CHEMISTRY OF THE SOLUTION OF PYROXYLINE IN ETHER AND ALCOHOL, OR "COLLODION."
The substitution compounds B and C, already alluded to as forming the Soluble Cotton of Photographers, are both abundantly soluble in Acetic Ether. This liquid however is not adapted for the purpose required, inasmuch as on evaporation it leaves the Pyroxyline in the form of a white powder, and not as a transparent layer.
The rectified Ether of commerce has been found to answer better than any other liquid as a solvent for Pyroxyline.
If the sp. gravity be about ·750, it contains invariably a small proportion of Alcohol, which appears to be necessary; the solution not taking place with absolutely pure Ether. The Pyroxyline, if properly prepared, begins almost immediately to gelatinize by the action of the Ether, and is soon completely dissolved. In this state it forms a slimy solution, which, when poured out on a glass plate, dries up into a horny transparent layer.
In preparing Collodion for Photographic purposes, we find that its physical properties are liable to considerable variation. Sometimes it appears very thin and fluid, flowing on the glass almost like water, whilst at others it is thick and glutinous. The causes of these differences will now engage our attention. They may be divided into two classes: first, those relating to the Pyroxyline; second, to the solvents employed.
a. Variation of Properties in different Samples of soluble Pyroxyline.—The substitution compounds A, B, C, and D differ, as already shown, in the percentage amount of Peroxide of Nitrogen present, and the former are more explosive and insoluble than the latter. But it often happens in preparing Pyroxyline, that two portions of Nitro-Sulphuric Acid taken from the same bottle yield products which vary in properties, although they are necessarily the same in composition.
Taking extremes in illustration, we notice two principal modifications of soluble Pyroxyline.
The first, when treated with the mixture of Ether and Alcohol, sinks down to a gummy or gelatinous mass, which gradually dissolves on agitation The solution is very fluid in proportion to the number of grains used, and when poured out spreads into a beautifully smooth and glassy surface, which is quite structureless, even when highly magnified. The film adheres tightly to the glass, and when the finger is drawn across it, separates in short fragments, and broken pieces.
The second variety produces a Collodion which is thick and glutinous, flowing over the glass in a slimy manner, and soon setting into numerous small waves and cellular spaces. The film lies loose upon the glass, is apt to contract on drying, and may be pushed off by the finger in the form of a connected skin.
This subject is not thoroughly understood, but it is known that the temperature of the Nitro-Sulphuric Acid at the time of immersing the Cotton influences the result. The soluble variety is produced by hot acids; the second, or glutinous, by the same acids employed cold, or only slightly warm. The best temperature appears to be from 130° to 155° Fahrenheit; if it rises much beyond that point, the acids act upon and dissolve the Cotton.