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The kinetics of oxidation of the mixture of S-phenylmercaptoacetic acid (PMA) and oxalic acid with pyridinium chlorochromate (PCC) in 30% (v/v) acetic acid-water exhibits a first-order dependence each in [PCC] and [PMA], at low concentrations of the latter. At high concentration of the substrate, a fractional order in [PMA] is observed. The rate increases linearly with [oxalic acid]. Increased reactivity in the presence of oxalic acid with carbon dioxide as one of the products is well explained by Rocek's mechanism for cooxidation, involving a ternary complex. Formation of a ternary complex at low concentrations and decomposition of the complex at higher concentrations of PMA is considered to be the respective rate-limiting step.
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582--586
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Bibliogr. 15 poz., tab., wykr.
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bwmeta1.element.baztech-article-BAR2-0001-0078