The co-oxidation of a mixture of phenylsulfinylacetic acid (PSAA) and oxalic acid (OxH 2 ) by Cr(VI) in 20% aceto n i trile - 80% water (v/v) medium follows third order kinetics, first order , each with respect to PSAA, OxH 2 and Cr(VI). The reaction involves nucleophilic attack of sulfur atom of PSAA on chromium of the oxidizing species, Cr(VI)-OxH 2 to form a ternary complex, Cr(VI)-OxH 2 -PSAA followed by a one-step three-electron reduction of Cr(VI) to Cr(III) and simultaneous oxidation of both the substrates. The reaction is catalysed by Mn 2+ ion while retarded by Al 3+ ion. Electron releasing substituents in the meta- and para-positions of the phenyl ring of PSAA enhance the rate of co-oxidation while electron withdrawing substituents retard s the reaction. The Hammett plots at different temperatures exhibit excellent correlation with negative ρ values. The reaction series obey isokinetic relationship and the observed isokinetic temperature is lying below the experimental range of temperature .
KeywordsPhenylsulfinylacetic AcidOxalic AcidCo-OxidationNucleophilic Attack of SulfurThree-Electron TransferSubstituent Effect
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