Abstract
The kinetics of the reaction between vanadium(V) and iodide ions have been studied in the absence of oxygen and in a range of acidity such that all quinquevalent vanadium is converted into hydroxovanadium(V) ion. The rate equation, obtained by a statistical treatment of the results is (i) where k1,5=(1·20 ± 0·04)× 10–2 l2 mol–2 s–1, -d[H4VO4+]/dt=k1,5[H4VO4+][l–][H+]+k2,5[H4VO4+][l–][H+]2+k4,5[H4VO4+][l–]2[H+]2(i) k 2,5 =(5·9 ± 0·4)× 10–2 l3 mol–3 s–1, and k4,5=(4·7 ± 0·4)× 10–1 l4 mol–4 s–1 at 25 °C and at ionic strength 0·4M (NaClO4). Equation (i) is found to fit the results of previous workers as well. A mechanism for the reaction is suggested, which is based on replacement in the co-ordination shell of the vanadium(V) atom before the redox process takes place.
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