SPIRITUS AUS CELLULOSE UND HOLZ.

E. SIMONSEN (Ztschr. angew. Chem., 1898, 3).

PRODUCTION OF ALCOHOL FROM CELLULOSE AND WOOD.

(pp. 50, 209) This investigation was undertaken with one main object—to determine the optimum conditions of treatment of wood-cellulose and of wood itself for conversion into 'fermentable sugar.' The process of 'inversion' or hydrolysis, by digestion with dilute acid at high temperature, involves the four main factors: pressure (i.e. temperature), concentration of acid, ratio of liquid to cellulose and duration of digestion. Each of these was varied in definite gradations, and the effect measured. The degree of action was measured in terms of 'reducing sugar,' calculated from the results of estimation by Fehling solution, as 'glucose' per cent. of original cellulose (or wood).

(a) Cellulose. [Wood-cellulose obtained by bisulphite process.]—With a proportion of total liquid to cellulose of 27 : 1, and using sulphuric acid as the hydrolysing agent, the optimum results were obtained with acids of 0.45-0.60 p.ct. (H{2}SO{4}) and pressures of 6-8 atm. The maximum yield of 'sugar' was 45 p.ct. of the cellulose.

Under the above conditions the maximum of conversion is attained in 2 hours.

Having now regard to the production of a solution of maximum concentration of dissolved solids, the following conditions were asertained to fulfil the requirement, and, in fact, may be regarded as the economic optimum:

Proportion of total liquid 6 times wt. of cellulose Concentration of acid 0.5 p.ct. H{2}SO{4} Pressure 10 atm. Duration of digestion 1.5 hour

giving a yield of 41 p.ct. 'reducing sugar' calculated to the original cellulose (dry).

Alcoholic Fermentation of Neutralised Extract.—The liquors were found to ferment freely, and on distillation to yield a quantity of alcohol equal to 70 p.ct. of the theoretical—i.e. on the basis of the numbers for copper oxide reduction.

(b) Hydrolytic 'Conversion' of Wood (Lignocellulose).—A similarly systematic investigation carried out upon pine sawdust established the following as optimum conditions:

Proportion of total liquid 5 times wt. of wood Concentration of acid 0.5 p.ct. H{2}SO{4} Pressure 9 atm. Duration of digestion 15 minutes

giving a yield of 20 p.ct. 'reducing sugar,' calculated from the 'Fehling' test.

Fermentation of the neutralised extracts gave variable results. The highest yields obtained were 60 p.ct. of theoretical, the author finally concluding that under properly controlled conditions of inversion and fermentation 100 kg. wood yield 6.5 l. absolute alcohol.

UeBER DIE URSACHE DER VON SIMONSEN BEOBACHTETEN UNVOLLSTAeNDIGKEIT DER VERGAeHRUNG DER AUS HOLZ BEREITETEN ZUCKERFLUeSSIGKEITEN.

B. TOLLENS (Ztschr. angew. Chem., 1898, 15).

ON THE CAUSE OF INCOMPLETE FERMENTATION OF SUGARS OBTAINED BY ACID HYDROLYSIS OF WOOD.

The author criticises Simonsen's explanation of the results obtained with extracts from pine wood. The incompleteness of fermentation of the products is certainly due in part to the presence of furfural-yielding carbohydrates, which are resistant to yeast. The pine woods contain 8-10 p.ct. of these constituents in their anhydride form ('pentosanes'). They yield readily to acid hydrolysis, and certainly constitute a considerable percentage of the dissolved products. A similar complex was obtained by the author in his investigation of peat (Berl. Ber. 30, 2571), and was found to be similarly incompletely attacked by yeast. The yields of alcohol corresponded with the proportion of the total carbohydrates disappearing. These were the hexose constituents of the hydrolysed complex, the pentoses (or 'furfuroids') surviving intact.

UEBER SULFITCELLULOSEABLAUGE.

H. SEIDEL (Ztschr. angew. Chem., 1900).

WASTE LIQUORS FROM BISULPHITE PROCESS.

(p. 210) Later researches confirm the conclusion that in the soluble by-products of these cellulose processes the S is combined as a SO_{3}H group. The following analyses of the isolated lignin sulphonic acid are cited:

C H S (a) Lindsey and Tollens 56.12 5.30 5.65 (b) Seidel (1) 56.27 5.87 5.52 (c) Seidel and Hanak (2) 53.69 5.22 8.80 (d) Street 50.22 5.64 7.67

The variations are due to the varying conditions of the digestion of the wood and to corresponding degrees of sulphonation of the original lignone group. Calculating the composition of the latter from the above numbers on the assumption that the S represents SO_{3}H, the following figures result:

(a) and (b) (c) (d) C 64.00 65.1 59.61 H 6.65 6.33 6.69

This author considers that beyond the empirical facts established by the above named[10] very little is yet known in regard to the constitution of the lignone complex.

Nor is there any satisfactory application of this by-product as yet evolved. Evaporation and combustion involve large losses of sulphur [D.R.P. 74,030, 83,438; Seidel and Hanak, Mitt. Techn. Gew. Mus. 1898]. A more complete regeneration of the sulphur has been the subject of a series of patents [D.R.P. 40,308, 69,892, 71,942, 78,306, 81,338], but the processes are inefficient through neglect of the actual state of combination of the S, viz. as an organic sulphonate. The process of V.B. Drewson (D.R.P. 67,889) consists in heating with lime under pressure, yielding calcium monosulphite (with sulphate and the lignone complex in insoluble form). The sulphite is redissolved as bisulphite by treatment with sulphurous acid. This process is relatively costly, and yields necessarily an impure lye. It has been proposed to employ the product as a foodstuff both in its original form and in the form of benzoate (D.R.P. 97,935); but its unsuitability is obvious from its composition. A method of destructive distillation has been patented (D.R.P. 45,951). The author has investigated the process, and finds that the yield of useful products is much too low for its economical development. Fusion with alkaline hydrates for the production of oxalic acid (D.R.P. 52,491) is also excluded by the low yield of the product.

