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Double Chlorides of Trivalent Tungsten

Double Chlorides of Trivalent Tungsten, with those of potassium, ammonium, rubidium, caesium, and thallium, have been prepared by reduction with tin of a solution of potassium tungstate in concentrated hydrochloric acid. They are all anhydrous, of the type R3W2Cl9, and are stable in the dry state. Conductivity and cryoscopic measurements show that the tungsten is present as part of a complex anion, and that in aqueous solution not more than four ions are produced by dissociation. The anion, W2Cl9''', is very stable, and the chlortungstates act as strong reducing agents on solutions of silver, gold, mercury, copper, and ferric salts; in the last case the reaction is quantitative. The following salts have been prepared:

Cr(NH3)6W2Cl9.2H2O, dark green, microscopic, rectangular prisms;
Co(NH3)6W2Cl9.6H2O, bright green, microcrystalline powder;
Cu(NH3)4NH4W2Cl9.H2O, and
Cu(NH3)4KW2Cl9.H2O, green crystalline powders;
Cd(NH3)4NH4W2Cl9;
Cd(NH3)4KW2Cl9;
[Ag(NH3)2]3W2Cl9, unstable.

These are generally sparingly soluble in water, the concentrated solutions being green, the more dilute, yellow.

A solution of the free acid, H3W2Cl9, is obtained by the action of hydriodic acid on a solution of the thallium salt; it has not, however, been isolated.

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