,,researches ,,on ,,cellulose #ahie-aijj ,,by ,,cross ,,bevan 7,c4 ,f4 ,,cross ,,and ,e4 ,j4 ,,bevan7 ,,second ,,edition ,,longmans1 ,,green1 ,,and ,,co4 #ci ,,paternoster ,,row1 ,,london ,,new ,,york1 ,,bombay1 ,,and ,,calcutta #aijg ,all rights reserved 99 99 99 99 99 ,transcriber's note3 ,for ,text3 ,a word surrounded by a cedilla such as this signifies that the word is bolded in the text4 ,a word surrounded by underscores like this signifies the word is italics in the text4 ,the italic and bold markup for single italized letters 7such as variables in equations7 and foreign abbreviations are deleted for easier reading4 ,for numbers and equations3 ,parentheses have been added to clarify fractions4 ,underscores before bracketed numbers in equations denote a subscript4 ,superscripts are designated with a caret and brackets1 e4g4 #aa4ac is #aa4a to the third power4 ,greek letters in equations are translated to their ,english version4 ,the sections in the ,table of ,contents are not used in the actual text4 ,they have been added for clarity4 ,minor typos have been corrected and footnotes moved to the end of the sections 99 99 99 99 99 ,,preface ,,to ,,second ,,edition ,this edition is a reprint of the first in response to a continuous demand for the book4 ,the matter1 consisting as it does largely of records1 does not call for any revision1 and1 as a contribution to the development of theory1 any particular interest which it has is associated with the date at which it was written4 ,the volume which has since appeared is the sequel1 and aims at an exposition of the subject to date4 ,,preface ,this volume1 which is intended as a supplement to the work which we published in #ahie1 gives a brief account of researches which have been subsequently published1 as well as of certain of our own investigations1 the results of which are now for the first time recorded4 ,we have not attempted to give the subject-matter the form of a connected record4 ,the contributions to the study of ',cellulose' which are noticed are spread over a large area1 are mostly 'sectional' in their aim1 and the only cohesion which we can give them is that of classifying them according to the plan of our original work4 ,their subject-matter is reproduced in the form of a precis1 as much condensed as possible2 of the more important papers the original title is given4 ,in all cases we have endeavoured to reproduce the ,author's main conclusions1 and in most cases without comment or criticism4 ,specialists will note that the basis of investigation is still in a great measure empirical2 and of this the most obvious criterion is the confusion attaching to the use of the very word ',cellulose4' ,this is due to various causes1 one of which is the curious specialisation of the term in ,germany as the equivalent of 'wood cellulose4' ,the restriction of this general or group term has had an influence even in scientific circles4 ,another influence preventing the recognition of the obvious and1 as we think1 inevitable basis of classification of the 'celluloses' is the empiricism of the methods of agricultural chemistry1 which as regards cellulose are so far chiefly concerned with its negative characteristics and the analytical determination of the indigestible residue of fodder plants4 ,physiologists1 again1 have their own views and methods in dealing with cellulose1 and have hitherto had but little regard to the work of the chemist in differentiating and classifying the celluloses on a systematic basis4 ,there are many sides to the subject1 and it is only by a sustained effort towards centralisation that the general recognition of a systematic basis can be secured4 ,we may1 we hope usefully1 direct attention to the conspicuous neglect of the subject in this country4 ,to the matter of the present volume1 excluding our own investigations1 there are but two contributions from ,english laboratories4 ,we invite the younger generation of students of chemistry to measure the probability of finding a working career in connection with the cellulose industries4 ,they will not find this invitation in the treatment accorded to the subject in text-books and lectures4 ,it is probable1 indeed1 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 basis2 whereas the former are quite insignificant by comparison4 ,a little reflection will prove that cellulose1 starch1 and sugar are of vast industrial moment in the order in which they are mentioned4 ,if it is an open question to what extent science follows industry1 or vice versa1 it is not open to doubt that scientific men1 and especially chemists1 are called in these days to lead and follow where industrial evolution is most active4 ,there is ample evidence of activity and great expansion in the cellulose industries1 especially in those which involve the chemistry of the raw material2 and the present volume should serve to show that there is rapid advance in the science of the subject4 ,hence our appeal to the workers not to neglect those opportunities which belong to the days of small beginnings4 ,we have especially to acknowledge the services of ,mr4 ,j4 ,f4 ,,briggs in investigations which are recorded on pp4 #cd-dj and pp4 #abe-acc of the text4 ,,contents ,,the ,,matter ,,of ,,this ,,volume ,,may ,,be ,,divided ,,into ,,the ,,following ,,sections ,,page ,,introduction--,,dealing ,,with ,,the ,,subject ,,in ,,general ,,outline #a ,,section ,i4 ,,general ,,chemistry ,,of ,,the ,,typical ,,cotton ,,cellulose #ac ,,ii4 ,,synthetical ,,derivatives--,,sulphocarbonates ,,and ,,esters #bg ,,iii4 ,,decompositions ,,of ,,cellulose ,,such ,,as ,,throw ,,light ,,on ,,the ,,problem ,,of ,,its ,,constitution #fg ,,iv4 ,,cellulose ,,group1 ,,including ,,hemicelluloses ,,and ,,tissue ,,constituents ,,of ,,fungi #ig ,v4 ,,furfuroids1 i4e4 ,,pentosanes ,,and ,,furfural-,,yielding ,,constituents ,,generally #aad ,,vi4 ,,the ,,lignocelluloses #abe ,,vii4 ,,pectic ,,group #aeb ,,viii4 ,,industrial ,,and ,,technical4 ,,general ,,review #aee ,,index ,,of ,,authors #agg ,,index ,,of ,,subjects #agh ,,cellulose ,,introduction ,in the period #ahie-aijj1 which has elapsed since the original publication of our work on ',cellulose1' there have appeared a large number of publications dealing with special points in the chemistry of cellulose4 ,so large has been the contribution of matter that it has been considered opportune to pass it under review2 and the present volume1 taking the form of a supplement to the original work1 is designed to incorporate this new matter and bring the subject as a whole to the level to which it is thereby to be raised4 ,some of our critics in reviewing the original work have pronounced it 'inchoate4' ,for this there are some explanations inherent in the matter itself4 ,it must be remembered that every special province of the science has its systematic beginning1 and in that stage of evolution makes a temporary 'law unto itself4' ,in the absence of a dominating theory or generalisation which1 when adopted1 gives it an organic connection with the general advance of the science1 there is no other course than to classify the subject-matter4 ,thus 'the carbohydrates' may be said to have been in the inchoate condition1 qualified by a certain classification1 prior to the pioneering investigations of ,fischer4 ,in attacking the already accumulated and so far classified material from the point of view of a dominating theory1 he found not only that the material fell into systematic order and grew rapidly under the stimulus of fruitful investigation1 but in turn contributed to the firmer establishment of the theoretical views to which the subject owed its systematic new birth4 ,on the other hand1 every chemist knows that it is only the simpler of the carbohydrates which are so individualised as to be connoted by a particular formula in the stereoisomeric system4 ,leaving the monoses1 there is even a doubt as to the constitution of cane sugar2 and the elements of uncertainty thicken as we approach the question of the chemical structure of starch4 ,this unique product of plant life has a literature of its own1 and how little of this is fully known to what we may term the 'average chemist' is seen by the methods he will employ for its quantitative estimation4 ,in one particular review of our work where we are taken to task for producing 'an aggravating book1 inchoate in the highest degree 444 disfigured by an obscurity of diction which must materially diminish its usefulness' ',nature1' #ahig1 p4 #bda1 the author1 who is a well-known and competent critic1 makes use of the short expression in regard to the more complex carbohydrates1 ',above cane sugar1 higher in the series1 all is chaos1' and in reference to starch1 'the subject is still enshrouded in mystery4' ,this 'material' complexity is at its maximum with the most complex members of the series1 which are the celluloses1 and we think accounts in part for the impatience of our critic4 ',obscurity of diction' is a personal quantity1 and we must leave that criticism to the fates4 ,we find also that many workers whose publications we notice in this present volume quite ignore the plan of the work1 though they make use of its matter4 ,we think it necessary to restate this plan1 which1 we are satisfied1 is systematic1 and1 in fact1 inevitable4 ,cellulose is in the first instance a structure1 and the anatomical relationships supply a certain basis of classification4 ,next1 it is known to us and is defined by the negative characteristics of resistance to hydrolytic actions and oxidations4 ,these are dealt with in the order of their intensity4 ,next we have the more positive definition by ultimate products of hydrolysis1 so far as they are known1 which discloses more particularly the presence of a greater or less proportion of furfural-yielding groups4 ,putting all these together as criteria of function and composition we find they supply common or general dividing lines1 within which groups of these products are contained4 ,the classification is natural1 and in that sense inevitable2 and it not only groups the physiological and chemical facts1 but the industrial also4 ,we do not propose to argue the question whether the latter adds any cogency to a scientific scheme4 ,we are satisfied that it does1 and we do not find any necessity to exclude a particular set of phenomena from consideration1 because they involve 'commercial' factors4 ,we have dealt with this classification in the original work 7p4 #gh71 and we discuss its essential basis in the present volume 7p4 #bh7 in connection with the definition of a 'normal' cellulose4 ,but the 'normal' cellulose is not the only cellulose1 any more than a primary alcohol or an aliphatic alcohol are the only alcohols4 ,this point is confused or ignored in several of the recent contributions of investigators4 ,it will suffice to cite one of these in illustration4 ,on p4 #af we give an account of an investigation of the several methods of estimating cellulose1 which is full of valuable and interesting matter4 ,the purpose of the author's elaborate comparative study is to decide which has the strongest claims to be regarded as the 'standard' method4 ,they appear to have a preference for the method of ,lange--viz4 that of heating at high temperatures 7#ahj deg47 with alkaline hydrates1 but the investigation shows that 7as we had definitely stated in our original work1 p4 #bad7 this is subject to large and variable errors4 ,the adverse judgment of the authors1 we may point out1 is entirely determined on the question of aggregate weight or yield1 and without reference to the ultimate composition or constitution of the final product4 ,none of the available criteria are applied to the product to determine whether it is a cellulose 7anhydride7 or a hydrate or a hydrolysed product4 ,after these alkali-fusion processes the method of chlorination is experimentally reviewed and dismissed for the reason that the product retains furfural-yielding groups1 which is1 from our point of view1 a particular recommendation1 i4e4 is evidence of the selective action of the chlorine and subsequent hydrolysis upon the lignone group4 ,as a matter of fact it is the only method yet available for isolating the cellulose from a lignocellulose by a treatment which is quantitatively to be accounted for in every detail of the reactions4 ,it does not yield a 'normal' cellulose1 and this is the expression which1 in our opinion1 the authors should have used4 ,it should have been pointed out1 moreover1 that1 as the cellulose is separated from actual condensed combination with the lignone groups1 it may be expected to be obtained in a hydrated form1 and also not as a homogeneous substance like the normal cotton cellulose4 ,the product is a cellulose of the second group of the classification4 ,another point in this investigation which we must criticise is the ultimate selection of the ,schulze method of prolonged maceration with nitric acid and a chlorate1 followed by suitable hydrolysis of the non-cellulose derivatives to soluble products4 ,apart from its exceptional inconvenience1 rendering it quite impracticable in laboratories which are concerned with the valuation of cellulosic raw materials for industrial purposes1 the attack of the reagent is complex and ill-defined4 ,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 celluloses4 ,the second division of the plan of our work was to define these constituents by bringing together all that had been established concerning them4 ,these groups are widely divergent in chemical character1 as are the compound celluloses in function in the plant4 ,consequently there is for each a special method of attack1 and it is a reversion to pure empiricism to expect any one treatment to act equally on the pectocelluloses1 lignocelluloses1 and cutocelluloses4 ,processes of isolating cellulose are really more strictly defined as methods of selective and regulated attack of the groups with which they occur1 combined or mixed4 ,a chemist familiar with such types as rhea or ramie 7pectocellulose71 jute 7lignocellulose71 and raffia 7cutocellulose7 knows exactly the specific treatment to apply to each for isolating the cellulose1 and must view with some surprise the appearance at this date of such 'universal prescriptions' as the process in question4 ,the third division of our plan of arrangement comprised the synthetical derivatives of the celluloses1 the sulphocarbonates first1 as peculiarly characteristic1 and then the esters1 chiefly the acetates1 benzoates1 and nitrates4 ,to these1 investigators appear to have devoted but little attention1 and the contribution of new matter in the present volume is mainly the result of our own researches4 ,it will appear from this work that an exhaustive study of the cellulose esters promises to assist very definitely in the study of constitutional problems4 ,this brings us to the fourth and1 to the theoretical chemist1 the most important aspect of the subject1 the problem of the actual molecular structure of the celluloses and compound celluloses4 ,it is herein we are of opinion that the subject makes a 'law unto itself4' ,if the constitution of starch is shrouded in mystery and can only be vaguely expressed by generalising a complex mass of statistics of its successive hydrolyses1 we can only still more vaguely guess at the distance which separates us from a mental picture of the cellulose unit4 ,we endeavour to show by our later investigations that this problem merges into that of the actual structure of cellulose in the mass4 ,it is definitely ascertained that a change in the molecule1 or reacting unit1 of a cellulose1 proportionately affects the structural properties of the derived compounds1 both sulphocarbonates and esters4 ,this is at least an indication that the properties of the visible aggregates are directly related to the actual configuration of the chemical units4 ,but it appears that we are barred from the present discussion of such a problem in absence of any theory of the solid state generally1 but more particularly of those forms of matter which are grouped together as 'colloids4' ,cellulose is distinguished by its inherent constructive functions1 and these functions take effect in the plastic or colloidal condition of the substance4 ,these properties are equally conspicuous in the synthetical derivatives of the compound4 ,without reference1 therefore1 to further speculations1 and not deterred by any apparent hopelessness of solving so large a problem1 it is clear that we have to exhaust this field by exact measurements of all the constants which can be reduced to numerical expression4 ,it is most likely that the issue may conflict with some of our current views of the molecular state which are largely drawn from a study of the relatively dissociated forms of matter4 ,but such conflicts are only those of enlargement1 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 themselves4 ,the cellulose group has been further differentiated by later investigations4 ,the fibrous celluloses of which the typical members receive important industrial applications1 graduate by insensible stages into the hemicelluloses which may be regarded as a well-established sub-group4 ,in considering their morphological and functional relationships it is evident that the graduation accords with their structure and the less permanent functions which they fulfil4 ,they are aggregates of monoses of the various types1 chiefly mannose1 galactose1 dextrose1 c41 so far as they have been investigated4 ,closely connected with this group are the constituents of the tissues of fungi4 ,the recent researches of ,winterstein and ,gilson1 which are noted in this present volume1 have established definitely that they contain a nitrogenous group in intimate combination with a carbohydrate complex4 ,this group is closely related to chitin1 yielding glucosamin and acetic acid as products of ultimate hydrolysis4 ,special interest attaches to these residues1 as they are in a sense intermediate products between the great groups of the carbohydrates and proteids 7,e4 ,fischer1 ,ber4 #ai1 #aibj71 and their further investigation by physiological methods may be expected to disclose a genetic connection4 ,the lignocelluloses have been further investigated4 ,certain new types have been added1 notably a soluble or 'pectic' form isolated from the juice of the white currant 7p4 #aeb71 and the pith-like wood of the ,a,eschynomene 7p4 #ace74 ,further researches on the typical fibrous lignocellulose have given us a basis for correcting some of the conclusions recorded in our original work1 and a study of the esters has thrown some light on the constitution of the complex 7p4 #acj74 ,of importance also is the identification of the hydroxyfurfurals as constituents of the lignocelluloses generally1 and the proof that the characteristic colour-reactions with phenols 7phloroglucinol7 may be ascribed to the presence of these compounds 7p4 #aaf74 ,the pectocelluloses have not been the subject of systematic chemical investigation1 but the researches of ,gilson 7',la ,cristallisation de la ,cellulose et la ,composition ,chimique de la ,membrane ,cellulaire ,vegetale1' ',la ,revue1' ',la ,cellule1' i4 ix47 are an important contribution to the natural history of cellulose1 especially in relation to the 'pectic' constituents of the parenchymatous celluloses4 ,indirectly also the researches of ,tollens on the 'pectins' have contributed to the subject in correcting some of the views which have had a text-book currency for a long period4 ,these are dealt with on p4 #aea4 ,the results establish that the pectins are rather the soluble hydrated form of cellulosic aggregates in which acid groups may be represented2 but such groups are not to be regarded as essentially characteristic of this class of compounds4 ,furfural-yielding ,substances 7,furfuroids74--,this group of plant products has been1 by later investigations1 more definitely and exclusively connected with the celluloses--i4e4 with the more permanent of plant tissues4 ,from the characteristic property of yielding furfural1 which they have in common with the pentoses1 they have been assumed to be the anhydrides of these ,c#e sugars or pentosanes2 but the direct evidence for this assumption has been shown to be wanting4 ,in regard to their origin the indirect evidences which have accumulated all point to their formation in the plant from hexoses4 ,of special interest1 in its bearings on this point1 is the direct transformation of levulose into furfural derivatives1 which takes place under the action of condensing agents4 ,the most characteristic is that produced by the action of anhydrous hydrobromic acid in presence of ether ,fenton1 yielding a brommethyl furfural ,c#f;,h#ab,o#f - #d;,h#b,o ,h,br ,c#e;,h#c4,o#b4;,,ch#b;,br with a ,br atom in the methyl group4 ,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 se4 ,to give them their full significance we must recall the later researches of ,brown and ,morris1 which establish that cane sugar is a primary or direct product of assimilation1 and that starch1 which had been assumed to be a species of universal matiere premiere1 is probably rather a general reserve for the elaborating work of the plant4 ,if now the aldose groups tend to pass over into the starch form1 representing a temporary overflow product of the assimilating energy1 it would appear that the ketose or levulose groups are preferentially used up in the elaboration of the permanent tissue4 ,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 hexoses1 whence we may conclude that in the plant-cell the transition from dextrose to levulose is a very simple and often occurring process4 ,we ourselves have contributed a link in this chain of evidence connecting the furfuroids of the plant with levulose or other keto-hexose4 ,we have shown that the hydroxyfurfurals are constituents of the lignocelluloses4 ,the proportion present in the free state is small1 and it is not difficult to show that they are products of breakdown of the lignone groups4 ,if we assume that such groups are derived ultimately from levulose1 we have to account for the detachment of the methyl group4 ,this1 however1 is not difficult1 and we need only call to mind that the lignocelluloses are characterised by the presence of methoxy groups and a residue which is directly and easily hydrolysed to acetic acid4 ,moreover1 the condensation need not be assumed to be a simple dehydration with attendant rearrangement2 it may very well be accompanied or preceded by fixation of oxygen4 ,leaving out the hypothetical discussion of minor variations1 there is a marked convergence of the evidence as to the main facts which establish the general relationships of the furfuroid group4 ,this group includes both saturated and unsaturated or condensed compounds4 ,the former are constituents of celluloses1 the latter of the lignone complex of the lignocelluloses4 ,the actual production of furfural by boiling with condensing acids is a quantitative measure of only a portion1 i4e4 certain members of the group4 ,the hydroxyfurfurals1 not being volatile1 are not measured in this way4 ,by secondary reactions they may yield some furfural1 but as they are highly reactive compounds1 and most readily condensed1 they are for the most part converted into complex 'tarry' products4 ,hence we have no means1 as yet1 of estimating those tissue constituents which yield hydroxyfurfurals2 also we have no measure of the furfurane-rings existing performed in such a condensed complex as lignone4 ,but1 chemists having added in the last few years a large number of facts and well-defined probabilities1 it is clear that the further investigation of the furfuroid group will take its stand upon a much more adequate basis than heretofore4 ,on the view of 'furfural-yielding' being co-extensive with 'pentose or pentosane1' not only were a number of important facts obscured or misinterpreted1 but there was a barrenness of suggestion of genetic relationships4 ,as the group has been widened very much beyond these limits1 it is clear that if any group term or designation is to be retained that of 'furfuroid' is 'neutral' in character1 and equally applicable to saturated substances of such widely divergent chemical character as pentoses1 hexosones1 glycuronic acid1 and perhaps1 most important of all1 levulose itself1 all of which are susceptible of condensation to furfural or furfurane derivatives1 as well as to those unsaturated compounds1 constituents of plant tissues which are already furfurane derivatives4 ,from the chemical point of view such terms are perhaps superfluous4 ,but physiological relationships have a significance of their own2 and there is a physiological or functional cohesion marking this group which calls for recognition1 at least for the time1 and we therefore propose to retain the term furfuroid4#a ,general ,experimental ,methods4--,in the investigation of the cellulose group it is clear that methods of ultimate hydrolysis are of first importance4 ,none are so convenient as those which are based on the action of sulphuric acid1 more or less concentrated 7,h#b,,so#d4c;,h#b,o - ,h#b,,so#d;,h#b,o74 ,such methods have been frequently employed in the investigations noted in this volume4 ,we notice a common deficiency in the interpretation of the results4 ,it appears to be sufficient to isolate and identify a crystalline monose1 without reference to the yield or proportion to the parent substance1 to establish some main point in connection with its constitution4 ,on the other hand1 it is clear that in hydrolysing a given cellulose-complex we ought to aim at complete1 i4e4 quantitative1 statistics4 ,the hydrolytic transformation of starch to dextrins and maltose has been followed in this way1 and the methods may serve as a model to which cellulose transformations should be approximated4 ,in fact1 what is very much wanted is a systematic re-examination of the typical celluloses in which all the constants of the terms between the original and the ultimate monose groups shall be determined4 ,such constants are similar to those for the starch-dextrose series1 viz4 opticity and cupric reduction4 ,various methods of fractionation are similarly available1 chiefly the precipitation of the intermediate 'dextrins' by alcohol4 ,where the original celluloses are homogeneous we should thus obtain transformation series1 similarly expressed to those of starch4 ,in the case of the celluloses which are mixtures1 or of complex constitution1 there are various methods of either fractionating the original1 or of selectively attacking particular monoses resulting from the transformation4 ,by methods which are approximately quantitative a mixture of groups1 such as we have1 for instance1 in jute cellulose1 could be followed through the several stages of their resolution into monoses4 ,to put the matter generally1 in these colloidal and complex carbohydrates the ordinary physical criteria of molecular weight are wanting4 ,therefore1 we cannot determine the relationship of a given product of decomposition to the parent molecule save by means of a quantitative mass-proportion4 ,physical criteria are only of determining value when associated with such constants as cupric reduction1 and these1 again1 must be referred to some arbitrary initial weight1 such as1 for convenience1 #ajj parts of the original4 ,instead of adopting these methods1 without which1 as a typical case1 the mechanism of starch conversions could not have been followed1 we have been content with a purely qualitative study of the analogous series obtainable from the celluloses under the action of sulphuric acid4 ,a very important field of investigation lies open1 especially to those who are generally familiar with the methods of studying starch conversions2 and we may hope in this direction for a series of valuable contributions to the problem of the actual constitution of the celluloses4 ,,footnotes3 #a ,in this we are confirmed by other writers4 ,see ,tollens1 ,j4 fuer ,landw4 #aija1 p4 #bg4 ,,section ,i4 ,,general ,,chemistry ,,of ,,the ,,typical ,,cotton ,,cellulose 7p4 #c7b ,ash ,constituents4--,it is frequently asserted that silica has a structural function sui generis in the plant skeleton1 having a relationship to the cellulosic constituents of the plant1 distinct from that of the inorganic ash components with which it is associated4 ,it should be noted that the matter has been specifically investigated in two directions4 ,in ,berl4 ,ber4 #e1 #efh 7,a4 ,ladenburg71 and again in #aa1 #hbb 7,w4 ,lange71 appear two papers ',on the ,nature of ,plant ,constituents containing ,silicon1' 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 plant1 the analogues of carbon compounds4 ,the conclusions arrived at are entirely negative4 ,in reference to the second assumption that the cuticular tissues of cereal straws1 of esparto1 of the bamboo1 owe their special properties to siliceous components1 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 medium4 ,in other words1 the structural peculiarities of the gramineae in these respects are due to the physical characteristics chiefly of the 7lignified7 cells of the hypodermal tissue1 and to the composition and arrangement of the cells of the cuticle4 ',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 ,fresenius1 ,ztschr4 ,anal ,chem4 #ahhc1 #bda4 ,it represents usually about #a_/ajjj mgr4 per #a sq4 cm4 of area of the paper4 ,the form of an 'ash' derived from a fibrous structure1 is that of the 'organic' original1 more or less1 according to its proportion and composition4 ,the proportion of 'natural ash' is seldom large enough1 nor are the components of such character as to give a coherent ash1 but if in the case of a fibrous structure it is combined or intimately mixed with inorganic compounds deposited within the fibres from solution1 the latter may be made to yield a perfect skeleton of the fibre after burning off the organic matter4 ,it is by such means that the mantles used in the ,welsbach system of incandescent lighting are prepared4 ,a purified cotton fabric--or yarn--is treated with a concentrated solution of the mixed nitrates of thorium and cerium1 and1 after drying1 the cellulose is burned away4 ,a perfect and coherent skeleton of the fabric is obtained1 composed of the mixed oxides4 ,such mantles have fulfilled the requirements of the industry up to the present time1 but later experiments forecast a notable improvement4 ,it has been found that artificial cellulose fibres can be spun with solutions containing considerable proportions of soluble compounds of these oxides4 ,such fibres1 when knitted into mantles and ignited1 yield an inorganic skeleton of the oxides of homogeneous structure and smooth contour4 ,de ,mare in #ahid1 and ,knofler in #ahie1 patented methods of preparing such cellulose threads containing the salts of thorium and cerium1 by spinning a collodion containing the latter in solution4 ,when finally ignited1 after being brought into the suitable mantle form1 there results a structure which proves vastly more durable than the original ,welsbach mantle4 ,the cause of the superiority is thus set forth by ,v4 ,h4 ,lewes in a recent publication 7,j4 ,soc4 of ,arts1 #aijj1 p4 #heh73 ',the alteration in physical structure has a most extraordinary effect upon the light-giving life of the mantle1 and also on its strength1 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 air1 and this seems to affect the ,welsbach structure far more than it does the ,clamond type1 with the result that when burned continuously the ,welsbach mantle falls to so low a pitch of light emissivity after #ejj to #fjj hours1 as to be a mere shadow of its former self1 giving not more than one-third of its original light1 whilst the ,knofler mantle keeps up its light-emitting power to a much greater extent1 and the ,lehner fabric is the most remarkable of all4 ,two ,lehner mantles which have now been burning continuously in my laboratory for over #c1jjj hours give at this moment a brighter light emissivity than most of the ,welsbachs do in their prime4' 444',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 mantles4' ,it has further been found that the oxides themselves can be dissolved in the cellulose alkaline sulphocarbonate 7viscose7 solution1 and artificial threads have been spun containing from #be to #cj p4ct4 of the oxides in homogeneous admixture with the cellulose4 ,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 production4 ,,untersuchungen ,ue,b,e,r ,,verschiedene ,,bestimmungsmethoden ,,der ,,cellulose4 ,h4 ,,suringar ,,and ,b4 ,,tollens 7,ztschr4 angew4 ,chem4 #ahif1 ,no4 #bc74 ,,investigation ,,of ,,methods ,,of ,,determining ,,cellulose4 ,introduction4--,this is an exhaustive bibliography of the subject1 describing also the various methods of cellulose estimation1 noted in historical sequence4 ,first1 the ,weende 'crude fibre' method 7,henneberg7 with modifications of ,wattenberg1 ,holdefleiss1 and others is dealt with4 ,the product of this treatment1 viz4 'crude fibre' is a mixture1 containing furfuroids and lignone compounds4 ,next follows a group of processes which aim at producing a 'pure cellulose' by eliminating lignone constituents1 for which the merely hydrolytic treatments of the ,weende method are ineffectual4 ,the method of ,f4 ,schulze--prolonged digestion with dilute nitric acid1 with addition of chlorate--has been largely employed1 though the composition of the product is more or less divergent from a 'pure cellulose4' ,dilute nitric acid at #fj-hj deg4 7,cross and ,bevan7 and a dilute mixture of nitric and sulphuric acids 7,lifschutz7 have been employed for isolating cellulose from the lignocelluloses4 ,hoffmeister modifies the method of ,schulze by substituting hydrochloric acid for the nitric acid4 ,treatment with the halogens associated with alkaline processes of hydrolysis is the basis of the methods of ,hugo ,muller 7bromine water7 and ,cross and ,bevan 7chlorine gas74 ,lastly1 the authors notice the methods based upon the action of the alkaline hydrates at high temperatures 7#ahj deg47 in presence of water 7,lange71 or of glycerin 7,gabriel74 ,the process of heating to #baj deg4 with glycerin only 7,hoenig7 yields a very impure and ill-defined product4 ,for comparative investigation of these processes certain celluloses and cellulosic materials were prepared as follows3 7a7 ',rag' cellulose4--,a chemical filter paper1 containing only cotton and linen celluloses1 was further purified by boiling with dilute acid and dilute alkali4 ,after thorough washing it was air-dried4 7b7 ,wood cellulose4--,pine wood sawdust was treated by digestion for fourteen days with dilute nitric acid with addition of chlorate 7,schulze74 ,the mass was washed and digested with alkaline lye 7#a4be p4ct4 ,,koh71 and exhaustively washed1 treated with dilute acetic acid2 again washed1 and finally air-dried4 ,this product was found to yield #b4c p4ct4 furfural on distillation with ,h,cl 7#a4jf sp4gr474 7c7 ,purified wood4--,pine wood sawdust was treated in succession with dilute alkalis and acids1 in the cold1 and with alcohol and ether until exhausted of products soluble in these liquids and reagents4 ,in addition to the above the authors have also employed jute fibre and raw cotton wool in their investigations4 ,they note that the yield of cellulose is in many cases sensibly lowered by treating the material after drying at the temperature of #ajj deg44 ,the material for treatment is therefore weighed in the air-dry condition1 and a similar sample weighed off for drying at #ajj deg4 for determination of moisture4 ,the main results of the experimental investigation are as follows3-- ,weende process further attacks the purified celluloses as follows3 ,wood cellulose losing in weight #h-i p4ct42 filter paper1 #f-g4e p4ct41 and the latter treated a second time loses a further #d-e p4ct4 ,it is clear1 therefore1 that the process is of purely empirical value4 ,schulze4--,this process gave a yield of #dg4f p4ct4 cellulose from pine wood4 ,the celluloses themselves1 treated by the process1 showed losses of #a-c p4ct4 in weight1 much less therefore than in the preceding case4 ,hoenig's method of heating with glycerin to #baj deg4 was found to yield products very far removed from 'cellulose4' ,the process may have a certain value in estimations of 'crude fibre1' but is dismissed from further consideration in relation to cellulose4 ,lange4--,the purpose of the investigation was to test the validity of the statement that the celluloses are not attacked by alkaline hydrates at #ahj deg44 ,experiments with pine wood yielded a series of percentages for cellulose varying from #cf to #da2 the 'purified wood' gave also variable numbers1 #dd to #di per cent4 ,it was found possible to limit these variations by altering the conditions in the later stages of isolating the product2 but further experiments on the celluloses themselves previously isolated by other processes showed that they were profoundly and variably attacked by the ',lange' treatment1 wood cellulose losing #ej per cent4 of its weight1 and filter paper 7cellulose7 losing #ae per cent4 ,further1 a specimen of jute yielded #eh per cent4 of cellulose by this method instead of the normal #gh per cent4 ,it was also found that the celluloses isolated by the process1 when subjected to a second treatment1 underwent a further large conversion into soluble derivatives1 and in a third treatment further losses of #e-aj per cent were obtained4 ,the authors attach value1 notwithstanding1 to the process which they state to yield an 'approximately pure cellulose1' and they describe a modified method embodying the improvements in detail resulting from their investigation4 ,gabriel's method of heating with a glycerin solution of alkaline hydrate is a combination of ',hoenig' and ',lange4' ,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 process4 ,thus1 notably in regard to furfural yielding constituents1 the latter yield #a-b p4ct4 furfural1 whereas specimens of 'jute cellulose' obtained by the ,gabriel process were found to yield #i to #ac p4ct4 furfural4 ,cross and ,bevan4--,chlorination process yielded in the hands of the authors results confirming the figures given in ',cellulose' for yield of cellulose4 ,investigation of the products for yield of furfural1 gave #i p4ct4 of this aldehyde showing the presence of celluloses1 other than the normal type4 ,conclusions4--,the subjoined table gives the mean numerical results for yield of end-product or 'cellulose' by the various methods4 ,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 process4 ,methods ,f4 ,schulze ,weende ,lange ,gabriel ,cross and ,bevan ---------------------------------------- ---------------------------------- ,wood cellulose #ih4ea #ia4eb #dh4bb #ee4ic -- ,filter paper cellulose #ii4fb #ie4fc #gh4ag #gi4gg -- ,swedish filter paper #if4eh -- #hd4gf -- -- ,ordinary filter paper #ih4ag #ic4ci #hf4eh -- -- ,cotton 7'wool'7 #ih4ch #hi4ih #fc4if #fg4hh -- ,jute -- -- #eg4ic #ga4fd #ge4bg ,purified wood -- -- #di4bg -- -- #df4ef ,raw wood #dg4fj -- #dj4hb -- -- #ch4hg ---------------------------------------- ---------------------------------- ,the final conclusion drawn from the results is that none of the processes fulfil the requirements of an ideal method4 ,those which may be carried out in a reasonably short time are deficient in two directions3 7#a7 they yield a 'cellulose' containing more or less oxycellulose2 7#b7 the celluloses themselves are attacked under the conditions of treatment1 and the end product or cellulose merely represents a particular and at the same time variable equilibrium1 as between the resistance of the cellulose and