Electron transfer reactions of vanadium(IV) with some oxyanion oxidants in aqueous perchloric acid. Part II. Reaction with chlorine(V)

Abstract

The reaction is predominantly of the first order in each reactant, but at higher reactant concentrations rate plots show an initial enhancement of slope. On the other hand the initial presence of Cl^–, the main product, results in a slight deceleration, V^V addition showing a similar but smaller effect. A small percentage of chlorine-containing product appears as ClO₂ and (even less) as Cl₂, which results in a ca. 7% departure from the expected V^IV :ClO₃^– stoicheiometry of 6 : 1. The second-order rate constant is 58·0 × 10^–4 l. mole^–1 sec.^–1 in ionic strength (NaClO₄) 0·50M at 21·2 °C.