BOUGHT WITH THE INCOME 
 FROM THE 
 
 SAGE ENDOWMENT FUND 
 
 THE GIFT OF 
 
 Henrg W. Sage 
 
 1891 
 
 A15W1 mim 
 
Cornell University Library 
 arV10477 
 
 Researches on cellulose 1895-1900 
 
 olin.anx 
 
 3 1924 031 240 454 
 

 With 
 
 14 Plates. Crown Zvo. 12s. net 
 
 I 
 
 
 
 CELLULOSE 
 
 
 AN 
 
 OUTLINE 
 
 OF THE CHEMISTRY OF THE STRUCTURAL 
 
 
 
 ELEMENTS OF PLANTS 
 
 
 
 With reference to their Natural History and 
 
 
 
 
 Industrial Uses 
 
 
 
 
 By CR,OSS and BEVAN 
 
 
 (C. 
 LONGMANS, 
 
 F. Cross, E. J. Bevan, and C. Beadle) 
 
 London 
 
 GREEN, & CO., 39 Paternoster Row, 
 
 
 
 New York and Bombay 
 
 
RESEARCHES ON CELLULOSE 
 
 895-1900 
 
 BY 
 
 CROSS & BEVAN 
 
 (C. F. CROSS AND E. J. BEVAN) 
 
 LONGMANS, GREEN, AND CO. 
 
 39 PATERNOSTER ROW, LONDON 
 
 NEW YORK AND 60MBAY 
 
 1901 
 
 K 
 
 AH rights reserved 
 
The original of tliis book is in 
 tine Cornell University Library. 
 
 There are no known copyright restrictions in 
 the United States on the use of the text. 
 
 http://www.archive.org/details/cu31924031240454 
 
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 prkcis, 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 con- 
 clusions, 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 
 limited equivalent of 'wood cellulose.' The restriction of this 
 
vi Cellulose 
 
 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 agricul- 
 tural 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 con- 
 spicuous 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 v.'orking career in connection 
 with the cellulose industries. They will not find this invi- 
 tation 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 
 
Preface vii 
 
 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 oppor- 
 tunities which belong to the days of small beginnings. 
 
 The book is printed on Standard Printing Paper, made 
 to the specification of the Society of Arts Committee (see 
 p. 1 60 of the text). 
 
 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 
 
 SECTION 
 
 I. GENERAL CHEMISTRY OF THE TYPICAL COTTON CELLULOSE I3 
 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 .... . II4 
 
 VI. THE LIGNOCELLULOSES . . . . I25 
 
 VII. PECTIC GROUP .... . . . 152 
 
 VIIL INDUSTRIAL AND TECHNICAL. GENERAL REVIEW . -155 
 
 INDEX OF AUTHORS ... . -177 
 
 INDEX OF SUBJECTS 178 
 
ERRATA AND MISPRINTS IN 
 'CELLULOSE,' 1895. 
 
 Table of Contents ; for 
 
 COMPOUND CELLULOSES 
 
 read 
 
 LiGNOCELLULOSES 
 
 COMPOUND CELLULOSES 
 
 ^9 
 89 
 
 Page 3, 
 .. 17. 
 If 20, 
 
 ,. 43. 
 
 .. 53. 
 
 ,, 76, 
 
 .. 77. 
 
 .. 123. 
 
 .. 124, 
 
 ,. I36. 
 
 ,. IS8. 
 
 ,, 171. 
 
 . 173. 
 . 179. 
 , 187, 
 , 21S. 
 . 2SS. 
 I 269, 
 . 271, 
 . 272, 
 
 line 3, cellulose in place o/' celluloses 
 ,, 24, they in place of that 
 ,, 17, This phrase should read : 'The time . . . varies of course with 
 
 the temperature and the concentration of the acid.' 
 ,, ■^, ioTmation in place 0/ comhMstion 
 ,, 30, action in place of effect 
 ,, 23, from in place of rom 
 ,, 15, C atoms in place o/O atoms 
 ,, 31, alkalis in place o/" alkali 
 ,, 4, which in place of vfhere 
 
 These statements as to composition of jute cellulose have 
 
 been revised. See page 134. 
 The statistics on this page have also been corrected and 
 prevised. See page 135. 
 ,, Table, Differences ; The ' 31 'So p.ct.' should be carried out into 
 the first column, and, added to the remainder, gives the 
 total of 100. This column requires completing by the usual 
 lines signifying addition and the 'loooo' immediately 
 below. 
 21, O4 in place o/O 
 4, this in place of thus 
 16, acid hydrolysis in place 0/ hydrolysis acid 
 27, ' Broom ' is wrongly described as ' Plantago Psyllium.' 
 29, Hypochlorite in place o/Hypochloric 
 14, insert of after proportion 
 36, insert these before problems 
 I, for in place of or 
 
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 ad- 
 vance 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 
 
 B 
 
2 Cellulose 
 
 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 knovvs that it is 
 only the simpler of the carbohydrates which are so indi- 
 vidualised 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 httle 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 com- 
 petent 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 tne 
 work, though they make use of its matter. We think it neces- 
 sary 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 
 
Introduction 3 
 
 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 dp 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. t6 
 we give an account of an investigation of the several methods 
 of estimating cellulose, which is full of valuable and inter- 
 esting matter. The purpose of the author's elaborate com- 
 parative 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 
 
 B 2 
 
4 Cellulose 
 
 point out, is entirely determined on the question of aggregate 
 weight or yield, and without reference to the ultimate compo- 
 sition 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 hydro- 
 lysed 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 sub- 
 sequent hydrolysis upon the lignone group. As a matter of 
 fact it is the only method yet available for isolating the cellu- 
 lose 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 hz expected to be obtained in a hydrated form, 
 and also not as a homogeneous substance Hke the normal 
 cotton cellulose. The product is a cellulose of the second 
 group of the classification. Another point in this investiga- 
 tion 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 
 
Introduction 5 
 
 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 metliod of attack, and it is a reversion to pure empiri- 
 cism to expect any one treatment to act equally on the pecto- 
 celluloses, 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 rafifia (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 sulphocarbo- 
 nates 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 com- 
 pound 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 ex- 
 pressed by generalising a complex mass of statistics of its 
 successive hydrolyses, we can only still more vaguely guess at 
 
6 Cellulose 
 
 the distance which separates us from a mental picture of the 
 cellulose unit. We endeavour to show by our later investiga- 
 tions 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, pro- 
 portionately 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 com- 
 pound. 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 re- 
 duced to numerical expression. It is most likely that the 
 issue may conflict with some of our current views of the mole- 
 cular 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 
 
Introduction 7 
 
 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 esta- 
 blished 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 investi- 
 gation 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 hydroxy- 
 furfurals 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 com- 
 pounds (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 
 
8 Cellulose 
 
 la Membrane Cellulaire Vegdtale,' ' 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 paren- 
 chymatous celluloses. Indirectly also the researches of 
 ToUens 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 C5 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 
 
 CaHi20s-4H20-t-HBr= CHj.Oa.CHaBr 
 
 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 
 
Introduction g 
 
 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 mature 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 hydroxyfur- 
 furals 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 pre- 
 sence 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 evi- 
 dence as to the main facts which establish the general relation- 
 ships of the furfuroid group. This group includes both 
 saturated and unsaturated or condensed compounds. The 
 
lo Cellulose 
 
 former are constituents of celluloses, the latter of the lignone 
 complex of the lignocelluloses. 
 
 The actual production of furfural by boiling with con- 
 densing acids is a quantitative measure of only a portion, ?.«. 
 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 signifi- 
 cance of their own ; and there is a physiological or functional 
 
Introduction 1 1 
 
 cohesion marking this group which calls for recognition, at 
 least for the time, and we therefore propose to retain the term 
 furfuroid.' 
 
 General Experimental Methods. — In the investigation of 
 the cellulose group it is clear that methods of ultimate hydro- 
 lysis are of first importance. None are so convenient as those 
 which are based on the action of sulphuric acid, more or less 
 concentrated (H2SO4.3H2O-H2SO4H2O). Such methods 
 have been frequently employed in the investigations noted in 
 this volume. We notice a common deficiency in the inter- 
 pretation 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 approxi- 
 mated. In fact, what is very much wanted is a systematic 
 re-examination of the typical celluloses in which all the con- 
 stants 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 
 
 ' In this we are confirmed by other writers. See Tollens, J. fiir 
 Landw. 1901, p. 27. 
 
1 2 Cellulose 
 
 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 mole- 
 cular 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-propor- 
 tion. Physical criteria are only of determining value when asso- 
 ciated with such constants as cupric reduction, and these, 
 again, must be referred to some arbitrary initial weight, such 
 as, for convenience, loo 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 im- 
 portant 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 consti- 
 tution of the celluloses. 
 
M organic Constituents 13 
 
 (p. 3) ' 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 con- 
 taining 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 assump- 
 tion that the cuticular tissues of cereal straws, of esparto, 
 of the bamboo, owe their special properties to siliceous com- 
 ponents, 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 compo- 
 sition an! arrangement of the cells of the cuticle. 
 
 ' This and other similar references are to the matter of the original 
 volume (1895). 
 
1 4 Cellulose 
 
 ' 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 
 itjW "^g""- Psr I 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 solu- 
 tion. 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 
 
Inorganic Constituents 15 
 
 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 con- 
 taining 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. 
 
1 6 Cellulose 
 
 UNTERSUCHUNGEN UBER VERSCHIEDENE BESTIM- 
 MUNGSMETHODEN DER CELLULOSE. 
 
 H. SuRiNGAR AND B. ToLLENS (Ztschr. angcw. Chem. 
 1896, No. 23). 
 
 INVESTIGATION OF METHOSS OF SETEBMINING CELLTTLOSE. 
 
 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 pro- 
 duct 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 ligno- 
 celluloses. Hoffraeister 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 Miiller 
 (bromine water) and Cross and Bevan (chlorine gas). I.astly, 
 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 (Honig) yields a very 
 impure and ill-defined product. 
 
Separation — Estimation \j 
 
 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. 
 
 (V) 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 (i"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 (i'o6 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 em- 
 ployed jute fibre and raw cotton wool in their investiga- 
 tions. 
 
 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. 
 
1 8 Cellulose 
 
 Schuhe. — 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. 
 
 Honig'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 i8o°- 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 cellu- 
 loses 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 yalue, notwith- 
 standing, 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. 
 
 GabrieFs method of heating with a glycerin solution of 
 alkaline hydrate is a combination of ' Honig ' and ' Lange ' 
 
Separation — Estimation 
 
 19 
 
 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 it, p.ct. 
 furfural. 
 
 Cross and Bevan. — Chlorination pn-ocess yielded in the 
 hands of the authors results confirming the figures given in 
 ' Cellulose ' for yield of cellulose. Investigation of the pro- 
 ducts 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. Schufze 
 
 Weende 
 
 Lange 
 
 Gabriel 
 
 Cross and 
 Bevan 
 
 Wood cellulose 
 Filter paper cellulose 
 Swedish filter paper . 
 Ordinary filter paper 
 Cotton (' wool ') 
 Jute 
 
 Purified wood . 
 Raw wood 
 
 98-51 
 99-62 
 96-58 
 98-17 
 98-38 
 
 47 -60 
 
 91-52 
 95-63 
 
 93-39 
 89-98 
 
 48-22 
 
 78-17 
 84-76 
 86-58 
 63-96 
 57-93 
 
 /49-27 
 
 146-56 
 
 ; 40-82 
 1 38-87 
 
 55-93 
 79 77 
 
 67-88 
 71-64 
 
 75-27 
 
 The final conclusion drawn from the results is that none 
 of the processes fulfil the requirements of an ideal method. 
 
20 Cellulose 
 
 Those which may be carried out in a reasonably short time 
 are deficient in two directions: (i) they yield a 'cellulose' 
 containing more or less oxycellulose ; (2) the celluloses them- 
 selves 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 con- 
 stituents. Schulze's method appears to give the nearest 
 approximation to the ' actual cellulose ' of the raw material. 
 
 (p. 8) Solutions of Cellulose— (i) 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 reprecipi- 
 tated 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 i p.ct. 
 in weight. This, however, is a 'net' result, and leaves un- 
 determined 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 concen- 
 
Solutions 2 1 
 
 trated 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]. 
 
 (V) 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 pro- 
 cess has not been industrially developed [E.P. 10,466/1894]. 
 
 (f) 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) CnprammoniTim 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 cellu- 
 lose 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. 39°-) 
 
22 Cellulose 
 
 (24) Mercerisation. — Notwithstanding the enormous 
 recent developments in the industrial application of the mer- 
 cerising 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 tech- 
 nical work on the subject. 
 
 DIE MERCERISATION DER BAUMWOLLE. 
 Paul Gardner (Berlin : 1898. J. Springer). 
 
 THE MEECEEISATION 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, ^''^^ 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 (i) 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 efiects 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 
 
Alkali- Cellulose 23 
 
 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 con- 
 cludes 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 othei 
 hand, realised the effect industrially, which Lowe certainiy 
 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 
 
24 
 
 Cellulose 
 
 are not such as to have an industrial value — i.e. a value pro- 
 portional to the cost of treatment. 
 
 (b) The lustre is determined by exposing the goods to 
 strong tension, either when under the action of the alkah, 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 deter- 
 mined by the action of the alkali. The following table 
 exhibits the variations of shrinkage of Egyptian when mer- 
 cerised without tension, under varying conditions as regards 
 the essential factors of the treatment — viz. (i) concentration 
 of the alkaline lye, (2) temperature, and (3) duration of action 
 (the latter being of subordinate moment) : — 
 
 Concentration of 
 
 S°T1. 
 
 !ye(NaOH) 
 
 
 Duration of action 
 
 1030 
 
 in minutes 
 
 
 
 Temperatures as 
 
 
 
 under :— 
 
 
 
 2° . 
 
 :> 
 
 
 
 iS'' . 
 
 3 
 
 
 
 30° . . . 
 
 3 0' 
 
 80° . . . 
 
 3 
 
 o°B, 
 
 i|io|3o 
 
 I5°B. 
 
 X 1 10 ko 
 
 25°B. 
 
 Iio 130 
 
 SO^B. 
 
 1 10 I30 
 
 SS'-B. 
 
 I 10 30 
 
 Percentage shrinkages (Egyptian yarns) as under : — 
 
 iS'a 
 
 i5'8 i9"3 
 
 6"oji9'o 
 9'8 i3'4 
 
 ig*8 
 
 20'Z 
 
 137 
 
 2I'S 
 21 'O 
 19*0 
 14-3 
 
 22 7 
 21 'a 
 
 18-5 
 
 i5'o 
 
 32*7 
 
 22*0 
 
 22 7 
 
 22'3 
 19-8 
 
 IS'S 
 
 94 2 
 
 23 '5 
 
 20'7 
 
 15 'o 
 
 245 
 23-8 
 
 21 "O 
 I5"2 
 
 247 
 
 24'7 
 
 2I'1 
 
 I5'4 
 
 The more important general indications of the above results 
 are — (i) The mercerisation action commences with a lye of 
 io°B., and increases with increased strength of the lye up to 
 a maximum at 3S°B. There is, however, a relatively slight 
 increase of action with the increase of caustic soda from 
 3o-4o°B. (2) For optimum action the temperature should 
 not exceed i5-2o°C. (3) The duration of action is of pro- 
 portionately 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. 
 
Alkali- Cellulose 25 
 
 (d) The question as to whether the process of ' mercerisa- 
 tion ' 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 con- 
 stitution 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= 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 mercerisa- 
 tion 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 
 
26 
 
 Cellulose 
 
 in the contour of the surface, which is smooth, and the oblitera- 
 tion at intervals of the canal. Hence the increased trans- 
 parency 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 descrip- 
 tion of the various practical systems of mercerisation of yarns 
 in general practice in Germany, and an account of the methods 
 a,dopted 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 investigatLon, 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 
 stag'e 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. 
 