the attack of the reagents employed2 this attack being by no means confined to the non-cellulose constituents4 ,schulze's method appears to give the nearest approximation to the 'actual cellulose' of the raw material4 99 99 99 99 99 7p4 #h7 ,,solutions ,,of ,,cellulose--7#a7 ,,zinc ,,chloride4--,to prepare a homogeneous solution of cellulose by means of the neutral chloride1 a prolonged digestion at or about #ajj deg4 with the concentrated reagent is required4 ,the dissolution of the cellulose is not a simple phenomenon1 but is attended with hydrolysis and a certain degree of condensation4 ,the latter result is evidenced by the formation of furfural1 the former by the presence of soluble carbohydrates in the solution obtained by diluting the original solution and filtering from the reprecipitated cellulose4 ,the authors have observed that in carefully conducted experiments cotton cellulose may be dissolved in the reagent1 and reprecipitated with a loss of only #a p4ct4 in weight4 ,this1 however1 is a 'net' result1 and leaves undetermined the degree of hydration of the recovered cellulose as of hydrolysis of the original to groups of lower molecular weights4 ,bronnert finds that a previous hydration of the cellulose--e4g4 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 cold4 7,u4,s4 patent1 #fdf1gii_/aijj4 ,see also p4 #ei47 ,industrial applications4--7a7 ,vulcanised fibre is prepared by treating paper with four times its weight of the concentrated aqueous solution 7#fe-ge deg4 ,b471 and in the resulting gelatinised condition is worked up into masses1 blocks1 sheets1 c41 of any required thickness4 ,the washing of these masses to remove the zinc salt is a very lengthy operation4 ,to render the product waterproof the process of nitration is sometimes superadded ,d4,r4,p4 #caha_/ahgh4 ,further details of manufacture are given in ,prakt4 ,handbuch d4 ,papierfabrikation1 p4 #agjc ,c4 ,hofmann4 7b7 ,calico-printing4--,the use of the solution as a thickener or colour vehicle1 more especially as a substitute for albumen in pigment styles1 was patented by ,e4 ,b4 ,manby1 but the process has not been industrially developed ,e4,p4 #aj1dff_/ahid4 7c7 ,artificial silk4--,this is a refinement of the earlier applications of the solution in spinning cellulose threads for conversion into carbon filaments for electrical glow-lamps4 ,this section will be found dealt with on p4 #ei4 7p4 #ac7 7#b7 ,cuprammonium solution4--,the application of the solution of cellulose in cuprammonium to the production of a fine filament in continuous length1 'artificial silk1' has been very considerably studied and developed in the period #ahig-aijj1 as evidenced by the series of patents of ,fremery and ,urban1 ,pauly1 ,bronnert1 and others4 ,the subject will also be found dealt with on p4 #eh4 99 99 99 99 99 7p4 #ae7 ,reactions of cellulose with iodine4--,in a recent paper1 ,f4 ,mylius deals with the reaction of starch and cellulose with iodine1 pointing out that the blue colouration depends upon the presence of water and iodides4 ,in absence of the latter1 and therefore in presence of compounds which destroy or absorb hydriodic acid--e4g4 iodic acid--there results a brown addition product4 ,the products in question have the characteristics of solid solutions of the halogen4 7,berl4 ,ber4 #ahie1 #cij47 7#bd7 ,mercerisation--,notwithstanding the enormous recent developments in the industrial application of the mercerising reaction1 there have been no noteworthy contributions to the theoretical aspects of the subject4 ,the following abstract gives an outline of the scope of an important technical work on the subject4 ,,die ,,mercerisation ,,der ,,baumwolle4 ,,paul ,,gardner 7,berlin3 #ahih4 ,j4 ,springer74 ,,the ,,mercerisation ,,of ,,cotton4 ,this monograph of some #aej pages is chiefly devoted to the patent literature of the subject4 ,the chemical and physical modifications of the cotton substance under the action of strong alkaline lye1 were set forth by ,mercer in #ahdd-e1 and there has resulted from subsequent investigations but little increase in our knowledge of the fundamental facts4 ,the treatment was industrially developed by ,mercer in certain directions1 chiefly 7#a7 for preparing webs of cloth required to stand considerable strain1 and 7#b7 for producing crepon effects by local or topical action of the alkali4 ,but the results achieved awakened but a transitory interest1 and the matter passed into oblivion2 so much so1 indeed1 that a ,german patent ,no4 #cj1iff was granted in #ahhd to the ,messrs4 ,depouilly for crepon effects due to the differential shrinkage of fabrics under mercerisation1 by processes and treatments long previously described by ,mercer4 ,such effects have had a considerable vogue in recent years1 but it was not until the discovery of the lustreing effect resulting from the association of the mercerising actions with the condition of strain or tension of the yarn or fabric that the industry in 'mercerised' goods was started on the lines which have led to the present colossal development4 ,the merit of this discovery is now generally recognised as belonging to ,thomas and ,prevost of ,crefeld1 notwithstanding that priority of patent right belongs to the ,english technologist1 ,h4 ,a4 ,lowe4 ,the author critically discusses the grounds of the now celebrated patent controversy1 arising out of the conflict of the claims of ,german patent #he1efd_/ahie of the former1 and ,english patent #ddeb_/ahij of the latter4 ,the author concludes that ,lowe's specification undoubtedly describes the lustreing effect of mercerising in much more definite terms than that of ,thomas and ,prevost4 ,these inventors1 on the other hand1 realised the effect industrially1 which ,lowe certainly failed to do1 as evidenced by his allowing the patent to lapse4 ,as an explanation of his failure1 the author suggests that ,lowe did not sufficiently extend his observations to goods made from ,egyptian and other long-stapled cottons1 in which class only are the full effects of the added lustre obtained4 ,following these original patents are the specifications of a number of inventions which1 however1 are of insignificant moment so far as introducing any essential variation of the mercerising treatment4 ,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 cloth4 ,the fourth section deals with the fundamental facts underlying the process and effects summed up in the term 'mercerisation4' ,these are as follows3-- 7a7 ,although all forms of fibrous celluloses are similarly affected by strong alkaline solutions1 it is only the ,egyptian and other long-stapled cottons--i4e4 the goods made from them--which under the treatment acquire the special high lustre which ranks as 'silky4' ,goods made from ,american cottons acquire a certain 'finish' and lustre1 but the effects are not such as to have an industrial value--i4e4 a value proportional to the cost of treatment4 7b7 ,the lustre is determined by exposing the goods to strong tension1 either when under the action of the alkali1 or subsequently1 but only when the cellulose is in the special condition of hydration which is the main chemical effect of the mercerising treatment4 7c7 ,the degree of tension required is approximately that which opposes the shrinkage in dimensions1 otherwise determined by the action of the alkali4 ,the following table exhibits the variations of shrinkage of ,egyptian when mercerised without tension1 under varying conditions as regards the essential factors of the treatment--viz4 7#a7 concentration of the alkaline lye1 7#b7 temperature1 and 7#c7 duration of action 7the latter being of subordinate moment73-- ,concentration of lye 7,na,o,h7 #e deg4,b4 #aj deg4,b4 #ae deg4,b #be deg4,b ,duration of action in #a #aj #cj #a #aj #cj #a #aj #cj minutes ,temperatures ,percentage shrinkages 7,egyptian yarns7 as under3-- as under3-- #b deg4 #j #j #j #a #a #a #ab4b #ae4b #ae4h #ai4b #ah deg4 #j #j #j #j #j #j #h4j #h4h #aa4h #ai4h #cj deg4 #j #j #j #j #j #j #d4f #d4f #f4j #ai4j #hj deg4 #j #j #j #j #j #j #c4e #c4e #i4h #ac4d ,concentration of lye 7,na,o,h7 #be deg4,b #cj deg4,b #ce deg4,b ,duration of action in #aj #cj #a #aj #cj #a #aj #cj minutes ,temperatures ,percentage shrinkages 7,egyptian yarns7 as under3-- as under3-- #b deg4 #ai4h #ba4e #bb4g #bb4g #bb4g #bd4b #bd4e #bd4g #ah deg4 #bj4a #ba4j #ba4b #bb4j #bb4c #bc4e #bc4h #bd4g #cj deg4 #ai4e #ai4j #ah4e #ai4e #ai4h #bj4g #ba4j #ba4a #hj deg4 #ac4g #ad4b #ae4j #ae4a #ae4e #ae4j #ae4b #ae4d ,the more important general indications of the above results are--7#a7 ,the mercerisation action commences with a lye of #aj deg4,b41 and increases with increased strength of the lye up to a maximum at #ce deg4,b4 ,there is1 however1 a relatively slight increase of action with the increase of caustic soda from #cj-dj deg4,b4 7#b7 ,for optimum action the temperature should not exceed #ae-bj deg4,c4 7#c7 ,the duration of action is of proportionately less influence as the concentration of the lye increases4 ,as the maximum effect is attained the action becomes practically instantaneous1 the only condition affecting it being that of penetration--i4e4 actual contact of cellulose and alkali4 7d7 ,the question as to whether the process of 'mercerisation' involves chemical as well as physical effects is briefly discussed4 ,the author is of opinion that1 as the degree of lustre obtained varies with the different varieties of cotton1 the differentiation is occasioned by differences in chemical constitution of these various cottons4 ,the influence of the chemical factors is also emphasised by the increased dyeing capacity of the mercerised goods1 which effect1 moreover1 is independent of those conditions of strain or tension under mercerisation which determine lustre4 ,it is found in effect that with a varied range of dye stuffs a given shade is produced with from #aj to #cj p4ct4 less colouring matter than is required for the ordinary1 i4e4 unmercerised1 goods4 ,in reference to the constants of strength and elasticity1 ,buntrock gives the following results of observations upon a #dje twofold yarn1 five threads of #ej cm4 length being taken for each test7,prometheus1 #ahig1 p4 #fij73 7a7 the original yarn broke under a load of #addj grms42 7b7 after mercerisation without tension the load required was #bdbj grms42 7c7 after mercerisation under strain1 #aiej grms4 ,mercerisation1 therefore1 increases the strength of the yarn from #cj to #ff p4ct41 the increase being lessened proportionately to the strain accompanying mercerisation4 ,elasticity1 as measured by the extension under the breaking load1 remains about the same in yarns mercerised under strain1 but when allowed to shrink under mercerisation there is an increase of #cj-dj p4ct4 over the original4 ,the change of form sustained by the individual fibres has been studied by ,h4 ,lange ,farberzeitung1 #ahih1 #aig-aih1 whose microphotographs of the cotton fibres1 both in length and cross-section1 are reproduced4 ,in general terms1 the change is from the flattened riband of the original fibre to a cylindrical tube with much diminished and rounded central canal4 ,the effect of strain under mercerisation is chiefly seen in the contour of the surface1 which is smooth1 and the obliteration at intervals of the canal4 ,hence the increased transparency and more complete reflection of the light from the surface1 and the consequent approximation to the optical properties of the silk fibre4 ,the work concludes with a section devoted to a description of the various practical systems of mercerisation of yarns in general practice in ,germany1 and an account of the methods adopted in dyeing the mercerised yarns4 ,,researches ,,on ,,mercerised ,,cotton4 ,a4 ,,fraenkel and ,p4 ,,friedlaender 7,mitt4 k4-k4 ,techn4 ,gew4 ,mus41 ,wien1 #ahih1 #cbf74 ,the authors1 after investigation1 are inclined to attribute the lustre of mercerised cotton to the absence of the cuticle1 which is destroyed and removed in the process1 partly by the chemical action of the alkali1 and partly by the stretching at one or other stage of the process4 ,the authors have investigated the action of alcoholic solutions of soda also4 ,the lustre effects are not obtained unless the action of water is associated4 ,in conclusion1 the authors give the following particulars of breaking strains and elasticity3-- ---------------------------------------- ---------------------------------- ,treatment ,experiments ,breaking strain ,elasticity ---------------------------------------- ---------------------------------- ,elongation ,grammes in mm4 ,cotton unmercerised4 #a #cfj #bj #b #cef #bj #c #cfj #bb ,mercerised with ,soda #ce deg4,b4 #a #ecj #dd #b #egj #dj #c #eei #ce ,alcoholic soda #aj p4ct4 #a #fde #bd cold #b #fjj #bg #c #faj #cc ,alcoholic soda #aj p4ct4 #e #gdj #cc hot #b #gcj #ch #c #fij #cj ---------------------------------------- ---------------------------------- ,,footnotes3 #b ,this and other similar references are to the matter of the original volume 7#ahie74 ,,section ,,ii4 ,,synthetical ,,derivatives--,,sulphocarbonates ,,and ,,esters 7p4 #be7 ,cellulose sulphocarbonate4--,further investigations of the reaction of formation as well as the various reactions of decomposition of the compound1 have not contributed any essential modification or development of the subject as originally described in the author's first communications4 ,a large amount of experimental matter has been accumulated in view of the ultimate contribution of the results to the general theory of colloidal solutions4 ,but viscose is a complex product and essentially variable1 through its pronounced tendency to progressive decomposition with reversion of the cellulose to its insoluble and uncombined condition4 ,the solution for this reason does not lend itself to exact measurement of its physical constants such as might elucidate in some measure the progressive molecular aggregation of the cellulose in assuming spontaneously the solid 7hydrate7 form4 ,reserving the discussion of these points1 therefore1 we confine ourselves to recording results which further elucidate special points4 ,normal and other celluloses4--,we may certainly use the sulphocarbonate reaction as a means of defining a normal cellulose4 ,as already pointed out1 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 7hydrate74 ,analysis of this cellulose shows a fall of carbon percentage from #dd4d to #dc4c1 corresponding with a change in composition from ,c#f;,h#aj,o#e to #d;,c#f;,h#aj,o#e4;,h#b,o4 ,the partial hydrolysis affects the whole molecule1 and is limited to this effect1 whereas1 in the case of celluloses of other types1 there is a fractionation of the mass1 a portion undergoing a further hydrolysis to compounds of lower molecular weight and permanently soluble4 ,thus in the case of the wood celluloses the percentage recovered from solution as viscose is from #ic to #ie p4ct4 ,it is evident that these celluloses are not homogeneous4 ,a similar conclusion results from the presence of furfural-yielding compounds with the observation that the hydrolysis to soluble derivatives mainly affects these derivatives4 ,in the empirical characterisation of a normal cellulose1 therefore1 we may include the property of quantitative regeneration or recovery from its solution as sulphocarbonate4 ,in the use of the word 'normal' as applied to a 'bleached' cotton1 we have further to show in what respects the sulphocarbonate reaction differentiates the bleached or purified cotton cellulose from the raw product4 ,the following experiments may be cited3 ,specimens of ,american and ,egyptian cottons in the raw state1 freed from mechanical1 i4e4 non-fibrous1 impurities1 were treated with a mercerising alkali1 and the alkali-cotton subsequently exposed to carbon disulphide4 ,the product of reaction was further treated as in the preparation of the ordinary solution2 but in place of the usual solution1 structureless and homogeneous1 it was observed to retain a fibrous character1 and the fibres1 though enormously swollen1 were not broken down by continued vigorous stirring4 ,after large dilution the solutions were filtered1 and the fibres then formed a gelatinous mass on the filters4 ,after purification1 the residue was dried and weighed4 ,the ,american cotton yielded #ij4j p4ct41 and the ,egyptian #ib4j p4ct4 of its substance in the form of this peculiar modification4 ,the experiment was repeated1 allowing an interval of #bd hours to elapse between the conversion into alkali-cotton and exposure of this to the carbon disulphide4 ,the quantitative results were identical4 ,there are many observations incidental to chemical treatments of cotton fabrics which tend to show that the bleaching process produces other effects than the mere removal of mechanical impurities4 ,in the sulphocarbonate reaction the raw cotton1 in fact1 behaves exactly as a compound cellulose4 ,whether the constitutional difference between raw and bleached cotton1 thus emphasised1 is due to the group of components of the raw cotton1 which are removed in the bleaching process1 or to internal constitutional changes determined by the bleaching treatments1 is a question which future investigation must decide4 ,the normal sulphocarbonate 7viscose74--,in the industrial applications of viscose it is important to maintain a certain standard of composition as of the essential physical properties of the solution1 notably viscosity4 ,it may be noted first that1 with the above-mentioned exception1 the various fibrous celluloses show but slight differences in regard to all the essential features of the reactions involved4 ,in the mercerising reaction1 or alkali-cellulose stage1 it is true the differences are considerable4 ,with celluloses of the wood and straw classes there is a considerable conversion into soluble alkali-celluloses4 ,if treated with water these are dissolved1 and on weighing back the cellulose1 after thorough washing1 treatment with acid1 and finally washing and drying1 it will be found to have lost from #ae to #bj p4ct4 in weight4 ,the lower grade of celluloses thus dissolved are only in part precipitated in acidifying the alkaline solution4 ,on the other hand1 after conversion into viscose1 the cellulose when regenerated re-aggregates a large proportion of these lower grade celluloses1 and the final loss is as stated above1 from #e to #g p4ct4 only4 ,secondly1 it is found that all the conditions obtaining in the alkali-cellulose stage affect the subsequent viscose reaction and the properties of the final solution4 ,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 disulphide4 ,an excess of alkali beyond the 'normal' proportion--viz4 #b,na,o,h per #a mol4 ,c#f;,h#aj,o#e--;has little influence upon the viscose reaction1 but lowers the viscosity of the solution of the sulphocarbonate prepared from it4 ,but this effect equally follows from addition of alkali to the viscose itself4 ,the alkali-cellulose changes with age2 there is a gradual alteration of the molecular structure of the cellulose1 of which the properties of the viscose when prepared are the best indication4 ,there is a progressive loss of viscosity of the solution1 and a corresponding deterioration in the structural properties of the cellulose when regenerated from it--especially marked in the film form4 ,in regard to viscosity the following observations are typical3-- 7a7 ,a viscose of #a4h p4ct4 cellulose prepared from an alkali-cellulose 7cotton7 fourteen days old4 7b7 ,viscose of #a4h p4ct4 cellulose from an alkali-cellulose 7cotton7 three days old4 7c7 ,glycerin diluted with #a_/c vol4 water4 a b b c ,diluted with equal vol4 water ,times of flow of equal volumes from #aab #cba #ajc #agj narrow orifice in seconds ,similarly the cellulose in reverting to the solid form from these 'degraded' solutions presents a proportionate loss of cohesion and aggregating power expressed by the inferior strength and elasticity of the products4 ,hence1 in the practical applications of the product where the latter properties are of first importance1 it is necessary to adopt normal standards1 such as above indicated1 and to carefully regulate all the conditions of treatment in each of the two main stages of reaction1 so that a product of any desired character may be invariably obtained4 ,incidentally to these investigations a number of observations have been made on the alkali-cellulose 7cotton7 after prolonged storage in closed vessels4 ,it is well known that starch undergoes hydrolysis in contact with aqueous alkalis of a similar character to that determined by acids ,bechamp1 ,annalen1 #ajj1 #cfe4 ,the recent researches of ,lobry de ,bruyn ,rec4 ,trav4 ,chim4 #ad1 #aef upon the action of alkaline hydrates in aqueous solution on the hexoses have established the important fact of the resulting mobility of the ,,co group1 and the interchangeable relationships of typical aldoses and ketoses4 ,it was1 therefore1 not improbable that profound hydrolytic changes should occur in the cellulose molecule when kept for prolonged periods as alkali-cellulose4 ,we may cite an extreme case4 ,a series of products were examined after #ab-ah months' storage4 ,they were found to contain only #c-e p4ct4 'soluble carbohydrates'2 these were precipitated by ,fehling's solution but without reduction on boiling4 ,they were1 therefore1 of the cellulose type4 ,on acidifying with sulphuric acid and distilling1 traces only of volatile acid were produced4 ,it is clear1 therefore1 that the change of molecular weight of the cellulose1 the disaggregation of the undoubtedly large molecule of the original 'normal' cellulose--which effects are immediately recognised in the viscose reactions of such products--are of such otherwise limited character that they do not affect the constitution of the unit groups4 ,we should also conclude that the cellulose type of constitution covers a very wide range of minor variations of molecular weight or aggregation4 ,the resistance of the normal cellulose to the action of alkalis under these hydrolysing conditions should be mentioned in conjunction with the observations of ,lange1 and the results of the later investigations of ,tollens1 on its resistance to 'fusion' with alkaline hydrates at high temperatures 7#ahj deg474 ,the degree of resistance has been established only on the empirical basis of weighing the product recovered from such treatment4 ,the product must be investigated by conversion into typical cellulose derivatives before we can pronounce upon the constitutional changes which certainly occur in the process4 ,but for the purpose of this discussion it is sufficient to emphasise the extraordinary resistance of the normal cellulose to the action of alkalis1 and to another of the more significant points of differentiation from starch4 ,chemical constants of cellulose sulphocarbonate 7solution74--,in investigations of the solutions we make use of various analytical methods1 which may be briefly described1 noting any results bearing upon special points4 ,total alkali4--,this constant is determined by titration in the usual way4 ,the cellulose ratio1 ,c#f;,h#aj,o#e 3 #b,na,o,h1 is within the ordinary error of observation1 #b 3 #a by weight4 ,a determination of alkali therefore determines the percentage of cellulose4 ,cellulose may be regenerated in various ways--viz4 by the action of heat1 of acids1 of various oxidising compounds4 ,it is purified for weighing by boiling in neutral sulphite of soda 7#b p4ct4 solution7 to remove sulphur1 and in very dilute acids 7#j4cc p4ct4 ,h,cl7 to decompose residues of 'organic' sulphur compounds4 ,it may also be treated with dilute oxidants4 ,after weighing it may be ignited to determine residual inorganic compounds4 ,sulphur4--,it has been proved by ,lindemann and ,motten ,bull4 ,acad4 ,r4 ,belg4 7#c71 #bc1 #hbg that the sulphur of sulphocarbonates 7as well as of sulphocyanides7 is fully oxidised 7to ,,so#c7 by the hypochlorites 7solutions at ordinary temperatures74 ,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 sulphur4 ,the sulphur present in the form of dithiocarbonates1 including the typical cellulose xanthogenic acid1 is approximately isolated and determined as ,,cs#b by adding a zinc salt in excess1 and distilling off the carbon disulphide from a water bath4 ,from freshly prepared solutions a large proportion of the disulphide originally interacting with the alkali and cellulose is recovered1 the result establishing the general conformity of the reaction to that typical of the alcohols4 ,on keeping the solutions there is a progressive interaction of the bisulphide and alkali1 with formation of trithiocarbonates and various sulphides4 ,in decomposing these products by acid reagents hydrogen sulphide and free sulphur are formed1 the estimation of which presents no special difficulties4 ,in the spontaneous decomposition of the solution a large proportion of the sulphur resumes the form of the volatile disulphide4 ,this is approximately measured by the loss in total sulphur in the following series of determinations1 in which a viscose of #h4e p4ct4 strength 7cellulose7 was dried down as a thin film upon glass plates1 and afterwards analysed3 7a7 ,proportion of sulphur to cellulose 7#ajj pts47 in original4 7b7 ,after spontaneous drying at ordinary temperature4 7c7 ,after drying at #dj deg4,c4 7d7 ,as in 7c71 followed1 by #b hours' heating at #ih deg44 7e7 ,as in 7c71 followed by #e hours' heating at #ih deg44 a b c d e ,total sulphur #dj4j #be4j #ca4j #bc4g #aj4d ,the dried product in 7b7 and 7c7 was entirely resoluble in water2 in 7d7 and 7e71 on the other hand1 the cellulose was fully regenerated1 and obtained as a transparent film4 ,iodine reaction4--,fresh solutions of the sulphocarbonate show a fairly constant reaction with normal iodine solution4 ,at the first point1 where the excess of iodine visibly persists1 there is complete precipitation of the cellulose as the bixanthic sulphide2 and this occurs when the proportion of iodine added reaches #c;,i#b 3 #d,na#b,o1 calculated to the total alkali4 ,other decompositions4--,the most interesting is the interaction which occurs between the cellulose xanthogenate and salts of ammonia1 which is taken advantage of by ,c4 ,h4 ,stearn in his patent process of spinning artificial threads from viscose4 ,the insoluble product which is formed in excess of the solution of ammonia salt is free from soda1 and contains #i-aj p4ct4 total sulphur4 ,the product retains its solubility in water for a short period4 ,the solution may be regarded as containing the ammonium cellulose xanthate4 ,this rapidly decomposes with liberation of ammonia and carbon disulphide1 and separation of cellulose 7hydrate74 ,as precipitated by ammonium-chloride solution the gelatinous thread contains #ae p4ct4 of cellulose1 with a sp4gr4 #a4a4 ,the process of 'fixing'--i4e4 decomposing the xanthic residue--consists in a short exposure to the boiling saline solution4 ,the further dehydration1 with increase of gravity and cellulose content1 is not considerable4 ,the thread in its final air-dry state has a sp4gr4 #a4dh4 99 99 99 99 99 ,cellulose ,benzoates4--,these derivatives have been further studied by the authors4 ,the conditions for the formation of the monobenzoate ,c#f;,h#i,o#d4,o4,,co4,ph are very similar to those required for the sulphocarbonate reaction4 ,the fibrous cellulose 7cotton71 treated with a #aj p4ct4 solution ,na,o,h1 and subsequently with benzoyl chloride1 gives about #ej p4ct4 of the theoretical yield of monobenzoate4 ,converted by #bj p4ct4 solution ,na,o,h into alkali-cellulose1 and with molecular proportions as below1 the following yields were obtained3-- ,calc4 for ,monobenzoate 7a7 ,c#f;,h#aj,o#e 3 #b4j-b4e ,na,o,h 3 ,c#f;,h#e4;,c,o,cl-- #aej4h #afd4j 7b7 ,c#f;,h#aj,o#e 3 #b4j-b4e ,na,o,h 3 #a4e mol4 ,c#f;,h#e;,c,o,cl #aei4j ,an examination of 7a7 showed that some dibenzoate 7about #g p4ct47 had been formed4 ,the product 77 was exhaustively treated with cuprammonium solution1 to which it yielded about #bj p4ct4 of its weight1 which was therefore unattacked cellulose4 ,under conditions as above1 but with #b4e mol4 ,c#f;,h#e;,c,o,cl1 a careful comparison was made of the behaviour of the three varieties of cotton1 which were taken in the unspun condition and previously fully bleached and purified4 ,sea ,island ,egyptian ,american ,aggregate yield of benzoate #aec #adh #aeb ,moisture in air dry state #e4bh #e4ce #e4ae ,proportion of dibenzoate p4ct4 #h4cj #ac4gj #i4d ,yield of cellulose by #eh4j #ed4j #eh4c saponification ,it appears from these results that the benzoate reaction may proceed to a higher limit 7dibenzoate7 in the case of ,egyptian cotton4 ,this would necessarily imply a higher limit of 'mercerisation1' under equal conditions of treatment with the alkaline hydrate4 ,it must be noted that in the conversion of the fibrous cellulose into these 7still7 fibrous monobenzoates1 there are certain mechanical conditions imported by the structural features of the ultimate fibres4 ,for the elimination of the influence of this factor a large number of quantitative comparisons will be necessary4 ,the above results are therefore only cited as typical of a method of comparative investigation1 more especially of the still open questions of the cause of the superior effects in mercerisation of certain cottons 7see p4 #bc74 ,it is quite probable that chemical as well as structural factors co-operate in further differentiating the cottons4 ,further investigation of the influence upon the benzoate reaction1 of increase of concentration of the soda lye1 used in the preliminary alkali cellulose reaction1 from #bj to #cc p4ct4 ,na,o,h1 established 7#a7 that there is no corresponding increase in the benzoylation1 and 7#b7 that this ester reaction and the sulphocarbonate reaction are closely parallel1 in that the degree and limit of reaction are predetermined by the conditions of formation of the alkali cellulose4 ,monobenzoate prepared as above described is resistant to all solvents of cellulose and of the cellulose esters1 and is therefore freed from cellulose by treatment with the former1 and from the higher benzoate by treatment with the latter4 ,several of these1 notably pyridine1 phenol and nitrobenzene1 cause considerable swelling and gelatinisation of the fibres1 but without solution4 ,structureless celluloses of the 'normal' type1 and insoluble therefore in alkaline lye1 treated under similar conditions to those described above for the fibrous celluloses1 yield a higher proportion of dibenzoate4 ,the following determinations were made with the cellulose 7hydrate7 regenerated from the sulphocarbonate3-- ,mol4 proportions of reagents ,yield ,dibenzoate p4ct4 ,c#f;,h#aj,o#e 3 #b,na,o,h 3 #b;,bz,cl #ade #cd4g ,caustic soda at #aj per cent4 ,na,o,h ,c#f;,h#aj,o#e 3 #d,na,o,h 3 #b;,bz,cl #afb #fb4g ,caustic soda at #bj per cent4 ,na,o,h ,limit of reaction4--,the cellulose in this form having shown itself more reactive1 it was taken as the basis for determining the maximum proportion of ,,oh groups yielding to this later reaction4 ,the systematic investigations of ,skraup ,monatsh4 #aj1 #chi have determined that as regards the interacting groups the molecular proportions #a ,,oh 3 #g ,na,o,h 3 #e ,bz,cl1 ensure complete or maximum esterification4 ,the maximum of ,,oh groups in cellulose being #d1 the reagents were taken in the proportion ,c#f;,h#aj,o#e 3 #d #g ,na,o,h 3 #e ,bz,cl4 ,the yield of crude product1 after purifying as far as possible from the excess of benzoic acid1 was #bdj p4ct4 calculated for dibenzoate #bbg p4ct44 ,on further investigating the crude product by treatment with solvents1 it was found to have still retained benzoic acid4 ,there was also present a proportion of only partially attacked cellulose 7monobenzoate74 ,the soluble benzoate amounted to #ij p4ct4 of the product4 ,it may be generally concluded that the dibenzoate represents the normal maximum but that with the hydrated and partly hydrolysed cellulose molecule1 as obtained by regeneration from the sulphocarbonate1 other ,,oh groups may react1 but they are only a fractional proportion in relation to the unit group ,c#f;,h#aj,o#e4 ,in this respect again there is a close parallelism between the sulphocarbonate and benzoyl-ester reactions4 ,the dibenzoate1 even when prepared from the fibrous celluloses1 is devoid of structure1 and its presence in admixture with the fibrous monobenzoate is at once recognised as it constitutes a structureless incrustation4 ,under the microscope its presence in however minute proportion is readily observed4 ,as stated it is soluble in certain of the ordinary solvents of the cellulose esters1 e4g4 chloroform1 acetic acid1 nitrobenzene1 pyridine1 and phenol4 ,it is not soluble in ether or alcohol4 ,hygroscopic moisture of benzoates4--,the crude monobenzoate retains #e4j-e4e p4ct4 moisture in the air-dry condition4 ,after removal of the residual cellulose this is reduced to #c4c p4ct4 under ordinary atmospheric conditions4 ,the purified dibenzoates retain #a4f p4ct4 under similar conditions4 ,analysis of benzoates4--,on saponification of these esters with alcoholic sodium hydrate1 anomalous results are obtained4 ,the acid numbers1 determined by titration in the usual way1 are #aj-bj p4ct4 in excess of the theoretical1 the difference increasing with the time of boiling4 ,similarly the residual cellulose shows a deficiency of #e-i p4ct4 ,it is by no means improbable that in the original ester reaction there is a constitutional change in the cellulose molecule causing it to break down in part under the hydrolysing treatment with formation of acid products4 ,this point is under investigation4 ,normal results as regards acid numbers1 on the other hand1 are obtained by saponification with sodium ethylate in the cold1 the product being digested with the half-saturated solution for #ab hours in a closed flask4 ,the following results with specimens of mono- and dibenzoate1 purified1 as far as possible1 may be cited3 ,combustion results ,saponification results ,calc4 ,c#f;,h#e4;,,cooh ,calc4 ,cellulose ,calc4 ,monobenzoate ,c #ef4fj #eh4fe ,h #e4jf #e4bf #df4j #de4i #eh4j #fj4h ,dibenzoate ,c #fc4aj #fd4hf ,h #c4dj #d4hf #fe4e #ff4f #cd4c #dj4c ,the divergence of the numbers1 especially for the dibenzoate1 in the case of the hydrogen1 and yield of cellulose on hydrolysis are noteworthy4 ,they confirm the probability of the occurrence of secondary changes in the ester reactions4 ,action of nitrating acid upon the benzoates4--,from the benzoates above described1 mixed nitro-nitric esters are obtained by the action of the mixture of nitric and sulphuric acids4 ,the residual ,,oh groups of the cellulose are esterified and substitution by an ,,no#b group takes place in the aromatic residue1 giving a mixed nitric nitrobenzoic ester4 ,the analysis of the products points to the entrance of #a ,,no#b group in the benzoyl residue in either case2 in the cellulose residue #a ,,oh readily reacts4 ,higher degrees of nitration are attained by the process of solution in concentrated nitric acid and precipitation by pouring into sulphuric acid4 ,in describing these mixed esters we shall find it necessary to adopt the ,c#ab unit formula4 ,in analysing these products we have employed the ,dumas method for total nitrogen4 ,for the ,o4,,no#b groups we have found the nitrometer and the ,schloesing methods to give concordant results4 ,for the ,,no#b groups it was thought that ,limpricht's method1 based upon reduction with stannous chloride in acid solution 7,h,cl71 would be available4 ,the quantitative results1 however1 were only approximate1 owing to the difficulty of confining the reduction to the ,,no#b groups of the nitrobenzoyl residue4 ,by reduction with ammonium sulphide the ,o4,,no#b groups were entirely removed as in the case of the cellulose nitrates2 the ,,no#b was reduced to ,,nh#b and there resulted a cellulose amidobenzoate1 which was diazotised and combined with amines and phenols to form yellow and red colouring matters1 the reacting residue remaining more or less firmly combined with the cellulose4 ,cellulose dinitrate-dinitrobenzoate1 and cellulose trinitrate-dinitrobenzoate4--,on treating the fibrous benzoate--which is a dibenzoate on the ,c#ab basis--with the acid mixture under the usual conditions1 a yellowish product is obtained1 with a yield of #adj-adb p4ct4 ,the nitrobenzoate is insoluble in ether alcohol1 but is soluble in acetone1 acetic acid1 and nitrobenzene4 ,in purifying the product the former solvent is used to remove any cellulose nitrates4 ,to obtain the maximum combination with nitroxy-groups1 the product was dissolved in concentrated nitric acid1 and the solution poured into sulphuric acid4 ,the following analytical results were obtained 7a7 for the product obtained directly from the fibrous benzoate and purified as indicated1 7b7 for the product from the further treatment of 7a7 as described3 ,found ,calc4 for 7a7 7b7 ,dinitrate ,trinitrate dinitrobenzoate dinitrobenzoate ,total ,nitrogen #g4hd #h4ig #g4ii #i4bd ,o4,,no#b #e4jj #e4de #d4jj #e4ed ,,no#b 7,aromatic7 #b4hd #c4eb #c4ii #c4gj ,with the two benzoyl groups converted into nitro-benzoyl in each product1 the limit of the ester reaction with the cellulose residue is reached at the third ,,oh group4 ,the nitrogen in the amidobenzoate resulting from the reduction with ammonium sulphide was #d4e p4ct4--as against #e4j p4ct4 calculated4 ,the moisture retained by the fibrous nitrate--nitrobenzoate--in the air-dry state was found to be #a4ig p4ct4 ,the product from the structureless dibenzoate or tetrabenzoate on the ,c#ab formula1 was prepared and analysed with the following results3 ,calc4 for ,mononitrate tetranitrobenzoate ,total ,nitrogen #f4gf #g4be ,o4,,no#b #a4cj #a4de ,,no#b 7,aromatic7 #e4df #e4hj ,the results were confirmed by the yield of product1 viz4 #aca p4ct4 as against the calculated #acf p4ct4 ,they afford further evidence of the generally low limit of esterification of the cellulose molecule4 ,from the formation of a 'normal' tetracetate--i4e4 octacetate of the ,c#ab unit--we conclude that #d_/e of the oxygen atoms are hydroxyl oxygen4 ,of the #h ,,oh groups five only react in the mixed esters described above1 and six only in the case of the simple nitric esters4 ,the ester reactions are probably not simple1 but accompanied by secondary reactions within the cellulose molecule4 99 99 99 99 99 7p4 #cd7 ,cellulose ,acetates4--,in the first edition 7p4 #ce7 we have committed ourselves to the statement that 'on boiling cotton with acetic anhydride and sodium acetate no reaction occurs4' ,this is erroneous4 ,the error arises1 however1 from the somewhat vague statements of ,schutzenberger's researches which are current in the text-books e4g4 ,beilstein1 #a ed4 p4 #ehf together with the statement that reaction only occurs at elevated temperatures 7#ahj deg474 ,as a matter of fact1 reaction takes place at the boiling temperature of the anhydride4 ,we have obtained the following results with bleached cotton3 ,yield ,calc4 for ,monoacetate ,c#f;,h#g,o#d,o4,c#b;,h#c,o ,ester reaction #aba p4ct4 #abe p4ct4 ,cellulose #gi4i #gi4i ,saponification ,acetic acid #bi4i #bi4d ,this product is formed without apparent structural alteration of the fibre4 ,it is entirely insoluble in all the ordinary solvents of the higher acetates4 ,moreover1 it entirely resists the actions of the special solvents of cellulose--e4g4 zinc chloride and cuprammonium4 ,the compound is in other respects equally stable and inert4 ,the hygroscopic moisture under ordinary atmospheric conditions is #c4b p4ct4 ,tetracetate4--,this product is now made on the manufacturing scale3 it has yet to establish its industrial value4 ,,nitrirung ,,von ,,kohlenhydraten4 ,w4 ,,will