Kinetics of oxidation of propane-1,3- and butane-1,4-diols by cerium(IV) in sulphuric acid

Abstract

Two cerium(IV) species, in sulphuric acid ∼ 1 M, CeSO 4 2+ and Ce(SO 4) 2, are the reactive species in an outer sphere oxidation of propane-1,3- and butane-1,4-diols. The reaction has a first order dependence both on [Ce(IV)] and [Diol], and a inverse dependence on [H 2SO 4] although the reaction is catalysed by H + at constant HSO 4 −. Two distinct paths of reaction, one involving the bimolecular collision of the reactants and the other involving the formation of an intermediate complex, are suggested in the mechanism and supported by the activation parameters. The rate controlling step is considered to be C-H fission.