SECTION II.. _on the Photographic Properties of the Salts of Silver._

On the Photographic Properties of the Salts of Silver.

In addition to the Salts of Silver described in the first Section of this Chapter there are many others well known to chemists, as the Acetate of Silver, the Sulphate, the Citrate of Silver, etc. Some occur in crystals which are soluble in water, whilst others are pulverulent and insoluble.

The Salts of Silver formed by colourless Acids are white when first prepared, and remain so if kept in a dark place; but they possess the remarkable peculiarity of being darkened in colour by exposure to Light.

Action of Light upon the Nitrate of Silver.--The Nitrate of Silver is one of the most permanent of the Silver salts. It may be preserved unchanged in the crystalline form, or in solution in distilled water, for an indefinite length of time, even when constantly exposed to the diffused light of day. This is partly explained by the nature of the acid with which Oxide of Silver is associated in the Salt; Nitric Acid, possessing strong oxidizing properties, being opposed to the darkening influence of Light upon the Silver compounds.

Nitrate of Silver may, however, be rendered susceptible to the influence of Light, by adding to its solution organic matter, vegetable or animal. The phenomena produced in this case are well illustrated by dipping a pledget of cotton-wool, or a sheet of white paper, in solution of Nitrate of Silver, and exposing it to the direct rays of the sun; it slowly darkens, until it becomes nearly black. The stains upon the skin produced by handling Nitrate of Silver are caused in the same way, and are seen most evidently when the part has been exposed to light.

The varieties of organic matter which especially facilitate the blackening of Nitrate of Silver are such as tend to absorb Oxygen; hence pure vegetable fibre, free from Chlorides, such, for instance, as the Swedish filtering-paper, is not rendered very sensitive by being simply brushed with solution of the Nitrate, but a little grape sugar added soon determines the decomposition.

Decomposition of Chloride, Bromide, and Iodide of Silver by Light.--Pure moist Chloride of Silver changes slowly from white to violet on exposure to light. Bromide of Silver becomes of a grey colour, but is less affected than the Chloride. Iodide of Silver (if free from excess of Nitrate of Silver) does not alter in appearance by exposure even to the sun's rays, but retains its yellow tint unchanged. Of these three compounds therefore Chloride of Silver is the most readily acted on by light, and papers prepared with this salt will become far darker on exposure than others coated with Bromide or Iodide of Silver.

The Chloride here spoken of is the compound prepared by adding a soluble Chloride to a solution of Nitrate of Silver: the product of the direct action of Chlorine upon metallic Silver is sometimes insensitive to light.

There are certain conditions which accelerate the action of light upon the Chloride of Silver. These are, first, an excess of Nitrate of Silver, and second, the presence of organic matter. Pure Chloride of Silver would be useless as a Photographic agent, but a Chloride with excess of Nitrate is very sensitive. Even Iodide of Silver, ordinarily unaffected, is blackened by light when moistened with a solution of the Nitrate of Silver.

The reader will understand that the Acetate, Sulphate, or any other soluble Salt of Silver, might be substituted for the Nitrate in this experiment.

Organic matter combined with Chloride and Nitrate of Silver gives a still higher degree of sensibility, and in this way the Photographic papers are prepared.

The blackening of Chloride of Silver by Light explained.--This may be studied by suspending pure Chloride of Silver in distilled water, and exposing it to the sun's rays for several days. When the process of darkening has proceeded to some extent, the supernatant liquid is found to contain free Chlorine, or, in place of it. Hydrochloric Acid (H Cl), the result of a subsequent action of the Chlorine upon the water.

The luminous rays appear to loosen the affinity of the elements Chlorine and Silver for each other; hence a portion of Chlorine is separated, and the white Protochloride is converted into the violet Subchloride of Silver. If an atom of Nitrate of Silver be present, the liberated Chlorine unites with it, displacing Nitric Acid, and forming again Chloride of Silver, which is decomposed in its turn. The excess of Nitrate of Silver thus exerts an accelerating influence upon the darkening of Chloride of Silver, by rendering the chain of chemical affinities more complete, and preventing an accumulation of Chlorine in the liquid, which would be a check to the continuance of the action.

