Reaction Kinetics and Mechanism of Copper(II) Catalyzed Oxidative Deamination and Decarboxylation of Ornithine by Peroxomonosulfate

Copper­(II) catalyzed and uncatalyzed oxidation of ornithine by peroxomonosulfate (PMS) was studied in acetic acid–sodium acetate buffered medium (pH 3.6–5.2). The catalyzed reaction was 2.6 times faster than the uncatalyzed reaction. The catalytic constant k c obtained in this study was 0.15 mol–1...

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Bibliographic Details
Published in:Industrial & engineering chemistry research 2012-05, Vol.51 (18), p.6310-6319
Main Authors: Kumar, Paramasivam Suresh, Raj, Radhakrishnan Mohan, Rani, Srinivasalu Kutti, Easwaramoorthy, Deivanayagam
Format: Article
Language:English
Subjects:
ACTIVATION
Applied sciences
Catalysis
Catalytic reactions
Chemical engineering
Chemistry
Constants
Decarboxylation
Entropy of activation
Exact sciences and technology
Formations
Free radicals
General and physical chemistry
Industrial engineering
KINETICS
Reactors
Spectra
SULFATES
Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry
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Summary:Copper­(II) catalyzed and uncatalyzed oxidation of ornithine by peroxomonosulfate (PMS) was studied in acetic acid–sodium acetate buffered medium (pH 3.6–5.2). The catalyzed reaction was 2.6 times faster than the uncatalyzed reaction. The catalytic constant k c obtained in this study was 0.15 mol–1 dm3 s–1. A negative value of entropy of activation obtained in this reaction revealed that the transition state was more rigid than the reactants. ESR spectral data ruled out the participation of free radical intermediate. Cyclic voltammetric and absorption studies confirmed the formation of copper–ornithine–PMS complex. HPLC analysis revealed that the product formed in this reaction was 4-aminobutanal, which was confirmed by NMR spectra.
ISSN:0888-5885
1520-5045
DOI:10.1021/ie202409p