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+Project Gutenberg's Researches on Cellulose, by C. F. Cross and E. J. Bevan
+
+This eBook is for the use of anyone anywhere at no cost and with
+almost no restrictions whatsoever.  You may copy it, give it away or
+re-use it under the terms of the Project Gutenberg License included
+with this eBook or online at www.gutenberg.org
+
+
+Title: Researches on Cellulose
+       1895-1900
+
+Author: C. F. Cross
+        E. J. Bevan
+
+Release Date: September 16, 2007 [EBook #22620]
+
+Language: English
+
+Character set encoding: ISO-8859-1
+
+*** START OF THIS PROJECT GUTENBERG EBOOK RESEARCHES ON CELLULOSE ***
+
+
+
+
+Produced by Juliet Sutherland, Josephine Paolucci and the
+Online Distributed Proofreading Team at http://www.pgdp.net.
+(This file was produced from images generously made
+available by The Internet Archive/Million Book Project).
+
+
+
+
+
+
+
+
+
+
+RESEARCHES ON CELLULOSE
+
+1895-1900
+
+BY
+
+CROSS & BEVAN
+
+(C. F. CROSS AND E. J. BEVAN)
+
+
+_SECOND EDITION_
+
+
+LONGMANS, GREEN, AND CO.
+39 PATERNOSTER ROW, LONDON
+NEW YORK, BOMBAY, AND CALCUTTA
+
+1907
+
+All rights reserved
+
+       *       *       *       *       *
+
+Transcriber's note:
+
+For Text: A word surrounded by a cedilla such as ~this~ signifies that
+the word is bolded in the text. A word surrounded by underscores like
+_this_ signifies the word is italics in the text. The italic and bold
+markup for single italized letters (such as variables in equations) and
+"foreign" abbreviations are deleted for easier reading.
+
+For numbers and equations: Parentheses have been added to clarify
+fractions. Underscores before bracketed numbers in equations denote a
+subscript. Superscripts are designated with a caret and brackets, e.g.
+11.1^{3} is 11.1 to the third power. Greek letters in equations are
+translated to their English version.
+
+The sections in the Table of Contents are not used in the actual text.
+They have been added for clarity.
+
+Minor typos have been corrected and footnotes moved to the end of the
+sections
+
+       *       *       *       *       *
+
+
+
+
+
+PREFACE TO SECOND EDITION
+
+
+This edition is a _reprint_ of the first in response to a continuous
+demand for the book. The matter, consisting as it does largely of
+records, does not call for any revision, and, as a contribution to the
+development of theory, any particular interest which it has is
+associated with the date at which it was written.
+
+The volume which has since appeared is the sequel, and aims at an
+exposition of the subject "to date".
+
+
+
+
+PREFACE
+
+
+This volume, which is intended as a supplement to the work which we
+published in 1895, gives a brief account of researches which have been
+subsequently published, as well as of certain of our own investigations,
+the results of which are now for the first time recorded.
+
+We have not attempted to give the subject-matter the form of a connected
+record. The contributions to the study of 'Cellulose' which are noticed
+are spread over a large area, are mostly 'sectional' in their aim, and
+the only cohesion which we can give them is that of classifying them
+according to the plan of our original work. Their subject-matter is
+reproduced in the form of a _pr�cis_, as much condensed as possible; of
+the more important papers the original title is given. In all cases we
+have endeavoured to reproduce the Author's main conclusions, and in most
+cases without comment or criticism.
+
+Specialists will note that the basis of investigation is still in a
+great measure empirical; and of this the most obvious criterion is the
+confusion attaching to the use of the very word 'Cellulose.' This is due
+to various causes, one of which is the curious specialisation of the
+term in Germany as the equivalent of 'wood cellulose.' The restriction
+of this general or group term has had an influence even in scientific
+circles. Another influence preventing the recognition of the obvious
+and, as we think, inevitable basis of classification of the 'celluloses'
+is the empiricism of the methods of agricultural chemistry, which as
+regards cellulose are so far chiefly concerned with its negative
+characteristics and the analytical determination of the indigestible
+residue of fodder plants. Physiologists, again, have their own views and
+methods in dealing with cellulose, and have hitherto had but little
+regard to the work of the chemist in differentiating and classifying the
+celluloses on a systematic basis. There are many sides to the subject,
+and it is only by a sustained effort towards centralisation that the
+general recognition of a systematic basis can be secured.
+
+We may, we hope usefully, direct attention to the conspicuous neglect of
+the subject in this country. To the matter of the present volume,
+excluding our own investigations, there are but two contributions from
+English laboratories. We invite the younger generation of students of
+chemistry to measure the probability of finding a working career in
+connection with the cellulose industries. They will not find this
+invitation in the treatment accorded to the subject in text-books and
+lectures. It is probable, indeed, that the impression produced by their
+studies is that the industries in coal-tar products largely exceed in
+importance those of which the carbohydrates are the basis; whereas the
+former are quite insignificant by comparison. A little reflection will
+prove that cellulose, starch, and sugar are of vast industrial moment in
+the order in which they are mentioned. If it is an open question to
+what extent science follows industry, or _vice versa_, it is not open to
+doubt that scientific men, and especially chemists, are called in these
+days to lead and follow where industrial evolution is most active. There
+is ample evidence of activity and great expansion in the cellulose
+industries, especially in those which involve the chemistry of the raw
+material; and the present volume should serve to show that there is
+rapid advance in the science of the subject. Hence our appeal to the
+workers not to neglect those opportunities which belong to the days of
+small beginnings.
+
+We have especially to acknowledge the services of Mr. J. F. BRIGGS in
+investigations which are recorded on pp. 34-40 and pp. 125-133 of the
+text.
+
+
+
+
+CONTENTS
+
+THE MATTER OF THIS VOLUME MAY BE DIVIDED INTO THE FOLLOWING SECTIONS
+
+
+                                                                 PAGE
+
+INTRODUCTION--DEALING WITH THE SUBJECT IN GENERAL OUTLINE           1
+
+
+SECTION
+
+I. GENERAL CHEMISTRY OF THE TYPICAL COTTON CELLULOSE               13
+
+II. SYNTHETICAL DERIVATIVES--SULPHOCARBONATES AND ESTERS           27
+
+III. DECOMPOSITIONS OF CELLULOSE SUCH AS THROW LIGHT
+     ON THE PROBLEM OF ITS CONSTITUTION                            67
+
+IV. CELLULOSE GROUP, INCLUDING HEMICELLULOSES AND
+    TISSUE CONSTITUENTS OF FUNGI                                   97
+
+V. FURFUROIDS, i.e. PENTOSANES AND FURFURAL-YIELDING
+   CONSTITUENTS GENERALLY                                         114
+
+VI. THE LIGNOCELLULOSES                                           125
+
+VII. PECTIC GROUP                                                 152
+
+VIII. INDUSTRIAL AND TECHNICAL. GENERAL REVIEW                    155
+
+
+INDEX OF AUTHORS                                                  177
+
+INDEX OF SUBJECTS                                                 178
+
+
+
+
+CELLULOSE
+
+
+
+
+INTRODUCTION
+
+
+In the period 1895-1900, which has elapsed since the original
+publication of our work on 'Cellulose,' there have appeared a large
+number of publications dealing with special points in the chemistry of
+cellulose. So large has been the contribution of matter that it has been
+considered opportune to pass it under review; and the present volume,
+taking the form of a supplement to the original work, is designed to
+incorporate this new matter and bring the subject as a whole to the
+level to which it is thereby to be raised. Some of our critics in
+reviewing the original work have pronounced it 'inchoate.' For this
+there are some explanations inherent in the matter itself. It must be
+remembered that every special province of the science has its systematic
+beginning, and in that stage of evolution makes a temporary 'law unto
+itself.' In the absence of a dominating theory or generalisation which,
+when adopted, gives it an organic connection with the general advance of
+the science, there is no other course than to classify the
+subject-matter. Thus 'the carbohydrates' may be said to have been in the
+inchoate condition, qualified by a certain classification, prior to the
+pioneering investigations of Fischer. In attacking the already
+accumulated and so far classified material from the point of view of a
+dominating theory, he found not only that the material fell into
+systematic order and grew rapidly under the stimulus of fruitful
+investigation, but in turn contributed to the firmer establishment of
+the theoretical views to which the subject owed its systematic new
+birth. On the other hand, every chemist knows that it is only the
+simpler of the carbohydrates which are so individualised as to be
+connoted by a particular formula in the stereoisomeric system. Leaving
+the monoses, there is even a doubt as to the constitution of cane sugar;
+and the elements of uncertainty thicken as we approach the question of
+the chemical structure of starch. This unique product of plant life has
+a literature of its own, and how little of this is fully known to what
+we may term the 'average chemist' is seen by the methods he will employ
+for its quantitative estimation. In one particular review of our work
+where we are taken to task for producing 'an aggravating book, inchoate
+in the highest degree ... disfigured by an obscurity of diction which
+must materially diminish its usefulness' ['Nature,' 1897, p. 241], the
+author, who is a well-known and competent critic, makes use of the short
+expression in regard to the more complex carbohydrates, 'Above cane
+sugar, higher in the series, all is chaos,' and in reference to starch,
+'the subject is still enshrouded in mystery.' This 'material' complexity
+is at its maximum with the most complex members of the series, which are
+the celluloses, and we think accounts in part for the impatience of our
+critic. 'Obscurity of diction' is a personal quantity, and we must leave
+that criticism to the fates. We find also that many workers whose
+publications we notice in this present volume quite ignore the _plan_ of
+the work, though they make use of its matter. We think it necessary to
+restate this plan, which, we are satisfied, is systematic, and, in fact,
+inevitable. Cellulose is in the first instance a _structure_, and the
+anatomical relationships supply a certain basis of classification. Next,
+it is known to us and is defined by the negative characteristics of
+resistance to hydrolytic actions and oxidations. These are dealt with in
+the order of their intensity. Next we have the more positive definition
+by ultimate products of hydrolysis, so far as they are known, which
+discloses more particularly the presence of a greater or less proportion
+of furfural-yielding groups. Putting all these together as criteria of
+function and composition we find they supply common or general dividing
+lines, within which groups of these products are contained. The
+classification is natural, and in that sense inevitable; and it not only
+groups the physiological and chemical facts, but the industrial also. We
+do not propose to argue the question whether the latter adds any cogency
+to a scientific scheme. We are satisfied that it does, and we do not
+find any necessity to exclude a particular set of phenomena from
+consideration, because they involve 'commercial' factors. We have dealt
+with this classification in the original work (p. 78), and we discuss
+its essential basis in the present volume (p. 28) in connection with the
+definition of a 'normal' cellulose. But the 'normal' cellulose is not
+the only cellulose, any more than a primary alcohol or an aliphatic
+alcohol are the only alcohols. This point is confused or ignored in
+several of the recent contributions of investigators. It will suffice to
+cite one of these in illustration. On p. 16 we give an account of an
+investigation of the several methods of estimating cellulose, which is
+full of valuable and interesting matter. The purpose of the author's
+elaborate comparative study is to decide which has the strongest claims
+to be regarded as the 'standard' method. They appear to have a
+preference for the method of Lange--viz. that of heating at high
+temperatures (180�) with alkaline hydrates, but the investigation shows
+that (as we had definitely stated in our original work, p. 214) this is
+subject to large and variable errors. The adverse judgment of the
+authors, we may point out, is entirely determined on the question of
+aggregate weight or yield, and without reference to the ultimate
+composition or constitution of the final product. None of the available
+criteria are applied to the product to determine whether it is a
+cellulose (anhydride) or a hydrate or a hydrolysed product. After these
+alkali-fusion processes the method of chlorination is experimentally
+reviewed and dismissed for the reason that the product retains
+furfural-yielding groups, which is, from our point of view, a particular
+recommendation, i.e. is evidence of the selective action of the chlorine
+and subsequent hydrolysis upon the lignone group. As a matter of fact it
+is the only method yet available for isolating the cellulose from a
+lignocellulose by a treatment which is quantitatively to be accounted
+for in every detail of the reactions. It does not yield a 'normal'
+cellulose, and this is the expression which, in our opinion, the authors
+should have used. It should have been pointed out, moreover, that, as
+the cellulose is separated from actual condensed combination with the
+lignone groups, it may be expected to be obtained in a hydrated form,
+and also not as a homogeneous substance like the normal cotton
+cellulose. The product is a cellulose of the second group of the
+classification. Another point in this investigation which we must
+criticise is the ultimate selection of the Schulze method of prolonged
+maceration with nitric acid and a chlorate, followed by suitable
+hydrolysis of the non-cellulose derivatives to soluble products. Apart
+from its exceptional inconvenience, rendering it quite impracticable in
+laboratories which are concerned with the valuation of cellulosic raw
+materials for industrial purposes, the attack of the reagent is complex
+and ill-defined. This criticism we would make general by pointing out
+that such processes quite ignore the specific characteristics of the
+non-cellulose components of the compound celluloses. The second division
+of the plan of our work was to define these constituents by bringing
+together all that had been established concerning them. These groups are
+widely divergent in chemical character, as are the compound celluloses
+in function in the plant. Consequently there is for each a special
+method of attack, and it is a reversion to pure empiricism to expect any
+one treatment to act equally on the pectocelluloses, lignocelluloses,
+and cutocelluloses. Processes of isolating cellulose are really more
+strictly defined as methods of selective and regulated attack of the
+groups with which they occur, combined or mixed. A chemist familiar with
+such types as rhea or ramie (pectocellulose), jute (lignocellulose), and
+raffia (cutocellulose) knows exactly the specific treatment to apply to
+each for isolating the cellulose, and must view with some surprise the
+appearance at this date of such 'universal prescriptions' as the process
+in question.
+
+The third division of our plan of arrangement comprised the synthetical
+derivatives of the celluloses, the sulphocarbonates first, as peculiarly
+characteristic, and then the esters, chiefly the acetates, benzoates,
+and nitrates. To these, investigators appear to have devoted but little
+attention, and the contribution of new matter in the present volume is
+mainly the result of our own researches. It will appear from this work
+that an exhaustive study of the cellulose esters promises to assist very
+definitely in the study of constitutional problems.
+
+This brings us to the fourth and, to the theoretical chemist, the most
+important aspect of the subject, the problem of the actual molecular
+structure of the celluloses and compound celluloses. It is herein we are
+of opinion that the subject makes a 'law unto itself.' If the
+constitution of starch is shrouded in mystery and can only be vaguely
+expressed by generalising a complex mass of statistics of its successive
+hydrolyses, we can only still more vaguely guess at the distance which
+separates us from a mental picture of the cellulose unit. We endeavour
+to show by our later investigations that this problem merges into that
+of the actual structure of cellulose in the mass. It is definitely
+ascertained that a change in the molecule, or reacting unit, of a
+cellulose, proportionately affects the structural properties of the
+derived compounds, both sulphocarbonates and esters. This is at least an
+indication that the properties of the visible aggregates are directly
+related to the actual configuration of the chemical units. But it
+appears that we are barred from the present discussion of such a problem
+in absence of any theory of the solid state generally, but more
+particularly of those forms of matter which are grouped together as
+'colloids.'
+
+Cellulose is distinguished by its inherent constructive functions, and
+these functions take effect in the plastic or colloidal condition of the
+substance. These properties are equally conspicuous in the synthetical
+derivatives of the compound. Without reference, therefore, to further
+speculations, and not deterred by any apparent hopelessness of solving
+so large a problem, it is clear that we have to exhaust this field by
+exact measurements of all the constants which can be reduced to
+numerical expression. It is most likely that the issue may conflict with
+some of our current views of the molecular state which are largely drawn
+from a study of the relatively dissociated forms of matter. But such
+conflicts are only those of enlargement, and we anticipate that all
+chemists look for an enlargement of the molecular horizon precisely in
+those regions where the forces of cell-life manifest themselves.
+
+The _cellulose group_ has been further differentiated by later
+investigations. The fibrous celluloses of which the typical members
+receive important industrial applications, graduate by insensible stages
+into the hemicelluloses which may be regarded as a well-established
+sub-group. In considering their morphological and functional
+relationships it is evident that the graduation accords with their
+structure and the less permanent functions which they fulfil. They are
+aggregates of monoses of the various types, chiefly mannose, galactose,
+dextrose, &c., so far as they have been investigated.
+
+Closely connected with this group are the constituents of the tissues of
+fungi. The recent researches of Winterstein and Gilson, which are noted
+in this present volume, have established definitely that they contain a
+nitrogenous group in intimate combination with a carbohydrate complex.
+This group is closely related to chitin, yielding glucosamin and acetic
+acid as products of ultimate hydrolysis. Special interest attaches to
+these residues, as they are in a sense intermediate products between the
+great groups of the carbohydrates and proteids (E. Fischer, Ber. 19,
+1920), and their further investigation by physiological methods may be
+expected to disclose a genetic connection.
+
+The _lignocelluloses_ have been further investigated. Certain new types
+have been added, notably a soluble or 'pectic' form isolated from the
+juice of the white currant (p. 152), and the pith-like wood of the
+�schynomene (p. 135).
+
+Further researches on the typical fibrous lignocellulose have given us a
+basis for correcting some of the conclusions recorded in our original
+work, and a study of the esters has thrown some light on the
+constitution of the complex (p. 130).
+
+Of importance also is the identification of the hydroxyfurfurals as
+constituents of the lignocelluloses generally, and the proof that the
+characteristic colour-reactions with phenols (phloroglucinol) may be
+ascribed to the presence of these compounds (p. 116).
+
+The _pectocelluloses_ have not been the subject of systematic chemical
+investigation, but the researches of Gilson ('La Cristallisation de la
+Cellulose et la Composition Chimique de la Membrane Cellulaire
+V�g�tale,' 'La Revue,' 'La Cellule,' i. ix.) are an important
+contribution to the natural history of cellulose, especially in relation
+to the 'pectic' constituents of the parenchymatous celluloses.
+Indirectly also the researches of Tollens on the 'pectins' have
+contributed to the subject in correcting some of the views which have
+had a text-book currency for a long period. These are dealt with on p.
+151. The results establish that the pectins are rather the soluble
+hydrated form of cellulosic aggregates in which acid groups may be
+represented; but such groups are not to be regarded as essentially
+characteristic of this class of compounds.
+
+~Furfural-yielding Substances~ (Furfuroids).--This group of plant products
+has been, by later investigations, more definitely and exclusively
+connected with the celluloses--i.e. with the more permanent of plant
+tissues. From the characteristic property of yielding furfural, which
+they have in common with the pentoses, they have been assumed to be the
+anhydrides of these C_{5} sugars or pentosanes; but the direct evidence
+for this assumption has been shown to be wanting. In regard to their
+origin the indirect evidences which have accumulated all point to their
+formation in the plant from hexoses. Of special interest, in its
+bearings on this point, is the direct transformation of levulose into
+furfural derivatives, which takes place under the action of condensing
+agents. The most characteristic is that produced by the action of
+anhydrous hydrobromic acid in presence of ether [Fenton], yielding a
+brommethyl furfural
+
+     C_{6}H_{12}O_{6} - 4H_{2}O + HBr = C_{5}H_{3}.O_{2}.CH_{2}Br
+
+with a Br atom in the methyl group. These researches of Fenton's appear
+to us to have the most obvious and direct bearings upon the genetic
+relationships of the plant furfuroids and not only _per se_. To give
+them their full significance we must recall the later researches of
+Brown and Morris, which establish that cane sugar is a primary or direct
+product of assimilation, and that starch, which had been assumed to be a
+species of universal _mati�re premi�re_, is probably rather a general
+reserve for the elaborating work of the plant. If now the aldose groups
+tend to pass over into the starch form, representing a temporary
+overflow product of the assimilating energy, it would appear that the
+ketose or levulose groups are preferentially used up in the elaboration
+of the permanent tissue. We must also take into consideration the
+researches of Lobry de Bruyn showing the labile functions of the typical
+CO group in both aldoses and hexoses, whence we may conclude that in the
+plant-cell the transition from dextrose to levulose is a very simple and
+often occurring process.
+
+We ourselves have contributed a link in this chain of evidence
+connecting the furfuroids of the plant with levulose or other
+keto-hexose. We have shown that the hydroxyfurfurals are constituents of
+the lignocelluloses. The proportion present in the free state is small,
+and it is not difficult to show that they are products of breakdown of
+the lignone groups. If we assume that such groups are derived ultimately
+from levulose, we have to account for the detachment of the methyl
+group. This, however, is not difficult, and we need only call to mind
+that the lignocelluloses are characterised by the presence of methoxy
+groups and a residue which is directly and easily hydrolysed to acetic
+acid. Moreover, the condensation need not be assumed to be a simple
+dehydration with attendant rearrangement; it may very well be
+accompanied or preceded by fixation of oxygen. Leaving out the
+hypothetical discussion of minor variations, there is a marked
+convergence of the evidence as to the main facts which establish the
+general relationships of the furfuroid group. This group includes both
+saturated and unsaturated or condensed compounds. The former are
+constituents of celluloses, the latter of the lignone complex of the
+lignocelluloses.
+
+The actual production of furfural by boiling with condensing acids is a
+quantitative measure of only a portion, i.e. certain members of the
+group. The hydroxyfurfurals, not being volatile, are not measured in
+this way. By secondary reactions they may yield some furfural, but as
+they are highly reactive compounds, and most readily condensed, they are
+for the most part converted into complex 'tarry' products. Hence we have
+no means, as yet, of estimating those tissue constituents which yield
+hydroxyfurfurals; also we have no measure of the furfurane-rings
+existing performed in such a condensed complex as lignone. But, chemists
+having added in the last few years a large number of facts and
+well-defined probabilities, it is clear that the further investigation
+of the furfuroid group will take its stand upon a much more adequate
+basis than heretofore. On the view of 'furfural-yielding' being
+co-extensive with 'pentose or pentosane,' not only were a number of
+important facts obscured or misinterpreted, but there was a barrenness
+of suggestion of genetic relationships. As the group has been widened
+very much beyond these limits, it is clear that if any group term or
+designation is to be retained that of 'furfuroid' is 'neutral' in
+character, and equally applicable to saturated substances of such widely
+divergent chemical character as pentoses, hexosones, glycuronic acid,
+and perhaps, most important of all, levulose itself, all of which are
+susceptible of condensation to furfural or furfurane derivatives, as
+well as to those unsaturated compounds, constituents of plant tissues
+which are already furfurane derivatives.
+
+From the chemical point of view such terms are perhaps superfluous. But
+physiological relationships have a significance of their own; and there
+is a physiological or functional cohesion marking this group which
+calls for recognition, at least for the time, and we therefore propose
+to retain the term furfuroid.[1]
+
+~General Experimental Methods.~--In the investigation of the cellulose
+group it is clear that methods of ultimate hydrolysis are of first
+importance. None are so convenient as those which are based on the
+action of sulphuric acid, more or less concentrated (H_{2}SO_{4}.3H_{2}O
+- H_{2}SO_{4}H_{2}O). Such methods have been frequently employed in the
+investigations noted in this volume. We notice a common deficiency in
+the interpretation of the results. It appears to be sufficient to
+isolate and identify a crystalline monose, without reference to the
+yield or proportion to the parent substance, to establish some main
+point in connection with its constitution. On the other hand, it is
+clear that in hydrolysing a given cellulose-complex we ought to aim at
+complete, i.e. _quantitative, statistics_. The hydrolytic transformation
+of starch to dextrins and maltose has been followed in this way, and the
+methods may serve as a model to which cellulose transformations should
+be approximated. In fact, what is very much wanted is a systematic
+re-examination of the typical celluloses in which all the constants of
+the terms between the original and the ultimate monose groups shall be
+determined. Such constants are similar to those for the starch-dextrose
+series, viz. opticity and cupric reduction. Various methods of
+fractionation are similarly available, chiefly the precipitation of the
+intermediate 'dextrins' by alcohol.
+
+Where the original celluloses are homogeneous we should thus obtain
+transformation series, similarly expressed to those of starch. In the
+case of the celluloses which are mixtures, or of complex constitution,
+there are various methods of either fractionating the original, or of
+selectively attacking particular monoses resulting from the
+transformation. By methods which are approximately quantitative a
+mixture of groups, such as we have, for instance, in jute cellulose,
+could be followed through the several stages of their resolution into
+monoses. To put the matter generally, in these colloidal and complex
+carbohydrates the ordinary physical criteria of molecular weight are
+wanting. Therefore, we cannot determine the relationship of a given
+product of decomposition to the parent molecule save by means of a
+quantitative mass-proportion. Physical criteria are only of determining
+value when associated with such constants as cupric reduction, and
+these, again, must be referred to some arbitrary initial weight, such
+as, for convenience, 100 parts of the original.
+
+Instead of adopting these methods, without which, as a typical case, the
+mechanism of starch conversions could not have been followed, we have
+been content with a purely qualitative study of the analogous series
+obtainable from the celluloses under the action of sulphuric acid. A
+very important field of investigation lies open, especially to those who
+are generally familiar with the methods of studying starch conversions;
+and we may hope in this direction for a series of valuable contributions
+to the problem of the actual constitution of the celluloses.
+
+FOOTNOTES:
+
+[1] In this we are confirmed by other writers. See Tollens, _J. f�r
+Landw._ 1901, p. 27.
+
+
+
+
+SECTION I. GENERAL CHEMISTRY OF THE TYPICAL COTTON CELLULOSE
+
+
+(p. 3)[2] ~Ash Constituents.~--It is frequently asserted that silica has a
+structural function _sui generis_ in the plant skeleton, having a
+relationship to the cellulosic constituents of the plant, distinct from
+that of the inorganic ash components with which it is associated. It
+should be noted that the matter has been specifically investigated in
+two directions. In Berl. Ber. 5, 568 (A. Ladenburg), and again in 11,
+822 (W. Lange), appear two papers 'On the Nature of Plant Constituents
+containing Silicon,' which contain the results of experimental
+investigations of equisetum species--distinguished for their
+exceptionally high 'ash' with large proportion of silica--to determine
+whether there are any grounds for assuming the existence of
+silicon-organic compounds in the plant, the analogues of carbon
+compounds. The conclusions arrived at are entirely negative. In
+reference to the second assumption that the cuticular tissues of cereal
+straws, of esparto, of the bamboo, owe their special properties to
+siliceous components, it has been shown by direct experiment upon the
+former that their rigidity and resistance to water are in no way
+affected by cultivation in a silica-free medium. In other words, the
+structural peculiarities of the gramine� in these respects are due to
+the physical characteristics chiefly of the (lignified) cells of the
+hypodermal tissue, and to the composition and arrangement of the cells
+of the cuticle.
+
+_'Swedish' filter papers_ of modern make are so far freed from inorganic
+constituents that the weight of the ash may be neglected in nearly all
+quantitative experiments [Fresenius, Ztschr. Anal Chem. 1883, 241]. It
+represents usually about 1/1000 mgr. per 1 sq. cm. of area of the paper.
+
+_The form of an 'ash'_ derived from a fibrous structure, is that of the
+'organic' original, more or less, according to its proportion and
+composition. The proportion of 'natural ash' is seldom large enough, nor
+are the components of such character as to give a coherent ash, but if
+in the case of a fibrous structure it is combined or intimately mixed
+with inorganic compounds deposited within the fibres from solution, the
+latter may be made to yield a perfect skeleton of the fibre after
+burning off the organic matter. It is by such means that the mantles
+used in the Welsbach system of incandescent lighting are prepared. A
+purified cotton fabric--or yarn--is treated with a concentrated solution
+of the mixed nitrates of thorium and cerium, and, after drying, the
+cellulose is burned away. A perfect and coherent skeleton of the fabric
+is obtained, composed of the mixed oxides. Such mantles have fulfilled
+the requirements of the industry up to the present time, but later
+experiments forecast a notable improvement. It has been found that
+artificial cellulose fibres can be spun with solutions containing
+considerable proportions of soluble compounds of these oxides. Such
+fibres, when knitted into mantles and ignited, yield an inorganic
+skeleton of the oxides of homogeneous structure and smooth contour. De
+Mare in 1894, and Knofler in 1895, patented methods of preparing such
+cellulose threads containing the salts of thorium and cerium, by
+spinning a collodion containing the latter in solution. When finally
+ignited, after being brought into the suitable mantle form, there
+results a structure which proves vastly more durable than the original
+Welsbach mantle. The cause of the superiority is thus set forth by V.
+H. Lewes in a recent publication (J. Soc. of Arts, 1900, p. 858): 'The
+alteration in physical structure has a most extraordinary effect upon
+the light-giving life of the mantle, and also on its strength, as after
+burning for a few hundred hours the constant bombardment of the mantle
+by dust particles drawn up by the rush of air in the chimney causes the
+formation of silicates on the surface of the mantle owing to silica
+being present in the air, and this seems to affect the Welsbach
+structure far more than it does the "Clamond" type, with the result that
+when burned continuously the Welsbach mantle falls to so low a pitch of
+light emissivity after 500 to 600 hours, as to be a mere shadow of its
+former self, giving not more than one-third of its original light,
+whilst the Knofler mantle keeps up its light-emitting power to a much
+greater extent, and the Lehner fabric is the most remarkable of all. Two
+Lehner mantles which have now been burning continuously in my laboratory
+for over 3,000 hours give at this moment a brighter light emissivity
+than most of the Welsbachs do in their prime.' ...'The new developments
+of the Clamond process form as important a step in the history of
+incandescent gas lighting as the discoveries which gave rise to the
+original mantles.'
+
+It has further been found that the oxides themselves can be dissolved in
+the cellulose alkaline sulphocarbonate (viscose) solution, and
+artificial threads have been spun containing from 25 to 30 p.ct. of the
+oxides in homogeneous admixture with the cellulose. This method has
+obvious advantages over the collodion method both in regard to the
+molecular relationship of the oxides to the cellulose and to cheapness
+of production.
+
+
+UNTERSUCHUNGEN �BER VERSCHIEDENE BESTIMMUNGSMETHODEN DER CELLULOSE.
+
+H. SURINGAR AND B. TOLLENS (Ztschr. angew. Chem. 1896, No. 23).
+
+~INVESTIGATION OF METHODS OF DETERMINING CELLULOSE.~
+
+_Introduction._--This is an exhaustive bibliography of the subject,
+describing also the various methods of cellulose estimation, noted in
+historical sequence. First, the Weende 'crude fibre' method (Henneberg)
+with modifications of Wattenberg, Holdefleiss, and others is dealt with.
+The product of this treatment, viz. 'crude fibre' is a mixture,
+containing furfuroids and lignone compounds. Next follows a group of
+processes which aim at producing a 'pure cellulose' by eliminating
+lignone constituents, for which the merely hydrolytic treatments of the
+Weende method are ineffectual. The method of F. Schulze--prolonged
+digestion with dilute nitric acid, with addition of chlorate--has been
+largely employed, though the composition of the product is more or less
+divergent from a 'pure cellulose.'
+
+Dilute nitric acid at 60-80� (Cross and Bevan) and a dilute mixture of
+nitric and sulphuric acids (Lifschutz) have been employed for isolating
+cellulose from the lignocelluloses. Hoffmeister modifies the method of
+Schulze by substituting hydrochloric acid for the nitric acid. Treatment
+with the halogens associated with alkaline processes of hydrolysis is
+the basis of the methods of Hugo Muller (bromine water) and Cross and
+Bevan (chlorine gas). Lastly, the authors notice the methods based upon
+the action of the alkaline hydrates at high temperatures (180�) in
+presence of water (Lange), or of glycerin (Gabriel). The process of
+heating to 210� with glycerin only (H�nig) yields a very impure and
+ill-defined product.
+
+For comparative investigation of these processes certain celluloses and
+cellulosic materials were prepared as follows:
+
+(a) _'Rag' cellulose._--A chemical filter paper, containing only
+cotton and linen celluloses, was further purified by boiling with dilute
+acid and dilute alkali. After thorough washing it was air-dried.
+
+(b) _Wood cellulose._--Pine wood sawdust was treated by digestion for
+fourteen days with dilute nitric acid with addition of chlorate
+(Schulze). The mass was washed and digested with alkaline lye (1.25
+p.ct. KOH), and exhaustively washed, treated with dilute acetic acid;
+again washed, and finally air-dried.
+
+This product was found to yield 2.3 p.ct. furfural on distillation with
+HCl (1.06 sp.gr.).
+
+(c) _Purified wood._--Pine wood sawdust was treated in succession with
+dilute alkalis and acids, in the cold, and with alcohol and ether until
+exhausted of products soluble in these liquids and reagents.
+
+In addition to the above the authors have also employed jute fibre and
+raw cotton wool in their investigations.
+
+They note that the yield of cellulose is in many cases sensibly lowered
+by treating the material after drying at the temperature of 100�. The
+material for treatment is therefore weighed in the air-dry condition,
+and a similar sample weighed off for drying at 100� for determination of
+moisture.
+
+The main results of the experimental investigation are as follows:--
+
+_Weende process_ further attacks the purified celluloses as follows:
+Wood cellulose losing in weight 8-9 p.ct.; filter paper, 6-7.5 p.ct.,
+and the latter treated a second time loses a further 4-5 p.ct. It is
+clear, therefore, that the process is of purely empirical value.
+
+_Schulze._--This process gave a yield of 47.6 p.ct. cellulose from pine
+wood. The celluloses themselves, treated by the process, showed losses
+of 1-3 p.ct. in weight, much less therefore than in the preceding case.
+
+_H�nig's_ method of heating with glycerin to 210� was found to yield
+products very far removed from 'cellulose.' The process may have a
+certain value in estimations of 'crude fibre,' but is dismissed from
+further consideration in relation to cellulose.
+
+_Lange._--The purpose of the investigation was to test the validity of
+the statement that the celluloses are not attacked by alkaline hydrates
+at 180�. Experiments with pine wood yielded a series of percentages for
+cellulose varying from 36 to 41; the 'purified wood' gave also variable
+numbers, 44 to 49 per cent. It was found possible to limit these
+variations by altering the conditions in the later stages of isolating
+the product; but further experiments on the celluloses themselves
+previously isolated by other processes showed that they were profoundly
+and variably attacked by the 'Lange' treatment, wood cellulose losing 50
+per cent. of its weight, and filter paper (cellulose) losing 15 per
+cent. Further, a specimen of jute yielded 58 per cent. of cellulose by
+this method instead of the normal 78 per cent. It was also found that
+the celluloses isolated by the process, when subjected to a second
+treatment, underwent a further large conversion into soluble
+derivatives, and in a third treatment further losses of 5-10 per cent
+were obtained. The authors attach value, notwithstanding, to the process
+which they state to yield an 'approximately pure cellulose,' and they
+describe a modified method embodying the improvements in detail
+resulting from their investigation.
+
+_Gabriel's_ method of heating with a glycerin solution of alkaline
+hydrate is a combination of 'H�nig' and 'Lange.' An extended
+investigation showed as in the case of the latter that the
+celluloses themselves are more or less profoundly attacked by the
+treatment--further that the celluloses isolated from lignocelluloses and
+other complex raw materials are much 'less pure' than those obtained by
+the Lange process. Thus, notably in regard to furfural yielding
+constituents, the latter yield 1-2 p.ct. furfural, whereas _specimens of
+'jute cellulose'_ obtained by the Gabriel process were found to yield _9
+to 13 p.ct. furfural_.
+
+_Cross and Bevan._--Chlorination process yielded in the hands of the
+authors results confirming the figures given in 'Cellulose' for yield of
+cellulose. Investigation of the products for yield of furfural, gave 9
+p.ct. of this aldehyde showing the presence of celluloses, other than
+the normal type.
+
+_Conclusions._--The subjoined table gives the mean numerical results for
+yield of end-product or 'cellulose' by the various methods. In the case
+of the 'celluloses' the results are those of the further action of the
+several processes on the end-product of a previous process.
+
+                       |                 Methods
+                       | F. Schulze | Weende | Lange | Gabriel |  Cross
+                       |            |        |       |         | and Bevan
+--------------------------------------------------------------------------
+Wood cellulose         | 98.51      | 91.52  | 48.22 | 55.93   | --
+Filter paper cellulose | 99.62      | 95.63  | 78.17 | 79.77   | --
+Swedish filter paper   | 96.58      |  --    | 84.76 |  --     | --
+Ordinary filter paper  | 98.17      | 93.39  | 86.58 |  --     | --
+Cotton ('wool')        | 98.38      | 89.98  | 63.96 | 67.88   | --
+Jute                   |  --        |  --    | 57.93 | 71.64   | 75.27
+Purified wood          |  --        |  --    |{49.27 |  --     | --
+                       |            |        |{46.56 |         |
+Raw wood               | 47.60      |  --    |{40.82 |  --     | --
+                       |            |        |{38.87 |         |
+--------------------------------------------------------------------------
+
+The final conclusion drawn from the results is that none of the
+processes fulfil the requirements of an ideal method. Those which may
+be carried out in a reasonably short time are deficient in two
+directions: (1) they yield a 'cellulose' containing more or less
+oxycellulose; (2) the celluloses themselves are attacked under the
+conditions of treatment, and the end product or cellulose merely
+represents a particular and at the same time variable equilibrium, as
+between the resistance of the cellulose and the attack of the reagents
+employed; this attack being by no means confined to the non-cellulose
+constituents. Schulze's method appears to give the nearest approximation
+to the 'actual cellulose' of the raw material.
+
+       *       *       *       *       *
+
+(p. 8) ~SOLUTIONS OF CELLULOSE~--(1) ~ZINC CHLORIDE.~--To prepare a
+homogeneous solution of cellulose by means of the neutral chloride, a
+prolonged digestion at or about 100� with the concentrated reagent is
+required. The dissolution of the cellulose is not a simple phenomenon,
+but is attended with hydrolysis and a certain degree of condensation.
+The latter result is evidenced by the formation of furfural, the former
+by the presence of soluble carbohydrates in the solution obtained by
+diluting the original solution and filtering from the reprecipitated
+cellulose. The authors have observed that in carefully conducted
+experiments cotton cellulose may be dissolved in the reagent, and
+reprecipitated with a loss of only 1 p.ct. in weight. This, however, is
+a 'net' result, and leaves undetermined the degree of hydration of the
+recovered cellulose as of hydrolysis of the original to groups of lower
+molecular weights. Bronnert finds that a previous hydration of the
+cellulose--e.g. by the process of alkaline mercerisation and removal of
+the alkali by washing--enables the zinc chloride to effect its
+dissolution by digestion in the cold. (U.S. patent, 646,799/1900. See
+also p. 59.)
+
+_Industrial applications._--(a) _Vulcanised fibre_ is prepared by
+treating paper with four times its weight of the concentrated aqueous
+solution (65-75� B.), and in the resulting gelatinised condition is
+worked up into masses, blocks, sheets, &c., of any required thickness.
+The washing of these masses to remove the zinc salt is a very lengthy
+operation.
+
+To render the product waterproof the process of nitration is sometimes
+superadded [D.R.P. 3181/1878]. Further details of manufacture are given
+in Prakt. Handbuch d. Papierfabrikation, p. 1703 [C. Hofmann].
+
+(b) _Calico-printing._--The use of the solution as a thickener or
+colour vehicle, more especially as a substitute for albumen in pigment
+styles, was patented by E. B. Manby, but the process has not been
+industrially developed [E.P. 10,466/1894].
+
+(c) _Artificial silk._--This is a refinement of the earlier
+applications of the solution in spinning cellulose threads for
+conversion into carbon filaments for electrical glow-lamps. This section
+will be found dealt with on p. 59.
+
+(p. 13) (2) ~Cuprammonium solution.~--The application of the solution of
+cellulose in cuprammonium to the production of a fine filament in
+continuous length, 'artificial silk,' has been very considerably studied
+and developed in the period 1897-1900, as evidenced by the series of
+patents of Fremery and Urban, Pauly, Bronnert, and others. The subject
+will also be found dealt with on p. 58.
+
+       *       *       *       *       *
+
+(p. 15) ~Reactions of cellulose with iodine.~--In a recent paper, F.
+Mylius deals with the reaction of starch and cellulose with iodine,
+pointing out that the blue colouration depends upon the presence of
+water and iodides. In absence of the latter, and therefore in presence
+of compounds which destroy or absorb hydriodic acid--e.g. iodic
+acid--there results a _brown_ addition product. The products in question
+have the characteristics of _solid solutions_ of the halogen. (Berl.
+Ber. 1895, 390.)
+
+(24) ~Mercerisation~--Notwithstanding the enormous recent developments in
+the industrial application of the mercerising reaction, there have been
+no noteworthy contributions to the theoretical aspects of the subject.
+The following abstract gives an outline of the scope of an important
+technical work on the subject.
+
+
+DIE MERCERISATION DER BAUMWOLLE.
+
+PAUL GARDNER (Berlin: 1898. J. Springer).
+
+~THE MERCERISATION OF COTTON.~
+
+This monograph of some 150 pages is chiefly devoted to the patent
+literature of the subject. The chemical and physical modifications of
+the cotton substance under the action of strong alkaline lye, were set
+forth by Mercer in 1844-5, and there has resulted from subsequent
+investigations but little increase in our knowledge of the fundamental
+facts. The treatment was industrially developed by Mercer in certain
+directions, chiefly (1) for preparing webs of cloth required to stand
+considerable strain, and (2) for producing cr�pon effects by local or
+topical action of the alkali. But the results achieved awakened but a
+transitory interest, and the matter passed into oblivion; so much so,
+indeed, that a German patent [No. 30,966] was granted in 1884 to the
+Messrs. Depouilly for cr�pon effects due to the differential shrinkage
+of fabrics under mercerisation, by processes and treatments long
+previously described by Mercer. Such effects have had a considerable
+vogue in recent years, but it was not until the discovery of the
+lustreing effect resulting from the association of the mercerising
+actions with the condition of strain or tension of the yarn or fabric
+that the industry in 'mercerised' goods was started on the lines which
+have led to the present colossal development. The merit of this
+discovery is now generally recognised as belonging to Thomas and Prevost
+of Crefeld, notwithstanding that priority of patent right belongs to the
+English technologist, H. A. Lowe.
+
+The author critically discusses the grounds of the now celebrated patent
+controversy, arising out of the conflict of the claims of German patent
+85,564/1895 of the former, and English patent 4452/1890 of the latter.
+The author concludes that Lowe's specification undoubtedly describes the
+lustreing effect of mercerising in much more definite terms than that of
+Thomas and Prevost. These inventors, on the other hand, realised the
+effect industrially, which Lowe certainly failed to do, as evidenced by
+his allowing the patent to lapse. As an explanation of his failure, the
+author suggests that Lowe did not sufficiently extend his observations
+to goods made from Egyptian and other long-stapled cottons, in which
+class only are the full effects of the added lustre obtained.
+
+Following these original patents are the specifications of a number of
+inventions which, however, are of insignificant moment so far as
+introducing any essential variation of the mercerising treatment.
+
+The third section of the work describes in detail the various mechanical
+devices which have been patented for carrying out the treatment on yarn
+and cloth.
+
+The fourth section deals with the fundamental facts underlying the
+process and effects summed up in the term 'mercerisation.' These are as
+follows:--
+
+(a) Although all forms of fibrous celluloses are similarly affected by
+strong alkaline solutions, it is only the Egyptian and other
+long-stapled cottons--i.e. the goods made from them--which under the
+treatment acquire the special high lustre which ranks as 'silky.' Goods
+made from American cottons acquire a certain 'finish' and lustre, but
+the effects are not such as to have an industrial value--i.e. a value
+proportional to the cost of treatment.
+
+(b) The lustre is determined by exposing the goods to strong tension,
+either when under the action of the alkali, or subsequently, but only
+when the cellulose is in the special condition of hydration which is the
+main chemical effect of the mercerising treatment.
+
+(c) The degree of tension required is approximately that which opposes
+the shrinkage in dimensions, otherwise determined by the action of the
+alkali. The following table exhibits the variations of shrinkage of
+Egyptian when mercerised without tension, under varying conditions as
+regards the essential factors of the treatment--viz. (1) concentration
+of the alkaline lye, (2) temperature, and (3) duration of action (the
+latter being of subordinate moment):--
+
+ _______________________________________________________________________
+|               |             |             |                    |      |
+| Concentration |             |             |                    |      |
+| of lye (NaOH) |    5�B.     |    10�B.    |        15�B        | 25�B |
+|               |   |    |    |   |    |    |      |      |      |      |
+| Duration of   |   |    |    |   |    |    |      |      |      |      |
+| action in     | 1 | 10 | 30 | 1 | 10 | 30 |   1  |  10  |  30  |      |
+| minutes       |   |    |    |   |    |    |      |      |      |      |
+|               |   |    |    |   |    |    |      |      |      |      |
+| Temperatures  |   Percentage shrinkages (Egyptian yarns) as under:--  |
+| as under:--   |   |    |    |   |    |    |      |      |      |      |
+|  2�           | 0 |  0 |  0 | 1 |  1 |  1 | 12.2 | 15.2 | 15.8 | 19.2 |
+| 18�           | 0 |  0 |  0 | 0 |  0 |  0 |  8.0 |  8.8 | 11.8 | 19.8 |
+| 30�           | 0 |  0 |  0 | 0 |  0 |  0 |  4.6 |  4.6 |  6.0 | 19.0 |
+| 80�           | 0 |  0 |  0 | 0 |  0 |  0 |  3.5 |  3.5 |  9.8 | 13.4 |
+|_______________|___|____|____|___|____|____|______|______|______|______|
+ _______________________________________________________________________
+|               |             |                    |                    |
+| Concentration |             |                    |                    |
+| of lye (NaOH) |     25�B    |        30�B        |        35�B        |
+|               |      |      |      |      |      |      |      |      |
+| Duration of   |      |      |      |      |      |      |      |      |
+| action in     |  10  |  30  |   1  |  10  |  30  |   1  |  10  |  30  |
+| minutes       |      |      |      |      |      |      |      |      |
+|               |      |      |      |      |      |      |      |      |
+| Temperatures  |   Percentage shrinkages (Egyptian yarns) as under:--  |
+| as under:--   |      |      |      |      |      |      |      |      |
+|  2�           | 19.8 | 21.5 | 22.7 | 22.7 | 22.7 | 24.2 | 24.5 | 24.7 |
+| 18�           | 20.1 | 21.0 | 21.2 | 22.0 | 22.3 | 23.5 | 23.8 | 24.7 |
+| 30�           | 19.5 | 19.0 | 18.5 | 19.5 | 19.8 | 20.7 | 21.0 | 21.1 |
+| 80�           | 13.7 | 14.2 | 15.0 | 15.1 | 15.5 | 15.0 | 15.2 | 15.4 |
+|_______________|______|______|______|______|______|______|______|______|
+
+The more important general indications of the above results are--(1) The
+mercerisation action commences with a lye of 10�B., and increases with
+increased strength of the lye up to a maximum at 35�B. There is,
+however, a relatively slight increase of action with the increase of
+caustic soda from 30-40�B. (2) For optimum action the temperature should
+not exceed 15-20�C. (3) The duration of action is of proportionately
+less influence as the concentration of the lye increases. As the maximum
+effect is attained the action becomes practically instantaneous, the
+only condition affecting it being that of penetration--i.e. actual
+contact of cellulose and alkali.
+
+(d) The question as to whether the process of 'mercerisation' involves
+chemical as well as physical effects is briefly discussed. The author is
+of opinion that, as the degree of lustre obtained varies with the
+different varieties of cotton, the differentiation is occasioned by
+differences in chemical constitution of these various cottons. The
+influence of the chemical factors is also emphasised by the increased
+dyeing capacity of the mercerised goods, which effect, moreover, is
+independent of those conditions of strain or tension under mercerisation
+which determine lustre. It is found in effect that with a varied range
+of dye stuffs a given shade is produced with from 10 to 30 p.ct. less
+colouring matter than is required for the ordinary, i.e. unmercerised,
+goods.
+
+In reference to the constants of strength and elasticity, Buntrock gives
+the following results of observations upon a 40^{5} twofold yarn, five
+threads of 50 cm. length being taken for each test(Prometheus, 1897, p.
+690): (a) the original yarn broke under a load of 1440 grms.; (b)
+after mercerisation without tension the load required was 2420 grms.;
+(c) after mercerisation under strain, 1950 grms. Mercerisation,
+therefore, increases the strength of the yarn from 30 to 66 p.ct., the
+increase being lessened proportionately to the strain accompanying
+mercerisation. _Elasticity_, as measured by the extension under the
+breaking load, remains about the same in yarns mercerised under strain,
+but when allowed to shrink under mercerisation there is an increase of
+30-40 p.ct. over the original.
+
+The _change of form_ sustained by the individual fibres has been studied
+by H. Lange [Farberzeitung, 1898, 197-198], whose microphotographs of
+the cotton fibres, both in length and cross-section, are reproduced. In
+general terms, the change is from the flattened riband of the original
+fibre to a cylindrical tube with much diminished and rounded central
+canal. The effect of strain under mercerisation is chiefly seen in the
+contour of the surface, which is smooth, and the obliteration at
+intervals of the canal. Hence the increased transparency and more
+complete reflection of the light from the surface, and the consequent
+approximation to the optical properties of the silk fibre.
+
+The work concludes with a section devoted to a description of the
+various practical systems of mercerisation of yarns in general practice
+in Germany, and an account of the methods adopted in dyeing the
+mercerised yarns.
+
+
+RESEARCHES ON MERCERISED COTTON.
+
+A. FRAENKEL and P. FRIEDLAENDER (Mitt. k.-k. Techn. Gew. Mus., Wien,
+1898, 326).
+
+The authors, after investigation, are inclined to attribute the lustre
+of mercerised cotton to the absence of the cuticle, which is destroyed
+and removed in the process, partly by the chemical action of the alkali,
+and partly by the stretching at one or other stage of the process. The
+authors have investigated the action of alcoholic solutions of soda
+also. The lustre effects are not obtained unless the action of water is
+associated.
+
+In conclusion, the authors give the following particulars of breaking
+strains and elasticity:--
+
+--------------------------------------------------------------------------
+Treatment                 | Experiments | Breaking strain |  Elasticity
+--------------------------------------------------------------------------
+                          |             |                 |  Elongation
+                          |             |     Grammes     |  in mm.
+                          |             |                 |
+Cotton unmercerised.      |       1     |       360       |   20
+                          |       2     |       356       |   20
+                          |       3     |       360       |   22
+                          |             |                 |
+Mercerised with           |             |                 |
+  Soda 35�B.              |       1     |       530       |   44
+                          |       2     |       570       |   40
+                          |       3     |       559       |   35
+                          |             |                 |
+  Alcoholic soda 10 p.ct. |       1     |       645       |   24
+    cold                  |       2     |       600       |   27
+                          |       3     |       610       |   33
+                          |             |                 |
+  Alcoholic soda 10 p.ct. |       5     |       740       |   33
+    hot                   |       2     |       730       |   38
+                          |       3     |       690       |   30
+--------------------------------------------------------------------------
+
+FOOTNOTES:
+
+[2] This and other similar references are to the matter of the original
+volume (1895).
+
+
+
+
+SECTION II. SYNTHETICAL DERIVATIVES--SULPHOCARBONATES AND ESTERS
+
+
+(p. 25) ~Cellulose sulphocarbonate.~--Further investigations of the
+reaction of formation as well as the various reactions of decomposition
+of the compound, have not contributed any essential modification or
+development of the subject as originally described in the author's first
+communications. A large amount of experimental matter has been
+accumulated in view of the ultimate contribution of the results to the
+general theory of colloidal solutions. But viscose is a complex product
+and essentially variable, through its pronounced tendency to progressive
+decomposition with reversion of the cellulose to its insoluble and
+uncombined condition. The solution for this reason does not lend itself
+to exact measurement of its physical constants such as might elucidate
+in some measure the progressive molecular aggregation of the cellulose
+in assuming spontaneously the solid (hydrate) form. Reserving the
+discussion of these points, therefore, we confine ourselves to recording
+results which further elucidate special points.
+
+_Normal and other celluloses._--We may certainly use the sulphocarbonate
+reaction as a means of defining a normal cellulose. As already pointed
+out, cotton cellulose passes quantitatively through the cycle of
+treatments involved in solution as sulphocarbonate and decomposition of
+the solution with regeneration as structureless or amorphous cellulose
+(hydrate).
+
+Analysis of this cellulose shows a fall of carbon percentage from 44.4
+to 43.3, corresponding with a change in composition from
+C_{6}H_{10}O_{5} to 4C_{6}H_{10}O_{5}.H_{2}O. The partial hydrolysis
+affects the whole molecule, and is limited to this effect, whereas, in
+the case of celluloses of other types, there is a fractionation of the
+mass, a portion undergoing a further hydrolysis to compounds of lower
+molecular weight and permanently soluble. Thus in the case of the wood
+celluloses the percentage recovered from solution as viscose is from 93
+to 95 p.ct. It is evident that these celluloses are not homogeneous. A
+similar conclusion results from the presence of furfural-yielding
+compounds with the observation that the hydrolysis to soluble
+derivatives mainly affects these derivatives. In the empirical
+characterisation of a normal cellulose, therefore, we may include the
+property of quantitative regeneration or recovery from its solution as
+sulphocarbonate.
+
+In the use of the word 'normal' as applied to a 'bleached' cotton, we
+have further to show in what respects the sulphocarbonate reaction
+differentiates the bleached or purified cotton cellulose from the raw
+product. The following experiments may be cited: Specimens of American
+and Egyptian cottons in the raw state, freed from mechanical, i.e.
+non-fibrous, impurities, were treated with a mercerising alkali, and the
+alkali-cotton subsequently exposed to carbon disulphide. The product of
+reaction was further treated as in the preparation of the ordinary
+solution; but in place of the usual solution, structureless and
+homogeneous, it was observed to retain a fibrous character, and the
+fibres, though enormously swollen, were not broken down by continued
+vigorous stirring. After large dilution the solutions were filtered, and
+the fibres then formed a gelatinous mass on the filters. After
+purification, the residue was dried and weighed. The American cotton
+yielded 90.0 p.ct., and the Egyptian 92.0 p.ct. of its substance in the
+form of this peculiar modification. The experiment was repeated,
+allowing an interval of 24 hours to elapse between the conversion into
+alkali-cotton and exposure of this to the carbon disulphide. The
+quantitative results were identical.
+
+There are many observations incidental to chemical treatments of cotton
+fabrics which tend to show that the bleaching process produces other
+effects than the mere removal of mechanical impurities. In the
+sulphocarbonate reaction the raw cotton, in fact, behaves exactly as a
+compound cellulose. Whether the constitutional difference between raw
+and bleached cotton, thus emphasised, is due to the group of components
+of the raw cotton, which are removed in the bleaching process, or to
+internal constitutional changes determined by the bleaching treatments,
+is a question which future investigation must decide.
+
+_The normal sulphocarbonate (viscose)._--In the industrial applications
+of viscose it is important to maintain a certain standard of composition
+as of the essential physical properties of the solution, notably
+viscosity. It may be noted first that, with the above-mentioned
+exception, the various fibrous celluloses show but slight differences in
+regard to all the essential features of the reactions involved. In the
+mercerising reaction, or alkali-cellulose stage, it is true the
+differences are considerable. With celluloses of the wood and straw
+classes there is a considerable conversion into soluble
+alkali-celluloses. If treated with water these are dissolved, and on
+weighing back the cellulose, after thorough washing, treatment with
+acid, and finally washing and drying, it will be found to have lost from
+15 to 20 p.ct. in weight. The lower grade of celluloses thus dissolved
+are only in part precipitated in acidifying the alkaline solution. On
+the other hand, after conversion into viscose, the cellulose when
+regenerated re-aggregates a large proportion of these lower grade
+celluloses, and the final loss is as stated above, from 5 to 7 p.ct.
+only.
+
+Secondly, it is found that all the conditions obtaining in the
+alkali-cellulose stage affect the subsequent viscose reaction and the
+properties of the final solution. The most important are obviously the
+proportion of alkali to cellulose and the length of time they are in
+contact before being treated with carbon disulphide. An excess of
+alkali beyond the 'normal' proportion--viz. 2NaOH per 1 mol.
+C_{6}H_{10}O_{5}--has little influence upon the viscose reaction, but
+lowers the viscosity of the solution of the sulphocarbonate prepared
+from it. But this effect equally follows from addition of alkali to the
+viscose itself. The alkali-cellulose changes with age; there is a
+gradual alteration of the molecular structure of the cellulose, of which
+the properties of the viscose when prepared are the best indication.
+There is a progressive loss of viscosity of the solution, and a
+corresponding deterioration in the structural properties of the
+cellulose when regenerated from it--especially marked in the film form.
+In regard to viscosity the following observations are typical:--
+
+     (a) A viscose of 1.8 p.ct. cellulose prepared from an
+     alkali-cellulose (cotton) fourteen days old.
+
+     (b) Viscose of 1.8 p.ct. cellulose from an alkali-cellulose
+     (cotton) three days old.
+
+     (c) Glycerin diluted with 1/3 vol. water.
+
+                                        a       b       b          c
+                                                    Diluted with
+                                                    equal vol.
+                                                      water
+Times of flow of equal volumes from    112     321     103        170
+  narrow orifice in seconds
+
+Similarly the cellulose in reverting to the solid form from these
+'degraded' solutions presents a proportionate loss of cohesion and
+aggregating power expressed by the inferior strength and elasticity of
+the products. Hence, in the practical applications of the product where
+the latter properties are of first importance, it is necessary to adopt
+normal standards, such as above indicated, and to carefully regulate all
+the conditions of treatment in each of the two main stages of reaction,
+so that a product of any desired character may be invariably obtained.
+
+Incidentally to these investigations a number of observations have been
+made on the alkali-cellulose (cotton) after prolonged storage in closed
+vessels. It is well known that starch undergoes hydrolysis in contact
+with aqueous alkalis of a similar character to that determined by acids
+[B�champ, Annalen, 100, 365]. The recent researches of Lobry de Bruyn
+[Rec. Trav. Chim. 14, 156] upon the action of alkaline hydrates in
+aqueous solution on the hexoses have established the important fact of
+the resulting mobility of the CO group, and the interchangeable
+relationships of typical aldoses and ketoses. It was, therefore, not
+improbable that profound hydrolytic changes should occur in the
+cellulose molecule when kept for prolonged periods as alkali-cellulose.
+
+We may cite an extreme case. A series of products were examined after
+12-18 months' storage. They were found to contain only 3-5 p.ct.
+'soluble carbohydrates'; these were precipitated by Fehling's solution
+but without reduction on boiling. They were, therefore, of the cellulose
+type. On acidifying with sulphuric acid and distilling, traces only of
+volatile acid were produced. It is clear, therefore, that the change of
+molecular weight of the cellulose, the disaggregation of the undoubtedly
+large molecule of the original 'normal' cellulose--which effects are
+immediately recognised in the viscose reactions of such products--are of
+such otherwise limited character that they do not affect the
+constitution of the unit groups. We should also conclude that the
+cellulose type of constitution covers a very wide range of minor
+variations of molecular weight or aggregation.
+
+The resistance of the normal cellulose to the action of alkalis under
+these hydrolysing conditions should be mentioned in conjunction with the
+observations of Lange, and the results of the later investigations of
+Tollens, on its resistance to 'fusion' with alkaline hydrates at high
+temperatures (180�). The degree of resistance has been established only
+on the empirical basis of weighing the product recovered from such
+treatment. The product must be investigated by conversion into typical
+cellulose derivatives before we can pronounce upon the constitutional
+changes which certainly occur in the process. But for the purpose of
+this discussion it is sufficient to emphasise the extraordinary
+resistance of the normal cellulose to the action of alkalis, and to
+another of the more significant points of differentiation from starch.
+
+_Chemical constants of cellulose sulphocarbonate (solution)._--In
+investigations of the solutions we make use of various analytical
+methods, which may be briefly described, noting any results bearing upon
+special points.
+
+_Total alkali._--This constant is determined by titration in the usual
+way. The cellulose ratio, C_{6}H_{10}O_{5} : 2NaOH, is within the
+ordinary error of observation, 2 : 1 by weight. A determination of alkali
+therefore determines the percentage of cellulose.
+
+_Cellulose_ may be regenerated in various ways--viz. by the action of
+heat, of acids, of various oxidising compounds. It is purified for
+weighing by boiling in neutral sulphite of soda (2 p.ct. solution) to
+remove sulphur, and in very dilute acids (0.33 p.ct. HCl) to decompose
+residues of 'organic' sulphur compounds. It may also be treated with
+dilute oxidants. After weighing it may be ignited to determine residual
+inorganic compounds.
+
+_Sulphur._--It has been proved by Lindemann and Motten [Bull. Acad. R.
+Belg. (3), 23, 827] that the sulphur of sulphocarbonates (as well as of
+sulphocyanides) is fully oxidised (to SO_{3}) by the hypochlorites
+(solutions at ordinary temperatures). The method may be adapted as
+required for any form of the products or by-products of the viscose
+reaction to be analysed for _total sulphur_.
+
+The sulphur present in the form of dithiocarbonates, including the
+typical cellulose xanthogenic acid, is approximately isolated and
+determined as CS_{2} by adding a zinc salt in excess, and distilling off
+the carbon disulphide from a water bath. From freshly prepared solutions
+a large proportion of the disulphide originally interacting with the
+alkali and cellulose is recovered, the result establishing the general
+conformity of the reaction to that typical of the alcohols. On keeping
+the solutions there is a progressive interaction of the bisulphide and
+alkali, with formation of trithiocarbonates and various sulphides. In
+decomposing these products by acid reagents hydrogen sulphide and free
+sulphur are formed, the estimation of which presents no special
+difficulties.
+
+In the spontaneous decomposition of the solution a large proportion of
+the sulphur resumes the form of the volatile disulphide. This is
+approximately measured by the loss in total sulphur in the following
+series of determinations, in which a viscose of 8.5 p.ct. strength
+(cellulose) was dried down as a thin film upon glass plates, and
+afterwards analysed:
+
+(a) Proportion of sulphur to cellulose (100 pts.) in original.
+(b) After spontaneous drying at ordinary temperature.
+(c) After drying at 40�C.
+(d) As in (c), followed, by 2 hours' heating at 98�.
+(e) As in (c), followed by 5 hours' heating at 98�.
+
+                          a     b     c     d     e
+         Total sulphur   40.0  25.0  31.0  23.7  10.4
+
+The dried product in (b) and (c) was entirely resoluble in water; in
+(d) and (e), on the other hand, the cellulose was fully regenerated,
+and obtained as a transparent film.
+
+_Iodine reaction._--Fresh solutions of the sulphocarbonate show a fairly
+constant reaction with normal iodine solution. At the first point, where
+the excess of iodine visibly persists, there is complete precipitation
+of the cellulose as the bixanthic sulphide; and this occurs when the
+proportion of iodine added reaches 3I_{2} : 4Na_{2}O, calculated to the
+total alkali.
+
+_Other decompositions._--The most interesting is the interaction which
+occurs between the cellulose xanthogenate and salts of ammonia, which is
+taken advantage of by C. H. Stearn in his patent process of spinning
+artificial threads from viscose. The insoluble product which is formed
+in excess of the solution of ammonia salt is free from soda, and
+contains 9-10 p.ct. total sulphur. The product retains its solubility in
+water for a short period. The solution may be regarded as containing the
+ammonium cellulose xanthate. This rapidly decomposes with liberation of
+ammonia and carbon disulphide, and separation of cellulose (hydrate). As
+precipitated by ammonium-chloride solution the gelatinous thread
+contains 15 p.ct. of cellulose, with a sp.gr. 1.1. The process of
+'fixing'--i.e. decomposing the xanthic residue--consists in a short
+exposure to the boiling saline solution. The further dehydration, with
+increase of gravity and cellulose content, is not considerable. The
+thread in its final air-dry state has a sp.gr. 1.48.
+
+       *       *       *       *       *
+
+~Cellulose Benzoates.~--These derivatives have been further studied by the
+authors. The conditions for the formation of the monobenzoate
+[C_{6}H_{9}O_{4}.O.CO.Ph] are very similar to those required for the
+sulphocarbonate reaction. The fibrous cellulose (cotton), treated with a
+10 p.ct. solution NaOH, and subsequently with benzoyl chloride, gives
+about 50 p.ct. of the theoretical yield of monobenzoate. Converted by 20
+p.ct. solution NaOH into alkali-cellulose, and with molecular
+proportions as below, the following yields were obtained:--
+
+                                                              Calc. for
+                                                             Monobenzoate
+(a) C_{6}H_{10}O_{5} : 2.0-2.5 NaOH : C_{6}H_{5}.COCl--       150.8}
+                                                                   }164.0
+(b) C_{6}H_{10}O_{5} : 2.0-2.5 NaOH : 1.5 mol. C_{6}H_{5}COCl 159.0}
+
+An examination of (a) showed that some dibenzoate (about 7 p.ct.) had
+been formed. The product () was exhaustively treated with cuprammonium
+solution, to which it yielded about 20 p.ct. of its weight, which was
+therefore unattacked cellulose.
+
+Under conditions as above, but with 2.5 mol. C_{6}H_{5}COCl, a careful
+comparison was made of the behaviour of the three varieties of cotton,
+which were taken in the unspun condition and previously fully bleached
+and purified.
+
+ ___________________________________________________________________
+|                                |            |          |          |
+|                                | Sea Island | Egyptian | American |
+|________________________________|____________|__________|__________|
+|                                |            |          |          |
+| Aggregate yield of benzoate    |   153      |  148     |  152     |
+| Moisture in air dry state      |     5.28   |    5.35  |    5.15  |
+| Proportion of dibenzoate p.ct. |     8.30   |   13.70  |    9.4   |
+| Yield of cellulose by          |    58.0    |   54.0   |   58.3   |
+|   saponification               |            |          |          |
+|________________________________|____________|__________|__________|
+
+It appears from these results that the benzoate reaction may proceed to
+a higher limit (dibenzoate) in the case of Egyptian cotton. This would
+necessarily imply a higher limit of 'mercerisation,' under equal
+conditions of treatment with the alkaline hydrate. It must be noted that
+in the conversion of the fibrous cellulose into these (still) fibrous
+monobenzoates, there are certain mechanical conditions imported by the
+structural features of the ultimate fibres. For the elimination of the
+influence of this factor a large number of quantitative comparisons will
+be necessary. The above results are therefore only cited as typical of a
+method of comparative investigation, more especially of the still open
+questions of the cause of the superior effects in mercerisation of
+certain cottons (see p. 23). It is quite probable that chemical as well
+as structural factors co-operate in further differentiating the cottons.
+
+Further investigation of the influence upon the benzoate reaction, of
+increase of concentration of the soda lye, used in the preliminary
+alkali cellulose reaction, from 20 to 33 p.ct. NaOH, established (1)
+that there is no corresponding increase in the benzoylation, and (2)
+that this ester reaction and the sulphocarbonate reaction are closely
+parallel, in that the degree and limit of reaction are predetermined by
+the conditions of formation of the alkali cellulose.
+
+_Monobenzoate_ prepared as above described is resistant to all solvents
+of cellulose and of the cellulose esters, and is therefore freed from
+cellulose by treatment with the former, and from the higher benzoate by
+treatment with the latter. Several of these, notably pyridine, phenol
+and nitrobenzene, cause considerable swelling and gelatinisation of the
+fibres, but without solution.
+
+_Structureless celluloses_ of the 'normal' type, and insoluble therefore
+in alkaline lye, treated under similar conditions to those described
+above for the fibrous celluloses, yield a higher proportion of
+dibenzoate. The following determinations were made with the cellulose
+(hydrate) regenerated from the sulphocarbonate:--
+
+Mol. proportions of reagents          Yield       Dibenzoate p.ct.
+C_{6}H_{10}O_{5} : 2NaOH : 2BzCl        145             34.7
+  [Caustic soda at 10 per cent. NaOH]
+
+C_{6}H_{10}O_{5} : 4NaOH : 2BzCl        162             62.7
+  [Caustic soda at 20 per cent. NaOH]
+
+_Limit of reaction._--The cellulose in this form having shown itself
+more reactive, it was taken as the basis for determining the maximum
+proportion of OH groups yielding to this later reaction. The systematic
+investigations of Skraup [Monatsh. 10, 389] have determined that as
+regards the interacting groups the molecular proportions 1 OH : 7 NaOH :
+5 BzCl, ensure complete or maximum esterification. The maximum of OH
+groups in cellulose being 4, the reagents were taken in the proportion
+C_{6}H_{10}O_{5} : 4 [7 NaOH : 5 BzCl]. The yield of crude product, after
+purifying as far as possible from the excess of benzoic acid, was 240
+p.ct. [calculated for dibenzoate 227 p.ct.]. On further investigating
+the crude product by treatment with solvents, it was found to have still
+retained benzoic acid. There was also present a proportion of only
+partially attacked cellulose (monobenzoate). The soluble benzoate
+amounted to 90 p.ct. of the product. It may be generally concluded that
+the dibenzoate represents the normal maximum but that with the hydrated
+and partly hydrolysed cellulose molecule, as obtained by regeneration
+from the sulphocarbonate, other OH groups may react, but they are only a
+fractional proportion in relation to the unit group C_{6}H_{10}O_{5}. In
+this respect again there is a close parallelism between the
+sulphocarbonate and benzoyl-ester reactions.
+
+_The dibenzoate_, even when prepared from the fibrous celluloses, is
+devoid of structure, and its presence in admixture with the fibrous
+monobenzoate is at once recognised as it constitutes a structureless
+incrustation. Under the microscope its presence in however minute
+proportion is readily observed. As stated it is soluble in certain of
+the ordinary solvents of the cellulose esters, e.g. chloroform, acetic
+acid, nitrobenzene, pyridine, and phenol. It is not soluble in ether or
+alcohol.
+
+_Hygroscopic moisture of benzoates._--The crude monobenzoate retains
+5.0-5.5 p.ct. moisture in the air-dry condition. After removal of the
+residual cellulose this is reduced to 3.3 p.ct. under ordinary
+atmospheric conditions. The purified dibenzoates retain 1.6 p.ct. under
+similar conditions.
+
+_Analysis of benzoates._--On saponification of these esters with
+alcoholic sodium hydrate, anomalous results are obtained. The acid
+numbers, determined by titration in the usual way, are 10-20 p.ct. in
+excess of the theoretical, the difference increasing with the time of
+boiling. Similarly the residual cellulose shows a deficiency of 5-9
+p.ct.
+
+It is by no means improbable that in the original ester reaction there
+is a constitutional change in the cellulose molecule causing it to break
+down in part under the hydrolysing treatment with formation of acid
+products. This point is under investigation. Normal results as regards
+acid numbers, on the other hand, are obtained by saponification with
+sodium ethylate in the cold, the product being digested with the
+half-saturated solution for 12 hours in a closed flask.
+
+The following results with specimens of mono- and dibenzoate, purified,
+as far as possible, may be cited:
+
+           Combustion results           Saponification results
+                      Calc.     C_{6}H_{5}.COOH  Calc.  Cellulose  Calc.
+Monobenzoate  C 56.60  58.65}
+              H  5.06   5.26}       46.0          45.9    58.0     60.8
+
+Dibenzoate    C 63.10  64.86}
+              H  3.40   4.86}       65.5          66.6    34.3     40.3
+
+The divergence of the numbers, especially for the dibenzoate, in the
+case of the hydrogen, and yield of cellulose on hydrolysis are
+noteworthy. They confirm the probability of the occurrence of secondary
+changes in the ester reactions.
+
+_Action of nitrating acid upon the benzoates._--From the benzoates above
+described, mixed nitro-nitric esters are obtained by the action of the
+mixture of nitric and sulphuric acids. The residual OH groups of the
+cellulose are esterified and substitution by an NO_{2} group takes place
+in the aromatic residue, giving a mixed nitric nitrobenzoic ester. The
+analysis of the products points to the entrance of 1 NO_{2} group in the
+benzoyl residue in either case; in the cellulose residue 1 OH readily
+reacts. Higher degrees of nitration are attained by the process of
+solution in concentrated nitric acid and precipitation by pouring into
+sulphuric acid. In describing these mixed esters we shall find it
+necessary to adopt the C_{12} unit formula.
+
+In analysing these products we have employed the Dumas method for _total
+nitrogen_. For the O.NO_{2} groups we have found the nitrometer and the
+Schloesing methods to give concordant results. For the NO_{2} groups it
+was thought that Limpricht's method, based upon reduction with stannous
+chloride in acid solution (HCl), would be available. The quantitative
+results, however, were only approximate, owing to the difficulty of
+confining the reduction to the NO_{2} groups of the nitrobenzoyl
+residue. By reduction with ammonium sulphide the O.NO_{2} groups were
+entirely removed as in the case of the cellulose nitrates; the NO_{2}
+was reduced to NH_{2} and there resulted a cellulose amidobenzoate,
+which was diazotised and combined with amines and phenols to form yellow
+and red colouring matters, the reacting residue remaining more or less
+firmly combined with the cellulose.
+
+_Cellulose dinitrate-dinitrobenzoate, and cellulose
+trinitrate-dinitrobenzoate._--On treating the fibrous benzoate--which is
+a dibenzoate on the C_{12} basis--with the acid mixture under the usual
+conditions, a yellowish product is obtained, with a yield of 140-142
+p.ct. The nitrobenzoate is insoluble in ether alcohol, but is soluble in
+acetone, acetic acid, and nitrobenzene. In purifying the product the
+former solvent is used to remove any cellulose nitrates. To obtain the
+maximum combination with nitroxy-groups, the product was dissolved in
+concentrated nitric acid, and the solution poured into sulphuric acid.
+
+The following analytical results were obtained (a) for the product
+obtained directly from the fibrous benzoate and purified as indicated,
+(b) for the product from the further treatment of (a) as described:
+
+                       Found                   Calc. for
+                    (a)       (b)       Dinitrate      Trinitrate
+                                     dinitrobenzoate dinitrobenzoate
+Total Nitrogen     7.84       8.97         7.99            9.24
+O.NO_{2}  "        5.00       5.45         4.00            5.54
+NO_{2} (Aromatic)  2.84       3.52         3.99            3.70
+
+With the two benzoyl groups converted into nitro-benzoyl in each
+product, the limit of the ester reaction with the cellulose residue is
+reached at the third OH group.
+
+The nitrogen in the amidobenzoate resulting from the reduction with
+ammonium sulphide was 4.5 p.ct.--as against 5.0 p.ct. calculated. The
+moisture retained by the fibrous nitrate--nitrobenzoate--in the air-dry
+state was found to be 1.97 p.ct.
+
+The product from the structureless dibenzoate or tetrabenzoate on the
+C_{12} formula, was prepared and analysed with the following results:
+
+                                              Calc. for
+                                    Mononitrate tetranitrobenzoate
+Total Nitrogen               6.76                7.25
+O.NO_{2}  "                  1.30                1.45
+NO_{2}    "  (Aromatic)      5.46                5.80
+
+The results were confirmed by the yield of product, viz. 131 p.ct. as
+against the calculated 136 p.ct. They afford further evidence of the
+generally low limit of esterification of the cellulose molecule. From
+the formation of a 'normal' tetracetate--i.e. octacetate of the C_{12}
+unit--we conclude that 4/5 of the oxygen atoms are hydroxyl oxygen. Of
+the 8 OH groups five only react in the mixed esters described above, and
+six only in the case of the simple nitric esters. The ester reactions
+are probably not simple, but accompanied by secondary reactions within
+the cellulose molecule.
+
+       *       *       *       *       *
+
+(p. 34) ~Cellulose Acetates.~--In the first edition (p. 35) we have
+committed ourselves to the statement that 'on boiling cotton with acetic
+anhydride and sodium acetate no reaction occurs.' This is erroneous. The
+error arises, however, from the somewhat vague statements of
+Schutzenberger's researches which are current in the text-books [e.g.
+Beilstein, 1 ed. p. 586] together with the statement that reaction only
+occurs at elevated temperatures (180�). As a matter of fact, reaction
+takes place at the boiling temperature of the anhydride. We have
+obtained the following results with bleached cotton:
+
+                                 Yield        Calc. for Monoacetate
+                                           C_{6}H_{7}O_{4}O.C_{2}H_{3}O
+
+Ester reaction                  121 p.ct.           125 p.ct.
+
+                 {Cellulose       79.9                79.9
+Saponification   {
+                 {Acetic acid     29.9                29.4
+
+This product is formed without apparent structural alteration of the
+fibre. It is entirely insoluble in all the ordinary solvents of the
+higher acetates. Moreover, it entirely resists the actions of the
+special solvents of cellulose--e.g. zinc chloride and cuprammonium. The
+compound is in other respects equally stable and inert. The hygroscopic
+moisture under ordinary atmospheric conditions is 3.2 p.ct.
+
+_Tetracetate._--This product is now made on the manufacturing scale: it
+has yet to establish its industrial value.
+
+
+NITRIRUNG VON KOHLENHYDRATEN.
+
+W. WILL und P. LENZE (Berl. Ber., 1898, 68).
+
+~NITRATES OF CARBOHYDRATES.~
+
+(p. 38) The authors have studied the nitric esters of a typical series
+of the now well-defined carbohydrates--pentoses, hexoses, both aldoses
+and ketoses--bioses and trioses, the nitrates being prepared under
+conditions designed to produce the highest degree of esterification.
+Starch, wood, gum, and cellulose were also included in the
+investigations. The products were analysed and their physical properties
+determined. They were more especially investigated in regard to
+temperatures of decomposition, which were found to lie considerably
+lower than that of the cellulose nitrates. They also show marked and
+variable instability at 50� C. A main purpose of the inquiry was to
+throw light upon a probable cause of the instability of the cellulose
+nitrates, viz. the presence of nitrates of hydrolysed products or
+carbohydrates of lower molecular weight.
+
+The most important results are these:
+
+_Monoses._--The _aldoses_ are fully esterified, in the pentoses 4 OH, in
+the hexoses 5 OH groups reacting. The pentose nitrates are comparatively
+stable at 50�; the hexose nitrates on the other hand are extremely
+unstable, showing a loss of weight of 30-40 p.ct. when kept 24 hours at
+this temperature.
+
+Xylose is differentiated by tending to pass into an anhydride form
+(C_{5}H_{10}O_{5}-H_{2}O) under this esterification. When treated in
+fact with the mixed acids, instead of by the process usually adopted by
+the authors of solution in nitric acid and subsequent addition of the
+sulphuric acid, it is converted into the dinitrate
+C_{5}H_{6}O_{2}.(NO_{3})_{2}.
+
+_Ketoses_ (C_{6}).--These are sharply differentiated from the corresponding
+aldoses by giving _tri_nitrates C_{6}H_{7}O_{2}(NO_{3})_{3} instead
+of _penta_nitrates, the remaining OH groups probably undergoing internal
+condensation. The products are, moreover, _extremely stable_. It is also
+noteworthy that levulose gave this same product, the trinitrate of the
+anhydride (levulosan) by both methods of nitration (_supra_).
+
+_The bisaccharides or bioses_ all give the octonitrates. The degree of
+instability is variable. Cane-sugar gives a very unstable nitrate. The
+lactose nitrate is more stable. Thus at 50� it loses only 0.7 p.ct. in
+weight in eight days; at 75� it loses 1 p.ct. in twenty-four hours, but
+with a rapid increase to 23 p.ct. in fifty-four hours. The maltose
+octonitrate melts (with decomposition) at a relatively high temperature,
+163�-164�. At 50�-75� it behaves much like the lactose nitrate.
+
+_Trisaccharide._--Raffinose yielded the product
+
+     C_{18}H_{21}O_{5}.(NO_{3})_{11}.
+
+_Starch_ yields the hexanitrate (C_{12}) by both methods of nitration.
+The product has a high melting and decomposing point, viz. 184�, and
+when thoroughly purified is quite stable. It is noted that a yield of
+157 p.ct. of this nitrate was obtained, and under identical conditions
+cellulose yielded 170 p.ct.
+
+_Wood gum_, from beech wood, gave a tetranitrate (C_{10} formula)
+insoluble in all the usual solvents for this group of esters.
+
+The authors point out in conclusion that the conditions of instability
+and decomposition of the nitrates of the monose-triose series are
+exactly those noted with the cellulose nitrates as directly prepared and
+freed from residues of the nitrating acids. They also lay stress upon
+the superior stability of the nitrates of the anhydrides, especially of
+the ketoses.
+
+
+NITRATED CARBOHYDRATES AS FOOD MATERIAL FOR MOULDS.
+
+THOMAS BOKORNY (Chem. Zeit., 1896, 20, 985-986).
+
+(p. 38) Cellulose trinitrate (nitrocellulose) will serve as a food
+supply for moulds when suspended in distilled water containing the
+requisite mineral matter and placed in the dark. The growth is rapid,
+and a considerable quantity of the vegetable growth accumulates round
+the masses of cellulose nitrate, but no growth is observed if mineral
+matter is absent. Cellulose itself cannot act as a food supply, and it
+seems probable that if glycerol is present cellulose nitrate is no
+longer made use of.
+
+
+NITRATION OF CELLULOSE, HYDROCELLULOSE, AND OXYCELLULOSE.
+
+LEO VIGNON (Compt. rend., 1898, 126, 1658-1661).
+
+(p. 38) Repeated treatment of cellulose, hydrocellulose, and
+oxycellulose with a mixture of sulphuric and nitric acids in large
+excess, together with successive analyses of the compounds produced,
+showed that the final product of the reaction corresponded, in each
+case, with the fixation of 11 NO groups by a molecule containing 24
+atoms of carbon. On exposure to air, nitrohydrocellulose becomes yellow
+and decomposes; nitro-oxycellulose is rather more stable, whilst
+nitrocellulose is unaffected. The behaviour of these nitro-derivatives
+with Schiff's reagent, Fehling's solution, and potash show that all
+three possess aldehydic characters, which are most marked in the case of
+nitro-oxycellulose. The latter also, when distilled with hydrochloric
+acid, yields a larger proportion of furfuraldehyde than is obtained from
+nitrocellulose and nitrohydrocellulose.
+
+       *       *       *       *       *
+
+~CELLULOSE NITRATES-EXPLOSIVES.~
+
+(p. 38) The uses of the cellulose nitrates as a basis for explosives are
+limited by their fibrous character. The conversion of these products
+into the structureless homogeneous solid or semi-solid form has the
+effect of controlling their combustion. The use of nitroglycerin as an
+agent for this purpose gives the curious result of the admixture of two
+high or blasting explosives to produce a new explosive capable of
+extended use for military purposes. The leading representatives of this
+class of propulsive explosives, or 'smokeless powders' are ballistite
+and cordite, the technology of which will be found fully discussed in
+special manuals of the subject. Since the contribution of these
+inventions to the development of cellulose chemistry does not go beyond
+the broad, general facts above mentioned, we must refer the reader for
+technical details to the manuals in question.
+
+There are, however, other means of arriving at structureless cellulose
+nitrates. One of these has been recently disclosed, and as the results
+involve chemical and technical points of novelty, which are dealt with
+in a scientific communication, we reproduce the paper in question,
+viz.:--
+
+
+A RE-INVESTIGATION OF THE CELLULOSE NITRATES.
+
+A. LUCK and C. F. CROSS (J. Soc. Chem. Ind., 1900).
+
+The starting-point of these investigations was a study of the nitrates
+obtained from the structureless cellulose obtained from the
+sulphocarbonate (viscose). This cellulose in the form of a fine meal was
+treated under identical conditions with a sample of pure cotton
+cellulose, viz. digested for 24 hours in an acid mixture containing in
+100 parts HNO_{3}--24 : H_{2}SO_{4}--70 : H_{2}O--6: the proportion of
+acid to cellulose being 60 : 1--. After careful purification the
+products were analysed with the following results:
+
+                                    Soluble in
+                       Nitrogen    Ether alcohol
+
+Fibrous nitrate         13.31         4.3 p.ct.
+Structureless nitrate   13.35         5.6  "
+
+Examined by the 'heat test' (at 80�) and the 'stability test' (at 135�)
+they exhibited the usual instability, and in equal degrees. Nor were the
+tests affected by exhaustive treatment with ether, benzene, and alcohol.
+From this it appears that the process of solution as sulphocarbonate and
+regeneration of the cellulose, though it eliminates certain constituents
+of an ordinary bleached cellulose, which might be expected to cause
+instability, has really no effect in this direction. It also appears
+that instability may be due to by-products of the esterification process
+derived from the cellulose itself.
+
+The investigation was then extended to liquids having a direct solvent
+action on these higher nitrates, more especially acetone. It was
+necessary, however, to avoid this solvent action proper, and having
+observed that dilution with water in increasing proportions produced a
+graduated succession of physical changes in the fibrous ester, we
+carried out a series of treatments with such diluted acetones.
+Quantities of the sample (A), purified as described, but still unstable,
+were treated each with five successive changes of the particular liquid,
+afterwards carefully freed from the acetone and dried at 40�C. The
+products, which were found to be more or less disintegrated, were then
+tested by the ordinary heat test, stability test, and explosion test,
+with the results shown in the table on next page.
+
+In this series of trials the sample 'A' was used in the condition of
+pulp, viz. as reduced by the process of wet-beating in a Hollander. A
+similar series was carried out with the guncotton in the condition in
+which it was directly obtained from the ester reaction. The results were
+similar to above, fully confirming the progressive character of the
+stabilisation with increasing proportions of acetone. These results
+prove that washing with the diluted acetone not only rendered the
+nitrate perfectly stable, but that the product was more stable than that
+obtained by the ordinary process of purification, viz. long-continued
+boiling and washing in water. We shall revert to this point after
+briefly dealing with the associated phenomenon of structural
+disintegration. This begins to be well marked when the proportion of
+acetone exceeds 80 p.ct. The optimum effect is obtained with mixtures of
+90 to 93 acetone and 10 to 7 water (by volume). In a slightly diluted
+acetone of such composition, the guncotton is instantly attacked, the
+action being quite different from the gelatinisation which precedes
+solution in the undiluted solvent. The fibrous character disappears, and
+the product assumes the form of a free, bulky, still opaque mass, which
+rapidly sinks to the bottom of the containing vessel. The disintegration
+of the bulk of the nitrate is associated with
+
+ __________________________________________________________________________
+|                   |                        |             |       |       |
+|                   |  Proportions by volume |             |       |       |
+|                   |________________________| Temperature | Heat  | Heat  |
+|                   |              |         |     of      | Test  | Test  |
+|                   |   Acetone    | Water   |  Explosion  |  80�  | 134�  |
+|___________________|______________|_________|_____________|_______|_______|
+|                   |              |         |             |       |       |
+|                 __|              |         |    Deg.     | Mins. | Mins. |
+|                   |      20      |   80    |    137      |   3   |   4   |
+|                   |      30      |   70    |    160      |   3   |   4   |
+|                   |      40      |   60    |    180      |   7   |  18   |
+|                   |              |         |             |       |   No  |
+|                   |              |         |             |       | fumes |
+|                   |              |         |             |       | after |
+| From 'A' sample.  |     50       |   50    |    187.5    |  55   |  100  |
+|                   |     60       |   40    |    187      |  45   |  100  |
+|                   |     70       |   30    |    185      |  45   |  100  |
+|                   |     80       |   20    |             |  50   |  100  |
+|                 __|     92       |    8    |    185      |  50   |  100  |
+|                   |  Structure-  |         |             |       |       |
+|                   | less powder. |         |             |       |       |
+|  "   'B' sample __|     50       |   50    |    183      |   35  |  100  |
+|  "   'C' sample   |  Ordinary service      |    185      |   10  |   41  |
+|                   |   guncotton            |             |       |       |
+|___________________|______________|_________|_____________|_______|_______|
+
+a certain solvent action, and on adding an equal bulk of water, the
+dissolved nitrate for the most part is precipitated, at the same time
+that the undissolved but disintegrated and swollen product undergoes
+further changes in the direction of increase of hardness and density.
+The product being now collected on a filter, freed from acetone by
+washing with water and dried, is a hard and dense powder the fineness of
+which varies according to the attendant conditions of treatment. With
+the main product in certain cases there is found associated a small
+proportion of nitrate retaining a fibrous character, which may be
+separated by means of a fine sieve. On examining such a residue, we
+found it to contain only 5.6 p.ct. N, and as it was insoluble in strong
+acetone, it may be regarded as a low nitrate or a mixture of such with
+unaltered cellulose. Confirming this we found that the product passing
+through the sieve showed an increase of nitrogen to 13.43 p.ct. from the
+13.31 p.ct. in the original. Tested by the heat test (50 minutes) and
+stability test (no fumes after 100 minutes), we found the products to
+have the characteristics previously noticed.
+
+It is clear, therefore, that this specifically regulated action of
+acetone produces the effects (a) of disintegration, and (b)
+stabilisation. It remains to determine whether the latter effect was
+due, as might be supposed, to the actual elimination of a compound or
+group of compounds present in the original nitrate, and to be regarded
+as the effective cause of instability. It is to be noted first that as a
+result of the treatment with the diluted acetone and further dilution
+after the specific action is completed, collecting the disintegrated
+product on a filter and washing with water, the loss of weight sustained
+amounts to 3 to 4 p.ct. This loss is due, therefore, to products
+remaining dissolved in the filtrate--that is to say, in the much diluted
+acetone. These filtrates are in fact opalescent from the presence of a
+portion of nitrate in a colloidal (hydrated) form. On distilling off the
+acetone, a precipitation is determined. The precipitates are nitrates of
+variable composition, analysis showing from 9 to 12 p.ct. of nitric
+nitrogen. The filtrate from these precipitates containing only
+fractional residues of acetone still shows opalescence. On
+long-continued boiling a further precipitation is determined, the
+filtrates from which are clear. It was in this final clear filtrate that
+the product assumed to cause the instability of the original nitrate
+would be present. The quantity, however, is relatively so small that we
+have only been able to obtain and examine it as residue from evaporation
+to dryness. An exhaustive qualitative examination established a number
+of negative characteristics, with the conclusion that the products were
+not direct derivatives of carbohydrates nor aromatic compounds. On the
+other hand the following positive points resulted. Although the original
+diluted acetone extract was neutral to test papers, yet the residue was
+acid in character. It contained combined nitric groups, fused below 200�
+giving off acid vapours, and afterwards burning with a smoky flame. On
+adding lead acetate to the original clear solution, a well-marked
+precipitation was determined. The lead compounds thus isolated are
+characteristic. They have been obtained in various ways and analysed.
+The composition varies with the character of the solution in which the
+lead compound is formed. Thus in the opalescent or milky solutions in
+which a proportion of cellulose nitrate is held in solution or
+semi-solution by the acetone still present, the lead acetate causes a
+dense coagulation. The precipitates dried and analysed showed 16-20
+p.ct. PbO and 11-9 p.ct. N. It is clear that the cellulose nitrates are
+associated in these precipitates with the lead salts of the acid
+compounds in question. When the latter are obtained from clear
+solutions, i.e. in absence of cellulose nitrates, they contain 60-63
+p.ct. PbO and 3.5 p.ct. N (obtained as NO).
+
+In further confirmation of the conclusion from these results, viz. that
+the nitrocelluloses with no tendency to combine with PbO are associated
+with acid products or by-products of the ester reaction combining with
+the oxide, the lead reagent was allowed to react in the presence of 90
+p.ct. acetone. Water was added, the disintegrated mass collected, washed
+with dilute acetic acid, and finally with water. Various estimations of
+the PbO fixed in this way have given numbers varying from 2 to 2.5 p.ct.
+Such products are perfectly stable. This particular effect of
+stabilisation appears, therefore, to depend upon the combination of
+certain acid products present in ordinary nitrocelluloses with metallic
+oxides. In order to further verify this conclusion, standard specimens
+of cellulose nitrates have been treated with a large number of metallic
+salts under varying conditions of action. It has been finally
+established (1) that the effects in question are more particularly
+determined by treatment with salts of lead and zinc, and (2) that the
+simplest method of treatment is that of boiling the cellulose nitrates
+with dilute aqueous solutions of salts of these metals, preferably the
+acetates. The following results may be cited, obtained by boiling a
+purified 'service' guncotton (sample C) with a 1 p.ct. solution of lead
+acetate and of zinc acetate respectively. After boiling 60 minutes the
+nitrates were washed free from the soluble metallic salts, dried and
+tested.
+
+ __________________________________________________
+|                          |           |           |
+|                          | Heat Test | Heat Test |
+|                          |   at 80�  |   at 134� |
+|__________________________|___________|___________|
+|                          |           |           |
+| Original sample C        |     10    |    41     |
+|Treated with lead acetate |     67    |    45     |
+|     "       zinc    "    |     91    |    45     |
+|__________________________|___________|___________|
+
+In conclusion we may briefly resume the main points arrived at in these
+investigations.
+
+_Causes of instability of cellulose nitrates._--The results of our
+experiments so far as to the causes of instability in cellulose nitrates
+may be summed up as follows:--
+
+(1) Traces of free nitrating acids, which can only occur in the finished
+products through careless manufacture, will undoubtedly cause
+instability, indicated strongly by the ordinary heat test at 80�, and to
+a less extent by the heat test at 134�.
+
+(2) Other compounds exist in more intimate association with the
+cellulose nitrates causing instability which cannot be removed by
+exhaustive washing with either hot or cold water, by digestion in cold
+dilute alkaline solutions such as sodium carbonate, or by extracting
+with ether, alcohol, benzene, &c.; these compounds, however, are soluble
+in the solvents of highly nitrated cellulose such as acetone, acetic
+ether, pyridine, &c., even when these liquids are so diluted with water
+or other non-solvent liquids to such an extent that they have little or
+no solvent action upon the cellulose nitrate itself. These solutions
+containing the bodies causing instability are neutral to test paper, but
+become acid upon evaporation by heating. (This probably explains the
+presence of free acid when guncotton is purified by long-continued
+boiling in water without any neutralising agent being present.)
+
+(3) The bodies causing instability are products or by-products of the
+original ester reaction, acid bodies containing nitroxy-groups, but
+otherwise of ill-defined characteristics. They combine with the oxides
+of zinc or lead, giving insoluble compounds. They are precipitated from
+their solutions in diluted acetone upon the addition of soluble salts of
+these metals.
+
+(4) Cellulose nitrates are rendered stable either by eliminating these
+compounds, or by combining them with the oxides of lead or zinc whilst
+still in association with cellulose nitrates.
+
+(5) Even the most perfectly purified nitrocellulose will slowly
+decompose with formation of unstable acid products by boiling for a long
+time in water. This effect is much more apparent at higher temperatures.
+
+_Dense structureless or non-fibrous cellulose nitrates_ can be
+industrially prepared (1) by nitrating the amorphous forms of cellulose
+obtained from its solution as sulphocarbonate (viscose). The cellulose
+in this condition reacts with the closest similarity to the original
+fibrous cellulose; the products are similar in composition and
+properties, including that of instability.
+
+(2) By treating the fibrous cellulose nitrates with liquid solvents of
+the high nitrate diluted with non-solvent liquids, and more especially
+water. The optimum effect is a specific disintegration or breaking down
+of their fibrous structure quite distinct from the gelatinisation which
+precedes solution in the undiluted solvent, and occurring within narrow
+limits of variation in the proportion of the diluting and non-solvent
+liquid--for industrial work the most convenient solution to employ is
+acetone diluted with about 10 p.ct. of water by volume.
+
+The industrial applications of these results are the basis of English
+patents 5286 (1898), 18,868 (1898), 18,233 (1898), Luck and Cross (this
+Journal, 1899, 400, 787).
+
+The structureless guncotton prepared as above described is of quite
+exceptional character, and entirely distinct from the ordinary fibrous
+nitrate or the nitrate prepared by precipitation from actual solution in
+an undiluted solvent.[3] By the process described, the nitrate is
+obtained at a low cost in the form of a very fine, dense, structureless,
+white powder of great purity and stability, entirely free from all
+mechanical impurities. The elimination of these mechanical impurities,
+and also to a very great extent of coloured compounds contained in the
+fibrous nitrate, makes the product also useful in the manufacture of
+celluloids, artificial silk, &c., whilst its very dense form gives it a
+great advantage over ordinary fibrous guncotton for use in shells and
+torpedoes, and for the manufacture of gelatinised gunpowders, &c. It can
+be compressed with ease into hard masses; and experiments are in
+progress with a view of producing from it, in admixture with 'retaining'
+ingredients, a military explosive manufactured by means of ordinary
+black gunpowder machinery and processes.
+
+_Manufacture of sporting powder._--The fact that the fibrous structure
+of ordinary guncotton or other cellulose nitrate can be completely or
+partially destroyed by treatment with diluted acetone and without
+attendant solution, constitutes a process of value for the manufacture
+of sporting powder having a base of cellulose nitrate of any degree of
+nitration. The following is a description of the hardening process.
+
+'Soft grains' are manufactured from ordinary guncotton or other
+cellulose nitrate either wholly or in combination with other
+ingredients, the process employed being the usual one of revolving in a
+drum in the damp state and sifting out the grains of suitable size after
+drying. These grains are then treated with diluted acetone, the degree
+of dilution being fixed according to the hardness and bulk of the
+finished grain it is desired to produce (J. Soc. Chem. Ind., 1899, 787).
+Owing to the wide limits of dilution and corresponding effect, the
+process allows of the production of either a 'bulk' or a 'condensed'
+powder.
+
+We prefer to use about five litres of the liquid to each one kilo. of
+grain operated upon, as this quantity allows of the grains being freely
+suspended in the liquid upon stirring. The grains are run into the
+liquid, which is then preferably heated to the boiling-point for a few
+minutes whilst the whole is gently stirred. Under this treatment the
+grains assume a more or less rounded gelatinous condition according to
+the strength of the liquid. There is, however, no solution of the
+guncotton and practically no tendency of the grains to cohere. Each
+grain, however, is acted upon _throughout_ and perfectly _equally_.
+After a few minutes' treatment, water is gradually added, when the
+grains rapidly harden. They are then freed from acetone and certain
+impurities by washing with water, heating, and drying. The process is of
+course carried out in a vessel provided with any means for gentle
+stirring and heating, and with an outlet for carrying off the
+volatilised solvent which is entirely recovered by condensation, the
+grains parting with the acetone with ease.
+
+_Stabilising cellulose nitrates._--The process is of especial value in
+rendering stable and inert the traces of unstable compounds which always
+remain in cellulose nitrate after the ordinary boiling and washing
+process. It is of greatest value in the manufacture of collodion cotton
+used for the preparation of gelatinous blasting explosives and all
+explosives composed of nitroglycerin and cellulose nitrates. Such
+mixtures seem peculiarly liable to decomposition if the cellulose
+nitrate is not of exceptional stability (J. Soc. Chem. Ind., 1899,
+787).
+
+
+EMPLOI DE LA CELLULOSE POUR LA FABRICATION DE FILS BRILLANTS IMITANT LA
+SOIE.
+
+E. BRONNERT (1) (Rev. Mat. Col., 1900, September, 267).
+
+V. ~USE OF CELLULOSE IN THE MANUFACTURE OF IMITATIONS OF SILK
+(LUSTRA-CELLULOSE).~
+
+(p. 45) _Introduction._--The problem of spinning a continuous thread of
+cellulose has received in later years several solutions. Mechanically
+all resolve themselves into the preparation of a structureless filtered
+solution of cellulose or a cellulose derivative, and forcing through
+capillary orifices into some medium which either absorbs or decomposes
+the solvent. The author notes here that the fineness and to a great
+extent the softness of the product depends upon the dimensions of the
+capillary orifice and concentration of the solution. The technical idea
+involved in the spinning of artificial fibres is an old one. R�aumur (2)
+forecast its possibility, Audemars of Lausanne took a patent as early as
+1855 (3) for transforming nitrocellulose into fine filaments which he
+called 'artificial silk.' The idea took practical shape only when it
+came to be used in connection with filaments for incandescent lamps. In
+this connection we may mention the names of the patentees:--Swinburne
+(4), Crookes, Weston (5), Swan (6), and Wynne and Powell (7). These
+inventors prepared the way for Chardonnet's work, which has been
+followed since 1888 with continually increasing success.
+
+At this date the lustra-celluloses known may be divided into four
+classes.
+
+1. 'Artificial silks' obtained from the nitrocelluloses.
+
+2. 'Lustra-cellulose' made from the solution of cellulose in
+cuprammonium.
+
+3. 'Lustra-cellulose' prepared from the solution of cellulose in
+chloride of zinc.
+
+4. 'Viscose silks,' by the decomposition of sulphocarbonate of cellulose
+(Cross and Bevan).
+
+GROUP 1. The early history of the Chardonnet process is discussed and
+some incidental causes of the earlier failures are dealt with. The
+process having been described in detail in so many publications the
+reader is referred to these for details. [See Bibliography, (1) and (2),
+(3) and (4).] The denitrating treatment was introduced in the period
+1888-90 and of course altogether changed the prospects of the industry;
+not only does it remove the high inflammability, but adds considerably
+to softness, lustre, and general textile quality. In Table I will be
+found some important constants for the nitrocellulose fibre; also the
+fibre after denitration and the comparative constants for natural silk.
+
+TABLE 1.
+
+ _______________________________________________________________________
+|                                          |           |                |
+|                                          | Tenacity  |   Elasticity   |
+|                                          | (grammes) | (% elongation) |
+|__________________________________________|___________|________________|
+|                                          |           |                |
+| Nitrocellulose according to Chardonnet   |           |                |
+|   German Patent No. 81,599               |    150    |       23       |
+| The same after denitration               |    110    |        8       |
+| Denitrated fibre moistened with water    |     25    |        --      |
+| Nitrocellulose: Bronnert's German Patent |           |                |
+|   No. 93,009                             |    125    |       28       |
+| The same after denitration (dry)         |    115    |       13       |
+| The same after denitration (wetted)      |     32    |       --       |
+| Natural silk                             |    300    |       18       |
+|__________________________________________|___________|________________|
+
+     1. Tenacity is the weight in grammes required to break the
+     thread.
+
+     2. Elasticity is the elongation per cent. at breaking.
+
+     The numbers are taken for thread of 100 deniers (450 metres of
+     0.05 grammes = 1 denier). It must be noted that according to
+     the concentration of the solution and variations in the process
+     of denitration the constants for the yarn are subject to very
+     considerable variation.
+
+In regard to the manufacture a number of very serious difficulties have
+been surmounted. First, instead of drying the nitrated cellulose, which
+often led to fires, &c., it was found better to take it moist from the
+centrifugal machine, in which condition it is dissolved (5). It was
+next found that with the concentrated collodion the thread could be spun
+direct into the air, and the use of water as a precipitant was thus
+avoided.
+
+With regard to denitration which is both a delicate and disagreeable
+operation: none of the agents recommended to substitute the sulphydrates
+have proved available. Of these the author mentions ferrous chloride
+(6), ferrous chloride in alcohol (7), formaldehyde (8),
+sulphocarbonates. The different sulphydrates (9) have very different
+effects. The calcium compound tends to harden and weaken the thread. The
+ammonia compound requires great care and is costly. The magnesium
+compound works rapidly and gives the strongest thread. Investigations
+have established the following point. In practice it is not necessary to
+combine the saponification of cellulose ester with complete reduction of
+the nitric acid split off. The latter requires eight molecules of
+hydrogen sulphide per one molecule tetranitrocellulose, but with
+precautions four molecules suffice. It is well known that the
+denitration is nearly complete, traces only of nitric groups surviving.
+Their reactions with diphenylamine allow a certain identification of
+artificial silks of this class. Various other inventors, e.g. Du Vivier
+(10), Cadoret (11), Lehner (12), have attempted the addition of other
+substances to modify the thread. These have all failed. Lehner, who
+persisted in his investigations, and with success, only attained this
+success, however, by leaving out all such extraneous matters. Lehner
+works with 10 p.ct. solutions; Chardonnet has continually aimed at
+higher concentration up to 20 p.ct. Lehner has been able very much to
+reduce his pressures of ejection in consequence; Chardonnet has had to
+increase up to pressures of 60 k. per cm. and higher. The latter
+involves very costly distributing apparatus. Lehner made next
+considerable advance by the discovery of the fact that the addition of
+sulphuric acid to the collodion caused increase of fluidity (13), which
+Lehner attributes to molecular change. Chardonnet found similar results
+from the addition of aldehyde and other reagents (14), but not such as
+to be employed for the more concentrated collodions. The author next
+refers to his discoveries (15) that alcoholic solutions of a number of
+substances, organic and inorganic, freely dissolve the lower cellulose
+nitrates. The most satisfactory of these substances is chloride of
+calcium (16). It is noted that acetate of ammonia causes rapid changes
+in the solution, which appear to be due to a species of hydrolysis. The
+result is sufficiently remarkable to call for further investigation. The
+chloride of calcium, it is thought possible, produces a direct
+combination of the alcohol with a reactive group of the nitrocellulose.
+The fluidity of this solution using one mol. CaCl_{2} per 1 mol.
+tetranitrate (17) reaches a maximum in half an hour's heating at
+60�-70�C. The fluidity is increased by starting from a cotton which has
+been previously mercerised. After nitration there is no objection to a
+chlorine bleach. Chardonnet has found on the other hand that in
+bleaching before nitration there is a loss of spinning quality in the
+collodion. The author considers that the new collodion can be used
+entirely in place of the ordinary ether-alcohol collodion. With regard
+to the properties of the denitrated products they fix all basic colours
+without mordant and may be regarded as oxycellulose therefore. The
+density of the thread is from 1.5 to 1.55. The thread of 100 deniers
+shows a mean breaking strain of 120 grammes with an elasticity of 8-12
+p.ct. The cardinal defect of these fibres is their property of
+combination with water. Many attempts have been made to confer
+water-resistance (18), but without success. Strehlenert has proposed the
+addition of formaldehyde (19), but this is without result (20). In
+reference to these effects of hydration, the author has made
+observations on cotton thread, of which the following table represents
+the numerical results:
+
+                                                       Breaking Strain
+                                                   Mean of 20 experiments
+
+Skein of bleached cotton without treatment                 825
+Skein of bleached cotton without treatment, but wetted     942
+Ditto after conversion into hexanitrate, dry               884
+The above, wetted                                          828
+The cotton denitrated from above, dry                      529
+The cotton denitrated as above and wetted                  206
+
+The author considers that other patents which have been taken for
+spinning nitrocellulose are of little practical account (21) and (22).
+The same conclusion also applies to the process of _Langhans_, who
+proposes to spin solutions of cellulose in sulphuric acid (23) (24) and
+mixtures of sulphuric acid and phosphoric acid.
+
+GROUP 2. _Lustra-cellulose._--Thread prepared by spinning solutions of
+cellulose in cuprammonium.
+
+This product is made by the Vereinigte Glanzstoff-Fabriken, Aachen,
+according to a series of patents under the names of H. Pauly, M. Fremery
+and Urban, Consortium mulhousien pour la fabrication de fils brillants,
+E. Bronnert, and E. Bronnert and Fremery and Urban (1). The first patent
+in this direction was taken by Despeissis in 1890 (2). It appears this
+inventor died shortly after taking the patent (3) The matter was later
+developed by Pauly (4) especially in overcoming the difficulty of
+preparing a solution of sufficient concentration. (It is to be noted
+that Pauly's patents rest upon a very slender foundation, being
+anticipated in every essential detail by the previous patent of
+Despeissis.) For this very great care is required, especially, first,
+the condition of low temperature, and, secondly, a regulated proportion
+of copper and ammonia to cellulose. The solution takes place more
+rapidly if the cellulose has been previously oxidised. Such cellulose
+gives an 8 p.ct. solution, and the thread obtained has the character of
+an oxycellulose, specially seen in its dyeing properties. The best
+results are obtained, it appears, by the preliminary mercerising
+treatment and placing the alkali cellulose in contact with copper and
+ammonia. (All reagents employed in molecular proportions.) The author
+notes that the so-called hydrocellulose (Girard) (5) is almost insoluble
+in cuprammonium, as is starch. It is rendered soluble by alkali
+treatment.
+
+GROUP 3. _Lustra-cellulose_ prepared by spinning a solution of cellulose
+in concentrated chloride of zinc.
+
+This solution has been known for a long time and used for making
+filaments for incandescent lamps. The cellulose threads, however, have
+very little tenacity. This is no doubt due to the conditions necessary
+for forming the solution, the prolonged digestion causing powerful
+hydrolysis (1). Neither the process of Wynne and Powell (2) nor that of
+Dreaper and Tompkins (3), who have endeavoured to bring the matter to a
+practical issue, are calculated to produce a thread taking a place as a
+textile. The author has described in his American patent (4) a method of
+effecting the solution in the cold, viz. again by first mercerising the
+cellulose and washing away the caustic soda. This product dissolves in
+the cold and the solution remains unaltered if kept at low temperature.
+Experiments are being continued with these modifications of the process,
+and the author anticipates successful results. The modifications having
+the effect of maintaining the high molecular weight of the cellulose, it
+would appear that these investigations confirm the theory of Cross and
+Bevan that the tenacity of a film or thread of structureless regenerated
+cellulose is directly proportional to the molecular weight of the
+cellulose, i.e. to its degree of molecular aggregation (5).
+
+GROUP 4. 'Viscose' silks obtained by spinning solutions of xanthate of
+cellulose.
+
+In 1892, Cross and Bevan patented the preparation of a new and curious
+compound of cellulose, the thiocarbonate (1) (2) (3). Great hopes were
+based upon this product at the time of its discovery. It was expected
+to yield a considerable industrial and financial profit and also to
+contribute to the scientific study of cellulose. The later patents of C.
+H. Stearn (4) describe the application of viscose to the spinning of
+artificial silk. The viscose is projected into solutions of chloride of
+ammonium and washed in a succession of saline solutions to remove the
+residual sulphur impurities. The author remarks that though it has a
+certain interest to have succeeded in making a thread from this compound
+and thus adding another to the processes existing for this purpose, he
+is not of opinion that it shows any advance on the lustra-cellulose (2)
+and (3). He also considers that the bisulphide of carbon, which must be
+regarded as a noxious compound, is a serious bar to the industrial use
+of the process, and for economic work he considers that the regeneration
+of ammonia from the precipitating liquors is necessary and would be as
+objectionable as the denitration baths in the collodion process. The
+final product not being on the market he does not pronounce a finally
+unfavourable opinion.
+
+The author and the Vereinigte Glanzstoff-Fabriken after long
+investigation have decided to make nothing but the lustra-cellulose (2)
+and (3). A new factory at Niedermorschweiler, near Mulhouse, is
+projected for this last production.
+
+
+BIBLIOGRAPHY
+
+_Introduction_
+
+(1) Bull. de la Soc. industr. de Mulhouse, 1900.
+
+(2) R�aumur, M�moire pour servir � l'histoire des insectes, 1874, 1, p.
+154.
+
+(3) English Pat. No. 283, Feb. 6, 1855.
+
+(4) Swinburne, Electrician, 18, 28, 1887, p. 256.
+
+(5) Weston (Swinburne), Electrician, 18, 1887, p. 287. Eng. Pat. No.
+22866, Sept. 12, 1882.
+
+(6) German Pat. No. 3029. English Pat. No. 161780, April 28, 1884
+(Swan).
+
+(7) Wynne-Powell, English Pat. No. 16805, Dec. 22, 1884.
+
+
+_Group I_
+
+(1) German Pat No. 38368, Dec. 20, 1885. German Pat. No. 46125, March 4,
+1888. German Pat. No. 56331, Feb. 6, 1890. German Pat. No. 81599, Oct.
+11, 1893. German Pat. No. 56655, April 23, 1890. French Pat. No. 231230,
+June 30, 1893.
+
+(2) Industrie textile, 1899, 1892. Wyss-Noef, Zeitschrift f�r angewandte
+Chemie, 1899, 30, 33. La Nature, Jan. 1, 1898, No. 1283. Revue g�n�rale
+des sciences, June 30, 1898.
+
+(3) German Pat. No. 46125, March 4, 1888. German Pat. No. 56655, April
+23, 1890.
+
+(4) Swan, English Pat. 161780, June 28, 1884. See also B�champ, Dict. de
+Chimie de Wurtz.
+
+(5) German Pat. No. 81599, Oct 11, 1893.
+
+(6) B�champ, art. Cellulose, Dict. de Chimie de Wurtz, p. 781.
+
+(7) Chardonnet, addit. March 3, 1897, to the French Pat. 231230, May 30,
+1893.
+
+(8) Knofler, French Pat. 247855, June 1, 1895. German Pat. 88556, March
+28, 1894.
+
+(9) B�champ, art. Cellulose, Dict. de Chimie de Wurtz. Blondeau, Ann.
+Chim. et Phys. (3), 1863, 68, p. 462.
+
+(10) Revue industrielle, 1890, p. 194. German Pat. 52977, March 7, 1889.
+
+(11) French Pat. 256854, June 2, 1896.
+
+(12) German Pat. 55949, Nov. 9, 1889. German Pat. 58508, Sept. 16, 1890.
+German Pat. 82555, Nov. 15, 1894.
+
+(13) German Pat. 58508, Sept. 16, 1900.
+
+(14) French Pat. 231230, June 30, 1893.
+
+(15) German Pat. 93009, Nov. 19, 1895. French Pat. 254703, March 12,
+1896. English Pat. 6858, March 28, 1896.
+
+(16) American Pat. 573132, Dec. 15, 1896.
+
+(17) This proportion is the most advantageous, and furnishes the best
+liquid collodions that can be spun.
+
+(18) French Pat. 259422, Sept. 3, 1896.
+
+(19) English Pat. 22540, 1896.
+
+(20) Application for German Pat. not granted, 4933 IV. 296, Mar. 16,
+1897.
+
+(21) German Pat. 96208, Feb. 10, 1897. Addit. Pat. 101844 and 102573,
+Dec. 10, 1897.
+
+(22) Oberle et Newbold, French Pat. 25828, July 22, 1896. Granquist,
+Engl. applic. 2379, Nov. 28, 1899.
+
+(23) German Pat. 72572, June 17, 1891.
+
+(24) Voy. Stern, Ber., 28, ch. 462.
+
+
+_Group II_
+
+(1) German Pat. 98642, Dec. 1, 1897 (Pauly). French Pat. 286692, March
+10, 1899, and addition of October 14, 1899 (Fremery and Urban). French
+Pat. 286726, March 11, 1899, and addition of December 4, 1899. German
+Pat. 111313, March 16, 1899 (Fremery and Urban). English Pat. 18884,
+Sept. 19, 1899 (Bronnert). English Pat. 13331, June 27, 1899 (Consort.
+mulhousien).
+
+(2) French Pat. 203741, Feb. 12, 1890.
+
+(3) The actual lapse of this patent is due to the death of Despeissis
+shortly after it was taken.
+
+(4) Without questioning the good faith of Pauly, it is nevertheless a
+fact that the original patent remains as a document, and therefore that
+the value of the Pauly patents is very questionable.
+
+(5) Girard, Ann. Chim. et Phys, 1881 (5), 24, p. 337-384.
+
+
+_Group III_
+
+(1) Cross and Bevan, Cellulose, 1895, p. 8.
+
+(2) English Pat. 16805, Dec. 22, 1884.
+
+(3) English Pat. 17901, July 30, 1897.
+
+(4) Bronnert, American Pat. 646799, April 3, 1900.
+
+(5) Cross and Bevan, Cellulose, 1895, p. 12.
+
+
+_Group IV_
+
+(1) English Pat. 8700, 1892. German Pat. 70999, Jan. 13, 1893.
+
+(2) English Pat. 4713, 1896. German Pat. 92590, Nov. 21, 1896.
+
+(3) Comptes rendus (loc. cit.). Berichte, c. 9, 65a.
+
+(4) English Pat. 1020, 1898. German Pat. 108511, Oct. 18, 1898.
+
+
+~Artificial Silk--Lustra-cellulose.~
+
+C. F. CROSS and E. J. BEVAN (J. Soc. Chem. Ind., 1896, 317).
+
+The object of this paper is mainly to correct current statements as to
+the artificial or 'cellulose silks' being explosive or highly
+inflammable (ibid., 1895, 720). A specimen of the 'Lehner' silk was
+found to retain only 0.19 p.ct. total nitrogen, showing that the
+denitration is sufficiently complete to dispose of any suggestion of
+high inflammability.
+
+The product yielded traces only of furfural; on boiling with a 1 p.ct.
+solution of sodium hydrate, the loss of weight was 9.14 p.ct.; but the
+solution had no reducing action on Fehling's solution. The product in
+denitration had therefore reverted completely to a cellulose (hydrate),
+no oxy-derivative being present.
+
+       *       *       *       *       *
+
+The authors enter a protest against the term 'artificial silk' as
+applied to these products, and suggest 'lustra-cellulose.'
+
+
+DIE K�NSTLICHE SEIDE-IHRE HERSTELLUNG, EIGENSCHAFTEN UND VERWENDUNG.
+
+CARL S�VERN, Berlin, 1900, J. Springer.
+
+~ARTIFICIAL SILK--ITS PRODUCTION, PROPERTIES, AND APPLICATIONS.~
+
+This work of some 130 pages is an important monograph on the subject of
+the preparation of artificial cellulose threads--so far as the technical
+elements of the problems involved are discussed and disclosed in the
+patent literature. The first section, in fact, consists almost
+exclusively of the several patent specifications in chronological order
+and ranged under the sub-sections: (a) The Spinning of Nitrocellulose
+(collodion); (b) The Spinning of other Solutions of Cellulose; (c)
+The Spinning of Solutions of the Nitrogenous Colloids.
+
+In the second section the author deals with the physical and chemical
+proportions of the artificial threads.
+
+_Chardonnet 'silk'_ is stated to have a mean diameter of 35�, but with
+considerable variations from the mean in the individual fibres; equally
+wide variations in form are observed in cross-section. The general form
+is elliptical, but the surface is marked by deep stri�, and the
+cross-section is therefore of irregular outline. This is due to
+irregular conditions of evaporation of the solvents, the thread being
+'spun' into the air from cylindrical orifices of regulated dimensions.
+Chardonnet states that when the collodion is spun into alcohol the
+resultant thread is a perfect cylinder (Compt. rend. 1889, 108, 962).
+The strength of the fibre is variously stated at from 50-80 p.ct. that
+of 'boiled off' China tram; the true elasticity is 4-5 p.ct., the
+elongation under the breaking strain 15-17 p.ct. The sp.gr. is 1.49,
+i.e. 3-5 p.ct. in excess of boiled off silk.
+
+_Lehner 'silk'_ exhibits the closest similarity to the Chardonnet
+product. In cross-section it is seen to be more regular in outline, and
+a round, pseudo-tubular form prevails, due to the conditions of
+shrinkage and collapse of the fibre in parting with the solvents, and in
+then dehydrating. The constants for 'breaking strain,' both in the
+original and moistened condition, for elasticity, &c., are closely
+approximate to those for the Chardonnet product.
+
+_Pauly 'silk'._--The form of the ultimate fibres is much more regular
+and the contour of the cross-section is smooth. The product shows more
+resistance to moisture and to alkaline solutions.
+
+_Viscose 'silk'_ is referred to in terms of a communication appearing in
+'Papier-Zeitung,' 1898, 2416.
+
+     In the above section the following publications are referred
+     to: Chardonnet, 'Compt. rend.,' 1887, 105, 900; and 1889, 108,
+     962; Silbermann, 'Die Seide,' 1897, v. 2, 143; Herzog,
+     'Farber-Zeitung,' 1894/5, 49-50; Thiele, ibid. 1897, 133; O.
+     Schlesinger, 'Papier-Zeitung,' 1895, 1578-81, 1610-12.
+
+
+_Action of Reagents upon Natural and Artificial Silks._
+
+1. _Potassium hydrate_ in solution of maximum concentration dissolves
+the silks proper, (a) China silk on slight warming, (b) Tussah silk
+on boiling. The cellulose 'silks' show swelling with discolouration, but
+the fibrous character is not destroyed even on boiling.
+
+2. _Potassium hydrate_ 40 p.ct. China silk dissolves completely at
+65�-85�; Tussah silk swells considerably at 75� and dissolves at
+100�-120�. The cellulose 'silks' are attacked with discolouration; at
+140� (boiling-point of the solution) there is progressive solvent
+action, but the action is incomplete. The Pauly product is most
+resistant.
+
+3. _Zinc chloride_, 40 p.ct. solution. Both the natural silks and
+lustra-celluloses are attacked at 100�, and on raising the temperature
+the further actions are as follows: China silk is completely dissolved
+at 110-120�; Tussah silk at 130-135�; the collodion products at
+140-145�; the Pauly product was again most resistant, dissolving at
+180�.
+
+4. _Alkaline cupric oxide_ (glycerin) solution was prepared by
+dissolving 10 grs. of the sulphate in 100 c.c. water, adding 5 grs.
+glycerin and 10 c.c. of 40 p.ct. KOH. In this solution the China silk
+dissolved at the ordinary temperature; Tussah silk and the
+lustra-celluloses were not appreciably affected.
+
+5. _Cuprammonium solution_ was prepared by dissolving the precipitated
+cupric hydrate in 24 p.ct. ammonia. In this reagent also the China silk
+dissolved, and the Tussah silk as well as the lustra-celluloses
+underwent no appreciable change.
+
+6. _An ammoniacal solution of nickel oxide_ was prepared by dissolving
+the precipitated hydrated oxide in concentrated ammonia. The China silk
+was dissolved by this reagent; Tussah silk and the lustra-celluloses
+entirely resisted its action.
+
+7. _Fehling's solution_ is a solvent of the natural silks, but is
+without action on the lustra-celluloses.
+
+8. _Chromic acid_--20 p.ct. CrO_{3}--solution dissolves both the natural
+silks and the lustra-celluloses at the boiling temperature of the
+solution.
+
+9. _Millon's reagent_, at the boiling solution, colours the natural
+silks violet: the lustra-celluloses give no reaction.
+
+10. _Concentrated nitric acid_ attacks the natural silks powerfully in
+the cold; the lustra-celluloses dissolve on heating.
+
+11. _Iodine solution_ (I in KI) colours the China silk a deep brown,
+Tussah a pale brown; the celluloses from collodion are coloured at first
+brown, then blue. The Pauly product, on the other hand, does not react.
+
+12. _Diphenylamine sulphate._--A solution of the base in concentrated
+sulphuric acid colours the natural silks a brown; the collodion 'silks'
+give a strong blue reaction due to the presence of residual
+nitro-groups. The Pauly product is not affected.
+
+13. _Brucin sulphate_ in presence of concentrated sulphuric acid colours
+the natural silks only slightly (brown); the collodion 'silks' give a
+strong red colouration. The Pauly product again is without reaction.
+
+14. _Water._--The natural silks do not soften in the mouth as do the
+lustra-celluloses.
+
+15. _Water of condition_ was determined by drying at 100�; the following
+percentages resulted (a). The percentages of water (b) taken up from
+the atmosphere after forty-three hours' exposure were:
+
+                                   (a)        (b)
+     China (raw) silk             7.97       2.24
+     Tussah silk                  8.26       5.00
+
+     Lustra-celluloses:
+
+     Chardonnet (Besan�on)       10.37       5.64
+         "    Spreitenbach       11.17       5.77
+     Lehner                      10.71       5.97
+     Pauly                       10.04       6.94
+
+16. _Behaviour on heating at 200�._--After two hours' heating at this
+temperature the following changes were noted:
+
+     China silk      Much discoloured (brown).
+     Tussah silk     Scarcely affected.
+
+Lustra-celluloses:
+
+     Chardonnet   Converted into a blue-black charcoal, retaining the
+     Lehner       form ofthe fibres.
+
+     Pauly       A bright yellow-brown colouration, without carbonisation.
+
+17. The _losses of weight_ accompanying these changes and calculated per
+100 parts of fibre dried at 100� were:
+
+     China silk       3.18
+     Tussah silk      2.95
+
+Lustra-celluloses:
+
+     Chardonnet      33.70
+     Lehner          26.56
+     Pauly            1.61
+
+18. _Inorganic constituents._--Determinations of the total ash gave for
+the first five of the above, numbers varying from 1.0 to 1.7 p.ct. The
+only noteworthy point in the comparison was the exceptionally small ash
+of the Pauly product, viz. 0.096 p.ct.
+
+19. _Total nitrogen._--The natural silks contain the 16-17 p.ct. N
+characteristic of the proteids. The lustra-celluloses contain 0.05-0.15
+p.ct. N which in those spun from collodion is present in the form of
+nitric groups.
+
+The points of chemical differentiation which are established by the
+above scheme of comparative investigation are summed up in tabular form.
+
+_Methods of dyeing._--The lustra-celluloses are briefly discussed. The
+specific relationship of these forms of cellulose to the colouring
+matters are in the main those of cotton, but they manifest in the
+dye-bath the somewhat intensified attraction which characterises
+mercerised cotton, or more generally the cellulose hydrates.
+
+_Industrial applications_ of the lustra-celluloses are briefly noticed
+in the concluding section of the book.
+
+FOOTNOTES:
+
+[3] With these products it is easy to observe that they have a definite
+fusion point 5�-10� below the temperature of explosion.
+
+
+
+
+SECTION III. DECOMPOSITIONS OF CELLULOSE SUCH AS THROW LIGHT ON THE
+PROBLEM OF ITS CONSTITUTION
+
+
+UEBER CELLULOSE.
+
+G. BUMCKE und R. WOLFFENSTEIN (Berl. Ber., 1899, 2493).
+
+(p. 54) _Theoretical Preface._--The purpose of these investigations is
+the closer characterisation of the products known as 'oxycellulose' and
+'hydracellulose,' which are empirical aggregates obtained by various
+processes of oxidation and hydrolysis; these processes act concurrently
+in the production of the oxycelluloses. The action of hydrogen peroxide
+was specially investigated. An oxycellulose resulted possessing strongly
+marked aldehydic characteristics. The authors commit themselves to an
+explanation of this paradoxical result, i.e. the production of a body
+of strongly 'reducing' properties by the action of an oxidising agent
+upon the inert cellulose molecule (? aggregate) as due to the
+_hydrolytic_ action of the peroxide: following Wurster (Ber. 22, 145),
+who similarly explained the production of reducing sugars from cane
+sugar by the action of the peroxide.
+
+The product in question is accordingly termed _hydralcellulose_. By the
+action of alkalis this is resolved into two bodies of alcoholic
+(cellulose) and acid ('acid cellulose') characteristics respectively.
+The latter in drying passes into a lactone. The acid product is also
+obtained from cellulose by the action of alkaline lye (boiling 30 p.ct.
+NaOH) and by solution in Schweizer's reagent.
+
+It is considered probable that the cellulose nitrates are hydrocellulose
+derivatives, and experimental evidence in favour of this conclusion is
+supplied by the results of 'nitrating' the celluloses and their oxy- and
+hydro- derivatives. Identical products were obtained.
+
+_Experimental investigations._--The filter paper employed as 'original
+cellulose,' giving the following numbers on analysis:
+
+     C   44.56    44.29    44.53    44.56
+     H    6.39     6.31     6.46     6.42
+
+was exposed to the action of pure distilled H_{2}O_{2} at 4-60 p.ct.
+strength, at ordinary temperatures until disintegrated: a result
+requiring from nineteen to thirty days. The series of products gave the
+following analytical results:
+
+     C   43.61   43.61   43.46   43.89   44.0   43.87   43.92   43.81
+     H    6.00    6.29    6.28    6.26    6.13   6.27    6.24    6.27
+
+results lying between the requirements of the formul�:
+
+     5 C_{6}H_{10}O_{5}.H_{2}O  and  8 C_{6}H_{10}O_{5}.H_{2}O.
+
+Hydrazones were obtained with 1.7-1.8 p.ct. N. Treated with caustic soda
+solution the hydrazones were dissolved in part: on reprecipitation a
+hydrazone of unaltered composition was obtained. The original product
+shows therefore a uniform distribution of the reactive CO- groups.
+
+The hydralcellulose boiled with Fehling's solution reduced 1/12 of the
+amount required for an equal weight of glucose.
+
+Digested with caustic soda solution it yielded 33 p.ct. of its weight of
+the soluble 'acid cellulose.' This product was purified and analysed
+with the following result: C 43.35 H 6.5. For the direct production of
+the 'acid' derivative, cellulose was boiled with successive quantities
+of 30 p.ct. NaOH until _dissolved_. It required eight treatments of one
+hour's duration. On adding sulphuric acid to the solutions the product
+was precipitated. Yield 40 p.ct. Analyses:
+
+     C    43.8     43.8     43.7
+     H     6.2      6.2      6.3
+
+The cellulose reprecipitated from solution in Schweizer's reagent gave
+similar analytical results:
+
+     C    43.9    43.8    44.0
+     H     6.5     6.3     6.4
+
+_Conversion into nitrates._--The original cellulose, hydral- and acid
+cellulose were each treated with 10 times their weight of HNO_{3} of
+1.48 sp.gr. and heated at 85� until the solution lost its initial
+viscosity.
+
+The products were precipitated by water and purified by solution in
+acetone from which two fractions were recovered, the one being
+relatively insoluble in ethyl alcohol. The various nitrates from the
+several original products proved to be of almost identical composition,
+
+     C 32.0   H 4.2    N 8.8
+
+with a molecular weight approximately 1350. The conclusion is that
+these products are all derivatives of a 'hydralcellulose'
+6C_{6}H_{10}O_{5}H_{2}O.
+
+
+FORMATION OF FURFURALDEHYDE FROM CELLULOSE, OXYCELLULOSE, AND
+HYDROCELLULOSE.
+
+By LEO VIGNON (Compt. rend., 1898, 126, 1355-1358).
+
+(p. 54) Hydrocellulose, oxycellulose, and 'reduced' cellulose, the last
+named being apparently identical with hydrocellulose, were obtained by
+heating carefully purified cotton wool (10 grams) in water (1,000 c.c.),
+with (1) 65 c.c. of hydrochloric acid (1.2 sp.gr.), (2) 65 c.c. of
+hydrochloric acid and 80 grams of potassium chlorate, (3) 65 c.c. of
+hydrochloric acid and 50 grams of stannous chloride. From these and some
+other substances, the following percentage yields of furfuraldehyde were
+obtained: Hydrocellulose, 0.854; oxycellulose, 2.113; reduced cellulose,
+0.860; starch, 0.800; bleached cotton, 1.800; oxycellulose, prepared by
+means of chromic acid, 3.500. Two specimens of oxycellulose were
+prepared by treating cotton wool with hydrochloric acid and potassium
+chlorate (A), and with sulphuric acid and potassium dichromate (B), and
+25 grams of each product digested with aqueous potash. Of the product A,
+16.20 grams were insoluble in potash, 2.45 grams were precipitated on
+neutralisation of the alkaline solution, and 6.35 grams remained in
+solution, whilst B yielded 11.16 grams of insoluble matter, 1.42 grams
+were precipitated by acid, and 12.42 grams remained in solution. The
+percentage yields of furfuraldehyde obtained from these fractions were
+as follows: A, insoluble, 0.86; precipitated, 4.35; dissolved, 1.10. B,
+insoluble, 0.76; precipitated, 5.11; dissolved, 1.54. It appears, from
+the foregoing results, that the cellulose molecule, after oxidation, is
+easily decomposed by potash, the insoluble and larger portion having all
+the characters of the original cellulose, whilst the soluble portion is
+of an aldehydic nature, and contains a substance, precipitable by acids,
+which yields a relatively large amount of furfuraldehyde.
+
+
+UNTERSUCHUNGEN �BER DIE OXYCELLULOSE.
+
+O. V. FABER und B. TOLLENS (Berl. Ber., 1899, 2589).
+
+~Investigations of Oxycellulose.~
+
+(p. 61) The author's results are tersely summed up in the following
+conclusions set forth at the end of the paper: The oxycelluloses are
+mixtures of cellulose and a derivative oxidised compound which contains
+one more atom O than cellulose (cellulose = C_{6}H_{10}O_{5}), and for
+which the special designation _Celloxin_ is proposed.
+
+Celloxin may be formulated C_{8}H_{6}O_{6} or C_{6}H_{10}O_{6}, of which
+the former is the more probable.
+
+The various oxycelluloses may be regarded as containing one celloxin
+group to 1-4 cellulose groups, according to the nature of the original
+cellulose, and the degree of oxidation to which subjected. These groups
+are in chemical union.
+
+Celloxin has not been isolated. On boiling the oxycelluloses with
+lime-milk it is converted into isosaccharinic and dioxybutyric acids.
+The insoluble residue from the treatment is cellulose.
+
+The following oxycelluloses were investigated:
+
+A. _Product of action of nitric acid upon pine wood_ (Lindsey and
+Tollens, Ann. 267, 366).--The oxycelluloses contained
+
+1 mol celloxin:  {2 mol. cellulose on 6 hours' heating
+                 {3 mol. cellulose on 3 hours' heating
+
+with a ratio H : O = 1 : 9 and 1 : 8.7 respectively: they yielded 7
+p.ct. furfural.
+
+B. _By action of bromine in presence of water and_ CaCO_{3} _upon
+cotton_.--Yield, (air-dry) 85 p.ct. Empirical composition
+C_{12}H_{20}O_{11} = C_{6}H_{10}O_{5}.C_{6}H_{10}O_{6}: yielded furfural
+1.7 p.ct.
+
+C. _Cotton and nitric acid at_ 100�, two and a half hours (Cross and
+Bevan).--Yield, 70 p.ct. Composition
+
+     4 C_{6}H_{10}O_{5}.C_{6}H_{8}O_{6}
+
+yielded furfural 2.3 p.ct.
+
+D. _Cotton and nitric acid at_ 100� (four hours).--A more highly
+oxidised product resulted, viz. 3 C_{6}H_{10}O_{5}.C_{6}H_{8}O_{6}:
+yielded furfural 3.2 p.ct.
+
+_By-products of oxidation._--The liquors from B were found to contain
+saccharic acid: the acid from C and B contained a dibasic acid which
+appeared to be tartaric acid.
+
+The isolation of (1) isosaccharinic and (2) dioxybutyric acid from the
+products of digestion of the oxycelluloses with lime-milk at 100� was
+effected by the separation of their respective calcium salts, (1) by
+direct crystallisation, (2) by precipitation alcohol after separation of
+the former.
+
+
+CELLULOSES, HYDRO- AND OXYCELLULOSES, AND CELLULOSE ESTERS.
+
+L. VIGNON (Bull. Soc. Chim., 1901 [3], 25, 130).
+
+(a) _Oxycelluloses from cotton, hemp, flax, and ramie._--The
+comparative oxidation of these celluloses, by treatment with HClO_{3}
+at 100�, gave remarkably uniform results, as shown by the following
+numbers, showing extreme variations: yields, 68-70 p.ct.; hydrazine
+reaction, N fixed 1.58-1.69; fixation of basic colouring matters
+(relative numbers), saffranine, 100-200, methylene blue, 100-106. The
+only points of difference noted were (1) hemp is somewhat more resistant
+to the acid oxidation; (2) the cotton oxycellulose shows a somewhat
+higher (25 p.ct.) cupric reduction.
+
+(b) _'Saccharification' of cellulose, cellulose hydrates, and
+hydrocellulose._--The products were digested with dilute hydrochloric
+acid six hours at 100�, and the cupric reduction of the soluble products
+determined and calculated to dextrose.
+
+  100 grms. of                   gave reducing products equal to Dextrose
+
+Purified cotton                                                      3.29
+  "      Hydrocellulose                                              9.70
+Cotton mercerised (NaOH 30� B.)                                      4.39
+Cotton mercerised (NaOH 40� B.)                                      3.51
+Cellulose reprecipitated from cuprammonium                           4.39
+Oxycellulose                                                        14.70
+Starch                                                              98.6
+
+These numbers show that cellulose may be hydrated both by mercerisation
+and solution, without affecting the constitutional relationships of the
+CO groups. The results also differentiate the cellulose series from
+starch in regard to hydrolysis.
+
+(c) _Cellulose and oxycellulose nitrates._--The nitric esters of
+cellulose have a strong reducting action on alkaline copper solutions.
