Shift of reaction pathway by added chloride ions in the oxidation of aromatic ketones by dichloroisocyanuric acid—A kinetic study
- Authors: Kumar Y.L.1, Nadh R.V.2, Radhakrishnamurti P.S.1
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Affiliations:
- Department of Chemistry
- GITAM University-Bengaluru Campus
- Issue: Vol 90, No 3 (2016)
- Pages: 552-559
- Section: Chemical Kinetics and Catalysis
- URL: https://bakhtiniada.ru/0036-0244/article/view/167861
- DOI: https://doi.org/10.1134/S0036024416030237
- ID: 167861
Cite item
Abstract
Role of added chloride ions on the shift of reaction pathway of oxidation of aromatic ketones (acetophenone, desoxybenzoin) by dichloroisocyanuric acid (DCICA) was studied in aqueous acetic acid—perchloric acid medium. Participation of enolic and protonated forms of ketones in the rate determining steps is manifested from zero and first orders with respect to the oxidant in absence and presence of added chloride ions, respectively. Positive and negative effects of acid and dielectric constant on the reaction rate were observed. The observations deduce plausible mechanisms involving (i) rate-determining formation of enol from the conjugate acid of the ketone (SH+) in the absence of added chloride ions and (ii) rapid formation of molecular chlorine species from HOCl (hydrolytic species of DCICA) in the presence of added chloride ions, which then interacts with SH+ in a rate-determining step prior to the rapid steps of product formation. The order of Arrhenius parameters substantiate the proposed plausible mechanisms based on order of reactants both in presence and absence of added chloride ions.
About the authors
Y. Lakshman Kumar
Department of Chemistry
Author for correspondence.
Email: doctornadh@yahoo.co.in
India, Guntur, 522006
R. Venkata Nadh
GITAM University-Bengaluru Campus
Email: doctornadh@yahoo.co.in
India, Karnataka, 561203
P. S. Radhakrishnamurti
Department of Chemistry
Email: doctornadh@yahoo.co.in
India, Guntur, 522006
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