| Abstract: | The kinetics of oxidation of methyl, ethyl, n-propyl, isopropyl, and n-butyl acetates to acetic acid and the corresponding aldehyde by the title oxidant in aqueous HCl medium at 40°C has been studied. The reaction shows first-order with respect to [oxidant] and fractional orders in [H+] and [ester]. An isokinetic relationship was observed with β = 374 K indicating enthalpy as the rate controlling factor. Attempts have been made to arrive at a linear free energy relationship through the Taft treatment. Electron releasing groups in the ester moiety increase the rate with ρ* = ?9.88. A two-pathway mechanism, consistent with the observed kinetic data, has been proposed. © 1993 John Wiley & Sons, Inc. |