+The author has studied this reaction quantitatively for the esters both
+of cellulose and oxycellulose, at two stages of 'nitration,' represented
+by 8.2-8.6 p.ct. and 13.5-13.9 p.ct. total nitrogen in the
+ester-products, respectively. The results are expressed in terms (c.c.)
+of the cupric reagent (Pasteur) reduced per 100 grs. compared with
+dextrose (=17767).
+
+    Cellulose maximum nitration (13.5 p.ct. N)             3640
+    Oxycellulose maximum nitration (13.9 p.ct. N)          3600
+    Cellulose minimum nitration (8.19 p.ct. N)             3700
+    Oxycellulose minimum nitration (8.56 p.ct. N)          3620
+
+The author concludes that, since the reducing action is independent of
+the degree of nitration, and is the same for cellulose and the
+oxycelluloses, the ester reaction in the case of the normal cellulose is
+accompanied by oxidation, the product being an oxycellulose ester.
+
+_Products of 'denitration'._--The esters were treated with ferrous
+chloride in boiling aqueous solution. The products were oxycelluloses,
+with a cupric reduction equal to that of an oxycellulose directly
+prepared by the action of HClO_{3}. On the other hand, by treatment with
+ammonium sulphide at 35�-40� 'denitrated' products were obtained without
+action on alkaline copper solutions.
+
+
+OXYCELLULOSES AND THE MOLECULAR WEIGHT OF CELLULOSE.
+
+H. NASTUKOFF (Berl. Ber. 33 [13] 2237).
+
+(p. 61) The author continues his investigations of the oxidation of
+cellulose. [Compare Bull. Mulhouse, 1892.] The products described were
+obtained by the action of hypochlorites and permanganates upon Swedish
+filter paper (Schleicher and Sch�ll).
+
+4. _Oxidation by hypochlorites._--(1) The cellulose was digested 24 hrs.
+with 35 times its weight of a filtered solution of bleaching power of
+4�B.; afterwards drained and exposed for 24 hrs. to the atmosphere.
+These treatments were then repeated. After washing, treatment with
+dilute acetic acid and again washing, the product was treated with a 10
+p.ct. NaOH solution. The oxycellulose was precipitated from the
+filtered solution: yield 45 p.ct. The residue when purified amounted to
+30 p.ct. of the original cellulose, with which it was identical in all
+essential properties.
+
+The oxycellulose, after purification, dried at 110�, gave the following
+analytical numbers:
+
+     C    43.64     43.78    43.32    43.13
+     H     6.17      6.21     5.98     6.08
+
+Its compound with phenylhydrazine (_loc. cit._) gave the following
+analytical numbers:
+
+     N      0.78     0.96    0.84
+
+(2) The reagents were as in (1), but the conditions varied by passing a
+stream of carbonic acid gas through the solution contained in a flask,
+until Cl compounds ceased to be given off. The analysis of the purified
+oxycellulose gave C 43.53, H 6.13.
+
+(3) The conditions were as in (2), but a much stronger hypochlorite
+solution--viz. 12�B.--was employed. The yield of oxycellulose
+precipitated from solution in soda lye (10 p.ct. NaOH) was 45 p.ct.
+There was only a slight residue of unattacked cellulose. The analytical
+numbers obtained were:
+
+    Oxycellulose              C  43.31   43.74   43.69
+        "                     H   6.47    6.42    6.51
+                              ________________________
+
+    Phenylhydrazine compound  N           0.62    0.81
+
+B. _Oxidation by permanganate_ (KMnO_{4}). (1) The cellulose 16 grms.
+was treated with 1100 c.c. of a 1 p.ct. solution of KMnO_{4} in
+successive portions. The MnO_{2} was removed from time to time by
+digesting the product with a dilute sulphuric acid (10 p.ct.
+H_{2}SO_{4}). The oxycellulose was purified as before, yield 40 p.ct.
+Analytical numbers:
+
+    Oxycellulose              C          42.12    42.9
+        "                     H           6.20     6.11
+                              ________________________
+
+    Phenylhydrazine compound  N   1.35    1.08     1.21
+
+(2) The cellulose (16 grms.) was digested 14 days with 2500 c.c. of 1
+p.ct. KMnO_{4} solution. The purified oxycellulose was identical in all
+respects with the above: yield 40 p.ct. C 42.66, H 6.19.
+
+(3) The cellulose (16 grms.) was heated in the water-bath with 1600 c.c.
+of 15 p.ct. H_{2}SO_{4} to which were added 18 grms. KMnO_{4}. The yield
+and composition of the oxycellulose was identical with the above. It
+appears from these results that the oxidation with hypochlorites acids 1
+atom of O to 4-6 of the unit groups C_{6}H_{10}O_{5}; and the oxidation
+with permanganate 2 atoms O per 4-6 units of C_{6}H_{10}O_{5}. The
+molecular proportion of N in the phenylhydrazine residue combining is
+fractional, representing 1 atom O, i.e. 1 CO group reacting per 4
+C_{36}H_{60}O_{31} and 6 C_{24}H_{49}O_{21} respectively, assuming the
+reaction to be a hydrazone reaction.
+
+Further investigations of the oxycelluloses by treatment with (a)
+sodium amalgam, (b) bromine (water), and (c) dilute nitric acid at
+110�, led to no positive results.
+
+By treatment with alcoholic soda (NaOH) the products were resolved into
+a soluble and insoluble portion, the properties of the latter being
+those of a cellulose (hydrate).
+
+_Molecular weight of cellulose and oxycellulose._--The author endeavours
+to arrive at numbers expressing these relations by converting the
+substances into acetates by Schutzenberger's method, and observing the
+boiling-points of their solution in nitrobenzene.
+
+
+FERMENTATION OF CELLULOSE
+
+V. OMELIANSKI (Compt. Rend., 1897, 125, 1131-1133).
+
+Pure paper was allowed to ferment in the presence of calcium carbonate
+at a temperature of 35� for 13 months. The products obtained from
+3.4743 grams of paper were: acids of the acetic series, 2.2402 grams;
+carbonic anhydride, 0.9722 grams; and hydrogen, 0.0138 gram. The acids
+were chiefly acetic and butyric acid, the ratio of the former to the
+latter being 1.7 : 1. Small quantities of valeric acid, higher alcohols,
+and odorous products were formed.
+
+The absence of methane from the products of fermentation is remarkable,
+but the formation of this gas seems to be due to a special organism
+readily distinguishable from the ferment that produces the fatty acids.
+This organism is at present under investigation.
+
+       *       *       *       *       *
+
+(p. 75) ~Constitution of Cellulose.~--It may be fairly premised that the
+problem of the constitution of cellulose cannot be solved independently
+of that of molecular aggregation. We find in effect that the structural
+properties of cellulose and its derivatives are directly connected with
+their constitution. So far we have only a superficial perception of this
+correlation. We know that a fibrous cellulose treated with acids or
+alkalis in such a way that only hydrolytic changes can take place is
+converted into a variety of forms of very different structural
+characteristics, and these products, while still preserving the main
+chemical characteristics of the original, show when converted into
+derivatives by simple synthesis, _e.g._ esters and sulphocarbonates, a
+corresponding differentiation of the physical properties of these
+derivatives, from the normal standard, and therefore that the new
+reacting unit determines a new physical aggregate. Thus the
+sulphocarbonate of a 'hydrocellulose' is formed with lower proportions
+of alkaline hydrate and carbon disulphide, gives solutions of relatively
+low viscosity, and, when decomposed to give a film or thread of the
+regenerated cellulose, these are found to be deficient in strength and
+elasticity. Similarly with the acetate. The normal acetate gives
+solutions of high viscosity, films of considerable tenacity, and when
+those are saponified the cellulose is regenerated as an unbroken film.
+The acetates of hydrolysed celluloses manifest a retrogradation in
+structural and physical properties, proportioned to the degree of
+hydrolysis of the original.
+
+We may take this opportunity of pointing out that the celluloses not
+only suggest with some definiteness the connection of the structural
+properties of visible aggregates--that is, of matter in the mass--with
+the configuration of the chemical molecule or reacting unit, but supply
+unique material for the actual experimental investigation of the
+problems involved. Of all the 'organic' colloids cellulose is the only
+one which can be converted into a variety of derivative forms, from each
+of which a regular solid can be produced in continuous length and of any
+prescribed dimensions. Thus we can compare the structural properties of
+cellulose with those of its hydrates, nitrates, acetates, and benzoates,
+in terms of measurements of breaking strain, extensibility, elasticity.
+Investigations in this field are being prosecuted, but the results are
+not as yet sufficiently elaborated for reduction to formul�. One
+striking general conclusion is, however, established, and that is that
+the structural properties of cellulose are but little affected by
+esterification and appear therefore to be a function of the special
+arrangement of the carbon atoms, i.e. of the molecular constitution.
+Also it is established that the molecular aggregate which constitutes a
+cellulose is of a resistant type, and undoubtedly persists in the
+solutions of the compounds.
+
+It may be urged that it is superfluous to import these questions of
+mass-aggregation into the problem of the chemical constitution of
+cellulose. But we shall find that the point again arises in attempting
+to define the reacting unit, which is another term for the molecule. In
+the majority of cases we rely for this upon physical measurements; and
+in fact the purely chemical determination of such quantities is
+inferential. Attempts have been made to determine the molecular weights
+of the cellulose esters in solution, by observations of depression of
+solidifying and boiling-points. But the numbers have little value. The
+only other well-defined compound is the sulphocarbonate. It has been
+pointed out that, by successive precipitations of this compound, there
+occurs a continual aggregation of the cellulose with dissociation of the
+alkali and CS residues and it has been found impossible to assign a
+limit to the dissociation, i.e. to fix a point at which the transition
+from soluble sulphocarbonate to insoluble cellulose takes place.
+
+On these grounds it will be seen we are reduced to a somewhat
+speculative treatment of the hypothetical ultimate unit group, which is
+taken as of C_{6} dimensions.
+
+As there has been no addition of experimental facts directly
+contributing to the solution of the problem, the material available for
+a discussion of the probabilities remains very much as stated in the
+first edition, pp. 75-77. It is now generally admitted that the
+tetracetate _n_ [C_{6}H_{6}O.(OAc)_{4}] is a normal cellulose ester;
+therefore that four of the five O atoms are hydroxylic. The fifth is
+undoubtedly carbonyl oxygen. The reactions of cellulose certainly
+indicate that the CO- group is ketonic rather than aldehydic. Even when
+attacked by strong sulphuric acid the resolution proceeds some
+considerable way before products are obtained reducing Fehling's
+solution. This is not easily reconcilable with any polyaldose formula.
+Nor is the resistance of cellulose to very severe alkaline treatments.
+The probability may be noted here that under the action of the alkaline
+hydrates there occurs a change of configuration. Lobry de Bruyn's
+researches on the change of position of the typical CO- group of the
+simple hexoses, in presence of alkalis, point very definitely in this
+direction. It is probable that in the formation of alkali cellulose
+there is a constitutional change of the cellulose, which may in effect
+be due to a migration of a CO- position within the unit group. Again
+also we have the interesting fact that structural changes accompany the
+chemical reaction. It is surprising that there should have been no
+investigation of these changes of external form and structure, otherwise
+than as mass effects. We cannot, therefore, say what may be the
+molecular interpretation of these effects. It has not yet been
+determined whether there are any intrinsic volume changes in the
+cellulose substance itself: and as regards what changes are determined
+in the reacting unit or molecule, we can only note a fruitful subject
+for future investigation. _A priori_ our views of the probable changes
+depend upon the assumed constitution of the unit group. If of the
+ordinary carbohydrate type, formulated with an open chain, there is
+little to surmise beyond the change of position of a CO- group. But
+alternative formul� have been proposed. Thus the tetracetate is a
+derivative to be reckoned with in the problem. It is formed under
+conditions which preclude constitutional changes within the unit groups.
+The temperature of the main reaction is 30�-40�, the reagents are used
+but little in excess of the quantitative proportions, and the yields are
+approximately quantitative. If now the derivative is formed entirely
+without the hydrolysis the empirical formula C_{6}H_{6}O.(OAc)_{4}
+justifies a closed-ring formula for the original viz.
+CO<[CHOH]_{4}>CH_{2}; and the preference for this formula depends upon
+the explanation it affords of the aggregation of the groups by way of
+CO-CH_{2} synthesis.
+
+The exact relationship of the tetracetate to the original cellulose is
+somewhat difficult to determine. The starting-point is a cellulose
+hydrate, since it is the product obtained by decomposition of the
+sulphocarbonate. The degree of _hydrolysis_ attending the cycle of
+reactions is indicated by the formula 4 C_{6}H_{10}O_{5}.H_{2}O. It has
+been already shown that this degree of hydrolysis does not produce
+molecular disaggregation. If this hydrate survived the acetylation it
+would of course affect the empirical composition, i.e. chiefly the
+carbon percentage, of the product. It may be here pointed out that the
+extreme variation of the carbon in this group of carbohydrate esters is
+as between C_{14}H_{20}O_{10} (C = 48.3 p.ct.) and C_{14}H_{18}O_{9} (C
+= 50.8 p.ct.) i.e. a tetracetate of C_{6}H_{12}O_{6} and
+C_{6}H_{10}O_{5} respectively. In the fractional intermediate terms it
+is clear that we come within the range of ordinary experimental errors,
+and to solve this critical point by way of ultimate analysis must
+involve an extended series of analyses with precautions for specially
+minimising and quantifying the error. The determination of the acetyl by
+saponification is also subject to an error sufficiently large to
+preclude the results being applied to solve the point. While, therefore,
+we must defer the final statement as to whether the tetracetate is
+produced from or contains a partly hydrolysed cellulose molecule, it is
+clear that at least a large proportion of the unit groups must be
+acetylated in the proportion C_{6}H_{6}O.(OAc)_{4}.
+
+It has been shown that by the method of Franchimont a higher proportion
+of acetyl groups can be introduced; but this result involves a
+destructive hydrolysis of the cellulose: the acetates are not
+derivatives of cellulose, but of products of hydrolytic decomposition.
+
+It appears, therefore, that with the normal limit of acetylation at the
+tetracetate the aggregation of the unit groups must depend upon the CO-
+groups and a ring formula of the general form CO<[CHOH]_{4}>CH_{2} is
+consistent with the facts.
+
+Vignon has proposed for cellulose the constitutional formula
+
+     O------CH
+     |      | \
+     |      O  \[CHOH]_{3}
+     |      |  /
+     CH_{2}-CH/
+
+with reference to the highest nitrate, and the decomposition of the
+nitrate by alkalis with formation of hydroxypyruvic acid. While these
+reactions afford no very sure ground for deductions as to constitutional
+relationships, it certainly appears that, if the aldose view of the unit
+group is to be retained, this form of the anhydride contains suggestions
+of the general tendency of the celluloses on treatment with condensing
+acids to split off formic acid in relatively large quantity [Ber. 1895,
+1940]; the condensation of the oxycelluloses to furfural; the
+non-formation of the normal hydroxy-dicarboxylic acids by nitric acid
+oxidations. Indirectly we may point out that any hypothesis which
+retains the polyaldose view of cellulose, and so fails to differentiate
+its constitution from that of starch, has little promise of progress.
+The above formula, moreover, concerns the assumed unit group, with no
+suggestion as to the mode of aggregation in the cellulose complex. Also
+there is no suggestion as to how far the formula is applicable to the
+celluloses considered as a group. In extending this view to the
+oxycelluloses, Vignon introduces the derived oxidised group
+
+     CHO.(CHOH)_{3}.CH . CO
+                    |_O__|
+
+--of which one is apportioned to three or four groups of the cellulose
+previously formulated: these groups in condensed union together
+constitute an oxycellulose.
+
+These views are in agreement with the experimental results obtained by
+Faber and Tollens (p. 71). They regard the oxycelluloses as compounds of
+'celloxin' C_{6}H_8{O}_{6} with 1-4 mols. unaltered cellulose; and the
+former they particularly refer to as a lactone of glycuronic acid. But
+on boiling with lime they obtain dioxybutyric and isosaccharinic acids;
+both of which are not very obviously related to the compounds formulated
+by Vignon. We revert with preference to a definitely ketonic formula,
+for which, moreover, some farther grounds remain to be mentioned. In the
+systematic investigation of the nitric esters of the carbohydrates (p.
+41) Will and Lenze have definitely differentiated the ketoses from the
+aldoses, as showing an internal condensation accompanying the ester
+reaction. Not only are the OH groups taking part in the latter
+consequently less by two than in the corresponding aldoses, but the
+nitrates show a much increased stability. This would give a simple
+explanation of the well-known facts obtaining in the corresponding
+esters of the normal cellulose. We may note here that an important item
+in the quantitative factors of the cellulose nitric ester reaction has
+been overlooked: that is, the yield calculated to the NO_{3} groups
+fixed. The theoretical yields for the higher nitrates are
+
+                     Yield p.ct.    N p.ct.
+                    of cellulose  of nitrate
+    Pentanitrate        169         12.7
+    Hexanitrate         183         14.1
+
+From such statistics as are recorded the yields are not in accordance
+with the above. There is a sensible deficiency. Thus Will and Lenze
+record a yield of 170 p.ct. for a product with 13.8 p.ct. N, indicating
+a deficiency of about 10 p.ct. As the by-products soluble in the acid
+mixture are extremely small, the deficiency represents approximately the
+water split off by an internal reaction. In this important point the
+celluloses behave as ketoses.
+
+In the lignocelluloses the condensed constituents of the complex are of
+well-marked ketonic, i.e. quinonic, type. In 'nitrating' the
+lignocelluloses this phenomenon of internal condensation is much more
+pronounced (see p. 131). As the reaction is mainly confined to the
+cellulose of the fibre, we have this additional evidence that the
+typical carbonyl is of ketonic function. It is still an open question
+whether the cellulose constituents of the lignocelluloses are
+progressively condensed--with progress of 'lignification'--to the
+unsaturated or lignone groups. There is much in favour of this view,
+the evidence being dealt with in the first edition, p. 180. The
+transition from a cellulose-ketone to the lignone-ketone involves a
+simple condensation without rearrangement; from which we may argue back
+to the greater probability of the ketonic structure of the cellulose. We
+must note, however, that the celluloses of the lignocelluloses are
+obtained as residues of various reactions, and are not homogeneous. They
+yield on boiling with condensing acids from 6 to 9 p.ct. furfural. It is
+usual to regard furfural as invariably produced from a pentose residue.
+But this interpretation ignores a number of other probable sources of
+the aldehyde. It must be particularly remembered that l�vulose is
+readily condensed (a) to a methylhydroxyfurfural
+
+C_{6}H_{1}O_{6} - 3H_{2}O = C_{6}H_{6}O_{3} = C_{5}(OH).H_{2}.(CH_{3})O_{2}
+
+and (b) by HBr, with further loss of OH, as under:
+
+C_{6}H_{12}O_{6} - 4H_{2}O + HBr = C_{5}H_{3}(CH_{2}Br)O
+
+and generally the ketoses are distinguished from the aldoses by their
+susceptibility to condensation. Such condensation of l�vulose has been
+effected by two methods: (a) by heating the concentrated aqueous
+solution with a small proportion of oxalic acid at 3 atm. pressure
+[Kiermayer, Chem. Ztg. 19, 100]; (b) by the action of hydrobromic acid
+(gas) in presence of anhydrous ether; the actual compound obtained being
+the omega-brommethyl derivative [Fenton, J. Chem. Soc. 1899, 423].
+
+This latter method is being extended to the investigation of typical
+celluloses, and the results appear to confirm the view that cellulose
+may be of ketonic constitution.
+
+The evidence which is obtainable from the synthetical side of the
+question rests of course mainly upon the physiological basis. There are
+two points which may be noted. Since the researches of Brown and Morris
+(J. Chem. Soc. 1893, 604) have altered our views of the relationships of
+starch and cane sugar to the assimilation process, and have placed the
+latter in the position of a primary product with starch as a species of
+overflow and reserve product, it appears that l�vulose must play an
+important part in the elaboration of cellulose. Moreover, A. J. Brown,
+in studying the cellulosic cell-collecting envelope produced by the
+_Bacterium xylinum_, found that the proportion of this product to the
+carbohydrate disappearing under the action of the ferment was highest in
+the case of l�vulose. These facts being also taken into consideration
+there is a concurrence of suggestion that the typical CO group in the
+celluloses is of ketonic character. That the typical cotton cellulose
+breaks down finally under the action of sulphuric acid to dextrose
+cannot be held to prove the aldehydic position of the carbonyls in the
+unit groups of the actual cellulose molecule or aggregate.
+
+We again are confronted with the problem of the aggregate and as to how
+far it may affect the constitution of the unit groups. That it modifies
+the functions or reactivity of the ultimate constituent groups we have
+seen from the study of the esters. Thus with the direct ester reactions
+the normal fibrous cellulose (C_{6}H_{16}O_{5}) yields a monoacetate,
+dibenzoate, and a trinitrate respectively under conditions which
+determine, with the simple hexoses and anhydrides, the maximum
+esterification, i.e. all the OH groups reacting. If the OH groups are of
+variable function, we should expect the CO groups _a fortiori_ to be
+susceptible of change of function, i.e. of position within the unit
+groups.
+
+But as to how far this is a problem of the constitution or phases of
+constitution of the unit groups or of the aggregate under reaction we
+have as yet no grounds to determine.
+
+The subjoined communication, appearing after the completion of the MS.
+of the book, and belonging to a date subsequent to the period intended
+to be covered, is nevertheless included by reason of its exceptional
+importance and special bearing on the constitutional problem above
+discussed.
+
+
+~THE ACTION OF HYDROGEN BROMINE ON CARBOHYDRATES.~[4]
+
+H. J. H. FENTON and MILDRED GOSTLING (J. Chem. Soc., 1901, 361).
+
+The authors have shown in a previous communication (Trans., 1898, 73,
+554) that certain classes of carbohydrates when acted upon at the
+ordinary temperature with dry hydrogen bromide in ethereal solution give
+an intense and beautiful purple colour.[5] It was further shown (Trans.,
+1899, 75, 423) that this purple substance, when neutralised with sodium
+carbonate and extracted with ether, yields golden-yellow prisms of
+omega-brommethylfurfural,
+
+     CH:C.CH_{2}Br
+     |  |
+     |  O
+     |  |
+     CH:C.CHO.
+
+This reaction is produced by l�vulose, sorbose, cane sugar, and inulin,
+an intense colour being given within an hour or two. Dextrose, maltose,
+milk sugar, galactose, and the polyhydric alcohols give, if anything,
+only insignificant colours, and these only after long standing. The
+authors therefore suggested that the reaction might be employed as a
+means of distinguishing these classes of carbohydrates, the rapid
+production of the purple colour being indicative of _ketohexoses_, or of
+substances which produce these by hydrolysis.
+
+By relying only on the production of the purple colour, however, a
+mistake might possibly arise, owing to the fact that _xylose_ gives a
+somewhat similar colour after standing for a few hours. Hence, the
+observations should be confirmed by isolation of the crystals of
+brommethylfurfural. No trace of this substance is obtained from the
+xylose product.
+
+In order to identify the substance, the ether extract, after
+neutralisation, is allowed to evaporate to a syrup, and crystallisation
+promoted either by rubbing with a glass rod, or by the more certain and
+highly characteristic method of 'sowing' with the most minute trace of
+omega-brommethylfurfural, when crystals are almost instantly formed.
+These are recrystallised from ether, or a mixture of ether and light
+petroleum, and further identified by the melting-point (59.5-60.5�),
+and, if considered desirable, by estimation of the bromine.
+
+It is now found, so reactive is the bromine atom in this compound, that
+the estimation may be accurately made by titration with silver nitrate
+according to Volhard's process, the crystals for this purpose being
+dissolved in dilute alcohol:
+
+0.1970 gram required 10.5 c.c. _N_/10 AgNO_{3}. Br = 42.63
+p.ct., calculated 42.32 p.ct.
+
+This method of applying hydrogen bromide in ethereal solution is, of
+course, unsuitable for investigations where a higher temperature has to
+be employed, or where long standing is necessary, since, under such
+circumstances, the ether itself is attacked. Wishing to make
+investigations under these conditions, the authors have tried several
+solvents, and, at present, find that chloroform is best suited to the
+purpose. In each of the following experiments, 10 grms. of the
+substance were covered with 250 c.c. of chloroform which had been
+saturated at 0� with dry hydrogen bromide. The mixture was contained in
+an accurately stoppered bottle, firmly secured with an iron clamp, and
+heated in a water-bath to about the boiling temperature for two hours.
+After standing for several hours, the mixture was treated with sodium
+carbonate (first anhydrous solid, and afterwards a few drops of strong
+solution), filtered, and the solution dried over calcium chloride. Most
+of the chloroform was then distilled off, and the remaining solution
+allowed to evaporate to a thick syrup in a weighed dish.
+
+The product was then tested for omega-brommethylfurfural by 'sowing'
+with the most minute trace of the substance, as described above. It was
+then warmed on a water-oven, kept in a vacuum desiccator over solid
+paraffin, and the weight estimated. When necessary, the product was
+recrystallised from ether, and further identified by the tests
+mentioned. The following results were obtained:
+
+                      Weight of
+                    crude residue.
+Swedish filter paper     3.0      crystallised at once by 'sowing.'
+Ordinary cotton          3.3          "                     "
+Mercerised cotton        2.1          "                     "
+Straw cellulose[6]       2.3          "                     "
+L�vulose                 2.2          "                     "
+Inulin                   1.3          "                     "
+Potato starch            0.37         "                     "
+Cane sugar               0.85         "                     "
+Dextrose                 0.33     uncrystallisable.
+Milk sugar               0.37         "
+Glycogen                 0.34         "
+Galactose                0.34         "
+
+The products from _dextrose_, _milk sugar_, and _galactose_ absolutely
+refused to crystallise even when extracted with ether and again
+evaporated, or by 'sowing,' stirring, &c.
+
+The _glycogen_ product deposited a very small amount of crystalline
+matter on standing, but the quantity was too minute for examination;
+moreover, it refused altogether to crystallise in contact with the
+aldehyde. It may fairly be stated, therefore, that these last four
+substances give absolutely negative results as regards the formation of
+omega-brommethylfurfural; if any is formed, its quantity is altogether
+too small to be detected.
+
+The specimen of _starch_ examined was freshly prepared from potato, and
+purified by digestion for twenty-four hours each with _N_/10 KOH, _N_/4
+HCl, and strong alcohol; it was then washed with water and allowed to
+dry in the air. It will be seen that this substance gave a positive
+result, but that the yield was extremely small, and might yet be due to
+impurity. Considering the importance of the behaviour of starch, for the
+purpose of drawing general conclusions from these observations, it was
+thought advisable to make further experiments with specimens which could
+be relied upon, and also to investigate the behaviour of dextrin. This
+the authors have been enabled to do upon a series of specimens specially
+prepared by C. O'Sullivan, and thus described by him:
+
+     1. Rice starch, specially purified by the permanganate method.
+
+     2. Wheat starch       "                "                 "
+
+     3. Oat starch, contains traces of oil, washed with dilute KOH
+     and dilute HCl.
+
+     4. Pea starch, first crop, washed with alkali, acid (HCl), and
+     strong alcohol.
+
+     5. Natural dextrin, D = 3.87, alpha_{D} = 194.7; K = 0.95, (c
+     2.628).
+
+     6. alpha-Dextrin, C equation purified without fermentation, 30
+     precipitations with alcohol (Trans., 1879, 35, 772).
+
+The examination of these specimens was conducted on a smaller scale, but
+under the same conditions as before, _one gram_ of the substance being
+treated with 12.5 c.c. of the saturated chloroform solution and heated
+in sealed tubes for two hours as above. The results were as follows:
+
+                    Weight of
+                  crude residue.
+1. Rice starch       0.046   crystallised at once by 'sowing.'
+2. Wheat starch      0.044        "                 "
+3. Oat starch        0.049        "                 "
+4. Pea starch        0.064        "                 "
+5. Natural dextrin   0.088        "                 "
+6. alpha-Dextrin     0.055        "                 "
+
+The results may therefore be summarised as follows:--Treated under these
+particular conditions all forms of cellulose give large yields of
+omega-brommethylfurfural, some varieties giving as much as 33 per cent.
+L�vulose, inulin, and cane sugar give yields varying from 22 to 8.5 per
+cent.; various starches give small yields (average about 4.5 per cent.);
+and dextrins 5 to 8 per cent., whereas dextrose, milk sugar, and
+galactose give, apparently, none at all.
+
+The yields represent the solid crystalline residue; this when purified
+by recrystallisation gives, probably, about three-quarters of its weight
+of pure crystals. (In the case of dextrose, &c., the yields represent
+the weight of syrup.)
+
+These numbers, however, by no means represent the maximum yields
+obtainable, owing to the comparatively slight solubility of hydrogen
+bromide in chloroform. The process was conducted in the above manner
+only for the sake of uniform comparison. The ether method previously
+described gives much larger yields; for example, 12 grms. of inulin
+treated with only 60 c.c. of the saturated ether gave 2.5 grms. of
+substance. For the purpose of obtaining larger yields, other methods are
+being investigated.
+
+The facts recorded above, taken in conjunction with those given in our
+previous communications, appear to point definitely to the following
+general conclusions. First, that the various forms of _cellulose_
+contain one or more groups or nuclei identical with that contained in
+_l�vulose_, and that such groups constitute the main or essential part
+of the molecule. Secondly, that similar groupings are contained in
+_starches_ and _dextrins_, but that the proportion of such groupings
+represents a relatively small part of the whole structure.
+
+The nature of this grouping is, according to the generally accepted
+constitution of _l�vulose_, the six-carbon chain with a ketonic group:
+
+     C�C�C�C�C�C
+             || .
+             O
+
+But the results might, on the other hand, be considered indicative of
+the anhydride or 'lacton' grouping, which Tollens suggested for
+l�vulose:
+
+     C�C�C�C�C�C
+        \   /
+         \ /  .
+          O
+
+The latter very simply represents the formation of
+omega-brommethylfurfural from l�vulose,[7]
+
+              ------O-----
+              |   H   H  |
+              |   |   |  |
+     OH�C-----C---C---C--C-----CH_{2}�OH
+        H_{2} OH  OH  OH H
+
+giving
+
+          H H
+     HC�C:C�C:C�CH_{2}Br
+      || \   /    ,
+      O   \ /
+           O
+
+
+although by a little further 'manipulation' of the symbols the change
+could, of course, be represented by reference to the ketonic formula.
+
+
+~The Ketonic Constitution of Cellulose.~
+
+C. F. CROSS and E. J. BEVAN (J. Chem. Soc., 1901, 366).
+
+In this paper the authors discuss more fully the theoretical bearings of
+the observations of Fenton and Gostling, the two papers being
+simultaneously communicated. The paper is mainly devoted to a review of
+the antecedent evidence, chemical and physiological, and to a general
+summing up in favour of the view that cellulose is a polyketose
+(anhydride).
+
+       *       *       *       *       *
+
+(p. 79) ~Composition of the Seed Hair of Eriodendron~ (~Anf.~)--Some
+interest attaches to the results of an analytical investigation which we
+have made of this silky floss. There is little doubt that cotton is
+entirely exceptional in its characteristics: both in structure and
+chemical composition it fails to show any adaptation to what we may
+regard as the _more obvious_ functions of a seed hair--which certainly
+do not demand either structural strength or chemical resistance. The
+following numbers determined for the kapok differentiate it widely from
+the cottons:
+
+     Ash, 1.3; moisture, 9.3; alkaline hydrolysis (loss) (a) 16.7,
+     (b) 21.8. Cellulose, by chlorination, &c., 71.1.
+
+In reacting with chloride it shows the presence of unsaturated groups,
+similar to the lignone of the woods. This was confirmed by a
+well-marked reaction with ferric ferricyanide with increase of weight
+due to the fixation of the blue cyanide.
+
+But the most characteristic feature is the high yield of furfural on
+boiling with condensing acids. The following numbers were determined:
+
+     Total furfural from original fibre    14.84
+     In residue from alkali hydrolysis     11.5
+     In cellulose isolated by Cl method    10.4
+
+Treated with sulphuric acids of concentration, (a) 92.1 grs.
+H_{2}SO_{4} per 100 c.c., (b) 105.8 grs. per 100 c.c., the fibres
+dissolve, and diluted immediately after complete solution it was
+resolved into
+
+                                      (a)        (b)
+
+Reprecipitated fraction               68.7       43.7
+Soluble fraction yielding furfural    13.2       14.3
+
+By these observations it is established that the furfuroids are of the
+cellulose type and behave very much as the furfuroids of the cereal
+celluloses.
+
+This group of seed hairs invites exhaustive investigation. The furfuroid
+constituents are easily isolated, and as they constitute at least
+one-third of the fibre substance it is especially from this point of
+view that they invite study.
+
+
+RECHERCHES SUR L'OXYCELLULOSE.
+
+L. VIGNON.
+
+~R�sum� of investigations (1898-1900) of Oxycellulose, published as a
+brochure~ (Rey, Lyon, 1900).
+
+(a) A typical oxycellulose prepared from cotton cellulose by the
+action of HClO_{3} (HCl + KClO_{3}) in dilute solution at 100� for one
+hour gave the following numbers:
+
+                                                  C        H        O
+Elementary composition                          43.55    6.03     50.42
+
+                                        Oxycellulose   Original cellulose
+  Analysis by Lange's method
+    Soluble in KOH (at 180�)               87.6           12.0
+    Insoluble in KOH (at 180�)             12.4           88.0
+
+                                           Oxycellulose  Original cellulose
+  Heat of combustion                        4124-4133      4190-4224
+Heat evolved in contact with 50 times wt.}
+  normal KOH per 100 grms.               }  1.3 cal.       0.74 cal.
+
+                                            Oxycellulose  Cellulose
+Absorption of colouring       } Saffranine       0.7          0.0
+matters at 100� per 100 grms. } Methylene blue   0.6          0.2
+
+(b) _Yield of furfural from cellulose, oxy- and
+hydro-cellulose._--From the hydrocelluloses variously prepared the
+author obtains 0.8 p.ct. furfural; from bleached cotton 1.8 p.ct.; and
+from the oxycelluloses variously prepared 2.0-3.5 p.ct. The 'furfuroid'
+is relatively more soluble in alkaline solutions (KOH) in the cold. The
+insoluble residue is a normal cellulose.
+
+(c) _Nitrates of cellulose, oxy- and hydro-cellulose._--Treated with
+the usual acid mixture (H_{2}SO_{4} 3 p., HNO_{3} 1 p.) under conditions
+for maximum action, the resulting esters showed uniformly a fixation of
+11.0 NO_{2} groups per unit mol. of C_{24}. The oxycellulose nitrate
+was treated directly with dilute solution of potassium hydrate in the
+cold. From the products of decomposition the author obtained the osazone
+of hydroxypyruvic acid [Will, Ber. 24, 400].
+
+(d) _Osazones of the oxycelluloses._--Oxycelluloses prepared by
+various methods are found to fix varying proportions of phenylhydrazine
+(residue), viz. from 3.4-8.5 p.ct. of the cellulose derivative reacting,
+corresponding with, i.e. calculated from, the nitrogen determined in the
+products (0.87-2.2 p.ct.). The reaction is assumed to be that of osazone
+formation.
+
+The author has also established a relation between the phenylhydrazine
+fixed and the furfural which the substance yields on boiling with
+condensing acids. This is illustrated by the subjoined series of
+numbers:
+
+                              Phenylhydrazine     Furfural
+                                 Fixed p.ct.    formed p.ct.
+Cotton (bleached)                   1.73            1.60
+Oxycellulose (HClO_{3})             7.94            2.09
+     "       (HClO)                 3.37            1.79
+     "       (CrO_{3}) (1)          7.03            3.00
+     "       (CrO_{3}) (2)          7.71            3.09
+     "       (CrO_{3}) (3)          8.48            3.50
+
+(e) _Constitution of cellulose and oxycellulose._--The results of
+these investigations are generalised as regards cellulose (C_6) by the
+constitutional formula
+
+                 CH--CH_{2}
+               / |   |
+     (CHOH)_{3}  O   |
+               \ |   |
+                 CH--O .
+
+The oxycelluloses contain the characteristic group
+
+                COH
+               /
+     (CHOH)_{3}
+               \
+                CH--CO
+                 \ /
+                  O
+
+in union with varying proportions of residual cellulose.
+
+
+QUANTITATIVE SEPARATION OF CELLULOSE-LIKE CARBOHYDRATES IN VEGETABLE
+SUBSTANCES.
+
+WILHELM HOFFMEISTER (Landw. Versuchs-Stat., 1897, 48, 401-411).
+
+To separate the hemicelluloses, celluloses, and the constituents of
+lignin without essential change, the substance, after being freed from
+fat, is extracted with dilute hydrochloric acid and ammonia, and the
+residue frequently agitated for a day or two with 5-6 p.ct. caustic soda
+solution. It is then diluted, the extract poured off, neutralised with
+hydrochloric acid, treated with sufficient alcohol, and the
+hemicellulose filtered, dried, and weighed. The residue from the soda
+extract is washed on a filter with hot water, and extracted with
+Schweizer's reagent.
+
+When the final residue (lignin) is subjected to prolonged extraction
+with boiling dilute ammonia (a suitable apparatus is described, with
+sketch) until the ammonia is no longer coloured, a residue is obtained
+which mostly dissolves in Schweizer's reagent, and on repeating the
+process the residue is found to consist largely of mineral matter. The
+dissolved cellulose-like substances often contain considerable amounts
+of pentosanes.
+
+According to the nature of the substance, the extraction with ammonia
+may take weeks, or months, or even longer; the ammonia extracts of hard
+woods (as lignum vit�) and of cork are dark brown, and give an odour of
+vanilla when evaporated down. The residues, which are insoluble in
+water, but redissolve in ammonia, have the properties of humic acids.
+Other vegetable substances, when extracted, yielded, besides humic
+acids, a compound, C_{6}H_{7}O_{2}, soluble in alcohol and chloroform,
+but insoluble in water, ether, and benzene; preparations from different
+sources melted between 200� and 210�.
+
+FOOTNOTES:
+
+[4] The original paper is reproduced with slight alterations.
+
+[5] This purple colour would appear to be due to a highly dissociable
+compound of omega-brommethylfurfural with hydrogen bromide. The aldehyde
+gives yellow or colourless solutions in various solvents, which are
+turned purple by a sufficient excess of hydrogen bromide. Dilution, or
+addition of water, at once discharges the colour.
+
+[6] Other forms of cellulose were also examined--for example, pinewood
+cellulose--and the substances separated from solution as thiocarbonate
+(powder and film). All of these gave good yields of
+omega-brommethylfurfural.
+
+[7] The change is empirically represented as
+
+C_{6}H_{12}O_{6} + HBr - 4H_{2}O = C_{6}H_{5}O_{2}Br.
+
+
+
+
+SECTION IV. CELLULOSE GROUP, INCLUDING HEMICELLULOSES AND TISSUE
+CONSTITUENTS OF FUNGI
+
+
+VERSUCHE ZUR BESTIMMUNG DES GEHALTS EINIGER PFLANZEN UND PFLANZENTEILE
+AN ZELLWANDBESTANDTEILEN AN HEMICELLULOSEN UND AN CELLULOSE.
+
+A. KLEIBER (Landw. Vers.-Stat., 1900, 54, 161).
+
+~ON THE DETERMINATION OF CELL-WALL CONSTITUENTS, HEMICELLULOSES AND
+CELLULOSE IN PLANTS AND PLANT TISSUES.~
+
+In a preliminary discussion the author critically compares the results
+of various of the methods in practice for the isolation and estimation
+of cellulose. The method of F. Schulze [digestion with dil. HNO_{3} with
+KClO_{3}--14 days, and afterwards treating the product with ammonia,
+&c.] is stated to be the 'best known' (presumably the most widely
+practised); W. Hoffmeister's modification of the above, in which the
+nitric acid is replaced by hydrochloric acid (10 p.ct. HCl) is next
+noted as reducing the time of digestion from 14 days to 1-2 days, and
+giving in many cases higher yields of cellulose. The methods of treating
+with the halogens, viz. bromine water (H. M�ller), chlorine gas (Cross
+and Bevan), and chlorine water, are dismissed with a bare mention,
+apparently on the basis of the conclusions of Suringar and Tollens
+(_q.v._). The method of Lange, the basis of which is a 'fusion' with
+alkaline hydrates at 180�, and the modified method of Gabriel, in which
+the 'fusion' with alkali takes place in presence of glycerin, are
+favourably mentioned.
+
+These methods were applied to a range of widely different raw materials
+to determine, by critical examination of the products, both as regards
+yield and composition, what title these latter have to be regarded as
+'pure cellulose.'
+
+This portion of the investigation is an extension of that of Suringar
+and Tollens, these latter confining themselves to celluloses of the
+'normal' groups, i.e. textile and paper-making celluloses. The present
+communication is a study of the tissue and cell-wall constituents of the
+following types:--
+
+     1. Green plants of false oat grass (_Arrhenatherium, E._).
+     2. Green plants of lucerne (_Medicago sativa_).
+     3. Leaves of the ash (_Fraxinus_).
+     4. Leaves of the walnut (_Juglans_).
+     5. Roots of the purple melic grass (_Molinia c�rulea_).
+     6. Roots of dandelion (_Taraxacum officinale_).
+     7. Roots of comfrey.
+     8. Coffee berries.
+     9. Wheat bran.
+
+These raw materials were treated for the quantitative estimation of
+cellulose by the method of Lange (b), Hoffmeister (c), and Schulze
+(d), and the numbers obtained are referred for comparison to the
+corresponding yields of 'crude fibre' (Rohfaser) by the standard method
+(a).
+
+As a first result the author dismisses Lange's method as hopeless: the
+results in successive determinations on the same materials showing
+variations up to 60 p.ct. The results by c and d are satisfactorily
+concordant: the yields of cellulose are higher than of 'crude fibre.'
+This is obviously due to the conservation of 'hemicellulose' products,
+which are hydrolysed and dissolved in the treatments for 'crude fibre'
+estimation. A modified method was next investigated, in which the
+process of digestion with acid chloroxy- compounds (c and d) was
+preceded by a treatment with boiling dilute acid. The yields of
+cellulose by this method (e) are more uniform, and show less
+divergence from the numbers for 'crude fibre.'
+
+The author's numerical results are given in a series of tables which
+include determinations of proteids and ash constituents, and the
+corresponding deductions from the crude weight in calculating to 'pure
+cellulose.' The subjoined extract will illustrate these main lines of
+investigation.
+
+ ___________________________________________________________
+|                |             |                            |
+|                | Crude Fibre |       Pure Cellulose       |
+|                |_____________|____________________________|
+|                |             |             |              |
+| Raw Material   |   Weende    | Hoffmeister | Hoffmeister, |
+|                |   Method.   |   Method.   | modified by  |
+|                |     (a)     |     (c)     |   Author.    |
+|                |             |             |     (e)      |
+|________________|_____________|_____________|______________|
+|                |             |             |              |
+| Oat grass      |   30.35     |    34.9     |     31.5     |
+| Lucerne        |   25.25     |    28.7     |     20.5     |
+| Leaves of ash  |   13.05     |    15.4     |     13.8     |
+| Roots of melic |   21.60     |    29.1     |     21.4     |
+| Coffee beans   |   18.30     |    35.1     |     23.3     |
+| Bran           |    8.2      |    19.3     |      9.3     |
+|________________|_____________|_____________|______________|
+
+The final conclusion drawn from these results is that the method of
+Hoffmeister yields a product containing variable proportions of
+hemicelluloses. These are eliminated by boiling with a dilute acid (1.25
+p.ct. H_{2}SO_{4}), which treatment may be carried out on the raw
+material--i.e. before exposure to the acid chlorate, or on the crude
+cellulose as ordinarily isolated.
+
+~Determination of Tissue-constituents.~--By the regulated action of
+certain solvents applied in succession, it appears that such
+constituents of the plant-complex can be removed as have no organic
+connection with the cellular skeleton: the residue from such treatments,
+conversely, fairly represents the true tissue-constituents. The author
+employs the method of digestion with cold dilute alkaline solutions
+(0.15 to 0.5 p.ct. NaOH), followed by exhaustive washing with cold and
+hot water, afterwards with cold and hot alcohol, and finally with ether.
+
+The residue is dried and weighed as crude product. When necessary, the
+proportions of ash and proteid constituents are determined and deducted
+from the 'crude product' which, thus corrected, may be taken as
+representing the 'carbohydrate' tissue constituents.
+
+~Determination of Hemicelluloses.~--By the process of boiling with dilute
+acids (1.25 p.ct. H_{2}SO_{4}) the hemicelluloses are attacked--i.e.
+hydrolysed and dissolved. The action of the acid though selective is, of
+course, not exclusively confined to these colloidal carbohydrates. The
+proteid and mineral constituents are attacked more or less, and the
+celluloses themselves are not entirely resistant to the action. The loss
+due to the latter may be neglected, but in calculating the hemicellulose
+constants from the gross loss the proteids and mineral constituents
+require to be taken into account in the usual way.
+
+
+QUANTITATIVE SEPARATION OF HEMICELLULOSE, CELLULOSE, AND LIGNIN.
+PRESENCE OF PENTOSANES IN THESE SUBSTANCES.
+
+WILHELM HOFFMEISTER (Landw. Versuchs-Stat, 1898, 50, 347-362).
+
+(p. 88) The separation of the cellulose-like carbohydrates of sunflower
+husks is described.
+
+In order to ascertain the effect of dilute ammonia on the cellulose
+substances of lignin, a dried 5 p.ct. caustic soda extract was extracted
+successively with 1, 2, 3, and 4 p.ct. sodium hydroxide solution. Five
+grams of the 2 p.ct. extract were then subjected to the action of
+ammonia vapour; the cellulose did not completely dissolve in six weeks.
+Cellulose insoluble in caustic soda (32 grms.) was next extracted with
+ammonia, in a similar manner, for 10 days, dried, and weighed. 30.46
+grms. remained, which, when treated with 5 p.ct. aqueous caustic soda,
+yielded 0.96 grm. (3 per cent.) of hemicellulose.
+
+When cellulose is dissolved in Schweizer's solution, the residue is, by
+repeated extraction with aqueous sodium hydroxide, completely converted
+into the soluble form. On evaporating the ammonia from the Schweizer's
+extract, at the ordinary temperature and on a water-bath respectively,
+different amounts of cellulose are obtained; more hemicellulose is
+obtained, by caustic soda, from the heated solution than from that which
+was not heated. In this operation the pentosanes are more influenced
+than the hexosanes; pentosanes are not always readily dissolved by
+caustic soda, and hexosanes are frequently more or less readily
+dissolved. Both occur in lignin, and are then undoubtedly indigestible.
+These points have to be considered in judging the digestibility of these
+carbohydrates.
+
+A comparison of analyses of clover, at different periods, in the first
+and second years of growth, shows that both cellulose (Schweizer's
+extract) and lignin increase in both constituents. In the second year
+the lignin alone increased to the end; the cellulose decreased at the
+end of June. In the first year it seemed an absolutely as well as
+relatively greater amount of cellulose, and lignin was produced in the
+second year; this, however, requires confirmation. The amount of
+pentosanes in the Schweizer extract was relatively greater in the second
+than in the first year, but decreased in the lignin more in the second
+year than in the first: this result is also given with reserve.
+
+
+DIE CONSTITUTION DER CELLULOSEN DER CEREALIEN.
+
+C. F. CROSS, E. J. BEVAN, and C. SMITH (Berl. Ber., 1896, 1457).
+
+~THE CONSTITUTION OF THE CEREAL CELLULOSES.~
+
+(p. 84) Straw cellulose is resolved by two methods of acid hydrolysis
+into a soluble furfural-yielding fraction, and an insoluble fraction
+closely resembling the normal cellulose. (a) The cellulose is
+dissolved in sulphuric acids of concentration, H_{2}SO_{4}.2H_{2}O,
+H_{2}SO_{4}.3H_{2}O. As soon as solution is complete, the acid is
+diluted. A precipitate of cellulose hydrate (60-70 p.ct.) is obtained,
+and the filtered solution contains 90-95 p.ct. of the furfuroids of the
+original cellulose. The process is difficult to control, however, in
+mass, and to obtain the latter in larger quantity the cellulose (b) is
+digested with six times its weight of 1 p.ct. H_{2}SO_{4} at 3 atm.
+pressure, the products of the action being (1) a disintegrated cellulose
+retaining only a small fraction (1/12) of the furfural-yielding groups,
+and (2) a slightly coloured solution of the hydrolised furfuroids. An
+investigation of the latter gave the following results: By oxidation
+with nitric acid no saccharic acid was obtained; showing the absence of
+dextrose. The numbers for cupric reduction were in excess of those
+obtained with the hexoses. The yield of ozazone was high, viz. 30 to 40
+p.ct. of the weight of the carbohydrate in solution. On fractionating,
+the melting-points of the fractions were found to lie between 146� and
+153�. Ultimate analysis gave numbers for C, H, and N identical with
+those of a pentosazone. The product of hydrolysis appears, therefore, to
+be xylose or a closely related derivative.
+
+All attempts to obtain a crystallisation of xylose from the solution
+neutralised (BaCO_{3}), filtered, and evaporated, failed. The reaction
+with phloroglucol and HCl, moreover, was not the characteristic red of
+the pentoses, but a deep violet. The product was then isolated as a dry
+residue by evaporating further and drying at 105�. Elementary analysis
+gave the numbers C 44.2, 44.5, and H 6.7, 6.3. Determinations of
+furfural gave 39.5 to 42.5 p.ct. On treating the original solution with
+hydrogen peroxide, and warming, oxidation set in, with evolution of
+CO_{2}. This was estimated (by absorption), giving numbers for CO_{2},
+19.5, 20.5, 20.1 p.ct. of the substance.
+
+The sum of these quantitative data is inconsistent with a pentose or
+pentosane formula; it is more satisfactorily expressed by the empirical
+formula
+
+                   O
+                  / \
+     C_{5}H_{8}O_{3} CH_{2},
+                  \ /
+                   O
+
+which represents a pentose monoformal. Attempts to synthesise a compound
+of this formula have been so far without success.
+
+
+UEBER EINIGE CHEMISCHE VORG�NGE IN DER GERSTENPFLANZE.
+
+C. F. CROSS, E. J. BEVAN, and C. SMITH (Berl. Ber., 1895, 2604).
+
+~THE CHEMICAL LIFE-HISTORY OF THE BARLEY PLANT.~
+
+(p. 84) Owing to the presence of 'furfuroids' in large proportion as
+constituents of the tissues of the stems of cereals, these plants afford
+convenient material for studying the problem of the constitution of the
+tissue-furfuroids, as well as their relationship to the normal
+celluloses. The growing barley plant was investigated at successive
+periods of growth. Yield of furfural was estimated on the whole plant
+and on the residue from a treatment with alkaline and acid solvents in
+the cold such as to remove all cell contents. This residue is described
+as 'permanent tissue.' The observations were carried out through two
+growing seasons--1894-5--which were very different in character, the
+former being rainy with low temperature, the latter being abnormal in
+the opposite direction, i.e. minimum rainfall and maximum sunshine. The
+barley selected for observation was that of two experimental plots of
+the Royal Agricultural Society's farm, one (No. 1) remaining permanently
+unmanured, and showing minimum yield, the other (No. 6) receiving such
+fertilising treatment as to give maximum yields.
+
+The numerical results are given in the annexed tables:
+
+Table Headings:
+
+A: Date
+B: Age of Crop
+C: Plot
+D: Dry Weight
+E: Furfural p.ct. of dry weight (a)
+F: Permanent tissue p.ct. dry weight
+G: Furfural from permanent tissue
+H: P.ct. of tissue
+I: P.ct. of entire plant
+J: Ratio a : c
+
+BARLEY CROP, WOBURN, 1894.
+
+ ________________________________________________________________________
+|         |          |     |      |      |      |             |          |
+|         |          |     |      |      |      |     [G]     |          |
+|         |          |     |      |      |      |_____________|          |
+|         |          |     |      |      |      |      |      |          |
+|   [A]   |    [B]   | [C] | [D]  | [E]  | [F]  | [H]  | [I]  |   [J]    |
+|_________|__________|_____|______|______|______|______|______|__________|
+|         |          |     |      |      |      |      |      |          |
+| May 7   |  6 weeks |  1  | 19.4 |  7.0 | 53.4 | 12.7 |  6.8 | 1.03 : 1 |
+|         |          |  6  | 14.7 |  7.0 | 55.9 | 10.3 |  5.7 | 1.23 : 1 |
+| June 4  | 10 weeks |  1  | 17.6 |  7.7 | 52.9 | 11.6 |  6.1 | 1.26 : 1 |
+|         |          |  6  | 13.5 |  8.1 | 58.5 | 13.4 |  7.8 | 1.04 : 1 |
+| July 10 | 15 weeks |  1  | 42.0 |  9.0 | 65.7 |  9.8 |  6.4 | 1.40 : 1 |
+|         |          |  6  | 32.9 | 10.6 | 65.7 | 12.5 |  8.2 | 1.30 : 1 |
+| Cut     | 21 weeks |  1  | 64.0 | 11.9 | 70.0 | 14.5 | 10.1 | 1.18 : 1 |
+| Aug. 21 |          |  6  | 64.6 | 13.4 | 70.5 | 15.0 | 10.6 | 1.26 : 1 |
+| Carried | 22 weeks |  1  | 84.0 | 12.7 | 75.0 | 16.5 | 12.4 | 1.02 : 1 |
+| Aug. 31 |          |  6  | 86.4 | 12.4 | 78.4 | 15.1 | 11.8 | 1.05 : 1 |
+|                                                                        |
+|   BARLEY CROP, WOBURN, 1895.                                           |
+|                                                                        |
+| May 15  |  7 weeks |  1  | 20.6 |  6.6 | 53.9 | 10.2 |  5.5 | 1.20 : 1 |
+|         |          |  6  | 17.8 |  5.8 | 56.7 |  9.6 |  5.4 | 1.07 : 1 |
+| June 18 | 12 weeks |  1  | 34.6 |  8.0 | 38.2 | 14.7 |  5.6 | 1.42 : 1 |
+|         |          |  6  | 33.4 |  7.6 | 44.5 | 15.0 |  6.7 | 1.14 : 1 |
+| July 16 | 16 weeks |  1  | 52.8 | 12.1 | 55.6 | 16.3 |  9.1 | 1.33 : 1 |
+|         |          |  6  | 54.4 | 10.6 | 46.2 | 19.1 |  8.8 | 1.20 : 1 |
+| Aug. 16 | 20 weeks |  1  | 66.8 |  9.2 | 49.1 | 17.0 |  8.3 | 1.10 : 1 |
+|         |          |  6  | 65.0 |  9.8 | 49.8 | 19.1 |  9.4 | 1.04 : 1 |
+| Sept. 3 | 22 weeks |  1  | 84.3 | 10.4 | 45.7 | 17.6 |  8.0 | 1.31 : 1 |
+|         |          |  6  | 86.3 | 10.2 | 45.3 | 17.3 |  7.8 | 1.30 : 1 |
+|_________|__________|_____|______|______|______|______|______|__________|
+
+The variations exhibited by these numbers are significant. It is clear,
+on the other hand, that the assimilation of the furfuroids does not vary
+in any important way with variations in conditions of atmosphere and
+soil nutrition. They are essentially _tissue_-constituents, and only at
+the flowering period is there any accumulation of these compounds in the
+alkali-soluble form. It has been previously shown (ibid. 27, 1061)
+that the proportion of furfuroids in the straw-celluloses of the
+paper-maker differs but little from that of the original straws. For the
+isolation of the celluloses the straws are treated by a severe process
+of alkaline hydrolysis, to which, therefore, the furfuroid groups offer
+equal resistance with the normal hexose groups with which they are
+associated in the complex.
+
+The furfuroids of the cereal straws are therefore not pentosanes. They
+are original products of assimilation, and not subject to secondary
+changes after elaboration such as to alter either their constitution or
+their relationship to the normal hexose groups of the tissue-complex.
+
+
+(1) CONSTITUTION OF THE CEREAL CELLULOSES
+
+(Chem. Soc. J. 1896, 804).
+
+
+(2) THE CARBOHYDRATES OF BARLEY STRAW
+
+(Chem. Soc. J. 1896, 1604).
+
+
+(3) THE CARBOHYDRATES OF THE CEREAL
+
+STRAWS (Chem. Soc. J. 1897, 1001).
+
+
+(4) THE CARBOHYDRATES OF BARLEY STRAW
+
+(Chem. Soc. J. 1898, 459).
+
+C. F. CROSS, E. J. BEVAN, and CLAUD SMITH.
+
+These are a series of investigations mainly devoted to establishing the
+identity of the furfural-yielding group which is a characteristic
+constituent.
+
+This 'furfuroid' while equally resistant to alkalis as the normal
+cellulose group with which it is associated, is selectively hydrolysed
+by acids. Thus straw cellulose dissolves in sulphuric acids of
+concentration H_{2}SO_{4}.2H_{2}O - H_{2}SO_{4}.3H_{2}O, and on diluting
+the normal cellulose is precipitated as a hydrate, and the furfuroid
+remains in solution. But this sharp separation is difficult to control
+in mass. By heating with a very dilute acid (1 p.ct. H_{2}SO_{4}) the
+conditions are more easily controlled, the most satisfactory results
+being obtained with 15 mins. heating at 3 atm. pressure.
+
+(1) Operating in this way upon brewers' grains the furfuroid was
+obtainable as the chief constituent of a solution for which the
+following experimental numbers were determined:--Total dissolved solids,
+28.0 p.ct. of original 'grains'; furfural, 39.5 p.ct. of total dissolved
+solids, as compared with 12.5 p.ct. of total original grains; cupric
+reduction (calc. to total solids), 110 (dextrose = 100) osazone; yield
+in 3 p.ct. solution, 35 p.ct. of weight of total solids.
+
+                                  Pentosazone
+     Analysis       N  17.1  17.3    17.07
+                    C  62.5  62.3    62.2
+                    H   6.4   6.5     6.1
+     Melting-point                146�-153�
+
+From these numbers it is seen that of the total furfuroids of the
+original 'grains' 84 p.ct. are thus obtained in solution in the fully
+hydrolysed form, which is that of a pentose or pentose derivative. It
+was, however, found impossible to obtain any crystallisation from the
+neutralised (BaCO_{3}) and concentrated solution, the syrup being kept
+for some weeks in a desiccator. It was noted at the same time that the
+colour reaction of the original solution with phloroglucol and
+hydrochloric acid was a deep violet, in contradistinction to the
+characteristic red of the pentoses. On oxidation with hydrogen peroxide,
+in the proportion of 1 mol. H_{2}O_{2} to 1 mol. of the carbohydrate in
+solution, carbonic anhydride was formed in quantity = 20.0 p.ct. of the
+latter.
+
+Fermentation (yeast) experiments also showed a divergence from the
+resistant behaviour of the pentoses, a considerable proportion of the
+furfuroid disappearing in a normal fermentation.
+
+(2) The quantitative methods above described were employed in
+investigating the barley plant at different stages of its growth. The
+green plant was extracted with alcohol, the residue freed from alcohol
+and subjected to acid hydrolysis.
+
+The hydrolysed extract was neutralised and fermented. In the early
+stages of growth the furfuroids were completely fermented, i.e.
+disappeared in the fermentation. In the later stages this proportion
+fell to 50 p.ct. In the earlier stages, moreover, the normal hexose
+constituents of the permanent tissue were hydrolysed in large proportion
+by the acid, whereas in the matured straw the hydrolysis is chiefly
+confined to the furfuroids. In the early stages also the permanent
+tissue yields an extract with relatively low cupric reduction, showing
+that the carbohydrates are dissolved by the acid in a more complex
+molecular condition.
+
+These observations confirm the view that the furfuroids take origin in a
+hexose-pentose series of transformations. The proportion of furfuroid
+groups to total carbohydrates varies but little, viz. from 1/3 in the
+early stages to a maximum of 1/4 at the flowering period. At this period
+the differentiation of the groups begins to be marked.
+
+Taking all the facts of (1) and (2), they are not inconsistent with the
+hypothesis of an internal transformation of a hexose to a
+pentose-monoformal. Such a change of position and function of oxygen
+from OH to CO within the group --CH.OH-- is a species of internal
+oxidation which reverses the reduction of formaldehyde groups in
+synthesising to sugars, and appears therefore of probable occurrence.
+
+These constitutional problems are followed up in (3) by the indirect
+method of differentiating the relationships of these furfuroids to yeast
+fermentation, from those of the pentoses. Straw and esparto celluloses
+are subjected to the processes of acid hydrolysis, and the neutralised
+extracts fermented. With high furfural numbers indicating that the
+furfuroids are the chief constituents of the extract, there is an active
+fermentation with production of alcohol. The cupric reduction falls in
+greater ratio to the original (unfermented) than the furfural.
+Observations on the pure pentoses--xylose and arabinose added to
+dextrose solutions, and then exposed to yeast action--show that in a
+vigorous fermentation not unduly prolonged the pentoses are unaffected,
+but that they do come within the influence of the yeast-cell when the
+latter is in a less vigorous condition, and when the hexoses are not
+present in relatively large proportion.
+
+(4) The observations on the growing plant were resumed with the view of
+artificially increasing the differentiation of the two main groups of
+carbohydrates. From a portion of a barley crop the inflorescence was
+removed as soon as it appeared. The crop was allowed to mature, and a
+full comparison instituted between the products of normal and abnormal
+growth. With a considerable difference in 'permanent tissue' (13 p.ct.
+less) and a still greater defect in cellulose (24 p.ct.), the constants
+for the furfuroids in relation to total carbohydrates were unaffected by
+the arrested development. This was also true of the behaviour of the
+hydrolysed extracts (acid processes) to yeast fermentation.
+
+(5) The extract obtained from the brewers' grains by the process
+described in (2) was investigated in relation to animal digestion. It
+has been now generally established that the furfuroids as constituents
+of fodder plants are digested and assimilated in large proportion in
+passing through animal digestive tracts, and in this respect behave
+differently from the pentoses. The furfuroids being obtained, as
+described, in a fully hydrolysed condition (monoses) the digestion
+problem presented itself in a new aspect, and was therefore attacked.
+
+The result of the comparative feeding experiments upon rabbits was to
+show that in this previously hydrolysed form the furfuroids are almost
+entirely digested and assimilated, no pentoses, moreover, appearing in
+the urine.
+
+Generally we may sum up the present solution of the problem of the
+relationship of the furfuroids to plant assimilation and growth as
+follows:--The pentoses are not produced as such in the process of
+assimilation; but furfural-yielding carbohydrates are produced directly
+and in approximately constant ratio to the total carbohydrates; they are
+mainly located in the permanent tissue; in the secondary changes of
+dehydration, &c., accompanying maturation they undergo such
+differentiation that they become readily separable by processes of acid
+hydrolysis from the more resistant normal celluloses; but in relation to
+alkaline treatments they maintain their intimate union with the latter.
+They are finally converted into pentoses by artificial treatments, and
+into pentosanes in the plant, with loss of 1 C atom in an oxidised form.
+The mechanism of this transformation of hexoses into pentoses is not
+cleared up. It is independent of external conditions, e.g.
+fertilisation and atmospheric oxidations, and is probably therefore a
+process of internal rearrangement of the character of an oxidation.
+
+
+ZUR KENNTNISS DER IN DEN MEMBRANEN DER PILZE ENTHALTENEN BESTANDTHEILE.
+
+E. WINTERSTEIN (Ztschr. Physiol. Chem., 1894, 521; 1895, 134).
+
+~ON THE CONSTITUENTS OF THE TISSUE OF FUNGI.~
+
+(p. 87) These two communications are a contribution of fundamental
+importance, and may be regarded as placing the question of the
+composition of the celluloses of these lowest types on a basis of
+well-defined fact. In the first place the author gives an exhaustive
+bibliography, beginning with the researches of Braconnot (1811), who
+regarded the cellular tissue of these organisms as a specialised
+substance, which he termed 'fungin.' Payen rejects this view, and
+regards the tissue, fully purified by the action of solvents, as a
+cellulose (C_{6}H_{10}O_{5}). This view is successively supported by
+Fromberg [Mulder, Allg. Phys. Chem., Braunschweig, 1851], Schlossberger
+and Doepping [Annalen, 52, 106], and Kaiser. De Bary, on a review of the
+evidence, adopts this view, but, as the purified substance fails to give
+the characteristic colour-reactions with iodine, he uses the qualifying
+term 'pilzcellulose' [Morph. u. Biol. d. Pilze u. Flechten, Leipzig,
+1884].
+
+C. Richter, on the other hand, shows that these reactions are merely a
+question of methods of purification or preparation [Sitzungsber. Acad.
+Wien, 82, 1, 494], and considers that the tissue-substance is an
+ordinary cellulose, with the ordinary reactions masked by the presence
+of impurities. In regard to the lower types of fungoid growth, such as
+yeast, the results of investigators are more at variance. The researches
+of Salkowski (p. 113) leave little doubt, however, that the
+cell-membrane is of the cellulosic type.
+
+The author's researches extend over a typical range of products obtained
+from _Boletus edulis, Agaricus campestris, Cantharellus cibarius,
+Morchella esculenta, Polyporus officinalis, Penicillium glaucum_, and
+certain undetermined species. The method of purification consisted
+mainly in (a) exhaustive treatments with ether and boiling alcohol,
+(b) digestion with alkaline hydrate (1-2 p.ct. NaOH) in the cold,
+(c) acid hydrolysis (2-3 p.ct. H_{2}SO_{4}) at 95�-100�, followed by a
+chloroxidation treatment by the processes of Schulze or Hoffmeister, and
+final alkaline hydrolysis.
+
+The products, i.e. residues, thus obtained were different in essential
+points from the celluloses isolated from the tissues of phanerogams
+similarly treated. Only in exceptional cases do they give blue reactions
+with iodine in presence of zinc chloride or sulphuric acid. The
+colourations are brown to red. They resist the action of cuprammonium
+solutions. They are for the most part soluble in alkaline hydrate
+solution (5-10 p.ct. NaOH) in the cold. They give small yields (1-2
+p.ct.) of furfural on boiling with 10 p.ct. HCl.Aq.
+
+Elementary analyses gave the following results, which are important in
+establishing the presence of a notable proportion of nitrogen, which has
+certainly been overlooked by the earlier observers:--
+
+ _________________________________________________________
+|                                      |      |     |     |
+|     'Cellulose' or residue from      |  C   |  H  |  N  |
+|______________________________________|______|_____|_____|
+|                                      |      |     |     |
+| Boletus edulis (Schulze process)     | 42.4 | 6.5 | 3.9 |
+| Boletus edulis (Hoffmeister process) | 44.6 | 6.3 | 3.6 |
+| Polyporus off.                       | 43.7 | 6.5 | 0.7 |
+| Cantharellus cib.                    | 44.9 | 6.8 | 3.0 |
+| Agaricus campestris                  | 44.3 | 6.6 | 3.6 |
+| Botrytis                             | 42.1 | 6.3 | 3.9 |
+| Penicillium glaucum                  |      |     | 3.3 |
+| Morchella esculenta                  |      |     | 2.5 |
+|______________________________________|______|_____|_____|
+
+It is next shown that this residual nitrogen is not in the form of
+residual proteids (1) by direct tests, all of which gave negative
+results, and (2) indirectly by the high degree of resistance to both
+alkaline and acid hydrolysis. The 'celluloses' are attacked by boiling
+dilute acids (1 p.ct. H_{2}SO_{4}), losing in weight from 10 to 23
+p.ct., the dissolved products having a cupric reduction value about 50
+p.ct. that of an equal weight of dextrose. As an extreme hydrolytic
+treatment the products were dissolved in 70 p.ct. H_{2}SO_{4}, allowed
+to stand 24 hours, then considerably diluted (to 3 p.ct. H_{2}SO_{4})
+and boiled to complete the inversion. The yields of glucose, calculated
+from the cupric reduction, were as follows:--
+
+     Boletus edulis       65.2 p.ct.
+     Polyporus off.       94.7   "
+     Agaricus campestris  59.1   "
+     Morchella esculenta  60.1   "
+     Cantharellus cib.    64.9   "
+     Botrytis             60.8   "
+
+It will be noted that the exceptionally high yield from the Polyporus
+cellulose is correlated with its exceptionally low nitrogen. By actual
+isolation of a crystalline dextrorotary sugar, by preparations of
+osazone and conversion into saccharic acid, it was proved that dextrose
+was the main product of hydrolysis. The second main product was shown to
+be acetic acid, the yield of which amounted to 8 p.ct. in several cases.
+
+Generally, therefore, it is proved that the more resistant tissue
+constituents of the fungi are not cellulose, but a complex of
+carbohydrates and nitrogenous groups in combination, the former being
+resolved into glucoses by acid hydrolysis, and the latter yielding
+acetic acid as a characteristic product of resolution together with the
+nitrogenous groups in the form of an uncrystallisable syrup.
+
+In the further prosecution of these investigations (2) the author
+proceeded from the supposition of the identity of the nitrogenous
+complex of the original with chitin, and adopted the method of
+Ledderhose (Ztschr. Physiol. Chem. 2, 213) for the isolation of
+glucosamin hydrochloride, which he succeeded in obtaining in the
+crystalline form. In the meantime E. Gilson had shown that these tissue
+substances in 'fusion' with alkaline hydrates yield a residue of a
+nitrogenous product (C_{14}H_{28}N_{2}O_{10}), which is soluble in
+dilute acids [Recherches Chim. sur la Membrane Cellulaire des
+Champignons, La Cellule, v. II, pt. 1]. This residue, which was termed
+mycosin by Gilson, has been similarly isolated by the author. It is
+proved, therefore, that the tissues of the fungi do contain a product
+resembling chitin. [See also Gilson, Compt. Rend. 120, 1000.] This
+constituent is in intimate union with the carbohydrate complex, which is
+resolved similarly to the hemicelluloses. Various intermediate terms of
+the hydrolytic series have been isolated. But the only fully identified
+product of resolution is the dextrose which finally results.
+
+
+UEBER DIE KOHLENHYDRATE D. HEFE.
+
+E. SALKOWSKI (Berl. Ber., 27, 3325).
+
+~ON THE CARBOHYDRATES OF YEAST.~
+
+The author has isolated the more resistant constituents of the
+cell-membrane by boiling with dilute alkalis, and exhaustively purifying
+with alcohol and ether.
+
+The residue was only a small percentage (3-4 p.ct) of the original, and
+retained only 0.45 p.ct. N.
+
+It was heated in a digester with water at 2-3 atm. steam-pressure, and
+thus resolved into approximately equal portions of soluble cellulose
+(a) and insoluble (b). The latter, giving no colour-reaction with
+iodine, is termed achroocellulose; the former reacts, and is therefore
+termed erythrocellulose. The former is easily separated from its
+opalescent solution. It has the empirical composition of cellulose. In
+the soluble form it resembles glycogen. The achroocellulose is isolated
+in the form of horny or agglomerated masses. It appears to be resolved
+by ultimate hydrolysis into dextrose and mannose.
+
+
+
+
+SECTION V. FURFUROIDS, i.e. PENTOSANES AND FURFURAL-YIELDING
+CONSTITUENTS GENERALLY
+
+
+(1) ~Reactions of the Carbohydrates with Hydrogen Peroxide.~
+
+C. F. CROSS, E. J. BEVAN, and CLAUD SMITH (J. Chem. Soc., 1898, 463).
+
+
+(2) ~Action of Hydrogen Peroxide on Carbohydrates in the Presence of
+Ferrous Salts.~
+
+R. S. MORRELL and J. M. CROFTS (J. Chem. Soc., 1899, 786).
+
+
+(3) ~Oxidation of Furfuraldehyde by Hydrogen Peroxide.~
+
+C. F. CROSS, E. J. BEVAN, and T. HEIBERG (J. Ch. Soc., 1899, 747).
+
+
+(4) EINWIRKUNG VON WASSERSTOFFHYPEROXID AUF UNGES�TTIGTE
+KOHLENWASSERSTOFFE.
+
+C. F. CROSS, E. J. BEVAN, and T. HEIBERG (Berl. Ber., 1900, 2015).
+
+~ACTION OF HYDROGEN PEROXIDE ON UNSATURATED HYDROCARBONS.~
+
+The above series of researches grew out of the observations incidental
+to the use of the peroxide on an oxidising agent in investigating the
+hydrolysed furfuroids (102). Certain remarkable observations had
+previously been made by H. J. H. Fenton (Ch. Soc. J., 1894, 899; 1895,
+774; 1896, 546) on the oxidation of tartaric acid by the peroxide,
+acting in presence of ferrous salts, the --CHOH--CHOH-- residue losing
+H_{2} with production of the unsaturated group, --OH.C=C.OH--. These
+investigations have subsequently been considerably developed and
+generalised by Fenton, but as the results have no immediate bearing on
+our main subject we must refer readers to the J. Chem. Soc., 1896-1900.
+
+From the mode of action diagnosed by Fenton it was to be expected that
+the CHOH groups of the carbohydrates would be oxidised to CO groups, and
+it has been established by the above investigations (1) and (2) that the
+particular group to be so affected in the hexoses is that contiguous to
+the typical
+
+        |
+     --CO
+
+group. There results, therefore, a dicarbonyl derivative ('osone'),
+which reacts directly with 2 mol. phenyl hydrazine in the cold to form
+an osazone. This was directly established for glucose, l�vulose,
+galactose, and arabinose (2). While this is the main result, the general
+study of the product shows that the oxidation is not simple nor in
+direct quantitative relationship to the H_{2}O_{2} employed. The
+molecular proportion of the aldoses affected appears to be in
+considerable excess, and the reaction is probably complicated by
+interior rearrangement.
+
+In the main, the original aldehydic group resists the oxidation. But a
+certain proportion of acid products are formed, probably tartronic acid.
+On distillation with condensing acids a large proportion of volatile
+monobasic acids (chiefly formic) are obtained. The proportion of
+furfural obtained amounts to 3-4 per cent. of the weight of the original
+carbohydrate.
+
+Since the general result of these oxidations is the substitution of an
+OH group for an H atom, it was of interest to determine the behaviour of
+furfural with the peroxide. The oxidation was carried out in dilute
+aqueous solution of the aldehyde at 20�-40�, using 2-3 mols. H_{2}O_{2}
+per 1 mol. C_{5}H_{4}O_{2}. The main product is a hydroxyfurfural, which
+was separated as a hydrazone. A small quantity of a monobasic acid was
+formed, which was identified as a hydroxypyromucic acid. Both aldehyde
+and acid appear to be the alpha beta derivatives. The aldehyde gives
+very characteristic colour reactions with phloroglucinol and resorcinol
+in presence of hydrochloric acid, which so closely resemble those of the
+lignocelluloses that there is little doubt that these particular
+reactions must be referred to the presence of the hydroxyfurfural as a
+normal constituent.
+
+The study of these oxidations was then extended to typical unsaturated
+hydrocarbons--viz. acetylene and benzene. (4) From the former the main
+product was acetic acid, but the attendant formation of traces of ethyl
+alcohol indicates that the hydrogen of the peroxide may take a direct
+part in this and other reactions. This view receives some support from
+the fact that the interaction of the H_{2}O_{2} with permanganates has
+now been established to be an oxidation of the H_{2} of the peroxide by
+the permanganate oxidation, with liberation, therefore, of the O_{2} of
+the peroxide as an unresolved molecule [Baeyer].
+
+Benzene itself is also powerfully attacked by the peroxide when shaken
+with a dilute solution in presence of iron salts. The products are
+phenol and pyrocatechol, with some quantity of an amorphous product
+probably formed by condensation of a quinone with the phenolic products
+of reaction.
+
+       *       *       *       *       *
+
+These types of oxidation effects now established give a definite
+significance to the physiological functions of the peroxide, which is a
+form of 'active oxygen' of extremely wide distribution. It would have
+been difficult _a priori_ to devise an oxidant without sensible action
+on aldehydic groups, yet delivering a powerful attack on hydrocarbon
+rings; or to have suggested a synthesis of the sugars from tartaric acid
+with a powerful oxidising treatment as the first and essential stage in
+the transformation.
+
+Our present knowledge of such actions and effects suggests a number of
+new clues to genetic relationships of carbon compounds within the plant.
+The conclusion is certainly justified that the origin of the pentoses is
+referable to oxidations of the hexoses, in which this form of 'active
+oxygen' plays an important part.
+
+We must note here the researches of O. Ruff, who has applied these
+oxidations with important results in the systematic investigation of the
+carbohydrates.
+
+
+UEBER DIE VERWANDLUNG DER _D_-GLUCONS�URE IN _D_-ARABINOSE (Berl. Ber.,
+1898, 1573).
+
+~CONVERSION OF _D_-GLUCONIC ACID INTO _D_-ARABINOSE.~
+
+       *       *       *       *       *
+
+_D_ UND _L_ ARABINOSE (_Ibid._ 1899, 550).
+
+       *       *       *       *       *
+
+ZUR KENNTNISS DER OXYGLUCONS�URE (_Ibid._ 1899, 2269).
+
+~ON OXYGLUCONIC ACID.~
+
+Ruff in these researches has realised a simple and direct transition
+from the hexoses to the pentoses. By oxidising gluconic acid with the
+peroxide the beta --CHOH-- group is converted into carbonyl at the same
+time that the terminal COOH [alpha] is oxidised to CO_{2}. The yields of
+the resulting pentose are large. Simultaneously there is formed an
+oxygluconic acid, which appears to be a ketonic acid of formula
+--CH_{2}OH.CO.(CHOH)_{3}.COOH--.
+
+From these results we see a further range of physiological
+probabilities; and with the concurrent actions of oxygen in the forms of
+or related to hydrogen peroxide on the one side, and ozone on the other,
+we are able to account in a simple way for the relationships of the
+'furfuroid' group, which may include a number of intermediate terms in
+the hexose-pentose series.
+
+Following in this direction of development of the subject is a study of
+the action of persulphuric acid upon furfural.
+
+
+EINWIRKUNG DES CARO'SCHEN REAGENS AUF FURFURAL.
+
+C. F. CROSS, E. J. BEVAN, and J. F. BRIGGS (Berl. Ber., 1900, 3132).
+
+Regarding this reagent as another form of 'active oxygen,' it is
+important to contrast its actions with those of the hydrogen peroxide.
+Instead of the beta-hydroxyfurfural (_ante_, 115) we obtain the
+delta-aldehyde as the first product. The aldehydic group is then
+oxidised, and as a result of attendant hydrolysis the ring is broken
+down and succinic acid is formed, the original aldehydic group of the
+furfural being split off in the form of formic acid. The reactions take
+place at the ordinary temperature and with the dilute form of the
+reagent described by Baeyer and Villiger (Ber. 32, 3625). These results
+have some special features of interest. The alpha delta-hydroxyfurfural
+has similar colour reactions to those of the alpha beta-derivative, and
+may also therefore be present as a constituent of the lignocelluloses.
+The tendency to attack in the 1�4 position in relation to an aldehydic
+group further widens the capabilities of 'active oxygen' in the plant
+cell. Lastly, this is the simplest transition yet disclosed from the
+succinyl to furfural grouping, being effected by a regulated proportion
+of oxygen, and under conditions of reaction which may be described as of
+the mildest. In regard to the wide-reaching functions of asparagin in
+plant life, we have a new suggestion of genetic connections with the
+furfuroids.
+
+
+VERGLEICH DER PENTOSEN-BESTIMMUNGSMETHODEN VERMITTELST PHENYLHYDRAZIN
+UND PHLOROGLUCIN.
+
+M. KR�GER (Inaug.-Diss., G�ttingen, 1895).
+
+~COMPARISON OF METHODS OF ESTIMATING FURFURAL AS HYDRAZONE AND
+PHLOROGLUCIDE.~
+
+The author traces the development of processes of estimating furfural
+(1) by precipitation with ammonia (furfuramide), (2) by volumetric
+estimation with standardised phenylhydrazine, (3) by weighing the
+hydrazone.
+
+In 1893 (Chem. Ztg. 17, 1745) Hotter described a method of quantitative
+condensation with pyrogallol requiring a temperature of 100�-110� for
+two hours. The insoluble product collected, washed, dried at 103�, and
+weighed, gives a weight of 1.974 grm. per 1 grm. furfural.
+
+Councler substitutes phloroglucinol for pyrogallol, with the advantage
+of doing away with the digestion at high temperature. (_Ibid._ 18, 966.)
+This process, requiring the presence of strong HCl, has the advantage of
+being applied directly to the acid distillate, in which form furfural is
+obtained as a product of condensation of pentoses, &c. A comparative
+investigation was made, precipitating furfural (a) as hydrazone in
+presence of acetic acid, and (b) as phloroglucide in presence of HCl
+(12 p.ct). In (a) by varying the weights of known quantities of
+furfural, and using the factor, hydrazone � 0.516 [+ 0.0104] in
+calculating from the weights of precipitates obtained, the maximum
+variations from the theoretical number were +1.71 and -1.74. In (b) it
+was found necessary to vary the factor from 0.52 to 0.55 in calculating
+from phloroglucide to furfural. The greatest _total_ range of variation
+was found to be 2.5 p.ct. The phenol process is therefore equally
+accurate, has the advantages above noted, and, in addition, is less
+liable to error from the pressure in the distillates obtained from
+vegetable substances of volatile products, e.g. ketonic compounds,
+accompanying the furfural.
+
+This method has been criticised by Helbel and Zeisel [Sitz.-ber, Wiener
+Akad. 1895, 104, ii. p. 335] on two grounds of error, viz. (1) the
+presence of diresorcinol in all ordinary preparations of phloroglucinol,
+and (2) changes in weight of the precipitate of phloroglucide on drying.
+The process was carried out comparatively with ordinary preparations,
+and with specially pure preparations of the phenol. The quantitative
+results were identical. The criticisms in question are therefore
+dismissed. Although the process is to be recommended for its simplicity
+and the satisfactory concordance of results it is to be noted that it
+rests upon an empirical basis, since the phloroglucide is not formed by
+the simple reaction 2 [C_{5}H_{4}O_{2} + C_{6}H_{6}O_{3}] - H_{2}O =
+C_{22}H_{18}O_{9}, but appears to have the composition
+C_{16}H_{12}O_{6}.
+
+In part ii. of this paper the author discusses the question of the
+probable extent in the sense of diversity of constitution of
+furfural-yielding constituents of plant-tissues. Glucoson was isolated
+from glucosazon, and found to yield 2.9-3.6 p.ct. furfural. Gluconic
+acid distilled with hydrochloric acid gave traces of furfural; so also
+with sulphuric acid and manganic oxide.
+
+Starch was oxidised with permanganate, and a mixture of products
+obtained of which one gave a characteristic violet colouration with
+phloroglucol, with an absorption-band at the D line. On distilling with
+HCl furfural was obtained in some quantity. The product in question was
+found to be very sensitive to the action of bases, and was destroyed by
+the incidental operation of neutralising the mixture of oxidised
+products with calcium carbonate. It was found impossible to isolate the
+compound.
+
+
+UNTERSUCHUNGEN UEBER DIE PENTOSANBESTIMMUNG MITTELST DER
+SALZS�URE-PHLORO-GLUCIN-METHODE.[8]
+
+E. KR�BER (Journ. f. Landwirthschaft, 1901, 357).
+
+~INVESTIGATION OF THE HYDROCHLORIC ACID-PHLOROGLUCINOL METHOD OF
+DETERMINING PENTOSANES.~
+
+This paper is the most complete investigation yet published of the now
+well-known method of precipitating and estimating furfural in acid
+solution by means of the trihydric phenol. In the last section of the
+paper is contained the most important result, the proof that the
+insoluble phloroglucide is formed according to the reaction
+
+     C_{5}H_{4}O_{2} + C_{6}H_{6}O_{3} - 2H_{2}O = C_{11}H_{6}O_{3},
+
+also, by varying the proportions of the pure reagents interacting, that
+the condensation takes place invariably according to this equation.
+
+Incidentally the following points were also established:--The solubility
+of the phloroglucide, under the conditions of finally separating in a
+condition for drying and weighing, is 1 mgr. per 100 c.c. of total
+solution, made up of the original acid solution, in which the
+precipitation takes place, and the wash-water required to purify from
+the acid. The phloroglucide is hygroscopic, and must be weighed out of
+contact with the air. The presence of diresorcinol is without influence
+on the result, provided a sufficient excess of actual phloroglucinol is
+employed. Thus even with a preparation containing 30 p.ct. of its weight
+of diresorcinol the influence of the latter is eliminated, provided a
+weight be taken equal to twice that of the furfural to be precipitated.
+The phenol must be perfectly dissolved by warming with dilute HCl (1.06
+sp.gr.) before adding to the furfural solution. For collecting the
+precipitate of phloroglucide the author employs the Gooch crucible.
+
+The paper contains a large number of quantitative results in proof of
+the various points established, and concludes with elaborate tables,
+giving the equivalents in the known pentoses and their anhydrides for
+any given weight of phloroglucide from 0.050 to 0.300 grm.
+
+
+UEBER DEN PENTOSAN-GEHALT VERSCHIEDENER MATERIALIEN.
+
+B. TOLLENS and H. GLAUBITZ (J. f�r Landwirthschaft, 1897, 97).
+
+~ON THE PENTOSANE CONSTITUENTS OF FODDER-PLANTS AND MALT.~
+
+(p. 171) (a) The authors have re-determined the yield of furfural from
+a large range of plant-products, using the phloroglucol method. The
+numbers approximate closely to those obtained by the hydrazone method.
+The following may be cited as typical:
+
+     Substance              Furfural p.ct.
+
+     Rye (G�ttingen)            6.03
+     Wheat (square head)        4.75
+     Barley (peacock)           4.33
+     Oats (G�ttingen)           7.72
+     Maize (American)           3.17
+     Meadow hay                11.63
+     Bran (wheat)              13.06
+     Malt                       6.07
+     Malt-sprouts               8.56
+     Sugar-beet (exhausted)    14.95
+
+(b) A comparison of wheat with wheat bran, &c. was made by grinding in
+a mortar and 'bolting' the flour through a fine silk sieve. The results
+showed:
+
+                              Furfural p.ct.
+     Original wheat               4.75
+     Fine flour                   1.73
+     Bran (24 p.ct. of wheat)    11.25
+     Wheat-bran of commerce      13.06
+
+It is evident that the pentosanes of wheat are localised in the more
+resistant tissues of the grain.
+
+(c) An investigation of the products obtained in the analytical
+process for 'crude fibre' gave the following:
+
+(1) In the case of brewers' grains:
+
+     100 grms. grains       gave furfural   = 29.43 pentosane
+                                              ---------------
+      20   "   crude fibre       "          =  2.52
+     Acid extract                "          = 22.76
+     Alkali  "                   "          =  1.20
+     Deficiency from total of original grains  2.95
+                                              -----
+
+                                              29.43
+
+(2) In the case of meadow hay:
+
+The crude fibre (30 p.ct.) obtained retained about one fourth (23.63
+p.ct.) of the total original pentosanes.
+
+(d) An investigation of barley-malt, malt-extract or wort, and
+finished beer showed the following: An increase of furfuroids in the
+process of malting, 100 pts. barley with 7.97 of 'pentosane' yielding 82
+of malt with 11.18 p.ct. 'pentosane'; confirming the observations of
+Cross and Bevan (Ber. 28, 2604). Of the total furfuroids of malt about
+1/4 are dissolved in the mashing process. In a fermentation for lager
+beer it was found that about /10 of the total furfuroids of the malt
+finally survive in the beer; the yield of furfural being 2.92 p.ct. of
+the 'total solids' of the beer. In a 'Schlempe' or 'pot ale,' from a
+distillery using to 1 part malt 4 parts raw grain (rye), yield of
+furfural was 9 p.ct. of the total solids.
+
+In a general review of the relationships of this group of plant-products
+it is pointed out that they are largely digested by animals, and
+probably have an equal 'assimilation' value to starch. They resist
+alcoholic fermentation, and must consequently be taken into account as
+constituents of beers and wines.
+
+
+UEBER DAS VERHALTEN DER PENTOSANE DER SAMEN BEIM KEIMEN.[9]
+
+A. SCH�NE and B. TOLLENS (Jour. f. Landwirthschaft, 1901, 349).
+
+~BEHAVIOUR OF PENTOSANES OF SEEDS IN GERMINATION.~
+
+The authors have investigated the germination of barley, wheat, and
+peas, in absence of light, and generally with exclusion of assimilating
+activity, to determine whether the oxidation with attendant loss of
+weight, which is the main chemical feature of the germination proper,
+affects the pentosanes of the seeds. The following are typical of the
+quantitative results obtained, which are stated in absolute weights, and
+not percentages.
+
+ _____________________________________________________________
+|        |               |                    |               |
+|        | Original seed |      Malt or       | Pentosane in  |
+|        |               | germinated product |               |
+|        |               |                    |_______________|
+|        |               |                    |       |       |
+|        |      A        |         B          |   A   |   B   |
+|________|_______________|____________________|_______|_______|
+|        |               |                    |       |       |
+| Barley |    500.00     |       434.88       | 39.58 | 40.38 |
+|   "    |    500.00     |       442.26       | 40.52 | 41.17 |
+| Peas   |    300.00     |       286.60       | 15.25 | 15.97 |
+|________|_______________|____________________|_______|_______|
+
+The authors conclude generally that there is a slight absolute increase
+in the pentosanes, and that the pentosanes do not belong to those
+reserve materials which undergo destructive oxidation during
+germination.
+
+In this they confirm the previously published results of De Chalmot,
+Cross and Bevan, and Gotze and Pfeiffer.
+
+
+UEBER DEN GEHALT DER BAUMWOLLE AN PENTOSAN.
+
+H. SURINGAR and B. TOLLENS (Ztschr. angew. Chem., 1897, I).
+
+~PENTOSANE CONSTITUENTS OF COTTON.~
+
+(p. 290) It has been stated by Link and Voswinkel (Pharm. Centralhalle,
+1893, 253), that raw cotton yields 'wood gum' as a product of
+hydrolysis. The authors were unable to obtain any pentoses as products
+of acid hydrolysis of raw cotton, and traces only of furfural-yielding
+carbohydrates. They conclude that raw cotton contains no appreciable
+quantity of pentosane.
+
+FOOTNOTES:
+
+[8] This paper appears during the printing of the author's original MS.
+
+[9] This paper appears during the printing of the author's original MS.
+
+
+
+
+SECTION VI. THE LIGNOCELLULOSES
+
+
+(p. 131) ~Lignocellulose Esters.~--By a fuller study of the ester
+reactions of the normal celluloses we have been able to throw some light
+on the constitutional problems involved; and we have extended the
+investigations to the jute fibre as a type of the lignocelluloses, from
+the results of which we get a clearer idea of the relationships of the
+constituent groups.
+
+Taking the empirical expression for the complex, i.e. the entire
+lignocellulose, the formula C_{12}H_{18}O_{9}, we shall be able to
+compare the ester derivatives with those of the celluloses, which we
+have also referred to a C_{12} unit. But we shall require also to deal
+with the constituent groups of the complex, which for the purposes of
+this discussion may be regarded as (a) a cellulose of normal
+characteristics--cellulose alpha; (b) a cellulose yielding furfural on
+boiling with condensing acids--cellulose beta; and (c) a much
+condensed, and in part benzenoid, group which we may continue to term
+the lig_none_ group.
+
+The latter has been specially examined with regard to its proportion of
+OH groups, as a necessary preliminary to the investigation of esters, in
+producing which the entire complex is employed. It will be shown that
+the ester groups can be actually localised in various ways, as in the
+main entering the cellulose residues alpha and beta. But that the
+lignone group takes little part in the reactions may be generally
+concluded on the evidence of its non-reactivity as an isolated
+derivative, (1) By chlorination, &c. it is isolated in the form of an
+amorphous body, but of constant composition, represented by the formula
+C_{19}H_{18}Cl_{4}O_{9}. This compound, soluble in acetic anhydride, was
+boiled with it for six hours after adding fused sodium acetate, and the
+product separated by pouring into water. The dilute acid filtered from
+the product contained no hydrochloric acid nor by-products of action.
+The product showed an increase of weight of 7.5 p.ct. For one acetyl per
+1 mol. C_{19}H_{18}Cl_{4}O the calculated increase is 8.0 p.ct. It is
+evident from the nature of the derivative that this result cannot be
+further verified by the usual analytical methods. (2) The chlorinated
+derivative is entirely soluble in sodium sulphite solution. This
+solution, shaken with benzoyl chloride, with addition of sodium hydrate
+in successive portions, shows only a small formation of insoluble
+benzoate, which separates as a tarry precipitate. (3) The empirical
+formula of the lignone complex in its isolated forms indicates that very
+little hydrolysis occurs in the processes of isolation. Thus the
+chlorinated product we may assume to be derived from the complex
+C_{19}H_{22}O_{9}. In the soluble by-products from the bisulphite
+processes of pulping wood the lignone exists as a sulphonated
+derivative, C_{24}H_{23}(OCH_{3})_{2}.(SO_{3}H).O_{7}. The original
+lignone may be regarded as passing into solution as a still condensed
+complex derived from C_{24}H_{26}O_{12} (Tollens). There is evidently
+little attendant hydroxylation, and another essential feature is the
+small molecular proportion of groups showing the typical sulphonation.
+
+It appears that in the lignone the elements are approximately in the
+relation C_{6} : H_{6} : O_{3}, and it may assist this discussion to
+formulate the main constitutional types consistent with this ratio,
+viz.:
+
+     (1) The trihydroxybenzenes C_{6}H_{3}(OH)_{3}.
+
+     (2) Methylhydroxyfurfural C_{5}H_{2}O.(OH)(CH_{3}).
+
+                                  (CH_{3})
+                                 /        \
+     (3) Methylhydroxypyrone CO<C_{4}H_{2} O
+                                 \        /
+                                    (OH)
+
+                             __________________
+                            |                  |
+     (4) Trioxycyclohexane CH--CH--CH--CH--CH--CH
+                            \   /   \   /   \   /
+                              O       O       O
+
+It is probable that all these types of condensation are represented in
+the lignone molecules, since the derivatives yielded in decompositions
+of more or less regulated character are either directly derived from or
+related to such groups. For the moment we pass over all but the general
+fact of complexity and the marked paucity of OH-groups. It would be of
+importance to be able to formulate the exact mode of union of the
+lignone with the cellulose residues to constitute the lignocellulose.
+The evidence, however, does not carry us farther than the probability of
+union by complicated groups and of large dimensions; for not only is the
+lignone isolated in condensed and non-hydroxylated forms, but the
+cellulose also is not hydrated or hydrolysed further than in the ratio
+3C_{6}H_{10}O_{5}.H_{2}O. It is probable, therefore, that the water
+combining with the residues at the moment of their resolution is
+relatively small.
+
+Lastly, we have to remember, when dealing with the statistical results
+of the reactions to be described, that the approximate proportions per
+cent. of the constituent groups are:
+
+     Cellulose alpha  65
+          "    beta   15  =  100 lignocellulose.
+     Lignone                  20
+
+~Jute Benzoates.~--In preparing the jute for treatment it was boiled in
+alkaline solution (1 per cent. NaOH), washed with water and dilute acid,
+again washed, dried, and weighed.
+
+In the ester reaction the reagents were employed in the proportion
+C_{12}H_{18}O_{9} : 3NaOH : 2C_{6}H_{5}COCl. A series of quantitative
+experiments gave yields of 126-130 p.ct. of benzoate [calculated for
+monobenzoate 134 p.ct.].
+
+The results were confirmed by ultimate analysis. The monobenzoate
+therefore represents a maximum, and this molecular proportion is
+one-half of that observed with the normal cellulose, calculated to the
+same unit.
+
+_Localisation of Benzoyl Group._--The entrance of the ester group
+affects the typical colour reactions of the lignocellulose, which are
+fainter. The ferric ferricyanide reaction almost disappears. The lignone
+group is unaffected, and combines with chlorine as in the original. The
+lignone chloride is removed by sodium sulphite solution, and the residue
+is a _cellulose benzoate_. The loss of weight due to the elimination of
+the lignone was 12.7 p.ct. Calculating per 100 of the original
+lignocellulose this becomes 16. These statistics further confirm the
+localisation of the benzoyl group in the cellulose residue. It is to be
+noted that the presence of the benzoyl group renders the cellulose more
+resistant to hydrolytic actions. Thus, to bring out this fact more
+prominently, we may calculate the yield of residual cellulose benzoate
+p.ct. of original jute, and we find it 109 p.ct. Taking a maximum
+proportion for original cellulose--viz. 85--this benzoate represents a
+yield of 129 p.ct., as against the theoretical for a monobenzoate, 132
+p.ct.
+
+_Furfural Numbers._--The percentage of furfural obtained by boiling with
+HCl of 1.06 sp.gr. was 3.02 and 3.29 in separate determinations.
+Calculating to the original lignocellulose, the percentage, 4.21,
+indicates a considerable loss of the furfural-yielding constituent. The
+effect was also apparent in the cellulose (benzoate) isolated by
+chlorination &c., the percentage being 1.39 p.ct., and calculated to the
+original jute benzoate 1.59 p.ct. Under the conditions adopted in
+dissolving away the chlorinated lignone the original non-benzoated
+lignocellulose would have yielded a cellulose giving 6 to 7 p.ct.
+furfural.
+
+Since the benzoyl group is hardly calculated to produce a constitutional
+change affecting the furfural constants, it was necessary to examine the
+effect of the preliminary alkaline treatment, and the change in the
+furfuroid group was in fact localised in this reaction. It was found
+that, on washing the alkali from the mercerised jute, and further
+purifying the residue, this latter yielded only 4.2 p.ct. furfural [3.4
+p.ct. on original fibre]. The alkaline solution and washings were
+acidified and distilled from 10 p.ct. HCl, yielding an additional 3.6
+p.ct. calculated to the original lignocellulose. By treatment with the
+concentrated alkali, therefore, the furfuroid of the original
+lignocellulose undergoes little change, but is selectively dissolved.
+This point is under further investigation.
+
+(p. 132) ~Acetylation of Lignocelluloses.~--Acetates are readily formed by
+boiling the lignocelluloses with acetic anhydride. The derivatives
+obtained from jute are only generally mentioned in the 1st edition (p.
+132). A further study of the reactions in regard to special points has
+led to some more definite results. The _yields_ of product by the
+ordinary and simple process are 114-115 p.ct. But on analysing the
+product an important discrepancy is revealed.
+
+For the saponification we employ a solution of sodium ethylate in the
+cold. The following numbers were obtained:
+
+                                       Acetic acid  Hydrocellulose residue
+                                           27.2            77.8
+Calc. for diacetate on C_{12}H_{18}O_{9}   30.8            78.4
+
+The derivative is approximately a diacetate, and on the assumption of a
+simple ester reaction the yield should be 127 p.ct. Assuming that the
+difference of 13 p.ct. is due to loss of water by internal condensation,
+it appears that for each acetyl group entering, 2 mol. H_{2}O are split
+off.
+
+The jute acetate showed the normal reaction with chlorine, and the
+lignone chloride was dissolved by treatment with sodium sulphite
+solution. The fibrous residue was colourless. It proved to be a
+cellulose acetate. The following numbers were obtained on
+saponification:
+
+                                          Acetic acid  Cellulose
+                                              31.6       70.0
+                                              30.9       68.8
+Calc. for diacetate on C_{12}H_{20}O_{10}     29.4       79.9
+
+The interpretation of these numbers appears to be this: in the original
+reaction with the lignocellulose it is the cellulose residue which is
+acetylated, and at the same time condensed. The cellulose residue which
+undergoes condensation is not of the normal constitution, since the
+normal cellulose is acetylated without condensation (see p. 41). On
+saponification a portion of the cellulose, in again combining with
+water, is hydrolysed to soluble products. The lignone group as it exists
+in the lignocellulose has no free OH groups, and probably no free
+aldehydic groups such as would react with the anhydride. Such groups
+may, however, be originally present, and may take part in the internal
+condensations which have been shown to occur. The furfural constants of
+the lignocellulose are unaffected by the acetylation and condensation.
+The hygroscopic moisture of the product is lowered from 10-11 p.ct. in
+the original to 4.5 p.ct. The ferric ferricyanide reaction is inhibited
+by the disappearance of the reactive groups, upon which this curious and
+characteristic phenomenon depends (1st ed.).
+
+~Acetylation of Benzoates.~--The cellulose dibenzoate (C_{12} basis) and
+the jute monobenzoate were acetylated under comparative conditions The
+results were as follows:
+
+                                                   C_{12} basis
+                                   Cellulose dibenzoate     Jute monobenzoate
+                                              Calc. for             Calc. for
+                                 Found     diacetate on  Found   diacetate on
+Ester reaction                              dibenzoate           monobenzoate
+Yield                            111 p.ct.    115 p.ct.  124 p.ct.  120 p.ct.
+
+Saponification  {Cellulose}
+                {Lignocellulose}    53.5        52.6        59.8       61.9
+                 NaOH combining     21.3        23.9        28.4       24.3
+
+From these results it would appear that the number of acetyl groups
+entering the benzoates is the same as with the unbenzoylated fibres, the
+benzoyl has no influence upon the hydroxyls as against the acetyl. At
+the same time the internal condensation noticed in the acetylation of
+the jute appears not to occur in the case of the benzoate.
+
+~Nitric Esters.~--The numbers resulting from the quantitative study of the
+ester reaction and product (1st ed. p. 133) show a very large divergence
+of the yield of product from that which would be calculated from its
+composition (N p.ct.) on the assumption that the ester reaction is
+simple. We have repeated the results, and find with a yield of 145 p.ct.
+that the product contains 11.8 p.ct. N.
+
+The reaction
+
+     C_{12}H_{18}O_{9} + 4HNO_{3} - 4H_{2}O
+
+gives a tetranitrate with 11.5 p.ct. N and a yield of 159 p.ct. The
+ester reaction, therefore, is not simple. There are two sources of the
+loss of weight. The first of these is evident from the occurrence of
+certain secondary reactions which result in the solution of a certain
+proportion of the fibre substance in the acid mixture. To determine this
+quantitatively we have devised a suitable variation of the method of
+combustion with chromic acid (1st ed.).
+
+The variation is required to meet the difficulty occasioned by the
+tension of the nitric acid and products of deoxidation. The mixed acids
+(10 c.c.), containing the organic by-products in solution, are
+carefully diluted in a small flask with an equal volume of water,
+preventing rise of temperature. Nitrous fumes are evolved during the
+dilution. Strong sulphuric acid (15 c.c.) is now added, and the residue
+of nitrous fumes expelled by a current of air, agitating the contents of
+the flask from time to time. The combustion with CrO_{3} is then
+proceeded with in the ordinary way. The gases evolved are measured
+(total volume) and calculated to C present in the form of products
+derived from the lignocellulose; and, assuming that this contains 47
+p.ct. C, we may express the result approximately in terms of the fibre
+substance. The method was controlled by blank experiments, in which
+citric acid was taken as a convenient carbon compound for combustion.
+The C found was 34.9 p.ct. as against 34.3 p.ct. calculated. By this
+method we find that with maximum yields of nitrate at 143-145 p.ct. the
+organic matter in solution in the acid mixture amounted to 4.9 to 5.3
+p.ct. of the original lignocellulose.
+
+Introducing this quantity as a correction of the yield of nitrate in the
+original reaction, we must express the 143 parts as obtained from 95 of
+fibre substance instead of 100.
+
+The yield per molecule C_{12}H_{18}O_{9} (= 306) is therefore 462,
+whereas for a tetranitrate formed by a simple ester reaction the yield
+should be 486. The difference (24) represents 1.5 mol. H_{2}O split off
+by internal condensation.
+
+The correction for total N is relatively small, raising it from 11.5 to
+12.2, which remains in close agreement with the experimental numbers.
+
+_Monobenzoate._--Treated with the acid mixture yields a mixed nitrate.
+The yield is 130 p.ct., and the product contains 7.6 p.ct. O.NO_{2}
+nitrogen. These numbers approximate to those required for reaction with
+4HNO_{3} groups, three of the residues entering the cellulose, and one
+(as NO_{2}) the benzene ring of the substituting group. For such a
+reaction the calculated numbers are: Yield 144 p.ct.; O.NO_{2} nitrogen
+7.1 p.ct.
+
+The experimental numbers require correcting for the amount of loss in
+the form of products soluble in the acid mixture, viz. 7.6 p.ct.; but
+they remain within the range of the experimental errors sufficiently to
+show that the benzoyl group limits the number of OH groups taking part
+in the ester reaction to three. The corrected yield per 1 mol. of jute
+benzoate (410) is 576, as against the calculated 590 for 4HNO_{3}
+reacting. A loss of 1H_{2}O per molecule by internal condensation is
+therefore indicated.
+
+~Denitration.~--The removal of the nitric groups from the esters is
+effected by digestion with ammonium sulphide. But the reactions are by
+no means simple. There is considerable hydrolysis of the lignocellulose
+to soluble products. Thus the _tetranitrate_ yields only 46.4 of
+denitrated fibre in place of the calculated 66. The product is a
+cellulose, yielding only 0.5 per cent. furfural. The hydrolysed
+by-products, moreover, when freed from sulphur and distilled from
+hydrochloric acid, yielded only an additional 2.5 p.ct. furfural,
+calculated to the original lignocellulose.
+
+These statistics confirm the evidence that the ester reaction is not
+simple. Such changes take place in the lignone-beta-cellulose complex
+that they revert, not to their original form, but to soluble derivatives
+of different constitution. The mixed nitrate from the benzoate is
+denitrated to a cellulose amidobenzoate, which confirms the localisation
+of a nitro-group in the benzoyl residue.
+
+(p. 157) ~General Characteristics of the Lignocelluloses.~--Later
+investigations have somewhat modified and simplified our views of the
+constitution of the typical lignocellulose (jute), so far as this can be
+dealt with by the statistics of its more important decompositions
+(original, pp. 157-161).
+
+~Cellulose.~--There is little doubt that the furfural-yielding groups of
+the original are isolated in the form of the beta-cellulose. Tollens
+emphasises this fact in his studies of cellulose-estimation methods. We
+had previously shown (original, p. 159) that the yield of furfural is
+not affected by the _chlorination_, but it appears from our numbers that
+only 50 p.ct. of these groups remain in the isolated cellulose, the
+residue undergoing hydrolysis to soluble compounds. In a carefully
+regulated hydrolysis following the chlorination it appears that the
+furfuroids are almost entirely conserved in the form of a cellulose.
+
+Moreover, an investigation of the products dissolved by sodium sulphite
+solution from the chlorinated fibre has shown that they are practically
+free from furfuroids. This enables us to exclude the furfural-yielding
+groups from the lignone complex. At the same time, through our later
+studies of the hydroxyfurfurals, it is certain that these products are
+represented in the fibre substance and probably in the lignone complex.
+
+~Chlorination Statistics.~--It has been pointed out by a correspondent--to
+whom we express our indebtedness--that we have made a mistake in
+calculating the proportion of lignone from the ratio of the Cl combining
+with the fibre substance or lignocellulose (p.ct), to that of the Cl
+_present in_ the isolated lignone chloride (p.ct.). The lignocellulose
+combines with chlorine in the ratio 100 : 8, but the lignone chloride
+_containing_ 26.7 of chlorine means that, neglecting the hydrogen
+substituted, 73 of lignone combine with the 27 of chlorine
+approximately. On the uniform percentage basis the calculated proportion
+of lignone would be 8/37, or a little over 20 p.ct.
+
+In regard to the proportion of hydration attending the resolution, we
+have shown on constitutional grounds that this must be relatively small.
+Assuming approximately the formula C_{19}H_{22}O_{9} for the lignone
+residue as it exists in combination, and the anhydride formula for the
+cellulose, these revised statistics now appear, as regards the carbon
+contents of the lignocellulose:
+
+          Cellulose, 44.4 C; lignone, 57.8.
+     80 � 44.4 � 100 = 35.52
+     20 � 57.8 � 100 = 11.56
+                       _____
+
+                       47.08 p.ct. C in lignocellulose.
+
+These conclusions are in accordance with the experimental facts, and,
+taken together with the new evidence we have accumulated from a study of
+the lignocellulose esters, we may sum up the constitutional points as
+follows: The lignocellulose is a complex of
+
+      Cellulose alpha        Cellulose beta                  Lignone
+           65 p.ct.              15 p.ct.                       20
+     Allied to the normal      Yielding furfural        One-third of which
+          celluloses         approximately 50 p.ct.      is of benzenoid
+                                                               type
+
+The lignone contains but little hydroxyl. The celluloses are in
+condensed hydroxyl union with the lignone, but the combination occurs by
+complexes of relatively large molecular weight.
+
+
+DIE CHEMIE DER LIGNOCELLULOSEN--EIN NEUER TYPUS.
+
+W. C. HANCOCK and O. W. DAHL (Berl. Ber., 1895, 1558).
+
+~Chemistry of Lignocelluloses--A New Type.~
+
+The stem of the aquatic _�schynomene aspera_ offers an exceptional
+instance of structural modification to serve the special function of a
+'float,' 1 grm. of substance occupying an apparent volume of 40-50 c.c.
+This pith-like substance is morphologically a true wood (De Bary), and
+the author's investigations now establish that it is in all fundamental
+points of chemical composition a lignocellulose, although from its
+colour reactions it has been considered by botanists to be a cellulose
+tissue containing a proportion of lignified cells. Thus the main tissue
+is stained blue by iodine in presence of hydriodic acid (1.5 s.g.), and
+the colour is not changed on washing. The ordinary lignocelluloses are
+stained a purple brown changed to brown on washing. The reactions with
+phloroglucol and with aniline salts, characteristic of these compounds,
+is only faintly marked in the main tissue, though strongly in certain
+individual cells.
+
+The following quantitative determinations, however, establish the close
+similarity of the product to the typical lignocelluloses:
+
+_Elementary Analysis._--C 46.55, H 6.7. _Furfural_ 11.6 p.ct., of which
+there remained in the residue from alkaline hydrolysis (71 p.ct.) 8.0,
+i.e. about 70 p.ct. The distribution of the furfuroids is therefore not
+affected by the alkaline treatment.
+
+_Chlorination._--The substance (after alkaline hydrolysis) takes up 16.9
+p.ct. Cl, of which approximately one-half is converted into hydrochloric
+acid.
+
+_Methoxyl._--O.CH_{3} estimated = 2.9 p.ct.
+
+_Ferric Ferricyanide Reaction._--Increase of weight due to blue cyanide
+fixed (1) 75 p.ct., (2) 96 p.ct. Ratio, Fe : CN = 1 : 2, 4.
+
+_Hydroxyl Reactions._--In the formation of nitric esters and in the
+sulphocarbonate reaction the substance gave results similar to those
+obtaining for the jute fibre.
+
+These results establish the general identity of this peculiar product of
+plant life with the lignocelluloses, at the same time that they show
+that certain of the colour reactions supposed to characterise the
+lignocelluloses are due to by-products which may or may not be present.
+
+(p. 172) ~Composition of Elder Pith.~--In a systematic investigation of
+the celluloses in relation to function we shall have to give special
+attention to the parenchymatous tissues of all kinds. These are, for
+structural reasons, not easily isolated, for which reason and their
+generally 'inferior' functions they do not present themselves to
+chemical observation in the same obvious way as do their fibrous
+relatives. The pith of the elder, however, _is_ readily obtained in
+convenient masses, and a preliminary investigation of the entire tissue
+has established the following points:
+
+The _reactions_ of the tissue are in all respects those of the
+lignocelluloses.
+
+_Composition._--Ash, 2.2 p.ct.; moisture in air-dry state, 12.3 p.ct.
+Alkaline hydrolysis (loss): (a) 14.77, (b) 17.84. Cellulose (yield),
+52.33 p.ct. Nitrate-reaction complicated by secondary reactions and
+yields low, 90.95 p.ct. _Sulphocarbonate reaction:_ Resists the
+treatment, less than 10 p.ct. passes into solution.
+
+_Furfural._--The original tissue yields 7.13 p.ct.; the residue from
+alkaline hydrolysis (b) 5.40 p.ct.
+
+This tissue is, therefore, a lignocellulose having the chemical
+characteristics typical of the group, but of less resistance to
+hydrolytic actions.
+
+The investigation will be prosecuted in reference to the cause of
+differentiation in this latter respect. Probably the pectocelluloses are
+represented in the tissue.
+
+
+~The Insoluble Carbohydrates of Wheat (grain).~
+
+H. C. SHERMAN (J. Amer. Chem. Soc., 1897, 291).
+
+(p. 171) This is a study of the constituents of the cell-walls of wheat
+grain. Bran was taken as the most convenient form of the raw material,
+being freed from starch by treatment with malt extract, and further
+treated (1) with cold dilute ammonia, (2) cold dilute soda lye (2 p.ct.
+NaOH), and (3) boiling 0.1 p.ct. NaOH. The product retained only 1.25
+p.ct. proteids, and yielded 15.62 p.ct. furfural.
+
+_Acid Hydrolysis._--The product was boiled 30 mins. with dilute acid
+(1.25 p.ct. H_{2}SO_{4}), and the solution boiled until the Fehling test
+showed no further increase of monoses. At the limit the reducing power
+of the dissolved carbohydrates was 91.3 p.ct., that of dextrose.
+Converted into osazones the analysis showed them to be _pure
+pentosazones_. The _hemicellulose_ of wheat is, therefore, according to
+the author, _pure pentosane_.
+
+_Residue._--This was a lignocellulose yielding 11.5 p.ct. furfural. It
+was subjected to a series of treatments with ferric ferricyanide, and
+the proportion of Prussian blue fixed was determined by increase of
+weight, viz. from 10 p.ct. to 47 p.ct. according to the conditions. The
+results confirmed those of Cross and Bevan first obtained with the
+typical lignocellulose (jute).
+
+_Chlorination._-The residue was boiled with dilute alkali, washed, and
+exposed to chlorine gas. The resulting lignone chloride was isolated by
+solution in alcohol, &c. It yielded 26.7 p.ct. Cl on analysis. In this
+and its properties it appeared to be identical with the product isolated
+by Cross and Bevan from jute, with the empirical formula
+C_{19}H_{18}Cl_{4}O_{9}.
+
+_Cellulose_ was isolated from the residue by three of the well-known
+methods, and the following comparative numbers are noteworthy:
+
+ _________________________________________________________________________
+|                             |              |            |               |
+|                             | F. Schulze   |   Lange    |  Cross and    |
+|      Method                 | Dil. HNO_{3} | Fusion KOH |    Bevan      |
+|                             |   KClO_{3}   |            | Chlorine, &c. |
+|_____________________________|______________|____________|_______________|
+|                             |              |            |               |
+| Cellulose p.ct. obtained    |    66.0      | 39.3-43.1  |    66.5       |
+| Furfural p.ct. of cellulose |     7.0      |   3.96     |     5.62      |
+| Residual nitrogen           |     0.22     |   0.03     |     0.00      |
+| Ferricyanide reaction,      |              |            |               |
+|   Prussian blue fixed       |     6.04     |   0.89     |     0.92      |
+|_____________________________|______________|____________|_______________|
+
+The author remarks: 'It is evident no one feature can be urged as a
+criterion in judging between the methods, but all must be taken into
+consideration. Such a comparison shows the superiority of the
+chlorination method.'
+
+The cellulose is not of the normal (cotton) type, since on treatment
+with sulphuric acid it dissolves with considerable discolouration, but
+only to the extent of about 80 per cent. The dissolved monoses converted
+into osazones were found to consist of hexoses only. The cellulose
+treated with caustic soda solution (5 p.ct. NaOH) in the cold yielded 20
+p.ct. of its weight of soluble constituents, but as the residue yielded
+3.34 p.ct. furfural the attack of the alkali is by no means confined to
+the furfuroids.
+
+~Animal Digestion of the Constituents of Bran.~--Observations on a steer
+fed upon wheat bran only established the following percentage digestion
+of the several constituents:
+
+     Soluble carbohydrates    96.9
+     Starch                  100.0
+     Free pentosanes          60.2
+     Cellulose                24.8
+     Lignin complex           36.7
+     Proteid                  82.96
+     Ether extract            42.73
+     _____________________   ______
+
+     Nitrogen-free extract    76.08
+     Crude fibre              32.21
+
+
+JOURNAL OF THE IMPERIAL INSTITUTE
+
+(Research Department, Vols. 1-2, 1895-6).
+
+(p. 109) In this journal appear a series of notices of the results of
+analyses of vegetable fibres by the method described in 'Report on
+Miscellaneous Fibres' (Col. Ind. Exhibition Reports, p. 368) [C. F.
+Cross]. These investigations deal with the following subjects:
+
+1895.     p. 29      Various Indian Fibres--more particularly Sida.
+            118      (a) Fibres from Victoria; (b) Special Analyses of
+       (a)               Samples of Jute; (c) Paper-making Fibres
+                         from S. Australia.
+            202      Fibres from Victoria.
+            287      Fibres from Victoria.
+            366      Sisal from Trinidad.
+            373      Rope-fibres from Grenada.
+       (b)  398      Report of Experiments on Indian Jute (1).
+            435}     Fifth and Sixth Report on Australian Fibres.
+            473}
+1896.        68      Hibiscus and Abroma Fibres.
+            104-5    Hibiscus, Urena, and Crotalaria Fibres.
+            141      Indian Sisal
+       (c)  182-3    Report of Experiments on Indian Jute (2).
+            264      Sanseviera from Assam.
+
+From the above we may draw the general conclusion that the scheme of
+investigation has been found in practice to answer its main purpose,
+viz. to afford such numerical constants as determine industrial values.
+In illustration we may cite (a) the results of analyses of specially
+selected samples of jute, from which it will be seen that there is a
+close concordance of value as ordinarily determined from external
+appearance, with the chemical constants as determined in the laboratory.
+
+ __________________________________________________________________
+|                            |                                     |
+|                            |          Quality of Jute            |
+|____________________________|_____________________________________|
+|                            |       |        |       |            |
+|                            |  Low  | Medium | Extra | Extra Fine |
+|____________________________|_______|________|_______|____________|
+|                            |       |        |       |            |
+| Moisture                   | 11.0  |  10.4  | 11.1  |     9.6    |
+| Ash                        |  0.87 |   2.8  |  1.0  |     0.7    |
+| Alkaline hydrolysis (a)    |       |        |       |            |
+|   5 mins. boiling          | 13.2  |  11.6  |  8.5  |     9.1    |
+| Alkaline hydrolysis (b)    |       |        |       |            |
+|   60 mins. boiling         | 16.1  |  17.5  | 12.5  |    13.1    |
+| Mercerising treatment      |  9.2  |  10.5  | 10.3  |     8.5    |
+| Nitration (increase p.ct.) | 36.6  |  35.7  | 37.5  |    36.7    |
+| Cellulose (yield)          | 71.4  |  70.0  | 79.0  |    77.7    |
+| Acid purification          |  2.6  |   1.3  |  1.9  |     2.0    |
+|____________________________|_______|________|_______|____________|
+
+A useful series of experiments, initiated by the Institute, is that
+noted under (b) and (c) above.
+
+(1) To ascertain the quality of the fibre extracted from the plant at
+different stages of growth, quantities of 400 lbs. of the stalks were
+cut at successive stages and the fibre isolated after steeping 14-20
+days. The fibre was shipped to England and chemically investigated, with
+the following results:
+
+No. 1. Cut before appearance of inflorescence.
+ "  2.  " after budding.
+ "  3.  " in flower.
+ "  4.  " after appearance of seed-pod.
+ "  5.  " when fully matured.
+
+ _________________________________________________________________
+|                           |       |       |      |      |       |
+|                           |  (1)  |  (2)  |  (3) |  (4) |  (5)  |
+|___________________________|_______|_______|______|______|_______|
+|                           |       |       |      |      |       |
+| Moisture                  | 11.55 |  8.74 | 10.7 | 10.0 |  9.72 |
+| Ash                       |  1.1  |  1.1  |  1.1 |  1.1 |  0.90 |
+| Alkaline hydrolysis (a)   |  6.2  |  8.5  |  9.7 |  8.9 |  7.3  |
+|    "         "      (b)   | 10.5  | 11.9  | 11.6 | 12.0 | 11.2  |
+| Mercerising treatment     | 10.2  | 10.7  | 12.0 |  8.1 | 11.0  |
+| Nitration                 | 37.2  | 32.1  | 32.2 | 33.2 | 36.6  |
+| Cellulose                 | 74.0  | 76.2  | 74.1 | 74.8 | 76.4  |
+| Acid purification         |  0.8  |  0.5  |  0.7 |  2.4 |  1.4  |
+|___________________________|_______|_______|______|______|_______|
+
+It will be thus seen that there are no changes of any essential kind in
+the chemical composition of the bast fibre throughout the life-history
+of the plant, confirming the conclusion that the 'incrustation' view of
+lignification is consistent only with the structural features of the
+changes, and so far as it has assumed the gradual overlaying of a
+cellulose fibre with the lignone substance it is not in accordance with
+the facts.
+
+Examination of the samples from the point of view of textile quality
+showed a superiority of No. 1 in fineness, softness, and strength; from
+this stage there is observed a progressive deterioration, but the No. 4
+sample (which was taken at the usual period of cutting) is superior to
+No. 5.
+
+In a further series of experiments (c) the jute was subjected to
+certain chemical treatments immediately after the separation of the
+fibre from the plant. These consisted in steeping (1) in solution of
+sodium carbonate, as well as of plant ashes, and (2) in sulphite of
+soda, the purpose of the treatments being to modify or arrest the
+changes which take place in the fibre when press-packed in bales for
+shipment. The samples were shipped from India under the usual conditions
+and examined soon after arrival. It was found that the chemical
+treatments had produced but small changes in chemical composition of the
+fibre-substance. The sulphite treatment was the more marked in
+influence, somewhat lowering the cellulose and nitration constants. The
+conclusion drawn from the results was that they afford no prospect of
+any useful modification, i.e. improvement of the textile quality of the
+fibre by any chemical treatments such as could be applied to the fibre
+on the spot before drying for press-packing and shipment.
+
+The other matters investigated in the Institute laboratory and reported
+on as indicated above are rather of commercial significance, and
+contributed no points of moment to the chemistry of cellulose.
+
+
+OBSERVATIONS ON SOME OF THE CHEMICAL SUBSTANCES IN THE TRUNKS OF TREES.
+
+F. H. STORER (Bull. Bussey Inst., 1897, 386).
+
+(p. 172) An examination of the outer and inner wood and of the bark of
+the grey birch, at different seasons of the year, gave the following
+yields of furfural p.ct. on the dry substance:
+
+ ________________________________
+|         |               |      |
+|         |     Wood      |      |
+|         |_______________| Bark |
+|         |       |       |      |
+|         | Inner | Outer |      |
+|_________|_______|_______|______|
+|         |       |       |      |
+| May     | 21.3  | 19.6  | 16.7 |
+| July    | 16.6  | 18.8  | 11.4 |
+| October | 16.2  | 16.3  | 12.3 |
+|_________|_______|_______|______|
+
+The paper contains the results of treating the woods and various
+vegetable products with hydrolysing agents in order of intensity: (a)
+Malt-extract at 60�C., (b) boiling dilute HCl (1.0 p.ct. HCl), and
+(c) boiling dilute HCl (2.5 p.ct.). The residues were found to yield
+considerable proportions of furfural. The following numbers are typical:
+
+ ________________________________________________________________________
+|                               |             |                          |
+|                               |     Birch   |        Stones of         |
+|                               |_____________|__________________________|
+|                               |      |      |        |         |       |
+|                               | Bark | Wood |  Date  | Apricot | Peach |
+|_______________________________|______|______|________|_________|_______|
+|                               |      |      |        |         |       |
+| Action of malt extract calcu- |      |      |        |         |       |
+| lated as starch dissolved     | 4.24 |  3.5 |   5.2  |   1.5   |   --  |
+|                               |      |      |        |         |       |
+| Residue boiled, 1 p.ct. HCl   |      |      | Mannan |         |       |
+| gave pentosanes dissolved.    |  --  | --   |  11.7  |  14.1   |  6.7  |
+|                               |      |      |        |         |       |
+| Residue yielded furfural      | 19.3 | 17.8 |   3.4  |   9.6   |  9.7  |
+|_______________________________|______|______|________|_________|_______|
+
+The proportion of pentosanes (furfuroids) removed, i.e. hydrolysed by
+boiling with hydrochloric acid of 2.5 p.ct. HCl, is shown by the
+following estimations of furfural:
+
+ _________________________________________________________________
+|                        |              |               |         |
+|                        |    Birch     |  Sugar maple  |         |
+|                        |______________|_______________| Apricot |
+|                        |       |      |       |       | stones  |
+|                        |  Bark | Wood | Outer | Inner |         |
+|                        |       |      |  wood |  wood |         |
+|________________________|_______|______|_______|_______|_________|
+|                        |       |      |       |       |         |
+| In original substance  | 16.7  | 19.6 |  18.2 |  20.7 |  18.4   |
+|                        |       |      |       |       |         |
+| In residue from action |  6.53 |  8.6 |   4.9 |   6.4 |   7.0   |
+| of 2.5 p.ct. HCl       |       |      |       |       |         |
+|________________________|_______|______|_______|_______|_________|
+
+_Wood Gum._--The paper contains some observations on the various methods
+of isolating this product. Attention is directed to the necessary
+impurity of the product, and to the fact that the numbers for furfural
+and for the xylose yielded by hydrolysis are considerably less than for
+a pure pentosane.
+
+_Estimation of Cellulose._--The author investigated the process of Lange
+and the 'celluloses' obtained from various raw materials. The products
+from the woods of birch and maple contained furfural-yielding
+constituents, represented by yields of 6-8 p.ct. furfural. Preference is
+given to the process by comparison with others, at the same time that it
+is recommended in all cases to examine the product for furfural
+quantitatively, converting the numbers into pentosane equivalents, and
+subtracting from the total 'cellulose' to give the true cellulose.
+
+
+ZUR KENNTNISS DER MUTTERSUBSTANZEN DES HOLZGUMMI.
+
+E. WINTERSTEIN (Ztschr. Physiol. Chem., 1892, 381).
+
+~ON THE MOTHER SUBSTANCES OF WOOD-GUM.~
+
+(p. 188) According to the text-books beech-wood may be regarded as the
+typical raw material for the preparation of the laboratory product known
+as wood-gum. The author has subjected beech-wood and beech-wood
+cellulose (Schulze process) to a range of hydrolytic treatments, acid
+and alkaline, in order to determine the conditions of selective action
+upon the mother substance of the wood-gum. In the main it appears that
+this group of furfuroids is equally resistant with the cellulose
+constituents of the wood; in fact, that the mother substance of wood-gum
+is a modified cellulose, and exists in the wood in chemical combination
+with the 'incrusting substances.'
+
+Of the author's experimental results the following may be cited as
+typical:
+
+                                                     Yield of furfural
+     Substance                                              p.ct.
+Original beech-wood                                         13.8
+
+After boiling 3 hrs. with 1.25 p.ct. H_{2}SO_{4} (residue)  10.1
+
+   "       "      "    "   5.0    "       "            "     5.6
+
+Cellulose--isolated by Schulze process (yield 53 p.ct.)      6.9
+
+    "      after further 14 days' digestion with the
+             Schulze acid (HNO_{3} + KClO_{3})               5.9
+
+    "      after extraction with 5 p.ct. NaOH in
+             cold (residue)                                  5.0
+
+    "      after second extraction with 5 p.ct. NaOH
+             in cold (residue)                               4.4
+
+
+UEBER DIE FRAGE NACH DEM URSPRUNG UNGES�TTIGER VERBINDUNGEN IN DER
+PFLANZE.
+
+C. F. CROSS, E. J. BEVAN, and C. SMITH (Berl. Ber., 1895, 1940).
+
+~ON THE SOURCE OF THE UNSATURATED COMPOUNDS OF THE PLANT.~
+
+(p. 179) In distilling for furfural by the usual methods of boiling
+cellulosic products with condensing acids, the furfural is accompanied
+by volatile acids, also products of decomposition of the cellulosic
+complex. A series of distillations was carried out with dilute sulphuric
+acids of varying concentration from 10-50 H_{2}SO_{4} : 90-50 H_{2}O by
+weight, using barley straw as a typical cellulosic material. The
+distillates were collected in successive fractions, and the furfural and
+volatile acid determined. The results are given in the form of curves.
+The aggregate yields were as follows:--
+
+Concentration of acid
+  (H_{2}SO_{4}) p.ct.            10    15    20    30    40    50
+
+Furfural yield p.ct. of straw     2.0   2.0   4.4  10.1  11.5  11.0
+
+Volatile acid (calculated
+  as acetic acid) p.ct. of straw  1.7   1.9   3.1   4.3   6.3  14.8
+
+With acids up to 20 p.ct. H_{2}SO_{4} both products are formed
+concurrently and in nearly equal quantity. With the 30 p.ct. acid there
+is a great increase in the total furfural, and with the 40 p.ct. acid it
+reaches nearly the maximum obtainable with HCl of 1.06 s.g. (Tollens),
+in this case 12.4 p.ct. The volatile acid increases, but in less ratio;
+it is also produced concurrently. With 50 p.ct. H_{2}SO_{4} the
+conditions are changed. The total furfural is rapidly formed, whereas
+the volatile acid continues to be formed long after the aldehyde ceases
+to come over. Moreover, whereas in the previous cases it was mainly
+acetic acid, it is now mainly formic acid. The method was then extended
+to a typical series of celluloses, heated with the more concentrated
+acid (40-50 p.ct. H_{2}SO_{4}), with the following results:
+
+ __________________________________________________
+|                        |       |                 |
+|                        |       |  Volatile acid  |
+|                        |       |_________________|
+|                        |       |        |        |
+|                        |       | Acetic | Formic |
+|________________________|_______|________|________|
+|                        |       |        |        |
+| Swedish filter-paper   |  0.3  |   2.7  |  17.2  |
+| Esparto cellulose      | 12.4  |   3.2  |  16.6  |
+| Bleached cotton        | trace |   3.1  |  13.2  |
+| Raw cotton (American)  |  --   |   5.0  |   9.4  |
+| Jute cellulose         |  5.2  |   4.9  |  22.7  |
+| Beech (wood) cellulose |  6.4  |   3.5     14.6  |
+|________________________|_______|________|________|
+
+The tendency in the hexoses and their polyanhydrides to split off one
+carbon atom in the oxidised form, throws some light on the furfurane
+type of condensation, which is represented in the lignocelluloses. We
+are still without any evidence as to the possible transition of the
+hexoses to benzenoid compounds. Such transitions would be more easily
+explained on the assumption that the celluloses are composed in part of
+polyanhydrides of the ketoses.
+
+
+SPIRITUS AUS CELLULOSE UND HOLZ.
+
+E. SIMONSEN (Ztschr. angew. Chem., 1898, 3).
+
+~PRODUCTION OF ALCOHOL FROM CELLULOSE AND WOOD.~
+
+(pp. 50, 209) This investigation was undertaken with one main object--to
+determine the optimum conditions of treatment of wood-cellulose and of
+wood itself for conversion into 'fermentable sugar.' The process of
+'inversion' or hydrolysis, by digestion with dilute acid at high
+temperature, involves the four main factors: pressure (i.e.
+temperature), concentration of acid, ratio of liquid to cellulose and
+duration of digestion. Each of these was varied in definite gradations,
+and the effect measured. The degree of action was measured in terms of
+'reducing sugar,' calculated from the results of estimation by Fehling
+solution, as 'glucose' per cent. of original cellulose (or wood).
+
+(a) _Cellulose._ [Wood-cellulose obtained by bisulphite
+process.]--With a proportion of total liquid to cellulose of 27 : 1, and
+using sulphuric acid as the hydrolysing agent, the optimum results were
+obtained with acids of 0.45-0.60 p.ct. (H_{2}SO_{4}) and pressures of
+6-8 atm. The maximum yield of 'sugar' was 45 p.ct. of the cellulose.
+
+Under the above conditions the maximum of conversion is attained in 2
+hours.
+
+Having now regard to the production of a solution of maximum
+_concentration_ of dissolved solids, the following conditions were
+asertained to fulfil the requirement, and, in fact, may be regarded as
+the economic optimum:
+
+     Proportion of total liquid  6 times wt. of cellulose
+     Concentration of acid       0.5 p.ct. H_{2}SO_{4}
+     Pressure                   10 atm.
+     Duration of digestion       1.5 hour
+
+giving a yield of 41 p.ct. 'reducing sugar' calculated to the original
+cellulose (dry).
+
+_Alcoholic Fermentation of Neutralised Extract._--The liquors were found
+to ferment freely, and on distillation to yield a quantity of alcohol
+equal to 70 p.ct. of the theoretical--i.e. on the basis of the numbers
+for copper oxide reduction.
+
+(b) _Hydrolytic 'Conversion' of Wood (Lignocellulose)._--A similarly
+systematic investigation carried out upon pine sawdust established the
+following as optimum conditions:
+
+     Proportion of total liquid  5 times wt. of wood
+     Concentration of acid       0.5 p.ct. H_{2}SO_{4}
+     Pressure                    9 atm.
+     Duration of digestion      15 minutes
+
+giving a yield of 20 p.ct. 'reducing sugar,' calculated from the
+'Fehling' test.
+
+_Fermentation_ of the neutralised extracts gave variable results. The
+highest yields obtained were 60 p.ct. of theoretical, the author finally
+concluding that under properly controlled conditions of inversion and
+fermentation 100 kg. wood yield 6.5 l. absolute alcohol.
+
+
+�BER DIE URSACHE DER VON SIMONSEN BEOBACHTETEN UNVOLLST�NDIGKEIT DER
+VERG�HRUNG DER AUS HOLZ BEREITETEN ZUCKERFL�SSIGKEITEN.
+
+B. TOLLENS (Ztschr. angew. Chem., 1898, 15).
+
+~ON THE CAUSE OF INCOMPLETE FERMENTATION OF SUGARS OBTAINED BY ACID
+HYDROLYSIS OF WOOD.~
+
+The author criticises Simonsen's explanation of the results obtained
+with extracts from pine wood. The incompleteness of fermentation of the
+products is certainly due in part to the presence of furfural-yielding
+carbohydrates, which are resistant to yeast. The pine woods contain 8-10
+p.ct. of these constituents in their anhydride form ('pentosanes'). They
+yield readily to acid hydrolysis, and certainly constitute a
+considerable percentage of the dissolved products. A similar complex was
+obtained by the author in his investigation of peat (Berl. Ber. 30,
+2571), and was found to be similarly incompletely attacked by yeast. The
+yields of alcohol corresponded with the proportion of the total
+carbohydrates disappearing. These were the hexose constituents of the
+hydrolysed complex, the pentoses (or 'furfuroids') surviving intact.
+
+
+UEBER SULFITCELLULOSEABLAUGE.
+
+H. SEIDEL (Ztschr. angew. Chem., 1900).
+
+~WASTE LIQUORS FROM BISULPHITE PROCESS.~
+
+(p. 210) Later researches confirm the conclusion that in the soluble
+by-products of these cellulose processes the S is combined as a SO_{3}H
+group. The following analyses of the isolated lignin sulphonic acid are
+cited:
+
+ ________________________________________________
+|                          |       |      |      |
+|                          |   C   |  H   |  S   |
+|__________________________|_______|______|______|
+|                          |       |      |      |
+| (a) Lindsey and Tollens  | 56.12 | 5.30 | 5.65 |
+| (b) Seidel           (1) | 56.27 | 5.87 | 5.52 |
+| (c) Seidel and Hanak (2) | 53.69 | 5.22 | 8.80 |
+| (d) Street               | 50.22 | 5.64 | 7.67 |
+|__________________________|_______|______|______|
+
+The variations are due to the varying conditions of the digestion of the
+wood and to corresponding degrees of sulphonation of the original
+lignone group. Calculating the composition of the latter from the above
+numbers on the assumption that the S represents SO_{3}H, the following
+figures result:
+
+ __________________________________
+|   |             |       |       |
+|   | (a) and (b) |  (c)  |  (d)  |
+|___|_____________|_______|_______|
+|   |             |       |       |
+| C |  64.00      | 65.1  | 59.61 |
+| H |   6.65      |  6.33 |  6.69 |
+|___|_____________|_______|_______|
+
+This author considers that beyond the empirical facts established by the
+above named[10] very little is yet known in regard to the constitution
+of the lignone complex.