The application of the liquor for tanning purposes (D.R.P. 72,161) appears promising from the fact that 28 p.ct. of the dry residue is removed by digestion with hide powder. This application has been extensively investigated, but without practical success. Various probable uses are suggested by the viscosity of the evaporated extract. As a substitute for glue in joinery work, bookbinding, &c., it has proved of little value. It is applied to some extent as a binding material in the manufacture of briquettes, also as a substitute for gelatin in the petroleum industry. Cross and Bevan (E.P. 1548/1883) and Mitscherlich (D.R.P. 93,944 and 93,945) precipitate a compound of the lignone complex and gelatin by adding a solution of the latter to the liquors. The compound is redissolved in weak alkaline solutions and employed in this form for engine-sizing papers. Ekman has patented a process (D.R.P. 81,643) for 'salting out' the lignone sulphonates, the product being resoluble in water and the solution having some of the properties of a solution of dextrin. Owing to its active chemical properties this product—'dextron'—has a limited capability of substituting dextrin. The suggestion to employ the evaporated extract as a reducing agent in indigo dyeing and printing has also proved unfruitful. The author's application of the soda salt of the lignone sulphonic acid as a reducing agent in chrome-mordanting wool and woollen goods (D.R.P. 99,682) is more successful in practice, and its industrial development shows satisfactory progress. The product is known as 'lignorosin.'

FOOTNOTES:

[10] See more particularly: Lindsey and Tollens, Annalen, 267, 341; Cross and Bevan's Cellulose, pp. 197-203; Street, Inaug.-Diss., Goettingen, 1892; Klason, Rep. d. Chem. Ztg. 1897, 261; Seidel and Hanak, Mitt. d. Techn. Gew. Mus. 1897-1898.



SECTION VII. PECTIC GROUP

UNTERSUCHUNGEN UeBER PECTINSTOFFE.

R. W. TROMP DE HAAS and B. TOLLENS (Lieb. Ann., 286, 278).

UeBER DIE CONSTITUTION DER PECTINSTOFFE, B. TOLLENS (ibid. 292).

INVESTIGATIONS OF PECTINS.

(p. 216) It is generally held that the pectins are, or contain, oxidised derivatives of the carbohydrates. The authors have isolated and analysed a series of these products, and the results fail to confirm a high ratio O : H. The following are the analytical numbers:

Pectin from Ash C H Ratio H : O Apple 6.2 43.4 6.4 1 : 7.9 Cherry 20.5 42.5 6.5 1 : 7.9 Rhubarb 4.2 43.3 6.8 1 : 7.4 Currant 5.0 47.1 5.9 1 : 8.5 Greengage 3.3 43.0 5.9 1 : 8.5 Turnip 7.3 41.0 5.9 1 : 9.0

Acid hydrolysis (4 p.ct. H{2}SO{4}) gave syrupy products not crystallisable—in certain cases the hydrolysis was accompanied by separation of insoluble cellulose. The insoluble product from currant pectin had the composition C 54.4, H 5.0.

Tollens points out that the results of empirical analysis are inconclusive; and that from the acid reactions of these products and their combination with bases, carboxylic groups are present, though probably in anhydride or ester form.

The pectins may be regarded as closely related to the mucilages (Pflanzenschleim), differing from them only by the presence of the oxidised groups in question.

UEBER DIE CONSTITUTION DER PECTINSTOFFE.

C. F. CROSS (Berl. Ber., 1895, 2609).

CONSTITUTION OF PECTINS.

It is pointed out that the composition of the pectin of white currants, as given in the preceding paper, is that of the typical lignocellulose, the jute fibre. The product was isolated and further investigated by the author. It gave 9.8 p.ct. furfural on boiling with HCl (1.06 s.g.), reacted freely with chlorine, giving quinone chlorides, and with ferric ferricyanide to form Prussian blue. This 'pectin' is therefore a form of soluble lignocellulose. The 'pectic' group consequently must be extended to include hydrated and soluble forms of the mixed complex of condensed and unsaturated groups with normal carbohydrates, such as constitute the fibrous lignocelluloses.

UEBER DAS PFLANZLICHE AMYLOID.

E. WINTERSTEIN (Ztschr. Physiol. Chem., 1892, 353).

ON VEGETABLE AMYLOID.

(p. 224) A group of constituents of many seeds, distinguished by giving slimy or ropy 'solutions' under the action of boiling water are designated 'amyloid.' They are reserve materials, and in this, as in the physical properties of their 'solutions,' they are very similar to starch. They are, however, not affected by diastase; and generally are more resistant to hydrolysis. Typical amyloids have been isolated by the author from seeds of Tropoeolum majus, Poeonia officinalis, and Impatiens Balsamina. The raw material was carefully purified by exhaustive treatment with ether and alcohol, &c.; the amyloid then extracted by boiling with water, and isolated by precipitation with alcohol. Elementary analysis gave the numbers C 43.2, H 6.1. On boiling with 12 p.ct. HCl it gave 15.3 p.ct. furfural; oxidised with nitric acid it yielded 10.4 p.ct. mucic acid. Specimens from the two first-named raw materials gave almost identical numbers.

Hydrolysis.—On boiling with dilute acids these products are gradually broken down, dissolving without residue. In this respect they are differentiated from the mucilages, which give a residue of cellulose (insoluble). From the solution the author isolated crystalline galactose, but failed to isolate a pentose. Dextrose was also not identified directly.

The tissue residues left after extracting the amyloid constituent, as above described, were subjected to acid hydrolysis. A complex of products was obtained, from which galactose was isolated. A furfural-yielding carbohydrate was also present in some quantity, but could not be isolated. The original seed tissues, therefore, contain an amyloid and a hemicellulose, the latter differentiated in its resistance to water. Both yield, however, to acid hydrolysis a complex of products of similar composition and constitution.

UEBER DEN GEHALT DES TORFES AN PENTOSANEN ODER FURFUROLGEBENDEN STOFFEN UND AN ANDEREN KOHLENHYDRATEN.

H. V. FEILITZEN and B. TOLLENS (Berl. Ber., 1897, 2,571).

CARBOHYDRATE CONSTITUENTS OF PEAT.

(p. 240) An investigation of typical peats taken at successive depths showed increasing percentage of carbon, and inversely a decreasing yield of furfural. The numbers may be compared with those for Sphagnum cuspidatum—with C = 49.80 p.ct., and furfural 7.99 p.ct., calculated to dry, ash-free substance:

_________ Depth at which taken C p.ct. Furfural p.ct. _____ __ ___ _ 20-100 cm. 51.08 6.93 I. 100-200 " 53.52 5.30 _ 200-300 " 58.66 3.19 _ Surface-20 " 55.47 3.40 II. 20-60 " 55.06 3.48 60-100 " 58.25 1.45 100-120 " 58.23 1.19 _ 180-200 " 57.57 1.80 _____ __ ___

Cellulose was estimated by the Lange method. The yield from Sphagnum was 21.1 p.ct.

From specimen I. at { 20-100 cm. 15.20 { 100-200 " 6.87

From the peat of lower depths no cellulose could be obtained.

