A KINETIC AND MECHANISTIC STUDY OF TUNGSTEN (VI) CATALYSIS OF PERBORATE OXIDATION OF SUBSTITUTED 5-OXO ACIDS
Authors/Creators
- 1. Department of Chemistry, Arignar Anna Government Arts College, Cheyyar, Tamilnadu
- 2. Department of Chemistry, Presidency College, Chennai, Tamilnadu
Description
In aqueous acetic acid medium tungsten (VI) catalyzes perborate oxidation of 5-oxo acids. In aqueous acetic acid solution perborate generates hydrogen peroxide. The rates of tungsten (VI) catalyzed perborate and hydrogen peroxide oxidations are almost the same. The ionic strength of the medium has no influence on the oxidation rate but the rate falls moderately with decrease of dielectric constant of the medium. Electron releasing substituents accelerate the reaction rate and electron withdrawing substituents retard the reaction. The order of reactivity among the studied 5-oxo acids is p-methoxy >> p-methyl > p-phenyl > -H > p-chloro > p-bromo > m-nitro. A mechanism consistent with the observed kinetic data is proposed and discussed. A suitable rate law is derived based on the mechanism.
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References
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