 
 I 
 
 360 
 
 20 
 
 Cotton unmercerised . 
 
 2 
 
 356 
 
 20 
 
 
 3 
 
 360 
 
 22 
 
 Mercerised with 
 
 I 
 
 53° 
 
 44 
 
 Soda 3S°B. . 
 
 2 
 
 570 
 
 40 
 
 
 3 
 
 559 
 
 35 
 
 Alcoholic soda 10 p. ct. 
 cold 
 
 I 
 2 
 
 645 
 600 
 
 24 
 27 
 
 
 3 
 
 610 
 
 33 
 
 Alcoholic soda 10 p. ct. 
 hot 
 
 5 
 
 740 
 
 3^ 
 
 2 
 
 730 
 
 38 
 
 
 3 
 
 690 
 
 30 
 
Sulphocarbonates 27 
 
 (p. 25) Cellulose sulphocarbonate. — Further in- 
 vestigations of the reaction of formation as well as the various 
 reactions of decomposition of the compound, have not contri- 
 buted 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 measure- 
 ment 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. Reserv- 
 ing 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 per- 
 centage from 44-4 to 43\3, corresponding with a change in 
 composition from CeHioO,, to 4C6H10O5.H2O. 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 
 
28 Cellulose 
 
 the percentage recovered from solution as viscose is from 93 to 
 95 p.ct. It is evident that these celluloses are not homo- 
 geneous. A similar conclusion results from the presence of 
 furfural-yielding compounds with the observation that the 
 hydrolysis to soluble derivatives mainly affects these deriva- 
 tives. In the empirical characterisation of a normal cellulose, 
 therefore, we may include the property of quantitative re- 
 generation 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 sulpho- 
 carbonate reaction differentiates the bleached or purified 
 cotton cellulose from the raw product. The following ex- 
 periments 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 subsecjuently 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 pecuhar modi- 
 fication. 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 
 
Sulphocarbonates 29 
 
 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 viscpse 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 ' 
 
30 Cellulose 
 
 proportion — viz. 2NaOH per i mol. CoHioO,, — has little 
 influence upon the viscose reaction, but lowers the viscosity 
 of the solution of the sulpho-carbonate 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 i'8 p. ct. cellulose prepared from an alkali- 
 cellulose (cotton) fourteen days old. 
 
 {b) Viscose of i'8 p. ct. cellulose from an alkali-cellulose 
 (cotton) three days old. 
 
 (f) Glycerin diluted with \ vol. water. 
 
 a b c 
 
 Diluted with 
 equal vol. 
 water 
 
 Times of flow of equal volumes froml 
 
 ■^ . J 112 321 103 170 
 
 narrow orifice m seconds J 
 
 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 observa- 
 tions have been made on the alkali-cellulose (cotton) after 
 
Sulphocarbonates 3 r 
 
 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 [Bdchamp, 
 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 o? 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 ' cellu- 
 lose — 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 men- 
 tioned 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 
 
32 Cellulose 
 
 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^HioO,, : 2NaOH, is 
 within the ordinary error of observation, 2 : i 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 
 (°'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 inor- 
 ganic compounds. 
 
 Sulphur. — It has been proved by Lindemann and Motten 
 [Bull. Acad. R. Belg. (3), 23, 827] that the sulphur of sulpho- 
 carbonates (as well as of sulphocyanides) is fully oxidised 
 (to SO3) by the hypochlorites (solutions at ordinary tempera- 
 tures). 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, in- 
 cluding the typical cellulose xanthogenic acid, is approximately 
 
Sulphocarbonates 3 3 
 
 isolated and determined as CSj 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 cellu- 
 lose 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°. 
 
 abode 
 
 Total sulphur . . 40-0 25-0 3ro 237 io'4 
 
 The dried product in (b) and (c) was entirely resoluble in 
 water ; in {d) and («), 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 3I2 : 4Na20, calculated to the total alkali. 
 
34 Cellulose 
 
 Other decotnpositions. — The most interesting is the inter- 
 action which occurs between the cellulose xanthogenate and 
 salts of ammonia, which is taken advantage of by C. H. 
 Steam 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 am- 
 monium-chloride solution the gelatinous thread contains 15 p.ct. 
 of cellulose, with a sp.gr. I'l. The process of ' fixing ' — i.e. 
 decomposing the xanthic residue — consists in a short exposure 
 to the boihng 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. i'48. 
 
 Cellulose Benzoates. — These derivatives have been further 
 studied by the authors. The conditions for the formation of 
 themonobenzoate[CjH904.0.CO.Ph] are very similar to those 
 required for the sulphocarbonate reaction. The fibrous cellu- 
 lose (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 pro- 
 portions as below, the following yields were obtained : — 
 
 Calc. for 
 Monobenzoate 
 
 (rt) CjH|„Oj : 2-o-2'S NaOH : CjHj.COCl— 150-8) 
 
 (A) C.H,„05 : 2-0-2-5 NaOH : 1-5 mol. C„H,C0C1 159-0) '''° 
 
 An examination of (a) showed that some dibehzoate (about 
 7 p.ct.) had been formed. The product {b) was exhaustively 
 
Esters 
 
 3S 
 
 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. C6H5COCI, 
 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. 
 
 Aggregate yield of benzoate 
 Moisture in air dry state . 
 Proportion of dibenzoate p.ct. . 
 Yield of cellulose by saponification • 
 
 Sea Island 
 
 Egyptian 
 
 American 
 
 153 
 
 148 
 
 152 
 
 5-28 
 
 5 -35 
 
 5-15 
 
 830 
 
 1370 
 
 94 
 
 580 
 
 54 -o 
 
 58-3 
 
 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 struc- 
 tural 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 there- 
 fore only cited as typical of a method of comparative investi- 
 gation, 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 (i) that there is no corresponding increase 
 in the benzoylation, and (2) that this ester reaction and the 
 
36 Cellulose 
 
 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. 
 
 Structureldss 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 sulpho- 
 carbonate : — 
 
 Mol. proponiuns of reagents Yield Dibenzoate p.ct. 
 
 C.HioO, : 2NaOH : 2BzCl . . 145 347 
 
 [Caustic soda at lo per cent. NaOH] 
 
 C,H,„0,, : 4NaOH : 2Bza . . 162 627 
 
 [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 i 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 CcH,o05.4 [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 investigation the crude product by treatment 
 with solvents, it was found to have still retained benzoic acid. 
 
Esters 
 
 37 
 
 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 ob- 
 tained by regeneration from the sulphocarbonate, other OH 
 groups may react, but they are only a fractional proportion in 
 relation to the unit group C5H10O3. 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 con- 
 stitutes 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 mono- 
 benzoate 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 di- 
 benzoates retain i'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 re- 
 action there is a constitutional change in the cellulose molecule 
 causing it to break down in part under the hydrolysing treat- 
 ment with formation of acid products. This point is under 
 
38 Cellulose 
 
 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 diben- 
 zoate, purified, as far as possible, may be cited : 
 
 Combustion results Saponification results 
 
 Calc. C.H,.COOH Calc. Cellulose Calc. 
 Monobenzoate ^ S6-6o 58-65 , ^ g g^^.g 
 
 H 5-06 5-26 \ ^ 'tJ y 3 
 
 L.ibenzoate . . ^, ^^'lo 64-86 j ^ ^g.g ^^ 
 
 H 3-40 4-86 ' 
 
 The divergence of the numbers, especially for the dibenzoate, 
 in the case of the hydrogen, and yield of cellulose on hydro- 
 lysis 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 ob- 
 tained 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^ group takes place in the aromatic 
 residue, giving a mixed nitric nitrobenzoic ester. The 
 analysis of the products points to the entrance of i NO2 group 
 in the benzoyl residue in either case ; in the cellulose residue 
 1 OH readily reacts. Higher degrees of nitration are at- 
 tained 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 Cj2 
 unit formula. 
 
 In analysing these products we have employed the Dumas 
 method for total nitrogen. For the O.NO2 groups we have found 
 the nitrometer and the Schloesing methods to give concordant 
 results. For the NO2 groups it was thought that Limpricht's 
 method, based upon reduction with stannous chloride in acid 
 
Esters 39 
 
 solution (HCl), would be available. The quantitative results, 
 however, were only approximate, owing to the difficulty of con- 
 fining the reduction to the NO2 groups of the nitrobenzoyl 
 residue. By reduction with ammonium sulphide the O.NO., 
 groups were entirely removed as in the case of the cellulose 
 nitrates ; the NO2 was reduced to NHj 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- 
 dinitrohenzoate. — On treating the fibrous benzoate — which is 
 a, dibenzoate on the C12 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 nitro- 
 benzene. 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 : 
 
 Calc. for 
 
 Dinitrate Trinitrate 
 
 dinitrobenzoate dinitrobenzoate 
 
 7-99 9-24 
 
 400 5 54 
 
 3-99 370 
 
 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. 
 
 
 Found 
 
 
 
 w 
 
 (*) 
 
 Total Nitrogen . 
 
 . 784 
 
 8-97 
 
 O.NO, „ 
 
 . 5'oo 
 
 S-4S 
 
 NOo (Aromatic) 
 
 . 2-84 
 
 3-52 
 
40 Cellulose 
 
 The nitrogen in the amidobenzoate resulting from the re- 
 duction with ammonium sulphide was 4*5 p.ct. — as against 
 5'o p.ct. calculated. The moisture retained by the fibrous 
 nitrate — nitrobenzoate — in the air dry state was found to be 
 I '97 p.ct. 
 
 The product from the structureless dibenzoate or tetra- 
 benzoate on the 0,2 formula, was prepared and analysed with 
 the following results : 
 
 
 
 Calc. for 
 
 
 
 Mononitrate tetranitrobenzoate 
 
 Total Nitrogen . 
 
 . 676 
 
 7 -25 
 
 O.NO, „ . . . 
 
 . 1-30 
 
 1-45 
 
 NO, „ (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 C12 unit — we conclude that 
 % 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 secon- 
 dary 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, how- 
 ever, from the somewhat vague statements of Schutzenberger's 
 researches w^hich are current in the text-books [e.g, Beilstein, 
 I 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 anhy- 
 
Esters 4 1 
 
 dride. We have obtained the following results with bleached 
 cotton : 
 
 v;»M Calc. for Monoacetate 
 
 '"^"' C.H,O..O.C,H.O 
 
 Ester reaction 121 p.ct, 125 p.ct. 
 
 Cellulose J79"9 79'9 
 
 Saponificatioii i , . • •- 
 '^ I Acetic acid 
 
 '29-9 29-4 
 
 This product is formed without apparent structural altera- 
 tion 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 manufac- 
 turing scale : it has yet to establish its industrial value. 
 
 NITRIRUNG VON KOHLENHYDRATEN. 
 
 W. Will und P. Lenze (Berl. Ber., 1898, 68). 
 
 mXBATES OF CABBOHYDBATES. 
 
 (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 pro- 
 , ducts were analysed and their physical properties determined. 
 They were more especially investigated in regard to tempera- 
 tures 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 
 
42 Cellulose 
 
 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 temperjiture. 
 
 Xylose is differentiated by tending to pass into an anhydride 
 form (CsHiflOs — H.2O) 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 
 
 Ketoses (C5). — These are sharply differentiated from the 
 corresponding aldoses by giving /r/nitrates CeH70.2(N03)3 
 instead of /ew/'anitrates, 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 un- 
 stable nitrate. The lactose nitrate is more stable. Thus at 
 50° it loses only 07 p.ct. in weight in eight days ; at 75° it 
 loses I 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 5o°-7S° degrees it behaves much like the lactose 
 nitrate. 
 
 Trisaccharide. — Rafifinose yielded the product 
 C,sH,,0,.(N03),,. 
 
 Starch yields the hexanitrate (C,2) by both methods of nitra- 
 
Esters 
 
 43 
 
 tion. 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,o 
 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 con- 
 taining the requisite mineral matter and placed in the dark. 
 The growth is rapid, and a considerable quantity of the vege- 
 table growth accumulates round the masses of cellulose nitrate, 
 but no growth is observed if mineral matter is absent. Cellu- 
 lose 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 
 
44 Cellulose 
 
 large excess, together with successive analyses -of the compounds 
 produced, showed that the final product of the reaction corre- 
 sponded, in each case, with the fixation of 1 1 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 un- 
 affected. 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 Hmited by their fibrous character. The 
 conversion of these products into the structureless homo- 
 geneous 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 representa- 
 tives 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 
 
Esters 45 
 
 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 HNO3 — 24: H2SO4 — 70: 
 HjO— 6:the proportion of acid to cellulose being 60:1—. 
 After careful purification the products were analysed with the 
 following results : 
 
 N"-g- Etlel^ato'ho. 
 
 Fibrous nitrate . .13-31 4-3 p. ct. 
 
 Structureless nitrate . I3'35 56 ,, 
 
 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 
 
46 Cellulose 
 
 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 
 ticatments 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 
 4o°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 con- 
 dition 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 pro- 
 portions 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 struc- 
 tural 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 
 
Esters 
 
 47 
 
 , 
 
 
 Proportions by volume 
 
 Tempera- 
 
 Heat 
 
 Heat 
 
 
 — 
 
 ture of 
 
 Test 
 
 Test 
 
 
 ! Acetone j Water 
 
 Explosion 
 
 80° 
 
 134° 
 
 
 ' 
 
 Deg. 
 
 Mins. 
 
 Mins, 
 
 
 
 20 
 
 80 
 
 137 
 
 3 
 
 4 
 
 
 
 30 
 
 70 
 
 160 
 
 3 
 
 4 
 
 
 
 40 
 
 60 
 
 180 
 
 7 
 
 18 
 
 No fumes 
 
 From 
 
 ' A ' sample . 
 
 SO 
 
 SO 
 
 187 -s 
 
 SS 
 
 after 
 100 
 
 
 
 60 1 40 
 
 187 
 
 45 
 
 100 
 
 
 
 1° 
 
 30 
 
 i8s 
 
 4S 
 
 1CX3 
 
 
 
 80 
 
 20 
 
 — 
 
 50 
 
 100 
 
 
 : 92 
 
 8 
 
 185 
 
 50 
 
 100 
 
 
 [ Structure- 
 
 
 
 
 
 
 
 less powder. 
 
 
 
 
 
 a 
 
 ' B ' sample 
 
 SO 
 
 50 
 
 183 
 
 3S 
 
 100 
 
 >i 
 
 ' C ' sample 
 
 Ordinary service 1 
 guncotton / 
 
 18s 
 
 10 
 
 41 
 
 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 accord- 
 ing to the attendant conditions of treatment. With the main 
 product in certain cases there is found associated a small pro- 
 portion 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 i3"43 p.ct. from the i3'3i 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. 
 
4S Cellulose 
 
 It is clear, therefore, that this specifically regulated action 
 of acetone produces the eifects {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 dis- 
 tilling off the acetone, a precipitation is determined. The pre- 
 cipitates are nitrates of variable composition, analysis showing 
 from 9 to 1 2 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 pre- 
 cipitation 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, js relatively so small that we have only been 
 able to obtain and examine it as residue from evaporation 
 to dryness. An exhaustive qualitative examination estabHshed 
 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- 
 
Esters 
 
 49 
 
 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 1 1-9 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 
 efiect of stabilisation appears, therefore, to depend upon the 
 combination of certain acid products present in ordinary nitro- 
 celluloses 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 con- 
 ditions of action. It has been finally established (i) 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. 
 
 E 
 
50 
 
 Cellulose 
 
 The following results may be cited, obtained by boiling a 
 purified ' service ' guncotton (sample C) with a i 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 
 at 80° 
 
 Heat Test 
 at 134° 
 
 Original sample C 
 
 Treated with lead acetate 
 
 „ zinc „ ... 
 
 10 
 91 
 
 41 
 45 
 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 maybe summed up as follows : — 
 
 (i) Traces of free nitrating acids, which can only occur in 
 the finished products through careless manufacture, will un- 
 doubtedly 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 actioji 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 
 
Esters 5 1 
 
 purified by long-continued boiling in water without any neutra- 
 lising 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 elimina- 
 ting these compounds, or by combining them with the oxides 
 of lead orpine 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 w^ater. This effect is much more 
 apparent at higher temperatures. 
 
