Acidic amino acids; bromamine-B; oxidation kinetics; acid medium
Kinetics of oxidation of acidic amino acids (glutamic acid (Glu) and aspartic acid (Asp)) by sodium N-bromobenzenesulphonamide (bromamine-B or BAB) has been carried out in aqueous HClO4 medium at 30°C. The rate shows first-order dependence each on [BAB]o and [amino acid]o and inverse first-order on [H+]. At [H+] > 0·60 mol dm−3, the rate levelled off indicating zero-order dependence on [H+] and, under these conditions, the rate has fractional order dependence on [amino acid]. Succinic and malonic acids have been identified as the products. Variation of ionic strength and addition of the reaction product benzenesulphonamide or halide ions had no significant effect on the reaction rate. There is positive effect of dielectric constant of the solvent. Proton inventory studies in H2O-D2O mixtures showed the involvement of a single exchangeable proton of the OH− ion in the transition state. Kinetic investigations have revealed that the order of reactivity is Asp > Glu. The rate laws proposed and derived in agreement with experimental results are discussed.