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Kinetics of Os(VIII) Catalyzed Oxidation of 2-Pyrrolidine Carboxylic Acid in Alkaline Medium using Sodium Periodate as Oxidant: A Mechanistic Approach

Madhu Gupta1, Amrita Srivastava1, Sheila Srivastava2, Ashish Verma1
Affiliation: 
1 Department of Chemistry, University of Lucknow, Lucknow, U.P., India 2 Chemical Laboratories Feroze Gandhi College, Raebareli, U.P., India She_ila72@yahoo.com
DOI: 
https://doi.org/10.23939/chcht13.03.326
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Abstract: 
The present paper deals with the kinetic and mechanistic investigation of Os(VIII) catalyzed oxidation of 2-pyrrolidinecarboxylic acid by sodium periodate (NaIO4) in alkaline medium in the temperature range of 303‒318 K. The experimental result shows a first order kinetics with respect to Os(VIII) and periodate while positive effect with respect to substrate i.e., 2-pyrrolidinecarboxylic acid was observed. The reaction showed negative effect for [OH-]. Negligible effect of Hg(OAc)2 and ionic strength of the medium was observed. The reaction is carried out in the presence of mercuric acetate as a scavenger. The reaction of sodium periodate and 2-pyrrolidinecarboxylic acid in alkaline medium shows 2:1 stoichiometry. The values of rate constants observed at different temperatures were utilized to calculate the activation parameters. A mechanism involving the complex formation between a catalyst, substrate and oxidant has been proposed. L-glutamic acid has been identified as the main oxidation product of the reaction using chromatography and spectroscopy. Based on kinetic data, the reaction stoichiometry and product analysis of the reaction a feasible mechanism has been proposed. The rate law has been derived from obtained kinetic data.
References: 

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