Kinetics and Mechanism of Ruthenium(III)-Catalyzed Oxidation of L-citrulline by Hexachloroplatinate(IV) in Perchloric Acid
Science Journal of Chemistry
Volume 4, Issue 5, October 2016, Pages: 53-60
Received: Aug. 29, 2016; Accepted: Sep. 5, 2016; Published: Sep. 24, 2016
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Authors
Ahmed Fawzy, Chemistry Department, Faculty of Applied Science, Umm Al-Qura University, Makkah, Saudi Arabia;Chemistry Department, Faculty of Science, Assiut University, Assiut, Egypt
Ishaq A. Zaafarany, Chemistry Department, Faculty of Applied Science, Umm Al-Qura University, Makkah, Saudi Arabia
Ismail I. Althagafi, Chemistry Department, Faculty of Applied Science, Umm Al-Qura University, Makkah, Saudi Arabia
Hatem M. Altass, Chemistry Department, Faculty of Applied Science, Umm Al-Qura University, Makkah, Saudi Arabia
Moataz H. Morad, Chemistry Department, Faculty of Applied Science, Umm Al-Qura University, Makkah, Saudi Arabia
Fahd A. Tirkistani, Chemistry Department, Faculty of Applied Science, Umm Al-Qura University, Makkah, Saudi Arabia
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Abstract
Oxidation kinetics of L-citrulline (Cit) by hexachloroplatinate(IV) (HCP) was studied spectrophotometrically in perchloric acid solutions in the presence of ruthenium(III) catalyst at a constant ionic strength of 1.8 mol dm-3 and at 20°C. The reaction rate was very slow in the absence of the catalyst. The reaction showed first order kinetics in both [HCP] and [Ru(III)] and less than unit order with respect to both [Cit] and [H+]. Increasing ionic strength and dielectric constant were found to increase the oxidation rate. Both spectral and kinetic evidences revealed formation of an intermediate complex between L-citrulline and ruthenium(III) prior to the rate-determining step. The complex reacts with the oxidant (HCP) by an inner-sphere mechanism leading to decomposition of the complex in the rate-determining step to give rise to the final oxidation products of L-citrulline which were identified by both spectroscopic and chemical tools as 4-(carbamoylamino) butyraldehyde, ammonia and carbon dioxide. The rate-law expression for the catalyzed reaction was deduced. The reaction constants involved in the different steps of the reaction mechanism have been evaluated. The activation parameters of the second order rate constant have been evaluated and discussed.
Keywords
L-Citrulline, Hexachloroplatinate(IV), Ruthenium(III), Oxidation, Kinetics, Mechanism
To cite this article
Ahmed Fawzy, Ishaq A. Zaafarany, Ismail I. Althagafi, Hatem M. Altass, Moataz H. Morad, Fahd A. Tirkistani, Kinetics and Mechanism of Ruthenium(III)-Catalyzed Oxidation of L-citrulline by Hexachloroplatinate(IV) in Perchloric Acid, Science Journal of Chemistry. Vol. 4, No. 5, 2016, pp. 53-60. doi: 10.11648/j.sjc.20160405.11
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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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