directed above, the volume of the solution made a +quarter of a liter, filtered, 200 cubic centimeters of the filtrate +converted into dextrose by hydrochloric acid, the volume completed to +half a liter with water and fifty cubic centimeters thereof oxidized +by the alkaline copper solution in the usual way. The amount of copper +obtained was 331 milligrams, corresponding to 174 milligrams of +dextrose. The amount of malt extract used in hydrolyzing the barley +<span class="pagenum"><a id="Page_201"></a>[Pg 201]</span> +mentioned above, was ten cubic centimeters. The diastatic solution +inverted with hydrochloric acid and treated as indicated above, yielded +191 milligrams of copper, corresponding to ninety-eight milligrams of +dextrose in ten cubic centimeters of the malt extract. The quantity of +malt extract represented in the final determination of copper, however, +was only one and six-tenths cubic centimeters. We then have:</p> + +<table class="spb1"> + <tbody><tr> + <td class="tdl">Total dextrose</td> + <td class="tdr_wsp"> 174</td> + <td class="tdr">milligrams</td> + </tr><tr> + <td class="tdl">Dextrose in one and six-tenths cubic centimeters</td> + <td class="tdr_wsp"> </td> + <td class="tdr"> </td> + </tr><tr> + <td class="tdl_ws2">malt extract</td> + <td class="tdr_wsp">16</td> + <td class="tdr">milligrams</td> + </tr><tr> + <td class="tdl">Dextrose corresponding to 240 milligrams</td> + <td class="tdr_wsp"> </td> + <td class="tdr"> </td> + </tr><tr> + <td class="tdl_ws2">of barley</td> + <td class="tdr_wsp">158</td> + <td class="tdr">milligrams</td> + </tr> + </tbody> +</table> + +<p>Calculated on the proportion that dextrose is to starch, as ten is to +nine, this is equivalent to 142 milligrams of starch. The percentage +of starch in the original substance, therefore, was equivalent to 142 +multiplied by 100, divided by 240, <i>viz.</i>, 59.17.</p> + +<p><b>182. Principles of the Methods of Determination.</b>—In the +approximately pure state in which starch exists in the trade, it may +be determined by conversion into dextrose and estimating the latter +by one of the methods given. It is probable that there is no known +method by which starch can be entirely converted into dextrose, and +all the methods of hydrolysis, when used for quantitive purposes, +must be standardized, not by the theoretical quantity of dextrose +which a given weight of pure starch should yield, but by the actual +quantity obtained. Starch is not largely converted into dextrose by +any of the diastatic ferments which produce principally maltose and +dextrins. Recourse must therefore be had to strong acids. In practice, +hydrochloric is the one usually employed. By the action of a hot +mineral acid, not only is starch converted into dextrose, but also +the dextrose found is subjected to changes. In such cases an opposing +action seems to be exerted by the hydrolytic agent, a part of the +dextrose formed suffering a partial condensation, and thus assuming +a state of higher molecular weight, approaching the constitution of +the dextrins. Another part of the dextrose may also suffer oxidation and +thus disappear entirely in respect of the further steps in starch analysis. +<span class="pagenum"><a id="Page_202"></a>[Pg 202]</span></p> + +<p>In such cases, the best the analyst can do is to conduct the hydrolysis +in as nearly as possible constant conditions, and to assume that the +percentage of dextrose present at a given time bears a constant ratio +to the quantity of starch hydrolyzed. In reality almost all the starch +appears finally as dextrose, and by proceeding on the assumption noted +above a fairly satisfactory accounting may be made of the remainder.</p> + +<p>Starch being insoluble, it cannot be determined directly by its +rotatory power. When heated for a few hours in contact with water at a +high pressure, starch becomes soluble, and in this state has a fairly +constant gyrodynat, <i>viz.</i>, [<i>a</i>]<span class="fs_80"><sub>D</sub></span> = 197°.</p> + +<p>Starch is also rendered soluble by rubbing it in a mortar for about ten +minutes with an excess of strong hydrochloric acid, and in this way +a quick approximate idea may be obtained of the percentage present. +Starch prepared in this manner, however, has a strong reducing power +on metallic salts, showing that a part of it has already, even in so +short a time, assumed the state of maltose or dextrose. The gyrodynat +of pure anhydrous starch in such conditions varies from [<i>a</i>]<span class="fs_80"><sub>D</sub></span> += 197° to [<i>a</i>]<span class="fs_80"><sub>D</sub></span> = 194°. Starch +is also rendered soluble by boiling with salicylic acid, whereby a +solution is obtained having a gyrodynat of [<i>a</i>]<span class="fs_80"><sub>D</sub></span> = +200°(circa). The methods of procedure for the analysis of starch will +be set forth in detail in the following paragraphs.</p> + +<p><b>183. Estimation of Water.</b>—In prepared or commercial starches +the water may be determined by heating in a partial vacuum. The +temperature at first should be low, not exceeding 60°. After drying +for an hour at that heat the temperature may be gradually increased. +The last traces of water come off from starch with difficulty, and the +final temperature may be carried a little beyond 100° without danger of +decomposition.</p> + +<p>Ost recommends the use of an atmosphere of hydrogen or illuminating +gas.<a id="FNanchor_148" href="#Footnote_148" class="fnanchor">[148]</a> +One and a half grams of the finely powdered sample are placed +in the drying tube described in paragraph <b><a href="#P_23">23</a></b>, and heated in a +stream of dry hydrogen. The temperature at first is kept at about 60° +for several hours and is then gradually increased to 120°. Ost states +that even at 150° the sample preserves its pure white color, but so +high a temperature is not necessary. Maercker, at the Halle station, +<span class="pagenum"><a id="Page_203"></a>[Pg 203]</span> +makes use of the same process, but employs illuminating gas instead +of hydrogen. The importance of beginning the desiccation at a low +temperature arises from the fact that at a higher temperature, before +the greater part of the water is driven off, the starch will suffer +a partial fusion and form a paste which is very difficult to dry. +The dried sample must be kept in a stoppered vessel to prevent the +absorption of hygroscopic moisture.</p> + +<p><b>184. Estimation of Ash.</b>—When the drying is accomplished in +a flat platinum dish, the same sample may serve for incineration. +Otherwise the incineration may be accomplished in another portion of +the sample by following directions already given.<a id="FNanchor_149" href="#Footnote_149" class="fnanchor">[149]</a></p> + +<p><b>185. Nitrogen.</b>—Even very pure samples of starch may contain +a little nitrogen which is most conveniently determined by moist +combustion.<a id="FNanchor_150" href="#Footnote_150" class="fnanchor">[150]</a></p> + +<p>As a rule, in commercial starches of good quality, the quantity of pure +starch may be considered to be the remainder after subtracting the sum +of the weights of water, ash and nitrogen multiplied by 6.25, from the +original weight of the sample taken.</p> + +<table class="spb1"> + <tbody><tr> + <td class="tdl"><i>Example</i>:—</td> + <td class="tdl_wsp"> </td> + <td class="tdr"> </td> + </tr><tr> + <td class="tdl_ws1">Per cent of</td> + <td class="tdl_wsp">moisture found</td> + <td class="tdr">12.85</td> + </tr><tr> + <td class="tdl_ws1"> ”  ” ”</td> + <td class="tdl_wsp">ash found</td> + <td class="tdr">0.08</td> + </tr><tr> + <td class="tdl_ws1"> ”  ” ”</td> + <td class="tdl_wsp">nitrogen × 6.25</td> + <td class="tdr bb">0.27</td> + </tr><tr> + <td class="tdc">Sum</td> + <td class="tdl"> </td> + <td class="tdr">13.20</td> + </tr><tr> + <td class="tdl_ws1">Per cent of</td> + <td class="tdl_wsp">pure starch in sample </td> + <td class="tdr">86.80</td> + </tr> + </tbody> +</table> + +<p>Samples of starch usually contain also traces of fat and fiber, and +these when present in weighable quantities, should be determined and +proper deductions made.</p> + +<p id="P_186"><b>186. Hydrolysis with Acids.</b>—The acids commonly chosen for +hydrolyzing starch are sulfuric and hydrochloric. The former has the +advantage of being more easily removed from the finished product but +the latter performs the work with less damage to the sugars formed. For +commercial purposes sulfuric and for analytical practice hydrochloric +acids are commonly employed. +<span class="pagenum"><a id="Page_204"></a>[Pg 204]</span></p> + +<div class="figcenter smcap"> + <img id="FIG_47B" src="images/fig47_2.jpg" alt="" width="300" height="402" > + <p class="center spb1">Figure 47 (bis). Maercker’s<br> Hydrolyzing Apparatus for Starch.</p> +</div> + +<p>The best process for analytical purposes is the one proposed by +Sachsse.<a id="FNanchor_151" href="#Footnote_151" class="fnanchor">[151]</a> +In this method the starch is heated with the hydrolyzing mixture in +the proportion of three grams to 200 cubic centimeters of water and +twenty of hydrochloric acid of 1.125 specific gravity, containing five +and six-tenths grams of the pure gas. The heating is continued for +three hours on a steam-bath. Maercker recommends, instead of the above +procedure, heating for two hours at gentle ebullition in an oil-bath. +In this method three grams of the starch are reduced to paste with 200 +cubic centimeters of water, and then boiled for two hours with fifteen +<span class="pagenum"><a id="Page_205"></a>[Pg 205]</span> +cubic centimeters of hydrochloric acid of 1.125 specific gravity. +The erlenmeyers in which the hydrolysis takes place are heated in an +oil-bath and are provided with reflux condensers made of long glass +tubes on which some bulbs have been blown, as shown in the accompanying +<a href="#FIG_47B">figure</a>. In all cases after hydrolysis the +solution is neutralized, made to a standard volume and an aliquot part, +after filtration, diluted to contain an amount of dextrose suited +to the use of the table by Allihn for calculating the percentage +of sugar. In diluting the solution preparatory to the estimation +of dextrose, it is well to remember that nine parts of starch will +furnish theoretically ten parts of dextrose. Since three grams of the +sample are used, containing approximately eighty-five per cent of +starch, the quantity of dextrose present is a little less than three +grams. The solution should therefore contain not less than 300 cubic +centimeters.</p> + +<p><b>187. Factor for Calculating Starch from the Dextrose +Obtained.</b>—If all the starch could be converted into dextrose +without loss, the quantity of it could be easily calculated +theoretically on the supposition that the formula of starch is +<b>(C₆H₁₀O₅)ₙ</b>. The factor by this assumption is, starch = dextrose × 0.90. +If the starch have the formula assigned to it by Nägeli, <i>viz.</i>, +<b>C₃₆H₆₂O₃₁</b> the formula becomes, starch = dextrose × 0.918.</p> + +<p>Ost prefers to work by Sachsse’s method and to use the factor 0.925 to +convert the dextrose into starch.<a id="FNanchor_152" href="#Footnote_152" class="fnanchor">[152]</a></p> + +<p>In view of all the facts in the case it appears that the analyst will +reach nearly correct results by converting the starch into dextrose +by heating for three hours at 100° with hydrochloric acid or for two +hours at gentle ebullition as directed above, determining the resultant +dextrose and multiplying the weight thereof by 0.92.</p> + +<p><b>188. Polarization of Starch.</b>—Starch may be prepared for +polarization by dissolving it in cold hydrochloric acid. The process +as carried out by Effront is as follows.<a id="FNanchor_153" href="#Footnote_153" class="fnanchor">[153]</a> +Five grams of starch are rubbed with twenty cubic centimeters of +cold concentrated hydrochloric acid for nearly ten minutes or until +the solution is quite clear. The volume is completed to 200 cubic +centimeters with water and the solution polarized. By this process +there is always produced a notable quantity of reducing sugars, and for +<span class="pagenum"><a id="Page_206"></a>[Pg 206]</span> +this reason it must be admitted that a portion of the starch has +suffered complete hydrolysis. Ost therefore recommends the use of an +acid of 1.17 specific gravity, and the gyrodynat of the soluble starch +thus produced is found to vary from [<i>a</i>]<span class="fs_80"><sub>D</sub></span> += 196°.3 to 196°.7. When acid of 1.20 specific gravity is employed the gyrodynat +falls to [<i>a</i>]<span class="fs_80"><sub>D</sub></span> = 194.2.<a id="FNanchor_154" href="#Footnote_154" class="fnanchor">[154]</a> +For approximately correct work the solution with the weaker hydrochloric +acid and subsequent polarization is to be recommended as the most rapid +method for starch determination.</p> + +<p>It will be of interest to add the observation that the gyrodynat +of maltose has lately been redetermined by Ost, who finds it to be +[<i>a</i>]<span class="fs_80"><sub>D</sub></span>²⁰ ° = 137°.04 ± 0.19.<a id="FNanchor_155" href="#Footnote_155" class="fnanchor">[155]</a></p> + +<p><b>189. Solutions of Starch at High Pressure.</b>—Starch may also be +brought into a condition suited to polarization by dissolving in water +at a high temperature and pressure. The solution is accomplished in an +autoclave as described in <b><a href="#P_181">181</a></b>.</p> + +<p>From two to three grams of starch are used and from eighty to ninety +cubic centimeters of water. The starch is first reduced to a pasty +state by heating with the water and, when evenly distributed throughout +the flask, is rendered soluble by heating from three to five hours in +an autoclave at from two to three atmospheres. The material is entirely +without action on an alkaline copper solution. After heating, the +volume of the solution is completed to 100 cubic centimeters and it is +then polarized. The gyrodynat of starch dissolved in this way varies +from [<i>a</i>]<span class="fs_80"><sub>D</sub></span> = 196°.5 to 197°.<a id="FNanchor_156" href="#Footnote_156" class="fnanchor">[156]</a></p> + +<p>Starch is prepared by Baudry for polarization by boiling with +salicylic acid.<a id="FNanchor_157" href="#Footnote_157" class="fnanchor">[157]</a> +The gyrodynat of starch dissolved in this way is [<i>a</i>]<span class="fs_80"><sub>D</sub></span> += 200°.25.</p> + +<p><b>190. Polarization after Solution in Dilute Nitric +Acid.</b>—Guichard recommends saccharification with ten per cent +nitric acid (ten cubic centimeters strong acid, ninety cubic +centimeters water).<a id="FNanchor_158" href="#Footnote_158" class="fnanchor">[158]</a> +This treatment, even after prolonged boiling, gives only a light straw +color to the solution which does not interfere with its polarization +with a laurent instrument.</p> + +<p>In working on cereals four grams of the finely ground material, in +which the bran and flour are intimately mixed, are used.</p> + +<p>The material is placed in a flask of about 500 cubic centimeters +<span class="pagenum"><a id="Page_207"></a>[Pg 207]</span> +capacity, with 100 cubic centimeters of the dilute acid. The flask is +closed with a stopper carrying a reflux condenser. After boiling for +an hour the contents of the flask are filtered and examined in the +saccharimeter. The dextrose formed is determined by the polarimetric +data and the quantity of starch transformed calculated from the +dextrose. The following formula is used:</p> + +<table class="spb1 fs_105"> + <tbody><tr> + <td class="tdl" rowspan="2"><i>A</i> = </td> + <td class="tdc bb"><i>av</i> × 25 × 0.016</td> + </tr><tr> + <td class="tdc">2 × 52.8</td> + </tr> + </tbody> +</table> + +<p>In this formula <i>a</i> = the rotation in angular degrees, <i>v</i> = +the volume of the liquid and <i>A</i> = the starch transformed.</p> + +<p>In this method no account is taken of the sucrose and other sugars +which are present in cereals. In the case of sucrose the left-handed +sugar produced by treatment with nitric acid would diminish the +rotation to the right and thus introduce an error. On the other hand +the dextrose formed from the fiber of the bran would be calculated as +starch. If these two errors should be compensating the method might +prove practical.</p> + +<p><b>191. Rapid Estimation Of Starch.</b>—For the rapid estimation of +starch in cereals, cattle foods and brewery refuse, Hibbard recommends +a method which is carried out as follows:</p> + +<p>The malt extract is prepared by covering ground, dry malt with water +containing from fifteen to twenty per cent of alcohol. The object of +adding alcohol is to preserve the filtered extract. It exercises a +slight retarding effect on the action of the diastase, but prevents the +malt extract from fermenting. After standing for a few hours in contact +with the malt, the liquid is separated by filtration and is then ready +for use. The substance in which the starch is to be determined should +be dry enough to be finely pulverized, but previous extraction with +ether is omitted. Enough of the material to contain at least half a +gram of starch is placed in a flask with fifty cubic centimeters of +water and from one to two cubic centimeters of malt extract added. The +mixture is at once heated to boiling with frequent shaking to prevent +the formation of clots. The addition of the diastase before boiling is +to aid in preventing the formation of lumps. After boiling a minute the +mixture is cooled to 60° and from two to three cubic centimeters of +the malt extract added. It is then slowly heated until it again boils, +<span class="pagenum"><a id="Page_208"></a>[Pg 208]</span> +consuming about fifteen minutes, when, after cooling, it is tested +with iodin for starch. If a blue color be produced the operation above +described is repeated until it fails to reappear. The mixture is then +made up to a standard volume, thrown on a linen filter and an aliquot +part of the filtrate, representing from 200 to 300 milligrams of +starch, is boiled with five cubic centimeters of hydrochloric acid, of +thirty per cent strength, for half an hour. The total volume of the +liquid before boiling should be completed to sixty cubic centimeters. +By the method above described, it is claimed that the determination of +starch in a cereal or similar substance can be completed within two +hours. The chief amount of time saved is in the heating with the malt +extract, which instead of being continued for two hours, as usually +directed, can be accomplished in thirty +minutes.<a id="FNanchor_159" href="#Footnote_159" class="fnanchor">[159]</a></p> + +<p><b>192. Precipitation of Starch with Barium Hydroxid.</b>—The tendency +of carbohydrate bodies to unite with the earthy bases has been utilized +by Asboth as a basis for the quantitive determination of +starch.<a id="FNanchor_160" href="#Footnote_160" class="fnanchor">[160]</a></p> + +<p>About three grams of the finely ground sample containing the starch, +or one gram of pure starch, are rubbed up in a mortar with water and +the detached starch remaining suspended in the wash water is poured +off. This operation is repeated until all the starch is removed. In +difficult cases hot water may be used. The starch thus separated is +heated in a quarter liter flask to the boiling point to reduce it to +the condition of paste. When the paste is cold it is treated with fifty +cubic centimeters of the barium hydroxid solution, the flask closed and +well shaken for two minutes. The volume is then completed to the mark +with forty-five per cent alcohol, the flask well shaken and allowed +to stand. In a short time the barium-starch compound separates and +settles. Fifty cubic centimeters of the clear supernatant liquor are +removed with a pipette, or the liquor may be passed through a filter +and the quantity mentioned removed for titration of the residual barium +hydroxid after the addition of a few drops of phenolphthalein solution.</p> + +<p>The quantity of barium hydroxid remaining, deducted from the original +quantity, gives the amount which has entered into composition with the +<span class="pagenum"><a id="Page_209"></a>[Pg 209]</span> +starch; the composition of the molecule being <b>BaOC₂₄H₄₀O₂₀</b>, which +contains 19.10 per cent of barium oxid and 80.90 per cent of starch.</p> + +<p>The set solution of barium hydroxid must be preserved from contact with +the carbon dioxid of the air. The burette should be directly attached +to the bottle holding the set solution, by any of the usual appliances, +and the air entering the bottle must be deprived of carbon dioxid. The +water used in the work must be also free of air, and this is secured by +boiling immediately before use.</p> + +<p class="blockquot"><i>Example.</i>—A sample of flour selected for +the analysis weighed 3.212 grams. The starch was separated and reduced +to paste in the manner described above. Thirty and four-tenths cubic +centimeters of tenth-normal hydrochloric acid were exactly neutralized +by ten cubic centimeters of the barium hydroxid solution. After +treatment as above described, fifty cubic centimeters of the clear +liquor, corresponding to ten cubic centimeters of the added barium +hydroxid, required 19.05 cubic centimeters of tenth-normal hydrochloric +acid. Then 30.4 - 19.05 = 11.35, and 11.35 x 5 = 56.75, which number +corresponds to the total titration of the residual barium hydroxid in +terms of tenth-normal hydrochloric acid. This number multiplied by +0.0324, <i>viz.</i>, starch corresponding to one equivalent of barium, +gave 1.8387 grams of starch or 57.24 per cent of the weight of flour employed.</p> + +<p>The barium hydroxid method has been given a thorough trial in this +laboratory and the results have been unsatisfactory when applied to +cereals. The principle of the process, however, appears to be sound, +and with a proper variation of working details, it may become practical.</p> + +<p><b>193. Disturbing Bodies in Starch Determinations.</b>—Stone has made +a comparison of the standard methods of starch determinations, and the +results of his work show that in the case of pure starch all of the +standard methods give approximately correct figures. For instance, in +the case of a pure potato starch, the following data were obtained:</p> + +<p>By inversion with hydrochloric acid, 85.75 per cent; by inversion with +oxalic and nitric acids, 85.75 per cent; by solution in salicylic acid, +85.47 per cent; and by precipitation with barium hydroxid, 85.58 per +cent.<a id="FNanchor_161" href="#Footnote_161" class="fnanchor">[161]</a></p> + +<p><span class="pagenum"><a id="Page_210"></a>[Pg 210]</span> +When these methods are used, however, for the determination of starch +in its original state, the widest variations are secured. Stone shows +that these variations are due chiefly to the inverting effect of the +reagents employed upon the pentosans present. In experiments made with +pure xylan obtained from wheat straw, the methods employed gave from +44.73 to 67.16 per cent of material, which would be calculated by +the usual methods as starch. Stone also shows that the pentosans are +practically unaffected by the action of diastase or malt extract. Pure +xylan treated with diastase, under the condition in which starch is +converted into maltose and other soluble carbohydrates, fails to give +any subsequent reaction whatever with alkaline copper solution. In +all cases, therefore, where starch occurs in conjunction with pentose +bodies, it is necessary to separate it by diastatic action before +applying any of the methods of conversion of the starch into dextrose +or its precipitation by barium hydroxid.</p> + +<p><b>194. Colorimetric Estimation of Starch.</b>—The production of the +intensely blue color which starch gives with iodin has been used not +only as the basis of a qualitive method, but also of many attempts at +quantitive determination. These attempts have, as a rule, been attended +with very unsatisfactory results, due both to the extraordinary +delicacy of the reaction and to the fact that starches of different +origin do not always give exactly the same intensity of tint when +present in the same quantity. At the present it must be admitted that +little should be expected of any quantitive colorimetric test.</p> + +<p>In case such a test is desired the procedure described by Dennstedt +and Voigtländer may be followed.<a id="FNanchor_162" href="#Footnote_162" class="fnanchor">[162]</a> +A weighed quantity of the starch-holding material, containing +approximately half a gram of starch, is placed in a two liter flask and +boiled with a liter of water. After cooling, the volume is completed to +two liters and the starch allowed to subside. Five cubic centimeters of +the clear supernatant liquor are placed in a graduated cylinder holding +100, and marked in half cubic centimeters. One drop of a solution of +iodin in potassium iodid is added and the volume completed to the mark. +A half gram of pure starch is treated in the same way and different +<span class="pagenum"><a id="Page_211"></a>[Pg 211]</span> +measured portions of the solution treated as above until the color of +the first cylinder is matched. From the quantity of pure starch in +the matched cylinder the quantity in the sample is determined. The +test should be made in duplicate or triplicate. If a violet color be +produced instead of a blue, it may be remedied by treating the sample +with alcohol before the starch granules are dissolved.</p> + +<p><b>195. Fixation of Iodin.</b>—In addition to forming a distinctive +blue color with iodin, starches have the power of fixing considerable +quantities of that substance. The starches of the cereals have this +power in a higher degree than those derived from potatoes. In presence +of a large excess of iodin the starches of rice and wheat have a +maximum iodin-fixing power of about nineteen per cent of their weight. +When only enough of iodin is employed to enter into combination +the percentage absorbed varies from nine to fifteen per cent. The +absorption of iodin by starches is a matter of importance from a +general chemical standpoint, but as at present determined has but +little analytical value. It is evident, however, that this absorption +must take place according to definite chemical quantities and the +researches of investigators may in the future discover some definite +quantitive method of measuring it.<a id="FNanchor_163" href="#Footnote_163" class="fnanchor">[163]</a></p> + +<p><b>196. Identification of Starches of Different Origin.</b>—It is +often important, especially in cases of suspected adulteration, to +determine the origin of the starch granules. For this purpose the +microscope is the sole resort. In many cases it is easy to determine +the origin of the starch by the size or the shape and marking of the +grains. In mixtures of more than one kind of starch the distinguishing +features of the several starches can be clearly made out in most +instances. There are, however, many instances where it is impossible to +discriminate by reason of the fact that the characteristics of starch +granules vary even in the same substance and from year to year with +varying conditions of culture.</p> + +<p>In many cases the illustrations of the forms and characteristics of +starch granules which are found in books are misleading and no reliance +can be placed on any illustrations which are not either photographs or +drawings made directly from them. In the microscopic study of starches +<span class="pagenum"><a id="Page_212"></a>[Pg 212]</span> +the analyst will be greatly helped by the following descriptions of the +characteristic appearance of the granules and the classifications based +thereon.<a id="FNanchor_164" href="#Footnote_164" class="fnanchor">[164]</a></p> + +<p><b>197. Vogel’s Table of the Different Starches and Arrowroots of +Commerce.</b>—<i>A.</i> Granules simple, bounded by rounded surfaces.</p> + +<ul class="index"> +<li class="isub1">I. Nucleus central, layers concentric.</li> +<li class="isub2"><i>a.</i> Mostly round, or from the side, lens-shaped.</li> +<li class="isub4">1. Large granules 0.0396-0.0528 mm, <i>rye starch</i>:</li> +<li class="isub4">2. Large granules 0.0352-0.0396 mm, <i>wheat starch</i>:</li> +<li class="isub4">3. Large granules 0.0264 mm, <i>barley starch</i>.</li> + +<li class="isub2"><i>b.</i> Egg-shaped, oval, kidney-shaped: Hilum often long and ragged:</li> +<li class="isub4">1. Large granules 0.032-0.079 mm, <i>leguminous starches</i>.</li> + +<li class="isub1">II. Nucleus eccentric, layers plainly eccentric or meniscus-shaped.</li> +<li class="isub2"><i>a.</i> Granules not at all or only slightly flattened:</li> +<li class="isub4">1. Nucleus mostly at the smaller end; 0.06-0.10 mm, <i>potato starch</i>:</li> +<li class="isub4">2. Nucleus mostly at the broader end or towards the middle</li> +<li class="isub5">in simple granules; 0.022-0.060 mm, <i>maranta starch</i>.</li> + +<li class="isub2"><i>b.</i> Granules more or less strongly flattened.</li> +<li class="isub4">1. Many drawn out to a short point at one end.</li> +<li class="isub7"><i>a.</i> At most 0.060 mm long, <i>curcuma starch</i>:</li> +<li class="isub7"><i>b.</i> As much as 0.132 mm long, <i>canna starch</i>:</li> +<li class="isub4">2. Many lengthened to bean-shaped, disk-shaped, or flattened;</li> +<li class="isub5">nucleus near the broader end; 0.044-0.075 mm, <i>banana starch</i>:</li> +<li class="isub4">3. Many strongly kidney-shaped; nucleus near the edge;</li> +<li class="isub5">0.048-0.056 mm, <i>sisyrinchium starch</i>:</li> +<li class="isub4">4. Egg-shaped; at one end reduced to a wedge, at the other enlarged;</li> +<li class="isub5">nucleus at smaller end; 0.05-0.07 mm, <i>yam starch</i>:</li> +</ul> + +<p><i>B.</i> Granules simple or compound, single granules or parts of +granules, either bounded entirely by plain surfaces, many-angled, or by +partly round surfaces. +<span class="pagenum"><a id="Page_213"></a>[Pg 213]</span></p> + +<ul class="index"> +<li class="isub1">I. Granules entirely angular.</li> +<li class="isub2">1. Many with prominent nucleus: At most 0.0066 mm, <i>rice starch</i>:</li> +<li class="isub2">2. Without a nucleus: The largest 0.0088 mm, <i>millet starch</i>:</li> + +<li class="isub1">II. Among the many-angled also rounded forms.</li> +<li class="isub2"><i>a.</i> No drum-shaped forms present, angular form predominating.</li> +<li class="isub4">1. Without nucleus or depression very small;</li> +<li class="isub7">0.0044 mm, <i>oat starch</i>:</li> +<li class="isub4">2. With nucleus or depression; 0.0132-0.0220 mm.</li> +<li class="isub7"><i>a.</i> Nucleus or its depression considerably rounded;</li> +<li class="isub9">here and there the granules united into differently</li> +<li class="isub9">formed groups; <i>buckwheat starch</i>:</li> +<li class="isub7"><i>b.</i> Nucleus mostly radiate or star-shaped; all the</li> +<li class="isub9">granules free; <i>maize</i> (<i>corn</i>) <i>starch</i>:</li> + +<li class="isub2"><i>b.</i> More or less numerous kettledrum and sugar-loaf like forms.</li> +<li class="isub4">1. Very numerous eccentric layers; the largest granules</li> +<li class="isub7">0.022-0.0352 mm, <i>batata</i> (sweet potato) <i>starch</i>:</li> +<li class="isub4">2. Without layers or rings; 0.008-0.022 mm.</li> +<li class="isub6"><i>a.</i> In the kettledrum-shaped granules the nucleal</li> +<li class="isub8">depression mostly widened on the flattened</li> +<li class="isub8">side; 0.008-0.022 mm, <i>cassava starch</i>:</li> +<li class="isub6"><i>b.</i> Depression wanting or not enlarged.</li> +<li class="isub8"><i>aa.</i> Nucleus small, eccentric; 0.008-0.016 mm,</li> +<li class="isub10"><i>pachyrhizus starch</i>:</li> +<li class="isub8"><i>bb.</i> Nucleus small, central, or wanting.</li> +<li class="isub10"><i>aaa.</i> Many irregular angular forms;</li> +<li class="isub12">0.008-0.0176 mm, <i>sechium starch</i>:</li> +<li class="isub10"><i>bbb.</i> But few angular forms; some with radiate,</li> +<li class="isub12">nucleal fissure; 0.008-0.0176 mm, <i>chestnut starch</i>.</li> +</ul> + +<p><i>C.</i> Granules simple and compound; predominant forms, oval, with +eccentric nucleus and numerous layers; the compound granule made up +of a large granule and one or more relatively small kettledrum-shaped +ones; 0.025-0.066 mm, <i>sago starch</i>. +<span class="pagenum"><a id="Page_214"></a>[Pg 214]</span></p> + +<p class="f120"><b>198. Muter’s Table for the Detection of Starches<br> + when Magnified about 230 Diameters.</b></p> + +<p class="f90">[All measurements are given in decimals of an inch.]</p> + +<p class="center"><span class="fs_120"><i>Group I</i>:</span> All more or less +oval in shape and having both hilum and rings visible.</p> + +<table class="spb1"> + <thead><tr> + <th class="tdc bb bt">Name.</th> + <th class="tdc bb bl bt">Shape.</th> + <th class="tdc bb bl bt">Normal<br> measurements. </th> + <th class="tdc bb bl bt">Remarks.</th> + </tr></thead> + <tbody><tr> + <td class="tdl bb">Tous les mois </td> + <td class="tdl_wsp bl bb">Oval, with flat ends</td> + <td class="tdc bl bb">0.00370<br> to 0.00185</td> + <td class="tdl_wsp bl bb">Hilum annular, near one<br>end and incomplete rings.</td> + </tr><tr> + <td class="tdl bb">Potato</td> + <td class="tdl_wsp bl bb">Oval</td> + <td class="tdc bl bb">0.00270<br>to 0.00148</td> + <td class="tdl_wsp bl bb">Hilum annular, rings incomplete,<br> + shape and size very variable.</td> + </tr><tr> + <td class="tdl bb">Bermuda<br> arrowroot</td> + <td class="tdl_wsp bl bb">Sack-shaped</td> + <td class="tdc bl bb">0.00148<br>to 0.00129</td> + <td class="tdl_wsp bl bb">Hilum distinct annular, shape<br>variable, rings faint.</td> + </tr><tr> + <td class="tdl bb">St. Vincent<br> arrowroot</td> + <td class="tdl_wsp bl bb">Oval-oblong</td> + <td class="tdc bl bb">0.00148<br>to 0.00129</td> + <td class="tdl_wsp bl bb">Hilum semi-lunar, rings faint,<br> + shape not very variable.</td> + </tr><tr> + <td class="tdl bb">Natal<br> arrowroot</td> + <td class="tdl_wsp bl bb">Broadly ovate</td> + <td class="tdc bl bb">0.00148<br>to 0.00129</td> + <td class="tdl_wsp bl bb">Hilum annular, in center and<br> + well marked complete rings.</td> + </tr><tr> + <td class="tdl bb">Galangal</td> + <td class="tdl_wsp bl bb">Skittle-shaped</td> + <td class="tdc bl bb">About 0.00135</td> + <td class="tdl_wsp bl bb">Hilum elongated, very faint<br>incomplete rings.</td> + </tr><tr> + <td class="tdl bb">Calumba</td> + <td class="tdl_wsp bl bb">Broadly pear-shaped</td> + <td class="tdc bl bb"> ” 0.00185</td> + <td class="tdl_wsp bl bb">Hilum semi-lunar, faint but<br> + complete rings, shape variable.</td> + </tr><tr> + <td class="tdl bb">Orris root</td> + <td class="tdl_wsp bl bb">Elongated-oblong</td> + <td class="tdc bl bb"> ” 0.00092</td> + <td class="tdl_wsp bl bb">Hilum faint, shape characteristic.</td> + </tr><tr> + <td class="tdl bb">Turmeric</td> + <td class="tdl_wsp bl bb">Oval-oblong, conical</td> + <td class="tdc bl bb"> ” 0.00148</td> + <td class="tdl_wsp bl bb">Very strongly marked<br>incomplete rings.</td> + </tr><tr> + <td class="tdl bb">Ginger</td> + <td class="tdl_wsp bl bb">Shortly conical, with <br>rounded angles.</td> + <td class="tdc bl bb"> ” 0.00148</td> + <td class="tdl_wsp bl bb">Hilum and rings scarcely<br>visible, shape variable<br> + but characteristic.</td> + </tr> + </tbody> +</table> + +<p class="spa2"><span class="pagenum"><a id="Page_215"></a>[Pg 215]</span></p> + +<p class="center"><span class="fs_120"><i>Group II</i>:</span> With strongly +developed hilum more or less stellate.</p> + +<table class="spb1"> + <thead><tr> + <th class="tdc bb bt">Name.</th> + <th class="tdc bb bl bt">Shape.</th> + <th class="tdc bb bl bt">Normal<br> measurements. </th> + <th class="tdc bb bl bt">Remarks.</th> + </tr></thead> + <tbody><tr> + <td class="tdl bb">Bean</td> + <td class="tdl_wsp bl bb">Oval-oblong</td> + <td class="tdc bl bb">About 0.00135</td> + <td class="tdl_wsp bl bb">Fairly uniform.</td> + </tr><tr> + <td class="tdl bb">Pea</td> + <td class="tdl_wsp bl bb">Like bean</td> + <td class="tdc bl bb">0.00111<br>to 0.00074</td> + <td class="tdl_wsp bl bb">Very variable in size,with granules<br>under preponderating.</td> + </tr><tr> + <td class="tdl bb">Lentil</td> + <td class="tdl_wsp bl bb">Like bean</td> + <td class="tdc bl bb">About 0.00111</td> + <td class="tdl_wsp bl bb">Hilum, a long depression<br>seldom radiate.</td> + </tr><tr> + <td class="tdl bb">Nutmeg  </td> + <td class="tdl_wsp bl bb">Rounded</td> + <td class="tdc bl bb"> ” 0.00055</td> + <td class="tdl_wsp bl bb">The small size and rounded<br>form distinctive.</td> + </tr><tr> + <td class="tdl bb">Dari</td> + <td class="tdl_wsp bl bb">Elongated hexagon</td> + <td class="tdc bl bb"> ” 0.00074</td> + <td class="tdl_wsp bl bb">Irregular appearance and great<br>convexity distinctive.</td> + </tr><tr> + <td class="tdl bb">Maize</td> + <td class="tdl_wsp bl bb">Round and polygonal </td> + <td class="tdc bl bb"> ” 0.00074</td> + <td class="tdl_wsp bl bb">The rounded angles of the<br>polygonalgranules distinctive.</td> + </tr> + </tbody> +</table> + +<p class="center spa2"><span class="fs_120"><i>Group III</i>:</span> +Hilum and rings practically invisible.</p> + +<table class="spb1"> + <thead><tr> + <th class="tdc bb bt">Name.</th> + <th class="tdc bb bl bt">Shape.</th> + <th class="tdc bb bl bt">Normal<br> measurements. </th> + <th class="tdc bb bl bt">Remarks.</th> + </tr></thead> + <tbody><tr> + <td class="tdl bb">Wheat</td> + <td class="tdl_wsp bl bb">Circular and flat</td> + <td class="tdc bl bb">0.00185<br>to 0.00009</td> + <td class="tdl_wsp bl bb">Very variable in size and very dull<br> polarization in water.</td> + </tr><tr> + <td class="tdl bb">Barley</td> + <td class="tdl_wsp bl bb">Slightly angular circles </td> + <td class="tdc bl bb">About 0.00073</td> + <td class="tdl_wsp bl bb">The majority measuring about 0.00373<br> + distinctive, and a few four times<br>this size.</td> + </tr><tr> + <td class="tdl bb">Rye</td> + <td class="tdl_wsp bl bb">Like barley</td> + <td class="tdc bl bb">0.00148<br>to 0.00009</td> + <td class="tdl_wsp bl bb">Small granules, quite round,<br>and here and there cracked.</td> + </tr><tr> + <td class="tdl bb">Jalap</td> + <td class="tdl_wsp bl bb">Like wheat</td> + <td class="tdc bl bb"> </td> + <td class="tdl_wsp bl bb">Polarizes brightly in water.</td> + </tr><tr> + <td class="tdl bb">Rhubarb</td> + <td class="tdl_ws2 bl bb">do.</td> + <td class="tdc bl bb">0.00055<br>to 0.00033</td> + <td class="tdl_wsp bl bb">Polarizes between jalap and wheat,<br> + and runs smaller and more convex.</td> + </tr><tr> + <td class="tdl">Senega</td> + <td class="tdl_wsp bl">Like wheat</td> + <td class="tdc bl">0.00148-0.00009</td> + <td class="tdl_wsp bl bb" rowspan="3">Measurements the only guide.</td> + </tr><tr> + <td class="tdl">Bayberry</td> + <td class="tdl_ws2 bl">do.</td> + <td class="tdc bl">0.00074-0.00011</td> + </tr><tr> + <td class="tdl bb">Sumbul</td> + <td class="tdl_ws2 bl bb">do.</td> + <td class="tdc bl bb">0.00074-0.00009</td> + </tr><tr> + <td class="tdl bb">Chestnut</td> + <td class="tdl_wsp bl bb">Very variable</td> + <td class="tdc bl bb">0.00090-0.00009</td> + <td class="tdl_wsp bl bb">Variable form, and small but<br>regular size, distinctive.</td> + </tr><tr> + <td class="tdl bb">Acorn</td> + <td class="tdl_wsp bl bb">Round-oval</td> + <td class="tdc bl bb">About 0.00074</td> + <td class="tdl_wsp bl bb">Small and uniform size, distinctive.</td> + </tr><tr> + <td class="tdl bb">Calabar bean</td> + <td class="tdl_wsp bl bb">Oval-oblong</td> + <td class="tdc bl bb">0.00296<br>to 0.00180</td> + <td class="tdl_wsp bl bb">Large size and shape characteristic.</td> + </tr><tr> + <td class="tdl bb">Licorice</td> + <td class="tdl_wsp bl bb">Elongated-oval</td> + <td class="tdc bl bb">About 0.00018</td> + <td class="tdl_wsp bl bb">Small size and shape distinctive.</td> + </tr><tr> + <td class="tdl bb">Hellebore<br> (green or black)</td> + <td class="tdl_wsp bl bb">Perfectly rotund</td> + <td class="tdc bl bb">0.00037<br>to 0.00009</td> + <td class="tdl_wsp bl bb">Small, regular size and rotundity,<br>distinctive.</td> + </tr><tr> + <td class="tdl bb">Hellebore<br> (white)</td> + <td class="tdl_wsp bl bb">Irregular</td> + <td class="tdc bl bb">0.00055<br>to 0.00009</td> + <td class="tdl_wsp bl bb">Irregular shape and faint central<br> + depression, distinctive.</td> + </tr> + </tbody> +</table> +<p class="spa2"><span class="pagenum"><a id="Page_216"></a>[Pg 216]</span></p> + +<p class="center spa2"><span class="fs_120"><i>Group IV</i>:</span> +More or less truncated at one end.</p> + +<table class="spb1"> + <thead><tr> + <th class="tdc bb bt">Name.</th> + <th class="tdc bb bl bt">Shape.</th> + <th class="tdc bb bl bt">Normal<br> measurements. </th> + <th class="tdc bb bl bt">Remarks.</th> + </tr></thead> + <tbody><tr> + <td class="tdl bb">Cassia</td> + <td class="tdl_wsp bl bb">Round</td> + <td class="tdc bl bb">0.00111<br>to 0.00018</td> + <td class="tdl_wsp bl bb">Round or muller shaped granules<br>and faint circular hilum.</td> + </tr><tr> + <td class="tdl bb">Cinnamon</td> + <td class="tdl_wsp bl bb">Like cassia</td> + <td class="tdc bl bb">0.00074<br>to 0.00009</td> + <td class="tdl_wsp bl bb">More frequently truncated than<br>cassia, and smaller.</td> + </tr><tr> + <td class="tdl bb">Sago (raw)</td> + <td class="tdl_wsp bl bb">Oval-ovate</td> + <td class="tdc bl bb">0.00260 <br>to 0.00111</td> + <td class="tdl_wsp bl bb">Has circular hilum at convex end<br>and rings faintly visible.</td> + </tr><tr> + <td class="tdl bb">Sago (prepared) </td> + <td class="tdl_ws2 bl bb">”</td> + <td class="tdc bl bb">0.00260<br>to 0.00111</td> + <td class="tdl_wsp bl bb">Has a large oval or circular depression,<br> + covering one-third nearly of each granule.</td> + </tr><tr> + <td class="tdl bb">Tapioca</td> + <td class="tdl_wsp bl bb">Roundish</td> + <td class="tdc bl bb">0.00074<br>to 0.00055</td> + <td class="tdl_wsp bl bb">A little over fifty per cent truncated<br> + by one facet, and a pearly hilum.</td> + </tr><tr> + <td class="tdl bb">Arum</td> + <td class="tdl_wsp bl bb">Like tapioca</td> + <td class="tdc bl bb">About 0.00056</td> + <td class="tdl_wsp bl bb">Smaller than tapioca and truncated<br>by two facets.</td> + </tr><tr> + <td class="tdl bb">Belladonna</td> + <td class="tdl_ws2 bl bb">do.</td> + <td class="tdc bl bb"> </td> + <td class="tdl_wsp bl bb">Not distinguishable from tapioca.</td> + </tr><tr> + <td class="tdl bb">Colchicum</td> + <td class="tdl_ws2 bl bb">do.</td> + <td class="tdc bl bb">About 0.00074</td> + <td class="tdl_wsp bl bb">Larger than tapioca, and contains<br> + many more truncated granules.</td> + </tr><tr> + <td class="tdl bb">Scammony</td> + <td class="tdl_ws2 bl bb">do.</td> + <td class="tdc bl bb"> ” 0.00045</td> + <td class="tdl_wsp bl bb">Smaller than tapioca, more irregular,<br> + and hilum not visible.</td> + </tr><tr> + <td class="tdl bb">Cancella</td> + <td class="tdl_wsp bl bb">Very variable </td> + <td class="tdc bl bb">0.00033-0.00022</td> + <td class="tdl_wsp bl bb">Very variable, form and small size<br>the only points.</td> + </tr><tr> + <td class="tdl bb">Podophyllum</td> + <td class="tdl_wsp bl bb">Like tapioca</td> + <td class="tdc bl bb">About 0.00040</td> + <td class="tdl_wsp bl bb">Like scammony, but has visible hilum<br> + in most of the granules.</td> + </tr><tr> + <td class="tdl bb">Aconite</td> + <td class="tdl_ws2 bl bb">do.</td> + <td class="tdc bl bb"> ” 0.00037</td> + <td class="tdl_wsp bl bb">Like tapioca, but half the size.</td> + </tr> + </tbody> +</table> + +<p class="spa2"><span class="pagenum"><a id="Page_217"></a>[Pg 217]</span></p> + +<p class="center spa2"><span class="fs_120"><i>Group V</i>:</span> +All granules more or less polygonal.</p> + +<table class="spb1"> + <thead><tr> + <th class="tdc bb bt">Name.</th> + <th class="tdc bb bl bt">Shape.</th> + <th class="tdc bb bl bt">Normal<br> measurements. </th> + <th class="tdc bb bl bt">Remarks.</th> + </tr></thead> + <tbody><tr> + <td class="tdl bb">Tacca</td> + <td class="tdl_wsp bl bb">Poly- or hexagonal </td> + <td class="tdc bl bb">0.00075<br>to 0.00037</td> + <td class="tdl_wsp bl bb">Distinguished from maize by<br>its sharp angles.</td> + </tr><tr> + <td class="tdl bb">Oat</td> + <td class="tdl_wsp bl bb">Polygonal</td> + <td class="tdc bl bb">About 0.00037</td> + <td class="tdl_wsp bl bb">Larger than rice and hilum visible<br>in some granules.</td> + </tr><tr> + <td class="tdl bb">Rice></td> + <td class="tdl_ws2 bl bb">do.</td> + <td class="tdc bl bb">0.00030-0.00020</td> + <td class="tdl_wsp bl bb">Measurement using one-eighth or<br> + one-twelfth inch power, and then<br>hilum visible.</td> + </tr><tr> + <td class="tdl bb">Pepper</td> + <td class="tdl_ws2 bl bb">do.</td> + <td class="tdc bl bb">0.00020-0.00002</td> + <td class="tdl_ws2 bl bb">Do.</td> + </tr><tr> + <td class="tdl bb">Ipecacuanha </td> + <td class="tdl_ws2 bl bb">do.</td> + <td class="tdc bl bb">About 0.00018</td> + <td class="tdl_wsp bl bb">Some round and truncated granules,<br> + adhering in groups of three.</td> + </tr> + </tbody> +</table> + +<p><span class="pagenum"><a id="Page_218"></a>[Pg 218]</span> +<b>199. Blyth’s Classification.</b>—Blyth gives the following scheme +for the identification of starch granules by their microscopic +appearance.<a id="FNanchor_165" href="#Footnote_165" class="fnanchor">[165]</a></p> + +<p><i>Division I.—Starches showing a play of colors with polarized light +and selenite plate</i>:</p> + +<p>The hilum and concentric rings are clearly visible, and all the starch +granules, oval or ovate. Canna arrowroot, potato, arrowroot, calumba, +orris root, ginger, galangal and turmeric belong to this division.</p> + +<p><i>Division II.—Starches showing no iridescence, or scarcely any, when +examined by polarized light and selenite</i>:</p> + +<p>Class I.—The concentric rings are all but invisible, and the hilum +stellate. The bean, pea, maize, lentil, dari and nutmeg starches are in +this class.</p> + +<p>Class II.—Starches which have both the concentric rings and hilum +invisible in the majority of granules: this important class includes +wheat, barley, rye, chestnut, acorn, and many starches in medicinal plants.</p> + +<p>Class III.—All the granules are truncated at one end. This class +includes sago, tapioca and arum, several drugs and cinnamon and cassia.</p> + +<p>Class IV.—In this class all the granules are angular in form and it +includes oats, tacca, rice, pepper and ipecacuanha.</p> + +<p><b>200. Preparation of Starches for Microscopical Examination.</b>—The +approximately pure starches of commerce may be prepared for microscopic +examination by rubbing them up with water and mounting some of the +suspended particles by one of the methods to be described below.</p> + +<p>In grains, seeds and nuts the starch is separated by grinding with +water and working through fine linen. The starch which is worked +through is allowed to subside, again beaten up with water if necessary +and the process continued until the grains are separated sufficiently +for microscopic examination. A little potash or soda lye may be used, +if necessary, to separate the granules from albuminous and other +adhering matter. The analyst should have a collection of samples of all +common starches of known origin for purposes of comparison. +<span class="pagenum"><a id="Page_219"></a>[Pg 219]</span></p> + +<p>The granules are mounted for examination by plain light in a medium +of glycerol and camphor water. When polarized light is used the +mounting should be in Canada balsam.<a id="FNanchor_166" href="#Footnote_166" class="fnanchor">[166]</a> +The reader can find excellent photomicrographs of the more common starches +in Griffith’s book.<a id="FNanchor_167" href="#Footnote_167" class="fnanchor">[167]</a></p> + +<p><b>201. Appearance in Balsam with Polarized Light.</b>—Mounted in +balsam the starches are scarcely visible under any form of illumination +with ordinary light, the index of refraction of the granules and the +balsam being so nearly alike. When, however, polarized light is used +the effect is a striking one. It is very easy to distinguish all the +characteristics, except the rings, the center of the cross being at the +nucleus of the granule.</p> + +<p>With the selenite plate a play of colors is produced, which is peculiar +to some of the starches and forms the basis of Blyth’s classification.</p> + +<p><b>202. Description Of Typical Starches.</b>—The more commonly +occurring starches are described by Richardson as they appear under the +microscope magnified about 350 +diameters.<a id="FNanchor_168" href="#Footnote_168" class="fnanchor">[168]</a></p> + +<p>The illustrations, with the exception of the cassava starch, and the +maize starch accompanying it were drawn by the late Dr. Geo. Marx from +photographs made by Richardson in this laboratory. The two samples +excepted were photographed for the author by Dr. G. L. Spencer.</p> + +<p><i>Maranta Starch.</i>—Of the same type as the potato starch are the +various arrowroots, the only one of which commonly met with in this +country being the Bermuda, the starch of the rhizome of <i>Maranta +arundinacea</i>, and the starch of turmeric.</p> + +<p>The granules are usually not so varied in size or shape as those of +the potato, averaging about 0.07 millimeter in length as may be seen +in <a href="#FIG_48">Fig. 48</a>. They are about the same size as the average of +the potato, but are not often found with the same maximum or minimum magnitude, +which circumstance, together with the fact that the end at which the +nucleus appears is broader in the maranta and more pointed in the +potato, enables one to distinguish the two starches without difficulty. +With polarized light the results are similar to those seen with potato +starch, and this is a ready means of distinguishing the two varieties, +<span class="pagenum"><a id="Page_220"></a>[Pg 220]</span> +by displaying in a striking way the form of the granule and position of +the hilum.</p> + +<p><i>Potato Starch.</i>—The starch grains of the potato are very +variable in size, being found from 0.05 to 0.10 millimeter in length, +and in shape from oval and allied forms to irregular and even round +in the smallest. These variations are illustrated in <a href="#FIG_49">Fig. 49</a>, +but the frequency of the smaller granules is not as evident as in some other +cases. The layers are visible in some granules with great distinctness +and in others hardly at all, being rather more prominent in the starch +as obtained from a freshly cut surface. The rings are more distinct, +too, near the hilum or nucleus, which in this, as in all tuberous +starches, is eccentric, shading off toward the broader or more expanded +portion of the granule. The hilum appears as a shadowy depression, +and with polarized light its position is well marked by the junction +of the arms of the cross. With polarized light and a selenite plate a +beautiful play of colors is obtained. The smaller granules, which are +nearly round, may readily be confused with other starches, but their +presence serves at once to distinguish this from maranta or Bermuda +arrowroot starch. Rarely compound granules are found composed of two or +three single ones each with its own nucleus.</p> + +<p><i>Ginger Starch.</i>—This starch is of the same class as those from +the potato and maranta and several others which are of underground +origin. In outline the granules are not oval like those named, but more +rectangular, having more obtuse angles in the larger ones and being +cylindrical or circular in outline in the smaller, as indicated in <a href="#FIG_50">Fig. 50</a>. +They average nearly the same size as maranta starch, but are much +more variable, both in size and form. The rings are scarcely visible +even with the most favorable illuminations.</p> + +<p><i>Sago Starch.</i>—This exists in two modifications in the market; as +raw and as prepared sago. In the prepared condition it is characterized +by a larger circular depression in the center of most of the granules. +The rings are not visible. They are mostly circular in form or +approaching it, and vary from 0.025 to 0.065 millimeter in diameter, as +indicated in <a href="#FIG_51">Fig. 51</a>.</p> + +<div class="figcontainer smcap"> + <div class="figsub"> + <p id="FIG_48" class="center"><b>Fig. 48.</b><br> </p> + <img src="images/fig48.jpg" alt="" width="300" height="251" > + <p class="center">Maranta Starch × 350.</p> + </div> + <div class="figsub"> + <p id="FIG_49" class="center"><b>Fig. 49.</b></p> + <img src="images/fig49.jpg" alt="" width="300" height="263" > + <p class="center">Potato Starch × 350.</p> + </div> +</div> + +<div class="figcontainer smcap"> + <div class="figsub"> + <p id="FIG_50" class="center"><b>Fig. 50.</b><br> </p> + <img src="images/fig50.jpg" alt="" width="300" height="185" > + <p class="center"> <br>Ginger Starch × 350.</p> + </div> + <div class="figsub"> + <p id="FIG_51" class="center"><b>Fig. 51.</b></p> + <img src="images/fig51.jpg" alt="" width="300" height="239" > + <p class="center">Sago Starch × 350.</p> + </div> +</div> + +<div class="figcontainer smcap"> + <div class="figsub"> + <p id="FIG_52" class="center"><b>Fig. 52.</b></p> + <img src="images/fig52.jpg" alt="" width="300" height="279" > + <p class="center">Pea Starch × 350.</p> + </div> + <div class="figsub"> + <p id="FIG_53" class="center"><b>Fig. 53.</b></p> + <img src="images/fig53.jpg" alt="" width="300" height="278" > + <p class="center">Bean Starch × 350.</p> + </div> +</div> + +<p class="center"><b>DRAWN BY GEO. MARX</b>.<span class="ws3">A. Hoen & Co., Lithocaustic</span></p> +<hr class="chap x-ebookmaker-drop"> + +<div class="figcontainer smcap"> + <div class="figsub"> + <p id="FIG_54" class="center"><b>Fig. 54.</b></p> + <img src="images/fig54.jpg" alt="" width="300" height="312" > + <p class="center">Wheat Starch × 350.</p> + </div> + <div class="figsub"> + <p id="FIG_55" class="center"><b>Fig. 55.</b></p> + <img src="images/fig55.jpg" alt="" width="250" height="330" > + <p class="center">Barley Starch × 350.</p> + </div> +</div> + +<div class="figcontainer smcap"> + <div class="figsub"> + <p id="FIG_56" class="center"><b>Fig. 56.</b></p> + <img src="images/fig56.jpg" alt="" width="300" height="289" > + <p class="center">Rye Starch × 350.</p> + </div> + <div class="figsub"> + <p id="FIG_57" class="center"><b>Fig. 57.</b></p> + <img src="images/fig57.jpg" alt="" width="300" height="278" > + <p class="center">Oat Starch × 350.</p> + </div> +</div> + +<div class="figcontainer smcap"> + <div class="figsub"> + <p id="FIG_58" class="center"><b>Fig. 58.</b><br> </p> + <img src="images/fig58.jpg" alt="" width="300" height="220" > + <p class="center">Indian Corn Starch × 350.</p> + </div> + <div class="figsub"> + <p id="FIG_59" class="center"><b>Fig. 59.</b></p> + <img src="images/fig59.jpg" alt="" width="250" height="248" > + <p class="center">Rice Starch × 350.</p> + </div> +</div> + +<p class="center"><b>DRAWN BY GEO. MARX</b>.<span class="ws3">A. Hoen & Co., +Lithocaustic</span></p> +<hr class="chap x-ebookmaker-drop"> + +<div class="figcenter smcap"> + <p class="center"><b>FIG. 60.</b></p> + <img id="FIG_60" src="images/fig60.jpg" alt="" width="400" height="380" > + <p class="center">Cassava Starch × 150.</p> + <p class="f80 spb1">PLAIN ILLUMINATION.</p> + <p class="center"><b>FIG. 61.</b></p> + <img id="FIG_61" src="images/fig61.jpg" alt="" width="400" height="380" > + <p class="center">Indian Corn Starch × 150.</p> + <p class="f80 spb1">PLAIN ILLUMINATION.</p> +</div> + +<p class="center spb2">A. Hoen & Co., Lithocaustic</p> + +<p><span class="pagenum"><a id="Page_221"></a>[Pg 221]</span> +<i>Pea and Bean Starches.</i>—These starches produce but a slight +effect with polarized light. The rings are scarcely visible, and the +hilum is stellate or much cracked along a median line, the bean more so +than the pea, the latter resembling fresh dough kneaded again into the +center as in making rolls, and the former the shape assumed by the same +after baking. The grains of both are somewhat variable in size, ranging +from 0.025 to 0.10 millimeter in length, as shown in +Figs. <a href="#FIG_52">52</a> and <a href="#FIG_53">53</a>.</p> + +<p><i>Wheat Starch</i> grains are quite variable in size, varying from +0.05 to 0.010 millimeter in diameter. They belong to the same class as +barley and rye, the hilum being invisible and the rings not prominent. +The granules are circular disks in form, and there are now and then +contorted depressions resembling those in pea starch. They are the +least regular of the three starches named and do not polarize actively. +The typical forms of these granules are shown in <a href="#FIG_54">Fig. 54</a>.</p> + +<p><i>Barley Starch</i> is quite similar to that of wheat, but the grains +do not vary so much in size, averaging 0.05 millimeter. They have rings +which are much more distinct, and very small granules adhering to the +largest in bud-like forms, as seen in <a href="#FIG_55">Fig. 55</a>.</p> + +<p><i>Rye Starch</i> is more variable in size, many of the granules +not exceeding 0.02 millimeter, while the largest reach 0.06 to 0.07 +millimeter. It lacks distinctive characteristics entirely, and is the +most simple in form of all the starches. <a href="#FIG_56">Fig. 56</a> +shows the appearance of the granules under the microscope.</p> + +<p><i>Oat Starch</i> is unique, being composed of large compound masses of +polyhedral granules from 0.12 to 0.02 millimeter in length, the single +granules averaging 0.02 to 0.015 millimeter. It does not polarize +actively, and displays neither rings nor hilum. The illustration, +<a href="#FIG_57">Fig. 57</a>, shows its nature with accuracy.</p> + +<p><i>Indian Corn Starch.</i>—The granules of maize starch are largely +of the same size, from 0.02 to 0.03 millimeter in diameter, with now +and then a few which are much smaller. They are mostly circular in +shape or rather polyhedral, with rounded angles, as shown in Figs. <a href="#FIG_58">58</a> +and <a href="#FIG_61">61</a>. They form very brilliant objects with polarized light, but +with ordinary illumination show but the faintest sign of rings and a +well-developed hilum, at times star-shaped, and at others more like a +circular depression.</p> + +<p><i>Rice Starch</i> is very similar to that of maize, and is easily +<span class="pagenum"><a id="Page_222"></a>[Pg 222]</span> +confused with it, the grains being about the same size. The grain, +however, is distinguished from it by its polygonal form, and its +well defined angles, as indicated in <a href="#FIG_59">Fig. 59</a>. +The hilum is more prominent and more often stellate or linear. Several +granules are at times united.</p> + +<p><i>Cassava Starch.</i>—This variety of starch is obtained from +the root of the sweet cassava, which grows in great profusion in +Florida. It is compared with maize starch in Figs. <a href="#FIG_60">60</a> +and <a href="#FIG_61">61</a>. In the illustration the granules are +represented as magnified 150 diameters. The grains of the cassava +starch measure about 0.012 millimeter in diameter and resemble very +nearly maize starch, except that they have greater evenness of +outline.<a id="FNanchor_169" href="#Footnote_169" class="fnanchor">[169]</a></p> + +<p>For further descriptions of starch grains the reader is referred to the +work of Griffith, already cited.</p> + +<p>These descriptions, it will be seen, do not agree entirely with those +of some other authors, but they are based on a somewhat extensive experience.</p> + +<p>There are peculiarities of size, shape and appearance of starch +granules, which must be allowed for, and the necessity for every +investigator to compare a starch which he is desirous of identifying +with authentic specimens, must always be recognized.</p> + +<h3>AUTHORITIES CITED IN PART SECOND.</h3> + +<div class="footnotes"> +<div class="footnote"><p class="no-indent"> +<a id="Footnote_23" href="#FNanchor_23" class="label">[23]</a> +Vines, Vegetable Physiology.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_24" href="#FNanchor_24" class="label">[24]</a> +Berichte der deutschen chemischen Gesellschaft, Band 23, S. 2136; +Stone, Agricultural Science Vol. 6, p. 180. Page 59, eighth line from +bottom insert “original” before “optical.” Page 60, second line from +top, read <i>d</i> instead of <i>l</i> fructose.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_25" href="#FNanchor_25" class="label">[25]</a> +Herles, Zeitschrift des Vereins für die Rübenzucker-Industrie, +1890. S. 217.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_26" href="#FNanchor_26" class="label">[26]</a> +Tucker; Wiechmann; Sidersky; von Lippman; Tollens and Spencer.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_27" href="#FNanchor_27" class="label">[27]</a> +Bulletin No. 28, Department of Agriculture, Division of Chemistry, p. 197.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_28" href="#FNanchor_28" class="label">[28]</a> +Physikalisch-Chemische Tabellen, S. 42.</p> +</div> + +<div class="footnote"><p class="no-indent"><a id="Footnote_29" href="#FNanchor_29" class="label">[29]</a> +Tucker’s Manual of Sugar Analysis, pp. 100 et seq.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_30" href="#FNanchor_30" class="label">[30]</a> +Vid. op. cit. supra, p. 108.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_31" href="#FNanchor_31" class="label">[31]</a> +Op. cit. supra, p. 109.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_32" href="#FNanchor_32" class="label">[32]</a> +Op. cit. supra, p. 110.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_33" href="#FNanchor_33" class="label">[33]</a> +Op. cit. supra, p. 114.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_34" href="#FNanchor_34" class="label">[34]</a> +Spencer’s Handbook for Sugar Manufacturers, p. 92.</p> +</div> + +<p><span class="pagenum"><a id="Page_223"></a>[Pg 223]</span></p> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_35" href="#FNanchor_35" class="label">[35]</a> +Landolt’s Handbook of the Polariscope, pp. 95 et seq.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_36" href="#FNanchor_36" class="label">[36]</a> +Robb, vid. op. cit. supra, p. 8.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_37" href="#FNanchor_37" class="label">[37]</a> +Spencer’s Handbook for Sugar Manufacturers, pp. 22 et seq. +Tucker’s Manual of Sugar Analysis, pp. 120 et seq.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_38" href="#FNanchor_38" class="label">[38]</a> +Sidersky; Traité d’Analyse des Matières Sucrées, p. 104.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_39" href="#FNanchor_39" class="label">[39]</a> +Journal of the American Chemical Society, 1893. Vol. 15, p. 121.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_40" href="#FNanchor_40" class="label">[40]</a> +Comptes rendus, 1879. Seance du 20th Octobre 1879; +Dingler’s polytechniches Journal, Band 223, S. 608.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_41" href="#FNanchor_41" class="label">[41]</a> +Landolt’s Handbook of the Polariscope. p. 120.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_42" href="#FNanchor_42" class="label">[42]</a> +Sidersky; Traité d’Analyse des Matières Sucrées, p. 97.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_43" href="#FNanchor_43" class="label">[43]</a> +Manual of Sugar Analysis, pp. 143 et seq.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_44" href="#FNanchor_44" class="label">[44]</a> +Landolt und Börnstein, Physikalisch-Chemische Tabellen. +S. 460.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_45" href="#FNanchor_45" class="label">[45]</a> +Bulletin No. 31. Department of Agriculture, Division of Chemistry, p. 232.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_46" href="#FNanchor_46" class="label">[46]</a> +Zeitschrift des Vereins für die Rübenzucker-Industrie. 1870, S. 223.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_47" href="#FNanchor_47" class="label">[47]</a> +Tucker’s Manual of Sugar Analysis, p. 164.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_48" href="#FNanchor_48" class="label">[48]</a> +(bis). Gerlach, Spencer’s Handbook for Sugar Manufacturers, p. 91.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_49" href="#FNanchor_49" class="label">[49]</a> +Vid. op. cit. supra, p. 45.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_50" href="#FNanchor_50" class="label">[50]</a> +Vid. loc. et op. cit. supra.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_51" href="#FNanchor_51" class="label">[51]</a> +Gill; Journal of the Chemical Society, Vol. 24, 1871, p. 91.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_52" href="#FNanchor_52" class="label">[52]</a> +Wiley; American Chemical Journal, Vol. 6, p. 289.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_53" href="#FNanchor_53" class="label">[53]</a> +Vid. op. cit. supra, p. 301.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_54" href="#FNanchor_54" class="label">[54]</a> +Zeitschrift des Vereins für die Rübenzucker-Industrie, 1890. S. 876.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_55" href="#FNanchor_55" class="label">[55]</a> +Weber and McPherson; Journal of the American Chemical Society. Vol. +17, p. 320; Bulletin No. 43. Department of Agriculture, Division of +Chemistry, p. 126.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_56" href="#FNanchor_56" class="label">[56]</a> +Zeitschrift des Vereins für die Rübenzucker-Industrie, 1888, S. 51.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_57" href="#FNanchor_57" class="label">[57]</a> +Vid. op. cit. supra, Ss, 699 und 763; 1890. S. 217.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_58" href="#FNanchor_58" class="label">[58]</a> +Bulletin de l’Association des Chimistes de Sucrerie et +de Distillerie, May, 1890, p. 431.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_59" href="#FNanchor_59" class="label">[59]</a> +Neue Zeitschrift für Rübenzucker-Industrie, Band 19, S. 71.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_60" href="#FNanchor_60" class="label">[60]</a> +Journal of the Chemical Society, Transactions, Vol. 57, pp. 834, et seq.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_61" href="#FNanchor_61" class="label">[61]</a> +Op. cit. supra, p. 866.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_62" href="#FNanchor_62" class="label">[62]</a> +Op. cit. supra, 1891, p. 46.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_63" href="#FNanchor_63" class="label">[63]</a> +Neue Zeitschrift für Rübenzucker-Industrie, Band 19, S. 71.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_64" href="#FNanchor_64" class="label">[64]</a> +From γῦρος and δῦνᾶτός (δύνᾶμις).</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_65" href="#FNanchor_65" class="label">[65]</a> +Landolt’s Handbook of the Polariscope, p. 125.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_66" href="#FNanchor_66" class="label">[66]</a> +Vid. op. cit. supra, pp. 48 et seq.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_67" href="#FNanchor_67" class="label">[67]</a> +Berichte der deutschen chemischen Gesellschaft, 1877, S. 1403.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_68" href="#FNanchor_68" class="label">[68]</a> +Die landwirtschaftlichen Versuchs-Stationen, Band 40, S. 307.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_69" href="#FNanchor_69" class="label">[69]</a> +Spencer’s Handbook for Sugar Manufacturers, p. 80; Landolt’s Handbook +of the Polariscope, p. 216; Tollens’ Handbuch der Kohlenhydrate.</p> +</div> + +<p><span class="pagenum"><a id="Page_224"></a>[Pg 224]</span></p> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_70" href="#FNanchor_70" class="label">[70]</a> +Annalen der Chemie and Pharmacie, May, 1870.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_71" href="#FNanchor_71" class="label">[71]</a> +Tucker’s Manual of Sugar Analysis, p. 208.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_72" href="#FNanchor_72" class="label">[72]</a> +Rapport fait a la Société d’Encouragement d’Agriculture; +Journal de Pharmacie et de Chimie, 1844. 3d serie, Tome 6, p. 301.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_73" href="#FNanchor_73" class="label">[73]</a> +Annalen der Chemie und Pharmacie, Band 39, S. 361.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_74" href="#FNanchor_74" class="label">[74]</a> +Jahrbücher für praktische Heilkunde, 1845, S. 509.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_75" href="#FNanchor_75" class="label">[75]</a> +Archives für Physiologische Heilkunde, 1848, Band 7, S 64.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_76" href="#FNanchor_76" class="label">[76]</a> +Rodewald and Tollens; Berichte der deutschen chemischen +Gesellschaft, Band 11, S. 2076.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_77" href="#FNanchor_77" class="label">[77]</a> +Chemical News, Vol. 39, p. 77.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_78" href="#FNanchor_78" class="label">[78]</a> +The Analyst, Vol. 19, p. 181.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_79" href="#FNanchor_79" class="label">[79]</a> +Gaud; Bulletin de l’Association des Chimistes de Sucrerie et de Distillerie, +Apr. 1895, p. 629; Comptes rendus, 1894, Tome 119, p. 604.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_80" href="#FNanchor_80" class="label">[80]</a> +Annalen der Chemie und Pharmacie, B. 72, S. 106.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_81" href="#FNanchor_81" class="label">[81]</a> +Journal of Analytical and Applied Chemistry, Vol. 4, p. 370.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_82" href="#FNanchor_82" class="label">[82]</a> +Wiley; Bulletin de l’Association des Chimistes de +Sucrerie et de Distillerie, April, 1884.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_83" href="#FNanchor_83" class="label">[83]</a> +Vid. op. cit. supra, 1895, p. 642; Comptes rendus, Tome 119, +1894, p. 650.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_84" href="#FNanchor_84" class="label">[84]</a> +Annual Report, United States Department of Agriculture, 1879, +p. 65; Zeitschrift für Analytische Chemie, Band 12, S. 296; +Mohr Titrirmethode, sechste auflage, S. 508.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_85" href="#FNanchor_85" class="label">[85]</a> +Comptes rendus, 1894, Tome 119, p. 478.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_86" href="#FNanchor_86" class="label">[86]</a> +Gazetta Chimica Italiana, Tome 6, p. 322.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_87" href="#FNanchor_87" class="label">[87]</a> +Sidersky; Traité d’Analyse des Matières Sucrées, p. 148.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_88" href="#FNanchor_88" class="label">[88]</a> +Vid. op. cit. supra, p. 149.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_89" href="#FNanchor_89" class="label">[89]</a> +Neue Zeitschrift für die Rübenzucker-Industrie, Band 22, S. 220.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_90" href="#FNanchor_90" class="label">[90]</a> +Zeitschrift des Vereins für Rübenzucker-Industrie, 1889, S. 933.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_91" href="#FNanchor_91" class="label">[91]</a> +Vid. op. cit. supra, 1887, S. 147.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_92" href="#FNanchor_92" class="label">[92]</a> +Berichte der deutschen chemischen Gesellschaft, Band 23, No. 14, S. 3003; +Zeitschrift des Vereins für die Rübenzucker-Industrie, 1891, S. 97.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_93" href="#FNanchor_93" class="label">[93]</a> +Ost; vid. op. et loc. cit. supra.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_94" href="#FNanchor_94" class="label">[94]</a> +Zeitschrift des Vereins für die Rübenzucker-Industrie, 1890, S. 187.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_95" href="#FNanchor_95" class="label">[95]</a> +Chemical News, Vol. 39, p. 77.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_96" href="#FNanchor_96" class="label">[96]</a> +The Analyst, 1894, p. 181.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_97" href="#FNanchor_97" class="label">[97]</a> +Chemical News, Vol. 71, p. 235.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_98" href="#FNanchor_98" class="label">[98]</a> +Journal de Pharmacie et de Chimie, 1894, Tome 30, p. 305.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_99" href="#FNanchor_99" class="label">[99]</a> +Pharmaceutical Journal, (3), 23, p. 208.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_100" href="#FNanchor_100" class="label">[100]</a> +Vid. op. cit. supra, (3), 25, p. 913.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_101" href="#FNanchor_101" class="label">[101]</a> +Sidersky; Bulletin de l’Association des Chimistes, +Juillet, 1886 et Sept. 1888.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_102" href="#FNanchor_102" class="label">[102]</a> +Bodenbender and Scheller; Zeitschrift des Vereins für die +Rübenzucker-Industrie, 1887, S. 138.</p> +</div> + +<p><span class="pagenum"><a id="Page_225"></a>[Pg 225]</span></p> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_103" href="#FNanchor_103" class="label">[103]</a> +Vid. op. cit. supra, 1889, S. 935.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_104" href="#FNanchor_104" class="label">[104]</a> +Ewell; Manuscript communication to author.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_105" href="#FNanchor_105" class="label">[105]</a> +Journal für praktische Chemie, 1880, Band 22, 46; Handbuch der +Spiritusfabrication, 1890, S. 79; Zeitschrift des Vereins für die +Rübenzucker-Industrie, 1879, S. 1050; <i>Ibid</i>, 1883, S. 769; +<i>Ibid</i>, 1889, S. 734.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_106" href="#FNanchor_106" class="label">[106]</a> +Handbuch der Spiritusfabrication, 1890, 79.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_107" href="#FNanchor_107" class="label">[107]</a> +Wein; Tabellen zur quantitativen Bestimmung der Zuckerarten, S. 13. +(The caption for the table on page 159 should read as on page 160.)</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_108" href="#FNanchor_108" class="label">[108]</a> +Zeitschrift des Vereins für die Rübenzucker-Industrie, +1889, S. 735.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_109" href="#FNanchor_109" class="label">[109]</a> +Bulletin No. 43, Department of Agriculture, Division of Chemistry, p. 209.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_110" href="#FNanchor_110" class="label">[110]</a> +Chemiker-Zeitung, 1893, S. 548.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_111" href="#FNanchor_111" class="label">[111]</a> +Wein; Tabellen zur quantitativen Bestimmung der Zuckerarten, S. 35.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_112" href="#FNanchor_112" class="label">[112]</a> +Berichte der deutschen chemischen Gesellschaft, Band 16, S. 661.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_113" href="#FNanchor_113" class="label">[113]</a> +Vid. op. cit. supra, Band 22, S. 87.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_114" href="#FNanchor_114" class="label">[114]</a> +Chemisches Centralblatt, 1895, Band 2, S. 66.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_115" href="#FNanchor_115" class="label">[115]</a> +Comptes rendus; Tome 112, No. 15, p. 799.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_116" href="#FNanchor_116" class="label">[116]</a> +Vid. op. cit. supra, Tome 94, p. 1517.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_117" href="#FNanchor_117" class="label">[117]</a> +Journal of the Chemical Society, June, 1888, p. 610. (In the formulas +for lactose and arabinose read H₂₂ and H₁₀ respectively.)</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_118" href="#FNanchor_118" class="label">[118]</a> +American Chemical Journal, Vol. 11, No. 7, p. 469.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_119" href="#FNanchor_119" class="label">[119]</a> +Chemisches Centralblatt, 1889, No. 7.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_120" href="#FNanchor_120" class="label">[120]</a> +American Chemical Journal, Vol. 17, No. 7, pp. 507, 517.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_121" href="#FNanchor_121" class="label">[121]</a> +Comptes rendus, Tome 118, p. 426.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_122" href="#FNanchor_122" class="label">[122]</a> +Justus Liebig’s Annalen der Chemie, 1890. Band 257, S. 160.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_123" href="#FNanchor_123" class="label">[123]</a> +Journal of Analytical and Applied Chemistry, Vol. 7, pp. 68 et seq.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_124" href="#FNanchor_124" class="label">[124]</a> +Flint and Tollens; Berichte der deutschen chemischen Gesellschaft, +Band 25, S. 2912.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_125" href="#FNanchor_125" class="label">[125]</a> +Vid. op. cit. supra, Band 23, S. 1751. (Read Günther.)</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_126" href="#FNanchor_126" class="label">[126]</a> +Journal of Analytical and Applied Chemistry, Vol. 5, p. 421.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_127" href="#FNanchor_127" class="label">[127]</a> +Vid. op. cit. supra, p. 426.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_128" href="#FNanchor_128" class="label">[128]</a> +Berichte der deutschen chemischen Gesellschaft, Band 24, S. 3575.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_129" href="#FNanchor_129" class="label">[129]</a> +Journal of Analytical and Applied Chemistry, Vol. 7, p. 74.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_130" href="#FNanchor_130" class="label">[130]</a> +Chemiker-Zeitung, Band 17, 1743.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_131" href="#FNanchor_131" class="label">[131]</a> +Vid. op. cit. supra, Band 18, N. 51, S. 966.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_132" href="#FNanchor_132" class="label">[132]</a> +Monatshefte für Chemie, Band 16, S. 283; Berichte der +deutschen chemischen Gesellschaft, Referate Band 28, S. 629.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_133" href="#FNanchor_133" class="label">[133]</a> +Papasogli; Bulletin de l’Association des Chimistes de +Sucrerie et de Distillerie, Juillet 1895, p. 68.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_134" href="#FNanchor_134" class="label">[134]</a> +Gans und Tollens; Zeitschrift des Vereins für die +Rübenzucker-Industrie, Band 38, S. 1126.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_135" href="#FNanchor_135" class="label">[135]</a> +Berichte der deutschen chemischen Gesellschaft, 20, S. 181; +Zeitschrift des Vereins für die Rübenzucker-Industrie, 1891, S. 895.</p> +</div> + +<p><span class="pagenum"><a id="Page_226"></a>[Pg 226]</span></p> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_136" href="#FNanchor_136" class="label">[136]</a> +Zeitschrift des Vereins für die Rübenzucker-Industrie, 1891, S. 891.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_137" href="#FNanchor_137" class="label">[137]</a> +Chemiker-Zeitung, 1888, No. 2; Zeitschrift des Vereins +für die Rübenzucker-Industrie, 1888, S. 347.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_138" href="#FNanchor_138" class="label">[138]</a> +Fischer; Berichte der deutschen chemischen Gesellschaft, +Band 20, S. 821; Band 21, Ss. 988; 2631.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_139" href="#FNanchor_139" class="label">[139]</a> +Zeitschrift für physiologische Chemie, Band 11, S. 492.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_140" href="#FNanchor_140" class="label">[140]</a> +Vid. op. cit. supra, Band 12, No. 4, Ss. 355 et seq; No. 5, +Ss. 377 et seq.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_141" href="#FNanchor_141" class="label">[141]</a> +Berichte der deutschen chemischen Gesellschaft, Band 20, S. 540.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_142" href="#FNanchor_142" class="label">[142]</a> +Sitzungsberichte der Mathematisch-Naturwissenschaften in Wien, +Band 93, Heft 2, S. 912.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_143" href="#FNanchor_143" class="label">[143]</a> +Tollens; Handbuch der Kohlenhydrate; von Lippmann, Chemie der Zuckerarten.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_144" href="#FNanchor_144" class="label">[144]</a> +Wilder Quarter-Century Book, 1893; Abdruck aus dem Centralblatt für +Bakteriologie und Parasitenkunde, Band 18, 1895, No. 1; American +Journal of Medical Sciences, Sept., 1895.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_145" href="#FNanchor_145" class="label">[145]</a> +Griffiths, Principal Starches used as Food; Nägeli’s +Beiträge zur näheren Kenntniss der Stärkegruppe.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_146" href="#FNanchor_146" class="label">[146]</a> +Zeitschrift für Physiologische Chemie, Band 12, Ss. 75-78.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_147" href="#FNanchor_147" class="label">[147]</a> +Maercker; Handbuch der Spiritusfabrikation, 1890, S. 90.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_148" href="#FNanchor_148" class="label">[148]</a> +Chemiker-Zeitung, Band 19, S. 1501.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_149" href="#FNanchor_149" class="label">[149]</a> +Paragraphs <b><a href="#P_28">28-32</a></b>, this volume.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_150" href="#FNanchor_150" class="label">[150]</a> +Vol. 2, p. 204.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_151" href="#FNanchor_151" class="label">[151]</a> +Chemisches Centralblatt, 1877, Band 8, S. 732.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_152" href="#FNanchor_152" class="label">[152]</a> +Chemiker-Zeitung, Band 19, S. 1501.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_153" href="#FNanchor_153" class="label">[153]</a> +Vid. op. cit. supra, S. 1502; Moniteur Scientifique, 1887, p. 538.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_154" href="#FNanchor_154" class="label">[154]</a> +Chemiker-Zeitung, Band 19, S. 1502.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_155" href="#FNanchor_155" class="label">[155]</a> +Vid. op. cit. supra, 1895, S. 1727.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_156" href="#FNanchor_156" class="label">[156]</a> +Chemiker-Zeitung, Band 19, S. 1502.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_157" href="#FNanchor_157" class="label">[157]</a> +Jahresberichte der Agrikulturchemie, 1892, S. 664.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_158" href="#FNanchor_158" class="label">[158]</a> +Journal de Pharmacie et de Chimie, 5ᵉ, Série, Tome 25, p. 394.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_159" href="#FNanchor_159" class="label">[159]</a> +Journal of the American Chemical Society, Vol. 17, p. 64.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_160" href="#FNanchor_160" class="label">[160]</a> +Repertorium der Analytischen Chemie, 1887, S. 299.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_161" href="#FNanchor_161" class="label">[161]</a> +Journal of the American Chemical Society, Vol. 16, p. 726.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_162" href="#FNanchor_162" class="label">[162]</a> +Förschungs Berichte über Lebensmittel, Hamburg; Abs., +The Analyst, Vol. 20, p. 210.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_163" href="#FNanchor_163" class="label">[163]</a> +Rouvier; Comptes rendus, Tome 107, pp. 272, 278; Tome 111, +pp. 64, 186; Tome 120, p. 1179.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_164" href="#FNanchor_164" class="label">[164]</a> +Bulletin 13, Department of Agriculture, Division of Chemistry, +pp. 154 et. seq.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_165" href="#FNanchor_165" class="label">[165]</a> +Foods, Their Composition and Analysis, p. 139.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_166" href="#FNanchor_166" class="label">[166]</a> +Richardson, Vid. op. cit. 142, p. 158.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_167" href="#FNanchor_167" class="label">[167]</a> +Principal Starches used as Food, Cirencester, Baily & Son, +Market Place.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_168" href="#FNanchor_168" class="label">[168]</a> +Vid. op. cit. 142, pp. 158 et seq.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_169" href="#FNanchor_169" class="label">[169]</a> +Bulletin 44, Department of Agriculture, Division of Chemistry, p. 14.</p> +</div> +</div> + +<hr class="chap x-ebookmaker-drop"> + +<div class="chapter"> +<p><span class="pagenum"><a id="Page_227"></a>[Pg 227]</span></p> +<h2 class="nobreak">PART THIRD.<br> +<span class="h_subtitle">PROCESSES FOR DETECTING AND DETERMINING SUGARS<br> +AND STARCHES AND OTHER CARBOHYDRATES IN CRUDE<br> +OR MANUFACTURED AGRICULTURAL PRODUCTS.</span></h2> +</div> + +<p id="P_203"><b>203. Introduction.</b>—In the preceding part directions have been +given for the estimation of sugars and starches in approximately +pure forms. In the present part will be described the most approved +methods of separating these bodies and other carbohydrates from crude +agricultural products and for their chemical examination. In many +respects the processes which in a small way are used for preparing +samples for analysis are employed on a large scale for technical and +manufacturing purposes. It is evident, however, that the following +paragraphs must be confined strictly to the analytical side of the +question inasmuch as anything more than mere references to technical +processes would lead into wide digressions.</p> + +<p>In the case of sugars the analyst is for the most part quite as much in +need of reliable methods of extraction and preparation as of processes +for analysis. With starches the matter is more simple and the chief +methods of separating them for examination were necessarily described +in the previous part.</p> + +<p>Sugars in fresh plants exist almost entirely in solution. This is +true of all the great sources of the sugar of commerce, <i>viz.</i>, +the palm, the maple, the sugar beet and sugar cane. This statement is +also true of fruits and the natural nectar of flowers. By natural or +artificial drying the sugar may be reduced to the solid or semisolid +state as in the cases of raisins and honey. In certain seeds, deficient +in water, sugars may possibly exist in a solid state naturally, as may +be the case with sucrose in the peanut and raffinose in cotton seed. +<span class="pagenum"><a id="Page_228"></a>[Pg 228]</span></p> + +<p>Starches on the other hand when soluble, are probably not true +starches, but they partake more or less of a dextrinoid nature. Fine +starch particles occur abundantly in the juices of some plants, +as for instance sorghum, where they are associated with sugar and +can be obtained from the expressed juice by subsidence. But even +in such a case it is not certain that the starch enters into the +general circulation. It is more likely formed locally by biochemical +condensation of its constituents. Starches in a soluble or semisoluble +state are transported, as a rule, to the tubers or seeds of plants +where they are accumulated in large quantities as a reserve food for +future growth. For a study of the plant metabolism whereby starch is +produced and for its histological and physiological properties the +reader may consult the standard authorities on vegetable physiology.<a id="FNanchor_170" href="#Footnote_170" class="fnanchor">[170]</a></p> + +<p><b>204. Sugar in the Sap of Trees.</b>—Many trees at certain seasons +of the year, carry large quantities of sugar in their sap. Among these +the maple and sugar palm are preeminent. The sap is secured by cutting +a pocket into the side of the tree or by boring into it and allowing +the sap to run into an appropriate receptacle through a spile. The +content of sugar in the sap of the maple and palm varies greatly. In +some cases it falls as low as one and a half and in others rises to as +much as six or seven per cent.<a id="FNanchor_171" href="#Footnote_171" class="fnanchor">[171]</a> +In most cases the sugar in the maple sap is pure sucrose, but towards +the end of the flowing season it may undergo changes of a viscous +nature due to fermentation, or inversion, forming traces of invert +sugar. In this country the sap of the maple may flow freely on any warm +day in winter, but the sugar season proper begins about February 15th +in Southern Ohio and Indiana, and about March 25th in Vermont. It lasts +from six weeks to two months. The sap flows best during moderately +warm, still days, after a light freeze.</p> + +<p>In addition to sugar the maple sap contains a trace of albuminoid +matters and some malic acid combined with lime. As a rule it can be +subjected to polarization without preliminary clarification.</p> + +<p><b>205. Determination of Sugar in Saps.</b>—In most cases the sap may +be directly polarized in a 200 millimeter tube. Its specific gravity is +<span class="pagenum"><a id="Page_229"></a>[Pg 229]</span> +obtained by a spindle or pyknometer, and the percentage of sugars taken +directly from the table on <a href="#P_58">page 73</a>, the degree brix +corresponding to the sugar percentage.</p> + +<p>On polarizing, the sugar percentage is calculated as follows:</p> + +<p>Multiply the specific gravity of the sap by 100 and divide the product +by 26.048. Divide the direct reading of the sap on the sugar scale by +the quotient obtained above, and the quotient thus obtained will be the +correct percentage of sugar in the original solution.</p> + +<p>The formula is applicable for those instruments in which 26.048 grams +represent the normal quantity of sugar which in 100 cubic centimeters +reads 100 divisions on the scale. When other factors are used they +should be substituted for 26.048 in the above formula.</p> + +<p>The principle of the calculation is based on the weight of the sap +which is contained in 100 cubic centimeters, and this is evidently +obtained by multiplying 100 by the specific gravity of the sap. Since +26.048 is the normal quantity of sugar in that volume of the solution +the quotient of the actual weight divided by that factor shows how many +times too great the observed polarization is. The simple division of +the polariscope reading by this factor gives the correct reading.</p> + +<p><i>Example</i>: Let the specific gravity of the sap be 1.015 and the +observed polarization be 15.0. Then the true percentage of sugar in the +sap is found by the equation:</p> + +<p class="f105">101.5 : 26.048 = 15.0 : <i>x</i>.</p> + +<p class="center">Whence <i>x</i> = 3.85 = percentage of sugar in the sap.</p> + +<p>The process outlined above is not applicable when a clarifying reagent +such as lead subacetate or alumina cream must be used. But even in +these cases it will not be found necessary to weigh the sap. A sugar +flask graduated at 100 and 110 cubic centimeters is used and filled to +the first mark with the sap, the specific gravity of which is known. +The clarifying reagent is added, the volume completed to the second +mark with water, and the contents of the flask well shaken and thrown +on a dry filter. The observation tube, which should be 220 millimeters +in length, is then filled with the clear filtrate and the rest of the +process is as described above. A 200 millimeter tube may also be used in +<span class="pagenum"><a id="Page_230"></a>[Pg 230]</span> +this case and the observed reading increased by one-tenth.</p> + +<div class="figcontainer smcap"> + <div class="figsub"> + <img id="FIG_62" src="images/fig62.jpg" alt="" width="350" height="438" > + <p class="center"> <br>Fig. 62.<br> Laboratory Cane Mill.</p> + </div> + <div id="FIG_63" class="figsub"> + <img src="images/fig63.jpg" alt="" width="150" height="476" > + <p class="center">Fig. 63.<br> Weighing<br> Pipette.</p> + </div> +</div> + +<p><b>206. Estimation of Sugar in the Sap of Sugar Cane and +Sorghum.</b>—In bodies like sugar cane and sorghum the sap containing +the sugar will not flow as in the cases of the maple and sugar palm. +The simplest way of securing the sap of the bodies named is to subject +them to pressure between rolls. A convenient method of obtaining the +sap or juice is by passing the cane through a small three-roll mill +indicated in the <a href="#FIG_62">figure</a>. Small mills of this +kind have been used in this division for many years and with entire +satisfaction. Small canes, such as sorghum, may be milled one at a +time, or even two or three when they are very small. In the case of +large canes, it is necessary that they be split and only half of them +used at once. The mill should not be crowded by the feed in such a way +as to endanger it or make it too difficult for the laborer to turn. +From fifty to sixty per cent of the weight of a cane in juice may be +obtained by passing it through one of these small mills. Experience +has shown that there is a little difference between the juice as first +expressed and the residual sap remaining in the bagasse, but the juice +first expressed may be used for analysis for control purposes as a fair +representative of all that the cane contains.</p> + +<p>To determine the percentage of juice expressed, the canes may be +weighed before passing through the mill and the juice collected. Its +weight divided by the weight of the original cane will give the per +cent of the juice expressed, calculated on the whole cane. Instead of +weighing the juice the bagasse may also be collected and weighed; but +on account of the rapidity with which it dries the operation should be +<span class="pagenum"><a id="Page_231"></a>[Pg 231]</span> +accomplished without delay. The expressed juice is clarified with lead +subacetate, filtered and polarized in the manner described in former +paragraphs. Instead of weighing the juice, its specific gravity may +be taken by an accurate spindle and the volume of it, equivalent to a +given weight, measured from a sucrose pipette.<a id="FNanchor_172" href="#Footnote_172" class="fnanchor">[172]</a></p> + +<p>A sucrose pipette for cane juice has a graduation on the upper part +of the stem which enables the operator to deliver double the normal +weight for the polariscope used, after having determined the density of +the juice by means of a spindle. A graduation of from 5° to 25° of the +brix spindle will be sufficient for all variations in the density of +the juice, or one covering a range of from 10° to 20° will suffice for +most instances. The greater the density of the juice the less volume +of it will be required for the weight mentioned. For general use, the +sucrose pipette is graduated on the stem to deliver from forty-eight +to 50.5 cubic centimeters, the graduations being in terms of the brix +spindle. The graduation of the stem of this instrument is shown in the +accompanying <a href="#FIG_62">figure</a>. In the use of the pipette it +is only necessary to fill it to the degree on the stem corresponding to +the degree brix found in the preliminary trial.</p> + +<p>The quantities of juice corresponding to each degree and fractional +degree of the brix spindle are given in the following table; calculated +for the normal weight 26.048 grams for the ventzke and for 16.19 grams +for the laurent scale. The measured quantities of juice are placed in +a 100 cubic centimeter sugar flask, treated with the proper quantity +of lead subacetate, the volume completed to the mark, and the juice +filtered and polarized in a 200 millimeter tube. The reading of the +polariscope is divided by two for the factor 26.048 and by three for +the factor 16.19. +<span class="pagenum"><a id="Page_232"></a>[Pg 232]</span></p> + +<p class="f120"><b><span class="smcap">Table for Use of Sucrose Pipettes.</span></b></p> + + +<table class="spb1"> + <thead><tr class="bt2"> + <th class="tdc bb"> Degrees <br>brix.</th> + <th class="tdc bb bl"> Cubic centimeters <br>of juice for<br>26.048 factor.<br> + Divide<br> reading by two.</th> + <th class="tdc bb bl2"> Degrees <br>brix.</th> + <th class="tdc bb bl"> Cubic centimeters <br>of juice for<br>16.19 factor.<br> + Divide<br> reading by three.</th> + </tr></thead> + <tbody><tr> + <td class="tdc"> 5.0</td> + <td class="tdc bl">51.1</td> + <td class="tdc bl2"> 5.0</td> + <td class="tdc bl">47.6</td> + </tr><tr> + <td class="tdc"> 5.4</td> + <td class="tdc bl">51.0</td> + <td class="tdc bl2"> 5.7</td> + <td class="tdc bl">47.5</td> + </tr><tr> + <td class="tdc"> 5.7</td> + <td class="tdc bl">50.9</td> + <td class="tdc bl2"> 6.3</td> + <td class="tdc bl">47.4</td> + </tr><tr> + <td class="tdc"> 6.4</td> + <td class="tdc bl">50.8</td> + <td class="tdc bl2"> 6.8</td> + <td class="tdc bl">47.3</td> + </tr><tr> + <td class="tdc"> 6.9</td> + <td class="tdc bl">50.7</td> + <td class="tdc bl2"> 7.3</td> + <td class="tdc bl">47.2</td> + </tr><tr> + <td class="tdc"> 7.4</td> + <td class="tdc bl">50.6</td> + <td class="tdc bl2"> 7.8</td> + <td class="tdc bl">47.1</td> + </tr><tr> + <td class="tdc"> 7.9</td> + <td class="tdc bl">50.5</td> + <td class="tdc bl2"> 8.3</td> + <td class="tdc bl">47.0</td> + </tr><tr> + <td class="tdc"> 8.4</td> + <td class="tdc bl">50.4</td> + <td class="tdc bl2"> 8.9</td> + <td class="tdc bl">46.9</td> + </tr><tr> + <td class="tdc"> 8.9</td> + <td class="tdc bl">50.3</td> + <td class="tdc bl2"> 9.5</td> + <td class="tdc bl">46.8</td> + </tr><tr> + <td class="tdc"> 9.4</td> + <td class="tdc bl">50.2</td> + <td class="tdc bl2">10.0</td> + <td class="tdc bl">46.7</td> + </tr><tr class="bb"> + <td class="tdc"> 9.9</td> + <td class="tdc bl">50.1</td> + <td class="tdc bl2">10.5</td> + <td class="tdc bl">46.6</td> + </tr><tr> + <td class="tdc">10.4</td> + <td class="tdc bl">50.0</td> + <td class="tdc bl2">11.0</td> + <td class="tdc bl">46.5</td> + </tr><tr> + <td class="tdc">10.9</td> + <td class="tdc bl">49.9</td> + <td class="tdc bl2">11.6</td> + <td class="tdc bl">46.4</td> + </tr><tr> + <td class="tdc">11.4</td> + <td class="tdc bl">49.8</td> + <td class="tdc bl2">12.1</td> + <td class="tdc bl">46.3</td> + </tr><tr> + <td class="tdc">11.9</td> + <td class="tdc bl">49.7</td> + <td class="tdc bl2">12.7</td> + <td class="tdc bl">46.2</td> + </tr><tr> + <td class="tdc">12.4</td> + <td class="tdc bl">49.6</td> + <td class="tdc bl2">13.3</td> + <td class="tdc bl">46.1</td> + </tr><tr> + <td class="tdc">12.9</td> + <td class="tdc bl">49.5</td> + <td class="tdc bl2">13.8</td> + <td class="tdc bl">46.0</td> + </tr><tr> + <td class="tdc">13.4</td> + <td class="tdc bl">49.4</td> + <td class="tdc bl2">14.3</td> + <td class="tdc bl">45.9</td> + </tr><tr> + <td class="tdc">13.9</td> + <td class="tdc bl">49.3</td> + <td class="tdc bl2">14.8</td> + <td class="tdc bl">45.8</td> + </tr><tr> + <td class="tdc">14.4</td> + <td class="tdc bl">49.2</td> + <td class="tdc bl2">15.3</td> + <td class="tdc bl">45.7</td> + </tr><tr class="bb"> + <td class="tdc">14.9</td> + <td class="tdc bl">49.1</td> + <td class="tdc bl2">15.9</td> + <td class="tdc bl">45.6</td> + </tr><tr> + <td class="tdc">15.4</td> + <td class="tdc bl">49.0</td> + <td class="tdc bl2">16.4</td> + <td class="tdc bl">45.5</td> + </tr><tr> + <td class="tdc">15.9</td> + <td class="tdc bl">48.9</td> + <td class="tdc bl2">17.0</td> + <td class="tdc bl">45.4</td> + </tr><tr> + <td class="tdc">16.4</td> + <td class="tdc bl">48.8</td> + <td class="tdc bl2">17.5</td> + <td class="tdc bl">45.3</td> + </tr><tr> + <td class="tdc">16.9</td> + <td class="tdc bl">48.7</td> + <td class="tdc bl2">18.0</td> + <td class="tdc bl">45.2</td> + </tr><tr> + <td class="tdc">17.4</td> + <td class="tdc bl">48.6</td> + <td class="tdc bl2">18.6</td> + <td class="tdc bl">45.1</td> + </tr><tr> + <td class="tdc">17.9</td> + <td class="tdc bl">48.5</td> + <td class="tdc bl2">19.1</td> + <td class="tdc bl">45.0</td> + </tr><tr> + <td class="tdc">18.4</td> + <td class="tdc bl">48.4</td> + <td class="tdc bl2">19.7</td> + <td class="tdc bl">44.9</td> + </tr><tr> + <td class="tdc">18.9</td> + <td class="tdc bl">48.3</td> + <td class="tdc bl2">20.2</td> + <td class="tdc bl">44.8</td> + </tr><tr> + <td class="tdc">19.4</td> + <td class="tdc bl">48.2</td> + <td class="tdc bl2"> </td> + <td class="tdc bl"> </td> + </tr><tr class="bb"> + <td class="tdc">19.9</td> + <td class="tdc bl">48.1</td> + <td class="tdc bl2"> </td> + <td class="tdc bl"> </td> + </tr> + </tbody> +</table> + +<p>In ordering sucrose pipettes the factor for which they are to be +graduated should be stated.</p> + +<p>It is evident also that with the help of the foregoing table the +measurements may be made by means of a burette. For instance, if the +degree brix is found to be 19.9, 48.1 cubic centimeters are to be used. +This quantity can be easily run from a burette. In order to make the +pipette more convenient it has been customary in this laboratory, as +practiced by Carr, to attach a glass tube with a stopcock by means of +<span class="pagenum"><a id="Page_233"></a>[Pg 233]</span> +a rubber tube to the upper part of the pipette, whereby the exact level +of the juice in the stem of the pipette can be easily set at any +required mark.</p> + +<p>In the polarization of dilute solutions, such as are found in the +saps and juices referred to above, it must not be forgotten that the +gyrodynat of the sucrose is increased as the density of the solution +is diminished. This change introduces a slight error into the work +which is of no consequence from a technical point of view, but +becomes a matter which must be considered in exact determinations. To +avoid the annoyance of calculating the gyrodynat for every degree of +concentration, tables have been constructed by Schmitz and Crampton by +means of which the actual percentage of sugar, corresponding to any +degree of polarization, is determined by inspection. These tables may +be used when extremely accurate work is required.<a id="FNanchor_173" href="#Footnote_173" class="fnanchor">[173]</a></p> + +<div class="figleft smcap"> + <img id="FIG_64" src="images/fig64.jpg" alt="" width="200" height="389" > + <p class="center spb1">Figure 64. Gird’s<br> Gravimeter.</p> +</div> + +<p><b>207. Measuring Sugar Juices with a Gravimeter.</b>—A convenient +method of weighing sugar juices is the gravimetric process designed by +Gird.<a id="FNanchor_174" href="#Footnote_174" class="fnanchor">[174]</a> +The apparatus is fully illustrated by <a href="#FIG_64">Fig. 64</a>. The hydrometer +F has a weight of 26.048 grams and its stem is also graduated in +degrees brix. The juice is poured into the cylinder A and allowed to +stand until air bubbles have escaped. In filling A the finger is held +over the orifice G so that the siphon tube B is completely filled, the +air escaping at the vent C. After the tube is filled the finger is +withdrawn from G and all the liquid which will run out at G allowed to +<span class="pagenum"><a id="Page_234"></a>[Pg 234]</span> +escape. The sugar flask D is now brought under G and the hydrometer F +allowed to descend into A. The hydrometer will displace exactly its +own weight of liquid. For convenience of reading, the index E may be +used which is set five degrees above the surface of the liquid in +A. The number of degrees brix read by E is then diminished by five. +The hydrometer has been improved since the description given by the +addition of a thermometer which, in addition to carrying a graduation +in degrees, also shows the correction to be made upon the degree brix +for each degree read. It is evident that the hydrometer may be made of +any weight, and thus the delivery of any desired amount of juice be secured.</p> + +<p><b>208. Determination of Reducing Bodies in Cane Juices.</b>—Sucrose +in cane juices is constantly accompanied with reducing sugars, or other +bodies which have a similar action on fehling liquor, which interfere +to a considerable degree with the practical manufacture of sugar. It is +important to determine with a moderate degree of accuracy the quantity +of these bodies. These sugars or reducing bodies are of a peculiar +nature. The author pointed out many years ago that these reducing +bodies were without action on polarized light, and for this reason +proposed the name anoptose as one characteristic of their nature.<a id="FNanchor_175" href="#Footnote_175" class="fnanchor">[175]</a> +It is also found that these bodies do not yield theoretically the quantity +of alcohol which a true sugar of the hexose type would give.<a id="FNanchor_176" href="#Footnote_176" class="fnanchor">[176]</a> +It is entirely probable, therefore, that they are quite different in +their nature from many of the commonly known sugars. On account of the +difficulty of separating these bodies in a pure state their actual +copper reducing power is not known. For practical purposes, however, it +is assumed to be the same as that of dextrose or invert sugar and the +percentage of these bodies present is calculated on that assumption. +In the determination of these sugars or reducing bodies, the quantity +weighed may be determined by an apparatus entirely similar to the +sucrose pipette just described above. The quantity of juice used should +be diluted as a rule to such a degree as not to contain more than one +per cent of the reducing bodies. For the best work, the juices should +be clarified with lead subacetate and the excess of lead removed with +sodium carbonate. For technical control work in sugar factories, this +<span class="pagenum"><a id="Page_235"></a>[Pg 235]</span> +process may be omitted as in such cases rapidity of work is a matter +of considerable importance and the approximate estimation of the total +quantity of reducing bodies is all that is desired.</p> + +<p>For volumetric work, the solution of copper and the method of +manipulation described in paragraph <b><a href="#P_117">117</a></b> are +most conveniently used.</p> + +<p><b>209. Preservation of Sugar Juices for Analysis.</b>—Lead subacetate +not only clarifies the juices of canes and thus permits of their more +exact analytical examination, but also exercises preservative effects +which enable it to be used as a preserving agent and thus greatly +diminish the amount of work necessary in the technical control of a +sugar factory. Instead, therefore, of the analyst being compelled to +make an examination of every sample of the juice, aliquot portions +representing the different quantities can be preserved and one analysis +made for all. This method has been thoroughly investigated by Edson, +who also finds that the errors, which may be introduced by the use of +the lead subacetate in the analytical work, may be entirely avoided by +using the normal lead acetate.<a id="FNanchor_177" href="#Footnote_177" class="fnanchor">[177]</a></p> + +<p>In the use of the normal lead acetate, much less acetic acid is +required in the polariscopic work than when the subacetate is used. +The normal lead acetate is not so good a clarifying agent as the +subacetate, but its efficiency in this respect is increased by the +addition of a little acetic acid. In its use, it is not necessary to +remove the lead, even for the determination of the reducing bodies.</p> + +<p>For further details in regard to the technical determination of +reducing bodies, special works may be consulted.<a id="FNanchor_178" href="#Footnote_178" class="fnanchor">[178]</a></p> + +<p><b>210. Direct Determination of Sugars in Canes.</b>—The methods, +which have just been described, of securing the juices of cane by +pressure and of determining the sugars therein, do not give the actual +percentage of sugar in the cane. An approximate result may be secured +by assuming that the cane is composed of ninety parts of juice and ten +parts of cellular tissues and other insoluble matters. This assumption +is approximately true in most cases, but there are often conditions +arising which render the data calculated on the above assumption +misleading. In any particular case in order to be certain that the +<span class="pagenum"><a id="Page_236"></a>[Pg 236]</span> +correct percentage of sugar is secured it will be necessary to +determine the fiber in the cane. This is an analytical process of +considerable labor and especially so on account of the difficulty of +securing samples which represent the average composition of the cane. +The fibrous structure of the canes, the hardness of their external +covering and the toughness of their nodes or joints render the +sampling extremely difficult. Moreover, the content of sugar varies +in different parts of the cane. The parts nearest the ground are, +as a rule, richer than the upper joints and this is especially true +of sugar cane. In order, therefore, to get a fair sample, even of a +single cane, all parts of it must be considered. Several methods of the +direct determination of sugar in canes have been proposed and will be +described below.</p> + +<div class="figcenter smcap"> + <img id="FIG_65" src="images/fig65.jpg" alt="" width="500" height="487" > + <p class="center">Figure 65. Machine for Cutting Canes.</p> +</div> + +<p><b>211. Methods of Cutting or Shredding the Cane for Analytical +Purposes.</b>—A simple method of cutting canes into small pieces which +will permit of an even sampling is very much to be desired. The cutting +<span class="pagenum"><a id="Page_237"></a>[Pg 237]</span> +apparatus shown in <a href="#FIG_65">Fig. 65</a> has been long in use in this +laboratory. The canes by it are cut into thin slices, but the cutting edge of +the knife being perpendicular to the length of the cane renders the use of the +instrument somewhat laborious and unsatisfactory. A considerable time +is required to cut a single cane and the slices which are formed should +be received in a vessel which will protect them as much as possible +from evaporation during the process of the work. Instead of the +apparatus above a small cane cutting machine arranged with four knives +on a revolving disk maybe used. The apparatus is shown in <a href="#FIG_66">Fig. 66</a>. +The cane is fed against the knives through the hole shown in the open front +of the apparatus and the knives thus strike the cane obliquely.<a id="FNanchor_179" href="#Footnote_179" class="fnanchor">[179]</a> +The knives can be set in the revolving disk at any desired position so +as to cut the canes into chips as fine as may be desired. The cossettes +furnished by this method may be sampled directly for the extraction of +the sugar. In the case of the cossettes from both instruments described +above a finer subdivision may be secured by passing them through a +sausage cutter.</p> + +<div class="figcenter smcap"> + <img id="FIG_66" src="images/fig66.jpg" alt="" width="600" height="388" > + <p class="center">Figure 66. Cane Cutting Mill.</p> +</div> + +<p>The best method for shredding canes, however, is to pass them through +the apparatus described on <a href="#Page_9">page 9</a>. That machine +gives an extremely fine, moist mass, which is of uniform nature and +capable of being directly sampled.</p> + +<p><span class="pagenum"><a id="Page_238"></a>[Pg 238]</span> +<b>212. Methods of Determination.</b>—Even the finely divided +material obtained by the machine just described is not suited to give +an instantaneous diffusion for polarization as is done by the finely +ground beet pulp to be described further on. For the determination of +sugar a proper weight of the cossettes or pulp obtained as described +above, taken after thorough mixing, is placed in a flask graduated +properly and treated with water.<a id="FNanchor_180" href="#Footnote_180" class="fnanchor">[180]</a></p> + +<p>The flask in which the mixture takes place should be marked to +compensate for the volume of the fiber of the cane. When the normal +weight of cane is taken for the ventzke scale, <i>viz.</i>, 26.048, the +flask should be graduated at 102.6 cubic centimeters. If double the +normal weight be taken, the flask should be graduated at 205.2 cubic +centimeters. This graduation is based on the assumption of the presence +of fiber amounting to ten per cent of the weight of the cossettes. The +fiber is so nearly the density of the juice obtained as to be regarded +as one gram equal to one cubic centimeter. The flask is at first filled +almost full of water and then warmed to near the boiling point for an +hour with frequent shaking. It is then filled to a little above the +mark, the contents well mixed and warmed for ten minutes more with +frequent shaking. After cooling, the volume is made up to the mark, +well shaken and poured upon a filter. The filtrate is collected in a +sugar flask marked at fifty and fifty-five cubic centimeters. When +filled to the first mark a proper quantity of lead subacetate is added, +the volume completed to the second mark with water, the contents of the +flask well shaken, poured upon a filter and the filtrate polarized in +the usual way.</p> + +<p>The reducing sugar is determined in an aliquot part of the filtrate by +one of the alkaline copper methods.</p> + +<p><b>213. Determination by Drying and Extraction.</b>—Instead of the +diffusion and polarization method just described, the fine pulp +obtained may be dried, the dried residue ground in a drug mill and +extracted with aqueous alcohol or with water.</p> + +<p>To facilitate the calculation when this method is employed, the water +content of a small portion of the well sampled pulp is determined. The +rest of the pulp is dried, first for a few hours at a temperature not +<span class="pagenum"><a id="Page_239"></a>[Pg 239]</span> +above 60° or 70°, and then at the temperature of boiling water, either +in the open air or a partial vacuum, until all the water is driven off. +The dried residue can then be preserved in well stoppered bottles for +the determination of sugar at any convenient period. The finely ground +dried residue for this purpose is placed in an extraction apparatus +and thoroughly exhausted with eighty per cent alcohol. The extract is +dried and weighed, giving the total weight of all sugars present. After +weighing, the extract is dissolved in water, made up to a definite +volume and the reducing sugars determined in an aliquot portion thereof +by the usual methods. The weight of reducing sugars found, calculated +for the whole extract deducted from the total weight of this extract +will give the weight of the sucrose in the sample. From this number the +content of sugar in the original cane is determined from the percentage +of water found in the original sample.</p> + +<p><i>Example.</i>—In a sample of finely pulped canes the content of +water is found to be 76.5 per cent. The thoroughly dried pulp is ground +and extracted with aqueous alcohol. Five grams give two and five-tenths +grams of the extract. The extract is dissolved in water, made up to +a definite volume and the reducing sugars determined in an aliquot +part and calculated for the whole, amounting to 150 milligrams. The +extract is therefore composed of 2.35 grams of sucrose and 0.15 gram +of reducing sugars. The calculation is now made to the original sample +which contained 76.5 per cent of water and 23.5 per cent of dry matter, +as follows:</p> + +<p class="f105">5 : <i>x</i> :: 23.5 : 100, whence <i>x</i> = 21.27,</p> + +<p>the weight of the original material corresponding to five grams of the +dry substance. The original composition of the sample is therefore +expressed by the following numbers:</p> + +<table class="spb1 fs_105"> + <tbody><tr> + <td class="tdl"> </td> + <td class="tdr">Per cent.</td> + </tr><tr> + <td class="tdl">Sucrose</td> + <td class="tdr_wsp">11.1</td> + </tr><tr> + <td class="tdl">Reducing sugars</td> + <td class="tdr_wsp">0.7</td> + </tr><tr> + <td class="tdl">Water</td> + <td class="tdr_wsp">76.5</td> + </tr><tr> + <td class="tdl">Fiber (insoluble matter)</td> + <td class="tdr_wsp">11.7</td> + </tr> + </tbody> +</table> + +<p><b>214. Examination of the Bagasse.</b>—The method just described for +<span class="pagenum"><a id="Page_240"></a>[Pg 240]</span> +the examination of canes may be also applied to the analysis of +bagasses, with the changes made necessary by the increased percentage +of fiber therein. On account of the large surface exposed by the +bagasse, the sampling, shredding and weighing should be accomplished as +speedily as possible to avoid loss of moisture.</p> + +<p>The optical examination of bagasses is rendered difficult by reason of +the uneven pressure to which the canes are subjected. With fairly good +milling in technical work the bagasses will have at least thirty per +cent of fiber. The method for the polariscopic examination is therefore +based upon that assumption, but the volume of the solution must be +changed for varying percentages of fiber in the bagasse. On account of +the smaller percentage of sugar, it is convenient to take double or +three times the normal weight of the bagasse for examination. Since +large sugar flasks are not commonly to be had the diffusion of the +bagasse may be conducted in a quarter liter flask. In a quarter liter +flask place 52.096 grams of the finely shredded bagasse, very nearly +fill the flask with water and extract the sugar as described for canes +in the foregoing paragraphs. In the weight of bagasse used there will +be, in round numbers, fifteen grams of fiber. When the volume of water +is completed to the mark the actual content of liquid in the flask will +therefore be only 235 cubic centimeters. Fifty cubic centimeters of the +filtrate are placed in a sugar flask marked at fifty and fifty-five +cubic centimeters, the proper quantity of lead subacetate solution +added, the volume completed to the upper mark, the contents of the +flask well shaken, filtered and polarized in a 200 millimeter tube. Let +the reading obtained be four degrees and increase this by one-tenth for +the increased volume of solution above fifty cubic centimeters. The +true reading is therefore four degrees and four-tenths. This reading, +however, must be corrected, because the original volume instead of +being 200 cubic centimeters, is 235 cubic centimeters. The actual +percentage of sugar in the sample examined is obtained by the following +proportion:</p> + +<p class="f105">200 : 235 = 4.4 : <i>x</i>.</p> + +<p>The correct reading is therefore 5°.2, the percentage of sugar in the +sample examined. +<span class="pagenum"><a id="Page_241"></a>[Pg 241]</span></p> + +<p>The results obtained by the method just described may vary somewhat +from the true percentage by reason of the variation of the content +of fiber in the bagasse. It is, however, sufficiently accurate for +technical control in sugar factories and on account of its rapidity +of execution is to be preferred for this purpose. More accurate +results would be obtained by drying the bagasse, and proceeding with +the examination in a manner entirely analogous to that described for +the extraction of sugar from dried canes by aqueous alcohol. In both +instances the reducing sugar is determined in the manner already +mentioned.</p> + +<p><b>215. Determination of Fiber in Cane.</b>—In estimating the content +of sugar in canes by the analysis of the expressed juices, it is +important to make frequent determinations of the fiber for the purpose +of obtaining correct data for calculation. In periods of excessive +drought, or when the canes are quite mature, the relative content of +fiber is increased, while, on the other hand, in case of immature +canes, or during excessive rainfalls, it is diminished. The chief +difficulty in determining the content of fiber in canes is found in +securing a representative sample. On account of the hard and fibrous +nature of the envelope and of their nodular tissues, canes are reduced +to a fine pulp with great difficulty by the apparatus in ordinary +use. A fairly homogeneous pulp, however, may be obtained by means of +the shredder described on <a href="#Page_9">page 9</a>. The canes having been +shredded as finely as possible, a weighed quantity is placed in any convenient +extraction apparatus and thoroughly exhausted with hot water. The +treatment with hot water should be continued until a few drops of the +extract evaporated on a watch glass will leave no sensible residue. +The residual fiber is dried to constant weight at the temperature of +boiling water, cooled in a desiccator and rapidly weighed and the +percentage of fiber calculated from the data obtained. On account of +the great difficulty of securing a homogeneous pulp, even with the best +shredding machines, the determination should be made in duplicate or +triplicate and the mean of the results entered as the percentage of +fiber. The term fiber as used in this sense, must not be confounded +with the same term employed in the analysis of fodders and feeding +<span class="pagenum"><a id="Page_242"></a>[Pg 242]</span> +stuffs. In the latter case the term is applied to the residue left +after the successive treatment of the material with boiling, dilute +acid and alkali. The analysis of canes for feeding purposes is +conducted in the general manner hereinafter described for fodders.</p> + +<p><b>216. Estimation of Sugar in Sugar Beets.</b>—The methods employed +for the determination of the sugar content of beets are analogous to +those used for canes, with such variations in the method of extraction +as are made possible and necessary by the difference in the nature +of these sacchariferous plants. The sugar beet is more free of fiber +and the hard and knotty substances composing the joints of plants +are entirely absent from their composition. For this reason they +are readily reduced to a fine pulp, from which the sugar is easily +extracted. The analytical processes are also greatly simplified by the +complete absence of reducing sugars from the juices of healthy beets. +The only sugar aside from sucrose which is present in these juices +is raffinose, and this is not found in healthy beets, except when +they have been injured by frost or long keeping. In practical work, +therefore, the determination of sucrose completes the analysis in so +far as sugars are concerned. Four methods of procedure will illustrate +all the principles of the various processes employed.</p> + +<p><b>217. Estimation of Sucrose in the Expressed Juice.</b>—In the +first method the beets are reduced by any good shredding machine, to +a fine pulp, which is placed in a press and the juice expressed. In +this liquor, after clarification with lead subacetate, the sucrose is +determined by the polariscope. The methods of measuring, clarifying and +polarizing are the same as those described for saccharine juices in +paragraphs <b><a href="#P_83">83-85</a></b>. The mean percentage of juice in the sugar beet +is ninety-five. The corrected polariscopic reading obtained multiplied +by 0.95 will give the percentage of sugar in the beet.</p> + +<p><i>Example.</i>—The solids in a sample of beet juice, as measured by a +brix spindle, are 17.5 per cent. Double the normal weight of the juice +is measured from a sucrose pipette, placed in a sugar flask, clarified, +the volume completed to 100 cubic centimeters, the contents of the +flask well shaken and filtered. The polariscopic reading obtained is +29°.0. Then (29.0 ÷ 2) × 0.95 = 13.8 = percentage of sucrose in the beet. +<span class="pagenum"><a id="Page_243"></a>[Pg 243]</span></p> + +<p><b>218. Instantaneous Diffusion.</b>—In the second process employed +for determining the sugar content of beets, the principle involved +depends on the use of a pulp so finely divided as to permit of +the almost instant diffusion of the sugar present throughout the +added liquid. This diffusion takes place even in the cold and the +process thus presents a convenient and rapid method for the accurate +determination of the percentage of sugar in beets. The pulping is +accomplished by means of the machine described on <a href="#Page_10">page 10</a>, +or the one shown in <a href="#FIG_67">Fig. 67</a>. The beet is pressed against the rapidly +revolving rasp by means of the grooved movable block and the finely divided pulp +is received in the box below. These machines afford a pulp which is +impalpable and which readily permits an almost instantaneous diffusion +of its sugar content.</p> + +<div class="figcenter smcap"> + <img id="FIG_67" src="images/fig67.jpg" alt="" width="450" height="505" > + <p class="center">Fig 67. Apparatus for Pulping Beets.</p> +</div> + +<p><b>219. Pellet’s Method of Cold Diffusion.</b>—The impalpable pulp +having been obtained, by one of the processes described, the content of +sugar therein is determined as follows:<a id="FNanchor_181" href="#Footnote_181" class="fnanchor">[181]</a></p> + +<p>A normal or double normal quantity of the pulp is quickly weighed, to +<span class="pagenum"><a id="Page_244"></a>[Pg 244]</span> +avoid evaporation, in a sugar dish with an appropriate lip, and washed +into the flask, which should be graduated, as shown in <a href="#FIG_68">Fig. 68</a>, +to allow for the volume of the fiber or marc of the beet. Since the beet +pulp contains, on an average, four per cent of marc, the volume which +is occupied thereby is assumed to be a little more than one cubic +centimeter. Since it is advisable to have as large a volume of water +as convenient, it is the practice of Pellet to wash the pulp into a +flask graduated at 201.35 cubic centimeters. If a 200 cubic centimeter +flask be used, the weight of the pulp should be 25.87 instead of +26.048 grams. After the pulp is washed into the flask, about six cubic +centimeters of lead subacetate of 30° baumé are added, together with a +little ether, to remove the foam. The flask is now gently shaken and +water added to the mark and the contents thoroughly shaken. If the pulp +is practically perfect, the filtration and polarization may follow +immediately. The filter into which the contents of the flask are poured +should be large enough to hold the whole quantity. It is recommended +to add a drop or two of strong acetic acid just before completing +the volume of the liquid in the flask to the mark. The polarization +should be made in a 400 millimeter tube, which will give directly the +percentage of sugar present. It is not necessary to heat the solution +in order to insure complete diffusion, but the temperature at which the +operation is conducted should be the ordinary one of the laboratory. +In case the pulp is not as fine as should be, the flask should be +allowed to stand for half an hour after filling, before filtration. +An insufficient amount of lead subacetate may permit some rotatory +bodies other than sugar to pass into solution, and care should be +taken to have always the proper quantity of clarifying material added. +The presence of these rotating bodies, mostly of a pectic nature, +may be shown by extracting the pulp first with cold water until all +the sugar is removed, and afterwards with boiling water. The liquor +obtained from the last precipitation will show a decided right-handed +rotation, unless first treated with lead subacetate, in which case +the polarization will be zero. A very extended experience with the +instantaneous cold aqueous diffusion has shown that the results +obtained thereby are quite as reliable as those given by hot alcoholic +or aqueous digestion.</p> + +<p><span class="pagenum"><a id="Page_245"></a>[Pg 245]</span> +<b>220. Flask for Cold Diffusion and Alcohol Digestion.</b>—For +convenience in washing the pulp into the sugar flask, the latter is +made with an enlarged mouth as shown in <a href="#FIG_68">Fig. 68</a>. +The dish holding the weighed quantity of pulp is held with the lip in +the mouth of the flask, and the pulp washed in by means of a jet of +water furnished from a pressure bottle or washing flask. The flask +shown is graduated for the normal weight of pulp, <i>viz.</i>, 26.048 +grams. The marking is on the constricted neck and extends from 100 to +101.3 cubic centimeters. This permits of making the proper allowance +for the volume occupied by the marc or fiber, but this is unnecessary +for the usual character of control analyses. In the case of healthy, +fresh beets, the volume occupied by the marc is nearly one and +three-tenths cubic centimeters for the normal polariscopic weight of +26.048 grams of pulp. For the laurent instrument this volume is nearly +one cubic centimeter.</p> + +<div class="figcenter smcap"> + <img id="FIG_68" src="images/fig68.jpg" alt="" width="500" height="451" > + <p class="center">Figure 68. Apparatus for Cold Diffusion.</p> +</div> + +<p id="P_221"><b>221. Extraction with Alcohol.</b>—The third method of determining +sugar in beets is by alcoholic extraction. The principle of the method +is based on the fact that aqueous alcohol of not more than eighty per +<span class="pagenum"><a id="Page_246"></a>[Pg 246]</span> +cent strength will extract all the sugar from the pulp, but will not +dissolve the pectic and other rotatory bodies, which, in solution, +are capable of disturbing the rotatory power of the sugar present. +It is also further to be observed that the rotatory power of pure +sucrose, in an aqueous alcoholic solution, is not sensibly different +from that which is observed in a purely aqueous liquid. The pulp, +which is to be extracted, should be in as fine a state of subdivision +as convenient, and the process may be carried on in any of the forms +of extraction apparatus already described, or in the apparatus shown +in <a href="#FIG_69">Fig. 69</a>. The extraction tube, of the ordinary +forms of apparatus, however, is scarcely large enough to hold the +required amount of pulp, and therefore special tubes and forms of +apparatus have been devised for this method of procedure. In weighing +the pulp for extraction, a quarter, half, or the exact amount required +for the polariscope employed, should be used. If the tubes are of +sufficient size the full weight may be taken, <i>viz.</i>, 26.048 +or 16.19 grams for the instruments in ordinary use. Since the pulp +contains a large quantity of water, the extraction could be commenced +with alcohol of standard strength, <i>viz.</i>, about ninety-five per +cent. The volume of alcohol employed should be such as will secure a +strength of from seventy to eighty per cent when mixed with the water +contained in the pulp. The flask receiving the extract should be kept +in continuous ebullition and the process may be regarded as complete +in about one hour, when the pulp has been properly prepared. The +method of extracting beet pulp with alcohol is due to Scheibler, and +in its present form the process is conducted according to the methods +described by Scheibler, Sickel, and Soxhlet.<a id="FNanchor_182" href="#Footnote_182" class="fnanchor">[182]</a></p> + +<div class="figcenter smcap"> + <img id="FIG_69" src="images/fig69.jpg" alt="" width="300" height="639" > + <p class="center">Fig. 69. Sickel-Soxhlet Extractor.</p> +</div> + +<p>If the pulp be obtained by any other means than that of a fine rasp, +the extraction of the sugar by the aqueous alcohol takes a long time, +and even a second extraction may be necessary. It is convenient to use +as a flask for holding the solvent, one already graduated at 100 or 110 +cubic centimeters. A flask especially constructed for this purpose, has +a constricted neck on which the graduations are made, and a wide mouth +serving to attach it to the extracting apparatus, as shown in <a href="#FIG_68">Fig. 68</a>. +When the extract is obtained in this way, it is not necessary to +transfer it to a new flask before preparing it for polarization. When +<span class="pagenum"><a id="Page_247"></a>[Pg 247]</span> +the extraction is complete, the source of heat is removed, and when all +the alcohol is collected in the flask, the latter is removed from the +extraction apparatus, cooled to room temperature, a sufficient quantity +of lead subacetate added, the flask well shaken, the volume completed +to the mark with water, again well shaken and the contents of the flask +thrown upon the filter. It is important to avoid loss of alcohol during +filtration. For this purpose it is best to have a folded filter and to +cover the funnel immediately after pouring the contents of the flask +upon the filter paper, with a second larger funnel. The stem of the +<span class="pagenum"><a id="Page_248"></a>[Pg 248]</span> +funnel carrying the filter paper, should dip well into the flask +receiving the filtrate. As in other cases of filtering sugar juices for +polarization, the first portions of the filtrate received should be +rejected. The percentage of sugar is obtained in the filtrate in the +usual way.</p> + +<p>Where a weight of pulp equal to the normal factor of the polariscope +employed is used, and the extract collected in a 100 cubic centimeter +flask, the percentage of sugar is directly obtained by making the +reading in a 200 millimeter tube. With other weights of pulp, or other +sizes of flask, the length of the observation tube may be changed or +the reading obtained corrected by multiplication or division by an +appropriate factor. A battery of sickel-soxhlet extractors is shown in +<a href="#FIG_69">Fig. 69</a>.<a id="FNanchor_183" href="#Footnote_183" class="fnanchor">[183]</a></p> + +<div class="figleft smcap"> + <img id="FIG_70" src="images/fig70.jpg" alt="" width="100" height="433" > + <p class="center">Fig. 70.</p> +</div> + +<p><b>222. Scheibler’s Extraction Tube.</b>—In order to secure a speedy +extraction of large quantities of pulp, Scheibler recommends the use of +the extraction tube shown in <a href="#FIG_70">Fig. 70</a>.<a id="FNanchor_184" href="#Footnote_184" class="fnanchor">[184]</a> +The apparatus is composed of three concentric glass cylinders. The +outer and middle cylinders are sealed together at the top, and the +inner one is movable and carries a perforated diaphragm below, for +filtering purposes. Near the top it is provided with small circular +openings, whereby the alcoholic vapors may gain access to the condenser +(not shown). The middle cylinder is provided with two series of +apertures, through the higher of which the vapor of alcohol passes to +the condenser, while the alcohol which has passed through the pulp and +collected between the inner and middle cylinders, flows back through +the lower into the flask (not shown) containing the boiling alcohol.</p> + +<p>The middle cylinder is provided with a curved bottom to prevent the +filtering end of the inner tube from resting too tightly against it.</p> + +<p>The tube containing the pulp is thus protected from the direct heat +of the alcoholic vapors during the progress of extraction by a thin +cushion of liquid alcohol.</p> + +<p><b>223. Alcoholic Digestion.</b>—The fourth method of determining +sugar in beet pulp, is by means of digestion with hot alcohol. The +<span class="pagenum"><a id="Page_249"></a>[Pg 249]</span> +principle of this method is precisely the same as that which is +involved in aqueous diffusion in the cold. The diffusion, however, +in the case of the alcohol, is not instantaneous, but is secured by +maintaining the mixture of the pulp and alcohol for some time at or +near the boiling point. The methods of preparing the pulp, weighing +it and introducing it into the digestion flask are precisely those +used for aqueous digestion, but in the present case a somewhat coarser +pulp may be employed. The method is commonly known as the rapp-degener +process.<a id="FNanchor_185" href="#Footnote_185" class="fnanchor">[185]</a></p> + +<p>Any convenient method of heating the alcohol may be used. In this +laboratory the flasks are held on a false bottom in a bath composed of +two parts of glycerol and one of water. One side of the bath holder +is made of glass, as shown in <a href="#FIG_71">Fig. 71</a>, in order +to keep the flasks in view. In order to avoid the loss of alcohol, +the digestion flask should be provided with a reflux condenser, or be +attached to an ordinary condenser, which will reduce the vapors of +alcohol again to a liquid. Unless the weather be very warm, the reflux +condenser may consist of a glass tube of rather wide bore and at least +one meter in length, as shown in <a href="#FIG_71">Fig. 71</a>. A +slight loss of alcohol during the digestion is of little consequence. A +convenient method of procedure is the following.</p> + +<p>Double the quantity of the beet pulp required for the ventzke +polariscope, <i>viz.</i>, 52.096 grams, weighed in a lipped metal +dish, is washed, by means of alcohol, into a flask marked at 202.6 +cubic centimeters, and the flask filled two-thirds with ninety-five +per cent alcohol and well shaken. Afterwards, a proper quantity of +lead subacetate is added, and then sufficient alcohol to complete the +volume to the mark. The flask is then attached to the condenser, placed +in a water-glycerol bath and heated to a temperature of 75° for about +forty-five minutes. At the end of this time, the flask is removed +from the bath and condenser, cooled quickly with water, alcohol added +to the mark and well shaken. The filtration should be accomplished +with precautions, to avoid the loss of alcohol mentioned in paragraph +<b><a href="#P_221">221</a></b>. The filtrate is examined in the polariscope in a 200 +millimeter tube, and the reading obtained gives directly the percentage +of sugar in the sample examined. Half the quantity of pulp mentioned, +in a 101.3 cubic centimeter flask, may also be used. A convenient form +<span class="pagenum"><a id="Page_250"></a>[Pg 250]</span> +of arranging a battery of flasks is shown in the accompanying figure.</p> + +<div class="figcenter smcap"> + <img id="FIG_71" src="images/fig71.jpg" alt="" width="400" height="482" > + <p class="center spb1">Fig. 71. Battery for Alcoholic Digestion.</p> +</div> + +<p><b>224. Determination of Sugar in Mother Beets.</b>—In selecting +mother beets for seed production, it is necessary to secure only those +of a high sugar content. This is accomplished by boring a hole about +two and a half centimeters in diameter obliquely through the beet by +means of the apparatus shown in <a href="#FIG_72">Fig. 72</a>.</p> + +<p>The beet is not injured for seed production by this process, and the +pulp obtained is used for the determination of sugar. The juice is +expressed by means of the small hand press shown in <a href="#FIG_73">Fig. 73</a>. +Since only a small quantity of juice is obtained, it is advisable to prepare +it for polarization in a sugar flask marked at fifty cubic centimeters. +The density of the juice, by reason of its small volume, is easiest +<span class="pagenum"><a id="Page_251"></a>[Pg 251]</span> +obtained by the hydrostatic balance, as described in paragraph +<b><a href="#P_53">53</a></b>. In lieu of this, the juice may be quickly weighed in a +counterbalanced dish on a balance giving results accurate to within +one milligram. The rest of the analytical process is similar to that +already described.</p> + +<div class="figcenter smcap"> + <img id="FIG_72" src="images/fig72.jpg" alt="" width="600" height="336" > + <p class="center spb1">Fig. 72. Rasp for Sampling Mother Beets.</p> + <img id="FIG_73" src="images/fig73.jpg" alt="" width="600" height="371" > + <p class="center spb1">Fig. 73. Hand Press for Beet Analysis.</p> + <img id="FIG_74" src="images/fig74.jpg" alt="" width="600" height="217" > + <p class="center spb1">Fig. 74.</p> +</div> + +<p><b>225. Aqueous Diffusion.</b>—The process of instantaneous aqueous +diffusion may also be applied to the examination of mother beets. For +<span class="pagenum"><a id="Page_252"></a>[Pg 252]</span> +this purpose the beets are perforated by a rasp, devised by Keil, shown +lying on the floor in <a href="#FIG_72">Fig. 72</a>, the characteristics of which +are shown in <a href="#FIG_74">Fig. 74</a>. The conical end of the rasp is roughened +in such a way as to reduce the beet to an impalpable pulp. This end is fastened by +a bayonet fastening to the cylindrical carrier or arm in such a way +that, by means of a groove in the conical end of the rasp, the pulp is +introduced into the cylinder. The cylinder is provided with a small +piston by means of which the pulp can be withdrawn when the cylindrical +portion of the rasp is detached from the driving machinery. It is +important that the rasp be driven at a high rate of speed, <i>viz.</i>, +from 1500 to 2000 revolutions a minute. The sample of pulp at this rate +of revolution is taken almost instantly, and with skilled manipulators +the whole operation of taking a sample, removing the rasp by means of +its bayonet fastenings, withdrawing the sample of pulp and replacing +the rasp ready for another operation does not consume more than from +ten to twenty seconds. From three to four samples may thus be taken in +a minute. The samples of pulp as taken are dropped into numbered dishes +corresponding to the numbers on the beets. One-quarter of the normal +weight for the polariscope is used for the analysis. The pulp is placed +in a fifty cubic centimeter flask, water and lead subacetate added, the +flask well shaken, filled to the mark with water, again well shaken, +the contents thrown on the filter, and the filtrate polarized in a 400 +millimeter tube, giving the direct percentage of sugar. For practical +purposes the percentage of marc in the beet may be neglected. If the +polarization take place in a 200 millimeter tube the number obtained +should be multiplied by two for the content of sugar.</p> + +<p>In numbering sugar beets which are to be analyzed for seed production, +it is found that a small perforated tin tag bearing a number may be +safely affixed to the beet by means of a tack. It is not safe to use +paper tags as they may become illegible by becoming wet before the +<span class="pagenum"><a id="Page_253"></a>[Pg 253]</span> +sorting of the beets is completed. Where from 1000 to 2000 beets +are to be examined in a day, the number of the beets and the dishes +corresponding thereto must be carefully controlled to avoid confusion +and mistakes.</p> + +<p><b>226. Determination of Sugars without Weighing.</b>—An ingenious +device for the rapid analysis of mother beets is based upon the use of +a machine which cuts from the beet a core of given dimensions and this +core is subsequently reduced to a pulp which is treated with cold water +and polarized in the manner described above. The cutting knives of the +sampler can be adjusted to take a core of any desired size. Since the +beets used for analysis have essentially the same specific gravity, the +cores thus taken weigh sensibly the same and the whole core is used +for the analysis, thus doing away with the necessity of weighing. The +core obtained is reduced to a pulp in a small machine so adjusted as +to permit the whole of the pulp, when prepared, to be washed directly +into the sugar flask. By the use of this machine a very large number of +analyses can be made in a single day, and this is highly important in +the selection of mother beets, for often 50,000 or 100,000 analyses are +to be made in a short time.</p> + +<div class="figcenter smcap"> + <img id="FIG_75A" src="images/fig75.jpg" alt="" width="600" height="213" > + <p class="center spb1">Fig. 75. Tube for Continuous Observation.</p> +</div> + +<p><b>227. Continuous Diffusion Tube.</b>—To avoid the delay occasioned +by filling and emptying observation tubes in polariscopic work, where +large numbers of analyses of canes and beets are to be made, Pellet +has devised a continuous diffusion tube, by means of which a solution, +which has just been observed, is rapidly and completely displaced by a +fresh solution. This tube, improved by Spencer, is shown in <a href="#FIG_75A">Fig. 75</a>. +The fresh solution is poured in at the funnel, displacing completely the +<span class="pagenum"><a id="Page_254"></a>[Pg 254]</span> +old solution which flows out through the tube at the other end. The +observer watches the field vision and is able to tell when the old +solution is completely displaced by the clearing of the field, at +which time the reading of the new solution can be quickly made. When +solutions are all ready for examination an expert observer can easily +read, by the aid of this device, from four to five of them in a minute.</p> + +<p><b>228. Analysis of Sirups and Massecuites.</b>—The general principles +which control the analysis of sirups and massecuites are the same +whether these products be derived from canes or beets. In the case +of the products of canes, the sirups or massecuites contain chiefly +sucrose, invert sugar, and other copper reducing bodies, inorganic +matters and water. In the case of products derived from sugar beets +the contents are chiefly sucrose, inorganic matters, a trace of invert +sugar, raffinose and water. The principles of the determination of +these various constituents have already been described.</p> + +<p><b>229. Specific Gravity.</b>—The specific gravity of sirups and +molasses can be determined by the spindle in the usual way, but in +the case of molasses which is quite dense, the spindle method is not +reliable. It is better, therefore, both in molasses and massecuites, +to determine the density by dilution. For this purpose, as described +by Spencer, a definite weight of material, from 200 to 250 grams, is +dissolved in water and the volume of the solution completed to half a +liter. A portion of the solution is then placed in a cylinder and the +quantity of total solids contained therein determined in the usual way +by a brix or specific gravity hydrometer. In case 250 grams of the +material be used the calculation of the brix degree for the original +material is conducted according to the following formula:</p> + +<table class="spb1 fs_105"> + <tbody><tr> + <td class="tdl" rowspan="2"><i>x</i> = </td> + <td class="tdc bb">G × <i>B</i> × <i>V</i></td> + </tr><tr> + <td class="tdc"><i>W</i></td> + </tr> + </tbody> +</table> + +<p>In the above formula <i>x</i> is the required brix degree, <i>V</i> +the volume of the solution, <i>B</i> the observed brix degree of the +solution, and G the corresponding specific gravity obtained from the +table on <a href="#Page_73">page 73</a>. When only small quantities of the material are at +hand the hydrostatic balance (<b><a href="#P_53">53</a></b>) should be employed. For this +<span class="pagenum"><a id="Page_255"></a>[Pg 255]</span> +purpose twenty-five grams of the material are dissolved in water and +the volume of the solution made up to 100 cubic centimeters. The sinker +of the hydrostatic balance is placed in the solution and equilibrium +secured by placing the weights upon the arm of the balance in the usual +manner. Since the arm of the balance is graduated to give, by direct +reading, the specific gravity, the density can be obtained at once.</p> + +<div class="blockquot"> +<p><i>Example.</i>—Let the position of the weights or riders upon the +balance arm be as follows:</p> + +<table class="spb1"> + <tbody><tr> + <td class="tdl">(1) at point of suspension of the bob </td> + <td class="tdr">= 1.000</td> + </tr><tr> + <td class="tdl">(3) at mark 7 on beam</td> + <td class="tdr">= 0.07 </td> + </tr><tr> + <td class="tdl">(4) at mark 9 on beam</td> + <td class="tdr">= 0.009</td> + </tr><tr> + <td class="tdl_ws2">Specific gravity</td> + <td class="tdr">= 1.079</td> + </tr> + </tbody> +</table> +</div> + +<p>The nearest brix degree corresponding to this specific gravity +(<b><a href="#P_58">58</a></b>) is 19. The total weight of the solution is equal to 100 × +1.079, <i>viz.</i>, 107.9 grams. Since the solution contains nineteen +per cent of solid matter as determined by the hydrostatic balance, the +total weight of solid matter therein is 107.9 × 19 ÷ 100 = 20.5 grams. +The total per cent. of solid matter in the original sample is therefore +20.5 ÷ 25 × 100 = 82 and the specific gravity corresponding thereto +(<a href="#Page_74">page 74</a>) is 1.42934.</p> + +<p>The specific gravity of a massecuite may also be determined in +pyknometers especially constructed for this +purpose.<a id="FNanchor_186" href="#Footnote_186" class="fnanchor">[186]</a></p> + +<p id="P_23"><b>230. Determination Of Water.</b>—The accurate determination of +water in sirups and massecuites is a matter of considerable difficulty. +The principles of conducting the process (<b><a href="#P_26">26</a></b>), applicable also +to the determination of water in honeys and other viscous liquids, +are as follows: In all cases where invert sugar is present the drying +should be conducted at a temperature not exceeding 75° or 80°. In +dense molasses and massecuites a weighed quantity should be dissolved +and made up to a definite volume and an aliquot portion taken for +the determination. In order to secure complete desiccation at a low +temperature, the drying should be accomplished in partial vacuum +(pages <a href="#Page_22">22</a>, <a href="#Page_23">23</a>). +The process of desiccation should be conducted in shallow, +flat-bottom dishes which may be conveniently and cheaply made of +aluminum and the process is hastened by filling the dish previously +<span class="pagenum"><a id="Page_256"></a>[Pg 256]</span> +with thoroughly dried fragments of pumice stone. When the sample does +not contain any invert sugar the desiccation can be safely accomplished +at the temperature of boiling water. Drying should be continued in all +cases until practically constant weight is obtained.</p> + +<p><b>231. Determination Of Ash.</b>—Ash is an important constituent of +the sirups, molasses, and massecuites from canes and exists in very +much larger quantities in the same products from beets. The ash may be +determined directly by careful incineration, but it is customary to add +a few drops of sulfuric acid, sufficient to combine with all the bases +present and be in slight excess. The presence of sulfuric acid is of +some advantage in the beginning of the carbonization and renders the +process somewhat easier of accomplishment. When sulfuric acid is used, +the weight of ash obtained must be diminished by one-tenth to allow for +the increased weight obtained by the conversion of the carbonates into +sulfates. In general, the principles and methods described on +<a href="#Page_36">pages 36-40</a> are to be employed.</p> + +<p><b>232. Determination of Reducing Sugars in Sirups, Molasses, and +Massecuites.</b>—The quantity of reducing sugars in the products +derived from the sugar beet, as a rule, is insignificant. In the +products from sugar cane there are large quantities of reducing matters +which, in general, are determined by any of the standard methods +already given. It has been shown by the author<a id="FNanchor_187" href="#Footnote_187" class="fnanchor">[187]</a> +that the juices of healthy sugar canes contain a small quantity of +invert sugar, but this statement has been contradicted by Bloufret.<a id="FNanchor_188" href="#Footnote_188" class="fnanchor">[188]</a> +It is certain, however, that the reducing bodies derived from the +products of manufacture of sugar cane and sorghum deport themselves in +a manner somewhat different from pure invert sugar. In the absence of +definite information in respect of the constitution of these bodies, +the methods applicable to dextrose and invert sugar may be applied.</p> + +<p>Since the paragraphs relating to these processes were printed some +important improvements in the preparation of the alkaline copper +solutions have been made. The copper carbonate solution, as has already +been said, is peculiarly suited to the determination of reducing sugars +in the presence of sucrose and the modified forms of this solution, and +<span class="pagenum"><a id="Page_257"></a>[Pg 257]</span> +the methods of employing them with invert sugar, dextrose, levulose, +and maltose, are described below.</p> + +<p><b>233. Estimation of Minute Quantities of Invert Sugar in +Mixtures.</b>—The method of Hiller and Meissl, paragraph <b><a href="#P_142">142</a></b>, +may be used for the estimation of small quantities of invert sugar +in mixtures. A modified form of Soldaini’s reagent is, however, to +be preferred for this purpose. Ost has proposed and tested a copper +carbonate solution for the purpose mentioned which gives reliable +results.<a id="FNanchor_189" href="#Footnote_189" class="fnanchor">[189]</a> +The solution has the following composition:</p> + +<table class="spb1"> + <tbody><tr> + <td class="tdl_top" rowspan="3">One liter contains</td> + <td class="tdr_wsp">3.6</td> + <td class="tdc">grams</td> + <td class="tdl_wsp">crystallized copper sulfate.</td> + </tr><tr> + <td class="tdr_wsp">250.0</td> + <td class="tdc">”</td> + <td class="tdl_wsp">potassium carbonate.</td> + </tr><tr> + <td class="tdr_wsp">100.0</td> + <td class="tdc">”</td> + <td class="tdl_wsp">hydrogen potassium sulfate.</td> + </tr> + </tbody> +</table> + +<p>This reagent undergoes no change when kept for a long while, especially +in large vessels. Even in smaller vessels it can be kept for a year or +more without undergoing any change.</p> + +<p>The method of analysis is the same as that described in paragraph +<b><a href="#P_128">128</a></b>, with the exception that the boiling is continued for only +five minutes instead of ten, and the quantities of the copper and sugar +solutions used are doubled, being 100 and fifty cubic centimeters +respectively. In no case must the solution used contain more than +thirty-eight milligrams of invert sugar. The quantity of sucrose in +the mixture is obtained by polarization (<b><a href="#P_94">94</a></b>). Ost has also +recalculated the reduction values of the common sugars for the strong +copper carbonate solution, and the numbers obtained are slightly +different from those given on <a href="#Page_142">page 142</a>.<a id="FNanchor_190" href="#Footnote_190" class="fnanchor">[190]</a></p> + +<p>For different percentages of invert sugar in mixtures of sucrose, the +quantities of invert sugar are calculated from the number of milligrams +of copper obtained by the following table: +<span class="pagenum"><a id="Page_258"></a>[Pg 258]</span></p> + +<ul class="index fs_110"> +<li class="isub4"><b>(A)</b> = Milligrams of copper obtained.</li> +<li class="isub4"><b>(B)</b> = Pure invert sugar.</li> +<li class="isub4"><b>(C)</b> = Invert sugar.</li> +<li class="isub4"><b>(D)</b> = Sucrose.</li> +</ul> + +<table class="spb1"> + <thead><tr> + <th class="tdc" colspan="2"> </th> + <th class="tdc bb fs_105" colspan="7"><span class="smcap">Milligrams of Invert Sugar in Mixtures of</span></th> + </tr><tr> + <th class="tdc" colspan="2"> </th> + <th class="tdc bl">5(C)</th> + <th class="tdc bl">2(C)</th> + <th class="tdc bl">1.5(C)</th> + <th class="tdc bl">1.0(C)</th> + <th class="tdc bl">0.8(C)</th> + <th class="tdc bl">0.6(C)</th> + <th class="tdc bl">0.5(C)</th> + </tr><tr> + <th class="tdc bb"> (A) </th> + <th class="tdc bb"> (B) </th> + <th class="tdc bl bb"> 95(D) </th> + <th class="tdc bl bb"> 98(D) </th> + <th class="tdc bl bb"> 98.5(D) </th> + <th class="tdc bl bb"> 99.0(D) </th> + <th class="tdc bl bb"> 99.2(D) </th> + <th class="tdc bl bb"> 99.4(D) </th> + <th class="tdc bl bb"> 99.5(D) </th> + </tr></thead> + <tbody><tr> + <td class="tdc">88</td> + <td class="tdr_wsp bl">37.9</td> + <td class="tdr_wsp bl">37.1</td> + <td class="tdr_wsp bl">36.0</td> + <td class="tdl_ws1 bl">35.4</td> + <td class="tdl_ws1 bl">34.7</td> + <td class="tdl_ws1 bl">34.2</td> + <td class="tdl_ws1 bl">33.9</td> + <td class="tdl_ws1 bl">33.6</td> + </tr><tr> + <td class="tdc">85</td> + <td class="tdr_wsp bl">36.3</td> + <td class="tdr_wsp bl">35.5</td> + <td class="tdr_wsp bl">34.5</td> + <td class="tdl_ws1 bl">34.0</td> + <td class="tdl_ws1 bl">33.4</td> + <td class="tdl_ws1 bl">32.9</td> + <td class="tdl_ws1 bl">32.5</td> + <td class="tdl_ws1 bl">32.2</td> + </tr><tr> + <td class="tdc">80</td> + <td class="tdr_wsp bl">33.9</td> + <td class="tdr_wsp bl">33.0</td> + <td class="tdr_wsp bl">33.2</td> + <td class="tdl_ws1 bl">31.7</td> + <td class="tdl_ws1 bl">31.2</td> + <td class="tdl_ws1 bl">30.7</td> + <td class="tdl_ws1 bl">30.2</td> + <td class="tdl_ws1 bl">29.9</td> + </tr><tr> + <td class="tdc">75</td> + <td class="tdr_wsp bl">31.6</td> + <td class="tdr_wsp bl">30.7</td> + <td class="tdr_wsp bl">30.0</td> + <td class="tdl_ws1 bl">29.5</td> + <td class="tdl_ws1 bl">29.0</td> + <td class="tdl_ws1 bl">28.5</td> + <td class="tdl_ws1 bl">28.1</td> + <td class="tdl_ws1 bl">27.7</td> + </tr><tr> + <td class="tdc">70</td> + <td class="tdr_wsp bl">29.4</td> + <td class="tdr_wsp bl">28.5</td> + <td class="tdr_wsp bl">27.8</td> + <td class="tdl_ws1 bl">27.4</td> + <td class="tdl_ws1 bl">26.8</td> + <td class="tdl_ws1 bl">26.4</td> + <td class="tdl_ws1 bl">25.9</td> + <td class="tdl_ws1 bl">25.6</td> + </tr><tr> + <td class="tdc">65</td> + <td class="tdr_wsp bl">27.3</td> + <td class="tdr_wsp bl">26.3</td> + <td class="tdr_wsp bl">25.7</td> + <td class="tdl_ws1 bl">25.3</td> + <td class="tdl_ws1 bl">24.7</td> + <td class="tdl_ws1 bl">24.3</td> + <td class="tdl_ws1 bl">23.8</td> + <td class="tdl_ws1 bl">23.5</td> + </tr><tr> + <td class="tdc">60</td> + <td class="tdr_wsp bl">25.2</td> + <td class="tdr_wsp bl">24.2</td> + <td class="tdr_wsp bl">23.6</td> + <td class="tdl_ws1 bl">23.2</td> + <td class="tdl_ws1 bl">22.6</td> + <td class="tdl_ws1 bl">22.2</td> + <td class="tdl_ws1 bl">21.8</td> + <td class="tdl_ws1 bl">21.5</td> + </tr><tr> + <td class="tdc">55</td> + <td class="tdr_wsp bl">23.1</td> + <td class="tdr_wsp bl">22.1</td> + <td class="tdr_wsp bl">21.6</td> + <td class="tdl_ws1 bl">21.2</td> + <td class="tdl_ws1 bl">20.6</td> + <td class="tdl_ws1 bl">20.2</td> + <td class="tdl_ws1 bl">19.8</td> + <td class="tdl_ws1 bl">19.6</td> + </tr><tr> + <td class="tdc">50</td> + <td class="tdr_wsp bl">21.2</td> + <td class="tdr_wsp bl">20.1</td> + <td class="tdr_wsp bl">19.6</td> + <td class="tdl_ws1 bl">19.2</td> + <td class="tdl_ws1 bl">18.6</td> + <td class="tdl_ws1 bl">18.3</td> + <td class="tdl_ws1 bl">17.9</td> + <td class="tdl_ws1 bl">17.7</td> + </tr><tr> + <td class="tdc">45</td> + <td class="tdr_wsp bl">19.3</td> + <td class="tdr_wsp bl">18.2</td> + <td class="tdr_wsp bl">17.6</td> + <td class="tdl_ws1 bl">17.2</td> + <td class="tdl_ws1 bl">16.7</td> + <td class="tdl_ws1 bl">16.3</td> + <td class="tdl_ws1 bl">16.0</td> + <td class="tdl_ws1 bl">15.8 </td> + </tr><tr> + <td class="tdc">40</td> + <td class="tdr_wsp bl">17.3</td> + <td class="tdr_wsp bl">16.3</td> + <td class="tdr_wsp bl">15.7</td> + <td class="tdl_ws1 bl">15.3</td> + <td class="tdl_ws1 bl">14.8</td> + <td class="tdl_ws1 bl">14.5</td> + <td class="tdl_ws1 bl">14.2</td> + <td class="tdl_ws1 bl">14.0</td> + </tr><tr> + <td class="tdc">35</td> + <td class="tdr_wsp bl">15.4</td> + <td class="tdr_wsp bl">14.5</td> + <td class="tdr_wsp bl">13.8</td> + <td class="tdl_ws1 bl">13.4</td> + <td class="tdl_ws1 bl">13.0</td> + <td class="tdl_ws1 bl">12.7</td> + <td class="tdl_ws1 bl">12.5</td> + <td class="tdl_ws1 bl">12.3</td> + </tr><tr> + <td class="tdc">30</td> + <td class="tdr_wsp bl">13.5</td> + <td class="tdr_wsp bl">12.6</td> + <td class="tdr_wsp bl">12.0</td> + <td class="tdl_ws1 bl">11.6</td> + <td class="tdl_ws1 bl">11.2</td> + <td class="tdl_ws1 bl">11.0</td> + <td class="tdl_ws1 bl">10.8</td> + <td class="tdl_ws1 bl">10.6</td> + </tr><tr> + <td class="tdc">25</td> + <td class="tdr_wsp bl">11.5</td> + <td class="tdr_wsp bl">10.8</td> + <td class="tdr_wsp bl">10.3</td> + <td class="tdl_ws1 bl">10.0</td> + <td class="tdl_ws1 bl"> 9.5</td> + <td class="tdl_ws1 bl"> 9.3</td> + <td class="tdl_ws1 bl"> 9.1</td> + <td class="tdl_ws1 bl"> 9.0</td> + </tr><tr> + <td class="tdc">20</td> + <td class="tdr_wsp bl"> 9.6</td> + <td class="tdr_wsp bl"> 9.1</td> + <td class="tdr_wsp bl"> 8.6</td> + <td class="tdl_ws1 bl"> 8.3</td> + <td class="tdl_ws1 bl"> 7.9</td> + <td class="tdl_ws1 bl"> 7.7</td> + <td class="tdl_ws1 bl"> 7.5</td> + <td class="tdl_ws1 bl"> 7.3</td> + </tr><tr> + <td class="tdc">15</td> + <td class="tdr_wsp bl"> 7.7</td> + <td class="tdr_wsp bl"> 7.3</td> + <td class="tdr_wsp bl"> 6.9</td> + <td class="tdl_ws1 bl"> 6.7</td> + <td class="tdl_ws1 bl"> 6.3</td> + <td class="tdl_ws1 bl"> 6.1</td> + <td class="tdl_ws1 bl"> 5.8</td> + <td class="tdl_ws1 bl"> 5.6</td> + </tr><tr class="bb"> + <td class="tdc">10</td> + <td class="tdr_wsp bl"> 5.8</td> + <td class="tdr_wsp bl"> 5.4</td> + <td class="tdr_wsp bl"> 5.1</td> + <td class="tdl_ws1 bl"> 5.0</td> + <td class="tdl_ws1 bl"> 4.7</td> + <td class="tdl_ws1 bl"> 4.5</td> + <td class="tdl_ws1 bl"> 4.2</td> + <td class="tdl_ws1 bl"> 3.9</td> + </tr> + </tbody> +</table> + +<table class="spb1"> + <thead><tr> + <th class="tdc"> </th> + <th class="tdc bb fs_105" colspan="6"><span class="smcap">Milligrams of Invert Sugar in Mixtures of</span></th> + </tr><tr> + <th class="tdc"> </th> + <th class="tdc bl">0.4(C)</th> + <th class="tdc bl">0.3(C)</th> + <th class="tdc bl">0.2(C)</th> + <th class="tdc bl">0.1(C)</th> + <th class="tdc bl">0.05(C)</th> + <th class="tdc bl">0.02(C)</th> + </tr><tr> + <th class="tdc bb"> (A) </th> + <th class="tdc bl bb"> 99.6(D) </th> + <th class="tdc bl bb"> 99.7(D) </th> + <th class="tdc bl bb"> 99.8(D) </th> + <th class="tdc bl bb"> 99.9(D) </th> + <th class="tdc bl bb"> 99.95(D) </th> + <th class="tdc bl bb"> 99.98(D) </th> + </tr></thead> + <tbody><tr> + <td class="tdc">88</td> + <td class="tdr_wsp bl">33.3</td> + <td class="tdr_wsp bl"> </td> + <td class="tdr_wsp bl"> </td> + <td class="tdl_ws1 bl"> </td> + <td class="tdl_ws1 bl"> </td> + <td class="tdl_ws1 bl"> </td> + </tr><tr> + <td class="tdc">85</td> + <td class="tdr_wsp bl">32.0</td> + <td class="tdr_wsp bl">31.8</td> + <td class="tdr_wsp bl"> </td> + <td class="tdl_ws1 bl"> </td> + <td class="tdl_ws1 bl"> </td> + <td class="tdl_ws1 bl"> </td> + </tr><tr> + <td class="tdc">80</td> + <td class="tdr_wsp bl">29.7</td> + <td class="tdr_wsp bl">29.5</td> + <td class="tdr_wsp bl"> </td> + <td class="tdl_ws1 bl"> </td> + <td class="tdl_ws1 bl"> </td> + <td class="tdl_ws1 bl"> </td> + </tr><tr> + <td class="tdc">75</td> + <td class="tdr_wsp bl">27.4</td> + <td class="tdr_wsp bl">27.2</td> + <td class="tdr_wsp bl"> </td> + <td class="tdl_ws1 bl"> </td> + <td class="tdl_ws1 bl"> </td> + <td class="tdl_ws1 bl"> </td> + </tr><tr> + <td class="tdc">70</td> + <td class="tdr_wsp bl">25.3</td> + <td class="tdr_wsp bl">25.0</td> + <td class="tdr_wsp bl"> </td> + <td class="tdl_ws1 bl"> </td> + <td class="tdl_ws1 bl"> </td> + <td class="tdl_ws1 bl"> </td> + </tr><tr> + <td class="tdc">65</td> + <td class="tdr_wsp bl">23.2</td> + <td class="tdr_wsp bl">22.8</td> + <td class="tdr_wsp bl"> </td> + <td class="tdl_ws1 bl"> </td> + <td class="tdl_ws1 bl"> </td> + <td class="tdl_ws1 bl"> </td> + </tr><tr> + <td class="tdc">60</td> + <td class="tdr_wsp bl">21.2</td> + <td class="tdr_wsp bl">20.8</td> + <td class="tdr_wsp bl">20.4</td> + <td class="tdl_ws1 bl"> </td> + <td class="tdl_ws1 bl"> </td> + <td class="tdl_ws1 bl"> </td> + </tr><tr> + <td class="tdc">55</td> + <td class="tdr_wsp bl">19.3</td> + <td class="tdr_wsp bl">18.9</td> + <td class="tdr_wsp bl">18.5</td> + <td class="tdl_ws1 bl"> </td> + <td class="tdl_ws1 bl"> </td> + <td class="tdl_ws1 bl"> </td> + </tr><tr> + <td class="tdc">50</td> + <td class="tdr_wsp bl">17.4</td> + <td class="tdr_wsp bl">17.0</td> + <td class="tdr_wsp bl">16.7</td> + <td class="tdl_ws1 bl"> </td> + <td class="tdl_ws1 bl"> </td> + <td class="tdl_ws1 bl"> </td> + </tr><tr> + <td class="tdc">45</td> + <td class="tdr_wsp bl">15.6</td> + <td class="tdr_wsp bl">15.3</td> + <td class="tdr_wsp bl">14.9</td> + <td class="tdl_ws1 bl"> </td> + <td class="tdl_ws1 bl"> </td> + <td class="tdl_ws1 bl"> </td> + </tr><tr> + <td class="tdc">40</td> + <td class="tdr_wsp bl">13.8</td> + <td class="tdr_wsp bl">13.5</td> + <td class="tdr_wsp bl">13.2</td> + <td class="tdl_ws1 bl"> </td> + <td class="tdl_ws1 bl"> </td> + <td class="tdl_ws1 bl"> </td> + </tr><tr> + <td class="tdc">35</td> + <td class="tdr_wsp bl">12.1</td> + <td class="tdr_wsp bl">11.9</td> + <td class="tdr_wsp bl">11.5</td> + <td class="tdl_ws1 bl">10.3</td> + <td class="tdl_ws1 bl"> </td> + <td class="tdl_ws1 bl"> </td> + </tr><tr> + <td class="tdc">30</td> + <td class="tdr_wsp bl">10.4</td> + <td class="tdr_wsp bl">10.2</td> + <td class="tdr_wsp bl"> 9.9</td> + <td class="tdl_ws1 bl"> 8.8</td> + <td class="tdl_ws1 bl"> </td> + <td class="tdl_ws1 bl"> </td> + </tr><tr> + <td class="tdc">25</td> + <td class="tdr_wsp bl"> 8.8</td> + <td class="tdr_wsp bl"> 8.6</td> + <td class="tdr_wsp bl"> 8.2</td> + <td class="tdl_ws1 bl"> 7.3</td> + <td class="tdl_ws1 bl"> </td> + <td class="tdl_ws1 bl"> </td> + </tr><tr> + <td class="tdc">20</td> + <td class="tdr_wsp bl"> 7.1</td> + <td class="tdr_wsp bl"> 6.9</td> + <td class="tdr_wsp bl"> 6.6</td> + <td class="tdl_ws1 bl"> 5.8</td> + <td class="tdl_ws1 bl"> 4.9</td> + <td class="tdl_ws1 bl"> </td> + </tr><tr> + <td class="tdc">15</td> + <td class="tdr_wsp bl"> 5.4</td> + <td class="tdr_wsp bl"> 5.2</td> + <td class="tdr_wsp bl"> 5.0</td> + <td class="tdl_ws1 bl"> 4.4</td> + <td class="tdl_ws1 bl"> 3.7</td> + <td class="tdl_ws1 bl"> 2.0</td> + </tr><tr class="bb"> + <td class="tdc">10</td> + <td class="tdr_wsp bl"> 3.8</td> + <td class="tdr_wsp bl"> 3.5</td> + <td class="tdr_wsp bl"> 3.4</td> + <td class="tdl_ws1 bl"> 3.0</td> + <td class="tdl_ws1 bl"> 2.5</td> + <td class="tdl_ws1 bl"> 1.7</td> + </tr> + </tbody> +</table> + +<p id="P_234"><b>234. Soldaini’s Method Adapted to Gravimetric Work.</b>—By reason +of their better keeping qualities and because of their less energetic +action on non-reducing sugars, copper carbonate solutions are to be +preferred to the alkaline copper tartrate solutions for gravimetric +determinations of reducing sugars in cane juices and sugar house +products, provided the difficulties which attend the manipulation +can be removed. Ost has succeeded in securing perfectly satisfactory +results with copper carbonate solution by slightly varying the +composition thereof and continuing the boiling, for the reduction of +the copper, ten minutes.<a id="FNanchor_191" href="#Footnote_191" class="fnanchor">[191]</a> +The copper solution is made as follows:</p> + +<table class="spb1"> + <tbody><tr> + <td class="tdr_wsp">17.5</td> + <td class="tdc">grams</td> + <td class="tdl_wsp">crystallized copper sulfate.</td> + </tr><tr> + <td class="tdr_wsp">250.0</td> + <td class="tdc">”</td> + <td class="tdl_wsp">potassium carbonate.</td> + </tr><tr> + <td class="tdr_wsp">100.0</td> + <td class="tdc">”</td> + <td class="tdl_wsp"><span class="ws2">”</span><span class="ws2">bicarbonate.</span></td> + </tr> + </tbody> +</table> + +<p>The above ingredients are dissolved in water and the volume of the +solution completed to one liter. The object of the potassium bicarbonate +<span class="pagenum"><a id="Page_259"></a>[Pg 259]</span> +is to secure in the solution an excess of carbon dioxid and thus +prevent the deposition of basic copper carbonate on keeping. The +manipulation is conducted as follows:</p> + +<p>One hundred cubic centimeters of the copper solution are mixed with +half that quantity of the sugar solution in a large erlenmeyer, which +is placed upon a wire gauze, heated quickly to boiling and kept in +ebullition just ten minutes. The sugar solution should contain not +less than eighty nor more than 150 milligrams of the reducing sugar, +and the quantity of the solution representing this should be diluted +to fifty cubic centimeters before mixing with the copper solution. +After boiling, the contents of the erlenmeyer are quickly cooled and +filtered with suction through an asbestos filter and the whole of the +copper suboxid washed into the filter tube. This precipitated suboxid +is washed once with a little potassium carbonate solution then with hot +water and finally with alcohol, well dried, heated to redness, and the +copper oxid obtained reduced to metallic copper in an atmosphere of +hydrogen entirely free of arsenic. From the weight of metallic copper +obtained the quantity of sugar which has been oxidized is calculated +from the tables below.</p> + +<p>It is evident that the process given above may be varied so as to +conform to the practice observed in this laboratory of cooling the +boiling solution sufficiently at once by adding to it an equal volume +of recently boiled, cold water, collecting the precipitated copper +suboxid in a gooch, and, after washing it, securing solution in nitric +acid and the precipitation of the copper by electrolysis. +<span class="pagenum"><a id="Page_260"></a>[Pg 260]</span></p> + +<p class="f120 spa1"><b><span class="smcap">Table Showing Milligrams Dextrose,<br> +Levulose and Invert Sugar Oxidized,<br>Corresponding to Milligrams of<br> +Copper Reduced.