Electron transfer at tetrahedral cobalt(II), part IV: kinetics of silver(I) catalysed chlorate reduction

Summary The very slow reduction of ClO _inf3 ^su– by CoW₁₂O₄₀]^6- is markedly catalysed by Ag¹ in aqueous HClO₄ solution at I = 1.0 M (NaClO₄). The reaction obeys the rate law: -dreductant]/dt where a = (1.28 ± 0.10) × 10^-4M^-1s^-1 and b = (2.22 ± 0.20) × 10^-4M^-3s^-1, at T = 60.1 ± 0.1°C and H⁺] = 0.10–1.50 M. Activation parameters have been determined for each pathway and the reaction is discussed in terms of the outer-sphere mechanism.Part III: ref. 1.