To produce the peculiar change by which Cotton is converted into Pyroxyline, both Nitric and Sulphuric Acids are, as a rule, required; but of the two the former is the most important. On analyzing Pyroxyline, Nitric Acid, or a body analogous to it, is detected in considerable quantity, but not Sulphuric Acid. The latter Acid, in fact, serves but a temporary purpose, viz. to prevent the Nitric Acid from dissolving the pyroxyline, which it would be liable to do if employed alone. The Sulphuric Acid prevents the solution by removing water from the Nitric Acid, and so producing a higher degree of concentration; Pyroxyline, although soluble in a dilute, is not so in the strong Acid, and hence it is preserved.
The property possessed by Oil of Vitriol of removing water from other bodies, is one with which it is well to be acquainted. A simple experiment will serve to illustrate it. Let a small vessel of any kind be filled to about two-thirds with Oil of Vitriol, and set aside for a few days; at the end of that time, and especially if the atmosphere be damp, it will have absorbed sufficient moisture to cause it to flow over the edge.
Now even the strongest reagents employed in chemistry contain, almost invariably, water in greater or lesser quantity. Pure Anhydrous Nitric Acid is a white, solid substance; Hydrochloric Acid is a gas: and the liquids sold under those names are merely solutions. The effect then of mixing strong Oil of Vitriol with aqueous Nitric Acid is to remove water in proportion to the amount used, and to produce a liquid containing Nitric Acid in a high state of concentration, and Sulphuric Acid more or less diluted. This liquid is the Nitro-Sulphuric Acid employed in the preparation of Pyroxyline.
Various forms of Pyroxyline.—Very soon after the first announcement of the discovery of Pyroxyline, most animated discussions arose amongst chemists with regard to its solubility and general properties. Some spoke of a "solution of Gun-Cotton in Ether;" whilst others denied its solubility in that menstruum; a third class, by following the process described, obtained a substance which was not explosive, and therefore could scarcely be termed Gun-Cotton.
On further investigations some of these anomalies were cleared up, and it was found that there were varieties of Pyroxyline, depending mainly upon the degree of strength of the Nitro-Sulphuric Acid employed in the preparation. Still the subject was obscure until the publication of researches by Mr. E. A. Hadow. These investigations, conducted in the Laboratory of King's College, London, were published in the Journal of the Chemical Society. Constant reference will be made to them in the following remarks.
We notice—first, the chemical constitution of Pyroxyline; secondly, its varieties; and thirdly, the means adopted to procure a Nitro-Sulphuric Acid of the proper strength.
a. Constitution of Pyroxyline.—Pyroxyline has been sometimes spoken of as a Salt of Nitric Acid, a Nitrate of Lignine. This view however is erroneous, since it can be shown that the substance present is not Nitric Acid, although analogous to it. It is the Peroxide of Nitrogen, which is intermediate in composition between Nitrous Acid (NO3) and Nitric Acid (NO5). Peroxide of Nitrogen (NO4) is a gaseous body of a dark red colour; it possesses no acid properties, and is incapable of forming a class of salts. In order to understand in what state this body is combined with cotton fibre to form Pyroxyline, it will be necessary to digress for a short time.
Law of Substitution.—By the careful study of the action of Chlorine, and of Nitric Acid, upon various organic substances, a remarkable series of compounds has been discovered, containing a portion of Chlorine or of Peroxide of Nitrogen in the place of Hydrogen. The peculiarity of these substances is, that they strongly resemble the originals in their physical, and often in their chemical properties. It might have been supposed that agents of such active chemical affinities as Chlorine and Oxide of Nitrogen would, by their mere presence in a body, produce a marked effect; yet it is not so in the case before us. The primitive type or constitution of the substance modified remains the same, even the crystalline form being often unaffected. It seems as if the body by which the Hydrogen had been displaced had stepped in quietly and taken up its position in the framework of the whole without disturbance. Many compounds of this kind are known; they are termed by chemists "substitution compounds." The law invariably observed is, that the substitution takes place in equal atoms: a single atom of Chlorine, for instance, displaces one of Hydrogen; two of Chlorine displace two of Hydrogen, and so on, until, in some cases, the whole of the latter element is separated.