Oxidation of carboxylic acids by cerium(IV) perchlorate. Part I

Abstract

The kinetics of oxidation of acetic acid by cerium(IV) perchlorate in perchloric acid were studied in the temperature range 50–60 °C by following the rate of disappearance of cerium(IV). The reaction order was unity in cerium(IV) and close to unity in acetic acid. With an increase in [H⁺] the rate increased and the reaction showed a positive salt effect. Evidence for complex formation between cerium(IV) and acetic acid was obtained both from spectrophotometry and Michaelis–Menten reciprocal plots. An inner-sphere mechanism involving rapid formation of complex, which then disproportionates to form the products, is suggested.