E. J. Bevan

“ 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. ”

“ We have shown that the hydroxyfurfurals are constituents of the lignocelluloses. The proportion present in the free state is small, and it is not difficult to show that they are products of breakdown of the lignone groups. If we assume that such groups are derived ultimately from levulose, we have to account for the detachment of the methyl group. This, however, is not difficult, and we need only call to mind that the lignocelluloses are characterised by the presence of methoxy groups and a residue which is directly and easily hydrolysed to acetic acid. ”

“ A large amount of experimental matter has been accumulated in view of the ultimate contribution of the results to the general theory of colloidal solutions. But viscose is a complex product and essentially variable, through its pronounced tendency to progressive decomposition with reversion of the cellulose to its insoluble and uncombined condition. The solution for this reason does not lend itself to exact measurement of its physical constants such as might elucidate in some measure the progressive molecular aggregation of the cellulose in assuming spontaneously the solid (hydrate) form. ”

“ 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. ”

“ Generally we may sum up the present solution of the problem of the relationship of the furfuroids to plant assimilation and growth as follows:—The pentoses are not produced as such in the process of assimilation; but furfural-yielding carbohydrates are produced directly and in approximately constant ratio to the total carbohydrates; they are mainly located in the permanent tissue; in the secondary changes of dehydration, &c., accompanying maturation they undergo such differentiation that they become readily separable by processes of acid hydrolysis from the more resistant normal celluloses ”

“ He also considers that the bisulphide of carbon, which must be regarded as a noxious compound, is a serious bar to the industrial use of the process, and for economic work he considers that the regeneration of ammonia from the precipitating liquors is necessary and would be as objectionable as the denitration baths in the collodion process. The final product not being on the market he does not pronounce a finally unfavourable opinion. ”

“ 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. ”

“ As the group has been widened very much beyond these limits, it is clear that if any group term or designation is to be retained that of 'furfuroid' is 'neutral' in character, and equally applicable to saturated substances of such widely divergent chemical character as pentoses, hexosones, glycuronic acid, and perhaps, most important of all, levulose itself, all of which are susceptible of condensation to furfural or furfurane derivatives, as well as to those unsaturated compounds, constituents of plant tissues which are already furfurane derivatives. ”

“ 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 Tropœolum majus, Pœonia officinalis, and Impatiens Balsamina. The raw material was carefully purified by exhaustive treatment with ether and alcohol, &c. ”

“ 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 [Pg 164] 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. ”

“ This view receives some support from the fact that the interaction of the H2O2 with permanganates has now been established to be an oxidation of the H2 of the peroxide by the permanganate oxidation, with liberation, therefore, of the O2 of the peroxide as an unresolved molecule [Baeyer] .
Benzene itself is also powerfully attacked by the peroxide when shaken with a dilute solution in presence of iron salts. The products are phenol and pyrocatechol, with some quantity of an amorphous product probably formed by condensation of a quinone with the phenolic products of reaction. ”

“ Mechanically all resolve themselves into the preparation of a structureless filtered solution of cellulose or a cellulose derivative, and forcing through capillary orifices into some medium which either absorbs or decomposes the solvent. The author notes here that the fineness and to a great extent the softness of the product depends upon the dimensions of the capillary orifice and concentration of the solution. The technical idea involved in the spinning of artificial fibres is an old one. ”

“ ZINC CHLORIDE.—To prepare a homogeneous solution of cellulose by means of the neutral chloride, a prolonged digestion at or about 100° with the concentrated reagent is required. The dissolution of the cellulose is not a simple phenomenon, but is attended with hydrolysis and a certain degree of condensation. The latter result is evidenced by the formation of furfural, the former by the presence of soluble carbohydrates in the solution obtained by diluting the original solution and filtering from the reprecipitated cellulose. ”

“ The transition from a cellulose-ketone to the lignone-ketone involves a simple condensation without rearrangement; from which we may argue back to the greater probability of the ketonic structure of the cellulose. We must note, however, that the celluloses of the lignocelluloses are obtained as residues of various reactions, and are not homogeneous. They yield on boiling with condensing acids from 6 to 9 p.ct. furfural. It is usual to regard furfural as invariably produced from a pentose residue. But this interpretation ignores a number of other probable sources of the aldehyde. ”

“ If now the aldose groups tend to pass over into the starch form, representing a temporary overflow product of the assimilating energy, it would appear that the ketose or levulose groups are preferentially used up in the elaboration of the permanent tissue. We must also take into consideration the researches of Lobry de Bruyn showing the labile functions of the typical CO group in both aldoses and hexoses, whence we may conclude that in the plant-cell the transition from dextrose to levulose is a very simple and often occurring process. ”

“ 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. ”