 Dense strudwreless or non-fibrous cellulose nitrates can be 
 industrially prepared (i) 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 dis- 
 integration 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 varia- 
 tion 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). 
 
52 Cellulose 
 
 The structureless guncotton prepared as above de- 
 scribed is of quite exceptional character, and entirely 
 distinct from the ordinary fibrous nitrate or the nitrate pre- 
 pared by precipitation from actual solution in an undiluted 
 solvent.' 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 manu- 
 facture 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 ' re- 
 training' 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 
 
 ' With these products it is easy to observe that thfy have a definite 
 fusion 1 oint _,°-lo° btlow the temperature of explosion. 
 
Esters 5 3 
 
 fixed according to the hardness and bulk of the finished grain 
 it is desired to produce (J. Soc. Cham. 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). 
 
54 Cellulose 
 
 EMPLOI DE LA CELLULOSE POUR LA FABRICATION 
 UE FILS BRILLANTS IMITANT LA SOIE. 
 
 E. Bronnert (i) (Rev. Mat. Col., 1900, September, 267). 
 
 V. USE OF CELLULOSE IN THE MANTTFACTUEE OF IMITA- 
 TIONS OF SILK ^L^JSTE4-CELHTL0SE). 
 
 (p. 45) Introduction. — The problem of spinning a con- 
 tinuous 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 dimen- 
 sions 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. 
 
Lustra-cellulose 
 
 55 
 
 4. ' Viscose silks,' by the decomposition of sulphocarbonate 
 of cellulose (Cross and Bevan). 
 
 Group i. 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 BibUography, (i) and (2), (3) and (4)]. The denitrating 
 treatment was introduced in the period 1888790 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 I. 
 
 - 
 
 Tenacity 
 (grammes) 
 
 Elasticlty 
 (% elongation) 
 
 Nitrocellulose according to Chardonnet 
 German Patent No. 81,599 . 
 
 The same after denitration 
 
 Denitrated fibre moistened with water 
 
 Nitrocellulose : Bronnert's German Paten 
 No. 93,009 .... 
 
 The same after denitration (dry) 
 
 The same after denitration (wetted) . 
 
 Natural silk 
 
 
 ISO 
 no 
 
 25 
 
 125 
 
 115 
 
 32 
 
 300 
 
 23 
 
 8 
 
 28 
 13 
 
 18 
 
 I. Tenacity is the weight in grammes required to break the thread. 
 
 \i.. Elasticity is the elongation per cent, at breaking. 
 
 The numbers are taken for thread of 100 deniers (450 metres of 0-05 
 grammes = I 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 
 
56 Cellulose 
 
 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 con- 
 sequence ; 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 
 
Lustra-cellulose 57 
 
 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 investiga- 
 tion. 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. 
 CaCla per i mol. tetranitrate (17) reaches a maximum in half 
 an hour's heating at 6o°-7o°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. Char- 
 donnet 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 oxycellalose 
 therefore. The density of the thread is from 1-5 to i -5 5. 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 
 
58 Cellulose 
 
 on cotton thread, of which the following table represents 
 the numerical results : 
 
 Breaking S rain 
 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 watted . . . 206 
 
 The author considers that other patents which have been 
 taken for spinning nitrocellulose are of little practical a:;count 
 (21) and (22). The same conclusion alsoapplies 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 (i). The iirst 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.) P'or 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 cel- 
 lulose has been previously oxidised. Such cellulose gives an 
 8 p.ct. solution, and the thread obtained has the character of an 
 oxy-cellulose, specially seen in its dyeing properties. The best 
 
Lustra-cellulose 59 
 
 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 propor- 
 tions.) The author notes that the so-called hydrocellulose 
 (Girard) (5) is almost insoluble in cuprammohium, 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 (i). 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. Experi- 
 ments are being continued with these modifications of the 
 process, and the author anticipates successful results. The 
 modifications having the effect of maintaining the high mole- 
 cular 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 thio-carbonate (i) 
 (2) (3). Great hopes were based upon this product at the 
 
6o Cellulose 
 
 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 re- 
 garded 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 Niedeimorsch- 
 weiler, near Mulhouse, is projected for this last production. 
 
 BlBLIOGR.\PHY 
 Introduction 
 
 (1) Bull, de la Soc. industr. de Mulhouse, 1900. 
 
 (2) R&umur, Memoire pour serviral'histoire des insectes, 1874, I, 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. N). 
 
 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 
 
 (I) 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. II, 1893. German Pat. No. 56655, April 23, 
 1890. French Pat. No. 231230, June 30, 1893. 
 
Lustra-cellulose 6r 
 
 (2) Industrie textile, 1899, 1892. Wyss-Noef, Zeitschrift fur angewandte 
 
 Chemie, 1899, 30, 33. La Nature, Jan. i, 1898, No. 1283. Revue 
 generate 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, 
 
 Diet, de Chimie de Wurtz. 
 
 (5) German Pat. No. 81599, Oct. II, 1893. 
 
 (6) Bechamp, art. Cellulose, Diet, 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 I, 1895. German Pat. 88556, 
 
 March 28, 1894. 
 
 (9) Bechamp, art. Cellulose, Diet, 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. I, 1897 (Pauly). French Pat. 286692, 
 
 March 10, 1899, and addition of October 14, 1899 (Fremery and 
 Urban). French Pat. 286726, March 11, 1899, ^"d addition of 
 December 4, 1899. German Pat. H1313, March 16, l899(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. 
 
62 Cellulose 
 
 (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- '2. 
 
 Group IV 
 
 (1) English Pat. 8700, 1892. German Pat. 70999, Jan. 13, 1893. 
 
 (2) English Pal. 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 state- 
 ments 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 o'lg 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 t 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-cellu- 
 lose.' 
 
Lustra-cellulose 63 
 
 DIE KUNSTLICHE SEIDE— IHRE HERSTELLUNG, 
 EIGENSCHAFTEN UND VERWENDUNG. 
 
 Carl Suvern, Berlin 1900, J. Springer. 
 
 ARTIFICIAL SILK— ITS PRODUCTION, PROPEETIES, AND 
 APPLICATIONS. 
 
 This work of some 130 pages is an important monograph 
 of 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 fi, but with considerable variations from the mean in the indi- 
 vidual 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 ir- 
 regiilar outline. This is due to irregular conditions of evapora- 
 tion 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 is-ry p.ct. 
 The sp.gr. is i-49, i.e. 3-5 p.ct. in excess of boiled off silk. 
 
 Lehner ' silk ' exhibits the closest similarity to the Char- 
 
64 Cellulose 
 
 donnet 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 ; 
 Silberraann, 'Die Seide,' 1897, v. 2, 143 ; Herzog, 'Farber-Zeitung, 
 1894/5, 49-50; Thiele, ibid. 1897, 133; O. Schlesinger, ' Papier- 
 Zeitung,' 1895, 1578-81, l5lO-I2. 
 
 Action of Reagents upon Natural and Artificial Silks. 
 
 1. Potassium hydrate in solution of maximum concentra- 
 tion dissolves the silks proper, {a) China silk on slight warm- 
 ing, (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 com- 
 pletely at 65°-85° ; Tussah silk swells considerably at 75° and 
 dissolves at ioo°-i2o°. 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 
 
Lustra-cellulose 65 
 
 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 i8o°- 
 
 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. CrOs — solution dissolves both 
 the natural silks and the lustra-celluloses at the boiling tem- 
 perature of the solution. 
 
 9. Milton'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 con- 
 centrated sulphuric acid colours the natural silks a brown ; 
 the collodion ' silks ' give a strong blue reaction due to the 
 
 F 
 
66 Cellulose 
 
 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 cotidition was determined by drying at 
 100° ; the following percentages resulted (a). The percen- 
 tages of water (U) taken up from the atmosphere after forty- 
 three hours' exposure were : 
 
 («) («) 
 
 China (raw) silk .... 7-97 2-24 
 
 Tussah silk ..... 8-26 5-00 
 
 Lustra-celluloses : 
 
 Chardonnet (Besanjon) . . . 10-37 5-64 
 
 ,, Spreitenbach . . . 11-17 577 
 
 Lehner 10-71 5-97 
 
 Pauly 10-04 6'94 
 
 16. Behaviour on heating at 200°. — After two hours' heat- 
 ing 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 of the fibres. 
 
 Paulv J ^ bright yellow-brown colouration, without car- 
 
 I bonisation. 
 
 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-cellulose 67 
 
 Lustra-celluloses : 
 
 Chardonnet ......... 337° 
 
 Lehner . . . 26-56 
 
 Pauly l-6i 
 
 18. Inorganic constituents. — Determinations of the total ash 
 gave for the first five of the above, numbers varying from i -o to 
 I 7 p.ct. The only noteworthy point in the comparison was 
 the exceptionally small ash of the Pauly product, viz. 0096 p.ct. 
 
 19. Total nitrogen. — The natural silks contain the 16-17 
 p.ct. N characteristic of the proteids. The lustra-celluloses 
 contain o'o5-o'i5 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 dis- 
 cussed. The specific relationships 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. 
 
 UEBER CELLULOSE. 
 G. BuMCKE und R. Wolffenstein (Berl. Ber., 1899, 2493). 
 
 (p. 54) Theoretical Preface. — The purpose of these inves- 
 tigations is the closer characterisation of the products known 
 as ' oxycellulose ' and ' hydracellulose,' which are empirical 
 aggregates obtained by various processes of oxidation and 
 
68 Cellulose 
 
 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 VVurster (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 hydral- 
 cellulose. By the action of alkalis this is resolved into two 
 bodies of alcoholic (cellulose) and acid (' acid cellulose ') charac- 
 teristics respectively. The latter in drying passes into a lactone. 
 I'he acid product is also obtained from cellulose by the action 
 of alkaline lye (boiling 30 p.ct. NaOH) ana 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 suppHed 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 H2O2 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 
 
Constitution 69 
 
 results lying between the requirements of the formulas : 
 
 5 C.H.'oOj.HjO and 8 C,H,„0,.H,0. 
 
 Hydrazones were obtained with i7-i'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 
 ■^^ 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 dura- 
 tion. On adding sulphuric acid to the solutions the product 
 was precipitated. Yield 40 p.ct. Analyses : 
 
 C 43-8 43-8 437 
 
 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 -o 
 
 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 
 HNOs 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 
 
70 Cellulose 
 
 various nitrates from the several original products proved to be 
 of almost identical composition, 
 
 C 320 H 42 N 8-8 
 
 with a molecular weight approximately 1350. The conclusion 
 is that these products are all derivatives of a ' hydralcellulose ' 
 6 CeH.oOe H,0. 
 
 FORMATION OF FURFURALDEHYDE FROM CELLU- 
 LOSE, OXYCELLULOSE, AND HYDROCELLULOSE. 
 
 By Leo Vignon (Compt. rend., 1S98, 126, 1355-1358). 
 
 (p. 54). Hydrocellulose, oxycellulose, and ' reduced ' cellu- 
 lose, the last named being apparently identical with hydrocellu- 
 lose, were obtained by heating carefully purified cotton wool (10 
 grams) in water (1,000 c.c), with (i) 65 c.c. of hydrochloric acid 
 {V2 sp.gr.), (2) 65 c.c. of hydrochloric acid and 80 grams of po- 
 tassium 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, i-8oo; 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, i6"2o 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 ii-i6 grams 
 of insoluble matter, i -42 grams were precipitated by acid, and 
 12-42 grams remained in solution. The percentage yields of 
 
Constitution 7 1 
 
 furfuraldehyde obtained from these fractions were as follows : 
 A, insoluble, 086; precipitated, 4"35 j dissolved, i-io. B, 
 insoluble, 076 ; precipitated, S'li ; 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 UBER DIE OXYCELLULOSE. 
 O. V. Faber und B. Tollens (Berl. Ber., 1899, 2589). 
 
 Inyestigations of Ozycellnlose. 
 
 (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 = CeHioOs), and for which the special designation 
 Celloxin is proposed. 
 
 Celloxin may be formulated CgHjOg or CsHioOg, 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 oxycellu- 
 loses with, lime-milk it is converted into isosaccharinic and 
 dioxybutyric acids. The insoluble residue from the treatment 
 is cellulose. 
 
72 Cellulose 
 
 The following oxycelluloses were investigated : 
 
 A. Product of action of nitric acid upon pine wood (Lindsey 
 and ToUens, Ann. 267, 366). — The oxycelluloses contained 
 
 , „ • J 2 mol. cellulose on 6 hours' heating 
 
 I moi. ceiioxm : | ^ ^^j ^,^11^1055 ^^ ^ fours' heating 
 
 with a ratio H : O = i 19 and i : 87 respectively : they 
 yielded 7 p.ct. furfural. 
 
 B. By action of bromine in presence of water and CaCOj 
 upon cotton. — Yield, (air-dry) 85 p.ct. Empirical composition 
 CuHjoOi, = CgHioOs.CgHioOs : yielded furfural 17 p.ct. 
 
 C. Cotton and nitric acid at 100°, two and a half hours 
 (Cross and Bevan). — Yield, 70 p.ct. Composition 
 
 4 CgHioOs-CeHgOg 
 yielded furfural 2 '3 p.ct. 
 
 D. Cotton and nitric acid at 100° (four hours). — A more 
 highly oxidised product resulted, viz. 3 CgHioOj.CeHjOe : 
 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 (i) isosaccharinic and (2) dioxybutyric acid 
 from the product^ of digestion of the oxycelluloses with lime- 
 milk at 100° was effected by the separation of their respective 
 calcium salts, (i) by direct crystallisation, (2) by precipitation 
 with alcohol after separation of the former. 
 
 CELLULOSES, HYDRO- AND OXY-CELLULOSES, 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 
 
Constitution 73 
 
 HClOj at 100°, gave remarkably uniform results, as shown by 
 the following numbers, showing extreme variations : yields, 
 68-70 p.ct. ; hydrazine reaction, N fixed i-58-i-69 ; fixation of 
 basic colouring matters (relative numbers), saffranine, 100-200, 
 methylene blue, 100-106. The only points of difference noted 
 were (i) hemp is somewhat more resistant to the acid oxida- 
 tion ; (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 hydro- 
 chloric 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 ...... 970 
 
 Cotton mercerised (NaOH 30°B. ) . . . .4-39 
 
 Cotton mercerised (NaOH 40°B. ) . . . . 3'5i 
 
 Cellulose reprecipitated from cuprammonium . . 4'39 
 Oxycellulose ........ 1470 
 
 Starch 98 6 
 
 These numbers show that cellulose may be hydrated both 
 by mercerisation and solution, without affecting the constitu- 
 tional relationships of the CO groups. The results also dif- 
 ferentiate the cellulose series from starch in regard to hydro- 
 lysis. 
 
 (c) Cellulose and oxycellulose nitrates. — The nitric esters of 
 cellulose have a strong reducing action on alkaline copper solu- 
 tions. 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 i3'5-i3'9 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). 
 
74 Cellulose 
 
 Cellulose maximum nitration (13-5 p.ct. N) . . . 3640 
 
 Oxycellulose maximum nitration (I3"9 p.ct. N) . . 3^°° 
 
 Cellulose minimum nitration (S'lg 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 pro- 
 duct being an oxycellulose ester. 
 
 Froducts 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 oxy- 
 cellulose directly prepared by the action of HCIO3. On the 
 other hand, by treatment with ammonium sulphide at 35°-4o° 
 ' 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 oxi- 
 dation of cellulose. [Compare Bull. Mulhouse, 1892. J The 
 products described were obtained by the action of hypochlorites 
 and perinanganates upon Swedish filter paper (Schleicher and 
 Schull). 
 
