Abstract: | The kinetics of oxidation of benzyl alcohol and substituted benzyl alcohols by sodium N-chloro-p-toluenesulfonamide (chloramine-T, CAT) in HClO4 (0.1–1 mol/dm3) containing Cl? ions, over the temperature range of 30–50°C have been studied. The reaction is of first order each with respect to alcohol and oxidant. The fractional order dependence of the rate on the concentrations of H+ and Cl? suggests a complex formation between RNCl? and HCl. In higher acidic chloride solution the rate of reaction is proportional to the concentrations of both H+ and Cl7hyphen;. The observed solvent isotope effect (k /k ) is 1.43 at 30°C. The reaction constant (p = ?1.66) and thermodynamic parameters are evaluated. Rate expressions and probable mechanisms for the observed kinetics have been suggested. |