Hydrolysis (acid).—On heating with 1 p.ct. H{2}SO{4} at 130-135 deg., soluble carbohydrates were obtained, amongst which mannose was identified, and galactose shown to be present in some quantity. After fermenting away the hexoses, the residue was treated with phenylhydrazine and an osazone separated. It contained 17.3 p.ct. N, but melted at 130 deg.. The substance could not be identified as an osazone of any of the yet known pentoses.



SECTION VIII. INDUSTRIAL AND TECHNICAL. GENERAL REVIEW

The Industrial Uses of Cellulose.

C. F. CROSS (Cantor Lectures, Soc. of Arts, 1897).

(p. 273) A series of three lectures, in which the more important industries in cellulose and its derivatives are dealt with on their scientific foundations, and by means of a selection of typical problems. In reference to textiles, the small number of vegetable fibres actually available, out of the endless variety afforded by the plant world, is referred to the number of conditions required to be fulfilled by the individual fibre, thus: yield per cent. of harvested weight or per unit of field area, ease of extraction, the absolute dimensions of the spinning unit, and the proportion of variation from the mean dimensions; the relative facility with which the unit fibre can be isolated preparatory to the final twisting operation; the chemical constants of the fibre substance, especially the percentage of cellulose and degree of resistance to hydrolysis. It is suggested that any important addition to the very limited number fulfilling the conditions, or any great improvement in these, can only result from very elaborate artificial selection and cultural developments on this basis.

The paper making fibres are shown to fall into a scheme of classification based on chemical constitution, and consisting of the four groups: (a) Cotton [flax, hemp, rhea], (b) wood celluloses, (c) esparto, straw, and (d) lignocelluloses. Papers being exposed to the natural disintegrating agencies, more especially oxygen, water (and hydrolysing agents generally), and micro-organisms, the relative resistance of the above groups of raw materials is discussed as an important condition of value. The indirect influence of the ordinary sizing and 'filling' materials is discussed. The paper-making quality of the fibrous raw materials is also discussed, not merely from the point of view of the form and dimensions of the ultimate fibres, but their capacity for 'colloidal hydration.' This is complementary to the action of rosin, i.e. resin acids, in the engine-sizing of papers; and the proof of the potency of this factor is seen in the superior effects obtained in sizing jointly with solutions of cellulose and, more particularly, viscose and rosin. Wurster's much-cited monograph of the subject of rosin-sizing ['Le Collage des Papiers,' Bull. Mulhouse, 1878] neglects to take into consideration the contribution of the cellulose hydrates to the total and complex sizing effect, and hence gives a partial view only of the function of the resin acids.

In further illustration of fundamental principles various developments in the textile industries are discussed, e.g. the bleaching of jute, cotton, and flax, and special developments in the spinning of rhea and flax.

The concluding lecture deals with later progress in the industrial applications of cellulose derivatives, chiefly the sulphocarbonate (viscose); the nitrates, in their applications to explosives, on the one hand, and the spinning of artificial fibres (lustra-cellulose), on the other; and the cellulose acetates.

La Viscose et le Viscoide.

C. H. BARDY (Bull. Soc. d'Enc. Ind. Nationale, 1900, March).

This is a report presented to the Committee of Economic Arts of the above Society, dealing with the industrial progress in products obtained by means of the sulphocarbonate of cellulose (viscose).

The following developments are noted:

Engine-sized Papers.—The viscose, by coating the fibres with regenerated cellulose hydrate, adds very much to the tensile strength of papers. Increase of 40-60 p.ct. is attainable by addition of cellulose in this form from 1-4 p.ct. on the weight of the paper.

Viscoid.—Solid aggregates are formed by incorporating viscose with mineral matters, hydrocarbons, &c. Products are cast or moulded into convenient forms, and, after purification and sufficient ageing, are available for various structural uses.

Paint.—The viscose is used as a vehicle for pigments, the mixture being used either as a paint or for coating papers with fine surfaces, such as required in the reproduction of photo-blocks. In these applications the extraordinary viscosity of the product conditions the economic use of the cellulose in competition with oils, on the one hand, and organic colloids, such as gelatine, casein, &c., on the other.

By suitable alteration of the formula for making the paint a product is obtained which has an extraordinary power of removing paint from old painted surfaces. The product has been officially adopted by the French Admiralty, and receives extensive application in removing the paint from ships.

Films.—Films are produced from the viscose itself in various ways. Plane or flat by solidifying the viscose on glass surfaces, removing the by-products and rolling the films. The film is also produced by applying the viscose on textile fabrics, drying down, and fixing on a stenter machine, then washing away the alkaline by-products from the fixed film. A large number of industrial effects are obtained by suitably varying the mixtures applied.

Cellulose-indiarubber.—The viscose, in its concentrated form, can be incorporated with rubber-hydrocarbon mixtures, and these mixtures can be used both as water-proofing films, as applied to textiles, or can be solidified into the class of goods known as 'mechanicals.' The cellulose not only cheapens the mixture, but produces new technical effects.

Spinning.—The viscose is spun by special methods, patented by C. H. Stearn. As produced in thread form, the diameters are approximately those of natural silk. In commercial form it is a multiple thread (of 15 or more units) at from 50-200 deniers on the silk counts. It is a thread of high lustre, and more nearly approaches the normal cellulose in chemical properties than any of the other artificial silks. It can also be spun in threads of very much larger diameter, which can be used as a substitute for horsehair, for carbonising for incandescent electric lamps, &c.

Cellulose Esters.—These are conveniently made from cellulose, regenerated from the solution as sulphocarbonate. The tetracetate is made from this product on the industrial scale. Nitrates are conveniently made by treatment with the ordinary mixed acids. For fuller details the original report may be consulted.

VISKOS.

R. W. STREHLENERT (Svensk Kemisk Tidskrift, Stockholm, 1900, p. 185).

A report on the industrial development of viscose, covering essentially the same ground as the above.

Ueber die Viscose.

B. M. MARGOSCHES (Reprint from Zeitschrift fuer die gesammte Textil-Industrie, 1900-01, Nos. 14-20).[11]

Report of Committee on the Deterioration of Paper.

(Soc. of Arts, 1898.)

(p. 304) The Report of a Representative Committee appointed by the Society of Arts to inquire into the question of qualities of book papers in relation to their several applications, and more especially for documents of permanent value.

