Journal of Industrial and Engineering Chemistry, Vol.12, No.5, 727-732, September, 2006
Kinetics and Mechanism of EDTA-Catalyzed Oxidation of (S)-Phenylmercaptoacetic Acid by Chromium(VI)
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The conversion of (S)-phenylmercaptoacetic acid to the corresponding sulfoxide was performed in 50 % (v/v) water-acetic acid mixture, in the presence of the disodium salt of ethylenediamminetetraacetic acid, the catalyst. The ionic strength had no appreciable effect on the reaction rate. The added Mn2+ retarded the rate considerably, suggesting a two-electron transfer in the rate-determining step. This notion is supported by the fact that added acrylonitrile had no effect on the rate of the reaction. The ratio k(D2O) / k(H2O) < 1 clearly indicates a significant solvent isotope effect. Highly negative entropy (ΔS#) values indicate a structured transition state. A mechanism is proposed involving the formation of a ternary complex, comprising ethylenediamminetetraacetic acid, Cr(VI), and (S)-phenylmercaptoacetic acid, in a fast step. The complex hydrolyzes in a subsequent slow rate-determining step, yielding the sulfoxide. Electron-releasing substituents in the phenyl ring accelerate the rate, while electron-withdrawing substituents retard the rate.
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