</span></b></p> + +<table class="spb1"> + <thead><tr> + <th class="tdc"> Copper. </th> + <th class="tdc"> Dextrose. </th> + <th class="tdc"> Levulose. </th> + <th class="tdc"> Invert. </th> + </tr></thead> + <tbody><tr> + <td class="tdc">435</td> + <td class="tdr_ws1">152.3</td> + <td class="tdr_ws1">145.9</td> + <td class="tdr_ws1">147.5</td> + </tr><tr> + <td class="tdc">430</td> + <td class="tdr_ws1">149.8</td> + <td class="tdr_ws1">143.4</td> + <td class="tdr_ws1">145.3</td> + </tr><tr> + <td class="tdc">425</td> + <td class="tdr_ws1">147.3</td> + <td class="tdr_ws1">140.9</td> + <td class="tdr_ws1">143.1</td> + </tr><tr> + <td class="tdc">420</td> + <td class="tdr_ws1">144.8</td> + <td class="tdr_ws1">138.4</td> + <td class="tdr_ws1">140.8</td> + </tr><tr> + <td class="tdc">415</td> + <td class="tdr_ws1">142.3</td> + <td class="tdr_ws1">135.9</td> + <td class="tdr_ws1">138.5</td> + </tr><tr> + <td class="tdc">410</td> + <td class="tdr_ws1">139.8</td> + <td class="tdr_ws1">133.5</td> + <td class="tdr_ws1">136.2</td> + </tr><tr> + <td class="tdc">405</td> + <td class="tdr_ws1">137.3</td> + <td class="tdr_ws1">131.1</td> + <td class="tdr_ws1">133.9</td> + </tr><tr> + <td class="tdc">400</td> + <td class="tdr_ws1">134.9</td> + <td class="tdr_ws1">128.7</td> + <td class="tdr_ws1">131.6</td> + </tr><tr> + <td class="tdc">395</td> + <td class="tdr_ws1">132.5</td> + <td class="tdr_ws1">126.4</td> + <td class="tdr_ws1">129.3</td> + </tr><tr> + <td class="tdc">390</td> + <td class="tdr_ws1">130.1</td> + <td class="tdr_ws1">124.1</td> + <td class="tdr_ws1">127.0</td> + </tr><tr> + <td class="tdc">385</td> + <td class="tdr_ws1">127.8</td> + <td class="tdr_ws1">121.8</td> + <td class="tdr_ws1">124.8</td> + </tr><tr> + <td class="tdc">380</td> + <td class="tdr_ws1">125.5</td> + <td class="tdr_ws1">119.5</td> + <td class="tdr_ws1">122.6</td> + </tr><tr> + <td class="tdc">375</td> + <td class="tdr_ws1">123.3</td> + <td class="tdr_ws1">117.2</td> + <td class="tdr_ws1">120.4</td> + </tr><tr class="bb"> + <td class="tdc">370</td> + <td class="tdr_ws1">121.1</td> + <td class="tdr_ws1">115.0</td> + <td class="tdr_ws1">118.2</td> + </tr><tr> + <td class="tdc">365</td> + <td class="tdr_ws1">119.0</td> + <td class="tdr_ws1">112.8</td> + <td class="tdr_ws1">116.0</td> + </tr><tr> + <td class="tdc">360</td> + <td class="tdr_ws1">116.9</td> + <td class="tdr_ws1">110.6</td> + <td class="tdr_ws1">113.9</td> + </tr><tr> + <td class="tdc">355</td> + <td class="tdr_ws1">114.8</td> + <td class="tdr_ws1">108.5</td> + <td class="tdr_ws1">111.8</td> + </tr><tr> + <td class="tdc">350</td> + <td class="tdr_ws1">112.8</td> + <td class="tdr_ws1">106.4</td> + <td class="tdr_ws1">109.8</td> + </tr><tr> + <td class="tdc">345</td> + <td class="tdr_ws1">110.8</td> + <td class="tdr_ws1">104.3</td> + <td class="tdr_ws1">107.8</td> + </tr><tr> + <td class="tdc">340</td> + <td class="tdr_ws1">108.8</td> + <td class="tdr_ws1">102.3</td> + <td class="tdr_ws1">105.8</td> + </tr><tr> + <td class="tdc">335</td> + <td class="tdr_ws1">106.8</td> + <td class="tdr_ws1">100.3</td> + <td class="tdr_ws1">103.8</td> + </tr><tr> + <td class="tdc">330</td> + <td class="tdr_ws1">104.9</td> + <td class="tdr_ws1">98.4</td> + <td class="tdr_ws1">101.8</td> + </tr><tr> + <td class="tdc">325</td> + <td class="tdr_ws1">103.0</td> + <td class="tdr_ws1">96.5</td> + <td class="tdr_ws1">99.9</td> + </tr><tr> + <td class="tdc">320</td> + <td class="tdr_ws1">101.1</td> + <td class="tdr_ws1">94.6</td> + <td class="tdr_ws1">98.0</td> + </tr><tr> + <td class="tdc">315</td> + <td class="tdr_ws1">99.2</td> + <td class="tdr_ws1">92.8</td> + <td class="tdr_ws1">96.2</td> + </tr><tr> + <td class="tdc">310</td> + <td class="tdr_ws1">97.4</td> + <td class="tdr_ws1">91.0</td> + <td class="tdr_ws1">94.4</td> + </tr><tr> + <td class="tdc">305</td> + <td class="tdr_ws1">95.6</td> + <td class="tdr_ws1">89.2</td> + <td class="tdr_ws1">92.6</td> + </tr><tr class="bb"> + <td class="tdc">300</td> + <td class="tdr_ws1">93.8</td> + <td class="tdr_ws1">87.5</td> + <td class="tdr_ws1">90.9</td> + </tr><tr> + <td class="tdc">295</td> + <td class="tdr_ws1">92.0</td> + <td class="tdr_ws1">85.8</td> + <td class="tdr_ws1">89.2</td> + </tr><tr> + <td class="tdc">290</td> + <td class="tdr_ws1">90.2</td> + <td class="tdr_ws1">84.1</td> + <td class="tdr_ws1">87.5</td> + </tr><tr> + <td class="tdc">285</td> + <td class="tdr_ws1">88.4</td> + <td class="tdr_ws1">82.4</td> + <td class="tdr_ws1">85.8</td> + </tr><tr> + <td class="tdc">280</td> + <td class="tdr_ws1">86.7</td> + <td class="tdr_ws1">80.8</td> + <td class="tdr_ws1">84.1</td> + </tr><tr> + <td class="tdc">275</td> + <td class="tdr_ws1">85.0</td> + <td class="tdr_ws1">79.2</td> + <td class="tdr_ws1">82.4</td> + </tr><tr> + <td class="tdc">270</td> + <td class="tdr_ws1">83.3</td> + <td class="tdr_ws1">77.6</td> + <td class="tdr_ws1">80.7</td> + </tr><tr> + <td class="tdc">265</td> + <td class="tdr_ws1">81.5</td> + <td class="tdr_ws1">76.1</td> + <td class="tdr_ws1">79.1</td> + </tr><tr> + <td class="tdc">260</td> + <td class="tdr_ws1">79.8</td> + <td class="tdr_ws1">74.6</td> + <td class="tdr_ws1">77.5</td> + </tr><tr> + <td class="tdc">255</td> + <td class="tdr_ws1">78.1</td> + <td class="tdr_ws1">73.1</td> + <td class="tdr_ws1">75.9</td> + </tr><tr> + <td class="tdc">250</td> + <td class="tdr_ws1">76.5</td> + <td class="tdr_ws1">71.6</td> + <td class="tdr_ws1">74.3</td> + </tr><tr> + <td class="tdc">245</td> + <td class="tdr_ws1">74.9</td> + <td class="tdr_ws1">70.1</td> + <td class="tdr_ws1">72.7</td> + </tr><tr> + <td class="tdc">240</td> + <td class="tdr_ws1">73.3</td> + <td class="tdr_ws1">68.6</td> + <td class="tdr_ws1">71.1</td> + </tr><tr> + <td class="tdc">235</td> + <td class="tdr_ws1">71.7</td> + <td class="tdr_ws1">67.2</td> + <td class="tdr_ws1">69.5</td> + </tr><tr class="bb"> + <td class="tdc">230</td> + <td class="tdr_ws1">70.1</td> + <td class="tdr_ws1">65.7</td> + <td class="tdr_ws1">68.0</td> + </tr><tr> + <td class="tdc">225</td> + <td class="tdr_ws1">68.5</td> + <td class="tdr_ws1">64.3</td> + <td class="tdr_ws1">66.5</td> + </tr><tr> + <td class="tdc">220</td> + <td class="tdr_ws1">66.9</td> + <td class="tdr_ws1">62.8</td> + <td class="tdr_ws1">65.0</td> + </tr><tr> + <td class="tdc">215</td> + <td class="tdr_ws1">65.3</td> + <td class="tdr_ws1">61.4</td> + <td class="tdr_ws1">63.5</td> + </tr><tr> + <td class="tdc">210</td> + <td class="tdr_ws1">63.8</td> + <td class="tdr_ws1">59.9</td> + <td class="tdr_ws1">62.0</td> + </tr><tr> + <td class="tdc">205</td> + <td class="tdr_ws1">62.2</td> + <td class="tdr_ws1">58.5</td> + <td class="tdr_ws1">60.5</td> + </tr><tr> + <td class="tdc">200</td> + <td class="tdr_ws1">60.7</td> + <td class="tdr_ws1">57.0</td> + <td class="tdr_ws1">59.0</td> + </tr><tr> + <td class="tdc">195</td> + <td class="tdr_ws1">59.1</td> + <td class="tdr_ws1">55.6</td> + <td class="tdr_ws1">57.5</td> + </tr><tr> + <td class="tdc">190</td> + <td class="tdr_ws1">57.6</td> + <td class="tdr_ws1">54.1</td> + <td class="tdr_ws1">56.0</td> + </tr><tr> + <td class="tdc">185</td> + <td class="tdr_ws1">56.0</td> + <td class="tdr_ws1">52.7</td> + <td class="tdr_ws1">54.5</td> + </tr><tr> + <td class="tdc">180</td> + <td class="tdr_ws1">54.5</td> + <td class="tdr_ws1">51.2</td> + <td class="tdr_ws1">53.1</td> + </tr><tr> + <td class="tdc">175</td> + <td class="tdr_ws1">53.0</td> + <td class="tdr_ws1">49.8</td> + <td class="tdr_ws1">51.6</td> + </tr><tr> + <td class="tdc">170</td> + <td class="tdr_ws1">51.5</td> + <td class="tdr_ws1">48.4</td> + <td class="tdr_ws1">50.2</td> + </tr><tr> + <td class="tdc">165</td> + <td class="tdr_ws1">50.0</td> + <td class="tdr_ws1">46.9</td> + <td class="tdr_ws1">48.7</td> + </tr><tr class="bb"> + <td class="tdc">160</td> + <td class="tdr_ws1">48.5</td> + <td class="tdr_ws1">45.5</td> + <td class="tdr_ws1">47.3</td> + </tr><tr> + <td class="tdc">155</td> + <td class="tdr_ws1">47.0</td> + <td class="tdr_ws1">44.1</td> + <td class="tdr_ws1">45.8</td> + </tr><tr> + <td class="tdc">150</td> + <td class="tdr_ws1">45.5</td> + <td class="tdr_ws1">42.7</td> + <td class="tdr_ws1">44.4</td> + </tr><tr> + <td class="tdc">145</td> + <td class="tdr_ws1">44.0</td> + <td class="tdr_ws1">41.3</td> + <td class="tdr_ws1">42.9</td> + </tr><tr> + <td class="tdc">140</td> + <td class="tdr_ws1">42.5</td> + <td class="tdr_ws1">39.9</td> + <td class="tdr_ws1">41.5</td> + </tr><tr> + <td class="tdc">135</td> + <td class="tdr_ws1">41.0</td> + <td class="tdr_ws1">38.5</td> + <td class="tdr_ws1">40.1</td> + </tr><tr> + <td class="tdc">130</td> + <td class="tdr_ws1">39.6</td> + <td class="tdr_ws1">37.1</td> + <td class="tdr_ws1">38.6</td> + </tr><tr> + <td class="tdc">125</td> + <td class="tdr_ws1">38.1</td> + <td class="tdr_ws1">35.7</td> + <td class="tdr_ws1">37.2</td> + </tr><tr> + <td class="tdc">120</td> + <td class="tdr_ws1">36.7</td> + <td class="tdr_ws1">34.3</td> + <td class="tdr_ws1">35.8</td> + </tr><tr> + <td class="tdc">115</td> + <td class="tdr_ws1">35.2</td> + <td class="tdr_ws1">32.9</td> + <td class="tdr_ws1">34.3</td> + </tr><tr> + <td class="tdc">110</td> + <td class="tdr_ws1">33.7</td> + <td class="tdr_ws1">31.6</td> + <td class="tdr_ws1">32.9</td> + </tr><tr> + <td class="tdc">105</td> + <td class="tdr_ws1">32.2</td> + <td class="tdr_ws1">30.3</td> + <td class="tdr_ws1">31.4</td> + </tr><tr> + <td class="tdc">100</td> + <td class="tdr_ws1">30.7</td> + <td class="tdr_ws1">29.0</td> + <td class="tdr_ws1">30.0</td> + </tr><tr> + <td class="tdc"> 95</td> + <td class="tdr_ws1">29.2</td> + <td class="tdr_ws1">27.7</td> + <td class="tdr_ws1">28.5</td> + </tr><tr> + <td class="tdc"> 90</td> + <td class="tdr_ws1">27.8</td> + <td class="tdr_ws1">26.4</td> + <td class="tdr_ws1">27.1</td> + </tr><tr> + <td class="tdc"> 85</td> + <td class="tdr_ws1">26.3</td> + <td class="tdr_ws1">25.1</td> + <td class="tdr_ws1">25.6</td> + </tr><tr> + <td class="tdc"> 80</td> + <td class="tdr_ws1">24.8</td> + <td class="tdr_ws1">23.8</td> + <td class="tdr_ws1">24.2</td> + </tr><tr> + <td class="tdc"> 75</td> + <td class="tdr_ws1">23.3</td> + <td class="tdr_ws1">21.5</td> + <td class="tdr_ws1">22.8</td> + </tr><tr class="bb"> + <td class="tdc"> 70</td> + <td class="tdr_ws1">21.8</td> + <td class="tdr_ws1">20.2</td> + <td class="tdr_ws1">21.4 + <span class="pagenum"><a id="Page_261"></a>[Pg 261]</span></td> + </tr> + </tbody> +</table> + +<p class="f120 spa2"><b><span class="smcap">Corresponding Table for Maltose.</span></b></p> + +<table class="spb1"> + <thead><tr class="bb"> + <th class="tdc"> Milligrams <br>copper<br>obtained.</th> + <th class="tdc"> Milligrams <br>maltose<br>anhydrid<br>oxidized.</th> + <th class="tdc"> Milligrams <br>maltose<br>hydrate<br>oxidized.</th> + </tr></thead> + <tbody><tr> + <td class="tdc">435</td> + <td class="tdc">263.7</td> + <td class="tdc">277.6</td> + </tr><tr> + <td class="tdc">430</td> + <td class="tdc">259.3</td> + <td class="tdc">273.0</td> + </tr><tr> + <td class="tdc">425</td> + <td class="tdc">255.0</td> + <td class="tdc">268.4</td> + </tr><tr> + <td class="tdc">420</td> + <td class="tdc">250.9</td> + <td class="tdc">264.1</td> + </tr><tr> + <td class="tdc">415</td> + <td class="tdc">247.0</td> + <td class="tdc">260.0</td> + </tr><tr> + <td class="tdc">410</td> + <td class="tdc">243.2</td> + <td class="tdc">256.0</td> + </tr><tr> + <td class="tdc">405</td> + <td class="tdc">339.4</td> + <td class="tdc">252.0</td> + </tr><tr> + <td class="tdc">400</td> + <td class="tdc">235.6</td> + <td class="tdc">248.0</td> + </tr><tr> + <td class="tdc">395</td> + <td class="tdc">231.9</td> + <td class="tdc">244.1</td> + </tr><tr> + <td class="tdc">390</td> + <td class="tdc">228.2</td> + <td class="tdc">240.2</td> + </tr><tr> + <td class="tdc">385</td> + <td class="tdc">224.6</td> + <td class="tdc">236.4</td> + </tr><tr> + <td class="tdc">380</td> + <td class="tdc">221.1</td> + <td class="tdc">232.7</td> + </tr><tr class="bb"> + <td class="tdc">375</td> + <td class="tdc">217.7</td> + <td class="tdc">229.1</td> + </tr><tr> + <td class="tdc">370</td> + <td class="tdc">214.4</td> + <td class="tdc">225.6</td> + </tr><tr> + <td class="tdc">365</td> + <td class="tdc">211.1</td> + <td class="tdc">222.2</td> + </tr><tr> + <td class="tdc">360</td> + <td class="tdc">207.9</td> + <td class="tdc">218.8</td> + </tr><tr> + <td class="tdc">355</td> + <td class="tdc">204.7</td> + <td class="tdc">215.4</td> + </tr><tr> + <td class="tdc">350</td> + <td class="tdc">201.5</td> + <td class="tdc">212.1</td> + </tr><tr> + <td class="tdc">345</td> + <td class="tdc">198.3</td> + <td class="tdc">208.7</td> + </tr><tr> + <td class="tdc">340</td> + <td class="tdc">195.2</td> + <td class="tdc">205.4</td> + </tr><tr> + <td class="tdc">335</td> + <td class="tdc">192.0</td> + <td class="tdc">202.1</td> + </tr><tr> + <td class="tdc">330</td> + <td class="tdc">188.8</td> + <td class="tdc">198.8</td> + </tr><tr> + <td class="tdc">325</td> + <td class="tdc">185.7</td> + <td class="tdc">195.4</td> + </tr><tr> + <td class="tdc">320</td> + <td class="tdc">182.5</td> + <td class="tdc">192.1</td> + </tr><tr> + <td class="tdc">315</td> + <td class="tdc">179.4</td> + <td class="tdc">188.8</td> + </tr><tr> + <td class="tdc">310</td> + <td class="tdc">176.3</td> + <td class="tdc">185.6</td> + </tr><tr class="bb"> + <td class="tdc">305</td> + <td class="tdc">173.3</td> + <td class="tdc">182.4</td> + </tr><tr> + <td class="tdc">300</td> + <td class="tdc">170.3</td> + <td class="tdc">179.2</td> + </tr><tr> + <td class="tdc">295</td> + <td class="tdc">167.3</td> + <td class="tdc">176.1</td> + </tr><tr> + <td class="tdc">290</td> + <td class="tdc">164.4</td> + <td class="tdc">173.0</td> + </tr><tr> + <td class="tdc">285</td> + <td class="tdc">161.4</td> + <td class="tdc">169.9</td> + </tr><tr> + <td class="tdc">280</td> + <td class="tdc">158.5</td> + <td class="tdc">166.8</td> + </tr><tr> + <td class="tdc">275</td> + <td class="tdc">155.5</td> + <td class="tdc">163.7</td> + </tr><tr> + <td class="tdc">270</td> + <td class="tdc">152.6</td> + <td class="tdc">160.7</td> + </tr><tr> + <td class="tdc">265</td> + <td class="tdc">149.7</td> + <td class="tdc">157.6</td> + </tr><tr> + <td class="tdc">260</td> + <td class="tdc">146.8</td> + <td class="tdc">154.6</td> + </tr><tr> + <td class="tdc">255</td> + <td class="tdc">143.9</td> + <td class="tdc">151.5</td> + </tr><tr> + <td class="tdc">250</td> + <td class="tdc">141.1</td> + <td class="tdc">148.5</td> + </tr><tr> + <td class="tdc">245</td> + <td class="tdc">138.2</td> + <td class="tdc">145.5</td> + </tr><tr> + <td class="tdc">240</td> + <td class="tdc">135.4</td> + <td class="tdc">142.5</td> + </tr><tr> + <td class="tdc">235</td> + <td class="tdc">132.5</td> + <td class="tdc">139.5</td> + </tr><tr> + <td class="tdc">230</td> + <td class="tdc">129.7</td> + <td class="tdc">136.5</td> + </tr><tr> + <td class="tdc">225</td> + <td class="tdc">126.8</td> + <td class="tdc">133.5</td> + </tr><tr> + <td class="tdc">220</td> + <td class="tdc">124.0</td> + <td class="tdc">130.6</td> + </tr><tr> + <td class="tdc">215</td> + <td class="tdc">121.2</td> + <td class="tdc">127.6</td> + </tr><tr> + <td class="tdc">210</td> + <td class="tdc">118.4</td> + <td class="tdc">124.7</td> + </tr><tr class="bb"> + <td class="tdc">205</td> + <td class="tdc">115.7</td> + <td class="tdc">121.8</td> + </tr><tr> + <td class="tdc">200</td> + <td class="tdc">112.9</td> + <td class="tdc">118.9</td> + </tr><tr> + <td class="tdc">195</td> + <td class="tdc">110.2</td> + <td class="tdc">116.0</td> + </tr><tr> + <td class="tdc">190</td> + <td class="tdc">107.4</td> + <td class="tdc">113.1</td> + </tr><tr> + <td class="tdc">185</td> + <td class="tdc">104.7</td> + <td class="tdc">110.2</td> + </tr><tr> + <td class="tdc">180</td> + <td class="tdc">101.9</td> + <td class="tdc">107.3</td> + </tr><tr> + <td class="tdc">175</td> + <td class="tdc"> 99.2</td> + <td class="tdc">104.4</td> + </tr><tr> + <td class="tdc">170</td> + <td class="tdc"> 96.4</td> + <td class="tdc">101.5</td> + </tr><tr> + <td class="tdc">165</td> + <td class="tdc"> 93.7</td> + <td class="tdc"> 98.6</td> + </tr><tr> + <td class="tdc">160</td> + <td class="tdc"> 90.9</td> + <td class="tdc"> 95.7</td> + </tr><tr> + <td class="tdc">155</td> + <td class="tdc"> 88.2</td> + <td class="tdc"> 92.8</td> + </tr><tr> + <td class="tdc">150</td> + <td class="tdc"> 85.4</td> + <td class="tdc"> 89.9</td> + </tr><tr> + <td class="tdc">145</td> + <td class="tdc"> 82.6</td> + <td class="tdc"> 87.0</td> + </tr><tr> + <td class="tdc">140</td> + <td class="tdc"> 79.9</td> + <td class="tdc"> 84.1</td> + </tr><tr> + <td class="tdc">135</td> + <td class="tdc"> 77.1</td> + <td class="tdc"> 81.2</td> + </tr><tr> + <td class="tdc">130</td> + <td class="tdc"> 74.4</td> + <td class="tdc"> 78.3</td> + </tr><tr> + <td class="tdc">125</td> + <td class="tdc"> 71.6</td> + <td class="tdc"> 75.4</td> + </tr><tr> + <td class="tdc">120</td> + <td class="tdc"> 68.9</td> + <td class="tdc"> 72.5</td> + </tr><tr> + <td class="tdc">115</td> + <td class="tdc"> 66.1</td> + <td class="tdc"> 69.6</td> + </tr><tr> + <td class="tdc">110</td> + <td class="tdc"> 63.4</td> + <td class="tdc"> 66.7</td> + </tr><tr class="bb"> + <td class="tdc">105</td> + <td class="tdc"> 60.6</td> + <td class="tdc"> 63.8</td> + </tr><tr> + <td class="tdc">100</td> + <td class="tdc"> 57.9</td> + <td class="tdc"> 60.9</td> + </tr><tr> + <td class="tdc"> 95</td> + <td class="tdc"> 55.1</td> + <td class="tdc"> 58.0</td> + </tr><tr> + <td class="tdc"> 90</td> + <td class="tdc"> 52.3</td> + <td class="tdc"> 55.1</td> + </tr><tr> + <td class="tdc"> 85</td> + <td class="tdc"> 49.6</td> + <td class="tdc"> 52.2</td> + </tr><tr> + <td class="tdc"> 80</td> + <td class="tdc"> 46.8</td> + <td class="tdc"> 59.3</td> + </tr><tr> + <td class="tdc"> 75</td> + <td class="tdc"> 44.1</td> + <td class="tdc"> 56.4</td> + </tr><tr class="bb"> + <td class="tdc"> 70</td> + <td class="tdc"> 41.4</td> + <td class="tdc"> 53.5</td> + </tr> + </tbody> +</table> + +<p><span class="pagenum"><a id="Page_262"></a>[Pg 262]</span> +<b>235. Weighing the Copper as Oxid.</b>—In the usual methods of the +determination of reducing bodies, the percentage is calculated either +volumetrically from the quantity of the sugar solution required to +decolorize a given volume of the alkaline copper solution, or the +reduced copper suboxid is brought into a metallic state by heating in +an atmosphere of hydrogen or by electrolytic deposition. A quicker +method of procedure is found in completing the oxidation of the cupric +oxid by heating to low redness in a current of air.<a id="FNanchor_192" href="#Footnote_192" class="fnanchor">[192]</a> For this +determination the precipitation of the cuprous oxid and its filtration +are made in the usual manner. The cuprous oxid is collected in a +filtering tube, made by drawing out to proper dimensions a piece of +combustion tube, and has a length of about twelve centimeters in all. +The unchanged part of the tube is about eight centimeters in length +and twelve millimeters in diameter. It is filled by first putting in +a plug of glass wool and covering this with an asbestos felt on top +of which another plug of glass wool is placed. After the cuprous oxid +is collected in the tube it is washed with boiling water, alcohol and +ether. The rubber tube connecting it with the suction is of sufficient +length to permit the tube being taken in one hand and brought into +a horizontal position over a bunsen. The tube is gradually heated, +rotating it meanwhile, until any residual moisture, alcohol or ether, +is driven off from the filtering material. The layer of glass wool +holding the cuprous oxid is gradually brought into the flame and as +the oxidation begins the material will be seen to glow. The heating is +continued for some time after the glowing has ceased, in all for three +or four minutes, the tube and the copper oxid which it contains being +brought to a low redness. The current of air passing over the red-hot +material in this time oxidizes it completely. The filtering tube, +before use, must be ignited and weighed in exactly the same manner as +described above. The heat is so applied as not to endanger the rubber +tube attached to one end of the filtering tube nor to burn the fingers +of the operator as he turns the tube during the heating. After complete +oxidation the tube is cooled in a desiccator and weighed, the increase +of weight giving the copper oxid. For the atomic weights, 63.3 copper +<span class="pagenum"><a id="Page_263"></a>[Pg 263]</span> +and 15.96 oxygen, one gram of copper oxid is equivalent to 0.79864 +gram of copper, and for the weights 63.17 copper and 15.96 oxygen, one +gram of copper oxid equals 0.79831 gram of copper. From the amount of +metallic copper calculated by one of these factors, the reducing sugar +is determined by the tables already given.</p> + +<p><b>236. Estimation of Dry Substance, Polarization and Apparent Purity +for Factory Control.</b>—For technical purposes the methods of +determining the above factors, proposed by Weisberg and applicable to +concentrated sirups, massecuites, and molasses, may be used.<a id="FNanchor_193" href="#Footnote_193" class="fnanchor">[193]</a> +Five times the half normal quantity of the material, <i>viz.</i>, 65.12 +grams, are placed in a quarter liter flask, dissolved in water and the +flask filled to the mark. In the well shaken mixture, which is allowed +to stand long enough to be free of air, the degree brix is estimated +by an accurate spindle. For example, in the case of molasses, let the +number obtained be 18.8.</p> + +<p>Fifty cubic centimeters of the solution are poured into a 100 cubic +centimeter flask, the proper quantity of lead subacetate added, the +flask filled to the mark with water, its contents filtered, and the +filtrate polarized in a 200 millimeter tube. Let the number obtained on +polarization be 22°.1. This number may be used in two ways. If it be +multiplied by two the polarization of the original sample is obtained; +in this case, <i>viz.</i>, 44°.2. In the second place, if 44.2 be +multiplied by 0.26048 and this product divided by the specific gravity +corresponding to 18°.8. <i>viz.</i>, 1.078, the quotient 10.68 is +secured representing the polarization or per cent of sugar contained in +the solution of which the degree brix was 18.8°. From the numbers 18.8 +and 10.68 the apparent purity of the solution, 56.8, is calculated, +<i>viz.</i>, 10.68 × 100 ÷ by 18.8. The original product as calculated +above gives a polarization of 44.2 and this number multiplied by 100 +and divided by 56.8 gives 77.8, or the apparent percentage of dry +matter. The original sample of molasses, therefore, had the following +composition:</p> + +<table class="spb1"> + <tbody><tr> + <td class="tdl">Degree brix (total solids)  </td> + <td class="tdc"> 77.8</td> + <td class="tdl_wsp">per cent.</td> + </tr><tr> + <td class="tdl">Sucrose</td> + <td class="tdc">44.2</td> + <td class="tdc">”</td> + </tr><tr> + <td class="tdl">Solids, not sucrose</td> + <td class="tdc">33.6</td> + <td class="tdc">”</td> + </tr><tr> + <td class="tdl">Apparent purity</td> + <td class="tdc">56.8</td> + <td class="tdc">”</td> + </tr> + </tbody> +</table> + +<p><span class="pagenum"><a id="Page_264"></a>[Pg 264]</span> +It is seen from the above that with a single weighing and a single +polarization, and within from ten to fifteen minutes, all needful +data in respect of the proper treatment of molasses for the practical +control and direction of a factory can be obtained.</p> + +<p>In case a laurent polariscope is used, five times the normal weight, +<i>viz.</i>, eighty-one grams of the raw material are used and the +process conducted as above.</p> + +<h3>SUCROSE, DEXTROSE, INVERT SUGAR, LEVULOSE,<br> MALTOSE, +RAFFINOSE, DEXTRIN AND<br> LACTOSE IN MIXTURES.</h3> + +<p id="P_237"><b>237. Occurrence.</b>—Sucrose and invert sugar are found together in +many commercial products, especially in raw sugars and molasses made +from sugar cane, and in these products sucrose is usually predominant. +They also form the principal saccharine contents of honey, the invert +sugar, in this case, being the chief ingredient.</p> + +<p>In commercial grape sugar, made from starch, dextrose is the important +constituent, while in the hydrolysis of starch by a diastatic ferment, +maltose is principally produced. In the manufacture of commercial +glucose by the saccharification of starch with sulfuric acid, dextrin, +maltose, and dextrose are the dominant products, while in the similar +substance midzu ame, maltose and dextrose are chiefly found, and only a +small quantity of dextrose.<a id="FNanchor_194" href="#Footnote_194" class="fnanchor">[194]</a> +In honeys derived from the exudations of coniferous trees are found +also polarizing bodies not enumerated above and presumably of a pentose +character.<a id="FNanchor_195" href="#Footnote_195" class="fnanchor">[195]</a> +In evaporated milks are usually found large quantities of sucrose +in addition to the natural sugar therein contained. These mixtures +of carbohydrates often present problems of great difficulty to the +analyst, and the following paragraphs will be devoted to an elucidation +of the best approved methods of solving them.</p> + +<h3>OPTICAL METHODS.</h3> + +<p id="P_238"><b>238. Sucrose and Invert Sugar.</b>—The chemical methods of +procedure to be followed in the case of a sample containing both +sucrose and invert sugar have been given in sufficient detail in +preceding paragraphs (<b><a href="#P_124">124</a>, <a href="#P_171">171</a></b>). +<span class="pagenum"><a id="Page_265"></a>[Pg 265]</span> +When, however, it is desirable to study further the composition of +the mixture, important changes in the method are rendered imperative. +While the estimation of the sucrose and the total invert sugar, or +the sum of the dextrose and levulose, is easy of accomplishment the +separate determination of the dextrose and levulose is not so readily +secured. In the latter case the total quantity of the two sugars may +be determined, and after the destruction or removal of one of them the +other be estimated in the usual way; or in the mixture the levulose can +be determined by the variation in its gyrodynat, caused by changes of +temperature.</p> + +<p><b>239. Optical Neutrality of Invert Sugar.</b>—The gyrodynat of +levulose decreases as the temperature rises (<b><a href="#P_107">107</a></b>) and at or +near a temperature of 87°.2, it becomes equal to that of dextrose, +and, therefore, pure invert sugar composed of equal molecules of +levulose and dextrose is optically neutral to polarized light at that +temperature. On this fact Chandler and Ricketts have based a method of +analysis which excludes any interference in polarization due to invert +sugar.<a id="FNanchor_196" href="#Footnote_196" class="fnanchor">[196]</a> +To secure the polarization at approximately a temperature +of 87°, a water-bath is placed between the nicols of an ordinary +polariscope in such a way as to hold a tubulated observation tube +in the optical axis of the instrument. The ends of the bath, in the +prolongation of this axis, are provided with clear glass disks. The +space between the cover glasses of the observation tube and the glass +disks of the bath is occupied by the water of the bath. When this is +kept at a constant temperature it does not interfere with the reading. +The observation tube may be of glass, but preferably is constructed of +metal plated with platinum on the inside. For the most exact work the +length of the observation tube, at 87°, is determined by measurement or +calculation. The bath is heated with alcohol lamps or other convenient +means. The arrangement of the apparatus is shown in <a href="#FIG_75B">Fig. 75</a>.</p> + +<p>In a mixture of sucrose and invert sugar any rotation of the plane +of polarized light at 87° is due to the sucrose alone. In a mixture +of dextrose and sucrose the polarization is determined, and, after +inversion, again determined at 87°. The latter number is due to +dextrose alone, and the difference between the two gives the rotation +due to sucrose. +<span class="pagenum"><a id="Page_266"></a>[Pg 266]</span></p> + +<div class="figcenter smcap"> + <img id="FIG_75B" src="images/fig75_2.jpg" alt="" width="400" height="462" > + <p class="center spb1">Fig. 75.—Chandler and Ricketts’ Polariscope.</p> +</div> + +<p><b>240. Sucrose and Raffinose.</b>—In raw sugars made from beet +molasses considerable quantities of raffinose are found. The method +of inversion and polarization in such cases is described in paragraph +<b><a href="#P_100">100</a></b>. In making the inversion by the method proposed by Lindet +(<b><a href="#P_95">95</a></b>), and conducting the polarization on a laurent instrument, a +slightly different formula, given below, is used; <i>viz.</i>:</p> + +<table class="spb1 fs_105"> + <tbody><tr> + <td class="tdr" rowspan="2"><i>S</i> = </td> + <td class="tdc bb"><i>C</i> - 0.4891<i>A</i></td> + </tr><tr> + <td class="tdc">0.810</td> + </tr><tr> + <td class="tdc" colspan="2"> </td> + </tr><tr> + <td class="tdl" rowspan="2">and <i>R</i> = </td> + <td class="tdc bb"><i>A</i> - <i>S</i></td> + </tr><tr> + <td class="tdc">1.54</td> + </tr> + </tbody> +</table> + +<p><span class="pagenum"><a id="Page_267"></a>[Pg 267]</span> +in which the several letters refer to the same factors as are indicated +by them in the formula of Creydt. In the application of the formula +just given the normal weight of the mixed raw sugars used is 16.2 +grams.<a id="FNanchor_197" href="#Footnote_197" class="fnanchor">[197]</a></p> + +<p><b>241. Optical Determination of Levulose.</b>—The determination of +levulose by optical methods alone is made possible by reason of the +fact that the gyrodynats of the sugars with which it is associated are +not sensibly affected by changes of temperature. The principle of the +process, as developed by the author, rests on the ascertainment of the +change in the gyrodynat of levulose when its rotation is observed at +widely separated temperatures.<a id="FNanchor_198" href="#Footnote_198" class="fnanchor">[198]</a> +The observation tube employed for reading at low temperatures is +provided with desiccating end tubes, which prevent the deposition of +moisture on the cover glasses. The relations of this device to the +optical parts of the apparatus are illustrated in <a href="#FIG_76">Fig. 76</a>.</p> + +<div class="figcenter smcap"> + <img id="FIG_76" src="images/fig76.jpg" alt="" width="600" height="320" > + <p class="center spb1">Fig. 76.—Apparatus for Polarimetric Observations<br> + at Low Temperatures.</p> +</div> + +<p>The protecting tubes are made of hard rubber and the desiccation is +secured by surrounding the space between the rubber and the perforated +metal axis with fragments of potash or calcium chlorid.</p> + +<p>The details of the construction are shown in a horizontal section +through the center of the observation tube in <a href="#FIG_77">Fig. 77</a>. In this figure +<span class="pagenum"><a id="Page_268"></a>[Pg 268]</span> +the observation tube, made of glass or metal, is represented by +<i>i</i>, the metal jacket, open at the top in the <b>V</b> shape as +described, by <i>k</i>. The observation tube is closed by the heavy +disk <i>b</i> made of non-polarizing glass. This disk is pressed +against the end of the observation tube by the rubber washer <i>a</i>, +when the drying system about to be described is screwed on to <i>k</i>. +The apparatus for keeping the cover glass dry is contained in the +hard rubber tube <i>m</i> and consists of a perforated cylinder of +brass <i>e</i>, supported at one end by the perforated disk <i>c</i> +and at the outer ends by the arms <i>d</i>. It is closed by a cover +glass of non-polarizing glass <i>s</i> and can be screwed on to the +system <i>h</i> at <i>n</i>. The space <i>p</i> is filled with coarse +fragments of caustic soda, potash, or calcium chlorid by removing the +cover glass <i>s</i>. The perforated disk <i>c</i> prevents any of the +fragments from entering the axis of observation. When the cover glass +<i>s</i> is replaced, it just touches the free end of the perforated +metal tube preventing any of the fragments of the drying material from +falling into the center at the outer end. When this drying tube is +placed in position, the contents of the observation tube <i>i</i> can +be kept at the temperature of zero for an indefinite time without the +deposition of a particle of moisture either upon the glass <i>b</i> or <i>s</i>.</p> + +<div class="figcenter smcap"> + <img id="FIG_77" src="images/fig77.jpg" alt="" width="600" height="318" > + <p class="center spb1">Fig. 77.—Construction of Desicating Tube.</p> +</div> + +<p><span class="pagenum"><a id="Page_269"></a>[Pg 269]</span> +For determining the rotation at a high temperature the apparatus of +Chandler and Ricketts (<b><a href="#P_238">238</a></b>) may be used or the following device: +The polarizing apparatus shown above, <a href="#FIG_76">Fig. 76</a>, may be used +after the <b>V</b> shape box is removed from the stand, which is so constructed +as to receive a large box covered with asbestos felt an inch thick. The +observation tube is held within this box in the same way as in the one +just described so that the hot water extends not only the entire length +of the tube but also covers the cover glasses. In both cases the cover +glasses are made of heavier glass and are much larger in diameter than +found in the ordinary tubes for polariscopes. The protecting cylinders +of hard rubber are not needed at high temperatures but can be left on +without detriment.</p> + +<p>The illustration, <a href="#FIG_78">Fig. 78</a>, shows the +arrangement of the apparatus with a silver tube in position, which can +be filled and emptied without removing it.</p> + +<div class="figcenter smcap"> + <img id="FIG_78" src="images/fig78.jpg" alt="" width="600" height="408" > + <p class="center spb1">Fig. 78.—Apparatus for Polarizing<br> at High Temperatures.</p> +</div> + +<p>In practice the water is heated with a jet of steam and an even +temperature is secured by a mechanical stirrer kept slowly in motion. +<span class="pagenum"><a id="Page_270"></a>[Pg 270]</span> +With such a box it is easy to maintain a temperature for several +hours which will not vary more than half a degree. The temperature +for reading the hot solutions was fixed at 88°, this being nearly the +temperature at which a mixture of equal molecules of levulose and +dextrose is optically inactive. In every case the sugar solutions were +made up to the standard volume at the temperatures at which they were +to be read and thus the variations due to expansion or contraction +were avoided. When solutions are read at a high temperature, they must +be made with freshly boiled water so as to avoid the evolution of air +bubbles which may otherwise obscure the field of vision.</p> + +<p>By means of the apparatus described it is easy for the analyst to make +a polarimetric reading at any temperature desired. In all cases the +observation tube should be left at least a half an hour and sometimes +longer in contact with the temperature control media before the reading +is made.</p> + +<p>The appearance of the field of vision is usually a pretty fair index +of the point of time at which a constant temperature is established +throughout all parts of the system. Any variation in temperature +produces a distortion of the field of vision while a constant fixed +temperature will disclose the field of vision in its true shape and +distinctness of outline.</p> + +<p><i>Principles of the Calculation.</i>—If 26.048 grams of pure sucrose +be dissolved in water and the volume made 100 cubic centimeters, it +will produce an angular rotation of 34°.68 when examined in a 200 +millimeter tube with polarized sodium monochromatic light. Upon the +cane sugar scale of an accurately graduated shadow instrument the +reading will be 100 divisions corresponding to 100 per cent of pure +sucrose.</p> + +<p>In the complete inversion of the cane sugar the reaction which takes +place is represented by the following formula:</p> + +<table class="spb1 fs_110"> + <tbody><tr> + <td class="tdc"> </td> + <td class="tdc"> </td> + <td class="tdc">—</td> + <td class="tdc">+</td> + </tr><tr> + <td class="tdr_wsp">C₁₂H₂₂O₁₁ +</td> + <td class="tdr_wsp">H₂0 =</td> + <td class="tdr_wsp">C₆H₁₂O₆ +</td> + <td class="tdl">C₆H₁₂O₆.</td> + </tr> + </tbody> +</table> + +<p>The minus and plus signs indicate that the resulting invert sugar is +a mixture of equal parts of levulose (<i>d</i> fructose) and dextrose +(<i>d</i> glucose). We are not concerned here with the fact that a +complete inversion of cane sugar is a matter of great difficulty nor +<span class="pagenum"><a id="Page_271"></a>[Pg 271]</span> +with the danger which is always experienced of destroying a part of +one of the products of inversion. They are matters which may cause +a variation in the analytical data afterward, but do not affect the +principles on which the process is based.</p> + +<p>In the inversion of 26.048 grams of cane sugar there are therefore +produced 13.71 grams of levulose and 13.71 grams of dextrose or, in +all, 27.42 grams of the mixed sugars.</p> + +<p>The angular rotation which would be produced by 13.71 grams of +dextrose in a volume of 100 cubic centimeters and through a column 200 +millimeters in length is, with sodium light, 14°.53 equivalent to 41.89 +divisions of the cane sugar scale. The specific rotatory power of a +dextrose solution of the density given is almost exactly 53, and this +number is used in the calculations.</p> + +<p>In a mixture of the two sugars under the conditions mentioned and at a +temperature of 0° the angular rotation observed is -15°.15 equivalent +to 43.37 divisions of the cane sugar scale.</p> + +<p>The + rotation due to the dextrose is 14°.53. Therefore the total +negative rotation due to levulose at 0° is 15°.15 + 14°.53 = +29°.68. Hence the gyrodynat of levulose at 0° and in the degree of +concentration noted is readily calculated from the formula</p> + +<table class="spb1 fs_105"> + <tbody><tr> + <td class="tdl" rowspan="2">[α]°<span class="fs_80"><sub>D</sub></span> = - </td> + <td class="tdc bb">29.68 × 100</td> + <td class="tdl_wsp" rowspan="2">= -108.24.</td> + </tr><tr> + <td class="tdc">2 × 13.71</td> + </tr> + </tbody> +</table> + +<p>Since at 88° (<i>circa</i>) the mixture of levulose and dextrose is +neutral to polarized light, it follows that at that temperature the +specific rotatory power of levulose is equal to that of dextrose, +<i>viz.</i>, 53°.</p> + +<p class="f105">[α]<span class="fs_80"><sub>D</sub></span>⁸⁸ ° = - 53°.</p> + +<p>The total variation in the specific rotatory power of levulose, between +zero and 88°, is 55°.24. The variation for each degree of temperature, +therefore, of the specific rotatory power of levulose is equal to +55.24 divided by 88, which is equal to 0.628. From these data it is +easy to calculate the specific rotatory power of levulose for any +given temperature. For instance, let it be required to determine the +<span class="pagenum"><a id="Page_272"></a>[Pg 272]</span> +gyrodynat of levulose at a temperature of 20°. It will be found equal +to 108.24 - 0.628 × 20 = 95.68. The required rotatory power is then +[<i>a</i>]²⁰ °<span class="fs_80"><sub>D</sub></span> = -95°.68.</p> + +<p>In these calculations the influence of the presence of hydrochloric +acid upon the rotatory power of the levulose is neglected.</p> + +<p>Since the variation in angular rotation in the mixture at different +temperatures is due almost wholly to the change in this property of the +levulose it follows that the variation for each degree of temperature +and each per cent of levulose can be calculated. Careful experiments +have shown that the variation in the rotatory power of levulose between +0° and 88° is represented by a straight line. For 13.71 grams per +100 cubic centimeters the variation for each degree of temperature +is equal to 43.37 ÷ 88 = 0.49 divisions on the cane sugar scale, or +15.15 ÷ 88 = 0°.1722 angular measure. If 13.71 grams of levulose in +100 cubic centimeters produce the deviations mentioned for each degree +of temperature, one gram would give the deviation obtained by the +following calculations:</p> + +<p>For the cane sugar scale 0.49 ÷ 13.71 = 0°.0357 and for angular +rotation 0.1722 ÷ 13.71 = 0.01256.</p> + +<p>The above data afford a simple formula for calculating the percentage +of levulose present from the variation observed in polarizing a +solution containing levulose, provided that the quantity of levulose +present is approximately fourteen grams per 100 cubic centimeters.</p> + +<p class="blockquot"><i>Example.</i>—Suppose in a given case the +difference of reading between a solution containing an unknown quantity +of levulose at 0° and 88° is equal to thirty divisions of the cane +sugar scale. What weight of levulose is present? We have already seen +that one gram in 100 cubic centimeters produces a variation of 0.0357 +division for 1°. For 88° this would amount to 3.1416 divisions. The +total weight of levulose present is therefore 30 ÷ 3.1416 = 9.549 +grams. In the case given 26.048 grams of honey were taken for the +examination. The percentage of levulose was therefore 9.549 × 100 ÷ +26.048 = 36.66 per cent.</p> + +<p>If it be inconvenient to determine the polarimetric observations at +<span class="pagenum"><a id="Page_273"></a>[Pg 273]</span> +temperatures so widely separated as 0° and 88° the interval may be +made less. In the above case if the readings had been made at 20° and +70° the total variation would have been only ⁵⁰/⁸⁸ of the one given, +<i>viz.</i>, 17.05 divisions of the cane sugar scale. The calculation +would then have proceeded as follows:</p> + +<p class="f105">0.0357 × 50 = 1.785.</p> + +<p>Then, 17.05 ÷ 1.785 = 9.552 grams of levulose, from which the actual +percentage of levulose can be calculated as above.</p> + +<p>With honeys the operation is to be conducted as follows:</p> + +<p>Since honeys contain approximately twenty per cent of water and in the +dry substance have approximately forty-five per cent of levulose, about +38.50 grams of the honey should be taken to get approximately 13.8 +grams of levulose.</p> + +<p>In the actual determination the calculations may be based on +the factors above noted, but without respect to the degree of +concentration. If half the quantity of dextrose noted be present its +specific rotatory power is only reduced to about 52°.75, and this will +make but little difference in the results. In the case of honey 13.024 +grams of the sample are conveniently used in the examination, half the +normal weight for the ventzke sugar scale. The error, however, due to +difference in concentration is quite compensated for by the ease of +clarification and manipulation. Alumina cream alone is used in the +clarification, thus avoiding the danger of heating the solution to a +high temperature in the presence of an excess of lead acetate.</p> + +<p>An interesting fact is observed in cooling solutions of honey to +0°. The maximum left hand rotation is not reached as soon as the +temperature reaches 0° but only after it has been kept at that +temperature for two or three hours. The line representing the change in +rotatory power in solutions of honey between 10° and 88° is practically +straight but from 10° to 0°, if measured by the readings taken without +delay, it is decidedly curved; the reading being less at first than +it is afterwards. After three hours the 0° becomes sensibly constant +and then the whole line is nearly straight, but still with a slight +deficiency in the reading at the 0°. For this reason the computations +should be based on readings between 10° and 88° rather than on a number +<span class="pagenum"><a id="Page_274"></a>[Pg 274]</span> +covering the whole range of temperature. Nevertheless, if the solution +be kept at 10° for three hours before the final reading is taken, no +error of any practical magnitude is introduced.</p> + +<p>The calculations given above, for the cane sugar scale, can also be +made in an exactly similar manner for angular rotation. The angular +variation produced by one gram of levulose for 1° of temperature +is 0°.01256. For 88° this would become 1°.10528. Suppose the total +observed angular deviation in a given case between 0° and 88° to be +10°.404, then the weight of levulose present is 10.404 ÷ 1.10528 = 9.413 grams.</p> + +<p>In the case mentioned 26.048 grams of honey were taken for the +examination. The percentage of levulose present, therefore, was +9.413 × 100 ÷ 26.048 = 36.13.</p> + +<p><b>241. General Formula for the Calculation of Percentage of +Levulose.</b>—Let <i>K</i> = deviation in divisions of the cane sugar +scale or in angular rotation produced by one gram of levulose for 1° +temperature.</p> + +<div class="blockquot"> +<p>Let <i>T</i> and <i>tʹ</i> = temperatures at which observations are made.</p> + +<p>Let <i>R</i> = observed deviation in rotation.</p> + +<p>Let <i>W</i> = weight of levulose obtained.</p> + +<p>Let <i>L</i> = per cent of levulose required.</p> +</div> + +<table class="spb1 fs_105"> + <tbody><tr> + <td class="tdl" rowspan="2">Then <i>L</i> = </td> + <td class="tdc bb"><i>R</i></td> + <td class="tdl_wsp" rowspan="2">÷ <i>W</i>.</td> + </tr><tr> + <td class="tdc"><i>K</i>(<i>T</i> - <i>tʹ</i>)</td> + </tr> + </tbody> +</table> + +<p>In most genuine honeys the value of <i>R</i> between 0° and 88° is +approximately thirty divisions of the cane sugar scale or 10° angular +measure for 26.048 grams in 100 cubic centimeters, read in a 200 +millimeter tube, or, for 13.024 grams in 100 cubic centimeters read in +a 400 millimeter tube.</p> + +<p>The method of analysis outlined above has been applied in the +examination of a large number of honeys with most satisfactory results. +It can also be applied with equal facility to other substances +containing levulose.</p> + +<p><b>242. Sucrose and Dextrose.</b>—In mixtures these two sugars are +easily determined by optical processes, provided no other bodies +sensibly affecting the plane of polarized light be present. The total +<span class="pagenum"><a id="Page_275"></a>[Pg 275]</span> +deviation due to both sugars is determined in the usual way. The +percentage of sucrose is afterwards found by the inversion method +(<b><a href="#P_92">92</a></b>). The rotation, in the first instance due to the sucrose, +is calculated from the amount of this body found by inversion, and +the residual rotation is caused by the dextrose. The percentage of +dextrose is easily calculated by a simple proportion into which the +numbers expressing the gyrodynats of sucrose and dextrose enter. When +the readings are made on a ventzke scale the calculations are made as +follows:</p> + +<table class="spb1"> + <tbody><tr> + <td class="tdl">Weight of sample used</td> + <td class="tdr">26.048</td> + <td class="tdl_top" rowspan="6"> grams.</td> + </tr><tr> + <td class="tdl">First polarization</td> + <td class="tdr_wsp">88°.5</td> + </tr><tr> + <td class="tdl">Polarization after inversion </td> + <td class="tdr_wsp">10°.5</td> + </tr><tr> + <td class="tdl">Temperature</td> + <td class="tdr_wsp">20°.0</td> + </tr><tr> + <td class="tdl">Percentage of sucrose</td> + <td class="tdr_wsp">58.4</td> + </tr><tr> + <td class="tdl">Rotation due to dextrose</td> + <td class="tdr_wsp">30°.1</td> + </tr> + </tbody> +</table> + +<p>Percentage of dextrose:</p> + +<p class="f105">66.5 : 53 = <i>x</i> : 30.1; whence <i>x</i> = 37.8.</p> + +<p>The sample examined therefore contains 58.4 per cent of sucrose and +37.8 per cent of dextrose.</p> + +<p>It is evident that the method just described is also applicable when +maltose, dextrin, or any other sugar or polarizing body, not sensibly +affected by the process of inversion to which the sucrose is subjected, +is substituted for dextrose. When, however, more than two optically +active bodies are present the purely polariscopic process is not +applicable. In such cases the chemical or the combined chemical and +optical methods described further on can be employed.</p> + +<p id="P_243"><b>243. Lactose in Milk.</b>—By reason of its definite gyrodynat +lactose in milk is quickly and accurately determined by optical +methods, when proper clarifying reagents are used to free the fluid +of fat and nitrogenous substances. Soluble albuminoids have definite +levogyratory powers and, if not entirely removed, serve to diminish the +rotation due to the lactose.</p> + +<p>Milk casein precipitated by magnesium sulfate has the following +gyrodynatic numbers assigned to it:<a id="FNanchor_199" href="#Footnote_199" class="fnanchor">[199]</a></p> + +<table class="spb1"> + <tbody><tr> + <td class="tdl">Dissolved</td> + <td class="tdr"> in </td> + <td class="tdl_wsp">water [<i>a</i>]<span class="fs_80"><sub>D</sub></span> = -80°</td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdc">”</td> + <td class="tdl_wsp">very dilute solution [<i>a</i>]<span class="fs_80"><sub>D</sub></span> = -87°.</td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdc">”</td> + <td class="tdl_wsp">dilute sodium hydroxid solution [<i>a</i>]<span class="fs_80"><sub>D</sub></span> = -76°.</td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdc">”</td> + <td class="tdl_wsp">strong potassium hydroxid solution [<i>a</i>]<span class="fs_80"><sub>D</sub></span> = -91°.</td> + </tr> + </tbody> +</table> + +<p><span class="pagenum"><a id="Page_276"></a>[Pg 276]</span> +The hydrates of albumen have rotation powers which vary from +[<i>a</i>]<sub>D</sub> = -71°.40 to [<i>a</i>]<sub>D</sub> = -79°-05. From the chaotic +state of knowledge concerning the specific rotating power of the +various albumens, it is impossible to assign any number which will +bear the test of criticism. For the present, however, this number may +be fixed at [<i>a</i>]<span class="fs_80"><sub>D</sub></span> = -70° for the albumens which remain in +solution in the liquids polarized for milk sugar.<a id="FNanchor_200" href="#Footnote_200" class="fnanchor">[200]</a></p> + +<p>Many reagents have been prepared for the removal of the disturbing +bodies from milk in order to make its polarization possible. Among +the precipitants which have been used in this laboratory may be +mentioned:<a id="FNanchor_201" href="#Footnote_201" class="fnanchor">[201]</a></p> + +<div class="blockquot"> +<p>(1) Saturated solution basic lead acetate, specific gravity 1.97:</p> + +<p>(2) Nitric acid solution of mercuric nitrate diluted with an equal +volume of water: (<b><a href="#P_88">88</a>.</b>)</p> + +<p>(3) Acetic acid, specific gravity 1.040, containing twenty-nine per +cent acetic acid:</p> + +<p>(4) Nitric acid, specific gravity 1.197, containing thirty per cent +nitric acid:</p> + +<p>(5) Sulfuric acid, specific gravity 1.255, containing thirty-one per +cent sulfuric acid:</p> + +<p>(6) Saturated solution of sodium chlorid:</p> + +<p>(7) Saturated solution of magnesium sulfate:</p> + +<p>(8) Solution of mercuric iodid in acetic acid, formula; potassium +iodid, 33.2 grams; mercuric chlorid, 13.5 grams; strong acetic acid, +20.0 cubic centimeters; water 640 cubic centimeters.</p> +</div> + +<p>Alcohol, ether, and many solutions of mineral salts, hydrochloric and +other acids are also used as precipitants for albumen, but none of them +presents any advantages.</p> + +<p>Experience has shown that the best results in polariscopic work are +secured by the use of either the mercuric iodid or the acid mercuric +nitrate for clarifying the milk. The latter reagent should be used +in quantities of about three cubic centimeters for each 100 of milk. +It is evident when it is desired to determine the residual nitrogen +in solution, the former reagent must be employed. The quantity of +albuminoid matter left in solution after clarification with mercurial +salts is so minute as to exert no sensible effect on the rotation of +the plane of polarized light produced by the lactose. +<span class="pagenum"><a id="Page_277"></a>[Pg 277]</span></p> + +<p>For purposes of calculation the gyrodynat of lactose in the ordinary +conditions of temperature and concentration may be represented by +[<i>a</i>]<span class="fs_80"><sub>D</sub></span> = 52°.5 +(<b><a href="#P_107">107</a></b>).</p> + +<p><i>Polarization.</i>—The proper weight of milk is placed in a sugar +flask, diluted with water, clarified with the mercuric salt, the volume +completed to the mark, and the contents shaken and poured on a filter. +The filtrate is polarized in tubes of convenient length. The observed +rotation may be expressed either in degrees of angular measurement or +of the sugar scale. The weight of milk used may be two or three times +that of the normal weight calculated for the instrument employed. +Instead of weighing the milk a corresponding volume determined by its +specific gravity may be delivered from a burette-pipette (<a href="#Page_231">p. 231</a>). +For the laurent polariscope three times, and for the half-shadow +instruments for lamplight, twice the normal weight of milk should be +used. For approximately sixty cubic centimeters of milk the flask +should be marked at 105 cubic centimeters in compensation for the +volume of precipitated solids or the reading obtained from a 100 cubic +centimeter flask, decreased by one-twentieth.</p> + +<p>For the laurent instrument the normal weight of lactose is determined +by the following proportions:</p> + +<p>Gyrodynat of sucrose, 66.5: lactose: 52.5 = <i>x</i>: 16.19.</p> + +<p>Whence <i>x</i> = 20.51, that is, the number of grams of pure lactose +in 100 cubic centimeters required to read 100 divisions of the sugar +scale of the instrument.</p> + +<p>For the ventzke scale the normal quantity of lactose required to read +100 divisions is found from the following equation:</p> + +<div class="blockquot"> +<p class="f105">66.4 : 52.5 = <i>x</i> : 26.048</p> + +<p>Whence <span class="fs_105"><i>x</i> = 32.74.</span></p> +</div> + +<p>In the one case three times the normal weight of milk is 61.53 and in +the other twice the normal weight, 65.48 grams.</p> + +<p id="P_244"><b>244. Error due to Volume of Precipitate.</b>—Vieth states that the +volume allowed for the precipitated solids in the original process, +<i>viz.</i>, two and four-tenths cubic centimeters, is not sufficiently +large.<a id="FNanchor_202" href="#Footnote_202" class="fnanchor">[202]</a> +In such cases it is quite difficult to decide on any arbitrary +correction based on the supposed quantities of fat and +<span class="pagenum"><a id="Page_278"></a>[Pg 278]</span> +albuminoids present. A better method than to try to compensate for +any arbitrary volume is to remove entirely the disturbing cause or +eliminate it by indirect means. To wash the precipitate free of sugar +without increasing the bulk of the filtrate unduly would be extremely +difficult and tend, moreover, to bring some of the precipitated matters +again into solution. It is better, therefore, to eliminate the error +by double dilution and polarization (<b><a href="#P_86">86</a></b>). The principle of this +method is based on the fact, that, within limits not sensibly affecting +the gyrodynat by reason of different densities, the polarizations of +two solutions of the same substance are inversely proportional to their +volumes.</p> + +<p>For convenience, it is recommended that the volumes of the samples in +each instance be 100 and 200 cubic centimeters, respectively, in which +case the true reading is obtained by the simple formula given in the +latter part of <b><a href="#P_86">86</a></b>.</p> + +<p>In this laboratory the double dilution method of determining the volume +of the precipitate is conducted as follows:<a id="FNanchor_203" href="#Footnote_203" class="fnanchor">[203]</a></p> + +<p>In each of two flasks marked at 100 and 200 cubic centimeters, +respectively, are placed 65.52 grams of milk, four cubic centimeters +of mercuric nitrate added, the volume completed to the mark and the +contents of the flask well shaken.</p> + +<p>After filtering, the polarization is made in a 400 millimeter tube +by means of the triple shadow polariscope described in <b><a href="#P_75">75</a></b>. +From the reading thus obtained the volume of the precipitate and the +degree of correction to be applied are calculated as in the subjoined +example. The flasks should be filled at near the temperature at which +the polarizations are made and the observation room must be kept at +practically a constant temperature of 20° to avoid the complications +which would be produced by changes in the gyrodynat of lactose and +the value of the quartz plates and wedges of the apparatus by marked +variations in temperature.</p> + +<p><i>Example.</i>—Weight of milk used in each case 65.52 grams.</p> + +<table class="spb1"> + <tbody><tr> + <td class="tdl">Polarimetric</td> + <td class="tdl_wsp">reading</td> + <td class="tdl_wsp">from</td> + <td class="tdl_wsp">the</td> + <td class="tdl_wsp">100</td> + <td class="tdl_wsp">cubic</td> + <td class="tdl_wsp">centimeter</td> + <td class="tdl_wsp">flask,</td> + <td class="tdl_wsp">20°.84</td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdc">”</td> + <td class="tdc">”</td> + <td class="tdc">”</td> + <td class="tdl_wsp">200</td> + <td class="tdc">”</td> + <td class="tdc">”</td> + <td class="tdc">”</td> + <td class="tdl_wsp">10°.15</td> + </tr> + </tbody> +</table> + +<ul class="index"> +<li class="isub2">Then 10.15 × 2 = 20.30</li> +<li class="isub5">20.84 - 20.30 = 0.54</li> +<li class="isub5">0.54 × 2 = 1.08</li> +<li class="isub5">20.84 - 1.08 = 19.76</li> +<li class="isub5">19.76 ÷ 4 = 4.94,</li> +</ul> + +<p class="no-indent"><span class="pagenum"><a id="Page_279"></a>[Pg 279]</span> +which is the corrected reading showing the percentage of lactose in the +sample used.</p> + +<p>The volume of the precipitate is calculated as follows:</p> + +<p>20.84 ÷ 4 = 5.21, the apparent percentage of lactose present.</p> + +<p>Then 5.21 : 4.94 = 100 : <i>x</i>.</p> + +<p>Whence <i>x</i> = 94.82. From this number it is seen that the true +volume of the milk solution polarized is 94.82 instead of 100 cubic +centimeters, whence the volume occupied by the precipitate is 100 - +94.82 = 5.18 cubic centimeters. So little time is required to conduct +the analysis by the double dilution method as to render it preferable +in all cases where incontestable data are desired. Where arbitrary +corrections are made the volume allowed for the precipitate may vary +from two and a half cubic centimeters in milks poor in fat, to six for +those with a high cream content.</p> + +<p>For milks of average composition sufficient accuracy is secured by +making an arbitrary correction of five cubic centimeters for the volume +of the precipitate.</p> + +<h3>SEPARATION OF SUGARS BY CHEMICAL<br> AND CHEMICAL-OPTICAL METHODS.</h3> + +<p><b>245. Conditions of Separation.</b>—In the foregoing paragraphs the +optical methods for determining certain sugars have been described. +Many cases arise, however, in which these processes are inapplicable or +insufficient. In these instances, the analyst, as a rule, will be able +to solve the problem presented by the purely chemical methods which +have been previously described, or by a combination of the chemical +and optical processes. Not only have the different sugars distinctive +relations to polarized light, but also they are oxidized by varying +quantities of metallic salts and these differences are sufficiently +pronounced to secure in nearly every instance, no matter how complex, +data of a high degree of accuracy.</p> + +<p>The carbohydrates of chief importance, from an agricultural point of +view, are starch and sucrose; while the alternation products of chief +importance, derived therefrom by chemical and biological means, are +dextrin, maltose, dextrose and invert sugar. +<span class="pagenum"><a id="Page_280"></a>[Pg 280]</span></p> + +<p><b>246. Sucrose, Levulose, and Dextrose.</b>—The purely chemical +methods of separating these three sugars have been investigated by +Wiechmann.<a id="FNanchor_204" href="#Footnote_204" class="fnanchor">[204]</a> +They are based on the data obtained by determining the percentage of +reducing sugars, both before and after the inversion of the sucrose, +and before and after the removal of the levulose. For the destruction +of the levulose, the method of Sieben is employed, and attention is +called to the fact that the complete removal of the levulose by this +process is difficult of accomplishment, and is probably attended with +alterations of the other sugars present.</p> + +<p><b>247. Sieben’s Method of Determining Levulose.</b>—The decomposing +action of hot hydrochloric acid on levulose, and its comparative +inaction on dextrose are the basis of Sieben’s process.<a id="FNanchor_205" href="#Footnote_205" class="fnanchor">[205]</a> +The hydrochloric acid employed should contain about 220 grams of the +pure gas per liter, that is, be of twenty-two per cent strength, +corresponding to 1.108 specific gravity. If the substance acted on be +invert sugar, its solution should be approximately of two and a half +per cent strength. To 100 cubic centimeters of such a solution, sixty +of the hydrochloric acid are added, and the mixture immersed in boiling +water for three hours.</p> + +<p>After quickly cooling, the acid is neutralized with sodium hydrate of +thirty-six times normal strength. Ten cubic centimeters of the hydrate +solution will thus neutralize the sixty of hydrochloric acid which have +been used to destroy the levulose. The work of Wiechmann discloses the +fact, easily prevised, that the method used for destroying levulose is +not always effective and that action of the reagent is not exclusively +confined to the levogyrate constituent of the mixture. Nevertheless, +data of reasonable accuracy may be secured by this process, which is +best carried out as described by Wiechmann. In this connection the +possibility of the polymerization of the dextrose molecules, when +heated with hydrochloric acid, must not be overlooked.</p> + +<p><b>248. The Analytical Process.</b>—The total quantity of invert sugar +in a given solution is determined by the methods already given +(<b><a href="#P_136">136</a>, <a href="#P_141">141</a></b>.) +<span class="pagenum"><a id="Page_281"></a>[Pg 281]</span></p> + +<p>After this has been accomplished, the levulose is destroyed as +described above, and the dextrose determined by any approved method +(<b><a href="#P_136">136</a>, <a href="#P_140">140</a></b>). In the presence +of sucrose, the sum of the reducing sugars is first determined as in +<b><a href="#P_136">136</a>, <a href="#P_142">142</a></b>. After the inversion +of the sucrose, the invert sugar is again determined, and the increased +quantity found, calculated to sucrose. The levulose is then destroyed +by hydrochloric acid, and the dextrose determined as described above. +The quantity of sucrose may also be determined by an optical method +(<b><a href="#P_91">91</a>, <a href="#P_92">92</a>, <a href="#P_94">94</a></b>.).</p> + +<p><b>249. Calculation of Results.</b>—If we represent by a the weight +of metallic copper reduced by the invert sugar present in a solution +containing sucrose, and by <i>b</i> that obtained after the inversion +of the sucrose, the quantity of copper corresponding to the sucrose is +<i>b - a</i> = <i>c</i>. After the destruction of the levulose, the +copper reduced by the residual dextrose may be represented by <i>d</i>. +The weight of copper equivalent to the levulose is, therefore, <i>b +- d</i> = <i>e</i>. From the tables already given, the corresponding +quantities of the sugars equivalent to <i>c, d</i>, and <i>e</i> are +directly taken. Example:</p> + +<table class="spb1"> + <tbody><tr> + <td class="tdl" rowspan="3"><i>a</i> =</td> + <td class="tdl_wsp" rowspan="3">300</td> + <td class="tdl_wsp" rowspan="3">milligrams</td> + <td class="tdc" rowspan="3"> = </td> + <td class="tdc" rowspan="3"><img src="images/cbl-3.jpg" alt="" width="16" height="57" ></td> + <td class="tdl_wsp">163.8</td> + <td class="tdl_wsp">milligrams</td> + <td class="tdl_wsp">invert sugar.</td> + </tr><tr> + <td class="tdl_wsp">156.5</td> + <td class="tdc">”</td> + <td class="tdl_wsp">dextrose.</td> + </tr><tr> + <td class="tdl_wsp">185.63</td> + <td class="tdc">”</td> + <td class="tdl_wsp">levulose.</td> + </tr><tr> + <td class="tdl"><i>b</i> =</td> + <td class="tdl_wsp">500</td> + <td class="tdc">”</td> + <td class="tdc" colspan="5"> </td> + </tr><tr> + <td class="tdl"><i>d</i> =</td> + <td class="tdl_wsp">275</td> + <td class="tdc">”</td> + <td class="tdc">=</td> + <td class="tdc"> </td> + <td class="tdl_wsp">142.8</td> + <td class="tdc">”</td> + <td class="tdl_wsp">dextrose.</td> + </tr><tr> + <td class="tdl"><i>c</i> =</td> + <td class="tdl_wsp">200</td> + <td class="tdc">”</td> + <td class="tdc">=</td> + <td class="tdc"> </td> + <td class="tdl_wsp">106.3</td> + <td class="tdc">”</td> + <td class="tdl_wsp">invert sugar.</td> + </tr><tr> + <td class="tdl"><i>e</i> =</td> + <td class="tdl_wsp">225</td> + <td class="tdc">”</td> + <td class="tdc">=</td> + <td class="tdc"> </td> + <td class="tdl_wsp">133.89</td> + <td class="tdc">”</td> + <td class="tdl_wsp">levulose.</td> + </tr> + </tbody> +</table> + +<p>The 106.3 milligrams of invert sugar equivalent to <i>c</i>, correspond +to 101 milligrams of sucrose. The quantity of dextrose equivalent to +275 milligrams of copper is 142.8. Of this amount 53.15 milligrams are +due to the inverted sucrose, leaving 89.65 milligrams arising from +the invert sugar and dextrose originally present. This quantity is +equivalent to 175 milligrams of copper.</p> + +<p>Of the 300 milligrams of copper obtained in the first instance, 125 +are due to levulose in the original sample, corresponding to 69.73 +milligrams which number, multiplied by two, gives the invert sugar +present.</p> +<p><span class="pagenum"><a id="Page_282"></a>[Pg 282]</span></p> +<p>The sample examined, therefore, had the following composition:</p> + +<table class="spb1"> + <tbody><tr> + <td class="tdl">Sucrose</td> + <td class="tdr">101.00</td> + <td class="tdl_wsp">milligrams.</td> + </tr><tr> + <td class="tdl">Invert sugar  </td> + <td class="tdr">139.46</td> + <td class="tdc">”</td> + </tr><tr> + <td class="tdl">Dextrose</td> + <td class="tdr bb">19.92</td> + <td class="tdc">”</td> + </tr><tr> + <td class="tdl_ws1">Sum</td> + <td class="tdr">260.38</td> + <td class="tdc">”</td> + </tr> + </tbody> +</table> + +<p>On the other hand, if the invert sugar be calculated from the quantity +corresponding to the 225 milligrams of copper corresponding to +<i>e</i>, the data will be very different from those given above. In +this instance of the levulose found corresponding to 225 milligrams +of copper, <i>viz.</i>, 133.89, 53.15 milligrams are due to the +inverted sucrose. Then the quantity due to the invert sugar at first +present is 133.89 - 53.15 = 80.74 milligrams. Since half the weight +of invert sugar is levulose, the total weight of the invert sugar at +first present is 161.48, leaving only 8.91 milligrams due to added +dextrose. The difficulties in these calculations doubtless arise from +the imperfect destruction of the levulose, and from variations in the +reducing action of sugars on copper salts in the presence of such large +quantities of sodium chlorid.</p> + +<p><b>250. Calculation from Data obtained with Copper Carbonate.</b>—The +wide variations observed in different methods of calculations in the +preceding paragraph, are due in part to the different degrees of +oxidation exerted on alkaline copper tartrate by the dextrose and +levulose. Better results are obtained by conducting the analytical work +with Ost’s modification of Soldaini’s solution (<b><a href="#P_128">128</a></b>).</p> + +<p>The relative quantities of levulose and dextrose oxidized by this +solution are almost identical, and the calculations, therefore, result +in nearly the same data, whether made from the numbers obtained with +the residual dextrose or from the levulose destroyed. The method of +applying this method is illustrated in the following calculation.</p> + +<p><i>Example.</i>—In a mixture of sucrose, invert sugar, and dextrose, +the quantities of copper obtained by using the copper carbonate +solution were as follows: +<span class="pagenum"><a id="Page_283"></a>[Pg 283]</span></p> + +<table class="spb1"> + <tbody><tr> + <td class="tdl">Copper</td> + <td class="tdl_wsp">obtained</td> + <td class="tdl_wsp">before</td> + <td class="tdl_wsp">inversion</td> + <td class="tdl_wsp">= <i>a</i> =</td> + <td class="tdl_wsp">150</td> + <td class="tdl_wsp">milligrams.</td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdc">”</td> + <td class="tdl_wsp">after</td> + <td class="tdl_ws2">”</td> + <td class="tdl_wsp">= <i>b</i> =</td> + <td class="tdl_wsp">250</td> + <td class="tdc">”</td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdc">”</td> + <td class="tdc">”</td> + <td class="tdl_wsp">destroying lev’e</td> + <td class="tdl_wsp">= <i>d</i> =</td> + <td class="tdl_wsp">137.5</td> + <td class="tdc">”</td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdl_wsp">equivalent</td> + <td class="tdc">to</td> + <td class="tdl_wsp">inverted sucrose</td> + <td class="tdl_wsp">= <i>b</i> - <i>a</i> = <i>c</i> =</td> + <td class="tdl_wsp">100</td> + <td class="tdc">”</td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdc">”</td> + <td class="tdc">”</td> + <td class="tdl_wsp">levulose</td> + <td class="tdl_wsp">= <i>b</i> - <i>d</i> = <i>e</i> =</td> + <td class="tdl_wsp">112.5</td> + <td class="tdc">”</td> + </tr> + </tbody> +</table> + +<table class="spb1"> + <tbody><tr> + <td class="tdl" rowspan="3"><i>a</i> =</td> + <td class="tdl_wsp" rowspan="3">150</td> + <td class="tdl_wsp" rowspan="3">milligrams</td> + <td class="tdl_wsp" rowspan="3">Cu</td> + <td class="tdl_wsp" rowspan="3">= </td> + <td class="tdc" rowspan="3"><img src="images/cbl-3.jpg" alt="" width="16" height="57" ></td> + <td class="tdl_wsp">44.0</td> + <td class="tdl_wsp">milligrams</td> + <td class="tdl_wsp">invert sugar</td> + </tr><tr> + <td class="tdl_wsp">45.3</td> + <td class="tdc">”</td> + <td class="tdl_wsp">dextrose</td> + </tr><tr> + <td class="tdl_wsp">42.5</td> + <td class="tdc">”</td> + <td class="tdl_wsp">levulose.</td> + </tr><tr> + <td class="tdl"><i>d</i> =</td> + <td class="tdl_wsp">137.5</td> + <td class="tdc">”</td> + <td class="tdc">”</td> + <td class="tdl_wsp">= </td> + <td class="tdc"> </td> + <td class="tdl_wsp">41.55</td> + <td class="tdc">”</td> + <td class="tdl_wsp">dextrose.</td> + </tr><tr> + <td class="tdl"><i>c</i> =</td> + <td class="tdl_wsp">100</td> + <td class="tdc">”</td> + <td class="tdc">”</td> + <td class="tdl_wsp">= </td> + <td class="tdc"> </td> + <td class="tdl_wsp">29.5</td> + <td class="tdc">”</td> + <td class="tdl_wsp">invert sugar</td> + </tr><tr> + <td class="tdl" colspan="7"> </td> + <td class="tdr_wsp">= 28.025</td> + <td class="tdl_wsp">sucrose.</td> + </tr><tr> + <td class="tdl"><i>e</i> =</td> + <td class="tdl_wsp">112.5</td> + <td class="tdc">”</td> + <td class="tdc">”</td> + <td class="tdl_wsp">= </td> + <td class="tdc"> </td> + <td class="tdl_wsp">31.9</td> + <td class="tdc">”</td> + <td class="tdl_wsp">levulose.</td> + </tr> + </tbody> +</table> + +<table class="spb1"> + <tbody><tr> + <td class="tdl">14.75</td> + <td class="tdl_wsp">milligrams</td> + <td class="tdl_wsp">of</td> + <td class="tdl_wsp">dextrose =</td> + <td class="tdl_wsp">48.5</td> + <td class="tdl_wsp">milligrams</td> + <td class="tdl_wsp">Cu.</td> + </tr><tr> + <td class="tdl">14.75</td> + <td class="tdc">”</td> + <td class="tdc">”</td> + <td class="tdl_wsp">levulose =</td> + <td class="tdl_wsp">51.5</td> + <td class="tdc">”</td> + <td class="tdc">”</td> + </tr> + </tbody> +</table> + +<p>137.5 - 48.5 = 89.0 milligrams Cu due to dextrose present before inversion.</p> + + +<table class="spb1"> + <tbody><tr> + <td class="tdl" rowspan="3">150.0 -</td> + <td class="tdl_wsp">89.0</td> + <td class="tdl_wsp">milligrams</td> + <td class="tdl_wsp">Cu</td> + <td class="tdl_wsp">= 27</td> + <td class="tdl_wsp">milligrams</td> + <td class="tdl_wsp">dextrose before inversion.</td> + </tr><tr> + <td class="tdl_wsp">89.0</td> + <td class="tdc">”</td> + <td class="tdc">”</td> + <td class="tdl_wsp">= 61.0</td> + <td class="tdc">”</td> + <td class="tdl_wsp">Cu due to levulose present before inversion.</td> + </tr><tr> + <td class="tdl_wsp">61.0</td> + <td class="tdc">”</td> + <td class="tdc">”</td> + <td class="tdl_wsp">= 17.8</td> + <td class="tdc">”</td> + <td class="tdl_wsp">levulose before inversion.</td> + </tr> + </tbody> +</table> + +<table class="spb1"> + <tbody><tr> + <td class="tdr">17.8 × 2 =</td> + <td class="tdl_wsp">35.6</td> + <td class="tdl_wsp">milligrams</td> + <td class="tdl_wsp">invert sugar</td> + <td class="tdl_wsp">present</td> + <td class="tdl_wsp">before</td> + <td class="tdl_wsp">inversion.</td> + </tr><tr> + <td class="tdl">27.0 - 17.8 =</td> + <td class="tdl_wsp"> 9.2</td> + <td class="tdc">”</td> + <td class="tdl_wsp">dextrose</td> + <td class="tdc">”</td> + <td class="tdc">”</td> + <td class="tdc">”</td> + </tr> + </tbody> +</table> + +<p class="no-indent fs_105">Again:</p> + +<ul class="index"> +<li class="isub2">112.5 - 51.5 = 61.0 milligrams Cu due to levulose present before inversion.</li> +<li class="isub2">61.0 milligrams Cu = 17.8 milligrams levulose.</li> +<li class="isub2">17.8 ” levulose indicate 35.6 milligrams invert sugar.</li> +<li class="isub2">Dextrose in invert sugar before inversion = 17.8 milligrams.</li> +<li class="isub2">Total dextrose before inversion = 27.0 milligrams.</li> +<li class="isub2">Dextrose above amount required for invert sugar = 27.0 - 17.8= 9.2 milligrams.</li> +</ul> + +<p>The respective quantities of the three sugars in the solution are, +therefore:</p> + +<table class="spb1"> + <tbody><tr> + <td class="tdl">Sucrose</td> + <td class="tdl_wsp">= 28.025</td> + <td class="tdl_wsp">milligrams.</td> + </tr><tr> + <td class="tdl">Invert sugar </td> + <td class="tdl_wsp">= 35.6</td> + <td class="tdc">”</td> + </tr><tr> + <td class="tdl">Dextrose</td> + <td class="tdl_wsp">= 9.2</td> + <td class="tdc">”</td> + </tr> + </tbody> +</table> + +<p>The calculations made from the later data (<b><a href="#P_234">234</a></b>) +give almost the same results.</p> + +<p><b>251. Winter’s Process.</b>—Winter has proposed a method of +separating dextrose and levulose in the presence of sucrose based on +<span class="pagenum"><a id="Page_284"></a>[Pg 284]</span> +the selective precipitation produced on treating mixtures of these +sugars in solution with ammoniacal lead acetate.<a id="FNanchor_206" href="#Footnote_206" class="fnanchor">[206]</a></p> + +<p>The reagent is prepared immediately before use by adding ammonia to +a solution of lead acetate until the opalescence which is at first +produced just disappears. The separation is based on the fact that +the compound of sucrose with the reagent is easily soluble in water, +while the salts formed with levulose and dextrose are insoluble. The +separation of the sugars is accomplished as follows:</p> + +<p>The ammoniacal lead acetate is added to the solution of the mixed +sugars until no further precipitate is produced. The precipitated +matters are digested with a large excess of water and finally separated +by filtration. The sucrose is found in the filtrate in the form of a +soluble lead compound, from which it is liberated by treatment with +carbon dioxid. The lead carbonate produced is separated by filtration +and the sucrose is estimated in an aliquot part of the filtrate by +optical or chemical methods. The precipitate containing the lead +compounds of dextrose and levulose is washed free of sucrose, suspended +in water and saturated with carbon dioxid. By this treatment the lead +compound with dextrose is decomposed and, on filtration, the dextrose +will be found in the filtrate, while the lead compound of the levulose +is retained upon the filter with the lead carbonate. After well washing +the precipitate, it is again suspended in water and saturated with +hydrogen sulfid. By this treatment the lead levulosate compound is +broken up and the levulose obtained, on subsequent filtration, in +the filtrate. The dextrose and levulose, after separation as above +described, may be determined in aliquot parts of their respective +filtrates by the usual gravimetric methods. Before determining the +levulose the solution should be heated until all excess of hydrogen +sulfid is expelled.</p> + +<p>This method was used especially by Winter in separating the various +sugars obtained in the juices of sugar cane. It has not been largely +adopted as a laboratory method, and on account of the time and trouble +required for its conduct, is not likely to assume any very great +practical importance.</p> + +<p><b>252. Separation of Sugars by Lead Oxid.</b>—In addition to the +combination with the earthy bases, sugar forms well defined compounds +<span class="pagenum"><a id="Page_285"></a>[Pg 285]</span> +with lead oxid. One of these compounds is of such a nature as to have +considerable analytical and technical value. Its composition and the +method of preparing it have been pointed out by Kassner.<a id="FNanchor_207" href="#Footnote_207" class="fnanchor">[207]</a></p> + +<p>Sucrose, under conditions to be described, forms with the lead oxid +a diplumbic saccharate, which separates in spheroidal crystals, and +has the composition corresponding to the formula <b>C₁₂H₁₈O₁₁Pb₂ + 5H₂O</b>. +The precipitation takes place quantitively and should be conducted as +follows:</p> + +<p>The substance containing the sucrose, which may be molasses, sirups +or concentrated juices, is diluted with enough water to make a sirup +which is not too viscous. Lead oxid suspended in water is stirred into +the mass in such proportion as to give about two parts of oxid to one +of the sugar. The stirring is continued for some time until the oxid +is thoroughly distributed throughout the mass and until it becomes +thick by the commencement of the formation of the saccharate. As soon +as the mass is sufficiently thickened to prevent the remaining lead +oxid from settling, the stirring may be discontinued and the mixture +is left for twenty-four hours, at the end of which time the sucrose +has all crystallized in the form of lead saccharate. The crystals of +lead saccharate can be separated by a centrifugal machine or by passing +through a filter press, and are thoroughly washed with cold water, in +which they are almost insoluble. The washed crystals are beaten up with +water into a thick paste and the lead separated as basic carbonate by +carbon dioxid. The sucrose is found in solution in the residual liquor +and is concentrated and crystallized in the usual way.</p> + +<p>Reducing sugars have a stronger affinity for the lead oxid than the +sucrose, and this fact is made use of to effect a nearly complete +separation when they are mixed together. In order to secure this the +lead oxid is added in the first place only in sufficient quantity to +combine with the reducing sugars present, the process being essentially +that described above. The reducing sugars which are precipitated as +lead dextrosates, lead levulosates, etc., are separated in the usual +way by a centrifugal or a filter press, and the resulting liquor, +which contains still nearly all the sucrose, is subjected to a second +<span class="pagenum"><a id="Page_286"></a>[Pg 286]</span> +precipitation by the addition of lead oxid. The second precipitation +obtained is almost pure diplumbic saccharate.</p> + +<p>In the precipitation of the sugar which is contained in the beet +molasses, where only a trace or very little invert sugar is present, +the sucrose is almost quantitively separated, and by the concentration +of the residual liquor, potash salts are easily obtained. In this case, +after the decomposition of the lead saccharate by carbon dioxid, the +residual sugar solution is found entirely free of lead. Where invert +sugar is present, however, in any considerable proportions, it is found +to exercise a slightly soluble influence on the lead saccharate, and +in this case a trace of lead may pass into solution. For technical +purposes, this is afterwards separated by hydrosulfuric acid or the +introduction of lime sulfid.</p> + +<p>Lead oxid is regenerated from the basic lead carbonate obtained by +heating in retorts to a little above 260°, and the carbon dioxid +evolved can also be used again in the technical process.</p> + +<p><b>253. Commercial Glucose and Grape Sugar.</b>—The commercial +products obtained by the hydrolysis of starch are known in the trade +as glucose or grape sugar. The former term is applied to the thick +sirup obtained by concentrating the products of a partial hydrolysis, +while the latter is applied to the solid semi-crystalline mass, secured +by continuing the hydrolyzing action until the intermediate products +are almost completely changed to dextrose. In this country the starch +employed is obtained almost exclusively from maize, and the hydrolyzing +agent used is sulfuric acid.<a id="FNanchor_208" href="#Footnote_208" class="fnanchor">[208]</a> +The products of conversion in glucose are chiefly dextrins and dextrose +with some maltose, and in grape sugar almost entirely dextrose. +When diastase is substituted for an acid, as the hydrolytic agent, +maltose is the chief product, the ferment having no power of producing +dextrose. In the glucose of Japan, known as midzu ame dextrin and +maltose are the chief constituents.<a id="FNanchor_209" href="#Footnote_209" class="fnanchor">[209]</a></p> + +<p>Commercial glucose is used chiefly by confectioners for manufacturing +table sirups and for adulterating honey and molasses.</p> + +<p>Commercial grape sugar is chiefly employed by brewers as a substitute +for barley and other grains. +<span class="pagenum"><a id="Page_287"></a>[Pg 287]</span></p> + +<p>In Europe, the starch which is converted into glucose, is derived +principally from potatoes. The method employed in conversion, whether +an acid or diastatic action, is revealed not only by the nature of +the product, but also by the composition of its ash. In the case of +diastatic conversion the ash of the sample will contain only a trace of +sulfates, no chlorin, and be strongly alkaline, while the product of +conversion with sulfuric acid will give an ash rich in sulfates with a +little lime and be less strongly alkaline.</p> + +<p>The process of manufacture in this country consists in treating the +starch, beaten to a cream with water, with sulfuric acid, usually under +pressure, until the product shows no blue color with iodin. The excess +of acid is removed with marble dust, the sirup separated by filtration, +whitened by bleaching with sulfurous acid or by passing it through +bone-black and evaporated to the proper consistence in a vacuum. The +solid sugar, consisting mostly of dextrose, is made in the same manner, +save that the heating with the acid is continued until the dextrin and +maltose are changed into maltose. The product is either obtained in +its ordinary hydrated form or by a special method of crystallization +secured as bright anhydrous crystals. Solutions of dextrose, when first +made, show birotation, but attain their normal gyrodynatic state on +standing for twenty-four hours in the cold, or immediately on boiling.</p> + +<p><b>254. Methods Of Separation.</b>—The accurate determination of the +quantities of the several optically active bodies formed in commercial +glucose is not possible by any of the methods now known. Approximately +accurate data may be secured by a large number of processes, and these +are based chiefly on the ascertainment of the rotation and reducing +power of the mixed sugars, the subsequent removal of the dextrose and +maltose by fermentation or oxidation and the final polarization of the +residue. The difficulties which attend these processes are alike in +all cases. Fermentation may not entirely remove the reducing sugars or +may act slightly on the dextrin. In like manner the oxidation of these +sugars by metallic salts may not entirely decompose them, may leave an +optically active residue, or may affect the optical activity of the +<span class="pagenum"><a id="Page_288"></a>[Pg 288]</span> +residual dextrin. The quantitive methods of separating these sugars +by means of phenylhydrazin, lead salts or earthy bases have not been +developed into reliable and applicable laboratory processes. At the +present time the analyst must be contented with processes confessedly +imperfect, but which, with proper precautions, yield data which are +nearly correct. The leading methods depending on fermentation and +oxidation combined with polarimetric observations will be described in +the subjoined paragraphs.</p> + +<p><b>255. Fermentation Method.</b>—This process is based on the +assumption that, under certain conditions, dextrose and maltose may +be removed from a solution and the dextrin be left unchanged. In +practice, approximately accurate results are obtained by this method, +although the assumed conditions are not strictly realized. In the +prosecution of this method the polarimetric reading of the mixed sugars +is made, and the maltose and dextrose removed therefrom by fermentation +with compressed yeast. The residual dextrins are determined by the +polariscope on the assumption that their average gyrodynat is 193. +In the calculation of the quantities of dextrose and maltose their +gyrodynats are fixed at 53 and 138 respectively. The total quantity +of reducing sugar is determined by the usual processes. The relative +reducing powers of dextrose and maltose are represented by 100 and 62 +respectively. The calculations are made by the following formulas:<a id="FNanchor_210" href="#Footnote_210" class="fnanchor">[210]</a></p> + +<ul class="index"> +<li class="isub2"><i>R</i> = reducing sugars as dextrose</li> +<li class="isub2"><i>d</i> = dextrose</li> +<li class="isub2"><i>m</i> = maltose</li> +<li class="isub2"><i>dʹ</i> = dextrin</li> +<li class="isub2"><i>P</i> = total polarization (calculated as apparent gyrodynat)</li> +<li class="isub2"><i>Pʹ</i> = rotation after fermentation (calculated as apparent gyrodynat).</li> +</ul> + +<table class="spb1"> + <tbody><tr> + <td class="tdl_top" rowspan="3">Whence </td> + <td class="tdl"><i>R</i></td> + <td class="tdl_wsp">= <i>d</i> + 0.62<i>m</i></td> + <td class="tdr">(1)</td> + </tr><tr> + <td class="tdl"><i>P</i></td> + <td class="tdl_wsp">= 53<i>d</i> + 138<i>m</i> + 163<i>dʹ</i><span class="ws2"> </span></td> + <td class="tdr">(2)</td> + </tr><tr> + <td class="tdl"><i>Pʹ</i></td> + <td class="tdl_wsp">= 193<i>dʹ</i></td> + <td class="tdr">(3)</td> + </tr> + </tbody> +</table> + +<p>From these three equations the values of <i>d</i>, <i>m</i>, and +<i>dʹ</i> are readily calculated: +<span class="pagenum"><a id="Page_289"></a>[Pg 289]</span></p> + +<p class="fs_105 spa1"><i>Example</i>: To find <i>d</i> and <i>m</i>:</p> + +<table class="spb1 fs_105"> + <tbody><tr> + <td class="tdr_top" rowspan="3">Subtract (3) from (2) </td> + <td class="tdr"><i>P</i> =</td> + <td class="tdl_wsp">53<i>d</i> + 133<i>m</i> + 193<i>dʹ</i></td> + <td class="tdr"> </td> + </tr><tr> + <td class="tdr bb"><i>Pʹ</i> =</td> + <td class="tdl_wsp bb"><span class="ws6">193<i>dʹ</i></span></td> + <td class="tdr"> </td> + </tr><tr> + <td class="tdl"><i>P</i> - <i>Pʹ</i> =</td> + <td class="tdl_wsp">53<i>d</i> + 138<i>m</i></td> + <td class="tdr">  (4)</td> + </tr><tr> + <td class="tdl" colspan="4"> </td> + </tr><tr> + <td class="tdl_top" rowspan="3">Multiply (1) by 53 and subtract from (4) </td> + <td class="tdr"><i>P</i> - <i>Pʹ</i> =</td> + <td class="tdl_wsp">53<i>d</i> + 138<i>m</i></td> + <td class="tdr"> </td> + </tr><tr> + <td class="tdr bb">53<i>R</i> =</td> + <td class="tdl_wsp bb">53<i>d</i> + 32.86<i>m</i></td> + <td class="tdr"> </td> + </tr><tr> + <td class="tdl"><i>P</i> - <i>Pʹ</i> -</td> + <td class="tdl_wsp">53<i>R</i> = 105.14<i>m</i></td> + <td class="tdr">  (5)</td> + </tr><tr> + <td class="tdl" colspan="4"> </td> + </tr><tr> + <td class="tdr_top" rowspan="2">Whence <i>m</i> = </td> + <td class="tdl bb"><i>P</i> - <i>Pʹ</i> - 53<i>R</i></td> + <td class="tdl"> </td> + <td class="tdl" rowspan="2"><span class="ws2">(6)</span></td> + </tr><tr> + <td class="tdc">105.14</td> + <td class="tdl"> </td> + </tr> + </tbody> +</table> + +<p class="f105"><i>d</i> = <i>R</i> - 0.62<i>m</i><span class="ws5">(7)</span></p> + +<table class="spb1 fs_105"> + <tbody><tr> + <td class="tdl" rowspan="2"><i>dʹ</i> = </td> + <td class="tdc bb"><i>Pʹ</i></td> + <td class="tdl" rowspan="2"><span class="ws7">(8)</span></td> + </tr><tr> + <td class="tdc">193</td> + </tr> + </tbody> +</table> + +<p>Sidersky assigns the values [<i>a</i>]<span class="fs_80"><sub>D</sub></span> += 138.3 and [<i>a</i>]<span class="fs_80"><sub>D</sub></span> = 194.8 to maltose +and dextrin respectively in the above formulas.<a id="FNanchor_211" href="#Footnote_211" class="fnanchor">[211]</a></p> + +<p><i>Illustration</i>: In the examination of a sample 26.048 grams of +midzu ame in 100 cubic centimeters were polarized in a 200 millimeter +tube and the following data were obtained:</p> + +<p>Polarization of sample in angular degrees 69°.06, which is equal to an +apparent gyrodynat of 132.6:</p> + +<p>Total reducing sugar as dextrose 33.33 per cent:</p> + +<p>Polarization in angular degrees after fermentation 30°.84 = +[<i>a</i>]<span class="fs_80"><sub>D</sub></span> = 59.2.</p> + +<p>Substituting these values in the several equations gives the following +numbers:</p> + +<ul class="index"> +<li class="isub2">(1)   0.3333 = <i>d</i> + 0.62<i>m</i></li> +<li class="isub2">(2)  132.6 = 53<i>d</i> + 138<i>m</i> + 193<i>dʹ</i></li> +<li class="isub2">(3)   59.2 = 193<i>dʹ</i></li> +<li class="isub2">(4)   73.4 = 53<i>d</i> + 138<i>m</i></li> +<li class="isub2">(5)   55.74 = 105.14<i>m</i></li> +<li class="isub2">(6) <i>m</i> = 0.5301 = 53.01 per cent.</li> +<li class="isub2">(7) <i>d</i> = 3333 - 3286 = 0.0047 = 00.47 per cent.</li> +<li class="isub2">(8) <i>dʹ</i> = 59.2 ÷ 193 = 0.3067 = 30.67 ” ”</li> +</ul> + +<p><span class="pagenum"><a id="Page_290"></a>[Pg 290]</span> +<i>Summary</i>: Sample of midzu ame:</p> + +<table class="spb1"> + <tbody><tr> + <td class="tdl">Percentage</td> + <td class="tdl_wsp">of</td> + <td class="tdl_wsp">dextrin</td> + <td class="tdr">30.67</td> + <td class="tdl_wsp">per</td> + <td class="tdl_wsp">cent.</td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdc">”</td> + <td class="tdl_wsp">maltose</td> + <td class="tdr">53.01</td> + <td class="tdc">”</td> + <td class="tdc">”</td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdc">”</td> + <td class="tdl_wsp">dextrose</td> + <td class="tdr">00.47</td> + <td class="tdc">”</td> + <td class="tdc">”</td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdc">”</td> + <td class="tdl_wsp">water</td> + <td class="tdr">14.61</td> + <td class="tdc">”</td> + <td class="tdc">”</td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdc">”</td> + <td class="tdl_wsp">ash</td> + <td class="tdr bb">00.31</td> + <td class="tdc">”</td> + <td class="tdc">”</td> + </tr><tr> + <td class="tdc"> </td> + <td class="tdc"> </td> + <td class="tdl_wsp">Sum</td> + <td class="tdr">99.07</td> + <td class="tdc">”</td> + <td class="tdc">”</td> + </tr><tr> + <td class="tdc"> </td> + <td class="tdc"> </td> + <td class="tdl_wsp">Undetermined  </td> + <td class="tdr">0.93</td> + <td class="tdc">”</td> + <td class="tdc">”</td> + </tr> + </tbody> +</table> + +<p>For polarization the lamplight shadow polariscope employed for sugar +may be used, and the degrees of the sugar (ventzke) scale converted +into angular degrees by multiplying by 0.3467.</p> + +<p>The process of fermentation is conducted as described in the paragraph +given further on, relating to the determination of lactose in the +presence of sucrose.</p> + +<p><b>256. The Oxidation Method.</b>—The removal of the reducing sugars +may be accomplished by oxidation instead of fermentation. The process +of analysis is in all respects similar to that described in the +foregoing paragraph, substituting oxidation for fermentation.<a id="FNanchor_212" href="#Footnote_212" class="fnanchor">[212]</a> +For the oxidizing agent mercuric cyanid is preferred, and it is +conveniently prepared by dissolving 120 grams of mercuric cyanid and +an equal quantity of sodium hydroxid in water mixing the solutions +and completing the volume to one liter. If a precipitate be formed +in mixing the solutions it should be removed by filtering through +asbestos. For the polarization, ten grams of the sugars in 100 cubic +centimeters is a convenient quantity. Ten cubic centimeters of +this solution are placed in a flask of water marked at fifty cubic +centimeters, a sufficient quantity of the mercuric cyanid added to +remain in slight excess after the oxidation is finished (from twenty to +twenty-five cubic centimeters) and the mixture heated to the boiling +point for three minutes. The alkali, after cooling, is neutralized with +strong hydrochloric acid and the passing from alkalinity to acidity +will be indicated by a discharge of the brown color which is produced +by heating with the alkaline mercuric cyanid. The heating with the +mercury salt should be conducted in a well ventilated fume chamber. +<span class="pagenum"><a id="Page_291"></a>[Pg 291]</span></p> + +<p>The calculation of the results is conducted by means of the formulas +given in the preceding paragraph. In the original paper describing +this method, it was stated that its accuracy depended on the complete +oxidation of the reducing sugar in a manner leaving no optically active +products, and on the inactivity of the reagents used in respect to the +dextrin present. These two conditions are not rigidly fulfilled, as is +shown by Wilson.<a id="FNanchor_213" href="#Footnote_213" class="fnanchor">[213]</a> +According to his data maltose leaves an optically active residue, which +gives a somewhat greater right hand rotation than is compensated for +by the diminished rotation of the dextrin. Wilson, however, confesses +that the dextrin used contained reducing sugars, which would not be the +case had it been prepared by the process of treating it with alkaline +mercuric cyanid as above indicated. Upon the whole, the oxidation +of the reducing sugar by a mercury salt gives results which, while +not strictly accurate, are probably as reliable as those afforded by +fermentation. The author has attempted to supplant both the oxidation +and fermentation methods by removing the reducing sugars with a +precipitating reagent, such as phenylhydrazin, but the methods are not +sufficiently developed for publication.</p> + +<p><b>257. Removal of Dextrose by Copper Acetate.</b>—Maercker first +called attention to the fact that Barfoed’s reagent (one part copper +acetate in fifteen parts of water, and 200 cubic centimeters of this +solution mixed with five cubic centimeters of thirty-eight per cent. +acetic acid) reacts readily with dextrose, while it is indifferent to +maltose and dextrins. Sieben’s method of removing dextrose is based on +this fact.<a id="FNanchor_214" href="#Footnote_214" class="fnanchor">[214]</a> +It is found that under certain conditions pure maltose +does not reduce either the acidified or neutral solution of copper +acetate, while dextrose or a mixture of dextrose and maltose does so +readily. It is also shown that the fermentation residue under suitable +conditions acts like maltose. Maltose solutions reduce the reagent +after boiling four minutes while at 40°-45° they have no effect even +after standing four days. The amount of copper deposited by dextrose, +under the latter conditions, is found to depend to a certain extent on +the amount of free acetic acid present, and as the solutions of copper +acetate always contain varying quantities of acetic acid which cannot +be removed without decomposition and precipitation of basic salt, the +<span class="pagenum"><a id="Page_292"></a>[Pg 292]</span> +use of an absolutely neutral solution is impracticable. The reagent +prepared according to Barfoed’s directions is almost saturated, but a +half normal solution is preferable. Sieben proposes two solutions: I, +containing 15.86 grams copper and 0.56 gram acetic anhydrid per liter; +II, containing 15.86 grams copper and three grams acetic anhydrid per +liter. The reduction of the dextrose is secured by placing 100 cubic +centimeters of the solution in a bottle, adding the sugar solution, +stoppering and keeping in a water-bath at 40°-45° two or three days. An +aliquot portion is then drawn off and the residual copper precipitated +by boiling with forty-five cubic centimeters of the alkali solution +of the fehling reagent and forty cubic centimeters of one per cent +dextrose solution, filtered and weighed as usual. The results show that +either solution can be used, and that standing for two days at 45° +is sufficient. One hundred cubic centimeters of the copper solution +are mixed with ten cubic centimeters of the sugar solution containing +from two-tenths to five-tenths gram of dextrose, as this dilution +gives the best results. No reduction is found to have taken place when +solutions containing five-tenths gram maltose or five-tenths gram +fermentation residue are used. The data can not be compiled in the +form of a table similar to Allihn’s, as it is impossible to obtain a +solution of uniform acidity each time, and the solution will have to be +standardized by means of a known pure dextrose solution and the result +obtained with the unknown sugar solution properly diluted compared with +this. This method of Sieben’s has never been practiced to any extent in +analytical separations and can not, therefore, be strongly recommended +without additional experience.</p> + +<p><b>258. Removal of Dextrin by Alcohol.</b>—By reason of its less +solubility, dextrin can be removed from a solution containing +also dextrose and maltose by precipitation with alcohol. It is +impracticable, however, to secure always that degree of alcoholic +concentration which will cause the coagulation of all the dextrins +without attacking the concomitant reducing sugars. In this laboratory +it has been found impossible to prepare a dextrin by alcoholic +precipitation, which did not contain bodies capable of oxidizing +alkaline copper solutions. +<span class="pagenum"><a id="Page_293"></a>[Pg 293]</span></p> + +<p>The solution containing the dextrin is brought to a sirupy consistence +by evaporation and treated with about ten volumes of ninety per cent +alcohol. After thorough mixing, the precipitated dextrin is collected +on a filter and well washed with alcohol of the strength noted. It is +then dried and weighed. If weaker solutions of dextrin are used, the +alcohol must be of correspondingly greater strength. In the filtrate +the residual maltose and dextrose may be separated and determined by +the chemical and optical methods already described.</p> + +<h3>CARBOHYDRATES IN MILK.</h3> + +<p id="P_259"><b>259. The Copper Tartrate Method.</b>—The lactose in milk is readily +estimated by the gravimetric copper method described in paragraph +<b>1<a href="#P_143">43</a></b>. Before the application of the process the casein and fat +of the milk should be removed by an appropriate precipitant, and an +aliquot part of the filtrate, diluted to contain about one per cent +of milk sugar, used for the determination. The clarification is very +conveniently secured by copper sulfate or acetic acid, as described +in the next paragraph. A proper correction should be made for the +volume occupied by the precipitate and, for general purposes, with +whole milk of fair quality this volume may be assumed to be five per +cent. One hundred grams of milk will give a precipitate occupying +approximately five cubic centimeters. In the analytical process, to +twenty cubic centimeters of milk, diluted with water to eighty, is +added a ten per cent solution of acetic acid, until a clear whey is +shown after standing a few minutes, when the volume is completed to 100 +cubic centimeters with water, and the whole, after thorough shaking, +thrown on a filter. An aliquot part of the filtrate is neutralized with +sodium carbonate and used for the lactose determination. This solution +contains approximately one per cent of lactose. In a convenient part +of it the lactose is determined and the quantity calculated for the +whole. This quantity represents the total lactose in the twenty +cubic centimeters of milk used. The weight of the milk is found by +multiplying twenty by its specific gravity. From this number the +percentage of lactose is easily found. In this process the milk is +clarified by the removal of its casein and fat. Other albuminoids +<span class="pagenum"><a id="Page_294"></a>[Pg 294]</span> +remain in solution and while these doubtless disturb the subsequent +determination of lactose, any attempt at their removal would be equally +as disadvantageous. The volume of the precipitate formed by good, whole +milk when the process is conducted as above described, is about one +cubic centimeter, for which a corresponding correction is readily made.</p> + +<p><b>260. The Official Method.</b>—The alkaline copper method +of determining lactose, adopted by the Association of Official +Agricultural Chemists, is essentially the procedure proposed by +Soxhlet.<a id="FNanchor_215" href="#Footnote_215" class="fnanchor">[215]</a></p> + +<p>Dilute twenty-five cubic centimeters of the milk, held in a half +liter flask, with 400 cubic centimeters of water and add ten cubic +centimeters of a solution of copper sulfate of the strength given for +Soxhlet’s modification of Fehling’s solution, <a href="#Page_129">page 129</a>; +add about seven and a half cubic centimeters of a solution of potassium +hydroxid of such strength that one volume of it is just sufficient +to completely precipitate the copper as hydroxid from one volume of +the solution of copper sulfate. In place of a solution of potassium +hydroxid of this strength eight and a half cubic centimeters of a half +normal solution of sodium hydroxid may be used. After the addition +of the alkali solution the mixture must still have an acid reaction +and contain copper in solution. Fill the flask to the mark, shake and +filter through a dry filter.</p> + +<p>Place fifty cubic centimeters of the mixed copper reagent in a beaker +and heat to the boiling point. While boiling briskly, add 100 cubic +centimeters of the lactose solution, prepared as directed above, and +boil for six minutes. Filter immediately and determine the amount of +copper reduced by one of the methods already given, <a href="#Page_149">pages 149-155</a>. +Obtain the weight of lactose equivalent to the weight of copper found +from the table on <a href="#MILK_SUGAR">page 163</a>.</p> + +<p><b>261. The Copper Cyanid Process.</b>—It has been found by Blyth that +the copper cyanid process of Gerrard gives practically the same results +in the determination of sugar in milk as are obtained by optical +methods.<a id="FNanchor_216" href="#Footnote_216" class="fnanchor">[216]</a> +The milk for this purpose is clarified, by precipitating the casein +with acetic acid in the following manner: +<span class="pagenum"><a id="Page_295"></a>[Pg 295]</span></p> + +<p>Twenty-five cubic centimeters of milk are diluted with an equal +volume of distilled water, and strong acetic acid added until the +casein begins to separate. The liquid is heated to boiling and, while +hot, centrifugated in any convenient machine. The supernatant liquid +obtained is separated by filtration and the solid matter thrown upon +the filter and well washed with hot water. The filtrate and washings +are cooled and completed to a volume of 100 cubic centimeters. This +liquid is of about the proper dilution for use with the copper cyanid +reagent. The percentage of sugar determined by this reagent agrees well +with that obtained by the optical method, when no other sugars than +lactose are present. If there be a notable difference in the results +of the two methods other sugars must be looked for. The presence of +dextrin may be determined by testing a few drops of the clear liquor +with iodin, which, in the presence of dextrin, gives a reddish color. +Other sugars are determined by obtaining their osazones. For this +purpose the filtrate obtained as above should be concentrated until +the volume is about thirty cubic centimeters. Any solid matter which +separates during the evaporation is removed by filtration. The osazones +are precipitated in the manner described in paragraph <b><a href="#P_147">147</a></b>. +On cooling, the almost solid crystalline mass obtained is placed on a +filter, washed with a little cold water, the crystals then pressed +between blotting paper and dried at a temperature of 100°. The dry +osazones obtained are dissolved in boiling absolute alcohol, of which +just sufficient is used to obtain complete solution. The alcoholic +solution is set aside for twelve hours and the separation of a +crystalline product after that time shows that dextrose or invert sugar +is present. Milk sugar alone gives no precipitate but only a slight +amorphous deposit. The lactosazone is precipitated by adding a little +water to the hot alcoholic solution and the crystals thus obtained +should be dissolved in boiling absolute alcohol and reprecipitated by +the addition of water at least three times in order to secure them +pure. The osazones are identified by their melting points, paragraph +<b><a href="#P_172">172</a></b>. The first part of this method does not appear to have any +advantage over the optical process by double dilution (<a href="#Page_278">p. 278</a>), +and requires more time. +<span class="pagenum"><a id="Page_296"></a>[Pg 296]</span></p> + +<p id="P_262"><b>262. Sugars in Evaporated Milks.</b>—In addition to the lactose +normally present in evaporated milks the analyst will, in most cases, +find large quantities of sucrose. The latter sugar is added as a +preservative and condiment. By reason of the ease with which sucrose +is hydrolyzed, evaporated milk containing it may have also some invert +sugar among its contents. A method of examination is desirable, +therefore, which will secure the determination of lactose, sucrose +and invert sugar in mixtures. The probability of the development of +galactose and dextrose during the evaporation and conservation of the +sample, is not great. The best method of conducting this work is the +one developed by Bigelow and McElroy.<a id="FNanchor_217" href="#Footnote_217" class="fnanchor">[217]</a> +The principle on which the method is based rests on the fact that in +certain conditions, easily supplied, the sucrose and invert sugar +present in a sample may be entirely removed by fermentation and the +residual lactose secured in an unchanged condition. The lactose is +finally estimated by one of the methods already described.</p> + +<p>The details of the process follow:</p> + +<p>On opening a package of evaporated milk, its entire contents are +transferred to a dish and well mixed. Several portions of about +twenty-five grams each are placed in flasks marked at 100 cubic +centimeters. To each of the flasks enough water is added to bring +all the sugars into solution and normal rotation is made certain by +boiling. After cooling, the contents of the flasks are clarified by +mercuric iodid in acetic acid solution. The clarifying reagent is +prepared by dissolving fifty-three grams of potassium iodid, twenty-two +grams of mercuric chlorid, and thirty-two cubic centimeters of +strongest acetic acid in water, mixing the solutions and completing +the volume to one liter. The clarification is aided by the use of +alumina cream (<b><a href="#P_84">84</a></b>). The flask is filled to the mark, and the +contents well shaken and poured on a filter. After rejecting the first +portion of the filtrate the residue is polarized in the usual manner. +Two or more separate portions of the sample are dissolved in water in +flasks of the size mentioned, heated to 55°, half a cake of compressed +yeast added to each and the temperature kept at 55° for five hours. +The residue in each flask is treated as above described, the mercuric +<span class="pagenum"><a id="Page_297"></a>[Pg 297]</span> +solution being added before cooling to prevent the fermentative action +of the yeast, and the polarization noted.</p> + +<p>By this treatment the sucrose is completely inverted, while the +lactose is not affected. The percentage of sucrose is calculated by +the formulas given in paragraph <b><a href="#P_94">94</a></b>, using the factor 142.6. At +the temperature noted the yeast exercises no fermentative, but only a +diastatic action.</p> + +<p>In each case the volume of the precipitated milk solids is determined +by the double dilution method, and the proper correction made (<a href="#Page_278">p. 278</a>). +The lactose remaining is determined by chemical or optical methods, +but it is necessary, in all cases where invert sugar is supposed to be +present, to determine the total reducing sugars in the original sample +as lactose. If the quantity thus determined and the amount of sucrose +found as above are sufficient to produce the rotation observed in the +first polarization, it is evident that no invert sugar is present. When +the polarization observed is less than is equivalent to the quantity +of sugar found, invert sugar is present, which tends to diminish the +rotation produced by the other sugars. In this case it is necessary to +remove both the sucrose and invert sugar by a process of fermentation, +which will leave the lactose unchanged.</p> + +<p>This is accomplished by conducting the fermentation in the presence +of potassium fluorid, which prevents the development of the lactic +ferments. For this purpose 350 grams of the evaporated milk are +dissolved in water and the solution boiled to secure the normal +rotation of the lactose. After cooling to 80°, the casein is thrown +down by adding a solution containing about four grams of glacial +phosphoric acid and keeping the temperature at 80° for about fifteen +minutes. After cooling to room temperature, the volume is completed +to one liter with water, well shaken and poured onto a filter. An +aliquot part of the filtrate is nearly neutralized with a noted volume +of potassium hydroxid. Enough water is added to make up, with the +volume of potassium hydroxid used, the total space occupied by the +precipitated solid, corresponding to that part of the filtrate, and if +necessary, refilter. The volume occupied by the precipitated solids is +easily determined by polarization and double dilution. The filtrate, +<span class="pagenum"><a id="Page_298"></a>[Pg 298]</span> +obtained from the process described above, is placed in portions of +100 cubic centimeters each in 200 cubic centimeter flasks with about +twenty milligrams of potassium fluorid in solution, and half a cake of +compressed yeast. The yeast is broken up and evenly distributed, and +the fermentation is allowed to proceed for ten days at a temperature +of from 25° to 30°. At the end of this time experience has shown that +all of the sucrose and invert sugar has disappeared, but the lactose +remains intact. The flasks are filled to the mark with water and the +lactose determined by chemical or optical methods. By comparing the +data obtained from the estimation of the total reducing sugars before +fermentation or inversion and the estimation of the lactose after +fermentation, the quantity of invert sugar is easily calculated. The +experience of this laboratory shows that invert sugar is rarely present +in evaporated milks, which is an indication that the sucrose added +thereto does not generally suffer hydrolysis. The mean percentage of +added sucrose found in evaporated milks is about forty.</p> + +<h3>SEPARATION AND DETERMINATION<br> OF STARCH.</h3> + +<p><b>263. Occurrence.</b>—Many bodies containing starch are presented +for the consideration of the agricultural analyst. First in importance +are the cereals, closely followed by the starchy root crops. Many +spices and other condiments also contain starchy matters. In the sap +of some plants, for instance sorghum, at certain seasons, considerable +quantities of starch occur. In the analysis of cereals and other +feeding stuffs, it has been the usual custom to make no separate +determination of starch, but to put together all soluble carbohydrates +and estimate their percentage by subtracting from 100 the sum of the +percentages of the other constituents of the sample. This aggregated +mass has been known as nitrogen-free extract. Recent advances in +methods of investigation render it advisable to determine the +starch and pentosan carbohydrates separately and to leave among the +undetermined bodies the other unclassed substances, chiefly of a +carbohydrate nature, soluble in boiling dilute acid and alkali. +<span class="pagenum"><a id="Page_299"></a>[Pg 299]</span></p> + +<p><b>264. Separation of Starch.</b>—Starch being insoluble in its natural +state, it is impossible to separate it from the other insoluble matters +of plants by any known process. In bringing it into solution it +undergoes certain changes of an unknown nature, but tending to produce +a dextrinoid body. Nevertheless, in order to procure the starch in a +state of purity suited to analytical processes, it becomes necessary +to dissolve the starch from the other insoluble bodies that naturally +accompany it. As has been shown in preceding paragraphs, there are only +two methods of securing the solution of starch which fully meet the +conditions of accurate analysis. These are the methods depending on the +use of diastatic ferments and on the employment of heat and pressure +in the presence of water. These two processes have been described in +considerable detail in paragraphs <b><a href="#P_179">179-181</a></b>. It is important, in +starch determinations, to remove from the sample the sugar and other +substances soluble in water and also the oils, when present in large +quantities, before subjecting it to the processes for rendering the +starch soluble.</p> + +<p><b>265. Desiccation of Amyliferous Bodies.</b>—The removal of +sugars and oils is best secured in amyliferous substances after they +are deprived of their moisture. As has already been suggested, the +desiccation should be commenced at a low temperature, not above 60°, +and continued at that point until the chief part of the water has +escaped. The operation may be conducted in one of the ways already +described (<a href="#Page_12">pp. 12-27</a>). There is great difference of opinion +among analysts in respect of the degree of temperature to which the sample +should be finally subjected, but for the purposes here in view, it will +not be found necessary to go above 105°. Before beginning the operation +the sample should be as finely divided as possible, and at its end the +dried residue should be ground and passed through a sieve of half a +millimeter mesh.</p> + +<p><b>266. Indirect Method of Determining: Water in Starch.</b>—It is +claimed by Block<a id="FNanchor_218" href="#Footnote_218" class="fnanchor">[218]</a> +that it is necessary to dry starch at 160° in order to get complete +dehydration. Wet starch as deposited with its maximum content of water +has nine molecules thereof, <i>viz.</i>, <b>C₆H₁₀O₅ + 9H₂O</b>. Ordinary +commercial starch has about eighteen per cent of water with a formula +of <b>C₆H₁₀O₅ + 2H₂O</b>. +<span class="pagenum"><a id="Page_300"></a>[Pg 300]</span></p> + +<p>The percentage of water may be determined by Block’s feculometer or +Block’s dose-fécule. The first apparatus determines the percentage of +anhydrous starch by volume, and the second by weight.</p> + +<p>Block’s assumption that starch can absorb only fifty per cent of its +weight of water is the basis of the determination.</p> + +<p>A noted weight of starch is rubbed up with water until saturated, the +water poured off, the starch weighed, dried on blotting paper until it +gives off no more moisture and again weighed. Half of the lost weight +is water, from which the original per cent of water can be calculated. +This at best seems to be a rough approximation and not suited to +rigorous scientific determination.</p> + +<p><b>267. Removal of Oil and Sugar.</b>—The dried, finely powdered +sample, obtained as described above, is placed in any convenient +extractor (<b><a href="#P_33">33-43</a></b>) and the oil or fat it contains removed by +the usual solvents. For ordinary purposes, even with cereals, this +preliminary extraction of the oil is not necessary, but it becomes so +with oily seeds containing starch. The sugar is subsequently removed +by extraction with eighty per cent alcohol and the residue is then +ready for the extraction of the starch. In most cases the extraction +with alcohol will be found sufficient. In some bodies, for instance +the sweet potato (batata), the quantity of sugar present is quite +large, and generally some of it is found. If not present in appreciable +amount, the alcohol extraction may also be omitted. The sample having +been prepared as indicated, the starch may be brought into solution by +one of the methods described in paragraphs <b><a href="#P_179">179-181</a></b>, preference +being given to the aqueous digestion in an autoclave. The dissolved +starch is washed out of the insoluble residue and determined by optical +or chemical methods <b><a href="#P_186">186-194</a></b>.</p> + +<p><b>268. Preparation of Diastase for Starch Solution.</b>—The methods +of preparing malt extract for use in starch analysis have been +described in paragraph <b><a href="#P_179">179</a></b>. If a purer form of diastase is +desired it may be prepared by following the directions given by Long +and Baker.<a id="FNanchor_219" href="#Footnote_219" class="fnanchor">[219]</a> +Digest 200 grams of ground malt for twenty-four hours +<span class="pagenum"><a id="Page_301"></a>[Pg 301]</span> +with three parts of twenty per cent alcohol. Separate the extract +by filtration and to the filtrate add about one and a half liters +of ninety-three per cent alcohol and stir vigorously. After the +precipitate has subsided the supernatant alcohol is removed by a +syphon, the precipitate is brought onto a filter and washed with +alcohol of a strength gradually increasing to anhydrous, and finally +with anhydrous ether. The diastase is dried in a vacuum over sulfuric +acid and finally reduced to a fine powder before using. Thus prepared, +it varies in appearance from a white to a slightly brownish powder. +Made at different times and from separate portions of malt, it may show +great differences in hydrolytic power.</p> + +<p><b>269. Estimation of Starch in Potatoes by Specific Gravity.</b>—A +roughly approximate determination of the quantity of starch in potatoes +can be made by determining their specific gravity. Since the specific +gravity of pure starch is 1.65, it follows that the richer a potato is +in starch the higher will be its specific gravity. The specific weight +of substances like potatoes is conveniently determined by suspending +them in water by a fine thread attached to the upper hook of a balance +pan. There may be a variation of the percentage of other constituents +in potatoes as well as of starch, and therefore the data obtained from +the following table can only be correct on the assumption that the +starch is the only variable. In practice, errors amounting to as much +as two per cent may be easily made, and therefore the method is useful +only for agronomic and commercial and not for scientific purposes. The +method is especially useful in the selection of potatoes of high starch +content for planting. The table is constructed on the weight in grams +in pure water of 10000 grams of potatoes and the corresponding per +cents of dry matter and starch are given. It is not always convenient +to use exactly 10000 grams of potatoes for the determination, but the +calculation for any given weight is easy.<a id="FNanchor_220" href="#Footnote_220" class="fnanchor">[220]</a></p> + +<div class="blockquot"> +<p><i>Example.</i>—Let the weight of a potato in air be 159 grams, and +its weight in water 14.8 grams.</p> + +<p>Then the weight of 10000 grams of potatoes of like nature in water +would be found from the equation 159: 10000 = 14.8: <i>x</i>.</p> + +<p>Whence <i>x</i> = 931 nearly.</p> +</div> + +<p><span class="pagenum"><a id="Page_302"></a>[Pg 302]</span> +In the table the nearest figure to 931 is 930, corresponding to +24.6 per cent of dry matter and 18.8 per cent of starch. When +the number found is half way between the numbers given in the +table the mean of the data above and below can be taken. In +other positions a proper interpolation can be made if desired but +for practical purposes the data corresponding to the nearest +number can be used.</p> + +<p class="f120 spa1"><b><span class="smcap">Table for Calculating Starch in Potatoes<br> +from Specific Gravity.</span></b></p> + +<table class="spb1"> + <thead><tr> + <th class="tdc bb">10000 grams<br>of potatoes<br>weigh in water.<br>Grams.</th> + <th class="tdc_bott bb">Per cent<br> dry matter. </th> + <th class="tdc_bott bb"> Per cent <br>starch.</th> + </tr></thead> + <tbody><tr> + <td class="tdc"> 750</td> + <td class="tdc">19.9</td> + <td class="tdc">14.1</td> + </tr><tr> + <td class="tdc"> 760</td> + <td class="tdc">20.1</td> + <td class="tdc">14.3</td> + </tr><tr> + <td class="tdc"> 770</td> + <td class="tdc">20.3</td> + <td class="tdc">14.5</td> + </tr><tr> + <td class="tdc"> 780</td> + <td class="tdc">20.7</td> + <td class="tdc">14.9</td> + </tr><tr> + <td class="tdc"> 790</td> + <td class="tdc">20.9</td> + <td class="tdc">15.1</td> + </tr><tr> + <td class="tdc"> 800</td> + <td class="tdc">21.2</td> + <td class="tdc">15.4</td> + </tr><tr> + <td class="tdc"> 810</td> + <td class="tdc">21.4</td> + <td class="tdc">15.6</td> + </tr><tr> + <td class="tdc"> 820</td> + <td class="tdc">21.6</td> + <td class="tdc">15.8</td> + </tr><tr> + <td class="tdc"> 830</td> + <td class="tdc">22.0</td> + <td class="tdc">16.2</td> + </tr><tr> + <td class="tdc"> 840</td> + <td class="tdc">22.2</td> + <td class="tdc">16.4</td> + </tr><tr> + <td class="tdc"> 850</td> + <td class="tdc">22.4</td> + <td class="tdc">16.6</td> + </tr><tr> + <td class="tdc"> 860</td> + <td class="tdc">22.7</td> + <td class="tdc">16.9</td> + </tr><tr> + <td class="tdc"> 870</td> + <td class="tdc">22.9</td> + <td class="tdc">17.1</td> + </tr><tr> + <td class="tdc"> 880</td> + <td class="tdc">23.1</td> + <td class="tdc">17.3</td> + </tr><tr class="bb"> + <td class="tdc"> 890</td> + <td class="tdc">23.5</td> + <td class="tdc">17.7</td> + </tr><tr> + <td class="tdc"> 900</td> + <td class="tdc">23.7</td> + <td class="tdc">17.9</td> + </tr><tr> + <td class="tdc"> 910</td> + <td class="tdc">24.0</td> + <td class="tdc">18.2</td> + </tr><tr> + <td class="tdc"> 920</td> + <td class="tdc">24.2</td> + <td class="tdc">18.4</td> + </tr><tr> + <td class="tdc"> 930</td> + <td class="tdc">24.6</td> + <td class="tdc">18.8</td> + </tr><tr> + <td class="tdc"> 940</td> + <td class="tdc">24.8</td> + <td class="tdc">19.0</td> + </tr><tr> + <td class="tdc"> 950</td> + <td class="tdc">25.0</td> + <td class="tdc">19.2</td> + </tr><tr> + <td class="tdc"> 960</td> + <td class="tdc">25.2</td> + <td class="tdc">19.4</td> + </tr><tr> + <td class="tdc"> 970</td> + <td class="tdc">25.5</td> + <td class="tdc">19.7</td> + </tr><tr> + <td class="tdc"> 980</td> + <td class="tdc">25.9</td> + <td class="tdc">20.1</td> + </tr><tr class="bb"> + <td class="tdc"> 990</td> + <td class="tdc">26.1</td> + <td class="tdc">20.3</td> + </tr><tr> + <td class="tdc">1000</td> + <td class="tdc">26.3</td> + <td class="tdc">20.5</td> + </tr><tr> + <td class="tdc">1010</td> + <td class="tdc">26.5</td> + <td class="tdc">20.7</td> + </tr><tr> + <td class="tdc">1020</td> + <td class="tdc">26.9</td> + <td class="tdc">21.1</td> + </tr><tr> + <td class="tdc">1030</td> + <td class="tdc">27.2</td> + <td class="tdc">21.4</td> + </tr><tr> + <td class="tdc">1040</td> + <td class="tdc">27.4</td> + <td class="tdc">21.6</td> + </tr><tr> + <td class="tdc">1050</td> + <td class="tdc">27.6</td> + <td class="tdc">21.8</td> + </tr><tr> + <td class="tdc">1060</td> + <td class="tdc">28.0</td> + <td class="tdc">22.2</td> + </tr><tr> + <td class="tdc">1070</td> + <td class="tdc">28.3</td> + <td class="tdc">22.5</td> + </tr><tr> + <td class="tdc">1080</td> + <td class="tdc">28.5</td> + <td class="tdc">22.7</td> + </tr><tr class="bb"> + <td class="tdc">1090</td> + <td class="tdc">28.7</td> + <td class="tdc">22.9</td> + </tr><tr> + <td class="tdc">1100</td> + <td class="tdc">29.1</td> + <td class="tdc">23.3</td> + </tr><tr> + <td class="tdc">1110</td> + <td class="tdc">29.3</td> + <td class="tdc">23.5</td> + </tr><tr> + <td class="tdc">1120</td> + <td class="tdc">29.5</td> + <td class="tdc">23.7</td> + </tr><tr> + <td class="tdc">1130</td> + <td class="tdc">29.8</td> + <td class="tdc">24.0</td> + </tr><tr> + <td class="tdc">1140</td> + <td class="tdc">30.2</td> + <td class="tdc">24.4</td> + </tr><tr> + <td class="tdc">1150</td> + <td class="tdc">30.4</td> + <td class="tdc">24.6</td> + </tr><tr> + <td class="tdc">1160</td> + <td class="tdc">30.6</td> + <td class="tdc">24.8</td> + </tr><tr> + <td class="tdc">1170</td> + <td class="tdc">31.0</td> + <td class="tdc">25.0</td> + </tr><tr> + <td class="tdc">1180</td> + <td class="tdc">31.3</td> + <td class="tdc">25.5</td> + </tr><tr class="bb"> + <td class="tdc">1190</td> + <td class="tdc">31.5</td> + <td class="tdc">25.7</td> + </tr><tr> + <td class="tdc">1200</td> + <td class="tdc">31.7</td> + <td class="tdc">25.9</td> + </tr><tr> + <td class="tdc">1210</td> + <td class="tdc">32.1</td> + <td class="tdc">26.3</td> + </tr><tr> + <td class="tdc">1220</td> + <td class="tdc">32.3</td> + <td class="tdc">26.5</td> + </tr><tr> + <td class="tdc">1230</td> + <td class="tdc">32.5</td> + <td class="tdc">26.7</td> + </tr><tr> + <td class="tdc">1240</td> + <td class="tdc">33.0</td> + <td class="tdc">27.2</td> + </tr><tr> + <td class="tdc">1250</td> + <td class="tdc">33.2</td> + <td class="tdc">27.4</td> + </tr><tr> + <td class="tdc">1260</td> + <td class="tdc">33.4</td> + <td class="tdc">27.6</td> + </tr><tr> + <td class="tdc">1270</td> + <td class="tdc">33.6</td> + <td class="tdc">27.8</td> + </tr><tr> + <td class="tdc">1280</td> + <td class="tdc">34.1</td> + <td class="tdc">28.3</td> + </tr><tr class="bb"> + <td class="tdc">1290</td> + <td class="tdc">34.3</td> + <td class="tdc">28.5</td> + </tr><tr> + <td class="tdc">1300</td> + <td class="tdc">34.5</td> + <td class="tdc">28.7</td> + </tr><tr> + <td class="tdc">1310</td> + <td class="tdc">34.9</td> + <td class="tdc">29.1</td> + </tr><tr> + <td class="tdc">1320</td> + <td class="tdc">35.1</td> + <td class="tdc">29.3</td> + </tr><tr> + <td class="tdc">1330</td> + <td class="tdc">35.4</td> + <td class="tdc">29.6</td> + </tr><tr> + <td class="tdc">1340</td> + <td class="tdc">35.8</td> + <td class="tdc">30.0</td> + </tr><tr> + <td class="tdc">1350</td> + <td class="tdc">36.0</td> + <td class="tdc">30.2</td> + </tr><tr> + <td class="tdc">1360</td> + <td class="tdc">36.2</td> + <td class="tdc">30.4</td> + </tr><tr class="bb"> + <td class="tdc">1370</td> + <td class="tdc">36.6</td> + <td class="tdc">30.8</td> + </tr> + </tbody> +</table> + +<p><span class="pagenum"><a id="Page_303"></a>[Pg 303]</span> +<b>270. Constitution of Cellulose.</b>—The group of bodies known as +cellulose comprises many members of essentially the same chemical +constitution but of varying properties. The centesimal composition of +pure cellulose is shown by the following numbers:</p> + +<table class="spb1"> + <tbody><tr> + <td class="tdl">Carbon,</td> + <td class="tdr_wsp">44.2</td> + <td class="tdl_wsp">per</td> + <td class="tdl_wsp">cent</td> + </tr><tr> + <td class="tdl">Hydrogen,  </td> + <td class="tdr_wsp">6.3</td> + <td class="tdc">”</td> + <td class="tdc">”</td> + </tr><tr> + <td class="tdl">Oxygen,</td> + <td class="tdr_wsp">49.5</td> + <td class="tdc">”</td> + <td class="tdc">”</td> + </tr> + </tbody> +</table> + +<p class="no-indent">corresponding to the formula <b>C₆H₁₀H₅</b>.</p> + +<p>According to the view of Cross and Bevan, cellulose conforms in respect +of its ultimate constitutional groups to the general features of the +simple carbohydrates, but differs from them by reason of a special +molecular configuration resulting in a suppression of the activity of +constituent groups in certain respects, and an increase in activity of +others.<a id="FNanchor_221" href="#Footnote_221" class="fnanchor">[221]</a></p> + +<p><b>271. Fiber and Cellulose.</b>—The carbohydrates of a plant +insoluble in water are not composed exclusively of starch. There are, +in addition to starch, pentosan fibers yielding pentose sugars on +hydrolysis and furfuraldehyd on distillation with a strong acid. The +quantitive methods for estimating the pentosan bodies are given in +paragraphs <b><a href="#P_150">150-157</a></b>. The method to be preferred +is that of Krug (<b><a href="#P_155">155</a></b>).</p> + +<p>In the estimation of cattlefoods and of plant substances in general the +residue insoluble in dilute boiling acid and alkali is called crude or +indigestible fiber.</p> + +<p>The principle on which the determination depends rests on the +assumption that all the protein, starch and other digestible +carbohydrates will be removed from the sample by successive digestion +at a boiling temperature with acid and alkali solutions of a given +strength. It is evident that the complex body obtained by the treatment +outlined above is not in any sense a definite chemical compound, but it +may be considered as being composed partly of cellulose.</p> + +<p id="P_272"><b>272. Official Method of Determining Crude Fiber.</b>—The method +of estimating crude fiber, adopted by the Association of Official +Agricultural Chemists, is as follows: +<a id="FNanchor_222" href="#Footnote_222" class="fnanchor">[222]</a></p> + +<p><span class="pagenum"><a id="Page_304"></a>[Pg 304]</span> +Extract two grams of the substance with ordinary ether, at least +almost completely, or use the residue from the determination of the +ether extract. To this residue, in a half liter flask, add 200 cubic +centimeters of boiling 1.25 per cent sulfuric acid; connect the flask +with an inverted condenser, the tube of which passes only a short +distance beyond the rubber stopper into the flask. Boil at once, and +continue the boiling for thirty minutes. A blast of air conducted into +the flask may serve to reduce the frothing of the liquid. Filter, wash +thoroughly with boiling water until the washings are no longer acid, +rinse the substance back into the same flask with 200 cubic centimeters +of a boiling 1.25 per cent solution of sodium hydroxid, free or nearly +free of sodium carbonate, boil at once and continue the boiling for +thirty minutes in the same manner as directed above for the treatment +with acid. Filter into a gooch, and wash with boiling water until the +washings are neutral, dry at 110°, weigh and incinerate completely. The +loss of weight is crude fiber.</p> + +<p>The filter used for the first filtration may be linen, one of the forms +of glass wool or asbestos filters, or any other form that secures clear +and reasonably rapid filtration. The solutions of sulfuric acid and +sodium hydroxid are to be made up of the specified strength, determined +accurately by titration and not merely from specific gravity.</p> + +<p>The experience of this laboratory has shown that results practically +identical with those got as above, are obtained by conducting the +digestions in hard glass beakers covered with watch glasses. The ease +of manipulation in the modification of the process just mentioned is a +sufficient justification for its use.</p> + +<p><b>273. Separation of Cellulose.</b>—Hoppe-Seyler observed that +cellulose, when melted with the alkalies at a temperature as high as +200°, was not sensibly attacked.<a id="FNanchor_223" href="#Footnote_223" class="fnanchor">[223]</a></p> + +<p>Lange has based a process for determining cellulose on this +observation.<a id="FNanchor_224" href="#Footnote_224" class="fnanchor">[224]</a></p> + +<p>The process, as improved by him, is carried out as follows:</p> + +<p>From five to ten grams of the substance are moistened with water and +placed in a porcelain dish with about three times their weight of +caustic alkali free of nitrates and about twenty cubic centimeters of +water. The porcelain dish should be deep and crucible shaped and should +<span class="pagenum"><a id="Page_305"></a>[Pg 305]</span> +be placed in an oil-bath, the temperature of which is easily +controlled. The contents of the dish are stirred with the thermometer +bulb until all foaming ceases and the temperature of the mixture is +then kept at from 175° to 180° for an hour. After the melt has cooled +to 80° about seventy-five cubic centimeters of hot water are added to +bring it into solution and it is then allowed to cool. The solution is +acidified with sulfuric and placed in large centrifugal tubes. After +being made slightly alkaline with soda lye, the tubes are subjected +to continued energetic centrifugal action until the cellulose is +separated. The supernatant liquid can be nearly all poured off and the +separated cellulose is broken up, treated with hot water and again +separated by centrifugal action. The cellulose is finally collected +upon the asbestos felt, washed with hot water, alcohol and ether, dried +and weighed. With a little practice it is possible to complete the +separation of cellulose in two and one-half hours.</p> + +<p><b>274. Solubility of Cellulose.</b>—Cellulose resembles starch in +its general insolubility, but, unlike starch, it may be dissolved in +some reagents and afterwards precipitated practically unchanged or in a +state of hydration. One of the simplest solvents of cellulose is zinc +chlorid in concentrated aqueous solution.</p> + +<p>The solution is accomplished with the aid of heat, adding one part by +weight of cotton to six parts of zinc chlorid dissolved in ten parts of +water.</p> + +<p>A homogeneous sirup is obtained by this process, which is used in the +arts for making the carbon filaments of incandescent electric lamps.</p> + +<p>In preparing the thread of cellulose, the solution, obtained as +described above, is allowed to flow, in a fine stream, into alcohol, +whereby a cellulose hydrate is precipitated, which is freed from zinc +hydroxid by digesting in hydrochloric acid.</p> + +<p>Hydrochloric acid may be substituted for water in preparing the reagent +above noted, whereby a solvent is secured which acts upon cellulose +readily in the cold.</p> + +<p>A solution of ammoniacal cupric oxid is one of the best solvents for +cellulose. The solution should contain from ten to fifteen per cent of +ammonia and from two to two and a half of cupric oxid. +<span class="pagenum"><a id="Page_306"></a>[Pg 306]</span></p> + +<p>In the preparation of this reagent, ammonium chlorid is added to a +solution of cupric salt and then sodium hydroxid in just sufficient +quantity to precipitate all of the copper as hydroxid. The precipitate +is well washed on a linen filter, squeezed as dry as possible and +dissolved in ammonia of 0.92 specific gravity. The cellulose is readily +precipitated from the solution in cuprammonium by the addition of +alcohol, sodium chlorid, sugar, or other dehydrating agents. Solutions +of cellulose are used in the arts for many purposes.<a id="FNanchor_225" href="#Footnote_225" class="fnanchor">[225]</a></p> + +<p><b>275. Qualitive Reactions for Detecting Cellulose.</b>—Cellulose +may be identified by its resistance to the action of oxidizing agents, +to the halogens and to alkaline solutions. It is further recognized by +the sirupy or gelatinous solutions it forms with the solvents mentioned +above. The cellulose hydrates precipitated from solutions have in some +instances the property of forming a blue color with iodin.</p> + +<p>A characteristic reaction of cellulose is secured as follows: To a +saturated solution of zinc hydrochlorate, of 2.00 specific gravity, are +added six parts by weight of potassium iodid dissolved in ten parts +of water and this solution is saturated with iodin. Cellulose treated +with this reagent is at once stained a deep blue violet color.<a id="FNanchor_226" href="#Footnote_226" class="fnanchor">[226]</a> +For the characteristics of cellulose occurring in wood the researches of +Lindsey may be consulted.<a id="FNanchor_227" href="#Footnote_227" class="fnanchor">[227]</a></p> + +<p><b>276. More Rarely Occurring Carbohydrates.</b>—It is not possible +here to give more space to the rarer forms of carbohydrates, to which +the attention of the agricultural analyst may be called. Nearly a +hundred kinds of sugars alone have been detected in the plant world. +For descriptions of the properties of these bodies and the methods of +their detection and determination, the standard works on carbohydrates +may be consulted.<a id="FNanchor_228" href="#Footnote_228" class="fnanchor">[228]</a></p> + +<h3>AUTHORITIES CITED IN PART THIRD.</h3> + +<div class="footnotes"> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_170" href="#FNanchor_170" class="label">[170]</a> +Vines; Physiology of Plants. Nägeli; Beiträge zur näheren +Kenntniss der Stärkegruppe.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_171" href="#FNanchor_171" class="label">[171]</a> +Bulletin 5, Department of Agriculture, Division of Chemistry, pp. 191 +et seq.: Bulletin 25, New Hampshire Experiment Station.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_172" href="#FNanchor_172" class="label">[172]</a> +Spencer; Handbook for Sugar Manufacturers, p. 31.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_173" href="#FNanchor_173" class="label">[173]</a> +Vid. op. cit. supra, pp. 102, 108.</p> +</div> + +<p><span class="pagenum"><a id="Page_307"></a>[Pg 307]</span></p> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_174" href="#FNanchor_174" class="label">[174]</a> +Journal of the American Chemical Society, Vol. 16, p. 677.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_175" href="#FNanchor_175" class="label">[175]</a> +Botanical Gazette, Vol. 12, No. 3.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_176" href="#FNanchor_176" class="label">[176]</a> +Bulletin de l’Association des Chimistes de Sucrerie et de +Distillerie, Tome 13, p. 133.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_177" href="#FNanchor_177" class="label">[177]</a> +Journal of Analytical and Applied Chemistry, Vol. 4, p. 381.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_178" href="#FNanchor_178" class="label">[178]</a> +Spencer’s Handbook for Sugar Manufacturers, pp. 30 et seq.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_179" href="#FNanchor_179" class="label">[179]</a> +Bulletin de l’Association des Chimistes de Sucrerie et de +Distillerie, Tome 13, p. 292.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_180" href="#FNanchor_180" class="label">[180]</a> +Vid. op. cit. supra, Tome 2, p. 369.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_181" href="#FNanchor_181" class="label">[181]</a> +Dosage du Sucre Cristallisable dans la Betterave, pp. 117 +et seq.: Journal of the American Chemical Society, Vol. 16, p. 266.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_182" href="#FNanchor_182" class="label">[182]</a> +Neue Zeitschrift für Rübenzucker-Industrie. Band 3, S. 342; Band 14, S. +286: Zeitschrift des Vereins für die Rübenzucker-Industrie, 1876, S. +692: Dingler’s Polytechnisches Journal, Band 232, S. 461.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_183" href="#FNanchor_183" class="label">[183]</a> +Sidersky: Traité d’ Analyse des Matières Sucrées, p. 304.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_184" href="#FNanchor_184" class="label">[184]</a> +Neue Zeitschrift für Rübenzucker-Industrie, Band 14, S. 286.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_185" href="#FNanchor_185" class="label">[185]</a> +Zeitschrift des Vereins für die Rübenzucker-Industrie, Band 32, S. 861.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_186" href="#FNanchor_186" class="label">[186]</a> +Spencer’s Handbook for Sugar Manufacturers, p. 42.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_187" href="#FNanchor_187" class="label">[187]</a> +Bulletin No. 4 of the Chemical Society of Washington, pp. 22, et seq.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_188" href="#FNanchor_188" class="label">[188]</a> +Vid. op. et loc. cit. 7.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_189" href="#FNanchor_189" class="label">[189]</a> +Chemiker-Zeitung, Band 19, S. 1830.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_190" href="#FNanchor_190" class="label">[190]</a> +Vid. op cit. supra, S. 1784.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_191" href="#FNanchor_191" class="label">[191]</a> +Vid. op. cit. supra, S. 1829.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_192" href="#FNanchor_192" class="label">[192]</a> +Zeitschrift des Vereins für die Rübenzucker-Industrie, 1895, S. 844.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_193" href="#FNanchor_193" class="label">[193]</a> +Journal des Fabricants de Sucre, 1895, No. 33.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_194" href="#FNanchor_194" class="label">[194]</a> +Journal of the American Chemical Society, Vol. 2, p. 387: +Agricultural Science, Feb. 1892.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_195" href="#FNanchor_195" class="label">[195]</a> +American Chemical Journal, Vol. 13, p. 24.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_196" href="#FNanchor_196" class="label">[196]</a> +Tucker; Manual of Sugar Analysis, p. 287: Wiechmann; Sugar Analysis, p. 51.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_197" href="#FNanchor_197" class="label">[197]</a> +Sidersky; vid. op. cit., 14, p. 197.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_198" href="#FNanchor_198" class="label">[198]</a> +Journal of the American Chemical Society, Vol. 18, p. 81: +Allen; Commercial Organic Analysis, Vol. 1, p. 291.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_199" href="#FNanchor_199" class="label">[199]</a> +Handbuch der Physiologisch- und Pathologisch-Chemischen Analyse, S. 286.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_200" href="#FNanchor_200" class="label">[200]</a> +Kühne und Chittenden; American Chemical Journal, Vol. 6, p. 45.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_201" href="#FNanchor_201" class="label">[201]</a> +Vid. op. cit. supra, p. 289.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_202" href="#FNanchor_202" class="label">[202]</a> +Analyst, Vol. 13, p. 64.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_203" href="#FNanchor_203" class="label">[203]</a> +Journal American Chemical Society, Vol. 18, p. 438.</p> +</div> + +<p><span class="pagenum"><a id="Page_308"></a>[Pg 308]</span></p> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_204" href="#FNanchor_204" class="label">[204]</a> +School of Mines Quarterly, Vols. 11 and 12.</p> + +<p>In a later method (School of Mines Quarterly, Vol. 13, No. 3) +Wiechman describes the separation of the sugars by one polariscopic and +two gravimetric determinations, one before and one after inversion. +The polariscopic examination is made in a ten per cent solution at a +temperature of 20°. The gyrodynats of sucrose, dextrose and levulose +at the temperature mentioned are fixed at 66.5, 53.5 and -81.9 +respectively. The gravimetric determinations are conducted according +to the methods already described. In the formulas for calculating +the results <i>a</i> represents sucrose, <i>b</i> reducing sugars, +<i>x</i> the dextrose, <i>y</i> the levulose, and <i>d</i> the observed +polarization expressed in degrees angular measure. The gyrodynats +of sucrose, dextrose and levulose divided by 100 are represented by +<i>s</i>, <i>d</i> and <i>l</i>. The calculations are made from the +following formulas:</p> + +<p class="center">(<i>as</i> + <i>xd</i>) - <i>yl</i> = <i>p</i>.<br> +(<i>as</i> + <i>xd</i>) = <i>p</i> + <i>yl</i>.<br> +<i>xd</i> = <i>p</i> + <i>yl</i> - <i>as</i>.</p> + +<table class="spb1"> + <tbody><tr> + <td class="tdl" rowspan="2"><i>x</i> = </td> + <td class="tdc bb"><i>p</i> + <i>yl</i> - <i>as</i></td> + </tr><tr> + <td class="tdc"><i>d</i></td> + </tr> + </tbody> +</table> + +<p>In this calculation the gyrodynat of levulose is about ten degrees +lower than that of most authorities.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_205" href="#FNanchor_205" class="label">[205]</a> +Vid. op. cit., 23, Band 24, S. 869.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_206" href="#FNanchor_206" class="label">[206]</a> +Vid. op. cit. supra, 1888, S. 782.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_207" href="#FNanchor_207" class="label">[207]</a> +Neue Zeitschrift für Rübenzucker-Industrie, Band 35, S. 166.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_208" href="#FNanchor_208" class="label">[208]</a> +Journal of the American Chemical Society, Vol. 2, p. 399: Science, +Oct. 1, 1881: Proceedings American Association for the Advancement of +Science, 1881, p. 61: Sugar Cane, Vol. 13, p. 533, pp. 61-66.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_209" href="#FNanchor_209" class="label">[209]</a> +Wiley and McElroy; Agricultural Science, Vol. 6, p. 57.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_210" href="#FNanchor_210" class="label">[210]</a> +Chemical News, Vol. 46, p. 175.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_211" href="#FNanchor_211" class="label">[211]</a> +Vid. op. cit, 14, p. 352.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_212" href="#FNanchor_212" class="label">[212]</a> +Vid. op. et loc. cit., 41.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_213" href="#FNanchor_213" class="label">[213]</a> +Vid. op. cit., 41, Vol. 65, p. 169.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_214" href="#FNanchor_214" class="label">[214]</a> +Zeitschrift des Vereins für die Rübenzucker-Industrie, 1884, S. 854.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_215" href="#FNanchor_215" class="label">[215]</a> +Bulletin 46, Division of Chemistry, U. S. Department of Agriculture, p. 60.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_216" href="#FNanchor_216" class="label">[216]</a> +The Analyst, Vol. 20, p. 121.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_217" href="#FNanchor_217" class="label">[217]</a> +Journal American Chemical Society, Vol. 15, p. 668.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_218" href="#FNanchor_218" class="label">[218]</a> +Comptes rendus, Tome 118, p. 147.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_219" href="#FNanchor_219" class="label">[219]</a> +Journal of the Chemical Society, Transactions, 1895, p. 735.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_220" href="#FNanchor_220" class="label">[220]</a> +Die agrikultur-chemische Versuchsstation, Halle, a/S., S. 114.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_221" href="#FNanchor_221" class="label">[221]</a> +Cellulose, p. 77.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_222" href="#FNanchor_222" class="label">[222]</a> +Vid. op. cit., 46, p. 63.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_223" href="#FNanchor_223" class="label">[223]</a> +Zeitschrift für physiologische Chemie, Band 13, S. 84.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_224" href="#FNanchor_224" class="label">[224]</a> +Zeitschrift für angewandte Chemie, 1895, S. 561.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_225" href="#FNanchor_225" class="label">[225]</a> +Vid. op. cit., 52, pp. 8 et seq.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_226" href="#FNanchor_226" class="label">[226]</a> +Vid. op. cit. supra, p. 15.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_227" href="#FNanchor_227" class="label">[227]</a> +Composition of Wood, Agricultural Science, Vol. 7, pp. 49, 97 and 161.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_228" href="#FNanchor_228" class="label">[228]</a> +Tollens; Handbuch der Kohlenhydrate: von Lippmann; Chemie der Zuckerarten.</p> +</div> +</div> + +<hr class="chap x-ebookmaker-drop"> + +<div class="chapter"> +<p><span class="pagenum"><a id="Page_309"></a>[Pg 309]</span></p> +<h2 class="nobreak">PART FOURTH.<br> +<span class="h_subtitle">FATS AND OILS.</span></h2> +</div> + +<p><b>277. Nomenclature.</b>—The terms fat and oil are often used +interchangeably and it is difficult in all cases to limit definitely +their application. The consistence of the substance at usual room +temperatures may be regarded as a point of demarcation. The term fat, +in this sense, is applied to glycerids which are solid or semi solid, +and oil to those which are quite or approximately liquid. A further +classification is found in the origin of the glycerids, and this gives +rise to the groups known as animal or vegetable fats and oils. In this +manual, in harmony with the practices mentioned above, the term fat +will be used to designate an animal or vegetable glycerid which is +solid, and the term oil one which is liquid at common room temperature, +<i>viz.</i>, about 20°. There are few animal oils, and few vegetable +fats when judged by this standard, and it therefore happens that the +term oil is almost synonymous with vegetable glycerid and fat with +a glycerid of animal origin. Nearly related to the fats and oils is +the group of bodies known as resins and waxes. This group of bodies, +however, can be distinguished from the fats and oils by chemical +characteristics. The waxes are ethers formed by the union of fatty +acids and alcohols of the ethane, and perhaps also of the ethylene +series.<a id="FNanchor_229" href="#Footnote_229" class="fnanchor">[229]</a> +This chemical difference is not easily expressed and the terms +themselves often add confusion to the meaning, as for instance, japan +wax is composed mostly of fats, and sperm oil is essentially a wax.</p> + +<p><b>278. Composition.</b>—Fats and oils are composed chiefly of salts +produced by the combination of the complex base glycerol with the fat +acids. Certain glycerids, as the lecithins, contain also phosphorus +in organic combinations, nitrogen, and possibly other inorganic +constituents in organic forms. By the action of alkalies the glycerids +are easily decomposed, the acid combining with the inorganic base and +<span class="pagenum"><a id="Page_310"></a>[Pg 310]</span> +the glycerol becoming free. The salts thus produced form the soaps +of commerce and the freed base, when collected and purified, is the +glycerol of the trade.</p> + +<p>When waxes are decomposed by alkalies, fatty acids and alcohols of the +ethane series are produced.</p> + +<p>The natural glycerids formed from glycerol, which is a trihydric +(triatomic) alcohol, are found in the neutral state composed of three +molecules of the acid, united with one of the base. If R represent the +radicle of the fat acid the general formula for the chemical process by +which the salt is produced is:</p> + +<table class="spb1"> + <tbody><tr> + <td class="tdc" colspan="2">Glycerol.</td> + <td class="tdc"> Acid.</td> + <td class="tdc" colspan="2">Salt.</td> + <td class="tdc"> Water.</td> + </tr><tr> + <td class="tdc"> </td> + <td class="tdl">O.H</td> + <td class="tdc"> </td> + <td class="tdc"> </td> + <td class="tdl">O.R</td> + <td class="tdc"> </td> + </tr><tr> + <td class="tdl">C₃H₅</td> + <td class="tdl">O.H</td> + <td class="tdl_wsp">+ 3R.OH =</td> + <td class="tdl_wsp">C₃H₅</td> + <td class="tdl">O.R</td> + <td class="tdl_wsp">+ 3H₂O.</td> + </tr><tr> + <td class="tdc"> </td> + <td class="tdl">O.H</td> + <td class="tdc"> </td> + <td class="tdc"> </td> + <td class="tdl">O.R</td> + <td class="tdc"> </td> + </tr> + </tbody> +</table> + +<p>The resulting salts are called triglycerids or neutral glycyl +ethers.<a id="FNanchor_230" href="#Footnote_230" class="fnanchor">[230]</a> +In natural animal and vegetable products, only the neutral salts are +found, the mono- and diglycerids resulting from artificial synthesis. +For this reason the prefix tri is not necessarily used in designating +the natural glycerids, stearin, for instance, meaning the same as tristearin.</p> + +<p><b>279. Principal Glycerids.</b>—The most important glycerids which +the analyst will find are the following:</p> + +<table class="spb1"> + <tbody><tr> + <td class="tdl">Olein,</td> + <td class="tdl_ws1">C₃H₅O(O.C₁₈H₃₃O)₃.</td> + </tr><tr> + <td class="tdl">Stearin,</td> + <td class="tdl_ws1">C₃H₅O(O.C₁₈H₃₅)₃.</td> + </tr><tr> + <td class="tdl">Palmitin,</td> + <td class="tdl_ws1">C₃H₅O(O.C₁₆H₃₁O)₃.</td> + </tr><tr> + <td class="tdl">Linolein,</td> + <td class="tdl_ws1">C₃H₅O(O.C₁₈H₃₁O)₃.</td> + </tr><tr> + <td class="tdl">Butyrin,</td> + <td class="tdl_ws1">C₃H₅O(O.C₄H₇O)₃.</td> + </tr> + </tbody> +</table> + +<p>Olein is the chief constituent of most oils; palmitin is found in palm +oil and many other natural glycerids; stearin is a leading constituent +of the fats of beeves and sheep, and butyrin is a characteristic +constituent of butter, which owes its flavor largely to this glycerid +and its nearly related concomitants.</p> + +<p id="P_280"><b>280. Extraction of Oils and Fats.</b>—Preparatory to a physical +and chemical study of the fats and oils is their separation from the +other organic matters with which they may be associated. In the case of +animal tissues this is usually accomplished by the application of heat. +<span class="pagenum"><a id="Page_311"></a>[Pg 311]</span> +The operation known as rendering may be conducted in many different +ways. For laboratory purposes, the animal tissues holding the fat +are placed in a convenient dish and a degree of heat applied which +will liquify all the fat particles and free them from their investing +membranes. The temperature employed should be as low as possible to +secure the desired effect, but fats can be subjected for some time to +a heat of a little more than 100°, without danger of decomposition. +The direct heat of a lamp, however, should not be applied, since it +is difficult to avoid too high a temperature at the point of contact +of the flame and dish. The dry heat of an air-bath or rendering in an +autoclave or by steam is preferable. The residual animal matter is +subjected to pressure and the combined liquid fat freed from foreign +matters by filtering through a jacket filter, which is kept at a +temperature above the solidifying point of the contents.</p> + +<p>On a large scale, as in rendering lard, the fat is separated by steam +in closed vats which are strong enough to withstand the steam pressure +employed. For analytical purposes it is best to extract the fat from +animal tissues in the manner described, since the action of solvents +is slow on fat particles enveloped in their containing membranes, and +the fats, when extracted, are liable to be contaminated with extraneous +matters. In dried and ground flesh meal, however, the fat may be +extracted with the usual solvents. For the quantitive determination of +fat in bones or flesh, the sample, as finely divided as possible, is +thoroughly dried, and the fat separated from an aliquot finely powdered +portion by extraction with chloroform, ether, or petroleum. The action +of anhydrous ether on dried and powdered animal matters is apparently +a continuous one. Dormeyer has shown that even after an extraction of +several months additional matter goes into solution.<a id="FNanchor_231" href="#Footnote_231" class="fnanchor">[231]</a> +The fat in such cases can be determined by saponification with +alcoholic potash and the estimation of the free fatty acids produced.</p> + +<p>From vegetable substances, such as seeds, the fat is extracted either +by pressure or by the use of solvents. For quantitive purposes, only +solvents are employed. The dry, finely ground material is exhausted +with anhydrous ether or petroleum spirit, in one of the convenient +<span class="pagenum"><a id="Page_312"></a>[Pg 312]</span> +forms of apparatus already described (<b><a href="#P_33">33->43</a></b>). In very +oily seeds great difficulty is experienced in securing a fine state +of subdivision suited to complete extraction. In such cases it is +advisable to conduct the process in two stages. In the first stage +the material, in coarse powder, is exhausted as far as possible and +the percentage of oil determined. The residue is then easily reduced +to a fine powder, in an aliquot part of which the remaining oil is +determined in the usual way.</p> + +<div class="figcenter smcap"> + <img id="FIG_79" src="images/fig79.jpg" alt="" width="400" height="484" > + <p class="center spb1">Fig. 79.—Oil Press.</p> +</div> + +<p>In securing oils for physical and chemical examination both pressure +and solution may be employed. The purest oils are secured by pressure +at a low temperature. To obtain anything like a good extraction some +sort of hydraulic pressure must be used. In this laboratory a press is +employed in which the first pressure is secured by a screw and this is +<span class="pagenum"><a id="Page_313"></a>[Pg 313]</span> +supplemented by hydraulic pressure in which glycerol is the +transmitting liquid. The construction of the press is shown in the +accompanying <a href="#FIG_79">figure</a>.</p> + +<p>The whole press is warmed to nearly 100°. The hot finely ground oily +material, enclosed in a cloth bag, is placed in the perforated cylinder +and compressed as firmly as possible by turning with the hands the +wheel shown at the top of the <a href="#FIG_79">figure</a>. The final +pressure is secured by the screw shown at the bottom of the figure +whereby a piston is driven into a cylinder containing glycerol. The +degree of pressure obtained is equal to 300 atmospheres.</p> + +<p>Even with the best laboratory hydraulic pressure not more than +two-thirds of the total oil contents of oleaginous seeds can be secured +and the process is totally inapplicable to securing the oil from +tissues when it exists in quantities of less than ten per cent. To get +practically all of the oil the best method is to extract with carefully +distilled petroleum of low boiling point.</p> + +<p>In the preparation of this reagent the petroleum ether of commerce, +containing bodies boiling at temperatures of from 35° to 80°, is +repeatedly fractioned by distillation until a product is obtained +which boils at from 45° to 60°. The distillation of this material +is conducted in a large flask heated with steam, furnished with a +column containing a number of separatory funnels and connected with an +appropriate condenser. The distillate is secured in a bottle packed +with broken ice, as shown in <a href="#FIG_80">Fig. 80</a>. A thermometer +suspended in the vapor of the petroleum serves to regulate the process. Too +much care to avoid accidents cannot be exercised in this operation. Not only +must steam be used in heating, but all flame and fire must be rigidly +excluded from the room in which the distillation takes place, and +the doors leading to other rooms where gas jets may be burning must +be kept closed. In the beginning of the process, as much as possible +of the petroleum boiling under 45° must be removed and rejected. The +distillation is then continued until the temperature rises above 60°. +The parts of the distillate saved between these temperatures are +redistilled under similar conditions. Other portions of the petroleum, +boiling at other temperatures, may be secured in the same way. The +<span class="pagenum"><a id="Page_314"></a>[Pg 314]</span> +products may be in a measure freed of unpleasant odors by redistilling +them from a mixture with lard. When used for quantitive purposes the +petroleum ether must leave no residue when evaporated at 100°.</p> + +<div class="figcenter smcap"> + <img id="FIG_80" src="images/fig80.jpg" alt="" width="400" height="453" > + <p class="center spb1">Fig. 80.—Apparatus for Fractional Distillation<br> of Petroleum Ether.</p> +</div> + +<p><b>281. Freeing Extracted Oils from Petroleum.</b>—The petroleum ether +which is used for extracting oils tends to give them an unpleasant odor +and flavor and its entire separation is a matter of some difficulty. +The greater part of the solvent may be recovered as described in +paragraph <b><a href="#P_43">43</a></b>. Heating the extracted oil for several hours in +thin layers, will remove the last traces of the solvent, but affords +<span class="pagenum"><a id="Page_315"></a>[Pg 315]</span> +opportunity for oxidation, especially in the case of drying oils. An +effective means of driving off the last traces of petroleum is to cause +a current of dry carbon dioxid to pass through the sample contained +in a cylinder and heated to a temperature of from 85° to 90°. The +atmosphere of the inert gas will preserve the oil from oxidation and +the sample will, as a rule, be found free of the petroleum odor after +about ten hours treatment. Ethyl ether or chloroform may be used +instead of petroleum, but these solvents act on other matters than +the glycerids, and the extract is therefore liable to be contaminated +with more impurities than when the petroleum ether is employed. Other +solvents for fats are carbon tetrachlorid, carbon disulfid, and +benzene. In general, petroleum ether should be employed in preference +to other solvents, except in the case of castor oil, which is +difficultly soluble in both petroleum and petroleum ethers.</p> + +<p><b>282. Freeing Fats Of Moisture.</b>—Any excess of water in glycerids +will accumulate at the bottom of the liquid sample and can be removed +by decanting the fat or separating it from the oil by any other +convenient method. The warm oil may be almost entirely freed of any +residual moisture by passing it through a dry filter paper in a jacket +funnel kept at a high temperature. A section showing the construction +of such a funnel with a folded filter paper in place, is shown in <a href="#FIG_81">Fig. 81</a>. +The final drying, when great exactness is required, is accomplished +in a vacuum, or in an atmosphere of inert gas, or in the cold in an +exsiccator over sulfuric acid. In drying, it is well to expose the +hot oil as little as possible to the action of the air. Wherever +convenient, it should be protected from oxidation by some inert gas or +a vacuum.</p> + +<p id="P_283"><b>283. Sampling for Analysis.</b>—It is a matter of some difficulty +to secure a representative sample of a fat or oil for analytical +purposes. The moisture in a fat is apt to be unevenly distributed, and +the sampling is to be accomplished in a manner to secure the greatest +possible uniformity. When the quantity of material is of considerable +quantity a trier may be used which will remove a cylindrical or partly +cylindrical mass from the whole length or depth. By securing several +<span class="pagenum"><a id="Page_316"></a>[Pg 316]</span> +subsamples of this kind, and well mixing them, an average sample of the +whole mass may be secured. Where the fat is found in different casks +or packages samples should be drawn from each as described above. The +subsamples are mixed together in weights corresponding to the different +casks from which they are taken and the mass obtained by this mixture +divided into three equal portions. Two of these parts are melted in a +dish at a temperature not exceeding 60°, with constant stirring, and +when fully liquid the third part is added. As a rule, the liquid fat +retains enough heat to melt the added quantity. As soon as the mixed +fats begin to grow pasty the mass is vigorously stirred to secure an +intimate mixture of the water and other foreign bodies.<a id="FNanchor_232" href="#Footnote_232" class="fnanchor">[232]</a></p> + +<div class="figcenter smcap"> + <img id="FIG_81" src="images/fig81.jpg" alt="" width="500" height="435" > + <p class="center spb1">Fig. 81.—Section Showing Construction of a Funnel<br> for Hot Filtration.</p> +</div> + +<p>In the case of butter fat the official chemists recommend that +subsamples be drawn from all parts of the package until about 500 grams +are secured. The portions thus drawn are to be perfectly melted in a +<span class="pagenum"><a id="Page_317"></a>[Pg 317]</span> +closed vessel at as low a temperature as possible, and when melted +the whole is to be shaken violently for some minutes till the mass is +homogeneous, and sufficiently solidified to prevent the separation of +the water and fat. A portion is then poured into the vessel from which +it is to be weighed for analysis, and this should nearly or quite fill +it. This sample should be kept in a cold place till analyzed.<a id="FNanchor_233" href="#Footnote_233" class="fnanchor">[233]</a></p> + +<p><b>284. Estimation of Water.</b>—In the official method for butter +fat, which may be applied to all kinds, about two grams are dried to +constant weight, at the temperature of boiling water, in a dish with +flat bottom, having a surface of at least twenty square centimeters.</p> + +<p>The use of clean dry sand or asbestos is admissible, and is necessary +if a dish with round bottom be employed.</p> + +<p>In the method recommended by Benedikt, about five grams of the sampled +fat are placed in a small flask or beaker and dried at 100° with +occasional stirring to bring the water to the surface.</p> + +<p>According to the method of Sonnenschein, the sample is placed in a +flask carrying a cork, with an arrangement of glass tubes, whereby a +current of dry air may be aspirated over the fat during the process +of drying. When the flask is properly fitted its weight is taken, the +fat put in and reweighed to get the exact amount. The fat is better +preserved by aspirating carbon dioxid instead of air.<a id="FNanchor_234" href="#Footnote_234" class="fnanchor">[234]</a> +The moisture may also be readily determined by drying on pumice stone, +as described in paragraph <b><a href="#P_26">26</a></b>. In this case it is well to conduct +the desiccation in vacuum or in an inert atmosphere to prevent oxidation.</p> + +<h3>PHYSICAL PROPERTIES OF FATS.</h3> + +<p id="P_285"><b>285. Specific Gravity.</b>—The specific gravity of an oil is +readily determined by a westphal balance (<b><a href="#P_53">53</a></b>), by a spindle, +by a sprengel tube, or more accurately by a pyknometer. The general +principles governing the conduct of the work have already been given +(<b><a href="#P_48">48-59</a></b>). The methods described for determining the density of +sugar solutions are essentially the same as those used for oils, but it +is to be remembered that oils and fats are lighter than water and the +<span class="pagenum"><a id="Page_318"></a>[Pg 318]</span> +graduation of the sinkers for the hydrostatic balance, and the +spindles for direct determination must be for such lighter liquids. +The necessity of determining the density of a fat at a temperature +above its melting point is manifest, and for this reason the use of +the pyknometer at a high temperature (40° to 100°) is to be preferred +to all the other processes, in the case of fats which are solid at +temperatures below 25°.</p> + +<div class="figcenter smcap"> + <img id="FIG_82" src="images/fig82.jpg" alt="" width="500" height="524" > + <p class="center spb1">Fig. 82.—Balance and Westphal Sinker.</p> +</div> + +<p>When great delicacy of manipulation is desired, combined with +rapid work, an analytical balance and westphal sinker may be used +conjointly.<a id="FNanchor_235" href="#Footnote_235" class="fnanchor">[235]</a> +In this case it is well to have two or three sinkers graduated for +20°, 25°, and 40°, respectively. Nearly all fats, when melted and +cooled to 40°, remain in a liquid state long enough to determine their +density. The sinkers are provided with delicate thermometers, and the +temperature, which at the beginning is a little above the degree at +which the sinker is graduated, is allowed to fall to just that degree, +when the equilibrium is secured in the usual manner. The sinker is +<span class="pagenum"><a id="Page_319"></a>[Pg 319]</span> +conveniently made to displace just five grams of distilled water at the +temperature of graduation, but it is evident that a round number is not +necessary, but only convenient for calculation.</p> + +<p><b>286. Expression of Specific Gravity.