und ,p4 ,,lenze 7,berl4 ,ber41 #ahih1 #fh74 ,,nitrates ,,of ,,carbohydrates4 7p4 #ch7 ,the authors have studied the nitric esters of a typical series of the now well-defined carbohydrates--pentoses1 hexoses1 both aldoses and ketoses--bioses and trioses1 the nitrates being prepared under conditions designed to produce the highest degree of esterification4 ,starch1 wood1 gum1 and cellulose were also included in the investigations4 ,the products were analysed and their physical properties determined4 ,they were more especially investigated in regard to temperatures of decomposition1 which were found to lie considerably lower than that of the cellulose nitrates4 ,they also show marked and variable instability at #ej deg4 ,c4 ,a main purpose of the inquiry was to throw light upon a probable cause of the instability of the cellulose nitrates1 viz4 the presence of nitrates of hydrolysed products or carbohydrates of lower molecular weight4 ,the most important results are these3 ,monoses4--,the aldoses are fully esterified1 in the pentoses #d ,,oh1 in the hexoses #e ,,oh groups reacting4 ,the pentose nitrates are comparatively stable at #ej deg42 the hexose nitrates on the other hand are extremely unstable1 showing a loss of weight of #cj-dj p4ct4 when kept #bd hours at this temperature4 ,xylose is differentiated by tending to pass into an anhydride form 7,c#e;,h#aj,o#e-;,h#b,o7 under this esterification4 ,when treated in fact with the mixed acids1 instead of by the process usually adopted by the authors of solution in nitric acid and subsequent addition of the sulphuric acid1 it is converted into the dinitrate ,c#e;,h#f,o#b47,,no#c7b4 ,ketoses 7,c#f74--,these are sharply differentiated from the corresponding aldoses by giving trinitrates ,c#f;,h#g,o#b7,,no#c7c instead of pentanitrates1 the remaining ,,oh groups probably undergoing internal condensation4 ,the products are1 moreover1 extremely stable4 ,it is also noteworthy that levulose gave this same product1 the trinitrate of the anhydride 7levulosan7 by both methods of nitration 7supra74 ,the bisaccharides or bioses all give the octonitrates4 ,the degree of instability is variable4 ,cane-sugar gives a very unstable nitrate4 ,the lactose nitrate is more stable4 ,thus at #ej deg4 it loses only #j4g p4ct4 in weight in eight days2 at #ge deg4 it loses #a p4ct4 in twenty-four hours1 but with a rapid increase to #bc p4ct4 in fifty-four hours4 ,the maltose octonitrate melts 7with decomposition7 at a relatively high temperature1 #afc deg4-#afd deg44 ,at #ej deg4-#ge deg4 it behaves much like the lactose nitrate4 ,trisaccharide4--,raffinose yielded the product ,c#ah;,h#ba,o#e47,,no#c7aa4 ,starch yields the hexanitrate 7,c#ab7 by both methods of nitration4 ,the product has a high melting and decomposing point1 viz4 #ahd deg41 and when thoroughly purified is quite stable4 ,it is noted that a yield of #aeg p4ct4 of this nitrate was obtained1 and under identical conditions cellulose yielded #agj p4ct4 ,wood gum1 from beech wood1 gave a tetranitrate 7,c#aj formula7 insoluble in all the usual solvents for this group of esters4 ,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 acids4 ,they also lay stress upon the superior stability of the nitrates of the anhydrides1 especially of the ketoses4 ,,nitrated ,,carbohydrates ,,as ,,food ,,material ,,for ,,moulds4 ,,thomas ,,bokorny 7,chem4 ,zeit41 #ahif1 #bj1 #ihe-ihf74 7p4 #ch7 ,cellulose trinitrate 7nitrocellulose7 will serve as a food supply for moulds when suspended in distilled water containing the requisite mineral matter and placed in the dark4 ,the growth is rapid1 and a considerable quantity of the vegetable growth accumulates round the masses of cellulose nitrate1 but no growth is observed if mineral matter is absent4 ,cellulose itself cannot act as a food supply1 and it seems probable that if glycerol is present cellulose nitrate is no longer made use of4 ,,nitration ,,of ,,cellulose1 ,,hydrocellulose1 ,,and ,,oxycellulose4 ,,leo ,,vignon 7,compt4 rend41 #ahih1 #abf1 #afeh-affa74 7p4 #ch7 ,repeated treatment of cellulose1 hydrocellulose1 and oxycellulose with a mixture of sulphuric and nitric acids in large excess1 together with successive analyses of the compounds produced1 showed that the final product of the reaction corresponded1 in each case1 with the fixation of #aa ,,no groups by a molecule containing #bd atoms of carbon4 ,on exposure to air1 nitrohydrocellulose becomes yellow and decomposes2 nitro-oxycellulose is rather more stable1 whilst nitrocellulose is unaffected4 ,the behaviour of these nitro-derivatives with ,schiff's reagent1 ,fehling's solution1 and potash show that all three possess aldehydic characters1 which are most marked in the case of nitro-oxycellulose4 ,the latter also1 when distilled with hydrochloric acid1 yields a larger proportion of furfuraldehyde than is obtained from nitrocellulose and nitrohydrocellulose4 99 99 99 99 99 ,,cellulose ,,nitrates-,,explosives4 7p4 #ch7 ,the uses of the cellulose nitrates as a basis for explosives are limited by their fibrous character4 ,the conversion of these products into the structureless homogeneous solid or semi-solid form has the effect of controlling their combustion4 ,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 purposes4 ,the leading representatives of this class of propulsive explosives1 or 'smokeless powders' are ballistite and cordite1 the technology of which will be found fully discussed in special manuals of the subject4 ,since the contribution of these inventions to the development of cellulose chemistry does not go beyond the broad1 general facts above mentioned1 we must refer the reader for technical details to the manuals in question4 ,there are1 however1 other means of arriving at structureless cellulose nitrates4 ,one of these has been recently disclosed1 and as the results involve chemical and technical points of novelty1 which are dealt with in a scientific communication1 we reproduce the paper in question1 viz43-- ,a ,,re-,,investigation ,,of ,,the ,,cellulose ,,nitrates4 ,a4 ,,luck and ,c4 ,f4 ,,cross 7,j4 ,soc4 ,chem4 ,ind41 #aijj74 ,the starting-point of these investigations was a study of the nitrates obtained from the structureless cellulose obtained from the sulphocarbonate 7viscose74 ,this cellulose in the form of a fine meal was treated under identical conditions with a sample of pure cotton cellulose1 viz4 digested for #bd hours in an acid mixture containing in #ajj parts ,,hno#c--bd 3 ,h#b,,so#d--gj 3 ,h#b,o--#f3 the proportion of acid to cellulose being #fj 3 #a--4 ,after careful purification the products were analysed with the following results3 ,soluble in ,nitrogen ,ether alcohol ,fibrous nitrate #ac4ca #d4c p4ct4 ,structureless nitrate #ac4ce #e4f ,examined by the 'heat test' 7at #hj deg47 and the 'stability test' 7at #ace deg47 they exhibited the usual instability1 and in equal degrees4 ,nor were the tests affected by exhaustive treatment with ether1 benzene1 and alcohol4 ,from this it appears that the process of solution as sulphocarbonate and regeneration of the cellulose1 though it eliminates certain constituents of an ordinary bleached cellulose1 which might be expected to cause instability1 has really no effect in this direction4 ,it also appears that instability may be due to by-products of the esterification process derived from the cellulose itself4 ,the investigation was then extended to liquids having a direct solvent action on these higher nitrates1 more especially acetone4 ,it was necessary1 however1 to avoid this solvent action proper1 and having observed that dilution with water in increasing proportions produced a graduated succession of physical changes in the fibrous ester1 we carried out a series of treatments with such diluted acetones4 ,quantities of the sample 7,a71 purified as described1 but still unstable1 were treated each with five successive changes of the particular liquid1 afterwards carefully freed from the acetone and dried at #dj deg4,c4 ,the products1 which were found to be more or less disintegrated1 were then tested by the ordinary heat test1 stability test1 and explosion test1 with the results shown in the table on next page4 ,in this series of trials the sample ',a' was used in the condition of pulp1 viz4 as reduced by the process of wet-beating in a ,hollander4 ,a similar series was carried out with the guncotton in the condition in which it was directly obtained from the ester reaction4 ,the results were similar to above1 fully confirming the progressive character of the stabilisation with increasing proportions of acetone4 ,these results prove that washing with the diluted acetone not only rendered the nitrate perfectly stable1 but that the product was more stable than that obtained by the ordinary process of purification1 viz4 long-continued boiling and washing in water4 ,we shall revert to this point after briefly dealing with the associated phenomenon of structural disintegration4 ,this begins to be well marked when the proportion of acetone exceeds #hj p4ct4 ,the optimum effect is obtained with mixtures of #ij to #ic acetone and #aj to #g water 7by volume74 ,in a slightly diluted acetone of such composition1 the guncotton is instantly attacked1 the action being quite different from the gelatinisation which precedes solution in the undiluted solvent4 ,the fibrous character disappears1 and the product assumes the form of a free1 bulky1 still opaque mass1 which rapidly sinks to the bottom of the containing vessel4 ,the disintegration of the bulk of the nitrate is associated with ,proportions by volume ,temperature ,heat ,heat of ,test ,test ,acetone ,water ,explosion #hj deg4 #acd deg4 ,deg4 ,mins4 ,mins4 #bj #hj #acg #c #d #cj #gj #afj #c #d #dj #fj #ahj #g #ah ,no fumes after ,from ',a' sample4 #ej #ej #ahg4e #ee #ajj #fj #dj #ahg #de #ajj #gj #cj #ahe #de #ajj #hj #bj #ej #ajj #ib #h #ahe #ej #ajj ,structure- less powder4 ',b' sample #ej #ej #ahc #ce #ajj ',c' sample ,ordinary service #ahe #aj #da guncotton a certain solvent action1 and on adding an equal bulk of water1 the dissolved nitrate for the most part is precipitated1 at the same time that the undissolved but disintegrated and swollen product undergoes further changes in the direction of increase of hardness and density4 ,the product being now collected on a filter1 freed from acetone by washing with water and dried1 is a hard and dense powder the fineness of which varies according to the attendant conditions of treatment4 ,with the main product in certain cases there is found associated a small proportion of nitrate retaining a fibrous character1 which may be separated by means of a fine sieve4 ,on examining such a residue1 we found it to contain only #e4f p4ct4 ,n1 and as it was insoluble in strong acetone1 it may be regarded as a low nitrate or a mixture of such with unaltered cellulose4 ,confirming this we found that the product passing through the sieve showed an increase of nitrogen to #ac4dc p4ct4 from the #ac4ca p4ct4 in the original4 ,tested by the heat test 7#ej minutes7 and stability test 7no fumes after #ajj minutes71 we found the products to have the characteristics previously noticed4 ,it is clear1 therefore1 that this specifically regulated action of acetone produces the effects 7a7 of disintegration1 and 7b7 stabilisation4 ,it remains to determine whether the latter effect was due1 as might be supposed1 to the actual elimination of a compound or group of compounds present in the original nitrate1 and to be regarded as the effective cause of instability4 ,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 completed1 collecting the disintegrated product on a filter and washing with water1 the loss of weight sustained amounts to #c to #d p4ct4 ,this loss is due1 therefore1 to products remaining dissolved in the filtrate--that is to say1 in the much diluted acetone4 ,these filtrates are in fact opalescent from the presence of a portion of nitrate in a colloidal 7hydrated7 form4 ,on distilling off the acetone1 a precipitation is determined4 ,the precipitates are nitrates of variable composition1 analysis showing from #i to #ab p4ct4 of nitric nitrogen4 ,the filtrate from these precipitates containing only fractional residues of acetone still shows opalescence4 ,on long-continued boiling a further precipitation is determined1 the filtrates from which are clear4 ,it was in this final clear filtrate that the product assumed to cause the instability of the original nitrate would be present4 ,the quantity1 however1 is relatively so small that we have only been able to obtain and examine it as residue from evaporation to dryness4 ,an exhaustive qualitative examination established a number of negative characteristics1 with the conclusion that the products were not direct derivatives of carbohydrates nor aromatic compounds4 ,on the other hand the following positive points resulted4 ,although the original diluted acetone extract was neutral to test papers1 yet the residue was acid in character4 ,it contained combined nitric groups1 fused below #bjj deg4 giving off acid vapours1 and afterwards burning with a smoky flame4 ,on adding lead acetate to the original clear solution1 a well-marked precipitation was determined4 ,the lead compounds thus isolated are characteristic4 ,they have been obtained in various ways and analysed4 ,the composition varies with the character of the solution in which the lead compound is formed4 ,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 present1 the lead acetate causes a dense coagulation4 ,the precipitates dried and analysed showed #af-bj p4ct4 ,pb,o and #aa-i p4ct4 ,n4 ,it is clear that the cellulose nitrates are associated in these precipitates with the lead salts of the acid compounds in question4 ,when the latter are obtained from clear solutions1 i4e4 in absence of cellulose nitrates1 they contain #fj-fc p4ct4 ,pb,o and #c4e p4ct4 ,n 7obtained as ,,no74 ,in further confirmation of the conclusion from these results1 viz4 that the nitrocelluloses with no tendency to combine with ,pb,o are associated with acid products or by-products of the ester reaction combining with the oxide1 the lead reagent was allowed to react in the presence of #ij p4ct4 acetone4 ,water was added1 the disintegrated mass collected1 washed with dilute acetic acid1 and finally with water4 ,various estimations of the ,pb,o fixed in this way have given numbers varying from #b to #b4e p4ct4 ,such products are perfectly stable4 ,this particular effect of stabilisation appears1 therefore1 to depend upon the combination of certain acid products present in ordinary nitrocelluloses with metallic oxides4 ,in order to further verify this conclusion1 standard specimens of cellulose nitrates have been treated with a large number of metallic salts under varying conditions of action4 ,it has been finally established 7#a7 that the effects in question are more particularly determined by treatment with salts of lead and zinc1 and 7#b7 that the simplest method of treatment is that of boiling the cellulose nitrates with dilute aqueous solutions of salts of these metals1 preferably the acetates4 ,the following results may be cited1 obtained by boiling a purified 'service' guncotton 7sample ,c7 with a #a p4ct4 solution of lead acetate and of zinc acetate respectively4 ,after boiling #fj minutes the nitrates were washed free from the soluble metallic salts1 dried and tested4 ,heat ,test ,heat ,test at #hj deg4 at #acd deg4 ,original sample ,c #aj #da ,treated with lead acetate #fg #de zinc #ia #de ,in conclusion we may briefly resume the main points arrived at in these investigations4 ,causes of instability of cellulose nitrates4--,the results of our experiments so far as to the causes of instability in cellulose nitrates may be summed up as follows3-- 7#a7 ,traces of free nitrating acids1 which can only occur in the finished products through careless manufacture1 will undoubtedly cause instability1 indicated strongly by the ordinary heat test at #hj deg41 and to a less extent by the heat test at #acd deg44 7#b7 ,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 water1 by digestion in cold dilute alkaline solutions such as sodium carbonate1 or by extracting with ether1 alcohol1 benzene1 c42 these compounds1 however1 are soluble in the solvents of highly nitrated cellulose such as acetone1 acetic ether1 pyridine1 c41 even when these liquids are so diluted with water or other non-solvent liquids to such an extent that they have little or no solvent action upon the cellulose nitrate itself4 ,these solutions containing the bodies causing instability are neutral to test paper1 but become acid upon evaporation by heating4 7,this probably explains the presence of free acid when guncotton is purified by long-continued boiling in water without any neutralising agent being present47 7#c7 ,the bodies causing instability are products or by-products of the original ester reaction1 acid bodies containing nitroxy-groups1 but otherwise of ill-defined characteristics4 ,they combine with the oxides of zinc or lead1 giving insoluble compounds4 ,they are precipitated from their solutions in diluted acetone upon the addition of soluble salts of these metals4 7#d7 ,cellulose nitrates are rendered stable either by eliminating these compounds1 or by combining them with the oxides of lead or zinc whilst still in association with cellulose nitrates4 7#e7 ,even the most perfectly purified nitrocellulose will slowly decompose with formation of unstable acid products by boiling for a long time in water4 ,this effect is much more apparent at higher temperatures4 ,dense structureless or non-fibrous cellulose nitrates can be industrially prepared 7#a7 by nitrating the amorphous forms of cellulose obtained from its solution as sulphocarbonate 7viscose74 ,the cellulose in this condition reacts with the closest similarity to the original fibrous cellulose2 the products are similar in composition and properties1 including that of instability4 7#b7 ,by treating the fibrous cellulose nitrates with liquid solvents of the high nitrate diluted with non-solvent liquids1 and more especially water4 ,the optimum effect is a specific disintegration or breaking down of their fibrous structure quite distinct from the gelatinisation which precedes solution in the undiluted solvent1 and occurring within narrow limits of variation in the proportion of the diluting and non-solvent liquid--for industrial work the most convenient solution to employ is acetone diluted with about #aj p4ct4 of water by volume4 ,the industrial applications of these results are the basis of ,english patents #ebhf 7#ahih71 #ah1hfh 7#ahih71 #ah1bcc 7#ahih71 ,luck and ,cross 7this ,journal1 #ahii1 #djj1 #ghg74 ,the structureless guncotton prepared as above described is of quite exceptional character1 and entirely distinct from the ordinary fibrous nitrate or the nitrate prepared by precipitation from actual solution in an undiluted solvent4#c ,by the process described1 the nitrate is obtained at a low cost in the form of a very fine1 dense1 structureless1 white powder of great purity and stability1 entirely free from all mechanical impurities4 ,the elimination of these mechanical impurities1 and also to a very great extent of coloured compounds contained in the fibrous nitrate1 makes the product also useful in the manufacture of celluloids1 artificial silk1 c41 whilst its very dense form gives it a great advantage over ordinary fibrous guncotton for use in shells and torpedoes1 and for the manufacture of gelatinised gunpowders1 c4 ,it can be compressed with ease into hard masses2 and experiments are in progress with a view of producing from it1 in admixture with 'retaining' ingredients1 a military explosive manufactured by means of ordinary black gunpowder machinery and processes4 ,manufacture of sporting powder4--,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 solution1 constitutes a process of value for the manufacture of sporting powder having a base of cellulose nitrate of any degree of nitration4 ,the following is a description of the hardening process4 ',soft grains' are manufactured from ordinary guncotton or other cellulose nitrate either wholly or in combination with other ingredients1 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 drying4 ,these grains are then treated with diluted acetone1 the degree of dilution being fixed according to the hardness and bulk of the finished grain it is desired to produce 7,j4 ,soc4 ,chem4 ,ind41 #ahii1 #ghg74 ,owing to the wide limits of dilution and corresponding effect1 the process allows of the production of either a 'bulk' or a 'condensed' powder4 ,we prefer to use about five litres of the liquid to each one kilo4 of grain operated upon1 as this quantity allows of the grains being freely suspended in the liquid upon stirring4 ,the grains are run into the liquid1 which is then preferably heated to the boiling-point for a few minutes whilst the whole is gently stirred4 ,under this treatment the grains assume a more or less rounded gelatinous condition according to the strength of the liquid4 ,there is1 however1 no solution of the guncotton and practically no tendency of the grains to cohere4 ,each grain1 however1 is acted upon throughout and perfectly equally4 ,after a few minutes' treatment1 water is gradually added1 when the grains rapidly harden4 ,they are then freed from acetone and certain impurities by washing with water1 heating1 and drying4 ,the process is of course carried out in a vessel provided with any means for gentle stirring and heating1 and with an outlet for carrying off the volatilised solvent which is entirely recovered by condensation1 the grains parting with the acetone with ease4 ,stabilising cellulose nitrates4--,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 process4 ,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 nitrates4 ,such mixtures seem peculiarly liable to decomposition if the cellulose nitrate is not of exceptional stability 7,j4 ,soc4 ,chem4 ,ind41 #ahii1 #ghg74 ,,emploi ,,de ,,la ,,cellulose ,,pour ,,la ,,fabrication ,,de ,,fils ,,brillants ,,imitant ,,la ,,soie4 ,e4 ,,bronnert 7#a7 7,rev4 ,mat4 ,col41 #aijj1 ,september1 #bfg74 ,v4 ,,use ,,of ,,cellulose ,,in ,,the ,,manufacture ,,of ,,imitations ,,of ,,silk 7,,lustra-,,cellulose74 7p4 #de7 ,introduction4--,the problem of spinning a continuous thread of cellulose has received in later years several solutions4 ,mechanically all resolve themselves into the preparation of a structureless filtered solution of cellulose or a cellulose derivative1 and forcing through capillary orifices into some medium which either absorbs or decomposes the solvent4 ,the author notes here that the fineness and to a great extent the softness of the product depends upon the dimensions of the capillary orifice and concentration of the solution4 ,the technical idea involved in the spinning of artificial fibres is an old one4 ,reaumur 7#b7 forecast its possibility1 ,audemars of ,lausanne took a patent as early as #ahee 7#c7 for transforming nitrocellulose into fine filaments which he called 'artificial silk4' ,the idea took practical shape only when it came to be used in connection with filaments for incandescent lamps4 ,in this connection we may mention the names of the patentees3--,swinburne 7#d71 ,crookes1 ,weston 7#e71 ,swan 7#f71 and ,wynne and ,powell 7#g74 ,these inventors prepared the way for ,chardonnet's work1 which has been followed since #ahhh with continually increasing success4 ,at this date the lustra-celluloses known may be divided into four classes4 #a4 ',artificial silks' obtained from the nitrocelluloses4 #b4 ',lustra-cellulose' made from the solution of cellulose in cuprammonium4 #c4 ',lustra-cellulose' prepared from the solution of cellulose in chloride of zinc4 #d4 ',viscose silks1' by the decomposition of sulphocarbonate of cellulose 7,cross and ,bevan74 ,,group #a4 ,the early history of the ,chardonnet process is discussed and some incidental causes of the earlier failures are dealt with4 ,the process having been described in detail in so many publications the reader is referred to these for details4 ,see ,bibliography1 7#a7 and 7#b71 7#c7 and 7#d74 ,the denitrating treatment was introduced in the period #ahhh-ij and of course altogether changed the prospects of the industry2 not only does it remove the high inflammability1 but adds considerably to softness1 lustre1 and general textile quality4 ,in ,table ,i will be found some important constants for the nitrocellulose fibre2 also the fibre after denitration and the comparative constants for natural silk4 ,,table #a4 ,tenacity ,elasticity 7grammes7 7 elongation7 ,nitrocellulose according to ,chardonnet ,german ,patent ,no4 #ha1eii #aej #bc ,the same after denitration #aaj #h ,denitrated fibre moistened with water #be -- ,nitrocellulose3 ,bronnert's ,german ,patent ,no4 #ic1jji #abe #bh ,the same after denitration 7dry7 #aae #ac ,the same after denitration 7wetted7 #cb -- ,natural silk #cjj #ah #a4 ,tenacity is the weight in grammes required to break the thread4 #b4 ,elasticity is the elongation per cent4 at breaking4 ,the numbers are taken for thread of #ajj deniers 7#dej metres of #j4je grammes #a denier74 ,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 variation4 ,in regard to the manufacture a number of very serious difficulties have been surmounted4 ,first1 instead of drying the nitrated cellulose1 which often led to fires1 c41 it was found better to take it moist from the centrifugal machine1 in which condition it is dissolved 7#e74 ,it was next found that with the concentrated collodion the thread could be spun direct into the air1 and the use of water as a precipitant was thus avoided4 ,with regard to denitration which is both a delicate and disagreeable operation3 none of the agents recommended to substitute the sulphydrates have proved available4 ,of these the author mentions ferrous chloride 7#f71 ferrous chloride in alcohol 7#g71 formaldehyde 7#h71 sulphocarbonates4 ,the different sulphydrates 7#i7 have very different effects4 ,the calcium compound tends to harden and weaken the thread4 ,the ammonia compound requires great care and is costly4 ,the magnesium compound works rapidly and gives the strongest thread4 ,investigations have established the following point4 ,in practice it is not necessary to combine the saponification of cellulose ester with complete reduction of the nitric acid split off4 ,the latter requires eight molecules of hydrogen sulphide per one molecule tetranitrocellulose1 but with precautions four molecules suffice4 ,it is well known that the denitration is nearly complete1 traces only of nitric groups surviving4 ,their reactions with diphenylamine allow a certain identification of artificial silks of this class4 ,various other inventors1 e4g4 ,du ,vivier 7#aj71 ,cadoret 7#aa71 ,lehner 7#ab71 have attempted the addition of other substances to modify the thread4 ,these have all failed4 ,lehner1 who persisted in his investigations1 and with success1 only attained this success1 however1 by leaving out all such extraneous matters4 ,lehner works with #aj p4ct4 solutions2 ,chardonnet has continually aimed at higher concentration up to #bj p4ct4 ,lehner has been able very much to reduce his pressures of ejection in consequence2 ,chardonnet has had to increase up to pressures of #fj k4 per cm4 and higher4 ,the latter involves very costly distributing apparatus4 ,lehner made next considerable advance by the discovery of the fact that the addition of sulphuric acid to the collodion caused increase of fluidity 7#ac71 which ,lehner attributes to molecular change4 ,chardonnet found similar results from the addition of aldehyde and other reagents 7#ad71 but not such as to be employed for the more concentrated collodions4 ,the author next refers to his discoveries 7#ae7 that alcoholic solutions of a number of substances1 organic and inorganic1 freely dissolve the lower cellulose nitrates4 ,the most satisfactory of these substances is chloride of calcium 7#af74 ,it is noted that acetate of ammonia causes rapid changes in the solution1 which appear to be due to a species of hydrolysis4 ,the result is sufficiently remarkable to call for further investigation4 ,the chloride of calcium1 it is thought possible1 produces a direct combination of the alcohol with a reactive group of the nitrocellulose4 ,the fluidity of this solution using one mol4 ,ca,cl#b per #a mol4 tetranitrate 7#ag7 reaches a maximum in half an hour's heating at #fj deg4-#gj deg4,c4 ,the fluidity is increased by starting from a cotton which has been previously mercerised4 ,after nitration there is no objection to a chlorine bleach4 ,chardonnet has found on the other hand that in bleaching before nitration there is a loss of spinning quality in the collodion4 ,the author considers that the new collodion can be used entirely in place of the ordinary ether-alcohol collodion4 ,with regard to the properties of the denitrated products they fix all basic colours without mordant and may be regarded as oxycellulose therefore4 ,the density of the thread is from #a4e to #a4ee4 ,the thread of #ajj deniers shows a mean breaking strain of #abj grammes with an elasticity of #h-ab p4ct4 ,the cardinal defect of these fibres is their property of combination with water4 ,many attempts have been made to confer water-resistance 7#ah71 but without success4 ,strehlenert has proposed the addition of formaldehyde 7#ai71 but this is without result 7#bj74 ,in reference to these effects of hydration1 the author has made observations on cotton thread1 of which the following table represents the numerical results3 ,breaking ,strain ,mean of #bj experiments ,skein of bleached cotton without treatment #hbe ,skein of bleached cotton without treatment1 but wetted #idb ,ditto after conversion into hexanitrate1 dry #hhd ,the above1 wetted #hbh ,the cotton denitrated from above1 dry #ebi ,the cotton denitrated as above and wetted #bjf ,the author considers that other patents which have been taken for spinning nitrocellulose are of little practical account 7#ba7 and 7#bb74 ,the same conclusion also applies to the process of ,langhans1 who proposes to spin solutions of cellulose in sulphuric acid 7#bc7 7#bd7 and mixtures of sulphuric acid and phosphoric acid4 ,,group #b4 ,lustra-cellulose4--,thread prepared by spinning solutions of cellulose in cuprammonium4 ,this product is made by the ,vereinigte ,glanzstoff-,fabriken1 ,aachen1 according to a series of patents under the names of ,h4 ,pauly1 ,m4 ,fremery and ,urban1 ,consortium mulhousien pour la fabrication de fils brillants1 ,e4 ,bronnert1 and ,e4 ,bronnert and ,fremery and ,urban 7#a74 ,the first patent in this direction was taken by ,despeissis in #ahij 7#b74 ,it appears this inventor died shortly after taking the patent 7#c7 ,the matter was later developed by ,pauly 7#d7 especially in overcoming the difficulty of preparing a solution of sufficient concentration4 7,it is to be noted that ,pauly's patents rest upon a very slender foundation1 being anticipated in every essential detail by the previous patent of ,despeissis47 ,for this very great care is required1 especially1 first1 the condition of low temperature1 and1 secondly1 a regulated proportion of copper and ammonia to cellulose4 ,the solution takes place more rapidly if the cellulose has been previously oxidised4 ,such cellulose gives an #h p4ct4 solution1 and the thread obtained has the character of an oxycellulose1 specially seen in its dyeing properties4 ,the best results are obtained1 it appears1 by the preliminary mercerising treatment and placing the alkali cellulose in contact with copper and ammonia4 7,all reagents employed in molecular proportions47 ,the author notes that the so-called hydrocellulose 7,girard7 7#e7 is almost insoluble in cuprammonium1 as is starch4 ,it is rendered soluble by alkali treatment4 ,,group #c4 ,lustra-cellulose prepared by spinning a solution of cellulose in concentrated chloride of zinc4 ,this solution has been known for a long time and used for making filaments for incandescent lamps4 ,the cellulose threads1 however1 have very little tenacity4 ,this is no doubt due to the conditions necessary for forming the solution1 the prolonged digestion causing powerful hydrolysis 7#a74 ,neither the process of ,wynne and ,powell 7#b7 nor that of ,dreaper and ,tompkins 7#c71 who have endeavoured to bring the matter to a practical issue1 are calculated to produce a thread taking a place as a textile4 ,the author has described in his ,american patent 7#d7 a method of effecting the solution in the cold1 viz4 again by first mercerising the cellulose and washing away the caustic soda4 ,this product dissolves in the cold and the solution remains unaltered if kept at low temperature4 ,experiments are being continued with these modifications of the process1 and the author anticipates successful results4 ,the modifications having the effect of maintaining the high molecular weight of the cellulose1 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 cellulose1 i4e4 to its degree of molecular aggregation 7#e74 ,,group #d4 ',viscose' silks obtained by spinning solutions of xanthate of cellulose4 ,in #ahib1 ,cross and ,bevan patented the preparation of a new and curious compound of cellulose1 the thiocarbonate 7#a7 7#b7 7#c74 ,great hopes were based upon this product at the time of its discovery4 ,it was expected to yield a considerable industrial and financial profit and also to contribute to the scientific study of cellulose4 ,the later patents of ,c4 ,h4 ,stearn 7#d7 describe the application of viscose to the spinning of artificial silk4 ,the viscose is projected into solutions of chloride of ammonium and washed in a succession of saline solutions to remove the residual sulphur impurities4 ,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 purpose1 he is not of opinion that it shows any advance on the lustra-cellulose 7#b7 and 7#c74 ,he also considers that the bisulphide of carbon1 which must be regarded as a noxious compound1 is a serious bar to the industrial use of the process1 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 process4 ,the final product not being on the market he does not pronounce a finally unfavourable opinion4 ,the author and the ,vereinigte ,glanzstoff-,fabriken after long investigation have decided to make nothing but the lustra-cellulose 7#b7 and 7#c74 ,a new factory at ,niedermorschweiler1 near ,mulhouse1 is projected for this last production4 ,,bibliography ,introduction 7#a7 ,bull4 de la ,soc4 industr4 de ,mulhouse1 #aijj4 7#b7 ,reaumur1 ,memoire pour servir a l'histoire des insectes1 #ahgd1 #a1 p4 #aed4 7#c7 ,english ,pat4 ,no4 #bhc1 ,feb4 #f1 #ahee4 7#d7 ,swinburne1 ,electrician1 #ah1 #bh1 #ahhg1 p4 #bef4 7#e7 ,weston 7,swinburne71 ,electrician1 #ah1 #ahhg1 p4 #bhg4 ,eng4 ,pat4 ,no4 #bbhff1 ,sept4 #ab1 #ahhb4 7#f7 ,german ,pat4 ,no4 #cjbi4 ,english ,pat4 ,no4 #afaghj1 ,april #bh1 #ahhd 7,swan74 7#g7 ,wynne-,powell1 ,english ,pat4 ,no4 #afhje1 ,dec4 #bb1 #ahhd4 ,group ,i 7#a7 ,german ,pat ,no4 #chcfh1 ,dec4 #bj1 #ahhe4 ,german ,pat4 ,no4 #dfabe1 ,march #d1 #ahhh4 ,german ,pat4 ,no4 #efcca1 ,feb4 #f1 #ahij4 ,german ,pat4 ,no4 #haeii1 ,oct4 #aa1 #ahic4 ,german ,pat4 ,no4 #effee1 ,april #bc1 #ahij4 ,french ,pat4 ,no4 #bcabcj1 ,june #cj1 #ahic4 7#b7 ,industrie textile1 #ahii1 #ahib4 ,wyss-,noef1 ,zeitschrift fuer angewandte ,chemie1 #ahii1 #cj1 #cc4 ,la ,nature1 ,jan4 #a1 #ahih1 ,no4 #abhc4 ,revue generale des sciences1 ,june #cj1 #ahih4 7#c7 ,german ,pat4 ,no4 #dfabe1 ,march #d1 #ahhh4 ,german ,pat4 ,no4 #effee1 ,april #bc1 #ahij4 7#d7 ,swan1 ,english ,pat4 #afaghj1 ,june #bh1 #ahhd4 ,see also ,bechamp1 ,dict4 de ,chimie de ,wurtz4 7#e7 ,german ,pat4 ,no4 #haeii1 ,oct #aa1 #ahic4 7#f7 ,bechamp1 art4 ,cellulose1 ,dict4 de ,chimie de ,wurtz1 p4 #gha4 7#g7 ,chardonnet1 addit4 ,march #c1 #ahig1 to the ,french ,pat4 #bcabcj1 ,may #cj1 #ahic4 7#h7 ,knofler1 ,french ,pat4 #bdghee1 ,june #a1 #ahie4 ,german ,pat4 #hheef1 ,march #bh1 #ahid4 7#i7 ,bechamp1 art4 ,cellulose1 ,dict4 de ,chimie de ,wurtz4 ,blondeau1 ,ann4 ,chim4 et ,phys4 7#c71 #ahfc1 #fh1 p4 #dfb4 7#aj7 ,revue industrielle1 #ahij1 p4 #aid4 ,german ,pat4 #ebigg1 ,march #g1 #ahhi4 7#aa7 ,french ,pat4 #befhed1 ,june #b1 #ahif4 7#ab7 ,german ,pat4 #eeidi1 ,nov4 #i1 #ahhi4 ,german ,pat4 #ehejh1 ,sept4 #af1 #ahij4 ,german ,pat4 #hbeee1 ,nov4 #ae1 #ahid4 7#ac7 ,german ,pat4 #ehejh1 ,sept4 #af1 #aijj4 7#ad7 ,french ,pat4 #bcabcj1 ,june #cj1 #ahic4 7#ae7 ,german ,pat4 #icjji1 ,nov4 #ai1 #ahie4 ,french ,pat4 #bedgjc1 ,march #ab1 #ahif4 ,english ,pat4 #fheh1 ,march #bh1 #ahif4 7#af7 ,american ,pat4 #egcacb1 ,dec4 #ae1 #ahif4 7#ag7 ,this proportion is the most advantageous1 and furnishes the best liquid collodions that can be spun4 7#ah7 ,french ,pat4 #beidbb1 ,sept4 #c1 #ahif4 7#ai7 ,english ,pat4 #bbedj1 #ahif4 7#bj7 ,application for ,german ,pat4 not granted1 #dicc ,,iv4 #bif1 ,mar4 #af1 #ahig4 7#ba7 ,german ,pat4 #ifbjh1 ,feb4 #aj1 #ahig4 ,addit4 ,pat4 #ajahdd and #ajbegc1 ,dec4 #aj1 #ahig4 7#bb7 ,oberle et ,newbold1 ,french ,pat4 #behbh1 ,july #bb1 #ahif4 ,granquist1 ,engl4 applic4 #bcgi1 ,nov4 #bh1 #ahii4 7#bc7 ,german ,pat4 #gbegb1 ,june #ag1 #ahia4 7#bd7 ,voy4 ,stern1 ,ber41 #bh1 ch4 #dfb4 ,group ,,ii 7#a7 ,german ,pat4 #ihfdb1 ,dec4 #a1 #ahig 7,pauly74 ,french ,pat4 #bhffib1 ,march #aj1 #ahii1 and addition of ,october #ad1 #ahii 7,fremery and ,urban74 ,french ,pat4 #bhfgbf1 ,march #aa1 #ahii1 and addition of ,december #d1 #ahii4 ,german ,pat4 #aaacac1 ,march #af1 #ahii 7,fremery and ,urban74 ,english ,pat4 #ahhhd1 ,sept4 #ai1 #ahii 7,bronnert74 ,english ,pat4 #accca1 ,june #bg1 #ahii 7,consort4 mulhousien74 7#b7 ,french ,pat4 #bjcgda1 ,feb4 #ab1 #ahij4 7#c7 ,the actual lapse of this patent is due to the death of ,despeissis shortly after it was taken4 7#d7 ,without questioning the good faith of ,pauly1 it is nevertheless a fact that the original patent remains as a document1 and therefore that the value of the ,pauly patents is very questionable4 7#e7 ,girard1 ,ann4 ,chim4 et ,phys1 #ahha 7#e71 #bd1 p4 #ccg-chd4 ,group ,,iii 7#a7 ,cross and ,bevan1 ,cellulose1 #ahie1 p4 #h4 7#b7 ,english ,pat4 #afhje1 ,dec4 #bb1 #ahhd4 7#c7 ,english ,pat4 #agija1 ,july #cj1 #ahig4 7#d7 ,bronnert1 ,american ,pat4 #fdfgii1 ,april #c1 #aijj4 7#e7 ,cross and ,bevan1 ,cellulose1 #ahie1 p4 #ab4 ,group ,,iv 7#a7 ,english ,pat4 #hgjj1 #ahib4 ,german ,pat4 #gjiii1 ,jan4 #ac1 #ahic4 7#b7 ,english ,pat4 #dgac1 #ahif4 ,german ,pat4 #ibeij1 ,nov4 #ba1 #ahif4 7#c7 ,comptes rendus 7loc4 cit474 ,berichte1 c4 #i1 #fe;a4 7#d7 ,english ,pat4 #ajbj1 #ahih4 ,german ,pat4 #ajheaa1 ,oct4 #ah1 #ahih4 ,artificial ,silk--,lustra-cellulose4 ,c4 ,f4 ,,cross and ,e4 ,j4 ,,bevan 7,j4 ,soc4 ,chem4 ,ind41 #ahif1 #cag74 ,the object of this paper is mainly to correct current statements as to the artificial or 'cellulose silks' being explosive or highly inflammable 7ibid41 #ahie1 #gbj74 ,a specimen of the ',lehner' silk was found to retain only #j4ai p4ct4 total nitrogen1 showing that the denitration is sufficiently complete to dispose of any suggestion of high inflammability4 ,the product yielded traces only of furfural2 on boiling with a #a p4ct4 solution of sodium hydrate1 the loss of weight was #i4ad p4ct42 but the solution had no reducing action on ,fehling's solution4 ,the product in denitration had therefore reverted completely to a cellulose 7hydrate71 no oxy-derivative being present4 99 99 99 99 99 ,the authors enter a protest against the term 'artificial silk' as applied to these products1 and suggest 'lustra-cellulose4' ,,die ,k,ue,n,s,t,l,i,c,h,e ,,seide-,,ihre ,,herstellung1 ,,eigenschaften ,,und ,,verwendung4 ,,carl ,s,ue,v,e,r,n1 ,berlin1 #aijj1 ,j4 ,springer4 ,,artificial ,,silk--,,its ,,production1 ,,properties1 ,,and ,,applications4 ,this work of some #acj pages is an important monograph on the subject of the preparation of artificial cellulose threads--so far as the technical elements of the problems involved are discussed and disclosed in the patent literature4 ,the first section1 in fact1 consists almost exclusively of the several patent specifications in chronological order and ranged under the sub-sections3 7a7 ,the ,spinning of ,nitrocellulose 7collodion72 7b7 ,the ,spinning of other ,solutions of ,cellulose2 7c7 ,the ,spinning of ,solutions of the ,nitrogenous ,colloids4 ,in the second section the author deals with the physical and chemical proportions of the artificial threads4 ,chardonnet 'silk' is stated to have a mean diameter of #ce mu1 but with considerable variations from the mean in the individual fibres2 equally wide variations in form are observed in cross-section4 ,the general form is elliptical1 but the surface is marked by deep striae1 and the cross-section is therefore of irregular outline4 ,this is due to irregular conditions of evaporation of the solvents1 the thread being 'spun' into the air from cylindrical orifices of regulated dimensions4 ,chardonnet states that when the collodion is spun into alcohol the resultant thread is a perfect cylinder 7,compt4 rend4 #ahhi1 #ajh1 #ifb74 ,the strength of the fibre is variously stated at from #ej-hj p4ct4 that of 'boiled off' ,china tram2 the true elasticity is #d-e p4ct41 the elongation under the breaking strain #ae-ag p4ct4 ,the sp4gr4 is #a4di1 i4e4 #c-e p4ct4 in excess of boiled off silk4 ,lehner 'silk' exhibits the closest similarity to the ,chardonnet product4 ,in cross-section it is seen to be more regular in outline1 and a round1 pseudo-tubular form prevails1 due to the conditions of shrinkage and collapse of the fibre in parting with the solvents1 and in then dehydrating4 ,the constants for 'breaking strain1' both in the original and moistened condition1 for elasticity1 c41 are closely approximate to those for the ,chardonnet product4 ,pauly 'silk'4--,the form of the ultimate fibres is much more regular and the contour of the cross-section is smooth4 ,the product shows more resistance to moisture and to alkaline solutions4 ,viscose 'silk' is referred to in terms of a communication appearing in ',papier-,zeitung1' #ahih1 #bdaf4 ,in the above section the following publications are referred to3 ,chardonnet1 ',compt4 rend41' #ahhg1 #aje1 #ijj2 and #ahhi1 #ajh1 #ifb2 ,silbermann1 ',die ,seide1' #ahig1 v4 #b1 #adc2 ,herzog1 ',farber-,zeitung1' #ahid_/e1 #di-ej2 ,thiele1 ibid4 #ahig1 #acc2 ,o4 ,schlesinger1 ',papier-,zeitung1' #ahie1 #aegh-ha1 #afaj-ab4 ,action of ,reagents upon ,natural and ,artificial ,silks4 #a4 ,potassium hydrate in solution of maximum concentration dissolves the silks proper1 7a7 ,china silk on slight warming1 7b7 ,tussah silk on boiling4 ,the cellulose 'silks' show swelling with discolouration1 but the fibrous character is not destroyed even on boiling4 #b4 ,potassium hydrate #dj p4ct4 ,china silk dissolves completely at #fe deg4-#he deg42 ,tussah silk swells considerably at #ge deg4 and dissolves at #ajj deg4-#abj deg44 ,the cellulose 'silks' are attacked with discolouration2 at #adj deg4 7boiling-point of the solution7 there is progressive solvent action1 but the action is incomplete4 ,the ,pauly product is most resistant4 #c4 ,zinc chloride1 #dj p4ct4 solution4 ,both the natural silks and lustra-celluloses are attacked at #ajj deg41 and on raising the temperature the further actions are as follows3 ,china silk is completely dissolved at #aaj-abj deg42 ,tussah silk at #acj-ace deg42 the collodion products at #adj-ade deg42 the ,pauly product was again most resistant1 dissolving at #ahj deg44 #d4 ,alkaline cupric oxide 7glycerin7 solution was prepared by dissolving #aj grs4 of the sulphate in #ajj c4c4 water1 adding #e grs4 glycerin and #aj c4c4 of #dj p4ct4 ,,koh4 ,in this solution the ,china silk dissolved at the ordinary temperature2 ,tussah silk and the lustra-celluloses were not appreciably affected4 #e4 ,cuprammonium solution was prepared by dissolving the precipitated cupric hydrate in #bd p4ct4 ammonia4 ,in this reagent also the ,china silk dissolved1 and the ,tussah silk as well as the lustra-celluloses underwent no appreciable change4 #f4 ,an ammoniacal solution of nickel oxide was prepared by dissolving the precipitated hydrated oxide in concentrated ammonia4 ,the ,china silk was dissolved by this reagent2 ,tussah silk and the lustra-celluloses entirely resisted its action4 #g4 ,fehling's solution is a solvent of the natural silks1 but is without action on the lustra-celluloses4 #h4 ,chromic acid--#bj p4ct4 ,cr,o#c--solution dissolves both the natural silks and the lustra-celluloses at the boiling temperature of the solution4 #i4 ,millon's reagent1 at the boiling solution1 colours the natural silks violet3 the lustra-celluloses give no reaction4 #aj4 ,concentrated nitric acid attacks the natural silks powerfully in the cold2 the lustra-celluloses dissolve on heating4 #aa4 ,iodine solution 7,i in ,,ki7 colours the ,china silk a deep brown1 ,tussah a pale brown2 the celluloses from collodion are coloured at first brown1 then blue4 ,the ,pauly product1 on the other hand1 does not react4 #ab4 ,diphenylamine sulphate4--,a solution of the base in concentrated sulphuric acid colours the natural silks a brown2 the collodion 'silks' give a strong blue reaction due to the presence of residual nitro-groups4 ,the ,pauly product is not affected4 #ac4 ,brucin sulphate in presence of concentrated sulphuric acid colours the natural silks only slightly 7brown72 the collodion 'silks' give a strong red colouration4 ,the ,pauly product again is without reaction4 #ad4 ,water4--,the natural silks do not soften in the mouth as do the lustra-celluloses4 #ae4 ,water of condition was determined by drying at #ajj deg42 the following percentages resulted 7a74 ,the percentages of water 7b7 taken up from the atmosphere after forty-three hours' exposure were3 7a7 7b7 ,china 7raw7 silk #g4ig #b4bd ,tussah silk #h4bf #e4jj ,lustra-celluloses3 ,chardonnet 7,besancon7 #aj4cg #e4fd ,spreitenbach #aa4ag #e4gg ,lehner #aj4ga #e4ig ,pauly #aj4jd #f4id #af4 ,behaviour on heating at #bjj deg44--,after two hours' heating at this temperature the following changes were noted3 ,china silk ,much discoloured 7brown74 ,tussah silk ,scarcely affected4 ,lustra-celluloses3 ,chardonnet ,converted into a blue-black charcoal1 retaining the ,lehner form ofthe fibres4 ,pauly ,a bright yellow-brown colouration1 without carbonisation4 #ag4 ,the losses of weight accompanying these changes and calculated per #ajj parts of fibre dried at #ajj deg4 were3 ,china silk #c4ah ,tussah silk #b4ie ,lustra-celluloses3 ,chardonnet #cc4gj ,lehner #bf4ef ,pauly #a4fa #ah4 ,inorganic constituents4--,determinations of the total ash gave for the first five of the above1 numbers varying from #a4j to #a4g p4ct4 ,the only noteworthy point in the comparison was the exceptionally small ash of the ,pauly product1 viz4 #j4jif p4ct4 #ai4 ,total nitrogen4--,the natural silks contain the #af-ag p4ct4 ,n characteristic of the proteids4 ,the lustra-celluloses contain #j4je-j4ae p4ct4 ,n which in those spun from collodion is present in the form of nitric groups4 ,the points of chemical differentiation which are established by the above scheme of comparative investigation are summed up in tabular form4 ,methods of dyeing4--,the lustra-celluloses are briefly discussed4 ,the specific relationship of these forms of cellulose to the colouring matters are in the main those of cotton1 but they manifest in the dye-bath the somewhat intensified attraction which characterises mercerised cotton1 or more generally the cellulose hydrates4 ,industrial applications of the lustra-celluloses are briefly noticed in the concluding section of the book4 ,,footnotes3 #c ,with these products it is easy to observe that they have a definite fusion point #e deg4-#aj deg4 below the temperature of explosion4 ,,section ,,iii4 ,,decompositions ,,of ,,cellulose ,,such ,,as ,,throw ,,light ,,on ,,the ,,problem ,,of ,,its ,,constitution ,,ueber ,,cellulose4 ,g4 ,,bumcke und ,r4 ,,wolffenstein 7,berl4 ,ber41 #ahii1 #bdic74 7p4 #ed7 ,theoretical ,preface4--,the purpose of these investigations is the closer characterisation of the products known as 'oxycellulose' and 'hydracellulose1' which are empirical aggregates obtained by various processes of oxidation and hydrolysis2 these processes act concurrently in the production of the oxycelluloses4 ,the action of hydrogen peroxide was specially investigated4 ,an oxycellulose resulted possessing strongly marked aldehydic characteristics4 ,the authors commit themselves to an explanation of this paradoxical result1 i4e4 the production of a body of strongly 'reducing' properties by the action of an oxidising agent upon the inert cellulose molecule 78 aggregate7 as due to the hydrolytic action of the peroxide3 following ,wurster 7,ber4 #bb1 #ade71 who similarly explained the production of reducing sugars from cane sugar by the action of the peroxide4 ,the product in question is accordingly termed hydralcellulose4 ,by the action of alkalis this is resolved into two bodies of alcoholic 7cellulose7 and acid 7'acid cellulose'7 characteristics respectively4 ,the latter in drying passes into a lactone4 ,the acid product is also obtained from cellulose by the action of alkaline lye 7boiling #cj p4ct4 ,na,o,h7 and by solution in ,schweizer's reagent4 ,it is considered probable that the cellulose nitrates are hydrocellulose derivatives1 and experimental evidence in favour of this conclusion is supplied by the results of 'nitrating' the celluloses and their oxy- and hydro- derivatives4 ,identical products were obtained4 ,experimental investigations4--,the filter paper employed as 'original cellulose1' giving the following numbers on analysis3 ,c #dd4ef #dd4bi #dd4ec #dd4ef ,h #f4ci #f4ca #f4df #f4db was exposed to the action of pure distilled ,h#b,o#b at #d-fj p4ct4 strength1 at ordinary temperatures until disintegrated3 a result requiring from nineteen to thirty days4 ,the series of products gave the following analytical results3 ,c #dc4fa #dc4fa #dc4df #dc4hi #dd4j #dc4hg #dc4ib #dc4ha ,h #f4jj #f4bi #f4bh #f4bf #f4ac #f4bg #f4bd #f4bg results lying between the requirements of the formulae3 #e ,c#f;,h#aj,o#e4;,h#b,o and #h ,c#f;,h#aj,o#e4;,h#b,o4 ,hydrazones were obtained with #a4g-a4h p4ct4 ,n4 ,treated with caustic soda solution the hydrazones were dissolved in part3 on reprecipitation a hydrazone of unaltered composition was obtained4 ,the original product shows therefore a uniform distribution of the reactive ,,co- groups4 ,the hydralcellulose boiled with ,fehling's solution reduced #a_/ab of the amount required for an equal weight of glucose4 ,digested with caustic soda solution it yielded #cc p4ct4 of its weight of the soluble 'acid cellulose4' ,this product was purified and analysed with the following result3 ,c #dc4ce ,h #f4e4 ,for the direct production of the 'acid' derivative1 cellulose was boiled with successive quantities of #cj p4ct4 ,na,o,h until dissolved4 ,it required eight treatments of one hour's duration4 ,on adding sulphuric acid to the solutions the product was precipitated4 ,yield #dj p4ct4 ,analyses3 ,c #dc4h #dc4h #dc4g ,h #f4b #f4b #f4c ,the cellulose reprecipitated from solution in ,schweizer's reagent gave similar analytical results3 ,c #dc4i #dc4h #dd4j ,h #f4e #f4c #f4d ,conversion into nitrates4--,the original cellulose1 hydral- and acid cellulose were each treated with #aj times their weight of ,,hno#c of #a4dh sp4gr4 and heated at #he deg4 until the solution lost its initial viscosity4 ,the products were precipitated by water and purified by solution in acetone from which two fractions were recovered1 the one being relatively insoluble in ethyl alcohol4 ,the various nitrates from the several original products proved to be of almost identical composition1 ,c #cb4j ,h #d4b ,n #h4h with a molecular weight approximately #acej4 ,the conclusion is that these products are all derivatives of a 'hydralcellulose' #f;,c#f;,h#aj,o#e;,h#b,o4 ,,formation ,,of ,,furfuraldehyde ,,from ,,cellulose1 ,,oxycellulose1 ,,and ,,hydrocellulose4 ,by ,,leo ,,vignon 7,compt4 rend41 #ahih1 #abf1 #acee-aceh74 7p4 #ed7 ,hydrocellulose1 oxycellulose1 and 'reduced' cellulose1 the last named being apparently identical with hydrocellulose1 were obtained by heating carefully purified cotton wool 7#aj grams7 in water 7#a1jjj c4c471 with 7#a7 #fe c4c4 of hydrochloric acid 7#a4b sp4gr471 7#b7 #fe c4c4 of hydrochloric acid and #hj grams of potassium chlorate1 7#c7 #fe c4c4 of hydrochloric acid and #ej grams of stannous chloride4 ,from these and some other substances1 the following percentage yields of furfuraldehyde were obtained3 ,hydrocellulose1 #j4hed2 oxycellulose1 #b4aac2 reduced cellulose1 #j4hfj2 starch1 #j4hjj2 bleached cotton1 #a4hjj2 oxycellulose1 prepared by means of chromic acid1 #c4ejj4 ,two specimens of oxycellulose were prepared by treating cotton wool with hydrochloric acid and potassium chlorate 7,a71 and with sulphuric acid and potassium dichromate 7,b71 and #be grams of each product digested with aqueous potash4 ,of the product ,a1 #af4bj grams were insoluble in potash1 #b4de grams were precipitated on neutralisation of the alkaline solution1 and #f4ce grams remained in solution1 whilst ,b yielded #aa4af grams of insoluble matter1 #a4db grams were precipitated by acid1 and #ab4db grams remained in solution4 ,the percentage yields of furfuraldehyde obtained from these fractions were as follows3 ,a1 insoluble1 #j4hf2 precipitated1 #d4ce2 dissolved1 #a4aj4 ,b1 insoluble1 #j4gf2 precipitated1 #e4aa2 dissolved1 #a4ed4 ,it appears1 from the foregoing results1 that the cellulose molecule1 after oxidation1 is easily decomposed by potash1 the insoluble and larger portion having all the characters of the original cellulose1 whilst the soluble portion is of an aldehydic nature1 and contains a substance1 precipitable by acids1 which yields a relatively large amount of furfuraldehyde4 ,,untersuchungen ,ue,b,e,r ,,die ,,oxycellulose4 ,o4 ,v4 ,,faber und ,b4 ,,tollens 7,berl4 ,ber41 #ahii1 #behi74 ,investigations of ,oxycellulose4 7p4 #fa7 ,the author's results are tersely summed up in the following conclusions set forth at the end of the paper3 ,the oxycelluloses are mixtures of cellulose and a derivative oxidised compound which contains one more atom ,o than cellulose 7cellulose ,c#f;,h#aj,o#e71 and for which the special designation ,celloxin is proposed4 ,celloxin may be formulated ,c#h;,h#f,o#f or ,c#f;,h#aj,o#f1 of which the former is the more probable4 ,the various oxycelluloses may be regarded as containing one celloxin group to #a-d cellulose groups1 according to the nature of the original cellulose1 and the degree of oxidation to which subjected4 ,these groups are in chemical union4 ,celloxin has not been isolated4 ,on boiling the oxycelluloses with lime-milk it is converted into isosaccharinic and dioxybutyric acids4 ,the insoluble residue from the treatment is cellulose4 ,the following oxycelluloses were investigated3 ,a4 ,product of action of nitric acid upon pine wood 7,lindsey and ,tollens1 ,ann4 #bfg1 #cff74--,the oxycelluloses contained #a mol celloxin3 #b mol4 cellulose on #f hours' heating #c mol4 cellulose on #c hours' heating with a ratio ,h 3 ,o #a 3 #i and #a 3 #h4g respectively3 they yielded #g p4ct4 furfural4 ,b4 ,by action of bromine in presence of water and ,ca,c,o#c upon cotton4--,yield1 7air-dry7 #he p4ct4 ,empirical composition ,c#ab;,h#bj,o#aa ,c#f;,h#aj,o#e4;,c#f;,h#aj,o#f3 yielded furfural #a4g p4ct4 ,c4 ,cotton and nitric acid at #ajj deg41 two and a half hours 7,cross and ,bevan74--,yield1 #gj p4ct4 ,composition #d ,c#f;,h#aj,o#e4;,c#f;,h#h,o#f yielded furfural #b4c p4ct4 ,d4 ,cotton and nitric acid at #ajj deg4 7four hours74--,a more highly oxidised product resulted1 viz4 #c ,c#f;,h#aj,o#e4;,c#f;,h#h,o#f3 yielded furfural #c4b p4ct4 ,by-products of oxidation4--,the liquors from ,b were found to contain saccharic acid3 the acid from ,c and ,b contained a dibasic acid which appeared to be tartaric acid4 ,the isolation of 7#a7 isosaccharinic and 7#b7 dioxybutyric acid from the products of digestion of the oxycelluloses with lime-milk at #ajj deg4 was effected by the separation of their respective calcium salts1 7#a7 by direct crystallisation1 7#b7 by precipitation alcohol after separation of the former4 ,,celluloses1 ,,hydro- ,,and ,,oxycelluloses1 ,,and ,,cellulose ,,esters4 ,l4 ,,vignon 7,bull4 ,soc4 ,chim41 #aija #c1 #be1 #acj74 7a7 ,oxycelluloses from cotton1 hemp1 flax1 and ramie4--,the comparative oxidation of these celluloses1 by treatment with ,h,cl,o#c at #ajj deg41 gave remarkably uniform results1 as shown by the following numbers1 showing extreme variations3 yields1 #fh-gj p4ct42 hydrazine reaction1 ,n fixed #a4eh-a4fi2 fixation of basic colouring matters 7relative numbers71 saffranine1 #ajj-bjj1 methylene blue1 #ajj-ajf4 ,the only points of difference noted were 7#a7 hemp is somewhat more resistant to the acid oxidation2 7#b7 the cotton oxycellulose shows a somewhat higher 7#be p4ct47 cupric reduction4 7b7 ',saccharification' of cellulose1 cellulose hydrates1 and hydrocellulose4--,the products were digested with dilute hydrochloric acid six hours at #ajj deg41 and the cupric reduction of the soluble products determined and calculated to dextrose4 #ajj grms4 of gave reducing products equal to ,dextrose ,purified cotton #c4bi ,hydrocellulose #i4gj ,cotton mercerised 7,na,o,h #cj deg4 ,b47 #d4ci ,cotton mercerised 7,na,o,h #dj deg4 ,b47 #c4ea ,cellulose reprecipitated from cuprammonium #d4ci ,oxycellulose #ad4gj ,starch #ih4f ,these numbers show that cellulose may be hydrated both by mercerisation and solution1 without affecting the constitutional relationships of the ,,co groups4 ,the results also differentiate the cellulose series from starch in regard to hydrolysis4 7c7 ,cellulose and oxycellulose nitrates4--,the nitric esters of cellulose have a strong reducting action on alkaline copper solutions4 ,the author has studied this reaction quantitatively for the esters both of cellulose and oxycellulose1 at two stages of 'nitration1' represented by #h4b-h4f p4ct4 and #ac4e-ac4i p4ct4 total nitrogen in the ester-products1 respectively4 ,the results are expressed in terms 7c4c47 of the cupric reagent 7,pasteur7 reduced per #ajj grs4 compared with dextrose 7#aggfg74 ,cellulose maximum nitration 7#ac4e p4ct4 ,n7 #cfdj ,oxycellulose maximum nitration 7#ac4i p4ct4 ,n7 #cfjj ,cellulose minimum nitration 7#h4ai p4ct4 ,n7 #cgjj ,oxycellulose minimum nitration 7#h4ef p4ct4 ,n7 #cfbj ,the author concludes that1 since the reducing action is independent of the degree of nitration1 and is the same for cellulose and the oxycelluloses1 the ester reaction in the case of the normal cellulose is accompanied by oxidation1 the product being an oxycellulose ester4 ,products of 'denitration'4--,the esters were treated with ferrous chloride in boiling aqueous solution4 ,the products were oxycelluloses1 with a cupric reduction equal to that of an oxycellulose directly prepared by the action of ,h,cl,o#c4 ,on the other hand1 by treatment with ammonium sulphide at #ce deg4-#dj deg4 'denitrated' products were obtained without action on alkaline copper solutions4 ,,oxycelluloses ,,and ,,the ,,molecular ,,weight ,,of ,,cellulose4 ,h4 ,,nastukoff 7,berl4 ,ber4 #cc #ac #bbcg74 7p4 #fa7 ,the author continues his investigations of the oxidation of cellulose4 ,compare ,bull4 ,mulhouse1 #ahib4 ,the products described were obtained by the action of hypochlorites and permanganates upon ,swedish filter paper 7,schleicher and ,schuell74 #d4 ,oxidation by hypochlorites4--7#a7 ,the cellulose was digested #bd hrs4 with #ce times its weight of a filtered solution of bleaching power of #d deg4,b42 afterwards drained and exposed for #bd hrs4 to the atmosphere4 ,these treatments were then repeated4 ,after washing1 treatment with dilute acetic acid and again washing1 the product was treated with a #aj p4ct4 ,na,o,h solution4 ,the oxycellulose was precipitated from the filtered solution3 yield #de p4ct4 ,the residue when purified amounted to #cj p4ct4 of the original cellulose1 with which it was identical in all essential properties4 ,the oxycellulose1 after purification1 dried at #aaj deg41 gave the following analytical numbers3 ,c #dc4fd #dc4gh #dc4cb #dc4ac ,h #f4ag #f4ba #e4ih #f4jh ,its compound with phenylhydrazine 7loc4 cit47 gave the following analytical numbers3 ,n #j4gh #j4if #j4hd 7#b7 ,the reagents were as in 7#a71 but the conditions varied by passing a stream of carbonic acid gas through the solution contained in a flask1 until ,cl compounds ceased to be given off4 ,the analysis of the purified oxycellulose gave ,c #dc4ec1 ,h #f4ac4 7#c7 ,the conditions were as in 7#b71 but a much stronger hypochlorite solution--viz4 #ab deg4,b4--was employed4 ,the yield of oxycellulose precipitated from solution in soda lye 7#aj p4ct4 ,na,o,h7 was #de p4ct4 ,there was only a slight residue of unattacked cellulose4 ,the analytical numbers obtained were3 ,oxycellulose ,c #dc4ca #dc4gd #dc4fi ,h #f4dg #f4db #f4ea ,phenylhydrazine compound ,n #j4fb #j4ha ,b4 ,oxidation by permanganate 7,k,mn,o#d74 7#a7 ,the cellulose #af grms4 was treated with #aajj c4c4 of a #a p4ct4 solution of ,k,mn,o#d in successive portions4 ,the ,mn,o#b was removed from time to time by digesting the product with a dilute sulphuric acid 7#aj p4ct4 ,h#b,,so#d74 ,the oxycellulose was purified as before1 yield #dj p4ct4 ,analytical numbers3 ,oxycellulose ,c #db4ab #db4i ,h #f4bj #f4aa ,phenylhydrazine compound ,n #a4ce #a4jh #a4ba 7#b7 ,the cellulose 7#af grms47 was digested #ad days with #bejj c4c4 of #a p4ct4 ,k,mn,o#d solution4 ,the purified oxycellulose was identical in all respects with the above3 yield #dj p4ct4 ,c #db4ff1 ,h #f4ai4 7#c7 ,the cellulose 7#af grms47 was heated in the water-bath with #afjj c4c4 of #ae p4ct4 ,h#b,,so#d to which were added #ah grms4 ,k,mn,o#d4 ,the yield and composition of the oxycellulose was identical with the above4 ,it appears from these results that the oxidation with hypochlorites acids #a atom of ,o to #d-f of the unit groups ,c#f;,h#aj,o#e2 and the oxidation with permanganate #b atoms ,o per #d-f units of ,c#f;,h#aj,o#e4 ,the molecular proportion of ,n in the phenylhydrazine residue combining is fractional1 representing #a atom ,o1 i4e4 #a ,,co group reacting per #d ,c#cf;,h#fj,o#ca and #f ,c#bd;,h#di,o#ba respectively1 assuming the reaction to be a hydrazone reaction4 ,further investigations of the oxycelluloses by treatment with 7a7 sodium amalgam1 7b7 bromine 7water71 and 7c7 dilute nitric acid at #aaj deg41 led to no positive results4 ,by treatment with alcoholic soda 7,na,o,h7 the products were resolved into a soluble and insoluble portion1 the properties of the latter being those of a cellulose 7hydrate74 ,molecular weight of cellulose and oxycellulose4--,the author endeavours to arrive at numbers expressing these relations by converting the substances into acetates by ,schutzenberger's method1 and observing the boiling-points of their solution in nitrobenzene4 ,,fermentation ,,of ,,cellulose ,v4 ,,omelianski 7,compt4 ,rend41 #ahig1 #abe1 #aaca-aacc74 ,pure paper was allowed to ferment in the presence of calcium carbonate at a temperature of #ce deg4 for #ac months4 ,the products obtained from #c4dgdc grams of paper were3 acids of the acetic series1 #b4bdjb grams2 carbonic anhydride1 #j4igbb grams2 and hydrogen1 #j4jach gram4 ,the acids were chiefly acetic and butyric acid1 the ratio of the former to the latter being #a4g 3 #a4 ,small quantities of valeric acid1 higher alcohols1 and odorous products were formed4 ,the absence of methane from the products of fermentation is remarkable1 but the formation of this gas seems to be due to a special organism readily distinguishable from the ferment that produces the fatty acids4 ,this organism is at present under investigation4 99 99 99 99 99 7p4 #ge7 ,constitution of ,cellulose4--,it may be fairly premised that the problem of the constitution of cellulose cannot be solved independently of that of molecular aggregation4 ,we find in effect that the structural properties of cellulose and its derivatives are directly connected with their constitution4 ,so far we have only a superficial perception of this correlation4 ,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 characteristics1 and these products1 while still preserving the main chemical characteristics of the original1 show when converted into derivatives by simple synthesis1 e4g4 esters and sulphocarbonates1 a corresponding differentiation of the physical properties of these derivatives1 from the normal standard1 and therefore that the new reacting unit determines a new physical aggregate4 ,thus the sulphocarbonate of a 'hydrocellulose' is formed with lower proportions of alkaline hydrate and carbon disulphide1 gives solutions of relatively low viscosity1 and1 when decomposed to give a film or thread of the regenerated cellulose1 these are found to be deficient in strength and elasticity4 ,similarly with the acetate4 ,the normal acetate gives solutions of high viscosity1 films of considerable tenacity1 and when those are saponified the cellulose is regenerated as an unbroken film4 ,the acetates of hydrolysed celluloses manifest a retrogradation in structural and physical properties1 proportioned to the degree of hydrolysis of the original4 ,we may take this opportunity of pointing out that the celluloses not only suggest with some definiteness the connection of the structural properties of visible aggregates--that is1 of matter in the mass--with the configuration of the chemical molecule or reacting unit1 but supply unique material for the actual experimental investigation of the problems involved4 ,of all the 'organic' colloids cellulose is the only one which can be converted into a variety of derivative forms1 from each of which a regular solid can be produced in continuous length and of any prescribed dimensions4 ,thus we can compare the structural properties of cellulose with those of its hydrates1 nitrates1 acetates1 and benzoates1 in terms of measurements of breaking strain1 extensibility1 elasticity4 ,investigations in this field are being prosecuted1 but the results are not as yet sufficiently elaborated for reduction to formulae4 ,one striking general conclusion is1 however1 established1 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 atoms1 i4e4 of the molecular constitution4 ,also it is established that the molecular aggregate which constitutes a cellulose is of a resistant type1 and undoubtedly persists in the solutions of the compounds4 ,it may be urged that it is superfluous to import these questions of mass-aggregation into the problem of the chemical constitution of cellulose4 ,but we shall find that the point again arises in attempting to define the reacting unit1 which is another term for the molecule4 ,in the majority of cases we rely for this upon physical measurements2 and in fact the purely chemical determination of such quantities is inferential4 ,attempts have been made to determine the molecular weights of the cellulose esters in solution1 by observations of depression of solidifying and boiling-points4 ,but the numbers have little value4 ,the only other well-defined compound is the sulphocarbonate4 ,it has been pointed out that1 by successive precipitations of this compound1 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 dissociation1 i4e4 to fix a point at which the transition from soluble sulphocarbonate to insoluble cellulose takes place4 ,on these grounds it will be seen we are reduced to a somewhat speculative treatment of the hypothetical ultimate unit group1 which is taken as of ,c#f dimensions4 ,as there has been no addition of experimental facts directly contributing to the solution of the problem1 the material available for a discussion of the probabilities remains very much as stated in the first edition1 pp4 #ge-gg4 ,it is now generally admitted that the tetracetate n ,c#f;,h#f,o47,o,ac7#d is a normal cellulose ester2 therefore that four of the five ,o atoms are hydroxylic4 ,the fifth is undoubtedly carbonyl oxygen4 ,the reactions of cellulose certainly indicate that the ,,co- group is ketonic rather than aldehydic4 ,even when attacked by strong sulphuric acid the resolution proceeds some considerable way before products are obtained reducing ,fehling's solution4 ,this is not easily reconcilable with any polyaldose formula4 ,nor is the resistance of cellulose to very severe alkaline treatments4 ,the probability may be noted here that under the action of the alkaline hydrates there occurs a change of configuration4 ,lobry de ,bruyn's researches on the change of position of the typical ,,co- group of the simple hexoses1 in presence of alkalis1 point very definitely in this direction4 ,it is probable that in the formation of alkali cellulose there is a constitutional change of the cellulose1 which may in effect be due to a migration of a ,,co- position within the unit group4 ,again also we have the interesting fact that structural changes accompany the chemical reaction4 ,it is surprising that there should have been no investigation of these changes of external form and structure1 otherwise than as mass effects4 ,we cannot1 therefore1 say what may be the molecular interpretation of these effects4 ,it has not yet been determined whether there are any intrinsic volume changes in the cellulose substance itself3 and as regards what changes are determined in the reacting unit or molecule1 we can only note a fruitful subject for future investigation4 ,a priori our views of the probable changes depend upon the assumed constitution of the unit group4 ,if of the ordinary carbohydrate type1 formulated with an open chain1 there is little to surmise beyond the change of position of a ,,co- group4 ,but alternative formulae have been proposed4 ,thus the tetracetate is a derivative to be reckoned with in the problem4 ,it is formed under conditions which preclude constitutional changes within the unit groups4 ,the temperature of the main reaction is #cj deg4-#dj deg41 the reagents are used but little in excess of the quantitative proportions1 and the yields are approximately quantitative4 ,if now the derivative is formed entirely without the hydrolysis the empirical formula ,c#f;,h#f,o47,o,ac7#d justifies a closed-ring formula for the original viz4 ,,co,,choh#d;,,ch#b2 and the preference for this formula depends upon the explanation it affords of the aggregation of the groups by way of ,,co-,,ch#b synthesis4 ,the exact relationship of the tetracetate to the original cellulose is somewhat difficult to determine4 ,the starting-point is a cellulose hydrate1 since it is the product obtained by decomposition of the sulphocarbonate4 ,the degree of hydrolysis attending the cycle of reactions is indicated by the formula #d ,c#f;,h#aj,o#e4;,h#b,o4 ,it has been already shown that this degree of hydrolysis does not produce molecular disaggregation4 ,if this hydrate survived the acetylation it would of course affect the empirical composition1 i4e4 chiefly the carbon percentage1 of the product4 ,it may be here pointed out that the extreme variation of the carbon in this group of carbohydrate esters is as between ,c#ad;,h#bj,o#aj 7,c #dh4c p4ct47 and ,c#ad;,h#ah,o#i 7,c #ej4h p4ct47 i4e4 a tetracetate of ,c#f;,h#ab,o#f and ,c#f;,h#aj,o#e respectively4 ,in the fractional intermediate terms it is clear that we come within the range of ordinary experimental errors1 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 error4 ,the determination of the acetyl by saponification is also subject to an error sufficiently large to preclude the results being applied to solve the point4 ,while1 therefore1 we must defer the final statement as to whether the tetracetate is produced from or contains a partly hydrolysed cellulose molecule1 it is clear that at least a large proportion of the unit groups must be acetylated in the proportion ,c#f;,h#f,o47,o,ac7#d4 ,it has been shown that by the method of ,franchimont a higher proportion of acetyl groups can be introduced2 but this result involves a destructive hydrolysis of the cellulose3 the acetates are not derivatives of cellulose1 but of products of hydrolytic decomposition4 ,it appears1 therefore1 that with the normal limit of acetylation at the tetracetate the aggregation of the unit groups must depend upon the ,,co- groups and a ring formula of the general form ,,co,,choh#d;,,ch#b is consistent with the facts4 ,vignon has proposed for cellulose the constitutional formula ,o------,,ch ,o ,,choh#c _/ ,,ch#b-;,,ch_/ with reference to the highest nitrate1 and the decomposition of the nitrate by alkalis with formation of hydroxypyruvic acid4 ,while these reactions afford no very sure ground for deductions as to constitutional relationships1 it certainly appears that1 if the aldose view of the unit group is to be retained1 this form of the anhydride contains suggestions of the general tendency of the celluloses on treatment with condensing acids to split off formic acid in relatively large quantity ,ber4 #ahie1 #aidj2 the condensation of the oxycelluloses to furfural2 the non-formation of the normal hydroxy-dicarboxylic acids by nitric acid oxidations4 ,indirectly we may point out that any hypothesis which retains the polyaldose view of cellulose1 and so fails to differentiate its constitution from that of starch1 has little promise of progress4 ,the above formula1 moreover1 concerns the assumed unit group1 with no suggestion as to the mode of aggregation in the cellulose complex4 ,also there is no suggestion as to how far the formula is applicable to the celluloses considered as a group4 ,in extending this view to the oxycelluloses1 ,vignon introduces the derived oxidised group ,,cho47,,choh7#c4;,,ch 4 ,,co ,o --of which one is apportioned to three or four groups of the cellulose previously formulated3 these groups in condensed union together constitute an oxycellulose4 ,these views are in agreement with the experimental results obtained by ,faber and ,tollens 7p4 #ga74 ,they regard the oxycelluloses as compounds of 'celloxin' ,c#f;,h#h,o#f with #a-d mols4 unaltered cellulose2 and the former they particularly refer to as a lactone of glycuronic acid4 ,but on boiling with lime they obtain dioxybutyric and isosaccharinic acids2 both of which are not very obviously related to the compounds formulated by ,vignon4 ,we revert with preference to a definitely ketonic formula1 for which1 moreover1 some farther grounds remain to be mentioned4 ,in the systematic investigation of the nitric esters of the carbohydrates 7p4 #da7 ,will and ,lenze have definitely differentiated the ketoses from the aldoses1 as showing an internal condensation accompanying the ester reaction4 ,not only are the ,,oh groups taking part in the latter consequently less by two than in the corresponding aldoses1 but the nitrates show a much increased stability4 ,this would give a simple explanation of the well-known facts obtaining in the corresponding esters of the normal cellulose4 ,we may note here that an important item in the quantitative factors of the cellulose nitric ester reaction has been overlooked3 that is1 the yield calculated to the ,,no#c groups fixed4 ,the theoretical yields for the higher nitrates are ,yield p4ct4 ,n p4ct4 of cellulose of nitrate ,pentanitrate #afi #ab4g ,hexanitrate #ahc #ad4a ,from such statistics as are recorded the yields are not in accordance with the above4 ,there is a sensible deficiency4 ,thus ,will and ,lenze record a yield of #agj p4ct4 for a product with #ac4h p4ct4 ,n1 indicating a deficiency of about #aj p4ct4 ,as the by-products soluble in the acid mixture are extremely small1 the deficiency represents approximately the water split off by an internal reaction4 ,in this important point the celluloses behave as ketoses4 ,in the lignocelluloses the condensed constituents of the complex are of well-marked ketonic1 i4e4 quinonic1 type4 ,in 'nitrating' the lignocelluloses this phenomenon of internal condensation is much more pronounced 7see p4 #aca74 ,as the reaction is mainly confined to the cellulose of the fibre1 we have this additional evidence that the typical carbonyl is of ketonic function4 ,it is still an open question whether the cellulose constituents of the lignocelluloses are progressively condensed--with progress of 'lignification'--to the unsaturated or lignone groups4 ,there is much in favour of this view1 the evidence being dealt with in the first edition1 p4 #ahj4 ,the transition from a cellulose-ketone to the lignone-ketone involves a simple condensation without rearrangement2 from which we may argue back to the greater probability of the ketonic structure of the cellulose4 ,we must note1 however1 that the celluloses of the lignocelluloses are obtained as residues of various reactions1 and are not homogeneous4 ,they yield on boiling with condensing acids from #f to #i p4ct4 furfural4 ,it is usual to regard furfural as invariably produced from a pentose residue4 ,but this interpretation ignores a number of other probable sources of the aldehyde4 ,it must be particularly remembered that laevulose is readily condensed 7a7 to a methylhydroxyfurfural ,c#f;,h#a,o#f - #c;,h#b,o ,c#f;,h#f,o#c ,c#e7,,oh74,h#b47;,,ch#c7,o#b and 7b7 by ,h,br1 with further loss of ,,oh1 as under3 ,c#f;,h#ab,o#f - #d;,h#b,o ,h,br ,c#e;,h#c7;,,ch#b;,br7,o and generally the ketoses are distinguished from the aldoses by their susceptibility to condensation4 ,such condensation of laevulose has been effected by two methods3 7a7 by heating the concentrated aqueous solution with a small proportion of oxalic acid at #c atm4 pressure ,kiermayer1 ,chem4 ,ztg4 #ai1 #ajj2 7b7 by the action of hydrobromic acid 7gas7 in presence of anhydrous ether2 the actual compound obtained being the omega-brommethyl derivative ,fenton1 ,j4 ,chem4 ,soc4 #ahii1 #dbc4 ,this latter method is being extended to the investigation of typical celluloses1 and the results appear to confirm the view that cellulose may be of ketonic constitution4 ,the evidence which is obtainable from the synthetical side of the question rests of course mainly upon the physiological basis4 ,there are two points which may be noted4 ,since the researches of ,brown and ,morris 7,j4 ,chem4 ,soc4 #ahic1 #fjd7 have altered our views of the relationships of starch and cane sugar to the assimilation process1 and have placed the latter in the position of a primary product with starch as a species of overflow and reserve product1 it appears that laevulose must play an important part in the elaboration of cellulose4 ,moreover1 ,a4 ,j4 ,brown1 in studying the cellulosic cell-collecting envelope produced by the ,bacterium xylinum1 found that the proportion of this product to the carbohydrate disappearing under the action of the ferment was highest in the case of laevulose4 ,these facts being also taken into consideration there is a concurrence of suggestion that the typical ,,co group in the celluloses is of ketonic character4 ,that the typical cotton cellulose breaks down finally under the action of sulphuric acid to dextrose cannot be held to prove the aldehydic position of the carbonyls in the unit groups of the actual cellulose molecule or aggregate4 ,we again are confronted with the problem of the aggregate and as to how far it may affect the constitution of the unit groups4 ,that it modifies the functions or reactivity of the ultimate constituent groups we have seen from the study of the esters4 ,thus with the direct ester reactions the normal fibrous cellulose 7,c#f;,h#af,o#e7 yields a