Abstract
Abstract The kinetics of oxidation of 2-propanone, 2-butanone, 2-pentanone, 3-pentanone, and 4-methyl-2-pentanone by sodium salt of N-bromo-p-toluenesulfonamide or bromamine-T (BAT) in presence of HClO4 was studied at 30 °C. The rate law is: −\fracd[BAT]dt=k[BAT]0[ketone]1[H+]1. Variation of ionic strength of medium or addition of reaction product p-toluenesulfonamide have no effect on the rate. The dielectric effect is positive. The acid-catalyzed enolization of ketone is assumed to be the rate-limiting step and enolization rate coefficients have been calculated. Proton inventory studies made in H2O–D2O mixtures have been employed to calculate the isotopic fractionation factors. Isokinetic temperature is 320 K indicating enthalpy as a controlling factor.
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