</b>—Much confusion arises +in the study of data of densities because the temperatures at which +the determinations are made are not expressed. The absolute specific +gravity would be a comparison of the weight of the object at 4°, with +water at the same temperature. It is evident that such determinations +are not always convenient, and for this reason the determinations of +density are usually made at other temperatures.</p> + +<p>In the case of a sinker, which at 35° displaces exactly five grams of +water, the following statements may be made: One cubic centimeter of +water at 35° weighs 0.994098 gram. The volume of a sinker displacing +five grams of water at that temperature is therefore 5.0297 cubic +centimeters. This volume of water at 4° weighs 5.0297 grams. In a given +case the sinker placed in an oil at 35° is found to displace a weight +equal to 4.5725 grams corresponding to a specific gravity of 35°/35° += 0.9145. From the foregoing data the following tabular summary is +constructed:</p> + +<table class="spb1"> + <tbody><tr> + <td class="tdl">Weight</td> + <td class="tdl_wsp">of</td> + <td class="tdl_wsp">5.0287</td> + <td class="tdl_wsp">cubic</td> + <td class="tdl_wsp">centimeters</td> + <td class="tdl_wsp">of</td> + <td class="tdl_wsp">oil</td> + <td class="tdl_wsp">at 35°,</td> + <td class="tdl_wsp">4.5725</td> + <td class="tdl_wsp">grams.</td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdc">”</td> + <td class="tdl_wsp">5.0297</td> + <td class="tdc">”</td> + <td class="tdc">”</td> + <td class="tdc">”</td> + <td class="tdl_wsp">water</td> + <td class="tdl_wsp">at 35°,</td> + <td class="tdl_wsp">5.0000</td> + <td class="tdc">”</td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdc">”</td> + <td class="tdl_wsp">5.0297</td> + <td class="tdc">”</td> + <td class="tdc">”</td> + <td class="tdc">”</td> + <td class="tdc">”</td> + <td class="tdl_wsp"> ” 4°,</td> + <td class="tdl_wsp">5.0297</td> + <td class="tdc">”</td> + </tr> + </tbody> +</table> + +<table class="spb1"> + <tbody><tr> + <td class="tdl">Relative</td> + <td class="tdl_wsp">weight</td> + <td class="tdl_wsp">of</td> + <td class="tdl_wsp">oil</td> + <td class="tdl_wsp">at</td> + <td class="tdl_wsp">35°,</td> + <td class="tdl_wsp">to</td> + <td class="tdl_wsp">water</td> + <td class="tdl_wsp">at</td> + <td class="tdl_wsp">35°,</td> + <td class="tdl_wsp">0.9145</td> + <td class="tdl_wsp">grams.</td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdc">”</td> + <td class="tdc">”</td> + <td class="tdc">”</td> + <td class="tdc">”</td> + <td class="tdl_wsp">35°,</td> + <td class="tdc">”</td> + <td class="tdc">”</td> + <td class="tdc">”</td> + <td class="tdl_wsp"> 4°,</td> + <td class="tdl_wsp">0.9092</td> + <td class="tdc">”</td> + </tr> + </tbody> +</table> + +<p><b>287. Coefficient of Expansion of Oils.</b>—Oils and fats of every +kind have almost the same coefficient of expansion with increasing +temperature. The coefficient of expansion is usually calculated by the +formula</p> + +<table class="spb1 fs_110"> + <tbody><tr> + <td class="tdl" rowspan="2">δ = </td> + <td class="tdc bb"><i>D</i>₀ - <i>D</i>₀ʹ</td> + </tr><tr> + <td class="tdc">(<i>tʹ</i> - <i>t</i>)<i>D</i>₀</td> + </tr> + </tbody> +</table> + +<p class="no-indent">in which δ represents the coefficient of +expansion, <i>D</i>₀ the density at the lowest temperature, <i>D</i>₀ʹ +the density at the highest temperature, <i>t</i> the lowest, and +<i>tʹ</i> the highest temperatures.</p> + +<p>In the investigations made by Crampton it was shown that the formula +would be more accurate, written as follows:<a id="FNanchor_236" href="#Footnote_236" class="fnanchor">[236]</a></p> + +<table class="spb1 fs_110"> + <tbody><tr> + <td class="tdl" rowspan="3">δ = <br> </td> + <td class="tdc bb"><i>D</i>₀ - <i>D</i>₀ʹ</td> + </tr><tr> + <td class="tdc_top">(<i>tʹ</i> - <i>t</i>) × <span class="u"><i>D</i>₀ + <i>D</i>₀ʹ</span></td> + </tr><tr> + <td class="tdl_ws2"><span class="ws2"> 2</span></td> + </tr> + </tbody> +</table> + +<p><span class="pagenum"><a id="Page_320"></a>[Pg 320]</span> +The absolute densities can be calculated from the formula Δ = δ + +<i>K</i>, in which Δ represents the coefficient of absolute expansion, +δ the apparent coefficient of expansions observed in glass vessels, and +<i>K</i> the cubical coefficient of expansion of the glass vessel. The +mean absolute coefficient of expansion for fats and oils, for 1° as +determined by experiment, is almost exactly 0.0008, and the apparent +coefficient of expansion nearly 0.00077.<a id="FNanchor_237" href="#Footnote_237" class="fnanchor">[237]</a></p> + +<p><b>288. Standard of Comparison.</b>—In expressing specific gravities +it is advisable to refer them always to water at 4°. The temperature at +which the observation is made should also be given. Thus the expression +of the specific gravity of lard, determined at different temperatures, +is made as follows:</p> + +<table class="spb1 fs_110"> + <tbody><tr> + <td class="tdl_ws1" colspan="2">15°.5</td> + </tr><tr> + <td class="tdl"><i>d</i> —— = </td> + <td class="tdc">0.89679;</td> + </tr><tr> + <td class="tdl_ws1" colspan="2"> 4°</td> + </tr> + </tbody> +</table> + +<table class="spb1 fs_110"> + <tbody><tr> + <td class="tdl_ws1" colspan="2">40°</td> + </tr><tr> + <td class="tdl"><i>d</i> —— = </td> + <td class="tdc">0.91181;</td> + </tr><tr> + <td class="tdl_ws1" colspan="2"> 4°</td> + </tr> + </tbody> +</table> + +<table class="spb1 fs_110"> + <tbody><tr> + <td class="tdl_ws1" colspan="2">100°</td> + </tr><tr> + <td class="tdl">and <i>d</i> —— = </td> + <td class="tdc">0.85997,</td> + </tr><tr> + <td class="tdl_ws1" colspan="2"> 4°</td> + </tr> + </tbody> +</table> + +<p class="no-indent">indicating the relative weights of the sample under examination at +15°.5, 40°, and 100°, respectively, to water at 4°.</p> + +<p><b>289. Densities of Common Fats and Oils.</b>—It is convenient to +have at hand some of the data representing the densities of common fats +and oils, and the following numbers are from results of determinations +made in this laboratory:<a id="FNanchor_238" href="#Footnote_238" class="fnanchor">[238]</a></p> + +<table class="spb1"> + <thead><tr class="fs_90"> + <th class="tdr" colspan="3">15°.5</th> + <th class="tdr" colspan="2">40°</th> + <th class="tdr" colspan="2">100°</th> + </tr><tr> + <th class="tdc">Temperature.</th> + <th class="tdc"><i>d</i> =</th> + <th class="tdc">—.</th> + <th class="tdc"> <i>d</i> =</th> + <th class="tdc">—.</th> + <th class="tdc"> <i>d</i> =</th> + <th class="tdc">—.</th> + </tr><tr class="fs_90"> + <th class="tdr" colspan="3">4°  </th> + <th class="tdr" colspan="2">4°  </th> + <th class="tdr" colspan="2">4°  </th> + </tr></thead> + <tbody><tr> + <td class="tdl">Leaf lard</td> + <td class="tdr_wsp" colspan="2">0.91181</td> + <td class="tdr_wsp" colspan="2">0.89679</td> + <td class="tdr_wsp" colspan="2">0.85997</td> + </tr><tr> + <td class="tdl">Lard stearin</td> + <td class="tdr_wsp" colspan="2">0.90965</td> + <td class="tdr_wsp" colspan="2"> 0.89443</td> + <td class="tdr_wsp" colspan="2"> 0.85750</td> + </tr><tr> + <td class="tdl">Oleostearin</td> + <td class="tdr_wsp" colspan="2">0.90714</td> + <td class="tdr_wsp" colspan="2">0.89223</td> + <td class="tdr_wsp" colspan="2">0.85572</td> + </tr><tr> + <td class="tdl">Crude cottonseed oil  </td> + <td class="tdr_wsp" colspan="2">0.92016</td> + <td class="tdr_wsp" colspan="2">0.90486</td> + <td class="tdr_wsp" colspan="2">0.86739</td> + </tr><tr> + <td class="tdl">Summer  ”<span class="ws2"> ”</span></td> + <td class="tdr_wsp" colspan="2">0.92055</td> + <td class="tdr_wsp" colspan="2">0.90496</td> + <td class="tdr_wsp" colspan="2">0.86681</td> + </tr><tr> + <td class="tdl">Winter   ”<span class="ws2"> ”</span></td> + <td class="tdr_wsp" colspan="2">0.92179</td> + <td class="tdr_wsp" colspan="2">0.90612</td> + <td class="tdr_wsp" colspan="2">0.86774</td> + </tr><tr> + <td class="tdl">Refined  ”<span class="ws2"> ”</span></td> + <td class="tdr_wsp" colspan="2">0.92150</td> + <td class="tdr_wsp" colspan="2">0.90573</td> + <td class="tdr_wsp" colspan="2">0.86714</td> + </tr><tr> + <td class="tdl">Compound lard ”</td> + <td class="tdr_wsp" colspan="2">0.91515</td> + <td class="tdr_wsp" colspan="2">0.90000</td> + <td class="tdr_wsp" colspan="2">0.86289</td> + </tr><tr> + <td class="tdl">Olive oil</td> + <td class="tdr_wsp" colspan="2">0.91505</td> + <td class="tdr_wsp" colspan="2">0.89965</td> + <td class="tdr_wsp" colspan="2">0.86168</td> + </tr> + </tbody> +</table> + +<p><b>290. Melting Point.</b>—The temperature at which fats become +sensibly liquid is a physical characteristic of some importance. +Unfortunately, the line of demarcation between the solid and liquid +states of this class of bodies is not very clear. Few of them pass +<i>per saltum</i> from one state to the other. In most cases there is +a gradual transition, which, between its initial and final points, may +show a difference of several degrees in temperature. It has been noted, +<span class="pagenum"><a id="Page_321"></a>[Pg 321]</span> +further, that fats recently melted behave differently from those which +have been solid for several hours. For this reason it is advisable, in +preparing glycerids for the determination of their melting point, to +fuse them the day before the examination is to be made. The temperature +at which a glycerid passes from a liquid to a solid state is usually +higher than that at which it resumes its solid form. If, however, the +change of temperature could be made with extreme slowness, exposing +the sample for many hours at near its critical temperature, these +differences would be much less marked.</p> + +<p>Many methods have been devised for determining the melting point of +fats, and none has been found that is satisfactory in every respect. In +some cases the moment at which fluidity occurs is assumed to be that +one when the small sample loses its opalescence and becomes clear. +In other cases the moment of fluidity is determined by the change of +shape of the sample or by observing the common phenomena presented by +a liquid body. In still other cases, the point at which the sample +becomes fluid is determined by the automatic completion of an electric +circuit, which is indicated by the ringing of a bell. This latter +process has been found very misleading in our experience. Only a few of +the proposed methods seem to demand attention here, and some of those, +depending on the visible liquefaction of a small quantity of the fat or +based on the physical property, possessed by all liquids when removed +from external stress, of assuming a spheroidal state will be described. +Other methods which may demand attention in any particular case may be +found in the works cited.<a id="FNanchor_239" href="#Footnote_239" class="fnanchor">[239]</a></p> + +<p><b>291. Determination in a Capillary Tube.</b>—A capillary tube +is dipped into the melted fat and when filled one end of the tube +is sealed in the lamp and it is then put aside in a cool place for +twenty-four hours. At the end of this time the tube is tied to the bulb +of a delicate thermometer the length used or filled with fat being of +the same length as the thermometer bulb. The thermometer and attached +fat are placed in water, oil, or other transparent media, and gently +warmed until the capillary column of fat becomes transparent. At this +moment the thermometric reading is made and entered as the melting +<span class="pagenum"><a id="Page_322"></a>[Pg 322]</span> +point of the fat. In comparative determinations the same length of +time should be observed in heating, otherwise discordant results +will be obtained. As in all other methods, the resulting members are +comparative and not absolute points of fusion, and the data secured by +two observers on the same sample may not agree, if different methods of +preparing the fat and different rates of fusion have been employed.</p> + +<div class="figleft smcap"> + <img id="FIG_83" src="images/fig83.jpg" alt="" width="100" height="237" > + <p class="center">Fig. 83.—<br>Melting<br> Point<br> Tubes.</p> +</div> + +<p>Several modifications of the method just described are practiced, and +perhaps with advantage in some cases. In one of these a small particle +of the fat is solidified in a bulb blown on a small tube, as indicated +in <a href="#FIG_83">Fig. 83</a>, tube <i>a</i>. The tube, in an +upright position, is heated in a convenient bath until the particle +of fat just begins to run assuming soon the position shown in tube +<i>b</i>. This temperature is determined by a thermometer, whose bulb +is kept in contact with the part of the observation tube containing +the fat particle. The rise of temperature is continued until the fat +collected at the bottom of the bulb is entirely transparent. This is +called the point of complete fusion.<a id="FNanchor_240" href="#Footnote_240" class="fnanchor">[240]</a></p> + +<p>Pohl covers the bulb of a thermometer with a thin film of fat, and the +instrument is then fixed in a test tube, in such a way as not to touch +the bottom, and the film of fat warmed by the air-bath until it fuses +and collects in a droplet at the end of the thermometer bulb.<a id="FNanchor_241" href="#Footnote_241" class="fnanchor">[241]</a></p> + +<p>Carr has modified this process by inserting the thermometer in a round +flask in such a way that the bulb of the thermometer is as nearly +as possible in the center. By this device the heating through the +intervening air is more regular and more readily controlled.<a id="FNanchor_242" href="#Footnote_242" class="fnanchor">[242]</a></p> + +<p>A particle of fat placed on the surface of clean mercury will melt +when the mercury is raised to the proper temperature. Where larger +quantities of the fat are employed, a small shot or pellet of mercury +may be placed upon the surface and the whole warmed until the metal +<span class="pagenum"><a id="Page_323"></a>[Pg 323]</span> +sinks. Of the above noted methods, the analyst will find some form +of capillary tube or the use of a film of the fat on the bulb of a +thermometer the most satisfactory.<a id="FNanchor_243" href="#Footnote_243" class="fnanchor">[243]</a></p> + +<p>Hehner and Angell have modified the sinking point method by increasing +the size of the sinker without a corresponding increase in weight. +This is accomplished by blowing a small pear-shaped float, nearly +one centimeter in diameter and about two long. The stem of the pear +is drawn out and broken off, and while the bulb is still warm, the +open end of the stem is held in mercury, and a small quantity of this +substance, sufficient in amount to cause the float to sink slowly +through a melted fat, is introduced into the bulb of the apparatus +and the stem sealed. The whole bulb should displace about one cubic +centimeter of liquid and weigh, after filling with mercury, about +three and four-tenths grams. In conducting the experiment about thirty +grams of the dry melted fat are placed in a large test tube and cooled +by immersing the tube in water at a temperature of 15°. The tube +containing the solidified fat is placed in a bath of cold water and the +sinker is placed in the center of the surface of the fat. The bath is +slowly heated until the float disappears. The temperature of the bath +is read just as the bulb part of the float disappears. The method is +recommended especially by the authors for butter fat investigations.<a id="FNanchor_244" href="#Footnote_244" class="fnanchor">[244]</a></p> + +<p><b>298. Melting Point Determined by the Spheroidal State.</b>—The +method described by the author, depending on the assumption of the +spheroidal state of a particle of liquid removed from all external +stress, has been found quite satisfactory in this laboratory, and has +been adopted by the official chemists.<a id="FNanchor_245" href="#Footnote_245" class="fnanchor">[245]</a> +In the preparation of the apparatus there are required:</p> + +<p>(<i>a</i>) a piece of ice floating in distilled water that has been +recently boiled, and (<i>b</i>) a mixture of alcohol and water of the +same specific gravity as the fat to be examined. This is prepared by +boiling distilled water and ninety-five per cent alcohol for a few +minutes to remove the gases which they may hold in solution. While +still hot, the water is poured into the test tube described below until +it is nearly half full. The test tube is then nearly filled with the +hot alcohol, which is carefully poured down the side of the inclined +tube to avoid too much mixing. If the alcohol is not added until the +<span class="pagenum"><a id="Page_324"></a>[Pg 324]</span> +water has cooled, the mixture will contain so many air bubbles as to +be unfit for use. These bubbles will gather on the disk of fat as the +temperature rises and finally force it to the top.</p> + +<div class="figcenter smcap"> + <img id="FIG_84" src="images/fig84.jpg" alt="" width="300" height="497" > + <p class="center spb1">Fig. 84.—Apparatus for the<br> Determination of Melting point.</p> +</div> + +<p>The apparatus for determining the melting point is shown in <a href="#FIG_84">Fig. 84</a>, +and consists of (<i>a</i>) an accurate thermometer reading +easily tenths of a degree; (<i>b</i>) a cathetometer for reading the +thermometer (but this may be done with an eye-glass if held steadily +and properly adjusted); (<i>c</i>) a thermometer; (<i>d</i>) a tall +beaker, thirty-five centimeters high and ten in diameter; (<i>e</i>) +a test tube thirty centimeters long and three and a half in diameter; +(<i>f</i>) a stand for supporting the apparatus; (<i>g</i>) some method +of stirring the water in the beaker (for example, a blowing bulb of +rubber, and a bent glass tube extending to near the bottom of the beaker).</p> + +<p>The disks of fat are prepared as follows: The melted and filtered fat +is allowed to fall from a dropping tube from a height of about twenty +cubic centimeters on a smooth piece of ice floating in recently boiled +distilled water. The disks thus formed are from one to one and a half +centimeters in diameter and weigh about 200 milligrams. By pressing the +ice under the water the disks are made to float on the surface, whence +<span class="pagenum"><a id="Page_325"></a>[Pg 325]</span> +they are easily removed with a steel spatula, which should be cooled in +the ice water before using. They should be prepared a day or at least a +few hours before using.</p> + +<p>The test tube containing the alcohol and water is placed in a tall +beaker, containing water and ice, until cold. The disk of fat is then +dropped into the tube from the spatula, and at once sinks until it +reaches a part of the tube where the density of the alcohol-water is +exactly equivalent to its own. Here it remains at rest and free from +the action of any force save that inherent in its own molecules.</p> + +<p>The delicate thermometer is placed in the test tube and lowered until +the bulb is just above the disk. In order to secure an even temperature +in all parts of the alcohol mixture in the vicinity of the disk, the +thermometer is gently moved from time to time in a circularly pendulous +manner.</p> + +<p>The disk having been placed in position, the water in the beaker is +slowly heated, and kept constantly stirred by means of the blowing +apparatus already described.</p> + +<p>When the temperature of the alcohol-water mixture rises to about +6° below the melting point, the disk of fat begins to shrivel, and +gradually rolls up into an irregular mass.</p> + +<p>The thermometer is now lowered until the fat particle is even with the +center of the bulb. The bulb of the thermometer should be small, so as +to indicate only the temperature of the mixture near the fat. A gentle +rotatory movement from time to time should be given to the thermometer +bulb. The rise of temperature should be so regulated that the last +2° of increment require about ten minutes. The mass of fat gradually +approaches the form of a sphere, and when it is sensibly so the reading +of the thermometer is to be made. As soon as the temperature is taken +the test tube is removed from the bath and placed again in the cooler. +A second tube, containing alcohol and water, is at once placed in the +bath. The test tube (ice water having been used as a cooler) is of +low enough temperature to cool the bath sufficiently. After the first +determination, which should be only a trial, the temperature of the +bath should be so regulated as to reach a maximum of about 1°.5 above +the melting point of the fat under examination. +<span class="pagenum"><a id="Page_326"></a>[Pg 326]</span></p> + +<p>The edge of the disk should not be allowed to touch the sides of the +tube. This accident rarely happens, but in case it should take place, +and the disk adhere to the sides of the tube, a new trial should be +made.</p> + +<p>Triplicate determinations should be made, and the second and third +results should show a near agreement.</p> + +<p class="center spa1"><i>Example.</i>—Melting point of sample of butter:</p> + +<table class="spb1"> + <tbody><tr> + <td class="tdl"> </td> + <td class="tdr">Degrees.</td> + </tr><tr> + <td class="tdl">First trial</td> + <td class="tdc">33.15</td> + </tr><tr> + <td class="tdl">Second trial<span class="ws3"> </span></td> + <td class="tdc">33.05</td> + </tr><tr> + <td class="tdl">Third trial</td> + <td class="tdc">33.00</td> + </tr> + </tbody> +</table> + +<p>The fatty acids, being soluble in alcohol, cannot be treated as the +ordinary glycerids. But even those glycerids which are slightly soluble +in alcohol may be subjected to the above treatment without fear of +experiencing any grave disturbance of the fusing points.</p> + +<p><b>293. Solidifying Point.</b>—The temperature at which a fat shows +incipient solidification is usually lower than the point of fusion. +The same difficulties are encountered in determining the temperature +of solidification as are presented in observing the true melting +point. The passage from a transparent liquid to an opaque solid is +gradual, showing all the phases of turbidity from beginning opalescence +to complete opacity. The best the analyst can do is to determine, +as accurately as possible, the temperature at which the more solid +glycerids of the mixture begin to form definite crystals. This point is +affected to a marked degree by the element of time. A fat cooled just +below its melting point will become solid after hours, or days, whereas +it could be quickly cooled far below that temperature and still be limpid.</p> + +<p>The methods of observation are the same for the glycerids and fatty +acids, and the general process of determination is sufficiently set +forth in the following description of the method as used in this +laboratory.<a id="FNanchor_246" href="#Footnote_246" class="fnanchor">[246]</a></p> + +<div class="figleft smcap"> + <img id="FIG_85" src="images/fig85.jpg" alt="" width="200" height="498" > + <p class="center">Fig. 85.—Apparatus<br> for Determining<br> Crystallizing Point.</p> +</div> + +<p>The melted fat or fat acid is placed in a test tube contained in a +large bottle, which serves as a jacket to protect the tube from sudden +or violent changes of temperature. The efficiency of the jacket may be +<span class="pagenum"><a id="Page_327"></a>[Pg 327]</span> +increased by exhausting the air therefrom, as in the apparatus for +determining the heat of bromination, hereafter described. A very +delicate thermometer, graduated in tenths of a degree, and having a +long bulb, is employed. By means of the reading glass, the reading can +be made in twentieths of a degree. The arrangement of the apparatus +is shown in <a href="#FIG_85">Fig. 85</a>. The test tube is nearly +filled with the melted matter. The bottom of the jacket should be +gently warmed to prevent a too rapid congelation in the bottom of the +test tube containing the melted fat, and the tube is to be so placed +as to leave an air space between it and the bottom of the bottle. The +thermometer is suspended in such a manner as to have the bulb as nearly +as possible in the center of the melted fat. The thermometer should +be protected from air currents and should be kept perfectly still. In +case the congealing point is lower than room temperature the jacket +may be immersed in a cooling mixture, the temperature of which is only +slightly below the freezing point of the fatty mass.</p> + +<p>When crystals of fat begin to form, the descent of the mercury in the +stem of the thermometer will become very slow and finally reach a +minimum, which should be noted. As the crystallization extends inwards +and approaches the bulb of the thermometer a point will be reached when +the mercury begins to rise. At this time the partially crystallized +mass should be vigorously stirred with the thermometer and again left +<span class="pagenum"><a id="Page_328"></a>[Pg 328]</span> +at rest in as nearly, the original position as possible. By this +operation the mercury will be made to rise and its maximum position +should be noted as the true crystallizing point of the whole mass. +In comparing different samples, it is important that the elements of +time in which the first crystallization takes place should be kept, as +nearly as possible, the same. A unit of one hour in cooling the mixture +from a temperature just above its point of fusion until the incipient +crystallization is noticed, is a convenient one for glycerids and for +fat acids.</p> + +<p><b>294. Determination of Refractive Power.</b>—The property of +refracting light is possessed by fats in different degrees and these +differences are of great help in analytical work. The examination may +be made by the simple refractometer of Abbe or Bertrand, or by the more +elaborate apparatus of Pulfrich.</p> + +<p>The comparative refractive power of fats can also be observed by +means of the oleorefractometer of Amagat-Jean or the differential +refractometer of Zune.<a id="FNanchor_247" href="#Footnote_247" class="fnanchor">[247]</a></p> + +<p>For details of the construction of these apparatus, with a description +of the optical principles on which they are based, the papers above +cited may be consulted. In this laboratory the instruments which +have been employed are three in number, <i>viz.</i>, Abbe’s small +refractometer, Pulfrich’s refractometer using yellow light, and the +oleorefractometer of Amagat-Jean. A brief description of the methods +of manipulating these instruments is all that can be attempted in this +manual.</p> + +<p><b>295. Refractive Index.</b>—Refractive index is an expression +employed to characterize the measurement of the degree of deflection +caused in a ray of light in passing from one transparent medium into +another. It is the quotient of the sine of the angle of the incident, +divided by the sine of the angle of the refracted ray.</p> + +<p>In the case of oils which remain liquid at room temperatures, the +determinations can be made without the aid of any device to maintain +liquidity. In the case of fat which becomes solid at ordinary room +temperatures, the determination must either be made in a room +artificially warmed or the apparatus must have some device, as in the +<span class="pagenum"><a id="Page_329"></a>[Pg 329]</span> +later instruments of Abbe and Pulfrich, and in the apparatus of +Amagat-Jean, whereby the sample under examination can be maintained +in a transparent condition. In each case the accuracy of the apparatus +should be tested by pure water, the refractive index of which at 18° +is 1.333. The refractive index is either read directly on the scale +as in Abbe’s instrument, or calculated from the angles measured as in +Pulfrich’s apparatus.</p> + +<div class="figcenter smcap"> + <img id="FIG_86" src="images/fig86.jpg" alt="" width="400" height="487" > + <p class="center spb1">Fig. 86.—Abbe’s Refractometer.</p> +</div> + +<p><b>296. Abbe’s Refractometer.</b>—For practical use the small +instrument invented by Abbe will be found sufficient. The one which has +been in use for many years in this laboratory is shown in <a href="#FIG_86">Fig. 86</a>. +The illustration represents the apparatus in the position preliminary to +reading the index. In preparing the sample of oil for observation the +instrument is turned on its axis until the prisms between which the +oil is placed assume a horizontal position, as is seen in <a href="#FIG_87">Fig. 87</a>. +The movable prism is unfastened and laid aside, the fixed prism covered +with a rectangular shaped piece of tissue paper on which one or two +drops of the oil are placed. The movable prism is replaced in such a +manner as to secure a complete separation of the two prisms by the film +of oiled tissue paper. A little practice will enable the analyst to +secure this result.</p> + +<p>After the paper disk holding the fat is secured by replacing the upper +prism, the apparatus is placed in its normal position and the index +moved until the light directed through the apparatus by the mirror +shows the field of vision divided into dark and light portions. The +dispersion apparatus is now turned until the rainbow colors on the part +between the dark and light fields have disappeared. Before doing this, +however, the telescope, the eyepiece of the apparatus, is so adjusted +<span class="pagenum"><a id="Page_330"></a>[Pg 330]</span> +as to bring the cross lines of the field of vision distinctly into +focus. The index of the apparatus is now moved back and forth until the +line of the two fields of vision falls exactly at the intersection of +the cross lines. The refractive index of the fat under examination is +then read directly upon the scale by means of a small magnifying glass. +To check the accuracy of the first reading, the dispersion apparatus +should be turned through an angle of 180° until the colors have again +disappeared, and, after adjustment, the scale of the instrument again +read. These two readings should nearly coincide, and their mean is the +true reading of the fat under examination.</p> + +<div class="figcenter smcap"> + <img id="FIG_87" src="images/fig87.jpg" alt="" width="600" height="408" > + <p class="center spb1">Fig. 87.—Charging Position of Refractometer.</p> +</div> + +<p>For butter fats the apparatus should be kept in a warm place, the +temperature of which does not fall below 30°. For reducing the results +obtained to a standard temperature, say 25°, the factor 0.000176 may be +used. As the temperature rises the refractive index falls.</p> + +<p class="blockquot"><i>Example.</i>—Refractive index of a butter fat +determined at 32°.4 = 1.4540, reduced to 25° as follows: 32.4 -25 = +7.4; 0.000176 × 7.4 = 0.0013; then 1.4540 + 0.0013 = 1.4553.</p> + +<p><span class="pagenum"><a id="Page_331"></a>[Pg 331]</span> +The instrument used should be set with distilled water at 18°, the +theoretical refractive index of water at that temperature being 1.333. +In the determination above given, the refractive index of pure water +measured 1.3300; hence the above numbers should be corrected for theory +by the addition of 0.0030, making the corrected index of the butter fat +mentioned at the temperature given, 1.4583.</p> + +<p><b>297. Pulfrich’s Refractometer.</b>—For exact scientific +measurements, Pulfrich’s apparatus has given here entire satisfaction. +In this instrument a larger quantity of the oil is required than for +the abbe, and this quantity is held in a cylindrical glass vessel luted +to the top of the prism. The method of accomplishing this and also an +illustration of the refraction of the rays of light are shown in <a href="#FIG_88">Fig. 88</a>.</p> + +<div class="figcenter smcap"> + <img id="FIG_88" src="images/fig88.jpg" alt="" width="300" height="238" > + <p class="center spb1">Fig. 88.—Prism of Pulfrich’s<br> Refractometer.</p> +</div> + +<p>The angle <i>i</i> is measured by a divided circle read with the aid of +a small telescope. The index of the prism of highly refractive glass +<i>N</i> is known. The oil is seen at <i>n</i>. The light used is the +yellow sodium ray (<i>D</i>). From the observed angle the refractive +index of n is calculated from the formula</p> + +<table class="spb1 fs_120"> + <tbody><tr> + <td class="tdl"><i>n</i> = </td> + <td class="tdc">√</td> + <td class="tdc bt"> <i>N</i>² - sin²<i>i</i>.</td> + </tr> + </tbody> +</table> + +<p>For convenience the values of <i>n</i> for all usual values of <i>i</i> +are computed once for all and arranged for use in tabular form. The +latest model of Pulfrich’s apparatus, arranged both for liquid and +solid bodies, and also for spectrometric observation is shown in <a href="#FIG_89">Fig. 89</a>.</p> + +<p>When the sodium light is used it is placed behind the apparatus and +the light is collected and reflected on the refractive prism by the +lens <i>N</i>. Through <i>H</i> and <i>G</i> is secured the micrometric +reading of the angle on the scale <i>D</i> by means of the telescopic +arrangement <i>F E</i>. For regulating the temperature of the oil and +adjacent parts, a stream of water at any desired temperature is made to +circulate through <i>L</i> and <i>S</i> in the direction indicated by +the arrows. The manner in which this is accomplished is shown in the +cross section of that part of the apparatus as indicated in <a href="#FIG_90">Fig. 90</a>. +<span class="pagenum"><a id="Page_332"></a>[Pg 332]</span></p> + +<div class="figcenter smcap"> + <img id="FIG_89" src="images/fig89.jpg" alt="" width="300" height="502" > + <p class="center spb1">Fig. 89.—Pulfrich’s New Refractometer.</p> +</div> +<p><span class="pagenum"><a id="Page_333"></a>[Pg 333]</span></p> + +<div class="figcontainer smcap"> + <div class="figsub"> + <img id="FIG_90" src="images/fig90.jpg" alt="" width="150" height="392" > + <p class="center">Fig. 90.—<br>Heating Apparatus<br>for Pulfrich’s<br>Refractometer.</p> + </div> + <div id="FIG_91" class="figsub"> + <img src="images/fig91.jpg" alt="" width="300" height="397" > + <p class="center">Fig. 91.—Spectrometer Attachment.</p> + </div> +</div> + +<p>For further details of the construction and operation of the apparatus +the original description may be consulted.<a id="FNanchor_248" href="#Footnote_248" class="fnanchor">[248]</a></p> + +<p>In case a spectrometric observation is desired the <i>H</i> ray, for +instance, is produced by the geissler tube <i>Q</i>, <a href="#FIG_91">Fig. 91</a>. +The light is concentrated and thrown upon the refractive prism by the lens +<i>P</i>, the lens <i>N</i>, <a href="#FIG_89">Fig. 89</a>, being removed +for this purpose.</p> + +<p>Tables, for correcting the dispersion and for calculating the indices +for each angle and fraction thereof, and for corrections peculiar to +the apparatus, accompany each instrument.</p> + +<p><b>298. Refractive Indices of some Common Oils.</b>—The following +<span class="pagenum"><a id="Page_334"></a>[Pg 334]</span> +numbers show the refractive indices obtained by Long for some of the +more common oils. The light used was the yellow ray of the sodium +flame.<a id="FNanchor_249" href="#Footnote_249" class="fnanchor">[249]</a></p> + +<table class="spb1"> + <thead><tr> + <th class="tdc" colspan="2">Name.</th> + <th class="tdc">Temperature.</th> + <th class="tdc"> Refractive <br>index.</th> + <th class="tdc"> Calculated<br>for 25°.</th> + </tr></thead> + <tbody><tr> + <td class="tdl" colspan="2">Olive oil (France)</td> + <td class="tdc">26°.6</td> + <td class="tdr_wsp">1.4673</td> + <td class="tdr_wsp">1.4677</td> + </tr><tr> + <td class="tdl" colspan="2">  ”  ” (California)</td> + <td class="tdc">25°.4</td> + <td class="tdr_wsp">1.4677</td> + <td class="tdr_wsp">1.4678</td> + </tr><tr> + <td class="tdl">Cottonseed</td> + <td class="tdl_wsp">oil</td> + <td class="tdc">24°.8</td> + <td class="tdr_wsp">1.4722</td> + <td class="tdr_wsp">1.4721</td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdl_ws1">”</td> + <td class="tdc">26°.3</td> + <td class="tdr_wsp">1.4703</td> + <td class="tdr_wsp">1.4709</td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdl_ws1">”</td> + <td class="tdc">25°.3</td> + <td class="tdr_wsp">1.4718</td> + <td class="tdr_wsp">1.4719</td> + </tr><tr> + <td class="tdl">Sesamé</td> + <td class="tdl_wsp">oil</td> + <td class="tdc">24°.8</td> + <td class="tdr_wsp">1.4728</td> + <td class="tdr_wsp">1.4728</td> + </tr><tr> + <td class="tdl_ws1"> ”</td> + <td class="tdl_wsp">”</td> + <td class="tdc">26°.8</td> + <td class="tdr_wsp">1.4710</td> + <td class="tdr_wsp">1.4716</td> + </tr><tr> + <td class="tdl">Castor</td> + <td class="tdl_wsp">”</td> + <td class="tdc">25°.4</td> + <td class="tdr_wsp">1.4771</td> + <td class="tdr_wsp">1.4773</td> + </tr><tr> + <td class="tdl">Lard</td> + <td class="tdl_wsp">”</td> + <td class="tdc">27°.3</td> + <td class="tdr_wsp">1.4657</td> + <td class="tdr_wsp">1.4666</td> + </tr><tr> + <td class="tdl">Peanut</td> + <td class="tdl_wsp">”</td> + <td class="tdc">25°.3</td> + <td class="tdr_wsp">1.4696</td> + <td class="tdr_wsp">1.4696</td> + </tr> + </tbody> +</table> + +<p>In case of the use of Abbe’s apparatus, in which diffused sunlight +is the source of the illumination, the numbers obtained cannot be +compared directly with those just given unless the apparatus be first +so adjusted as to read with distilled water at 18°, 1.333. In this case +the reading of the scale gives the index as determined by the yellow +ray. The numbers obtained with Abbe’s instrument for some common oils +are given below.<a id="FNanchor_250" href="#Footnote_250" class="fnanchor">[250]</a></p> + +<p>In the determinations the instrument was set with water at 18°, reading +1.3300, and they were corrected by adding 0.0030 in order to compensate +for the error of the apparatus.</p> + +<table class="spb1"> + <thead><tr> + <th class="tdc">Material.</th> + <th class="tdc"> Calculated <br> for 25°.</th> + <th class="tdc">Corrected<br> index.</th> + </tr></thead> + <tbody><tr> + <td class="tdl">Lard</td> + <td class="tdc">1.4620</td> + <td class="tdc">1.4650</td> + </tr><tr> + <td class="tdl">Cotton oil</td> + <td class="tdc">1.4674</td> + <td class="tdc">1.4704</td> + </tr><tr> + <td class="tdl">Olive oil stearin</td> + <td class="tdc">1.4582</td> + <td class="tdc">1.4610</td> + </tr><tr> + <td class="tdl">Lard stearin</td> + <td class="tdc">1.4594</td> + <td class="tdc">1.4624</td> + </tr> + </tbody> +</table> + +<p id="P_299"><b>299. Oleorefractometer.</b>—Instead of measuring the angular value +of the refractive power of an oil it may be compared with some standard +on a purely arbitrary scale. Such an apparatus is illustrated by the +oleorefractometer of Amagat-Jean, or by Zeiss’s butyrorefractometer.</p> + +<p>In the first named instrument, <a href="#FIG_92">Fig. 92</a>, the oil to be +examined is compared directly with another typical oil and the shadow produced +by the difference in refraction is located on a scale read by a telescope +and graduated for two different temperatures.<a id="FNanchor_251" href="#Footnote_251" class="fnanchor">[251]</a> +The internal structure of the apparatus is shown in <a href="#FIG_91">Fig. 93</a>. +<span class="pagenum"><a id="Page_335"></a>[Pg 335]</span></p> + +<div class="figcenter smcap"> + <img id="FIG_92" src="images/fig92.jpg" alt="" width="400" height="609" > + <p class="center spb1">Fig. 92.—Oleorefractometer.</p> + <img id="FIG_93" src="images/fig93.jpg" alt="" width="600" height="350" > + <p class="center spb1">Fig. 93.—Section Showing Construction of Oleorefractometer.</p> +</div> + +<p><span class="pagenum"><a id="Page_336"></a>[Pg 336]</span> +In the center of the apparatus a metal cylinder, <i>A</i>, is found +carrying two plate glass pieces, <i>C B</i>, so placed as to form an +angle of 107°. This cylinder is placed in a larger one, provided with +two circular glass windows. To these two openings are fixed to the +right and left, the telescopic attachments, <i>G</i>, <i>V, S, E</i>, +and the apparatus <i>M, H, Sʹ</i>, <i>Eʹ</i>, for rendering the rays +of light parallel. The field of vision is divided into two portions, +light and dark, by a semicircular stop inserted in the collimator, +and contains the double scale shown in the <a href="#FIG_93">figure</a> +placed at <i>H</i>. The field of vision is illuminated by a gas or oil lamp +placed at a convenient distance from the collimator. The inner metallic cylinder +<i>A</i> is surrounded with an outer one, to which the optical parts +are attached at <i>D Dʹ</i> by means of plane glass plates. This +cylinder is in turn contained in the large water cylinder <i>P P</i>, +carrying a thermometer in the opening shown at the top on the left. The +manipulation of the apparatus is very simple. The outer cylinder is +filled with water, at a temperature below 22°, the middle one with the +typical oil furnished with the instrument, the cover of the apparatus +carrying the thermometer placed in position and the cup-shaped funnel +inserted in the cylinder <i>A</i>, which is at first also filled +with the typical oil. The whole system is next brought slowly to +the temperature of 22° by means of the lamp shown in <a href="#FIG_92">Fig. 92</a>. +The telescope is adjusted to bring the scale of the field of vision into +focus and the line dividing the light and shadow of the field should +fall exactly on 0°<i>a</i>. If this be not the case the 0° is adjusted +by screws provided for that purpose until it is in proper position. +The typical oil is withdrawn from <i>A</i> by the cock <i>R</i>, the +cylinder washed with a little of the oil to be examined and then filled +therewith. On again observing the field of vision the line separating +the shadow from the light will be found moved to the right or left, +if the oil have an index different from that of the typical oil. The +position of the dividing line is read on the scale.</p> + +<p>For fats the temperature of the apparatus is brought exactly to 45° and +the scale 0°b is used. In other respects the manipulation for the fats +is exactly that described for oils. In the use of 0°a, in case the room +<span class="pagenum"><a id="Page_337"></a>[Pg 337]</span> +be warmer than 22°, all the liquids employed should be cooled below 22° +before being placed in the apparatus. It is then only necessary to wait +until the room temperature warms the system to 22°. In the case of fats +it is advisable to heat all the liquids to about 50° and allow them to +cool to 45° instead of heating them to that temperature by means of the +lamp.</p> + +<p>One grave objection to this instrument is found in the absence of the +proper scientific spirit controlling its manufacture and sale, as +evidenced by the attempt to preserve the secret of the composition +of the typical oil and the negligence in testing the scale of the +instruments which will be pointed out further along.</p> + +<p>According to Jean<a id="FNanchor_252" href="#Footnote_252" class="fnanchor">[252]</a> +the common oils, when purified, give the following readings at 22°:</p> + +<table class="spb1"> + <tbody><tr> + <td class="tdl">Peanut</td> + <td class="tdl_wsp">oil</td> + <td class="tdr_wsp">+3.5</td> + <td class="tdc"> to </td> + <td class="tdr">+6.5</td> + </tr><tr> + <td class="tdl">Colza</td> + <td class="tdc">”</td> + <td class="tdr_wsp">+17.5</td> + <td class="tdc">”</td> + <td class="tdr">+21.0</td> + </tr><tr> + <td class="tdl">Cotton</td> + <td class="tdc">”</td> + <td class="tdr_wsp">+18.0</td> + <td class="tdc">”</td> + <td class="tdr">+18.0</td> + </tr><tr> + <td class="tdl">Linseed</td> + <td class="tdc">”</td> + <td class="tdr_wsp">+47.0</td> + <td class="tdc">”</td> + <td class="tdr">+54.5</td> + </tr><tr> + <td class="tdl">Lard</td> + <td class="tdc">”</td> + <td class="tdr_wsp">+5.5</td> + <td class="tdc">”</td> + <td class="tdr">+5.5</td> + </tr><tr> + <td class="tdl">Olive</td> + <td class="tdc">”</td> + <td class="tdr_wsp">+1.5</td> + <td class="tdc">”</td> + <td class="tdr">0.0</td> + </tr><tr> + <td class="tdl">Sesamé</td> + <td class="tdc">”</td> + <td class="tdr_wsp">+17.5</td> + <td class="tdc">”</td> + <td class="tdr">+19.0</td> + </tr><tr> + <td class="tdl" colspan="2">Oleomargarin</td> + + <td class="tdr_wsp">  -15.0</td> + <td class="tdc">”</td> + <td class="tdr">-15.0</td> + </tr><tr> + <td class="tdl">Butter</td> + <td class="tdl_wsp">fat</td> + <td class="tdr_wsp">-30.0</td> + <td class="tdc">”</td> + <td class="tdr">-30.0</td> + </tr><tr> + <td class="tdl">Mutton</td> + <td class="tdl_wsp">oil</td> + <td class="tdr_wsp">0.0</td> + <td class="tdc">”</td> + <td class="tdr">0.0</td> + </tr><tr> + <td class="tdl">Fish</td> + <td class="tdc">”</td> + <td class="tdr_wsp">+38.0</td> + <td class="tdc">”</td> + <td class="tdr">+38.0</td> + </tr> + </tbody> +</table> + +<p>In this instrument, therefore, vegetable and fish oils, as a rule, show +a right hand, and animal fats a left hand deviation.</p> + +<p>The oleorefractometer has been extensively used in this laboratory and +the data obtained thereby have been found useful. We have not found, +however, the values fixed by Jean to be constant. The numbers for lard +have varied from -3.0 to -10.0, and other fats have shown almost as +wide a variation from the values assigned by him.</p> + +<p>Jean states that the number for lard, determined by the +oleorefractometer, is -12, and he gives a definite number for each of +the common oils and fats. On trying the pure lards of known origin in +this instrument, I have never yet found one that showed a deviation of +-12 divisions of the scale; but I have no doubt that there are many +such lards in existence. The pure normal lards derived from the fat of +<span class="pagenum"><a id="Page_338"></a>[Pg 338]</span> +a single animal would naturally show greater variations in their +chemical and physical properties, than a typical lard derived from +the mixed fats of a great many animals. In leaf lard, rendered in the +laboratory, the reading of the oleorefractometer was found to be -10°, +while with the intestinal lard it was -9°. On the other hand, a lard +rendered from the fat from the back of the animal showed a reading of +only -3°, and a typical cottonseed oil a reading of +12°. According +to the statement of Jean, a lard which gives even as low a refractive +number as -9, by his instrument, would be adjudged at least one-quarter +cottonseed oil.</p> + +<p>After a thorough trial of the instrument of Jean, I am convinced that +it is of great diagnostic value, but if used in the arbitrary manner +indicated by the author it would lead to endless error and confusion. +In other words, this instrument is of greater value in analyses than +Abbe’s ordinary refractometer, because it gives a wider expansion in +the limits of the field of vision, and therefore can be more accurately +read, but it is far from affording a certain means of discovering +traces of adulteration with other fats.</p> + +<p><b>300. Variations in the Instruments.</b>—In the use of the +oleorefractometer, attention should be called to the fact that, through +some negligence in manufacture, the instruments do not give, in all +instances, the same reading with the same substance. Allen obtained the +following data with a sample of lard examined in three instruments, +<i>viz.</i>, 4°.5, 6°, and 11°. Such wide differences in the scales +of the instruments cannot fail to disparage the value of comparative +determinations.</p> + +<p>The variations in samples of known origin, when read on the same +instrument, however, will show the range of error to which the +determinations made with the oleorefractometer are subject. Pearmain +has tabulated a large number of observations of this kind, covering 240 +samples of oils.<a id="FNanchor_253" href="#Footnote_253" class="fnanchor">[253]</a></p> + +<p>Following are the data relating to the most important oils. +<span class="pagenum"><a id="Page_339"></a>[Pg 339]</span></p> + +<table class="spb1"> + <thead><tr> + <th class="tdc"> </th> + <th class="tdc"><span class="smcap">At</span> 22°.</th> + <th class="tdc"> </th> + <th class="tdc"> </th> + </tr><tr> + <th class="tdc">Name of oil.</th> + <th class="tdc">Highest<br>reading.<br> Degrees. </th> + <th class="tdc">Lowest<br>reading.<br> Degrees. </th> + <th class="tdc">Mean<br>reading.<br> Degrees. </th> + </tr></thead> + <tbody><tr> + <td class="tdl">Almond</td> + <td class="tdr_ws1">10.5</td> + <td class="tdr_ws1">8.0</td> + <td class="tdr_ws1">9.5</td> + </tr><tr> + <td class="tdl">Peanut</td> + <td class="tdr_ws1">7.0</td> + <td class="tdr_ws1">5.0</td> + <td class="tdr_ws1">6.0</td> + </tr><tr> + <td class="tdl">Castor</td> + <td class="tdr_ws1">42.0</td> + <td class="tdr_ws1">39.0</td> + <td class="tdr_ws1">40.0</td> + </tr><tr> + <td class="tdl">Codliver</td> + <td class="tdr_ws1">46.0</td> + <td class="tdr_ws1">40.0</td> + <td class="tdr_ws1">44.0</td> + </tr><tr> + <td class="tdl">Cottonseed (crude)</td> + <td class="tdr_ws1">17.0</td> + <td class="tdr_ws1">16.0</td> + <td class="tdr_ws1">16.5</td> + </tr><tr> + <td class="tdl"><span class="ws2">”</span><span class="ws2">(refined)</span></td> + <td class="tdr_ws1">23.0</td> + <td class="tdr_ws1">17.0</td> + <td class="tdr_ws1">21.5</td> + </tr><tr> + <td class="tdl">Lard oil</td> + <td class="tdr_ws1">-1.0</td> + <td class="tdr_ws1">0.0</td> + <td class="tdr_ws1">0.0</td> + </tr><tr> + <td class="tdl">Linseed (crude)</td> + <td class="tdr_ws1">52.0</td> + <td class="tdr_ws1">48.0</td> + <td class="tdr_ws1">50.0</td> + </tr><tr> + <td class="tdl"><span class="ws2">”</span> (refined)</td> + <td class="tdr_ws1">54.0</td> + <td class="tdr_ws1">50.0</td> + <td class="tdr_ws1">52.5</td> + </tr><tr> + <td class="tdl">Olive</td> + <td class="tdr_ws1">3.5</td> + <td class="tdr_ws1">1.0</td> + <td class="tdr_ws1">2.0</td> + </tr><tr> + <td class="tdl">Rape</td> + <td class="tdr_ws1">20.0</td> + <td class="tdr_ws1">16.0</td> + <td class="tdr_ws1">17.5</td> + </tr><tr> + <td class="tdl">Sesamé</td> + <td class="tdr_ws1">17.0</td> + <td class="tdr_ws1">13.0</td> + <td class="tdr_ws1">15.5</td> + </tr><tr> + <td class="tdl">Sunflower</td> + <td class="tdr_ws1">35.0</td> + <td class="tdr_ws1">35.0</td> + <td class="tdr_ws1">35.0</td> + </tr><tr> + <td class="tdl">Tallow oil</td> + <td class="tdr_ws1">-5.0</td> + <td class="tdr_ws1">-1.0</td> + <td class="tdr_ws1">-3.0</td> + </tr><tr> + <td class="tdl">Oleic acid</td> + <td class="tdr_ws1">-33.0</td> + <td class="tdr_ws1">-29.0</td> + <td class="tdr_ws1">-32.0</td> + </tr><tr> + <td class="tdl" colspan="4"> </td> + </tr><tr> + <td class="tdl"> </td> + <td class="tdr_ws1"><b><span class="smcap">At</span> 45°.</b></td> + <td class="tdr_ws1"> </td> + <td class="tdr_ws1"> </td> + </tr><tr> + <td class="tdl">Butter</td> + <td class="tdr_ws1">-34.0</td> + <td class="tdr_ws1">-25.0</td> + <td class="tdr_ws1">-30.0</td> + </tr><tr> + <td class="tdl">Oleomargarin</td> + <td class="tdr_ws1">-18.0</td> + <td class="tdr_ws1">-13.0</td> + <td class="tdr_ws1">-15.0</td> + </tr><tr> + <td class="tdl">Lard</td> + <td class="tdr_ws1">-14.0</td> + <td class="tdr_ws1">-8.0</td> + <td class="tdr_ws1">-10.5</td> + </tr><tr> + <td class="tdl">Tallow</td> + <td class="tdr_ws1">-18.0</td> + <td class="tdr_ws1">-15.0</td> + <td class="tdr_ws1">-16.0</td> + </tr><tr> + <td class="tdl">Paraffin</td> + <td class="tdr_ws1">58.5</td> + <td class="tdr_ws1">54.0</td> + <td class="tdr_ws1">56.0</td> + </tr> + </tbody> +</table> + +<div class="figcenter smcap"> + <img id="FIG_94" src="images/fig94.jpg" alt="" width="400" height="523" > + <p class="center spb1">Fig. 94.—Butyrorefractometer.</p> +</div> + +<p id="P_301"><b>301. Butyrorefractometer.</b>—Another instrument graduated on an +arbitrary scale is the butyrorefractometer of Zeiss. This apparatus, +which resembles in some respects the instrument of Abbe, differs +therefrom essentially in dispensing with the revolving prisms of +Amici, whereby the chromatic fringing due to dispersion is corrected, +and on having the scale fixed for one substance, in this instance, +pure butter fat. The form of the instrument is shown in <a href="#FIG_94">Fig. 94</a>. +The achromatization for the butter fat is secured in the prisms between +which a film of the fat is placed, as in the Abbe instrument. When +a fat, differing from that for which the instrument is graduated is +introduced, the fringes of the dark and light portions of the field +will not only be colored (difference in dispersion), but the line of +<span class="pagenum"><a id="Page_340"></a>[Pg 340]</span> +separation will also be displaced (difference in refractive power). The +apparatus is therefore used in the differential determination of these +two properties. It must not be forgotten, however, that butter fats +differ so much in these properties among themselves as to make possible +the condemnation of a pure as an adulterated sample.</p> + +<p><b>302. Method of Charging the Apparatus.</b>—The prism casing of +the instrument is opened by turning the pin <i>F</i> to the right and +pushing the half <i>B</i> of the prism casing aside. The prism and its +appendages must be cleaned with the greatest care, the best means for this +purpose being soft clean linen moistened with a little alcohol or ether.</p> + +<p>Melt the sample of butter in a spoon and pour it upon a small paper +filter held between the fingers and apply the first two or three drops +of clear butter fat so obtained to the surface of the prism contained +in prism casing <i>B</i>. For this purpose the apparatus should be +raised with the left hand so as to place the prism surface in a +horizontal position.</p> + +<p>Press <i>B</i> against <i>A</i> and replace <i>F</i> by turning it in +the opposite direction into its original position; thereby <i>B</i> is +prevented from falling back and both prism surfaces are kept in close contact.</p> + +<p><b>303. Method of Observation.</b>—While looking into the telescope, +give the mirror <i>J</i> such a position as to render the critical line +which separates the bright left part of the field from the dark right +part distinctly visible. It may also be necessary to move or turn the +instrument about a little. First it will be necessary to ascertain +whether the space between the prism surfaces be uniformly filled with +butter, for, if not, the critical line will not be distinct.</p> + +<p>By allowing a current of water of constant temperature to flow through +the apparatus, some time previous to the taking of the reading, the at +first somewhat hazy critical line approaches in a short time, generally +after a minute, a fixed position and quickly attains its greatest +distinctness. When this point has been reached note the appearance of +the critical line (<i>i. e.</i>, whether colorless or colored and in +the latter case of what color); also note the position of the critical +line on the centesimal scale, which admits of the tenth divisions being +<span class="pagenum"><a id="Page_341"></a>[Pg 341]</span> +conveniently estimated, and at the same time read the thermometer. By +making an extended series of successive readings and by employing an +assistant for melting and preparing the small samples of butter, from +twenty-five to thirty refractometric butter tests may, after a little +practice, be made in an hour.</p> + +<p>The readings of the refractive indices of a large number of butter +samples made at 25° are, by means of a table which will be found +below, directly reduced to scale divisions and yield the following +equivalents:<a id="FNanchor_254" href="#Footnote_254" class="fnanchor">[254]</a></p> + +<table class="spb1 fs_90"> + <tbody><tr> + <td class="tdl">Natural butter</td> + <td class="tdl_wsp">(1.4590-1.4620) : 49.5-54.0</td> + <td class="tdl_wsp">scale</td> + <td class="tdl_wsp">divisions.</td> + </tr><tr> + <td class="tdl">Margarin</td> + <td class="tdl_wsp">(1.4650-1.4700) : 58.6-66.4</td> + <td class="tdc">”</td> + <td class="tdc">”</td> + </tr><tr> + <td class="tdl">Mixtures</td> + <td class="tdl_wsp">(1.4620-1.4690) : 54.0-64.8</td> + <td class="tdc">”</td> + <td class="tdc">”</td> + </tr> + </tbody> +</table> + +<p>Whenever, in the refractometric examination of butter at a temperature +of 25°, higher values than 54.0 are found for the critical lines these +samples will, according to Wollny, by chemical analysis, always be +found to be adulterated; but in all samples in which the value for +the position of the critical line does not fall below 52.5, chemical +analysis maybe dispensed with and the samples may be pronounced to be +pure butter.</p> + +<p>In calculating the position of the critical line for other temperatures +than 25° allow for 1° variation of temperature a mean value of 0.55 +scale division. The following table, which has been compiled in this +manner, shows the values corresponding to various temperatures, each +value being the upper limit of scale divisions admissible in pure butter:</p> + +<table class="spb1 fs_90"> + <tbody><tr> + <td class="tdc">Temp.</td> <td class="tdc"> Sc. div. </td> + <td class="tdc">Temp.</td> <td class="tdc"> Sc. div. </td> + <td class="tdc">Temp.</td> <td class="tdc"> Sc. div. </td> + <td class="tdc">Temp.</td> <td class="tdc"> Sc. div. </td> + </tr><tr> + <td class="tdc">45°</td> <td class="tdc">41.5</td> + <td class="tdc">40°</td> <td class="tdc">44.2</td> + <td class="tdc">35°</td> <td class="tdc">47.0</td> + <td class="tdc">30°</td> <td class="tdc">49.8</td> + </tr><tr> + <td class="tdc">44°</td> <td class="tdc">42.0</td> + <td class="tdc">39°</td> <td class="tdc">44.8</td> + <td class="tdc">34°</td> <td class="tdc">47.5</td> + <td class="tdc">29°</td> <td class="tdc">50.3</td> + </tr><tr> + <td class="tdc">43°</td> <td class="tdc">42.6</td> + <td class="tdc">38°</td> <td class="tdc">45.3</td> + <td class="tdc">33°</td> <td class="tdc">48.1</td> + <td class="tdc">28°</td> <td class="tdc">50.8</td> + </tr><tr> + <td class="tdc">42°</td> <td class="tdc">43.1</td> + <td class="tdc">37°</td> <td class="tdc">45.9</td> + <td class="tdc">32°</td> <td class="tdc">48.6</td> + <td class="tdc">27°</td> <td class="tdc">51.4</td> + </tr><tr> + <td class="tdc">41°</td> <td class="tdc">43.7</td> + <td class="tdc">36°</td> <td class="tdc">46.4</td> + <td class="tdc">31°</td> <td class="tdc">49.2</td> + <td class="tdc">26°</td> <td class="tdc">51.9</td> + </tr><tr> + <td class="tdc">40°</td> <td class="tdc">44.2</td> + <td class="tdc">35°</td> <td class="tdc">47.0</td> + <td class="tdc">30°</td> <td class="tdc">49.8</td> + <td class="tdc">25°</td> <td class="tdc">52.5</td> + </tr> + </tbody> +</table> + +<p>If, therefore, at any temperature between 45° and 25° values be found +for the critical line, which are less than the values corresponding to +the same temperature according to the table, the sample of butter may +safely be pronounced to be natural, <i>i. e.</i>, unadulterated butter. +If the reading show higher numbers for the critical line the sample +should be reserved for chemical analysis. A special thermometer for use +in the examination of butter will be described in the section devoted +to dairy products. +<span class="pagenum"><a id="Page_342"></a>[Pg 342]</span></p> + +<p><b>304. Range of Application of the Butyrorefractometer.</b>—The +extended range of the ocular scale of the refractometer, <i>n</i> = +1.42 to 1.49, which embraces the refractive indices of the majority of +oils and fats, renders the instrument applicable for testing oils and +fats and also for examining glycerol.</p> + +<p>By reference to the subjoined table the scale divisions may be +transformed into terms of refractive indices. It gives the refractive +indices for yellow light for every ten divisions of the scale. The +differential column Δ gives the change of the refractive indices in +terms of the fourth decimal per scale division. Owing to the accuracy +with which the readings can be taken (0.1 scale division) the error of the +value of <i>n</i> rarely exceeds one unit of the fourth decimal of <i>n</i>.</p> + +<p class="f120 spa1"><b><span class="smcap">Table of Refractive Indices.</span></b></p> + +<table class="spb1 fs_90"> + <thead><tr> + <th class="tdc">Scale div.</th> + <th class="tdc">n<span class="fs_80"><sub>D</sub></span>.</th> + <th class="tdc fs_120">Δ.</th> + <th class="tdc"> Scale div.</th> + <th class="tdc">n<span class="fs_80"><sub>D</sub></span>.</th> + <th class="tdc fs_120">Δ.</th> + </tr></thead> + <tbody><tr> + <td class="tdc"> 0</td> + <td class="tdc">1.4220</td> + <td class="tdc">8.0</td> + <td class="tdc">50</td> + <td class="tdc">1.4593</td> + <td class="tdc">6.6</td> + </tr><tr> + <td class="tdc">10</td> + <td class="tdc">  1.4300  </td> + <td class="tdc">7.7</td> + <td class="tdc">60</td> + <td class="tdc">  1.4650  </td> + <td class="tdc">6.4</td> + </tr><tr> + <td class="tdc">20</td> + <td class="tdc">1.4377</td> + <td class="tdc">7.5</td> + <td class="tdc">70</td> + <td class="tdc">1.4723</td> + <td class="tdc">6.0</td> + </tr><tr> + <td class="tdc">30</td> + <td class="tdc">1.4452</td> + <td class="tdc">7.2</td> + <td class="tdc">80</td> + <td class="tdc">1.4783</td> + <td class="tdc">5.7</td> + </tr><tr> + <td class="tdc">40</td> + <td class="tdc">1.4524</td> + <td class="tdc">6.9</td> + <td class="tdc">90</td> + <td class="tdc">1.4840</td> + <td class="tdc">5.5</td> + </tr><tr> + <td class="tdc">50</td> + <td class="tdc">1.4593</td> + <td class="tdc"> </td> + <td class="tdc">100 </td> + <td class="tdc">1.4895</td> + <td class="tdc"> </td> + </tr> + </tbody> +</table> + +<p>The process of observation is precisely the same as that already +described. In cases, however, where the critical line presents very +broad fringes (turpentine, linseed oil, etc.) it is advisable to repeat +the reading with the aid of a sodium flame.</p> + +<p><b>305. Viscosity.</b>—An important property of an oil, especially +when its lubricating qualities are considered, is the measure of +the friction which the particles exert on other bodies and among +themselves, in other words, its viscosity. In the measure of this +property no definite element can be considered, but the analyst must +be content with comparing the given sample with the properties of some +other liquid regarded as a standard. The usual method of procedure +consists in determining the time required for equal volumes of the two +liquids to pass through an orifice of given dimensions, under identical +conditions of temperature and pressure. In many instances the viscosity +of oils is determined by comparing them with water or rape oil, while, +<span class="pagenum"><a id="Page_343"></a>[Pg 343]</span> +in other cases, a solution of sugar is employed as the standard of measurement.</p> + +<p>In case rape oil be taken as a standard and its viscosity represented +by 100 the number representing the viscosity of any other oil may be +found by multiplying the number of seconds required for the outflow of +fifty cubic centimeters by 100 and dividing by 535. If the specific +gravity vary from that of rape oil, <i>viz.</i>, 0.915, at 15°, a +correction must be made by multiplying the result obtained above by the +specific gravity of the sample and dividing the product by 0.915. If +<i>n</i> be the observed time of outflow in seconds and <i>s</i> the +specific gravity the viscosity is expressed as follows:<a id="FNanchor_255" href="#Footnote_255" class="fnanchor">[255]</a></p> + +<table class="spb1 fs_105"> + <tbody><tr> + <td class="tdl" rowspan="2"><i>V</i> = </td> + <td class="tdc bb"><i>n</i> × 100 × <i>s</i></td> + <td class="tdl" rowspan="2"> = </td> + <td class="tdc bb"><i>n</i> × 100 × <i>s</i></td> + </tr><tr> + <td class="tdc">535 × 0.195</td> + <td class="tdc">489.525</td> + </tr> + </tbody> +</table> + +<div class="figleft smcap"> + <img id="FIG_95" src="images/fig95.jpg" alt="" width="200" height="585" > + <p class="center">Fig. 95.—<br>Doolittle’s<br> Viscosimeter.</p> +</div> + +<p>It is important that the height of the oil in the cylinders from which +it is delivered be kept constant, and this is secured by supplying +additional quantities, on the principle of the mariotte bottle.</p> + +<p><b>306. The Torsion Viscosimeter.</b>—In this laboratory the torsion +viscosimeter, based on the principle described by Babcock is used. +The instrument employed is the one described by Doolittle.<a id="FNanchor_256" href="#Footnote_256" class="fnanchor">[256]</a> +The construction of the apparatus is illustrated in <a href="#FIG_95">Fig. 95</a>.</p> + +<p>A steel wire is suspended from a firm support and fastened to a stem +which passes through a graduated horizontal disk, thus permitting the +accurate measurement of the torsion of the wire. The disk is adjusted +so that the index point reads exactly <i>0</i>, thus showing that there +is no torsion in the wire. A brass cylinder seven centimeters long by +five in diameter, having a slender stem by which to suspend it, is +<span class="pagenum"><a id="Page_344"></a>[Pg 344]</span> +immersed in the oil and fastened by a thumbscrew to the lower part of +the stem of the disk. The oil cup is surrounded by a bath of water or +high fire-test oil, according to the temperature at which it is desired +to determine the viscosity. This temperature obtained, while the disk +is resting on its supports, the wire is twisted 360° by rotating the +milled head at the top. The disk being released, the cylinder rotates +in the oil by virtue of the torsion of the wire.</p> + +<p>The action now observed is identical with that of the simple pendulum.</p> + +<p>If there were no resistance to be overcome, the disk would return to +0, and the momentum thus acquired would carry it 360° in the opposite +direction. But the resistance of the oil to the rotation of the +cylinder causes the revolution to fall short of 360°, and the greater +the viscosity of the oil the greater will be the resistance, and also +the retardation. This retardation is found to be a very delicate +measure of the viscosity of the oil.</p> + +<p>This retardation may be read in a number of ways, but the simplest +is to read directly the number of degrees of retardation between the +first and second complete arcs covered by the rotating pendulum. For +example, suppose the wire be twisted 360° and the disk released so that +rotation begins. In order to obtain an absolute reading to start from, +which shall be independent of any slight error in adjustment, ignore +the starting point and make the first reading of the index at the end +of the first swing. The disk is allowed to complete a vibration and +the needle is read again at its nearest approach to the first point +read. The difference in the two readings will measure the retardation +due to the viscosity of the liquid. In order to eliminate errors +duplicate determinations are made, the milled head being rotated in an +opposite direction in the second one. The mean of the two readings will +represent the true retardation. Each instrument is standardized in a +solution of pure cane sugar, as proposed by Babcock, and the viscosity, +in each case, is a number representing the number of grams of sugar in +100 cubic centimeters, which, at 22°, would produce the retardation noted.</p> + +<p>Each instrument is accompanied by a table which contains the necessary +<span class="pagenum"><a id="Page_345"></a>[Pg 345]</span> +corrections for it and the number expressing the viscosity, +corresponding to the different degrees of retardation, as read on the +index. The following numbers, representing the viscosity of some oils +as determined by the method of Doolittle, were obtained by Krug.<a id="FNanchor_257" href="#Footnote_257" class="fnanchor">[257]</a></p> + +<table class="spb1"> + <tbody><tr> + <td class="tdl">Peanut</td> + <td class="tdl_wsp">oil</td> + <td class="tdr">  48.50</td> + </tr><tr> + <td class="tdl">Olive</td> + <td class="tdc">”</td> + <td class="tdr">53.00</td> + </tr><tr> + <td class="tdl">Cottonseed</td> + <td class="tdc">”</td> + <td class="tdr">46.25</td> + </tr><tr> + <td class="tdl">Linseed</td> + <td class="tdc">”</td> + <td class="tdr">33.50</td> + </tr> + </tbody> +</table> + +<p id="P_307"><b>307. Microscopic Appearance.</b>—When fats are allowed to slowly +crystallize from an ethereal solution they may afford crystalline +forms, which, when examined with a magnifying glass, yield valuable +indications of the nature and origin of the substance under +examination.<a id="FNanchor_258" href="#Footnote_258" class="fnanchor">[258]</a></p> + +<p>The method of securing fat crystals for microscopic examination, which +has been used in this laboratory, is as follows: From two to five +grams of the fat are placed in a test tube and dissolved in from ten +to twenty cubic centimeters of ether. The tube is loosely stoppered +with cotton and allowed to stand, for fifteen hours or longer, in a +moderately warm room where no sudden changes of temperature are likely +to take place. It is advisable to prepare several solutions of the same +substance with varying properties of solvent, for it is not possible +to secure in a given instance those conditions which produce the most +characteristic crystals. The rate and time of the crystallization +should be such that the microscopic examination can take place when +only a small portion of the fat has separated in a crystalline +condition. A drop of the mass containing the crystals is removed by +means of a pipette, placed on a slide, a drop of cotton or olive +oil added, a cover glass gently pressed down on the mixture and the +preparation subjected to microscopic examination. Several slides should +be prepared from the same or different crystallizations. Sometimes the +results of an examination made in this way are very definite, but the +analyst must be warned not to expect definite data in all cases. Often +the microscopic investigations result in the production of negative or +misleading observations, and, at best, this method of procedure must be +regarded only as helpful and confirmatory.</p> + +<p>A modification of the method of preparation described above has been +<span class="pagenum"><a id="Page_346"></a>[Pg 346]</span> +suggested by Gladding.<a id="FNanchor_259" href="#Footnote_259" class="fnanchor">[259]</a> +About five grams of the melted fat are placed in a small erlenmeyer, +dissolved in a mixture of ten cubic centimeters of absolute alcohol +mixed with half that quantity of ether. The flask is stoppered with +a plug of cotton and allowed to stand in a cool place for about half +an hour. By this treatment the more easily crystallizable portions of +the fat separate in a crystalline form, while the triolein and its +nearly related glycerids remain in solution. The crystalline product is +separated by filtration through paper wet with alcohol and washed once +with the solvent mentioned above. After drying in the air for some time +the crystals are removed from the paper and dissolved in twenty-five +cubic centimeters of ether, the cotton plug inserted, and the +erlenmeyer placed, in a standing position, in a large beaker containing +water. The water jacket prevents any sudden changes of temperature and +affords an opportunity for the uniform evaporation of the ether which +should continue for fifteen hours or longer in a cool place.</p> + +<p>Other solvents, <i>viz.</i>, alcohol, chloroform, carbon disulfid, +carbon tetrachlorid, petroleum and petroleum ether have been +extensively used in the preparation of fat crystals for microscopic +examination, but in our experience none of these is equal to ether when +used as already described.</p> + +<p id="P_308"><b>308. Microscopic Appearance of Crystals of Fats.</b>—For an +extended study and illustration of the characteristics of fat crystals +the bulletin of the Division of Chemistry, already cited, may be +consulted. In the case of lard, there is a tendency, more or less +pronounced, to form prismatic crystals with rhombic ends. Beef fat on +the other hand shows a tendency to form fan-shaped crystals in which +the radii are often curved.</p> + +<p>Typical crystals of swine and beef fat are shown in the accompanying +figures, <a href="#FIG_96">96</a> and <a href="#FIG_97">97</a>.<a id="FNanchor_260" href="#Footnote_260" class="fnanchor">[260]</a> +In mixtures of swine and beef fats the typical crystals are not always +developed, but in most cases the fan-shaped crystals of the beef fat +will appear more or less modified when that fat forms twenty per cent +or more of the mixture. When only five or ten per cent of the beef fat +on the one hand or a like amount of swine fat on the other are present +the expectation of developing any characteristic crystals of the +minimum constituent is not likely to be realized. +<span class="pagenum"><a id="Page_347"></a>[Pg 347]</span></p> + +<p>The typical crystals of lard are thought by some experts to be palmitin +and those of beef fat stearin, but no direct evidence has been adduced +in support of these <i>a priori</i> theories.</p> + +<p>In the experience of this laboratory, as described by Crampton,<a id="FNanchor_261" href="#Footnote_261" class="fnanchor">[261]</a> +the differences between the typical crystallization of beef and swine +fats are plainly shown. In mixed fats, on the contrary, confusing +observations are often made. In a mixture of ten per cent of beef +and ninety per cent of swine fats a uniform kind of crystallization +is observed, not distinctly typical, but the characteristics of the +lard crystals predominate. In many cases a positive identification +of the crystals is only made possible by repeated crystallizations. +In the examination of so-called refined lards, which are mixtures of +lard and beef fat, the form of aggregation of the crystals is found +to resemble the fan-shaped typical forms of beef fat. When the single +crystals, however, are examined with a higher magnifying power, they +are not found to be pointed but blunt, and some present the appearance +of plates with oblique terminations, but not so characteristic as +those obtained from pure lard. In other cases in compound lards no +beef fat crystals are observed and these lards may have been made +partly of cotton oil stearin. When a lard crystal presents its edge +to observation it may readily escape identification, or may even be +mistaken for a crystal of beef fat. In order to insure a side view the +cover glass should be pressed down with a slight rotatory movement, +whereby some of the lard crystals at least may be made to present a +side view.</p> + +<p><b>309. Observation of Fat Crystals with Polarized Light.</b>—The +appearance of fat crystals, when observed by means of polarized light +alone or with the adjunct of a selenite plate, is often of value in +distinguishing the nature and origin of the sample.<a id="FNanchor_262" href="#Footnote_262" class="fnanchor">[262]</a></p> + +<p>Every fat and oil which is amorphous will present the same set of +phenomena when observed with polarized light through a selenite plate, +but when a fat has been melted and allowed to cool slowly the field of +vision will appear mottled and particolored when thus examined. This +method has been largely used in the technical examination of butter for +<span class="pagenum"><a id="Page_348"></a>[Pg 348]</span> +adulterants, and the microscope is extensively employed by the chemists +of the Bureau of Internal Revenue for this purpose. In the examination +of the crystals of butter fat by polarized light a cross is usually +observed when the nicols are turned at the proper angle, but the cross, +while almost uniformly seen with butter, is not distinctive, since +other fats often show it. These forms of crystals are best obtained by +heating the butter fat to the boiling-point of water for about a minute +and then allowing it to slowly solidify, and stand for twenty-four hours.</p> + +<p>Pure butter, properly made, is never subjected to fusion, and hence, +when examined through a selenite plate, presents a uniform field of +vision similarly illuminated and tinted throughout. In oleomargarin, +the fats are sometimes, during their preparation, in a fused condition. +The field of vision is therefore filled to a greater or less extent +with crystals more or less perfect in form. Some of these crystals, +being doubly refracting, will impart to a selenite field a mottled +appearance. Such a phenomenon is therefore indicative of a fraudulent +butter or of one which has been at some time subjected to a temperature +at or above its fusing point.</p> + +<p><b>310. Spectroscopic Examination of Oils.</b>—The presence of +chlorophyll or of its alteration products is a characteristic of crude +oils of vegetable origin. In refined oils, even when of a vegetable +origin, all traces of the chlorophyll products may disappear. The +absorption bands given by oils are not all alike and in doubtful cases +a suspected sample should be compared with one of known origin.</p> + +<p>In conducting the examination, the oil in a glass vessel with parallel +sides, is placed in front of the slit of the spectroscope and any +absorption band is located by means of the common divided scale and by +the color of the spectrum on which it falls. Olive and linseed oils +give three sharply defined absorption bands, a very dark one in the +red, a faint one on the orange and a well marked one in the green.</p> + +<p>Sesame, arachis, poppyseed and cottonseed oils also show absorption +bands. Castor and almond oils do not affect the spectrum.</p> + +<div class="figcenter smcap"> + <p class="f110"><b>Fig. 96.</b></p> + <img id="FIG_96" src="images/fig96.jpg" alt="" width="500" height="495" > + <p class="center spb1">Lard Crystals × 65.</p> + <p class="f110"><b>Fig. 97.</b></p> + <img id="FIG_97" src="images/fig97.jpg" alt="" width="500" height="492" > + <p class="center">Refined Lard (beef fat) Crystals × 65.</p> + <p class="spb2">A. Hoen & Co., Lithocaustic.</p> +</div> + +<p><span class="pagenum"><a id="Page_349"></a>[Pg 349]</span> +Rape and flaxseed oils absorb a part of the spectrum but do not affect +the rest of it. The spectroscope is of little practical utility in oil +analysis.<a id="FNanchor_263" href="#Footnote_263" class="fnanchor">[263]</a></p> + +<p><b>311. Critical Temperature of Solution.</b>—The study of the +critical temperature of solution of oils has been made by Crismer, +who finds it of value in analytical work.<a id="FNanchor_264" href="#Footnote_264" class="fnanchor">[264]</a> +If a fatty substance be heated under pressure, with a solvent, <i>e. +g.</i>, alcohol, it will be noticed that as the temperature rises the +meniscus of separation of the two liquids tends to become a horizontal +plane. If at this point the contents of the tube be thoroughly mixed +by shaking and then be left at rest, a point will soon be reached at +which the two liquids again separate, and this point is distinctly a +function of temperature. Following is a description of a convenient +method of determining the critical temperature of the solution of fats +and oils for experimental purposes. Tubes are prepared for holding the +reagents in such a way that, after the introduction of the fat and +alcohol, they can be easily sealed. The capacity of these tubes should +be about five cubic centimeters. They should be charged with about one +cubic centimeter of the dry filtered fat and about twice that quantity +of ninety-five per cent alcohol. Care should be exercised to avoid +touching the upper sides of the tube with the reagents. When charged +the tubes are sealed in the flame of a lamp and attached to the bulb of +a delicate thermometer in such a manner as to have the surface of its +liquid contents even with the top of the bulb. The tube is conveniently +fastened to the thermometer by a platinum wire. For duplicate +determinations two tubes may be fastened to the same thermometric bulb. +The apparatus thus prepared is placed in a large vessel filled with +strong sulfuric acid. The operator should be careful to protect himself +from the danger which might arise from an explosion of the sealed tubes +during heating. It is advisable in all cases to observe the reaction +through a large pane of clear glass. The bath of sulfuric acid is +heated by any convenient means and an even temperature throughout the +mass is secured by stirring with the thermometer and its attachments. +When the meniscus which separates the two liquids becomes a horizontal +plane the thermometer is removed and the liquid in the tubes well mixed +<span class="pagenum"><a id="Page_350"></a>[Pg 350]</span> +until it appear homogeneous. The thermometer is replaced in the bath, +which is allowed to cool slowly, and the phenomena which take place +in the sealed tubes are carefully noted. The critical temperature +of solution is that at which the two liquids begin to separate. +This moment is easily noted. It is, moreover, preceded by a similar +phenomenon taking place in the capillary part of the tube which retains +a drop of the mixture on shaking. In this droplet an opalescence +is first noted. In the mass of the liquid this opalescence, a few +seconds afterwards, is observed to permeate the whole, followed by the +formation of zones and finally of the reappearance of the meniscus of +separation between the two liquids. The temperature at this moment of +opalescence preceding the separation of the liquid is the critical +temperature of solution. With alcohol of 0.8195 specific gravity, at +15°.5 (ninety-five per cent), the observed critical temperatures for +some of the more common fats and oils are as given below:</p> + +<table class="spb1"> + <tbody><tr> + <td class="tdl" colspan="2">Butter fat</td> + <td class="tdr">100°.0</td> + </tr><tr> + <td class="tdl" colspan="2">Oleomargarin</td> + <td class="tdr">125°.0</td> + </tr><tr> + <td class="tdl">Peanut</td> + <td class="tdl">oil</td> + <td class="tdr">123°.0</td> + </tr><tr> + <td class="tdl">Cotton</td> + <td class="tdl_wsp">”</td> + <td class="tdr">116°.0</td> + </tr><tr> + <td class="tdl">Olive</td> + <td class="tdl_wsp">”</td> + <td class="tdr">123°.0</td> + </tr><tr> + <td class="tdl">Sesamé</td> + <td class="tdl_wsp">”</td> + <td class="tdr">121°.0</td> + </tr><tr> + <td class="tdl">Colza</td> + <td class="tdl_wsp">”</td> + <td class="tdr">132°.5</td> + </tr><tr> + <td class="tdl" colspan="2">Mutton tallow</td> + <td class="tdr">116°.0</td> + </tr><tr> + <td class="tdl" colspan="2">Beef marrow</td> + <td class="tdr">125°.0</td> + </tr><tr> + <td class="tdl" colspan="2">Nut oil</td> + <td class="tdr"><span class="ws2"> </span>100°.5</td> + </tr> + </tbody> +</table> + +<p>When the alcohol is not pure or if it be of a different density from +that named, the numbers expressing the critical temperature of solution +will vary from those given above.</p> + +<p><b>312. Polarization.</b>—The pure glycerids are generally neutral to +polarized light. In oils the degree of polarization obtained is often +variable, sometimes to the right and sometimes to the left. Olive oil, +as a rule, shows a slight right hand polarization. Peanut, sesamé, and +cottonseed oils vary in polarizing power, but in no case is it very +marked. Castor oil polarizes slightly to the right.</p> + +<p>In determining the polarizing power of an oil it should be obtained in +a perfectly limpid state by filtration and observed through a tube of +<span class="pagenum"><a id="Page_351"></a>[Pg 351]</span> +convenient length, as a rule, 200 millimeters. The deviation obtained +may be expressed in divisions of the sugar scale of the instrument or +in degrees of angular rotation.</p> + +<p><b>313. Turbidity Temperature.</b>—The turbidity temperature of a +fat, when dissolved in glacial acetic acid, as suggested by Valenta, +may prove of some diagnostic value.<a id="FNanchor_265" href="#Footnote_265" class="fnanchor">[265]</a> +The fats are dissolved, with the aid of heat, in glacial acetic acid +and, on slowly cooling, the temperature at which they become turbid is +observed. The following data observed by Jones are given for +comparison.<a id="FNanchor_266" href="#Footnote_266" class="fnanchor">[266]</a></p> + +<p>The numbers represent the turbidity temperature of the fat when treated +with the glacial acetic acid, and allowed to cool slowly. Butter fat, +from 40° to 70°, mostly from 52° to 65°; oleomargarin, 95° to 106°; +rape oil, 101°; sesamé oil, 77°; linseed oil, 53° to 57°; lard oil, +96°; olive oil, 89°; peanut oil, 61° to 88°.</p> + +<p>It is important in this test that the acetic acid be absolutely +glacial. About three cubic centimeters of the glacial acetic acid, and +three of the fat, should be used.</p> + +<h3>CHEMICAL PROPERTIES.</h3> + +<p><b>314. Solubility in Alcohol.</b>—As has already been noted, the +glycerids are freely soluble in ether, chloroform, carbon bisulfid, +acetone, carbon tetrachlorid, and some other less commonly used +solvents. Their solubility in absolute alcohol is variable and the +determination of its degree may often be useful in analytical work.</p> + +<p>The method used by Milliau for determining the degree of solubility +is as follows:<a id="FNanchor_267" href="#Footnote_267" class="fnanchor">[267]</a> +The fatty matter is deprived of its free acids by shaking for half +an hour with twice its volume of ninety-five per cent alcohol. After +standing until the liquids are separated, the oil or fat is drawn off +and washed three times with distilled water. The sample is deprived +of water by filtering through a hot jacket filter and a given weight +of the dry sample is well shaken with twice its weight of absolute +alcohol. A weighed portion of the alcoholic solution obtained is +evaporated to remove the alcohol and the weight of the residual fat +determined. From the data obtained the percentage of solubility is +<span class="pagenum"><a id="Page_352"></a>[Pg 352]</span> +calculated. Olive oils, when treated as described above, show a +solubility of about forty-three parts per thousand of absolute alcohol, +cotton oil sixty-two parts, sesamé forty-one parts, peanut sixty-six +parts, colza twenty parts, and flaxseed seventy parts per thousand.</p> + +<p><b>315. Coloration Produced by Oxidants.</b>—When oils and fats are +mixed with oxidizing reagents, such as sulfuric and nitric acids, the +glycerids are partly decomposed with the production of colors which +have some analytical significance. The most simple method of applying +these tests is by the use of a thick porcelain plate provided with +small cup-shaped depressions for holding the few drops of material +required. Two or three drops of the oil under examination are placed +in each of the cups, a like quantity of the oxidizing reagent added, +and the mixture stirred with a small glass rod. The colors produced +are carefully noted and the mixture is allowed to remain at room +temperature for at least twelve hours in order that the final tint may +be observed. The sulfuric acid used for this reaction should have a +specific gravity of one and seven-tenths and the nitric acid should +have the usual commercial strength of the strongest acid. Pure lard, +when treated with sulfuric acid, as above described, shows but little +change of color while the vegetable oils mostly turn brown or black. In +addition to the reagents mentioned many others, including sulfuric and +nitric acids, sulfuric acid and potassium bichromate, chlorin, ammonia, +hydrogen peroxid, sodium hydroxid and aqua regia are used. Only a few +of these tests seem to have sufficient analytical importance to merit +any detailed description.<a id="FNanchor_268" href="#Footnote_268" class="fnanchor">[268]</a></p> + +<p id="P_316"><b>316. Coloration in Large Masses.</b>—Instead of applying the color +test in the small way just described, larger quantities of the fat may +be used, either in the natural state or after solution in petroleum +or other solvent. For this purpose about ten cubic centimeters of +the oil are shaken with a few drops of sulfuric acid or sulfuric and +nitric acids. Lard, when thus treated (five drops of sulfuric acid to +ten cubic centimeters of lard) shows practically no coloration. When +treated with an equal volume of sulfuric acid and shaken, the lard on +separating has a brown-red tint.<a id="FNanchor_269" href="#Footnote_269" class="fnanchor">[269]</a></p> + +<p><span class="pagenum"><a id="Page_353"></a>[Pg 353]</span> +Olive oil, with a few drops of sulfuric acid, gives a green color, +while cottonseed, peanut and other vegetable oils, when thus treated +with sulfuric and nitric acids, show brown to black coloration. The +delicacy of the reaction may be increased by first dissolving the fat +or oil in petroleum ether.</p> + +<p>In the use of the coloration test with solvents, a convenient method +is to dissolve about one cubic centimeter of the fat in a test tube in +petroleum ether, add one drop of strong sulfuric acid and shake.</p> + +<p>In the case of lard, the color does not change or becomes yellow +or red. Cottonseed oil, similarly treated, shows a brown or black +color.<a id="FNanchor_270" href="#Footnote_270" class="fnanchor">[270]</a></p> + +<p><b>317. Special Nitric Acid Test.</b>—A special nitric acid test for +cottonseed oil is made with nitric acid of exactly 1.375 specific +gravity at 15°. This test is especially valuable in detecting +cottonseed in olive oil. The operation is conveniently conducted by +shaking together equal volumes of the oil and acid in a test tube until +an intimate mixture or emulsion is secured. When any considerable +quantity of cottonseed oil is present an immediate brown coloration +is produced, from the intensity of which the relative proportion of +cottonseed oil in the case of a mixture may be roughly approximated. +When only a little cottonseed oil is present in the mixture, the test +tube containing the reagents should be set aside for several hours +before the final observation is made.</p> + +<p id="P_318"><b>318. Coloration with Phosphomolybdic Acid.</b>—Among the color +tests, one which we have found of use is the coloration produced in +certain oils, mostly of a vegetable origin, by phosphomolybdic +acid.<a id="FNanchor_271" href="#Footnote_271" class="fnanchor">[271]</a></p> + +<p>The method of applying the test is extremely simple. A few cubic +centimeters of the oil or melted lard are dissolved in an equal volume +of chloroform, and a third volume of ten per cent phosphomolybdic acid +added. The mouth of the test tube is closed with the thumb, and the +whole is violently shaken. On being left in repose, the phosphomolybdic +acid gathers at the top, and the coloration produced therein is easily +observed. Cottonseed oil and peanut oil both give a beautiful green when +<span class="pagenum"><a id="Page_354"></a>[Pg 354]</span> +treated in this way, which is turned to a blue on the addition of +ammonia. Linseed oil gives a green color, but forms a kind of emulsion +which obscures the color to some extent. The pure lards rendered in +the laboratory give no coloration whatever to the reagent, but it +retains its beautiful amber color in every case. Mixtures containing +as little as ten per cent cottonseed oil and ninety per cent lard, +show a distinct greenish tint, while twenty per cent cottonseed oil +gives a distinct green. This reaction, therefore, may be considered +of great value, and on account of its easy application it should come +into wide use. But it is probable that different samples of cottonseed +oil, refined to different degrees or in different ways, vary in their +deportment with phosphomolybdic acid as they do with silver nitrate. In +other words, there may be some samples of cottonseed oil which will not +give the green color when treated as above, or so faintly as to have no +diagnostic value in mixtures.</p> + +<p>This reaction shows itself with nearly all vegetable oils but those +which have been chemically treated either for the purpose of bleaching, +or for the removal of the acidity, do not respond to the test at all, +or else in a feeble manner, and that only after standing some time. +Lard, goose fat, tallow, deer fat, butter fat, etc., show no change in +color on being treated with this reagent, either with or without the +addition of alkali. The presence of a small quantity of vegetable oil +betrays itself by the appearance of the above mentioned coloration, +the intensity of which forms an approximate measure of the amount of +vegetable oil present in the sample. In experiments with suspected +lards, which deviated in their iodin absorption numbers from those of +genuine lard, the results were concordant, the color deepening as the +iodin figure rose. The mineral fats (paraffin, vaselin) are without +action on this reagent, and the only animal fat which reduces it is +codliver oil.</p> + +<p>In like manner some samples of lard may be found which exhibit a +deportment with this reagent similar to that shown with vegetable oils, +and tallow and lard oil have been shown to give more distinct reactions +than some of the vegetable oils.<a id="FNanchor_272" href="#Footnote_272" class="fnanchor">[272]</a></p> + +<p>The phosphomolybdic acid may be prepared by precipitating a solution of +<span class="pagenum"><a id="Page_355"></a>[Pg 355]</span> +ammonium molybdate with sodium phosphate and dissolving the washed +precipitate in a warm solution of sodium carbonate. The solution is +evaporated to dryness and the dry residue subjected to heat. If a blue +coloration be produced it may be discharged by adding a little nitric +acid and reheating. The residue is dissolved in water, acidified with +nitric and made of such a strength as to contain about ten per cent of +the substance.</p> + +<p><b>319. Coloration with Picric Acid.</b>—If to ten cubic centimeters +of oil a cold saturated solution of picric acid in ether be added and +the latter be allowed to evaporate slowly, the acid remains dissolved +in the oil, to which it communicates a brown color.</p> + +<p>Pure lard, after the evaporation of the ether, appears of a +citron-yellow color; if cottonseed oil be present, however, the mixture +assumes a brown-red color.<a id="FNanchor_273" href="#Footnote_273" class="fnanchor">[273]</a></p> + +<p id="P_320"><b>320. Coloration with Silver Nitrate.</b>—A modification of Bechi’s +method of reducing silver nitrate, given further on, has been proposed +by Brullé.<a id="FNanchor_274" href="#Footnote_274" class="fnanchor">[274]</a> +The reagent employed consists of twenty-five parts of silver nitrate +in 1,000 parts of alcohol of ninety-five per cent strength. Twelve +cubic centimeters of the oil to be examined and five of the reagent are +placed in a test tube, held in a vessel containing boiling water, and +the ebullition continued for about twenty minutes. At the end of this +time an olive oil, even if it be an impure one, will show a beautiful +green tint. With seed oils the results are quite different. Cotton oil +submitted to this treatment becomes completely black. Peanut oil shows +at first a brown-red coloration and finally a somewhat green tint, +losing its transparency. Sesamé oil is distinguished by a red-brown +tint very pronounced and remaining red. Colza oil takes on a yellowish +green coloration, becomes turbid and is easily distinguished in its +reaction from olive oil. In mixtures of olive oil with the other oils, +any notable proportion of the seed oils can be easily determined by the +above reactions. Natural butter treated with this reagent retains its +primitive color. That containing margarin becomes a brick-red and as +little as five per cent of margarin in butter can be detected by this +test. With ten per cent the tint is very pronounced. +<span class="pagenum"><a id="Page_356"></a>[Pg 356]</span></p> + +<p><b>321. Coloration with Stannic Bromid.</b>—This reagent is prepared +by adding dry bromin, drop by drop, to powdered or granulated tin +held in a flask immersed in ice water, until a persistent red color +indicates that the bromin is in excess. In the application of this +reagent three or four drops of it are added successively to a little +less than that quantity of the oil, the mixture well stirred and set +aside for a few minutes. The unsaponifiable matters of castor oil give +a green color when thus treated, sandal wood oil a blood-red color and +cedar oil a purplish color.<a id="FNanchor_275" href="#Footnote_275" class="fnanchor">[275]</a></p> + +<p><b>322. Coloration with Auric Chlorid.</b>—The use of auric chlorid +for producing colorations in oils and fats was first proposed by +Hirschsohn.<a id="FNanchor_276" href="#Footnote_276" class="fnanchor">[276]</a> +One gram of auric chlorid is dissolved in 200 cubic centimeters of +chloroform and about six drops of this reagent added to five cubic +centimeters of the oil to be tested. In the case of cottonseed oil a +beautiful red color is produced.</p> + +<p>I have found that even pure lards give a trace of color sometimes with +this reagent, and therefore the production of a slight red tint cannot +in all cases be regarded as conclusive of the presence of cottonseed +oil.<a id="FNanchor_277" href="#Footnote_277" class="fnanchor">[277]</a></p> + +<p>In general, it may be said that the color reactions with fats and oils +have a certain qualitive and sorting value, and in any doubtful case +they should not be omitted. Their value can only be established by +comparison under identical conditions with a large number of fats and +oils of known purity. The analyst must not depend too confidingly on +the data found in books, but must patiently work out these reactions +for himself.</p> + +<p><b>323. Thermal Reactions.</b>—The measurement of the heat produced +by mixing glycerids with reagents which decompose them or excite other +speedy chemical reactions, gives valuable analytical data. These +measurements may be made in any convenient form of calorimeter. The +containing vessel for the reagents should be made of platinum or some +other good conducting metal not affected by them.</p> + +<p>The heat produced is measured in the usual way by the increment in +temperature noted in the mass of water surrounding the containing +<span class="pagenum"><a id="Page_357"></a>[Pg 357]</span> +vessel. The determination of the heat produced in chemical reactions is +a tedious and delicate operation requiring special forms of apparatus +for different substances. The time element in these operations is +a matter of importance, since it is necessary to work in rooms +subject to slight changes of temperature and to leave the apparatus +for some time at rest, in order to bring it and its contents to a +uniform temperature. For these reasons the more elaborate methods of +calorimetric examination are not well suited to ordinary analytical +work, and the reader is referred to standard works on thermal +chemistry for the details of such operations.<a id="FNanchor_278" href="#Footnote_278" class="fnanchor">[278]</a> +For our purpose here a description of two simple thermal processes, +easily and quickly conducted, will be sufficient, while a description +of the method of determining the heat of combustion of foods will be +given in another place.</p> + +<p><b>324. Heat of Sulfuric Saponification.</b>—Maumené was the first to +utilize the production of heat caused by mixing sulfuric acid with a +fat as an analytical process.<a id="FNanchor_279" href="#Footnote_279" class="fnanchor">[279]</a> +In conducting the process a sulfuric acid of constant strength should +be employed inasmuch as the rise of temperature produced by a strong +acid is much greater than when a weaker acid is employed. The process +is at best only comparative and it is evident that the total rise of +temperature in any given case depends on the strength of the acid, the +character, and purity of the fat or oil, the nature of the apparatus +and its degree of insulation, the method of mixing and the initial +temperature. For this reason the data given by different analysts vary +greatly.<a id="FNanchor_280" href="#Footnote_280" class="fnanchor">[280]</a> +For some of the methods of conducting the operation the reader may +consult the work of Allen, cited above, or other authorities.<a id="FNanchor_281" href="#Footnote_281" class="fnanchor">[281]</a></p> + +<p>In this laboratory the process is conducted as follows:<a id="FNanchor_282" href="#Footnote_282" class="fnanchor">[282]</a> +The initial temperature of the reagents should be a constant one. For +oils 20° is a convenient starting point and for fats about 35°, at +which temperature most of them are soft enough to be easily mixed with +the reagent. The acid employed should be the pure monohydrated form, +specific gravity at 20°, 1.845.</p> + +<p>The apparatus used is shown in <a href="#FIG_98">Fig. 98</a>. +<span class="pagenum"><a id="Page_358"></a>[Pg 358]</span></p> + +<div class="figcenter smcap"> + <img id="FIG_98" src="images/fig98.jpg" alt="" width="500" height="467" > + <p class="center spb1">Fig. 98.—Apparatus for Determining Rise<br> + of Temperature with Sulfuric Acid.</p> +</div> + +<p>The test tube which holds the reagents is twenty-four centimeters in +length and five in diameter. It is provided with a stopper having three +perforations, one for a delicate thermometer, one for a bulb funnel for +delivering the sulfuric acid, and one to guide a stirring rod bent into +a spiral as shown. The thermometer is read with a magnifying glass. +Fifty cubic centimeters of the fat are placed in the test tube and ten +of sulfuric acid in the funnel and the apparatus is exposed at the +temperature desired until all parts of it, together with the reagents, +have reached the same degree. The test tube holding the oil should be +placed in a vacuum-jacket tube, such as will be described in paragraph +<b><a href="#P_316">316</a></b>. The oil is allowed to run in as rapidly as possible from +the funnel and the stirring rod is moved up and down two or three times +<span class="pagenum"><a id="Page_359"></a>[Pg 359]</span> +until the oil and acid are well mixed. Care must be exercised to stir +no more than is necessary for good mixing. The mercury is observed +as it ascends in the tube of the thermometer and its maximum height +is noted. With the glass it is easy to read to tenths, when the +thermometer is graduated in fifths of a degree. When oils are tested +which produce a rise of temperature approaching 100°, in the above +circumstances, (cottonseed, linseed and some others) either smaller +quantities should be used or the oil diluted with some inert substance +or dissolved in some inert solvent of high boiling point. For a study +of the variations produced in the rise of temperature when varying +proportions of oil and acid are used, the work of Munroe may be +consulted.<a id="FNanchor_283" href="#Footnote_283" class="fnanchor">[283]</a></p> + +<p>The thermélaeometer described by Jean is a somewhat complicated piece +of apparatus and does not possess any advantage over the simple form +described above.<a id="FNanchor_284" href="#Footnote_284" class="fnanchor">[284]</a></p> + +<p>Instead of expressing the data obtained in thermal degrees showing the +rise of temperature, Thompson and Ballentyne refer them to the heat +produced in mixing sulfuric acid and water.<a id="FNanchor_285" href="#Footnote_285" class="fnanchor">[285]</a></p> + +<p>The observed thermal degree of the oil and acid divided by that of +the water and acid is termed the specific temperature reaction. +For convenience in writing, this quotient is multiplied by 100. +The respective quantities of acid and water are ten and fifty +cubic centimeters. This method of calculation has the advantage of +eliminating to a certain degree the variations which arise in the use +of sulfuric acid of differing specific gravities. In the following +table are given the comparative data obtained for some common oils.<a id="FNanchor_286" href="#Footnote_286" class="fnanchor">[286]</a></p> + +<table class="spb1"> + <thead><tr> + <th class="tdc bb"> </th> + <th class="tdc bb bl bt" colspan="2">Acid of 95.4<br>per cent.</th> + <th class="tdc bb bl bt" colspan="2">Acid of 96.8<br>per cent.</th> + <th class="tdc bb bl bt br" colspan="2">Acid of 99<br>per cent.</th> + </tr><tr> + <th class="tdc bb">Kind of oil.</th> + <th class="tdc bl bb">Rise of temp.<br>with the oil.</th> + <th class="tdc bl bb">Specific temp.<br>reaction.</th> + <th class="tdc bl bb">Rise of temp.<br>with the oil.</th> + <th class="tdc bl bb">Specific temp.<br>reaction.</th> + <th class="tdc bl bb">Rise of temp.<br>with the oil.</th> + <th class="tdc bl bb br">Specific temp.<br>reaction.</th> + </tr></thead> + <tbody><tr> + <td class="tdc"> </td> + <td class="tdc">0°</td> + <td class="tdc">0°</td> + <td class="tdc">0°</td> + <td class="tdc">0°</td> + <td class="tdc">0°</td> + <td class="tdc">0°</td> + </tr><tr> + <td class="tdl">Olive oil</td> + <td class="tdc">36.5</td> + <td class="tdc"> 95</td> + <td class="tdc">39.4</td> + <td class="tdc">85</td> + <td class="tdc">44.8</td> + <td class="tdc"> 96</td> + </tr><tr> + <td class="tdl">Rapeseed oil</td> + <td class="tdc">49.0</td> + <td class="tdc">127</td> + <td class="tdc">37.0</td> + <td class="tdc">89</td> + <td class="tdc">58.0</td> + <td class="tdc">124</td> + </tr><tr> + <td class="tdl">Castor oil</td> + <td class="tdc">34.0</td> + <td class="tdc"> 88</td> + <td class="tdc"> </td> + <td class="tdc"> </td> + <td class="tdc"> </td> + <td class="tdc"> </td> + </tr><tr> + <td class="tdl">Linseed oil</td> + <td class="tdc">104.5 </td> + <td class="tdc">270</td> + <td class="tdc"> </td> + <td class="tdc"> </td> + <td class="tdc">125.2 </td> + <td class="tdc">269</td> + </tr> + </tbody> +</table> + +<p><b>325. Method of Richmond.</b>—The rise of temperature produced by +<span class="pagenum"><a id="Page_360"></a>[Pg 360]</span> +mixing an oil and sulfuric acid is determined by Richmond in a simple +calorimeter, which is constructed by fitting a small deep beaker inside +a larger one with a packing of cotton. The heat capacity of the system +is determined by adding to ten grams of water, in the inner beaker, +at room temperature, twenty-five grams of water of a noted higher +temperature and observing the temperature of the mixture. The cooling +of the system, during the time required for one determination of heat +of sulfuric saponification, does not exceed one per cent of the whole +number of calories produced.<a id="FNanchor_287" href="#Footnote_287" class="fnanchor">[287]</a> +Between the limits of ninety-two per cent and one hundred per cent the +rise of temperature observed is directly proportional to the strength +of the acid.</p> + +<p><i>Relative Maumené Figure.</i>—The total heat evolved per mean +molecule is called by Richmond the relative maumené figure. It is +calculated as follows:</p> + +<ul class="index"> +<li class="isub1">Let <i>x</i> = percentage of sulfuric acid in the acid employed;</li> +<li class="isub2"><i>h</i> = heat capacity of calorimeter in grams of water;</li> +<li class="isub2"><i>R</i> = observed rise of temperature (twenty-five grams of</li> +<li class="isub4">oil, five cubic centimeters sulfuric acid);</li> +<li class="isub2"><i>K</i> = potash absorbed for saponification (19.5 per cent of</li> +<li class="isub4">potassium hydroxid, standard of comparison);</li> +<li class="isub2"><i>M</i> = relative maumené figure:</li> +</ul> + +<table class="spb1 fs_105"> + <tbody><tr> + <td class="tdl" rowspan="2">Then<span class="ws2"><i>M</i></span> = <i>R</i> × </td> + <td class="tdc bb">21.5</td> + <td class="tdl" rowspan="2"> × </td> + <td class="tdc bb">20 + <i>h</i></td> + <td class="tdl" rowspan="2"> × </td> + <td class="tdc bb">19.5</td> + </tr><tr> + <td class="tdc"><i>x</i> - 78.5</td> + <td class="tdc">20</td> + <td class="tdc"><i>K</i></td> + </tr> + </tbody> +</table> + +<p><b>326. Heat of Bromination.</b>—The rise of temperature caused by +mixing fats with sulfuric acid has long been used to discriminate +between different fats and oils. Hehner and Mitchell propose a similar +reaction based upon the rise of temperature produced by mixing bromin +with the sample.<a id="FNanchor_288" href="#Footnote_288" class="fnanchor">[288]</a> +The action of bromin on unsaturated fatty bodies is instantaneous and +is attended with a considerable evolution of heat. Since the action of +bromin on many of the oils is very violent it is necessary to dilute +the reagent with chloroform or glacial acetic acid. Owing to its high +boiling point the acetic acid has some advantage over chloroform for +this purpose. The tests are conveniently made in a vacuum-jacket tube. +<span class="pagenum"><a id="Page_361"></a>[Pg 361]</span> +In such a tube there is no loss of heat by radiation. The bromin is +measured in a pipette having at its upper end a tube filled with +caustic lime held between plugs of asbestos. The bromin sample to be +tested and the diluent employed are kept at the same temperature before +beginning the trial. They are quickly mixed and the rise of temperature +noted. The oil is first dissolved in the chloroform and the bromin then +added.</p> + +<p>A somewhat constant relation is noticed between the rise of temperature +and the iodin number when one gram of oil, ten cubic centimeters of +chloroform and one cubic centimeter of bromin are used.</p> + +<p>If the rise in temperature in degrees be multiplied by 5.5 the product +is approximately the iodin number of the sample. Thus a sample of lard +gave a rise in temperature of 10°.6 and an iodin number of 57.15. The +number obtained by multiplying 10.6 by 5.5 is 58.3.</p> + +<p>In like manner the numbers obtained for some common oils are as follows:</p> + +<table class="spb1"> + <thead><tr> + <th class="tdc">Material.</th> + <th class="tdc">Rise of<br>  temperature <br> with bromin.</th> + <th class="tdc"> Iodin No. </th> + <th class="tdc">Calculated<br> Iodin No.</th> + </tr></thead> + <tbody><tr> + <td class="tdl">Butter fat</td> + <td class="tdr_ws1">6.6</td> + <td class="tdr_ws1">37.1</td> + <td class="tdr_ws1">36.3</td> + </tr><tr> + <td class="tdl">Olive oil</td> + <td class="tdr_ws1">15.0</td> + <td class="tdr_ws1">80.8</td> + <td class="tdr_ws1">82.5</td> + </tr><tr> + <td class="tdl">Maize ”</td> + <td class="tdr_ws1">21.5</td> + <td class="tdr_ws1">122.0</td> + <td class="tdr_ws1">118.2</td> + </tr><tr> + <td class="tdl">Cotton ”</td> + <td class="tdr_ws1">19.4</td> + <td class="tdr_ws1">107.1</td> + <td class="tdr_ws1">106.7</td> + </tr><tr> + <td class="tdl">Castor ”</td> + <td class="tdr_ws1">15.0</td> + <td class="tdr_ws1">83.8</td> + <td class="tdr_ws1">82.5</td> + </tr><tr> + <td class="tdl">Linseed oil</td> + <td class="tdr_ws1">30.4</td> + <td class="tdr_ws1">160.7</td> + <td class="tdr_ws1">167.2</td> + </tr><tr> + <td class="tdl">Codliver ”</td> + <td class="tdr_ws1">28.0</td> + <td class="tdr_ws1">144.0</td> + <td class="tdr_ws1">140.0</td> + </tr> + </tbody> +</table> + +<p><b>327. Modification of the Heat of Bromination Method.</b>—The method +described above by Hehner and Mitchell presents many grave difficulties +in manipulation, on account of the inconvenience of handling liquid +bromin. The process is made practicable by dissolving both the oil or +fat and the bromin in chloroform, or better in carbon tetrachlorid, in +which condition the bromin solution is easily handled by means of a +special pipette.<a id="FNanchor_289" href="#Footnote_289" class="fnanchor">[289]</a></p> + +<p>In order to make a number of analyses of the same sample ten grams of +the fat may be dissolved in chloroform or carbon tetrachlorid and the +volume completed with the same solvent to fifty cubic centimeters. In +like manner twenty cubic centimeters of the bromin are dissolved in one +<span class="pagenum"><a id="Page_362"></a>[Pg 362]</span> +of the solvents named and the volume completed to 100 cubic centimeters +therewith.</p> + +<p>For convenience of manipulation the solutions are thus made of such a +strength that five cubic centimeters of each represent one gram of the +fat and one cubic centimeter of the liquid bromin respectively.</p> + +<div class="figcenter smcap"> + <img id="FIG_99" src="images/fig99.jpg" alt="" width="500" height="592" > + <p class="center spb1">Fig. 99. Apparatus for Determining Heat of Bromination.</p> +</div> + +<p>The apparatus used for the work is shown in the accompanying <a href="#FIG_99">figure</a>. +The pipette for handling the bromin solution is so arranged as to be +<span class="pagenum"><a id="Page_363"></a>[Pg 363]</span> +filled by the pressure of a rubber bulb, thus avoiding the danger of +sucking the bromin vapor into the mouth. The filling is secured by +keeping the bromin solution in a heavy erlenmeyer with a side tubulure +such as is used for filtering under pressure. The solutions are +mixed in a long tube, held in a larger vessel, from which the air is +exhausted to secure a minimum radiation of heat. A delicate thermometer +graduated in tenths serves to register the rise of temperature. The fat +solution is first placed in the test tube, with care not to pour it +down the sides of the tube but to add it by means of a pipette reaching +nearly to the bottom. The whole apparatus having been allowed to come +to a standard temperature the bromin solution is allowed to run in +quickly from the pipette. No stirring is required as the liquids are +sufficiently mixed by the addition of the bromin solution. The mercury +in the thermometer rapidly rises and is read at its maximum point by +means of a magnifying glass. With a thermometer graduated in tenths, it +is easy to read to twentieths of a degree.</p> + +<p>It is evident that the rise of temperature obtained depends on +similar conditions to those mentioned in connection with sulfuric +saponification. Each system of apparatus must be carefully calibrated +under standard conditions and when this is done the comparative rise +of temperature obtained with various oils and fats will prove of +great analytical use. It is evident that the ratio of this rise of +temperature to the iodin number must be determined for every system of +apparatus and for every method of manipulation employed, and no fixed +factor can be given that will apply in every case.</p> + +<p>With the apparatus above described and with the method of manipulation +given the following data were obtained for the oils mentioned:</p> + +<table class="spb1"> + <tbody><tr> + <td class="tdl"> </td> + <td class="tdc">Rise of<br> temperature.</td> + </tr><tr> + <td class="tdl">Olive oil</td> + <td class="tdc">20°.5</td> + </tr><tr> + <td class="tdl">Refined cottonseed oil  </td> + <td class="tdc">25°.7</td> + </tr><tr> + <td class="tdl">Sunflowerseed oil</td> + <td class="tdc">28°.4</td> + </tr><tr> + <td class="tdl">Calycanthusseed oil</td> + <td class="tdc">29°.0</td> + </tr> + </tbody> +</table> + +<p>Bromin and chloroform, when mixed together, give off heat, due to +the chemical reaction resulting from the substitution of bromin for +<span class="pagenum"><a id="Page_364"></a>[Pg 364]</span> +hydrogen in the chloroform molecule and the formation of hydrobromic +acid. For this reason the data obtained, when chloroform is used as a +solvent, are slightly higher than with carbon tetrachlorid. The use of +the latter reagent is therefore to be preferred.</p> + +<p><b>328. Haloid Addition Numbers.</b>—Many of the glycerids possess the +property of combining directly with the haloids and forming thereby +compounds in which the haloid, by simple addition, has become a part of +the molecule. Olein is a type of this class of unsaturated glycerids. +The process may take place promptly as in the case of bromin or move +slowly as with iodin. The quantity of the haloid absorbed is best +determined in the residual matter and not by an examination of the fat +compound. By reason of the ease with which the amount of free iodin in +solution can be determined, this substance is the one which is commonly +employed in analytical operation on fats.</p> + +<p>In general, the principle of the operation depends on bringing the fat +and haloid together in a proper solution and allowing the addition +to take place by simple contact. The quantity of the haloid in the +original solution being known, the amount which remains in solution +after the absorption is complete, deducted from that originally +present, will give the quantity which has entered into combination with +the glycerid.</p> + +<p><b>329. Hübl’s Process.</b>—In determining the quantity of iodin +which will combine with a fat, the method first proposed by Hübl, +or some modification thereof, is universally employed.<a id="FNanchor_290" href="#Footnote_290" class="fnanchor">[290]</a> +In the determination of the iodin number of a glycerid it is important that +it be accomplished under set conditions and that iodid be always present +in large excess. It is only when data are obtained in the way noted +that they can be regarded as useful for comparison and determination. +Many modifications of Hübl’s process have been proposed, but it is +manifestly impracticable to give even a summary of them here. As +practiced in the chemical laboratory of the Agricultural Department and +by the Association of Official Agricultural Chemists, it is carried out +as follows:<a id="FNanchor_291" href="#Footnote_291" class="fnanchor">[291]</a></p> + +<h4>(1) <span class="allsmcap">PREPARATION OF REAGENTS.</span></h4> + +<p>(<i>a</i>). <i>Iodin Solution.</i>—Dissolve twenty-five grams of pure +<span class="pagenum"><a id="Page_365"></a>[Pg 365]</span> +iodin in 500 cubic centimeters of ninety-five per cent alcohol. +Dissolve thirty grams of mercuric chlorid in 500 cubic centimeters of +ninety-five per cent alcohol. The latter solution, if necessary, is +filtered, and then the two solutions mixed. The mixed solution should +be allowed to stand twelve hours before using.</p> + +<p>(<i>b</i>). <i>Decinormal Sodium Thiosulfate Solution.</i>—Dissolve +24.8 grams of chemically pure sodium thiosulfate, freshly pulverized +as finely as possible and dried between filter or blotting paper, +and dilute with water to one liter, at the temperature at which the +titrations are to be made.</p> + +<p>(<i>c</i>). <i>Starch Paste.</i>—One gram of starch is boiled in 200 +cubic centimeters of distilled water for ten minutes and cooled to room +temperature.</p> + +<p>(<i>d</i>). <i>Solution of Potassium Iodid.</i>—One hundred and fifty +grams of potassium iodid are dissolved in water and the volume made up +to one liter.</p> + +<p>(<i>e</i>). <i>Solution of Potassium Bichromate.</i>—Dissolve 3.874 +grams of chemically pure potassium bichromate in distilled water +and make the volume up to one liter at the temperature at which the +titrations are to be made.</p> + +<h4>(2). <span class="allsmcap">DETERMINATION.</span></h4> + +<p>(<i>a</i>). <i>Standardizing the Sodium Thiosulfate +Solution.</i>—Place twenty cubic centimeters of the potassium +bichromate solution, to which have been added ten cubic centimeters of +the solution of potassium iodid, in a glass stopper flask. Add to this +mixture five cubic centimeters of strong hydrochloric acid. Allow the +solution of sodium thiosulfate to flow slowly into the flask until the +yellow color of the liquid has almost disappeared. Add a few drops of +the starch paste, and with constant shaking continue to add the sodium +thiosulfate solution until the blue color just disappears. The number +of cubic centimeters of thiosulfate solution used multiplied by five is +equivalent to one gram of iodin. +<span class="pagenum"><a id="Page_366"></a>[Pg 366]</span></p> + +<p class="blockquot"><i>Example.</i>—Twenty cubic centimeters of +potassium bichromate solution required 16.2 sodium thiosulfate; then +16.2 × 5 = 81 = number cubic centimeters of thiosulfate solution +equivalent to one gram of iodin. Then one cubic centimeter thiosulfate +solution = 0.0124 gram of iodin: (Theory for decinormal solution of +sodium thiosulfate, one cubic centimeter = 0.0127 gram of iodin.)</p> + +<p>(<i>b</i>). <i>Weighing the Sample.</i>—About one gram of butter +fat is placed in a glass stopper flask, holding about 300 cubic +centimeters, with the precautions to be mentioned for weighing the fat +for determining volatile acids.</p> + +<p>(<i>c</i>). <i>Absorption of Iodin.</i>—The fat in the flask is +dissolved in ten cubic centimeters of chloroform. After complete +solution has taken place thirty cubic centimeters of the iodin solution +(1) (<i>a</i>) are added. The flask is now placed in a dark place and +allowed to stand, with occasional shaking, for three hours.</p> + +<p>(<i>d</i>). <i>Titration of the Unabsorbed Iodin.</i>—One hundred +cubic centimeters of distilled water are added to the contents of the +flask, together with twenty cubic centimeters of the potassium iodid +solution. Any iodin which may be noticed upon the stopper of the flask +should be washed back into the flask with the potassium iodid solution. +The excess of iodin is taken up with the sodium thiosulfate solution, +which is run in gradually, with constant shaking, until the yellow +color of the solution has almost disappeared. A few drops of starch +paste are added, and the titration continued until the blue color +has entirely disappeared. Toward the end of the reaction the flask +should be stoppered and violently shaken, so that any iodin remaining +in solution in the chloroform may be taken up by the potassium iodid +solution in the water. A sufficient quantity of sodium thiosulfate +solution should be added to prevent a reappearance of any blue color in +the flask for five minutes.</p> + +<p>(<i>e</i>). <i>Setting the Value of the Iodin Solution by the +Thiosulfate Solution.</i>—At the time of adding the iodin solution +to the fat, two flasks of the same size as those used for the +determination should be employed for conducting the operation described +above, but without the presence of any fat. In every other respect the +performance of the blank experiments should be just as described. These +blank experiments must be made each time the iodin solution is used.</p> + +<p><i>Example of Blank Determinations.</i>—Thirty cubic centimeters of +<span class="pagenum"><a id="Page_367"></a>[Pg 367]</span> +iodin solution required 46.4 cubic centimeters of sodium thiosulfate +solution: Thirty cubic centimeters of iodin solution required 46.8 +cubic centimeters of sodium thiosulfate solution: Mean, 46.6 cubic +centimeters.</p> + +<table class="spb1"> + <tbody><tr> + <td class="tdl">Weight of fat</td> + <td class="tdr">1.0479</td> + <td class="tdl_wsp">grams</td> + <td class="tdl_wsp"> </td> + </tr><tr> + <td class="tdl">Quantity of iodin solution used</td> + <td class="tdr">30.0</td> + <td class="tdl_wsp">cubic</td> + <td class="tdl_wsp">centimeters</td> + </tr><tr> + <td class="tdl">Thiosulfate equivalent to iodin used</td> + <td class="tdr">46.6</td> + <td class="tdc">”</td> + <td class="tdc">”</td> + </tr><tr> + <td class="tdl">Thiosulfate equivalent to remaining iodin</td> + <td class="tdr">14.7</td> + <td class="tdc">”</td> + <td class="tdc">”</td> + </tr><tr> + <td class="tdl">Thiosulfate equivalent to iodin absorbed</td> + <td class="tdr">31.9</td> + <td class="tdc">”</td> + <td class="tdc">”</td> + </tr><tr> + <td class="tdl" colspan="4">Percent of iodin absorbed, 31.9 × 0.0124 × 100 ÷ 1.0479 = 37.75.</td> + </tr> + </tbody> +</table> + +<p><b>330. Character of Chemical Reaction.</b>—The exact nature of +the chemical process which takes place in this reaction is not +definitely known. Hübl supposed that the products formed were +chloro-iodid-additive compounds, and he obtained a greasy product from +oleic acid, to which he ascribed the formula <b>C₁₈H₃₄IClO₂</b>. By others it +is thought that chlorin alone may be added to the molecule.<a id="FNanchor_292" href="#Footnote_292" class="fnanchor">[292]</a></p> + +<p>In general, it may be said that none of the glycerids capable +of absorbing halogens is able to take on a quantity equivalent +to theory.<a id="FNanchor_293" href="#Footnote_293" class="fnanchor">[293]</a> +While the saturated fatty acids (stearic series) theoretically are not +able to absorb iodin some of them are found to do so to a small degree. +It is evident, therefore, that it is not possible to calculate the +percentage of unsaturated glycerids in a fat from their iodin number +alone. According to the data worked out by Schweitzer and Lungwitz both +addition and substitution of iodin take place during the reaction.<a id="FNanchor_294" href="#Footnote_294" class="fnanchor">[294]</a> +This fact they determined by titration with potassium iodate and iodid +according to the formula <b>5HI + HIO₃ = 6I + 6H₂O</b>. The authors +confess that whenever free hydriodic acid is found in the mixture that +iodin substitution has taken place and that for each atom of hydrogen +eliminated from the fat molecule two atoms of iodin disappear, one as +the substitute and the other in the form of hydriodic acid. When carbon +bisulfid or tetrachlorid is used as a solvent no substitution takes +place and pure additive compounds are formed.</p> + +<p>The following process is recommended to secure a pure iodin addition to +<span class="pagenum"><a id="Page_368"></a>[Pg 368]</span> +a glycerid: About one gram or a little less of the oil or fat is placed +in a glass stopper flask, to which are added about seven-tenths of a +gram of powdered mercuric chlorid and twenty-five cubic centimeters of +a solution of iodin in carbon bisulfid. The stopper is made tight by +smearing it with powdered potassium iodid, tied down, and the mixture +is heated for some time under pressure. By this method it is found that +no hydriodic acid is formed, and hence all the iodin which disappears +is added to the molecule of the glycerid. The additive numbers obtained +for some oils are appended:</p> + +<table class="spb1"> + <tbody><tr> + <td class="tdc bb">Oil.</td> + <td class="tdc bb">Time of<br>heating.</td> + <td class="tdc bb">Temperature.</td> + <td class="tdc bb">Per cent<br> iodin added. </td> + <td class="tdc bb">Per cent<br> hübl number. </td> + </tr><tr> + <td class="tdl">Lard oil</td> + <td class="tdl_wsp">30 minutes.</td> + <td class="tdc">50°.0</td> + <td class="tdc"> 73.0</td> + <td class="tdc"> 78.4</td> + </tr><tr> + <td class="tdl">Cottonseed oil </td> + <td class="tdl_wsp">2 hours.</td> + <td class="tdc">50°.0</td> + <td class="tdc">103.0</td> + <td class="tdc">106.5</td> + </tr><tr> + <td class="tdl">Oleic acid</td> + <td class="tdl_wsp">2 ”</td> + <td class="tdc">65°.5</td> + <td class="tdc"> 93.8</td> + <td class="tdc"> </td> + </tr> + </tbody> +</table> + +<p><b>331. Solution in Carbon Tetrachlorid.</b>—Gantter has called +attention to the fact that the amount of iodin absorbed by fat does +not depend alone upon the proportion of iodin present but also upon +the amount of mercuric chlorid in the solution.<a id="FNanchor_295" href="#Footnote_295" class="fnanchor">[295]</a> +Increasing amounts of mercuric chlorid cause uniformly a much greater +absorption of the iodin. For this reason he proposes to discard the use +of mercuric chlorid altogether for the hübl test and to use a solvent +which will at the same time dissolve both the iodin and the fat. For +this purpose he uses carbon tetrachlorid. The solutions are prepared as +follows:</p> + +<p><i>Iodin Solution.</i>—Ten grams of iodin are dissolved in one liter +of carbon tetrachlorid.</p> + +<p>In the preparation of this solution the iodin must not be thrown +directly into the flask before the addition of the tetrachlorid. Iodin +dissolves very slowly in carbon tetrachlorid and the solution is made +by placing it in a sufficiently large weighing glass and adding a +portion of the carbon tetrachlorid thereto. The solution is facilitated +by stirring with a glass rod until the added tetrachlorid is apparently +charged with the dissolved iodin. The dissolved portion is then poured +into a liter flask, new portions added to the iodin and this process +continued until the iodin is completely dissolved, and then sufficient +additional quantities of the tetrachlorid are added to fill the flask +up to the mark. +<span class="pagenum"><a id="Page_369"></a>[Pg 369]</span></p> + +<p><b>332. Sodium Thiosulfate Solution.</b>—Dissolve 19.528 grams of pure +sodium thiosulfate in 1000 cubic centimeters of water. For determining +the strength of the solution by titration, the solution of iodin in +carbon tetrachlorid and a solution of sodium thiosulfate in water are +each placed in a burette. A given volume of the iodin solution is +first run into a flask with a glass stopper and afterward the sodium +thiosulfate added little by little until, after a vigorous shaking, +the liquid has only a little color. Some solution of starch is then +added and shaken until the mixture becomes deep blue. The sodium +thiosulfate solution is added drop by drop, with vigorous shaking after +each addition, until the solution is completely decolorized. If both +solutions have been correctly made with pure materials they will be of +equal strength; that is, ten cubic centimeters of the iodin solution +will be exactly decolorized by ten cubic centimeters of the sodium +thiosulfate solution.</p> + +<p><b>333. Method of Conducting the Absorption.</b>—The quantity of the +fat or oil employed should range from 100 to 200 milligrams, according +to the absorption equivalent. These quantities should be placed in +flasks with glass stoppers in the ordinary way. In the flasks are +placed exactly fifty cubic centimeters of the iodin solution equivalent +to 500 milligrams of iodin, and the flask is then stoppered and shaken +until the fat or oil is completely dissolved. In order to avoid the +volatilization of the iodin finally, sufficient water is poured into +the flask to form a layer about one millimeter in thickness over the +solution containing the iodin and fat. The stopper should be carefully +inserted and the flask allowed to stand at rest for fifty hours.</p> + +<p><b>334. Estimation of the Iodin Number.</b>—This is determined in the +usual way by titration of the amount of iodin left in excess after the +absorption as above described. The iodin number is to be expressed +by the number of milligrams of iodin which are absorbed by each 100 +milligrams of fat.</p> + +<p><i>Example.</i>—One hundred and one milligrams of flaxseed oil were +dissolved in fifty cubic centimeters of the carbon tetrachlorid +solution of iodin and allowed to stand as above described for fifty +<span class="pagenum"><a id="Page_370"></a>[Pg 370]</span> +hours. At the end of this time, 42.3 cubic centimeters of the sodium +thiosulfate solution were required to decolorize the excess of iodin +remaining.</p> + +<p><i>Statement of Results.</i>—Fifty cubic centimeters of the sodium +thiosulfate equal 500 milligrams of iodin; therefore, 42.3 cubic +centimeters of the thiosulfate solution equal 423 milligrams of iodin. +The difference equals seventy-seven milligrams of iodin absorbed by 101 +milligrams of the flaxseed oil. Therefore, the iodin number equivalent +and the milligrams of iodin absorbed by 100 milligrams of flaxseed oil +equal 76.2.</p> + +<p>It is evident from the above determination that the iodin number of +the oil, when obtained in the manner described, is less than half that +secured by the usual hübl process. Since the solvent employed, however, +is more stable than chloroform when in contact with iodin or bromin, +the proposed variation is one worthy of the careful attention of +analysts.</p> + +<p>McIlhiney has called especial attention to the low numbers given by the +method of Gantter, and from a study of the data obtained concludes that +iodin alone will not saturate glycerids, no matter what the solvents +may be.<a id="FNanchor_296" href="#Footnote_296" class="fnanchor">[296]</a></p> + +<p>It is clear, therefore, that the process of Gantter cannot give numbers +which are comparable with those obtained by the usual iodin method. Any +comparative value possessed by the data given by the process of Gantter +must be derived by confining it to the numbers secured by the carbon +tetrachlorid process alone.</p> + +<p><b>335. Substitution of Iodin Monochlorid for Hübl’s +Reagent.</b>—Ephraim has shown that iodin monochlorid may be +conveniently substituted for the hübl reagent with the advantage +that it can be safely used at once, while the hübl reagent undergoes +somewhat rapid changes when first prepared. The present disadvantage of +the process is found in the fact that the iodin monochlorid of commerce +is not quite pure and each new lot requires to be titrated for the +determination of its purity.</p> + +<p>The reagent is prepared of such a strength as to contain 16.25 grams of +iodin monochlorid per liter. The solvent used is alcohol. The operation +is carried out precisely as in the hübl method, substituting the +alcoholic solution of iodin monochlorid for the iodin reagent proposed +<span class="pagenum"><a id="Page_371"></a>[Pg 371]</span> +by Hübl.<a id="FNanchor_297" href="#Footnote_297" class="fnanchor">[297]</a> +If the iodin monochlorid solution, after acting on the oil, be titrated +without previous addition of potassium iodid a new value is obtained, +the chloriodin number. In titrating, the sodium thiosulfate is added +until the liquid, which is made brown by the separated iodin, becomes +yellow. At this point the solution is diluted, starch paste added, and +the titration completed.</p> + +<p><b>336. Preservation of the Hübl Reagent.</b>—To avoid the trouble due +to changes in the strength of Hübl’s reagent, Mahle adds hydrochloric +acid to it at the time of its preparation.<a id="FNanchor_298" href="#Footnote_298" class="fnanchor">[298]</a> +The reagent is prepared as follows: Twenty-five grams of iodin +dissolved in a quarter of a liter of ninety-five per cent alcohol +are mixed with the same quantity of mercuric chlorid in 200 cubic +centimeters of alcohol, the same weight of hydrochloric acid of 1.19 +specific gravity added and the volume of the mixture completed to +half a liter with alcohol. After five days such a solution gave, on +titration, 49.18 instead of 49.31 grams per liter of iodin.</p> + +<p>It will be observed that this solution is double the usual strength, +but this does not influence the accuracy of the analytical data +obtained. It appears that the hübl number is not, therefore, an iodin +number, but expresses the total quantity of iodin, chlorin and oxygen +absorbed by the fat during the progress of the reaction.</p> + +<p><b>337. Bromin Addition Number.</b>—In the process of Hübl and others +an attempt is made to determine the quantity of a halogen, <i>e.g.</i>, +iodin, which the oil, fat or resin will absorb under certain +conditions. The numbers obtained, however, represent this absorption +only approximately, because the halogen may disappear through +substitution as well as absorption. Whether or not a halogen is added, +<i>i. e.</i>, absorbed or substituted, may be determined experimentally.</p> + +<p>The principle on which the determination depends rests on the fact that +a halogen, <i>e. g.</i>, bromin, forms a molecule of hydrobromic acid +for every atom of bromin substituted, while in a simple absorption +of the halogen no such action takes place. If, therefore, bromin be +brought into contact with a fat, oil or resin, the determination of the +<span class="pagenum"><a id="Page_372"></a>[Pg 372]</span> +quantity of hydrobromic acid formed will rigidly determine the quantity +of bromin substituted during the reaction. If this quantity be deducted +from the total bromin which has disappeared, the relative quantities of +the halogen added and substituted are at once determined. In the method +of McIlhiney<a id="FNanchor_299" href="#Footnote_299" class="fnanchor">[299]</a> +bromin is used instead of iodin because the addition figures of iodin +are in general much too low.</p> + +<p><i>The Reagents.</i>—The following solutions are employed:</p> + +<div class="blockquot"> +<p>1. One-third normal bromin dissolved in carbon tetrachlorid:</p> + +<p>2. One-tenth normal sodium thiosulfate:</p> + +<p>3. One-tenth normal potassium hydroxid.</p> +</div> + +<p><i>The Manipulation.</i>—From a quarter to one gram of the fat, oil +or resin, is dissolved in ten cubic centimeters of carbon tetrachlorid +in a dry bottle of 500 cubic centimeters capacity, provided with a +well-ground glass stopper. An excess of the bromin solution is added, +the bottle tightly stoppered, well shaken and placed in the dark. At +the end of eighteen hours the bottle is placed in a freezing mixture +and cooled until a partial vacuum is formed. A piece of wide rubber +tubing an inch and a half long is slipped over the lip of the bottle so +as to form a well about the stopper. This well having been filled with +water the stopper is lifted and the water is sucked into the bottle +absorbing all the hydrobromic acid which has been formed. The well +should be kept filled with water, as it is gradually taken in until in +all twenty-five cubic centimeters have been added. The bottle is next +well shaken and from ten to twenty cubic centimeters of a twenty per +cent potassium iodid solution added.</p> + +<p>The excess of bromin liberates a corresponding amount of iodin, which +is determined by the thiosulfate solution in the usual way, after +adding about seventy-five cubic centimeters of water. The total bromin +which has disappeared is then calculated from the data obtained, +the strength of the original bromin solution having been previously +determined. The contents of the bottle are next transferred to a +separatory funnel, the aqueous portion separated, filtered through a +linen filter, a few drops of thiosulfate solution added, if a blue +color persist, and the free hydrobromic acid determined by titration +with potassium hydroxid, using methyl orange as indicator. The end +<span class="pagenum"><a id="Page_373"></a>[Pg 373]</span> +reaction is best observed by placing the solution in a porcelain +dish, adding the alkali in slight excess, and titrating back with +tenth-normal hydrochloric acid until the pink tint is perceived. +From the number of cubic centimeters of alkali used the amount of +bromin present as hydrobromic acid is calculated, and this expressed +as percentage gives the bromin substitution figure. The bromin +substitution figure multiplied by two and subtracted from the total +absorption gives the addition figure.</p> + +<p>Following are the data for some common substances:</p> + +<table class="spb1"> + <thead><tr> + <th class="tdc bb" colspan="3">Substance.</th> + <th class="tdc bb">Total bromin<br> absorption in <br>eighteen hours.</th> + <th class="tdc bb">Bromin<br> addition <br>figure.</th> + <th class="tdc bb">Bromin<br> substitution <br>figure.</th> + </tr></thead> + <tbody><tr> + <td class="tdl" colspan="3">Rosin</td> + <td class="tdc">212.70</td> + <td class="tdc"> 0.00</td> + <td class="tdc">106.35 </td> + </tr><tr> + <td class="tdl">Raw</td> + <td class="tdl_wsp">linseed</td> + <td class="tdl_wsp">oil</td> + <td class="tdc">102.88</td> + <td class="tdc">102.88</td> + <td class="tdc">00.00</td> + </tr><tr> + <td class="tdl">Boiled</td> + <td class="tdc">”</td> + <td class="tdc">”</td> + <td class="tdc">103.92</td> + <td class="tdc">103.92</td> + <td class="tdc">00.00</td> + </tr><tr> + <td class="tdl">Salad</td> + <td class="tdl_wsp">cotton</td> + <td class="tdc">”</td> + <td class="tdc"> 65.54</td> + <td class="tdc"> 64.26</td> + <td class="tdc"> 0.64</td> + </tr><tr> + <td class="tdl">Sperm</td> + <td class="tdl_wsp"> </td> + <td class="tdc">”</td> + <td class="tdc"> 56.60</td> + <td class="tdc"> 54.52</td> + <td class="tdc"> 1.04</td> + </tr> + </tbody> +</table> + +<p>By the process just described it is possible to detect mixtures of +rosins and rosin oils with animal and vegetable oils. In this respect +it possesses undoubted advantages over the older methods.</p> + +<p><b>338. Method Of Hehner.</b>—The absorption of bromin which takes +place when unsaturated fats are brought into contact with that reagent +was made the basis of an analytical process, proposed by Allen as +long ago as 1880.<a id="FNanchor_300" href="#Footnote_300" class="fnanchor">[300]</a> +In the further study of the phenomena of bromin absorption, as +indicated by McIlhiney, Hehner modified the method as indicated +below.<a id="FNanchor_301" href="#Footnote_301" class="fnanchor">[301]</a> +From one to three grams of the sample are placed in a tared +wide-mouthed flask and dissolved in a little chloroform. Bromin is +added to the solution, drop by drop, until it is in decided excess. +The flask is placed on a steam-bath and heated until the greater +part of the bromin is evaporated, when some more chloroform is added +and the heating continued until all the free bromin has escaped. The +flask is put in a bath at 125° and dried to constant weight. A little +acrolein and hydrobromic acid escape during the drying and the residue +may be colored, or a heavy bromo oil be obtained. The gain in weight +<span class="pagenum"><a id="Page_374"></a>[Pg 374]</span> +represents the bromin absorbed. The bromin number may be converted into +the iodin number by multiplying by 1.5875.<a id="FNanchor_302" href="#Footnote_302" class="fnanchor">[302]</a></p> + +<div class="figleft smcap"> + <img id="FIG_100" src="images/fig100.jpg" alt="" width="100" height="365" > + <p class="center">Fig. 100.—<br>Olein<br> Tube.</p> +</div> + +<p id="P_339"><b>339. Halogen Absorption and Addition of Fat Acids.</b>—Instead of +employing the natural glycerids for determining the degree of action +with the halogens the acids may be separated by some of the processes +of saponification hereafter described and used as directed for the +glycerids themselves. It is doubtful if any practical advantage arises +from this variation of the process. If the fat acids be separated, +however, it is possible to get some valuable data from the halogen +absorption of the fractions. Theoretically the stearic series of acids +would suffer no change in contact with halogens while the oleic series +is capable of a maximum absorptive and additive action. On this fact is +based a variation of the iodin process in which an attempt is made to +separate the oleic acid from its congeners and to apply the halogen to +the separated product.</p> + +<p>The method of separation devised by Muter is carried out as +follows:<a id="FNanchor_303" href="#Footnote_303" class="fnanchor">[303]</a> +The separatory or olein tube consists of a wide burette stem, provided +with a lateral stopcock, and drawn out below to secure a clamp delivery +tube, and at the top expanded into a bulb closed with a ground glass +stopper, as shown in <a href="#FIG_100">Fig. 100</a>. Forty cubic centimeters +of liquid are placed in the tube and the surface is marked 0. Above this the +graduation is continued in cubic centimeters to 250, which figure is +just below the bulb at the top.</p> + +<p>The process of analysis is conducted as follows: About three grams of +the oil or fat are placed in a flask, with fifty cubic centimeters of +alcoholic potash lye, containing enough potassium hydroxid to ensure +complete saponification. The flask is closed and heated on a water-bath +until saponification is complete. The pressure flask to be described +hereafter may be conveniently used. After cooling, the excess of alkali +is neutralized with acetic acid in presence of phenolphthalien and then +alcoholic potash added until a faint pink color is produced. In a large +porcelain dish place 200 cubic centimeters of water and thirty of a ten +per cent solution of lead acetate and boil. Pour slowly, with constant +<span class="pagenum"><a id="Page_375"></a>[Pg 375]</span> +stirring, into the boiling liquid the soap solution prepared as above +described, and allow to cool, meanwhile continuing the stirring. At the +end, the liquid remaining is poured off and the solid residue washed +with hot water by decantation.</p> + +<p>The precipitate of lead salts is finally removed from the dish into a +stoppered bottle, the dish washed with pure ether, the washings added +to the bottle together with enough ether to make the total volume +thereof 120 cubic centimeters. The closed bottle is allowed to stand +for twelve hours with occasional shaking, by which time the lead oleate +will have been completely dissolved. The insoluble lead salts are next +separated by filtration, and the filtrate collected in the olein tube. +The washing is accomplished by ether and, to avoid loss, the funnel +is covered with a glass plate. The ethereal solution of lead oleate +is decomposed by dilute hydrochloric acid, using about forty cubic +centimeters of a mixture containing one part of strong acid to four +of water. The olein tube is closed and shaken until the decomposition +is complete, which will be indicated by the clearing of the ethereal +solution. The tube is allowed to remain at rest until the liquids +separate and the aqueous solution is run out from the pinch-cock at the +lower end. The residue is washed with water by shaking, the water drawn +off as just described, and the process continued until all acidity is +removed.</p> + +<p>Water is then added until the separating plane between the two liquids +is at the zero of the graduation, and enough ether added to make the +ethereal solution of a desired volume, say 200 cubic centimeters. +After well mixing, the ethereal solution or an aliquot part thereof, +<i>e.g.</i>, fifty cubic centimeters, is removed by the side tubulure +and nearly the whole of the ether removed from the portion by +distillation. To the residue are added fifty cubic centimeters of pure +alcohol and the solution is titrated for oleic acid with decinormal +sodium hydroxid solution. Each cubic centimeter of the hydroxid +solution used is equivalent to 0.0282 gram of oleic acid. The total +quantity of oleic acid contained in the amount of fat used is readily +calculated from the data obtained. +<span class="pagenum"><a id="Page_376"></a>[Pg 376]</span></p> + +<p>To determine the iodin absorption of the free acid another measured +quantity of the ethereal solution containing as nearly as possible half +a gram of oleic acid, is withdrawn from the olein tube, and the ether +removed in an atmosphere of pure carbon dioxid. To the residue, without +allowing it to come in contact with the air, fifty cubic centimeters +of Hübl’s reagent are added and the flask put aside in the dark for +twelve hours. At the end of this time thirty-five cubic centimeters of +a ten per cent solution of potassium iodid are added, the contents of +the flask made up to a quarter of a liter with water, fifteen cubic +centimeters of chloroform added, and the excess of iodin titrated +in the way already described. The percentage of iodin absorbed is +calculated as already indicated.</p> + +<p>Lane has proposed a more rapid process for the above determination.<a id="FNanchor_304" href="#Footnote_304" class="fnanchor">[304]</a> +The lead soaps are precipitated in a large erlenmeyer and cooled +rapidly in water, giving the flask meanwhile a circular motion which +causes the soaps to adhere to its walls. Wash with hot water, rinsing +once with alcohol, add 120 cubic centimeters of ether, attach a reflux +condenser, and boil until the lead oleate is dissolved, cool slowly, to +allow any lead stearate which has passed into solution to separate, and +filter into the olein tube. The rest of the operation is conducted as +described above. The percentage of oleic acid and its iodin absorption +in the following glycerids are given in the table below:</p> + +<table class="spb1"> + <tbody><tr class="fs_90"> + <td class="tdl"> </td> + <td class="tdc">Cottonseed<br> oil.</td> + <td class="tdc">  Lard.  </td> + <td class="tdc">Peanut oil.</td> + </tr><tr> + <td class="tdl">Per cent oleic acid</td> + <td class="tdc"> 75.16</td> + <td class="tdc">64.15</td> + <td class="tdc"> 79.84</td> + </tr><tr> + <td class="tdl">Per cent iodin absorbed</td> + <td class="tdc">141.96</td> + <td class="tdc">99.48</td> + <td class="tdc">114.00</td> + </tr> + </tbody> +</table> + +<p id="P_340"><b>340. Saponification.</b>—In many of the analytical operations which +are conducted on the glycerids it is necessary to decompose them. +When this is accomplished by the action of a base which displaces +the glycerol from its combination with the fat acids, the resulting +salts are known as soaps and the process is named saponification. In +general use the term saponification is applied, not only strictly, as +above defined, but also broadly, including the setting free of the +glycerol either by the action of strong acids or by the application +of superheated steam. In chemical processes the saponification of a +<span class="pagenum"><a id="Page_377"></a>[Pg 377]</span> +glycerid is almost always accomplished by means of soda or potash +lye. This may be in aqueous or alcoholic solution and the process is +accomplished either hot or cold, in open vessels or under pressure. +It is only important that the alkali and glycerid be brought into +intimate contact. The rate of saponification is a function of the +intimacy of contact, the nature of the solvent and the temperature. For +chemical purposes, it is best that the decomposition of the glycerid be +accomplished at a low temperature and for most samples this is secured +by dissolving the alkali in alcohol.</p> + +<p>In respect of solvents, that one would be most desirable, from +theoretical considerations, which acts on both the glycerids and +alkalies. In the next rank would be those which dissolve one or the +other of the materials and are easily miscible, as, for instance, +carbon tetrachlorid for the glycerid and alcohol for the alkali. +As a rule, the glycerid is not brought into solution before the +saponification process is commenced. Instead of using an alcoholic +solution of sodium or potassium hydroxid the sodium or potassium +alcoholate may be employed, made by dissolving metallic sodium or +potassium in alcohol. It is probable, however, that a little water is +always necessary to complete the process.</p> + +<p>If a fat be dissolved in ether and treated with sodium alcoholate, +a granular deposit of soap is soon formed and the saponification is +completed in twenty-four hours. As much as 150 grams of fat can be +saponified with ten grams of metallic sodium dissolved in 250 cubic +centimeters of absolute alcohol.<a id="FNanchor_305" href="#Footnote_305" class="fnanchor">[305]</a> +For practical purposes the alcoholic solution of the hydroxid is sufficient.</p> + +<p>The chemical changes which fats undergo on saponification are of a +simple kind. When the process is accomplished by means of alkalies, +the alkaline base takes the place of the glycerol as indicated in the +following equation:</p> + +<table class="spb1 fs_105"> + <tbody><tr> + <td class="tdc">Triolein 884.</td> + <td class="tdl"> </td> + <td class="tdl"> Potassium<br> hydroxid 168.</td> + <td class="tdl"> </td> + </tr><tr> + <td class="tdl">C₃H₅(O.C₁₈H₃₃O)₃</td> + <td class="tdc"> + </td> + <td class="tdl">  3KOH</td> + <td class="tdl"> =</td> + </tr><tr> + <td class="tdc" colspan="4"> </td> + </tr><tr> + <td class="tdc"> Potassium<br> oleate 960.</td> + <td class="tdl"> </td> + <td class="tdl">Glycerol 92.</td> + <td class="tdl"> </td> + </tr><tr> + <td class="tdc">(KO.C₁₈H₃₃O)₃</td> + <td class="tdl"> + </td> + <td class="tdc">C₃H₅(OH)₃.</td> + <td class="tdc"> </td> + </tr> + </tbody> +</table> + +<p>The actual changes which take place in ordinary saponification are +not so simple, however, since natural glycerids are mixtures of +several widely differing fats, each of which has its own rate of +<span class="pagenum"><a id="Page_378"></a>[Pg 378]</span> +decomposition. Palmitin and stearin, for instance, are saponified more +readily than olein and some of the saponifiable constituents of resins +and waxes are extremely resistant to the action of alkalies. The above +equation may be regarded as typical for saponification in aqueous or +alcoholic solutions in open dishes or under pressure. If the alkali +used be prepared by dissolving metallic sodium or potassium in absolute +alcohol (sodium alcoholate or ethoxid) the reaction which takes place +is probably represented by the equation given below:</p> + +<p class="f105">C₃H₅(O.C₁₈H₃₃O)₃ + 3C₂H₅.ONa = C₃H₅(ONa)₃ + 3C₁₈H₃₃O.O.C₂H₅,</p> + +<p class="no-indent">in which it is seen that complete saponification +cannot occur without the absorption of some water, by which the sodium +glyceroxid is converted into glycerol and sodium hydroxid, the latter +compound eventually uniting with the ethyl ether of the fat acid.<a id="FNanchor_306" href="#Footnote_306" class="fnanchor">[306]</a></p> + +<p>Glycerids are decomposed when heated with water under a pressure of +about sixteen atmospheres or when subjected to a current of superheated +steam at 200°. The reaction consists in the addition of the elements +of water, whereby the glyceryl radicle is converted into free glycerol +and the fat acid is set free. The chemical change which ensues is shown +below:</p> + +<p class="f105">C₃H₅(O.C₁₈H₃₃O)₃ + 3H₂O = 3C₁₈H₃₄O₂ + C₃H₅(OH)₃.</p> + +<p>The details of saponification with sulfuric acid are of no interest +from an analytical point of view.<a id="FNanchor_307" href="#Footnote_307" class="fnanchor">[307]</a></p> + +<p id="P_341"><b>341. Saponification in an Open Dish.</b>—The simplest method of +saponifying fats is to treat them with the alkaline reagent in an +open dish. In all cases the process is accelerated by the application +of heat. Vigorous stirring also aids the process by securing a more +intimate mixture of the ingredients. This method of decomposing +glycerids, however, is not applicable in cases where volatile ethers +may be developed. These ethers may escape saponification and thus +prevent the formation of the maximum quantity of soap. While not suited +to exact quantitive work, the method is convenient in the preparation +of fat acids which are to be the basis of subsequent analytical +<span class="pagenum"><a id="Page_379"></a>[Pg 379]</span> +operations, as, for instance, in the preparation of fat acids for +testing with silver nitrate. Large porcelain dishes are conveniently +used and the heat is applied in any usual way, with care to avoid +scorching the fat.</p> + +<p><b>342. Saponification under Pressure.</b>—The method of +saponification which has given the best satisfaction in my work and +which has been adopted by the Association of Official Agricultural +Chemists is described below.<a id="FNanchor_308" href="#Footnote_308" class="fnanchor">[308]</a></p> + +<p><i>Reagents.</i>—The reagents employed are a solution of pure potash +containing 100 grams of the hydroxid dissolved in fifty-eight grams of +recently boiled distilled water, alcohol of approximately ninety-five +per cent strength redistilled over caustic soda, and sodium hydroxid +solution prepared as follows:</p> + +<p>One hundred grams of sodium hydroxid are dissolved in 100 cubic +centimeters of distilled water. The caustic soda should be as free as +possible from carbonates, and be preserved from contact with the air.</p> + +<p><i>Apparatus.</i>—A saponification flask; it has a round bottom and a +ring near the top, by means of which the stopper can be tied down. The +flask is arranged for heating as shown in <a href="#FIG_101">Fig. 101</a>. +A pipette graduated to deliver forty cubic centimeters is recommended +as being more convenient than a burette for measuring the solutions: A +pipette with a long stem graduated to deliver 5.75 cubic centimeters at 50°.</p> + +<p><i>Manipulation.</i>—The fat to be examined should be melted and kept +in a dry warm place at about 60° for two or three hours, until the +water has entirely separated. The clear supernatant fat is poured off +and filtered through a dry filter paper in a jacket funnel containing +boiling water. Should the filtered fat, in a fused state, not be +perfectly clear, it must be filtered a second time. The final drying is +accomplished at 100° in a thin layer in a flat bottom dish, in partial +vacuum or an atmosphere of inert gas.</p> + +<p>The saponification flasks are prepared by thoroughly washing with +water, alcohol, and ether, wiping perfectly dry on the outside, +and heating for one hour at the temperature of boiling water. The +hard flasks used in moist combustions with sulfuric acid for the +<span class="pagenum"><a id="Page_380"></a>[Pg 380]</span> +determination of nitrogen are well suited for this work. The flasks +should be placed in a tray by the side of the balance and covered with +a silk handkerchief until they are perfectly cool. They must not be +wiped with a silk handkerchief within fifteen or twenty minutes of the +time they are weighed or else the electricity developed will interfere +with weighing. The weight of the flasks having been accurately +determined, they are charged with the melted fat in the following way:</p> + +<div class="figcenter smcap"> + <img id="FIG_101" src="images/fig101.jpg" alt="" width="500" height="617" > + <p class="center spb1">Fig. 101.—Apparatus for Saponifying under Pressure.</p> +</div> + +<p>The pipette with a long stem, marked to deliver 5.75 cubic centimeters, +is warmed to a temperature of about 50°. The fat, having been poured +back and forth once or twice into a dry beaker in order to thoroughly +mix it, is taken up in the pipette, the nozzle of the pipette having +been previously wiped to remove any externally adhering fat, is carried +to near the bottom of the flask and 5.75 cubic centimeters of fat +allowed to flow into the flask. After the flasks have been charged in +<span class="pagenum"><a id="Page_381"></a>[Pg 381]</span> +this way they should be re-covered with the silk handkerchief and allowed +to stand for fifteen or twenty minutes, when they are again weighed.</p> + +<p><b>343. Methods of Saponification.</b>—<i>In the Presence of +Alcohol.</i>—Ten cubic centimeters of ninety-five per cent alcohol +are added to the fat in the flask, and then two cubic centimeters of +the sodium hydroxid solution. A soft cork stopper is inserted and +tied down with a piece of twine. The saponification is completed by +placing the flask upon the water or steam-bath. The flask during the +saponification, which should last one hour, should be gently rotated +from time to time, being careful not to project the soap for any +distance up its sides. At the end of an hour the flask, after having +been cooled to near the room temperature, is opened.</p> + +<p><i>Without the Use of Alcohol.</i>—To avoid the danger of loss from +the formation of ethers, and the trouble of removing the alcohol +after saponification, the fat may be saponified with a solution of +caustic potash in a closed flask without using alcohol. The operation +is carried on exactly as indicated above for saponification in the +presence of alcohol, using potassium instead of sodium hydroxid +solution. For the saponification, use two cubic centimeters of the +potassium hydroxid solution which are poured on the fat after it has +solidified in the flask. Great care must be taken that none of the +fat be allowed to rise on the sides of the saponifying flask to a +point where it cannot be reached by the alkali. During the process of +saponification the flask can only be very gently rotated in order to +avoid the difficulty mentioned. This process is not recommended with +any apparatus except a closed flask with round bottom. Potash is used +instead of soda so as to form a softer soap and thus allow a more +perfect saponification.</p> + +<p>The saponification may also be conducted as follows: The alkali and fat +in the melted state are shaken vigorously in the saponification flask +until a complete emulsion is secured. The rest of the operation is then +conducted as above.</p> + +<p><b>344. Saponification in the Cold.</b>—By reason of the danger of +loss from volatile ethers in the hot alcoholic saponification, a method +<span class="pagenum"><a id="Page_382"></a>[Pg 382]</span> +for successfully conducting the operation in the cold is desirable. +Such a process has been worked out by Henriques.<a id="FNanchor_309" href="#Footnote_309" class="fnanchor">[309]</a> +It is based upon the previous solution of the fat in petroleum ether, +in which condition it is so easily attacked by the alcoholic alkali +as to make the use of heat during the saponification unnecessary. The +process is conveniently conducted in a porcelain dish covered with a +watch glass. Five grams of the fat are dissolved in twenty-five cubic +centimeters of petroleum ether and treated with an equal quantity +of four per cent alcoholic soda lye. The process of saponification +begins at once and is often indicated by the separation of sodium +salts. It is best to allow the action to continue over night and, +with certain difficultly saponifiable bodies, such as wool fat and +waxes, for twenty-four hours. In the case of butter fat an odor of +butyric ether may be perceived at first but it soon disappears. After +the saponification is complete, the excess of alkali is determined +by titration in the usual way with set hydrochloric acid, using +phenolphthalien as indicator. For the determination of volatile acids, +the mixture, after saponification is complete, is evaporated rapidly +to dryness, the solid matter being reduced to powder with a glass +rod, after which it is transferred to a distilling flask and the +volatile acids secured by the usual processes. In comparison with the +saponification and reichert-meissl numbers obtained with hot alcoholic +potash, the numbers given by the cold process are found to be slightly +higher with those fats which give easily volatile ethers. On account of +the simplicity of the process and the absence of danger of loss from +ethers, it is to be recommended instead of the older methods in case +a more extended trial of it should establish the points of excellence +claimed above.</p> + +<p id="P_345"><b>345. Saponification Value.</b>—The number of milligrams of +potassium hydroxid required to completely saturate one gram of a fat +is known as the saponification value of the glycerid. The process of +determining this value, as worked out by Koettstorfer and modified in +the laboratory of the Department of Agriculture, is as +follows:<a id="FNanchor_310" href="#Footnote_310" class="fnanchor">[310]</a></p> + +<p><span class="pagenum"><a id="Page_383"></a>[Pg 383]</span> +The saponification is accomplished with the aid of potassium hydroxid +and in the flask and manner described in the preceding paragraph. About +two grams of the fat will be found a convenient quantity. Great care +must be exercised in measuring the alkaline solution, the same pipette +being used in each case and the same time for draining being allowed in +every instance. Blanks are always to be conducted with each series of +examinations. As soon as the saponification is complete, the flask is +removed from the bath, allowed to cool and its contents are titrated +with seminormal hydrochloric acid and phenolphthalien as indicator. +The number expressing the saponification value is obtained by +subtracting the number of cubic centimeters of seminormal hydrochloric +acid required to neutralize the alkali after saponification from +that required to neutralize the alkali of the blank determinations, +multiplying the result by 28.06 and dividing the product by the number +of grams of fat employed.</p> + +<div class="blockquot"> +<p><i>Example.</i>—Weight of sample of fat used 1.532 grams: Number of +cubic centimeters half normal hydrochloric acid required to saturate +blank, 22.5: Number of cubic centimeters of half normal hydrochloric +acid required to saturate the alkali after saponification 12.0: +Difference, 10.5 cubic centimeters:</p> + +<p>Then 10.50 × 28.06 ÷ 1.532 = 192.3.</p> + +<p>This latter number represents the saponification value of the sample.</p> +</div> + +<p><b>346. Saponification Equivalent.</b>—Allen defines the +saponification equivalent as the number of grams of fat saponified by +one equivalent, <i>viz.</i>, 56.1 grams of potassium hydroxid.<a id="FNanchor_311" href="#Footnote_311" class="fnanchor">[311]</a> +The saponification equivalent is readily calculated from the saponification +value using it as a divisor and 56100 as a dividend. Conversely +the saponification value may be obtained by dividing 56100 by the +saponification equivalent. No advantage is gained by the introduction +of a new term so nearly related to saponification value.</p> + +<p><b>347. Saponification Value of Pure Glycerids.</b>—The theoretical +<span class="pagenum"><a id="Page_384"></a>[Pg 384]</span> +saponification values of pure glycerids are given in the following +table.<a id="FNanchor_312" href="#Footnote_312" class="fnanchor">[312]</a></p> + +<table class="spb1"> + <thead><tr> + <th class="tdc bb">Name.</th> + <th class="tdc bb">Symbol.</th> + <th class="tdc bb">Molecular<br>weight.</th> + <th class="tdc bb"> Saponification<br>value.</th> + </tr></thead> + <tbody><tr> + <td class="tdl">Butyrin</td> + <td class="tdl_ws1 fs_110">C₃H₅(O.C₄H₇O)₃</td> + <td class="tdc">302</td> + <td class="tdc">557.3</td> + </tr><tr> + <td class="tdl">Valerin</td> + <td class="tdl_ws1 fs_110">C₃H₅(O.C₅H₉O)₃</td> + <td class="tdc">344</td> + <td class="tdc">489.2</td> + </tr><tr> + <td class="tdl">Caproin</td> + <td class="tdl_ws1 fs_110">C₃H₅(O.C₆H₁₁O)₃</td> + <td class="tdc">386</td> + <td class="tdc">438.3</td> + </tr><tr> + <td class="tdl">Caprin</td> + <td class="tdl_ws1 fs_110">C₃H₅(O.C₁₀H₁₉O)₃</td> + <td class="tdc">554</td> + <td class="tdc">305.0</td> + </tr><tr> + <td class="tdl">Laurin</td> + <td class="tdl_ws1 fs_110">C₃H₅(O.C₁₂H₂₃O)₃</td> + <td class="tdc">638</td> + <td class="tdc">263.8</td> + </tr><tr> + <td class="tdl">Myristin</td> + <td class="tdl_ws1 fs_110">C₃H₅(O.C₁₄H₂₇O)₃</td> + <td class="tdc">722</td> + <td class="tdc">233.1</td> + </tr><tr> + <td class="tdl">Palmitin</td> + <td class="tdl_ws1 fs_110">C₃H₃(O.C₁₆H₃₁O)₃</td> + <td class="tdc">806</td> + <td class="tdc">208.8</td> + </tr><tr> + <td class="tdl">Stearin</td> + <td class="tdl_ws1 fs_110">C₃H₅(O.C₁₈H₃₅O)₃</td> + <td class="tdc">890</td> + <td class="tdc">189.1</td> + </tr><tr> + <td class="tdl">Olein</td> + <td class="tdl_ws1 fs_110">C₃H₅(O.C₁₈H₃₃O)₃</td> + <td class="tdc">884</td> + <td class="tdc">190.4</td> + </tr><tr> + <td class="tdl">Linolein</td> + <td class="tdl_ws1 fs_110">C₃H₅(O.C₁₈H₃₁O)₃</td> + <td class="tdc">878</td> + <td class="tdc">191.7</td> + </tr><tr> + <td class="tdl">Ricinolein</td> + <td class="tdl_ws1 fs_110">C₃H₅(O.C₁₈H₃₃O₂)₃</td> + <td class="tdc">932</td> + <td class="tdc">180.6</td> + </tr><tr> + <td class="tdl">Euricin</td> + <td class="tdl_ws1 fs_110">C₃H₅(O.C₂₂H₁₄O)₃</td> + <td class="tdc">1052 </td> + <td class="tdc">160.0</td> + </tr> + </tbody> +</table> + +<p>From the above table it is seen that in each series of glycerids the +saponification equivalent falls as the molecular weight rises.</p> + +<p><b>348. Acetyl Value.</b>—Hydroxy acids and alcohols, when heated with +glacial acetic acid, undergo a change which consists in substituting +the radicle of acetic acid for the hydrogen atom of the alcoholic +hydroxyl group. This change is illustrated by the equations below:<a id="FNanchor_313" href="#Footnote_313" class="fnanchor">[313]</a></p> + +<div class="blockquot"> +<p><i>For a Fat Acid</i>:</p> + +<table class="spb1 fs_105"> + <tbody><tr> + <td class="tdc">Ricinoleic acid.</td> + <td class="tdl"> </td> + <td class="tdl">Acetic anhydrid.</td> + <td class="tdl"> </td> + </tr><tr> + <td class="tdl">C₁₇H₃₂(OH).COOH</td> + <td class="tdl"> + </td> + <td class="tdl">(C₂H₃O)₂O</td> + <td class="tdl"> =</td> + </tr><tr> + <td class="tdc" colspan="4"> </td> + </tr><tr> + <td class="tdc">Acetyl-ricinoleic acid.</td> + <td class="tdl"> </td> + <td class="tdl">Acetic acid.</td> + <td class="tdl"> </td> + </tr><tr> + <td class="tdc">C₁₇H₃₂(O.C₂H₃O)COOH</td> + <td class="tdl"> + </td> + <td class="tdl">HC₂H₃O₂.</td> + <td class="tdc"> </td> + </tr> + </tbody> +</table> + +<p><i>For an Alcohol</i>:</p> + +<table class="spb1 fs_105"> + <tbody><tr> + <td class="tdc">Cetyl alcohol.</td> + <td class="tdl"> </td> + <td class="tdl">Acetic anhydrid.</td> + <td class="tdl"> </td> + </tr><tr> + <td class="tdl">C₁₆H₃₃.OH</td> + <td class="tdl"> + </td> + <td class="tdl">(C₂H₃O)₂O</td> + <td class="tdl"> =</td> + </tr><tr> + <td class="tdc" colspan="4"> </td> + </tr><tr> + <td class="tdc">Cetyl acetate.</td> + <td class="tdl"> </td> + <td class="tdl">Acetic acid.</td> + <td class="tdl"> </td> + </tr><tr> + <td class="tdc">C₁₆H₃₃.C₂H₃O</td> + <td class="tdl"> + </td> + <td class="tdl">HC₂H₃O₂.</td> + <td class="tdc"> </td> + </tr> + </tbody> +</table> +</div> + +<p><i>Determination.</i>—The method of determining the acetyl value +of a fat or alcohol has been described by Benedikt and Ulzer.<a id="FNanchor_314" href="#Footnote_314" class="fnanchor">[314]</a> +The operation is conducted on the fat acids and not on the glycerids +containing them.