[8] Silver precipitated by Gallic or Pyrogallic Acid does not appear to be free from organic matter, and probably contains also a small proportion of Oxygen.
In remarking upon these peculiarities in the molecular condition of precipitated Silver, it should be observed that the appearance of a metal whilst in mass is no indication of its colour when in the state of fine powder. Platinum and Iron, both bright metals, and susceptible of a high polish, are dull and intensely black when in a fine state of division; Gold is of a purple or yellowish brown; Mercury a dirty grey.
Reduction of the Hydracid Salts of Silver.—By the term Hydracid is meant Salts of Silver which contain no Oxygen or Oxygen-acids, but simply elements like Chlorine or Iodine combined with Silver. These elements are characterized by forming acids with Hydrogen, which acids are hence called Hydracids. Hydrochloric Acid (HCl) is an example; so also is Hydriodic Acid (HI).
The reduction of the Hydracid Salts requires to be discussed separately, because it is evidently different from that already described; the reducing agent tending only to absorb Oxygen, which is not present in these salts. The explanation is as follows: When a Chloride of a noble metal is reduced by a developer, an atom of water, composed of Oxygen and Hydrogen, takes a part in the reaction. The Oxygen of the water passes to the developer, the Hydrogen to the Chlorine.
To illustrate this, take a solution of Chloride of Gold, and add to it a little Sulphate of Iron. A yellow deposit of metallic Gold soon forms, and the supernatant liquid is found, by testing, to be acid from free Hydrochloric Acid. The following simple diagram, in which however the number of the atoms concerned is omitted, may assist the comprehension of the change.
| Compound Atom of Chloride of Gold. | Compound Atom of Water. | Atom of Sulphate of Iron. |
The symbol Au represents Gold, Cl Chlorine, H Hydrogen, and O Oxygen. Observe that the molecules H and O separate from each other and pass in opposite directions: the latter unites with the Sulphate of Iron; the former meets Cl, and produces Hydrochloric Acid (HCl), whilst the atom of Gold is left alone.
Hence there is no theoretical difficulty in supposing a reduction of Iodide of Silver by a developer, if we associate with the Iodide an atom of water to furnish the Oxygen. Unless the sensitive plate however has been exposed to the light, the reduction does not readily take place; nor can it be produced under any circumstances, with or without light, when the whole of the free Nitrate of Silver has been washed away from the plate. Pure Iodide of Silver is therefore unaffected by a developer, and the compound which blackens on the application of Sulphate of Iron or Pyrogallic acid is an Iodide with excess of Nitrate of Silver.