Kinetic Studies of Oxidation of Secondary Amines by Chloramine-T in Aqueous Perchloric Acid Medium Catalyzed by Ru(III)

Abstract

The kinetics of ruthenium(III) catalyzed oxidation of the secondary amines–diethylamine, dipropylamine, di-isopropylamine and dibutylamine by chloramine-T (CAT) in aqueous perchloric acid medium has been studied. The reaction rate shows a first order depenence each on CAT, sec.-amine and Ru(III). The reaction rate shows an inverse fractional order dependence on acid concentration. Added halide ions and the reaction rate. Variation of ionic strength and dielectric constant of the medium has no influence on the reaction. The activation parameters have been evaluated. It was observed that the rate of oxidation of sec.-amine by CAT increase in the order DEA < DPA < DBA < DIPA. Also it was found that DH^# and DS^# are linearly related and an isokinetic relatonship is observed with ioskinetic temperature b as 394 K, indicating enthalpy as controlling factor. Mechanisms consistent with experimental rate law have been proposed.