</p> + +<p>The insoluble fat acids are prepared as directed in paragraph +<b><a href="#P_340">340</a></b>.</p> + +<p>From twenty to fifty grams of the fat acids are boiled with an equal +volume of acetic anhydrid, in a flask with a reflux condenser, for two +hours. The contents of the flask are transferred to a larger vessel of +<span class="pagenum"><a id="Page_385"></a>[Pg 385]</span> +about one liter capacity, mixed with half a liter of water and boiled +for half an hour. To prevent bumping, some bubbles of carbon dioxid +are drawn through the liquid by means of a tube drawn out to a fine +point and extending nearly to the bottom of the flask. The liquids +are allowed to separate into two layers and the water is removed with +a syphon. The oily matters are treated several times with boiling +water until the acetic acid is all washed out. The acetylated fat +acids are filtered through a dry hot jacket filter and an aliquot +part, from three to five grams, is dissolved in absolute alcohol. +After the addition of phenolphthalien the mixture is titrated as in +the determination of the saponification value. The acid value thus +obtained is designated as the acetyl acid value. A measured quantity +of alcoholic potash, standardized by seminormal hydrochloric acid, +is added, the mixture boiled and the excess of alkali determined by +titration. The quantity of alkali consumed in this process measures the +acetyl value. The sum of the acetyl acid and the acetyl values is the +acetyl saponification value. The acetyl value is therefore equal to +the difference of the saponification and acid values of the acetylated +fat acids. In other words, the acetyl value indicates the number of +milligrams of potassium hydroxid required to neutralize the acetic acid +obtained by the saponification of one gram of the acetylated fat acids.</p> + +<p class="blockquot"><i>Example.</i>—A portion of the fat acids acetylated as described, +weighing 3.379 grams, is exactly neutralized by 17.2 cubic centimeters +of seminormal potassium hydroxid solution, corresponding to 17.2 × +0.02805 = 0.4825 gram of the hydroxid, hence 0.4825 × 1000 ÷ 3.379 = +142.8, the acetyl acid value of the sample.</p> + +<p>After the addition of 32.8 cubic centimeters more of the seminormal +potash solution, the mixture is boiled to saponify the acetylated +fat acids. The residual potash requires 14.2 cubic centimeters of +seminormal hydrochloric acid. The quantity of potash required for +the acetic acid is therefore 32.8 - 14.3 = 18.5 cubic centimeters or +18.5 × 0.02805 = 0.5189 gram of potassium hydroxid. Then 0.5189 × +1000 ÷ 3.379 = 153.6 = acetyl value of sample. The sum of these two +values, <i>viz.</i>, 142.8 and 153.6 is 296.4, which is the acetyl +<span class="pagenum"><a id="Page_386"></a>[Pg 386]</span> +saponification value of the sample. As with the iodin numbers, however, +it is also found that acids of the oleic series give an acetyl value +when treated as above, and it has been proposed by Lewkowitsch to +determine, in lieu of the data obtained, the actual quantity of acetic +acid absorbed by fats.<a id="FNanchor_315" href="#Footnote_315" class="fnanchor">[315]</a> +This is accomplished by saponifying the acetylated product with +alcoholic potash and determining the free acetic acid by distillation, +in a manner entirely analogous to that used for estimating volatile fat +acids described further on.</p> + +<p>The rôle which the acetyl value plays in analytical determinations is +interesting, but the data it gives are not to be valued too highly.</p> + +<p id="P_349"><b>349. Determination of Volatile Fat Acids.</b>—The fat acids which +are volatile at the temperature of boiling water, consist chiefly of +butyric and its associated acids occurring in the secretions of the +mammary glands. Among vegetable glycerids cocoanut oil is the only +common one which has any notable content of volatile acids. The boiling +points of the above acids, in a pure state, are much higher than the +temperature of boiling water; for instance, butyric acid boils at about +162°. By the expression volatile acids, in analytical practice, is +meant those which are carried over at 100°, or a little above, with +the water vapor, whatever be their boiling point. The great difficulty +of removing the volatile from the non-volatile fat acids has prevented +the formulation of any method whereby a sharp and complete separation +can be accomplished. The analyst, at the present time, must be content +with some approximate process which, under like conditions, will give +comparable results. Instead, therefore, of attempting a definite +determination, he confines his work to securing a partial separation +and in expressing the degree of volatile acidity in terms of a standard +alkali. To this end, a definite weight of the fat is saponified, the +resulting soap decomposed with an excess of fixed acid, and a definite +volume of distillate collected and its acidity determined by titration +with decinormal alkali. The weight of fat operated on is either two and +a half<a id="FNanchor_316" href="#Footnote_316" class="fnanchor">[316]</a> +or five grams.<a id="FNanchor_317" href="#Footnote_317" class="fnanchor">[317]</a></p> + +<p>Numerous minor variations have been proposed in the process, the most +important of which is in the use of phosphoric instead of sulfuric acid +<span class="pagenum"><a id="Page_387"></a>[Pg 387]</span> +in the distillation. An extended experience with both acids has shown +that no danger is to be apprehended in the use of sulfuric acid and +that on the whole it is to be preferred to phosphoric.<a id="FNanchor_318" href="#Footnote_318" class="fnanchor">[318]</a></p> + +<p>The process as used in this laboratory and as adopted by the official +agricultural chemists is conducted as follows:<a id="FNanchor_319" href="#Footnote_319" class="fnanchor">[319]</a></p> + +<p><b>350. Removal of the Alcohol.</b>—The saponification is accomplished +in the manner already described, (<b><a href="#P_341">341-344</a></b>) and when alcoholic +potash is used proceed as follows:</p> + +<p>The stopper having been laid loosely in the mouth of the flask, the +alcohol is removed by dipping the flask into a steam-bath. The steam +should cover the whole of the flask except the neck. After the alcohol +is nearly removed, frothing may be noticed in the soap, and to avoid +any loss from this cause or any creeping of the soap up the sides of +the flask, it should be removed from the bath and shaken to and fro +until the frothing disappears. The last traces of alcohol vapor may be +removed from the flask by waving it briskly, mouth down, to and fro.</p> + +<p><i>Dissolving the Soap.</i>—After the removal of the alcohol the +soap should be dissolved by adding 100 cubic centimeters of recently +boiled distilled water, or eighty cubic centimeters when aqueous +potassium hydroxid has been used for saponification, and warming on the +steam-bath, with occasional shaking, until the solution of the soap is +complete.</p> + +<p><i>Setting free the Fat Acids.</i>—When the soap solution has cooled +to about 60° or 70°, the fat acids are separated by adding forty cubic +centimeters of dilute sulfuric acid solution containing twenty-five +grams of acid in one liter, or sixty cubic centimeters when aqueous +potassium hydroxid has been used for saponification.</p> + +<p><i>Melting the Fat Acid Emulsion.</i>—The flask is restoppered as in +the first instance and the fat acid emulsion melted by replacing the +flask on the steam-bath. According to the nature of the fat examined, +the time required for the fusion of the fatty acid emulsions may vary +from a few minutes to several hours.</p> + +<p><i>The Distillation.</i>—After the fat acids are completely melted, +which can be determined by their forming a transparent, oily layer on +<span class="pagenum"><a id="Page_388"></a>[Pg 388]</span> +the surface of the water, the flask is cooled to room temperature, +and a few pieces of pumice stone added. The pumice stone is prepared +by throwing it, at a white heat, into distilled water, and keeping it +under water until used. The flask is connected with a glass condenser, +<a href="#FIG_102">Fig. 102</a>, slowly heated with a naked flame +until ebullition begins, and then the distillation continued by +regulating the flame in such a way as to collect 110 cubic centimeters +of the distillate in, as nearly as possible, thirty minutes. The +distillate should be received in a flask accurately marked at 110 cubic +centimeters.</p> + +<div class="figcenter smcap"> + <img id="FIG_102" src="images/fig102.jpg" alt="" width="600" height="390" > + <p class="center spb1">Fig. 102.—Apparatus for the Distillation of Volatile Acids.</p> +</div> + +<p><i>Titration of the Volatile Acids.</i>—The 110 cubic centimeters +of distillate, after thorough mixing, are filtered through perfectly +dry filter paper, 100 cubic centimeters of the filtered distillate +poured into a beaker holding about a quarter of a liter, half a cubic +centimeter of phenolphthalien solution added and decinormal barium +hydroxid solution run in until a red color is produced. The contents +of the beaker are then returned to the measuring flask to remove any +acid remaining therein, poured again into the beaker, and the titration +continued until the red color produced remains apparently unchanged for +two or three minutes, The number of cubic centimeters of decinormal +<span class="pagenum"><a id="Page_389"></a>[Pg 389]</span> +barium hydroxid solution required should be increased by one-tenth to +represent the entire distillate.</p> + +<p>The number thus obtained expresses, in cubic centimeters of decinormal +alkali solution, the volatile acidity of the sample. In each case +blank distillations of the reagents used should be conducted under +identical conditions, especially when alcoholic alkali is used for +saponification. It is difficult to secure alcohol which will not yield +a trace of volatile acid in the conditions named. The quantity of +decinormal alkali required to neutralize the blank distillate is to be +deducted from that obtained with the sample of fat.</p> + +<p id="P_351"><b>351. Determination of Soluble and Insoluble Fat Acids.</b>—The +volatile fat acids are more or less soluble in water, while those which +are not distillable in a current of steam are quite insoluble. It is +advisable, therefore, to separate these two classes of fat acids, and +the results thus obtained are perhaps more decidedly quantitive than +are given by the distillation process just described. The methods used +for determining the percentage of insoluble acids are essentially those +of Hehner.<a id="FNanchor_320" href="#Footnote_320" class="fnanchor">[320]</a> +Many variations of the process have been proposed, especially in respect +of the soluble acids.<a id="FNanchor_321" href="#Footnote_321" class="fnanchor">[321]</a></p> + +<p>The process, as conducted in this laboratory and approved by the +Association of Official Agricultural Chemists, is as follows:</p> + +<p><i>Preparation of Reagents.—Sodium Hydroxid Solution.</i>—A +decinormal solution of sodium hydroxid is used. Each cubic centimeter +contains 0.0040 gram of sodium hydroxid and neutralizes 0.0088 gram of +butyric acid (<b>C₄H₈O₂</b>).</p> + +<p><i>Alcoholic Potash Solution.</i>—Dissolve forty grams of good caustic +potash in one liter of ninety-five per cent alcohol redistilled over +caustic potash or soda. The solution must be clear and the potassium +hydroxid free from carbonates.</p> + +<p><i>Standard Acid Solution.</i>—Prepare accurately a half normal +solution of hydrochloric acid.</p> + +<p><i>Indicator.</i>—Dissolve one gram of phenolphthalien in 100 cubic +centimeters of ninety-five per cent alcohol.</p> + +<p><i>Determination.—Soluble Acids.</i>—About five grams of the sample +are placed in the saponification flask already described, fifty cubic +<span class="pagenum"><a id="Page_390"></a>[Pg 390]</span> +centimeters of the alcoholic potash solution added, the flask stoppered +and placed in the steam-bath until the fat is entirely saponified. The +operation may be facilitated by occasional agitation. The alcoholic +potash is always measured with the same pipette and uniformity further +secured by allowing it to drain the same length of time (thirty +seconds). Two or three blank experiments are conducted at the same time.</p> + +<p>In from five to thirty minutes, according to the nature of the fat, the +liquid will appear perfectly homogeneous and, when this is the case, +the saponification is complete and the flask is removed and cooled. +When sufficiently cool, the stopper is removed and the contents of +the flask rinsed with a little ninety-five per cent alcohol into an +erlenmeyer, of about 200 cubic centimeters capacity, which is placed on +the steam-bath together with the blanks until the alcohol is evaporated.</p> + +<p>The blanks are titrated with half normal hydrochloric acid, using +phenolphthalien as indicator, and one cubic centimeter more of the half +normal hydrochloric acid than is required to neutralize the potash in +the blanks is run into each of the flasks containing the fat acids. The +flask is connected with a reflux condenser and placed on the steam-bath +until the separated fat acids form a clear stratum on the upper surface +of the liquid. The flask and contents are cooled in ice-water.</p> + +<p>The fat acids having quite solidified, the liquid contents of the flask +are poured through a dry filter into a liter flask, taking care not +to break the cake. Between 200 and 300 cubic centimeters of water are +brought into the flask, the cork with the condenser reinserted and the +flask placed on the steam-bath until the cake of acid is thoroughly +melted. During the melting of the cake of fat acids, the flask should +occasionally be agitated with a rotary motion in such a way that its +contents are not made to touch the cork. When the fat acids have again +separated into an oily layer, the flask and its contents are cooled +in ice-water and the liquid filtered through the same filter into the +same liter flask as before. This treatment with hot water, followed +by cooling and filtration of the wash water, is repeated three times, +the washings being added to the first filtrate. The mixed washings and +<span class="pagenum"><a id="Page_391"></a>[Pg 391]</span> +filtrate are made up to one liter, and 100 cubic centimeters +thereof in duplicate are titrated with decinormal sodium hydroxid. +The number of cubic centimeters of sodium hydroxid required for +each 100 cubic centimeters of the filtrate is multiplied by ten. +The number so obtained represents the volume of decinormal sodium +hydroxid neutralized by the soluble fat acids of the fat, plus that +corresponding to the excess of the standard acid used, <i>viz.</i>, one +cubic centimeter. The number is therefore to be diminished by five, +corresponding to the excess of one cubic centimeter of half normal +acid. This corrected volume multiplied by 0.0088 gives the weight of +soluble acids as butyric acid in the amount of fat saponified.</p> + +<p><i>Insoluble Acids.</i>—The flask containing the cake of insoluble +fat acids from the above determination and the paper through which the +soluble fat acids have been filtered are allowed to drain and dry for +twelve hours, when the cake, together with as much of the fat acids +as can be removed from the filter paper, is transferred to a weighed +evaporating dish. The funnel, with the filter, is then placed in an +erlenmeyer and the paper thoroughly washed with absolute alcohol. The +flask is rinsed with the washings from the filter paper, then with pure +alcohol, and the rinsings transferred to the evaporating dish. The dish +is placed on the steam-bath until the alcohol is evaporated, dried for +two hours at 100°, cooled in a desiccator and weighed. It is again +placed in the air-bath for two hours, cooled as before and weighed. +If there be any considerable decrease in weight, reheat two hours and +weigh again. The final weighing gives the weight of insoluble fat acids +in the sample, from which the percentage is easily calculated.</p> + +<p>The quantity of non-volatile and insoluble acids in common glycerids +is from ninety-five to ninety-seven parts in 100. The glycerids yield +almost the same proportion of fat acids and glycerol when the acids are +insoluble and have high molecular weights. When the acids are soluble +and the molecular weight low the proportion of acids decreases and that +of glycerol increases.</p> + +<p>In the following table will be found the data secured by quantitive +<span class="pagenum"><a id="Page_392"></a>[Pg 392]</span> +saponification and separation of soluble and insoluble acids found in +the more common glycerids:<a id="FNanchor_322" href="#Footnote_322" class="fnanchor">[322]</a></p> + +<table class="spb1"> + <thead><tr> + <th class="tdc bl bb bt2" colspan="2"> </th> + <th class="tdc_bott bt2 bl bb" colspan="2"> Molecular weight of </th> + <th class="tdc bt2 bl br bb" colspan="2"> Yield per 100 parts <br>of glycerid.</th> + </tr><tr> + <th class="tdc bl bb"> Glycerid. </th> + <th class="tdc bl bb"> Fat acid. </th> + <th class="tdc bl bb">Glycerid.</th> + <th class="tdc bl bb">Fat acid.</th> + <th class="tdc bl bb">Fat acid.</th> + <th class="tdc bl bb br">Glycerol.</th> + </tr></thead> + <tbody><tr> + <td class="tdl">Stearin</td> + <td class="tdl_ws1">Stearic</td> + <td class="tdc">890</td> + <td class="tdc">284</td> + <td class="tdc">95.73</td> + <td class="tdc">10.34</td> + </tr><tr> + <td class="tdl">Olein</td> + <td class="tdl_ws1">Oleic</td> + <td class="tdc">884</td> + <td class="tdc">282</td> + <td class="tdc">95.70</td> + <td class="tdc">10.41</td> + </tr><tr> + <td class="tdl">Palmitin</td> + <td class="tdl_ws1">Palmitic</td> + <td class="tdc">806</td> + <td class="tdc">256</td> + <td class="tdc">95.28</td> + <td class="tdc">11.42</td> + </tr><tr> + <td class="tdl">Myristin</td> + <td class="tdl_ws1">Myristic</td> + <td class="tdc">722</td> + <td class="tdc">228</td> + <td class="tdc">94.47</td> + <td class="tdc">12.74</td> + </tr><tr> + <td class="tdl">Laurin</td> + <td class="tdl_ws1">Lauric</td> + <td class="tdc">638</td> + <td class="tdc">200</td> + <td class="tdc">94.95</td> + <td class="tdc">14.42</td> + </tr><tr> + <td class="tdl">Caprin</td> + <td class="tdl_ws1">Capric</td> + <td class="tdc">594</td> + <td class="tdc">172</td> + <td class="tdc">93.14</td> + <td class="tdc">15.48</td> + </tr><tr> + <td class="tdl">Caproin</td> + <td class="tdl_ws1">Caproic</td> + <td class="tdc">386</td> + <td class="tdc">116</td> + <td class="tdc">90.16</td> + <td class="tdc">23.83</td> + </tr><tr> + <td class="tdl">Butyrin</td> + <td class="tdl_ws1">Butyric</td> + <td class="tdc">302</td> + <td class="tdc"> 88</td> + <td class="tdc">87.41</td> + <td class="tdc">30.46</td> + </tr> + </tbody> +</table> + +<p>The general expression for the saponification of a neutral fat is +<b>C₃H₅O₃.R₃ + 3H₂O = 3R.OH + C₃H₈O₃</b>, in which R represents the acid +radicle. It is evident from this that the yield of more than 100 parts +of fat acids and glycerol given by glycerids is due to the absorption +of water during the reaction.</p> + +<p><b>352. Formulas for General Calculations.</b>—For calculating the +theoretical yields of fat acids and glycerol, the following general +formulas may be used:</p> + +<ul class="index"> +<li class="isub1">Let <i>M</i> = the molecular weight of the fat acid:</li> +<li class="isub3"><i>K</i> = saponification value:</li> +<li class="isub3"><i>F</i> = the quantity of free fat acids in the glycerid:</li> +<li class="isub3"><i>N</i> = the quantity of neutral fat in the glycerid:</li> +<li class="isub3"><i>A</i> = the number of milligrams of potassium hydroxid required</li> +<li class="isub5">to saturate the free acid in one gram of the sample.</li> +<li class="isub1"> </li> +<li class="isub1">The free acid is determined by the method given below.</li> +</ul> + +<p><i>M</i> grams of a fat acid require 56100 milligrams of potassium +hydroxid for complete neutralization while <i>F</i> grams corresponding +to 100 grams of fat are saturated by 100 × <i>A</i> milligrams of the alkali.</p> + +<p class="f105">Then <i>M</i> : 56100 = <i>F</i> : 100<i>A</i>.</p> + +<table class="spb1 fs_105"> + <tbody><tr> + <td class="tdl" rowspan="2">Whence <i>F</i> = </td> + <td class="tdc bb"><i>AM</i></td> + <td class="tdr" rowspan="2"><span class="ws4">(1).</span></td> + </tr><tr> + <td class="tdc">561</td> + </tr> + </tbody> +</table> + +<p>Likewise since <i>M</i> grams of fat acid require the quantity of +potassium hydroxid mentioned above we have: +<span class="pagenum"><a id="Page_393"></a>[Pg 393]</span></p> + +<p class="f105">1 : <i>K</i> = <i>M</i> : 56100,</p> + +<table class="spb1 fs_105"> + <tbody><tr> + <td class="tdl" rowspan="2">Whence <i>M</i> = </td> + <td class="tdc bb">56100</td> + <td class="tdr" rowspan="2"><span class="ws4">(2).</span></td> + </tr><tr> + <td class="tdc"><i>K</i></td> + </tr> + </tbody> +</table> + +<p>Substituting this value of <i>M</i> in (1) we have</p> + +<table class="spb1 fs_105"> + <tbody><tr> + <td class="tdl" rowspan="2"><i>F</i> = </td> + <td class="tdc bb"><i>A</i> × 56100</td> + <td class="tdl" rowspan="2"> = </td> + <td class="tdc bb">100<i>A</i></td> + <td class="tdr" rowspan="2"><span class="ws3">(3).</span></td> + </tr><tr> + <td class="tdc">561 × <i>K</i></td> + <td class="tdc">561 × <i>K</i></td> + </tr> + </tbody> +</table> + +<p>It is evident that it is not necessary to calculate the acid value +(<i>A</i>) of the sample and the saponification value (<i>K</i>) of the +free fat acids, the ratio <i>A</i>/<i>K</i> alone being required. It +will be sufficient therefore to substitute for <i>A</i> and <i>K</i> +the number of cubic centimeters of alkali solutions required for +one gram of the fat and one gram of the fat acids, respectively. If +<i>a</i> and <i>b</i> represent these numbers the formula may be written</p> + +<table class="spb1 fs_105"> + <tbody><tr> + <td class="tdl" rowspan="2"><i>F</i> = </td> + <td class="tdc bb">100<i>a</i></td> + <td class="tdr" rowspan="2"><span class="ws10">(4);</span></td> + </tr><tr> + <td class="tdc"><i>b</i></td> + </tr> + </tbody> +</table> + +<table class="spb1 fs_105"> + <tbody><tr> + <td class="tdl" rowspan="2">and <i>N</i> = 100 - <i>F</i> = </td> + <td class="tdc bb">100<i>a</i></td> + <td class="tdr" rowspan="2"><span class="ws4">(5).</span></td> + </tr><tr> + <td class="tdc"><i>b</i></td> + </tr> + </tbody> +</table> + +<p>To simplify the determinations, it may be assumed that the free fat +acids have the same molecular weight as those still in combination +with the glycerol in any given sample. On this assumption, the +process may be carried on by determining the acid value <i>A</i> and +the saponification value <i>K</i> for the total fat acids. The mean +molecular weight <i>M</i>, the percentage of free fat acids <i>F</i>, +and the proportion of neutral fat <i>N</i>, may then be calculated from +the formulas (2), (3), (4), and (5).</p> + +<p>Further, let <i>G</i> = the quantity of glycerol and <i>L</i> that of +fat acids obtainable from one gram of neutral fat, that is, <span class="fs_120">¹/₁₀₀</span> +of <i>H</i> the percentage of total fat acids.</p> + +<p>The molecular weight of the neutral fat in each case is 3<i>M</i> + 38. +Therefore, 3<i>M</i> + 38 parts of neutral fat yield 3<i>M</i> parts of +fat acids and ninety-two parts of glycerol (<b>C₃H₈O₃</b> = 92).</p> + +<table class="spb1 fs_105"> + <tbody><tr> + <td class="tdl" rowspan="2">Then <i>L</i> = </td> + <td class="tdc bb"><i>H</i></td> + <td class="tdl" rowspan="2"> = </td> + <td class="tdc bb">3<i>M</i></td> + <td class="tdl" rowspan="2"><span class="ws3">(6);</span></td> + </tr><tr> + <td class="tdc">100</td> + <td class="tdc">3<i>M</i> + 38</td> + </tr> + </tbody> +</table> + +<table class="spb1 fs_105"> + <tbody><tr> + <td class="tdl" rowspan="2">and <i>G</i> = </td> + <td class="tdc bb">92</td> + <td class="tdl" rowspan="2"><span class="ws6">(7).</span></td> + </tr><tr> + <td class="tdc">3<i>M</i> + 38</td> + </tr> + </tbody> +</table> + +<p><i>N</i> per cent of neutral fat yields, therefore, on saponification, +<span class="pagenum"><a id="Page_394"></a>[Pg 394]</span> +the following theoretical quantities of fat acids <i>F</i>, and +glycerol <i>G</i> expressed as parts per hundred.</p> + +<table class="spb1 fs_105"> + <tbody><tr> + <td class="tdl" rowspan="2"><i>F</i> = <i>N</i> × </td> + <td class="tdc bb">3<i>M</i></td> + <td class="tdl" rowspan="2"><span class="ws6">(8);</span></td> + </tr><tr> + <td class="tdc">3<i>M</i> + 38</td> + </tr> + </tbody> +</table> + +<table class="spb1 fs_105"> + <tbody><tr> + <td class="tdl" rowspan="2">and <i>G</i> = <i>N</i> × </td> + <td class="tdc bb">92</td> + <td class="tdl" rowspan="2"><span class="ws4">(9).</span></td> + </tr><tr> + <td class="tdc">3<i>M</i> + 38</td> + </tr> + </tbody> +</table> + +<p>Formula (9) expresses also the total yield of glycerol from any given +sample. For a further discussion of this part of the subject a work of +a more technical character may be consulted.<a id="FNanchor_323" href="#Footnote_323" class="fnanchor">[323]</a></p> + +<p><b>353. Determination of a Free Fat Acid in a Fat.</b>—The principle +of the method rests upon the comparative accuracy with which a free fat +acid can be titrated with a set alkali solution when phenolphthalien +is used as an indicator. Among the many methods of manipulation which +the analyst has at his command there is probably none more simple and +accurate than that depending on the solution of the sample in alcohol, +ether, chloroform, or carbon tetrachlorid. Any acidity of the solvent +is determined by separate titration and the proper correction made. +Either an aqueous or alcoholic solution of the alkali may be used, +preferably the latter. The alkaline solution may be approximately or +exactly decinormal, but it is easier to make it approximately so and +to determine its real value before each operation by titration against +a standard decinormal solution of acid. About ten grams of the sample +and fifty cubic centimeters of the solvent will be found convenient +quantities.</p> + +<p><i>Example.</i>—Ten grams of rancid olive oil dissolved in +alcohol ether require three and eight-tenths cubic centimeters of a +solution of alcoholic potash to saturate the free acid present. When +titrated with decinormal acid the potash solution is found to contain +25.7 milligrams of potassium hydroxid in each cubic centimeter. The +specific gravity of the oil is 0.917 and the weight used therefore 9.17 +grams. Then the total quantity of potassium hydroxid required for the +neutralization of the acid is 25.7 × 3.8 = 97.7 milligrams.</p> + +<p>The acid value <i>A</i> is therefore:</p> + +<table class="spb1 fs_105"> + <tbody><tr> + <td class="tdl" rowspan="2"><i>A</i> = </td> + <td class="tdc bb">3.8 × 25.7</td> + <td class="tdl" rowspan="2"> = 10.6</td> + </tr><tr> + <td class="tdc">9.17</td> + </tr> + </tbody> +</table> + +<p><span class="pagenum"><a id="Page_395"></a>[Pg 395]</span> +It is customary to regard free acid as oleic, molecular weight 282. On +this assumption the percentage of free acids in the above case is found +by the formula</p> + +<table class="spb1 fs_105"> + <tbody><tr> + <td class="tdl" rowspan="2"><i>A</i> (per cent) = </td> + <td class="tdc bb">3.8 × 25.7 × 282</td> + <td class="tdl" rowspan="2"> = 5.35</td> + </tr><tr> + <td class="tdc">561 × 9.17</td> + </tr> + </tbody> +</table> + +<p><b>354. Identification of Oils and Fats.</b>—Properly, the methods +of identifying and isolating the different oils and fats should +be looked for in works on food adulteration. There are, however, +many characteristics of these glycerids which can be advantageously +discussed in a work of this kind. Many cases arise in which the analyst +is called upon to determine the nature of a fat and discover whether +it be admixed with other glycerids. It is important often to know in +a given case whether an oil be of animal or vegetable origin. Many of +the methods of analysis already described are found useful in such +discriminations. For instance, a large amount of soluble or volatile +acids in the sample under examination, would indicate the presence +of a fat derived from milk while the form of the crystals in a solid +fat would give a clue to whether it were the product of the ox or the +swine. In the succeeding paragraphs will be briefly outlined some of +the more important additional methods of determining the nature and +origin of fats and oils of which the history is unknown.</p> + +<p>The data obtained by means of the methods which have been described, +both physical and chemical, are all useful in judging the character and +nature of a glycerid of unknown origin. The colorations produced by +oxidizing agents, in the manner already set forth will be found useful, +especially when joined to those obtained with cottonseed and sesame +oils yet to be described. For instance, the red coloration produced by +nitric acid of 1.37 specific gravity is regarded by some authorities +as characteristic of cottonseed oil as well as the reduction by it of +silver nitrate. The coloration tests with silver nitrate (paragraph +<b><a href="#P_320">320</a></b>) and with phosphomolydic acid (paragraph <b><a href="#P_318">318</a></b>) +are also helpful in classifying oils in respect of their animal or +vegetable origin. The careful consideration of these tests, together +with a study of the numbers obtained by treating the samples with iodin, +<span class="pagenum"><a id="Page_396"></a>[Pg 396]</span> +and the heat of bromination and sulfuric saponification, is commended +to all who are interested in classifying oils. In addition to these +reactions a few specific tests are added for more detailed work.</p> + +<p><b>355. Consistence.</b>—It has already been said that oils are mostly +of vegetable origin and the solid fats of animal derivation. In the +animal economy it would be a source of disturbance to have in the +tissues a large body of fat which would remain in a liquid state at the +normal temperature of the body. Nearly all the animal fats are found to +have a higher melting point than the body containing them. An exception +is found in the case of butter fat, but it should be remembered that +this fat is an excretion and not intended for tissue building until +it has undergone subsequent digestion. Fish oils are another notable +exception to the rule, but in this case these oils can hardly be +regarded as true glycerids in the ordinary sense of that term.</p> + +<p>In general, it may be said that a sample of a glycerid, which in its +natural state remains liquid at usual room temperatures, is probably +an oil of vegetable origin. Fish oils have also an odor and taste +which prevent them from being confounded with vegetable oils. In oils +which are manufactured from animal glycerids such as lard oil, the +discrimination is more difficult but peculiarities of taste and color +are generally perceptible.</p> + +<p><b>356. Nature of the Fat Acid.</b>—When it is not possible to +discriminate between samples by the sensible physical properties +just described, much light can be thrown on their origin by the +determination of their other physical properties, such as specific +gravity, refractive index, melting point, etc., in the manner already +fully described. Further light may be furnished by saponification and +separation of the fat acids. The relative quantities of oleic, stearic, +palmitic, and other acids will help to a correct judgment in respect +of the nature of the sample. The vegetable oils and lard oils, for +instance, consist chiefly of olein; lard and tallow contain a large +proportion of stearin; palm oil and butter fat contain considerable +<span class="pagenum"><a id="Page_397"></a>[Pg 397]</span> +portions of palmitin, and the latter is distinguished moreover by the +presence of soluble and volatile acids combined as butyrin and its +associated glycerids.</p> + +<p>Oleic acid can be rather readily separated from stearic and palmitic +by reason of the solubility of its lead salts in ether. One method of +accomplishing this separation has already been described (paragraph <b><a href="#P_339">339</a></b>).</p> + +<p><b>357. Separation with Lime.</b>—A quicker, though perhaps not as +accurate a separation of the oleic from the palmitic and stearic acids, +is accomplished by means of lime according to the method developed by +Bondzyuski and Rufi.<a id="FNanchor_324" href="#Footnote_324" class="fnanchor">[324]</a> +This process is used chiefly, however, to separate the free fat acids +(palmitic, stearic) from the neutral fat and the free oleic acid. It +probably has no point of superiority over the lead process.</p> + +<p><b>358. Separation of the Glycerids.</b>—The fact that olein is liquid +at temperatures allowing palmitin and stearin to remain solid, permits +of a rough separation of these two classes of bodies by mechanical +means. The mixed fats are first melted and allowed to cool very slowly. +In these conditions the stearin and palmitin separate from the olein in +a crystalline form and the olein is removed by pressure through bags. +In this way lard is separated into lard oil, consisting chiefly of +olein, and lard stearin, consisting largely of stearin. Beef (caul) fat +is in a similar manner separated into a liquid (oleo-oil) and a solid +(oleo-stearin) portion. It is evident that these separations are only +approximate, but by repeated fractionations a moderately pure olein or +stearin may be obtained.</p> + +<p><b>359. Separation as Lead Salts.</b>—Muter’s process, with a special +piece of apparatus, has already been described (<b><a href="#P_339">339</a></b>). For +general analytical work the special tube may be omitted. In a mixture +of insoluble free fat acids all are precipitated by lead acetate, and +the resulting soap may be extracted with ether, either with successive +shakings or in a continuous extraction apparatus. In this latter case +a little of the lead stearate or palmitate may pass into solution in +the hot ether and afterwards separate on cooling. When the operation +is conducted on from two to three grams of the dry mixed acids, the +percentage proportions of the soluble and insoluble acids (in ether) +<span class="pagenum"><a id="Page_398"></a>[Pg 398]</span> +can be determined. The lead salt which passes into solution can be +decomposed and the oleic acid removed, dried and weighed. Dilute +hydrochloric acid is a suitable reagent for decomposing the lead soap. +The difference between the weight of the oleic acid and that of the +mixed acids before conversion into lead soap furnishes the basis for +the calculation. For further details in respect of the fat acids the +reader may consult special analytical works.<a id="FNanchor_325" href="#Footnote_325" class="fnanchor">[325]</a></p> + +<p><b>360. Separation of Arachidic Acid.</b>—Peanut oil is easily +distinguished from other vegetable glycerids by the presence of +arachidic acid.</p> + +<p>The method used in this laboratory for separating arachidic acid is +a modification of the usual methods based on the process as carried +out by Milliau.<a id="FNanchor_326" href="#Footnote_326" class="fnanchor">[326]</a> +About twenty grams of the oil are saponified with alcoholic soda, using +twenty cubic centimeters of 36° baumé soda solution diluted with 100 +cubic centimeters of ninety per cent alcohol. When the saponification +is complete, the soda is converted into the lead soap by treatment with +a slight excess of a saturated alcoholic solution of lead acetate. Good +results are also obtained by using dilute alcohol, <i>viz.</i>, fifty +per cent, instead of ninety per cent, in preparing the lead acetate solution.</p> + +<p>While still warm the supernatant liquid is decanted, the precipitate +washed by decantation with warm ninety per cent alcohol and triturated +with ether in a mortar four times, decanting the ethereal solution in +each instance. By this treatment all of the lead oleate and hypogaeate +are removed and are found in the ethereal solution, from which they can +be recovered and the acids set free by hydrochloric acid and determined +in the usual way.</p> + +<p>The residue is transferred to a large dish containing two or three +liters of pure water and decomposed by the addition of about fifty +cubic centimeters of strong hydrochloric acid. The lead chlorid formed +is soluble in the large quantity of water present, which should be +warm enough to keep the free acids in a liquid state in which form +they float as a clear oily liquid on the surface. The free acids are +decanted and washed with warm water to remove the last traces of lead +<span class="pagenum"><a id="Page_399"></a>[Pg 399]</span> +chlorid and hydrochloric acid. The last traces of water are removed +by drying in a thin layer in vacuo. Practically all of the acids, +originally present in the sample except oleic and hypogaeic, are thus +obtained in a free state and their weight is determined.</p> + +<p>The arachidic acid may be separated almost quantitively by dissolving +the mixed acids in forty cubic centimeters of ninety per cent alcohol, +adding a drop of hydrochloric acid, cooling to 16° and allowing to +stand until the arachidic acid has crystallized. The crystals are +purified by washing twice with twenty cubic centimeters of ninety +per cent and three times with the same quantity of seventy per cent +alcohol. The residual impure arachidic acid is dissolved in boiling +absolute alcohol, poured through a filter and washed with pure hot +alcohol. The filtrate is evaporated to dryness and heated to 100° until +a constant weight is obtained. From the above data, the percentages of +oleic, hypogaeic, arachidic and other acids in the sample examined are +calculated.</p> + +<p>In the above process, owing to the pasty state of the lead soaps, the +trituration in a mortar with ether is found troublesome. The extraction +of the lead oleate and hypogaeate is facilitated by throwing the pasty +ethereal mass on a filter and washing it thoroughly with successive +portions of about fifty cubic centimeters of ether. By this variation, +it was found by Krug in this laboratory, that less ether was required +and a more complete removal of the lead oleate effected. The solution +of the lead oleate is completed by about half a dozen washings with +ether as above described. The extraction may also be secured by +placing the lead soaps in a large extracting apparatus and proceeding +as directed in paragraph <b><a href="#P_40">40</a></b>. The residue is washed from the +filter paper into a large porcelain dish and decomposed as already +described with hydrochloric acid. After the separation is complete, the +mixture is cooled until the acids are solid. The solid acids are then +transferred to a smaller dish, freed of water and dissolved in ether. +The ethereal solution is washed with water to remove any traces of +lead salt or of hydrochloric acid. After the removal of the ether, the +arachidic acid is separated as has already been described. +<span class="pagenum"><a id="Page_400"></a>[Pg 400]</span></p> + +<p>The melting point of pure arachidic acid varies from 73° to 75°.</p> + +<p><b>361. Detection of Arachis</b> (<b>Peanut</b>) <b>Oil.</b>—Kreis +has modified the usual process of Renard for the detection of arachis +oil, by precipitating the solution of the fat acid with an alcoholic +instead of an aqueous solution of lead acetate, in a manner quite +similar to that described above.<a id="FNanchor_327" href="#Footnote_327" class="fnanchor">[327]</a> +The fat acids are obtained in the usual manner, washed with hot water +and the acids from twenty grams of the oil dissolved in 100 cubic +centimeters of ninety per cent alcohol. The solution is cooled in +ice-water and the fat acids precipitated by the addition of fifteen +grams of lead acetate dissolved in 150 cubic centimeters of ninety +per cent alcohol. The precipitate, after standing for two hours, is +separated by filtration through cotton wool and is extracted for six +hours with ether. The residue is boiled with 250 cubic centimeters of +five per cent hydrochloric acid until the fat acids appear as a clear +oily layer upon the surface. The acids thus obtained are washed with +hot water to remove lead chlorid, dried by pressing between blotting +paper, dissolved in 100 cubic centimeters of ninety per cent alcohol, +cooled to 15° and allowed to stand for several hours, after which +time any arachidic acid present is separated by crystallization and +identified in the usual manner.</p> + +<p>When it is not important to obtain all of the acid present, the process +may be simplified in the following manner:</p> + +<p>The fat acids obtained from twenty grams of oil are dissolved in 300 +cubic centimeters of ether and treated at the temperature of ice-water +with a quantity of the alcoholic lead acetate solution mentioned above. +Lead oleate remains in solution and the precipitate which forms after +a few hours consists almost wholly of the lead salts of the solid fat +acids. The precipitate is collected, washed with ether and identified +in the usual manner.</p> + +<p><b>362. Cottonseed Oil, Bechi’s Test.</b>—Crude, fresh cottonseed oil, +when not too highly colored, and generally the refined article, may be +distinguished from other oils by the property of reducing silver salts +<span class="pagenum"><a id="Page_401"></a>[Pg 401]</span> +in certain conditions. The reaction was first noticed by Bechi and has +been the subject of extensive discussions.<a id="FNanchor_328" href="#Footnote_328" class="fnanchor">[328]</a></p> + +<p>The process as proposed by Bechi has been modified in many ways but +apparently without improving it. It is conducted as follows: One gram +of silver nitrate is dissolved in 200 cubic centimeters of ninety-eight +per cent alcohol and forty cubic centimeters of ether and one drop of +nitric acid added to the mixture. Ten cubic centimeters of the oil +are shaken in a test tube with one cubic centimeter of this reagent, +and then with ten cubic centimeters of a mixture containing 100 +cubic centimeters of amyl alcohol and ten of colza oil. The mixture +is divided into two portions, one of which is put aside for future +comparison and the other plunged into boiling water for fifteen +minutes. A deep brown or black color, due to the reduction of silver, +reveals the presence of cottonseed oil.</p> + +<p>In this laboratory the heating is accomplished in a small porcelain +dish on which is often deposited a brilliant mirror of metallic silver. +The white color of the porcelain also serves as a background for the +observation of the coloration produced. In most instances a green color +has been noticed after the reduction of the silver is practically +complete. Unless cottonseed oil has been boiled or refined in some +unusual way, the test, as applied above, is rarely negative. The +reduction of the silver is doubtless due to some aldehydic principle, +present in extremely minute quantities, and which may be removed by +some methods of technical treatment. The silver nitrate test therefore +is reliable when the reduction takes place, but the absence of a distinct +reaction may not in all cases prove the absence of cottonseed oil.</p> + +<p><b>363. Milliau’s Process.</b>—Milliau has proposed the application +of the silver salt directly to the free fat acids of the oil instead +of to the oil itself.<a id="FNanchor_329" href="#Footnote_329" class="fnanchor">[329]</a> +About fifteen cubic centimeters of the oil are saponified with +alcoholic potash in the usual manner, 150 cubic centimeters of +water added to the dish and the mixture boiled until the alcohol is +evaporated. The fat acids are freed by the addition of decinormal +sulfuric acid and as they rise to the surface in a pasty condition are +removed with a spoon. The free acids are washed with distilled water. +<span class="pagenum"><a id="Page_402"></a>[Pg 402]</span> +The water is drained off and the free acids dissolved in fifteen +cubic centimeters of ninety-two per cent alcohol and two cubic +centimeters of a three per cent solution of silver nitrate. The test +tube containing the mixture is well shaken and placed in a water-bath, +out of contact with light, and left until about one-third of the +alcohol is evaporated. Ten cubic centimeters of water are added, the +heating continued for a few minutes and the color of the supernatant +fat acids observed. The presence of cottonseed oil is revealed by the +production of a lustrous precipitate which colors the fat acids black. +In some cases the process of Milliau gives better results than the +original method of Bechi, but this is not always the case. It does +away with the use of amyl alcohol and colza oil, but its manipulation is +more difficult. In all doubtful cases the analyst should apply both methods.</p> + +<p><b>364. Detection of Sesame Oil.</b>—Milliau has pointed out a +characteristic reaction of this oil which may be used with advantage +in cases of doubtful identity.<a id="FNanchor_330" href="#Footnote_330" class="fnanchor">[330]</a> +The identification is based on the fact that the free acids of sesame +oil, or some concomitant thereof, give a rose-red color when brought in +contact with a solution of sugar in hydrochloric acid.</p> + +<p>The analytical process is conducted as follows: About fifteen grams +of the oil are saponified with alcoholic soda and when the reaction +is complete treated with 200 cubic centimeters of hot water and +boiled until the alcohol is removed. The fat acids are set free with +decinormal sulfuric acid and removed with a spoon as they rise to the +surface in a pasty state, in which condition they are washed by shaking +with water in a large test tube. When washed, the acids are placed in +an oven at 105° until the greater part of the water is evaporated and +the acids begin to become fluid. At this point they are treated with +half their volume of hydrochloric acid saturated with finely ground +sugar. On shaking the mixture, a rose color is developed which is +characteristic of the sesame oil. Other oils give either no coloration +or at most a yellow tint.</p> + +<p><b>365. The Sulfur Chlorid Reaction.</b>—Some vegetable oils, when +treated with sulfur chlorid, give a hard product similar to elaidin, +while lard does not. This reaction is therefore helpful in +<span class="pagenum"><a id="Page_403"></a>[Pg 403]</span> +discriminating between some vegetable and animal glycerids. The process +which is described by Warren has been used with some satisfaction in +this laboratory.<a id="FNanchor_331" href="#Footnote_331" class="fnanchor">[331]</a></p> + +<p>Five grams of the oil or fat are placed in a tared porcelain dish and +treated with two cubic centimeters of carbon bisulfid and the same +quantity of sulfur chlorid. The dish is placed on a steam-bath and its +contents stirred until the reaction is well under way. The heating is +continued until all volatile products are evaporated, the hard mass +being well rubbed up to facilitate the escape of imprisoned vapors. +The powdered or pasty mass is transferred to a filter and washed with +carbon bisulfid to remove all unaltered oil. The washing with carbon +bisulfid is hastened by pressure and about 200 cubic centimeters of the +solvent should be used. After drying, the weight of insoluble matter is +obtained and deducted from the total weight of the sample used.</p> + +<p>The color and tenacity of the hard, insoluble portion are +characteristic. The quantitive part of the operation appears to have +but little value, but applied qualitively in this laboratory it +produces hard, leathery masses with cotton, olive and peanut oils, +and but little change in lard and beef fats. Qualitively applied, +the process is conducted as described above but without making the +weighings. In this instance it is as easy of application as the process +of Bechi and is deserving of greater attention than has been given it +by analysts.</p> + +<p>In the combination which takes place between the sulfur and the fat it +is probable that only addition products are formed, since the quantity +of alkali required for saponification is not diminished by previously +treating the fat with sulfur chlorid.<a id="FNanchor_332" href="#Footnote_332" class="fnanchor">[332]</a> +The reactions which take place are probably well represented by the +following equations, in which oleic acid is treated with sulfur chlorid:</p> + +<p class="f105">C₁₈H₃₄O₂ + S = C₁₈H₃₄S.O₂. <br> +C₁₈H₃₄S.O₂ + NaOH = C₁₈H₃₄SO₂Na + H₂O.</p> + +<p><b>366. Detection of Cholesterin and Phytosterin in +Glycerids.</b>—Cholesterin is often found in animal glycerids and a +corresponding body, phytosterin, is sometimes found in oils of a +<span class="pagenum"><a id="Page_404"></a>[Pg 404]</span> +vegetable origin.<a id="FNanchor_333" href="#Footnote_333" class="fnanchor">[333]</a> +When one of these two bodies is present it may be useful in +distinguishing between animal and vegetable glycerids. They are +detected as follows: Fifty grams of the glycerids in each case are +saponified with alcoholic alkali, preferably potash, in order to have a +soft soap. After saponification is complete, the alcohol is evaporated +and the residual soap dissolved in two liters of water. The mixture +is shaken with ether and the ethereal solution evaporated to a small +bulk. The residue, which may contain a small quantity of unsaponified +fat, is again treated with alcoholic potash and subjected a second +time to the action of ether, as indicated above, with the addition of +a few drops of water and of alcohol if the emulsion separate slowly. +The ethereal extract finally secured is allowed to evaporate slowly +and the cholesterin (phytosterin) is obtained in a crystalline form. +The melting point of the cholesterin crystals is 146° and that of the +phytosterin 132°.</p> + +<p>Cholesterin crystallizes in thin rhombic tables while phytosterin +separates in stellar aggregates or in bundles of long needles.</p> + +<p>When dissolved in chloroform the two products show different color +reactions with sulfuric acid, cholesterin giving a cherry and +phytosterin a blue-red tint. In a mixture of animal and vegetable +glycerids the two products are obtained together and the melting point +of the mixture may afford some idea of the relative quantities of each +present. It is evident, however, that no reliable judgment can be +formed from these data of the relative proportions of the two kinds of +glycerids in the original sample.</p> + +<p><b>367. Cholesterin and Paraffin in Ether Extracts.</b>—In ethereal +extracts of some bodies, especially of flowers of the chrysanthemum, +paraffin is found combined with cholesterin. The two bodies may be +separated as follows:<a id="FNanchor_334" href="#Footnote_334" class="fnanchor">[334]</a></p> + +<p>The ether extract is treated with aqueous then with alcoholic potash +several times; the residue soluble in ether is a solid body melting at +from 70° to 100°.</p> + +<p>If the ethereal solution be cooled in a mixture of snow and salt, a +crystalline deposit is formed. This substance, purified by repeated +<span class="pagenum"><a id="Page_405"></a>[Pg 405]</span> +precipitations, is obtained colorless in fine crystalline scales +melting at 64°. It is very soluble in ether, benzene and chloroform, +almost insoluble in cold alcohol, and somewhat soluble in hot.</p> + +<p>Its percentage composition is:</p> + +<table class="spb1 fs_90"> + <tbody><tr> + <td class="tdl"> </td> + <td class="tdr">Per cent.</td> + </tr><tr> + <td class="tdl">Carbon<span class="ws3"> </span></td> + <td class="tdc">85.00</td> + </tr><tr> + <td class="tdl">Hydrogen</td> + <td class="tdc">14.95</td> + </tr> + </tbody> +</table> + +<p>It is therefore a paraffin.</p> + +<p>The ethereal solution, freed by the above process from paraffin, leaves +on evaporation a crystalline mass which is cholesterin, retaining +still a small quantity of fat matters. In treating the crystals with +alcoholic potash these fat bodies are saponified and the residue is +taken up with ether. The cholesterin is obtained in fine needles +melting at from 170° to 176°. It presents all the reactions of +cholesterin, especially the characteristic reaction with chloroform and +sulfuric acid.</p> + +<p><b>368. Absorption of Oxygen.</b>—Among oils a distinction is made +between those which oxidize readily and those which are of a more +stable composition. Linseed oil, for instance, in presence of certain +metallic oxids, absorbs oxygen readily and is a type of the drying +oils, while olive oil represents the opposite type.</p> + +<p>The method of determining the quantity of oxygen absorbed is due to +Livache and is carried out as follows:<a id="FNanchor_335" href="#Footnote_335" class="fnanchor">[335]</a></p> + +<p>Precipitated metallic lead (by zinc) is mixed in a flat dish, with +the oil to be tested, in the proportions of one gram of lead to +three-quarters of a gram of oil, and exposed to the air and light of +the workroom. The dish is weighed from time to time until there is no +longer any increase in weight.</p> + +<p>Instead of lead, finely divided copper has been used by Krug in this +laboratory, but the percentage of absorption of oxygen is not so +high with copper as with lead. Krug found the quantities of oxygen +absorbed, after nine days, by the samples treated with copper and lead +respectively to be the following: +<span class="pagenum"><a id="Page_406"></a>[Pg 406]</span></p> + +<table class="spb1"> + <tbody><tr class="fs_90"> + <td class="tdl"> </td> + <td class="tdc">Copper, per cent<br> oxygen absorbed. </td> + <td class="tdc">Lead, per cent<br> oxygen absorbed. </td> + </tr><tr> + <td class="tdl">Olive oil</td> + <td class="tdc">1.69</td> + <td class="tdc">2.03</td> + </tr><tr> + <td class="tdl">Cottonseed oil</td> + <td class="tdc">4.25</td> + <td class="tdc">5.30</td> + </tr><tr> + <td class="tdl">Peanut oil</td> + <td class="tdc">2.74</td> + <td class="tdc">3.87</td> + </tr><tr> + <td class="tdl">Linseed oil</td> + <td class="tdc">5.55</td> + <td class="tdc">7.32</td> + </tr> + </tbody> +</table> + +<p>Livache found that linseed oil absorbed about twice as much oxygen as +indicated by the data just given.</p> + +<p><b>369. Elaidin Reactions.</b>—In discriminating between oils and fats +having a preponderance of olein and others with a smaller proportion of +that glycerid, the conversion of the olein into its isomer elaidin is +of diagnostic value. The following will be found a convenient method of +applying this test:<a id="FNanchor_336" href="#Footnote_336" class="fnanchor">[336]</a></p> + +<p>About ten cubic centimeters of the oil are placed in a test tube +together with half that quantity of nitric acid and one gram of +mercury. The mixture is shaken until the mercury dissolves when the +mass is allowed to remain at rest for twenty minutes. At the end of +this time it is again shaken and placed aside. In from one to three +hours the reaction is complete. Olive, peanut and lard oils give +very hard elaidins. The depth to which a plunger of given weight and +dimensions sinks into an elaidin mixture at a given temperature, has +been used as a measure of the percentage of olein contained in the +sample of oil, but it is evident that such a determination is only +roughly approximate. Copper may be used instead of mercury for the +generation of the oxids of nitrogen, but it is not so effective. The +vapors of nitric oxids may also be conducted directly into the oil +from a convenient generator. The reaction may also be accomplished +by shaking the oil with nitric acid and adding, a drop at a time, a +solution of potassium nitrite.</p> + +<h3>AUTHORITIES CITED IN PART FOURTH.</h3> +<div class="footnotes"> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_229" href="#FNanchor_229" class="label">[229]</a> +Benedikt and Lewkowitsch; Oils, Fats, Waxes, p. 1.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_230" href="#FNanchor_230" class="label">[230]</a> +Op. cit. supra, p. 46.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_231" href="#FNanchor_231" class="label">[231]</a> +Archiv für Physiologie, 1895, Band 61, S. 341: +Chemiker-Zeitung Repertorium, Band 16, S. 338.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_232" href="#FNanchor_232" class="label">[232]</a> +Vid. op. cit. 1, p. 63.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_233" href="#FNanchor_233" class="label">[233]</a> +Bulletin No. 46, Division of Chemistry, U. S. Department of Agriculture, p. 25.</p> +</div> + +<p><span class="pagenum"><a id="Page_407"></a>[Pg 407]</span></p> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_234" href="#FNanchor_234" class="label">[234]</a> +Journal of the Society of Chemical Industry, 1886, p. 508.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_235" href="#FNanchor_235" class="label">[235]</a> +Bulletin No. 13, Division of Chemistry, U. S. Department of Agriculture, p. 423.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_236" href="#FNanchor_236" class="label">[236]</a> +Vid. op. cit. supra, p. 435.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_237" href="#FNanchor_237" class="label">[237]</a> +Vid. op. cit. supra, p. 437.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_238" href="#FNanchor_238" class="label">[238]</a> +Vid. op. et loc. cit. supra.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_239" href="#FNanchor_239" class="label">[239]</a> +Benedikt and Lewkowitsch; Oils, Fats, and Waxes, pp. 96 +et seq.: Zune; Analyse des Beurres, pp. 26 et seq.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_240" href="#FNanchor_240" class="label">[240]</a> +Journal of the Society of Chemical Industry, 1885, p. 535.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_241" href="#FNanchor_241" class="label">[241]</a> +Vid. op. cit. 1, p. 97.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_242" href="#FNanchor_242" class="label">[242]</a> +Vid. op. cit. 7, p. 443.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_243" href="#FNanchor_243" class="label">[243]</a> +Vid. op. cit. 1, pp. 97 and 98.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_244" href="#FNanchor_244" class="label">[244]</a> +Butter, its Analysis and Adulterations, p. 24.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_245" href="#FNanchor_245" class="label">[245]</a> +Bulletin No. 46, Division of Chemistry, U. S. Department of Agriculture, p. 34.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_246" href="#FNanchor_246" class="label">[246]</a> +Vid. op. cit. 7, p. 447.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_247" href="#FNanchor_247" class="label">[247]</a> +Analyse des Beurres, pp. 33 et 63: Zeitschrift für Instrumentenkunde, +1887, Ss. 16, 55, 392, 444: Zeitschrift für physikalische Chemie, Band +18, S. 294. (Ou. pp. 328-9 and 334 read Amagat for Armagat.)</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_248" href="#FNanchor_248" class="label">[248]</a> +Zeitschrift für physikalische Chemie, Band 18, S. 294.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_249" href="#FNanchor_249" class="label">[249]</a> +American Chemical Journal, Vol. 10, p. 392.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_250" href="#FNanchor_250" class="label">[250]</a> +Vid. op. cit. 7, pp. 473 et seq.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_251" href="#FNanchor_251" class="label">[251]</a> +Jean; Chimie Analytique des Matiéres Grasses, p. 26.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_252" href="#FNanchor_252" class="label">[252]</a> +Vid. op. cit. supra, p. 31.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_253" href="#FNanchor_253" class="label">[253]</a> +The Analyst, Vol. 20, p. 135.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_254" href="#FNanchor_254" class="label">[254]</a> +Schlussbericht über die Butteruntersuchungsfrage, +Milchwirthschaftlicher Verein, Korrespondenzblatt, No. 39, 1891, S. 15.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_255" href="#FNanchor_255" class="label">[255]</a> +Vid. op. cit. 7, p. 75.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_256" href="#FNanchor_256" class="label">[256]</a> +Journal of the American Chemical Society, Vol. 15, p. 173.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_257" href="#FNanchor_257" class="label">[257]</a> +Communicated by Krug to author.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_258" href="#FNanchor_258" class="label">[258]</a> +Vid. op. cit. 7, pp. 449 et seq.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_259" href="#FNanchor_259" class="label">[259]</a> +Vid. op. cit. 28, Vol. 18, p. 189.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_260" href="#FNanchor_260" class="label">[260]</a> +Vid. op. cit. 7, Plates 32 and 35.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_261" href="#FNanchor_261" class="label">[261]</a> +Vid. op. cit. supra, p. 452.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_262" href="#FNanchor_262" class="label">[262]</a> +Vid. op. cit. supra., p. 93.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_263" href="#FNanchor_263" class="label">[263]</a> +Vogel; Practische Spectralanalyse, S. 279: Zune; Analyse +des Beurres, Tome 2, p. 48: Benedikt and Lewkowitsch; Oils, +Fats, Waxes, p. 83.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_264" href="#FNanchor_264" class="label">[264]</a> +Bulletin de l’Association Belge des Chimistes, Tome 9, p. 145.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_265" href="#FNanchor_265" class="label">[265]</a> +Journal of the Chemical Society, Abstracts, Vol. 46, p. 1078: +Dingler’s Polytechnisches Journal, Band 252, S. 296.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_266" href="#FNanchor_266" class="label">[266]</a> +The Analyst, July 1894, p. 152.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_267" href="#FNanchor_267" class="label">[267]</a> +Rapport sur les Procédé pour reconnâitre les +Falsifications des Huiles d’Olive, p. 37.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_268" href="#FNanchor_268" class="label">[268]</a> +Vid. op. cit. 7, p. 251.</p> +</div> + +<p><span class="pagenum"><a id="Page_408"></a>[Pg 408]</span></p> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_269" href="#FNanchor_269" class="label">[269]</a> +Taylor; Annual Report U. S. Department of Agriculture, 1877, p. 622: +Milliau; Journal of the American Chemical Society, Vol. 15, p. 153.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_270" href="#FNanchor_270" class="label">[270]</a> +Gantter; Zeitschrift für analytische Chemie, 1893, Band 32, S. 303.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_271" href="#FNanchor_271" class="label">[271]</a> +Welmans; Journal of the Society of Chemical Industry, 1892, p. 548.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_272" href="#FNanchor_272" class="label">[272]</a> +Vid. op. cit. 1, p. 254.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_273" href="#FNanchor_273" class="label">[273]</a> +Pharmaceutische Zeitung, 1891, p. 798: The Analyst, Vol. 17, p. 59.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_274" href="#FNanchor_274" class="label">[274]</a> +Comptes rendus, Tome 112, p. 105.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_275" href="#FNanchor_275" class="label">[275]</a> +Pearmain and Moor; The Analyst, Vol. 20, p. 174.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_276" href="#FNanchor_276" class="label">[276]</a> +Pharmaceutische Zeitschrift für Russland, 1888, S. 721: +American Journal of Pharmacy, 1889, p. 23.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_277" href="#FNanchor_277" class="label">[277]</a> +Vid. op. cit. 7, p. 502.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_278" href="#FNanchor_278" class="label">[278]</a> +Muir; Elements of Thermal Chemistry, p. 25 et seq.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_279" href="#FNanchor_279" class="label">[279]</a> +Comptes rendus, Tome 35 (1852), p. 572.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_280" href="#FNanchor_280" class="label">[280]</a> +Allen; Commercial Organic Analysis, Vol. 2, p. 56.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_281" href="#FNanchor_281" class="label">[281]</a> +Vid. op. cit. 1, p. 235; et op. cit. 23, p. 217.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_282" href="#FNanchor_282" class="label">[282]</a> +Vid. op. cit. 7, p. 44.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_283" href="#FNanchor_283" class="label">[283]</a> +Vid. op. cit. supra, p. 445: Proceedings American Public +Health Association, Vol. 10.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_284" href="#FNanchor_284" class="label">[284]</a> +Vid. op. cit. 23, p. 61.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_285" href="#FNanchor_285" class="label">[285]</a> +Journal of the Society of Chemical Industry, 1891, p. 234.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_286" href="#FNanchor_286" class="label">[286]</a> +Vid. op. cit. 1, p. 240.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_287" href="#FNanchor_287" class="label">[287]</a> +The Analyst, Vol. 22, p. 58.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_288" href="#FNanchor_288" class="label">[288]</a> +Vid. op. cit. supra, Vol. 20, p. 146.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_289" href="#FNanchor_289" class="label">[289]</a> +Journal of the American Chemical Society, Vol. 17, p. 378.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_290" href="#FNanchor_290" class="label">[290]</a> +Dingler’s Polytechnisches Journal, 1884, Ss. 253-281: +Journal of the Society of Chemical Industry, 1884, p. 641.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_291" href="#FNanchor_291" class="label">[291]</a> +Bulletin No. 46, Division of Chemistry, U. S. Department of Agriculture, p. 32.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_292" href="#FNanchor_292" class="label">[292]</a> +Liebermann; Berichte der deutschen chemischen +Gessellschaft, Band 24, S. 4117.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_293" href="#FNanchor_293" class="label">[293]</a> +Vid. op. cit. 1, p. 136.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_294" href="#FNanchor_294" class="label">[294]</a> +Vid. op. cit. 57, 1895, pp. 130 and 1030.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_295" href="#FNanchor_295" class="label">[295]</a> +Zeitschrift für analytische Chemie, Band 32, Ss. 181 et seq.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_296" href="#FNanchor_296" class="label">[296]</a> +Vid. op. cit. 61, Vol. 16, p. 372.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_297" href="#FNanchor_297" class="label">[297]</a> +Zeitschrift für angewandte Chemie, 1895, S. 254.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_298" href="#FNanchor_298" class="label">[298]</a> +Chemiker-Zeitung, Band 19, Ss. 1786 and 1831.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_299" href="#FNanchor_299" class="label">[299]</a> +Vid. op. cit. 61, Vol. 16, p. 277.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_300" href="#FNanchor_300" class="label">[300]</a> +Pharmaceutical Journal, Sept. 25, 1880.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_301" href="#FNanchor_301" class="label">[301]</a> +Vid. op. cit. 59, Vol. 20, p. 50.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_302" href="#FNanchor_302" class="label">[302]</a> +Williams; vid. op. cit. supra, Vol. 20, p. 277.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_303" href="#FNanchor_303" class="label">[303]</a> +Vid. op. cit. 59, 1889, p. 61.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_304" href="#FNanchor_304" class="label">[304]</a> +Vid. op. cit. 61, Vol. 15, p. 110.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_305" href="#FNanchor_305" class="label">[305]</a> + Zeitschrift für physiologische Chemie, Band 14, S. 599; +Band 12, S. 321; Band 16, S. 152.</p> +</div> + +<p><span class="pagenum"><a id="Page_409"></a>[Pg 409]</span></p> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_306" href="#FNanchor_306" class="label">[306]</a> +Vid. op. cit. 1, p. 60.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_307" href="#FNanchor_307" class="label">[307]</a> +Vid. op. cit. supra, p. 557.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_308" href="#FNanchor_308" class="label">[308]</a> +Vid. op. cit. 7, p. 459; vid. op. cit. 63, p. 27.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_309" href="#FNanchor_309" class="label">[309]</a> +Vid. op. cit. 69, 1895, S. 721.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_310" href="#FNanchor_310" class="label">[310]</a> +Vid. op. cit. 67, Band 18, S. 199: vid. op. cit. 7, pp. 58-461: +vid. op. cit. 63, p. 30.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_311" href="#FNanchor_311" class="label">[311]</a> +Vid. op. cit. 52, p. 40.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_312" href="#FNanchor_312" class="label">[312]</a> +Vid. op. cit. 1, p. 119.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_313" href="#FNanchor_313" class="label">[313]</a> +Vid. op. cit. supra, p. 127.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_314" href="#FNanchor_314" class="label">[314]</a> +Monatshefte für Chemie und verwandte Theile anderer +Wissenschaften, Band 8, S. 40.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_315" href="#FNanchor_315" class="label">[315]</a> +Vid. op. cit. 57, 1890, p. 846.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_316" href="#FNanchor_316" class="label">[316]</a> +Reichert; vid. op. cit. 67, Band 18, S. 68.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_317" href="#FNanchor_317" class="label">[317]</a> +Meissl; vid. op. cit. 62, Band 233, S. 229.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_318" href="#FNanchor_318" class="label">[318]</a> +Vid. op. cit. 1, p. 121.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_319" href="#FNanchor_319" class="label">[319]</a> +Vid. op. cit. 63, p. 28.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_320" href="#FNanchor_320" class="label">[320]</a> +Vid. op. cit. 67, Band 16, S. 145; Band 18, S. 68: vid. +op. cit. 7, p. 53: vid. op. cit. 59, 1877, p. 147.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_321" href="#FNanchor_321" class="label">[321]</a> +Vid. op. cit. 57, 1888, pp. 526 and 697: American +Chemical Journal, Vol. 10, p. 326: vid. op. cit. 1, pp. 123-127.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_322" href="#FNanchor_322" class="label">[322]</a> +Vid. op. cit. 1, p. 143.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_323" href="#FNanchor_323" class="label">[323]</a> +Vid. op. ch. 7, p. 143.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_324" href="#FNanchor_324" class="label">[324]</a> +Vid. op. cit. 67, 1890, S. 4.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_325" href="#FNanchor_325" class="label">[325]</a> +Allen; Commercial Organic Analysis, Vol. 2, pp. 224-236.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_326" href="#FNanchor_326" class="label">[326]</a> +Analyse Chimique des Matiéres Grasses, p. 13.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_327" href="#FNanchor_327" class="label">[327]</a> +Chemiker-Zeitung, Band 19, S. 451.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_328" href="#FNanchor_328" class="label">[328]</a> +Annali del Laboratorio Chimico, 1891-92, p. 197: +Bulletin No. 13, Division of Chemistry, U. S. Department of +Agriculture, p. 465: Journal of Analytical and Applied Chemistry, Vol. +1, p. 449; Vol. 2, pp. 119 and 275; vid. op. cit. 311.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_329" href="#FNanchor_329" class="label">[329]</a> +Rapport presenté a l’Academie Sciences le 20 fevrier, +1883: Analyse des Matiéres Grasses, p. 17: Bulletin No. 13, Division of +Chemistry, U. S. Department of Agriculture, p. 446.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_330" href="#FNanchor_330" class="label">[330]</a> +Analyse des Matiéres Grasses, p. 15.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_331" href="#FNanchor_331" class="label">[331]</a> +Chemical News, 1888, p. 113: Bulletin No. 13, Division +of Chemistry, U. S. Department of Agriculture, p. 468.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_332" href="#FNanchor_332" class="label">[332]</a> +Vid. op. cit. 69, 1895, S. 535.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_333" href="#FNanchor_333" class="label">[333]</a> +Justus Liebig’s Annalen der Chemie, Band 192, S. 178: +vid. op. cit. 67, Band 26, S. 575: vid. op. cit. 7, p. 514.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_334" href="#FNanchor_334" class="label">[334]</a> +Journal de Pharmacie et de Chimie, 1889, p. 447.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_335" href="#FNanchor_335" class="label">[335]</a> +Moniteur Scientifique, Tome 13, p. 263: vid. op. cit. 69, 1884, S. 262.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_336" href="#FNanchor_336" class="label">[336]</a> +Vid. op. cit. 7, p. 515.</p> +</div> +</div> + +<hr class="chap x-ebookmaker-drop"> + +<div class="chapter"> +<p><span class="pagenum"><a id="Page_410"></a>[Pg 410]</span></p> +<h2 class="nobreak">PART FIFTH.<br> +<span class="h_subtitle">SEPARATION AND ESTIMATION OF<br> BODIES CONTAINING NITROGEN.</span></h2> +</div> + +<p><b>370. Nature of Nitrogenous Bodies.</b>—The nitrogenous bodies, +valuable as foods, belong to the general class of proteids and +albuminoids. They are composed chiefly of carbon, hydrogen, oxygen, +sulfur and nitrogen. Some of them, as lecithin and nuclein, contain +phosphorus instead of sulfur, but these resemble the fats rather than +the proteids.</p> + +<p>Nitrogenous organic bodies of the class mentioned above are designated +by the general name proteids. The term albumin is restricted in a +physiological sense to a certain class of proteids. The term albuminoid +is often used synonymously, as above, for proteids, but, more strictly +speaking, it should be reserved for that class of bodies such as +gelatin, mucin, keratin and the like, not really proteids, but, +nevertheless, closely resembling them.<a id="FNanchor_337" href="#Footnote_337" class="fnanchor">[337]</a> +In chemical composition the proteids are characterized by the relative +constancy of their nitrogen content, the mean percentage of this +element being about sixteen, but varying in some instances more than +two units from that number.</p> + +<p><b>371. Classification of Proteids.</b>—Many classifications of the +proteids have been given based on physical, chemical and physiological +characteristics. In respect of origin, they are divided into two +great classes, <i>viz.</i>, vegetable and animal. In respect of their +physical and chemical properties the following classification of the +proteids may be made.<a id="FNanchor_338" href="#Footnote_338" class="fnanchor">[338]</a></p> + +<p><i>Albumins.</i>—These are proteids soluble in water and not +precipitated from their aqueous solutions by sodium chlorid or +magnesium sulfate. They are easily coagulated by heat and are +represented by three great classes, <i>viz.</i>, egg-, serum-, and +lactalbumin.</p> + +<p>Egg albumin occurs in the white of egg; serum albumin is found in the +serum of the blood. Vegetable albumins have been prepared from wheat, +<span class="pagenum"><a id="Page_411"></a>[Pg 411]</span> +rye, potatoes, and papaws. (<i>Carica Papaya</i>). These vegetable +albumins are coagulated by heat at about 70° and are not precipitated +by the salt solutions named above, nor by acetic acid. The myrosin of +mustard seeds also resembles vegetable albumin.</p> + +<p><i>Globulins.</i>—These bodies are insoluble in water, soluble +in dilute solutions of neutral salts, but precipitated therefrom +by saturation with sodium chlorid or magnesium sulfate. They are +coagulated by heat. Among others belonging to this group are serum +globulin, fibrinogen, myosin, crystalin, and globin.</p> + +<p>Serum globulin is found in the serum of blood; cell globulin is found +in lymph cells; fibrinogen occurs in the blood plasma; plasmin, in +blood plasma; myosin, in dead muscles; vitellin, in the yolk of eggs; +crystalin, in the lens of the eye; haemoglobin, in the red pigment of +the blood; haemocyanin, in the blood of certain low grade animals.</p> + +<p>Vegetable globulins are found in the cereals, leguminous plants, +papaws and other vegetables, and are divided into two groups, myosins +and paraglobulins. The vegetable myosins coagulate at from 55° to +60° and are precipitated from a saline solution by removing the salt +by dialysis. In this form, however, they lose their true nature as +globulins, becoming insoluble in weak saline solutions.</p> + +<p>The vegetable paraglobulins are coagulated at from 70° to 75°. +Vegetable vitellin, which is not included in this classification, can +be obtained in a crystalline form and of remarkable purity.<a id="FNanchor_339" href="#Footnote_339" class="fnanchor">[339]</a></p> + +<p><i>Albuminates.</i>—This name is given to the compounds of the +proteids with metallic oxids or bases, and also to acid and alkali +albumins. They are insoluble in water or dilute neutral salts, but +easily soluble in strong acids or alkalies. Casein is a type of this group.</p> + +<p>Acid albumin is made from egg albumin by treatment with hydrochloric +acid; alkali albumin is formed in egg albumin by the action of a dilute +alkali; trinitroalbumin is formed from dry albumin by treatment with +nitric acid; casein or caseinogen is the chief proteid in milk.</p> + +<p>The chief vegetable albuminates are legumin and conglutin. Legumin is a +vegetable casein and occurs chiefly in peas, beans and other leguminous +<span class="pagenum"><a id="Page_412"></a>[Pg 412]</span> +seeds. It is prepared by extracting the meal of the seeds mentioned +with dilute alkali, filtering the extract, precipitating with acetic +acid, washing the precipitate with alcohol, and drying over sulfuric +acid. Treated with sulfuric acid it yields leucin, tyrosin and glutamic +and aspartic acids. Conglutin is prepared in a similar manner from almonds.</p> + +<p>It is probable that these bodies do not exist as such in the fresh +seeds in question but are produced therein from the other proteids +by the alkali used in extraction. A further description of vegetable +proteids will be found in the special paragraphs devoted to the study +of these bodies in the principal cereals.</p> + +<p><i>Proteoses.</i>—This name is applied to proteids which are not +coagulated by heat, but most of them are precipitated by saturated +solutions of neutral salts. They are also precipitated by nitric acid. +They are formed from other proteids by the action of proteolytic +ferments. The albumoses represent this group.</p> + +<p>Protoalbumose is soluble in distilled water and weak saline solutions +and is precipitated by mercuric chlorid and copper sulfate.</p> + +<p>Heteroalbumose is insoluble in distilled water, but soluble in weak +saline solutions, from which it separates when the salts are removed +by dialysis. Deuteroalbumose is soluble in distilled water and saline +solutions and is not precipitated on saturation with sodium chlorid. It +is thrown out by mercuric chlorid but not by copper sulfate.</p> + +<p>Vegetable proteoses are known as phytalbumoses, two of which have been +found in the juice of the papaw mentioned above. They have also been +found in cereals.</p> + +<p><i>Peptones.</i>—These bodies are very soluble in water but are not +thrown out by heat, by saturation with neutral salts, nor by nitric +acid. They are completely precipitated by tannin and by strong alcohol.</p> + +<p>The peptones are the only soluble proteids which are not precipitated +by saturation with ammonium sulfate. The principal animal varieties are +hemi- and anti-peptones. These forms of proteids do not appear to exist +as such in vegetable products but are produced in large quantities by +treating other proteids with pepsin or pancreatin. In sprouting plants, +there appears to be a widely diffused ferment capable of converting the +<span class="pagenum"><a id="Page_413"></a>[Pg 413]</span> +proteids of the cotyledons into peptonoid bodies and thus fitting them +for entering the tissues of the new plant.</p> + +<p><i>Insoluble Proteids.</i>—This class includes a miscellaneous +collection of nitrogenous bodies not belonging to any of the definite +groups already mentioned. Fibrin and gluten are types of these +insoluble bodies. Fibrin is formed from the fibrinogen of fresh blood +and causes coagulation. When washed free of red blood corpuscles it is +a white elastic solid. It is insoluble in water and is converted into +albumoses and peptones by trypsin and pepsin. It swells up when treated +with a very weak one-tenth per cent solution of hydrochloric acid and +dissolves to acid albumin when heated therewith.</p> + +<p>Gluten is the most important of the insoluble vegetable proteids and +forms the chief part of the nitrogenous constituents of wheat. It is +readily prepared by washing wheat flour in cold water, as will be +described further on. It is probably a composite body formed by the +process of extraction from at least two proteid bodies existing in +wheat. When dried it forms a horny elastic mass of a yellow-gray color. +Gluten is composed of two bodies, one soluble the other insoluble +in alcohol. The part insoluble in alcohol has been called vegetable +fibrin, and the soluble part is subdivided into two portions, one +unicedin or vegetable unicin, and the other glutin (gliadin) or +vegetable gelatin. Gluten, according to some authorities, does not +properly exist in wheat flour, but is formed therein by the action +of water and certain ferments from free existing proteids. A better +explanation of the composition of gluten is that of Osborne, which will +be given further on.</p> + +<p><b>372. Albuminoids.</b>—In this paragraph the term albuminoids is not +employed as synonymous with proteids but as characteristic of a class +of bodies nearly resembling them, but, nevertheless, differing from +them in many important particulars. Following is an abstract of their +classification as given in Watt’s dictionary.<a id="FNanchor_340" href="#Footnote_340" class="fnanchor">[340]</a></p> + +<p><i>Collagen.</i>—The nitrogenous portions of connective tissues are +largely composed of collagen. By boiling water it is converted into +gelatin. It may be prepared from tendons as follows: The tendinous +<span class="pagenum"><a id="Page_414"></a>[Pg 414]</span> +tissues are shredded as finely as possible and extracted with cold +water to remove the soluble proteids. Thereafter they are subjected +for several days to the action of lime water, which dissolves the +cement holding the fibers together. The residual insoluble matter is +washed with water, weak acetic acid, and again with water. The residue +is chiefly collagen, mixed, however, with some elastin and nuclein. +With dilute acids and alkalies collagen swells up after the manner of +fibrin. The organic nitrogenous matter of bone consists largely of +collagen, which is sometimes called ossein.</p> + +<p><i>Gelatin.</i>—When the white fibers of collagen, obtained as above, +are subjected to the action of boiling water or of steam under pressure +they dissolve and form gelatin. Isinglass is a gelatin made from the +swimming bladder of the sturgeon or other fish. Glue is an impure +gelatin obtained from hides and bones. Pure gelatin may be prepared +from the commercial article by removing all soluble salts therefrom by +treatment with cold water, dissolving in hot water and filtering into +ninety per cent alcohol. The gelatin separates in the form of white +filaments and these are removed and dried. Gelatin is insoluble in +cold but soluble in hot water. It is insoluble in alcohol, ether and +chloroform. Its hot aqueous solutions deflect the plane of polarized +light to the left. Its gyrodynat varies with temperature and degree of +dilution and is also influenced by acids and alkalies. At 30° it is +[α]<span class="fs_80"><sub>D</sub></span>³⁰° = -130.</p> + +<p>Gelatin is not precipitated by acetic acid nor lead acetate solution, +in which respect it differs from chondrin.</p> + +<p>If boiled for a day, or in a short time if heated to 140° in a sealed +tube, gelatin loses its power of setting and is split up into two +peptonoid bodies, semi-glutin and hemi-collin. Gelatin is easily +digested but cannot take the place of other proteids in nutrition.</p> + +<p><i>Mucin.</i>—This albuminoid, together with globulin, forms the +principal part of connective tissue. It is also present in large +quantities in mucus and is the chief lubricant of mucous membranes. It +is extremely difficult to prepare mucin in a state of purity, and it is +<span class="pagenum"><a id="Page_415"></a>[Pg 415]</span> +not certain that it has ever been accomplished. It is precipitated +but not rendered subsequently insoluble by sodium chlorid, magnesium +sulfate and alcohol. When boiled with sulfuric acid it yields leucin +and tyrosin and, with caustic soda, pyrocatechin.</p> + +<p><i>Met- and Paralbumin.</i>—Metalbumin is a form of mucin and differs +from paralbumin by giving no precipitate when boiled. Both bodies yield +reducing sugars when boiled with dilute sulfuric acid.</p> + +<p><i>Nuclein.</i>—The nitrogenous matters which form the nuclei of the +ultimate cells are called nuclein. Nuclein resembles mucin in many +physical properties but contains phosphorus. It is also, like mucin, +resistant to pepsin digestion. The nuclein of eggs and milk probably +contains iron. Nuclein is found also in cells of vegetable origin and +in yeast and mildew.</p> + +<p><i>Nucleoproteids.</i>—These are bodies which yield both nuclein +and albumin when boiled with water or treated with dilute acids or +alkalies. Many nucleoproteids have the physical properties of mucus and +the sliminess of the bile and of the synovial liquid is due to them. +They are the chief nitrogenous constituent of all protoplasm.</p> + +<p><i>Chondrin.</i>—Chondrin is obtained from cartilage by boiling +with water. The solutions of chondrin set on cooling in the manner +of gelatin. They are precipitated by the same reagents used for +throwing out gelatin and mucin. Chondrin is also levorotatory. By some +authorities chondrin is regarded as a mixture of gelatin and mucin.</p> + +<p><i>Elastin.</i>—The elastic fibers of connective tissue are composed +of this material. It can be prepared from the neck muscles by boiling +with ether and alcohol to remove fats and then for a day and a half +with water to extract the collagens. The residue is boiled with strong +acetic acid and thereafter with strong soda until the fibers begin to +smell. It is then treated with weak acetic acid and for a day with +dilute hydrochloric acid. The acid is removed by washing with water +and the residue is elastin. There is no solvent which acts on elastin +without decomposing it. It is digested by both pepsin and trypsin with +the formation of peptones. +<span class="pagenum"><a id="Page_416"></a>[Pg 416]</span></p> + +<p><i>Keratin.</i>—This nitrogenous substance is found chiefly in hairs, +nails, and horns. It is essentially an alteration proteid product due +to peripheral exposure. It is prepared by digesting the fine ground +material successively with ether, alcohol, water and dilute acids. The +residue is keratin. An imperfect aqueous solution may be secured by +heating for a long time under pressure to 200°. It is also dissolved +by boiling the materials mentioned above with alkalies, and when the +solution thus obtained is treated with water, hydrogen sulfid is +evolved, showing that the sulfur of the molecule is loosely combined.</p> + +<p>Horn swells up when treated with dilute acetic acid and dissolves in +the boiling glacial acid. When treated with hot dilute sulfuric acid it +yields aspartic and volatile fat acids, leucin and tyrosin. Keratin, +when burning, gives off a characteristic odor as is perceived in +burning hair.</p> + +<p><i>Other Albuminoids.</i>—Among the albuminoids of less importance +may be mentioned neurokeratin found in the medullary sheath of nerve +fibers; chitin occurring in the tissues of certain invertebrates; +conchiolin, found in the shells of mussels and snails; spongin, +occurring in sponges; fibroin forming silk and spiders webs; and hyalin +or hyalogen found in edible birds’ nests.</p> + +<p>The nitrogenous bases in flesh which are soluble in cold water, +<i>viz.</i>, kreatin, kreatinin, carnin, sarkin and xanthin are not +classed among the albuminoid bodies, since they have a much higher +percentage of nitrogen than is found in true proteid bodies, and are +further differentiated from them by the absence of sulfur.</p> + +<p><b>373. Other Forms of Nitrogen.</b>—In addition to the proteids and +albuminoids mentioned above, agricultural products may contain nitrogen +in the form of ammonia, amid nitrogen and nitric acid. The quantities +of nitrogen thus combined are not large but often of sufficient +magnitude to demand special study. In general, these bodies belong to +transition products, representing stages in the transfer of nitrogen +from the simple to complex forms of combination, or the reverse.</p> + +<p>For instance, the nitrogen which finally appears in the proteids of a +<span class="pagenum"><a id="Page_417"></a>[Pg 417]</span> +plant has entered its organism chiefly as nitric acid, and the +nitric acid which is found in a vegetable product is therefore a +representative of the quantity of unabsorbed nitrogen present in +the tissues at the moment when the vital activity of the plant is +arrested. In some instances, it is found that the absorption of +nitrates by vegetable tissues takes place in far larger quantities than +is necessary for their nutrition, and in these cases the excess of +nitrates accumulates, sometimes to a remarkable extent. In a case cited +in the reports of the Kansas Agricultural Experiment Station, where +Indian corn was grown on ground which had been used for a hog pen, the +quantity of potassium nitrate found in the dried stalks was somewhat +remarkable. When one of the stalks was cut in two and tapped lightly +upon a table, crystals of potassium nitrate were easily obtained in the +form of fine powder. On splitting the cornstalk the crystals in the +pith could be seen without the aid of a microscope. On igniting a piece +of the dried stalk it burned rapidly with deflagration. The percentage +of potassium nitrate in the dried material was 18.8. Cattle eating this +fodder were poisoned.<a id="FNanchor_341" href="#Footnote_341" class="fnanchor">[341]</a></p> + +<p>In preserved meat products large quantities of oxidized nitrogen are +often found, and these come from the use of potassium nitrate as a +preserving and coloring agent. Ammonia is rarely found in vegetable +tissues in greater quantities than mere traces, but may often exist in +weighable amounts in animal products.</p> + +<p>Amid nitrogen is found rather constantly associated with proteid +matters in vegetable products. Asparagin and glutamin are instances +of amid bodies of frequent occurrence. Betain and cholin are found in +cottonseed.</p> + +<p>The occurrence of nitrogen, in the form of alkaloids, is of interest +to agricultural chemists in this country, chiefly from its presence +as nicotin in tobacco and from a toxicological point of view, but +in other localities the production of alkaloids, as for instance in +opium, tea and coffee, is a staple agricultural industry. The methods +of separating and determining these forms of nitrogen will be given +further on. This description can evidently not include an extended +compilation of the methods of separating and determining alkaloidal +bodies, with the exception of those with which the agricultural analyst +<span class="pagenum"><a id="Page_418"></a>[Pg 418]</span> +will be called upon frequently to deal, <i>viz.</i>, nicotin and +caffein and nitrogenous bases such as betain and cholin.</p> + +<h3>QUALITIVE TESTS FOR<br> NITROGENOUS BODIES.</h3> + +<p><b>374. Nitric Acid.</b>—Any nitric acid or nitrate which an +agricultural product may contain may be leached out by treating the +fine-ground material with cold water. From vegetable matters this +extract is evaporated to a small bulk, filtered, if necessary, and +tested for nitric acid by the usual treatment with ferrous sulfate +and sulfuric acid. In the case of vegetable substances there will not +usually be enough of organic matter to interfere with the delicacy of +the reaction, but in animal extracts this may occur. Colored extracts +should be decolorized with animal char (bone-black) before they are +subjected to examination. It is not well to attempt to remove the +organic matters, but, since they are more insoluble in water than the +nitrates, the solution containing both may be evaporated to dryness +and treated with a quantity of cold water insufficient for complete +solution. The nitrates will be found in the solution obtained in a +larger proportionate quantity than before.</p> + +<p><b>375. Amid Nitrogen.</b>—One or more atoms of the hydrogen in +ammonia may be replaced by acid or basic bodies (alcohol radicles). +In the former cases amids, in the latter amins result. In the ratio +of displacement there are formed primary, secondary, and tertiary +bodies determined by the number of hydrogen atoms replaced. The primary +amids are the only ones of these bodies that are of interest in this +connection.</p> + +<p>The amids are easily decomposed, even on heating with water and the +more readily with acids and alkalies, the amido radicle being converted +into ammonia. A type of these reactions is given below.</p> + +<p class="f105">CH₃.CO.NH₂ + H₂O = CH₂.CO.OH + H₃N.</p> + +<p>On boiling an amid with hydrochloric acid, the ammonia is procured +as chlorid whence it is easily expelled by heating with an alkali. +In a body free of ammonia, an amid is easily detected by subjecting +the substance containing it to the action of hot hydrochloric acid, +filtering, neutralizing the free acid with sodium hydroxid, adding an +<span class="pagenum"><a id="Page_419"></a>[Pg 419]</span> +excess thereof and distilling into an acid.<a id="FNanchor_342" href="#Footnote_342" class="fnanchor">[342]</a> In case the quantity +of ammonia produced is very small it may be detected by the nessler +reagent.<a id="FNanchor_343" href="#Footnote_343" class="fnanchor">[343]</a> +Amids are soluble in a fresh, well washed preparation of cupric hydrate +suspended in water. The hydrate also passes into solution forming a +liquid of a deep blue color.</p> + +<p>If amids be added to a cold solution of potassium nitrate in sulfuric +acid free nitrogen is evolved.</p> + +<p><b>376. Ammoniacal Nitrogen.</b>—This combination of nitrogen may be +detected by distilling the sample, or an aqueous extract thereof, with +magnesia or barium carbonate. The ammonia is collected in an acid and +detected therein by the usual qualitive reactions.</p> + +<p><b>377. Proteid Nitrogen.</b>—There are a few general qualitive +reactions for proteid nitrogen and some special ones for distinct forms +thereof. Below will be given a few of those reactions which are of most +importance to the agricultural analyst:</p> + +<p><i>Conversion into Ammonia.</i>—All proteid matters are converted +into ammonia on boiling with strong sulfuric acid in presence of an +oxygen carrier. Mercury is the substance usually selected to effect the +transfer of the oxygen. Bodies which are found to be free of nitrates, +ammonia and amids, are subjected directly to oxidation with sulfuric +acid, and the ammonia produced thereby is distilled and detected in +the manner already suggested. If nitrogen be present in the form of +ammonia, amids and nitrates, the substance may be heated with an acid, +hydrochloric or acetic, thrown on a filter, washed with hot dilute acid +and the residue tested as above for proteid nitrogen.</p> + +<p><i>Biuret Reaction.</i>—When proteid matter is dissolved in sulfuric +acid, the solution, made alkaline with potassium hydroxid and treated +with a few drops of a solution of copper sulfate, gives a violet +coloration. This is commonly known as the biuret reaction, because the +substance <b>C₂H₆N₃O₂</b>, biuret, left on heating urea to 160° gives the +coloration noted in the conditions mentioned.</p> + +<p>It has been found by Bigelow, in this laboratory, that if a solution is +to be examined containing a very small amount of a proteid or similar +body, the copper sulfate solution should not contain more than four +<span class="pagenum"><a id="Page_420"></a>[Pg 420]</span> +grams of <b>CuSO₄.5H₂O</b> in 100 cubic centimeters of water, and the test +should first be made by adding to the solution one or two drops of +this copper sulfate solution, and then a strong excess of potassium +or sodium hydroxid. The test may be repeated, using from one-half to +two cubic centimeters of the copper sulfate solution, according to the +amount of proteid present. If too much of the copper sulfate solution +be employed its color may conceal that of the reaction.</p> + +<p>Heating to the boiling point sometimes makes the violet color more +distinct.</p> + +<p>If a solid is to be examined it is first suspended in water, and in +this state treated in the same manner as a solution. If solution is not +complete, the mixture should be filtered when the color produced may be +observed in the filtrate.</p> + +<p>Proteoses and peptones give a red to red-violet and other proteids a +violet to violet-blue coloration.</p> + +<p><i>Xanthoproteic Reaction.</i>—Strong nitric acid produces a yellow +coloration of proteid matter, which is intensified on warming. On +treating the yellow mixture with ammonia in slight excess the color is +changed to an orange or red tint.</p> + +<p><b>378. Qualitive Tests for Albumin.</b>—Albumin is one of the chief +proteids and exists in both animal and vegetable substances. It is +soluble in cold water and may therefore be separated from many of its +nearly related bodies which are insoluble in that menstruum. In aqueous +solutions its presence may be determined by the general reactions for +proteid matters given above or by the following tests:</p> + +<p><i>Precipitation by Heat.</i>—Albumin is coagulated by heat. Vegetable +albumins become solid at about 65° and those of animal origin at a +somewhat higher temperature (75°). Some forms of animal albumin, +however, as for instance that contained in the serum, coagulate at a +lower temperature.</p> + +<p><i>Precipitation by Acids.</i>—Dilute acids also precipitate albumins +especially with the aid of heat. Practically all the albumins are +thrown out of solution by application of heat in the presence of dilute +acids.</p> + +<p><i>Mercuric Salts.</i>—Acid mercuric nitrate and a mixture of mercuric +chlorid, potassium iodid and acetic acid completely precipitate all +albuminous matters.<a id="FNanchor_344" href="#Footnote_344" class="fnanchor">[344]</a></p> + +<p><span class="pagenum"><a id="Page_421"></a>[Pg 421]</span> +The yellow or red color produced on heating albumin with the mercuric +nitrate is known as Million’s reaction.</p> + +<p><b>379. Qualitive Test for Peptones and Albuminates.</b>—When peptones +and albuminates are dissolved in an excess of glacial acetic acid and +the solution treated with sulfuric acid a violet color is produced and +also a faint fluorescence.</p> + +<p><i>Separation of Peptones and Albumoses.</i>—In a solution of peptones +and albumoses the latter may be precipitated by saturating the solution +with finely powdered zinc or ammonium sulfate.</p> + +<p><i>Action of Phosphotungstic Acid.</i>—All proteid matters in aqueous, +alkaline or acid solutions, are precipitated by sodium phosphotungstate +in a strongly acid solution. Acetic, phosphoric, or sulfuric acid may +be used for producing the required acidity, preference being given to +the latter.</p> + +<p><i>Action of Trichloracetic Acid.</i>—In the precipitation of albumin +by trichloracetic acid, there is formed a compound of the two bodies +which to 100 parts of albumin has 26.8 parts of the trichloracetic acid.</p> + +<p>The different albuminoid bodies obtained by precipitation behave in +a similar manner. There are formed flocculent precipitates insoluble +both in dilute and concentrated acids in the cold and also at a high +temperature, with the exception of the hemialbumose compound.<a id="FNanchor_345" href="#Footnote_345" class="fnanchor">[345]</a></p> + +<p>Albumin peptone, however, gives with the acid named in concentrated +solution a precipitate easily soluble in an excess of the reagent. In +the analysis of cow’s milk but not of human milk, this acid can be used +for the estimation of the albuminoid substances. With both kinds of +milk it can be used for the estimation of the albumin after the removal +of the casein.</p> + +<p>After precipitation of the albuminoid bodies, the milk sugar can be +estimated by polarizing the filtrate and, volumetrically after removal +of the excess of the acid by evaporation. By means of trichloracetic +acid it is possible to separate albumin peptone from mucus and mucus +peptone. A similar reaction is also produced by dichloracetic acid, but +the reaction with this last agent is less delicate than with the other. +Neither mucus nor albumin is precipitated by chloracetic acid. +<span class="pagenum"><a id="Page_422"></a>[Pg 422]</span></p> + +<p><b>380. Action of Albumins on Polarized Light.</b>—Many of the +albumins and albuminates, when in solution, strongly deflect the plane +of polarized light to the left.<a id="FNanchor_346" href="#Footnote_346" class="fnanchor">[346]</a></p> + +<p>The gyrodynats of some of the albumins and albuminates are given below:</p> + +<table class="spb1"> + <tbody><tr> + <td class="tdl">Serum albumin</td> + <td class="tdl_ws1">[α]<span class="fs_80"><sub>D</sub></span> =</td> + <td class="tdl_wsp">-57°.3 to -64°.6.</td> + </tr><tr> + <td class="tdl">Egg albumin</td> + <td class="tdl_ws1">[α]<span class="fs_80"><sub>D</sub></span> =</td> + <td class="tdl_wsp">-35°.5 to -38°.1.</td> + </tr><tr> + <td class="tdl">Serum globulin</td> + <td class="tdl_ws1">[α]<span class="fs_80"><sub>D</sub></span> =</td> + <td class="tdl_wsp">-47°.8.</td> + </tr><tr> + <td class="tdl">Milk albumin</td> + <td class="tdl_ws1">[α]<span class="fs_80"><sub>D</sub></span> =</td> + <td class="tdl_wsp">-76°.0 to -91°.0.</td> + </tr> + </tbody> +</table> + +<p>Our knowledge of the gyrodynatic numbers of the proteids and allied +bodies is too fragmentary to be of any great help in analytical work. +In practice, the rotatory power of these bodies becomes a disturbing +force in the determination of milk sugar.<a id="FNanchor_347" href="#Footnote_347" class="fnanchor">[347]</a> +A further study of this property of certain proteids may lead to +analytical processes for their detection and determination, but no +reliable methods for this can now be recorded.</p> + +<p><b>381. Alkaloidal Nitrogen.</b>—Only a general statement can be made +here in respect of the detection of alkaloidal nitrogen in vegetable +or animal tissues. Alkaloids are not found in healthy animal tissues +and the description of methods for isolating and detecting ptomaines is +foreign to the purpose of this work. In vegetable tissues the presence +of alkaloids may be established by the following methods of examination.</p> + +<p>The fine-ground tissues are made to pass a sieve of half millimeter +mesh and when suspended in water are acidified with sulfuric. The +mixture is then thoroughly extracted by shaking in a separatory funnel +with petroleum ether, benzene and chloroform, successively. Some +resins, glucosids and a few alkaloidal bodies not important here are +extracted by this treatment.</p> + +<p>The residue is made distinctly alkaline with ammonia and treated +as above with the same solvents. In the solution obtained as last +mentioned nearly all the alkaloidal bodies found in plants are contained.</p> + +<p>All the alkaloids in a plant may be obtained by digesting the finely +divided material with dilute sulfuric acid. The acid solution thus +obtained is made nearly neutral with ammonia or magnesia, concentrated +<span class="pagenum"><a id="Page_423"></a>[Pg 423]</span> +to a sirup, and gums, mucilage, etc. thrown out by adding about three +volumes of ninety-five per cent alcohol. The alkaloids are found in the +filtrate. The alcohol is evaporated from the filtrate and the residue +tested for alkaloids by group reagents.<a id="FNanchor_348" href="#Footnote_348" class="fnanchor">[348]</a> +Potassium mercuric iodid and phosphotungstic and molybdic acids are +types of these reagents.</p> + +<p>The same group reagents may also be applied to the extracts obtained +with petroleum ether, benzene and chloroform, in all cases, after the +removal of the solvents by evaporation.</p> + +<h3>ESTIMATION OF NITROGENOUS BODIES<br> IN AGRICULTURAL PRODUCTS.</h3> + +<p><b>382. Total Nitrogen.</b>—Any one of the methods heretofore +described for the estimation of total nitrogen in soils or fertilizers +is applicable for the same purpose to agricultural products. One +among these, however, is so superior in the matter of convenience and +certainty, as to make it preferable to any other. The moist combustion +of the sample with sulfuric acid with subsequent distillation of the +ammonia produced is the process which is to be recommended.<a id="FNanchor_349" href="#Footnote_349" class="fnanchor">[349]</a></p> + +<p>The usual precautions for securing a representative sample should be +observed, but no further directions are needed. In all cases hereafter, +where the estimation of nitrogen is enjoined, it is understood that the +moist combustion process is to be used unless otherwise stated.</p> + +<p><b>383. Estimation of Ammoniacal Nitrogen.</b>—If the distillation +of ammonia be accomplished with the aid of magnesia alba or barium +carbonate it may be safely conducted on the finely ground materials +or, in case of animal bodies, in as fine a state of subdivision as +may be conveniently secured. Since the salts of ammonia are easily +soluble in water they may be all obtained in aqueous solution, and the +distillation of this solution with magnesia gives correct results. +Experience has shown that the stronger alkalies, such as sodium and +potassium hydroxids, cannot be safely used in the distillation of +ammonia from mixtures containing organic nitrogenous materials because +<span class="pagenum"><a id="Page_424"></a>[Pg 424]</span> +of the tendency of these bodies to decomposition, in the circumstances, +yielding a portion of their nitrogen as ammonia. Barium carbonate acts +with less vigor on non-ammoniacal nitrogenous matters than magnesia, +and in some cases, as pointed out further on, may be substituted +therefor with advantage. There is no danger of failing to obtain a part +of the ammonia on distillation with magnesia provided the latter does +not contain more than a trace of carbonate.<a id="FNanchor_350" href="#Footnote_350" class="fnanchor">[350]</a></p> + +<p>When no easily decomposable organic nitrogenous matters are present, +the distillation may be conducted with the stronger alkalies in the +manner prescribed.<a id="FNanchor_351" href="#Footnote_351" class="fnanchor">[351]</a> +All the necessary details of conducting the distillation are found in +the preceding volumes of this work.</p> + +<p><b>384. Estimation of Amid Nitrogen.</b>—In bodies containing no +ammonia, or from which the ammonia has been removed by the method +described in the preceding paragraph, the nitrogen in the amid bodies +is converted into ammonia by boiling for about an hour with five per +cent sulfuric or hydrochloric acid. The ammonia thus produced is +estimated in the usual manner after distillation over magnesia free +of carbonate. The free acid is exactly neutralized with sodium or +potassium carbonate before the addition of the magnesia. The results +are given in terms of asparagin. The reaction which takes place in the +decomposition of the amid body is indicated by the following equation:</p> + +<table class="spb1 fs_105"> + <tbody><tr> + <td class="tdl_ws1">Asparagin.</td> + <td class="tdl"> </td> + <td class="tdl">Sulfuric<br> acid.</td> + <td class="tdl"> </td> + </tr><tr> + <td class="tdl">2C₄H₈N₂O₃ + 2H₂O</td> + <td class="tdl"> + </td> + <td class="tdl">H₂SO₄</td> + <td class="tdl"> =</td> + </tr><tr> + <td class="tdc" colspan="4"> </td> + </tr><tr> + <td class="tdc">Aspartic acid.</td> + <td class="tdl"> </td> + <td class="tdc">Ammonium<br>sulfate.</td> + <td class="tdl"> </td> + </tr><tr> + <td class="tdc">2C₄H₇NO₄</td> + <td class="tdl"> + </td> + <td class="tdl">(H₄N)₂SO₄.</td> + <td class="tdc"> </td> + </tr> + </tbody> +</table> + +<p>Half of the nitrogen contained in the amid body is thus obtained as +ammonia.</p> + +<p>It is advisable to calculate all the amid nitrogen in agricultural +products as asparagin.</p> + +<p><b>385. Sachsse’s Method.</b>—A method for the determination of amid +bodies by liberation of free nitrogen has been described by Sachsse +and Kormann.<a id="FNanchor_352" href="#Footnote_352" class="fnanchor">[352]</a> +It is based on the reaction which takes place when amid bodies are +brought into contact with nitrites in presence of an acid. The mixture +of the reagents by which the gas is set free is accomplished in the +<span class="pagenum"><a id="Page_425"></a>[Pg 425]</span> +apparatus shown in <a href="#FIG_103">Fig. 103</a>. The vessel <i>A</i> +has a capacity of about fifty cubic centimeters and carries a stopper +with three perforations for the arrangement shown.</p> + +<div class="figcontainer smcap"> + <div class="figsub"> + <img id="FIG_103" src="images/fig103.jpg" alt="" width="185" height="405" > + <p class="center">Fig. 103.—Apparatus<br> for Amid Nitrogen.</p> + </div> + <div id="FIG_104" class="figsub"> + <img src="images/fig104.jpg" alt="" width="300" height="401" > + <p class="center">Fig. 104.—Sachsse’s Eudiometer.</p> + </div> +</div> + +<p>About six cubic centimeters of a concentrated aqueous solution of +potassium nitrite are placed in <i>A</i> and the lower parts of the +tubes <i>a</i> and <i>b</i> are filled with water to a little above +<i>e</i> in order to exclude the air therefrom. Dilute sulfuric acid +is placed in one of the funnels and an aqueous solution of the amid +in the other. The air is displaced from the empty part of <i>A</i> by +introducing the sulfuric acid, a little at a time, whereby nitrous acid +and nitric oxid are evolved. This operation is continued until all the +air has been driven out through <i>c d</i>, the open end of <i>d</i> +being kept in the liquid in the dish shown in <a href="#FIG_104">Fig. 104</a>. +The eudiometer in which the evolved nitrogen is measured is shown in +<a href="#FIG_104">Fig. 104</a>, and should have a capacity of about +fifty cubic centimeters, and be graduated to fifths. It is filled with +the solution of ferrous sulfate contained in <i>B</i> by sucking at +<i>g</i>, after which the clamp <i>h</i> is replaced, the cock <i>f</i> +closed, and the free end of <i>d</i> placed in the lower end of the +eudiometer. The solution of the amid is run slowly into the generator +<i>A</i>, <a href="#FIG_103">Fig. 103</a>, together with small additional quantities +of the sulfuric acid when the evolution of gas becomes slow. From time to time +<i>h</i> is opened and fresh quantities of the ferrous solution allowed +<span class="pagenum"><a id="Page_426"></a>[Pg 426]</span> +to flow into the eudiometer. Any trace of the amid remaining in the +funnel is washed into <i>A</i> with pure water, with care to avoid the +introduction of air. When the liquid in <i>A</i> assumes a permanent +blue color the decomposition is complete. The residual gas is driven +out of <i>A</i> by filling with water. The tubes <i>d</i> and <i>h</i>, +after all the nitric oxid is absorbed, are removed from the eudiometer +which is transferred to a cylinder containing water and immersed +therein until the two liquid surfaces are at the same level and the +volume of the nitrogen observed. After correction for temperature and +pressure, the weight of the nitrogen is calculated. Twenty-eight parts +by weight of nitrogen correspond to 150 of pure asparagin, 181 of +tyrosin and 131 of leucin.<a id="FNanchor_353" href="#Footnote_353" class="fnanchor">[353]</a> +This method of procedure is difficult of manipulation and is apt to +give results that are too high. It cannot be preferred to the more +simple and accurate processes already described.</p> + +<p><b>386. Preparation of Asparagin.</b>—In case the analyst desires to +prepare a quantity of asparagin for comparative purposes it may be +easily accomplished in the following way: A sufficient quantity of +pease or beans is sprouted in a dark place and allowed to grow until +the reserve food of the seed is exhausted. The young sprouts are +gathered, shredded and subjected to strong pressure. The juice thus +obtained is boiled to coagulate the albumin, and thrown on a filter. +The filtrate is evaporated to a thin sirup and set aside to allow the +asparagin to separate in a crystallized form. If the crystals at first +formed are colored they may be dissolved, decolorized with bone-black, +and recrystallized. Instead of the above method the young shoots may be +shredded, extracted with hot water and the extract treated as above. A +larger yield of the asparagin is obtained by the latter process than by +the one mentioned above.<a id="FNanchor_354" href="#Footnote_354" class="fnanchor">[354]</a></p> + +<p><b>387. Detection and Estimation of Asparagin and Glutamin.</b>—Of all +the amid bodies asparagin is the most important from an agricultural +standpoint, because of its wide distribution in vegetable products.<a id="FNanchor_355" href="#Footnote_355" class="fnanchor">[355]</a> +Asparagin is easily obtained from the aqueous extracts of plants by +crystallization.<a id="FNanchor_356" href="#Footnote_356" class="fnanchor">[356]</a> +In addition to its crystalline characteristics asparagin may be +identified by the following tests. Heated with alkalies, including +<span class="pagenum"><a id="Page_427"></a>[Pg 427]</span> +barium hydroxid, asparagin yields ammonia. Boiled with dilute acids +it forms ammonium salts. A warm aqueous solution dissolves freshly +prepared copper hydroxid with the production of a deep blue color. +Sometimes, on cooling, crystals of the copper compound formed are +separated. Asparagin crystallizes with one molecule of water. Glutamin +gives essentially the reactions characteristic of asparagin, but +crystallizes without water in small white needles. Asparagin is +easily detected with the aid of the microscope by placing sections of +vegetable tissues containing it in alcohol. After some time microscopic +crystals of asparagin are separated. The presence of large quantities +of soluble carbohydrates seriously interferes with the separation of +asparagin in crystalline form.</p> + +<p>For the detection of glutamin the liquid containing it is boiled with +dilute hydrochloric acid, by which ammonia and glutamic acid are +formed. On the addition of lead acetate to the solution the glutamic +acid is thrown out as a lead salt, in which, after its decomposition +with hydrogen sulfid, the characteristic properties of glutamic acid +can be established.</p> + +<p>The above process is chronophagous and also uncertain where the +quantity of glutamin is very small and that of other soluble organic +matters very large. A much better process, both for the detection +of glutamin and asparagin, is the following, based on the property +possessed by mercuric nitrate of precipitating amids.</p> + +<p>The aqueous extract containing the amid bodies is mixed with lead +acetate until all precipitable matters are thrown out and the mixture +poured into a filter. To the filtrate is added a moderately acid +solution of mercuric nitrate. The precipitate produced is collected +on a filter, washed, suspended in water, decomposed with hydrogen +sulfid and again filtered. The amid bodies (glutamin, asparagin, etc.) +are found in the filtrate and can be detected and estimated by the +processes already described. A reaction showing the presence of an amid +body is not a positive proof of the presence of asparagin or glutamin, +since among other amids, allantoin may be present. This substance is +<span class="pagenum"><a id="Page_428"></a>[Pg 428]</span> +found in the sprouts of young plants and also in certain cereals, as +shown by researches in this laboratory.<a id="FNanchor_357" href="#Footnote_357" class="fnanchor">[357]</a> +Allantoin, glutamin, and asparagin, when obtained in solution by +the above process, may be secured, by careful evaporation and +recrystallization, in well defined crystalline forms. Asparagin gives +lustrous, rhombic prisms, easily soluble in hot water, but insoluble in +alcohol and ether.</p> + +<p>Allantoin is regarded as a diureid of glyoxalic acid and has the +composition represented by the formula C₄H₆N₄O₃. It crystallizes in +lustrous prisms having practically the same solubility as asparagin.</p> + +<p>Glutamin is the amid of amidoglutaric acid. It crystallizes in fine +needles. Its structural formula is represented as</p> + +<ul class="index fs_105"> +<li class="isub7">CO.NH₂</li> +<li class="isub7">/</li> +<li class="isub3">C₃H₅(NH₂)</li> +<li class="isub7">\</li> +<li class="isub7">CO₂H.</li> +</ul> + +<p><b>387. Cholin and Betain.</b>—Cholin is a nitrogenous base found +in both animal and plant tissues. Its name is derived from the +circumstance that it was first discovered in the bile. It is found in +the brain, yolk of eggs, hops, beets, cottonseed and many other bodies. +When united with glycerolphosphoric acid it forms lecithin, a compound +of great physiological importance. From a chemical point of view, +cholin is oxyethyltrimethyl-ammonium hydroxid,</p> + +<ul class="index fs_105"> +<li class="isub5">OH</li> +<li class="isub5">/</li> +<li class="isub3">C₂H₄<span class="ws6">; (C₅H₁₅NO₂).</span></li> +<li class="isub5">\</li> +<li class="isub5">N(CH₃)₃.OH</li> +</ul> + +<p>It is crystallized with difficulty and is deliquescent. Its most +important compound, from an analytical point of view, is its platinum +salt <b>C₅H₁₄ONCl₂PtCl₄</b>. This salt crystallizes in red-yellow plates and +is insoluble in alcohol.</p> + +<p>Betain, <b>C₅H₁₁NO₂</b>, is the product of the oxidation of cholin.</p> + +<p>In this laboratory the bases are separated from cottonseed and from +each other by the process described below.<a id="FNanchor_358" href="#Footnote_358" class="fnanchor">[358]</a></p> + +<p>About five pounds of fine-ground cottonseed cake are extracted with +seventy per cent alcohol. The material should not be previously treated +with dilute mineral acids because of the danger of converting a part +of the cholin into betain. The alcohol is removed from the filtered +extract and the residue dissolved in water. The aqueous solution is +treated with lead acetate until no further precipitation takes place, +thrown on a filter, the lead removed from the filtrate with hydrogen +<span class="pagenum"><a id="Page_429"></a>[Pg 429]</span> +sulfid and the liquid evaporated to a viscous syrup. The sirup is +extracted with alcohol containing one per cent of hydrochloric acid. +The solution thus obtained is placed in a deep beaker and the bases +precipitated by means of an alcoholic solution of mercuric chlorid. +The complete separation of the salts requires at least two weeks.</p> + +<p>The double salts of the bases and mercury thus obtained, after freeing +from the mother liquor, are recrystallized from a solution in water +and from the pure product thus obtained the mercury is removed after +solution in water, by hydrogen sulfid. The filtrate, after separating +the mercury, contains the bases as chlorids (hydrochlorates). The +solution of the chlorids is evaporated slowly in (pene) vacuo to a +thick sirup and set over sulfuric acid to facilitate crystallization. +The hydrochlorates are obtained in this way colorless and in +well-shaped crystalline forms.</p> + +<p>In a quantitive determination, a small amount of the fine meal is +extracted at once with one per cent hydrochloric acid in seventy per +cent alcohol, the salts obtained purified as above and weighed.</p> + +<p>The following process serves to determine the relative proportions of +cholin and betain in a mixture of the two bases.</p> + +<p>A definite weight of the chlorids, prepared as directed above, is +extracted by absolute alcohol. This treatment dissolves all the cholin +chlorid and a little of the betain salt. The alcoholic solution is +evaporated and again extracted with absolute alcohol. This process is +repeated three times and at the end the cholin chlorid is obtained +free of betain. In a sample of cottonseed cake examined in this +laboratory the two bases were found present in the following relative +proportions, <i>viz.</i>, cholin 17.5 per cent, betain 82.5 per cent. +Thus purified the cholin is finally precipitated by platinum chlorid. +For a description of the special reaction, by means of which cholin and +betain are differentiated, the paper cited above may be consulted.</p> + +<p>These bodies have acquired an economic interest on account of their +occurrence in cottonseed meal, which is so extensively used as a cattle +food. It is evident from the relative proportions in which they occur +<span class="pagenum"><a id="Page_430"></a>[Pg 430]</span> +that the less nocuous base, betain, is the more abundant. It is +possible, however, that the base originally formed is cholin and that +betain is a secondary product.</p> + +<p>Experience has shown that it is not safe to feed cottonseed meal to +very young animals, while moderate rations thereof may be given to +full-grown animals without much expectation of deleterious results. In +the case of toxic effects it is fair to presume that a meal has been +fed in which the cholin is relatively more abundant than the betain.</p> + +<p><b>389. Lecithin.</b>—Lecithin is a nitrogenous body, allied both to +the fats and proteids and containing glycerol and phosphoric acid. Its +percentage composition is represented with some accuracy by the formula +<b>C₄₂H₈₆NPO₉</b>, or according to Hoppe-Seyler, <b>C₄₄H₉₀NPO₉</b>. It appears to +be a compound of cholin with glycerolphosphoric acid. It is widely +distributed both in animal and vegetable organisms, in the latter +especially in pease and beans.</p> + +<p>From a physiological point of view, lecithin is highly important as the +medium for the passage of phosphorus from the organic to the inorganic +state, and the reverse. This function of lecithin has been thoroughly +investigated in this laboratory by Maxwell.<a id="FNanchor_359" href="#Footnote_359" class="fnanchor">[359]</a></p> + +<p>In the extraction of lecithin from seeds (pease, beans, etc.) it is not +possible to secure the whole of the substance by treatment with ether +alone.<a id="FNanchor_360" href="#Footnote_360" class="fnanchor">[360]</a></p> + +<p>The extraction of the lecithin may, however, be entirely accomplished +by successive treatments for periods of about fifteen hours with pure +ether and alcohol. This is better than to mix the solvents, since, in +this case, the ether having the lower boiling point is chiefly active +in the extraction. When the extraction is accomplished by digestion +and not in a continuous extracting apparatus the two solvents may be +mixed together and thus used with advantage. After the evaporation of +the solvents, the lecithin is ignited with mixed sodium and potassium +carbonate whereby the organic phosphorus is secured without loss in an +inorganic form. Where greater care is desired, the method described for +organic phosphorus in soils may be used.<a id="FNanchor_361" href="#Footnote_361" class="fnanchor">[361]</a> +The inorganic phosphorus thus obtained is estimated in the usual way as +magnesium pyrophosphate. +<span class="pagenum"><a id="Page_431"></a>[Pg 431]</span></p> + +<p>For analytical purposes, the extraction of lecithin from vegetable +substances is conducted in this laboratory as follows:<a id="FNanchor_362" href="#Footnote_362" class="fnanchor">[362]</a> +The fine-ground pea or bean meal is placed in an extraction apparatus +and treated continuously with anhydrous ether for fifteen hours. The +ether in the apparatus is replaced with absolute alcohol and the +extraction continued for six hours longer. The alcoholic extract is +evaporated to dryness and treated with ether. The part of the lecithin +at first insoluble in ether becomes soluble therein after it has been +removed from the vegetable tissues by alcohol. Moreover, any trace of +inorganic phosphorus which may have been removed by the alcohol, is +left undissolved on subsequent treatment with ether. The ether extract +from the alcohol residue is added to that obtained directly, the ether +removed by evaporation, and the total lecithin oxidized and the residue +used for the estimation of phosphorus as already described.</p> + +<p>In determining the lecithin in eggs, the procedure employed for +vegetable tissues is slightly changed.<a id="FNanchor_363" href="#Footnote_363" class="fnanchor">[363]</a> +The whole egg, excluding the shell, is placed in a flask with a reflux +condenser and boiled for six hours with absolute alcohol. The alcohol +is then removed from the flask by evaporation and the residue treated +in like manner with ether for ten hours. The ether is removed and the +dry residue rubbed to a fine powder, placed in an extractor and treated +with pure ether for ten hours. The extract thus secured is oxidized +after the removal of the ether by fusion with mixed alkaline carbonates +and the phosphorus determined in the usual way.</p> + +<p><b>390. Factor for Calculating Results.</b>—The percentage of lecithin +is calculated from the weight of magnesium pyrophosphate obtained by +multiplying it by the factor, 7.2703.<a id="FNanchor_364" href="#Footnote_364" class="fnanchor">[364]</a> +This factor is calculated from the second formula for lecithin given +above, in which the percentage of phosphorus pentoxid, <b>P₂O₅</b>, is +8.789.</p> + +<p class="blockquot"><i>Example.</i>—In fifty-four grams of egg, +exclusive of the shell, is found an amount of organic phosphorus +yielding 0.0848 gram of magnesium pyrophosphate. Then 0.0848 × 7.2703 += 0.61652 and 0.61652 × 100 ÷ 54 = 1.14. Therefore the percentage of +lecithin in the egg is 1.14.</p> + +<p><span class="pagenum"><a id="Page_432"></a>[Pg 432]</span> +<b>391. Estimation of Alkaloidal Nitrogen.</b>—The alkaloids contain +nitrogen in a form more difficult of oxidation than that contained in +proteid or albuminoid forms. It is doubtful whether any of the nitrogen +in alkaloids becomes available for plant nutrition by any of the usual +processes of fermentation and decay to which nitrogenous bodies are +submitted in the soil. Likewise, it is true that it is not attacked by +the digestive processes in any way preparatory to its assimilation as +food by the animal tissues. Alkaloidal nitrogen is therefore not to be +regarded as a food either for the animal or plant.</p> + +<p>For the general methods of estimating alkaloids the reader is referred +to standard works on plant chemistry and toxicology. The alkaloids of +interest in this manual are those which are found in tobacco, tea, +coffee and a few other products of agricultural importance. The best +methods of isolating and estimating these bodies will be given in the +part of the volume devoted to the special consideration of the articles +mentioned.</p> + +<h3>SEPARATION OF PROTEID BODIES<br> IN VEGETABLE PRODUCTS.</h3> + +<p id="P_392"><b>392. Preliminary Treatment.</b>—The chief disturbing components +of vegetable tissues, in respect of their influence on the separation +and estimation of the proteid constituents, are fats and oils and +coloring matters. In many cases these bodies are present in such +small quantities as to be negligible, as, for instance, in rice. In +other cases they exist in such large proportions as to present almost +insuperable difficulties to analytical operations, as is the case with +oily seeds. In all instances, however, it is best to remove these +bodies, even when present in small proportions, provided it can be done +without altering the character of the proteid bodies. This is secured +by extracting the fine-ground vegetable material first with petroleum +ether, and afterwards with strong alcohol and ether. Practically, all +of the fatty bodies and the greater part of the most objectionable +coloring matters are removed by this treatment. The extraction should +in all cases be made at low temperatures, not exceeding 35°, to avoid +the coagulating effect of higher temperatures upon the albuminous +bodies which may be present. +<span class="pagenum"><a id="Page_433"></a>[Pg 433]</span></p> + +<p>In this laboratory, fatty seeds, as for instance peanuts, are first +ground into coarse meal, then extracted with petroleum ether, ground +to a fine meal and the fat extraction completed with petroleum ether, +ninety-five per cent alcohol and pure sulfuric ether. The residue of +the last solvent may be removed by aspirating air through the extracted +meal. In some cases, it is advisable to extract with ethyl ether before +as well as after the alcoholic extraction. This treatment removes at +least a part of the water and prevents the dilution of the first part +of alcohol added to such an extent as to make it dissolve some of the +proteid matters. In each case, a portion of the alcoholic extract +should be tested qualitively for proteid matter. If any be found, +stronger alcohol should be used for, at least, the first extraction. A +portion of the meal, prepared as above directed, is extracted with a +ten per cent solution of sodium chlorid, as described further on, and a +measured portion of the filtered extract diluted with water until the +proteid matter in solution begins to be precipitated. By this treatment +the proper strength of the salt solution, to be used for the subsequent +extraction, is determined. To save time in dialyzing, the solution of +salt employed as a solvent should be as dilute as possible.</p> + +<p>The mixture of meal and solvent sometimes filters with difficulty. +In these cases, it is advisable to first pour it into a linen bag +from which the liquid portion can be removed by gentle pressure and +subsequently filtered through paper. As a last resort, the liquid +secured from the linen filter can be saturated with ammonium, zinc or +magnesium sulfate, whereby all the proteid matters are thrown out. +After filtering, the residue is again dissolved in salt solution and +can then be readily filtered through paper.</p> + +<p>The clear filtrate should be tested by fractional precipitation by heat +and the final filtrate by acetic acid, as will be described further on.</p> + +<p>The proteid matter may be further freed from amid compounds by +treatment with copper sulfate.<a id="FNanchor_365" href="#Footnote_365" class="fnanchor">[365]</a> +This treatment is not advisable, however, except for the purpose of +determining the total proteid nitrogen in the sample. The action of the +<span class="pagenum"><a id="Page_434"></a>[Pg 434]</span> +water, heat and cupric sulfate combined is capable of inducing grave +changes in the character of the residual matter which would seriously +interfere with the results of subsequent studies of the nature of the +proteid bodies.</p> + +<p>In many instances, as with cereal grains, the separation of the proteid +bodies is accomplished by no further preliminary treatment than is +necessary to reduce them to the proper degree of fineness.</p> + +<p><b>393. Diversity of Character.</b>—The proteids which occur in +vegetable products are found in all parts of the tissues of the plants, +but in cereals especially in the seeds. In grass crops and in some +of the legumes, such as clover, the nitrogenous matters are chiefly +found in the straw and leaves. The general classification of these +bodies has already been given, but each kind of plant presents marked +variations, not only in the relative proportions of the different +classes, but also in variations in the nature of each class. For this +reason the study of vegetable proteids is, in some respects, a new +research for each kind of plant examined. There are, however, some +general principles which the analyst must follow in his work, and an +attempt will be made here to establish these and to construct thereon +a rational method of conducting the investigation. In the separation +and estimation of complex bodies so nearly related to each other, it is +difficult not only to secure satisfactory results, but also to prevent +the transformation of some forms of proteid matter into others nearly +related thereto by the action of the solvents used for separation and +precipitation.</p> + +<p><b>394. Separation of Gluten from Wheat Flour.</b>—The most important +proteid in wheat is the body known as gluten, a commercial name given +to the nitrogenous matters insoluble in cold water. The gluten thus +obtained does not represent a single chemical compound, but is a +complex consisting of at least two proteid bodies, which together form +an elastic, pasty mass, insoluble in cold water containing a trace +of mineral salts. This mass has the property of holding mechanically +entangled among its particles bubbles of gas, which, expanding under +the action of heat during cooking, give to bread made of glutenous +flours its porous property. +<span class="pagenum"><a id="Page_435"></a>[Pg 435]</span></p> + +<p>In respect of proteids, the American wheats, as a rule, are quite +equal to those of foreign origin. This is an important characteristic +when it is remembered that both the milling and food values of a wheat +depend largely on the nitrogenous matter which is present. It must +not be forgotten, however, that merely a high percentage of proteids +is not always a sure indication of the milling value of a wheat. The +percentage of gluten to the other proteid constituents of a wheat is +not always constant, and it is the gluten content of a flour on which +its bread making qualities chiefly depend. The percentage of moist +gluten gives, in a rough way, the property of the glutenous matter of +absorbing and holding water under conditions as nearly constant as +can be obtained. In general, it may be said that the ratio between +the moist gluten and the dry gluten in a given sample is an index for +comparison with other substances in the same sample. Upon the whole, +however, the percentage of dry gluten must be regarded as the safer +index of quality. In respect of the content of glutenous matter, our +domestic wheats are distinctly superior to those of foreign origin. +They are even better than the Canadian wheats in this respect. It may +be fairly inferred, therefore, that while our domestic wheats give a +flour slightly inferior in nutritive properties to that derived from +foreign samples, it is nevertheless better adapted for baking purposes, +and this quality more than compensates for its slight deficiency in +respect of nutrition, a deficiency, which, however, is so minute as to +be hardly worth considering.<a id="FNanchor_366" href="#Footnote_366" class="fnanchor">[366]</a></p> + +<p>The gluten is separated in this laboratory from the other constituents +of a flour by the following process:</p> + +<p>Ten grams of the fine-ground flour are placed in a porcelain dish, well +wet with nearly an equal weight of water at a temperature of not to +exceed 15°, and the mass worked into a ball with a spatula, taking care +that none of it adheres to the walls of the dish. The ball of dough is +allowed to stand for an hour, at the end of which time it is held in +the hand and kneaded in a stream of cold water until the starch and +soluble matter are removed. The ball of gluten thus obtained is placed +in cold water and allowed to remain for an hour when it is removed, +pressed as dry as possible between the hands, rolled into a ball, +<span class="pagenum"><a id="Page_436"></a>[Pg 436]</span> +placed in a flat bottom dish and weighed. The weight obtained is +entered as moist gluten. The dish containing the ball of gluten is +dried for twenty hours in a steam-bath, again weighed, and the weight +of material obtained entered as dry gluten. The determination of dry +and moist gluten cannot in any sense be regarded as an isolation and +estimation of a definite chemical compound. For millers’ and bakers’ +purposes, however, the numbers thus obtained have a high practical +value. A typical wheat grown in this country will contain about 26.50 +per cent of moist and 10.25 per cent of dry gluten.</p> + +<p>The gluten of wheat is composed of two proteid bodies, gliadin and +glutenin.<a id="FNanchor_367" href="#Footnote_367" class="fnanchor">[367]</a> +Gliadin contains 17.66 per cent, and glutenin 17.49 per cent of +nitrogen. Gliadin forms a sticky mass when mixed with water and is +prevented from passing into solution by the small content of mineral +salts present in the flour. It serves to bind together the other +ingredients of the flour, thus rendering the dough tough and coherent. +Glutenin serves to fix the gliadin and thus to make it firm and solid. +Glutenin alone cannot yield gluten in the absence of gliadin, nor +gliadin without the help of glutenin. Soluble metallic salts are also +necessary to the formation of gluten, and act as suggested above, by +preventing the solution of the gliadin in water, during the process of +washing out the starch. No fermentation takes place in the formation of +gluten from the ingredients named.</p> + +<p>The gluten, which is obtained in an impure state by the process above +described, is, therefore, not to be regarded as existing as such in the +wheat kernel or flour made therefrom, but to arise by a union of its +elements by the action of water.</p> + +<p><b>395. Extraction with Water.</b>—It is quite impossible to get an +extract from fine-ground vegetable matter in pure water because the +soluble salts of the sample pass at once into solution and then a pure +water solvent becomes an extremely dilute saline solution. The aqueous +extract may, however, be subjected to dialysis, whereby the saline +matter is removed and the proteid matter, not precipitated during the +dialytic process, may be regarded as that part of it in the original +sample soluble in pure water. Nevertheless, in many instances, it is +<span class="pagenum"><a id="Page_437"></a>[Pg 437]</span> +important to obtain an extract with cold water. In oatmeal the +aqueous extract is obtained by Osborne as follows:<a id="FNanchor_368" href="#Footnote_368" class="fnanchor">[368]</a> +Five pounds of fine-ground meal are shaken occasionally with six liters +of cold water for twenty-four hours, the liquid removed by filtration +and pressure and the extraction continued with another equal portion +of water in the manner noted. The two liquid extracts are united and +saturated with commercial ammonium sulfate which precipitates all +the dissolved proteid matter. The filtrate obtained is collected on +a filter, washed with a saturated solution of ammonium sulfate and +removed as completely as possible from the filter paper by means of +a spatula. Any residual precipitate remaining on the paper is washed +into the vessel containing the removed precipitate and the undissolved +precipitate well beaten up in the liquid, which is placed in a dialyzer +with a little thymol, to prevent fermentation, and subjected to +dialysis for about two weeks. At the end of that time, the contents +of the dialyzer are practically free of sulfates. The contents of the +dialyzers are then thrown on a filter and in the filtrate are found +those proteids first extracted with water, precipitated with ammonium +sulfate and redissolved from this precipitated state by pure water. In +the case of oatmeal, this proteid matter is not coagulated by heat, and +may be obtained in the dry state by the evaporation of the filtrate +last mentioned at a low temperature in vacuo. It is evident that the +character of the proteid matter thus obtained will vary with the nature +of the substance examined. In the case of oats, it appears to be a +proteose and not an albumin.</p> + +<p><b>396. Action of Water on Composition of Proteids.</b>—When a +body, such as oatmeal, containing many proteids of nearly related +character, is exposed to the action of a large excess of water, the +proteid bodies may undergo important changes whereby their relations +to solvents are changed. After oatmeal has been extracted with water, +as described above, the proteid matter originally soluble in dilute +alcohol undergoes an alteration and assumes different properties. The +same remark is applicable to the proteid body soluble in dilute potash. +Nearly all the proteid matter of oatmeal is soluble in dilute potash, if +<span class="pagenum"><a id="Page_438"></a>[Pg 438]</span> +this solvent be applied directly, but if the sample be previously +treated with water or a ten per cent salt solution the subsequent +proportion of proteid matter soluble in dilute potash is greatly +diminished.<a id="FNanchor_369" href="#Footnote_369" class="fnanchor">[369]</a> +Water applied directly to the oatmeal apparently dissolves an acid +albumin, a globulin or globulins, and a proteose. The bodies, however, +soluble in water, exist only in small quantities in oatmeal. Experience +has shown that in most instances, it is safer to begin the extraction +of a cereal for proteid matter with a dilute salt solution rather than +with water, and to determine the matters soluble in water alone by +subsequent dialysis.</p> + +<p><b>397. Extraction with Dilute Salt Solution.</b>—In general, it +is advisable to begin the work of separating vegetable proteids by +extracting the sample with a dilute brine usually of ten per cent +strength. As conducted by Osborne and Voorhees, on wheat flour, the +manipulation is carried on as follows:<a id="FNanchor_370" href="#Footnote_370" class="fnanchor">[370]</a></p> + +<p>The fine-ground whole wheat flour, about four kilograms, is shaken with +twice that weight of a ten per cent sodium chlorid solution, strained +through a sieve, to break up lumps, and allowed to settle for sixteen +hours. At the end of this time, about half of the supernatant liquid +is removed by a siphon or by decantation and filtered. Two liters +more of the salt solution are added, the mixture well stirred and the +whole brought onto the filter used above. The filtrate is collected +in successive convenient portions and each portion, as soon as it is +obtained, is saturated with ammonium sulfate. All the proteid matter is +precipitated by this reagent. The precipitate is collected on a filter, +redissolved in a convenient quantity of the salt solution and dialyzed +for fourteen days or until all sulfates and chlorids are removed. The +proteid matter, which is separated on dialysis, in this instance, is a +globulin.</p> + +<p>The proteid matter not precipitated on dialysis is assumed to be that +part of the original substance soluble in water.</p> + +<p>A part of the water soluble proteid matter obtained as above is +coagulated by heat at from 50° to 80°. The part not separated by heat +gives a precipitate on saturation with sodium chlorid.</p> + +<p>In wheat there are found soluble in water two albumins and a +proteose.<a id="FNanchor_371" href="#Footnote_371" class="fnanchor">[371]</a></p> + +<p><span class="pagenum"><a id="Page_439"></a>[Pg 439]</span> +In separating the albumin coagulating at a low boiling point from the +dialyzed solution mentioned above, it is heated to 60° for an hour, +the precipitate collected on a gooch, washed with hot water (60°), and +then successively with ninety-five per cent alcohol, water-free alcohol +and ether. On drying the residual voluminous matter on the filter over +sulfuric acid, it becomes dense and horny, having in an ash free state, +according to Osborne, the following composition:</p> + +<table class="spb1"> + <tbody><tr> + <td class="tdl"> </td> + <td class="tdr">Per cent.</td> + </tr><tr> + <td class="tdl">Carbon</td> + <td class="tdc">53.06</td> + </tr><tr> + <td class="tdl">Hydrogen<span class="ws3"> </span></td> + <td class="tdc"> 6.82</td> + </tr><tr> + <td class="tdl">Nitrogen</td> + <td class="tdc">17.01</td> + </tr><tr> + <td class="tdl">Sulfur</td> + <td class="tdc"> 1.30</td> + </tr><tr> + <td class="tdl">Oxygen</td> + <td class="tdc">21.81</td> + </tr> + </tbody> +</table> + +<p><b>398. Treatment without Precipitation with Ammonium +Sulfate.</b>—Where abundant means are at hand for dialyzing large +volumes of solution, the preliminary treatment of the solution made +with ten per cent sodium chlorid with ammonium sulfate may be omitted.</p> + +<p>When the precipitated proteids are to be used for the estimation of +the nitrogen therein contained, it has been proposed to substitute +the corresponding zinc salt for the ammonium sulfate.<a id="FNanchor_372" href="#Footnote_372" class="fnanchor">[372]</a> +This reagent has given satisfactory results in this laboratory and while +a larger experience is desirable before commending it as an acceptable +substitute in all cases, yet its obvious advantage, in being free of +nitrogen for the use mentioned, entitles it to careful consideration.</p> + +<p>The manipulation, with the exception of the precipitation with ammonium +sulfate, is the same as that described in the preceding paragraph. The +globulins are completely precipitated when the dialysis is complete and +may be separated from the soluble albumins and proteoses by filtration.</p> + +<p id="P_399"><b>399. Separation of the Bodies Soluble in +Water.</b>—<i>Albumins.</i>—By the methods of treatment just +described, the proteid matters soluble in ten per cent sodium chlorid +solution are separated into two classes, <i>viz.</i>, globulins +insoluble in pure water and albumins and proteoses soluble in pure +water. The aqueous solution will also contain any amids or nitrogenous +<span class="pagenum"><a id="Page_440"></a>[Pg 440]</span> +bases soluble in the dilute saline solution and in water. Osborne and +Voorhees have found that the best way of separating the albumins in +the pure aqueous solution is by the application of heat.<a id="FNanchor_373" href="#Footnote_373" class="fnanchor">[373]</a> +By means of a fractional coagulation the albumins are divided into classes, +<i>viz.</i>, those separating at from 60° to 65° and those remaining in +solution at that temperature but separating up to 85°. The respective +quantities of these albumins are determined by collecting them in a +filter and estimating the nitrogen therein by moist combustion in the +usual way. Even a larger number of albumins may be secured, as in the +maize kernel, by such a fractional precipitation by means of heat. +Chittenden and Osborne find in this instance that the precipitation +begins at about 40°.<a id="FNanchor_374" href="#Footnote_374" class="fnanchor">[374]</a></p> + +<p><i>Proteose.</i>—After the separation of the albumins by heat the +filtrate may still contain proteid matter. This matter belongs to +the proteose class. It may be partially secured by concentrating the +filtrate, after the removal of the albumins, to a small bulk when a +part of the proteose body will separate. It may be thrown out entirely +by treating the filtrate above mentioned with fine-ground salt until it +is saturated or by adding salt until the solution contains about twenty +per cent thereof and precipitating the proteose by acetic acid.<a id="FNanchor_375" href="#Footnote_375" class="fnanchor">[375]</a></p> + +<p><b>400. Separation of the Globulins.</b>—The globulins which are +extracted with ten per cent solution of sodium chlorid and precipitated +on dialysis may be separated by fractional solution into several +bodies of nearly related properties. This solution is conveniently +accomplished by saline solvents of increasing strength. In the case of +the maize globulins, Chittenden and Osborne employ dilute solutions of +common salt for effecting the separation, beginning with a quarter of a +per cent and ending with a two per cent mixture.<a id="FNanchor_376" href="#Footnote_376" class="fnanchor">[376]</a></p> + +<p><b>401. Proteids Soluble in Dilute Alcohol.</b>—Some of the proteid +bodies which are soluble in dilute salt solution and in water are also +soluble in alcohol. Since these bodies are more easily identified +by the processes already described, attention will be given in this +paragraph solely to those proteid bodies which are insoluble in water +or dilute salt solution and are soluble in dilute alcohol. +<span class="pagenum"><a id="Page_441"></a>[Pg 441]</span></p> + +<p>For the extraction of these bodies, the residue, left after extraction +with a ten per cent solution of sodium chlorid or with water, is +mixed with enough strong alcohol to secure by the admixture with the +water present in the sample an alcohol of about seventy-five per cent +strength. The mixture is well shaken and digested for some time, at a +temperature of about 46°, and thrown on a filter which is kept at about +the same temperature. The residue is again mixed with alcohol of the +same strength (seventy-five per cent) using about four liters for two +and a half kilos of the original material. During the second digestion +the temperature is kept at about 60°. The latter operation is repeated +three times and in each case the filtrate obtained is evaporated +separately.<a id="FNanchor_377" href="#Footnote_377" class="fnanchor">[377]</a> +This process is especially applicable to the meal from maize kernels, +which contains a high relative percentage of an alcohol soluble +proteid, zein.</p> + +<p>The chief part of the zein is found in the first two extracts, obtained +as described above. On evaporation, the zein separates as a tough, +leathery, yellow-colored mass on the walls of the containing vessel. It +is cut into small pieces and digested for several days in cold, pure +alcohol. This is followed by digestion with a mixture of ether and +pure alcohol, and finally with pure ether. By this treatment a part of +the zein becomes insoluble in seventy-five per cent alcohol. The part +soluble in dilute alcohol is precipitated by pouring it into water.</p> + +<p>Another method of preparing zein is to extract the meal with +seventy-five per cent alcohol after it has been treated with a ten per +cent salt solution.</p> + +<p>In this case the extraction is continued with seventy-five per cent +alcohol in successive portions until no more proteid matter passes +into solution. The several extracts are united and the alcohol removed +by distillation, by which process the zein is separated. It is washed +with distilled water, until the sodium chlorid is removed, dissolved in +warm alcohol of about eighty per cent strength and any insoluble matter +removed by filtration. On evaporating the filtrate nearly to dryness, +the zein is separated and pressed as free of water as possible, +yielding a yellow, elastic substance resembling molasses candy. This +preparation is purified by digestion with pure alcohol and ether in the +<span class="pagenum"><a id="Page_442"></a>[Pg 442]</span> +manner described. The two zeins which are secured by the treatment, one +soluble and the other insoluble in alcohol, are practically identical +in composition.<a id="FNanchor_378" href="#Footnote_378" class="fnanchor">[378]</a></p> + +<p>Zein freshly precipitated by pouring its alcoholic solution in water +is wholly insoluble in water, and, on boiling therewith, is changed +into the variety insoluble in dilute alcohol. Boiled with dilute +sulfuric acid, six in 300 cubic centimeters of water, it melts, forming +a gummy mass, which is very slowly attacked by the acid yielding +proteoses and peptones. Heated with stronger sulfuric acid it undergoes +decomposition, yielding leucin, tyrosin, and glutamic acid.</p> + +<p><b>402. Solvent Action of Acids and Alkalies.</b>—In the preceding +paragraphs, a synopsis has been given of the methods of separating +proteid matters in such a manner as to secure them in a pure state in +the same conditions as they exist in the natural substances. A very +large percentage of the proteid matter is still left undissolved after +extraction with the solvents already mentioned.</p> + +<p>Often important information may be gained concerning the nature of the +residual proteid matters by fractional extraction with dilute acids +and alkalies. When the strength of these solutions is such that they +contain about one per cent of the acid or alkali, the whole of the +proteid matter may be dissolved by boiling successively with acid and +alkali for half an hour. The proteid matter passing into solution in +these cases is usually changed in character, assuming the nature of +proteoses or allied bodies, when treated with an acid, and becoming +albuminates when boiled with an alkali. Easily soluble carbohydrate +matter is also removed by this treatment so that the residue obtained +consists largely of cellulose and is known as crude or insoluble fiber. +The removal of all the bodies soluble in dilute boiling acid and alkali +is accomplished by the method described in paragraph <b><a href="#P_272">272</a></b>.</p> + +<p>For research purposes, the solvent action of dilute alkali is of chief +importance to the analyst, and the extraction of the proteid matter, +after all that is soluble in water, common salt solution and alcohol +<span class="pagenum"><a id="Page_443"></a>[Pg 443]</span> +has been removed, should commence with a solution of potassium or +sodium hydroxid containing not over two-tenths per cent of the alkali.</p> + +<p>It has been shown by Osborne that the solvent action of very dilute +alkali, in the cold, may be exerted without changing the character of +the dissolved proteid.<a id="FNanchor_379" href="#Footnote_379" class="fnanchor">[379]</a></p> + +<p><b>403. Method of Extraction.</b>—The solvent employed is usually +a two-tenths per cent solution of potassium hydroxid. It may be +added directly to the substance or may follow extraction with water, +salt solution or alcohol. In the former case, the manipulation +is illustrated by the following description of the treatment of +oatmeal:<a id="FNanchor_380" href="#Footnote_380" class="fnanchor">[380]</a></p> + +<p>One hundred grams of oatmeal are mixed with half a liter of a +two-tenths per cent potassium hydroxid solution and allowed to stand +for some time at room temperature. The mixture is strained through +a cloth to remove the chaff and the residue is stirred with another +small portion of the solvent, again strained in the same cloth and the +residue squeezed dry. The strained liquids are united and enough more +of the solvent added to make the volume 700 cubic centimeters. After +standing for some time, the insoluble matter settles to the bottom of +the vessel and the supernatant liquid is decanted. More solvent is +added to the residue, well mixed therewith and treated as above. It is +advisable to make a third extraction in the same way. The extracts are +united, passed through a filter, the proteid matter in solution thrown +out by acetic acid, washed with water, alcohol and ether and dried over +sulfuric acid.</p> + +<p>The methods of procedure, when the sample has been previously extracted +with water, salt solution or alcohol, are essentially the same as that +just described and the reader may consult the paper of Osborne for +details.<a id="FNanchor_381" href="#Footnote_381" class="fnanchor">[381]</a></p> + +<p><b>404. Methods of Drying Separated Proteids.</b>—In the preceding +paragraphs, the analyst has been directed, in most instances, to +dry the proteid matter, after it is secured in as pure a form as +possible, at room temperature, over sulfuric acid. By this treatment +the preparation may be obtained in a form suited to the study of its +physical properties, since its solubility has not been affected by +<span class="pagenum"><a id="Page_444"></a>[Pg 444]</span> +subjecting it to a high temperature. When it is desired to use the +sample only for chemical analysis it is not necessary to wait on the +slow process above mentioned. In this case the sample may be dried in +an inert atmosphere at the temperature of a steam-bath or even at 110°. +It is better, however, to avoid so high a temperature and to conduct +the desiccation in vacuo at a heat not above that of boiling water. The +sample, before drying, should be reduced to the finest possible state +of comminution, otherwise particles of aqueous vapor may be retained +with great tenacity.</p> + +<p>In many cases it is advisable to dry the sample pretty thoroughly, then +grind to a fine powder and finish the desiccation with the pulverulent +mass. This treatment can be followed when the quantity of the material +is considerably in excess of that required for the analytical +operations.</p> + +<p><b>405. Determination of Ash.</b>—No method of treatment is known +by means of which vegetable proteid matters may be obtained entirely +free of mineral matters. The mineral bases may be naturally present +in the proteid matter as organic and inorganic salts, or they may be +mechanically entangled therewith, having been derived either from +the other tissues of the plant or from the solvents employed. It is +necessary in calculating the analytical data to base the computation on +the ash free substance. The percentage of ash is determined by any of +the standard processes or by heating the sample in a combustion tube, +to very low redness, in a current of oxygen. The total residue obtained +is used in calculating the percentage of ash, and the weights of +material subsequently used for the determination of carbon, hydrogen, +nitrogen and sulfur are corrected for the calculations by deducting the +quantity of mineral matter contained therein.</p> + +<p>By reason of the highly hygroscopic nature of the dry proteid bodies, +they must be kept over a desiccating material and weighed quickly on a +balance, in an atmosphere which is kept free of moisture by the usual methods.</p> + +<p><b>406. Carbon and Hydrogen.</b>—Carbon and hydrogen are estimated in +proteid matters by combustion with copper oxid. Osborne prefers to burn +the sample in a platinum boat in a current of air or of oxygen free of +<span class="pagenum"><a id="Page_445"></a>[Pg 445]</span> +moisture and carbon dioxid.<a id="FNanchor_382" href="#Footnote_382" class="fnanchor">[382]</a> +It is advisable to use also a layer of lead chromate in addition to +the copper oxid and metallic copper. The method of conducting the +combustion has already been described.<a id="FNanchor_383" href="#Footnote_383" class="fnanchor">[383]</a> +The analyst should have at his disposal a quantity of pure sugar, which +may be used from time to time in testing the accuracy of the work. +In beginning a series of combustions this precaution should never be +omitted. The addition of the lead chromate is to make more certain the +absorption of oxidized sulfur produced during the combustion.</p> + +<p id="P_407"><b>407. Estimation of Nitrogen.</b>—In most cases it is found +convenient, during the progress of separating vegetable proteids, to +determine the quantity of each kind by estimating the nitrogen by moist +combustion and computing the quantity of proteid matter by multiplying +the nitrogen by 6.25. The estimation of the nitrogen is made either on +an aliquot part of the extract or by direct treatment of the residue.</p> + +<p>In the pure extracted proteid matter the nitrogen is most conveniently +determined by moist combustion, but it may also be obtained either by +combustion with soda-lime or with copper oxid, or by other reliable +methods.<a id="FNanchor_384" href="#Footnote_384" class="fnanchor">[384]</a></p> + +<p>The percentages of nitrogen found in the principal proteid bodies, +together with the factors for computing the weights of the proteid +bodies from the weights of nitrogen found, are given below:</p> + +<table class="spb1"> + <thead><tr> + <th class="tdc bb"> Name of body. </th> + <th class="tdc bb"> Percentage of nitrogen. </th> + <th class="tdc bb">Factor.</th> + </tr></thead> + <tbody><tr> + <td class="tdl">Mucin</td> + <td class="tdl_ws1">13.80 to 14.13</td> + <td class="tdl_ws1">7.25 to 7.08</td> + </tr><tr> + <td class="tdl">Chondrin</td> + <td class="tdl_ws1">14.20 to 14.65</td> + <td class="tdl_ws1">7.04 to 6.83</td> + </tr><tr> + <td class="tdl">Albuminates</td> + <td class="tdl_ws1">13.87</td> + <td class="tdl_ws1">7.21</td> + </tr><tr> + <td class="tdl">Oat proteids</td> + <td class="tdl_ws1">15.85</td> + <td class="tdl_ws1">6.31</td> + </tr><tr> + <td class="tdl">Serum globulin</td> + <td class="tdl_ws1">15.63</td> + <td class="tdl_ws1">6.40</td> + </tr><tr> + <td class="tdl">Egg albumin</td> + <td class="tdl_ws1">15.71 to 17.85</td> + <td class="tdl_ws1">6.37 to 5.60</td> + </tr><tr> + <td class="tdl">Maize proteids</td> + <td class="tdl_ws1">16.06</td> + <td class="tdl_ws1">6.22</td> + </tr><tr> + <td class="tdl">Casein</td> + <td class="tdl_ws1">15.41 to 16.29</td> + <td class="tdl_ws1">6.49 to 6.13</td> + </tr><tr> + <td class="tdl">Serum albumin</td> + <td class="tdl_ws1">15.96</td> + <td class="tdl_ws1">6.27</td> + </tr><tr> + <td class="tdl">Syntonin</td> + <td class="tdl_ws1">16.10</td> + <td class="tdl_ws1">6.21</td> + </tr><tr> + <td class="tdl">Keratin</td> + <td class="tdl_ws1">16.20 to 17.70</td> + <td class="tdl_ws1">6.17 to 5.65</td> + </tr><tr> + <td class="tdl">Fibrinogen</td> + <td class="tdl_ws1">16.65</td> + <td class="tdl_ws1">6.01</td> + </tr><tr> + <td class="tdl">Peptones</td> + <td class="tdl_ws1">16.66 to 17.13</td> + <td class="tdl_ws1">6.00 to 5.84</td> + </tr><tr> + <td class="tdl">Elastin</td> + <td class="tdl_ws1">16.75</td> + <td class="tdl_ws1">5.97</td> + </tr><tr> + <td class="tdl">Wheat proteids</td> + <td class="tdl_ws1">16.80 to 18.39</td> + <td class="tdl_ws1">5.95 to 5.44</td> + </tr><tr> + <td class="tdl">Fibrin</td> + <td class="tdl_ws1">16.91</td> + <td class="tdl_ws1">5.91</td> + </tr><tr> + <td class="tdl">Flax seed proteids</td> + <td class="tdl_ws1">17.70 to 18.78</td> + <td class="tdl_ws1">5.65 to 5.33</td> + </tr> + </tbody> +</table> + +<p><span class="pagenum"><a id="Page_446"></a>[Pg 446]</span> +<b>408. Determination of Sulfur.</b>—Sulfur is a characteristic +constituent of the proteid bodies, existing in quantities approximating +one per cent of their weight.</p> + +<p>In the estimation of sulfur, it is first converted into sulfuric acid, +which is thrown out by a soluble barium salt and the sulfur finally +weighed as barium sulfate.</p> + +<p>All the sulfur existing in the organic state in a proteid may be +obtained by burning in a current of oxygen and conducting the gaseous +products of combustion through solid sodium or potassium carbonate +at or near a red heat.<a id="FNanchor_385" href="#Footnote_385" class="fnanchor">[385]</a> +The organic sulfur may also be converted into sulfuric acid by fusing +the proteid body with a mixture of sodium hydroxid and potassium +nitrate. The fused mass, after cooling, is dissolved in water, the +solution acidified with hydrochloric, evaporated to dryness to +decompose nitrates and remove excess of hydrochloric acid and dissolved +in a large excess of water. After standing for a day, the solution is +filtered and the sulfuric acid thrown out of the hot filtrate with a +slight excess of barium chlorid solution. The usual precautions in +precipitating, filtering and igniting the barium sulfate are to be +observed.<a id="FNanchor_386" href="#Footnote_386" class="fnanchor">[386]</a></p> + +<p><b>409. General Observations.</b>—In the preceding paragraphs have +been stated the general principles upon which the separation of +vegetable proteid matters depends, and a description has been given +of the several processes by which this separation is accomplished. In +each case, however, special conditions exist which require special +modifications of the general processes, and these can only be +successfully secured by the skill, judgment and patient labor of the +investigator. Many of these cases have been already worked out, and the +valuable data secured by Chittenden, Osborne and others, are accessible +to the analyst in the papers already cited. In the case of the proteids +in the peanut, a similar work has been done in this laboratory by +Bigelow, the data of which have not yet been published. It is only +by a careful study of the work already done as outlined here and as +published in full in the cited papers, that the analyst will be able to +secure trustworthy guidance for future investigations. +<span class="pagenum"><a id="Page_447"></a>[Pg 447]</span></p> + +<p><b>410. Dialysis.</b>—One of the most important of the operations +connected with the separation and analysis of proteids is the removal +of the salts whereby their solutions are secured. This is accomplished +by subjecting the solutions of the proteid matters to dialysis. The +solution is placed in bags made of parchment dialysis paper. These +bags are tied about a glass tube, whereby access may be had to their +contents during the progress of the work. Since the volume of the +liquid increases during the process, the bags should not be filled too +full in the beginning.</p> + +<div class="figcenter smcap"> + <img id="FIG_105" src="images/fig105.jpg" alt="" width="600" height="369" > + <p class="center spb1">Fig. 105. Dialyzing Apparatus.</p> +</div> + +<p>In this laboratory the dialysis is carried out by Bigelow with the +city water from the Potomac, which is first passed through a battery +of porous porcelain filtering tubes to remove any suspended silt or +micro-organisms. If unfiltered water be used, the germs therein cause +a fermentation in the proteid matter, which seriously interferes with +the value of the data obtained, and which can only be avoided by the +use of an antiseptic, such as an alcoholic solution of thymol. Even +with filtered water, the use of a few drops of the solution mentioned +is often necessary. To avoid the use of too great quantities of the +filtered water, the dialyzers are arranged <i>en batterie</i>, as shown +in the <a href="#FIG_105">figure</a>. The filtered water enters the first vessel and thence +<span class="pagenum"><a id="Page_448"></a>[Pg 448]</span> +passes through all. The parchment bags are frequently changed from +vessel to vessel, each being brought successively into the first vessel +in contact with the fresh water. In some cases the final steps in the +dialysis may be accomplished in distilled water.</p> + +<p>It is advisable to conduct a fractional preliminary dialysis of the +salt solution containing proteids in such a way as to secure the +globulins precipitated in each interval of twenty-four hours. Each +portion thus secured may be examined with the microscope. Usually a +period of two weeks is required to entirely remove the mineral salts +from solution. If prepared parchment tubes be used for the dialysis, +they should be first tested for leaks, and should not be more than half +filled. By the use of a large number of these tubes a greater surface +is exposed to dialytic action, and the time required to complete the +operation is correspondingly decreased.</p> + +<h3>SEPARATION AND ESTIMATION OF<br> NITROGENOUS BODIES IN ANIMAL PRODUCTS.</h3> + +<p id="P_411"><b>411. Preparation of the Sample.</b>—Animal products present many +difficulties in respect of the reduction thereof to a sufficiently +comminuted condition for analytical examination. In the case of bones, +the choppers used for preparing them for feeding to fowls are the most +efficient apparatus for reducing them to fragments. In this condition +they may be ground to a finer state in a sausage machine. The flesh of +animals may be reduced by this machine, with two or three grindings, +to a fairly homogeneous mass. Subsequent grinding in a mortar with +powdered glass or sharp sand may serve to reduce the sample to a finer +pulp, but is not usually necessary and should be avoided when possible. +The sample thus prepared serves for the estimation of water, ash +and fat by methods already described. The sample should be prepared +in quantities of considerable magnitude, the whole of any organ or +separate portion of the body being used when possible. In examining the +whole body the relative weights of blood, bones, viscera, muscle, hide +and other parts should first of all be ascertained and noted.