Kinetics of oxidation of sec-butanol and cyclohexanol by aquocerium(IV) ions in aqueous perchlorate media
Abstract
The oxidations of sec-butanol and cyclohexanol by CeIV in aqueous perchlorate media are inner-sphere reactions analogous to the oxidation of isopropanol by CeIV. The formation equilibrium constants for the Ce4+R1R2CHOHaq complexes are of the same order as that for the Ce4+(CH3)2CHOHaq complex. The oxidation involves two rate-determining steps, the first-order decomposition of Ce4+R1R2CHOHaq and of Ce4+R1R2CHO–aq. Energies and entropies of activation for both reactions, and energies and entropies of formation of both complexes are calculated. These data are compared with similar data for isopropanol.