“ But we shall find that the point again arises in attempting to define the reacting unit, which is another term for the molecule. In the majority of cases we [Pg 79] rely for this upon physical measurements; and in fact the purely chemical determination of such quantities is inferential. Attempts have been made to determine the molecular weights of the cellulose esters in solution, by observations of depression of solidifying and boiling-points. But the numbers have little value. The only other well-defined compound is the sulphocarbonate. ”

“ General Experimental Methods.—In the investigation of the cellulose group it is clear that methods of ultimate hydrolysis are of first importance. None are so convenient as those which are based on the action of sulphuric acid, more or less concentrated (H2SO4.3H2O - H2SO4H2O) . Such methods have been frequently employed in the investigations noted in this volume. We notice a common deficiency in the interpretation of the results. ”

“ There is little doubt, however, that the question of the [Pg 172] 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 ”

“ 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. ”

“ We know that a fibrous cellulose treated with acids or alkalis in such a way that only hydrolytic changes can take place is converted into a variety of forms of very different structural characteristics, and these products, while still preserving the main chemical characteristics of the original, show when converted into derivatives by simple synthesis, e.g. esters and sulphocarbonates, a corresponding differentiation of the physical properties of these derivatives, from the normal standard, and therefore that the new reacting unit determines a new physical aggregate. ”

“ The author next refers to his discoveries (15) that alcoholic solutions of a number of substances, organic and inorganic, freely dissolve the lower cellulose nitrates. The most satisfactory of these substances is chloride of calcium (16) . It is noted that acetate of ammonia causes rapid changes in the solution, which appear to be due to a species of hydrolysis. The result is sufficiently remarkable to call for further investigation. The chloride of calcium, it is thought possible, produces a direct combination of the alcohol with a reactive group of the nitrocellulose. ”

“ On the other hand, it is clear that in hydrolysing a given cellulose-complex we ought to aim at complete, i.e. quantitative, statistics. The hydrolytic transformation of starch to dextrins and maltose has been followed in this way, and the methods may serve as a model to which cellulose transformations should be approximated. In fact, what is very much wanted is a systematic re-examination of the typical celluloses in which all the constants of the terms between the original and the ultimate monose groups shall be determined. ”

“ Those which may be carried out in a reasonably short time are deficient in two directions: (1) they yield a 'cellulose' containing more or less oxycellulose; (2) the celluloses themselves are attacked under the conditions of treatment, and the end product or cellulose merely represents a particular and at the same time variable equilibrium, as between the resistance of the cellulose and the attack of the reagents employed; this attack being by no means confined to the non-cellulose constituents. ”

“ It is by such means that the mantles used in the Welsbach system of incandescent lighting are prepared. A purified cotton fabric—or yarn—is treated with a concentrated solution of the mixed nitrates of thorium and cerium, and, after drying, the cellulose is burned away. A perfect and coherent skeleton of the fabric is obtained, composed of the mixed oxides. Such mantles have fulfilled the requirements of the industry up to the present time, but later experiments forecast a notable improvement. ”

“ It must be remembered that every special province of the science has its systematic beginning, and in that stage of evolution makes a temporary 'law unto itself.' In the absence of a dominating theory or generalisation which, when adopted, gives it an organic connection with the general advance of the science, there is no other course than to classify the subject-matter. Thus 'the carbohydrates' may be said to have been in the inchoate condition, qualified by a certain classification, prior to the pioneering investigations of Fischer. ”

“ The oxycelluloses are mixtures of cellulose and a derivative oxidised compound which contains one more atom O than cellulose (cellulose = C6H10O5) , and for which the special designation Celloxin is proposed.
Celloxin may be formulated C8H6O6 or C6H10O6, of which the former is the more probable.
The various oxycelluloses may be regarded as containing one celloxin group to 1-4 cellulose groups, according to the nature of the original cellulose, and the degree of oxidation to which subjected. These groups are in chemical union. ”

“ In a preliminary discussion the author critically compares the results of various of the methods in practice for the isolation and estimation of cellulose. The method of F. Schulze [digestion with dil. HNO3 with KClO3—14 days, and afterwards treating the product with ammonia, &c.] is stated to be the 'best known' (presumably the most widely practised) ; W. Hoffmeister's modification of the above, in which the nitric acid is replaced by hydrochloric acid (10 p.ct. HCl) is next noted as reducing the time of digestion from 14 days to 1-2 days, and giving in many cases higher yields of cellulose. ”

“ The product is a cellulose of the second group of the classification. Another point in this investigation which we must criticise is the ultimate selection of the Schulze method of prolonged maceration with nitric acid and a chlorate, followed by suitable hydrolysis of the non-cellulose derivatives to soluble products. Apart from its exceptional inconvenience, rendering it quite impracticable in laboratories which are concerned with the valuation of cellulosic raw materials for industrial purposes, the attack of the reagent is complex and ill-defined. ”