Abstract
The oxidation of aliphatic primary amines, n-propylamine (PA) and -butylamine (BA), by chloramine-B (CAB) and chloramine-T (CAT) in aqueous alkaline medium has been kinetically studied at 318 K. The reaction follows the experimental rate law: rate k′ [oxidant] [amine] 0 [OH − ] x , where oxidant is CAT or CAB and x is fractional. Additions of chloride ions, the reduction product, sulfonamide, and sodium perchlorate, which is used for changing the ionic strength of the solvent medium, have no effect on the reaction rate. However, the rate varies with change in dielectric constant of the medium. The reaction has been studied in the temperature range, 313–323K, and the activation parameters have been evaluated. A suitable mechanism consistent with the observed kinetic data has been proposed and the rate law derived.
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