</p> + +<p><b>412. Treatment of Muscular Tissues for Nitrogenous Bodies.</b>—For +<span class="pagenum"><a id="Page_449"></a>[Pg 449]</span> +the present purpose a brief sketch of the method of separating the +nitrogenous bodies in the muscular tissues of the body is all that +can be attempted. For methods of examining the different organs and +parts of the body in greater detail, standard works on physiological +chemistry may be consulted.<a id="FNanchor_387" href="#Footnote_387" class="fnanchor">[387]</a></p> + +<p><i>Extraction with Cold Water.</i>—A noted quantity of the finely +divided tissues is mixed with several volumes of ice cold water and +well rubbed occasionally for several hours, the temperature meanwhile +being kept low. The mixture is poured into a linen bag and the liquid +portion removed by gentle pressure. The residue in like manner is +treated with fresh portions of cold water until it gives up no further +soluble matters. An aliquot portion of the extract is concentrated +to a small bulk and serves for the determination of total nitrogen. +The methods of separating and estimating nitrogenous bodies in flesh +soluble in water will be given in considerable detail further on.</p> + +<p><i>Extraction with Ammonium Chlorid and Hydrochloric Acid.</i>—The +residue, after exhaustion with cold water, is extracted with a solution +of ammonium chlorid containing 150 grams of the salt in a liter. This +method of extraction is entirely similar to that with water just +described. Globulins and myosin pass into solution by this treatment. +The residual mass is washed as free as possible of the solvent and +is then further extracted with dilute hydrochloric acid containing +four cubic centimeters of the fuming acid in a liter. The treatment +with dilute acid is continued until no further substance passes +into solution. This is determined by neutralizing a portion of the +extract with sodium carbonate, or by the direct addition of potassium +ferrocyanid. In either case absence of a precipitate indicates that no +nitrogenous matters are present in the solution.</p> + +<p><i>Extraction with Alkali.</i>—The residue from the acid extraction +is washed with water until the acid is removed and then extracted in a +similar manner with a dilute solution of sodium or potassium hydroxid +containing not to exceed two grams of the caustic to the liter. When +this residue is finally washed with water and a little acetic acid, +it will be found that practically all the purely albuminous bodies +contained in the tissues have been extracted with the exception of any +<span class="pagenum"><a id="Page_450"></a>[Pg 450]</span> +fibrin, which the blood, present in the tissues at the commencement of +the extraction, may have contained. The extract should be acidified +with acetic as soon as obtained.</p> + +<p><i>Extraction with Boiling Water.</i>—The residual matter boiled +for some time with water will part with its collagen, which, when +transformed by the heat into glutin, passes into solution.</p> + +<p>The sarcolemma, membranes, elastic fibers and keratin remain +undissolved.</p> + +<p><b>413. Contents of the Several Extracts.</b>—By the systematic +treatment of muscular tissues in the manner just described, the +nitrogenous bodies they contain are separated into five classes, +<i>viz.</i>:</p> + +<p><i>Cold Water Extract.</i>—This contains serum albumin, serum +globulin, muscle albumin, myosin, mucin and peptone.</p> + +<p><i>Ammonium Chlorid Extract.</i>—This solution contains the globulins +and also in many cases some myosin and serum globulin.</p> + +<p><i>Hydrochloric Acid Extract.</i>—When the extractive matter removed +by hydrochloric acid, thrown out by sodium carbonate and well washed +with water, has a neutral reaction, it consists of syntonin, when acid, +of an albuminate.</p> + +<p><i>Alkali Extract.</i>—The acid albumin of the animal tissue is found +in the alkaline solution and may be thrown out by making the solution +slightly acid.</p> + +<p><i>Insoluble Residue.</i>—The fifth class contains the insoluble +nitrogenous bodies mentioned above.</p> + +<p><b>414. General Observations.</b>—Only a brief résumé of the methods +of treating animal tissues for nitrogenous bases is given above, since +a more elaborate discussion of these principles and methods would +lead too far away from the main purpose of this manual. For practical +purposes, the most important of these bodies are those soluble in water +and the methods of treating these will be handled at some length. +Unfortunately, the methods of determining the exact qualities of these +bodies are not as satisfactory in case of animal as in vegetable +nitrogenous bodies. The flesh bases, soluble in water, contain a much +larger percentage of nitrogen than is found in true proteid bodies, and +<span class="pagenum"><a id="Page_451"></a>[Pg 451]</span> +therefore the multiplication of the weight of nitrogen found therein by +6.25 does not give even a near approximation of the actual quantities +of the nitrogenous bodies present in the sample.</p> + +<p>Some of the flesh bases contain more than twice as much nitrogen as +is found in proteids, and in such cases 3.12, and not 6.25, would be +the more correct factor to use in the computation. When possible, +therefore, these bodies should be precipitated and weighed after +drying, but this is not practicable in many instances. The sole +resource of the chemist in such cases is to determine the nature of the +body as nearly as possible by qualitive reactions, then to determine +the total nitrogen therein and multiply its weight by the corresponding +factor. The principal flesh bases have the following percentages of +nitrogen and the approximate factors for calculating analytical data +are also given:</p> + +<table class="spb1"> + <thead><tr> + <th class="tdc bb">Name of base.</th> + <th class="tdc bb">Formula.</th> + <th class="tdc bb">Per cent<br> nitrogen. </th> + <th class="tdc bb">Factor.</th> + </tr></thead> + <tbody><tr> + <td class="tdl">Glutin</td> + <td class="tdl_ws1 fs_105">C₁₃H₂₀N₄O₅</td> + <td class="tdc">17.95</td> + <td class="tdc">5.57</td> + </tr><tr> + <td class="tdl">Carnin</td> + <td class="tdl_ws1 fs_105">C₇H₈N₄O₂</td> + <td class="tdc">31.11</td> + <td class="tdc">3.21</td> + </tr><tr> + <td class="tdl">Kreatin</td> + <td class="tdl_ws1 fs_105">C₄H₁₉N₃O₂</td> + <td class="tdc">32.06</td> + <td class="tdc">3.12</td> + </tr><tr> + <td class="tdl">Kreatinin</td> + <td class="tdl_ws1 fs_105">C₄H₇N₃O₂</td> + <td class="tdc">37.17</td> + <td class="tdc">2.69</td> + </tr><tr> + <td class="tdl">Sarkin</td> + <td class="tdl_ws1 fs_105">C₅H₄N₄O</td> + <td class="tdc">41.18</td> + <td class="tdc">2.43</td> + </tr> + </tbody> +</table> + +<p><b>415. Composition of Meat Extracts.</b>—The meat extracts of +commerce contain all the constituents of meat that are soluble in +warm water. The parts which are soluble in warm water and not in cold +are found in the cold aqueous solution as suspended or sedimentary +matters. Among the nitrogenous bodies present are included albumin, +albumose and peptone among the proteids, carnin, kreatin, kreatinin, +sarkin and xanthin among the non-proteids, and inosinic and uric acids +and urea among other nitrogenous bodies. Among the non-nitrogenous +bodies are found lactic and butyric acids, inosit and glycogen. Among +mineral bodies occurs the phosphates and chlorids of the common bases. +In addition to these bodies, meat extracts may also contain gelatin +and other decomposition products of proteid matter. Since meat extract +is supposed to be prepared by the digestion of the meat free of bones +and put in cold water or in warm water not above 75°, the presence of +<span class="pagenum"><a id="Page_452"></a>[Pg 452]</span> +gelatin would indicate a different method of preparation, <i>viz.</i>, +either by boiling water or water heated above the boiling point under +pressure. In a properly prepared extract, the percentage of gelatin is +very small.</p> + +<p>Approximately one-tenth of the whole nitrogen present is in the form +of albumoses and only a trace as peptones. By far the greater part of +the nitrogen exists as flesh bases (kreatin, etc.). The composition of +three meat extracts, numbers one and two solid and number three liquid, +is given in the subjoined table.<a id="FNanchor_388" href="#Footnote_388" class="fnanchor">[388]</a></p> + +<table class="spb1"> + <thead><tr> + <th class="tdc" colspan="3"> </th> + <th class="tdc bb">No. 1.<br> Per cent. </th> + <th class="tdc bb">No. 2.<br> Per cent. </th> + <th class="tdc bb">No. 3.<br> Per cent. </th> + </tr></thead> + <tbody><tr> + <td class="tdl" colspan="3">Total nitrogen</td> + <td class="tdc">9.28</td> + <td class="tdc">9.14</td> + <td class="tdc">2.77</td> + </tr><tr> + <td class="tdl">Nitrogen</td> + <td class="tdl_wsp">as</td> + <td class="tdl_wsp">albumin</td> + <td class="tdc">trace</td> + <td class="tdc">0.08</td> + <td class="tdc">trace</td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdc">”</td> + <td class="tdl_wsp">albumose</td> + <td class="tdc">0.96</td> + <td class="tdc">1.21</td> + <td class="tdc">0.70</td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdc">”</td> + <td class="tdl_wsp">peptone</td> + <td class="tdc">trace</td> + <td class="tdc">trace</td> + <td class="tdc">none</td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdc">”</td> + <td class="tdl_wsp">flesh bases</td> + <td class="tdc">6.81</td> + <td class="tdc">5.97</td> + <td class="tdc">1.56</td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdc">”</td> + <td class="tdl_wsp">ammonia</td> + <td class="tdc">0.47</td> + <td class="tdc">0.41</td> + <td class="tdc">0.09</td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdl_wsp">in</td> + <td class="tdl_wsp">compounds insoluble in</td> + <td class="tdc" colspan="3"> </td> + </tr><tr> + <td class="tdc"> </td> + <td class="tdc"> </td> + <td class="tdl_ws1">sixty-six per cent alcohol</td> + <td class="tdc">0.21</td> + <td class="tdc">0.33</td> + <td class="tdc">0.25</td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdc">”</td> + <td class="tdl_wsp">other bodies</td> + <td class="tdc">0.83</td> + <td class="tdc">1.14</td> + <td class="tdc">0.17</td> + </tr> + </tbody> +</table> + +<p id="P_417"><b>417. Analysis of Meat Extracts.</b>—The analysis of a meat extract +should include the determination of the water, ash and total nitrogen. +After multiplying the nitrogen which exists as proteids by 6.25 and +adding together the percentages of all the ingredients, ash, water, +etc., including ammonia, the sum is to be subtracted from 100 and the +difference entered as non-nitrogenous organic matter. The nature of +this conglomerate has already been explained.</p> + +<p><i>Water.</i>—It is advisable to determine the water in a partial +vacuum (<b><a href="#P_20">20</a></b>) or in an atmosphere of hydrogen +(<b><a href="#P_23">23-25</a></b>).</p> + +<p>The water may also be determined in solid extracts by placing about +five grams of the material in a flat bottom tin foil dish about +fifty-five millimeters in diameter and twenty millimeters deep. The +material is dissolved in enough warm water to fill the dish a little +over one-half and the liquid is then absorbed by adding a weighed +quantity of fibrous asbestos or of dry fragments of pumice stone. +The asbestos is to be preferred because of the fact that it may be +subsequently cut into small bits for the determination of the gelatin. +<span class="pagenum"><a id="Page_453"></a>[Pg 453]</span> +The dish thus prepared is dried to constant weight in a steam-bath +or vacuum oven. The weight of the dish and of the added absorbent, +together with that of the material employed and of the dried dish and +its contents, give the data for calculating the percentage of water. +The contents of the dish are used as described further on for the +determination of gelatin. In liquid extracts the water is determined in +an entirely analogous manner, using about twenty grams of the material +and omitting the solution in water.</p> + +<p>In solid extracts, the part insoluble in cold water is determined +separately.</p> + +<p><i>Ash.</i>—The ash is determined by ignition at the lowest possible +temperature, best in a muffle (<b><a href="#P_28">28-32</a></b>). The ash should be +examined qualitively. Where a quantitive analysis is desired, larger +quantities of the extract are incinerated and the constituents of the +ash determined in the usual way.<a id="FNanchor_389" href="#Footnote_389" class="fnanchor">[389]</a></p> + +<p><i>Total Nitrogen.</i>—Since nitrates are not present unless added +in the manufacture, the total nitrogen is best determined by moist +combustion.<a id="FNanchor_390" href="#Footnote_390" class="fnanchor">[390]</a></p> + +<p><i>Nitric Nitrogen.</i>—The extract should be tested for nitrates and +if present they are determined in the manner already described.<a id="FNanchor_391" href="#Footnote_391" class="fnanchor">[391]</a></p> + +<p><i>Ammoniacal Nitrogen.</i>—When ammonia is present it is determined +by distillation with magnesia.<a id="FNanchor_392" href="#Footnote_392" class="fnanchor">[392]</a></p> + +<p>Since boiling with magnesia may cause the distillation of more +ammonia than is present as ammonium salts, the plus being due to the +decomposition of some other nitrogenous compounds, Stutzer replaces the +magnesia with barium carbonate.<a id="FNanchor_393" href="#Footnote_393" class="fnanchor">[393]</a></p> + +<p><i>Proteid Nitrogen Insoluble in Sixty-Two Per Cent Alcohol.</i>—The +aqueous solution is treated with strong alcohol until the mixture +contains about sixty-two per cent of the reagent. The precipitate +produced is separated by filtration, washed with sixty-two per cent +alcohol and the nitrogen therein determined.</p> + +<p><i>Albumose Nitrogen.</i>—This is secured by saturating the aqueous +solution with zinc or ammonium sulfate. The separated albumoses are +skimmed from the surface, thrown in a filter, washed with a saturated +<span class="pagenum"><a id="Page_454"></a>[Pg 454]</span> +solution of zinc sulfate and the nitrogen determined therein by moist +combustion. In the filtrate from the above separation, peptone is +detected qualitively by adding a few drops of dilute solution of copper +sulfate (biuret reaction).</p> + +<p><i>Kreatin, Kreatinin and Other Flesh Bases.</i>—The clear, aqueous +solution of the extract is acidified with sulfuric, mixed with a +solution of sodium phosphotungstate and allowed to stand for about +six days. The precipitate is collected, washed with a solution of +the precipitant, and the nitrogen therein determined. The nitrogen +found, less that due to ammonia, represents the total nitrogenous +matter precipitated by the phosphotungstic acid. From this quantity +is deducted the nitrogen in the proteids, precipitated by sixty-two +per cent alcohol and by ammonium or zinc sulfate, and the remainder +represents the nitrogen in flesh bases.</p> + +<p>The nitrogen thrown out by the phosphotungstic acid is deducted from +the total nitrogen, and the remainder represents the nitrogenous bodies +not precipitable by the reagent named.</p> + +<p>This method of separating the nitrogenous matters in meat extracts is +based on the observation that these bodies contain at most only a small +quantity of peptones, so small as to be safely negligible.<a id="FNanchor_394" href="#Footnote_394" class="fnanchor">[394]</a></p> + +<p><i>Quantities used for Analysis.</i>—In conducting the separations +above noted, it will be found convenient to use in each case about +five grams of the solid or twenty of the liquid extract. In the +nitrogen determinations, the weight of the sample should be inversely +proportional to its content of nitrogen.</p> + +<p><b>417. Preparation of the Phosphotungstic Reagent.</b>—The +phosphotungstic reagent is conveniently prepared as follows:</p> + +<p>Dissolve 120 grams of sodium phosphate and 200 of sodium tungstate in +one liter of water and add to the solution 100 cubic centimeters of +strong sulfuric acid. When the reagent is prepared for general purposes +it is customary to acidify with nitric, but in the present instance, +inasmuch as the precipitate is used for the determination of nitrogen, +it is evident that sulfuric should be substituted for nitric acid. In +<span class="pagenum"><a id="Page_455"></a>[Pg 455]</span> +all cases the analyst must be assured of the strong acidity of the +reagent, and in addition to this the solutions of proteid matter to +which the reagent is added must first be made strongly acid with +sulfuric.</p> + +<p><b>418. Zinc Sulfate as Reagent for Separating Albumoses from +Peptones.</b>—When the albumoses are separated from the peptones, by +precipitation with ammonium sulfate, there may be danger of some of +this reagent adhering to the albumose, and in this way the quantity of +nitrogen obtained on analysis may be increased. To avoid an accident of +this kind Bömer replaces the ammonium by zinc sulfate.<a id="FNanchor_395" href="#Footnote_395" class="fnanchor">[395]</a></p> + +<p>Since the precipitation of the albumoses by saturated saline solutions +depends on their hydrolytic power, the substitution of another salt +for ammonium sulfate capable of strongly attracting water, may be made +if that salt does not possess any objectionable property. Crystallized +zinc sulfate will dissolve in less than its own weight of cold water +and is therefore well suited for the purpose in view.</p> + +<p>In the case of a meat extract, the precipitation is accomplished as +follows: Fifty cubic centimeters of the extract, freed from all solid +matter by filtration and containing about two grams of the soluble +proteids, are saturated in the cold with finely powdered zinc sulfate. +The separated albumoses collect on the surface and are skimmed off, +poured on a filter and washed with cold saturated zinc sulfate +solution. The filter and its contents are used for the determination of +nitrogen by moist combustion.<a id="FNanchor_396" href="#Footnote_396" class="fnanchor">[396]</a></p> + +<p>The filtrate from the precipitated albumoses gives no biuret reaction, +and, therefore, as in the use of ammonium sulfate, is free of albumin.</p> + +<p>The biuret reaction is applied to the zinc sulfate filtrate as follows: +The filtrate is greatly diluted with water and freed of zinc by means +of a saturated solution of sodium carbonate. The filtrate free of zinc +is evaporated on the steam-bath, made strongly alkaline with sodium +hydroxid and treated with a few drops of a two per cent copper sulfate +solution, added successively.</p> + +<p>Another advantage possessed by the zinc sulfate is found in the fact +<span class="pagenum"><a id="Page_456"></a>[Pg 456]</span> +that in the filtrate from the separated albumoses the peptones and +other flesh bases can be thrown out by phosphotungstic acid. Before the +application of the reagent, the filtrate should be made strongly acid +by adding about an equal volume of dilute sulfuric acid (one part of +acid to four of water.)</p> + +<p>The nitrogen in the precipitate thus obtained is determined by moist +combustion in the manner already suggested.</p> + +<p>If the proteid matters contain salts of ammonium it is probable +that a difficultly soluble double sulfate of zinc and ammonium, +<b>(NH₄)₂SO₄.ZnSO₄.6H₂O</b>, will be found in the precipitate. Ammonium salts, +if present, should therefore be removed by distillation with magnesia. +It is better, however, to throw down the ammonia with the first zinc +precipitate, distil this with magnesia and determine the amount of +nitrogen derived from the ammonia compounds. In a second sample, the +total nitrogen is determined by moist combustion and the difference +between the two results gives that due to albumoses.</p> + +<p><b>419. Examination for Muscular Tissue.</b>—Some samples of meat +extracts contain small quantities of finely ground muscular tissue. For +detecting this the extract is treated with cold water and the insoluble +residue examined with a microscope. If muscular tissue be found, about +eight grams of the extract or twenty-five of the fluid preparation, are +treated with cold water, the insoluble matter collected upon a filter, +washed with cold water, and the nitrogen determined in the residue. The +percentage of nitrogen multiplied by 6.25 gives the quantity of muscle +fiber proteids present. The filtrate from the above determination +is acidified with acetic, boiled, any precipitate which is formed +collected and the nitrogen therein determined. The nitrogen obtained +multiplied by 6.25 gives the quantity of coagulable albumin present. +An aliquot portion of the filtrate is used for the determination of +nitrogen and the percentage therein found, deducted from the total +nitrogen of the sample, gives a remainder which may be used as a +representative of the whole of the nitrogen present in the form of +albumin and muscular tissue.</p> + +<p><b>420. Estimation of Gelatin.</b>—The tin foil dish and its contents +used for the determination of water, as above described, are cut into +<span class="pagenum"><a id="Page_457"></a>[Pg 457]</span> +small pieces, placed in a beaker and extracted four times with +absolute alcohol. After the removal of the alcohol, the residue is +extracted with ice water containing ten per cent of alcohol, in +which a small piece of ice is kept to avoid a rise of temperature. +The beaker should be shaken during the extraction, which should last +for about two minutes. Where large numbers of samples are treated +at once, any convenient form of shaking machine may be employed. At +least two extractions with ice water must be made. The residue is then +collected upon a filter and washed with ice water until the washings +are completely colorless. The residue on the filter is replaced in +the beaker, boiled with water, well washed on the filter with boiling +water, the filtrate and washings concentrated and the nitrogen therein +determined.</p> + +<p>The principle of this determination is based on the fact that gelatin +is almost completely insoluble in ice water while serum peptones and +albumin peptones are almost completely soluble in that reagent. On +the other hand, the flesh bases and the proteids present are almost +completely removed by the preliminary treatment with alcohol and ice +water or are left undissolved by the hot water. The solution in boiling +water, therefore, contains practically nothing but gelatin.<a id="FNanchor_397" href="#Footnote_397" class="fnanchor">[397]</a></p> + +<p>In a later article, Stutzer modifies the method given above as +follows:<a id="FNanchor_398" href="#Footnote_398" class="fnanchor">[398]</a></p> + +<p>Of dry and moist extracts from five to seven grams and of liquid +extracts from twenty to twenty-five grams are used for the +determination and placed in tin foil dishes, as described above. In +case of solid extracts, a sufficient quantity of warm water is added to +completely dissolve them, the solution being facilitated by stirring. +In case the solution is too thin it should be concentrated before going +further. It is treated with a sufficient amount of dust-free ignited +sand to completely absorb it, and the dish and its contents are then +dried to a constant weight. The dried contents of the dish are rubbed +up in a mortar, the dish cut into fine bits, and all placed in a +beaker. The solid syrphete<a id="FNanchor_399" href="#Footnote_399" class="fnanchor">[399]</a> +is extracted four times with 100 cubic centimeters of absolute alcohol, +the alcohol in each case being poured through an asbestos filter for +<span class="pagenum"><a id="Page_458"></a>[Pg 458]</span> +the purpose of collecting any matters suspended therein. In a large +flask are placed 100 grams of alcohol, 300 grams of ice and 600 grams +of cold water, and the flask is placed in a large vessel and packed +with finely divided ice. Four beakers marked <i>b, c, d, e</i> are +also placed in ice and the beaker containing the syrphete, left after +extraction with absolute alcohol as above mentioned, is marked <i>a</i> +and also placed in pounded ice. The extraction with cold alcoholic +water proceeds as follows:</p> + +<p>In beaker <i>a</i> are poured 100 cubic centimeters of the mixture in +the large flask, its contents are stirred for two minutes and then the +liquid portion poured off into beaker <i>b</i> to which, at the same +time, a piece of ice is added. In beaker <i>a</i> are poured again 100 +cubic centimeters from the large flask, treated as above described, +and the liquid extract poured into beaker <i>c</i>. In like manner the +extraction in beaker <i>a</i> is continued until each of the beakers +has received its portion of the extract. By this time the liquid +over the sand in beaker <i>a</i> should be completely colorless. The +filtration of the liquid extract is accomplished as follows:</p> + +<p>In a funnel of about seven centimeters diameter is placed a perforated +porcelain plate about four centimeters in diameter which is covered +with asbestos felt with long fiber. Three filters are prepared in this +way. On the first filter are poured the contents of beaker <i>b</i>. +After the liquid has passed through, the sand and other residue in +beaker <i>a</i> are transferred to the filter and the beaker and +residue washed with the alcoholic ice water from the large flask. The +filtration should be accomplished under pressure. On the second filter +are poured the contents of beaker <i>c</i>. On the third filter the +contents of beakers <i>d</i> and <i>e</i>. The washing with alcoholic +ice water from the large flask is continued in each instance until the +filtrate is colorless. At the same time the asbestos filter, which was +used in the first instance for filtering the absolute alcohol extract, +is washed with the alcoholic ice water mixture from the large flask. At +the end the sand remaining in beaker a together with all the asbestos +filters are brought together into a porcelain dish, boiled two or +three times with water, the aqueous solution filtered and the filtrate +concentrated and used for the estimation of the nitrogen. The quantity +<span class="pagenum"><a id="Page_459"></a>[Pg 459]</span> +of nitrogen found multiplied by 6.25 represents the proteid matter in +the gelatin of the sample.</p> + +<p>The object of the multiple filters, described above, is to accelerate +the process, and they are required because the gelatin quickly occludes +the filter pores. For this reason the asbestos filters are found +to operate better than those made of paper. It should be mentioned +that the residue of the peptones insoluble in alcohol may contain, +in addition to gelatin, also small quantities of albumoses. From the +quantity of albumose nitrogen found, it is understood that the nitrogen +in the form of coagulable albumin, determined as described in the first +process mentioned above, is to be deducted, since these coagulable +albumins are insoluble in alcohol.</p> + +<p><b>421. Estimation of Nitrogen in the Flesh Bases Soluble in +Alcohol.</b>—About five grams of the dry extract, ten grams of the +extract containing water or twenty-five grams of the liquid extract +are placed in a beaker and enough water added in each case to make +about twenty-five cubic centimeters in all. Usually no water need be +added to the liquid extracts. Very thin peptone solutions should be +evaporated until the content of water is reduced to seventy-five per +cent. The solution, prepared as above indicated, is treated slowly +with constant stirring with 250 cubic centimeters of absolute alcohol, +the stirring continued for some minutes and the vessel set aside for +twelve hours, at the end of which time the precipitate is separated by +filtration and washed repeatedly with strong alcohol. Leucin, tyrosin +and a part of the flesh bases are dissolved by alcohol. The alcohol is +removed by distillation and the residue dissolved in water. Any flocky +residue which remains on solution with water is removed by filtration, +the nitrogen determined therein and the quantity thereof added to the +albumose nitrogen found, as hereafter described.</p> + +<p>The volume of the aqueous solution is completed with water to half a +liter. One hundred cubic centimeters of this solution are used for the +determination of total nitrogen, and another 100 cubic centimeters for +the determination of ammoniacal nitrogen by distillation with barium +<span class="pagenum"><a id="Page_460"></a>[Pg 460]</span> +carbonate. A part of the ammonia may have escaped during the +preliminary distillation of the alcohol and therefore the amount found +may not represent the whole amount originally present. The use of the +above determination is principally to ascertain the correction to be +made in the amount of total nitrogen found in the first 100 cubic +centimeters of the solution.</p> + +<p><b>422. Treatment of the Residue Insoluble in Alcohol.</b>—The +residue insoluble in alcohol is washed from the filter into the beaker +in which the first solution was made. The aqueous mixture is warmed +on a water-bath until the alcohol adhering to the precipitate is +completely evaporated, when the contents of the beaker are poured upon +a filter free of nitrogen. A small part of the albumose, by reason of +the treatment with alcohol, tends to remain undissolved, and it is +advisable to collect this albumose upon a filter, wash it well with hot +water and estimate the nitrogen therein. The quantity of nitrogen thus +found is to be added to the albumose nitrogen determined as described +later on.</p> + +<p>The total filtrate obtained from the last filtration is made up to +a volume of half a liter, of which fifty cubic centimeters are used +for the determination of total nitrogen, fifty cubic centimeters for +the determination of gelatin, albumose and peptone, and 100 cubic +centimeters for the residual peptones. The albumose, together with the +gelatin and peptones carried down with it, is precipitated with zinc or +ammonium sulfate solution, and its per cent calculated from the amount +of nitrogen found in the precipitate. The true peptone is determined by +subtracting the quantity of nitrogen determined as albumose from the +total nitrogen in solution.</p> + +<p>The rest of the liquid, <i>viz.</i>, 300 cubic centimeters, is +evaporated to a small volume and tested qualitively for true peptones +as follows:</p> + +<p>To separate the albumose and gelatin a concentrated liquor is treated +with an excess of finely divided ammonium sulfate so that a part of +the salt remains undissolved. The separated albumose, gelatin and +undissolved ammonium salts are collected on a filter, the filtrate +mixed with a few drops of dilute copper sulfate solution and a +<span class="pagenum"><a id="Page_461"></a>[Pg 461]</span> +considerable quantity of concentrated soda or potash lye added. Care +should be taken that the quantity of copper is not too great, otherwise +the peculiar red coloration will be obscured by the blue color of the +copper solution.</p> + +<p><b>423. Pancreas Peptone.</b>—The filtrate obtained as described +above, by treating the portion of the material insoluble in alcohol +with warm water, contains in addition to the albumose and gelatin the +whole of the pancreas peptone which may be present. To separate this +peptone, 100 cubic centimeters of the aqueous solution are evaporated +in a porcelain dish until the volume does not exceed ten cubic +centimeters. When cool, at least 100 cubic centimeters of a saturated +cooled solution of ammonium sulfate solution are added, the mixture +thoroughly stirred, the precipitate collected upon a filter and washed +with a cold saturated solution of ammonium sulfate. The contents of +the filter are dissolved in boiling water, the filter thoroughly +washed and the filtrate and washings evaporated in a porcelain dish +with the addition of barium carbonate until, on the addition of new +quantities of barium carbonate, no further trace of ammonia can be +discovered. The residue is extracted with water, the barium sulfate and +carbonate present separated by filtration, well washed and the nitrogen +determined in the evaporated filtrate and washings in the usual way and +multiplied by 6.25 to determine the quantity of pancreas peptone.</p> + +<p><b>424. Albumose Peptone.</b>—A part of the albumose peptone which may +be present is determined in conjunction with the other bodies mentioned +above. The chief quantity is found in the solution of the residue +insoluble in alcohol in the following manner:</p> + +<p>Fifty cubic centimeters of the solution of this residue in hot water +are mixed with an equal volume of dilute sulfuric acid, one volume +of acid to three of water, in the cold, and a solution of sodium +phosphotungstate added until it produces no further precipitate. The +precipitate is washed with dilute sulfuric acid and the nitrogen +determined therein. The nitrogen thus found is derived from the +albumose, pancreas peptone and gelatin. The quantity of nitrogen in the +pancreas peptone and gelatin, as above described, is subtracted from +<span class="pagenum"><a id="Page_462"></a>[Pg 462]</span> +the total quantity found in the phosphotungstic acid precipitated, and +the remainder represents the nitrogen due to the albumose.</p> + +<p><b>425. Nitrogen in the Form of Flesh Bases Insoluble in +Alcohol.</b>—This is determined by subtracting the quantity of +nitrogen, determined by the phosphotungstic acid method already +described, from the total quantity of nitrogen found in the precipitate +insoluble in alcohol and soluble in water.</p> + +<h3>AUTHORITIES CITED IN PART FIFTH.</h3> +<div class="footnotes"> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_337" href="#FNanchor_337" class="label">[337]</a> +Watts’ Dictionary of Chemistry, new edition, Vol. 4, p. 327.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_338" href="#FNanchor_338" class="label">[338]</a> +Vid. op. cit. supra, p. 330.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_339" href="#FNanchor_339" class="label">[339]</a> +Barbieri, Journal für praktische Chemie, neue Folge Band 18, S. 114.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_340" href="#FNanchor_340" class="label">[340]</a> +Vid. op. cit. 1, p. 339.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_341" href="#FNanchor_341" class="label">[341]</a> +Bulletin No. 49, Kansas Experiment Station, May, 1895.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_342" href="#FNanchor_342" class="label">[342]</a> +This work, Vol. 2, p. 208.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_343" href="#FNanchor_343" class="label">[343]</a> +Vid. op. cit. supra, Vol. 1, p. 570.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_344" href="#FNanchor_344" class="label">[344]</a> +Wiley, American Chemical Journal, Vol. 6, No. 5, p. 289.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_345" href="#FNanchor_345" class="label">[345]</a> +Obermayer, Chemiker-Zeitung Repertorium, Oct. 1889, S. 269.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_346" href="#FNanchor_346" class="label">[346]</a> + Hoppe-Seyler, Handbuch der physiologisch- und +pathologisch-chemischen Analyse, S. 269.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_347" href="#FNanchor_347" class="label">[347]</a> +Wiley, American Chemical Journal, Vol. 6, p. 289.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_348" href="#FNanchor_348" class="label">[348]</a> +Dragendorff’s Plant Analysis, p. 55.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_349" href="#FNanchor_349" class="label">[349]</a> +This work, Vol. 2, pp. 192 et seq.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_350" href="#FNanchor_350" class="label">[350]</a> +Chemiker-Zeitung, Band 20, S. 151.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_351" href="#FNanchor_351" class="label">[351]</a> +This work, Vol. 2, p. 207.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_352" href="#FNanchor_352" class="label">[352]</a> +Landwirtschaftlichen Versuchs-Stationen, Band 17, S. 321: +Zeitschrift für analytische Chemie, Band 14, S. 380.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_353" href="#FNanchor_353" class="label">[353]</a> +Vid. op. cit. 12, p. 245.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_354" href="#FNanchor_354" class="label">[354]</a> +Landwirtschaftlichen Versuchs-Stationen, Band 16, S. 61.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_355" href="#FNanchor_355" class="label">[355]</a> +Berichte der deutschen chemischen Gesellschaft, Band 10, +Ss. 85, 199; Band 16, S. 312: Chemiker-Zeitung, Band 20, S. 145.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_356" href="#FNanchor_356" class="label">[356]</a> +Zeitschrift für analytische Chemie, Band 22, S. 325.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_357" href="#FNanchor_357" class="label">[357]</a> +Richardson and Crampton, Berichte der deutschen +chemischen Gesellschaft, Band 19, S. 1180.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_358" href="#FNanchor_358" class="label">[358]</a> +Maxwell, American Chemical Journal, Vol. 13, p. 470.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_359" href="#FNanchor_359" class="label">[359]</a> +Vid. op. cit. supra, Vol. 15, p. 185.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_360" href="#FNanchor_360" class="label">[360]</a> +Vid. op. cit. supra, Vol. 13, p. 13: Schulze, Zeitschrift +physiologische Chemie, Band 14, S. 491.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_361" href="#FNanchor_361" class="label">[361]</a> +This work, Vol. I, p. 411.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_362" href="#FNanchor_362" class="label">[362]</a> +Vid. op. cit., 22, Vol. 13, p. 15.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_363" href="#FNanchor_363" class="label">[363]</a> +Vid. op. cit. supra, Vol. 15, p. 188.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_364" href="#FNanchor_364" class="label">[364]</a> +Hoppe-Seyler, Handbuch der physiologisch- und +pathologisch-chemischen Analyse, S. 169.</p> +</div> + +<p><span class="pagenum"><a id="Page_463"></a>[Pg 463]</span></p> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_365" href="#FNanchor_365" class="label">[365]</a> +This work, Vol. 2, p. 225.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_366" href="#FNanchor_366" class="label">[366]</a> +Bulletin No. 45, Division of Chemistry, U. S. Department of Agriculture, p. 51.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_367" href="#FNanchor_367" class="label">[367]</a> +Osborne and Voorhees, American Chemical Journal, Vol. 15, p. 470.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_368" href="#FNanchor_368" class="label">[368]</a> +Vid. op. cit. supra, Vol. 13, p. 385.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_369" href="#FNanchor_369" class="label">[369]</a> +Vid. op. cit. supra, p. 412.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_370" href="#FNanchor_370" class="label">[370]</a> +Vid. op. cit. supra, Vol. 15, p. 402.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_371" href="#FNanchor_371" class="label">[371]</a> +Vid. op. cit. supra, p. 404.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_372" href="#FNanchor_372" class="label">[372]</a> +Zeitschrift für analytische Chemie, Band 34, S. 562.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_373" href="#FNanchor_373" class="label">[373]</a> +Vid. op. cit. 34, p. 404.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_374" href="#FNanchor_374" class="label">[374]</a> +Vid. op. cit. 3, p. 455.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_375" href="#FNanchor_375" class="label">[375]</a> +Osborne and Voorhees, vid. op. cit. 34, p. 409.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_376" href="#FNanchor_376" class="label">[376]</a> +Vid. op. cit. supra, Vol. 13, p. 464.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_377" href="#FNanchor_377" class="label">[377]</a> +Chittenden and Osborne, op. cit. supra, Vol. 14, p. 32.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_378" href="#FNanchor_378" class="label">[378]</a> +Vid. op. cit. supra, p. 41.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_379" href="#FNanchor_379" class="label">[379]</a> +Vid. op. cit. supra, p. 639.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_380" href="#FNanchor_380" class="label">[380]</a> +Vid. op. cit. supra, Vol. 13, p. 399.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_381" href="#FNanchor_381" class="label">[381]</a> +Vid. op. cit. supra, pp. 395, 400, 401.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_382" href="#FNanchor_382" class="label">[382]</a> +Vid. op. cit. supra, p. 409.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_383" href="#FNanchor_383" class="label">[383]</a> +This work, Vol. 1, p. 319.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_384" href="#FNanchor_384" class="label">[384]</a> +This work, Vol. 2, pp. 169 et seq.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_385" href="#FNanchor_385" class="label">[385]</a> +Vid. op. cit. 47, p. 420.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_386" href="#FNanchor_386" class="label">[386]</a> +Osborne, vid. op. cit. 44, p. 410.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_387" href="#FNanchor_387" class="label">[387]</a> +Hoppe-Seyler, Handbuch der physiologisch- und +pathologisch-chemischen Analyse.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_388" href="#FNanchor_388" class="label">[388]</a> +König und Bömer, Zeitschrift für analytische Chemie, Band 34, S. 560.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_389" href="#FNanchor_389" class="label">[389]</a> +This work, Vol. 2, pp. 297, 298.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_390" href="#FNanchor_390" class="label">[390]</a> +Vid. op. cit. supra, p. 184.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_391" href="#FNanchor_391" class="label">[391]</a> +Vid. op. cit. supra, p. 206.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_392" href="#FNanchor_392" class="label">[392]</a> +This work, Vol. I, p. 450; Vol. 2, p. 226.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_393" href="#FNanchor_393" class="label">[393]</a> +Zeitschrift für analytische Chemie, Band 34, S. 377.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_394" href="#FNanchor_394" class="label">[394]</a> +König und Bömer, vid. op. cit. supra, S. 560.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_395" href="#FNanchor_395" class="label">[395]</a> +Vid. op. cit. supra, S. 562.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_396" href="#FNanchor_396" class="label">[396]</a> +Vid. op. cit. 53, p. 184.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_397" href="#FNanchor_397" class="label">[397]</a> +Vid. op. cit. 57, S. 374.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_398" href="#FNanchor_398" class="label">[398]</a> +Vid. op. cit. supra, S. 568.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_399" href="#FNanchor_399" class="label">[399]</a> +From συρφετος.</p> +</div> +</div> + +<hr class="chap x-ebookmaker-drop"> + +<div class="chapter"> +<p><span class="pagenum"><a id="Page_464"></a>[Pg 464]</span></p> +<h2 class="nobreak">PART SIXTH.<br> +<span class="h_subtitle">DAIRY PRODUCTS.</span></h2> +</div> + +<p><b>426. Introductory.</b>—The importance of dairy products has led to +the publication of a vast amount of literature relating thereto, and +it seems almost a hopeless task to present even a typical abstract of +the various analytical processes which have been proposed and used in +their study. The general principles which have been developed in the +preceding parts of this volume are applicable to the study of dairy +products, and the analyst who is guided by them can intelligently +examine the bodies specially considered in the present part. There +have been developed, however, many valuable processes for the special +examination of dairy products, which are of such a nature that they +could not be properly discussed in the preceding pages. In the present +part an effort will be made to present in a typical form the most +important of these processes and to state the general principles on +which they are based. This subject is naturally subdivided into three +parts, <i>viz.</i>, milk, butter and cheese. The milk sugar industry is +not of sufficient importance to receive a special classification.</p> + +<h3>MILK.</h3> + +<p><b>427. Composition of Milk.</b>—The composition of milk not only +varies with the genus and species of the mammal from which it is +derived, but also depends in a marked degree on idiosyncrasy.<a id="FNanchor_400" href="#Footnote_400" class="fnanchor">[400]</a></p> + +<p>Milk is a mixture containing water, proteids, fat, carbohydrates, +organic and inorganic acids and mineral salts. There have also been +observed in milk in minute quantities ammonia, urea, hypoxanthin, +chyme, chyle, biliverdin, cholesterin, mucin, lecithin, kreatin, leucin +and tyrosin. In the fermentation which milk undergoes in incipient +decomposition there is sometimes developed from the proteid matter, as +pointed out by Vaughn, a ptomaine, tyrotoxicon, which is a virulent +poison.<a id="FNanchor_401" href="#Footnote_401" class="fnanchor">[401]</a> +The presence of these last named bodies is of interest chiefly to the +physiologist and pathologist and can receive no further attention here. +<span class="pagenum"><a id="Page_465"></a>[Pg 465]</span></p> + +<p>From a nutritive point of view, the important components of milk are +the fats, proteids and sugar, but especially in the nourishment of the +young the value of lime and phosphoric acid must be remembered. The +mean composition of the most important milks, as determined by recent +analyses, is given below:</p> + +<table class="spb1"> + <thead><tr> + <th class="tdc"> </th> + <th class="tdc bb">Water.<br> Per cent. </th> + <th class="tdc bb">Sugar.<br> Per cent. </th> + <th class="tdc bb">Proteids.<br> Per cent. </th> + <th class="tdc bb">Fat.<br> Per cent. </th> + <th class="tdc bb">Ash.<br> Per cent. </th> + </tr></thead> + <tbody><tr> + <td class="tdl">Cow</td> + <td class="tdc">86.90</td> + <td class="tdc">4.80</td> + <td class="tdc">3.60</td> + <td class="tdc">4.00</td> + <td class="tdc">0.70</td> + </tr><tr> + <td class="tdl">Human</td> + <td class="tdc">88.75</td> + <td class="tdc">6.00</td> + <td class="tdc">1.50</td> + <td class="tdc">3.45</td> + <td class="tdc">0.30</td> + </tr><tr> + <td class="tdl">Goat</td> + <td class="tdc">85.70</td> + <td class="tdc">4.45</td> + <td class="tdc">4.30</td> + <td class="tdc">4.75</td> + <td class="tdc">0.80</td> + </tr><tr> + <td class="tdl">Ass</td> + <td class="tdc">89.50</td> + <td class="tdc">6.25</td> + <td class="tdc">2.00</td> + <td class="tdc">1.75</td> + <td class="tdc">0.50</td> + </tr><tr> + <td class="tdl">Mare</td> + <td class="tdc">90.75</td> + <td class="tdc">5.70</td> + <td class="tdc">2.00</td> + <td class="tdc">1.20</td> + <td class="tdc">0.35</td> + </tr><tr> + <td class="tdl">Sheep</td> + <td class="tdc">80.80</td> + <td class="tdc">4.90</td> + <td class="tdc">6.55</td> + <td class="tdc">6.85</td> + <td class="tdc">0.90</td> + </tr> + </tbody> +</table> + +<p>The mean composition of milk, as given by Watts and König, is given in +the following tables:</p> + +<table class="spb1"> + <thead><tr class="smcap fs_120"> + <th class="tdc"> </th> + <th class="tdc" colspan="6">Watts.</th> + </tr><tr> + <th class="tdc"> </th> + <th class="tdc_bott bb"> Water. </th> + <th class="tdc_bott bb"> Solids. </th> + <th class="tdc_bott bb"> Proteids. </th> + <th class="tdc_bott bb"> Fats. </th> + <th class="tdc_bott bb"> Sugar. </th> + <th class="tdc bb"> Mineral <br>Salts.</th> + </tr></thead> + <tbody><tr> + <td class="tdl">Woman</td> + <td class="tdc">87.65</td> + <td class="tdc">12.35</td> + <td class="tdc">3.07</td> + <td class="tdc">3.91</td> + <td class="tdc">5.01</td> + <td class="tdc">0.17</td> + </tr><tr> + <td class="tdl">Ass</td> + <td class="tdc">90.70</td> + <td class="tdc"> 9.30</td> + <td class="tdc">1.70</td> + <td class="tdc">1.55</td> + <td class="tdc">5.80</td> + <td class="tdc">0.50</td> + </tr><tr> + <td class="tdl">Cow</td> + <td class="tdc">86.56</td> + <td class="tdc">13.44</td> + <td class="tdc">4.08</td> + <td class="tdc">4.03</td> + <td class="tdc">4.60</td> + <td class="tdc">0.73</td> + </tr><tr> + <td class="tdl">Goat</td> + <td class="tdc">86.76</td> + <td class="tdc">13.24</td> + <td class="tdc">4.23</td> + <td class="tdc">4.48</td> + <td class="tdc">3.91</td> + <td class="tdc">0.62</td> + </tr><tr> + <td class="tdl">Sheep</td> + <td class="tdc">83.31</td> + <td class="tdc">16.69</td> + <td class="tdc">5.73</td> + <td class="tdc">6.05</td> + <td class="tdc">3.96</td> + <td class="tdc">0.68</td> + </tr><tr> + <td class="tdl">Mare</td> + <td class="tdc">82.84</td> + <td class="tdc">17.16</td> + <td class="tdc">1.64</td> + <td class="tdc">6.87</td> + <td class="tdc" colspan="2">8.65</td> + </tr> + </tbody> +</table> + +<table class="spb1"> + <thead><tr class="smcap fs_120"> + <th class="tdc" colspan="6">König.</th> + </tr><tr> + <th class="tdc"> </th> + <th class="tdc_bott bb"> Water. </th> + <th class="tdc_bott bb"> Fat. </th> + <th class="tdc bb"> Casein and <br>albumin.</th> + <th class="tdc_bott bb">Milk<br> Sugar. </th> + <th class="tdc bb"> Ash. </th> + </tr></thead> + <tbody><tr> + <td class="tdl">Woman</td> + <td class="tdc">87.41</td> + <td class="tdc">3.78</td> + <td class="tdc">2.29</td> + <td class="tdc">6.21</td> + <td class="tdc">0.31</td> + </tr><tr> + <td class="tdl">Mare</td> + <td class="tdc">90.78</td> + <td class="tdc">1.21</td> + <td class="tdc">1.99</td> + <td class="tdc">5.67</td> + <td class="tdc">0.35</td> + </tr><tr> + <td class="tdl">Ass</td> + <td class="tdc">89.64</td> + <td class="tdc">1.63</td> + <td class="tdc">2.22</td> + <td class="tdc">5.99</td> + <td class="tdc">0.51</td> + </tr><tr> + <td class="tdl">Cow</td> + <td class="tdc">87.17</td> + <td class="tdc">3.69</td> + <td class="tdc">3.55</td> + <td class="tdc">4.88</td> + <td class="tdc">0.71</td> + </tr> + </tbody> +</table> + +<p>The average composition of 120,540 samples of cow milk, as determined +by analysis, extending over a period of eleven years, was found by +Vieth to be as follows:<a id="FNanchor_402" href="#Footnote_402" class="fnanchor">[402]</a></p> + +<table class="spb1"> + <tbody><tr> + <td class="tdl"> </td> + <td class="tdr">Per cent.</td> + </tr><tr> + <td class="tdl">Total solids</td> + <td class="tdc">12.9</td> + </tr><tr> + <td class="tdl">Solids not fat  </td> + <td class="tdc"> 8.8</td> + </tr><tr> + <td class="tdl">Fat</td> + <td class="tdc"> 4.1</td> + </tr> + </tbody> +</table> + +<p><span class="pagenum"><a id="Page_466"></a>[Pg 466]</span> +The quantity of solids and fat in milk is less after longer than after +shorter periods between milkings.</p> + +<p>The quantity of solids and fat in cow milk is less in the spring than +in the autumn.</p> + +<p>The chief organic acid naturally present in milk is citric, which +exists probably in combination with lime.</p> + +<p>The mean content of citric acid in milk is about one-tenth of one per +cent.<a id="FNanchor_403" href="#Footnote_403" class="fnanchor">[403]</a></p> + +<p>Citric acid is not found in human milk, and probably exists only in the +mammary secretions of herbivores.</p> + +<p>Among the mineral acids of milk, phosphoric is the most important, but +a part of the phosphorus found as phosphoric acid in the ash of milk +may come from pre-existing organic phosphorus (lecithin, nuclein).</p> + +<p>The sulfuric acid, which is found in the ash of milk, is derived from +the sulfur of the proteid matter during ignition.</p> + +<p>Lactic acid is developed from lactose during the souring of milk as the +result of bacterial activity.</p> + +<p>Gases are also found in solutions of milk, notably carbon dioxid, which +gives to freshly drawn milk its brothy appearance.</p> + +<p>The ash of milk has the following composition expressed as grams per +liter of the original milk:<a id="FNanchor_404" href="#Footnote_404" class="fnanchor">[404]</a></p> + +<table class="spb1"> + <thead><tr> + <th class="tdc bb">Component.</th> + <th class="tdc bb">Grams<br>per liter.</th> + <th class="tdc bb">Probable form<br>of combination.</th> + <th class="tdc bb">Grams<br>per liter.</th> + </tr></thead> + <tbody><tr> + <td class="tdl bb" rowspan="2">Chlorin</td> + <td class="tdr bb" rowspan="2">0.90</td> + <td class="tdl_ws1">sodium chlorid</td> + <td class="tdr">0.962</td> + </tr><tr> + <td class="tdl_ws1 bb">potassium chlorid</td> + <td class="tdr bb">0.830</td> + </tr><tr> + <td class="tdl bb" rowspan="5">Phosphoric acid</td> + <td class="tdr bb" rowspan="5">2.42</td> + <td class="tdl_ws1">KH₂PO₄</td> + <td class="tdr">1.156</td> + </tr><tr> + <td class="tdl_ws1">K₂HPO₄</td> + <td class="tdr">0.853</td> + </tr><tr> + <td class="tdl_ws1">MgHPO₄</td> + <td class="tdr">0.336</td> + </tr><tr> + <td class="tdl_ws1">CaHPO₄</td> + <td class="tdr">0.671</td> + </tr><tr> + <td class="tdl_ws1 bb">Ca₃(PO₄)₂</td> + <td class="tdr bb">0.806</td> + </tr><tr> + <td class="tdl"></td> + <td class="tdr"></td> + <td class="tdl_ws1"></td> + <td class="tdr"></td> + </tr><tr> + <td class="tdl bb" rowspan="2">Potassium</td> + <td class="tdr bb" rowspan="2">1.80</td> + <td class="tdl_ws1">(as shown above)</td> + <td class="tdr"> </td> + </tr><tr> + <td class="tdl_ws2 bb">and as potassium citrate</td> + <td class="tdr bb">0.495</td> + </tr><tr> + <td class="tdl bb">Sodium</td> + <td class="tdr bb">0.49</td> + <td class="tdl_ws1 bb">sodium chlorid</td> + <td class="tdr bb">0.962</td> + + </tr><tr> + <td class="tdl bb" rowspan="2">Lime</td> + <td class="tdr bb" rowspan="2">1.90</td> + <td class="tdl_ws1">(as shown above)</td> + <td class="tdr"> </td> + </tr><tr> + <td class="tdl_ws2 bb">and as calcium citrate</td> + <td class="tdr bb">2.133</td> + </tr><tr> + <td class="tdl bb">Magnesia</td> + <td class="tdr bb">0.20</td> + <td class="tdl_ws1 bb">MgHPO₄</td> + <td class="tdr bb">0.336</td> + </tr> + </tbody> +</table> + +<p>The percentage composition of the ash of milk, according to Fleischmann +<span class="pagenum"><a id="Page_467"></a>[Pg 467]</span> +and Schrott, is expressed as follows:<a id="FNanchor_405" href="#Footnote_405" class="fnanchor">[405]</a></p> + +<table class="spb1"> + <tbody><tr> + <td class="tdr" colspan="3">Per cent.</td> + </tr><tr> + <td class="tdl">Potassium oxid,</td> + <td class="tdl_wsp fs_105">K₂O</td> + <td class="tdr_wsp">25.42</td> + </tr><tr> + <td class="tdl">Sodium oxid,</td> + <td class="tdl_wsp fs_105">Na₂O</td> + <td class="tdr_wsp">10.94</td> + </tr><tr> + <td class="tdl">Calcium oxid,</td> + <td class="tdl_wsp fs_105">CaO</td> + <td class="tdr_wsp">21.45</td> + </tr><tr> + <td class="tdl">Magnesium oxid,</td> + <td class="tdl_wsp fs_105">MgO</td> + <td class="tdr_wsp">2.54</td> + </tr><tr> + <td class="tdl">Iron oxid,</td> + <td class="tdl_wsp fs_105">Fe₂O₃</td> + <td class="tdr_wsp">0.11</td> + </tr><tr> + <td class="tdl">Sulfuric acid,</td> + <td class="tdl_wsp fs_105">SO₃</td> + <td class="tdr_wsp">4.11</td> + </tr><tr> + <td class="tdl">Phosphoric acid,</td> + <td class="tdl_wsp fs_105">P₂O₅</td> + <td class="tdr_wsp">24.11</td> + </tr><tr> + <td class="tdl">Chlorin,</td> + <td class="tdl_wsp fs_105">Cl</td> + <td class="tdr_wsp bb">14.60</td> + </tr><tr> + <td class="tdl" colspan="2"> </td> + <td class="tdr_wsp">103.28</td> + </tr><tr> + <td class="tdl">Less</td> + <td class="tdl_wsp">Cl as O  </td> + <td class="tdr_wsp bb">3.28</td> + </tr><tr> + <td class="tdl" colspan="2"> </td> + <td class="tdr_wsp">100.00</td> + </tr> + </tbody> +</table> + +<p><b>428. Alterability of Milk.</b>—The natural souring and coagulation +of milk is attributed by most authorities to bacterial action produced +by infection from the air or containing vessels.<a id="FNanchor_406" href="#Footnote_406" class="fnanchor">[406]</a> +Pasteur, however, shows that fresh milk sterilized at a temperature of +110° may be exposed to the air without danger of souring.<a id="FNanchor_407" href="#Footnote_407" class="fnanchor">[407]</a> +After about three days, however, a fermentation is set up which is +totally different from that produced by the microzymes naturally +present in the milk. This point has been further investigated by +Béchamp, who finds that the natural souring of milk is accomplished +without the evolution of any gas, while the fermentation produced in +sterilized milk by the microbes of the air, is uniformly attended by a +gaseous development.<a id="FNanchor_408" href="#Footnote_408" class="fnanchor">[408]</a> +As a result of his investigations, he concludes that the souring of +milk takes place spontaneously by reason of milk being an organic +matter, in the physiological sense of the term, and that this +alteration is produced solely by the natural microzymes of the milk.</p> + +<p>According to Béchamp, the milk derived from healthy animals is capable +of spontaneous alteration, which consists in the development of lactic +acid and alcohol, and of curd in those milks which contain caseinates +produced by the precipitating action of the acids formed. Oxygen and +the germs which are present in the air, according to him, have nothing +to do with this alteration in the properties of milk. Milk belongs to +that class of organic bodies like blood, which are called organic from +a physiological point of view, on account of containing automatic forces +<span class="pagenum"><a id="Page_468"></a>[Pg 468]</span> +which produce rapid changes therein when they are withdrawn from the +living organisms.</p> + +<p>After milk has become sour by the spontaneous action of the microzymes +which it contains, there are developed micro-organisms, such as +vibriones and bacteria from a natural evolution from the microzymes.</p> + +<p>Milk which is sterilized at a high temperature, <i>viz.</i>, that of +boiling water or above, is no longer milk in the true physiological +sense of that term. The globules of the milk undergo changes and +the microzymes a modification of their functions, so that in milk +thus altered by heat, they are able to produce a coagulation without +development of acidity. The microzymes thus modified, however, retain +to a large extent their ability to become active. Human milk differs +from cow milk in containing neither caseinates nor casein, but special +proteid bodies, and also a galactozyme or galactozymase functionally +very different from that which exists in cow milk. The extractive +matter is also a special kind, consisting of milk globules and +microzymes belonging particularly to it and containing three times less +phosphate and mineral salts than cow milk. Boiling the milk of the cow +or other animals does not render it similar to that of woman. There is +no treatment, therefore, of any milk which renders it entirely suited +to the nourishment of infants. The composition of the milk of the cow +may be represented by three groups:</p> + +<p>1. Organic elements in suspension; consisting chiefly of the globules +of the milk, which are mostly composed of the fat, of an epidermoid +membrane containing mineral matter of special soluble albumins and of +microzymes containing also mineral matter.</p> + +<p>2. Dissolved constituents; consisting of caseinates, lactalbuminates, +galactozymase, holding phosphates in combination, lactose, extractive +matter, organic phosphates of lime, acetates, urea and alcohol.</p> + +<p>3. Mineral matters in solution; consisting of sodium and calcium +chlorids, carbon dioxid and oxygen.<a id="FNanchor_409" href="#Footnote_409" class="fnanchor">[409]</a></p> + +<p>It will be noticed from the above classification that Béchamp fails to +mention citrate of lime. It is scarcely necessary to add to this brief +<span class="pagenum"><a id="Page_469"></a>[Pg 469]</span> +résumé of the theories of Béchamp that they are entirely at variance +with the opinions held by nearly all his contemporaries.</p> + +<p><b>429. Effects of Boiling on Milk.</b>—On boiling, the albumin in +milk is coagulated and on separating the proteid bodies by saturation +with magnesium sulfate no albumin is found in the filtrate. The total +casein precipitated from boiled is therefore greater than from unboiled +milk. Jager has shown that the casein can be precipitated from boiled +milk by rennet, but with greater difficulty than from unboiled.<a id="FNanchor_410" href="#Footnote_410" class="fnanchor">[410]</a> +According to this author in 3.75 per cent of proteid in milk there are +found 3.15 per cent of casein, 0.35 of albumin and 0.25 of globulin.</p> + +<p><b>430. Appearance of the Milk.</b>—The color, taste, odor and other +sensible characters of the milk are to be observed and noted at the +time the sample is secured. Any variation from the faint yellow color +of the milk is due to some abnormal state. A reddish tint indicates +the admixture of blood, while a blue color is characteristic of the +presence of unusual micro-organisms. Odor and taste will reveal often +the character of the food which the animals have eaten. Any marked +departure of the sample from the properties of normal milk should at +once lead to its condemnation for culinary or dietetic purposes.</p> + +<p><b>431. Micro-Organisms of the Milk.</b>—Milk is a natural culture +solution for the growth of micro-organisms, and they multiply therein +with almost incredible rapidity. Some of these are useful, as, for +instance, those which are active in the ripening of cream, and others +are of an injurious nature, producing fermentations which destroy the +sugars or proteids of the milk and develop acid, alcohol, mucous or +ptomaine products. It is not possible here to even enumerate the kinds +of micro-organisms which abound in milk and the reader is referred to +the standard works on that subject.<a id="FNanchor_411" href="#Footnote_411" class="fnanchor">[411]</a></p> + +<p>For analytical purposes it is important that the sample be kept as +free as possible of all micro-organisms, good or bad, which may be +accomplished by some of the methods given below.</p> + +<p><b>432. Sampling Milk.</b>—It is not difficult to secure for +<span class="pagenum"><a id="Page_470"></a>[Pg 470]</span> +examination representative samples of milk, if the proper precautions +be taken. On the other hand, the ease and rapidity with which a milk +undergoes profound changes render necessary a careful control of the +methods of taking samples. The most rapid changes to which a mass of +milk is obnoxious are due to the separation of the fat particles and +to the action of bacteria. Even after standing for a few minutes, it +will be found that the fat globules are not evenly distributed. Before +securing the sample for analysis, it is necessary to well stir or mix +the milk. A mean sample may also be secured from a can of milk by the +sampling tube devised by Scovell, which will be described below.</p> + +<p>In securing samples, a full detailed description of the cow or herd +furnishing them is desirable, together with all other data which seem +to illustrate in any way the general and particular conditions of the +dairy. Samples are to be preserved in clean, well stoppered vessels, +properly numbered and securely sealed.</p> + +<div class="figcenter smcap"> + <img id="FIG_106" src="images/fig106.jpg" alt="" width="600" height="233" > + <p class="center spb1">Fig. 106.—Scovell’s Milk Sampling Tube.</p> +</div> + +<p><b>433. Scovell’s Milk Sampler.</b>—In sampling large quantities of +milk in pails or shipping cans, it is exceedingly inconvenient to mix +the milk by pouring from one vessel to another or by any easy process +of stirring. In order to get representative samples in such conditions, +Scovell has put in use a sampler, by means of which a typical portion +of the milk may be withdrawn from a can without either pouring or +stirring. The construction of the sampler is shown in <a href="#FIG_106">Fig. 106</a>, +representing it in outline and longitudinal section. The tube <i>a</i>, +made of brass, is open at both ends and of any convenient dimensions. +Its lower end slides in a large tube <i>b</i>, closed at the bottom and +having three elliptical, lateral openings <i>c</i>, which admit the +milk as the tube is slowly depressed in the contents of the can. In +<span class="pagenum"><a id="Page_471"></a>[Pg 471]</span> +getting the sample, <i>a</i> is raised as shown in profile. When the +bottom of <i>b</i> reaches the bottom of the can <i>a</i> is pushed +down as shown in the section. The milk contained in the sampler is then +readily withdrawn.</p> + +<p><b>434. Preserving Milk for Analysis.</b>—Pasteurizing or boiling the +sample is not advisable by reason of the changes produced in the milk +by heat. The milk sample may be preserved by adding to it a little +chloroform, one part in 100 being sufficient. Boric and salicylic acids +may also be used, but not so advantageously as formaldehyd or mercuric +chlorid. Rideal has observed that one part of formaldehyd will preserve +10,000 parts of milk in a fresh state for seven days. The formaldehyd +sold in the trade contains about one part of formaldehyd in 320 of +the mixture. One-half pint of this commercial article is sufficient +for about twenty gallons of milk, corresponding to about one part of +pure formaldehyd to 45,000 parts of milk. Rideal much prefers formalin +(formaldehyd) to borax or boric acid as a milk preservative. No ill +effects due to its toxic action have been observed, even when it is +consumed in a one per cent solution.<a id="FNanchor_412" href="#Footnote_412" class="fnanchor">[412]</a></p> + +<p>Samples of milk can be kept in this way from four to six weeks by +adding about one drop of the commercial formaldehyd to each ounce of +sample. The analyst should remember in such cases that the formaldehyd +may not all escape on evaporation, on account of forming some kind of +a compound with the constituents of the milk, as is pointed out by +Bevan.<a id="FNanchor_413" href="#Footnote_413" class="fnanchor">[413]</a></p> + +<p>Bevan suggests that the formaldehyd may not actually be retained in the +sample, but that the increase in the apparent amount of total solids +is due to the conversion of the lactose into galactose. This point, +however, has not been determined.</p> + +<p>Richmond and Boseley propose to detect formalin by means of +diphenylamin. A solution of diphenylamin is made with water, with the +help of just enough sulfuric acid to secure a proper solvent effect. +The liquid to be tested, which is supposed to contain formaldehyd, or +the distillate therefrom, is added to this solution and boiled. If +formaldehyd be present, a white flocculent precipitate is deposited, +which is colored green if the acid used contain nitrates. For other +methods of detecting formalin and for a partial literature of the +subject the paper mentioned above may be consulted. +<span class="pagenum"><a id="Page_472"></a>[Pg 472]</span></p> + +<p>One gram of fine-ground mercuric chlorid dissolved in 2,000 grams of +milk will preserve it, practically unchanged, for several days. One +gram of potassium bichromate dissolved in one liter of milk will also +preserve it for some time. Thymol, hydrochloric acid, carbon disulfid, +ether and other antiseptics may also be employed. No more of the +preserving agent should be used than is required to keep the milk until +the analysis is completed.</p> + +<p>All methods of preservation are rendered more efficient by the +maintenance of a low temperature, whereby the vitality of the bacteria +is greatly reduced.</p> + +<p><b>435. Freezing Point of Milk.</b>—By reason of its content of sugar +and other dissolved solids, the freezing point of milk is depressed +below 0°. A good idea of the purity of whole milk is secured by +subjecting it to a kryoscopic test. The apparatus employed for this +purpose is that used in general analytical work in the determination of +freezing points. Pure full milk freezes at about 0°.55 below zero, and +any marked variation from this number shows adulteration or abnormal +composition.<a id="FNanchor_414" href="#Footnote_414" class="fnanchor">[414]</a> +A simple apparatus, especially adapted to milk, is described by +Beckmann.<a id="FNanchor_415" href="#Footnote_415" class="fnanchor">[415]</a> +The kryoscopic investigation may also be extended to butter fat +dissolved in benzol.</p> + +<p><b>436. Electric Conductivity of Milk.</b>—The electric conductivity +of milk may also be used as an index of its composition. The addition +of water to milk diminishes its conductivity.<a id="FNanchor_416" href="#Footnote_416" class="fnanchor">[416]</a> +This method of investigation has at present but little practical value.</p> + +<p><b>437. Viscosity Of Milk.</b>—The viscosity of milk may be determined +by the methods already described. Any variation from the usual degree +of fluidity is indicated either by the abstraction of some of the contents +of the milk, the addition of some adulterant or the result of fermentation.</p> + +<p><b>438. Acidity and Alkalinity of Milk.</b>—Fresh milk of normal +constitution has an amphoteric reaction. It will redden blue and blue +red litmus paper. This arises from the presence in the milk of both +neutral and acid phosphates of the alkalies. A saturated alkaline +phosphate, <i>i. e.</i>, one in which all the acid hydrogen of the acid +<span class="pagenum"><a id="Page_473"></a>[Pg 473]</span> +has been replaced by the base has an alkaline reaction while the +acid phosphates react acid. When fresh milk is boiled its reaction +becomes strongly alkaline and this arises chiefly from the escape +of the dissolved carbon dioxid. By the action of micro-organisms on +the lactose of milk, the alkaline reaction soon becomes acid, and +delicate test paper will show this decomposition long before it becomes +perceptible to the taste. It is advisable to test the reactions of the +milk as soon as possible after it is drawn from the udder, both before +and after boiling.</p> + +<p><b>439. Determination of the Acidity of Milk.</b>—In the determination +of the acidity of milk it is important that it first be freed of the +carbon dioxid it contains.<a id="FNanchor_417" href="#Footnote_417" class="fnanchor">[417]</a> +Van Slyke has found that too high results are obtained by the direct +titration of milk for acidity, and when the milk is previously diluted +the results are also somewhat too high.<a id="FNanchor_418" href="#Footnote_418" class="fnanchor">[418]</a> +Good results are got by diluting the milk with hot water and boiling +for a short time to expel the carbon dioxid. Twenty-five cubic +centimeters of milk are diluted with water to about a quarter of a +liter, as above, two cubic centimeters of a one per cent alcoholic +phenolphthalien added and the titration accomplished by decinormal +alkali. This variation of the methods of procedure, suggested by +Hopkins and Powers, appears to be the best process at present known for +the determination of acidity. The reader is referred to the paper cited +above for references to other methods which have been proposed.</p> + +<p><b>440. Opacity Of Milk.</b>—The white color and opacity of milk are +doubtless due to the presence of the suspended fat particles and to +the colloid casein. On the latter it is probably principally dependent +since the color of milk is not very sensibly changed after it has +passed the extractor, which leaves not to exceed one-tenth of one per +cent of fat in it. Some idea of the quality of the milk, however, may +be obtained by determining its opacity. This is accomplished by the use +of a lactoscope. The one generally employed was devised by Feser and is +shown in <a href="#FIG_107">Fig. 107</a>.</p> + +<p>The instrument consists of a cylindrical glass vessel of a little more +<span class="pagenum"><a id="Page_474"></a>[Pg 474]</span> +than 100 cubic centimeters content, in the lower part of which is set a +cone of white glass marked with black lines. Into this part are placed +four cubic centimeters of milk. A small quantity of water is added and +the contents of the vessel shaken. This operation is repeated until the +black lines on the white glass just become visible. The graduations on +the left side show the volume of water which is necessary to bring the +dark lines into view, while those on the right indicate approximately +the percentage of fat present.</p> + +<p>Among the other lactoscopes which have been used may be mentioned +those of Donné, Vogel, Hoppe-Seyler, Trommer, Seidlitz, Reischauer, +Mittelstrass, Hénocque, and Heusner.<a id="FNanchor_419" href="#Footnote_419" class="fnanchor">[419]</a> +Since the invention of so many quick and accurate methods of fat +estimation these instruments have little more than a historical interest.</p> + +<div class="figcenter smcap"> + <img id="FIG_107" src="images/fig107.jpg" alt="" width="600" height="268" > + <p class="center spb1">Fig. 107.—Lactoscope, Lactometer and Creamometer.</p> +</div> + +<p><b>441. Creamometry.</b>—The volume of cream which a sample of milk +affords under arbitrary conditions of time and temperature is sometimes +of value in judging the quality of milk. A convenient creamometer is +a small cylinder graduated in such a way that the volume of cream +separated in a given time can be easily noted. There are many kinds of +apparatus used for this purpose, a typical one being shown in <a href="#FIG_107">Fig. 107</a>.</p> + +<p>The usual time of setting is twenty-four hours. A quicker determination +is secured by placing the milk in strong glass graduated tubes and +subjecting these to centrifugal action. The process is not exact and +is now rarely practiced as an analytical method, even for valuing the +butter making properties of milk.</p> + +<p><b>442. Specific Gravity.</b>—The specific gravity of milk is +uniformly referred to a temperature of 15°. Generally no attempt is made +<span class="pagenum"><a id="Page_475"></a>[Pg 475]</span> +to free the milk of dissolved gases beforehand. This should not be +done by boiling but by placing the sample in a vacuum for some time. +Any of the methods described for determining specific gravity in sugar +solutions may be used for milk (<b><a href="#P_48">48-59</a></b>). The specific gravity of +milk varies in general from 1.028 to 1.034. Nearly all good cow milk +from herds will show a specific gravity varying from 1.030 to 1.032. In +extreme cases from single cows the limits may exceed those first given +above, but such milk cannot be regarded as normal.</p> + +<p>Increasing quantities of solids not fat in solution, tend to increase +the specific gravity, while an excess of fat tends to diminish it. +There is a general ratio existing between the solids not fat and the +fat in cow milk, which may be expressed as 9: 4. The removal of +cream and the addition of water in such a manner as not to affect the +specific gravity of the sample disturbs this ratio.</p> + +<p>The determination of the specific gravity alone, therefore, cannot be +relied upon as an index of the purity of a milk.</p> + +<p><b>443.</b> <b>Lactometry.</b>—A hydrometer especially constructed +for use in determining the density of milk is called a lactometer. In +this country the one most commonly used is known as the lactometer +of the New York Board of Health. It is a hydrometer, delicately +constructed, with a large cylindrical air space and a small stem +carrying the thermometric and lactometric scales. It is shown held +in the creamometer in <a href="#FIG_107">Fig. 107</a>. The milk is brought +to a temperature of 60° F. and the reading of the lactometer scale +observed. This is converted into a number expressing the specific +gravity by means of a table of corresponding values given below. Each +mark on the scale of the instrument corresponds to two degrees and +these marks extend from 0° to 120°. The numbers of this scale can be +converted into those corresponding to the direct reading instrument, +described in the next paragraph, by multiplying them by 0.29.</p> + +<p>The minimum density for whole milk at 60° F. is fixed by this +instrument at 100°, corresponding to a specific gravity of 1.029. The +instrument is also constructed without the thermometric scale. The mean +<span class="pagenum"><a id="Page_476"></a>[Pg 476]</span> +density of many thousand samples of pure milk, as observed by the New +York authorities, is 1.0319.</p> + +<p>The specific gravity is easily secured, and while not of itself +decisive, should always be determined. The specific gravity of milk +increases for some time after it is drawn and should be made both when +fresh and after the lapse of several hours.<a id="FNanchor_420" href="#Footnote_420" class="fnanchor">[420]</a></p> + +<p class="f120"><b><span class="smcap">Table Showing Specific Gravities Corresponding<br> +to Degrees of the New York Board Of Health<br>Lactometer. Temperature 60° F.</span></b></p> + +<table class="spb1"> + <thead><tr> + <th class="tdc bb"> Degree. </th> + <th class="tdc bb"> Sp. gr. </th> + <th class="tdc bb"> Degree. </th> + <th class="tdc bb"> Sp. gr. </th> + </tr></thead> + <tbody><tr> + <td class="tdc"> 90</td> + <td class="tdc">1.02619</td> + <td class="tdc">106</td> + <td class="tdc">1.03074</td> + </tr><tr> + <td class="tdc"> 91</td> + <td class="tdc">1.02639</td> + <td class="tdc">107</td> + <td class="tdc">1.03103</td> + </tr><tr> + <td class="tdc"> 92</td> + <td class="tdc">1.02668</td> + <td class="tdc">108</td> + <td class="tdc">1.03132</td> + </tr><tr> + <td class="tdc"> 93</td> + <td class="tdc">1.02697</td> + <td class="tdc">109</td> + <td class="tdc">1.03161</td> + </tr><tr> + <td class="tdc"> 94</td> + <td class="tdc">1.02726</td> + <td class="tdc">110</td> + <td class="tdc">1.03190</td> + </tr><tr> + <td class="tdc"> 95</td> + <td class="tdc">1.02755</td> + <td class="tdc">111</td> + <td class="tdc">1.03219</td> + </tr><tr> + <td class="tdc"> 96</td> + <td class="tdc">1.02784</td> + <td class="tdc">112</td> + <td class="tdc">1.03248</td> + </tr><tr> + <td class="tdc"> 97</td> + <td class="tdc">1.02813</td> + <td class="tdc">113</td> + <td class="tdc">1.03277</td> + </tr><tr> + <td class="tdc"> 98</td> + <td class="tdc">1.02842</td> + <td class="tdc">114</td> + <td class="tdc">1.03306</td> + </tr><tr> + <td class="tdc"> 99</td> + <td class="tdc">1.02871</td> + <td class="tdc">115</td> + <td class="tdc">1.03335</td> + </tr><tr> + <td class="tdc">100</td> + <td class="tdc">1.02900</td> + <td class="tdc">116</td> + <td class="tdc">1.03364</td> + </tr><tr> + <td class="tdc">101</td> + <td class="tdc">1.02929</td> + <td class="tdc">117</td> + <td class="tdc">1.03393</td> + </tr><tr> + <td class="tdc">102</td> + <td class="tdc">1.02958</td> + <td class="tdc">118</td> + <td class="tdc">1.03422</td> + </tr><tr> + <td class="tdc">103</td> + <td class="tdc">1.02987</td> + <td class="tdc">119</td> + <td class="tdc">1.03451</td> + </tr><tr> + <td class="tdc">104</td> + <td class="tdc">1.03016</td> + <td class="tdc">120</td> + <td class="tdc">1.03480</td> + </tr><tr> + <td class="tdc">105</td> + <td class="tdc">1.03045</td> + <td class="tdc"> </td> + <td class="tdc"> </td> + </tr> + </tbody> +</table> + +<p><b>444.</b> <b>Direct Reading Lactometer.</b>—A more convenient form +of lactometer is one which gives the specific gravity directly on the +scale. The figures given represent those found in the second and third +decimal places of the number expressing the specific gravity. Thus 31 +on the scale indicates a specific gravity of 1.031. This instrument is +also known as the lactometer of Quévenne. For use with milk, the scale +of the instrument does not need to embrace a wider limit than from +25 to 35, and such an instrument is capable of giving more delicate +readings than when the scale extends from 14 to 42, as is usually the +case with the quévenne instrument.</p> + +<p>Langlet has invented a lactoscope with a scale, showing the corrections +to be applied for temperatures other than 15°. A detailed description +of this instrument, as well as the one proposed by Pinchon, is +unnecessary.<a id="FNanchor_421" href="#Footnote_421" class="fnanchor">[421]</a></p> + +<p><span class="pagenum"><a id="Page_477"></a>[Pg 477]</span> +<b>445. Density of Sour Milk.</b>—Coagulated milk cannot be used +directly for the determination of the specific gravity, both because of +its consistence and by reason of the fact that the fat is more or less +completely separated. In such a case, the casein may be dissolved by +the addition of a measured quantity of a solvent of a known specific +gravity, the density of the resulting solution determined and that +of the original milk calculated from the observed data. Ammonia is a +suitable solvent for this purpose.<a id="FNanchor_422" href="#Footnote_422" class="fnanchor">[422]</a></p> + +<p><b>446. Density of the Milk Serum.</b>—The specific gravity of the +milk serum, after the removal of the fat and casein by precipitation +and filtration, may also be determined. For normal cow milk the number +is about 1.027.</p> + +<p id="P_447"><b>447. Total Solids.</b>—The direct gravimetric determination of the +total solids in milk is attended with many difficulties, and has been +the theme of a very extended periodical literature. A mere examination +of the many processes which have been proposed would require several +pages.</p> + +<p>The most direct method of procedure is to dry a small quantity of milk +in a flat-bottom dish to constant weight on a steam-bath. The surface +of the dish should be very large, even for one or two grams of milk; +in fact the relation between the quantity of milk and the surface of +the dish should be such that the fluid is just sufficient in amount to +moisten the bottom of the dish with the thinnest possible film. The +dish, during drying, is kept in a horizontal position at least until +its contents will not flow. The water of the sample will be practically +all evaporated in about two hours. The operation may be accelerated by +drying in vacuo.</p> + +<p>The drying may also be accomplished by using a flat-bottom dish +containing some absorbent, such as sand, pumice stone, asbestos or +crysolite. The milk may also be absorbed by a dried paper coil and +dried thereon (<b><a href="#P_26">26</a></b>).</p> + +<p>It is convenient to determine the water in the sample subsequently +to be used for the gravimetric determination of the fat, and this is +secured by the adoption of the paper coil method, as suggested by the +author, or by the use of a perforated metal tube containing porous +asbestos, as proposed by Babcock.<a id="FNanchor_423" href="#Footnote_423" class="fnanchor">[423]</a></p> + +<p><span class="pagenum"><a id="Page_478"></a>[Pg 478]</span> +The process is conveniently carried out as follows:</p> + +<p>Provide a hollow cylinder of perforated sheet metal sixty millimeters +long and twenty millimeters in diameter, closed five millimeters from +one end by a disk of the same material. The perforations should be +about 0.7 millimeter in diameter and as close together as possible. +Fill loosely with from one and a half to two and a half grams of dry +woolly asbestos and weigh. Introduce a weighed quantity of milk (about +five grams). Dry at 100° for four hours. During the first part of the +drying the door of the oven should be left partly open to allow escape +of moisture. Cool in a desiccator and weigh. Repeat the drying until +the weight remains constant. Place in an extractor and treat with +anhydrous ether for two hours. Evaporate the ether and dry the fat at +100°. The extracted fat is weighed and the number thus obtained may be +checked by drying and weighing the cylinder containing the residue.</p> + +<p>The asbestos best suited for use in this process should be of a woolly +nature, quite absorbent, and, previous to use, be ignited to free it +of moisture and organic matter. A variety of serpentine, crysolite is +sometimes used instead of asbestos. When the content of water alone is +desired, it is accurately determined by drying in vacuo over pumice +stone (<a href="#Page_33">page 33</a>).</p> + +<p>The methods above mentioned are typical and will prove a sufficient +guide for conducting the desiccation, either as described or by any +modification of the methods which may be preferred.</p> + +<p><b>448. Calculation of Total Solids.</b>—By reason of the ease and +celerity with which the density of a milk and its content of fat +can be obtained, analysts have found it convenient to calculate the +percentage of total solids instead of determining it directly. This +is accomplished by arbitrary formulas based on the data of numerous +analyses. These formulas give satisfactory results when the samples do +not vary widely from the normal and may be used with advantage in most cases.</p> + +<p>Among the earliest formulas for the calculation may be mentioned those +of Fleischmann and Morgen,<a id="FNanchor_424" href="#Footnote_424" class="fnanchor">[424]</a> +Behrend and Morgen,<a id="FNanchor_425" href="#Footnote_425" class="fnanchor">[425]</a> +Claus, Stutzer and Meyer,<a id="FNanchor_426" href="#Footnote_426" class="fnanchor">[426]</a> Hehner,<a id="FNanchor_427" href="#Footnote_427" class="fnanchor">[427]</a> +and Hehner and Richmond.<a id="FNanchor_428" href="#Footnote_428" class="fnanchor">[428]</a> +Without doing more than citing these papers it will be sufficient here +<span class="pagenum"><a id="Page_479"></a>[Pg 479]</span> +to give the formulas as corrected by the most recent experience.</p> + +<p>In the formula worked out by Babcock the specific gravity of the sample +is represented by <i>S</i>, the fat by <i>F</i>, and the solids not fat +by <i>t</i>. The formula is written as follows:<a id="FNanchor_429" href="#Footnote_429" class="fnanchor">[429]</a></p> + +<table class="spb1 fs_105"> + <tbody><tr> + <td class="tdl" rowspan="2"><i>t</i> = <span class="fs_200">(</span> </td> + <td class="tdc bb">100<i>S</i> - <i>FS</i></td> + <td class="tdl" rowspan="2"><span class="fs_200"> )</span> + (250 - 2.5 <i>F</i>).</td> + </tr><tr> + <td class="tdc">100 - 1.0753<i>FS</i></td> + </tr> + </tbody> +</table> + +<p>In this formula it is assumed that the difference between the specific +gravity of the milk serum and that of water is directly proportional +to the per cent of solids in the serum, but this assumption is not +strictly correct. Even in extreme cases, however, the error does not +amount to more than 0.05 per cent.</p> + +<p>Since a given amount of milk sugar increases the density of a milk +more than the same quantity of casein, it is evident that the formula +would not apply to those instances in which the ratio between these two +ingredients is greatly disturbed, as for instance, the whey.</p> + +<p>The formula of Hehner and Richmond, in its latest form, is expressed as +follows:</p> + +<table class="spb1 fs_105"> + <tbody><tr> + <td class="tdl" rowspan="2"><i>T</i> = 0.2625 </td> + <td class="tdc bb"> <i>G</i> </td> + <td class="tdl" rowspan="2"> + 1.2<i>F</i>,</td> + </tr><tr> + <td class="tdc"><i>D</i></td> + </tr> + </tbody> +</table> + +<p class="no-indent">in which <i>T</i> represents the total solids, +<i>G</i> the reading of the quévenne lactometer, <i>D</i> the specific +gravity, and <i>F</i> the fat.</p> + +<div class="blockquot"> +<p><i>Example.</i>—Let the reading of the lactometer be 31, corresponding +to <i>D</i> 1.031, and the percentage of fat be three and five-tenths, +what is the percentage of the total solids?</p> + +<p>Substituting these values in the formulas we have</p> + +<table class="spb1 fs_105"> + <tbody><tr> + <td class="tdl" rowspan="2"><i>T</i> = 0.2625 </td> + <td class="tdc bb">31</td> + <td class="tdl" rowspan="2"> + 1.2 × 3.5 = 12.09.</td> + </tr><tr> + <td class="tdc">1.031</td> + </tr> + </tbody> +</table> + +<p>To simplify the calculations, Richmond’s formula may be written</p> + +<table class="spb1 fs_105"> + <tbody><tr> + <td class="tdl" rowspan="2"><i>T</i> = </td> + <td class="tdc bb"> <i>G</i> </td> + <td class="tdl" rowspan="2"> + </td> + <td class="tdc bb"> 6<i>F</i> </td> + <td class="tdl" rowspan="2"> + 0.14.</td> + </tr><tr> + <td class="tdc">4</td> + <td class="tdc">5</td> + </tr> + </tbody> +</table> + +<p>Calculated by this shortened formula from the above data <i>T</i> = +12.09, the same as given in the larger formula.</p> +</div> + +<p>Calculating the solids not fat in the hypothetical case given above +by Babcock’s formula, we get <i>t</i> = 8.46, and this plus 3.5 gives 11.96, +which is slightly lower than the number obtained by the richmond process. +<span class="pagenum"><a id="Page_480"></a>[Pg 480]</span></p> + +<p>The babcock formula may be simplified by substituting the number +expressing the reading of the quévenne lactometer for that donating the +specific gravity, in other words, the specific gravity multiplied by +100 and the quotient diminished by 1000.</p> + +<p>The formulas for solids not fat and total solids then become</p> + +<table class="spb1 fs_105"> + <tbody><tr> + <td class="tdl" rowspan="2"><i>t</i> = </td> + <td class="tdc bb"> <i>L</i> </td> + <td class="tdl" rowspan="2"> + 0.2<i>F</i>, and <i>T</i> = </td> + <td class="tdc bb"> <i>L</i> </td> + <td class="tdl" rowspan="2"> + 1.2<i>F</i>,</td> + </tr><tr> + <td class="tdc">4</td> + <td class="tdc">4</td> + </tr> + </tbody> +</table> + +<p class="no-indent">in which <i>L</i> represents the reading of the +lactometer. By the addition of the constant factor 0.14 the results +calculated by the formula of Babcock are the same as those obtained by +the method of Richmond.</p> + +<p>In the following table are given the solids not fat in milks as +calculated by Babcock’s formula. To obtain the total solids add the +per cent of fat to solids not fat. To obtain total solids according to +Richmond’s formula increase that number by 0.14.</p> + +<p class="f120"><b><span class="smcap">Table Showing Per Cent of Solids not Fat in Milk<br> +Corresponding to Quévenne’s Lactometer Readings<br>and Per Cent of Fat.</span></b></p> + +<table class="spb1"> + <thead><tr> + <th class="tdc bt">Per<br>cent</th> + <th class="tdc bb bl bt" colspan="11">Lactometer reading at 60° F.</th> + </tr><tr> + <th class="tdc bb br"> of fat. </th> + <th class="tdc bb"> 26. </th> <th class="tdc bb"> 27. </th> + <th class="tdc bb"> 28. </th> <th class="tdc bb"> 29. </th> + <th class="tdc bb"> 30. </th> <th class="tdc bb"> 31. </th> + <th class="tdc bb"> 32. </th> <th class="tdc bb"> 33. </th> + <th class="tdc bb"> 34. </th> <th class="tdc bb"> 35. </th> + <th class="tdc bb"> 36 . </th> + </tr></thead> + <tbody><tr> + <td class="tdc">0.0</td> <td class="tdc">6.50</td> + <td class="tdc">6.75</td> <td class="tdc">7.00</td> + <td class="tdc">7.25</td> <td class="tdc">7.50</td> + <td class="tdc">7.75</td> <td class="tdc">8.00</td> + <td class="tdc">8.25</td> <td class="tdc">8.50</td> + <td class="tdc">8.75</td> <td class="tdc">9.00</td> + </tr><tr> + <td class="tdc">0.1</td> <td class="tdc">6.52</td> + <td class="tdc">6.77</td> <td class="tdc">7.02</td> + <td class="tdc">7.27</td> <td class="tdc">7.52</td> + <td class="tdc">7.77</td> <td class="tdc">8.02</td> + <td class="tdc">8.27</td> <td class="tdc">8.52</td> + <td class="tdc">8.77</td> <td class="tdc">9.02</td> + </tr><tr> + <td class="tdc">0.2</td> <td class="tdc">6.54</td> + <td class="tdc">6.79</td> <td class="tdc">7.04</td> + <td class="tdc">7.29</td> <td class="tdc">7.54</td> + <td class="tdc">7.79</td> <td class="tdc">8.04</td> + <td class="tdc">8.29</td> <td class="tdc">8.54</td> + <td class="tdc">8.79</td> <td class="tdc">9.04</td> + </tr><tr> + <td class="tdc">0.3</td> <td class="tdc">6.56</td> + <td class="tdc">6.81</td> <td class="tdc">7.06</td> + <td class="tdc">7.31</td> <td class="tdc">7.56</td> + <td class="tdc">7.81</td> <td class="tdc">8.06</td> + <td class="tdc">8.31</td> <td class="tdc">8.56</td> + <td class="tdc">8.81</td> <td class="tdc">9.06</td> + </tr><tr> + <td class="tdc">0.4</td> <td class="tdc">6.58</td> + <td class="tdc">6.83</td> <td class="tdc">7.08</td> + <td class="tdc">7.33</td> <td class="tdc">7.58</td> + <td class="tdc">7.83</td> <td class="tdc">8.08</td> + <td class="tdc">8.33</td> <td class="tdc">8.58</td> + <td class="tdc">8.83</td> <td class="tdc">9.08</td> + </tr><tr> + <td class="tdc">0.5</td> <td class="tdc">6.60</td> + <td class="tdc">6.85</td> <td class="tdc">7.10</td> + <td class="tdc">7.35</td> <td class="tdc">7.60</td> + <td class="tdc">7.85</td> <td class="tdc">8.10</td> + <td class="tdc">8.35</td> <td class="tdc">8.60</td> + <td class="tdc">8.85</td> <td class="tdc">9.10</td> + </tr><tr> + <td class="tdc">0.6</td> <td class="tdc">6.62</td> + <td class="tdc">6.87</td> <td class="tdc">7.12</td> + <td class="tdc">7.37</td> <td class="tdc">7.62</td> + <td class="tdc">7.87</td> <td class="tdc">8.12</td> + <td class="tdc">8.37</td> <td class="tdc">8.62</td> + <td class="tdc">8.87</td> <td class="tdc">9.12</td> + </tr><tr> + <td class="tdc">0.7</td> <td class="tdc">6.64</td> + <td class="tdc">6.89</td> <td class="tdc">7.14</td> + <td class="tdc">7.39</td> <td class="tdc">7.64</td> + <td class="tdc">7.89</td> <td class="tdc">8.14</td> + <td class="tdc">8.39</td> <td class="tdc">8.64</td> + <td class="tdc">8.89</td> <td class="tdc">9.14</td> + </tr><tr> + <td class="tdc">0.8</td> <td class="tdc">6.66</td> + <td class="tdc">6.91</td> <td class="tdc">7.16</td> + <td class="tdc">7.41</td> <td class="tdc">7.66</td> + <td class="tdc">7.91</td> <td class="tdc">8.16</td> + <td class="tdc">8.41</td> <td class="tdc">8.66</td> + <td class="tdc">8.91</td> <td class="tdc">9.16</td> + </tr><tr> + <td class="tdc bb">0.9</td> <td class="tdc bb">6.68</td> + <td class="tdc bb">6.93</td> <td class="tdc bb">7.18</td> + <td class="tdc bb">7.43</td> <td class="tdc bb">7.68</td> + <td class="tdc bb">7.93</td> <td class="tdc bb">8.18</td> + <td class="tdc bb">8.43</td> <td class="tdc bb">8.68</td> + <td class="tdc bb">8.93</td> <td class="tdc bb">9.18</td> + </tr><tr> + <td class="tdc">1.0</td> <td class="tdc">6.70</td> + <td class="tdc">6.95</td> <td class="tdc">7.20</td> + <td class="tdc">7.45</td> <td class="tdc">7.70</td> + <td class="tdc">7.95</td> <td class="tdc">8.20</td> + <td class="tdc">8.45</td> <td class="tdc">8.70</td> + <td class="tdc">8.95</td> <td class="tdc">9.20</td> + </tr><tr> + <td class="tdc">1.1</td> <td class="tdc">6.72</td> + <td class="tdc">6.97</td> <td class="tdc">7.22</td> + <td class="tdc">7.47</td> <td class="tdc">7.72</td> + <td class="tdc">7.97</td> <td class="tdc">8.22</td> + <td class="tdc">8.47</td> <td class="tdc">8.72</td> + <td class="tdc">8.97</td> <td class="tdc">9.22</td> + </tr><tr> + <td class="tdc">1.2</td> <td class="tdc">6.74</td> + <td class="tdc">6.99</td> <td class="tdc">7.24</td> + <td class="tdc">7.49</td> <td class="tdc">7.74</td> + <td class="tdc">7.99</td> <td class="tdc">8.24</td> + <td class="tdc">8.49</td> <td class="tdc">8.74</td> + <td class="tdc">8.99</td> <td class="tdc">9.24</td> + </tr><tr> + <td class="tdc">1.3</td> <td class="tdc">6.76</td> + <td class="tdc">7.01</td> <td class="tdc">7.26</td> + <td class="tdc">7.51</td> <td class="tdc">7.76</td> + <td class="tdc">8.01</td> <td class="tdc">8.26</td> + <td class="tdc">8.51</td> <td class="tdc">8.76</td> + <td class="tdc">9.01</td> <td class="tdc">9.26</td> + </tr><tr> + <td class="tdc">1.4</td> <td class="tdc">6.78</td> + <td class="tdc">7.03</td> <td class="tdc">7.28</td> + <td class="tdc">7.53</td> <td class="tdc">7.78</td> + <td class="tdc">8.03</td> <td class="tdc">8.28</td> + <td class="tdc">8.53</td> <td class="tdc">8.78</td> + <td class="tdc">9.03</td> <td class="tdc">9.28</td> + </tr><tr> + <td class="tdc">1.5</td> <td class="tdc">6.80</td> + <td class="tdc">7.05</td> <td class="tdc">7.30</td> + <td class="tdc">7.55</td> <td class="tdc">7.80</td> + <td class="tdc">8.05</td> <td class="tdc">8.30</td> + <td class="tdc">8.55</td> <td class="tdc">8.80</td> + <td class="tdc">9.05</td> <td class="tdc">9.30</td> + </tr><tr> + <td class="tdc">1.6</td> <td class="tdc">6.82</td> + <td class="tdc">7.07</td> <td class="tdc">7.32</td> + <td class="tdc">7.57</td> <td class="tdc">7.82</td> + <td class="tdc">8.07</td> <td class="tdc">8.32</td> + <td class="tdc">8.57</td> <td class="tdc">8.82</td> + <td class="tdc">9.07</td> <td class="tdc">9.32</td> + </tr><tr> + <td class="tdc">1.7</td> <td class="tdc">6.84</td> + <td class="tdc">7.09</td> <td class="tdc">7.34</td> + <td class="tdc">7.59</td> <td class="tdc">7.84</td> + <td class="tdc">8.09</td> <td class="tdc">8.34</td> + <td class="tdc">8.59</td> <td class="tdc">8.84</td> + <td class="tdc">9.09</td> <td class="tdc">9.34</td> + </tr><tr> + <td class="tdc">1.8</td> <td class="tdc">6.86</td> + <td class="tdc">7.11</td> <td class="tdc">7.36</td> + <td class="tdc">7.61</td> <td class="tdc">7.86</td> + <td class="tdc">8.11</td> <td class="tdc">8.36</td> + <td class="tdc">8.61</td> <td class="tdc">8.86</td> + <td class="tdc">9.11</td> <td class="tdc">9.37</td> + </tr><tr> + <td class="tdc bb">1.9</td> <td class="tdc bb">6.88</td> + <td class="tdc bb">7.13</td> <td class="tdc bb">7.38</td> + <td class="tdc bb">7.63</td> <td class="tdc bb">7.88</td> + <td class="tdc bb">8.13</td> <td class="tdc bb">8.38</td> + <td class="tdc bb">8.63</td> <td class="tdc bb">8.88</td> + <td class="tdc bb">9.14</td> <td class="tdc bb">9.39</td> + </tr><tr> + <td class="tdc">2.0</td> <td class="tdc">6.90</td> + <td class="tdc">7.15</td> <td class="tdc">7.40</td> + <td class="tdc">7.65</td> <td class="tdc">7.90</td> + <td class="tdc">8.15</td> <td class="tdc">8.40</td> + <td class="tdc">8.66</td> <td class="tdc">8.91</td> + <td class="tdc">9.16</td> <td class="tdc">9.41 + <span class="pagenum"><a id="Page_481"></a>[Pg 481]</span></td> + </tr><tr> + <td class="tdc">2.1</td> <td class="tdc">6.92</td> + <td class="tdc">7.17</td> <td class="tdc">7.42</td> + <td class="tdc">7.67</td> <td class="tdc">7.92</td> + <td class="tdc">8.17</td> <td class="tdc">8.42</td> + <td class="tdc">8.68</td> <td class="tdc">8.93</td> + <td class="tdc">9.18</td> <td class="tdc">9.43</td> + </tr><tr> + <td class="tdc">2.2</td> <td class="tdc">6.94</td> + <td class="tdc">7.19</td> <td class="tdc">7.44</td> + <td class="tdc">7.69</td> <td class="tdc">7.94</td> + <td class="tdc">8.19</td> <td class="tdc">8.44</td> + <td class="tdc">8.70</td> <td class="tdc">8.95</td> + <td class="tdc">9.20</td> <td class="tdc">9.45</td> + </tr><tr> + <td class="tdc">2.3</td> <td class="tdc">6.96</td> + <td class="tdc">7.21</td> <td class="tdc">7.46</td> + <td class="tdc">7.71</td> <td class="tdc">7.96</td> + <td class="tdc">8.21</td> <td class="tdc">8.46</td> + <td class="tdc">8.72</td> <td class="tdc">8.97</td> + <td class="tdc">9.22</td> <td class="tdc">9.47</td> + </tr><tr> + <td class="tdc">2.4</td> <td class="tdc">6.98</td> + <td class="tdc">7.23</td> <td class="tdc">7.48</td> + <td class="tdc">7.73</td> <td class="tdc">7.98</td> + <td class="tdc">8.23</td> <td class="tdc">8.48</td> + <td class="tdc">8.74</td> <td class="tdc">8.99</td> + <td class="tdc">9.24</td> <td class="tdc">9.49</td> + </tr><tr> + <td class="tdc">2.5</td> <td class="tdc">7.00</td> + <td class="tdc">7.25</td> <td class="tdc">7.50</td> + <td class="tdc">7.75</td> <td class="tdc">8.00</td> + <td class="tdc">8.25</td> <td class="tdc">8.50</td> + <td class="tdc">8.76</td> <td class="tdc">9.01</td> + <td class="tdc">9.26</td> <td class="tdc">9.51</td> + </tr><tr> + <td class="tdc">2.6</td> <td class="tdc">7.02</td> + <td class="tdc">7.27</td> <td class="tdc">7.52</td> + <td class="tdc">7.77</td> <td class="tdc">8.02</td> + <td class="tdc">8.27</td> <td class="tdc">8.52</td> + <td class="tdc">8.78</td> <td class="tdc">9.03</td> + <td class="tdc">9.28</td> <td class="tdc">9.53</td> + </tr><tr> + <td class="tdc">2.7</td> <td class="tdc">7.04</td> + <td class="tdc">7.29</td> <td class="tdc">7.54</td> + <td class="tdc">7.79</td> <td class="tdc">8.04</td> + <td class="tdc">8.29</td> <td class="tdc">8.54</td> + <td class="tdc">8.80</td> <td class="tdc">9.05</td> + <td class="tdc">9.30</td> <td class="tdc">9.55</td> + </tr><tr> + <td class="tdc">2.8</td> <td class="tdc">7.06</td> + <td class="tdc">7.31</td> <td class="tdc">7.56</td> + <td class="tdc">7.81</td> <td class="tdc">8.06</td> + <td class="tdc">8.31</td> <td class="tdc">8.57</td> + <td class="tdc">8.82</td> <td class="tdc">9.07</td> + <td class="tdc">9.32</td> <td class="tdc">9.57</td> + </tr><tr> + <td class="tdc bb">2.9</td> <td class="tdc bb">7.08</td> + <td class="tdc bb">7.33</td> <td class="tdc bb">7.58</td> + <td class="tdc bb">7.83</td> <td class="tdc bb">8.08</td> + <td class="tdc bb">8.33</td> <td class="tdc bb">8.59</td> + <td class="tdc bb">8.84</td> <td class="tdc bb">9.09</td> + <td class="tdc bb">9.34</td> <td class="tdc bb">9.59</td> + </tr><tr> + <td class="tdc">3.0</td> <td class="tdc">7.10</td> + <td class="tdc">7.35</td> <td class="tdc">7.60</td> + <td class="tdc">7.85</td> <td class="tdc">8.10</td> + <td class="tdc">8.36</td> <td class="tdc">8.61</td> + <td class="tdc">8.86</td> <td class="tdc">9.11</td> + <td class="tdc">9.36</td> <td class="tdc">9.61</td> + </tr><tr> + <td class="tdc">3.1</td> <td class="tdc">7.12</td> + <td class="tdc">7.37</td> <td class="tdc">7.62</td> + <td class="tdc">7.87</td> <td class="tdc">8.13</td> + <td class="tdc">8.38</td> <td class="tdc">8.63</td> + <td class="tdc">8.88</td> <td class="tdc">9.13</td> + <td class="tdc">9.38</td> <td class="tdc">9.64</td> + </tr><tr> + <td class="tdc">3.2</td> <td class="tdc">7.14</td> + <td class="tdc">7.39</td> <td class="tdc">7.64</td> + <td class="tdc">7.89</td> <td class="tdc">8.15</td> + <td class="tdc">8.40</td> <td class="tdc">8.65</td> + <td class="tdc">8.90</td> <td class="tdc">9.15</td> + <td class="tdc">9.41</td> <td class="tdc">9.66</td> + </tr><tr> + <td class="tdc">3.3</td> <td class="tdc">7.16</td> + <td class="tdc">7.41</td> <td class="tdc">7.66</td> + <td class="tdc">7.92</td> <td class="tdc">8.17</td> + <td class="tdc">8.42</td> <td class="tdc">8.67</td> + <td class="tdc">8.92</td> <td class="tdc">9.18</td> + <td class="tdc">9.43</td> <td class="tdc">9.68</td> + </tr><tr> + <td class="tdc">3.4</td> <td class="tdc">7.18</td> + <td class="tdc">7.43</td> <td class="tdc">7.69</td> + <td class="tdc">7.94</td> <td class="tdc">8.19</td> + <td class="tdc">8.44</td> <td class="tdc">8.69</td> + <td class="tdc">8.94</td> <td class="tdc">9.20</td> + <td class="tdc">9.45</td> <td class="tdc">9.70</td> + </tr><tr> + <td class="tdc">3.5</td> <td class="tdc">7.20</td> + <td class="tdc">7.45</td> <td class="tdc">7.71</td> + <td class="tdc">7.96</td> <td class="tdc">8.21</td> + <td class="tdc">8.46</td> <td class="tdc">8.71</td> + <td class="tdc">8.96</td> <td class="tdc">9.22</td> + <td class="tdc">9.47</td> <td class="tdc">9.72</td> + </tr><tr> + <td class="tdc">3.6</td> <td class="tdc">7.22</td> + <td class="tdc">7.48</td> <td class="tdc">7.73</td> + <td class="tdc">7.98</td> <td class="tdc">8.23</td> + <td class="tdc">8.48</td> <td class="tdc">8.73</td> + <td class="tdc">8.98</td> <td class="tdc">9.24</td> + <td class="tdc">9.49</td> <td class="tdc">9.74</td> + </tr><tr> + <td class="tdc">3.7</td> <td class="tdc">7.24</td> + <td class="tdc">7.50</td> <td class="tdc">7.75</td> + <td class="tdc">8.00</td> <td class="tdc">8.25</td> + <td class="tdc">8.50</td> <td class="tdc">8.75</td> + <td class="tdc">9.00</td> <td class="tdc">9.26</td> + <td class="tdc">9.51</td> <td class="tdc">9.76</td> + </tr><tr> + <td class="tdc">3.8</td> <td class="tdc">7.26</td> + <td class="tdc">7.52</td> <td class="tdc">7.77</td> + <td class="tdc">8.02</td> <td class="tdc">8.27</td> + <td class="tdc">8.52</td> <td class="tdc">8.77</td> + <td class="tdc">9.02</td> <td class="tdc">9.28</td> + <td class="tdc">9.53</td> <td class="tdc">9.78</td> + </tr><tr> + <td class="tdc bb">3.9</td> <td class="tdc bb">7.28</td> + <td class="tdc bb">7.54</td> <td class="tdc bb">7.79</td> + <td class="tdc bb">8.04</td> <td class="tdc bb">8.29</td> + <td class="tdc bb">8.54</td> <td class="tdc bb">8.79</td> + <td class="tdc bb">9.04</td> <td class="tdc bb">9.30</td> + <td class="tdc bb">9.55</td> <td class="tdc bb">9.80</td> + </tr><tr> + <td class="tdc">4.0</td> <td class="tdc">7.30</td> + <td class="tdc">7.56</td> <td class="tdc">7.81</td> + <td class="tdc">8.06</td> <td class="tdc">8.31</td> + <td class="tdc">8.56</td> <td class="tdc">8.81</td> + <td class="tdc">9.06</td> <td class="tdc">9.32</td> + <td class="tdc">9.57</td> <td class="tdc">9.83</td> + </tr><tr> + <td class="tdc">4.1</td> <td class="tdc">7.32</td> + <td class="tdc">7.58</td> <td class="tdc">7.83</td> + <td class="tdc">8.08</td> <td class="tdc">8.33</td> + <td class="tdc">8.58</td> <td class="tdc">8.83</td> + <td class="tdc">9.08</td> <td class="tdc">9.34</td> + <td class="tdc">9.59</td> <td class="tdc">9.85</td> + </tr><tr> + <td class="tdc">4.2</td> <td class="tdc">7.34</td> + <td class="tdc">7.60</td> <td class="tdc">7.85</td> + <td class="tdc">8.10</td> <td class="tdc">8.35</td> + <td class="tdc">8.60</td> <td class="tdc">8.85</td> + <td class="tdc">9.11</td> <td class="tdc">9.36</td> + <td class="tdc">9.62</td> <td class="tdc">9.87</td> + </tr><tr> + <td class="tdc">4.3</td> <td class="tdc">7.36</td> + <td class="tdc">7.62</td> <td class="tdc">7.87</td> + <td class="tdc">8.12</td> <td class="tdc">8.37</td> + <td class="tdc">8.62</td> <td class="tdc">8.88</td> + <td class="tdc">9.13</td> <td class="tdc">9.38</td> + <td class="tdc">9.64</td> <td class="tdc">9.89</td> + </tr><tr> + <td class="tdc">4.4</td> <td class="tdc">7.38</td> + <td class="tdc">7.64</td> <td class="tdc">7.89</td> + <td class="tdc">8.14</td> <td class="tdc">8.39</td> + <td class="tdc">8.64</td> <td class="tdc">8.90</td> + <td class="tdc">9.15</td> <td class="tdc">9.40</td> + <td class="tdc">9.66</td> <td class="tdc">9.91</td> + </tr><tr> + <td class="tdc">4.5</td> <td class="tdc">7.40</td> + <td class="tdc">7.66</td> <td class="tdc">7.91</td> + <td class="tdc">8.16</td> <td class="tdc">8.41</td> + <td class="tdc">8.66</td> <td class="tdc">8.92</td> + <td class="tdc">9.17</td> <td class="tdc">9.42</td> + <td class="tdc">9.68</td> <td class="tdc">9.93</td> + </tr><tr> + <td class="tdc">4.6</td> <td class="tdc">7.43</td> + <td class="tdc">7.68</td> <td class="tdc">7.93</td> + <td class="tdc">8.18</td> <td class="tdc">8.43</td> + <td class="tdc">8.68</td> <td class="tdc">8.94</td> + <td class="tdc">9.19</td> <td class="tdc">9.44</td> + <td class="tdc">9.70</td> <td class="tdc">9.95</td> + </tr><tr> + <td class="tdc">4.7</td> <td class="tdc">7.45</td> + <td class="tdc">7.70</td> <td class="tdc">7.95</td> + <td class="tdc">8.20</td> <td class="tdc">8.45</td> + <td class="tdc">8.70</td> <td class="tdc">8.96</td> + <td class="tdc">9.21</td> <td class="tdc">9.46</td> + <td class="tdc">9.72</td> <td class="tdc">9.97</td> + </tr><tr> + <td class="tdc">4.8</td> <td class="tdc">7.47</td> + <td class="tdc">7.72</td> <td class="tdc">7.97</td> + <td class="tdc">8.22</td> <td class="tdc">8.47</td> + <td class="tdc">8.72</td> <td class="tdc">8.98</td> + <td class="tdc">9.23</td> <td class="tdc">9.48</td> + <td class="tdc">9.74</td> <td class="tdc">9.99</td> + </tr><tr> + <td class="tdc bb">4.9</td> <td class="tdc bb">7.49</td> + <td class="tdc bb">7.74</td> <td class="tdc bb">7.99</td> + <td class="tdc bb">8.24</td> <td class="tdc bb">8.49</td> + <td class="tdc bb">8.74</td> <td class="tdc bb">9.00</td> + <td class="tdc bb">9.25</td> <td class="tdc bb">9.50</td> + <td class="tdc bb">9.76</td> <td class="tdc bb">10.01 </td> + </tr><tr> + <td class="tdc">5.0</td> <td class="tdc">7.51</td> + <td class="tdc">7.76</td> <td class="tdc">8.01</td> + <td class="tdc">8.26</td> <td class="tdc">8.51</td> + <td class="tdc">8.76</td> <td class="tdc">9.02</td> + <td class="tdc">9.27</td> <td class="tdc">9.52</td> + <td class="tdc">9.78</td> <td class="tdc">10.03 </td> + </tr><tr> + <td class="tdc">5.1</td> <td class="tdc">7.53</td> + <td class="tdc">7.78</td> <td class="tdc">8.03</td> + <td class="tdc">8.28</td> <td class="tdc">8.53</td> + <td class="tdc">8.79</td> <td class="tdc">9.04</td> + <td class="tdc">9.29</td> <td class="tdc">9.54</td> + <td class="tdc">9.80</td> <td class="tdc">10.05 </td> + </tr><tr> + <td class="tdc">5.2</td> <td class="tdc">7.55</td> + <td class="tdc">7.80</td> <td class="tdc">8.05</td> + <td class="tdc">8.30</td> <td class="tdc">8.55</td> + <td class="tdc">8.81</td> <td class="tdc">9.06</td> + <td class="tdc">9.31</td> <td class="tdc">9.56</td> + <td class="tdc">9.82</td> <td class="tdc">10.07 </td> + </tr><tr> + <td class="tdc">5.3</td> <td class="tdc">7.57</td> + <td class="tdc">7.82</td> <td class="tdc">8.07</td> + <td class="tdc">8.32</td> <td class="tdc">8.57</td> + <td class="tdc">8.83</td> <td class="tdc">9.08</td> + <td class="tdc">9.33</td> <td class="tdc">9.58</td> + <td class="tdc">9.84</td> <td class="tdc">10.09 </td> + </tr><tr> + <td class="tdc">5.4</td> <td class="tdc">7.59</td> + <td class="tdc">7.84</td> <td class="tdc">8.09</td> + <td class="tdc">8.34</td> <td class="tdc">8.60</td> + <td class="tdc">8.85</td> <td class="tdc">9.10</td> + <td class="tdc">9.36</td> <td class="tdc">9.61</td> + <td class="tdc">9.86</td> <td class="tdc">10.11 </td> + </tr><tr> + <td class="tdc">5.5</td> <td class="tdc">7.61</td> + <td class="tdc">7.86</td> <td class="tdc">8.11</td> + <td class="tdc">8.36</td> <td class="tdc">8.62</td> + <td class="tdc">8.87</td> <td class="tdc">9.12</td> + <td class="tdc">9.38</td> <td class="tdc">9.63</td> + <td class="tdc">9.88</td> <td class="tdc">10.13 </td> + </tr><tr> + <td class="tdc">5.6</td> <td class="tdc">7.63</td> + <td class="tdc">7.88</td> <td class="tdc">8.13</td> + <td class="tdc">8.39</td> <td class="tdc">8.64</td> + <td class="tdc">8.89</td> <td class="tdc">9.15</td> + <td class="tdc">9.40</td> <td class="tdc">9.65</td> + <td class="tdc">9.90</td> <td class="tdc">10.15 </td> + </tr><tr> + <td class="tdc">5.7</td> <td class="tdc">7.65</td> + <td class="tdc">7.90</td> <td class="tdc">8.15</td> + <td class="tdc">8.41</td> <td class="tdc">8.66</td> + <td class="tdc">8.91</td> <td class="tdc">9.17</td> + <td class="tdc">9.42</td> <td class="tdc">9.67</td> + <td class="tdc">9.92</td> <td class="tdc">10.17 </td> + </tr><tr> + <td class="tdc">5.8</td> <td class="tdc">7.67</td> + <td class="tdc">7.92</td> <td class="tdc">8.17</td> + <td class="tdc">8.43</td> <td class="tdc">8.68</td> + <td class="tdc">8.94</td> <td class="tdc">9.19</td> + <td class="tdc">9.44</td> <td class="tdc">9.69</td> + <td class="tdc">9.94</td> <td class="tdc">10.19 </td> + </tr><tr> + <td class="tdc">5.9</td> <td class="tdc">7.69</td> + <td class="tdc">7.94</td> <td class="tdc">8.20</td> + <td class="tdc">8.45</td> <td class="tdc">8.70</td> + <td class="tdc">8.96</td> <td class="tdc">9.21</td> + <td class="tdc">9.46</td> <td class="tdc">9.71</td> + <td class="tdc">9.96</td> <td class="tdc">10.22 </td> + </tr><tr> + <td class="tdc bb">6.0</td> <td class="tdc bb">7.71</td> + <td class="tdc bb">7.96</td> <td class="tdc bb">8.22</td> + <td class="tdc bb">8.47</td> <td class="tdc bb">8.72</td> + <td class="tdc bb">8.98</td> <td class="tdc bb">9.23</td> + <td class="tdc bb">9.48</td> <td class="tdc bb">9.73</td> + <td class="tdc bb">9.98</td> <td class="tdc bb">10.24 </td> + </tr> + </tbody> +</table> + +<p><span class="pagenum"><a id="Page_482"></a>[Pg 482]</span> +<b>449. Determination of Ash.</b>—In the determination of the solid +residue obtained by drying milk, it is important to observe the +directions already given (<b><a href="#P_28">28-32</a></b>).</p> + +<p>In the direct ignition of the sample, a portion of the sulfur and +phosphorus may escape oxidation and be lost as volatile compounds. +This loss may be avoided by the use of proper oxidizing agents or by +conducting the combustion as heretofore described.<a id="FNanchor_430" href="#Footnote_430" class="fnanchor">[430]</a> +In the official method, it is directed to add six cubic centimeters +of nitric acid to twenty of milk, evaporate to dryness and ignite the +residue at a low red heat until free of carbon.<a id="FNanchor_431" href="#Footnote_431" class="fnanchor">[431]</a> +It is doubtful if this precaution be entirely sufficient to save all +the sulfur and phosphorus, but the method is evidently more reliable +than the common one of direct ignition without any oxidizing reagent +whatever.</p> + +<h3>ESTIMATION OF FAT.</h3> + +<p><b>450. Form of Fat in Milk.</b>—The fat in milk occurs in the form +of globules suspended in the liquid, in other words in the form of an +emulsion. Many authorities have asserted that each globule of fat is +contained in a haptogenic membrane composed presumably of nitrogenous +matter, but there is no convincing evidence of the truth of this +opinion. The weight of experimental evidence is in the opposite +direction. The supposed action of the membrane and the phenomena +produced thereby are more easily explained by the surface tension +existing between the fat globules and the menstruum in which they are +suspended.</p> + +<p>Babcock affirms that the spontaneous coagulation of the fibrin present +in milk tends to draw the fat globules into clusters, and this tendency +can be arrested by adding a little soda or potash lye to the milk as +soon as it is drawn.<a id="FNanchor_432" href="#Footnote_432" class="fnanchor">[432]</a></p> + +<p>The diameter of the fat globules is extremely variable, extending in +some cases from two to twenty micromillimeters. In cow milk, the usual +diameters are from three to five micromillimeters.</p> + +<p><b>451. Number of Fat Globules in Milk.</b>—The number of fat globules +<span class="pagenum"><a id="Page_483"></a>[Pg 483]</span> +in milk depends on their size and the percentage of fat. It is evident +that no definite statement of the number can be made. There is a +tendency, on the part of the globules, to diminish in size and increase +in number as the period of lactation is prolonged. To avoid large +numbers, it is convenient to give the number of globules in 0.0001 +cubic millimeter. This number may be found within wide limits depending +on the individual, race, food and other local conditions to which the +animal or herd is subjected. In general, in whole milk this number will +be found between 140 and 250.</p> + +<p><b>452. Method of Counting Globules.</b>—The number of globules in +milk is computed with the aid of the microscope. The most convenient +method is the one devised by Babcock.<a id="FNanchor_433" href="#Footnote_433" class="fnanchor">[433]</a> +In carrying out this +computation, capillary tubes, from two to three centimeters long and +about one-tenth millimeter in internal diameter, are provided. The +exact diameter of each tube, in at least three points, is determined +by the micrometer attachment of the microscope, and from these +measurements the mean diameter of the tube is calculated. This known, +its cubic content for any given length is easily computed. Ten cubic +centimeters of the milk are diluted with distilled water to half a +liter and one end of a capillary tube dipped therein. The tube is +quickly filled with diluted milk and each end is closed with a little +wax to prevent evaporation. Several of these tubes being thus prepared, +they are placed in a horizontal position on the stage of the microscope +and covered with glycerol and a cover glass. The tubes are left at +rest for some time until all the fat globules have attached themselves +to the upper surfaces, in which position they are easily counted. +The micrometer is so placed as to lie parallel with the tubes, and +the number of globules, corresponding to each division of its scale, +counted. The mean number of globules corresponding to each division of +the micrometer scale is thus determined.</p> + +<p>To compare the data obtained with each tube they are reduced to a +common basis of the number of globules found in a length of fifty +divisions of the micrometer scale in a tube having a diameter of 100 +divisions, using the formula</p> + +<table class="spb1 fs_105"> + <tbody><tr> + <td class="tdl" rowspan="2"><i>N</i> = </td> + <td class="tdc bb">10000<i>n</i></td> + </tr><tr> + <td class="tdc"><i>d</i>²</td> + </tr> + </tbody> +</table> + +<p><span class="pagenum"><a id="Page_484"></a>[Pg 484]</span> +in which <i>n</i> = the number of globules found in the standard +length of tube measured and <i>d</i> = the diameter of the tube. It +is not difficult to actually count all the globules in a length of +fifty divisions of the scale, but the computation may also be made +from the mean numbers found in a few divisions. The usual number of +globules found in a length of 0.1 millimeter in a tube 0.1 millimeter +in diameter, varies from fifty to one hundred.</p> + +<div class="blockquot"> +<p><i>Example.</i>—The length of one division of the micrometer scale is +0.002 millimeter, and the internal diameter of the tube 0.1 millimeter. +The content of a tube, of a length of 0.002 × 50 = 0.1 millimeter, is +therefore 0.0007854 cubic millimeter.</p> + +<p>The cubic content of a tube 100 scale divisions in diameter and fifty +in length is 0.0031416 cubic millimeter. The number of globules found +in fifty divisions of the tubes used is 40. Then the number which would +be contained in a tube of a diameter of 100 divisions of the micrometer +scale and a length of fifty divisions thereof is</p> + +<table class="spb1 fs_105"> + <tbody><tr> + <td class="tdl" rowspan="2"><i>N</i> = </td> + <td class="tdc bb">10000<i>n</i></td> + <td class="tdl" rowspan="2"> = </td> + <td class="tdc bb">400000</td> + <td class="tdl" rowspan="2"> = 160.</td> + </tr><tr> + <td class="tdc"><i>d</i>²</td> + <td class="tdc">2500</td> + </tr> + </tbody> +</table> + +<p>Since the milk is diluted fifty times, the actual number of globules +corresponding to the volume given is 8000. It is convenient to reduce +the observations to some definite volume, <i>exempla gratia</i>, 0.0001 +cubic centimeter. The equation for this in the above instance is +0.0031416: 0.0001 = 8000: <i>x</i>, whence <i>x</i> = 223, = number +of fat globules in 0.0001 cubic millimeter.</p> +</div> + +<p>In one cubic millimeter of milk there are therefore 2,230,000 fat +globules, and in one cubic centimeter 2,230,000,000 globules. In a +single drop of milk there are from one to two hundred million fat +globules.<a id="FNanchor_434" href="#Footnote_434" class="fnanchor">[434]</a></p> + +<p><b>453. Classification of Methods of Determining Fat in Milk.</b>—The +fat, being the most valuable of the constituents of milk, is the +subject of a number of analytical processes. An effort will be made +here to classify these various methods and to illustrate each class +with one or more typical processes. In general the methods may be +divided into analytical and commercial, those of the first class being +used for scientific and of the other for trade purposes. For normal +milk, some of the trade methods have proved to be quite as accurate as +<span class="pagenum"><a id="Page_485"></a>[Pg 485]</span> +the more chronokleptic analytical processes to which, in disputed +cases, a final appeal must be taken. When the analyst is called upon to +determine the fat in a large number of samples of milk some one of the +trade methods may often be adopted with great advantage.</p> + +<p><b>454. Dry Extraction Methods.</b>—Among the oldest and most reliable +methods of determining fat in milk, are included those processes based +on the principle of drying the milk and extracting the fat from the +residue by an appropriate solvent. The solvents generally employed are +ether and petroleum spirit of low boiling point. The methods of drying +are legion.</p> + +<p>In extracting with ether, it must not be forgotten that other bodies +than fat may pass into solution on the one hand and on the other any +substituted glycerid, such as lecithin or nuclein, which may be present +may escape solution, at least in part. Perhaps petroleum spirit, +boiling at from 45° to 60°, is the best solvent for fat, but it is +almost the universal custom in this and other countries to use ether.</p> + +<p id="P_455"><b>455. The Official Methods.</b>—In the methods adopted by the +Association of Official Agricultural Chemists two processes are +recommended.</p> + +<p>(1) <i>The Asbestos Process</i>: In this process it is directed to +extract the residue from the determination of water by the asbestos +method (<b><a href="#P_447">447</a></b>) with anhydrous pure ether until the fat is removed, +evaporate the ether, dry the fat at 100° and weigh. The fat may also be +determined by difference, after drying the extracted cylinders at 100°.</p> + +<p>(2) <i>Paper Coil Method</i>: This is essentially the method proposed +by Adams as modified by the author.<a id="FNanchor_435" href="#Footnote_435" class="fnanchor">[435]</a> +Coils made of thick filter paper are cut into strips 6.25 by 62.5 +centimeters, thoroughly extracted with ether and alcohol, or the weight +of the extract corrected by a constant obtained for the paper. If this +latter method be used, a small amount of anhydrous sodium carbonate +should be added. Paper free of matters soluble in ether is also to be +had for this purpose. From a weighing bottle about five grams of milk +are transferred to the coil by a pipette, taking care to keep dry the +<span class="pagenum"><a id="Page_486"></a>[Pg 486]</span> +lower end of the coil. The coil, dry end down, is placed on a piece +of glass, and dried at a temperature of boiling water for one hour, +or better, dried in hydrogen at a temperature of boiling water, +transferred to an extraction apparatus and extracted with absolute +ether or petroleum spirit boiling at about 45°. The extracted fat is +dried in hydrogen and weighed. Experience has shown that drying in +hydrogen is not necessary. The fat may be conveniently dried in partial vacuo.</p> + +<p><b>456. Variations of Extraction Method.</b>—The method of preparing +the milk for fat extraction is capable of many variations. Some of the +most important follow:</p> + +<p>(1) <i>Evaporation on Sand</i>: The sand should be pure, dry and of +uniform size of grain. It may be held in a dish or tube. The dish may +be made of tin foil, so that it can be introduced with its contents +into the extraction apparatus after the desiccation is complete. For +this purpose, it is cut into fragments of convenient size after its +contents have been poured into the extractor. The scissors used are +washed with the solvent.</p> + +<p>(2) <i>Evaporation on Kieselguhr</i>: Dry kieselguhr (infusorial +earth, tripoli) may take the place of the sand as above noted. The +manipulation is the same as with sand.</p> + +<p>(3) <i>Evaporation on Plaster of Paris</i>,<a id="FNanchor_436" href="#Footnote_436" class="fnanchor">[436]</a> +(<i>Soxhlet Method</i>),<a id="FNanchor_437" href="#Footnote_437" class="fnanchor">[437]</a> +(4) <i>On Pumice Stone</i>, (5) <i>On Powdered Glass</i>, (6) <i>On +Chrysolite</i>:<a id="FNanchor_438" href="#Footnote_438" class="fnanchor">[438]</a> +The manipulation in these cases is conducted as with sand and no +detailed description is required.</p> + +<p>(7) <i>Evaporation on Organic Substances</i>: These variations would +fall under the general heading of drying on paper. The following +materials have been used; <i>viz.</i>, sponge,<a id="FNanchor_439" href="#Footnote_439" class="fnanchor">[439]</a> +lint,<a id="FNanchor_440" href="#Footnote_440" class="fnanchor">[440]</a> +and wood pulp.<a id="FNanchor_441" href="#Footnote_441" class="fnanchor">[441]</a> +In these variations the principal precautions to be observed are to +secure the organic material in a dry state and free of any matter +soluble in the solvent used.</p> + +<p>(8) <i>Dehydration with Anhydrous Copper Sulfate</i>: In this process +the water of the sample is absorbed by powdered anhydrous copper +sulfate, the residual mass extracted and the butter fat obtained +determined by saponification and titration.<a id="FNanchor_442" href="#Footnote_442" class="fnanchor">[442]</a> +In the manipulation about twenty grams of the anhydrous copper sulfate +<span class="pagenum"><a id="Page_487"></a>[Pg 487]</span> +are placed in a mortar, a depression made therein in such a manner that +ten cubic centimeters of milk can be poured into it without wetting +it through to the mortar. The water is soon absorbed when the mass is +ground with a little dry sand and transferred to the extractor.</p> + +<p>Petroleum spirit of low boiling point is used as a solvent, successive +portions of about fifteen cubic centimeters each being forced through +the powdered mass under pressure. Two or three treatments with the +petroleum are required. The residual butter fat, after the evaporation +of the petroleum, is saponified with a measured portion, about +twenty-five cubic centimeters, of seminormal alcoholic potash lye. The +residual alkali is determined by titration with seminormal hydrochloric +acid in the usual manner. From the data obtained is calculated the +quantity of alkali employed in the saponification. The weight of butter +fat extracted is then calculated on the assumption that 230 milligrams +of potash are required to saponify one gram of the fat.</p> + +<p><b>457. Gypsum Method for Sour Milk.</b>—In sour milk, extraction +of the dry residue with ether is attended with danger of securing a +part of the free lactic acid in the extract. This may be avoided, at +least in part, by making the milk neutral or slightly alkaline before +desiccation. This method is illustrated by a variation of Soxhlet’s +method of drying on gypsum proposed by Kühn.<a id="FNanchor_443" href="#Footnote_443" class="fnanchor">[443]</a> +The curdled milk is treated with potash lye of forty per cent strength +until the reaction is slightly alkaline. For absorbing the sample +before drying, a mixture is employed consisting of twenty-five grams +of plaster of paris, four of precipitated carbonate of lime and two +of acid potassium sulfate. To this mixture ten grams of the milk, +rendered alkaline as above noted, are added in a desiccating dish, the +excess of moisture evaporated at 100°, the residual mass finely ground +and extracted with ether for four hours. A little gypsum may be found +in the solution, but in such small quantities as not to interfere +seriously with the accuracy of the results obtained.</p> + +<p><b>458. Estimation of Fat in Altered Milk.</b>—In altered milk the +lactose has usually undergone a fermentation affording considerable +quantities of lactic acid. If such milks be treated by the extraction +method for fat, the results will always be too high, because of the +solubility of lactic acid in ether. +<span class="pagenum"><a id="Page_488"></a>[Pg 488]</span></p> + +<p>Vizern<a id="FNanchor_444" href="#Footnote_444" class="fnanchor">[444]</a> +has proposed to avoid this error by first warming the soured +milk for a few minutes to 40°, at which temperature the clabber is +easily divided by vigorous shaking. Of the milk thus prepared, thirty +grams are diluted with two or three volumes of water and poured onto a +smooth and moistened filter. The vessel and filter are washed several +times until the filtrate presents no further acid reaction. The filter +and its contents are next placed in a vessel containing some fine +washed sand. A small quantity of water is added, sufficient to form a +paste. With a stirring rod, the filter is entirely broken up and the +whole mass thoroughly mixed. Dried on the water bath the material is +subjected to extraction in the ordinary way. Several analyses made +on fresh milk and on milk kept for several months show that almost +identical results are obtained.</p> + +<p>In respect of this process there would be danger, on long standing, +of the formation of free acids from butter glycerids, and these acids +would be removed by the process of washing prescribed. In this case the +quantity of fat obtained would be less than in the original sample.</p> + +<p><b>459. Comparison of Methods.</b>—An immense amount of work has been +done by analysts in comparing the various types of extraction methods +outlined above.<a id="FNanchor_445" href="#Footnote_445" class="fnanchor">[445]</a></p> + +<p>The consensus of opinion is that good results are obtained by all the +methods when properly conducted, and preference is given to the two +methods finally adopted by the Association of Official Chemists. As +solvents, pure ether and petroleum spirit of low boiling point are +preferred. The direct extraction gravimetric processes are important, +since it is to these that all the other quicker and easier methods must +appeal for the proof of their accuracy.</p> + +<p><b>460. Wet Extraction Methods.</b>—It has been found quite +impracticable to extract the fat from milk by shaking it directly with +the solvent. An emulsion is produced whereby the solvent itself becomes +incorporated with the other constituents of the milk, and from which it +is not separated easily even with the aid of whirling. The disturbing +element which prevents the separation of the solvent is doubtless the +<span class="pagenum"><a id="Page_489"></a>[Pg 489]</span> +colloid casein, since, when this is previously rendered soluble, the +separation of the solvent holding the fat is easily accomplished.</p> + +<p>The principle on which the methods of wet extraction are based is a +simple one; <i>viz.</i>, to secure a complete or partial solution +of the casein and subsequently to extract the fat with a solvent +immiscible with water. The methods may be divided into three great +classes; <i>viz.</i>, (1) those in which the solvent is evaporated from +the whole of the extracted fat and the residual matters weighed; (2) +processes in which an aliquot part of the fat solution is employed and +the total fat calculated from the data secured; (3) the density of the +fat solution is determined at a definite temperature and the percentage +of fat corresponding thereto determined from tables or otherwise. +Methods (1) and (2) are practically identical in principle and one +or the other may be applied according to convenience or to local +considerations. The methods may be further subdivided in respect of the +reagents used to secure complete or partial solution of the casein, as, +for instance, alkali or acid.<a id="FNanchor_446" href="#Footnote_446" class="fnanchor">[446]</a></p> + +<p><b>461. Solution in an Acid.</b>—A good type of these processes is the +method of Schmid.<a id="FNanchor_447" href="#Footnote_447" class="fnanchor">[447]</a> +In this process ten cubic centimeters of milk are placed in a test +tube of about five times that content, graduated to measure small +volumes. An equal quantity of hydrochloric acid is added, the mixture +shaken, boiled until it turns dark brown, and cooled quickly. The +fat is extracted by shaking with thirty cubic centimeters of ether. +After standing some time the ethereal solution separates and its +volume is noted. An aliquot part of the solution is removed, the +solvent evaporated, and the weight of fat in the whole determined by +calculation.</p> + +<p>The schmid process has been improved by Stokes,<a id="FNanchor_448" href="#Footnote_448" class="fnanchor">[448]</a> +Hill,<a id="FNanchor_449" href="#Footnote_449" class="fnanchor">[449]</a> +and Richmond.<a id="FNanchor_450" href="#Footnote_450" class="fnanchor">[450]</a> +The most important of these variations consists in weighing instead of +measuring the milk employed, thus insuring greater accuracy. Dyer and +Roberts affirm that the ether dissolves some of the caramel products +formed on boiling condensed milk with hydrochloric acid, and that the +data obtained in such cases by the process of Schmid are too high.<a id="FNanchor_451" href="#Footnote_451" class="fnanchor">[451]</a></p> + +<p>Since lactic acid is also slightly soluble in ether, sour milk should +not be extracted with that solvent. In these cases petroleum spirit, or +<span class="pagenum"><a id="Page_490"></a>[Pg 490]</span> +a mixture of petroleum and ether, as suggested by Pinette, may be +used.<a id="FNanchor_452" href="#Footnote_452" class="fnanchor">[452]</a> +Another variation consists in extracting the fat with several portions +of the solvent and evaporating all the extracts thus obtained to get +the total fat. This method is perhaps the best of those in which the +fat is extracted from the residual liquid after the decomposition of +the casein by an acid, and may be recommended as both reliable and +typical within the limitations mentioned above.</p> + +<p><b>462. Solution in an Alkali.</b>—The casein of milk is not so +readily dissolved in an alkali as in an acid, but the solution is +sufficient to permit the extraction of the fat. Soda and potash lyes +and ammonia are the alkaline bodies usually employed. To promote the +separation of the emulsions, alcohol is added with advantage. The +principle of the process rests on the observed power of an alkali +to free the fat globules sufficiently to allow them to dissolve in +ether or some other solvent. When the solvent has separated from the +emulsion at first formed, the whole or a part of it is used for the +determination of fat in a manner entirely analogous to that employed +in the process with the acid solutions described above. There are many +methods based on this principle, and some of the typical ones will be +given below. Experience has shown that extraction from an alkaline +solution is more troublesome and less perfect than from an acid and +these alkaline methods are, therefore, not so much practiced now as +they were formerly.</p> + +<p><b>463. Method of Short.</b>—Instead of measuring the volume of the +separated fat, Short has proposed a method in which the casein is +dissolved in an alkali and the fat at the same time saponified. The +soap thus produced is decomposed by sulfuric acid and the volume of the +separated fat acids noted. This volume represents eighty-seven per cent +of the corresponding volume of fat.<a id="FNanchor_453" href="#Footnote_453" class="fnanchor">[453]</a></p> + +<p>The solvent employed is a mixture of sodium and potassium hydroxids, +containing in one liter 125 and 150 grams, respectively, of these +alkalies. The sample of milk is mixed with half its volume of the +reagent and placed in boiling water for two hours. By this treatment +<span class="pagenum"><a id="Page_491"></a>[Pg 491]</span> +the casein is dissolved and the fat saponified. After cooling to about +60°, the soap is decomposed by the addition of equal parts of sulfuric +and acetic acids. The tubes containing the mixture are again placed in +boiling water for an hour and they are then filled with boiling water +to within one inch of the top. The tubes may either be furnished with a +graduation or the column of fat be measured by a scale.</p> + +<p><b>464. Method of Thörner.</b>—The process of Short is conducted by +Thörner as follows:<a id="FNanchor_454" href="#Footnote_454" class="fnanchor">[454]</a></p> + +<p>Ten cubic centimeters of milk measured at 15° are saponified, in +tubes fitting a centrifugal, by the addition of one and a half cubic +centimeters of an alcoholic potash lye, containing 160 grams of +potassium hydroxid per liter, or one cubic centimeter of an aqueous +fifty per cent soda lye. The saponification is hastened by setting the +tubes in boiling water, where they remain for two minutes. The soap +formed is decomposed with a strong acid, sulfuric preferred, the tubes +placed in the centrifugal and whirled for four minutes, when the fat +acids will be formed in the narrow graduated part of the tube and the +volume occupied thereby is noted after immersion in boiling water. +Thörner’s process is not followed in this country, but is used to a +considerable extent in Germany.<a id="FNanchor_455" href="#Footnote_455" class="fnanchor">[455]</a></p> + +<p><b>465. Liebermann’s Method.</b>—In this method, fifty cubic +centimeters of milk, at ordinary temperatures, are placed in a glass +cylinder twenty-five centimeters high and about four and a half +internal diameter; five cubic centimeters of potash lye of 1.27 +specific gravity are added, the cylinder closed with a well fitting +cork stopper and thoroughly shaken.<a id="FNanchor_456" href="#Footnote_456" class="fnanchor">[456]</a> +After shaking, fifty cubic centimeters of petroleum spirit, boiling +point about 60°, are added. The cylinder is again stoppered and +vigorously shaken until an emulsion is formed. To this emulsion fifty +cubic centimeters of alcohol of ninety-five per cent strength are +added, and the whole again thoroughly shaken. After four or five +minutes the petroleum spirit, containing the fat, separates. In order +to insure an absolute separation of the fat, however, the shaking may +be repeated three or four times for about one-quarter minute, waiting +each time between the shakings until the spirit separates. +<span class="pagenum"><a id="Page_492"></a>[Pg 492]</span></p> + +<p>Of the separated petroleum spirit twenty cubic centimeters are placed +in a small weighed flask. The use of the flask is recommended on +account of the ease with which the petroleum spirit can be evaporated +without danger of loss of fat. Instead of the flask a weighed beaker or +other weighed dish may be employed.</p> + +<p>The petroleum spirit is carefully evaporated on a water-bath and the +residue dried at 110° to 120° for one hour. The weight found multiplied +by five gives the content of fat in 100 cubic centimeters of the +milk. The percentage by weight can then be calculated by taking into +consideration the specific gravity of the milk employed.</p> + +<p>The results obtained by this method agree well with those obtained by +the paper coil method, when petroleum spirit instead of sulfuric ether +is used as the solvent for the fat. Sulfuric ether, however, gives +an apparently higher content of fat because of the solution of other +bodies not fat present in the milk.</p> + +<p><b>466. Densimetric Methods.</b>—Instead of evaporating the separated +fat solution and weighing the residue, its density may be determined +and the percentage of fat dissolved therein obtained by calculation, +or more conveniently from tables. The typical method of this kind is +due to Soxhlet, and until the introduction of modern rapid volumetric +processes, it was used perhaps more extensively than any other +proceeding for the determination of fat in milk.<a id="FNanchor_457" href="#Footnote_457" class="fnanchor">[457]</a> +The reagents employed in the process are ether saturated with water and +a potash lye containing 400 grams of potash in a liter. The principle +of the process is based on the assumption that a milk made alkaline +with potash will give up all its fat when shaken with ether and the +quantity of fat in solution can be determined by ascertaining the +specific gravity of the ethereal solution. +<span class="pagenum"><a id="Page_493"></a>[Pg 493]</span></p> + +<div class="figcenter smcap"> + <img id="FIG_108" src="images/fig108.jpg" alt="" width="400" height="514" > + <p class="center spb1">Fig. 108. Areometric Fat Apparatus.</p> +</div> + +<p><span class="pagenum"><a id="Page_494"></a>[Pg 494]</span> +The apparatus is arranged as shown in <a href="#FIG_108">Fig. 108</a>, +whereby it is easy to drive the ethereal fat solution into the +measuring vessel by means of the bellows shown. In the bottle, seen +at the right of the engraving are placed 200 cubic centimeters of +milk, ten of the potash lye and sixty of the aqueous ether. The milk +and potash are first added and well shaken, the ether then added, and +the contents of the bottle are shaken until a homogeneous emulsion +is formed. The bottle is then set aside for the separation of the +ethereal solution, which is promoted by gently jarring it from time to +time. When the chief part of the solution has separated, a sufficient +quantity of it is driven over into the measuring apparatus, by means +of the air bulbs, to float the hydrometer contained in the inner +cylinder. After a few moments the scale of the oleometer is read and +the percentage of fat calculated from the table. All the measurements +are made at a temperature of 17°.5. The temperature is preserved +constant by filling the outer cylinder of the apparatus with water. +If the room be warmer than 17°.5, the water added should be at a +temperature slightly below that and <i>vice versa</i>. The oleometer +carries a thermometer which indicates the moment when the reading is to +be made.</p> + +<p>The scale of the oleometer is graduated arbitrarily from 43 to 66, +corresponding to the specific gravities 0.743 and 0.766, respectively, +or to corresponding fat contents of 2.07 and 5.12 per cent, in the +milk, a range which covers most normal milks.</p> + +<p>In the use of the table the per cents corresponding to parts of an +oleometer division can be easily calculated.</p> + +<p class="f120 spa1"><b><span class="smcap">Table for Calculating +Per Cent of Fat in Milk<br>by Areometric Method of Soxhlet.</span></b></p> + +<table class="spb1"> + <thead><tr> + <th class="tdc bb">Reading of <br>oleometer.</th> + <th class="tdc bb"> Per cent fat <br>in milk.</th> + <th class="tdc bb">Reading of <br>oleometer.</th> + <th class="tdc bb"> Per cent fat <br>in milk.</th> + </tr></thead> + <tbody><tr> + <td class="tdc">43</td> + <td class="tdc">2.07</td> + <td class="tdc">55</td> + <td class="tdc">3.49</td> + </tr><tr> + <td class="tdc">44</td> + <td class="tdc">2.18</td> + <td class="tdc">56</td> + <td class="tdc">3.63</td> + </tr><tr> + <td class="tdc">45</td> + <td class="tdc">2.30</td> + <td class="tdc">57</td> + <td class="tdc">3.75</td> + </tr><tr> + <td class="tdc">46</td> + <td class="tdc">2.40</td> + <td class="tdc">58</td> + <td class="tdc">3.90</td> + </tr><tr> + <td class="tdc">47</td> + <td class="tdc">2.52</td> + <td class="tdc">59</td> + <td class="tdc">4.03</td> + </tr><tr> + <td class="tdc">48</td> + <td class="tdc">2.64</td> + <td class="tdc">60</td> + <td class="tdc">4.18</td> + </tr><tr> + <td class="tdc">49</td> + <td class="tdc">2.76</td> + <td class="tdc">61</td> + <td class="tdc">4.32</td> + </tr><tr> + <td class="tdc">50</td> + <td class="tdc">2.88</td> + <td class="tdc">62</td> + <td class="tdc">4.47</td> + </tr><tr> + <td class="tdc">51</td> + <td class="tdc">3.00</td> + <td class="tdc">63</td> + <td class="tdc">4.63</td> + </tr><tr> + <td class="tdc">52</td> + <td class="tdc">3.12</td> + <td class="tdc">64</td> + <td class="tdc">4.79</td> + </tr><tr> + <td class="tdc">53</td> + <td class="tdc">3.25</td> + <td class="tdc">65</td> + <td class="tdc">4.95</td> + </tr><tr> + <td class="tdc">54</td> + <td class="tdc">3.37</td> + <td class="tdc">66</td> + <td class="tdc">5.12</td> + </tr> + </tbody> +</table> + +<p><b>467. Application of the Areometric Method.</b>—Soxhlet’s method, as +outlined above, with many modifications, has been extensively used in +<span class="pagenum"><a id="Page_495"></a>[Pg 495]</span> +Europe and to a limited degree in this country, and the results +obtained are in general satisfactory, when the sample is a mixed one +from a large number of cows and of average composition.</p> + +<p>The author has shown that the process is not applicable to abnormal +milk and often not to milk derived from one animal alone.<a id="FNanchor_458" href="#Footnote_458" class="fnanchor">[458]</a></p> + +<p>The chief difficulty is found in securing a separation of the emulsion. +This trouble can usually be readily overcome by whirling. Any +centrifugal machine, which can receive the bottle in which the emulsion +is made, may be employed for that purpose.</p> + +<p>Since the introduction of more modern and convenient methods of fat +determination, the areometric method has fallen into disuse and perhaps +is no longer practiced in this country. It is valuable now chiefly from +the fact that many of the recorded analyses of milk fat were made by +it, and also for its typical character in representing all methods of +analysis of fat in milk based on the density of ethereal solutions.</p> + +<p><b>468. The Lactobutyrometer.</b>—A typical instrument for measuring +the volume of fat in a milk is known as Marchand’s lactobutyrometer. +It is based on the observation that ether will dissolve the fat from +milk when the casein is wholly or partly dissolved by an alkali, and +further, that the fat in an impure form can be separated from its +ethereal solution by the action of alcohol. Experience has shown +that all the fat is not separated from the ethereal solution by this +process, and also that the part separated is a saturated solution in +ether. The method cannot be rigorously placed in the two classes given +above, but being volumetric demands consideration here chiefly because +of its historical interest.<a id="FNanchor_459" href="#Footnote_459" class="fnanchor">[459]</a></p> + +<p>The instrument employed by Marchand is a tube about thirty centimeters +long and twelve in diameter, closed at one end and marked in three +portions of ten cubic centimeters each. The upper part is divided in +tenths of a cubic centimeter. The superior divisions are subdivided so +that the readings can be made to hundredths of a cubic centimeter.</p> + +<p>The tube is filled with milk to the first mark and two or three drops of +<span class="pagenum"><a id="Page_496"></a>[Pg 496]</span> +a twenty-five per cent solution of soda lye added thereto. Ether is +poured in to the second mark, the tube closed and vigorously shaken. +Alcohol of about ninety per cent strength is added to the upper mark, +the tube closed, shaken and allowed to stand in a vertical position, +with occasional jolting, until the separation of the liquids is +complete. In order to promote the separation the tube is placed in a +cylinder containing water at 40°.</p> + +<p>When the separation is complete the milk serum is found at the bottom, +the mixture of alcohol and ether in the middle and the fat at the top. +The mixture of ether and alcohol contains 0.126 gram of fat, and each +cubic centimeter of the separated ether fat 0.233 gram of fat. The +total volume of the separated fat, multiplied by 0.233, and the product +increased by 0.126, will give the weight of fat in the ten cubic +centimeters of milk employed.</p> + +<p class="blockquot"><i>Example.</i>—Milk used, ten cubic centimeters +of 1.032 specific gravity = 10.32 grams. The observed volume of the +saturated ether fat solution is two cubic centimeters. Then the weight +of fat is 2 × 0.233 + 0.126 = 0.592 gram. The percentage of fat in the +sample is 0.592 × 100 ÷ 10.32 = 5.74.</p> + +<p>In the apparatus used in this laboratory the upper division of the +graduation is marked 12.6, because this represents the quantity of fat +which remains in the ether-alcohol mixture for one liter of milk. From +this point the graduation is extended downward to ninety-five, which, +for ten cubic centimeters of milk, represents 0.95 gram. After the fat +has separated, enough ninety-five per cent alcohol is added to bring +the upper surface exactly to the graduation 12.6. The number of grams +per liter of milk is then read directly from the scale.</p> + +<p>In respect of applicability, the observation made regarding Soxhlet’s +areometric method may be repeated.</p> + +<p>In practical work in this country the lactobutyrometer is no longer +used, but many of the recorded determinations of fat in milk have been +made by this method.</p> + +<p><b>469. Volumetric Methods.</b>—For practical purposes, the volumetric +methods of estimating fat in milk have entirely superseded all the +<span class="pagenum"><a id="Page_497"></a>[Pg 497]</span> +other processes. It has been found that the fat readily separates in a +pure state from the other constituents of milk whenever the casein is +rendered completely soluble; whereas no process has yet been devised +whereby the fat can be easily separated in a pure state from milk +which has not been treated with some reagent capable of effecting a +solution of the casein. The volumetric methods may be divided into two +classes; <i>viz.</i>, (1) Those in which the fat is separated by the +simple action of gravity, and (2) those in which the natural action +of gravity is supplanted by centrifugal motion. Each of these classes +embraces a large number of variations and some of the typical ones will +be described in the following paragraphs. As solvents for the casein a +large number of reagents has been used, including alkalies and single +and mixed acids. In practice, preference is given to the least complex +and most easily prepared solvents.</p> + +<p><b>470. Method Of Patrick.</b>—A typical illustration of the method +of collecting the fat after solution of the casein, without the aid of +whirling, is found in the process devised by Patrick.<a id="FNanchor_460" href="#Footnote_460" class="fnanchor">[460]</a></p> + +<p>The solvent employed is a mixture of acetic, sulfuric and hydrochloric +acids, saturated with sodium sulfate, in the respective volumetric +proportions of nine, five and two. The separation is accomplished in a +large test tube drawn out near the top into a constricted neck which is +graduated to measure the volume of the separated fat or to give direct +percentage results.</p> + +<p>The tube should have a content of about twenty-five cubic centimeters +below the upper mark on the neck. In use 10.4 cubic centimeters of +milk and a sufficient quantity of the mixed acids to fill it nearly +to the upper mark are placed in the tube, together with a piece of +pumice stone, and the mixture boiled. On cooling below 100°, the fat +will separate and the volume thereof may be measured in the constricted +portion of the tube. The volume of the fat may be converted into weight +on multiplying by 0.88 at 60°, or more conveniently the percentage of +fat be taken from a table. In practice, the tube is filled with the +milk and acid mixture nearly up to the neck, its contents well mixed +and additional acid mixture added until the liquid is raised in the +tube above the neck. After mixing a second time, the contents are +<span class="pagenum"><a id="Page_498"></a>[Pg 498]</span> +boiled for five minutes and the fat allowed to collect in the expanded +part of the tube above the neck. When the fat has collected, the +mixture is boiled gently a second time for a few minutes. By this +treatment the fat is mixed with the upper portions of the acid liquid +and clarified. The clearing of the fat may be hastened by sprinkling +over it a little effloresced sodium sulfate. The fat is brought into +the graduated neck by opening a small orifice in the belly of the tube, +which is closed by means of a rubber band. When the temperature has +reached 60°, the space occupied by the fat is noted and the numbers +obtained express the percentage of fat in the sample.</p> + +<p>This process is illustrative of the principle of analysis, but is no +longer used in analytical determinations.</p> + +<p><b>471. The Lactocrite.</b>—One of the earliest methods for fat +estimation in milk, depending on the solution of the casein and the +collection of the fat by means of whirling, is based on the use of a +centrifugal machine known as the lactocrite. This apparatus is modeled +very like the machine usually employed for creamery work,<a id="FNanchor_461" href="#Footnote_461" class="fnanchor">[461]</a> +and at one time was extensively used, but it has now given place to less +troublesome and expensive machines. The acid mixture for freeing the +fat of casein is composed of glacial acetic acid carrying five per cent +of sulfuric. The samples of milk are heated with the acid mixture in +test tubes provided with stoppers and short glass tubes to return the +condensation products. The hot mixture is poured into a small metallic +cylindrical cup holding about three cubic centimeters. This cup fits +by means of an accurately ground shoulder on a metal casing, carrying +inside a heavy glass graduated tube of small internal diameter. The +excess of the milk mixture escapes through a small aperture in the +metallic screw cap of the metal holder. The metal holder is cut away on +both sides in order to expose the graduations on the glass tube. The +glass tube is held water-tight by means of perforated elastic washers. +Thus prepared the tubes are inserted in the radial holes of a revolving +steel disk previously heated to a temperature of 60°. The whirling is +accomplished in a few minutes by imparting to the steel disk a speed of +about 6,000 revolutions per minute. At the end of this operation the +fat is found in a clear column in the small glass tube and the number +<span class="pagenum"><a id="Page_499"></a>[Pg 499]</span> +of the divisions it occupies in this tube is noted. Each division of +the scale represents one-tenth per cent of fat.</p> + +<p>This apparatus is capable of giving accurate results when all its parts +are in good working order. In this laboratory the chief difficulty which +its use has presented is in keeping the joints in the glass metal tube tight.</p> + +<p>This description of the apparatus is given to secure an illustration of +the principle involved, a principle which has been worked out in later +times into some of the most rapid and practical processes of estimating +fat in milk.</p> + +<p><b>472. Modification of Lindström.</b>—Many modifications have been +proposed for conducting the determination of fat by means of the +lactocrite, but they do not involve any new principle and are of +doubtful merit. In the modification suggested by Lindström, which +has attained quite an extended practical application, the solvent +mixture is composed of lactic and sulfuric acids and the butyrometer +tubes are so changed as to permit the collection of the fat in the +graduated neck after whirling, by means of adding water. The apparatus +is also adjusted to secure the congelation of the fat column before +its volume is noted.<a id="FNanchor_462" href="#Footnote_462" class="fnanchor">[462]</a> +The analyst can read the fat volume at his leisure when it is in +the solid state and is not confused by changes of volume during the +observation. The best acid mixture has been found to be composed of 100 +volumes of lactic, an equal amount of acetic and fifteen volumes of +sulfuric acids.<a id="FNanchor_463" href="#Footnote_463" class="fnanchor">[463]</a></p> + +<div class="figleft smcap"> + <img id="FIG_109" src="images/fig109.jpg" alt="" width="200" height="395" > + <p class="center">Fig. 109.<br> Babcock’s Butyrometer<br> and Acid Measure.</p> +</div> + +<p id="P_473"><b>473. The Babcock Method.</b>—Among the many quick volumetric +methods which have been proposed for the determination of fat in +milk, none has secured so wide an application as that suggested by +Babcock.<a id="FNanchor_464" href="#Footnote_464" class="fnanchor">[464]</a></p> + +<p>The chief point of advantage in the use of this method is found in +effecting the solution of the casein by means of sulfuric acid of about +1.83 specific gravity. By this reagent the casein is dissolved in a few +moments without the aid of any other heat than that generated by mixing +the milk with the reagent. The bottle in which the separation is made +is shown in <a href="#FIG_109">Fig. 109</a>. The graduations on the neck are based +on the use of eighteen grams of milk. To avoid the trouble of weighing, the milk +<span class="pagenum"><a id="Page_500"></a>[Pg 500]</span> +is measured from a pipette graduated to deliver eighteen grams of milk +of the usual specific gravity. While it is true that normal milk may +vary somewhat in its density, it has been found that a pipette marked +at 17.6 cubic centimeters delivers a weight which can be safely assumed +to vary but slightly from the one desired. The graduated bottle holds +easily thirty-five cubic centimeters of liquid in its expanded portion +and the volume of milk just noted is mixed with an equal volume of +sulfuric acid, conveniently measured from the lip cylinder shown in the +<a href="#FIG_109">figure</a>. The complete mixture of the milk and +acid is effected by gently rotating the bottle until its contents are +homogeneous. The final color of the mixture varies from dark brown to black.</p> + +<p>While still hot, the bottles are placed in a centrifugal machine and +whirled for at least five minutes. The most convenient machine, where +it is available, is the one driven by a jet of steam. The revolutions +of the centrifugal should be at least 700 per minute for a twenty inch +and 1,200 for a twelve inch wheel. After five minutes the bottles are +removed and filled to the upper mark or nearly so with hot water, +replaced in the machine and whirled for at least one minute. The fat +will then be found in a clearly defined column in the graduated neck of +the bottle. In reading the scale, the extreme limits between the lowest +point marked by the lower meniscus and the highest point marked by the +edge of the upper meniscus are to be regarded as the termini of the fat +column.</p> + +<p>In testing cream by the babcock process, it may either be diluted until +<span class="pagenum"><a id="Page_501"></a>[Pg 501]</span> +the column of fat secured is contained in the graduated part of the +neck or specially graduated bottles may be used.</p> + +<p><i>Condensed Milk</i>: In applying the babcock test to condensed +milk, it is necessary to weigh the sample and to use only about eight +grams.<a id="FNanchor_465" href="#Footnote_465" class="fnanchor">[465]</a> +This quantity is placed in the bottle and dissolved in ten cubic +centimeters of water and the analysis completed as above. The reading +noted is multiplied by eighteen and divided by the weight of the sample +taken.</p> + +<p><i>Skim Milk</i>: In determining the fat in skim milk and whey, it is +desirable to use a bottle of double the usual capacity, but with the same +graduation on the neck. The percentage of fat noted is divided by two.</p> + +<p><i>Cheese</i>: Five grams are a convenient quantity of cheese to +employ. To this quantity in the bottle are added fifteen cubic +centimeters of hot water and the flask gently shaken and warmed until +the cheese is softened. The treatment with acid and whirling are the +same as described above. The noted reading is multiplied by eighteen +and divided by five.</p> + +<p><b>474. Solution in Amyl Alcohol and Hydrochloric and Sulfuric +Acids.</b>—Leffmann and Beam have proposed to aid the solution of +the casein in sulfuric acid by the previous addition to the milk of a +mixture of equal volumes of amyl alcohol and hydrochloric acid.<a id="FNanchor_466" href="#Footnote_466" class="fnanchor">[466]</a> +In this process the same graduated flasks may be used as in the +babcock process, or a special flask may be employed. In this case the +graduation of the neck is for fifteen cubic centimeters of milk, and +each one and a half cubic centimeters is divided into eighty-six parts. +The quantity of milk noted is placed in the flask, together with three +cubic centimeters of the mixture of amyl alcohol and hydrochloric acid, +and well shaken. To the mixture, sulfuric acid of 1.83 specific gravity +is added until the belly of the flask is nearly full and the contents +well mixed by shaking. When the casein is dissolved, the addition of +the sulfuric acid is continued until the flask is filled to the upper +mark and again the contents mixed. It is well to close the mouth of +the flask with a stopper while shaking. The bottle is placed in a +centrifugal and whirled for a few moments, when the fat is collected in +the graduated neck and its volume noted. +<span class="pagenum"><a id="Page_502"></a>[Pg 502]</span></p> + +<p>The process is also known in this country as the beimling method.<a id="FNanchor_467" href="#Footnote_467" class="fnanchor">[467]</a> +The fat separated in the above process is probably mixed with a little +fusel oil, and therefore it is advisable to use the specially graduated +bottle instead of one marked in absolute volumes.<a id="FNanchor_468" href="#Footnote_468" class="fnanchor">[468]</a></p> + +<p>The method, when conducted according to the details found in the +papers cited, gives accurate results, but is somewhat more complicated +than the babcock process and is not now used to any great extent in +analytical work.</p> + +<p id="P_475"><b>475. Method of Gerber.</b>—The method proposed by Gerber for +estimating fat in milk is based on the processes of Babcock, Beimling +and Beam already described. The tubes in which the decomposition of the +milk and the measurement of the fat are accomplished are of two kinds, +one open at only one end for milk and the other open at both ends for +cheese. They are closed during the separation by rubber stoppers.<a id="FNanchor_469" href="#Footnote_469" class="fnanchor">[469]</a></p> + +<div class="figcenter smcap"> + <img id="FIG_110" src="images/fig110.jpg" alt="" width="600" height="450" > + <p class="center spb1">Fig. 110. Gerber’s Butyrometers.</p> +</div> + +<p>The apparatus have been greatly improved and simplified since the first +description of them was published and have come into extensive use in +Europe and to a limited extent in this country.<a id="FNanchor_470" href="#Footnote_470" class="fnanchor">[470]</a></p> + +<p><span class="pagenum"><a id="Page_503"></a>[Pg 503]</span> +The butyrometer tubes are made of various sizes and shapes, but the +most convenient are those noted above as shown in <a href="#FIG_110">Fig. 110</a>.</p> + +<p>Before adding the strong sulfuric acid, one cubic centimeter of amyl +alcohol is mixed with the milk in the butyrometer. This admixture +serves to clarify the fat and render the reading more easy.</p> + +<p>The centrifugal is run by hand, and the required speed of rotation is +given it by means of a cord wrapped spirally about its axis, as shown +in <a href="#FIG_111">Fig. 111</a>. The cord in the new machines is +replaced by a leather strap working on a ratchet.</p> + +<div class="figcenter smcap"> + <img id="FIG_111" src="images/fig111.jpg" alt="" width="500" height="500" > + <p class="center spb1">Fig. 111. Gerber’s Centrifugal.</p> +</div> + +<p>The process is more speedy than that of Babcock, and the results have +been shown by a large experience to be reliable and accurate.</p> + +<p>The sulfuric acid employed is of 1.825 to 1.830 specific gravity. There +is no danger of loss by the formation of volatile ethers where the +quantity of amyl alcohol used does not exceed one cubic centimeter. +In a comparison of the respective merits of the methods of Babcock, +Thörner and Gerber, made by Hausamann, the first place is awarded to +the Gerber process.<a id="FNanchor_471" href="#Footnote_471" class="fnanchor">[471]</a> +In the <a href="#FIG_110">figure 110</a>, the butyrometers marked 2, 5 +<span class="pagenum"><a id="Page_504"></a>[Pg 504]</span> +and 8 are for milk, and those numbered 1, 3 and 7 are for cream and +cheese. In conducting the analysis, ten cubic centimeters of the +sulfuric acid are placed in the butyrometer with one cubic centimeter +of the amyl alcohol. When mixed, eleven cubic centimeters of the +milk are added and the contents of the tube well mixed, the tube +stoppered and placed in the centrifugal. The larger tubes, open at both +ends, require double the quantities of the reagents mentioned. The +measurements are made at about 15°.</p> + +<p>Minute directions for conducting the analyses with milk, skim milk, +buttermilk, cream, condensed milk, cheese and butter accompany each +apparatus.</p> + +<h3>PROTEID BODIES IN MILK.</h3> + +<p><b>476. Kinds of Proteid Bodies in Milk.</b>—The proteid bodies in +milk are all found in at least partial solution. Some authorities state +that a portion of the casein is present in the form of fine particles +suspended after the manner of the fat globules.<a id="FNanchor_472" href="#Footnote_472" class="fnanchor">[472]</a> +The number and kind of proteid bodies are not known with definiteness. +Among those which are known with certainty are casein, albumin, peptone +and fibrin. The latter body was discovered in milk by Babcock.<a id="FNanchor_473" href="#Footnote_473" class="fnanchor">[473]</a> +Lactoglobulin and lactoprotein are also names given to imperfectly +known proteid bodies in milk. Lactoprotein is not precipitated either +by acids or by heat and is therefore probably a peptone. By far the +greater part of the proteid matters in milk is casein. Casein has been +called caseinogen by Halliburton,<a id="FNanchor_474" href="#Footnote_474" class="fnanchor">[474]</a> +and paracasein by Schulze and Röse.<a id="FNanchor_475" href="#Footnote_475" class="fnanchor">[475]</a> +Casein has intimate relations to the mineral matters in milk, and is +probably itself made up of several proteid bodies of slightly differing +properties. In general all that class of proteid matter contained in +milk which is precipitated by rennet or a weak acid, or spontaneously +on the development of lactic acid, is designated by the term casein, +while the albumins and peptones in similar conditions remain in +solution. Casein contains phosphorus, presumably as nuclein. Fibrin is +recognized in milk by the reactions it gives with hydrogen peroxid or +gum guiacum. The decomposition of hydrogen peroxid is not a certain +test for fibrin, inasmuch as pus and many other bodies will produce the +<span class="pagenum"><a id="Page_505"></a>[Pg 505]</span> +same effect. If the milk decompose hydrogen peroxid, however, before +and not after boiling, an additional proof of the presence of fibrin +is obtained, since boiled fibrin does not act on the reagent.<a id="FNanchor_476" href="#Footnote_476" class="fnanchor">[476]</a> +The gum guiacum test is applied by dipping a strip of filter paper into the +milk and drying. The solution of gum guiacum is applied to the dried +paper and the presence of fibrin is recognized by the blue color which +is produced. The fibrin is probably changed into some other proteid +during the ripening of cream in which the fibrin is chiefly found. The +albumin in milk is coagulated by boiling, while the casein remains +practically unaffected when subjected to that temperature.</p> + +<p><b>477. Estimation of Total Proteid Matter.</b>—The total proteid +matter in milk is determined by any of the general methods applicable +to the estimation of total nitrogen, but the moist combustion method +is by far the most convenient. From the total nitrogen, that which +represents ammonia or other nonproteid nitrogenous bodies, is to +be deducted and the remainder multiplied by an appropriate factor. +Practically all the nitrogen obtained is derived from the proteid +matters and, as a rule, no correction is necessary. The factors +employed for calculating the weight of proteid matter from the nitrogen +obtained vary from 6.25 to 7.04. It is desirable that additional +investigations be made to determine the magnitude of this factor. It +is suggested that provisionally the factor 6.40 be used. In the method +adopted by the Association of Official Agricultural Chemists it is +directed that about five grams of milk be placed in the oxidizing flask +and treated without previous evaporation exactly as described for the +estimation of total nitrogen in the absence of nitrates. The nitrogen +obtained is multiplied by 6.25 to get the total proteid matter.<a id="FNanchor_477" href="#Footnote_477" class="fnanchor">[477]</a> +In order to prevent the too great dilution of the sulfuric acid, the milk +may be evaporated to dryness or nearly so before oxidation. In this +laboratory it is conveniently done by placing the milk first in the +oxidizing flask, connecting this with the vacuum service and placing +the flask in hot water. The aqueous contents of the milk are quickly +given off at a temperature not exceeding 85°, and the time required is +only a few minutes. +<span class="pagenum"><a id="Page_506"></a>[Pg 506]</span></p> + +<p>The milk may also be dried in dishes made of thin glass or tin foil +and, after desiccation, introduced with the fragments of the dishes +into the oxidizing flask.</p> + +<p>The preliminary drying in the oxidizing flask is recommended as the +best.</p> + +<p>Söldner oxidizes the nitrogen in human milk by boiling ten cubic +centimeters thereof for three hours with twenty-five of sulfuric +acid, fifty milligrams of copper oxid and three drops of a four per +cent platinic chlorid solution, and, after distilling the ammonia, +uses the factor 6.39 for calculating the proteid matter. According to +this author human milk is much less rich in nitrogenous constituents +than is generally supposed, containing not more than one and a half +per cent thereof in average samples collected at least a month after +parturition.