The report first discusses the two directions of depreciation of papers in use: (1) Actual disintegration shown by loss of resistance to fracture by simple strain, and by loss of elasticity—i.e. increase of brittleness; (2) discolouration. These are independent effects, but often concurrent. They are the result of chemical changes of the cellulose basis of the paper, brought about by acids or oxidants used in the process of manufacture, and not completely removed from the pulp, or by acid products of bleaching—e.g. oxycelluloses or chlorinated derivatives; again, by the changes of starch used as a 'sizing' agent, or by oxidations induced by rosin constituents when the rosin is used in excess. Discolouration is an attendant phenomenon of these changes, but is more frequently due to the presence of the lower-grade celluloses (esparto and straw) and the lignocelluloses (mechanical wood-pulp).

The physical and chemical qualities of papers depending primarily upon their fibrous or pulp basis, and in a secondary degree upon the kind and proportion of the constituents added for the purpose of filling and 'sizing,' the report concludes with the following recommendations, positive and negative, under these heads:

The Committee find that the practical evidence as to permanence fully confirms the classification given in the Cantor Lectures on 'Cellulose,' 1897 [J. Soc. Arts, xlv. 690-696], and which ranges the paper-making fibres in four classes:

(A) Cotton, flax, and hemp (rhea).

(B) Wood celluloses, (a) sulphite process and (b) soda and 'sulphate' process.

(C) Esparto and straw celluloses.

(D) Mechanical wood-pulp.

In regard, therefore, to papers for books and documents of permanent value, the selection must be taken in this order, and always with due regard to the fulfilment of the conditions of normal treatment above dealt with as common to all papers.

The Committee have been desirous of bringing their investigations to a practical conclusion in specific terms—viz. by the suggestion of standards of quality. It is evident that in the majority of cases there is little fault to find with the practical adjustments which rule the trade. They are, therefore, satisfied to limit their specific findings to the following—viz. (1) normal standard of quality for book-papers required for publications of permanent value. For such papers they specify as follows:

Fibres: Not less than 70 p.ct of fibres of class A; class D excluded.

Sizing: Not more than 2 p.ct. rosin, and finished with the normal acidity of pure alum; starch excluded.

Loading: Not more than 10 p.ct. total mineral matter (ash).

(2) With regard to written documents, it must be evident that the proper materials are those of class A, and that the paper should be pure and sized with gelatin, and not with rosin. All imitations of high-class writing-papers which are, in fact, merely disguised printing-papers, should be carefully avoided.

Appendix.—To the Report is added 'Abstracts of Papers' in 'Mittheilungen aus den Koniglichen Technischen Versuchsanstalten, Berlin,' for the years 1885-1896 inclusive—which is, in fact, a summary of the investigations of the Institution in connection with paper and paper-standards.

* * * * *

(p. 273) Special Industrial Developments.—From the point of view of the chemist there has been a very large development of the cellulose industries during the last five years. This is not so much marked by the gradual and progressive growth of the well-established industries, as by the success of the newer ones, with the attendant forecast of enormous developments of the industries in artificial products, the manufacture of which rests upon a purely chemical basis. We can, of course, only treat them from this limited standpoint, and so far as they involve and elucidate chemical principles.

I. Chemical Treatments of Raw Materials.

(a) Flax-spinning.—The treatment of the roving on the spinning-frame by the addition of reagents to the macerating liquid—otherwise and usually hot water—continues to be justified by results. The technical basis of the process and the reactions determined in the spinning-trough by the alkaline salts used—chiefly sulphite and phosphate of soda—is set forth in the original work, p. 280. Since that time a sufficient period has elapsed to judge the effects, both technical and industrial, by the results of a commercial undertaking based on the exclusive use of the process. Such a concern is the Irish Flax Spinning Company of Belfast. At this mill the experience is uniform and fully established that by means of the process the drawing, i.e. spinning, quality of inferior flaxes is very considerably appreciated, enabling the spinner to use such flaxes for yarns of fineness which are unattainable by the ordinary method of spinning through hot water. Notwithstanding the success of this undertaking the development of the method is still inconsiderable. It is none the less a further and forcible demonstration of the existence of margins of increased technical effect which it is the work of the scientific technologist to exploit.

(b) Wood-pulp and Methods of Manufacture.—There is a steady growth in the consumption of wood-pulps (cellulose) relatively to other materials. In regard to the paper-trade of the world, this continues to be one of the most prominent characteristics of its evolution. In the United Kingdom the conditions of its competition are of a more special kind by reason of the firm foothold of esparto, which is a most important staple in the manufacture of fine printings. Whereas the consumption of esparto remains nearly stationary at about 200,000 tons per annum, the importation of wood-pulps has shown the extraordinary rate of increase of doubling itself every five years. But in the group 'wood-pulps' the trade returns have until recently included the 'mechanical' or ground wood-pulps. From 1898 we have separate returns for the chemical or cellulose pulps, and in 1899 the tonnage reached nearly to that of esparto, with a total money value about 80 p.ct. greater. When it is remembered that this is one of the newer chemical industries in cellulose products, and that these large commercial results have been accomplished during a period of twenty years, we are impressed with the scope of the industrial outlook to the chemist, afforded by the arts of which cellulose is the foundation.

It may be noted that there have been no important developments in the purely chemical processes involved in the several systems of preparing cellulose from wood. The acid methods (bisulphite processes) have developed much more extensively than the alkaline, the latter including the caustic soda and the mixed sulphide ('Dahl') process. The bisulphite processes depended in the earlier stages upon the efficiency of lead-lined digesters. But the problem of acid-resisting linings has been much more perfectly solved in later years in the various types of cement and other silicate linings now in use. The relative permanency of these linings has had an important effect on the costs of production. Further economies result from the use of digesters of enormous capacity, dealing with as much as 100 tons of wood at one operation. As a combined result of economic production and active competition, the selling prices of 'sulphite pulp' have moved steadily downwards in relation to other half-stuffs and raw materials. As a necessary consequence the prices of those which it has gradually displaced have depreciated, and a study of the price and tonnage-equilibrium as between rags, esparto, and wood-pulp over a series of years forms an interesting object-lesson in the struggle for survival which is an especial mark of modern industry. For these matters the reader is referred to the special literature of the paper-making industry.[12]

