It has been stated by some who have given attention to the subject, that the image is formed in all cases of pure metallic Silver, and that any observable variations in its colour and properties, are due to a difference in the molecular arrangement of the particles. But this hypothesis, although involving much that is correct, yet does not contain the whole truth, for it is evident that the chemical properties of the Photographic image often bear no resemblance to those of a metal. One Photograph may also differ essentially from another, so that we are led to infer the existence of two varieties, the first of which is less of a metallic nature than the second.
In investigating the subject, the principal point appeared to be to examine the action of light upon Chloride of Silver, and afterwards to associate the Chloride with organic matter in order to imitate the conditions under which Photographs are obtained.
The following is an epitome of the conclusions arrived at:—
Action of Light upon Chloride of Silver.—The process is accompanied by a separation of Chlorine, but its product is not a mere mixture of Chloride of Silver and Metallic Silver; if it were so, we cannot suppose that the darkening would take place beneath the surface of Nitric Acid, which it is found to do. A definite Subchloride of Silver seems to be formed, the most important property of which is its decomposition by fixing agents, such as Ammonia, and Hyposulphite of Soda, both of which destroy the violet colour, dissolving out Protochloride of Silver, and leaving a small quantity of a grey residue of metallic Silver.
Inasmuch therefore as all Photographic pictures require fixing, we may conclude that if they could be produced upon pure and isolated Chloride of Silver (which however is not the case), they would consist solely of metallic Silver.
Decomposition of organic Salts of Silver by Light.—Compounds of Oxide of Silver with organic bodies, are as a rule darkened by exposure to light, but the process does not always consist in a simple reduction to the metallic state. This assertion is proved by the employment of the following tests.
a. Mercury.—Little or no amalgamation takes place on triturating the darkened salt with this metal.
b. Ammonia and fixing agents.—These usually produce only a limited amount of action. Thus, the Albuminate of Protoxide of Silver is perfectly soluble in Ammonia; but after having been reddened by exposure to light, it is little or not at all affected.
c. Potash.—Animal matters coagulated by Nitrate of Silver, and reduced by the sun's rays, are dissolved by boiling Potash, the solution being clear and of a blood-red colour. Metallic Silver, it is presumed, if present, would remain insoluble.
d. Boiling Water.—Gelatine treated with Nitrate of Silver and exposed to light, loses its characteristic property of dissolving in hot water. This experiment is conclusive.