Oxidation of butylamine and isobutylamine by diperodatocuprate(III) in alkaline medium - A kinetic and mechanistic study

Abstract

The kinetics of oxidation of butylamine and isobutylamine by diperodatocuprate(III) (DPC) in alkaline medium has been studied spectrophotometrically in the temperatures range of 20-40 ℃. All data follow pseudo-first order reaction in [DPC] under experimental conditions. It was found that the reaction showed pseudo-first order with respect to DPC and 1 < n_ap < 2 to reductant. The rate constant k_obs increased with increase in [reductant], however, the k_obs decreased with increase in [IO₄^-] and [OH^-]. In addition, there was a negative salt effect. Through the determined experimentally found that the rate of isobutylamine was higher than butylamine. The reaction constants involved in the different steps of the mechanisms are calculated. Activation parameters, which were controlled by slow step of the mechanism are discussed and thermodynamic quantities are determined. Therefore, the activation parameters at 298.2 K were calculated.