• P Subramaniam

      Articles written in Journal of Chemical Sciences

    • Mechanism of the oxidation of alkyl aryl and diphenyl sulphoxides by peroxomonosulphate

      R Suthakaran P Subramaniam C Srinivasan

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      Detailed kinetic investigations of the oxidation of methyl phenyl sulphoxide and diphenyl sulphoxide by peroxomonosulphate in aqueous acetic acid medium reveal that the reactions are first-order, both in the sulphoxide and in the oxidant. Studies with substituted phenyl methyl sulphoxides and 4,4′-disubstituted diphenyl sulphoxides show that electron-releasing groups accelerate the rate of oxidation and electron-withdrawing groups retard it. A fair correlation between log k2 and Hammett substituent constants has been observed in the two series. The mechanism proposed involves the rate-determining nucleophilic attack of the sulphoxide sulphur at the outer terminal peroxo oxygen atom of HSO5.

    • Quantitative treatment of the ortho-effect in reactions of ortho-substituted phenylmercaptoacetic acids

      C Srinivasan P Subramaniam

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      The kinetics of oxidation of ortho-substituted phenylmercaptoacetic acids by bromamine T and metaperiodate ion and also thepka values of these acids have been studied. Regression analyses of the rate and equilibrium data indicate that the ortho-substituent effect can be explained by the electrical effects alone, and that in these acids when the reaction site is in close proximity to the ortho-substituent or not, the steric effect is insignificant. The rates of oxidation and the ionization constants of these acids are largely controlled by the inductive effect.

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