It is not a little remarkable that the main by-product of these bisulphite processes—the sulphonated derivatives of the lignone constituents of the wood—is still for the most part an absolute waste, notwithstanding the many investigations of technologists and attempts to convert it to industrial use (see p. 149). Seeing that it represents a percentage on the wood pulped equal to that of the cellulose obtained, it is a waste of potentially valuable material which can only be termed colossal. Moreover, as a waste to be discharged into water-courses, it becomes a source of burden and expense to the manufacturer, and with the increasing restrictions on the pollution of rivers it is in many localities a difficulty to be reckoned with only by the cessation of the industry. The problem in such cases becomes that of dealing with it destructively, i.e. by evaporation and burning. In this treatment the obviously high calorific value of the dissolved organic matter (lignone) appears on the 'credit' side. But where calcium and magnesium bisulphites are used, the residue from calcination is practically without value. It appears, however, that by substituting soda as the base the alkali is recoverable in such a form as to be directly available for the alkaline-sulphide or 'Dahl' process. As a more complicated alternative the soda admits of being recovered on the lines of the old black-ash or Leblanc process, and the sulphur by the now well-established 'Chance' process, for which, of course, an addition of lime is necessary to the fully evaporated liquors previously to calcining. The engineering features of the system, so far as regards evaporating and calcining, are the same. For economic working there is required (a) evaporation by multiple effect and (b) calcining on the continuous rotary principle. For the latter a special modification has been devised so that the draught of air is concurrent with the movement of the charge in the furnace, securing a progressively increasing temperature within the furnace. This interesting development of the chemical engineering of wood-pulp systems has been elaborated by two well-known technologists, Drewson and Dorenfeldt, and readers who wish to inform themselves in detail of these developments are referred to the various publications of these inventors.

Assuming the present necessity of a destructive treatment of the by-products of the bisulphite processes, the scheme has many advantages. The soda-bisulphite liquors are more economically prepared; the pulp obtained is superior in paper-making quality to that resulting from the lime or magnesia (bisulphite) processes: it is more economically bleached.

Then, as pointed out, the soda may on the one plan be obtained in a form in which it is immediately available as a powerful hydrolysing alkali in the manufacture of a 'soda' pulp. These two systems become, therefore, in a new sense complementary to one another. Lastly, it is obvious that the employment of soda as the base opens out a new vista for developing the electrolytic processes of decomposing common salt.

The authors have assisted in preparing plans for a comprehensive industrial scheme combining all these more modern developments. In this scheme it is only the combination which is novel, and as it involves no new principles in the chemical treatments of the materials we are not further concerned with it than to have briefly sketched its economic basis. This may be summed up in result in the important question of cost and selling price, and the estimate is well grounded that by means of this scheme bleached wood-pulp can be sold on the English market at 10l. a ton. It is important to note this figure and to compare it with the prices of twenty years ago. The fall has been continuous, notwithstanding the influence of the opposing factors of increasing consumption, exhaustion of accessible supply of timber, and relative appreciation of the essential costs of steam, chemicals, and labour. It is important in forecasting the future, since the youngest and apparently most promising of the 'artificial' cellulose industries employs wood-cellulose by preference as its raw material (see p. 173).

As a last point it must be considered that as chemists we are bound to anticipate the realisation of value in the soluble by-products of the bisulphite processes. Outside the intrinsic interest attaching to the solution of this problem, it carries with it the promise of a further economy in the production of wood-cellulose.

Bleaching of Vegetable Textiles.—By far the largest of these industries are those which are engaged in producing the 'pure white' on cotton and flax goods. The process, considered chemically, is simply that of isolating a pure cellulose, and we endeavoured to give due prominence to this view in the original work. It is important to insist upon it for the reason that this view gives the due proportion of chemical value to the several contributory treatments—alkaline hydrolyses (caustic lime and soda boils), hypochlorite oxidations, and incidental acid treatments (souring). The first of these is by far the largest contributor of 'chemical work,' though the second, by being the agent for the actual whitening effect or bleaching action proper, occupies a position of often exaggerated importance.

In bleaching processes there has been no radical change of system on the large scale since the introduction of the 'Mather' kier in 1885, and the associated change from lime and ash boiling to the caustic soda circulating boil with reduced volume of lye, which this mechanical device rendered practicable. It is outside the scope of this work to follow up this branch of technology in any detail, and we cannot discuss the evolution of systems on variations of detail where no essential principle is involved. But we have to notice a very recent development which has only just begun its industrial career, and which does give effect to a principle of treatment not previously applied. This is tersely stated by its originator, William Mather,[13] in the expression, 'it is more economical to make liquids pass through cloth than to make cloth pass through liquids.' The starting point of this development is the invention of a complete self-contained machine in which a rolled batch of cloth can receive a succession of chemical treatments, with accessory washings—the solutions, or wash waters, being circulated through the cloth. The essential fact on which this system is based is that a perfect liquid circulation can be maintained from selvedge to selvedge through the folds of a tightly rolled batch of cloth. Such circulation is therefore quite independent of the diameter of the batch. If we consider a cloth under chemical treatment with solutions, it is clear that the reactions and interchanges of soluble matters within the cloth, within the twisted elements of the yarn, and in the last grade of distribution within the actual ultimate fibres, are subject to capillary transmission, and osmotic exchange. There is a mixture of these molecular effects, with the circulation in mass, sweeping both faces of the cloth. It is obvious that for the mass effect a relatively very small volume of circulating liquid is necessary to maintain uniform conditions of action. In the actual disposition of the machine the rolled batch of cloth nearly fills the cylindrical space of what we may call the reaction chamber, and the circulation of the liquid is maintained by a circulating pump and a differential pressure in the horizontal plane across and through the folds of the batch. This is in the meantime kept in slow revolution. For a full description of these mechanical details the reader is referred to the original patent specifications [Engl. Pat. 23,400, 23,401; 1900, W. Mather]. If we again consider the principles involved, they are very much as set forth in our original work (pp. 288-291). Boiling processes in which a relatively large volume of liquid is used are wasteful of steam, the active agent is unnecessarily diluted or used in superfluous quantity, and the soluble by-products, being continually removed as formed, cannot so effectively contribute by secondary actions to the chemical work. The new mechanical appliance enables us to further reduce the volume of liquid required in the alkaline-hydrolytic treatment of vegetable textiles, and where advantageous to bring the treatment down (or up) to a process of steaming with the active agent dissolved in a minimum proportion of water relative to the cloth. This concentration of effect is of importance in flax cloth, and especially linen treatment, where the peculiarly resistant cutocelluloses have to be attacked and a considerable proportion of waxy by-products to be removed. These points are the basis of the special process of Cross and Parkes [Engl. Pat. 25,076/ 99] for steaming flax (and cotton) goods with an emulsion containing, in addition to the special hydrolysing agent—caustic soda—mixtures of soap with 'mineral' or other oils, the presence of which effectually aids the removal of the by-products in question.

A complete system on these lines is now working on the industrial scale in the Belfast district. The results are not merely economical in largely reducing the number of alkaline boiling treatments required on the old plan of pan or 'pot' boiling, but are visible in the strength and finish of the linens so treated.

