Mechanism of Oxidation of Alanine by Chloroaurate(III) Complexes in Acid Medium: Kinetics of the Rate Processes

作者:Sen Pratik K*; Gani Nasimul; Midya Jayanta K; Pal Biswajit
来源:International Journal of Chemical Kinetics, 2009, 41(7): 473-482.
DOI:10.1002/kin.20422

摘要

The kinetics of the oxidation of alanine by chloroaurate(III) complexes in acetate buffer medium has been investigated. The major oxidation product of alanine has been identified as acetaldehyde by H-1 NMR spectroscopy. Under the experimental conditions, AuCl4- and AuCl3(OH)(-) are the effective oxidizing species of gold(III). The reaction is first order with respect to Au(III) as well as alanine. The effects of H+ and Cl- on the second-order rate constant V have been analyzed, and accordingly the rate law has been deduced: k(2)' = (k(1)[H+][Cl-] + k(3)K(4)K(5))/(K4K5+[H+][Cl-]). Increasing dielectric constant of the medium has an accelerating effect on the reaction rate. Activation parameters associated with the overall reaction have been calculated. A mechanism involving the two effective oxidizing species of gold(III) and zwitterionic species of alanine, consistent with the rate law, has been proposed.

  • 出版日期2009-7