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Higher oxides of silver

Electrolysis of Silver nitrate solution at 0° C. yields at the anode a black, crystalline substance of metallic lustre. It readily loses oxygen, Silver nitrate entering into solution, and the residual crystals of silver peroxynitrate have the formula 2Ag3O4,AgNO3. It changes slowly, with evolution of oxygen, into 3Ag2O,AgNO3. According to Weber, the presence of between 15 and 25 per cent, of nitric acid inhibits the deposition of the peroxynitrate at the anode, but produces a brown solution. Weber regards the oxide portion of the salt as having the formula Ag(AgO2)2, analogous to that of magnetic iron oxide, and considers it to be the silver salt of an unstable argentic acid, HAgO2. It is a compound of silver in which the metal has a valency greater than unity.

An analogous derivative of the oxide Ag3O4 has been prepared by the electrolysis of silver fluoride. It has the formula 2Ag3O4,AgF.

A peroxide, probably Ag2O3, is stated to be produced by anodic oxidation of silver in acid solution. When solutions of sodium or potassium persulphate react with silver or Silver nitrate, a peroxide with a higher percentage of oxygen than Ag2O2 is produced, the process being attended by catalytic decomposition of the persulphate with formation of the acid sulphate. Ammonium persulphate does not yield a peroxide, but the ammonium radical becomes oxidized to nitric acid.
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