<a id="FNanchor_478" href="#Footnote_478" class="fnanchor">[478]</a></p> + +<p><b>478. Precipitation of Total Proteids with Copper Sulfate.</b>—This +method of throwing out the total proteids of milk is due to +Ritthausen.<a id="FNanchor_479" href="#Footnote_479" class="fnanchor">[479]</a> +The proteids and fat are precipitated together by the addition of a +measured volume of copper sulfate solution, containing 63.92 grams +of the crystallized salt in one liter. The process, as modified by +Pfeiffer, is conducted as follows:<a id="FNanchor_480" href="#Footnote_480" class="fnanchor">[480]</a></p> + +<p>Ten grams of milk are diluted with ten times that much water, five +cubic centimeters of the copper sulfate solution added and then soda +lye solution drop by drop until the copper is just precipitated. This +is determined by testing a few drops of the filtrate with soda lye, +which, when the copper is precipitated, will give neither a turbidity +nor a blue color.</p> + +<p>The mixture is poured into a dry tared filter, the precipitate washed +with hot water, dried to constant weight and weighed. The fat is +removed from the dry pulverized mass by extraction with ether and the +residue dried and weighed.</p> + +<p>The quantity of copper oxyhydrate contained in the precipitate is +calculated from the quantity of the copper solution used and amounts +to 0.2026 gram. The casein thus prepared contains not only the copper +compound named, but also some of the sodium sulfate formed on the +addition of the soda lye and other mineral salts present in the milk +and from which it is quite impossible to completely free it. There are +also many other objections to the process, and the product is of such a +nature as to render the data obtained by the method very doubtful. +<span class="pagenum"><a id="Page_507"></a>[Pg 507]</span></p> + +<p>This method is chiefly valuable on account of its historical interest. +Not only are the drying and weighing of the precipitate rendered +unnecessary by the modern methods of determining nitrogen, but there +are numerous sources of error which seem to throw doubt on the accuracy +of the results. The copper hydroxid does not lose all its water even on +drying at 125°.<a id="FNanchor_481" href="#Footnote_481" class="fnanchor">[481]</a> +The method therefore can only be recommended for practical purposes +when all the tedious processes of drying, extracting and calculating +the quantity of copper oxid are abandoned and the moist washed +precipitate used directly for the determination of nitrogen.</p> + +<p><b>479. Proteid Bodies by Ammonium Sulfate.</b>—All the proteid bodies +except peptones are precipitated from milk on saturation with ammonium +sulfate. This method has little analytical value because of the +presence of nitrogenous salt in the precipitate. Zinc sulfate may be +substituted for the ammonium salt and thus a determination of proteid +matter other than peptone be obtained. This result subtracted from the +total proteid nitrogen gives that due to peptone.</p> + +<p id="P_480"><b>480. Total Proteid Matter by Tannic Acid.</b>—For the determination +of the total proteid matter in milk Sebelien uses the following +process.<a id="FNanchor_482" href="#Footnote_482" class="fnanchor">[482]</a> +From three to five grams are diluted with three or four volumes of +water, a few drops of a saline solution added (sodium phosphate, sodium +chlorid, magnesium sulfate, <i>et similia</i>), and the proteid bodies +thrown out with an excess of tannic acid solution. The precipitate +is washed with an excess of the precipitant and the nitrogen therein +determined and multiplied by 6.37.</p> + +<p><b>481. Separation of Casein from Albumin.</b>—Sebelien prefers +magnesium sulfate or sodium chlorid to acetic acid as the best reagent +for separating casein from lactalbumin. Of the two saline reagents +mentioned, the former is the better. The milk is first diluted +with a double volume of the saturated saline solution and then the +fine powdered salt added until saturation is secured. The casein +is completely thrown out by this treatment, collected on a filter, +washed with the saturated saline solution, and the nitrogen therein +<span class="pagenum"><a id="Page_508"></a>[Pg 508]</span> +determined. The difference between the total and casein nitrogen gives +the quantity due to the albumin plus the almost negligible quantity due +to globulin.<a id="FNanchor_483" href="#Footnote_483" class="fnanchor">[483]</a></p> + +<p><b>482. Van Slyke’s Method of Estimating Casein.</b>—The casein may +be separated from the other albuminoids in milk by the procedure +proposed by Van Slyke.<a id="FNanchor_484" href="#Footnote_484" class="fnanchor">[484]</a> +Ten grams of the fresh milk are diluted with ninety cubic centimeters +of water and the temperature raised to 40°. The casein is thrown down +with a ten per cent solution of acetic acid, of which about one and a +half cubic centimeters are required. The mixture is well stirred and +the precipitate allowed to subside. The whey is decanted onto a filter, +and the precipitate washed two or three times with cold water, brought +finally onto the filter and washed once or twice with cold water. +The filter paper and its contents are used for the determination of +nitrogen in the usual way. The casein is calculated from the nitrogen +found by multiplication by the factor 6.25. Milk may be preserved +for this method of determination by adding to it one part of finely +powdered mercuric chlorid for each two thousand parts of the sample. +The method is not applicable to curdled milk.</p> + +<p><b>483. Theory of Precipitation.</b>—Most authorities now agree in +supposing that the state of semisolution in which the casein is held in +milk is secured by the presence of mineral matters in the milk, in some +intimate combination with the casein. Among these bodies lime is of +the most importance. The action of the dilute acid is chiefly on these +mineral bodies, releasing them from combination with the casein, which, +being insoluble in the milk serum, is precipitated.</p> + +<p><b>484. Factors for Calculation.</b>—Most analysts still use the +common proteid factor, 6.25, in calculating the quantity of proteids +from the nitrogen determined by analysis. For casein many different +factors have been proposed. According to Makeris the factor varies from +6.83 to 7.04.<a id="FNanchor_485" href="#Footnote_485" class="fnanchor">[485]</a> +Munk gives 6.34 for human and 6.37 for cow milk.<a id="FNanchor_486" +href="#Footnote_486" class="fnanchor">[486]</a> Sebelien adopts the +latter factor, and Hammersten nearly the same; <i>viz.</i>, 6.39. The +weight of authority, at the present time, favors a factor considerably +above 6.25 for calculating the casein and, in fact, the total proteids +of milk from the weight of nitrogen obtained. +<span class="pagenum"><a id="Page_509"></a>[Pg 509]</span></p> + +<p><b>485. Béchamp’s Method of Preparing Pure Casein.</b>—The casein in +about one liter of milk is precipitated by adding gradually about three +grams of glacial acetic acid diluted with water. The addition of the +acid is arrested at the moment when litmus paper shows a slightly acid +reaction. The precipitate thus produced, containing all the casein, +the milk globules and the microzymes, is separated by filtration, +being washed by decantation before collecting it on the filter. On +the filter it is washed with distilled water and the fat removed by +shaking with ether. The residue is suspended in water, dissolved in the +least possible quantity of ammonium carbonate, any insoluble residue +(microzymes, globules) separated by filtration and the pure casein +thrown out of the filtrate by the addition of acetic acid. The washing +with distilled water, solution in ammonium carbonate, filtration and +reprecipitation are repeated three or four times in order to obtain +the casein entirely free of other substances. Casein thus prepared is +burned to a carbon free ash with difficulty and contains but little +over one-tenth per cent of mineral matter.<a id="FNanchor_487" href="#Footnote_487" class="fnanchor">[487]</a></p> + +<p><b>486. Separation of Casein with Carbon Dioxid.</b>—The +supersaturation of the lime compounds of casein with carbon dioxid +diminishes the solvent action of the lime and thus helps to throw out +the proteid matter. For this reason Hoppe-Seyler recommends the use +of carbon dioxid to promote the precipitation of the casein.<a id="FNanchor_488" href="#Footnote_488" class="fnanchor">[488]</a> +The milk is diluted with about twenty volumes of water and treated, drop by +drop, with very dilute acetic acid as long as a precipitate is formed. +A stream of pure carbon dioxid is conducted through the mixture for +half an hour, and it is allowed to remain at rest for twelve hours, +when the casein will have all gone down and the supernatant liquid will +be clear. Albumins and peptones are not thrown out by this treatment.</p> + +<p>The method of precipitation is advantageously modified by saturating +the diluted milk with carbon dioxid before adding the acetic acid, less +of the latter being required when used in the order just noted.<a id="FNanchor_489" href="#Footnote_489" class="fnanchor">[489]</a></p> + +<p><b>487. Separation of Albumin.</b>—In the filtrate from the casein +<span class="pagenum"><a id="Page_510"></a>[Pg 510]</span> +precipitate the albumin may be separated by heating to 80°. It may also +be precipitated by tannic acid, in which case it may contain a little +globulin. It may also be thrown out by saturation with ammonium or +zinc sulfates. The latter reagent is to be preferred when the nitrogen +is to be determined in the precipitate. The quantities of albumin and +globulin, especially the latter, present in milk are small compared +with its content of casein.</p> + +<p><b>488. Separation of Globulin.</b>—The presence of globulin in milk +is demonstrated by Sebelien in the following manner:<a id="FNanchor_490" href="#Footnote_490" class="fnanchor">[490]</a> +The milk is saturated with finely powdered common salt and the precipitate +produced is separated by filtration. This filtrate in turn is +saturated with magnesium sulfate. The precipitate produced by this +reagent is collected on a filter, dissolved in water and precipitated +by saturation with sodium chlorid. This process is repeated several +times. The final precipitate is proved to be globulin by the following +reactions: When a solution of it is dialyzed the proteid body +separates as a flocculent precipitate, which is easily dissolved in +a weak solution of common salt. The clear solution thus obtained +becomes turbid on adding water, and more so after the addition of a +little acetic acid. A neutral solution of the body is also completely +precipitated by saturation with sodium chlorid. These reactions serve +to identify the body as a globulin and not an albumin. All the globulin +in milk is not obtained by the process, since a part of it is separated +with the casein in the first precipitation.</p> + +<p><b>489. Other Precipitants of Milk Proteids.</b>—Many other reagents +besides those mentioned have been used for precipitating milk +proteids, wholly or in part. Among these may be mentioned the dilute +mineral acids, lactic acid, rennet, mercuric iodid in acetic acid, +phosphotungstic acid, acid mercuric nitrate, lead acetate and many +others.</p> + +<p>It has been shown by the author that many of these precipitants do not +remove all the nitrogen but that among others the mercury salts are +effective.<a id="FNanchor_491" href="#Footnote_491" class="fnanchor">[491]</a> +When nitrogen is to be subsequently determined the acid mercuric +nitrate cannot be employed. +<span class="pagenum"><a id="Page_511"></a>[Pg 511]</span></p> + +<p><b>490. Precipitation by Dialysis.</b>—Since the casein is supposed to +be held in solution by the action of salts it is probable that it may +be precipitated by removing these salts by dialysis.</p> + +<p><b>491. Carbohydrates in Milk.</b>—The methods of determining lactose +in milk, both by the copper reduction and optical processes, have been +fully set forth in foregoing paragraphs (<b><a href="#P_243">243</a>, +<a href="#P_244">244</a>, <a href="#P_259">259</a>, <a href="#P_262">262</a></b>). +In general, the optical method by double dilution is to be preferred +as practically exact and capable of application with the minimum +consumption of time.<a id="FNanchor_492" href="#Footnote_492" class="fnanchor">[492]</a> +For normal milks a single polarization is entirely sufficient, making +an arbitrary correction for the volume occupied by the precipitated +proteids and fat. This correction is conveniently placed at six and a +half per cent of the volume of milk employed.</p> + +<p>The polarimetric estimation of lactose in human milk is likely to give +erroneous results by reason of the existence in the serum of polarizing +bodies not precipitable by the reagents commonly employed for the +removal of proteids.<a id="FNanchor_493" href="#Footnote_493" class="fnanchor">[493]</a> +The same statement may be made in respect of ass and mare milk. The use +of acetopicric acid for removing disturbing bodies, as proposed by +Thibonet<a id="FNanchor_494" href="#Footnote_494" class="fnanchor">[494]</a> +does not insure results free from error. With the milks above +mentioned, it is safer to rely on the data obtained by the alkaline +copper reagents.</p> + +<p><b>492. Dextrinoid Body in Milk.</b>—In treating the precipitate, +produced in milk by copper sulfate, with alcohol and ether for the +purpose of removing the fat, Ritthausen isolated a dextrin like body +quite different from lactose in its properties.<a id="FNanchor_495" href="#Footnote_495" class="fnanchor">[495]</a> +The alcohol ether extract evaporated to dryness leaves a mass not +wholly soluble in ether, and therefore not composed of fat. This +residue extracted with ether, presents flocky particles, soluble in +water and mostly precipitated therefrom by alcohol. This body has a +slight reducing effect on alkaline copper salts and produces a gray +color with bismuth nitrate. The quantity of this material is so minute +as to lead Ritthausen to observe that it does not sensibly affect the +fat determinations when not separated. It is not clearly demonstrated +that it is a dextrinoid body and the analyst need not fear that the +optical determination of milk sugar will be sensibly affected thereby.</p> + +<p>Raumer and Späth assume that certain discrepancies, observed by them in +<span class="pagenum"><a id="Page_512"></a>[Pg 512]</span> +the data obtained for lactose by the copper and optical methods, are +due to the presence of this dextrinoid body, but no positive proof +thereof is adduced.<a id="FNanchor_496" href="#Footnote_496" class="fnanchor">[496]</a></p> + +<p><b>493. Amyloid Bodies in Milk.</b>—Herz has observed in milk a body +having some of the characteristics of starch.<a id="FNanchor_497" href="#Footnote_497" class="fnanchor">[497]</a> +Observed by the microscope, these particles have some of the +characteristics of the starch grains of vegetables, with a diameter +of from ten to thirty-five micromillimeters. They are colored blue by +iodin. When boiled with water, however, these particles differ from +starch in not forming a paste. The particles are most abundant in the +turbid layer found immediately beneath the ether fat solution in the +areometric process of Soxhlet.</p> + +<p>The amyloid particles may be collected from cheese and butter by +boiling with water, when they settle and can be observed on the +sediment after freeing of fat by ether.</p> + +<p>Some of the statements regarding the adulteration of dairy products +with starch may have been made erroneously by reason of the natural +occurrence of these particles.</p> + +<p>As in the case of the dextrin like body mentioned above this starchy +substance, if it really exist, occurs in too minute a quantity to +influence the results of any of the analytical methods heretofore +described.</p> + +<p>In connection with the supposed presence of an amyloid body in milk, +it should be remembered that certain decomposition nitrogenous bodies +give practically the same reactions as are noted above.<a id="FNanchor_498" href="#Footnote_498" class="fnanchor">[498]</a> +Among these may be mentioned chitin, which occurs very extensively in +the animal world. The proof of the existence of dextrinoid and amyloid +bodies in milk rests on evidence which should be thoroughly revised +before being undoubtedly accepted.</p> + +<h3>ANALYSIS OF BUTTER.</h3> + +<p><b>494. General Principles.</b>—The general analysis of butter fat +is conducted in accordance with the methods described in the part of +this volume devoted to the examination of fats and oils. The methods of +sampling, drying, filtering, and of determining physical and chemical +properties, are there developed in sufficient detail to guide the +<span class="pagenum"><a id="Page_513"></a>[Pg 513]</span> +analyst in all operations of a general nature. There remain for +consideration here only the special processes practiced in butter +analysis and which are not applied to fats in general. These processes +naturally relate to the study of those properties of a distinctive +nature, by means of which butter is differentiated from other fats for +which it may be mistaken or with which it may be adulterated. These +special studies, therefore, are directed chiefly to the consideration +of the peculiar physical properties of butter fat, to its content of +volatile acids and to its characteristic forms of crystallization as +observed with the aid of the microscope. For dietetic, economic and +legal reasons, it is highly important that the analyst be able to +distinguish a pure butter from any substitute therefor.</p> + +<p><b>495. Appearance of Melted Butter.</b>—Fresh, pure butter, when +slowly melted, shows after a short time the butter fat completely +separated, of a delicate yellow color and quite transparent. Old +samples of butter do not give a fat layer of equal transparency. +Oleomargarin, or any artificial butter when similarly treated, gives +a fat layer opalescent or opaque. By means of this simple test an +easy separation of pure from adulterated butter may be effected. In +mixtures, the degree of turbidity shown by the separated fats may be +regarded as a rough index of the amount of adulteration. In conducting +the work, the samples of butter, in convenient quantities according to +the size of the containing vessel, are placed in beakers and warmed +slowly at a temperature not exceeding 50°. After a lapse of half an +hour the observations are made.</p> + +<p>If one part of the melted butter be shaken with two volumes of warm +water (40°) and set aside for five minutes the fat is still found as an +emulsion, while oleomargarin, similarly treated, shows the fat mostly +separated. This process has some merit, but must not be too highly +valued.<a id="FNanchor_499" href="#Footnote_499" class="fnanchor">[499]</a></p> + +<p><b>496. Microscopic Examination of Butter.</b>—The microscope is +helpful in judging the purity of butter and the admixture of foreign +fats, if not in too small quantity to be of any commercial importance, +can easily be detected by this means.<a id="FNanchor_500" href="#Footnote_500" class="fnanchor">[500]</a> +The methods of preparing butter fat in a crystalline state are the same +as those described in paragraphs <b><a href="#P_307">307-309</a></b>. The crystals of butter +<span class="pagenum"><a id="Page_514"></a>[Pg 514]</span> +fat differ greatly in appearance with the different methods of +preparation. When butter is melted, filtered, heated to the boiling +point of water and slowly cooled, it forms spheroidal crystalline +masses as seen by the microscope, which present a well defined cross +with polarized light. This cross is not peculiar to butter fat, but is +developed therein with greater distinctiveness than in other fats of +animal origin.</p> + +<p>Pure, fresh, unmelted butter, when viewed with polarized light through +a plate of selenite, presents a field of vision of uniform tint, +varying with the relative positions of the nicols. When foreign fats, +previously melted, as in rendering, are mixed with the butter the +crystallization they undergo disturbs this uniformity of tint and the +field of vision appears particolored. Old, rancid or melted butter may +give rise to the same or similar phenomena under like conditions of +examination. The microscope thus becomes a most valuable instrument for +sorting butters and in distinguishing them in a preliminary way from +oleomargarin.</p> + +<div class="figcenter smcap"> + <img id="FIG_112" src="images/fig112.jpg" alt="" width="600" height="102" > + <p class="center spb1">Fig. 112. Thermometer for Butyrorefractometer.</p> +</div> + +<p><b>497. Judgment of Suspected Butter or Lard by Refractive +Power.</b>—In discriminating between pure and adulterated butters by +the aid of the butyrorefractometer (<b><a href="#P_301">301</a></b>), the absolute reading +of the instrument is of less importance than the difference which is +detected between the highest permissible numbers, for any degree of +temperature, and the actual reading obtained at that temperature. These +differences, within certain limits, do not perceptibly vary with the +temperature, and heretofore they have been determined with the aid of +a table, and in this respect the observations have been made the more +laborious.</p> + +<p>Wollny has rendered these tables unnecessary by constructing a +thermometer in which the mercury column does not indicate degrees of +temperature, but the highest permissible number for butter or lard +at the temperature of observation. The scale of the instrument is so +adjusted as to include temperatures of from 30° to 40°, which renders +it suited to the examination of butter and lard. The oleothermometer is +shown in <a href="#FIG_112">Fig. 112</a>. +<span class="pagenum"><a id="Page_515"></a>[Pg 515]</span></p> + +<p>The side of the scale <i>B</i> is for butter and that marked <i>S</i> +for lard. The use of the instrument is the simplest possible. The +sample of fat is placed in the prisms in the usual manner. When the +mercury in the thermometer is at rest, the scale of the instrument +is read. In the case of a butter, if the reading of the scale give a +higher number than that indicated by the thermometer, the sample is +pronounced suspicious and the degree of suspicion is proportional to +the difference of the two readings.</p> + +<p id="P_498"><b>498. Estimation of Water, Fat, Casein, Ash and Salt.</b>—The +methods proposed by the author for conducting these determinations, +with minor amendments, have been adopted by the Association of Official +Agricultural Chemists.<a id="FNanchor_501" href="#Footnote_501" class="fnanchor">[501]</a></p> + +<p><i>Water.</i>—The sample held in a flat bottom dish is dried to +constant weight at about 100°. The weight of the sample used should +be proportional to the area of the bottom of the dish, which should +be just covered by the film of melted fat. The dish may be previously +partly filled with sand, asbestos or pumice stone. The drying may take +place in the air, in an inert gas or in a vacuum.</p> + +<p><i>Fat.</i>—The fat in a sample of butter is readily determined by +treating the contents of the dish after the determination of water with +an appropriate solvent.</p> + +<p>The process is conducted as follows:</p> + +<p>The dry butter from the water determination is dissolved in the dish +with ether or petroleum spirit. The contents of the dish are then +transferred to a weighed gooch with the aid of a wash bottle containing +the solvent, and washed till free of fat. The crucible and contents are +heated at the temperature of boiling water till the weight is constant. +The weight of fat is calculated by difference from the data obtained.</p> + +<p>The fat may also be determined by drying the butter on asbestos or +sand, and subsequently extracting the fat by anhydrous alcohol free +ether. The extract, after evaporation of the ether, is dried to +constant weight at the temperature of boiling water and weighed. +<span class="pagenum"><a id="Page_516"></a>[Pg 516]</span></p> + +<p><i>Casein or Curd and Ash.</i>—The crucible containing the residue +from the fat determination is covered and heated, gently at first, +gradually raising the temperature to just below redness. The cover +may then be removed and the heat continued till the contents of the +crucible are white. The loss in weight of the crucible and contents +represents casein or curd, and the residue is mineral matter or ash.</p> + +<p><i>Salt.</i>—It is the usual custom in the manufacture of butter in +this country to add, as a condiment, a certain proportion of salt. +In Europe, the butter offered for consumption is usually unsalted. A +convenient method of determining the quantity of salt is found in the +removal thereof, from the sample, by repeated washing with hot water +and in determining the salt in the wash water by precipitation with +silver nitrate. The operation is conducted as follows: From five to +ten grams of the sample are placed in a separatory funnel, hot water +added, the stopper inserted and the contents of the funnel well shaken. +After standing until the fat has all collected on top of the water, the +stopcock is opened and the water is allowed to run into an erlenmeyer, +being careful to let none of the fat globules pass. Hot water is again +added to the beaker, and the extraction is repeated several times, +using each time from ten to twenty cubic centimeters of water. The +resulting washings contain all but a mere trace of the sodium chlorid +originally present in the butter. The sodium chlorid is determined in +the filtrate by a set solution of silver nitrate, using a few drops of +a solution of potassium chromate as an indicator.</p> + +<p>It is evident that the quantity of salt may also be determined from the +ash or mineral matter obtained, as above noted, by the same process. +If desirable, which is rarely the case, the gravimetric method of +estimating the silver chlorid may be used.</p> + +<p><b>499. Volatile or Soluble Acids.</b>—The distinguishing feature +of butter, from a chemical point of view, is found in its content of +volatile or soluble fat acids. Among the volatile acids are reckoned +those which are carried over in a current of steam at a temperature +only slightly higher than that of boiling water. As soluble acids are +<span class="pagenum"><a id="Page_517"></a>[Pg 517]</span> +regarded those which pass without great difficulty into solution in hot +water. These two classes are composed essentially of the same acids. +Of these butyric is the most important, followed by caproic, caprylic +and capric acids. Small quantities or rather traces of acetic, lauric, +myristic and arachidic acids are also sometimes found in butter. +Palmitic, stearic and oleic acids also occur in large quantities. The +above named acids, in combination with glycerol, form the butter fat.</p> + +<p><b>500. Relative Proportion of Ingredients.</b>—The composition +of butter fat is given differently by different authorities.<a id="FNanchor_502" href="#Footnote_502" class="fnanchor">[502]</a> +A typical dry butter fat may be regarded as having the following +composition:</p> + +<table class="spb1"> + <tbody><tr> + <td class="tdr" colspan="2">  Per cent.</td> + </tr><tr> + <td class="tdl">Butyrin</td> + <td class="tdr">7.00</td> + </tr><tr> + <td class="tdl">Caproin, Caprylin and Caprin   </td> + <td class="tdr">2.30</td> + </tr><tr> + <td class="tdl">Olein</td> + <td class="tdr">37.70</td> + </tr><tr> + <td class="tdl">Palmitin, stearin, etc.</td> + <td class="tdr">53.00</td> + </tr> + </tbody> +</table> + +<p>Pure butter fat consists principally of the above glycerids, some +coloring principles, varying in quantity and composition with the food +of the animal, and a trace of lecithin, cholesterol, phytosterol and a +lipochrome.</p> + +<p><b>501. Estimation of Volatile or Soluble Acids.</b>—The volatile +or soluble acids in butter fat are estimated by the methods already +described (<b><a href="#P_349">349</a>, <a href="#P_351">351</a></b>). +In practice preference is given to the method of determining volatile +acids, based on the principle that under standard conditions +practically all the acids of this nature are secured in a certain +volume of the distillate. This assumption is not strictly true, but the +method offers a convenient and reliable manner of obtaining results +which, if not absolute, are at least comparative.</p> + +<p>The quantity of acid distilled is determined by titration with tenth +normal alkali and for convenience the data are expressed in terms of +the volume of the alkali consumed. Five grams of normal butter fat +will give a distillate, under the conditions given, requiring about +twenty-eight cubic centimeters of tenth normal alkali for complete +saturation. This is known as the reichert-meissl number. Occasionally +this number may rise to thirty-two or may sink to twenty-five. Cases +<span class="pagenum"><a id="Page_518"></a>[Pg 518]</span> +have been reported where it fell below the latter number, but such +samples cannot be regarded as normal butter.</p> + +<p>The determination of the reichert-meissl number is the most important +of the chemical processes applied to butter fat analysis.</p> + +<p><b>502. Saponification Value and Reichert Number.</b>—It may often be +convenient to make the same sample of butter fat serve both for the +determination of the saponification value and of the reichert number. +For this purpose it is convenient to use exactly five grams of the +dry filtered fat. The saponification may be accomplished either under +pressure or by attaching a reflux condenser to the flask as suggested +by Bremer.<a id="FNanchor_503" href="#Footnote_503" class="fnanchor">[503]</a> +When the saponification, which is accomplished with alcoholic potash +lye containing about 1.25 grams in each ten cubic centimeters of +seventy per cent alcohol, is finished, and the contents of the flask +are cooled, the residual alkali is titrated with a set sulfuric acid +solution, using phenolphthalein as indicator. When the color has almost +disappeared, an additional quantity of the indicator is added and the +titration continued until the liquid is of an amber tint. A sample of +the alkali, treated as above, is titrated at the same time and from the +two sets of data obtained, the saponification number is calculated as +indicated in paragraph (<b><a href="#P_345">345</a></b>).</p> + +<p>A few drops of the alcoholic lye are added to the contents of the flask +and the alcohol removed by evaporation. The residual soap and potassium +sulfate are dissolved in 100 cubic centimeters of recently boiled +water, some pieces of pumice added, and the volatile acids removed by +distillation in the usual way after adding an excess of sulfuric acid. +It is important to conduct blank distillations in the same form of +apparatus to determine the magnitude of any corrections to be made. +The size of the distilling flask and the form of apparatus to prevent +mechanical projection of sulfuric acid into the distillate should be +the same in all cases.</p> + +<p><b>503. Modification of the Reichert-Meissl Method.</b>—Kreis has +proposed the use of strong sulfuric acid for saponifying the fats, the +<span class="pagenum"><a id="Page_519"></a>[Pg 519]</span> +saponification and distillation being accomplished in one operation. +A source of error of some inconvenience in this method is due to the +development of sulfurous acid by the reducing action of the organic +matter on the oil of vitriol. Pinette proposes to avoid this difficulty +by adding, before the distillation is begun, sufficient potassium +permanganate to produce a permanent red coloration. By this means the +sulfurous acid is completely oxidized and its transfer to the standard +alkali during distillation entirely prevented. The same result is +accomplished by Micko by the use of potassium bichromate. The details +of the manipulation are as follows:<a id="FNanchor_504" href="#Footnote_504" class="fnanchor">[504]</a></p> + +<p>About five grams of the fused fat (butter or oleomargarin) are placed +in a flask of approximately 300 cubic centimeters capacity. After +cooling, there are added ten cubic centimeters of sulfuric acid +containing three grams of water to each ninety-seven grams of the +strongest acid.</p> + +<p>The fat and acid are well mixed by a gentle rotatory motion of the +flask and placed in a water bath at a temperature of 35° (<i>circa</i>) +for fifteen minutes. At the end of this time the flask is removed from +the bath and 125 cubic centimeters of water added, little by little, +keeping the contents cool. Next are added four cubic centimeters of a +four per cent solution of potassium bichromate. The contents of the +flask are vigorously shaken and, after five minutes, a solution of +ferrous sulfate is added gradually from a burette until the reaction +with a drop of potassium ferrocyanid shows a slight excess of the iron +salt. The volume of the liquor in the flask is then increased to 150 +cubic centimeters by the addition of water and 110 cubic centimeters +distilled. After mixing and filtering through a dry filter, the acid +in 100 cubic centimeters is determined by standard tenth normal barium +hydroxid solution and the number thus obtained increased by one-tenth +representing the total acid obtained.</p> + +<p><b>504. Elimination of Sulfurous Acid.</b>—Prager and Stern<a id="FNanchor_505" href="#Footnote_505" class="fnanchor">[505]</a> +propose to eliminate the sulfurous acid by a stream of air, succeeded +by one of carbon dioxid, and proceed as follows: Five grams of the +butter fat are brought into a liter flask, ten cubic centimeters of +strong sulfuric acid are added and the flask is kept for ten minutes at +<span class="pagenum"><a id="Page_520"></a>[Pg 520]</span> +30-32° with constant agitation. When the liquid is cold, air is +bubbled through it until the odor of sulfurous acid has disappeared. +One hundred cubic centimeters of water are added, with precautions +against rise of temperature, and carbon dioxid is bubbled through for +ten minutes. This is then displaced by a stream of air for another ten +minutes, the delivery tube is washed into the flask with fifty cubic +centimeters of water and the distillation is effected. The following +results are quoted:</p> + +<p>Cubic centimeters of tenth normal alkali required by five grams of +butter fat:</p> + +<table class="spb1"> + <tbody><tr class="fs_90"> + <td class="tdr" colspan="2"> </td> + <td class="tdc"> Reichert-Meissl. </td> + <td class="tdc"> Prager-Stern. </td> + </tr><tr> + <td class="tdl">Sample</td> + <td class="tdl_wsp"><i>a</i></td> + <td class="tdc">29.86</td> + <td class="tdc">29.60</td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdl_wsp"><i>b</i></td> + <td class="tdc">30.23</td> + <td class="tdc">29.65</td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdl_wsp"><i>c</i></td> + <td class="tdc">28.34</td> + <td class="tdc">27.76</td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdl_wsp"><i>d</i></td> + <td class="tdc">28.20</td> + <td class="tdc">28.10</td> + </tr> + </tbody> +</table> + +<p>The authors do not comment on the possibility of loss of acids +other than sulfurous in the stream of air, but they admit that +further investigation is requisite to render the suggestion of Kreis +serviceable.</p> + +<p><b>505. Errors Due to Poor Glass.</b>—The easy solubility of the glass +holding the reagents is the cause of some of the difficulties attending +the determination of the saponification value. The separated silica +tends to carry down, mechanically, a part of the alkali. This is shown +by the fact that after the color has been discharged by titration +with acid and the flask set aside a reappearance of the red color is +noticed, after a time, beginning at the bottom of the flask.<a id="FNanchor_506" href="#Footnote_506" class="fnanchor">[506]</a> +In order to avoid difficulties of this nature, either cold saponification +should be practiced or the digestion vessels used for moist combustion +in sulfuric acid be employed.</p> + +<p>Errors may also be easily introduced by the use of uncalibrated +burettes and from the employment of varying quantities of the +phenolphthalein solution.</p> + +<p><b>506. Estimation of the Molecular Weight of Butter and Butter +Substitutes.</b>—Garelli and Carono have proposed a method for +discriminating between butter and its substitutes by the kryoskopic +determination of molecular weights. +<span class="pagenum"><a id="Page_521"></a>[Pg 521]</span></p> + +<p>The molecular weights of stearin, palmitin and olein are 890, 806 +and 884, and of butyrin, caproin and caprylin 303, 386 and 470 +respectively. Pure butter, therefore, has a lower mean molecular weight +than margarin.</p> + +<p>The method and apparatus of Beckmann are used in the determination, +fifteen grams of benzol being employed as a solvent.</p> + +<p>The constant for the molecular depression of the benzol is found to be +53.</p> + +<p>The molecular weight obtained with samples of pure butter varied from +696 to 716, and for oleomargarin from 780 to 883.</p> + +<p>The figures obtained with mixtures of twenty, twenty-five, thirty-three +and fifty per cent of margarin with butter were 761, 720, 728 and 749 +respectively. The method can be relied upon to classify samples as follows:</p> + +<ul class="index fs_105"> +<li class="isub3">1. Pure butter.</li> +<li class="isub3">2. Butter containing margarin.</li> +<li class="isub3">3. Suspicious butter.<a id="FNanchor_507" href="#Footnote_507" class="fnanchor">[507]</a></li> +</ul> + +<p><b>507. Substitutes and Adulterants of Butter.</b>—In this country, +butter is never adulterated with cocoa or sesame oil, as is sometimes +the case in other lands. The common substitute for butter here is +oleomargarin, and the most common butter adulterant, neutral lard. The +methods of analyses, by means of which these bodies can be identified, +have already been sufficiently described. By the use of certain +digestive ferments and other bodies, butter may be made to hold an +excessive quantity of casein, sugar and water in the form of a somewhat +permanent emulsion.<a id="FNanchor_508" href="#Footnote_508" class="fnanchor">[508]</a> +This form of adulteration is revealed at once on melting the sample.</p> + +<p><b>508. Furfurol Reaction with Sesame Oil.</b>—Olive oil and sometimes +butter are mixed with the cheaper body, sesame oil. The latter is +detected with certainty, from the red coloration it gives when mixed +with furfurol and hydrochloric acid. Instead of furfurol, some body +yielding it when subjected to the action of hydrochloric acid, +<i>viz.</i>, sucrose or a pentose sugar, may be used. It has been +found by Wauters, however, that an alcoholic solution of two grams of +furfuraldehyd in 100 cubic centimeters of alcohol is the best reagent. +One-tenth of a cubic centimeter of this reagent is used for each +test.<a id="FNanchor_509" href="#Footnote_509" class="fnanchor">[509]</a></p> + +<p><span class="pagenum"><a id="Page_522"></a>[Pg 522]</span> +The test is made as follows: The quantity of the furfuraldehyd solution +mentioned above is mixed with ten cubic centimeters of hydrochloric +acid, and there are added, without mixing, an equal volume of the +suspected oil. On standing, a red coloration is produced at the zone of +separation of the two liquids. If the oil be sesame, the coloration is +produced instantly. As little as one per cent of sesame in a mixed oil +will show the color in two minutes. The manipulation is also varied by +shaking together the reagents and the melted butter. Turmeric, which +is sometimes used in coloring butter, also gives the rose-red color +when treated with hydrochloric acid, but turmeric supplies its own +furfuraldehyd. It is easy to distinguish therefore the coloration due +to sesame oil, which is developed only when furfuraldehyd is present, +from that due to the turmeric, which is produced without the aid of the +special reagent.</p> + +<p><b>509. Butter Colors.</b>—Where cows are deprived of green food and +root crops, such as carrots, and kept on a poorly balanced ration, the +butter made from their milk may be almost colorless. To remedy this +defect it is quite a common practice to color the product artificially. +Almost the sole coloring matter used in this country is anatto.<a id="FNanchor_510" href="#Footnote_510" class="fnanchor">[510]</a> +Other coloring matters which are occasionally employed are turmeric, +saffron, marigold leaves, yellow wood (<i>Chlorophora tinctoria</i>), +carrot juice, chrome yellow (lead chromate) and dinitrocresol.</p> + +<p>The use of small quantities of anatto, turmeric or saffron is +unobjectionable, from a sanitary point of view, but this is not the +case with such a substance as lead chromate. The detection of anatto or +saffron in butter may be accomplished by the method of Cornwall.<a id="FNanchor_511" href="#Footnote_511" class="fnanchor">[511]</a> +About five grams of the warm filtered fat are dissolved in about fifty +cubic centimeters of ordinary ether, in a wide tube, and the solution +is vigorously shaken for from ten to fifteen seconds, with from twelve +to fifteen cubic centimeters of a very dilute solution of caustic +potash or soda in water, only alkaline enough to give a distinct +reaction with turmeric paper, and to remain alkaline after separating +from the ethereal fat solution. The corked tube is set aside, and in +a few hours, at most, the greater part of the aqueous solution, now +<span class="pagenum"><a id="Page_523"></a>[Pg 523]</span> +colored more or less yellow by the anatto, can be drawn from beneath +the ether with a pipette or by a stopcock below, in a sufficiently +clear state to be evaporated to dryness and tested in the usual way +with a drop of concentrated sulfuric acid.</p> + +<p>Sometimes it is well to further purify the aqueous solution by shaking +it with some fresh ether before evaporating it, and any fat globules +that may float on its surface during evaporation should be removed by +touching them with a slip of filter paper; but the solution should not +be filtered, because the filter paper may retain much of the coloring +matter.</p> + +<p>The dry yellow or slightly orange residue turns blue or violet blue +with sulfuric acid, then quickly green, and finally brownish or +somewhat violet this final change being variable, according to the +purity of the extract.</p> + +<p>Saffron can be extracted in the same way; it differs from anatto very +decidedly, the most important difference being in the absence of the +green coloration.</p> + +<p>Genuine butter, free from foreign coloring matter, imparts at most a +very pale yellow color to the alkaline solution; but it is important +to note that a mere green coloration of the dry residue on addition +of sulfuric acid is not a certain indication of anatto (as some books +state) because the writer has thus obtained from genuine butter, +free from foreign coloring matter, a dirty green coloration, but not +preceded by any blue or violet-blue tint.</p> + +<p>Blank tests should be made with the ether.</p> + +<p>Turmeric is easily identified by the brownish to reddish stratum that +forms between the ethereal fat solution and the alkaline solution +before they are intimately mixed. It may be even better recognized by +carefully bringing a feebly alkaline solution of ammonia in alcohol +beneath the ethereal fat solution with a pipette, and gently agitating +the two, so as to mix them partially.</p> + +<p>Another method of separating artificial coloring matter has been +proposed by Martin.<a id="FNanchor_512" href="#Footnote_512" class="fnanchor">[512]</a></p> + +<p>A method of determining the relative amount of butter color has been +<span class="pagenum"><a id="Page_524"></a>[Pg 524]</span> +worked out by Babcock.<a id="FNanchor_513" href="#Footnote_513" class="fnanchor">[513]</a></p> + +<h3>EXAMINATION OF CHEESE.</h3> + +<p><b>510. Composition Of Cheese.</b>—Pure cheese is made from whole +milk by precipitating the casein with rennet. The precipitated casein +carries down also the fat of the milk and a little lactose and whey +remain incorporated with the cheesy mass. The ingredients of cheese +are therefore those of the whole milk less the greater part of the +whey, <i>id est</i>, milk sugar, lactalbumin, globulin, soluble mineral +matters and water. In the conversion of the crude precipitate noted +above into the cheese of commerce, it is subjected to a ripening +process which is chiefly conditioned by bacterial action. It is not +possible here to enter into a discussion of methods of isolating +and identifying the bacteria which promote or retard the ripening +process.<a id="FNanchor_514" href="#Footnote_514" class="fnanchor">[514]</a> +As a rule, about a month is required for the curing process, before the +cheeses are ready for boxing and shipment. The most important changes +during ripening take place in the proteid matter, which is so altered +as to become more palatable and more digestible as a result of the +bacterial activity.</p> + +<p>The percentage composition of the principal cheeses of commerce are +shown in the following table:<a id="FNanchor_515" href="#Footnote_515" class="fnanchor">[515]</a></p> + +<table class="spb1"> + <thead><tr> + <th class="tdc"> </th> + <th class="tdc bb">Water,<br> Per cent. </th> + <th class="tdc bb">Casein,<br> Per cent. </th> + <th class="tdc bb">Fat,<br> Per cent. </th> + <th class="tdc bb">Sugar,<br> Per cent. </th> + <th class="tdc bb">Ash,<br> Per cent. </th> + </tr></thead> + <tbody><tr> + <td class="tdl">Cheddar</td> + <td class="tdc">34.38</td> + <td class="tdc">26.38</td> + <td class="tdc">32.71</td> + <td class="tdc">2.95</td> + <td class="tdc">3.58</td> + </tr><tr> + <td class="tdl">Cheshire</td> + <td class="tdc">32.59</td> + <td class="tdc">32.51</td> + <td class="tdc">26.06</td> + <td class="tdc">4.53</td> + <td class="tdc">4.31</td> + </tr><tr> + <td class="tdl">Stilton</td> + <td class="tdc">30.35</td> + <td class="tdc">28.85</td> + <td class="tdc">35.39</td> + <td class="tdc">1.59</td> + <td class="tdc">3.83</td> + </tr><tr> + <td class="tdl">Brie</td> + <td class="tdc">50.35</td> + <td class="tdc">17.18</td> + <td class="tdc">25.12</td> + <td class="tdc">1.94</td> + <td class="tdc">5.41</td> + </tr><tr> + <td class="tdl">Neufchatel</td> + <td class="tdc">44.47</td> + <td class="tdc">14.60</td> + <td class="tdc">33.70</td> + <td class="tdc">4.24</td> + <td class="tdc">2.99</td> + </tr><tr> + <td class="tdl">Roquefort</td> + <td class="tdc">31.20</td> + <td class="tdc">27.63</td> + <td class="tdc">33.16</td> + <td class="tdc">2.00</td> + <td class="tdc">6.01</td> + </tr><tr> + <td class="tdl">Edam</td> + <td class="tdc">36.28</td> + <td class="tdc">24.06</td> + <td class="tdc">30.26</td> + <td class="tdc">4.60</td> + <td class="tdc">4.90</td> + </tr><tr> + <td class="tdl">Swiss</td> + <td class="tdc">35.80</td> + <td class="tdc">24.44</td> + <td class="tdc">37.40</td> + <td class="tdc"> </td> + <td class="tdc">2.36</td> + </tr><tr> + <td class="tdl">Full cream,</td> + <td class="tdc" rowspan="2">38.60</td> + <td class="tdc" rowspan="2">25.35</td> + <td class="tdc" rowspan="2">30.25</td> + <td class="tdc" rowspan="2">2.03</td> + <td class="tdc" rowspan="2">4.07</td> + </tr><tr> + <td class="tdl_ws1">(mean of 143 analyses)</td> + </tr> + </tbody> +</table> + +<p>It is evident that the composition of the cheese will vary with +the milk from which it is made and the manipulation to which it +is subjected. A good American green cheese made from milk of +the composition noted below will have the composition which is +appended.<a id="FNanchor_516" href="#Footnote_516" class="fnanchor">[516]</a></p> + +<p class="f120"><b> <span class="smcap">Table Showing Mean Composition of<br> +Milk and Cheese Made Therefrom.</span></b></p> + +<table class="spb1"> + <thead><tr> + <th class="tdc" colspan="3"> </th> + <th class="tdc"> Milk. </th> + <th class="tdc"> Cheese. </th> + </tr></thead> + <tbody><tr> + <td class="tdl">Per</td> + <td class="tdl_wsp">cent.</td> + <td class="tdl_wsp">water</td> + <td class="tdr">87.38</td> + <td class="tdr_ws1">36.70</td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdc">”</td> + <td class="tdl_wsp">fat</td> + <td class="tdr">3.73</td> + <td class="tdr_ws1">34.18</td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdc">”</td> + <td class="tdl_wsp">proteids</td> + <td class="tdr">3.13</td> + <td class="tdr_ws1">23.44</td> + </tr><tr> + <td class="tdc">”</td> + <td class="tdc">”</td> + <td class="tdl_wsp">sugar, ash etc.  </td> + <td class="tdr">5.76</td> + <td class="tdr_ws1">5.68</td> + </tr> + </tbody> +</table> + +<p><span class="pagenum"><a id="Page_525"></a>[Pg 525]</span> +From the above it is seen that in full milk cheese the ratio of fat to +casein is 1.46: 1, and to solids not fat 1.17: 1. This is a point of +some importance in judging the purity of a cheese. When the full milk +of a mixed herd is used the percentage of fat in a cheese will always +be considerably higher than that of casein.</p> + +<p><b>511. Manipulation of the Milk.</b>—When sweet milk is received at +the cheese factory, a starter of sour milk is added to it in order +to hasten its ripening. When it is thought that the proper degree of +acidity has been secured, it is subjected to a rennet test. In this +test 160 cubic centimeters of the milk are heated to 30° and mixed +with five cubic centimeters of the rennet solution made by diluting +five cubic centimeters of the rennet of commerce with fifty cubic +centimeters of water. The number of seconds required for the milk +to curdle is noted. The observation is facilitated by distributing +throughout the milk a few fine fragments of charcoal. The contents of +the vessel are given a circular motion and, at the moment of setting, +the movement of the black particles is suddenly arrested. If coloring +matter be added to the milk, it should be done before it becomes sour. +The quantity of rennet required is determined by the nature of the +cheese which it is desired to make. For a cheese to be rapidly cured, +enough rennet should be added to produce coagulation in from fifteen +to twenty minutes, and when slow curing is practiced in from thirty +to forty-five minutes. When the mass is solid so that it can be cut +with a knife, the temperature is raised to 37°, and it is tested on a +hot iron until it forms threads an eighth of an inch in length. This +test is made by applying an iron heated nearly to redness to the curd. +When the curd is in proper condition threads from a few millimeters to +two centimeters in length are formed, when the iron is withdrawn. The +longer threads indicate, but only to a limited extent, a higher degree +of acidity.<a id="FNanchor_517" href="#Footnote_517" class="fnanchor">[517]</a> +This test is usually made about two and one-half hours from the time of +coagulation. The whey is then drawn off through a strainer and the curd +is placed on racks with linen bottoms in order that the residual whey +may escape, the curd being stirred meanwhile. In from fifteen to twenty +<span class="pagenum"><a id="Page_526"></a>[Pg 526]</span> +minutes it can be cut into blocks eight or ten inches square and turned +over. This is repeated several times in order to facilitate the escape +of the whey. When the curd assumes a stringy condition, it is run +through a mill and cut into small bits and is ready for salting, being +cooled to 27° before the salt is added. From two to three pounds of +salt are used for each 100 pounds of curd. The curd is then placed in +the molds and pressed into the desired form. The cheeses thus prepared +are placed on shelves in the ripening room and the rinds greased. They +should be turned and rubbed every day during the ripening, which takes +place at a temperature of from 15° to 18°.<a id="FNanchor_518" href="#Footnote_518" class="fnanchor">[518]</a></p> + +<p><b>512. Official Methods of Analysis.</b>—The methods of cheese +analysis recommended by the Association of Official Agricultural +Chemists are provisional and are not binding on its members. They are +as follows:<a id="FNanchor_519" href="#Footnote_519" class="fnanchor">[519]</a></p> + +<p><i>Preparation of Sample.</i>—Where the cheese can be cut, a narrow +wedge reaching from the edge to the center will more nearly represent +the average composition than any other sample. This should be chopped +quite fine, with care to avoid evaporation of water, and the several +portions for analysis taken from the mixed mass. When the sample is +obtained with a cheese trier, a plug perpendicular to the surface +one-third of the distance from the edge to the center of the cheese +more nearly represents the average composition than any other. The +plug should either reach entirely or half way through the cheese. For +inspection purposes the rind may be rejected, but for investigations +where the absolute quantity of fat in the cheese is required the rind +should be included in the sample. It is well, when admissible, to +secure two or three plugs on different sides of the cheese, and, after +splitting them lengthwise with a sharp knife, use portions of each for +the different determinations.</p> + +<p><i>Determination of Water.</i>—From five to ten grams of cheese are +placed in thin slices in a weighed platinum or porcelain dish which +contains a small quantity of freshly ignited asbestos to absorb the +fat. The dish is heated in a water oven for ten hours and weighed; the +loss in weight is considered as water. If preferred, the dish may be +placed in a desiccator over concentrated sulfuric acid and dried to +<span class="pagenum"><a id="Page_527"></a>[Pg 527]</span> +constant weight. In some cases this may require as much as two months. +The acid should be renewed when the cheese has become nearly dry.</p> + +<p><i>Determination of Ether Extract.</i>—Grind from five to ten grams +of cheese in a small mortar with about twice its weight of anhydrous +copper sulfate. The grinding should continue until the cheese is finely +pulverized and evenly distributed throughout the mass, which will have +a uniform light blue color. This mixture is transferred to a glass tube +having a strong filter paper, supported by a piece of muslin, tied over +one end. Put a little anhydrous copper sulfate into the tube next to +the filter before introducing the mixture containing the cheese. On top +of the mixture place a tuft of ignited asbestos, and place the tube in +a continuous extraction apparatus and treat with anhydrous ether for +fifteen hours. Dry the fat obtained at 100° to constant weight.</p> + +<p><i>Determination of Nitrogen.</i>—The nitrogen is determined by the +kjeldahl method, using about two grams of cheese, and multiplying the +percentage of nitrogen found by 6.25 for proteid compounds.</p> + +<p><i>Determination of Ash.</i>—The dry residue from the water +determination may be used for the ash determination. If the cheese be +rich in fat, the asbestos will be saturated therewith. This may be +carefully ignited and the fat allowed to burn, the asbestos acting as a +wick. No extra heat should be applied during this operation, as there +is danger of spurting. When the flame has died out, the burning may be +completed in a muffle at low redness. When desired, the salt may be +determined in the ash in the manner specified under butter +(<b><a href="#P_498">498</a></b>).</p> + +<p><i>Determination of Other Constituents.</i>—The sum of the percentages +of the different constituents, determined as above, subtracted from 100 +will give the amount of organic acids, milk sugar etc., in the cheese.</p> + +<p><b>513. Process of Mueller.</b>—The process of Müller,<a id="FNanchor_520" href="#Footnote_520" class="fnanchor">[520]</a> +as modified by Kruger,<a id="FNanchor_521" href="#Footnote_521" class="fnanchor">[521]</a> +is conducted as follows: About ten grams of a good average sample of +cheese are rubbed in a porcelain mortar with a mixture of three parts +of alcohol and one part of ether. After the mixed liquids have been in +<span class="pagenum"><a id="Page_528"></a>[Pg 528]</span> +contact with the cheese five or ten minutes they are poured upon a +weighed filter of from fifteen to sixteen centimeters diameter, and +this process is repeated from one to three times, after which the +contents of the mortar are brought upon the filter. The filtrate +is received in a weighed flask, the alcohol ether driven off by +evaporation and the residue dried. Since it is difficult to get all the +particles of cheese free from the mortar, it is advisable to perform +the above process in a weighed dish which can afterwards be washed +thoroughly with ether and alcohol and dried and the amount of matter +remaining thereon accounted for. The residue remaining in the flask +after drying is treated several times with pure warm ether, and the +residue also remaining upon the filter mentioned above is completely +extracted with ether. The dried residue obtained in this way from the +filter plus the residue in the flask which received the filtrate, plus +the amount left upon the dish in which the cheese was originally rubbed +up, constitute the total dry matter of the cheese freed of fat. All +the material soluble in ether should be collected together, dried and +weighed as fat.</p> + +<p>By this process the cheesy mass is converted into a fine powder which +can be easily and completely freed from fat by ether, and can be dried +without becoming a gummy or horny mass.</p> + +<p>For the estimation of the nitrogen, about three grams of the well +grated cheese are used and the nitrogen determined by moist combustion +with sulfuric acid.<a id="FNanchor_522" href="#Footnote_522" class="fnanchor">[522]</a></p> + +<p>For the estimation of ash, about five grams are carbonized, extracted +with water, and the ash determined as described below.<a id="FNanchor_523" href="#Footnote_523" class="fnanchor">[523]</a></p> + +<p>Char from two to three grams of the substance and burn to whiteness +at the lowest possible red heat. If a white ash cannot be obtained in +this manner, exhaust the charred mass with water, collect the insoluble +residue on a filter, burn, add this ash to the residue from the +evaporation of the aqueous extract and heat the whole to a low redness +till the ash is white.</p> + +<p><b>514. Separation of Fat from Cheese.</b>—It is often desirable to +secure a considerable quantity of the cheese fat for physical and +chemical examination without the necessity of effecting a complete +quantitive separation. In this laboratory this is accomplished by the +method of Henzold.<a id="FNanchor_524" href="#Footnote_524" class="fnanchor">[524]</a> +The cheese, in quantities of about 300 grams, is cut into fragments +<span class="pagenum"><a id="Page_529"></a>[Pg 529]</span> +about the size of a pea and treated with 700 cubic centimeters of +potash lye, which has previously been brought to a temperature of about +20°. The strength of the lye should be such that about fifty grams of +the caustic potash are contained in each liter of the solution.</p> + +<p>The treatment is conveniently conducted in a wide neck flask and the +solution of the casein is promoted by vigorous shaking. After from five +to ten minutes, it will be found that the casein is dissolved and the +fat is found swimming upon the surface of the solution in the form of +lumps. The lumps of fat are collected in as large a mass as possible by +a gentle shaking to and fro. Cold water is poured into the flask until the +fat is driven up into the neck, whence it is removed by means of a spoon.</p> + +<p>The fat obtained in this way is washed a few times with as little cold +water as possible in order to remove the residue of potash lye which +it may contain. Experience shows that the fat by this treatment is +not perceptibly attacked by the potash lye. In a short time, by this +procedure, the fat is practically all separated and is then easily +prepared for chemical analysis by filtering and drying in the manner +already described (<b><a href="#P_283">283</a></b>). The fat may also be separated, but +with less convenience, by partially drying the sample, reducing it to +a finely divided state and applying any of the usual solvents. The +solvent is removed from the extract by evaporation and the residual fat +is filtered and prepared for examination as usual.</p> + +<p><b>515. Filled Cheese.</b>—The skim milk coming from the separators +is unfortunately too often used for cheese making. The abstracted fat +is replaced with a cheaper one, usually lard. These spurious cheeses +are found in nearly every market and are generally sold as genuine. +The purchasers only discover the fraud when the cheese is consumed. +Many of the States have forbidden by statute the manufacture and sale +of this fraudulent article. Imported cheeses may also be regarded +with suspicion, inasmuch as the method of preparing filled cheese is +well known and extensively practiced abroad. A mere determination of +the percentage of fat in the sample is not an index of the purity of +the cheese. It is necessary to extract the fat by one of the methods +already described and, after drying and filtering, to submit the +suspected fat to a microscopic and chemical examination. A low content +<span class="pagenum"><a id="Page_530"></a>[Pg 530]</span> +of volatile fat acid and the occurrence of crystalline forms foreign to +butter will furnish the data for a competent judgment.</p> + +<p>When the reichert-meissl number falls below twenty-five the sample +may be regarded with suspicion. The detection of the characteristic +crystals of lard or tallow is reliable corroborating evidence +(<b><a href="#P_308">308</a></b>).</p> + +<p>It is stated by Kühn<a id="FNanchor_525" href="#Footnote_525" class="fnanchor">[525]</a> +that the margarin factory of Mohr, at Bahrenfeld-Altona, has made for +many years a perfect emulsion of fat with skim milk. This product has +been much used in the manufacture of filled cheese which is often found +upon the German market.</p> + +<p><b>516. Separation of the Nitrogenous Bodies in Cheese.</b>—The +general methods of separation already described for proteid bodies +(<b><a href="#P_417">417-425</a></b>) are also applicable to the different nitrogenous +bodies present in cheese, representing the residue of these bodies +as originally occurring in the milk, and also the products which are +formed therefrom during the period of ripening. For practical dietary +and analytical purposes, these bodies may be considered in three groups:</p> + +<p>(<i>a</i>) The useless (from a nutrient point of view) nitrogenous +bodies, including ammonia, nitric acid, the phenylamido-propionic +acids, tyrosin, leucin and other amid bodies.</p> + +<p>(<i>b</i>) The albumoses and peptones, products of fermentation soluble +in boiling water.</p> + +<p>(<i>c</i>) The caseins and albuminates, insoluble in boiling water.</p> + +<p>The group of bodies under (<i>a</i>), according to Stutzer, may be +separated from the groups (<i>b</i>) and (<i>c</i>) by means of +phosphotungstic acid. For this purpose a portion of an intimate +mixture of fine sand and cheese (100 cheese, 400 sand) corresponding +to five grams of cheese, is shaken for fifteen minutes with 150 cubic +centimeters of water. After remaining at rest for another fifteen +minutes 100 cubic centimeters of dilute sulfuric acid (one acid, three +water) are added, followed by treatment with the phosphotungstic acid +as long as any precipitate is produced. The mixture is thrown on a +filter and the insoluble matters washed with dilute sulfuric acid until +the filtrate amounts to half a liter. Of this quantity an aliquot part +(200 cubic centimeters) is used for the determination of nitrogen. From +<span class="pagenum"><a id="Page_531"></a>[Pg 531]</span> +the quantity of nitrogen found, that representing the ammonia, as +determined in a separate portion, is deducted and the remainder +represents the nitrogen present in the cheese as amids.<a id="FNanchor_526" href="#Footnote_526" class="fnanchor">[526]</a></p> + +<p><i>Albumoses and Peptones.</i>—Albumoses and peptones are determined +in cheese by the following method:<a id="FNanchor_527" href="#Footnote_527" class="fnanchor">[527]</a> +A quantity of the sand mixture already described, corresponding to five +grams of the cheese, is treated with about 100 cubic centimeters of +water, heated to boiling, and the clear liquid above the sand poured +into a flask of half a liter capacity. The extraction is continued with +successive portions of water in like manner until the volume of the +extract is nearly half a liter. When cold, the volume of the extract is +completed to half a liter with water, the liquor filtered, 200 cubic +centimeters of the filtrate treated with an equal volume of dilute +sulfuric acid (one to three) and phosphotungstic acid added until no +further precipitate takes place. The nitrogen is determined in the +precipitate after filtration and washing with dilute sulfuric acid.</p> + +<p><i>Casein and Albuminates.</i>—The quantity of casein and albuminates +in cheese is calculated by subtracting from the total nitrogen that +corresponding to ammonia, amids, that in the indigestible residue and +that corresponding to the albumose and peptone. In three samples of +cheese, <i>viz.</i>, camembert, swiss, and gervais, Stutzer found the +nitrogen, determined as above, distributed as follows:<a id="FNanchor_528" href="#Footnote_528" class="fnanchor">[528]</a></p> + +<table class="spb1"> + <tbody><tr> + <td class="tdl"> </td> + <td class="tdc"> Camembert. </td> + <td class="tdc"> Swiss. </td> + <td class="tdc"> Gervais. </td> + </tr><tr> + <td class="tdl">N as ammonia</td> + <td class="tdc">13.0</td> + <td class="tdc">3.7</td> + <td class="tdc">1.6</td> + </tr><tr> + <td class="tdl">N as amids</td> + <td class="tdc">38.5</td> + <td class="tdc">9.0</td> + <td class="tdc">5.2</td> + </tr><tr> + <td class="tdl">N as albumose peptone</td> + <td class="tdc">30.5</td> + <td class="tdc">8.6</td> + <td class="tdc">15.5 </td> + </tr><tr> + <td class="tdl">N indigestible</td> + <td class="tdc"> 4.0</td> + <td class="tdc">2.4</td> + <td class="tdc">8.6</td> + </tr><tr> + <td class="tdl">N as casein, albuminates</td> + <td class="tdc">14.0</td> + <td class="tdc">76.3 </td> + <td class="tdc">69.1 </td> + </tr> + </tbody> +</table> + +<p><i>Ammoniacal Nitrogen.</i>—The ammoniacal nitrogen is determined by +mixing a quantity of the sand-cheese corresponding to five grams of +cheese, with 200 cubic centimeters of water, adding an excess of barium +carbonate and collecting the ammonia by distillation in the usual way.</p> + +<p><i>Digestible Proteids.</i>—The digestible proteids in cheese are +determined by the process of artificial digestion, which will be described +in the part of this volume treating of the nutritive value of foods. +<span class="pagenum"><a id="Page_532"></a>[Pg 532]</span></p> + +<p>These data show the remarkable changes which the proteids undergo where +the ripening is carried very far as in the camembert cheese.</p> + +<p><b>517. Koumiss.</b>—Fermented mare milk has long been a favorite +beverage in the East, where it is known as koumiss. In Europe and +this country cow milk is employed in the manufacture of fermented +milk, although it is less rich in lactose than mare milk. The process +of manufacture is simple, provided a suitable starter is at hand. +A portion of a previous brewing is the most convenient one, the +fermentation being promoted by the addition of a little yeast. After +the process of fermentation is finished the koumiss is placed in +bottles and preserved in a horizontal position in a cellar, where the +temperature is not allowed to rise above 12°.</p> + +<p><b>518. Determination of Carbon Dioxid.</b>—The carbon dioxid in +koumiss is conveniently estimated by connecting the bottle by means +of a champagne tap with a system of absorption bulbs.<a id="FNanchor_529" href="#Footnote_529" class="fnanchor">[529]</a> +The exit tube from the koumiss bottle passes first into an erlenmeyer, +which serves to break and retain any bubbles that pass over. The water is +next removed by means of sulfuric acid. The koumiss bottle is placed in +a bath of water which is raised to the boiling point as the evolution +of the gas is accomplished. The arrangement of the apparatus is shown +in <a href="#FIG_113">Fig. 113</a>. At the end of the operation any residual +carbon dioxid in the apparatus is removed by aspiration after removing +the tap and connecting it with a soda-lime tube to hold the carbon +dioxid in the air. A large balance suited to weighing the koumiss +bottle is required for this determination. The carbon dioxid may also +be determined, but less accurately, by loss of weight in the koumiss +bottle after adding weight of water retained in the apparatus.</p> + +<p><b>519. Acidity.</b>—Although koumiss may contain a trace of acetic +acid, it is best to determine the acid as lactic. The clarification is +most easily accomplished by mixing the koumiss with an equal volume +of ninety-five per cent alcohol, shaking and filtering. The first +filtrate will usually be found clear. If not it is refiltered. In an +aliquot part of the filtrate the acidity is determined by titration +with tenth-normal sodium hydroxid solution, using phenolphthalein as +indicator. The necessary corrections for dilution and volume of the +precipitated casein are to be made. A linen filter may be used when +paper is found too slow. +<span class="pagenum"><a id="Page_533"></a>[Pg 533]</span></p> + +<div class="figcenter smcap"> + <img id="FIG_113" src="images/fig113.jpg" alt="" width="600" height="273" > + <p class="center spb1">Fig. 113. Apparatus for Determining Carbon + Dioxid in Koumiss.</p> +</div> + +<p><span class="pagenum"><a id="Page_534"></a>[Pg 534]</span> +<b>520. Alcohol.</b>—Half a liter of koumiss, to which 100 cubic +centimeters of water have been added, is distilled until the distillate +amounts to 500 cubic centimeters.</p> + +<p>If the distillate be turbid 100 cubic centimeters of water are added +and the distillation repeated. The alcohol is determined by the +processes described hereafter.</p> + +<p><b>521. Lactose.</b>—The milk sugar may be determined by any of +the methods described, but most conveniently by double dilution and +polarization (<b><a href="#P_86">86</a></b>).</p> + +<p><b>522. Fat.</b>—Evaporate twenty grams of the sample to dryness and +extract with pure ether or petroleum spirit in the manner already +described (<b><a href="#P_455">455</a></b>).</p> + +<p>The analysis is more quickly accomplished by the volumetric method of +Babcock or Gerber (<b><a href="#P_473">473-475</a></b>).</p> + +<p><b>523. Proteids.</b>—The total proteids are most easily estimated by +the official kjeldahl method.<a id="FNanchor_530" href="#Footnote_530" class="fnanchor">[530]</a> +The separation of the proteid bodies is accomplished by the methods +described in paragraphs <b><a href="#P_475">475-489</a></b>.</p> + +<p>In addition to the methods already described for separating the soluble +and suspended proteid bodies in milk, and which may be used also for +koumiss, the following should also be mentioned as of especial worth:</p> + +<p><i>Separation by Filtration through Porous Porcelain.</i>—A purely +physical method, and one which is to be recommended by reason of the +absence of any chemical action upon the different proteid matters, +is that proposed by Lehmann, depending upon the principle that when +milk is forced through porous porcelain, the albumin passes through +together with the milk, sugar and other soluble constituents as a clear +filtrate, while the casein and fat are perfectly retained.<a id="FNanchor_531" href="#Footnote_531" class="fnanchor">[531]</a></p> + +<p>By this method it is quite certain that the albumin and other perfectly +soluble proteids of milk may be obtained in the purest form. +<span class="pagenum"><a id="Page_535"></a>[Pg 535]</span></p> + +<p><i>Separation by Precipitation with Alum.</i>—Probably the best +chemical method of separating the two classes of proteid matters +is that proposed by Schlosmann, which is effected by means of +precipitating the casein with a solution of alum.<a id="FNanchor_532" href="#Footnote_532" class="fnanchor">[532]</a></p> + +<p>The principle of this separation rests upon the fact that a solution +of potash alum, when added to milk diluted with four or five times its +volume of water, will completely separate the casein without affecting +the albumin or globulin. The operation is conducted as follows:</p> + +<p>Ten cubic centimeters of the milk are diluted with from three to five +times that quantity of water and warmed to a temperature of about +40°. One cubic centimeter of a concentrated solution of potash alum +is added, the mixture well stirred and the coagula which are formed +allowed to subside. If the coagulation of the casein does not take +place promptly, a small addition of the alum solution is made, usually +not exceeding half a cubic centimeter, until the precipitation is +complete. The temperature during the process should be kept as nearly +as possible 40°. After a few minutes, the mixture is poured upon a +filter and the filtrate, if not perfectly clear, is poured back until +it is secured free of turbidity. In difficult cases the filtration may +be promoted by the addition of some common salt or calcium phosphate, +the latter acting mechanically in holding back the fine particles of +casein. The precipitate is washed with water at a temperature of 40°, +and afterwards with alcohol, not allowing the alcohol wash water to +flow into the filtrate. When the water has been chiefly removed from +the precipitate by washing with alcohol, the fat of the precipitated +casein is removed with ether and the residue used for the determination +of nitrogen in the usual way. The albumin is removed from the filtrate +by a tannin solution in the manner already described (<b><a href="#P_480">480</a></b>). +If it be desired to separate the albumin and globulin, the methods +described in paragraph <b><a href="#P_399">399</a></b> may be used.</p> + +<p><b>524. Mercurial Method.</b>—A volumetric method for determining the +total proteid matter in milk has lately been proposed by Deniges.<a id="FNanchor_533" href="#Footnote_533" class="fnanchor">[533]</a> +It is based upon the observation that in the precipitation of proteid +<span class="pagenum"><a id="Page_536"></a>[Pg 536]</span> +matter by mercury salts, a definite quantity of mercury in proportion +to the amount of proteid, is carried down therewith. The precipitation +is made with a mercurial salt of known strength and the excess of the +mercurial salt in the filtrate is determined by titration. For the +details of the manipulation, the paper cited above may be consulted.</p> + +<p><b>525. Water and Ash.</b>—From two to five grams of the koumiss are +dried to constant weight in a flat platinum dish over ignited sand, +asbestos or pumice stone, and the dried residue incinerated.</p> + +<p><b>526. Composition of Koumiss.</b>—The composition of koumiss varies +with the character of the milk used and the extent of the fermentation. +Some of the data obtained by analysts are given below:<a id="FNanchor_534" href="#Footnote_534" class="fnanchor">[534]</a></p> + +<p class="f120 spa1"><b><span class="smcap">Composition of Koumiss.</span></b></p> + +<table class="spb1"> + <thead><tr> + <th class="tdc_bott">Kind of milk.</th> + <th class="tdc_bott bb">Water,<br> Per cent. </th> + <th class="tdc_bott bb">Sugar,<br> Per cent. </th> + <th class="tdc_bott bb">Alcohol,<br> Per cent. </th> + <th class="tdc_bott bb">Fat,<br> Per cent. </th> + <th class="tdc_bott bb">Proteid,<br> Per cent. </th> + <th class="tdc bb">Carbon<br>dioxid,<br> Per cent. </th> + <th class="tdc_bott bb">Acidity,<br> Per cent. </th> + </tr></thead> + <tbody><tr> + <td class="tdl">Cow</td> + <td class="tdc">89.32</td> + <td class="tdc">4.38</td> + <td class="tdc">0.76</td> + <td class="tdc">2.08</td> + <td class="tdc">2.56</td> + <td class="tdc">0.83</td> + <td class="tdc">0.47</td> + </tr><tr> + <td class="tdl">Probably cow skim’d</td> + <td class="tdc"> </td> + <td class="tdc">3.95</td> + <td class="tdc">1.38</td> + <td class="tdc">0.88</td> + <td class="tdc">2.89</td> + <td class="tdc"> </td> + <td class="tdc">0.82</td> + </tr><tr> + <td class="tdl">Mare</td> + <td class="tdc">91.87</td> + <td class="tdc">0.79</td> + <td class="tdc">2.89</td> + <td class="tdc">1.19</td> + <td class="tdc">1.91</td> + <td class="tdc"> </td> + <td class="tdc">1.04</td> + </tr> + </tbody> +</table> + +<p>From the above it is seen that koumiss is made either from whole or +skim milk, and that the percentage of alcohol may vary within large +limits, its proportion being inverse to that of the milk sugar.</p> + +<p>Koumiss is a beverage which is very palatable, easily digested and one +which is not appreciated in this country in proportion to its merits, +especially for the use of invalids.</p> + +<h3>AUTHORITIES CITED IN PART SIXTH.</h3> +<div class="footnotes"> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_400" href="#FNanchor_400" class="label">[400]</a> +Wiley; Proceedings of the Society for the Promotion of Agricultural Science, +1889, p. 84. (Omit “food” before idiosyncrasy.)</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_401" href="#FNanchor_401" class="label">[401]</a> +Pharmaceutical Journal and Transactions, Series 3, Vol. 18, p. 479.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_402" href="#FNanchor_402" class="label">[402]</a> +The Analyst, 1892, p. 85.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_403" href="#FNanchor_403" class="label">[403]</a> +Henkel; Wiener Landwirtschaftliche Zeitung, 1888, S. 401: Bulletin No. 24, +Division of Chemistry, U. S. Department of Agriculture, p. 155.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_404" href="#FNanchor_404" class="label">[404]</a> +Die Landwirtschaftlichen Versuchs-Stationen, Band 35, S. 351: Bulletin +No. 24, Division of Chemistry, U. S. Department of Agriculture, p. 151.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_405" href="#FNanchor_405" class="label">[405]</a> +Baumeister; Milch und Molkerei-Producte, S. 16.</p> +</div> + +<p><span class="pagenum"><a id="Page_537"></a>[Pg 537]</span></p> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_406" href="#FNanchor_406" class="label">[406]</a> +Bulletins Nos. 9 and 25 of the Office of Experiment Stations, U. S. +Department of Agriculture: Farmers’ Bulletins Nos. 9 and 29, U. S. +Department of Agriculture.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_407" href="#FNanchor_407" class="label">[407]</a> +Annales de Chimie et de Physique, 3e Série, Tome 64, p. 61.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_408" href="#FNanchor_408" class="label">[408]</a> +Bulletin de la Société Chimique de Paris, 3ᵉ Série, Tome 15-16, p. 248.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_409" href="#FNanchor_409" class="label">[409]</a> +Vid. op. cit. supra, p. 453.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_410" href="#FNanchor_410" class="label">[410]</a> +Central-Blatt für medicinische Wissenschaft, Band 34, S. 145.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_411" href="#FNanchor_411" class="label">[411]</a> +Conn; Farmers’ Bulletins 9 and 25, Office of Experiment Stations, U. S. +Department of Agriculture: Farmers’ Bulletins 9 and 29, Department of +Agriculture: Les Microbes et leur Rôle dans la Laiterie Freudenreich: +Langlois, Le Lait, pp. 95 et seq.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_412" href="#FNanchor_412" class="label">[412]</a> +The Analyst, Vol. 20, p. 157.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_413" href="#FNanchor_413" class="label">[413]</a> +Vid. op. cit. supra, p. 152.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_414" href="#FNanchor_414" class="label">[414]</a> +Forschungs-Berichte über Lebensmittel etc., Band 2, S. 368.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_415" href="#FNanchor_415" class="label">[415]</a> +Vid. op. cit. supra, Band 1, S. 422.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_416" href="#FNanchor_416" class="label">[416]</a> +Vid. op. cit. supra, S. 372.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_417" href="#FNanchor_417" class="label">[417]</a> +Hopkins and Powers; Bulletin No. 47, Division of Chemistry, +U. S. Department of Agriculture, p. 127.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_418" href="#FNanchor_418" class="label">[418]</a> +Bulletin No. 38, Division of Chemistry, U. S. Department of Agriculture, p. 118.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_419" href="#FNanchor_419" class="label">[419]</a> +Becke; Die Milchprüfungs-Methoden, S. 45: Rouvier; Le Lait, p. 45.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_420" href="#FNanchor_420" class="label">[420]</a> +The Analyst, 1890, Vol. 16, p. 170.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_421" href="#FNanchor_421" class="label">[421]</a> +Rouvier; Le Lait, p. 35.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_422" href="#FNanchor_422" class="label">[422]</a> +Central-Blatt für Nahrungs und Genussmittel Chemie, Band 13, S. 277.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_423" href="#FNanchor_423" class="label">[423]</a> +Bulletin No. 46, Division of Chemistry, U. S. Department of Agriculture, p. 36.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_424" href="#FNanchor_424" class="label">[424]</a> +Journal für Landwirtschaft, 1882, S. 293; 1885, S. 251.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_425" href="#FNanchor_425" class="label">[425]</a> +Vid. op. cit. supra, 1879, S. 249.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_426" href="#FNanchor_426" class="label">[426]</a> +Forschungen auf dem Gebiete der Viehhaltung, 1879, S. 265.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_427" href="#FNanchor_427" class="label">[427]</a> +The Analyst, Vol. 7, p. 129.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_428" href="#FNanchor_428" class="label">[428]</a> +Vid. op. cit. supra, Vol. 13, p. 26.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_429" href="#FNanchor_429" class="label">[429]</a> +Bulletin No. 47, Division of Chemistry, U. S. Department of Agriculture, p. 123.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_430" href="#FNanchor_430" class="label">[430]</a> +This work, Vol. 1, page 411.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_431" href="#FNanchor_431" class="label">[431]</a> +Bulletin No. 16, Division of Chemistry, U. S. Department of Agriculture, p. 36.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_432" href="#FNanchor_432" class="label">[432]</a> +Sixth Annual Report Wisconsin Agricultural Experiment Station, p. 64.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_433" href="#FNanchor_433" class="label">[433]</a> +Fourth Annual Report New York (Geneva) Agricultural Experiment Station, p. 298.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_434" href="#FNanchor_434" class="label">[434]</a> +Woll; Seventh Annual Report Wisconsin Agricultural Experiment Station, p. 238.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_435" href="#FNanchor_435" class="label">[435]</a> +The Analyst, 1885, p. 46: Bulletin No. 13, Part 1, +Division of Chemistry, U. S. Department of Agriculture, p. 86.</p> +</div> + +<p><span class="pagenum"><a id="Page_538"></a>[Pg 538]</span></p> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_436" href="#FNanchor_436" class="label">[436]</a> +Haidlen; Die Milchprüfungs-Methoden, S. 12.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_437" href="#FNanchor_437" class="label">[437]</a> +Dingler’s polytechnisches Journal, Band 232, S. 461.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_438" href="#FNanchor_438" class="label">[438]</a> +Macfarlane; The Analyst, Vol. 18, p. 73.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_439" href="#FNanchor_439" class="label">[439]</a> +Duclaux; Le Lait, p. 176.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_440" href="#FNanchor_440" class="label">[440]</a> +Abraham; The Analyst, Vol. 9, p. 22.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_441" href="#FNanchor_441" class="label">[441]</a> +Gantter; Zeitschrift für analytische Chemie, Band 26, S. 677.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_442" href="#FNanchor_442" class="label">[442]</a> +Morse, Piggot and Burton; American Chemical Journal, Vol. 9, pp. 108 and 222.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_443" href="#FNanchor_443" class="label">[443]</a> +Chemiker-Zeitung Repertorium, 1889, S. 228.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_444" href="#FNanchor_444" class="label">[444]</a> +Journal de Pharmacie et de Chimie, 1890, p. 460.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_445" href="#FNanchor_445" class="label">[445]</a> +Richmond; The Analyst, Vol. 17, p. 48: Bulletins 28, 31, 35, 38, 43, +and 46, Division of Chemistry, U. S. Department of Agriculture.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_446" href="#FNanchor_446" class="label">[446]</a> +Bulletin No. 28, Division of Chemistry, U. S. Department of Agriculture, p. 31.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_447" href="#FNanchor_447" class="label">[447]</a> +Zeitschrift für analytische Chemie, Band 27, S. 464.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_448" href="#FNanchor_448" class="label">[448]</a> +Chemical News, Nov. 1889.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_449" href="#FNanchor_449" class="label">[449]</a> +The Analyst, Vol. 16, p. 67.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_450" href="#FNanchor_450" class="label">[450]</a> +Vid. op. cit. supra, Vol. 18, p. 53.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_451" href="#FNanchor_451" class="label">[451]</a> +Vid. op. cit. supra, Vol. 17, p. 81.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_452" href="#FNanchor_452" class="label">[452]</a> +Chemiker-Zeitung, Band 15, S. 1833.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_453" href="#FNanchor_453" class="label">[453]</a> +Journal of Analytical Chemistry, 1888, Vol. 2, p. 371: +Fifth Annual Report Wisconsin Agricultural Experiment Station.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_454" href="#FNanchor_454" class="label">[454]</a> +Molkerei Zeitung, 1892, No. 1; Chemisches Central-Blatt, 1892, Band 2, S. 429.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_455" href="#FNanchor_455" class="label">[455]</a> +Chemiker-Zeitung, Band 18, S. 1816; Band 19, S. 348.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_456" href="#FNanchor_456" class="label">[456]</a> +Zeitschrift für analytische Chemie, Band 32, S. 168.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_457" href="#FNanchor_457" class="label">[457]</a> +Zeitschrift des Landwirtschaftlichen Vereins in Bayern, 1880; +Zeitschrift für analytische Chemie, Band 20, S. 452.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_458" href="#FNanchor_458" class="label">[458]</a> +Bulletin No. 13, Division of Chemistry, U. S. Department of Agriculture, p. 92.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_459" href="#FNanchor_459" class="label">[459]</a> +Instruction sur l’Emploi du Lactobutyrometer, Paris, 1856 +et 1878: Becke; Die Milchprüfungs-Methoden, S. 66.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_460" href="#FNanchor_460" class="label">[460]</a> +Bulletin No. 8, Iowa Agricultural Experiment Station, p. 295.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_461" href="#FNanchor_461" class="label">[461]</a> +Dingler’s polytechnisches Journal, Band 261, S. 219.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_462" href="#FNanchor_462" class="label">[462]</a> +Milch Zeitung, Band 21, S. 496.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_463" href="#FNanchor_463" class="label">[463]</a> +Op. cit. supra, Band 22, S. 85.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_464" href="#FNanchor_464" class="label">[464]</a> +Bulletin No. 24, Wisconsin Agricultural Experiment Station.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_465" href="#FNanchor_465" class="label">[465]</a> +Bulletin No. 31, Wisconsin Agricultural Experiment Station.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_466" href="#FNanchor_466" class="label">[466]</a> +The Analyst, Vol. 17, p. 83.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_467" href="#FNanchor_467" class="label">[467]</a> +Bulletin No. 21, Vermont Agricultural Experiment Station.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_468" href="#FNanchor_468" class="label">[468]</a> +Vid. op. cit. 67, Vol. 17, p. 144; Vol. 18, p. 130; Vol. 19, p. 62.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_469" href="#FNanchor_469" class="label">[469]</a> +Chemiker-Zeitung, Band 16, S. 1839.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_470" href="#FNanchor_470" class="label">[470]</a> +Vid. op. cit. supra, Band 19, S. 348; Band 18, S. 1816.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_471" href="#FNanchor_471" class="label">[471]</a> +Vid. op. cit. supra, Band 19, S. 348.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_472" href="#FNanchor_472" class="label">[472]</a> +Comptes rendus, Tome 107, p. 772; Hoppe-Seyler’s Handbuch +der Physiologisch- und Pathologisch-Chemischen Analyse, S. 479.</p> +</div> + +<p><span class="pagenum"><a id="Page_539"></a>[Pg 539]</span></p> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_473" href="#FNanchor_473" class="label">[473]</a> +Proceedings of the Society for the Promotion of Agricultural Science, 1888, p. 13.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_474" href="#FNanchor_474" class="label">[474]</a> +Journal of Physiology, Vol. 11, p. 459.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_475" href="#FNanchor_475" class="label">[475]</a> +Die Land wirtschaftlichen Versuchs-Stationen, Band 31, S. 131.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_476" href="#FNanchor_476" class="label">[476]</a> +Sixth Annual Report of the Wisconsin Agricultural Experiment Station, p. 64.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_477" href="#FNanchor_477" class="label">[477]</a> +Bulletin No. 46, Division of Chemistry, U. S. Department of Agriculture, p. 36.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_478" href="#FNanchor_478" class="label">[478]</a> +Zeitschrift für Biologie, Band 33, S. 43.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_479" href="#FNanchor_479" class="label">[479]</a> +Journal für praktische Chemie, {2}, Band 15, S. 329.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_480" href="#FNanchor_480" class="label">[480]</a> +Vid. op. cit. 79, Band 33, {Neue Folge, 15}, S. 55.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_481" href="#FNanchor_481" class="label">[481]</a> +Stenberg; Zeitschrift für physiologische Chemie, Band 13, S. 138.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_482" href="#FNanchor_482" class="label">[482]</a> +Vid. op. cit. supra, S. 137.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_483" href="#FNanchor_483" class="label">[483]</a> +Vid. op. cit. supra, S. 160.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_484" href="#FNanchor_484" class="label">[484]</a> +Journal of the American Chemical Society, Vol. 15, p. 644.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_485" href="#FNanchor_485" class="label">[485]</a> +Handbuch der Physiologisch- und Pathologisch-Chemischen +Analyse, S. 285. (Read, Makris instead of Makeris.)</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_486" href="#FNanchor_486" class="label">[486]</a> +Zeitschrift für Biologie, Band 23, S. 64.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_487" href="#FNanchor_487" class="label">[487]</a> +Bulletin de la Société Chimique de Paris, 3ᵉ Série, Tome 11, p. 152.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_488" href="#FNanchor_488" class="label">[488]</a> +Vid. op. cit. 86, S. 487.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_489" href="#FNanchor_489" class="label">[489]</a> +Zeitschrift für Nahrungsmittel-Untersuchung, Band 10, S. 104.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_490" href="#FNanchor_490" class="label">[490]</a> +Zeitschrift für physiologische Chemie, Band 9, S. 445.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_491" href="#FNanchor_491" class="label">[491]</a> +American Chemical Journal, Vol. 6, p. 289.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_492" href="#FNanchor_492" class="label">[492]</a> +Journal of the American Chemical Society, Vol. 18, p. 428.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_493" href="#FNanchor_493" class="label">[493]</a> +Journal de Pharmacie et de Chimie, 6e Série, Tome 4, p. 65.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_494" href="#FNanchor_494" class="label">[494]</a> +Contribution à l’Étude des Lactoses, Thèse pour le diplôme supérieure +de Pharmacie, Paris, 1892. (Read Thibault instead of Thibonet.)</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_495" href="#FNanchor_495" class="label">[495]</a> +Journal für praktische Chemie, Neue Folge, Band 15, S. 348.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_496" href="#FNanchor_496" class="label">[496]</a> +Zeitschrift für angewandte Chemie, 1896, S. 72.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_497" href="#FNanchor_497" class="label">[497]</a> +Chemisches Central-Blatt, 1892, Band 2, S. 1028.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_498" href="#FNanchor_498" class="label">[498]</a> +Vid. op. cit. supra, Band 21, S. 753.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_499" href="#FNanchor_499" class="label">[499]</a> +Vid. op. cit. 90, S. 86.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_500" href="#FNanchor_500" class="label">[500]</a> +Bulletin No. 13, Division of Chemistry, U. S. Department of Agriculture, pp. 29 et seq.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_501" href="#FNanchor_501" class="label">[501]</a> +Vid. op. cit. supra, pp. 73-75: Bulletin No. 46, +Division of Chemistry, U. S. Department of Agriculture, p. 26.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_502" href="#FNanchor_502" class="label">[502]</a> +Benedikt and Lewkowitsch; Oils, Fats and Waxes, p. 490.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_503" href="#FNanchor_503" class="label">[503]</a> +Forsuchungs-Berichte über Lebensmittel, 1895, Band 2, S. 424; +Chemiker-Zeitung Repertorium, 1896, Band 20, S. 15.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_504" href="#FNanchor_504" class="label">[504]</a> +Revue Internationale des Falsifications, Mai, 1893, p. 157.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_505" href="#FNanchor_505" class="label">[505]</a> +Chemiker-Zeitung, 1893, Band 17, S. 468.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_506" href="#FNanchor_506" class="label">[506]</a> +Zeitschrift für angewandte Chemie, 1896, S. 177.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_507" href="#FNanchor_507" class="label">[507]</a> +Vid. op. cit. 90, Aug. 26, 1894, S. 219; Le Stazioni +Sperimentali Agrarie Italiane, 1893, pp. 25-77.</p> +</div> + +<p><span class="pagenum"><a id="Page_540"></a>[Pg 540]</span></p> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_508" href="#FNanchor_508" class="label">[508]</a> +Farmers’ Bulletin No. 12, U. S. Department of Agriculture.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_509" href="#FNanchor_509" class="label">[509]</a> +Bulletin de l’Association Belge des Chimistes, Tome 9, p. 279.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_510" href="#FNanchor_510" class="label">[510]</a> +Vid. op. cit. 101, p. 26.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_511" href="#FNanchor_511" class="label">[511]</a> +Vid. op. cit. supra, p. 27: Chemical News, Vol. 55, p. 49.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_512" href="#FNanchor_512" class="label">[512]</a> +Vid. op. cit. 111, p. 28.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_513" href="#FNanchor_513" class="label">[513]</a> +Vid. op. et. loc. cit. supra.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_514" href="#FNanchor_514" class="label">[514]</a> +Russell; Dairy Bacteriology.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_515" href="#FNanchor_515" class="label">[515]</a> +Woll; Dairy Calendar, p. 223.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_516" href="#FNanchor_516" class="label">[516]</a> +Van Slyke; Bulletin 82, New Series, New York Agricultural Experiment Station, p. 654.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_517" href="#FNanchor_517" class="label">[517]</a> +Babcock; Twelfth Annual Report Wisconsin Agricultural Experiment Station, p. 133.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_518" href="#FNanchor_518" class="label">[518]</a> +Woll; Dairy Calendar, 1895, p. 220.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_519" href="#FNanchor_519" class="label">[519]</a> +Bulletin No. 46, Division of Chemistry, U. S. Department of Agriculture, p. 37.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_520" href="#FNanchor_520" class="label">[520]</a> +Landwirtschaftliches Jahrbuch, 1872, part 1.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_521" href="#FNanchor_521" class="label">[521]</a> +Molkerei Zeitung, 1893, Nos. 20, 22.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_522" href="#FNanchor_522" class="label">[522]</a> +This work, Vol. 2, p. 204.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_523" href="#FNanchor_523" class="label">[523]</a> +Vid. op. cit. 120, p. 24.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_524" href="#FNanchor_524" class="label">[524]</a> +Milch Zeitung, 1895, Band 24, S. 729: Chemiker-Zeitung Repertorium, Band 19, S. 372.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_525" href="#FNanchor_525" class="label">[525]</a> +Chemiker-Zeitung, 1895, S. 554.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_526" href="#FNanchor_526" class="label">[526]</a> +Zeitschrift für analytische Chemie, Band 35, S. 497.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_527" href="#FNanchor_527" class="label">[527]</a> +Vid. op. cit. supra, S. 499.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_528" href="#FNanchor_528" class="label">[528]</a> +Vid. op. cit. supra, S. 502.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_529" href="#FNanchor_529" class="label">[529]</a> +Bulletin No. 13, Division of Chemistry, U. S. Department of Agriculture, pp. 118, 293.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_530" href="#FNanchor_530" class="label">[530]</a> +This work, Vol. 2, p. 204.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_531" href="#FNanchor_531" class="label">[531]</a> +Pflüger’s Archiv, Band 56, S. 558.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_532" href="#FNanchor_532" class="label">[532]</a> +Hoppe-Seyler’s Zeitschrift für physiologische Chemie, Band 22, S. 213.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_533" href="#FNanchor_533" class="label">[533]</a> +Bulletin de la Société Chimique de Paris, Tomes 15-16, p. 1126.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_534" href="#FNanchor_534" class="label">[534]</a> +American Chemical Journal, Vol. 8, p. 200: Bulletin 13, +Division of Chemistry, U. S. Department of Agriculture, p. 120.</p> +</div> +</div> + +<hr class="chap x-ebookmaker-drop"> + +<div class="chapter"> +<p><span class="pagenum"><a id="Page_541"></a>[Pg 541]</span></p> +<h2 class="nobreak">PART SEVENTH.<br> +<span class="h_subtitle">MISCELLANEOUS AGRICULTURAL PRODUCTS.</span></h2> +</div> + +<p><b>527. Classification.</b>—In the preceding parts have been set forth +the fundamental principles underlying the conduct of agricultural +analysis and a résumé of the best practice of the art. The analyst, as +a rule, will seldom be required to undertake investigations which are +unnoticed in the preceding pages. Cases will arise, however, in which +problems are presented which can not be solved by the rules already +elucidated. In respect of the great classes of agricultural bodies, +it will be observed that dairy products have already received special +mention. In respect of foods and fodders in general, it is evident that +they are chiefly composed of moisture, ash, carbohydrates, oils and +proteid matters. The methods of identifying, separating and estimating +these constituents have been fully set forth. It is not necessary, +therefore, to study in this part the analytical processes which are +applicable to cereals, cattle foods and other food products, further +than is necessary to present in the most important cases a working +résumé of principles and methods. There remain, however, certain +products of importance which require some special modifications of +treatment, and it is to these that the present part will be chiefly +devoted. Among these are found tobacco, tea and coffee, fruits, +fermented and distilled drinks and certain animal products. It is +evident that an enumeration of all agricultural products, with a +description of their methods of examination, would be impracticable in +the available space and undesirable by reason of the repetition which +would be required. In each case the analyst, in possession of the +methods described, will be able to adapt the means at his disposal to +the desired purpose to better advantage than any rigid directions could +possibly secure. +<span class="pagenum"><a id="Page_542"></a>[Pg 542]</span></p> + +<p>In respect of the analytical methods of determining the nutritive +value of foods, they may be divided into chemical and physiological. +The chemical methods embrace the thermal and artificial digestion +investigations, and the physiological include those which are carried +out with the help of the animal organisms. In the latter case the +digestive process is checked by the analysis of the foods before +ingestion and of the excreta of all kinds during and after digestion.</p> + +<p>It is evident that a detailed description of this method should be +looked for in works devoted to physiological chemistry.</p> + +<h3>CEREALS AND CEREAL FOODS.</h3> + +<p><b>528. General Analysis.</b>—The cereals are prepared for analysis +by grinding until the fragments pass a sieve having circular +perforations half a millimeter in diameter. The moisture, ash, ether +extract, proteids and carbohydrates are determined by some one of the +processes already described in detail. In this country the methods +of the Association of Official Agricultural Chemists are generally +followed.<a id="FNanchor_535" href="#Footnote_535" class="fnanchor">[535]</a> +For convenience these methods are summarized below.</p> + +<p><i>Moisture.</i>—Dry from two to three grams of the fine-ground sample +for five hours, at the temperature of boiling water, in a current of +dry hydrogen. If the substance be held in a glass vessel, the latter +should not be in contact with the boiling water.</p> + +<p><i>Ash.</i>—Char from two to three grams of the sample and burn to +whiteness at the lowest possible red heat. If a white ash can not be +obtained in this manner, exhaust the charred mass with water, collect +the insoluble residue on a filter, burn it, add this ash to the residue +from the evaporation of the aqueous extract and heat the whole to low +redness until the ash is white.</p> + +<p><i>Ether Extract.</i>—Pure ether is prepared by washing the commercial +article four or five times with water to free it of the chief part +of the alcohol it contains. The residual water is mostly removed by +treating the liquid with caustic soda or potash. Any residual alcohol +or water is finally removed by the action of metallic sodium. The ether +thus prepared is stoppered, after the evolution of hydrogen has ceased, +<span class="pagenum"><a id="Page_543"></a>[Pg 543]</span> +and is kept over metallic sodium. Immediately before use it should be +distilled out of contact with moist air.</p> + +<p>The residue from the determination of moisture, as described above, is +extracted in an appropriate apparatus (<b><a href="#P_39">39</a></b>) with the pure ether +for sixteen hours. The extract is dried to constant weight. The weight +may be checked by drying and weighing the extraction tube and its +contents before and after the operation.</p> + +<p><i>Crude Proteids.</i>—Proceed as in the method of determining +nitrogen in the absence of nitrates and multiply the weight of nitrogen +obtained by 6.25. This factor is a general one, but should not be +rigidly applied. In each instance, according to the nature of the +cereal, the appropriate factor, pointed out in paragraph <b><a href="#P_407">407</a></b> +should be used, and the factor 6.25 be applied only in those cases +where a special factor is not given. The factors for the common cereals +are wheat 5.70, rye 5.62, oats 6.06, maize 6.22, barley 5.82 and flaxseed 5.62.</p> + +<p>For separating the proteid matters consult paragraphs <b><a href="#P_392">392-410</a></b>. +In the case of wheat the methods of Teller may be consulted.<a id="FNanchor_536" href="#Footnote_536" class="fnanchor">[536]</a></p> + +<p><i>Amid Nitrogen.</i>—The albuminoid nitrogen is determined as +directed in paragraph <b><a href="#P_203">203</a></b> of volume II. The difference between +this number and that representing the total nitrogen gives the nitrogen +as amids.</p> + +<p><i>Fiber and Carbohydrates.</i>—The methods of analysis are described +in detail in Part Third.</p> + +<p><b>529. Bread.</b>—In general, the same processes are followed in +bread analysis as are used with cereals and flours. In addition to +the regular analytical processes, breads are to be examined for +adulterants, bleaching and coloring matters, and for the purpose of +determining the changes which have taken place in their nutrient +constituents in the processes of fermentation and cooking.</p> + +<p><i>Temperature of Baking.</i>—The interior of a loaf during the +process of baking does not attain the high temperature commonly +supposed. This temperature is rarely found to be more than one degree +above the boiling point of water.<a id="FNanchor_537" href="#Footnote_537" class="fnanchor">[537]</a> +In biscuits and other thin cakes, which become practically dry and +which by reason of their thinness are the more readily penetrated by +heat, the temperature may go as high as 110°.</p> + +<p><i>Soluble Extract.</i>—The quantity of matters both in flour and +bread, soluble in cold water, is determined by extraction in the usual +<span class="pagenum"><a id="Page_544"></a>[Pg 544]</span> +way and drying the extract. Soluble albuminoids, sugars and mineral +salts are extracted by this process. When possible, the operation should +be conducted both on the bread and the flour from which it is made.</p> + +<p><i>Color.</i>—In baker’s parlance is found an apparent contradiction +of terms, since it speaks of bread with “no color” when the loaf is +dark brown, while a white loaf is said to have a high color. An ideal +color for the interior of a loaf is a light cream tint, which is +more desirable than a pure white.<a id="FNanchor_538" href="#Footnote_538" class="fnanchor">[538]</a> +The texture, odor and flavor of the loaf are also to be considered, but +these are properties of more importance to the technical expert than to +the analyst.</p> + +<p><i>Quantity of Water.</i>—It is not possible to set a rule of +limitation in respect of the quantity of water a bread should hold. For +full loaves, perhaps forty per cent is not too high a maximum, while +some authors put it as low as thirty-four per cent. Some flours are +capable of holding more water than others, and the loaf should have +just enough water to impart to the slice of bread the requisite degree +of softness and the proper texture. Most breads will have a content of +water ranging from thirty to forty per cent. In biscuits and other thin +cakes the moisture is much less in quantity.</p> + +<p><i>Acidity.</i>—The acidity of both bread and flour is determined by +shaking ten grams of the sample with 200 cubic centimeters of distilled +water for fifteen minutes, pouring the mass on a filter and titrating +an aliquot part of the filtrate with tenth-normal alkali. The acidity +is reckoned as lactic acid in the case of breads raised by fermentation.</p> + +<p><i>Nature of Nitrogenous Compounds.</i>—The methods of investigation +are described in paragraphs <b><a href="#P_392">392-410</a></b>.</p> + +<p><b>530. Determination of Alum in Bread.</b>—The presence of alum in +bread may be detected by means of logwood. Five grams of fresh logwood +chips are digested with 100 cubic centimeters of amyl alcohol. One +cubic centimeter of this decoction and the same quantity of a saturated +solution of ammonium carbonate are mixed with ten grams of flour and +an equal quantity of water. With pure flour, a slight pink tint is +<span class="pagenum"><a id="Page_545"></a>[Pg 545]</span> +produced. In the presence of alum the color changes to a lavender or +blue, which is persistent on heating.</p> + +<p>The test may be varied by diluting five cubic centimeters of the +reagents mentioned with ninety cubic centimeters of water and pouring +the mixture over ten grams of the crumbled bread. After standing for +five minutes, any residual liquid is poured off and the residue, washed +once with a little water, is dried in a steam bath, when the blue color +is developed if alum be present.<a id="FNanchor_539" href="#Footnote_539" class="fnanchor">[539]</a></p> + +<p><b>531. Chemical Changes Produced by Baking.</b>—Changes of a chemical +nature, produced in bread by baking, are found chiefly in modifications +of the starch and proteids. The starch is partly converted into dextrin +and the albumins are coagulated. The changes in digestion coefficient +are determined by the methods which follow. The fermentations which +precede the baking are due to the usual decompositions of the +carbohydrates under the influence of yeast germs.</p> + +<h3>FODDERS, GRASSES<br> AND ENSILAGE.</h3> + +<p><b>532. General Principles.</b>—The analyst, in examining the fibrous +foods of cattle, is expected to determine moisture, ash, fiber and +other carbohydrates, ether extract and albuminoid and amid nitrogen. If +a more exhaustive study be required, the sugar and starch are separated +from the other non-nitrogenous matters, the carbohydrate bodies +yielding furfuraldehyd separately determined and the ash subjected to +a quantitive analysis. The processes are conducted in harmony with the +principles and methods of procedure fully set forth in the preceding pages.</p> + +<p>Green fodders and grasses are easily dried and sampled by comminution +in the shredder described on <a href="#Page_9">page 9</a>, and roots +by that shown on <a href="#Page_10">page 10</a>. The moisture is +determined by drying a small sample of the shredded mass, while the +rest of it is dried, first at about 60° and finally at 100°, or a +little above, ground to a fine powder and subjected to analysis by +methods already described. The food values as obtained by analysis +should be compared, when possible, with those secured by natural and +artificial digestion. +<span class="pagenum"><a id="Page_546"></a>[Pg 546]</span></p> + +<p>Ensilage is shredded and analyzed in precisely the same way, but in +drying, the content of volatile acids formed during fermentation must +be considered. In other words, the loss on drying ensilage at 100°, or +slightly above, is due not only to the escape of water but also to the +volatilization of the acetic acid, which is one of the final products +of fermentation which the mass undergoes in the silo.</p> + +<p><b>533. Organic Acids in Ensilage.</b>—In the examination of ensilage, +the organic acids which are present may be determined by the processes +described in following paragraphs. The acetic acid, formed chiefly +by fermentation, is conveniently determined by the method given for +tobacco further on. Lactic acid is detected and estimated by expressing +the juice from a sample of ensilage, removing the acetic acid by +distillation, repeated once or twice, and treating the filtered residue +with zinc carbonate in excess, filtering and determining the zinc +lactate in the filtrate. The zinc is determined by the method described +for evaporated apples and the lactic acid calculated from the weight of +zinc found. Crystallized zinc lactate contains 18.18 per cent of water +and 27.27 per cent of zinc oxid.<a id="FNanchor_540" href="#Footnote_540" class="fnanchor">[540]</a></p> + +<p><b>534. Changes due to Fermentation in the Silo.</b>—Silage differs +from green fodder in having less starch and sugar, more acetic and +lactic acids and alcohol and a higher proportion of amid to albuminoid +nitrogen.<a id="FNanchor_541" href="#Footnote_541" class="fnanchor">[541]</a> +There is also a considerable loss of nitrogenous substances in +ensilage, due probably to their conversion into ammonium acetate, which +is lost on drying.</p> + +<p><b>535. Alcohol in Ensilage.</b>—The fermentation which takes place +in the silo is not wholly of an alcoholic nature, as the development +of lactic acid, noted above, clearly indicates. The alcohol which +is formed may escape and but small quantities can be detected in +the ripened product. So small is this quantity of alcohol that it +appears to be useless to try to secure a quantitive estimation of it. +Qualitively, it may be detected by collecting it in a distillate, which +is neutralized or made slightly alkaline with soda or potash lye and +redistilled. The greater part of the alcohol will be found in the first +few cubic centimeters, which are made alkaline with potash lye and as +<span class="pagenum"><a id="Page_547"></a>[Pg 547]</span> +much iodin added as can be without giving a red tint to the solution. +Any alcohol which is present will soon separate as iodoform.</p> + +<p><b>536. Comparative Values of Fodder and Ensilage.</b>—In judging of +the comparative values of green and dry fodders for feeding purposes, +it is necessary to secure representative samples in the green, quickly +dried and ensilaged condition. It is quite certain that the greater +part of the sugar contained in green fodders is lost both by natural +curing and by placing in a silo. When well cured by the usual processes +there is but little loss of nitrogenous matters, but in the silo this +loss is of considerable magnitude, amounting in some instances to as +much as thirty per cent.</p> + +<p>The ideal way of preparing green fodders in order to preserve the +maximum food value efficiently, is to shred them and dry rapidly by +artificial heat, or in the sunlight, until they are in a condition +which insures freedom from fermentation. In this condition, when placed +in bales, under heavy pressure, the food constituents are preserved in +the highest available form. The immense sugar content of the stalks of +maize and sorghum could be preserved in this way almost indefinitely.</p> + +<h3>FLESH PRODUCTS.</h3> + +<p><b>537. Names Of Meats.</b>—The parts of the animal from which the +meats are taken have received distinctive names, which serve to +designate the parts of the carcass offered for sale. These names are +not invariable and naturally are quite different in many markets. In +this country there is some degree of uniformity among butchers in +naming the meats from different parts. The names in scientific use +for the parts of mutton, beef and pork are found in the accompanying +illustrations.<a id="FNanchor_542" href="#Footnote_542" class="fnanchor">[542]</a></p> + +<p><b>538. Sampling.</b>—When possible the whole animal should constitute +the sample. The relative weights of blood, intestinal organs, hide, +hoofs, horns, bones and edible flesh are determined as accurately as +possible. The general method of preparing samples of animal products is +given in paragraph <b><a href="#P_5">5</a></b>. +<span class="pagenum"><a id="Page_548"></a>[Pg 548]</span></p> + +<div class="figcenter smcap"> + <img id="FIG_114" src="images/fig114.jpg" alt="" width="600" height="395" > + <p class="center">Fig. 114.</p> + <img id="FIG_115" src="images/fig115.jpg" alt="" width="600" height="376" > + <p class="center">Fig. 115.</p> + <img id="FIG_116" src="images/fig116.jpg" alt="" width="600" height="372" > + <p class="center">Fig. 116.</p> + <p class="f105 spb1">Names of Cuts of Meat.</p> +</div> + +<p><span class="pagenum"><a id="Page_549"></a>[Pg 549]</span> +The method of sampling employed by Atwater and Woods is essentially +that just noted.<a id="FNanchor_543" href="#Footnote_543" class="fnanchor">[543]</a> +The sample, as received at the laboratory, is weighed, the flesh +(edible portion) is then separated from the refuse (skin, bones etc.) +and both portions weighed. There is always a slight loss in the +separation, evidently due to evaporation and to small fragments of +the tissues that adhere to the hands and to the implements used in +preparing the sample. The perfect separation of the flesh from the +other tissues is difficult, but the loss resulting from this is small. +In sampling the material for analysis, it is finely chopped, either in +a tray or in a sausage cutter, and in each case is well mixed.</p> + +<p><b>539. Methods of Analysis.</b>—The general methods for the analyses +of food products are applicable to meats and animal products in +general. In the separation of the nitrogenous constituents the methods +described in paragraphs <b><a href="#P_411">411-414</a></b> are followed. It is +not safe to estimate as proteids the total nitrogen multiplied by 6.25, since the +flesh bases have much higher percentages of nitrogen than are found +in proteid matters. As indicated in paragraph <b><a href="#P_280">280</a></b> the +complete extraction of dried meats by ether is difficult of accomplishment. +After a few hours it may be assumed that the total extract will +represent the fat, although additional soluble matters are obtained +by continuing the process. The heat producing power may be calculated +from the analytical data secured. The methods which have been described +in the preceding pages will be found sufficient for guidance in the +examination of animal products, and the analyst will find them, when +modified to suit particular cases, adapted to the isolation and +estimation of proximate food principles.</p> + +<p>The methods of analyses followed by Atwater and Woods are given +below:<a id="FNanchor_544" href="#Footnote_544" class="fnanchor">[544]</a></p> + +<p><i>Water and Water-Free Substance.</i>—The drying is done in ordinary +water ovens at a temperature of nominally 100°, but actually at 96° and +98°. For each analysis of animal tissues (flesh) one or more samples of +from fifty to one hundred grams of the freshly chopped substance are +weighed on a small plate, heated for from twenty-four to forty-eight +<span class="pagenum"><a id="Page_550"></a>[Pg 550]</span> +hours, cooled, allowed to stand in the open air for about twenty-four +hours, weighed, ground, sifted through a sieve with circular holes +one-half millimeter in diameter, bottled and set aside for analysis. +In case of fat samples which cannot be worked through so fine a sieve, +either a coarser sieve is used or the substance crushed as finely as +practicable and bottled without sifting.</p> + +<p>For the complete desiccation, about two grams of material are dried for +three hours. It is extremely difficult to get an absolutely constant +weight, though it is found that this is in most cases approximately +attained in four hours.</p> + +<p><i>Nitrogen, Protein, Albuminoids etc.</i>—The nitrogen is determined +in the partly dried substance by the method of Kjeldahl. The protein +is calculated by multiplying the percentage of nitrogen by 6.25. +The nitrogenous matters in meats and fish, <i>i. e.</i>, in the +materials which have practically no carbohydrates, are also estimated +by subtracting the sum of ether extract and ash from the water-free +substance, or the sum of water, ether extract and ash from the fresh +substance, the remainder being taken as proteids, albuminoids etc., +by difference. While this is not an absolutely correct measure of the +total nitrogenous matter, it is doubtless more nearly so than the +product of the nitrogen multiplied by 6.25.</p> + +<p><i>Fat (Ether Extract).</i>—The fat is extracted with ether in +the usual manner. The point at which the extraction is complete is +not always easy to determine. For the most part, the extraction is +continued for such time as experience indicates to be sufficient, and +then the flask is replaced by another and the extraction repeated until +the new flask shows no increase in weight.</p> + +<p>According to experience, the fat of many animal tissues is much more +difficult to extract than that of most vegetable substances. In +general, the greater the percentage of fat in a substance the more +difficult is the removal of the last traces. Dried flesh is frequently +so hard that the fineness of the material to be extracted seems to be a +very important matter.</p> + +<p><i>Ash.</i>—Ash is determined by the method recommended by the +Association of Official Agricultural Chemists. +<span class="pagenum"><a id="Page_551"></a>[Pg 551]</span></p> + +<p><i>Food Value—Potential Energy.</i>—The food materials are not +necessarily burned in the calorimeter, but the fuel value of a pound of +each of the foods, as given in the tables, is obtained by multiplying +the number of hundredths of a pound of protein and of carbohydrates by +18.6 and the number of hundredths of a pound of fat by 42.2, and taking +the sum of these three products as the number of calories of potential +energy in the materials.</p> + +<p>More reliable results are obtained by using the factors obtained by +Stohmann; <i>viz.</i>, 5731 calories for proteids, 9500 calories for +common glycerids, 9231 calories for butter fat, 3746 calories for +pentose sugars, 3749 calories for dextrose and levulose and 3953 +calories for sucrose and milk sugar.<a id="FNanchor_545" href="#Footnote_545" class="fnanchor">[545]</a></p> + +<p><b>540. Further Examination of Nitrogenous Bodies.</b>—It is evident +that both of the methods proposed above for the examination of the +nitrogenous constituents of meats are unreliable. If the total nitrogen +be determined and multiplied by 6.25 the product does not by any means +represent the true quantity of nitrogenous matter since the flesh bases +contain in some instances more than twenty-five per cent of nitrogen.</p> + +<p>If, on the other hand, the water, ash and fat in a meat sample be +determined and the sum of their per cents be subtracted from 100, the +difference represents the nitrogenous bodies plus all undetermined +matters and errors of analysis. The assumption that meats are free +of carbohydrates is not tenable since glycogen is constantly found +therein and in horse flesh in comparatively large amounts. In a +thoroughly scientific analysis of meats, the nitrogenous bodies should +be separated and determined by groups, according to the principles +developed in paragraphs <b><a href="#P_411">411-414</a></b>. This process requires +a great amount of analytical work and in general it will be sufficient to make +a cold water extract to secure the flesh bases and a hot water extract +to secure the gelatin. The nitrogen is then determined in each of +these portions separately. The nitrogen in the cold water extract is +multiplied by four, in the hot water extract by six and in the residue +by 6.25. The sum of these products represents approximately the total +nitrogenous matter in the sample. +<span class="pagenum"><a id="Page_552"></a>[Pg 552]</span></p> + +<p>Aqueous extracts containing nitrogen are easily prepared for moist +combustion by placing them in the digestion flasks, connecting the +latter with the vacuum service and evaporating the contents of the +flask nearly to dryness. The sulfuric acid is then added and the +nitrogen converted into ammonia and determined in the usual manner.</p> + +<p><b>541. Fractional Analysis of Meats.</b>—A better idea of the +composition of a meat is obtained by separating its constituents into +several groups by the action of different solvents. This method has +been elaborated by Knorr.<a id="FNanchor_546" href="#Footnote_546" class="fnanchor">[546]</a></p> + +<p>The separation of the meats in edible portion and waste and the +determination of moisture and fat are conducted as already described. +The residue from the fat extraction is exhausted with alcohol, and +in the extract are found the nitrogenous bases kreatin, kreatinin, +sarkin and xanthin, and urea, lactic, butyric, acetic and formic acids, +glycogen and inosit. In the residue from the alcohol extraction, the +proteid nitrogen is determined in a separate sample.</p> + +<p>A separate portion of the sample is ground to a fine paste and +repeatedly rubbed up with cold water, which is poured through a tared +filter. When the extraction is complete, the filter and its contents +are dried and the dry residue determined. This residue represents +the nitrogenous constituents of the muscle fibers and their sheaths +together with any other bodies insoluble in cold water. The filtrate +from the cold water extraction is heated to boiling to precipitate +the albuminous matters which are collected, dried and weighed, or the +nitrogen therein determined and the albuminous matters calculated by +multiplying by the usual factor. The filtrate from the coagulated +albuminous bodies is evaporated to dryness and weighed. It consists +essentially of the same materials as the alcoholic extract mentioned +above. The ash and nitrogen in the aqueous extract are also determined.</p> + +<p>The mean content of the edible parts of common meats, expressed as per +cents in groups as mentioned, follow: +<span class="pagenum"><a id="Page_553"></a>[Pg 553]</span></p> + +<table class="spb1"> + <tbody><tr> + <td class="tdr" colspan="2">Per cent.</td> + </tr><tr> + <td class="tdl">Water</td> + <td class="tdr">73.11</td> + </tr><tr> + <td class="tdl">Ash</td> + <td class="tdr">1.18</td> + </tr><tr> + <td class="tdl">Total soluble matter</td> + <td class="tdr">26.89</td> + </tr><tr> + <td class="tdl">Phosphoric acid</td> + <td class="tdr">0.49</td> + </tr><tr> + <td class="tdr" colspan="2"> <br>Per cent.</td> + </tr><tr> + <td class="tdl">Proteids insoluble in cold water</td> + <td class="tdr">13.76</td> + </tr><tr> + <td class="tdl_ws1 bb">Of which coagulable by heat</td> + <td class="tdr bb">2.24</td> + </tr><tr> + <td class="tdl bb">Cold water extract</td> + <td class="tdr bb">3.56</td> + </tr><tr> + <td class="tdl">Ash in water extract</td> + <td class="tdr">1.09</td> + </tr><tr> + <td class="tdl_ws1">Of which phosphoric acid</td> + <td class="tdr">0.38</td> + </tr><tr> + <td class="tdr" colspan="2"> <br>Per cent.</td> + </tr><tr> + <td class="tdl">Fat</td> + <td class="tdr">4.93</td> + </tr><tr> + <td class="tdl">Alcohol extract</td> + <td class="tdr">3.03</td> + </tr><tr> + <td class="tdl">Proteids in residue from alcohol<span class="ws3"> </span></td> + <td class="tdr">17.88</td> + </tr><tr> + <td class="tdl">Total nitrogen in sample</td> + <td class="tdr">3.37</td> + </tr> + </tbody> +</table> + +<p><b>542. Estimation of Starch in Sausages.</b>—Starchy substances are +sometimes added to sausages for the purpose of increasing their weight. +The presence of starch in a sausage is easily detected by iodin. The +quantity may be determined by the following process:<a id="FNanchor_547" href="#Footnote_547" class="fnanchor">[547]</a></p> + +<p>The principle of the process is based upon the observation that while +starch is easily soluble in an aqueous solution of the alkalies, it +is insoluble in an alcoholic solution thereof. The chief constituents +of meat, <i>viz.</i>, fat and proteid matters, on the other hand, +are readily soluble in an alcoholic solution of potash or soda. This +renders the separation of the starch easy. The sample is warmed on a +water bath with a considerable excess of an eight per cent solution of +potassium hydroxid in alcohol whereby the fat and flesh are quickly +dissolved. The starch and other carbohydrate bodies, remain in an +undissolved state. In order to prevent the gelatinizing of the soap +which is formed, the mass is diluted with warm alcohol, the insoluble +residue collected upon a filter and washed with alcohol until the +alkaline reaction disappears. The residue is then treated with aqueous +potassium hydroxid solution, whereby the starch is brought into +solution and, after filtration, is treated with alcohol until it is +all precipitated. The precipitated starch is collected upon a filter, +washed with alcohol and finally with ether, dried and weighed. Starch +<span class="pagenum"><a id="Page_554"></a>[Pg 554]</span> +prepared in this way contains a considerable quantity of potash, the +amount of which can be determined by incineration. In order to avoid +this trouble, the starch, after separation in the first instance +as above mentioned and solution in aqueous potassium hydroxid, +is precipitated on the addition of enough acetic to render the +solution slightly acid. The precipitated starch, in this instance, +is practically free of potash, since potassium acetate is soluble in +alcohol.</p> + +<p><b>543. Detection of Horse Flesh.</b>—Since horse flesh has become +an important article of human food and is often sold as beef and +sausage, a method of distinguishing it is desirable. The comparative +anatomist is able to detect horse flesh when accompanied by its bones, +or in portions sufficiently large for the identification of muscular +characteristics. It is well known that horse flesh contains a much +higher percentage of glycogen than is found in other edible meats. +Niebel has based a method of detecting horse flesh upon this fact, the +glycogen being converted into dextrose and determined in the usual way. +Whenever the percentage of reducing sugars in the dry fat-free flesh +exceeds one per cent, Niebel infers that the sample under examination +is horse flesh.<a id="FNanchor_548" href="#Footnote_548" class="fnanchor">[548]</a></p> + +<p>The reaction for horse flesh, proposed by Bräutigam and Edelmann, is +preferred by Baumert. In this test about fifty grams of the flesh are +boiled for an hour with 200 cubic centimeters of water, the filtered +bouillon evaporated to about half its volume, treated with dilute +nitric acid and the clear filtrate covered with iodin water. Horse +flesh, by reason of its high glycogen content, produces a burgundy +red zone at the points of contact of the two liquids. In the case of +sausages, if starch have been added, a blue zone is produced, and if +dextrin be present, a red zone, both of which obscure the glycogen +reaction. The starch is easily removed by treating the bouillon with +glacial acetic acid. No method is at present known for separating +dextrin from glycogen. The detection of horse flesh is a matter of +considerable importance to agriculture as well as to the consumers, +especially of sausages. A considerable quantity of horse flesh is +annually sent to the market, little of which presumably is sold under +<span class="pagenum"><a id="Page_555"></a>[Pg 555]</span> +its own name. As a cheap substitute for beef and pork in sausages, its +use must be regarded as fraudulent, although no objection can be urged +against its sale when offered under its own name.<a id="FNanchor_549" href="#Footnote_549" class="fnanchor">[549]</a></p> + +<h3>METHODS OF DIGESTION.</h3> + +<p><b>544. Artificial Digestion.</b>—The nutrient values of cereals and +other foods are determined both by chemical analysis and by digestion +experiments. The heat forming properties of foods are disclosed by +combustion in a calorimeter, but the quantity of heat produced is not +in every case a guide to the ascertainment of the nutritive value. This +is more certainly shown, especially in the case of proteid bodies, by +the action of the natural digestive ferments.</p> + +<p>It is probable that the digestion, which is secured by the action of +these ferments without the digestive organs, is not always the same as +the natural process, but when the conditions which prevail in natural +digestion are imitated as closely as possible the effects produced can +be considered as approximately those of the alimentary canal in healthy +action.</p> + +<p>Three classes of ferments are active in artificial digestion, +<i>viz.</i>, amylolytic ferments, serving to hydrolyze starch and +sugars and to convert them into dextrose, maltose and levulose, +aliphalytic ferments, which decompose the glycerids and proteolytic +ferments, which act on the nitrogenous constituents of foods. When +these ferments are made to act on foods under proper conditions of +acidity and temperature, artificial digestion ensues, and by the +measurement of the extent of the action an approximate estimate of +their digestibility can be secured. In artificial digestion, the +temperature should be kept near that of the body, <i>viz.</i>, at about 40°.</p> + +<p>The soluble ferments which are active in the digestion of foods, as +has been intimated, comprise three great classes. Among the first +class, <i>viz.</i>, the amylolytic ferments, are included not only those +which convert starch into dextrose, but also those which cause the +hydrolysis of sugars in general. Among these may be mentioned ptyalin, +invertase, trehalase, maltase, lactase, diastase, inulase, pectase and +cyto-hydrolytic ferments which act upon the celluloses and other fibers. +<span class="pagenum"><a id="Page_556"></a>[Pg 556]</span></p> + +<p>Among the aliphalytic ferments, in addition to those which act also +upon proteid matter, may be mentioned a special one, lipase.</p> + +<p>In the third class of ferments are found pepsin, trypsin or pancreatin +and papain.</p> + +<p>For the latest information in regard to the nature of the soluble +ferments and their nomenclature, the work of Bourquelot may be +consulted.<a id="FNanchor_550" href="#Footnote_550" class="fnanchor">[550]</a></p> + +<p><b>545. Amylytic Ferments.</b>—A very active ferment of this kind is +found in the saliva. Saliva may be easily collected from school boys, +who will be found willing to engage in its production if supplied with +a chewing gum. A gum free of sugar is to be used, or if the chewing +gum of commerce is employed, the saliva should not be collected until +the sugar has disappeared. A dozen boys with vigorous chewing will +soon provide a sufficient quantity of saliva for practical use. The +amylolytic digestion is conducted in the apparatus hereinafter described +for digestion with pepsin and pancreatin. The starch or sugar in fine +powder is mixed with ten parts of water and one part of saliva and +kept at about 37°.5 for a definite time. The product is then examined +for starch, sucrose, maltose, dextrose, dextrin and levulose by the +processes already described. In natural digestion the hydrolysis of the +carbohydrates is not completed in the mouth. The action of the ferment +is somewhat diminished in the stomach, but not perhaps until half an +hour after eating. The dilute hydrochloric acid in the stomach, which +accumulates some time after eating, is not active in this hydrolysis. +On the contrary the amylolytic ferment of the saliva is somewhat +enfeebled by the presence of an acid. The active principle of the +saliva is ptyalin.</p> + +<p>The diastatic hydrolysis of starch has already been described +(<b><a href="#P_179">179</a></b>). It is best secured at a somewhat +higher temperature than that of the human stomach.</p> + +<p><b>546. Aliphalytic Ferments.</b>—In the hydrolysis of glycerids in +the process of digestion the fat acids and glycerol are set free. +Whether the glycerids be completely hydrolyzed before absorption is not +definitely known. In certain cases where large quantities of oil have +<span class="pagenum"><a id="Page_557"></a>[Pg 557]</span> +been exhibited for remedial purposes, the fat acids and soaps have been +found in spherical masses in the dejecta<a id="FNanchor_551" href="#Footnote_551" class="fnanchor">[551]</a> +and have been mistaken for gall stones.</p> + +<p>The fat which enters the chyle appears to be mostly unchanged, except +that it is emulsified.<a id="FNanchor_552" href="#Footnote_552" class="fnanchor">[552]</a> +The aliphalytic ferment can be prepared from the fresh pancreas, +preferably from animals that have not been fed for forty hours before +killing. It is important to prepare the ferment entirely free of +any trace of acid. The fresh glands are rubbed to a fine paste with +powdered glass and extracted for four days with pure glycerol, to which +one part of one per cent soda solution has been added. The filtered +liquor contains aliphalytic, proteolytic and amylytic ferments, and is +employed for saponification by shaking with the fat to form an emulsion +and keeping the mixture, with occasional shaking, at a temperature of +from 40° to 60°. The free acids can be titrated or separated from the +unsaponified fats by solution in alcohol.<a id="FNanchor_553" href="#Footnote_553" class="fnanchor">[553]</a></p> + +<p>Heretofore it has not been possible to separate a pure aliphalytic +ferment from any of the digestive glands. The digestion of carbohydrates +and that of fats are intimately associated, and these two classes of +foods seem to play nearly the same rôle in the animal economy.</p> + +<p>The aliphalytic ferments, prepared from the fresh pancreas, act also on +the glucosids and other ester-like carbohydrate bodies. Since the fats +may be regarded as ethers, the double action indicates the similarity +of composition in the two classes of bodies.<a id="FNanchor_554" href="#Footnote_554" class="fnanchor">[554]</a> +The aliphalytic ferments exist also in plants and have been isolated +from rape seed.<a id="FNanchor_555" href="#Footnote_555" class="fnanchor">[555]</a></p> + +<p><b>547. Proteolytic Ferments.</b>—The most important process in +artificial digestion is the one relating to the action of the ferments +on proteid matters. The hydrolysis of fats and carbohydrates by natural +ferments takes place best in an alkaline medium, while in the case of +proteids when pepsin is used an acid medium is preferred. Since the +acidity of the stomach is due chiefly to hydrochloric, that acid is +employed in artificial digestion. The hydrolyte used is uniformly the +natural ferment of the gastric secretions, <i>viz.</i>, pepsin; but +this is often followed by the pancreatic ferment, (pancreatin, trypsin) +<span class="pagenum"><a id="Page_558"></a>[Pg 558]</span> +in an alkaline medium. During the digestion, the proteids are changed +into peptones, and the measurement of this change determines the degree +of digestion. The total proteid matter is determined in the sample, +and after the digestion is completed, the soluble peptones are removed +by washing and the residual insoluble proteid matter determined by +moist combustion. The difference in the two determinations shows the +quantity of proteid matter digested. The investigations of Kühn on the +digestion of proteids may be profitably consulted.<a id="FNanchor_556" href="#Footnote_556" class="fnanchor">[556]</a> +For a summary of digestion experiments in this country the résumé +prepared by Gordon may be consulted.<a id="FNanchor_557" href="#Footnote_557" class="fnanchor">[557]</a> +The method followed in this laboratory is fully described by Bigelow and +Hamilton.<a id="FNanchor_558" href="#Footnote_558" class="fnanchor">[558]</a></p> + +<p><b>548. Ferments Employed.</b>—Both the pepsins of commerce and those +prepared directly from the stomachs of pigs may be used. The commercial +scale pepsin is found, as a rule, entirely satisfactory, and more +uniform results are secured by its use than from pepsin solutions made +from time to time from pig stomachs. In the preparation of the pepsin +solution one gram of the best scale pepsin is dissolved in one liter +of 0.33 per cent hydrochloric acid. Two grams of the sample of food +products, in fine powder, are suspended in 100 cubic centimeters of the +solution and kept, with frequent shaking, at a temperature of 40° for +twelve hours. The contents of the flask are poured on a wet filter, the +residue on the filter well washed with water not above 40°, the filter +paper and its contents transferred to a kjeldahl flask and the residual +nitrogen determined and multiplied by 6.25 to get the undigested +proteid matter. A large number of digestions can be conducted at once +in a bath shown in <a href="#FIG_117">Fig. 117</a>.<a id="FNanchor_559" href="#Footnote_559" class="fnanchor">[559]</a> +The quantity of water in the bath should be as large as possible.</p> + +<p><b>549. Digestion in Pepsin and Pancreatin.</b>—The digestion of the +proteids is not as a rule wholly accomplished by the stomach juices, +and, therefore, in order to secure in artificial digestion results +approximating those produced in the living organism, it is necessary +to follow the treatment with pepsin by a similar one with the pancreas +<span class="pagenum"><a id="Page_559"></a>[Pg 559]</span> +juices. The method employed in this laboratory is essentially that of +Stutzer modified by Wilson.<a id="FNanchor_560" href="#Footnote_560" class="fnanchor">[560]</a></p> + +<div class="figcenter smcap"> + <img id="FIG_117" src="images/fig117.jpg" alt="" width="600" height="273" > + <p class="center spb1">Fig. 117. Bath for Artificial Digestion.</p> +</div> + +<p><span class="pagenum"><a id="Page_560"></a>[Pg 560]</span> +The residue from the pepsin digestion, after washing, is treated for +six hours at near 40° with 100 cubic centimeters of pancreas solution, +prepared as follows:</p> + +<p>Free the pancreas of a healthy steer of fat, pass it through a sausage +grinder, rub one kilogram in a mortar with fine sand and allow to stand +for a day or longer. Add three liters of lime water, one of glycerol, +of 1.23 specific gravity, and a little chloroform and set aside for +six days. Separate the liquor by pressure in a bag and filter it +through paper. Before using, mix a quarter of a liter of the filtrate +with three-quarters of a liter of water and five grams of dry sodium +carbonate, or its equivalent crystallized, heat from 38° to 40° for +two hours and filter.<a id="FNanchor_561" href="#Footnote_561" class="fnanchor">[561]</a> +In order to avoid the trouble of preparing the pancreas solution pure +active pancreatin may be used.<a id="FNanchor_562" href="#Footnote_562" class="fnanchor">[562]</a> +One and a half grams of pure pancreatin and three grams of sodium +carbonate are dissolved in one liter of water and 100 cubic centimeters +of this solution are used for each two grams of the sample. In all +cases where commercial pepsin and pancreatin are used, their activity +should be tested with bodies such as boiled whites of eggs, whose +coefficient of digestibility is well known and those samples be +rejected which do not prove to have the required activity.<a id="FNanchor_563" href="#Footnote_563" class="fnanchor">[563]</a></p> + +<p><b>550. Digestion in Pancreas Extract.</b>—In order to save the time +required for successive digestions in pepsin and pancreatin Niebling +has proposed to make the digestion in the pancreas extract alone.<a id="FNanchor_564" href="#Footnote_564" class="fnanchor">[564]</a> +This process and also a slight modification of it have been used with +success by Bigelow and McElroy.<a id="FNanchor_565" href="#Footnote_565" class="fnanchor">[565]</a> +Two grams of the sample are washed with ether and placed in a digestion +flask with 100 cubic centimeters of two-tenths per cent hydrochloric +acid. The contents of the flask are boiled for fifteen minutes, cooled, +and made slightly alkaline with sodium carbonate. One hundred cubic +centimeters of the unfiltered pancreas solution, prepared as directed +above, are added and the digestion continued at 40° for six hours. The +residue is thrown on a filter, washed, and the nitrogen determined. +The method is simplified by the substitution of active commercial +pancreatin for pancreas extract. The solution of the ferment is made of +the same strength as is specified above. +<span class="pagenum"><a id="Page_561"></a>[Pg 561]</span></p> + +<p><b>551. Artificial Digestion of Cheese.</b>—The artificial digestion +of cheese is conducted by Stutzer as follows:<a id="FNanchor_566" href="#Footnote_566" class="fnanchor">[566]</a></p> + +<p>The digestive liquor is prepared from the fresh stomachs of pigs by +cutting them into fine pieces and mixing with five liters of water and +100 cubic centimeters of hydrochloric acid for each stomach. To prevent +decomposition, two and a half grams of thymol, previously dissolved in +alcohol, are added to each 600 cubic centimeters of the mixture. The +mixture is allowed to stand for a day with occasional shaking, poured +into a flannel bag and the liquid portion allowed to drain without +pressing. The liquor obtained in this way is filtered, first through +coarse and then through fine paper, and when thus prepared will keep +several months without change. It is advisable to determine the content +of hydrochloric acid in the liquor by titration and this content should +be two-tenths of a per cent. The cheese to be digested is mixed with +sand as previously described, freed of fat by extraction with ether, +and a quantity corresponding to five grams of cheese placed in a +beaker, covered with half a liter of the digestive liquor and kept at +a temperature of 40° for forty-eight hours. At intervals of two hours +the flasks are well shaken and five cubic centimeters of a ten per +cent solution of hydrochloric acid added and this treatment continued +until the quantity of hydrochloric acid amounts to one per cent. After +the digestion is finished, the contents of the beaker are thrown on a +filter, washed with water and the nitrogen determined in the usual way +in the residue. By allowing the pepsin solution to act for two days as +described above, the subsequent digestion with pancreas solution is +superfluous.</p> + +<p><b>552. Suggestions Regarding Manipulation.</b>—The filter papers +should be as quick working as possible to secure the separation of +all undissolved particles. They should be of sufficient size to hold +the whole contents of the digestion flask at once, since if allowed +to become empty and partially dry, filtration is greatly impeded. The +residue should be dried at once if not submitted immediately to moist +combustion. After drying, the determination of the nitrogen can be made +at any convenient time. Beaker flasks, <i>i. e.</i>, lip erlenmeyers +<span class="pagenum"><a id="Page_562"></a>[Pg 562]</span> +with a wide mouth are most convenient for holding the materials during +digestion. The flasks are most conveniently held by a crossed rubber +band attached at either end to pins in the wooden slats extending +across the digestive bath. The bath should be suspended by cords from +supports on the ceiling and a gentle rotatory motion imparted to it +resembling the peristaltic action attending natural digestion.</p> + +<p><b>553. Natural Digestion.</b>—The digestion of foods by natural +processes is determined chiefly by the classes of ferments already +noted. The principle underlying digestive experiments with the animal +organism may be stated as follows: A given weight of food of known +composition is fed to a healthy animal under the conditions of careful +control and preparation already mentioned. The solid dejecta of the +animal during a given period are collected and weighed daily, being +received directly from the animal in an appropriate bag, safely +secured, as is shown in the accompanying <a href="#FIG_118">figure</a>. +The dejecta are weighed, dried, ground to a fine powder, mixed and +a representative part analyzed. The difference between the solid +bodies in the dejecta and those given in the food during the period +of experiment represents those nutrients which have been digested and +absorbed during the passage of the food through the alimentary canal. +The urine, containing solid bodies representing the waste of the animal +organism, does not require to be analyzed for the simple control of +digestive activity outlined above. In a complete determination of this +kind the exhalations from the surface of the body and from the lungs +are also determined. In the latter case the human animal is selected +for the experiment; in the former it is more convenient to employ the +lower animals, such as the sheep and cow.</p> + +<p>The arrangement of the stalls and of the apparatus for collecting the +excreta should be such as is both convenient and effective.<a id="FNanchor_567" href="#Footnote_567" class="fnanchor">[567]</a></p> + +<p>The method of constructing a bag for attachment to a sheep is shown in +<a href="#FIG_118">Fig. 118</a>. It is made according to the directions given by +Gay, of heavy cloth and in such a way as to fit closely the posterior parts of the +animal.<a id="FNanchor_568" href="#Footnote_568" class="fnanchor">[568]</a> +When attached, its appearance is shown in <a href="#FIG_119">Fig. 119</a>. +<span class="pagenum"><a id="Page_563"></a>[Pg 563]</span></p> + +<div class="figcontainer smcap"> + <div class="figsub"> + <p class="spa3"> </p> + <img id="FIG_118" src="images/fig118.jpg" alt="" width="300" height="129" > + <p class="center spa2">Fig. 118.—Bag for<br> Collecting Feces.</p> + </div> + <div id="FIG_119" class="figsub"> + <img src="images/fig119.jpg" alt="" width="200" height="458" > + <p class="center">Fig. 119.—Fecal Bag Attachment.</p> + </div> +</div> + +<p>Healthy animals in the prime of life are used, and the feeding +experiments are conducted with as large a number of animals as +possible, in order to eliminate the effects of idiosyncrasy. The food +used is previously prepared in abundant quantity and its composition +determined by the analysis of an average sample.</p> + +<p>The feeding period is divided into two parts. In the first part the +animal is fed for a few days with the selected food until it is certain +that all the excreta are derived from the nutrients used. In the second +part the same food is continued and the excreta collected, weighed, the +moisture determined, and the total weight of the water-free excreta +ascertained. The first part should be of at least seven and the second +of at least five days duration. The urine and dung are analyzed +separately. Males are preferred for the digestion experiments because +of the greater ease of collecting the urine and feces without mixing. +For ordinary purposes the feces only are collected. The methods of +analysis do not differ from those described for the determination of +the usual ingredients of a food.</p> + +<p><i>Example.</i>—The following data taken from the results of digestive +<span class="pagenum"><a id="Page_564"></a>[Pg 564]</span> +experiments, obtained at the Maine Station, will illustrate the method +of comparing the composition of the food with that of the feces and +of determining the degree of digestion which the proteids and other +constituents of the food have undergone.</p> + +<p class="f120"><b><span class="smcap">Composition of Maize Fodder and of Feces<br> +Therefrom after Feeding to Sheep.</span></b></p> + +<table class="spb1"> + <thead><tr> + <th class="tdc fs_110" colspan="7"><span class="smcap">Before Drying.</span></th> + </tr><tr> + <th class="tdc bb">Food</th> + <th class="tdc bb">Water,<br> per cent. </th> + <th class="tdc bb">Ash,<br> per cent. </th> + <th class="tdc bb">Proteid,<br> per cent. </th> + <th class="tdc bb">Fiber,<br> per cent. </th> + <th class="tdc bb">Fat,<br> per cent. </th> + <th class="tdc bb">Undetermined,<br>per cent.</th> + </tr></thead> + <tbody><tr> + <td class="tdl">Sweet maize</td> + <td class="tdc">83.85</td> + <td class="tdc">1.13</td> + <td class="tdc">2.18</td> + <td class="tdc">4.14</td> + <td class="tdc">0.62</td> + <td class="tdc">8.08</td> + </tr><tr> + <td class="tdl">Feces</td> + <td class="tdc">72.01</td> + <td class="tdc">...</td> + <td class="tdc">...</td> + <td class="tdc">...</td> + <td class="tdc">...</td> + <td class="tdc">...</td> + </tr><tr> + <td class="tdc fs_110" colspan="7"> <br><b><span class="smcap">Dry.</span></b></td> + </tr><tr> + <td class="tdc bb"><b>Food</b></td> + <td class="tdc bb"> </td> + <td class="tdc bb"><b>Ash,<br> per cent. </b></td> + <td class="tdc bb"><b>Proteid,<br> per cent. </b></td> + <td class="tdc bb"><b>Fiber,<br> per cent. </b></td> + <td class="tdc bb"><b>Fat,<br> per cent. </b></td> + <td class="tdc bb"><b>Undetermined,<br>per cent.</b></td> + </tr><tr> + <td class="tdl">Sweet maize</td> + <td class="tdc"> </td> + <td class="tdc"> 7.01</td> + <td class="tdc">13.52</td> + <td class="tdc">25.63</td> + <td class="tdc">3.86</td> + <td class="tdc">49.98</td> + </tr><tr> + <td class="tdl">Feces</td> + <td class="tdc"> </td> + <td class="tdc">14.42</td> + <td class="tdc">17.52</td> + <td class="tdc">19.34</td> + <td class="tdc">2.68</td> + <td class="tdc">46.04</td> + </tr><tr> + <td class="tdc fs_110" colspan="7"> <br><b><span class="smcap">Daily Weights.</span></b></td> + </tr><tr> + <td class="tdc bb"><b>Food</b></td> + <td class="tdc bb"> </td> + <td class="tdc bb"> </td> + <td class="tdc bb"> </td> + <td class="tdc bb"> </td> + <td class="tdc bb"><b> Green, <br>grams.</b></td> + <td class="tdc bb"><b>Dry,<br> grams. </b></td> + </tr><tr> + <td class="tdl">Sweet maize</td> + <td class="tdc"> </td> + <td class="tdc"> </td> + <td class="tdc"> </td> + <td class="tdc"> </td> + <td class="tdc">2521</td> + <td class="tdc">407</td> + </tr><tr> + <td class="tdl">Feces</td> + <td class="tdc"> </td> + <td class="tdc"> </td> + <td class="tdc"> </td> + <td class="tdc"> </td> + <td class="tdc"> 445</td> + <td class="tdc">125</td> + </tr><tr> + <td class="tdc fs_110" colspan="7"> <br><b><span class="smcap">Per Cent Digested.</span></b></td> + </tr><tr> + <td class="tdc bb"><b>Food</b></td> + <td class="tdc bb"> </td> + <td class="tdc bb"><b>Ash,</b></td> + <td class="tdc bb"><b>Proteid,</b></td> + <td class="tdc bb"><b>Fiber,</b></td> + <td class="tdc bb"><b>Undetermined,</b></td> + <td class="tdc bb"><b>Fat,</b></td> + </tr><tr> + <td class="tdl">Sweet maize</td> + <td class="tdc"> </td> + <td class="tdc">37.0</td> + <td class="tdc">60.2</td> + <td class="tdc">76.9</td> + <td class="tdc">71.8</td> + <td class="tdc">78.3</td> + </tr> + </tbody> +</table> + +<p>In the above instance it is seen that the coefficient of digestibility +extended from 37.0 per cent in the case of the mineral components +of the food, to 78.3 per cent in the case of the fats. These data +are taken only from the results obtained from a single sheep and one +article of food. The mean data secured from two animals and three kinds +of maize fodder show the following per cents of digestibility: Ash +39.4, proteid 61.8, fiber 76.7, undetermined matters 72.1, fat 76.4. +The undetermined matters are those usually known as nitrogen free +extract and composed chiefly of pentosans and other carbohydrates.<a id="FNanchor_569" href="#Footnote_569" class="fnanchor">[569]</a></p> + +<p><b>554. Natural Digestibility of Pentosans.</b>—The digestibility +of pentosan bodies in foods under the influence of natural ferments +has been investigated by Lindsey and Holland.<a id="FNanchor_570" href="#Footnote_570" class="fnanchor">[570]</a> +The feeding and +collection of the feces is carried on as described above and the +relative proportions of pentosan bodies in the foods and feces +<span class="pagenum"><a id="Page_565"></a>[Pg 565]</span> +determined by estimating the furfuraldehyd as prescribed in paragraph +<b><a href="#P_150">150</a></b>.<a id="FNanchor_571" href="#Footnote_571" class="fnanchor">[571]</a></p> + +<h3>PRESERVED MEATS.</h3> + +<p><b>555. Methods of Examination.</b>—In general the methods of +examination are the same as those applied in the study of fresh +meats. The contents of water, salt and other preservatives, fat and +nitrogenous matters are of most importance. When not already in a fine +state, the preserved meats are run through meat cutters until reduced +to a fine pulp. Most potted meats are already in a state of subdivision +well suited to analytical work. The composition of preserved meats has +been thoroughly studied in this laboratory by Davis.<a id="FNanchor_572" href="#Footnote_572" class="fnanchor">[572]</a></p> + +<p><b>556. Estimation Of Fat.</b>—Attention has already been called to +the difficulty of extracting the fat from meats by ether or other +solvents.<a id="FNanchor_573" href="#Footnote_573" class="fnanchor">[573]</a> +In preserved meats, as well as in fresh, it is preferable to adopt some +method which will permit of the decomposition of the other organic +matters and the separation of the fat in a free state. The most +promising methods are those employed in milk analyses for the solution +of nitrogenous matters. Sulfuric or hydrochloric acid may be used for +this purpose, preference being given to sulfuric. The separated fats +may be taken up with ether or separated by centrifugal action. A method +of this kind for preserved meats, suggested by Hefelmann, is described below.</p> + +<p>About six grams of the moist preserved meat are placed in a calibrated +test tube and dissolved in twenty-five cubic centimeters of fuming +hydrochloric acid. The tube is placed in a water bath, quickly heated +to boiling and kept at that temperature for half an hour. About twenty +cubic centimeters of cold water are added and the temperature lowered +to 30°, then twenty cubic centimeters of ether and the tube gently +shaken to promote the solution of the fat. When the ether layer has +separated, its volume is read and an aliquot part removed by means of a +pipette, dried and weighed. The separation of the ethereal solution is +greatly promoted by whirling.</p> + +<p>The mean proportions of the ingredients of preserved meats are about +as follows: +<span class="pagenum"><a id="Page_566"></a>[Pg 566]</span></p> + +<table class="spb1"> + <tbody><tr> + <td class="tdl"> </td> + <td class="tdr">Per cent.</td> + </tr><tr> + <td class="tdl_ws1">Water</td> + <td class="tdr_ws1">67.0</td> + </tr><tr> + <td class="tdl_ws1">Dry matter</td> + <td class="tdr_ws1">33.0</td> + </tr><tr> + <td class="tdl" colspan="2"> </td> + </tr><tr class="fs_105"> + <td class="tdl">Of which</td> + <td class="tdr_ws1"> </td> + </tr><tr> + <td class="tdl_ws1">Nitrogenous bodies</td> + <td class="tdr_ws1">19.0</td> + </tr><tr> + <td class="tdl_ws1">Fats</td> + <td class="tdr_ws1">10.5</td> + </tr><tr> + <td class="tdl_ws1">Ash and undetermined</td> + <td class="tdr_ws1"> 3.5</td> + </tr> + </tbody> +</table> + +<p><b>557. Meat Preservatives.</b>—Various bodies are used to give taste +and color to preserved meats and to preserve them from fermentation. +The most important of these bodies are common salt, potassium and +sodium nitrates, sulfurous, boric, benzoic and salicylic acids, +formaldehyd, saccharin and hydronaphthol. A thorough study of the +methods of detecting and isolating these bodies has been made in this +laboratory by Davis and the results are yet to be published as a part +of Bulletin 13.</p> + +<h3>DETERMINATION OF NUTRITIVE VALUES.</h3> + +<p><b>558. Nutritive Value of Foods.</b>—The value of a food as a +nutrient depends on the amount of heat it gives on combustion in the +tissues of the body, <i>i. e.</i> oxidation, and in its fitness to +nourish the tissues of the body, to promote growth and repair waste. +The foods which supply heat to the body are organic in their nature and +are typically represented by fats and carbohydrates. The foods which +promote growth and supply waste are not only those which preeminently +supply heat, but also include the inorganic bodies and organic +nitrogenous matters represented typically by the proteids. It is not +proper to say that one class of food is definitely devoted to heat +forming and another to tissue building, inasmuch as the same substance +may play an important rôle in both directions. As heat formers, +carbohydrates and proteids have an almost equal value, as measured by +combustion in oxygen, while fat has a double value for this purpose. +The assumption that combustion in oxygen forms a just criterion for +determining the value of a food must not be taken too literally. There +are only a few bodies of the vast number which burn in oxygen that are +capable of assimilation and oxidation by the animal organism. Only +those parts of the food that become soluble and assimilable under +the action of the digestive ferments, take part in nutrition and the +<span class="pagenum"><a id="Page_567"></a>[Pg 567]</span> +percentage of food materials digested varies within wide limits but +rarely approaches 100. It may be safely said that less than two-thirds +of the total food materials ingested are dissolved, absorbed, +decomposed and assimilated in the animal system. We have no means +of knowing how far the decomposition (oxidation) extends before +assimilation, and therefore no theoretical means of calculating the +quantity of heat which is produced during the progress of digestion. +The vital thermostat is far more delicate than any mechanical +contrivance for regulating temperature and the quantity of food, in a +state of health, converted into heat, is just sufficient to maintain +the temperature of the body at a normal degree. Any excess of heat +produced, as by violent muscular exertion, is dissipated through the +lungs, the perspiration and other secretions of the body.</p> + +<p>Pure cellulose or undigestible fiber, when burned in oxygen, will +give a thermal value approximating that of sugar, but no illustration +is required to show that when taken into the system the bodily heat +afforded by it is insignificant in quantity.</p> + +<p>Thermal values, therefore, have little comparative usefulness +in determining nutritive worth, except when applied to foods of +approximately the same digestive coefficient.</p> + +<p><b>559. Comparative Value of Food Constituents.</b>—It has already +been noted that, judged by combustion in oxygen, carbohydrates +and proteids have about half the thermal value possessed by fats. +Commercially, the values of foods depend in a far greater degree on +their flavor and cooking qualities than upon the amount of nutrition +they contain. Butter fat, which is scarcely more nutritious than +tallow, is worth twice as much in the market, while the prices paid for +vegetables and fruits are not based to any great extent on their food +properties.<a id="FNanchor_574" href="#Footnote_574" class="fnanchor">[574]</a> +In cereals, especially in wheat, the quantity of fat is relatively +small, and starch is the preponderating element. In meats, +carbohydrates are practically eliminated and fats and proteids are the +predominating constituents.</p> + +<p>In the markets, fats and proteids command far higher prices than sugars +and starches. The relative commercial food value of a cereal may be +roughly approximated by multiplying the percentages of fat and protein +<span class="pagenum"><a id="Page_568"></a>[Pg 568]</span> +by two and a half and adding the products to the percentage of +carbohydrates less insoluble fiber. This method was adopted in valuing +the cereals at the World’s Columbian Exposition.<a id="FNanchor_575" href="#Footnote_575" class="fnanchor">[575]</a></p> + +<p><b>560. Nutritive Ratio.</b>—In solid foods the nutritive ratio +is that existing between the percentage of proteids and that of +carbohydrates, increased by multiplying the fat by two and a half and +adding the product. In a cereal containing twelve per cent of protein, +seventy-two of carbohydrates, exclusive of fiber, and three of fat, the +ratio is 12: 72 + 3 × 2.5 = 6.5. Instead of calculating the nutritive +ratio directly from the data obtained by analysis, it may be reckoned +from the per cents of the three substances in the sample multiplied by +their digestive coefficient. Since the relative amounts of proteids, +fats and carbohydrates digested do not greatly differ, the numerical +expression of the nutritive ratio is nearly the same when obtained by +each of these methods of calculation.</p> + +<p>Where the proportion of protein is relatively large the ratio is called +narrow, 1: 4 ... 6. When the proportion of protein is relatively small +the ratio is called broad 1: 8 ... 12. In feeding, the nutritive ratio +is varied in harmony with the purpose in view, a narrow ratio favoring +the development of muscular energy, and a wide one promoting the +deposition of fat and the development of heat. These principles guide +the scientific farmer in mixing rations for his stock, the work horses +receiving a comparatively narrow and the beeves a relatively wide ratio +in their food.</p> + +<p><b>561. Calorimetric Analyses of Foods.</b>—The general principles of +calorimetry have been already noticed. The theoretical and chemical +relations of calorimetry have been fully discussed by Berthelot, +Thomsen, Ostwald and Muir.<a id="FNanchor_576" href="#Footnote_576" class="fnanchor">[576]</a> +In the analyses of foods the values as determined by calculation or +combustion are of importance in determining the nutritive relations.</p> + +<p>Atwater has presented a résumé of the history and importance of +the calorimetric investigations of foods to which the analyst is +referred.<a id="FNanchor_577" href="#Footnote_577" class="fnanchor">[577]</a></p> + +<p>In the computation of food values the percentages of proteids, +carbohydrates and fats are determined and the required data obtained by +<span class="pagenum"><a id="Page_569"></a>[Pg 569]</span> +applying the factors 4100, 5500 and 9300 calories for one gram of +carbohydrates, proteids and fats respectively.</p> + +<p>For most purposes the computed values are sufficient, but it is well to +check them from time to time by actual combustions in a calorimeter.</p> + +<p><b>562. Combustion in Oxygen.</b>—The author made a series of +combustions of carbonaceous materials in oxygen at the laboratory of +Purdue University in 1877, the ignition being secured by a platinum +wire rendered incandescent by the electric current. The data obtained +were unsatisfactory on account of the crudeness of the apparatus. The +discovery of the process of burning the samples in oxygen at a high +pressure has made it possible to get expressions of thermal data which +while not yet perfect, possess a working degree of accuracy. The best +form of bomb calorimeter heretofore employed is that of Hempel, as +modified by Atwater and Woods.<a id="FNanchor_578" href="#Footnote_578" class="fnanchor">[578]</a></p> + +<p>A section of this calorimeter, with all the parts in place, is shown in +<a href="#FIG_120">Fig. 120</a>.</p> + +<p>In the figure the steel cylinder <i>A</i>, about 12.5 centimeters deep +and 6.2 in diameter, represents the chamber in which the combustion +takes place. Its walls are about half a centimeter thick and it weighs +about three kilograms. It is closed, when all the parts are ready and +the sample in place, by the collar <i>C</i>, which is secured gas tight +by means of a powerful spanner. The cover is provided with a neck +<i>D</i> carrying a screw <i>E</i> and a valve screw <i>F</i>. In the +neck <i>D</i>, where the bottom of the cylinder screw <i>E</i> rests, +is a shoulder fitted with a lead washer. Through <i>G</i> the oxygen +used for combustion is introduced. The upper edge of the cylinder +<i>A</i> is beveled and fits into a groove in the cover <i>B</i>, +carrying a soft metal washer. To facilitate the screwing on of the +cover, ball bearings <i>KK</i>, made of hard steel, are introduced +between the collar and the cover. The platinum wires <i>H</i> and +<i>I</i> support the platinum crucible holding the combustible bodies +which are ignited by raising the spiral iron wire connecting them +to the temperature of fusion by an electric current. The combustion +apparatus when charged is immersed in a metal cylinder <i>M</i>, +containing water and resting on small cylinders of cork. The water is +<span class="pagenum"><a id="Page_570"></a>[Pg 570]</span> +stirred by the apparatus <i>LL</i>. The cylinder <i>M</i> is contained +in two large concentric cylinders, <i>N</i>, <i>O</i>, made of +non-conducting materials and covered with disks of hard rubber. The +space between <i>O</i> and <i>N</i> may be filled with water. The +temperature is measured by the thermometer <i>P</i>, graduated to +hundredths of a degree and the reading is best accomplished by means of +a cathetometer.