 4. Oxidation by hypochlorites. — (i) 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 
 
Constitution 75 
 
 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 4378 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 (i), but the conditions varied 
 
 by passing a stream of carbonic acid gas through the solution 
 
 contained in a flask, until CI compounds ceased to be given 
 
 off. The analysis of the purified oxycellulose gave C 43'53, 
 
 H6'i3. 
 
 (3) The conditions were as in (2), but a much stronger 
 
 hypochlorite solution — viz. i2°B. — was employed. The yield 
 
 of oxycellulose precipitated from solution in soda lye (lo 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 o-8i 
 
 B. Oxidation by permanganate {KM.nO^. (i) The cellu- 
 lose 16 grms. was treated with iioo c.c. of a i p.ct. solution 
 of KMn04 in successive portions. The MnOj was removed 
 from time to time by digesting the product with a dilute 
 sulphuric acid (10 p.ct. H2SO4). The oxycellulose was purified 
 as before, yield 40 p.ct. Analytical numbers : 
 
 Oxycellulose . . .0 42-12 42-9 
 
 ,, . . . . H 6-20 611 
 
 Phenylhydrazine compound . N 1-35 I -08 I -21 
 
76 Cellulose 
 
 (2) The cellulose (16 grms.) was digested 14 days with 
 2500 c.c. of I p.ct. KMn04 solution. The purified oxy- 
 cellulose was identical in all respects with the above : yield 
 40 p.ct. C 42'66, H 6T9. 
 
 (3) The cellulose (16 grms.) was heated in the water-bath 
 with 1600 c.c. of 15 p.ct. HjSOj to which were added 18 grms. 
 KMn04. The yield and composition of the oxycellulose was 
 identical with the above. It appears from these results that 
 the oxidation with hypochlorites adds i atom of O to 4-6 of 
 the unit groups CeHioO^ ; and the oxidation with permanganate 
 2 atoms O per 4-6 units of CgHjoOs. The molecular pro- 
 portion of N in the phenylhydrazine . residue combining is 
 fractional, representing i atom O, i.e. i CO group reacting per 
 4 CaeHjoOji and 6 C24H40O21 respectively, assuming the 
 reaction to be a hydrazone reaction. 
 
 Further investigations of the oxycelluloses by treatment 
 with (a) sodium amalgam, (p) 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 presence of calcium 
 carbonate at a temperature of about 35° for 13 months. The 
 
Constitution yy 
 
 products obtained from 3"4743 grams of paper were : acids of 
 the acetic series, 2'2402 grams ; carbonic anhydride, o'9722 
 grams ; and hydrogen, o'oi38 gram. The acids were chiefly 
 acetic and butyric acid, the ratio of the former to the latter 
 bemg 17 : i. 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 aggrega- 
 tion. 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 preserv- 
 ing 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 
 
78 Cellulose 
 
 and elasticity. Similarly with the acetate. The normal acetate 
 gives solutions of high viscosity, films of considerable tenacity, 
 and when these 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 cellu- 
 loses 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 experi- 
 mental 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 ag- 
 gregate which constitutes a cellulose is of a resistant type, and 
 undoubtedly persists in the solutions of the compounds. 
 
 It may b? urged that it is superfluous to import these ques- 
 tions 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 
 
Constitution yg 
 
 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 depres- 
 sion of solidifying and boiUng-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 some- 
 what speculative treatment of the hypothetical ultimate unit 
 group, which is taken as of Cg 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 [C6H50.(OAc)4j 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 treat- 
 ments. The probability may be noted here that under the 
 action of the alkaline hydrates there occurs a change of con- 
 figuration. 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 
 
8o Cellulose 
 
 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 can- 
 not, 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 3o°-4o°, the reagents are 
 used but little in excess of the quantitative proportions, and 
 the yields are approximately quantitative. If now the deriva- 
 tive is formed entirely without hydrolysis the empirical 
 formula C5HoO.(OAc)4 justifies a closed-ring formula for the 
 original, viz. CO < [CHOH]4> CHj ; and the preference for 
 this formula depends upon the explanation it affords of the 
 aggregation of the groups by way of CO-CH2 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 hydro- 
 lysis attending the cycle of reactions is indicated by the 
 
Constitution 8 1 
 
 formula 4 C^HioOs-HjO. It has been already shown that this 
 degree of hydrolysis does not produce molecular disaggrega- 
 tion. If this hydrate survived the acetylation it would of .course 
 affect the empirical composition, i.e. chiefly the carbon per- 
 centage, 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 C14H20O10 (C=48'3 p.ct.) and C14H18O9 
 (C=5o-8 p.ct.) i.e. a tetracetate of CgHuOe and C^HioOj 
 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 de- 
 termination 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 C6H50.(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 acetyla- 
 tion at tiie tetracetate the aggregation of the unit groups must 
 depend upon the CO- groups and a ring formula of the general 
 form CO<[CHOH]4>CH2 is consistent with the facts. 
 
 Vignon has proposed for cellulose the constitutional formula 
 O— CH\ 
 
 O ^[CHOHjj with reference to the highest nit.-ate, 
 
 CH,-CH/ 
 
82 Cellulose 
 
 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 con- 
 densing acids to split off formic acid in relatively large quan- 
 tity [Ber. 1895, 1940] ; the condensation of the oxycelluloses 
 to furfural ; the non-formation of the normal hydroxy-dicarb- 
 oxylic 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 com- 
 plex. Also there is no suggestion as to how far the formula is 
 applicable to the celluloses considered as a group. In extend- 
 ing this view to the oxycelluloses, Vignon introduces the 
 
 derived oxidised group CHO.(CHOH)3.CH . CO— of which 
 
 I— 0-J 
 
 one is apportioned to three or four groups of the cellulose pre- 
 viously formulated : these groups in condensed union together 
 constitute an oxycellulose. 
 
 These views are in agreement with the experimental results 
 obtained by Faber and ToUens (p. 71). They regard the 
 oxycelluloses as compounds of ' celloxin ' CeHgOg with 1-4 
 mols. unaltered cellulose ; and the former they more 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 
 
Constitution 83 
 
 of the carbohydrates (p. 41) Will and Ixnze 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 correspond- 
 ing 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 NO3 groups fixed. The theoretical yields for the higher 
 nitrates are 
 
 Yield p.ct. 
 of celluluse 
 
 N p.ct. 
 of nitrate 
 
 litiate . . . .169 
 
 127 
 
 litrate . . . . liij 
 
 I4-I 
 
 From such statistics as are recorded the yields are not in 
 accordance with the above. There is a sensible deficiency. 
 Thus ^Vill and Lenze record a yield of 1 70 p.ct. for a product with 
 1 3 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 con- 
 densation 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 un- 
 
 G 2 
 
84 Cellulose 
 
 saturated 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 methyl- 
 hydroxyfurfural 
 
 QH,206-3H20=C6H603=C,(OH).Hj.(CH3)02 
 and (b) by HBr, with further loss of OH, as under : 
 CgH, jOs - 4H2O + HBr=C5H3(CH2Br)02 
 
 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. looj ; 
 {b) by the action of hydrobromic acid (gas) in presence of 
 anhydrous ether ; the actual compound obtained being the 
 w-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 
 
Constitution 85 
 
 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 m the 
 position of a primary product with starch as a species of over- 
 flow and reserve product, it appears that lasvulose 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 car- 
 bonyls 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 (CeHjeOs) yields a monoacetate, a dibenzoate, and a 
 trinitrate respectively under conditions which determine, wi th 
 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. 
 
86 Cellulose 
 
 The subjoined communication, appearing after the com- 
 pletion of the MS. of the book, and belonging to a date 
 subsequent to the period intended to be covered, is neverthe- 
 less included by reason of its exceptional importance and 
 special bearing on the constitutional problem above discussed. 
 
 The Action of Hydrogen Bromide on Carbohydrates.' 
 
 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.'' 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 w-brommethylfurfural, 
 
 CH:CCH,Br 
 I 6 
 
 CH:C-CHO 
 
 This reaction is produced by Isevulose, sorbose, cane sugar, 
 and inulin, an intense colour being given within an hour or 
 two. Dextrose, maltose, milk sugar, galactose, and the poly- 
 hydric 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 
 
 ' The original paper is reproduced with slight alterations. 
 
 '' This purple colour would appear to be due to a highly dissociable 
 compound of m-brommethylfurfural with hydrogen bromide. The al- 
 dehyde 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. 
 
Constitution 87 
 
 distinguishing these classes of carbohydrates, the rapid pro- 
 duction 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 crystal- 
 lisation 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 <d 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 (59'5-6o'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-I970 gram required lo'S c.c. Njio AgNOs- 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 
 
88 
 
 Cellulose 
 
 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 (D-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 . 
 Ordinary cotton . 
 Mercerised cotton 
 
 . 3-0 crystallised at 01 
 
 ■ 3-3 
 
 ■ 2-1 
 
 Straw cellulose' . 
 
 • 23 
 
 Lsevulose . 
 
 2-2 
 
 Inulin . 
 Potato starch 
 
 . 1-3 
 . 0-37 
 
 Cane sugar . 
 Dextrose 
 
 . 0-85 
 
 . 033 uncrystallisable 
 
 Milk sugar . 
 Glycogen . 
 Galactose . 
 
 . 0-37 
 
 • 0-34 .. 
 
 . 0-34 
 
 ' Other forms of cellulose were also examined— for example, pine- 
 wood cellulose -and the substances separated from solution as thiocar- 
 bonate (powder and film). All uf these gave good yields of a-brom- 
 methylfurfural. 
 
Constitution 89 
 
 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 abso- 
 lutely negative results as regards the formation of w-brom- 
 methylfurfural ; 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\\o KOH, Nj\ 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 ex- 
 periments 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 speci- 
 mens specially prepared by C. O'SuUivan, 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, [0]^ = 1947 ; K = 0-95, (<: 2-628). 
 
 6. a-Dextrin, C equation purified without fermentation, 30 pre- 
 cipitations with alcohol (Trans., 1879, 35, 772). 
 
90 
 
 Cellulose 
 
 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. 
 
 I. 
 
 Rice starch . 
 
 . 0-046 crystall 
 
 2. 
 
 Wheat starch 
 
 . 0-044 
 
 3- 
 
 Oat starch . 
 
 . 0-049 
 
 4- 
 
 Pea starch . 
 
 . 0-064 
 
 5- 
 
 Natural dextrin . 
 
 . o-o88 
 
 &. 
 
 a-Dextrin . 
 
 • 0055 
 
 sed at once by ' sowing. 
 
 The results may therefore be summarised as follows : — 
 Treated under these particular conditions all forms of cellulose 
 give large yields of <u-brommethylfurfural, some varieties 
 giving as much as 33 per cent. Lsevulose, 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 recry stall isation 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. 
 
Constitution 91 
 
 C/f 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 Icevulose, 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 Isevulose, the six-carbon chain with a 
 ketonic group : 
 
 c-ccc-c-c 
 
 1 1 
 O 
 
 But the results might, on the other hand, be considered 
 indicative of the anhydride or ' lacton ' grouping, which ToUens 
 suggested for laevulose : 
 
 c-c-c-c-cc 
 
 \/ - 
 O 
 
 The latter very simply represents the formation of w-bromo- 
 methylfurfural from laevulose,^ 
 
 , O , 
 
 H H 
 
 OH-C C C C C CH,-OH 
 
 jH, OiiH OH On'VL 
 
 giving 
 
 HH 
 HC-C:CC:C-CHjBr 
 
 II \/ 
 
 o O 
 
 ' The change is empirically represented as 
 
 C,H„0„ + HBr - 4HP = C„H,0,Br. 
 
92 Cellulose 
 
 a though 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 (anhy- 
 dride). 
 
 (p. 79) Composition of the Seed Hair of Eriodendron (Anf.). 
 — Some interest attaches to the results of an analytical investi- 
 gation 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 follow- 
 ing numbers determined for the kapok differentiate it widely 
 from the cottons : 
 
 Ash, i'3; moisture, 9^3; alkaline hydrolysis (loss) (a) 
 167, (b) 2i'8. Cellulose, by chlorination, &c., yi'i. 
 
 In reacting with chlorine it shows the presence of unsatu- 
 rated groups, similar to the lignone of the woods. This was 
 
Constitution 93 
 
 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 o 
 furfural on boiling with condensing acids. The following 
 numbers were determined : 
 
 Total furfural from original fibre . . . 14 '84 
 In residue from alkali hydrolysis . . . 1 1 -5 
 In cellulose isolated by CI method . . . iO'4 
 
 Treated with sulphuric acids of concentration, (a) 92 -i grs. 
 H2SO4 per 100 c.c, (b) 105 '8 grs. per 100 c.c, the fibres dis- 
 solve, and diluted immediately after complete solution it was 
 resolved into 
 
 
 W 
 
 (*) 
 
 Reprecipitated fraction . 
 
 . 687 
 
 437 
 
 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 con- 
 stitute at least one third of the fibre substance it is especially 
 from this point of view that they invite study. 
 
94 Cellulose 
 
 RECHERCHES SUR L'OXYCELLULOSE. 
 
 L. ViGNON. 
 
 B^Bume of InvestigationB (1898-1900) of OzycelluIoBe, published 
 as a brochnre (Rey, Lyon, 1900). 
 
 (a) A typical oxycellulose prepared from cotton cellulose 
 by the action of HCIO3 (HCl + KClOj) in dilute solution at 
 100° for one hour gave the following numbers : 
 
 c H o 
 
 Elementary composition . . . 43'5S 6'03 5o'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 ceMulose 
 
 Heat of combustion . . 4124-4133 4190-4224 
 
 Heat evolved in contact with 50 times wt. 1 , 
 
 1 ,^^tr \ J'Scal. 074 cal. 
 
 normal KOH per 100 grms. ' 
 
 Oxycellulose CeJlulnse 
 
 Absorption of colouring matters I Saffranine . . 07 00 
 
 at 100° per 100 grms. . ' Methylene blue . 0-6 o'2 
 
 (p) Yield of furfural from cellulose, oxy- and hydro-cellulose. 
 From the hydrocelluloses variously prepared the author obtains 
 o'8 p.ct. furfural; from bleached cotton i-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 (HJSO4 3 p., HNO3 i p) under 
 conditions for maximum action, the resulting esters showed 
 uniformly a fixation of ii'o NO2 groups per unit mol. of C24. 
 
Constitution 95 
 
 The oxycellulose nitrate was treated directly with dilute solu- 
 tion of potassium hydrate in the cold. From the products of 
 decomposition the author obtained the osazone of hydroxy- 
 pyruvic 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 cellu- 
 lose derivative reacting, corresponding with, i.e. calculated 
 from, the nitrogen determined in the products (o'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: 
 
 Cotton (bleached) 
 Oxycellulose (HCIO.) . 
 
 (HCIO) . 
 
 (CrO,) (I) 
 
 (CrO,) (2) 
 
 (CrO,) (3) 
 
 (ef Constitution of cellulose and oxycellulose. — The results of 
 these investigations are generalised as regards cellulose (Cg) by 
 
 /CH — CH2 
 I 
 11^^ <.v^..a.....uu.w..u. .„w>^..^ ^v..^^v-^*/3v O . The 
 
 \ I 
 \CH— O 
 
 oxycelluloses contain the characteristic group 
 
 /COH 
 (CH0H)3/ in union with varying proportions of 
 
 ^CH— CO 
 
 \o/ 
 
 residual cellulose. 
 
 Phenylhydrazine 
 
 Furfural 
 
 Fixed p.ct. 
 
 formed p.ct. 
 
 • 173 
 
 I -60 
 
 • 7-94 
 
 2-09 
 
 • 3-37 
 
 179 
 
 • 7-03 
 
 3-00 
 
 • 771 
 
 3-09 
 
 . 8-48 
 
 3-50 
 
g6 Cellulose 
 
 QUANTITATIVE SEPARATION OF CELLULOSE-LIKE 
 CARBOHYDRATES IN VEGETABLE SUBSTANCES. 
 
