Part 9 (1/2)

The oxycellulose, after purification, dried at 110, gave the following a.n.a.lytical numbers:

C 43.64 43.78 43.32 43.13 H 6.17 6.21 5.98 6.08

Its compound with phenylhydrazine (_loc. cit._) gave the following a.n.a.lytical numbers:

N 0.78 0.96 0.84

(2) The reagents were as in (1), but the conditions varied by pa.s.sing a stream of carbonic acid gas through the solution contained in a flask, until Cl compounds ceased to be given off. The a.n.a.lysis of the purified oxycellulose gave C 43.53, H 6.13.

(3) The conditions were as in (2), but a much stronger hypochlorite solution--viz. 12B.--was employed. The yield of oxycellulose precipitated from solution in soda lye (10 p.ct. NaOH) was 45 p.ct.

There was only a slight residue of unattacked cellulose. The a.n.a.lytical numbers obtained were:

Oxycellulose C 43.31 43.74 43.69 ” H 6.47 6.42 6.51 ________________________

Phenylhydrazine compound N 0.62 0.81

B. _Oxidation by permanganate_ (KMnO_{4}). (1) The cellulose 16 grms.

was treated with 1100 c.c. of a 1 p.ct. solution of KMnO_{4} in successive portions. The MnO_{2} was removed from time to time by digesting the product with a dilute sulphuric acid (10 p.ct.

H_{2}SO_{4}). The oxycellulose was purified as before, yield 40 p.ct.

a.n.a.lytical numbers:

Oxycellulose C 42.12 42.9 ” H 6.20 6.11 ________________________

Phenylhydrazine compound N 1.35 1.08 1.21

(2) The cellulose (16 grms.) was digested 14 days with 2500 c.c. of 1 p.ct. KMnO_{4} solution. The purified oxycellulose was identical in all respects with the above: yield 40 p.ct. C 42.66, H 6.19.

(3) The cellulose (16 grms.) was heated in the water-bath with 1600 c.c.

of 15 p.ct. H_{2}SO_{4} to which were added 18 grms. KMnO_{4}. The yield and composition of the oxycellulose was identical with the above. It appears from these results that the oxidation with hypochlorites acids 1 atom of O to 4-6 of the unit groups C_{6}H_{10}O_{5}; and the oxidation with permanganate 2 atoms O per 4-6 units of C_{6}H_{10}O_{5}. The molecular proportion of N in the phenylhydrazine residue combining is fractional, representing 1 atom O, i.e. 1 CO group reacting per 4 C_{36}H_{60}O_{31} and 6 C_{24}H_{49}O_{21} respectively, a.s.suming the reaction to be a hydrazone reaction.

Further investigations of the oxycelluloses by treatment with (a) sodium amalgam, (b) bromine (water), and (c) dilute nitric acid at 110, led to no positive results.

By treatment with alcoholic soda (NaOH) the products were resolved into a soluble and insoluble portion, the properties of the latter being those of a cellulose (hydrate).

_Molecular weight of cellulose and oxycellulose._--The author endeavours to arrive at numbers expressing these relations by converting the substances into acetates by Schutzenberger's method, and observing the boiling-points of their solution in nitrobenzene.

FERMENTATION OF CELLULOSE

V. OMELIANSKI (Compt. Rend., 1897, 125, 1131-1133).

Pure paper was allowed to ferment in the presence of calcium carbonate at a temperature of 35 for 13 months. The products obtained from 3.4743 grams of paper were: acids of the acetic series, 2.2402 grams; carbonic anhydride, 0.9722 grams; and hydrogen, 0.0138 gram. The acids were chiefly acetic and butyric acid, the ratio of the former to the latter being 1.7 : 1. Small quant.i.ties of valeric acid, higher alcohols, and odorous products were formed.

The absence of methane from the products of fermentation is remarkable, but the formation of this gas seems to be due to a special organism readily distinguishable from the ferment that produces the fatty acids.

This organism is at present under investigation.

(p. 75) ~Const.i.tution of Cellulose.~--It may be fairly premised that the problem of the const.i.tution of cellulose cannot be solved independently of that of molecular aggregation. We find in effect that the structural properties of cellulose and its derivatives are directly connected with their const.i.tution. So far we have only a superficial perception of this correlation. We know that a fibrous cellulose treated with acids or alkalis in such a way that only hydrolytic changes can take place is converted into a variety of forms of very different structural characteristics, and these products, while still preserving the main chemical characteristics of the original, show when converted into derivatives by simple synthesis, _e.g._ esters and sulphocarbonates, a corresponding differentiation of the physical properties of these derivatives, from the normal standard, and therefore that the new reacting unit determines a new physical aggregate. Thus the sulphocarbonate of a 'hydrocellulose' is formed with lower proportions of alkaline hydrate and carbon disulphide, gives solutions of relatively low viscosity, and, when decomposed to give a film or thread of the regenerated cellulose, these are found to be deficient in strength and elasticity. Similarly with the acetate. The normal acetate gives solutions of high viscosity, films of considerable tenacity, and when those are saponified the cellulose is regenerated as an unbroken film.

The acetates of hydrolysed celluloses manifest a retrogradation in structural and physical properties, proportioned to the degree of hydrolysis of the original.

We may take this opportunity of pointing out that the celluloses not only suggest with some definiteness the connection of the structural properties of visible aggregates--that is, of matter in the ma.s.s--with the configuration of the chemical molecule or reacting unit, but supply unique material for the actual experimental investigation of the problems involved. Of all the 'organic' colloids cellulose is the only one which can be converted into a variety of derivative forms, from each of which a regular solid can be produced in continuous length and of any prescribed dimensions. Thus we can compare the structural properties of cellulose with those of its hydrates, nitrates, acetates, and benzoates, in terms of measurements of breaking strain, extensibility, elasticity.

Investigations in this field are being prosecuted, but the results are not as yet sufficiently elaborated for reduction to formulae. One striking general conclusion is, however, established, and that is that the structural properties of cellulose are but little affected by esterification and appear therefore to be a function of the special arrangement of the carbon atoms, i.e. of the molecular const.i.tution.

Also it is established that the molecular aggregate which const.i.tutes a cellulose is of a resistant type, and undoubtedly persists in the solutions of the compounds.