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Phosphorus Thiophosphites

These salts may be regarded as derived from mono-, H3PSO2, di-, H3PS2O and tri-thiophosphorous acids, H3PS3. They were prepared, with other products, by heating metals with a mixture of sulphur and phosphorus, e.g. Ag3PS3, or metallic sulphides with phosphorus sulphides, e.g. Cu3PS3 from Cu2S and P2S5. When P4S3 was dissolved in alkalies phosphine, hydrogen and phosphorus were produced. By evaporation in vacuo crystals of Na2H(PSO2).2H2O were obtained. With an excess of sodium hydroxide, after long standing, the normal salt Na3PSO2 was deposited. When the alkali was replaced by Na2S the evaporation in vacuo gave Na2H(PS2O).2½H2O. An ammonium salt, (NH4)2H(PSO2).H2O, has been prepared similarly from P4S3 and solution of ammonia after long standing at 0° C. Solutions of these salts gave a characteristic yellow to red precipitate when mixed with a solution of lead acetate. When the salts were heated or their solutions were boiled, H2S was evolved and phosphites produced.

Thiohypophosphates, for example those of copper, silver and nickel, Cu2P2S6, Ag4P2S6, and Ni2P2S6, respectively, have been prepared by heating the metals with phosphorus and sulphur. The ease with which they are decomposed by water depends on the electroaffinity of the metal. Thus the zinc salt is decomposed by boiling water, while the nickel salt, which forms grey hexagonal crystals, is scarcely affected by water.

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