 WiLHELM Hoffmf:ister (Landw. Versuchs-Stat., 1897, 
 48, 401-41 1). 
 
 To separate the hemicelluloses, celluloses, and the consti- 
 tuents 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, CgH^Oj, soluble in alcohol and 
 chloroform, but insoluble in water, ether, and benzene ; pre- 
 parations from different sources melted between 200° and 210°. 
 
Cellulose Group gy 
 
 VERSUCHE ZUR BESTIMMUNG DES GEHALTS 
 EINIGER PFLANZEN UND PFLANZENTEILE AX 
 ZELLWANDBESTANDTEILEN AN HEMICELLU- 
 LOSEN UND AN CELLULOSE. 
 
 A. Kleiber (Landw. Vers.-Stat., 1900, 54, 161). 
 
 ON THE DETEKMINATION OF CELL-WALL CONSTITUENTS, 
 HEIIICELLUL0SE3 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 isola- 
 tion and estimation of cellulose. The method off. Schulze 
 [digestion with dil. HNO3 with KCIO3 — 14 days, and after- 
 wards 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. Miiller), 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 {l-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 pro- 
 ducts, 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 
 
 H 
 
98 Cellulose 
 
 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. (}reen plants of false oat grass {Arrhenatherium, E.). 
 
 2. Green plants of lucerne {Medicago saliva). 
 
 3. Leaves of the ash {Fraxinus). 
 
 4. Leaves of the walnut ( Juglans). 
 
 5. Roots of the purple melic grass {Molinia ccsruha). 
 
 6. Roots of dandelion (^Taraxacum t/fficittale). 
 
 7. Roots of comfrey. 
 
 8. Coffee berries. 
 
 9. Wheat bran. 
 
 These raw materials were treated for the quantitative esti- 
 mation 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 con- 
 stituents, and the corresponding deductions from the crude 
 
Cellulose Group 
 
 99 
 
 weight in calculating to ' pure cellulose.' The subjoined 
 extract will illustrate these main lines of investigation 
 
 Raw Material 
 
 Crude Fibre Pure Cellulose 
 
 Weende 
 
 Method. 
 
 (a) 
 
 Hoffmeister 
 
 Method. 
 (0 
 
 Hoffmeister, 
 
 modified by 
 
 Author. 
 
 Oat grass 
 Lucerne 
 Leaves of ash 
 Roots of melic 
 Coffee beans . 
 Bran 
 
 30-35 
 25-25 
 1305 
 2 1 -60 
 18-30 
 8-2 
 
 34-9 
 28-7 
 
 15-4 
 29-1 
 
 35-1 
 19-3 
 
 31-5 
 20-5 
 13-8 
 21-4 
 
 23-3 
 93 
 
 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. H2SO4), 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 con- 
 stituents are determined and deducted from the ' crude 
 
loo Cellulose 
 
 product,' which, thus corrected, may be taken as representing 
 the ' carbohydrate ' tissue constituents. 
 
 Determination of Hemicelluloses.— By the process of 
 boiling with dilute acids (i"2 5 p.ct. H2SO4) 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 PEN- 
 TOSANES 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 i, 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. 3o'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 
 
Cellulose Group lOl 
 
 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 hemi- 
 cellulose is obtained, by caustic soda, from the heated 
 solution than from that which was not heated. In this opera- 
 tion 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. Sevan, and C. Smith (Berl. Ber., 
 1896, 1457). 
 
 THE CONSTITUTION OF THE CEBEAL CEIITTLOSES. 
 
 (p. 84) Straw cellulose is resolved by two methods of acid 
 hydrolysis into a soluble furfural-yielding fraction, and an in- 
 
I02 Cellulose 
 
 soluble fraction closely resembling the normal cellulose, (a) The 
 cellulose is dissolved in sulphuric acids of concentration, 
 H2SO4.2H2O, H2SO4.3H2O. As soon as solution is com- 
 plete, 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 dige.sted with 
 six times its weight of i p.ct. H2SO4 at 3 atm. pressure, 
 the products of the action being (i) a disintegrated cellulose 
 retaining only a small fraction (.1^) 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 he 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 (BaCOa), 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'S, and H 6'7, 6'3. Determina- 
 tions of furfural gave 39*5 to 42-5 p.ct. On treating the 
 original solution with hydrogen peroxide, and warming, oxida- 
 tion set in, with evolution of CO2. This was estimated (by 
 
Cellulose Group 103 
 
 absorption), giving numbers for CO2, 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 ex- 
 pressed by the empirical formula C5H803<q>CH2, which 
 
 represents a pentose monoformal. Attempts to synthesise a 
 compound of this formula have been so far without success. 
 
 UEBER EINIGE CHEMISCHE VORGANGE IN DER 
 GERSTENPFLANZE. 
 
 C. F. Cross, E. J. Bevan, and C. Smith (Berl. Ber., 
 189s, 2604). 
 
 THE CHEMICAL IIFE-HISTOKY OF THE BABIEY PLANT. 
 
 (p. 84) Owing to the presence of'furfuroids' in large propor- 
 tion 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 barlev 
 plant was investigated at successive periods of growth. Yielo 
 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. i) 
 remaining permanently unmanured, and showing minimum 
 yield,. the other (No. 6) receiving such fertilising treatment as 
 to give maximum yields. 
 
lO-i. Cdlulosc 
 
 The numerical results are given in the annexed tables : 
 
 u 
 
 
 .2 
 
 
 ONNO-^f^-PlOO 
 
 P5 
 
 
 g 
 
 c 
 
 ^1 
 
 OOI^-OO^N-'^O -^00 
 
 
 
 vo loo i^ys 00 o O N — 
 
 ^ 
 
 
 2 
 
 . 3 
 
 r^MvO -^00 u-ju-)0 iJ^"-! 
 
 j3 
 
 H.- 
 
 <N O i-H ro O^ « Tt u-)vc LO 
 
 
 
 c * 
 
 i 
 
 i| 
 
 Tj-o^ONu^t^r^O"-)0 ■* 
 
 --a 
 
 r^>j-iNoo vnu-iO "~ioo 
 \f\\r\\f% lOvO vO 1^ t^ t^ r-^ 
 
 VO "^ O OS o ^o 
 
 yi T^^p r^ ^ 00 ro ^ p CO 
 
 O OS ^ invo OS r^ Os 1^ r^ 
 
 OS I^ N ii",VO « -H 00 f^ ro 
 
 ' VO '-' O "^ SO 
 
 O 
 PS 
 
 u 
 
 > 
 
 w 
 
 pi 
 « 
 
 
 vbob 
 
 
 0\ 0\ ii~, u-( 
 
 lo 
 
 U^f*^TfU^Tf«l-Tf-<e-Tj- 
 
 vO 00 O \0 ►-• 
 
 VD 
 
 N 00 ri- N 
 
 vO 
 
 lOOO 
 
 1^ M 
 
 o 
 
 Q^OsO O 
 
 
 
 
 
 
 \0 00 vo 
 
 ■^00 
 
 TfOO O r^ r^ 
 
 O 
 
 I^ -^ 
 
 ■r w 
 
 -d-vO u-i -rt-io 
 
 N 
 
 
 ro in i^vo vo 00 00 
 
 X "Ml 
 
 bo 
 < 
 
 1^ 
 
 w 
 
 VO 
 
 s 
 
 
 U-, 
 
 00 
 
 vO 
 
 so 
 
 ro 
 
 ^ 
 % 
 
 4) 
 
 c 
 
 3 
 
 1— » 
 
 60 
 
 a 
 
Cellulose Group 105 
 
 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 AV^ae-constituents, and only at the flowering period 
 is there any accumulation of these compounds in the alkali- 
 soluble form. It has been previously shown {jbid. 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 pento- 
 sanes. They are original products of assimilation, and not 
 subject to secor^dary changes after elaboration such as to alter 
 either their constitution or their relationship to the normal 
 hexose groups of the tissue-complex. 
 
 (I) CONSTITUTION OF THE CEREAL CELLULOSES 
 (Chem. Soc. J. 1896, 804). 
 
 (3) 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 
 
io6 Cellulose 
 
 hydrolysed by acids. Thus straw cellulose dissolves in sul- 
 phuric acids of concentration H2SO4.2H2O-H2SO4.3H2O, 
 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 (i p.ct. H2SO4) the conditions are 
 more easily controlled, the most satisfactory results being 
 obtained with 15 mins. heating at 3 atm. pressure. 
 
 (i) 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"S p.ct. of total dissolved solids, as compared with 12 -5 p.ct. 
 of total original grains ; cupric reduction (calc. to total solids), 
 1 10 (dextrose = 100) osazone ; yield in 3 p.ct. solution, 35 p.ct. 
 of weight of total solids. 
 
 Pentosazone 
 Analysis . . N I7'i I7'3 17'07 
 C 62-5 62-3 622 
 H 6-4 6-5 6-1 
 
 Melting-point .... 146°-! 53° 
 
 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 (BaCOs) 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 hydro- 
 chloric acid was a deep violet, in contradistinction to the 
 characteristic red of the pentoses. On oxidation with hydrogen 
 peroxide, in the proportion of i mol. HjOa to i mol. of the 
 carbohydrate in solution, carbonic anhydride was formed in 
 quantity = 2o'o p.ct. of the latter. 
 
Cellulose Group 107 
 
 Fermentation (yeast) experiments also showed a divergence 
 from the resistant behaviour of the pentoses, a consider- 
 able proportion of the furfuroid disappearing in a normal 
 fermentation. 
 
 (2) The quantitative methods above described were em- 
 ployed 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 \ in the early stages to a maximum of \ at 
 the flowering period. At this period the differentiation of the 
 groups begins to be marked. 
 
 Taking all the facts of (i) 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 
 
1 08 Cellulose 
 
 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. Obser- 
 vations 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 insti- 
 tuted 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 con- 
 stants 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 an mal 
 digestion. It has been now generally estabhshed 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 
 
Cellulose Group 109 
 
 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 assimi- 
 lation 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 con- 
 stant ratio to the total carbohydrates ; they are mainly located 
 in the permanent tissue ; in the secondary changes of dehy- 
 dration &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 inti- 
 mate union with the latter. They are finally converted into 
 pentoses by artificial treatments, and into pentosanes in the 
 plant, with loss of i 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 there- 
 fore a process of internal re-arrangement of the character of an 
 oxidation. 
 
 ZUR KENNTNISS DER IN DEN MEMBRANEN DER 
 PILZE ENTHALTENEN BESTANUTHEILE. 
 
 E. WiNTERSTEiN (Ztschr. Physiol. Chem., 1894, 521 ; 
 
 1895. 134)- 
 ON THE COKSTITUENTS OF THE TISSUE OF FUNGI. 
 
 (p. 87) These two communications are a contribution of 
 fundamental importance, and may be regarded as p'acing the 
 
1 10 Cellulose 
 
 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^HjoO^). This view is successively supported by Fromberg 
 [Mulder, Allg. Phys. Chem., Braunschweig, 185 1], Schloss- 
 berger 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 ' pilzcellu- 
 lose' [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 prepara- 
 tion [Sitzungsber. Acad. Wien, 82, i, 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 httle 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 treat- 
 ments with ether and boiling alcohol, {b) digestion with alka- 
 line hydrate (1-2 p.ct. NaOH) in the cold, {c) acid hydrolysis 
 (2-3 p.ct. H2SO4) at 95°-ioo'', followed by a chloroxidation 
 treatment by the processes of Schulze or Hoffmeister, and final 
 alkaline hydrolysis. 
 
Cellulose Group 
 
 III 
 
 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) . 
 Boletus edulis (Hoffmeisier process) . 
 Polyporus off. . 
 Cantharelius cib. .... 
 
 42-4 
 44-6 
 437 
 44-9 
 
 6-S 
 6-3 
 6-S 
 6-8 
 
 3-9 
 3-6 
 07 
 3-0 
 
 Agaricus campestris . 
 
 Botrytis ... . . 
 
 Penicillium glaucum .... 
 
 44-3 
 42-1 
 
 6-6 
 6-3 
 
 3-6 
 3-9 
 3 3 
 
 Morchella esculenta . 
 
 — 
 
 — 
 
 2-5 
 
 It is next shown that this residual nitrogen is not in the 
 form of residual proteids (i) by direct tests, all of which gave 
 negative results, and (2) indirectly by the high degree of re- 
 sistance to both alkaline and acid hydrolysis. The ' celluloses ' 
 are attacked by boiling dilute acids (i p.ct. HjSOj), 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. H2SO4, allowed to stand 24 hours, 
 then considerably diluted (to 3 • p.ct. H2SO4) and boiled to 
 
1 1 2 Cellulose 
 
 complete the inversion. The yields of glucose, calculated 
 from the cupric reduction, were as follows : — 
 
 Boletus edulis . 
 
 . 65-2 p.ct 
 
 Polyporus off. . 
 
 ■ 947 ., 
 
 Agaricus campestris . 
 
 ■ 59-1 „ 
 
 Morchella esculenta 
 
 . 6o-i ,, 
 
 Cantharellus cib. 
 
 • 64-9 ,, 
 
 Botrytis .... 
 
 . 6o-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 com- 
 plex 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 tissue 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 mean- 
 time E? Gilson had shown that these tissue substances in 
 ' fusion ' with alkaline hydrates yield a residue of a nitrogenous 
 product (CnHagNaOio), which is soluble in dilute acids 
 [Recherches Chim. sur la Membrane Cellulaire des Cham- 
 
Cellulose Group 1 13 
 
 pignons, La Cellule, v. 11, pt. i]. 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). 
 OK THE CARBOHYDEATES OF YEAST. 
 
 The author has isolated the more resistant constituents of 
 the cell-membrane by boiling with dilute alkalis, and exhaus- 
 tively 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 por- 
 tions of soluble cellulose (a) and insoluble (b). The latter, 
 giving no colour-reaction with iodine, is termed achroo- 
 cellulose ; the former reacts, and is therefore termed erythro- 
 cellulose. 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. 
 
 I 
 
114 Cellulose 
 
 (i) 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 Fnrfuraldehyde by Hydrogen Peroxide. 
 
 C. F. Cross, E. J. Bevan, and T. Heiberg (J. Ch. Soc. 
 1899, 747. 
 
 (4) EINWIRKUNG VON WASSERSTOFFHYPEROXID 
 AUF UNGESATTIGTE KOHLENWASSERSTOFFE. 
 
 C. F. Cross, E. J. Bevan, and T. Heiberg (Berl. Bar., 1900, 
 
 2015). 
 
 ACTION OP HYDBOGEN PEROXIDE ON ITNSATUHATED 
 HYDEOCAEBONS. 
 
 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 remark- 
 able 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 H2 with 
 production of the unsaturated group, — OH.C = C.OH — . 
 These investigations have subsequently been considerably de- 
 veloped and generalised by Fenton, but as the results have no 
 
Furfuroids 1 1 5 
 
 immediate bearing on our main subject we must refer readers 
 
 to the J. Chem. Soc. 1 896-1 900. 
 
 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 (i) and (2) that the particular 
 
 group to be so affected in the hexoses is that contiguous to 
 
 I 
 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, Isevulose, 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 HjOj employed. The mole- 
 cular proportion of the aldoses affected appears to be in con- 
 siderable 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 con- 
 densing 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 substitu- 
 tion 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 2o°-4o°, using 2-3 mols. HjOjper i mol. CSH4O2. 
 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 a yS derivatives.. The 
 
Ii6 Cellulose 
 
 aldehyde gives very characteristic colour reactions with phloro- 
 glucinol 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 H2O2 with permanganates 
 has now been established to be an oxidation of the Hj of the 
 peroxide by the permanganate oxidation, with liberation, 
 therefore, of the Oj 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 
 
Furfuroids 1 1 7 
 
 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 oxida- 
 tions 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 i)-GLUCON- 
 SAURE IN ZJ-ARABINOSE (Berl. Ber., 1898, 1573). 
 
 COKVEESION OF Z>-eHTCONIC ACID INTO X»-ABABINOSE. 
 