For cotton bleaching the costs may be put down at a fraction of those of the Irish linen bleach. The economical advantages of the new system are obviously less in relation to the lesser total costs. But there are other points which have come into more prominent influence. The mechanical wear and tear on the cloth is considerable in the ordinary process, more especially in the mangle-washes. As a result the adjustment of warp and weft is more or less disturbed. These defects are absent from a system which operates on the cloth in a fixed position.

But as we are mainly concerned with the purely chemical factors we cannot pretend to deal with textile questions. We have to notice the remaining element of chemical economy as it involves a fundamental principle. The practice of washing residues or products of reaction free from reagents and soluble by-products involves a well-known mathematical law, under which the rate of purification is a function rather of the number of successive changes of washing liquid than of the volume of the latter. The ordinary practice of textile washings entirely ignores this principle, and the consumption of water in consequence may reach many thousand times the economic minimum. With supplies of water often in indefinite excess of requirements, even in this most wasteful method, bleachers are in no need to consider the question of consumption. But leaving aside particular and local considerations of advantage the fact is that the new system gives control of the practice of washing, enabling the operator to adapt an important element of the daily routine to a fundamental principle which has been almost universally ignored.

In the oxidising processes which follow the alkaline treatments, the hypochlorites are still the staple agents. Owing to the steady relative fall in the selling prices of the permanganates these are coming into more extensive use, but the consumption is still small, and they are mainly used for certain special effects, chiefly in linen or more generally flax cloth bleaching.

Paper-pulp Spinning.—Paper is a continuous web or fabric produced by the interlocking of the structural fibrous units of the well-known short length. In Japan and other countries paper is made to serve for all or some of the purposes for which we employ string or twine, and to give the necessary tensile strength the paper is twisted or rolled on itself. Such twisting, however, adds nothing to the intrinsic tensile qualities of the original paper.

A new technical effect is realised in this direction by the treatment of paper-pulp in the process of its conversion into a continuous web: The pulp is formed into continuous strips of convenient breadth (usually from 2 to 8 mm.), these receive a 'rolling-up' treatment immediately following the squeeze of the press rolls by which the superfluous water is removed: they are then further but incompletely dried, and in this condition are subjected to a final spinning or twisting treatment on ring-spinning machinery of special construction.

Such a process was originally patented by C. Kellner in this country (E.P. No. 20,225/1891), and is fully described in his specification. Later improvements in detail were patented by G. Tuerk (E.P. 4621/1892).

A joint system is now being industrially developed in Germany by the Altdamm-Stahlhammer Pulp and Paper Company under the technical direction of Dr. Max Mueller, and there appears to be every prospect of the product taking a position as a staple textile.

The process has only the incidental interest in connection with our main subject, that it employs chiefly the 'chemical' pulps or celluloses as raw materials. The industrial future of the application must, of course, be largely determined by costs of production, as the directions of application in the weaving industries will be limited by the necessarily inferior grade of tensile strength belonging to these products and the degree by which this is lowered on complete wetting. All these questions have been duly weighed by those engaged in this interesting development, and the conclusion of those qualified to judge is that the new industry has vindicated for itself a permanent position.

II. The Chemical Derivatives of Cellulose, in their industrial aspects, have come to occupy a profoundly important position in the world's affairs. In the way of any essential alteration of the perspective from that obtaining in 1895 we have nothing to chronicle. No new derivatives of industrial importance have been added in that period; but certain new methods incidental to the preparation of well-known compounds or for converting them into more generally available forms have been introduced, and these are contributing to the rapid expansion of the 'artificial' cellulose industries.

Of the cellulose esters the nitrates are still the only group in industrial use. There uses for explosives have attained immense proportions, and their applications for structural purposes are continually on the increase. The manufacture of smokeless powders on the one hand, and of celluloid and xylonite (both in the form of films and solid aggregates) on the other, has taken no new departure. The industry in 'artificial silks' or 'lustra-celluloses,' by the collodion processes also, whilst presenting features of unusual interest attaching to rapid expansion, has been barren of contribution of fundamental scientific or technical importance. The tetracetate is now manufactured on the large scale, but the product has yet to make its market.

The process of mercerising cotton yarns and cloth has been developed to an industry of colossal dimensions, and the growth has been especially rapid during the last five years. Significant of the technical progress in these two industries, with their common aim of appreciating cellulose in the scale of textiles by approximating its external properties in those of silk, is the appearance of a monograph of the technology of each, notices of which have been previously given (pp. 22-26).

There is little doubt, however, that the question of the future industry in the various forms of cellulose, thread, film, structureless powder or solid aggregate, obtainable by artificial means, mainly turns upon cost of production. Irrespective of cost, there would, no doubt, be a market for all these products, based upon such of their properties or effects as are indispensable and not otherwise obtainable. As an illustration, we may cite the extraordinary selling prices of 40-50 fr. per kilo, for the 'artificial silks' (collodion process) which ruled some three years ago; and we may note that for a special application of viscose the dissolved cellulose is paid for at the rate of 10 per lb. These facts are certainly worthy of mention, and should be borne in mind as an index of some special features of modern manufacturing industry. But with a material like cellulose rendered available in a new shape the question which always arises more prominently than that of limited uses at high prices is that of consumption on the extensive scale which marks the older and well-known products. That question is rapidly solving itself in this country as regards the 'artificial silks.' There is at present a limited market at 9s.-10s. per lb., a price which on the one side excludes extensive consumption, and on the other practically bars manufacture in this country by any of the collodion systems. It will appear from a very elementary calculation of what we may call the theoretical costs that the above selling price would not have a remunerative margin. The theoretical costs are made up of

Raw materials[14] {Cotton. Nitrating acid. Ether-alcohol (solvent). {Denitrating chemicals.

{(a) Nitrating and preparing collodion. Denitrating { and bleaching. Labour {(b) Textile operations. Spinning. Winding and twisting. {Rewinding.

Power {Making, filtering, and distributing collodion. {Driving textile machinery.

Added to which are the costs of expert management and supervision and general establishment expenses. It is evident that raw materials make up a large fraction of the total cost; also that a very large item is the waste work of converting the cellulose into nitrate, only to remove the nitric groups so soon as the cellulose is obtained as thread.