</p> + +<div class="figcenter smcap"> + <img id="FIG_120" src="images/fig120.jpg" alt="" width="400" height="651" > + <p class="center spb1">Fig. 120. Hempel and Atwater’s<br> Calorimeter.</p> +</div> + +<p><b>563. The Williams Calorimeter.</b>—The calorimeter bomb has been +improved by Williams by making it of aluminum bronze of a spheroidal +shape. The interior of the bomb is plated with gold. By an ingenious +arrangement of contacts the firing is secured by means of a permanently +insulated electrode fixed in the side of the bomb. The calorimetric +water, as well as that in the insulating vessel, is stirred by means of +an electrical screw so regulated as to produce no appreciable degree of +heat mechanically. The combustion is started by fusing a fine platinum +wire of definite length and thickness by means of an electric current. +The heat value of this fusion is determined and the calories produced +deducted from the total calories of the combustion. The valve admitting +<span class="pagenum"><a id="Page_571"></a>[Pg 571]</span> +the oxygen is sealed automatically on breaking connection with the +oxygen cylinder. The effluent gases, at the end of the combustion, may +be withdrawn through an alkaline solution and any nitric acid therein +thus be fixed and determined.<a id="FNanchor_579" href="#Footnote_579" class="fnanchor">[579]</a></p> + +<p><b>564. Manipulation and Calculation.</b>—The material to be burned +is conveniently prepared by pressing it into tablets. The oxygen is +supplied from cylinders, of which two should be used, one at a pressure +of more than twenty atmospheres. By this arrangement a pump is not +required.</p> + +<p>In practical use, a known weight of the substance to be burned is +placed in the platinum capsule, the cover of the bomb screwed on, +after all adjustments have been made, and the apparatus immersed in +the water contained in <i>M</i>, which should be about 2° below room +temperature. All the covers are placed in position and the temperature, +of the water in <i>M</i> begins to rise. Readings of the thermometer +are taken at intervals of about one minute for six minutes, at which +time the temperature of the bomb and calorimetric water may be regarded +as sensibly the same. The electric current is turned on, the iron wire +at once melts, ignites the substance and the combustion rapidly takes +place. In the case of bodies which do not burn readily Atwater adds +to them some naphthalene, the thermal value of which is previously +determined. The calories due to the combustion of the added naphthalene +are deducted from the total calories obtained.</p> + +<p>The temperature of the water in <i>M</i> rises rapidly at first, and +readings are made at intervals of one minute for five minutes, and then +again after ten minutes. The first of the initial readings, the one at +the moment of turning on the current, and the last one mentioned above +are the data from which the correction, made necessary by the influence +of the temperature of the room, is calculated by the following +formulas.<a id="FNanchor_580" href="#Footnote_580" class="fnanchor">[580]</a></p> + +<p>The preliminary readings of the thermometer at one minute intervals are +represented by <i>t</i>₁, <i>t</i>₂, <i>t</i>₃ ... <i>t</i>ₙ₁. The last +observation tₙ₁ is taken as the beginning temperature of the combustion +and is represented in the formulas for calculations by Θ₁. The readings +after combustion are also made at intervals of one minute, and are +designated by Θ₂, Θ₃ ... Θₙ. The readings are continued until there is +no observed change between the last two. Generally this is secured by +five or six readings. +<span class="pagenum"><a id="Page_572"></a>[Pg 572]</span></p> + +<p>The third period of observations begins with the last reading Θₙ, +which in the next series is represented by <i>tʹ</i>₁, <i>tʹ</i>₂ ... +<i>tʹ</i>ₙ₂.</p> + +<p>In order to make the formulas less cumbersome let</p> + +<table class="spb1 fs_110"> + <tbody><tr> + <td class="tdc bb"><i>t</i>ₙ₁ - <i>t</i>₁</td> + <td class="tdl" rowspan="2"> = <i>v</i>,</td> + </tr><tr> + <td class="tdc"><i>n</i>₁ - 1</td> + </tr> + </tbody> +</table> + +<table class="spb1 fs_110"> + <tbody><tr> + <td class="tdc bb"><i>tʹ</i>ₙ₁ - <i>tʹ</i>₁</td> + <td class="tdl" rowspan="2"> = <i>vʹ</i>,</td> + </tr><tr> + <td class="tdc"><i>n</i>₂ - 1</td> + </tr> + </tbody> +</table> + +<table class="spb1 fs_110"> + <tbody><tr> + <td class="tdc bb"><i>t</i>₁ + <i>t</i>₂ + <i>t</i>₃ ... <i>t</i>ₙ₁</td> + <td class="tdl" rowspan="2"> = <i>t</i>,</td> + </tr><tr> + <td class="tdc"><i>n</i>₁</td> + </tr> + </tbody> +</table> + +<table class="spb1 fs_110"> + <tbody><tr> + <td class="tdl" rowspan="2">and  </td> + <td class="tdc bb"><i>tʹ</i>₁ + <i>tʹ</i>₂ + <i>tʹ</i>₃ ... <i>tʹ</i>ₙ₂</td> + <td class="tdl" rowspan="2"> = <i>tʹ</i>.</td> + </tr><tr> + <td class="tdc"><i>n</i>₂</td> + </tr> + </tbody> +</table> + +<p>The correction to be made to the difference between Θₙ - Θ₁ for the +influence of the outside temperature is determined by the formula of +Regnault-Pfaundler, which is as follows:</p> + +<table class="spb1 fs_120"> + <tbody><tr> + <td class="tdl" rowspan="2">∑ Δ<i>t</i> = </td> + <td class="tdc bb"><i>v</i> - <i>vʹ</i></td> + <td class="tdc" rowspan="2"><span class="fs_200"> (</span> </td> + <td class="tdr"><sup>ⁿ⁻¹</sup></td> + <td class="tdl fs_150" rowspan="2">∑</td> + <td class="tdl" rowspan="2"> Θ<i>r</i> + </td> + <td class="tdr bb">Θₙ + Θ₁</td> + <td class="tdl" rowspan="2"> - <i>nt</i> <span class="fs_200">)</span> - (<i>n</i> - 1)<i>v</i>,</td> + </tr><tr> + <td class="tdc"><i>tʹ</i> - <i>t</i></td> + <td class="tdr"> <sup>₁</sup> </td> + <td class="tdc">2</td> + + </tr> + </tbody> +</table> + +<table class="spb1 fs_105"> + <tbody><tr> + <td class="tdr"><sub>n-1</sub></td> + <td class="tdc"> </td> + </tr><tr> + <td class="tdl">in which <span class="fs_120">∑</span></td> + <td class="tdl"> Θ<i>r</i></td> + </tr><tr> + <td class="tdr"><sup>1</sup> </td> + <td class="tdc"> </td> + </tr> + </tbody> +</table> + +<p class="no-indent">is calculated from the observation of the +thermometer Θ₁, Θ₂ etc., made immediately after the combustion. It is +equal to the sum of observations Θ₁, Θ₂ etc., increased by an arbitrary +factor equivalent to (Θ₂ - Θ₁)/9, which is made necessary by reason +of the irregularity of the temperature increase during the first +minute after combustion, the mean temperature during that minute being +somewhat higher than the mean of the temperatures at the commencement +and end of that time.</p> + +<p>The quantity of heat formed by the combustion of the iron wire used for +igniting the sample is to be deducted from the total heat produced. +This correction may be determined once for all, the weight of the +iron wire used being noted and that of any unburned portion being +ascertained after the combustion.</p> + +<p>Ten milligrams of iron, on complete combustion, will give sixteen calories.</p> + +<p>In the combustion of substances containing nitrogen, or in case the +free nitrogen of the air be not wholly expelled from the apparatus +before the burning, nitric acid is formed which is dissolved by the +water produced. +<span class="pagenum"><a id="Page_573"></a>[Pg 573]</span></p> + +<p>The heat produced by the solution of nitric acid in water is 14.3 +calories per gram molecule. The quantity of nitric acid formed is +determined by titration and a corresponding reduction made in the total +calculated calories.</p> + +<p>In the titration of nitric acid it is advisable to make use of an +alkaline solution, of which one liter is equivalent to 4.406 grams of +nitric acid. One cubic centimeter of the reagent is equivalent to a +quantity of nitric acid represented by one calorie.</p> + +<p>Since the materials of which the bomb is composed have a specific heat +different from that of water, it is necessary to compute the water +thermal value of each apparatus.</p> + +<p>The hydrothermal equivalent of the whole apparatus is most simply +determined by immersing it at a given temperature in water of a +different temperature.<a id="FNanchor_581" href="#Footnote_581" class="fnanchor">[581]</a> +With small apparatus this method is quite sufficient, but there are +many difficulties attending its application to large systems weighing +several kilograms. In these cases the hydrothermal equivalent may be +calculated from the specific heats of the various components of the apparatus.</p> + +<p>In calculating these values the specific heats of the various +components of the apparatus are as follows:</p> + +<table class="spb1"> + <tbody><tr> + <td class="tdl">Brass</td> + <td class="tdl_ws1">0.093</td> + </tr><tr> + <td class="tdl">Steel</td> + <td class="tdl_ws1">0.1097</td> + </tr><tr> + <td class="tdl">Platinum</td> + <td class="tdl_ws1">0.0324</td> + </tr><tr> + <td class="tdl">Copper</td> + <td class="tdl_ws1">0.09245</td> + </tr><tr> + <td class="tdl">Lead</td> + <td class="tdl_ws1">0.0315</td> + </tr><tr> + <td class="tdl">Oxygen</td> + <td class="tdl_ws1">0.2389</td> + </tr><tr> + <td class="tdl">Glass</td> + <td class="tdl_ws1">0.190</td> + </tr><tr> + <td class="tdl">Mercury</td> + <td class="tdl_ws1">0.0332</td> + </tr><tr> + <td class="tdl">Hard rubber<span class="ws2"> </span></td> + <td class="tdl_ws1">0.33125</td> + </tr> + </tbody> +</table> + +<p><i>Example.</i>—It is required to calculate the hydrothermal value of +a calorimeter composed of the following substances:</p> + +<table class="spb1"> + <tbody><tr> + <td class="tdl"> </td> + <td class="tdc bb" colspan="2"><b>Hydrothermal<br>value.</b></td> + </tr><tr> + <td class="tdl">Steel bomb and cover, 2850 grams × 0.1097</td> + <td class="tdr">312.65</td> + <td class="tdl_wsp">grams.</td> + </tr><tr> + <td class="tdl">Platinum lining, capsule and wires, 120 grams × 0.0324</td> + <td class="tdr">3.89</td> + <td class="tdc">”</td> + </tr><tr> + <td class="tdl">Lead washer, 100 grams × 0.0315</td> + <td class="tdr">3.15</td> + <td class="tdc">”</td> + </tr><tr> + <td class="tdl">Brass outer cylinder, 500 grams × 0.093</td> + <td class="tdr">46.50</td> + <td class="tdc">”</td> + </tr><tr> + <td class="tdl">Mercury in thermometer, 10 grams × 0.0332</td> + <td class="tdr">0.33</td> + <td class="tdc">”</td> + </tr><tr> + <td class="tdl">Glass (part of thermometer in water), 10 grams × 0.19</td> + <td class="tdr">1.90</td> + <td class="tdc">”</td> + </tr><tr> + <td class="tdl">Brass stirring apparatus (part in water), 100 grams × 0.093</td> + <td class="tdr bb">9.30</td> + <td class="tdc">”</td> + </tr><tr> + <td class="tdl_ws2">Total water value of system</td> + <td class="tdr"> 377.72</td> + <td class="tdc">”</td> + </tr> + </tbody> +</table> + +<p><span class="pagenum"><a id="Page_574"></a>[Pg 574]</span> +When a bomb of 300 cubic centimeters capacity is filled with oxygen at +a pressure of twenty-four atmospheres it will hold about ten grams of +the gas, equivalent to a water value of 2.40 grams. Hence the water +value of the above system when charged, assuming the bomb to be of the +capacity mentioned, is 380.12 grams.</p> + +<p>If the cylinder holding the water be made of fiber or other +non-conducting substance, its specific heat is best determined by +filling it in a known temperature with water at a definite different +temperature.</p> + +<p>It is advisable to have the water cylinder of such a size as to permit +the use of a quantity of water for the total immersion of the bomb +which will weigh, with the water value of the apparatus, an even number +of grams. In the case above, 2622.28 grams of water placed in the +cylinder will make a water value of 3,000 grams, which is one quite +convenient for calculation.</p> + +<p><b>565. Computing the Calories of Combustion.</b>—In the preceding +paragraph has been given a brief account of the construction of the +calorimeter and of the methods of standardizing it and securing the +necessary corrections in the data directly obtained in its use. An +illustration of the details of computing the calories of combustion +taken from the paper of Stohmann, Kleber and Langbein, will be a +sufficient guide for the analyst in conducting the combustion and in +the use of the data obtained.<a id="FNanchor_582" href="#Footnote_582" class="fnanchor">[582]</a></p> + +<div class="blockquot"> +<p>Weight of substance burned, 1.07 grams.</p> + +<p>Water value of system (water + apparatus), 2,500 grams.</p> + +<p>Preliminary thermometric readings, <i>t</i>₁ = 26.8; <i>t</i>₂ = 27.2; +<i>t</i>₃ = 27.7; <i>t</i>₄ = 28.1; <i>t</i>₅ = 28.5; <i>t</i>ₙ₁ = 28.9.</p> + +<p>Thermometric reading after combustion, Θ₁ = 28.9; Θ₂ = 202; Θ₃ = 213; +Θ₄ = 214.2; Θₙ = 214.0.</p> + +<p>Final thermometric readings, <i>tʹ</i>₁ = 214.0; <i>tʹ</i>₂ = 213.8; +<i>tʹ</i>₃ = 213.6; <i>tʹ</i>₄ = 213.5; <i>tʹ</i>₅ = 213.3; <i>tʹ</i>₆ += 213.1; <i>tʹ</i>₇ = 212.9; <i>tʹ</i>₈ = 212.7; <i>tʹ</i>₉ = 212.6; +<i>tʹ</i>₁₀ = 212.4; <i>tʹ</i>ₙ₂ = 212.2.</p> + +<p>From the formulas given above the following numerical values are +computed:</p> + +<p><span class="pagenum"><a id="Page_575"></a>[Pg 575]</span></p> + +<ul class="index"> +<li class="isub3"><i>v</i> = 0.42.</li> +<li class="isub3"><i>vʹ</i> = -0.18.</li> +<li class="isub3"><i>t</i> = 27.9.</li> +<li class="isub3"><i>tʹ</i> = 213.1.</li> +<li class="isub3"><i>n</i> = 5.</li> +</ul> + +<table class="spb1 fs_105"> + <tbody><tr> + <td class="tdr"><sub>n-1</sub></td> + <td class="tdc" colspan="3"> </td> + </tr><tr> + <td class="tdl"><span class="fs_150">∑</span></td> + <td class="tdl"> Θ<i>r</i> = Θ₁ + Θ₂ + Θ₃ + Θ₄ + </td> + <td class="tdc bb">Θ₂ - Θ₁</td> + <td class="tdl"> = 667.</td> + </tr><tr> + <td class="tdr"><sup>1</sup> </td> + <td class="tdc"> </td> + <td class="tdc">9</td> + <td class="tdc"> </td> + </tr> + </tbody> +</table> + +<p>Substituting these values in the formula of Regnault-Pfaundler, the +value of the correction for the influence of the external air is</p> + +<table class="spb1"> + <tbody><tr> + <td class="tdl fs_120" rowspan="2">∑ Δ<i>t</i> = </td> + <td class="tdc fs_300" rowspan="2">[ </td> + <td class="tdc bb">0.42 - (-0.18)</td> + <td class="tdl fs_200" rowspan="2"> (</td> + <td class="tdl" rowspan="2"> 677 + </td> + <td class="tdr bb">214 + 29</td> + <td class="tdl" rowspan="2"> - (5 × 27.9)</td> + <td class="tdl fs_200" rowspan="2">)</td> + <td class="tdl" rowspan="2"> - (4 × 0.42)</td> + <td class="tdc fs_300" rowspan="2">]</td> + <td class="tdl" rowspan="2"> = 0.45,</td> + </tr><tr> + <td class="tdc">213.1 - 27.9</td> + <td class="tdc">2</td> + </tr> + </tbody> +</table> + +<p class="no-indent">which is to be added to the end temperature (Θₙ = 214.0).</p> + +<p>The computation is then made from the following data:</p> + +<table class="spb1"> + <tbody><tr> + <td class="tdl">Corrected end temperature (Θₙ + 0.45)</td> + <td class="tdr">  214.45</td> + <td class="tdc"> = </td> + <td class="tdr">15°.3699</td> + </tr><tr> + <td class="tdl">Beginning temperature (Θ₁)</td> + <td class="tdr">28.90</td> + <td class="tdc">=</td> + <td class="tdr">12°.8406</td> + </tr><tr> + <td class="tdl">Increase in temperature</td> + <td class="tdr">185.55</td> + <td class="tdc">=</td> + <td class="tdr">2°.5293</td> + </tr><tr> + <td class="tdl">Total calories 2.5293 × 25000</td> + <td class="tdr"> </td> + <td class="tdc">=</td> + <td class="tdr">6323.3</td> + </tr><tr> + <td class="tdl" colspan="3">Of which there were due to iron burned</td> + <td class="tdr">9.1</td> + </tr><tr> + <td class="tdl" colspan="3"> ”  ”   ”  ” nitric acid dissolved</td> + <td class="tdr">8.2</td> + </tr><tr> + <td class="tdl" colspan="3">Total calories due to one gram of substance</td> + <td class="tdr">5893.5</td> + </tr> + </tbody> +</table> +</div> + +<p>The thermometric readings are given in the divisions of the thermometer +which in this case are so adjusted as to have the number 28.90 +correspond to 12°.8406, and each division is nearly equivalent to +0°.014 thermometric degree.</p> + +<p>The number of calories above given is the proper one when the +computation is made to refer to constant volume. By reason of the +consumption of oxygen and the change of temperature, although mutually +compensatory, the pressure may be changed at the end of the operation. +The conversion of the data obtained at constant volume referred to +constant pressure may be made by the following formula, in which +[<i>Q</i>] represents the calories from constant volume and <i>Q</i> +the desired data for constant pressure, <i>O</i> the number of oxygen +atoms, <i>H</i> the number of hydrogen atoms in a molecule of the +substance, and 0.291 a constant for a temperature of about 18°, at +which the observations should be made. +<span class="pagenum"><a id="Page_576"></a>[Pg 576]</span></p> + +<table class="spb1 fs_105"> + <tbody><tr> + <td class="tdl" rowspan="2"><i>Q</i> = [<i>Q</i>] +</td> + <td class="tdc fs_200" rowspan="2"> ( </td> + <td class="tdc bb"><i>H</i></td> + <td class="tdc" rowspan="2"> - <i>O</i></td> + <td class="tdc fs_200" rowspan="2">)</td> + <td class="tdc" rowspan="2"> 0.291.</td> + </tr><tr> + <td class="tdc">2</td> + </tr> + </tbody> +</table> + +<p id="P_566"><b>566. Calorimetric Equivalents.</b>—By the term calorie is +understood the quantity of heat required to raise one gram of water, +at an initial temperature of about 18°, one degree. The term ‘Calorie’ +denotes the quantity of heat, in like conditions, required to raise one +kilogram of water one degree.</p> + +<p>For purposes of comparison and for assisting the analyst in adjusting +his apparatus so as to give reliable results, the following data, +giving the calories of some common food materials, are given:</p> + +<table class="spb1"> + <thead><tr> + <th class="tdc bl bb bt" rowspan="2">Substance.<br>Proteids.</th> + <th class="tdc bl bb bt" rowspan="2"> Calories. </th> + <th class="tdc bl br bb bt fs_110" colspan="5">Chemical composition.</th> + </tr><tr class="fs_110"> + <th class="tdc bl bb">C.</th> + <th class="tdc bb">H.</th> + <th class="tdc bb">N.</th> + <th class="tdc bb">S.</th> + <th class="tdc bb br">O.</th> + </tr></thead> + <tbody><tr> + <td class="tdl"> </td> + <td class="tdc"> </td> + <td class="tdc"> Per cent. </td> + <td class="tdc"> Per cent. </td> + <td class="tdc"> Per cent. </td> + <td class="tdc"> Per cent. </td> + <td class="tdc"> Per cent. </td> + </tr><tr> + <td class="tdl">Serum albumin</td> + <td class="tdc">5917.8</td> + <td class="tdc">53.93</td> + <td class="tdc">7.65</td> + <td class="tdc">15.15</td> + <td class="tdc">1.18</td> + <td class="tdc">22.09</td> + </tr><tr> + <td class="tdl">Casein</td> + <td class="tdc">5867.0</td> + <td class="tdc">54.02</td> + <td class="tdc">7.33</td> + <td class="tdc">15.52</td> + <td class="tdc">0.75</td> + <td class="tdc">22.38</td> + </tr><tr> + <td class="tdl bb">Egg albumin</td> + <td class="tdc bb">5735.0</td> + <td class="tdc bb">52.95</td> + <td class="tdc bb">7.50</td> + <td class="tdc bb">15.19</td> + <td class="tdc bb">1.51</td> + <td class="tdc bb">22.85</td> + </tr><tr> + <td class="tdl">Meat free of fat and</td> + <td class="tdc bb" rowspan="2">5720.0</td> + <td class="tdc bb" rowspan="2">52.11</td> + <td class="tdc bb" rowspan="2">6.76</td> + <td class="tdc bb" rowspan="2">18.14</td> + <td class="tdc bb" rowspan="2">0.96</td> + <td class="tdc bb" rowspan="2">22.66</td> + </tr><tr> + <td class="tdl_wsp bb">extracted with water</td> + </tr><tr> + <td class="tdl">Peptone</td> + <td class="tdc">5298.8</td> + <td class="tdc">50.10</td> + <td class="tdc">6.45</td> + <td class="tdc">16.42</td> + <td class="tdc">1.24</td> + <td class="tdc">25.79</td> + </tr><tr> + <td class="tdl">Proteids (mean) Glycerids.</td> + <td class="tdc">5730.8</td> + <td class="tdc">52.71</td> + <td class="tdc">7.09</td> + <td class="tdc">16.02</td> + <td class="tdc">1.03</td> + <td class="tdc">23.15</td> + </tr><tr> + <td class="tdl">Butterfat</td> + <td class="tdc">9231.3</td> + <td class="tdc" colspan="5"> </td> + </tr><tr> + <td class="tdl">Linseed oil</td> + <td class="tdc">9488.0</td> + <td class="tdc" colspan="5"> </td> + </tr><tr> + <td class="tdl">Olive oil</td> + <td class="tdc">9467.0</td> + <td class="tdc" colspan="5"> </td> + </tr><tr> + <td class="tdl" colspan="7"> </td> + </tr><tr> + <td class="tdl" colspan="2">Carbohydrates.</td> + <td class="tdc" colspan="2"> </td> + <td class="tdl_ws1" colspan="3"><b>Formula.</b></td> + </tr><tr> + <td class="tdl_ws1">Arabinose</td> + <td class="tdc">3722.0</td> + <td class="tdc" colspan="2"> </td> + <td class="tdl" colspan="3">C₅H₁₀O₅</td> + </tr><tr> + <td class="tdl_ws1">Xylose</td> + <td class="tdc">3746.0</td> + <td class="tdc" colspan="2"> </td> + <td class="tdl" colspan="3">C₅H₁₀O₅</td> + </tr><tr> + <td class="tdl_ws1">Dextrose</td> + <td class="tdc">3742.6</td> + <td class="tdc" colspan="2"> </td> + <td class="tdl" colspan="3">C₆H₁₂O₆</td> + </tr><tr> + <td class="tdl_ws1">Levulose</td> + <td class="tdc">3755.0</td> + <td class="tdc" colspan="2"> </td> + <td class="tdl" colspan="3">C₆H₁₂O₆</td> + </tr><tr> + <td class="tdl_ws1">Sucrose</td> + <td class="tdc">3955.2</td> + <td class="tdc" colspan="2"> </td> + <td class="tdl" colspan="3">C₁₂H₂₂O₁₁</td> + </tr><tr> + <td class="tdl_ws1">Lactose</td> + <td class="tdc">3736.8</td> + <td class="tdc" colspan="2"> </td> + <td class="tdl" colspan="3">C₁₂H₂₂O₁₁ + H₂O</td> + </tr><tr> + <td class="tdl_ws1">Maltose</td> + <td class="tdc">3949.3</td> + <td class="tdc" colspan="2"> </td> + <td class="tdl" colspan="3">C₁₂H₂₂O₁₁</td> + </tr> + </tbody> +</table> + +<p><b>567. Distinction between Butter and Oleomargarin.</b>—Theoretically +the heats of combustion of butter fat and oleomargarin are different +and de Schweinitz and Emery propose to utilize this difference for +analytical purposes.<a id="FNanchor_583" href="#Footnote_583" class="fnanchor">[583]</a> +The samples of pure butter fat examined by them afforded 9320, 9327 and +9362 calories, respectively. The calories obtained for various samples +<span class="pagenum"><a id="Page_577"></a>[Pg 577]</span> +of oleomargarin varied from 9574 to 9795. On mixing butter fat and +oleomargarin, a progressive increase in calorimetric power is found, +corresponding to the percentage of the latter constituent. Lards +examined at the same time gave from 9503 to 9654 calories.</p> + +<h3>FRUITS, MELONS AND VEGETABLES.</h3> + +<p><b>568. Preparation of Sample.</b>—Fresh fruits and vegetables are +most easily prepared for analysis by passing them through the pulping +machine described on <a href="#Page_9">page 9</a>. Preliminary to the pulping +they should be separated into skins, cores, seeds and edible portions, and the +respective weights of these bodies noted. Each part is separately +reduced to a pulp and, at once, a small quantity of the well mixed +substance placed in a flat bottom dish and dried, first at a low +temperature, and finally at 100°, or somewhat higher, and the +percentage of water contained in the sample determined. The bulk of +the sample, three or four kilograms, is dried on a tray of tinned or +aluminum wire, first at a low and then at a high temperature, until +all or nearly all the moisture is driven off. The dried pulp is then +ground to as fine a powder as possible and subjected to the ordinary +processes of analysis; <i>viz.</i>, the determination of the moisture, +ash, nitrogen, fiber, fat and carbohydrates.</p> + +<p>In this method of analysis it is customary to determine the +carbohydrates, exclusive of fiber, by subtracting the sum of the per +cents of the other constituents and the nitrogen multiplied by 6.25 +from 100.</p> + +<p><b>569. Separation of the Carbohydrates.</b>—It is often desirable to +determine the relative proportions of the more important carbohydrates +which are found in fruits and vegetables. The pentoses and pentosans +are estimated by the method described in paragraph <b><a href="#P_150">150</a></b>. +The cane sugar, dextrose and levulose are determined by extracting a portion of +the substance with eighty per cent alcohol and estimating the reducing +sugars in the extract before and after inversion by the processes +described in paragraphs <b><a href="#P_238">238-251</a></b>. The percentages of +sugars deducted from the percentage of carbohydrates, exclusive of fiber, give +the quantity of gums, pentosans, cellulose and pectose bodies present.</p> + +<p>Pectose exists chiefly in unripe fruits. By the action of the fruit +<span class="pagenum"><a id="Page_578"></a>[Pg 578]</span> +acids and of a ferment, pectose, in the process of ripening, is +changed into pectin and similar hydrolyzed bodies soluble in water. +The gelatinous properties of boiled fruits and fruit juices are due to +these bodies, boiling accelerating their formation. In very ripe fruits +the pectin is completely transformed into pectic acids. The galactan is +estimated as described in <b><a href="#P_585">585</a></b>.</p> + +<p><b>570. Examination of the Fresh Matter.</b>—To avoid the changes +which take place in drying fruits and vegetables, it is necessary to +examine them in the fresh state. The samples may be first separated +into meat and waste, as suggested above, or shredded as a whole. +The moisture in the pulp is determined as indicated above, and in +a separate portion the soluble matters are extracted by repeated +treatment with cold water. The seeds, skins, cellulose, pectose and +other insoluble bodies are thus separated from the sugars, pectins, +pectic and other acids, and other soluble matters. The insoluble +residue is rapidly dried and the relative proportions of soluble +and insoluble matters determined. The estimation of these bodies is +accomplished in the usual way.</p> + +<p><b>571. Examination of Fruit and Vegetable Juices.</b>—The fruits and +vegetables are pulped, placed in a press and the juices extracted. +The pressure should be as strong as possible and the press described +in paragraph <b><a href="#P_280">280</a></b> is well suited to this purpose. +The specific gravity of the expressed juice is obtained and the sucrose therein +determined by polarization before and after inversion. The reducing +sugars and the relative proportions of dextrose and levulose are +determined in the usual manner. In grape juice dextrose is the +predominant sugar while in many other fruits left hand or optically +inactive sugars predominate. Soluble gums, dextrin, pectin etc., may be +separated from the sugars by careful precipitation with alcohol, or the +total solids, ash, nitrogen, ether extract and acids be determined and +the carbohydrates estimated by difference. From the carbohydrates the +total percentage of sugars is deducted and the remainder represents the +quantity of pectin, gum and other carbohydrates present.</p> + +<p><b>572. Separation of Pectin.</b>—Pectin exists in considerable +<span class="pagenum"><a id="Page_579"></a>[Pg 579]</span> +quantities in the juice of ripe fruits (pears) and may be obtained in +an approximately pure state from the juices by first removing proteids +by the careful addition of tannin, throwing out the soluble lime +salts with oxalic acid and precipitating the pectin with alcohol. On +boiling with water, pectin is converted into parapectin, which gives +a precipitate with lead acetate. Boiling with dilute acids converts +pectin into metapectin, which is precipitated by a barium salt.</p> + +<p>Pectic acid may be obtained by boiling an aqueous extract (carrots) +with sodium carbonate and precipitating the pectic with hydrochloric +acid. It is a jelly-like body and dries to a horny mass.</p> + +<p><b>573. Determination of Free Acid.</b>—The free acid, or rather total +acidity of fruits, is determined by the titration of their aqueous +extracts or expressed juices with a set alkali. In common fruits and +vegetables the acidity is calculated to malic <b>C₄H₆O₅</b>, in grapes to +tartaric <b>C₄H₆O₆</b>, and in citrous fruits to citric acid <b>C₆H₈O₇</b>. Many +other acids are found in fruits and vegetables, but those mentioned are +predominant in the classes given.</p> + +<p><b>574. Composition of Common Fruits.</b>—The composition of common +fruits in this country has been extensively investigated at the +California Station and the following data are derived chiefly from its +bulletins.<a id="FNanchor_584" href="#Footnote_584" class="fnanchor">[584]</a></p> + +<ul class="index"> +<li class="isub3"><b>(A)</b> = Total sugars in juice.</li> +<li class="isub3"><b>(B)</b> = Sucrose in juice.</li> +<li class="isub3"><b>(C)</b> = Dry organic matter.</li> +</ul> + +<table class="spb1"> + <thead><tr> + <th class="tdc_bott">Name.</th> + <th class="tdc">Total<br>weight.</th> + <th class="tdc">Rind<br>skin.</th> + <th class="tdc_bott">Seed.</th> + <th class="tdc_bott">Pulp.</th> + <th class="tdc_bott">Juice.</th> + <th class="tdc_bott fs_110">(A)</th> + <th class="tdc_bott fs_110">(B)</th> + </tr></thead> + <tbody><tr> + <td class="tdl"> </td> + <td class="tdc">grams.</td> + <td class="tdc"> per cent. </td> + <td class="tdc"> per cent. </td> + <td class="tdc"> per cent. </td> + <td class="tdc">cubic<br>centimeters.</td> + <td class="tdc"> Per cent. </td> + <td class="tdc"> Per cent. </td> + </tr><tr> + <td class="tdl">Naval orange</td> + <td class="tdc">300</td> + <td class="tdc">28.4</td> + <td class="tdc"> </td> + <td class="tdc">27.7</td> + <td class="tdc">107</td> + <td class="tdc">9.92</td> + <td class="tdc">4.80</td> + </tr><tr> + <td class="tdl">Mediterranean sweet orange</td> + <td class="tdc">202</td> + <td class="tdc">27.0</td> + <td class="tdc">0.8 </td> + <td class="tdc">24.0</td> + <td class="tdc"> 86</td> + <td class="tdc">9.70</td> + <td class="tdc">4.35</td> + </tr><tr> + <td class="tdl">St. Michael’s orange</td> + <td class="tdc">138</td> + <td class="tdc">19.2</td> + <td class="tdc">1.6 </td> + <td class="tdc">25.9</td> + <td class="tdc">65.4</td> + <td class="tdc">8.71</td> + <td class="tdc">3.48</td> + </tr><tr> + <td class="tdl">Malta Blood orange</td> + <td class="tdc">177</td> + <td class="tdc">31.0</td> + <td class="tdc"> </td> + <td class="tdc">24.0</td> + <td class="tdc">71.0</td> + <td class="tdc">10.30 </td> + <td class="tdc">5.85</td> + </tr><tr> + <td class="tdl">Eureka lemon</td> + <td class="tdc">104</td> + <td class="tdc">32  </td> + <td class="tdc">0.12</td> + <td class="tdc">24.5</td> + <td class="tdc"> 38</td> + <td class="tdc">2.08</td> + <td class="tdc">0.57</td> + </tr><tr> + <td class="tdl"> </td> + <td class="tdc"> </td> + <td class="tdc"><b>Flesh</b></td> + <td class="tdc"> </td> + <td class="tdc"> </td> + <td class="tdc"><b>Per cent</b></td> + <td class="tdc"> </td> + <td class="tdc"> </td> + </tr><tr> + <td class="tdl">Apricot</td> + <td class="tdc">62.4</td> + <td class="tdc">93.85</td> + <td class="tdc">6.15</td> + <td class="tdc">10.0</td> + <td class="tdc">90.0</td> + <td class="tdc">13.31</td> + <td class="tdc"> </td> + </tr><tr> + <td class="tdl">Prune</td> + <td class="tdc">25.6</td> + <td class="tdc">94.2 </td> + <td class="tdc">5.8 </td> + <td class="tdc">21.2</td> + <td class="tdc">78.8</td> + <td class="tdc">20.0 </td> + <td class="tdc"> </td> + </tr><tr> + <td class="tdl">Plum</td> + <td class="tdc">60.4</td> + <td class="tdc">95.2 </td> + <td class="tdc">4.8 </td> + <td class="tdc">24.7</td> + <td class="tdc">75.3</td> + <td class="tdc">17.97</td> + <td class="tdc"> </td> + </tr><tr> + <td class="tdl">Peach</td> + <td class="tdc">185  </td> + <td class="tdc">93.8 </td> + <td class="tdc">6.2 </td> + <td class="tdc">22.5</td> + <td class="tdc">77.5</td> + <td class="tdc">17.0 </td> + <td class="tdc"> </td> + </tr><tr> + <td class="tdl"> </td> + <td class="tdc"> </td> + <td class="tdc"><b>Skin</b></td> + <td class="tdc"><b>Cores</b></td> + <td class="tdc"> </td> + <td class="tdc"> </td> + <td class="tdc"> </td> + <td class="tdc"> </td> + </tr><tr> + <td class="tdl">Apple</td> + <td class="tdc">183</td> + <td class="tdc">17.0</td> + <td class="tdc">7.0</td> + <td class="tdc"> </td> + <td class="tdc"> </td> + <td class="tdc">10.26‡</td> + <td class="tdc">1.53‡</td> + </tr><tr> + <td class="tdr_ws1" colspan="8">‡ In whole fresh fruit.  </td> + </tr> + </tbody> +</table> + +<table class="spb1"> + <thead><tr> + <th class="tdc" rowspan="2">Name.</th> + <th class="tdc" rowspan="2">Acid</th> + <th class="tdc bb" colspan="4">In whole fruit.</th> + </tr><tr> + <th class="tdc bl">Nitrogenous<br>bodies.</th> + <th class="tdc_bott">Water.</th> + <th class="tdc_bott">(C)</th> + <th class="tdc_bott br">Ash.</th> + </tr></thead> + <tbody><tr> + <td class="tdl"> </td> + <td class="tdc"> per cent. </td> + <td class="tdc"> per cent. </td> + <td class="tdc"> per cent. </td> + <td class="tdc"> per cent. </td> + <td class="tdc"> per cent. </td> + </tr><tr> + <td class="tdl">Naval orange</td> + <td class="tdc">1.02</td> + <td class="tdc">1.31</td> + <td class="tdc">86.56</td> + <td class="tdc">13.04</td> + <td class="tdc">0.40</td> + </tr><tr> + <td class="tdl">Mediterranean sweet orange</td> + <td class="tdc">1.38</td> + <td class="tdc">0.96</td> + <td class="tdc">85.83</td> + <td class="tdc">13.06</td> + <td class="tdc">0.41</td> + </tr><tr> + <td class="tdl">St. Michael’s orange</td> + <td class="tdc">1.35</td> + <td class="tdc">1.43</td> + <td class="tdc">84.10</td> + <td class="tdc">15.42</td> + <td class="tdc">0.48</td> + </tr><tr> + <td class="tdl">Malta Blood orange</td> + <td class="tdc">1.61</td> + <td class="tdc">1.05</td> + <td class="tdc">84.50</td> + <td class="tdc">15.05</td> + <td class="tdc">0.45</td> + </tr><tr> + <td class="tdl">Eureka lemon</td> + <td class="tdc">7.66</td> + <td class="tdc">0.94</td> + <td class="tdc">85.99</td> + <td class="tdc">13.50</td> + <td class="tdc">0.51</td> + </tr><tr> + <td class="tdc" colspan="6"> </td> + </tr><tr> + <td class="tdl">Apricot</td> + <td class="tdc">0.68</td> + <td class="tdc">1.25</td> + <td class="tdc">85.16</td> + <td class="tdc">14.35</td> + <td class="tdc">0.49</td> + </tr><tr> + <td class="tdl">Prune</td> + <td class="tdc">0.40</td> + <td class="tdc">1.01</td> + <td class="tdc">77.38</td> + <td class="tdc">22.18</td> + <td class="tdc">0.44</td> + </tr><tr> + <td class="tdl">Plum</td> + <td class="tdc">0.48</td> + <td class="tdc">1.33</td> + <td class="tdc">77.43</td> + <td class="tdc">22.04</td> + <td class="tdc">0.53</td> + </tr><tr> + <td class="tdl">Peach</td> + <td class="tdc">0.25</td> + <td class="tdc"> </td> + <td class="tdc">82.50</td> + <td class="tdc">16.95</td> + <td class="tdc">0.55</td> + </tr><tr> + <td class="tdc" colspan="6"> </td> + </tr><tr> + <td class="tdl">Apple<a id="FNanchor_585" href="#Footnote_585" class="fnanchor">[585]</a></td> + <td class="tdc"> </td> + <td class="tdc">0.11</td> + <td class="tdc">86.43</td> + <td class="tdc">13.28</td> + <td class="tdc">0.29</td> + </tr> + </tbody> +</table> + +<p><span class="pagenum"><a id="Page_580"></a>[Pg 580]</span> +<b>575. Composition of Ash of Fruits.</b>—Two or three kilograms of +the dried sample are incinerated at a low temperature and burned to +a white ash in accordance with the directions given in +paragraphs <b><a href="#P_28">28-32</a></b>.</p> + +<p>The composition of the ash is determined by the methods already +described.<a id="FNanchor_586" href="#Footnote_586" class="fnanchor">[586]</a></p> + +<p>The pure ash of some common whole fruits has the following +composition:<a id="FNanchor_587" href="#Footnote_587" class="fnanchor">[587]</a></p> + +<ul class="index"> +<li class="isub3"><b>(A)</b> = Per cent pure ash in fruit.</li> +<li class="isub3"><b>(B)</b> = Per cent manganomanganic oxid.</li> +<li class="isub3"><b>(C)</b> = Per cent phosphorus pentoxid.</li> +<li class="isub3"><b>(D)</b> = Per cent sulfur trioxid.</li> +</ul> + +<table class="spb1"> + <thead><tr> + <th class="tdc_bott">Name.</th> + <th class="tdc_bott fs_110"> (A) </th> + <th class="tdc"> Per cent <br>potash.</th> + <th class="tdc"> Per cent <br>soda.</th> + <th class="tdc"> Per cent <br>lime.</th> + <th class="tdc">Per cent<br> magnesia. </th> + <th class="tdc">Per cent<br> ferric oxid. </th> + <th class="tdc_bott fs_110"> (B) </th> + </tr></thead> + <tbody><tr> + <td class="tdl">Prune</td> + <td class="tdc">0.47</td> + <td class="tdc">63.83</td> + <td class="tdc">2.65</td> + <td class="tdc">4.66</td> + <td class="tdc">5.47</td> + <td class="tdc">2.72</td> + <td class="tdc">0.39</td> + </tr><tr> + <td class="tdl">Apricot</td> + <td class="tdc">0.51</td> + <td class="tdc">59.36</td> + <td class="tdc">10.26 </td> + <td class="tdc">3.17</td> + <td class="tdc">3.68</td> + <td class="tdc">1.68</td> + <td class="tdc">0.37</td> + </tr><tr> + <td class="tdl">Orange</td> + <td class="tdc">0.43</td> + <td class="tdc">48.94</td> + <td class="tdc">2.50</td> + <td class="tdc">22.71 </td> + <td class="tdc">5.34</td> + <td class="tdc">0.97</td> + <td class="tdc">0.37</td> + </tr><tr> + <td class="tdl">Lemon</td> + <td class="tdc">0.53</td> + <td class="tdc">48.26</td> + <td class="tdc">1.76</td> + <td class="tdc">29.87 </td> + <td class="tdc">4.40</td> + <td class="tdc">0.43</td> + <td class="tdc">0.28</td> + </tr><tr> + <td class="tdl">Apple</td> + <td class="tdc">1.44</td> + <td class="tdc">35.68</td> + <td class="tdc">26.09 </td> + <td class="tdc">4.08</td> + <td class="tdc">8.75</td> + <td class="tdc">1.40</td> + <td class="tdc"> </td> + </tr><tr> + <td class="tdl">Pear</td> + <td class="tdc">1.97</td> + <td class="tdc">54.69</td> + <td class="tdc">8.52</td> + <td class="tdc">7.98</td> + <td class="tdc">5.22</td> + <td class="tdc">1.04</td> + <td class="tdc"> </td> + </tr><tr> + <td class="tdl">Peach</td> + <td class="tdc">4.90</td> + <td class="tdc">27.95</td> + <td class="tdc">0.23</td> + <td class="tdc">8.81</td> + <td class="tdc">17.66 </td> + <td class="tdc">0.55</td> + <td class="tdc"> </td> + </tr><tr> + <td class="tdc" colspan="8"> </td> + </tr><tr> + <td class="tdl"><b>Name.</b></td> + <td class="tdc"><b>(C)</b></td> + <td class="tdc"><b>(D)</b></td> + <td class="tdc"><b>Per cent<br>silica.</b></td> + <td class="tdc"><b>Per cent<br>chlorin.</b></td> + <td class="tdc" rowspan="8" colspan="3"> </td> + </tr><tr> + <td class="tdl">Prune</td> + <td class="tdc">14.08</td> + <td class="tdc">2.68</td> + <td class="tdc">3.07</td> + <td class="tdc">0.34</td> + </tr><tr> + <td class="tdl">Apricot</td> + <td class="tdc">13.09</td> + <td class="tdc">2.63</td> + <td class="tdc">5.23</td> + <td class="tdc">0.45</td> + </tr><tr> + <td class="tdl">Orange</td> + <td class="tdc">12.37</td> + <td class="tdc">5.25</td> + <td class="tdc">0.65</td> + <td class="tdc">0.92</td> + </tr><tr> + <td class="tdl">Lemon</td> + <td class="tdc">11.09</td> + <td class="tdc">2.84</td> + <td class="tdc">0.66</td> + <td class="tdc">0.39</td> + </tr><tr> + <td class="tdl">Apple</td> + <td class="tdc">13.59</td> + <td class="tdc">6.09</td> + <td class="tdc">4.32</td> + <td class="tdc" rowspan="3"> </td> + </tr><tr> + <td class="tdl">Pear</td> + <td class="tdc">15.20</td> + <td class="tdc">5.69</td> + <td class="tdc">1.49</td> + </tr><tr> + <td class="tdl">Peach</td> + <td class="tdc">43.63</td> + <td class="tdc">0.37</td> + <td class="tdc"> </td> + </tr> + </tbody> +</table> + +<p><b>576. Dried Fruits.</b>—A method of preserving fruits largely +practiced consists in subjecting them, in thin slices or whole, to +the action of hot air until the greater part of the moisture is +driven off. The technique of the process is fully described in recent +publications.<a id="FNanchor_588" href="#Footnote_588" class="fnanchor">[588]</a> +It has been shown by Richards that fruit subjected to rapid evaporation +undergoes but little change aside from the loss of water.<a id="FNanchor_589" href="#Footnote_589" class="fnanchor">[589]</a></p> + +<p>In the analyses of dried fruits the methods already described are used. +The presence of pectin renders the filtration of the aqueous extract +somewhat difficult, and in many cases it is advisable to determine the +sugars present in the extract without previous filtration.</p> + +<p><b>577. Zinc in Evaporated Fruits.</b>—Fruits are commonly evaporated +on trays made of galvanized iron. In these instances a portion of +the zinc is dissolved by the fruit acids, and will be found as zinc +malate etc., in the finished product. The presence of zinc salts is +objectionable for hygienic reasons, and therefore the employment of +<span class="pagenum"><a id="Page_581"></a>[Pg 581]</span> +galvanized trays should be discontinued. The presence of zinc in +evaporated fruits may be detected by the following process.<a id="FNanchor_590" href="#Footnote_590" class="fnanchor">[590]</a> +The sample is placed in a large platinum dish and heated slowly until dry +and in incipient combustion. The flame is removed and the combustion +allowed to proceed, the lamp being applied from time to time in case +the burning ceases. When the mass is burned out it will be found +to consist of ash and char, which are ground to a fine powder and +extracted with hydrochloric or nitric acid. The residual char is burned +to a white ash at a low temperature, the ash extracted with acid, the +soluble portion added to the first extract and the whole filtered. +The iron in the filtrate is oxidized by boiling with bromin water and +the boiling continued until the excess of bromin is removed. A drop +of methyl orange is placed in the liquid and ammonia added until it +is only faintly acid. The iron is precipitated by adding fifty cubic +centimeters of a solution containing 250 grams of ammonium acetate in +a liter and raising the temperature to about 80°. The precipitate is +separated by filtration and washed with water at 80° until free of +chlorids. The filtrate is saturated with hydrogen sulfid, allowed to +stand until the zinc sulfid settles and poured on a close filter. It is +often necessary to return the filtrate several times before it becomes +limpid. The collected precipitate is washed with a saturated solution +of hydrogen sulfid containing a little acetic acid. The precipitate +and filter are transferred to a crucible, dried, ignited and the zinc +weighed as oxid. Small quantities of zinc salts added to fresh apples +which were dried and treated as above described, were recovered by this +method without loss. Other methods of estimating zinc in dried fruits +are given in the bulletin cited.</p> + +<p>Evaporated apples contain a mean content of 23.85 per cent of water and +0.931 per cent of ash.</p> + +<p>The mean quantity of zinc oxid found in samples of apples dried in +the United States is ten milligrams for each 100 grams of the fruit, +an amount entirely too small to produce any toxic effects. When zinc +exists in the soil it will be found as a natural constituent in the +crop.<a id="FNanchor_591" href="#Footnote_591" class="fnanchor">[591]</a></p> + +<p><b>578. Composition of Watermelons and Muskmelons.</b>—In the +examination of melons a separation of the rind, seeds and meat is +<span class="pagenum"><a id="Page_582"></a>[Pg 582]</span> +somewhat difficult of accomplishment, since the line of demarcation is +not distinct. In watermelons the separation of rind and meat is made +at the point where the red color of the meat disappears. In muskmelons +no such definite point is found and in the examination of these they +are taken as a whole. The total moisture, ash and nitrogen may be +determined in the whole mass or in the separate portions. The sugars +are most conveniently determined in the expressed juices. The mean +composition of the melons given below is that obtained from analyses +made in the Department of Agriculture.<a id="FNanchor_592" href="#Footnote_592" class="fnanchor">[592]</a></p> + +<table class="spb1 spa1"> + <thead><tr> + <th class="tdc fs_120" colspan="5"><span class="smcap">Composition of Melons.</span></th> + </tr><tr> + <th class="tdc"> </th> + <th class="tdc bb">Total weight,<br>grams.</th> + <th class="tdc bb">Juice,<br>per cent.</th> + <th class="tdc bb">Total<br>proteids,<br>per cent.</th> + <th class="tdc bb">Ash,<br>per cent.</th> + </tr></thead> + <tbody><tr> + <td class="tdc" rowspan="2">Watermelons</td> + <td class="tdc" rowspan="2">10330</td> + <td class="tdc">meat 83.99</td> + <td class="tdc" rowspan="2">6.12</td> + <td class="tdc" rowspan="2">0.37</td> + </tr><tr> + <td class="tdc">rind 81.02</td> + </tr><tr> + <td class="tdc">Muskmelons</td> + <td class="tdc">3407</td> + <td class="tdr">80.23</td> + <td class="tdc">6.45</td> + <td class="tdc">0.57</td> + </tr><tr> + <td class="tdc fs_120" colspan="5"><b><span class="smcap"> <br>Composition of Juice.</span></b></td> + </tr><tr> + <td class="tdc"> </td> + <td class="tdc_bott bb"><b>Sucrose<br>in juice,<br>per cent.</b></td> + <td class="tdc bb" colspan="2"><b>Reducing<br> sugars<br>in juice,<br>per cent.</b></td> + <td class="tdc_bott bb"><b>Ash<br>per cent.</b></td> + </tr><tr> + <td class="tdc" rowspan="2">Watermelons</td> + <td class="tdc">meat 1.92</td> + <td class="tdc" colspan="2">meat 4.33</td> + <td class="tdc">meat 0.31</td> + </tr><tr> + <td class="tdc">rind 0.34</td> + <td class="tdc" colspan="2">rind 2.47</td> + <td class="tdc">rind 0.38</td> + </tr><tr> + <td class="tdc">Muskmelons</td> + <td class="tdr_ws1">1.02</td> + <td class="tdc" colspan="2">   3.04</td> + <td class="tdr">0.53</td> + </tr> + </tbody> +</table> + +<h3>TEA AND COFFEE.</h3> + +<p><b>579. Special Analysis.</b>—Aside from the examination of teas and +coffees for adulterants, the only special determinations which are +required in analyses are the estimation of the alkaloid (caffein) and +of the tannin contained therein. It is chiefly to the alkaloid that the +stimulating effects of the beverages made from tea and coffee are due. +The determination of the quantity of tannin contained in tea and coffee +is accomplished by the processes described under the chapter devoted to +that glucosid.</p> + +<p>The general analysis, <i>viz.</i>, the estimation of water, ether +extract, total nitrogen, fiber, carbohydrates and ash, with the +exceptions noted above, is conducted by the methods which have already +been given.</p> + +<p>For detailed instructions concerning the detection of adulterants of +tea and coffee the bulletins of the Chemical Division, Department of +Agriculture, may be consulted.<a id="FNanchor_593" href="#Footnote_593" class="fnanchor">[593]</a></p> + +<p><span class="pagenum"><a id="Page_583"></a>[Pg 583]</span> +<b>580. Estimation of Caffein</b> (<b>Thein</b>).—The method adopted +by Spencer, after a thorough trial of all the usual processes for +estimating this alkaloid, is as follows:<a id="FNanchor_594" href="#Footnote_594" class="fnanchor">[594]</a> +To three grams of the finely powdered tea or coffee, in a 300 cubic +centimeter flask, add about a quarter of a liter of water, slowly heat +to the boiling point, using a fragment of tallow to prevent frothing, +and boil gently for half an hour. When boiling begins, the flask should +be nearly filled with hot water and more added from time to time to +compensate for the loss due to evaporation. After cooling, add a +strong solution of basic lead acetate until no further precipitation +is produced, complete the volume to the mark with water, mix and throw +on a filter. Precipitate the lead from the filtrate by hydrogen sulfid +and filter. Boil a measured volume of this filtrate to expel the excess +of hydrogen sulfid, cool and add sufficient water to compensate for +the evaporation. Transfer fifty cubic centimeters of this solution to +a separatory funnel and shake seven times with chloroform. Collect the +chloroform solution in a tared flask and remove the solvent by gentle +distillation. A safety bulb, such as is used in the kjeldahl nitrogen +method, should be employed to prevent entrainment of caffein with the +chloroform vapors.</p> + +<p>The extraction with chloroform is nearly complete after shaking out +four times; a delicate test, however, will usually reveal the presence +of caffein in the watery residue even after five or six extractions, +hence seven extractions are recommended for precautionary reasons. The +residual caffein is dried at 75° for two hours and weighed.</p> + +<p>The principal objection which has been made to Spencer’s method is +that the boiling with water is not continued for a sufficient length +of time. For the water extraction, Allen prescribes at least six hours +cohobation.<a id="FNanchor_595" href="#Footnote_595" class="fnanchor">[595]</a> +In this method six grams of the powdered substance are boiled with +half a liter of water for six hours in a flask, with a condenser, the +decoction filtered, the volume of the filtrate completed to 600 cubic +centimeters with the wash water, heated to boiling, and four cubic +centimeters of strong lead acetate solution added, the mixture boiled +for ten minutes, filtered and half a liter of the filtrate evaporated +<span class="pagenum"><a id="Page_584"></a>[Pg 584]</span> +to fifty cubic centimeters. The excess of lead is removed with sodium +phosphate and the filtrate and washings concentrated to about forty +cubic centimeters. The caffein is removed by shaking four times with +chloroform. Older but less desirable processes are fully described by +Allen.<a id="FNanchor_596" href="#Footnote_596" class="fnanchor">[596]</a></p> + +<p>In France this method is known as the process of Petit and Legrip, and +it has been worked out in great detail by Grandval and Lajoux and by +Petit and Terbat.<a id="FNanchor_597" href="#Footnote_597" class="fnanchor">[597]</a></p> + +<p><b>581. Estimation of Caffein by Precipitation with Iodin.</b>—The +caffein in this method is extracted, the extract clarified by lead +acetate and the excess of lead removed as in Spencer’s process +described above. The caffein is determined in the acidified aqueous +solution thus prepared, according to the plan proposed by Gomberg, as +follows:<a id="FNanchor_598" href="#Footnote_598" class="fnanchor">[598]</a></p> + +<p>Definite volumes of the aqueous solution of the caffein are acidulated +with sulfuric and the alkaloid precipitated by an excess of a set +solution of iodin in potassium iodid. After filtering, the excess of +iodin in an aliquot part of the filtrate is determined by titration +with a tenth normal solution of sodium thiosulfate. The filtration +of the iodin liquor is accomplished on glass wool or asbestos. The +results of the analyses are calculated from the composition of the +precipitated caffein periodid; <i>viz.</i>, <b>C₈H₁₀N₄O₂.HI.I₄</b>. The weight +of the alkaloid is calculated from the amount of iodin required for the +precipitation by the equation <b>4I: C₈H₁₀N₄O₂ = 508: 194</b>. From this +equation it is shown that one part of iodin is equivalent to 0.3819 +part of caffein, or one cubic centimeter of tenth normal iodin solution +is equal to 0.00485 gram of iodin.</p> + +<p>In practice, it is recommended to divide the aqueous extract of the +alkaloid, prepared as directed above, into two portions, one of which +is treated with the iodin reagent without further preparation, and +the other after acidulation with sulfuric. After ten minutes, the +residual iodin is estimated in each of the solutions as indicated +above. The one portion, containing only the acetic acid resulting from +the decomposition of the lead acetate, serves to indicate whether +the aqueous solution of the caffein contains other bodies than that +alkaloid capable of forming a precipitate with the reagent, since the +caffein itself is not precipitated even in presence of strong acetic acid. +<span class="pagenum"><a id="Page_585"></a>[Pg 585]</span></p> + +<p>In the solution acidulated with sulfuric, the caffein, together with +the other bodies capable of combining with iodin, is precipitated. The +residual iodin is determined in each case, and thus the quantity which +is united with the caffein is easily ascertained. The weight of iodin +which has entered into the precipitated caffein periodid multiplied by +0.3819 gives the weight of the caffein in the solution.</p> + +<p>Gomberg’s method has been subjected to a careful comparative study by +Spencer and has been much improved by him in important particulars.<a id="FNanchor_599" href="#Footnote_599" class="fnanchor">[599]</a></p> + +<p>It is especially necessary to secure the complete expulsion of +the hydrogen sulfid and to observe certain precautions in the +addition of the iodin reagent. The precipitation should be made in a +glass-stoppered flask, shaking thoroughly after the addition of the +iodin and collecting the precipitate on a gooch. As thus modified, the +iodin process gives results comparable with those obtained by Spencer’s +method, and it can also be used to advantage in estimating caffein in +headache tablets in the presence of acetanilid.</p> + +<p><b>582. Freeing Caffein of Chlorophyll.</b>—Any chlorophyll which +may pass into solution and be found in the caffein may be removed +by dissolving the caffein in ten per cent sulfuric acid, filtering, +neutralizing with ammonia and evaporating to dryness. The residue is +taken up with chloroform, the chloroform removed at a low temperature +and the pure caffein thus obtained.<a id="FNanchor_600" href="#Footnote_600" class="fnanchor">[600]</a></p> + +<p><b>583. Proteid Nitrogen.</b>—The proteid nitrogen in tea and coffee +may be determined in the residue after extraction of the alkaloid +by boiling water as described above. More easily it is secured by +determining the total nitrogen in the sample and deducting therefrom +the nitrogen present as caffein. The remainder, multiplied by 6.25, +will give the quantity of proteid matter.</p> + +<p><b>584. Carbohydrates of the Coffee Bean.</b>—The carbohydrates of the +coffee bean include those common to vegetable substances; <i>viz.</i>, +cellulose, pentosan bodies (xylan, araban), fiber etc., together +with certain sugars, of which sucrose is pointed out by Ewell as the +chief.<a id="FNanchor_601" href="#Footnote_601" class="fnanchor">[601]</a> +In smaller quantities are found a galactose yielding body (galactan), +as pointed out by Maxwell, a dextrinoid and a trace of a sugar reducing +<span class="pagenum"><a id="Page_586"></a>[Pg 586]</span> +alkaline copper solution.</p> + +<p>The sucrose may be separated from the coffee bean by the following +process:<a id="FNanchor_602" href="#Footnote_602" class="fnanchor">[602]</a> +The finely ground flour is extracted with seventy per cent alcohol, the +extract clarified with lead acetate, filtered, the lead removed from +the filtrate with hydrogen sulfid, the excess of the gas removed by +boiling, the filtrate evaporated in a partial vacuum to a sirup and the +sucrose crystallized from a solution of the sirup in alcohol.</p> + +<p>For a quantitive determination, ten grams of the coffee flour are +extracted with ether and the residue with seventy-five per cent +alcohol. This process, conducted in a continuous extraction apparatus, +should be continued for at least twenty-four hours. The alcohol is +removed by evaporation, the residue dissolved in water, clarified with +basic lead acetate, filtered, the precipitate washed, the lead removed, +again filtered, the filtrate washed and wash water and filtrate made to +a definite volume. In an aliquot part of this solution the sugars +are determined by the alkaline copper method, both before and after +inversion. From the data obtained the percentage of sucrose is calculated.</p> + +<p>In a coffee examined by Ewell the percentage of sucrose was found to be +6.34. The pentose yielding constituents of the coffee bean amount to +from eight to ten per cent.</p> + +<p>When coffee meal is extracted with a five per cent solution of sodium +carbonate, a gummy substance is obtained, which is precipitable by +alcohol. This gum, after washing with hydrochloric acid containing +alcohol, gives a gray, translucent, hard mass on drying. On hydrolysis +it yielded 75.2 per cent of dextrose, on distillation with hydrochloric +acid, thirteen per cent of furfuraldehyd and, on oxidation with nitric +acid, 18.7 per cent of mucic acid. This gum, therefore, consists +chiefly of a mixture of galactan, xylan and araban.</p> + +<p id="P_585"><b>585. Estimation of Galactan.</b>—From three to five grams of the +substance supposed to contain galactan are placed in a beaker with +sixty cubic centimeters of nitric acid of 1.15 specific gravity. The +mixture is evaporated on a steam bath until it is reduced to one-third +<span class="pagenum"><a id="Page_587"></a>[Pg 587]</span> +of its original volume, allowed to stand for twenty-four hours, ten +cubic centimeters of water added, well stirred and again allowed +to stand for twenty-four hours, until the mucic acid is separated +in a crystalline form. To remove impurities from the mucic acid it +is separated by filtration, washed with not to exceed twenty cubic +centimeters of water, placed together with the filter in the beaker, +from twenty-five to thirty cubic centimeters of ammonium carbonate +solution, containing one part of dry ammonium carbonate, nineteen +parts of water and one part of ammonium hydroxid, added and heated to +near the boiling point. The mucic acid is dissolved by the ammonium +carbonate solution and any insoluble impurity separated by filtration, +the filtrate being received in a platinum dish, the residue well washed +and the entire filtrate and wash water evaporated to dryness on a steam +bath acidified with dilute nitric, well stirred and allowed to stand +until the mucic acid separates in a crystalline form. The separation +is usually accomplished in half an hour, after which time the crystals +of mucic acid are collected on a tared filter, or gooch, and washed +with not to exceed fifteen cubic centimeters of water followed with +sixty cubic centimeters of alcohol, then with ether, dried at 100° +and weighed. For computing the amount of galactose, one gram of the +mucic acid is equal to 1.333 of galactose and one gram of galactose is +equal to nine-tenths gram of galactan. Before the commencement of the +operation, the material should be freed of fatty matters in the case of +oily seeds and other substances similar thereto.<a id="FNanchor_603" href="#Footnote_603" class="fnanchor">[603]</a></p> + +<p id="P_586"><b>586. Revised Factors for Pentosans.</b>—The factors given in +paragraph <b><a href="#P_154">154</a></b> have lately been recalculated by Mann, +Kruger and Tollens, and as a result of their investigations the following factors +are now recommended.<a id="FNanchor_604" href="#Footnote_604" class="fnanchor">[604]</a> +The quantity of furfurol is derived from the weight of furfurolhydrazone +obtained by the formula:</p> + +<ul class="index fs_105"> +<li class="isub3">1. Furfurolhydrazone × 0.516 + 0.0104 = furfurol.</li> +<li class="isub3">2. Furfurol × 1.84 = pentosans.</li> +<li class="isub3">3. Furfurol × 1.64 = xylan.</li> +<li class="isub3">4. Furfurol × 2.02 = araban.</li> +</ul> + +<p>The pentoses (xylose, arabinose) may be calculated from the pentosans +(xylan, araban) by dividing by 0.88. +<span class="pagenum"><a id="Page_588"></a>[Pg 588]</span></p> + +<p>The method of procedure preferred for the estimation of the pentosans +is that described in paragraph <b><a href="#P_157">157</a></b>. The phloroglucin +is dissolved in hydrochloric acid of 1.06 specific gravity before it is +added to the furfurol distillate. The latest factor for converting +the phloroglucid obtained into furfurol is to divide by 1.82 for +small quantities and 1.93 for large quantities. After the furfurol is +obtained, the factors given above are applied.</p> + +<p><b>587. Application of Roentgen Rays to Analysis.</b>—The detection +of mineral matters in vegetable substances by roentgen photography has +been proposed by Ranvez.<a id="FNanchor_605" href="#Footnote_605" class="fnanchor">[605]</a> +This process will prove extremely valuable in detecting the lacing +of teas with mineral substances. Practically, it has been applied by +Ranvez in the detection of mineral substances mixed with saffron with +fraudulent intent.</p> + +<p>Barium sulfate is often mixed with saffron for the purpose of +increasing its weight. Pure saffron and adulterated samples are +enclosed in capsules of black paper and exposed on the same sensitive +plate for a definite time to the rays emanating from a crookes tube. +In this case the pure saffron forms only a very faint shadow in the +developed negative, while the parts to which barium sulfate are +attached produce strong shadows. The principle involved is applicable +to a wide range of analytical research.</p> + +<h3>TANNINS AND ALLIED BODIES.</h3> + +<p><b>588. Occurrence and Composition.</b>—The tannins and allied bodies, +which are of importance in this connection, are those which occur in +food products and beverages and also those made use of in the leather +industry. The term tannin is applied to a large class of astringent +substances, many of which are glucosids. Tannic acid is the chief +constituent of the tannins, and is found in a state of comparative +purity in nutgalls. The source from which the tannic acid is derived +is indicated by a prefix to the name, <i>e. g.</i>, gallotannic, from +nutgalls, and caffetannic, from coffee etc. The tannins have lately +been the theme of a critical study by Trimble, and the reader is +referred to his work for an exhaustive study of the subject.<a id="FNanchor_606" href="#Footnote_606" class="fnanchor">[606]</a> +Tannin is one of the most widely diffused compounds, occurring in hundreds +<span class="pagenum"><a id="Page_589"></a>[Pg 589]</span> +of plants. Commercially, the oaks and hemlocks are the most important +plants containing tannin. The sumach, mangrove, canaigre, palmetto and +many others have also been utilized as commercial sources of tannin. +The tannins as a class are amorphous and odorless. They are slightly +acid and strongly astringent. Their colors vary from dark brown to +pure white. They are soluble in water, alcohol, ether and glycerol and +insoluble in chloroform, benzol, petroleum ether, carbon bisulfid and +the oils. The tannins give blue or green precipitates with iron salts +and most of them brown precipitates with potassium bichromate. They are +all precipitated by gelatin or albumin. Tannins are not only generally +of a glucosidal nature, but are found quite constantly associated with +reducing sugars, or in unstable combination therewith.</p> + +<p>The reducing sugars may be separated from the tannin by precipitating +the latter with lead acetate and determining the glucose in the +filtrate after the removal of the lead. A separate portion of the +tannin is hydrolyzed with sulfuric or hydrochloric acid and the +reducing sugars again determined. Any excess of sugars over the first +determination is due to the hydrolysis of the tannin glucosid.</p> + +<p id="P_589"><b>589. Detection and Estimation of Tannins.</b>—The qualitive +reactions above mentioned serve to detect the presence of a tannin. Of +the iron salts ferric acetate or chlorid is preferred. Ferrous salts +do not give any reaction with dilute tannin solutions. An ammoniacal +solution of potassium ferricyanid forms with tannins a deep red color +changing to brown. In quantitive work the tannins are mostly determined +by precipitation with metallic salts, by treatment with gelatin or hide +powder, or by oxidation with potassium permanganate. Directions for the +estimation of glucosids in general are found in Dragendorff’s book.<a id="FNanchor_607" href="#Footnote_607" class="fnanchor">[607]</a></p> + +<p><b>590. Precipitation with Metallic Salts.</b>—The methods depending +on precipitation of the tannins with metallic salts are but little +used and only one of them will be mentioned here. A full description +of the others is contained in Trimble’s book.<a id="FNanchor_608" href="#Footnote_608" class="fnanchor">[608]</a> +A method for the determination of caffetannic acid in coffee has been +<span class="pagenum"><a id="Page_590"></a>[Pg 590]</span> +worked out by Krug and used with some satisfaction.<a id="FNanchor_609" href="#Footnote_609" class="fnanchor">[609]</a></p> + +<p>In this method two grams of the coffee meal are digested for thirty-six +hours with ten cubic centimeters of water, a little more than twice +that volume of ninety-five per cent alcohol added and the digestion +continued for a day. The contents of the flask are poured on a filter +and the residue washed with alcohol. The filtrate contains tannin, +caffetannic acid and traces of coloring matter and fat. It is heated +to the boiling point and clarified with a solution of lead acetate. +A caffetannate of lead containing forty-nine per cent of the metal +is precipitated. As soon as the precipitate has become flocculent it +is collected on a filter, washed with ninety per cent alcohol until +the soluble lead salts are all removed, then with ether and dried. +The composition of the precipitate is represented by the formula +<b>Pb₃(C₁₅H₁₅O₈)₂</b>. The caffetannic acid is calculated by the equation: +Weight of precipitate: weight of caffetannic acid = 1267: 652.</p> + +<p><b>591. The Gelatin Method.</b>—The precipitation of tannin with +gelatin is the basis of a process for its quantitive estimation which, +according to Trimble, is conducted as follows:<a id="FNanchor_610" href="#Footnote_610" class="fnanchor">[610]</a> +Two and a half grams of gelatin and ten grams of alum are dissolved +in water and the volume of the solution made up to one liter. The +solution of gelatin and also that of the tannin are heated to 70° and +the tannin is precipitated by adding the gelatin reagent slowly, with +constant stirring, until the precipitate coagulates, and, on settling, +leaves a clear liquor in which no further precipitate is produced on +adding a few drops more of the reagent. In case the clearing of the +mixture do not take place readily, the process should be repeated with +a more dilute tannin solution. The precipitate is collected on two +counterpoised filter papers one placed inside the other, dried at 110° +and weighed, the empty filter paper being placed on the pan with the +weights. For pure tannin (gallotannic acid) fifty-four per cent of the +weight of the precipitate are tannin. Ammonium chlorid and common salt +have been used in place of the alum in preparing the reagent, but if +the proportion of alum mentioned above be used, satisfactory results +will be obtained in most cases. +<span class="pagenum"><a id="Page_591"></a>[Pg 591]</span></p> + +<p><b>592. The Hide Powder Method.</b>—The principle of this method is +based on the change in specific gravity, <i>i. e.</i>, total solids, +which a tannin solution will undergo when brought into contact with +raw hides in a state of fine subdivision. The hide powder absorbs the +tannin, and the total solid content of the solution is correspondingly +diminished. The method is conducted according to the official +directions as follows:<a id="FNanchor_611" href="#Footnote_611" class="fnanchor">[611]</a></p> + +<p><i>Preparation of the Sample.</i>—The bark, wood, leaves or other +materials holding the tannins, are dried and ground to a fine powder +and thoroughly extracted with water as mentioned below. In each case +the solution or extraction is made as thorough as possible and the +volume of the extract is made up to a definite amount.</p> + +<p><i>Quantity of Tanning Material.</i>—Use such an amount of the tanning +material as shall give in 100 cubic centimeters of the filtered +solution about one gram of dry solids. In the case of barks, woods, +leaves and similar materials, transfer to a half liter flask, fill +the flask with water at approximately 80° and let stand over night in +a bath which is kept at 80°, cool, fill to the mark, shake well and +filter. In the case of extracts and sweet liquors, wash the proper +quantity into a half liter flask with water at approximately 80°, +almost filling the flask, cool and fill to the mark.</p> + +<p><i>Determination of Moisture.</i>—Dry five grams of the sample in a +flat bottom dish at the temperature of boiling water until the weight +becomes constant.</p> + +<p><i>Determination of Total Solids.</i>—Shake the solution, which should +be at a temperature of about 20°, and immediately remove 100 cubic +centimeters with a pipette, evaporate in a weighed dish and dry to +constant weight at the temperature of boiling water.</p> + +<p><i>Determination of Soluble Solids.</i>—Filter a portion of the +solution through a folded filter, returning the filtrate to the filter +twice and adding a teaspoonful of kaolin, if necessary. Evaporate 100 +cubic centimeters of the filtrate and dry as above.</p> + +<p><i>Determination of Tanning Substances.</i>—Extract twenty grams of +hide powder by shaking for five minutes with 250 cubic centimeters of +water, filter through well washed muslin or linen, repeat the operation +three times and dry as much as possible in a suitable press. Weigh the +<span class="pagenum"><a id="Page_592"></a>[Pg 592]</span> +wet powder and determine the residual moisture in about one-fourth +of the whole by drying to constant weight at 100°. Shake 200 cubic +centimeters of the unfiltered solution of the tannin with the rest +of the moist hide powder for about five minutes, add five grams of +barium sulfate, shake for one minute and filter through a schleicher +and schüll folded filter, No. 590, fifteen centimeters in diameter, +returning the first twenty-five cubic centimeters of the filtrate. +Evaporate 100 cubic centimeters of the clear filtrate and dry the +residue to constant weight at a temperature of boiling water. The +difference between the soluble solids obtained in the filtered tannin +solution and the residue as obtained above is the amount of tanning +material absorbed by the hide powder. This weight must be corrected for +the water retained by the hide powder. The shaking must be conducted +by means of a mechanical shaker, in order to remove all the tannin +substance from the solution. The simple machine used by druggists, and +known as the milkshake, is recommended.</p> + +<p><i>Testing the Hide Powder.</i>—Shake ten grams of the hide powder +with 200 cubic centimeters of water for five minutes, filter through +muslin or linen, squeeze out thoroughly by hand, replace the residue +in the flask and repeat the operation twice with the same quantity of +water. Pass the last filtrate through paper until a perfectly clear +liquid is obtained. Evaporate 100 cubic centimeters of the final +filtrate in a weighed dish, dry at 100° until the weight is constant. +If the residue amount to more than ten milligrams the sample should be +rejected. The hide powder must be kept in a dry place and tested once a +month.</p> + +<p>Prepare a solution of pure gallotannic acid by dissolving five grams in +one liter of water. Determine the total solids by evaporating 100 cubic +centimeters of this solution and drying to constant weight. Treat 200 +cubic centimeters of the solution with hide powder exactly as described +above. The hide powder must absorb at least ninety-five per cent of +the total solids present. The gallotannic acid used must be completely +soluble in water, alcohol, acetone and acetic ether and should contain +not more than one per cent of substances not removed by digesting with +excess of yellow mercuric oxid on the steam bath for two hours. +<span class="pagenum"><a id="Page_593"></a>[Pg 593]</span></p> + +<p><i>Testing the Non-Tannin Filtrate. For Tannin</i>:—Test a small +portion of the clear non-tannin filtrate with a few drops of a ten +per cent solution of gelatin. A cloudiness indicates the presence +of tannin, in which case the determination must be repeated, using +twenty-five grams of hide powder instead of twenty grams.</p> + +<p><i>For Soluble Hide</i>:—To a small portion of the clear non-tannin +filtrate, add a few drops of the original solution, previously filtered +to remove reds. A cloudiness indicates the presence of soluble hide +due to incomplete washing of the hide powder. In this case, repeat the +determination with perfectly washed hide powder.</p> + +<p><b>593. The Permanganate Gelatin Method.</b>—This process, which is +essentially the method of Löwenthal, as improved by Councler, Schroeder +and Proctor and as used by Spencer for the determination of tannin in +teas, is conducted as described below.<a id="FNanchor_612" href="#Footnote_612" class="fnanchor">[612]</a> +The principle of the process is based on the oxidation of all bodies +in solution oxidizable by potassium permanganate, the subsequent +precipitation of the tannin by a gelatin solution, and the final +oxidation, by means of permanganate, of the remaining organic bodies. +The difference between the total oxidizable matter and that left after +the precipitation of the tannin represents the tannin originally in solution.</p> + +<p><i>Reagents Required.</i>—The following reagents are necessary to the +proper conduct of the potassium permanganate process:</p> + +<p>(1). Potassium permanganate solution containing about one and a third +grams of the salt in a liter:</p> + +<p>The potassium permanganate solution is set by titration against the +decinormal oxalic acid solution mentioned below. The end reaction with +the indicator must be of the same tint in all the titrations, <i>i. +e.</i>, either golden yellow or pink.</p> + +<p>(2). Tenth-normal oxalic acid solution for determining the exact titer +of the permanganate solution:</p> + +<p>(3). Indigo-carmin solution to be used as an indicator and containing +six grams of indigo-carmin and fifty cubic centimeters of sulfuric acid in +a liter. The indigo-carmin must be very pure and quite free of indigo-blue. +<span class="pagenum"><a id="Page_594"></a>[Pg 594]</span></p> + +<p>(4). Gelatin solution, prepared by digesting twenty-five grams of +gelatin at room temperature for one hour in a saturated solution of +sodium chlorid, then heating until solution is complete, cooling and +making the volume up to one liter:</p> + +<p>(5). A salt acid solution, made by adding to 975 cubic centimeters of +a saturated solution of sodium chlorid, enough strong sulfuric acid to +bring the volume of the mixture to one liter:</p> + +<p>(6). Powdered kaolin for promoting filtration.</p> + +<p><i>The Process.</i>—Five grams of the finely powdered tea (or other +vegetable substance containing tannin) are boiled with distilled water +in a flask of half a liter capacity for half an hour. The distilled +water should be at room temperature when poured over the powdered tea. +After cooling, the volume of the decoction is completed to half a +liter, and the contents of the flask poured on a filter. To ten cubic +centimeters of the filtered tea infusion are added two and a half times +as much of the indigo-carmin solution and about three-quarters of a +liter of distilled water.</p> + +<p>The permanganate solution is run in from a burette, a little at a time, +with vigorous stirring, until the color changes to a light green, and +then drop by drop until the final color selected for the end of the +reaction, golden yellow or faint pink, is obtained. The number of cubic +centimeters of permanganate required is noted and represented by a in +the formula below. The titration should be made in triplicate and the +mean of the two more nearly agreeing readings taken as the correct one.</p> + +<p>One hundred cubic centimeters of the filtered tea infusion, obtained +as directed above, are mixed with half that quantity of the gelatin +reagent, the first named quantity of the acid salt solution added, +together with ten grams of the powdered kaolin, the mixture well +shaken for several minutes and poured on a filter. Twenty-five cubic +centimeters of the filtrate, corresponding to ten of the original +tea solution are titrated with the permanganate reagent, under the +conditions given above, and the reading of the burette made and +represented by <i>b</i>. The quantity of permanganate solution, +<i>viz.</i>, <i>c</i>, required to oxidize the tannin is calculated +from the formula <i>a - b</i> = <i>c</i>. The relation between the +permanganate, oxalic acid and tannin is such that 0.04157 gram of +gallotannic acid is equivalent to 0.063 gram of oxalic acid. The +<span class="pagenum"><a id="Page_595"></a>[Pg 595]</span> +relation between the oxalic acid solution and the permanganate having +been previously determined the data for calculating the quantity of +tannin, estimated as gallotannic acid, are at hand.</p> + +<p><b>594. The Permanganate Hide Powder Method.</b>—Instead of throwing +out the tannin with gelatin it may be absorbed by hide powder. The +principle of the process, save this modification, is the same as in +the method just described. As described by Trimble, the analysis is +conducted according to the following directions:<a id="FNanchor_613" href="#Footnote_613" class="fnanchor">[613]</a></p> + +<p><i>Reagents Required.</i>—The reagents required for conducting the +permanganate hide powder process are as follows:</p> + +<p>1. <i>Permanganate Solution.</i>—Ten grams of pure potassium +permanganate are dissolved in six liters of water. The solution is +standardized with pure tannin. The moisture in the pure tannin is +determined by drying at 100° to constant weight and then a quantity of +the undried substance, representing two grams of the dried material, is +dissolved in one liter of water. Ten cubic centimeters of this solution +and double that quantity of the indigo solution to be described below, +are mixed with three-quarters of a liter of water and the permanganate +solution added from a burette with constant stirring until the liquid +assumes a greenish color and then, drop by drop, until a pure yellow +color with a pinkish rim is obtained. Fifty cubic centimeters of the +pure tannin solution are digested, with frequent shaking, with three +grams of hide powder which has been previously well moistened and dried +in a press for eighteen or twenty hours, the contents of the flask +thrown on a filter and ten cubic centimeters of the filtrate titrated +with the permanganate solution as directed above. The difference +between the amount of permanganate solution required for the first and +second titrations represents the amount of pure tannin or oxidizable +matter removed by the hide powder.</p> + +<p>2. <i>Indigo Solution.</i>—The indicator which is used in the +titrations is prepared by dissolving thirty grams of sodium +sulfindigotate in three liters of dilute sulfuric acid made by adding +one volume of the strong acid to three volumes of water. The solution +is shaken for a few minutes, thrown upon a filter and the insoluble +<span class="pagenum"><a id="Page_596"></a>[Pg 596]</span> +residue washed with sufficient water to make the volume of the filtrate +six liters.</p> + +<p>3. <i>Hide Powder.</i>—The hide powder used should be white, wooly in +character and sufficiently well extracted with water to afford no other +extract capable of oxidizing the permanganate solution.</p> + +<p><i>The Process.</i>—The reagents having been prepared and tested as +above, the solution of the substance containing the tannin, prepared +as described further on, is titrated first with the permanganate +solution in the manner already given. Fifty cubic centimeters of the +tannin solution are then shaken, from, time to time for eighteen hours, +with three grams of hide powder, thrown upon a filter and ten cubic +centimeters of the filtrate titrated with the potassium permanganate as +above described. From the data obtained, the quantity of permanganate +solution corresponding to the tannin removed by the hide powder is +easily calculated. The value of the permanganate solution having been +previously set with a pure tannin, renders easy of calculation the +corresponding amount of pure tannin in the solution under examination.</p> + +<p><b>595. Preparation of the Tannin Infusion.</b>—A sample weighing +about a kilogram should be secured, representing as nearly as possible +the whole of the materials containing tannin in a given lot. The sample +is reduced to a fine powder and passed through a sieve containing +apertures about a millimeter in diameter. The quantity of the sample +used for the extraction depends largely upon its content of tannin. +Five grams of nutgalls, ten grams of sumach or twenty grams of oak +bark represent about the quantities necessary for these classes of +tannin-holding materials. The sample is boiled for half an hour with +half a liter of water, filtered through a linen bag into a liter flask +and washed and pressed with enough water to make the volume of the +filtrate equal to one liter. The proper quantities of this solution are +used for the analytical processes described above.</p> + +<h3>TOBACCO.</h3> + +<p><b>596. Fermented and Unfermented Tobacco.</b>—Samples of tobacco may +<span class="pagenum"><a id="Page_597"></a>[Pg 597]</span> +reach the analyst either in the fermented or unfermented state. As a +basis for comparison, it is advisable in all cases to determine the +constituents of the sample before fermentation sets in. The analysis, +after fermentation is complete, will then show the changes of a +chemical nature which it has undergone during the process of curing and +sweating. Only tobacco which has undergone fermentation is found to be +in a suitable condition for consumption. In addition to the natural +constituents of tobacco, it may contain, in the manufactured state, +flavoring ingredients such as licorice and sugar, coloring matters and +in some instances, it is said, opium or other stimulating drugs. It +is believed, however, that opium is not often found in manufactured +tobacco, and it has never been found in this laboratory in cigarettes, +although all the standard brands have been examined for it.<a id="FNanchor_614" href="#Footnote_614" class="fnanchor">[614]</a></p> + +<p>In researches made at the Connecticut Station it is shown that +fermentation produces but little change in the relative quantities +of nitric acid, ammonia, fiber and starch in the leaves, while those +of nicotin, albuminoids and amids are diminished. This is not in +harmony with the generally accepted theory that starch is inverted and +fermented during the process.<a id="FNanchor_615" href="#Footnote_615" class="fnanchor">[615]</a></p> + +<p>The nature of the ferments which are active in producing the changes +which tobacco undergoes in curing, is not definitely understood. Some +of the organic constituents of the tobacco undergo a considerable +change during the process. Any sugar which is found in the freshly +cured leaves disappears wholly or in part. As products of fermentation +may also be found succinic, fumaric, formic, acetic, propionic and +butyric acids.</p> + +<p><b>597. Acid and Basic Constituents of Tobacco.</b>—In unfermented +and fermented tobacco are found certain organic acids, among the most +important of which are citric, malic, oxalic, pectic and tannic. Of +the inorganic acids the chief which are found are nitric, sulfuric +and hydrochloric. Among the bases ammonia and nicotin are the most +important. Ammonia is found in the unfermented tobacco in only small +quantities, but in the fermented product it may sometimes reach as high +as half a per cent. The presence of these two nitrogenous bases in +<span class="pagenum"><a id="Page_598"></a>[Pg 598]</span> +tobacco renders the estimation of the proteid matter contained therein +somewhat tedious and difficult.</p> + +<p><b>598. Composition of Tobacco Ash.</b>—The mineral constituents of +tobacco are highly important from a commercial point of view. The +burning properties of tobacco depend largely upon the nature of its +mineral constituents. A sample containing a large quantity of chlorids +burns much less freely than one in which the sulfates and nitrates +predominate. For this reason, the use of potash fertilizers containing +large amounts of chlorin is injudicious in tobacco culture, the +carbonates and sulfates of potash being preferred. The leaves of the +tobacco plant contain a much larger percentage of mineral constituents +than the stems, their respective contents of pure ash, that is ash free +from carbon dioxid, carbon and sand, being about seventeen and seven. +The pure ash of the leaves has the following mean composition: Potash +29.1 per cent, soda 3.2 per cent, lime 36.0 per cent, magnesia 7.4 per +cent, iron oxid 2.0 per cent, phosphoric acid 4.7 per cent, sulfuric +acid 6.0 per cent, silica 5.8 per cent, and chlorin 6.7 per cent.<a id="FNanchor_616" href="#Footnote_616" class="fnanchor">[616]</a></p> + +<p><b>599. Composition of Tobacco.</b>—The mean composition of some of +the more important varieties of water-free tobacco is shown in the +following table:<a id="FNanchor_617" href="#Footnote_617" class="fnanchor">[617]</a></p> + +<table class="spb1 spa1"> + <thead><tr> + <th class="tdc"> </th> + <th class="tdc bb"> Havana, <br>per cent.</th> + <th class="tdc bb"> Sumatra, <br>per cent.</th> + <th class="tdc bb"> Kentucky, <br>per cent.</th> + <th class="tdc bb">Java,<br> per cent. </th> + </tr></thead> + <tbody><tr> + <td class="tdl">Nicotin</td> + <td class="tdr_ws1">3.98</td> + <td class="tdr_ws1">2.38</td> + <td class="tdr_ws1">4.59</td> + <td class="tdr_ws1">3.30</td> + </tr><tr> + <td class="tdl">Malic acid</td> + <td class="tdr_ws1">12.11</td> + <td class="tdr_ws1">11.11</td> + <td class="tdr_ws1">11.57</td> + <td class="tdr_ws1">6.04</td> + </tr><tr> + <td class="tdl">Citric acid</td> + <td class="tdr_ws1">2.05</td> + <td class="tdr_ws1">2.53</td> + <td class="tdr_ws1">3.40</td> + <td class="tdr_ws1">3.30</td> + </tr><tr> + <td class="tdl">Oxalic acid</td> + <td class="tdr_ws1">1.53</td> + <td class="tdr_ws1">2.97</td> + <td class="tdr_ws1">2.03</td> + <td class="tdr_ws1">3.38</td> + </tr><tr> + <td class="tdl">Acetic acid</td> + <td class="tdr_ws1">0.42</td> + <td class="tdr_ws1">0.29</td> + <td class="tdr_ws1">0.43</td> + <td class="tdr_ws1">0.22</td> + </tr><tr> + <td class="tdl">Tannic acid</td> + <td class="tdr_ws1">1.13</td> + <td class="tdr_ws1">0.98</td> + <td class="tdr_ws1">1.48</td> + <td class="tdr_ws1">0.51</td> + </tr><tr> + <td class="tdl">Nitric acid</td> + <td class="tdr_ws1">1.32</td> + <td class="tdr_ws1">0.60</td> + <td class="tdr_ws1">1.88</td> + <td class="tdr_ws1">0.23</td> + </tr><tr> + <td class="tdl">Pectic acid</td> + <td class="tdr_ws1">11.36</td> + <td class="tdr_ws1">11.88</td> + <td class="tdr_ws1">8.22</td> + <td class="tdr_ws1">10.13</td> + </tr><tr> + <td class="tdl">Cellulose</td> + <td class="tdr_ws1">15.76</td> + <td class="tdr_ws1">10.59</td> + <td class="tdr_ws1">12.48</td> + <td class="tdr_ws1">11.82</td> + </tr><tr> + <td class="tdl">Ammonia</td> + <td class="tdr_ws1">0.49</td> + <td class="tdr_ws1">0.06</td> + <td class="tdr_ws1">0.19</td> + <td class="tdr_ws1">0.23</td> + </tr><tr> + <td class="tdl">Soluble nitrogenous matter</td> + <td class="tdr_ws1">7.74</td> + <td class="tdr_ws1">8.84</td> + <td class="tdr_ws1">13.90</td> + <td class="tdr_ws1">10.39</td> + </tr><tr> + <td class="tdl">Insoluble<span class="ws2">”</span><span class="ws3">”</span></td> + <td class="tdr_ws1">9.75</td> + <td class="tdr_ws1">7.97</td> + <td class="tdr_ws1">8.10</td> + <td class="tdr_ws1">9.53</td> + </tr><tr> + <td class="tdl">Residue and chlorophyll</td> + <td class="tdr_ws1">5.15</td> + <td class="tdr_ws1">8.63</td> + <td class="tdr_ws1">1.99</td> + <td class="tdr_ws1">6.45</td> + </tr><tr> + <td class="tdl">Oil</td> + <td class="tdr_ws1">1.03</td> + <td class="tdr_ws1">1.26</td> + <td class="tdr_ws1">2.28</td> + <td class="tdr_ws1">0.81</td> + </tr><tr> + <td class="tdl">Ash</td> + <td class="tdr_ws1">17.50</td> + <td class="tdr_ws1">17.03</td> + <td class="tdr_ws1">14.36</td> + <td class="tdr_ws1">18.46</td> + </tr><tr> + <td class="tdl">Undetermined</td> + <td class="tdr_ws1">8.68</td> + <td class="tdr_ws1">12.88</td> + <td class="tdr_ws1">13.10</td> + <td class="tdr_ws1">15.20</td> + </tr> + </tbody> +</table> + +<p><span class="pagenum"><a id="Page_599"></a>[Pg 599]</span> +Among the undetermined matters are included those of a gummy or +resinous composition not extracted by ether, the exact nature of +which is not well understood, and the starches, sugars, pentosans and +galactan.</p> + +<p>Tobacco grown in more northern latitudes has less nicotin than the +samples given in the foregoing table.</p> + +<p>The following table shows the composition of tobacco grown in +Connecticut:<a id="FNanchor_618" href="#Footnote_618" class="fnanchor">[618]</a></p> + +<ul class="index fs_105 spa1"> +<li class="isub3"><b>(A)</b> = Unfermented,</li> +<li class="isub3"><b>(B)</b> = Fermented,</li> +</ul> + + <table class="spb1 spa1"> + <thead><tr> + <th class="tdc"> </th> + <th class="tdc fs_105" colspan="2"> Upper leaves. </th> + <th class="tdc fs_105" colspan="2"> Short seconds. </th> + <th class="tdc fs_105" colspan="2"> First wrappers. </th> + </tr><tr> + <th class="tdc"> </th> + <th class="tdc bb fs_105">(A)<br>%</th> + <th class="tdc bb fs_105">(B)<br>%</th> + <th class="tdc bb fs_105">(A)<br>%</th> + <th class="tdc bb fs_105">(B)<br>%</th> + <th class="tdc bb fs_105">(A)<br>%</th> + <th class="tdc bb fs_105">(B)<br>%</th> + </tr></thead> + <tbody><tr> + <td class="tdl">Water</td> + <td class="tdr_wsp">23.50</td> + <td class="tdr_wsp">23.40</td> + <td class="tdr_wsp">27.40</td> + <td class="tdr_wsp">21.10</td> + <td class="tdr_wsp">27.50</td> + <td class="tdr_wsp">24.90</td> + </tr><tr> + <td class="tdl">Pure ash</td> + <td class="tdr_wsp">14.89</td> + <td class="tdr_wsp">15.27</td> + <td class="tdr_wsp">22.85</td> + <td class="tdr_wsp">25.25</td> + <td class="tdr_wsp">15.84</td> + <td class="tdr_wsp">16.22</td> + </tr><tr> + <td class="tdl">Nicotin</td> + <td class="tdr_wsp">2.50</td> + <td class="tdr_wsp">1.79</td> + <td class="tdr_wsp">0.77</td> + <td class="tdr_wsp">0.50</td> + <td class="tdr_wsp">1.26</td> + <td class="tdr_wsp">1.44</td> + </tr><tr> + <td class="tdl">Nitric acid</td> + <td class="tdr_wsp">1.89</td> + <td class="tdr_wsp">1.97</td> + <td class="tdr_wsp">2.39</td> + <td class="tdr_wsp">2.82</td> + <td class="tdr_wsp">2.59</td> + <td class="tdr_wsp">2.35</td> + </tr><tr> + <td class="tdl">Ammonia</td> + <td class="tdr_wsp">0.67</td> + <td class="tdr_wsp">0.71</td> + <td class="tdr_wsp">0.16</td> + <td class="tdr_wsp">0.16</td> + <td class="tdr_wsp">0.33</td> + <td class="tdr_wsp">0.47</td> + </tr><tr> + <td class="tdl">Proteids</td> + <td class="tdr_wsp">12.19</td> + <td class="tdr_wsp">13.31</td> + <td class="tdr_wsp">6.69</td> + <td class="tdr_wsp">6.81</td> + <td class="tdr_wsp">11.31</td> + <td class="tdr_wsp">11.62</td> + </tr><tr> + <td class="tdl">Fiber</td> + <td class="tdr_wsp">7.90</td> + <td class="tdr_wsp">8.78</td> + <td class="tdr_wsp">7.89</td> + <td class="tdr_wsp">8.95</td> + <td class="tdr_wsp">9.92</td> + <td class="tdr_wsp">10.42</td> + </tr><tr> + <td class="tdl">Starch</td> + <td class="tdr_wsp">3.20</td> + <td class="tdr_wsp">3.36</td> + <td class="tdr_wsp">2.62</td> + <td class="tdr_wsp">3.01</td> + <td class="tdr_wsp">2.89</td> + <td class="tdr_wsp">3.08</td> + </tr><tr> + <td class="tdl">Oil and fat</td> + <td class="tdr_wsp">3.87</td> + <td class="tdr_wsp">3.42</td> + <td class="tdr_wsp">2.95</td> + <td class="tdr_wsp">3.04</td> + <td class="tdr_wsp">2.84</td> + <td class="tdr_wsp">2.92</td> + </tr><tr> + <td class="tdl">Undeterm’d</td> + <td class="tdr_wsp">29.39</td> + <td class="tdr_wsp">27.99</td> + <td class="tdr_wsp">26.28</td> + <td class="tdr_wsp">28.36</td> + <td class="tdr_wsp">25.52</td> + <td class="tdr_wsp">26.88</td> + </tr> + </tbody> +</table> + +<p><b>600. Estimation of Water.</b>—In the estimation of water in +vegetable substances, as has already been noted, it is usual to dry +them in the air or partial vacuum, or in an inert gas, at a temperature +of 100° until a constant weight is reached. By this process, not only +the water, but all substances volatile at the temperature and in the +conditions mentioned are expelled. The quantity of these volatile +substances in vegetable matter, as a rule, is insignificant and hence +the total loss may be estimated as water. In the case of tobacco a +far different condition is presented, inasmuch as the nicotin, which +sometimes amounts to five per cent of the weight of the sample, is also +volatile under the conditions mentioned. It is advisable, therefore, to +dry the sample of tobacco at a temperature not above fifty degrees and +in a vacuum as complete as possible. Tobacco is also extremely rich in +its content of crystallized mineral salts, containing often water of +crystallization, and there is danger of this crystal water being lost +when the sample is dried at 100°. The desiccation is conveniently made +in the apparatus described on <a href="#Page_22">page 22</a>. If a high vacuum be employed, +<span class="pagenum"><a id="Page_600"></a>[Pg 600]</span> +<i>viz.</i>, about twenty-five inches of mercury, it is better not to +allow the temperature to go above 40° or 45°. A rather rapid current of +dry air should be allowed to pass through the apparatus for the more +speedy removal of the moisture and a dish containing sulfuric acid +may also be placed inside of the drying apparatus. It is possible by +proceeding in this way to secure constant weight in the sample after a +few hours.</p> + +<p><b>601. Estimation of Nitric Acid.</b>—The nitric acid in a sample +of tobacco is most easily estimated by the ferrous chlorid +process.<a id="FNanchor_619" href="#Footnote_619" class="fnanchor">[619]</a></p> + +<p>The sample is best prepared by making an alcoholic extract which is +accomplished by exhausting about twenty-five grams of the fine tobacco +powder with 200 cubic centimeters for forty per cent alcohol made +slightly alkaline by soda lye. The mixture is boiled in a flask with +a reflux condenser for about an hour. After cooling, the volume is +completed to a definite quantity, and, after filtering, an aliquot +part is used for the analytical process. It is evident that the nitric +acid cannot be estimated in this case after previous reduction to +ammonia by zinc or iron on account of the presence of ammonia in the +sample itself. If, however, the amount of ammonia be determined in a +separate portion of the sample, the nitric acid may be reduced in the +usual way, by zinc or iron, the total quantity of ammonia determined by +distillation, the quantity originally present in the sample deducted +and the residual ammonia calculated to nitric acid.</p> + +<p><b>602. Sulfuric and Hydrochloric Acids.</b>—These two acids are +determined in the ash of the sample by the usual methods. The sulfuric +acid thus found represents the original sulfuric acid in combination +with the bases in the mineral parts of the plant, together with that +produced by the oxidation of the organic sulfur during combustion. +In order to avoid all loss of sulfur during the combustion, the +precautions already given should be observed. The separation of the +sulfur pre-existing as sulfates from that converted into sulfates during +the combustion is accomplished as previously directed.<a id="FNanchor_620" href="#Footnote_620" class="fnanchor">[620]</a> +For ordinary purposes, this separation is not necessary.</p> + +<p>To avoid loss of chlorin from volatilization during incineration the +<span class="pagenum"><a id="Page_601"></a>[Pg 601]</span> +temperature should be kept at the lowest possible point until the mass +is charred, the soluble salts extracted from the charred mass and the +incineration completed as usual.</p> + +<p><b>603. Oxalic, Citric and Malic Acids.</b>—The separation and +estimation of organic acids from vegetable tissues is a matter of great +difficulty, especially when they exist as is usually the case, in very +minute proportions. During incineration, the salts of the inorganic +acids are converted into carbonates and the subsequent examination of +the ash gives no indication of the character of the original acids. In +the case of tobacco, the organic acids of chief importance, from an +analytical point of view, are oxalic, citric and malic. These acids may +be extracted and separated by the following process:<a id="FNanchor_621" href="#Footnote_621" class="fnanchor">[621]</a></p> + +<p>Ten grams of the dry tobacco powder are rubbed up in a mortar with +twelve cubic centimeters of dilute sulfuric acid (one to five) and then +absorbed with coarse pumice stone powder in sufficient quantity to +cause all the liquid to disappear. The mass is placed in an extraction +apparatus of proper size and thoroughly extracted with ether until a +drop of the extract leaves no acid residue on evaporation. Usually +about ten hours are required. The organic acids are thus separated +from the mineral acids. The ether is removed from the extract and the +residue dissolved in hot water, cooled, filtered, if necessary several +times, until the solution is separated from the fat and resin which +have been extracted by the ether. The filtrate is neutralized with +ammonia, slightly acidified with acetic and the oxalic acid contained +therein thrown out by means of a dilute solution of calcium acetate, +which must not be added in excess. The calcium oxalate is separated by +filtration, and determined as lime oxid. To the filtrate is added drop +by drop, with constant stirring, a dilute solution of lead acetate, +prepared by mixing one part of a saturated solution of lead acetate +with four parts of water. When the precipitate formed has settled, the +clear supernatant liquid is tested by adding a drop of acetic acid +and a few drops of the dilute lead acetate. In case a precipitate +be formed, the addition of the lead acetate is continued until a +precipitate is secured which will immediately dissolve in acetic acid. +<span class="pagenum"><a id="Page_602"></a>[Pg 602]</span> +At this moment the citric acid is almost completely precipitated. +In order to avoid the accumulation of the acetic acid by reason of +the repetition of the process as above described, the mixture is +neutralized each time with dilute ammonia. The precipitated neutral +lead citrate obtained by the above process, is separated by filtration +and, in order to avoid its decomposition when washed with pure water, +it is washed with a very dilute acetic acid solution of lead acetate. +The washing and filtration are accomplished as quickly as possible, +and the final washing is made with alcohol of thirty-six per cent +strength. In the filtrate the residual lead citrate, together with a +little lead malate, are precipitated by the alcohol used as the wash +and this precipitate is also separated by filtration. The filtrate +containing the greater part of the malic acid is evaporated to remove +the alcohol and treated with lead acetate in excess. Afterwards it +is mixed with five times its volume of thirty-six per cent alcohol +containing a half per cent of acetic acid. In these conditions the lead +malate is completely precipitated as neutral salt, and after standing a +few hours, is separated by filtration. The three precipitates, obtained +as above, are dried at 100° and weighed. If the precipitates have +been collected on filter paper they should be removed as completely +as possible, the papers incinerated in the usual way and any reduced +lead converted into nitrate and oxid by treatment with nitric acid and +subsequent ignition. From the quantities of lead oxid obtained, the +weights of the citric and malic acids are computed. The precipitate +which is obtained by the action of alcohol, above noted, is also dried +and ignited and the lead oxid found divided equally between the citric +and malic acids, the respective quantities of which found, are included +in computing their total weights. The weight of the citric acid is +calculated from the formula <b>(C₆H₅O₇)₂Pb₃ + H₂O</b>, and that of the malic +acid from the formula <b>C₄H₄O₅Pb + H₂O</b>.</p> + +<p><b>604. Acetic Acid.</b>—For the determination of the volatile acids +of the fatty series existing in tobacco, the following process, also +due to Schlösing, may be followed:<a id="FNanchor_622" href="#Footnote_622" class="fnanchor">[622]</a></p> + +<p>The apparatus employed is shown in <a href="#FIG_121">Fig. 12</a>1. Ten grams of the pulverized +<span class="pagenum"><a id="Page_603"></a>[Pg 603]</span> +tobacco, moistened with water and mixed with a little powdered tartaric +acid, are placed in the tube <i>A</i>. The two ends of the tube, +<i>A</i>, are stoppered with asbestos or glass wool. Steam, generated +in the flask, <i>D</i>, is passed into <i>B</i>. After fifteen minutes, +or as soon as it is certain that the contents of <i>A</i> have reached +a temperature of 100°, the dish, <i>F</i>, containing mercury, is +placed in the position shown in the <a href="#FIG_121">figure</a>. The steam, +by this arrangement, is forced into the lower end of <i>A</i>, passes into the +condenser <i>E</i>, and the condensed water collected in <i>C</i>. The +operation should be so conducted as to avoid any condensation of water +in <i>B</i>. It is advisable during the progress of the distillation, +which should continue for at least twenty minutes, to neutralize from +time to time the acetic acid collected in <i>C</i> by a set solution of +dilute alkali, or, an excess of the alkaline solution may be placed in +<i>C</i> and the part not neutralized by the acetic acid determined at +the end of the distillation by titration.</p> + +<div class="figcenter smcap"> + <img id="FIG_121" src="images/fig121.jpg" alt="" width="600" height="297" > + <p class="center spb1">Fig. 121.—Apparatus for Acetic Acid.</p> +</div> + +<p><b>605. Pectic Acid.</b>—Under this term are included not only the +pectic acid but all the other bodies of a pectose nature contained in +tobacco. These bodies are of considerable interest, although they do +not belong to the most important constituents. In fresh tobacco leaves +are found three pectin bodies. One pectin is soluble in water, another +is an insoluble pectose and the third is the pectose body forming +salts with the alkalies, <i>i. e.</i>, true pectic acid. In fermented +tobacco pectic acid is found chiefly in combination with lime in the +ribs of the leaves, serving to give them the necessary stiffness. For +the estimation of the pectin bodies (mucilage) the powdered tobacco is +<span class="pagenum"><a id="Page_604"></a>[Pg 604]</span> +thoroughly extracted with cold water. An aliquot part of the aqueous +extract is mixed with two volumes of strong alcohol and allowed to +stand in a well closed vessel in a cool place for twenty-four hours. +The precipitate is collected on a filter, washed with sixty-six per +cent alcohol, dried and weighed. The dried residue is incinerated and +the amount of ash determined. In general, vegetable mucilages contain +about five per cent of ash. If more than this be found, it is due to +the solution of the salts of the organic acids contained in the sample. +A dried vegetable mucilage, obtained as above, dissolves in water to +a mucilaginous liquid which does not reduce alkaline copper solution +until it has been hydrolyzed by boiling with a dilute mineral acid.<a id="FNanchor_623" href="#Footnote_623" class="fnanchor">[623]</a></p> + +<p><b>606. Tannic Acid.</b>—This acid is separated and estimated by the +processes given in paragraphs <b><a href="#P_589">589-595</a></b>.</p> + +<p><b>607. Starch and Sugar.</b>—The unfermented leaves of tobacco +contain considerable quantities of carbohydrates in addition to woody +fiber, pentosans, galactan and cellulose. Among these, starch is the +most important. Sugar exists in small quantities in the fresh leaf, +usually not over one per cent. During fermentation, according to some +authorities, the starch is partially converted into sugar and the +latter substance disappears under the action of the alcoholic ferments. +It has been found at the Connecticut Station, however, that the starch +content of the leaf does not decrease during fermentation. The starch +and sugar may be determined in the fresh leaves by the methods already +given.</p> + +<p>In the manufacture of certain grades of tobacco it is customary to add +a quantity of sugar. The analyst may thus be called upon to determine +in some cases whether the sugar found in a sample is natural or added. +The occurrence of natural sugars in tobacco has been investigated at +the instance of the British Treasury.<a id="FNanchor_624" href="#Footnote_624" class="fnanchor">[624]</a></p> + +<p>The natural sugars which may be found in sun dried tobaccos usually +disappear entirely during the process of fermentation. It was found by +the Somerset House chemists that the content of sugar in commercial +tobaccos varies from none at all to over fifteen per cent. A remarkable +example of this variation is reported in two samples from this country, +<span class="pagenum"><a id="Page_605"></a>[Pg 605]</span> +one of which, grown in Kentucky, contained no sugar, and the other +grown in Virginia, 15.2 per cent.</p> + +<p>It was noticed that the saccharin matters in the tobaccos examined +were neutral to polarized light. They are determined by their copper +reducing power. The tobacco sugars are therefore to be classed with the +reducing bodies, not optically active, found in the juices of sorghum +and sugar canes.</p> + +<p><b>608. Ammonia.</b>—As has already been intimated, ammonia exists +only in minute quantities in fresh tobacco leaves, but in considerable +quantities after fermentation. In the estimation of ammonia, twenty +grams of the tobacco powder are digested with 250 cubic centimeters of +water, acidulated with sulfuric and after an hour enough water added +to make the total quantity 400 cubic centimeters. After filtration, an +aliquot part of the filtrate, about 200 cubic centimeters, is treated +with magnesium oxid in excess and the ammonia and nicotin removed by +distillation in a current of steam. The distillate is collected in +dilute sulfuric acid of known strength. The total amount of the two +bases is determined by titration and the quantity of base representing +the nicotin, which has been determined in a separate sample, subtracted +in order to obtain the weight of the ammonia.<a id="FNanchor_625" href="#Footnote_625" class="fnanchor">[625]</a></p> + +<p>The ammonia in tobacco is determined by Nessler in the following +manner:<a id="FNanchor_626" href="#Footnote_626" class="fnanchor">[626]</a></p> + +<p>The powdered tobacco is mixed with water and magnesium oxid and after +standing for several hours it is distilled in a current of steam, the +distillate received in dilute sulfuric acid and the process continued +until a drop of the distillate gives no reaction for ammonia with the +nessler reagent. The excess of sulfuric acid in the distillate is +neutralized with pure sodium carbonate and the nicotin precipitated +by a neutral solution of mercuric iodid and potassium iodid. The +precipitate is separated by filtration, the filtrate treated with +sodium sulfid, and the ammonia again obtained by distillation with +an alkali, collected in dilute solution of set sulfuric acid and +determined by titration. The difference of the two determinations +represents the ammonia.</p> + +<p><b>609. Nicotin.</b>—In this laboratory McElroy has made a study of +<span class="pagenum"><a id="Page_606"></a>[Pg 606]</span> +some of the best approved methods for determining nicotin, and finds +the most simple and reliable to be that proposed by Kissling.<a id="FNanchor_627" href="#Footnote_627" class="fnanchor">[627]</a> +The finely powdered tobacco should be dried at a temperature not +exceeding 60°, or it may be partially dried at that temperature before +grinding and the final drying completed afterwards. Twenty grams of +the powdered sample are intimately mixed by means of a pestle with +ten cubic centimeters of dilute alcoholic solution of soda lye, made +by dissolving six grams of sodium hydroxid in forty cubic centimeters +of water and completing the volume to 100 cubic centimeters with +ninety-five per cent alcohol. The mass is transferred to an extraction +paper cylinder, placed in an extraction apparatus and extracted for +three hours with ether. The ether is nearly all removed by careful +distillation, the residue mixed with fifty cubic centimeters of a very +dilute soda lye solution (4 to 100) and subjected to distillation in +a current of steam. The flask containing the nicotin extract should +be connected with the condensing apparatus by a safety bulb as is +usual in the distillation of substances containing fixed alkali. The +distillation should be conducted rapidly and in such a manner that when +200 cubic centimeters of the distillate have been collected, not more +than fifteen cubic centimeters of the liquid remain in the distillation +flask. In the distillate, the nicotin is determined by titration +with a set solution of dilute sulfuric acid, using rosolic acid or +phenacetolin as indicator. It is advisable to titrate each fifty cubic +centimeters of the distillate as it is received and the distillation is +continued until the last fifty cubic centimeters give no appreciable +quantity of the alkaloid. In the calculations one molecule of sulfuric +acid is equivalent to two molecules of nicotin according to the equation</p> + +<ul class="index"> +<li class="isub4"><b>H₂SO₄</b> = <b>(C₁₀H₁₄N₂)₂</b>.</li> +<li class="isub5">98<span class="ws4">324</span></li> +</ul> + +<p><i>Polarization Method.</i>—Popovici has based a method of detecting +the quantity of nicotin in tobacco on its property of rotating the +plane of polarized light.<a id="FNanchor_628" href="#Footnote_628" class="fnanchor">[628]</a> +The gyrodynat of pure nicotin is expressed by the formula +[<i>a</i>]<span class="fs_80"><sub>D</sub></span> = -161°.6. When ten +parts of nicotin are mixed with ninety parts of water, this value +becomes -74°.1. By reason of this great depression in gyrodynatic value +<span class="pagenum"><a id="Page_607"></a>[Pg 607]</span> +Popovici determined the relation which exists between the dilute +solutions of nicotin and the number of minutes of angular rotation +produced on polarization in a 200 millimeter tube. In a solution in +which two grams of nicotin are contained in fifty cubic centimeters, +each minute of angular rotation is found to correspond to 6.5 +milligrams of nicotin. For one gram in solution in the same volume one +minute of angular rotation corresponds to 5.9 milligrams and for a half +gram in solution to 5.7 milligrams.</p> + +<p>The nicotin is prepared for polarization by extracting with ether, as +indicated in the previous paragraph, and the ethereal solution from +twenty grams of tobacco is shaken with a concentrated solution of +sodium phosphotungstate in nitric acid by means of which nicotin and +ammonia are precipitated and rapidly settle. The supernatant liquid +is carefully poured off and the residue made up to a volume of fifty +cubic centimeters with distilled water and the nicotin freed from any +of its compounds by the addition of eight grams of finely powdered +barium hydroxid. In order to promote the decomposition of the nicotin +compounds the mixture should be shaken at intervals for several hours. +The at first blue precipitate changes into blue green and finally into +yellow. It is separated by filtration and the somewhat yellow colored +filtrate placed in an observation tube, polarized, the polarization +calculated to minutes of angular rotation and the number of minutes +thus found multiplied by the nearest factor given above.</p> + +<p>The analyst will find a description of other methods of estimating +nicotin in tobacco in the periodical literature of analytical +chemistry.<a id="FNanchor_629" href="#Footnote_629" class="fnanchor">[629]</a></p> + +<p><b>610. Estimation of Amid Nitrogen.</b>—For the estimation of amid +nitrogen ten grams of the powdered tobacco are digested with 100 +cubic centimeters of forty per cent alcohol, the extract separated by +filtration, acidified with sulfuric and the albumin, peptone, nicotin +and ammonia precipitated with as little phosphotungstic acid as +possible. The precipitate is separated by filtration and seventy-five +cubic centimeters of the filtrate evaporated in a thin glass or tin +foil capsule after the addition of a little barium chlorid and the +nitrogen determined in the residue. The nitrogen thus obtained is that +<span class="pagenum"><a id="Page_608"></a>[Pg 608]</span> +which was present in an amid state. The nitrogen present as amids, +ammonia and nicotin subtracted from the total nitrogen leaves that +present as protein.</p> + +<p><b>611. Fractional Extraction of Tobacco.</b>—To determine the +character of the soluble constituents of tobacco it is advisable +to subject it to a fractional extraction with different reagents. +The reagents usually employed in the order mentioned are petroleum +ether, ether, absolute alcohol, water, dilute soda lye and dilute +hydrochloric acid. The extract obtained by petroleum ether contains +vegetable wax, chlorophyll and its alteration products, fat, ethereal +oils, and resin bodies. The extract with ether may be divided into +water soluble and alcohol soluble bodies. Among the first are small +quantities of glucosids and nicotin while in the alcoholic solution +resin predominates.</p> + +<p>The alcoholic extract is also divided into water soluble and alcohol +soluble parts. The first contains the nicotin, which is insoluble in +ether, in combination with acids, together with tannic acid and allied +bodies and also the sugar. The part insoluble in water consists chiefly +of resin.</p> + +<p>The aqueous solution contains the vegetable mucilages (pectin) soluble +carbohydrates, soluble proteids and organic acids.</p> + +<p>The dilute soda lye solution contains chiefly proteids.</p> + +<p>The dilute hydrochloric acid solution contains the starch and the +oxalic acid originally combined with lime. The extractions with dilute +soda lye and dilute hydrochloric acid should be made at a boiling +temperature. The residual matter consists of a mixture of carbohydrate +bodies to which the term crude fiber is usually applied.</p> + +<p><b>612. Burning Qualities.</b>—When tobacco is to be used for the +manufacture of cigars, or cigarettes, or for smoking in pipes, its +ability to keep burning is a matter of great importance. The tobacco, +when once ignited, should burn for some time and form, a fluffy ash, +free of fused mineral particles. A tobacco with good burning properties +is one containing nitrates in considerable quantity, not too much sugar +and starch, a porous cellular structure and comparatively free of +chlorin. In determining comparative burning properties the tests may be +<span class="pagenum"><a id="Page_609"></a>[Pg 609]</span> +applied to the single leaf or the tobacco may be first rolled into a +cigar form and burned in an artificial smoker.</p> + +<div class="figleft smcap"> + <img id="FIG_122" src="images/fig122.jpg" alt="" width="200" height="509" > + <p class="center">Fig. 122.<br> Apparatus for Smoking.</p> +</div> + +<p>In applying the test to the leaf it is important that the ignition +be made with a fuse without flame, which maintains a uniform burning +power. Any good slow burning fuse may be used and it is applied to the +leaf in such a way that a hole may be burned in it, leaving its edges +uniformly ignited. The number of seconds elapsing before the last spark +is extinguished is noted. At the Connecticut Experiment Station a +lighter, proposed by Nessler, is employed. It is prepared by digesting +eighty grams of gum arabic in 120 cubic centimeters, and forty grams of +gum tragacanth in a quarter of a liter of water for two days, mixing +the mucilaginous masses and adding ten grams of potassium nitrate and +about 350 grams of pulverized charcoal. The mixture is rolled, on a +plate sprinkled with charcoal, into sticks a few inches in length and +of the diameter of a cigar and dried at a gentle heat. These fuses +burn slowly and without smoke and are well suited for lighting tobacco +leaves. Several tests, at least six, should be made with each leaf. +Leaves having a uniform burning power should be used as comparators and +the number of seconds they burn be designated by 100. It is important +that all the samples to be tested be exposed for a day or two to the +same atmosphere in order that they may have, as nearly as possible, +the same content of moisture. The burning tests, when possible, should +be made both before and after fermentation. As a rule fermentation +improves the burning quality of second rate leaves, but has little +effect on leaves of the first quality.</p> + +<p><b>613. Artificial Smoker.</b>—For the purpose of comparing the +burning properties of cigars, or of leaves rolled into cigar form, the +artificial smoking apparatus devised by Penfield and modified in this +laboratory is employed.<a id="FNanchor_630" href="#Footnote_630" class="fnanchor">[630]</a> +The construction of the apparatus is shown in the accompanying <a href="#FIG_122">figure.</a></p> + +<p>The lighted cigar is set in the tube at the left, so that air entering +<span class="pagenum"><a id="Page_610"></a>[Pg 610]</span> +the test-tube must pass through the cigar. The test-tube contains +enough water to seal the end of the tube carrying the cigar, and is +connected with the aspirator on the right by the <b>T</b> tube, as +shown. An arm of the <b>T</b> dips just beneath the surface of the +liquid in the cup in the center. Water flows in a slow stream into the +aspirator through the tube at the extreme right, forcing the air out +through the arm of the <b>T</b> until the siphon begins to act. While +the water is voided through the long arm of the siphon, air enters +through the cigar, the liquid rising in the <b>T</b>. The action of +the apparatus is automatic and intermittent. When the cigar is about +one-third burned, it is removed without disturbing the ash cone, and +the latter examined and compared with other samples as a standard. The +sealing liquid of the long arm of the <b>T</b> may be mercury or water. +In case mercury be used, care must be taken not to immerse the open end +of the <b>T</b> more than one millimeter therein.</p> + +<h3>FERMENTED BEVERAGES.</h3> + +<p><b>614. Description.</b>—Among fermented beverages are included +those drinks, containing alcohol, prepared by fermenting the sugars +or starches of fruits, cereals or other agricultural products. Wine +and beer, in their various forms, and cider are the chief members +of this class of bodies. Koumiss, although a fermented beverage, is +not included in this classification, having been noticed under dairy +products. The large number of artificial drinks, made by mixing alcohol +with fruit and synthesized essences, is also excluded, although the +methods of analysis which are used may be applied also to them.</p> + +<p>Fermented beverages containing less than two per cent of alcohol are +<span class="pagenum"><a id="Page_611"></a>[Pg 611]</span> +usually regarded as non-intoxicating drinks. Beers are of several +varieties, and the term includes lager beer, ale, porter and stout. +Distilled liquors are obtained by separating the alcohols and other +volatile matters from the products of fermentation by distillation. +It is not practicable here to attempt a description of the methods of +preparing fermented drinks. Special works on this branch of the subject +are easy of access.<a id="FNanchor_631" href="#Footnote_631" class="fnanchor">[631]</a></p> + +<p><b>615. Important Constituents.</b>—Alcohol is the most important +constituent of fermented beverages. The solid matters, commonly called +extract, which are obtained on evaporation are composed of dextrins, +sugars, organic acids, nitrogenous bodies and mineral matters affording +ash on combustion. Of these the dextrins and sugars form the chief part +and the proteid bodies nearly ten per cent in the case of beers made of +malt and hops. In beers the bitter principles derived from hops, while +not important by reason of quantity, are of the utmost consequence from +a gustatory and hygienic point of view. The ash of fermented beverages +varies with their nature, or with the character of the water used +in making the mash. In the manufacture of beer, water containing a +considerable proportion of gypsum is often used, and this substance is +sometimes added in the course of manufacture, especially of wine. The +presence of common salt in the ash in any notable quantity is evidence +of the addition of this condiment, either to improve the taste of the +beverage or to increase the thirst of the drinker. In cider the organic +acids, especially malic, are of importance.</p> + +<p>Glycerol is a product of fermentation and of the hydrolysis of the fats +and oils in the substances fermented.</p> + +<p><b>616. Specific Gravity.</b>—In order to secure uniformity of +expression, the specific gravity of fermented beverages is determined +at about 15°.6, although that is a temperature much below the average +found in American laboratories. The specific gravity may be determined +by an alcoholometer, pyknometer or hydrostatic balance in harmony with +the directions given in paragraphs <b><a href="#P_48">48-54</a></b> +and <b><a href="#P_285">285</a></b>. By reason of the extractive +matters held in solution, fermented beverages are usually heavier than +water, even if the content of alcohol be twenty per cent or more. On +the other hand distilled liquors are lighter than water. +<span class="pagenum"><a id="Page_612"></a>[Pg 612]</span></p> + +<p><b>617. Determination of Alcohol.</b>—The determination of the +percentage of alcohol present in a solution is based on two general +principles. On the one hand, and this is the base of the methods in +common use, the alcohol is secured mixed only with water and its amount +determined by ascertaining the specific gravity of the mixture. On the +other hand the quantity of alcohol in a mixture may be determined by +ascertaining the temperature of the vapors produced on boiling. This +is the principle involved in the use of the ebullioscope. The latter +method is not employed to any extent in this country.</p> + +<p><i>Use of the Alcoholometer.</i>—The alcoholometer usually employed +is known by the name of Gay-Lussac, who first made practical use of it +in the determination of alcohol. It is constructed in such a way as to +read directly the volume of absolute alcohol contained in one hundred +volumes of the liquid at a temperature of 15°.6. The instruments +employed should be carefully calibrated and thoroughly cleaned by +washing with absolute alcohol before use. The stem of the instrument +must be kept free from any greasy substance, and this is secured by +washing it with ether. After this last washing the analyst should be +careful not to touch the stem of the instrument with his fingers. It is +most convenient to make the determination exactly at 15°.6, but when +made at other temperatures the reading of the instrument is corrected +by tables which may be found in works especially devoted to the +analysis of wines.<a id="FNanchor_632" href="#Footnote_632" class="fnanchor">[632]</a></p> + +<p>In this country the alcoholometer is used to some extent, but the +official method is based upon the determination of the specific gravity +by an instrument constructed in every respect like the alcoholometer, +but giving the specific gravity of the liquor at 15°.6 instead of its +percentage by volume in alcohol. The reading of the instrument having +been determined at a temperature of 15°.6, the corresponding percentage +of alcohol by volume or by weight is taken directly from the table +given further on.</p> + +<div class="figcenter smcap"> + <img id="FIG_123" src="images/fig123.jpg" alt="" width="400" height="485" > + <p class="center spb1">Fig. 123. Metal Distilling Apparatus.</p> +</div> + +<p><i>Methods of Distillation.</i>—The metal apparatus employed in the +laboratory of the Department of Agriculture, for the distillation of +fermented beverages in order to determine the percentage of alcohol by +<span class="pagenum"><a id="Page_613"></a>[Pg 613]</span> +the method given above, is shown in the accompanying <a href="#FIG_123">figure</a>. +The apparatus consists of a retort of copper carried on supports in such a +way as to permit an alcohol or bunsen lamp to be placed under it. It +is connected with a block tin condenser and the distillate is received +in a tall graduated cylinder placed under the condenser in such a way +as to prevent the loss of any alcohol in the form of vapor. Exactly +300 cubic centimeters of the wine or fermented beverage are used for +the distillation. Any acid which the wine contains is first saturated +with calcium carbonate before placing in the retort. Exactly 100 +cubic centimeters of distillate are collected and the volume of the +distillate is completed to 300 cubic centimeters by the addition of +recently distilled water.<a id="FNanchor_633" href="#Footnote_633" class="fnanchor">[633]</a> +The cylinder containing the distillate is brought to a temperature of 15°.6, +the alcoholometer inserted and its reading taken with the usual precautions.</p> + +<p><i>Official Method.</i>—The alcoholometers employed in the official +methods are calibrated to agree with those used by the officers of the +Bureau of Internal Revenue. They are most conveniently constructed, +carrying the thermometer scale in the same stem with that showing +the specific gravity. It is highly important that the analyst assure +himself of the exact calibration of the instrument before using it. +Inasmuch as the volume of the distillate may not be suited in all cases +to the use of a large alcoholometer, it is customary in this laboratory +to determine the specific gravity by means of the hydrostatic balance, +as described further on. Attention is also called to the fact that, +in the official method, directions are not given to neutralize the +free acid of the fermented beverage before the distillation. Since the +Internal Revenue Bureau is concerned chiefly with the determination of +alcohol in distilled liquors, this omission is of little consequence. +Even in ordinary fermented beverages the percentage of volatile acids, +(acetic etc.,) is so small as to make the error due to the failure to +<span class="pagenum"><a id="Page_614"></a>[Pg 614]</span> +neutralize it of but little consequence. In order, however, to avoid +every possibility of error, it is recommended that in all instances the +free acids of the sample be neutralized before distillation. In this +laboratory, the distillations are conducted in a glass apparatus shown +in the accompanying <a href="#FIG_124">figure</a>. The manipulation +is as follow:<a id="FNanchor_634" href="#Footnote_634" class="fnanchor">[634]</a></p> + +<div class="figcenter smcap"> + <img id="FIG_124" src="images/fig124.jpg" alt="" width="400" height="482" > + <p class="center spb1">Fig. 124. Distilling Apparatus.</p> +</div> + +<p>One hundred cubic centimeters of the liquor are placed in a flask of +from 250 to 300 cubic centimeters capacity, fifty cubic centimeters +of water added, the flask attached to a vertical condenser by means +of a bent bulb tube, 100 cubic centimeters distilled and the specific +gravity of the distillate determined. The distillate is also weighed, +or its weight calculated from the specific gravity. The corresponding +percentage of alcohol by weight is obtained from the appended table, +and this figure multiplied by the weight of the distillate, and the +<span class="pagenum"><a id="Page_615"></a>[Pg 615]</span> +result divided by the weight of the sample, gives the per cent of +alcohol by weight contained therein.</p> + +<p>The percentage of alcohol by volume of the liquor is the same as that +of the distillate, and is obtained directly from the appended table.</p> + +<p>In distilled liquors about thirty grams are diluted to 150 cubic +centimeters, 100 cubic centimeters distilled and the per cent of +alcohol by weight determined as above.</p> + +<p>The percentage of alcohol by volume in the distillate is obtained from +the appended table. This figure divided by the number expressing the +volume in cubic centimeters of the liquor taken for the determination +(calculated from the specific gravity), and the result multiplied by +100 gives the per cent of alcohol by volume in the original liquor.</p> + +<p><b>618. Determining the Specific Gravity of the Distillate.</b>—The +specific gravity of the distillate may be determined by the pyknometer, +alcoholometer, hydrostatic balance or in any accurate way. The volume +of the distillate is not always large enough to be conveniently used +with an alcoholometer, especially the large ones employed by the Bureau +of Internal Revenue. In the laboratory of the Agricultural Department, +it is customary to determine the density of the distillate by the +hydrostatic balance shown in paragraph <b><a href="#P_285">285</a></b>. The +specific gravity is in each case determined at 15°.6, referred to water of +the same temperature, or if at a different temperature calculated thereto.</p> + +<p><b>619. Table for Use with Hydrostatic Plummet.</b>—It is more +convenient to determine the density of the alcoholic distillate at room +temperature than to reduce it to the standard for which the plummet is +graduated. In the case of a plummet which displaces exactly five grams, +or multiple thereof, of distilled water at 15°.6, the corrections for +temperatures between 12°.2 and 30° are found in the following table, +prepared by Bigelow.<a id="FNanchor_635" href="#Footnote_635" class="fnanchor">[635]</a></p> + +<p>If the weight of the alcoholic solution displaced be 4.96075 grams the +apparent specific gravity 0.99215 and the temperature of observation +25°.4, the correction, which is additive, as given in the table is +0.00191 and the true specific gravity is 0.99406 and the percentage of +alcohol by volume 4.08. +<span class="pagenum"><a id="Page_616"></a>[Pg 616]</span></p> + +<p>When the plummet does not exactly displace five grams of water at +15°.6, but nearly so, the table may still be used.</p> + +<p>For example, suppose the weight of water displaced be 4.9868 instead of +five grams. The apparent specific gravity of the water by this plummet +is 0.99736 and the difference between this and the true specific +gravity is 0.00264, which is a constant correction to be added to the +specific gravity as determined in each case.</p> + +<p class="f120 spa1"><b><span class="smcap">Correction Table for Specific Gravity.</span></b></p> + +<p class="center"><i>Below 15°.6 Subtract; Above 15°.6 Add.</i></p> + +<table class="spb1 spa1"> + <thead><tr> + <th class="tdc bb"> Temp. </th> + <th class="tdc bb"> Correction. </th> + <th class="tdc bb"> Temp. </th> + <th class="tdc bb"> Correction. </th> + <th class="tdc bb"> Temp. </th> + <th class="tdc bb"> Correction. </th> + </tr></thead> + <tbody><tr> + <td class="tdc">12.2</td> + <td class="tdc">0.00047</td> + <td class="tdc">18.2</td> + <td class="tdc">0.00043</td> + <td class="tdc">24.2</td> + <td class="tdc">0.00163</td> + </tr><tr> + <td class="tdc">12.4</td> + <td class="tdc">0.00044</td> + <td class="tdc">18.4</td> + <td class="tdc">0.00046</td> + <td class="tdc">24.4</td> + <td class="tdc">0.00167</td> + </tr><tr> + <td class="tdc">12.6</td> + <td class="tdc">0.00042</td> + <td class="tdc">18.6</td> + <td class="tdc">0.00050</td> + <td class="tdc">24.6</td> + <td class="tdc">0.00172</td> + </tr><tr> + <td class="tdc">12.8</td> + <td class="tdc">0.00039</td> + <td class="tdc">18.8</td> + <td class="tdc">0.00053</td> + <td class="tdc">24.8</td> + <td class="tdc">0.00176</td> + </tr><tr> + <td class="tdc">13.0</td> + <td class="tdc">0.00037</td> + <td class="tdc">19.0</td> + <td class="tdc">0.00057</td> + <td class="tdc">25.0</td> + <td class="tdc">0.00181</td> + </tr><tr> + <td class="tdc">13.2</td> + <td class="tdc">0.00634</td> + <td class="tdc">19.2</td> + <td class="tdc">0.00061</td> + <td class="tdc">25.2</td> + <td class="tdc">0.00186</td> + </tr><tr> + <td class="tdc">13.4</td> + <td class="tdc">0.00032</td> + <td class="tdc">19.4</td> + <td class="tdc">0.00065</td> + <td class="tdc">25.4</td> + <td class="tdc">0.00191</td> + </tr><tr> + <td class="tdc">13.6</td> + <td class="tdc">0.00029</td> + <td class="tdc">19.6</td> + <td class="tdc">0.00068</td> + <td class="tdc">25.6</td> + <td class="tdc">0.00195</td> + </tr><tr> + <td class="tdc">13.8</td> + <td class="tdc">0.00027</td> + <td class="tdc">19.8</td> + <td class="tdc">0.00072</td> + <td class="tdc">25.8</td> + <td class="tdc">0.00200</td> + </tr><tr> + <td class="tdc">14.0</td> + <td class="tdc">0.00024</td> + <td class="tdc">20.0</td> + <td class="tdc">0.00076</td> + <td class="tdc">26.0</td> + <td class="tdc">0.00205</td> + </tr><tr> + <td class="tdc">14.2</td> + <td class="tdc">0.00021</td> + <td class="tdc">20.2</td> + <td class="tdc">0.00080</td> + <td class="tdc">26.2</td> + <td class="tdc">0.00210</td> + </tr><tr> + <td class="tdc">14.4</td> + <td class="tdc">0.00018</td> + <td class="tdc">20.4</td> + <td class="tdc">0.00084</td> + <td class="tdc">26.4</td> + <td class="tdc">0.00215</td> + </tr><tr> + <td class="tdc">14.6</td> + <td class="tdc">0.00015</td> + <td class="tdc">20.6</td> + <td class="tdc">0.00087</td> + <td class="tdc">26.6</td> + <td class="tdc">0.00220</td> + </tr><tr> + <td class="tdc">14.8</td> + <td class="tdc">0.00012</td> + <td class="tdc">20.8</td> + <td class="tdc">0.00091</td> + <td class="tdc">26.8</td> + <td class="tdc">0.00225</td> + </tr><tr> + <td class="tdc">15.0</td> + <td class="tdc">0.00009</td> + <td class="tdc">21.0</td> + <td class="tdc">0.00095</td> + <td class="tdc">27.0</td> + <td class="tdc">0.00230</td> + </tr><tr> + <td class="tdc">15.2</td> + <td class="tdc">0.00006</td> + <td class="tdc">21.2</td> + <td class="tdc">0.00099</td> + <td class="tdc">27.2</td> + <td class="tdc">0.00235</td> + </tr><tr> + <td class="tdc bb">15.4</td> + <td class="tdc bb">0.00003</td> + <td class="tdc">21.4</td> + <td class="tdc">0.00103</td> + <td class="tdc"> 27.4</td> + <td class="tdc">0.00240</td> + </tr><tr> + <td class="tdc bb"><b>15.6</b></td> + <td class="tdc bb"><b>0.00000</b></td> + <td class="tdc">21.6</td> + <td class="tdc">0.00107</td> + <td class="tdc">27.6</td> + <td class="tdc">0.00246</td> + </tr><tr> + <td class="tdc">15.8</td> + <td class="tdc">0.00003</td> + <td class="tdc">21.8</td> + <td class="tdc">0.00111</td> + <td class="tdc">27.8</td> + <td class="tdc">0.00251</td> + </tr><tr> + <td class="tdc">16.0</td> + <td class="tdc">0.00006</td> + <td class="tdc">22.0</td> + <td class="tdc">0.00115</td> + <td class="tdc">28.0</td> + <td class="tdc">0.00256</td> + </tr><tr> + <td class="tdc">16.2</td> + <td class="tdc">0.00009</td> + <td class="tdc">22.2</td> + <td class="tdc">0.00119</td> + <td class="tdc">28.2</td> + <td class="tdc">0.00261</td> + </tr><tr> + <td class="tdc">16.4</td> + <td class="tdc">0.00012</td> + <td class="tdc">22.4</td> + <td class="tdc">0.00123</td> + <td class="tdc">28.4</td> + <td class="tdc">0.00267</td> + </tr><tr> + <td class="tdc">16.6</td> + <td class="tdc">0.00016</td> + <td class="tdc">22.6</td> + <td class="tdc">0.00128</td> + <td class="tdc">28.6</td> + <td class="tdc">0.00272</td> + </tr><tr> + <td class="tdc">16.8</td> + <td class="tdc">0.00019</td> + <td class="tdc">22.8</td> + <td class="tdc">0.00132</td> + <td class="tdc">28.8</td> + <td class="tdc">0.00278</td> + </tr><tr> + <td class="tdc">17.0</td> + <td class="tdc">0.00022</td> + <td class="tdc">23.0</td> + <td class="tdc">0.00136</td> + <td class="tdc">29.0</td> + <td class="tdc">0.00283</td> + </tr><tr> + <td class="tdc">17.2</td> + <td class="tdc">0.00025</td> + <td class="tdc">23.2</td> + <td class="tdc">0.00140</td> + <td class="tdc">29.2</td> + <td class="tdc">0.00288</td> + </tr><tr> + <td class="tdc">17.4</td> + <td class="tdc">0.00029</td> + <td class="tdc">23.4</td> + <td class="tdc">0.00145</td> + <td class="tdc">29.4</td> + <td class="tdc">0.00294</td> + </tr><tr> + <td class="tdc">17.6</td> + <td class="tdc">0.00032</td> + <td class="tdc">23.6</td> + <td class="tdc">0.00149</td> + <td class="tdc">29.6</td> + <td class="tdc">0.00299</td> + </tr><tr> + <td class="tdc">17.8</td> + <td class="tdc">0.00036</td> + <td class="tdc">23.8</td> + <td class="tdc">0.00154</td> + <td class="tdc">29.8</td> + <td class="tdc">0.00306</td> + </tr><tr> + <td class="tdc">18.0</td> + <td class="tdc">0.00039</td> + <td class="tdc">24.0</td> + <td class="tdc">0.00158</td> + <td class="tdc">30.0</td> + <td class="tdc">0.00311</td> + </tr> + </tbody> +</table> + +<p>The table is only accurate when the distillate does not contain over +seven nor less than three per cent of alcohol. If the distillate +contain more than seven per cent of alcohol it is diluted and the +compensating correction made.</p> + +<p><b>620. Calculating Results.</b>—The specific gravity of the alcoholic +distillate having been determined by any approved method and corrected +to a temperature of 15°.6, the corresponding per cents of alcohol by +volume and by weight are found by consulting the following table.<a id="FNanchor_636" href="#Footnote_636" class="fnanchor">[636]</a> +If, for example, the corrected specific gravity be exactly that given +in any figure of the table the corresponding per cents are directly +read. If the specific gravity found fall between two numbers in the +table the corresponding per cents are determined by interpolation. +<span class="pagenum"><a id="Page_617"></a>[Pg 617]</span></p> + +<p class="f120"><b><span class="smcap">Table Showing Percentage of Alcohol<br> + by Weight and by Volume.</span></b></p> + +<table class="spb1"> + <thead><tr> + <th class="tdc bb bt bl">Specific<br>gravity at<br> 15°.6./15°.6. </th> + <th class="tdc bb bt bl">Per cent<br>alcohol<br> by volume. </th> + <th class="tdc bb bt bl br">Per cent<br>alcohol<br> by weight. </th> + </tr></thead> + <tbody><tr> + <td class="tdr_ws1 bl">1.00000</td> + <td class="tdr_ws1 bl">0.00</td> + <td class="tdr_ws1 bl br">0.00</td> + </tr><tr> + <td class="tdr_ws1 bl">0.99992</td> + <td class="tdr_ws1 bl">.05</td> + <td class="tdr_ws1 bl br">.04</td> + </tr><tr> + <td class="tdr_ws1 bl">984</td> + <td class="tdr_ws1 bl">.10</td> + <td class="tdr_ws1 bl br">.08</td> + </tr><tr> + <td class="tdr_ws1 bl">976</td> + <td class="tdr_ws1 bl">.15</td> + <td class="tdr_ws1 bl br">.12</td> + </tr><tr> + <td class="tdr_ws1 bl">968</td> + <td class="tdr_ws1 bl">.20</td> + <td class="tdr_ws1 bl br">.16</td> + </tr><tr> + <td class="tdr_ws1 bl">961</td> + <td class="tdr_ws1 bl">.25</td> + <td class="tdr_ws1 bl br">.20</td> + </tr><tr> + <td class="tdr_ws1 bl">953</td> + <td class="tdr_ws1 bl">.30</td> + <td class="tdr_ws1 bl br">.24</td> + </tr><tr> + <td class="tdr_ws1 bl">945</td> + <td class="tdr_ws1 bl">.35</td> + <td class="tdr_ws1 bl br">.28</td> + </tr><tr> + <td class="tdr_ws1 bl">937</td> + <td class="tdr_ws1 bl">.40</td> + <td class="tdr_ws1 bl br">.32</td> + </tr><tr> + <td class="tdr_ws1 bl bb">930</td> + <td class="tdr_ws1 bl bb">.45</td> + <td class="tdr_ws1 bl br bb">.36</td> + </tr><tr> + <td class="tdr_ws1 bl">.99923</td> + <td class="tdr_ws1 bl">0.50</td> + <td class="tdr_ws1 bl br">0.40</td> + </tr><tr> + <td class="tdr_ws1 bl">915</td> + <td class="tdr_ws1 bl">.55</td> + <td class="tdr_ws1 bl br">.44</td> + </tr><tr> + <td class="tdr_ws1 bl">907</td> + <td class="tdr_ws1 bl">.60</td> + <td class="tdr_ws1 bl br">.48</td> + </tr><tr> + <td class="tdr_ws1 bl">900</td> + <td class="tdr_ws1 bl">.65</td> + <td class="tdr_ws1 bl br">.52</td> + </tr><tr> + <td class="tdr_ws1 bl">892</td> + <td class="tdr_ws1 bl">.70</td> + <td class="tdr_ws1 bl br">.56</td> + </tr><tr> + <td class="tdr_ws1 bl">884</td> + <td class="tdr_ws1 bl">.75</td> + <td class="tdr_ws1 bl br">.60</td> + </tr><tr> + <td class="tdr_ws1 bl">877</td> + <td class="tdr_ws1 bl">.80</td> + <td class="tdr_ws1 bl br">.64</td> + </tr><tr> + <td class="tdr_ws1 bl">869</td> + <td class="tdr_ws1 bl">.85</td> + <td class="tdr_ws1 bl br">.67</td> + </tr><tr> + <td class="tdr_ws1 bl">861</td> + <td class="tdr_ws1 bl">.90</td> + <td class="tdr_ws1 bl br">.71</td> + </tr><tr> + <td class="tdr_ws1 bl bb">854</td> + <td class="tdr_ws1 bl bb">.95</td> + <td class="tdr_ws1 bl br bb">.75</td> + </tr><tr> + <td class="tdr_ws1 bl">.99849</td> + <td class="tdr_ws1 bl">1.00</td> + <td class="tdr_ws1 bl br">0.79</td> + </tr><tr> + <td class="tdr_ws1 bl">842</td> + <td class="tdr_ws1 bl">.05</td> + <td class="tdr_ws1 bl br">.83</td> + </tr><tr> + <td class="tdr_ws1 bl">834</td> + <td class="tdr_ws1 bl">.10</td> + <td class="tdr_ws1 bl br">.87</td> + </tr><tr> + <td class="tdr_ws1 bl">827</td> + <td class="tdr_ws1 bl">.15</td> + <td class="tdr_ws1 bl br">.91</td> + </tr><tr> + <td class="tdr_ws1 bl">819</td> + <td class="tdr_ws1 bl">.20</td> + <td class="tdr_ws1 bl br">.95</td> + </tr><tr> + <td class="tdr_ws1 bl">812</td> + <td class="tdr_ws1 bl">.25</td> + <td class="tdr_ws1 bl br">.99</td> + </tr><tr> + <td class="tdr_ws1 bl">805</td> + <td class="tdr_ws1 bl">.30</td> + <td class="tdr_ws1 bl br">1.03</td> + </tr><tr> + <td class="tdr_ws1 bl">797</td> + <td class="tdr_ws1 bl">.35</td> + <td class="tdr_ws1 bl br">.07</td> + </tr><tr> + <td class="tdr_ws1 bl">790</td> + <td class="tdr_ws1 bl">.40</td> + <td class="tdr_ws1 bl br">.11</td> + </tr><tr> + <td class="tdr_ws1 bl bb">782</td> + <td class="tdr_ws1 bl bb">.45</td> + <td class="tdr_ws1 bl br bb">.15</td> + </tr><tr> + <td class="tdr_ws1 bl">.99775</td> + <td class="tdr_ws1 bl">1.50</td> + <td class="tdr_ws1 bl br">1.19</td> + </tr><tr> + <td class="tdr_ws1 bl">768</td> + <td class="tdr_ws1 bl">.55</td> + <td class="tdr_ws1 bl br">.23</td> + </tr><tr> + <td class="tdr_ws1 bl">760</td> + <td class="tdr_ws1 bl">.60</td> + <td class="tdr_ws1 bl br">.27</td> + </tr><tr> + <td class="tdr_ws1 bl">753</td> + <td class="tdr_ws1 bl">.65</td> + <td class="tdr_ws1 bl br">.31</td> + </tr><tr> + <td class="tdr_ws1 bl">745</td> + <td class="tdr_ws1 bl">.70</td> + <td class="tdr_ws1 bl br">.35</td> + </tr><tr> + <td class="tdr_ws1 bl">738</td> + <td class="tdr_ws1 bl">.75</td> + <td class="tdr_ws1 bl br">.39</td> + </tr><tr> + <td class="tdr_ws1 bl">731</td> + <td class="tdr_ws1 bl">.80</td> + <td class="tdr_ws1 bl br">.43</td> + </tr><tr> + <td class="tdr_ws1 bl">723</td> + <td class="tdr_ws1 bl">.85</td> + <td class="tdr_ws1 bl br">.47</td> + </tr><tr> + <td class="tdr_ws1 bl">716</td> + <td class="tdr_ws1 bl">.90</td> + <td class="tdr_ws1 bl br">.51</td> + </tr><tr> + <td class="tdr_ws1 bl bb">708</td> + <td class="tdr_ws1 bl bb">.95</td> + <td class="tdr_ws1 bl br bb">.55</td> + </tr><tr> + <td class="tdr_ws1 bl">.99701</td> + <td class="tdr_ws1 bl">2.00</td> + <td class="tdr_ws1 bl br">1.59</td> + </tr><tr> + <td class="tdr_ws1 bl">694</td> + <td class="tdr_ws1 bl">.05</td> + <td class="tdr_ws1 bl br">.63</td> + </tr><tr> + <td class="tdr_ws1 bl">687</td> + <td class="tdr_ws1 bl">.10</td> + <td class="tdr_ws1 bl br">.67</td> + </tr><tr> + <td class="tdr_ws1 bl">679</td> + <td class="tdr_ws1 bl">.15</td> + <td class="tdr_ws1 bl br">.71</td> + </tr><tr> + <td class="tdr_ws1 bl">672</td> + <td class="tdr_ws1 bl">.20</td> + <td class="tdr_ws1 bl br">.75</td> + </tr><tr> + <td class="tdr_ws1 bl">665</td> + <td class="tdr_ws1 bl">.25</td> + <td class="tdr_ws1 bl br">.79</td> + </tr><tr> + <td class="tdr_ws1 bl">658</td> + <td class="tdr_ws1 bl">.30</td> + <td class="tdr_ws1 bl br">.83</td> + </tr><tr> + <td class="tdr_ws1 bl">651</td> + <td class="tdr_ws1 bl">.35</td> + <td class="tdr_ws1 bl br">.87</td> + </tr><tr> + <td class="tdr_ws1 bl">643</td> + <td class="tdr_ws1 bl">.40</td> + <td class="tdr_ws1 bl br">.91</td> + </tr><tr> + <td class="tdr_ws1 bl bb">636</td> + <td class="tdr_ws1 bl bb">.45</td> + <td class="tdr_ws1 bl br bb">.95</td> + </tr><tr> + <td class="tdr_ws1 bl">0.99629</td> + <td class="tdr_ws1 bl">2.50</td> + <td class="tdr_ws1 bl br">1.99</td> + </tr><tr> + <td class="tdr_ws1 bl">622</td> + <td class="tdr_ws1 bl">.55</td> + <td class="tdr_ws1 bl br">2.03</td> + </tr><tr> + <td class="tdr_ws1 bl">615</td> + <td class="tdr_ws1 bl">.60</td> + <td class="tdr_ws1 bl br">.07</td> + </tr><tr> + <td class="tdr_ws1 bl">607</td> + <td class="tdr_ws1 bl">.65</td> + <td class="tdr_ws1 bl br">.11</td> + </tr><tr> + <td class="tdr_ws1 bl">600</td> + <td class="tdr_ws1 bl">.70</td> + <td class="tdr_ws1 bl br">.15</td> + </tr><tr> + <td class="tdr_ws1 bl">593</td> + <td class="tdr_ws1 bl">.75</td> + <td class="tdr_ws1 bl br">.19</td> + </tr><tr> + <td class="tdr_ws1 bl">586</td> + <td class="tdr_ws1 bl">.80</td> + <td class="tdr_ws1 bl br">.23</td> + </tr><tr> + <td class="tdr_ws1 bl">579</td> + <td class="tdr_ws1 bl">.85</td> + <td class="tdr_ws1 bl br">.27</td> + </tr><tr> + <td class="tdr_ws1 bl">571</td> + <td class="tdr_ws1 bl">.90</td> + <td class="tdr_ws1 bl br">.31</td> + </tr><tr> + <td class="tdr_ws1 bl bb">564</td> + <td class="tdr_ws1 bl bb">.95</td> + <td class="tdr_ws1 bl br bb">.35</td> + </tr><tr> + <td class="tdr_ws1 bl">.99557</td> + <td class="tdr_ws1 bl">3.00</td> + <td class="tdr_ws1 bl br">2.39</td> + </tr><tr> + <td class="tdr_ws1 bl">550</td> + <td class="tdr_ws1 bl">.05</td> + <td class="tdr_ws1 bl br">.43</td> + </tr><tr> + <td class="tdr_ws1 bl">543</td> + <td class="tdr_ws1 bl">.10</td> + <td class="tdr_ws1 bl br">.47</td> + </tr><tr> + <td class="tdr_ws1 bl">536</td> + <td class="tdr_ws1 bl">.15</td> + <td class="tdr_ws1 bl br">.51</td> + </tr><tr> + <td class="tdr_ws1 bl">529</td> + <td class="tdr_ws1 bl">.20</td> + <td class="tdr_ws1 bl br">.55</td> + </tr><tr> + <td class="tdr_ws1 bl">522</td> + <td class="tdr_ws1 bl">.25</td> + <td class="tdr_ws1 bl br">.59</td> + </tr><tr> + <td class="tdr_ws1 bl">515</td> + <td class="tdr_ws1 bl">.30</td> + <td class="tdr_ws1 bl br">.64</td> + </tr><tr> + <td class="tdr_ws1 bl">508</td> + <td class="tdr_ws1 bl">.35</td> + <td class="tdr_ws1 bl br">.68</td> + </tr><tr> + <td class="tdr_ws1 bl">501</td> + <td class="tdr_ws1 bl">.40</td> + <td class="tdr_ws1 bl br">.72</td> + </tr><tr> + <td class="tdr_ws1 bl bb">494</td> + <td class="tdr_ws1 bl bb">.45</td> + <td class="tdr_ws1 bl br bb">.76</td> + </tr><tr> + <td class="tdr_ws1 bl">.99487</td> + <td class="tdr_ws1 bl">3.50</td> + <td class="tdr_ws1 bl br">2.80</td> + </tr><tr> + <td class="tdr_ws1 bl">480</td> + <td class="tdr_ws1 bl">.55</td> + <td class="tdr_ws1 bl br">.84</td> + </tr><tr> + <td class="tdr_ws1 bl">473</td> + <td class="tdr_ws1 bl">.60</td> + <td class="tdr_ws1 bl br">.88</td> + </tr><tr> + <td class="tdr_ws1 bl">466</td> + <td class="tdr_ws1 bl">.65</td> + <td class="tdr_ws1 bl br">.92</td> + </tr><tr> + <td class="tdr_ws1 bl">459</td> + <td class="tdr_ws1 bl">.70</td> + <td class="tdr_ws1 bl br">.96</td> + </tr><tr> + <td class="tdr_ws1 bl">452</td> + <td class="tdr_ws1 bl">.75</td> + <td class="tdr_ws1 bl br">3.00</td> + </tr><tr> + <td class="tdr_ws1 bl">445</td> + <td class="tdr_ws1 bl">.80</td> + <td class="tdr_ws1 bl br">.04</td> + </tr><tr> + <td class="tdr_ws1 bl">438</td> + <td class="tdr_ws1 bl">.85</td> + <td class="tdr_ws1 bl br">.08</td> + </tr><tr> + <td class="tdr_ws1 bl">431</td> + <td class="tdr_ws1 bl">.90</td> + <td class="tdr_ws1 bl br">.12</td> + </tr><tr> + <td class="tdr_ws1 bl bb">424</td> + <td class="tdr_ws1 bl bb">.95</td> + <td class="tdr_ws1 bl br bb">.16</td> + </tr><tr> + <td class="tdr_ws1 bl">.99417</td> + <td class="tdr_ws1 bl">4.00</td> + <td class="tdr_ws1 bl br">3.20</td> + </tr><tr> + <td class="tdr_ws1 bl">410</td> + <td class="tdr_ws1 bl">.05</td> + <td class="tdr_ws1 bl br">.24</td> + </tr><tr> + <td class="tdr_ws1 bl">403</td> + <td class="tdr_ws1 bl">.10</td> + <td class="tdr_ws1 bl br">.28</td> + </tr><tr> + <td class="tdr_ws1 bl">397</td> + <td class="tdr_ws1 bl">.15</td> + <td class="tdr_ws1 bl br">.32</td> + </tr><tr> + <td class="tdr_ws1 bl">390</td> + <td class="tdr_ws1 bl">.20</td> + <td class="tdr_ws1 bl br">.36</td> + </tr><tr> + <td class="tdr_ws1 bl">383</td> + <td class="tdr_ws1 bl">.25</td> + <td class="tdr_ws1 bl br">.40</td> + </tr><tr> + <td class="tdr_ws1 bl">376</td> + <td class="tdr_ws1 bl">.30</td> + <td class="tdr_ws1 bl br">.44</td> + </tr><tr> + <td class="tdr_ws1 bl">369</td> + <td class="tdr_ws1 bl">.35</td> + <td class="tdr_ws1 bl br">.48</td> + </tr><tr> + <td class="tdr_ws1 bl">363</td> + <td class="tdr_ws1 bl">.40</td> + <td class="tdr_ws1 bl br">.52</td> + </tr><tr> + <td class="tdr_ws1 bl bb">356</td> + <td class="tdr_ws1 bl bb">.45</td> + <td class="tdr_ws1 bl br bb">.56</td> + </tr><tr> + <td class="tdr_ws1 bl">.99349</td> + <td class="tdr_ws1 bl">4.50</td> + <td class="tdr_ws1 bl br">3.60</td> + </tr><tr> + <td class="tdr_ws1 bl">342</td> + <td class="tdr_ws1 bl">.55</td> + <td class="tdr_ws1 bl br">.64</td> + </tr><tr> + <td class="tdr_ws1 bl">335</td> + <td class="tdr_ws1 bl">.60</td> + <td class="tdr_ws1 bl br">.68</td> + </tr><tr> + <td class="tdr_ws1 bl">329</td> + <td class="tdr_ws1 bl">.65</td> + <td class="tdr_ws1 bl br">.72</td> + </tr><tr> + <td class="tdr_ws1 bl">322</td> + <td class="tdr_ws1 bl">.70</td> + <td class="tdr_ws1 bl br">.76</td> + </tr><tr> + <td class="tdr_ws1 bl">315</td> + <td class="tdr_ws1 bl">.75</td> + <td class="tdr_ws1 bl br">.80</td> 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class="tdr_ws1 bl br">.39</td> + </tr><tr> + <td class="tdr_ws1 bl">053</td> + <td class="tdr_ws1 bl">.75</td> + <td class="tdr_ws1 bl br">.44</td> + </tr><tr> + <td class="tdr_ws1 bl">044</td> + <td class="tdr_ws1 bl">.80</td> + <td class="tdr_ws1 bl br">.49</td> + </tr><tr> + <td class="tdr_ws1 bl">035</td> + <td class="tdr_ws1 bl">.85</td> + <td class="tdr_ws1 bl br">.53</td> + </tr><tr> + <td class="tdr_ws1 bl">026</td> + <td class="tdr_ws1 bl">.90</td> + <td class="tdr_ws1 bl br">.58</td> + </tr><tr> + <td class="tdr_ws1 bl bb">017</td> + <td class="tdr_ws1 bl bb">.95</td> + <td class="tdr_ws1 bl br bb">.62</td> + </tr><tr> + <td class="tdr_ws1 bl">.94008</td> + <td class="tdr_ws1 bl">47.00</td> + <td class="tdr_ws1 bl br">39.67</td> + </tr><tr> + <td class="tdr_ws1 bl">.93999</td> + <td class="tdr_ws1 bl">.05</td> + <td class="tdr_ws1 bl br">.72</td> + </tr><tr> + <td class="tdr_ws1 bl">990</td> + <td class="tdr_ws1 bl">.10</td> + <td class="tdr_ws1 bl br">.76</td> + </tr><tr> + <td class="tdr_ws1 bl">980</td> + <td class="tdr_ws1 bl">.15</td> + <td class="tdr_ws1 bl br">.81</td> + </tr><tr> + <td class="tdr_ws1 bl">971</td> + <td class="tdr_ws1 bl">.20</td> + <td class="tdr_ws1 bl br">.85</td> + </tr><tr> + <td class="tdr_ws1 bl">962</td> + <td class="tdr_ws1 bl">.25</td> + <td class="tdr_ws1 bl br">.90</td> + </tr><tr> + <td class="tdr_ws1 bl">953</td> + <td class="tdr_ws1 bl">.30</td> + <td class="tdr_ws1 bl br">.95</td> + </tr><tr> + <td class="tdr_ws1 bl">944</td> + <td class="tdr_ws1 bl">.35</td> + <td class="tdr_ws1 bl br">.99</td> + </tr><tr> + <td class="tdr_ws1 bl">934</td> + <td class="tdr_ws1 bl">.40</td> + <td class="tdr_ws1 bl br">40.04</td> + </tr><tr> + <td class="tdr_ws1 bl bb">925</td> + <td class="tdr_ws1 bl bb">.45</td> + <td class="tdr_ws1 bl br bb">.08</td> + </tr><tr> + <td class="tdr_ws1 bl">0.93916</td> + <td class="tdr_ws1 bl">47.50</td> + <td class="tdr_ws1 bl br">40.13</td> + </tr><tr> + <td class="tdr_ws1 bl">906</td> + <td class="tdr_ws1 bl">.55</td> + <td class="tdr_ws1 bl br">.18</td> + </tr><tr> + <td class="tdr_ws1 bl">898</td> + <td class="tdr_ws1 bl">.60</td> + <td class="tdr_ws1 bl br">.22</td> + </tr><tr> + <td class="tdr_ws1 bl">888</td> + <td class="tdr_ws1 bl">.65</td> + <td class="tdr_ws1 bl br">.27</td> + </tr><tr> + <td class="tdr_ws1 bl">879</td> + <td class="tdr_ws1 bl">.70</td> + <td class="tdr_ws1 bl br">.32</td> + </tr><tr> + <td class="tdr_ws1 bl">870</td> + <td class="tdr_ws1 bl">.75</td> + <td class="tdr_ws1 bl br">.37</td> + </tr><tr> + <td class="tdr_ws1 bl">861</td> + <td class="tdr_ws1 bl">.80</td> + <td class="tdr_ws1 bl br">.41</td> + </tr><tr> + <td class="tdr_ws1 bl">852</td> + <td class="tdr_ws1 bl">.85</td> + <td class="tdr_ws1 bl br">.46</td> + </tr><tr> + <td class="tdr_ws1 bl">842</td> + <td class="tdr_ws1 bl">.90</td> + <td class="tdr_ws1 bl br">.51</td> + </tr><tr> + <td class="tdr_ws1 bl bb">833</td> + <td class="tdr_ws1 bl bb">.95</td> + <td class="tdr_ws1 bl br bb">.55</td> + </tr><tr> + <td class="tdr_ws1 bl">.93824</td> + <td class="tdr_ws1 bl">48.00</td> + <td class="tdr_ws1 bl br">40.60</td> + </tr><tr> + <td class="tdr_ws1 bl">815</td> + <td class="tdr_ws1 bl">.05</td> + <td class="tdr_ws1 bl br">.65</td> + </tr><tr> + <td class="tdr_ws1 bl">808</td> + <td class="tdr_ws1 bl">.10</td> + <td class="tdr_ws1 bl br">.69</td> + </tr><tr> + <td class="tdr_ws1 bl">796</td> + <td class="tdr_ws1 bl">.15</td> + <td class="tdr_ws1 bl br">.74</td> + </tr><tr> + <td class="tdr_ws1 bl">786</td> + <td class="tdr_ws1 bl">.20</td> + <td class="tdr_ws1 bl br">.78</td> + </tr><tr> + <td class="tdr_ws1 bl">777</td> + <td class="tdr_ws1 bl">.25</td> + <td class="tdr_ws1 bl br">.83</td> + </tr><tr> + <td class="tdr_ws1 bl">768</td> + <td class="tdr_ws1 bl">.30</td> + <td class="tdr_ws1 bl br">.88</td> + </tr><tr> + <td class="tdr_ws1 bl">758</td> + <td class="tdr_ws1 bl">.35</td> + <td class="tdr_ws1 bl br">.92</td> + </tr><tr> + <td class="tdr_ws1 bl">740</td> + <td class="tdr_ws1 bl">.40</td> + <td class="tdr_ws1 bl br">.97</td> + </tr><tr> + <td class="tdr_ws1 bl bb">739</td> + <td class="tdr_ws1 bl bb">.45</td> + <td class="tdr_ws1 bl br bb">41.01</td> + </tr><tr> + <td class="tdr_ws1 bl">.93730</td> + <td class="tdr_ws1 bl">48.50</td> + <td class="tdr_ws1 bl br">41.06</td> + </tr><tr> + <td class="tdr_ws1 bl">721</td> + <td class="tdr_ws1 bl">.55</td> + <td class="tdr_ws1 bl br">.11</td> + </tr><tr> + <td class="tdr_ws1 bl">711</td> + <td class="tdr_ws1 bl">.60</td> + <td class="tdr_ws1 bl br">.15</td> + </tr><tr> + <td class="tdr_ws1 bl">702</td> + <td class="tdr_ws1 bl">.65</td> + <td class="tdr_ws1 bl br">.20</td> + </tr><tr> + <td class="tdr_ws1 bl">692</td> + <td class="tdr_ws1 bl">.70</td> + <td class="tdr_ws1 bl br">.24</td> + </tr><tr> + <td class="tdr_ws1 bl">683</td> + <td class="tdr_ws1 bl">.75</td> + <td class="tdr_ws1 bl br">.29</td> + </tr><tr> + <td class="tdr_ws1 bl">673</td> + <td class="tdr_ws1 bl">.80</td> + <td class="tdr_ws1 bl br">.34</td> + </tr><tr> + <td class="tdr_ws1 bl">664</td> + <td class="tdr_ws1 bl">.85</td> + <td class="tdr_ws1 bl br">.38</td> + </tr><tr> + <td class="tdr_ws1 bl">655</td> + <td class="tdr_ws1 bl">.90</td> + <td class="tdr_ws1 bl br">.43</td> + </tr><tr> + <td class="tdr_ws1 bl bb">645</td> + <td class="tdr_ws1 bl bb">.95</td> + <td class="tdr_ws1 bl br bb">.47</td> + </tr><tr> + <td class="tdr_ws1 bl">.93636</td> + <td class="tdr_ws1 bl">49.00</td> + <td class="tdr_ws1 bl br">41.52</td> + </tr><tr> + <td class="tdr_ws1 bl">626</td> + <td class="tdr_ws1 bl">.05</td> + <td class="tdr_ws1 bl br">.57</td> + </tr><tr> + <td class="tdr_ws1 bl">617</td> + <td class="tdr_ws1 bl">.10</td> + <td class="tdr_ws1 bl br">.61</td> + </tr><tr> + <td class="tdr_ws1 bl">607</td> + <td class="tdr_ws1 bl">.15</td> + <td class="tdr_ws1 bl br">.66</td> + </tr><tr> + <td class="tdr_ws1 bl">598</td> + <td class="tdr_ws1 bl">.20</td> + <td class="tdr_ws1 bl br">.71</td> + </tr><tr> + <td class="tdr_ws1 bl">588</td> + <td class="tdr_ws1 bl">.25</td> + <td class="tdr_ws1 bl br">.76</td> + </tr><tr> + <td class="tdr_ws1 bl">578</td> + <td class="tdr_ws1 bl">.30</td> + <td class="tdr_ws1 bl br">.80</td> + </tr><tr> + <td class="tdr_ws1 bl">569</td> + <td class="tdr_ws1 bl">.35</td> + <td class="tdr_ws1 bl br">.85</td> + </tr><tr> + <td class="tdr_ws1 bl">559</td> + <td class="tdr_ws1 bl">.40</td> + <td class="tdr_ws1 bl br">.90</td> + </tr><tr> + <td class="tdr_ws1 bl bb">550</td> + <td class="tdr_ws1 bl bb">.45</td> + <td class="tdr_ws1 bl br bb">.94</td> + </tr><tr> + <td class="tdr_ws1 bl">.93540</td> + <td class="tdr_ws1 bl">49.50</td> + <td class="tdr_ws1 bl br">41.99</td> + </tr><tr> + <td class="tdr_ws1 bl">530</td> + <td class="tdr_ws1 bl">.55</td> + <td class="tdr_ws1 bl br">42.04</td> + </tr><tr> + <td class="tdr_ws1 bl">521</td> + <td class="tdr_ws1 bl">.60</td> + <td class="tdr_ws1 bl br">.08</td> + </tr><tr> + <td class="tdr_ws1 bl">511</td> + <td class="tdr_ws1 bl">.65</td> + <td class="tdr_ws1 bl br">.13</td> + </tr><tr> + <td class="tdr_ws1 bl">502</td> + <td class="tdr_ws1 bl">.70</td> + <td class="tdr_ws1 bl br">.18</td> + </tr><tr> + <td class="tdr_ws1 bl">492</td> + <td class="tdr_ws1 bl">.75</td> + <td class="tdr_ws1 bl br">.23</td> + </tr><tr> + <td class="tdr_ws1 bl">482</td> + <td class="tdr_ws1 bl">.80</td> + <td class="tdr_ws1 bl br">.27</td> + </tr><tr> + <td class="tdr_ws1 bl">473</td> + <td class="tdr_ws1 bl">.85</td> + <td class="tdr_ws1 bl br">.32</td> + </tr><tr> + <td class="tdr_ws1 bl">463</td> + <td class="tdr_ws1 bl">.90</td> + <td class="tdr_ws1 bl br">.37</td> + </tr><tr> + <td class="tdr_ws1 bl bb">454</td> + <td class="tdr_ws1 bl bb">.95</td> + <td class="tdr_ws1 bl br bb">.41</td> + </tr> + </tbody> +</table> + +<p><span class="pagenum"><a id="Page_622"></a>[Pg 622]</span> +<b>621. Determination of Percentage of Alcohol by Means Of Vapor +Temperature.</b>—The temperature of a mixture of alcohol and water +vapors is less than that of water alone and the depression is inversely +proportional to the quantity of alcohol present. This principle is +utilized in the construction of the ebullioscope or ebulliometer. +In this apparatus the temperature of pure boiling water vapor is +determined by a preliminary experiment. This point must be frequently +revised in order to correct it for variations in barometric pressure. +The water is withdrawn from the boiler of the apparatus, the same +volume of a wine or beer placed therein, and the vapor temperature +again determined. By comparing the boiling point of the wine, with a +scale calibrated for different percentages of alcohol, the quantity +of spirit present is determined. When water vapor is at 100° a <i>vin +ordinaire</i> having eight per cent of alcohol gives a vapor at 93°.8. +The presence of extractive matters in the sample, which tend to raise +its boiling point, is neglected in the calculation of results.</p> + +<p><b>622. Improved Ebullioscope.</b>—The principle mentioned in the +above paragraph may be applied with a considerable degree of accuracy, +by using the improved ebullioscope described below.<a id="FNanchor_637" href="#Footnote_637" class="fnanchor">[637]</a></p> + +<p>The apparatus consists of a glass flask F, shaped somewhat like an +erlenmeyer, closed at the top with a rubber stopper carrying a central +aperture for the insertion of the delicate thermometer A B, and a +lateral smaller aperture for connecting the interior of the flask with +the condenser D. The return of the condensed vapors from D is effected +through the tube entering the flask F in such a manner as to deliver +the condensed liquid beneath the surface of the liquid in F as shown +in the <a href="#FIG_125">figure</a>. The flask F contains pieces of scrap +platinum or pumice stone to prevent bumping and secure an even ebullition. +The flask F rests upon a disk of asbestos, perforated in such a way as to +have the opening fully covered by the bottom of the flask. To protect F against +the influence of air currents it is enclosed in the glass cylinder E +resting on the asbestos disk below and closed with a detachable soft +rubber cover at the top. The temperature between the cylinder E and the +<span class="pagenum"><a id="Page_623"></a>[Pg 623]</span> +flask F is measured by the thermometer C and the flame of the lamp +G should be so adjusted as to bring the temperature between the +flask F and the cylinder E to about 90° at the time of reading the +thermometer B. The bulb of the thermometer B may be protected by a +thin glass tube carrying distilled water, so adjusted as to prevent +the escape of the watery vapor into F. The thermometer B is such as +is used for determining molecular weights by the cryoscopic method. +It has a cistern at A which holds any excess of mercury not needed in +<i>adjusting the thermometer</i> for any required temperature.</p> + +<div class="figcenter smcap"> + <img id="FIG_125" src="images/fig125.jpg" alt="" width="300" height="605" > + <p class="center spb1">Fig. 125. Improved Ebullioscope.</p> +</div> + +<p>A second apparatus, exactly similar to the one described, is +conveniently used for measuring the changes in <i>barometric</i> +pressure during the process of the analysis. The temperature of the +vapor of boiling water having been first determined, the beer or wine +is placed in F, and the temperature of the vapor of the boiling liquid +determined after the temperature of the air layer between E and F +reaches about 90°, measured on the thermometer C. By using alcoholic +mixtures of known strength the depression for each changing per cent of +alcohol is determined for each system of apparatus employed, and this +having once been done, the percentage of alcohol in any unknown liquid +is at once determined by inspecting the thermometer, the bulb of which +<span class="pagenum"><a id="Page_624"></a>[Pg 624]</span> +is immersed in the vapor from the boiling liquid. In the apparatus +<a href="#FIG_125">figured</a>, a depression of 0°.8 is equivalent to +one per cent of alcohol by volume. Full directions for the manipulation +of the apparatus may be found in the paper cited above.</p> + +<p><b>623. Total Fixed Matters.</b>—The residue left on evaporating a +fermented beverage to dryness is commonly known as extractive matter, +or simply extract. It is composed chiefly of unfermented carbohydrates, +organic acids, nitrogenous bodies, glycerol and mineral substances. +Hydrochloric and sulfuric acids may also be found therein. If any +non-volatile preservatives have been used in the sample, such as +borax, salicylates and the like, these will also be found in the +solid residue. The bodies which escape are water, alcohols, ethers +and essential oils. The character of the residue left by wines and +beers is evidently different. In each case it should contain typical +components which aid in judging of the purity of the sample. For +instance, in beers the substitution for malt of carbohydrate bodies +comparatively free of proteids, produces a beer containing a deficiency +of nitrogenous bodies. Pure malt beer will rarely have less than +one-half of a per cent of proteids, while beer made largely of glucose, +rice or hominy grits, will have a much smaller quantity. First will be +described below the methods of determining the fixed residue left on +evaporation, and thereafter the processes for ascertaining its leading +components.</p> + +<p><b>624. Methods of the Official Chemists.</b>—Two methods are in use +by the official chemists for determining the fixed solids in fermented +beverages.<a id="FNanchor_638" href="#Footnote_638" class="fnanchor">[638]</a> +They are as follows:</p> + +<p><i>Direct Method.</i>—Fifty cubic centimeters of the sample are +weighed, placed in a platinum dish about eighty millimeters in diameter +and capable of holding about seventy-five cubic centimeters and +evaporated on the steam bath to a sirupy consistence. The residue is +heated for two and a half hours in a drying oven at the temperature of +boiling water and weighed.</p> + +<p><i>In Sweet Wines.</i>—Ten cubic centimeters of the liquor are weighed +and diluted to 100 with water. Fifty cubic centimeters of this solution +are evaporated as described above.</p> + +<p><i>Optional Method.</i>—Fifty cubic centimeters of the sample are +placed in a platinum or porcelain dish and evaporated on the steam bath +<span class="pagenum"><a id="Page_625"></a>[Pg 625]</span> +until the volume is reduced to one-third. The dealcoholized liquid +is washed into a fifty cubic centimeter flask, cooled and made up to +the original volume. It is mixed thoroughly and the specific gravity +ascertained with a pyknometer, hydrostatic balance or an accurately +standardized hydrometer. The percentage of total solids is obtained +from the appended table. The column on the left of the specific gravity +gives the percentage of extract in a wine, as calculated by Hager, +and that on the right the percentage of extract in a beer or wort, +as calculated by Schultze. According to Baumert, however, Schultze’s +table gives results which approximate more closely the data obtained by +direct estimation than does Hager’s.</p> + +<p class="f120 spa1"><b><span class="smcap">Tables of Hager and Schultze for<br> +the Determination of Extract<br>by the Indirect Method.