+
+Nor is there any satisfactory application of this by-product as yet
+evolved. Evaporation and combustion involve large losses of sulphur
+[D.R.P. 74,030, 83,438; Seidel and Hanak, Mitt. Techn. Gew. Mus. 1898].
+A more complete regeneration of the sulphur has been the subject of a
+series of patents [D.R.P. 40,308, 69,892, 71,942, 78,306, 81,338], but
+the processes are inefficient through neglect of the actual state of
+combination of the S, viz. as an organic sulphonate. The process of V.B.
+Drewson (D.R.P. 67,889) consists in heating with lime under pressure,
+yielding calcium monosulphite (with sulphate and the lignone complex in
+insoluble form). The sulphite is redissolved as bisulphite by treatment
+with sulphurous acid. This process is relatively costly, and yields
+necessarily an impure lye. It has been proposed to employ the product as
+a foodstuff both in its original form and in the form of benzoate
+(D.R.P. 97,935); but its unsuitability is obvious from its composition.
+A method of destructive distillation has been patented (D.R.P. 45,951).
+The author has investigated the process, and finds that the yield of
+useful products is much too low for its economical development. Fusion
+with alkaline hydrates for the production of oxalic acid (D.R.P. 52,491)
+is also excluded by the low yield of the product.
+
+The application of the liquor for tanning purposes (D.R.P. 72,161)
+appears promising from the fact that 28 p.ct. of the dry residue is
+removed by digestion with hide powder. This application has been
+extensively investigated, but without practical success. Various
+probable uses are suggested by the viscosity of the evaporated extract.
+As a substitute for glue in joinery work, bookbinding, &c., it has
+proved of little value. It is applied to some extent as a binding
+material in the manufacture of briquettes, also as a substitute for
+gelatin in the petroleum industry. Cross and Bevan (E.P. 1548/1883) and
+Mitscherlich (D.R.P. 93,944 and 93,945) precipitate a compound of the
+lignone complex and gelatin by adding a solution of the latter to the
+liquors. The compound is redissolved in weak alkaline solutions and
+employed in this form for engine-sizing papers. Ekman has patented a
+process (D.R.P. 81,643) for 'salting out' the lignone sulphonates, the
+product being resoluble in water and the solution having some of the
+properties of a solution of dextrin. Owing to its active chemical
+properties this product--'dextron'--has a limited capability of
+substituting dextrin. The suggestion to employ the evaporated extract as
+a reducing agent in indigo dyeing and printing has also proved
+unfruitful. The author's application of the soda salt of the lignone
+sulphonic acid as a reducing agent in chrome-mordanting wool and woollen
+goods (D.R.P. 99,682) is more successful in practice, and its industrial
+development shows satisfactory progress. The product is known as
+'lignorosin.'
+
+FOOTNOTES:
+
+[10] See more particularly: Lindsey and Tollens, _Annalen_, 267, 341;
+Cross and Bevan's _Cellulose_, pp. 197-203; Street, Inaug.-Diss.,
+G�ttingen, 1892; Klason, _Rep. d. Chem. Ztg._ 1897, 261; Seidel and
+Hanak, _Mitt. d. Techn. Gew. Mus._ 1897-1898.
+
+
+
+
+SECTION VII. PECTIC GROUP
+
+
+UNTERSUCHUNGEN �BER PECTINSTOFFE.
+
+R. W. TROMP DE HAAS and B. TOLLENS (Lieb. Ann., 286, 278).
+
+�BER DIE CONSTITUTION DER PECTINSTOFFE, B. TOLLENS (ibid. 292).
+
+~INVESTIGATIONS OF PECTINS.~
+
+(p. 216) It is generally held that the pectins are, or contain, oxidised
+derivatives of the carbohydrates. The authors have isolated and analysed
+a series of these products, and the results fail to confirm a high
+ratio O : H. The following are the analytical numbers:
+
+ ________________________________________________
+|              |      |      |     |             |
+| Pectin from  |  Ash |   C  |  H  | Ratio H : O |
+|______________|______|______|_____|_____________|
+|              |      |      |     |             |
+| Apple        |  6.2 | 43.4 | 6.4 |   1 : 7.9   |
+| Cherry       | 20.5 | 42.5 | 6.5 |   1 : 7.9   |
+| Rhubarb      |  4.2 | 43.3 | 6.8 |   1 : 7.4   |
+| Currant      |  5.0 | 47.1 | 5.9 |   1 : 8.5   |
+| Greengage    |  3.3 | 43.0 | 5.9 |   1 : 8.5   |
+| Turnip       |  7.3 | 41.0 | 5.9 |   1 : 9.0   |
+|______________|______|______|_____|_____________|
+
+Acid hydrolysis (4 p.ct. H_{2}SO_{4}) gave syrupy products not
+crystallisable--in certain cases the hydrolysis was accompanied by
+separation of insoluble cellulose. The insoluble product from currant
+pectin had the composition C 54.4, H 5.0.
+
+Tollens points out that the results of empirical analysis are
+inconclusive; and that from the acid reactions of these products and
+their combination with bases, carboxylic groups are present, though
+probably in anhydride or ester form.
+
+The pectins may be regarded as closely related to the mucilages
+(_Pflanzenschleim_), differing from them only by the presence of the
+oxidised groups in question.
+
+
+UEBER DIE CONSTITUTION DER PECTINSTOFFE.
+
+C. F. CROSS (Berl. Ber., 1895, 2609).
+
+~CONSTITUTION OF PECTINS.~
+
+It is pointed out that the composition of the pectin of white currants,
+as given in the preceding paper, is that of the typical lignocellulose,
+the jute fibre. The product was isolated and further investigated by the
+author. It gave 9.8 p.ct. furfural on boiling with HCl (1.06 s.g.),
+reacted freely with chlorine, giving quinone chlorides, and with ferric
+ferricyanide to form Prussian blue. This 'pectin' is therefore a form
+of soluble lignocellulose. The 'pectic' group consequently must be
+extended to include hydrated and soluble forms of the mixed complex of
+condensed and unsaturated groups with normal carbohydrates, such as
+constitute the fibrous lignocelluloses.
+
+
+UEBER DAS PFLANZLICHE AMYLOID.
+
+E. WINTERSTEIN (Ztschr. Physiol. Chem., 1892, 353).
+
+~ON VEGETABLE AMYLOID.~
+
+(p. 224) A group of constituents of many seeds, distinguished by giving
+slimy or ropy 'solutions' under the action of boiling water are
+designated 'amyloid.' They are reserve materials, and in this, as in the
+physical properties of their 'solutions,' they are very similar to
+starch. They are, however, not affected by diastase; and generally are
+more resistant to hydrolysis. Typical amyloids have been isolated by the
+author from seeds of _Tropoeolum majus, Poeonia officinalis_, and
+_Impatiens Balsamina_. The raw material was carefully purified by
+exhaustive treatment with ether and alcohol, &c.; the amyloid then
+extracted by boiling with water, and isolated by precipitation with
+alcohol. Elementary analysis gave the numbers C 43.2, H 6.1. On boiling
+with 12 p.ct. HCl it gave 15.3 p.ct. furfural; oxidised with nitric acid
+it yielded 10.4 p.ct. mucic acid. Specimens from the two first-named raw
+materials gave almost identical numbers.
+
+_Hydrolysis._--On boiling with dilute acids these products are gradually
+broken down, dissolving without residue. In this respect they are
+differentiated from the mucilages, which give a residue of cellulose
+(insoluble). From the solution the author isolated crystalline
+galactose, but failed to isolate a pentose. Dextrose was also not
+identified directly.
+
+The tissue residues left after extracting the amyloid constituent, as
+above described, were subjected to acid hydrolysis. A complex of
+products was obtained, from which galactose was isolated. A
+furfural-yielding carbohydrate was also present in some quantity, but
+could not be isolated. The original seed tissues, therefore, contain an
+amyloid and a hemicellulose, the latter differentiated in its resistance
+to water. Both yield, however, to acid hydrolysis a complex of products
+of similar composition and constitution.
+
+
+UEBER DEN GEHALT DES TORFES AN PENTOSANEN ODER FURFUROLGEBENDEN STOFFEN
+UND AN ANDEREN KOHLENHYDRATEN.
+
+H. V. FEILITZEN and B. TOLLENS (Berl. Ber., 1897, 2,571).
+
+~CARBOHYDRATE CONSTITUENTS OF PEAT.~
+
+(p. 240) An investigation of typical peats taken at successive depths
+showed increasing percentage of carbon, and inversely a decreasing yield
+of furfural. The numbers may be compared with those for _Sphagnum
+cuspidatum_--with C = 49.80 p.ct., and furfural 7.99 p.ct., calculated
+to dry, ash-free substance:
+
+ __________________________________________________
+|                       |         |                |
+|  Depth at which taken | C p.ct. | Furfural p.ct. |
+|_______________________|_________|________________|
+|      _                |         |                |
+|     |      20-100 cm. |  51.08  |      6.93      |
+|  I. |     100-200  "  |  53.52  |      5.30      |
+|     |_    200-300  "  |  58.66  |      3.19      |
+|      _                |         |                |
+|     |  Surface-20  "  |  55.47  |      3.40      |
+| II. |       20-60  "  |  55.06  |      3.48      |
+|     |      60-100  "  |  58.25  |      1.45      |
+|     |     100-120  "  |  58.23  |      1.19      |
+|     |_    180-200  "  |  57.57  |      1.80      |
+|_______________________|_________|________________|
+
+_Cellulose_ was estimated by the Lange method. The yield from _Sphagnum_
+was 21.1 p.ct.
+
+From specimen I. at {  20-100 cm.   15.20
+                    { 100-200  "     6.87
+
+From the peat of lower depths no cellulose could be obtained.
+
+_Hydrolysis_ (acid).--On heating with 1 p.ct. H_{2}SO_{4} at 130-135�,
+soluble carbohydrates were obtained, amongst which mannose was
+identified, and galactose shown to be present in some quantity. After
+fermenting away the hexoses, the residue was treated with
+phenylhydrazine and an osazone separated. It contained 17.3 p.ct. N, but
+melted at 130�. The substance could not be identified as an osazone of
+any of the yet known pentoses.
+
+
+
+
+SECTION VIII. INDUSTRIAL AND TECHNICAL. GENERAL REVIEW
+
+
+~The Industrial Uses of Cellulose.~
+
+C. F. CROSS (Cantor Lectures, Soc. of Arts, 1897).
+
+(p. 273) A series of three lectures, in which the more important
+industries in cellulose and its derivatives are dealt with on their
+scientific foundations, and by means of a selection of typical problems.
+In reference to textiles, the small number of vegetable fibres actually
+available, out of the endless variety afforded by the plant world, is
+referred to the number of conditions required to be fulfilled by the
+individual fibre, thus: yield per cent. of harvested weight or per unit
+of field area, ease of extraction, the absolute dimensions of the
+spinning unit, and the proportion of variation from the mean dimensions;
+the relative facility with which the unit fibre can be isolated
+preparatory to the final twisting operation; the chemical constants of
+the fibre substance, especially the percentage of cellulose and degree
+of resistance to hydrolysis. It is suggested that any important addition
+to the very limited number fulfilling the conditions, or any great
+improvement in these, can only result from very elaborate artificial
+selection and cultural developments on this basis.
+
+The paper making fibres are shown to fall into a scheme of
+classification based on chemical constitution, and consisting of the
+four groups: (a) Cotton [flax, hemp, rhea], (b) wood celluloses,
+(c) esparto, straw, and (d) lignocelluloses. Papers being exposed to
+the natural disintegrating agencies, more especially oxygen, water (and
+hydrolysing agents generally), and micro-organisms, the relative
+resistance of the above groups of raw materials is discussed as an
+important condition of value. The indirect influence of the ordinary
+sizing and 'filling' materials is discussed. The paper-making quality of
+the fibrous raw materials is also discussed, not merely from the point
+of view of the form and dimensions of the ultimate fibres, but their
+capacity for 'colloidal hydration.' This is complementary to the action
+of rosin, i.e. resin acids, in the engine-sizing of papers; and the
+proof of the potency of this factor is seen in the superior effects
+obtained in sizing jointly with solutions of cellulose and, more
+particularly, viscose and rosin. Wurster's much-cited monograph of the
+subject of rosin-sizing ['Le Collage des Papiers,' Bull. Mulhouse, 1878]
+neglects to take into consideration the contribution of the cellulose
+hydrates to the total and complex sizing effect, and hence gives a
+partial view only of the function of the resin acids.
+
+In further illustration of fundamental principles various developments
+in the textile industries are discussed, e.g. the bleaching of jute,
+cotton, and flax, and special developments in the spinning of rhea and
+flax.
+
+The concluding lecture deals with later progress in the industrial
+applications of cellulose derivatives, chiefly the sulphocarbonate
+(viscose); the nitrates, in their applications to explosives, on the one
+hand, and the spinning of artificial fibres (lustra-cellulose), on the
+other; and the cellulose acetates.
+
+
+~La Viscose et le Viscoide.~
+
+C. H. BARDY (Bull. Soc. d'Enc. Ind. Nationale, 1900, March).
+
+This is a report presented to the Committee of Economic Arts of the
+above Society, dealing with the industrial progress in products obtained
+by means of the sulphocarbonate of cellulose (viscose).
+
+The following developments are noted:
+
+_Engine-sized Papers._--The viscose, by coating the fibres with
+regenerated cellulose hydrate, adds very much to the tensile strength of
+papers. Increase of 40-60 p.ct. is attainable by addition of cellulose
+in this form from 1-4 p.ct. on the weight of the paper.
+
+_Viscoid._--Solid aggregates are formed by incorporating viscose with
+mineral matters, hydrocarbons, &c. Products are cast or moulded into
+convenient forms, and, after purification and sufficient ageing, are
+available for various structural uses.
+
+_Paint._--The viscose is used as a vehicle for pigments, the mixture
+being used either as a paint or for coating papers with fine surfaces,
+such as required in the reproduction of photo-blocks. In these
+applications the extraordinary viscosity of the product conditions the
+economic use of the cellulose in competition with oils, on the one hand,
+and organic colloids, such as gelatine, casein, &c., on the other.
+
+By suitable alteration of the formula for making the paint a product is
+obtained which has an extraordinary power of removing paint from old
+painted surfaces. The product has been officially adopted by the French
+Admiralty, and receives extensive application in removing the paint from
+ships.
+
+_Films._--Films are produced from the viscose itself in various ways.
+Plane or flat by solidifying the viscose on glass surfaces, removing the
+by-products and rolling the films. The film is also produced by
+applying the viscose on textile fabrics, drying down, and fixing on a
+stenter machine, then washing away the alkaline by-products from the
+fixed film. A large number of industrial effects are obtained by
+suitably varying the mixtures applied.
+
+_Cellulose-indiarubber._--The viscose, in its concentrated form, can be
+incorporated with rubber-hydrocarbon mixtures, and these mixtures can be
+used both as water-proofing films, as applied to textiles, or can be
+solidified into the class of goods known as 'mechanicals.' The cellulose
+not only cheapens the mixture, but produces new technical effects.
+
+_Spinning._--The viscose is spun by special methods, patented by C. H.
+Stearn. As produced in thread form, the diameters are approximately
+those of natural silk. In commercial form it is a multiple thread (of 15
+or more units) at from 50-200 deniers on the silk counts. It is a thread
+of high lustre, and more nearly approaches the normal cellulose in
+chemical properties than any of the other artificial silks. It can also
+be spun in threads of very much larger diameter, which can be used as a
+substitute for horsehair, for carbonising for incandescent electric
+lamps, &c.
+
+_Cellulose Esters._--These are conveniently made from cellulose,
+regenerated from the solution as sulphocarbonate. The tetracetate is
+made from this product on the industrial scale. Nitrates are
+conveniently made by treatment with the ordinary mixed acids. For fuller
+details the original report may be consulted.
+
+
+VISKOS.
+
+R. W. STREHLENERT (Svensk Kemisk Tidskrift, Stockholm, 1900, p. 185).
+
+A report on the industrial development of viscose, covering essentially
+the same ground as the above.
+
+
+~Ueber die Viscose.~
+
+B. M. MARGOSCHES (Reprint from Zeitschrift f�r die gesammte
+Textil-Industrie, 1900-01, Nos. 14-20).[11]
+
+
+~Report of Committee on the Deterioration of Paper.~
+
+(Soc. of Arts, 1898.)
+
+(p. 304) The Report of a Representative Committee appointed by the
+Society of Arts to inquire into the question of qualities of book papers
+in relation to their several applications, and more especially for
+documents of permanent value.
+
+The report first discusses the two directions of depreciation of papers
+in use: (1) Actual disintegration shown by loss of resistance to
+fracture by simple strain, and by loss of elasticity--i.e. increase of
+brittleness; (2) discolouration. These are independent effects, but
+often concurrent. They are the result of chemical changes of the
+cellulose basis of the paper, brought about by acids or oxidants used in
+the process of manufacture, and not completely removed from the pulp, or
+by acid products of bleaching--e.g. oxycelluloses or chlorinated
+derivatives; again, by the changes of starch used as a 'sizing' agent,
+or by oxidations induced by rosin constituents when the rosin is used in
+excess. Discolouration is an attendant phenomenon of these changes, but
+is more frequently due to the presence of the lower-grade celluloses
+(esparto and straw) and the lignocelluloses (mechanical wood-pulp).
+
+The physical and chemical qualities of papers depending primarily upon
+their fibrous or pulp basis, and in a secondary degree upon the kind and
+proportion of the constituents added for the purpose of filling and
+'sizing,' the report concludes with the following recommendations,
+positive and negative, under these heads:
+
+The Committee find that the practical evidence as to permanence fully
+confirms the classification given in the Cantor Lectures on 'Cellulose,'
+1897 [J. Soc. Arts, xlv. 690-696], and which ranges the paper-making
+fibres in four classes:
+
+(A) Cotton, flax, and hemp (rhea).
+
+(B) Wood celluloses, (a) sulphite process and (b) soda and
+'sulphate' process.
+
+(C) Esparto and straw celluloses.
+
+(D) Mechanical wood-pulp.
+
+In regard, therefore, to papers for books and documents of permanent
+value, the selection must be taken in this order, and always with due
+regard to the fulfilment of the conditions of normal treatment above
+dealt with as common to all papers.
+
+The Committee have been desirous of bringing their investigations to a
+practical conclusion in specific terms--viz. by the suggestion of
+standards of quality. It is evident that in the majority of cases there
+is little fault to find with the practical adjustments which rule the
+trade. They are, therefore, satisfied to limit their specific findings
+to the following--viz. (1) normal standard of quality for book-papers
+required for publications of permanent value. For such papers they
+specify as follows:
+
+Fibres: Not less than 70 p.ct of fibres of class A; class D excluded.
+
+Sizing: Not more than 2 p.ct. rosin, and finished with the normal
+acidity of pure alum; starch excluded.
+
+Loading: Not more than 10 p.ct. total mineral matter (ash).
+
+(2) With regard to written documents, it must be evident that the proper
+materials are those of class A, and that the paper should be pure and
+sized with gelatin, and not with rosin. All imitations of high-class
+writing-papers which are, in fact, merely disguised printing-papers,
+should be carefully avoided.
+
+_Appendix._--To the Report is added 'Abstracts of Papers' in
+'Mittheilungen aus den Koniglichen Technischen Versuchsanstalten,
+Berlin,' for the years 1885-1896 inclusive--which is, in fact, a summary
+of the investigations of the Institution in connection with paper and
+paper-standards.
+
+       *       *       *       *       *
+
+(p. 273) ~Special Industrial Developments.~--From the point of view of the
+chemist there has been a very large development of the cellulose
+industries during the last five years. This is not so much marked by the
+gradual and progressive growth of the well-established industries, as by
+the success of the newer ones, with the attendant forecast of enormous
+developments of the industries in artificial products, the manufacture
+of which rests upon a purely chemical basis. We can, of course, only
+treat them from this limited standpoint, and so far as they involve and
+elucidate chemical principles.
+
+
+~I. Chemical Treatments of Raw Materials.~
+
+(a) ~Flax-spinning.~--The treatment of the roving on the spinning-frame
+by the addition of reagents to the macerating liquid--otherwise and
+usually hot water--continues to be justified by results. The technical
+basis of the process and the reactions determined in the spinning-trough
+by the alkaline salts used--chiefly sulphite and phosphate of soda--is
+set forth in the original work, p. 280. Since that time a sufficient
+period has elapsed to judge the effects, both technical and industrial,
+by the results of a commercial undertaking based on the exclusive use of
+the process. Such a concern is the Irish Flax Spinning Company of
+Belfast. At this mill the experience is uniform and fully established
+that by means of the process the drawing, i.e. spinning, quality of
+inferior flaxes is very considerably appreciated, enabling the spinner
+to use such flaxes for yarns of fineness which are unattainable by the
+ordinary method of spinning through hot water. Notwithstanding the
+success of this undertaking the development of the method is still
+inconsiderable. It is none the less a further and forcible demonstration
+of the existence of margins of increased technical effect which it is
+the work of the scientific technologist to exploit.
+
+(b) ~Wood-pulp and Methods of Manufacture.~--There is a steady growth in
+the consumption of wood-pulps (cellulose) relatively to other materials.
+In regard to the paper-trade of the world, this continues to be one of
+the most prominent characteristics of its evolution. In the United
+Kingdom the conditions of its competition are of a more special kind by
+reason of the firm foothold of esparto, which is a most important staple
+in the manufacture of fine printings. Whereas the consumption of esparto
+remains nearly stationary at about 200,000 tons per annum, the
+importation of wood-pulps has shown the extraordinary rate of increase
+of doubling itself every five years. But in the group 'wood-pulps' the
+trade returns have until recently included the 'mechanical' or ground
+wood-pulps. From 1898 we have separate returns for the chemical or
+cellulose pulps, and in 1899 the tonnage reached nearly to that of
+esparto, with a total money value about 80 p.ct. greater. When it is
+remembered that this is one of the newer chemical industries in
+cellulose products, and that these large commercial results have been
+accomplished during a period of twenty years, we are impressed with the
+scope of the industrial outlook to the chemist, afforded by the arts of
+which cellulose is the foundation.
+
+It may be noted that there have been no important developments in the
+purely chemical processes involved in the several systems of preparing
+cellulose from wood. The acid methods (bisulphite processes) have
+developed much more extensively than the alkaline, the latter including
+the caustic soda and the mixed sulphide ('Dahl') process. The bisulphite
+processes depended in the earlier stages upon the efficiency of
+lead-lined digesters. But the problem of acid-resisting linings has been
+much more perfectly solved in later years in the various types of cement
+and other silicate linings now in use. The relative permanency of these
+linings has had an important effect on the costs of production. Further
+economies result from the use of digesters of enormous capacity, dealing
+with as much as 100 tons of wood at one operation. As a combined result
+of economic production and active competition, the selling prices of
+'sulphite pulp' have moved steadily downwards in relation to other
+half-stuffs and raw materials. As a necessary consequence the prices of
+those which it has gradually displaced have depreciated, and a study of
+the price and tonnage-equilibrium as between rags, esparto, and
+wood-pulp over a series of years forms an interesting object-lesson in
+the struggle for survival which is an especial mark of modern industry.
+For these matters the reader is referred to the special literature of
+the paper-making industry.[12]
+
+It is not a little remarkable that the main by-product of these
+bisulphite processes--the sulphonated derivatives of the lignone
+constituents of the wood--is still for the most part an absolute waste,
+notwithstanding the many investigations of technologists and attempts to
+convert it to industrial use (see p. 149). Seeing that it represents a
+percentage on the wood pulped equal to that of the cellulose obtained,
+it is a waste of potentially valuable material which can only be termed
+colossal. Moreover, as a waste to be discharged into water-courses, it
+becomes a source of burden and expense to the manufacturer, and with the
+increasing restrictions on the pollution of rivers it is in many
+localities a difficulty to be reckoned with only by the cessation of the
+industry. The problem in such cases becomes that of dealing with it
+destructively, i.e. by evaporation and burning. In this treatment the
+obviously high calorific value of the dissolved organic matter (lignone)
+appears on the 'credit' side. But where calcium and magnesium
+bisulphites are used, the residue from calcination is practically
+without value. It appears, however, that by substituting soda as the
+base the alkali is recoverable in such a form as to be directly
+available for the alkaline-sulphide or 'Dahl' process. As a more
+complicated alternative the soda admits of being recovered on the lines
+of the old black-ash or Leblanc process, and the sulphur by the now
+well-established 'Chance' process, for which, of course, an addition of
+lime is necessary to the fully evaporated liquors previously to
+calcining. The engineering features of the system, so far as regards
+evaporating and calcining, are the same. For economic working there is
+required (a) evaporation by multiple effect and (b) calcining on the
+continuous rotary principle. For the latter a special modification has
+been devised so that the draught of air is concurrent with the movement
+of the charge in the furnace, securing a progressively increasing
+temperature within the furnace. This interesting development of the
+chemical engineering of wood-pulp systems has been elaborated by two
+well-known technologists, Drewson and Dorenfeldt, and readers who wish
+to inform themselves in detail of these developments are referred to the
+various publications of these inventors.
+
+Assuming the present necessity of a destructive treatment of the
+by-products of the bisulphite processes, the scheme has many advantages.
+The soda-bisulphite liquors are more economically prepared; the pulp
+obtained is superior in paper-making quality to that resulting from the
+lime or magnesia (bisulphite) processes: it is more economically
+bleached.
+
+Then, as pointed out, the soda may on the one plan be obtained in a form
+in which it is immediately available as a powerful hydrolysing alkali in
+the manufacture of a 'soda' pulp. These two systems become, therefore,
+in a new sense complementary to one another. Lastly, it is obvious that
+the employment of soda as the base opens out a new vista for developing
+the electrolytic processes of decomposing common salt.
+
+The authors have assisted in preparing plans for a comprehensive
+industrial scheme combining all these more modern developments. In this
+scheme it is only the combination which is novel, and as it involves no
+new principles in the chemical treatments of the materials we are not
+further concerned with it than to have briefly sketched its economic
+basis. This may be summed up in result in the important question of cost
+and selling price, and the estimate is well grounded that by means of
+this scheme _bleached wood-pulp_ can be sold on the English market at
+10l. a ton. It is important to note this figure and to compare it with
+the prices of twenty years ago. The fall has been continuous,
+notwithstanding the influence of the opposing factors of increasing
+consumption, exhaustion of accessible supply of timber, and relative
+appreciation of the essential costs of steam, chemicals, and labour. It
+is important in forecasting the future, since the youngest and
+apparently most promising of the 'artificial' cellulose industries
+employs wood-cellulose by preference as its raw material (see p. 173).
+
+As a last point it must be considered that as chemists we are bound to
+anticipate the realisation of value in the soluble by-products of the
+bisulphite processes. Outside the intrinsic interest attaching to the
+solution of this problem, it carries with it the promise of a further
+economy in the production of wood-cellulose.
+
+~Bleaching of Vegetable Textiles.~--By far the largest of these industries
+are those which are engaged in producing the 'pure white' on cotton and
+flax goods. The process, considered chemically, is simply that of
+isolating a pure cellulose, and we endeavoured to give due prominence to
+this view in the original work. It is important to insist upon it for
+the reason that this view gives the due proportion of chemical value to
+the several contributory treatments--alkaline hydrolyses (caustic lime
+and soda boils), hypochlorite oxidations, and incidental acid treatments
+(souring). The first of these is by far the largest contributor of
+'chemical work,' though the second, by being the agent for the actual
+whitening effect or bleaching action proper, occupies a position of
+often exaggerated importance.
+
+In bleaching processes there has been no radical change of system on the
+large scale since the introduction of the 'Mather' kier in 1885, and the
+associated change from lime and ash boiling to the caustic soda
+circulating boil with reduced volume of lye, which this mechanical
+device rendered practicable. It is outside the scope of this work to
+follow up this branch of technology in any detail, and we cannot discuss
+the evolution of systems on variations of detail where no essential
+principle is involved. But we have to notice a very recent development
+which has only just begun its industrial career, and which does give
+effect to a principle of treatment not previously applied. This is
+tersely stated by its originator, William Mather,[13] in the
+expression, 'it is more economical to make liquids pass through cloth
+than to make cloth pass through liquids.' The starting point of this
+development is the invention of a complete self-contained machine in
+which a rolled batch of cloth can receive a succession of chemical
+treatments, with accessory washings--the solutions, or wash waters,
+being circulated through the cloth. The essential fact on which this
+system is based is that a perfect liquid circulation can be maintained
+from selvedge to selvedge through the folds of a tightly rolled batch of
+cloth. Such circulation is therefore quite independent of the diameter
+of the batch. If we consider a cloth under chemical treatment with
+solutions, it is clear that the reactions and interchanges of soluble
+matters within the cloth, within the twisted elements of the yarn, and
+in the last grade of distribution within the actual ultimate fibres, are
+subject to capillary transmission, and osmotic exchange. There is a
+mixture of these molecular effects, with the circulation in mass,
+sweeping both faces of the cloth. It is obvious that for the mass effect
+a relatively very small volume of circulating liquid is necessary to
+maintain uniform conditions of action. In the actual disposition of the
+machine the rolled batch of cloth nearly fills the cylindrical space of
+what we may call the reaction chamber, and the circulation of the liquid
+is maintained by a circulating pump and a differential pressure in the
+horizontal plane across and through the folds of the batch. This is in
+the meantime kept in slow revolution. For a full description of these
+mechanical details the reader is referred to the original patent
+specifications [Engl. Pat. 23,400, 23,401; 1900, W. Mather]. If we again
+consider the principles involved, they are very much as set forth in
+our original work (pp. 288-291). Boiling processes in which a
+relatively large volume of liquid is used are wasteful of steam, the
+active agent is unnecessarily diluted or used in superfluous quantity,
+and the soluble by-products, being continually removed as formed, cannot
+so effectively contribute by secondary actions to the chemical work. The
+new mechanical appliance enables us to further reduce the volume of
+liquid required in the alkaline-hydrolytic treatment of vegetable
+textiles, and where advantageous to bring the treatment down (or up) to
+a process of steaming with the active agent dissolved in a minimum
+proportion of water relative to the cloth. This concentration of effect
+is of importance in flax cloth, and especially linen treatment, where
+the peculiarly resistant cutocelluloses have to be attacked and a
+considerable proportion of waxy by-products to be removed. These points
+are the basis of the special process of Cross and Parkes [Engl. Pat.
+25,076/ 99] for steaming flax (and cotton) goods with an emulsion
+containing, in addition to the special hydrolysing agent--caustic
+soda--mixtures of soap with 'mineral' or other oils, the presence of
+which effectually aids the removal of the by-products in question.
+
+A complete system on these lines is now working on the industrial scale
+in the Belfast district. The results are not merely economical in
+largely reducing the number of alkaline boiling treatments required on
+the old plan of pan or 'pot' boiling, but are visible in the strength
+and finish of the linens so treated.
+
+For cotton bleaching the costs may be put down at a fraction of those of
+the Irish linen bleach. The economical advantages of the new system are
+obviously less in relation to the lesser total costs. But there are
+other points which have come into more prominent influence. The
+mechanical wear and tear on the cloth is considerable in the ordinary
+process, more especially in the mangle-washes. As a result the
+adjustment of warp and weft is more or less disturbed. These defects are
+absent from a system which operates on the cloth in a fixed position.
+
+But as we are mainly concerned with the purely chemical factors we
+cannot pretend to deal with textile questions. We have to notice the
+remaining element of chemical economy as it involves a fundamental
+principle. The practice of washing residues or products of reaction free
+from reagents and soluble by-products involves a well-known mathematical
+law, under which the rate of purification is a function rather of the
+_number_ of successive changes of washing liquid than of the volume of
+the latter. The ordinary practice of textile washings entirely ignores
+this principle, and the consumption of water in consequence may reach
+many thousand times the economic minimum. With supplies of water often
+in indefinite excess of requirements, even in this most wasteful method,
+bleachers are in no need to consider the question of consumption. But
+leaving aside particular and local considerations of advantage the fact
+is that the new system gives control of the practice of washing,
+enabling the operator to adapt an important element of the daily routine
+to a fundamental principle which has been almost universally ignored.
+
+In the oxidising processes which follow the alkaline treatments, the
+hypochlorites are still the staple agents. Owing to the steady relative
+fall in the selling prices of the permanganates these are coming into
+more extensive use, but the consumption is still small, and they are
+mainly used for certain special effects, chiefly in linen or more
+generally flax cloth bleaching.
+
+~Paper-pulp Spinning.~--Paper is a continuous web or fabric produced by
+the interlocking of the structural fibrous units of the well-known short
+length. In Japan and other countries paper is made to serve for all or
+some of the purposes for which we employ string or twine, and to give
+the necessary tensile strength the paper is twisted or rolled on itself.
+Such twisting, however, adds nothing to the intrinsic tensile qualities
+of the original paper.
+
+A new technical effect is realised in this direction by the treatment of
+paper-pulp in the process of its conversion into a continuous web: The
+pulp is formed into continuous strips of convenient breadth (usually
+from 2 to 8 mm.), these receive a 'rolling-up' treatment immediately
+following the squeeze of the press rolls by which the superfluous water
+is removed: they are then further but incompletely dried, and in this
+condition are subjected to a final spinning or twisting treatment on
+ring-spinning machinery of special construction.
+
+Such a process was originally patented by C. Kellner in this country
+(E.P. No. 20,225/1891), and is fully described in his specification.
+Later improvements in detail were patented by G. T�rk (E.P. 4621/1892).
+
+A joint system is now being industrially developed in Germany by the
+Altdamm-Stahlhammer Pulp and Paper Company under the technical direction
+of Dr. Max M�ller, and there appears to be every prospect of the product
+taking a position as a staple textile.
+
+The process has only the incidental interest in connection with our main
+subject, that it employs chiefly the 'chemical' pulps or celluloses as
+raw materials. The industrial future of the application must, of course,
+be largely determined by costs of production, as the directions of
+application in the weaving industries will be limited by the necessarily
+inferior grade of tensile strength belonging to these products and the
+degree by which this is lowered on complete wetting. All these questions
+have been duly weighed by those engaged in this interesting development,
+and the conclusion of those qualified to judge is that the new industry
+has vindicated for itself a permanent position.
+
+~II. The Chemical Derivatives of Cellulose~, in their industrial aspects,
+have come to occupy a profoundly important position in the world's
+affairs. In the way of any essential alteration of the perspective from
+that obtaining in 1895 we have nothing to chronicle. No new derivatives
+of industrial importance have been added in that period; but certain new
+methods incidental to the preparation of well-known compounds or for
+converting them into more generally available forms have been
+introduced, and these are contributing to the rapid expansion of the
+'artificial' cellulose industries.
+
+Of the cellulose esters the nitrates are still the only group in
+industrial use. There uses for explosives have attained immense
+proportions, and their applications for structural purposes are
+continually on the increase. The manufacture of smokeless powders on the
+one hand, and of celluloid and xylonite (both in the form of films and
+solid aggregates) on the other, has taken no new departure. The industry
+in 'artificial silks' or 'lustra-celluloses,' by the collodion processes
+also, whilst presenting features of unusual interest attaching to rapid
+expansion, has been barren of contribution of fundamental scientific or
+technical importance. The tetracetate is now manufactured on the large
+scale, but the product has yet to make its market.
+
+The process of mercerising cotton yarns and cloth has been developed to
+an industry of colossal dimensions, and the growth has been especially
+rapid during the last five years. Significant of the technical progress
+in these two industries, with their common aim of appreciating cellulose
+in the scale of textiles by approximating its external properties in
+those of silk, is the appearance of a monograph of the technology of
+each, notices of which have been previously given (pp. 22-26).
+
+There is little doubt, however, that the question of the future
+industry in the various forms of cellulose, thread, film, structureless
+powder or solid aggregate, obtainable by artificial means, mainly turns
+upon cost of production. Irrespective of cost, there would, no doubt, be
+a market for all these products, based upon such of their properties or
+effects as are indispensable and not otherwise obtainable. As an
+illustration, we may cite the extraordinary selling prices of 40-50 fr.
+per kilo, for the 'artificial silks' (collodion process) which ruled
+some three years ago; and we may note that for a special application of
+viscose the dissolved cellulose is paid for at the rate of 10 per
+lb. These facts are certainly worthy of mention, and should be borne in
+mind as an index of some special features of modern manufacturing
+industry. But with a material like cellulose rendered available in a new
+shape the question which always arises more prominently than that of
+limited uses at high prices is that of consumption on the extensive
+scale which marks the older and well-known products. That question is
+rapidly solving itself in this country as regards the 'artificial
+silks.' There is at present a limited market at 9s.-10s. per lb., a
+price which on the one side excludes extensive consumption, and on the
+other practically bars manufacture in this country by any of the
+collodion systems. It will appear from a very elementary calculation of
+what we may call the theoretical costs that the above selling price
+would not have a remunerative margin. The theoretical costs are made up
+of
+
+Raw materials[14]  {Cotton. Nitrating acid. Ether-alcohol (solvent).
+                   {Denitrating chemicals.
+
+                   {(a) Nitrating and preparing collodion. Denitrating
+                   { and bleaching.
+Labour             {(b) Textile operations. Spinning. Winding and twisting.
+                   {Rewinding.
+
+Power              {Making, filtering, and distributing collodion.
+                   {Driving textile machinery.
+
+Added to which are the costs of expert management and supervision and
+general establishment expenses. It is evident that raw materials make up
+a large fraction of the total cost; also that a very large item is the
+waste work of converting the cellulose into nitrate, only to remove the
+nitric groups so soon as the cellulose is obtained as thread.
+
+It is clear that the aqueous solutions of cellulose have a double
+advantage in this respect--not only do they readily yield an
+approximately pure cellulose as a direct product of regeneration or
+decomposition, but the first cost of the solution is very much less.
+With these newer products, therefore, the spinning problem enters on a
+new phase of struggle. It is certain that at selling prices at or about
+5s. to 7s., very large markets will be open to the product or
+products. The two processes which are or may be able to fulfil this
+demand are those based (1) on cuprammonium solutions of cellulose, (2)
+on the sulphocarbonate or viscose. As regards _first cost_ of the
+solution the latter has a large advantage. One ton of wood pulp (at
+12l.) can certainly be obtained in solution in a condition ready for
+spinning at a total cost (materials) of less than 30l. The
+cuprammonium process, so far as 'outside' information goes, requires for
+production of the solution (1) cotton as raw material, (2) ammonia
+(calc. as concentrated aqueous) equal to 1-1/2 times its weight, and
+(3) metallic copper 25 p.ct. of its weight; and the costs are
+approximately 100l. per ton. It is obvious that the materials are
+recoverable from the precipitating-bath, but at a certain added cost. We
+have no statements as to the proportion recoverable nor the costs
+incurred, and we are therefore unable to measure the total net cost of
+the regenerated cellulose by this process. It is certainly much less
+than by the collodion processes. As to the textile quality of the
+thread, the product has not yet been on a sufficiently wide selling
+basis for that to have been determined. There are a great many factors
+which enter here. Not merely the external characters of lustre,
+softness, and translucency, but the all-important quality of uniformity
+of thread. The collodion-spinning is a process still very defective in
+this respect, and the defect is no doubt referable to the difficulty of
+securing absolute physical invariability of the collodion. It is to be
+regretted, in the interests of scientific development, that none of the
+technologists who have published investigations of these processes have
+entered into the discussion of the fundamental factors of the spinning
+processes; we are, therefore, unable at this stage to discuss these
+elements of a full comparison in greater detail. We cannot, for this
+reason, say how far the cuprammonium process diverges in point of
+control from the standard of the collodion processes. Of the 'viscose'
+product we have a more intimate knowledge, and it certainly reaches a
+higher general standard than the older and now well-known artificial
+silks. The process is also sufficiently developed to enable the total
+costs of production to be estimated at a figure less than one-half that
+of the 'collodion' processes. This would assure to this system an
+_entr�e_ in this country, and a basis of expansion limited only by the
+ordinary laws of supply and demand.
+
+This prospect is opened up precisely at the moment when, for various
+reasons connected both with the difficulties of manufacture and the
+narrowing of the margin of profit, the proprietors of the two systems of
+collodion-spinning have decided to abandon all idea of manufacturing by
+these systems in this country.[15] We leave the discussion of the
+industrial problem at this point.
+
+In regard to other developments based upon the exceptional character and
+properties of the sulphocarbonate, their further discussion will
+exemplify no general principles; and as regards technical detail they
+have been dealt with in the papers previously noticed.
+
+As a purely general question, if there is to be any industry in these
+'artificial' forms of cellulose, commensurate with the magnitude that
+usually belongs to the cellulose industries, it must come by way of a
+plastic or soluble form prepared at low cost, and conserving the
+essential molecular properties of the cellulose aggregate. These are the
+particular features of the sulphocarbonate. The obvious difficulties in
+the way of its industrial applications are those caused by the presence
+of alkali and sulphur compounds. These are dealt with by appropriate
+chemical means; but the fact that there is a special chemistry of the
+product has rendered its industrial progress slow. The work of the last
+five years in this, as in other applications of cellulose in its many
+derived forms, has resulted in a considerable addition to the domain of
+practical chemistry.
+
+Further developments will make an increasing demand upon our grasp of
+the fundamental constitutional problems, to which it is the main purpose
+of the present volume to contribute.
+
+FOOTNOTES:
+
+[11] This is the most complete notice that has appeared and the
+bibliography is exhaustive. The publication comes into our hands too
+late to be noticed in detail.
+
+[12] _Text-book on Paper-making_, Cross and Bevan (Spon, London: second
+edition, 1900). _Chemistry of Paper-making_, Griffin and Little (New
+York, 1894: Howard Lockwood & Co.). _Handbuch d. Papierfabrikation_, C.
+Hofmann (Berlin). _Paper Trade Review_, London (weekly).
+_Papier-Zeitung_, Berlin.
+
+[13] William Mather, M.P., of the firm of Mather & Platt, Limited,
+Manchester.
+
+[14] The actual costs varying considerably in the various countries, we
+cannot make any specific statement. But from estimates we have made, the
+costs of obtaining cotton in filtered solution as collodion multiply its
+value by 12-14, the denitrations adding further costs and raising this
+multiple to 18-20. In the same estimates we arrived at the conclusion
+that the item for raw materials made up 60 p.ct. of the total cost of
+the yarn.
+
+[15] The recent failure of a French company founded for the exploitation
+of the cuprammonium process may be taken as showing that it presents
+very considerable technical difficulties. It is a matter of common
+knowledge that this company _estimated_ the costs of production to be
+such as to enable the product to be sold at 12 fr. per kilo., whereas
+the costs actually obtaining were a large multiple of this figure.
+
+
+
+
+INDEX OF AUTHORS
+
+
+Bardy, C. H., 157
+
+Bokorny, T., 43
+
+Bronnert, E., 54
+
+Bumcke, G., and Wolffenstein, R., 67
+
+Buntrock, 25
+
+
+Cross, C. F., 139, 152, 155
+
+Cross, C. F., and Bevan, E. J., 92
+
+Cross, C. F., Bevan, E. J., and Briggs, J. F., 118
+
+Cross, C. F., Bevan, E. J., and Heiberg, T., 114
+
+Cross, C. F., Bevan, E. J., and Smith, C., 101, 103, 105, 114, 145
+
+
+De Haas, R. W. T., and Tollens, B., 151
+
+
+Faber, O. v., and Tollens, B., 71
+
+Feilitzen, H. v., and Tollens, B., 154
+
+Fenton, H. J. H., 8
+
+Fenton, H. J. H., and Gostling, M., 86
+
+Fraenkel, A., and Friedlaender, P., 26
+
+
+Gardner, P., 22
+
+Gilson, E., 112
+
+
+Hancock, W. C., and Dahl, O. W., 135
+
+Hoffmeister, W., 96, 100
+
+
+Kleiber, A., 97
+
+Kr�ber, E., 121
+
+Kr�ger, M., 119
+
+
+Lange, H., 25
+
+Lewes, V. H., 15
+
+Luck, A., and Cross, C. F., 45
+
+
+Margosches, B. M., 159
+
+Morrell, R. S., and Crofts, J. M., 114
+
+Mylius, F., 21
+
+
+Nastukoff, H., 74
+
+
+Omelianski, V., 76
+
+
+Ruff, O., 117
+
+
+Salkowski, E., 113
+
+Sch�ne, A., and Tollens, B., 124
+
+Seidel, H., 149
+
+Sherman, H. C., 137
+
+Simonsen, E., 146
+
+Storer, F. H., 142
+
+Strehlenert, R. W., 158
+
+Suringar, H., and Tollens, B., 16, 124
+
+S�vern, C., 63
+
+
+Tollens, B., 148, 151
+
+Tollens, B., and Glaubitz, H., 122
+
+
+Vignon, L., 43, 70, 72, 94
+
+
+Will, W., and Lenze, P., 41
+
+Winterstein, E., 109, 144, 153
+
+
+
+
+INDEX OF SUBJECTS
+
+
+Acetone, action on cellulose nitrates of diluted, 46
+
+Acid-cellulose, 68
+
+Acids, volatile, from cellulose, 145
+
+_�schynomene aspera_, 135
+
+Alcohol from cellulose and wood, 146
+
+Alcoholic soda, mercerisation results with, 26
+
+Alkali-cellulose, effects of long storage on, 31
+
+Amyloid, vegetable, 153
+
+Arabinose from gluconic acid, 117
+
+'Ash' of plants, 13
+
+
+_Bacterium xylinum_, 85
+
+Barley plant, chemical processes in the, 103
+
+---- straw, carbohydrates of, 105
+
+Bleaching, 166
+
+Bran, digestion of, 139
+
+Brommethylfurfural, 8, 84, 86
+
+
+Carbohydrates, action of hydrogen bromide on, 86;
+  action of hydrogen peroxide on, 114;
+  nitrated, as food for mould fungi, 43;
+  nitrates of, 41;
+  quantitative separation of, 96
+
+Carbohydrates of barley straw, 105;
+  of wheat, 137;
+  of yeast, 113
+
+'Caro's reagent,' 118
+
+'Celloxin,' 71
+
+Cellulose, alcohol from, 146;
+  constitution of, 77, 92;
+  fermentation of, 76;
+  industrial uses of, 155;
+  iodine reaction of, 21;
+  methods for the estimation of, 3, 4, 16, 19, 97;
+  nitration of, 43;
+  saccharification of, 73;
+  ultimate hydrolysis of, 11;
+  volatile acids from, 145
+
+---- acetates, monoacetate, formation of, 40;
+  tetracetate, constitution of, 80
+
+---- benzoates, 34;
+  from structureless cellulose, 36;
+  from three varieties of cotton, 35;
+  monobenzoate, properties of, 36;
+  dibenzoate, properties of, 37;
+  acetylation of, 130;
+  nitration of, 38
+
+---- derivatives, commercial aspects of, 171;
+  saccharification of, 73
+
+---- nitrates, 44, 45, 83;
+  structureless, 45, 51;
+  cupric reducing power of, 73;
+  instability of, 50, 53
+
+---- sulphocarbonate, 27;
+  effects of the nature of the cellulose, 28;
+
+---- ---- solutions, analysis of, 32;
+  iodine reaction of, 33;
+  loss of carbon bisulphide, 33;
+  viscosity of, 30
+
+Cell-wall constituents, 97
+
+Cereal celluloses, 101, 105
+
+Chitin, 112
+
+Chlorination, Cross and Bevan's method, 19;
+  statistics of, 134
+
+Chloro-lignone, 126
+
+Collodion. _See_ Silk, artificial
+
+Cotton, lustreing effect of mercerisation, 23;
+  mercerised, structural properties of, 25;
+  pentosane content of, 148
+
+'Crude fibre,' 17
+
+Cuprammonium solvent, 21, 58, 173
+
+Currants, pectin of, 152
+
+
+Denitration of collodion silk, 56;
+  of jute nitrate, 133;
+  products of, 74
+
+Dioxybutyric acid, 71
+
+
+Elder pith, 137
+
+Eriodendron, seed hair of, 92
+
+Explosives, 44;
+  sporting powders, 52
+
+
+Fermentation of cellulose, 76;
+  of furfuroids, 108;
+  of sugar from wood, 148
+
+Fibres, report on miscellaneous, 139
+
+Flax boiling, 168;
+  spinning, 161
+
+Fodder plants, pentosanes of, 122
+
+Fungi, tissue constituents of, 109
+
+Furfural from cellulose, oxycellulose, and hydrocellulose, 70;
+  derivative from l�vulose, 8;
+  estimation as hydrazone and phloroglucide, 119, 121;
+  oxidation of, 114, 118 (_refer also_ 'Pentosanes')
+
+Furfuroids, 8, 10, 102, 105;
+  assimilation of, 108
+
+
+Gabriel's method of cellulose estimation, 18
+
+Gluconic acid, action of hydrogen peroxide on, 117
+
+Glucosamin, 112
+
+
+Hemicellulose, 96, 97;
+  determination and separation of, 100
+
+H�nig's method of cellulose estimation, 18
+
+'Hydralcellulose,' 68
+
+Hydrocellulose, 73;
+  nitration of, 43
+
+Hydrogen peroxide, oxidations with, 114
+
+Hydroxyfurfural in lignocellulose, 9, 116, 118
+
+
+Incandescent mantles of artificial silk, 14, 15
+
+Industrial appliances of cellulose, 155
+
+Iodine reaction of cellulose, 21
+
+Isosaccharinic acid, 71
+
+
+Jute, composition of, 141;
+  quality of, 140;
+  treatment of, 142 (_refer also_ Lignocellulose)
+
+---- acetate, 129
+
+---- benzoate, 127;
+  acetylation of, 130;
+  nitration of, 132
+
+---- nitrate, 131
+
+
+Ketoses, physiological importance of, 9
+
+
+Lange method of cellulose estimation, 18, 98
+
+Lead compounds of nitrated carbohydrates, 49
+
+Lignin, 100
+
+Lignocellulose, constitution of, 133;
+  esters of, 125;
+  hydroxyfurfural in, 9;
+  new type of, 135
+
+Lignone complex, properties of, 126
+
+'Lignorosin,' 151
+
+'Lustra-cellulose.' _See_ Silk, artificial
+
+
+Malt, pentosanes of, 122
+
+Mather system of boiling textiles, 167
+
+Mercerization, 22; shrinkage during, 24
+
+Mercerised yarn, strength and elasticity of, 25, 26
+
+Methylhydroxyfurfural, 84
+
+Mould fungi, nitrated carbohydrates as food for, 43
+
+Mycosin, 113
+
+
+Nitrated carbohydrates, lead compounds of, 49
+
+Nitrates of carbohydrates, 41
+
+Nitrocellulose (_see_ Cellulose nitrates);
+  silk, 55
+
+'Normal' cellulose, definition of, 27
+
+Normal paper, 160
+
+
+Oxycellulose esters, 72;
+  nitration of, 43;
+  researches on, 71, 72, 74;
+  _r�sum�_ of properties, 94
+
+Oxygluconic acid, 117
+
+
+Paper, deterioration of, 155;
+  normal standard, 160;
+  pulp, spinning of, 169
+
+Peat, constituents of, 154
+
+Pectins, 151, 152
+
+Pentosanes, 100, 109, 144;
+  constituents of cotton, 124;
+  constituents of fodder, 122;
+  estimation of, 121;
+  of seeds during germination, 124
+
+'Permanent tissue,' 103
+
+Phloroglucinol, 119, 121
+
+Plant tissues, carbohydrates of, 96, 97, 99
+
+Plants, source of unsaturated compounds in, 145
+
+Powders, manufacture of sporting, 52
+
+
+Saccharification of cellulose and derivatives, 73
+
+Schulze method of cellulose estimation, 18, 98
+
+Schweizer solution, 101
+
+Seeds, pentosanes in germinating, 124
+
+Silica in plant tissues, 13
+
+Silk, artificial, 54, 62, 63, 172;
+  bibliography of, 60;
+  from cuprammonium, 58, 64, 173;
+  from nitrocellulose (collodion), 55, 63, 172;
+  from viscose, 59;
+  from zinc chloride, 59;
+  reactions of, 64
+
+---- natural, reactions of, 64
+
+Straws, 101, 105
+
+Succinic acid from furfural, 118
+
+Sulphite waste liquors, 149, 164
+
+'Swedish' filter paper, 14
+
+
+Tissue constituents, 99, 109
+
+Trees, composition of trunk woods, 142
+
+
+Viscose and viscoid, 157, 158, 159
+
+---- silk, 59, 175
+
+---- ---- specific gravity of, 34 (_refer also_ Cellulose
+sulphocarbonate)
+
+'Vulcanised fibre,' 20
+
+
+Weende, method of cellulose estimation (crude fibre), 17, 98
+
+Welsbach mantles, 14;
+  Clamond type, 15
+
+Wheat grain, insoluble carbohydrates of, 137
+
+Wood, alcohol from, 146, 148
+
+Wood-cellulose, waste liquors, 149
+
+Wood-gum, 144
+
+Wood-pulp, processes, 162
+
+Wood, trunks of trees, 142
+
+
+Yeast, carbohydrates of, 113
+
+
+Zinc chloride, artificial silk, 59;
+  solvent action of, 20
+
+
+
+
+
+
+End of the Project Gutenberg EBook of Researches on Cellulose, by 
+C. F. Cross and E. J. Bevan
+
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+Project Gutenberg's Researches on Cellulose, by C. F. Cross and E. J. Bevan
+
+This eBook is for the use of anyone anywhere at no cost and with
+almost no restrictions whatsoever.  You may copy it, give it away or
+re-use it under the terms of the Project Gutenberg License included
+with this eBook or online at www.gutenberg.org
+
+
+Title: Researches on Cellulose
+       1895-1900
+
+Author: C. F. Cross
+        E. J. Bevan
+
+Release Date: September 16, 2007 [EBook #22620]
+
+Language: English
+
+Character set encoding: ISO-8859-1
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+*** START OF THIS PROJECT GUTENBERG EBOOK RESEARCHES ON CELLULOSE ***
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+
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+
+
+
+
+<h1>RESEARCHES ON CELLULOSE</h1>
+
+<h4>1895-1900</h4>
+
+<h3>BY</h3>
+
+<h2>CROSS &amp; BEVAN</h2>
+
+<h4>(C. F. CROSS AND E. J. BEVAN)</h4>
+
+
+<h3><i>SECOND EDITION</i></h3>
+
+
+<p class="center">
+LONGMANS, GREEN, AND CO.<br />
+39 PATERNOSTER ROW, LONDON<br />
+NEW YORK, BOMBAY, AND CALCUTTA<br />
+<br />
+1907<br />
+<br />
+All rights reserved<br />
+</p>
+
+<p class="notes">Transcriber's note: The sections in the Table of Contents are not used in the actual text.
+They have been added for clarity. Minor typos have been corrected and footnotes moved to the end of the
+sections</p>
+
+
+
+<hr style="width: 65%;" />
+<h2>PREFACE TO SECOND EDITION</h2>
+
+
+<p>This edition is a <i>reprint</i> of the first in response to a continuous
+demand for the book. The matter, consisting as it does largely of
+records, does not call for any revision, and, as a contribution to the
+development of theory, any particular interest which it has is
+associated with the date at which it was written.</p>
+
+<p>The volume which has since appeared is the sequel, and aims at an
+exposition of the subject "to date".</p>
+
+
+
+<hr style="width: 65%;" />
+<h2>PREFACE</h2>
+
+
+<p>This volume, which is intended as a supplement to the work which we
+published in 1895, gives a brief account of researches which have been
+subsequently published, as well as of certain of our own investigations,
+the results of which are now for the first time recorded.</p>
+
+<p>We have not attempted to give the subject-matter the form of a connected
+record. The contributions to the study of 'Cellulose' which are noticed
+are spread over a large area, are mostly 'sectional' in their aim, and
+the only cohesion which we can give them is that of classifying them
+according to the plan of our original work. Their subject-matter is
+reproduced in the form of a <i>pr&eacute;cis</i>, as much condensed as possible; of
+the more important papers the original title is given. In all cases we
+have endeavoured to reproduce the Author's main conclusions, and in most
+cases without comment or criticism.</p>
+
+<p>Specialists will note that the basis of investigation is still in a
+great measure empirical; and of this the most obvious criterion is the
+confusion attaching to the use of the very word 'Cellulose.' This is due
+to various causes, one of which is the curious specialisation of the
+term in Germany as the equivalent of 'wood cellulose.' The restriction
+of this general or group term has had an influence even in scientific
+circles. Another influence preventing the recognition of the obvious
+and, as we think, inevitable basis of classification of the 'celluloses'
+is the empiricism of the methods of agricultural chemistry, which as
+regards cellulose are so far chiefly concerned with its negative
+characteristics and the analytical determination of the indigestible
+residue of fodder plants. Physiologists, again, have their own views and
+methods in dealing with cellulose, and have hitherto had but little
+regard to the work of the chemist in differentiating and classifying the
+celluloses on a systematic basis. There are many sides to the subject,
+and it is only by a sustained effort towards centralisation that the
+general recognition of a systematic basis can be secured.</p>
+
+<p>We may, we hope usefully, direct attention to the conspicuous neglect of
+the subject in this country. To the matter of the present volume,
+excluding our own investigations, there are but two contributions from
+English laboratories. We invite the younger generation of students of
+chemistry to measure the probability of finding a working career in
+connection with the cellulose industries. They will not find this
+invitation in the treatment accorded to the subject in text-books and
+lectures. It is probable, indeed, that the impression produced by their
+studies is that the industries in coal-tar products largely exceed in
+importance those of which the carbohydrates are the basis; whereas the
+former are quite insignificant by comparison. A little reflection will
+prove that cellulose, starch, and sugar are of vast industrial moment in
+the order in which they are mentioned. If it is an open question to
+what extent science follows industry, or <i>vice versa</i>, it is not open to
+doubt that scientific men, and especially chemists, are called in these
+days to lead and follow where industrial evolution is most active. There
+is ample evidence of activity and great expansion in the cellulose
+industries, especially in those which involve the chemistry of the raw
+material; and the present volume should serve to show that there is
+rapid advance in the science of the subject. Hence our appeal to the
+workers not to neglect those opportunities which belong to the days of
+small beginnings.</p>
+
+<p>We have especially to acknowledge the services of Mr. J. F. <span class="smcap">Briggs</span> in
+investigations which are recorded on pp. 34-40 and pp. 125-133 of the
+text.</p>
+
+
+
+<hr style="width: 65%;" />
+<h2>CONTENTS</h2>
+
+<h3>THE MATTER OF THIS VOLUME MAY BE DIVIDED INTO THE FOLLOWING SECTIONS</h3>
+
+
+<p>
+<span class="linenum">PAGE</span><br />
+<br />
+INTRODUCTION&mdash;DEALING WITH THE SUBJECT IN GENERAL OUTLINE           <span class="linenum"><a href="#Page_1">1</a></span><br />
+<br />
+<br />
+SECTION<br />
+<br />
+I. GENERAL CHEMISTRY OF THE TYPICAL COTTON CELLULOSE               <span class="linenum"><a href="#Page_13">13</a></span><br />
+<br />
+II. SYNTHETICAL DERIVATIVES&mdash;SULPHOCARBONATES AND ESTERS   <span class="linenum"><a href="#Page_27">27</a></span><br />
+<br />
+III. DECOMPOSITIONS OF CELLULOSE SUCH AS THROW LIGHT ON THE PROBLEM OF ITS CONSTITUTION  <span class="linenum"><a href="#Page_67">67</a></span><br />
+<br />
+IV. CELLULOSE GROUP, INCLUDING HEMICELLULOSES AND TISSUE CONSTITUENTS OF FUNGI  <span class="linenum"><a href="#Page_97">97</a></span><br />
+<br />
+V. FURFUROIDS, <i>i.e.</i> PENTOSANES AND FURFURAL-YIELDING  CONSTITUENTS GENERALLY               <span class="linenum"><a href="#Page_114">114</a></span><br />
+<br />
+VI. THE LIGNOCELLULOSES                                           <span class="linenum"><a href="#Page_125">125</a></span><br />
+<br />
+VII. PECTIC GROUP                                                 <span class="linenum"><a href="#Page_152">152</a></span><br />
+<br />
+VIII. INDUSTRIAL AND TECHNICAL. GENERAL REVIEW                    <span class="linenum"><a href="#Page_155">155</a></span><br />
+<br />
+<br />
+INDEX OF AUTHORS                                                  <span class="linenum"><a href="#Page_177">177</a></span><br />
+<br />
+INDEX OF SUBJECTS                                                 <span class="linenum"><a href="#Page_178">178</a></span><br />
+</p>
+
+
+
+<hr style="width: 65%;" />
+<h2>CELLULOSE</h2>
+
+
+
+<hr style="width: 65%;" />
+<p><span class='pagenum'><a name="Page_1" id="Page_1">[Pg 1]</a></span></p>
+<h2>INTRODUCTION</h2>
+
+
+<p>In the period 1895-1900, which has elapsed since the original
+publication of our work on 'Cellulose,' there have appeared a large
+number of publications dealing with special points in the chemistry of
+cellulose. So large has been the contribution of matter that it has been
+considered opportune to pass it under review; and the present volume,
+taking the form of a supplement to the original work, is designed to
+incorporate this new matter and bring the subject as a whole to the
+level to which it is thereby to be raised. Some of our critics in
+reviewing the original work have pronounced it 'inchoate.' For this
+there are some explanations inherent in the matter itself. It must be
+remembered that every special province of the science has its systematic
+beginning, and in that stage of evolution makes a temporary 'law unto
+itself.' In the absence of a dominating theory or generalisation which,
+when adopted, gives it an organic connection with the general advance of
+the science, there is no other course than to classify the
+subject-matter. Thus 'the carbohydrates' may be said to have been in the
+inchoate condition, qualified by a certain classification, prior to the
+pioneering investigations of Fischer. In attacking the already
+accumulated and so far classified material from the point of view of a
+dominating theory, he found not only that the material fell into
+systematic order<span class='pagenum'><a name="Page_2" id="Page_2">[Pg 2]</a></span> and grew rapidly under the stimulus of fruitful
+investigation, but in turn contributed to the firmer establishment of
+the theoretical views to which the subject owed its systematic new
+birth. On the other hand, every chemist knows that it is only the
+simpler of the carbohydrates which are so individualised as to be
+connoted by a particular formula in the stereoisomeric system. Leaving
+the monoses, there is even a doubt as to the constitution of cane sugar;
+and the elements of uncertainty thicken as we approach the question of
+the chemical structure of starch. This unique product of plant life has
+a literature of its own, and how little of this is fully known to what
+we may term the 'average chemist' is seen by the methods he will employ
+for its quantitative estimation. In one particular review of our work
+where we are taken to task for producing 'an aggravating book, inchoate
+in the highest degree ... disfigured by an obscurity of diction which
+must materially diminish its usefulness' ['Nature,' 1897, p. 241], the
+author, who is a well-known and competent critic, makes use of the short
+expression in regard to the more complex carbohydrates, 'Above cane
+sugar, higher in the series, all is chaos,' and in reference to starch,
+'the subject is still enshrouded in mystery.' This 'material' complexity
+is at its maximum with the most complex members of the series, which are
+the celluloses, and we think accounts in part for the impatience of our
+critic. 'Obscurity of diction' is a personal quantity, and we must leave
+that criticism to the fates. We find also that many workers whose
+publications we notice in this present volume quite ignore the <i>plan</i> of
+the work, though they make use of its matter. We think it necessary to
+restate this plan, which, we are satisfied, is systematic, and, in fact,
+inevitable. Cellulose is in the first instance a <i>structure</i>, and the
+anatomical relationships supply a certain basis of classification. Next,
+it is known to us and is defined<span class='pagenum'><a name="Page_3" id="Page_3">[Pg 3]</a></span> by the negative characteristics of
+resistance to hydrolytic actions and oxidations. These are dealt with in
+the order of their intensity. Next we have the more positive definition
+by ultimate products of hydrolysis, so far as they are known, which
+discloses more particularly the presence of a greater or less proportion
+of furfural-yielding groups. Putting all these together as criteria of
+function and composition we find they supply common or general dividing
+lines, within which groups of these products are contained. The
+classification is natural, and in that sense inevitable; and it not only
+groups the physiological and chemical facts, but the industrial also. We
+do not propose to argue the question whether the latter adds any cogency
+to a scientific scheme. We are satisfied that it does, and we do not
+find any necessity to exclude a particular set of phenomena from
+consideration, because they involve 'commercial' factors. We have dealt
+with this classification in the original work (p. 78), and we discuss
+its essential basis in the present volume (p. 28) in connection with the
+definition of a 'normal' cellulose. But the 'normal' cellulose is not
+the only cellulose, any more than a primary alcohol or an aliphatic
+alcohol are the only alcohols. This point is confused or ignored in
+several of the recent contributions of investigators. It will suffice to
+cite one of these in illustration. On p. 16 we give an account of an
+investigation of the several methods of estimating cellulose, which is
+full of valuable and interesting matter. The purpose of the author's
+elaborate comparative study is to decide which has the strongest claims
+to be regarded as the 'standard' method. They appear to have a
+preference for the method of Lange&mdash;viz. that of heating at high
+temperatures (180&deg;) with alkaline hydrates, but the investigation shows
+that (as we had definitely stated in our original work, p. 214) this is
+subject to large and variable errors. The adverse judgment of the
+authors, we may<span class='pagenum'><a name="Page_4" id="Page_4">[Pg 4]</a></span> point out, is entirely determined on the question of
+aggregate weight or yield, and without reference to the ultimate
+composition or constitution of the final product. None of the available
+criteria are applied to the product to determine whether it is a
+cellulose (anhydride) or a hydrate or a hydrolysed product. After these
+alkali-fusion processes the method of chlorination is experimentally
+reviewed and dismissed for the reason that the product retains
+furfural-yielding groups, which is, from our point of view, a particular
+recommendation, i.e. is evidence of the selective action of the chlorine
+and subsequent hydrolysis upon the lignone group. As a matter of fact it
+is the only method yet available for isolating the cellulose from a
+lignocellulose by a treatment which is quantitatively to be accounted
+for in every detail of the reactions. It does not yield a 'normal'
+cellulose, and this is the expression which, in our opinion, the authors
+should have used. It should have been pointed out, moreover, that, as
+the cellulose is separated from actual condensed combination with the
+lignone groups, it may be expected to be obtained in a hydrated form,
+and also not as a homogeneous substance like the normal cotton
+cellulose. The product is a cellulose of the second group of the
+classification. Another point in this investigation which we must
+criticise is the ultimate selection of the Schulze method of prolonged
+maceration with nitric acid and a chlorate, followed by suitable
+hydrolysis of the non-cellulose derivatives to soluble products. Apart
+from its exceptional inconvenience, rendering it quite impracticable in
+laboratories which are concerned with the valuation of cellulosic raw
+materials for industrial purposes, the attack of the reagent is complex
+and ill-defined. This criticism we would make general by pointing out
+that such processes quite ignore the specific characteristics of the
+non-cellulose components of the compound celluloses. The second division
+of the plan of our<span class='pagenum'><a name="Page_5" id="Page_5">[Pg 5]</a></span> work was to define these constituents by bringing
+together all that had been established concerning them. These groups are
+widely divergent in chemical character, as are the compound celluloses
+in function in the plant. Consequently there is for each a special
+method of attack, and it is a reversion to pure empiricism to expect any
+one treatment to act equally on the pectocelluloses, lignocelluloses,
+and cutocelluloses. Processes of isolating cellulose are really more
+strictly defined as methods of selective and regulated attack of the
+groups with which they occur, combined or mixed. A chemist familiar with
+such types as rhea or ramie (pectocellulose), jute (lignocellulose), and
+raffia (cutocellulose) knows exactly the specific treatment to apply to
+each for isolating the cellulose, and must view with some surprise the
+appearance at this date of such 'universal prescriptions' as the process
+in question.</p>
+
+<p>The third division of our plan of arrangement comprised the synthetical
+derivatives of the celluloses, the sulphocarbonates first, as peculiarly
+characteristic, and then the esters, chiefly the acetates, benzoates,
+and nitrates. To these, investigators appear to have devoted but little
+attention, and the contribution of new matter in the present volume is
+mainly the result of our own researches. It will appear from this work
+that an exhaustive study of the cellulose esters promises to assist very
+definitely in the study of constitutional problems.</p>
+
+<p>This brings us to the fourth and, to the theoretical chemist, the most
+important aspect of the subject, the problem of the actual molecular
+structure of the celluloses and compound celluloses. It is herein we are
+of opinion that the subject makes a 'law unto itself.' If the
+constitution of starch is shrouded in mystery and can only be vaguely
+expressed by generalising a complex mass of statistics of its successive
+hydrolyses, we can only still more vaguely guess at<span class='pagenum'><a name="Page_6" id="Page_6">[Pg 6]</a></span> the distance which
+separates us from a mental picture of the cellulose unit. We endeavour
+to show by our later investigations that this problem merges into that
+of the actual structure of cellulose in the mass. It is definitely
+ascertained that a change in the molecule, or reacting unit, of a
+cellulose, proportionately affects the structural properties of the
+derived compounds, both sulphocarbonates and esters. This is at least an
+indication that the properties of the visible aggregates are directly
+related to the actual configuration of the chemical units. But it
+appears that we are barred from the present discussion of such a problem
+in absence of any theory of the solid state generally, but more
+particularly of those forms of matter which are grouped together as
+'colloids.'</p>
+
+<p>Cellulose is distinguished by its inherent constructive functions, and
+these functions take effect in the plastic or colloidal condition of the
+substance. These properties are equally conspicuous in the synthetical
+derivatives of the compound. Without reference, therefore, to further
+speculations, and not deterred by any apparent hopelessness of solving
+so large a problem, it is clear that we have to exhaust this field by
+exact measurements of all the constants which can be reduced to
+numerical expression. It is most likely that the issue may conflict with
+some of our current views of the molecular state which are largely drawn
+from a study of the relatively dissociated forms of matter. But such
+conflicts are only those of enlargement, and we anticipate that all
+chemists look for an enlargement of the molecular horizon precisely in
+those regions where the forces of cell-life manifest themselves.</p>
+
+<p>The <i>cellulose group</i> has been further differentiated by later
+investigations. The fibrous celluloses of which the typical members
+receive important industrial applications, graduate by insensible stages
+into the hemicelluloses which may be regarded as a well-established
+sub-group. In considering<span class='pagenum'><a name="Page_7" id="Page_7">[Pg 7]</a></span> their morphological and functional
+relationships it is evident that the graduation accords with their
+structure and the less permanent functions which they fulfil. They are
+aggregates of monoses of the various types, chiefly mannose, galactose,
+dextrose, &amp;c., so far as they have been investigated.</p>
+
+<p>Closely connected with this group are the constituents of the tissues of
+fungi. The recent researches of Winterstein and Gilson, which are noted
+in this present volume, have established definitely that they contain a
+nitrogenous group in intimate combination with a carbohydrate complex.
+This group is closely related to chitin, yielding glucosamin and acetic
+acid as products of ultimate hydrolysis. Special interest attaches to
+these residues, as they are in a sense intermediate products between the
+great groups of the carbohydrates and proteids (E. Fischer, Ber. 19,
+1920), and their further investigation by physiological methods may be
+expected to disclose a genetic connection.</p>
+
+<p>The <i>lignocelluloses</i> have been further investigated. Certain new types
+have been added, notably a soluble or 'pectic' form isolated from the
+juice of the white currant (p. 152), and the pith-like wood of the
+&AElig;schynomene (p. 135).</p>
+
+<p>Further researches on the typical fibrous lignocellulose have given us a
+basis for correcting some of the conclusions recorded in our original
+work, and a study of the esters has thrown some light on the
+constitution of the complex (p. 130).</p>
+
+<p>Of importance also is the identification of the hydroxyfurfurals as
+constituents of the lignocelluloses generally, and the proof that the
+characteristic colour-reactions with phenols (phloroglucinol) may be
+ascribed to the presence of these compounds (p. 116).</p>
+
+<p>The <i>pectocelluloses</i> have not been the subject of systematic chemical
+investigation, but the researches of Gilson ('La Cristallisation de la
+Cellulose et la Composition Chimique de<span class='pagenum'><a name="Page_8" id="Page_8">[Pg 8]</a></span> la Membrane Cellulaire
+V&eacute;g&eacute;tale,' 'La Revue,' 'La Cellule,' i. ix.) are an important
+contribution to the natural history of cellulose, especially in relation
+to the 'pectic' constituents of the parenchymatous celluloses.
+Indirectly also the researches of Tollens on the 'pectins' have
+contributed to the subject in correcting some of the views which have
+had a text-book currency for a long period. These are dealt with on p.
+151. The results establish that the pectins are rather the soluble
+hydrated form of cellulosic aggregates in which acid groups may be
+represented; but such groups are not to be regarded as essentially
+characteristic of this class of compounds.</p>
+
+<p><b>Furfural-yielding Substances</b> (Furfuroids).&mdash;This group of plant products
+has been, by later investigations, more definitely and exclusively
+connected with the celluloses&mdash;i.e. with the more permanent of plant
+tissues. From the characteristic property of yielding furfural, which
+they have in common with the pentoses, they have been assumed to be the
+anhydrides of these C<sub>5</sub> sugars or pentosanes; but the direct evidence
+for this assumption has been shown to be wanting. In regard to their
+origin the indirect evidences which have accumulated all point to their
+formation in the plant from hexoses. Of special interest, in its
+bearings on this point, is the direct transformation of levulose into
+furfural derivatives, which takes place under the action of condensing
+agents. The most characteristic is that produced by the action of
+anhydrous hydrobromic acid in presence of ether [Fenton], yielding a
+brommethyl furfural</p>
+
+<p>
+<span style="margin-left: 2.5em;">C<sub>6</sub>H<sub>12</sub>O<sub>6</sub> - 4H<sub>2</sub>O + HBr = C<sub>5</sub>H<sub>3</sub>.O<sub>2</sub>.CH<sub>2</sub>Br</span><br />
+</p>
+
+<p>with a Br atom in the methyl group. These researches of Fenton's appear
+to us to have the most obvious and direct bearings upon the genetic
+relationships of the plant furfuroids and not only <i>per se</i>. To give
+them their full significance we<span class='pagenum'><a name="Page_9" id="Page_9">[Pg 9]</a></span> must recall the later researches of
+Brown and Morris, which establish that cane sugar is a primary or direct
+product of assimilation, and that starch, which had been assumed to be a
+species of universal <i>mati&egrave;re premi&egrave;re</i>, is probably rather a general
+reserve for the elaborating work of the plant. If now the aldose groups
+tend to pass over into the starch form, representing a temporary
+overflow product of the assimilating energy, it would appear that the
+ketose or levulose groups are preferentially used up in the elaboration
+of the permanent tissue. We must also take into consideration the
+researches of Lobry de Bruyn showing the labile functions of the typical
+CO group in both aldoses and hexoses, whence we may conclude that in the
+plant-cell the transition from dextrose to levulose is a very simple and
+often occurring process.</p>
+
+<p>We ourselves have contributed a link in this chain of evidence
+connecting the furfuroids of the plant with levulose or other
+keto-hexose. We have shown that the hydroxyfurfurals are constituents of
+the lignocelluloses. The proportion present in the free state is small,
+and it is not difficult to show that they are products of breakdown of
+the lignone groups. If we assume that such groups are derived ultimately
+from levulose, we have to account for the detachment of the methyl
+group. This, however, is not difficult, and we need only call to mind
+that the lignocelluloses are characterised by the presence of methoxy
+groups and a residue which is directly and easily hydrolysed to acetic
+acid. Moreover, the condensation need not be assumed to be a simple
+dehydration with attendant rearrangement; it may very well be
+accompanied or preceded by fixation of oxygen. Leaving out the
+hypothetical discussion of minor variations, there is a marked
+convergence of the evidence as to the main facts which establish the
+general relationships of the furfuroid group. This group includes both
+saturated and unsaturated or condensed compounds. The<span class='pagenum'><a name="Page_10" id="Page_10">[Pg 10]</a></span> former are
+constituents of celluloses, the latter of the lignone complex of the
+lignocelluloses.</p>
+
+<p>The actual production of furfural by boiling with condensing acids is a
+quantitative measure of only a portion, i.e. certain members of the
+group. The hydroxyfurfurals, not being volatile, are not measured in
+this way. By secondary reactions they may yield some furfural, but as
+they are highly reactive compounds, and most readily condensed, they are
+for the most part converted into complex 'tarry' products. Hence we have
+no means, as yet, of estimating those tissue constituents which yield
+hydroxyfurfurals; also we have no measure of the furfurane-rings
+existing performed in such a condensed complex as lignone. But, chemists
+having added in the last few years a large number of facts and
+well-defined probabilities, it is clear that the further investigation
+of the furfuroid group will take its stand upon a much more adequate
+basis than heretofore. On the view of 'furfural-yielding' being
+co-extensive with 'pentose or pentosane,' not only were a number of
+important facts obscured or misinterpreted, but there was a barrenness
+of suggestion of genetic relationships. As the group has been widened
+very much beyond these limits, it is clear that if any group term or
+designation is to be retained that of 'furfuroid' is 'neutral' in
+character, and equally applicable to saturated substances of such widely
+divergent chemical character as pentoses, hexosones, glycuronic acid,
+and perhaps, most important of all, levulose itself, all of which are
+susceptible of condensation to furfural or furfurane derivatives, as
+well as to those unsaturated compounds, constituents of plant tissues
+which are already furfurane derivatives.</p>
+
+<p>From the chemical point of view such terms are perhaps superfluous. But
+physiological relationships have a significance of their own; and there
+is a physiological or functional<span class='pagenum'><a name="Page_11" id="Page_11">[Pg 11]</a></span> cohesion marking this group which
+calls for recognition, at least for the time, and we therefore propose
+to retain the term furfuroid.<a name="FNanchor_1_1" id="FNanchor_1_1"></a><a href="#Footnote_1_1" class="fnanchor">[1]</a></p>
+
+<p><b>General Experimental Methods.</b>&mdash;In the investigation of the cellulose
+group it is clear that methods of ultimate hydrolysis are of first
+importance. None are so convenient as those which are based on the
+action of sulphuric acid, more or less concentrated (H<sub>2</sub>SO<sub>4</sub>.3H<sub>2</sub>O
+- H<sub>2</sub>SO<sub>4</sub>H<sub>2</sub>O). Such methods have been frequently employed in the
+investigations noted in this volume. We notice a common deficiency in
+the interpretation of the results. It appears to be sufficient to
+isolate and identify a crystalline monose, without reference to the
+yield or proportion to the parent substance, to establish some main
+point in connection with its constitution. On the other hand, it is
+clear that in hydrolysing a given cellulose-complex we ought to aim at
+complete, i.e. <i>quantitative, statistics</i>. The hydrolytic transformation
+of starch to dextrins and maltose has been followed in this way, and the
+methods may serve as a model to which cellulose transformations should
+be approximated. In fact, what is very much wanted is a systematic
+re-examination of the typical celluloses in which all the constants of
+the terms between the original and the ultimate monose groups shall be
+determined. Such constants are similar to those for the starch-dextrose
+series, viz. opticity and cupric reduction. Various methods of
+fractionation are similarly available, chiefly the precipitation of the
+intermediate 'dextrins' by alcohol.</p>
+
+<p>Where the original celluloses are homogeneous we should thus obtain
+transformation series, similarly expressed to those of starch. In the
+case of the celluloses which are mixtures, or of complex constitution,
+there are various methods of<span class='pagenum'><a name="Page_12" id="Page_12">[Pg 12]</a></span> either fractionating the original, or of
+selectively attacking particular monoses resulting from the
+transformation. By methods which are approximately quantitative a
+mixture of groups, such as we have, for instance, in jute cellulose,
+could be followed through the several stages of their resolution into
+monoses. To put the matter generally, in these colloidal and complex
+carbohydrates the ordinary physical criteria of molecular weight are
+wanting. Therefore, we cannot determine the relationship of a given
+product of decomposition to the parent molecule save by means of a
+quantitative mass-proportion. Physical criteria are only of determining
+value when associated with such constants as cupric reduction, and
+these, again, must be referred to some arbitrary initial weight, such
+as, for convenience, 100 parts of the original.</p>
+
+<p>Instead of adopting these methods, without which, as a typical case, the
+mechanism of starch conversions could not have been followed, we have
+been content with a purely qualitative study of the analogous series
+obtainable from the celluloses under the action of sulphuric acid. A
+very important field of investigation lies open, especially to those who
+are generally familiar with the methods of studying starch conversions;
+and we may hope in this direction for a series of valuable contributions
+to the problem of the actual constitution of the celluloses.</p>
+
+<div class="footnotes"><h3>FOOTNOTES:</h3>
+
+<div class="footnote"><p><a name="Footnote_1_1" id="Footnote_1_1"></a><a href="#FNanchor_1_1"><span class="label">[1]</span></a> In this we are confirmed by other writers. See Tollens, <i>J.
+f&uuml;r Landw.</i> 1901, p. 27.</p></div>
+</div>
+
+
+<hr style="width: 65%;" />
+<p><span class='pagenum'><a name="Page_13" id="Page_13">[Pg 13]</a></span></p>
+<h2>SECTION I. GENERAL CHEMISTRY OF THE TYPICAL COTTON CELLULOSE</h2>
+
+
+<p>(p. 3)<a name="FNanchor_2_2" id="FNanchor_2_2"></a><a href="#Footnote_2_2" class="fnanchor">[2]</a> <b>Ash Constituents.</b>&mdash;It is frequently asserted that silica has a
+structural function <i>sui generis</i> in the plant skeleton, having a
+relationship to the cellulosic constituents of the plant, distinct from
+that of the inorganic ash components with which it is associated. It
+should be noted that the matter has been specifically investigated in
+two directions. In Berl. Ber. 5, 568 (A. Ladenburg), and again in 11,
+822 (W. Lange), appear two papers 'On the Nature of Plant Constituents
+containing Silicon,' which contain the results of experimental
+investigations of equisetum species&mdash;distinguished for their
+exceptionally high 'ash' with large proportion of silica&mdash;to determine
+whether there are any grounds for assuming the existence of
+silicon-organic compounds in the plant, the analogues of carbon
+compounds. The conclusions arrived at are entirely negative. In
+reference to the second assumption that the cuticular tissues of cereal
+straws, of esparto, of the bamboo, owe their special properties to
+siliceous components, it has been shown by direct experiment upon the
+former that their rigidity and resistance to water are in no way
+affected by cultivation in a silica-free medium. In other words, the
+structural peculiarities of the gramine&aelig; in these respects are due to
+the physical characteristics chiefly of the (lignified) cells of the
+hypodermal tissue, and to the composition and arrangement of the cells
+of the cuticle.<span class='pagenum'><a name="Page_14" id="Page_14">[Pg 14]</a></span></p>
+
+<p><i>'Swedish' filter papers</i> of modern make are so far freed from inorganic
+constituents that the weight of the ash may be neglected in nearly all
+quantitative experiments [Fresenius, Ztschr. Anal Chem. 1883, 241]. It
+represents usually about 1/1000 mgr. per 1 sq. cm. of area of the paper.</p>
+
+<p><i>The form of an 'ash'</i> derived from a fibrous structure, is that of the
+'organic' original, more or less, according to its proportion and
+composition. The proportion of 'natural ash' is seldom large enough, nor
+are the components of such character as to give a coherent ash, but if
+in the case of a fibrous structure it is combined or intimately mixed
+with inorganic compounds deposited within the fibres from solution, the
+latter may be made to yield a perfect skeleton of the fibre after
+burning off the organic matter. It is by such means that the mantles
+used in the Welsbach system of incandescent lighting are prepared. A
+purified cotton fabric&mdash;or yarn&mdash;is treated with a concentrated solution
+of the mixed nitrates of thorium and cerium, and, after drying, the
+cellulose is burned away. A perfect and coherent skeleton of the fabric
+is obtained, composed of the mixed oxides. Such mantles have fulfilled
+the requirements of the industry up to the present time, but later
+experiments forecast a notable improvement. It has been found that
+artificial cellulose fibres can be spun with solutions containing
+considerable proportions of soluble compounds of these oxides. Such
+fibres, when knitted into mantles and ignited, yield an inorganic
+skeleton of the oxides of homogeneous structure and smooth contour. De
+Mare in 1894, and Knofler in 1895, patented methods of preparing such
+cellulose threads containing the salts of thorium and cerium, by
+spinning a collodion containing the latter in solution. When finally
+ignited, after being brought into the suitable mantle form, there
+results a structure which proves vastly more durable than the original
+Welsbach mantle. The<span class='pagenum'><a name="Page_15" id="Page_15">[Pg 15]</a></span> cause of the superiority is thus set forth by V.
+H. Lewes in a recent publication (J. Soc. of Arts, 1900, p. 858): 'The
+alteration in physical structure has a most extraordinary effect upon
+the light-giving life of the mantle, and also on its strength, as after
+burning for a few hundred hours the constant bombardment of the mantle
+by dust particles drawn up by the rush of air in the chimney causes the
+formation of silicates on the surface of the mantle owing to silica
+being present in the air, and this seems to affect the Welsbach
+structure far more than it does the "Clamond" type, with the result that
+when burned continuously the Welsbach mantle falls to so low a pitch of
+light emissivity after 500 to 600 hours, as to be a mere shadow of its
+former self, giving not more than one-third of its original light,
+whilst the Knofler mantle keeps up its light-emitting power to a much
+greater extent, and the Lehner fabric is the most remarkable of all. Two
+Lehner mantles which have now been burning continuously in my laboratory
+for over 3,000 hours give at this moment a brighter light emissivity
+than most of the Welsbachs do in their prime.' ...'The new developments
+of the Clamond process form as important a step in the history of
+incandescent gas lighting as the discoveries which gave rise to the
+original mantles.'</p>
+
+<p>It has further been found that the oxides themselves can be dissolved in
+the cellulose alkaline sulphocarbonate (viscose) solution, and
+artificial threads have been spun containing from 25 to 30 p.ct. of the
+oxides in homogeneous admixture with the cellulose. This method has
+obvious advantages over the collodion method both in regard to the
+molecular relationship of the oxides to the cellulose and to cheapness
+of production.<span class='pagenum'><a name="Page_16" id="Page_16">[Pg 16]</a></span></p>
+
+
+<h3>UNTERSUCHUNGEN &Uuml;BER VERSCHIEDENE BESTIMMUNGSMETHODEN DER CELLULOSE.</h3>
+
+<h4><span class="smcap">H. Suringar and B. Tollens</span> (Ztschr. angew. Chem. 1896, No. 23).</h4>
+
+<h3><b>INVESTIGATION OF METHODS OF DETERMINING CELLULOSE.</b></h3>
+
+<p><i>Introduction.</i>&mdash;This is an exhaustive bibliography of the subject,
+describing also the various methods of cellulose estimation, noted in
+historical sequence. First, the Weende 'crude fibre' method (Henneberg)
+with modifications of Wattenberg, Holdefleiss, and others is dealt with.
+The product of this treatment, viz. 'crude fibre' is a mixture,
+containing furfuroids and lignone compounds. Next follows a group of
+processes which aim at producing a 'pure cellulose' by eliminating
+lignone constituents, for which the merely hydrolytic treatments of the
+Weende method are ineffectual. The method of F. Schulze&mdash;prolonged
+digestion with dilute nitric acid, with addition of chlorate&mdash;has been
+largely employed, though the composition of the product is more or less
+divergent from a 'pure cellulose.'</p>
+
+<p>Dilute nitric acid at 60-80&deg; (Cross and Bevan) and a dilute mixture of
+nitric and sulphuric acids (Lifschutz) have been employed for isolating
+cellulose from the lignocelluloses. Hoffmeister modifies the method of
+Schulze by substituting hydrochloric acid for the nitric acid. Treatment
+with the halogens associated with alkaline processes of hydrolysis is
+the basis of the methods of Hugo Muller (bromine water) and Cross and
+Bevan (chlorine gas). Lastly, the authors notice the methods based upon
+the action of the alkaline hydrates at high temperatures (180&deg;) in
+presence of water (Lange), or of glycerin (Gabriel). The process of
+heating to 210&deg; with glycerin only (H&ouml;nig) yields a very impure and
+ill-defined product.<span class='pagenum'><a name="Page_17" id="Page_17">[Pg 17]</a></span></p>
+
+<p>For comparative investigation of these processes certain celluloses and
+cellulosic materials were prepared as follows:</p>
+
+<p>(<i>a</i>) <i>'Rag' cellulose.</i>&mdash;A chemical filter paper, containing only
+cotton and linen celluloses, was further purified by boiling with dilute
+acid and dilute alkali. After thorough washing it was air-dried.</p>
+
+<p>(<i>b</i>) <i>Wood cellulose.</i>&mdash;Pine wood sawdust was treated by digestion for
+fourteen days with dilute nitric acid with addition of chlorate
+(Schulze). The mass was washed and digested with alkaline lye (1.25
+p.ct. KOH), and exhaustively washed, treated with dilute acetic acid;
+again washed, and finally air-dried.</p>
+
+<p>This product was found to yield 2.3 p.ct. furfural on distillation with
+HCl (1.06 sp.gr.).</p>
+
+<p>(c) <i>Purified wood.</i>&mdash;Pine wood sawdust was treated in succession with
+dilute alkalis and acids, in the cold, and with alcohol and ether until
+exhausted of products soluble in these liquids and reagents.</p>
+
+<p>In addition to the above the authors have also employed jute fibre and
+raw cotton wool in their investigations.</p>
+
+<p>They note that the yield of cellulose is in many cases sensibly lowered
+by treating the material after drying at the temperature of 100&deg;. The
+material for treatment is therefore weighed in the air-dry condition,
+and a similar sample weighed off for drying at 100&deg; for determination of
+moisture.</p>
+
+<p>The main results of the experimental investigation are as follows:&mdash;</p>
+
+<p><i>Weende process</i> further attacks the purified celluloses as follows:
+Wood cellulose losing in weight 8-9 p.ct.; filter paper, 6-7.5 p.ct.,
+and the latter treated a second time loses a further 4-5 p.ct. It is
+clear, therefore, that the process is of purely empirical value.<span class='pagenum'><a name="Page_18" id="Page_18">[Pg 18]</a></span></p>
+
+<p><i>Schulze.</i>&mdash;This process gave a yield of 47.6 p.ct. cellulose from pine
+wood. The celluloses themselves, treated by the process, showed losses
+of 1-3 p.ct. in weight, much less therefore than in the preceding case.</p>
+
+<p><i>H&ouml;nig's</i> method of heating with glycerin to 210&deg; was found to yield
+products very far removed from 'cellulose.' The process may have a
+certain value in estimations of 'crude fibre,' but is dismissed from
+further consideration in relation to cellulose.</p>
+
+<p><i>Lange.</i>&mdash;The purpose of the investigation was to test the validity of
+the statement that the celluloses are not attacked by alkaline hydrates
+at 180&deg;. Experiments with pine wood yielded a series of percentages for
+cellulose varying from 36 to 41; the 'purified wood' gave also variable
+numbers, 44 to 49 per cent. It was found possible to limit these
+variations by altering the conditions in the later stages of isolating
+the product; but further experiments on the celluloses themselves
+previously isolated by other processes showed that they were profoundly
+and variably attacked by the 'Lange' treatment, wood cellulose losing 50
+per cent. of its weight, and filter paper (cellulose) losing 15 per
+cent. Further, a specimen of jute yielded 58 per cent. of cellulose by
+this method instead of the normal 78 per cent. It was also found that
+the celluloses isolated by the process, when subjected to a second
+treatment, underwent a further large conversion into soluble
+derivatives, and in a third treatment further losses of 5-10 per cent
+were obtained. The authors attach value, notwithstanding, to the process
+which they state to yield an 'approximately pure cellulose,' and they
+describe a modified method embodying the improvements in detail
+resulting from their investigation.</p>
+
+<p><i>Gabriel's</i> method of heating with a glycerin solution of alkaline
+hydrate is a combination of 'H&ouml;nig' and 'Lange.'<span class='pagenum'><a name="Page_19" id="Page_19">[Pg 19]</a></span> An extended
+investigation showed as in the case of the latter that the celluloses
+themselves are more or less profoundly attacked by the
+treatment&mdash;further that the celluloses isolated from lignocelluloses and
+other complex raw materials are much 'less pure' than those obtained by
+the Lange process. Thus, notably in regard to furfural yielding
+constituents, the latter yield 1-2 p.ct. furfural, whereas <i>specimens of
+'jute cellulose'</i> obtained by the Gabriel process were found to yield <i>9
+to 13 p.ct. furfural</i>.</p>
+
+<p><i>Cross and Bevan.</i>&mdash;Chlorination process yielded in the hands of the
+authors results confirming the figures given in 'Cellulose' for yield of
+cellulose. Investigation of the products for yield of furfural, gave 9
+p.ct. of this aldehyde showing the presence of celluloses, other than
+the normal type.</p>
+
+<p><i>Conclusions.</i>&mdash;The subjoined table gives the mean numerical results for
+yield of end-product or 'cellulose' by the various methods. In the case
+of the 'celluloses' the results are those of the further action of the
+several processes on the end-product of a previous process.</p>
+
+
+
+<div class='center'>
+<table border="1" cellpadding="4" cellspacing="0" summary="">
+<tr><td align='left'></td><td colspan="5"> Methods</td></tr>
+<tr><td align='left'></td><td align='left'> F. Schulze</td><td align='left'> Weende</td><td align='left'> Lange</td><td align='left'> Gabriel</td><td align='left'> Cross and Bevan</td></tr>
+<tr><td align='left'>Wood cellulose</td><td align='left'> 98.51</td><td align='left'> 91.52</td><td align='left'> 48.22</td><td align='left'> 55.93</td><td align='left'> &mdash;</td></tr>
+<tr><td align='left'>Filter paper cellulose</td><td align='left'> 99.62</td><td align='left'> 95.63</td><td align='left'> 78.17</td><td align='left'> 79.77</td><td align='left'> &mdash;</td></tr>
+<tr><td align='left'>Swedish filter paper</td><td align='left'> 96.58</td><td align='left'> &mdash;</td><td align='left'> 84.76</td><td align='left'> &mdash;</td><td align='left'> &mdash;</td></tr>
+<tr><td align='left'>Ordinary filter paper</td><td align='left'> 98.17</td><td align='left'> 93.39</td><td align='left'> 86.58</td><td align='left'> &mdash;</td><td align='left'> &mdash;</td></tr>
+<tr><td align='left'>Cotton ('wool')</td><td align='left'> 98.38</td><td align='left'> 89.98</td><td align='left'> 63.96</td><td align='left'> 67.88</td><td align='left'> &mdash;</td></tr>
+<tr><td align='left'>Jute</td><td align='left'> &mdash;</td><td align='left'> &mdash;</td><td align='left'> 57.93</td><td align='left'> 71.64</td><td align='left'> 75.27</td></tr>
+<tr><td align='left'>Purified wood</td><td align='left'> &mdash;</td><td align='left'> &mdash;</td><td align='left'>{49.27<br /> {46.56</td><td align='left'> &mdash;</td><td align='left'> &mdash;</td></tr>
+<tr><td align='left'>Raw wood</td><td align='left'> 47.60</td><td align='left'> &mdash;</td><td align='left'>{40.82 <br />{38.87</td><td align='left'> &mdash;</td><td align='left'> &mdash;</td></tr>
+</table></div>
+
+<p>The final conclusion drawn from the results is that none of the
+processes fulfil the requirements of an ideal method.<span class='pagenum'><a name="Page_20" id="Page_20">[Pg 20]</a></span> Those which may
+be carried out in a reasonably short time are deficient in two
+directions: (1) they yield a 'cellulose' containing more or less
+oxycellulose; (2) the celluloses themselves are attacked under the
+conditions of treatment, and the end product or cellulose merely
+represents a particular and at the same time variable equilibrium, as
+between the resistance of the cellulose and the attack of the reagents
+employed; this attack being by no means confined to the non-cellulose
+constituents. Schulze's method appears to give the nearest approximation
+to the 'actual cellulose' of the raw material.</p>
+
+<hr style='width: 45%;' />
+
+<p>(p. 8) <b>SOLUTIONS OF CELLULOSE</b>&mdash;(1) <b>ZINC CHLORIDE.</b>&mdash;To prepare a
+homogeneous solution of cellulose by means of the neutral chloride, a
+prolonged digestion at or about 100&deg; with the concentrated reagent is
+required. The dissolution of the cellulose is not a simple phenomenon,
+but is attended with hydrolysis and a certain degree of condensation.
+The latter result is evidenced by the formation of furfural, the former
+by the presence of soluble carbohydrates in the solution obtained by
+diluting the original solution and filtering from the reprecipitated
+cellulose. The authors have observed that in carefully conducted
+experiments cotton cellulose may be dissolved in the reagent, and
+reprecipitated with a loss of only 1 p.ct. in weight. This, however, is
+a 'net' result, and leaves undetermined the degree of hydration of the
+recovered cellulose as of hydrolysis of the original to groups of lower
+molecular weights. Bronnert finds that a previous hydration of the
+cellulose&mdash;e.g. by the process of alkaline mercerisation and removal of
+the alkali by washing&mdash;enables the zinc chloride to effect its
+dissolution by digestion in the cold. (U.S. patent, 646,799/1900. See
+also p. 59.)</p>
+
+<p><i>Industrial applications.</i>&mdash;(a) <i>Vulcanised fibre</i> is prepared by
+treating paper with four times its weight of the concentrated<span class='pagenum'><a name="Page_21" id="Page_21">[Pg 21]</a></span> aqueous
+solution (65-75&deg; B.), and in the resulting gelatinised condition is
+worked up into masses, blocks, sheets, &amp;c., of any required thickness.
+The washing of these masses to remove the zinc salt is a very lengthy
+operation.</p>
+
+<p>To render the product waterproof the process of nitration is sometimes
+superadded [D.R.P. 3181/1878]. Further details of manufacture are given
+in Prakt. Handbuch d. Papierfabrikation, p. 1703 [C. Hofmann].</p>
+
+<p>(<i>b</i>) <i>Calico-printing.</i>&mdash;The use of the solution as a thickener or
+colour vehicle, more especially as a substitute for albumen in pigment
+styles, was patented by E. B. Manby, but the process has not been
+industrially developed [E.P. 10,466 / 1894].</p>
+
+<p>(<i>c</i>) <i>Artificial silk.</i>&mdash;This is a refinement of the earlier
+applications of the solution in spinning cellulose threads for
+conversion into carbon filaments for electrical glow-lamps. This section
+will be found dealt with on p. 59.</p>
+
+<p>(p. 13) (2) <b>Cuprammonium solution.</b>&mdash;The application of the solution of
+cellulose in cuprammonium to the production of a fine filament in
+continuous length, 'artificial silk,' has been very considerably studied
+and developed in the period 1897-1900, as evidenced by the series of
+patents of Fremery and Urban, Pauly, Bronnert, and others. The subject
+will also be found dealt with on p. 58.</p>
+
+<hr style='width: 45%;' />
+
+<p>(p. 15) <b>Reactions of cellulose with iodine.</b>&mdash;In a recent paper, F.
+Mylius deals with the reaction of starch and cellulose with iodine,
+pointing out that the blue colouration depends upon the presence of
+water and iodides. In absence of the latter, and therefore in presence
+of compounds which destroy or absorb hydriodic acid&mdash;e.g. iodic
+acid&mdash;there results a <i>brown</i> addition product. The products in question
+have the characteristics of <i>solid solutions</i> of the halogen. (Berl.
+Ber. 1895, 390.)<span class='pagenum'><a name="Page_22" id="Page_22">[Pg 22]</a></span></p>
+
+<p>(24) <b>Mercerisation</b>&mdash;Notwithstanding the enormous recent developments in
+the industrial application of the mercerising reaction, there have been
+no noteworthy contributions to the theoretical aspects of the subject.
+The following abstract gives an outline of the scope of an important
+technical work on the subject.</p>
+
+
+<h3>DIE MERCERISATION DER BAUMWOLLE.</h3>
+
+<h4><span class="smcap">Paul Gardner</span> (Berlin: 1898. J. Springer).</h4>
+
+<h3><b>THE MERCERISATION OF COTTON.</b></h3>
+
+<p>This monograph of some 150 pages is chiefly devoted to the patent
+literature of the subject. The chemical and physical modifications of
+the cotton substance under the action of strong alkaline lye, were set
+forth by Mercer in 1844-5, and there has resulted from subsequent
+investigations but little increase in our knowledge of the fundamental
+facts. The treatment was industrially developed by Mercer in certain
+directions, chiefly (1) for preparing webs of cloth required to stand
+considerable strain, and (2) for producing cr&ecirc;pon effects by local or
+topical action of the alkali. But the results achieved awakened but a
+transitory interest, and the matter passed into oblivion; so much so,
+indeed, that a German patent [No. 30,966] was granted in 1884 to the
+Messrs. Depouilly for cr&ecirc;pon effects due to the differential shrinkage
+of fabrics under mercerisation, by processes and treatments long
+previously described by Mercer. Such effects have had a considerable
+vogue in recent years, but it was not until the discovery of the
+lustreing effect resulting from the association of the mercerising
+actions with the condition of strain or tension of the yarn or fabric
+that the industry in 'mercerised' goods was started on the lines which
+have led to the present<span class='pagenum'><a name="Page_23" id="Page_23">[Pg 23]</a></span> colossal development. The merit of this
+discovery is now generally recognised as belonging to Thomas and Prevost
+of Crefeld, notwithstanding that priority of patent right belongs to the
+English technologist, H. A. Lowe.</p>
+
+<p>The author critically discusses the grounds of the now celebrated patent
+controversy, arising out of the conflict of the claims of German patent
+85,564/1895 of the former, and English patent 4452/1890 of the latter.
+The author concludes that Lowe's specification undoubtedly describes the
+lustreing effect of mercerising in much more definite terms than that of
+Thomas and Prevost. These inventors, on the other hand, realised the
+effect industrially, which Lowe certainly failed to do, as evidenced by
+his allowing the patent to lapse. As an explanation of his failure, the
+author suggests that Lowe did not sufficiently extend his observations
+to goods made from Egyptian and other long-stapled cottons, in which
+class only are the full effects of the added lustre obtained.</p>
+
+<p>Following these original patents are the specifications of a number of
+inventions which, however, are of insignificant moment so far as
+introducing any essential variation of the mercerising treatment.</p>
+
+<p>The third section of the work describes in detail the various mechanical
+devices which have been patented for carrying out the treatment on yarn
+and cloth.</p>
+
+<p>The fourth section deals with the fundamental facts underlying the
+process and effects summed up in the term 'mercerisation.' These are as
+follows:&mdash;</p>
+
+<p>(<i>a</i>) Although all forms of fibrous celluloses are similarly affected by
+strong alkaline solutions, it is only the Egyptian and other
+long-stapled cottons&mdash;i.e. the goods made from them&mdash;which under the
+treatment acquire the special high lustre which ranks as 'silky.' Goods
+made from American cottons acquire a certain 'finish' and lustre, but
+the effects<span class='pagenum'><a name="Page_24" id="Page_24">[Pg 24]</a></span> are not such as to have an industrial value&mdash;i.e. a value
+proportional to the cost of treatment.</p>
+
+<p>(<i>b</i>) The lustre is determined by exposing the goods to strong tension,
+either when under the action of the alkali, or subsequently, but only
+when the cellulose is in the special condition of hydration which is the
+main chemical effect of the mercerising treatment.</p>
+
+<p>(<i>c</i>) The degree of tension required is approximately that which opposes
+the shrinkage in dimensions, otherwise determined by the action of the
+alkali. The following table exhibits the variations of shrinkage of
+Egyptian when mercerised without tension, under varying conditions as
+regards the essential factors of the treatment&mdash;viz. (1) concentration
+of the alkaline lye, (2) temperature, and (3) duration of action (the
+latter being of subordinate moment):&mdash;</p>
+
+<div class='center'>
+<table border="1" cellpadding="4" cellspacing="0" summary="">
+<tr><td align='left'>Concentration of lye (NaOH)</td><td colspan="3"> 5&deg;B.</td><td colspan="3"> 10&deg;B.</td><td colspan="3"> 15&deg;B</td><td colspan="3"> 25&deg;B</td><td colspan="3"> 30&deg;B</td><td colspan="3"> 35&deg;B</td></tr>
+<tr><td align='left'>Duration of action in minutes</td><td align='left'> 1</td><td align='left'> 10</td><td align='left'> 30</td><td align='left'> 1</td><td align='left'> 10</td><td align='left'> 30</td><td align='left'> 1</td><td align='left'> 10</td><td align='left'> 30</td><td align='left'> 1</td><td align='left'> 10</td><td align='left'> 30</td><td align='left'> 1</td><td align='left'> 10</td><td align='left'> 30</td><td align='left'> 1</td><td align='left'> 10</td><td align='left'> 30</td></tr>
+<tr><td align='left'>Temperatures as under:&mdash;</td><td colspan="18"> Percentage shrinkages (Egyptian yarns) as under:&mdash;</td></tr>
+<tr><td align='center'>2&deg;</td><td align='left'> 0</td><td align='left'> 0</td><td align='left'> 0</td><td align='left'> 1</td><td align='left'> 1</td><td align='left'> 1</td><td align='left'> 12.2</td><td align='left'> 15.2</td><td align='left'> 15.8</td><td align='left'> 19.2</td><td align='left'> 19.8</td><td align='left'> 21.5</td><td align='left'> 22.7</td><td align='left'> 22.7</td><td align='left'> 22.7</td><td align='left'> 24.2</td><td align='left'> 24.5</td><td align='left'> 24.7</td></tr>
+<tr><td align='center'>18&deg;</td><td align='left'> 0</td><td align='left'> 0</td><td align='left'> 0</td><td align='left'> 0</td><td align='left'> 0</td><td align='left'> 0</td><td align='left'> 8.0</td><td align='left'> 8.8</td><td align='left'> 11.8</td><td align='left'> 19.8</td><td align='left'> 20.1</td><td align='left'> 21.0</td><td align='left'> 21.2</td><td align='left'> 22.0</td><td align='left'> 22.3</td><td align='left'> 23.5</td><td align='left'> 23.8</td><td align='left'> 24.7</td></tr>
+<tr><td align='center'>30&deg;</td><td align='left'> 0</td><td align='left'> 0</td><td align='left'> 0</td><td align='left'> 0</td><td align='left'> 0</td><td align='left'> 0</td><td align='left'> 4.6</td><td align='left'> 4.6</td><td align='left'> 6.0</td><td align='left'> 19.0</td><td align='left'> 19.5</td><td align='left'> 19.0</td><td align='left'> 18.5</td><td align='left'> 19.5</td><td align='left'> 19.8</td><td align='left'> 20.7</td><td align='left'> 21.0</td><td align='left'> 21.1</td></tr>
+<tr><td align='center'>80&deg;</td><td align='left'> 0</td><td align='left'> 0</td><td align='left'> 0</td><td align='left'> 0</td><td align='left'> 0</td><td align='left'> 0</td><td align='left'> 3.5</td><td align='left'> 3.5</td><td align='left'> 9.8</td><td align='left'> 13.4</td><td align='left'> 13.7</td><td align='left'> 14.2</td><td align='left'> 15.0</td><td align='left'> 15.1</td><td align='left'> 15.5</td><td align='left'> 15.0</td><td align='left'> 15.2</td><td align='left'> 15.4</td></tr>
+</table></div>
+
+<p>The more important general indications of the above results are&mdash;(1) The
+mercerisation action commences with a lye of 10&deg;B., and increases with
+increased strength of the lye up to a maximum at 35&deg;B. There is,
+however, a relatively slight increase of action with the increase of
+caustic soda from 30-40&deg;B. (2) For optimum action the temperature should
+not exceed 15-20&deg;C. (3) The duration of action is of proportionately
+less influence as the concentration of the lye increases. As the maximum
+effect is attained the action becomes practically instantaneous, the
+only condition affecting it being that of penetration&mdash;i.e. actual
+contact of cellulose and alkali.<span class='pagenum'><a name="Page_25" id="Page_25">[Pg 25]</a></span></p>
+
+<p>(<i>d</i>) The question as to whether the process of 'mercerisation' involves
+chemical as well as physical effects is briefly discussed. The author is
+of opinion that, as the degree of lustre obtained varies with the
+different varieties of cotton, the differentiation is occasioned by
+differences in chemical constitution of these various cottons. The
+influence of the chemical factors is also emphasised by the increased
+dyeing capacity of the mercerised goods, which effect, moreover, is
+independent of those conditions of strain or tension under mercerisation
+which determine lustre. It is found in effect that with a varied range
+of dye stuffs a given shade is produced with from 10 to 30 p.ct. less
+colouring matter than is required for the ordinary, i.e. unmercerised,
+goods.</p>
+
+<p>In reference to the constants of strength and elasticity, Buntrock gives
+the following results of observations upon a 40<sup>5</sup> twofold yarn, five
+threads of 50 cm. length being taken for each test(Prometheus, 1897, p.
+690): (<i>a</i>) the original yarn broke under a load of 1440 grms.; (<i>b</i>)
+after mercerisation without tension the load required was 2420 grms.;
+(<i>c</i>) after mercerisation under strain, 1950 grms. Mercerisation,
+therefore, increases the strength of the yarn from 30 to 66 p.ct., the
+increase being lessened proportionately to the strain accompanying
+mercerisation. <i>Elasticity</i>, as measured by the extension under the
+breaking load, remains about the same in yarns mercerised under strain,
+but when allowed to shrink under mercerisation there is an increase of
+30-40 p.ct. over the original.</p>
+
+<p>The <i>change of form</i> sustained by the individual fibres has been studied
+by H. Lange [Farberzeitung, 1898, 197-198], whose microphotographs of
+the cotton fibres, both in length and cross-section, are reproduced. In
+general terms, the change is from the flattened riband of the original
+fibre to a cylindrical tube with much diminished and rounded central
+canal. The effect of strain under mercerisation is chiefly seen<span class='pagenum'><a name="Page_26" id="Page_26">[Pg 26]</a></span> in the
+contour of the surface, which is smooth, and the obliteration at
+intervals of the canal. Hence the increased transparency and more
+complete reflection of the light from the surface, and the consequent
+approximation to the optical properties of the silk fibre.</p>
+
+<p>The work concludes with a section devoted to a description of the
+various practical systems of mercerisation of yarns in general practice
+in Germany, and an account of the methods adopted in dyeing the
+mercerised yarns.</p>
+
+
+<h3>RESEARCHES ON MERCERISED COTTON.</h3>
+
+<h4><span class="smcap">A. Fraenkel</span> and <span class="smcap">P. Friedlaender</span> (Mitt. k.-k. Techn. Gew. Mus., Wien,
+1898, 326).</h4>
+
+<p>The authors, after investigation, are inclined to attribute the lustre
+of mercerised cotton to the absence of the cuticle, which is destroyed
+and removed in the process, partly by the chemical action of the alkali,
+and partly by the stretching at one or other stage of the process. The
+authors have investigated the action of alcoholic solutions of soda
+also. The lustre effects are not obtained unless the action of water is
+associated.</p>
+
+<p>In conclusion, the authors give the following particulars of breaking
+strains and elasticity:&mdash;</p>
+
+
+<div class='center'>
+<table border="1" cellpadding="4" cellspacing="0" summary="">
+<tr><td align='left'>Treatment</td><td align='left'> Experiments</td><td align='left'> Breaking strain<br /> Grammes</td><td align='left'> Elasticity Elongation in mm.</td></tr>
+<tr><td rowspan="3">Cotton unmercerised.</td><td align='left'> 1</td><td align='left'> 360</td><td align='left'> 20</td></tr>
+<tr><td align='left'> 2</td><td align='left'> 356</td><td align='left'> 20</td></tr>
+<tr><td align='left'> 3</td><td align='left'> 360</td><td align='left'> 22</td></tr>
+<tr><td rowspan="3">Mercerised with Soda 35&deg;B.</td><td align='left'> 1</td><td align='left'> 530</td><td align='left'> 44</td></tr>
+<tr><td align='left'> 2</td><td align='left'> 570</td><td align='left'> 40</td></tr>
+<tr><td align='left'> 3</td><td align='left'> 559</td><td align='left'> 35</td></tr>
+<tr><td rowspan="3">Alcoholic soda 10 p.ct. cold</td><td align='left'> 1</td><td align='left'> 645</td><td align='left'> 24</td></tr>
+<tr><td align='left'> 2</td><td align='left'> 600</td><td align='left'> 27</td></tr>
+<tr><td align='left'> 3</td><td align='left'> 610</td><td align='left'> 33</td></tr>
+<tr><td rowspan="3">Alcoholic soda 10 p.ct. hot</td><td align='left'> 5</td><td align='left'> 740</td><td align='left'> 33</td></tr>
+<tr><td align='left'> 2</td><td align='left'> 730</td><td align='left'> 38</td></tr>
+<tr><td align='left'> 3</td><td align='left'> 690</td><td align='left'> 30</td></tr>
+</table></div>
+<p><br /><br /><br />&nbsp;</p>
+
+<div class="footnotes"><h3>FOOTNOTES:</h3>
+
+<div class="footnote"><p><a name="Footnote_2_2" id="Footnote_2_2"></a><a href="#FNanchor_2_2"><span class="label">[2]</span></a> This and other similar references are to the matter of the
+original volume (1895).</p></div>
+</div>
+
+
+<hr style="width: 65%;" />
+<p><span class='pagenum'><a name="Page_27" id="Page_27">[Pg 27]</a></span></p>
+<h2>SECTION II. SYNTHETICAL DERIVATIVES&mdash;SULPHOCARBONATES AND ESTERS</h2>
+
+
+<p>(p. 25) <b>Cellulose sulphocarbonate.</b>&mdash;Further investigations of the
+reaction of formation as well as the various reactions of decomposition
+of the compound, have not contributed any essential modification or
+development of the subject as originally described in the author's first
+communications. A large amount of experimental matter has been
+accumulated in view of the ultimate contribution of the results to the
+general theory of colloidal solutions. But viscose is a complex product
+and essentially variable, through its pronounced tendency to progressive
+decomposition with reversion of the cellulose to its insoluble and
+uncombined condition. The solution for this reason does not lend itself
+to exact measurement of its physical constants such as might elucidate
+in some measure the progressive molecular aggregation of the cellulose
+in assuming spontaneously the solid (hydrate) form. Reserving the
+discussion of these points, therefore, we confine ourselves to recording
+results which further elucidate special points.</p>
+
+<p><i>Normal and other celluloses.</i>&mdash;We may certainly use the sulphocarbonate
+reaction as a means of defining a normal cellulose. As already pointed
+out, cotton cellulose passes quantitatively through the cycle of
+treatments involved in solution as sulphocarbonate and decomposition of
+the solution with regeneration as structureless or amorphous cellulose
+(hydrate).</p>
+
+<p>Analysis of this cellulose shows a fall of carbon percentage from 44.4
+to 43.3, corresponding with a change in composition from
+C<sub>6</sub>H<sub>10</sub>O<sub>5</sub> to 4C<sub>6</sub>H<sub>10</sub>O<sub>5</sub>.H<sub>2</sub>O. The partial hydrolysis
+affects the whole molecule, and is limited to this effect, whereas, in
+the case of celluloses of other types, there is a fractionation of the
+mass, a portion undergoing a further hydrolysis to compounds of lower
+molecular weight and permanently soluble. Thus in the case of the wood
+celluloses<span class='pagenum'><a name="Page_28" id="Page_28">[Pg 28]</a></span> the percentage recovered from solution as viscose is from 93
+to 95 p.ct. It is evident that these celluloses are not homogeneous. A
+similar conclusion results from the presence of furfural-yielding
+compounds with the observation that the hydrolysis to soluble
+derivatives mainly affects these derivatives. In the empirical
+characterisation of a normal cellulose, therefore, we may include the
+property of quantitative regeneration or recovery from its solution as
+sulphocarbonate.</p>
+
+<p>In the use of the word 'normal' as applied to a 'bleached' cotton, we
+have further to show in what respects the sulphocarbonate reaction
+differentiates the bleached or purified cotton cellulose from the raw
+product. The following experiments may be cited: Specimens of American
+and Egyptian cottons in the raw state, freed from mechanical, i.e.
+non-fibrous, impurities, were treated with a mercerising alkali, and the
+alkali-cotton subsequently exposed to carbon disulphide. The product of
+reaction was further treated as in the preparation of the ordinary
+solution; but in place of the usual solution, structureless and
+homogeneous, it was observed to retain a fibrous character, and the
+fibres, though enormously swollen, were not broken down by continued
+vigorous stirring. After large dilution the solutions were filtered, and
+the fibres then formed a gelatinous mass on the filters. After
+purification, the residue was dried and weighed. The American cotton
+yielded 90.0 p.ct., and the Egyptian 92.0 p.ct. of its substance in the
+form of this peculiar modification. The experiment was repeated,
+allowing an interval of 24 hours to elapse between the conversion into
+alkali-cotton and exposure of this to the carbon disulphide. The
+quantitative results were identical.</p>
+
+<p>There are many observations incidental to chemical treatments of cotton
+fabrics which tend to show that the bleaching process produces other
+effects than the mere<span class='pagenum'><a name="Page_29" id="Page_29">[Pg 29]</a></span> removal of mechanical impurities. In the
+sulphocarbonate reaction the raw cotton, in fact, behaves exactly as a
+compound cellulose. Whether the constitutional difference between raw
+and bleached cotton, thus emphasised, is due to the group of components
+of the raw cotton, which are removed in the bleaching process, or to
+internal constitutional changes determined by the bleaching treatments,
+is a question which future investigation must decide.</p>
+
+<p><i>The normal sulphocarbonate (viscose).</i>&mdash;In the industrial applications
+of viscose it is important to maintain a certain standard of composition
+as of the essential physical properties of the solution, notably
+viscosity. It may be noted first that, with the above-mentioned
+exception, the various fibrous celluloses show but slight differences in
+regard to all the essential features of the reactions involved. In the
+mercerising reaction, or alkali-cellulose stage, it is true the
+differences are considerable. With celluloses of the wood and straw
+classes there is a considerable conversion into soluble
+alkali-celluloses. If treated with water these are dissolved, and on
+weighing back the cellulose, after thorough washing, treatment with
+acid, and finally washing and drying, it will be found to have lost from
+15 to 20 p.ct. in weight. The lower grade of celluloses thus dissolved
+are only in part precipitated in acidifying the alkaline solution. On
+the other hand, after conversion into viscose, the cellulose when
+regenerated re-aggregates a large proportion of these lower grade
+celluloses, and the final loss is as stated above, from 5 to 7 p.ct.
+only.</p>
+
+<p>Secondly, it is found that all the conditions obtaining in the
+alkali-cellulose stage affect the subsequent viscose reaction and the
+properties of the final solution. The most important are obviously the
+proportion of alkali to cellulose and the length of time they are in
+contact before being treated with carbon disulphide. An excess of alkali
+beyond the 'normal'<span class='pagenum'><a name="Page_30" id="Page_30">[Pg 30]</a></span> proportion&mdash;viz. 2NaOH per 1 mol.
+C<sub>6</sub>H<sub>10</sub>O<sub>5</sub>&mdash;has little influence upon the viscose reaction, but
+lowers the viscosity of the solution of the sulphocarbonate prepared
+from it. But this effect equally follows from addition of alkali to the
+viscose itself. The alkali-cellulose changes with age; there is a
+gradual alteration of the molecular structure of the cellulose, of which
+the properties of the viscose when prepared are the best indication.
+There is a progressive loss of viscosity of the solution, and a
+corresponding deterioration in the structural properties of the
+cellulose when regenerated from it&mdash;especially marked in the film form.
+In regard to viscosity the following observations are typical:&mdash;</p>
+
+<div class="blockquot"><p>(<i>a</i>) A viscose of 1.8 p.ct. cellulose prepared from an
+alkali-cellulose (cotton) fourteen days old.</p>
+
+<p>(<i>b</i>) Viscose of 1.8 p.ct. cellulose from an alkali-cellulose
+(cotton) three days old.</p>
+
+<p>(<i>c</i>) Glycerin diluted with 1/3 vol. water.</p></div>
+
+
+<div class='center'>
+<table border="0" cellpadding="4" cellspacing="0" summary="">
+<tr><td align='left'></td><td align='center'><i>a</i></td><td align='center'><i>b</i></td><td align='center'><i>b</i></td><td align='center'><i>c</i></td></tr>
+<tr><td align='left'></td><td align='center'></td><td align='left'></td><td align='center'>Diluted with<br /> equal vol. water</td></tr>
+<tr><td align='left'>Times of flow of equal volumes from narrow orifice in seconds</td><td align='center'>112</td><td align='center'>321</td><td align='center'>103</td><td align='center'>170</td></tr>
+</table></div>
+
+<p>Similarly the cellulose in reverting to the solid form from these
+'degraded' solutions presents a proportionate loss of cohesion and
+aggregating power expressed by the inferior strength and elasticity of
+the products. Hence, in the practical applications of the product where
+the latter properties are of first importance, it is necessary to adopt
+normal standards, such as above indicated, and to carefully regulate all
+the conditions of treatment in each of the two main stages of reaction,
+so that a product of any desired character may be invariably obtained.</p>
+
+<p>Incidentally to these investigations a number of observations have been
+made on the alkali-cellulose (cotton) after<span class='pagenum'><a name="Page_31" id="Page_31">[Pg 31]</a></span> prolonged storage in closed
+vessels. It is well known that starch undergoes hydrolysis in contact
+with aqueous alkalis of a similar character to that determined by acids
+[B&eacute;champ, Annalen, 100, 365]. The recent researches of Lobry de Bruyn
+[Rec. Trav. Chim. 14, 156] upon the action of alkaline hydrates in
+aqueous solution on the hexoses have established the important fact of
+the resulting mobility of the CO group, and the interchangeable
+relationships of typical aldoses and ketoses. It was, therefore, not
+improbable that profound hydrolytic changes should occur in the
+cellulose molecule when kept for prolonged periods as alkali-cellulose.</p>
+
+<p>We may cite an extreme case. A series of products were examined after
+12-18 months' storage. They were found to contain only 3-5 p.ct.
+'soluble carbohydrates'; these were precipitated by Fehling's solution
+but without reduction on boiling. They were, therefore, of the cellulose
+type. On acidifying with sulphuric acid and distilling, traces only of
+volatile acid were produced. It is clear, therefore, that the change of
+molecular weight of the cellulose, the disaggregation of the undoubtedly
+large molecule of the original 'normal' cellulose&mdash;which effects are
+immediately recognised in the viscose reactions of such products&mdash;are of
+such otherwise limited character that they do not affect the
+constitution of the unit groups. We should also conclude that the
+cellulose type of constitution covers a very wide range of minor
+variations of molecular weight or aggregation.</p>
+
+<p>The resistance of the normal cellulose to the action of alkalis under
+these hydrolysing conditions should be mentioned in conjunction with the
+observations of Lange, and the results of the later investigations of
+Tollens, on its resistance to 'fusion' with alkaline hydrates at high
+temperatures (180&deg;). The degree of resistance has been established only
+on the empirical basis of weighing the product recovered from such<span class='pagenum'><a name="Page_32" id="Page_32">[Pg 32]</a></span>
+treatment. The product must be investigated by conversion into typical
+cellulose derivatives before we can pronounce upon the constitutional
+changes which certainly occur in the process. But for the purpose of
+this discussion it is sufficient to emphasise the extraordinary
+resistance of the normal cellulose to the action of alkalis, and to
+another of the more significant points of differentiation from starch.</p>
+
+<p><i>Chemical constants of cellulose sulphocarbonate (solution).</i>&mdash;In
+investigations of the solutions we make use of various analytical
+methods, which may be briefly described, noting any results bearing upon
+special points.</p>
+
+<p><i>Total alkali.</i>&mdash;This constant is determined by titration in the usual
+way. The cellulose ratio, C<sub>6</sub>H<sub>10</sub>O<sub>5</sub>: 2NaOH, is within the
+ordinary error of observation, 2: 1 by weight. A determination of alkali
+therefore determines the percentage of cellulose.</p>
+
+<p><i>Cellulose</i> may be regenerated in various ways&mdash;viz. by the action of
+heat, of acids, of various oxidising compounds. It is purified for
+weighing by boiling in neutral sulphite of soda (2 p.ct. solution) to
+remove sulphur, and in very dilute acids (0.33 p.ct. HCl) to decompose
+residues of 'organic' sulphur compounds. It may also be treated with
+dilute oxidants. After weighing it may be ignited to determine residual
+inorganic compounds.</p>
+
+<p><i>Sulphur.</i>&mdash;It has been proved by Lindemann and Motten [Bull. Acad. R.