 D UND / ARABINOSE {Ibid. 1899, 550). 
 
 ZUR KENNTNISS DER OXYGLUCONSAURE {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 yS — CHOH — group 
 is converted into carbonyl at the same time that the terminal 
 COOH (a) IS oxidised to COj. The yields of the resulting 
 pentose are large. Simultaneously there is formed an oxy- 
 gluconic acid, which appears to be a ketonic acid of formula 
 — CH20H.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 
 
1 1 8 Cellulose 
 
 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 a ;8-hydroxyfurfural (ante, 115) we 
 obtain the a S-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 a S-hydroxyfurfural has 
 similar colour reactions to those of the a /3-derivative, and 
 may also therefore be present as a constituent of the ligno- 
 celluloses. The tendency to attack in the i'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. 
 
Furfuroids 119 
 
 VERGLEICH DER PENTOSEN-BESTIMMUNGSME- 
 THODEN VERMITTELST PHENYLHYDRAZIN UND 
 PHLOROGLUCIN. 
 
 M. Kruger (Inaug.-Diss., Gottingen, 1895). 
 
 COMFABISON OF METHODS OF ESTIMATINa FUBFUBAI AS 
 HYSBAZONE AND FHLOBOGITTCIDE. 
 
 The author traces the development of processes of esti- 
 mating furfural (i) by precipitation with ammonia (furfuramide), 
 (2) by volumetric estimation with standardised phenylhydra- 
 zine, (3) by weighing the hydrazone. 
 
 In 1893 (Chem. Ztg. 17, 1745) Hotter described a method 
 of quantitative condensation with pyrogallol requiring a tem- 
 perature of ioo°-i 10° for two hours. The insoluble product 
 collected, washed, dried at 103°, and weighed, gives a weight of 
 I '974 grm. per i grm. furfural. 
 
 Councler substitutes phloroglucinol for pyrogallol, with the 
 advantage of doing away with the digestion at high tempera- 
 ture. (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 investiga- 
 tion 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 o"Si6[-|- o'oi04] in calculating from the weights of preci- 
 pitates obtained, the maximum variations from the theoretical 
 number were +171 and — 174. In ip) it was found neces- 
 sary to vary the factor from 0-52 to 0*55 in calculating from 
 phloroglucide to furfural. The greatest total range of varia- 
 tion was found to be 2*5 p.ct. The phenol process is therefore 
 equally accurate, has the advantages above noted, and, in 
 
1 20 Cellulose 
 
 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. (i) the presence of diresorcinol in all ordinary pre- 
 parations 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 there- 
 fore 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[C5H402 + CeHjOj] — HjO = CjjHigOg, but appears to 
 have the composition Ci6H,206. 
 
 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"g-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. 
 
Furfuroids 121 
 
 UNTERSUCHUNGEN UEBER DIE PENTOSANBESTIM- 
 MUNG MITTELST DER SALZSAURE-PHLORO- 
 GLUCIN-METHODE.i 
 
 E. Krober (Journ. f. Landwirthschaft, 1901, 357). 
 
 INVESTIGATION OF THE HYDBOCHIOBIC ACID-PHIOEOBUJ- 
 CINOL METHOI) OF SETEBMIKINO FENTOSANES. 
 
 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 
 
 QH.Oa + CsHgOj - 2HjO = CuHsOa, 
 
 also, by varying the proportions of the pure reagents inter- 
 acting, 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 
 I 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 pre- 
 cipitated. The phenol must be perfectly dissolved by warming 
 with dilute HCl (i '06 sp.gr.) before adding to the furfural 
 
 ' This paper appears during the printiDg^ of the author's original MSS. 
 
122 
 
 Cellulose 
 
 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 o'3oo grm. 
 
 UEBER DEN PENTOSAN-GEHALT VERSCHIEDENER 
 MATERIALIEN. 
 
 B. ToLLENS and H. Gl-^ubitz (J. fiir Landwirtschaft, 
 
 1897, 97)- 
 
 ON THE PENTOSANS CONSTITUENTS OF FODDEK-PLANTS AND 
 
 MALT. 
 
 (p. 171) {a) The authors have re-determined the yield of 
 furfural from a large range of plant-products, using the phloro- 
 glucol method. The numbers approximate closely to those 
 obtained by the hydrazone method. The following may be 
 cited as typical : 
 
 Substance 
 Rye (Gbttingen) 
 Wheat (square head) 
 Barley (peacock) 
 Oats (Gbttingen) 
 Maize (American) 
 Meadow hay 
 Bran (wheat) 
 Malt 
 
 Malt-sprouts 
 Sugar-beet (exhausted) 
 
 Furfural p.ct. 
 6-03 
 
 475 
 4-33 
 772 
 
 3-I7 
 11-63 
 13-06 
 6-07 
 8-56 
 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 
 
Furfuroids 123 
 
 It is evident that the pentosa^es of wheat are localised in the 
 more resistant tissues of the grain. 
 
 (c) An investigation of the products obtained in the analy- 
 tical process for ' crude fibre ' gave the following : 
 
 (i) In the case of brewers' grains : 
 
 100 grms. grains . gave furfural = 29-43 pentosane 
 
 20 ,, crude fibre „ ,, = 2-52 
 
 ■ Acid extract . . ,, „ =2276 
 
 Alkali ,, . . ,, „ = I '20 
 
 Deficiency from total of original grains 2 95 
 
 29^3 
 
 (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 fur- 
 furoids in the process of malting, 100 pts. barley with 7^97 
 of ' pentosane ' yielding 82 of malt with 1 1 'iS p.ct. ' pentosane ' ; 
 confirming the observations of Cross and Bevan (Ber. 28, 
 2604). Of the total furfuroids of malt about \ are dissolved 
 in the mashing process. In a fermentation for lager beer 
 it was found that about ^V o^ 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 i 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 conse- 
 quently be taken into account as constituents of beers and 
 wines. 
 
124 
 
 Cellulose 
 
 UEBER DAS VERHALTEN DER PENTOSANE DER 
 SAMEN BEIM KEIMEN.^ 
 
 A. ScHONE and B. Tollens (Jour. f. Landwirthschaft, 
 1901, 349). 
 
 BEHAVIOTIB OF FSNIOSANDS OF SEEDS IN GEBniNATIOir. 
 
 The authors have investigated the germination of barley, 
 wheat, and peas, in absence of light, and generally with exclu- 
 sion of assimilating activity, to determine whether the oxida- 
 tion 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 per- 
 centages. 
 
 — 
 
 Original seed 
 A 
 
 Malt or 
 germinated product 
 
 B 
 
 Pentosane in 
 
 A 
 
 B 
 
 Barley . 
 Peas . 
 
 500-00 
 500-00 
 300-00 
 
 434-88 
 442-26 
 286-60 
 
 39-58 
 
 40-52 
 15-25 
 
 40-38 
 41-17 
 15-97 
 
 The authors conclude generally that there is a slight abso- 
 lute 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. Cham., 
 1897, i). 
 
 PENTOSANE CONSTITUENTS OF COTTON, 
 (p. 290) It has been stated by Link and Voswinkel 
 (Pharm. Centralhalle, 1893, 253), that raw cotton yields 
 ' This paper appears during the printing of the author's original MSS. 
 
Furfur oids 125 
 
 ' 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. 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 CuHigOg, we shall be able 
 to compare the ester derivatives with those of the celluloses, 
 which we have also referred to a C,2 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 a; (^) a 
 cellulose yielding furfural on boiling with condensing acids — 
 cellulose /8 ; and (c) a much condensed, and in part benze- 
 noid, group which we may continue to term the lignone 
 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 a and p. 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, (i) By 
 
126 Cellulose 
 
 chlorination &c. it is isolated in the form of an amorphous 
 body, but of constant composition, represented by the formula 
 C|9H,sCl409. 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 hydro- 
 chloric acid nor by-products of action. The product showed 
 an increase of weight of 7-5 p.ct. For one acetyl per i mol. 
 Ci9H]8Cl40g the calculated increase is 8-o 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 hydro- 
 lysis occurs in the processes of isolation. Thus the chlorinated 
 product we may assume to be derived from the complex 
 CigH220i). In the soluble by-products from the bisulphite 
 processes of pulping wood the lignone exists as a sulphonated 
 derivative, C24H23(OCH3)2.(S03H).07. The original lignone 
 may be regarded as passing into solution as a still condensed 
 complex derived from C24H26O12 (ToUens). There is evi- 
 dently 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 approxi- 
 mately in the relation Ce : Hg : O3, and it may assist this dis- 
 cussion to formulate the main constitutional types consistent 
 with this ratio, viz. : 
 
 (i) The trihydroxybenzenes C6H3(OH)3. 
 
 (2) Methylhydroxyfurfural C5H20.(OH)(CH3). 
 
Lignocelluloses 1 27 
 
 /(CH3) 
 (3) Methylhydroxypyrone CO^CiHa J^O. 
 
 \(0H) 
 
 (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 com- 
 plexity 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 
 SQHioOj.H.jO. 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 a . 65 
 
 ^ ■ IS 
 Lignone . 20 
 
 = 100 lignocellulose. 
 
 Jute Benzoates. — In preparing the jute for treatment 
 it was boiled in alkaline solution (i per cent. NaOH), washed 
 with water and dilute acid, again washed, dried, and weighed. 
 
 In the ester reaction the reagents were employed in the 
 
128 Cellulose 
 
 proportion CijHigOg : 3NaOH : 2C5H5COCI. 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 ligno- 
 cellulose, which are fainter. The ferric ferricyanide re- 
 action 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 promi- 
 nently, 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 i'o6 sp.gr. was 3'02 and 3'29 in separate 
 determinations. Calculating to the original ligno-cellulose, 
 the percentage, 4'2i, indicates a considerable loss of the 
 furfural-yielding constituent. The effect was also apparent in 
 the cellulose (benzoate) isolated by chlorination &c., the per- 
 centage being i'39 p.ct., and calculated to the original jute 
 benzoate i'59 p.ct. Under the conditions adopted in dis- 
 
Lignocelluloses 1 29 
 
 solving 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 treat- 
 ment with the concentrated alkali, therefore, the furfuroid of 
 the original lignocellulose undergoes little change, but is 
 selectively dissolved. This point is under further investi- 
 gation. 
 
 (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 ist edition (p. 132). A 
 further study of 'the reactions in regard to special points 
 has led to some more definite results. The yields of pro- 
 duct by the ordinary and simple process are 1 14-1 15 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,2H,^09 30-8 
 
 78-4 
 
 The derivative is approximately a diacetate, and on the 
 assumption of a simple ester reaction the yield should be 
 
 K 
 
1 30 Cellulose 
 
 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. HjO 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 Qy}i.J^^^ 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 acetyl- 
 ated without condensation (see p. 41). On saponilicatioH 
 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 pro- 
 bably 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 ligno- 
 cellulose are unaffected by the acetylation and condensation. 
 The hygroscopic moisture of the product is lowered from 
 10- II 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 (ist ed.). 
 
 Acetylation of Benzoates. — The cellulose dibenzoate (Cu 
 
Lignocelluloses 1 3 1 
 
 basis) and the jute monobenzoate were acetylated under 
 comparative conditions. The results were as follows : 
 
 
 
 
 C,„ basis 
 
 
 
 Cellulose 
 
 dibenzoate Jute monobenzoate 
 Calc. for Cal . for 
 
 
 
 Found 
 
 diacetate on Found diacetate on 
 
 Ester reaction 
 
 
 
 dibenzoate monobenzoate 
 
 Yield . 
 
 . * . 
 
 III p.ct. 
 
 115 p.ct. 124 p.ct. 120 p.ct. 
 
 Saponification 
 
 j Cellulose 1 
 1 Lignocellulose l" 
 
 S3'5 
 
 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 (ist 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 
 
 Ci2H,809+4HN03-4H20 
 
 gives a tetranitrate with ii'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 quanti- 
 tatively we have devised a suitable variation of the method of 
 combustion with chromic acid (ist 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 
 
132 Cellulose 
 
 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 CrOs is then pro- 
 reeded 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 convenieht 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 ligno- 
 cellulose. 
 
 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 Ci2H,809 (= 306) is therefore 
 462, whereas for a tetranitrate formed by a simple ester 
 reaction the yield should be 486. The difference (24) repre- 
 sents i"S mol. H2O split off by internal condensation. 
 
 The correction for total N is relatively small, raising it 
 from 115 to i2'2, which remains in close agreement with the 
 experimental numbers. 
 
 MonobenzoaU. — Treated with the acid mixture yields a 
 mixed nitrate. The yield is 130 p.ct., and the product con- 
 tains 7-6 p.ct. O.NOj nitrogen. These numbers approximate 
 to those required for reaction with 4HNO3 groups, three of 
 the residues entering the cellulose, and one (as NOj) the 
 
L ignocelluloses 1 3 3 
 
 benzene ring of the substituting group. For such a reaction 
 the calculated numbers are : Yield 144 p.ct. ; O.NO2 nitrogen 
 7'i 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 i mol. of 
 jute benzoate (410) is 576, as against the calculated 590 for 
 4HNO3 reacting. A loss of iHjO 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 con- 
 siderable 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- 
 ^-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 
 amido-benzoate, which confirms the localisation of a nitro- 
 group in the benzoyl residue. 
 
 (p. 157) General Characteristics of the Ligno- 
 celluloses. — 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 
 
1 34 Cellulose 
 
 statistics of its more important decompositions (original, 
 pp. 1 57-161). 
 
 Cellulose. — There is little doubt that the furfural-yield- 
 ing groups of the original are isolated in the form of the 
 yS-cellulose. ToUens 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 repre- 
 sented 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 CI combining with the fibre 
 substance or lignocellulose (p.ct.), to that of the Q\ present in 
 the isolated lignone chloride (p.ct.). The lignocellulose com- 
 bines with chlorine in the ratio 100 : 8, but the lignone 
 chloride containing 267 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 ^.^ or a little over 
 20 p.ct. 
 
L ignocelluloses 135 
 
 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 
 
 C19H22O9 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 a 
 
 CeIIulo.se ^ 
 
 Lignone 
 
 65 p.ct. 
 
 15 p.ct. 
 
 20 
 
 Allied to the normal 
 
 Vield"ng furfural ap- 
 
 One-third of which 
 
 celluloses 
 
 proximately 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, i5S8)- 
 
 CHEMISTEY OF LIGNOCELLtTLOSES— 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,' i grm. of substance occupying an 
 apparent volume of 40-50 c.c. This pith-like substance is 
 
1 36 Cellulose 
 
 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 (i'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 
 compoundSj is only faintly marked in the main tissue, though 
 strongly in certain individual cells. 
 
 The following quantitative determinations, however, es- 
 tablish the close similarity of the product to the typical ligno- 
 celluloses : 
 
 Elementary Analysis. — C 46"55, H 67. Furfural 1 1 '6 p.ct., 
 of which there remained in the residue from alkaline hydrolysis 
 (71 p.ct.) 8*o, i.e. about 70 p.ct. The distribution of the 
 lurfuroids is therefore not affected by the alkaline treatment. 
 
 Chlorination. — The substance (after alkaline hydrolysis) 
 takes up i6'9 p.ct. CI, of which approximately one-half is 
 converted into hydrochloric acid. 
 
 Metkoxyl. — O.CH3 estimated = 2-9 p.ct. 
 
 Ferric Ferricyanide Reaction. — Increase of weight due to 
 blue cyanide fixed (i) 75 p.ct, (2) 96 p.ct. Ratio, Fe : CN 
 = I : 2, 4. 
 
 Hydroxy I 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 piant 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. 
 
L ignocelluloses 137 
 
 (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 observa- 
 tion in the same obvious way as do their fibrous relatives. 
 The pith of the elder, however, is readily obtained in con- 
 venient 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, 
 r2'3 p.ct. Alkaline hydrolysis (loss): (a) 14'TJ, (i) i7"84. 
 Cellulose (yield), 52-33 p.ct. Nitrate-reaction complicated by 
 secondary reactions and yields low, go'gs p.ct. Sulpho- 
 carbonate 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 (p) 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 (i) with cold dilute ammonia. 
 