It is clear that the aqueous solutions of cellulose have a double advantage in this respect—not only do they readily yield an approximately pure cellulose as a direct product of regeneration or decomposition, but the first cost of the solution is very much less. With these newer products, therefore, the spinning problem enters on a new phase of struggle. It is certain that at selling prices at or about 5s. to 7s., very large markets will be open to the product or products. The two processes which are or may be able to fulfil this demand are those based (1) on cuprammonium solutions of cellulose, (2) on the sulphocarbonate or viscose. As regards first cost of the solution the latter has a large advantage. One ton of wood pulp (at 12l.) can certainly be obtained in solution in a condition ready for spinning at a total cost (materials) of less than 30l. The cuprammonium process, so far as 'outside' information goes, requires for production of the solution (1) cotton as raw material, (2) ammonia (calc. as concentrated aqueous) equal to 1-1/2 times its weight, and (3) metallic copper 25 p.ct. of its weight; and the costs are approximately 100l. per ton. It is obvious that the materials are recoverable from the precipitating-bath, but at a certain added cost. We have no statements as to the proportion recoverable nor the costs incurred, and we are therefore unable to measure the total net cost of the regenerated cellulose by this process. It is certainly much less than by the collodion processes. As to the textile quality of the thread, the product has not yet been on a sufficiently wide selling basis for that to have been determined. There are a great many factors which enter here. Not merely the external characters of lustre, softness, and translucency, but the all-important quality of uniformity of thread. The collodion-spinning is a process still very defective in this respect, and the defect is no doubt referable to the difficulty of securing absolute physical invariability of the collodion. It is to be regretted, in the interests of scientific development, that none of the technologists who have published investigations of these processes have entered into the discussion of the fundamental factors of the spinning processes; we are, therefore, unable at this stage to discuss these elements of a full comparison in greater detail. We cannot, for this reason, say how far the cuprammonium process diverges in point of control from the standard of the collodion processes. Of the 'viscose' product we have a more intimate knowledge, and it certainly reaches a higher general standard than the older and now well-known artificial silks. The process is also sufficiently developed to enable the total costs of production to be estimated at a figure less than one-half that of the 'collodion' processes. This would assure to this system an entree in this country, and a basis of expansion limited only by the ordinary laws of supply and demand.

This prospect is opened up precisely at the moment when, for various reasons connected both with the difficulties of manufacture and the narrowing of the margin of profit, the proprietors of the two systems of collodion-spinning have decided to abandon all idea of manufacturing by these systems in this country.[15] We leave the discussion of the industrial problem at this point.

In regard to other developments based upon the exceptional character and properties of the sulphocarbonate, their further discussion will exemplify no general principles; and as regards technical detail they have been dealt with in the papers previously noticed.

As a purely general question, if there is to be any industry in these 'artificial' forms of cellulose, commensurate with the magnitude that usually belongs to the cellulose industries, it must come by way of a plastic or soluble form prepared at low cost, and conserving the essential molecular properties of the cellulose aggregate. These are the particular features of the sulphocarbonate. The obvious difficulties in the way of its industrial applications are those caused by the presence of alkali and sulphur compounds. These are dealt with by appropriate chemical means; but the fact that there is a special chemistry of the product has rendered its industrial progress slow. The work of the last five years in this, as in other applications of cellulose in its many derived forms, has resulted in a considerable addition to the domain of practical chemistry.

Further developments will make an increasing demand upon our grasp of the fundamental constitutional problems, to which it is the main purpose of the present volume to contribute.

FOOTNOTES:

[11] This is the most complete notice that has appeared and the bibliography is exhaustive. The publication comes into our hands too late to be noticed in detail.

[12] Text-book on Paper-making, Cross and Bevan (Spon, London: second edition, 1900). Chemistry of Paper-making, Griffin and Little (New York, 1894: Howard Lockwood & Co.). Handbuch d. Papierfabrikation, C. Hofmann (Berlin). Paper Trade Review, London (weekly). Papier-Zeitung, Berlin.

[13] William Mather, M.P., of the firm of Mather & Platt, Limited, Manchester.

[14] The actual costs varying considerably in the various countries, we cannot make any specific statement. But from estimates we have made, the costs of obtaining cotton in filtered solution as collodion multiply its value by 12-14, the denitrations adding further costs and raising this multiple to 18-20. In the same estimates we arrived at the conclusion that the item for raw materials made up 60 p.ct. of the total cost of the yarn.

[15] The recent failure of a French company founded for the exploitation of the cuprammonium process may be taken as showing that it presents very considerable technical difficulties. It is a matter of common knowledge that this company estimated the costs of production to be such as to enable the product to be sold at 12 fr. per kilo., whereas the costs actually obtaining were a large multiple of this figure.



INDEX OF AUTHORS

Bardy, C. H., 157

Bokorny, T., 43

Bronnert, E., 54

Bumcke, G., and Wolffenstein, R., 67

Buntrock, 25

Cross, C. F., 139, 152, 155

Cross, C. F., and Bevan, E. J., 92

Cross, C. F., Bevan, E. J., and Briggs, J. F., 118

Cross, C. F., Bevan, E. J., and Heiberg, T., 114

Cross, C. F., Bevan, E. J., and Smith, C., 101, 103, 105, 114, 145

De Haas, R. W. T., and Tollens, B., 151

Faber, O. v., and Tollens, B., 71

Feilitzen, H. v., and Tollens, B., 154

Fenton, H. J. H., 8

Fenton, H. J. H., and Gostling, M., 86

Fraenkel, A., and Friedlaender, P., 26

Gardner, P., 22

Gilson, E., 112

Hancock, W. C., and Dahl, O. W., 135

Hoffmeister, W., 96, 100

Kleiber, A., 97

Kroeber, E., 121

Krueger, M., 119

Lange, H., 25

Lewes, V. H., 15

Luck, A., and Cross, C. F., 45

Margosches, B. M., 159

Morrell, R. S., and Crofts, J. M., 114

Mylius, F., 21

Nastukoff, H., 74

Omelianski, V., 76

Ruff, O., 117

Salkowski, E., 113

Schoene, A., and Tollens, B., 124

Seidel, H., 149

Sherman, H. C., 137

Simonsen, E., 146

Storer, F. H., 142

Strehlenert, R. W., 158

Suringar, H., and Tollens, B., 16, 124

Suevern, C., 63

Tollens, B., 148, 151

Tollens, B., and Glaubitz, H., 122

Vignon, L., 43, 70, 72, 94

Will, W., and Lenze, P., 41

Winterstein, E., 109, 144, 153



INDEX OF SUBJECTS

Acetone, action on cellulose nitrates of diluted, 46

Acid-cellulose, 68

Acids, volatile, from cellulose, 145

AEschynomene aspera, 135

Alcohol from cellulose and wood, 146

Alcoholic soda, mercerisation results with, 26

Alkali-cellulose, effects of long storage on, 31

Amyloid, vegetable, 153

Arabinose from gluconic acid, 117

'Ash' of plants, 13

Bacterium xylinum, 85

Barley plant, chemical processes in the, 103

—— straw, carbohydrates of, 105

Bleaching, 166

Bran, digestion of, 139

Brommethylfurfural, 8, 84, 86

Carbohydrates, action of hydrogen bromide on, 86; action of hydrogen peroxide on, 114; nitrated, as food for mould fungi, 43; nitrates of, 41; quantitative separation of, 96

