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Potassium Pentachlor-rhodite, K2RhCl5

Potassium Pentachlor-rhodite, K2RhCl5, is obtained in the anhydrous condition when finely divided rhodium is heated to redness with potassium chloride in a current of chlorine (Berzelius).

The mass is extracted with water and crystallised. Berzelius suggested the formula RhCl3. 2KCl. 2H2O, but Leidie was unable to confirm the presence of water. It seems probable, therefore, that Berzelius had obtained a mixture of salts.

Another method of preparing this salt consists in mixing solutions of rhodium trichloride and an excess of potassium chloride; on allowing to crystallise, the anhydrous salt, K2RhCl5, separates out in ortho- rhombic crystals, of reddish colour, but slightly soluble in water and insoluble in alcohol.

The dihydrate of this salt, K2RhCl5.2H2O, was stated by Claus1 to be formed on adding potassium chloride to a solution of sodium chlor-rhodite. It crystallises in small brown prisms which do not effloresce, and are rather difficultly soluble in water.

The monohydrate, K2RhCl5.H2O, is obtained on fusing spongy rhodium with twice its weight of potassium chloride in a stream of chlorine. On cooling, the mass is extracted with water, and the solution, evaporated under reduced pressure, deposits deep red crystals of the monohydrated salt. If the mother-liquors are now saturated with hydrogen chloride to precipitate the excess of potassium chloride, and evaporated, dark red, sparingly soluble crystals of potassium chlor-rhodite, K3RhCl6.3H2O, are obtained.

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