Kinetic Investigations of Positive Halogen Reactions. Oxidation of Semicarbazide by Chloramine-T and Dichloramine-T

Department of Post-Graduate Studies and Research in Chemistry, Mangalore University, Mangalagangothri-574 199 Manuscript received 14 September 1987, revised 28 September 1988, accepted 2 November 1988 Kinetics of oxidation of semicarbazide (SC) by chloramines--T (CAT) in aqueous perchioric acid medium and dichloramine-T (DCT) in 1 : 1 (v/v) water—methanol medium have been studied. Oxidation of semicarbazide by CAT and DCT followed the rate laws,\(\frac{d[{CAT]}}{dt} = [CAT]2\) {k+k′[H+}] and -\(\frac{d[DCT]}{dt}\)=\(\frac{k''[DCT][H+]}{1+K[H+]}\)respectively. Effects of addition of reaction product and variations in ionic strength and dielectric constant of the medium have also been Investigated. Mechanisms in accord with the observed rate laws are discussied