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1 2003

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Kinetics and Mechanism of Oxidative Degradation of L-Proline by Alkaline Diperiodatonickelate(IV)- A Free Radical Intervention and Decarboxylation

Mulla R., Gurubasavaraj H., Nandibewoor S.

Polish Journal of Chemistry

2003

Vol. 77 / nr 12

1833-1840

The kinetics of oxidation of L-proline by diperiodatonickelate(IV) (DPN) in aqueous alkaline medium at a constant ionic strength of 0.50 mol dm-3 was studied spectrophotometrically. The reaction is of first order in [DPN], zero order in [alkali] and less than unit order in [L-proline]. Addition of periodate has no effect on the rate of reaction. Effect of added products, ionic strength and dielectric constant of the reaction medium have been investigated. The main products were identified by spot test and IR spectra.Amechanism involving the diperiodatonickelate(IV) (DPN) as the reactive species of the oxidant has been proposed. The reaction constants involved in the different steps of mechanism are calculated. The activation parameters with respect to slow step of the mechanism are computed and discussed and thermodynamic quantities are also calculated. The isokinetic temperature was determined and discussed.