+Belg. (3), 23, 827] that the sulphur of sulphocarbonates (as well as of
+sulphocyanides) is fully oxidised (to SO<sub>3</sub>) by the hypochlorites
+(solutions at ordinary temperatures). The method may be adapted as
+required for any form of the products or by-products of the viscose
+reaction to be analysed for <i>total sulphur</i>.</p>
+
+<p>The sulphur present in the form of dithiocarbonates, including the
+typical cellulose xanthogenic acid, is approximately<span class='pagenum'><a name="Page_33" id="Page_33">[Pg 33]</a></span> isolated and
+determined as CS<sub>2</sub> by adding a zinc salt in excess, and distilling off
+the carbon disulphide from a water bath. From freshly prepared solutions
+a large proportion of the disulphide originally interacting with the
+alkali and cellulose is recovered, the result establishing the general
+conformity of the reaction to that typical of the alcohols. On keeping
+the solutions there is a progressive interaction of the bisulphide and
+alkali, with formation of trithiocarbonates and various sulphides. In
+decomposing these products by acid reagents hydrogen sulphide and free
+sulphur are formed, the estimation of which presents no special
+difficulties.</p>
+
+<p>In the spontaneous decomposition of the solution a large proportion of
+the sulphur resumes the form of the volatile disulphide. This is
+approximately measured by the loss in total sulphur in the following
+series of determinations, in which a viscose of 8.5 p.ct. strength
+(cellulose) was dried down as a thin film upon glass plates, and
+afterwards analysed:</p>
+
+<p>
+(<i>a</i>) Proportion of sulphur to cellulose (100 pts.) in original.<br />
+(<i>b</i>) After spontaneous drying at ordinary temperature.<br />
+(<i>c</i>) After drying at 40&deg;C.<br />
+(<i>d</i>) As in (<i>c</i>), followed, by 2 hours' heating at 98&deg;.<br />
+(<i>e</i>) As in (<i>c</i>), followed by 5 hours' heating at 98&deg;.<br />
+</p>
+
+
+<div class='center'>
+<table border="0" cellpadding="4" cellspacing="0" summary="">
+<tr><td align='left'></td><td align='center'><i>a</i></td><td align='center'><i>b</i></td><td align='center'><i>c</i></td><td align='center'><i>d</i></td><td align='center'><i>e</i></td></tr>
+<tr><td align='left'>Total sulphur</td><td align='center'>40.0</td><td align='center'>25.0</td><td align='center'>31.0</td><td align='center'>23.7</td><td align='center'>10.4</td></tr>
+</table></div>
+<p>The dried product in (<i>b</i>) and (<i>c</i>) was entirely resoluble in water; in
+(<i>d</i>) and (<i>e</i>), on the other hand, the cellulose was fully regenerated,
+and obtained as a transparent film.</p>
+
+<p><i>Iodine reaction.</i>&mdash;Fresh solutions of the sulphocarbonate show a fairly
+constant reaction with normal iodine solution. At the first point, where
+the excess of iodine visibly persists, there is complete precipitation
+of the cellulose as the bixanthic sulphide; and this occurs when the
+proportion of iodine added reaches 3I<sub>2</sub>: 4Na<sub>2</sub>O, calculated to the
+total alkali.<span class='pagenum'><a name="Page_34" id="Page_34">[Pg 34]</a></span></p>
+
+<p><i>Other decompositions.</i>&mdash;The most interesting is the interaction which
+occurs between the cellulose xanthogenate and salts of ammonia, which is
+taken advantage of by C. H. Stearn in his patent process of spinning
+artificial threads from viscose. The insoluble product which is formed
+in excess of the solution of ammonia salt is free from soda, and
+contains 9-10 p.ct. total sulphur. The product retains its solubility in
+water for a short period. The solution may be regarded as containing the
+ammonium cellulose xanthate. This rapidly decomposes with liberation of
+ammonia and carbon disulphide, and separation of cellulose (hydrate). As
+precipitated by ammonium-chloride solution the gelatinous thread
+contains 15 p.ct. of cellulose, with a sp.gr. 1.1. The process of
+'fixing'&mdash;i.e. decomposing the xanthic residue&mdash;consists in a short
+exposure to the boiling saline solution. The further dehydration, with
+increase of gravity and cellulose content, is not considerable. The
+thread in its final air-dry state has a sp.gr. 1.48.</p>
+
+<hr style='width: 45%;' />
+
+<p><b>Cellulose Benzoates.</b>&mdash;These derivatives have been further studied by the
+authors. The conditions for the formation of the monobenzoate
+[C<sub>6</sub>H<sub>9</sub>O<sub>4</sub>.O.CO.Ph] are very similar to those required for the
+sulphocarbonate reaction. The fibrous cellulose (cotton), treated with a
+10 p.ct. solution NaOH, and subsequently with benzoyl chloride, gives
+about 50 p.ct. of the theoretical yield of monobenzoate. Converted by 20
+p.ct. solution NaOH into alkali-cellulose, and with molecular
+proportions as below, the following yields were obtained:&mdash;</p>
+
+
+<div class='center'>
+<table border="0" cellpadding="4" cellspacing="0" summary="">
+<tr><td align='left'></td><td align='left'></td><td align='left'>Calc. for<br /> Monobenzoate</td></tr>
+<tr><td align='left'>(<i>a</i>) C<sub>6</sub>H<sub>10</sub>O<sub>5</sub> : 2.0-2.5 NaOH : C<sub>6</sub>H<sub>5</sub>.COCl&mdash;</td><td align='left'>150.8}</td><td rowspan="2">164.0</td></tr>
+<tr><td align='left'>(<i>b</i>) C<sub>6</sub>H<sub>10</sub>O<sub>5</sub> : 2.0-2.5 NaOH : 1.5 mol. C<sub>6</sub>H<sub>5</sub>COCl</td><td align='left'>159.0}</td></tr>
+</table></div>
+
+<p>An examination of (<i>a</i>) showed that some dibenzoate (about 7 p.ct.) had
+been formed. The product () was exhaustively<span class='pagenum'><a name="Page_35" id="Page_35">[Pg 35]</a></span> treated with cuprammonium
+solution, to which it yielded about 20 p.ct. of its weight, which was
+therefore unattacked cellulose.</p>
+
+<p>Under conditions as above, but with 2.5 mol. C<sub>6</sub>H<sub>5</sub>COCl, a careful
+comparison was made of the behaviour of the three varieties of cotton,
+which were taken in the unspun condition and previously fully bleached
+and purified.</p>
+
+
+<div class='center'>
+<table border="0" cellpadding="4" cellspacing="0" summary="">
+<tr><td align='left'></td><td align='center'> Sea Island</td><td align='center'> Egyptian</td><td align='center'> American</td></tr>
+<tr><td align='center'>Aggregate yield of benzoate</td><td align='center'> 153</td><td align='center'> 148</td><td align='center'> 152</td></tr>
+<tr><td align='center'>Moisture in air dry state</td><td align='center'> 5.28</td><td align='center'> 5.35</td><td align='center'> 5.15</td></tr>
+<tr><td align='center'>Proportion of dibenzoate p.ct.</td><td align='center'> 8.30</td><td align='center'> 13.70</td><td align='center'> 9.4</td></tr>
+<tr><td align='center'>Yield of cellulose by saponification</td><td align='center'> 58.0</td><td align='center'> 54.0</td><td align='center'> 58.3</td></tr>
+</table></div>
+
+<p>It appears from these results that the benzoate reaction may proceed to
+a higher limit (dibenzoate) in the case of Egyptian cotton. This would
+necessarily imply a higher limit of 'mercerisation,' under equal
+conditions of treatment with the alkaline hydrate. It must be noted that
+in the conversion of the fibrous cellulose into these (still) fibrous
+monobenzoates, there are certain mechanical conditions imported by the
+structural features of the ultimate fibres. For the elimination of the
+influence of this factor a large number of quantitative comparisons will
+be necessary. The above results are therefore only cited as typical of a
+method of comparative investigation, more especially of the still open
+questions of the cause of the superior effects in mercerisation of
+certain cottons (see p. 23). It is quite probable that chemical as well
+as structural factors co-operate in further differentiating the cottons.</p>
+
+<p>Further investigation of the influence upon the benzoate reaction, of
+increase of concentration of the soda lye, used in the preliminary
+alkali cellulose reaction, from 20 to 33 p.ct. NaOH, established (1)
+that there is no corresponding increase in the benzoylation, and (2)
+that this ester reaction and the<span class='pagenum'><a name="Page_36" id="Page_36">[Pg 36]</a></span> sulphocarbonate reaction are closely
+parallel, in that the degree and limit of reaction are predetermined by
+the conditions of formation of the alkali cellulose.</p>
+
+<p><i>Monobenzoate</i> prepared as above described is resistant to all solvents
+of cellulose and of the cellulose esters, and is therefore freed from
+cellulose by treatment with the former, and from the higher benzoate by
+treatment with the latter. Several of these, notably pyridine, phenol
+and nitrobenzene, cause considerable swelling and gelatinisation of the
+fibres, but without solution.</p>
+
+<p><i>Structureless celluloses</i> of the 'normal' type, and insoluble therefore
+in alkaline lye, treated under similar conditions to those described
+above for the fibrous celluloses, yield a higher proportion of
+dibenzoate. The following determinations were made with the cellulose
+(hydrate) regenerated from the sulphocarbonate:&mdash;</p>
+
+
+
+<div class='center'>
+<table border="0" cellpadding="4" cellspacing="0" summary="">
+<tr><td align='left'>Mol. proportions of reagents</td><td align='center'>Yield</td><td align='center'>Dibenzoate p.ct.</td></tr>
+<tr><td align='left'>C<sub>6</sub>H<sub>10</sub>O<sub>5</sub> : 2NaOH : 2BzCl</td><td align='center'>145</td><td align='center'>34.7</td></tr>
+<tr><td align='left'>&nbsp;&nbsp;&nbsp;&nbsp;[Caustic soda at 10 per cent. NaOH]</td></tr>
+<tr><td align='left'>C<sub>6</sub>H<sub>10</sub>O<sub>5</sub> : 4NaOH : 2BzCl</td><td align='center'>162</td><td align='center'>62.7</td></tr>
+<tr><td align='left'>&nbsp;&nbsp;&nbsp;&nbsp;[Caustic soda at 20 per cent. NaOH]</td></tr>
+</table></div>
+
+
+<p><i>Limit of reaction.</i>&mdash;The cellulose in this form having shown itself
+more reactive, it was taken as the basis for determining the maximum
+proportion of OH groups yielding to this later reaction. The systematic
+investigations of Skraup [Monatsh. 10, 389] have determined that as
+regards the interacting groups the molecular proportions 1 OH: 7 NaOH: 5
+BzCl, ensure complete or maximum esterification. The maximum of OH
+groups in cellulose being 4, the reagents were taken in the proportion
+C<sub>6</sub>H<sub>10</sub>O<sub>5</sub>: 4 [7 NaOH: 5 BzCl]. The yield of crude product, after
+purifying as far as possible from the excess of benzoic acid, was 240
+p.ct. [calculated for dibenzoate 227 p.ct.]. On further investigating
+the crude product by treatment with solvents, it was found to have still
+retained benzoic acid.<span class='pagenum'><a name="Page_37" id="Page_37">[Pg 37]</a></span> There was also present a proportion of only
+partially attacked cellulose (monobenzoate). The soluble benzoate
+amounted to 90 p.ct. of the product. It may be generally concluded that
+the dibenzoate represents the normal maximum but that with the hydrated
+and partly hydrolysed cellulose molecule, as obtained by regeneration
+from the sulphocarbonate, other OH groups may react, but they are only a
+fractional proportion in relation to the unit group C<sub>6</sub>H<sub>10</sub>O<sub>5</sub>. In
+this respect again there is a close parallelism between the
+sulphocarbonate and benzoyl-ester reactions.</p>
+
+<p><i>The dibenzoate</i>, even when prepared from the fibrous celluloses, is
+devoid of structure, and its presence in admixture with the fibrous
+monobenzoate is at once recognised as it constitutes a structureless
+incrustation. Under the microscope its presence in however minute
+proportion is readily observed. As stated it is soluble in certain of
+the ordinary solvents of the cellulose esters, e.g. chloroform, acetic
+acid, nitrobenzene, pyridine, and phenol. It is not soluble in ether or
+alcohol.</p>
+
+<p><i>Hygroscopic moisture of benzoates.</i>&mdash;The crude monobenzoate retains
+5.0-5.5 p.ct. moisture in the air-dry condition. After removal of the
+residual cellulose this is reduced to 3.3 p.ct. under ordinary
+atmospheric conditions. The purified dibenzoates retain 1.6 p.ct. under
+similar conditions.</p>
+
+<p><i>Analysis of benzoates.</i>&mdash;On saponification of these esters with
+alcoholic sodium hydrate, anomalous results are obtained. The acid
+numbers, determined by titration in the usual way, are 10-20 p.ct. in
+excess of the theoretical, the difference increasing with the time of
+boiling. Similarly the residual cellulose shows a deficiency of 5-9
+p.ct.</p>
+
+<p>It is by no means improbable that in the original ester reaction there
+is a constitutional change in the cellulose molecule causing it to break
+down in part under the hydrolysing treatment with formation of acid
+products. This point is under<span class='pagenum'><a name="Page_38" id="Page_38">[Pg 38]</a></span> investigation. Normal results as regards
+acid numbers, on the other hand, are obtained by saponification with
+sodium ethylate in the cold, the product being digested with the
+half-saturated solution for 12 hours in a closed flask.</p>
+
+<p>The following results with specimens of mono- and dibenzoate, purified,
+as far as possible, may be cited:</p>
+
+
+
+<div class='center'>
+<table border="0" cellpadding="4" cellspacing="0" summary="">
+<tr><td align='left'></td><td colspan="3">Combustion results</td><td colspan="4">Saponification results</td></tr>
+<tr><td align='left'></td><td align='left'></td><td align='left'></td><td align='left'>Calc.</td><td align='left'>C<sub>6</sub>H<sub>5</sub>.COOH</td><td align='left'>Calc.</td><td align='left'>Cellulose</td><td align='left'>Calc.</td></tr>
+<tr><td align='left'>Monobenzoate</td><td align='left'>C</td><td align='left'>56.60</td><td align='center'>58.65}</td><td rowspan="2">46.0</td><td rowspan="2">45.9</td><td rowspan="2">58.0</td><td rowspan="2">60.8</td></tr>
+<tr><td align='left'></td><td align='left'>H</td><td align='left'>5.06</td><td align='center'>5.26}</td></tr>
+<tr><td align='left'>Dibenzoate</td><td align='left'>C</td><td align='left'>63.10</td><td align='center'>64.86}</td><td rowspan="2">65.5</td><td rowspan="2">66.6</td><td rowspan="2">34.3</td><td rowspan="2">40.3</td></tr>
+<tr><td align='left'></td><td align='left'>H</td><td align='left'>3.40</td><td align='center'>4.86}</td></tr>
+</table></div>
+
+<p>The divergence of the numbers, especially for the dibenzoate, in the
+case of the hydrogen, and yield of cellulose on hydrolysis are
+noteworthy. They confirm the probability of the occurrence of secondary
+changes in the ester reactions.</p>
+
+<p><i>Action of nitrating acid upon the benzoates.</i>&mdash;From the benzoates above
+described, mixed nitro-nitric esters are obtained by the action of the
+mixture of nitric and sulphuric acids. The residual OH groups of the
+cellulose are esterified and substitution by an NO<sub>2</sub> group takes place
+in the aromatic residue, giving a mixed nitric nitrobenzoic ester. The
+analysis of the products points to the entrance of 1 NO<sub>2</sub> group in the
+benzoyl residue in either case; in the cellulose residue 1 OH readily
+reacts. Higher degrees of nitration are attained by the process of
+solution in concentrated nitric acid and precipitation by pouring into
+sulphuric acid. In describing these mixed esters we shall find it
+necessary to adopt the C<sub>12</sub> unit formula.</p>
+
+<p>In analysing these products we have employed the Dumas method for <i>total
+nitrogen</i>. For the O.NO<sub>2</sub> groups we have found the nitrometer and the
+Schloesing methods to give concordant results. For the NO<sub>2</sub> groups it
+was thought that Limpricht's method, based upon reduction with stannous
+chloride in acid<span class='pagenum'><a name="Page_39" id="Page_39">[Pg 39]</a></span> solution (HCl), would be available. The quantitative
+results, however, were only approximate, owing to the difficulty of
+confining the reduction to the NO<sub>2</sub> groups of the nitrobenzoyl
+residue. By reduction with ammonium sulphide the O.NO<sub>2</sub> groups were
+entirely removed as in the case of the cellulose nitrates; the NO<sub>2</sub>
+was reduced to NH<sub>2</sub> and there resulted a cellulose amidobenzoate,
+which was diazotised and combined with amines and phenols to form yellow
+and red colouring matters, the reacting residue remaining more or less
+firmly combined with the cellulose.</p>
+
+<p><i>Cellulose dinitrate-dinitrobenzoate, and cellulose
+trinitrate-dinitrobenzoate.</i>&mdash;On treating the fibrous benzoate&mdash;which is
+a dibenzoate on the C<sub>12</sub> basis&mdash;with the acid mixture under the usual
+conditions, a yellowish product is obtained, with a yield of 140-142
+p.ct. The nitrobenzoate is insoluble in ether alcohol, but is soluble in
+acetone, acetic acid, and nitrobenzene. In purifying the product the
+former solvent is used to remove any cellulose nitrates. To obtain the
+maximum combination with nitroxy-groups, the product was dissolved in
+concentrated nitric acid, and the solution poured into sulphuric acid.</p>
+
+<p>The following analytical results were obtained (<i>a</i>) for the product
+obtained directly from the fibrous benzoate and purified as indicated,
+(<i>b</i>) for the product from the further treatment of (<i>a</i>) as described:</p>
+
+<div class='center'>
+<table border="0" cellpadding="4" cellspacing="0" summary="">
+<tr><td align='left'></td><td align='left'></td><td colspan="2">Found</td><td colspan="2">Calc. for</td></tr>
+<tr><td align='left'></td><td align='left'></td><td align='left'>(<i>a</i>)</td><td align='left'>(<i>b</i>)</td><td align='left'>Dinitrate dinitrobenzoate</td><td align='left'>Trinitrate dinitrobenzoate</td></tr>
+<tr><td align='left'>Total</td><td align='left'>Nitrogen</td><td align='center'>7.84</td><td align='center'>8.97</td><td align='center'>7.99</td><td align='center'>9.24</td></tr>
+<tr><td align='left'>O.NO<sub>2</sub></td><td align='left'>"</td><td align='center'>5.00</td><td align='center'>5.45</td><td align='center'>4.00</td><td align='center'>5.54</td></tr>
+<tr><td align='left'>NO<sub>2</sub></td><td align='left'>" (Aromatic)</td><td align='center'>2.84</td><td align='center'>3.52</td><td align='center'>3.99</td><td align='center'>3.70</td></tr>
+</table></div>
+
+
+<p>With the two benzoyl groups converted into nitro-benzoyl in each
+product, the limit of the ester reaction with the cellulose residue is
+reached at the third OH group.<span class='pagenum'><a name="Page_40" id="Page_40">[Pg 40]</a></span></p>
+
+<p>The nitrogen in the amidobenzoate resulting from the reduction with
+ammonium sulphide was 4.5 p.ct.&mdash;as against 5.0 p.ct. calculated. The
+moisture retained by the fibrous nitrate&mdash;nitrobenzoate&mdash;in the air-dry
+state was found to be 1.97 p.ct.</p>
+
+<p>The product from the structureless dibenzoate or tetrabenzoate on the
+C<sub>12</sub> formula, was prepared and analysed with the following results:</p>
+
+<div class='center'>
+<table border="0" cellpadding="4" cellspacing="0" summary="">
+<tr><td align='left'></td><td align='left'></td><td align='left'></td><td align='left'>Calc. for Mononitrate<br /> tetranitrobenzoate</td></tr>
+<tr><td align='left'>Total</td><td align='left'>Nitrogen</td><td align='left'>6.76</td><td align='center'>7.25</td></tr>
+<tr><td align='left'>O.NO<sub>2</sub></td><td align='left'>"</td><td align='left'>1.30</td><td align='center'>1.45</td></tr>
+<tr><td align='left'>NO<sub>2</sub></td><td align='left'>" (Aromatic)</td><td align='left'>5.46</td><td align='center'>5.80</td></tr>
+</table></div>
+
+<p>The results were confirmed by the yield of product, viz. 131 p.ct. as
+against the calculated 136 p.ct. They afford further evidence of the
+generally low limit of esterification of the cellulose molecule. From
+the formation of a 'normal' tetracetate&mdash;i.e. octacetate of the C<sub>12</sub>
+unit&mdash;we conclude that 4/5 of the oxygen atoms are hydroxyl oxygen. Of
+the 8 OH groups five only react in the mixed esters described above, and
+six only in the case of the simple nitric esters. The ester reactions
+are probably not simple, but accompanied by secondary reactions within
+the cellulose molecule.</p>
+
+<hr style='width: 45%;' />
+
+<p>(p. 34) <b>Cellulose Acetates.</b>&mdash;In the first edition (p. 35) we have
+committed ourselves to the statement that 'on boiling cotton with acetic
+anhydride and sodium acetate no reaction occurs.' This is erroneous. The
+error arises, however, from the somewhat vague statements of
+Schutzenberger's researches which are current in the text-books [e.g.
+Beilstein, 1 ed. p. 586] together with the statement that reaction only
+occurs at elevated temperatures (180&deg;). As a matter of fact, reaction
+takes place at the boiling temperature of the anhydride.<span class='pagenum'><a name="Page_41" id="Page_41">[Pg 41]</a></span> We have
+obtained the following results with bleached cotton:</p>
+
+<div class='center'>
+<table border="0" cellpadding="4" cellspacing="0" summary="">
+<tr><td align='left'></td><td align='left'></td><td align='left'>Yield</td><td align='left'>Calc. for Monoacetate</td></tr>
+<tr><td align='left'></td><td align='left'></td><td align='left'></td><td align='left'>C<sub>6</sub>H<sub>7</sub>O<sub>4</sub>O.C<sub>2</sub>H<sub>3</sub>O</td></tr>
+<tr><td align='left'>Ester reaction</td><td align='left'></td><td align='left'>121 p.ct.</td><td align='center'>125 p.ct.</td></tr>
+<tr><td align='left'>Saponification</td><td align='left'>{Cellulose</td><td align='left'>79.9</td><td align='center'>79.9</td></tr>
+<tr><td align='left'></td><td align='left'>{Acetic acid</td><td align='left'>29.9</td><td align='center'>29.4</td></tr>
+</table></div>
+
+
+<p>This product is formed without apparent structural alteration of the
+fibre. It is entirely insoluble in all the ordinary solvents of the
+higher acetates. Moreover, it entirely resists the actions of the
+special solvents of cellulose&mdash;e.g. zinc chloride and cuprammonium. The
+compound is in other respects equally stable and inert. The hygroscopic
+moisture under ordinary atmospheric conditions is 3.2 p.ct.</p>
+
+<p><i>Tetracetate.</i>&mdash;This product is now made on the manufacturing scale: it
+has yet to establish its industrial value.</p>
+
+
+<h3>NITRIRUNG VON KOHLENHYDRATEN.</h3>
+
+<h4><span class="smcap">W. Will</span> und <span class="smcap">P. Lenze</span> (Berl. Ber., 1898, 68).</h4>
+
+<h3><b>NITRATES OF CARBOHYDRATES.</b></h3>
+
+<p>(p. 38) The authors have studied the nitric esters of a typical series
+of the now well-defined carbohydrates&mdash;pentoses, hexoses, both aldoses
+and ketoses&mdash;bioses and trioses, the nitrates being prepared under
+conditions designed to produce the highest degree of esterification.
+Starch, wood, gum, and cellulose were also included in the
+investigations. The products were analysed and their physical properties
+determined. They were more especially investigated in regard to
+temperatures of decomposition, which were found to lie considerably
+lower than that of the cellulose nitrates. They also show marked and
+variable instability at 50&deg; C. A main purpose of the inquiry was to
+throw light upon a probable cause of the instability of the cellulose
+nitrates, viz. the presence of nitrates<span class='pagenum'><a name="Page_42" id="Page_42">[Pg 42]</a></span> of hydrolysed products or
+carbohydrates of lower molecular weight.</p>
+
+<p>The most important results are these:</p>
+
+<p><i>Monoses.</i>&mdash;The <i>aldoses</i> are fully esterified, in the pentoses 4 OH, in
+the hexoses 5 OH groups reacting. The pentose nitrates are comparatively
+stable at 50&deg;; the hexose nitrates on the other hand are extremely
+unstable, showing a loss of weight of 30-40 p.ct. when kept 24 hours at
+this temperature.</p>
+
+<p>Xylose is differentiated by tending to pass into an anhydride form
+(C<sub>5</sub>H<sub>10</sub>O<sub>5</sub>-H<sub>2</sub>O) under this esterification. When treated in
+fact with the mixed acids, instead of by the process usually adopted by
+the authors of solution in nitric acid and subsequent addition of the
+sulphuric acid, it is converted into the dinitrate
+C<sub>5</sub>H<sub>6</sub>O<sub>2</sub>.(NO<sub>3</sub>)<sub>2</sub>.</p>
+
+<p><i>Ketoses</i> (C<sub>6</sub>).&mdash;These are sharply differentiated from the
+corresponding aldoses by giving <i>tri</i>nitrates
+C<sub>6</sub>H<sub>7</sub>O<sub>2</sub>(NO<sub>3</sub>)<sub>3</sub> instead of <i>penta</i>nitrates, the remaining OH
+groups probably undergoing internal condensation. The products are,
+moreover, <i>extremely stable</i>. It is also noteworthy that levulose gave
+this same product, the trinitrate of the anhydride (levulosan) by both
+methods of nitration (<i>supra</i>).</p>
+
+<p><i>The bisaccharides or bioses</i> all give the octonitrates. The degree of
+instability is variable. Cane-sugar gives a very unstable nitrate. The
+lactose nitrate is more stable. Thus at 50&deg; it loses only 0.7 p.ct. in
+weight in eight days; at 75&deg; it loses 1 p.ct. in twenty-four hours, but
+with a rapid increase to 23 p.ct. in fifty-four hours. The maltose
+octonitrate melts (with decomposition) at a relatively high temperature,
+163&deg;-164&deg;. At 50&deg;-75&deg; it behaves much like the lactose nitrate.</p>
+
+<p><i>Trisaccharide.</i>&mdash;Raffinose yielded the product</p>
+
+<p>
+<span style="margin-left: 2.5em;">C<sub>18</sub>H<sub>21</sub>O<sub>5</sub>.(NO<sub>3</sub>)<sub>11</sub>.</span><br />
+</p>
+
+<p><i>Starch</i> yields the hexanitrate (C<sub>12</sub>) by both methods of nitration.
+The product has a high melting and decomposing point,<span class='pagenum'><a name="Page_43" id="Page_43">[Pg 43]</a></span> viz. 184&deg;, and
+when thoroughly purified is quite stable. It is noted that a yield of
+157 p.ct. of this nitrate was obtained, and under identical conditions
+cellulose yielded 170 p.ct.</p>
+
+<p><i>Wood gum</i>, from beech wood, gave a tetranitrate (C<sub>10</sub> formula)
+insoluble in all the usual solvents for this group of esters.</p>
+
+<p>The authors point out in conclusion that the conditions of instability
+and decomposition of the nitrates of the monose-triose series are
+exactly those noted with the cellulose nitrates as directly prepared and
+freed from residues of the nitrating acids. They also lay stress upon
+the superior stability of the nitrates of the anhydrides, especially of
+the ketoses.</p>
+
+
+<h3>NITRATED CARBOHYDRATES AS FOOD MATERIAL FOR MOULDS.</h3>
+
+<h4><span class="smcap">Thomas Bokorny</span> (Chem. Zeit., 1896, 20, 985-986).</h4>
+
+<p>(p. 38) Cellulose trinitrate (nitrocellulose) will serve as a food
+supply for moulds when suspended in distilled water containing the
+requisite mineral matter and placed in the dark. The growth is rapid,
+and a considerable quantity of the vegetable growth accumulates round
+the masses of cellulose nitrate, but no growth is observed if mineral
+matter is absent. Cellulose itself cannot act as a food supply, and it
+seems probable that if glycerol is present cellulose nitrate is no
+longer made use of.</p>
+
+
+<h3>NITRATION OF CELLULOSE, HYDROCELLULOSE, AND OXYCELLULOSE.</h3>
+
+<h4><span class="smcap">Leo Vignon</span> (Compt. rend., 1898, 126, 1658-1661).</h4>
+
+<p>(p. 38) Repeated treatment of cellulose, hydrocellulose, and
+oxycellulose with a mixture of sulphuric and nitric acids in<span class='pagenum'><a name="Page_44" id="Page_44">[Pg 44]</a></span> large
+excess, together with successive analyses of the compounds produced,
+showed that the final product of the reaction corresponded, in each
+case, with the fixation of 11 NO groups by a molecule containing 24
+atoms of carbon. On exposure to air, nitrohydrocellulose becomes yellow
+and decomposes; nitro-oxycellulose is rather more stable, whilst
+nitrocellulose is unaffected. The behaviour of these nitro-derivatives
+with Schiff's reagent, Fehling's solution, and potash show that all
+three possess aldehydic characters, which are most marked in the case of
+nitro-oxycellulose. The latter also, when distilled with hydrochloric
+acid, yields a larger proportion of furfuraldehyde than is obtained from
+nitrocellulose and nitrohydrocellulose.</p>
+
+<hr style='width: 45%;' />
+
+<h3><b>CELLULOSE NITRATES-EXPLOSIVES.</b></h3>
+
+<p>(p. 38) The uses of the cellulose nitrates as a basis for explosives are
+limited by their fibrous character. The conversion of these products
+into the structureless homogeneous solid or semi-solid form has the
+effect of controlling their combustion. The use of nitroglycerin as an
+agent for this purpose gives the curious result of the admixture of two
+high or blasting explosives to produce a new explosive capable of
+extended use for military purposes. The leading representatives of this
+class of propulsive explosives, or 'smokeless powders' are ballistite
+and cordite, the technology of which will be found fully discussed in
+special manuals of the subject. Since the contribution of these
+inventions to the development of cellulose chemistry does not go beyond
+the broad, general facts above mentioned, we must refer the reader for
+technical details to the manuals in question.</p>
+
+<p>There are, however, other means of arriving at structureless cellulose
+nitrates. One of these has been recently disclosed, and as the results
+involve chemical and technical points of<span class='pagenum'><a name="Page_45" id="Page_45">[Pg 45]</a></span> novelty, which are dealt with
+in a scientific communication, we reproduce the paper in question,
+viz.:&mdash;</p>
+
+
+<h3>A RE-INVESTIGATION OF THE CELLULOSE NITRATES.</h3>
+
+<h4><span class="smcap">A. Luck</span> and <span class="smcap">C. F. Cross</span> (J. Soc. Chem. Ind., 1900).</h4>
+
+<p>The starting-point of these investigations was a study of the nitrates
+obtained from the structureless cellulose obtained from the
+sulphocarbonate (viscose). This cellulose in the form of a fine meal was
+treated under identical conditions with a sample of pure cotton
+cellulose, viz. digested for 24 hours in an acid mixture containing in
+100 parts HNO<sub>3</sub>&mdash;24 : H<sub>2</sub>SO<sub>4</sub>&mdash;70: H<sub>2</sub>O&mdash;6: the proportion of
+acid to cellulose being 60 : 1&mdash;. After careful purification the
+products were analysed with the following results:</p>
+
+
+<div class='center'>
+<table border="0" cellpadding="4" cellspacing="0" summary="">
+<tr><td align='left'></td><td align='left'>Nitrogen</td><td align='left'>Soluble in Ether alcohol</td></tr>
+<tr><td align='left'>Fibrous nitrate</td><td align='center'>13.31</td><td align='center'>4.3 p.ct.</td></tr>
+<tr><td align='left'>Structureless nitrate</td><td align='center'>13.35</td><td align='center'>5.6&nbsp; "</td></tr>
+</table></div>
+
+<p>Examined by the 'heat test' (at 80&deg;) and the 'stability test' (at 135&deg;)
+they exhibited the usual instability, and in equal degrees. Nor were the
+tests affected by exhaustive treatment with ether, benzene, and alcohol.
+From this it appears that the process of solution as sulphocarbonate and
+regeneration of the cellulose, though it eliminates certain constituents
+of an ordinary bleached cellulose, which might be expected to cause
+instability, has really no effect in this direction. It also appears
+that instability may be due to by-products of the esterification process
+derived from the cellulose itself.</p>
+
+<p>The investigation was then extended to liquids having a direct solvent
+action on these higher nitrates, more especially acetone. It was
+necessary, however, to avoid this solvent<span class='pagenum'><a name="Page_46" id="Page_46">[Pg 46]</a></span> action proper, and having
+observed that dilution with water in increasing proportions produced a
+graduated succession of physical changes in the fibrous ester, we
+carried out a series of treatments with such diluted acetones.
+Quantities of the sample (A), purified as described, but still unstable,
+were treated each with five successive changes of the particular liquid,
+afterwards carefully freed from the acetone and dried at 40&deg;C. The
+products, which were found to be more or less disintegrated, were then
+tested by the ordinary heat test, stability test, and explosion test,
+with the results shown in the table on next page.</p>
+
+<p>In this series of trials the sample 'A' was used in the condition of
+pulp, viz. as reduced by the process of wet-beating in a Hollander. A
+similar series was carried out with the guncotton in the condition in
+which it was directly obtained from the ester reaction. The results were
+similar to above, fully confirming the progressive character of the
+stabilisation with increasing proportions of acetone. These results
+prove that washing with the diluted acetone not only rendered the
+nitrate perfectly stable, but that the product was more stable than that
+obtained by the ordinary process of purification, viz. long-continued
+boiling and washing in water. We shall revert to this point after
+briefly dealing with the associated phenomenon of structural
+disintegration. This begins to be well marked when the proportion of
+acetone exceeds 80 p.ct. The optimum effect is obtained with mixtures of
+90 to 93 acetone and 10 to 7 water (by volume). In a slightly diluted
+acetone of such composition, the guncotton is instantly attacked, the
+action being quite different from the gelatinisation which precedes
+solution in the undiluted solvent. The fibrous character disappears, and
+the product assumes the form of a free, bulky, still opaque mass, which
+rapidly sinks to the bottom of the containing vessel. The disintegration
+of the bulk of the nitrate is associated with<span class='pagenum'><a name="Page_47" id="Page_47">[Pg 47]</a></span></p>
+
+
+<div class='center'>
+<table border="1" cellpadding="4" cellspacing="0" summary="">
+<tr><td rowspan="2">--</td><td colspan="2"> Proportions by volume</td><td align='left'>&nbsp;</td><td align='left'>&nbsp;</td><td align='left'>&nbsp;</td></tr>
+<tr><td align='left'> Acetone</td><td align='left'> Water</td><td align='left'> Temperature of Explosion</td><td align='left'> Heat Test 80&deg;</td><td align='left'> Heat Test 134&deg;</td></tr>
+<tr><td rowspan="10"> From 'A' sample.</td><td align='left'>&nbsp;</td><td align='left'>&nbsp;</td><td align='left'> Deg.</td><td align='left'> Mins.</td><td align='left'> Mins.</td></tr>
+<tr><td align='left'> 20</td><td align='left'> 80</td><td align='left'> 137</td><td align='left'> 3</td><td align='left'> 4</td></tr>
+<tr><td align='left'> 30</td><td align='left'> 70</td><td align='left'> 160</td><td align='left'> 3</td><td align='left'> 4</td></tr>
+<tr><td align='left'> 40</td><td align='left'> 60</td><td align='left'> 180</td><td align='left'> 7</td><td align='left'> 18</td></tr>
+<tr><td align='left'>&nbsp;</td><td align='left'>&nbsp;</td><td align='left'>&nbsp;</td><td align='left'>&nbsp;</td><td align='left'> No fumes after</td></tr>
+<tr><td align='left'> 50</td><td align='left'> 50</td><td align='left'> 187.5</td><td align='left'> 55</td><td align='left'> 100</td></tr>
+<tr><td align='left'> 60</td><td align='left'> 40</td><td align='left'> 187</td><td align='left'> 45</td><td align='left'> 100</td></tr>
+<tr><td align='left'> 70</td><td align='left'> 30</td><td align='left'> 185</td><td align='left'> 45</td><td align='left'> 100</td></tr>
+<tr><td align='left'> 80</td><td align='left'> 20</td><td align='left'>--</td><td align='left'> 50</td><td align='left'> 100</td></tr>
+<tr><td align='left'> 92</td><td align='left'> 8</td><td align='left'> 185</td><td align='left'> 50</td><td align='left'> 100</td></tr>
+<tr><td align='left'>&nbsp;</td><td colspan="2"> Structureless powder.</td><td align='left'>&nbsp;</td><td align='left'>&nbsp;</td><td align='left'>&nbsp;</td></tr>
+<tr><td align='left'>&nbsp;&nbsp;"&nbsp;&nbsp;&nbsp; 'B' sample</td><td align='left'>50</td><td align='left'> 50</td><td align='left'> 183</td><td align='left'> 35</td><td align='left'> 100</td></tr>
+<tr><td align='left'>&nbsp;&nbsp;"&nbsp;&nbsp;&nbsp; 'C' sample</td><td colspan="2"> Ordinary service guncotton</td><td align='left'> 185</td><td align='left'> 10</td><td align='left'> 41</td></tr>
+</table></div>
+
+
+
+<p>a certain solvent action, and on adding an equal bulk of water, the
+dissolved nitrate for the most part is precipitated, at the same time
+that the undissolved but disintegrated and swollen product undergoes
+further changes in the direction of increase of hardness and density.
+The product being now collected on a filter, freed from acetone by
+washing with water and dried, is a hard and dense powder the fineness of
+which varies according to the attendant conditions of treatment. With
+the main product in certain cases there is found associated a small
+proportion of nitrate retaining a fibrous character, which may be
+separated by means of a fine sieve. On examining such a residue, we
+found it to contain only 5.6 p.ct. N, and as it was insoluble in strong
+acetone, it may be regarded as a low nitrate or a mixture of such with
+unaltered cellulose. Confirming this we found that the product passing
+through the sieve showed an increase of nitrogen to 13.43 p.ct. from the
+13.31 p.ct. in the original. Tested by the heat test (50 minutes) and
+stability test (no fumes after 100 minutes), we found the products to
+have the characteristics previously noticed.<span class='pagenum'><a name="Page_48" id="Page_48">[Pg 48]</a></span></p>
+
+<p>It is clear, therefore, that this specifically regulated action of
+acetone produces the effects (<i>a</i>) of disintegration, and (<i>b</i>)
+stabilisation. It remains to determine whether the latter effect was
+due, as might be supposed, to the actual elimination of a compound or
+group of compounds present in the original nitrate, and to be regarded
+as the effective cause of instability. It is to be noted first that as a
+result of the treatment with the diluted acetone and further dilution
+after the specific action is completed, collecting the disintegrated
+product on a filter and washing with water, the loss of weight sustained
+amounts to 3 to 4 p.ct. This loss is due, therefore, to products
+remaining dissolved in the filtrate&mdash;that is to say, in the much diluted
+acetone. These filtrates are in fact opalescent from the presence of a
+portion of nitrate in a colloidal (hydrated) form. On distilling off the
+acetone, a precipitation is determined. The precipitates are nitrates of
+variable composition, analysis showing from 9 to 12 p.ct. of nitric
+nitrogen. The filtrate from these precipitates containing only
+fractional residues of acetone still shows opalescence. On
+long-continued boiling a further precipitation is determined, the
+filtrates from which are clear. It was in this final clear filtrate that
+the product assumed to cause the instability of the original nitrate
+would be present. The quantity, however, is relatively so small that we
+have only been able to obtain and examine it as residue from evaporation
+to dryness. An exhaustive qualitative examination established a number
+of negative characteristics, with the conclusion that the products were
+not direct derivatives of carbohydrates nor aromatic compounds. On the
+other hand the following positive points resulted. Although the original
+diluted acetone extract was neutral to test papers, yet the residue was
+acid in character. It contained combined nitric groups, fused below 200&deg;
+giving off acid vapours, and afterwards burning with a smoky flame. On
+adding lead acetate to the original clear solution, a well-marked<span class='pagenum'><a name="Page_49" id="Page_49">[Pg 49]</a></span>
+precipitation was determined. The lead compounds thus isolated are
+characteristic. They have been obtained in various ways and analysed.
+The composition varies with the character of the solution in which the
+lead compound is formed. Thus in the opalescent or milky solutions in
+which a proportion of cellulose nitrate is held in solution or
+semi-solution by the acetone still present, the lead acetate causes a
+dense coagulation. The precipitates dried and analysed showed 16-20
+p.ct. PbO and 11-9 p.ct. N. It is clear that the cellulose nitrates are
+associated in these precipitates with the lead salts of the acid
+compounds in question. When the latter are obtained from clear
+solutions, i.e. in absence of cellulose nitrates, they contain 60-63
+p.ct. PbO and 3.5 p.ct. N (obtained as NO).</p>
+
+<p>In further confirmation of the conclusion from these results, viz. that
+the nitrocelluloses with no tendency to combine with PbO are associated
+with acid products or by-products of the ester reaction combining with
+the oxide, the lead reagent was allowed to react in the presence of 90
+p.ct. acetone. Water was added, the disintegrated mass collected, washed
+with dilute acetic acid, and finally with water. Various estimations of
+the PbO fixed in this way have given numbers varying from 2 to 2.5 p.ct.
+Such products are perfectly stable. This particular effect of
+stabilisation appears, therefore, to depend upon the combination of
+certain acid products present in ordinary nitrocelluloses with metallic
+oxides. In order to further verify this conclusion, standard specimens
+of cellulose nitrates have been treated with a large number of metallic
+salts under varying conditions of action. It has been finally
+established (1) that the effects in question are more particularly
+determined by treatment with salts of lead and zinc, and (2) that the
+simplest method of treatment is that of boiling the cellulose nitrates
+with dilute aqueous solutions of salts of these metals, preferably the
+acetates.<span class='pagenum'><a name="Page_50" id="Page_50">[Pg 50]</a></span> The following results may be cited, obtained by boiling a
+purified 'service' guncotton (sample C) with a 1 p.ct. solution of lead
+acetate and of zinc acetate respectively. After boiling 60 minutes the
+nitrates were washed free from the soluble metallic salts, dried and
+tested.</p>
+
+
+<div class='center'>
+<table border="0" cellpadding="4" cellspacing="0" summary="">
+<tr><td align='left'></td><td align='center'> Heat Test at 80&deg;</td><td align='center'> Heat Test at 134&deg;</td></tr>
+<tr><td align='left'>Original sample C</td><td align='center'> 10</td><td align='center'> 41</td></tr>
+<tr><td align='left'>Treated with lead acetate</td><td align='center'> 67</td><td align='center'> 45</td></tr>
+<tr><td align='left'>&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;"&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;zinc&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;"</td><td align='center'> 91</td><td align='center'> 45</td></tr>
+</table></div>
+
+
+<p>In conclusion we may briefly resume the main points arrived at in these
+investigations.</p>
+
+<p><i>Causes of instability of cellulose nitrates.</i>&mdash;The results of our
+experiments so far as to the causes of instability in cellulose nitrates
+may be summed up as follows:&mdash;</p>
+
+<p>(1) Traces of free nitrating acids, which can only occur in the finished
+products through careless manufacture, will undoubtedly cause
+instability, indicated strongly by the ordinary heat test at 80&deg;, and to
+a less extent by the heat test at 134&deg;.</p>
+
+<p>(2) Other compounds exist in more intimate association with the
+cellulose nitrates causing instability which cannot be removed by
+exhaustive washing with either hot or cold water, by digestion in cold
+dilute alkaline solutions such as sodium carbonate, or by extracting
+with ether, alcohol, benzene, &amp;c.; these compounds, however, are soluble
+in the solvents of highly nitrated cellulose such as acetone, acetic
+ether, pyridine, &amp;c., even when these liquids are so diluted with water
+or other non-solvent liquids to such an extent that they have little or
+no solvent action upon the cellulose nitrate itself. These solutions
+containing the bodies causing instability are neutral to test paper, but
+become acid upon evaporation by heating. (This probably explains the
+presence of free acid when guncotton is<span class='pagenum'><a name="Page_51" id="Page_51">[Pg 51]</a></span> purified by long-continued
+boiling in water without any neutralising agent being present.)</p>
+
+<p>(3) The bodies causing instability are products or by-products of the
+original ester reaction, acid bodies containing nitroxy-groups, but
+otherwise of ill-defined characteristics. They combine with the oxides
+of zinc or lead, giving insoluble compounds. They are precipitated from
+their solutions in diluted acetone upon the addition of soluble salts of
+these metals.</p>
+
+<p>(4) Cellulose nitrates are rendered stable either by eliminating these
+compounds, or by combining them with the oxides of lead or zinc whilst
+still in association with cellulose nitrates.</p>
+
+<p>(5) Even the most perfectly purified nitrocellulose will slowly
+decompose with formation of unstable acid products by boiling for a long
+time in water. This effect is much more apparent at higher temperatures.</p>
+
+<p><i>Dense structureless or non-fibrous cellulose nitrates</i> can be
+industrially prepared (1) by nitrating the amorphous forms of cellulose
+obtained from its solution as sulphocarbonate (viscose). The cellulose
+in this condition reacts with the closest similarity to the original
+fibrous cellulose; the products are similar in composition and
+properties, including that of instability.</p>
+
+<p>(2) By treating the fibrous cellulose nitrates with liquid solvents of
+the high nitrate diluted with non-solvent liquids, and more especially
+water. The optimum effect is a specific disintegration or breaking down
+of their fibrous structure quite distinct from the gelatinisation which
+precedes solution in the undiluted solvent, and occurring within narrow
+limits of variation in the proportion of the diluting and non-solvent
+liquid&mdash;for industrial work the most convenient solution to employ is
+acetone diluted with about 10 p.ct. of water by volume.</p>
+
+<p>The industrial applications of these results are the basis of English
+patents 5286 (1898), 18,868 (1898), 18,233 (1898), Luck and Cross (this
+Journal, 1899, 400, 787).<span class='pagenum'><a name="Page_52" id="Page_52">[Pg 52]</a></span></p>
+
+<p>The structureless guncotton prepared as above described is of quite
+exceptional character, and entirely distinct from the ordinary fibrous
+nitrate or the nitrate prepared by precipitation from actual solution in
+an undiluted solvent.<a name="FNanchor_3_3" id="FNanchor_3_3"></a><a href="#Footnote_3_3" class="fnanchor">[3]</a> By the process described, the nitrate is
+obtained at a low cost in the form of a very fine, dense, structureless,
+white powder of great purity and stability, entirely free from all
+mechanical impurities. The elimination of these mechanical impurities,
+and also to a very great extent of coloured compounds contained in the
+fibrous nitrate, makes the product also useful in the manufacture of
+celluloids, artificial silk, &amp;c., whilst its very dense form gives it a
+great advantage over ordinary fibrous guncotton for use in shells and
+torpedoes, and for the manufacture of gelatinised gunpowders, &amp;c. It can
+be compressed with ease into hard masses; and experiments are in
+progress with a view of producing from it, in admixture with 'retaining'
+ingredients, a military explosive manufactured by means of ordinary
+black gunpowder machinery and processes.</p>
+
+<p><i>Manufacture of sporting powder.</i>&mdash;The fact that the fibrous structure
+of ordinary guncotton or other cellulose nitrate can be completely or
+partially destroyed by treatment with diluted acetone and without
+attendant solution, constitutes a process of value for the manufacture
+of sporting powder having a base of cellulose nitrate of any degree of
+nitration. The following is a description of the hardening process.</p>
+
+<p>'Soft grains' are manufactured from ordinary guncotton or other
+cellulose nitrate either wholly or in combination with other
+ingredients, the process employed being the usual one of revolving in a
+drum in the damp state and sifting out the grains of suitable size after
+drying. These grains are then treated with diluted acetone, the degree
+of dilution being<span class='pagenum'><a name="Page_53" id="Page_53">[Pg 53]</a></span> fixed according to the hardness and bulk of the
+finished grain it is desired to produce (J. Soc. Chem. Ind., 1899, 787).
+Owing to the wide limits of dilution and corresponding effect, the
+process allows of the production of either a 'bulk' or a 'condensed'
+powder.</p>
+
+<p>We prefer to use about five litres of the liquid to each one kilo. of
+grain operated upon, as this quantity allows of the grains being freely
+suspended in the liquid upon stirring. The grains are run into the
+liquid, which is then preferably heated to the boiling-point for a few
+minutes whilst the whole is gently stirred. Under this treatment the
+grains assume a more or less rounded gelatinous condition according to
+the strength of the liquid. There is, however, no solution of the
+guncotton and practically no tendency of the grains to cohere. Each
+grain, however, is acted upon <i>throughout</i> and perfectly <i>equally</i>.
+After a few minutes' treatment, water is gradually added, when the
+grains rapidly harden. They are then freed from acetone and certain
+impurities by washing with water, heating, and drying. The process is of
+course carried out in a vessel provided with any means for gentle
+stirring and heating, and with an outlet for carrying off the
+volatilised solvent which is entirely recovered by condensation, the
+grains parting with the acetone with ease.</p>
+
+<p><i>Stabilising cellulose nitrates.</i>&mdash;The process is of especial value in
+rendering stable and inert the traces of unstable compounds which always
+remain in cellulose nitrate after the ordinary boiling and washing
+process. It is of greatest value in the manufacture of collodion cotton
+used for the preparation of gelatinous blasting explosives and all
+explosives composed of nitroglycerin and cellulose nitrates. Such
+mixtures seem peculiarly liable to decomposition if the cellulose
+nitrate is not of exceptional stability (J. Soc. Chem. Ind., 1899,
+787).<span class='pagenum'><a name="Page_54" id="Page_54">[Pg 54]</a></span></p>
+
+
+<h3>EMPLOI DE LA CELLULOSE POUR LA FABRICATION DE FILS BRILLANTS IMITANT LA
+SOIE.</h3>
+
+<h4><span class="smcap">E. Bronnert</span> (1) (Rev. Mat. Col., 1900, September, 267).</h4>
+
+<h3>V. USE OF CELLULOSE IN THE MANUFACTURE OF IMITATIONS OF SILK
+(LUSTRA-CELLULOSE).</h3>
+
+<p>(p. 45) <i>Introduction.</i>&mdash;The problem of spinning a continuous thread of
+cellulose has received in later years several solutions. Mechanically
+all resolve themselves into the preparation of a structureless filtered
+solution of cellulose or a cellulose derivative, and forcing through
+capillary orifices into some medium which either absorbs or decomposes
+the solvent. The author notes here that the fineness and to a great
+extent the softness of the product depends upon the dimensions of the
+capillary orifice and concentration of the solution. The technical idea
+involved in the spinning of artificial fibres is an old one. R&eacute;aumur (2)
+forecast its possibility, Audemars of Lausanne took a patent as early as
+1855 (3) for transforming nitrocellulose into fine filaments which he
+called 'artificial silk.' The idea took practical shape only when it
+came to be used in connection with filaments for incandescent lamps. In
+this connection we may mention the names of the patentees:&mdash;Swinburne
+(4), Crookes, Weston (5), Swan (6), and Wynne and Powell (7). These
+inventors prepared the way for Chardonnet's work, which has been
+followed since 1888 with continually increasing success.</p>
+
+<p>At this date the lustra-celluloses known may be divided into four
+classes.</p>
+
+<p>1. 'Artificial silks' obtained from the nitrocelluloses.</p>
+
+<p>2. 'Lustra-cellulose' made from the solution of cellulose in
+cuprammonium.</p>
+
+<p>3. 'Lustra-cellulose' prepared from the solution of cellulose in
+chloride of zinc.<span class='pagenum'><a name="Page_55" id="Page_55">[Pg 55]</a></span></p>
+
+<p>4. 'Viscose silks,' by the decomposition of sulphocarbonate of cellulose
+(Cross and Bevan).</p>
+
+<p><span class="smcap">Group</span> 1. The early history of the Chardonnet process is discussed and
+some incidental causes of the earlier failures are dealt with. The
+process having been described in detail in so many publications the
+reader is referred to these for details. [See Bibliography, (1) and (2),
+(3) and (4).] The denitrating treatment was introduced in the period
+1888-90 and of course altogether changed the prospects of the industry;
+not only does it remove the high inflammability, but adds considerably
+to softness, lustre, and general textile quality. In Table I will be
+found some important constants for the nitrocellulose fibre; also the
+fibre after denitration and the comparative constants for natural silk.</p>
+
+<h4><span class="smcap">Table</span> 1.</h4>
+
+<div class='center'>
+<table border="1" cellpadding="4" cellspacing="0" summary="">
+<tr><td align='left'>&nbsp;</td><td align='left'> Tenacity</td><td align='left'> Elasticity</td></tr>
+<tr><td align='left'>&nbsp;</td><td align='left'> (grammes)</td><td align='left'> (% elongation)</td></tr>
+<tr><td align='left'>Nitrocellulose according to Chardonnet German Patent No. 81,599</td><td align='left'> 150</td><td align='left'> 23</td></tr>
+<tr><td align='left'>The same after denitration</td><td align='left'> 110</td><td align='left'> 8</td></tr>
+<tr><td align='left'>Denitrated fibre moistened with water</td><td align='left'> 25</td><td align='left'> &mdash;</td></tr>
+<tr><td align='left'>Nitrocellulose: Bronnert's German Patent No. 93,009</td><td align='left'> 125</td><td align='left'> 28</td></tr>
+<tr><td align='left'>The same after denitration (dry)</td><td align='left'> 115</td><td align='left'> 13</td></tr>
+<tr><td align='left'>The same after denitration (wetted)</td><td align='left'> 32</td><td align='left'> &mdash;</td></tr>
+<tr><td align='left'>Natural silk</td><td align='left'> 300</td><td align='left'> 18</td></tr>
+</table></div>
+
+<div class="blockquot"><p>1. Tenacity is the weight in grammes required to break the
+thread.</p>
+
+<p>2. Elasticity is the elongation per cent. at breaking.</p>
+
+<p>The numbers are taken for thread of 100 deniers (450 metres of
+0.05 grammes = 1 denier). It must be noted that according to
+the concentration of the solution and variations in the process
+of denitration the constants for the yarn are subject to very
+considerable variation.</p></div>
+
+<p>In regard to the manufacture a number of very serious difficulties have
+been surmounted. First, instead of drying the nitrated cellulose, which
+often led to fires, &amp;c., it was found better to take it moist from the
+centrifugal machine, in which<span class='pagenum'><a name="Page_56" id="Page_56">[Pg 56]</a></span> condition it is dissolved (5). It was
+next found that with the concentrated collodion the thread could be spun
+direct into the air, and the use of water as a precipitant was thus
+avoided.</p>
+
+<p>With regard to denitration which is both a delicate and disagreeable
+operation: none of the agents recommended to substitute the sulphydrates
+have proved available. Of these the author mentions ferrous chloride
+(6), ferrous chloride in alcohol (7), formaldehyde (8),
+sulphocarbonates. The different sulphydrates (9) have very different
+effects. The calcium compound tends to harden and weaken the thread. The
+ammonia compound requires great care and is costly. The magnesium
+compound works rapidly and gives the strongest thread. Investigations
+have established the following point. In practice it is not necessary to
+combine the saponification of cellulose ester with complete reduction of
+the nitric acid split off. The latter requires eight molecules of
+hydrogen sulphide per one molecule tetranitrocellulose, but with
+precautions four molecules suffice. It is well known that the
+denitration is nearly complete, traces only of nitric groups surviving.
+Their reactions with diphenylamine allow a certain identification of
+artificial silks of this class. Various other inventors, e.g. Du Vivier
+(10), Cadoret (11), Lehner (12), have attempted the addition of other
+substances to modify the thread. These have all failed. Lehner, who
+persisted in his investigations, and with success, only attained this
+success, however, by leaving out all such extraneous matters. Lehner
+works with 10 p.ct. solutions; Chardonnet has continually aimed at
+higher concentration up to 20 p.ct. Lehner has been able very much to
+reduce his pressures of ejection in consequence; Chardonnet has had to
+increase up to pressures of 60 k. per cm. and higher. The latter
+involves very costly distributing apparatus. Lehner made next
+considerable advance<span class='pagenum'><a name="Page_57" id="Page_57">[Pg 57]</a></span> by the discovery of the fact that the addition of
+sulphuric acid to the collodion caused increase of fluidity (13), which
+Lehner attributes to molecular change. Chardonnet found similar results
+from the addition of aldehyde and other reagents (14), but not such as
+to be employed for the more concentrated collodions. The author next
+refers to his discoveries (15) that alcoholic solutions of a number of
+substances, organic and inorganic, freely dissolve the lower cellulose
+nitrates. The most satisfactory of these substances is chloride of
+calcium (16). It is noted that acetate of ammonia causes rapid changes
+in the solution, which appear to be due to a species of hydrolysis. The
+result is sufficiently remarkable to call for further investigation. The
+chloride of calcium, it is thought possible, produces a direct
+combination of the alcohol with a reactive group of the nitrocellulose.
+The fluidity of this solution using one mol. CaCl<sub>2</sub> per 1 mol.
+tetranitrate (17) reaches a maximum in half an hour's heating at
+60&deg;-70&deg;C. The fluidity is increased by starting from a cotton which has
+been previously mercerised. After nitration there is no objection to a
+chlorine bleach. Chardonnet has found on the other hand that in
+bleaching before nitration there is a loss of spinning quality in the
+collodion. The author considers that the new collodion can be used
+entirely in place of the ordinary ether-alcohol collodion. With regard
+to the properties of the denitrated products they fix all basic colours
+without mordant and may be regarded as oxycellulose therefore. The
+density of the thread is from 1.5 to 1.55. The thread of 100 deniers
+shows a mean breaking strain of 120 grammes with an elasticity of 8-12
+p.ct. The cardinal defect of these fibres is their property of
+combination with water. Many attempts have been made to confer
+water-resistance (18), but without success. Strehlenert has proposed the
+addition of formaldehyde (19), but this is without result (20). In
+reference to these effects of hydration, the author has made
+observations<span class='pagenum'><a name="Page_58" id="Page_58">[Pg 58]</a></span> on cotton thread, of which the following table represents
+the numerical results:</p>
+
+
+<div class='center'>
+<table border="0" cellpadding="4" cellspacing="0" summary="">
+<tr><td align='left'></td><td align='center'>Breaking Strain</td></tr>
+<tr><td align='left'></td><td align='center'>Mean of 20 experiments</td></tr>
+<tr><td align='left'>Skein of bleached cotton without treatment</td><td align='center'>825</td></tr>
+<tr><td align='left'>Skein of bleached cotton without treatment, but wetted</td><td align='center'>942</td></tr>
+<tr><td align='left'>Ditto after conversion into hexanitrate, dry</td><td align='center'>884</td></tr>
+<tr><td align='left'>The above, wetted</td><td align='center'>828</td></tr>
+<tr><td align='left'>The cotton denitrated from above, dry</td><td align='center'>529</td></tr>
+<tr><td align='left'>The cotton denitrated as above and wetted</td><td align='center'>206</td></tr>
+</table></div>
+
+<p>The author considers that other patents which have been taken for
+spinning nitrocellulose are of little practical account (21) and (22).
+The same conclusion also applies to the process of <i>Langhans</i>, who
+proposes to spin solutions of cellulose in sulphuric acid (23) (24) and
+mixtures of sulphuric acid and phosphoric acid.</p>
+
+<p><span class="smcap">Group</span> 2. <i>Lustra-cellulose.</i>&mdash;Thread prepared by spinning solutions of
+cellulose in cuprammonium.</p>
+
+<p>This product is made by the Vereinigte Glanzstoff-Fabriken, Aachen,
+according to a series of patents under the names of H. Pauly, M. Fremery
+and Urban, Consortium mulhousien pour la fabrication de fils brillants,
+E. Bronnert, and E. Bronnert and Fremery and Urban (1). The first patent
+in this direction was taken by Despeissis in 1890 (2). It appears this
+inventor died shortly after taking the patent (3) The matter was later
+developed by Pauly (4) especially in overcoming the difficulty of
+preparing a solution of sufficient concentration. (It is to be noted
+that Pauly's patents rest upon a very slender foundation, being
+anticipated in every essential detail by the previous patent of
+Despeissis.) For this very great care is required, especially, first,
+the condition of low temperature, and, secondly, a regulated proportion
+of copper and ammonia to cellulose. The solution takes place more
+rapidly if the cellulose has been previously oxidised. Such cellulose
+gives an 8 p.ct. solution, and the thread obtained has the character of
+an oxycellulose, specially seen in its dyeing properties. The best<span class='pagenum'><a name="Page_59" id="Page_59">[Pg 59]</a></span>
+results are obtained, it appears, by the preliminary mercerising
+treatment and placing the alkali cellulose in contact with copper and
+ammonia. (All reagents employed in molecular proportions.) The author
+notes that the so-called hydrocellulose (Girard) (5) is almost insoluble
+in cuprammonium, as is starch. It is rendered soluble by alkali
+treatment.</p>
+
+<p><span class="smcap">Group</span> 3. <i>Lustra-cellulose</i> prepared by spinning a solution of cellulose
+in concentrated chloride of zinc.</p>
+
+<p>This solution has been known for a long time and used for making
+filaments for incandescent lamps. The cellulose threads, however, have
+very little tenacity. This is no doubt due to the conditions necessary
+for forming the solution, the prolonged digestion causing powerful
+hydrolysis (1). Neither the process of Wynne and Powell (2) nor that of
+Dreaper and Tompkins (3), who have endeavoured to bring the matter to a
+practical issue, are calculated to produce a thread taking a place as a
+textile. The author has described in his American patent (4) a method of
+effecting the solution in the cold, viz. again by first mercerising the
+cellulose and washing away the caustic soda. This product dissolves in
+the cold and the solution remains unaltered if kept at low temperature.
+Experiments are being continued with these modifications of the process,
+and the author anticipates successful results. The modifications having
+the effect of maintaining the high molecular weight of the cellulose, it
+would appear that these investigations confirm the theory of Cross and
+Bevan that the tenacity of a film or thread of structureless regenerated
+cellulose is directly proportional to the molecular weight of the
+cellulose, i.e. to its degree of molecular aggregation (5).</p>
+
+<p><span class="smcap">Group</span> 4. 'Viscose' silks obtained by spinning solutions of xanthate of
+cellulose.</p>
+
+<p>In 1892, Cross and Bevan patented the preparation of a new and curious
+compound of cellulose, the thiocarbonate (1) (2) (3). Great hopes were
+based upon this product at the<span class='pagenum'><a name="Page_60" id="Page_60">[Pg 60]</a></span> time of its discovery. It was expected
+to yield a considerable industrial and financial profit and also to
+contribute to the scientific study of cellulose. The later patents of C.
+H. Stearn (4) describe the application of viscose to the spinning of
+artificial silk. The viscose is projected into solutions of chloride of
+ammonium and washed in a succession of saline solutions to remove the
+residual sulphur impurities. The author remarks that though it has a
+certain interest to have succeeded in making a thread from this compound
+and thus adding another to the processes existing for this purpose, he
+is not of opinion that it shows any advance on the lustra-cellulose (2)
+and (3). He also considers that the bisulphide of carbon, which must be
+regarded as a noxious compound, is a serious bar to the industrial use
+of the process, and for economic work he considers that the regeneration
+of ammonia from the precipitating liquors is necessary and would be as
+objectionable as the denitration baths in the collodion process. The
+final product not being on the market he does not pronounce a finally
+unfavourable opinion.</p>
+
+<p>The author and the Vereinigte Glanzstoff-Fabriken after long
+investigation have decided to make nothing but the lustra-cellulose (2)
+and (3). A new factory at Niedermorschweiler, near Mulhouse, is
+projected for this last production.</p>
+
+
+<h4>BIBLIOGRAPHY</h4>
+
+<h5><i>Introduction</i></h5>
+
+<p>(1) Bull. de la Soc. industr. de Mulhouse, 1900.</p>
+
+<p>(2) R&eacute;aumur, M&eacute;moire pour servir &agrave; l'histoire des insectes, 1874, 1, p.
+154.</p>
+
+<p>(3) English Pat. No. 283, Feb. 6, 1855.</p>
+
+<p>(4) Swinburne, Electrician, 18, 28, 1887, p. 256.</p>
+
+<p>(5) Weston (Swinburne), Electrician, 18, 1887, p. 287. Eng. Pat. No.
+22866, Sept. 12, 1882.</p>
+
+<p>(6) German Pat. No. 3029. English Pat. No. 161780, April 28, 1884
+(Swan).</p>
+
+<p>(7) Wynne-Powell, English Pat. No. 16805, Dec. 22, 1884.</p>
+
+
+<h5><i>Group I</i></h5>
+
+<p>(1) German Pat No. 38368, Dec. 20, 1885. German Pat. No. 46125, March 4,
+1888. German Pat. No. 56331, Feb. 6, 1890. German Pat. No. 81599, Oct.
+11, 1893. German Pat. No. 56655, April 23, 1890. French Pat. No. 231230,
+June 30, 1893.<span class='pagenum'><a name="Page_61" id="Page_61">[Pg 61]</a></span></p>
+
+<p>(2) Industrie textile, 1899, 1892. Wyss-Noef, Zeitschrift f&uuml;r angewandte
+Chemie, 1899, 30, 33. La Nature, Jan. 1, 1898, No. 1283. Revue g&eacute;n&eacute;rale
+des sciences, June 30, 1898.</p>
+
+<p>(3) German Pat. No. 46125, March 4, 1888. German Pat. No. 56655, April
+23, 1890.</p>
+
+<p>(4) Swan, English Pat. 161780, June 28, 1884. See also B&eacute;champ, Dict. de
+Chimie de Wurtz.</p>
+
+<p>(5) German Pat. No. 81599, Oct 11, 1893.</p>
+
+<p>(6) B&eacute;champ, art. Cellulose, Dict. de Chimie de Wurtz, p. 781.</p>
+
+<p>(7) Chardonnet, addit. March 3, 1897, to the French Pat. 231230, May 30,
+1893.</p>
+
+<p>(8) Knofler, French Pat. 247855, June 1, 1895. German Pat. 88556, March
+28, 1894.</p>
+
+<p>(9) B&eacute;champ, art. Cellulose, Dict. de Chimie de Wurtz. Blondeau, Ann.
+Chim. et Phys. (3), 1863, 68, p. 462.</p>
+
+<p>(10) Revue industrielle, 1890, p. 194. German Pat. 52977, March 7, 1889.</p>
+
+<p>(11) French Pat. 256854, June 2, 1896.</p>
+
+<p>(12) German Pat. 55949, Nov. 9, 1889. German Pat. 58508, Sept. 16, 1890.
+German Pat. 82555, Nov. 15, 1894.</p>
+
+<p>(13) German Pat. 58508, Sept. 16, 1900.</p>
+
+<p>(14) French Pat. 231230, June 30, 1893.</p>
+
+<p>(15) German Pat. 93009, Nov. 19, 1895. French Pat. 254703, March 12,
+1896. English Pat. 6858, March 28, 1896.</p>
+
+<p>(16) American Pat. 573132, Dec. 15, 1896.</p>
+
+<p>(17) This proportion is the most advantageous, and furnishes the best
+liquid collodions that can be spun.</p>
+
+<p>(18) French Pat. 259422, Sept. 3, 1896.</p>
+
+<p>(19) English Pat. 22540, 1896.</p>
+
+<p>(20) Application for German Pat. not granted, 4933 IV. 296, Mar. 16,
+1897.</p>
+
+<p>(21) German Pat. 96208, Feb. 10, 1897. Addit. Pat. 101844 and 102573,
+Dec. 10, 1897.</p>
+
+<p>(22) Oberle et Newbold, French Pat. 25828, July 22, 1896. Granquist,
+Engl. applic. 2379, Nov. 28, 1899.</p>
+
+<p>(23) German Pat. 72572, June 17, 1891.</p>
+
+<p>(24) Voy. Stern, Ber., 28, ch. 462.</p>
+
+
+<h5><i>Group II</i></h5>
+
+<p>(1) German Pat. 98642, Dec. 1, 1897 (Pauly). French Pat. 286692, March
+10, 1899, and addition of October 14, 1899 (Fremery and Urban). French
+Pat. 286726, March 11, 1899, and addition of December 4, 1899. German
+Pat. 111313, March 16, 1899 (Fremery and Urban). English Pat. 18884,
+Sept. 19, 1899 (Bronnert). English Pat. 13331, June 27, 1899 (Consort.
+mulhousien).</p>
+
+<p>(2) French Pat. 203741, Feb. 12, 1890.</p>
+
+<p>(3) The actual lapse of this patent is due to the death of Despeissis
+shortly after it was taken.<span class='pagenum'><a name="Page_62" id="Page_62">[Pg 62]</a></span></p>
+
+<p>(4) Without questioning the good faith of Pauly, it is nevertheless a
+fact that the original patent remains as a document, and therefore that
+the value of the Pauly patents is very questionable.</p>
+
+<p>(5) Girard, Ann. Chim. et Phys, 1881 (5), 24, p. 337-384.</p>
+
+
+<h5><i>Group III</i></h5>
+
+<p>(1) Cross and Bevan, Cellulose, 1895, p. 8.</p>
+
+<p>(2) English Pat. 16805, Dec. 22, 1884.</p>
+
+<p>(3) English Pat. 17901, July 30, 1897.</p>
+
+<p>(4) Bronnert, American Pat. 646799, April 3, 1900.</p>
+
+<p>(5) Cross and Bevan, Cellulose, 1895, p. 12.</p>
+
+
+<h5><i>Group IV</i></h5>
+
+<p>(1) English Pat. 8700, 1892. German Pat. 70999, Jan. 13, 1893.</p>
+
+<p>(2) English Pat. 4713, 1896. German Pat. 92590, Nov. 21, 1896.</p>
+
+<p>(3) Comptes rendus (loc. cit.). Berichte, c. 9, 65a.</p>
+
+<p>(4) English Pat. 1020, 1898. German Pat. 108511, Oct. 18, 1898.</p>
+
+
+<h3><b>Artificial Silk&mdash;Lustra-cellulose.</b></h3>
+
+<h4><span class="smcap">C. F. Cross</span> and <span class="smcap">E. J. Bevan</span> (J. Soc. Chem. Ind., 1896, 317).</h4>
+
+<p>The object of this paper is mainly to correct current statements as to
+the artificial or 'cellulose silks' being explosive or highly
+inflammable (<i>ibid.</i>, 1895, 720). A specimen of the 'Lehner' silk was
+found to retain only 0.19 p.ct. total nitrogen, showing that the
+denitration is sufficiently complete to dispose of any suggestion of
+high inflammability.</p>
+
+<p>The product yielded traces only of furfural; on boiling with a 1 p.ct.
+solution of sodium hydrate, the loss of weight was 9.14 p.ct.; but the
+solution had no reducing action on Fehling's solution. The product in
+denitration had therefore reverted completely to a cellulose (hydrate),
+no oxy-derivative being present.</p>
+
+<hr style='width: 45%;' />
+
+<p>The authors enter a protest against the term 'artificial silk' as
+applied to these products, and suggest 'lustra-cellulose.'<span class='pagenum'><a name="Page_63" id="Page_63">[Pg 63]</a></span></p>
+
+
+<h3>DIE K&Uuml;NSTLICHE SEIDE-IHRE HERSTELLUNG, EIGENSCHAFTEN UND VERWENDUNG.</h3>
+
+<h4><span class="smcap">Carl S&uuml;vern</span>, Berlin, 1900, J. Springer.</h4>
+
+<h3><b>ARTIFICIAL SILK&mdash;ITS PRODUCTION, PROPERTIES, AND APPLICATIONS.</b></h3>
+
+<p>This work of some 130 pages is an important monograph on the subject of
+the preparation of artificial cellulose threads&mdash;so far as the technical
+elements of the problems involved are discussed and disclosed in the
+patent literature. The first section, in fact, consists almost
+exclusively of the several patent specifications in chronological order
+and ranged under the sub-sections: (<i>a</i>) The Spinning of Nitrocellulose
+(collodion); (<i>b</i>) The Spinning of other Solutions of Cellulose; (<i>c</i>)
+The Spinning of Solutions of the Nitrogenous Colloids.</p>
+
+<p>In the second section the author deals with the physical and chemical
+proportions of the artificial threads.</p>
+
+<p><i>Chardonnet 'silk'</i> is stated to have a mean diameter of 35&micro;, but with
+considerable variations from the mean in the individual fibres; equally
+wide variations in form are observed in cross-section. The general form
+is elliptical, but the surface is marked by deep stri&aelig;, and the
+cross-section is therefore of irregular outline. This is due to
+irregular conditions of evaporation of the solvents, the thread being
+'spun' into the air from cylindrical orifices of regulated dimensions.
+Chardonnet states that when the collodion is spun into alcohol the
+resultant thread is a perfect cylinder (Compt. rend. 1889, 108, 962).
+The strength of the fibre is variously stated at from 50-80 p.ct. that
+of 'boiled off' China tram; the true elasticity is 4-5 p.ct., the
+elongation under the breaking strain 15-17 p.ct. The sp.gr. is 1.49,
+i.e. 3-5 p.ct. in excess of boiled off silk.</p>
+
+<p><i>Lehner 'silk'</i> exhibits the closest similarity to the Chardonnet<span class='pagenum'><a name="Page_64" id="Page_64">[Pg 64]</a></span>
+product. In cross-section it is seen to be more regular in outline, and
+a round, pseudo-tubular form prevails, due to the conditions of
+shrinkage and collapse of the fibre in parting with the solvents, and in
+then dehydrating. The constants for 'breaking strain,' both in the
+original and moistened condition, for elasticity, &amp;c., are closely
+approximate to those for the Chardonnet product.</p>
+
+<p><i>Pauly 'silk'.</i>&mdash;The form of the ultimate fibres is much more regular
+and the contour of the cross-section is smooth. The product shows more
+resistance to moisture and to alkaline solutions.</p>
+
+<p><i>Viscose 'silk'</i> is referred to in terms of a communication appearing in
+'Papier-Zeitung,' 1898, 2416.</p>
+
+<div class="blockquot"><p>In the above section the following publications are referred
+to: Chardonnet, 'Compt. rend.,' 1887, 105, 900; and 1889, 108,
+962; Silbermann, 'Die Seide,' 1897, v. 2, 143; Herzog,
+'Farber-Zeitung,' 1894/5, 49-50; Thiele, ibid. 1897, 133; O.
+Schlesinger, 'Papier-Zeitung,' 1895, 1578-81, 1610-12.</p></div>
+
+
+<h4><i>Action of Reagents upon Natural and Artificial Silks.</i></h4>
+
+<p>1. <i>Potassium hydrate</i> in solution of maximum concentration dissolves
+the silks proper, (<i>a</i>) China silk on slight warming, (<i>b</i>) Tussah silk
+on boiling. The cellulose 'silks' show swelling with discolouration, but
+the fibrous character is not destroyed even on boiling.</p>
+
+<p>2. <i>Potassium hydrate</i> 40 p.ct. China silk dissolves completely at
+65&deg;-85&deg;; Tussah silk swells considerably at 75&deg; and dissolves at
+100&deg;-120&deg;. The cellulose 'silks' are attacked with discolouration; at
+140&deg; (boiling-point of the solution) there is progressive solvent
+action, but the action is incomplete. The Pauly product is most
+resistant.</p>
+
+<p>3. <i>Zinc chloride</i>, 40 p.ct. solution. Both the natural silks and
+lustra-celluloses are attacked at 100&deg;, and on raising the temperature
+the further actions are as follows: China silk is<span class='pagenum'><a name="Page_65" id="Page_65">[Pg 65]</a></span> completely dissolved
+at 110-120&deg;; Tussah silk at 130-135&deg;; the collodion products at
+140-145&deg;; the Pauly product was again most resistant, dissolving at
+180&deg;.</p>
+
+<p>4. <i>Alkaline cupric oxide</i> (glycerin) solution was prepared by
+dissolving 10 grs. of the sulphate in 100 c.c. water, adding 5 grs.
+glycerin and 10 c.c. of 40 p.ct. KOH. In this solution the China silk
+dissolved at the ordinary temperature; Tussah silk and the
+lustra-celluloses were not appreciably affected.</p>
+
+<p>5. <i>Cuprammonium solution</i> was prepared by dissolving the precipitated
+cupric hydrate in 24 p.ct. ammonia. In this reagent also the China silk
+dissolved, and the Tussah silk as well as the lustra-celluloses
+underwent no appreciable change.</p>
+
+<p>6. <i>An ammoniacal solution of nickel oxide</i> was prepared by dissolving
+the precipitated hydrated oxide in concentrated ammonia. The China silk
+was dissolved by this reagent; Tussah silk and the lustra-celluloses
+entirely resisted its action.</p>
+
+<p>7. <i>Fehling's solution</i> is a solvent of the natural silks, but is
+without action on the lustra-celluloses.</p>
+
+<p>8. <i>Chromic acid</i>&mdash;20 p.ct. CrO<sub>3</sub>&mdash;solution dissolves both the natural
+silks and the lustra-celluloses at the boiling temperature of the
+solution.</p>
+
+<p>9. <i>Millon's reagent</i>, at the boiling solution, colours the natural
+silks violet: the lustra-celluloses give no reaction.</p>
+
+<p>10. <i>Concentrated nitric acid</i> attacks the natural silks powerfully in
+the cold; the lustra-celluloses dissolve on heating.</p>
+
+<p>11. <i>Iodine solution</i> (I in KI) colours the China silk a deep brown,
+Tussah a pale brown; the celluloses from collodion are coloured at first
+brown, then blue. The Pauly product, on the other hand, does not react.</p>
+
+<p>12. <i>Diphenylamine sulphate.</i>&mdash;A solution of the base in concentrated
+sulphuric acid colours the natural silks a brown; the collodion 'silks'
+give a strong blue reaction due to the<span class='pagenum'><a name="Page_66" id="Page_66">[Pg 66]</a></span> presence of residual
+nitro-groups. The Pauly product is not affected.</p>
+
+<p>13. <i>Brucin sulphate</i> in presence of concentrated sulphuric acid colours
+the natural silks only slightly (brown); the collodion 'silks' give a
+strong red colouration. The Pauly product again is without reaction.</p>
+
+<p>14. <i>Water.</i>&mdash;The natural silks do not soften in the mouth as do the
+lustra-celluloses.</p>
+
+<p>15. <i>Water of condition</i> was determined by drying at 100&deg;; the following
+percentages resulted (<i>a</i>). The percentages of water (<i>b</i>) taken up from
+the atmosphere after forty-three hours' exposure were:</p>
+
+
+<div class='center'>
+<table border="0" cellpadding="4" cellspacing="0" summary="">
+<tr><td align='left'></td><td align='center'>(<i>a</i>)</td><td align='center'>(<i>b</i>)</td></tr>
+<tr><td align='left'>China (raw) silk</td><td align='center'>7.97</td><td align='center'>2.24</td></tr>
+<tr><td align='left'>Tussah silk</td><td align='center'>8.26</td><td align='center'>5.00</td></tr>
+<tr><td align='left'>Lustra-celluloses:</td></tr>
+<tr><td align='left'>Chardonnet (Besan&ccedil;on)</td><td align='center'>10.37</td><td align='center'>5.64</td></tr>
+<tr><td align='left'>&nbsp;&nbsp;&nbsp;&nbsp;"&nbsp;&nbsp;&nbsp;&nbsp;Spreitenbach</td><td align='center'>11.17</td><td align='center'>5.77</td></tr>
+<tr><td align='left'>Lehner</td><td align='center'>10.71</td><td align='center'>5.97</td></tr>
+<tr><td align='left'>Pauly</td><td align='center'>10.04</td><td align='center'>6.94</td></tr>
+</table></div>
+
+<p>16. <i>Behaviour on heating at 200&deg;.</i>&mdash;After two hours' heating at this
+temperature the following changes were noted:</p>
+
+
+<div class='center'>
+<table border="0" cellpadding="4" cellspacing="0" summary="">
+<tr><td align='left'>China silk</td><td align='left'>Much discoloured (brown).</td></tr>
+<tr><td align='left'>Tussah silk</td><td align='left'>Scarcely affected.</td></tr>
+<tr><td align='left'>Lustra-celluloses:</td></tr>
+<tr><td align='left'>Chardonnet</td><td rowspan="2">Converted into a blue-black charcoal, retaining the form of the fibres.</td></tr>
+<tr><td align='left'>Lehner</td></tr>
+<tr><td align='left'>Pauly</td><td align='left'>A bright yellow-brown colouration, without carbonisation.</td></tr>
+</table></div>
+
+<p>17. The <i>losses of weight</i> accompanying these changes and calculated per
+100 parts of fibre dried at 100&deg; were:</p>
+
+<div class='center'>
+<table border="0" cellpadding="4" cellspacing="0" summary="">
+<tr><td align='left'>China silk</td><td align='center'>3.18</td></tr>
+<tr><td align='left'>Tussah silk</td><td align='center'>2.95</td></tr>
+</table></div>
+
+<p><span class='pagenum'><a name="Page_67" id="Page_67">[Pg 67]</a></span></p>
+
+
+<div class='center'>
+<table border="0" cellpadding="4" cellspacing="0" summary="">
+<tr><td align='left'>Lustra-celluloses:</td></tr>
+<tr><td align='left'>Chardonnet</td><td align='center'>33.70</td></tr>
+<tr><td align='left'>Lehner</td><td align='center'>26.56</td></tr>
+<tr><td align='left'>Pauly</td><td align='center'>1.61</td></tr>
+</table></div>
+
+<p>18. <i>Inorganic constituents.</i>&mdash;Determinations of the total ash gave for
+the first five of the above, numbers varying from 1.0 to 1.7 p.ct. The
+only noteworthy point in the comparison was the exceptionally small ash
+of the Pauly product, viz. 0.096 p.ct.</p>
+
+<p>19. <i>Total nitrogen.</i>&mdash;The natural silks contain the 16-17 p.ct. N
+characteristic of the proteids. The lustra-celluloses contain 0.05-0.15
+p.ct. N which in those spun from collodion is present in the form of
+nitric groups.</p>
+
+<p>The points of chemical differentiation which are established by the
+above scheme of comparative investigation are summed up in tabular form.</p>
+
+<p><i>Methods of dyeing.</i>&mdash;The lustra-celluloses are briefly discussed. The
+specific relationship of these forms of cellulose to the colouring
+matters are in the main those of cotton, but they manifest in the
+dye-bath the somewhat intensified attraction which characterises
+mercerised cotton, or more generally the cellulose hydrates.</p>
+
+<p><i>Industrial applications</i> of the lustra-celluloses are briefly noticed
+in the concluding section of the book.</p>
+
+<div class="footnotes"><h3>FOOTNOTES:</h3>
+
+<div class="footnote"><p><a name="Footnote_3_3" id="Footnote_3_3"></a><a href="#FNanchor_3_3"><span class="label">[3]</span></a> With these products it is easy to observe that they have a
+definite fusion point 5&deg;-10&deg; below the temperature of explosion.</p></div>
+</div>
+
+
+<hr style="width: 65%;" />
+<h2>SECTION III. DECOMPOSITIONS OF CELLULOSE SUCH AS THROW LIGHT ON THE
+PROBLEM OF ITS CONSTITUTION</h2>
+
+
+<h3>UEBER CELLULOSE.</h3>
+
+<h4><span class="smcap">G. Bumcke</span> und <span class="smcap">R. Wolffenstein</span> (Berl. Ber., 1899, 2493).</h4>
+
+<p>(p. 54) <i>Theoretical Preface.</i>&mdash;The purpose of these investigations is
+the closer characterisation of the products known as 'oxycellulose' and
+'hydracellulose,' which are empirical aggregates obtained by various
+processes of oxidation and<span class='pagenum'><a name="Page_68" id="Page_68">[Pg 68]</a></span> hydrolysis; these processes act concurrently
+in the production of the oxycelluloses. The action of hydrogen peroxide
+was specially investigated. An oxycellulose resulted possessing strongly
+marked aldehydic characteristics. The authors commit themselves to an
+explanation of this paradoxical result, <i>i.e.</i> the production of a body
+of strongly 'reducing' properties by the action of an oxidising agent
+upon the inert cellulose molecule (? aggregate) as due to the
+<i>hydrolytic</i> action of the peroxide: following Wurster (Ber. 22, 145),
+who similarly explained the production of reducing sugars from cane
+sugar by the action of the peroxide.</p>
+
+<p>The product in question is accordingly termed <i>hydralcellulose</i>. By the
+action of alkalis this is resolved into two bodies of alcoholic
+(cellulose) and acid ('acid cellulose') characteristics respectively.
+The latter in drying passes into a lactone. The acid product is also
+obtained from cellulose by the action of alkaline lye (boiling 30 p.ct.
+NaOH) and by solution in Schweizer's reagent.</p>
+
+<p>It is considered probable that the cellulose nitrates are hydrocellulose
+derivatives, and experimental evidence in favour of this conclusion is
+supplied by the results of 'nitrating' the celluloses and their oxy- and
+hydro- derivatives. Identical products were obtained.</p>
+
+<p><i>Experimental investigations.</i>&mdash;The filter paper employed as 'original
+cellulose,' giving the following numbers on analysis:</p>
+
+
+<div class='center'>
+<table border="0" cellpadding="4" cellspacing="0" summary="">
+<tr><td align='left'></td><td align='left'>C</td><td align='right'>44.56</td><td align='right'>44.29</td><td align='right'>44.53</td><td align='right'>44.56</td></tr>
+<tr><td align='left'></td><td align='left'>H</td><td align='right'>6.39</td><td align='right'>6.31</td><td align='right'>6.46</td><td align='right'>6.42</td></tr>
+</table></div>
+
+<p>was exposed to the action of pure distilled H<sub>2</sub>O<sub>2</sub> at 4-60 p.ct.
+strength, at ordinary temperatures until disintegrated: a result
+requiring from nineteen to thirty days. The series of products gave the
+following analytical results:</p>
+
+
+<div class='center'>
+<table border="0" cellpadding="4" cellspacing="0" summary="">
+<tr><td align='left'></td><td align='left'>C</td><td align='right'>43.61</td><td align='right'>43.61</td><td align='right'>43.46</td><td align='right'>43.89</td><td align='right'>44.0</td><td align='right'>43.87</td><td align='right'>43.92</td><td align='right'>43.81</td></tr>
+<tr><td align='left'></td><td align='left'>H</td><td align='right'>6.00</td><td align='right'>6.29</td><td align='right'>6.28</td><td align='right'>6.26</td><td align='right'>6.13</td><td align='right'>6.27</td><td align='right'>6.24</td><td align='right'>6.27</td></tr>
+</table></div>
+
+<p><span class='pagenum'><a name="Page_69" id="Page_69">[Pg 69]</a></span></p>
+
+<p>results lying between the requirements of the formul&aelig;:</p>
+
+<p>
+<span style="margin-left: 2.5em;">5 C<sub>6</sub>H<sub>10</sub>O<sub>5</sub>.H<sub>2</sub>O&nbsp; and&nbsp; 8 C<sub>6</sub>H<sub>10</sub>O<sub>5</sub>.H<sub>2</sub>O.</span><br />
+</p>
+
+<p>Hydrazones were obtained with 1.7-1.8 p.ct. N. Treated with caustic soda
+solution the hydrazones were dissolved in part: on reprecipitation a
+hydrazone of unaltered composition was obtained. The original product
+shows therefore a uniform distribution of the reactive CO- groups.</p>
+
+<p>The hydralcellulose boiled with Fehling's solution reduced 1/12 of the
+amount required for an equal weight of glucose.</p>
+
+<p>Digested with caustic soda solution it yielded 33 p.ct. of its weight of
+the soluble 'acid cellulose.' This product was purified and analysed
+with the following result: C 43.35 H 6.5. For the direct production of
+the 'acid' derivative, cellulose was boiled with successive quantities
+of 30 p.ct. NaOH until <i>dissolved</i>. It required eight treatments of one
+hour's duration. On adding sulphuric acid to the solutions the product
+was precipitated. Yield 40 p.ct. Analyses:</p>
+
+
+<div class='center'>
+<table border="0" cellpadding="4" cellspacing="0" summary="">
+<tr><td align='left'></td><td align='left'>C</td><td align='right'>43.8</td><td align='right'>43.8</td><td align='right'>43.7</td></tr>
+<tr><td align='left'></td><td align='left'>H</td><td align='right'>6.2</td><td align='right'>6.2</td><td align='right'>6.3</td></tr>
+</table></div>
+
+<p>The cellulose reprecipitated from solution in Schweizer's reagent gave
+similar analytical results:</p>
+
+
+<div class='center'>
+<table border="0" cellpadding="4" cellspacing="0" summary="">
+<tr><td align='left'></td><td align='left'>C</td><td align='right'>43.9</td><td align='right'>43.8</td><td align='right'>44.0</td></tr>
+<tr><td align='left'></td><td align='left'>H</td><td align='right'>6.5</td><td align='right'>6.3</td><td align='right'>6.4</td></tr>
+</table></div>
+
+<p><i>Conversion into nitrates.</i>&mdash;The original cellulose, hydral- and acid
+cellulose were each treated with 10 times their weight of HNO<sub>3</sub> of
+1.48 sp.gr. and heated at 85&deg; until the solution lost its initial
+viscosity.</p>
+
+<p>The products were precipitated by water and purified by solution in
+acetone from which two fractions were recovered, the one being
+relatively insoluble in ethyl alcohol. The<span class='pagenum'><a name="Page_70" id="Page_70">[Pg 70]</a></span> various nitrates from the
+several original products proved to be of almost identical composition,</p>
+
+<p>
+<span style="margin-left: 2.5em;">C 32.0&nbsp;  H 4.2&nbsp; &nbsp; N 8.8</span><br />
+</p>
+
+<p>with a molecular weight approximately 1350. The conclusion is that these
+products are all derivatives of a 'hydralcellulose' 6
+C<sub>6</sub>H<sub>10</sub>O<sub>5</sub>H<sub>2</sub>O.</p>
+
+
+<h3>FORMATION OF FURFURALDEHYDE FROM CELLULOSE, OXYCELLULOSE, AND
+HYDROCELLULOSE.</h3>
+
+<h4>By <span class="smcap">Leo Vignon</span> (Compt. rend., 1898, 126, 1355-1358).</h4>
+
+<p>(p. 54) Hydrocellulose, oxycellulose, and 'reduced' cellulose, the last
+named being apparently identical with hydrocellulose, were obtained by
+heating carefully purified cotton wool (10 grams) in water (1,000 c.c.),
+with (1) 65 c.c. of hydrochloric acid (1.2 sp.gr.), (2) 65 c.c. of
+hydrochloric acid and 80 grams of potassium chlorate, (3) 65 c.c. of
+hydrochloric acid and 50 grams of stannous chloride. From these and some
+other substances, the following percentage yields of furfuraldehyde were
+obtained: Hydrocellulose, 0.854; oxycellulose, 2.113; reduced cellulose,
+0.860; starch, 0.800; bleached cotton, 1.800; oxycellulose, prepared by
+means of chromic acid, 3.500. Two specimens of oxycellulose were
+prepared by treating cotton wool with hydrochloric acid and potassium
+chlorate (A), and with sulphuric acid and potassium dichromate (B), and
+25 grams of each product digested with aqueous potash. Of the product A,
+16.20 grams were insoluble in potash, 2.45 grams were precipitated on
+neutralisation of the alkaline solution, and 6.35 grams remained in
+solution, whilst B yielded 11.16 grams of insoluble matter, 1.42 grams
+were precipitated by acid, and 12.42 grams remained in solution. The
+percentage yields of<span class='pagenum'><a name="Page_71" id="Page_71">[Pg 71]</a></span> furfuraldehyde obtained from these fractions were
+as follows: A, insoluble, 0.86; precipitated, 4.35; dissolved, 1.10. B,
+insoluble, 0.76; precipitated, 5.11; dissolved, 1.54. It appears, from
+the foregoing results, that the cellulose molecule, after oxidation, is
+easily decomposed by potash, the insoluble and larger portion having all
+the characters of the original cellulose, whilst the soluble portion is
+of an aldehydic nature, and contains a substance, precipitable by acids,
+which yields a relatively large amount of furfuraldehyde.</p>
+
+
+<h3>UNTERSUCHUNGEN &Uuml;BER DIE OXYCELLULOSE.</h3>
+
+<h4><span class="smcap">O. v. Faber</span> und <span class="smcap">B. Tollens</span> (Berl. Ber., 1899, 2589).</h4>
+
+<h3>Investigations of Oxycellulose.</h3>
+
+<p>(p. 61) The author's results are tersely summed up in the following
+conclusions set forth at the end of the paper: The oxycelluloses are
+mixtures of cellulose and a derivative oxidised compound which contains
+one more atom O than cellulose (cellulose = C<sub>6</sub>H<sub>10</sub>O<sub>5</sub>), and for
+which the special designation <i>Celloxin</i> is proposed.</p>
+
+<p>Celloxin may be formulated C<sub>8</sub>H<sub>6</sub>O<sub>6</sub> or C<sub>6</sub>H<sub>10</sub>O<sub>6</sub>, of which
+the former is the more probable.</p>
+
+<p>The various oxycelluloses may be regarded as containing one celloxin
+group to 1-4 cellulose groups, according to the nature of the original
+cellulose, and the degree of oxidation to which subjected. These groups
+are in chemical union.</p>
+
+<p>Celloxin has not been isolated. On boiling the oxycelluloses with
+lime-milk it is converted into isosaccharinic and dioxybutyric acids.
+The insoluble residue from the treatment is cellulose.<span class='pagenum'><a name="Page_72" id="Page_72">[Pg 72]</a></span></p>
+
+<p>The following oxycelluloses were investigated:</p>
+
+<p>A. <i>Product of action of nitric acid upon pine wood</i> (Lindsey and
+Tollens, Ann. 267, 366).&mdash;The oxycelluloses contained</p>
+
+<p>
+1 mol celloxin:  {2 mol. cellulose on 6 hours' heating<br />
+<span style="margin-left: 5.5em;">{3 mol. cellulose on 3 hours' heating</span><br />
+</p>
+
+<p>with a ratio H: O = 1: 9 and 1: 8.7 respectively: they yielded 7 p.ct.
+furfural.</p>
+
+<p>B. <i>By action of bromine in presence of water and</i> CaCO<sub>3</sub> <i>upon
+cotton</i>.&mdash;Yield, (air-dry) 85 p.ct. Empirical composition
+C<sub>12</sub>H<sub>20</sub>O<sub>11</sub> = C<sub>6</sub>H<sub>10</sub>O<sub>5</sub>.C<sub>6</sub>H<sub>10</sub>O<sub>6</sub>: yielded furfural
+1.7 p.ct.</p>
+
+<p>C. <i>Cotton and nitric acid at</i> 100&deg;, two and a half hours (Cross and
+Bevan).&mdash;Yield, 70 p.ct. Composition</p>
+
+<p>
+<span style="margin-left: 2.5em;">4 C<sub>6</sub>H<sub>10</sub>O<sub>5</sub>.C<sub>6</sub>H<sub>8</sub>O<sub>6</sub></span><br />
+</p>
+
+<p>yielded furfural 2.3 p.ct.</p>
+
+<p>D. <i>Cotton and nitric acid at</i> 100&deg; (four hours).&mdash;A more highly
+oxidised product resulted, viz. 3 C<sub>6</sub>H<sub>10</sub>O<sub>5</sub>.C<sub>6</sub>H<sub>8</sub>O<sub>6</sub>:
+yielded furfural 3.2 p.ct.</p>
+
+<p><i>By-products of oxidation.</i>&mdash;The liquors from B were found to contain
+saccharic acid: the acid from C and B contained a dibasic acid which
+appeared to be tartaric acid.</p>
+
+<p>The isolation of (1) isosaccharinic and (2) dioxybutyric acid from the
+products of digestion of the oxycelluloses with lime-milk at 100&deg; was
+effected by the separation of their respective calcium salts, (1) by
+direct crystallisation, (2) by precipitation alcohol after separation of
+the former.</p>
+
+
+<h3>CELLULOSES, HYDRO- AND OXYCELLULOSES, AND CELLULOSE ESTERS.</h3>
+
+<h4><span class="smcap">L. Vignon</span> (Bull. Soc. Chim., 1901 [3], 25, 130).</h4>
+
+<p>(<i>a</i>) <i>Oxycelluloses from cotton, hemp, flax, and ramie.</i>&mdash;The
+<span class='pagenum'><a name="Page_73" id="Page_73">[Pg 73]</a></span>comparative oxidation of these celluloses, by treatment with HClO<sub>3</sub>
+at 100&deg;, gave remarkably uniform results, as shown by the following
+numbers, showing extreme variations: yields, 68-70 p.ct.; hydrazine
+reaction, N fixed 1.58-1.69; fixation of basic colouring matters
+(relative numbers), saffranine, 100-200, methylene blue, 100-106. The
+only points of difference noted were (1) hemp is somewhat more resistant
+to the acid oxidation; (2) the cotton oxycellulose shows a somewhat
+higher (25 p.ct.) cupric reduction.</p>
+
+<p>(<i>b</i>) <i>'Saccharification' of cellulose, cellulose hydrates, and
+hydrocellulose.</i>&mdash;The products were digested with dilute hydrochloric
+acid six hours at 100&deg;, and the cupric reduction of the soluble products
+determined and calculated to dextrose.</p>
+
+
+<div class='center'>
+<table border="0" cellpadding="4" cellspacing="0" summary="">
+<tr><td align='left'>100 grms. of</td><td align='left'>gave reducing products equal to Dextrose</td></tr>
+<tr><td align='left'>Purified cotton</td><td align='center'>3.29</td></tr>
+<tr><td align='left'>&nbsp;&nbsp;&nbsp;&nbsp;"&nbsp;&nbsp;&nbsp;&nbsp;Hydrocellulose</td><td align='center'>9.70</td></tr>
+<tr><td align='left'>Cotton mercerised (NaOH 30&deg; B.)</td><td align='center'>4.39</td></tr>
+<tr><td align='left'>Cotton mercerised (NaOH 40&deg; B.)</td><td align='center'>3.51</td></tr>
+<tr><td align='left'>Cellulose reprecipitated from cuprammonium</td><td align='center'>4.39</td></tr>
+<tr><td align='left'>Oxycellulose</td><td align='center'>14.70</td></tr>
+<tr><td align='left'>Starch</td><td align='center'>98.6</td></tr>
+</table></div>
+
+
+<p>These numbers show that cellulose may be hydrated both by mercerisation
+and solution, without affecting the constitutional relationships of the
+CO groups. The results also differentiate the cellulose series from
+starch in regard to hydrolysis.</p>
+
+<p>(<i>c</i>) <i>Cellulose and oxycellulose nitrates.</i>&mdash;The nitric esters of
+cellulose have a strong reducting action on alkaline copper solutions.
+The author has studied this reaction quantitatively for the esters both
+of cellulose and oxycellulose, at two stages of 'nitration,' represented
+by 8.2-8.6 p.ct. and 13.5-13.9 p.ct. total nitrogen in the
+ester-products, respectively. The results are expressed in terms (c.c.)
+of the cupric reagent (Pasteur) reduced per 100 grs. compared with
+dextrose (=17767).<span class='pagenum'><a name="Page_74" id="Page_74">[Pg 74]</a></span></p>
+
+
+<div class='center'>
+<table border="0" cellpadding="4" cellspacing="0" summary="">
+<tr><td align='left'>Cellulose maximum nitration (13.5 p.ct. N)</td><td align='left'>3640</td></tr>
+<tr><td align='left'>Oxycellulose maximum nitration (13.9 p.ct. N)</td><td align='left'>3600</td></tr>
+<tr><td align='left'>Cellulose minimum nitration (8.19 p.ct. N)</td><td align='left'>3700</td></tr>
+<tr><td align='left'>Oxycellulose minimum nitration (8.56 p.ct. N)</td><td align='left'>3620</td></tr>
+</table></div>
+
+<p>The author concludes that, since the reducing action is independent of
+the degree of nitration, and is the same for cellulose and the
+oxycelluloses, the ester reaction in the case of the normal cellulose is
+accompanied by oxidation, the product being an oxycellulose ester.</p>
+
+<p><i>Products of 'denitration'.</i>&mdash;The esters were treated with ferrous
+chloride in boiling aqueous solution. The products were oxycelluloses,
+with a cupric reduction equal to that of an oxycellulose directly
+prepared by the action of HClO<sub>3</sub>. On the other hand, by treatment with
+ammonium sulphide at 35&deg;-40&deg; 'denitrated' products were obtained without
+action on alkaline copper solutions.</p>
+
+
+<h3>OXYCELLULOSES AND THE MOLECULAR WEIGHT OF CELLULOSE.</h3>
+
+<h4><span class="smcap">H. Nastukoff</span> (Berl. Ber. 33 [13] 2237).</h4>
+
+<p>(p. 61) The author continues his investigations of the oxidation of
+cellulose. [Compare Bull. Mulhouse, 1892.] The products described were
+obtained by the action of hypochlorites and permanganates upon Swedish
+filter paper (Schleicher and Sch&uuml;ll).</p>
+
+<p>4. <i>Oxidation by hypochlorites.</i>&mdash;(1) The cellulose was digested 24 hrs.
+with 35 times its weight of a filtered solution of bleaching power of
+4&deg;B.; afterwards drained and exposed for 24 hrs. to the atmosphere.
+These treatments were then repeated. After washing, treatment with
+dilute acetic acid and again washing, the product was treated with a 10
+p.ct. NaOH<span class='pagenum'><a name="Page_75" id="Page_75">[Pg 75]</a></span> solution. The oxycellulose was precipitated from the
+filtered solution: yield 45 p.ct. The residue when purified amounted to
+30 p.ct. of the original cellulose, with which it was identical in all
+essential properties.</p>
+
+<p>The oxycellulose, after purification, dried at 110&deg;, gave the following
+analytical numbers:</p>
+
+
+<div class='center'>
+<table border="0" cellpadding="4" cellspacing="0" summary="">
+<tr><td align='left'></td><td align='left'>C</td><td align='right'>43.64</td><td align='right'>43.78</td><td align='right'>43.32</td><td align='right'>43.13</td></tr>
+<tr><td align='left'></td><td align='left'>H</td><td align='right'>6.17</td><td align='right'>6.21</td><td align='right'>5.98</td><td align='right'>6.08</td></tr>
+</table></div>
+<p>Its compound with phenylhydrazine (<i>loc. cit.</i>) gave the following
+analytical numbers:</p>
+
+
+<div class='center'>
+<table border="0" cellpadding="4" cellspacing="0" summary="">
+<tr><td align='left'></td><td align='left'>N</td><td align='left'>0.78</td><td align='left'>0.96</td><td align='left'>0.84</td></tr>
+</table></div>
+
+<p>(2) The reagents were as in (1), but the conditions varied by passing a
+stream of carbonic acid gas through the solution contained in a flask,
+until Cl compounds ceased to be given off. The analysis of the purified
+oxycellulose gave C 43.53, H 6.13.</p>
+
+<p>(3) The conditions were as in (2), but a much stronger hypochlorite
+solution&mdash;viz. 12&deg;B.&mdash;was employed. The yield of oxycellulose
+precipitated from solution in soda lye (10 p.ct. NaOH) was 45 p.ct.
+There was only a slight residue of unattacked cellulose. The analytical
+numbers obtained were:</p>
+
+
+<div class='center'>
+<table border="0" cellpadding="4" cellspacing="0" summary="">
+<tr><td align='left'>Oxycellulose</td><td align='left'>C</td><td align='right'>43.31</td><td align='right'>43.74</td><td align='right'>43.69</td></tr>
+<tr><td align='left'>&nbsp;&nbsp;&nbsp;&nbsp;"&nbsp;&nbsp;&nbsp;&nbsp;</td><td align='left'>H</td><td align='right'>6.47</td><td align='right'>6.42</td><td align='right'>6.51</td></tr>
+<tr><td align='left'></td><td colspan="4">________________________</td></tr>
+<tr><td align='left'>Phenylhydrazine compound</td><td align='left'>N</td><td align='left'></td><td align='right'>0.62</td><td align='right'>0.81</td></tr>
+</table></div>
+
+<p>B. <i>Oxidation by permanganate</i> (KMnO<sub>4</sub>). (1) The cellulose 16 grms.
+was treated with 1100 c.c. of a 1 p.ct. solution of KMnO<sub>4</sub> in
+successive portions. The MnO<sub>2</sub> was removed from time to time by
+digesting the product with a dilute sulphuric acid (10 p.ct.
+H<sub>2</sub>SO<sub>4</sub>). The oxycellulose was purified as before, yield 40 p.ct.
+Analytical numbers:</p>
+
+<div class='center'>
+<table border="0" cellpadding="4" cellspacing="0" summary="">
+<tr><td align='left'>Oxycellulose</td><td align='left'>C</td><td align='left'></td><td align='right'>42.12</td><td align='left'>42.9</td></tr>
+<tr><td align='left'>&nbsp;&nbsp;&nbsp;&nbsp;"&nbsp;&nbsp;&nbsp;&nbsp;</td><td align='left'>H</td><td align='left'></td><td align='right'>6.20</td><td align='right'>6.11</td></tr>
+<tr><td align='left'></td><td colspan="4">________________________</td></tr>
+<tr><td align='left'>Phenylhydrazine compound</td><td align='left'>N</td><td align='right'>1.35</td><td align='right'>1.08</td><td align='right'>1.21</td></tr>
+</table></div>
+
+<p><span class='pagenum'><a name="Page_76" id="Page_76">[Pg 76]</a></span></p>
+
+<p>(2) The cellulose (16 grms.) was digested 14 days with 2500 c.c. of 1
+p.ct. KMnO<sub>4</sub> solution. The purified oxycellulose was identical in all
+respects with the above: yield 40 p.ct. C 42.66, H 6.19.</p>
+
+<p>(3) The cellulose (16 grms.) was heated in the water-bath with 1600 c.c.
+of 15 p.ct. H<sub>2</sub>SO<sub>4</sub> to which were added 18 grms. KMnO<sub>4</sub>. The yield
+and composition of the oxycellulose was identical with the above. It
+appears from these results that the oxidation with hypochlorites acids 1
+atom of O to 4-6 of the unit groups C<sub>6</sub>H<sub>10</sub>O<sub>5</sub>; and the oxidation
+with permanganate 2 atoms O per 4-6 units of C<sub>6</sub>H<sub>10</sub>O<sub>5</sub>. The
+molecular proportion of N in the phenylhydrazine residue combining is
+fractional, representing 1 atom O, <i>i.e.</i> 1 CO group reacting per 4
+C<sub>36</sub>H<sub>60</sub>O<sub>31</sub> and 6 C<sub>24</sub>H<sub>49</sub>O<sub>21</sub> respectively, assuming the
+reaction to be a hydrazone reaction.</p>
+
+<p>Further investigations of the oxycelluloses by treatment with (<i>a</i>)
+sodium amalgam, (<i>b</i>) bromine (water), and (<i>c</i>) dilute nitric acid at
+110&deg;, led to no positive results.</p>
+
+<p>By treatment with alcoholic soda (NaOH) the products were resolved into
+a soluble and insoluble portion, the properties of the latter being
+those of a cellulose (hydrate).</p>
+
+<p><i>Molecular weight of cellulose and oxycellulose.</i>&mdash;The author endeavours
+to arrive at numbers expressing these relations by converting the
+substances into acetates by Schutzenberger's method, and observing the
+boiling-points of their solution in nitrobenzene.</p>
+
+
+<h3>FERMENTATION OF CELLULOSE</h3>
+
+<h4><span class="smcap">V. Omelianski</span> (Compt. Rend., 1897, 125, 1131-1133).</h4>
+
+<p>Pure paper was allowed to ferment in the presence of calcium carbonate
+at a temperature of 35&deg; for 13 months. The<span class='pagenum'><a name="Page_77" id="Page_77">[Pg 77]</a></span> products obtained from
+3.4743 grams of paper were: acids of the acetic series, 2.2402 grams;
+carbonic anhydride, 0.9722 grams; and hydrogen, 0.0138 gram. The acids
+were chiefly acetic and butyric acid, the ratio of the former to the
+latter being 1.7: 1. Small quantities of valeric acid, higher alcohols,
+and odorous products were formed.</p>
+
+<p>The absence of methane from the products of fermentation is remarkable,
+but the formation of this gas seems to be due to a special organism
+readily distinguishable from the ferment that produces the fatty acids.
+This organism is at present under investigation.</p>
+
+<hr style='width: 45%;' />
+
+<p>(p. 75) <b>Constitution of Cellulose.</b>&mdash;It may be fairly premised that the
+problem of the constitution of cellulose cannot be solved independently
+of that of molecular aggregation. We find in effect that the structural
+properties of cellulose and its derivatives are directly connected with
+their constitution. So far we have only a superficial perception of this
+correlation. We know that a fibrous cellulose treated with acids or
+alkalis in such a way that only hydrolytic changes can take place is
+converted into a variety of forms of very different structural
+characteristics, and these products, while still preserving the main
+chemical characteristics of the original, show when converted into
+derivatives by simple synthesis, <i>e.g.</i> esters and sulphocarbonates, a
+corresponding differentiation of the physical properties of these
+derivatives, from the normal standard, and therefore that the new
+reacting unit determines a new physical aggregate. Thus the
+sulphocarbonate of a 'hydrocellulose' is formed with lower proportions
+of alkaline hydrate and carbon disulphide, gives solutions of relatively
+low viscosity, and, when decomposed to give a film or thread of the
+regenerated cellulose, these are found to be deficient in strength<span class='pagenum'><a name="Page_78" id="Page_78">[Pg 78]</a></span> and
+elasticity. Similarly with the acetate. The normal acetate gives
+solutions of high viscosity, films of considerable tenacity, and when
+those are saponified the cellulose is regenerated as an unbroken film.
+The acetates of hydrolysed celluloses manifest a retrogradation in
+structural and physical properties, proportioned to the degree of
+hydrolysis of the original.</p>
+
+<p>We may take this opportunity of pointing out that the celluloses not
+only suggest with some definiteness the connection of the structural
+properties of visible aggregates&mdash;that is, of matter in the mass&mdash;with
+the configuration of the chemical molecule or reacting unit, but supply
+unique material for the actual experimental investigation of the
+problems involved. Of all the 'organic' colloids cellulose is the only
+one which can be converted into a variety of derivative forms, from each
+of which a regular solid can be produced in continuous length and of any
+prescribed dimensions. Thus we can compare the structural properties of
+cellulose with those of its hydrates, nitrates, acetates, and benzoates,
+in terms of measurements of breaking strain, extensibility, elasticity.
+Investigations in this field are being prosecuted, but the results are
+not as yet sufficiently elaborated for reduction to formul&aelig;. One
+striking general conclusion is, however, established, and that is that
+the structural properties of cellulose are but little affected by
+esterification and appear therefore to be a function of the special
+arrangement of the carbon atoms, i.e. of the molecular constitution.
+Also it is established that the molecular aggregate which constitutes a
+cellulose is of a resistant type, and undoubtedly persists in the
+solutions of the compounds.</p>
+
+<p>It may be urged that it is superfluous to import these questions of
+mass-aggregation into the problem of the chemical constitution of
+cellulose. But we shall find that the point again arises in attempting
+to define the reacting unit, which is another term for the molecule. In
+the majority of cases we<span class='pagenum'><a name="Page_79" id="Page_79">[Pg 79]</a></span> rely for this upon physical measurements; and
+in fact the purely chemical determination of such quantities is
+inferential. Attempts have been made to determine the molecular weights
+of the cellulose esters in solution, by observations of depression of
+solidifying and boiling-points. But the numbers have little value. The
+only other well-defined compound is the sulphocarbonate. It has been
+pointed out that, by successive precipitations of this compound, there
+occurs a continual aggregation of the cellulose with dissociation of the
+alkali and CS residues and it has been found impossible to assign a
+limit to the dissociation, i.e. to fix a point at which the transition
+from soluble sulphocarbonate to insoluble cellulose takes place.</p>
+
+<p>On these grounds it will be seen we are reduced to a somewhat
+speculative treatment of the hypothetical ultimate unit group, which is
+taken as of C<sub>6</sub> dimensions.</p>
+
+<p>As there has been no addition of experimental facts directly
+contributing to the solution of the problem, the material available for
+a discussion of the probabilities remains very much as stated in the
+first edition, pp. 75-77. It is now generally admitted that the
+tetracetate <i>n</i> [C<sub>6</sub>H<sub>6</sub>O.(OAc)<sub>4</sub>] is a normal cellulose ester;
+therefore that four of the five O atoms are hydroxylic. The fifth is
+undoubtedly carbonyl oxygen. The reactions of cellulose certainly
+indicate that the CO- group is ketonic rather than aldehydic. Even when
+attacked by strong sulphuric acid the resolution proceeds some
+considerable way before products are obtained reducing Fehling's
+solution. This is not easily reconcilable with any polyaldose formula.
+Nor is the resistance of cellulose to very severe alkaline treatments.
+The probability may be noted here that under the action of the alkaline
+hydrates there occurs a change of configuration. Lobry de Bruyn's
+researches on the change of position of the typical CO- group of the
+simple hexoses, in presence of alkalis, point very definitely in this
+direction. It<span class='pagenum'><a name="Page_80" id="Page_80">[Pg 80]</a></span> is probable that in the formation of alkali cellulose
+there is a constitutional change of the cellulose, which may in effect
+be due to a migration of a CO- position within the unit group. Again
+also we have the interesting fact that structural changes accompany the
+chemical reaction. It is surprising that there should have been no
+investigation of these changes of external form and structure, otherwise
+than as mass effects. We cannot, therefore, say what may be the
+molecular interpretation of these effects. It has not yet been
+determined whether there are any intrinsic volume changes in the
+cellulose substance itself: and as regards what changes are determined
+in the reacting unit or molecule, we can only note a fruitful subject
+for future investigation. <i>A priori</i> our views of the probable changes
+depend upon the assumed constitution of the unit group. If of the
+ordinary carbohydrate type, formulated with an open chain, there is
+little to surmise beyond the change of position of a CO- group. But
+alternative formul&aelig; have been proposed. Thus the tetracetate is a
+derivative to be reckoned with in the problem. It is formed under
+conditions which preclude constitutional changes within the unit groups.
+The temperature of the main reaction is 30&deg;-40&deg;, the reagents are used
+but little in excess of the quantitative proportions, and the yields are
+approximately quantitative. If now the derivative is formed entirely
+without the hydrolysis the empirical formula C<sub>6</sub>H<sub>6</sub>O.(OAc)<sub>4</sub>
+justifies a closed-ring formula for the original viz.
+CO&lt;[CHOH]<sub>4</sub>&gt;CH<sub>2</sub>; and the preference for this formula depends upon
+the explanation it affords of the aggregation of the groups by way of
+CO-CH<sub>2</sub> synthesis.</p>
+
+<p>The exact relationship of the tetracetate to the original cellulose is
+somewhat difficult to determine. The starting-point is a cellulose
+hydrate, since it is the product obtained by decomposition of the
+sulphocarbonate. The degree of <i>hydrolysis</i> attending the cycle of
+<span class='pagenum'><a name="Page_81" id="Page_81">[Pg 81]</a></span>reactions is indicated by the formula 4 C<sub>6</sub>H<sub>10</sub>O<sub>5</sub>.H<sub>2</sub>O. It has
+been already shown that this degree of hydrolysis does not produce
+molecular disaggregation. If this hydrate survived the acetylation it
+would of course affect the empirical composition, i.e. chiefly the
+carbon percentage, of the product. It may be here pointed out that the
+extreme variation of the carbon in this group of carbohydrate esters is
+as between C<sub>14</sub>H<sub>20</sub>O<sub>10</sub> (C = 48.3 p.ct.) and C<sub>14</sub>H<sub>18</sub>O<sub>9</sub> (C
+= 50.8 p.ct.) i.e. a tetracetate of C<sub>6</sub>H<sub>12</sub>O<sub>6</sub> and
+C<sub>6</sub>H<sub>10</sub>O<sub>5</sub> respectively. In the fractional intermediate terms it
+is clear that we come within the range of ordinary experimental errors,
+and to solve this critical point by way of ultimate analysis must
+involve an extended series of analyses with precautions for specially
+minimising and quantifying the error. The determination of the acetyl by
+saponification is also subject to an error sufficiently large to
+preclude the results being applied to solve the point. While, therefore,
+we must defer the final statement as to whether the tetracetate is
+produced from or contains a partly hydrolysed cellulose molecule, it is
+clear that at least a large proportion of the unit groups must be
+acetylated in the proportion C<sub>6</sub>H<sub>6</sub>O.(OAc)<sub>4</sub>.</p>
+
+<p>It has been shown that by the method of Franchimont a higher proportion
+of acetyl groups can be introduced; but this result involves a
+destructive hydrolysis of the cellulose: the acetates are not
+derivatives of cellulose, but of products of hydrolytic decomposition.</p>
+
+<p>It appears, therefore, that with the normal limit of acetylation at the
+tetracetate the aggregation of the unit groups must depend upon the CO-
+groups and a ring formula of the general form CO&lt;[CHOH]<sub>4</sub>&gt;CH<sub>2</sub> is
+consistent with the facts.</p>
+
+<p>Vignon has proposed for cellulose the constitutional formula</p>
+
+<div class="floatl" style="width: 239px;">
+<img src="images/image1.jpg" width="239" height="100" alt="" title="" />
+</div>
+
+<p>with reference to the highest nitrate, and the decomposition of the
+nitrate by alkalis with formation of hydroxypyruvic acid. While these
+reactions afford no very sure ground for deductions as to constitutional<span class='pagenum'><a name="Page_82" id="Page_82">[Pg 82]</a></span>
+relationships, it certainly appears that, if the aldose view of the unit
+group is to be retained, this form of the anhydride contains suggestions
+of the general tendency of the celluloses on treatment with condensing
+acids to split off formic acid in relatively large quantity [Ber. 1895,
+1940]; the condensation of the oxycelluloses to furfural; the
+non-formation of the normal hydroxy-dicarboxylic acids by nitric acid
+oxidations. Indirectly we may point out that any hypothesis which
+retains the polyaldose view of cellulose, and so fails to differentiate
+its constitution from that of starch, has little promise of progress.
+The above formula, moreover, concerns the assumed unit group, with no
+suggestion as to the mode of aggregation in the cellulose complex. Also
+there is no suggestion as to how far the formula is applicable to the
+celluloses considered as a group. In extending this view to the
+oxycelluloses, Vignon introduces the derived oxidised group</p>
+
+<div class="floatl" style="width: 326px;">
+<img src="images/image2.jpg" width="326" height="69" alt="" title="" />
+</div>
+
+
+<p>&mdash;of which one is apportioned to three or four groups of the cellulose
+previously formulated: these groups in condensed union together
+constitute an oxycellulose.</p>
+
+<p>These views are in agreement with the experimental results obtained by
+Faber and Tollens (p. 71). They regard the oxycelluloses as compounds of
+'celloxin' C<sub>6</sub>H_8{O}<sub>6</sub> with 1-4 mols. unaltered cellulose; and the
+former they particularly refer to as a lactone of glycuronic acid. But
+on boiling with lime they obtain dioxybutyric and isosaccharinic acids;
+both of which are not very obviously related to the compounds formulated
+by Vignon. We revert with preference to a definitely ketonic formula,
+for which, moreover, some farther grounds remain to be mentioned. In the
+systematic investigation of the nitric esters<span class='pagenum'><a name="Page_83" id="Page_83">[Pg 83]</a></span> of the carbohydrates (p.
+41) Will and Lenze have definitely differentiated the ketoses from the
+aldoses, as showing an internal condensation accompanying the ester
+reaction. Not only are the OH groups taking part in the latter
+consequently less by two than in the corresponding aldoses, but the
+nitrates show a much increased stability. This would give a simple
+explanation of the well-known facts obtaining in the corresponding
+esters of the normal cellulose. We may note here that an important item
+in the quantitative factors of the cellulose nitric ester reaction has
+been overlooked: that is, the yield calculated to the NO<sub>3</sub> groups
+fixed. The theoretical yields for the higher nitrates are</p>
+
+
+<div class='center'>
+<table border="0" cellpadding="4" cellspacing="0" summary="">
+<tr><td align='left'></td><td align='left'>Yield p.ct. of cellulose</td><td align='left'>N p.ct. of nitrate</td></tr>
+<tr><td align='left'>Pentanitrate</td><td align='center'>169</td><td align='center'>12.7</td></tr>
+<tr><td align='left'>Hexanitrate</td><td align='center'>183</td><td align='center'>14.1</td></tr>
+</table></div>
+
+<p>From such statistics as are recorded the yields are not in accordance
+with the above. There is a sensible deficiency. Thus Will and Lenze
+record a yield of 170 p.ct. for a product with 13.8 p.ct. N, indicating
+a deficiency of about 10 p.ct. As the by-products soluble in the acid
+mixture are extremely small, the deficiency represents approximately the
+water split off by an internal reaction. In this important point the
+celluloses behave as ketoses.</p>
+
+<p>In the lignocelluloses the condensed constituents of the complex are of
+well-marked ketonic, i.e. quinonic, type. In 'nitrating' the
+lignocelluloses this phenomenon of internal condensation is much more
+pronounced (see p. 131). As the reaction is mainly confined to the
+cellulose of the fibre, we have this additional evidence that the
+typical carbonyl is of ketonic function. It is still an open question
+whether the cellulose constituents of the lignocelluloses are
+progressively condensed&mdash;with progress of 'lignification'&mdash;to the
+unsaturated<span class='pagenum'><a name="Page_84" id="Page_84">[Pg 84]</a></span> or lignone groups. There is much in favour of this view,
+the evidence being dealt with in the first edition, p. 180. The
+transition from a cellulose-ketone to the lignone-ketone involves a
+simple condensation without rearrangement; from which we may argue back
+to the greater probability of the ketonic structure of the cellulose. We
+must note, however, that the celluloses of the lignocelluloses are
+obtained as residues of various reactions, and are not homogeneous. They
+yield on boiling with condensing acids from 6 to 9 p.ct. furfural. It is
+usual to regard furfural as invariably produced from a pentose residue.
+But this interpretation ignores a number of other probable sources of
+the aldehyde. It must be particularly remembered that l&aelig;vulose is
+readily condensed (<i>a</i>) to a methylhydroxyfurfural</p>
+
+<p>
+<span style="margin-left: 2.5em;">C<sub>6</sub>H<sub>1</sub>O<sub>6</sub> - 3H<sub>2</sub>O = C<sub>6</sub>H<sub>6</sub>O<sub>3</sub> = C<sub>5</sub>(OH).H<sub>2</sub>.(CH<sub>3</sub>)O<sub>2</sub></span><br />
+</p>
+
+<p>and (<i>b</i>) by HBr, with further loss of OH, as under:</p>
+
+<p>
+<span style="margin-left: 2.5em;">C<sub>6</sub>H<sub>12</sub>O<sub>6</sub> - 4H<sub>2</sub>O + HBr = C<sub>5</sub>H<sub>3</sub>(CH<sub>2</sub>Br)O</span><br />
+</p>
+
+<p>and generally the ketoses are distinguished from the aldoses by their
+susceptibility to condensation. Such condensation of l&aelig;vulose has been
+effected by two methods: (<i>a</i>) by heating the concentrated aqueous
+solution with a small proportion of oxalic acid at 3 atm. pressure
+[Kiermayer, Chem. Ztg. 19, 100]; (<i>b</i>) by the action of hydrobromic acid
+(gas) in presence of anhydrous ether; the actual compound obtained being
+the &#969;-brommethyl derivative [Fenton, J. Chem. Soc. 1899, 423].</p>
+
+<p>This latter method is being extended to the investigation of typical
+celluloses, and the results appear to confirm the view that cellulose
+may be of ketonic constitution.</p>
+
+<p>The evidence which is obtainable from the synthetical side of the
+question rests of course mainly upon the physiological<span class='pagenum'><a name="Page_85" id="Page_85">[Pg 85]</a></span> basis. There are
+two points which may be noted. Since the researches of Brown and Morris
+(J. Chem. Soc. 1893, 604) have altered our views of the relationships of
+starch and cane sugar to the assimilation process, and have placed the
+latter in the position of a primary product with starch as a species of
+overflow and reserve product, it appears that l&aelig;vulose must play an
+important part in the elaboration of cellulose. Moreover, A. J. Brown,
+in studying the cellulosic cell-collecting envelope produced by the
+<i>Bacterium xylinum</i>, found that the proportion of this product to the
+carbohydrate disappearing under the action of the ferment was highest in
+the case of l&aelig;vulose. These facts being also taken into consideration
+there is a concurrence of suggestion that the typical CO group in the
+celluloses is of ketonic character. That the typical cotton cellulose
+breaks down finally under the action of sulphuric acid to dextrose
+cannot be held to prove the aldehydic position of the carbonyls in the
+unit groups of the actual cellulose molecule or aggregate.</p>
+
+<p>We again are confronted with the problem of the aggregate and as to how
+far it may affect the constitution of the unit groups. That it modifies
+the functions or reactivity of the ultimate constituent groups we have
+seen from the study of the esters. Thus with the direct ester reactions
+the normal fibrous cellulose (C<sub>6</sub>H<sub>16</sub>O<sub>5</sub>) yields a monoacetate,
+dibenzoate, and a trinitrate respectively under conditions which
+determine, with the simple hexoses and anhydrides, the maximum
+esterification, i.e. all the OH groups reacting. If the OH groups are of
+variable function, we should expect the CO groups <i>a fortiori</i> to be
+susceptible of change of function, i.e. of position within the unit
+groups.</p>
+
+<p>But as to how far this is a problem of the constitution or phases of
+constitution of the unit groups or of the aggregate under reaction we
+have as yet no grounds to determine.<span class='pagenum'><a name="Page_86" id="Page_86">[Pg 86]</a></span></p>
+
+<p>The subjoined communication, appearing after the completion of the MS.
+of the book, and belonging to a date subsequent to the period intended
+to be covered, is nevertheless included by reason of its exceptional
+importance and special bearing on the constitutional problem above
+discussed.</p>
+
+
+<h3>THE ACTION OF HYDROGEN BROMINE ON CARBOHYDRATES.<a name="FNanchor_4_4" id="FNanchor_4_4"></a><a href="#Footnote_4_4" class="fnanchor">[4]</a></h3>
+
+<h4><span class="smcap">H. J. H. Fenton</span> and <span class="smcap">Mildred Gostling</span> (J. Chem. Soc., 1901, 361).</h4>
+
+<p>The authors have shown in a previous communication (Trans., 1898, 73,
+554) that certain classes of carbohydrates when acted upon at the
+ordinary temperature with dry hydrogen bromide in ethereal solution give
+an intense and beautiful purple colour.<a name="FNanchor_5_5" id="FNanchor_5_5"></a><a href="#Footnote_5_5" class="fnanchor">[5]</a> It was further shown (Trans.,
+1899, 75, 423) that this purple substance, when neutralised with sodium
+carbonate and extracted with ether, yields golden-yellow prisms of
+&#969;-brommethylfurfural,</p>
+
+<div class="figcenter" style="width: 274px;">
+<img src="images/image3.jpg" width="274" height="176" alt="" title="" />
+</div>
+
+<p>This reaction is produced by l&aelig;vulose, sorbose, cane sugar, and inulin,
+an intense colour being given within an hour or two. Dextrose, maltose,
+milk sugar, galactose, and the polyhydric alcohols give, if anything,
+only insignificant colours, and these only after long standing. The
+authors therefore suggested that the reaction might be employed as a
+means of<span class='pagenum'><a name="Page_87" id="Page_87">[Pg 87]</a></span> distinguishing these classes of carbohydrates, the rapid
+production of the purple colour being indicative of <i>ketohexoses</i>, or of
+substances which produce these by hydrolysis.</p>
+
+<p>By relying only on the production of the purple colour, however, a
+mistake might possibly arise, owing to the fact that <i>xylose</i> gives a
+somewhat similar colour after standing for a few hours. Hence, the
+observations should be confirmed by isolation of the crystals of
+brommethylfurfural. No trace of this substance is obtained from the
+xylose product.</p>
+
+<p>In order to identify the substance, the ether extract, after
+neutralisation, is allowed to evaporate to a syrup, and crystallisation
+promoted either by rubbing with a glass rod, or by the more certain and
+highly characteristic method of 'sowing' with the most minute trace of
+&#969;-brommethylfurfural, when crystals are almost instantly formed.
+These are recrystallised from ether, or a mixture of ether and light
+petroleum, and further identified by the melting-point (59.5-60.5&deg;),
+and, if considered desirable, by estimation of the bromine.</p>
+
+<p>It is now found, so reactive is the bromine atom in this compound, that
+the estimation may be accurately made by titration with silver nitrate
+according to Volhard's process, the crystals for this purpose being
+dissolved in dilute alcohol:</p>
+
+<p>0.1970 gram required 10.5 c.c. <i>N</i>/10 AgNO<sub>3</sub>. Br = 42.63
+p.ct., calculated 42.32 p.ct.</p>
+
+<p>This method of applying hydrogen bromide in ethereal solution is, of
+course, unsuitable for investigations where a higher temperature has to
+be employed, or where long standing is necessary, since, under such
+circumstances, the ether itself is attacked. Wishing to make
+investigations under these conditions, the authors have tried several
+solvents, and, at present, find that chloroform is best suited to the
+purpose. In each of the following experiments, 10 grms. of the<span class='pagenum'><a name="Page_88" id="Page_88">[Pg 88]</a></span>
+substance were covered with 250 c.c. of chloroform which had been
+saturated at 0&deg; with dry hydrogen bromide. The mixture was contained in
+an accurately stoppered bottle, firmly secured with an iron clamp, and
+heated in a water-bath to about the boiling temperature for two hours.
+After standing for several hours, the mixture was treated with sodium
+carbonate (first anhydrous solid, and afterwards a few drops of strong
+solution), filtered, and the solution dried over calcium chloride. Most
+of the chloroform was then distilled off, and the remaining solution
+allowed to evaporate to a thick syrup in a weighed dish.</p>
+
+<p>The product was then tested for &#969;-brommethylfurfural by 'sowing'
+with the most minute trace of the substance, as described above. It was
+then warmed on a water-oven, kept in a vacuum desiccator over solid
+paraffin, and the weight estimated. When necessary, the product was
+recrystallised from ether, and further identified by the tests
+mentioned. The following results were obtained:</p>
+
+
+
+<div class='center'>
+<table border="0" cellpadding="4" cellspacing="0" summary="">
+<tr><td align='left'></td><td colspan="2">Weight of crude residue.</td></tr>
+<tr><td align='left'>Swedish filter paper</td><td align='left'>3.0</td><td align='left'>crystallised at once</td><td align='left'> by 'sowing.'</td></tr>
+<tr><td align='left'>Ordinary cotton</td><td align='left'>3.3</td><td align='center'>"</td><td align='center'>"</td></tr>
+<tr><td align='left'>Mercerised cotton</td><td align='left'>2.1</td><td align='center'>"</td><td align='center'>"</td></tr>
+<tr><td align='left'>Straw cellulose<a name="FNanchor_6_6" id="FNanchor_6_6"></a><a href="#Footnote_6_6" class="fnanchor">[6]</a></td><td align='left'>2.3</td><td align='center'>"</td><td align='center'>"</td></tr>
+<tr><td align='left'>L&aelig;vulose</td><td align='left'>2.2</td><td align='center'>"</td><td align='center'>"</td></tr>
+<tr><td align='left'>Inulin</td><td align='left'>1.3</td><td align='center'>"</td><td align='center'>"</td></tr>
+<tr><td align='left'>Potato starch</td><td align='left'>0.37</td><td align='center'>"</td><td align='center'>"</td></tr>
+<tr><td align='left'>Cane sugar</td><td align='left'>0.85</td><td align='center'>"</td><td align='center'>"</td></tr>
+<tr><td align='left'>Dextrose</td><td align='left'>0.33</td><td align='left'>uncrystallisable.</td></tr>
+<tr><td align='left'>Milk sugar</td><td align='left'>0.37</td><td align='center'>"</td></tr>
+<tr><td align='left'>Glycogen</td><td align='left'>0.34</td><td align='center'>"</td></tr>
+<tr><td align='left'>Galactose</td><td align='left'>0.34</td><td align='center'>"</td></tr>
+</table></div>
+
+
+<p><span class='pagenum'><a name="Page_89" id="Page_89">[Pg 89]</a></span></p>
+<p>The products from <i>dextrose</i>, <i>milk sugar</i>, and <i>galactose</i> absolutely
+refused to crystallise even when extracted with ether and again
+evaporated, or by 'sowing,' stirring, &amp;c.</p>
+
+<p>The <i>glycogen</i> product deposited a very small amount of crystalline
+matter on standing, but the quantity was too minute for examination;
+moreover, it refused altogether to crystallise in contact with the
+aldehyde. It may fairly be stated, therefore, that these last four
+substances give absolutely negative results as regards the formation of
+&#969;-brommethylfurfural; if any is formed, its quantity is altogether
+too small to be detected.</p>
+
+<p>The specimen of <i>starch</i> examined was freshly prepared from potato, and
+purified by digestion for twenty-four hours each with <i>N</i>/10 KOH, <i>N</i>/4
+HCl, and strong alcohol; it was then washed with water and allowed to
+dry in the air. It will be seen that this substance gave a positive
+result, but that the yield was extremely small, and might yet be due to
+impurity. Considering the importance of the behaviour of starch, for the
+purpose of drawing general conclusions from these observations, it was
+thought advisable to make further experiments with specimens which could
+be relied upon, and also to investigate the behaviour of dextrin. This
+the authors have been enabled to do upon a series of specimens specially
+prepared by C. O'Sullivan, and thus described by him:</p>
+
+<div class="blockquot"><p>1. Rice starch, specially purified by the permanganate method.</p>
+
+<p>2. Wheat starch &nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp; " &nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp; &nbsp;&nbsp;&nbsp;"&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;"</p>
+
+<p>3. Oat starch, contains traces of oil, washed with dilute KOH
+and dilute HCl.</p>
+
+<p>4. Pea starch, first crop, washed with alkali, acid (HCl), and
+strong alcohol.</p>
+
+<p>5. Natural dextrin, D = 3.87, &#945;<sub>D</sub> = 194.7; K = 0.95, (<i>c</i>
+2.628).</p>
+
+<p>6. &#945;-Dextrin, C equation purified without fermentation, 30
+precipitations with alcohol (Trans., 1879, 35, 772).</p></div><p><span class='pagenum'><a name="Page_90" id="Page_90">[Pg 90]</a></span></p>
+
+<p>The examination of these specimens was conducted on a smaller scale, but
+under the same conditions as before, <i>one gram</i> of the substance being
+treated with 12.5 c.c. of the saturated chloroform solution and heated
+in sealed tubes for two hours as above. The results were as follows:</p>
+
+
+<div class='center'>
+<table border="0" cellpadding="4" cellspacing="0" summary="">
+<tr><td align='left'></td><td colspan="2">Weight of crude residue.</td></tr>
+<tr><td align='left'>1. Rice starch</td><td align='left'>0.046</td><td align='left'>crystallised at once</td><td align='left'> by 'sowing.'</td></tr>
+<tr><td align='left'>2. Wheat starch</td><td align='left'>0.044</td><td align='center'>"</td><td align='center'>"</td></tr>
+<tr><td align='left'>3. Oat starch</td><td align='left'>0.049</td><td align='center'>"</td><td align='center'>"</td></tr>
+<tr><td align='left'>4. Pea starch</td><td align='left'>0.064</td><td align='center'>"</td><td align='center'>"</td></tr>
+<tr><td align='left'>5. Natural dextrin</td><td align='left'>0.088</td><td align='center'>"</td><td align='center'>"</td></tr>
+<tr><td align='left'>6. &#945;-Dextrin</td><td align='left'>0.055</td><td align='center'>"</td><td align='center'>"</td></tr>
+</table></div>
+
+
+<p>The results may therefore be summarised as follows:&mdash;Treated under these
+particular conditions all forms of cellulose give large yields of
+&#969;-brommethylfurfural, some varieties giving as much as 33 per cent.
+L&aelig;vulose, inulin, and cane sugar give yields varying from 22 to 8.5 per
+cent.; various starches give small yields (average about 4.5 per cent.);
+and dextrins 5 to 8 per cent., whereas dextrose, milk sugar, and
+galactose give, apparently, none at all.</p>
+
+<p>The yields represent the solid crystalline residue; this when purified
+by recrystallisation gives, probably, about three-quarters of its weight
+of pure crystals. (In the case of dextrose, &amp;c., the yields represent
+the weight of syrup.)</p>
+
+<p>These numbers, however, by no means represent the maximum yields
+obtainable, owing to the comparatively slight solubility of hydrogen
+bromide in chloroform. The process was conducted in the above manner
+only for the sake of uniform comparison. The ether method previously
+described gives much larger yields; for example, 12 grms. of inulin
+treated with only 60 c.c. of the saturated ether gave 2.5 grms.<span class='pagenum'><a name="Page_91" id="Page_91">[Pg 91]</a></span> of
+substance. For the purpose of obtaining larger yields, other methods are
+being investigated.</p>
+
+<p>The facts recorded above, taken in conjunction with those given in our
+previous communications, appear to point definitely to the following
+general conclusions. First, that the various forms of <i>cellulose</i>
+contain one or more groups or nuclei identical with that contained in
+<i>l&aelig;vulose</i>, and that such groups constitute the main or essential part
+of the molecule. Secondly, that similar groupings are contained in
+<i>starches</i> and <i>dextrins</i>, but that the proportion of such groupings
+represents a relatively small part of the whole structure.</p>
+
+<p>The nature of this grouping is, according to the generally accepted
+constitution of <i>l&aelig;vulose</i>, the six-carbon chain with a ketonic group:</p>
+
+
+<div class="figcenter" style="width: 207px;">
+<img src="images/image4.jpg" width="207" height="89" alt="" title="" />
+</div>
+
+<p>But the results might, on the other hand, be considered indicative of
+the anhydride or 'lacton' grouping, which Tollens suggested for
+l&aelig;vulose:</p>
+
+<div class="figcenter" style="width: 159px;">
+<img src="images/image5.jpg" width="159" height="108" alt="" title="" />
+</div>
+
+<p>The latter very simply represents the formation of
+&#969;-brommethylfurfural from l&aelig;vulose,<a name="FNanchor_7_7" id="FNanchor_7_7"></a><a href="#Footnote_7_7" class="fnanchor">[7]</a></p>
+
+<div class="figcenter" style="width: 523px;">
+<img src="images/image6.jpg" width="523" height="142" alt="" title="" />
+</div>
+
+<p>giving</p>
+
+<div class="figcenter" style="width: 257px;">
+<img src="images/image7.jpg" width="257" height="114" alt="" title="" />
+</div>
+
+
+<p><span class='pagenum'><a name="Page_92" id="Page_92">[Pg 92]</a></span></p>
+
+<p>although by a little further 'manipulation' of the symbols the change
+could, of course, be represented by reference to the ketonic formula.</p>
+
+
+<h3>The Ketonic Constitution of Cellulose.</h3>
+
+<h4><span class="smcap">C. F. Cross</span> and <span class="smcap">E. J. Bevan</span> (J. Chem. Soc., 1901, 366).</h4>
+
+<p>In this paper the authors discuss more fully the theoretical bearings of
+the observations of Fenton and Gostling, the two papers being
+simultaneously communicated. The paper is mainly devoted to a review of
+the antecedent evidence, chemical and physiological, and to a general
+summing up in favour of the view that cellulose is a polyketose
+(anhydride).</p>
+
+<hr style='width: 45%;' />
+
+<p>(p. 79) <b>Composition of the Seed Hair of Eriodendron</b> (<b>Anf.</b>)&mdash;Some
+interest attaches to the results of an analytical investigation which we
+have made of this silky floss. There is little doubt that cotton is
+entirely exceptional in its characteristics: both in structure and
+chemical composition it fails to show any adaptation to what we may
+regard as the <i>more obvious</i> functions of a seed hair&mdash;which certainly
+do not demand either structural strength or chemical resistance. The
+following numbers determined for the kapok differentiate it widely from
+the cottons:</p>
+
+<div class="blockquot"><p>Ash, 1.3; moisture, 9.3; alkaline hydrolysis (loss) (<i>a</i>) 16.7,
+(<i>b</i>) 21.8. Cellulose, by chlorination, &amp;c., 71.1.</p></div>
+
+<p>In reacting with chloride it shows the presence of unsaturated groups,
+similar to the lignone of the woods. This was<span class='pagenum'><a name="Page_93" id="Page_93">[Pg 93]</a></span> confirmed by a
+well-marked reaction with ferric ferricyanide with increase of weight
+due to the fixation of the blue cyanide.</p>
+
+<p>But the most characteristic feature is the high yield of furfural on
+boiling with condensing acids. The following numbers were determined:</p>
+
+
+<div class='center'>
+<table border="0" cellpadding="4" cellspacing="0" summary="">
+<tr><td align='left'>Total furfural from original fibre</td><td align='left'>14.84</td></tr>
+<tr><td align='left'>In residue from alkali hydrolysis</td><td align='left'>11.5</td></tr>
+<tr><td align='left'>In cellulose isolated by Cl method</td><td align='left'>10.4</td></tr>
+</table></div>
+
+<p>Treated with sulphuric acids of concentration, (<i>a</i>) 92.1 grs.
+H<sub>2</sub>SO<sub>4</sub> per 100 c.c., (<i>b</i>) 105.8 grs. per 100 c.c., the fibres
+dissolve, and diluted immediately after complete solution it was
+resolved into</p>
+
+
+<div class='center'>
+<table border="0" cellpadding="4" cellspacing="0" summary="">
+<tr><td align='left'></td><td align='left'>(<i>a</i>) </td><td align='left'>(<i>b</i>)</td></tr>
+<tr><td align='left'>Reprecipitated fraction</td><td align='left'>68.7</td><td align='left'>43.7</td></tr>
+<tr><td align='left'>Soluble fraction yielding furfural</td><td align='left'>13.2</td><td align='left'>14.3</td></tr>
+</table></div>
+
+<p>By these observations it is established that the furfuroids are of the
+cellulose type and behave very much as the furfuroids of the cereal
+celluloses.</p>
+
+<p>This group of seed hairs invites exhaustive investigation. The furfuroid
+constituents are easily isolated, and as they constitute at least
+one-third of the fibre substance it is especially from this point of
+view that they invite study.<span class='pagenum'><a name="Page_94" id="Page_94">[Pg 94]</a></span></p>
+
+
+<h3>RECHERCHES SUR L'OXYCELLULOSE.</h3>
+
+<h4><span class="smcap">L. Vignon.</span></h4>
+
+<h3>R&eacute;sum&eacute; of investigations (1898-1900) of Oxycellulose, published as a
+brochure (Rey, Lyon, 1900).</h3>
+
+<p>(<i>a</i>) A typical oxycellulose prepared from cotton cellulose by the
+action of HClO<sub>3</sub> (HCl + KClO<sub>3</sub>) in dilute solution at 100&deg; for one
+hour gave the following numbers:</p>
+
+
+<div class='center'>
+<table border="0" cellpadding="4" cellspacing="0" summary="">
+<tr><td align='left'></td><td align='center'>C</td><td align='center'>H</td><td align='center'>O</td></tr>
+<tr><td align='left'>Elementary composition</td><td align='center'>43.55</td><td align='center'>6.03</td><td align='center'>50.42</td></tr>
+<tr><td align='left'></td><td align='center'>Oxycellulose</td><td align='center'>Original cellulose</td></tr>
+<tr><td align='left'>Analysis by Lange's method</td></tr>
+<tr><td align='left'>Soluble in KOH (at 180&deg;)</td><td align='center'>87.6</td><td align='center'>12.0</td></tr>
+<tr><td align='left'>Insoluble in KOH (at 180&deg;)</td><td align='center'>12.4</td><td align='center'>88.0</td></tr>
+<tr><td align='left'></td><td align='center'>Oxycellulose</td><td align='center'>Original cellulose</td></tr>
+<tr><td align='left'>Heat of combustion</td><td align='center'>4124-4133</td><td align='center'>4190-4224</td></tr>
+<tr><td align='left'>Heat evolved in contact with 50 times wt. normal KOH per 100 grms.</td><td align='center'>1.3 cal.</td><td align='center'>0.74 cal.</td></tr>
+<tr><td align='left'></td><td align='left'></td><td align='center'>Oxycellulose</td><td align='center'>Cellulose</td></tr>
+<tr><td align='left'>Absorption of colouring matters at 100&deg; per 100 grms.</td><td align='left'>Saffranine</td><td align='center'>0.7</td><td align='center'>0.0</td></tr>
+<tr><td align='left'></td><td align='left'>Methylene blue</td><td align='center'>0.6</td><td align='center'>0.2</td></tr>
+</table></div>
+
+<p>(<i>b</i>) <i>Yield of furfural from cellulose, oxy- and
+hydro-cellulose.</i>&mdash;From the hydrocelluloses variously prepared the
+author obtains 0.8 p.ct. furfural; from bleached cotton 1.8 p.ct.; and
+from the oxycelluloses variously prepared 2.0-3.5 p.ct. The 'furfuroid'
+is relatively more soluble in alkaline solutions (KOH) in the cold. The
+insoluble residue is a normal cellulose.</p>
+
+<p>(<i>c</i>) <i>Nitrates of cellulose, oxy- and hydro-cellulose.</i>&mdash;Treated with
+the usual acid mixture (H<sub>2</sub>SO<sub>4</sub> 3 p., HNO<sub>3</sub> 1 p.) under conditions
+for maximum action, the resulting esters showed uniformly a fixation of
+<span class='pagenum'><a name="Page_95" id="Page_95">[Pg 95]</a></span>11.0 NO<sub>2</sub> groups per unit mol. of C<sub>24</sub>. The oxycellulose nitrate
+was treated directly with dilute solution of potassium hydrate in the
+cold. From the products of decomposition the author obtained the osazone
+of hydroxypyruvic acid [Will, Ber. 24, 400].</p>
+
+<p>(<i>d</i>) <i>Osazones of the oxycelluloses.</i>&mdash;Oxycelluloses prepared by
+various methods are found to fix varying proportions of phenylhydrazine
+(residue), viz. from 3.4-8.5 p.ct. of the cellulose derivative reacting,
+corresponding with, i.e. calculated from, the nitrogen determined in the
+products (0.87-2.2 p.ct.). The reaction is assumed to be that of osazone
+formation.</p>
+
+<p>The author has also established a relation between the phenylhydrazine
+fixed and the furfural which the substance yields on boiling with
+condensing acids. This is illustrated by the subjoined series of
+numbers:</p>
+
+
+<div class='center'>
+<table border="0" cellpadding="4" cellspacing="0" summary="">
+<tr><td align='left'></td><td align='left'></td><td align='center'>Fixed p.ct.</td><td align='center'>formed p.ct.</td></tr>
+<tr><td align='left'>Cotton (bleached)</td><td align='left'></td><td align='center'>1.73</td><td align='center'>1.60</td></tr>
+<tr><td align='left'>Oxycellulose</td><td align='center'>(HClO<sub>3</sub>)</td><td align='center'>7.94</td><td align='center'>2.09</td></tr>
+<tr><td align='center'>"</td><td align='left'>(HClO)</td><td align='center'>3.37</td><td align='center'>1.79</td></tr>
+<tr><td align='center'>"</td><td align='left'>(CrO<sub>3</sub>) (1)</td><td align='center'>7.03</td><td align='center'>3.00</td></tr>
+<tr><td align='center'>"</td><td align='left'>(CrO<sub>3</sub>) (2)</td><td align='center'>7.71</td><td align='center'>3.09</td></tr>
+<tr><td align='center'>"</td><td align='left'>(CrO<sub>3</sub>) (3)</td><td align='center'>8.48</td><td align='center'>3.50</td></tr>
+</table></div>
+
+<p>(<i>e</i>) <i>Constitution of cellulose and oxycellulose.</i>&mdash;The results of
+these investigations are generalised as regards cellulose (C_6) by the
+constitutional formula</p>
+
+<div class="figcenter" style="width: 274px;">
+<img src="images/image8.jpg" width="274" height="98" alt="" title="" />
+</div>
+
+<p>The oxycelluloses contain the characteristic group</p>
+
+
+<div class="figcenter" style="width: 180px;">
+<img src="images/image9.jpg" width="180" height="90" alt="" title="" />
+</div>
+
+<p>
+in union with varying proportions of residual cellulose.</p>
+
+<p><span class='pagenum'><a name="Page_96" id="Page_96">[Pg 96]</a></span></p>
+
+<h3>QUANTITATIVE SEPARATION OF CELLULOSE-LIKE CARBOHYDRATES IN VEGETABLE
+SUBSTANCES.</h3>
+
+<h4><span class="smcap">Wilhelm Hoffmeister</span> (Landw. Versuchs-Stat., 1897, 48, 401-411).</h4>
+
+<p>To separate the hemicelluloses, celluloses, and the constituents of
+lignin without essential change, the substance, after being freed from
+fat, is extracted with dilute hydrochloric acid and ammonia, and the
+residue frequently agitated for a day or two with 5-6 p.ct. caustic soda
+solution. It is then diluted, the extract poured off, neutralised with
+hydrochloric acid, treated with sufficient alcohol, and the
+hemicellulose filtered, dried, and weighed. The residue from the soda
+extract is washed on a filter with hot water, and extracted with
+Schweizer's reagent.</p>
+
+<p>When the final residue (lignin) is subjected to prolonged extraction
+with boiling dilute ammonia (a suitable apparatus is described, with
+sketch) until the ammonia is no longer coloured, a residue is obtained
+which mostly dissolves in Schweizer's reagent, and on repeating the
+process the residue is found to consist largely of mineral matter. The
+dissolved cellulose-like substances often contain considerable amounts
+of pentosanes.</p>
+
+<p>According to the nature of the substance, the extraction with ammonia
+may take weeks, or months, or even longer; the ammonia extracts of hard
+woods (as lignum vit&aelig;) and of cork are dark brown, and give an odour of
+vanilla when evaporated down. The residues, which are insoluble in
+water, but redissolve in ammonia, have the properties of humic acids.