138 
 
 Cellulose 
 
 (2) cold dilute soda lye (2 p.ct. NaOH), and (3) boiling 
 o'l p.ct. NaOH. The product retained only 125 p.ct. 
 proteids, and yielded 15 '6 2 p.ct. furfural. 
 
 Acid Hydrolysis. — The product was boiled 30 mins. with 
 dilute acid (1-25 p.ct. H2SO4), and the solution boiled until 
 the Fehling test showed no further increase of monoses. 
 At the limit the reducing power of the dissolved carbo- 
 hydrates was 9 1 '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 
 267 p.ct. CI 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 CigHjgCl^Og. 
 
 Cellulose was isolated from the residue by three of the 
 well-known methods, and the following comparative numbers 
 are noteworthy : 
 
 Method 
 
 F. Schuize 
 
 Dil. 
 
 HN0, + KC10, 
 
 Lange 
 Fusion KOH 
 
 Cross and 
 
 Bevan 
 
 Chlorine, &c. 
 
 Cellulose p.ct. obtained 
 Furfural p.ct. of cellulose 
 Residual nitrogen . 
 Ferricyanide reaction, 
 Prussian blue fixed . 
 
 660 
 
 7-0 
 
 0-22 
 6-04 
 
 39-3-43-I 
 3-96 
 0-03 
 
 0-89 
 
 66 -s 
 S-62 
 
 0-00 
 
 0-92 
 
Lis^nocelluloses 
 
 139 
 
 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 con- 
 fined to the furfuroids. 
 
 Animal Digestion of the Constituents of Bran. — Observa- 
 tions on a steer fed upon wheat bran only established the 
 following percentage digestion of the several constituents : 
 
 Soluble carbohydrates 
 
 Starch 
 
 Free pentosanes 
 
 Cellulose . 
 
 Lignin complex 
 
 Proteid . 
 
 Ether extract . 
 
 
 
 96-9 
 loo-o 
 
 60 -2 
 24-8 
 367 
 82-96 
 
 4273 
 
 Nitrogen-free extract. 
 Crude fibre 
 
 76-08 
 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 
 
140 
 
 . Cellulose 
 
 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 
 (a) of Samples of Jute ; [f) 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 (i). 
 
 435 
 
 Fifth and Sixth Report on Australian Fibres. 
 
 1896. 68 Hibiscus and Abroma Fibres. 
 
 104-5 Hibiscus, Urena, and Crotalaria Fibres. 
 
 141 Indian Sisal. 
 
 (<r) 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 
 
 
 II-O 
 
 10-4 
 
 II-I 
 
 9-6 
 
 Ash . . . 
 
 . 
 
 0-87 
 
 2-8 
 
 I'O 
 
 07 
 
 /Alkaline hydrolysis 
 5 mins. boiling 
 
 (a) 
 
 13-2 
 
 11-6 
 
 8-5 
 
 9-1 
 
 
 
 
 
 
 i Alkaline hydrolysis 
 
 {i) 
 
 161 
 
 I7-S 
 
 12-5 
 
 13-1 
 
 60 mins. boiling 
 
 
 
 
 
 
 ^ Mercerising treatment 
 
 . 
 
 9-2 
 
 105 
 
 IO-3 
 
 8-5 
 
 Nitration (increase p.ct.). 
 
 366 
 
 357 
 
 37-5 
 
 367 
 
 Cellulose (yield) 
 
 
 71 '4 
 
 70-0 
 
 790 
 
 777 
 
 Acid purification 
 
 ■ 
 
 2-6 
 
 1-3 
 
 I '9 
 
 2-0 
 
Lienocelluloses 
 
 141 
 
 A useful series of experiments, initiated by the Institute is 
 that noted under {b) and {c) above. 
 
 (i) 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. I . Cut before appearance of inflorescence. 
 ,,2. ,, after budding. 
 ,,3. „ in flower. 
 ,,4. ,, after appearance of seed-pod. 
 ,,5. ,, when fully matured. 
 
 , — 
 
 (0 
 
 W 
 
 (3) 
 
 (4) 
 
 (■i) 
 
 Moisture 
 
 ; '^^■^S 
 
 874 
 
 107 
 
 lo-o 
 
 972 
 
 Ash . 
 
 i '■' 
 
 II 
 
 i-i 
 
 II 
 
 o-go 
 
 Alkaline hydrolysis (a) . 
 
 ' 6-2 
 
 8-5 
 
 97 
 
 8-9 
 
 7-3 
 
 „ (*) . 
 
 IO-5 
 
 II-9 
 
 II -6 
 
 I20 
 
 1 1 -2 
 
 1 Mercerising treatment 
 
 102 
 
 107 
 
 I2-0 
 
 8-1 
 
 II-O 
 
 1 Nitration 
 
 37-2 
 
 32-1 
 
 32-2 
 
 33 2 
 
 366 
 
 Cellulose 
 
 ! 74 -o 
 
 76-2 • 
 
 74-1 
 
 74-8 
 
 76-4 
 
 Acid purification . 
 
 1 0-8 
 
 o-S 
 
 07 
 
 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 con- 
 clusion 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. i 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. 
 
142 Cellulose 
 
 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 
 (i) 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. Stoker (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 : 
 
L ignocelluloses 
 
 143 
 
 
 Wood 
 
 Bark 
 
 Inner 
 
 Outer 
 
 May .... 
 July .... 
 October 
 
 21-3 
 
 166 
 162 
 
 19-6 
 188 
 
 16-3 
 
 167 
 II-4 
 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 6o°C., (^) boiling dilute HCl 
 (I'op.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 cal- 
 culated as starch dissolved . 
 
 Residue boiled, 1 p.ct. HCl 
 gave pentosanes dissolved . 
 Residue yielded furfural. 
 
 4-24 
 19-3 
 
 3-S 
 
 S-2 
 
 Man nan 
 
 117 
 
 3-4 
 
 i-s 
 141 
 
 9-6 
 
 67 
 97 
 
 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 
 
 wood 
 
 Inner 
 wood 
 
 In original substance 
 In residue from action of 2-5 
 p.ct. HCl .... 
 
 167 
 
 6-S3 
 
 ig-6 
 8-6 
 
 i8-2 
 4-9 
 
 207 
 
 6-4 
 
 iS'4 
 7-0 
 
 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. 
 
144 Cellulose 
 
 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 re- 
 commended in all cases to examine the product for furfural 
 quantitatively, converting the numbers into pentosane equiva- 
 lents, 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 UOTHEB SUBSTANCES OF WOOD-GUIt. 
 
 , (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 alkahne, 
 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 ' in- 
 crusting 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 i -25 p.ct. H^SOj (residue) . lO'i 
 
Ltgnocelluloses 145 
 
 Yield of furfural 
 Substance p.ct. 
 
 Cellulose— isolated by Schulze process (yield 53 p.ct. ) 6 '9 
 
 „ after further 14 days' digestion with the 
 
 Schulze acid (HN0, + KC10,) . . 5-9 
 ,, after extraction with 5 p.ct. NaOH in 
 
 cold (residue) i . 1 . .5-0 
 ,, after second extraction with 5 p.ct. NaOH 
 
 in cold (residue) 4-4 
 
 UEBER DIE FRAGE NACH DEM URSPRUNG 
 UNGESATTIGER VERBINDUNGEN IN DER 
 PFLANZE. 
 
 C. F. Cross, E. J. Bevan, and C. Smith (Berl. Ber., 
 189s, 1940). 
 
 ON THE SOTIECE OF THE UNSATITEATED 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 decomposi- 
 tion of the cellulosic complex. A series of distillations was 
 carried out with dilute sulphuric acids of varying concentra- 
 tion from 10-50 H2SO4 : 90-50 HjO 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 
 
 (HjSOJ p.ct. . . 10 IS 20 30 40 so 
 Furfural yield p.ct. of 
 
 straw . . . 2-0 20 44 lO-l II'S ll-o 
 Volatile acid (calculated 
 
 as acetic acid) p.ct. of 
 
 straw , . . 17 1-9 3-1 4'3 6"3 H'S 
 
 With acids up to 20 p.ct. H2SO4 both products are formed 
 concurrently and in nearly equal quantity. With the 30 p.ct. 
 
 L 
 
146 
 
 Cellulose 
 
 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 i'o6 s.g. (Tollens), in this case i2-4 p.ct. The vola- 
 tile acid increases, but in less ratio ; it is also produced 
 concurrently. With 50 p.ct. H2SO4 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. H2SO4), with the following 
 results : 
 
 
 - 
 
 Volatile acid 
 
 
 Acetic 
 
 Formic 
 
 Swedish filter-paper 
 Esparto cellulose . 
 Bleached cotton . 
 Raw cotton (American) . 
 J ute cellulose 
 Beech (wood) cellulose 
 
 03 
 12-4 
 trace 
 
 5-2 
 6-4 
 
 27 
 
 3-2 
 
 31 
 
 4-9 
 3-5 
 
 17-2 
 
 i6-6 
 132 
 
 9 4 
 227 
 14-6 
 
 The tendency in the hexoses and their polyanhydrides to 
 iplit off one carbon atom in the oxidised form, throws some 
 light on the furfurane type of condensation, which is repre- 
 sented in the lignocelluloses. We are still without any evidence 
 as to the possible transition of the hexoses to benzenoid com- 
 pounds. 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). 
 
 JPEOSTTCTION OF ALCOHOL FB.OU CELLULOSE AND WOOD. 
 
 (pp. 50, 209) This investigation was undertaken with one 
 
 main object — to determine the optimum conditions of treat- 
 
L ignocelluloses i zj 7 
 
 ment of wood-cellulose and of wood itself for conversion into 
 'fermentable sugar.' The process of 'inversion' or hydro- 
 lysis, by digestion with dilute acid at high temperature, involves 
 the four main factors : pressure (i.e. temperature), concentra- 
 tion 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 o-45-o'6o p.ct. 
 (H2SO4) 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 con- 
 ditions were ascertained 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^SO^ 
 
 Pressure ..... lo atm. 
 
 Duration of digestion . . • 1 'S 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 
 
148 Cellulose 
 
 similarly systematic investigation carried out upon pine sawdust 
 established the following as optimum condi'.ions : 
 
 Proportion of total liquid . . 5 times wt. of wood 
 
 Concentration of acid . . , 0'5 p.ct. H^SO, 
 
 Pressure ..... 9 atm. 
 
 Duration of digestion . . IS 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 the theoretical, 
 the author finally concluding that under properly controlled 
 conditions of inversion and fermentation 100 kg. wood yield 
 6-5 1. absolute alcohol. 
 
 tJBER DIE URSACHE DER VON 'SIMONSEN 
 BEOBACHTETEN UNVOLLSTANDIGKEIT DER 
 VERGAHRUNG DER AUS HOLZ BEREITETEN 
 ZUCKERFLUSSIGKEITEN. 
 
 B. ToLLENS (Ztschr. angew. Chem., 1898, 15). 
 
 ON THE CAUSE OF INCOMPLETE FEEMENTATION OF 8UGABS 
 OBTAINED BY ACID HYDEOLYSIS 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'). 
 I'hey 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 investiga- 
 tions of peat (Berl. Ber. 30, 257 1), and was found to be similarly 
 incompletely attacked by yeast. The yields of alcohol corre- 
 
Lignocelluloses 
 
 149 
 
 sponded with the proportion of the total carbohydrates dis- 
 appearing. These were the hexose constituents of the 
 hydrolysed complex, the pentoses (or ' furfuroids ') surviving 
 intact. 
 
 UEBER SULFITCELLULOSEABLAUGE. 
 
 H. Seidel (Ztschr. angew. Chem., 1900). 
 
 WASTE LIQUOES FBOM BISTTLFHITE PROCESS. 
 
 (p. 210) Later researches confirm the conclusion that in 
 the soluble by-products of these cellulose processes the S is 
 combined as a SO3H group. The following analyses of the 
 isolated lignin sulphonic acid are cited : 
 
 (a) Lindsey and ToUens . 
 
 [b) Seidel . . (i) 
 
 [c) Seidel and Hanak (2) 
 
 (d) Street 
 
 H 
 
 S 
 
 5-3° 
 
 5-65 
 
 5-87 
 
 5-52 
 
 5 '22 
 
 8 -80 
 
 5-64 
 
 7-67 
 
 The variations are due to the varying conditions of the diges- 
 tion 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 SO3H, the following figures result : 
 
 
 (a) and (*) 
 
 w 
 
 (d) 
 
 c . . . . 
 H . . . . 
 
 64-00 
 665 
 
 651 
 
 6-33 
 
 59-61 
 6-69 
 
 This author considers that beyond the empirical facts 
 established by the above named ' very little is yet known in 
 regard to the constitution of the lignone complex. 
 
 ' See more particularly : Lindsey and Tollens, Annalen, 267, 341 ; 
 Cross and Bevan's Cellulose, pp. 197-203 ; Street, Inaug. -Diss. , Gbttingen, 
 
I So Cellulose 
 
 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 regenera- 
 tion 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 pro- 
 cesses 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 dis- 
 tillation 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 
 
 1892 ; Kla.son, Rep. d. Chem. Ztg. 1897, 261 ; Seidel and Hanak, 
 Mitt. d. Techn. Gew. Mus. 1 897- 1898. 
 
Lignocelluloses 151 
 
 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 re- 
 dissolved in weak alkaline solutions and employed in this 
 form for engine-sizing papers. Ekman has patented a process 
 (D.R.P. 81,643) fo"" '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 applica- 
 tion of the soda salt of the lignone sulphonic acid as a re- 
 ducing 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.' 
 
 UNTERSUCHUNGEN UBER PECTINSTOFFE. 
 
 R. W. Tromp de Haas and B. Tollens (Lieb. Ann., 
 \ 286, 278). 
 
 iJBER DIE CONSTITUTION DER PECTINSTOFFE 
 
 B. Tollens {fbid. 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 
 
152 
 
 Cellulose 
 
 results fail to confirm a high ratio O : H. 
 are the analytical numbers : 
 
 The following 
 
 Pectin from 
 
 Ash 
 
 C 
 
 H 
 
 Ratio H : 
 
 Apple .... 
 
 6-2 
 
 43-4 
 
 6-4 
 
 
 7-9 
 
 Cherry .... 
 
 20 -5 
 
 42-5 
 
 6-s 
 
 
 7-9 
 
 Rhubarb .... 
 
 4-2 
 
 43 -3 
 
 6-8 
 
 
 7-4 
 
 Currant .... 
 
 50 
 
 47-1 
 
 S-9 
 
 
 8-S 
 
 Greengage 
 
 3-3 
 
 43 'o 
 
 5-9 
 
 
 S..5 
 
 Turnip .... 
 
 7-3 
 
 41 
 
 5-9 
 
 
 90 
 
 Acid hydrolysis (4 p.ct. H2SO4) 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. 
 
 ToUens points out that the results of empirical analysis are 
 inconclusive ; and that from the acid reactions of these pro- 
 ducts 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 {Pflanzenschleifn), 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). 
 
 COSSTITUTION 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. fur- 
 fural on boiling with HCl (i'o6 s.g.), reacted freely with 
 chlorine, giving quinone chlorides, and with ferric ferricyanide 
 to form Prussian blue. This ' pectin ' is therefore a form 
 
Pectic Group 153 
 
 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 VE&EIABLE AMYLOID. 
 
 (p. 224) A group of constituents of many seeds, dis- 
 tinguished 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 Tropceolum majus, Fceonia 
 officinalis, and Itnpatiens 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 6t. On boiling with 
 12 p.ct. H CI it gave is"3 p.ct. furfural; oxidised with nitric 
 acid it yielded io'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 solu- 
 tion 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 con- 
 
154 
 
 Cellulose 
 
 stituent, 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 pre- 
 sent in some quantity, but could not be isolated. The original 
 seed tissues, therefore, contain an amyloid and a hemi- 
 cellulose, 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 UNU 
 AN ANDEREN KOHLENHYDRATEN. 
 
