A Text-book of Paper-making. C. F. Cross
refraction, not, as has been shown by experiment, by virtue of its state of aggregation, but of its molecular constitution (Sachs). {7}
Animal Cellulose.
—The mantles of many of the mollusca, e.g. the Pyrosomidæ, Salpidæ, and Phallusia mammillaris, contain a resistant substance which, after isolation by chemical treatment, has been found to be identical both in composition and properties with vegetable cellulose. Cellulose has also been stated to occur in degenerated human spleen and in certain parts of the brain.
Compounds of Cellulose.
—The chemical inertness of cellulose is a matter of everyday experience in the laboratory, where it fulfils the important function of a filtering medium in the greater number of separations of solids from liquids. Its combinations with acids and with basic oxides are, as might be expected, few and of little stability. It has been shown by Mills that cellulose (cotton) in common with certain other organic fibrous substances, when immersed in dilute solutions of the acids or basic oxides, condenses these bodies within itself at the expense of the surrounding solution, which is proportionately weakened. This effect of concentration is sufficiently uniform and constant to lead us to assign it to a chemical cause, and the view is strengthened by a consideration of the relative effects upon the various acids and bases which have been investigated, and brought to the following numerical expression:—Weight of cotton 3 grm. (with 6·9 per cent. H2O and 0·05 per cent. ash)—i.e. 2·893 anhydrous fibre. Strength of solution about 0·5 grm. of the reagent in 250 cc.
| Temp. | Time. | Weight absorbed. | |
|---|---|---|---|
| H2SO4 | 4° C. (39° F.) | 3 min | 0·00495 |
| HCl | „ | „ | 0·00733 |
| NaOH | „ | „ | 0·02020 |
The molecular ratio of the absorption, in the two latter, is 3 HCl : 10 NaOH, and it is noteworthy that the same ratio was observed for silk.
Cellulose removes barium hydrate from its solution in wafer to form with it an insoluble compound. On adding lead acetate to the solution of cellulose in the ammonio-copper reagent, so prepared as to contain no carbonate, a {8} precipitate is obtained consisting of a compound of cellulose with lead oxide, but in variable proportions. The compound C6H10O5PbO is formed by the action of finely-divided lead oxide upon the above solution. Quite recently it has been shown (O’Shea, Chem. News, May 28th, 1886) that when dilute solutions of lead are passed through ordinary filter paper, a certain amount is retained which cannot be removed by washing.
Cellulose does not combine with metallic salts, a fact which has been established incidentally to researches upon the mode of action of mordants.
The combinations of cellulose with acid radicles (ethereal salts) are both definite and stable.
Triacetyl Cellulose [C6H7 (C2H3O)3 O5] is formed by treating cellulose with six times its weight of acetic anhydride at 180° C. (356° F.). The product of the reaction is a syrupy solution from which the compound in question separates on dilution with water as a white flocculent precipitate.
Triacetyl cellulose is insoluble in alcohol and in ether, but soluble in glacial acetic acid. It is easily saponified by boiling with a solution of potassium hydrate, the cellulose being regenerated. No derivative containing more than three acetyl groups has been obtained; but a mixture of the mono-and di-acetyl cellulose is formed in treating cellulose with only twice its weight of acetic anhydride, the formation of these bodies being unattended by their solution.
Whenever cellulose, in any form, is brought into contact with strong nitric acid at a low temperature, a nitro product, or a nitrate, is formed. The extent of the nitration depends upon the concentration of the acid, on the time of contact of the cellulose with it, and on the state of the physical division of the cellulose itself.
Knop, and also Kamarsch, and Heeren, found that a mixture of sulphuric acid and nitric acid also formed nitrates of cellulose; and still later (1847), Millon and Gaudin employed a mixture of sulphuric acid and nitrates of soda or potash, which they found to have the same effect. {9}
Several well characterised nitrates have been formed, but it is a very difficult matter to prepare any one in a state of purity, and without admixture of a higher or lower nitrated body.
The following are known:—
Hexa-nitrate, C12H14O4(NO3)6,* gun cotton. In the formation of this body, nitric acid of sp. gr. 1·5, and sulphuric acid of sp. gr. 1·84 are mixed, in varying proportions, about 3 of nitric to 1 of sulphuric (sometimes this proportion is reversed), and cotton is immersed in this at a temperature not exceeding 10° C. (50° F.) for 24 hours: 100 parts of cellulose yield about 175 of cellulose nitrate. The hexa-nitrate so prepared is insoluble in alcohol, ether, or mixtures of both, in glacial acetic acid or in methyl alcohol. Acetone dissolves it very slowly. This is the most explosive gun-cotton. It ignites at 160°–170° C. (320°–338° F.). According to Eder the mixtures of nitre and sulphuric acid do not give this nitrate. Ordinary gun cotton may contain as much as 12 per cent. of nitrates soluble in ether-alcohol. The hexa-nitrate seems to be the only one quite insoluble in ether-alcohol.* To represent the series of cellulose nitrates so as to avoid fractional proportions, the ordinary empirical formula is doubled and the nomenclature has reference to this double molecule.
Penta-nitrate, C12H15O5(NO3)5. This composition has been very commonly ascribed to gun-cotton. It is difficult, if not impossible, to prepare it in a state of purity by the direct action of the acid on cellulose. The best method is the one devised by Eder, making use of the property discovered by de Vrij, that gun-cotton (hexa-nitrate) dissolves in nitric acid at about 80°–90° C. (176°–194° F.) and is precipitated, as the pentanitrate, by concentrated sulphuric acid after cooling to 0° C. (32° F.); after mixing with a larger volume of water, and washing the precipitate with water and then with alcohol, it is dissolved in ether-alcohol, and again precipitated with water, when it is obtained pure.This nitrate is insoluble in alcohol, but dissolves readily {10} in ether-alcohol, and slightly in acetic acid. Strong potash solution converts this nitrate into the di-nitrate, C12H18O8 (NO3)2.
The tetra- and tri-nitrates (collodion pyroxyline) are generally formed together when cellulose is treated with a more dilute nitric acid, and at a higher temperature, and for a much shorter time (13 to 20 minutes), than in the formation of the hexa-nitrate. It is not possible to separate them, as they are soluble to the same extent in ether-alcohol, acetic ether, acetic acid or wood spirit.On treatment with concentrated nitric and sulphuric acids, both the tri-and tetra-nitrates are converted into penta-nitrate and hexa-nitrate. Potash and ammonia convert them into di-nitrate.
Cellulose di-nitrate, C18H13O8 (NO3)2 always results as the final product of the action of alkalis on the other nitrates, and also from the action of hot, somewhat dilute, nitric acid on cellulose. The di-nitrate is very soluble in ether-alcohol, acetic ether, and in absolute alcohol. Further action of alkalis on the di-nitrate results in a complete decomposition of the molecule, some organic acids and tarry matters being