+Other vegetable substances, when extracted, yielded, besides humic
+acids, a compound, C<sub>6</sub>H<sub>7</sub>O<sub>2</sub>, soluble in alcohol and chloroform,
+but insoluble in water, ether, and benzene; preparations from different
+sources melted between 200&deg; and 210&deg;.</p>
+
+<div class="footnotes"><h3>FOOTNOTES:</h3>
+
+<div class="footnote"><p><a name="Footnote_4_4" id="Footnote_4_4"></a><a href="#FNanchor_4_4"><span class="label">[4]</span></a> The original paper is reproduced with slight alterations.</p></div>
+
+<div class="footnote"><p><a name="Footnote_5_5" id="Footnote_5_5"></a><a href="#FNanchor_5_5"><span class="label">[5]</span></a> This purple colour would appear to be due to a highly
+dissociable compound of &#969;-brommethylfurfural with hydrogen bromide.
+The aldehyde gives yellow or colourless solutions in various solvents,
+which are turned purple by a sufficient excess of hydrogen bromide.
+Dilution, or addition of water, at once discharges the colour.</p></div>
+
+<div class="footnote"><p><a name="Footnote_6_6" id="Footnote_6_6"></a><a href="#FNanchor_6_6"><span class="label">[6]</span></a> Other forms of cellulose were also examined&mdash;for example,
+pinewood cellulose&mdash;and the substances separated from solution as
+thiocarbonate (powder and film). All of these gave good yields of
+&#969;-brommethylfurfural.</p></div>
+
+<div class="footnote"><p><a name="Footnote_7_7" id="Footnote_7_7"></a><a href="#FNanchor_7_7"><span class="label">[7]</span></a> The change is empirically represented as
+<br />
+<span style="margin-left: 2.5em;">C<sub>6</sub>H<sub>12</sub>O<sub>6</sub> + HBr - 4H<sub>2</sub>O = C<sub>6</sub>H<sub>5</sub>O<sub>2</sub>Br.</span><br />
+</p>
+</div>
+</div>
+
+
+<hr style="width: 65%;" />
+<p><span class='pagenum'><a name="Page_97" id="Page_97">[Pg 97]</a></span></p>
+<h2>SECTION IV. CELLULOSE GROUP, INCLUDING HEMICELLULOSES AND TISSUE CONSTITUENTS OF FUNGI</h2>
+
+<h3>VERSUCHE ZUR BESTIMMUNG DES GEHALTS EINIGER PFLANZEN UND PFLANZENTEILE
+AN ZELLWANDBESTANDTEILEN AN HEMICELLULOSEN UND AN CELLULOSE.</h3>
+
+<h4><span class="smcap">A. Kleiber</span> (Landw. Vers.-Stat., 1900, 54, 161).</h4>
+
+<h3>ON THE DETERMINATION OF CELL-WALL CONSTITUENTS, HEMICELLULOSES AND
+CELLULOSE IN PLANTS AND PLANT TISSUES.</h3>
+
+<p>In a preliminary discussion the author critically compares the results
+of various of the methods in practice for the isolation and estimation
+of cellulose. The method of F. Schulze [digestion with dil. HNO<sub>3</sub> with
+KClO<sub>3</sub>&mdash;14 days, and afterwards treating the product with ammonia,
+&amp;c.] is stated to be the 'best known' (presumably the most widely
+practised); W. Hoffmeister's modification of the above, in which the
+nitric acid is replaced by hydrochloric acid (10 p.ct. HCl) is next
+noted as reducing the time of digestion from 14 days to 1-2 days, and
+giving in many cases higher yields of cellulose. The methods of treating
+with the halogens, viz. bromine water (H. M&uuml;ller), chlorine gas (Cross
+and Bevan), and chlorine water, are dismissed with a bare mention,
+apparently on the basis of the conclusions of Suringar and Tollens
+(<i>q.v.</i>). The method of Lange, the basis of which is a 'fusion' with
+alkaline hydrates at 180&deg;, and the modified method of Gabriel, in which
+the 'fusion' with alkali takes place in presence of glycerin, are
+favourably mentioned.</p>
+
+<p>These methods were applied to a range of widely different raw materials
+to determine, by critical examination of the products, both as regards
+yield and composition, what title these latter have to be regarded as
+'pure cellulose.'</p>
+
+<p>This portion of the investigation is an extension of that of Suringar
+and Tollens, these latter confining themselves to<span class='pagenum'><a name="Page_98" id="Page_98">[Pg 98]</a></span> celluloses of the
+'normal' groups, i.e. textile and paper-making celluloses. The present
+communication is a study of the tissue and cell-wall constituents of the
+following types:&mdash;</p>
+
+<p>
+<span style="margin-left: 2.5em;">1. Green plants of false oat grass (<i>Arrhenatherium, E.</i>).</span><br />
+<span style="margin-left: 2.5em;">2. Green plants of lucerne (<i>Medicago sativa</i>).</span><br />
+<span style="margin-left: 2.5em;">3. Leaves of the ash (<i>Fraxinus</i>).</span><br />
+<span style="margin-left: 2.5em;">4. Leaves of the walnut (<i>Juglans</i>).</span><br />
+<span style="margin-left: 2.5em;">5. Roots of the purple melic grass (<i>Molinia c&aelig;rulea</i>).</span><br />
+<span style="margin-left: 2.5em;">6. Roots of dandelion (<i>Taraxacum officinale</i>).</span><br />
+<span style="margin-left: 2.5em;">7. Roots of comfrey.</span><br />
+<span style="margin-left: 2.5em;">8. Coffee berries.</span><br />
+<span style="margin-left: 2.5em;">9. Wheat bran.</span><br />
+</p>
+
+<p>These raw materials were treated for the quantitative estimation of
+cellulose by the method of Lange (<i>b</i>), Hoffmeister (<i>c</i>), and Schulze
+(<i>d</i>), and the numbers obtained are referred for comparison to the
+corresponding yields of 'crude fibre' (Rohfaser) by the standard method
+(<i>a</i>).</p>
+
+<p>As a first result the author dismisses Lange's method as hopeless: the
+results in successive determinations on the same materials showing
+variations up to 60 p.ct. The results by <i>c</i> and <i>d</i> are satisfactorily
+concordant: the yields of cellulose are higher than of 'crude fibre.'
+This is obviously due to the conservation of 'hemicellulose' products,
+which are hydrolysed and dissolved in the treatments for 'crude fibre'
+estimation. A modified method was next investigated, in which the
+process of digestion with acid chloroxy- compounds (<i>c</i> and <i>d</i>) was
+preceded by a treatment with boiling dilute acid. The yields of
+cellulose by this method (<i>e</i>) are more uniform, and show less
+divergence from the numbers for 'crude fibre.'</p>
+
+<p>The author's numerical results are given in a series of tables which
+include determinations of proteids and ash constituents, and the
+corresponding deductions from the crude<span class='pagenum'><a name="Page_99" id="Page_99">[Pg 99]</a></span> weight in calculating to 'pure
+cellulose.' The subjoined extract will illustrate these main lines of
+investigation.</p>
+
+
+<div class='center'>
+<table border="1" cellpadding="4" cellspacing="0" summary="">
+<tr><td rowspan="2">Raw Material</td><td align='center'> Crude Fibre</td><td colspan="2"> Pure Cellulose</td></tr>
+<tr><td align='center'> Weende Method.<br />(<i>a</i>)</td><td align='center'> Hoffmeister Method.<br />(<i>c</i>)</td><td align='center'> Hoffmeister, modified by Author.<br />(<i>e</i>)</td></tr>
+<tr><td align='left'>Oat grass</td><td align='center'> 30.35</td><td align='center'> 34.9</td><td align='center'> 31.5</td></tr>
+<tr><td align='left'>Lucerne</td><td align='center'> 25.25</td><td align='center'> 28.7</td><td align='center'> 20.5</td></tr>
+<tr><td align='left'>Leaves of ash</td><td align='center'> 13.05</td><td align='center'> 15.4</td><td align='center'> 13.8</td></tr>
+<tr><td align='left'>Roots of melic</td><td align='center'> 21.60</td><td align='center'> 29.1</td><td align='center'> 21.4</td></tr>
+<tr><td align='left'>Coffee beans</td><td align='center'> 18.30</td><td align='center'> 35.1</td><td align='center'> 23.3</td></tr>
+<tr><td align='left'>Bran</td><td align='center'> 8.2</td><td align='center'> 19.3</td><td align='center'> 9.3</td></tr>
+</table></div>
+
+<p>The final conclusion drawn from these results is that the method of
+Hoffmeister yields a product containing variable proportions of
+hemicelluloses. These are eliminated by boiling with a dilute acid (1.25
+p.ct. H<sub>2</sub>SO<sub>4</sub>), which treatment may be carried out on the raw
+material&mdash;<i>i.e.</i> before exposure to the acid chlorate, or on the crude
+cellulose as ordinarily isolated.</p>
+
+<p><b>Determination of Tissue-constituents.</b>&mdash;By the regulated action of
+certain solvents applied in succession, it appears that such
+constituents of the plant-complex can be removed as have no organic
+connection with the cellular skeleton: the residue from such treatments,
+conversely, fairly represents the true tissue-constituents. The author
+employs the method of digestion with cold dilute alkaline solutions
+(0.15 to 0.5 p.ct. NaOH), followed by exhaustive washing with cold and
+hot water, afterwards with cold and hot alcohol, and finally with ether.</p>
+
+<p>The residue is dried and weighed as crude product. When necessary, the
+proportions of ash and proteid constituents are determined and deducted
+from the 'crude<span class='pagenum'><a name="Page_100" id="Page_100">[Pg 100]</a></span> product' which, thus corrected, may be taken as
+representing the 'carbohydrate' tissue constituents.</p>
+
+<p><b>Determination of Hemicelluloses.</b>&mdash;By the process of boiling with dilute
+acids (1.25 p.ct. H<sub>2</sub>SO<sub>4</sub>) the hemicelluloses are attacked&mdash;i.e.
+hydrolysed and dissolved. The action of the acid though selective is, of
+course, not exclusively confined to these colloidal carbohydrates. The
+proteid and mineral constituents are attacked more or less, and the
+celluloses themselves are not entirely resistant to the action. The loss
+due to the latter may be neglected, but in calculating the hemicellulose
+constants from the gross loss the proteids and mineral constituents
+require to be taken into account in the usual way.</p>
+
+
+<h3>QUANTITATIVE SEPARATION OF HEMICELLULOSE, CELLULOSE, AND LIGNIN.
+PRESENCE OF PENTOSANES IN THESE SUBSTANCES.</h3>
+
+<h4><span class="smcap">Wilhelm Hoffmeister</span> (Landw. Versuchs-Stat, 1898, 50, 347-362).</h4>
+
+<p>(p. 88) The separation of the cellulose-like carbohydrates of sunflower
+husks is described.</p>
+
+<p>In order to ascertain the effect of dilute ammonia on the cellulose
+substances of lignin, a dried 5 p.ct. caustic soda extract was extracted
+successively with 1, 2, 3, and 4 p.ct. sodium hydroxide solution. Five
+grams of the 2 p.ct. extract were then subjected to the action of
+ammonia vapour; the cellulose did not completely dissolve in six weeks.
+Cellulose insoluble in caustic soda (32 grms.) was next extracted with
+ammonia, in a similar manner, for 10 days, dried, and weighed. 30.46
+grms. remained, which, when treated with 5 p.ct. aqueous caustic soda,
+yielded 0.96 grm. (3 per cent.) of hemicellulose.</p>
+
+<p>When cellulose is dissolved in Schweizer's solution, the<span class='pagenum'><a name="Page_101" id="Page_101">[Pg 101]</a></span> residue is, by
+repeated extraction with aqueous sodium hydroxide, completely converted
+into the soluble form. On evaporating the ammonia from the Schweizer's
+extract, at the ordinary temperature and on a water-bath respectively,
+different amounts of cellulose are obtained; more hemicellulose is
+obtained, by caustic soda, from the heated solution than from that which
+was not heated. In this operation the pentosanes are more influenced
+than the hexosanes; pentosanes are not always readily dissolved by
+caustic soda, and hexosanes are frequently more or less readily
+dissolved. Both occur in lignin, and are then undoubtedly indigestible.
+These points have to be considered in judging the digestibility of these
+carbohydrates.</p>
+
+<p>A comparison of analyses of clover, at different periods, in the first
+and second years of growth, shows that both cellulose (Schweizer's
+extract) and lignin increase in both constituents. In the second year
+the lignin alone increased to the end; the cellulose decreased at the
+end of June. In the first year it seemed an absolutely as well as
+relatively greater amount of cellulose, and lignin was produced in the
+second year; this, however, requires confirmation. The amount of
+pentosanes in the Schweizer extract was relatively greater in the second
+than in the first year, but decreased in the lignin more in the second
+year than in the first: this result is also given with reserve.</p>
+
+
+<h3>DIE CONSTITUTION DER CELLULOSEN DER CEREALIEN.</h3>
+
+<h4><span class="smcap">C. F. Cross, E. J. Bevan</span>, and <span class="smcap">C. Smith</span> (Berl. Ber., 1896, 1457).</h4>
+
+<h3>THE CONSTITUTION OF THE CEREAL CELLULOSES.</h3>
+
+<p>(p. 84) Straw cellulose is resolved by two methods of acid hydrolysis
+into a soluble furfural-yielding fraction, and an insoluble<span class='pagenum'><a name="Page_102" id="Page_102">[Pg 102]</a></span> fraction
+closely resembling the normal cellulose. (<i>a</i>) The cellulose is
+dissolved in sulphuric acids of concentration, H<sub>2</sub>SO<sub>4</sub>.2H<sub>2</sub>O,
+H<sub>2</sub>SO<sub>4</sub>.3H<sub>2</sub>O. As soon as solution is complete, the acid is
+diluted. A precipitate of cellulose hydrate (60-70 p.ct.) is obtained,
+and the filtered solution contains 90-95 p.ct. of the furfuroids of the
+original cellulose. The process is difficult to control, however, in
+mass, and to obtain the latter in larger quantity the cellulose (<i>b</i>) is
+digested with six times its weight of 1 p.ct. H<sub>2</sub>SO<sub>4</sub> at 3 atm.
+pressure, the products of the action being (1) a disintegrated cellulose
+retaining only a small fraction (1/12) of the furfural-yielding groups,
+and (2) a slightly coloured solution of the hydrolised furfuroids. An
+investigation of the latter gave the following results: By oxidation
+with nitric acid no saccharic acid was obtained; showing the absence of
+dextrose. The numbers for cupric reduction were in excess of those
+obtained with the hexoses. The yield of ozazone was high, viz. 30 to 40
+p.ct. of the weight of the carbohydrate in solution. On fractionating,
+the melting-points of the fractions were found to lie between 146&deg; and
+153&deg;. Ultimate analysis gave numbers for C, H, and N identical with
+those of a pentosazone. The product of hydrolysis appears, therefore, to
+be xylose or a closely related derivative.</p>
+
+<p>All attempts to obtain a crystallisation of xylose from the solution
+neutralised (BaCO<sub>3</sub>), filtered, and evaporated, failed. The reaction
+with phloroglucol and HCl, moreover, was not the characteristic red of
+the pentoses, but a deep violet. The product was then isolated as a dry
+residue by evaporating further and drying at 105&deg;. Elementary analysis
+gave the numbers C 44.2, 44.5, and H 6.7, 6.3. Determinations of
+furfural gave 39.5 to 42.5 p.ct. On treating the original solution with
+hydrogen peroxide, and warming, oxidation set in, with evolution of
+<span class='pagenum'><a name="Page_103" id="Page_103">[Pg 103]</a></span>CO<sub>2</sub>. This was estimated (by absorption), giving numbers for CO<sub>2</sub>,
+19.5, 20.5, 20.1 p.ct. of the substance.</p>
+
+<p>The sum of these quantitative data is inconsistent with a pentose or
+pentosane formula; it is more satisfactorily expressed by the empirical
+formula</p>
+
+<div class="figcenter" style="width: 251px;">
+<img src="images/image10.jpg" width="251" height="60" alt="" title="" />
+</div>
+
+<p>which represents a pentose monoformal. Attempts to synthesise a compound
+of this formula have been so far without success.</p>
+
+
+<h3>UEBER EINIGE CHEMISCHE VORG&Auml;NGE IN DER GERSTENPFLANZE.</h3>
+
+<h4><span class="smcap">C. F. Cross, E. J. Bevan</span>, and <span class="smcap">C. Smith</span> (Berl. Ber., 1895, 2604).</h4>
+
+<h3>THE CHEMICAL LIFE-HISTORY OF THE BARLEY PLANT.</h3>
+
+<p>(p. 84) Owing to the presence of 'furfuroids' in large proportion as
+constituents of the tissues of the stems of cereals, these plants afford
+convenient material for studying the problem of the constitution of the
+tissue-furfuroids, as well as their relationship to the normal
+celluloses. The growing barley plant was investigated at successive
+periods of growth. Yield of furfural was estimated on the whole plant
+and on the residue from a treatment with alkaline and acid solvents in
+the cold such as to remove all cell contents. This residue is described
+as 'permanent tissue.' The observations were carried out through two
+growing seasons&mdash;1894-5&mdash;which were very different in character, the
+former being rainy with low temperature, the latter being abnormal in
+the opposite direction, i.e. minimum rainfall and maximum sunshine. The
+barley selected for observation was that of two experimental plots of
+the Royal Agricultural Society's farm, one (No. 1) remaining permanently
+unmanured, and showing minimum yield, the other (No. 6) receiving such
+fertilising treatment as to give maximum yields.<span class='pagenum'><a name="Page_104" id="Page_104">[Pg 104]</a></span></p>
+
+<p>The numerical results are given in the annexed tables:</p>
+
+
+<h3>BARLEY CROP, WOBURN, 1894.</h3>
+
+
+<div class='center'>
+<table border="1" cellpadding="4" cellspacing="0" summary="">
+<tr><td rowspan="2"> Date</td><td rowspan="2"> Age of Crop</td><td rowspan="2"> Plot</td><td rowspan="2"> Dry Weight</td><td rowspan="2"> Furfural p.ct. of dry weight(<i>a</i>)</td><td rowspan="2"> Permanent tissue p.ct. dry weight</td><td colspan="2"> Furfural from permanent tissue</td></tr>
+<tr><td align='left'> P.ct. of tissue</td><td align='left'> P.ct. of entire plant</td><td align='left'> Ratio <i>a</i> : <i>c</i></td></tr>
+<tr><td rowspan="2"> May 7</td><td rowspan="2"> 6 weeks</td><td align='left'> 1</td><td align='left'> 19.4</td><td align='left'> 7.0</td><td align='left'> 53.4</td><td align='left'> 12.7</td><td align='left'> 6.8</td><td align='left'> 1.03 : 1</td></tr>
+<tr><td align='left'> 6</td><td align='left'> 14.7</td><td align='left'> 7.0</td><td align='left'> 55.9</td><td align='left'> 10.3</td><td align='left'> 5.7</td><td align='left'> 1.23 : 1</td></tr>
+<tr><td rowspan="2"> June 4</td><td rowspan="2"> 10 weeks</td><td align='left'> 1</td><td align='left'> 17.6</td><td align='left'> 7.7</td><td align='left'> 52.9</td><td align='left'> 11.6</td><td align='left'> 6.1</td><td align='left'> 1.26 : 1</td></tr>
+<tr><td align='left'> 6</td><td align='left'> 13.5</td><td align='left'> 8.1</td><td align='left'> 58.5</td><td align='left'> 13.4</td><td align='left'> 7.8</td><td align='left'> 1.04 : 1</td></tr>
+<tr><td rowspan="2"> July 10</td><td rowspan="2"> 15 weeks</td><td align='left'> 1</td><td align='left'> 42.0</td><td align='left'> 9.0</td><td align='left'> 65.7</td><td align='left'> 9.8</td><td align='left'> 6.4</td><td align='left'> 1.40 : 1</td></tr>
+<tr><td align='left'> 6</td><td align='left'> 32.9</td><td align='left'> 10.6</td><td align='left'> 65.7</td><td align='left'> 12.5</td><td align='left'> 8.2</td><td align='left'> 1.30 : 1</td></tr>
+<tr><td rowspan="2"> Cut  Aug. 21</td><td rowspan="2"> 21 weeks</td><td align='left'> 1</td><td align='left'> 64.0</td><td align='left'> 11.9</td><td align='left'> 70.0</td><td align='left'> 14.5</td><td align='left'> 10.1</td><td align='left'> 1.18 : 1</td></tr>
+<tr><td align='left'> 6</td><td align='left'> 64.6</td><td align='left'> 13.4</td><td align='left'> 70.5</td><td align='left'> 15.0</td><td align='left'> 10.6</td><td align='left'> 1.26 : 1</td></tr>
+<tr><td rowspan="2"> Carried Aug. 31</td><td rowspan="2"> 22 weeks</td><td align='left'> 1</td><td align='left'> 84.0</td><td align='left'> 12.7</td><td align='left'> 75.0</td><td align='left'> 16.5</td><td align='left'> 12.4</td><td align='left'> 1.02 : 1</td></tr>
+<tr><td align='left'> 6</td><td align='left'> 86.4</td><td align='left'> 12.4</td><td align='left'> 78.4</td><td align='left'> 15.1</td><td align='left'> 11.8</td><td align='left'> 1.05 : 1</td></tr>
+<tr><td colspan="9"> BARLEY CROP, WOBURN, 1895.</td></tr>
+<tr><td rowspan="2"> May 15</td><td rowspan="2"> 7 weeks</td><td align='left'> 1</td><td align='left'> 20.6</td><td align='left'> 6.6</td><td align='left'> 53.9</td><td align='left'> 10.2</td><td align='left'> 5.5</td><td align='left'> 1.20 : 1</td></tr>
+<tr><td align='left'> 6</td><td align='left'> 17.8</td><td align='left'> 5.8</td><td align='left'> 56.7</td><td align='left'> 9.6</td><td align='left'> 5.4</td><td align='left'> 1.07 : 1</td></tr>
+<tr><td rowspan="2"> June 18</td><td rowspan="2"> 12 weeks</td><td align='left'> 1</td><td align='left'> 34.6</td><td align='left'> 8.0</td><td align='left'> 38.2</td><td align='left'> 14.7</td><td align='left'> 5.6</td><td align='left'> 1.42 : 1</td></tr>
+<tr><td align='left'> 6</td><td align='left'> 33.4</td><td align='left'> 7.6</td><td align='left'> 44.5</td><td align='left'> 15.0</td><td align='left'> 6.7</td><td align='left'> 1.14 : 1</td></tr>
+<tr><td rowspan="2"> July 16</td><td rowspan="2"> 16 weeks</td><td align='left'> 1</td><td align='left'> 52.8</td><td align='left'> 12.1</td><td align='left'> 55.6</td><td align='left'> 16.3</td><td align='left'> 9.1</td><td align='left'> 1.33 : 1</td></tr>
+<tr><td align='left'> 6</td><td align='left'> 54.4</td><td align='left'> 10.6</td><td align='left'> 46.2</td><td align='left'> 19.1</td><td align='left'> 8.8</td><td align='left'> 1.20 : 1</td></tr>
+<tr><td rowspan="2"> Aug. 16</td><td rowspan="2"> 20 weeks</td><td align='left'> 1</td><td align='left'> 66.8</td><td align='left'> 9.2</td><td align='left'> 49.1</td><td align='left'> 17.0</td><td align='left'> 8.3</td><td align='left'> 1.10 : 1</td></tr>
+<tr><td align='left'> 6</td><td align='left'> 65.0</td><td align='left'> 9.8</td><td align='left'> 49.8</td><td align='left'> 19.1</td><td align='left'> 9.4</td><td align='left'> 1.04 : 1</td></tr>
+<tr><td rowspan="2"> Sept. 3</td><td rowspan="2"> 22 weeks</td><td align='left'> 1</td><td align='left'> 84.3</td><td align='left'> 10.4</td><td align='left'> 45.7</td><td align='left'> 17.6</td><td align='left'> 8.0</td><td align='left'> 1.31 : 1</td></tr>
+<tr><td align='left'> 6</td><td align='left'> 86.3</td><td align='left'> 10.2</td><td align='left'> 45.3</td><td align='left'> 17.3</td><td align='left'> 7.8</td><td align='left'> 1.30 : 1</td></tr>
+</table></div>
+
+
+<p><span class='pagenum'><a name="Page_105" id="Page_105">[Pg 105]</a></span></p>
+
+<p>The variations exhibited by these numbers are significant. It is clear,
+on the other hand, that the assimilation of the furfuroids does not vary
+in any important way with variations in conditions of atmosphere and
+soil nutrition. They are essentially <i>tissue</i>-constituents, and only at
+the flowering period is there any accumulation of these compounds in the
+alkali-soluble form. It has been previously shown (<i>ibid.</i> 27, 1061)
+that the proportion of furfuroids in the straw-celluloses of the
+paper-maker differs but little from that of the original straws. For the
+isolation of the celluloses the straws are treated by a severe process
+of alkaline hydrolysis, to which, therefore, the furfuroid groups offer
+equal resistance with the normal hexose groups with which they are
+associated in the complex.</p>
+
+<p>The furfuroids of the cereal straws are therefore not pentosanes. They
+are original products of assimilation, and not subject to secondary
+changes after elaboration such as to alter either their constitution or
+their relationship to the normal hexose groups of the tissue-complex.</p>
+
+
+<h3>(1) CONSTITUTION OF THE CEREAL CELLULOSES</h3>
+
+<h4>(Chem. Soc. J. 1896, 804).</h4>
+
+
+<h3>(2) THE CARBOHYDRATES OF BARLEY STRAW</h3>
+
+<h4>(Chem. Soc. J. 1896, 1604).</h4>
+
+
+<h3>(3) THE CARBOHYDRATES OF THE CEREAL</h3>
+
+<h4>STRAWS (Chem. Soc. J. 1897, 1001).</h4>
+
+
+<h3>(4) THE CARBOHYDRATES OF BARLEY STRAW</h3>
+
+<h4>(Chem. Soc. J. 1898, 459).</h4>
+
+<h4><span class="smcap">C. F. cross, E. J. Bevan</span>, and <span class="smcap">Claud Smith</span>.</h4>
+
+<p>These are a series of investigations mainly devoted to establishing the
+identity of the furfural-yielding group which is a characteristic
+constituent.</p>
+
+<p>This 'furfuroid' while equally resistant to alkalis as the normal
+cellulose group with which it is associated, is selectively<span class='pagenum'><a name="Page_106" id="Page_106">[Pg 106]</a></span> hydrolysed
+by acids. Thus straw cellulose dissolves in sulphuric acids of
+concentration H<sub>2</sub>SO<sub>4</sub>.2H<sub>2</sub>O - H<sub>2</sub>SO<sub>4</sub>.3H<sub>2</sub>O, and on diluting
+the normal cellulose is precipitated as a hydrate, and the furfuroid
+remains in solution. But this sharp separation is difficult to control
+in mass. By heating with a very dilute acid (1 p.ct. H<sub>2</sub>SO<sub>4</sub>) the
+conditions are more easily controlled, the most satisfactory results
+being obtained with 15 mins. heating at 3 atm. pressure.</p>
+
+<p>(1) Operating in this way upon brewers' grains the furfuroid was
+obtainable as the chief constituent of a solution for which the
+following experimental numbers were determined:&mdash;Total dissolved solids,
+28.0 p.ct. of original 'grains'; furfural, 39.5 p.ct. of total dissolved
+solids, as compared with 12.5 p.ct. of total original grains; cupric
+reduction (calc. to total solids), 110 (dextrose = 100) osazone; yield
+in 3 p.ct. solution, 35 p.ct. of weight of total solids.</p>
+
+
+<div class='center'>
+<table border="0" cellpadding="4" cellspacing="0" summary="">
+<tr><td align='left'></td><td align='left'></td><td align='left'></td><td align='left'></td><td align='left'>Pentosazone</td></tr>
+<tr><td align='left'>Analysis</td><td align='left'>N</td><td align='left'>17.1</td><td align='left'>17.3</td><td align='left'>17.07</td></tr>
+<tr><td align='left'></td><td align='left'>C</td><td align='left'>62.5</td><td align='left'>62.3</td><td align='left'>62.2</td></tr>
+<tr><td align='left'></td><td align='left'>H</td><td align='left'>6.4</td><td align='left'>6.5</td><td align='left'>6.1</td></tr>
+<tr><td align='left'>Melting-point</td><td align='left'></td><td align='left'></td><td align='left'></td><td align='left'>146&deg;-153&deg;</td></tr>
+</table></div>
+
+<p>From these numbers it is seen that of the total furfuroids of the
+original 'grains' 84 p.ct. are thus obtained in solution in the fully
+hydrolysed form, which is that of a pentose or pentose derivative. It
+was, however, found impossible to obtain any crystallisation from the
+neutralised (BaCO<sub>3</sub>) and concentrated solution, the syrup being kept
+for some weeks in a desiccator. It was noted at the same time that the
+colour reaction of the original solution with phloroglucol and
+hydrochloric acid was a deep violet, in contradistinction to the
+characteristic red of the pentoses. On oxidation with hydrogen peroxide,
+in the proportion of 1 mol. H<sub>2</sub>O<sub>2</sub> to 1 mol. of the carbohydrate in
+solution, carbonic anhydride was formed in quantity = 20.0 p.ct. of the
+latter.<span class='pagenum'><a name="Page_107" id="Page_107">[Pg 107]</a></span></p>
+
+<p>Fermentation (yeast) experiments also showed a divergence from the
+resistant behaviour of the pentoses, a considerable proportion of the
+furfuroid disappearing in a normal fermentation.</p>
+
+<p>(2) The quantitative methods above described were employed in
+investigating the barley plant at different stages of its growth. The
+green plant was extracted with alcohol, the residue freed from alcohol
+and subjected to acid hydrolysis.</p>
+
+<p>The hydrolysed extract was neutralised and fermented. In the early
+stages of growth the furfuroids were completely fermented, i.e.
+disappeared in the fermentation. In the later stages this proportion
+fell to 50 p.ct. In the earlier stages, moreover, the normal hexose
+constituents of the permanent tissue were hydrolysed in large proportion
+by the acid, whereas in the matured straw the hydrolysis is chiefly
+confined to the furfuroids. In the early stages also the permanent
+tissue yields an extract with relatively low cupric reduction, showing
+that the carbohydrates are dissolved by the acid in a more complex
+molecular condition.</p>
+
+<p>These observations confirm the view that the furfuroids take origin in a
+hexose-pentose series of transformations. The proportion of furfuroid
+groups to total carbohydrates varies but little, viz. from 1/3 in the
+early stages to a maximum of 1/4 at the flowering period. At this period
+the differentiation of the groups begins to be marked.</p>
+
+<p>Taking all the facts of (1) and (2), they are not inconsistent with the
+hypothesis of an internal transformation of a hexose to a
+pentose-monoformal. Such a change of position and function of oxygen
+from OH to CO within the group &mdash;CH.OH&mdash; is a species of internal
+oxidation which reverses the reduction of formaldehyde groups in
+synthesising to sugars, and appears therefore of probable occurrence.</p>
+
+<p>These constitutional problems are followed up in (3) by the<span class='pagenum'><a name="Page_108" id="Page_108">[Pg 108]</a></span> indirect
+method of differentiating the relationships of these furfuroids to yeast
+fermentation, from those of the pentoses. Straw and esparto celluloses
+are subjected to the processes of acid hydrolysis, and the neutralised
+extracts fermented. With high furfural numbers indicating that the
+furfuroids are the chief constituents of the extract, there is an active
+fermentation with production of alcohol. The cupric reduction falls in
+greater ratio to the original (unfermented) than the furfural.
+Observations on the pure pentoses&mdash;xylose and arabinose added to
+dextrose solutions, and then exposed to yeast action&mdash;show that in a
+vigorous fermentation not unduly prolonged the pentoses are unaffected,
+but that they do come within the influence of the yeast-cell when the
+latter is in a less vigorous condition, and when the hexoses are not
+present in relatively large proportion.</p>
+
+<p>(4) The observations on the growing plant were resumed with the view of
+artificially increasing the differentiation of the two main groups of
+carbohydrates. From a portion of a barley crop the inflorescence was
+removed as soon as it appeared. The crop was allowed to mature, and a
+full comparison instituted between the products of normal and abnormal
+growth. With a considerable difference in 'permanent tissue' (13 p.ct.
+less) and a still greater defect in cellulose (24 p.ct.), the constants
+for the furfuroids in relation to total carbohydrates were unaffected by
+the arrested development. This was also true of the behaviour of the
+hydrolysed extracts (acid processes) to yeast fermentation.</p>
+
+<p>(5) The extract obtained from the brewers' grains by the process
+described in (2) was investigated in relation to animal digestion. It
+has been now generally established that the furfuroids as constituents
+of fodder plants are digested and assimilated in large proportion in
+passing through animal digestive tracts, and in this respect behave
+differently from the pentoses. The furfuroids being obtained, as
+described, in<span class='pagenum'><a name="Page_109" id="Page_109">[Pg 109]</a></span> a fully hydrolysed condition (monoses) the digestion
+problem presented itself in a new aspect, and was therefore attacked.</p>
+
+<p>The result of the comparative feeding experiments upon rabbits was to
+show that in this previously hydrolysed form the furfuroids are almost
+entirely digested and assimilated, no pentoses, moreover, appearing in
+the urine.</p>
+
+<p>Generally we may sum up the present solution of the problem of the
+relationship of the furfuroids to plant assimilation and growth as
+follows:&mdash;The pentoses are not produced as such in the process of
+assimilation; but furfural-yielding carbohydrates are produced directly
+and in approximately constant ratio to the total carbohydrates; they are
+mainly located in the permanent tissue; in the secondary changes of
+dehydration, &amp;c., accompanying maturation they undergo such
+differentiation that they become readily separable by processes of acid
+hydrolysis from the more resistant normal celluloses; but in relation to
+alkaline treatments they maintain their intimate union with the latter.
+They are finally converted into pentoses by artificial treatments, and
+into pentosanes in the plant, with loss of 1 C atom in an oxidised form.
+The mechanism of this transformation of hexoses into pentoses is not
+cleared up. It is independent of external conditions, <i>e.g.</i>
+fertilisation and atmospheric oxidations, and is probably therefore a
+process of internal rearrangement of the character of an oxidation.</p>
+
+
+<h3>ZUR KENNTNISS DER IN DEN MEMBRANEN DER PILZE ENTHALTENEN BESTANDTHEILE.</h3>
+
+<h4><span class="smcap">E. Winterstein</span> (Ztschr. Physiol. Chem., 1894, 521; 1895, 134).</h4>
+
+<h3><b>ON THE CONSTITUENTS OF THE TISSUE OF FUNGI.</b></h3>
+
+<p>(p. 87) These two communications are a contribution of fundamental
+importance, and may be regarded as placing the<span class='pagenum'><a name="Page_110" id="Page_110">[Pg 110]</a></span> question of the
+composition of the celluloses of these lowest types on a basis of
+well-defined fact. In the first place the author gives an exhaustive
+bibliography, beginning with the researches of Braconnot (1811), who
+regarded the cellular tissue of these organisms as a specialised
+substance, which he termed 'fungin.' Payen rejects this view, and
+regards the tissue, fully purified by the action of solvents, as a
+cellulose (C<sub>6</sub>H<sub>10</sub>O<sub>5</sub>). This view is successively supported by
+Fromberg [Mulder, Allg. Phys. Chem., Braunschweig, 1851], Schlossberger
+and Doepping [Annalen, 52, 106], and Kaiser. De Bary, on a review of the
+evidence, adopts this view, but, as the purified substance fails to give
+the characteristic colour-reactions with iodine, he uses the qualifying
+term 'pilzcellulose' [Morph. u. Biol. d. Pilze u. Flechten, Leipzig,
+1884].</p>
+
+<p>C. Richter, on the other hand, shows that these reactions are merely a
+question of methods of purification or preparation [Sitzungsber. Acad.
+Wien, 82, 1, 494], and considers that the tissue-substance is an
+ordinary cellulose, with the ordinary reactions masked by the presence
+of impurities. In regard to the lower types of fungoid growth, such as
+yeast, the results of investigators are more at variance. The researches
+of Salkowski (p. 113) leave little doubt, however, that the
+cell-membrane is of the cellulosic type.</p>
+
+<p>The author's researches extend over a typical range of products obtained
+from <i>Boletus edulis, Agaricus campestris, Cantharellus cibarius,
+Morchella esculenta, Polyporus officinalis, Penicillium glaucum</i>, and
+certain undetermined species. The method of purification consisted
+mainly in (<i>a</i>) exhaustive treatments with ether and boiling alcohol,
+(<i>b</i>) digestion with alkaline hydrate (1-2 p.ct. NaOH) in the cold,
+(<i>c</i>) acid hydrolysis (2-3 p.ct. H<sub>2</sub>SO<sub>4</sub>) at 95&deg;-100&deg;, followed by a
+chloroxidation treatment by the processes of Schulze or Hoffmeister, and
+final alkaline hydrolysis.<span class='pagenum'><a name="Page_111" id="Page_111">[Pg 111]</a></span></p>
+
+<p>The products, i.e. residues, thus obtained were different in essential
+points from the celluloses isolated from the tissues of phanerogams
+similarly treated. Only in exceptional cases do they give blue reactions
+with iodine in presence of zinc chloride or sulphuric acid. The
+colourations are brown to red. They resist the action of cuprammonium
+solutions. They are for the most part soluble in alkaline hydrate
+solution (5-10 p.ct. NaOH) in the cold. They give small yields (1-2
+p.ct.) of furfural on boiling with 10 p.ct. HCl.Aq.</p>
+
+<p>Elementary analyses gave the following results, which are important in
+establishing the presence of a notable proportion of nitrogen, which has
+certainly been overlooked by the earlier observers:&mdash;</p>
+
+
+<div class='center'>
+<table border="1" cellpadding="4" cellspacing="0" summary="">
+<tr><td align='left'>'Cellulose' or residue from</td><td align='left'> C</td><td align='left'> H</td><td align='left'> N</td></tr>
+<tr><td align='left'>Boletus edulis (Schulze process)</td><td align='left'> 42.4</td><td align='left'> 6.5</td><td align='left'> 3.9</td></tr>
+<tr><td align='left'>Boletus edulis (Hoffmeister process)</td><td align='left'> 44.6</td><td align='left'> 6.3</td><td align='left'> 3.6</td></tr>
+<tr><td align='left'>Polyporus off.</td><td align='left'> 43.7</td><td align='left'> 6.5</td><td align='left'> 0.7</td></tr>
+<tr><td align='left'>Cantharellus cib.</td><td align='left'> 44.9</td><td align='left'> 6.8</td><td align='left'> 3.0</td></tr>
+<tr><td align='left'>Agaricus campestris</td><td align='left'> 44.3</td><td align='left'> 6.6</td><td align='left'> 3.6</td></tr>
+<tr><td align='left'>Botrytis</td><td align='left'> 42.1</td><td align='left'> 6.3</td><td align='left'> 3.9</td></tr>
+<tr><td align='left'>Penicillium glaucum</td><td align='left'> &mdash;</td><td align='left'> &mdash;</td><td align='left'> 3.3</td></tr>
+<tr><td align='left'>Morchella esculenta</td><td align='left'> &mdash;</td><td align='left'> &mdash;</td><td align='left'> 2.5</td></tr>
+</table></div>
+
+<p>It is next shown that this residual nitrogen is not in the form of
+residual proteids (1) by direct tests, all of which gave negative
+results, and (2) indirectly by the high degree of resistance to both
+alkaline and acid hydrolysis. The 'celluloses' are attacked by boiling
+dilute acids (1 p.ct. H<sub>2</sub>SO<sub>4</sub>), losing in weight from 10 to 23
+p.ct., the dissolved products having a cupric reduction value about 50
+p.ct. that of an equal weight of dextrose. As an extreme hydrolytic
+treatment the products were dissolved in 70 p.ct. H<sub>2</sub>SO<sub>4</sub>, allowed
+to stand 24 hours, then considerably diluted (to 3 p.ct. H<sub>2</sub>SO<sub>4</sub>)
+and boiled to<span class='pagenum'><a name="Page_112" id="Page_112">[Pg 112]</a></span> complete the inversion. The yields of glucose, calculated
+from the cupric reduction, were as follows:&mdash;</p>
+
+
+<div class='center'>
+<table border="0" cellpadding="4" cellspacing="0" summary="">
+<tr><td align='left'>Boletus edulis</td><td align='left'>65.2</td><td align='left'>p.ct.</td></tr>
+<tr><td align='left'>Polyporus off.</td><td align='left'>94.7</td><td align='center'>"</td></tr>
+<tr><td align='left'>Agaricus campestris</td><td align='left'>59.1</td><td align='center'>"</td></tr>
+<tr><td align='left'>Morchella esculenta</td><td align='left'>60.1</td><td align='center'>"</td></tr>
+<tr><td align='left'>Cantharellus cib.</td><td align='left'>64.9</td><td align='center'>"</td></tr>
+<tr><td align='left'>Botrytis</td><td align='left'>60.8</td><td align='center'>"</td></tr>
+</table></div>
+
+<p>It will be noted that the exceptionally high yield from the Polyporus
+cellulose is correlated with its exceptionally low nitrogen. By actual
+isolation of a crystalline dextrorotary sugar, by preparations of
+osazone and conversion into saccharic acid, it was proved that dextrose
+was the main product of hydrolysis. The second main product was shown to
+be acetic acid, the yield of which amounted to 8 p.ct. in several cases.</p>
+
+<p>Generally, therefore, it is proved that the more resistant tissue
+constituents of the fungi are not cellulose, but a complex of
+carbohydrates and nitrogenous groups in combination, the former being
+resolved into glucoses by acid hydrolysis, and the latter yielding
+acetic acid as a characteristic product of resolution together with the
+nitrogenous groups in the form of an uncrystallisable syrup.</p>
+
+<p>In the further prosecution of these investigations (2) the author
+proceeded from the supposition of the identity of the nitrogenous
+complex of the original with chitin, and adopted the method of
+Ledderhose (Ztschr. Physiol. Chem. 2, 213) for the isolation of
+glucosamin hydrochloride, which he succeeded in obtaining in the
+crystalline form. In the meantime E. Gilson had shown that these tissue
+substances in 'fusion' with alkaline hydrates yield a residue of a
+nitrogenous product (C<sub>14</sub>H<sub>28</sub>N<sub>2</sub>O<sub>10</sub>), which is soluble in
+dilute acids [Recherches Chim. sur la Membrane Cellulaire des
+Champignons,<span class='pagenum'><a name="Page_113" id="Page_113">[Pg 113]</a></span> La Cellule, v. II, pt. 1]. This residue, which was termed
+mycosin by Gilson, has been similarly isolated by the author. It is
+proved, therefore, that the tissues of the fungi do contain a product
+resembling chitin. [See also Gilson, Compt. Rend. 120, 1000.] This
+constituent is in intimate union with the carbohydrate complex, which is
+resolved similarly to the hemicelluloses. Various intermediate terms of
+the hydrolytic series have been isolated. But the only fully identified
+product of resolution is the dextrose which finally results.</p>
+
+
+<h3>UEBER DIE KOHLENHYDRATE D. HEFE.</h3>
+
+<h4><span class="smcap">E. Salkowski</span> (Berl. Ber., 27, 3325).</h4>
+
+<h3>ON THE CARBOHYDRATES OF YEAST.</h3>
+
+<p>The author has isolated the more resistant constituents of the
+cell-membrane by boiling with dilute alkalis, and exhaustively purifying
+with alcohol and ether.</p>
+
+<p>The residue was only a small percentage (3-4 p.ct) of the original, and
+retained only 0.45 p.ct. N.</p>
+
+<p>It was heated in a digester with water at 2-3 atm. steam-pressure, and
+thus resolved into approximately equal portions of soluble cellulose
+(<i>a</i>) and insoluble (<i>b</i>). The latter, giving no colour-reaction with
+iodine, is termed achroocellulose; the former reacts, and is therefore
+termed erythrocellulose. The former is easily separated from its
+opalescent solution. It has the empirical composition of cellulose. In
+the soluble form it resembles glycogen. The achroocellulose is isolated
+in the form of horny or agglomerated masses. It appears to be resolved
+by ultimate hydrolysis into dextrose and mannose.</p>
+
+
+
+<hr style="width: 65%;" />
+<p><span class='pagenum'><a name="Page_114" id="Page_114">[Pg 114]</a></span></p>
+<h2>SECTION V. FURFUROIDS, <i>i.e.</i> PENTOSANES AND FURFURAL-YIELDING
+CONSTITUENTS GENERALLY</h2>
+
+
+<h3>(1) Reactions of the Carbohydrates with Hydrogen Peroxide.</h3>
+
+<h4><span class="smcap">C. F. Cross, E. J. Bevan,</span> and <span class="smcap">Claud Smith</span> (J. Chem. Soc., 1898, 463).
+</h4>
+
+<h3>(2) Action of Hydrogen Peroxide on Carbohydrates in the Presence of
+Ferrous Salts.</h3>
+
+<h4><span class="smcap">R. S. Morrell</span> and <span class="smcap">J. M. Crofts</span> (J. Chem. Soc., 1899, 786).</h4>
+
+
+<h3>(3) <b>Oxidation of Furfuraldehyde by Hydrogen Peroxide.</b></h3>
+
+<h4><span class="smcap">C. F. Cross, E. J. Bevan,</span> and <span class="smcap">T. Heiberg</span> (J. Ch. Soc., 1899, 747).</h4>
+
+
+<h3>(4) EINWIRKUNG VON WASSERSTOFFHYPEROXID AUF UNGES&Auml;TTIGTE
+KOHLENWASSERSTOFFE.</h3>
+
+<h4><span class="smcap">C. F. Cross, E. J. Bevan</span>, and <span class="smcap">T. Heiberg</span> (Berl. Ber., 1900, 2015).</h4>
+
+<h3><b>ACTION OF HYDROGEN PEROXIDE ON UNSATURATED HYDROCARBONS.</b></h3>
+
+<p>The above series of researches grew out of the observations incidental
+to the use of the peroxide on an oxidising agent in investigating the
+hydrolysed furfuroids (102). Certain remarkable observations had
+previously been made by H. J. H. Fenton (Ch. Soc. J., 1894, 899; 1895,
+774; 1896, 546) on the oxidation of tartaric acid by the peroxide,
+acting in presence of ferrous salts, the &mdash;CHOH&mdash;CHOH&mdash; residue losing
+H<sub>2</sub> with production of the unsaturated group,<br /> &mdash;OH.C=C.OH&mdash;. These
+investigations have subsequently been considerably developed and
+generalised by Fenton, but as the results have no<span class='pagenum'><a name="Page_115" id="Page_115">[Pg 115]</a></span> immediate bearing on
+our main subject we must refer readers to the J. Chem. Soc., 1896-1900.</p>
+
+<p>From the mode of action diagnosed by Fenton it was to be expected that
+the CHOH groups of the carbohydrates would be oxidised to CO groups, and
+it has been established by the above investigations (1) and (2) that the
+particular group to be so affected in the hexoses is that contiguous to
+the typical</p>
+
+<p>
+<span style="margin-left: 4em;">|</span><br />
+<span style="margin-left: 2.5em;">&mdash;CO</span><br />
+</p>
+
+<p>group. There results, therefore, a dicarbonyl derivative ('osone'),
+which reacts directly with 2 mol. phenyl hydrazine in the cold to form
+an osazone. This was directly established for glucose, l&aelig;vulose,
+galactose, and arabinose (2). While this is the main result, the general
+study of the product shows that the oxidation is not simple nor in
+direct quantitative relationship to the H<sub>2</sub>O<sub>2</sub> employed. The
+molecular proportion of the aldoses affected appears to be in
+considerable excess, and the reaction is probably complicated by
+interior rearrangement.</p>
+
+<p>In the main, the original aldehydic group resists the oxidation. But a
+certain proportion of acid products are formed, probably tartronic acid.
+On distillation with condensing acids a large proportion of volatile
+monobasic acids (chiefly formic) are obtained. The proportion of
+furfural obtained amounts to 3-4 per cent. of the weight of the original
+carbohydrate.</p>
+
+<p>Since the general result of these oxidations is the substitution of an
+OH group for an H atom, it was of interest to determine the behaviour of
+furfural with the peroxide. The oxidation was carried out in dilute
+aqueous solution of the aldehyde at 20&deg;-40&deg;, using 2-3 mols. H<sub>2</sub>O<sub>2</sub>
+per 1 mol. C<sub>5</sub>H<sub>4</sub>O<sub>2</sub>. The main product is a hydroxyfurfural, which
+was separated as a hydrazone. A small quantity of a monobasic acid was
+formed, which was identified as a hydroxypyromucic acid. Both aldehyde
+and acid appear to be the &#945; &#946; derivatives. The<span class='pagenum'><a name="Page_116" id="Page_116">[Pg 116]</a></span> aldehyde gives
+very characteristic colour reactions with phloroglucinol and resorcinol
+in presence of hydrochloric acid, which so closely resemble those of the
+lignocelluloses that there is little doubt that these particular
+reactions must be referred to the presence of the hydroxyfurfural as a
+normal constituent.</p>
+
+<p>The study of these oxidations was then extended to typical unsaturated
+hydrocarbons&mdash;viz. acetylene and benzene. (4) From the former the main
+product was acetic acid, but the attendant formation of traces of ethyl
+alcohol indicates that the hydrogen of the peroxide may take a direct
+part in this and other reactions. This view receives some support from
+the fact that the interaction of the H<sub>2</sub>O<sub>2</sub> with permanganates has
+now been established to be an oxidation of the H<sub>2</sub> of the peroxide by
+the permanganate oxidation, with liberation, therefore, of the O<sub>2</sub> of
+the peroxide as an unresolved molecule [Baeyer].</p>
+
+<p>Benzene itself is also powerfully attacked by the peroxide when shaken
+with a dilute solution in presence of iron salts. The products are
+phenol and pyrocatechol, with some quantity of an amorphous product
+probably formed by condensation of a quinone with the phenolic products
+of reaction.</p>
+
+<hr style='width: 45%;' />
+
+<p>These types of oxidation effects now established give a definite
+significance to the physiological functions of the peroxide, which is a
+form of 'active oxygen' of extremely wide distribution. It would have
+been difficult <i>a priori</i> to devise an oxidant without sensible action
+on aldehydic groups, yet delivering a powerful attack on hydrocarbon
+rings; or to have suggested a synthesis of the sugars from tartaric acid
+with a powerful oxidising treatment as the first and essential stage in
+the transformation.</p>
+
+<p>Our present knowledge of such actions and effects suggests<span class='pagenum'><a name="Page_117" id="Page_117">[Pg 117]</a></span> a number of
+new clues to genetic relationships of carbon compounds within the plant.
+The conclusion is certainly justified that the origin of the pentoses is
+referable to oxidations of the hexoses, in which this form of 'active
+oxygen' plays an important part.</p>
+
+<p>We must note here the researches of O. Ruff, who has applied these
+oxidations with important results in the systematic investigation of the
+carbohydrates.</p>
+
+
+<h3>UEBER DIE VERWANDLUNG DER <i>D</i>-GLUCONS&Auml;URE IN <i>D</i>-ARABINOSE (Berl. Ber.,
+1898, 1573).</h3>
+
+<h3><b>CONVERSION OF <i>D</i>-GLUCONIC ACID INTO <i>D</i>-ARABINOSE.</b></h3>
+
+<hr style='width: 45%;' />
+
+<h3><i>D</i> UND <i>L</i> ARABINOSE (<i>Ibid.</i> 1899, 550).</h3>
+
+<hr style='width: 45%;' />
+
+<h3>ZUR KENNTNISS DER OXYGLUCONS&Auml;URE (<i>Ibid.</i> 1899, 2269).</h3>
+
+<h3><b>ON OXYGLUCONIC ACID.</b></h3>
+
+<p>Ruff in these researches has realised a simple and direct transition
+from the hexoses to the pentoses. By oxidising gluconic acid with the
+peroxide the &#946; &mdash;CHOH&mdash; group is converted into carbonyl at the same
+time that the terminal COOH [&#945;] is oxidised to CO<sub>2</sub>. The yields of
+the resulting pentose are large. Simultaneously there is formed an
+oxygluconic acid, which appears to be a ketonic acid of formula
+&mdash;CH<sub>2</sub>OH.CO.(CHOH)<sub>3</sub>.COOH&mdash;.</p>
+
+<p>From these results we see a further range of physiological
+probabilities; and with the concurrent actions of oxygen in the forms of
+or related to hydrogen peroxide on the one side, and ozone on the other,
+we are able to account in a simple way for the relationships of the
+'furfuroid' group, which may<span class='pagenum'><a name="Page_118" id="Page_118">[Pg 118]</a></span> include a number of intermediate terms in
+the hexose-pentose series.</p>
+
+<p>Following in this direction of development of the subject is a study of
+the action of persulphuric acid upon furfural.</p>
+
+
+<h3>EINWIRKUNG DES CARO'SCHEN REAGENS AUF FURFURAL.</h3>
+
+<h4><span class="smcap">C. F. Cross, E. J. Bevan</span>, and <span class="smcap">J. F. Briggs</span> (Berl. Ber., 1900, 3132).</h4>
+
+<p>Regarding this reagent as another form of 'active oxygen,' it is
+important to contrast its actions with those of the hydrogen peroxide.
+Instead of the &#946;-hydroxyfurfural (<i>ante</i>, 115) we obtain the
+&#948;-aldehyde as the first product. The aldehydic group is then
+oxidised, and as a result of attendant hydrolysis the ring is broken
+down and succinic acid is formed, the original aldehydic group of the
+furfural being split off in the form of formic acid. The reactions take
+place at the ordinary temperature and with the dilute form of the
+reagent described by Baeyer and Villiger (Ber. 32, 3625). These results
+have some special features of interest. The &#945; &#948;-hydroxyfurfural
+has similar colour reactions to those of the &#945; &#946;-derivative, and
+may also therefore be present as a constituent of the lignocelluloses.
+The tendency to attack in the 1&middot;4 position in relation to an aldehydic
+group further widens the capabilities of 'active oxygen' in the plant
+cell. Lastly, this is the simplest transition yet disclosed from the
+succinyl to furfural grouping, being effected by a regulated proportion
+of oxygen, and under conditions of reaction which may be described as of
+the mildest. In regard to the wide-reaching functions of asparagin in
+plant life, we have a new suggestion of genetic connections with the
+furfuroids.<span class='pagenum'><a name="Page_119" id="Page_119">[Pg 119]</a></span></p>
+
+
+<h3>VERGLEICH DER PENTOSEN-BESTIMMUNGSMETHODEN VERMITTELST PHENYLHYDRAZIN
+UND PHLOROGLUCIN.</h3>
+
+<h4><span class="smcap">M. Kr&uuml;ger</span> (Inaug.-Diss., G&ouml;ttingen, 1895).</h4>
+
+<h3><b>COMPARISON OF METHODS OF ESTIMATING FURFURAL AS HYDRAZONE AND
+PHLOROGLUCIDE.</b></h3>
+
+<p>The author traces the development of processes of estimating furfural
+(1) by precipitation with ammonia (furfuramide), (2) by volumetric
+estimation with standardised phenylhydrazine, (3) by weighing the
+hydrazone.</p>
+
+<p>In 1893 (Chem. Ztg. 17, 1745) Hotter described a method of quantitative
+condensation with pyrogallol requiring a temperature of 100&deg;-110&deg; for
+two hours. The insoluble product collected, washed, dried at 103&deg;, and
+weighed, gives a weight of 1.974 grm. per 1 grm. furfural.</p>
+
+<p>Councler substitutes phloroglucinol for pyrogallol, with the advantage
+of doing away with the digestion at high temperature. (<i>Ibid.</i> 18, 966.)
+This process, requiring the presence of strong HCl, has the advantage of
+being applied directly to the acid distillate, in which form furfural is
+obtained as a product of condensation of pentoses, &amp;c. A comparative
+investigation was made, precipitating furfural (<i>a</i>) as hydrazone in
+presence of acetic acid, and (<i>b</i>) as phloroglucide in presence of HCl
+(12 p.ct). In (<i>a</i>) by varying the weights of known quantities of
+furfural, and using the factor, hydrazone &times; 0.516 [+ 0.0104] in
+calculating from the weights of precipitates obtained, the maximum
+variations from the theoretical number were +1.71 and -1.74. In (<i>b</i>) it
+was found necessary to vary the factor from 0.52 to 0.55 in calculating
+from phloroglucide to furfural. The greatest <i>total</i> range of variation
+was found to be 2.5 p.ct. The phenol process is therefore equally
+accurate, has the advantages above noted, and, in<span class='pagenum'><a name="Page_120" id="Page_120">[Pg 120]</a></span> addition, is less
+liable to error from the pressure in the distillates obtained from
+vegetable substances of volatile products, e.g. ketonic compounds,
+accompanying the furfural.</p>
+
+<p>This method has been criticised by Helbel and Zeisel [Sitz.-ber, Wiener
+Akad. 1895, 104, ii. p. 335] on two grounds of error, viz. (1) the
+presence of diresorcinol in all ordinary preparations of phloroglucinol,
+and (2) changes in weight of the precipitate of phloroglucide on drying.
+The process was carried out comparatively with ordinary preparations,
+and with specially pure preparations of the phenol. The quantitative
+results were identical. The criticisms in question are therefore
+dismissed. Although the process is to be recommended for its simplicity
+and the satisfactory concordance of results it is to be noted that it
+rests upon an empirical basis, since the phloroglucide is not formed by
+the simple reaction 2 [C<sub>5</sub>H<sub>4</sub>O<sub>2</sub> + C<sub>6</sub>H<sub>6</sub>O<sub>3</sub>] - H<sub>2</sub>O =
+C<sub>22</sub>H<sub>18</sub>O<sub>9</sub>, but appears to have the composition
+C<sub>16</sub>H<sub>12</sub>O<sub>6</sub>.</p>
+
+<p>In part ii. of this paper the author discusses the question of the
+probable extent in the sense of diversity of constitution of
+furfural-yielding constituents of plant-tissues. Glucoson was isolated
+from glucosazon, and found to yield 2.9-3.6 p.ct. furfural. Gluconic
+acid distilled with hydrochloric acid gave traces of furfural; so also
+with sulphuric acid and manganic oxide.</p>
+
+<p>Starch was oxidised with permanganate, and a mixture of products
+obtained of which one gave a characteristic violet colouration with
+phloroglucol, with an absorption-band at the D line. On distilling with
+HCl furfural was obtained in some quantity. The product in question was
+found to be very sensitive to the action of bases, and was destroyed by
+the incidental operation of neutralising the mixture of oxidised
+products with calcium carbonate. It was found impossible to isolate the
+compound.<span class='pagenum'><a name="Page_121" id="Page_121">[Pg 121]</a></span></p>
+
+
+<h3>UNTERSUCHUNGEN UEBER DIE PENTOSANBESTIMMUNG MITTELST DER
+SALZS&Auml;URE-PHLORO-GLUCIN-METHODE.<a name="FNanchor_8_8" id="FNanchor_8_8"></a><a href="#Footnote_8_8" class="fnanchor">[8]</a></h3>
+
+<h4><span class="smcap">E. Kr&ouml;ber</span> (Journ. f. Landwirthschaft, 1901, 357).</h4>
+
+<h3><b>INVESTIGATION OF THE HYDROCHLORIC ACID-PHLOROGLUCINOL METHOD OF
+DETERMINING PENTOSANES.</b></h3>
+
+<p>This paper is the most complete investigation yet published of the now
+well-known method of precipitating and estimating furfural in acid
+solution by means of the trihydric phenol. In the last section of the
+paper is contained the most important result, the proof that the
+insoluble phloroglucide is formed according to the reaction</p>
+
+<p>
+<span style="margin-left: 2.5em;">C<sub>5</sub>H<sub>4</sub>O<sub>2</sub> + C<sub>6</sub>H<sub>6</sub>O<sub>3</sub> - 2H<sub>2</sub>O = C<sub>11</sub>H<sub>6</sub>O<sub>3</sub>,</span><br />
+</p>
+
+<p>also, by varying the proportions of the pure reagents interacting, that
+the condensation takes place invariably according to this equation.</p>
+
+<p>Incidentally the following points were also established:&mdash;The solubility
+of the phloroglucide, under the conditions of finally separating in a
+condition for drying and weighing, is 1 mgr. per 100 c.c. of total
+solution, made up of the original acid solution, in which the
+precipitation takes place, and the wash-water required to purify from
+the acid. The phloroglucide is hygroscopic, and must be weighed out of
+contact with the air. The presence of diresorcinol is without influence
+on the result, provided a sufficient excess of actual phloroglucinol is
+employed. Thus even with a preparation containing 30 p.ct. of its weight
+of diresorcinol the influence of the latter is eliminated, provided a
+weight be taken equal to twice that of the furfural to be precipitated.
+The phenol must be perfectly dissolved by warming with dilute HCl (1.06
+sp.gr.) before adding to the furfural<span class='pagenum'><a name="Page_122" id="Page_122">[Pg 122]</a></span> solution. For collecting the
+precipitate of phloroglucide the author employs the Gooch crucible.</p>
+
+<p>The paper contains a large number of quantitative results in proof of
+the various points established, and concludes with elaborate tables,
+giving the equivalents in the known pentoses and their anhydrides for
+any given weight of phloroglucide from 0.050 to 0.300 grm.</p>
+
+
+<h3>UEBER DEN PENTOSAN-GEHALT VERSCHIEDENER MATERIALIEN.</h3>
+
+<h4><span class="smcap">B. Tollens</span> and <span class="smcap">H. Glaubitz</span> (J. f&uuml;r Landwirthschaft, 1897, 97).</h4>
+
+<h3><b>ON THE PENTOSANE CONSTITUENTS OF FODDER-PLANTS AND MALT.</b></h3>
+
+<p>(p. 171) (<i>a</i>) The authors have re-determined the yield of furfural from
+a large range of plant-products, using the phloroglucol method. The
+numbers approximate closely to those obtained by the hydrazone method.
+The following may be cited as typical:</p>
+
+
+<div class='center'>
+<table border="0" cellpadding="4" cellspacing="0" summary="">
+<tr><td align='left'>Substance</td><td align='left'>Furfural p.ct.</td></tr>
+<tr><td align='left'>Rye (G&ouml;ttingen)</td><td align='left'>6.03</td></tr>
+<tr><td align='left'>Wheat (square head)</td><td align='left'>4.75</td></tr>
+<tr><td align='left'>Barley (peacock)</td><td align='left'>4.33</td></tr>
+<tr><td align='left'>Oats (G&ouml;ttingen)</td><td align='left'>7.72</td></tr>
+<tr><td align='left'>Maize (American)</td><td align='left'>3.17</td></tr>
+<tr><td align='left'>Meadow hay</td><td align='left'>11.63</td></tr>
+<tr><td align='left'>Bran (wheat)</td><td align='left'>13.06</td></tr>
+<tr><td align='left'>Malt</td><td align='left'>6.07</td></tr>
+<tr><td align='left'>Malt-sprouts</td><td align='left'>8.56</td></tr>
+<tr><td align='left'>Sugar-beet (exhausted)</td><td align='left'>14.95</td></tr>
+</table></div>
+
+<p>(<i>b</i>) A comparison of wheat with wheat bran, &amp;c. was made by grinding in
+a mortar and 'bolting' the flour through a fine silk sieve. The results
+showed:</p>
+
+
+<div class='center'>
+<table border="0" cellpadding="4" cellspacing="0" summary="">
+<tr><td align='left'></td><td align='left'>Furfural p.ct.</td></tr>
+<tr><td align='left'>Original wheat</td><td align='left'>4.75</td></tr>
+<tr><td align='left'>Fine flour</td><td align='left'>1.73</td></tr>
+<tr><td align='left'>Bran (24 p.ct. of wheat)</td><td align='left'>11.25</td></tr>
+<tr><td align='left'>Wheat-bran of commerce</td><td align='left'>13.06</td></tr>
+</table></div>
+
+
+<p><span class='pagenum'><a name="Page_123" id="Page_123">[Pg 123]</a></span></p>
+
+<p>It is evident that the pentosanes of wheat are localised in the more
+resistant tissues of the grain.</p>
+
+<p>(<i>c</i>) An investigation of the products obtained in the analytical
+process for 'crude fibre' gave the following:</p>
+
+<p>(1) In the case of brewers' grains:</p>
+
+
+
+<div class='center'>
+<table border="0" cellpadding="4" cellspacing="0" summary="">
+<tr><td align='left'>100 grms. grains</td><td align='left'>gave furfural</td><td align='left'>=</td><td align='right'>29.43</td><td align='left'> pentosane</td></tr>
+<tr><td align='left'></td><td align='left'></td><td align='left'></td><td colspan="2">&mdash;&mdash;&mdash;&mdash;&mdash;&mdash;&mdash;</td></tr>
+<tr><td align='left'> 20 &nbsp;&nbsp;" crude fibre</td><td align='center'>"</td><td align='left'>=</td><td align='right'>2.52</td></tr>
+<tr><td align='left'>Acid extract</td><td align='center'>"</td><td align='left'>=</td><td align='right'> 22.76</td></tr>
+<tr><td align='left'>Alkali &nbsp;&nbsp;"</td><td align='center'>"</td><td align='left'>=</td><td align='right'>1.20</td></tr>
+<tr><td align='left'>Deficiency from</td><td align='left'>total of original grains</td><td align='left'></td><td align='right'>2.95</td></tr>
+<tr><td align='left'></td><td align='left'></td><td align='left'></td><td align='left'>&mdash;&mdash;&mdash;</td></tr>
+<tr><td align='left'></td><td align='left'></td><td align='left'></td><td align='right'>29.43</td></tr>
+</table></div>
+
+
+<p>(2) In the case of meadow hay:</p>
+
+<p>The crude fibre (30 p.ct.) obtained retained about one fourth (23.63
+p.ct.) of the total original pentosanes.</p>
+
+<p>(<i>d</i>) An investigation of barley-malt, malt-extract or wort, and
+finished beer showed the following: An increase of furfuroids in the
+process of malting, 100 pts. barley with 7.97 of 'pentosane' yielding 82
+of malt with 11.18 p.ct. 'pentosane'; confirming the observations of
+Cross and Bevan (Ber. 28, 2604). Of the total furfuroids of malt about
+1/4 are dissolved in the mashing process. In a fermentation for lager
+beer it was found that about /10 of the total furfuroids of the malt
+finally survive in the beer; the yield of furfural being 2.92 p.ct. of
+the 'total solids' of the beer. In a 'Schlempe' or 'pot ale,' from a
+distillery using to 1 part malt 4 parts raw grain (rye), yield of
+furfural was 9 p.ct. of the total solids.</p>
+
+<p>In a general review of the relationships of this group of plant-products
+it is pointed out that they are largely digested by animals, and
+probably have an equal 'assimilation' value to starch. They resist
+alcoholic fermentation, and must consequently be taken into account as
+constituents of beers and wines.<span class='pagenum'><a name="Page_124" id="Page_124">[Pg 124]</a></span></p>
+
+
+<h3>UEBER DAS VERHALTEN DER PENTOSANE DER SAMEN BEIM KEIMEN.<a name="FNanchor_9_9" id="FNanchor_9_9"></a><a href="#Footnote_9_9" class="fnanchor">[9]</a></h3>
+
+<h4><span class="smcap">A. Sch&ouml;ne</span> and <span class="smcap">B. Tollens</span> (Jour. f. Landwirthschaft, 1901, 349).</h4>
+
+<h3><b>BEHAVIOUR OF PENTOSANES OF SEEDS IN GERMINATION.</b></h3>
+
+<p>The authors have investigated the germination of barley, wheat, and
+peas, in absence of light, and generally with exclusion of assimilating
+activity, to determine whether the oxidation with attendant loss of
+weight, which is the main chemical feature of the germination proper,
+affects the pentosanes of the seeds. The following are typical of the
+quantitative results obtained, which are stated in absolute weights, and
+not percentages.</p>
+
+
+<div class='center'>
+<table border="1" cellpadding="4" cellspacing="0" summary="">
+<tr><td align='left'>--</td><td align='left'> Original seed</td><td align='left'> Malt or germinated product</td><td colspan="2"> Pentosane in</td></tr>
+<tr><td align='left'>&nbsp;</td><td align='center'> A</td><td align='center'> B</td><td align='center'> A</td><td align='center'> B</td></tr>
+<tr><td align='left'>Barley</td><td align='center'> 500.00</td><td align='center'> 434.88</td><td align='center'> 39.58</td><td align='center'> 40.38</td></tr>
+<tr><td align='center'>"</td><td align='center'> 500.00</td><td align='center'> 442.26</td><td align='center'> 40.52</td><td align='center'> 41.17</td></tr>
+<tr><td align='left'>Peas</td><td align='center'> 300.00</td><td align='center'> 286.60</td><td align='center'> 15.25</td><td align='center'> 15.97</td></tr>
+</table></div>
+
+<p>The authors conclude generally that there is a slight absolute increase
+in the pentosanes, and that the pentosanes do not belong to those
+reserve materials which undergo destructive oxidation during
+germination.</p>
+
+<p>In this they confirm the previously published results of De Chalmot,
+Cross and Bevan, and Gotze and Pfeiffer.</p>
+
+
+<h3>UEBER DEN GEHALT DER BAUMWOLLE AN PENTOSAN.</h3>
+
+<h4><span class="smcap">H. Suringar</span> and <span class="smcap">B. Tollens</span> (Ztschr. angew. Chem., 1897, I).</h4>
+
+<h3><b>PENTOSANE CONSTITUENTS OF COTTON.</b></h3>
+
+<p>(p. 290) It has been stated by Link and Voswinkel (Pharm. Centralhalle,
+1893, 253), that raw cotton yields<span class='pagenum'><a name="Page_125" id="Page_125">[Pg 125]</a></span> 'wood gum' as a product of
+hydrolysis. The authors were unable to obtain any pentoses as products
+of acid hydrolysis of raw cotton, and traces only of furfural-yielding
+carbohydrates. They conclude that raw cotton contains no appreciable
+quantity of pentosane.</p>
+
+<div class="footnotes"><h3>FOOTNOTES:</h3>
+
+<div class="footnote"><p><a name="Footnote_8_8" id="Footnote_8_8"></a><a href="#FNanchor_8_8"><span class="label">[8]</span></a> This paper appears during the printing of the author's
+original MS.</p></div>
+
+<div class="footnote"><p><a name="Footnote_9_9" id="Footnote_9_9"></a><a href="#FNanchor_9_9"><span class="label">[9]</span></a> This paper appears during the printing of the author's
+original MS.</p></div>
+</div>
+
+
+<hr style="width: 65%;" />
+<h2><a name="SECTION_VI_THE_LIGNOCELLULOSES" id="SECTION_VI_THE_LIGNOCELLULOSES"></a>SECTION VI. THE LIGNOCELLULOSES</h2>
+
+
+<p>(p. 131) <b>Lignocellulose Esters.</b>&mdash;By a fuller study of the ester
+reactions of the normal celluloses we have been able to throw some light
+on the constitutional problems involved; and we have extended the
+investigations to the jute fibre as a type of the lignocelluloses, from
+the results of which we get a clearer idea of the relationships of the
+constituent groups.</p>
+
+<p>Taking the empirical expression for the complex, i.e. the entire
+lignocellulose, the formula C<sub>12</sub>H<sub>18</sub>O<sub>9</sub>, we shall be able to
+compare the ester derivatives with those of the celluloses, which we
+have also referred to a C<sub>12</sub> unit. But we shall require also to deal
+with the constituent groups of the complex, which for the purposes of
+this discussion may be regarded as (<i>a</i>) a cellulose of normal
+characteristics&mdash;cellulose &#945;; (<i>b</i>) a cellulose yielding furfural on
+boiling with condensing acids&mdash;cellulose &#946;; and (<i>c</i>) a much
+condensed, and in part benzenoid, group which we may continue to term
+the lig<i>none</i> group.</p>
+
+<p>The latter has been specially examined with regard to its proportion of
+OH groups, as a necessary preliminary to the investigation of esters, in
+producing which the entire complex is employed. It will be shown that
+the ester groups can be actually localised in various ways, as in the
+main entering the cellulose residues &#945; and &#946;. But that the
+lignone group takes little part in the reactions may be generally
+concluded on the evidence of its non-reactivity as an isolated
+derivative, (1) By<span class='pagenum'><a name="Page_126" id="Page_126">[Pg 126]</a></span> chlorination, &amp;c. it is isolated in the form of an
+amorphous body, but of constant composition, represented by the formula
+C<sub>19</sub>H<sub>18</sub>Cl<sub>4</sub>O<sub>9</sub>. This compound, soluble in acetic anhydride, was
+boiled with it for six hours after adding fused sodium acetate, and the
+product separated by pouring into water. The dilute acid filtered from
+the product contained no hydrochloric acid nor by-products of action.
+The product showed an increase of weight of 7.5 p.ct. For one acetyl per
+1 mol. C<sub>19</sub>H<sub>18</sub>Cl<sub>4</sub>O the calculated increase is 8.0 p.ct. It is
+evident from the nature of the derivative that this result cannot be
+further verified by the usual analytical methods. (2) The chlorinated
+derivative is entirely soluble in sodium sulphite solution. This
+solution, shaken with benzoyl chloride, with addition of sodium hydrate
+in successive portions, shows only a small formation of insoluble
+benzoate, which separates as a tarry precipitate. (3) The empirical
+formula of the lignone complex in its isolated forms indicates that very
+little hydrolysis occurs in the processes of isolation. Thus the
+chlorinated product we may assume to be derived from the complex
+C<sub>19</sub>H<sub>22</sub>O<sub>9</sub>. In the soluble by-products from the bisulphite
+processes of pulping wood the lignone exists as a sulphonated
+derivative, C<sub>24</sub>H<sub>23</sub>(OCH<sub>3</sub>)<sub>2</sub>.(SO<sub>3</sub>H).O<sub>7</sub>. The original
+lignone may be regarded as passing into solution as a still condensed
+complex derived from C<sub>24</sub>H<sub>26</sub>O<sub>12</sub> (Tollens). There is evidently
+little attendant hydroxylation, and another essential feature is the
+small molecular proportion of groups showing the typical sulphonation.</p>
+
+<p>It appears that in the lignone the elements are approximately in the
+relation C<sub>6</sub>: H<sub>6</sub>: O<sub>3</sub>, and it may assist this discussion to
+formulate the main constitutional types consistent with this ratio,
+viz.:</p>
+
+<p>
+<span style="margin-left: 2.5em;">(1) The trihydroxybenzenes C<sub>6</sub>H<sub>3</sub>(OH)<sub>3</sub>.</span><br />
+
+<span class='pagenum'><a name="Page_127" id="Page_127">[Pg 127]</a></span>
+
+<span style="margin-left: 2.5em;">(2) Methylhydroxyfurfural C<sub>5</sub>H<sub>2</sub>O.(OH)(CH<sub>3</sub>).</span><br />
+<span style="margin-left: 2.5em;">(3) Methylhydroxypyrone</span><br /></p>
+<div class="figcenter" style="width: 159px;">
+<img src="images/image11.jpg" width="159" height="80" alt="" title="" />
+</div>
+
+<p><span style="margin-left: 2.5em;">(4) Trioxycyclohexane</span><br /></p>
+<div class="figcenter" style="width: 200px;">
+<img src="images/image12.jpg" width="200" height="52" alt="" title="" />
+</div>
+
+
+<p>It is probable that all these types of condensation are represented in
+the lignone molecules, since the derivatives yielded in decompositions
+of more or less regulated character are either directly derived from or
+related to such groups. For the moment we pass over all but the general
+fact of complexity and the marked paucity of OH-groups. It would be of
+importance to be able to formulate the exact mode of union of the
+lignone with the cellulose residues to constitute the lignocellulose.
+The evidence, however, does not carry us farther than the probability of
+union by complicated groups and of large dimensions; for not only is the
+lignone isolated in condensed and non-hydroxylated forms, but the
+cellulose also is not hydrated or hydrolysed further than in the ratio
+3C<sub>6</sub>H<sub>10</sub>O<sub>5</sub>.H<sub>2</sub>O. It is probable, therefore, that the water
+combining with the residues at the moment of their resolution is
+relatively small.</p>
+
+<p>Lastly, we have to remember, when dealing with the statistical results
+of the reactions to be described, that the approximate proportions per
+cent. of the constituent groups are:</p>
+
+
+<div class='center'>
+<table border="0" cellpadding="4" cellspacing="0" summary="">
+<tr><td align='left'>Cellulose</td><td align='center'> &#945;</td><td align='center'>65</td><td align='right'>}</td></tr>
+<tr><td align='center'>"</td><td align='center'>&#946;</td><td align='left'>15</td><td align='right'>}</td><td align='left'>=</td><td align='left'>100 lignocellulose.</td></tr>
+<tr><td align='left'>Lignone</td><td align='center'></td><td align='center'>20</td><td align='right'>}</td></tr>
+</table></div>
+
+
+<p><b>Jute Benzoates.</b>&mdash;In preparing the jute for treatment it was boiled in
+alkaline solution (1 per cent. NaOH), washed with water and dilute acid,
+again washed, dried, and weighed.</p>
+
+<p>In the ester reaction the reagents were employed in the<span class='pagenum'><a name="Page_128" id="Page_128">[Pg 128]</a></span> proportion
+C<sub>12</sub>H<sub>18</sub>O<sub>9</sub>: 3NaOH: 2C<sub>6</sub>H<sub>5</sub>COCl. A series of quantitative
+experiments gave yields of 126-130 p.ct. of benzoate [calculated for
+monobenzoate 134 p.ct.].</p>
+
+<p>The results were confirmed by ultimate analysis. The monobenzoate
+therefore represents a maximum, and this molecular proportion is
+one-half of that observed with the normal cellulose, calculated to the
+same unit.</p>
+
+<p><i>Localisation of Benzoyl Group.</i>&mdash;The entrance of the ester group
+affects the typical colour reactions of the lignocellulose, which are
+fainter. The ferric ferricyanide reaction almost disappears. The lignone
+group is unaffected, and combines with chlorine as in the original. The
+lignone chloride is removed by sodium sulphite solution, and the residue
+is a <i>cellulose benzoate</i>. The loss of weight due to the elimination of
+the lignone was 12.7 p.ct. Calculating per 100 of the original
+lignocellulose this becomes 16. These statistics further confirm the
+localisation of the benzoyl group in the cellulose residue. It is to be
+noted that the presence of the benzoyl group renders the cellulose more
+resistant to hydrolytic actions. Thus, to bring out this fact more
+prominently, we may calculate the yield of residual cellulose benzoate
+p.ct. of original jute, and we find it 109 p.ct. Taking a maximum
+proportion for original cellulose&mdash;viz. 85&mdash;this benzoate represents a
+yield of 129 p.ct., as against the theoretical for a monobenzoate, 132
+p.ct.</p>
+
+<p><i>Furfural Numbers.</i>&mdash;The percentage of furfural obtained by boiling with
+HCl of 1.06 sp.gr. was 3.02 and 3.29 in separate determinations.
+Calculating to the original lignocellulose, the percentage, 4.21,
+indicates a considerable loss of the furfural-yielding constituent. The
+effect was also apparent in the cellulose (benzoate) isolated by
+chlorination &amp;c., the percentage being 1.39 p.ct., and calculated to the
+original jute benzoate 1.59 p.ct. Under the conditions adopted in
+dissolving<span class='pagenum'><a name="Page_129" id="Page_129">[Pg 129]</a></span> away the chlorinated lignone the original non-benzoated
+lignocellulose would have yielded a cellulose giving 6 to 7 p.ct.
+furfural.</p>
+
+<p>Since the benzoyl group is hardly calculated to produce a constitutional
+change affecting the furfural constants, it was necessary to examine the
+effect of the preliminary alkaline treatment, and the change in the
+furfuroid group was in fact localised in this reaction. It was found
+that, on washing the alkali from the mercerised jute, and further
+purifying the residue, this latter yielded only 4.2 p.ct. furfural [3.4
+p.ct. on original fibre]. The alkaline solution and washings were
+acidified and distilled from 10 p.ct. HCl, yielding an additional 3.6
+p.ct. calculated to the original lignocellulose. By treatment with the
+concentrated alkali, therefore, the furfuroid of the original
+lignocellulose undergoes little change, but is selectively dissolved.
+This point is under further investigation.</p>
+
+<p>(p. 132) <b>Acetylation of Lignocelluloses.</b>&mdash;Acetates are readily formed by
+boiling the lignocelluloses with acetic anhydride. The derivatives
+obtained from jute are only generally mentioned in the 1st edition (p.
+132). A further study of the reactions in regard to special points has
+led to some more definite results. The <i>yields</i> of product by the
+ordinary and simple process are 114-115 p.ct. But on analysing the
+product an important discrepancy is revealed.</p>
+
+<p>For the saponification we employ a solution of sodium ethylate in the
+cold. The following numbers were obtained:</p>
+
+
+<div class='center'>
+<table border="0" cellpadding="4" cellspacing="0" summary="">
+<tr><td align='left'></td><td align='left'>Acetic acid</td><td align='left'>Hydrocellulose residue</td></tr>
+<tr><td align='left'></td><td align='center'>27.2</td><td align='center'>77.8</td></tr>
+<tr><td align='left'>Calc. for diacetate on C<sub>12</sub>H<sub>18</sub>O<sub>9</sub></td><td align='center'>30.8</td><td align='center'>78.4</td></tr>
+</table></div>
+
+<p>The derivative is approximately a diacetate, and on the assumption of a
+simple ester reaction the yield should be<span class='pagenum'><a name="Page_130" id="Page_130">[Pg 130]</a></span> 127 p.ct. Assuming that the
+difference of 13 p.ct. is due to loss of water by internal condensation,
+it appears that for each acetyl group entering, 2 mol. H<sub>2</sub>O are split
+off.</p>
+
+<p>The jute acetate showed the normal reaction with chlorine, and the
+lignone chloride was dissolved by treatment with sodium sulphite
+solution. The fibrous residue was colourless. It proved to be a
+cellulose acetate. The following numbers were obtained on
+saponification:</p>
+
+
+<div class='center'>
+<table border="0" cellpadding="4" cellspacing="0" summary="">
+<tr><td align='left'></td><td align='left'>Acetic acid</td><td align='left'>Cellulose</td></tr>
+<tr><td align='left'></td><td align='center'>31.6</td><td align='center'>70.0</td></tr>
+<tr><td align='left'></td><td align='center'>30.9</td><td align='center'>68.8</td></tr>
+<tr><td align='left'>Calc. for diacetate on C<sub>12</sub>H<sub>20</sub>O<sub>10</sub></td><td align='center'>29.4</td><td align='center'>79.9</td></tr>
+</table></div>
+
+<p>The interpretation of these numbers appears to be this: in the original
+reaction with the lignocellulose it is the cellulose residue which is
+acetylated, and at the same time condensed. The cellulose residue which
+undergoes condensation is not of the normal constitution, since the
+normal cellulose is acetylated without condensation (see p. 41). On
+saponification a portion of the cellulose, in again combining with
+water, is hydrolysed to soluble products. The lignone group as it exists
+in the lignocellulose has no free OH groups, and probably no free
+aldehydic groups such as would react with the anhydride. Such groups
+may, however, be originally present, and may take part in the internal
+condensations which have been shown to occur. The furfural constants of
+the lignocellulose are unaffected by the acetylation and condensation.
+The hygroscopic moisture of the product is lowered from 10-11 p.ct. in
+the original to 4.5 p.ct. The ferric ferricyanide reaction is inhibited
+by the disappearance of the reactive groups, upon which this curious and
+characteristic phenomenon depends (1st ed.).</p>
+
+<p><span class='pagenum'><a name="Page_131" id="Page_131">[Pg 131]</a></span></p><p><b>Acetylation of Benzoates.</b>&mdash;The cellulose dibenzoate (C<sub>12</sub> basis) and
+the jute monobenzoate were acetylated under comparative conditions The
+results were as follows:</p>
+
+
+
+
+<div class='center'>
+<table border="0" cellpadding="4" cellspacing="0" summary="">
+<tr><td align='left'></td><td align='left'></td><td colspan="4">C12 basis</td></tr>
+<tr><td align='left'></td><td align='left'></td><td colspan="2">Cellulose dibenzoate</td><td colspan="2">Jute monobenzoate</td></tr>
+<tr><td align='left'></td><td align='left'></td><td align='left'>Found</td><td align='left'>Calc. for diacetate<br /> on dibenzoate</td><td align='left'>Found</td><td align='left'>Calc. for diacetate<br /> on monobenzoate</td></tr>
+<tr><td align='left'>Ester reaction</td></tr>
+<tr><td align='left'>Yield</td><td align='left'></td><td align='center'>111 p.ct.</td><td align='center'>115 p.ct.</td><td align='center'>124 p.ct.</td><td align='center'>120 p.ct.</td></tr>
+<tr><td align='left'>Saponification</td><td align='left'>{Cellulose}</td><td rowspan="2">53.5</td><td rowspan="2">52.6</td><td rowspan="2">59.8</td><td rowspan="2">61.9</td></tr>
+<tr><td align='left'></td><td align='left'>{Lignocellulose}</td></tr>
+<tr><td align='left'></td><td align='left'>NaOH combining</td><td align='center'>21.3</td><td align='center'>23.9</td><td align='center'>28.4</td><td align='center'>24.3</td></tr>
+</table></div>
+
+
+
+<p>From these results it would appear that the number of acetyl groups
+entering the benzoates is the same as with the unbenzoylated fibres, the
+benzoyl has no influence upon the hydroxyls as against the acetyl. At
+the same time the internal condensation noticed in the acetylation of
+the jute appears not to occur in the case of the benzoate.</p>
+
+<p><b>Nitric Esters.</b>&mdash;The numbers resulting from the quantitative study of the
+ester reaction and product (1st ed. p. 133) show a very large divergence
+of the yield of product from that which would be calculated from its
+composition (N p.ct.) on the assumption that the ester reaction is
+simple. We have repeated the results, and find with a yield of 145 p.ct.
+that the product contains 11.8 p.ct. N.</p>
+
+<p>The reaction</p>
+
+<p>
+<span style="margin-left: 2.5em;">C<sub>12</sub>H<sub>18</sub>O<sub>9</sub> + 4HNO<sub>3</sub> - 4H<sub>2</sub>O</span><br />
+</p>
+
+<p>gives a tetranitrate with 11.5 p.ct. N and a yield of 159 p.ct. The
+ester reaction, therefore, is not simple. There are two sources of the
+loss of weight. The first of these is evident from the occurrence of
+certain secondary reactions which result in the solution of a certain
+proportion of the fibre substance in the acid mixture. To determine this
+quantitatively we have devised a suitable variation of the method of
+combustion with chromic acid (1st ed.).</p>
+
+<p>The variation is required to meet the difficulty occasioned by the
+tension of the nitric acid and products of deoxidation. The mixed acids
+(10 c.c.), containing the organic by-products<span class='pagenum'><a name="Page_132" id="Page_132">[Pg 132]</a></span> in solution, are
+carefully diluted in a small flask with an equal volume of water,
+preventing rise of temperature. Nitrous fumes are evolved during the
+dilution. Strong sulphuric acid (15 c.c.) is now added, and the residue
+of nitrous fumes expelled by a current of air, agitating the contents of
+the flask from time to time. The combustion with CrO<sub>3</sub> is then
+proceeded with in the ordinary way. The gases evolved are measured
+(total volume) and calculated to C present in the form of products
+derived from the lignocellulose; and, assuming that this contains 47
+p.ct. C, we may express the result approximately in terms of the fibre
+substance. The method was controlled by blank experiments, in which
+citric acid was taken as a convenient carbon compound for combustion.
+The C found was 34.9 p.ct. as against 34.3 p.ct. calculated. By this
+method we find that with maximum yields of nitrate at 143-145 p.ct. the
+organic matter in solution in the acid mixture amounted to 4.9 to 5.3
+p.ct. of the original lignocellulose.</p>
+
+<p>Introducing this quantity as a correction of the yield of nitrate in the
+original reaction, we must express the 143 parts as obtained from 95 of
+fibre substance instead of 100.</p>
+
+<p>The yield per molecule C<sub>12</sub>H<sub>18</sub>O<sub>9</sub> (= 306) is therefore 462,
+whereas for a tetranitrate formed by a simple ester reaction the yield
+should be 486. The difference (24) represents 1.5 mol. H<sub>2</sub>O split off
+by internal condensation.</p>
+
+<p>The correction for total N is relatively small, raising it from 11.5 to
+12.2, which remains in close agreement with the experimental numbers.</p>
+
+<p><i>Monobenzoate.</i>&mdash;Treated with the acid mixture yields a mixed nitrate.
+The yield is 130 p.ct., and the product contains 7.6 p.ct. O.NO<sub>2</sub>
+nitrogen. These numbers approximate to those required for reaction with
+4HNO<sub>3</sub> groups, three of the residues entering the cellulose, and one
+<span class='pagenum'><a name="Page_133" id="Page_133">[Pg 133]</a></span>(as NO<sub>2</sub>) the benzene ring of the substituting group. For such a
+reaction the calculated numbers are: Yield 144 p.ct.; O.NO<sub>2</sub> nitrogen
+7.1 p.ct.</p>
+
+<p>The experimental numbers require correcting for the amount of loss in
+the form of products soluble in the acid mixture, viz. 7.6 p.ct.; but
+they remain within the range of the experimental errors sufficiently to
+show that the benzoyl group limits the number of OH groups taking part
+in the ester reaction to three. The corrected yield per 1 mol. of jute
+benzoate (410) is 576, as against the calculated 590 for 4HNO<sub>3</sub>
+reacting. A loss of 1H<sub>2</sub>O per molecule by internal condensation is
+therefore indicated.</p>
+
+<p><b>Denitration.</b>&mdash;The removal of the nitric groups from the esters is
+effected by digestion with ammonium sulphide. But the reactions are by
+no means simple. There is considerable hydrolysis of the lignocellulose
+to soluble products. Thus the <i>tetranitrate</i> yields only 46.4 of
+denitrated fibre in place of the calculated 66. The product is a
+cellulose, yielding only 0.5 per cent. furfural. The hydrolysed
+by-products, moreover, when freed from sulphur and distilled from
+hydrochloric acid, yielded only an additional 2.5 p.ct. furfural,
+calculated to the original lignocellulose.</p>
+
+<p>These statistics confirm the evidence that the ester reaction is not
+simple. Such changes take place in the lignone-&#946;-cellulose complex
+that they revert, not to their original form, but to soluble derivatives
+of different constitution. The mixed nitrate from the benzoate is
+denitrated to a cellulose amidobenzoate, which confirms the localisation
+of a nitro-group in the benzoyl residue.</p>
+
+<p>(p. 157) <b>General Characteristics of the Lignocelluloses.</b>&mdash;Later
+investigations have somewhat modified and simplified our views of the
+constitution of the typical lignocellulose (jute), so far as this can be
+dealt with by the<span class='pagenum'><a name="Page_134" id="Page_134">[Pg 134]</a></span> statistics of its more important decompositions
+(original, pp. 157-161).</p>
+
+<p><b>Cellulose.</b>&mdash;There is little doubt that the furfural-yielding groups of
+the original are isolated in the form of the &#946;-cellulose. Tollens
+emphasises this fact in his studies of cellulose-estimation methods. We
+had previously shown (original, p. 159) that the yield of furfural is
+not affected by the <i>chlorination</i>, but it appears from our numbers that
+only 50 p.ct. of these groups remain in the isolated cellulose, the
+residue undergoing hydrolysis to soluble compounds. In a carefully
+regulated hydrolysis following the chlorination it appears that the
+furfuroids are almost entirely conserved in the form of a cellulose.</p>
+
+<p>Moreover, an investigation of the products dissolved by sodium sulphite
+solution from the chlorinated fibre has shown that they are practically
+free from furfuroids. This enables us to exclude the furfural-yielding
+groups from the lignone complex. At the same time, through our later
+studies of the hydroxyfurfurals, it is certain that these products are
+represented in the fibre substance and probably in the lignone complex.</p>
+
+<p><b>Chlorination Statistics.</b>&mdash;It has been pointed out by a correspondent&mdash;to
+whom we express our indebtedness&mdash;that we have made a mistake in
+calculating the proportion of lignone from the ratio of the Cl combining
+with the fibre substance or lignocellulose (p.ct), to that of the Cl
+<i>present in</i> the isolated lignone chloride (p.ct.). The lignocellulose
+combines with chlorine in the ratio 100: 8, but the lignone chloride
+<i>containing</i> 26.7 of chlorine means that, neglecting the hydrogen
+substituted, 73 of lignone combine with the 27 of chlorine
+approximately. On the uniform percentage basis the calculated proportion
+of lignone would be 8/37, or a little over 20 p.ct.<span class='pagenum'><a name="Page_135" id="Page_135">[Pg 135]</a></span></p>
+
+<p>In regard to the proportion of hydration attending the resolution, we
+have shown on constitutional grounds that this must be relatively small.
+Assuming approximately the formula C<sub>19</sub>H<sub>22</sub>O<sub>9</sub> for the lignone
+residue as it exists in combination, and the anhydride formula for the
+cellulose, these revised statistics now appear, as regards the carbon
+contents of the lignocellulose:</p>
+
+
+<div class='center'>
+<table border="0" cellpadding="4" cellspacing="0" summary="">
+<tr><td align='left'>Cellulose, 44.4 C; lignone, 57.8.</td></tr>
+<tr><td align='right'>80 &times; 44.4 &divide; 100</td><td align='left'>=</td><td align='left'>35.52</td></tr>
+<tr><td align='right'>20 &times; 57.8 &divide; 100</td><td align='left'>=</td><td align='left'>11.56</td></tr>
+<tr><td align='left'></td><td align='left'></td><td align='left'>_____</td></tr>
+<tr><td align='left'></td><td align='left'></td><td align='left'>47.08 p.ct. C in lignocellulose.</td></tr>
+</table></div>
+
+
+<p>These conclusions are in accordance with the experimental facts, and,
+taken together with the new evidence we have accumulated from a study of
+the lignocellulose esters, we may sum up the constitutional points as
+follows: The lignocellulose is a complex of</p>
+
+
+
+<div class='center'>
+<table border="0" cellpadding="4" cellspacing="4" summary="">
+<tr><td align='center'>Cellulose &#945;</td><td align='center'>Cellulose &#946;</td><td align='center'>Lignone</td></tr>
+<tr><td align='center'>65 p.ct.</td><td align='center'>15 p.ct.</td><td align='center'>20</td></tr>
+<tr><td align='center'>Allied to the normal celluloses</td><td align='center'>Yielding furfural approximately 50 p.ct.</td><td align='center'>One-third of which is of benzenoid type</td></tr>
+</table></div>
+
+<p>The lignone contains but little hydroxyl. The celluloses are in
+condensed hydroxyl union with the lignone, but the combination occurs by
+complexes of relatively large molecular weight.</p>
+
+
+<h3>DIE CHEMIE DER LIGNOCELLULOSEN&mdash;EIN NEUER TYPUS.</h3>
+
+<h4><span class="smcap">W. C. Hancock</span> and <span class="smcap">O. W. Dahl</span> (Berl. Ber., 1895, 1558).</h4>
+
+<h3><b>Chemistry of Lignocelluloses&mdash;A New Type.</b></h3>
+
+<p>The stem of the aquatic <i>&AElig;schynomene aspera</i> offers an exceptional
+instance of structural modification to serve the special function of a
+'float,' 1 grm. of substance occupying an apparent volume of 40-50 c.c.
+This pith-like substance is<span class='pagenum'><a name="Page_136" id="Page_136">[Pg 136]</a></span> morphologically a true wood (De Bary), and
+the author's investigations now establish that it is in all fundamental
+points of chemical composition a lignocellulose, although from its
+colour reactions it has been considered by botanists to be a cellulose
+tissue containing a proportion of lignified cells. Thus the main tissue
+is stained blue by iodine in presence of hydriodic acid (1.5 s.g.), and
+the colour is not changed on washing. The ordinary lignocelluloses are
+stained a purple brown changed to brown on washing. The reactions with
+phloroglucol and with aniline salts, characteristic of these compounds,
+is only faintly marked in the main tissue, though strongly in certain
+individual cells.</p>
+
+<p>The following quantitative determinations, however, establish the close
+similarity of the product to the typical lignocelluloses:</p>
+
+<p><i>Elementary Analysis.</i>&mdash;C 46.55, H 6.7. <i>Furfural</i> 11.6 p.ct., of which
+there remained in the residue from alkaline hydrolysis (71 p.ct.) 8.0,
+i.e. about 70 p.ct. The distribution of the furfuroids is therefore not
+affected by the alkaline treatment.</p>
+
+<p><i>Chlorination.</i>&mdash;The substance (after alkaline hydrolysis) takes up 16.9
+p.ct. Cl, of which approximately one-half is converted into hydrochloric
+acid.</p>
+
+<p><i>Methoxyl.</i>&mdash;O.CH<sub>3</sub> estimated = 2.9 p.ct.</p>
+
+<p><i>Ferric Ferricyanide Reaction.</i>&mdash;Increase of weight due to blue cyanide
+fixed (1) 75 p.ct., (2) 96 p.ct. Ratio, Fe: CN = 1: 2, 4.</p>
+
+<p><i>Hydroxyl Reactions.</i>&mdash;In the formation of nitric esters and in the
+sulphocarbonate reaction the substance gave results similar to those
+obtaining for the jute fibre.</p>
+
+<p>These results establish the general identity of this peculiar product of
+plant life with the lignocelluloses, at the same time that they show
+that certain of the colour reactions supposed to characterise the
+lignocelluloses are due to by-products which may or may not be present.<span class='pagenum'><a name="Page_137" id="Page_137">[Pg 137]</a></span></p>
+
+<p>(p. 172) <b>Composition of Elder Pith.</b>&mdash;In a systematic investigation of
+the celluloses in relation to function we shall have to give special
+attention to the parenchymatous tissues of all kinds. These are, for
+structural reasons, not easily isolated, for which reason and their
+generally 'inferior' functions they do not present themselves to
+chemical observation in the same obvious way as do their fibrous
+relatives. The pith of the elder, however, <i>is</i> readily obtained in
+convenient masses, and a preliminary investigation of the entire tissue
+has established the following points:</p>
+
+<p>The <i>reactions</i> of the tissue are in all respects those of the
+lignocelluloses.</p>
+
+<p><i>Composition.</i>&mdash;Ash, 2.2 p.ct.; moisture in air-dry state, 12.3 p.ct.
+Alkaline hydrolysis (loss): (<i>a</i>) 14.77, (<i>b</i>) 17.84. Cellulose (yield),
+52.33 p.ct. Nitrate-reaction complicated by secondary reactions and
+yields low, 90.95 p.ct. <i>Sulphocarbonate reaction:</i> Resists the
+treatment, less than 10 p.ct. passes into solution.</p>
+
+<p><i>Furfural.</i>&mdash;The original tissue yields 7.13 p.ct.; the residue from
+alkaline hydrolysis (<i>b</i>) 5.40 p.ct.</p>
+
+<p>This tissue is, therefore, a lignocellulose having the chemical
+characteristics typical of the group, but of less resistance to
+hydrolytic actions.</p>
+
+<p>The investigation will be prosecuted in reference to the cause of
+differentiation in this latter respect. Probably the pectocelluloses are
+represented in the tissue.</p>
+
+
+<h3><b>The Insoluble Carbohydrates of Wheat (grain).</b></h3>
+
+<h4><span class="smcap">H. C. Sherman</span> (J. Amer. Chem. Soc., 1897, 291).</h4>
+
+<p>(p. 171) This is a study of the constituents of the cell-walls of wheat
+grain. Bran was taken as the most convenient form of the raw material,
+being freed from starch by treatment with malt extract, and further
+treated (1) with cold dilute ammonia,<span class='pagenum'><a name="Page_138" id="Page_138">[Pg 138]</a></span> (2) cold dilute soda lye (2 p.ct.
+NaOH), and (3) boiling 0.1 p.ct. NaOH. The product retained only 1.25
+p.ct. proteids, and yielded 15.62 p.ct. furfural.</p>
+
+<p><i>Acid Hydrolysis.</i>&mdash;The product was boiled 30 mins. with dilute acid
+(1.25 p.ct. H<sub>2</sub>SO<sub>4</sub>), and the solution boiled until the Fehling test
+showed no further increase of monoses. At the limit the reducing power
+of the dissolved carbohydrates was 91.3 p.ct., that of dextrose.
+Converted into osazones the analysis showed them to be <i>pure
+pentosazones</i>. The <i>hemicellulose</i> of wheat is, therefore, according to
+the author, <i>pure pentosane</i>.</p>
+
+<p><i>Residue.</i>&mdash;This was a lignocellulose yielding 11.5 p.ct. furfural. It
+was subjected to a series of treatments with ferric ferricyanide, and
+the proportion of Prussian blue fixed was determined by increase of
+weight, viz. from 10 p.ct. to 47 p.ct. according to the conditions. The
+results confirmed those of Cross and Bevan first obtained with the
+typical lignocellulose (jute).</p>
+
+<p><i>Chlorination.</i>-The residue was boiled with dilute alkali, washed, and
+exposed to chlorine gas. The resulting lignone chloride was isolated by
+solution in alcohol, &amp;c. It yielded 26.7 p.ct. Cl on analysis. In this
+and its properties it appeared to be identical with the product isolated
+by Cross and Bevan from jute, with the empirical formula
+C<sub>19</sub>H<sub>18</sub>Cl<sub>4</sub>O<sub>9</sub>.</p>
+
+<p><i>Cellulose</i> was isolated from the residue by three of the well-known
+methods, and the following comparative numbers are noteworthy:</p>
+
+<div class='center'>
+<table border="1" cellpadding="4" cellspacing="0" summary="">
+<tr><td align='left'>Method</td><td align='left'> F. Schulze<br /> Dil. HNO<sub>3</sub> KClO<sub>3</sub></td><td align='left'>Lange Fusion<br /> KOH</td><td align='left'> Cross and Bevan<br /> Chlorine, &amp;c.</td></tr>
+<tr><td align='left'>Cellulose p.ct. obtained</td><td align='center'> 66.0</td><td align='center'> 39.3-43.1</td><td align='center'> 66.5</td></tr>
+<tr><td align='left'>Furfural p.ct. of cellulose</td><td align='center'> 7.0</td><td align='center'> 3.96</td><td align='center'> 5.62</td></tr>
+<tr><td align='left'>Residual nitrogen</td><td align='center'> 0.22</td><td align='center'> 0.03</td><td align='center'> 0.00</td></tr>
+<tr><td align='left'>Ferricyanide reaction, Prussian blue fixed</td><td align='center'> 6.04</td><td align='center'> 0.89</td><td align='center'> 0.92</td></tr>
+</table></div>
+
+
+
+<p><span class='pagenum'><a name="Page_139" id="Page_139">[Pg 139]</a></span></p>
+
+<p>The author remarks: 'It is evident no one feature can be urged as a
+criterion in judging between the methods, but all must be taken into
+consideration. Such a comparison shows the superiority of the
+chlorination method.'</p>
+
+<p>The cellulose is not of the normal (cotton) type, since on treatment
+with sulphuric acid it dissolves with considerable discolouration, but
+only to the extent of about 80 per cent. The dissolved monoses converted
+into osazones were found to consist of hexoses only. The cellulose
+treated with caustic soda solution (5 p.ct. NaOH) in the cold yielded 20
+p.ct. of its weight of soluble constituents, but as the residue yielded
+3.34 p.ct. furfural the attack of the alkali is by no means confined to
+the furfuroids.</p>
+
+<p><b>Animal Digestion of the Constituents of Bran.</b>&mdash;Observations on a steer
+fed upon wheat bran only established the following percentage digestion
+of the several constituents:</p>
+
+<div class='center'>
+<table border="0" cellpadding="4" cellspacing="0" summary="">
+<tr><td align='left'>Soluble carbohydrates</td><td align='left'>96.9</td></tr>
+<tr><td align='left'>Starch</td><td align='left'>100.0</td></tr>
+<tr><td align='left'>Free pentosanes</td><td align='left'>60.2</td></tr>
+<tr><td align='left'>Cellulose</td><td align='left'>24.8</td></tr>
+<tr><td align='left'>Lignin complex</td><td align='left'>36.7</td></tr>
+<tr><td align='left'>Proteid</td><td align='left'>82.96</td></tr>
+<tr><td align='left'>Ether extract</td><td align='left'>42.73</td></tr>
+<tr><td align='left'>_____________________</td><td align='left'>______</td></tr>
+<tr><td align='left'>Nitrogen-free extract</td><td align='left'>76.08</td></tr>
+<tr><td align='left'>Crude fibre</td><td align='left'>32.21</td></tr>
+</table></div>
+
+
+<h3>JOURNAL OF THE IMPERIAL INSTITUTE</h3>
+
+<h4>(Research Department, Vols. 1-2, 1895-6).</h4>
+
+<p>(p. 109) In this journal appear a series of notices of the results of
+analyses of vegetable fibres by the method described in 'Report on
+Miscellaneous Fibres' (Col. Ind. Exhibition<span class='pagenum'><a name="Page_140" id="Page_140">[Pg 140]</a></span> Reports, p. 368) [C. F.
+Cross]. These investigations deal with the following subjects:</p>
+
+<p>
+1895.     p. 29      Various Indian Fibres&mdash;more particularly Sida.<br />
+(<i>a</i>)  118      (<i>a</i>) Fibres from Victoria; (<i>b</i>) SpecialAnalyses ofSamples of Jute; (<i>c</i>) Paper-making Fibres from S. Australia.<br />
+<span style="margin-left: 6em;">202&nbsp; &nbsp; &nbsp; Fibres from Victoria.</span><br />
+<span style="margin-left: 6em;">287&nbsp; &nbsp; &nbsp; Fibres from Victoria.</span><br />
+<span style="margin-left: 6em;">366&nbsp; &nbsp; &nbsp; Sisal from Trinidad.</span><br />
+<span style="margin-left: 6em;">373&nbsp; &nbsp; &nbsp; Rope-fibres from Grenada.</span><br />
+(<i>b</i>)  398      Report of Experiments on Indian Jute (1).<br />
+<span style="margin-left: 6em;">435}&nbsp; &nbsp;  Fifth and Sixth Report on Australian Fibres.</span><br />
+<span style="margin-left: 6em;">473}</span><br />
+1896.        68      Hibiscus and Abroma Fibres.<br />
+<span style="margin-left: 6em;">104-5&nbsp; &nbsp; Hibiscus, Urena, and Crotalaria Fibres.</span><br />
+<span style="margin-left: 6em;">141&nbsp; &nbsp; &nbsp; Indian Sisal</span><br />
+(<i>c</i>)  182-3    Report of Experiments on Indian Jute (2).<br />
+<span style="margin-left: 6em;">264&nbsp; &nbsp; &nbsp; Sanseviera from Assam.</span><br />
+</p>
+
+<p>From the above we may draw the general conclusion that the scheme of
+investigation has been found in practice to answer its main purpose,
+viz. to afford such numerical constants as determine industrial values.
+In illustration we may cite (<i>a</i>) the results of analyses of specially
+selected samples of jute, from which it will be seen that there is a
+close concordance of value as ordinarily determined from external
+appearance, with the chemical constants as determined in the laboratory.</p>
+
+
+<div class='center'>
+<table border="1" cellpadding="4" cellspacing="0" summary="">
+<tr><td align='left'></td><td colspan="4"> Quality of Jute</td></tr>
+<tr><td align='left'></td><td align='center'> Low</td><td align='center'> Medium</td><td align='center'> Extra</td><td align='center'> Extra Fine</td></tr>
+<tr><td align='left'>Moisture</td><td align='center'> 11.0</td><td align='center'> 10.4</td><td align='center'> 11.1</td><td align='center'> 9.6</td></tr>
+<tr><td align='left'>Ash</td><td align='center'> 0.87</td><td align='center'> 2.8</td><td align='center'> 1.0</td><td align='center'> 0.7</td></tr>
+<tr><td align='left'>Alkaline hydrolysis (<i>a</i>) 5 mins. boiling</td><td align='center'> 13.2</td><td align='center'> 11.6</td><td align='center'> 8.5</td><td align='center'> 9.1</td></tr>
+<tr><td align='left'>Alkaline hydrolysis (<i>b</i>) 60 mins. boiling </td><td align='center'>16.1</td><td align='center'> 17.5</td><td align='center'> 12.5</td><td align='center'> 13.1</td></tr>
+<tr><td align='left'>Mercerising treatment</td><td align='left'> 9.2</td><td align='center'> 10.5</td><td align='center'> 10.3</td><td align='center'> 8.5</td></tr>
+<tr><td align='left'>Nitration (increase p.ct.)</td><td align='center'> 36.6</td><td align='center'> 35.7</td><td align='center'> 37.5</td><td align='center'> 36.7</td></tr>
+<tr><td align='left'>Cellulose (yield)</td><td align='center'> 71.4</td><td align='center'> 70.0</td><td align='center'> 79.0</td><td align='center'> 77.7</td></tr>
+<tr><td align='left'>Acid purification</td><td align='center'> 2.6</td><td align='center'> 1.3</td><td align='center'> 1.9</td><td align='center'> 2.0</td></tr>
+</table></div>
+
+<p><span class='pagenum'><a name="Page_141" id="Page_141">[Pg 141]</a></span></p>
+
+<p>A useful series of experiments, initiated by the Institute, is that
+noted under (<i>b</i>) and (<i>c</i>) above.</p>
+
+<p>(1) To ascertain the quality of the fibre extracted from the plant at
+different stages of growth, quantities of 400 lbs. of the stalks were
+cut at successive stages and the fibre isolated after steeping 14-20
+days. The fibre was shipped to England and chemically investigated, with
+the following results:</p>
+
+
+
+<div class='center'>
+<table border="0" cellpadding="4" cellspacing="0" summary="">
+<tr><td align='left'>No.</td><td align='left'>1.</td><td align='left'>Cut</td><td align='left'>before appearance of inflorescence.</td></tr>
+<tr><td align='left'> "</td><td align='left'>2.</td><td align='center'>"</td><td align='left'>after budding.</td></tr>
+<tr><td align='left'> "</td><td align='left'>3.</td><td align='center'>"</td><td align='left'>in flower.</td></tr>
+<tr><td align='left'> "</td><td align='left'>4.</td><td align='center'>"</td><td align='left'>after appearance of seed-pod.</td></tr>
+<tr><td align='left'> "</td><td align='left'>5.</td><td align='center'>"</td><td align='left'>when fully matured.</td></tr>
+</table></div>
+
+
+<div class='center'>
+<table border="0" cellpadding="4" cellspacing="0" summary="">
+<tr><td align='left'></td><td align='center'> (1)</td><td align='center'> (2)</td><td align='center'> (3)</td><td align='center'> (4)</td><td align='center'> (5)</td></tr>
+<tr><td align='left'>Moisture</td><td align='left'> 11.55</td><td align='center'> 8.74</td><td align='center'> 10.7</td><td align='center'> 10.0</td><td align='center'> 9.72</td></tr>
+<tr><td align='left'>Ash</td><td align='left'> 1.1</td><td align='center'> 1.1</td><td align='center'> 1.1</td><td align='center'> 1.1</td><td align='center'> 0.90</td></tr>
+<tr><td align='left'>Alkaline hydrolysis (<i>a</i>)</td><td align='center'> 6.2</td><td align='center'> 8.5</td><td align='center'> 9.7</td><td align='center'> 8.9</td><td align='center'> 7.3</td></tr>
+<tr><td align='left'>&nbsp;&nbsp;&nbsp;&nbsp;"&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp; " &nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;(<i>b</i>)</td><td align='center'> 10.5</td><td align='center'> 11.9</td><td align='center'> 11.6</td><td align='center'> 12.0</td><td align='center'> 11.2</td></tr>
+<tr><td align='left'>Mercerising treatment</td><td align='left'> 10.2</td><td align='center'> 10.7</td><td align='center'> 12.0</td><td align='center'> 8.1</td><td align='center'> 11.0</td></tr>
+<tr><td align='left'>Nitration</td><td align='left'> 37.2</td><td align='center'> 32.1</td><td align='center'> 32.2</td><td align='center'> 33.2</td><td align='center'> 36.6</td></tr>
+<tr><td align='left'>Cellulose</td><td align='left'> 74.0</td><td align='center'> 76.2</td><td align='center'> 74.1</td><td align='center'> 74.8</td><td align='center'> 76.4</td></tr>
+<tr><td align='left'>Acid purification</td><td align='center'> 0.8</td><td align='center'> 0.5</td><td align='center'> 0.7</td><td align='center'> 2.4</td><td align='center'> 1.4</td></tr>
+</table></div>
+
+<p>It will be thus seen that there are no changes of any essential kind in
+the chemical composition of the bast fibre throughout the life-history
+of the plant, confirming the conclusion that the 'incrustation' view of
+lignification is consistent only with the structural features of the
+changes, and so far as it has assumed the gradual overlaying of a
+cellulose fibre with the lignone substance it is not in accordance with
+the facts.</p>
+
+<p>Examination of the samples from the point of view of textile quality
+showed a superiority of No. 1 in fineness, softness, and strength; from
+this stage there is observed a progressive deterioration, but the No. 4
+sample (which was taken at the usual period of cutting) is superior to
+No. 5.<span class='pagenum'><a name="Page_142" id="Page_142">[Pg 142]</a></span></p>
+
+<p>In a further series of experiments (<i>c</i>) the jute was subjected to
+certain chemical treatments immediately after the separation of the
+fibre from the plant. These consisted in steeping (1) in solution of
+sodium carbonate, as well as of plant ashes, and (2) in sulphite of
+soda, the purpose of the treatments being to modify or arrest the
+changes which take place in the fibre when press-packed in bales for
+shipment. The samples were shipped from India under the usual conditions
+and examined soon after arrival. It was found that the chemical
+treatments had produced but small changes in chemical composition of the
+fibre-substance. The sulphite treatment was the more marked in
+influence, somewhat lowering the cellulose and nitration constants. The
+conclusion drawn from the results was that they afford no prospect of
+any useful modification, i.e. improvement of the textile quality of the
+fibre by any chemical treatments such as could be applied to the fibre
+on the spot before drying for press-packing and shipment.</p>
+
+<p>The other matters investigated in the Institute laboratory and reported
+on as indicated above are rather of commercial significance, and
+contributed no points of moment to the chemistry of cellulose.</p>
+
+
+<h3>OBSERVATIONS ON SOME OF THE CHEMICAL SUBSTANCES IN THE TRUNKS OF TREES.</h3>
+
+<h4><span class="smcap">F. H. Storer</span> (Bull. Bussey Inst., 1897, 386).</h4>
+
+<p>(p. 172) An examination of the outer and inner wood and of the bark of
+the grey birch, at different seasons of the year, gave the following
+yields of furfural p.ct. on the dry substance:<span class='pagenum'><a name="Page_143" id="Page_143">[Pg 143]</a></span></p>
+
+
+<div class='center'>
+<table border="1" cellpadding="4" cellspacing="0" summary="">
+<tr><td align='left'></td><td colspan="2"> Wood</td><td rowspan="2"> Bark</td></tr>
+<tr><td align='left'></td><td align='left'> Inner</td><td align='left'> Outer</td></tr>
+<tr><td align='left'>May</td><td align='left'> 21.3</td><td align='left'> 19.6</td><td align='left'> 16.7</td></tr>
+<tr><td align='left'>July</td><td align='left'> 16.6</td><td align='left'> 18.8</td><td align='left'> 11.4</td></tr>
+<tr><td align='left'>October</td><td align='left'> 16.2</td><td align='left'> 16.3</td><td align='left'> 12.3</td></tr>
+</table></div>
+
+
+<p>The paper contains the results of treating the woods and various
+vegetable products with hydrolysing agents in order of intensity: (<i>a</i>)
+Malt-extract at 60&deg;C., (<i>b</i>) boiling dilute HCl (1.0 p.ct. HCl), and
+(<i>c</i>) boiling dilute HCl (2.5 p.ct.). The residues were found to yield
+considerable proportions of furfural. The following numbers are typical:</p>
+
+
+
+<div class='center'>
+<table border="1" cellpadding="4" cellspacing="0" summary="">
+<tr><td align='left'></td><td colspan="2"> Birch</td><td colspan="3"> Stones of</td></tr>
+<tr><td align='left'></td><td align='left'> Bark</td><td align='left'> Wood</td><td align='left'> Date</td><td align='left'> Apricot</td><td align='left'> Peach</td></tr>
+<tr><td align='left'>Action of malt extract calculated as starch dissolved</td><td align='left'> 4.24</td><td align='left'> 3.5</td><td align='left'> 5.2</td><td align='left'> 1.5</td><td align='left'> &mdash;</td></tr>
+<tr><td align='left'>&nbsp;</td><td align='left'>&nbsp;</td><td align='left'>&nbsp;</td><td align='left'>Mannan</td><td align='left'>&nbsp;</td><td align='left'>&nbsp;</td></tr>
+<tr><td align='left'>Residue boiled, 1 p.ct. HCl gave pentosanes dissolved.</td><td align='left'> &mdash;</td><td align='left'> &mdash;</td><td align='left'> 11.7</td><td align='left'> 14.1</td><td align='left'> 6.7</td></tr>
+<tr><td align='left'>Residue yielded furfural</td><td align='left'> 19.3</td><td align='left'> 17.8</td><td align='left'> 3.4</td><td align='left'> 9.6</td><td align='left'> 9.7</td></tr>
+</table></div>
+
+
+<p>The proportion of pentosanes (furfuroids) removed, i.e. hydrolysed by
+boiling with hydrochloric acid of 2.5 p.ct. HCl, is shown by the
+following estimations of furfural:</p>
+
+<div class='center'>
+<table border="1" cellpadding="4" cellspacing="0" summary="">
+<tr><td align='left'></td><td colspan="2"> Birch</td><td colspan="2"> Sugar maple</td><td rowspan="2"> Apricot stones</td></tr>
+<tr><td align='left'></td><td align='left'> Bark</td><td align='left'> Wood</td><td align='left'> Outer wood</td><td align='left'> Inner wood</td></tr>
+<tr><td align='left'>In original substance</td><td align='left'> 16.7</td><td align='left'> 19.6</td><td align='left'> 18.2</td><td align='left'> 20.7</td><td align='left'> 18.4</td></tr>
+<tr><td align='left'>In residue from action of 2.5 p.ct. HCl</td><td align='left'> 6.53</td><td align='left'> 8.6</td><td align='left'> 4.9</td><td align='left'> 6.4</td><td align='left'> 7.0</td></tr>
+</table></div>
+
+
+<p><i>Wood Gum.</i>&mdash;The paper contains some observations on the various methods
+of isolating this product. Attention is directed to the necessary
+impurity of the product, and to the fact that the numbers for furfural
+and for the xylose yielded by hydrolysis are considerably less than for
+a pure pentosane.<span class='pagenum'><a name="Page_144" id="Page_144">[Pg 144]</a></span></p>
+
+<p><i>Estimation of Cellulose.</i>&mdash;The author investigated the process of Lange
+and the 'celluloses' obtained from various raw materials. The products
+from the woods of birch and maple contained furfural-yielding
+constituents, represented by yields of 6-8 p.ct. furfural. Preference is
+given to the process by comparison with others, at the same time that it
+is recommended in all cases to examine the product for furfural
+quantitatively, converting the numbers into pentosane equivalents, and
+subtracting from the total 'cellulose' to give the true cellulose.</p>
+
+
+<h3>ZUR KENNTNISS DER MUTTERSUBSTANZEN DES HOLZGUMMI.</h3>
+
+<h4><span class="smcap">E. Winterstein</span> (Ztschr. Physiol. Chem., 1892, 381).</h4>
+
+<h3><b>ON THE MOTHER SUBSTANCES OF WOOD-GUM.</b></h3>
+
+<p>(p. 188) According to the text-books beech-wood may be regarded as the
+typical raw material for the preparation of the laboratory product known
+as wood-gum. The author has subjected beech-wood and beech-wood
+cellulose (Schulze process) to a range of hydrolytic treatments, acid
+and alkaline, in order to determine the conditions of selective action
+upon the mother substance of the wood-gum. In the main it appears that
+this group of furfuroids is equally resistant with the cellulose
+constituents of the wood; in fact, that the mother substance of wood-gum
+is a modified cellulose, and exists in the wood in chemical combination
+with the 'incrusting substances.'</p>
+
+<p>Of the author's experimental results the following may be cited as
+typical:</p>
+
+
+
+<div class='center'>
+<table border="0" cellpadding="4" cellspacing="0" summary="">
+<tr><td align='left'>Substance</td><td align='left'>Yield of furfural p.ct.</td></tr>
+<tr><td align='left'>Original beech-wood</td><td align='center'>13.8</td></tr>
+<tr><td align='left'>After boiling 3 hrs. with 1.25 p.ct. H<sub>2</sub>SO<sub>4</sub> (residue)</td><td align='center'>10.1</td></tr>
+<tr><td align='left'>&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;"&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;" &nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;" &nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;"&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;5.0&nbsp;&nbsp;&nbsp;&nbsp;&nbsp; "&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;" &nbsp;&nbsp;&nbsp;&nbsp;&nbsp;"&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;</td><td align='center'>5.6</td></tr>
+</table></div>
+
+
+<p><span class='pagenum'><a name="Page_145" id="Page_145">[Pg 145]</a></span></p>
+
+
+<div class='center'>
+<table border="0" cellpadding="4" cellspacing="0" summary="">
+<tr><td align='center'>Cellulose</td><td align='left'>&mdash;isolated by Schulze process (yield 53 p.ct.)</td><td align='left'>6.9</td></tr>
+<tr><td align='center'>"</td><td align='left'>after further 14 days' digestion with the Schulze acid (HNO<sub>3</sub> + KClO<sub>3</sub>)</td><td align='left'>5.9</td></tr>
+<tr><td align='center'>"</td><td align='left'>after extraction with 5 p.ct. NaOH in cold (residue)</td><td align='left'>5.0</td></tr>
+<tr><td align='center'>"</td><td align='left'>after second extraction with 5 p.ct. NaOH in cold (residue)</td><td align='left'>4.4</td></tr>
+</table></div>
+
+
+
+<h3>UEBER DIE FRAGE NACH DEM URSPRUNG UNGES&Auml;TTIGER VERBINDUNGEN IN DER PFLANZE.</h3>
+
+<h4><span class="smcap">C. F. Cross, E. J. Bevan</span>, and <span class="smcap">C. Smith</span> (Berl. Ber., 1895, 1940).</h4>
+
+<h3><b>ON THE SOURCE OF THE UNSATURATED COMPOUNDS OF THE PLANT.</b></h3>
+
+<p>(p. 179) In distilling for furfural by the usual methods of boiling
+cellulosic products with condensing acids, the furfural is accompanied
+by volatile acids, also products of decomposition of the cellulosic
+complex. A series of distillations was carried out with dilute sulphuric
+acids of varying concentration from 10-50 H<sub>2</sub>SO<sub>4</sub>: 90-50 H<sub>2</sub>O by
+weight, using barley straw as a typical cellulosic material. The
+distillates were collected in successive fractions, and the furfural and
+volatile acid determined. The results are given in the form of curves.
+The aggregate yields were as follows:&mdash;</p>
+
+
+<div class='center'>
+<table border="0" cellpadding="4" cellspacing="0" summary="">
+<tr><td align='left'>Concentration of acid (H<sub>2</sub>SO<sub>4</sub>) p.ct.</td><td align='left'>10</td><td align='left'>15</td><td align='left'>20</td><td align='left'>30</td><td align='left'>40</td><td align='left'>50</td></tr>
+<tr><td align='left'>Furfural yield p.ct. of straw</td><td align='left'>2.0</td><td align='left'>2.0</td><td align='left'>4.4</td><td align='left'>10.1</td><td align='left'>11.5</td><td align='left'>11.0</td></tr>
+<tr><td align='left'>Volatile acid (calculated as acetic acid) p.ct. of straw</td><td align='left'>1.7</td><td align='left'>1.9</td><td align='left'>3.1</td><td align='left'>4.3</td><td align='left'>6.3</td><td align='left'>14.8</td></tr>
+</table></div>
+
+
+<p>With acids up to 20 p.ct. H<sub>2</sub>SO<sub>4</sub> both products are formed
+concurrently and in nearly equal quantity. With the 30 p.ct.<span class='pagenum'><a name="Page_146" id="Page_146">[Pg 146]</a></span> acid there
+is a great increase in the total furfural, and with the 40 p.ct. acid it
+reaches nearly the maximum obtainable with HCl of 1.06 s.g. (Tollens),
+in this case 12.4 p.ct. The volatile acid increases, but in less ratio;
+it is also produced concurrently. With 50 p.ct. H<sub>2</sub>SO<sub>4</sub> the
+conditions are changed. The total furfural is rapidly formed, whereas
+the volatile acid continues to be formed long after the aldehyde ceases
+to come over. Moreover, whereas in the previous cases it was mainly
+acetic acid, it is now mainly formic acid. The method was then extended
+to a typical series of celluloses, heated with the more concentrated
+acid (40-50 p.ct. H<sub>2</sub>SO<sub>4</sub>), with the following results:</p>
+
+
+<div class='center'>
+<table border="1" cellpadding="4" cellspacing="0" summary="">
+<tr><td align='left'> &mdash;</td><td align='left'> &mdash;</td><td colspan="2"> Volatile acid</td></tr>
+<tr><td align='left'>&nbsp;</td><td align='left'>&nbsp;</td><td align='left'> Acetic</td><td align='left'> Formic</td></tr>
+<tr><td align='left'>Swedish filter-paper</td><td align='left'> 0.3</td><td align='left'> 2.7</td><td align='left'> 17.2</td></tr>
+<tr><td align='left'>Esparto cellulose</td><td align='left'> 12.4</td><td align='left'> 3.2</td><td align='left'> 16.6</td></tr>
+<tr><td align='left'>Bleached cotton</td><td align='left'> trace</td><td align='left'> 3.1</td><td align='left'> 13.2</td></tr>
+<tr><td align='left'>Raw cotton (American)</td><td align='left'> &mdash;</td><td align='left'> 5.0</td><td align='left'> 9.4</td></tr>
+<tr><td align='left'>Jute cellulose</td><td align='left'> 5.2</td><td align='left'> 4.9</td><td align='left'> 22.7</td></tr>
+<tr><td align='left'>Beech (wood) cellulose</td><td align='left'> 6.4</td><td align='left'> 3.5</td><td align='left'> 14.6</td></tr>
+</table></div>
+
+<p>The tendency in the hexoses and their polyanhydrides to split off one
+carbon atom in the oxidised form, throws some light on the furfurane
+type of condensation, which is represented in the lignocelluloses. We
+are still without any evidence as to the possible transition of the
+hexoses to benzenoid compounds. Such transitions would be more easily
+explained on the assumption that the celluloses are composed in part of
+polyanhydrides of the ketoses.</p>
+
+
+<h3>SPIRITUS AUS CELLULOSE UND HOLZ.</h3>
+
+<h4><span class="smcap">E. Simonsen</span> (Ztschr. angew. Chem., 1898, 3).</h4>
+
+<h3><b>PRODUCTION OF ALCOHOL FROM CELLULOSE AND WOOD.</b></h3>
+
+<p>(pp. 50, 209) This investigation was undertaken with one main object&mdash;to
+determine the optimum conditions of treatment<span class='pagenum'><a name="Page_147" id="Page_147">[Pg 147]</a></span> of wood-cellulose and of
+wood itself for conversion into 'fermentable sugar.' The process of
+'inversion' or hydrolysis, by digestion with dilute acid at high
+temperature, involves the four main factors: pressure (i.e.
