Kinetics and mechanism of ruthenium(III) chloride catalyzed oxidation of formic acid by peroxomonosulphuric acid in acid aqueous medium - An appraisal of hydride ion transfer

Abstract

The kinetics of ruthenium(III) chloride catalyzed oxidation of formic acid by peroxomonosulpuric acid (PMS) have been studied in acid aqueous medium. The stoichiometry corresponds to the reaction as represented by the eq. (1), HCO 2 H + HSO 5 - →Ru III CO 2 + H 2 O + HSO 4 - (1) The rate of reaction is independent of the per-acid concentration. However, formic acid exhibits a complex dependence. The kinetic rate law is represented by the eq. (2), - d[PMS]/dt = kKK h [Ru III ][HCO 2 H]/[H + ] + Kh + KKh[HCO 2 H] (2) A plausible reaction mechanism has been suggested.