monoacetate1 dibenzoate1 and a trinitrate respectively under conditions which determine1 with the simple hexoses and anhydrides1 the maximum esterification1 i4e4 all the ,,oh groups reacting4 ,if the ,,oh groups are of variable function1 we should expect the ,,co groups a fortiori to be susceptible of change of function1 i4e4 of position within the unit groups4 ,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 determine4 ,the subjoined communication1 appearing after the completion of the ,,ms4 of the book1 and belonging to a date subsequent to the period intended to be covered1 is nevertheless included by reason of its exceptional importance and special bearing on the constitutional problem above discussed4 ,,the ,,action ,,of ,,hydrogen ,,bromine ,,on ,,carbohydrates4#d ,h4 ,j4 ,h4 ,,fenton and ,,mildred ,,gostling 7,j4 ,chem4 ,soc41 #aija1 #cfa74 ,the authors have shown in a previous communication 7,trans41 #ahih1 #gc1 #eed7 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 colour4#e ,it was further shown 7,trans41 #ahii1 #ge1 #dbc7 that this purple substance1 when neutralised with sodium carbonate and extracted with ether1 yields golden-yellow prisms of omega-brommethylfurfural1 ,,ch3,c4,,ch#b;,br ,o ,,ch3,c4,,cho4 ,this reaction is produced by laevulose1 sorbose1 cane sugar1 and inulin1 an intense colour being given within an hour or two4 ,dextrose1 maltose1 milk sugar1 galactose1 and the polyhydric alcohols give1 if anything1 only insignificant colours1 and these only after long standing4 ,the authors therefore suggested that the reaction might be employed as a means of distinguishing these classes of carbohydrates1 the rapid production of the purple colour being indicative of ketohexoses1 or of substances which produce these by hydrolysis4 ,by relying only on the production of the purple colour1 however1 a mistake might possibly arise1 owing to the fact that xylose gives a somewhat similar colour after standing for a few hours4 ,hence1 the observations should be confirmed by isolation of the crystals of brommethylfurfural4 ,no trace of this substance is obtained from the xylose product4 ,in order to identify the substance1 the ether extract1 after neutralisation1 is allowed to evaporate to a syrup1 and crystallisation promoted either by rubbing with a glass rod1 or by the more certain and highly characteristic method of 'sowing' with the most minute trace of omega-brommethylfurfural1 when crystals are almost instantly formed4 ,these are recrystallised from ether1 or a mixture of ether and light petroleum1 and further identified by the melting-point 7#ei4e-fj4e deg471 and1 if considered desirable1 by estimation of the bromine4 ,it is now found1 so reactive is the bromine atom in this compound1 that the estimation may be accurately made by titration with silver nitrate according to ,volhard's process1 the crystals for this purpose being dissolved in dilute alcohol3 #j4aigj gram required #aj4e c4c4 ,n_/#aj ,ag,n,o#c4 ,br #db4fc p4ct41 calculated #db4cb p4ct4 ,this method of applying hydrogen bromide in ethereal solution is1 of course1 unsuitable for investigations where a higher temperature has to be employed1 or where long standing is necessary1 since1 under such circumstances1 the ether itself is attacked4 ,wishing to make investigations under these conditions1 the authors have tried several solvents1 and1 at present1 find that chloroform is best suited to the purpose4 ,in each of the following experiments1 #aj grms4 of the substance were covered with #bej c4c4 of chloroform which had been saturated at #j deg4 with dry hydrogen bromide4 ,the mixture was contained in an accurately stoppered bottle1 firmly secured with an iron clamp1 and heated in a water-bath to about the boiling temperature for two hours4 ,after standing for several hours1 the mixture was treated with sodium carbonate 7first anhydrous solid1 and afterwards a few drops of strong solution71 filtered1 and the solution dried over calcium chloride4 ,most of the chloroform was then distilled off1 and the remaining solution allowed to evaporate to a thick syrup in a weighed dish4 ,the product was then tested for omega-brommethylfurfural by 'sowing' with the most minute trace of the substance1 as described above4 ,it was then warmed on a water-oven1 kept in a vacuum desiccator over solid paraffin1 and the weight estimated4 ,when necessary1 the product was recrystallised from ether1 and further identified by the tests mentioned4 ,the following results were obtained3 ,weight of crude residue4 ,swedish filter paper #c4j crystallised at once by 'sowing4' ,ordinary cotton #c4c ,mercerised cotton #b4a ,straw cellulose#f #b4c ,laevulose #b4b ,inulin #a4c ,potato starch #j4cg ,cane sugar #j4he ,dextrose #j4cc uncrystallisable4 ,milk sugar #j4cg ,glycogen #j4cd ,galactose #j4cd ,the products from dextrose1 milk sugar1 and galactose absolutely refused to crystallise even when extracted with ether and again evaporated1 or by 'sowing1' stirring1 c4 ,the glycogen product deposited a very small amount of crystalline matter on standing1 but the quantity was too minute for examination2 moreover1 it refused altogether to crystallise in contact with the aldehyde4 ,it may fairly be stated1 therefore1 that these last four substances give absolutely negative results as regards the formation of omega-brommethylfurfural2 if any is formed1 its quantity is altogether too small to be detected4 ,the specimen of starch examined was freshly prepared from potato1 and purified by digestion for twenty-four hours each with ,n_/#aj ,,koh1 ,n_/#d ,h,cl1 and strong alcohol2 it was then washed with water and allowed to dry in the air4 ,it will be seen that this substance gave a positive result1 but that the yield was extremely small1 and might yet be due to impurity4 ,considering the importance of the behaviour of starch1 for the purpose of drawing general conclusions from these observations1 it was thought advisable to make further experiments with specimens which could be relied upon1 and also to investigate the behaviour of dextrin4 ,this the authors have been enabled to do upon a series of specimens specially prepared by ,c4 ,o',sullivan1 and thus described by him3 #a4 ,rice starch1 specially purified by the permanganate method4 #b4 ,wheat starch #c4 ,oat starch1 contains traces of oil1 washed with dilute ,,koh and dilute ,h,cl4 #d4 ,pea starch1 first crop1 washed with alkali1 acid 7,h,cl71 and strong alcohol4 #e4 ,natural dextrin1 ,d #c4hg1 alpha,d #aid4g2 ,k #j4ie1 7c #b4fbh74 #f4 alpha-,dextrin1 ,c equation purified without fermentation1 #cj precipitations with alcohol 7,trans41 #ahgi1 #ce1 #ggb74 ,the examination of these specimens was conducted on a smaller scale1 but under the same conditions as before1 one gram of the substance being treated with #ab4e c4c4 of the saturated chloroform solution and heated in sealed tubes for two hours as above4 ,the results were as follows3 ,weight of crude residue4 #a4 ,rice starch #j4jdf crystallised at once by 'sowing4' #b4 ,wheat starch #j4jdd #c4 ,oat starch #j4jdi #d4 ,pea starch #j4jfd #e4 ,natural dextrin #j4jhh #f4 alpha-,dextrin #j4jee ,the results may therefore be summarised as follows3--,treated under these particular conditions all forms of cellulose give large yields of omega-brommethylfurfural1 some varieties giving as much as #cc per cent4 ,laevulose1 inulin1 and cane sugar give yields varying from #bb to #h4e per cent42 various starches give small yields 7average about #d4e per cent472 and dextrins #e to #h per cent41 whereas dextrose1 milk sugar1 and galactose give1 apparently1 none at all4 ,the yields represent the solid crystalline residue2 this when purified by recrystallisation gives1 probably1 about three-quarters of its weight of pure crystals4 7,in the case of dextrose1 c41 the yields represent the weight of syrup47 ,these numbers1 however1 by no means represent the maximum yields obtainable1 owing to the comparatively slight solubility of hydrogen bromide in chloroform4 ,the process was conducted in the above manner only for the sake of uniform comparison4 ,the ether method previously described gives much larger yields2 for example1 #ab grms4 of inulin treated with only #fj c4c4 of the saturated ether gave #b4e grms4 of substance4 ,for the purpose of obtaining larger yields1 other methods are being investigated4 ,the facts recorded above1 taken in conjunction with those given in our previous communications1 appear to point definitely to the following general conclusions4 ,first1 that the various forms of cellulose contain one or more groups or nuclei identical with that contained in laevulose1 and that such groups constitute the main or essential part of the molecule4 ,secondly1 that similar groupings are contained in starches and dextrins1 but that the proportion of such groupings represents a relatively small part of the whole structure4 ,the nature of this grouping is1 according to the generally accepted constitution of laevulose1 the six-carbon chain with a ketonic group3 ,c4,c4,c4,c4,c4,c 4 ,o ,but the results might1 on the other hand1 be considered indicative of the anhydride or 'lacton' grouping1 which ,tollens suggested for laevulose3 ,c4,c4,c4,c4,c4,c _/ _/ 4 ,o ,the latter very simply represents the formation of omega-brommethylfurfural from laevulose1#g ------,o----- ,h ,h ,,oh4,c-----,c---,c---,c--,c-----,,ch#b4 ,,oh ,h#b ,,oh ,,oh ,,oh ,h giving ,h ,h ,,hc4,c3,c4,c3,c4,,ch#b;,br _/ 1 ,o _/ ,o although by a little further 'manipulation' of the symbols the change could1 of course1 be represented by reference to the ketonic formula4 ,the ,ketonic ,constitution of ,cellulose4 ,c4 ,f4 ,,cross and ,e4 ,j4 ,,bevan 7,j4 ,chem4 ,soc41 #aija1 #cff74 ,in this paper the authors discuss more fully the theoretical bearings of the observations of ,fenton and ,gostling1 the two papers being simultaneously communicated4 ,the paper is mainly devoted to a review of the antecedent evidence1 chemical and physiological1 and to a general summing up in favour of the view that cellulose is a polyketose 7anhydride74 99 99 99 99 99 7p4 #gi7 ,composition of the ,seed ,hair of ,eriodendron 7,anf47--,some interest attaches to the results of an analytical investigation which we have made of this silky floss4 ,there is little doubt that cotton is entirely exceptional in its characteristics3 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 resistance4 ,the following numbers determined for the kapok differentiate it widely from the cottons3 ,ash1 #a4c2 moisture1 #i4c2 alkaline hydrolysis 7loss7 7a7 #af4g1 7b7 #ba4h4 ,cellulose1 by chlorination1 c41 #ga4a4 ,in reacting with chloride it shows the presence of unsaturated groups1 similar to the lignone of the woods4 ,this was confirmed by a well-marked reaction with ferric ferricyanide with increase of weight due to the fixation of the blue cyanide4 ,but the most characteristic feature is the high yield of furfural on boiling with condensing acids4 ,the following numbers were determined3 ,total furfural from original fibre #ad4hd ,in residue from alkali hydrolysis #aa4e ,in cellulose isolated by ,cl method #aj4d ,treated with sulphuric acids of concentration1 7a7 #ib4a grs4 ,h#b,,so#d per #ajj c4c41 7b7 #aje4h grs4 per #ajj c4c41 the fibres dissolve1 and diluted immediately after complete solution it was resolved into 7a7 7b7 ,reprecipitated fraction #fh4g #dc4g ,soluble fraction yielding furfural #ac4b #ad4c ,by these observations it is established that the furfuroids are of the cellulose type and behave very much as the furfuroids of the cereal celluloses4 ,this group of seed hairs invites exhaustive investigation4 ,the furfuroid constituents are easily isolated1 and as they constitute at least one-third of the fibre substance it is especially from this point of view that they invite study4 ,,recherches ,,sur ,l',,oxycellulose4 ,l4 ,,vignon4 ,resume of investigations 7#ahih-aijj7 of ,oxycellulose1 published as a brochure 7,rey1 ,lyon1 #aijj74 7a7 ,a typical oxycellulose prepared from cotton cellulose by the action of ,h,cl,o#c 7,h,cl ,k,cl,o#c7 in dilute solution at #ajj deg4 for one hour gave the following numbers3 ,c ,h ,o ,elementary composition #dc4ee #f4jc #ej4db ,oxycellulose ,original cellulose ,analysis by ,lange's method ,soluble in ,,koh 7at #ahj deg47 #hg4f #ab4j ,insoluble in ,,koh 7at #ahj deg47 #ab4d #hh4j ,oxycellulose ,original cellulose ,heat of combustion #dabd-dacc #daij-dbbd ,heat evolved in contact with #ej times wt4 normal ,,koh per #ajj grms4 #a4c cal4 #j4gd cal4 ,oxycellulose ,cellulose ,absorption of colouring ,saffranine #j4g #j4j matters at #ajj deg4 per #ajj grms4 ,methylene blue #j4f #j4b 7b7 ,yield of furfural from cellulose1 oxy- and hydro-cellulose4--,from the hydrocelluloses variously prepared the author obtains #j4h p4ct4 furfural2 from bleached cotton #a4h p4ct42 and from the oxycelluloses variously prepared #b4j-c4e p4ct4 ,the 'furfuroid' is relatively more soluble in alkaline solutions 7,,koh7 in the cold4 ,the insoluble residue is a normal cellulose4 7c7 ,nitrates of cellulose1 oxy- and hydro-cellulose4--,treated with the usual acid mixture 7,h#b,,so#d #c p41 ,,hno#c #a p47 under conditions for maximum action1 the resulting esters showed uniformly a fixation of #aa4j ,,no#b groups per unit mol4 of ,c#bd4 ,the oxycellulose nitrate was treated directly with dilute solution of potassium hydrate in the cold4 ,from the products of decomposition the author obtained the osazone of hydroxypyruvic acid ,will1 ,ber4 #bd1 #djj4 7d7 ,osazones of the oxycelluloses4--,oxycelluloses prepared by various methods are found to fix varying proportions of phenylhydrazine 7residue71 viz4 from #c4d-h4e p4ct4 of the cellulose derivative reacting1 corresponding with1 i4e4 calculated from1 the nitrogen determined in the products 7#j4hg-b4b p4ct474 ,the reaction is assumed to be that of osazone formation4 ,the author has also established a relation between the phenylhydrazine fixed and the furfural which the substance yields on boiling with condensing acids4 ,this is illustrated by the subjoined series of numbers3 ,phenylhydrazine ,furfural ,fixed p4ct4 formed p4ct4 ,cotton 7bleached7 #a4gc #a4fj ,oxycellulose 7,h,cl,o#c7 #g4id #b4ji 7,h,cl,o7 #c4cg #a4gi 7,cr,o#c7 7#a7 #g4jc #c4jj 7,cr,o#c7 7#b7 #g4ga #c4ji 7,cr,o#c7 7#c7 #h4dh #c4ej 7e7 ,constitution of cellulose and oxycellulose4--,the results of these investigations are generalised as regards cellulose 7,c#f7 by the constitutional formula ,,ch--,,ch#b _/ 7,,choh7#c ,o ,,ch--,o 4 ,the oxycelluloses contain the characteristic group ,,coh _/ 7,,choh7#c ,,ch--,,co _/ ,o in union with varying proportions of residual cellulose4 ,,quantitative ,,separation ,,of ,,cellulose-,,like ,,carbohydrates ,,in ,,vegetable ,,substances4 ,,wilhelm ,,hoffmeister 7,landw4 ,versuchs-,stat41 #ahig1 #dh1 #dja-daa74 ,to separate the hemicelluloses1 celluloses1 and the constituents of lignin without essential change1 the substance1 after being freed from fat1 is extracted with dilute hydrochloric acid and ammonia1 and the residue frequently agitated for a day or two with #e-f p4ct4 caustic soda solution4 ,it is then diluted1 the extract poured off1 neutralised with hydrochloric acid1 treated with sufficient alcohol1 and the hemicellulose filtered1 dried1 and weighed4 ,the residue from the soda extract is washed on a filter with hot water1 and extracted with ,schweizer's reagent4 ,when the final residue 7lignin7 is subjected to prolonged extraction with boiling dilute ammonia 7a suitable apparatus is described1 with sketch7 until the ammonia is no longer coloured1 a residue is obtained which mostly dissolves in ,schweizer's reagent1 and on repeating the process the residue is found to consist largely of mineral matter4 ,the dissolved cellulose-like substances often contain considerable amounts of pentosanes4 ,according to the nature of the substance1 the extraction with ammonia may take weeks1 or months1 or even longer2 the ammonia extracts of hard woods 7as lignum vitae7 and of cork are dark brown1 and give an odour of vanilla when evaporated down4 ,the residues1 which are insoluble in water1 but redissolve in ammonia1 have the properties of humic acids4 ,other vegetable substances1 when extracted1 yielded1 besides humic acids1 a compound1 ,c#f;,h#g,o#b1 soluble in alcohol and chloroform1 but insoluble in water1 ether1 and benzene2 preparations from different sources melted between #bjj deg4 and #baj deg44 ,,footnotes3 #d ,the original paper is reproduced with slight alterations4 #e ,this purple colour would appear to be due to a highly dissociable compound of omega-brommethylfurfural with hydrogen bromide4 ,the aldehyde gives yellow or colourless solutions in various solvents1 which are turned purple by a sufficient excess of hydrogen bromide4 ,dilution1 or addition of water1 at once discharges the colour4 #f ,other forms of cellulose were also examined--for example1 pinewood cellulose--and the substances separated from solution as thiocarbonate 7powder and film74 ,all of these gave good yields of omega-brommethylfurfural4 #g ,the change is empirically represented as ,c#f;,h#ab,o#f ,h,br - #d;,h#b,o ,c#f;,h#e,o#b;,br4 ,,section ,,iv4 ,,cellulose ,,group1 ,,including ,,hemicelluloses ,,and ,,tissue ,,constituents ,,of ,,fungi ,,versuche ,,zur ,,bestimmung ,,des ,,gehalts ,,einiger ,,pflanzen ,,und ,,pflanzenteile ,,an ,,zellwandbestandteilen ,,an ,,hemicellulosen ,,und ,,an ,,cellulose4 ,a4 ,,kleiber 7,landw4 ,vers4-,stat41 #aijj1 #ed1 #afa74 ,,on ,,the ,,determination ,,of ,,cell-,,wall ,,constituents1 ,,hemicelluloses ,,and ,,cellulose ,,in ,,plants ,,and ,,plant ,,tissues4 ,in a preliminary discussion the author critically compares the results of various of the methods in practice for the isolation and estimation of cellulose4 ,the method of ,f4 ,schulze digestion with dil4 ,,hno#c with ,k,cl,o#c--ad days1 and afterwards treating the product with ammonia1 c4 is stated to be the 'best known' 7presumably the most widely practised72 ,w4 ,hoffmeister's modification of the above1 in which the nitric acid is replaced by hydrochloric acid 7#aj p4ct4 ,h,cl7 is next noted as reducing the time of digestion from #ad days to #a-b days1 and giving in many cases higher yields of cellulose4 ,the methods of treating with the halogens1 viz4 bromine water 7,h4 ,mueller71 chlorine gas 7,cross and ,bevan71 and chlorine water1 are dismissed with a bare mention1 apparently on the basis of the conclusions of ,suringar and ,tollens 7q4v474 ,the method of ,lange1 the basis of which is a 'fusion' with alkaline hydrates at #ahj deg41 and the modified method of ,gabriel1 in which the 'fusion' with alkali takes place in presence of glycerin1 are favourably mentioned4 ,these methods were applied to a range of widely different raw materials to determine1 by critical examination of the products1 both as regards yield and composition1 what title these latter have to be regarded as 'pure cellulose4' ,this portion of the investigation is an extension of that of ,suringar and ,tollens1 these latter confining themselves to celluloses of the 'normal' groups1 i4e4 textile and paper-making celluloses4 ,the present communication is a study of the tissue and cell-wall constituents of the following types3-- #a4 ,green plants of false oat grass 7,arrhenatherium1 ,e474 #b4 ,green plants of lucerne 7,medicago sativa74 #c4 ,leaves of the ash 7,fraxinus74 #d4 ,leaves of the walnut 7,juglans74 #e4 ,roots of the purple melic grass 7,molinia caerulea74 #f4 ,roots of dandelion 7,taraxacum officinale74 #g4 ,roots of comfrey4 #h4 ,coffee berries4 #i4 ,wheat bran4 ,these raw materials were treated for the quantitative estimation of cellulose by the method of ,lange 7b71 ,hoffmeister 7c71 and ,schulze 7d71 and the numbers obtained are referred for comparison to the corresponding yields of 'crude fibre' 7,rohfaser7 by the standard method 7a74 ,as a first result the author dismisses ,lange's method as hopeless3 the results in successive determinations on the same materials showing variations up to #fj p4ct4 ,the results by c and d are satisfactorily concordant3 the yields of cellulose are higher than of 'crude fibre4' ,this is obviously due to the conservation of 'hemicellulose' products1 which are hydrolysed and dissolved in the treatments for 'crude fibre' estimation4 ,a modified method was next investigated1 in which the process of digestion with acid chloroxy- compounds 7c and d7 was preceded by a treatment with boiling dilute acid4 ,the yields of cellulose by this method 7e7 are more uniform1 and show less divergence from the numbers for 'crude fibre4' ,the author's numerical results are given in a series of tables which include determinations of proteids and ash constituents1 and the corresponding deductions from the crude weight in calculating to 'pure cellulose4' ,the subjoined extract will illustrate these main lines of investigation4 ,crude ,fibre ,pure ,cellulose ,raw ,material ,weende ,hoffmeister ,hoffmeister1 ,method4 ,method4 modified by 7a7 7c7 ,author4 7e7 ,oat grass #cj4ce #cd4i #ca4e ,lucerne #be4be #bh4g #bj4e ,leaves of ash #ac4je #ae4d #ac4h ,roots of melic #ba4fj #bi4a #ba4d ,coffee beans #ah4cj #ce4a #bc4c ,bran #h4b #ai4c #i4c ,the final conclusion drawn from these results is that the method of ,hoffmeister yields a product containing variable proportions of hemicelluloses4 ,these are eliminated by boiling with a dilute acid 7#a4be p4ct4 ,h#b,,so#d71 which treatment may be carried out on the raw material--i4e4 before exposure to the acid chlorate1 or on the crude cellulose as ordinarily isolated4 ,determination of ,tissue-constituents4--,by the regulated action of certain solvents applied in succession1 it appears that such constituents of the plant-complex can be removed as have no organic connection with the cellular skeleton3 the residue from such treatments1 conversely1 fairly represents the true tissue-constituents4 ,the author employs the method of digestion with cold dilute alkaline solutions 7#j4ae to #j4e p4ct4 ,na,o,h71 followed by exhaustive washing with cold and hot water1 afterwards with cold and hot alcohol1 and finally with ether4 ,the residue is dried and weighed as crude product4 ,when necessary1 the proportions of ash and proteid constituents are determined and deducted from the 'crude product' which1 thus corrected1 may be taken as representing the 'carbohydrate' tissue constituents4 ,determination of ,hemicelluloses4--,by the process of boiling with dilute acids 7#a4be p4ct4 ,h#b,,so#d7 the hemicelluloses are attacked--i4e4 hydrolysed and dissolved4 ,the action of the acid though selective is1 of course1 not exclusively confined to these colloidal carbohydrates4 ,the proteid and mineral constituents are attacked more or less1 and the celluloses themselves are not entirely resistant to the action4 ,the loss due to the latter may be neglected1 but in calculating the hemicellulose constants from the gross loss the proteids and mineral constituents require to be taken into account in the usual way4 ,,quantitative ,,separation ,,of ,,hemicellulose1 ,,cellulose1 ,,and ,,lignin4 ,,presence ,,of ,,pentosanes ,,in ,,these ,,substances4 ,,wilhelm ,,hoffmeister 7,landw4 ,versuchs-,stat1 #ahih1 #ej1 #cdg-cfb74 7p4 #hh7 ,the separation of the cellulose-like carbohydrates of sunflower husks is described4 ,in order to ascertain the effect of dilute ammonia on the cellulose substances of lignin1 a dried #e p4ct4 caustic soda extract was extracted successively with #a1 #b1 #c1 and #d p4ct4 sodium hydroxide solution4 ,five grams of the #b p4ct4 extract were then subjected to the action of ammonia vapour2 the cellulose did not completely dissolve in six weeks4 ,cellulose insoluble in caustic soda 7#cb grms47 was next extracted with ammonia1 in a similar manner1 for #aj days1 dried1 and weighed4 #cj4df grms4 remained1 which1 when treated with #e p4ct4 aqueous caustic soda1 yielded #j4if grm4 7#c per cent47 of hemicellulose4 ,when cellulose is dissolved in ,schweizer's solution1 the residue is1 by repeated extraction with aqueous sodium hydroxide1 completely converted into the soluble form4 ,on evaporating the ammonia from the ,schweizer's extract1 at the ordinary temperature and on a water-bath respectively1 different amounts of cellulose are obtained2 more hemicellulose is obtained1 by caustic soda1 from the heated solution than from that which was not heated4 ,in this operation the pentosanes are more influenced than the hexosanes2 pentosanes are not always readily dissolved by caustic soda1 and hexosanes are frequently more or less readily dissolved4 ,both occur in lignin1 and are then undoubtedly indigestible4 ,these points have to be considered in judging the digestibility of these carbohydrates4 ,a comparison of analyses of clover1 at different periods1 in the first and second years of growth1 shows that both cellulose 7,schweizer's extract7 and lignin increase in both constituents4 ,in the second year the lignin alone increased to the end2 the cellulose decreased at the end of ,june4 ,in the first year it seemed an absolutely as well as relatively greater amount of cellulose1 and lignin was produced in the second year2 this1 however1 requires confirmation4 ,the amount of pentosanes in the ,schweizer extract was relatively greater in the second than in the first year1 but decreased in the lignin more in the second year than in the first3 this result is also given with reserve4 ,,die ,,constitution ,,der ,,cellulosen ,,der ,,cerealien4 ,c4 ,f4 ,,cross1 ,e4 ,j4 ,,bevan1 and ,c4 ,,smith 7,berl4 ,ber41 #ahif1 #adeg74 ,,the ,,constitution ,,of ,,the ,,cereal ,,celluloses4 7p4 #hd7 ,straw cellulose is resolved by two methods of acid hydrolysis into a soluble furfural-yielding fraction1 and an insoluble fraction closely resembling the normal cellulose4 7a7 ,the cellulose is dissolved in sulphuric acids of concentration1 ,h#b,,so#d4b;,h#b,o1 ,h#b,,so#d4c;,h#b,o4 ,as soon as solution is complete1 the acid is diluted4 ,a precipitate of cellulose hydrate 7#fj-gj p4ct47 is obtained1 and the filtered solution contains #ij-ie p4ct4 of the furfuroids of the original cellulose4 ,the process is difficult to control1 however1 in mass1 and to obtain the latter in larger quantity the cellulose 7b7 is digested with six times its weight of #a p4ct4 ,h#b,,so#d at #c atm4 pressure1 the products of the action being 7#a7 a disintegrated cellulose retaining only a small fraction 7#a_/ab7 of the furfural-yielding groups1 and 7#b7 a slightly coloured solution of the hydrolised furfuroids4 ,an investigation of the latter gave the following results3 ,by oxidation with nitric acid no saccharic acid was obtained2 showing the absence of dextrose4 ,the numbers for cupric reduction were in excess of those obtained with the hexoses4 ,the yield of ozazone was high1 viz4 #cj to #dj p4ct4 of the weight of the carbohydrate in solution4 ,on fractionating1 the melting-points of the fractions were found to lie between #adf deg4 and #aec deg44 ,ultimate analysis gave numbers for ,c1 ,h1 and ,n identical with those of a pentosazone4 ,the product of hydrolysis appears1 therefore1 to be xylose or a closely related derivative4 ,all attempts to obtain a crystallisation of xylose from the solution neutralised 7,ba,c,o#c71 filtered1 and evaporated1 failed4 ,the reaction with phloroglucol and ,h,cl1 moreover1 was not the characteristic red of the pentoses1 but a deep violet4 ,the product was then isolated as a dry residue by evaporating further and drying at #aje deg44 ,elementary analysis gave the numbers ,c #dd4b1 #dd4e1 and ,h #f4g1 #f4c4 ,determinations of furfural gave #ci4e to #db4e p4ct4 ,on treating the original solution with hydrogen peroxide1 and warming1 oxidation set in1 with evolution of ,,co#b4 ,this was estimated 7by absorption71 giving numbers for ,,co#b1 #ai4e1 #bj4e1 #bj4a p4ct4 of the substance4 ,the sum of these quantitative data is inconsistent with a pentose or pentosane formula2 it is more satisfactorily expressed by the empirical formula ,o _/ ,c#e;,h#h,o#c ,,ch#b1 _/ ,o which represents a pentose monoformal4 ,attempts to synthesise a compound of this formula have been so far without success4 ,,ueber ,,einige ,,chemische ,v,o,r,g,ae,n,g,e ,,in ,,der ,,gerstenpflanze4 ,c4 ,f4 ,,cross1 ,e4 ,j4 ,,bevan1 and ,c4 ,,smith 7,berl4 ,ber41 #ahie1 #bfjd74 ,,the ,,chemical ,,life-,,history ,,of ,,the ,,barley ,,plant4 7p4 #hd7 ,owing to the presence of 'furfuroids' in large proportion as constituents of the tissues of the stems of cereals1 these plants afford convenient material for studying the problem of the constitution of the tissue-furfuroids1 as well as their relationship to the normal celluloses4 ,the growing barley plant was investigated at successive periods of growth4 ,yield of furfural was estimated on the whole plant and on the residue from a treatment with alkaline and acid solvents in the cold such as to remove all cell contents4 ,this residue is described as 'permanent tissue4' ,the observations were carried out through two growing seasons--#ahid-e--which were very different in character1 the former being rainy with low temperature1 the latter being abnormal in the opposite direction1 i4e4 minimum rainfall and maximum sunshine4 ,the barley selected for observation was that of two experimental plots of the ,royal ,agricultural ,society's farm1 one 7,no4 #a7 remaining permanently unmanured1 and showing minimum yield1 the other 7,no4 #f7 receiving such fertilising treatment as to give maximum yields4 ,the numerical results are given in the annexed tables3 ,table ,headings3 ,a3 ,date ,b3 ,age of ,crop ,c3 ,plot ,d3 ,dry ,weight ,e3 ,furfural p4ct4 of dry weight 7a7 ,f3 ,permanent tissue p4ct4 dry weight ,g3 ,furfural from permanent tissue ,h3 ,p4ct4 of tissue ,i3 ,p4ct4 of entire plant ,j3 ,ratio a 3 c ,,barley ,,crop1 ,,woburn1 #ahid4 ,g ,a ,b ,c ,d ,e ,f ,h ,i ,j ,may #g #f weeks #a #ai4d #g4j #ec4d #ab4g #f4h #a4jc 3 #a #f #ad4g #g4j #ee4i #aj4c #e4g #a4bc 3 #a ,june #d #aj weeks #a #ag4f #g4g #eb4i #aa4f #f4a #a4bf 3 #a #f #ac4e #h4a #eh4e #ac4d #g4h #a4jd 3 #a ,july #aj #ae weeks #a #db4j #i4j #fe4g #i4h #f4d #a4dj 3 #a #f #cb4i #aj4f #fe4g #ab4e #h4b #a4cj 3 #a ,cut #ba weeks #a #fd4j #aa4i #gj4j #ad4e #aj4a #a4ah 3 #a ,aug4 #ba #f #fd4f #ac4d #gj4e #ae4j #aj4f #a4bf 3 #a ,carried #bb weeks #a #hd4j #ab4g #ge4j #af4e #ab4d #a4jb 3 #a ,aug4 #ca #f #hf4d #ab4d #gh4d #ae4a #aa4h #a4je 3 #a ,,barley ,,crop1 ,,woburn1 #ahie4 ,may #ae #g weeks #a #bj4f #f4f #ec4i #aj4b #e4e #a4bj 3 #a #f #ag4h #e4h #ef4g #i4f #e4d #a4jg 3 #a ,june #ah #ab weeks #a #cd4f #h4j #ch4b #ad4g #e4f #a4db 3 #a #f #cc4d #g4f #dd4e #ae4j #f4g #a4ad 3 #a ,july #af #af weeks #a #eb4h #ab4a #ee4f #af4c #i4a #a4cc 3 #a #f #ed4d #aj4f #df4b #ai4a #h4h #a4bj 3 #a ,aug4 #af #bj weeks #a #ff4h #i4b #di4a #ag4j #h4c #a4aj 3 #a #f #fe4j #i4h #di4h #ai4a #i4d #a4jd 3 #a ,sept4 #c #bb weeks #a #hd4c #aj4d #de4g #ag4f #h4j #a4ca 3 #a #f #hf4c #aj4b #de4c #ag4c #g4h #a4cj 3 #a ,the variations exhibited by these numbers are significant4 ,it is clear1 on the other hand1 that the assimilation of the furfuroids does not vary in any important way with variations in conditions of atmosphere and soil nutrition4 ,they are essentially tissue-constituents1 and only at the flowering period is there any accumulation of these compounds in the alkali-soluble form4 ,it has been previously shown 7ibid4 #bg1 #ajfa7 that the proportion of furfuroids in the straw-celluloses of the paper-maker differs but little from that of the original straws4 ,for the isolation of the celluloses the straws are treated by a severe process of alkaline hydrolysis1 to which1 therefore1 the furfuroid groups offer equal resistance with the normal hexose groups with which they are associated in the complex4 ,the furfuroids of the cereal straws are therefore not pentosanes4 ,they are original products of assimilation1 and not subject to secondary changes after elaboration such as to alter either their constitution or their relationship to the normal hexose groups of the tissue-complex4 7#a7 ,,constitution ,,of ,,the ,,cereal ,,celluloses 7,chem4 ,soc4 ,j4 #ahif1 #hjd74 7#b7 ,,the ,,carbohydrates ,,of ,,barley ,,straw 7,chem4 ,soc4 ,j4 #ahif1 #afjd74 7#c7 ,,the ,,carbohydrates ,,of ,,the ,,cereal ,,straws 7,chem4 ,soc4 ,j4 #ahig1 #ajja74 7#d7 ,,the ,,carbohydrates ,,of ,,barley ,,straw 7,chem4 ,soc4 ,j4 #ahih1 #dei74 ,c4 ,f4 ,,cross1 ,e4 ,j4 ,,bevan1 and ,,claud ,,smith4 ,these are a series of investigations mainly devoted to establishing the identity of the furfural-yielding group which is a characteristic constituent4 ,this 'furfuroid' while equally resistant to alkalis as the normal cellulose group with which it is associated1 is selectively hydrolysed by acids4 ,thus straw cellulose dissolves in sulphuric acids of concentration ,h#b,,so#d4b;,h#b,o - ,h#b,,so#d4c;,h#b,o1 and on diluting the normal cellulose is precipitated as a hydrate1 and the furfuroid remains in solution4 ,but this sharp separation is difficult to control in mass4 ,by heating with a very dilute acid 7#a p4ct4 ,h#b,,so#d7 the conditions are more easily controlled1 the most satisfactory results being obtained with #ae mins4 heating at #c atm4 pressure4 7#a7 ,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 determined3--,total dissolved solids1 #bh4j p4ct4 of original 'grains'2 furfural1 #ci4e p4ct4 of total dissolved solids1 as compared with #ab4e p4ct4 of total original grains2 cupric reduction 7calc4 to total solids71 #aaj 7dextrose #ajj7 osazone2 yield in #c p4ct4 solution1 #ce p4ct4 of weight of total solids4 ,pentosazone ,analysis ,n #ag4a #ag4c #ag4jg ,c #fb4e #fb4c #fb4b ,h #f4d #f4e #f4a ,melting-point #adf deg4-#aec deg4 ,from these numbers it is seen that of the total furfuroids of the original 'grains' #hd p4ct4 are thus obtained in solution in the fully hydrolysed form1 which is that of a pentose or pentose derivative4 ,it was1 however1 found impossible to obtain any crystallisation from the neutralised 7,ba,c,o#c7 and concentrated solution1 the syrup being kept for some weeks in a desiccator4 ,it was noted at the same time that the colour reaction of the original solution with phloroglucol and hydrochloric acid was a deep violet1 in contradistinction to the characteristic red of the pentoses4 ,on oxidation with hydrogen peroxide1 in the proportion of #a mol4 ,h#b,o#b to #a mol4 of the carbohydrate in solution1 carbonic anhydride was formed in quantity #bj4j p4ct4 of the latter4 ,fermentation 7yeast7 experiments also showed a divergence from the resistant behaviour of the pentoses1 a considerable proportion of the furfuroid disappearing in a normal fermentation4 7#b7 ,the quantitative methods above described were employed in investigating the barley plant at different stages of its growth4 ,the green plant was extracted with alcohol1 the residue freed from alcohol and subjected to acid hydrolysis4 ,the hydrolysed extract was neutralised and fermented4 ,in the early stages of growth the furfuroids were completely fermented1 i4e4 disappeared in the fermentation4 ,in the later stages this proportion fell to #ej p4ct4 ,in the earlier stages1 moreover1 the normal hexose constituents of the permanent tissue were hydrolysed in large proportion by the acid1 whereas in the matured straw the hydrolysis is chiefly confined to the furfuroids4 ,in the early stages also the permanent tissue yields an extract with relatively low cupric reduction1 showing that the carbohydrates are dissolved by the acid in a more complex molecular condition4 ,these observations confirm the view that the furfuroids take origin in a hexose-pentose series of transformations4 ,the proportion of furfuroid groups to total carbohydrates varies but little1 viz4 from #a_/c in the early stages to a maximum of #a_/d at the flowering period4 ,at this period the differentiation of the groups begins to be marked4 ,taking all the facts of 7#a7 and 7#b71 they are not inconsistent with the hypothesis of an internal transformation of a hexose to a pentose-monoformal4 ,such a change of position and function of oxygen from ,,oh to ,,co within the group --,,ch4,,oh-- is a species of internal oxidation which reverses the reduction of formaldehyde groups in synthesising to sugars1 and appears therefore of probable occurrence4 ,these constitutional problems are followed up in 7#c7 by the indirect method of differentiating the relationships of these furfuroids to yeast fermentation1 from those of the pentoses4 ,straw and esparto celluloses are subjected to the processes of acid hydrolysis1 and the neutralised extracts fermented4 ,with high furfural numbers indicating that the furfuroids are the chief constituents of the extract1 there is an active fermentation with production of alcohol4 ,the cupric reduction falls in greater ratio to the original 7unfermented7 than the furfural4 ,observations on the pure pentoses--xylose and arabinose added to dextrose solutions1 and then exposed to yeast action--show that in a vigorous fermentation not unduly prolonged the pentoses are unaffected1 but that they do come within the influence of the yeast-cell when the latter is in a less vigorous condition1 and when the hexoses are not present in relatively large proportion4 7#d7 ,the observations on the growing plant were resumed with the view of artificially increasing the differentiation of the two main groups of carbohydrates4 ,from a portion of a barley crop the inflorescence was removed as soon as it appeared4 ,the crop was allowed to mature1 and a full comparison instituted between the products of normal and abnormal growth4 ,with a considerable difference in 'permanent tissue' 7#ac p4ct4 less7 and a still greater defect in cellulose 7#bd p4ct471 the constants for the furfuroids in relation to total carbohydrates were unaffected by the arrested development4 ,this was also true of the behaviour of the hydrolysed extracts 7acid processes7 to yeast fermentation4 7#e7 ,the extract obtained from the brewers' grains by the process described in 7#b7 was investigated in relation to animal digestion4 ,it has been now generally established that the furfuroids as constituents of fodder plants are digested and assimilated in large proportion in passing through animal digestive tracts1 and in this respect behave differently from the pentoses4 ,the furfuroids being obtained1 as described1 in a fully hydrolysed condition 7monoses7 the digestion problem presented itself in a new aspect1 and was therefore attacked4 ,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 assimilated1 no pentoses1 moreover1 appearing in the urine4 ,generally we may sum up the present solution of the problem of the relationship of the furfuroids to plant assimilation and growth as follows3--,the pentoses are not produced as such in the process of assimilation2 but furfural-yielding carbohydrates are produced directly and in approximately constant ratio to the total carbohydrates2 they are mainly located in the permanent tissue2 in the secondary changes of dehydration1 c41 accompanying maturation they undergo such differentiation that they become readily separable by processes of acid hydrolysis from the more resistant normal celluloses2 but in relation to alkaline treatments they maintain their intimate union with the latter4 ,they are finally converted into pentoses by artificial treatments1 and into pentosanes in the plant1 with loss of #a ,c atom in an oxidised form4 ,the mechanism of this transformation of hexoses into pentoses is not cleared up4 ,it is independent of external conditions1 e4g4 fertilisation and atmospheric oxidations1 and is probably therefore a process of internal rearrangement of the character of an oxidation4 ,,zur ,,kenntniss ,,der ,,in ,,den ,,membranen ,,der ,,pilze ,,enthaltenen ,,bestandtheile4 ,e4 ,,winterstein 7,ztschr4 ,physiol4 ,chem41 #ahid1 #eba2 #ahie1 #acd74 ,,on ,,the ,,constituents ,,of ,,the ,,tissue ,,of ,,fungi4 7p4 #hg7 ,these two communications are a contribution of fundamental importance1 and may be regarded as placing the question of the composition of the celluloses of these lowest types on a basis of well-defined fact4 ,in the first place the author gives an exhaustive bibliography1 beginning with the researches of ,braconnot 7#ahaa71 who regarded the cellular tissue of these organisms as a specialised substance1 which he termed 'fungin4' ,payen rejects this view1 and regards the tissue1 fully purified by the action of solvents1 as a cellulose 7,c#f;,h#aj,o#e74 ,this view is successively supported by ,fromberg ,mulder1 ,allg4 ,phys4 ,chem41 ,braunschweig1 #ahea1 ,schlossberger and ,doepping ,annalen1 #eb1 #ajf1 and ,kaiser4 ,de ,bary1 on a review of the evidence1 adopts this view1 but1 as the purified substance fails to give the characteristic colour-reactions with iodine1 he uses the qualifying term 'pilzcellulose' ,morph4 u4 ,biol4 d4 ,pilze u4 ,flechten1 ,leipzig1 #ahhd4 ,c4 ,richter1 on the other hand1 shows that these reactions are merely a question of methods of purification or preparation ,sitzungsber4 ,acad4 ,wien1 #hb1 #a1 #did1 and considers that the tissue-substance is an ordinary cellulose1 with the ordinary reactions masked by the presence of impurities4 ,in regard to the lower types of fungoid growth1 such as yeast1 the results of investigators are more at variance4 ,the researches of ,salkowski 7p4 #aac7 leave little doubt1 however1 that the cell-membrane is of the cellulosic type4 ,the author's researches extend over a typical range of products obtained from ,boletus edulis1 ,agaricus campestris1 ,cantharellus cibarius1 ,morchella esculenta1 ,polyporus officinalis1 ,penicillium glaucum1 and certain undetermined species4 ,the method of purification consisted mainly in 7a7 exhaustive treatments with ether and boiling alcohol1 7b7 digestion with alkaline hydrate 7#a-b p4ct4 ,na,o,h7 in the cold1 7c7 acid hydrolysis 7#b-c p4ct4 ,h#b,,so#d7 at #ie deg4-#ajj deg41 followed by a chloroxidation treatment by the processes of ,schulze or ,hoffmeister1 and final alkaline hydrolysis4 ,the products1 i4e4 residues1 thus obtained were different in essential points from the celluloses isolated from the tissues of phanerogams similarly treated4 ,only in exceptional cases do they give blue reactions with iodine in presence of zinc chloride or sulphuric acid4 ,the colourations are brown to red4 ,they resist the action of cuprammonium solutions4 ,they are for the most part soluble in alkaline hydrate solution 7#e-aj p4ct4 ,na,o,h7 in the cold4 ,they give small yields 7#a-b p4ct47 of furfural on boiling with #aj p4ct4 ,h,cl4,aq4 ,elementary analyses gave the following results1 which are important in establishing the presence of a notable proportion of nitrogen1 which has certainly been overlooked by the earlier observers3-- ',cellulose' or residue from ,c ,h ,n ,boletus edulis 7,schulze process7 #db4d #f4e #c4i ,boletus edulis 7,hoffmeister process7 #dd4f #f4c #c4f ,polyporus off4 #dc4g #f4e #j4g ,cantharellus cib4 #dd4i #f4h #c4j ,agaricus campestris #dd4c #f4f #c4f ,botrytis #db4a #f4c #c4i ,penicillium glaucum #c4c ,morchella esculenta #b4e ,it is next shown that this residual nitrogen is not in the form of residual proteids 7#a7 by direct tests1 all of which gave negative results1 and 7#b7 indirectly by the high degree of resistance to both alkaline and acid hydrolysis4 ,the 'celluloses' are attacked by boiling dilute acids 7#a p4ct4 ,h#b,,so#d71 losing in weight from #aj to #bc p4ct41 the dissolved products having a cupric reduction value about #ej p4ct4 that of an equal weight of dextrose4 ,as an extreme hydrolytic treatment the products were dissolved in #gj p4ct4 ,h#b,,so#d1 allowed to stand #bd hours1 then considerably diluted 7to #c p4ct4 ,h#b,,so#d7 and boiled to complete the inversion4 ,the yields of glucose1 calculated from the cupric reduction1 were as follows3-- ,boletus edulis #fe4b p4ct4 ,polyporus off4 #id4g ,agaricus campestris #ei4a ,morchella esculenta #fj4a ,cantharellus cib4 #fd4i ,botrytis #fj4h ,it will be noted that the exceptionally high yield from the ,polyporus cellulose is correlated with its exceptionally low nitrogen4 ,by actual isolation of a crystalline dextrorotary sugar1 by preparations of osazone and conversion into saccharic acid1 it was proved that dextrose was the main product of hydrolysis4 ,the second main product was shown to be acetic acid1 the yield of which amounted to #h p4ct4 in several cases4 ,generally1 therefore1 it is proved that the more resistant tissue constituents of the fungi are not cellulose1 but a complex of carbohydrates and nitrogenous groups in combination1 the former being resolved into glucoses by acid hydrolysis1 and the latter yielding acetic acid as a characteristic product of resolution together with the nitrogenous groups in the form of an uncrystallisable syrup4 ,in the further prosecution of these investigations 7#b7 the author proceeded from the supposition of the identity of the nitrogenous complex of the original with chitin1 and adopted the method of ,ledderhose 7,ztschr4 ,physiol4 ,chem4 #b1 #bac7 for the isolation of glucosamin hydrochloride1 which he succeeded in obtaining in the crystalline form4 ,in the meantime ,e4 ,gilson had shown that these tissue substances in 'fusion' with alkaline hydrates yield a residue of a nitrogenous product 7,c#ad;,h#bh,n#b,o#aj71 which is soluble in dilute acids ,recherches ,chim4 sur la ,membrane ,cellulaire des ,champignons1 ,la ,cellule1 v4 ,,ii1 pt4 #a4 ,this residue1 which was termed mycosin by ,gilson1 has been similarly isolated by the author4 ,it is proved1 therefore1 that the tissues of the fungi do contain a product resembling chitin4 ,see also ,gilson1 ,compt4 ,rend4 #abj1 #ajjj4 ,this constituent is in intimate union with the carbohydrate complex1 which is resolved similarly to the hemicelluloses4 ,various intermediate terms of the hydrolytic series have been isolated4 ,but the only fully identified product of resolution is the dextrose which finally results4 ,,ueber ,,die ,,kohlenhydrate ,d4 ,,hefe4 ,e4 ,,salkowski 7,berl4 ,ber41 #bg1 #ccbe74 ,,on ,,the ,,carbohydrates ,,of ,,yeast4 ,the author has isolated the more resistant constituents of the cell-membrane by boiling with dilute alkalis1 and exhaustively purifying with alcohol and ether4 ,the residue was only a small percentage 7#c-d p4ct7 of the original1 and retained only #j4de p4ct4 ,n4 ,it was heated in a digester with water at #b-c atm4 steam-pressure1 and thus resolved into approximately equal portions of soluble cellulose 7a7 and insoluble 7b74 ,the latter1 giving no colour-reaction with iodine1 is termed achroocellulose2 the former reacts1 and is therefore termed erythrocellulose4 ,the former is easily separated from its opalescent solution4 ,it has the empirical composition of cellulose4 ,in the soluble form it resembles glycogen4 ,the achroocellulose is isolated in the form of horny or agglomerated masses4 ,it appears to be resolved by ultimate hydrolysis into dextrose and mannose4 ,,section ,v4 ,,furfuroids1 i4e4 ,,pentosanes ,,and ,,furfural-,,yielding ,,constituents ,,generally 7#a7 ,reactions of the ,carbohydrates with ,hydrogen ,peroxide4 ,c4 ,f4 ,,cross1 ,e4 ,j4 ,,bevan1 and ,,claud ,,smith 7,j4 ,chem4 ,soc41 #ahih1 #dfc74 7#b7 ,action of ,hydrogen ,peroxide on ,carbohydrates in the ,presence of ,ferrous ,salts4 ,r4 ,s4 ,,morrell and ,j4 ,m4 ,,crofts 7,j4 ,chem4 ,soc41 #ahii1 #ghf74 7#c7 ,oxidation of ,furfuraldehyde by ,hydrogen ,peroxide4 ,c4 ,f4 ,,cross1 ,e4 ,j4 ,,bevan1 and ,t4 ,,heiberg 7,j4 ,ch4 ,soc41 #ahii1 #gdg74 7#d7 ,,einwirkung ,,von ,,wasserstoffhyperoxid ,,auf ,u,n,g,e,s,ae,t,t,i,g,t,e ,,kohlenwasserstoffe4 ,c4 ,f4 ,,cross1 ,e4 ,j4 ,,bevan1 and ,t4 ,,heiberg 7,berl4 ,ber41 #aijj1 #bjae74 ,,action ,,of ,,hydrogen ,,peroxide ,,on ,,unsaturated ,,hydrocarbons4 ,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 7#ajb74 ,certain remarkable observations had previously been made by ,h4 ,j4 ,h4 ,fenton 7,ch4 ,soc4 ,j41 #ahid1 #hii2 #ahie1 #ggd2 #ahif1 #edf7 on the oxidation of tartaric acid by the peroxide1 acting in presence of ferrous salts1 the --,,choh--,,choh-- residue losing ,h#b with production of the unsaturated group1 --,,oh4,c,c4,,oh--4 ,these investigations have subsequently been considerably developed and generalised by ,fenton1 but as the results have no immediate bearing on our main subject we must refer readers to the ,j4 ,chem4 ,soc41 #ahif-aijj4 ,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 groups1 and it has been established by the above investigations 7#a7 and 7#b7 that the particular group to be so affected in the hexoses is that contiguous to the typical --,,co group4 ,there results1 therefore1 a dicarbonyl derivative 7'osone'71 which reacts directly with #b mol4 phenyl hydrazine in the cold to form an osazone4 ,this was directly established for glucose1 laevulose1 galactose1 and arabinose 7#b74 ,while this is the main result1 the general study of the product shows that the oxidation is not simple nor in direct quantitative relationship to the ,h#b,o#b employed4 ,the molecular proportion of the aldoses affected appears to be in considerable excess1 and the reaction is probably complicated by interior rearrangement4 ,in the main1 the original aldehydic group resists the oxidation4 ,but a certain proportion of acid products are formed1 probably tartronic acid4 ,on distillation with condensing acids a large proportion of volatile monobasic acids 7chiefly formic7 are obtained4 ,the proportion of furfural obtained amounts to #c-d per cent4 of the weight of the original carbohydrate4 ,since the general result of these oxidations is the substitution of an ,,oh group for an ,h atom1 it was of interest to determine the behaviour of furfural with the peroxide4 ,the oxidation was carried out in dilute aqueous solution of the aldehyde at #bj deg4-#dj deg41 using #b-c mols4 ,h#b,o#b per #a mol4 ,c#e;,h#d,o#b4 ,the main product is a hydroxyfurfural1 which was separated as a hydrazone4 ,a small quantity of a monobasic acid was formed1 which was identified as a hydroxypyromucic acid4 ,both aldehyde and acid appear to be the alpha beta derivatives4 ,the aldehyde gives very characteristic colour reactions with phloroglucinol and resorcinol in presence of hydrochloric acid1 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 constituent4 ,the study of these oxidations was then extended to typical unsaturated hydrocarbons--viz4 acetylene and benzene4 7#d7 ,from the former the main product was acetic acid1 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 reactions4 ,this view receives some support from the fact that the interaction of the ,h#b,o#b with permanganates has now been established to be an oxidation of the ,h#b of the peroxide by the permanganate oxidation1 with liberation1 therefore1 of the ,o#b of the peroxide as an unresolved molecule ,baeyer4 ,benzene itself is also powerfully attacked by the peroxide when shaken with a dilute solution in presence of iron salts4 ,the products are phenol and pyrocatechol1 with some quantity of an amorphous product probably formed by condensation of a quinone with the phenolic products of reaction4 99 99 99 99 99 ,these types of oxidation effects now established give a definite significance to the physiological functions of the peroxide1 which is a form of 'active oxygen' of extremely wide distribution4 ,it would have been difficult a priori to devise an oxidant without sensible action on aldehydic groups1 yet delivering a powerful attack on hydrocarbon rings2 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 transformation4 ,our present knowledge of such actions and effects suggests a number of new clues to genetic relationships of carbon compounds within the plant4 ,the conclusion is certainly justified that the origin of the pentoses is referable to oxidations of the hexoses1 in which this form of 'active oxygen' plays an important part4 ,we must note here the researches of ,o4 ,ruff1 who has applied these oxidations with important results in the systematic investigation of the carbohydrates4 ,,ueber ,,die ,,verwandlung ,,der ,d-,g,l,u,c,o,n,s,ae,u,r,e ,,in ,d-,,arabinose 7,berl4 ,ber41 #ahih1 #aegc74 ,,conversion ,,of ,d-,,gluconic ,,acid ,,into ,d-,,arabinose4 99 99 99 99 99 ,d ,,und ,l ,,arabinose 7,ibid4 #ahii1 #eej74 99 99 99 99 99 ,,zur ,,kenntniss ,,der ,o,x,y,g,l,u,c,o,n,s,ae,u,r,e 7,ibid4 #ahii1 #bbfi74 ,,on ,,oxygluconic ,,acid4 ,ruff in these researches has realised a simple and direct transition from the hexoses to the pentoses4 ,by oxidising gluconic acid with the peroxide the beta --,,choh-- group is converted into carbonyl at the same time that the terminal ,,cooh alpha is oxidised to ,,co#b4 ,the yields of the resulting pentose are large4 ,simultaneously there is formed an oxygluconic acid1 which appears to be a ketonic acid of formula --,,ch#b,,oh4,,co47,,choh7#c4;,,cooh--4 ,from these results we see a further range of physiological probabilities2 and with the concurrent actions of oxygen in the forms of or related to hydrogen peroxide on the one side1 and ozone on the other1 we are able to account in a simple way for the relationships of the 'furfuroid' group1 which may include a number of intermediate terms in the hexose-pentose series4 ,following in this direction of development of the subject is a study of the action of persulphuric acid upon furfural4 ,,einwirkung ,,des ,,caro',,schen ,,reagens ,,auf ,,furfural4 ,c4 ,f4 ,,cross1 ,e4 ,j4 ,,bevan1 and ,j4 ,f4 ,,briggs 7,berl4 ,ber41 #aijj1 #cacb74 ,regarding this reagent as another form of 'active oxygen1' it is important to contrast its actions with those of the hydrogen peroxide4 ,instead of the beta-hydroxyfurfural 7ante1 #aae7 we obtain the delta-aldehyde as the first product4 ,the aldehydic group is then oxidised1 and as a result of attendant hydrolysis the ring is broken down and succinic acid is formed1 the original aldehydic group of the furfural being split off in the form of formic acid4 ,the reactions take place at the ordinary temperature and with the dilute form of the reagent described by ,baeyer and ,villiger 7,ber4 #cb1 #cfbe74 ,these results have some special features of interest4 ,the alpha delta-hydroxyfurfural has similar colour reactions to those of the alpha beta-derivative1 and may also therefore be present as a constituent of the lignocelluloses4 ,the tendency to attack in the #a4d position in relation to an aldehydic group further widens the capabilities of 'active oxygen' in the plant cell4 ,lastly1 this is the simplest transition yet disclosed from the succinyl to furfural grouping1 being effected by a regulated proportion of oxygen1 and under conditions of reaction which may be described as of the mildest4 ,in regard to the wide-reaching functions of asparagin in plant life1 we have a new suggestion of genetic connections with the furfuroids4 ,,vergleich ,,der ,,pentosen-,,bestimmungsmethoden ,,vermittelst ,,phenylhydrazin ,,und ,,phloroglucin4 ,m4 ,k,r,ue,g,e,r 7,inaug4-,diss41 ,goettingen1 #ahie74 ,,comparison ,,of ,,methods ,,of ,,estimating ,,furfural ,,as ,,hydrazone ,,and ,,phloroglucide4 ,the author traces the development of processes of estimating furfural 7#a7 by precipitation with ammonia 7furfuramide71 7#b7 by volumetric estimation with standardised phenylhydrazine1 7#c7 by weighing the hydrazone4 ,in #ahic 7,chem4 ,ztg4 #ag1 #agde7 ,hotter described a method of quantitative condensation with pyrogallol requiring a temperature of #ajj deg4-#aaj deg4 for two hours4 ,the insoluble product collected1 washed1 dried at #ajc deg41 and weighed1 gives a weight of #a4igd grm4 per #a grm4 furfural4 ,councler substitutes phloroglucinol for pyrogallol1 with the advantage of doing away with the digestion at high temperature4 7,ibid4 #ah1 #iff47 ,this process1 requiring the presence of strong ,h,cl1 has the advantage of being applied directly to the acid distillate1 in which form furfural is obtained as a product of condensation of pentoses1 c4 ,a comparative investigation was made1 precipitating furfural 7a7 as hydrazone in presence of acetic acid1 and 7b7 as phloroglucide in presence of ,h,cl 7#ab p4ct74 ,in 7a7 by varying the weights of known quantities of furfural1 and using the factor1 hydrazone x #j4eaf #j4jajd in calculating from the weights of precipitates obtained1 the maximum variations from the theoretical number were #a4ga and -#a4gd4 ,in 7b7 it was found necessary to vary the factor from #j4eb to #j4ee in calculating from phloroglucide to furfural4 ,the greatest total range of variation was found to be #b4e p4ct4 ,the phenol process is therefore equally accurate1 has the advantages above noted1 and1 in addition1 is less liable to error from the pressure in the distillates obtained from vegetable substances of volatile products1 e4g4 ketonic compounds1 accompanying the furfural4 ,this method has been criticised by ,helbel and ,zeisel ,sitz4-ber1 ,wiener ,akad4 #ahie1 #ajd1 ii4 p4 #cce on two grounds of error1 viz4 7#a7 the presence of diresorcinol in all ordinary preparations of phloroglucinol1 and 7#b7 changes in weight of the precipitate of phloroglucide on drying4 ,the process was carried out comparatively with ordinary preparations1 and with specially pure preparations of the phenol4 ,the quantitative results were identical4 ,the criticisms in question are therefore dismissed4 ,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 basis1 since the phloroglucide is not formed by the simple reaction #b ,c#e;,h#d,o#b ,c#f;,h#f,o#c - ,h#b,o ,c#bb;,h#ah,o#i1 but appears to have the composition ,c#af;,h#ab,o#f4 ,in part ii4 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-tissues4 ,glucoson was isolated from glucosazon1 and found to yield #b4i-c4f p4ct4 furfural4 ,gluconic acid distilled with hydrochloric acid gave traces of furfural2 so also with sulphuric acid and manganic oxide4 ,starch was oxidised with permanganate1 and a mixture of products obtained of which one gave a characteristic violet colouration with phloroglucol1 with an absorption-band at the ,d line4 ,on distilling with ,h,cl furfural was obtained in some quantity4 ,the product in question was found to be very sensitive to the action of bases1 and was destroyed by the incidental operation of neutralising the mixture of oxidised products with calcium carbonate4 ,it was found impossible to isolate the compound4 ,,untersuchungen ,,ueber ,,die ,,pentosanbestimmung ,,mittelst ,,der ,s,a,l,z,s,ae,u,r,e-,,phloro-,,glucin-,, methode4#h ,e4 ,k,r,oe,b,e,r 7,journ4 f4 ,landwirthschaft1 #aija1 #ceg74 ,,investigation ,,of ,,the ,,hydrochloric ,,acid-,,phloroglucinol ,,method ,,of ,,determining ,,pentosanes4 ,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 phenol4 ,in the last section of the paper is contained the most important result1 the proof that the insoluble phloroglucide is formed according to the reaction ,c#e;,h#d,o#b ,c#f;,h#f,o#c - #b;,h#b,o ,c#aa;,h#f,o#c1 also1 by varying the proportions of the pure reagents interacting1 that the condensation takes place invariably according to this equation4 ,incidentally the following points were also established3--,the solubility of the phloroglucide1 under the conditions of finally separating in a condition for drying and weighing1 is #a mgr4 per #ajj c4c4 of total solution1 made up of the original acid solution1 in which the precipitation takes place1 and the wash-water required to purify from the acid4 ,the phloroglucide is hygroscopic1 and must be weighed out of contact with the air4 ,the presence of diresorcinol is without influence on the result1 provided a sufficient excess of actual phloroglucinol is employed4 ,thus even with a preparation containing #cj p4ct4 of its weight of diresorcinol the influence of the latter is eliminated1 provided a weight be taken equal to twice that of the furfural to be precipitated4 ,the phenol must be perfectly dissolved by warming with dilute ,h,cl 7#a4jf sp4gr47 before adding to the furfural solution4 ,for collecting the precipitate of phloroglucide the author employs the ,gooch crucible4 ,the paper contains a large number of quantitative results in proof of the various points established1 and concludes with elaborate tables1 giving the equivalents in the known pentoses and their anhydrides for any given weight of phloroglucide from #j4jej to #j4cjj grm4 ,,ueber ,,den ,,pentosan-,,gehalt ,,verschiedener ,,materialien4 ,b4 ,,tollens and ,h4 ,,glaubitz 7,j4 fuer ,landwirthschaft1 #ahig1 #ig74 ,,on ,,the ,,pentosane ,,constituents ,,of ,,fodder-,,plants ,,and ,,malt4 7p4 #aga7 7a7 ,the authors have re-determined the yield of furfural from a large range of plant-products1 using the phloroglucol method4 ,the numbers approximate closely to those obtained by the hydrazone method4 ,the following may be cited as typical3 ,substance ,furfural p4ct4 ,rye 7,goettingen7 #f4jc ,wheat 7square head7 #d4ge ,barley 7peacock7 #d4cc ,oats 7,goettingen7 #g4gb ,maize 7,american7 #c4ag ,meadow hay #aa4fc ,bran 7wheat7 #ac4jf ,malt #f4jg ,malt-sprouts #h4ef ,sugar-beet 7exhausted7 #ad4ie 7b7 ,a comparison of wheat with wheat bran1 c4 was made by grinding in a mortar and 'bolting' the flour through a fine silk sieve4 ,the results showed3 ,furfural p4ct4 ,original wheat #d4ge ,fine flour #a4gc ,bran 7#bd p4ct4 of wheat7 #aa4be ,wheat-bran of commerce #ac4jf ,it is evident that the pentosanes of wheat are localised in the more resistant tissues of the grain4 7c7 ,an investigation of the products obtained in the analytical process for 'crude fibre' gave the following3 7#a7 ,in the case of brewers' grains3 #ajj grms4 grains gave furfural #bi4dc pentosane --------------- #bj crude fibre #b4eb ,acid extract #bb4gf ,alkali #a4bj ,deficiency from total of original grains #b4ie ----- #bi4dc 7#b7 ,in the case of meadow hay3 ,the crude fibre 7#cj p4ct47 obtained retained about one fourth 7#bc4fc p4ct47 of the total original pentosanes4 7d7 ,an investigation of barley-malt1 malt-extract or wort1 and finished beer showed the following3 ,an increase of furfuroids in the process of malting1 #ajj pts4 barley with #g4ig of 'pentosane' yielding #hb of malt with #aa4ah p4ct4 'pentosane'2 confirming the observations of ,cross and ,bevan 7,ber4 #bh1 #bfjd74 ,of the total furfuroids of malt about #a_/d are dissolved in the mashing process4 ,in a fermentation for lager beer it was found that about _/#aj of the total furfuroids of the malt finally survive in the beer2 the yield of furfural being #b4ib p4ct4 of the 'total solids' of the beer4 ,in a ',schlempe' or 'pot ale1' from a distillery using to #a part malt #d parts raw grain 7rye71 yield of furfural was #i p4ct4 of the total solids4 ,in a general review of the relationships of this group of plant-products it is pointed out that they are largely digested by animals1 and probably have an equal 'assimilation' value to starch4 ,they resist alcoholic fermentation1 and must consequently be taken into account as constituents of beers and wines4 ,,ueber ,,das ,,verhalten ,,der ,,pentosane ,,der ,,samen ,,beim ,,keimen4#i ,a4 ,s,c,h,oe,n,e and ,b4 ,,tollens 7,jour4 f4 ,landwirthschaft1 #aija1 #cdi74 ,,behaviour ,,of ,,pentosanes ,,of ,,seeds ,,in ,,germination4 ,the authors have investigated the germination of barley1 wheat1 and peas1 in absence of light1 and generally with exclusion of assimilating activity1 to determine whether the oxidation with attendant loss of weight1 which is the main chemical feature of the germination proper1 affects the pentosanes of the seeds4 ,the following are typical of the quantitative results obtained1 which are stated in absolute weights1 and not percentages4 ,original seed ,malt or ,pentosane in germinated product ,a ,b ,a ,b ,barley #ejj4jj #dcd4hh #ci4eh #dj4ch #ejj4jj #ddb4bf #dj4eb #da4ag ,peas #cjj4jj #bhf4fj #ae4be #ae4ig ,the authors conclude generally that there is a slight absolute increase in the pentosanes1 and that the pentosanes do not belong to those reserve materials which undergo destructive oxidation during germination4 ,in this they confirm the previously published results of ,de ,chalmot1 ,cross and ,bevan1 and ,gotze and ,pfeiffer4 ,,ueber ,,den ,,gehalt ,,der ,,baumwolle ,,an ,,pentosan4 ,h4 ,,suringar and ,b4 ,,tollens 7,ztschr4 angew4 ,chem41 #ahig1 ,i74 ,,pentosane ,,constituents ,,of ,,cotton4 7p4 #bij7 ,it has been stated by ,link and ,voswinkel 7,pharm4 ,centralhalle1 #ahic1 #bec71 that raw cotton yields 'wood gum' as a product of hydrolysis4 ,the authors were unable to obtain any pentoses as products of acid hydrolysis of raw cotton1 and traces only of furfural-yielding carbohydrates4 ,they conclude that raw cotton contains no appreciable quantity of pentosane4 ,,footnotes3 #h ,this paper appears during the printing of the author's original ,,ms4 #i ,this paper appears during the printing of the author's original ,,ms4 ,,section ,,vi4 ,,the ,,lignocelluloses 7p4 #aca7 ,lignocellulose ,esters4--,by a fuller study of the ester reactions of the normal celluloses we have been able to throw some light on the constitutional problems involved2 and we have extended the investigations to the jute fibre as a type of the lignocelluloses1 from the results of which we get a clearer idea of the relationships of the constituent groups4 ,taking the empirical expression for the complex1 i4e4 the entire lignocellulose1 the formula ,c#ab;,h#ah,o#i1 we shall be able to compare the ester derivatives with those of the celluloses1 which we have also referred to a ,c#ab unit4 ,but we shall require also to deal with the constituent groups of the complex1 which for the purposes of this discussion may be regarded as 7a7 a cellulose of normal characteristics--cellulose alpha2 7b7 a cellulose yielding furfural on boiling with condensing acids--cellulose beta2 and 7c7 a much condensed1 and in part benzenoid1 group which we may continue to term the lignone group4 ,the latter has been specially examined with regard to its proportion of ,,oh groups1 as a necessary preliminary to the investigation of esters1 in producing which the entire complex is employed4 ,it will be shown that the ester groups can be actually localised in various ways1 as in the main entering the cellulose residues alpha and beta4 ,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 derivative1 7#a7 ,by chlorination1 c4 it is isolated in the form of an amorphous body1 but of constant composition1 represented by the formula ,c#ai;,h#ah;,cl#d,o#i4 ,this compound1 soluble in acetic anhydride1 was boiled with it for six hours after adding fused sodium acetate1 and the product separated by pouring into water4 ,the dilute acid filtered from the product contained no hydrochloric acid nor by-products of action4 ,the product showed an increase of weight of #g4e p4ct4 ,for one acetyl per #a mol4 ,c#ai;,h#ah;,cl#d,o the calculated increase is #h4j p4ct4 ,it is evident from the nature of the derivative that this result cannot be further verified by the usual analytical methods4 7#b7 ,the chlorinated derivative is entirely soluble in sodium sulphite solution4 ,this solution1 shaken with benzoyl chloride1 with addition of sodium hydrate in successive portions1 shows only a small formation of insoluble benzoate1 which separates as a tarry precipitate4 7#c7 ,the empirical formula of the lignone complex in its isolated forms indicates that very little hydrolysis occurs in the processes of isolation4 ,thus the chlorinated product we may assume to be derived from the complex ,c#ai;,h#bb,o#i4 ,in the soluble by-products from the bisulphite processes of pulping wood the lignone exists as a sulphonated derivative1 ,c#bd;,h#bc7,,och#c7b47,,so#c;,h74,o#g4 ,the original lignone may be regarded as passing into solution as a still condensed complex derived from ,c#bd;,h#bf,o#ab 7,tollens74 ,there is evidently little attendant hydroxylation1 and another essential feature is the small molecular proportion of groups showing the typical sulphonation4 ,it appears that in the lignone the elements are approximately in the relation ,c#f 3 ,h#f 3 ,o#c1 and it may assist this discussion to formulate the main constitutional types consistent with this ratio1 viz43 7#a7 ,the trihydroxybenzenes ,c#f;,h#c7,,oh7#c4 7#b7 ,methylhydroxyfurfural ,c#e;,h#b,o47,,oh77,,ch#c74 7,,ch#c7 _/ 7#c7 ,methylhydroxypyrone ,,co,c#d;,h#b ,o _/ 7,,oh7 7#d7 ,trioxycyclohexane ,,ch--,,ch--,,ch--,,ch--,,ch--,,ch _/ _/ _/ ,o ,o ,o ,it is probable that all these types of condensation are represented in the lignone molecules1 since the derivatives yielded in decompositions of more or less regulated character are either directly derived from or related to such groups4 ,for the moment we pass over all but the general fact of complexity and the marked paucity of ,,oh-groups4 ,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 lignocellulose4 ,the evidence1 however1 does not carry us farther than the probability of union by complicated groups and of large dimensions2 for not only is the lignone isolated in condensed and non-hydroxylated forms1 but the cellulose also is not hydrated or hydrolysed further than in the ratio #c;,c#f;,h#aj,o#e4;,h#b,o4 ,it is probable1 therefore1 that the water combining with the residues at the moment of their resolution is relatively small4 ,lastly1 we have to remember1 when dealing with the statistical results of the reactions to be described1 that the approximate proportions per cent4 of the constituent groups are3 ,cellulose alpha #fe beta #ae #ajj lignocellulose4 ,lignone #bj ,jute ,benzoates4--,in preparing the jute for treatment it was boiled in alkaline solution 7#a per cent4 ,na,o,h71 washed with water and dilute acid1 again washed1 dried1 and weighed4 ,in the ester reaction the reagents were employed in the proportion ,c#ab;,h#ah,o#i 3 #c,na,o,h 3 #b;,c#f;,h#e;,c,o,cl4 ,a series of quantitative experiments gave yields of #abf-acj p4ct4 of benzoate calculated for monobenzoate #acd p4ct44 ,the results were confirmed by ultimate analysis4 ,the monobenzoate therefore represents a maximum1 and this molecular proportion is one-half of that observed with the normal cellulose1 calculated to the same unit4 ,localisation of ,benzoyl ,group4--,the entrance of the ester group affects the typical colour reactions of the lignocellulose1 which are fainter4 ,the ferric ferricyanide reaction almost disappears4 ,the lignone group is unaffected1 and combines with chlorine as in the original4 ,the lignone chloride is removed by sodium sulphite solution1 and the residue is a cellulose benzoate4 ,the loss of weight due to the elimination of the lignone was #ab4g p4ct4 ,calculating per #ajj of the original lignocellulose this becomes #af4 ,these statistics further confirm the localisation of the benzoyl group in the cellulose residue4 ,it is to be noted that the presence of the benzoyl group renders the cellulose more resistant to hydrolytic actions4 ,thus1 to bring out this fact more prominently1 we may calculate the yield of residual cellulose benzoate p4ct4 of original jute1 and we find it #aji p4ct4 ,taking a maximum proportion for original cellulose--viz4 #he--this benzoate represents a yield of #abi p4ct41 as against the theoretical for a monobenzoate1 #acb p4ct4 ,furfural ,numbers4--,the percentage of furfural obtained by boiling with ,h,cl of #a4jf sp4gr4 was #c4jb and #c4bi in separate determinations4 ,calculating to the original lignocellulose1 the percentage1 #d4ba1 indicates a considerable loss of the furfural-yielding constituent4 ,the effect was also apparent in the cellulose 7benzoate7 isolated by chlorination c41 the percentage being #a4ci p4ct41 and calculated to the original jute benzoate #a4ei p4ct4 ,under the conditions adopted in dissolving away the chlorinated lignone the original non-benzoated lignocellulose would have yielded a cellulose giving #f to #g p4ct4 furfural4 ,since the benzoyl group is hardly calculated to produce a constitutional change affecting the furfural constants1 it was necessary to examine the effect of the preliminary alkaline treatment1 and the change in the furfuroid group was in fact localised in this reaction4 ,it was found that1 on washing the alkali from the mercerised jute1 and further purifying the residue1 this latter yielded only #d4b p4ct4 furfural #c4d p4ct4 on original fibre4 ,the alkaline solution and washings were acidified and distilled from #aj p4ct4 ,h,cl1 yielding an additional #c4f p4ct4 calculated to the original lignocellulose4 ,by treatment with the concentrated alkali1 therefore1 the furfuroid of the original lignocellulose undergoes little change1 but is selectively dissolved4 ,this point is under further investigation4 7p4 #acb7 ,acetylation of ,lignocelluloses4--,acetates are readily formed by boiling the lignocelluloses with acetic anhydride4 ,the derivatives obtained from jute are only generally mentioned in the #ast edition 7p4 #acb74 ,a further study of the reactions in regard to special points has led to some more definite results4 ,the yields of product by the ordinary and simple process are #aad-aae p4ct4 ,but on analysing the product an important discrepancy is revealed4 ,for the saponification we employ a solution of sodium ethylate in the cold4 ,the following numbers were obtained3 ,acetic acid ,hydrocellulose residue #bg4b #gg4h ,calc4 for diacetate on ,c#ab;,h#ah,o#i #cj4h #gh4d ,the derivative is approximately a diacetate1 and on the assumption of a simple ester reaction the yield should be #abg p4ct4 ,assuming that the difference of #ac p4ct4 is due to loss of water by internal condensation1 it appears that for each acetyl group entering1 #b mol4 ,h#b,o are split off4 ,the jute acetate showed the normal reaction with chlorine1 and the lignone chloride was dissolved by treatment with sodium sulphite solution4 ,the fibrous residue was colourless4 ,it proved to be a cellulose acetate4 ,the following numbers were obtained on saponification3 ,acetic acid ,cellulose #ca4f #gj4j #cj4i #fh4h ,calc4 for diacetate on ,c#ab;,h#bj,o#aj #bi4d #gi4i ,the interpretation of these numbers appears to be this3 in the original reaction with the lignocellulose it is the cellulose residue which is acetylated1 and at the same time condensed4 ,the cellulose residue which undergoes condensation is not of the normal constitution1 since the normal cellulose is acetylated without condensation 7see p4 #da74 ,on saponification a portion of the cellulose1 in again combining with water1 is hydrolysed to soluble products4 ,the lignone group as it exists in the lignocellulose has no free ,,oh groups1 and probably no free aldehydic groups such as would react with the anhydride4 ,such groups may1 however1 be originally present1 and may take part in the internal condensations which have been shown to occur4 ,the furfural constants of the lignocellulose are unaffected by the acetylation and condensation4 ,the hygroscopic moisture of the product is lowered from #aj-aa p4ct4 in the original to #d4e p4ct4 ,the ferric ferricyanide reaction is inhibited by the disappearance of the reactive groups1 upon which this curious and characteristic phenomenon depends 7#ast ed474 ,acetylation of ,benzoates4--,the cellulose dibenzoate 7,c#ab basis7 and the jute monobenzoate were acetylated under comparative conditions ,the results were as follows3 ,c#ab basis ,cellulose dibenzoate ,jute monobenzoate ,calc4 for ,calc4 for ,found diacetate on ,found diacetate on ,ester reaction dibenzoate monobenzoate ,yield #aaa p4ct4 #aae p4ct4 #abd p4ct4 #abj p4ct4 ,saponification ,cellulose ,lignocellulose #ec4e #eb4f #ei4h #fa4i ,na,o,h combining #ba4c #bc4i #bh4d #bd4c ,from these results it would appear that the number of acetyl groups entering the benzoates is the same as with the unbenzoylated fibres1 the benzoyl has no influence upon the hydroxyls as against the acetyl4 ,at the same time the internal condensation noticed in the acetylation of the jute appears not to occur in the case of the benzoate4 ,nitric ,esters4--,the numbers resulting from the quantitative study of the ester reaction and product 7#ast ed4 p4 #acc7 show a very large divergence of the yield of product from that which would be calculated from its composition 7,n p4ct47 on the assumption that the ester reaction is simple4 ,we have repeated the results1 and find with a yield of #ade p4ct4 that the product contains #aa4h p4ct4 ,n4 ,the reaction ,c#ab;,h#ah,o#i #d;,,hno#c - #d;,h#b,o gives a tetranitrate with #aa4e p4ct4 ,n and a yield of #aei p4ct4 ,the ester reaction1 therefore1 is not simple4 ,there are two sources of the loss of weight4 ,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 mixture4 ,to determine this quantitatively we have devised a suitable variation of the method of combustion with chromic acid 7#ast ed474 ,the variation is required to meet the difficulty occasioned by the tension of the nitric acid and products of deoxidation4 ,the mixed acids 7#aj c4c471 containing the organic by-products in solution1 are carefully diluted in a small flask with an equal volume of water1 preventing rise of temperature4 ,nitrous fumes are evolved during the dilution4 ,strong sulphuric acid 7#ae c4c47 is now added1 and the residue of nitrous fumes expelled by a current of air1 agitating the contents of the flask from time to time4 ,the combustion with ,cr,o#c is then proceeded with in the ordinary way4 ,the gases evolved are measured 7total volume7 and calculated to ,c present in the form of products derived from the lignocellulose2 and1 assuming that this contains #dg p4ct4 ,c1 we may express the result approximately in terms of the fibre substance4 ,the method was controlled by blank experiments1 in which citric acid was taken as a convenient carbon compound for combustion4 ,the ,c found was #cd4i p4ct4 as against #cd4c p4ct4 calculated4 ,by this method we find that with maximum yields of nitrate at #adc-ade p4ct4 the organic matter in solution in the acid mixture amounted to #d4i to #e4c p4ct4 of the original lignocellulose4 ,introducing this quantity as a correction of the yield of nitrate in the original reaction1 we must express the #adc parts as obtained from #ie of fibre substance instead of #ajj4 ,the yield per molecule ,c#ab;,h#ah,o#i 7 #cjf7 is therefore #dfb1 whereas for a tetranitrate formed by a simple ester reaction the yield should be #dhf4 ,the difference 7#bd7 represents #a4e mol4 ,h#b,o split off by internal condensation4 ,the correction for total ,n is relatively small1 raising it from #aa4e to #ab4b1 which remains in close agreement with the experimental numbers4 ,monobenzoate4--,treated with the acid mixture yields a mixed nitrate4 ,the yield is #acj p4ct41 and the product contains #g4f p4ct4 ,o4,,no#b nitrogen4 ,these numbers approximate to those required for reaction with #d;,,hno#c groups1 three of the residues entering the cellulose1 and one 7as ,,no#b7 the benzene ring of the substituting group4 ,for such a reaction the calculated numbers are3 ,yield #add p4ct42 ,o4,,no#b nitrogen #g4a p4ct4 ,the experimental numbers require correcting for the amount of loss in the form of products soluble in the acid mixture1 viz4 #g4f p4ct42 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 three4 ,the corrected yield per #a mol4 of jute benzoate 7#daj7 is #egf1 as against the calculated #eij for #d;,,hno#c reacting4 ,a loss of #a;,h#b,o per molecule by internal condensation is therefore indicated4 ,denitration4--,the removal of the nitric groups from the esters is effected by digestion with ammonium sulphide4 ,but the reactions are by no means simple4 ,there is considerable hydrolysis of the lignocellulose to soluble products4 ,thus the tetranitrate yields only #df4d of denitrated fibre in