Kinetics and Mechanism of Oxidation of Hydroxylamine Hydrochloride by Chloramine - B in Perchloric Acid Medium

Department of Chemistry, University of Mysore, Manasagangotri, Mysore-570 006

Manuscript received 24 September 1987, revised 29 February 1988, accepted 15 March 1988

The kinetics of oxidation of hydroxylamine hydrochloride (HH) by chloramine-B (CAB) in perchloric acid medium have been studied at 0°. The reaction shows a first order dependence each in [CAB] and [HH]. The reaction Is catalysed by [H⁺] and [CI^-], and the order in both [H⁺[ and [CI^-] Is fractional. Addition of the reaction product, benzene sulphonamide and increase in ionic strength of the medium have negligible influence on the rate of reaction. The effect of changing the dielectric constant of the medium on the reaction rate has been studied. Thermodynamic parameters have been calculated and a mechanism consistent with the experimental results is proposed.