</span></b></p> + +<table class="spb1"> + <thead><tr> + <th class="tdc bb bl bt2"> Hager. </th> + <th class="tdc bb bl bt2"> Specific gravity. </th> + <th class="tdc bb bl br bt2"> Schultze. </th> + </tr></thead> + <tbody><tr> + <td class="tdc bl">0.84</td> + <td class="tdc bl">1.0038</td> + <td class="tdc bl br">1.00</td> + </tr><tr> + <td class="tdc bl">0.86</td> + <td class="tdc bl">1.0039</td> + <td class="tdc bl br">1.02</td> + </tr><tr> + <td class="tdc bl">0.88</td> + <td class="tdc bl">1.0040</td> + <td class="tdc bl br">1.05</td> + </tr><tr> + <td class="tdc bl">0.90</td> + <td class="tdc bl">1.0041</td> + <td class="tdc bl br">1.08</td> + </tr><tr> + <td class="tdc bl">0.92</td> + <td class="tdc bl">1.0042</td> + <td class="tdc bl br">1.10</td> + </tr><tr> + <td class="tdc bl">0.94</td> + <td class="tdc bl">1.0043</td> + <td class="tdc bl br">1.13</td> + </tr><tr> + <td class="tdc bl">0.96</td> + <td class="tdc bl">1.0044</td> + <td class="tdc bl br">1.15</td> + </tr><tr> + <td class="tdc bl">0.98</td> + <td class="tdc bl">1.0045</td> + <td class="tdc bl br">1.18</td> + </tr><tr> + <td class="tdc bl">1.00</td> + <td class="tdc bl">1.0046</td> + <td class="tdc bl br">1.21</td> + </tr><tr> + <td class="tdc bl">1.02</td> + <td class="tdc bl">1.0047</td> + <td class="tdc bl br">1.23</td> + </tr><tr> + <td class="tdc bl">1.04</td> + <td class="tdc bl">1.0048</td> + <td class="tdc bl br">1.26</td> + </tr><tr> + <td class="tdc bl bb">1.06</td> + <td class="tdc bl bb">1.0049</td> + <td class="tdc bl br bb">1.29</td> + </tr><tr> + <td class="tdc bl">1.08</td> + <td class="tdc bl">1.0050</td> + <td class="tdc bl br">1.31</td> + </tr><tr> + <td class="tdc bl">1.10</td> + <td class="tdc bl">1.0051</td> + <td class="tdc bl br">1.34</td> + </tr><tr> + <td class="tdc bl">1.12</td> + <td class="tdc bl">1.0052</td> + <td class="tdc bl br">1.36</td> + </tr><tr> + <td class="tdc bl">1.15</td> + <td class="tdc bl">1.0053</td> + <td class="tdc bl br">1.39</td> + </tr><tr> + <td class="tdc bl">1.17</td> + <td class="tdc bl">1.0054</td> + <td class="tdc bl br">1.41</td> + </tr><tr> + <td class="tdc bl">1.19</td> + <td class="tdc bl">1.0055</td> + <td class="tdc bl br">1.44</td> + </tr><tr> + <td class="tdc bl">1.22</td> + <td class="tdc bl">1.0056</td> + <td class="tdc bl br">1.46</td> + </tr><tr> + <td class="tdc bl">1.25</td> + <td class="tdc bl">1.0057</td> + <td class="tdc bl br">1.49</td> + </tr><tr> + <td class="tdc bl">1.27</td> + <td class="tdc bl">1.0058</td> + <td class="tdc bl br">1.51</td> + </tr><tr> + <td class="tdc bl bb">1.30</td> + <td class="tdc bl bb">1.0059</td> + <td class="tdc bl br bb">1.54</td> + </tr><tr> + <td class="tdc bl">1.32</td> + <td class="tdc bl">1.0060</td> + <td class="tdc bl br">1.56</td> + </tr><tr> + <td class="tdc bl">1.34</td> + <td class="tdc bl">1.0061</td> + <td class="tdc bl br">1.59</td> + </tr><tr> + <td class="tdc bl">1.37</td> + <td class="tdc bl">1.0062</td> + <td class="tdc bl br">1.62</td> + </tr><tr> + <td class="tdc bl">1.39</td> + <td class="tdc bl">1.0063</td> + <td class="tdc bl br">1.64</td> + </tr><tr> + <td class="tdc bl">1.42</td> + <td class="tdc bl">1.0064</td> + <td class="tdc bl br">1.67</td> + </tr><tr> + <td class="tdc bl">1.44</td> + <td class="tdc bl">1.0065</td> + <td class="tdc bl br">1.69</td> + </tr><tr> + <td class="tdc bl">1.46</td> + <td class="tdc bl">1.0066</td> + <td class="tdc bl br">1.72</td> + </tr><tr> + <td class="tdc bl">1.48</td> + <td class="tdc bl">1.0067</td> + <td class="tdc bl br">1.74</td> + </tr><tr> + <td class="tdc bl">1.50</td> + <td class="tdc bl">1.0068</td> + <td class="tdc bl br">1.77</td> + </tr><tr> + <td class="tdc bl bb">1.52</td> + <td class="tdc bl bb">1.0069</td> + <td class="tdc bl br bb">1.79</td> + </tr><tr> + <td class="tdc bl">1.55</td> + <td class="tdc bl">1.0070</td> + <td class="tdc bl br">1.82</td> + </tr><tr> + <td class="tdc bl">1.57</td> + <td class="tdc bl">1.0071</td> + <td class="tdc bl br">1.84</td> + </tr><tr> + <td class="tdc bl">1.59</td> + <td class="tdc bl">1.0072</td> + <td class="tdc bl br">1.87</td> + </tr><tr> + <td class="tdc bl">1.61</td> + <td class="tdc bl">1.0073</td> + <td class="tdc bl br">1.90</td> + </tr><tr> + <td class="tdc bl">1.64</td> + <td class="tdc bl">1.0074</td> + <td class="tdc bl br">1.92</td> + </tr><tr> + <td class="tdc bl">1.66</td> + <td class="tdc bl">1.0075</td> + <td class="tdc bl br">1.95</td> + </tr><tr> + <td class="tdc bl">1.68</td> + <td class="tdc bl">1.0076</td> + <td class="tdc bl br">1.97</td> + </tr><tr> + <td class="tdc bl">1.70</td> + <td class="tdc bl">1.0077</td> + <td class="tdc bl br">2.00</td> + </tr><tr> + <td class="tdc bl">1.72</td> + <td class="tdc bl">1.0078</td> + <td class="tdc bl br">2.02</td> + </tr><tr> + <td class="tdc bl bb">1.75</td> + <td class="tdc bl bb">1.0079</td> + <td class="tdc bl br bb">2.05</td> + </tr><tr> + <td class="tdc bl">1.77</td> + <td class="tdc bl">1.0080</td> + <td class="tdc bl br">2.07</td> + </tr><tr> + <td class="tdc bl">1.79</td> + <td class="tdc bl">1.0081</td> + <td class="tdc bl br">2.10</td> + </tr><tr> + <td class="tdc bl">1.82</td> + <td class="tdc bl">1.0082</td> + <td class="tdc bl br">2.12</td> + </tr><tr> + <td class="tdc bl">1.84</td> + <td class="tdc bl">1.0083</td> + <td class="tdc bl br">2.15</td> + </tr><tr> + <td class="tdc bl">1.86</td> + <td class="tdc bl">1.0084</td> + <td class="tdc bl br">2.17</td> + </tr><tr> + <td class="tdc bl">1.88</td> + <td class="tdc bl">1.0085</td> + <td class="tdc bl br">2.20</td> + </tr><tr> + <td class="tdc bl">1.90</td> + <td class="tdc bl">1.0086</td> + <td class="tdc bl br">2.23</td> + </tr><tr> + <td class="tdc bl">1.92</td> + <td class="tdc bl">1.0087</td> + <td class="tdc bl br">2.25</td> + </tr><tr> + <td class="tdc bl">1.94</td> + <td class="tdc bl">1.0088</td> + <td class="tdc bl br">2.28</td> + </tr><tr> + <td class="tdc bl bb">1.96</td> + <td class="tdc bl bb">1.0089</td> + <td class="tdc bl br bb">2.30</td> + </tr><tr> + <td class="tdc bl">1.98</td> + <td class="tdc bl">1.0090</td> + <td class="tdc bl br">2.33</td> + </tr><tr> + <td class="tdc bl">2.00</td> + <td class="tdc bl">1.0091</td> + <td class="tdc bl br">2.35</td> + </tr><tr> + <td class="tdc bl">2.03</td> + <td class="tdc bl">1.0092</td> + <td class="tdc bl br">2.38</td> + </tr><tr> + <td class="tdc bl">2.05</td> + <td class="tdc bl">1.0093</td> + <td class="tdc bl br">2.41</td> + </tr><tr> + <td class="tdc bl">2.07</td> + <td class="tdc bl">1.0094</td> + <td class="tdc bl br">2.43</td> + </tr><tr> + <td class="tdc bl">2.09</td> + <td class="tdc bl">1.0095</td> + <td class="tdc bl br">2.46</td> + </tr><tr> + <td class="tdc bl">2.11</td> + <td class="tdc bl">1.0096</td> + <td class="tdc bl br">2.48</td> + </tr><tr> + <td class="tdc bl">2.14</td> + <td class="tdc bl">1.0097</td> + <td class="tdc bl br">2.51</td> + </tr><tr> + <td class="tdc bl">2.16</td> + <td class="tdc bl">1.0098</td> + <td class="tdc bl br">2.53</td> + </tr><tr> + <td class="tdc bl bb">2.18</td> + <td class="tdc bl bb">1.0099</td> + <td class="tdc bl br bb">2.56</td> + </tr><tr> + <td class="tdc bl">2.21</td> + <td class="tdc bl">1.0100</td> + <td class="tdc bl br">2.58</td> + </tr><tr> + <td class="tdc bl">2.23</td> + <td class="tdc bl">1.0101</td> + <td class="tdc bl br">2.61</td> + </tr><tr> + <td class="tdc bl">2.25</td> + <td class="tdc bl">1.0102</td> + <td class="tdc bl br">2.64</td> + </tr><tr> + <td class="tdc bl">2.27</td> + <td class="tdc bl">1.0103</td> + <td class="tdc bl br">2.66</td> + </tr><tr> + <td class="tdc bl">2.30</td> + <td class="tdc bl">1.0104</td> + <td class="tdc bl br">2.69</td> + </tr><tr> + <td class="tdc bl">2.32</td> + <td class="tdc bl">1.0105</td> + <td class="tdc bl br">2.71</td> + </tr><tr> + <td class="tdc bl">2.34</td> + <td class="tdc bl">1.0106</td> + <td class="tdc bl br">2.74</td> + </tr><tr> + <td class="tdc bl">2.36</td> + <td class="tdc bl">1.0107</td> + <td class="tdc bl br">2.76</td> + </tr><tr> + <td class="tdc bl">2.38</td> + <td class="tdc bl">1.0108</td> + <td class="tdc bl br">2.79</td> + </tr><tr> + <td class="tdc bl bb">2.40</td> + <td class="tdc bl bb">1.0109</td> + <td class="tdc bl br bb">2.82</td> + </tr><tr> + <td class="tdc bl">2.42</td> + <td class="tdc bl">1.0110</td> + <td class="tdc bl br">2.84</td> + </tr><tr> + <td class="tdc bl">2.44</td> + <td class="tdc bl">1.0111</td> + <td class="tdc bl br">2.87</td> + </tr><tr> + <td class="tdc bl">2.46</td> + <td class="tdc bl">1.0112</td> + <td class="tdc bl br">2.89</td> + </tr><tr> + <td class="tdc bl">2.48</td> + <td class="tdc bl">1.0113</td> + <td class="tdc bl br">2.92</td> + </tr><tr> + <td class="tdc bl">2.50</td> + <td class="tdc bl">1.0114</td> + <td class="tdc bl br">2.94</td> + </tr><tr> + <td class="tdc bl">2.52</td> + <td class="tdc bl">1.0115</td> + <td class="tdc bl br">2.97</td> + </tr><tr> + <td class="tdc bl">2.54</td> + <td class="tdc bl">1.0116</td> + <td class="tdc bl br">2.99</td> + </tr><tr> + <td class="tdc bl">2.57</td> + <td class="tdc bl">1.0117</td> + <td class="tdc bl br">3.02</td> + </tr><tr> + <td class="tdc bl">2.59</td> + <td class="tdc bl">1.0118</td> + <td class="tdc bl br">3.05</td> + </tr><tr> + <td class="tdc bl bb">2.61</td> + <td class="tdc bl bb">1.0119</td> + <td class="tdc bl br bb">3.07</td> + </tr><tr> + <td class="tdc bl">2.64</td> + <td class="tdc bl">1.0120</td> + <td class="tdc bl br">3.10</td> + </tr><tr> + <td class="tdc bl">2.66</td> + <td class="tdc bl">1.0121</td> + <td class="tdc bl br">3.12</td> + </tr><tr> + <td class="tdc bl">2.68</td> + <td class="tdc bl">1.0122</td> + <td class="tdc bl br">3.15</td> + </tr><tr> + <td class="tdc bl">2.70</td> + <td class="tdc bl">1.0123</td> + <td class="tdc bl br">3.17</td> + </tr><tr> + <td class="tdc bl">2.72</td> + <td class="tdc bl">1.0124</td> + <td class="tdc bl br">3.20</td> + </tr><tr> + <td class="tdc bl">2.75</td> + <td class="tdc bl">1.0125</td> + <td class="tdc bl br">3.23</td> + </tr><tr> + <td class="tdc bl">2.77</td> + <td class="tdc bl">1.0126</td> + <td class="tdc bl br">3.25</td> + </tr><tr> + <td class="tdc bl">2.79</td> + <td class="tdc bl">1.0127</td> + <td class="tdc bl br">3.28</td> + </tr><tr> + <td class="tdc bl">2.82</td> + <td class="tdc bl">1.0128</td> + <td class="tdc bl br">3.30</td> + </tr><tr> + <td class="tdc bl bb">2.84</td> + <td class="tdc bl bb">1.0129</td> + <td class="tdc bl br bb">3.33</td> + </tr><tr> + <td class="tdc bl">2.86</td> + <td class="tdc bl">1.0130</td> + <td class="tdc bl br">3.35</td> + </tr><tr> + <td class="tdc bl">2.88</td> + <td class="tdc bl">1.0131</td> + <td class="tdc bl br">3.38</td> + </tr><tr> + <td class="tdc bl">2.90</td> + <td class="tdc bl">1.0132</td> + <td class="tdc bl br">3.41</td> + </tr><tr> + <td class="tdc bl">2.92</td> + <td class="tdc bl">1.0133</td> + <td class="tdc bl br">3.43</td> + </tr><tr> + <td class="tdc bl">2.94</td> + <td class="tdc bl">1.0134</td> + <td class="tdc bl br">3.46</td> + </tr><tr> + <td class="tdc bl">2.96</td> + <td class="tdc bl">1.0135</td> + <td class="tdc bl br">3.48</td> + </tr><tr> + <td class="tdc bl">2.98</td> + <td class="tdc bl">1.0136</td> + <td class="tdc bl br">3.51</td> + </tr><tr> + <td class="tdc bl bb">3.00</td> + <td class="tdc bl bb">1.0137</td> + <td class="tdc bl br bb">3.54</td> + </tr> + </tbody> +</table> + +<p>If it be desired to use this table for the examination of liquors +containing a higher percentage of extract, Schultze’s table (intended +originally for wort) may be consulted.</p> + +<p>Gautier regards the fixed solids as the residue obtained on +evaporating, in a flat platinum dish, ten cubic centimeters of wine at +100° for four hours and a half.<a id="FNanchor_639" href="#Footnote_639" class="fnanchor">[639]</a></p> + +<p><span class="pagenum"><a id="Page_626"></a>[Pg 626]</span> +The official French method is as follows: Twenty cubic centimeters of +wine are placed in a flat bottom, platinum dish of such a diameter +that the depth of the liquid therein does not exceed one millimeter. +The dish should be immersed as totally as possible in the steam. The +heating is continued for six hours.</p> + +<p>The following method is used at the municipal laboratory of Paris:</p> + +<p>Twenty-five cubic centimeters of wine are placed in a flat bottom, +platinum dish seventy millimeters in diameter and twenty-five deep. The +dish is placed on a water bath in such a manner that it just touches +the surface of the water which is kept at a constant level. The heating +is continued for seven hours.<a id="FNanchor_640" href="#Footnote_640" class="fnanchor">[640]</a></p> + +<p><b>625. Determination in a Vacuum.</b>—To avoid the changes and +decomposition produced by heating, the fixed solids may also be +determined by drying the sample in a vacuum over sulfuric acid. In +this laboratory, it has been found that the process may be greatly +facilitated by connecting the desiccating apparatus with the vacuum +service of the working desks in which a vacuum corresponding to a +mercurial column of 600 millimeters is obtained. The desiccator is +provided with a valve whereby a minute current of dry air is allowed +to flow through it. This current is not large enough to lessen the +vacuum but is sufficient to greatly accelerate the rapidity of the +evaporation. The evaporation is hastened also, in a marked degree, by +absorbing the liquid with a piece of filter paper previously dried in a +vacuum. When it is desired to examine the residue, however, it must be +obtained in a flat dish exposing a large surface to evaporation.</p> + +<p><b>626. Estimation of Water.</b>—It is evident that the percentage of +water in a fermented beverage is easily calculated when the percentage +of alcohol by weight and that of the dry residue are known. In a given +case, if the number of grams of alcohol in 100 of the sample be five +and that of fixed solids four and a half, the quantity of water therein +is 100 - (5.0 + 4.5) = 90.5 grams. In this case the volatile essences +are counted as water, but these, at most, are so small in quantity as +to be practically unweighable. Nevertheless, it must be admitted that +<span class="pagenum"><a id="Page_627"></a>[Pg 627]</span> +direct drying, in many cases, may give erroneous results, especially +when the sample contains an abundance of ethers and of glycerol. The +loss which takes place on evaporation may be diminished by adding to +the sample, before evaporation, a known weight of potassium sulfate +in crystals, which serves to increase the surface of evaporation, to +hasten the process and to obtain a quantity of residue in excess of +that secured by direct evaporation in an open dish.</p> + +<p><b>627. Total Acidity.</b>—The acidity found in fermented beverages +is due both to the natural acids of the materials from which they are +made, and to those caused by fermentation. The typical acids also +indicate the nature of the original materials, as malic in cider and +tartaric in wine. The acids of beers are due almost exclusively to +fermentation, and acetic is probably the dominant one. In determining +total acidity, it is not always convenient to ascertain beforehand what +acid predominates, nor to accurately distribute the acid among its +various components. In the analytical work it is advisable, therefore, +to estimate the total acid of cider as malic, of wines as tartaric and +of beers as acetic. The process of titration is conducted as follows:</p> + +<p>Expel any carbon dioxid that is present by continued shaking. Transfer +ten cubic centimeters to a beaker and, in the case of white wines, add +about ten drops of a neutral litmus solution. Add decinormal sodium +hydroxid solution until the red color changes to violet. Then add the +reagent, a few drops at a time, until a drop of the liquid, placed on +delicate red litmus paper, shows an alkaline reaction.</p> + +<p>One cubic centimeter of decinormal sodium hydroxid solution = 0.0075 +gram tartaric, 0.0067 of malic and 0.006 gram of acetic acid.</p> + +<p><b>628. Determination of Volatile Acids.</b>—Fifty cubic centimeters +of the sample, to which a little tannin has been added to prevent +foaming, are distilled in a current of steam. The flask is heated until +the liquid boils, when the lamp under it is turned down and the steam +passed through until 200 cubic centimeters have been collected in the +<span class="pagenum"><a id="Page_628"></a>[Pg 628]</span> +receiver. The distillate is titrated with decinormal sodium hydroxid +solution and the result expressed as acetic acid.</p> + +<p>One cubic centimeter of decinormal sodium hydroxid solution = 0.0060 +gram acetic acid.</p> + +<p>The acidity due to volatile acids may be determined by ascertaining the +total acidity as above described, evaporating 100 cubic centimeters to +one-third of their volume, restoring the original volume with water and +again titrating. The difference between the first and second titrations +represents the volatile acidity.</p> + +<p>A method of determining volatile acidity in wines, without the +application of heat, has been proposed by de la Source.<a id="FNanchor_641" href="#Footnote_641" class="fnanchor">[641]</a> +The sample, five cubic centimeters, freed of carbon dioxid by shaking, +is placed in a flat dish about eight centimeters in diameter. In a +separate portion of the sample, the total acidity is determined in the +presence of phenolphthalien by a set solution of barium hydroxid, one +cubic centimeter of which is equal to four milligrams of sulfuric acid. +The sample in the flat dish is placed in a desiccator, which contains +both sulfuric acid and solid potassium hydroxid, and left for two days, +by which time it is practically dry. The residue is dissolved in two +cubic centimeters of warm water and the dish is kept in the desiccator +for an additional two days. By this time the volatile acids, even +acetic, will have disappeared and the residual acidity is determined +after solution in water.</p> + +<p>The method is also applicable when wines have been treated with an +alkali. In this case two samples of five cubic centimeters each are +acidified with two cubic centimeters of a solution of tartaric acid +containing twenty-five grams per liter. This treatment sets free the +volatile acids, and their quantity is determined as before.</p> + +<p><b>629. Titration with Phenolphthalien.</b>—The total acidity is also +easily determined by titration with a set alkali, using phenolphthalien +as indicator. Colored liquors must be treated with animal black before +the analysis. The sample is shaken to expel carbon dioxid and five +cubic centimeters added to 100 of water containing phenolphthalien. The +<span class="pagenum"><a id="Page_629"></a>[Pg 629]</span> +set alkali (tenth normal soda) is added until the red color is +discharged. Even wines having a considerable degree of color may be +titrated in this way.<a id="FNanchor_642" href="#Footnote_642" class="fnanchor">[642]</a> +The acidity, expressed as tartaric, may be stated as due to sulfuric by +dividing by 1.53.</p> + +<p><b>630. Determination of Tartaric Acid.</b>—The determination of +potassium bitartrate is necessary when an estimation of the free +tartaric acid is desired.<a id="FNanchor_643" href="#Footnote_643" class="fnanchor">[643]</a></p> + +<p>Fifty cubic centimeters of wine are placed in a porcelain dish and +evaporated to a sirupy consistence, a little quartz sand being added +to render subsequent extraction easier. After cooling, seventy cubic +centimeters of ninety-six per cent alcohol are added with constant +stirring. After standing for twelve hours, at as low a temperature as +practicable, the solution is filtered and the precipitate washed with +alcohol until the filtrate is no longer acid. The alcoholic filtrate +is preserved for the estimation of the tartaric acid. The filter and +precipitate are returned to the porcelain dish and repeatedly treated +with hot water, each extraction being filtered into a flask or beaker +until the washings are neutral. The combined aqueous filtrates and +washings are titrated with decinormal sodium hydroxid solution.</p> + +<p>One cubic centimeter of decinormal sodium hydroxid solution = 0.0188 +gram potassium bitartrate.</p> + +<p>The alcoholic filtrate is made up to a definite volume with water and +divided into two equal portions. One portion is exactly neutralized +with decinormal sodium hydroxid solution, the other portion added, +the alcohol evaporated, the residue washed into a porcelain dish and +treated as above.</p> + +<p>One cubic centimeter decinormal sodium hydroxid solution = 0.0075 gram +tartaric acid.</p> + +<p>As, however, only half of the free tartaric acid is determined by this +method:</p> + +<p>One cubic centimeter decinormal sodium hydroxid = 0.0150 gram of +tartaric acid.</p> + +<p><b>631. Modified Berthelot-Fleury Method.</b>—Ten cubic centimeters of +wine are neutralized with potassium hydroxid solution and mixed in a +graduated cylinder with forty cubic centimeters of the same sample. To +<span class="pagenum"><a id="Page_630"></a>[Pg 630]</span> +one-fifth of the volume, corresponding to ten cubic centimeters of +wine, fifty cubic centimeters of a mixture of equal parts of alcohol +and ether are added and allowed to stand twenty-four hours. The +precipitated potassium bitartrate is separated by filtration, dissolved +in water and titrated. The excess of potassium bitartrate over the +amount of that constituent present in the wine corresponds to the free +tartaric acid.<a id="FNanchor_644" href="#Footnote_644" class="fnanchor">[644]</a></p> + +<p><b>632. Determination of Tartaric, Malic and Succinic Acids.</b>—Two +hundred cubic centimeters of wine are evaporated to one-half, cooled +and lead subacetate solution added until the reaction is alkaline.<a id="FNanchor_645" href="#Footnote_645" class="fnanchor">[645]</a> +The precipitate is separated by filtration and washed with cold +water until the filtrate shows only a slight reaction for lead. +The precipitate is washed from the filter into a beaker, by means +of hot water, and treated hot with hydrogen sulfid until all the +lead is converted into sulfid. It is then filtered hot and the lead +sulfid washed with hot water until the washings are no longer acid. +The filtrate and washings are evaporated to fifty cubic centimeters +and accurately neutralized with potassium hydroxid. An excess of a +saturated solution of calcium acetate is added and the liquid allowed +to stand from four to six hours with frequent stirring. It is then +filtered and the precipitate washed until the filtrate amounts to +exactly 100 cubic centimeters. The precipitate of calcium tartrate is +converted into calcium oxid by igniting in a platinum crucible. After +cooling, from ten to fifteen cubic centimeters of normal hydrochloric +acid are added, the solution washed into a beaker and accurately +titrated with normal potassium hydroxid solution. Every cubic +centimeter of normal acid saturated by the calcium oxid is equivalent +to 0.0750 gram tartaric acid. To the amount so obtained, 0.0286 gram +must be added, representing the tartaric acid held in solution in the +filtrate as calcium tartrate. The sum represents the total tartaric +acid in the wine.</p> + +<p>The filtrate from the calcium tartrate is evaporated to about +twenty-five cubic centimeters, cooled and mixed with three times its +volume of ninety-six per cent alcohol. After standing several hours, +the precipitate is collected on a weighed filter, dried at 100° and +weighed. It represents the calcium salts of malic, succinic and +<span class="pagenum"><a id="Page_631"></a>[Pg 631]</span> +sulfuric acids and of the tartaric acid which remained in solution. +This precipitate is dissolved in a minimum quantity of hydrochloric +acid, filtered and the filter washed with hot water. Potassium +carbonate solution is added to the hot filtrate, and the precipitated +calcium carbonate separated by filtration and washed. The filtrate +contains the potassium salts of the above named acids. It is +neutralized with acetic acid, evaporated to a small volume and +precipitated hot with barium chlorid. The precipitate of barium +succinate and sulfate is separated by filtration, washed with hot +water and treated on the filter with dilute hydrochloric acid. The +barium sulfate remaining is washed, dried, ignited and weighed. In +the filtrate, which contains the barium succinate, the barium is +precipitated hot with sulfuric acid, washed, dried, ignited and +weighed. Two hundred and twenty-three parts of barium sulfate equal 118 +parts of succinic acid. The succinic and sulfuric acids, as well as the +tartaric acid remaining in solution, which is equal to 0.0286 gram, +are to be calculated as calcium salts and the result deducted from the +total weight of the calcium precipitate. The remainder is the calcium +malate, of which 172 parts equal 134 parts malic acid.</p> + +<p>According to Macagno, succinic acid may be estimated in wines by the +following process:<a id="FNanchor_646" href="#Footnote_646" class="fnanchor">[646]</a> +One liter of the wine is digested with lead hydroxid, evaporated on the +water bath and the residue extracted with strong alcohol. The residual +salts of lead are boiled with a ten per cent solution of ammonium +nitrate, which dissolves the salts of succinic acid. The solution is +filtered, the lead removed by hydrogen sulfid, boiled, neutralized +with ammonia and treated with ferric chlorid as long as a precipitate +is formed. The ferric succinate is separated by filtration, washed and +ignited. The succinic acid is calculated from the weight of ferric oxid +obtained.</p> + +<p>Malic acid in wines and ciders is determined by the method of Berthelot +in the following manner:<a id="FNanchor_647" href="#Footnote_647" class="fnanchor">[647]</a> +The sample is evaporated until reduced to a tenth of its volume. To +the residue an equal volume of ninety per cent alcohol is added and +the mixture set aside for some time. The tartaric acid and tartrates +separate, together with the greater part of the salts of lime which may +be present. +<span class="pagenum"><a id="Page_632"></a>[Pg 632]</span></p> + +<p>The supernatant liquid is decanted and a small quantity of lime +added to it until in slight excess of that required to neutralize +the acidity. Calcium malate is separated mixed with lime. The solid +matters are separated by filtration, dissolved in a ten per cent +solution of nitric acid, from which the lime bimalate will separate in +a crystalline form. The weight of calcium bimalate multiplied by 0.59 +gives that of the malic acid.</p> + +<p><b>633. Polarizing Bodies in Fermented Beverages.</b>—The study of +the nature of the carbohydrates, which constitute an important part of +the solid matters dissolved in fermented beverages, is of the greatest +importance. These bodies consist of grape sugars, sucrose, tartaric +acid and the unfermented hydrolytic products derived from starch. A +natural grape sugar (chiefly dextrose) is found in wines. Sucrose +is also a very important constituent of sweet wines. The hydrolytic +products of starch are found in beers, either as a residue from the +fermentation of malt or from the rice, glucose, hominy grits etc., +added in brewing. The character and quantities of these residues can +be determined by the methods already given in the parts of this volume +relating to sugars and starches. For convenience, however, and for +special application to the investigation of fermented beverages a +résumé of the methods adopted by the official chemists follows:<a id="FNanchor_648" href="#Footnote_648" class="fnanchor">[648]</a></p> + +<p><b>634. Determination of Reducing Sugars.</b>—The reducing sugars are +estimated as dextrose, and may be determined by any of the methods +given for the estimation thereof (<b><a href="#P_113">113-140</a></b>).</p> + +<p><b>635. Polarization.</b>—All results are to be stated as the +polarization of the undiluted sample. The triple field shadow +saccharimeter is recommended, and the results are expressed in the +terms of the sugar scale of this instrument. If any other instrument +be used, or if it be desirable to convert to angular rotation, the +following factors may be employed:</p> + +<table class="spb1 fs_90"> + <tbody><tr> + <td class="tdl">1° Schmidt and Haensch</td> + <td class="tdl_wsp">= 0°.3468</td> + <td class="tdl_wsp">angular rotation D.</td> + </tr><tr> + <td class="tdl">1° angular rotation D</td> + <td class="tdl_wsp">= 2°.8835</td> + <td class="tdl_wsp">Schmidt and Haensch.</td> + </tr><tr> + <td class="tdl">1° Schmidt and Haensch</td> + <td class="tdl_wsp">= 2°.6048</td> + <td class="tdl_wsp">Wild (sugar scale).</td> + </tr><tr> + <td class="tdl">1° Wild (sugar scale)</td> + <td class="tdl_wsp">= 0°.3840</td> + <td class="tdl_wsp">Schmidt and Haensch.</td> + </tr><tr> + <td class="tdl">1° Wild (sugar scale)</td> + <td class="tdl_wsp">= 0°.1331</td> + <td class="tdl_wsp">angular rotation D.</td> + </tr><tr> + <td class="tdl">1° angular rotation D</td> + <td class="tdl_wsp">= 0°.7511</td> + <td class="tdl_wsp">Wild (sugar scale).</td> + </tr><tr> + <td class="tdl">1° Laurent (sugar scale)</td> + <td class="tdl_wsp">= 0°.2167</td> + <td class="tdl_wsp">angular rotation D.</td> + </tr><tr> + <td class="tdl">1° angular rotation D</td> + <td class="tdl_wsp">= 4°.6154</td> + <td class="tdl_wsp">Laurent (sugar scale).</td> + </tr> + </tbody> +</table> + +<p><span class="pagenum"><a id="Page_633"></a>[Pg 633]</span> +In the above table D represents the angular rotation produced with +yellow monochromatic light.</p> + +<p>(<i>a</i>) <i>In White Wines or Beers.</i>—Sixty cubic centimeters of +wine are decolorized with three cubic centimeters of lead subacetate +solution and filtered. Thirty cubic centimeters of the filtrate are +treated with one and five-tenths cubic centimeters of a saturated +solution of sodium carbonate, filtered and polarized. This gives a +solution of nearly ten to eleven, which must be considered in the +calculation, and the polariscope reading must accordingly be increased +one-tenth.</p> + +<p>(<i>b</i>) <i>In Red Wines.</i>—Sixty cubic centimeters of wine are +decolorized with six cubic centimeters of lead subacetate solution and +filtered. To thirty cubic centimeters of the filtrate, three cubic +centimeters of a saturated solution of sodium carbonate are added, +filtered and the filtrate polarized. The dilution in this case is +nearly five to six, and the polariscope reading must accordingly be +increased one-fifth.</p> + +<p>(<i>c</i>) <i>In Sweet Wines.</i> (1) <i>Before Inversion.</i>—One +hundred cubic centimeters are decolorized with two cubic centimeters of +lead subacetate solution and filtered after the addition of eight cubic +centimeters of water. One-half cubic centimeter of a saturated solution +of sodium carbonate and four and five-tenths cubic centimeters of water +are added to fifty-five cubic centimeters of the filtrate, the liquids +mixed, filtered and polarized. The polariscope reading is multiplied by 1.2.</p> + +<p>(2) <i>After Inversion.</i>—Thirty-three cubic centimeters of the +filtrate from the lead subacetate in (1) are placed in a flask with +three cubic centimeters of strong hydrochloric acid. After mixing +well, the flask is placed in water and heated until a thermometer, +placed in the flask with the bulb as near the center of the liquid as +possible, marks 68°, consuming about fifteen minutes in the heating. +It is then removed, cooled quickly to room temperature, filtered and +polarized, the temperature being noted. The polariscope reading is +multiplied by 1.2. Because of the action of lead subacetate on invert +sugar (<b><a href="#P_87">87</a></b>) it is advisable to decolorize the +samples with other reagents (<b><a href="#P_87">87-89</a></b>).</p> + +<p>(3) <i>After Fermentation.</i>—Fifty cubic centimeters of wine, which +<span class="pagenum"><a id="Page_634"></a>[Pg 634]</span> +have been dealcoholized by evaporation and made up to the original +volume with water, are mixed, in a small flask, with well washed +beer yeast and kept at 30° until fermentation has ceased, which +requires from two to three days. The liquid is washed into a 100 cubic +centimeter flask, a few drops of a solution of acid mercuric nitrate +and then lead subacetate solution, followed by sodium carbonate, added. +The flask is filled to the mark with water, shaken, the solution +filtered and polarized and the reading multiplied by two.</p> + +<p><b>636. Application of Analytical Methods.</b>—(1) <i>There is no +rotation.</i>—This may be due to the absence of any rotatory body, +to the simultaneous presence of the dextrorotatory nonfermentable +constituents of commercial dextrose and levorotatory sugar, or to the +simultaneous presence of dextrorotatory cane sugar and levorotatory +invert sugar.</p> + +<p>(<i>a</i>) <i>The Wine is Inverted.</i>—A levorotation shows that the +sample contains cane sugar.</p> + +<p>(<i>b</i>) <i>The Wine is Fermented.</i>—A dextrorotation shows +that both levorotatory sugar and the unfermentable constituents of +commercial dextrose are present.</p> + +<p>If no change take place in either (<i>a</i>) or (<i>b</i>) in the +rotation, it proves the absence of unfermented cane sugar, the unfermentable +constituents of commercial dextrose and of levorotatory sugar.</p> + +<p>(2) <i>There is right rotation.</i>—This may be caused by unfermented +cane sugar, the unfermentable constituents of commercial dextrose or both.</p> + +<p>(<i>a</i>) The sugar is inverted:</p> + +<p>(<i>a</i>₁) <i>It rotates to the left after inversion.</i>—Unfermented +cane sugar is present.</p> + +<p>(<i>a</i>₂) <i>It rotates more than 2°.3 to the right.</i>—The +unfermentable constituents of commercial dextrose are present.</p> + +<p>(<i>a</i>₃) <i>It rotates less than 2°.3 and more than 0°.9 to the +right.</i>—It is in this case treated as follows:</p> + +<p>Two hundred and ten cubic centimeters of the sample are evaporated to a +thin sirup with a few drops of a twenty per cent solution of potassium +acetate. To the residue 200 cubic centimeters of ninety per cent +alcohol are added with constant stirring. The alcoholic solution is +<span class="pagenum"><a id="Page_635"></a>[Pg 635]</span> +filtered into a flask and the alcohol removed by distillation until +about five cubic centimeters remain. The residue is mixed with washed +bone-black, filtered into a graduated cylinder and washed until the +filtrate amounts to thirty cubic centimeters. When the filtrate shows +a dextrorotation of more than 1°.5, it indicates the presence of +unfermentable constituents of commercial dextrose.</p> + +<p>(3) <i>There is left rotation.</i>—The sample contains unfermented +levorotatory sugar, derived either from the must or mash or from +the inversion of added cane sugar. It may, however, also contain +unfermented cane sugar and the unfermentable constituents of commercial +dextrose.</p> + +<p>(<i>a</i>) The wine sugars are fermented according to directions in +<b><a href="#P_262">262</a></b>.</p> + +<p>(<i>a</i>₁) <i>It polarizes 3° after fermentation.</i>—It contains +only levorotatory sugar.</p> + +<p>(<i>a</i>₂) <i>It rotates to the right.</i>— It contains both +levorotatory sugar and the unfermentable constituents of commercial +dextrose.</p> + +<p>(<i>b</i>₁) The sucrose is inverted according to (<i>c</i>), in (2).</p> + +<p>(<i>b</i>₂) It is more strongly levorotatory after inversion. In +contains both levorotatory sugar and unfermented cane sugar.</p> + +<p><b>637. Estimation of Sucrose, Dextrose, Invert Sugar, Maltose and +Dextrin.</b>—The total and relative quantities of these carbohydrates +are determined by the processes already described (<b><a href="#P_237">237-262</a></b>).</p> + +<p><b>638. Determination of Glycerol.</b>—(<i>a</i>) <i>In Dry Wines +and Beers.</i>—One hundred cubic centimeters of wine are evaporated +in a porcelain dish to about ten cubic centimeters, a little quartz +sand and milk of lime added and the evaporation carried almost to +dryness. The residue is mixed with fifty cubic centimeters of ninety +per cent alcohol, using a glass pestle or spatula to break up any solid +particles, heated to boiling on the water bath, allowed to settle and +the liquid filtered into a small flask. The residue is repeatedly +extracted in a similar manner, with small portions of boiling alcohol, +until the filtrate in the flask amounts to about 150 cubic centimeters. +A little quartz sand is added, the flask connected with a condenser and +<span class="pagenum"><a id="Page_636"></a>[Pg 636]</span> +the alcohol slowly distilled until about ten cubic centimeters remain. +The evaporation is continued on the water bath until the residue +becomes sirupy. It is cooled and dissolved in ten cubic centimeters of +absolute alcohol. The solution may be facilitated by gentle heating +on the steam bath. Fifteen cubic centimeters of anhydrous ether are +added, the flask stoppered and allowed to stand until the precipitate +has collected on the sides and bottom of the flask. The clear liquid +is decanted into a tared weighing bottle, the precipitate repeatedly +washed with a few cubic centimeters of a mixture of one part of +absolute alcohol and one and five-tenths parts anhydrous ether and the +washings added to the solution. The ether-alcohol is evaporated on +the steam bath, the residue dried one hour in a water oven, weighed, +the amount of ash determined and its weight deducted from that of the +weighed residue to get the quantity of glycerol.</p> + +<p>(<i>b</i>) <i>In Sweet Wines.</i>—One hundred cubic centimeters of +wine are evaporated on the steam bath to a sirupy consistence, a little +quartz sand being added to render subsequent extraction easier. The +residue is repeatedly treated with absolute alcohol until the united +extracts amount to from 100 to 150 cubic centimeters. The solution is +collected in a flask and for every part of alcohol one and five-tenths +parts of ether are added, the liquid well shaken and allowed to stand +until it becomes clear. The supernatant liquor is decanted into a +beaker and the precipitate washed with a few cubic centimeters of +a mixture of one part alcohol and one and five-tenths parts ether. +The united liquids are distilled, the evaporation being finished on +the water bath, the residue is dissolved in water, transferred to a +porcelain dish and treated as under (<i>a</i>).</p> + +<p><b>639. Determination of Coloring Matters in Wines.</b>—The methods +of detecting the more commonly occurring coloring matters in wines as +practiced by the official chemists are given below.</p> + +<p>(<i>a</i>) <i>Cazeneuve Reaction.</i>—Add two-tenths gram of +precipitated mercuric oxid to ten cubic centimeters of wine, shake for +one minute and filter.</p> + +<p>Pure wines give filtrates which are colorless or light yellow, while +the presence of a more or less red coloration indicates that an anilin +color has been added to the wine. +<span class="pagenum"><a id="Page_637"></a>[Pg 637]</span></p> + +<p>(<i>b</i>) <i>Method of Sostegni and Carpentieri.</i>—Evaporate the +alcohol from 200 cubic centimeters of wine. Add from two to four cubic +centimeters of a ten per cent solution of hyrochloric acid, immerse +therein some threads of fat-free wool and boil for five minutes. Remove +the threads, wash them with cold water acidified with hydrochloric, +then with hot water acidified with hydrochloric, then with pure water +and dissolve the color in a boiling mixture of fifty cubic centimeters +of water and two cubic centimeters of concentrated ammonia. Replace +the threads by new ones, acidify with hydrochloric and boil again for +five minutes. In the presence of anilin colors to the amount of two +milligrams per liter, the threads are dyed as follows:</p> + +<table class="spb1"> + <tbody><tr> + <td class="tdl">Safranin</td> + <td class="tdr">light rose-red.</td> + </tr><tr> + <td class="tdl">Vinolin</td> + <td class="tdr">rose-red to violet.</td> + </tr><tr> + <td class="tdl">Bordeaux-red  </td> + <td class="tdr">rose-red to violet.</td> + </tr><tr> + <td class="tdl">Ponceau-red</td> + <td class="tdr">rose-red.</td> + </tr><tr> + <td class="tdl">Tropæolin oo</td> + <td class="tdr">straw yellow.</td> + </tr><tr> + <td class="tdl">Tropæolin ooo</td> + <td class="tdr">light orange.</td> + </tr> + </tbody> +</table> + +<p>(<i>c</i>) <i>Detection of Fuchsin and Orseille.</i>—To twenty cubic +centimeters of wine add ten cubic centimeters of lead acetate solution, +heat slightly and mix by shaking. Filter into a test-tube, add two +cubic centimeters of amyl alcohol and shake. If the amyl alcohol be +colored red, separate it and divide it into two portions. To one add +hydrochloric acid, to the other ammonia. When the color is due to +fuchsin, the amyl alcohol will in both cases be decolorized; when due +to orseille, the ammonia will change the color of the amyl alcohol to +purple-violet.</p> + +<p><b>640. Determination of Ash.</b>—The residue from the direct extract +determination is incinerated at as low a heat as possible. Repeated +moistening, drying and heating to low redness is advisable to get rid +of all organic substances. When a quantitive analysis of the ash is +desired, large quantities of the sample are evaporated to dryness and +the residue incinerated with the usual precautions.</p> + +<p><b>641. Determination Of Potash.</b>—(<i>a</i>) <i>Kayser’s +Method.</i>—Dissolve seven-tenths gram pure sodium hydroxid and two +grams of tartaric acid in 100 cubic centimeters of wine, add 150 cubic +<span class="pagenum"><a id="Page_638"></a>[Pg 638]</span> +centimeters of ninety-two to ninety-four per cent alcohol and allow +the liquid to stand twenty-four hours. The precipitated potassium +bitartrate is collected on a small filter and washed with fifty per +cent alcohol until the filtrate amounts to 260 cubic centimeters. The +precipitate and filter are transferred to the beaker in which the +precipitation was made, the precipitate dissolved in hot water, the +volume made up to 200 cubic centimeters and fifty cubic centimeters +thereof titrated with decinormal sodium hydroxid solution, adding 0.004 +gram to the final result, representing the potash which remains in +solution as bitartrate.</p> + +<p>(<i>b</i>) <i>Platinum Chlorid Method.</i>—Evaporate 100 cubic +centimeters of the wine to dryness, incinerate the residue and +determine the potash as in ash analysis.<a id="FNanchor_649" href="#Footnote_649" class="fnanchor">[649]</a></p> + +<p><b>642. Determination of Sulfurous Acid.</b>—One hundred cubic +centimeters of wine are distilled in a current of carbon dioxid, after +the addition of phosphoric acid, until about fifty cubic centimeters +have passed over. The distillate is collected in accurately set iodin +solution. When the distillation is finished, the excess of iodin is +determined with set sodium thiosulfate solution and the sulfurous acid +calculated from the iodin used.</p> + +<p><b>643. Detection of Salicylic Acid.</b>—(<i>a</i>) <i>Spica’s +Method.</i>—Acidify 100 cubic centimeters of the liquor with sulfuric +and extract with sulfuric ether. Evaporate the extract to dryness, warm +the residue carefully with one drop of concentrated nitric acid and add +two or three drops of ammonia. The presence of salicylic acid in the +liquor is indicated by the formation of a yellow color due to ammonium +picrate and may be confirmed by dyeing therein a thread of fat-free wool.</p> + +<p>(<i>b</i>) <i>Bigelow’s Method.</i>—Place 100 cubic centimeters of the +wine in a separatory funnel, add five cubic centimeters of sulfuric +acid (1-3) and extract with a sufficient quantity of a mixture of eight +or nine parts of ether to one part of petroleum ether. Throw away the +aqueous part of the extract, wash the ether once with water, then shake +thoroughly with about fifty cubic centimeters of water, to which from +<span class="pagenum"><a id="Page_639"></a>[Pg 639]</span> +six to eight drops of a one-half per cent solution of ferric chlorid +have been added. Discard the aqueous solution, which contains the +greater part of the tannin in combination with iron, wash again with +water, transfer the ethereal solution to a porcelain dish and allow +to evaporate spontaneously. Heat the dish on the steam bath, take up +the residue with one or two cubic centimeters of water, filter into +a test-tube and add one to two drops of one-half per cent solution +of ferric chlorid. The presence of salicylic acid is indicated by +the appearance of a violet-red coloration. In the case of red wines, +a second extraction of the residue with ether mixture is sometimes +necessary. This method cannot be used in the examination of beers and ales.</p> + +<p>(<i>c</i>) <i>Girard’s Method.</i>—Extract a portion of the acidified +liquor with ether as in the preceding methods, evaporate the extract +to dryness and exhaust the residue with petroleum ether. The residue +from the petroleum ether extract is dissolved in water and treated with +a few drops of a very dilute solution of ferric chlorid. The presence +of salicylic acid is indicated by the appearance of a violet-red coloration.</p> + +<p><b>644. Detection of Gum and Dextrin.</b>—Four cubic centimeters of +the sample are mixed with ten cubic centimeters of ninety-six per cent +alcohol. When gum arabic or dextrin is present, a lumpy, thick and +stringy precipitate is produced, whereas pure wine becomes at first +opalescent and then gives a flocculent precipitate.</p> + +<p><b>645. Determination of Nitrogen.</b>—The best method of determining +nitrogen in fermented beverages is the common one of moist combustion +with sulfuric acid. The sample is placed in the kjeldahl digestion +flask, which is attached to the vacuum service and placed in a +steam bath until its contents are dry or nearly so. The process is +then conducted in harmony with the well known methods. Where large +quantities of the sample are to be employed, as in drinks containing +but little nitrogen, the preliminary evaporation may be accomplished in +an open dish, the contents of which are transferred to the digestion +flask before any solid matter is deposited. The same procedure may be +followed when the sample foams too much on heating. +<span class="pagenum"><a id="Page_640"></a>[Pg 640]</span></p> + +<p><b>646. Substitutes for Hops.</b>—It is often claimed that cheap and +deleterious bitters are used in brewing in order to save hops. While +it is doubtless true that foreign bitters are sometimes employed, the +experience of this laboratory goes to show that such an adulteration +is not very prevalent in this country.<a id="FNanchor_650" href="#Footnote_650" class="fnanchor">[650]</a> +Possibly strychnin, picrotoxin, quassin, gentian and other bitter +principles have sometimes been found in beer, but their use is no +longer common. It is difficult to decide in every case whether or not +foreign bitters have been added. A common process is to treat the +sample with lead acetate, filter, remove the lead from the filtrate +and detect any remaining bitters by the taste. All the hop bitters +are removed by the above process. Any remaining bitter taste is due +to other substances. For the methods of detecting the special bitter +principles in hops and other substances, the work of Dragendorff may be +consulted.<a id="FNanchor_651" href="#Footnote_651" class="fnanchor">[651]</a></p> + +<p><b>647. Bouquet of Fermented and Distilled Liquors.</b>—The bouquet +of fermented and distilled liquors is due to the presence of volatile +matters which may have three different origins. In the first place the +materials from which these beverages are made contain essential oils +and other odoriferous principles.<a id="FNanchor_652" href="#Footnote_652" class="fnanchor">[652]</a> +In the grape, for instance, the essential oils are found particularly +in the skins. These essential principles may be secured by distilling +the skins of grapes in a current of steam. This method of separation, +however, cannot be regarded as strictly quantitive.</p> + +<p>In the second place, the yeasts which produce the alcoholic +fermentation are also capable of producing odoriferous products. +These minute vegetations, resembling in their biological relations +the mushrooms, grow in the soil and reach their maturity at about +the time of the harvest of the grapes. Their spores are transmitted +through the air, reach the expressed grape juice and produce the vinous +fermentation. The particular odor due to any given yeast persists +through many generations of culture showing that the body which +produces the odor is the direct result of the vegetable activity of the +yeast. A beer yeast, after many generations of culture, will still give +a product which smells like beer, and in like manner a wine yeast will +produce one which has the odor of wine. The quantity of odorant matter +<span class="pagenum"><a id="Page_641"></a>[Pg 641]</span> +produced by this vegetable action is so minute as to escape detection +in a quantitive or qualitive way by chemical means. These subtle +perfumes arise moreover not only from the breaking up of the sugar +molecule, but are also the direct results of molecular synthesis +accomplished under the influence of the yeast itself.</p> + +<p>In the third place, the fermented and distilled liquors contain +odoriferous principles due to the chemical reactions which take place +by the breaking up of the sugar and other molecules during the process +of fermentation. The alcohols and acids produced have distinct odors by +which they are often recognized. This is particularly true of ethylic, +propylic, butylic, amylic and oenanthylic alcohols and acetic acid. +These alcohols themselves also undergo oxidation, passing first into +the state of aldehyds which, together with ethers, produce the peculiar +aroma which is found in various fruits. The etherification noted above +is of course preceded by the formation of acids corresponding to the +various aldehyds present. The formation of these ethers takes place +very slowly during aging, and it therefore requires three or four +years for the proper ripening of wines or distilled liquors. By means +of artificial heat, electricity and aeration, the oxidizing processes +above noted may be hastened, but it is doubtful whether the products +arising from this artificial treatment are as perfect as those which +are formed in the natural processes.</p> + +<h3>AUTHORITIES CITED IN PART SEVENTH.</h3> +<div class="footnotes"> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_535" href="#FNanchor_535" class="label">[535]</a> +Bulletin 46, Chemical Division U. S. Department of Agriculture, pp. 24-25.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_536" href="#FNanchor_536" class="label">[536]</a> +Bulletin 42, Arkansas Agricultural Experiment Station, pp. 81 et seq.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_537" href="#FNanchor_537" class="label">[537]</a> +Balland; Recherches sur les Blés, les Farines et le Pain, p. 229.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_538" href="#FNanchor_538" class="label">[538]</a> +Jago; Flour and Bread, p. 457.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_539" href="#FNanchor_539" class="label">[539]</a> +Jago; op. cit. supra, p. 465.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_540" href="#FNanchor_540" class="label">[540]</a> +Richardson; Journal of the Chemical Society, Transactions, +1885, pp. 84 et seq.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_541" href="#FNanchor_541" class="label">[541]</a> +Auct. et op. cit. supra, pp. 80 et seq.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_542" href="#FNanchor_542" class="label">[542]</a> +Bulletin 28, Office of Experiment Stations, U. S. +Department of Agriculture, pp. 9, 10.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_543" href="#FNanchor_543" class="label">[543]</a> +Bulletin 29, Office of Experiment Stations U. S. Department of Agriculture, p. 8.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_544" href="#FNanchor_544" class="label">[544]</a> +Op. et. loc. cit. supra.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_545" href="#FNanchor_545" class="label">[545]</a> +Experiment Station Record, Vol. 6, pp. 590 et seq.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_546" href="#FNanchor_546" class="label">[546]</a> +Annual Report, U. S. Department of Agriculture, 1884, p. 365.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_547" href="#FNanchor_547" class="label">[547]</a> +Forschungs-Berichte über Lebensmittel, Band 3, S. 142.</p> +</div> + +<p><span class="pagenum"><a id="Page_642"></a>[Pg 642]</span></p> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_548" href="#FNanchor_548" class="label">[548]</a> +Zeitschrift für angewandte Chemie, 1895, S. 620.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_549" href="#FNanchor_549" class="label">[549]</a> +Op. et loc. cit. supra.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_550" href="#FNanchor_550" class="label">[550]</a> +Les Ferments Solubles; Diastases—Enzymes.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_551" href="#FNanchor_551" class="label">[551]</a> +Wiley; Medical News, July, 1888.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_552" href="#FNanchor_552" class="label">[552]</a> +Virchow’s Archiv., Band 123, S. 230: Journal of the +Chemical Society, Abstracts, 1892, p. 755.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_553" href="#FNanchor_553" class="label">[553]</a> +Ladenberg; Handwörterbuch der Chemie, Band 4, S. 122.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_554" href="#FNanchor_554" class="label">[554]</a> +Chemisches Centralblatt, 1892, Band 2, S. 579.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_555" href="#FNanchor_555" class="label">[555]</a> +Op. cit. supra, 1890, Band 2, S. 628.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_556" href="#FNanchor_556" class="label">[556]</a> +Die Landwirtschaftlichen Versuchs-Stationen, Band 44, S. 188; +Experiment Station Record, Vol. 6, p. 12.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_557" href="#FNanchor_557" class="label">[557]</a> +Experiment Station Record, Vol. 6, pp. 5 et seq. +(Read Jordan instead of Gordon.)</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_558" href="#FNanchor_558" class="label">[558]</a> +Journal of the American Chemical Society, Vol. 16, pp. 590 et seq.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_559" href="#FNanchor_559" class="label">[559]</a> +From photograph made in this laboratory by Bigelow.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_560" href="#FNanchor_560" class="label">[560]</a> +Journal of the Society of Chemical Industry, Vol. 10, p. 118.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_561" href="#FNanchor_561" class="label">[561]</a> +Die Landwirtschaftlichen Versuchs-Stationen, Band 36, S. 321: +Bulletin 13, Chemical Division, U. S. Department of Agriculture, p. 1028.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_562" href="#FNanchor_562" class="label">[562]</a> +Wilson; Vid. op. et loc. cit. 26.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_563" href="#FNanchor_563" class="label">[563]</a> +U. S. Dispensatory, p. 1088.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_564" href="#FNanchor_564" class="label">[564]</a> +Landwirtschaftliche Jahrbücher, 1890, Band 19, S. 149.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_565" href="#FNanchor_565" class="label">[565]</a> +Bulletin 13, Chemical Division, U.S. Department of Agriculture, p. 1028.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_566" href="#FNanchor_566" class="label">[566]</a> +Zeitschrift für analytische Chemie, Band 35, S. 498.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_567" href="#FNanchor_567" class="label">[567]</a> +Annual Report of the Maine Agricultural Experiment Station, 1891, +p. 25: Gay; Annales Agronomiques, 1885, p. 145, et 1896, pp. 145 et seq.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_568" href="#FNanchor_568" class="label">[568]</a> +Annales Agronomiques, Tome 21, pp. 149, 150.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_569" href="#FNanchor_569" class="label">[569]</a> +Vid. op. et loc. cit. primo sub 33.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_570" href="#FNanchor_570" class="label">[570]</a> +Twelfth Annual Report of the Massachusetts Agricultural Experiment Station, +1894, p. 175.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_571" href="#FNanchor_571" class="label">[571]</a> +See also paragraph <b><a href="#P_586">586</a></b> this volume.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_572" href="#FNanchor_572" class="label">[572]</a> +Manuscript prepared for publication as a part of Bulletin 13, +Chemical Division, U. S. Department of Agriculture.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_573" href="#FNanchor_573" class="label">[573]</a> +Vid. this volume, paragraph <b><a href="#P_280">280</a></b>.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_574" href="#FNanchor_574" class="label">[574]</a> +Vid. op. cit. 31, p. 1020.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_575" href="#FNanchor_575" class="label">[575]</a> +Bulletin 45, Chemical Division, U.S. Department of Agriculture, p. 12.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_576" href="#FNanchor_576" class="label">[576]</a> +Berthelot; Essai de Chimie Mécanique: Thomsen; Thermo Chemische +Untersuchungen: Ostwald; Algemeine Chemie: Muir; Elements of Thermal +Chemistry.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_577" href="#FNanchor_577" class="label">[577]</a> +Bulletin 21, Office of Experiment Stations, U. S. Department of +Agriculture, pp. 113 et seq.: Seventh Annual Report Connecticut +(Storr’s) Agricultural Experiment Station, pp. 133 et seq.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_578" href="#FNanchor_578" class="label">[578]</a> +Vid. op. et loc. cit. 43.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_579" href="#FNanchor_579" class="label">[579]</a> +From personal inspection by author in Williams’ laboratory, +161 Tremont St., Boston, Mass.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_580" href="#FNanchor_580" class="label">[580]</a> +Journal für praktische Chemie, Band 147 {Neue Folge Band 39}, +Ss. 517 et seq.</p> +</div> + +<p><span class="pagenum"><a id="Page_643"></a>[Pg 643]</span></p> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_581" href="#FNanchor_581" class="label">[581]</a> +Berthelot; Annales de Chemie et de Physique, 6e Série, Tome 10, p. 439.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_582" href="#FNanchor_582" class="label">[582]</a> +Vid. op. cit. 46, Ss. 522-523. The data in paragraph <b><a href="#P_566">566</a></b> +are taken from Stohmann, Zeitschrift für Biologie, Band 31, S. 364 and +Experiment Station Record, Vol. 6, p. 590.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_583" href="#FNanchor_583" class="label">[583]</a> +Journal of the American Chemical Society, Vol. 18, p. 174.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_584" href="#FNanchor_584" class="label">[584]</a> +Bulletins 93, 97, 101 and 102, California Agricultural Experiment Station.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_585" href="#FNanchor_585" class="label">[585]</a> +Annual Report, U. S. Department of Agriculture, 1886, p. 354.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_586" href="#FNanchor_586" class="label">[586]</a> +This work, Vol. 2, p. 318.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_587" href="#FNanchor_587" class="label">[587]</a> +Vid. California Bulletins cited under 50: Wolff; Aschen Analyse, S. 126.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_588" href="#FNanchor_588" class="label">[588]</a> +Bulletin 100, Cornell Agricultural Experiment Station: Bulletin 48, +Chemical Division, U. S. Department of Agriculture.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_589" href="#FNanchor_589" class="label">[589]</a> +Vid. op. cit. 51, p. 353.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_590" href="#FNanchor_590" class="label">[590]</a> +Vid. op. cit. ultimo sub 54.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_591" href="#FNanchor_591" class="label">[591]</a> +Bulletin No. 42, Arkansas Agricultural Experiment Station, p. 78.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_592" href="#FNanchor_592" class="label">[592]</a> +Annual Report, U. S. Department of Agriculture, 1884, p. 347.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_593" href="#FNanchor_593" class="label">[593]</a> +Spencer; Bulletin 13, U. S. Department of Agriculture, pp. 875 et seq.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_594" href="#FNanchor_594" class="label">[594]</a> +Journal of Analytical and Applied Chemistry, Vol. 4, p. 390; Bulletin +13, Chemical Division, U. S. Department of Agriculture, p. 889.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_595" href="#FNanchor_595" class="label">[595]</a> +Pharmaceutical Journal, Vol. 52, p. 213.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_596" href="#FNanchor_596" class="label">[596]</a> +Commercial Organic Analysis, Vol. 3, part 2, p. 484.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_597" href="#FNanchor_597" class="label">[597]</a> +Journal de Pharmacie et de Chimie, 6ᵉ Série, Tome 3, p. 529.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_598" href="#FNanchor_598" class="label">[598]</a> +Journal of the American Chemical Society, Vol. 18, p. 338.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_599" href="#FNanchor_599" class="label">[599]</a> +Manuscript communication to author.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_600" href="#FNanchor_600" class="label">[600]</a> +Vid. op. cit. 63, p. 533.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_601" href="#FNanchor_601" class="label">[601]</a> +American Chemical Journal, Vol. 14, p. 473.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_602" href="#FNanchor_602" class="label">[602]</a> +Op. et loc. cit. supra.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_603" href="#FNanchor_603" class="label">[603]</a> +Lindsey; Report made to Thirteenth Annual Convention of the Association +of Official Agricultural Chemists, Nov. 6th, 1896: Tollens; Handbuch +der Kohlenhydrate, Band 2, S. 52.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_604" href="#FNanchor_604" class="label">[604]</a> +Zeitschrift für angewandte Chemie, 1896, p. 195,</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_605" href="#FNanchor_605" class="label">[605]</a> +Comptes rendus hebdomadaires de Seances de l’Academie des Sciences, Tome 122, p. 841.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_606" href="#FNanchor_606" class="label">[606]</a> +The Tannins, two volumes.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_607" href="#FNanchor_607" class="label">[607]</a> +Dragendorff; Plant Analysis.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_608" href="#FNanchor_608" class="label">[608]</a> +The Tannins, Vol. 1, p. 33.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_609" href="#FNanchor_609" class="label">[609]</a> +Bulletin 13, Chemical Division, U. S. Department of Agriculture, p. 908.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_610" href="#FNanchor_610" class="label">[610]</a> +Vid. op. cit. 74, p. 38.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_611" href="#FNanchor_611" class="label">[611]</a> +Bulletin 46, Chemical Division, U. S. Department of Agriculture, p. +77 as revised at 13th annual meeting of the Association of Official +Agricultural Chemists.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_612" href="#FNanchor_612" class="label">[612]</a> +Vid. op. cit. 75, p. 890: Zeitschrift für analytische Chemie, Band 25, +S. 121: Journal of the Society of Chemical Industry, Vol. 3, p. 82: +Trimble; The Tannins, Vol. 1, p. 44.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_613" href="#FNanchor_613" class="label">[613]</a> +Vid. op. cit. 74, p. 48.</p> +</div> + +<p><span class="pagenum"><a id="Page_644"></a>[Pg 644]</span></p> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_614" href="#FNanchor_614" class="label">[614]</a> +McElroy; Analyses made in this laboratory.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_615" href="#FNanchor_615" class="label">[615]</a> +Annual Report Connecticut Agricultural Experiment Station +(New Haven) 1892, p. 30.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_616" href="#FNanchor_616" class="label">[616]</a> +Kissling; Tabakkunde, S. 40.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_617" href="#FNanchor_617" class="label">[617]</a> +Vid. op. cit. supra, S. 58.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_618" href="#FNanchor_618" class="label">[618]</a> +Vid. op. cit. 81, p. 29.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_619" href="#FNanchor_619" class="label">[619]</a> +This work, Vol 1, pp. 500 et seq.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_620" href="#FNanchor_620" class="label">[620]</a> +This work, Vol. 1, p. 420.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_621" href="#FNanchor_621" class="label">[621]</a> +Vid. op. cit. 82, S. 62.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_622" href="#FNanchor_622" class="label">[622]</a> +Vid. op. cit. supra, S. 64.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_623" href="#FNanchor_623" class="label">[623]</a> +Dragendorff; Plant Analysis, p. 65.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_624" href="#FNanchor_624" class="label">[624]</a> +Sugar, 1896, March 15th, p. 11.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_625" href="#FNanchor_625" class="label">[625]</a> +Vid. op. cit. 82, S. 65.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_626" href="#FNanchor_626" class="label">[626]</a> +Der Tabak, S. 144.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_627" href="#FNanchor_627" class="label">[627]</a> +Vid. op. cit. 82, S. 65: Zeitschrift für analytische Chemie, Band 21, +S. 76: Band 22, S. 199: Band 32, S. 277: Band 34, Ss. 413-731.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_628" href="#FNanchor_628" class="label">[628]</a> +Zeitschrift für physiologische Chemie Band 13, S. 445: Band 14, S. 182.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_629" href="#FNanchor_629" class="label">[629]</a> +Zeitschrift für analytische Chemie, Band 34, S. 413, Band 35, Ss. 309, 731.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_630" href="#FNanchor_630" class="label">[630]</a> +Annual Report Connecticut Agricultural Experiment Station +(New Haven), 1892, p. 17.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_631" href="#FNanchor_631" class="label">[631]</a> +Buell; The Cider-makers’ Manual: Southby; Systematic Text-Book of +Practical Brewing: Moritz and Morris; Text-Book of the Science of Brewing.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_632" href="#FNanchor_632" class="label">[632]</a> +Gautier; Sophistication et Analyse des Vins, p. 49.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_633" href="#FNanchor_633" class="label">[633]</a> +Auct. et. op. cit. supra, p. 44.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_634" href="#FNanchor_634" class="label">[634]</a> +Bulletin 46, Chemical Division, U. S. Department of Agriculture, p. 63.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_635" href="#FNanchor_635" class="label">[635]</a> +Manuscript not yet published.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_636" href="#FNanchor_636" class="label">[636]</a> +Vid. op. cit. 100, pp. 95 et seq.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_637" href="#FNanchor_637" class="label">[637]</a> +Wiley; Journal of the American Chemical Society, Vol. 18, p. 1063.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_638" href="#FNanchor_638" class="label">[638]</a> +Vid. op. cit. 100, p. 70.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_639" href="#FNanchor_639" class="label">[639]</a> +Vid. op. cit. 98, p. 65.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_640" href="#FNanchor_640" class="label">[640]</a> +Vid. op. cit. 98, p. 67.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_641" href="#FNanchor_641" class="label">[641]</a> +The Analyst, Vol. 21, p. 158.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_642" href="#FNanchor_642" class="label">[642]</a> +Vid. op. cit. 98, p. 98.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_643" href="#FNanchor_643" class="label">[643]</a> +Vid. op. cit. 100, p. 74.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_644" href="#FNanchor_644" class="label">[644]</a> +Vid. op. cit. 100, p. 75.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_645" href="#FNanchor_645" class="label">[645]</a> +Vid. op. cit. 100, p. 75.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_646" href="#FNanchor_646" class="label">[646]</a> +Bulletin de la Société Chimique de Paris, Série {2}, Tome 24, p. 288; +Berichte der deutschen chemischen Gesellschaft, Band 8, S. 257.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_647" href="#FNanchor_647" class="label">[647]</a> +Vid. op. cit. 98, p. 120.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_648" href="#FNanchor_648" class="label">[648]</a> +Bulletin 46, Chemical Division U. S. Department of Agriculture, pp. 72, et. seq.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_649" href="#FNanchor_649" class="label">[649]</a> +This work, Vol. 2, pp. 267 and 326.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_650" href="#FNanchor_650" class="label">[650]</a> +Bulletin 13, Chemical Division, U. S. Department of Agriculture, p. 296.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_651" href="#FNanchor_651" class="label">[651]</a> +Plant Analysis, pp. 38, et seq.</p> +</div> + +<div class="footnote"><p class="no-indent"> +<a id="Footnote_652" href="#FNanchor_652" class="label">[652]</a> +Repertoire de Pharmacie, Série 3e, Tome 7, p. 436.</p> +</div> +</div> + +<hr class="chap x-ebookmaker-drop"> + +<div class="chapter"> +<p><span class="pagenum"><a id="Page_645"></a>[Pg 645]</span></p> +<h2 class="nobreak">INDEX.</h2> +</div> + +<ul class="index"> +<li class="isub20 fs_110">Page.</li> +<li class="isub7 fs_120"><b>A</b></li> +<li class="isub2">Abbe, refractometer, <a href="#Page_329">329</a></li> +<li class="isub2">Acetic acid, estimation in tobacco, <a href="#Page_602">602</a></li> +<li class="isub2">Acetyl value, <a href="#Page_384">384</a>, <a href="#Page_385">385</a></li> +<li class="isub2">Acidity, estimation in fermented beverages, <a href="#Page_27">27</a></li> +<li class="isub3">of milk, determination, <a href="#Page_473">473</a></li> +<li class="isub2">Acids, determination in fruits and vegetables, <a href="#Page_579">579</a></li> +<li class="isub2">Agricultural products, classification of miscellaneous, <a href="#Page_541">541</a></li> +<li class="isub3">description, <a href="#Page_1">1</a></li> +<li class="isub2">Air-bath, drying, <a href="#Page_16">16</a></li> +<li class="isub2">Albumin, definition, <a href="#Page_410">410</a></li> +<li class="isub3">gyrodynals of hydrates, <a href="#Page_276">276</a></li> +<li class="isub3">precipitants in milk, <a href="#Page_276">276</a></li> +<li class="isub3">qualitive tests, <a href="#Page_420">420</a></li> +<li class="isub3">separation in milk, <a href="#Page_509">509</a></li> +<li class="isub2">Albuminates, definition and properties, <a href="#Page_411">411</a></li> +<li class="isub3">estimation in cheese, <a href="#Page_531">531</a></li> +<li class="isub3">qualitive tests, <a href="#Page_421">421</a></li> +<li class="isub2">Albuminoids, <a href="#Page_413">413</a></li> +<li class="isub3">definition, <a href="#Page_410">410</a></li> +<li class="isub2">Albumins, action, on polarized light, <a href="#Page_422">422</a></li> +<li class="isub3">gyrodynats, <a href="#Page_422">422</a></li> +<li class="isub3">properties, <a href="#Page_410">410</a></li> +<li class="isub3">separation, <a href="#Page_439">439</a></li> +<li class="isub2">Albumose peptone, <a href="#Page_461">461</a></li> +<li class="isub2">Albumoses, estimation, in cheese, <a href="#Page_531">531</a></li> +<li class="isub3">separation, from peptones, <a href="#Page_455">455</a></li> +<li class="isub2">Alcohol, calculating, in fermented beverages, <a href="#Page_616">616</a></li> +<li class="isub3">digestion, <a href="#Page_245">245</a></li> +<li class="isub3">estimation, by vapor temperature, <a href="#Page_622">622</a></li> +<li class="isub4">in ensilage, <a href="#Page_546">546</a></li> +<li class="isub5">fermented beverages, <a href="#Page_612">612</a></li> +<li class="isub5">koumiss, <a href="#Page_534">534</a></li> +<li class="isub5">sugar analysis, <a href="#Page_186">186</a></li> +<li class="isub3">reagent for precipitating dextrin, <a href="#Page_292">292</a></li> +<li class="isub3">table showing percentage, <a href="#Page_617">617-621</a></li> +<li class="isub2">Alcoholic digestion, sugar beets, <a href="#Page_248">248-250</a></li> +<li class="isub2">Alcoholometer, <a href="#Page_612">612</a></li> +<li class="isub2">Aliphalytic ferments, <a href="#Page_556">556</a></li> +<li class="isub2">Alkali, action on reducing sugars, <a href="#Page_131">131</a>, <a href="#Page_132">132</a></li> +<li class="isub2">Alkaline copper solutions, comparison, <a href="#Page_127">127-129</a></li> +<li class="isub2">Alkaloidal nitrogen, estimation, <a href="#Page_432">432</a></li> +<li class="isub3">qualitive tests, <a href="#Page_422">422</a>, <a href="#Page_423">423</a></li> +<li class="isub2">Alkaloids, occurrence, <a href="#Page_417">417</a></li> +<li class="isub2">Allantoin, <a href="#Page_428">428</a></li> +<li class="isub2">Allein and Gaud, modification of Pavy’s process, <a href="#Page_145">145</a></li> +<li class="isub2">Allen, modification of Pavy’s process, <a href="#Page_144">144</a></li> +<li class="isub3">potassium cyanid process, <a href="#Page_146">146</a></li> +<li class="isub2">Allihn, gravimetric dextrose method, <a href="#Page_155">155-158</a> + <span class="pagenum"><a id="Page_646"></a>[Pg 646]</span></li> +<li class="isub2">Alum, occurrence, in bread, <a href="#Page_544">544</a></li> +<li class="isub5">reagent for casein, <a href="#Page_535">535</a></li> +<li class="isub2">Alumina cream, clarification, <a href="#Page_100">100</a></li> +<li class="isub2">Aluminum dishes, drying, <a href="#Page_33">33</a></li> +<li class="isub2">Amagat-Jean, refractometer, <a href="#Page_334">334-338</a></li> +<li class="isub2">Amid nitrogen, estimation, <a href="#Page_424">424</a></li> +<li class="isub3">in cereals, <a href="#Page_543">543</a></li> +<li class="isub4">tobacco, <a href="#Page_607">607</a></li> +<li class="isub3">occurrence, <a href="#Page_417">417</a></li> +<li class="isub3">qualitive test, <a href="#Page_418">418</a></li> +<li class="isub3">separation, in cheese, <a href="#Page_530">530</a></li> +<li class="isub2">Ammonia, estimation, in tobacco, <a href="#Page_605">605</a></li> +<li class="isub2">Ammoniacal copper solution, <a href="#Page_143">143</a></li> +<li class="isub3">nitrogen, estimation, <a href="#Page_423">423</a>, <a href="#Page_424">424</a></li> +<li class="isub4">in cheese, <a href="#Page_531">531</a></li> +<li class="isub3">qualitive test, <a href="#Page_419">419</a></li> +<li class="isub2">Ammonium sulfate, reagent for milk proteids, <a href="#Page_507">507</a></li> +<li class="isub3">precipitating proteids, <a href="#Page_433">433</a></li> +<li class="isub2">Amyl alcohol, use, in milk fat analysis, <a href="#Page_501">501</a></li> +<li class="isub2">Amyliferous bodies, desiccation, <a href="#Page_299">299</a></li> +<li class="isub2">Amyloid bodies in milk, <a href="#Page_512">512</a></li> +<li class="isub2">Amylolytic ferments, <a href="#Page_556">556</a></li> +<li class="isub2">Anatto, <a href="#Page_522">522</a></li> +<li class="isub2">Animal products, sampling, <a href="#Page_448">448</a></li> +<li class="isub3">substances, preparation, <a href="#Page_4">4</a>, <a href="#Page_5">5</a></li> +<li class="isub2">Anoptose, <a href="#Page_234">234</a></li> +<li class="isub2">Antipeptones, <a href="#Page_412">412</a></li> +<li class="isub2">Aqueous diffusion, sugar beet analysis, <a href="#Page_251">251</a>, <a href="#Page_252">252</a></li> +<li class="isub2">Araban, occurrence, <a href="#Page_586">586</a></li> +<li class="isub2">Arabinose, molecular weight, <a href="#Page_177">177</a></li> +<li class="isub2">Arachidic acid, separation, <a href="#Page_398">398</a>, <a href="#Page_399">399</a></li> +<li class="isub2">Areometric method, application in milk fat analysis, <a href="#Page_494">494</a>, <a href="#Page_495">495</a></li> +<li class="isub2">Areometry, <a href="#Page_70">70</a></li> +<li class="isub2">Artificial digestion, <a href="#Page_555">555</a></li> +<li class="isub3">manipulation, <a href="#Page_561">561</a></li> +<li class="isub3">smoker, <a href="#Page_609">609</a></li> +<li class="isub2">Ash, composition, in milk, <a href="#Page_466">466</a>, <a href="#Page_467">467</a></li> +<li class="isub4">of fruit, <a href="#Page_580">580</a></li> +<li class="isub3">estimation, <a href="#Page_36">36</a></li> +<li class="isub4">in butter, <a href="#Page_516">516</a></li> +<li class="isub5">cereals, <a href="#Page_542">542</a></li> +<li class="isub5">fermented beverages, <a href="#Page_637">637</a></li> +<li class="isub5">koumiss, <a href="#Page_536">536</a></li> +<li class="isub5">meats, <a href="#Page_550">550</a></li> +<li class="isub5">milk, <a href="#Page_482">482</a></li> +<li class="isub5">proteids, <a href="#Page_444">444</a></li> +<li class="isub3">German method, <a href="#Page_39">39</a></li> +<li class="isub2">Asparagin, <a href="#Page_417">417</a></li> +<li class="isub3">estimation, <a href="#Page_426">426</a>, <a href="#Page_427">427</a></li> +<li class="isub3">preparation, <a href="#Page_426">426</a></li> +<li class="isub2">Aspartic acid, <a href="#Page_412">412</a></li> +<li class="isub2">Atwater and Woods, calorimeter, <a href="#Page_569">569</a></li> +<li class="isub3">methods of meat analysis, <a href="#Page_549">549</a></li> +<li class="isub3">preparation of fish, <a href="#Page_12">12</a></li> +<li class="isub2">Auric chlorid, color test with fats and oils, <a href="#Page_356">356</a></li> +<li class="isub2">Authorities cited in Part</li> +<li class="isub3">Fifth, <a href="#Page_462">462</a>, <a href="#Page_463">463</a></li> +<li class="isub3">First, <a href="#Page_56">56</a>, <a href="#Page_57">57</a> + <span class="pagenum"><a id="Page_647"></a>[Pg 647]</span></li> +<li class="isub3">Fourth, <a href="#Page_406">406-409</a></li> +<li class="isub3">Second, <a href="#Page_222">222</a></li> +<li class="isub3">Seventh, <a href="#Page_641">641-644</a></li> +<li class="isub3">Sixth, <a href="#Page_536">536-540</a></li> +<li class="isub3">Third, <a href="#Page_306">306-308</a></li> + +<li class="isub7 ifrst fs_120"><b>B</b></li> +<li class="isub2">Babcock, formula, for calculating total solids, <a href="#Page_479">479</a>, <a href="#Page_480">480</a></li> +<li class="isub3">method of counting fat globules, <a href="#Page_483">483</a>, <a href="#Page_484">484</a></li> +<li class="isub4">milk fat analysis, <a href="#Page_499">499</a>, <a href="#Page_500">500</a></li> +<li class="isub2">Bacteria, reactions, on sugar, <a href="#Page_196">196</a></li> +<li class="isub2">Bagasse, analysis, <a href="#Page_239">239</a>, <a href="#Page_240">240</a></li> +<li class="isub2">Barfoed, reagent, for removing dextrose, <a href="#Page_291">291</a>, <a href="#Page_292">292</a></li> +<li class="isub2">Barium saccharate, <a href="#Page_187">187</a></li> +<li class="isub2">Barley starch, <a href="#Page_221">221</a></li> +<li class="isub2">Basic lead acetate, clarification, <a href="#Page_101">101</a></li> +<li class="isub2">Baumé and brix degrees, comparison, <a href="#Page_73">73</a></li> +<li class="isub2">Bean starch, <a href="#Page_220">220</a></li> +<li class="isub2">Bechi’s test for cottonseed oil, <a href="#Page_400">400</a>, <a href="#Page_401">401</a></li> +<li class="isub2">Beet rasp, <a href="#Page_10">10</a>, <a href="#Page_251">251</a></li> +<li class="isub2">Beimling, method of milk fat analysis, <a href="#Page_502">502</a></li> +<li class="isub2">Betain, <a href="#Page_417">417</a></li> +<li class="isub3">separation from cholin, <a href="#Page_429">429</a></li> +<li class="isub2">Bigelow and McElroy, estimation of sugar in evaporated milks, <a href="#Page_296">296-298</a></li> +<li class="isub3">method of dialysis, <a href="#Page_447">447</a></li> +<li class="isub3">table for correcting hydrostatic plummet, <a href="#Page_615">615</a></li> +<li class="isub2">Biliverdin, occurrence in milk, <a href="#Page_464">464</a></li> +<li class="isub2">Birotation, <a href="#Page_118">118</a></li> +<li class="isub3">mathematical theory, <a href="#Page_177">177</a>, <a href="#Page_178">178</a></li> +<li class="isub2">Biuret reaction, <a href="#Page_419">419</a></li> +<li class="isub2">Block, feculometer, <a href="#Page_300">300</a></li> +<li class="isub2">Bone-black, decolorization, <a href="#Page_104">104</a></li> +<li class="isub2">Bordeaux-red, determination, in wines, <a href="#Page_637">637</a></li> +<li class="isub2">Bouquet of fermented and distilled liquors, <a href="#Page_640">640</a>, <a href="#Page_641">641</a></li> +<li class="isub2">Bread, acidity, <a href="#Page_544">544</a></li> +<li class="isub3">amount of water, <a href="#Page_544">544</a></li> +<li class="isub3">baking, temperature, <a href="#Page_543">543</a></li> +<li class="isub3">chemical changes in baking, <a href="#Page_545">545</a></li> +<li class="isub3">color, <a href="#Page_544">544</a></li> +<li class="isub3">methods of analysis, <a href="#Page_543">543-545</a></li> +<li class="isub3">nitrogenous compounds, <a href="#Page_544">544</a></li> +<li class="isub3">soluble extract, <a href="#Page_543">543</a></li> +<li class="isub2">Brix and baumé degrees, comparison, <a href="#Page_73">73</a></li> +<li class="isub2">Bromin addition number, <a href="#Page_371">371-373</a></li> +<li class="isub2">Brullé, color test for fats and oils, <a href="#Page_355">355</a></li> +<li class="isub2">Butter, adulterants, <a href="#Page_521">521</a></li> +<li class="isub3">appearance of melted, <a href="#Page_513">513</a></li> +<li class="isub4">with polarized light, <a href="#Page_514">514</a></li> +<li class="isub3">calorimetric distinction, from oleomargarin, <a href="#Page_576">576</a></li> +<li class="isub3">colors, <a href="#Page_522">522</a></li> +<li class="isub4">detection, <a href="#Page_523">523</a></li> +<li class="isub3">fat analysis, classification of methods, <a href="#Page_484">484</a></li> +<li class="isub4">estimation, <a href="#Page_482">482-504</a></li> +<li class="isub3">methods of analysis, <a href="#Page_512">512-523</a></li> +<li class="isub3">microscopic examination, <a href="#Page_513">513</a></li> +<li class="isub3">molecular weight, <a href="#Page_520">520</a> + <span class="pagenum"><a id="Page_648"></a>[Pg 648]</span></li> +<li class="isub3">refractive index, <a href="#Page_514">514</a></li> +<li class="isub3">relative proportion of ingredients, <a href="#Page_517">517</a></li> +<li class="isub3">substitutes, molecular weight, <a href="#Page_520">520</a>, <a href="#Page_521">521</a></li> +<li class="isub2">Butyrin, <a href="#Page_310">310</a></li> +<li class="isub2">Butyrorefractometer, <a href="#Page_339">339-341</a></li> +<li class="isub3">range of application, <a href="#Page_342">342</a></li> + +<li class="isub7 ifrst fs_120"><b>C</b></li> +<li class="isub2">Caffein, estimation, <a href="#Page_583">583</a></li> +<li class="isub2">Caffetannic acid, <a href="#Page_590">590</a></li> +<li class="isub2">Calcium saccharates, <a href="#Page_188">188</a></li> +<li class="isub2">Caldwell, hydrogen drying oven, <a href="#Page_26">26</a>, <a href="#Page_27">27</a></li> +<li class="isub2">Calories, computation, <a href="#Page_574">574-578</a></li> +<li class="isub3">definition, <a href="#Page_576">576</a></li> +<li class="isub2">Calorimeter, description, <a href="#Page_569">569</a></li> +<li class="isub3">formulas for calculation, <a href="#Page_572">572</a></li> +<li class="isub3">hydrothermal value, <a href="#Page_573">573</a></li> +<li class="isub3">manipulation, <a href="#Page_571">571</a></li> +<li class="isub2">Calorimetric equivalents, <a href="#Page_576">576</a></li> +<li class="isub2">Calorimetry, <a href="#Page_568">568-576</a></li> +<li class="isub2">Canada balsam, mounting starches, <a href="#Page_219">219</a></li> +<li class="isub2">Cane cutting machines, <a href="#Page_236">236</a>, <a href="#Page_237">237</a></li> +<li class="isub3">pulp, determination of sugar, <a href="#Page_238">238</a></li> +<li class="isub4">drying and extraction, <a href="#Page_238">238</a></li> +<li class="isub3">sugar, gyrodynat, <a href="#Page_117">117</a>, <a href="#Page_118">118</a></li> +<li class="isub2">Carbohydrates, <a href="#Page_58">58</a></li> +<li class="isub3">estimation in cereals, <a href="#Page_543">543</a></li> +<li class="isub3">kind, <a href="#Page_58">58</a></li> +<li class="isub3">milk, <a href="#Page_511">511</a></li> +<li class="isub3">molecular weights, <a href="#Page_175">175</a></li> +<li class="isub3">nomenclature, <a href="#Page_59">59</a></li> +<li class="isub3">occurrence, <a href="#Page_58">58</a></li> +<li class="isub4">in coffee, <a href="#Page_585">585</a></li> +<li class="isub4">of rare, <a href="#Page_306">306</a></li> +<li class="isub3">separation, <a href="#Page_279">279</a></li> +<li class="isub4">in fruits and vegetables, <a href="#Page_577">577</a></li> +<li class="isub2">Carbon, estimation in proteids, <a href="#Page_444">444</a></li> +<li class="isub3">dioxid, determination, in sugar analysis, <a href="#Page_186">186</a></li> +<li class="isub4">estimation, in koumiss, <a href="#Page_532">532</a></li> +<li class="isub4">reagent for casein, <a href="#Page_509">509</a></li> +<li class="isub3">tetrachlorid, reagent in iodin addition, <a href="#Page_368">368</a></li> +<li class="isub2">Carnin, <a href="#Page_416">416</a></li> +<li class="isub3">composition, <a href="#Page_451">451</a></li> +<li class="isub2">Carr, vacuum drying oven, <a href="#Page_22">22</a>, <a href="#Page_23">23</a></li> +<li class="isub2">Casein, estimation, in butter, <a href="#Page_516">516</a></li> +<li class="isub4">cheese, <a href="#Page_531">531</a></li> +<li class="isub4">with mercurial salts, <a href="#Page_535">535</a></li> +<li class="isub3">factors for calculating, <a href="#Page_508">508</a></li> +<li class="isub3">method of estimating, <a href="#Page_508">508</a></li> +<li class="isub3">precipitants in milk, <a href="#Page_276">276</a></li> +<li class="isub3">precipitation, by alum, <a href="#Page_535">535</a></li> +<li class="isub3">preparation, <a href="#Page_509">509</a></li> +<li class="isub3">separation, by filtering through porous porcelain, <a href="#Page_534">534</a></li> +<li class="isub4">from albumin, <a href="#Page_507">507</a></li> +<li class="isub3">solution, in acid, <a href="#Page_489">489</a></li> +<li class="isub3">theory of precipitation, <a href="#Page_508">508</a></li> +<li class="isub2">Caseinogen, <a href="#Page_504">504</a> + <span class="pagenum"><a id="Page_649"></a>[Pg 649]</span></li> +<li class="isub2">Cassava starch, <a href="#Page_222">222</a></li> +<li class="isub2">Cattle foods, <a href="#Page_545">545</a></li> +<li class="isub2">Cellulose, constitution, <a href="#Page_303">303</a></li> +<li class="isub3">qualitive reactions, <a href="#Page_306">306</a></li> +<li class="isub3">separation, <a href="#Page_304">304</a></li> +<li class="isub3">solubility, <a href="#Page_305">305</a></li> +<li class="isub2">Cereals, general principles of analysis, <a href="#Page_542">542</a></li> +<li class="isub2">Chalmot and Tollens, method of estimating pentosans, <a href="#Page_182">182</a></li> +<li class="isub2">Chandler and Ricketts, polariscope, <a href="#Page_266">266</a></li> +<li class="isub2">Cheese, artificial digestion, <a href="#Page_561">561</a></li> +<li class="isub3">composition, <a href="#Page_524">524</a></li> +<li class="isub3">constituents, <a href="#Page_530">530</a></li> +<li class="isub3">filled, <a href="#Page_529">529</a></li> +<li class="isub3">methods of analysis, <a href="#Page_526">526-533</a></li> +<li class="isub3">manufacture, <a href="#Page_525">525</a></li> +<li class="isub3">proteids, separation, <a href="#Page_530">530</a>, <a href="#Page_531">531</a></li> +<li class="isub2">Chitin, <a href="#Page_416">416</a></li> +<li class="isub3">character of reaction, <a href="#Page_512">512</a></li> +<li class="isub2">Chlorophyll, separation, from caffein, <a href="#Page_585">585</a></li> +<li class="isub2">Cholesterin, detection, <a href="#Page_403">403</a>, <a href="#Page_404">404</a></li> +<li class="isub3">occurrence, in milk, <a href="#Page_464">464</a></li> +<li class="isub2">Cholin, <a href="#Page_417">417</a></li> +<li class="isub3">separation, from cottonseed, <a href="#Page_428">428</a>, <a href="#Page_429">429</a></li> +<li class="isub2">Chondrin, <a href="#Page_415">415</a></li> +<li class="isub2">Chrome yellow, <a href="#Page_522">522</a></li> +<li class="isub2">Chrysolite, use, in drying, <a href="#Page_486">486</a></li> +<li class="isub2">Chyle, occurrence, in milk, <a href="#Page_464">464</a></li> +<li class="isub2">Chyme, occurrence, in milk, <a href="#Page_464">464</a></li> +<li class="isub2">Citric acid, estimation, in tobacco, <a href="#Page_601">601</a></li> +<li class="isub3">occurrence, in milk, <a href="#Page_466">466</a></li> +<li class="isub2">Clerget, method of inversion, <a href="#Page_105">105-107</a></li> +<li class="isub2">Cobaltous nitrate, reagent for nitrate, <a href="#Page_189">189</a></li> +<li class="isub2">Collagen, <a href="#Page_413">413</a></li> +<li class="isub2">Coloring matters, determination, in wines, <a href="#Page_636">636</a>, <a href="#Page_637">637</a></li> +<li class="isub2">Combustion products, <a href="#Page_36">36</a>, <a href="#Page_37">37</a></li> +<li class="isub2">Conchiolin, <a href="#Page_416">416</a></li> +<li class="isub2">Conglutin, <a href="#Page_411">411</a></li> +<li class="isub2">Constant monochromatic flame, <a href="#Page_85">85</a></li> +<li class="isub2">Control observation tube, <a href="#Page_95">95</a>, <a href="#Page_96">96</a></li> +<li class="isub2">Copper carbonate process, <a href="#Page_138">138-140</a></li> +<li class="isub4">use, in estimating sucrose, dextrose and levulose, <a href="#Page_282">282</a>, <a href="#Page_283">283</a></li> +<li class="isub3">cyanid, reagent for estimating lactose, <a href="#Page_294">294</a>, <a href="#Page_295">295</a></li> +<li class="isub3">oxid, weighing, in sugar analysis, <a href="#Page_262">262</a></li> +<li class="isub3">reagent in determining oxygen absorption of oils, <a href="#Page_405">405</a></li> +<li class="isub3">salts, reduction, by sugar, <a href="#Page_123">123</a></li> +<li class="isub3">solution, action on dextrose, <a href="#Page_125">125</a></li> +<li class="isub3">sulfate, reagent for milk proteids, <a href="#Page_506">506</a></li> +<li class="isub4">separating proteid from amid nitrogen, <a href="#Page_433">433</a></li> +<li class="isub3">titration of residual, <a href="#Page_148">148</a>, <a href="#Page_149">149</a></li> +<li class="isub2">Cottonseed oil, detection, <a href="#Page_400">400</a></li> +<li class="isub2">Courtonne, ash muffle, <a href="#Page_40">40</a></li> +<li class="isub2">Crampton, preparation of fat crystals, <a href="#Page_347">347</a></li> +<li class="isub2">Creamometry, <a href="#Page_474">474</a></li> +<li class="isub2">Creydt, formula, <a href="#Page_110">110</a></li> +<li class="isub2">Crismer, critical temperature, <a href="#Page_349">349</a>, <a href="#Page_350">350</a></li> +<li class="isub2">Critical temperature, fats and oils, <a href="#Page_349">349</a></li> +<li class="isub2">Crude proteids, estimation, in cereals, <a href="#Page_543">543</a> + <span class="pagenum"><a id="Page_650"></a>[Pg 650]</span></li> +<li class="isub2">Crystallin, <a href="#Page_411">411</a></li> +<li class="isub2">Crystallization, temperature, <a href="#Page_327">327</a></li> +<li class="isub2">Cuprous oxid, specific gravity, <a href="#Page_137">137</a></li> +<li class="isub2">Curd, estimation, in butter, <a href="#Page_516">516</a></li> + +<li class="isub7 ifrst fs_120"><b>D</b></li> +<li class="isub2">Dairy products, importance, <a href="#Page_464">464</a></li> +<li class="isub2">Davis, meat preservatives, <a href="#Page_566">566</a></li> +<li class="isub2">Density, determination, <a href="#Page_63">63</a></li> +<li class="isub3">of sour milk, <a href="#Page_477">477</a></li> +<li class="isub2">Deuteroalbumose, <a href="#Page_412">412</a></li> +<li class="isub2">Dextrin, detection, in fermented beverages, <a href="#Page_639">639</a></li> +<li class="isub3">occurrence, in glucose, <a href="#Page_264">264</a></li> +<li class="isub3">precipitation, by alcohol, <a href="#Page_292">292</a></li> +<li class="isub3">separation, from dextrose and maltose, <a href="#Page_287">287-293</a></li> +<li class="isub2">Dextrinoid bodies in milk, <a href="#Page_511">511</a></li> +<li class="isub2">Dextrosazone, <a href="#Page_193">193</a></li> +<li class="isub2">Dextrose, action of alkaline copper solution, <a href="#Page_125">125</a></li> +<li class="isub3">estimation, in presence of sucrose, <a href="#Page_274">274</a>, <a href="#Page_275">275</a></li> +<li class="isub4">and levulose, <a href="#Page_280">280-285</a></li> +<li class="isub3">group, qualitive test, <a href="#Page_190">190</a></li> +<li class="isub3">gyrodynat, <a href="#Page_118">118</a></li> +<li class="isub3">molecular weight, <a href="#Page_176">176</a></li> +<li class="isub3">removal, by copper acetate, <a href="#Page_291">291</a></li> +<li class="isub3">separation from maltose and dextrin, <a href="#Page_287">287-293</a></li> +<li class="isub3">table for calculating, from copper, <a href="#Page_260">260</a></li> +<li class="isub2">Dialysis, <a href="#Page_447">447</a></li> +<li class="isub3">application, for precipitating milk proteids, <a href="#Page_511">511</a></li> +<li class="isub2">Diastase, action, on starch, <a href="#Page_198">198</a></li> +<li class="isub3">preparation, <a href="#Page_300">300</a></li> +<li class="isub2">Diffusion, instantaneous, <a href="#Page_243">243</a></li> +<li class="isub2">Digestion, alcoholic, <a href="#Page_245">245</a></li> +<li class="isub2">Distillation, methods, <a href="#Page_612">612</a>, <a href="#Page_613">613</a></li> +<li class="isub2">Doolittle, viscosimeter, <a href="#Page_343">343</a>, <a href="#Page_344">344</a></li> +<li class="isub2">Double dilution, milk analysis, <a href="#Page_278">278</a></li> +<li class="isub3">polarization, <a href="#Page_102">102</a></li> +<li class="isub2">Dreef grinding machine, <a href="#Page_11">11</a></li> +<li class="isub2">Dry substance, estimation, for factory control, <a href="#Page_263">263</a></li> +<li class="isub2">Drying samples, general principles, <a href="#Page_34">34</a>, <a href="#Page_35">35</a></li> + +<li class="isub7 ifrst fs_120"><b>E</b></li> +<li class="isub2">Earth bases, reagents for precipitating sugar, <a href="#Page_187">187</a></li> +<li class="isub2">Ebullioscope, <a href="#Page_622">622</a>, <a href="#Page_623">623</a></li> +<li class="isub2">Edson, preserving sugar juices, <a href="#Page_235">235</a></li> +<li class="isub2">Elaidin, <a href="#Page_406">406</a></li> +<li class="isub2">Elastin, <a href="#Page_415">415</a></li> +<li class="isub2">Electric drying oven, <a href="#Page_19">19</a></li> +<li class="isub2">Ensilage, alcohol, <a href="#Page_546">546</a></li> +<li class="isub3">changes, due to fermentation, <a href="#Page_546">546</a></li> +<li class="isub3">comparative value, <a href="#Page_547">547</a></li> +<li class="isub3">organic acids, <a href="#Page_546">546</a></li> +<li class="isub2">Ether extract, estimation, in cereals, <a href="#Page_542">542</a></li> +<li class="isub3">solvent, <a href="#Page_41">41</a></li> +<li class="isub2">Evaporated fruits, <a href="#Page_580">580</a></li> +<li class="isub3">milk, estimation of sugar, <a href="#Page_296">296</a></li> +<li class="isub2">Ewell, method of estimating coffee carbohydrates, <a href="#Page_585">585</a> + <span class="pagenum"><a id="Page_651"></a>[Pg 651]</span></li> +<li class="isub3">permanganate method, <a href="#Page_136">136</a></li> +<li class="isub2">Excreta, collection, <a href="#Page_562">562</a>, <a href="#Page_563">563</a></li> +<li class="isub2">Extract, composition, in fermented beverages, <a href="#Page_624">624</a></li> +<li class="isub3">estimation, by indirect method, <a href="#Page_625">625</a></li> +<li class="isub4">in fermented beverages, <a href="#Page_624">624</a></li> +<li class="isub4">vacuum, <a href="#Page_626">626</a></li> +<li class="isub2">Extraction apparatus, <a href="#Page_43">43-51</a></li> +<li class="isub3">by digestion, <a href="#Page_42">42</a></li> +<li class="isub4">percolation, <a href="#Page_43">43</a></li> +<li class="isub3">compact apparatus, <a href="#Page_48">48-51</a></li> +<li class="isub3">methods, <a href="#Page_41">41</a>, <a href="#Page_42">42</a></li> +<li class="isub3">with alcohol, <a href="#Page_245">245</a></li> + +<li class="isub7 ifrst fs_120"><b>F</b></li> +<li class="isub2">Fat acids, determinations of nature, <a href="#Page_396">396</a></li> +<li class="isub4">formulas for calculating yield, <a href="#Page_392">392</a>, <a href="#Page_393">393</a></li> +<li class="isub4">temperature of crystallization, <a href="#Page_327">327</a></li> +<li class="isub3">crystals, appearance, with polarized light, <a href="#Page_347">347</a></li> +<li class="isub4">microscopic appearance, <a href="#Page_346">346</a>, <a href="#Page_347">347</a></li> +<li class="isub3">estimation, in altered milk, <a href="#Page_487">487</a>, <a href="#Page_488">488</a></li> +<li class="isub4">butter, <a href="#Page_515">515</a></li> +<li class="isub4">koumiss, <a href="#Page_534">534</a></li> +<li class="isub4">meats, <a href="#Page_550">550</a></li> +<li class="isub4">preserved meats, <a href="#Page_563">563</a></li> +<li class="isub3">extraction, methods, adapted to milk, <a href="#Page_486">486</a></li> +<li class="isub3">form of globules in milk, <a href="#Page_482">482</a></li> +<li class="isub3">globules, method of counting, <a href="#Page_483">483</a></li> +<li class="isub4">number, in milk, <a href="#Page_482">482</a></li> +<li class="isub3">in milk, classification of methods of analysis, <a href="#Page_484">484</a></li> +<li class="isub4">comparison of methods of analysis, <a href="#Page_488">488</a></li> +<li class="isub4">wet extraction methods, <a href="#Page_488">488</a></li> +<li class="isub2">Fats and oils, coloration, produced by oxidants, <a href="#Page_352">352</a></li> +<li class="isub4">consistence, <a href="#Page_396">396</a></li> +<li class="isub4">drying, for analysis, <a href="#Page_316">316</a></li> +<li class="isub4">estimation of water, <a href="#Page_317">317</a></li> +<li class="isub4">extraction, <a href="#Page_41">41</a></li> +<li class="isub4">melting point, <a href="#Page_320">320-323</a></li> +<li class="isub4">microscopic appearance, <a href="#Page_345">345</a></li> +<li class="isub4">physical properties, <a href="#Page_317">317-345</a></li> +<li class="isub4">polarization, <a href="#Page_350">350</a></li> +<li class="isub4">preparation, for microscope, <a href="#Page_345">345</a>, <a href="#Page_346">346</a></li> +<li class="isub4">refractive index, <a href="#Page_328">328</a></li> +<li class="isub4">sampling, <a href="#Page_315">315</a></li> +<li class="isub4">solubility, in alcohol, <a href="#Page_351">351</a></li> +<li class="isub4">specific gravity, <a href="#Page_317">317-319</a></li> +<li class="isub4">table of densities, <a href="#Page_320">320</a></li> +<li class="isub4">temperature of crystallization, <a href="#Page_327">327</a></li> +<li class="isub4">thermal reactions, <a href="#Page_356">356-363</a></li> +<li class="isub4">turbidity temperature, <a href="#Page_351">351</a></li> +<li class="isub3">composition, <a href="#Page_309">309</a>, <a href="#Page_310">310</a></li> +<li class="isub3">freeing, of moisture, <a href="#Page_315">315</a></li> +<li class="isub3">nomenclature, <a href="#Page_309">309</a></li> +<li class="isub2">Feculometer, Block, <a href="#Page_300">300</a></li> +<li class="isub2">Fehling solutions, comparison, <a href="#Page_127">127</a></li> +<li class="isub3">composition, <a href="#Page_126">126</a></li> +<li class="isub3">historical, <a href="#Page_124">124</a></li> +<li class="isub2">Fermentation, method of separating sugars, <a href="#Page_288">288</a>, <a href="#Page_289">289</a> + <span class="pagenum"><a id="Page_652"></a>[Pg 652]</span></li> +<li class="isub3">use, in sugar analysis, <a href="#Page_185">185</a></li> +<li class="isub2">Fermented beverages, constituents, <a href="#Page_611">611</a></li> +<li class="isub3">description, <a href="#Page_610">610</a></li> +<li class="isub3">distillation, <a href="#Page_612">612-614</a></li> +<li class="isub3">polarization, <a href="#Page_632">632</a></li> +<li class="isub3">specific gravity, <a href="#Page_611">611</a></li> +<li class="isub2">Ferments, aliphalytic, <a href="#Page_556">556</a></li> +<li class="isub3">amylolytic, <a href="#Page_556">556</a></li> +<li class="isub3">proteolytic, <a href="#Page_557">557</a></li> +<li class="isub2">Fiber, estimation, <a href="#Page_303">303</a>, <a href="#Page_304">304</a></li> +<li class="isub3">in canes, <a href="#Page_241">241</a></li> +<li class="isub4">cereals, <a href="#Page_543">543</a></li> +<li class="isub3">occurrence, <a href="#Page_303">303</a></li> +<li class="isub2">Fibrin, <a href="#Page_413">413</a>, <a href="#Page_504">504</a></li> +<li class="isub2">Fibrinogen, <a href="#Page_411">411</a></li> +<li class="isub2">Fibroin, <a href="#Page_416">416</a></li> +<li class="isub2">Field of vision, appearance, <a href="#Page_81">81</a></li> +<li class="isub2">Filled cheese, <a href="#Page_529">529</a></li> +<li class="isub2">Fischer, carbohydrates, <a href="#Page_59">59</a></li> +<li class="isub2">Fish, preparation, <a href="#Page_12">12</a></li> +<li class="isub2">Flesh bases, treatment of residue, insoluble in alcohol, <a href="#Page_460">460</a></li> +<li class="isub2">Foods, constituents, comparative values, <a href="#Page_567">567</a></li> +<li class="isub3">fuel value, <a href="#Page_551">551</a></li> +<li class="isub3">nutritive values, <a href="#Page_566">566</a></li> +<li class="isub3">potential energy, <a href="#Page_551">551</a></li> +<li class="isub2">Free fat acid, determination, <a href="#Page_394">394</a></li> +<li class="isub2">Fruits, composition, <a href="#Page_579">579</a></li> +<li class="isub3">evaporated, <a href="#Page_580">580</a></li> +<li class="isub3">sampling, <a href="#Page_577">577</a></li> +<li class="isub2">Fuchsin, detection, in wines, <a href="#Page_637">637</a></li> +<li class="isub2">Furfurol, determination, <a href="#Page_180">180</a></li> +<li class="isub3">precipitation, with pyrogalol, <a href="#Page_183">183</a></li> +<li class="isub3">qualitive tests, for sugars, <a href="#Page_194">194</a></li> +<li class="isub3">reactions, <a href="#Page_194">194</a>, <a href="#Page_195">195</a></li> + +<li class="isub7 ifrst fs_120"><b>G</b></li> +<li class="isub2">Galactan, method of estimating, <a href="#Page_586">586</a></li> +<li class="isub3">occurrence, <a href="#Page_586">586</a></li> +<li class="isub2">Galactosazone, <a href="#Page_193">193</a></li> +<li class="isub2">Galactose, products of oxidation, with nitric acid, <a href="#Page_191">191</a></li> +<li class="isub2">Gelatin, <a href="#Page_414">414</a></li> +<li class="isub3">estimation, <a href="#Page_456">456-459</a></li> +<li class="isub3">reagent for tannins, <a href="#Page_590">590</a></li> +<li class="isub2">Gerber, butyrometer, <a href="#Page_502">502</a></li> +<li class="isub3">method of milk fat analysis, <a href="#Page_502">502-503</a></li> +<li class="isub2">Gerrard, potassium cyanid process, <a href="#Page_146">146</a></li> +<li class="isub2">Ginger starch, <a href="#Page_220">220</a></li> +<li class="isub2">Gird, gravimeter, <a href="#Page_233">233</a></li> +<li class="isub2">Glacial acetic acid, reagent for fats and oils, <a href="#Page_351">351</a></li> +<li class="isub2">Gladding, method of preparing fats for the microscope, <a href="#Page_346">346</a></li> +<li class="isub2">Glass, errors due to poor, <a href="#Page_520">520</a></li> +<li class="isub2">Gliadin, <a href="#Page_436">436</a></li> +<li class="isub2">Globin, <a href="#Page_411">411</a></li> +<li class="isub2">Globulin, separation in milk, <a href="#Page_510">510</a></li> +<li class="isub2">Globulins, properties, <a href="#Page_411">411</a></li> +<li class="isub3">separation, <a href="#Page_440">440</a> + <span class="pagenum"><a id="Page_653"></a>[Pg 653]</span></li> +<li class="isub2">Glucosazone, <a href="#Page_171">171</a></li> +<li class="isub2">Glucose, commercial, <a href="#Page_286">286</a></li> +<li class="isub3">process of manufacture, <a href="#Page_287">287</a></li> +<li class="isub2">Glutamic acid, <a href="#Page_412">412</a></li> +<li class="isub2">Glutamin, <a href="#Page_417">417</a></li> +<li class="isub3">estimation, <a href="#Page_426">426</a>, <a href="#Page_427">427</a></li> +<li class="isub2">Gluten, <a href="#Page_413">413</a></li> +<li class="isub3">composition, <a href="#Page_426">426</a></li> +<li class="isub3">separation, from wheat flour, <a href="#Page_434">434</a>, <a href="#Page_435">435</a></li> +<li class="isub2">Glutenin, <a href="#Page_436">436</a></li> +<li class="isub2">Glutin, <a href="#Page_413">413</a></li> +<li class="isub3">composition, <a href="#Page_451">451</a></li> +<li class="isub2">Glycerids, principal, <a href="#Page_310">310</a></li> +<li class="isub3">saponification value, <a href="#Page_383">383</a>, <a href="#Page_384">384</a></li> +<li class="isub3">separation, <a href="#Page_397">397</a></li> +<li class="isub2">Glycerol, estimation, in fermented beverages, <a href="#Page_635">635</a>, <a href="#Page_636">636</a></li> +<li class="isub3">formulas for calculating yield, <a href="#Page_392">392</a>, <a href="#Page_393">393</a></li> +<li class="isub2">Gomberg, method of estimating caffein, <a href="#Page_584">584</a>, <a href="#Page_585">585</a></li> +<li class="isub2">Grape sugar, birotation, <a href="#Page_287">287</a></li> +<li class="isub3">commercial, <a href="#Page_264">264</a>, <a href="#Page_286">286</a></li> +<li class="isub2">Gravimeter, <a href="#Page_233">233</a></li> +<li class="isub2">Green samples, grinding, <a href="#Page_9">9</a></li> +<li class="isub2">Grinding apparatus, <a href="#Page_6">6-11</a></li> +<li class="isub2">Gum, detection, in fermented beverages, <a href="#Page_639">639</a></li> +<li class="isub2">Gypsum, use, in drying sour milk, <a href="#Page_487">487</a></li> +<li class="isub2">Gyrodynat, definition, <a href="#Page_116">116</a></li> + +<li class="isub7 ifrst fs_120"><b>H</b></li> +<li class="isub2">Haemocyanin, <a href="#Page_411">411</a></li> +<li class="isub2">Haemoglobin, <a href="#Page_411">411</a></li> +<li class="isub2">Halle drying apparatus, <a href="#Page_29">29</a></li> +<li class="isub2">Haloid absorption by fat acids, <a href="#Page_374">374-376</a></li> +<li class="isub3">addition numbers, <a href="#Page_364">364</a></li> +<li class="isub2">Heat of bromination, improved method of determining, <a href="#Page_361">361-363</a></li> +<li class="isub2">Hehner and Mitchell, method of determining heat of bromination, <a href="#Page_361">361</a></li> +<li class="isub4">Richmond, formula for calculating total solids, <a href="#Page_479">479</a>, <a href="#Page_480">480</a></li> +<li class="isub4">bromin addition number, <a href="#Page_373">373</a></li> +<li class="isub2">Hemi-peptones, <a href="#Page_412">412</a></li> +<li class="isub2">Hempel, calorimeter, <a href="#Page_569">569</a></li> +<li class="isub2">Heteroalbumose, <a href="#Page_412">412</a></li> +<li class="isub2">Hibbard, estimation of starch, <a href="#Page_207">207</a></li> +<li class="isub2">Hide powder, reagent for tannins, <a href="#Page_590">590</a></li> +<li class="isub3">testing, <a href="#Page_592">592</a></li> +<li class="isub2">Honey, composition, <a href="#Page_264">264</a></li> +<li class="isub2">Hoppe-Seyler, cellulose, separation, <a href="#Page_304">304</a></li> +<li class="isub2">Hops, bitter principles, <a href="#Page_640">640</a></li> +<li class="isub3">substitutes, <a href="#Page_640">640</a></li> +<li class="isub2">Horse flesh, detection, <a href="#Page_554">554</a></li> +<li class="isub2">Hübl’s process, <a href="#Page_364">364-367</a></li> +<li class="isub3">reagent, preservation, <a href="#Page_371">371</a></li> +<li class="isub2">Hyalin, <a href="#Page_416">416</a></li> +<li class="isub2">Hyalogen, <a href="#Page_416">416</a></li> +<li class="isub2">Hydrochloric acid, estimation, in tobacco, <a href="#Page_600">600</a></li> +<li class="isub2">Hydrogen, drying, <a href="#Page_24">24</a></li> +<li class="isub3">estimation, in proteids, <a href="#Page_444">444</a></li> +<li class="isub2">Hydrometer, balling, <a href="#Page_71">71</a></li> +<li class="isub3">baumé, <a href="#Page_71">71</a> + <span class="pagenum"><a id="Page_654"></a>[Pg 654]</span></li> +<li class="isub3">brix, <a href="#Page_71">71</a></li> +<li class="isub2">Hydrometers, <a href="#Page_71">71</a></li> +<li class="isub2">Hydrometry, correction for temperature, <a href="#Page_72">72</a></li> +<li class="isub2">Hydrostatic balance, <a href="#Page_68">68</a></li> +<li class="isub3">plummet, <a href="#Page_615">615</a></li> +<li class="isub4">correction table, <a href="#Page_615">615</a></li> +<li class="isub2">Hypogaeic acid, separation, <a href="#Page_399">399</a></li> +<li class="isub2">Hypoxanthin, occurrence, in milk, <a href="#Page_464">464</a></li> + +<li class="isub7 ifrst fs_120"><b>I</b></li> +<li class="isub2">Impurities, error due, <a href="#Page_74">74</a></li> +<li class="isub2">Incineration, purpose and conduct, <a href="#Page_37">37</a>, <a href="#Page_38">38</a></li> +<li class="isub2">Insoluble fat acids, determination, <a href="#Page_391">391</a>, <a href="#Page_392">392</a></li> +<li class="isub2">Inversion, application of the process, <a href="#Page_114">114</a></li> +<li class="isub3">calculation of results, <a href="#Page_108">108</a>, <a href="#Page_109">109</a></li> +<li class="isub3">determination of sucrose, <a href="#Page_105">105</a></li> +<li class="isub3">influence of strength of solution, <a href="#Page_108">108</a></li> +<li class="isub4">time of heating, <a href="#Page_108">108</a></li> +<li class="isub2">Invert sugar, estimation of minute quantities, <a href="#Page_257">257</a></li> +<li class="isub3">gyrodynat, <a href="#Page_119">119</a></li> +<li class="isub3">influence of temperature on gyrodynat, <a href="#Page_265">265</a></li> +<li class="isub3">occurrence, <a href="#Page_264">264</a></li> +<li class="isub3">official method, <a href="#Page_161">161-162</a></li> +<li class="isub3">optical neutrality, <a href="#Page_265">265</a></li> +<li class="isub3">separation and estimation, <a href="#Page_264">264</a></li> +<li class="isub3">table for calculating, from copper, <a href="#Page_260">260</a></li> +<li class="isub4">estimating, <a href="#Page_159">159</a>, <a href="#Page_258">258</a></li> +<li class="isub2">Invertase, determination of activity, <a href="#Page_111">111</a>, <a href="#Page_112">112</a></li> +<li class="isub3">use, in inversion, <a href="#Page_110">110</a>, <a href="#Page_111">111</a></li> +<li class="isub2">Invertose, molecular weight, <a href="#Page_177">177</a></li> +<li class="isub2">Iodin addition, <a href="#Page_364">364-367</a></li> +<li class="isub4">character of chemical reaction, <a href="#Page_367">367</a></li> +<li class="isub3">monochlorid, substitution for hübl reagent, <a href="#Page_370">370</a></li> +<li class="isub3">number, estimation, <a href="#Page_369">369-370</a></li> +<li class="isub3">reaction with starch, <a href="#Page_196">196</a></li> +<li class="isub3">reagent for caffein, <a href="#Page_584">584</a></li> + +<li class="isub7 ifrst fs_120"><b>J</b></li> +<li class="isub2">Juices, analysis of fruit and vegetable, <a href="#Page_578">578</a></li> + +<li class="isub7 ifrst fs_120"><b>K</b></li> +<li class="isub2">Keratin, <a href="#Page_416">416</a></li> +<li class="isub2">Kieselguhr, use in drying, <a href="#Page_486">486</a></li> +<li class="isub2">Knorr, extraction apparatus, <a href="#Page_44">44</a></li> +<li class="isub3">fractional analysis of meats, <a href="#Page_552">552</a></li> +<li class="isub2">Koettstorfer, saponification value, <a href="#Page_382">382</a>, <a href="#Page_383">383</a></li> +<li class="isub2">Koumiss, acidity, <a href="#Page_532">532</a></li> +<li class="isub3">composition, <a href="#Page_532">532</a>, <a href="#Page_536">536</a></li> +<li class="isub2">Kreatin, <a href="#Page_416">416</a></li> +<li class="isub3">composition, <a href="#Page_431">431</a></li> +<li class="isub3">determination, <a href="#Page_454">454</a></li> +<li class="isub3">occurrence in milk, <a href="#Page_464">464</a></li> +<li class="isub2">Kreatinin, <a href="#Page_416">416</a></li> +<li class="isub3">composition, <a href="#Page_451">451</a></li> +<li class="isub3">determination, <a href="#Page_454">454</a></li> +<li class="isub2">Krug, method of determining oxygen absorption of oils, <a href="#Page_405">405</a>, <a href="#Page_406">406</a></li> +<li class="isub4">estimating pentosans, <a href="#Page_179">179</a>, <a href="#Page_183">183</a></li> +<li class="isub3">separation of oleic and hypogaeic acids, <a href="#Page_399">399</a></li> +<li class="isub3">viscosity of oils, <a href="#Page_345">345</a> + <span class="pagenum"><a id="Page_655"></a>[Pg 655]</span></li> +<li class="isub7 ifrst fs_120"><b>L</b></li> +<li class="isub2">Lactobutyrometer, <a href="#Page_495">495</a>, <a href="#Page_496">496</a></li> +<li class="isub2">Lactocrite, use in milk fat analysis, <a href="#Page_498">498</a></li> +<li class="isub2">Lactoglobulin, <a href="#Page_504">504</a></li> +<li class="isub2">Lactometer, direct reading, <a href="#Page_476">476</a></li> +<li class="isub3">New York Board of Health, <a href="#Page_476">476</a></li> +<li class="isub2">Lactometry, <a href="#Page_475">475</a>, <a href="#Page_476">476</a></li> +<li class="isub2">Lactoprotein, <a href="#Page_504">504</a></li> +<li class="isub2">Lactosazone, precipitation, <a href="#Page_295">295</a></li> +<li class="isub2">Lactoscopes, <a href="#Page_473">473</a>, <a href="#Page_474">474</a></li> +<li class="isub2">Lactose, estimation, <a href="#Page_293">293</a></li> +<li class="isub4">in Koumiss, <a href="#Page_534">534</a></li> +<li class="isub5">milk, <a href="#Page_275">275</a></li> +<li class="isub3">gyrodynat, <a href="#Page_119">119</a></li> +<li class="isub3">molecular weight, <a href="#Page_177">177</a></li> +<li class="isub3">official method of estimation, <a href="#Page_294">294</a></li> +<li class="isub2">Laurent lamp, <a href="#Page_83">83</a>, <a href="#Page_84">84</a></li> +<li class="isub3">polariscope, <a href="#Page_83">83</a></li> +<li class="isub4">construction, <a href="#Page_86">86-88</a></li> +<li class="isub4">manipulation, <a href="#Page_88">88</a></li> +<li class="isub2">Lead acetate, preserving agent, <a href="#Page_235">235</a></li> +<li class="isub3">oxid, separation of sugars, <a href="#Page_284">284</a>, <a href="#Page_285">285</a></li> +<li class="isub3">reagent for determining oxygen absorption of oils, <a href="#Page_405">405</a></li> +<li class="isub3">salts, reagents for separating fat acids, <a href="#Page_397">397</a></li> +<li class="isub3">solutions, errors, <a href="#Page_102">102</a></li> +<li class="isub3">subacetate, action on levulose, <a href="#Page_103">103</a></li> +<li class="isub2">Lecithin, extraction from seeds, <a href="#Page_430">430</a>, <a href="#Page_431">431</a></li> +<li class="isub3">factors for calculating, <a href="#Page_431">431</a></li> +<li class="isub3">occurrence and properties, <a href="#Page_430">430</a></li> +<li class="isub4">in milk, <a href="#Page_464">464</a></li> +<li class="isub2">Leffmann and Beam, method of milk fat analysis, <a href="#Page_501">501</a></li> +<li class="isub2">Legumin, <a href="#Page_411">411</a></li> +<li class="isub2">Leucin, <a href="#Page_412">412</a></li> +<li class="isub3">occurrence in milk, <a href="#Page_464">464</a></li> +<li class="isub2">Levulosazone, <a href="#Page_193">193</a></li> +<li class="isub2">Levulose, estimation, <a href="#Page_168">168</a></li> +<li class="isub4">in presence of sucrose and dextrose, <a href="#Page_280">280-285</a></li> +<li class="isub3">general formula for calculation, <a href="#Page_274">274</a></li> +<li class="isub3">gyrodynat, <a href="#Page_119">119</a></li> +<li class="isub3">optical determination, <a href="#Page_267">267</a></li> +<li class="isub3">preparation, <a href="#Page_167">167</a></li> +<li class="isub3">principles of calculation, <a href="#Page_270">270-273</a></li> +<li class="isub3">table for calculating from copper, <a href="#Page_260">260</a></li> +<li class="isub3">estimation, <a href="#Page_169">169-171</a></li> +<li class="isub2">Liebermann, method of milk fat analysis, <a href="#Page_471">471</a>, <a href="#Page_492">492</a></li> +<li class="isub2">Liebig ente, <a href="#Page_28">28</a></li> +<li class="isub2">Light, kind used for polarization, <a href="#Page_82">82</a></li> +<li class="isub2">Lindet, method of inversion, <a href="#Page_109">109</a>, <a href="#Page_110">110</a></li> +<li class="isub2">Lindsey and Holland, digestibility of pentosans, <a href="#Page_564">564</a></li> +<li class="isub2">Lindström, modification of lactocrite, <a href="#Page_499">499</a></li> +<li class="isub2">Lineolin, <a href="#Page_310">310</a></li> +<li class="isub2">Lint, use, in drying, <a href="#Page_486">486</a></li> +<li class="isub2">Livache, method of determining oxygen absorption, <a href="#Page_405">405</a></li> +<li class="isub2">Long and Baker, diastase preparation, <a href="#Page_300">300</a> + <span class="pagenum"><a id="Page_656"></a>[Pg 656]</span></li> +<li class="isub3">table of refractive indices, <a href="#Page_334">334</a></li> + +<li class="isub7 ifrst fs_120"><b>Mc</b></li> +<li class="isub2">McElroy and Bigelow, estimation of sugar in</li> +<li class="isub5">evaporated milks, <a href="#Page_296">296-298</a></li> +<li class="isub3">estimation of nicotin, <a href="#Page_605">605</a></li> +<li class="isub2">McIlhiney, bromin addition number, <a href="#Page_372">372</a></li> + +<li class="isub7 ifrst fs_120"><b>M</b></li> +<li class="isub2">Maercker, apparatus for hydrolysis of starch, <a href="#Page_204">204</a></li> +<li class="isub3">method of sugar analysis, <a href="#Page_153">153-155</a></li> +<li class="isub2">Magnesium sulfate, reagent for precipitating proteids, <a href="#Page_433">433</a></li> +<li class="isub2">Maize starch, <a href="#Page_221">221</a></li> +<li class="isub2">Malic acid, estimation in fermented beverages, <a href="#Page_630">630</a>, <a href="#Page_631">631</a></li> +<li class="isub3">tobacco, <a href="#Page_601">601</a></li> +<li class="isub2">Malt extract, <a href="#Page_301">301</a></li> +<li class="isub2">Maltosazone, <a href="#Page_193">193</a></li> +<li class="isub2">Maltose, estimation, <a href="#Page_165">165</a></li> +<li class="isub3">gyrodynat, <a href="#Page_119">119</a>, <a href="#Page_206">206</a></li> +<li class="isub3">molecular weight, <a href="#Page_177">177</a></li> +<li class="isub3">occurrence, in glucose, <a href="#Page_264">264</a></li> +<li class="isub3">separation from dextrin and dextrose, <a href="#Page_287">287-293</a></li> +<li class="isub3">table for calculating from copper, <a href="#Page_261">261</a></li> +<li class="isub4">determination, <a href="#Page_165">165-167</a></li> +<li class="isub2">Maple sugar, <a href="#Page_228">228</a></li> +<li class="isub3">conditions of manufacture, <a href="#Page_228">228</a></li> +<li class="isub2">Maranta starch, <a href="#Page_219">219</a></li> +<li class="isub2">Massecuites, analysis, <a href="#Page_254">254</a></li> +<li class="isub3">determination of ash, <a href="#Page_256">256</a></li> +<li class="isub4">reducing sugars, <a href="#Page_256">256</a></li> +<li class="isub4">water, <a href="#Page_255">255</a></li> +<li class="isub2">Maumené, heat of sulfuric saponification, <a href="#Page_357">357</a>, <a href="#Page_358">358</a></li> +<li class="isub2">Maxwell, method of extracting lecithin, <a href="#Page_430">430</a>, <a href="#Page_431">431</a></li> +<li class="isub2">Meat extracts, analysis, <a href="#Page_452">452-454</a></li> +<li class="isub3">composition, <a href="#Page_451">451</a>, <a href="#Page_452">452</a></li> +<li class="isub2">Meats, estimation of proteids, <a href="#Page_550">550</a></li> +<li class="isub3">fractional analysis, <a href="#Page_552">552</a></li> +<li class="isub3">methods of analysis, <a href="#Page_549">549-554</a></li> +<li class="isub3">sampling, <a href="#Page_547">547</a></li> +<li class="isub3">scientific names,<a href="#Page_547">547</a></li> +<li class="isub2">Meissl, table for invert sugar, <a href="#Page_158">158</a></li> +<li class="isub2">Melons, sampling, <a href="#Page_577">577</a></li> +<li class="isub2">Melting point, determination by spheroidal state, <a href="#Page_323">323-326</a></li> +<li class="isub3">methods of determining, <a href="#Page_321">321-326</a></li> +<li class="isub3">of fats and oils, <a href="#Page_320">320-323</a></li> +<li class="isub2">Mercuric compounds, clarification, <a href="#Page_104">104</a></li> +<li class="isub3">cyanid, reagent for destroying reducing sugars, <a href="#Page_290">290</a>, <a href="#Page_291">291</a></li> +<li class="isub3">salts, reagent for casein, <a href="#Page_535">535</a></li> +<li class="isub4">reduction by sugar, <a href="#Page_121">121</a></li> +<li class="isub2">Metabolism, vegetable and animal, <a href="#Page_2">2</a></li> +<li class="isub2">Metalbumin, <a href="#Page_415">415</a></li> +<li class="isub2">Methyl blue, qualitive test for invert sugar, <a href="#Page_192">192</a></li> +<li class="isub2">Micro-organisms, occurrence in milk, <a href="#Page_469">469</a></li> +<li class="isub2">Midzu ame, Japan glucose, <a href="#Page_286">286</a></li> +<li class="isub3">composition, <a href="#Page_264">264</a></li> +<li class="isub2">Milk, acidity, <a href="#Page_475">475</a></li> +<li class="isub3">alkalinity, <a href="#Page_472">472</a></li> +<li class="isub3">alterabitity, <a href="#Page_467">467</a>, <a href="#Page_468">468</a> + <span class="pagenum"><a id="Page_657"></a>[Pg 657]</span></li> +<li class="isub3">appearance, <a href="#Page_469">469</a></li> +<li class="isub3">carbohydrates, <a href="#Page_293">293</a>, <a href="#Page_511">511</a></li> +<li class="isub3">composition, <a href="#Page_464">464</a>, <a href="#Page_465">465</a>, <a href="#Page_468">468</a></li> +<li class="isub3">determination of total solids, <a href="#Page_477">477</a></li> +<li class="isub3">effects of boiling, <a href="#Page_469">469</a></li> +<li class="isub3">electric conductivity, <a href="#Page_472">472</a></li> +<li class="isub3">error due to volume of precipitate in polarization, <a href="#Page_277">277</a></li> +<li class="isub3">fat analysis, volumetric methods, <a href="#Page_496">496-504</a></li> +<li class="isub4">extraction, asbestos process, <a href="#Page_485">485</a></li> +<li class="isub5">paper coil method, <a href="#Page_485">485</a></li> +<li class="isub5">variation of methods, <a href="#Page_486">486</a></li> +<li class="isub3">freezing point, <a href="#Page_472">472</a></li> +<li class="isub3">mean composition, <a href="#Page_465">465</a></li> +<li class="isub3">opacity, <a href="#Page_473">473</a></li> +<li class="isub3">polarization, <a href="#Page_277">277</a></li> +<li class="isub3">preservatives, <a href="#Page_471">471</a>, <a href="#Page_472">472</a></li> +<li class="isub3">proteids, <a href="#Page_504">504</a></li> +<li class="isub4">estimation, <a href="#Page_505">505</a></li> +<li class="isub4">precipitants, <a href="#Page_510">510</a></li> +<li class="isub3">sampling, <a href="#Page_469">469</a>, <a href="#Page_470">470</a></li> +<li class="isub3">serum, density, <a href="#Page_477">477</a></li> +<li class="isub3">specific gravity, <a href="#Page_474">474</a></li> +<li class="isub3">sterilized, <a href="#Page_468">468</a></li> +<li class="isub3">sugar, estimation, <a href="#Page_163">163</a>, <a href="#Page_164">164</a></li> +<li class="isub4">table for estimation, <a href="#Page_163">163</a></li> +<li class="isub3">viscosity, <a href="#Page_472">472</a></li> +<li class="isub2">Millian, method for determining solubility, <a href="#Page_351">351</a></li> +<li class="isub3">modification of Bechi’s test, <a href="#Page_401">401</a></li> +<li class="isub3">process of separating arachidic acid, <a href="#Page_398">398</a></li> +<li class="isub2">Million’s reagent, <a href="#Page_421">421</a></li> +<li class="isub2">Mills, grinding, <a href="#Page_7">7-11</a></li> +<li class="isub2">Mitscherlich, determination of ash, <a href="#Page_83">83</a></li> +<li class="isub4">reducing sugars, <a href="#Page_256">256</a></li> +<li class="isub4">water, <a href="#Page_255">255</a></li> +<li class="isub3">specific gravity, <a href="#Page_254">254</a>, <a href="#Page_255">255</a></li> +<li class="isub2">Monochromatic flame, constant, <a href="#Page_85">85</a></li> +<li class="isub2">Mother beets, determination of sugar, <a href="#Page_250">250</a>, <a href="#Page_251">251</a></li> +<li class="isub2">Mucic acid, test for lactose, <a href="#Page_190">190</a></li> +<li class="isub2">Mucin, <a href="#Page_414">414</a></li> +<li class="isub2">Munroe, thermal reactions of oils, <a href="#Page_359">359</a></li> +<li class="isub2">Muscular tissues, occurrence in meat extracts, <a href="#Page_456">456</a></li> +<li class="isub3">separation of nitrogenous bodies, <a href="#Page_448">448-450</a></li> +<li class="isub2">Muskmelons, composition, <a href="#Page_581">581</a>, <a href="#Page_582">582</a></li> +<li class="isub2">Muter, method of determining haloid addition, <a href="#Page_374">374-376</a></li> +<li class="isub3">process of separating fat acids, <a href="#Page_397">397</a></li> +<li class="isub3">table, for identifying starches, <a href="#Page_214">214-217</a></li> +<li class="isub2">Mycsin, <a href="#Page_411">411</a></li> +<li class="isub2">Myrosin, <a href="#Page_411">411</a></li> + +<li class="isub7 ifrst fs_120"><b>N</b></li> +<li class="isub2">Natural digestion, <a href="#Page_562">562</a></li> +<li class="isub2">Neuclein, <a href="#Page_415">415</a></li> +<li class="isub2">Neucleoproteids, <a href="#Page_415">415</a></li> +<li class="isub2">Neurokeratin, <a href="#Page_416">416</a></li> +<li class="isub2">Nickel prism, <a href="#Page_77">77</a></li> +<li class="isub3">theory, <a href="#Page_77">77-80</a> + <span class="pagenum"><a id="Page_658"></a>[Pg 658]</span></li> +<li class="isub2">Nicotin, estimation in tobacco, <a href="#Page_605">605-607</a></li> +<li class="isub3">gyrodynat, <a href="#Page_606">606</a></li> +<li class="isub3">polarization, <a href="#Page_606">606</a></li> +<li class="isub2">Nitric acid, color test, fats and oils, <a href="#Page_353">353</a></li> +<li class="isub3">estimation in tobacco, <a href="#Page_600">600</a></li> +<li class="isub3">qualitive test, <a href="#Page_418">418</a></li> +<li class="isub2">Nitrogen, estimation in fermented beverages, <a href="#Page_639">639</a></li> +<li class="isub5">flesh bases, <a href="#Page_459">459</a></li> +<li class="isub5">proteids, <a href="#Page_445">445</a></li> +<li class="isub4">of total, <a href="#Page_423">423</a></li> +<li class="isub3">percentage in proteids, <a href="#Page_445">445</a></li> +<li class="isub2">Nitrogenous bases, occurrence in animal tissues, <a href="#Page_450">450</a>, <a href="#Page_451">451</a></li> +<li class="isub3">bodies, composition, <a href="#Page_410">410</a></li> +<li class="isub4">estimation in meats, <a href="#Page_551">551</a></li> +<li class="isub4">occurrence in animal products, <a href="#Page_448">448-462</a></li> +<li class="isub4">qualitive tests, <a href="#Page_418">418-421</a></li> +<li class="isub4">separation in cheese, <a href="#Page_530">530</a></li> +<li class="isub2">Nutritive ratio, <a href="#Page_568">568</a></li> +<li class="isub3">values, <a href="#Page_566">566</a></li> + +<li class="isub7 ifrst fs_120"><b>O</b></li> +<li class="isub2">Oat starch, <a href="#Page_221">221</a></li> +<li class="isub2">Observation tube, continuous, <a href="#Page_253">253</a></li> +<li class="isub2">Oil press, <a href="#Page_312">312</a></li> +<li class="isub3">removal from starchy bodies, <a href="#Page_300">300</a></li> +<li class="isub2">Oils and fats, extraction, <a href="#Page_310">310</a>, <a href="#Page_314">314</a></li> +<li class="isub4">identification, <a href="#Page_395">395</a>, <a href="#Page_406">406</a></li> +<li class="isub4">physical properties, <a href="#Page_317">317</a>, <a href="#Page_345">345</a></li> +<li class="isub3">coefficient of expansion, <a href="#Page_319">319</a></li> +<li class="isub3">composition, <a href="#Page_309">309</a>, <a href="#Page_310">310</a></li> +<li class="isub3">heat of bromination, <a href="#Page_360">360</a></li> +<li class="isub3">nomenclature, <a href="#Page_309">309</a></li> +<li class="isub3">spectroscopic examination, <a href="#Page_348">348</a></li> +<li class="isub2">Oleic acid separation from palmitic, <a href="#Page_397">397</a></li> +<li class="isub2">Olein, <a href="#Page_310">310</a></li> +<li class="isub2">Oleomargarin, calometric distinction from butter, <a href="#Page_576">576</a></li> +<li class="isub2">Oleorefractometer, <a href="#Page_334">334</a></li> +<li class="isub2">Oleothermometer, <a href="#Page_514">514</a></li> +<li class="isub2">Organic acids, occurrence in ensilage, <a href="#Page_546">546</a></li> +<li class="isub2">Orseille, detection in wines, <a href="#Page_637">637</a></li> +<li class="isub2">Osazones, melting points, <a href="#Page_193">193</a></li> +<li class="isub2">Ost, copper carbonate method, <a href="#Page_258">258</a>, <a href="#Page_259">259</a></li> +<li class="isub3">solution, <a href="#Page_257">257</a></li> +<li class="isub2">Oven, electric, <a href="#Page_19">19</a></li> +<li class="isub3">hydrogen drying, <a href="#Page_25">25</a>, <a href="#Page_27">27</a></li> +<li class="isub3">steam coil, <a href="#Page_20">20</a>, <a href="#Page_21">21</a></li> +<li class="isub3">water jacket, drying, <a href="#Page_14">14</a></li> +<li class="isub2">Oxalic acid, estimation in tobacco, <a href="#Page_601">601</a></li> +<li class="isub2">Oxygen, absorption by oils, <a href="#Page_405">405</a></li> +<li class="isub3">combustion, <a href="#Page_569">569</a></li> + +<li class="isub7 ifrst fs_120"><b>P</b></li> +<li class="isub2">Palm sugar, <a href="#Page_228">228</a></li> +<li class="isub2">Palmitic acid, separation from oleic, <a href="#Page_397">397</a></li> +<li class="isub2">Palmitin, <a href="#Page_310">310</a></li> +<li class="isub2">Pancreas extract, digestion, <a href="#Page_560">560</a> + <span class="pagenum"><a id="Page_659"></a>[Pg 659]</span></li> +<li class="isub3">peptone, <a href="#Page_461">461</a></li> +<li class="isub2">Pancreatin digestion, <a href="#Page_558">558</a></li> +<li class="isub3">preparation, <a href="#Page_560">560</a></li> +<li class="isub2">Paraffin, occurrence in plants, <a href="#Page_404">404</a>, <a href="#Page_405">405</a></li> +<li class="isub2">Paralbumin, <a href="#Page_415">415</a></li> +<li class="isub2">Patrick, volumetric method of milk fat analysis, <a href="#Page_497">497</a></li> +<li class="isub2">Pavy’s process, <a href="#Page_143">143</a></li> +<li class="isub2">Pea starch, <a href="#Page_220">220</a></li> +<li class="isub2">Peanut oil, detection, <a href="#Page_400">400</a></li> +<li class="isub2">Pectic acid, estimation in tobacco, <a href="#Page_603">603</a></li> +<li class="isub2">Pectin, occurrence, <a href="#Page_577">577</a>, <a href="#Page_578">578</a></li> +<li class="isub3">separation, <a href="#Page_578">578</a></li> +<li class="isub2">Pectose, occurrence, <a href="#Page_577">577</a></li> +<li class="isub2">Pellet, continuous observation tube, <a href="#Page_253">253</a></li> +<li class="isub3">method of cold diffusion, <a href="#Page_243">243</a>, <a href="#Page_244">244</a></li> +<li class="isub2">Pentosans, digestibility, <a href="#Page_564">564</a></li> +<li class="isub3">estimation, <a href="#Page_178">178</a></li> +<li class="isub3">revised factors for calculating, <a href="#Page_587">587</a></li> +<li class="isub2">Pentose sugars, estimation, <a href="#Page_177">177</a></li> +<li class="isub2">Pepsin digestion, <a href="#Page_558">558</a></li> +<li class="isub3">preparation, <a href="#Page_558">558</a></li> +<li class="isub2">Peptones, <a href="#Page_412">412</a></li> +<li class="isub3">qualitive tests, <a href="#Page_420">420</a>, <a href="#Page_421">421</a></li> +<li class="isub3">separation from albumoses, <a href="#Page_455">455</a></li> +<li class="isub4">in cheese, <a href="#Page_531">531</a></li> +<li class="isub2">Permanganate gelatin, method for tannins, <a href="#Page_593">593</a>, <a href="#Page_594">594</a></li> +<li class="isub3">hide powder method for tannins, <a href="#Page_595">595</a></li> +<li class="isub3">process, <a href="#Page_132">132</a></li> +<li class="isub4">modified by Ewell, <a href="#Page_136">136</a></li> +<li class="isub2">Peska’s process, <a href="#Page_144">144</a></li> +<li class="isub2">Petroleum ether, preparation, <a href="#Page_312">312</a></li> +<li class="isub4">removal from extracted oils, <a href="#Page_314">314</a></li> +<li class="isub4">solvent, <a href="#Page_41">41</a></li> +<li class="isub2">Phenylhydrazin, action on sugars, <a href="#Page_172">172</a>, <a href="#Page_174">174</a></li> +<li class="isub3">compounds with sugar, <a href="#Page_192">192</a></li> +<li class="isub3">reagent for precipitating furfurol, <a href="#Page_180">180</a></li> +<li class="isub4">sugar, <a href="#Page_171">171</a></li> +<li class="isub2">Phloroglucin, modification of furfurol method, <a href="#Page_588">588</a></li> +<li class="isub3">reagent for precipitating furfurol, <a href="#Page_184">184</a></li> +<li class="isub2">Phosphomolybdic acid, color test, fats and oils, <a href="#Page_353">353</a></li> +<li class="isub2">Phosphorus, loss of organic in combustion, <a href="#Page_37">37</a></li> +<li class="isub2">Phosphotungstic acid, preparation of reagent, <a href="#Page_454">454</a></li> +<li class="isub2">Phytalbumoses, <a href="#Page_412">412</a></li> +<li class="isub2">Phytosterin, detection, <a href="#Page_403">403</a>, <a href="#Page_404">404</a></li> +<li class="isub2">Picric acid, color test, with fats and oils, <a href="#Page_355">355</a></li> +<li class="isub2">Plasmin, <a href="#Page_411">411</a></li> +<li class="isub2">Plaster of paris, use in drying, <a href="#Page_486">486</a></li> +<li class="isub2">Polarimeter, <a href="#Page_83">83</a></li> +<li class="isub2">Polarimètre, <a href="#Page_83">83</a></li> +<li class="isub2">Polarimetry, general principles, <a href="#Page_92">92</a>, <a href="#Page_93">93</a></li> +<li class="isub2">Polariscope, adjustment, <a href="#Page_93">93</a>, <a href="#Page_94">94</a></li> +<li class="isub4">of quartz plates, <a href="#Page_96">96</a>, <a href="#Page_97">97</a></li> +<li class="isub3">definition, <a href="#Page_80">80</a></li> +<li class="isub3">for estimating levulose, <a href="#Page_267">267</a>, <a href="#Page_270">270</a></li> +<li class="isub3">kinds, <a href="#Page_80">80</a>, <a href="#Page_81">81</a></li> +<li class="isub3">rotation instruments, <a href="#Page_82">82</a> + <span class="pagenum"><a id="Page_660"></a>[Pg 660]</span></li> +<li class="isub2">Polaristrobometer, <a href="#Page_83">83</a></li> +<li class="isub2">Polarization, analytical use of data in</li> +<li class="isub7">fermented beverages, <a href="#Page_634">634</a>, <a href="#Page_635">635</a></li> +<li class="isub3">for factory control, <a href="#Page_263">263</a></li> +<li class="isub3">of fermented beverages, <a href="#Page_632">632</a>, <a href="#Page_633">633</a></li> +<li class="isub2">Polarized light, <a href="#Page_75">75</a>, <a href="#Page_76">76</a></li> +<li class="isub3">application to butter analysis, <a href="#Page_514">514</a></li> +<li class="isub3">relation to sugar analysis, <a href="#Page_74">74</a></li> +<li class="isub2">Politis, method of sugar analysis, <a href="#Page_148">148</a></li> +<li class="isub2">Ponceau-red, detection in wines, <a href="#Page_637">637</a></li> +<li class="isub2">Potash, estimation in wines, <a href="#Page_637">637</a></li> +<li class="isub2">Potassium cyanid, use in sugar analysis, <a href="#Page_146">146</a></li> +<li class="isub3">hydroxid, solvent for proteids, <a href="#Page_443">443</a></li> +<li class="isub3">nitrate, occurrence in maize stalks, <a href="#Page_417">417</a></li> +<li class="isub4">preserving agent, <a href="#Page_417">417</a></li> +<li class="isub3">permanganate, reagent for tannins, <a href="#Page_593">593</a></li> +<li class="isub2">Potato starch, <a href="#Page_220">220</a></li> +<li class="isub2">Potatoes, estimation of starch, <a href="#Page_301">301</a>, <a href="#Page_302">302</a></li> +<li class="isub2">Powdered glass, use in drying, <a href="#Page_486">486</a></li> +<li class="isub2">Preserved meats, <a href="#Page_563">563</a></li> +<li class="isub2">Proteid bodies, separation, <a href="#Page_432">432</a>, <a href="#Page_448">448</a></li> +<li class="isub3">nitrogen, estimation in tea and coffee, <a href="#Page_585">585</a></li> +<li class="isub4">qualitive test, <a href="#Page_419">419</a>, <a href="#Page_420">420</a></li> +<li class="isub2">Proteids, action of acids, <a href="#Page_442">442</a></li> +<li class="isub3">classification, <a href="#Page_410">410</a></li> +<li class="isub3">diversity of character, <a href="#Page_434">434</a></li> +<li class="isub3">estimation in cereals, <a href="#Page_543">543</a></li> +<li class="isub5">koumiss, <a href="#Page_534">534</a></li> +<li class="isub5">meats, <a href="#Page_550">550</a></li> +<li class="isub5">milk, <a href="#Page_505">505</a></li> +<li class="isub4">of digestible in cheese, <a href="#Page_531">531</a></li> +<li class="isub3">general principles of separation, <a href="#Page_446">446</a></li> +<li class="isub3">insoluble, <a href="#Page_413">413</a></li> +<li class="isub3">kinds in milk, <a href="#Page_504">504</a></li> +<li class="isub3">methods of drying, <a href="#Page_443">443</a>, <a href="#Page_444">444</a></li> +<li class="isub4">precipitation, <a href="#Page_439">439</a></li> +<li class="isub3">separation, soluble in water, <a href="#Page_439">439</a>, <a href="#Page_440">440</a></li> +<li class="isub3">soluble in dilute alcohol, <a href="#Page_440">440</a></li> +<li class="isub4">salt solution, <a href="#Page_438">438</a></li> +<li class="isub4">water, <a href="#Page_436">436</a></li> +<li class="isub3">solution in alkalies, <a href="#Page_442">442</a></li> +<li class="isub2">Proteolytic ferments, <a href="#Page_557">557</a></li> +<li class="isub2">Proteoses, definition and properties, <a href="#Page_412">412</a></li> +<li class="isub3">separation, <a href="#Page_440">440</a></li> +<li class="isub2">Protoalbumose, <a href="#Page_412">412</a></li> +<li class="isub2">Pulfrich, refractometer, <a href="#Page_331">331</a>, <a href="#Page_333">333</a></li> +<li class="isub2">Pumice stone, use in drying, <a href="#Page_33">33</a>, <a href="#Page_486">486</a></li> +<li class="isub2">Purity, apparent, <a href="#Page_263">263</a></li> +<li class="isub2">Pyknometer, formulas for calculating volume, <a href="#Page_67">67</a></li> +<li class="isub3">use, <a href="#Page_63">63</a>, <a href="#Page_64">64</a></li> +<li class="isub4">at high temperature, <a href="#Page_65">65</a>, <a href="#Page_66">66</a></li> +<li class="isub2">Pyrogalol, reagent for furfurol determination, <a href="#Page_183">183</a></li> + +<li class="isub7 ifrst fs_120"><b>Q</b></li> +<li class="isub2">Quartz plates, <a href="#Page_96">96</a>, <a href="#Page_97">97</a></li> +<li class="isub3">applicability, <a href="#Page_98">98</a></li> +<li class="isub3">corrections, <a href="#Page_97">97</a>, <a href="#Page_98">98</a></li> +<li class="isub2">Quévenne, lactometer, <a href="#Page_466">466</a> +<span class="pagenum"><a id="Page_661"></a>[Pg 661]</span></li> + +<li class="isub7 ifrst fs_120"><b>R</b></li> +<li class="isub2">Raffinose, estimation, <a href="#Page_115">115</a></li> +<li class="isub4">in presence of sucrose, <a href="#Page_266">266</a></li> +<li class="isub3">gyrodynat, <a href="#Page_119">119</a></li> +<li class="isub3">molecular weight, <a href="#Page_177">177</a></li> +<li class="isub2">Raoul, method of determining molecular weights, <a href="#Page_175">175</a></li> +<li class="isub2">Reducing sugars, estimation, <a href="#Page_234">234</a></li> +<li class="isub4">in fermented beverages, <a href="#Page_632">632</a></li> +<li class="isub3">factors for computation, <a href="#Page_141">141</a>, <a href="#Page_142">142</a></li> +<li class="isub3">relation to quantity of copper suboxid, <a href="#Page_141">141</a></li> +<li class="isub2">Refractive index of fats and oils, <a href="#Page_328">328</a></li> +<li class="isub3">indices, <a href="#Page_333">333</a>, <a href="#Page_334">334</a></li> +<li class="isub2">Refractometers, <a href="#Page_329">329</a>, <a href="#Page_333">333</a></li> +<li class="isub3">variation, <a href="#Page_338">338</a></li> +<li class="isub2">Regnault-Pfaundler, calorimetric formula, <a href="#Page_572">572</a></li> +<li class="isub2">Reichert number, <a href="#Page_518">518</a>, <a href="#Page_519">519</a></li> +<li class="isub2">Resorcin, qualitive test for levulose, <a href="#Page_191">191</a></li> +<li class="isub2">Richmond, thermal reaction of oils, <a href="#Page_359">359</a>, <a href="#Page_360">360</a></li> +<li class="isub2">Ritthausen, method of precipitating milk proteids, <a href="#Page_506">506</a></li> +<li class="isub2">Roentgen rays, application to analyses, <a href="#Page_588">588</a></li> +<li class="isub2">Rye starch, <a href="#Page_221">221</a></li> + +<li class="isub7 ifrst fs_120"><b>S</b></li> +<li class="isub2">Saccharic acid, test for dextrose group, <a href="#Page_190">190</a></li> +<li class="isub2">Sachsse’s method of determining amid bodies, <a href="#Page_424">424</a>, <a href="#Page_425">425</a></li> +<li class="isub3">solution, <a href="#Page_122">122</a></li> +<li class="isub2">Saffron, <a href="#Page_522">522</a></li> +<li class="isub2">Safranin, detection in wines, <a href="#Page_637">637</a></li> +<li class="isub2">Sago starch, <a href="#Page_220">220</a></li> +<li class="isub2">Salicylic acid, detection in fermented beverages, <a href="#Page_638">638</a>, <a href="#Page_639">639</a></li> +<li class="isub2">Salt, estimation in butter, <a href="#Page_516">516</a></li> +<li class="isub2">Samples, collecting, <a href="#Page_5">5</a></li> +<li class="isub3">grinding, <a href="#Page_6">6</a></li> +<li class="isub3">preparation, <a href="#Page_3">3</a>, <a href="#Page_4">4</a></li> +<li class="isub3">preserving, <a href="#Page_5">5</a></li> +<li class="isub2">Sand, use in drying, <a href="#Page_486">486</a></li> +<li class="isub2">Saponification, <a href="#Page_376">376</a>, <a href="#Page_384">384</a></li> +<li class="isub3">chemical reactions, <a href="#Page_377">377</a>, <a href="#Page_378">378</a></li> +<li class="isub3">equivalent, <a href="#Page_383">383</a></li> +<li class="isub3">in the cold, <a href="#Page_381">381</a>, <a href="#Page_382">382</a></li> +<li class="isub3">methods of conducting, <a href="#Page_378">378</a>, <a href="#Page_382">382</a></li> +<li class="isub3">under pressure, <a href="#Page_379">379</a>, <a href="#Page_380">380</a></li> +<li class="isub3">value, <a href="#Page_382">382</a>, <a href="#Page_383">383</a></li> +<li class="isub4">of butter, <a href="#Page_518">518</a></li> +<li class="isub3">with alcohol, <a href="#Page_381">381</a></li> +<li class="isub3">without alcohol, <a href="#Page_381">381</a></li> +<li class="isub2">Sarkin, <a href="#Page_416">416</a></li> +<li class="isub3">composition, <a href="#Page_451">451</a></li> +<li class="isub2">Sausages, occurrence of starch, <a href="#Page_553">553</a></li> +<li class="isub2">Scheibler, double polarization, <a href="#Page_102">102</a></li> +<li class="isub3">extraction tube, <a href="#Page_248">248</a></li> +<li class="isub2">Schmidt, method of milk fat analysis, <a href="#Page_489">489</a></li> +<li class="isub2">deSchweinitz and Emery, calorimetric distinction between</li> +<li class="isub7">butter and oleomargarin, <a href="#Page_576">576</a></li> +<li class="isub2">Schweitzer and Lungwitz, iodin addition, <a href="#Page_367">367</a>, <a href="#Page_368">368</a> + <span class="pagenum"><a id="Page_662"></a>[Pg 662]</span></li> +<li class="isub2">Scovell, milk sampler, <a href="#Page_470">470</a></li> +<li class="isub2">Selenite plate, microscopic examination of starches, <a href="#Page_219">219</a></li> +<li class="isub3">use in examination of fat crystals, <a href="#Page_343">343</a></li> +<li class="isub2">Sesame oil, detection, <a href="#Page_402">402</a></li> +<li class="isub3">furfurol reaction, <a href="#Page_521">521</a></li> +<li class="isub2">Shadow polariscope, <a href="#Page_90">90</a></li> +<li class="isub2">Short, method of milk fat analysis, <a href="#Page_490">490</a></li> +<li class="isub2">Shredding apparatus, <a href="#Page_9">9</a>, <a href="#Page_10">10</a>, <a href="#Page_236">236</a></li> +<li class="isub2">Sidersky, modification of Soldaini’s process, <a href="#Page_147">147</a></li> +<li class="isub2">Sieben, method of determining levulose, <a href="#Page_280">280</a></li> +<li class="isub2">Silver nitrate, color test with fats and oils, <a href="#Page_355">355</a></li> +<li class="isub2">Sirups, analysis, <a href="#Page_254">254</a></li> +<li class="isub3">determination of ash, <a href="#Page_256">256</a></li> +<li class="isub4">reducing sugars, <a href="#Page_256">256</a></li> +<li class="isub4">water, <a href="#Page_255">255</a></li> +<li class="isub3">specific gravity, <a href="#Page_254">254</a></li> +<li class="isub2">Sodium chlorid, reagent for extracting proteids, <a href="#Page_433">433</a></li> +<li class="isub3">thiosulfate solution, preparation, <a href="#Page_369">369</a></li> +<li class="isub2">Soldaini copper carbonate process, <a href="#Page_139">139</a>, <a href="#Page_140">140</a></li> +<li class="isub3">gravimetric method, <a href="#Page_258">258</a></li> +<li class="isub2">Soleil-Ventzke polariscope, <a href="#Page_88">88</a>, <a href="#Page_89">89</a></li> +<li class="isub2">Solidifying point of fats and oils, <a href="#Page_326">326</a>, <a href="#Page_327">327</a></li> +<li class="isub2">Soluble acids, estimation in butter, <a href="#Page_517">517</a></li> +<li class="isub3">fat acids, determination, <a href="#Page_389">389</a>, <a href="#Page_390">390</a></li> +<li class="isub2">Solvent, recovery, <a href="#Page_53">53</a>, <a href="#Page_55">55</a></li> +<li class="isub3">in open dish, <a href="#Page_55">55</a></li> +<li class="isub2">Solvents, <a href="#Page_52">52</a>, <a href="#Page_53">53</a></li> +<li class="isub3">object, <a href="#Page_40">40</a></li> +<li class="isub2">Sour milk, density, <a href="#Page_477">477</a></li> +<li class="isub2">Soxhlet, areometric method of milk fat estimation, <a href="#Page_492">492</a>, <a href="#Page_494">494</a></li> +<li class="isub3">extraction apparatus, <a href="#Page_47">47</a></li> +<li class="isub2">Specific gravity, areometric method, <a href="#Page_70">70</a></li> +<li class="isub4">determination in distillate, <a href="#Page_615">615</a></li> +<li class="isub4">example, <a href="#Page_68">68</a></li> +<li class="isub4">method of expressing, <a href="#Page_319">319</a></li> +<li class="isub4">standard of comparison, <a href="#Page_320">320</a></li> +<li class="isub3">heats of materials in calorimeter, <a href="#Page_573">573</a></li> +<li class="isub3">rotatory power, <a href="#Page_115">115</a>, <a href="#Page_116">116</a></li> +<li class="isub4">causes of variation, <a href="#Page_117">117</a></li> +<li class="isub2">Spectroscopy, oils and fats, <a href="#Page_348">348</a></li> +<li class="isub2">Spencer, air-drying oven, <a href="#Page_17">17</a></li> +<li class="isub3">method of estimating caffein, <a href="#Page_583">583</a></li> +<li class="isub3">observation tube, <a href="#Page_253">253</a></li> +<li class="isub2">Spheroidal state, melting point, <a href="#Page_323">323</a>, <a href="#Page_326">326</a></li> +<li class="isub2">Sponge, use in drying, <a href="#Page_486">486</a></li> +<li class="isub2">Spongin, <a href="#Page_416">416</a></li> +<li class="isub2">Stannic bromate, color test with fats and oils, <a href="#Page_356">356</a></li> +<li class="isub2">Starch, colorimetric estimation, <a href="#Page_210">210</a></li> +<li class="isub3">composition, <a href="#Page_196">196</a></li> +<li class="isub3">disturbing bodies in estimation, <a href="#Page_209">209</a></li> +<li class="isub3">estimation in potatoes, <a href="#Page_301">301</a>, <a href="#Page_302">302</a></li> +<li class="isub5">sausages, <a href="#Page_553">553</a></li> +<li class="isub4">of ash, <a href="#Page_203">203</a></li> +<li class="isub5">nitrogen, <a href="#Page_203">203</a></li> +<li class="isub5">water, <a href="#Page_202">202</a>, <a href="#Page_299">299</a></li> +<li class="isub4">with barium hydroxid, <a href="#Page_208">208</a> + <span class="pagenum"><a id="Page_663"></a>[Pg 663]</span></li> +<li class="isub3">factor for calculating from dextrose, <a href="#Page_205">205</a></li> +<li class="isub3">fixation of iodin, <a href="#Page_211">211</a></li> +<li class="isub3">gyrodynat of soluble, <a href="#Page_206">206</a></li> +<li class="isub3">hydrolysis at high temperatures, <a href="#Page_199">199</a></li> +<li class="isub4">in an autoclave, <a href="#Page_199">199</a>, <a href="#Page_200">200</a></li> +<li class="isub4">with acids, <a href="#Page_203">203</a>, <a href="#Page_204">204</a></li> +<li class="isub3">occurrence, <a href="#Page_298">298</a></li> +<li class="isub4">in tobacco, <a href="#Page_604">604</a></li> +<li class="isub3">particles, separation, <a href="#Page_197">197</a></li> +<li class="isub3">polarization, <a href="#Page_205">205</a></li> +<li class="isub3">principles of determination, <a href="#Page_201">201</a></li> +<li class="isub3">properties, <a href="#Page_196">196</a></li> +<li class="isub3">rapid estimation, <a href="#Page_207">207</a></li> +<li class="isub3">separation, <a href="#Page_399">399</a></li> +<li class="isub3">solution at high pressure, <a href="#Page_206">206</a></li> +<li class="isub4">in nitric acid, <a href="#Page_206">206</a></li> +<li class="isub2">Starches, classification, <a href="#Page_218">218</a></li> +<li class="isub3">description of typical, <a href="#Page_219">219</a></li> +<li class="isub3">identification, <a href="#Page_211">211</a></li> +<li class="isub3">microscopic examination, <a href="#Page_219">219</a></li> +<li class="isub3">occurrence in the juices of plants, <a href="#Page_228">228</a></li> +<li class="isub2">Steam coil oven, <a href="#Page_20">20</a>, <a href="#Page_21">21</a></li> +<li class="isub2">Stearin, <a href="#Page_310">310</a></li> +<li class="isub2">Stone, method of estimating pentosans, <a href="#Page_181">181</a></li> +<li class="isub2">Strontium saccharates, <a href="#Page_187">187</a></li> +<li class="isub2">Stutzer, artificial digestion of cheese, <a href="#Page_561">561</a></li> +<li class="isub3">method of estimating gelatin, <a href="#Page_457">457</a></li> +<li class="isub2">Succinic acid, estimation in fermented beverages, <a href="#Page_630">630</a>, <a href="#Page_631">631</a></li> +<li class="isub2">Sucrose, cobaltous nitrate test, <a href="#Page_189">189</a></li> +<li class="isub3">estimation in coffee, <a href="#Page_586">586</a></li> +<li class="isub4">presence of dextrose, <a href="#Page_274">274</a></li> +<li class="isub5">levulose and dextrose, <a href="#Page_280">280</a>, <a href="#Page_285">285</a></li> +<li class="isub5">raffinose, <a href="#Page_266">266</a></li> +<li class="isub3">molecular weight, <a href="#Page_176">176</a></li> +<li class="isub3">occurrence, <a href="#Page_264">264</a></li> +<li class="isub3">pipette, <a href="#Page_231">231</a>, <a href="#Page_232">232</a></li> +<li class="isub3">qualitive optical test, <a href="#Page_188">188</a></li> +<li class="isub3">separation and estimation, <a href="#Page_264">264</a></li> +<li class="isub2">Sugar analysis, chemical methods, <a href="#Page_120">120</a></li> +<li class="isub3">classification of methods, <a href="#Page_61">61</a>, <a href="#Page_62">62</a></li> +<li class="isub3">general remarks, <a href="#Page_104">104</a></li> +<li class="isub3">gravimetric copper methods, <a href="#Page_149">149</a>, <a href="#Page_170">170</a></li> +<li class="isub4">Halle method, <a href="#Page_153">153</a>, <a href="#Page_155">155</a></li> +<li class="isub3">laboratory gravimetric method, <a href="#Page_150">150-153</a></li> +<li class="isub3">permanganate process, <a href="#Page_132">132-135</a></li> +<li class="isub3">volumetric laboratory method, <a href="#Page_129">129</a>, <a href="#Page_130">130</a></li> +<li class="isub4">methods, <a href="#Page_121">121</a></li> +<li class="isub2">Sugar beets, analysis, <a href="#Page_242">242</a></li> +<li class="isub4">apparatus for grinding, <a href="#Page_10">10</a></li> +<li class="isub4">extraction with alcohol, <a href="#Page_245">245</a>, <a href="#Page_247">247</a></li> +<li class="isub3">content in maple sap, <a href="#Page_228">228</a></li> +<li class="isub3">direct determination in canes, <a href="#Page_235">235</a></li> +<li class="isub3">estimation in cane and beet pulp, <a href="#Page_238">238</a></li> +<li class="isub4">sap, <a href="#Page_228">228-230</a></li> +<li class="isub4">sugar beets, <a href="#Page_242">242</a></li> +<li class="isub3">extraction from plants, <a href="#Page_230">230</a> + <span class="pagenum"><a id="Page_664"></a>[Pg 664]</span></li> +<li class="isub3">flask, diffusion and alcohol digestion, <a href="#Page_245">245</a></li> +<li class="isub2">Sugar flasks, <a href="#Page_98">98</a>, <a href="#Page_99">99</a></li> +<li class="isub3">instantaneous diffusion, <a href="#Page_243">243</a></li> +<li class="isub3">juices, preservation, <a href="#Page_235">235</a></li> +<li class="isub3">mills, <a href="#Page_230">230</a></li> +<li class="isub3">preparation of pure, <a href="#Page_60">60</a></li> +<li class="isub3">removal from starchy bodies, <a href="#Page_300">300</a></li> +<li class="isub3">solutions, preparation for polarization, <a href="#Page_99">99-104</a></li> +<li class="isub4">specific gravity, <a href="#Page_62">62</a></li> +<li class="isub2">Sugars, determination in dried material, <a href="#Page_239">239</a></li> +<li class="isub4">without weighing, <a href="#Page_253">253</a></li> +<li class="isub3">estimation in fermented beverages, <a href="#Page_632">632</a>, <a href="#Page_635">635</a></li> +<li class="isub3">hexose, <a href="#Page_59">59</a></li> +<li class="isub3">miscellaneous qualitive tests, <a href="#Page_193">193</a></li> +<li class="isub3">occurrence in tobacco, <a href="#Page_604">604</a></li> +<li class="isub3">optical properties, <a href="#Page_74">74</a>, <a href="#Page_75">75</a></li> +<li class="isub3">pentose, <a href="#Page_59">59</a></li> +<li class="isub3">qualitive tests, <a href="#Page_188">188</a></li> +<li class="isub3">separation by lead oxid, <a href="#Page_284">284</a>, <a href="#Page_285">285</a></li> +<li class="isub3">state of existence in plants, <a href="#Page_227">227</a></li> +<li class="isub2">Sulfur chlorid, reagent for oils, <a href="#Page_402">402</a>, <a href="#Page_403">403</a></li> +<li class="isub3">determination in proteids, <a href="#Page_446">446</a></li> +<li class="isub3">loss of organic in combustion, <a href="#Page_37">37</a></li> +<li class="isub2">Sulfuric acid, color test for fats and oils, <a href="#Page_352">352</a></li> +<li class="isub4">estimation in tobacco, <a href="#Page_600">600</a></li> +<li class="isub3">saponification, <a href="#Page_357">357</a>, <a href="#Page_358">358</a></li> +<li class="isub2">Sulfurous acid, elimination, <a href="#Page_519">519</a></li> +<li class="isub3">estimation in fermented beverage, <a href="#Page_638">638</a></li> + +<li class="isub7 ifrst fs_120"><b>T</b></li> +<li class="isub2">Tannic acid, estimation in tobacco, <a href="#Page_604">604</a></li> +<li class="isub3">reagent for milk proteids, <a href="#Page_507">507</a></li> +<li class="isub2">Tannin, composition, <a href="#Page_588">588</a></li> +<li class="isub3">detection, <a href="#Page_589">589</a>, <a href="#Page_593">593</a></li> +<li class="isub3">estimation <a href="#Page_589">589</a>, <a href="#Page_596">596</a></li> +<li class="isub4">by hide powder method, <a href="#Page_590">590</a>, <a href="#Page_592">592</a></li> +<li class="isub3">infusion, preparation, <a href="#Page_596">596</a></li> +<li class="isub3">occurrence, <a href="#Page_588">588</a></li> +<li class="isub3">permanganate gelatin method, <a href="#Page_593">593</a>, <a href="#Page_594">594</a></li> +<li class="isub3">precipitation with metallic salts, <a href="#Page_589">589</a></li> +<li class="isub2">Tartaric acid, estimation in wine, <a href="#Page_229">229</a>, <a href="#Page_230">230</a></li> +<li class="isub2">Tea and coffee, <a href="#Page_582">582</a></li> +<li class="isub2">Thein, <a href="#Page_583">583</a></li> +<li class="isub2">Thermal reactions, fats and oils, <a href="#Page_356">356</a>, <a href="#Page_363">363</a></li> +<li class="isub2">Thermostat for steam bath, <a href="#Page_15">15</a></li> +<li class="isub2">Thörner, method of milk fat analysis, <a href="#Page_491">491</a></li> +<li class="isub2">Tobacco, acid and basic constituents, <a href="#Page_597">597</a></li> +<li class="isub3">burning qualities, <a href="#Page_608">608</a></li> +<li class="isub3">composition, <a href="#Page_598">598</a>, <a href="#Page_599">599</a></li> +<li class="isub4">of ash, <a href="#Page_598">598</a></li> +<li class="isub3">fermentation, <a href="#Page_596">596</a>, <a href="#Page_597">597</a></li> +<li class="isub3">fractional extraction, <a href="#Page_608">608</a></li> +<li class="isub2">Tollens and Günther, method of estimating pentosans, <a href="#Page_180">180</a></li> +<li class="isub2">Torsion Viscosimeter, <a href="#Page_342">342</a></li> +<li class="isub2">Total solids, calculation, <a href="#Page_478">478</a></li> +<li class="isub3">formulas for calculating, <a href="#Page_479">479</a>, <a href="#Page_480">480</a></li> +<li class="isub2">Trinitroalbumin, <a href="#Page_411">411</a></li> +<li class="isub2">Triple shadow polariscope, <a href="#Page_91">91</a>, <a href="#Page_92">92</a></li> +<li class="isub2">Tropæolin, detection in wines, <a href="#Page_637">637</a> + <span class="pagenum"><a id="Page_665"></a>[Pg 665]</span></li> +<li class="isub2">Turbidity temperature, fats and oils, <a href="#Page_351">351</a></li> +<li class="isub2">Turmeric, <a href="#Page_522">522</a></li> +<li class="isub2">Tyrosin, <a href="#Page_412">412</a></li> +<li class="isub3">occurrence in milk, <a href="#Page_464">464</a></li> +<li class="isub2">Tyrotoxicon, occurrence in milk, <a href="#Page_464">464</a></li> + +<li class="isub7 ifrst fs_120"><b>U</b></li> +<li class="isub2">Ulsch, drying oven, <a href="#Page_31">31</a></li> +<li class="isub2">Unicedin, <a href="#Page_413">413</a></li> +<li class="isub2">Urea, occurrence, in milk, <a href="#Page_464">464</a></li> + +<li class="isub7 ifrst fs_120"><b>V</b></li> +<li class="isub2">Vacuum, drying, <a href="#Page_18">18</a></li> +<li class="isub2">Van Slyke, method of estimating casein, <a href="#Page_508">508</a></li> +<li class="isub2">Vegetable substances, preparation, <a href="#Page_3">3</a>, <a href="#Page_4">4</a></li> +<li class="isub2">Vegetables, sampling, <a href="#Page_577">577</a></li> +<li class="isub2">Vinolin, detection in wines, <a href="#Page_637">637</a></li> +<li class="isub2">Viscosimetry, <a href="#Page_342">342</a>, <a href="#Page_345">345</a></li> +<li class="isub2">Viscosity of fats and oils, <a href="#Page_342">342</a></li> +<li class="isub2">Viscous liquids, drying, <a href="#Page_32">32</a>, <a href="#Page_33">33</a></li> +<li class="isub2">Vitellin, <a href="#Page_411">411</a></li> +<li class="isub2">Vogel, table for identifying starches, <a href="#Page_212">212</a>, <a href="#Page_213">213</a></li> +<li class="isub2">Volatile acids, estimation in butter, <a href="#Page_517">517</a></li> +<li class="isub5">fermented beverages, <a href="#Page_627">627</a>, <a href="#Page_628">628</a></li> +<li class="isub3">bodies, drying, <a href="#Page_13">13</a></li> +<li class="isub3">fat acids, determination, <a href="#Page_386">386</a>, <a href="#Page_388">388</a></li> +<li class="isub4">distillation, <a href="#Page_387">387</a>, <a href="#Page_388">388</a></li> +<li class="isub4">titration, <a href="#Page_388">388</a></li> +<li class="isub2">Volume of precipitate, calculation, <a href="#Page_279">279</a></li> + +<li class="isub7 ifrst fs_120"><b>W</b></li> +<li class="isub2">Water, action on composition of proteids, <a href="#Page_437">437</a></li> +<li class="isub3">estimation in butter, <a href="#Page_515">515</a></li> +<li class="isub4">cereals, <a href="#Page_542">542</a></li> +<li class="isub4">fermented beverages, <a href="#Page_626">626</a></li> +<li class="isub4">fruits and vegetables, <a href="#Page_578">578</a></li> +<li class="isub4">koumiss, <a href="#Page_536">536</a></li> +<li class="isub4">meats, <a href="#Page_549">549</a></li> +<li class="isub4">tobacco, <a href="#Page_599">599</a></li> +<li class="isub2">Watermelons, composition, <a href="#Page_581">581</a>, <a href="#Page_582">582</a></li> +<li class="isub2">Wax, occurrence in tobacco, <a href="#Page_608">608</a></li> +<li class="isub2">Waxes, composition, <a href="#Page_309">309</a></li> +<li class="isub2">Westphal balance, <a href="#Page_69">69</a></li> +<li class="isub2">Wheat starch, <a href="#Page_221">221</a></li> +<li class="isub2">Wiechmann, formula for calculating sugars, <a href="#Page_307">307</a></li> +<li class="isub3">method of estimating levulose, sucrose and dextrose, <a href="#Page_280">280</a>, <a href="#Page_281">281</a></li> +<li class="isub2">Williams, calorimeter, <a href="#Page_570">570</a></li> +<li class="isub2">Winter, estimation of levulose and dextrose</li> +<li class="isub7">in presence of sucrose, <a href="#Page_283">283</a>, <a href="#Page_284">284</a></li> +<li class="isub2">Wood pulp, use in drying, <a href="#Page_486">486</a></li> +<li class="isub2">Wrampelmayer, drying oven, <a href="#Page_30">30</a></li> + +<li class="isub7 ifrst fs_120"><b>X</b></li> +<li class="isub2">Xanthin, <a href="#Page_416">416</a></li> +<li class="isub2">Xanthoproteic reaction, <a href="#Page_420">420</a></li> +<li class="isub2">Xylan, occurrence, <a href="#Page_586">586</a></li> + +<li class="isub7 ifrst fs_120"><b>Y</b></li> +<li class="isub2">Yeast, inversion, <a href="#Page_113">113</a></li> + +<li class="isub7 ifrst fs_120"><b>Z</b></li> +<li class="isub2">Zein, <a href="#Page_441">441</a></li> +<li class="isub2">Zeiss, butyrorefractometer, <a href="#Page_339">339</a>, <a href="#Page_341">341</a></li> +<li class="isub2">Zinc, occurrence, in evaporated fruits, <a href="#Page_380">380</a>, <a href="#Page_581">581</a></li> +<li class="isub3">sulfate, reagent for precipitating proteids, <a href="#Page_433">433</a></li> +<li class="isub3">separating albumoses from peptones, <a href="#Page_455">455</a></li> +</ul> + +<hr class="chap x-ebookmaker-drop"> + +<div class="chapter"> +<p><span class="pagenum"><a id="Page_666"></a>[Pg 666]</span></p> +<h2 class="nobreak">CORRECTIONS FOR VOL. I.</h2> +</div> + +<div class="blockquot"> +<p class="neg-indent">Page 5, 11th line, insert “ten” before “thousand.”</p> + +<p class="neg-indent">Page 21, read “Magdeburg” instead of “Madgeburg” in both instances.</p> + +<p class="neg-indent">Page 61, for per cent. of oxygen in ulmin read “28.7” instead of “8.7.”</p> + +<p class="neg-indent">Page 62, for per cent. of carbon in apocrenic acid read “54.4” instead of “34.4.”</p> + +<p class="neg-indent">Page 112, 2d line from bottom, read “14” instead of “13.”</p> + +<p class="neg-indent">Page 140, the sentence beginning “The burette is lowered etc.” is +repeated. <i>Dele</i> one of them.</p> + +<p class="neg-indent">Page 141, 6th line, insert “or air dried” after “moisture.”</p> + +<p class="neg-indent">Page 141, in example read 10.25, 10.22, 13.07 and 76.21 for 9.52, 9.22, +12.07, and 60.35 respectively.</p> + +<p class="neg-indent">Page 158, 3d line of <b>172</b>, insert “and estimating soluble matters +therein” after “flow.”</p> + +<p class="neg-indent">Page 159, omit “√<span class="over">   </span>” in first formula.</p> + +<p class="neg-indent">Page 293, 12th line, read “U” for “V.”</p> + +<p class="neg-indent">Page 309, last line, read “sixth” for “sixteenth.”</p> + +<p class="neg-indent">Page 312, 1st line, read “atmosphere” instead of “room.”</p> + +<p class="neg-indent">Page 315, 6th and 7th lines, read <b>299</b>, and <b>300</b>, for +<b>294</b>, and <b>295</b>, respectively.</p> + +<p class="neg-indent">Page 323, 3d line from bottom, read <b>301</b> for <b>299</b>.</p> + +<p class="neg-indent">Page 333, 5th line of <b>316</b>, insert after “is” “to eliminate +carbon dioxid and.”</p> + +<p class="neg-indent">Page 354, 3d line from end of (6) insert after “solution” “acidified +with acetic and;” same line, transfer “r” from “ther,” to “pecipitate.”</p> + +<p class="neg-indent">Page 357, 6th line from end of (4) insert after “difference” “and the +phosphoric acid estimated as in <b>380</b>, deducted therefrom.”</p> + +<p class="neg-indent">Page 367, 4th line, add after “taken,” “The phosphoric acid may be +determined as described in <b>372</b>, or following paragraphs.”</p> + +<p class="neg-indent">Page 410, line 21, <i>dele</i> “dilute” and insert “one per cent +nitric.”</p> + +<p class="neg-indent">Page 410, line 25, after “capsule” insert “adding water once or twice.”</p> + +<p class="neg-indent">Page 449, 4th line read “hydrobromic” for “hydrochloric.”</p> + +<p class="neg-indent">Page 457, reference “30” read “Band 38” instead of “Band 37.”</p> + +<p class="neg-indent">Page 468, 8th line, <i>dele</i> “or gypsum” and read “200” instead of +“50.”</p> + +<p class="neg-indent">Page 471, last line, read “not” for “very.”</p> + +<p class="neg-indent">Page 472, 4th line, insert “un” before “successful.”</p> + +<p class="neg-indent">Page 496, 5th line, insert “the” before “soil.”</p> + +<p class="neg-indent">Page 515, next to last and last lines, read “stannous” instead of +“zinc.”</p> + +<p class="neg-indent">Page 516, second line, read “stannous” instead of “zinc.”</p> + +<p class="neg-indent">Page 557, 9th line of <b>500</b> read “red-yellow” instead of “blue.”</p> +</div> + +<h2 class="nobreak">CORRECTIONS FOR VOL. II.</h2> +<div class="blockquot"> + +<p class="neg-indent">Page 14, line 21, read “61.74 per cent.” for “16.74 per cent.”</p> + +<p class="neg-indent">Page 23, 8th line from bottom, read “0.0025.” for “0.0035.”</p> + +<p class="neg-indent">Page 54, 9th line, read “white” instead of “yellow.”</p> + +<p class="neg-indent">Page 54, 13th line, read “phosphate” instead of “phosphomolybdate.” +<span class="pagenum"><a id="Page_667"></a>[Pg 667]</span></p> + +<p class="neg-indent">Page 57, 8th line from bottom, read “saturated” instead of “citrate.”</p> + +<p class="neg-indent">Page 73, read “Kosmann” in 10th line of paragraph <b>72</b> for “Kormann.”</p> + +<p class="neg-indent">Page 158, reference number 72, read “1889” instead of “1888.”</p> +</div> + +<h2 class="nobreak">CORRECTIONS FOR VOL. III.</h2> +<div class="blockquot"> + +<p class="neg-indent">Page 11, name of Figure 4 read “Dreef” instead of “Dree.”</p> + +<p class="neg-indent">Page 40, fifth and seventh lines, read “Courtonne” instead of “Courtoune.”</p> + +<p class="neg-indent">Page 59, eighth line from bottom, insert “original” before “optical.”</p> + +<p class="neg-indent">Page 60, second line, read “<i>d</i>” instead of “<i>l</i>” before “fructose.”</p> + +<p class="neg-indent">Page 68, legend of Figure 29, read “areometers” instead of “aereometers.”</p> + +<p class="neg-indent">Page 146, sixth line from bottom, insert “cyanid” after “potassium.”</p> + +<p class="neg-indent">Page 159, instead of headings for table as given, substitute those on +page 160.</p> + +<p class="neg-indent">Page 177, in formula for lactose, read “H₂₂” instead of “H₃₂”; in formula +for arabinose, read “H₁₀” instead of “H₁₉.”</p> + +<p class="neg-indent">Page 180, seventh line from bottom, read “Günther” instead of “Gunther.”</p> + +<p class="neg-indent">Page 191, read paragraph <b>169</b>. Seventh line read “resorcin” instead +of “resorsin.”</p> + +<p class="neg-indent">Page 268, legend of Figure 77, read “Desiccating” instead of “Dessicating.”</p> + +<p class="neg-indent">Page 288, in formula (2) read “53d” instead of “54d.”</p> + +<p class="neg-indent">Pages 328, 329 and 334, read “Amagat” instead of “Armagat.”</p> + +<p class="neg-indent">Page 348, fourth line from bottom, omit accent in “sesame.”</p> + +<p class="neg-indent">Page 365, (b) first line, read 24.8 instead of 24.6.</p> + +<p class="neg-indent">Page 424, 4th line from bottom, read “nitrites” instead of “nitrates.”</p> + +<p class="neg-indent">Page 425, 4th and 5th lines, read “nitrite” instead of “nitrate.”</p> + +<p class="neg-indent">Page 445, in table of factors for computing proteids under Maize Proteids, +read “16.06 and 6.22” instead of “15.64 and 6.39” respectively.</p> + +<p class="neg-indent">Page 451, sixth line from bottom, read “occur” instead of “occurs.”</p> + +<p class="neg-indent">Page 464, twelfth line from bottom, <i>dele</i> “food.”</p> + +<p class="neg-indent">Page 499, ninth line from bottom, read “Babcock.”</p> + +<p class="neg-indent">Page 543, sixteenth line, read “6.06 and 6.22” for “6.31 and 6.39” +respectively.</p> + +<p class="neg-indent">Pages 555-556, read “amylolytic” for “amylytic.”</p> + +<p class="neg-indent">Page 555, fifth and seventeenth lines from bottom, insert after “into +dextrin, maltose.”</p> + +<p class="neg-indent">Page 572, second equation, read “<i>tʹ</i>ₙ₂” instead of “<i>tʹ</i>ₙ₁.”</p> + +<p class="neg-indent">Page 573, 3rd line from bottom, read “stirring” for “storing.”</p> + +<p class="neg-indent">Page 574, 6th line from bottom, read “Θ₄” for “O_4.”</p> + +<p class="neg-indent">Page 575, 16th line from bottom, insert “one gram of” before “substance.”</p> + +<p class="neg-indent">Page 576 instead of 567, fourth line of paragraph 566, read “Calorie” +instead of “calorie.”</p> + +<p class="neg-indent">Page 644, <i>dele</i> “Band 12, Ss. 64 und 199” in reference 94.</p> +</div> + +<hr class="chap x-ebookmaker-drop"> + +<div class="chapter"> +<div class="transnote bbox spa2"> +<p class="f120 spa1">Transcriber’s Notes:</p> +<hr class="r10"> +<p>The cover image was created by the transcriber, and is in the public domain.</p> +<p>New original cover art included with this eBook is granted to the public domain.</p> +<p>Deprecated spellings were not corrected.</p> +<p>The illustrations have been moved so that they do not break up + paragraphs and so that they are next to the text they illustrate.</p> +<p>Typographical and punctuation errors have been silently corrected.</p> +</div></div> + +<div style='text-align:center'>*** END OF THE PROJECT GUTENBERG EBOOK 75389 ***</div> +</body> +</html> + diff --git a/75389-h/images/cbl-2.jpg b/75389-h/images/cbl-2.jpg Binary files differnew file mode 100644 index 0000000..826baeb --- /dev/null +++ b/75389-h/images/cbl-2.jpg diff --git a/75389-h/images/cbl-3.jpg b/75389-h/images/cbl-3.jpg 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