place of the calculated #ff4 ,the product is a cellulose1 yielding only #j4e per cent4 furfural4 ,the hydrolysed by-products1 moreover1 when freed from sulphur and distilled from hydrochloric acid1 yielded only an additional #b4e p4ct4 furfural1 calculated to the original lignocellulose4 ,these statistics confirm the evidence that the ester reaction is not simple4 ,such changes take place in the lignone-beta-cellulose complex that they revert1 not to their original form1 but to soluble derivatives of different constitution4 ,the mixed nitrate from the benzoate is denitrated to a cellulose amidobenzoate1 which confirms the localisation of a nitro-group in the benzoyl residue4 7p4 #aeg7 ,general ,characteristics of the ,lignocelluloses4--,later investigations have somewhat modified and simplified our views of the constitution of the typical lignocellulose 7jute71 so far as this can be dealt with by the statistics of its more important decompositions 7original1 pp4 #aeg-afa74 ,cellulose4--,there is little doubt that the furfural-yielding groups of the original are isolated in the form of the beta-cellulose4 ,tollens emphasises this fact in his studies of cellulose-estimation methods4 ,we had previously shown 7original1 p4 #aei7 that the yield of furfural is not affected by the chlorination1 but it appears from our numbers that only #ej p4ct4 of these groups remain in the isolated cellulose1 the residue undergoing hydrolysis to soluble compounds4 ,in a carefully regulated hydrolysis following the chlorination it appears that the furfuroids are almost entirely conserved in the form of a cellulose4 ,moreover1 an investigation of the products dissolved by sodium sulphite solution from the chlorinated fibre has shown that they are practically free from furfuroids4 ,this enables us to exclude the furfural-yielding groups from the lignone complex4 ,at the same time1 through our later studies of the hydroxyfurfurals1 it is certain that these products are represented in the fibre substance and probably in the lignone complex4 ,chlorination ,statistics4--,it has been pointed out by a correspondent--to whom we express our indebtedness--that we have made a mistake in calculating the proportion of lignone from the ratio of the ,cl combining with the fibre substance or lignocellulose 7p4ct71 to that of the ,cl present in the isolated lignone chloride 7p4ct474 ,the lignocellulose combines with chlorine in the ratio #ajj 3 #h1 but the lignone chloride containing #bf4g of chlorine means that1 neglecting the hydrogen substituted1 #gc of lignone combine with the #bg of chlorine approximately4 ,on the uniform percentage basis the calculated proportion of lignone would be #h_/cg1 or a little over #bj p4ct4 ,in regard to the proportion of hydration attending the resolution1 we have shown on constitutional grounds that this must be relatively small4 ,assuming approximately the formula ,c#ai;,h#bb,o#i for the lignone residue as it exists in combination1 and the anhydride formula for the cellulose1 these revised statistics now appear1 as regards the carbon contents of the lignocellulose3 ,cellulose1 #dd4d ,c2 lignone1 #eg4h4 #hj x #dd4d _/ #ajj #ce4eb #bj x #eg4h _/ #ajj #aa4ef #dg4jh p4ct4 ,c in lignocellulose4 ,these conclusions are in accordance with the experimental facts1 and1 taken together with the new evidence we have accumulated from a study of the lignocellulose esters1 we may sum up the constitutional points as follows3 ,the lignocellulose is a complex of ,cellulose alpha ,cellulose beta ,lignone #fe p4ct4 #ae p4ct4 #bj ,allied to the normal ,yielding furfural ,one-third of which celluloses approximately #ej p4ct4 is of benzenoid type ,the lignone contains but little hydroxyl4 ,the celluloses are in condensed hydroxyl union with the lignone1 but the combination occurs by complexes of relatively large molecular weight4 ,,die ,,chemie ,,der ,,lignocellulosen--,,ein ,,neuer ,,typus4 ,w4 ,c4 ,,hancock and ,o4 ,w4 ,,dahl 7,berl4 ,ber41 #ahie1 #aeeh74 ,chemistry of ,lignocelluloses--,a ,new ,type4 ,the stem of the aquatic ,a,eschynomene aspera offers an exceptional instance of structural modification to serve the special function of a 'float1' #a grm4 of substance occupying an apparent volume of #dj-ej c4c4 ,this pith-like substance is morphologically a true wood 7,de ,bary71 and the author's investigations now establish that it is in all fundamental points of chemical composition a lignocellulose1 although from its colour reactions it has been considered by botanists to be a cellulose tissue containing a proportion of lignified cells4 ,thus the main tissue is stained blue by iodine in presence of hydriodic acid 7#a4e s4g471 and the colour is not changed on washing4 ,the ordinary lignocelluloses are stained a purple brown changed to brown on washing4 ,the reactions with phloroglucol and with aniline salts1 characteristic of these compounds1 is only faintly marked in the main tissue1 though strongly in certain individual cells4 ,the following quantitative determinations1 however1 establish the close similarity of the product to the typical lignocelluloses3 ,elementary ,analysis4--,c #df4ee1 ,h #f4g4 ,furfural #aa4f p4ct41 of which there remained in the residue from alkaline hydrolysis 7#ga p4ct47 #h4j1 i4e4 about #gj p4ct4 ,the distribution of the furfuroids is therefore not affected by the alkaline treatment4 ,chlorination4--,the substance 7after alkaline hydrolysis7 takes up #af4i p4ct4 ,cl1 of which approximately one-half is converted into hydrochloric acid4 ,methoxyl4--,o4,,ch#c estimated #b4i p4ct4 ,ferric ,ferricyanide ,reaction4--,increase of weight due to blue cyanide fixed 7#a7 #ge p4ct41 7#b7 #if p4ct4 ,ratio1 ,fe 3 ,,cn #a 3 #b1 #d4 ,hydroxyl ,reactions4--,in the formation of nitric esters and in the sulphocarbonate reaction the substance gave results similar to those obtaining for the jute fibre4 ,these results establish the general identity of this peculiar product of plant life with the lignocelluloses1 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 present4 7p4 #agb7 ,composition of ,elder ,pith4--,in a systematic investigation of the celluloses in relation to function we shall have to give special attention to the parenchymatous tissues of all kinds4 ,these are1 for structural reasons1 not easily isolated1 for which reason and their generally 'inferior' functions they do not present themselves to chemical observation in the same obvious way as do their fibrous relatives4 ,the pith of the elder1 however1 is readily obtained in convenient masses1 and a preliminary investigation of the entire tissue has established the following points3 ,the reactions of the tissue are in all respects those of the lignocelluloses4 ,composition4--,ash1 #b4b p4ct42 moisture in air-dry state1 #ab4c p4ct4 ,alkaline hydrolysis 7loss73 7a7 #ad4gg1 7b7 #ag4hd4 ,cellulose 7yield71 #eb4cc p4ct4 ,nitrate-reaction complicated by secondary reactions and yields low1 #ij4ie p4ct4 ,sulphocarbonate reaction3 ,resists the treatment1 less than #aj p4ct4 passes into solution4 ,furfural4--,the original tissue yields #g4ac p4ct42 the residue from alkaline hydrolysis 7b7 #e4dj p4ct4 ,this tissue is1 therefore1 a lignocellulose having the chemical characteristics typical of the group1 but of less resistance to hydrolytic actions4 ,the investigation will be prosecuted in reference to the cause of differentiation in this latter respect4 ,probably the pectocelluloses are represented in the tissue4 ,the ,insoluble ,carbohydrates of ,wheat 7grain74 ,h4 ,c4 ,,sherman 7,j4 ,amer4 ,chem4 ,soc41 #ahig1 #bia74 7p4 #aga7 ,this is a study of the constituents of the cell-walls of wheat grain4 ,bran was taken as the most convenient form of the raw material1 being freed from starch by treatment with malt extract1 and further treated 7#a7 with cold dilute ammonia1 7#b7 cold dilute soda lye 7#b p4ct4 ,na,o,h71 and 7#c7 boiling #j4a p4ct4 ,na,o,h4 ,the product retained only #a4be p4ct4 proteids1 and yielded #ae4fb p4ct4 furfural4 ,acid ,hydrolysis4--,the product was boiled #cj mins4 with dilute acid 7#a4be p4ct4 ,h#b,,so#d71 and the solution boiled until the ,fehling test showed no further increase of monoses4 ,at the limit the reducing power of the dissolved carbohydrates was #ia4c p4ct41 that of dextrose4 ,converted into osazones the analysis showed them to be pure pentosazones4 ,the hemicellulose of wheat is1 therefore1 according to the author1 pure pentosane4 ,residue4--,this was a lignocellulose yielding #aa4e p4ct4 furfural4 ,it was subjected to a series of treatments with ferric ferricyanide1 and the proportion of ,prussian blue fixed was determined by increase of weight1 viz4 from #aj p4ct4 to #dg p4ct4 according to the conditions4 ,the results confirmed those of ,cross and ,bevan first obtained with the typical lignocellulose 7jute74 ,chlorination4-,the residue was boiled with dilute alkali1 washed1 and exposed to chlorine gas4 ,the resulting lignone chloride was isolated by solution in alcohol1 c4 ,it yielded #bf4g p4ct4 ,cl on analysis4 ,in this and its properties it appeared to be identical with the product isolated by ,cross and ,bevan from jute1 with the empirical formula ,c#ai;,h#ah;,cl#d,o#i4 ,cellulose was isolated from the residue by three of the well-known methods1 and the following comparative numbers are noteworthy3 ,f4 ,schulze ,lange ,cross and ,method ,dil4 ,,hno#c ,fusion ,,koh ,bevan ,k,cl,o#c ,chlorine1 c4 ,cellulose p4ct4 obtained #ff4j #ci4c-dc4a #ff4e ,furfural p4ct4 of cellulose #g4j #c4if #e4fb ,residual nitrogen #j4bb #j4jc #j4jj ,ferricyanide reaction1 ,prussian blue fixed #f4jd #j4hi #j4ib ,the author remarks3 ',it is evident no one feature can be urged as a criterion in judging between the methods1 but all must be taken into consideration4 ,such a comparison shows the superiority of the chlorination method4' ,the cellulose is not of the normal 7cotton7 type1 since on treatment with sulphuric acid it dissolves with considerable discolouration1 but only to the extent of about #hj per cent4 ,the dissolved monoses converted into osazones were found to consist of hexoses only4 ,the cellulose treated with caustic soda solution 7#e p4ct4 ,na,o,h7 in the cold yielded #bj p4ct4 of its weight of soluble constituents1 but as the residue yielded #c4cd p4ct4 furfural the attack of the alkali is by no means confined to the furfuroids4 ,animal ,digestion of the ,constituents of ,bran4--,observations on a steer fed upon wheat bran only established the following percentage digestion of the several constituents3 ,soluble carbohydrates #if4i ,starch #ajj4j ,free pentosanes #fj4b ,cellulose #bd4h ,lignin complex #cf4g ,proteid #hb4if ,ether extract #db4gc ,nitrogen-free extract #gf4jh ,crude fibre #cb4ba ,,journal ,,of ,,the ,,imperial ,,institute 7,research ,department1 ,vols4 #a-b1 #ahie-f74 7p4 #aji7 ,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' 7,col4 ,ind4 ,exhibition ,reports1 p4 #cfh7 ,c4 ,f4 ,cross4 ,these investigations deal with the following subjects3 #ahie4 p4 #bi ,various ,indian ,fibres--more particularly ,sida4 #aah 7a7 ,fibres from ,victoria2 7b7 ,special ,analyses of 7a7 ,samples of ,jute2 7c7 ,paper-making ,fibres from ,s4 ,australia4 #bjb ,fibres from ,victoria4 #bhg ,fibres from ,victoria4 #cff ,sisal from ,trinidad4 #cgc ,rope-fibres from ,grenada4 7b7 #cih ,report of ,experiments on ,indian ,jute 7#a74 #dce ,fifth and ,sixth ,report on ,australian ,fibres4 #dgc #ahif4 #fh ,hibiscus and ,abroma ,fibres4 #ajd-e ,hibiscus1 ,urena1 and ,crotalaria ,fibres4 #ada ,indian ,sisal 7c7 #ahb-c ,report of ,experiments on ,indian ,jute 7#b74 #bfd ,sanseviera from ,assam4 ,from the above we may draw the general conclusion that the scheme of investigation has been found in practice to answer its main purpose1 viz4 to afford such numerical constants as determine industrial values4 ,in illustration we may cite 7a7 the results of analyses of specially selected samples of jute1 from which it will be seen that there is a close concordance of value as ordinarily determined from external appearance1 with the chemical constants as determined in the laboratory4 ,quality of ,jute ,low ,medium ,extra ,extra ,fine ,moisture #aa4j #aj4d #aa4a #i4f ,ash #j4hg #b4h #a4j #j4g ,alkaline hydrolysis 7a7 #e mins4 boiling #ac4b #aa4f #h4e #i4a ,alkaline hydrolysis 7b7 #fj mins4 boiling #af4a #ag4e #ab4e #ac4a ,mercerising treatment #i4b #aj4e #aj4c #h4e ,nitration 7increase p4ct47 #cf4f #ce4g #cg4e #cf4g ,cellulose 7yield7 #ga4d #gj4j #gi4j #gg4g ,acid purification #b4f #a4c #a4i #b4j ,a useful series of experiments1 initiated by the ,institute1 is that noted under 7b7 and 7c7 above4 7#a7 ,to ascertain the quality of the fibre extracted from the plant at different stages of growth1 quantities of #djj lbs4 of the stalks were cut at successive stages and the fibre isolated after steeping #ad-bj days4 ,the fibre was shipped to ,england and chemically investigated1 with the following results3 ,no4 #a4 ,cut before appearance of inflorescence4 #b4 after budding4 #c4 in flower4 #d4 after appearance of seed-pod4 #e4 when fully matured4 7#a7 7#b7 7#c7 7#d7 7#e7 ,moisture #aa4ee #h4gd #aj4g #aj4j #i4gb ,ash #a4a #a4a #a4a #a4a #j4ij ,alkaline hydrolysis 7a7 #f4b #h4e #i4g #h4i #g4c 7b7 #aj4e #aa4i #aa4f #ab4j #aa4b ,mercerising treatment #aj4b #aj4g #ab4j #h4a #aa4j ,nitration #cg4b #cb4a #cb4b #cc4b #cf4f ,cellulose #gd4j #gf4b #gd4a #gd4h #gf4d ,acid purification #j4h #j4e #j4g #b4d #a4d ,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 plant1 confirming the conclusion that the 'incrustation' view of lignification is consistent only with the structural features of the changes1 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 facts4 ,examination of the samples from the point of view of textile quality showed a superiority of ,no4 #a in fineness1 softness1 and strength2 from this stage there is observed a progressive deterioration1 but the ,no4 #d sample 7which was taken at the usual period of cutting7 is superior to ,no4 #e4 ,in a further series of experiments 7c7 the jute was subjected to certain chemical treatments immediately after the separation of the fibre from the plant4 ,these consisted in steeping 7#a7 in solution of sodium carbonate1 as well as of plant ashes1 and 7#b7 in sulphite of soda1 the purpose of the treatments being to modify or arrest the changes which take place in the fibre when press-packed in bales for shipment4 ,the samples were shipped from ,india under the usual conditions and examined soon after arrival4 ,it was found that the chemical treatments had produced but small changes in chemical composition of the fibre-substance4 ,the sulphite treatment was the more marked in influence1 somewhat lowering the cellulose and nitration constants4 ,the conclusion drawn from the results was that they afford no prospect of any useful modification1 i4e4 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 shipment4 ,the other matters investigated in the ,institute laboratory and reported on as indicated above are rather of commercial significance1 and contributed no points of moment to the chemistry of cellulose4 ,,observations ,,on ,,some ,,of ,,the ,,chemical ,,substances ,,in ,,the ,,trunks ,,of ,,trees4 ,f4 ,h4 ,,storer 7,bull4 ,bussey ,inst41 #ahig1 #chf74 7p4 #agb7 ,an examination of the outer and inner wood and of the bark of the grey birch1 at different seasons of the year1 gave the following yields of furfural p4ct4 on the dry substance3 ,wood ,bark ,inner ,outer ,may #ba4c #ai4f #af4g ,july #af4f #ah4h #aa4d ,october #af4b #af4c #ab4c ,the paper contains the results of treating the woods and various vegetable products with hydrolysing agents in order of intensity3 7a7 ,malt-extract at #fj deg4,c41 7b7 boiling dilute ,h,cl 7#a4j p4ct4 ,h,cl71 and 7c7 boiling dilute ,h,cl 7#b4e p4ct474 ,the residues were found to yield considerable proportions of furfural4 ,the following numbers are typical3 ,birch ,stones of ,bark ,wood ,date ,apricot ,peach ,action of malt extract calcu- lated as starch dissolved #d4bd #c4e #e4b #a4e -- ,residue boiled1 #a p4ct4 ,h,cl ,mannan gave pentosanes dissolved4 -- -- #aa4g #ad4a #f4g ,residue yielded furfural #ai4c #ag4h #c4d #i4f #i4g ,the proportion of pentosanes 7furfuroids7 removed1 i4e4 hydrolysed by boiling with hydrochloric acid of #b4e p4ct4 ,h,cl1 is shown by the following estimations of furfural3 ,birch ,sugar maple ,apricot stones ,bark ,wood ,outer ,inner wood wood ,in original substance #af4g #ai4f #ah4b #bj4g #ah4d ,in residue from action #f4ec #h4f #d4i #f4d #g4j of #b4e p4ct4 ,h,cl ,wood ,gum4--,the paper contains some observations on the various methods of isolating this product4 ,attention is directed to the necessary impurity of the product1 and to the fact that the numbers for furfural and for the xylose yielded by hydrolysis are considerably less than for a pure pentosane4 ,estimation of ,cellulose4--,the author investigated the process of ,lange and the 'celluloses' obtained from various raw materials4 ,the products from the woods of birch and maple contained furfural-yielding constituents1 represented by yields of #f-h p4ct4 furfural4 ,preference is given to the process by comparison with others1 at the same time that it is recommended in all cases to examine the product for furfural quantitatively1 converting the numbers into pentosane equivalents1 and subtracting from the total 'cellulose' to give the true cellulose4 ,,zur ,,kenntniss ,,der ,,muttersubstanzen ,,des ,,holzgummi4 ,e4 ,,winterstein 7,ztschr4 ,physiol4 ,chem41 #ahib1 #cha74 ,,on ,,the ,,mother ,,substances ,,of ,,wood-,,gum4 7p4 #ahh7 ,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-gum4 ,the author has subjected beech-wood and beech-wood cellulose 7,schulze process7 to a range of hydrolytic treatments1 acid and alkaline1 in order to determine the conditions of selective action upon the mother substance of the wood-gum4 ,in the main it appears that this group of furfuroids is equally resistant with the cellulose constituents of the wood2 in fact1 that the mother substance of wood-gum is a modified cellulose1 and exists in the wood in chemical combination with the 'incrusting substances4' ,of the author's experimental results the following may be cited as typical3 ,yield of furfural ,substance p4ct4 ,original beech-wood #ac4h ,after boiling #c hrs4 with #a4be p4ct4 ,h#b,,so#d 7residue7 #aj4a #e4j #e4f ,cellulose--isolated by ,schulze process 7yield #ec p4ct47 #f4i after further #ad days' digestion with the ,schulze acid 7,,hno#c ,k,cl,o#c7 #e4i after extraction with #e p4ct4 ,na,o,h in cold 7residue7 #e4j after second extraction with #e p4ct4 ,na,o,h in cold 7residue7 #d4d ,,ueber ,,die ,,frage ,,nach ,,dem ,,ursprung ,u,n,g,e,s,ae,t,t,i,g,e,r ,,verbindungen ,,in ,,der ,,pflanze4 ,c4 ,f4 ,,cross1 ,e4 ,j4 ,,bevan1 and ,c4 ,,smith 7,berl4 ,ber41 #ahie1 #aidj74 ,,on ,,the ,,source ,,of ,,the ,,unsaturated ,,compounds ,,of ,,the ,,plant4 7p4 #agi7 ,in distilling for furfural by the usual methods of boiling cellulosic products with condensing acids1 the furfural is accompanied by volatile acids1 also products of decomposition of the cellulosic complex4 ,a series of distillations was carried out with dilute sulphuric acids of varying concentration from #aj-ej ,h#b,,so#d 3 #ij-ej ,h#b,o by weight1 using barley straw as a typical cellulosic material4 ,the distillates were collected in successive fractions1 and the furfural and volatile acid determined4 ,the results are given in the form of curves4 ,the aggregate yields were as follows3-- ,concentration of acid 7,h#b,,so#d7 p4ct4 #aj #ae #bj #cj #dj #ej ,furfural yield p4ct4 of straw #b4j #b4j #d4d #aj4a #aa4e #aa4j ,volatile acid 7calculated as acetic acid7 p4ct4 of straw #a4g #a4i #c4a #d4c #f4c #ad4h ,with acids up to #bj p4ct4 ,h#b,,so#d both products are formed concurrently and in nearly equal quantity4 ,with the #cj p4ct4 acid there is a great increase in the total furfural1 and with the #dj p4ct4 acid it reaches nearly the maximum obtainable with ,h,cl of #a4jf s4g4 7,tollens71 in this case #ab4d p4ct4 ,the volatile acid increases1 but in less ratio2 it is also produced concurrently4 ,with #ej p4ct4 ,h#b,,so#d the conditions are changed4 ,the total furfural is rapidly formed1 whereas the volatile acid continues to be formed long after the aldehyde ceases to come over4 ,moreover1 whereas in the previous cases it was mainly acetic acid1 it is now mainly formic acid4 ,the method was then extended to a typical series of celluloses1 heated with the more concentrated acid 7#dj-ej p4ct4 ,h#b,,so#d71 with the following results3 ,volatile acid ,acetic ,formic ,swedish filter-paper #j4c #b4g #ag4b ,esparto cellulose #ab4d #c4b #af4f ,bleached cotton trace #c4a #ac4b ,raw cotton 7,american7 -- #e4j #i4d ,jute cellulose #e4b #d4i #bb4g ,beech 7wood7 cellulose #f4d #c4e #ad4f ,the tendency in the hexoses and their polyanhydrides to split off one carbon atom in the oxidised form1 throws some light on the furfurane type of condensation1 which is represented in the lignocelluloses4 ,we are still without any evidence as to the possible transition of the hexoses to benzenoid compounds4 ,such transitions would be more easily explained on the assumption that the celluloses are composed in part of polyanhydrides of the ketoses4 ,,spiritus ,,aus ,,cellulose ,,und ,,holz4 ,e4 ,,simonsen 7,ztschr4 angew4 ,chem41 #ahih1 #c74 ,,production ,,of ,,alcohol ,,from ,,cellulose ,,and ,,wood4 7pp4 #ej1 #bji7 ,this investigation was undertaken with one main object--to determine the optimum conditions of treatment of wood-cellulose and of wood itself for conversion into 'fermentable sugar4' ,the process of 'inversion' or hydrolysis1 by digestion with dilute acid at high temperature1 involves the four main factors3 pressure 7i4e4 temperature71 concentration of acid1 ratio of liquid to cellulose and duration of digestion4 ,each of these was varied in definite gradations1 and the effect measured4 ,the degree of action was measured in terms of 'reducing sugar1' calculated from the results of estimation by ,fehling solution1 as 'glucose' per cent4 of original cellulose 7or wood74 7a7 ,cellulose4 ,wood-cellulose obtained by bisulphite process4--,with a proportion of total liquid to cellulose of #bg 3 #a1 and using sulphuric acid as the hydrolysing agent1 the optimum results were obtained with acids of #j4de-j4fj p4ct4 7,h#b,,so#d7 and pressures of #f-h atm4 ,the maximum yield of 'sugar' was #de p4ct4 of the cellulose4 ,under the above conditions the maximum of conversion is attained in #b hours4 ,having now regard to the production of a solution of maximum concentration of dissolved solids1 the following conditions were asertained to fulfil the requirement1 and1 in fact1 may be regarded as the economic optimum3 ,proportion of total liquid #f times wt4 of cellulose ,concentration of acid #j4e p4ct4 ,h#b,,so#d ,pressure #aj atm4 ,duration of digestion #a4e hour giving a yield of #da p4ct4 'reducing sugar' calculated to the original cellulose 7dry74 ,alcoholic ,fermentation of ,neutralised ,extract4--,the liquors were found to ferment freely1 and on distillation to yield a quantity of alcohol equal to #gj p4ct4 of the theoretical--i4e4 on the basis of the numbers for copper oxide reduction4 7b7 ,hydrolytic ',conversion' of ,wood 7,lignocellulose74--,a similarly systematic investigation carried out upon pine sawdust established the following as optimum conditions3 ,proportion of total liquid #e times wt4 of wood ,concentration of acid #j4e p4ct4 ,h#b,,so#d ,pressure #i atm4 ,duration of digestion #ae minutes giving a yield of #bj p4ct4 'reducing sugar1' calculated from the ',fehling' test4 ,fermentation of the neutralised extracts gave variable results4 ,the highest yields obtained were #fj p4ct4 of theoretical1 the author finally concluding that under properly controlled conditions of inversion and fermentation #ajj kg4 wood yield #f4e l4 absolute alcohol4 ,ue,b,e,r ,,die ,,ursache ,,der ,,von ,,simonsen ,,beobachteten ,u,n,v,o,l,l,s,t,ae,n,d,i,g,k,e,i,t ,,der ,v,e,r,g,ae,h,r,u,n,g ,,der ,,aus ,,holz ,,bereiteten ,z,u,c,k,e,r,f,l,ue,s,s,i,g,k,e,i,t,e,n4 ,b4 ,,tollens 7,ztschr4 angew4 ,chem41 #ahih1 #ae74 ,,on ,,the ,,cause ,,of ,,incomplete ,,fermentation ,,of ,,sugars ,,obtained ,,by ,,acid ,,hydrolysis ,,of ,,wood4 ,the author criticises ,simonsen's explanation of the results obtained with extracts from pine wood4 ,the incompleteness of fermentation of the products is certainly due in part to the presence of furfural-yielding carbohydrates1 which are resistant to yeast4 ,the pine woods contain #h-aj p4ct4 of these constituents in their anhydride form 7'pentosanes'74 ,they yield readily to acid hydrolysis1 and certainly constitute a considerable percentage of the dissolved products4 ,a similar complex was obtained by the author in his investigation of peat 7,berl4 ,ber4 #cj1 #bega71 and was found to be similarly incompletely attacked by yeast4 ,the yields of alcohol corresponded with the proportion of the total carbohydrates disappearing4 ,these were the hexose constituents of the hydrolysed complex1 the pentoses 7or 'furfuroids'7 surviving intact4 ,,ueber ,,sulfitcelluloseablauge4 ,h4 ,,seidel 7,ztschr4 angew4 ,chem41 #aijj74 ,,waste ,,liquors ,,from ,,bisulphite ,,process4 7p4 #baj7 ,later researches confirm the conclusion that in the soluble by-products of these cellulose processes the ,s is combined as a ,,so#c;,h group4 ,the following analyses of the isolated lignin sulphonic acid are cited3 ,c ,h ,s 7a7 ,lindsey and ,tollens #ef4ab #e4cj #e4fe 7b7 ,seidel 7#a7 #ef4bg #e4hg #e4eb 7c7 ,seidel and ,hanak 7#b7 #ec4fi #e4bb #h4hj 7d7 ,street #ej4bb #e4fd #g4fg ,the variations are due to the varying conditions of the digestion of the wood and to corresponding degrees of sulphonation of the original lignone group4 ,calculating the composition of the latter from the above numbers on the assumption that the ,s represents ,,so#c;,h1 the following figures result3 7a7 and 7b7 7c7 7d7 ,c #fd4jj #fe4a #ei4fa ,h #f4fe #f4cc #f4fi ,this author considers that beyond the empirical facts established by the above named#aj very little is yet known in regard to the constitution of the lignone complex4 ,nor is there any satisfactory application of this by-product as yet evolved4 ,evaporation and combustion involve large losses of sulphur ,d4,r4,p4 #gd1jcj1 #hc1dch2 ,seidel and ,hanak1 ,mitt4 ,techn4 ,gew4 ,mus4 #ahih4 ,a more complete regeneration of the sulphur has been the subject of a series of patents ,d4,r4,p4 #dj1cjh1 #fi1hib1 #ga1idb1 #gh1cjf1 #ha1cch1 but the processes are inefficient through neglect of the actual state of combination of the ,s1 viz4 as an organic sulphonate4 ,the process of ,v4,b4 ,drewson 7,d4,r4,p4 #fg1hhi7 consists in heating with lime under pressure1 yielding calcium monosulphite 7with sulphate and the lignone complex in insoluble form74 ,the sulphite is redissolved as bisulphite by treatment with sulphurous acid4 ,this process is relatively costly1 and yields necessarily an impure lye4 ,it has been proposed to employ the product as a foodstuff both in its original form and in the form of benzoate 7,d4,r4,p4 #ig1ice72 but its unsuitability is obvious from its composition4 ,a method of destructive distillation has been patented 7,d4,r4,p4 #de1iea74 ,the author has investigated the process1 and finds that the yield of useful products is much too low for its economical development4 ,fusion with alkaline hydrates for the production of oxalic acid 7,d4,r4,p4 #eb1dia7 is also excluded by the low yield of the product4 ,the application of the liquor for tanning purposes 7,d4,r4,p4 #gb1afa7 appears promising from the fact that #bh p4ct4 of the dry residue is removed by digestion with hide powder4 ,this application has been extensively investigated1 but without practical success4 ,various probable uses are suggested by the viscosity of the evaporated extract4 ,as a substitute for glue in joinery work1 bookbinding1 c41 it has proved of little value4 ,it is applied to some extent as a binding material in the manufacture of briquettes1 also as a substitute for gelatin in the petroleum industry4 ,cross and ,bevan 7,e4,p4 #aedh_/ahhc7 and ,mitscherlich 7,d4,r4,p4 #ic1idd and #ic1ide7 precipitate a compound of the lignone complex and gelatin by adding a solution of the latter to the liquors4 ,the compound is redissolved in weak alkaline solutions and employed in this form for engine-sizing papers4 ,ekman has patented a process 7,d4,r4,p4 #ha1fdc7 for 'salting out' the lignone sulphonates1 the product being resoluble in water and the solution having some of the properties of a solution of dextrin4 ,owing to its active chemical properties this product--'dextron'--has a limited capability of substituting dextrin4 ,the suggestion to employ the evaporated extract as a reducing agent in indigo dyeing and printing has also proved unfruitful4 ,the author's application of the soda salt of the lignone sulphonic acid as a reducing agent in chrome-mordanting wool and woollen goods 7,d4,r4,p4 #ii1fhb7 is more successful in practice1 and its industrial development shows satisfactory progress4 ,the product is known as 'lignorosin4' ,,footnotes3 #aj ,see more particularly3 ,lindsey and ,tollens1 ,annalen1 #bfg1 #cda2 ,cross and ,bevan's ,cellulose1 pp4 #aig-bjc2 ,street1 ,inaug4-,diss41 ,goettingen1 #ahib2 ,klason1 ,rep4 d4 ,chem4 ,ztg4 #ahig1 #bfa2 ,seidel and ,hanak1 ,mitt4 d4 ,techn4 ,gew4 ,mus4 #ahig-ahih4 ,,section ,,vii4 ,,pectic ,,group ,,untersuchungen ,ue,b,e,r ,,pectinstoffe4 ,r4 ,w4 ,,tromp ,,de ,,haas and ,b4 ,,tollens 7,lieb4 ,ann41 #bhf1 #bgh74 ,ue,b,e,r ,,die ,,constitution ,,der ,,pectinstoffe1 ,b4 ,,tollens 7ibid4 #bib74 ,,investigations ,,of ,,pectins4 7p4 #baf7 ,it is generally held that the pectins are1 or contain1 oxidised derivatives of the carbohydrates4 ,the authors have isolated and analysed a series of these products1 and the results fail to confirm a high ratio ,o 3 ,h4 ,the following are the analytical numbers3 ,pectin from ,ash ,c ,h ,ratio ,h 3 ,o ,apple #f4b #dc4d #f4d #a 3 #g4i ,cherry #bj4e #db4e #f4e #a 3 #g4i ,rhubarb #d4b #dc4c #f4h #a 3 #g4d ,currant #e4j #dg4a #e4i #a 3 #h4e ,greengage #c4c #dc4j #e4i #a 3 #h4e ,turnip #g4c #da4j #e4i #a 3 #i4j ,acid hydrolysis 7#d p4ct4 ,h#b,,so#d7 gave syrupy products not crystallisable--in certain cases the hydrolysis was accompanied by separation of insoluble cellulose4 ,the insoluble product from currant pectin had the composition ,c #ed4d1 ,h #e4j4 ,tollens points out that the results of empirical analysis are inconclusive2 and that from the acid reactions of these products and their combination with bases1 carboxylic groups are present1 though probably in anhydride or ester form4 ,the pectins may be regarded as closely related to the mucilages 7,pflanzenschleim71 differing from them only by the presence of the oxidised groups in question4 ,,ueber ,,die ,,constitution ,,der ,,pectinstoffe4 ,c4 ,f4 ,,cross 7,berl4 ,ber41 #ahie1 #bfji74 ,,constitution ,,of ,,pectins4 ,it is pointed out that the composition of the pectin of white currants1 as given in the preceding paper1 is that of the typical lignocellulose1 the jute fibre4 ,the product was isolated and further investigated by the author4 ,it gave #i4h p4ct4 furfural on boiling with ,h,cl 7#a4jf s4g471 reacted freely with chlorine1 giving quinone chlorides1 and with ferric ferricyanide to form ,prussian blue4 ,this 'pectin' is therefore a form of soluble lignocellulose4 ,the 'pectic' group consequently must be extended to include hydrated and soluble forms of the mixed complex of condensed and unsaturated groups with normal carbohydrates1 such as constitute the fibrous lignocelluloses4 ,,ueber ,,das ,,pflanzliche ,,amyloid4 ,e4 ,,winterstein 7,ztschr4 ,physiol4 ,chem41 #ahib1 #cec74 ,,on ,,vegetable ,,amyloid4 7p4 #bbd7 ,a group of constituents of many seeds1 distinguished by giving slimy or ropy 'solutions' under the action of boiling water are designated 'amyloid4' ,they are reserve materials1 and in this1 as in the physical properties of their 'solutions1' they are very similar to starch4 ,they are1 however1 not affected by diastase2 and generally are more resistant to hydrolysis4 ,typical amyloids have been isolated by the author from seeds of ,tropoeolum majus1 ,poeonia officinalis1 and ,impatiens ,balsamina4 ,the raw material was carefully purified by exhaustive treatment with ether and alcohol1 c42 the amyloid then extracted by boiling with water1 and isolated by precipitation with alcohol4 ,elementary analysis gave the numbers ,c #dc4b1 ,h #f4a4 ,on boiling with #ab p4ct4 ,h,cl it gave #ae4c p4ct4 furfural2 oxidised with nitric acid it yielded #aj4d p4ct4 mucic acid4 ,specimens from the two first-named raw materials gave almost identical numbers4 ,hydrolysis4--,on boiling with dilute acids these products are gradually broken down1 dissolving without residue4 ,in this respect they are differentiated from the mucilages1 which give a residue of cellulose 7insoluble74 ,from the solution the author isolated crystalline galactose1 but failed to isolate a pentose4 ,dextrose was also not identified directly4 ,the tissue residues left after extracting the amyloid constituent1 as above described1 were subjected to acid hydrolysis4 ,a complex of products was obtained1 from which galactose was isolated4 ,a furfural-yielding carbohydrate was also present in some quantity1 but could not be isolated4 ,the original seed tissues1 therefore1 contain an amyloid and a hemicellulose1 the latter differentiated in its resistance to water4 ,both yield1 however1 to acid hydrolysis a complex of products of similar composition and constitution4 ,,ueber ,,den ,,gehalt ,,des ,,torfes ,,an ,,pentosanen ,,oder ,,furfurolgebenden ,,stoffen ,,und ,,an ,,anderen ,,kohlenhydraten4 ,h4 ,v4 ,,feilitzen and ,b4 ,,tollens 7,berl4 ,ber41 #ahig1 #b1ega74 ,,carbohydrate ,,constituents ,,of ,,peat4 7p4 #bdj7 ,an investigation of typical peats taken at successive depths showed increasing percentage of carbon1 and inversely a decreasing yield of furfural4 ,the numbers may be compared with those for ,sphagnum cuspidatum--with ,c #di4hj p4ct41 and furfural #g4ii p4ct41 calculated to dry1 ash-free substance3 ,depth at which taken ,c p4ct4 ,furfural p4ct4 #bj-ajj cm4 #ea4jh #f4ic ,i4 #ajj-bjj #ec4eb #e4cj #bjj-cjj #eh4ff #c4ai ,surface-#bj #ee4dg #c4dj ,,ii4 #bj-fj #ee4jf #c4dh #fj-ajj #eh4be #a4de #ajj-abj #eh4bc #a4ai #ahj-bjj #eg4eg #a4hj ,cellulose was estimated by the ,lange method4 ,the yield from ,sphagnum was #ba4a p4ct4 ,from specimen ,i4 at #bj-ajj cm4 #ae4bj #ajj-bjj #f4hg ,from the peat of lower depths no cellulose could be obtained4 ,hydrolysis 7acid74--,on heating with #a p4ct4 ,h#b,,so#d at #acj-ace deg41 soluble carbohydrates were obtained1 amongst which mannose was identified1 and galactose shown to be present in some quantity4 ,after fermenting away the hexoses1 the residue was treated with phenylhydrazine and an osazone separated4 ,it contained #ag4c p4ct4 ,n1 but melted at #acj deg44 ,the substance could not be identified as an osazone of any of the yet known pentoses4 ,,section ,,viii4 ,,industrial ,,and ,,technical4 ,,general ,,review ,the ,industrial ,uses of ,cellulose4 ,c4 ,f4 ,,cross 7,cantor ,lectures1 ,soc4 of ,arts1 #ahig74 7p4 #bgc7 ,a series of three lectures1 in which the more important industries in cellulose and its derivatives are dealt with on their scientific foundations1 and by means of a selection of typical problems4 ,in reference to textiles1 the small number of vegetable fibres actually available1 out of the endless variety afforded by the plant world1 is referred to the number of conditions required to be fulfilled by the individual fibre1 thus3 yield per cent4 of harvested weight or per unit of field area1 ease of extraction1 the absolute dimensions of the spinning unit1 and the proportion of variation from the mean dimensions2 the relative facility with which the unit fibre can be isolated preparatory to the final twisting operation2 the chemical constants of the fibre substance1 especially the percentage of cellulose and degree of resistance to hydrolysis4 ,it is suggested that any important addition to the very limited number fulfilling the conditions1 or any great improvement in these1 can only result from very elaborate artificial selection and cultural developments on this basis4 ,the paper making fibres are shown to fall into a scheme of classification based on chemical constitution1 and consisting of the four groups3 7a7 ,cotton flax1 hemp1 rhea1 7b7 wood celluloses1 7c7 esparto1 straw1 and 7d7 lignocelluloses4 ,papers being exposed to the natural disintegrating agencies1 more especially oxygen1 water 7and hydrolysing agents generally71 and micro-organisms1 the relative resistance of the above groups of raw materials is discussed as an important condition of value4 ,the indirect influence of the ordinary sizing and 'filling' materials is discussed4 ,the paper-making quality of the fibrous raw materials is also discussed1 not merely from the point of view of the form and dimensions of the ultimate fibres1 but their capacity for 'colloidal hydration4' ,this is complementary to the action of rosin1 i4e4 resin acids1 in the engine-sizing of papers2 and the proof of the potency of this factor is seen in the superior effects obtained in sizing jointly with solutions of cellulose and1 more particularly1 viscose and rosin4 ,wurster's much-cited monograph of the subject of rosin-sizing ',le ,collage des ,papiers1' ,bull4 ,mulhouse1 #ahgh neglects to take into consideration the contribution of the cellulose hydrates to the total and complex sizing effect1 and hence gives a partial view only of the function of the resin acids4 ,in further illustration of fundamental principles various developments in the textile industries are discussed1 e4g4 the bleaching of jute1 cotton1 and flax1 and special developments in the spinning of rhea and flax4 ,the concluding lecture deals with later progress in the industrial applications of cellulose derivatives1 chiefly the sulphocarbonate 7viscose72 the nitrates1 in their applications to explosives1 on the one hand1 and the spinning of artificial fibres 7lustra-cellulose71 on the other2 and the cellulose acetates4 ,la ,viscose et le ,viscoide4 ,c4 ,h4 ,,bardy 7,bull4 ,soc4 d',enc4 ,ind4 ,nationale1 #aijj1 ,march74 ,this is a report presented to the ,committee of ,economic ,arts of the above ,society1 dealing with the industrial progress in products obtained by means of the sulphocarbonate of cellulose 7viscose74 ,the following developments are noted3 ,engine-sized ,papers4--,the viscose1 by coating the fibres with regenerated cellulose hydrate1 adds very much to the tensile strength of papers4 ,increase of #dj-fj p4ct4 is attainable by addition of cellulose in this form from #a-d p4ct4 on the weight of the paper4 ,viscoid4--,solid aggregates are formed by incorporating viscose with mineral matters1 hydrocarbons1 c4 ,products are cast or moulded into convenient forms1 and1 after purification and sufficient ageing1 are available for various structural uses4 ,paint4--,the viscose is used as a vehicle for pigments1 the mixture being used either as a paint or for coating papers with fine surfaces1 such as required in the reproduction of photo-blocks4 ,in these applications the extraordinary viscosity of the product conditions the economic use of the cellulose in competition with oils1 on the one hand1 and organic colloids1 such as gelatine1 casein1 c41 on the other4 ,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 surfaces4 ,the product has been officially adopted by the ,french ,admiralty1 and receives extensive application in removing the paint from ships4 ,films4--,films are produced from the viscose itself in various ways4 ,plane or flat by solidifying the viscose on glass surfaces1 removing the by-products and rolling the films4 ,the film is also produced by applying the viscose on textile fabrics1 drying down1 and fixing on a stenter machine1 then washing away the alkaline by-products from the fixed film4 ,a large number of industrial effects are obtained by suitably varying the mixtures applied4 ,cellulose-indiarubber4--,the viscose1 in its concentrated form1 can be incorporated with rubber-hydrocarbon mixtures1 and these mixtures can be used both as water-proofing films1 as applied to textiles1 or can be solidified into the class of goods known as 'mechanicals4' ,the cellulose not only cheapens the mixture1 but produces new technical effects4 ,spinning4--,the viscose is spun by special methods1 patented by ,c4 ,h4 ,stearn4 ,as produced in thread form1 the diameters are approximately those of natural silk4 ,in commercial form it is a multiple thread 7of #ae or more units7 at from #ej-bjj deniers on the silk counts4 ,it is a thread of high lustre1 and more nearly approaches the normal cellulose in chemical properties than any of the other artificial silks4 ,it can also be spun in threads of very much larger diameter1 which can be used as a substitute for horsehair1 for carbonising for incandescent electric lamps1 c4 ,cellulose ,esters4--,these are conveniently made from cellulose1 regenerated from the solution as sulphocarbonate4 ,the tetracetate is made from this product on the industrial scale4 ,nitrates are conveniently made by treatment with the ordinary mixed acids4 ,for fuller details the original report may be consulted4 ,,viskos4 ,r4 ,w4 ,,strehlenert 7,svensk ,kemisk ,tidskrift1 ,stockholm1 #aijj1 p4 #ahe74 ,a report on the industrial development of viscose1 covering essentially the same ground as the above4 ,ueber die ,viscose4 ,b4 ,m4 ,,margosches 7,reprint from ,zeitschrift fuer die gesammte ,textil-,industrie1 #aijj-ja1 ,nos4 #ad-bj74aa ,report of ,committee on the ,deterioration of ,paper4 7,soc4 of ,arts1 #ahih47 7p4 #cjd7 ,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 applications1 and more especially for documents of permanent value4 ,the report first discusses the two directions of depreciation of papers in use3 7#a7 ,actual disintegration shown by loss of resistance to fracture by simple strain1 and by loss of elasticity--i4e4 increase of brittleness2 7#b7 discolouration4 ,these are independent effects1 but often concurrent4 ,they are the result of chemical changes of the cellulose basis of the paper1 brought about by acids or oxidants used in the process of manufacture1 and not completely removed from the pulp1 or by acid products of bleaching--e4g4 oxycelluloses or chlorinated derivatives2 again1 by the changes of starch used as a 'sizing' agent1 or by oxidations induced by rosin constituents when the rosin is used in excess4 ,discolouration is an attendant phenomenon of these changes1 but is more frequently due to the presence of the lower-grade celluloses 7esparto and straw7 and the lignocelluloses 7mechanical wood-pulp74 ,the physical and chemical qualities of papers depending primarily upon their fibrous or pulp basis1 and in a secondary degree upon the kind and proportion of the constituents added for the purpose of filling and 'sizing1' the report concludes with the following recommendations1 positive and negative1 under these heads3 ,the ,committee find that the practical evidence as to permanence fully confirms the classification given in the ,cantor ,lectures on ',cellulose1' #ahig ,j4 ,soc4 ,arts1 xlv4 #fij-fif1 and which ranges the paper-making fibres in four classes3 7,a7 ,cotton1 flax1 and hemp 7rhea74 7,b7 ,wood celluloses1 7a7 sulphite process and 7b7 soda and 'sulphate' process4 7,c7 ,esparto and straw celluloses4 7,d7 ,mechanical wood-pulp4 ,in regard1 therefore1 to papers for books and documents of permanent value1 the selection must be taken in this order1 and always with due regard to the fulfilment of the conditions of normal treatment above dealt with as common to all papers4 ,the ,committee have been desirous of bringing their investigations to a practical conclusion in specific terms--viz4 by the suggestion of standards of quality4 ,it is evident that in the majority of cases there is little fault to find with the practical adjustments which rule the trade4 ,they are1 therefore1 satisfied to limit their specific findings to the following--viz4 7#a7 normal standard of quality for book-papers required for publications of permanent value4 ,for such papers they specify as follows3 ,fibres3 ,not less than #gj p4ct of fibres of class ,a2 class ,d excluded4 ,sizing3 ,not more than #b p4ct4 rosin1 and finished with the normal acidity of pure alum2 starch excluded4 ,loading3 ,not more than #aj p4ct4 total mineral matter 7ash74 7#b7 ,with regard to written documents1 it must be evident that the proper materials are those of class ,a1 and that the paper should be pure and sized with gelatin1 and not with rosin4 ,all imitations of high-class writing-papers which are1 in fact1 merely disguised printing-papers1 should be carefully avoided4 ,appendix4--,to the ,report is added ',abstracts of ,papers' in ',mittheilungen aus den ,koniglichen ,technischen ,versuchsanstalten1 ,berlin1' for the years #ahhe-ahif inclusive--which is1 in fact1 a summary of the investigations of the ,institution in connection with paper and paper-standards4 99 99 99 99 99 7p4 #bgc7 ,special ,industrial ,developments4--,from the point of view of the chemist there has been a very large development of the cellulose industries during the last five years4 ,this is not so much marked by the gradual and progressive growth of the well-established industries1 as by the success of the newer ones1 with the attendant forecast of enormous developments of the industries in artificial products1 the manufacture of which rests upon a purely chemical basis4 ,we can1 of course1 only treat them from this limited standpoint1 and so far as they involve and elucidate chemical principles4 ,i4 ,chemical ,treatments of ,raw ,materials4 7a7 ,flax-spinning4--,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 results4 ,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 work1 p4 #bhj4 ,since that time a sufficient period has elapsed to judge the effects1 both technical and industrial1 by the results of a commercial undertaking based on the exclusive use of the process4 ,such a concern is the ,irish ,flax ,spinning ,company of ,belfast4 ,at this mill the experience is uniform and fully established that by means of the process the drawing1 i4e4 spinning1 quality of inferior flaxes is very considerably appreciated1 enabling the spinner to use such flaxes for yarns of fineness which are unattainable by the ordinary method of spinning through hot water4 ,notwithstanding the success of this undertaking the development of the method is still inconsiderable4 ,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 exploit4 7b7 ,wood-pulp and ,methods of ,manufacture4--,there is a steady growth in the consumption of wood-pulps 7cellulose7 relatively to other materials4 ,in regard to the paper-trade of the world1 this continues to be one of the most prominent characteristics of its evolution4 ,in the ,united ,kingdom the conditions of its competition are of a more special kind by reason of the firm foothold of esparto1 which is a most important staple in the manufacture of fine printings4 ,whereas the consumption of esparto remains nearly stationary at about #bjj1jjj tons per annum1 the importation of wood-pulps has shown the extraordinary rate of increase of doubling itself every five years4 ,but in the group 'wood-pulps' the trade returns have until recently included the 'mechanical' or ground wood-pulps4 ,from #ahih we have separate returns for the chemical or cellulose pulps1 and in #ahii the tonnage reached nearly to that of esparto1 with a total money value about #hj p4ct4 greater4 ,when it is remembered that this is one of the newer chemical industries in cellulose products1 and that these large commercial results have been accomplished during a period of twenty years1 we are impressed with the scope of the industrial outlook to the chemist1 afforded by the arts of which cellulose is the foundation4 ,it may be noted that there have been no important developments in the purely chemical processes involved in the several systems of preparing cellulose from wood4 ,the acid methods 7bisulphite processes7 have developed much more extensively than the alkaline1 the latter including the caustic soda and the mixed sulphide 7',dahl'7 process4 ,the bisulphite processes depended in the earlier stages upon the efficiency of lead-lined digesters4 ,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 use4 ,the relative permanency of these linings has had an important effect on the costs of production4 ,further economies result from the use of digesters of enormous capacity1 dealing with as much as #ajj tons of wood at one operation4 ,as a combined result of economic production and active competition1 the selling prices of 'sulphite pulp' have moved steadily downwards in relation to other half-stuffs and raw materials4 ,as a necessary consequence the prices of those which it has gradually displaced have depreciated1 and a study of the price and tonnage-equilibrium as between rags1 esparto1 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 industry4 ,for these matters the reader is referred to the special literature of the paper-making industry4#ab ,it is not a little remarkable that the main by-product of these bisulphite processes--the sulphonated derivatives of the lignone constituents of the wood--is still for the most part an absolute waste1 notwithstanding the many investigations of technologists and attempts to convert it to industrial use 7see p4 #adi74 ,seeing that it represents a percentage on the wood pulped equal to that of the cellulose obtained1 it is a waste of potentially valuable material which can only be termed colossal4 ,moreover1 as a waste to be discharged into water-courses1 it becomes a source of burden and expense to the manufacturer1 and with the increasing restrictions on the pollution of rivers it is in many localities a difficulty to be reckoned with only by the cessation of the industry4 ,the problem in such cases becomes that of dealing with it destructively1 i4e4 by evaporation and burning4 ,in this treatment the obviously high calorific value of the dissolved organic matter 7lignone7 appears on the 'credit' side4 ,but where calcium and magnesium bisulphites are used1 the residue from calcination is practically without value4 ,it appears1 however1 that by substituting soda as the base the alkali is recoverable in such a form as to be directly available for the alkaline-sulphide or ',dahl' process4 ,as a more complicated alternative the soda admits of being recovered on the lines of the old black-ash or ,leblanc process1 and the sulphur by the now well-established ',chance' process1 for which1 of course1 an addition of lime is necessary to the fully evaporated liquors previously to calcining4 ,the engineering features of the system1 so far as regards evaporating and calcining1 are the same4 ,for economic working there is required 7a7 evaporation by multiple effect and 7b7 calcining on the continuous rotary principle4 ,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 furnace1 securing a progressively increasing temperature within the furnace4 ,this interesting development of the chemical engineering of wood-pulp systems has been elaborated by two well-known technologists1 ,drewson and ,dorenfeldt1 and readers who wish to inform themselves in detail of these developments are referred to the various publications of these inventors4 ,assuming the present necessity of a destructive treatment of the by-products of the bisulphite processes1 the scheme has many advantages4 ,the soda-bisulphite liquors are more economically prepared2 the pulp obtained is superior in paper-making quality to that resulting from the lime or magnesia 7bisulphite7 processes3 it is more economically bleached4 ,then1 as pointed out1 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' pulp4 ,these two systems become1 therefore1 in a new sense complementary to one another4 ,lastly1 it is obvious that the employment of soda as the base opens out a new vista for developing the electrolytic processes of decomposing common salt4 ,the authors have assisted in preparing plans for a comprehensive industrial scheme combining all these more modern developments4 ,in this scheme it is only the combination which is novel1 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 basis4 ,this may be summed up in result in the important question of cost and selling price1 and the estimate is well grounded that by means of this scheme bleached wood-pulp can be sold on the ,english market at #ajl4 a ton4 ,it is important to note this figure and to compare it with the prices of twenty years ago4 ,the fall has been continuous1 notwithstanding the influence of the opposing factors of increasing consumption1 exhaustion of accessible supply of timber1 and relative appreciation of the essential costs of steam1 chemicals1 and labour4 ,it is important in forecasting the future1 since the youngest and apparently most promising of the 'artificial' cellulose industries employs wood-cellulose by preference as its raw material 7see p4 #agc74 ,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 processes4 ,outside the intrinsic interest attaching to the solution of this problem1 it carries with it the promise of a further economy in the production of wood-cellulose4 ,bleaching of ,vegetable ,textiles4--,by far the largest of these industries are those which are engaged in producing the 'pure white' on cotton and flax goods4 ,the process1 considered chemically1 is simply that of isolating a pure cellulose1 and we endeavoured to give due prominence to this view in the original work4 ,it is important to insist upon it for the reason that this view gives the due proportion of chemical value to the several contributory treatments--alkaline hydrolyses 7caustic lime and soda boils71 hypochlorite oxidations1 and incidental acid treatments 7souring74 ,the first of these is by far the largest contributor of 'chemical work1' though the second1 by being the agent for the actual whitening effect or bleaching action proper1 occupies a position of often exaggerated importance4 ,in bleaching processes there has been no radical change of system on the large scale since the introduction of the ',mather' kier in #ahhe1 and the associated change from lime and ash boiling to the caustic soda circulating boil with reduced volume of lye1 which this mechanical device rendered practicable4 ,it is outside the scope of this work to follow up this branch of technology in any detail1 and we cannot discuss the evolution of systems on variations of detail where no essential principle is involved4 ,but we have to notice a very recent development which has only just begun its industrial career1 and which does give effect to a principle of treatment not previously applied4 ,this is tersely stated by its originator1 ,william ,mather1#ac in the expression1 'it is more economical to make liquids pass through cloth than to make cloth pass through liquids4' ,the starting point of this development is the invention of a complete self-contained machine in which a rolled batch of cloth can receive a succession of chemical treatments1 with accessory washings--the solutions1 or wash waters1 being circulated through the cloth4 ,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 cloth4 ,such circulation is therefore quite independent of the diameter of the batch4 ,if we consider a cloth under chemical treatment with solutions1 it is clear that the reactions and interchanges of soluble matters within the cloth1 within the twisted elements of the yarn1 and in the last grade of distribution within the actual ultimate fibres1 are subject to capillary transmission1 and osmotic exchange4 ,there is a mixture of these molecular effects1 with the circulation in mass1 sweeping both faces of the cloth4 ,it is obvious that for the mass effect a relatively very small volume of circulating liquid is necessary to maintain uniform conditions of action4 ,in the actual disposition of the machine the rolled batch of cloth nearly fills the cylindrical space of what we may call the reaction chamber1 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 batch4 ,this is in the meantime kept in slow revolution4 ,for a full description of these mechanical details the reader is referred to the original patent specifications ,engl4 ,pat4 #bc1djj1 #bc1dja2 #aijj1 ,w4 ,mather4 ,if we again consider the principles involved1 they are very much as set forth in our original work 7pp4 #bhh-bia74 ,boiling processes in which a relatively large volume of liquid is used are wasteful of steam1 the active agent is unnecessarily diluted or used in superfluous quantity1 and the soluble by-products1 being continually removed as formed1 cannot so effectively contribute by secondary actions to the chemical work4 ,the new mechanical appliance enables us to further reduce the volume of liquid required in the alkaline-hydrolytic treatment of vegetable textiles1 and where advantageous to bring the treatment down 7or up7 to a process of steaming with the active agent dissolved in a minimum proportion of water relative to the cloth4 ,this concentration of effect is of importance in flax cloth1 and especially linen treatment1 where the peculiarly resistant cutocelluloses have to be attacked and a considerable proportion of waxy by-products to be removed4 ,these points are the basis of the special process of ,cross and ,parkes ,engl4 ,pat4 #be1jgf_/ #ii for steaming flax 7and cotton7 goods with an emulsion containing1 in addition to the special hydrolysing agent--caustic soda--mixtures of soap with 'mineral' or other oils1 the presence of which effectually aids the removal of the by-products in question4 ,a complete system on these lines is now working on the industrial scale in the ,belfast district4 ,the results are not merely economical in largely reducing the number of alkaline boiling treatments required on the old plan of pan or 'pot' boiling1 but are visible in the strength and finish of the linens so treated4 ,for cotton bleaching the costs may be put down at a fraction of those of the ,irish linen bleach4 ,the economical advantages of the new system are obviously less in relation to the lesser total costs4 ,but there are other points which have come into more prominent influence4 ,the mechanical wear and tear on the cloth is considerable in the ordinary process1 more especially in the mangle-washes4 ,as a result the adjustment of warp and weft is more or less disturbed4 ,these defects are absent from a system which operates on the cloth in a fixed position4 ,but as we are mainly concerned with the purely chemical factors we cannot pretend to deal with textile questions4 ,we have to notice the remaining element of chemical economy as it involves a fundamental principle4 ,the practice of washing residues or products of reaction free from reagents and soluble by-products involves a well-known mathematical law1 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 latter4 ,the ordinary practice of textile washings entirely ignores this principle1 and the consumption of water in consequence may reach many thousand times the economic minimum4 ,with supplies of water often in indefinite excess of requirements1 even in this most wasteful method1 bleachers are in no need to consider the question of consumption4 ,but leaving aside particular and local considerations of advantage the fact is that the new system gives control of the practice of washing1 enabling the operator to adapt an important element of the daily routine to a fundamental principle which has been almost universally ignored4 ,in the oxidising processes which follow the alkaline treatments1 the hypochlorites are still the staple agents4 ,owing to the steady relative fall in the selling prices of the permanganates these are coming into more extensive use1 but the consumption is still small1 and they are mainly used for certain special effects1 chiefly in linen or more generally flax cloth bleaching4 ,paper-pulp ,spinning4--,paper is a continuous web or fabric produced by the interlocking of the structural fibrous units of the well-known short length4 ,in ,japan and other countries paper is made to serve for all or some of the purposes for which we employ string or twine1 and to give the necessary tensile strength the paper is twisted or rolled on itself4 ,such twisting1 however1 adds nothing to the intrinsic tensile qualities of the original paper4 ,a new technical effect is realised in this direction by the treatment of paper-pulp in the process of its conversion into a continuous web3 ,the pulp is formed into continuous strips of convenient breadth 7usually from #b to #h mm471 these receive a 'rolling-up' treatment immediately following the squeeze of the press rolls by which the superfluous water is removed3 they are then further but incompletely dried1 and in this condition are subjected to a final spinning or twisting treatment on ring-spinning machinery of special construction4 ,such a process was originally patented by ,c4 ,kellner in this country 7,e4,p4 ,no4 #bj1bbe_/ahia71 and is fully described in his specification4 ,later improvements in detail were patented by ,g4 ,tuerk 7,e4,p4 #dfba_/ahib74 ,a joint system is now being industrially developed in ,germany by the ,altdamm-,stahlhammer ,pulp and ,paper ,company under the technical direction of ,dr4 ,max ,mueller1 and there appears to be every prospect of the product taking a position as a staple textile4 ,the process has only the incidental interest in connection with our main subject1 that it employs chiefly the 'chemical' pulps or celluloses as raw materials4 ,the industrial future of the application must1 of course1 be largely determined by costs of production1 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 wetting4 ,all these questions have been duly weighed by those engaged in this interesting development1 and the conclusion of those qualified to judge is that the new industry has vindicated for itself a permanent position4 ,,ii4 ,the ,chemical ,derivatives of ,cellulose1 in their industrial aspects1 have come to occupy a profoundly important position in the world's affairs4 ,in the way of any essential alteration of the perspective from that obtaining in #ahie we have nothing to chronicle4 ,no new derivatives of industrial importance have been added in that period2 but certain new methods incidental to the preparation of well-known compounds or for converting them into more generally available forms have been introduced1 and these are contributing to the rapid expansion of the 'artificial' cellulose industries4 ,of the cellulose esters the nitrates are still the only group in industrial use4 ,there uses for explosives have attained immense proportions1 and their applications for structural purposes are continually on the increase4 ,the manufacture of smokeless powders on the one hand1 and of celluloid and xylonite 7both in the form of films and solid aggregates7 on the other1 has taken no new departure4 ,the industry in 'artificial silks' or 'lustra-celluloses1' by the collodion processes also1 whilst presenting features of unusual interest attaching to rapid expansion1 has been barren of contribution of fundamental scientific or technical importance4 ,the tetracetate is now manufactured on the large scale1 but the product has yet to make its market4 ,the process of mercerising cotton yarns and cloth has been developed to an industry of colossal dimensions1 and the growth has been especially rapid during the last five years4 ,significant of the technical progress in these two industries1 with their common aim of appreciating cellulose in the scale of textiles by approximating its external properties in those of silk1 is the appearance of a monograph of the technology of each1 notices of which have been previously given 7pp4 #bb-bf74 ,there is little doubt1 however1 that the question of the future industry in the various forms of cellulose1 thread1 film1 structureless powder or solid aggregate1 obtainable by artificial means1 mainly turns upon cost of production4 ,irrespective of cost1 there would1 no doubt1 be a market for all these products1 based upon such of their properties or effects as are indispensable and not otherwise obtainable4 ,as an illustration1 we may cite the extraordinary selling prices of #dj-ej fr4 per kilo1 for the 'artificial silks' 7collodion process7 which ruled some three years ago2 and we may note that for a special application of viscose the dissolved cellulose is paid for at the rate of #aj per lb4 ,these facts are certainly worthy of mention1 and should be borne in mind as an index of some special features of modern manufacturing industry4 ,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 products4 ,that question is rapidly solving itself in this country as regards the 'artificial silks4' ,there is at present a limited market at #is4-#ajs4 per lb41 a price which on the one side excludes extensive consumption1 and on the other practically bars manufacture in this country by any of the collodion systems4 ,it will appear from a very elementary calculation of what we may call the theoretical costs that the above selling price would not have a remunerative margin4 ,the theoretical costs are made up of ,raw materials#ad ,cotton4 ,nitrating acid4 ,ether-alcohol 7solvent74 ,denitrating chemicals4 7a7 ,nitrating and preparing collodion4 ,denitrating and bleaching4 ,labour 7b7 ,textile operations4 ,spinning4 ,winding and twisting4 ,rewinding4 ,power ,making1 filtering1 and distributing collodion4 ,driving textile machinery4 ,added to which are the costs of expert management and supervision and general establishment expenses4 ,it is evident that raw materials make up a large fraction of the total cost2 also that a very large item is the waste work of converting the cellulose into nitrate1 only to remove the nitric groups so soon as the cellulose is obtained as thread4 ,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 decomposition1 but the first cost of the solution is very much less4 ,with these newer products1 therefore1 the spinning problem enters on a new phase of struggle4 ,it is certain that at selling prices at or about #es4 to #gs41 very large markets will be open to the product or products4 ,the two processes which are or may be able to fulfil this demand are those based 7#a7 on cuprammonium solutions of cellulose1 7#b7 on the sulphocarbonate or viscose4 ,as regards first cost of the solution the latter has a large advantage4 ,one ton of wood pulp 7at #abl47 can certainly be obtained in solution in a condition ready for spinning at a total cost 7materials7 of less than #cjl4 ,the cuprammonium process1 so far as 'outside' information goes1 requires for production of the solution 7#a7 cotton as raw material1 7#b7 ammonia 7calc4 as concentrated aqueous7 equal to #a-a_/b times its weight1 and 7#c7 metallic copper #be p4ct4 of its weight2 and the costs are approximately #ajjl4 per ton4 ,it is obvious that the materials are recoverable from the precipitating-bath1 but at a certain added cost4 ,we have no statements as to the proportion recoverable nor the costs incurred1 and we are therefore unable to measure the total net cost of the regenerated cellulose by this process4 ,it is certainly much less than by the collodion processes4 ,as to the textile quality of the thread1 the product has not yet been on a sufficiently wide selling basis for that to have been determined4 ,there are a great many factors which enter here4 ,not merely the external characters of lustre1 softness1 and translucency1 but the all-important quality of uniformity of thread4 ,the collodion-spinning is a process still very defective in this respect1 and the defect is no doubt referable to the difficulty of securing absolute physical invariability of the collodion4 ,it is to be regretted1 in the interests of scientific development1 that none of the technologists who have published investigations of these processes have entered into the discussion of the fundamental factors of the spinning processes2 we are1 therefore1 unable at this stage to discuss these elements of a full comparison in greater detail4 ,we cannot1 for this reason1 say how far the cuprammonium process diverges in point of control from the standard of the collodion processes4 ,of the 'viscose' product we have a more intimate knowledge1 and it certainly reaches a higher general standard than the older and now well-known artificial silks4 ,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' processes4 ,this would assure to this system an entree in this country1 and a basis of expansion limited only by the ordinary laws of supply and demand4 ,this prospect is opened up precisely at the moment when1 for various reasons connected both with the difficulties of manufacture and the narrowing of the margin of profit1 the proprietors of the two systems of collodion-spinning have decided to abandon all idea of manufacturing by these systems in this country4#ae ,we leave the discussion of the industrial problem at this point4 ,in regard to other developments based upon the exceptional character and properties of the sulphocarbonate1 their further discussion will exemplify no general principles2 and as regards technical detail they have been dealt with in the papers previously noticed4 ,as a purely general question1 if there is to be any industry in these 'artificial' forms of cellulose1 commensurate with the magnitude that usually belongs to the cellulose industries1 it must come by way of a plastic or soluble form prepared at low cost1 and conserving the essential molecular properties of the cellulose aggregate4 ,these are the particular features of the sulphocarbonate4 ,the obvious difficulties in the way of its industrial applications are those caused by the presence of alkali and sulphur compounds4 ,these are dealt with by appropriate chemical means2 but the fact that there is a special chemistry of the product has rendered its industrial progress slow4 ,the work of the last five years in this1 as in other applications of cellulose in its many derived forms1 has resulted in a considerable addition to the domain of practical chemistry4 ,further developments will make an increasing demand upon our grasp of the fundamental constitutional problems1 to which it is the main purpose of the present volume to contribute4 ,,footnotes3 #aa ,this is the most complete notice that has appeared and the bibliography is exhaustive4 ,the publication comes into our hands too late to be noticed in detail4 #ab ,text-book on ,paper-making1 ,cross and ,bevan 7,spon1 ,london3 second edition1 #aijj74 ,chemistry of ,paper-making1 ,griffin and ,little 7,new ,york1 #ahid3 ,howard ,lockwood ,co474 ,handbuch d4 ,papierfabrikation1 ,c4 ,hofmann 7,berlin74 ,paper ,trade ,review1 ,london 7weekly74 ,papier-,zeitung1 ,berlin4 #ac ,william ,mather1 ,m4,p41 of the firm of ,mather ,platt1 ,limited1 ,manchester4 #ad ,the actual costs varying considerably in the various countries1 we cannot make any specific statement4 ,but from estimates we have made1 the costs of obtaining cotton in filtered solution as collodion multiply its value by #ab-ad1 the denitrations adding further costs and raising this multiple to #ah-bj4 ,in the same estimates we arrived at the conclusion that the item for raw materials made up #fj p4ct4 of the total cost of the yarn4 #ae ,the recent failure of a ,french company founded for the exploitation of the cuprammonium process may be taken as showing that it presents very considerable technical difficulties4 ,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 #ab fr4 per kilo41 whereas the costs actually obtaining were a large multiple of this figure4 ,,index ,,of ,,authors ,bardy1 ,c4 ,h41 #aeg ,bokorny1 ,t41 #dc ,bronnert1 ,e41 #ed ,bumcke1 ,g41 and ,wolffenstein1 ,r41 #fg ,buntrock1 #be ,cross1 ,c4 ,f41 #aci1 #aeb1 #aee ,cross1 ,c4 ,f41 and ,bevan1 ,e4 ,j41 #ib ,cross1 ,c4 ,f41 ,bevan1 ,e4 ,j41 and ,briggs1 ,j4 ,f41 #aah ,cross1 ,c4 ,f41 ,bevan1 ,e4 ,j41 and ,heiberg1 ,t41 #aad ,cross1 ,c4 ,f41 ,bevan1 ,e4 ,j41 and ,smith1 ,c41 #aja1 #ajc1 #aje1 #aad1 #ade ,de ,haas1 ,r4 ,w4 ,t41 and ,tollens1 ,b41 #aea ,faber1 ,o4 v41 and ,tollens1 ,b41 #ga ,feilitzen1 ,h4 v41 and ,tollens1 ,b41 #aed ,fenton1 ,h4 ,j4 ,h41 #h ,fenton1 ,h4 ,j4 ,h41 and ,gostling1 ,m41 #hf ,fraenkel1 ,a41 and ,friedlaender1 ,p41 #bf ,gardner1 ,p41 #bb ,gilson1 ,e41 #aab ,hancock1 ,w4 ,c41 and ,dahl1 ,o4 ,w41 #ace ,hoffmeister1 ,w41 #if1 #ajj ,kleiber1 ,a41 #ig ,kroeber1 ,e41 #aba ,krueger1 ,m41 #aai ,lange1 ,h41 #be ,lewes1 ,v4 ,h41 #ae ,luck1 ,a41 and ,cross1 ,c4 ,f41 #de ,margosches1 ,b4 ,m41 #aei ,morrell1 ,r4 ,s41 and ,crofts1 ,j4 ,m41 #aad ,mylius1 ,f41 #ba ,nastukoff1 ,h41 #gd ,omelianski1 ,v41 #gf ,ruff1 ,o41 #aag ,salkowski1 ,e41 #aac ,schoene1 ,a41 and ,tollens1 ,b41 #abd ,seidel1 ,h41 #adi ,sherman1 ,h4 ,c41 #acg ,simonsen1 ,e41 #adf ,storer1 ,f4 ,h41 #adb ,strehlenert1 ,r4 ,w41 #aeh ,suringar1 ,h41 and ,tollens1 ,b41 #af1 #abd ,suevern1 ,c41 #fc ,tollens1 ,b41 #adh1 #aea ,tollens1 ,b41 and ,glaubitz1 ,h41 #abb ,vignon1 ,l41 #dc1 #gj1 #gb1 #id ,will1 ,w41 and ,lenze1 ,p41 #da ,winterstein1 ,e41 #aji1 #add1 #aec ,,index ,,of ,,subjects ,acetone1 action on cellulose nitrates of diluted1 #df ,acid-cellulose1 #fh ,acids1 volatile1 from cellulose1 #ade ,a,eschynomene aspera1 #ace ,alcohol from cellulose and wood1 #adf ,alcoholic soda1 mercerisation results with1 #bf ,alkali-cellulose1 effects of long storage on1 #ca ,amyloid1 vegetable1 #aec ,arabinose from gluconic acid1 #aag ',ash' of plants1 #ac ,bacterium xylinum1 #he ,barley plant1 chemical processes in the1 #ajc ---- straw1 carbohydrates of1 #aje ,bleaching1 #aff ,bran1 digestion of1 #aci ,brommethylfurfural1 #h1 #hd1 #hf ,carbohydrates1 action of hydrogen bromide on1 #hf2 action of hydrogen peroxide on1 #aad2 nitrated1 as food for mould fungi1 #dc2 nitrates of1 #da2 quantitative separation of1 #if ,carbohydrates of barley straw1 #aje2 of wheat1 #acg2 of yeast1 #aac ',caro's reagent1' #aah ',celloxin1' #ga ,cellulose1 alcohol from1 #adf2 constitution of1 #gg1 #ib2 fermentation of1 #gf2 industrial uses of1 #aee2 iodine reaction of1 #ba2 methods for the estimation of1 #c1 #d1 #af1 #ai1 #ig2 nitration of1 #dc2 saccharification of1 #gc2 ultimate hydrolysis of1 #aa2 volatile acids from1 #ade ---- acetates1 monoacetate1 formation of1 #dj2 tetracetate1 constitution of1 #hj ---- benzoates1 #cd2 from structureless cellulose1 #cf2 from three varieties of cotton1 #ce2 monobenzoate1 properties of1 #cf2 dibenzoate1 properties of1 #cg2 acetylation of1 #acj2 nitration of1 #ch ---- derivatives1 commercial aspects of1 #aga2 saccharification of1 #gc ---- nitrates1 #dd1 #de1 #hc2 structureless1 #de1 #ea2 cupric reducing power of1 #gc2 instability of1 #ej1 #ec ---- sulphocarbonate1 #bg2 effects of the nature of the cellulose1 #bh2 ---- ---- solutions1 analysis of1 #cb2 iodine reaction of1 #cc2 loss of carbon bisulphide1 #cc2 viscosity of1 #cj ,cell-wall constituents1 #ig ,cereal celluloses1 #aja1 #aje ,chitin1 #aab ,chlorination1 ,cross and ,bevan's method1 #ai2 statistics of1 #acd ,chloro-lignone1 #abf ,collodion4 ,see ,silk1 artificial ,cotton1 lustreing effect of mercerisation1 #bc2 mercerised1 structural properties of1 #be2 pentosane content of1 #adh ',crude fibre1' #ag ,cuprammonium solvent1 #ba1 #eh1 #agc ,currants1 pectin of1 #aeb ,denitration of collodion silk1 #ef2 of jute nitrate1 #acc2 products of1 #gd ,dioxybutyric acid1 #ga ,elder pith1 #acg ,eriodendron1 seed hair of1 #ib ,explosives1 #dd2 sporting powders1 #eb ,fermentation of cellulose1 #gf2 of furfuroids1 #ajh2 of sugar from wood1 #adh ,fibres1 report on miscellaneous1 #aci ,flax boiling1 #afh2 spinning1 #afa ,fodder plants1 pentosanes of1 #abb ,fungi1 tissue constituents of1 #aji ,furfural from cellulose1 oxycellulose1 and hydrocellulose1 #gj2 derivative from laevulose1 #h2 estimation as hydrazone and phloroglucide1 #aai1 #aba2 oxidation of1 #aad1 #aah 7refer also ',pentosanes'7 ,furfuroids1 #h1 #aj1 #ajb1 #aje2 assimilation of1 #ajh ,gabriel's method of cellulose estimation1 #ah ,gluconic acid1 action of hydrogen peroxide on1 #aag ,glucosamin1 #aab ,hemicellulose1 #if1 #ig2 determination and separation of1 #ajj ,hoenig's method of cellulose estimation1 #ah ',hydralcellulose1' #fh ,hydrocellulose1 #gc2 nitration of1 #dc ,hydrogen peroxide1 oxidations with1 #aad ,hydroxyfurfural in lignocellulose1 #i1 #aaf1 #aah ,incandescent mantles of artificial silk1 #ad1 #ae ,industrial appliances of cellulose1 #aee ,iodine reaction of cellulose1 #ba ,isosaccharinic acid1 #ga ,jute1 composition of1 #ada2 quality of1 #adj2 treatment of1 #adb 7refer also ,lignocellulose7 ---- acetate1 #abi ---- benzoate1 #abg2 acetylation of1 #acj2 nitration of1 #acb ---- nitrate1 #aca ,ketoses1 physiological importance of1 #i ,lange method of cellulose estimation1 #ah1 #ih ,lead compounds of nitrated carbohydrates1 #di ,lignin1 #ajj ,lignocellulose1 constitution of1 #acc2 esters of1 #abe2 hydroxyfurfural in1 #i2 new type of1 #ace ,lignone complex1 properties of1 #abf ',lignorosin1' #aea ',lustra-cellulose4' ,see ,silk1 artificial ,malt1 pentosanes of1 #abb ,mather system of boiling textiles1 #afg ,mercerization1 #bb2 shrinkage during1 #bd ,mercerised yarn1 strength and elasticity of1 #be1 #bf ,methylhydroxyfurfural1 #hd ,mould fungi1 nitrated carbohydrates as food for1 #dc ,mycosin1 #aac ,nitrated carbohydrates1 lead compounds of1 #di ,nitrates of carbohydrates1 #da ,nitrocellulose 7see ,cellulose nitrates72 silk1 #ee ',normal' cellulose1 definition of1 #bg ,normal paper1 #afj ,oxycellulose esters1 #gb2 nitration of1 #dc2 researches on1 #ga1 #gb1 #gd2 resume of properties1 #id ,oxygluconic acid1 #aag ,paper1 deterioration of1 #aee2 normal standard1 #afj2 pulp1 spinning of1 #afi ,peat1 constituents of1 #aed ,pectins1 #aea1 #aeb ,pentosanes1 #ajj1 #aji1 #add2 constituents of cotton1 #abd2 constituents of fodder1 #abb2 estimation of1 #aba2 of seeds during germination1 #abd ',permanent tissue1' #ajc ,phloroglucinol1 #aai1 #aba ,plant tissues1 carbohydrates of1 #if1 #ig1 #ii ,plants1 source of unsaturated compounds in1 #ade ,powders1 manufacture of sporting1 #eb ,saccharification of cellulose and derivatives1 #gc ,schulze method of cellulose estimation1 #ah1 #ih ,schweizer solution1 #aja ,seeds1 pentosanes in germinating1 #abd ,silica in plant tissues1 #ac ,silk1 artificial1 #ed1 #fb1 #fc1 #agb2 bibliography of1 #fj2 from cuprammonium1 #eh1 #fd1 #agc2 from nitrocellulose 7collodion71 #ee1 #fc1 #agb2 from viscose1 #ei2 from zinc chloride1 #ei2 reactions of1 #fd ---- natural1 reactions of1 #fd ,straws1 #aja1 #aje ,succinic acid from furfural1 #aah ,sulphite waste liquors1 #adi1 #afd ',swedish' filter paper1 #ad ,tissue constituents1 #ii1 #aji ,trees1 composition of trunk woods1 #adb ,viscose and viscoid1 #aeg1 #aeh1 #aei ---- silk1 #ei1 #age ---- ---- specific gravity of1 #cd 7refer also ,cellulose sulphocarbonate7 ',vulcanised fibre1' #bj ,weende1 method of cellulose estimation 7crude fibre71 #ag1 #ih ,welsbach mantles1 #ad2 ,clamond type1 #ae ,wheat grain1 insoluble carbohydrates of1 #acg ,wood1 alcohol from1 #adf1 #adh ,wood-cellulose1 waste liquors1 #adi ,wood-gum1 #add ,wood-pulp1 processes1 #afb ,wood1 trunks of trees1 #adb ,yeast1 carbohydrates of1 #aac ,zinc chloride1 artificial silk1 #ei2 solvent action of1 #bj