Effect of Silver(I) Catalyst on the Oxidation of L-asparagine by Alkaline Hexacyanoferrate(III): A Kinetic and Mechanistic Approach
Modern Chemistry
Volume 4, Issue 1, February 2016, Pages: 6-15
Received: Jan. 28, 2016; Accepted: Feb. 8, 2016; Published: Feb. 25, 2016
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Authors
Ahmed Fawzy, Chemistry Department, Faculty of Applied Science, UmmAl-Qura University, Makkah, Saudi Arabia; Chemistry Department, Faculty of Science, Assiut University, Assiut, Egypt
Ishaq Zaafarany, Chemistry Department, Faculty of Applied Science, UmmAl-Qura University, Makkah, Saudi Arabia
Ameena Al-Bonayan, Chemistry Department, Faculty of Applied Science, UmmAl-Qura University, Makkah, Saudi Arabia
Zakiya Al-Mallah, Chemistry Department, Faculty of Applied Science, UmmAl-Qura University, Makkah, Saudi Arabia
Reem Shah, Chemistry Department, Faculty of Applied Science, UmmAl-Qura University, Makkah, Saudi Arabia
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Abstract
The kinetics of oxidation of L-asparagine (Asn) by hexacyanoferrate(III) (HCF) has been investigated in alkaline medium in the absence and presence of silver(I) catalyst at a constant ionic strength of 0.5 mol dm−3 and at 20°C. The progress of both uncatalyzed and silver(I)-catalyzed oxidations was followed spectrophotometrically. Both reactions showed a first order dependence with respect to [HCF], whereas the orders with respect to [Asn] and [OH] were less than unity. The catalyzed reaction exhibited a first order dependence in [AgI]. Increasing both ionic strength and dielectric constant of the reaction medium increased the rate of uncatalyzed reaction and did not affect significantly the rate of catalyzed reaction. Addition of the reaction product, HCF(II) to the reaction mixture had no affect on the rate. Appropriate reaction mechanisms for both uncatalyzed and catalyzed oxidations explaining all of the observed kinetic results has been proposed. The catalyzed reaction has been shown to proceed via formation of a silver(I)-asparagine intermediate complex, which reacted with the oxidant by an inner-sphere mechanism leading to decomposition of the complex in the rate-determining step to yield the final oxidation products which were identified as α-formyl acetamide, ammonia, and carbon dioxide. The rate law expressions associated with the reaction mechanisms were derived.
Keywords
L-asparagine, Hexacyanoferrate(III), Silver(I), Kinetics, Mechanism, Oxidation
To cite this article
Ahmed Fawzy, Ishaq Zaafarany, Ameena Al-Bonayan, Zakiya Al-Mallah, Reem Shah, Effect of Silver(I) Catalyst on the Oxidation of L-asparagine by Alkaline Hexacyanoferrate(III): A Kinetic and Mechanistic Approach, Modern Chemistry. Vol. 4, No. 1, 2016, pp. 6-15. doi: 10.11648/j.mc.20160401.12
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Copyright © 2016 Authors retain the copyright of this article.
This article is an open access article distributed under the Creative Commons Attribution License (http://creativecommons.org/licenses/by/4.0/) which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
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