Carbohydrates of barley straw, 105; of wheat, 137; of yeast, 113

'Caro's reagent,' 118

'Celloxin,' 71

Cellulose, alcohol from, 146; constitution of, 77, 92; fermentation of, 76; industrial uses of, 155; iodine reaction of, 21; methods for the estimation of, 3, 4, 16, 19, 97; nitration of, 43; saccharification of, 73; ultimate hydrolysis of, 11; volatile acids from, 145

—— acetates, monoacetate, formation of, 40; tetracetate, constitution of, 80

—— benzoates, 34; from structureless cellulose, 36; from three varieties of cotton, 35; monobenzoate, properties of, 36; dibenzoate, properties of, 37; acetylation of, 130; nitration of, 38

—— derivatives, commercial aspects of, 171; saccharification of, 73

—— nitrates, 44, 45, 83; structureless, 45, 51; cupric reducing power of, 73; instability of, 50, 53

—— sulphocarbonate, 27; effects of the nature of the cellulose, 28;

—— —— solutions, analysis of, 32; iodine reaction of, 33; loss of carbon bisulphide, 33; viscosity of, 30

Cell-wall constituents, 97

Cereal celluloses, 101, 105

Chitin, 112

Chlorination, Cross and Bevan's method, 19; statistics of, 134

Chloro-lignone, 126

Collodion. See Silk, artificial

Cotton, lustreing effect of mercerisation, 23; mercerised, structural properties of, 25; pentosane content of, 148

'Crude fibre,' 17

Cuprammonium solvent, 21, 58, 173

Currants, pectin of, 152

Denitration of collodion silk, 56; of jute nitrate, 133; products of, 74

Dioxybutyric acid, 71

Elder pith, 137

Eriodendron, seed hair of, 92

Explosives, 44; sporting powders, 52

Fermentation of cellulose, 76; of furfuroids, 108; of sugar from wood, 148

Fibres, report on miscellaneous, 139

Flax boiling, 168; spinning, 161

Fodder plants, pentosanes of, 122

Fungi, tissue constituents of, 109

Furfural from cellulose, oxycellulose, and hydrocellulose, 70; derivative from laevulose, 8; estimation as hydrazone and phloroglucide, 119, 121; oxidation of, 114, 118 (refer also 'Pentosanes')

Furfuroids, 8, 10, 102, 105; assimilation of, 108

Gabriel's method of cellulose estimation, 18

Gluconic acid, action of hydrogen peroxide on, 117

Glucosamin, 112

Hemicellulose, 96, 97; determination and separation of, 100

Hoenig's method of cellulose estimation, 18

'Hydralcellulose,' 68

Hydrocellulose, 73; nitration of, 43

Hydrogen peroxide, oxidations with, 114

Hydroxyfurfural in lignocellulose, 9, 116, 118

Incandescent mantles of artificial silk, 14, 15

Industrial appliances of cellulose, 155

Iodine reaction of cellulose, 21

Isosaccharinic acid, 71

Jute, composition of, 141; quality of, 140; treatment of, 142 (refer also Lignocellulose)

—— acetate, 129

—— benzoate, 127; acetylation of, 130; nitration of, 132

—— nitrate, 131

Ketoses, physiological importance of, 9

Lange method of cellulose estimation, 18, 98

Lead compounds of nitrated carbohydrates, 49

Lignin, 100

Lignocellulose, constitution of, 133; esters of, 125; hydroxyfurfural in, 9; new type of, 135

Lignone complex, properties of, 126

'Lignorosin,' 151

'Lustra-cellulose.' See Silk, artificial

Malt, pentosanes of, 122

Mather system of boiling textiles, 167

Mercerization, 22; shrinkage during, 24

Mercerised yarn, strength and elasticity of, 25, 26

Methylhydroxyfurfural, 84

Mould fungi, nitrated carbohydrates as food for, 43

Mycosin, 113

Nitrated carbohydrates, lead compounds of, 49

Nitrates of carbohydrates, 41

Nitrocellulose (see Cellulose nitrates); silk, 55

'Normal' cellulose, definition of, 27

Normal paper, 160

Oxycellulose esters, 72; nitration of, 43; researches on, 71, 72, 74; resume of properties, 94

Oxygluconic acid, 117

Paper, deterioration of, 155; normal standard, 160; pulp, spinning of, 169

Peat, constituents of, 154

Pectins, 151, 152

Pentosanes, 100, 109, 144; constituents of cotton, 124; constituents of fodder, 122; estimation of, 121; of seeds during germination, 124

'Permanent tissue,' 103

Phloroglucinol, 119, 121

Plant tissues, carbohydrates of, 96, 97, 99

Plants, source of unsaturated compounds in, 145

Powders, manufacture of sporting, 52

Saccharification of cellulose and derivatives, 73

Schulze method of cellulose estimation, 18, 98

Schweizer solution, 101

Seeds, pentosanes in germinating, 124

Silica in plant tissues, 13

Silk, artificial, 54, 62, 63, 172; bibliography of, 60; from cuprammonium, 58, 64, 173; from nitrocellulose (collodion), 55, 63, 172; from viscose, 59; from zinc chloride, 59; reactions of, 64

—— natural, reactions of, 64

Straws, 101, 105

Succinic acid from furfural, 118

Sulphite waste liquors, 149, 164

'Swedish' filter paper, 14

Tissue constituents, 99, 109

Trees, composition of trunk woods, 142

Viscose and viscoid, 157, 158, 159

—— silk, 59, 175

—— —— specific gravity of, 34 (refer also Cellulose sulphocarbonate)

'Vulcanised fibre,' 20

Weende, method of cellulose estimation (crude fibre), 17, 98

Welsbach mantles, 14; Clamond type, 15

Wheat grain, insoluble carbohydrates of, 137

Wood, alcohol from, 146, 148

Wood-cellulose, waste liquors, 149

Wood-gum, 144

Wood-pulp, processes, 162

Wood, trunks of trees, 142

Yeast, carbohydrates of, 113

Zinc chloride, artificial silk, 59; solvent action of, 20

THE END