A Kenitic Study of Oxidation of Propylamine, Butylamine by Chloramine-T and Chloramine-B in Aqueous Hydrochloric Acid Medium

M. K. Veeraiah* , A. S. Ananda Murthy+ and M. Veerabhdraswamy++

Department of Chemistry, Sri Siddhartha Institute of Technology Tumkur -572 105 (India)

Kinetics of oxidation of n-propylamine and n-butylamine by Chloramine-T (CAT) and Chloramine-B (CAB) has been investigated in aqueous hydrochloric acid medium at 313K.The reaction showed a first order behavior with respect to the oxidants while showing zero order with respect to both amine and [H+]. Added chloride ions, the reaction product p-toluene sulphonamide / benzene sulphonamide, variation of ionic strength had no effect on the reaction rate. Decrease in dielectric constant (D) of the reaction medium increased the rate of reaction initially upto a D value of 63. Further the reaction rate either decreased slightly (in case of CAB oxidation) or levelled off (in case of CAT oxidation). The free acidic form of chloramine (RNHCI) was identified has the reactive species participating in a slow hydrolysis to release HOCI that reacts in a fast step with the neutral amine molecule. The reaction has been studied at different temperatures and activation parameters have been evaluated. A mechanism consistent with experimental result has been proposed.

Kinetics; Propylamine; Butylamine; Chloramine T. and B