Kinetics and mechanism of the ruthenium(III)-catalysed oxidation of aliphatic acids by peroxodiphosphate in acetate buffers

Abstract

The kinetics of oxidation of aliphatic acids (AAs), such as propionic acid, butyric acid, isobutyric acid and valeric acids, by peroxodiphosphate (PDP) using ruthenium(III) as catalyst in aqueous H2SO4 at constant ionic strength and different acidities were studied. The ruthenium(III)-catalysed oxidation is first order in [PDP] and fractional order in [AA]. The order with respect to [Ru m ] is fractional. An analysis of the rate dependence upon [H +] suggests that H3P208 is the active oxidizing species in the oxidation. A mechanism consistent with the rate law is proposed.