Action of Light upon organic Salts of Silver.--On adding diluted Albumen, or white of egg, to solution of Nitrate of Silver, a flocculent deposit forms which is a compound of the animal matter with Protoxide of Silver, and is known as "Albuminate of Silver." This substance is at first quite white, but on exposure to light it turns to a brick-red colour. The change which takes place is one of deoxidation, the Protoxide of Silver losing a portion of its Oxygen, and a Suboxide of Silver, the product of the reduction, remaining in union with the oxidized Albumen. The red compound may therefore be loosely designated as an Albuminate of Suboxide of Silver.

Gelatine does not precipitate Nitrate of Silver in the same manner as Albumen: but if a sheet of transparent Gelatine be allowed to imbibe a solution of the Nitrate, it becomes of a clear ruby-red tint on exposure to light, and a true chemical compound of Gelatine, or a product of its oxidation, with a low Oxide of Silver, is produced.

Caseine, the animal principle of milk, is coagulated by Nitrate of Silver, and the red substance formed on exposing the curds to light may be viewed as analogous in composition to the corresponding compounds with Albumen and Gelatine.

Many other organic salts of Silver are darkened by light. The white Citrate of Protoxide of Silver changes to a red substance, reacting with chemical tests in the same manner as Wöhler's Citrate of Suboxide of Silver, which he obtained by reducing the ordinary Citrate in Hydrogen Gas. Glycyrrhizin, the Sugar of Liquorice, also forms a white compound with Oxide of Silver which becomes brown or red in the sun's rays.

For further particulars on the action of light upon the Salts of Silver associated with organic matter, see the Author's paper on the composition of the photographic image, in the eighth Chapter.

SIMPLE EXPERIMENTS ILLUSTRATING THE ACTION OF LIGHT UPON A SENSITIVE LAYER OF CHLORIDE OF SILVER ON PAPER.

In the performance of the most simple experiments on the decomposition of Silver Salts by Light, the student may employ ordinary test-tubes, in which small quantities of the two liquids required for the double decomposition may be mixed together.

When however concentrated solutions are used in this way, the insoluble Silver Salt falls in dense and clotted masses, which, exposed to the sun's rays, quickly blacken on the exterior, but the inside is protected, and remains white. It is of importance therefore in Photography that the sensitive material should exist in the form of a surface, in order that the various particles of which it is composed may each one individually be brought into relation with the disturbing force.

Full directions for the preparation of sensitive Photographic paper are given in the second division of this work. The following is the theory of the process:--A sheet of paper is treated with solution of Chloride of Sodium or Ammonium, and subsequently with Nitrate of Silver; hence results a formation of Chloride of Silver in a fine state of division, with an excess of Nitrate of Silver, the Silver bath having been purposely made stronger in proportion than the salting solution.

Illustrative Experiment No. I.--Place a square of sensitive paper (prepared according to the directions given in the Second Part of the work) in the direct rays of the sun, and observe the gradual process of darkening which takes place; the surface passes through a variety of changes in colour until it becomes of a deep chocolate-brown. If the Light is tolerably intense, the brown shades are probably reached in from three to five minutes; but the sensibility of the paper, and also the nature of the tints, will vary much with the character of the organic matter present.

Experiment No. II.--Lay a device cut from black paper upon a sheet of sensitive paper, and compress the two together by means of a sheet of glass. After a proper length of exposure the figure will be exactly copied, the tint however being reversed: the black paper protecting the sensitive Chloride beneath, produces a white figure upon a dark ground.

Experiment No. III.--Repeat the last experiment, substituting a piece of lace or gauze-wire for the paper device. This is intended to show the minuteness with which objects can be copied, since the smallest filament will be distinctly represented.

Experiment No. IV.--Take an engraving in which the contrast of light and shade is tolerably well marked, and having laid it closely in contact with the sensitive paper, expose as before. This experiment shows that the surface darkens in degrees proportionate to the intensity of the light, so that the half shadows of the engraving are accurately maintained, and a pleasing gradation of tone produced.

In the darkening of Photographic papers, the action of the light is quite superficial, and although the black colour may be intense, yet the amount of reduced Silver which forms it is so small that it cannot conveniently be estimated by chemical reagents. This is well shown by the results of an analysis performed by the Author, in which the total weight of Silver obtained from a blackened sheet measuring nearly 24 by 18 inches amounted to less than half a grain. It becomes therefore of great importance in preparing sensitive paper to attend to the condition of the surface layer of particles, the action rarely extending to those beneath. The use of Albumen, Gelatine, etc., which will be explained in the eighth Chapter, has reference to this amongst other advantages, and secures a better and more sharply defined print.