Abstract
The behaviour of vanadium in molten ammonium hydrogenosulphate (t=200°C, P(H2O)=0.03 atm) has been studied. Vanadium only exists at the +IV and +V oxidation states. From potentiometric and solubility measurements, it can be concluded that the following species are formed: vanadium(IV) exists as vanadyl ion (VO2+) in acid media, as vanadyl sulphate (VOSO4) hardly soluble in neutral media, which can be dissolved in basic media as VO(SO4)22−. Vanadium(V) is always soluble, as pervanadyl ion (VO2+) in acid media and as VO2SO4− in basic media. The standard potential E0 of the electrochemical system V(V)/V(IV) and the acido-basic constants from which the potential-pH diagram is established, age given (E0=0.677 V; K1[VO2+, VOSO4]=101.00; K2[VOSO4, VO(SO4)22−] =10−2.87; δ(VOSO4)=10−2.06; K[VO2+, VO2SO4−]=10−1.14).
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