+temperature), concentration of acid, ratio of liquid to cellulose and
+duration of digestion. Each of these was varied in definite gradations,
+and the effect measured. The degree of action was measured in terms of
+'reducing sugar,' calculated from the results of estimation by Fehling
+solution, as 'glucose' per cent. of original cellulose (or wood).</p>
+
+<p>(<i>a</i>) <i>Cellulose.</i> [Wood-cellulose obtained by bisulphite
+process.]&mdash;With a proportion of total liquid to cellulose of 27:1, and
+using sulphuric acid as the hydrolysing agent, the optimum results were
+obtained with acids of 0.45-0.60 p.ct. (H<sub>2</sub>SO<sub>4</sub>) and pressures of
+6-8 atm. The maximum yield of 'sugar' was 45 p.ct. of the cellulose.</p>
+
+<p>Under the above conditions the maximum of conversion is attained in 2
+hours.</p>
+
+<p>Having now regard to the production of a solution of maximum
+<i>concentration</i> of dissolved solids, the following conditions were
+asertained to fulfil the requirement, and, in fact, may be regarded as
+the economic optimum:</p>
+
+
+<div class='center'>
+<table border="0" cellpadding="4" cellspacing="0" summary="">
+<tr><td align='left'>Proportion of total liquid</td><td align='center'>6 times wt. of cellulose</td></tr>
+<tr><td align='left'>Concentration of acid</td><td align='center'>0.5 p.ct. H<sub>2</sub>SO<sub>4</sub></td></tr>
+<tr><td align='left'>Pressure</td><td align='center'>10 atm.</td></tr>
+<tr><td align='left'>Duration of digestion</td><td align='center'>1.5 hour</td></tr>
+</table></div>
+
+<p>giving a yield of 41 p.ct. 'reducing sugar' calculated to the original
+cellulose (dry).</p>
+
+<p><i>Alcoholic Fermentation of Neutralised Extract.</i>&mdash;The liquors were found
+to ferment freely, and on distillation to yield a quantity of alcohol
+equal to 70 p.ct. of the theoretical&mdash;i.e. on the basis of the numbers
+for copper oxide reduction.</p>
+
+<p>(<i>b</i>) <i>Hydrolytic 'Conversion' of Wood (Lignocellulose).</i>&mdash;A<span class='pagenum'><a name="Page_148" id="Page_148">[Pg 148]</a></span> similarly
+systematic investigation carried out upon pine sawdust established the
+following as optimum conditions:</p>
+
+
+<div class='center'>
+<table border="0" cellpadding="4" cellspacing="0" summary="">
+<tr><td align='left'>Proportion of total liquid</td><td align='center'>5 times wt. of wood</td></tr>
+<tr><td align='left'>Concentration of acid</td><td align='center'>0.5 p.ct. H<sub>2</sub>SO<sub>4</sub></td></tr>
+<tr><td align='left'>Pressure</td><td align='center'>9 atm.</td></tr>
+<tr><td align='left'>Duration of digestion</td><td align='center'>15 minutes</td></tr>
+</table></div>
+
+<p>giving a yield of 20 p.ct. 'reducing sugar,' calculated from the
+'Fehling' test.</p>
+
+<p><i>Fermentation</i> of the neutralised extracts gave variable results. The
+highest yields obtained were 60 p.ct. of theoretical, the author finally
+concluding that under properly controlled conditions of inversion and
+fermentation 100 kg. wood yield 6.5 l. absolute alcohol.</p>
+
+
+<h3>&Uuml;BER DIE URSACHE DER VON SIMONSEN BEOBACHTETEN UNVOLLST&Auml;NDIGKEIT DER
+VERG&Auml;HRUNG DER AUS HOLZ BEREITETEN ZUCKERFL&Uuml;SSIGKEITEN.</h3>
+
+<h4><span class="smcap">B. Tollens</span> (Ztschr. angew. Chem., 1898, 15).</h4>
+
+<h3><b>ON THE CAUSE OF INCOMPLETE FERMENTATION OF SUGARS OBTAINED BY ACID
+HYDROLYSIS OF WOOD.</b></h3>
+
+<p>The author criticises Simonsen's explanation of the results obtained
+with extracts from pine wood. The incompleteness of fermentation of the
+products is certainly due in part to the presence of furfural-yielding
+carbohydrates, which are resistant to yeast. The pine woods contain 8-10
+p.ct. of these constituents in their anhydride form ('pentosanes'). They
+yield readily to acid hydrolysis, and certainly constitute a
+considerable percentage of the dissolved products. A similar complex was
+obtained by the author in his investigation of peat (Berl. Ber. 30,
+2571), and was found to be similarly incompletely attacked by yeast. The
+yields of alcohol corresponded<span class='pagenum'><a name="Page_149" id="Page_149">[Pg 149]</a></span> with the proportion of the total
+carbohydrates disappearing. These were the hexose constituents of the
+hydrolysed complex, the pentoses (or 'furfuroids') surviving intact.</p>
+
+
+<h3>UEBER SULFITCELLULOSEABLAUGE.</h3>
+
+<h4><span class="smcap">H. Seidel</span> (Ztschr. angew. Chem., 1900).</h4>
+
+<h3><b>WASTE LIQUORS FROM BISULPHITE PROCESS.</b></h3>
+
+<p>(p. 210) Later researches confirm the conclusion that in the soluble
+by-products of these cellulose processes the S is combined as a SO<sub>3</sub>H
+group. The following analyses of the isolated lignin sulphonic acid are
+cited:</p>
+
+<div class='center'>
+<table border="1" cellpadding="4" cellspacing="0" summary="">
+<tr><td align='left'></td><td align='center'> C</td><td align='center'> H</td><td align='center'> S</td></tr>
+<tr><td align='left'>(<i>a</i>) Lindsey and Tollens</td><td align='left'> 56.12</td><td align='left'> 5.30</td><td align='left'> 5.65</td></tr>
+<tr><td align='left'>(<i>b</i>) Seidel&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;    (1)</td><td align='left'> 56.27</td><td align='left'> 5.87</td><td align='left'> 5.52</td></tr>
+<tr><td align='left'>(<i>c</i>) Seidel and Hanak (2)</td><td align='left'> 53.69</td><td align='left'> 5.22</td><td align='left'> 8.80</td></tr>
+<tr><td align='left'>(<i>d</i>) Street</td><td align='left'> 50.22</td><td align='left'> 5.64</td><td align='left'> 7.67</td></tr>
+</table></div>
+
+
+<p>The variations are due to the varying conditions of the digestion of the
+wood and to corresponding degrees of sulphonation of the original
+lignone group. Calculating the composition of the latter from the above
+numbers on the assumption that the S represents SO<sub>3</sub>H, the following
+figures result:</p>
+
+
+<div class='center'>
+<table border="1" cellpadding="4" cellspacing="0" summary="">
+<tr><td align='left'>&nbsp;</td><td align='left'> (<i>a</i>) and (<i>b</i>)</td><td align='left'> (<i>c</i>)</td><td align='left'> (<i>d</i>)</td></tr>
+<tr><td align='left'>C</td><td align='left'> 64.00</td><td align='left'> 65.1</td><td align='left'> 59.61</td></tr>
+<tr><td align='left'>H</td><td align='left'> 6.65</td><td align='left'> 6.33</td><td align='left'> 6.69</td></tr>
+</table></div>
+<p>This author considers that beyond the empirical facts established by the
+above named<a name="FNanchor_10_10" id="FNanchor_10_10"></a><a href="#Footnote_10_10" class="fnanchor">[10]</a> very little is yet known in regard to the constitution
+of the lignone complex.<span class='pagenum'><a name="Page_150" id="Page_150">[Pg 150]</a></span></p>
+
+<p>Nor is there any satisfactory application of this by-product as yet
+evolved. Evaporation and combustion involve large losses of sulphur
+[D.R.P. 74,030, 83,438; Seidel and Hanak, Mitt. Techn. Gew. Mus. 1898].
+A more complete regeneration of the sulphur has been the subject of a
+series of patents [D.R.P. 40,308, 69,892, 71,942, 78,306, 81,338], but
+the processes are inefficient through neglect of the actual state of
+combination of the S, viz. as an organic sulphonate. The process of V.B.
+Drewson (D.R.P. 67,889) consists in heating with lime under pressure,
+yielding calcium monosulphite (with sulphate and the lignone complex in
+insoluble form). The sulphite is redissolved as bisulphite by treatment
+with sulphurous acid. This process is relatively costly, and yields
+necessarily an impure lye. It has been proposed to employ the product as
+a foodstuff both in its original form and in the form of benzoate
+(D.R.P. 97,935); but its unsuitability is obvious from its composition.
+A method of destructive distillation has been patented (D.R.P. 45,951).
+The author has investigated the process, and finds that the yield of
+useful products is much too low for its economical development. Fusion
+with alkaline hydrates for the production of oxalic acid (D.R.P. 52,491)
+is also excluded by the low yield of the product.</p>
+
+<p>The application of the liquor for tanning purposes (D.R.P. 72,161)
+appears promising from the fact that 28 p.ct. of the dry residue is
+removed by digestion with hide powder. This application has been
+extensively investigated, but without practical success. Various
+probable uses are suggested by the viscosity of the evaporated extract.
+As a substitute for glue in joinery work, bookbinding, &amp;c., it has
+proved of little value. It is applied to some extent as a binding
+material in the<span class='pagenum'><a name="Page_151" id="Page_151">[Pg 151]</a></span> manufacture of briquettes, also as a substitute for
+gelatin in the petroleum industry. Cross and Bevan (E.P. 1548/1883) and
+Mitscherlich (D.R.P. 93,944 and 93,945) precipitate a compound of the
+lignone complex and gelatin by adding a solution of the latter to the
+liquors. The compound is redissolved in weak alkaline solutions and
+employed in this form for engine-sizing papers. Ekman has patented a
+process (D.R.P. 81,643) for 'salting out' the lignone sulphonates, the
+product being resoluble in water and the solution having some of the
+properties of a solution of dextrin. Owing to its active chemical
+properties this product&mdash;'dextron'&mdash;has a limited capability of
+substituting dextrin. The suggestion to employ the evaporated extract as
+a reducing agent in indigo dyeing and printing has also proved
+unfruitful. The author's application of the soda salt of the lignone
+sulphonic acid as a reducing agent in chrome-mordanting wool and woollen
+goods (D.R.P. 99,682) is more successful in practice, and its industrial
+development shows satisfactory progress. The product is known as
+'lignorosin.'</p>
+
+<div class="footnotes"><h3>FOOTNOTES:</h3>
+
+<div class="footnote"><p><a name="Footnote_10_10" id="Footnote_10_10"></a><a href="#FNanchor_10_10"><span class="label">[10]</span></a> See more particularly: Lindsey and Tollens, <i>Annalen</i>,
+267, 341; Cross and Bevan's <i>Cellulose</i>, pp. 197-203; Street,
+Inaug.-Diss., G&ouml;ttingen, 1892; Klason, <i>Rep. d. Chem. Ztg.</i> 1897, 261;
+Seidel and Hanak, <i>Mitt. d. Techn. Gew. Mus.</i> 1897-1898.</p></div>
+</div>
+
+
+<hr style="width: 65%;" />
+<p><span class='pagenum'><a name="Page_152" id="Page_152">[Pg 152]</a></span></p>
+<h2>SECTION VII. PECTIC GROUP</h2>
+
+<h3>UNTERSUCHUNGEN &Uuml;BER PECTINSTOFFE.</h3>
+
+<h4><span class="smcap">R. W. Tromp de Haas</span> and <span class="smcap">B. Tollens</span> (Lieb. Ann., 286, 278).</h4>
+
+<h3>&Uuml;BER DIE CONSTITUTION DER PECTINSTOFFE, <span class="smcap">B. Tollens</span> (<i>ibid.</i> 292).</h3>
+
+<h4><b>INVESTIGATIONS OF PECTINS.</b></h4>
+
+<p>(p. 216) It is generally held that the pectins are, or contain, oxidised
+derivatives of the carbohydrates. The authors have isolated and analysed
+a series of these products, and the results fail to confirm a high
+ratio O : H. The following are the analytical numbers:</p>
+
+
+<div class='center'>
+<table border="1" cellpadding="4" cellspacing="0" summary="">
+<tr><td align='left'>Pectin from</td><td align='left'> Ash</td><td align='left'> C</td><td align='left'> H</td><td align='left'> Ratio H : O</td></tr>
+<tr><td align='left'>Apple</td><td align='left'> 6.2</td><td align='left'> 43.4</td><td align='left'> 6.4</td><td align='left'> 1 : 7.9</td></tr>
+<tr><td align='left'>Cherry</td><td align='left'> 20.5</td><td align='left'> 42.5</td><td align='left'> 6.5</td><td align='left'> 1 : 7.9</td></tr>
+<tr><td align='left'>Rhubarb</td><td align='left'> 4.2</td><td align='left'> 43.3</td><td align='left'> 6.8</td><td align='left'> 1 : 7.4</td></tr>
+<tr><td align='left'>Currant</td><td align='left'> 5.0</td><td align='left'> 47.1</td><td align='left'> 5.9</td><td align='left'> 1 : 8.5</td></tr>
+<tr><td align='left'>Greengage</td><td align='left'> 3.3</td><td align='left'> 43.0</td><td align='left'> 5.9</td><td align='left'> 1 : 8.5</td></tr>
+<tr><td align='left'>Turnip</td><td align='left'> 7.3</td><td align='left'> 41.0</td><td align='left'> 5.9</td><td align='left'> 1 : 9.0</td></tr>
+</table></div>
+
+
+<p>Acid hydrolysis (4 p.ct. H<sub>2</sub>SO<sub>4</sub>) gave syrupy products not
+crystallisable&mdash;in certain cases the hydrolysis was accompanied by
+separation of insoluble cellulose. The insoluble product from currant
+pectin had the composition C 54.4, H 5.0.
+</p>
+
+<p>Tollens points out that the results of empirical analysis are
+inconclusive; and that from the acid reactions of these products and
+their combination with bases, carboxylic groups are present, though
+probably in anhydride or ester form.</p>
+
+<p>The pectins may be regarded as closely related to the mucilages
+(<i>Pflanzenschleim</i>), differing from them only by the presence of the
+oxidised groups in question.</p>
+
+
+<h3>UEBER DIE CONSTITUTION DER PECTINSTOFFE.</h3>
+
+<h4>C. F. Cross (Berl. Ber., 1895, 2609).</h4>
+
+<h3>CONSTITUTION OF PECTINS.</h3>
+
+<p>It is pointed out that the composition of the pectin of white currants,
+as given in the preceding paper, is that of the typical lignocellulose,
+the jute fibre. The product was isolated and further investigated by the
+author. It gave 9.8 p.ct. furfural on boiling with HCl (1.06 s.g.),
+reacted freely with chlorine, giving quinone chlorides, and with ferric
+<span class='pagenum'><a name="Page_153" id="Page_153">[Pg 153]</a></span>ferricyanide to form Prussian blue. This 'pectin' is therefore a form
+of soluble lignocellulose. The 'pectic' group consequently must be
+extended to include hydrated and soluble forms of the mixed complex of
+condensed and unsaturated groups with normal carbohydrates, such as
+constitute the fibrous lignocelluloses.</p>
+
+
+<h3>UEBER DAS PFLANZLICHE AMYLOID.</h3>
+
+<h4>E. Winterstein (Ztschr. Physiol. Chem., 1892, 353).</h4>
+
+<h3>ON VEGETABLE AMYLOID.</h3>
+
+<p>(p. 224) A group of constituents of many seeds, distinguished by giving
+slimy or ropy 'solutions' under the action of boiling water are
+designated 'amyloid.' They are reserve materials, and in this, as in the
+physical properties of their 'solutions,' they are very similar to
+starch. They are, however, not affected by diastase; and generally are
+more resistant to hydrolysis. Typical amyloids have been isolated by the
+author from seeds of <i>Trop&oelig;olum majus, P&oelig;onia officinalis</i>, and
+<i>Impatiens Balsamina</i>. The raw material was carefully purified by
+exhaustive treatment with ether and alcohol, &amp;c.; the amyloid then
+extracted by boiling with water, and isolated by precipitation with
+alcohol. Elementary analysis gave the numbers C 43.2, H 6.1. On boiling
+with 12 p.ct. HCl it gave 15.3 p.ct. furfural; oxidised with nitric acid
+it yielded 10.4 p.ct. mucic acid. Specimens from the two first-named raw
+materials gave almost identical numbers.</p>
+
+<p><i>Hydrolysis.</i>&mdash;On boiling with dilute acids these products are gradually
+broken down, dissolving without residue. In this respect they are
+differentiated from the mucilages, which give a residue of cellulose
+(insoluble). From the solution the author isolated crystalline
+galactose, but failed to isolate a pentose. Dextrose was also not
+identified directly.</p>
+
+<p><span class='pagenum'><a name="Page_154" id="Page_154">[Pg 154]</a></span></p>
+
+<p>The tissue residues left after extracting the amyloid constituent, as
+above described, were subjected to acid hydrolysis. A complex of
+products was obtained, from which galactose was isolated. A
+furfural-yielding carbohydrate was also present in some quantity, but
+could not be isolated. The original seed tissues, therefore, contain an
+amyloid and a hemicellulose, the latter differentiated in its resistance
+to water. Both yield, however, to acid hydrolysis a complex of products
+of similar composition and constitution.</p>
+
+
+<h3>UEBER DEN GEHALT DES TORFES AN PENTOSANEN ODER FURFUROLGEBENDEN STOFFEN
+UND AN ANDEREN KOHLENHYDRATEN.</h3>
+
+<h4>H. v. Feilitzen and B. Tollens (Berl. Ber., 1897, 2,571).</h4>
+
+<h3>CARBOHYDRATE CONSTITUENTS OF PEAT.</h3>
+
+<p>(p. 240) An investigation of typical peats taken at successive depths
+showed increasing percentage of carbon, and inversely a decreasing yield
+of furfural. The numbers may be compared with those for <i>Sphagnum
+cuspidatum</i>&mdash;with C = 49.80 p.ct., and furfural 7.99 p.ct., calculated
+to dry, ash-free substance:</p>
+
+
+
+<div class='center'>
+<table border="1" cellpadding="4" cellspacing="0" summary="">
+<tr><td colspan="2">Depth at which taken</td><td align='left'> C p.ct.</td><td align='left'> Furfural p.ct.</td></tr>
+<tr><td rowspan="3">I.</td><td align='left'> 20-100 cm.</td><td align='left'> 51.08</td><td align='left'> 6.93</td></tr>
+<tr><td align='left'> 100-200 "</td><td align='left'> 53.52</td><td align='left'> 5.30</td></tr>
+<tr><td align='left'> 200-300 "</td><td align='left'> 58.66</td><td align='left'> 3.19</td></tr>
+<tr><td rowspan="5">II.</td><td align='left'> Surface-20 "</td><td align='left'> 55.47</td><td align='left'> 3.40</td></tr>
+<tr><td align='left'> 20-60 "</td><td align='left'> 55.06</td><td align='left'> 3.48</td></tr>
+<tr><td align='left'> 60-100 "</td><td align='left'> 58.25</td><td align='left'> 1.45</td></tr>
+<tr><td align='left'> 100-120 "</td><td align='left'> 58.23</td><td align='left'> 1.19</td></tr>
+<tr><td align='left'> 180-200 "</td><td align='left'> 57.57</td><td align='left'> 1.80</td></tr>
+</table></div>
+
+
+<p><i>Cellulose</i> was estimated by the Lange method. The yield from <i>Sphagnum</i>
+was 21.1 p.ct.</p>
+
+
+<div class='center'>
+<table border="0" cellpadding="4" cellspacing="0" summary="">
+<tr><td align='left'>From specimen I. at</td><td align='left'>{ 20-100 cm.</td><td align='left'>15.20</td></tr>
+<tr><td align='left'></td><td align='left'>{100-200&nbsp;&nbsp;&nbsp;&nbsp;"</td><td align='left'>6.87</td></tr>
+</table></div>
+
+<p><span class='pagenum'><a name="Page_155" id="Page_155">[Pg 155]</a></span></p>
+
+<p>From the peat of lower depths no cellulose could be obtained.</p>
+
+<p><i>Hydrolysis</i> (acid).&mdash;On heating with 1 p.ct. H<sub>2</sub>SO<sub>4</sub> at 130-135&deg;,
+soluble carbohydrates were obtained, amongst which mannose was
+identified, and galactose shown to be present in some quantity. After
+fermenting away the hexoses, the residue was treated with
+phenylhydrazine and an osazone separated. It contained 17.3 p.ct. N, but
+melted at 130&deg;. The substance could not be identified as an osazone of
+any of the yet known pentoses.</p>
+
+
+
+<hr style="width: 65%;" />
+<h2>SECTION VIII. INDUSTRIAL AND TECHNICAL. GENERAL REVIEW</h2>
+
+
+<h3><b>The Industrial Uses of Cellulose.</b></h3>
+
+<h4><span class="smcap">C. F. Cross</span> (Cantor Lectures, Soc. of Arts, 1897).</h4>
+
+<p>(p. 273) A series of three lectures, in which the more important
+industries in cellulose and its derivatives are dealt with on their
+scientific foundations, and by means of a selection of typical problems.
+In reference to textiles, the small number of vegetable fibres actually
+available, out of the endless variety afforded by the plant world, is
+referred to the number of conditions required to be fulfilled by the
+individual fibre, thus: yield per cent. of harvested weight or per unit
+of field area, ease of extraction, the absolute dimensions of the
+spinning unit, and the proportion of variation from the mean dimensions;
+the relative facility with which the unit fibre can be isolated
+preparatory to the final twisting operation; the chemical constants of
+the fibre substance, especially the percentage of cellulose and degree
+of resistance to hydrolysis. It is suggested that any important addition
+to the very limited number fulfilling the conditions, or any great
+improvement in these, can only result from very elaborate artificial
+selection and cultural developments on this basis.<span class='pagenum'><a name="Page_156" id="Page_156">[Pg 156]</a></span></p>
+
+<p>The paper making fibres are shown to fall into a scheme of
+classification based on chemical constitution, and consisting of the
+four groups: (<i>a</i>) Cotton [flax, hemp, rhea], (<i>b</i>) wood celluloses,
+(<i>c</i>) esparto, straw, and (<i>d</i>) lignocelluloses. Papers being exposed to
+the natural disintegrating agencies, more especially oxygen, water (and
+hydrolysing agents generally), and micro-organisms, the relative
+resistance of the above groups of raw materials is discussed as an
+important condition of value. The indirect influence of the ordinary
+sizing and 'filling' materials is discussed. The paper-making quality of
+the fibrous raw materials is also discussed, not merely from the point
+of view of the form and dimensions of the ultimate fibres, but their
+capacity for 'colloidal hydration.' This is complementary to the action
+of rosin, i.e. resin acids, in the engine-sizing of papers; and the
+proof of the potency of this factor is seen in the superior effects
+obtained in sizing jointly with solutions of cellulose and, more
+particularly, viscose and rosin. Wurster's much-cited monograph of the
+subject of rosin-sizing ['Le Collage des Papiers,' Bull. Mulhouse, 1878]
+neglects to take into consideration the contribution of the cellulose
+hydrates to the total and complex sizing effect, and hence gives a
+partial view only of the function of the resin acids.</p>
+
+<p>In further illustration of fundamental principles various developments
+in the textile industries are discussed, e.g. the bleaching of jute,
+cotton, and flax, and special developments in the spinning of rhea and
+flax.</p>
+
+<p>The concluding lecture deals with later progress in the industrial
+applications of cellulose derivatives, chiefly the sulphocarbonate
+(viscose); the nitrates, in their applications to explosives, on the one
+hand, and the spinning of artificial fibres (lustra-cellulose), on the
+other; and the cellulose acetates.<span class='pagenum'><a name="Page_157" id="Page_157">[Pg 157]</a></span></p>
+
+
+<h3><b>La Viscose et le Viscoide.</b></h3>
+
+<h4><span class="smcap">C. H. Bardy</span> (Bull. Soc. d'Enc. Ind. Nationale, 1900, March).</h4>
+
+<p>This is a report presented to the Committee of Economic Arts of the
+above Society, dealing with the industrial progress in products obtained
+by means of the sulphocarbonate of cellulose (viscose).</p>
+
+<p>The following developments are noted:</p>
+
+<p><i>Engine-sized Papers.</i>&mdash;The viscose, by coating the fibres with
+regenerated cellulose hydrate, adds very much to the tensile strength of
+papers. Increase of 40-60 p.ct. is attainable by addition of cellulose
+in this form from 1-4 p.ct. on the weight of the paper.</p>
+
+<p><i>Viscoid.</i>&mdash;Solid aggregates are formed by incorporating viscose with
+mineral matters, hydrocarbons, &amp;c. Products are cast or moulded into
+convenient forms, and, after purification and sufficient ageing, are
+available for various structural uses.</p>
+
+<p><i>Paint.</i>&mdash;The viscose is used as a vehicle for pigments, the mixture
+being used either as a paint or for coating papers with fine surfaces,
+such as required in the reproduction of photo-blocks. In these
+applications the extraordinary viscosity of the product conditions the
+economic use of the cellulose in competition with oils, on the one hand,
+and organic colloids, such as gelatine, casein, &amp;c., on the other.</p>
+
+<p>By suitable alteration of the formula for making the paint a product is
+obtained which has an extraordinary power of removing paint from old
+painted surfaces. The product has been officially adopted by the French
+Admiralty, and receives extensive application in removing the paint from
+ships.</p>
+
+<p><i>Films.</i>&mdash;Films are produced from the viscose itself in various ways.
+Plane or flat by solidifying the viscose on glass surfaces, removing the
+by-products and rolling the films. The<span class='pagenum'><a name="Page_158" id="Page_158">[Pg 158]</a></span> film is also produced by
+applying the viscose on textile fabrics, drying down, and fixing on a
+stenter machine, then washing away the alkaline by-products from the
+fixed film. A large number of industrial effects are obtained by
+suitably varying the mixtures applied.</p>
+
+<p><i>Cellulose-indiarubber.</i>&mdash;The viscose, in its concentrated form, can be
+incorporated with rubber-hydrocarbon mixtures, and these mixtures can be
+used both as water-proofing films, as applied to textiles, or can be
+solidified into the class of goods known as 'mechanicals.' The cellulose
+not only cheapens the mixture, but produces new technical effects.</p>
+
+<p><i>Spinning.</i>&mdash;The viscose is spun by special methods, patented by C. H.
+Stearn. As produced in thread form, the diameters are approximately
+those of natural silk. In commercial form it is a multiple thread (of 15
+or more units) at from 50-200 deniers on the silk counts. It is a thread
+of high lustre, and more nearly approaches the normal cellulose in
+chemical properties than any of the other artificial silks. It can also
+be spun in threads of very much larger diameter, which can be used as a
+substitute for horsehair, for carbonising for incandescent electric
+lamps, &amp;c.</p>
+
+<p><i>Cellulose Esters.</i>&mdash;These are conveniently made from cellulose,
+regenerated from the solution as sulphocarbonate. The tetracetate is
+made from this product on the industrial scale. Nitrates are
+conveniently made by treatment with the ordinary mixed acids. For fuller
+details the original report may be consulted.</p>
+
+
+<h3>VISKOS.</h3>
+
+<h4><span class="smcap">R. W. Strehlenert</span> (Svensk Kemisk Tidskrift, Stockholm, 1900, p. 185).</h4>
+
+<p>A report on the industrial development of viscose, covering essentially
+the same ground as the above.<span class='pagenum'><a name="Page_159" id="Page_159">[Pg 159]</a></span></p>
+
+
+<h3><b>Ueber die Viscose.</b></h3>
+
+<h4><span class="smcap">B. M. Margosches</span> (Reprint from Zeitschrift f&uuml;r die gesammte
+Textil-Industrie, 1900-01, Nos. 14-20).<a name="FNanchor_11_11" id="FNanchor_11_11"></a><a href="#Footnote_11_11" class="fnanchor">[11]</a></h4>
+
+
+<h3><b>Report of Committee on the Deterioration of Paper.</b></h3>
+
+<h4>(Soc. of Arts, 1898.)</h4>
+
+<p>(p. 304) The Report of a Representative Committee appointed by the
+Society of Arts to inquire into the question of qualities of book papers
+in relation to their several applications, and more especially for
+documents of permanent value.</p>
+
+<p>The report first discusses the two directions of depreciation of papers
+in use: (1) Actual disintegration shown by loss of resistance to
+fracture by simple strain, and by loss of elasticity&mdash;i.e. increase of
+brittleness; (2) discolouration. These are independent effects, but
+often concurrent. They are the result of chemical changes of the
+cellulose basis of the paper, brought about by acids or oxidants used in
+the process of manufacture, and not completely removed from the pulp, or
+by acid products of bleaching&mdash;e.g. oxycelluloses or chlorinated
+derivatives; again, by the changes of starch used as a 'sizing' agent,
+or by oxidations induced by rosin constituents when the rosin is used in
+excess. Discolouration is an attendant phenomenon of these changes, but
+is more frequently due to the presence of the lower-grade celluloses
+(esparto and straw) and the lignocelluloses (mechanical wood-pulp).</p>
+
+<p>The physical and chemical qualities of papers depending primarily upon
+their fibrous or pulp basis, and in a secondary degree upon the kind and
+proportion of the constituents added<span class='pagenum'><a name="Page_160" id="Page_160">[Pg 160]</a></span> for the purpose of filling and
+'sizing,' the report concludes with the following recommendations,
+positive and negative, under these heads:</p>
+
+<p>The Committee find that the practical evidence as to permanence fully
+confirms the classification given in the Cantor Lectures on 'Cellulose,'
+1897 [J. Soc. Arts, xlv. 690-696], and which ranges the paper-making
+fibres in four classes:</p>
+
+<p>(<span class="smcap">A</span>) Cotton, flax, and hemp (rhea).</p>
+
+<p>(<span class="smcap">B</span>) Wood celluloses, (<i>a</i>) sulphite process and (<i>b</i>) soda and
+'sulphate' process.</p>
+
+<p>(<span class="smcap">C</span>) Esparto and straw celluloses.</p>
+
+<p>(<span class="smcap">D</span>) Mechanical wood-pulp.</p>
+
+<p>In regard, therefore, to papers for books and documents of permanent
+value, the selection must be taken in this order, and always with due
+regard to the fulfilment of the conditions of normal treatment above
+dealt with as common to all papers.</p>
+
+<p>The Committee have been desirous of bringing their investigations to a
+practical conclusion in specific terms&mdash;viz. by the suggestion of
+standards of quality. It is evident that in the majority of cases there
+is little fault to find with the practical adjustments which rule the
+trade. They are, therefore, satisfied to limit their specific findings
+to the following&mdash;viz. (1) normal standard of quality for book-papers
+required for publications of permanent value. For such papers they
+specify as follows:</p>
+
+<p>Fibres: Not less than 70 p.ct of fibres of class A; class D excluded.</p>
+
+<p>Sizing: Not more than 2 p.ct. rosin, and finished with the normal
+acidity of pure alum; starch excluded.</p>
+
+<p>Loading: Not more than 10 p.ct. total mineral matter (ash).</p>
+
+<p>(2) With regard to written documents, it must be evident that the proper
+materials are those of class A, and that the<span class='pagenum'><a name="Page_161" id="Page_161">[Pg 161]</a></span> paper should be pure and
+sized with gelatin, and not with rosin. All imitations of high-class
+writing-papers which are, in fact, merely disguised printing-papers,
+should be carefully avoided.</p>
+
+<p><i>Appendix.</i>&mdash;To the Report is added 'Abstracts of Papers' in
+'Mittheilungen aus den Koniglichen Technischen Versuchsanstalten,
+Berlin,' for the years 1885-1896 inclusive&mdash;which is, in fact, a summary
+of the investigations of the Institution in connection with paper and
+paper-standards.</p>
+
+<hr style='width: 45%;' />
+
+<p>(p. 273) <b>Special Industrial Developments.</b>&mdash;From the point of view of the
+chemist there has been a very large development of the cellulose
+industries during the last five years. This is not so much marked by the
+gradual and progressive growth of the well-established industries, as by
+the success of the newer ones, with the attendant forecast of enormous
+developments of the industries in artificial products, the manufacture
+of which rests upon a purely chemical basis. We can, of course, only
+treat them from this limited standpoint, and so far as they involve and
+elucidate chemical principles.</p>
+
+
+<h4><b>I. Chemical Treatments of Raw Materials.</b></h4>
+
+<p>(<i>a</i>) <b>Flax-spinning.</b>&mdash;The treatment of the roving on the spinning-frame
+by the addition of reagents to the macerating liquid&mdash;otherwise and
+usually hot water&mdash;continues to be justified by results. The technical
+basis of the process and the reactions determined in the spinning-trough
+by the alkaline salts used&mdash;chiefly sulphite and phosphate of soda&mdash;is
+set forth in the original work, p. 280. Since that time a sufficient
+period has elapsed to judge the effects, both technical and industrial,
+by the results of a commercial undertaking based on the exclusive use of
+the process. Such a concern is<span class='pagenum'><a name="Page_162" id="Page_162">[Pg 162]</a></span> the Irish Flax Spinning Company of
+Belfast. At this mill the experience is uniform and fully established
+that by means of the process the drawing, <i>i.e.</i> spinning, quality of
+inferior flaxes is very considerably appreciated, enabling the spinner
+to use such flaxes for yarns of fineness which are unattainable by the
+ordinary method of spinning through hot water. Notwithstanding the
+success of this undertaking the development of the method is still
+inconsiderable. It is none the less a further and forcible demonstration
+of the existence of margins of increased technical effect which it is
+the work of the scientific technologist to exploit.</p>
+
+<p>(<i>b</i>) <b>Wood-pulp and Methods of Manufacture.</b>&mdash;There is a steady growth in
+the consumption of wood-pulps (cellulose) relatively to other materials.
+In regard to the paper-trade of the world, this continues to be one of
+the most prominent characteristics of its evolution. In the United
+Kingdom the conditions of its competition are of a more special kind by
+reason of the firm foothold of esparto, which is a most important staple
+in the manufacture of fine printings. Whereas the consumption of esparto
+remains nearly stationary at about 200,000 tons per annum, the
+importation of wood-pulps has shown the extraordinary rate of increase
+of doubling itself every five years. But in the group 'wood-pulps' the
+trade returns have until recently included the 'mechanical' or ground
+wood-pulps. From 1898 we have separate returns for the chemical or
+cellulose pulps, and in 1899 the tonnage reached nearly to that of
+esparto, with a total money value about 80 p.ct. greater. When it is
+remembered that this is one of the newer chemical industries in
+cellulose products, and that these large commercial results have been
+accomplished during a period of twenty years, we are impressed with the
+scope of the industrial outlook to the chemist, afforded by the arts of
+which cellulose is the foundation.<span class='pagenum'><a name="Page_163" id="Page_163">[Pg 163]</a></span></p>
+
+<p>It may be noted that there have been no important developments in the
+purely chemical processes involved in the several systems of preparing
+cellulose from wood. The acid methods (bisulphite processes) have
+developed much more extensively than the alkaline, the latter including
+the caustic soda and the mixed sulphide ('Dahl') process. The bisulphite
+processes depended in the earlier stages upon the efficiency of
+lead-lined digesters. But the problem of acid-resisting linings has been
+much more perfectly solved in later years in the various types of cement
+and other silicate linings now in use. The relative permanency of these
+linings has had an important effect on the costs of production. Further
+economies result from the use of digesters of enormous capacity, dealing
+with as much as 100 tons of wood at one operation. As a combined result
+of economic production and active competition, the selling prices of
+'sulphite pulp' have moved steadily downwards in relation to other
+half-stuffs and raw materials. As a necessary consequence the prices of
+those which it has gradually displaced have depreciated, and a study of
+the price and tonnage-equilibrium as between rags, esparto, and
+wood-pulp over a series of years forms an interesting object-lesson in
+the struggle for survival which is an especial mark of modern industry.
+For these matters the reader is referred to the special literature of
+the paper-making industry.<a name="FNanchor_12_12" id="FNanchor_12_12"></a><a href="#Footnote_12_12" class="fnanchor">[12]</a></p>
+
+<p>It is not a little remarkable that the main by-product of these
+bisulphite processes&mdash;the sulphonated derivatives of the lignone
+constituents of the wood&mdash;is still for the most part an absolute waste,
+notwithstanding the many investigations of technologists and attempts to
+convert it to industrial use (see<span class='pagenum'><a name="Page_164" id="Page_164">[Pg 164]</a></span> p. 149). Seeing that it represents a
+percentage on the wood pulped equal to that of the cellulose obtained,
+it is a waste of potentially valuable material which can only be termed
+colossal. Moreover, as a waste to be discharged into water-courses, it
+becomes a source of burden and expense to the manufacturer, and with the
+increasing restrictions on the pollution of rivers it is in many
+localities a difficulty to be reckoned with only by the cessation of the
+industry. The problem in such cases becomes that of dealing with it
+destructively, <i>i.e.</i> by evaporation and burning. In this treatment the
+obviously high calorific value of the dissolved organic matter (lignone)
+appears on the 'credit' side. But where calcium and magnesium
+bisulphites are used, the residue from calcination is practically
+without value. It appears, however, that by substituting soda as the
+base the alkali is recoverable in such a form as to be directly
+available for the alkaline-sulphide or 'Dahl' process. As a more
+complicated alternative the soda admits of being recovered on the lines
+of the old black-ash or Leblanc process, and the sulphur by the now
+well-established 'Chance' process, for which, of course, an addition of
+lime is necessary to the fully evaporated liquors previously to
+calcining. The engineering features of the system, so far as regards
+evaporating and calcining, are the same. For economic working there is
+required (<i>a</i>) evaporation by multiple effect and (<i>b</i>) calcining on the
+continuous rotary principle. For the latter a special modification has
+been devised so that the draught of air is concurrent with the movement
+of the charge in the furnace, securing a progressively increasing
+temperature within the furnace. This interesting development of the
+chemical engineering of wood-pulp systems has been elaborated by two
+well-known technologists, Drewson and Dorenfeldt, and readers who wish
+to inform themselves in detail of these developments are referred to the
+various publications of these inventors.<span class='pagenum'><a name="Page_165" id="Page_165">[Pg 165]</a></span></p>
+
+<p>Assuming the present necessity of a destructive treatment of the
+by-products of the bisulphite processes, the scheme has many advantages.
+The soda-bisulphite liquors are more economically prepared; the pulp
+obtained is superior in paper-making quality to that resulting from the
+lime or magnesia (bisulphite) processes: it is more economically
+bleached.</p>
+
+<p>Then, as pointed out, the soda may on the one plan be obtained in a form
+in which it is immediately available as a powerful hydrolysing alkali in
+the manufacture of a 'soda' pulp. These two systems become, therefore,
+in a new sense complementary to one another. Lastly, it is obvious that
+the employment of soda as the base opens out a new vista for developing
+the electrolytic processes of decomposing common salt.</p>
+
+<p>The authors have assisted in preparing plans for a comprehensive
+industrial scheme combining all these more modern developments. In this
+scheme it is only the combination which is novel, and as it involves no
+new principles in the chemical treatments of the materials we are not
+further concerned with it than to have briefly sketched its economic
+basis. This may be summed up in result in the important question of cost
+and selling price, and the estimate is well grounded that by means of
+this scheme <i>bleached wood-pulp</i> can be sold on the English market at
+10<i>l.</i> a ton. It is important to note this figure and to compare it with
+the prices of twenty years ago. The fall has been continuous,
+notwithstanding the influence of the opposing factors of increasing
+consumption, exhaustion of accessible supply of timber, and relative
+appreciation of the essential costs of steam, chemicals, and labour. It
+is important in forecasting the future, since the youngest and
+apparently most promising of the 'artificial' cellulose industries
+employs wood-cellulose by preference as its raw material (see p. 173).<span class='pagenum'><a name="Page_166" id="Page_166">[Pg 166]</a></span></p>
+
+<p>As a last point it must be considered that as chemists we are bound to
+anticipate the realisation of value in the soluble by-products of the
+bisulphite processes. Outside the intrinsic interest attaching to the
+solution of this problem, it carries with it the promise of a further
+economy in the production of wood-cellulose.</p>
+
+<p><b>Bleaching of Vegetable Textiles.</b>&mdash;By far the largest of these industries
+are those which are engaged in producing the 'pure white' on cotton and
+flax goods. The process, considered chemically, is simply that of
+isolating a pure cellulose, and we endeavoured to give due prominence to
+this view in the original work. It is important to insist upon it for
+the reason that this view gives the due proportion of chemical value to
+the several contributory treatments&mdash;alkaline hydrolyses (caustic lime
+and soda boils), hypochlorite oxidations, and incidental acid treatments
+(souring). The first of these is by far the largest contributor of
+'chemical work,' though the second, by being the agent for the actual
+whitening effect or bleaching action proper, occupies a position of
+often exaggerated importance.</p>
+
+<p>In bleaching processes there has been no radical change of system on the
+large scale since the introduction of the 'Mather' kier in 1885, and the
+associated change from lime and ash boiling to the caustic soda
+circulating boil with reduced volume of lye, which this mechanical
+device rendered practicable. It is outside the scope of this work to
+follow up this branch of technology in any detail, and we cannot discuss
+the evolution of systems on variations of detail where no essential
+principle is involved. But we have to notice a very recent development
+which has only just begun its industrial career, and which does give
+effect to a principle of treatment not previously applied. This is
+tersely stated by its originator,<span class='pagenum'><a name="Page_167" id="Page_167">[Pg 167]</a></span> William Mather,<a name="FNanchor_13_13" id="FNanchor_13_13"></a><a href="#Footnote_13_13" class="fnanchor">[13]</a> in the
+expression, 'it is more economical to make liquids pass through cloth
+than to make cloth pass through liquids.' The starting point of this
+development is the invention of a complete self-contained machine in
+which a rolled batch of cloth can receive a succession of chemical
+treatments, with accessory washings&mdash;the solutions, or wash waters,
+being circulated through the cloth. The essential fact on which this
+system is based is that a perfect liquid circulation can be maintained
+from selvedge to selvedge through the folds of a tightly rolled batch of
+cloth. Such circulation is therefore quite independent of the diameter
+of the batch. If we consider a cloth under chemical treatment with
+solutions, it is clear that the reactions and interchanges of soluble
+matters within the cloth, within the twisted elements of the yarn, and
+in the last grade of distribution within the actual ultimate fibres, are
+subject to capillary transmission, and osmotic exchange. There is a
+mixture of these molecular effects, with the circulation in mass,
+sweeping both faces of the cloth. It is obvious that for the mass effect
+a relatively very small volume of circulating liquid is necessary to
+maintain uniform conditions of action. In the actual disposition of the
+machine the rolled batch of cloth nearly fills the cylindrical space of
+what we may call the reaction chamber, and the circulation of the liquid
+is maintained by a circulating pump and a differential pressure in the
+horizontal plane across and through the folds of the batch. This is in
+the meantime kept in slow revolution. For a full description of these
+mechanical details the reader is referred to the original patent
+specifications [Engl. Pat. 23,400, 23,401; 1900, W. Mather]. If we again
+consider the principles involved, they are very much as set forth in
+our<span class='pagenum'><a name="Page_168" id="Page_168">[Pg 168]</a></span> original work (pp. 288-291). Boiling processes in which a
+relatively large volume of liquid is used are wasteful of steam, the
+active agent is unnecessarily diluted or used in superfluous quantity,
+and the soluble by-products, being continually removed as formed, cannot
+so effectively contribute by secondary actions to the chemical work. The
+new mechanical appliance enables us to further reduce the volume of
+liquid required in the alkaline-hydrolytic treatment of vegetable
+textiles, and where advantageous to bring the treatment down (or up) to
+a process of steaming with the active agent dissolved in a minimum
+proportion of water relative to the cloth. This concentration of effect
+is of importance in flax cloth, and especially linen treatment, where
+the peculiarly resistant cutocelluloses have to be attacked and a
+considerable proportion of waxy by-products to be removed. These points
+are the basis of the special process of Cross and Parkes [Engl. Pat.
+25,076/ 99] for steaming flax (and cotton) goods with an emulsion
+containing, in addition to the special hydrolysing agent&mdash;caustic
+soda&mdash;mixtures of soap with 'mineral' or other oils, the presence of
+which effectually aids the removal of the by-products in question.</p>
+
+<p>A complete system on these lines is now working on the industrial scale
+in the Belfast district. The results are not merely economical in
+largely reducing the number of alkaline boiling treatments required on
+the old plan of pan or 'pot' boiling, but are visible in the strength
+and finish of the linens so treated.</p>
+
+<p>For cotton bleaching the costs may be put down at a fraction of those of
+the Irish linen bleach. The economical advantages of the new system are
+obviously less in relation to the lesser total costs. But there are
+other points which have come into more prominent influence. The
+mechanical wear and tear on the cloth is considerable in the ordinary
+process, more<span class='pagenum'><a name="Page_169" id="Page_169">[Pg 169]</a></span> especially in the mangle-washes. As a result the
+adjustment of warp and weft is more or less disturbed. These defects are
+absent from a system which operates on the cloth in a fixed position.</p>
+
+<p>But as we are mainly concerned with the purely chemical factors we
+cannot pretend to deal with textile questions. We have to notice the
+remaining element of chemical economy as it involves a fundamental
+principle. The practice of washing residues or products of reaction free
+from reagents and soluble by-products involves a well-known mathematical
+law, under which the rate of purification is a function rather of the
+<i>number</i> of successive changes of washing liquid than of the volume of
+the latter. The ordinary practice of textile washings entirely ignores
+this principle, and the consumption of water in consequence may reach
+many thousand times the economic minimum. With supplies of water often
+in indefinite excess of requirements, even in this most wasteful method,
+bleachers are in no need to consider the question of consumption. But
+leaving aside particular and local considerations of advantage the fact
+is that the new system gives control of the practice of washing,
+enabling the operator to adapt an important element of the daily routine
+to a fundamental principle which has been almost universally ignored.</p>
+
+<p>In the oxidising processes which follow the alkaline treatments, the
+hypochlorites are still the staple agents. Owing to the steady relative
+fall in the selling prices of the permanganates these are coming into
+more extensive use, but the consumption is still small, and they are
+mainly used for certain special effects, chiefly in linen or more
+generally flax cloth bleaching.</p>
+
+<p><b>Paper-pulp Spinning.</b>&mdash;Paper is a continuous web or fabric produced by
+the interlocking of the structural fibrous units of the well-known short
+length. In Japan and other<span class='pagenum'><a name="Page_170" id="Page_170">[Pg 170]</a></span> countries paper is made to serve for all or
+some of the purposes for which we employ string or twine, and to give
+the necessary tensile strength the paper is twisted or rolled on itself.
+Such twisting, however, adds nothing to the intrinsic tensile qualities
+of the original paper.</p>
+
+<p>A new technical effect is realised in this direction by the treatment of
+paper-pulp in the process of its conversion into a continuous web: The
+pulp is formed into continuous strips of convenient breadth (usually
+from 2 to 8 mm.), these receive a 'rolling-up' treatment immediately
+following the squeeze of the press rolls by which the superfluous water
+is removed: they are then further but incompletely dried, and in this
+condition are subjected to a final spinning or twisting treatment on
+ring-spinning machinery of special construction.</p>
+
+<p>Such a process was originally patented by C. Kellner in this country
+(E.P. No. 20,225/1891), and is fully described in his specification.
+Later improvements in detail were patented by G. T&uuml;rk (E.P. 4621/1892).</p>
+
+<p>A joint system is now being industrially developed in Germany by the
+Altdamm-Stahlhammer Pulp and Paper Company under the technical direction
+of Dr. Max M&uuml;ller, and there appears to be every prospect of the product
+taking a position as a staple textile.</p>
+
+<p>The process has only the incidental interest in connection with our main
+subject, that it employs chiefly the 'chemical' pulps or celluloses as
+raw materials. The industrial future of the application must, of course,
+be largely determined by costs of production, as the directions of
+application in the weaving industries will be limited by the necessarily
+inferior grade of tensile strength belonging to these products and the
+degree by which this is lowered on complete wetting. All these questions
+have been duly weighed by those engaged in this interesting development,
+and the conclusion of those<span class='pagenum'><a name="Page_171" id="Page_171">[Pg 171]</a></span> qualified to judge is that the new industry
+has vindicated for itself a permanent position.</p>
+
+<p><b>II. The Chemical Derivatives of Cellulose</b>, in their industrial aspects,
+have come to occupy a profoundly important position in the world's
+affairs. In the way of any essential alteration of the perspective from
+that obtaining in 1895 we have nothing to chronicle. No new derivatives
+of industrial importance have been added in that period; but certain new
+methods incidental to the preparation of well-known compounds or for
+converting them into more generally available forms have been
+introduced, and these are contributing to the rapid expansion of the
+'artificial' cellulose industries.</p>
+
+<p>Of the cellulose esters the nitrates are still the only group in
+industrial use. There uses for explosives have attained immense
+proportions, and their applications for structural purposes are
+continually on the increase. The manufacture of smokeless powders on the
+one hand, and of celluloid and xylonite (both in the form of films and
+solid aggregates) on the other, has taken no new departure. The industry
+in 'artificial silks' or 'lustra-celluloses,' by the collodion processes
+also, whilst presenting features of unusual interest attaching to rapid
+expansion, has been barren of contribution of fundamental scientific or
+technical importance. The tetracetate is now manufactured on the large
+scale, but the product has yet to make its market.</p>
+
+<p>The process of mercerising cotton yarns and cloth has been developed to
+an industry of colossal dimensions, and the growth has been especially
+rapid during the last five years. Significant of the technical progress
+in these two industries, with their common aim of appreciating cellulose
+in the scale of textiles by approximating its external properties in
+those of silk, is the appearance of a monograph of the technology of
+each, notices of which have been previously given (pp. 22-26).</p>
+
+<p>There is little doubt, however, that the question of the<span class='pagenum'><a name="Page_172" id="Page_172">[Pg 172]</a></span> future
+industry in the various forms of cellulose, thread, film, structureless
+powder or solid aggregate, obtainable by artificial means, mainly turns
+upon cost of production. Irrespective of cost, there would, no doubt, be
+a market for all these products, based upon such of their properties or
+effects as are indispensable and not otherwise obtainable. As an
+illustration, we may cite the extraordinary selling prices of 40-50 fr.
+per kilo, for the 'artificial silks' (collodion process) which ruled
+some three years ago; and we may note that for a special application of
+viscose the dissolved cellulose is paid for at the rate of 10<i>s.</i> per
+lb. These facts are certainly worthy of mention, and should be borne in
+mind as an index of some special features of modern manufacturing
+industry. But with a material like cellulose rendered available in a new
+shape the question which always arises more prominently than that of
+limited uses at high prices is that of consumption on the extensive
+scale which marks the older and well-known products. That question is
+rapidly solving itself in this country as regards the 'artificial
+silks.' There is at present a limited market at 9<i>s.</i>-10<i>s.</i> per lb., a
+price which on the one side excludes extensive consumption, and on the
+other practically bars manufacture in this country by any of the
+collodion systems. It will appear from a very elementary calculation of
+what we may call the theoretical costs that the above selling price
+would not have a remunerative margin. The theoretical costs are made up
+of</p>
+
+<p><span class='pagenum'><a name="Page_173" id="Page_173">[Pg 173]</a></span><br /></p>
+
+
+<div class='center'>
+<table border="0" cellpadding="4" cellspacing="0" summary="">
+<tr><td align='left'>Raw materials<a name="FNanchor_14_14" id="FNanchor_14_14"></a><a href="#Footnote_14_14" class="fnanchor">[14]</a></td><td align='left'>Cotton. Nitrating acid. Ether-alcohol (solvent). Denitrating chemicals.</td></tr>
+<tr><td align='left'>Labour</td><td align='left'>(<i>a</i>) Nitrating and preparing collodion. Denitrating and bleaching.<br /> (<i>b</i>) Textile operations. Spinning. Winding and twisting. Rewinding.</td></tr>
+<tr><td align='left'>Power</td><td align='left'>Making, filtering, and distributing collodion. Driving textile machinery.</td></tr>
+</table></div>
+
+
+<p>Added to which are the costs of expert management and supervision and
+general establishment expenses. It is evident that raw materials make up
+a large fraction of the total cost; also that a very large item is the
+waste work of converting the cellulose into nitrate, only to remove the
+nitric groups so soon as the cellulose is obtained as thread.</p>
+
+<p>It is clear that the aqueous solutions of cellulose have a double
+advantage in this respect&mdash;not only do they readily yield an
+approximately pure cellulose as a direct product of regeneration or
+decomposition, but the first cost of the solution is very much less.
+With these newer products, therefore, the spinning problem enters on a
+new phase of struggle. It is certain that at selling prices at or about
+5<i>s.</i> to 7<i>s.</i>, very large markets will be open to the product or
+products. The two processes which are or may be able to fulfil this
+demand are those based (1) on cuprammonium solutions of cellulose, (2)
+on the sulphocarbonate or viscose. As regards <i>first cost</i> of the
+solution the latter has a large advantage. One ton of wood pulp (at
+12<i>l.</i>) can certainly be obtained in solution in a condition ready for
+spinning at a total cost (materials) of less than 30<i>l.</i> The
+cuprammonium process, so far as 'outside' information goes, requires for
+production of the solution (1) cotton as raw material, (2) ammonia
+(calc. as concentrated aqueous) equal to 1-1/2 times its weight, and<span class='pagenum'><a name="Page_174" id="Page_174">[Pg 174]</a></span>
+(3) metallic copper 25 p.ct. of its weight; and the costs are
+approximately 100<i>l.</i> per ton. It is obvious that the materials are
+recoverable from the precipitating-bath, but at a certain added cost. We
+have no statements as to the proportion recoverable nor the costs
+incurred, and we are therefore unable to measure the total net cost of
+the regenerated cellulose by this process. It is certainly much less
+than by the collodion processes. As to the textile quality of the
+thread, the product has not yet been on a sufficiently wide selling
+basis for that to have been determined. There are a great many factors
+which enter here. Not merely the external characters of lustre,
+softness, and translucency, but the all-important quality of uniformity
+of thread. The collodion-spinning is a process still very defective in
+this respect, and the defect is no doubt referable to the difficulty of
+securing absolute physical invariability of the collodion. It is to be
+regretted, in the interests of scientific development, that none of the
+technologists who have published investigations of these processes have
+entered into the discussion of the fundamental factors of the spinning
+processes; we are, therefore, unable at this stage to discuss these
+elements of a full comparison in greater detail. We cannot, for this
+reason, say how far the cuprammonium process diverges in point of
+control from the standard of the collodion processes. Of the 'viscose'
+product we have a more intimate knowledge, and it certainly reaches a
+higher general standard than the older and now well-known artificial
+silks. The process is also sufficiently developed to enable the total
+costs of production to be estimated at a figure less than one-half that
+of the 'collodion' processes. This would assure to this system an
+<i>entr&eacute;e</i> in this country, and a basis of expansion limited only by the
+ordinary laws of supply and demand.</p>
+
+<p>This prospect is opened up precisely at the moment when, for various
+reasons connected both with the difficulties of<span class='pagenum'><a name="Page_175" id="Page_175">[Pg 175]</a></span> manufacture and the
+narrowing of the margin of profit, the proprietors of the two systems of
+collodion-spinning have decided to abandon all idea of manufacturing by
+these systems in this country.<a name="FNanchor_15_15" id="FNanchor_15_15"></a><a href="#Footnote_15_15" class="fnanchor">[15]</a> We leave the discussion of the
+industrial problem at this point.</p>
+
+<p>In regard to other developments based upon the exceptional character and
+properties of the sulphocarbonate, their further discussion will
+exemplify no general principles; and as regards technical detail they
+have been dealt with in the papers previously noticed.</p>
+
+<p>As a purely general question, if there is to be any industry in these
+'artificial' forms of cellulose, commensurate with the magnitude that
+usually belongs to the cellulose industries, it must come by way of a
+plastic or soluble form prepared at low cost, and conserving the
+essential molecular properties of the cellulose aggregate. These are the
+particular features of the sulphocarbonate. The obvious difficulties in
+the way of its industrial applications are those caused by the presence
+of alkali and sulphur compounds. These are dealt with by appropriate
+chemical means; but the fact that there is a special chemistry of the
+product has rendered its industrial progress slow. The work of the last
+five years in this, as in other applications of cellulose in its many
+derived forms, has resulted in a considerable addition to the domain of
+practical chemistry.</p>
+
+<p>Further developments will make an increasing demand upon our grasp of
+the fundamental constitutional problems, to which it is the main purpose
+of the present volume to contribute.</p>
+
+<div class="footnotes"><h3>FOOTNOTES:</h3>
+
+<div class="footnote"><p><a name="Footnote_11_11" id="Footnote_11_11"></a><a href="#FNanchor_11_11"><span class="label">[11]</span></a> This is the most complete notice that has appeared and the
+bibliography is exhaustive. The publication comes into our hands too
+late to be noticed in detail.</p></div>
+
+<div class="footnote"><p><a name="Footnote_12_12" id="Footnote_12_12"></a><a href="#FNanchor_12_12"><span class="label">[12]</span></a> <i>Text-book on Paper-making</i>, Cross and Bevan (Spon,
+London: second edition, 1900). <i>Chemistry of Paper-making</i>, Griffin and
+Little (New York, 1894: Howard Lockwood &amp; Co.). <i>Handbuch d.
+Papierfabrikation</i>, C. Hofmann (Berlin). <i>Paper Trade Review</i>, London
+(weekly). <i>Papier-Zeitung</i>, Berlin.</p></div>
+
+<div class="footnote"><p><a name="Footnote_13_13" id="Footnote_13_13"></a><a href="#FNanchor_13_13"><span class="label">[13]</span></a> William Mather, M.P., of the firm of Mather &amp; Platt,
+Limited, Manchester.</p></div>
+
+<div class="footnote"><p><a name="Footnote_14_14" id="Footnote_14_14"></a><a href="#FNanchor_14_14"><span class="label">[14]</span></a> The actual costs varying considerably in the various
+countries, we cannot make any specific statement. But from estimates we
+have made, the costs of obtaining cotton in filtered solution as
+collodion multiply its value by 12-14, the denitrations adding further
+costs and raising this multiple to 18-20. In the same estimates we
+arrived at the conclusion that the item for raw materials made up 60
+p.ct. of the total cost of the yarn.</p></div>
+
+<div class="footnote"><p><a name="Footnote_15_15" id="Footnote_15_15"></a><a href="#FNanchor_15_15"><span class="label">[15]</span></a> The recent failure of a French company founded for the
+exploitation of the cuprammonium process may be taken as showing that it
+presents very considerable technical difficulties. It is a matter of
+common knowledge that this company <i>estimated</i> the costs of production
+to be such as to enable the product to be sold at 12 fr. per kilo.,
+whereas the costs actually obtaining were a large multiple of this
+figure.</p></div>
+</div>
+
+
+<hr style="width: 65%;" />
+<p><span class='pagenum'><a name="Page_177" id="Page_177">[Pg 177]</a></span></p>
+<h2>INDEX OF AUTHORS</h2>
+
+
+<p>
+Bardy, C. H., <a href='#Page_157'>157</a><br />
+<br />
+Bokorny, T., <a href='#Page_43'>43</a><br />
+<br />
+Bronnert, E., <a href='#Page_54'>54</a><br />
+<br />
+Bumcke, G., and Wolffenstein, R., <a href='#Page_67'>67</a><br />
+<br />
+Buntrock, <a href='#Page_25'>25</a><br />
+<br />
+<br />
+Cross, C. F., <a href='#Page_139'>139</a>, <a href='#Page_152'>152</a>, <a href='#Page_155'>155</a><br />
+<br />
+Cross, C. F., and Bevan, E. J., <a href='#Page_92'>92</a><br />
+<br />
+Cross, C. F., Bevan, E. J., and Briggs, J. F., <a href='#Page_118'>118</a><br />
+<br />
+Cross, C. F., Bevan, E. J., and Heiberg, T., <a href='#Page_114'>114</a><br />
+<br />
+Cross, C. F., Bevan, E. J., and Smith, C., <a href='#Page_101'>101</a>, <a href='#Page_103'>103</a>, <a href='#Page_105'>105</a>, <a href='#Page_114'>114</a>, <a href='#Page_145'>145</a><br />
+<br />
+<br />
+De Haas, R. W. T., and Tollens, B., <a href='#Page_151'>151</a><br />
+<br />
+<br />
+Faber, O. v., and Tollens, B., <a href='#Page_71'>71</a><br />
+<br />
+Feilitzen, H. v., and Tollens, B., <a href='#Page_154'>154</a><br />
+<br />
+Fenton, H. J. H., <a href='#Page_8'>8</a><br />
+<br />
+Fenton, H. J. H., and Gostling, M., <a href='#Page_86'>86</a><br />
+<br />
+Fraenkel, A., and Friedlaender, P., <a href='#Page_26'>26</a><br />
+<br />
+<br />
+Gardner, P., <a href='#Page_22'>22</a><br />
+<br />
+Gilson, E., <a href='#Page_112'>112</a><br />
+<br />
+<br />
+Hancock, W. C., and Dahl, O. W., <a href='#Page_135'>135</a><br />
+<br />
+Hoffmeister, W., <a href='#Page_96'>96</a>, <a href='#Page_100'>100</a><br />
+<br />
+<br />
+Kleiber, A., <a href='#Page_97'>97</a><br />
+<br />
+Kr&ouml;ber, E., <a href='#Page_121'>121</a><br />
+<br />
+Kr&uuml;ger, M., <a href='#Page_119'>119</a><br />
+<br />
+<br />
+Lange, H., <a href='#Page_25'>25</a><br />
+<br />
+Lewes, V. H., <a href='#Page_15'>15</a><br />
+<br />
+Luck, A., and Cross, C. F., <a href='#Page_45'>45</a><br />
+<br />
+<br />
+Margosches, B. M., <a href='#Page_159'>159</a><br />
+<br />
+Morrell, R. S., and Crofts, J. M., <a href='#Page_114'>114</a><br />
+<br />
+Mylius, F., <a href='#Page_21'>21</a><br />
+<br />
+<br />
+Nastukoff, H., <a href='#Page_74'>74</a><br />
+<br />
+<br />
+Omelianski, V., <a href='#Page_76'>76</a><br />
+<br />
+<br />
+Ruff, O., <a href='#Page_117'>117</a><br />
+<br />
+<br />
+Salkowski, E., <a href='#Page_113'>113</a><br />
+<br />
+Sch&ouml;ne, A., and Tollens, B., <a href='#Page_124'>124</a><br />
+<br />
+Seidel, H., <a href='#Page_149'>149</a><br />
+<br />
+Sherman, H. C., <a href='#Page_137'>137</a><br />
+<br />
+Simonsen, E., <a href='#Page_146'>146</a><br />
+<br />
+Storer, F. H., <a href='#Page_142'>142</a><br />
+<br />
+Strehlenert, R. W., <a href='#Page_158'>158</a><br />
+<br />
+Suringar, H., and Tollens, B., <a href='#Page_16'>16</a>, <a href='#Page_124'>124</a><br />
+<br />
+S&uuml;vern, C., <a href='#Page_63'>63</a><br />
+<br />
+<br />
+Tollens, B., <a href='#Page_148'>148</a>, <a href='#Page_151'>151</a><br />
+<br />
+Tollens, B., and Glaubitz, H., <a href='#Page_122'>122</a><br />
+<br />
+<br />
+Vignon, L., <a href='#Page_43'>43</a>, <a href='#Page_70'>70</a>, <a href='#Page_72'>72</a>, <a href='#Page_94'>94</a><br />
+<br />
+<br />
+Will, W., and Lenze, P., <a href='#Page_41'>41</a><br />
+<br />
+Winterstein, E., <a href='#Page_109'>109</a>, <a href='#Page_144'>144</a>, <a href='#Page_153'>153</a><br />
+</p>
+
+
+
+<hr style="width: 65%;" />
+<p><span class='pagenum'><a name="Page_178" id="Page_178">[Pg 178]</a></span></p>
+<h2>INDEX OF SUBJECTS</h2>
+
+
+<p>
+Acetone, action on cellulose nitrates of diluted, <a href='#Page_46'>46</a><br />
+<br />
+Acid-cellulose, <a href='#Page_68'>68</a><br />
+<br />
+Acids, volatile, from cellulose, <a href='#Page_145'>145</a><br />
+<br />
+<i>&AElig;schynomene aspera</i>, <a href='#Page_135'>135</a><br />
+<br />
+Alcohol from cellulose and wood, <a href='#Page_146'>146</a><br />
+<br />
+Alcoholic soda, mercerisation results with, <a href='#Page_26'>26</a><br />
+<br />
+Alkali-cellulose, effects of long storage on, <a href='#Page_31'>31</a><br />
+<br />
+Amyloid, vegetable, <a href='#Page_153'>153</a><br />
+<br />
+Arabinose from gluconic acid, <a href='#Page_117'>117</a><br />
+<br />
+'Ash' of plants, <a href='#Page_13'>13</a><br />
+<br />
+<br />
+<i>Bacterium xylinum</i>, <a href='#Page_85'>85</a><br />
+<br />
+Barley plant, chemical processes in the, <a href='#Page_103'>103</a><br />
+<br />
+---- straw, carbohydrates of, <a href='#Page_105'>105</a><br />
+<br />
+Bleaching, <a href='#Page_166'>166</a><br />
+<br />
+Bran, digestion of, <a href='#Page_139'>139</a><br />
+<br />
+Brommethylfurfural, <a href='#Page_8'>8</a>, <a href='#Page_84'>84</a>, <a href='#Page_86'>86</a><br />
+<br />
+<br />
+Carbohydrates, action of hydrogen bromide on, <a href='#Page_86'>86</a>;<br />
+<span style="margin-left: 1em;">action of hydrogen peroxide on, <a href='#Page_114'>114</a>;</span><br />
+<span style="margin-left: 1em;">nitrated, as food for mould fungi, <a href='#Page_43'>43</a>;</span><br />
+<span style="margin-left: 1em;">nitrates of, <a href='#Page_41'>41</a>;</span><br />
+<span style="margin-left: 1em;">quantitative separation of, <a href='#Page_96'>96</a></span><br />
+<br />
+Carbohydrates of barley straw, <a href='#Page_105'>105</a>;<br />
+<span style="margin-left: 1em;">of wheat, <a href='#Page_137'>137</a>;</span><br />
+<span style="margin-left: 1em;">of yeast, <a href='#Page_113'>113</a></span><br />
+<br />
+'Caro's reagent,' <a href='#Page_118'>118</a><br />
+<br />
+'Celloxin,' <a href='#Page_71'>71</a><br />
+<br />
+Cellulose, alcohol from, <a href='#Page_146'>146</a>;<br />
+<span style="margin-left: 1em;">constitution of, <a href='#Page_77'>77</a>, <a href='#Page_92'>92</a>;</span><br />
+<span style="margin-left: 1em;">fermentation of, <a href='#Page_76'>76</a>;</span><br />
+<span style="margin-left: 1em;">industrial uses of, <a href='#Page_155'>155</a>;</span><br />
+<span style="margin-left: 1em;">iodine reaction of, <a href='#Page_21'>21</a>;</span><br />
+<span style="margin-left: 1em;">methods for the estimation of, <a href='#Page_3'>3</a>, <a href='#Page_4'>4</a>, <a href='#Page_16'>16</a>, <a href='#Page_19'>19</a>, <a href='#Page_97'>97</a>;</span><br />
+<span style="margin-left: 1em;">nitration of, <a href='#Page_43'>43</a>;</span><br />
+<span style="margin-left: 1em;">saccharification of, <a href='#Page_73'>73</a>;</span><br />
+<span style="margin-left: 1em;">ultimate hydrolysis of, <a href='#Page_11'>11</a>;</span><br />
+<span style="margin-left: 1em;">volatile acids from, <a href='#Page_145'>145</a></span><br />
+<br />
+---- acetates, monoacetate, formation of, <a href='#Page_40'>40</a>;<br />
+<span style="margin-left: 1em;">tetracetate, constitution of, <a href='#Page_80'>80</a></span><br />
+<br />
+---- benzoates, <a href='#Page_34'>34</a>;<br />
+<span style="margin-left: 1em;">from structureless cellulose, <a href='#Page_36'>36</a>;</span><br />
+<span style="margin-left: 1em;">from three varieties of cotton, <a href='#Page_35'>35</a>;</span><br />
+<span style="margin-left: 1em;">monobenzoate, properties of, <a href='#Page_36'>36</a>;</span><br />
+<span style="margin-left: 1em;">dibenzoate, properties of, <a href='#Page_37'>37</a>;</span><br />
+<span style="margin-left: 1em;">acetylation of, <a href='#Page_130'>130</a>;</span><br />
+<span style="margin-left: 1em;">nitration of, <a href='#Page_38'>38</a></span><br />
+<br />
+---- derivatives, commercial aspects of, <a href='#Page_171'>171</a>;<br />
+<span style="margin-left: 1em;">saccharification of, <a href='#Page_73'>73</a></span><br />
+<br />
+---- nitrates, <a href='#Page_44'>44</a>, <a href='#Page_45'>45</a>, <a href='#Page_83'>83</a>;<br />
+<span style="margin-left: 1em;">structureless, <a href='#Page_45'>45</a>, <a href='#Page_51'>51</a>;</span><br />
+<span style="margin-left: 1em;">cupric reducing power of, <a href='#Page_73'>73</a>;</span><br />
+<span style="margin-left: 1em;">instability of, <a href='#Page_50'>50</a>, <a href='#Page_53'>53</a></span><br />
+<br />
+---- sulphocarbonate, <a href='#Page_27'>27</a>;<br />
+<span style="margin-left: 1em;">effects of the nature of the cellulose, <a href='#Page_28'>28</a>;</span><br />
+<br />
+---- &mdash;&mdash; solutions, analysis of, <a href='#Page_32'>32</a>;<br />
+<span style="margin-left: 1em;">iodine reaction of, <a href='#Page_33'>33</a>;</span><br />
+<span style="margin-left: 1em;">loss of carbon bisulphide, <a href='#Page_33'>33</a>;</span><br />
+<span style="margin-left: 1em;">viscosity of, <a href='#Page_30'>30</a></span><br />
+<br />
+Cell-wall constituents, <a href='#Page_97'>97</a><br />
+<br />
+Cereal celluloses, <a href='#Page_101'>101</a>, <a href='#Page_105'>105</a><br />
+<br />
+Chitin, <a href='#Page_112'>112</a><br />
+<br />
+Chlorination, Cross and Bevan's method, <a href='#Page_19'>19</a>;<br />
+<span style="margin-left: 1em;">statistics of, <a href='#Page_134'>134</a></span><br />
+<br />
+Chloro-lignone, <a href='#Page_126'>126</a><br />
+<br />
+Collodion. <i>See</i> Silk, artificial<br />
+<br />
+Cotton, lustreing effect of mercerisation, <a href='#Page_23'>23</a>;<br />
+<span style="margin-left: 1em;">mercerised, structural properties of, <a href='#Page_25'>25</a>;</span><br />
+<span style="margin-left: 1em;">pentosane content of, <a href='#Page_148'>148</a></span><br />
+<span class='pagenum'><a name="Page_179" id="Page_179">[Pg 179]</a></span><br />
+'Crude fibre,' <a href='#Page_17'>17</a><br />
+<br />
+Cuprammonium solvent, <a href='#Page_21'>21</a>, <a href='#Page_58'>58</a>, <a href='#Page_173'>173</a><br />
+<br />
+Currants, pectin of, <a href='#Page_152'>152</a><br />
+<br />
+<br />
+Denitration of collodion silk, <a href='#Page_56'>56</a>;<br />
+<span style="margin-left: 1em;">of jute nitrate, <a href='#Page_133'>133</a>;</span><br />
+<span style="margin-left: 1em;">products of, <a href='#Page_74'>74</a></span><br />
+<br />
+Dioxybutyric acid, <a href='#Page_71'>71</a><br />
+<br />
+<br />
+Elder pith, <a href='#Page_137'>137</a><br />
+<br />
+Eriodendron, seed hair of, <a href='#Page_92'>92</a><br />
+<br />
+Explosives, <a href='#Page_44'>44</a>;<br />
+<span style="margin-left: 1em;">sporting powders, <a href='#Page_52'>52</a></span><br />
+<br />
+<br />
+Fermentation of cellulose, <a href='#Page_76'>76</a>;<br />
+<span style="margin-left: 1em;">of furfuroids, <a href='#Page_108'>108</a>;</span><br />
+<span style="margin-left: 1em;">of sugar from wood, <a href='#Page_148'>148</a></span><br />
+<br />
+Fibres, report on miscellaneous, <a href='#Page_139'>139</a><br />
+<br />
+Flax boiling, <a href='#Page_168'>168</a>;<br />
+<span style="margin-left: 1em;">spinning, <a href='#Page_161'>161</a></span><br />
+<br />
+Fodder plants, pentosanes of, <a href='#Page_122'>122</a><br />
+<br />
+Fungi, tissue constituents of, <a href='#Page_109'>109</a><br />
+<br />
+Furfural from cellulose, oxycellulose, and hydrocellulose, <a href='#Page_70'>70</a>;<br />
+<span style="margin-left: 1em;">derivative from l&aelig;vulose, <a href='#Page_8'>8</a>;</span><br />
+<span style="margin-left: 1em;">estimation as hydrazone and phloroglucide, <a href='#Page_119'>119</a>, <a href='#Page_121'>121</a>;</span><br />
+<span style="margin-left: 1em;">oxidation of, <a href='#Page_114'>114</a>, <a href='#Page_118'>118</a> (<i>refer also</i> 'Pentosanes')</span><br />
+<br />
+Furfuroids, <a href='#Page_8'>8</a>, <a href='#Page_10'>10</a>, <a href='#Page_102'>102</a>, <a href='#Page_105'>105</a>;<br />
+<span style="margin-left: 1em;">assimilation of, <a href='#Page_108'>108</a></span><br />
+<br />
+<br />
+Gabriel's method of cellulose estimation, <a href='#Page_18'>18</a><br />
+<br />
+Gluconic acid, action of hydrogen peroxide on, <a href='#Page_117'>117</a><br />
+<br />
+Glucosamin, <a href='#Page_112'>112</a><br />
+<br />
+<br />
+Hemicellulose, <a href='#Page_96'>96</a>, <a href='#Page_97'>97</a>;<br />
+<span style="margin-left: 1em;">determination and separation of, <a href='#Page_100'>100</a></span><br />
+<br />
+H&ouml;nig's method of cellulose estimation, <a href='#Page_18'>18</a><br />
+<br />
+'Hydralcellulose,' <a href='#Page_68'>68</a><br />
+<br />
+Hydrocellulose, <a href='#Page_73'>73</a>;<br />
+<span style="margin-left: 1em;">nitration of, <a href='#Page_43'>43</a></span><br />
+<br />
+Hydrogen peroxide, oxidations with, <a href='#Page_114'>114</a><br />
+<br />
+Hydroxyfurfural in lignocellulose, <a href='#Page_9'>9</a>, <a href='#Page_116'>116</a>, <a href='#Page_118'>118</a><br />
+<br />
+<br />
+Incandescent mantles of artificial silk, <a href='#Page_14'>14</a>, <a href='#Page_15'>15</a><br />
+<br />
+Industrial appliances of cellulose, <a href='#Page_155'>155</a><br />
+<br />
+Iodine reaction of cellulose, <a href='#Page_21'>21</a><br />
+<br />
+Isosaccharinic acid, <a href='#Page_71'>71</a><br />
+<br />
+<br />
+Jute, composition of, <a href='#Page_141'>141</a>;<br />
+<span style="margin-left: 1em;">quality of, <a href='#Page_140'>140</a>;</span><br />
+<span style="margin-left: 1em;">treatment of, <a href='#Page_142'>142</a> (<i>refer also</i> Lignocellulose)</span><br />
+<br />
+---- acetate, <a href='#Page_129'>129</a><br />
+<br />
+---- benzoate, <a href='#Page_127'>127</a>;<br />
+<span style="margin-left: 1em;">acetylation of, <a href='#Page_130'>130</a>;</span><br />
+<span style="margin-left: 1em;">nitration of, <a href='#Page_132'>132</a></span><br />
+<br />
+---- nitrate, <a href='#Page_131'>131</a><br />
+<br />
+<br />
+Ketoses, physiological importance of, <a href='#Page_9'>9</a><br />
+<br />
+<br />
+Lange method of cellulose estimation, <a href='#Page_18'>18</a>, <a href='#Page_98'>98</a><br />
+<br />
+Lead compounds of nitrated carbohydrates, <a href='#Page_49'>49</a><br />
+<br />
+Lignin, <a href='#Page_100'>100</a><br />
+<br />
+Lignocellulose, constitution of, <a href='#Page_133'>133</a>;<br />
+<span style="margin-left: 1em;">esters of, <a href='#Page_125'>125</a>;</span><br />
+<span style="margin-left: 1em;">hydroxyfurfural in, <a href='#Page_9'>9</a>;</span><br />
+<span style="margin-left: 1em;">new type of, <a href='#Page_135'>135</a></span><br />
+<br />
+Lignone complex, properties of, <a href='#Page_126'>126</a><br />
+<br />
+'Lignorosin,' <a href='#Page_151'>151</a><br />
+<br />
+'Lustra-cellulose.' <i>See</i> Silk, artificial<br />
+<br />
+<br />
+Malt, pentosanes of, <a href='#Page_122'>122</a><br />
+<br />
+Mather system of boiling textiles, <a href='#Page_167'>167</a><br />
+<br />
+Mercerization, <a href='#Page_22'>22</a>;
+<span style="margin-left: 1em;">shrinkage during, <a href='#Page_24'>24</a></span><br />
+<br />
+Mercerised yarn, strength and elasticity of, <a href='#Page_25'>25</a>, <a href='#Page_26'>26</a><br />
+<br />
+Methylhydroxyfurfural, <a href='#Page_84'>84</a><br />
+<br />
+Mould fungi, nitrated carbohydrates as food for, <a href='#Page_43'>43</a><br />
+<br />
+Mycosin, <a href='#Page_113'>113</a><br />
+<br />
+<br />
+Nitrated carbohydrates, lead compounds of, <a href='#Page_49'>49</a><br />
+<br />
+Nitrates of carbohydrates, <a href='#Page_41'>41</a><br />
+<br />
+Nitrocellulose (<i>see</i> Cellulose nitrates);<br />
+<span style="margin-left: 1em;">silk, <a href='#Page_55'>55</a></span><br />
+<span class='pagenum'><a name="Page_180" id="Page_180">[Pg 180]</a></span><br />
+'Normal' cellulose, definition of, <a href='#Page_27'>27</a><br />
+<br />
+Normal paper, <a href='#Page_160'>160</a><br />
+<br />
+<br />
+Oxycellulose esters, <a href='#Page_72'>72</a>;<br />
+<span style="margin-left: 1em;">nitration of, <a href='#Page_43'>43</a>;</span><br />
+<span style="margin-left: 1em;">researches on, <a href='#Page_71'>71</a>, <a href='#Page_72'>72</a>, <a href='#Page_74'>74</a>;</span><br />
+<span style="margin-left: 1em;"><i>r&eacute;sum&eacute;</i> of properties, <a href='#Page_94'>94</a></span><br />
+<br />
+Oxygluconic acid, <a href='#Page_117'>117</a><br />
+<br />
+<br />
+Paper, deterioration of, <a href='#Page_155'>155</a>;<br />
+<span style="margin-left: 1em;">normal standard, <a href='#Page_160'>160</a>;</span><br />
+<span style="margin-left: 1em;">pulp, spinning of, <a href='#Page_169'>169</a></span><br />
+<br />
+Peat, constituents of, <a href='#Page_154'>154</a><br />
+<br />
+Pectins, <a href='#Page_151'>151</a>, <a href='#Page_152'>152</a><br />
+<br />
+Pentosanes, <a href='#Page_100'>100</a>, <a href='#Page_109'>109</a>, <a href='#Page_144'>144</a>;<br />
+<span style="margin-left: 1em;">constituents of cotton, <a href='#Page_124'>124</a>;</span><br />
+<span style="margin-left: 1em;">constituents of fodder, <a href='#Page_122'>122</a>;</span><br />
+<span style="margin-left: 1em;">estimation of, <a href='#Page_121'>121</a>;</span><br />
+<span style="margin-left: 1em;">of seeds during germination, <a href='#Page_124'>124</a></span><br />
+<br />
+'Permanent tissue,' <a href='#Page_103'>103</a><br />
+<br />
+Phloroglucinol, <a href='#Page_119'>119</a>, <a href='#Page_121'>121</a><br />
+<br />
+Plant tissues, carbohydrates of, <a href='#Page_96'>96</a>, <a href='#Page_97'>97</a>, <a href='#Page_99'>99</a><br />
+<br />
+Plants, source of unsaturated compounds in, <a href='#Page_145'>145</a><br />
+<br />
+Powders, manufacture of sporting, <a href='#Page_52'>52</a><br />
+<br />
+<br />
+Saccharification of cellulose and derivatives, <a href='#Page_73'>73</a><br />
+<br />
+Schulze method of cellulose estimation, <a href='#Page_18'>18</a>, <a href='#Page_98'>98</a><br />
+<br />
+Schweizer solution, <a href='#Page_101'>101</a><br />
+<br />
+Seeds, pentosanes in germinating, <a href='#Page_124'>124</a><br />
+<br />
+Silica in plant tissues, <a href='#Page_13'>13</a><br />
+<br />
+Silk, artificial, <a href='#Page_54'>54</a>, <a href='#Page_62'>62</a>, <a href='#Page_63'>63</a>, <a href='#Page_172'>172</a>;<br />
+<span style="margin-left: 1em;">bibliography of, <a href='#Page_60'>60</a>;</span><br />
+<span style="margin-left: 1em;">from cuprammonium, <a href='#Page_58'>58</a>, <a href='#Page_64'>64</a>, <a href='#Page_173'>173</a>;</span><br />
+<span style="margin-left: 1em;">from nitrocellulose (collodion), <a href='#Page_55'>55</a>, <a href='#Page_63'>63</a>, <a href='#Page_172'>172</a>;</span><br />
+<span style="margin-left: 1em;">from viscose, <a href='#Page_59'>59</a>;</span><br />
+<span style="margin-left: 1em;">from zinc chloride, <a href='#Page_59'>59</a>;</span><br />
+<span style="margin-left: 1em;">reactions of, <a href='#Page_64'>64</a></span><br />
+<br />
+---- natural, reactions of, <a href='#Page_64'>64</a><br />
+<br />
+Straws, <a href='#Page_101'>101</a>, <a href='#Page_105'>105</a><br />
+<br />
+Succinic acid from furfural, <a href='#Page_118'>118</a><br />
+<br />
+Sulphite waste liquors, <a href='#Page_149'>149</a>, <a href='#Page_164'>164</a><br />
+<br />
+'Swedish' filter paper, <a href='#Page_14'>14</a><br />
+<br />
+<br />
+Tissue constituents, <a href='#Page_99'>99</a>, <a href='#Page_109'>109</a><br />
+<br />
+Trees, composition of trunk woods, <a href='#Page_142'>142</a><br />
+<br />
+<br />
+Viscose and viscoid, <a href='#Page_157'>157</a>, <a href='#Page_158'>158</a>, <a href='#Page_159'>159</a><br />
+<br />
+---- silk, <a href='#Page_59'>59</a>, <a href='#Page_175'>175</a><br />
+<br />
+---- &mdash;&mdash; specific gravity of, <a href='#Page_34'>34</a> (<i>refer also</i> Cellulose<br />
+sulphocarbonate)<br />
+<br />
+'Vulcanised fibre,' <a href='#Page_20'>20</a><br />
+<br />
+<br />
+Weende, method of cellulose estimation (crude fibre), <a href='#Page_17'>17</a>, <a href='#Page_98'>98</a><br />
+<br />
+Welsbach mantles, <a href='#Page_14'>14</a>;<br />
+<span style="margin-left: 1em;">Clamond type, <a href='#Page_15'>15</a></span><br />
+<br />
+Wheat grain, insoluble carbohydrates of, <a href='#Page_137'>137</a><br />
+<br />
+Wood, alcohol from, <a href='#Page_146'>146</a>, <a href='#Page_148'>148</a><br />
+<br />
+Wood-cellulose, waste liquors, <a href='#Page_149'>149</a><br />
+<br />
+Wood-gum, <a href='#Page_144'>144</a><br />
+<br />
+Wood-pulp, processes, <a href='#Page_162'>162</a><br />
+<br />
+Wood, trunks of trees, <a href='#Page_142'>142</a><br />
+<br />
+<br />
+Yeast, carbohydrates of, <a href='#Page_113'>113</a><br />
+<br />
+<br />
+Zinc chloride, artificial silk, <a href='#Page_59'>59</a>;<br />
+<span style="margin-left: 1em;">solvent action of, <a href='#Page_20'>20</a></span><br />
+</p>
+
+
+
+
+
+
+
+
+
+<pre>
+
+
+
+
+
+End of the Project Gutenberg EBook of Researches on Cellulose, by 
+C. F. Cross and E. J. Bevan
+
+*** END OF THIS PROJECT GUTENBERG EBOOK RESEARCHES ON CELLULOSE ***
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+Project Gutenberg's Researches on Cellulose, by C. F. Cross and E. J. Bevan
+
+This eBook is for the use of anyone anywhere at no cost and with
+almost no restrictions whatsoever.  You may copy it, give it away or
+re-use it under the terms of the Project Gutenberg License included
+with this eBook or online at www.gutenberg.org
+
+
+Title: Researches on Cellulose
+       1895-1900
+
+Author: C. F. Cross
+        E. J. Bevan
+
+Release Date: September 16, 2007 [EBook #22620]
+
+Language: English
+
+Character set encoding: ASCII
+
+*** START OF THIS PROJECT GUTENBERG EBOOK RESEARCHES ON CELLULOSE ***
+
+
+
+
+Produced by Juliet Sutherland, Josephine Paolucci and the
+Online Distributed Proofreading Team at http://www.pgdp.net.
+(This file was produced from images generously made
+available by The Internet Archive/Million Book Project).
+
+
+
+
+
+
+
+
+
+
+RESEARCHES ON CELLULOSE
+
+1895-1900
+
+BY
+
+CROSS & BEVAN
+
+(C. F. CROSS AND E. J. BEVAN)
+
+
+_SECOND EDITION_
+
+
+LONGMANS, GREEN, AND CO.
+39 PATERNOSTER ROW, LONDON
+NEW YORK, BOMBAY, AND CALCUTTA
+
+1907
+
+All rights reserved
+
+       *       *       *       *       *
+
+Transcriber's note:
+
+For Text: A word surrounded by a cedilla such as ~this~ signifies that
+the word is bolded in the text. A word surrounded by underscores like
+_this_ signifies the word is italics in the text. The italic and bold
+markup for single italized letters (such as variables in equations) and
+"foreign" abbreviations are deleted for easier reading.
+
+For numbers and equations: Parentheses have been added to clarify
+fractions. Underscores before bracketed numbers in equations denote a
+subscript. Superscripts are designated with a caret and brackets, e.g.
+11.1^{3} is 11.1 to the third power. Greek letters in equations are
+translated to their English version.
+
+The sections in the Table of Contents are not used in the actual text.
+They have been added for clarity.
+
+Minor typos have been corrected and footnotes moved to the end of the
+sections
+
+       *       *       *       *       *
+
+
+
+
+
+PREFACE TO SECOND EDITION
+
+
+This edition is a _reprint_ of the first in response to a continuous
+demand for the book. The matter, consisting as it does largely of
+records, does not call for any revision, and, as a contribution to the
+development of theory, any particular interest which it has is
+associated with the date at which it was written.
+
+The volume which has since appeared is the sequel, and aims at an
+exposition of the subject "to date".
+
+
+
+
+PREFACE
+
+
+This volume, which is intended as a supplement to the work which we
+published in 1895, gives a brief account of researches which have been
+subsequently published, as well as of certain of our own investigations,
+the results of which are now for the first time recorded.
+
+We have not attempted to give the subject-matter the form of a connected
+record. The contributions to the study of 'Cellulose' which are noticed
+are spread over a large area, are mostly 'sectional' in their aim, and
+the only cohesion which we can give them is that of classifying them
+according to the plan of our original work. Their subject-matter is
+reproduced in the form of a _precis_, as much condensed as possible; of
+the more important papers the original title is given. In all cases we
+have endeavoured to reproduce the Author's main conclusions, and in most
+cases without comment or criticism.
+
+Specialists will note that the basis of investigation is still in a
+great measure empirical; and of this the most obvious criterion is the
+confusion attaching to the use of the very word 'Cellulose.' This is due
+to various causes, one of which is the curious specialisation of the
+term in Germany as the equivalent of 'wood cellulose.' The restriction
+of this general or group term has had an influence even in scientific
+circles. Another influence preventing the recognition of the obvious
+and, as we think, inevitable basis of classification of the 'celluloses'
+is the empiricism of the methods of agricultural chemistry, which as
+regards cellulose are so far chiefly concerned with its negative
+characteristics and the analytical determination of the indigestible
+residue of fodder plants. Physiologists, again, have their own views and
+methods in dealing with cellulose, and have hitherto had but little
+regard to the work of the chemist in differentiating and classifying the
+celluloses on a systematic basis. There are many sides to the subject,
+and it is only by a sustained effort towards centralisation that the
+general recognition of a systematic basis can be secured.
+
+We may, we hope usefully, direct attention to the conspicuous neglect of
+the subject in this country. To the matter of the present volume,
+excluding our own investigations, there are but two contributions from
+English laboratories. We invite the younger generation of students of
+chemistry to measure the probability of finding a working career in
+connection with the cellulose industries. They will not find this
+invitation in the treatment accorded to the subject in text-books and
+lectures. It is probable, indeed, that the impression produced by their
+studies is that the industries in coal-tar products largely exceed in
+importance those of which the carbohydrates are the basis; whereas the
+former are quite insignificant by comparison. A little reflection will
+prove that cellulose, starch, and sugar are of vast industrial moment in
+the order in which they are mentioned. If it is an open question to
+what extent science follows industry, or _vice versa_, it is not open to
+doubt that scientific men, and especially chemists, are called in these
+days to lead and follow where industrial evolution is most active. There
+is ample evidence of activity and great expansion in the cellulose
+industries, especially in those which involve the chemistry of the raw
+material; and the present volume should serve to show that there is
+rapid advance in the science of the subject. Hence our appeal to the
+workers not to neglect those opportunities which belong to the days of
+small beginnings.
+
+We have especially to acknowledge the services of Mr. J. F. BRIGGS in
+investigations which are recorded on pp. 34-40 and pp. 125-133 of the
+text.
+
+
+
+
+CONTENTS
+
+THE MATTER OF THIS VOLUME MAY BE DIVIDED INTO THE FOLLOWING SECTIONS
+
+
+                                                                 PAGE
+
+INTRODUCTION--DEALING WITH THE SUBJECT IN GENERAL OUTLINE           1
+
+
+SECTION
+
+I. GENERAL CHEMISTRY OF THE TYPICAL COTTON CELLULOSE               13
+
+II. SYNTHETICAL DERIVATIVES--SULPHOCARBONATES AND ESTERS           27
+
+III. DECOMPOSITIONS OF CELLULOSE SUCH AS THROW LIGHT
+     ON THE PROBLEM OF ITS CONSTITUTION                            67
+
+IV. CELLULOSE GROUP, INCLUDING HEMICELLULOSES AND
+    TISSUE CONSTITUENTS OF FUNGI                                   97
+
+V. FURFUROIDS, i.e. PENTOSANES AND FURFURAL-YIELDING
+   CONSTITUENTS GENERALLY                                         114
+
+VI. THE LIGNOCELLULOSES                                           125
+
+VII. PECTIC GROUP                                                 152
+
+VIII. INDUSTRIAL AND TECHNICAL. GENERAL REVIEW                    155
+
+
+INDEX OF AUTHORS                                                  177
+
+INDEX OF SUBJECTS                                                 178
+
+
+
+
+CELLULOSE
+
+
+
+
+INTRODUCTION
+
+
+In the period 1895-1900, which has elapsed since the original
+publication of our work on 'Cellulose,' there have appeared a large
+number of publications dealing with special points in the chemistry of
+cellulose. So large has been the contribution of matter that it has been
+considered opportune to pass it under review; and the present volume,
+taking the form of a supplement to the original work, is designed to
+incorporate this new matter and bring the subject as a whole to the
+level to which it is thereby to be raised. Some of our critics in
+reviewing the original work have pronounced it 'inchoate.' For this
+there are some explanations inherent in the matter itself. It must be
+remembered that every special province of the science has its systematic
+beginning, and in that stage of evolution makes a temporary 'law unto
+itself.' In the absence of a dominating theory or generalisation which,
+when adopted, gives it an organic connection with the general advance of
+the science, there is no other course than to classify the
+subject-matter. Thus 'the carbohydrates' may be said to have been in the
+inchoate condition, qualified by a certain classification, prior to the
+pioneering investigations of Fischer. In attacking the already
+accumulated and so far classified material from the point of view of a
+dominating theory, he found not only that the material fell into
+systematic order and grew rapidly under the stimulus of fruitful
+investigation, but in turn contributed to the firmer establishment of
+the theoretical views to which the subject owed its systematic new
+birth. On the other hand, every chemist knows that it is only the
+simpler of the carbohydrates which are so individualised as to be
+connoted by a particular formula in the stereoisomeric system. Leaving
+the monoses, there is even a doubt as to the constitution of cane sugar;
+and the elements of uncertainty thicken as we approach the question of
+the chemical structure of starch. This unique product of plant life has
+a literature of its own, and how little of this is fully known to what
+we may term the 'average chemist' is seen by the methods he will employ
+for its quantitative estimation. In one particular review of our work
+where we are taken to task for producing 'an aggravating book, inchoate
+in the highest degree ... disfigured by an obscurity of diction which
+must materially diminish its usefulness' ['Nature,' 1897, p. 241], the
+author, who is a well-known and competent critic, makes use of the short
+expression in regard to the more complex carbohydrates, 'Above cane
+sugar, higher in the series, all is chaos,' and in reference to starch,
+'the subject is still enshrouded in mystery.' This 'material' complexity
+is at its maximum with the most complex members of the series, which are
+the celluloses, and we think accounts in part for the impatience of our
+critic. 'Obscurity of diction' is a personal quantity, and we must leave
+that criticism to the fates. We find also that many workers whose
+publications we notice in this present volume quite ignore the _plan_ of
+the work, though they make use of its matter. We think it necessary to
+restate this plan, which, we are satisfied, is systematic, and, in fact,
+inevitable. Cellulose is in the first instance a _structure_, and the
+anatomical relationships supply a certain basis of classification. Next,
+it is known to us and is defined by the negative characteristics of
+resistance to hydrolytic actions and oxidations. These are dealt with in
+the order of their intensity. Next we have the more positive definition
+by ultimate products of hydrolysis, so far as they are known, which
+discloses more particularly the presence of a greater or less proportion
+of furfural-yielding groups. Putting all these together as criteria of
+function and composition we find they supply common or general dividing
+lines, within which groups of these products are contained. The
+classification is natural, and in that sense inevitable; and it not only
+groups the physiological and chemical facts, but the industrial also. We
+do not propose to argue the question whether the latter adds any cogency
+to a scientific scheme. We are satisfied that it does, and we do not
+find any necessity to exclude a particular set of phenomena from
+consideration, because they involve 'commercial' factors. We have dealt
+with this classification in the original work (p. 78), and we discuss
+its essential basis in the present volume (p. 28) in connection with the
+definition of a 'normal' cellulose. But the 'normal' cellulose is not
+the only cellulose, any more than a primary alcohol or an aliphatic
+alcohol are the only alcohols. This point is confused or ignored in
+several of the recent contributions of investigators. It will suffice to
+cite one of these in illustration. On p. 16 we give an account of an
+investigation of the several methods of estimating cellulose, which is
+full of valuable and interesting matter. The purpose of the author's
+elaborate comparative study is to decide which has the strongest claims
+to be regarded as the 'standard' method. They appear to have a
+preference for the method of Lange--viz. that of heating at high
+temperatures (180 deg.) with alkaline hydrates, but the investigation shows
+that (as we had definitely stated in our original work, p. 214) this is
+subject to large and variable errors. The adverse judgment of the
+authors, we may point out, is entirely determined on the question of
+aggregate weight or yield, and without reference to the ultimate
+composition or constitution of the final product. None of the available
+criteria are applied to the product to determine whether it is a
+cellulose (anhydride) or a hydrate or a hydrolysed product. After these
+alkali-fusion processes the method of chlorination is experimentally
+reviewed and dismissed for the reason that the product retains
+furfural-yielding groups, which is, from our point of view, a particular
+recommendation, i.e. is evidence of the selective action of the chlorine
+and subsequent hydrolysis upon the lignone group. As a matter of fact it
+is the only method yet available for isolating the cellulose from a
+lignocellulose by a treatment which is quantitatively to be accounted
+for in every detail of the reactions. It does not yield a 'normal'
+cellulose, and this is the expression which, in our opinion, the authors
+should have used. It should have been pointed out, moreover, that, as
+the cellulose is separated from actual condensed combination with the
+lignone groups, it may be expected to be obtained in a hydrated form,
+and also not as a homogeneous substance like the normal cotton
+cellulose. The product is a cellulose of the second group of the
+classification. Another point in this investigation which we must
+criticise is the ultimate selection of the Schulze method of prolonged
+maceration with nitric acid and a chlorate, followed by suitable
+hydrolysis of the non-cellulose derivatives to soluble products. Apart
+from its exceptional inconvenience, rendering it quite impracticable in
+laboratories which are concerned with the valuation of cellulosic raw
+materials for industrial purposes, the attack of the reagent is complex
+and ill-defined. This criticism we would make general by pointing out
+that such processes quite ignore the specific characteristics of the
+non-cellulose components of the compound celluloses. The second division
+of the plan of our work was to define these constituents by bringing
+together all that had been established concerning them. These groups are
+widely divergent in chemical character, as are the compound celluloses
+in function in the plant. Consequently there is for each a special
+method of attack, and it is a reversion to pure empiricism to expect any
+one treatment to act equally on the pectocelluloses, lignocelluloses,
+and cutocelluloses. Processes of isolating cellulose are really more
+strictly defined as methods of selective and regulated attack of the
+groups with which they occur, combined or mixed. A chemist familiar with
+such types as rhea or ramie (pectocellulose), jute (lignocellulose), and
+raffia (cutocellulose) knows exactly the specific treatment to apply to
+each for isolating the cellulose, and must view with some surprise the
+appearance at this date of such 'universal prescriptions' as the process
+in question.
+
+The third division of our plan of arrangement comprised the synthetical
+derivatives of the celluloses, the sulphocarbonates first, as peculiarly
+characteristic, and then the esters, chiefly the acetates, benzoates,
+and nitrates. To these, investigators appear to have devoted but little
+attention, and the contribution of new matter in the present volume is
+mainly the result of our own researches. It will appear from this work
+that an exhaustive study of the cellulose esters promises to assist very
+definitely in the study of constitutional problems.
+
+This brings us to the fourth and, to the theoretical chemist, the most
+important aspect of the subject, the problem of the actual molecular
+structure of the celluloses and compound celluloses. It is herein we are
+of opinion that the subject makes a 'law unto itself.' If the
+constitution of starch is shrouded in mystery and can only be vaguely
+expressed by generalising a complex mass of statistics of its successive
+hydrolyses, we can only still more vaguely guess at the distance which
+separates us from a mental picture of the cellulose unit. We endeavour
+to show by our later investigations that this problem merges into that
+of the actual structure of cellulose in the mass. It is definitely
+ascertained that a change in the molecule, or reacting unit, of a
+cellulose, proportionately affects the structural properties of the
+derived compounds, both sulphocarbonates and esters. This is at least an
+indication that the properties of the visible aggregates are directly
+related to the actual configuration of the chemical units. But it
+appears that we are barred from the present discussion of such a problem
+in absence of any theory of the solid state generally, but more
+particularly of those forms of matter which are grouped together as
+'colloids.'
+
+Cellulose is distinguished by its inherent constructive functions, and
+these functions take effect in the plastic or colloidal condition of the
+substance. These properties are equally conspicuous in the synthetical
+derivatives of the compound. Without reference, therefore, to further
+speculations, and not deterred by any apparent hopelessness of solving
+so large a problem, it is clear that we have to exhaust this field by
+exact measurements of all the constants which can be reduced to
+numerical expression. It is most likely that the issue may conflict with
+some of our current views of the molecular state which are largely drawn
+from a study of the relatively dissociated forms of matter. But such
+conflicts are only those of enlargement, and we anticipate that all
+chemists look for an enlargement of the molecular horizon precisely in
+those regions where the forces of cell-life manifest themselves.
+
+The _cellulose group_ has been further differentiated by later
+investigations. The fibrous celluloses of which the typical members
+receive important industrial applications, graduate by insensible stages
+into the hemicelluloses which may be regarded as a well-established
+sub-group. In considering their morphological and functional
+relationships it is evident that the graduation accords with their
+structure and the less permanent functions which they fulfil. They are
+aggregates of monoses of the various types, chiefly mannose, galactose,
+dextrose, &c., so far as they have been investigated.
+
+Closely connected with this group are the constituents of the tissues of
+fungi. The recent researches of Winterstein and Gilson, which are noted
+in this present volume, have established definitely that they contain a
+nitrogenous group in intimate combination with a carbohydrate complex.
+This group is closely related to chitin, yielding glucosamin and acetic
+acid as products of ultimate hydrolysis. Special interest attaches to
+these residues, as they are in a sense intermediate products between the
+great groups of the carbohydrates and proteids (E. Fischer, Ber. 19,
+1920), and their further investigation by physiological methods may be
+expected to disclose a genetic connection.
+
+The _lignocelluloses_ have been further investigated. Certain new types
+have been added, notably a soluble or 'pectic' form isolated from the
+juice of the white currant (p. 152), and the pith-like wood of the
+AEschynomene (p. 135).
+
+Further researches on the typical fibrous lignocellulose have given us a
+basis for correcting some of the conclusions recorded in our original
+work, and a study of the esters has thrown some light on the
+constitution of the complex (p. 130).
+
+Of importance also is the identification of the hydroxyfurfurals as
+constituents of the lignocelluloses generally, and the proof that the
+characteristic colour-reactions with phenols (phloroglucinol) may be
+ascribed to the presence of these compounds (p. 116).
+
+The _pectocelluloses_ have not been the subject of systematic chemical
+investigation, but the researches of Gilson ('La Cristallisation de la
+Cellulose et la Composition Chimique de la Membrane Cellulaire
+Vegetale,' 'La Revue,' 'La Cellule,' i. ix.) are an important
+contribution to the natural history of cellulose, especially in relation
+to the 'pectic' constituents of the parenchymatous celluloses.
+Indirectly also the researches of Tollens on the 'pectins' have
+contributed to the subject in correcting some of the views which have
+had a text-book currency for a long period. These are dealt with on p.
+151. The results establish that the pectins are rather the soluble
+hydrated form of cellulosic aggregates in which acid groups may be
+represented; but such groups are not to be regarded as essentially
+characteristic of this class of compounds.
+
+~Furfural-yielding Substances~ (Furfuroids).--This group of plant products
+has been, by later investigations, more definitely and exclusively
+connected with the celluloses--i.e. with the more permanent of plant
+tissues. From the characteristic property of yielding furfural, which
+they have in common with the pentoses, they have been assumed to be the
+anhydrides of these C_{5} sugars or pentosanes; but the direct evidence
+for this assumption has been shown to be wanting. In regard to their
+origin the indirect evidences which have accumulated all point to their
+formation in the plant from hexoses. Of special interest, in its
+bearings on this point, is the direct transformation of levulose into
+furfural derivatives, which takes place under the action of condensing
+agents. The most characteristic is that produced by the action of
+anhydrous hydrobromic acid in presence of ether [Fenton], yielding a
+brommethyl furfural
+
+     C_{6}H_{12}O_{6} - 4H_{2}O + HBr = C_{5}H_{3}.O_{2}.CH_{2}Br
+
+with a Br atom in the methyl group. These researches of Fenton's appear
+to us to have the most obvious and direct bearings upon the genetic
+relationships of the plant furfuroids and not only _per se_. To give
+them their full significance we must recall the later researches of
+Brown and Morris, which establish that cane sugar is a primary or direct
+product of assimilation, and that starch, which had been assumed to be a
+species of universal _matiere premiere_, is probably rather a general
+reserve for the elaborating work of the plant. If now the aldose groups
+tend to pass over into the starch form, representing a temporary
+overflow product of the assimilating energy, it would appear that the
+ketose or levulose groups are preferentially used up in the elaboration
+of the permanent tissue. We must also take into consideration the
+researches of Lobry de Bruyn showing the labile functions of the typical
+CO group in both aldoses and hexoses, whence we may conclude that in the
+plant-cell the transition from dextrose to levulose is a very simple and
+often occurring process.
+
+We ourselves have contributed a link in this chain of evidence
+connecting the furfuroids of the plant with levulose or other
+keto-hexose. We have shown that the hydroxyfurfurals are constituents of
+the lignocelluloses. The proportion present in the free state is small,
+and it is not difficult to show that they are products of breakdown of
+the lignone groups. If we assume that such groups are derived ultimately
+from levulose, we have to account for the detachment of the methyl
+group. This, however, is not difficult, and we need only call to mind
+that the lignocelluloses are characterised by the presence of methoxy
+groups and a residue which is directly and easily hydrolysed to acetic
+acid. Moreover, the condensation need not be assumed to be a simple
+dehydration with attendant rearrangement; it may very well be
+accompanied or preceded by fixation of oxygen. Leaving out the
+hypothetical discussion of minor variations, there is a marked
+convergence of the evidence as to the main facts which establish the
+general relationships of the furfuroid group. This group includes both
+saturated and unsaturated or condensed compounds. The former are
+constituents of celluloses, the latter of the lignone complex of the
+lignocelluloses.
+
+The actual production of furfural by boiling with condensing acids is a
+quantitative measure of only a portion, i.e. certain members of the
+group. The hydroxyfurfurals, not being volatile, are not measured in
+this way. By secondary reactions they may yield some furfural, but as
+they are highly reactive compounds, and most readily condensed, they are
+for the most part converted into complex 'tarry' products. Hence we have
+no means, as yet, of estimating those tissue constituents which yield
+hydroxyfurfurals; also we have no measure of the furfurane-rings
+existing performed in such a condensed complex as lignone. But, chemists
+having added in the last few years a large number of facts and
+well-defined probabilities, it is clear that the further investigation
+of the furfuroid group will take its stand upon a much more adequate
+basis than heretofore. On the view of 'furfural-yielding' being
+co-extensive with 'pentose or pentosane,' not only were a number of
+important facts obscured or misinterpreted, but there was a barrenness
+of suggestion of genetic relationships. As the group has been widened
+very much beyond these limits, it is clear that if any group term or
+designation is to be retained that of 'furfuroid' is 'neutral' in
+character, and equally applicable to saturated substances of such widely
+divergent chemical character as pentoses, hexosones, glycuronic acid,
+and perhaps, most important of all, levulose itself, all of which are
+susceptible of condensation to furfural or furfurane derivatives, as
+well as to those unsaturated compounds, constituents of plant tissues
+which are already furfurane derivatives.
+
+From the chemical point of view such terms are perhaps superfluous. But
+physiological relationships have a significance of their own; and there
+is a physiological or functional cohesion marking this group which
+calls for recognition, at least for the time, and we therefore propose
+to retain the term furfuroid.[1]
+
+~General Experimental Methods.~--In the investigation of the cellulose
+group it is clear that methods of ultimate hydrolysis are of first
+importance. None are so convenient as those which are based on the
+action of sulphuric acid, more or less concentrated (H_{2}SO_{4}.3H_{2}O
+- H_{2}SO_{4}H_{2}O). Such methods have been frequently employed in the
+investigations noted in this volume. We notice a common deficiency in
+the interpretation of the results. It appears to be sufficient to
+isolate and identify a crystalline monose, without reference to the
+yield or proportion to the parent substance, to establish some main
+point in connection with its constitution. On the other hand, it is
+clear that in hydrolysing a given cellulose-complex we ought to aim at
+complete, i.e. _quantitative, statistics_. The hydrolytic transformation
+of starch to dextrins and maltose has been followed in this way, and the
+methods may serve as a model to which cellulose transformations should
+be approximated. In fact, what is very much wanted is a systematic
+re-examination of the typical celluloses in which all the constants of
+the terms between the original and the ultimate monose groups shall be
+determined. Such constants are similar to those for the starch-dextrose
+series, viz. opticity and cupric reduction. Various methods of
+fractionation are similarly available, chiefly the precipitation of the
+intermediate 'dextrins' by alcohol.
+
+Where the original celluloses are homogeneous we should thus obtain
+transformation series, similarly expressed to those of starch. In the
+case of the celluloses which are mixtures, or of complex constitution,
+there are various methods of either fractionating the original, or of
+selectively attacking particular monoses resulting from the
+transformation. By methods which are approximately quantitative a
+mixture of groups, such as we have, for instance, in jute cellulose,
+could be followed through the several stages of their resolution into
+monoses. To put the matter generally, in these colloidal and complex
+carbohydrates the ordinary physical criteria of molecular weight are
+wanting. Therefore, we cannot determine the relationship of a given
+product of decomposition to the parent molecule save by means of a
+quantitative mass-proportion. Physical criteria are only of determining
+value when associated with such constants as cupric reduction, and
+these, again, must be referred to some arbitrary initial weight, such
+as, for convenience, 100 parts of the original.
+
+Instead of adopting these methods, without which, as a typical case, the
+mechanism of starch conversions could not have been followed, we have
+been content with a purely qualitative study of the analogous series
+obtainable from the celluloses under the action of sulphuric acid. A
+very important field of investigation lies open, especially to those who
+are generally familiar with the methods of studying starch conversions;
+and we may hope in this direction for a series of valuable contributions
+to the problem of the actual constitution of the celluloses.
+
+FOOTNOTES:
+
+[1] In this we are confirmed by other writers. See Tollens, _J. fuer
+Landw._ 1901, p. 27.
+
+
+
+
+SECTION I. GENERAL CHEMISTRY OF THE TYPICAL COTTON CELLULOSE
+
+
+(p. 3)[2] ~Ash Constituents.~--It is frequently asserted that silica has a
+structural function _sui generis_ in the plant skeleton, having a
+relationship to the cellulosic constituents of the plant, distinct from
+that of the inorganic ash components with which it is associated. It
+should be noted that the matter has been specifically investigated in
+two directions. In Berl. Ber. 5, 568 (A. Ladenburg), and again in 11,
+822 (W. Lange), appear two papers 'On the Nature of Plant Constituents
+containing Silicon,' which contain the results of experimental
+investigations of equisetum species--distinguished for their
+exceptionally high 'ash' with large proportion of silica--to determine
+whether there are any grounds for assuming the existence of
+silicon-organic compounds in the plant, the analogues of carbon
+compounds. The conclusions arrived at are entirely negative. In
+reference to the second assumption that the cuticular tissues of cereal
+straws, of esparto, of the bamboo, owe their special properties to
+siliceous components, it has been shown by direct experiment upon the
+former that their rigidity and resistance to water are in no way
+affected by cultivation in a silica-free medium. In other words, the
+structural peculiarities of the gramineae in these respects are due to
+the physical characteristics chiefly of the (lignified) cells of the
+hypodermal tissue, and to the composition and arrangement of the cells
+of the cuticle.
+
+_'Swedish' filter papers_ of modern make are so far freed from inorganic
+constituents that the weight of the ash may be neglected in nearly all
+quantitative experiments [Fresenius, Ztschr. Anal Chem. 1883, 241]. It
+represents usually about 1/1000 mgr. per 1 sq. cm. of area of the paper.
+
+_The form of an 'ash'_ derived from a fibrous structure, is that of the
+'organic' original, more or less, according to its proportion and
+composition. The proportion of 'natural ash' is seldom large enough, nor
+are the components of such character as to give a coherent ash, but if
+in the case of a fibrous structure it is combined or intimately mixed
+with inorganic compounds deposited within the fibres from solution, the
+latter may be made to yield a perfect skeleton of the fibre after
+burning off the organic matter. It is by such means that the mantles
+used in the Welsbach system of incandescent lighting are prepared. A
+purified cotton fabric--or yarn--is treated with a concentrated solution
+of the mixed nitrates of thorium and cerium, and, after drying, the
+cellulose is burned away. A perfect and coherent skeleton of the fabric
+is obtained, composed of the mixed oxides. Such mantles have fulfilled
+the requirements of the industry up to the present time, but later
+experiments forecast a notable improvement. It has been found that
+artificial cellulose fibres can be spun with solutions containing
+considerable proportions of soluble compounds of these oxides. Such
+fibres, when knitted into mantles and ignited, yield an inorganic
+skeleton of the oxides of homogeneous structure and smooth contour. De
+Mare in 1894, and Knofler in 1895, patented methods of preparing such
+cellulose threads containing the salts of thorium and cerium, by
+spinning a collodion containing the latter in solution. When finally
+ignited, after being brought into the suitable mantle form, there
+results a structure which proves vastly more durable than the original
+Welsbach mantle. The cause of the superiority is thus set forth by V.
+H. Lewes in a recent publication (J. Soc. of Arts, 1900, p. 858): 'The
+alteration in physical structure has a most extraordinary effect upon
+the light-giving life of the mantle, and also on its strength, as after
+burning for a few hundred hours the constant bombardment of the mantle
+by dust particles drawn up by the rush of air in the chimney causes the
+formation of silicates on the surface of the mantle owing to silica
+being present in the air, and this seems to affect the Welsbach
+structure far more than it does the "Clamond" type, with the result that
+when burned continuously the Welsbach mantle falls to so low a pitch of
+light emissivity after 500 to 600 hours, as to be a mere shadow of its
+former self, giving not more than one-third of its original light,
+whilst the Knofler mantle keeps up its light-emitting power to a much
+greater extent, and the Lehner fabric is the most remarkable of all. Two
+Lehner mantles which have now been burning continuously in my laboratory
+for over 3,000 hours give at this moment a brighter light emissivity
+than most of the Welsbachs do in their prime.' ...'The new developments
+of the Clamond process form as important a step in the history of
+incandescent gas lighting as the discoveries which gave rise to the
+original mantles.'
+
+It has further been found that the oxides themselves can be dissolved in
+the cellulose alkaline sulphocarbonate (viscose) solution, and
+artificial threads have been spun containing from 25 to 30 p.ct. of the
+oxides in homogeneous admixture with the cellulose. This method has
+obvious advantages over the collodion method both in regard to the
+molecular relationship of the oxides to the cellulose and to cheapness
+of production.
+
+
+UNTERSUCHUNGEN UeBER VERSCHIEDENE BESTIMMUNGSMETHODEN DER CELLULOSE.
+
+H. SURINGAR AND B. TOLLENS (Ztschr. angew. Chem. 1896, No. 23).
+
+~INVESTIGATION OF METHODS OF DETERMINING CELLULOSE.~
+
+_Introduction._--This is an exhaustive bibliography of the subject,
+describing also the various methods of cellulose estimation, noted in
+historical sequence. First, the Weende 'crude fibre' method (Henneberg)
+with modifications of Wattenberg, Holdefleiss, and others is dealt with.
+The product of this treatment, viz. 'crude fibre' is a mixture,
+containing furfuroids and lignone compounds. Next follows a group of
+processes which aim at producing a 'pure cellulose' by eliminating
+lignone constituents, for which the merely hydrolytic treatments of the
+Weende method are ineffectual. The method of F. Schulze--prolonged
+digestion with dilute nitric acid, with addition of chlorate--has been
+largely employed, though the composition of the product is more or less
+divergent from a 'pure cellulose.'
+
+Dilute nitric acid at 60-80 deg. (Cross and Bevan) and a dilute mixture of
+nitric and sulphuric acids (Lifschutz) have been employed for isolating
+cellulose from the lignocelluloses. Hoffmeister modifies the method of
+Schulze by substituting hydrochloric acid for the nitric acid. Treatment
+with the halogens associated with alkaline processes of hydrolysis is
+the basis of the methods of Hugo Muller (bromine water) and Cross and
+Bevan (chlorine gas). Lastly, the authors notice the methods based upon
+the action of the alkaline hydrates at high temperatures (180 deg.) in
+presence of water (Lange), or of glycerin (Gabriel). The process of
+heating to 210 deg. with glycerin only (Hoenig) yields a very impure and
+ill-defined product.
+
+For comparative investigation of these processes certain celluloses and
+cellulosic materials were prepared as follows:
+
+(a) _'Rag' cellulose._--A chemical filter paper, containing only
+cotton and linen celluloses, was further purified by boiling with dilute
+acid and dilute alkali. After thorough washing it was air-dried.
+
+(b) _Wood cellulose._--Pine wood sawdust was treated by digestion for
+fourteen days with dilute nitric acid with addition of chlorate
+(Schulze). The mass was washed and digested with alkaline lye (1.25
+p.ct. KOH), and exhaustively washed, treated with dilute acetic acid;
+again washed, and finally air-dried.
+
+This product was found to yield 2.3 p.ct. furfural on distillation with
+HCl (1.06 sp.gr.).
+
+(c) _Purified wood._--Pine wood sawdust was treated in succession with
+dilute alkalis and acids, in the cold, and with alcohol and ether until
+exhausted of products soluble in these liquids and reagents.
+
+In addition to the above the authors have also employed jute fibre and
+raw cotton wool in their investigations.
+
+They note that the yield of cellulose is in many cases sensibly lowered
+by treating the material after drying at the temperature of 100 deg.. The
+material for treatment is therefore weighed in the air-dry condition,
+and a similar sample weighed off for drying at 100 deg. for determination of
+moisture.
+
+The main results of the experimental investigation are as follows:--
+
+_Weende process_ further attacks the purified celluloses as follows:
+Wood cellulose losing in weight 8-9 p.ct.; filter paper, 6-7.5 p.ct.,
+and the latter treated a second time loses a further 4-5 p.ct. It is
+clear, therefore, that the process is of purely empirical value.
+
+_Schulze._--This process gave a yield of 47.6 p.ct. cellulose from pine
+wood. The celluloses themselves, treated by the process, showed losses
+of 1-3 p.ct. in weight, much less therefore than in the preceding case.
+
+_Hoenig's_ method of heating with glycerin to 210 deg. was found to yield
+products very far removed from 'cellulose.' The process may have a
+certain value in estimations of 'crude fibre,' but is dismissed from
+further consideration in relation to cellulose.
+
+_Lange._--The purpose of the investigation was to test the validity of
+the statement that the celluloses are not attacked by alkaline hydrates
+at 180 deg.. Experiments with pine wood yielded a series of percentages for
+cellulose varying from 36 to 41; the 'purified wood' gave also variable
+numbers, 44 to 49 per cent. It was found possible to limit these
+variations by altering the conditions in the later stages of isolating
+the product; but further experiments on the celluloses themselves
+previously isolated by other processes showed that they were profoundly
+and variably attacked by the 'Lange' treatment, wood cellulose losing 50
+per cent. of its weight, and filter paper (cellulose) losing 15 per
+cent. Further, a specimen of jute yielded 58 per cent. of cellulose by
+this method instead of the normal 78 per cent. It was also found that
+the celluloses isolated by the process, when subjected to a second
+treatment, underwent a further large conversion into soluble
+derivatives, and in a third treatment further losses of 5-10 per cent
+were obtained. The authors attach value, notwithstanding, to the process
+which they state to yield an 'approximately pure cellulose,' and they
+describe a modified method embodying the improvements in detail
+resulting from their investigation.
+
+_Gabriel's_ method of heating with a glycerin solution of alkaline
+hydrate is a combination of 'Hoenig' and 'Lange.' An extended
+investigation showed as in the case of the latter that the
+celluloses themselves are more or less profoundly attacked by the
+treatment--further that the celluloses isolated from lignocelluloses and
+other complex raw materials are much 'less pure' than those obtained by
+the Lange process. Thus, notably in regard to furfural yielding
+constituents, the latter yield 1-2 p.ct. furfural, whereas _specimens of
+'jute cellulose'_ obtained by the Gabriel process were found to yield _9
+to 13 p.ct. furfural_.
+
+_Cross and Bevan._--Chlorination process yielded in the hands of the
+authors results confirming the figures given in 'Cellulose' for yield of
+cellulose. Investigation of the products for yield of furfural, gave 9
+p.ct. of this aldehyde showing the presence of celluloses, other than
+the normal type.
+
+_Conclusions._--The subjoined table gives the mean numerical results for
+yield of end-product or 'cellulose' by the various methods. In the case
+of the 'celluloses' the results are those of the further action of the
+several processes on the end-product of a previous process.
+
+                       |                 Methods
+                       | F. Schulze | Weende | Lange | Gabriel |  Cross
+                       |            |        |       |         | and Bevan
+--------------------------------------------------------------------------
+Wood cellulose         | 98.51      | 91.52  | 48.22 | 55.93   | --
+Filter paper cellulose | 99.62      | 95.63  | 78.17 | 79.77   | --
+Swedish filter paper   | 96.58      |  --    | 84.76 |  --     | --
+Ordinary filter paper  | 98.17      | 93.39  | 86.58 |  --     | --
+Cotton ('wool')        | 98.38      | 89.98  | 63.96 | 67.88   | --
+Jute                   |  --        |  --    | 57.93 | 71.64   | 75.27
+Purified wood          |  --        |  --    |{49.27 |  --     | --
+                       |            |        |{46.56 |         |
+Raw wood               | 47.60      |  --    |{40.82 |  --     | --
+                       |            |        |{38.87 |         |
+--------------------------------------------------------------------------
+
+The final conclusion drawn from the results is that none of the
+processes fulfil the requirements of an ideal method. Those which may
+be carried out in a reasonably short time are deficient in two
+directions: (1) they yield a 'cellulose' containing more or less
+oxycellulose; (2) the celluloses themselves are attacked under the
+conditions of treatment, and the end product or cellulose merely
+represents a particular and at the same time variable equilibrium, as
+between the resistance of the cellulose and the attack of the reagents
+employed; this attack being by no means confined to the non-cellulose
+constituents. Schulze's method appears to give the nearest approximation
+to the 'actual cellulose' of the raw material.
+
+       *       *       *       *       *
+
+(p. 8) ~SOLUTIONS OF CELLULOSE~--(1) ~ZINC CHLORIDE.~--To prepare a
+homogeneous solution of cellulose by means of the neutral chloride, a
+prolonged digestion at or about 100 deg. with the concentrated reagent is
+required. The dissolution of the cellulose is not a simple phenomenon,
+but is attended with hydrolysis and a certain degree of condensation.
+The latter result is evidenced by the formation of furfural, the former
+by the presence of soluble carbohydrates in the solution obtained by
+diluting the original solution and filtering from the reprecipitated
+cellulose. The authors have observed that in carefully conducted
+experiments cotton cellulose may be dissolved in the reagent, and
+reprecipitated with a loss of only 1 p.ct. in weight. This, however, is
+a 'net' result, and leaves undetermined the degree of hydration of the
+recovered cellulose as of hydrolysis of the original to groups of lower
+molecular weights. Bronnert finds that a previous hydration of the
+cellulose--e.g. by the process of alkaline mercerisation and removal of
+the alkali by washing--enables the zinc chloride to effect its
+dissolution by digestion in the cold. (U.S. patent, 646,799/1900. See
+also p. 59.)
+
+_Industrial applications._--(a) _Vulcanised fibre_ is prepared by
+treating paper with four times its weight of the concentrated aqueous
+solution (65-75 deg. B.), and in the resulting gelatinised condition is
+worked up into masses, blocks, sheets, &c., of any required thickness.
+The washing of these masses to remove the zinc salt is a very lengthy
+operation.
+
+To render the product waterproof the process of nitration is sometimes
+superadded [D.R.P. 3181/1878]. Further details of manufacture are given
+in Prakt. Handbuch d. Papierfabrikation, p. 1703 [C. Hofmann].
+
+(b) _Calico-printing._--The use of the solution as a thickener or
+colour vehicle, more especially as a substitute for albumen in pigment
+styles, was patented by E. B. Manby, but the process has not been
+industrially developed [E.P. 10,466/1894].
+
+(c) _Artificial silk._--This is a refinement of the earlier
+applications of the solution in spinning cellulose threads for
+conversion into carbon filaments for electrical glow-lamps. This section
+will be found dealt with on p. 59.
+
+(p. 13) (2) ~Cuprammonium solution.~--The application of the solution of
+cellulose in cuprammonium to the production of a fine filament in
+continuous length, 'artificial silk,' has been very considerably studied
+and developed in the period 1897-1900, as evidenced by the series of
+patents of Fremery and Urban, Pauly, Bronnert, and others. The subject
+will also be found dealt with on p. 58.
+
+       *       *       *       *       *
+
+(p. 15) ~Reactions of cellulose with iodine.~--In a recent paper, F.
+Mylius deals with the reaction of starch and cellulose with iodine,
+pointing out that the blue colouration depends upon the presence of
+water and iodides. In absence of the latter, and therefore in presence
+of compounds which destroy or absorb hydriodic acid--e.g. iodic
+acid--there results a _brown_ addition product. The products in question
+have the characteristics of _solid solutions_ of the halogen. (Berl.
+Ber. 1895, 390.)
+
+(24) ~Mercerisation~--Notwithstanding the enormous recent developments in
+the industrial application of the mercerising reaction, there have been
+no noteworthy contributions to the theoretical aspects of the subject.
+The following abstract gives an outline of the scope of an important
+technical work on the subject.
+
+
+DIE MERCERISATION DER BAUMWOLLE.
+
+PAUL GARDNER (Berlin: 1898. J. Springer).
+
+~THE MERCERISATION OF COTTON.~
+
+This monograph of some 150 pages is chiefly devoted to the patent
+literature of the subject. The chemical and physical modifications of
+the cotton substance under the action of strong alkaline lye, were set
+forth by Mercer in 1844-5, and there has resulted from subsequent
+investigations but little increase in our knowledge of the fundamental
+facts. The treatment was industrially developed by Mercer in certain
+directions, chiefly (1) for preparing webs of cloth required to stand
+considerable strain, and (2) for producing crepon effects by local or
+topical action of the alkali. But the results achieved awakened but a
+transitory interest, and the matter passed into oblivion; so much so,
+indeed, that a German patent [No. 30,966] was granted in 1884 to the
+Messrs. Depouilly for crepon effects due to the differential shrinkage
+of fabrics under mercerisation, by processes and treatments long
+previously described by Mercer. Such effects have had a considerable
+vogue in recent years, but it was not until the discovery of the
+lustreing effect resulting from the association of the mercerising
+actions with the condition of strain or tension of the yarn or fabric
+that the industry in 'mercerised' goods was started on the lines which
+have led to the present colossal development. The merit of this
+discovery is now generally recognised as belonging to Thomas and Prevost
+of Crefeld, notwithstanding that priority of patent right belongs to the
+English technologist, H. A. Lowe.
+
+The author critically discusses the grounds of the now celebrated patent
+controversy, arising out of the conflict of the claims of German patent
+85,564/1895 of the former, and English patent 4452/1890 of the latter.
+The author concludes that Lowe's specification undoubtedly describes the
+lustreing effect of mercerising in much more definite terms than that of
+Thomas and Prevost. These inventors, on the other hand, realised the
+effect industrially, which Lowe certainly failed to do, as evidenced by
+his allowing the patent to lapse. As an explanation of his failure, the
+author suggests that Lowe did not sufficiently extend his observations
+to goods made from Egyptian and other long-stapled cottons, in which
+class only are the full effects of the added lustre obtained.
+
+Following these original patents are the specifications of a number of
+inventions which, however, are of insignificant moment so far as
+introducing any essential variation of the mercerising treatment.
+
+The third section of the work describes in detail the various mechanical
+devices which have been patented for carrying out the treatment on yarn
+and cloth.
+
+The fourth section deals with the fundamental facts underlying the
+process and effects summed up in the term 'mercerisation.' These are as
+follows:--
+
+(a) Although all forms of fibrous celluloses are similarly affected by
+strong alkaline solutions, it is only the Egyptian and other
+long-stapled cottons--i.e. the goods made from them--which under the
+treatment acquire the special high lustre which ranks as 'silky.' Goods
+made from American cottons acquire a certain 'finish' and lustre, but
+the effects are not such as to have an industrial value--i.e. a value
+proportional to the cost of treatment.
+
+(b) The lustre is determined by exposing the goods to strong tension,
+either when under the action of the alkali, or subsequently, but only
+when the cellulose is in the special condition of hydration which is the
+main chemical effect of the mercerising treatment.
+
+(c) The degree of tension required is approximately that which opposes
+the shrinkage in dimensions, otherwise determined by the action of the
+alkali. The following table exhibits the variations of shrinkage of
+Egyptian when mercerised without tension, under varying conditions as
+regards the essential factors of the treatment--viz. (1) concentration
+of the alkaline lye, (2) temperature, and (3) duration of action (the
+latter being of subordinate moment):--
+
+ _______________________________________________________________________
+|               |             |             |                    |      |
+| Concentration |             |             |                    |      |
+| of lye (NaOH) |    5 deg.B.     |    10 deg.B.    |        15 deg.B        | 25 deg.B |
+|               |   |    |    |   |    |    |      |      |      |      |
+| Duration of   |   |    |    |   |    |    |      |      |      |      |
+| action in     | 1 | 10 | 30 | 1 | 10 | 30 |   1  |  10  |  30  |      |
+| minutes       |   |    |    |   |    |    |      |      |      |      |
+|               |   |    |    |   |    |    |      |      |      |      |
+| Temperatures  |   Percentage shrinkages (Egyptian yarns) as under:--  |
+| as under:--   |   |    |    |   |    |    |      |      |      |      |
+|  2 deg.           | 0 |  0 |  0 | 1 |  1 |  1 | 12.2 | 15.2 | 15.8 | 19.2 |
+| 18 deg.           | 0 |  0 |  0 | 0 |  0 |  0 |  8.0 |  8.8 | 11.8 | 19.8 |
+| 30 deg.           | 0 |  0 |  0 | 0 |  0 |  0 |  4.6 |  4.6 |  6.0 | 19.0 |
+| 80 deg.           | 0 |  0 |  0 | 0 |  0 |  0 |  3.5 |  3.5 |  9.8 | 13.4 |
+|_______________|___|____|____|___|____|____|______|______|______|______|
+ _______________________________________________________________________
+|               |             |                    |                    |
+| Concentration |             |                    |                    |
+| of lye (NaOH) |     25 deg.B    |        30 deg.B        |        35 deg.B        |
+|               |      |      |      |      |      |      |      |      |
+| Duration of   |      |      |      |      |      |      |      |      |
+| action in     |  10  |  30  |   1  |  10  |  30  |   1  |  10  |  30  |
+| minutes       |      |      |      |      |      |      |      |      |
+|               |      |      |      |      |      |      |      |      |
+| Temperatures  |   Percentage shrinkages (Egyptian yarns) as under:--  |
+| as under:--   |      |      |      |      |      |      |      |      |
+|  2 deg.           | 19.8 | 21.5 | 22.7 | 22.7 | 22.7 | 24.2 | 24.5 | 24.7 |
+| 18 deg.           | 20.1 | 21.0 | 21.2 | 22.0 | 22.3 | 23.5 | 23.8 | 24.7 |
+| 30 deg.           | 19.5 | 19.0 | 18.5 | 19.5 | 19.8 | 20.7 | 21.0 | 21.1 |
+| 80 deg.           | 13.7 | 14.2 | 15.0 | 15.1 | 15.5 | 15.0 | 15.2 | 15.4 |
+|_______________|______|______|______|______|______|______|______|______|
+
+The more important general indications of the above results are--(1) The
+mercerisation action commences with a lye of 10 deg.B., and increases with
+increased strength of the lye up to a maximum at 35 deg.B. There is,
+however, a relatively slight increase of action with the increase of
+caustic soda from 30-40 deg.B. (2) For optimum action the temperature should
+not exceed 15-20 deg.C. (3) The duration of action is of proportionately
+less influence as the concentration of the lye increases. As the maximum
+effect is attained the action becomes practically instantaneous, the
+only condition affecting it being that of penetration--i.e. actual
+contact of cellulose and alkali.
+
+(d) The question as to whether the process of 'mercerisation' involves
+chemical as well as physical effects is briefly discussed. The author is
+of opinion that, as the degree of lustre obtained varies with the
+different varieties of cotton, the differentiation is occasioned by
+differences in chemical constitution of these various cottons. The
+influence of the chemical factors is also emphasised by the increased
+dyeing capacity of the mercerised goods, which effect, moreover, is
+independent of those conditions of strain or tension under mercerisation
+which determine lustre. It is found in effect that with a varied range
+of dye stuffs a given shade is produced with from 10 to 30 p.ct. less
+colouring matter than is required for the ordinary, i.e. unmercerised,
+goods.
+
+In reference to the constants of strength and elasticity, Buntrock gives
+the following results of observations upon a 40^{5} twofold yarn, five
+threads of 50 cm. length being taken for each test(Prometheus, 1897, p.
+690): (a) the original yarn broke under a load of 1440 grms.; (b)
+after mercerisation without tension the load required was 2420 grms.;
+(c) after mercerisation under strain, 1950 grms. Mercerisation,
+therefore, increases the strength of the yarn from 30 to 66 p.ct., the
+increase being lessened proportionately to the strain accompanying
+mercerisation. _Elasticity_, as measured by the extension under the
+breaking load, remains about the same in yarns mercerised under strain,
+but when allowed to shrink under mercerisation there is an increase of
+30-40 p.ct. over the original.
+
+The _change of form_ sustained by the individual fibres has been studied
+by H. Lange [Farberzeitung, 1898, 197-198], whose microphotographs of
+the cotton fibres, both in length and cross-section, are reproduced. In
+general terms, the change is from the flattened riband of the original
+fibre to a cylindrical tube with much diminished and rounded central
+canal. The effect of strain under mercerisation is chiefly seen in the
+contour of the surface, which is smooth, and the obliteration at
+intervals of the canal. Hence the increased transparency and more
+complete reflection of the light from the surface, and the consequent
+approximation to the optical properties of the silk fibre.
+
+The work concludes with a section devoted to a description of the
+various practical systems of mercerisation of yarns in general practice
+in Germany, and an account of the methods adopted in dyeing the
+mercerised yarns.
+
+
+RESEARCHES ON MERCERISED COTTON.
+
+A. FRAENKEL and P. FRIEDLAENDER (Mitt. k.-k. Techn. Gew. Mus., Wien,
+1898, 326).
+
+The authors, after investigation, are inclined to attribute the lustre
+of mercerised cotton to the absence of the cuticle, which is destroyed
+and removed in the process, partly by the chemical action of the alkali,
+and partly by the stretching at one or other stage of the process. The
+authors have investigated the action of alcoholic solutions of soda
+also. The lustre effects are not obtained unless the action of water is
+associated.
+
+In conclusion, the authors give the following particulars of breaking
+strains and elasticity:--
+
+--------------------------------------------------------------------------
+Treatment                 | Experiments | Breaking strain |  Elasticity
+--------------------------------------------------------------------------
+                          |             |                 |  Elongation
+                          |             |     Grammes     |  in mm.
+                          |             |                 |
+Cotton unmercerised.      |       1     |       360       |   20
+                          |       2     |       356       |   20
+                          |       3     |       360       |   22
+                          |             |                 |
+Mercerised with           |             |                 |
+  Soda 35 deg.B.              |       1     |       530       |   44
+                          |       2     |       570       |   40
+                          |       3     |       559       |   35
+                          |             |                 |
+  Alcoholic soda 10 p.ct. |       1     |       645       |   24
+    cold                  |       2     |       600       |   27
+                          |       3     |       610       |   33
+                          |             |                 |
+  Alcoholic soda 10 p.ct. |       5     |       740       |   33
+    hot                   |       2     |       730       |   38
+                          |       3     |       690       |   30
+--------------------------------------------------------------------------
+
+FOOTNOTES:
+
+[2] This and other similar references are to the matter of the original
+volume (1895).
+
+
+
+
+SECTION II. SYNTHETICAL DERIVATIVES--SULPHOCARBONATES AND ESTERS
+
+
+(p. 25) ~Cellulose sulphocarbonate.~--Further investigations of the
+reaction of formation as well as the various reactions of decomposition
+of the compound, have not contributed any essential modification or
+development of the subject as originally described in the author's first
+communications. A large amount of experimental matter has been
+accumulated in view of the ultimate contribution of the results to the
+general theory of colloidal solutions. But viscose is a complex product
+and essentially variable, through its pronounced tendency to progressive
+decomposition with reversion of the cellulose to its insoluble and
+uncombined condition. The solution for this reason does not lend itself
+to exact measurement of its physical constants such as might elucidate
+in some measure the progressive molecular aggregation of the cellulose
+in assuming spontaneously the solid (hydrate) form. Reserving the
+discussion of these points, therefore, we confine ourselves to recording
+results which further elucidate special points.
+
+_Normal and other celluloses._--We may certainly use the sulphocarbonate
+reaction as a means of defining a normal cellulose. As already pointed
+out, cotton cellulose passes quantitatively through the cycle of
+treatments involved in solution as sulphocarbonate and decomposition of
+the solution with regeneration as structureless or amorphous cellulose
+(hydrate).
+
+Analysis of this cellulose shows a fall of carbon percentage from 44.4
+to 43.3, corresponding with a change in composition from
+C_{6}H_{10}O_{5} to 4C_{6}H_{10}O_{5}.H_{2}O. The partial hydrolysis
+affects the whole molecule, and is limited to this effect, whereas, in
+the case of celluloses of other types, there is a fractionation of the
+mass, a portion undergoing a further hydrolysis to compounds of lower
+molecular weight and permanently soluble. Thus in the case of the wood
+celluloses the percentage recovered from solution as viscose is from 93
+to 95 p.ct. It is evident that these celluloses are not homogeneous. A
+similar conclusion results from the presence of furfural-yielding
+compounds with the observation that the hydrolysis to soluble
+derivatives mainly affects these derivatives. In the empirical
+characterisation of a normal cellulose, therefore, we may include the
+property of quantitative regeneration or recovery from its solution as
+sulphocarbonate.
+
+In the use of the word 'normal' as applied to a 'bleached' cotton, we
+have further to show in what respects the sulphocarbonate reaction
+differentiates the bleached or purified cotton cellulose from the raw
+product. The following experiments may be cited: Specimens of American
+and Egyptian cottons in the raw state, freed from mechanical, i.e.
+non-fibrous, impurities, were treated with a mercerising alkali, and the
+alkali-cotton subsequently exposed to carbon disulphide. The product of
+reaction was further treated as in the preparation of the ordinary
+solution; but in place of the usual solution, structureless and
+homogeneous, it was observed to retain a fibrous character, and the
+fibres, though enormously swollen, were not broken down by continued
+vigorous stirring. After large dilution the solutions were filtered, and
+the fibres then formed a gelatinous mass on the filters. After
+purification, the residue was dried and weighed. The American cotton
+yielded 90.0 p.ct., and the Egyptian 92.0 p.ct. of its substance in the
+form of this peculiar modification. The experiment was repeated,
+allowing an interval of 24 hours to elapse between the conversion into
+alkali-cotton and exposure of this to the carbon disulphide. The
+quantitative results were identical.
