Abstract
The kinetics of the oxidative degradation of dipeptide glycyl-glycine (Gly-Gly) by water-soluble colloidal MnO(2) in acidic medium has been studied by employing visible spectrophotometer in the aqueous and micellar media at 35°C. To obtain the rate constants as functions of [Gly-Gly], [MnO(2)] and [HClO(4)], pseudo-first-order conditions were maintained in each kinetic run. The first-order-rate is observed with respect to [MnO(2)], whereas fractional-order-rates are determined in both [Gly-Gly] and [HClO(4)]. The addition of sodium pyrophosphate and sodium fluoride has composite effects (catalytic and inhibition). The reaction proceeds through the fast adsorption of Gly-Gly on the surface of the colloidal MnO(2). The observed results are discussed in terms of Michaelis-Menten/Langmuir-Hinshelwood model. The Arrhenius and Eyring equations are found valid for the reaction over a range of temperatures and different activation parameters have been evaluated. A probable reaction mechanism, in agreement with the observed kinetic results, has been proposed and discussed. The influence of changes in the surfactant concentrations on the observed rate constant is also investigated and the reaction followed the same type of kinetic behavior in micellar media. The pseudo-first-order rate constant (k(ψ)) is found to increase about two-fold with increase in [TX-100]. The catalytic effect of nonionic surfactant TX-100 is explained in terms of the mathematical model proposed by Tuncay et al.