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Vanadyl Sulphites

Normal sulphites containing tetravalent vanadium have not hitherto been prepared in consequence of the readiness with which hydrolysis takes place. A considerable number of vanadyl sulphites are, however, known, as well as their double salts, which, no doubt, are heteropoly-acid compounds.

When a mixture of the oxides V2O3 and V2O4, resulting from the decomposition of ammonium metavanadate, is treated in boiling aqueous solution with sulphur dioxide, a blue liquid is obtained from which under suitable conditions the following blue, crystalline hydrates of vanadyl sulphite, VOSO3, can be isolated: VOSO3.3H2O; VOSO3. 4H2O; VOSO3.8H2O. The liquid also gives rise to an amorphous, green, hydrated, basic vanadyl sulphite, VO2.VOSO3.4½H2O or 2VO2.SO2.4½H2O. Another blue, crystalline complex sulphite, having the composition 4VO2.3SO2.10H2O, has been prepared by a similar process, and by reducing barium metavanadate in aqueous suspension, the blue, crystalline compound 3VO2.2SO2.4½H2O results.

Double Salts of Vanadyl Sulphite

By the action of sulphur dioxide on vanadates in the presence of varying molecular proportions of alkali sulphites, two series of alkali vanadyl sulphites have been obtained.

Series I

This consists of blue compounds having the general formula R2O.3VO2.2SO2.xH2O, which can be regarded as derivatives of the vanadyl sulphite, 3VO2.2SO2.4½H2O, which can be alternatively written, H2O.3VO2.2SO2.3½H2O. The following have been prepared: (NH4)2O.3VO2.2SO2.H2O; Na2O.3VO2.2SO2.3H2O; K2O.3VO2.2SO2; and ZnO.3VO2.2SO2.

Series II

This comprises green substances which are generally less stable than the members of former series, and have the general formula R2O.VO2.2SO2.xH2O. The following are known:

(NH4)2SO3.VOSO3.1 or 2 H2O or (NH4)2O.VO2.2SO2.1 or 2H2O.
Na2SO3.VOSO3.5H2O or Na2O.VO2.2SO2.5H2O.
K2SO3.VOSO3.2H2O or K2O.VO2.2SO2.2H2O.

In addition to the foregoing, Gain has prepared a large number of alkali vanadyl sulphites in which the proportions of basic oxide, vanadium dioxide, and sulphur dioxide vary considerably:

2(NH4)2O.10VO2.7SO2.16H2O;
2K2O.6VO2.5SO2.5H2O;
(NH4)2O.6VO2.4SO2.4H2O;
K2O.4VO2.3SO2.2H2O;
5Li2O.2VO2.6SO2.8H2O;
K2O.6VO2.4SO2.5H2O;
Na2O.4VO2.3SO2.4H2O;
2Rb2O.4VO2.3SO2.2H2O;
Na2O.10VO2.6SO2.2H2O;
Rb2O.2VO2.3SO2.4H2O;
3Cs2O.2VO2.4SO2.8H2O;
2Tl2O.2VO2.3SO2.4H2O;
Tl2O.6VO2.4SO2.8H2O;

It is improbable that these are all true individual chemical compounds.

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