+
+There are many observations incidental to chemical treatments of cotton
+fabrics which tend to show that the bleaching process produces other
+effects than the mere removal of mechanical impurities. In the
+sulphocarbonate reaction the raw cotton, in fact, behaves exactly as a
+compound cellulose. Whether the constitutional difference between raw
+and bleached cotton, thus emphasised, is due to the group of components
+of the raw cotton, which are removed in the bleaching process, or to
+internal constitutional changes determined by the bleaching treatments,
+is a question which future investigation must decide.
+
+_The normal sulphocarbonate (viscose)._--In the industrial applications
+of viscose it is important to maintain a certain standard of composition
+as of the essential physical properties of the solution, notably
+viscosity. It may be noted first that, with the above-mentioned
+exception, the various fibrous celluloses show but slight differences in
+regard to all the essential features of the reactions involved. In the
+mercerising reaction, or alkali-cellulose stage, it is true the
+differences are considerable. With celluloses of the wood and straw
+classes there is a considerable conversion into soluble
+alkali-celluloses. If treated with water these are dissolved, and on
+weighing back the cellulose, after thorough washing, treatment with
+acid, and finally washing and drying, it will be found to have lost from
+15 to 20 p.ct. in weight. The lower grade of celluloses thus dissolved
+are only in part precipitated in acidifying the alkaline solution. On
+the other hand, after conversion into viscose, the cellulose when
+regenerated re-aggregates a large proportion of these lower grade
+celluloses, and the final loss is as stated above, from 5 to 7 p.ct.
+only.
+
+Secondly, it is found that all the conditions obtaining in the
+alkali-cellulose stage affect the subsequent viscose reaction and the
+properties of the final solution. The most important are obviously the
+proportion of alkali to cellulose and the length of time they are in
+contact before being treated with carbon disulphide. An excess of
+alkali beyond the 'normal' proportion--viz. 2NaOH per 1 mol.
+C_{6}H_{10}O_{5}--has little influence upon the viscose reaction, but
+lowers the viscosity of the solution of the sulphocarbonate prepared
+from it. But this effect equally follows from addition of alkali to the
+viscose itself. The alkali-cellulose changes with age; there is a
+gradual alteration of the molecular structure of the cellulose, of which
+the properties of the viscose when prepared are the best indication.
+There is a progressive loss of viscosity of the solution, and a
+corresponding deterioration in the structural properties of the
+cellulose when regenerated from it--especially marked in the film form.
+In regard to viscosity the following observations are typical:--
+
+     (a) A viscose of 1.8 p.ct. cellulose prepared from an
+     alkali-cellulose (cotton) fourteen days old.
+
+     (b) Viscose of 1.8 p.ct. cellulose from an alkali-cellulose
+     (cotton) three days old.
+
+     (c) Glycerin diluted with 1/3 vol. water.
+
+                                        a       b       b          c
+                                                    Diluted with
+                                                    equal vol.
+                                                      water
+Times of flow of equal volumes from    112     321     103        170
+  narrow orifice in seconds
+
+Similarly the cellulose in reverting to the solid form from these
+'degraded' solutions presents a proportionate loss of cohesion and
+aggregating power expressed by the inferior strength and elasticity of
+the products. Hence, in the practical applications of the product where
+the latter properties are of first importance, it is necessary to adopt
+normal standards, such as above indicated, and to carefully regulate all
+the conditions of treatment in each of the two main stages of reaction,
+so that a product of any desired character may be invariably obtained.
+
+Incidentally to these investigations a number of observations have been
+made on the alkali-cellulose (cotton) after prolonged storage in closed
+vessels. It is well known that starch undergoes hydrolysis in contact
+with aqueous alkalis of a similar character to that determined by acids
+[Bechamp, Annalen, 100, 365]. The recent researches of Lobry de Bruyn
+[Rec. Trav. Chim. 14, 156] upon the action of alkaline hydrates in
+aqueous solution on the hexoses have established the important fact of
+the resulting mobility of the CO group, and the interchangeable
+relationships of typical aldoses and ketoses. It was, therefore, not
+improbable that profound hydrolytic changes should occur in the
+cellulose molecule when kept for prolonged periods as alkali-cellulose.
+
+We may cite an extreme case. A series of products were examined after
+12-18 months' storage. They were found to contain only 3-5 p.ct.
+'soluble carbohydrates'; these were precipitated by Fehling's solution
+but without reduction on boiling. They were, therefore, of the cellulose
+type. On acidifying with sulphuric acid and distilling, traces only of
+volatile acid were produced. It is clear, therefore, that the change of
+molecular weight of the cellulose, the disaggregation of the undoubtedly
+large molecule of the original 'normal' cellulose--which effects are
+immediately recognised in the viscose reactions of such products--are of
+such otherwise limited character that they do not affect the
+constitution of the unit groups. We should also conclude that the
+cellulose type of constitution covers a very wide range of minor
+variations of molecular weight or aggregation.
+
+The resistance of the normal cellulose to the action of alkalis under
+these hydrolysing conditions should be mentioned in conjunction with the
+observations of Lange, and the results of the later investigations of
+Tollens, on its resistance to 'fusion' with alkaline hydrates at high
+temperatures (180 deg.). The degree of resistance has been established only
+on the empirical basis of weighing the product recovered from such
+treatment. The product must be investigated by conversion into typical
+cellulose derivatives before we can pronounce upon the constitutional
+changes which certainly occur in the process. But for the purpose of
+this discussion it is sufficient to emphasise the extraordinary
+resistance of the normal cellulose to the action of alkalis, and to
+another of the more significant points of differentiation from starch.
+
+_Chemical constants of cellulose sulphocarbonate (solution)._--In
+investigations of the solutions we make use of various analytical
+methods, which may be briefly described, noting any results bearing upon
+special points.
+
+_Total alkali._--This constant is determined by titration in the usual
+way. The cellulose ratio, C_{6}H_{10}O_{5} : 2NaOH, is within the
+ordinary error of observation, 2 : 1 by weight. A determination of alkali
+therefore determines the percentage of cellulose.
+
+_Cellulose_ may be regenerated in various ways--viz. by the action of
+heat, of acids, of various oxidising compounds. It is purified for
+weighing by boiling in neutral sulphite of soda (2 p.ct. solution) to
+remove sulphur, and in very dilute acids (0.33 p.ct. HCl) to decompose
+residues of 'organic' sulphur compounds. It may also be treated with
+dilute oxidants. After weighing it may be ignited to determine residual
+inorganic compounds.
+
+_Sulphur._--It has been proved by Lindemann and Motten [Bull. Acad. R.
+Belg. (3), 23, 827] that the sulphur of sulphocarbonates (as well as of
+sulphocyanides) is fully oxidised (to SO_{3}) by the hypochlorites
+(solutions at ordinary temperatures). The method may be adapted as
+required for any form of the products or by-products of the viscose
+reaction to be analysed for _total sulphur_.
+
+The sulphur present in the form of dithiocarbonates, including the
+typical cellulose xanthogenic acid, is approximately isolated and
+determined as CS_{2} by adding a zinc salt in excess, and distilling off
+the carbon disulphide from a water bath. From freshly prepared solutions
+a large proportion of the disulphide originally interacting with the
+alkali and cellulose is recovered, the result establishing the general
+conformity of the reaction to that typical of the alcohols. On keeping
+the solutions there is a progressive interaction of the bisulphide and
+alkali, with formation of trithiocarbonates and various sulphides. In
+decomposing these products by acid reagents hydrogen sulphide and free
+sulphur are formed, the estimation of which presents no special
+difficulties.
+
+In the spontaneous decomposition of the solution a large proportion of
+the sulphur resumes the form of the volatile disulphide. This is
+approximately measured by the loss in total sulphur in the following
+series of determinations, in which a viscose of 8.5 p.ct. strength
+(cellulose) was dried down as a thin film upon glass plates, and
+afterwards analysed:
+
+(a) Proportion of sulphur to cellulose (100 pts.) in original.
+(b) After spontaneous drying at ordinary temperature.
+(c) After drying at 40 deg.C.
+(d) As in (c), followed, by 2 hours' heating at 98 deg..
+(e) As in (c), followed by 5 hours' heating at 98 deg..
+
+                          a     b     c     d     e
+         Total sulphur   40.0  25.0  31.0  23.7  10.4
+
+The dried product in (b) and (c) was entirely resoluble in water; in
+(d) and (e), on the other hand, the cellulose was fully regenerated,
+and obtained as a transparent film.
+
+_Iodine reaction._--Fresh solutions of the sulphocarbonate show a fairly
+constant reaction with normal iodine solution. At the first point, where
+the excess of iodine visibly persists, there is complete precipitation
+of the cellulose as the bixanthic sulphide; and this occurs when the
+proportion of iodine added reaches 3I_{2} : 4Na_{2}O, calculated to the
+total alkali.
+
+_Other decompositions._--The most interesting is the interaction which
+occurs between the cellulose xanthogenate and salts of ammonia, which is
+taken advantage of by C. H. Stearn in his patent process of spinning
+artificial threads from viscose. The insoluble product which is formed
+in excess of the solution of ammonia salt is free from soda, and
+contains 9-10 p.ct. total sulphur. The product retains its solubility in
+water for a short period. The solution may be regarded as containing the
+ammonium cellulose xanthate. This rapidly decomposes with liberation of
+ammonia and carbon disulphide, and separation of cellulose (hydrate). As
+precipitated by ammonium-chloride solution the gelatinous thread
+contains 15 p.ct. of cellulose, with a sp.gr. 1.1. The process of
+'fixing'--i.e. decomposing the xanthic residue--consists in a short
+exposure to the boiling saline solution. The further dehydration, with
+increase of gravity and cellulose content, is not considerable. The
+thread in its final air-dry state has a sp.gr. 1.48.
+
+       *       *       *       *       *
+
+~Cellulose Benzoates.~--These derivatives have been further studied by the
+authors. The conditions for the formation of the monobenzoate
+[C_{6}H_{9}O_{4}.O.CO.Ph] are very similar to those required for the
+sulphocarbonate reaction. The fibrous cellulose (cotton), treated with a
+10 p.ct. solution NaOH, and subsequently with benzoyl chloride, gives
+about 50 p.ct. of the theoretical yield of monobenzoate. Converted by 20
+p.ct. solution NaOH into alkali-cellulose, and with molecular
+proportions as below, the following yields were obtained:--
+
+                                                              Calc. for
+                                                             Monobenzoate
+(a) C_{6}H_{10}O_{5} : 2.0-2.5 NaOH : C_{6}H_{5}.COCl--       150.8}
+                                                                   }164.0
+(b) C_{6}H_{10}O_{5} : 2.0-2.5 NaOH : 1.5 mol. C_{6}H_{5}COCl 159.0}
+
+An examination of (a) showed that some dibenzoate (about 7 p.ct.) had
+been formed. The product () was exhaustively treated with cuprammonium
+solution, to which it yielded about 20 p.ct. of its weight, which was
+therefore unattacked cellulose.
+
+Under conditions as above, but with 2.5 mol. C_{6}H_{5}COCl, a careful
+comparison was made of the behaviour of the three varieties of cotton,
+which were taken in the unspun condition and previously fully bleached
+and purified.
+
+ ___________________________________________________________________
+|                                |            |          |          |
+|                                | Sea Island | Egyptian | American |
+|________________________________|____________|__________|__________|
+|                                |            |          |          |
+| Aggregate yield of benzoate    |   153      |  148     |  152     |
+| Moisture in air dry state      |     5.28   |    5.35  |    5.15  |
+| Proportion of dibenzoate p.ct. |     8.30   |   13.70  |    9.4   |
+| Yield of cellulose by          |    58.0    |   54.0   |   58.3   |
+|   saponification               |            |          |          |
+|________________________________|____________|__________|__________|
+
+It appears from these results that the benzoate reaction may proceed to
+a higher limit (dibenzoate) in the case of Egyptian cotton. This would
+necessarily imply a higher limit of 'mercerisation,' under equal
+conditions of treatment with the alkaline hydrate. It must be noted that
+in the conversion of the fibrous cellulose into these (still) fibrous
+monobenzoates, there are certain mechanical conditions imported by the
+structural features of the ultimate fibres. For the elimination of the
+influence of this factor a large number of quantitative comparisons will
+be necessary. The above results are therefore only cited as typical of a
+method of comparative investigation, more especially of the still open
+questions of the cause of the superior effects in mercerisation of
+certain cottons (see p. 23). It is quite probable that chemical as well
+as structural factors co-operate in further differentiating the cottons.
+
+Further investigation of the influence upon the benzoate reaction, of
+increase of concentration of the soda lye, used in the preliminary
+alkali cellulose reaction, from 20 to 33 p.ct. NaOH, established (1)
+that there is no corresponding increase in the benzoylation, and (2)
+that this ester reaction and the sulphocarbonate reaction are closely
+parallel, in that the degree and limit of reaction are predetermined by
+the conditions of formation of the alkali cellulose.
+
+_Monobenzoate_ prepared as above described is resistant to all solvents
+of cellulose and of the cellulose esters, and is therefore freed from
+cellulose by treatment with the former, and from the higher benzoate by
+treatment with the latter. Several of these, notably pyridine, phenol
+and nitrobenzene, cause considerable swelling and gelatinisation of the
+fibres, but without solution.
+
+_Structureless celluloses_ of the 'normal' type, and insoluble therefore
+in alkaline lye, treated under similar conditions to those described
+above for the fibrous celluloses, yield a higher proportion of
+dibenzoate. The following determinations were made with the cellulose
+(hydrate) regenerated from the sulphocarbonate:--
+
+Mol. proportions of reagents          Yield       Dibenzoate p.ct.
+C_{6}H_{10}O_{5} : 2NaOH : 2BzCl        145             34.7
+  [Caustic soda at 10 per cent. NaOH]
+
+C_{6}H_{10}O_{5} : 4NaOH : 2BzCl        162             62.7
+  [Caustic soda at 20 per cent. NaOH]
+
+_Limit of reaction._--The cellulose in this form having shown itself
+more reactive, it was taken as the basis for determining the maximum
+proportion of OH groups yielding to this later reaction. The systematic
+investigations of Skraup [Monatsh. 10, 389] have determined that as
+regards the interacting groups the molecular proportions 1 OH : 7 NaOH :
+5 BzCl, ensure complete or maximum esterification. The maximum of OH
+groups in cellulose being 4, the reagents were taken in the proportion
+C_{6}H_{10}O_{5} : 4 [7 NaOH : 5 BzCl]. The yield of crude product, after
+purifying as far as possible from the excess of benzoic acid, was 240
+p.ct. [calculated for dibenzoate 227 p.ct.]. On further investigating
+the crude product by treatment with solvents, it was found to have still
+retained benzoic acid. There was also present a proportion of only
+partially attacked cellulose (monobenzoate). The soluble benzoate
+amounted to 90 p.ct. of the product. It may be generally concluded that
+the dibenzoate represents the normal maximum but that with the hydrated
+and partly hydrolysed cellulose molecule, as obtained by regeneration
+from the sulphocarbonate, other OH groups may react, but they are only a
+fractional proportion in relation to the unit group C_{6}H_{10}O_{5}. In
+this respect again there is a close parallelism between the
+sulphocarbonate and benzoyl-ester reactions.
+
+_The dibenzoate_, even when prepared from the fibrous celluloses, is
+devoid of structure, and its presence in admixture with the fibrous
+monobenzoate is at once recognised as it constitutes a structureless
+incrustation. Under the microscope its presence in however minute
+proportion is readily observed. As stated it is soluble in certain of
+the ordinary solvents of the cellulose esters, e.g. chloroform, acetic
+acid, nitrobenzene, pyridine, and phenol. It is not soluble in ether or
+alcohol.
+
+_Hygroscopic moisture of benzoates._--The crude monobenzoate retains
+5.0-5.5 p.ct. moisture in the air-dry condition. After removal of the
+residual cellulose this is reduced to 3.3 p.ct. under ordinary
+atmospheric conditions. The purified dibenzoates retain 1.6 p.ct. under
+similar conditions.
+
+_Analysis of benzoates._--On saponification of these esters with
+alcoholic sodium hydrate, anomalous results are obtained. The acid
+numbers, determined by titration in the usual way, are 10-20 p.ct. in
+excess of the theoretical, the difference increasing with the time of
+boiling. Similarly the residual cellulose shows a deficiency of 5-9
+p.ct.
+
+It is by no means improbable that in the original ester reaction there
+is a constitutional change in the cellulose molecule causing it to break
+down in part under the hydrolysing treatment with formation of acid
+products. This point is under investigation. Normal results as regards
+acid numbers, on the other hand, are obtained by saponification with
+sodium ethylate in the cold, the product being digested with the
+half-saturated solution for 12 hours in a closed flask.
+
+The following results with specimens of mono- and dibenzoate, purified,
+as far as possible, may be cited:
+
+           Combustion results           Saponification results
+                      Calc.     C_{6}H_{5}.COOH  Calc.  Cellulose  Calc.
+Monobenzoate  C 56.60  58.65}
+              H  5.06   5.26}       46.0          45.9    58.0     60.8
+
+Dibenzoate    C 63.10  64.86}
+              H  3.40   4.86}       65.5          66.6    34.3     40.3
+
+The divergence of the numbers, especially for the dibenzoate, in the
+case of the hydrogen, and yield of cellulose on hydrolysis are
+noteworthy. They confirm the probability of the occurrence of secondary
+changes in the ester reactions.
+
+_Action of nitrating acid upon the benzoates._--From the benzoates above
+described, mixed nitro-nitric esters are obtained by the action of the
+mixture of nitric and sulphuric acids. The residual OH groups of the
+cellulose are esterified and substitution by an NO_{2} group takes place
+in the aromatic residue, giving a mixed nitric nitrobenzoic ester. The
+analysis of the products points to the entrance of 1 NO_{2} group in the
+benzoyl residue in either case; in the cellulose residue 1 OH readily
+reacts. Higher degrees of nitration are attained by the process of
+solution in concentrated nitric acid and precipitation by pouring into
+sulphuric acid. In describing these mixed esters we shall find it
+necessary to adopt the C_{12} unit formula.
+
+In analysing these products we have employed the Dumas method for _total
+nitrogen_. For the O.NO_{2} groups we have found the nitrometer and the
+Schloesing methods to give concordant results. For the NO_{2} groups it
+was thought that Limpricht's method, based upon reduction with stannous
+chloride in acid solution (HCl), would be available. The quantitative
+results, however, were only approximate, owing to the difficulty of
+confining the reduction to the NO_{2} groups of the nitrobenzoyl
+residue. By reduction with ammonium sulphide the O.NO_{2} groups were
+entirely removed as in the case of the cellulose nitrates; the NO_{2}
+was reduced to NH_{2} and there resulted a cellulose amidobenzoate,
+which was diazotised and combined with amines and phenols to form yellow
+and red colouring matters, the reacting residue remaining more or less
+firmly combined with the cellulose.
+
+_Cellulose dinitrate-dinitrobenzoate, and cellulose
+trinitrate-dinitrobenzoate._--On treating the fibrous benzoate--which is
+a dibenzoate on the C_{12} basis--with the acid mixture under the usual
+conditions, a yellowish product is obtained, with a yield of 140-142
+p.ct. The nitrobenzoate is insoluble in ether alcohol, but is soluble in
+acetone, acetic acid, and nitrobenzene. In purifying the product the
+former solvent is used to remove any cellulose nitrates. To obtain the
+maximum combination with nitroxy-groups, the product was dissolved in
+concentrated nitric acid, and the solution poured into sulphuric acid.
+
+The following analytical results were obtained (a) for the product
+obtained directly from the fibrous benzoate and purified as indicated,
+(b) for the product from the further treatment of (a) as described:
+
+                       Found                   Calc. for
+                    (a)       (b)       Dinitrate      Trinitrate
+                                     dinitrobenzoate dinitrobenzoate
+Total Nitrogen     7.84       8.97         7.99            9.24
+O.NO_{2}  "        5.00       5.45         4.00            5.54
+NO_{2} (Aromatic)  2.84       3.52         3.99            3.70
+
+With the two benzoyl groups converted into nitro-benzoyl in each
+product, the limit of the ester reaction with the cellulose residue is
+reached at the third OH group.
+
+The nitrogen in the amidobenzoate resulting from the reduction with
+ammonium sulphide was 4.5 p.ct.--as against 5.0 p.ct. calculated. The
+moisture retained by the fibrous nitrate--nitrobenzoate--in the air-dry
+state was found to be 1.97 p.ct.
+
+The product from the structureless dibenzoate or tetrabenzoate on the
+C_{12} formula, was prepared and analysed with the following results:
+
+                                              Calc. for
+                                    Mononitrate tetranitrobenzoate
+Total Nitrogen               6.76                7.25
+O.NO_{2}  "                  1.30                1.45
+NO_{2}    "  (Aromatic)      5.46                5.80
+
+The results were confirmed by the yield of product, viz. 131 p.ct. as
+against the calculated 136 p.ct. They afford further evidence of the
+generally low limit of esterification of the cellulose molecule. From
+the formation of a 'normal' tetracetate--i.e. octacetate of the C_{12}
+unit--we conclude that 4/5 of the oxygen atoms are hydroxyl oxygen. Of
+the 8 OH groups five only react in the mixed esters described above, and
+six only in the case of the simple nitric esters. The ester reactions
+are probably not simple, but accompanied by secondary reactions within
+the cellulose molecule.
+
+       *       *       *       *       *
+
+(p. 34) ~Cellulose Acetates.~--In the first edition (p. 35) we have
+committed ourselves to the statement that 'on boiling cotton with acetic
+anhydride and sodium acetate no reaction occurs.' This is erroneous. The
+error arises, however, from the somewhat vague statements of
+Schutzenberger's researches which are current in the text-books [e.g.
+Beilstein, 1 ed. p. 586] together with the statement that reaction only
+occurs at elevated temperatures (180 deg.). As a matter of fact, reaction
+takes place at the boiling temperature of the anhydride. We have
+obtained the following results with bleached cotton:
+
+                                 Yield        Calc. for Monoacetate
+                                           C_{6}H_{7}O_{4}O.C_{2}H_{3}O
+
+Ester reaction                  121 p.ct.           125 p.ct.
+
+                 {Cellulose       79.9                79.9
+Saponification   {
+                 {Acetic acid     29.9                29.4
+
+This product is formed without apparent structural alteration of the
+fibre. It is entirely insoluble in all the ordinary solvents of the
+higher acetates. Moreover, it entirely resists the actions of the
+special solvents of cellulose--e.g. zinc chloride and cuprammonium. The
+compound is in other respects equally stable and inert. The hygroscopic
+moisture under ordinary atmospheric conditions is 3.2 p.ct.
+
+_Tetracetate._--This product is now made on the manufacturing scale: it
+has yet to establish its industrial value.
+
+
+NITRIRUNG VON KOHLENHYDRATEN.
+
+W. WILL und P. LENZE (Berl. Ber., 1898, 68).
+
+~NITRATES OF CARBOHYDRATES.~
+
+(p. 38) The authors have studied the nitric esters of a typical series
+of the now well-defined carbohydrates--pentoses, hexoses, both aldoses
+and ketoses--bioses and trioses, the nitrates being prepared under
+conditions designed to produce the highest degree of esterification.
+Starch, wood, gum, and cellulose were also included in the
+investigations. The products were analysed and their physical properties
+determined. They were more especially investigated in regard to
+temperatures of decomposition, which were found to lie considerably
+lower than that of the cellulose nitrates. They also show marked and
+variable instability at 50 deg. C. A main purpose of the inquiry was to
+throw light upon a probable cause of the instability of the cellulose
+nitrates, viz. the presence of nitrates of hydrolysed products or
+carbohydrates of lower molecular weight.
+
+The most important results are these:
+
+_Monoses._--The _aldoses_ are fully esterified, in the pentoses 4 OH, in
+the hexoses 5 OH groups reacting. The pentose nitrates are comparatively
+stable at 50 deg.; the hexose nitrates on the other hand are extremely
+unstable, showing a loss of weight of 30-40 p.ct. when kept 24 hours at
+this temperature.
+
+Xylose is differentiated by tending to pass into an anhydride form
+(C_{5}H_{10}O_{5}-H_{2}O) under this esterification. When treated in
+fact with the mixed acids, instead of by the process usually adopted by
+the authors of solution in nitric acid and subsequent addition of the
+sulphuric acid, it is converted into the dinitrate
+C_{5}H_{6}O_{2}.(NO_{3})_{2}.
+
+_Ketoses_ (C_{6}).--These are sharply differentiated from the corresponding
+aldoses by giving _tri_nitrates C_{6}H_{7}O_{2}(NO_{3})_{3} instead
+of _penta_nitrates, the remaining OH groups probably undergoing internal
+condensation. The products are, moreover, _extremely stable_. It is also
+noteworthy that levulose gave this same product, the trinitrate of the
+anhydride (levulosan) by both methods of nitration (_supra_).
+
+_The bisaccharides or bioses_ all give the octonitrates. The degree of
+instability is variable. Cane-sugar gives a very unstable nitrate. The
+lactose nitrate is more stable. Thus at 50 deg. it loses only 0.7 p.ct. in
+weight in eight days; at 75 deg. it loses 1 p.ct. in twenty-four hours, but
+with a rapid increase to 23 p.ct. in fifty-four hours. The maltose
+octonitrate melts (with decomposition) at a relatively high temperature,
+163 deg.-164 deg.. At 50 deg.-75 deg. it behaves much like the lactose nitrate.
+
+_Trisaccharide._--Raffinose yielded the product
+
+     C_{18}H_{21}O_{5}.(NO_{3})_{11}.
+
+_Starch_ yields the hexanitrate (C_{12}) by both methods of nitration.
+The product has a high melting and decomposing point, viz. 184 deg., and
+when thoroughly purified is quite stable. It is noted that a yield of
+157 p.ct. of this nitrate was obtained, and under identical conditions
+cellulose yielded 170 p.ct.
+
+_Wood gum_, from beech wood, gave a tetranitrate (C_{10} formula)
+insoluble in all the usual solvents for this group of esters.
+
+The authors point out in conclusion that the conditions of instability
+and decomposition of the nitrates of the monose-triose series are
+exactly those noted with the cellulose nitrates as directly prepared and
+freed from residues of the nitrating acids. They also lay stress upon
+the superior stability of the nitrates of the anhydrides, especially of
+the ketoses.
+
+
+NITRATED CARBOHYDRATES AS FOOD MATERIAL FOR MOULDS.
+
+THOMAS BOKORNY (Chem. Zeit., 1896, 20, 985-986).
+
+(p. 38) Cellulose trinitrate (nitrocellulose) will serve as a food
+supply for moulds when suspended in distilled water containing the
+requisite mineral matter and placed in the dark. The growth is rapid,
+and a considerable quantity of the vegetable growth accumulates round
+the masses of cellulose nitrate, but no growth is observed if mineral
+matter is absent. Cellulose itself cannot act as a food supply, and it
+seems probable that if glycerol is present cellulose nitrate is no
+longer made use of.
+
+
+NITRATION OF CELLULOSE, HYDROCELLULOSE, AND OXYCELLULOSE.
+
+LEO VIGNON (Compt. rend., 1898, 126, 1658-1661).
+
+(p. 38) Repeated treatment of cellulose, hydrocellulose, and
+oxycellulose with a mixture of sulphuric and nitric acids in large
+excess, together with successive analyses of the compounds produced,
+showed that the final product of the reaction corresponded, in each
+case, with the fixation of 11 NO groups by a molecule containing 24
+atoms of carbon. On exposure to air, nitrohydrocellulose becomes yellow
+and decomposes; nitro-oxycellulose is rather more stable, whilst
+nitrocellulose is unaffected. The behaviour of these nitro-derivatives
+with Schiff's reagent, Fehling's solution, and potash show that all
+three possess aldehydic characters, which are most marked in the case of
+nitro-oxycellulose. The latter also, when distilled with hydrochloric
+acid, yields a larger proportion of furfuraldehyde than is obtained from
+nitrocellulose and nitrohydrocellulose.
+
+       *       *       *       *       *
+
+~CELLULOSE NITRATES-EXPLOSIVES.~
+
+(p. 38) The uses of the cellulose nitrates as a basis for explosives are
+limited by their fibrous character. The conversion of these products
+into the structureless homogeneous solid or semi-solid form has the
+effect of controlling their combustion. The use of nitroglycerin as an
+agent for this purpose gives the curious result of the admixture of two
+high or blasting explosives to produce a new explosive capable of
+extended use for military purposes. The leading representatives of this
+class of propulsive explosives, or 'smokeless powders' are ballistite
+and cordite, the technology of which will be found fully discussed in
+special manuals of the subject. Since the contribution of these
+inventions to the development of cellulose chemistry does not go beyond
+the broad, general facts above mentioned, we must refer the reader for
+technical details to the manuals in question.
+
+There are, however, other means of arriving at structureless cellulose
+nitrates. One of these has been recently disclosed, and as the results
+involve chemical and technical points of novelty, which are dealt with
+in a scientific communication, we reproduce the paper in question,
+viz.:--
+
+
+A RE-INVESTIGATION OF THE CELLULOSE NITRATES.
+
+A. LUCK and C. F. CROSS (J. Soc. Chem. Ind., 1900).
+
+The starting-point of these investigations was a study of the nitrates
+obtained from the structureless cellulose obtained from the
+sulphocarbonate (viscose). This cellulose in the form of a fine meal was
+treated under identical conditions with a sample of pure cotton
+cellulose, viz. digested for 24 hours in an acid mixture containing in
+100 parts HNO_{3}--24 : H_{2}SO_{4}--70 : H_{2}O--6: the proportion of
+acid to cellulose being 60 : 1--. After careful purification the
+products were analysed with the following results:
+
+                                    Soluble in
+                       Nitrogen    Ether alcohol
+
+Fibrous nitrate         13.31         4.3 p.ct.
+Structureless nitrate   13.35         5.6  "
+
+Examined by the 'heat test' (at 80 deg.) and the 'stability test' (at 135 deg.)
+they exhibited the usual instability, and in equal degrees. Nor were the
+tests affected by exhaustive treatment with ether, benzene, and alcohol.
+From this it appears that the process of solution as sulphocarbonate and
+regeneration of the cellulose, though it eliminates certain constituents
+of an ordinary bleached cellulose, which might be expected to cause
+instability, has really no effect in this direction. It also appears
+that instability may be due to by-products of the esterification process
+derived from the cellulose itself.
+
+The investigation was then extended to liquids having a direct solvent
+action on these higher nitrates, more especially acetone. It was
+necessary, however, to avoid this solvent action proper, and having
+observed that dilution with water in increasing proportions produced a
+graduated succession of physical changes in the fibrous ester, we
+carried out a series of treatments with such diluted acetones.
+Quantities of the sample (A), purified as described, but still unstable,
+were treated each with five successive changes of the particular liquid,
+afterwards carefully freed from the acetone and dried at 40 deg.C. The
+products, which were found to be more or less disintegrated, were then
+tested by the ordinary heat test, stability test, and explosion test,
+with the results shown in the table on next page.
+
+In this series of trials the sample 'A' was used in the condition of
+pulp, viz. as reduced by the process of wet-beating in a Hollander. A
+similar series was carried out with the guncotton in the condition in
+which it was directly obtained from the ester reaction. The results were
+similar to above, fully confirming the progressive character of the
+stabilisation with increasing proportions of acetone. These results
+prove that washing with the diluted acetone not only rendered the
+nitrate perfectly stable, but that the product was more stable than that
+obtained by the ordinary process of purification, viz. long-continued
+boiling and washing in water. We shall revert to this point after
+briefly dealing with the associated phenomenon of structural
+disintegration. This begins to be well marked when the proportion of
+acetone exceeds 80 p.ct. The optimum effect is obtained with mixtures of
+90 to 93 acetone and 10 to 7 water (by volume). In a slightly diluted
+acetone of such composition, the guncotton is instantly attacked, the
+action being quite different from the gelatinisation which precedes
+solution in the undiluted solvent. The fibrous character disappears, and
+the product assumes the form of a free, bulky, still opaque mass, which
+rapidly sinks to the bottom of the containing vessel. The disintegration
+of the bulk of the nitrate is associated with
+
+ __________________________________________________________________________
+|                   |                        |             |       |       |
+|                   |  Proportions by volume |             |       |       |
+|                   |________________________| Temperature | Heat  | Heat  |
+|                   |              |         |     of      | Test  | Test  |
+|                   |   Acetone    | Water   |  Explosion  |  80 deg.  | 134 deg.  |
+|___________________|______________|_________|_____________|_______|_______|
+|                   |              |         |             |       |       |
+|                 __|              |         |    Deg.     | Mins. | Mins. |
+|                   |      20      |   80    |    137      |   3   |   4   |
+|                   |      30      |   70    |    160      |   3   |   4   |
+|                   |      40      |   60    |    180      |   7   |  18   |
+|                   |              |         |             |       |   No  |
+|                   |              |         |             |       | fumes |
+|                   |              |         |             |       | after |
+| From 'A' sample.  |     50       |   50    |    187.5    |  55   |  100  |
+|                   |     60       |   40    |    187      |  45   |  100  |
+|                   |     70       |   30    |    185      |  45   |  100  |
+|                   |     80       |   20    |             |  50   |  100  |
+|                 __|     92       |    8    |    185      |  50   |  100  |
+|                   |  Structure-  |         |             |       |       |
+|                   | less powder. |         |             |       |       |
+|  "   'B' sample __|     50       |   50    |    183      |   35  |  100  |
+|  "   'C' sample   |  Ordinary service      |    185      |   10  |   41  |
+|                   |   guncotton            |             |       |       |
+|___________________|______________|_________|_____________|_______|_______|
+
+a certain solvent action, and on adding an equal bulk of water, the
+dissolved nitrate for the most part is precipitated, at the same time
+that the undissolved but disintegrated and swollen product undergoes
+further changes in the direction of increase of hardness and density.
+The product being now collected on a filter, freed from acetone by
+washing with water and dried, is a hard and dense powder the fineness of
+which varies according to the attendant conditions of treatment. With
+the main product in certain cases there is found associated a small
+proportion of nitrate retaining a fibrous character, which may be
+separated by means of a fine sieve. On examining such a residue, we
+found it to contain only 5.6 p.ct. N, and as it was insoluble in strong
+acetone, it may be regarded as a low nitrate or a mixture of such with
+unaltered cellulose. Confirming this we found that the product passing
+through the sieve showed an increase of nitrogen to 13.43 p.ct. from the
+13.31 p.ct. in the original. Tested by the heat test (50 minutes) and
+stability test (no fumes after 100 minutes), we found the products to
+have the characteristics previously noticed.
+
+It is clear, therefore, that this specifically regulated action of
+acetone produces the effects (a) of disintegration, and (b)
+stabilisation. It remains to determine whether the latter effect was
+due, as might be supposed, to the actual elimination of a compound or
+group of compounds present in the original nitrate, and to be regarded
+as the effective cause of instability. It is to be noted first that as a
+result of the treatment with the diluted acetone and further dilution
+after the specific action is completed, collecting the disintegrated
+product on a filter and washing with water, the loss of weight sustained
+amounts to 3 to 4 p.ct. This loss is due, therefore, to products
+remaining dissolved in the filtrate--that is to say, in the much diluted
+acetone. These filtrates are in fact opalescent from the presence of a
+portion of nitrate in a colloidal (hydrated) form. On distilling off the
+acetone, a precipitation is determined. The precipitates are nitrates of
+variable composition, analysis showing from 9 to 12 p.ct. of nitric
+nitrogen. The filtrate from these precipitates containing only
+fractional residues of acetone still shows opalescence. On
+long-continued boiling a further precipitation is determined, the
+filtrates from which are clear. It was in this final clear filtrate that
+the product assumed to cause the instability of the original nitrate
+would be present. The quantity, however, is relatively so small that we
+have only been able to obtain and examine it as residue from evaporation
+to dryness. An exhaustive qualitative examination established a number
+of negative characteristics, with the conclusion that the products were
+not direct derivatives of carbohydrates nor aromatic compounds. On the
+other hand the following positive points resulted. Although the original
+diluted acetone extract was neutral to test papers, yet the residue was
+acid in character. It contained combined nitric groups, fused below 200 deg.
+giving off acid vapours, and afterwards burning with a smoky flame. On
+adding lead acetate to the original clear solution, a well-marked
+precipitation was determined. The lead compounds thus isolated are
+characteristic. They have been obtained in various ways and analysed.
+The composition varies with the character of the solution in which the
+lead compound is formed. Thus in the opalescent or milky solutions in
+which a proportion of cellulose nitrate is held in solution or
+semi-solution by the acetone still present, the lead acetate causes a
+dense coagulation. The precipitates dried and analysed showed 16-20
+p.ct. PbO and 11-9 p.ct. N. It is clear that the cellulose nitrates are
+associated in these precipitates with the lead salts of the acid
+compounds in question. When the latter are obtained from clear
+solutions, i.e. in absence of cellulose nitrates, they contain 60-63
+p.ct. PbO and 3.5 p.ct. N (obtained as NO).
+
+In further confirmation of the conclusion from these results, viz. that
+the nitrocelluloses with no tendency to combine with PbO are associated
+with acid products or by-products of the ester reaction combining with
+the oxide, the lead reagent was allowed to react in the presence of 90
+p.ct. acetone. Water was added, the disintegrated mass collected, washed
+with dilute acetic acid, and finally with water. Various estimations of
+the PbO fixed in this way have given numbers varying from 2 to 2.5 p.ct.
+Such products are perfectly stable. This particular effect of
+stabilisation appears, therefore, to depend upon the combination of
+certain acid products present in ordinary nitrocelluloses with metallic
+oxides. In order to further verify this conclusion, standard specimens
+of cellulose nitrates have been treated with a large number of metallic
+salts under varying conditions of action. It has been finally
+established (1) that the effects in question are more particularly
+determined by treatment with salts of lead and zinc, and (2) that the
+simplest method of treatment is that of boiling the cellulose nitrates
+with dilute aqueous solutions of salts of these metals, preferably the
+acetates. The following results may be cited, obtained by boiling a
+purified 'service' guncotton (sample C) with a 1 p.ct. solution of lead
+acetate and of zinc acetate respectively. After boiling 60 minutes the
+nitrates were washed free from the soluble metallic salts, dried and
+tested.
+
+ __________________________________________________
+|                          |           |           |
+|                          | Heat Test | Heat Test |
+|                          |   at 80 deg.  |   at 134 deg. |
+|__________________________|___________|___________|
+|                          |           |           |
+| Original sample C        |     10    |    41     |
+|Treated with lead acetate |     67    |    45     |
+|     "       zinc    "    |     91    |    45     |
+|__________________________|___________|___________|
+
+In conclusion we may briefly resume the main points arrived at in these
+investigations.
+
+_Causes of instability of cellulose nitrates._--The results of our
+experiments so far as to the causes of instability in cellulose nitrates
+may be summed up as follows:--
+
+(1) Traces of free nitrating acids, which can only occur in the finished
+products through careless manufacture, will undoubtedly cause
+instability, indicated strongly by the ordinary heat test at 80 deg., and to
+a less extent by the heat test at 134 deg..
+
+(2) Other compounds exist in more intimate association with the
+cellulose nitrates causing instability which cannot be removed by
+exhaustive washing with either hot or cold water, by digestion in cold
+dilute alkaline solutions such as sodium carbonate, or by extracting
+with ether, alcohol, benzene, &c.; these compounds, however, are soluble
+in the solvents of highly nitrated cellulose such as acetone, acetic
+ether, pyridine, &c., even when these liquids are so diluted with water
+or other non-solvent liquids to such an extent that they have little or
+no solvent action upon the cellulose nitrate itself. These solutions
+containing the bodies causing instability are neutral to test paper, but
+become acid upon evaporation by heating. (This probably explains the
+presence of free acid when guncotton is purified by long-continued
+boiling in water without any neutralising agent being present.)
+
+(3) The bodies causing instability are products or by-products of the
+original ester reaction, acid bodies containing nitroxy-groups, but
+otherwise of ill-defined characteristics. They combine with the oxides
+of zinc or lead, giving insoluble compounds. They are precipitated from
+their solutions in diluted acetone upon the addition of soluble salts of
+these metals.
+
+(4) Cellulose nitrates are rendered stable either by eliminating these
+compounds, or by combining them with the oxides of lead or zinc whilst
+still in association with cellulose nitrates.
+
+(5) Even the most perfectly purified nitrocellulose will slowly
+decompose with formation of unstable acid products by boiling for a long
+time in water. This effect is much more apparent at higher temperatures.
+
+_Dense structureless or non-fibrous cellulose nitrates_ can be
+industrially prepared (1) by nitrating the amorphous forms of cellulose
+obtained from its solution as sulphocarbonate (viscose). The cellulose
+in this condition reacts with the closest similarity to the original
+fibrous cellulose; the products are similar in composition and
+properties, including that of instability.
+
+(2) By treating the fibrous cellulose nitrates with liquid solvents of
+the high nitrate diluted with non-solvent liquids, and more especially
+water. The optimum effect is a specific disintegration or breaking down
+of their fibrous structure quite distinct from the gelatinisation which
+precedes solution in the undiluted solvent, and occurring within narrow
+limits of variation in the proportion of the diluting and non-solvent
+liquid--for industrial work the most convenient solution to employ is
+acetone diluted with about 10 p.ct. of water by volume.
+
+The industrial applications of these results are the basis of English
+patents 5286 (1898), 18,868 (1898), 18,233 (1898), Luck and Cross (this
+Journal, 1899, 400, 787).
+
+The structureless guncotton prepared as above described is of quite
+exceptional character, and entirely distinct from the ordinary fibrous
+nitrate or the nitrate prepared by precipitation from actual solution in
+an undiluted solvent.[3] By the process described, the nitrate is
+obtained at a low cost in the form of a very fine, dense, structureless,
+white powder of great purity and stability, entirely free from all
+mechanical impurities. The elimination of these mechanical impurities,
+and also to a very great extent of coloured compounds contained in the
+fibrous nitrate, makes the product also useful in the manufacture of
+celluloids, artificial silk, &c., whilst its very dense form gives it a
+great advantage over ordinary fibrous guncotton for use in shells and
+torpedoes, and for the manufacture of gelatinised gunpowders, &c. It can
+be compressed with ease into hard masses; and experiments are in
+progress with a view of producing from it, in admixture with 'retaining'
+ingredients, a military explosive manufactured by means of ordinary
+black gunpowder machinery and processes.
+
+_Manufacture of sporting powder._--The fact that the fibrous structure
+of ordinary guncotton or other cellulose nitrate can be completely or
+partially destroyed by treatment with diluted acetone and without
+attendant solution, constitutes a process of value for the manufacture
+of sporting powder having a base of cellulose nitrate of any degree of
+nitration. The following is a description of the hardening process.
+
+'Soft grains' are manufactured from ordinary guncotton or other
+cellulose nitrate either wholly or in combination with other
+ingredients, the process employed being the usual one of revolving in a
+drum in the damp state and sifting out the grains of suitable size after
+drying. These grains are then treated with diluted acetone, the degree
+of dilution being fixed according to the hardness and bulk of the
+finished grain it is desired to produce (J. Soc. Chem. Ind., 1899, 787).
+Owing to the wide limits of dilution and corresponding effect, the
+process allows of the production of either a 'bulk' or a 'condensed'
+powder.
+
+We prefer to use about five litres of the liquid to each one kilo. of
+grain operated upon, as this quantity allows of the grains being freely
+suspended in the liquid upon stirring. The grains are run into the
+liquid, which is then preferably heated to the boiling-point for a few
+minutes whilst the whole is gently stirred. Under this treatment the
+grains assume a more or less rounded gelatinous condition according to
+the strength of the liquid. There is, however, no solution of the
+guncotton and practically no tendency of the grains to cohere. Each
+grain, however, is acted upon _throughout_ and perfectly _equally_.
+After a few minutes' treatment, water is gradually added, when the
+grains rapidly harden. They are then freed from acetone and certain
+impurities by washing with water, heating, and drying. The process is of
+course carried out in a vessel provided with any means for gentle
+stirring and heating, and with an outlet for carrying off the
+volatilised solvent which is entirely recovered by condensation, the
+grains parting with the acetone with ease.
+
+_Stabilising cellulose nitrates._--The process is of especial value in
+rendering stable and inert the traces of unstable compounds which always
+remain in cellulose nitrate after the ordinary boiling and washing
+process. It is of greatest value in the manufacture of collodion cotton
+used for the preparation of gelatinous blasting explosives and all
+explosives composed of nitroglycerin and cellulose nitrates. Such
+mixtures seem peculiarly liable to decomposition if the cellulose
+nitrate is not of exceptional stability (J. Soc. Chem. Ind., 1899,
+787).
+
+
+EMPLOI DE LA CELLULOSE POUR LA FABRICATION DE FILS BRILLANTS IMITANT LA
+SOIE.
+
+E. BRONNERT (1) (Rev. Mat. Col., 1900, September, 267).
+
+V. ~USE OF CELLULOSE IN THE MANUFACTURE OF IMITATIONS OF SILK
+(LUSTRA-CELLULOSE).~
+
+(p. 45) _Introduction._--The problem of spinning a continuous thread of
+cellulose has received in later years several solutions. Mechanically
+all resolve themselves into the preparation of a structureless filtered
+solution of cellulose or a cellulose derivative, and forcing through
+capillary orifices into some medium which either absorbs or decomposes
+the solvent. The author notes here that the fineness and to a great
+extent the softness of the product depends upon the dimensions of the
+capillary orifice and concentration of the solution. The technical idea
+involved in the spinning of artificial fibres is an old one. Reaumur (2)
+forecast its possibility, Audemars of Lausanne took a patent as early as
+1855 (3) for transforming nitrocellulose into fine filaments which he
+called 'artificial silk.' The idea took practical shape only when it
+came to be used in connection with filaments for incandescent lamps. In
+this connection we may mention the names of the patentees:--Swinburne
+(4), Crookes, Weston (5), Swan (6), and Wynne and Powell (7). These
+inventors prepared the way for Chardonnet's work, which has been
+followed since 1888 with continually increasing success.
+
+At this date the lustra-celluloses known may be divided into four
+classes.
+
+1. 'Artificial silks' obtained from the nitrocelluloses.
+
+2. 'Lustra-cellulose' made from the solution of cellulose in
+cuprammonium.
+
+3. 'Lustra-cellulose' prepared from the solution of cellulose in
+chloride of zinc.
+
+4. 'Viscose silks,' by the decomposition of sulphocarbonate of cellulose
+(Cross and Bevan).
+
+GROUP 1. The early history of the Chardonnet process is discussed and
+some incidental causes of the earlier failures are dealt with. The
+process having been described in detail in so many publications the
+reader is referred to these for details. [See Bibliography, (1) and (2),
+(3) and (4).] The denitrating treatment was introduced in the period
+1888-90 and of course altogether changed the prospects of the industry;
+not only does it remove the high inflammability, but adds considerably
+to softness, lustre, and general textile quality. In Table I will be
+found some important constants for the nitrocellulose fibre; also the
+fibre after denitration and the comparative constants for natural silk.
+
+TABLE 1.
+
+ _______________________________________________________________________
+|                                          |           |                |
+|                                          | Tenacity  |   Elasticity   |
+|                                          | (grammes) | (% elongation) |
+|__________________________________________|___________|________________|
+|                                          |           |                |
+| Nitrocellulose according to Chardonnet   |           |                |
+|   German Patent No. 81,599               |    150    |       23       |
+| The same after denitration               |    110    |        8       |
+| Denitrated fibre moistened with water    |     25    |        --      |
+| Nitrocellulose: Bronnert's German Patent |           |                |
+|   No. 93,009                             |    125    |       28       |
+| The same after denitration (dry)         |    115    |       13       |
+| The same after denitration (wetted)      |     32    |       --       |
+| Natural silk                             |    300    |       18       |
+|__________________________________________|___________|________________|
+
+     1. Tenacity is the weight in grammes required to break the
+     thread.
+
+     2. Elasticity is the elongation per cent. at breaking.
+
+     The numbers are taken for thread of 100 deniers (450 metres of
+     0.05 grammes = 1 denier). It must be noted that according to
+     the concentration of the solution and variations in the process
+     of denitration the constants for the yarn are subject to very
+     considerable variation.
+
+In regard to the manufacture a number of very serious difficulties have
+been surmounted. First, instead of drying the nitrated cellulose, which
+often led to fires, &c., it was found better to take it moist from the
+centrifugal machine, in which condition it is dissolved (5). It was
+next found that with the concentrated collodion the thread could be spun
+direct into the air, and the use of water as a precipitant was thus
+avoided.
+
+With regard to denitration which is both a delicate and disagreeable
+operation: none of the agents recommended to substitute the sulphydrates
+have proved available. Of these the author mentions ferrous chloride
+(6), ferrous chloride in alcohol (7), formaldehyde (8),
+sulphocarbonates. The different sulphydrates (9) have very different
+effects. The calcium compound tends to harden and weaken the thread. The
+ammonia compound requires great care and is costly. The magnesium
+compound works rapidly and gives the strongest thread. Investigations
+have established the following point. In practice it is not necessary to
+combine the saponification of cellulose ester with complete reduction of
+the nitric acid split off. The latter requires eight molecules of
+hydrogen sulphide per one molecule tetranitrocellulose, but with
+precautions four molecules suffice. It is well known that the
+denitration is nearly complete, traces only of nitric groups surviving.
+Their reactions with diphenylamine allow a certain identification of
+artificial silks of this class. Various other inventors, e.g. Du Vivier
+(10), Cadoret (11), Lehner (12), have attempted the addition of other
+substances to modify the thread. These have all failed. Lehner, who
+persisted in his investigations, and with success, only attained this
+success, however, by leaving out all such extraneous matters. Lehner
+works with 10 p.ct. solutions; Chardonnet has continually aimed at
+higher concentration up to 20 p.ct. Lehner has been able very much to
+reduce his pressures of ejection in consequence; Chardonnet has had to
+increase up to pressures of 60 k. per cm. and higher. The latter
+involves very costly distributing apparatus. Lehner made next
+considerable advance by the discovery of the fact that the addition of
+sulphuric acid to the collodion caused increase of fluidity (13), which
+Lehner attributes to molecular change. Chardonnet found similar results
+from the addition of aldehyde and other reagents (14), but not such as
+to be employed for the more concentrated collodions. The author next
+refers to his discoveries (15) that alcoholic solutions of a number of
+substances, organic and inorganic, freely dissolve the lower cellulose
+nitrates. The most satisfactory of these substances is chloride of
+calcium (16). It is noted that acetate of ammonia causes rapid changes
+in the solution, which appear to be due to a species of hydrolysis. The
+result is sufficiently remarkable to call for further investigation. The
+chloride of calcium, it is thought possible, produces a direct
+combination of the alcohol with a reactive group of the nitrocellulose.
+The fluidity of this solution using one mol. CaCl_{2} per 1 mol.
+tetranitrate (17) reaches a maximum in half an hour's heating at
+60 deg.-70 deg.C. The fluidity is increased by starting from a cotton which has
+been previously mercerised. After nitration there is no objection to a
+chlorine bleach. Chardonnet has found on the other hand that in
+bleaching before nitration there is a loss of spinning quality in the
+collodion. The author considers that the new collodion can be used
+entirely in place of the ordinary ether-alcohol collodion. With regard
+to the properties of the denitrated products they fix all basic colours
+without mordant and may be regarded as oxycellulose therefore. The
+density of the thread is from 1.5 to 1.55. The thread of 100 deniers
+shows a mean breaking strain of 120 grammes with an elasticity of 8-12
+p.ct. The cardinal defect of these fibres is their property of
+combination with water. Many attempts have been made to confer
+water-resistance (18), but without success. Strehlenert has proposed the
+addition of formaldehyde (19), but this is without result (20). In
+reference to these effects of hydration, the author has made
+observations on cotton thread, of which the following table represents
+the numerical results:
+
+                                                       Breaking Strain
+                                                   Mean of 20 experiments
+
+Skein of bleached cotton without treatment                 825
+Skein of bleached cotton without treatment, but wetted     942
+Ditto after conversion into hexanitrate, dry               884
+The above, wetted                                          828
+The cotton denitrated from above, dry                      529
+The cotton denitrated as above and wetted                  206
+
+The author considers that other patents which have been taken for
+spinning nitrocellulose are of little practical account (21) and (22).
+The same conclusion also applies to the process of _Langhans_, who
+proposes to spin solutions of cellulose in sulphuric acid (23) (24) and
+mixtures of sulphuric acid and phosphoric acid.
+
+GROUP 2. _Lustra-cellulose._--Thread prepared by spinning solutions of
+cellulose in cuprammonium.
+
+This product is made by the Vereinigte Glanzstoff-Fabriken, Aachen,
+according to a series of patents under the names of H. Pauly, M. Fremery
+and Urban, Consortium mulhousien pour la fabrication de fils brillants,
+E. Bronnert, and E. Bronnert and Fremery and Urban (1). The first patent
+in this direction was taken by Despeissis in 1890 (2). It appears this
+inventor died shortly after taking the patent (3) The matter was later
+developed by Pauly (4) especially in overcoming the difficulty of
+preparing a solution of sufficient concentration. (It is to be noted
+that Pauly's patents rest upon a very slender foundation, being
+anticipated in every essential detail by the previous patent of
+Despeissis.) For this very great care is required, especially, first,
+the condition of low temperature, and, secondly, a regulated proportion
+of copper and ammonia to cellulose. The solution takes place more
+rapidly if the cellulose has been previously oxidised. Such cellulose
+gives an 8 p.ct. solution, and the thread obtained has the character of
+an oxycellulose, specially seen in its dyeing properties. The best
+results are obtained, it appears, by the preliminary mercerising
+treatment and placing the alkali cellulose in contact with copper and
+ammonia. (All reagents employed in molecular proportions.) The author
+notes that the so-called hydrocellulose (Girard) (5) is almost insoluble
+in cuprammonium, as is starch. It is rendered soluble by alkali
+treatment.
+
+GROUP 3. _Lustra-cellulose_ prepared by spinning a solution of cellulose
+in concentrated chloride of zinc.
+
+This solution has been known for a long time and used for making
+filaments for incandescent lamps. The cellulose threads, however, have
+very little tenacity. This is no doubt due to the conditions necessary
+for forming the solution, the prolonged digestion causing powerful
+hydrolysis (1). Neither the process of Wynne and Powell (2) nor that of
+Dreaper and Tompkins (3), who have endeavoured to bring the matter to a
+practical issue, are calculated to produce a thread taking a place as a
+textile. The author has described in his American patent (4) a method of
+effecting the solution in the cold, viz. again by first mercerising the
+cellulose and washing away the caustic soda. This product dissolves in
+the cold and the solution remains unaltered if kept at low temperature.
+Experiments are being continued with these modifications of the process,
+and the author anticipates successful results. The modifications having
+the effect of maintaining the high molecular weight of the cellulose, it
+would appear that these investigations confirm the theory of Cross and
+Bevan that the tenacity of a film or thread of structureless regenerated
+cellulose is directly proportional to the molecular weight of the
+cellulose, i.e. to its degree of molecular aggregation (5).
+
+GROUP 4. 'Viscose' silks obtained by spinning solutions of xanthate of
+cellulose.
+
+In 1892, Cross and Bevan patented the preparation of a new and curious
+compound of cellulose, the thiocarbonate (1) (2) (3). Great hopes were
+based upon this product at the time of its discovery. It was expected
+to yield a considerable industrial and financial profit and also to
+contribute to the scientific study of cellulose. The later patents of C.
+H. Stearn (4) describe the application of viscose to the spinning of
+artificial silk. The viscose is projected into solutions of chloride of
+ammonium and washed in a succession of saline solutions to remove the
+residual sulphur impurities. The author remarks that though it has a
+certain interest to have succeeded in making a thread from this compound
+and thus adding another to the processes existing for this purpose, he
+is not of opinion that it shows any advance on the lustra-cellulose (2)
+and (3). He also considers that the bisulphide of carbon, which must be
+regarded as a noxious compound, is a serious bar to the industrial use
+of the process, and for economic work he considers that the regeneration
+of ammonia from the precipitating liquors is necessary and would be as
+objectionable as the denitration baths in the collodion process. The
+final product not being on the market he does not pronounce a finally
+unfavourable opinion.
+
+The author and the Vereinigte Glanzstoff-Fabriken after long
+investigation have decided to make nothing but the lustra-cellulose (2)
+and (3). A new factory at Niedermorschweiler, near Mulhouse, is
+projected for this last production.
+
+
+BIBLIOGRAPHY
+
+_Introduction_
+
+(1) Bull. de la Soc. industr. de Mulhouse, 1900.
+
+(2) Reaumur, Memoire pour servir a l'histoire des insectes, 1874, 1, p.
+154.
+
+(3) English Pat. No. 283, Feb. 6, 1855.
+
+(4) Swinburne, Electrician, 18, 28, 1887, p. 256.
+
+(5) Weston (Swinburne), Electrician, 18, 1887, p. 287. Eng. Pat. No.
+22866, Sept. 12, 1882.
+
+(6) German Pat. No. 3029. English Pat. No. 161780, April 28, 1884
+(Swan).
+
+(7) Wynne-Powell, English Pat. No. 16805, Dec. 22, 1884.
+
+
+_Group I_
+
+(1) German Pat No. 38368, Dec. 20, 1885. German Pat. No. 46125, March 4,
+1888. German Pat. No. 56331, Feb. 6, 1890. German Pat. No. 81599, Oct.
+11, 1893. German Pat. No. 56655, April 23, 1890. French Pat. No. 231230,
+June 30, 1893.
+
+(2) Industrie textile, 1899, 1892. Wyss-Noef, Zeitschrift fuer angewandte
+Chemie, 1899, 30, 33. La Nature, Jan. 1, 1898, No. 1283. Revue generale
+des sciences, June 30, 1898.
+
+(3) German Pat. No. 46125, March 4, 1888. German Pat. No. 56655, April
+23, 1890.
+
+(4) Swan, English Pat. 161780, June 28, 1884. See also Bechamp, Dict. de
+Chimie de Wurtz.
+
+(5) German Pat. No. 81599, Oct 11, 1893.
+
+(6) Bechamp, art. Cellulose, Dict. de Chimie de Wurtz, p. 781.
+
+(7) Chardonnet, addit. March 3, 1897, to the French Pat. 231230, May 30,
+1893.
+
+(8) Knofler, French Pat. 247855, June 1, 1895. German Pat. 88556, March
+28, 1894.
+
+(9) Bechamp, art. Cellulose, Dict. de Chimie de Wurtz. Blondeau, Ann.
+Chim. et Phys. (3), 1863, 68, p. 462.
+
+(10) Revue industrielle, 1890, p. 194. German Pat. 52977, March 7, 1889.
+
+(11) French Pat. 256854, June 2, 1896.
+
+(12) German Pat. 55949, Nov. 9, 1889. German Pat. 58508, Sept. 16, 1890.
+German Pat. 82555, Nov. 15, 1894.
+
+(13) German Pat. 58508, Sept. 16, 1900.
+
+(14) French Pat. 231230, June 30, 1893.
+
+(15) German Pat. 93009, Nov. 19, 1895. French Pat. 254703, March 12,
+1896. English Pat. 6858, March 28, 1896.
+
+(16) American Pat. 573132, Dec. 15, 1896.
+
+(17) This proportion is the most advantageous, and furnishes the best
+liquid collodions that can be spun.
+
+(18) French Pat. 259422, Sept. 3, 1896.
+
+(19) English Pat. 22540, 1896.
+
+(20) Application for German Pat. not granted, 4933 IV. 296, Mar. 16,
+1897.
+
+(21) German Pat. 96208, Feb. 10, 1897. Addit. Pat. 101844 and 102573,
+Dec. 10, 1897.
+
+(22) Oberle et Newbold, French Pat. 25828, July 22, 1896. Granquist,
+Engl. applic. 2379, Nov. 28, 1899.
+
+(23) German Pat. 72572, June 17, 1891.
+
+(24) Voy. Stern, Ber., 28, ch. 462.
+
+
+_Group II_
+
+(1) German Pat. 98642, Dec. 1, 1897 (Pauly). French Pat. 286692, March
+10, 1899, and addition of October 14, 1899 (Fremery and Urban). French
+Pat. 286726, March 11, 1899, and addition of December 4, 1899. German
+Pat. 111313, March 16, 1899 (Fremery and Urban). English Pat. 18884,
+Sept. 19, 1899 (Bronnert). English Pat. 13331, June 27, 1899 (Consort.
+mulhousien).
+
+(2) French Pat. 203741, Feb. 12, 1890.
+
+(3) The actual lapse of this patent is due to the death of Despeissis
+shortly after it was taken.
+
+(4) Without questioning the good faith of Pauly, it is nevertheless a
+fact that the original patent remains as a document, and therefore that
+the value of the Pauly patents is very questionable.
+
+(5) Girard, Ann. Chim. et Phys, 1881 (5), 24, p. 337-384.
+
+
+_Group III_
+
+(1) Cross and Bevan, Cellulose, 1895, p. 8.
+
+(2) English Pat. 16805, Dec. 22, 1884.
+
+(3) English Pat. 17901, July 30, 1897.
+
+(4) Bronnert, American Pat. 646799, April 3, 1900.
+
+(5) Cross and Bevan, Cellulose, 1895, p. 12.
+
+
+_Group IV_
+
+(1) English Pat. 8700, 1892. German Pat. 70999, Jan. 13, 1893.
+
+(2) English Pat. 4713, 1896. German Pat. 92590, Nov. 21, 1896.
+
+(3) Comptes rendus (loc. cit.). Berichte, c. 9, 65a.
+
+(4) English Pat. 1020, 1898. German Pat. 108511, Oct. 18, 1898.
+
+
+~Artificial Silk--Lustra-cellulose.~
+
+C. F. CROSS and E. J. BEVAN (J. Soc. Chem. Ind., 1896, 317).
+
+The object of this paper is mainly to correct current statements as to
+the artificial or 'cellulose silks' being explosive or highly
+inflammable (ibid., 1895, 720). A specimen of the 'Lehner' silk was
+found to retain only 0.19 p.ct. total nitrogen, showing that the
+denitration is sufficiently complete to dispose of any suggestion of
+high inflammability.
+
+The product yielded traces only of furfural; on boiling with a 1 p.ct.
+solution of sodium hydrate, the loss of weight was 9.14 p.ct.; but the
+solution had no reducing action on Fehling's solution. The product in
+denitration had therefore reverted completely to a cellulose (hydrate),
+no oxy-derivative being present.
+
+       *       *       *       *       *
+
+The authors enter a protest against the term 'artificial silk' as
+applied to these products, and suggest 'lustra-cellulose.'
+
+
+DIE KUeNSTLICHE SEIDE-IHRE HERSTELLUNG, EIGENSCHAFTEN UND VERWENDUNG.
+
+CARL SUeVERN, Berlin, 1900, J. Springer.
+
+~ARTIFICIAL SILK--ITS PRODUCTION, PROPERTIES, AND APPLICATIONS.~
+
+This work of some 130 pages is an important monograph on the subject of
+the preparation of artificial cellulose threads--so far as the technical
+elements of the problems involved are discussed and disclosed in the
+patent literature. The first section, in fact, consists almost
+exclusively of the several patent specifications in chronological order
+and ranged under the sub-sections: (a) The Spinning of Nitrocellulose
+(collodion); (b) The Spinning of other Solutions of Cellulose; (c)
+The Spinning of Solutions of the Nitrogenous Colloids.
+
+In the second section the author deals with the physical and chemical
+proportions of the artificial threads.
+
+_Chardonnet 'silk'_ is stated to have a mean diameter of 35 mu, but with
+considerable variations from the mean in the individual fibres; equally
+wide variations in form are observed in cross-section. The general form
+is elliptical, but the surface is marked by deep striae, and the
+cross-section is therefore of irregular outline. This is due to
+irregular conditions of evaporation of the solvents, the thread being
+'spun' into the air from cylindrical orifices of regulated dimensions.
+Chardonnet states that when the collodion is spun into alcohol the
+resultant thread is a perfect cylinder (Compt. rend. 1889, 108, 962).
+The strength of the fibre is variously stated at from 50-80 p.ct. that
+of 'boiled off' China tram; the true elasticity is 4-5 p.ct., the
+elongation under the breaking strain 15-17 p.ct. The sp.gr. is 1.49,
+i.e. 3-5 p.ct. in excess of boiled off silk.
+
+_Lehner 'silk'_ exhibits the closest similarity to the Chardonnet
+product. In cross-section it is seen to be more regular in outline, and
+a round, pseudo-tubular form prevails, due to the conditions of
+shrinkage and collapse of the fibre in parting with the solvents, and in
+then dehydrating. The constants for 'breaking strain,' both in the
+original and moistened condition, for elasticity, &c., are closely
+approximate to those for the Chardonnet product.
+
+_Pauly 'silk'._--The form of the ultimate fibres is much more regular
+and the contour of the cross-section is smooth. The product shows more
+resistance to moisture and to alkaline solutions.
+
+_Viscose 'silk'_ is referred to in terms of a communication appearing in
+'Papier-Zeitung,' 1898, 2416.
+
+     In the above section the following publications are referred
+     to: Chardonnet, 'Compt. rend.,' 1887, 105, 900; and 1889, 108,
+     962; Silbermann, 'Die Seide,' 1897, v. 2, 143; Herzog,
+     'Farber-Zeitung,' 1894/5, 49-50; Thiele, ibid. 1897, 133; O.
+     Schlesinger, 'Papier-Zeitung,' 1895, 1578-81, 1610-12.
+
+
+_Action of Reagents upon Natural and Artificial Silks._
+
+1. _Potassium hydrate_ in solution of maximum concentration dissolves
+the silks proper, (a) China silk on slight warming, (b) Tussah silk
+on boiling. The cellulose 'silks' show swelling with discolouration, but
+the fibrous character is not destroyed even on boiling.
+
+2. _Potassium hydrate_ 40 p.ct. China silk dissolves completely at
+65 deg.-85 deg.; Tussah silk swells considerably at 75 deg. and dissolves at
+100 deg.-120 deg.. The cellulose 'silks' are attacked with discolouration; at
+140 deg. (boiling-point of the solution) there is progressive solvent
+action, but the action is incomplete. The Pauly product is most
+resistant.
+
+3. _Zinc chloride_, 40 p.ct. solution. Both the natural silks and
+lustra-celluloses are attacked at 100 deg., and on raising the temperature
+the further actions are as follows: China silk is completely dissolved
+at 110-120 deg.; Tussah silk at 130-135 deg.; the collodion products at
+140-145 deg.; the Pauly product was again most resistant, dissolving at
+180 deg..
+
+4. _Alkaline cupric oxide_ (glycerin) solution was prepared by
+dissolving 10 grs. of the sulphate in 100 c.c. water, adding 5 grs.
+glycerin and 10 c.c. of 40 p.ct. KOH. In this solution the China silk
+dissolved at the ordinary temperature; Tussah silk and the
+lustra-celluloses were not appreciably affected.
+
+5. _Cuprammonium solution_ was prepared by dissolving the precipitated
+cupric hydrate in 24 p.ct. ammonia. In this reagent also the China silk
+dissolved, and the Tussah silk as well as the lustra-celluloses
+underwent no appreciable change.
+
+6. _An ammoniacal solution of nickel oxide_ was prepared by dissolving
+the precipitated hydrated oxide in concentrated ammonia. The China silk
+was dissolved by this reagent; Tussah silk and the lustra-celluloses
+entirely resisted its action.
+
+7. _Fehling's solution_ is a solvent of the natural silks, but is
+without action on the lustra-celluloses.
+
+8. _Chromic acid_--20 p.ct. CrO_{3}--solution dissolves both the natural
+silks and the lustra-celluloses at the boiling temperature of the
+solution.
+
+9. _Millon's reagent_, at the boiling solution, colours the natural
+silks violet: the lustra-celluloses give no reaction.
+
+10. _Concentrated nitric acid_ attacks the natural silks powerfully in
+the cold; the lustra-celluloses dissolve on heating.
+
+11. _Iodine solution_ (I in KI) colours the China silk a deep brown,
+Tussah a pale brown; the celluloses from collodion are coloured at first
+brown, then blue. The Pauly product, on the other hand, does not react.
+
+12. _Diphenylamine sulphate._--A solution of the base in concentrated
+sulphuric acid colours the natural silks a brown; the collodion 'silks'
+give a strong blue reaction due to the presence of residual
+nitro-groups. The Pauly product is not affected.
+
+13. _Brucin sulphate_ in presence of concentrated sulphuric acid colours
+the natural silks only slightly (brown); the collodion 'silks' give a
+strong red colouration. The Pauly product again is without reaction.
+
+14. _Water._--The natural silks do not soften in the mouth as do the
+lustra-celluloses.
+
+15. _Water of condition_ was determined by drying at 100 deg.; the following
+percentages resulted (a). The percentages of water (b) taken up from
+the atmosphere after forty-three hours' exposure were:
+
+                                   (a)        (b)
+     China (raw) silk             7.97       2.24
+     Tussah silk                  8.26       5.00
+
+     Lustra-celluloses:
+
+     Chardonnet (Besancon)       10.37       5.64
+         "    Spreitenbach       11.17       5.77
+     Lehner                      10.71       5.97
+     Pauly                       10.04       6.94
+
+16. _Behaviour on heating at 200 deg.._--After two hours' heating at this
+temperature the following changes were noted:
+
+     China silk      Much discoloured (brown).
+     Tussah silk     Scarcely affected.
+
+Lustra-celluloses:
+
+     Chardonnet   Converted into a blue-black charcoal, retaining the
+     Lehner       form ofthe fibres.
+
+     Pauly       A bright yellow-brown colouration, without carbonisation.
+
+17. The _losses of weight_ accompanying these changes and calculated per
+100 parts of fibre dried at 100 deg. were:
+
+     China silk       3.18
+     Tussah silk      2.95
+
+Lustra-celluloses:
+
+     Chardonnet      33.70
+     Lehner          26.56
+     Pauly            1.61
+
+18. _Inorganic constituents._--Determinations of the total ash gave for
+the first five of the above, numbers varying from 1.0 to 1.7 p.ct. The
+only noteworthy point in the comparison was the exceptionally small ash
+of the Pauly product, viz. 0.096 p.ct.
+
+19. _Total nitrogen._--The natural silks contain the 16-17 p.ct. N
+characteristic of the proteids. The lustra-celluloses contain 0.05-0.15
+p.ct. N which in those spun from collodion is present in the form of
+nitric groups.
+
+The points of chemical differentiation which are established by the
+above scheme of comparative investigation are summed up in tabular form.
+
+_Methods of dyeing._--The lustra-celluloses are briefly discussed. The
+specific relationship of these forms of cellulose to the colouring
+matters are in the main those of cotton, but they manifest in the
+dye-bath the somewhat intensified attraction which characterises
+mercerised cotton, or more generally the cellulose hydrates.
+
+_Industrial applications_ of the lustra-celluloses are briefly noticed
+in the concluding section of the book.
+
+FOOTNOTES:
+
+[3] With these products it is easy to observe that they have a definite
+fusion point 5 deg.-10 deg. below the temperature of explosion.
+
+
+
+
+SECTION III. DECOMPOSITIONS OF CELLULOSE SUCH AS THROW LIGHT ON THE
+PROBLEM OF ITS CONSTITUTION
+
+
+UEBER CELLULOSE.
+
+G. BUMCKE und R. WOLFFENSTEIN (Berl. Ber., 1899, 2493).
+
+(p. 54) _Theoretical Preface._--The purpose of these investigations is
+the closer characterisation of the products known as 'oxycellulose' and
+'hydracellulose,' which are empirical aggregates obtained by various
+processes of oxidation and hydrolysis; these processes act concurrently
+in the production of the oxycelluloses. The action of hydrogen peroxide
+was specially investigated. An oxycellulose resulted possessing strongly
+marked aldehydic characteristics. The authors commit themselves to an
+explanation of this paradoxical result, i.e. the production of a body
+of strongly 'reducing' properties by the action of an oxidising agent
+upon the inert cellulose molecule (? aggregate) as due to the
+_hydrolytic_ action of the peroxide: following Wurster (Ber. 22, 145),
+who similarly explained the production of reducing sugars from cane
+sugar by the action of the peroxide.
+
+The product in question is accordingly termed _hydralcellulose_. By the
+action of alkalis this is resolved into two bodies of alcoholic
+(cellulose) and acid ('acid cellulose') characteristics respectively.
+The latter in drying passes into a lactone. The acid product is also
+obtained from cellulose by the action of alkaline lye (boiling 30 p.ct.
+NaOH) and by solution in Schweizer's reagent.
+
+It is considered probable that the cellulose nitrates are hydrocellulose
+derivatives, and experimental evidence in favour of this conclusion is
+supplied by the results of 'nitrating' the celluloses and their oxy- and
+hydro- derivatives. Identical products were obtained.
+
+_Experimental investigations._--The filter paper employed as 'original
+cellulose,' giving the following numbers on analysis:
+
+     C   44.56    44.29    44.53    44.56
+     H    6.39     6.31     6.46     6.42
+
+was exposed to the action of pure distilled H_{2}O_{2} at 4-60 p.ct.
+strength, at ordinary temperatures until disintegrated: a result
+requiring from nineteen to thirty days. The series of products gave the
+following analytical results:
+
+     C   43.61   43.61   43.46   43.89   44.0   43.87   43.92   43.81
+     H    6.00    6.29    6.28    6.26    6.13   6.27    6.24    6.27
+
+results lying between the requirements of the formulae:
+
+     5 C_{6}H_{10}O_{5}.H_{2}O  and  8 C_{6}H_{10}O_{5}.H_{2}O.
+
+Hydrazones were obtained with 1.7-1.8 p.ct. N. Treated with caustic soda
+solution the hydrazones were dissolved in part: on reprecipitation a
+hydrazone of unaltered composition was obtained. The original product
+shows therefore a uniform distribution of the reactive CO- groups.
+
+The hydralcellulose boiled with Fehling's solution reduced 1/12 of the
+amount required for an equal weight of glucose.
+
+Digested with caustic soda solution it yielded 33 p.ct. of its weight of
+the soluble 'acid cellulose.' This product was purified and analysed
+with the following result: C 43.35 H 6.5. For the direct production of
+the 'acid' derivative, cellulose was boiled with successive quantities
+of 30 p.ct. NaOH until _dissolved_. It required eight treatments of one
+hour's duration. On adding sulphuric acid to the solutions the product
+was precipitated. Yield 40 p.ct. Analyses:
+
+     C    43.8     43.8     43.7
+     H     6.2      6.2      6.3
+
+The cellulose reprecipitated from solution in Schweizer's reagent gave
+similar analytical results:
+
+     C    43.9    43.8    44.0
+     H     6.5     6.3     6.4
+
+_Conversion into nitrates._--The original cellulose, hydral- and acid
+cellulose were each treated with 10 times their weight of HNO_{3} of
+1.48 sp.gr. and heated at 85 deg. until the solution lost its initial
+viscosity.
+
+The products were precipitated by water and purified by solution in
+acetone from which two fractions were recovered, the one being
+relatively insoluble in ethyl alcohol. The various nitrates from the
+several original products proved to be of almost identical composition,
+
+     C 32.0   H 4.2    N 8.8
+
+with a molecular weight approximately 1350. The conclusion is that
+these products are all derivatives of a 'hydralcellulose'
+6C_{6}H_{10}O_{5}H_{2}O.
+
+
+FORMATION OF FURFURALDEHYDE FROM CELLULOSE, OXYCELLULOSE, AND
+HYDROCELLULOSE.
+
+By LEO VIGNON (Compt. rend., 1898, 126, 1355-1358).
+
+(p. 54) Hydrocellulose, oxycellulose, and 'reduced' cellulose, the last
+named being apparently identical with hydrocellulose, were obtained by
+heating carefully purified cotton wool (10 grams) in water (1,000 c.c.),
+with (1) 65 c.c. of hydrochloric acid (1.2 sp.gr.), (2) 65 c.c. of
+hydrochloric acid and 80 grams of potassium chlorate, (3) 65 c.c. of
+hydrochloric acid and 50 grams of stannous chloride. From these and some
+other substances, the following percentage yields of furfuraldehyde were
+obtained: Hydrocellulose, 0.854; oxycellulose, 2.113; reduced cellulose,
+0.860; starch, 0.800; bleached cotton, 1.800; oxycellulose, prepared by
+means of chromic acid, 3.500. Two specimens of oxycellulose were
+prepared by treating cotton wool with hydrochloric acid and potassium
+chlorate (A), and with sulphuric acid and potassium dichromate (B), and
+25 grams of each product digested with aqueous potash. Of the product A,
+16.20 grams were insoluble in potash, 2.45 grams were precipitated on
+neutralisation of the alkaline solution, and 6.35 grams remained in
+solution, whilst B yielded 11.16 grams of insoluble matter, 1.42 grams
+were precipitated by acid, and 12.42 grams remained in solution. The
+percentage yields of furfuraldehyde obtained from these fractions were
+as follows: A, insoluble, 0.86; precipitated, 4.35; dissolved, 1.10. B,
+insoluble, 0.76; precipitated, 5.11; dissolved, 1.54. It appears, from
+the foregoing results, that the cellulose molecule, after oxidation, is
+easily decomposed by potash, the insoluble and larger portion having all
+the characters of the original cellulose, whilst the soluble portion is
+of an aldehydic nature, and contains a substance, precipitable by acids,
+which yields a relatively large amount of furfuraldehyde.
+
+
+UNTERSUCHUNGEN UeBER DIE OXYCELLULOSE.
+
+O. V. FABER und B. TOLLENS (Berl. Ber., 1899, 2589).
+
+~Investigations of Oxycellulose.~
+
+(p. 61) The author's results are tersely summed up in the following
+conclusions set forth at the end of the paper: The oxycelluloses are
+mixtures of cellulose and a derivative oxidised compound which contains
+one more atom O than cellulose (cellulose = C_{6}H_{10}O_{5}), and for
+which the special designation _Celloxin_ is proposed.
+
+Celloxin may be formulated C_{8}H_{6}O_{6} or C_{6}H_{10}O_{6}, of which
+the former is the more probable.
+
+The various oxycelluloses may be regarded as containing one celloxin
+group to 1-4 cellulose groups, according to the nature of the original
+cellulose, and the degree of oxidation to which subjected. These groups
+are in chemical union.
+
+Celloxin has not been isolated. On boiling the oxycelluloses with
+lime-milk it is converted into isosaccharinic and dioxybutyric acids.
+The insoluble residue from the treatment is cellulose.
+
+The following oxycelluloses were investigated:
+
+A. _Product of action of nitric acid upon pine wood_ (Lindsey and
+Tollens, Ann. 267, 366).--The oxycelluloses contained
+
+1 mol celloxin:  {2 mol. cellulose on 6 hours' heating
+                 {3 mol. cellulose on 3 hours' heating
+
+with a ratio H : O = 1 : 9 and 1 : 8.7 respectively: they yielded 7
+p.ct. furfural.
+
+B. _By action of bromine in presence of water and_ CaCO_{3} _upon
+cotton_.--Yield, (air-dry) 85 p.ct. Empirical composition
+C_{12}H_{20}O_{11} = C_{6}H_{10}O_{5}.C_{6}H_{10}O_{6}: yielded furfural
+1.7 p.ct.
+
+C. _Cotton and nitric acid at_ 100 deg., two and a half hours (Cross and
+Bevan).--Yield, 70 p.ct. Composition
+
+     4 C_{6}H_{10}O_{5}.C_{6}H_{8}O_{6}
+
+yielded furfural 2.3 p.ct.
+
+D. _Cotton and nitric acid at_ 100 deg. (four hours).--A more highly
+oxidised product resulted, viz. 3 C_{6}H_{10}O_{5}.C_{6}H_{8}O_{6}:
+yielded furfural 3.2 p.ct.
+
+_By-products of oxidation._--The liquors from B were found to contain
+saccharic acid: the acid from C and B contained a dibasic acid which
+appeared to be tartaric acid.
+
+The isolation of (1) isosaccharinic and (2) dioxybutyric acid from the
+products of digestion of the oxycelluloses with lime-milk at 100 deg. was
+effected by the separation of their respective calcium salts, (1) by
+direct crystallisation, (2) by precipitation alcohol after separation of
+the former.
+
+
+CELLULOSES, HYDRO- AND OXYCELLULOSES, AND CELLULOSE ESTERS.
+
+L. VIGNON (Bull. Soc. Chim., 1901 [3], 25, 130).
+
+(a) _Oxycelluloses from cotton, hemp, flax, and ramie._--The
+comparative oxidation of these celluloses, by treatment with HClO_{3}
+at 100 deg., gave remarkably uniform results, as shown by the following
+numbers, showing extreme variations: yields, 68-70 p.ct.; hydrazine
+reaction, N fixed 1.58-1.69; fixation of basic colouring matters
+(relative numbers), saffranine, 100-200, methylene blue, 100-106. The
+only points of difference noted were (1) hemp is somewhat more resistant
+to the acid oxidation; (2) the cotton oxycellulose shows a somewhat
+higher (25 p.ct.) cupric reduction.
+
+(b) _'Saccharification' of cellulose, cellulose hydrates, and
+hydrocellulose._--The products were digested with dilute hydrochloric
+acid six hours at 100 deg., and the cupric reduction of the soluble products
+determined and calculated to dextrose.
+
+  100 grms. of                   gave reducing products equal to Dextrose
+
+Purified cotton                                                      3.29
+  "      Hydrocellulose                                              9.70
+Cotton mercerised (NaOH 30 deg. B.)                                      4.39
+Cotton mercerised (NaOH 40 deg. B.)                                      3.51
+Cellulose reprecipitated from cuprammonium                           4.39
+Oxycellulose                                                        14.70
+Starch                                                              98.6
+
+These numbers show that cellulose may be hydrated both by mercerisation
+and solution, without affecting the constitutional relationships of the
+CO groups. The results also differentiate the cellulose series from
+starch in regard to hydrolysis.
+
+(c) _Cellulose and oxycellulose nitrates._--The nitric esters of
+cellulose have a strong reducting action on alkaline copper solutions.
+The author has studied this reaction quantitatively for the esters both
+of cellulose and oxycellulose, at two stages of 'nitration,' represented
+by 8.2-8.6 p.ct. and 13.5-13.9 p.ct. total nitrogen in the
+ester-products, respectively. The results are expressed in terms (c.c.)
+of the cupric reagent (Pasteur) reduced per 100 grs. compared with
+dextrose (=17767).
+
+    Cellulose maximum nitration (13.5 p.ct. N)             3640
+    Oxycellulose maximum nitration (13.9 p.ct. N)          3600
+    Cellulose minimum nitration (8.19 p.ct. N)             3700
+    Oxycellulose minimum nitration (8.56 p.ct. N)          3620
+
+The author concludes that, since the reducing action is independent of
+the degree of nitration, and is the same for cellulose and the
+oxycelluloses, the ester reaction in the case of the normal cellulose is
+accompanied by oxidation, the product being an oxycellulose ester.
+
+_Products of 'denitration'._--The esters were treated with ferrous
+chloride in boiling aqueous solution. The products were oxycelluloses,
+with a cupric reduction equal to that of an oxycellulose directly
+prepared by the action of HClO_{3}. On the other hand, by treatment with
+ammonium sulphide at 35 deg.-40 deg. 'denitrated' products were obtained without
+action on alkaline copper solutions.
+
+
+OXYCELLULOSES AND THE MOLECULAR WEIGHT OF CELLULOSE.
+
+H. NASTUKOFF (Berl. Ber. 33 [13] 2237).
+
+(p. 61) The author continues his investigations of the oxidation of
+cellulose. [Compare Bull. Mulhouse, 1892.] The products described were
+obtained by the action of hypochlorites and permanganates upon Swedish
+filter paper (Schleicher and Schuell).
+
+4. _Oxidation by hypochlorites._--(1) The cellulose was digested 24 hrs.
+with 35 times its weight of a filtered solution of bleaching power of
+4 deg.B.; afterwards drained and exposed for 24 hrs. to the atmosphere.
+These treatments were then repeated. After washing, treatment with
+dilute acetic acid and again washing, the product was treated with a 10
+p.ct. NaOH solution. The oxycellulose was precipitated from the
+filtered solution: yield 45 p.ct. The residue when purified amounted to
+30 p.ct. of the original cellulose, with which it was identical in all
+essential properties.
+
+The oxycellulose, after purification, dried at 110 deg., gave the following
+analytical numbers:
+
+     C    43.64     43.78    43.32    43.13
+     H     6.17      6.21     5.98     6.08
+
+Its compound with phenylhydrazine (_loc. cit._) gave the following
+analytical numbers:
+
+     N      0.78     0.96    0.84
+
+(2) The reagents were as in (1), but the conditions varied by passing a
+stream of carbonic acid gas through the solution contained in a flask,
+until Cl compounds ceased to be given off. The analysis of the purified
+oxycellulose gave C 43.53, H 6.13.
+
+(3) The conditions were as in (2), but a much stronger hypochlorite
+solution--viz. 12 deg.B.--was employed. The yield of oxycellulose
+precipitated from solution in soda lye (10 p.ct. NaOH) was 45 p.ct.
+There was only a slight residue of unattacked cellulose. The analytical
+numbers obtained were:
+
+    Oxycellulose              C  43.31   43.74   43.69
+        "                     H   6.47    6.42    6.51
+                              ________________________
+
+    Phenylhydrazine compound  N           0.62    0.81
+
+B. _Oxidation by permanganate_ (KMnO_{4}). (1) The cellulose 16 grms.
+was treated with 1100 c.c. of a 1 p.ct. solution of KMnO_{4} in
+successive portions. The MnO_{2} was removed from time to time by
+digesting the product with a dilute sulphuric acid (10 p.ct.
+H_{2}SO_{4}). The oxycellulose was purified as before, yield 40 p.ct.
+Analytical numbers:
+
+    Oxycellulose              C          42.12    42.9
+        "                     H           6.20     6.11
+                              ________________________
+
+    Phenylhydrazine compound  N   1.35    1.08     1.21
+
+(2) The cellulose (16 grms.) was digested 14 days with 2500 c.c. of 1
+p.ct. KMnO_{4} solution. The purified oxycellulose was identical in all
+respects with the above: yield 40 p.ct. C 42.66, H 6.19.
+
+(3) The cellulose (16 grms.) was heated in the water-bath with 1600 c.c.
+of 15 p.ct. H_{2}SO_{4} to which were added 18 grms. KMnO_{4}. The yield
+and composition of the oxycellulose was identical with the above. It
+appears from these results that the oxidation with hypochlorites acids 1
+atom of O to 4-6 of the unit groups C_{6}H_{10}O_{5}; and the oxidation
+with permanganate 2 atoms O per 4-6 units of C_{6}H_{10}O_{5}. The
+molecular proportion of N in the phenylhydrazine residue combining is
+fractional, representing 1 atom O, i.e. 1 CO group reacting per 4
+C_{36}H_{60}O_{31} and 6 C_{24}H_{49}O_{21} respectively, assuming the
+reaction to be a hydrazone reaction.
+
+Further investigations of the oxycelluloses by treatment with (a)
+sodium amalgam, (b) bromine (water), and (c) dilute nitric acid at
+110 deg., led to no positive results.
+
+By treatment with alcoholic soda (NaOH) the products were resolved into
+a soluble and insoluble portion, the properties of the latter being
+those of a cellulose (hydrate).
+
+_Molecular weight of cellulose and oxycellulose._--The author endeavours
+to arrive at numbers expressing these relations by converting the
+substances into acetates by Schutzenberger's method, and observing the
+boiling-points of their solution in nitrobenzene.
+
+
+FERMENTATION OF CELLULOSE
+
+V. OMELIANSKI (Compt. Rend., 1897, 125, 1131-1133).
+
+Pure paper was allowed to ferment in the presence of calcium carbonate
+at a temperature of 35 deg. for 13 months. The products obtained from
+3.4743 grams of paper were: acids of the acetic series, 2.2402 grams;
+carbonic anhydride, 0.9722 grams; and hydrogen, 0.0138 gram. The acids
+were chiefly acetic and butyric acid, the ratio of the former to the
+latter being 1.7 : 1. Small quantities of valeric acid, higher alcohols,
+and odorous products were formed.
+
+The absence of methane from the products of fermentation is remarkable,
+but the formation of this gas seems to be due to a special organism
+readily distinguishable from the ferment that produces the fatty acids.
+This organism is at present under investigation.
+
+       *       *       *       *       *
+
+(p. 75) ~Constitution of Cellulose.~--It may be fairly premised that the
+problem of the constitution of cellulose cannot be solved independently
+of that of molecular aggregation. We find in effect that the structural
+properties of cellulose and its derivatives are directly connected with
+their constitution. So far we have only a superficial perception of this
+correlation. We know that a fibrous cellulose treated with acids or
+alkalis in such a way that only hydrolytic changes can take place is
+converted into a variety of forms of very different structural
+characteristics, and these products, while still preserving the main
+chemical characteristics of the original, show when converted into
+derivatives by simple synthesis, _e.g._ esters and sulphocarbonates, a
+corresponding differentiation of the physical properties of these
+derivatives, from the normal standard, and therefore that the new
+reacting unit determines a new physical aggregate. Thus the
+sulphocarbonate of a 'hydrocellulose' is formed with lower proportions
+of alkaline hydrate and carbon disulphide, gives solutions of relatively
+low viscosity, and, when decomposed to give a film or thread of the
+regenerated cellulose, these are found to be deficient in strength and
+elasticity. Similarly with the acetate. The normal acetate gives
+solutions of high viscosity, films of considerable tenacity, and when
+those are saponified the cellulose is regenerated as an unbroken film.
+The acetates of hydrolysed celluloses manifest a retrogradation in
+structural and physical properties, proportioned to the degree of
+hydrolysis of the original.
+
+We may take this opportunity of pointing out that the celluloses not
+only suggest with some definiteness the connection of the structural
+properties of visible aggregates--that is, of matter in the mass--with
+the configuration of the chemical molecule or reacting unit, but supply
+unique material for the actual experimental investigation of the
+problems involved. Of all the 'organic' colloids cellulose is the only
+one which can be converted into a variety of derivative forms, from each
+of which a regular solid can be produced in continuous length and of any
+prescribed dimensions. Thus we can compare the structural properties of
+cellulose with those of its hydrates, nitrates, acetates, and benzoates,
+in terms of measurements of breaking strain, extensibility, elasticity.
+Investigations in this field are being prosecuted, but the results are
+not as yet sufficiently elaborated for reduction to formulae. One
+striking general conclusion is, however, established, and that is that
+the structural properties of cellulose are but little affected by
+esterification and appear therefore to be a function of the special
+arrangement of the carbon atoms, i.e. of the molecular constitution.
+Also it is established that the molecular aggregate which constitutes a
+cellulose is of a resistant type, and undoubtedly persists in the
+solutions of the compounds.
+
+It may be urged that it is superfluous to import these questions of
+mass-aggregation into the problem of the chemical constitution of
+cellulose. But we shall find that the point again arises in attempting
+to define the reacting unit, which is another term for the molecule. In
+the majority of cases we rely for this upon physical measurements; and
+in fact the purely chemical determination of such quantities is
+inferential. Attempts have been made to determine the molecular weights
+of the cellulose esters in solution, by observations of depression of
+solidifying and boiling-points. But the numbers have little value. The
+only other well-defined compound is the sulphocarbonate. It has been
+pointed out that, by successive precipitations of this compound, there
+occurs a continual aggregation of the cellulose with dissociation of the
+alkali and CS residues and it has been found impossible to assign a
+limit to the dissociation, i.e. to fix a point at which the transition
+from soluble sulphocarbonate to insoluble cellulose takes place.
+
+On these grounds it will be seen we are reduced to a somewhat
+speculative treatment of the hypothetical ultimate unit group, which is
+taken as of C_{6} dimensions.
+
+As there has been no addition of experimental facts directly
+contributing to the solution of the problem, the material available for
+a discussion of the probabilities remains very much as stated in the
+first edition, pp. 75-77. It is now generally admitted that the
+tetracetate _n_ [C_{6}H_{6}O.(OAc)_{4}] is a normal cellulose ester;
+therefore that four of the five O atoms are hydroxylic. The fifth is
+undoubtedly carbonyl oxygen. The reactions of cellulose certainly
+indicate that the CO- group is ketonic rather than aldehydic. Even when
+attacked by strong sulphuric acid the resolution proceeds some
+considerable way before products are obtained reducing Fehling's
+solution. This is not easily reconcilable with any polyaldose formula.
+Nor is the resistance of cellulose to very severe alkaline treatments.
+The probability may be noted here that under the action of the alkaline
+hydrates there occurs a change of configuration. Lobry de Bruyn's
+researches on the change of position of the typical CO- group of the
+simple hexoses, in presence of alkalis, point very definitely in this
+direction. It is probable that in the formation of alkali cellulose
+there is a constitutional change of the cellulose, which may in effect
+be due to a migration of a CO- position within the unit group. Again
+also we have the interesting fact that structural changes accompany the
+chemical reaction. It is surprising that there should have been no
+investigation of these changes of external form and structure, otherwise
+than as mass effects. We cannot, therefore, say what may be the
+molecular interpretation of these effects. It has not yet been
+determined whether there are any intrinsic volume changes in the
+cellulose substance itself: and as regards what changes are determined
+in the reacting unit or molecule, we can only note a fruitful subject
+for future investigation. _A priori_ our views of the probable changes
+depend upon the assumed constitution of the unit group. If of the
+ordinary carbohydrate type, formulated with an open chain, there is
+little to surmise beyond the change of position of a CO- group. But
+alternative formulae have been proposed. Thus the tetracetate is a
+derivative to be reckoned with in the problem. It is formed under
+conditions which preclude constitutional changes within the unit groups.
+The temperature of the main reaction is 30 deg.-40 deg., the reagents are used
+but little in excess of the quantitative proportions, and the yields are
+approximately quantitative. If now the derivative is formed entirely
+without the hydrolysis the empirical formula C_{6}H_{6}O.(OAc)_{4}
+justifies a closed-ring formula for the original viz.
+CO<[CHOH]_{4}>CH_{2}; and the preference for this formula depends upon
+the explanation it affords of the aggregation of the groups by way of
+CO-CH_{2} synthesis.
+
+The exact relationship of the tetracetate to the original cellulose is
+somewhat difficult to determine. The starting-point is a cellulose
+hydrate, since it is the product obtained by decomposition of the
+sulphocarbonate. The degree of _hydrolysis_ attending the cycle of
+reactions is indicated by the formula 4 C_{6}H_{10}O_{5}.H_{2}O. It has
+been already shown that this degree of hydrolysis does not produce
+molecular disaggregation. If this hydrate survived the acetylation it
+would of course affect the empirical composition, i.e. chiefly the
+carbon percentage, of the product. It may be here pointed out that the
+extreme variation of the carbon in this group of carbohydrate esters is
+as between C_{14}H_{20}O_{10} (C = 48.3 p.ct.) and C_{14}H_{18}O_{9} (C
+= 50.8 p.ct.) i.e. a tetracetate of C_{6}H_{12}O_{6} and
+C_{6}H_{10}O_{5} respectively. In the fractional intermediate terms it
+is clear that we come within the range of ordinary experimental errors,
+and to solve this critical point by way of ultimate analysis must
+involve an extended series of analyses with precautions for specially
+minimising and quantifying the error. The determination of the acetyl by
+saponification is also subject to an error sufficiently large to
+preclude the results being applied to solve the point. While, therefore,
+we must defer the final statement as to whether the tetracetate is
+produced from or contains a partly hydrolysed cellulose molecule, it is
+clear that at least a large proportion of the unit groups must be
+acetylated in the proportion C_{6}H_{6}O.(OAc)_{4}.
+
+It has been shown that by the method of Franchimont a higher proportion
+of acetyl groups can be introduced; but this result involves a
+destructive hydrolysis of the cellulose: the acetates are not
+derivatives of cellulose, but of products of hydrolytic decomposition.
+
+It appears, therefore, that with the normal limit of acetylation at the
+tetracetate the aggregation of the unit groups must depend upon the CO-
+groups and a ring formula of the general form CO<[CHOH]_{4}>CH_{2} is
+consistent with the facts.
+
+Vignon has proposed for cellulose the constitutional formula
+
+     O------CH
+     |      | \
+     |      O  \[CHOH]_{3}
+     |      |  /
+     CH_{2}-CH/
+
+with reference to the highest nitrate, and the decomposition of the
+nitrate by alkalis with formation of hydroxypyruvic acid. While these
+reactions afford no very sure ground for deductions as to constitutional
+relationships, it certainly appears that, if the aldose view of the unit
+group is to be retained, this form of the anhydride contains suggestions
+of the general tendency of the celluloses on treatment with condensing
+acids to split off formic acid in relatively large quantity [Ber. 1895,
+1940]; the condensation of the oxycelluloses to furfural; the
+non-formation of the normal hydroxy-dicarboxylic acids by nitric acid
+oxidations. Indirectly we may point out that any hypothesis which
+retains the polyaldose view of cellulose, and so fails to differentiate
+its constitution from that of starch, has little promise of progress.
+The above formula, moreover, concerns the assumed unit group, with no
+suggestion as to the mode of aggregation in the cellulose complex. Also
+there is no suggestion as to how far the formula is applicable to the
+celluloses considered as a group. In extending this view to the
+oxycelluloses, Vignon introduces the derived oxidised group
+
+     CHO.(CHOH)_{3}.CH . CO
+                    |_O__|
+
+--of which one is apportioned to three or four groups of the cellulose
+previously formulated: these groups in condensed union together
+constitute an oxycellulose.
+
+These views are in agreement with the experimental results obtained by
+Faber and Tollens (p. 71). They regard the oxycelluloses as compounds of
+'celloxin' C_{6}H_8{O}_{6} with 1-4 mols. unaltered cellulose; and the
+former they particularly refer to as a lactone of glycuronic acid. But
+on boiling with lime they obtain dioxybutyric and isosaccharinic acids;
+both of which are not very obviously related to the compounds formulated
+by Vignon. We revert with preference to a definitely ketonic formula,
+for which, moreover, some farther grounds remain to be mentioned. In the
+systematic investigation of the nitric esters of the carbohydrates (p.
+41) Will and Lenze have definitely differentiated the ketoses from the
+aldoses, as showing an internal condensation accompanying the ester
+reaction. Not only are the OH groups taking part in the latter
+consequently less by two than in the corresponding aldoses, but the
+nitrates show a much increased stability. This would give a simple
+explanation of the well-known facts obtaining in the corresponding
+esters of the normal cellulose. We may note here that an important item
+in the quantitative factors of the cellulose nitric ester reaction has
+been overlooked: that is, the yield calculated to the NO_{3} groups
+fixed. The theoretical yields for the higher nitrates are
+
+                     Yield p.ct.    N p.ct.
+                    of cellulose  of nitrate
+    Pentanitrate        169         12.7
+    Hexanitrate         183         14.1
+
+From such statistics as are recorded the yields are not in accordance
+with the above. There is a sensible deficiency. Thus Will and Lenze
+record a yield of 170 p.ct. for a product with 13.8 p.ct. N, indicating
+a deficiency of about 10 p.ct. As the by-products soluble in the acid
+mixture are extremely small, the deficiency represents approximately the
+water split off by an internal reaction. In this important point the
+celluloses behave as ketoses.
+
+In the lignocelluloses the condensed constituents of the complex are of
+well-marked ketonic, i.e. quinonic, type. In 'nitrating' the
+lignocelluloses this phenomenon of internal condensation is much more
+pronounced (see p. 131). As the reaction is mainly confined to the
+cellulose of the fibre, we have this additional evidence that the
+typical carbonyl is of ketonic function. It is still an open question
+whether the cellulose constituents of the lignocelluloses are
+progressively condensed--with progress of 'lignification'--to the
+unsaturated or lignone groups. There is much in favour of this view,
+the evidence being dealt with in the first edition, p. 180. The
+transition from a cellulose-ketone to the lignone-ketone involves a
+simple condensation without rearrangement; from which we may argue back
+to the greater probability of the ketonic structure of the cellulose. We
+must note, however, that the celluloses of the lignocelluloses are
+obtained as residues of various reactions, and are not homogeneous. They
+yield on boiling with condensing acids from 6 to 9 p.ct. furfural. It is
+usual to regard furfural as invariably produced from a pentose residue.
+But this interpretation ignores a number of other probable sources of
+the aldehyde. It must be particularly remembered that laevulose is
+readily condensed (a) to a methylhydroxyfurfural
+
+C_{6}H_{1}O_{6} - 3H_{2}O = C_{6}H_{6}O_{3} = C_{5}(OH).H_{2}.(CH_{3})O_{2}
+
+and (b) by HBr, with further loss of OH, as under:
+
+C_{6}H_{12}O_{6} - 4H_{2}O + HBr = C_{5}H_{3}(CH_{2}Br)O
+
+and generally the ketoses are distinguished from the aldoses by their
+susceptibility to condensation. Such condensation of laevulose has been
+effected by two methods: (a) by heating the concentrated aqueous
+solution with a small proportion of oxalic acid at 3 atm. pressure
+[Kiermayer, Chem. Ztg. 19, 100]; (b) by the action of hydrobromic acid
+(gas) in presence of anhydrous ether; the actual compound obtained being
+the omega-brommethyl derivative [Fenton, J. Chem. Soc. 1899, 423].
+
+This latter method is being extended to the investigation of typical
+celluloses, and the results appear to confirm the view that cellulose
+may be of ketonic constitution.
+
+The evidence which is obtainable from the synthetical side of the
+question rests of course mainly upon the physiological basis. There are
+two points which may be noted. Since the researches of Brown and Morris
+(J. Chem. Soc. 1893, 604) have altered our views of the relationships of
+starch and cane sugar to the assimilation process, and have placed the
+latter in the position of a primary product with starch as a species of
+overflow and reserve product, it appears that laevulose must play an
+important part in the elaboration of cellulose. Moreover, A. J. Brown,
+in studying the cellulosic cell-collecting envelope produced by the
+_Bacterium xylinum_, found that the proportion of this product to the
+carbohydrate disappearing under the action of the ferment was highest in
+the case of laevulose. These facts being also taken into consideration
+there is a concurrence of suggestion that the typical CO group in the
+celluloses is of ketonic character. That the typical cotton cellulose
+breaks down finally under the action of sulphuric acid to dextrose
+cannot be held to prove the aldehydic position of the carbonyls in the
+unit groups of the actual cellulose molecule or aggregate.
+
+We again are confronted with the problem of the aggregate and as to how
+far it may affect the constitution of the unit groups. That it modifies
+the functions or reactivity of the ultimate constituent groups we have
+seen from the study of the esters. Thus with the direct ester reactions
+the normal fibrous cellulose (C_{6}H_{16}O_{5}) yields a monoacetate,
+dibenzoate, and a trinitrate respectively under conditions which
+determine, with the simple hexoses and anhydrides, the maximum
+esterification, i.e. all the OH groups reacting. If the OH groups are of
+variable function, we should expect the CO groups _a fortiori_ to be
+susceptible of change of function, i.e. of position within the unit
+groups.
+
+But as to how far this is a problem of the constitution or phases of
+constitution of the unit groups or of the aggregate under reaction we
+have as yet no grounds to determine.
+
+The subjoined communication, appearing after the completion of the MS.
+of the book, and belonging to a date subsequent to the period intended
+to be covered, is nevertheless included by reason of its exceptional
+importance and special bearing on the constitutional problem above
+discussed.
+
+
+~THE ACTION OF HYDROGEN BROMINE ON CARBOHYDRATES.~[4]
+
+H. J. H. FENTON and MILDRED GOSTLING (J. Chem. Soc., 1901, 361).
+
+The authors have shown in a previous communication (Trans., 1898, 73,
+554) that certain classes of carbohydrates when acted upon at the
+ordinary temperature with dry hydrogen bromide in ethereal solution give
+an intense and beautiful purple colour.[5] It was further shown (Trans.,
+1899, 75, 423) that this purple substance, when neutralised with sodium
+carbonate and extracted with ether, yields golden-yellow prisms of
+omega-brommethylfurfural,
+
+     CH:C.CH_{2}Br
+     |  |
+     |  O
+     |  |
+     CH:C.CHO.
+
+This reaction is produced by laevulose, sorbose, cane sugar, and inulin,
+an intense colour being given within an hour or two. Dextrose, maltose,
+milk sugar, galactose, and the polyhydric alcohols give, if anything,
+only insignificant colours, and these only after long standing. The
+authors therefore suggested that the reaction might be employed as a
+means of distinguishing these classes of carbohydrates, the rapid
+production of the purple colour being indicative of _ketohexoses_, or of
+substances which produce these by hydrolysis.
+
+By relying only on the production of the purple colour, however, a
+mistake might possibly arise, owing to the fact that _xylose_ gives a
+somewhat similar colour after standing for a few hours. Hence, the
+observations should be confirmed by isolation of the crystals of
+brommethylfurfural. No trace of this substance is obtained from the
+xylose product.
+
+In order to identify the substance, the ether extract, after
+neutralisation, is allowed to evaporate to a syrup, and crystallisation
+promoted either by rubbing with a glass rod, or by the more certain and
+highly characteristic method of 'sowing' with the most minute trace of
+omega-brommethylfurfural, when crystals are almost instantly formed.
+These are recrystallised from ether, or a mixture of ether and light
+petroleum, and further identified by the melting-point (59.5-60.5 deg.),
+and, if considered desirable, by estimation of the bromine.
+
+It is now found, so reactive is the bromine atom in this compound, that
+the estimation may be accurately made by titration with silver nitrate
+according to Volhard's process, the crystals for this purpose being
+dissolved in dilute alcohol:
+
+0.1970 gram required 10.5 c.c. _N_/10 AgNO_{3}. Br = 42.63
+p.ct., calculated 42.32 p.ct.
+
+This method of applying hydrogen bromide in ethereal solution is, of
+course, unsuitable for investigations where a higher temperature has to
+be employed, or where long standing is necessary, since, under such
+circumstances, the ether itself is attacked. Wishing to make
+investigations under these conditions, the authors have tried several
+solvents, and, at present, find that chloroform is best suited to the
+purpose. In each of the following experiments, 10 grms. of the
+substance were covered with 250 c.c. of chloroform which had been
+saturated at 0 deg. with dry hydrogen bromide. The mixture was contained in
+an accurately stoppered bottle, firmly secured with an iron clamp, and
+heated in a water-bath to about the boiling temperature for two hours.
+After standing for several hours, the mixture was treated with sodium
+carbonate (first anhydrous solid, and afterwards a few drops of strong
+solution), filtered, and the solution dried over calcium chloride. Most
+of the chloroform was then distilled off, and the remaining solution
+allowed to evaporate to a thick syrup in a weighed dish.
+
+The product was then tested for omega-brommethylfurfural by 'sowing'
+with the most minute trace of the substance, as described above. It was
+then warmed on a water-oven, kept in a vacuum desiccator over solid
+paraffin, and the weight estimated. When necessary, the product was
+recrystallised from ether, and further identified by the tests
+mentioned. The following results were obtained:
+
+                      Weight of
+                    crude residue.
+Swedish filter paper     3.0      crystallised at once by 'sowing.'
+Ordinary cotton          3.3          "                     "
+Mercerised cotton        2.1          "                     "
+Straw cellulose[6]       2.3          "                     "
+Laevulose                 2.2          "                     "
+Inulin                   1.3          "                     "
+Potato starch            0.37         "                     "
+Cane sugar               0.85         "                     "
+Dextrose                 0.33     uncrystallisable.
+Milk sugar               0.37         "
+Glycogen                 0.34         "
+Galactose                0.34         "
+
+The products from _dextrose_, _milk sugar_, and _galactose_ absolutely
+refused to crystallise even when extracted with ether and again
+evaporated, or by 'sowing,' stirring, &c.
+
+The _glycogen_ product deposited a very small amount of crystalline
+matter on standing, but the quantity was too minute for examination;
+moreover, it refused altogether to crystallise in contact with the
+aldehyde. It may fairly be stated, therefore, that these last four
+substances give absolutely negative results as regards the formation of
+omega-brommethylfurfural; if any is formed, its quantity is altogether
+too small to be detected.
+
+The specimen of _starch_ examined was freshly prepared from potato, and
+purified by digestion for twenty-four hours each with _N_/10 KOH, _N_/4
+HCl, and strong alcohol; it was then washed with water and allowed to
+dry in the air. It will be seen that this substance gave a positive
+result, but that the yield was extremely small, and might yet be due to
+impurity. Considering the importance of the behaviour of starch, for the
+purpose of drawing general conclusions from these observations, it was
+thought advisable to make further experiments with specimens which could
+be relied upon, and also to investigate the behaviour of dextrin. This
+the authors have been enabled to do upon a series of specimens specially
+prepared by C. O'Sullivan, and thus described by him:
+
+     1. Rice starch, specially purified by the permanganate method.
+
+     2. Wheat starch       "                "                 "
+
+     3. Oat starch, contains traces of oil, washed with dilute KOH
+     and dilute HCl.
+
+     4. Pea starch, first crop, washed with alkali, acid (HCl), and
+     strong alcohol.
+
+     5. Natural dextrin, D = 3.87, alpha_{D} = 194.7; K = 0.95, (c
+     2.628).
+
+     6. alpha-Dextrin, C equation purified without fermentation, 30
+     precipitations with alcohol (Trans., 1879, 35, 772).
+
+The examination of these specimens was conducted on a smaller scale, but
+under the same conditions as before, _one gram_ of the substance being
+treated with 12.5 c.c. of the saturated chloroform solution and heated
+in sealed tubes for two hours as above. The results were as follows:
+
+                    Weight of
+                  crude residue.
+1. Rice starch       0.046   crystallised at once by 'sowing.'
+2. Wheat starch      0.044        "                 "
+3. Oat starch        0.049        "                 "
+4. Pea starch        0.064        "                 "
+5. Natural dextrin   0.088        "                 "
+6. alpha-Dextrin     0.055        "                 "
+
+The results may therefore be summarised as follows:--Treated under these
+particular conditions all forms of cellulose give large yields of
+omega-brommethylfurfural, some varieties giving as much as 33 per cent.
+Laevulose, inulin, and cane sugar give yields varying from 22 to 8.5 per
+cent.; various starches give small yields (average about 4.5 per cent.);
+and dextrins 5 to 8 per cent., whereas dextrose, milk sugar, and
+galactose give, apparently, none at all.
+
+The yields represent the solid crystalline residue; this when purified
+by recrystallisation gives, probably, about three-quarters of its weight
+of pure crystals. (In the case of dextrose, &c., the yields represent
+the weight of syrup.)
+
+These numbers, however, by no means represent the maximum yields
+obtainable, owing to the comparatively slight solubility of hydrogen
+bromide in chloroform. The process was conducted in the above manner
+only for the sake of uniform comparison. The ether method previously
+described gives much larger yields; for example, 12 grms. of inulin
+treated with only 60 c.c. of the saturated ether gave 2.5 grms. of
+substance. For the purpose of obtaining larger yields, other methods are
+being investigated.
+
+The facts recorded above, taken in conjunction with those given in our
+previous communications, appear to point definitely to the following
+general conclusions. First, that the various forms of _cellulose_
+contain one or more groups or nuclei identical with that contained in
+_laevulose_, and that such groups constitute the main or essential part
+of the molecule. Secondly, that similar groupings are contained in
+_starches_ and _dextrins_, but that the proportion of such groupings
+represents a relatively small part of the whole structure.
+
+The nature of this grouping is, according to the generally accepted
+constitution of _laevulose_, the six-carbon chain with a ketonic group:
+
+     C.C.C.C.C.C
+             || .
+             O
+
+But the results might, on the other hand, be considered indicative of
+the anhydride or 'lacton' grouping, which Tollens suggested for
+laevulose:
+
+     C.C.C.C.C.C
+        \   /
+         \ /  .
+          O
+
+The latter very simply represents the formation of
+omega-brommethylfurfural from laevulose,[7]
+
+              ------O-----
+              |   H   H  |
+              |   |   |  |
+     OH.C-----C---C---C--C-----CH_{2}.OH
+        H_{2} OH  OH  OH H
+
+giving
+
+          H H
+     HC.C:C.C:C.CH_{2}Br
+      || \   /    ,
+      O   \ /
+           O
+
+
+although by a little further 'manipulation' of the symbols the change
+could, of course, be represented by reference to the ketonic formula.
+
+
+~The Ketonic Constitution of Cellulose.~
+
+C. F. CROSS and E. J. BEVAN (J. Chem. Soc., 1901, 366).
+
+In this paper the authors discuss more fully the theoretical bearings of
+the observations of Fenton and Gostling, the two papers being
+simultaneously communicated. The paper is mainly devoted to a review of
+the antecedent evidence, chemical and physiological, and to a general
+summing up in favour of the view that cellulose is a polyketose
+(anhydride).
+
+       *       *       *       *       *
+
+(p. 79) ~Composition of the Seed Hair of Eriodendron~ (~Anf.~)--Some
+interest attaches to the results of an analytical investigation which we
+have made of this silky floss. There is little doubt that cotton is
+entirely exceptional in its characteristics: both in structure and
+chemical composition it fails to show any adaptation to what we may
+regard as the _more obvious_ functions of a seed hair--which certainly
+do not demand either structural strength or chemical resistance. The
+following numbers determined for the kapok differentiate it widely from
+the cottons:
+
+     Ash, 1.3; moisture, 9.3; alkaline hydrolysis (loss) (a) 16.7,
+     (b) 21.8. Cellulose, by chlorination, &c., 71.1.
+
+In reacting with chloride it shows the presence of unsaturated groups,
+similar to the lignone of the woods. This was confirmed by a
+well-marked reaction with ferric ferricyanide with increase of weight
+due to the fixation of the blue cyanide.
+
+But the most characteristic feature is the high yield of furfural on
+boiling with condensing acids. The following numbers were determined:
+
+     Total furfural from original fibre    14.84
+     In residue from alkali hydrolysis     11.5
+     In cellulose isolated by Cl method    10.4
+
+Treated with sulphuric acids of concentration, (a) 92.1 grs.
+H_{2}SO_{4} per 100 c.c., (b) 105.8 grs. per 100 c.c., the fibres
+dissolve, and diluted immediately after complete solution it was
+resolved into
+
+                                      (a)        (b)
+
+Reprecipitated fraction               68.7       43.7
+Soluble fraction yielding furfural    13.2       14.3
+
+By these observations it is established that the furfuroids are of the
+cellulose type and behave very much as the furfuroids of the cereal
+celluloses.
+
+This group of seed hairs invites exhaustive investigation. The furfuroid
+constituents are easily isolated, and as they constitute at least
+one-third of the fibre substance it is especially from this point of
+view that they invite study.
+
+
+RECHERCHES SUR L'OXYCELLULOSE.
+
+L. VIGNON.
+
+~Resume of investigations (1898-1900) of Oxycellulose, published as a
+brochure~ (Rey, Lyon, 1900).
+
+(a) A typical oxycellulose prepared from cotton cellulose by the
+action of HClO_{3} (HCl + KClO_{3}) in dilute solution at 100 deg. for one
+hour gave the following numbers:
+
+                                                  C        H        O
+Elementary composition                          43.55    6.03     50.42
+
+                                        Oxycellulose   Original cellulose
+  Analysis by Lange's method
+    Soluble in KOH (at 180 deg.)               87.6           12.0
+    Insoluble in KOH (at 180 deg.)             12.4           88.0
+
+                                           Oxycellulose  Original cellulose
+  Heat of combustion                        4124-4133      4190-4224
+Heat evolved in contact with 50 times wt.}
+  normal KOH per 100 grms.               }  1.3 cal.       0.74 cal.
+
+                                            Oxycellulose  Cellulose
+Absorption of colouring       } Saffranine       0.7          0.0
+matters at 100 deg. per 100 grms. } Methylene blue   0.6          0.2
+
+(b) _Yield of furfural from cellulose, oxy- and
+hydro-cellulose._--From the hydrocelluloses variously prepared the
+author obtains 0.8 p.ct. furfural; from bleached cotton 1.8 p.ct.; and
+from the oxycelluloses variously prepared 2.0-3.5 p.ct. The 'furfuroid'
+is relatively more soluble in alkaline solutions (KOH) in the cold. The
+insoluble residue is a normal cellulose.
+
+(c) _Nitrates of cellulose, oxy- and hydro-cellulose._--Treated with
+the usual acid mixture (H_{2}SO_{4} 3 p., HNO_{3} 1 p.) under conditions
+for maximum action, the resulting esters showed uniformly a fixation of
+11.0 NO_{2} groups per unit mol. of C_{24}. The oxycellulose nitrate
+was treated directly with dilute solution of potassium hydrate in the
+cold. From the products of decomposition the author obtained the osazone
+of hydroxypyruvic acid [Will, Ber. 24, 400].
+
+(d) _Osazones of the oxycelluloses._--Oxycelluloses prepared by
+various methods are found to fix varying proportions of phenylhydrazine
+(residue), viz. from 3.4-8.5 p.ct. of the cellulose derivative reacting,
+corresponding with, i.e. calculated from, the nitrogen determined in the
+products (0.87-2.2 p.ct.). The reaction is assumed to be that of osazone
+formation.
+
+The author has also established a relation between the phenylhydrazine
+fixed and the furfural which the substance yields on boiling with
+condensing acids. This is illustrated by the subjoined series of
+numbers:
+
+                              Phenylhydrazine     Furfural
+                                 Fixed p.ct.    formed p.ct.
+Cotton (bleached)                   1.73            1.60
+Oxycellulose (HClO_{3})             7.94            2.09
+     "       (HClO)                 3.37            1.79
+     "       (CrO_{3}) (1)          7.03            3.00
+     "       (CrO_{3}) (2)          7.71            3.09
+     "       (CrO_{3}) (3)          8.48            3.50
+
+(e) _Constitution of cellulose and oxycellulose._--The results of
+these investigations are generalised as regards cellulose (C_6) by the
+constitutional formula
+
+                 CH--CH_{2}
+               / |   |
+     (CHOH)_{3}  O   |
+               \ |   |
+                 CH--O .
+
+The oxycelluloses contain the characteristic group
+
+                COH
+               /
+     (CHOH)_{3}
+               \
+                CH--CO
+                 \ /
+                  O
+
+in union with varying proportions of residual cellulose.
+
+
+QUANTITATIVE SEPARATION OF CELLULOSE-LIKE CARBOHYDRATES IN VEGETABLE
+SUBSTANCES.
+
+WILHELM HOFFMEISTER (Landw. Versuchs-Stat., 1897, 48, 401-411).
+
+To separate the hemicelluloses, celluloses, and the constituents of
+lignin without essential change, the substance, after being freed from
+fat, is extracted with dilute hydrochloric acid and ammonia, and the
+residue frequently agitated for a day or two with 5-6 p.ct. caustic soda
+solution. It is then diluted, the extract poured off, neutralised with
+hydrochloric acid, treated with sufficient alcohol, and the
+hemicellulose filtered, dried, and weighed. The residue from the soda
+extract is washed on a filter with hot water, and extracted with
+Schweizer's reagent.
+
+When the final residue (lignin) is subjected to prolonged extraction
+with boiling dilute ammonia (a suitable apparatus is described, with
+sketch) until the ammonia is no longer coloured, a residue is obtained
+which mostly dissolves in Schweizer's reagent, and on repeating the
+process the residue is found to consist largely of mineral matter. The
+dissolved cellulose-like substances often contain considerable amounts
+of pentosanes.
+
+According to the nature of the substance, the extraction with ammonia
+may take weeks, or months, or even longer; the ammonia extracts of hard
+woods (as lignum vitae) and of cork are dark brown, and give an odour of
+vanilla when evaporated down. The residues, which are insoluble in
+water, but redissolve in ammonia, have the properties of humic acids.
+Other vegetable substances, when extracted, yielded, besides humic
+acids, a compound, C_{6}H_{7}O_{2}, soluble in alcohol and chloroform,
+but insoluble in water, ether, and benzene; preparations from different
+sources melted between 200 deg. and 210 deg..
+
+FOOTNOTES:
+
+[4] The original paper is reproduced with slight alterations.
+
+[5] This purple colour would appear to be due to a highly dissociable
+compound of omega-brommethylfurfural with hydrogen bromide. The aldehyde
+gives yellow or colourless solutions in various solvents, which are
+turned purple by a sufficient excess of hydrogen bromide. Dilution, or
+addition of water, at once discharges the colour.
+
+[6] Other forms of cellulose were also examined--for example, pinewood
+cellulose--and the substances separated from solution as thiocarbonate
+(powder and film). All of these gave good yields of
+omega-brommethylfurfural.
+
+[7] The change is empirically represented as
+
+C_{6}H_{12}O_{6} + HBr - 4H_{2}O = C_{6}H_{5}O_{2}Br.
+
+
+
+
+SECTION IV. CELLULOSE GROUP, INCLUDING HEMICELLULOSES AND TISSUE
+CONSTITUENTS OF FUNGI
+
+
+VERSUCHE ZUR BESTIMMUNG DES GEHALTS EINIGER PFLANZEN UND PFLANZENTEILE
+AN ZELLWANDBESTANDTEILEN AN HEMICELLULOSEN UND AN CELLULOSE.
+
+A. KLEIBER (Landw. Vers.-Stat., 1900, 54, 161).
+
+~ON THE DETERMINATION OF CELL-WALL CONSTITUENTS, HEMICELLULOSES AND
+CELLULOSE IN PLANTS AND PLANT TISSUES.~
+
+In a preliminary discussion the author critically compares the results
+of various of the methods in practice for the isolation and estimation
+of cellulose. The method of F. Schulze [digestion with dil. HNO_{3} with
+KClO_{3}--14 days, and afterwards treating the product with ammonia,
+&c.] is stated to be the 'best known' (presumably the most widely
+practised); W. Hoffmeister's modification of the above, in which the
+nitric acid is replaced by hydrochloric acid (10 p.ct. HCl) is next
+noted as reducing the time of digestion from 14 days to 1-2 days, and
+giving in many cases higher yields of cellulose. The methods of treating
+with the halogens, viz. bromine water (H. Mueller), chlorine gas (Cross
+and Bevan), and chlorine water, are dismissed with a bare mention,
+apparently on the basis of the conclusions of Suringar and Tollens
+(_q.v._). The method of Lange, the basis of which is a 'fusion' with
+alkaline hydrates at 180 deg., and the modified method of Gabriel, in which
+the 'fusion' with alkali takes place in presence of glycerin, are
+favourably mentioned.
+
+These methods were applied to a range of widely different raw materials
+to determine, by critical examination of the products, both as regards
+yield and composition, what title these latter have to be regarded as
+'pure cellulose.'
+
+This portion of the investigation is an extension of that of Suringar
+and Tollens, these latter confining themselves to celluloses of the
+'normal' groups, i.e. textile and paper-making celluloses. The present
+communication is a study of the tissue and cell-wall constituents of the
+following types:--
+
+     1. Green plants of false oat grass (_Arrhenatherium, E._).
+     2. Green plants of lucerne (_Medicago sativa_).
+     3. Leaves of the ash (_Fraxinus_).
+     4. Leaves of the walnut (_Juglans_).
+     5. Roots of the purple melic grass (_Molinia caerulea_).
+     6. Roots of dandelion (_Taraxacum officinale_).
+     7. Roots of comfrey.
+     8. Coffee berries.
+     9. Wheat bran.
+
+These raw materials were treated for the quantitative estimation of
+cellulose by the method of Lange (b), Hoffmeister (c), and Schulze
+(d), and the numbers obtained are referred for comparison to the
+corresponding yields of 'crude fibre' (Rohfaser) by the standard method
+(a).
+
+As a first result the author dismisses Lange's method as hopeless: the
+results in successive determinations on the same materials showing
+variations up to 60 p.ct. The results by c and d are satisfactorily
+concordant: the yields of cellulose are higher than of 'crude fibre.'
+This is obviously due to the conservation of 'hemicellulose' products,
+which are hydrolysed and dissolved in the treatments for 'crude fibre'
+estimation. A modified method was next investigated, in which the
+process of digestion with acid chloroxy- compounds (c and d) was
+preceded by a treatment with boiling dilute acid. The yields of
+cellulose by this method (e) are more uniform, and show less
+divergence from the numbers for 'crude fibre.'
+
+The author's numerical results are given in a series of tables which
+include determinations of proteids and ash constituents, and the
+corresponding deductions from the crude weight in calculating to 'pure
+cellulose.' The subjoined extract will illustrate these main lines of
+investigation.
+
+ ___________________________________________________________
+|                |             |                            |
+|                | Crude Fibre |       Pure Cellulose       |
+|                |_____________|____________________________|
+|                |             |             |              |
+| Raw Material   |   Weende    | Hoffmeister | Hoffmeister, |
+|                |   Method.   |   Method.   | modified by  |
+|                |     (a)     |     (c)     |   Author.    |
+|                |             |             |     (e)      |
+|________________|_____________|_____________|______________|
+|                |             |             |              |
+| Oat grass      |   30.35     |    34.9     |     31.5     |
+| Lucerne        |   25.25     |    28.7     |     20.5     |
+| Leaves of ash  |   13.05     |    15.4     |     13.8     |
+| Roots of melic |   21.60     |    29.1     |     21.4     |
+| Coffee beans   |   18.30     |    35.1     |     23.3     |
+| Bran           |    8.2      |    19.3     |      9.3     |
+|________________|_____________|_____________|______________|
+
+The final conclusion drawn from these results is that the method of
+Hoffmeister yields a product containing variable proportions of
+hemicelluloses. These are eliminated by boiling with a dilute acid (1.25
+p.ct. H_{2}SO_{4}), which treatment may be carried out on the raw
+material--i.e. before exposure to the acid chlorate, or on the crude
+cellulose as ordinarily isolated.
+
+~Determination of Tissue-constituents.~--By the regulated action of
+certain solvents applied in succession, it appears that such
+constituents of the plant-complex can be removed as have no organic
+connection with the cellular skeleton: the residue from such treatments,
+conversely, fairly represents the true tissue-constituents. The author
+employs the method of digestion with cold dilute alkaline solutions
+(0.15 to 0.5 p.ct. NaOH), followed by exhaustive washing with cold and
+hot water, afterwards with cold and hot alcohol, and finally with ether.
+
+The residue is dried and weighed as crude product. When necessary, the
+proportions of ash and proteid constituents are determined and deducted
+from the 'crude product' which, thus corrected, may be taken as
+representing the 'carbohydrate' tissue constituents.
+
+~Determination of Hemicelluloses.~--By the process of boiling with dilute
+acids (1.25 p.ct. H_{2}SO_{4}) the hemicelluloses are attacked--i.e.
+hydrolysed and dissolved. The action of the acid though selective is, of
+course, not exclusively confined to these colloidal carbohydrates. The
+proteid and mineral constituents are attacked more or less, and the
+celluloses themselves are not entirely resistant to the action. The loss
+due to the latter may be neglected, but in calculating the hemicellulose
+constants from the gross loss the proteids and mineral constituents
+require to be taken into account in the usual way.
+
+
+QUANTITATIVE SEPARATION OF HEMICELLULOSE, CELLULOSE, AND LIGNIN.
+PRESENCE OF PENTOSANES IN THESE SUBSTANCES.
+
+WILHELM HOFFMEISTER (Landw. Versuchs-Stat, 1898, 50, 347-362).
+
+(p. 88) The separation of the cellulose-like carbohydrates of sunflower
+husks is described.
+
+In order to ascertain the effect of dilute ammonia on the cellulose
+substances of lignin, a dried 5 p.ct. caustic soda extract was extracted
+successively with 1, 2, 3, and 4 p.ct. sodium hydroxide solution. Five
+grams of the 2 p.ct. extract were then subjected to the action of
+ammonia vapour; the cellulose did not completely dissolve in six weeks.
+Cellulose insoluble in caustic soda (32 grms.) was next extracted with
+ammonia, in a similar manner, for 10 days, dried, and weighed. 30.46
+grms. remained, which, when treated with 5 p.ct. aqueous caustic soda,
+yielded 0.96 grm. (3 per cent.) of hemicellulose.
+
+When cellulose is dissolved in Schweizer's solution, the residue is, by
+repeated extraction with aqueous sodium hydroxide, completely converted
+into the soluble form. On evaporating the ammonia from the Schweizer's
+extract, at the ordinary temperature and on a water-bath respectively,
+different amounts of cellulose are obtained; more hemicellulose is
+obtained, by caustic soda, from the heated solution than from that which
+was not heated. In this operation the pentosanes are more influenced
+than the hexosanes; pentosanes are not always readily dissolved by
+caustic soda, and hexosanes are frequently more or less readily
+dissolved. Both occur in lignin, and are then undoubtedly indigestible.
+These points have to be considered in judging the digestibility of these
+carbohydrates.
+
+A comparison of analyses of clover, at different periods, in the first
+and second years of growth, shows that both cellulose (Schweizer's
+extract) and lignin increase in both constituents. In the second year
+the lignin alone increased to the end; the cellulose decreased at the
+end of June. In the first year it seemed an absolutely as well as
+relatively greater amount of cellulose, and lignin was produced in the
+second year; this, however, requires confirmation. The amount of
+pentosanes in the Schweizer extract was relatively greater in the second
+than in the first year, but decreased in the lignin more in the second
+year than in the first: this result is also given with reserve.
+
+
+DIE CONSTITUTION DER CELLULOSEN DER CEREALIEN.
+
+C. F. CROSS, E. J. BEVAN, and C. SMITH (Berl. Ber., 1896, 1457).
+
+~THE CONSTITUTION OF THE CEREAL CELLULOSES.~
+
+(p. 84) Straw cellulose is resolved by two methods of acid hydrolysis
+into a soluble furfural-yielding fraction, and an insoluble fraction
+closely resembling the normal cellulose. (a) The cellulose is
+dissolved in sulphuric acids of concentration, H_{2}SO_{4}.2H_{2}O,
+H_{2}SO_{4}.3H_{2}O. As soon as solution is complete, the acid is
+diluted. A precipitate of cellulose hydrate (60-70 p.ct.) is obtained,
+and the filtered solution contains 90-95 p.ct. of the furfuroids of the
+original cellulose. The process is difficult to control, however, in
+mass, and to obtain the latter in larger quantity the cellulose (b) is
+digested with six times its weight of 1 p.ct. H_{2}SO_{4} at 3 atm.
+pressure, the products of the action being (1) a disintegrated cellulose
+retaining only a small fraction (1/12) of the furfural-yielding groups,
+and (2) a slightly coloured solution of the hydrolised furfuroids. An
+investigation of the latter gave the following results: By oxidation
+with nitric acid no saccharic acid was obtained; showing the absence of
+dextrose. The numbers for cupric reduction were in excess of those
+obtained with the hexoses. The yield of ozazone was high, viz. 30 to 40
+p.ct. of the weight of the carbohydrate in solution. On fractionating,
+the melting-points of the fractions were found to lie between 146 deg. and
+153 deg.. Ultimate analysis gave numbers for C, H, and N identical with
+those of a pentosazone. The product of hydrolysis appears, therefore, to
+be xylose or a closely related derivative.
+
+All attempts to obtain a crystallisation of xylose from the solution
+neutralised (BaCO_{3}), filtered, and evaporated, failed. The reaction
+with phloroglucol and HCl, moreover, was not the characteristic red of
+the pentoses, but a deep violet. The product was then isolated as a dry
+residue by evaporating further and drying at 105 deg.. Elementary analysis
+gave the numbers C 44.2, 44.5, and H 6.7, 6.3. Determinations of
+furfural gave 39.5 to 42.5 p.ct. On treating the original solution with
+hydrogen peroxide, and warming, oxidation set in, with evolution of
+CO_{2}. This was estimated (by absorption), giving numbers for CO_{2},
+19.5, 20.5, 20.1 p.ct. of the substance.
+
+The sum of these quantitative data is inconsistent with a pentose or
+pentosane formula; it is more satisfactorily expressed by the empirical
+formula
+
+                   O
+                  / \
+     C_{5}H_{8}O_{3} CH_{2},
+                  \ /
+                   O
+
+which represents a pentose monoformal. Attempts to synthesise a compound
+of this formula have been so far without success.
+
+
+UEBER EINIGE CHEMISCHE VORGAeNGE IN DER GERSTENPFLANZE.
+
+C. F. CROSS, E. J. BEVAN, and C. SMITH (Berl. Ber., 1895, 2604).
+
+~THE CHEMICAL LIFE-HISTORY OF THE BARLEY PLANT.~
+
+(p. 84) Owing to the presence of 'furfuroids' in large proportion as
+constituents of the tissues of the stems of cereals, these plants afford
+convenient material for studying the problem of the constitution of the
+tissue-furfuroids, as well as their relationship to the normal
+celluloses. The growing barley plant was investigated at successive
+periods of growth. Yield of furfural was estimated on the whole plant
+and on the residue from a treatment with alkaline and acid solvents in
+the cold such as to remove all cell contents. This residue is described
+as 'permanent tissue.' The observations were carried out through two
+growing seasons--1894-5--which were very different in character, the
+former being rainy with low temperature, the latter being abnormal in
+the opposite direction, i.e. minimum rainfall and maximum sunshine. The
+barley selected for observation was that of two experimental plots of
+the Royal Agricultural Society's farm, one (No. 1) remaining permanently
+unmanured, and showing minimum yield, the other (No. 6) receiving such
+fertilising treatment as to give maximum yields.
+
+The numerical results are given in the annexed tables:
+
+Table Headings:
+
+A: Date
+B: Age of Crop
+C: Plot
+D: Dry Weight
+E: Furfural p.ct. of dry weight (a)
+F: Permanent tissue p.ct. dry weight
+G: Furfural from permanent tissue
+H: P.ct. of tissue
+I: P.ct. of entire plant
+J: Ratio a : c
+
+BARLEY CROP, WOBURN, 1894.
+
+ ________________________________________________________________________
+|         |          |     |      |      |      |             |          |
+|         |          |     |      |      |      |     [G]     |          |
+|         |          |     |      |      |      |_____________|          |
+|         |          |     |      |      |      |      |      |          |
+|   [A]   |    [B]   | [C] | [D]  | [E]  | [F]  | [H]  | [I]  |   [J]    |
+|_________|__________|_____|______|______|______|______|______|__________|
+|         |          |     |      |      |      |      |      |          |
+| May 7   |  6 weeks |  1  | 19.4 |  7.0 | 53.4 | 12.7 |  6.8 | 1.03 : 1 |
+|         |          |  6  | 14.7 |  7.0 | 55.9 | 10.3 |  5.7 | 1.23 : 1 |
+| June 4  | 10 weeks |  1  | 17.6 |  7.7 | 52.9 | 11.6 |  6.1 | 1.26 : 1 |
+|         |          |  6  | 13.5 |  8.1 | 58.5 | 13.4 |  7.8 | 1.04 : 1 |
+| July 10 | 15 weeks |  1  | 42.0 |  9.0 | 65.7 |  9.8 |  6.4 | 1.40 : 1 |
+|         |          |  6  | 32.9 | 10.6 | 65.7 | 12.5 |  8.2 | 1.30 : 1 |
+| Cut     | 21 weeks |  1  | 64.0 | 11.9 | 70.0 | 14.5 | 10.1 | 1.18 : 1 |
+| Aug. 21 |          |  6  | 64.6 | 13.4 | 70.5 | 15.0 | 10.6 | 1.26 : 1 |
+| Carried | 22 weeks |  1  | 84.0 | 12.7 | 75.0 | 16.5 | 12.4 | 1.02 : 1 |
+| Aug. 31 |          |  6  | 86.4 | 12.4 | 78.4 | 15.1 | 11.8 | 1.05 : 1 |
+|                                                                        |
+|   BARLEY CROP, WOBURN, 1895.                                           |
+|                                                                        |
+| May 15  |  7 weeks |  1  | 20.6 |  6.6 | 53.9 | 10.2 |  5.5 | 1.20 : 1 |
+|         |          |  6  | 17.8 |  5.8 | 56.7 |  9.6 |  5.4 | 1.07 : 1 |
+| June 18 | 12 weeks |  1  | 34.6 |  8.0 | 38.2 | 14.7 |  5.6 | 1.42 : 1 |
+|         |          |  6  | 33.4 |  7.6 | 44.5 | 15.0 |  6.7 | 1.14 : 1 |
+| July 16 | 16 weeks |  1  | 52.8 | 12.1 | 55.6 | 16.3 |  9.1 | 1.33 : 1 |
+|         |          |  6  | 54.4 | 10.6 | 46.2 | 19.1 |  8.8 | 1.20 : 1 |
+| Aug. 16 | 20 weeks |  1  | 66.8 |  9.2 | 49.1 | 17.0 |  8.3 | 1.10 : 1 |
+|         |          |  6  | 65.0 |  9.8 | 49.8 | 19.1 |  9.4 | 1.04 : 1 |
+| Sept. 3 | 22 weeks |  1  | 84.3 | 10.4 | 45.7 | 17.6 |  8.0 | 1.31 : 1 |
+|         |          |  6  | 86.3 | 10.2 | 45.3 | 17.3 |  7.8 | 1.30 : 1 |
+|_________|__________|_____|______|______|______|______|______|__________|
+
+The variations exhibited by these numbers are significant. It is clear,
+on the other hand, that the assimilation of the furfuroids does not vary
+in any important way with variations in conditions of atmosphere and
+soil nutrition. They are essentially _tissue_-constituents, and only at
+the flowering period is there any accumulation of these compounds in the
+alkali-soluble form. It has been previously shown (ibid. 27, 1061)
+that the proportion of furfuroids in the straw-celluloses of the
+paper-maker differs but little from that of the original straws. For the
+isolation of the celluloses the straws are treated by a severe process
+of alkaline hydrolysis, to which, therefore, the furfuroid groups offer
+equal resistance with the normal hexose groups with which they are
+associated in the complex.