 H. V. Feilitzen and B. Tollens (Berl. Ber., 1897, 2,571). 
 
 CABBOHYSBATE CONSTITXTENIS 07 FEAT. 
 
 (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. 
 
 SI -08 
 
 6-93 
 
 I. 
 
 100-200 ,, ... 
 
 53-52 
 
 5-30 
 
 
 1 200-300 ,, ... 
 
 58-66 
 
 3-19 
 
 
 Surface- 20 „ . . . 
 
 55-47 
 
 3-40 
 
 
 20- 60 ,, ... 
 
 55-06 
 
 3-48 
 
 II. 
 
 60-100 „ ... 
 
 58-25 
 
 1-45 
 
 
 100-120 ,, ... 
 
 5823 
 
 1-19 
 
 
 I 180-200 „ ... 
 
 57-57 
 
 I -So 
 
 Cellulose was estimated by the Lange method, 
 from Sphagnum was 2i-i p.ct. 
 
 The yield 
 
 From specimen I. at J 
 
 00 cm. 15-20 
 „ 6-87 
 
Industrial Developments 155 
 
 From the peat of lower depths no cellulose could be 
 obtained. 
 
 Hydrolysis (acid). — On heating with i p.ct. H2SO4 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. 
 
 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 im- 
 portant 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 con- 
 ditions 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 dimen- 
 sions ; 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 hydro- 
 lysis. It is suggested that any important addition to the very 
 limited number fulfilling the conditions, or any great improve- 
 ment in these, can only result from very elaborate artificial 
 selection and cultural developments on this basis. 
 
1 56 Cellulose 
 
 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 siEing 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 
 sulpho-carbonate (viscose) ; the nitrates, in their applications 
 to explosives, on the one hand, and the spinning of artificial 
 fibres (lustracellulose), on the other ; and the cellulose 
 acetates. 
 
. Industrial Developments 157 
 
 La Viscose et le Viscoide. 
 
 C. H. Bardy (Bull. Soc. d'Enc. Ind. Nationale, igoo, 
 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 vis- 
 cosity 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 
 
158 Cellulose 
 
 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 com- 
 mercial 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. 
 
Industrial Developments 159 
 
 Ueber die Viscose. 
 
 B. M. Margoschks (Reprint from Zeitschrift fiir die gesammte 
 Textil-Industrie, 1900-01, Nos. 14-20).' 
 
 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 iirst discusses the two directions of depreciation 
 of papers in use : (i) 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 chlori- 
 nated 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 freqiiently 
 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 
 
 ' This is the most complete notice that has appeared and the biblio- 
 graphy is exhaustive. The publication comes into our hands too late to 
 be noticed in detail. 
 
i6o Cellulose 
 
 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 Can- 
 tor 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 {p) 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 in- 
 vestigations 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, there- 
 fore, satisfied to limit their specific findings to the following — 
 viz. (i) 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 
 
Industrial Developments 1 6 1 
 
 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 Versuchs- 
 anstalten, 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 de- 
 velopment 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 
 
 M 
 
1 62 Cellulose 
 
 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. Not- 
 withstanding 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. 
 
Industrial Developments 163 
 
 It may be noted that there have been no important de- 
 velopments in the purely chemical processes involved in the 
 several systems of preparing cellulose from wood. The acid 
 methods' (bisiilphite processes) have developed much more 
 extensively than the alkaline, the latter including the caustic 
 soda and the mixed sulphide (' Dahl ') process. Ttie bisulphite 
 processes depended in the earher 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 econo- 
 mies 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 Com- 
 petition, 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-equihbrium 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.' 
 
 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 mcst part an 
 absolute waste, notwithstanding the many investigations of 
 technologists and attempts to convert it to industrial use (see 
 
 ' Text-book on Paper-making, Cros5 and Sevan (Spon, London : 
 second edition, 1900). Chemistry of Paper-making., Griffin and Little 
 (New York, 1894: Howard Lock wood & Co.). Handbach d. Papier- 
 fabrikation, C. Hofmann (Berlin). Paper Trade Reuiev), London (weekly). 
 Papier-Zeitung, Berlin. 
 
164 Cellulose 
 
 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 pollu- 
 tion 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 mag- 
 nesium bisulphites are used, the residue from calcination is 
 practically without value. It appears, however, that by sub- 
 stituting soda as the base the alkali is recoverable in such a 
 form as to be directly available for the alkaline-sulphide or 
 ' I )ahl ' 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 cal- 
 cining. The engineering features of the system, so far as 
 regards e\aporating and calcining, are the same. For economic 
 working there is required (a) evaporation by multiple effect 
 and [h) 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 develop- 
 ments are referred to the various publications of these inventors 
 
Industrial Developments 165 
 
 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 mag- 
 nesia (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 com- 
 prehensive 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 10/. 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, notwith- 
 standing 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. 1 73). 
 
1 66 Cellulose 
 
 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 chemicail 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 whiten- 
 ing effect or bleaching action proper, occupies a position of 
 often exaggerated importance. 
 
 In bleaching processes there has been no radical change 
 of systehi 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 yery 
 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, 
 
Industrial Developments 167 
 
 William Mather, ' 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 develop- 
 ment 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 solu- 
 tions, 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 eifect 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. ^3i40o 1900, W. Mather]. If we again consider 
 
 the principles involved, they are very much as set forth in our 
 
 ' William Mather, M.P., of the firm of Mather & Piatt, Limited, 
 Manchester. 
 
1 68 Cellulose 
 
 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 re- 
 moved 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 pro- 
 portion 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 
 
Industrial Developments 169 
 
 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 in- 
 definite 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 con- 
 siderations 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 funda- 
 mental principle which has been almost universally ignored. 
 
 In the oxidising processes which follow the alkaline treat- 
 ments, the hypochlorites are still the staple agents. Owing to 
 the steady relative fall in the selling prices of the per- 
 manganates 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 
 
170 Cellulose 
 
 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 
 recede a 'roUing-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. Tiirk (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 Miiller, 
 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 
 
Industrial Developments 171 
 
 qualified to judge is that the new industry has vindicated for 
 itself a permanent position. 
 
 II. The Chemical Derivatives of Cellulose, in their in- 
 dustrial 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 com- 
 pounds 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. Their 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 ' lustracelluloses,' by the collodion processes also, whilst 
 presenting features of unusual interest attaching to rapid expan- 
 sion, 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 to 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 
 
172 Cellulose 
 
 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 indis- 
 pensable 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 applica- 
 tion of viscose the dissolved cellulose is paid for at the rate of 
 I as. 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 
 ^s.-xos. per lb., a price which on the one side excludes exten- 
 sive consumption, and on the other practically bars manufac- 
 ture in this country by any of the collodion systems. It will ap- 
 pear 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 
 
 Cotton. Nitrating acid. Ether- 
 Raw materials ' . . alcohol (solvent). Denitrating 
 ^ chemicals. 
 
 ' 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 con- 
 clusion that the item for raw materials made up 60 p.ct. of the total cost 
 of the yarn. 
 
Industrial Developments 173 
 
 1(a) Nitrating and preparing col- 
 lodion. Denitrating and 
 bleaching. 
 {b) Textile operations. Spinning. 
 Winding and twisting. Re- 
 winding. 
 
 /Making, filtering, and distributing 
 Power . ... collodion. Driving textile ma- 
 
 chinery. 
 
 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 solu- 
 tion 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 5J. to 7^., 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 (i) on cupiammonium 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 12/.) can certainly be obtained in solu- 
 tion in a condition ready for spinning at a total cost (materials) 
 of less than 30/. The cuprammonium process, so far as 
 • outside ' information goes, requires for production of the 
 solution (i) cotton as raw material, (2) ammonia (calc. as 
 concentrated aqueous) equal to i^ times its weight, and 
 
1/4 Cellulose 
 
 (3) metallic copper 25 p.ct. of its weight ; and the costs are 
 approximately 100/. 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 in- 
 variability of the collodion. It is to be regretted, in the 
 interests of scientific development, that none of the techno- 
 logists 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 cupram- 
 monium 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 orlly 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 
 
Industrial Developments 175 
 
 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.^ We leave the discussion of the industrial 
 problem at this point. 
 
 In regard to other developments based upon the excep- 
 tional 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 appli- 
 cations 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. 
 
 ' The recent failure of a French company founded for the exploita- 
 tion 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., 1S7 
 Bokomy, T. , 43 
 Bronnert, E., 54 
 Bumcke, G. , and 
 WolflFenstein, R., 67 
 Buntrock, 25 
 
 Cross, C. F., 139, 
 
 152. iSS 
 Cross, C. F., and 
 
 Bevan, E. J., 92 
 Cross, C. F., Bevan, 
 
 E. T., and Briggs, 
 
 J. F"., 118 
 Cross, C. F., Bevan, 
 
 E. J., and Heiberg, 
 
 T., 114 
 Cross, C. F., Bevan, 
 
 E. J., and Smith, 
 
 C, loi, 103, los, 
 
 114, HS 
 
 De Haas, R. W. T., 
 and ToUens, B. , 
 151 
 
 Faber, O. v., and 
 ToUens, B., 71 
 
 Feilitzen, H. v., and 
 ToUens, B., 154 
 
 Fenton, H. J. H., 8 
 
 Fenton, H.J. H., and 
 GostUng, M., 86 
 
 Fraenkel, A. , and 
 Friedlaender, P. , 26 
 
 Gardner, P., 22 
 GUson, E., 112 
 
 Hancock, W. C, 
 and Dahl, O. W., 
 
 13s 
 Hoffmeister, W., 96, 
 100 
 
 Kleiber, a., 97 
 Krober, E., 121 
 Kriiger, M., 119 
 
 Lange, H., 25 
 Lewes, V. H., IJ 
 Luck, A., and Cross, 
 C. F.. 45 
 
 Margosches, E. M., 
 
 159 
 MorreU, R. S., and 
 
 Crofts, J. M., 114 
 MyUus, F., 21 
 
 Nastukoff, H., 74 
 
 Omelianski, v., 76 
 Ruff, O., 117 
 
 Salkowski, E., 113 
 Schone, A., and Tol- 
 
 lens, B., 124 
 Seidel, H., 149 
 Sherman, H. C., 137 
 Simonsen, E., 146 
 Storer, F. H., 142 
 Strehlenert, R. W., 
 
 158 
 Suringar, H. , and 
 
 ToUens, B., 16, 124 
 Silvern, C, 63 
 
 TOLLENS, B., 148, 
 
 151 
 ToUens, B. , and Glau- 
 bitz, H., 122 
 
 ViGNON, L., 43, 70, 
 72. 94 
 
 Will, W., and Lenze, 
 
 P., 41 
 Winterstein, E., 109, 
 
 144. IS3 
 
INDEX OF SUBJECTS 
 
 Acetone, action on cellulose 
 
 nitrates of diluted, 46 
 Acid-cellulose, 68 
 Acids, volatile, from cellulose, 145 
 ^■Eschynomene 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 
 
 Bcuterium xylinwn^ 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 hydro- 
 gen 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, 1 37 ; of yeast, 113 
 
 ' Caro's reagent,' 118 
 
 ' Celloxin,' 71 
 
 Cellulose, alcohol from, 146 : con- 
 stitution of, 77, 92 ; fermentation 
 of, 76 ; industrial uses of, 155 ; 
 
 iodine reaction of, 21 ; methods 
 for the estimation of, 3, 4, 16, 
 I9i 97 ; nitration of, 43 ; sac- 
 charification of, 73 ; ultimate 
 hydrolysis of, II ; volatile acids 
 from, 14s 
 
 — 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, 
 1 30 ; nitration of, 38 
 
 — derivatives, commercial aspects 
 of, 171 ; saccharification of, 73 
 
 — nitrates, 44, 45, 83 ; structure- 
 less, 45, 51 ; cupric reducing 
 power of, 73 ; instability of, 50, 
 
 S3 
 
 — 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, loi, 105 
 
 Chitin, 112 
 
 Chlorination, Cross and Sevan's 
 method, 19 ; statistics of, 134 
 
 Chloro-lignone, 126 
 
 Collodion. See Silk, artificial 
 
 Cotton, lustreing effect of mercerisa- 
 tion, 23 ; mercerised, structural 
 properties of, 25 ; pentosane con- 
 tent of, 148 
 
Index 
 
 179 
 
 'Crude fibre,' 17 
 
 Cuprammonium solvent, 21, 58, 
 
 173 
 Currants, pectin of, 152 
 
 Denitration of collodion silk, 56 ; 
 of jute nitrate, 133; products of, 
 
 Dioxybutyric acid, 71 
 
 Elder pith, 137 
 Eriodendron, seed hair of, g? 
 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, oxycellu- 
 lose, and hydrocellulose, 70 ; 
 derivative from Isevulose, 8 ; esti- 
 mation as hydrazone and phloro- 
 glucide, 119, 121 ; oxidation of, 
 114^ 118 (referalso 'Pentosanes') 
 Furfuroids, 8, 10, 102, 105 ; assim- 
 ilation of, 108 
 
 Gabriel's method of cellulose esti- 
 mation, 18 
 
 Gluconic acid, action of hydrogen 
 peroxide on, 117 
 
 Glucosamine, H2 
 
 Hemicellulose, 96, 97 ; deter- 
 mination and separation of, 1 00 
 
 Honig's method of cellulose estima- 
 tion, 18 
 
 ' Hydralcellulose,' 68 
 
 Hydrocellulose, 73 ; nitration of, 
 
 '*3 
 Hydrogen peroxide, oxidations 
 
 with, 114 
 Hydroxyfiirfural in lignocellulose, 
 
 9, 116, 118 
 
 Incandescent mantles of artificial 
 » silk, 14, 15 
 Industrial appliances of cellulose, 
 
 Iodine reaction of cellulose, 21 
 Isosaccharinic acid, 7 1 
 
 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 estima- 
 tion, 18, 98 
 
 Lead compounds of nitrated carbo- 
 hydrates, 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, arti- 
 ficial 
 
 Malt, pentosanes of, 122 
 Mather system of boiling textiles, 
 
 167 
 Mercerisation, 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, 
 
 compounds of, 49 
 Nitrates of carbohydrates, 41 
 
 lead 
 
i8o 
 
 Cellulose 
 
 Nitro-cellulose {see Cellulose ni- 
 trates) ; silk, 55 
 
 ' Normal ' cellulose, definition oT, 
 27 
 
 Normal paper, 160 
 
 OxYCELLULOSE esters, 72 ; nitra- 
 tion of, 43 ; researches on, 71, 
 72, 74 ; risunii of properties, 
 94 
 
 Oxygluconic acid, 117 
 
 Paper, deterioration of, 155 ; nor- 
 mal standard, 160 ; pulp, spin- 
 ning of, 169 
 
 Peat, constituents of, 154 
 
 Pectins, 151, 152 
 
 Pentosanes, 100, 109, 144 ; con- 
 stituents of cotton, 124 ; constitu- 
 ents of fodder, 122 ; estimation 
 of, 121 ; of seeds during germina- 
 tion, 124 
 
 ' Permanent tissue,' 103 
 
 Phloroglucinol, 119, 121 
 
 Plant tissues, carbohydrates of, 96, 
 
 97. 99 
 
 Plants, source of unsaturated com- 
 pounds in, 145 
 
 Powders, manufacture of sporting, 
 52 
 
 Saccharification of cellulose 
 and derivatives, 73 
 
 Schulze method of cellulose estima- 
 tion, 18, 98 
 
 Schweizer solution, lot 
 
 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, loi, 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 esti- 
 mation (crude fibre), I7;98 
 
 Welsbach mantles, 14 ; Clamond 
 type, 15 
 
 Wheat grain, insoluble carbohy- 
 drates of, 137 
 
 Wood, alcohol from, 140, 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 
 
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