+
+The furfuroids of the cereal straws are therefore not pentosanes. They
+are original products of assimilation, and not subject to secondary
+changes after elaboration such as to alter either their constitution or
+their relationship to the normal hexose groups of the tissue-complex.
+
+
+(1) CONSTITUTION OF THE CEREAL CELLULOSES
+
+(Chem. Soc. J. 1896, 804).
+
+
+(2) THE CARBOHYDRATES OF BARLEY STRAW
+
+(Chem. Soc. J. 1896, 1604).
+
+
+(3) THE CARBOHYDRATES OF THE CEREAL
+
+STRAWS (Chem. Soc. J. 1897, 1001).
+
+
+(4) THE CARBOHYDRATES OF BARLEY STRAW
+
+(Chem. Soc. J. 1898, 459).
+
+C. F. CROSS, E. J. BEVAN, and CLAUD SMITH.
+
+These are a series of investigations mainly devoted to establishing the
+identity of the furfural-yielding group which is a characteristic
+constituent.
+
+This 'furfuroid' while equally resistant to alkalis as the normal
+cellulose group with which it is associated, is selectively hydrolysed
+by acids. Thus straw cellulose dissolves in sulphuric acids of
+concentration H_{2}SO_{4}.2H_{2}O - H_{2}SO_{4}.3H_{2}O, and on diluting
+the normal cellulose is precipitated as a hydrate, and the furfuroid
+remains in solution. But this sharp separation is difficult to control
+in mass. By heating with a very dilute acid (1 p.ct. H_{2}SO_{4}) the
+conditions are more easily controlled, the most satisfactory results
+being obtained with 15 mins. heating at 3 atm. pressure.
+
+(1) Operating in this way upon brewers' grains the furfuroid was
+obtainable as the chief constituent of a solution for which the
+following experimental numbers were determined:--Total dissolved solids,
+28.0 p.ct. of original 'grains'; furfural, 39.5 p.ct. of total dissolved
+solids, as compared with 12.5 p.ct. of total original grains; cupric
+reduction (calc. to total solids), 110 (dextrose = 100) osazone; yield
+in 3 p.ct. solution, 35 p.ct. of weight of total solids.
+
+                                  Pentosazone
+     Analysis       N  17.1  17.3    17.07
+                    C  62.5  62.3    62.2
+                    H   6.4   6.5     6.1
+     Melting-point                146 deg.-153 deg.
+
+From these numbers it is seen that of the total furfuroids of the
+original 'grains' 84 p.ct. are thus obtained in solution in the fully
+hydrolysed form, which is that of a pentose or pentose derivative. It
+was, however, found impossible to obtain any crystallisation from the
+neutralised (BaCO_{3}) and concentrated solution, the syrup being kept
+for some weeks in a desiccator. It was noted at the same time that the
+colour reaction of the original solution with phloroglucol and
+hydrochloric acid was a deep violet, in contradistinction to the
+characteristic red of the pentoses. On oxidation with hydrogen peroxide,
+in the proportion of 1 mol. H_{2}O_{2} to 1 mol. of the carbohydrate in
+solution, carbonic anhydride was formed in quantity = 20.0 p.ct. of the
+latter.
+
+Fermentation (yeast) experiments also showed a divergence from the
+resistant behaviour of the pentoses, a considerable proportion of the
+furfuroid disappearing in a normal fermentation.
+
+(2) The quantitative methods above described were employed in
+investigating the barley plant at different stages of its growth. The
+green plant was extracted with alcohol, the residue freed from alcohol
+and subjected to acid hydrolysis.
+
+The hydrolysed extract was neutralised and fermented. In the early
+stages of growth the furfuroids were completely fermented, i.e.
+disappeared in the fermentation. In the later stages this proportion
+fell to 50 p.ct. In the earlier stages, moreover, the normal hexose
+constituents of the permanent tissue were hydrolysed in large proportion
+by the acid, whereas in the matured straw the hydrolysis is chiefly
+confined to the furfuroids. In the early stages also the permanent
+tissue yields an extract with relatively low cupric reduction, showing
+that the carbohydrates are dissolved by the acid in a more complex
+molecular condition.
+
+These observations confirm the view that the furfuroids take origin in a
+hexose-pentose series of transformations. The proportion of furfuroid
+groups to total carbohydrates varies but little, viz. from 1/3 in the
+early stages to a maximum of 1/4 at the flowering period. At this period
+the differentiation of the groups begins to be marked.
+
+Taking all the facts of (1) and (2), they are not inconsistent with the
+hypothesis of an internal transformation of a hexose to a
+pentose-monoformal. Such a change of position and function of oxygen
+from OH to CO within the group --CH.OH-- is a species of internal
+oxidation which reverses the reduction of formaldehyde groups in
+synthesising to sugars, and appears therefore of probable occurrence.
+
+These constitutional problems are followed up in (3) by the indirect
+method of differentiating the relationships of these furfuroids to yeast
+fermentation, from those of the pentoses. Straw and esparto celluloses
+are subjected to the processes of acid hydrolysis, and the neutralised
+extracts fermented. With high furfural numbers indicating that the
+furfuroids are the chief constituents of the extract, there is an active
+fermentation with production of alcohol. The cupric reduction falls in
+greater ratio to the original (unfermented) than the furfural.
+Observations on the pure pentoses--xylose and arabinose added to
+dextrose solutions, and then exposed to yeast action--show that in a
+vigorous fermentation not unduly prolonged the pentoses are unaffected,
+but that they do come within the influence of the yeast-cell when the
+latter is in a less vigorous condition, and when the hexoses are not
+present in relatively large proportion.
+
+(4) The observations on the growing plant were resumed with the view of
+artificially increasing the differentiation of the two main groups of
+carbohydrates. From a portion of a barley crop the inflorescence was
+removed as soon as it appeared. The crop was allowed to mature, and a
+full comparison instituted between the products of normal and abnormal
+growth. With a considerable difference in 'permanent tissue' (13 p.ct.
+less) and a still greater defect in cellulose (24 p.ct.), the constants
+for the furfuroids in relation to total carbohydrates were unaffected by
+the arrested development. This was also true of the behaviour of the
+hydrolysed extracts (acid processes) to yeast fermentation.
+
+(5) The extract obtained from the brewers' grains by the process
+described in (2) was investigated in relation to animal digestion. It
+has been now generally established that the furfuroids as constituents
+of fodder plants are digested and assimilated in large proportion in
+passing through animal digestive tracts, and in this respect behave
+differently from the pentoses. The furfuroids being obtained, as
+described, in a fully hydrolysed condition (monoses) the digestion
+problem presented itself in a new aspect, and was therefore attacked.
+
+The result of the comparative feeding experiments upon rabbits was to
+show that in this previously hydrolysed form the furfuroids are almost
+entirely digested and assimilated, no pentoses, moreover, appearing in
+the urine.
+
+Generally we may sum up the present solution of the problem of the
+relationship of the furfuroids to plant assimilation and growth as
+follows:--The pentoses are not produced as such in the process of
+assimilation; but furfural-yielding carbohydrates are produced directly
+and in approximately constant ratio to the total carbohydrates; they are
+mainly located in the permanent tissue; in the secondary changes of
+dehydration, &c., accompanying maturation they undergo such
+differentiation that they become readily separable by processes of acid
+hydrolysis from the more resistant normal celluloses; but in relation to
+alkaline treatments they maintain their intimate union with the latter.
+They are finally converted into pentoses by artificial treatments, and
+into pentosanes in the plant, with loss of 1 C atom in an oxidised form.
+The mechanism of this transformation of hexoses into pentoses is not
+cleared up. It is independent of external conditions, e.g.
+fertilisation and atmospheric oxidations, and is probably therefore a
+process of internal rearrangement of the character of an oxidation.
+
+
+ZUR KENNTNISS DER IN DEN MEMBRANEN DER PILZE ENTHALTENEN BESTANDTHEILE.
+
+E. WINTERSTEIN (Ztschr. Physiol. Chem., 1894, 521; 1895, 134).
+
+~ON THE CONSTITUENTS OF THE TISSUE OF FUNGI.~
+
+(p. 87) These two communications are a contribution of fundamental
+importance, and may be regarded as placing the question of the
+composition of the celluloses of these lowest types on a basis of
+well-defined fact. In the first place the author gives an exhaustive
+bibliography, beginning with the researches of Braconnot (1811), who
+regarded the cellular tissue of these organisms as a specialised
+substance, which he termed 'fungin.' Payen rejects this view, and
+regards the tissue, fully purified by the action of solvents, as a
+cellulose (C_{6}H_{10}O_{5}). This view is successively supported by
+Fromberg [Mulder, Allg. Phys. Chem., Braunschweig, 1851], Schlossberger
+and Doepping [Annalen, 52, 106], and Kaiser. De Bary, on a review of the
+evidence, adopts this view, but, as the purified substance fails to give
+the characteristic colour-reactions with iodine, he uses the qualifying
+term 'pilzcellulose' [Morph. u. Biol. d. Pilze u. Flechten, Leipzig,
+1884].
+
+C. Richter, on the other hand, shows that these reactions are merely a
+question of methods of purification or preparation [Sitzungsber. Acad.
+Wien, 82, 1, 494], and considers that the tissue-substance is an
+ordinary cellulose, with the ordinary reactions masked by the presence
+of impurities. In regard to the lower types of fungoid growth, such as
+yeast, the results of investigators are more at variance. The researches
+of Salkowski (p. 113) leave little doubt, however, that the
+cell-membrane is of the cellulosic type.
+
+The author's researches extend over a typical range of products obtained
+from _Boletus edulis, Agaricus campestris, Cantharellus cibarius,
+Morchella esculenta, Polyporus officinalis, Penicillium glaucum_, and
+certain undetermined species. The method of purification consisted
+mainly in (a) exhaustive treatments with ether and boiling alcohol,
+(b) digestion with alkaline hydrate (1-2 p.ct. NaOH) in the cold,
+(c) acid hydrolysis (2-3 p.ct. H_{2}SO_{4}) at 95 deg.-100 deg., followed by a
+chloroxidation treatment by the processes of Schulze or Hoffmeister, and
+final alkaline hydrolysis.
+
+The products, i.e. residues, thus obtained were different in essential
+points from the celluloses isolated from the tissues of phanerogams
+similarly treated. Only in exceptional cases do they give blue reactions
+with iodine in presence of zinc chloride or sulphuric acid. The
+colourations are brown to red. They resist the action of cuprammonium
+solutions. They are for the most part soluble in alkaline hydrate
+solution (5-10 p.ct. NaOH) in the cold. They give small yields (1-2
+p.ct.) of furfural on boiling with 10 p.ct. HCl.Aq.
+
+Elementary analyses gave the following results, which are important in
+establishing the presence of a notable proportion of nitrogen, which has
+certainly been overlooked by the earlier observers:--
+
+ _________________________________________________________
+|                                      |      |     |     |
+|     'Cellulose' or residue from      |  C   |  H  |  N  |
+|______________________________________|______|_____|_____|
+|                                      |      |     |     |
+| Boletus edulis (Schulze process)     | 42.4 | 6.5 | 3.9 |
+| Boletus edulis (Hoffmeister process) | 44.6 | 6.3 | 3.6 |
+| Polyporus off.                       | 43.7 | 6.5 | 0.7 |
+| Cantharellus cib.                    | 44.9 | 6.8 | 3.0 |
+| Agaricus campestris                  | 44.3 | 6.6 | 3.6 |
+| Botrytis                             | 42.1 | 6.3 | 3.9 |
+| Penicillium glaucum                  |      |     | 3.3 |
+| Morchella esculenta                  |      |     | 2.5 |
+|______________________________________|______|_____|_____|
+
+It is next shown that this residual nitrogen is not in the form of
+residual proteids (1) by direct tests, all of which gave negative
+results, and (2) indirectly by the high degree of resistance to both
+alkaline and acid hydrolysis. The 'celluloses' are attacked by boiling
+dilute acids (1 p.ct. H_{2}SO_{4}), losing in weight from 10 to 23
+p.ct., the dissolved products having a cupric reduction value about 50
+p.ct. that of an equal weight of dextrose. As an extreme hydrolytic
+treatment the products were dissolved in 70 p.ct. H_{2}SO_{4}, allowed
+to stand 24 hours, then considerably diluted (to 3 p.ct. H_{2}SO_{4})
+and boiled to complete the inversion. The yields of glucose, calculated
+from the cupric reduction, were as follows:--
+
+     Boletus edulis       65.2 p.ct.
+     Polyporus off.       94.7   "
+     Agaricus campestris  59.1   "
+     Morchella esculenta  60.1   "
+     Cantharellus cib.    64.9   "
+     Botrytis             60.8   "
+
+It will be noted that the exceptionally high yield from the Polyporus
+cellulose is correlated with its exceptionally low nitrogen. By actual
+isolation of a crystalline dextrorotary sugar, by preparations of
+osazone and conversion into saccharic acid, it was proved that dextrose
+was the main product of hydrolysis. The second main product was shown to
+be acetic acid, the yield of which amounted to 8 p.ct. in several cases.
+
+Generally, therefore, it is proved that the more resistant tissue
+constituents of the fungi are not cellulose, but a complex of
+carbohydrates and nitrogenous groups in combination, the former being
+resolved into glucoses by acid hydrolysis, and the latter yielding
+acetic acid as a characteristic product of resolution together with the
+nitrogenous groups in the form of an uncrystallisable syrup.
+
+In the further prosecution of these investigations (2) the author
+proceeded from the supposition of the identity of the nitrogenous
+complex of the original with chitin, and adopted the method of
+Ledderhose (Ztschr. Physiol. Chem. 2, 213) for the isolation of
+glucosamin hydrochloride, which he succeeded in obtaining in the
+crystalline form. In the meantime E. Gilson had shown that these tissue
+substances in 'fusion' with alkaline hydrates yield a residue of a
+nitrogenous product (C_{14}H_{28}N_{2}O_{10}), which is soluble in
+dilute acids [Recherches Chim. sur la Membrane Cellulaire des
+Champignons, La Cellule, v. II, pt. 1]. This residue, which was termed
+mycosin by Gilson, has been similarly isolated by the author. It is
+proved, therefore, that the tissues of the fungi do contain a product
+resembling chitin. [See also Gilson, Compt. Rend. 120, 1000.] This
+constituent is in intimate union with the carbohydrate complex, which is
+resolved similarly to the hemicelluloses. Various intermediate terms of
+the hydrolytic series have been isolated. But the only fully identified
+product of resolution is the dextrose which finally results.
+
+
+UEBER DIE KOHLENHYDRATE D. HEFE.
+
+E. SALKOWSKI (Berl. Ber., 27, 3325).
+
+~ON THE CARBOHYDRATES OF YEAST.~
+
+The author has isolated the more resistant constituents of the
+cell-membrane by boiling with dilute alkalis, and exhaustively purifying
+with alcohol and ether.
+
+The residue was only a small percentage (3-4 p.ct) of the original, and
+retained only 0.45 p.ct. N.
+
+It was heated in a digester with water at 2-3 atm. steam-pressure, and
+thus resolved into approximately equal portions of soluble cellulose
+(a) and insoluble (b). The latter, giving no colour-reaction with
+iodine, is termed achroocellulose; the former reacts, and is therefore
+termed erythrocellulose. The former is easily separated from its
+opalescent solution. It has the empirical composition of cellulose. In
+the soluble form it resembles glycogen. The achroocellulose is isolated
+in the form of horny or agglomerated masses. It appears to be resolved
+by ultimate hydrolysis into dextrose and mannose.
+
+
+
+
+SECTION V. FURFUROIDS, i.e. PENTOSANES AND FURFURAL-YIELDING
+CONSTITUENTS GENERALLY
+
+
+(1) ~Reactions of the Carbohydrates with Hydrogen Peroxide.~
+
+C. F. CROSS, E. J. BEVAN, and CLAUD SMITH (J. Chem. Soc., 1898, 463).
+
+
+(2) ~Action of Hydrogen Peroxide on Carbohydrates in the Presence of
+Ferrous Salts.~
+
+R. S. MORRELL and J. M. CROFTS (J. Chem. Soc., 1899, 786).
+
+
+(3) ~Oxidation of Furfuraldehyde by Hydrogen Peroxide.~
+
+C. F. CROSS, E. J. BEVAN, and T. HEIBERG (J. Ch. Soc., 1899, 747).
+
+
+(4) EINWIRKUNG VON WASSERSTOFFHYPEROXID AUF UNGESAeTTIGTE
+KOHLENWASSERSTOFFE.
+
+C. F. CROSS, E. J. BEVAN, and T. HEIBERG (Berl. Ber., 1900, 2015).
+
+~ACTION OF HYDROGEN PEROXIDE ON UNSATURATED HYDROCARBONS.~
+
+The above series of researches grew out of the observations incidental
+to the use of the peroxide on an oxidising agent in investigating the
+hydrolysed furfuroids (102). Certain remarkable observations had
+previously been made by H. J. H. Fenton (Ch. Soc. J., 1894, 899; 1895,
+774; 1896, 546) on the oxidation of tartaric acid by the peroxide,
+acting in presence of ferrous salts, the --CHOH--CHOH-- residue losing
+H_{2} with production of the unsaturated group, --OH.C=C.OH--. These
+investigations have subsequently been considerably developed and
+generalised by Fenton, but as the results have no immediate bearing on
+our main subject we must refer readers to the J. Chem. Soc., 1896-1900.
+
+From the mode of action diagnosed by Fenton it was to be expected that
+the CHOH groups of the carbohydrates would be oxidised to CO groups, and
+it has been established by the above investigations (1) and (2) that the
+particular group to be so affected in the hexoses is that contiguous to
+the typical
+
+        |
+     --CO
+
+group. There results, therefore, a dicarbonyl derivative ('osone'),
+which reacts directly with 2 mol. phenyl hydrazine in the cold to form
+an osazone. This was directly established for glucose, laevulose,
+galactose, and arabinose (2). While this is the main result, the general
+study of the product shows that the oxidation is not simple nor in
+direct quantitative relationship to the H_{2}O_{2} employed. The
+molecular proportion of the aldoses affected appears to be in
+considerable excess, and the reaction is probably complicated by
+interior rearrangement.
+
+In the main, the original aldehydic group resists the oxidation. But a
+certain proportion of acid products are formed, probably tartronic acid.
+On distillation with condensing acids a large proportion of volatile
+monobasic acids (chiefly formic) are obtained. The proportion of
+furfural obtained amounts to 3-4 per cent. of the weight of the original
+carbohydrate.
+
+Since the general result of these oxidations is the substitution of an
+OH group for an H atom, it was of interest to determine the behaviour of
+furfural with the peroxide. The oxidation was carried out in dilute
+aqueous solution of the aldehyde at 20 deg.-40 deg., using 2-3 mols. H_{2}O_{2}
+per 1 mol. C_{5}H_{4}O_{2}. The main product is a hydroxyfurfural, which
+was separated as a hydrazone. A small quantity of a monobasic acid was
+formed, which was identified as a hydroxypyromucic acid. Both aldehyde
+and acid appear to be the alpha beta derivatives. The aldehyde gives
+very characteristic colour reactions with phloroglucinol and resorcinol
+in presence of hydrochloric acid, which so closely resemble those of the
+lignocelluloses that there is little doubt that these particular
+reactions must be referred to the presence of the hydroxyfurfural as a
+normal constituent.
+
+The study of these oxidations was then extended to typical unsaturated
+hydrocarbons--viz. acetylene and benzene. (4) From the former the main
+product was acetic acid, but the attendant formation of traces of ethyl
+alcohol indicates that the hydrogen of the peroxide may take a direct
+part in this and other reactions. This view receives some support from
+the fact that the interaction of the H_{2}O_{2} with permanganates has
+now been established to be an oxidation of the H_{2} of the peroxide by
+the permanganate oxidation, with liberation, therefore, of the O_{2} of
+the peroxide as an unresolved molecule [Baeyer].
+
+Benzene itself is also powerfully attacked by the peroxide when shaken
+with a dilute solution in presence of iron salts. The products are
+phenol and pyrocatechol, with some quantity of an amorphous product
+probably formed by condensation of a quinone with the phenolic products
+of reaction.
+
+       *       *       *       *       *
+
+These types of oxidation effects now established give a definite
+significance to the physiological functions of the peroxide, which is a
+form of 'active oxygen' of extremely wide distribution. It would have
+been difficult _a priori_ to devise an oxidant without sensible action
+on aldehydic groups, yet delivering a powerful attack on hydrocarbon
+rings; or to have suggested a synthesis of the sugars from tartaric acid
+with a powerful oxidising treatment as the first and essential stage in
+the transformation.
+
+Our present knowledge of such actions and effects suggests a number of
+new clues to genetic relationships of carbon compounds within the plant.
+The conclusion is certainly justified that the origin of the pentoses is
+referable to oxidations of the hexoses, in which this form of 'active
+oxygen' plays an important part.
+
+We must note here the researches of O. Ruff, who has applied these
+oxidations with important results in the systematic investigation of the
+carbohydrates.
+
+
+UEBER DIE VERWANDLUNG DER _D_-GLUCONSAeURE IN _D_-ARABINOSE (Berl. Ber.,
+1898, 1573).
+
+~CONVERSION OF _D_-GLUCONIC ACID INTO _D_-ARABINOSE.~
+
+       *       *       *       *       *
+
+_D_ UND _L_ ARABINOSE (_Ibid._ 1899, 550).
+
+       *       *       *       *       *
+
+ZUR KENNTNISS DER OXYGLUCONSAeURE (_Ibid._ 1899, 2269).
+
+~ON OXYGLUCONIC ACID.~
+
+Ruff in these researches has realised a simple and direct transition
+from the hexoses to the pentoses. By oxidising gluconic acid with the
+peroxide the beta --CHOH-- group is converted into carbonyl at the same
+time that the terminal COOH [alpha] is oxidised to CO_{2}. The yields of
+the resulting pentose are large. Simultaneously there is formed an
+oxygluconic acid, which appears to be a ketonic acid of formula
+--CH_{2}OH.CO.(CHOH)_{3}.COOH--.
+
+From these results we see a further range of physiological
+probabilities; and with the concurrent actions of oxygen in the forms of
+or related to hydrogen peroxide on the one side, and ozone on the other,
+we are able to account in a simple way for the relationships of the
+'furfuroid' group, which may include a number of intermediate terms in
+the hexose-pentose series.
+
+Following in this direction of development of the subject is a study of
+the action of persulphuric acid upon furfural.
+
+
+EINWIRKUNG DES CARO'SCHEN REAGENS AUF FURFURAL.
+
+C. F. CROSS, E. J. BEVAN, and J. F. BRIGGS (Berl. Ber., 1900, 3132).
+
+Regarding this reagent as another form of 'active oxygen,' it is
+important to contrast its actions with those of the hydrogen peroxide.
+Instead of the beta-hydroxyfurfural (_ante_, 115) we obtain the
+delta-aldehyde as the first product. The aldehydic group is then
+oxidised, and as a result of attendant hydrolysis the ring is broken
+down and succinic acid is formed, the original aldehydic group of the
+furfural being split off in the form of formic acid. The reactions take
+place at the ordinary temperature and with the dilute form of the
+reagent described by Baeyer and Villiger (Ber. 32, 3625). These results
+have some special features of interest. The alpha delta-hydroxyfurfural
+has similar colour reactions to those of the alpha beta-derivative, and
+may also therefore be present as a constituent of the lignocelluloses.
+The tendency to attack in the 1.4 position in relation to an aldehydic
+group further widens the capabilities of 'active oxygen' in the plant
+cell. Lastly, this is the simplest transition yet disclosed from the
+succinyl to furfural grouping, being effected by a regulated proportion
+of oxygen, and under conditions of reaction which may be described as of
+the mildest. In regard to the wide-reaching functions of asparagin in
+plant life, we have a new suggestion of genetic connections with the
+furfuroids.
+
+
+VERGLEICH DER PENTOSEN-BESTIMMUNGSMETHODEN VERMITTELST PHENYLHYDRAZIN
+UND PHLOROGLUCIN.
+
+M. KRUeGER (Inaug.-Diss., Goettingen, 1895).
+
+~COMPARISON OF METHODS OF ESTIMATING FURFURAL AS HYDRAZONE AND
+PHLOROGLUCIDE.~
+
+The author traces the development of processes of estimating furfural
+(1) by precipitation with ammonia (furfuramide), (2) by volumetric
+estimation with standardised phenylhydrazine, (3) by weighing the
+hydrazone.
+
+In 1893 (Chem. Ztg. 17, 1745) Hotter described a method of quantitative
+condensation with pyrogallol requiring a temperature of 100 deg.-110 deg. for
+two hours. The insoluble product collected, washed, dried at 103 deg., and
+weighed, gives a weight of 1.974 grm. per 1 grm. furfural.
+
+Councler substitutes phloroglucinol for pyrogallol, with the advantage
+of doing away with the digestion at high temperature. (_Ibid._ 18, 966.)
+This process, requiring the presence of strong HCl, has the advantage of
+being applied directly to the acid distillate, in which form furfural is
+obtained as a product of condensation of pentoses, &c. A comparative
+investigation was made, precipitating furfural (a) as hydrazone in
+presence of acetic acid, and (b) as phloroglucide in presence of HCl
+(12 p.ct). In (a) by varying the weights of known quantities of
+furfural, and using the factor, hydrazone x 0.516 [+ 0.0104] in
+calculating from the weights of precipitates obtained, the maximum
+variations from the theoretical number were +1.71 and -1.74. In (b) it
+was found necessary to vary the factor from 0.52 to 0.55 in calculating
+from phloroglucide to furfural. The greatest _total_ range of variation
+was found to be 2.5 p.ct. The phenol process is therefore equally
+accurate, has the advantages above noted, and, in addition, is less
+liable to error from the pressure in the distillates obtained from
+vegetable substances of volatile products, e.g. ketonic compounds,
+accompanying the furfural.
+
+This method has been criticised by Helbel and Zeisel [Sitz.-ber, Wiener
+Akad. 1895, 104, ii. p. 335] on two grounds of error, viz. (1) the
+presence of diresorcinol in all ordinary preparations of phloroglucinol,
+and (2) changes in weight of the precipitate of phloroglucide on drying.
+The process was carried out comparatively with ordinary preparations,
+and with specially pure preparations of the phenol. The quantitative
+results were identical. The criticisms in question are therefore
+dismissed. Although the process is to be recommended for its simplicity
+and the satisfactory concordance of results it is to be noted that it
+rests upon an empirical basis, since the phloroglucide is not formed by
+the simple reaction 2 [C_{5}H_{4}O_{2} + C_{6}H_{6}O_{3}] - H_{2}O =
+C_{22}H_{18}O_{9}, but appears to have the composition
+C_{16}H_{12}O_{6}.
+
+In part ii. of this paper the author discusses the question of the
+probable extent in the sense of diversity of constitution of
+furfural-yielding constituents of plant-tissues. Glucoson was isolated
+from glucosazon, and found to yield 2.9-3.6 p.ct. furfural. Gluconic
+acid distilled with hydrochloric acid gave traces of furfural; so also
+with sulphuric acid and manganic oxide.
+
+Starch was oxidised with permanganate, and a mixture of products
+obtained of which one gave a characteristic violet colouration with
+phloroglucol, with an absorption-band at the D line. On distilling with
+HCl furfural was obtained in some quantity. The product in question was
+found to be very sensitive to the action of bases, and was destroyed by
+the incidental operation of neutralising the mixture of oxidised
+products with calcium carbonate. It was found impossible to isolate the
+compound.
+
+
+UNTERSUCHUNGEN UEBER DIE PENTOSANBESTIMMUNG MITTELST DER
+SALZSAeURE-PHLORO-GLUCIN-METHODE.[8]
+
+E. KROeBER (Journ. f. Landwirthschaft, 1901, 357).
+
+~INVESTIGATION OF THE HYDROCHLORIC ACID-PHLOROGLUCINOL METHOD OF
+DETERMINING PENTOSANES.~
+
+This paper is the most complete investigation yet published of the now
+well-known method of precipitating and estimating furfural in acid
+solution by means of the trihydric phenol. In the last section of the
+paper is contained the most important result, the proof that the
+insoluble phloroglucide is formed according to the reaction
+
+     C_{5}H_{4}O_{2} + C_{6}H_{6}O_{3} - 2H_{2}O = C_{11}H_{6}O_{3},
+
+also, by varying the proportions of the pure reagents interacting, that
+the condensation takes place invariably according to this equation.
+
+Incidentally the following points were also established:--The solubility
+of the phloroglucide, under the conditions of finally separating in a
+condition for drying and weighing, is 1 mgr. per 100 c.c. of total
+solution, made up of the original acid solution, in which the
+precipitation takes place, and the wash-water required to purify from
+the acid. The phloroglucide is hygroscopic, and must be weighed out of
+contact with the air. The presence of diresorcinol is without influence
+on the result, provided a sufficient excess of actual phloroglucinol is
+employed. Thus even with a preparation containing 30 p.ct. of its weight
+of diresorcinol the influence of the latter is eliminated, provided a
+weight be taken equal to twice that of the furfural to be precipitated.
+The phenol must be perfectly dissolved by warming with dilute HCl (1.06
+sp.gr.) before adding to the furfural solution. For collecting the
+precipitate of phloroglucide the author employs the Gooch crucible.
+
+The paper contains a large number of quantitative results in proof of
+the various points established, and concludes with elaborate tables,
+giving the equivalents in the known pentoses and their anhydrides for
+any given weight of phloroglucide from 0.050 to 0.300 grm.
+
+
+UEBER DEN PENTOSAN-GEHALT VERSCHIEDENER MATERIALIEN.
+
+B. TOLLENS and H. GLAUBITZ (J. fuer Landwirthschaft, 1897, 97).
+
+~ON THE PENTOSANE CONSTITUENTS OF FODDER-PLANTS AND MALT.~
+
+(p. 171) (a) The authors have re-determined the yield of furfural from
+a large range of plant-products, using the phloroglucol method. The
+numbers approximate closely to those obtained by the hydrazone method.
+The following may be cited as typical:
+
+     Substance              Furfural p.ct.
+
+     Rye (Goettingen)            6.03
+     Wheat (square head)        4.75
+     Barley (peacock)           4.33
+     Oats (Goettingen)           7.72
+     Maize (American)           3.17
+     Meadow hay                11.63
+     Bran (wheat)              13.06
+     Malt                       6.07
+     Malt-sprouts               8.56
+     Sugar-beet (exhausted)    14.95
+
+(b) A comparison of wheat with wheat bran, &c. was made by grinding in
+a mortar and 'bolting' the flour through a fine silk sieve. The results
+showed:
+
+                              Furfural p.ct.
+     Original wheat               4.75
+     Fine flour                   1.73
+     Bran (24 p.ct. of wheat)    11.25
+     Wheat-bran of commerce      13.06
+
+It is evident that the pentosanes of wheat are localised in the more
+resistant tissues of the grain.
+
+(c) An investigation of the products obtained in the analytical
+process for 'crude fibre' gave the following:
+
+(1) In the case of brewers' grains:
+
+     100 grms. grains       gave furfural   = 29.43 pentosane
+                                              ---------------
+      20   "   crude fibre       "          =  2.52
+     Acid extract                "          = 22.76
+     Alkali  "                   "          =  1.20
+     Deficiency from total of original grains  2.95
+                                              -----
+
+                                              29.43
+
+(2) In the case of meadow hay:
+
+The crude fibre (30 p.ct.) obtained retained about one fourth (23.63
+p.ct.) of the total original pentosanes.
+
+(d) An investigation of barley-malt, malt-extract or wort, and
+finished beer showed the following: An increase of furfuroids in the
+process of malting, 100 pts. barley with 7.97 of 'pentosane' yielding 82
+of malt with 11.18 p.ct. 'pentosane'; confirming the observations of
+Cross and Bevan (Ber. 28, 2604). Of the total furfuroids of malt about
+1/4 are dissolved in the mashing process. In a fermentation for lager
+beer it was found that about /10 of the total furfuroids of the malt
+finally survive in the beer; the yield of furfural being 2.92 p.ct. of
+the 'total solids' of the beer. In a 'Schlempe' or 'pot ale,' from a
+distillery using to 1 part malt 4 parts raw grain (rye), yield of
+furfural was 9 p.ct. of the total solids.
+
+In a general review of the relationships of this group of plant-products
+it is pointed out that they are largely digested by animals, and
+probably have an equal 'assimilation' value to starch. They resist
+alcoholic fermentation, and must consequently be taken into account as
+constituents of beers and wines.
+
+
+UEBER DAS VERHALTEN DER PENTOSANE DER SAMEN BEIM KEIMEN.[9]
+
+A. SCHOeNE and B. TOLLENS (Jour. f. Landwirthschaft, 1901, 349).
+
+~BEHAVIOUR OF PENTOSANES OF SEEDS IN GERMINATION.~
+
+The authors have investigated the germination of barley, wheat, and
+peas, in absence of light, and generally with exclusion of assimilating
+activity, to determine whether the oxidation with attendant loss of
+weight, which is the main chemical feature of the germination proper,
+affects the pentosanes of the seeds. The following are typical of the
+quantitative results obtained, which are stated in absolute weights, and
+not percentages.
+
+ _____________________________________________________________
+|        |               |                    |               |
+|        | Original seed |      Malt or       | Pentosane in  |
+|        |               | germinated product |               |
+|        |               |                    |_______________|
+|        |               |                    |       |       |
+|        |      A        |         B          |   A   |   B   |
+|________|_______________|____________________|_______|_______|
+|        |               |                    |       |       |
+| Barley |    500.00     |       434.88       | 39.58 | 40.38 |
+|   "    |    500.00     |       442.26       | 40.52 | 41.17 |
+| Peas   |    300.00     |       286.60       | 15.25 | 15.97 |
+|________|_______________|____________________|_______|_______|
+
+The authors conclude generally that there is a slight absolute increase
+in the pentosanes, and that the pentosanes do not belong to those
+reserve materials which undergo destructive oxidation during
+germination.
+
+In this they confirm the previously published results of De Chalmot,
+Cross and Bevan, and Gotze and Pfeiffer.
+
+
+UEBER DEN GEHALT DER BAUMWOLLE AN PENTOSAN.
+
+H. SURINGAR and B. TOLLENS (Ztschr. angew. Chem., 1897, I).
+
+~PENTOSANE CONSTITUENTS OF COTTON.~
+
+(p. 290) It has been stated by Link and Voswinkel (Pharm. Centralhalle,
+1893, 253), that raw cotton yields 'wood gum' as a product of
+hydrolysis. The authors were unable to obtain any pentoses as products
+of acid hydrolysis of raw cotton, and traces only of furfural-yielding
+carbohydrates. They conclude that raw cotton contains no appreciable
+quantity of pentosane.
+
+FOOTNOTES:
+
+[8] This paper appears during the printing of the author's original MS.
+
+[9] This paper appears during the printing of the author's original MS.
+
+
+
+
+SECTION VI. THE LIGNOCELLULOSES
+
+
+(p. 131) ~Lignocellulose Esters.~--By a fuller study of the ester
+reactions of the normal celluloses we have been able to throw some light
+on the constitutional problems involved; and we have extended the
+investigations to the jute fibre as a type of the lignocelluloses, from
+the results of which we get a clearer idea of the relationships of the
+constituent groups.
+
+Taking the empirical expression for the complex, i.e. the entire
+lignocellulose, the formula C_{12}H_{18}O_{9}, we shall be able to
+compare the ester derivatives with those of the celluloses, which we
+have also referred to a C_{12} unit. But we shall require also to deal
+with the constituent groups of the complex, which for the purposes of
+this discussion may be regarded as (a) a cellulose of normal
+characteristics--cellulose alpha; (b) a cellulose yielding furfural on
+boiling with condensing acids--cellulose beta; and (c) a much
+condensed, and in part benzenoid, group which we may continue to term
+the lig_none_ group.
+
+The latter has been specially examined with regard to its proportion of
+OH groups, as a necessary preliminary to the investigation of esters, in
+producing which the entire complex is employed. It will be shown that
+the ester groups can be actually localised in various ways, as in the
+main entering the cellulose residues alpha and beta. But that the
+lignone group takes little part in the reactions may be generally
+concluded on the evidence of its non-reactivity as an isolated
+derivative, (1) By chlorination, &c. it is isolated in the form of an
+amorphous body, but of constant composition, represented by the formula
+C_{19}H_{18}Cl_{4}O_{9}. This compound, soluble in acetic anhydride, was
+boiled with it for six hours after adding fused sodium acetate, and the
+product separated by pouring into water. The dilute acid filtered from
+the product contained no hydrochloric acid nor by-products of action.
+The product showed an increase of weight of 7.5 p.ct. For one acetyl per
+1 mol. C_{19}H_{18}Cl_{4}O the calculated increase is 8.0 p.ct. It is
+evident from the nature of the derivative that this result cannot be
+further verified by the usual analytical methods. (2) The chlorinated
+derivative is entirely soluble in sodium sulphite solution. This
+solution, shaken with benzoyl chloride, with addition of sodium hydrate
+in successive portions, shows only a small formation of insoluble
+benzoate, which separates as a tarry precipitate. (3) The empirical
+formula of the lignone complex in its isolated forms indicates that very
+little hydrolysis occurs in the processes of isolation. Thus the
+chlorinated product we may assume to be derived from the complex
+C_{19}H_{22}O_{9}. In the soluble by-products from the bisulphite
+processes of pulping wood the lignone exists as a sulphonated
+derivative, C_{24}H_{23}(OCH_{3})_{2}.(SO_{3}H).O_{7}. The original
+lignone may be regarded as passing into solution as a still condensed
+complex derived from C_{24}H_{26}O_{12} (Tollens). There is evidently
+little attendant hydroxylation, and another essential feature is the
+small molecular proportion of groups showing the typical sulphonation.
+
+It appears that in the lignone the elements are approximately in the
+relation C_{6} : H_{6} : O_{3}, and it may assist this discussion to
+formulate the main constitutional types consistent with this ratio,
+viz.:
+
+     (1) The trihydroxybenzenes C_{6}H_{3}(OH)_{3}.
+
+     (2) Methylhydroxyfurfural C_{5}H_{2}O.(OH)(CH_{3}).
+
+                                  (CH_{3})
+                                 /        \
+     (3) Methylhydroxypyrone CO<C_{4}H_{2} O
+                                 \        /
+                                    (OH)
+
+                             __________________
+                            |                  |
+     (4) Trioxycyclohexane CH--CH--CH--CH--CH--CH
+                            \   /   \   /   \   /
+                              O       O       O
+
+It is probable that all these types of condensation are represented in
+the lignone molecules, since the derivatives yielded in decompositions
+of more or less regulated character are either directly derived from or
+related to such groups. For the moment we pass over all but the general
+fact of complexity and the marked paucity of OH-groups. It would be of
+importance to be able to formulate the exact mode of union of the
+lignone with the cellulose residues to constitute the lignocellulose.
+The evidence, however, does not carry us farther than the probability of
+union by complicated groups and of large dimensions; for not only is the
+lignone isolated in condensed and non-hydroxylated forms, but the
+cellulose also is not hydrated or hydrolysed further than in the ratio
+3C_{6}H_{10}O_{5}.H_{2}O. It is probable, therefore, that the water
+combining with the residues at the moment of their resolution is
+relatively small.
+
+Lastly, we have to remember, when dealing with the statistical results
+of the reactions to be described, that the approximate proportions per
+cent. of the constituent groups are:
+
+     Cellulose alpha  65
+          "    beta   15  =  100 lignocellulose.
+     Lignone                  20
+
+~Jute Benzoates.~--In preparing the jute for treatment it was boiled in
+alkaline solution (1 per cent. NaOH), washed with water and dilute acid,
+again washed, dried, and weighed.
+
+In the ester reaction the reagents were employed in the proportion
+C_{12}H_{18}O_{9} : 3NaOH : 2C_{6}H_{5}COCl. A series of quantitative
+experiments gave yields of 126-130 p.ct. of benzoate [calculated for
+monobenzoate 134 p.ct.].
+
+The results were confirmed by ultimate analysis. The monobenzoate
+therefore represents a maximum, and this molecular proportion is
+one-half of that observed with the normal cellulose, calculated to the
+same unit.
+
+_Localisation of Benzoyl Group._--The entrance of the ester group
+affects the typical colour reactions of the lignocellulose, which are
+fainter. The ferric ferricyanide reaction almost disappears. The lignone
+group is unaffected, and combines with chlorine as in the original. The
+lignone chloride is removed by sodium sulphite solution, and the residue
+is a _cellulose benzoate_. The loss of weight due to the elimination of
+the lignone was 12.7 p.ct. Calculating per 100 of the original
+lignocellulose this becomes 16. These statistics further confirm the
+localisation of the benzoyl group in the cellulose residue. It is to be
+noted that the presence of the benzoyl group renders the cellulose more
+resistant to hydrolytic actions. Thus, to bring out this fact more
+prominently, we may calculate the yield of residual cellulose benzoate
+p.ct. of original jute, and we find it 109 p.ct. Taking a maximum
+proportion for original cellulose--viz. 85--this benzoate represents a
+yield of 129 p.ct., as against the theoretical for a monobenzoate, 132
+p.ct.
+
+_Furfural Numbers._--The percentage of furfural obtained by boiling with
+HCl of 1.06 sp.gr. was 3.02 and 3.29 in separate determinations.
+Calculating to the original lignocellulose, the percentage, 4.21,
+indicates a considerable loss of the furfural-yielding constituent. The
+effect was also apparent in the cellulose (benzoate) isolated by
+chlorination &c., the percentage being 1.39 p.ct., and calculated to the
+original jute benzoate 1.59 p.ct. Under the conditions adopted in
+dissolving away the chlorinated lignone the original non-benzoated
+lignocellulose would have yielded a cellulose giving 6 to 7 p.ct.
+furfural.
+
+Since the benzoyl group is hardly calculated to produce a constitutional
+change affecting the furfural constants, it was necessary to examine the
+effect of the preliminary alkaline treatment, and the change in the
+furfuroid group was in fact localised in this reaction. It was found
+that, on washing the alkali from the mercerised jute, and further
+purifying the residue, this latter yielded only 4.2 p.ct. furfural [3.4
+p.ct. on original fibre]. The alkaline solution and washings were
+acidified and distilled from 10 p.ct. HCl, yielding an additional 3.6
+p.ct. calculated to the original lignocellulose. By treatment with the
+concentrated alkali, therefore, the furfuroid of the original
+lignocellulose undergoes little change, but is selectively dissolved.
+This point is under further investigation.
+
+(p. 132) ~Acetylation of Lignocelluloses.~--Acetates are readily formed by
+boiling the lignocelluloses with acetic anhydride. The derivatives
+obtained from jute are only generally mentioned in the 1st edition (p.
+132). A further study of the reactions in regard to special points has
+led to some more definite results. The _yields_ of product by the
+ordinary and simple process are 114-115 p.ct. But on analysing the
+product an important discrepancy is revealed.
+
+For the saponification we employ a solution of sodium ethylate in the
+cold. The following numbers were obtained:
+
+                                       Acetic acid  Hydrocellulose residue
+                                           27.2            77.8
+Calc. for diacetate on C_{12}H_{18}O_{9}   30.8            78.4
+
+The derivative is approximately a diacetate, and on the assumption of a
+simple ester reaction the yield should be 127 p.ct. Assuming that the
+difference of 13 p.ct. is due to loss of water by internal condensation,
+it appears that for each acetyl group entering, 2 mol. H_{2}O are split
+off.
+
+The jute acetate showed the normal reaction with chlorine, and the
+lignone chloride was dissolved by treatment with sodium sulphite
+solution. The fibrous residue was colourless. It proved to be a
+cellulose acetate. The following numbers were obtained on
+saponification:
+
+                                          Acetic acid  Cellulose
+                                              31.6       70.0
+                                              30.9       68.8
+Calc. for diacetate on C_{12}H_{20}O_{10}     29.4       79.9
+
+The interpretation of these numbers appears to be this: in the original
+reaction with the lignocellulose it is the cellulose residue which is
+acetylated, and at the same time condensed. The cellulose residue which
+undergoes condensation is not of the normal constitution, since the
+normal cellulose is acetylated without condensation (see p. 41). On
+saponification a portion of the cellulose, in again combining with
+water, is hydrolysed to soluble products. The lignone group as it exists
+in the lignocellulose has no free OH groups, and probably no free
+aldehydic groups such as would react with the anhydride. Such groups
+may, however, be originally present, and may take part in the internal
+condensations which have been shown to occur. The furfural constants of
+the lignocellulose are unaffected by the acetylation and condensation.
+The hygroscopic moisture of the product is lowered from 10-11 p.ct. in
+the original to 4.5 p.ct. The ferric ferricyanide reaction is inhibited
+by the disappearance of the reactive groups, upon which this curious and
+characteristic phenomenon depends (1st ed.).
+
+~Acetylation of Benzoates.~--The cellulose dibenzoate (C_{12} basis) and
+the jute monobenzoate were acetylated under comparative conditions The
+results were as follows:
+
+                                                   C_{12} basis
+                                   Cellulose dibenzoate     Jute monobenzoate
+                                              Calc. for             Calc. for
+                                 Found     diacetate on  Found   diacetate on
+Ester reaction                              dibenzoate           monobenzoate
+Yield                            111 p.ct.    115 p.ct.  124 p.ct.  120 p.ct.
+
+Saponification  {Cellulose}
+                {Lignocellulose}    53.5        52.6        59.8       61.9
+                 NaOH combining     21.3        23.9        28.4       24.3
+
+From these results it would appear that the number of acetyl groups
+entering the benzoates is the same as with the unbenzoylated fibres, the
+benzoyl has no influence upon the hydroxyls as against the acetyl. At
+the same time the internal condensation noticed in the acetylation of
+the jute appears not to occur in the case of the benzoate.
+
+~Nitric Esters.~--The numbers resulting from the quantitative study of the
+ester reaction and product (1st ed. p. 133) show a very large divergence
+of the yield of product from that which would be calculated from its
+composition (N p.ct.) on the assumption that the ester reaction is
+simple. We have repeated the results, and find with a yield of 145 p.ct.
+that the product contains 11.8 p.ct. N.
+
+The reaction
+
+     C_{12}H_{18}O_{9} + 4HNO_{3} - 4H_{2}O
+
+gives a tetranitrate with 11.5 p.ct. N and a yield of 159 p.ct. The
+ester reaction, therefore, is not simple. There are two sources of the
+loss of weight. The first of these is evident from the occurrence of
+certain secondary reactions which result in the solution of a certain
+proportion of the fibre substance in the acid mixture. To determine this
+quantitatively we have devised a suitable variation of the method of
+combustion with chromic acid (1st ed.).
+
+The variation is required to meet the difficulty occasioned by the
+tension of the nitric acid and products of deoxidation. The mixed acids
+(10 c.c.), containing the organic by-products in solution, are
+carefully diluted in a small flask with an equal volume of water,
+preventing rise of temperature. Nitrous fumes are evolved during the
+dilution. Strong sulphuric acid (15 c.c.) is now added, and the residue
+of nitrous fumes expelled by a current of air, agitating the contents of
+the flask from time to time. The combustion with CrO_{3} is then
+proceeded with in the ordinary way. The gases evolved are measured
+(total volume) and calculated to C present in the form of products
+derived from the lignocellulose; and, assuming that this contains 47
+p.ct. C, we may express the result approximately in terms of the fibre
+substance. The method was controlled by blank experiments, in which
+citric acid was taken as a convenient carbon compound for combustion.
+The C found was 34.9 p.ct. as against 34.3 p.ct. calculated. By this
+method we find that with maximum yields of nitrate at 143-145 p.ct. the
+organic matter in solution in the acid mixture amounted to 4.9 to 5.3
+p.ct. of the original lignocellulose.
+
+Introducing this quantity as a correction of the yield of nitrate in the
+original reaction, we must express the 143 parts as obtained from 95 of
+fibre substance instead of 100.
+
+The yield per molecule C_{12}H_{18}O_{9} (= 306) is therefore 462,
+whereas for a tetranitrate formed by a simple ester reaction the yield
+should be 486. The difference (24) represents 1.5 mol. H_{2}O split off
+by internal condensation.
+
+The correction for total N is relatively small, raising it from 11.5 to
+12.2, which remains in close agreement with the experimental numbers.
+
+_Monobenzoate._--Treated with the acid mixture yields a mixed nitrate.
+The yield is 130 p.ct., and the product contains 7.6 p.ct. O.NO_{2}
+nitrogen. These numbers approximate to those required for reaction with
+4HNO_{3} groups, three of the residues entering the cellulose, and one
+(as NO_{2}) the benzene ring of the substituting group. For such a
+reaction the calculated numbers are: Yield 144 p.ct.; O.NO_{2} nitrogen
+7.1 p.ct.
+
+The experimental numbers require correcting for the amount of loss in
+the form of products soluble in the acid mixture, viz. 7.6 p.ct.; but
+they remain within the range of the experimental errors sufficiently to
+show that the benzoyl group limits the number of OH groups taking part
+in the ester reaction to three. The corrected yield per 1 mol. of jute
+benzoate (410) is 576, as against the calculated 590 for 4HNO_{3}
+reacting. A loss of 1H_{2}O per molecule by internal condensation is
+therefore indicated.
+
+~Denitration.~--The removal of the nitric groups from the esters is
+effected by digestion with ammonium sulphide. But the reactions are by
+no means simple. There is considerable hydrolysis of the lignocellulose
+to soluble products. Thus the _tetranitrate_ yields only 46.4 of
+denitrated fibre in place of the calculated 66. The product is a
+cellulose, yielding only 0.5 per cent. furfural. The hydrolysed
+by-products, moreover, when freed from sulphur and distilled from
+hydrochloric acid, yielded only an additional 2.5 p.ct. furfural,
+calculated to the original lignocellulose.
+
+These statistics confirm the evidence that the ester reaction is not
+simple. Such changes take place in the lignone-beta-cellulose complex
+that they revert, not to their original form, but to soluble derivatives
+of different constitution. The mixed nitrate from the benzoate is
+denitrated to a cellulose amidobenzoate, which confirms the localisation
+of a nitro-group in the benzoyl residue.
+
+(p. 157) ~General Characteristics of the Lignocelluloses.~--Later
+investigations have somewhat modified and simplified our views of the
+constitution of the typical lignocellulose (jute), so far as this can be
+dealt with by the statistics of its more important decompositions
+(original, pp. 157-161).
+
+~Cellulose.~--There is little doubt that the furfural-yielding groups of
+the original are isolated in the form of the beta-cellulose. Tollens
+emphasises this fact in his studies of cellulose-estimation methods. We
+had previously shown (original, p. 159) that the yield of furfural is
+not affected by the _chlorination_, but it appears from our numbers that
+only 50 p.ct. of these groups remain in the isolated cellulose, the
+residue undergoing hydrolysis to soluble compounds. In a carefully
+regulated hydrolysis following the chlorination it appears that the
+furfuroids are almost entirely conserved in the form of a cellulose.
+
+Moreover, an investigation of the products dissolved by sodium sulphite
+solution from the chlorinated fibre has shown that they are practically
+free from furfuroids. This enables us to exclude the furfural-yielding
+groups from the lignone complex. At the same time, through our later
+studies of the hydroxyfurfurals, it is certain that these products are
+represented in the fibre substance and probably in the lignone complex.
+
+~Chlorination Statistics.~--It has been pointed out by a correspondent--to
+whom we express our indebtedness--that we have made a mistake in
+calculating the proportion of lignone from the ratio of the Cl combining
+with the fibre substance or lignocellulose (p.ct), to that of the Cl
+_present in_ the isolated lignone chloride (p.ct.). The lignocellulose
+combines with chlorine in the ratio 100 : 8, but the lignone chloride
+_containing_ 26.7 of chlorine means that, neglecting the hydrogen
+substituted, 73 of lignone combine with the 27 of chlorine
+approximately. On the uniform percentage basis the calculated proportion
+of lignone would be 8/37, or a little over 20 p.ct.
+
+In regard to the proportion of hydration attending the resolution, we
+have shown on constitutional grounds that this must be relatively small.
+Assuming approximately the formula C_{19}H_{22}O_{9} for the lignone
+residue as it exists in combination, and the anhydride formula for the
+cellulose, these revised statistics now appear, as regards the carbon
+contents of the lignocellulose:
+
+          Cellulose, 44.4 C; lignone, 57.8.
+     80 x 44.4 / 100 = 35.52
+     20 x 57.8 / 100 = 11.56
+                       _____
+
+                       47.08 p.ct. C in lignocellulose.
+
+These conclusions are in accordance with the experimental facts, and,
+taken together with the new evidence we have accumulated from a study of
+the lignocellulose esters, we may sum up the constitutional points as
+follows: The lignocellulose is a complex of
+
+      Cellulose alpha        Cellulose beta                  Lignone
+           65 p.ct.              15 p.ct.                       20
+     Allied to the normal      Yielding furfural        One-third of which
+          celluloses         approximately 50 p.ct.      is of benzenoid
+                                                               type
+
+The lignone contains but little hydroxyl. The celluloses are in
+condensed hydroxyl union with the lignone, but the combination occurs by
+complexes of relatively large molecular weight.
+
+
+DIE CHEMIE DER LIGNOCELLULOSEN--EIN NEUER TYPUS.
+
+W. C. HANCOCK and O. W. DAHL (Berl. Ber., 1895, 1558).
+
+~Chemistry of Lignocelluloses--A New Type.~
+
+The stem of the aquatic _AEschynomene aspera_ offers an exceptional
+instance of structural modification to serve the special function of a
+'float,' 1 grm. of substance occupying an apparent volume of 40-50 c.c.
+This pith-like substance is morphologically a true wood (De Bary), and
+the author's investigations now establish that it is in all fundamental
+points of chemical composition a lignocellulose, although from its
+colour reactions it has been considered by botanists to be a cellulose
+tissue containing a proportion of lignified cells. Thus the main tissue
+is stained blue by iodine in presence of hydriodic acid (1.5 s.g.), and
+the colour is not changed on washing. The ordinary lignocelluloses are
+stained a purple brown changed to brown on washing. The reactions with
+phloroglucol and with aniline salts, characteristic of these compounds,
+is only faintly marked in the main tissue, though strongly in certain
+individual cells.
+
+The following quantitative determinations, however, establish the close
+similarity of the product to the typical lignocelluloses:
+
+_Elementary Analysis._--C 46.55, H 6.7. _Furfural_ 11.6 p.ct., of which
+there remained in the residue from alkaline hydrolysis (71 p.ct.) 8.0,
+i.e. about 70 p.ct. The distribution of the furfuroids is therefore not
+affected by the alkaline treatment.
+
+_Chlorination._--The substance (after alkaline hydrolysis) takes up 16.9
+p.ct. Cl, of which approximately one-half is converted into hydrochloric
+acid.
+
+_Methoxyl._--O.CH_{3} estimated = 2.9 p.ct.
+
+_Ferric Ferricyanide Reaction._--Increase of weight due to blue cyanide
+fixed (1) 75 p.ct., (2) 96 p.ct. Ratio, Fe : CN = 1 : 2, 4.
+
+_Hydroxyl Reactions._--In the formation of nitric esters and in the
+sulphocarbonate reaction the substance gave results similar to those
+obtaining for the jute fibre.
+
+These results establish the general identity of this peculiar product of
+plant life with the lignocelluloses, at the same time that they show
+that certain of the colour reactions supposed to characterise the
+lignocelluloses are due to by-products which may or may not be present.
+
+(p. 172) ~Composition of Elder Pith.~--In a systematic investigation of
+the celluloses in relation to function we shall have to give special
+attention to the parenchymatous tissues of all kinds. These are, for
+structural reasons, not easily isolated, for which reason and their
+generally 'inferior' functions they do not present themselves to
+chemical observation in the same obvious way as do their fibrous
+relatives. The pith of the elder, however, _is_ readily obtained in
+convenient masses, and a preliminary investigation of the entire tissue
+has established the following points:
+
+The _reactions_ of the tissue are in all respects those of the
+lignocelluloses.
+
+_Composition._--Ash, 2.2 p.ct.; moisture in air-dry state, 12.3 p.ct.
+Alkaline hydrolysis (loss): (a) 14.77, (b) 17.84. Cellulose (yield),
+52.33 p.ct. Nitrate-reaction complicated by secondary reactions and
+yields low, 90.95 p.ct. _Sulphocarbonate reaction:_ Resists the
+treatment, less than 10 p.ct. passes into solution.
+
+_Furfural._--The original tissue yields 7.13 p.ct.; the residue from
+alkaline hydrolysis (b) 5.40 p.ct.
+
+This tissue is, therefore, a lignocellulose having the chemical
+characteristics typical of the group, but of less resistance to
+hydrolytic actions.
+
+The investigation will be prosecuted in reference to the cause of
+differentiation in this latter respect. Probably the pectocelluloses are
+represented in the tissue.
+
+
+~The Insoluble Carbohydrates of Wheat (grain).~
+
+H. C. SHERMAN (J. Amer. Chem. Soc., 1897, 291).
+
+(p. 171) This is a study of the constituents of the cell-walls of wheat
+grain. Bran was taken as the most convenient form of the raw material,
+being freed from starch by treatment with malt extract, and further
+treated (1) with cold dilute ammonia, (2) cold dilute soda lye (2 p.ct.
+NaOH), and (3) boiling 0.1 p.ct. NaOH. The product retained only 1.25
+p.ct. proteids, and yielded 15.62 p.ct. furfural.
+
+_Acid Hydrolysis._--The product was boiled 30 mins. with dilute acid
+(1.25 p.ct. H_{2}SO_{4}), and the solution boiled until the Fehling test
+showed no further increase of monoses. At the limit the reducing power
+of the dissolved carbohydrates was 91.3 p.ct., that of dextrose.
+Converted into osazones the analysis showed them to be _pure
+pentosazones_. The _hemicellulose_ of wheat is, therefore, according to
+the author, _pure pentosane_.
+
+_Residue._--This was a lignocellulose yielding 11.5 p.ct. furfural. It
+was subjected to a series of treatments with ferric ferricyanide, and
+the proportion of Prussian blue fixed was determined by increase of
+weight, viz. from 10 p.ct. to 47 p.ct. according to the conditions. The
+results confirmed those of Cross and Bevan first obtained with the
+typical lignocellulose (jute).
+
+_Chlorination._-The residue was boiled with dilute alkali, washed, and
+exposed to chlorine gas. The resulting lignone chloride was isolated by
+solution in alcohol, &c. It yielded 26.7 p.ct. Cl on analysis. In this
+and its properties it appeared to be identical with the product isolated
+by Cross and Bevan from jute, with the empirical formula
+C_{19}H_{18}Cl_{4}O_{9}.
+
+_Cellulose_ was isolated from the residue by three of the well-known
+methods, and the following comparative numbers are noteworthy:
+
+ _________________________________________________________________________
+|                             |              |            |               |
+|                             | F. Schulze   |   Lange    |  Cross and    |
+|      Method                 | Dil. HNO_{3} | Fusion KOH |    Bevan      |
+|                             |   KClO_{3}   |            | Chlorine, &c. |
+|_____________________________|______________|____________|_______________|
+|                             |              |            |               |
+| Cellulose p.ct. obtained    |    66.0      | 39.3-43.1  |    66.5       |
+| Furfural p.ct. of cellulose |     7.0      |   3.96     |     5.62      |
+| Residual nitrogen           |     0.22     |   0.03     |     0.00      |
+| Ferricyanide reaction,      |              |            |               |
+|   Prussian blue fixed       |     6.04     |   0.89     |     0.92      |
+|_____________________________|______________|____________|_______________|
+
+The author remarks: 'It is evident no one feature can be urged as a
+criterion in judging between the methods, but all must be taken into
+consideration. Such a comparison shows the superiority of the
+chlorination method.'
+
+The cellulose is not of the normal (cotton) type, since on treatment
+with sulphuric acid it dissolves with considerable discolouration, but
+only to the extent of about 80 per cent. The dissolved monoses converted
+into osazones were found to consist of hexoses only. The cellulose
+treated with caustic soda solution (5 p.ct. NaOH) in the cold yielded 20
+p.ct. of its weight of soluble constituents, but as the residue yielded
+3.34 p.ct. furfural the attack of the alkali is by no means confined to
+the furfuroids.
+
+~Animal Digestion of the Constituents of Bran.~--Observations on a steer
+fed upon wheat bran only established the following percentage digestion
+of the several constituents:
+
+     Soluble carbohydrates    96.9
+     Starch                  100.0
+     Free pentosanes          60.2
+     Cellulose                24.8
+     Lignin complex           36.7
+     Proteid                  82.96
+     Ether extract            42.73
+     _____________________   ______
+
+     Nitrogen-free extract    76.08
+     Crude fibre              32.21
+
+
+JOURNAL OF THE IMPERIAL INSTITUTE
+
+(Research Department, Vols. 1-2, 1895-6).
+
+(p. 109) In this journal appear a series of notices of the results of
+analyses of vegetable fibres by the method described in 'Report on
+Miscellaneous Fibres' (Col. Ind. Exhibition Reports, p. 368) [C. F.
+Cross]. These investigations deal with the following subjects:
+
+1895.     p. 29      Various Indian Fibres--more particularly Sida.
+            118      (a) Fibres from Victoria; (b) Special Analyses of
+       (a)               Samples of Jute; (c) Paper-making Fibres
+                         from S. Australia.
+            202      Fibres from Victoria.
+            287      Fibres from Victoria.
+            366      Sisal from Trinidad.
+            373      Rope-fibres from Grenada.
+       (b)  398      Report of Experiments on Indian Jute (1).
+            435}     Fifth and Sixth Report on Australian Fibres.
+            473}
+1896.        68      Hibiscus and Abroma Fibres.
+            104-5    Hibiscus, Urena, and Crotalaria Fibres.
+            141      Indian Sisal
+       (c)  182-3    Report of Experiments on Indian Jute (2).
+            264      Sanseviera from Assam.
+
+From the above we may draw the general conclusion that the scheme of
+investigation has been found in practice to answer its main purpose,
+viz. to afford such numerical constants as determine industrial values.
+In illustration we may cite (a) the results of analyses of specially
+selected samples of jute, from which it will be seen that there is a
+close concordance of value as ordinarily determined from external
+appearance, with the chemical constants as determined in the laboratory.
+
+ __________________________________________________________________
+|                            |                                     |
+|                            |          Quality of Jute            |
+|____________________________|_____________________________________|
+|                            |       |        |       |            |
+|                            |  Low  | Medium | Extra | Extra Fine |
+|____________________________|_______|________|_______|____________|
+|                            |       |        |       |            |
+| Moisture                   | 11.0  |  10.4  | 11.1  |     9.6    |
+| Ash                        |  0.87 |   2.8  |  1.0  |     0.7    |
+| Alkaline hydrolysis (a)    |       |        |       |            |
+|   5 mins. boiling          | 13.2  |  11.6  |  8.5  |     9.1    |
+| Alkaline hydrolysis (b)    |       |        |       |            |
+|   60 mins. boiling         | 16.1  |  17.5  | 12.5  |    13.1    |
+| Mercerising treatment      |  9.2  |  10.5  | 10.3  |     8.5    |
+| Nitration (increase p.ct.) | 36.6  |  35.7  | 37.5  |    36.7    |
+| Cellulose (yield)          | 71.4  |  70.0  | 79.0  |    77.7    |
+| Acid purification          |  2.6  |   1.3  |  1.9  |     2.0    |
+|____________________________|_______|________|_______|____________|
+
+A useful series of experiments, initiated by the Institute, is that
+noted under (b) and (c) above.
+
+(1) To ascertain the quality of the fibre extracted from the plant at
+different stages of growth, quantities of 400 lbs. of the stalks were
+cut at successive stages and the fibre isolated after steeping 14-20
+days. The fibre was shipped to England and chemically investigated, with
+the following results:
+
+No. 1. Cut before appearance of inflorescence.
+ "  2.  " after budding.
+ "  3.  " in flower.
+ "  4.  " after appearance of seed-pod.
+ "  5.  " when fully matured.
+
+ _________________________________________________________________
+|                           |       |       |      |      |       |
+|                           |  (1)  |  (2)  |  (3) |  (4) |  (5)  |
+|___________________________|_______|_______|______|______|_______|
+|                           |       |       |      |      |       |
+| Moisture                  | 11.55 |  8.74 | 10.7 | 10.0 |  9.72 |
+| Ash                       |  1.1  |  1.1  |  1.1 |  1.1 |  0.90 |
+| Alkaline hydrolysis (a)   |  6.2  |  8.5  |  9.7 |  8.9 |  7.3  |
+|    "         "      (b)   | 10.5  | 11.9  | 11.6 | 12.0 | 11.2  |
+| Mercerising treatment     | 10.2  | 10.7  | 12.0 |  8.1 | 11.0  |
+| Nitration                 | 37.2  | 32.1  | 32.2 | 33.2 | 36.6  |
+| Cellulose                 | 74.0  | 76.2  | 74.1 | 74.8 | 76.4  |
+| Acid purification         |  0.8  |  0.5  |  0.7 |  2.4 |  1.4  |
+|___________________________|_______|_______|______|______|_______|
+
+It will be thus seen that there are no changes of any essential kind in
+the chemical composition of the bast fibre throughout the life-history
+of the plant, confirming the conclusion that the 'incrustation' view of
+lignification is consistent only with the structural features of the
+changes, and so far as it has assumed the gradual overlaying of a
+cellulose fibre with the lignone substance it is not in accordance with
+the facts.
+
+Examination of the samples from the point of view of textile quality
+showed a superiority of No. 1 in fineness, softness, and strength; from
+this stage there is observed a progressive deterioration, but the No. 4
+sample (which was taken at the usual period of cutting) is superior to
+No. 5.
+
+In a further series of experiments (c) the jute was subjected to
+certain chemical treatments immediately after the separation of the
+fibre from the plant. These consisted in steeping (1) in solution of
+sodium carbonate, as well as of plant ashes, and (2) in sulphite of
+soda, the purpose of the treatments being to modify or arrest the
+changes which take place in the fibre when press-packed in bales for
+shipment. The samples were shipped from India under the usual conditions
+and examined soon after arrival. It was found that the chemical
+treatments had produced but small changes in chemical composition of the
+fibre-substance. The sulphite treatment was the more marked in
+influence, somewhat lowering the cellulose and nitration constants. The
+conclusion drawn from the results was that they afford no prospect of
+any useful modification, i.e. improvement of the textile quality of the
+fibre by any chemical treatments such as could be applied to the fibre
+on the spot before drying for press-packing and shipment.
+
+The other matters investigated in the Institute laboratory and reported
+on as indicated above are rather of commercial significance, and
+contributed no points of moment to the chemistry of cellulose.
+
+
+OBSERVATIONS ON SOME OF THE CHEMICAL SUBSTANCES IN THE TRUNKS OF TREES.
+
+F. H. STORER (Bull. Bussey Inst., 1897, 386).
+
+(p. 172) An examination of the outer and inner wood and of the bark of
+the grey birch, at different seasons of the year, gave the following
+yields of furfural p.ct. on the dry substance:
+
+ ________________________________
+|         |               |      |
+|         |     Wood      |      |
+|         |_______________| Bark |
+|         |       |       |      |
+|         | Inner | Outer |      |
+|_________|_______|_______|______|
+|         |       |       |      |
+| May     | 21.3  | 19.6  | 16.7 |
+| July    | 16.6  | 18.8  | 11.4 |
+| October | 16.2  | 16.3  | 12.3 |
+|_________|_______|_______|______|
+
+The paper contains the results of treating the woods and various
+vegetable products with hydrolysing agents in order of intensity: (a)
+Malt-extract at 60 deg.C., (b) boiling dilute HCl (1.0 p.ct. HCl), and
+(c) boiling dilute HCl (2.5 p.ct.). The residues were found to yield
+considerable proportions of furfural. The following numbers are typical:
+
+ ________________________________________________________________________
+|                               |             |                          |
+|                               |     Birch   |        Stones of         |
+|                               |_____________|__________________________|
+|                               |      |      |        |         |       |
+|                               | Bark | Wood |  Date  | Apricot | Peach |
+|_______________________________|______|______|________|_________|_______|
+|                               |      |      |        |         |       |
+| Action of malt extract calcu- |      |      |        |         |       |
+| lated as starch dissolved     | 4.24 |  3.5 |   5.2  |   1.5   |   --  |
+|                               |      |      |        |         |       |
+| Residue boiled, 1 p.ct. HCl   |      |      | Mannan |         |       |
+| gave pentosanes dissolved.    |  --  | --   |  11.7  |  14.1   |  6.7  |
+|                               |      |      |        |         |       |
+| Residue yielded furfural      | 19.3 | 17.8 |   3.4  |   9.6   |  9.7  |
+|_______________________________|______|______|________|_________|_______|
+
+The proportion of pentosanes (furfuroids) removed, i.e. hydrolysed by
+boiling with hydrochloric acid of 2.5 p.ct. HCl, is shown by the
+following estimations of furfural:
+
+ _________________________________________________________________
+|                        |              |               |         |
+|                        |    Birch     |  Sugar maple  |         |
+|                        |______________|_______________| Apricot |
+|                        |       |      |       |       | stones  |
+|                        |  Bark | Wood | Outer | Inner |         |
+|                        |       |      |  wood |  wood |         |
+|________________________|_______|______|_______|_______|_________|
+|                        |       |      |       |       |         |
+| In original substance  | 16.7  | 19.6 |  18.2 |  20.7 |  18.4   |
+|                        |       |      |       |       |         |
+| In residue from action |  6.53 |  8.6 |   4.9 |   6.4 |   7.0   |
+| of 2.5 p.ct. HCl       |       |      |       |       |         |
+|________________________|_______|______|_______|_______|_________|
+
+_Wood Gum._--The paper contains some observations on the various methods
+of isolating this product. Attention is directed to the necessary
+impurity of the product, and to the fact that the numbers for furfural
+and for the xylose yielded by hydrolysis are considerably less than for
+a pure pentosane.
+
+_Estimation of Cellulose._--The author investigated the process of Lange
+and the 'celluloses' obtained from various raw materials. The products
+from the woods of birch and maple contained furfural-yielding
+constituents, represented by yields of 6-8 p.ct. furfural. Preference is
+given to the process by comparison with others, at the same time that it
+is recommended in all cases to examine the product for furfural
+quantitatively, converting the numbers into pentosane equivalents, and
+subtracting from the total 'cellulose' to give the true cellulose.
+
+
+ZUR KENNTNISS DER MUTTERSUBSTANZEN DES HOLZGUMMI.
+
+E. WINTERSTEIN (Ztschr. Physiol. Chem., 1892, 381).
+
+~ON THE MOTHER SUBSTANCES OF WOOD-GUM.~
+
+(p. 188) According to the text-books beech-wood may be regarded as the
+typical raw material for the preparation of the laboratory product known
+as wood-gum. The author has subjected beech-wood and beech-wood
+cellulose (Schulze process) to a range of hydrolytic treatments, acid
+and alkaline, in order to determine the conditions of selective action
+upon the mother substance of the wood-gum. In the main it appears that
+this group of furfuroids is equally resistant with the cellulose
+constituents of the wood; in fact, that the mother substance of wood-gum
+is a modified cellulose, and exists in the wood in chemical combination
+with the 'incrusting substances.'
+
+Of the author's experimental results the following may be cited as
+typical:
+
+                                                     Yield of furfural
+     Substance                                              p.ct.
+Original beech-wood                                         13.8
+
+After boiling 3 hrs. with 1.25 p.ct. H_{2}SO_{4} (residue)  10.1
+
+   "       "      "    "   5.0    "       "            "     5.6
+
+Cellulose--isolated by Schulze process (yield 53 p.ct.)      6.9
+
+    "      after further 14 days' digestion with the
+             Schulze acid (HNO_{3} + KClO_{3})               5.9
+
+    "      after extraction with 5 p.ct. NaOH in
+             cold (residue)                                  5.0
+
+    "      after second extraction with 5 p.ct. NaOH
+             in cold (residue)                               4.4
+
+
+UEBER DIE FRAGE NACH DEM URSPRUNG UNGESAeTTIGER VERBINDUNGEN IN DER
+PFLANZE.
+
+C. F. CROSS, E. J. BEVAN, and C. SMITH (Berl. Ber., 1895, 1940).
+
+~ON THE SOURCE OF THE UNSATURATED COMPOUNDS OF THE PLANT.~
+
+(p. 179) In distilling for furfural by the usual methods of boiling
+cellulosic products with condensing acids, the furfural is accompanied
+by volatile acids, also products of decomposition of the cellulosic
+complex. A series of distillations was carried out with dilute sulphuric
+acids of varying concentration from 10-50 H_{2}SO_{4} : 90-50 H_{2}O by
+weight, using barley straw as a typical cellulosic material. The
+distillates were collected in successive fractions, and the furfural and
+volatile acid determined. The results are given in the form of curves.
+The aggregate yields were as follows:--
+
+Concentration of acid
+  (H_{2}SO_{4}) p.ct.            10    15    20    30    40    50
+
+Furfural yield p.ct. of straw     2.0   2.0   4.4  10.1  11.5  11.0
+
+Volatile acid (calculated
+  as acetic acid) p.ct. of straw  1.7   1.9   3.1   4.3   6.3  14.8
+
+With acids up to 20 p.ct. H_{2}SO_{4} both products are formed
+concurrently and in nearly equal quantity. With the 30 p.ct. acid there
+is a great increase in the total furfural, and with the 40 p.ct. acid it
+reaches nearly the maximum obtainable with HCl of 1.06 s.g. (Tollens),
+in this case 12.4 p.ct. The volatile acid increases, but in less ratio;
+it is also produced concurrently. With 50 p.ct. H_{2}SO_{4} the
+conditions are changed. The total furfural is rapidly formed, whereas
+the volatile acid continues to be formed long after the aldehyde ceases
+to come over. Moreover, whereas in the previous cases it was mainly
+acetic acid, it is now mainly formic acid. The method was then extended
+to a typical series of celluloses, heated with the more concentrated
+acid (40-50 p.ct. H_{2}SO_{4}), with the following results:
+
+ __________________________________________________
+|                        |       |                 |
+|                        |       |  Volatile acid  |
+|                        |       |_________________|
+|                        |       |        |        |
+|                        |       | Acetic | Formic |
+|________________________|_______|________|________|
+|                        |       |        |        |
+| Swedish filter-paper   |  0.3  |   2.7  |  17.2  |
+| Esparto cellulose      | 12.4  |   3.2  |  16.6  |
+| Bleached cotton        | trace |   3.1  |  13.2  |
+| Raw cotton (American)  |  --   |   5.0  |   9.4  |
+| Jute cellulose         |  5.2  |   4.9  |  22.7  |
+| Beech (wood) cellulose |  6.4  |   3.5     14.6  |
+|________________________|_______|________|________|
+
+The tendency in the hexoses and their polyanhydrides to split off one
+carbon atom in the oxidised form, throws some light on the furfurane
+type of condensation, which is represented in the lignocelluloses. We
+are still without any evidence as to the possible transition of the
+hexoses to benzenoid compounds. Such transitions would be more easily
+explained on the assumption that the celluloses are composed in part of
+polyanhydrides of the ketoses.
+
+
+SPIRITUS AUS CELLULOSE UND HOLZ.
+
+E. SIMONSEN (Ztschr. angew. Chem., 1898, 3).
+
+~PRODUCTION OF ALCOHOL FROM CELLULOSE AND WOOD.~
+
+(pp. 50, 209) This investigation was undertaken with one main object--to
+determine the optimum conditions of treatment of wood-cellulose and of
+wood itself for conversion into 'fermentable sugar.' The process of
+'inversion' or hydrolysis, by digestion with dilute acid at high
+temperature, involves the four main factors: pressure (i.e.
+temperature), concentration of acid, ratio of liquid to cellulose and
+duration of digestion. Each of these was varied in definite gradations,
+and the effect measured. The degree of action was measured in terms of
+'reducing sugar,' calculated from the results of estimation by Fehling
+solution, as 'glucose' per cent. of original cellulose (or wood).
+
+(a) _Cellulose._ [Wood-cellulose obtained by bisulphite
+process.]--With a proportion of total liquid to cellulose of 27 : 1, and
+using sulphuric acid as the hydrolysing agent, the optimum results were
+obtained with acids of 0.45-0.60 p.ct. (H_{2}SO_{4}) and pressures of
+6-8 atm. The maximum yield of 'sugar' was 45 p.ct. of the cellulose.
+
+Under the above conditions the maximum of conversion is attained in 2
+hours.
+
+Having now regard to the production of a solution of maximum
+_concentration_ of dissolved solids, the following conditions were
+asertained to fulfil the requirement, and, in fact, may be regarded as
+the economic optimum:
+
+     Proportion of total liquid  6 times wt. of cellulose
+     Concentration of acid       0.5 p.ct. H_{2}SO_{4}
+     Pressure                   10 atm.
+     Duration of digestion       1.5 hour
+
+giving a yield of 41 p.ct. 'reducing sugar' calculated to the original
+cellulose (dry).
+
+_Alcoholic Fermentation of Neutralised Extract._--The liquors were found
+to ferment freely, and on distillation to yield a quantity of alcohol
+equal to 70 p.ct. of the theoretical--i.e. on the basis of the numbers
+for copper oxide reduction.
+
+(b) _Hydrolytic 'Conversion' of Wood (Lignocellulose)._--A similarly
+systematic investigation carried out upon pine sawdust established the
+following as optimum conditions:
+
+     Proportion of total liquid  5 times wt. of wood
+     Concentration of acid       0.5 p.ct. H_{2}SO_{4}
+     Pressure                    9 atm.
+     Duration of digestion      15 minutes
+
+giving a yield of 20 p.ct. 'reducing sugar,' calculated from the
+'Fehling' test.
+
+_Fermentation_ of the neutralised extracts gave variable results. The
+highest yields obtained were 60 p.ct. of theoretical, the author finally
+concluding that under properly controlled conditions of inversion and
+fermentation 100 kg. wood yield 6.5 l. absolute alcohol.
+
+
+UeBER DIE URSACHE DER VON SIMONSEN BEOBACHTETEN UNVOLLSTAeNDIGKEIT DER
+VERGAeHRUNG DER AUS HOLZ BEREITETEN ZUCKERFLUeSSIGKEITEN.
+
+B. TOLLENS (Ztschr. angew. Chem., 1898, 15).
+
+~ON THE CAUSE OF INCOMPLETE FERMENTATION OF SUGARS OBTAINED BY ACID
+HYDROLYSIS OF WOOD.~
+
+The author criticises Simonsen's explanation of the results obtained
+with extracts from pine wood. The incompleteness of fermentation of the
+products is certainly due in part to the presence of furfural-yielding
+carbohydrates, which are resistant to yeast. The pine woods contain 8-10
+p.ct. of these constituents in their anhydride form ('pentosanes'). They
+yield readily to acid hydrolysis, and certainly constitute a
+considerable percentage of the dissolved products. A similar complex was
+obtained by the author in his investigation of peat (Berl. Ber. 30,
+2571), and was found to be similarly incompletely attacked by yeast. The
+yields of alcohol corresponded with the proportion of the total
+carbohydrates disappearing. These were the hexose constituents of the
+hydrolysed complex, the pentoses (or 'furfuroids') surviving intact.
+
+
+UEBER SULFITCELLULOSEABLAUGE.
+
+H. SEIDEL (Ztschr. angew. Chem., 1900).
+
+~WASTE LIQUORS FROM BISULPHITE PROCESS.~
+
+(p. 210) Later researches confirm the conclusion that in the soluble
+by-products of these cellulose processes the S is combined as a SO_{3}H
+group. The following analyses of the isolated lignin sulphonic acid are
+cited:
+
+ ________________________________________________
+|                          |       |      |      |
+|                          |   C   |  H   |  S   |
+|__________________________|_______|______|______|
+|                          |       |      |      |
+| (a) Lindsey and Tollens  | 56.12 | 5.30 | 5.65 |
+| (b) Seidel           (1) | 56.27 | 5.87 | 5.52 |
+| (c) Seidel and Hanak (2) | 53.69 | 5.22 | 8.80 |
+| (d) Street               | 50.22 | 5.64 | 7.67 |
+|__________________________|_______|______|______|
+
+The variations are due to the varying conditions of the digestion of the
+wood and to corresponding degrees of sulphonation of the original
+lignone group. Calculating the composition of the latter from the above
+numbers on the assumption that the S represents SO_{3}H, the following
+figures result:
+
+ __________________________________
+|   |             |       |       |
+|   | (a) and (b) |  (c)  |  (d)  |
+|___|_____________|_______|_______|
+|   |             |       |       |
+| C |  64.00      | 65.1  | 59.61 |
+| H |   6.65      |  6.33 |  6.69 |
+|___|_____________|_______|_______|
+
+This author considers that beyond the empirical facts established by the
+above named[10] very little is yet known in regard to the constitution
+of the lignone complex.
+
+Nor is there any satisfactory application of this by-product as yet
+evolved. Evaporation and combustion involve large losses of sulphur
+[D.R.P. 74,030, 83,438; Seidel and Hanak, Mitt. Techn. Gew. Mus. 1898].
+A more complete regeneration of the sulphur has been the subject of a
+series of patents [D.R.P. 40,308, 69,892, 71,942, 78,306, 81,338], but
+the processes are inefficient through neglect of the actual state of
+combination of the S, viz. as an organic sulphonate. The process of V.B.
+Drewson (D.R.P. 67,889) consists in heating with lime under pressure,
+yielding calcium monosulphite (with sulphate and the lignone complex in
+insoluble form). The sulphite is redissolved as bisulphite by treatment
+with sulphurous acid. This process is relatively costly, and yields
+necessarily an impure lye. It has been proposed to employ the product as
+a foodstuff both in its original form and in the form of benzoate
+(D.R.P. 97,935); but its unsuitability is obvious from its composition.
+A method of destructive distillation has been patented (D.R.P. 45,951).
+The author has investigated the process, and finds that the yield of
+useful products is much too low for its economical development. Fusion
+with alkaline hydrates for the production of oxalic acid (D.R.P. 52,491)
+is also excluded by the low yield of the product.
+
+The application of the liquor for tanning purposes (D.R.P. 72,161)
+appears promising from the fact that 28 p.ct. of the dry residue is
+removed by digestion with hide powder. This application has been
+extensively investigated, but without practical success. Various
+probable uses are suggested by the viscosity of the evaporated extract.
+As a substitute for glue in joinery work, bookbinding, &c., it has
+proved of little value. It is applied to some extent as a binding
+material in the manufacture of briquettes, also as a substitute for
+gelatin in the petroleum industry. Cross and Bevan (E.P. 1548/1883) and
+Mitscherlich (D.R.P. 93,944 and 93,945) precipitate a compound of the
+lignone complex and gelatin by adding a solution of the latter to the
+liquors. The compound is redissolved in weak alkaline solutions and
+employed in this form for engine-sizing papers. Ekman has patented a
+process (D.R.P. 81,643) for 'salting out' the lignone sulphonates, the
+product being resoluble in water and the solution having some of the
+properties of a solution of dextrin. Owing to its active chemical
+properties this product--'dextron'--has a limited capability of
+substituting dextrin. The suggestion to employ the evaporated extract as
+a reducing agent in indigo dyeing and printing has also proved
+unfruitful. The author's application of the soda salt of the lignone
+sulphonic acid as a reducing agent in chrome-mordanting wool and woollen
+goods (D.R.P. 99,682) is more successful in practice, and its industrial
+development shows satisfactory progress. The product is known as
+'lignorosin.'
+
+FOOTNOTES:
+
+[10] See more particularly: Lindsey and Tollens, _Annalen_, 267, 341;
+Cross and Bevan's _Cellulose_, pp. 197-203; Street, Inaug.-Diss.,
+Goettingen, 1892; Klason, _Rep. d. Chem. Ztg._ 1897, 261; Seidel and
+Hanak, _Mitt. d. Techn. Gew. Mus._ 1897-1898.
+
+
+
+
+SECTION VII. PECTIC GROUP
+
+
+UNTERSUCHUNGEN UeBER PECTINSTOFFE.
+
+R. W. TROMP DE HAAS and B. TOLLENS (Lieb. Ann., 286, 278).
+
+UeBER DIE CONSTITUTION DER PECTINSTOFFE, B. TOLLENS (ibid. 292).
+
+~INVESTIGATIONS OF PECTINS.~
+
+(p. 216) It is generally held that the pectins are, or contain, oxidised
+derivatives of the carbohydrates. The authors have isolated and analysed
+a series of these products, and the results fail to confirm a high
+ratio O : H. The following are the analytical numbers:
+
+ ________________________________________________
+|              |      |      |     |             |
+| Pectin from  |  Ash |   C  |  H  | Ratio H : O |
+|______________|______|______|_____|_____________|
+|              |      |      |     |             |
+| Apple        |  6.2 | 43.4 | 6.4 |   1 : 7.9   |
+| Cherry       | 20.5 | 42.5 | 6.5 |   1 : 7.9   |
+| Rhubarb      |  4.2 | 43.3 | 6.8 |   1 : 7.4   |
+| Currant      |  5.0 | 47.1 | 5.9 |   1 : 8.5   |
+| Greengage    |  3.3 | 43.0 | 5.9 |   1 : 8.5   |
+| Turnip       |  7.3 | 41.0 | 5.9 |   1 : 9.0   |
+|______________|______|______|_____|_____________|
+
+Acid hydrolysis (4 p.ct. H_{2}SO_{4}) gave syrupy products not
+crystallisable--in certain cases the hydrolysis was accompanied by
+separation of insoluble cellulose. The insoluble product from currant
+pectin had the composition C 54.4, H 5.0.
+
+Tollens points out that the results of empirical analysis are
+inconclusive; and that from the acid reactions of these products and
+their combination with bases, carboxylic groups are present, though
+probably in anhydride or ester form.
+
+The pectins may be regarded as closely related to the mucilages
+(_Pflanzenschleim_), differing from them only by the presence of the
+oxidised groups in question.
+
+
+UEBER DIE CONSTITUTION DER PECTINSTOFFE.
+
+C. F. CROSS (Berl. Ber., 1895, 2609).
+
+~CONSTITUTION OF PECTINS.~
+
+It is pointed out that the composition of the pectin of white currants,
+as given in the preceding paper, is that of the typical lignocellulose,
+the jute fibre. The product was isolated and further investigated by the
+author. It gave 9.8 p.ct. furfural on boiling with HCl (1.06 s.g.),
+reacted freely with chlorine, giving quinone chlorides, and with ferric
+ferricyanide to form Prussian blue. This 'pectin' is therefore a form
+of soluble lignocellulose. The 'pectic' group consequently must be
+extended to include hydrated and soluble forms of the mixed complex of
+condensed and unsaturated groups with normal carbohydrates, such as
+constitute the fibrous lignocelluloses.
+
+
+UEBER DAS PFLANZLICHE AMYLOID.
+
+E. WINTERSTEIN (Ztschr. Physiol. Chem., 1892, 353).
+
+~ON VEGETABLE AMYLOID.~
+
+(p. 224) A group of constituents of many seeds, distinguished by giving
+slimy or ropy 'solutions' under the action of boiling water are
+designated 'amyloid.' They are reserve materials, and in this, as in the
+physical properties of their 'solutions,' they are very similar to
+starch. They are, however, not affected by diastase; and generally are
+more resistant to hydrolysis. Typical amyloids have been isolated by the
+author from seeds of _Tropoeolum majus, Poeonia officinalis_, and
+_Impatiens Balsamina_. The raw material was carefully purified by
+exhaustive treatment with ether and alcohol, &c.; the amyloid then
+extracted by boiling with water, and isolated by precipitation with
+alcohol. Elementary analysis gave the numbers C 43.2, H 6.1. On boiling
+with 12 p.ct. HCl it gave 15.3 p.ct. furfural; oxidised with nitric acid
+it yielded 10.4 p.ct. mucic acid. Specimens from the two first-named raw
+materials gave almost identical numbers.
+
+_Hydrolysis._--On boiling with dilute acids these products are gradually
+broken down, dissolving without residue. In this respect they are
+differentiated from the mucilages, which give a residue of cellulose
+(insoluble). From the solution the author isolated crystalline
+galactose, but failed to isolate a pentose. Dextrose was also not
+identified directly.
+
+The tissue residues left after extracting the amyloid constituent, as
+above described, were subjected to acid hydrolysis. A complex of
+products was obtained, from which galactose was isolated. A
+furfural-yielding carbohydrate was also present in some quantity, but
+could not be isolated. The original seed tissues, therefore, contain an
+amyloid and a hemicellulose, the latter differentiated in its resistance
+to water. Both yield, however, to acid hydrolysis a complex of products
+of similar composition and constitution.
+
+
+UEBER DEN GEHALT DES TORFES AN PENTOSANEN ODER FURFUROLGEBENDEN STOFFEN
+UND AN ANDEREN KOHLENHYDRATEN.
+
+H. V. FEILITZEN and B. TOLLENS (Berl. Ber., 1897, 2,571).
+
+~CARBOHYDRATE CONSTITUENTS OF PEAT.~
+
+(p. 240) An investigation of typical peats taken at successive depths
+showed increasing percentage of carbon, and inversely a decreasing yield
+of furfural. The numbers may be compared with those for _Sphagnum
+cuspidatum_--with C = 49.80 p.ct., and furfural 7.99 p.ct., calculated
+to dry, ash-free substance:
+
+ __________________________________________________
+|                       |         |                |
+|  Depth at which taken | C p.ct. | Furfural p.ct. |
+|_______________________|_________|________________|
+|      _                |         |                |
+|     |      20-100 cm. |  51.08  |      6.93      |
+|  I. |     100-200  "  |  53.52  |      5.30      |
+|     |_    200-300  "  |  58.66  |      3.19      |
+|      _                |         |                |
+|     |  Surface-20  "  |  55.47  |      3.40      |
+| II. |       20-60  "  |  55.06  |      3.48      |
+|     |      60-100  "  |  58.25  |      1.45      |
+|     |     100-120  "  |  58.23  |      1.19      |
+|     |_    180-200  "  |  57.57  |      1.80      |
+|_______________________|_________|________________|
+
+_Cellulose_ was estimated by the Lange method. The yield from _Sphagnum_
+was 21.1 p.ct.
+
+From specimen I. at {  20-100 cm.   15.20
+                    { 100-200  "     6.87
+
+From the peat of lower depths no cellulose could be obtained.
+
+_Hydrolysis_ (acid).--On heating with 1 p.ct. H_{2}SO_{4} at 130-135 deg.,
+soluble carbohydrates were obtained, amongst which mannose was
+identified, and galactose shown to be present in some quantity. After
+fermenting away the hexoses, the residue was treated with
+phenylhydrazine and an osazone separated. It contained 17.3 p.ct. N, but
+melted at 130 deg.. The substance could not be identified as an osazone of
+any of the yet known pentoses.
+
+
+
+
+SECTION VIII. INDUSTRIAL AND TECHNICAL. GENERAL REVIEW
+
+
+~The Industrial Uses of Cellulose.~
+
+C. F. CROSS (Cantor Lectures, Soc. of Arts, 1897).
+
+(p. 273) A series of three lectures, in which the more important
+industries in cellulose and its derivatives are dealt with on their
+scientific foundations, and by means of a selection of typical problems.
+In reference to textiles, the small number of vegetable fibres actually
+available, out of the endless variety afforded by the plant world, is
+referred to the number of conditions required to be fulfilled by the
+individual fibre, thus: yield per cent. of harvested weight or per unit
+of field area, ease of extraction, the absolute dimensions of the
+spinning unit, and the proportion of variation from the mean dimensions;
+the relative facility with which the unit fibre can be isolated
+preparatory to the final twisting operation; the chemical constants of
+the fibre substance, especially the percentage of cellulose and degree
+of resistance to hydrolysis. It is suggested that any important addition
+to the very limited number fulfilling the conditions, or any great
+improvement in these, can only result from very elaborate artificial
+selection and cultural developments on this basis.
+
+The paper making fibres are shown to fall into a scheme of
+classification based on chemical constitution, and consisting of the
+four groups: (a) Cotton [flax, hemp, rhea], (b) wood celluloses,
+(c) esparto, straw, and (d) lignocelluloses. Papers being exposed to
+the natural disintegrating agencies, more especially oxygen, water (and
+hydrolysing agents generally), and micro-organisms, the relative
+resistance of the above groups of raw materials is discussed as an
+important condition of value. The indirect influence of the ordinary
+sizing and 'filling' materials is discussed. The paper-making quality of
+the fibrous raw materials is also discussed, not merely from the point
+of view of the form and dimensions of the ultimate fibres, but their
+capacity for 'colloidal hydration.' This is complementary to the action
+of rosin, i.e. resin acids, in the engine-sizing of papers; and the
+proof of the potency of this factor is seen in the superior effects
+obtained in sizing jointly with solutions of cellulose and, more
+particularly, viscose and rosin. Wurster's much-cited monograph of the
+subject of rosin-sizing ['Le Collage des Papiers,' Bull. Mulhouse, 1878]
+neglects to take into consideration the contribution of the cellulose
+hydrates to the total and complex sizing effect, and hence gives a
+partial view only of the function of the resin acids.
+
+In further illustration of fundamental principles various developments
+in the textile industries are discussed, e.g. the bleaching of jute,
+cotton, and flax, and special developments in the spinning of rhea and
+flax.
+
+The concluding lecture deals with later progress in the industrial
+applications of cellulose derivatives, chiefly the sulphocarbonate
+(viscose); the nitrates, in their applications to explosives, on the one
+hand, and the spinning of artificial fibres (lustra-cellulose), on the
+other; and the cellulose acetates.
+
+
+~La Viscose et le Viscoide.~
+
+C. H. BARDY (Bull. Soc. d'Enc. Ind. Nationale, 1900, March).
+
+This is a report presented to the Committee of Economic Arts of the
+above Society, dealing with the industrial progress in products obtained
+by means of the sulphocarbonate of cellulose (viscose).
+
+The following developments are noted:
+
+_Engine-sized Papers._--The viscose, by coating the fibres with
+regenerated cellulose hydrate, adds very much to the tensile strength of
+papers. Increase of 40-60 p.ct. is attainable by addition of cellulose
+in this form from 1-4 p.ct. on the weight of the paper.
+
+_Viscoid._--Solid aggregates are formed by incorporating viscose with
+mineral matters, hydrocarbons, &c. Products are cast or moulded into
+convenient forms, and, after purification and sufficient ageing, are
+available for various structural uses.
+
+_Paint._--The viscose is used as a vehicle for pigments, the mixture
+being used either as a paint or for coating papers with fine surfaces,
+such as required in the reproduction of photo-blocks. In these
+applications the extraordinary viscosity of the product conditions the
+economic use of the cellulose in competition with oils, on the one hand,
+and organic colloids, such as gelatine, casein, &c., on the other.
+
+By suitable alteration of the formula for making the paint a product is
+obtained which has an extraordinary power of removing paint from old
+painted surfaces. The product has been officially adopted by the French
+Admiralty, and receives extensive application in removing the paint from
+ships.
+
+_Films._--Films are produced from the viscose itself in various ways.
+Plane or flat by solidifying the viscose on glass surfaces, removing the
+by-products and rolling the films. The film is also produced by
+applying the viscose on textile fabrics, drying down, and fixing on a
+stenter machine, then washing away the alkaline by-products from the
+fixed film. A large number of industrial effects are obtained by
+suitably varying the mixtures applied.
+
+_Cellulose-indiarubber._--The viscose, in its concentrated form, can be
+incorporated with rubber-hydrocarbon mixtures, and these mixtures can be
+used both as water-proofing films, as applied to textiles, or can be
+solidified into the class of goods known as 'mechanicals.' The cellulose
+not only cheapens the mixture, but produces new technical effects.
+
+_Spinning._--The viscose is spun by special methods, patented by C. H.
+Stearn. As produced in thread form, the diameters are approximately
+those of natural silk. In commercial form it is a multiple thread (of 15
+or more units) at from 50-200 deniers on the silk counts. It is a thread
+of high lustre, and more nearly approaches the normal cellulose in
+chemical properties than any of the other artificial silks. It can also
+be spun in threads of very much larger diameter, which can be used as a
+substitute for horsehair, for carbonising for incandescent electric
+lamps, &c.
+
+_Cellulose Esters._--These are conveniently made from cellulose,
+regenerated from the solution as sulphocarbonate. The tetracetate is
+made from this product on the industrial scale. Nitrates are
+conveniently made by treatment with the ordinary mixed acids. For fuller
+details the original report may be consulted.
+
+
+VISKOS.
+
+R. W. STREHLENERT (Svensk Kemisk Tidskrift, Stockholm, 1900, p. 185).
+
+A report on the industrial development of viscose, covering essentially
+the same ground as the above.
+
+
+~Ueber die Viscose.~
+
+B. M. MARGOSCHES (Reprint from Zeitschrift fuer die gesammte
+Textil-Industrie, 1900-01, Nos. 14-20).[11]
+
+
+~Report of Committee on the Deterioration of Paper.~
+
+(Soc. of Arts, 1898.)
+
+(p. 304) The Report of a Representative Committee appointed by the
+Society of Arts to inquire into the question of qualities of book papers
+in relation to their several applications, and more especially for
+documents of permanent value.
+
+The report first discusses the two directions of depreciation of papers
+in use: (1) Actual disintegration shown by loss of resistance to
+fracture by simple strain, and by loss of elasticity--i.e. increase of
+brittleness; (2) discolouration. These are independent effects, but
+often concurrent. They are the result of chemical changes of the
+cellulose basis of the paper, brought about by acids or oxidants used in
+the process of manufacture, and not completely removed from the pulp, or
+by acid products of bleaching--e.g. oxycelluloses or chlorinated
+derivatives; again, by the changes of starch used as a 'sizing' agent,
+or by oxidations induced by rosin constituents when the rosin is used in
+excess. Discolouration is an attendant phenomenon of these changes, but
+is more frequently due to the presence of the lower-grade celluloses
+(esparto and straw) and the lignocelluloses (mechanical wood-pulp).
+
+The physical and chemical qualities of papers depending primarily upon
+their fibrous or pulp basis, and in a secondary degree upon the kind and
+proportion of the constituents added for the purpose of filling and
+'sizing,' the report concludes with the following recommendations,
+positive and negative, under these heads:
+
+The Committee find that the practical evidence as to permanence fully
+confirms the classification given in the Cantor Lectures on 'Cellulose,'
+1897 [J. Soc. Arts, xlv. 690-696], and which ranges the paper-making
+fibres in four classes:
+
+(A) Cotton, flax, and hemp (rhea).
+
+(B) Wood celluloses, (a) sulphite process and (b) soda and
+'sulphate' process.
+
+(C) Esparto and straw celluloses.
+
+(D) Mechanical wood-pulp.
+
+In regard, therefore, to papers for books and documents of permanent
+value, the selection must be taken in this order, and always with due
+regard to the fulfilment of the conditions of normal treatment above
+dealt with as common to all papers.
+
+The Committee have been desirous of bringing their investigations to a
+practical conclusion in specific terms--viz. by the suggestion of
+standards of quality. It is evident that in the majority of cases there
+is little fault to find with the practical adjustments which rule the
+trade. They are, therefore, satisfied to limit their specific findings
+to the following--viz. (1) normal standard of quality for book-papers
+required for publications of permanent value. For such papers they
+specify as follows:
+
+Fibres: Not less than 70 p.ct of fibres of class A; class D excluded.
+
+Sizing: Not more than 2 p.ct. rosin, and finished with the normal
+acidity of pure alum; starch excluded.
+
+Loading: Not more than 10 p.ct. total mineral matter (ash).
+
+(2) With regard to written documents, it must be evident that the proper
+materials are those of class A, and that the paper should be pure and
+sized with gelatin, and not with rosin. All imitations of high-class
+writing-papers which are, in fact, merely disguised printing-papers,
+should be carefully avoided.
+
+_Appendix._--To the Report is added 'Abstracts of Papers' in
+'Mittheilungen aus den Koniglichen Technischen Versuchsanstalten,
+Berlin,' for the years 1885-1896 inclusive--which is, in fact, a summary
+of the investigations of the Institution in connection with paper and
+paper-standards.
+
+       *       *       *       *       *
+
+(p. 273) ~Special Industrial Developments.~--From the point of view of the
+chemist there has been a very large development of the cellulose
+industries during the last five years. This is not so much marked by the
+gradual and progressive growth of the well-established industries, as by
+the success of the newer ones, with the attendant forecast of enormous
+developments of the industries in artificial products, the manufacture
+of which rests upon a purely chemical basis. We can, of course, only
+treat them from this limited standpoint, and so far as they involve and
+elucidate chemical principles.
+
+
+~I. Chemical Treatments of Raw Materials.~
+
+(a) ~Flax-spinning.~--The treatment of the roving on the spinning-frame
+by the addition of reagents to the macerating liquid--otherwise and
+usually hot water--continues to be justified by results. The technical
+basis of the process and the reactions determined in the spinning-trough
+by the alkaline salts used--chiefly sulphite and phosphate of soda--is
+set forth in the original work, p. 280. Since that time a sufficient
+period has elapsed to judge the effects, both technical and industrial,
+by the results of a commercial undertaking based on the exclusive use of
+the process. Such a concern is the Irish Flax Spinning Company of
+Belfast. At this mill the experience is uniform and fully established
+that by means of the process the drawing, i.e. spinning, quality of
+inferior flaxes is very considerably appreciated, enabling the spinner
+to use such flaxes for yarns of fineness which are unattainable by the
+ordinary method of spinning through hot water. Notwithstanding the
+success of this undertaking the development of the method is still
+inconsiderable. It is none the less a further and forcible demonstration
+of the existence of margins of increased technical effect which it is
+the work of the scientific technologist to exploit.
+
+(b) ~Wood-pulp and Methods of Manufacture.~--There is a steady growth in
+the consumption of wood-pulps (cellulose) relatively to other materials.
+In regard to the paper-trade of the world, this continues to be one of
+the most prominent characteristics of its evolution. In the United
+Kingdom the conditions of its competition are of a more special kind by
+reason of the firm foothold of esparto, which is a most important staple
+in the manufacture of fine printings. Whereas the consumption of esparto
+remains nearly stationary at about 200,000 tons per annum, the
+importation of wood-pulps has shown the extraordinary rate of increase
+of doubling itself every five years. But in the group 'wood-pulps' the
+trade returns have until recently included the 'mechanical' or ground
+wood-pulps. From 1898 we have separate returns for the chemical or
+cellulose pulps, and in 1899 the tonnage reached nearly to that of
+esparto, with a total money value about 80 p.ct. greater. When it is
+remembered that this is one of the newer chemical industries in
+cellulose products, and that these large commercial results have been
+accomplished during a period of twenty years, we are impressed with the
+scope of the industrial outlook to the chemist, afforded by the arts of
+which cellulose is the foundation.
+
+It may be noted that there have been no important developments in the
+purely chemical processes involved in the several systems of preparing
+cellulose from wood. The acid methods (bisulphite processes) have
+developed much more extensively than the alkaline, the latter including
+the caustic soda and the mixed sulphide ('Dahl') process. The bisulphite
+processes depended in the earlier stages upon the efficiency of
+lead-lined digesters. But the problem of acid-resisting linings has been
+much more perfectly solved in later years in the various types of cement
+and other silicate linings now in use. The relative permanency of these
+linings has had an important effect on the costs of production. Further
+economies result from the use of digesters of enormous capacity, dealing
+with as much as 100 tons of wood at one operation. As a combined result
+of economic production and active competition, the selling prices of
+'sulphite pulp' have moved steadily downwards in relation to other
+half-stuffs and raw materials. As a necessary consequence the prices of
+those which it has gradually displaced have depreciated, and a study of
+the price and tonnage-equilibrium as between rags, esparto, and
+wood-pulp over a series of years forms an interesting object-lesson in
+the struggle for survival which is an especial mark of modern industry.
+For these matters the reader is referred to the special literature of
+the paper-making industry.[12]
+
+It is not a little remarkable that the main by-product of these
+bisulphite processes--the sulphonated derivatives of the lignone
+constituents of the wood--is still for the most part an absolute waste,
+notwithstanding the many investigations of technologists and attempts to
+convert it to industrial use (see p. 149). Seeing that it represents a
+percentage on the wood pulped equal to that of the cellulose obtained,
+it is a waste of potentially valuable material which can only be termed
+colossal. Moreover, as a waste to be discharged into water-courses, it
+becomes a source of burden and expense to the manufacturer, and with the
+increasing restrictions on the pollution of rivers it is in many
+localities a difficulty to be reckoned with only by the cessation of the
+industry. The problem in such cases becomes that of dealing with it
+destructively, i.e. by evaporation and burning. In this treatment the
+obviously high calorific value of the dissolved organic matter (lignone)
+appears on the 'credit' side. But where calcium and magnesium
+bisulphites are used, the residue from calcination is practically
+without value. It appears, however, that by substituting soda as the
+base the alkali is recoverable in such a form as to be directly
+available for the alkaline-sulphide or 'Dahl' process. As a more
+complicated alternative the soda admits of being recovered on the lines
+of the old black-ash or Leblanc process, and the sulphur by the now
+well-established 'Chance' process, for which, of course, an addition of
+lime is necessary to the fully evaporated liquors previously to
+calcining. The engineering features of the system, so far as regards
+evaporating and calcining, are the same. For economic working there is
+required (a) evaporation by multiple effect and (b) calcining on the
+continuous rotary principle. For the latter a special modification has
+been devised so that the draught of air is concurrent with the movement
+of the charge in the furnace, securing a progressively increasing
+temperature within the furnace. This interesting development of the
+chemical engineering of wood-pulp systems has been elaborated by two
+well-known technologists, Drewson and Dorenfeldt, and readers who wish
+to inform themselves in detail of these developments are referred to the
+various publications of these inventors.
+
+Assuming the present necessity of a destructive treatment of the
+by-products of the bisulphite processes, the scheme has many advantages.
+The soda-bisulphite liquors are more economically prepared; the pulp
+obtained is superior in paper-making quality to that resulting from the
+lime or magnesia (bisulphite) processes: it is more economically
+bleached.
+
+Then, as pointed out, the soda may on the one plan be obtained in a form
+in which it is immediately available as a powerful hydrolysing alkali in
+the manufacture of a 'soda' pulp. These two systems become, therefore,
+in a new sense complementary to one another. Lastly, it is obvious that
+the employment of soda as the base opens out a new vista for developing
+the electrolytic processes of decomposing common salt.
+
+The authors have assisted in preparing plans for a comprehensive
+industrial scheme combining all these more modern developments. In this
+scheme it is only the combination which is novel, and as it involves no
+new principles in the chemical treatments of the materials we are not
+further concerned with it than to have briefly sketched its economic
+basis. This may be summed up in result in the important question of cost
+and selling price, and the estimate is well grounded that by means of
+this scheme _bleached wood-pulp_ can be sold on the English market at
+10l. a ton. It is important to note this figure and to compare it with
+the prices of twenty years ago. The fall has been continuous,
+notwithstanding the influence of the opposing factors of increasing
+consumption, exhaustion of accessible supply of timber, and relative
+appreciation of the essential costs of steam, chemicals, and labour. It
+is important in forecasting the future, since the youngest and
+apparently most promising of the 'artificial' cellulose industries
+employs wood-cellulose by preference as its raw material (see p. 173).
+
+As a last point it must be considered that as chemists we are bound to
+anticipate the realisation of value in the soluble by-products of the
+bisulphite processes. Outside the intrinsic interest attaching to the
+solution of this problem, it carries with it the promise of a further
+economy in the production of wood-cellulose.
+
+~Bleaching of Vegetable Textiles.~--By far the largest of these industries
+are those which are engaged in producing the 'pure white' on cotton and
+flax goods. The process, considered chemically, is simply that of
+isolating a pure cellulose, and we endeavoured to give due prominence to
+this view in the original work. It is important to insist upon it for
+the reason that this view gives the due proportion of chemical value to
+the several contributory treatments--alkaline hydrolyses (caustic lime
+and soda boils), hypochlorite oxidations, and incidental acid treatments
+(souring). The first of these is by far the largest contributor of
+'chemical work,' though the second, by being the agent for the actual
+whitening effect or bleaching action proper, occupies a position of
+often exaggerated importance.
+
+In bleaching processes there has been no radical change of system on the
+large scale since the introduction of the 'Mather' kier in 1885, and the
+associated change from lime and ash boiling to the caustic soda
+circulating boil with reduced volume of lye, which this mechanical
+device rendered practicable. It is outside the scope of this work to
+follow up this branch of technology in any detail, and we cannot discuss
+the evolution of systems on variations of detail where no essential
+principle is involved. But we have to notice a very recent development
+which has only just begun its industrial career, and which does give
+effect to a principle of treatment not previously applied. This is
+tersely stated by its originator, William Mather,[13] in the
+expression, 'it is more economical to make liquids pass through cloth
+than to make cloth pass through liquids.' The starting point of this
+development is the invention of a complete self-contained machine in
+which a rolled batch of cloth can receive a succession of chemical
+treatments, with accessory washings--the solutions, or wash waters,
+being circulated through the cloth. The essential fact on which this
+system is based is that a perfect liquid circulation can be maintained
+from selvedge to selvedge through the folds of a tightly rolled batch of
+cloth. Such circulation is therefore quite independent of the diameter
+of the batch. If we consider a cloth under chemical treatment with
+solutions, it is clear that the reactions and interchanges of soluble
+matters within the cloth, within the twisted elements of the yarn, and
+in the last grade of distribution within the actual ultimate fibres, are
+subject to capillary transmission, and osmotic exchange. There is a
+mixture of these molecular effects, with the circulation in mass,
+sweeping both faces of the cloth. It is obvious that for the mass effect
+a relatively very small volume of circulating liquid is necessary to
+maintain uniform conditions of action. In the actual disposition of the
+machine the rolled batch of cloth nearly fills the cylindrical space of
+what we may call the reaction chamber, and the circulation of the liquid
+is maintained by a circulating pump and a differential pressure in the
+horizontal plane across and through the folds of the batch. This is in
+the meantime kept in slow revolution. For a full description of these
+mechanical details the reader is referred to the original patent
+specifications [Engl. Pat. 23,400, 23,401; 1900, W. Mather]. If we again
+consider the principles involved, they are very much as set forth in
+our original work (pp. 288-291). Boiling processes in which a
+relatively large volume of liquid is used are wasteful of steam, the
+active agent is unnecessarily diluted or used in superfluous quantity,
+and the soluble by-products, being continually removed as formed, cannot
+so effectively contribute by secondary actions to the chemical work. The
+new mechanical appliance enables us to further reduce the volume of
+liquid required in the alkaline-hydrolytic treatment of vegetable
+textiles, and where advantageous to bring the treatment down (or up) to
+a process of steaming with the active agent dissolved in a minimum
+proportion of water relative to the cloth. This concentration of effect
+is of importance in flax cloth, and especially linen treatment, where
+the peculiarly resistant cutocelluloses have to be attacked and a
+considerable proportion of waxy by-products to be removed. These points
+are the basis of the special process of Cross and Parkes [Engl. Pat.
+25,076/ 99] for steaming flax (and cotton) goods with an emulsion
+containing, in addition to the special hydrolysing agent--caustic
+soda--mixtures of soap with 'mineral' or other oils, the presence of
+which effectually aids the removal of the by-products in question.
+
+A complete system on these lines is now working on the industrial scale
+in the Belfast district. The results are not merely economical in
+largely reducing the number of alkaline boiling treatments required on
+the old plan of pan or 'pot' boiling, but are visible in the strength
+and finish of the linens so treated.
+
+For cotton bleaching the costs may be put down at a fraction of those of
+the Irish linen bleach. The economical advantages of the new system are
+obviously less in relation to the lesser total costs. But there are
+other points which have come into more prominent influence. The
+mechanical wear and tear on the cloth is considerable in the ordinary
+process, more especially in the mangle-washes. As a result the
+adjustment of warp and weft is more or less disturbed. These defects are
+absent from a system which operates on the cloth in a fixed position.
+
+But as we are mainly concerned with the purely chemical factors we
+cannot pretend to deal with textile questions. We have to notice the
+remaining element of chemical economy as it involves a fundamental
+principle. The practice of washing residues or products of reaction free
+from reagents and soluble by-products involves a well-known mathematical
+law, under which the rate of purification is a function rather of the
+_number_ of successive changes of washing liquid than of the volume of
+the latter. The ordinary practice of textile washings entirely ignores
+this principle, and the consumption of water in consequence may reach
+many thousand times the economic minimum. With supplies of water often
+in indefinite excess of requirements, even in this most wasteful method,
+bleachers are in no need to consider the question of consumption. But
+leaving aside particular and local considerations of advantage the fact
+is that the new system gives control of the practice of washing,
+enabling the operator to adapt an important element of the daily routine
+to a fundamental principle which has been almost universally ignored.
+
+In the oxidising processes which follow the alkaline treatments, the
+hypochlorites are still the staple agents. Owing to the steady relative
+fall in the selling prices of the permanganates these are coming into
+more extensive use, but the consumption is still small, and they are
+mainly used for certain special effects, chiefly in linen or more
+generally flax cloth bleaching.
+
+~Paper-pulp Spinning.~--Paper is a continuous web or fabric produced by
+the interlocking of the structural fibrous units of the well-known short
+length. In Japan and other countries paper is made to serve for all or
+some of the purposes for which we employ string or twine, and to give
+the necessary tensile strength the paper is twisted or rolled on itself.
+Such twisting, however, adds nothing to the intrinsic tensile qualities
+of the original paper.
+
+A new technical effect is realised in this direction by the treatment of
+paper-pulp in the process of its conversion into a continuous web: The
+pulp is formed into continuous strips of convenient breadth (usually
+from 2 to 8 mm.), these receive a 'rolling-up' treatment immediately
+following the squeeze of the press rolls by which the superfluous water
+is removed: they are then further but incompletely dried, and in this
+condition are subjected to a final spinning or twisting treatment on
+ring-spinning machinery of special construction.
+
+Such a process was originally patented by C. Kellner in this country
+(E.P. No. 20,225/1891), and is fully described in his specification.
+Later improvements in detail were patented by G. Tuerk (E.P. 4621/1892).
+
+A joint system is now being industrially developed in Germany by the
+Altdamm-Stahlhammer Pulp and Paper Company under the technical direction
+of Dr. Max Mueller, and there appears to be every prospect of the product
+taking a position as a staple textile.
+
+The process has only the incidental interest in connection with our main
+subject, that it employs chiefly the 'chemical' pulps or celluloses as
+raw materials. The industrial future of the application must, of course,
+be largely determined by costs of production, as the directions of
+application in the weaving industries will be limited by the necessarily
+inferior grade of tensile strength belonging to these products and the
+degree by which this is lowered on complete wetting. All these questions
+have been duly weighed by those engaged in this interesting development,
+and the conclusion of those qualified to judge is that the new industry
+has vindicated for itself a permanent position.
+
+~II. The Chemical Derivatives of Cellulose~, in their industrial aspects,
+have come to occupy a profoundly important position in the world's
+affairs. In the way of any essential alteration of the perspective from
+that obtaining in 1895 we have nothing to chronicle. No new derivatives
+of industrial importance have been added in that period; but certain new
+methods incidental to the preparation of well-known compounds or for
+converting them into more generally available forms have been
+introduced, and these are contributing to the rapid expansion of the
+'artificial' cellulose industries.
+
+Of the cellulose esters the nitrates are still the only group in
+industrial use. There uses for explosives have attained immense
+proportions, and their applications for structural purposes are
+continually on the increase. The manufacture of smokeless powders on the
+one hand, and of celluloid and xylonite (both in the form of films and
+solid aggregates) on the other, has taken no new departure. The industry
+in 'artificial silks' or 'lustra-celluloses,' by the collodion processes
+also, whilst presenting features of unusual interest attaching to rapid
+expansion, has been barren of contribution of fundamental scientific or
+technical importance. The tetracetate is now manufactured on the large
+scale, but the product has yet to make its market.
+
+The process of mercerising cotton yarns and cloth has been developed to
+an industry of colossal dimensions, and the growth has been especially
+rapid during the last five years. Significant of the technical progress
+in these two industries, with their common aim of appreciating cellulose
+in the scale of textiles by approximating its external properties in
+those of silk, is the appearance of a monograph of the technology of
+each, notices of which have been previously given (pp. 22-26).
+
+There is little doubt, however, that the question of the future
+industry in the various forms of cellulose, thread, film, structureless
+powder or solid aggregate, obtainable by artificial means, mainly turns
+upon cost of production. Irrespective of cost, there would, no doubt, be
+a market for all these products, based upon such of their properties or
+effects as are indispensable and not otherwise obtainable. As an
+illustration, we may cite the extraordinary selling prices of 40-50 fr.
+per kilo, for the 'artificial silks' (collodion process) which ruled
+some three years ago; and we may note that for a special application of
+viscose the dissolved cellulose is paid for at the rate of 10 per
+lb. These facts are certainly worthy of mention, and should be borne in
+mind as an index of some special features of modern manufacturing
+industry. But with a material like cellulose rendered available in a new
+shape the question which always arises more prominently than that of
+limited uses at high prices is that of consumption on the extensive
+scale which marks the older and well-known products. That question is
+rapidly solving itself in this country as regards the 'artificial
+silks.' There is at present a limited market at 9s.-10s. per lb., a
+price which on the one side excludes extensive consumption, and on the
+other practically bars manufacture in this country by any of the
+collodion systems. It will appear from a very elementary calculation of
+what we may call the theoretical costs that the above selling price
+would not have a remunerative margin. The theoretical costs are made up
+of
+
+Raw materials[14]  {Cotton. Nitrating acid. Ether-alcohol (solvent).
+                   {Denitrating chemicals.
+
+                   {(a) Nitrating and preparing collodion. Denitrating
+                   { and bleaching.
+Labour             {(b) Textile operations. Spinning. Winding and twisting.
+                   {Rewinding.
+
+Power              {Making, filtering, and distributing collodion.
+                   {Driving textile machinery.
+
+Added to which are the costs of expert management and supervision and
+general establishment expenses. It is evident that raw materials make up
+a large fraction of the total cost; also that a very large item is the
+waste work of converting the cellulose into nitrate, only to remove the
+nitric groups so soon as the cellulose is obtained as thread.
+
+It is clear that the aqueous solutions of cellulose have a double
+advantage in this respect--not only do they readily yield an
+approximately pure cellulose as a direct product of regeneration or
+decomposition, but the first cost of the solution is very much less.
+With these newer products, therefore, the spinning problem enters on a
+new phase of struggle. It is certain that at selling prices at or about
+5s. to 7s., very large markets will be open to the product or
+products. The two processes which are or may be able to fulfil this
+demand are those based (1) on cuprammonium solutions of cellulose, (2)
+on the sulphocarbonate or viscose. As regards _first cost_ of the
+solution the latter has a large advantage. One ton of wood pulp (at
+12l.) can certainly be obtained in solution in a condition ready for
+spinning at a total cost (materials) of less than 30l. The
+cuprammonium process, so far as 'outside' information goes, requires for
+production of the solution (1) cotton as raw material, (2) ammonia
+(calc. as concentrated aqueous) equal to 1-1/2 times its weight, and
+(3) metallic copper 25 p.ct. of its weight; and the costs are
+approximately 100l. per ton. It is obvious that the materials are
+recoverable from the precipitating-bath, but at a certain added cost. We
+have no statements as to the proportion recoverable nor the costs
+incurred, and we are therefore unable to measure the total net cost of
+the regenerated cellulose by this process. It is certainly much less
+than by the collodion processes. As to the textile quality of the
+thread, the product has not yet been on a sufficiently wide selling
+basis for that to have been determined. There are a great many factors
+which enter here. Not merely the external characters of lustre,
+softness, and translucency, but the all-important quality of uniformity
+of thread. The collodion-spinning is a process still very defective in
+this respect, and the defect is no doubt referable to the difficulty of
+securing absolute physical invariability of the collodion. It is to be
+regretted, in the interests of scientific development, that none of the
+technologists who have published investigations of these processes have
+entered into the discussion of the fundamental factors of the spinning
+processes; we are, therefore, unable at this stage to discuss these
+elements of a full comparison in greater detail. We cannot, for this
+reason, say how far the cuprammonium process diverges in point of
+control from the standard of the collodion processes. Of the 'viscose'
+product we have a more intimate knowledge, and it certainly reaches a
+higher general standard than the older and now well-known artificial
+silks. The process is also sufficiently developed to enable the total
+costs of production to be estimated at a figure less than one-half that
+of the 'collodion' processes. This would assure to this system an
+_entree_ in this country, and a basis of expansion limited only by the
+ordinary laws of supply and demand.
+
+This prospect is opened up precisely at the moment when, for various
+reasons connected both with the difficulties of manufacture and the
+narrowing of the margin of profit, the proprietors of the two systems of
+collodion-spinning have decided to abandon all idea of manufacturing by
+these systems in this country.[15] We leave the discussion of the
+industrial problem at this point.
+
+In regard to other developments based upon the exceptional character and
+properties of the sulphocarbonate, their further discussion will
+exemplify no general principles; and as regards technical detail they
+have been dealt with in the papers previously noticed.
+
+As a purely general question, if there is to be any industry in these
+'artificial' forms of cellulose, commensurate with the magnitude that
+usually belongs to the cellulose industries, it must come by way of a
+plastic or soluble form prepared at low cost, and conserving the
+essential molecular properties of the cellulose aggregate. These are the
+particular features of the sulphocarbonate. The obvious difficulties in
+the way of its industrial applications are those caused by the presence
+of alkali and sulphur compounds. These are dealt with by appropriate
+chemical means; but the fact that there is a special chemistry of the
+product has rendered its industrial progress slow. The work of the last
+five years in this, as in other applications of cellulose in its many
+derived forms, has resulted in a considerable addition to the domain of
+practical chemistry.
+
+Further developments will make an increasing demand upon our grasp of
+the fundamental constitutional problems, to which it is the main purpose
+of the present volume to contribute.
+
+FOOTNOTES:
+
+[11] This is the most complete notice that has appeared and the
+bibliography is exhaustive. The publication comes into our hands too
+late to be noticed in detail.
+
+[12] _Text-book on Paper-making_, Cross and Bevan (Spon, London: second
+edition, 1900). _Chemistry of Paper-making_, Griffin and Little (New
+York, 1894: Howard Lockwood & Co.). _Handbuch d. Papierfabrikation_, C.
+Hofmann (Berlin). _Paper Trade Review_, London (weekly).
+_Papier-Zeitung_, Berlin.
+
+[13] William Mather, M.P., of the firm of Mather & Platt, Limited,
+Manchester.
+
+[14] The actual costs varying considerably in the various countries, we
+cannot make any specific statement. But from estimates we have made, the
+costs of obtaining cotton in filtered solution as collodion multiply its
+value by 12-14, the denitrations adding further costs and raising this
+multiple to 18-20. In the same estimates we arrived at the conclusion
+that the item for raw materials made up 60 p.ct. of the total cost of
+the yarn.
+
+[15] The recent failure of a French company founded for the exploitation
+of the cuprammonium process may be taken as showing that it presents
+very considerable technical difficulties. It is a matter of common
+knowledge that this company _estimated_ the costs of production to be
+such as to enable the product to be sold at 12 fr. per kilo., whereas
+the costs actually obtaining were a large multiple of this figure.
+
+
+
+
+INDEX OF AUTHORS
+
+
+Bardy, C. H., 157
+
+Bokorny, T., 43
+
+Bronnert, E., 54
+
+Bumcke, G., and Wolffenstein, R., 67
+
+Buntrock, 25
+
+
+Cross, C. F., 139, 152, 155
+
+Cross, C. F., and Bevan, E. J., 92
+
+Cross, C. F., Bevan, E. J., and Briggs, J. F., 118
+
+Cross, C. F., Bevan, E. J., and Heiberg, T., 114
+
+Cross, C. F., Bevan, E. J., and Smith, C., 101, 103, 105, 114, 145
+
+
+De Haas, R. W. T., and Tollens, B., 151
+
+
+Faber, O. v., and Tollens, B., 71
+
+Feilitzen, H. v., and Tollens, B., 154
+
+Fenton, H. J. H., 8
+
+Fenton, H. J. H., and Gostling, M., 86
+
+Fraenkel, A., and Friedlaender, P., 26
+
+
+Gardner, P., 22
+
+Gilson, E., 112
+
+
+Hancock, W. C., and Dahl, O. W., 135
+
+Hoffmeister, W., 96, 100
+
+
+Kleiber, A., 97
+
+Kroeber, E., 121
+
+Krueger, M., 119
+
+
+Lange, H., 25
+
+Lewes, V. H., 15
+
+Luck, A., and Cross, C. F., 45
+
+
+Margosches, B. M., 159
+
+Morrell, R. S., and Crofts, J. M., 114
+
+Mylius, F., 21
+
+
+Nastukoff, H., 74
+
+
+Omelianski, V., 76
+
+
+Ruff, O., 117
+
+
+Salkowski, E., 113
+
+Schoene, A., and Tollens, B., 124
+
+Seidel, H., 149
+
+Sherman, H. C., 137
+
+Simonsen, E., 146
+
+Storer, F. H., 142
+
+Strehlenert, R. W., 158
+
+Suringar, H., and Tollens, B., 16, 124
+
+Suevern, C., 63
+
+
+Tollens, B., 148, 151
+
+Tollens, B., and Glaubitz, H., 122
+
+
+Vignon, L., 43, 70, 72, 94
+
+
+Will, W., and Lenze, P., 41
+
+Winterstein, E., 109, 144, 153
+
+
+
+
+INDEX OF SUBJECTS
+
+
+Acetone, action on cellulose nitrates of diluted, 46
+
+Acid-cellulose, 68
+
+Acids, volatile, from cellulose, 145
+
+_AEschynomene aspera_, 135
+
+Alcohol from cellulose and wood, 146
+
+Alcoholic soda, mercerisation results with, 26
+
+Alkali-cellulose, effects of long storage on, 31
+
+Amyloid, vegetable, 153
+
+Arabinose from gluconic acid, 117
+
+'Ash' of plants, 13
+
+
+_Bacterium xylinum_, 85
+
+Barley plant, chemical processes in the, 103
+
+---- straw, carbohydrates of, 105
+
+Bleaching, 166
+
+Bran, digestion of, 139
+
+Brommethylfurfural, 8, 84, 86
+
+
+Carbohydrates, action of hydrogen bromide on, 86;
+  action of hydrogen peroxide on, 114;
+  nitrated, as food for mould fungi, 43;
+  nitrates of, 41;
+  quantitative separation of, 96
+
+Carbohydrates of barley straw, 105;
+  of wheat, 137;
+  of yeast, 113
+
+'Caro's reagent,' 118
+
+'Celloxin,' 71
+
+Cellulose, alcohol from, 146;
+  constitution of, 77, 92;
+  fermentation of, 76;
+  industrial uses of, 155;
+  iodine reaction of, 21;
+  methods for the estimation of, 3, 4, 16, 19, 97;
+  nitration of, 43;
+  saccharification of, 73;
+  ultimate hydrolysis of, 11;
+  volatile acids from, 145
+
+---- acetates, monoacetate, formation of, 40;
+  tetracetate, constitution of, 80
+
+---- benzoates, 34;
+  from structureless cellulose, 36;
+  from three varieties of cotton, 35;
+  monobenzoate, properties of, 36;
+  dibenzoate, properties of, 37;
+  acetylation of, 130;
+  nitration of, 38
+
+---- derivatives, commercial aspects of, 171;
+  saccharification of, 73
+
+---- nitrates, 44, 45, 83;
+  structureless, 45, 51;
+  cupric reducing power of, 73;
+  instability of, 50, 53
+
+---- sulphocarbonate, 27;
+  effects of the nature of the cellulose, 28;
+
+---- ---- solutions, analysis of, 32;
+  iodine reaction of, 33;
+  loss of carbon bisulphide, 33;
+  viscosity of, 30
+
+Cell-wall constituents, 97
+
+Cereal celluloses, 101, 105
+
+Chitin, 112
+
+Chlorination, Cross and Bevan's method, 19;
+  statistics of, 134
+
+Chloro-lignone, 126
+
+Collodion. _See_ Silk, artificial
+
+Cotton, lustreing effect of mercerisation, 23;
+  mercerised, structural properties of, 25;
+  pentosane content of, 148
+
+'Crude fibre,' 17
+
+Cuprammonium solvent, 21, 58, 173
+
+Currants, pectin of, 152
+
+
+Denitration of collodion silk, 56;
+  of jute nitrate, 133;
+  products of, 74
+
+Dioxybutyric acid, 71
+
+
+Elder pith, 137
+
+Eriodendron, seed hair of, 92
+
+Explosives, 44;
+  sporting powders, 52
+
+
+Fermentation of cellulose, 76;
+  of furfuroids, 108;
+  of sugar from wood, 148
+
+Fibres, report on miscellaneous, 139
+
+Flax boiling, 168;
+  spinning, 161
+
+Fodder plants, pentosanes of, 122
+
+Fungi, tissue constituents of, 109
+
+Furfural from cellulose, oxycellulose, and hydrocellulose, 70;
+  derivative from laevulose, 8;
+  estimation as hydrazone and phloroglucide, 119, 121;
+  oxidation of, 114, 118 (_refer also_ 'Pentosanes')
+
+Furfuroids, 8, 10, 102, 105;
+  assimilation of, 108
+
+
+Gabriel's method of cellulose estimation, 18
+
+Gluconic acid, action of hydrogen peroxide on, 117
+
+Glucosamin, 112
+
+
+Hemicellulose, 96, 97;
+  determination and separation of, 100
+
+Hoenig's method of cellulose estimation, 18
+
+'Hydralcellulose,' 68
+
+Hydrocellulose, 73;
+  nitration of, 43
+
+Hydrogen peroxide, oxidations with, 114
+
+Hydroxyfurfural in lignocellulose, 9, 116, 118
+
+
+Incandescent mantles of artificial silk, 14, 15
+
+Industrial appliances of cellulose, 155
+
+Iodine reaction of cellulose, 21
+
+Isosaccharinic acid, 71
+
+
+Jute, composition of, 141;
+  quality of, 140;
+  treatment of, 142 (_refer also_ Lignocellulose)
+
+---- acetate, 129
+
+---- benzoate, 127;
+  acetylation of, 130;
+  nitration of, 132
+
+---- nitrate, 131
+
+
+Ketoses, physiological importance of, 9
+
+
+Lange method of cellulose estimation, 18, 98
+
+Lead compounds of nitrated carbohydrates, 49
+
+Lignin, 100
+
+Lignocellulose, constitution of, 133;
+  esters of, 125;
+  hydroxyfurfural in, 9;
+  new type of, 135
+
+Lignone complex, properties of, 126
+
+'Lignorosin,' 151
+
+'Lustra-cellulose.' _See_ Silk, artificial
+
+
+Malt, pentosanes of, 122
+
+Mather system of boiling textiles, 167
+
+Mercerization, 22; shrinkage during, 24
+
+Mercerised yarn, strength and elasticity of, 25, 26
+
+Methylhydroxyfurfural, 84
+
+Mould fungi, nitrated carbohydrates as food for, 43
+
+Mycosin, 113
+
+
+Nitrated carbohydrates, lead compounds of, 49
+
+Nitrates of carbohydrates, 41
+
+Nitrocellulose (_see_ Cellulose nitrates);
+  silk, 55
+
+'Normal' cellulose, definition of, 27
+
+Normal paper, 160
+
+
+Oxycellulose esters, 72;
+  nitration of, 43;
+  researches on, 71, 72, 74;
+  _resume_ of properties, 94
+
+Oxygluconic acid, 117
+
+
+Paper, deterioration of, 155;
+  normal standard, 160;
+  pulp, spinning of, 169
+
+Peat, constituents of, 154
+
+Pectins, 151, 152
+
+Pentosanes, 100, 109, 144;
+  constituents of cotton, 124;
+  constituents of fodder, 122;
+  estimation of, 121;
+  of seeds during germination, 124
+
+'Permanent tissue,' 103
+
+Phloroglucinol, 119, 121
+
+Plant tissues, carbohydrates of, 96, 97, 99
+
+Plants, source of unsaturated compounds in, 145
+
+Powders, manufacture of sporting, 52
+
+
+Saccharification of cellulose and derivatives, 73
+
+Schulze method of cellulose estimation, 18, 98
+
+Schweizer solution, 101
+
+Seeds, pentosanes in germinating, 124
+
+Silica in plant tissues, 13
+
+Silk, artificial, 54, 62, 63, 172;
+  bibliography of, 60;
+  from cuprammonium, 58, 64, 173;
+  from nitrocellulose (collodion), 55, 63, 172;
+  from viscose, 59;
+  from zinc chloride, 59;
+  reactions of, 64
+
+---- natural, reactions of, 64
+
+Straws, 101, 105
+
+Succinic acid from furfural, 118
+
+Sulphite waste liquors, 149, 164
+
+'Swedish' filter paper, 14
+
+
+Tissue constituents, 99, 109
+
+Trees, composition of trunk woods, 142
+
+
+Viscose and viscoid, 157, 158, 159
+
+---- silk, 59, 175
+
+---- ---- specific gravity of, 34 (_refer also_ Cellulose
+sulphocarbonate)
+
+'Vulcanised fibre,' 20
+
+
+Weende, method of cellulose estimation (crude fibre), 17, 98
+
+Welsbach mantles, 14;
+  Clamond type, 15
+
+Wheat grain, insoluble carbohydrates of, 137
+
+Wood, alcohol from, 146, 148
+
+Wood-cellulose, waste liquors, 149
+
+Wood-gum, 144
+
+Wood-pulp, processes, 162
+
+Wood, trunks of trees, 142
+
+
+Yeast, carbohydrates of, 113
+
+
+Zinc chloride, artificial silk, 59;
+  solvent action of, 20
+
+
+
+
+
+
+End of the Project Gutenberg EBook of Researches on Cellulose, by
+C. F. Cross and E. J. Bevan
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