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.
| Published in | Science Journal of Chemistry (Volume 4, Issue 5) |
| DOI | 10.11648/j.sjc.20160405.11 |
| Page(s) | 53-60 |
| Creative Commons |
This is an Open Access article, distributed under the terms of the Creative Commons Attribution 4.0 International License (http://creativecommons.org/licenses/by/4.0/), which permits unrestricted use, distribution and reproduction in any medium or format, provided the original work is properly cited. |
| Copyright |
Copyright © The Author(s), 2016. Published by Science Publishing Group |
L-Citrulline, Hexachloroplatinate(IV), Ruthenium(III), Oxidation, Kinetics, Mechanism
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APA Style
Ahmed Fawzy, Ishaq A. Zaafarany, Ismail I. Althagafi, Hatem M. Altass, Moataz H. Morad, et al. (2016). Kinetics and Mechanism of Ruthenium(III)-Catalyzed Oxidation of L-citrulline by Hexachloroplatinate(IV) in Perchloric Acid. Science Journal of Chemistry, 4(5), 53-60. https://doi.org/10.11648/j.sjc.20160405.11
ACS Style
Ahmed Fawzy; Ishaq A. Zaafarany; Ismail I. Althagafi; Hatem M. Altass; Moataz H. Morad, et al. Kinetics and Mechanism of Ruthenium(III)-Catalyzed Oxidation of L-citrulline by Hexachloroplatinate(IV) in Perchloric Acid. Sci. J. Chem. 2016, 4(5), 53-60. doi: 10.11648/j.sjc.20160405.11
AMA Style
Ahmed Fawzy, Ishaq A. Zaafarany, Ismail I. Althagafi, Hatem M. Altass, Moataz H. Morad, et al. Kinetics and Mechanism of Ruthenium(III)-Catalyzed Oxidation of L-citrulline by Hexachloroplatinate(IV) in Perchloric Acid. Sci J Chem. 2016;4(5):53-60. doi: 10.11648/j.sjc.20160405.11
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Download@article{10.11648/j.sjc.20160405.11,
author = {Ahmed Fawzy and Ishaq A. Zaafarany and Ismail I. Althagafi and Hatem M. Altass and Moataz H. Morad and Fahd A. Tirkistani},
title = {Kinetics and Mechanism of Ruthenium(III)-Catalyzed Oxidation of L-citrulline by Hexachloroplatinate(IV) in Perchloric Acid},
journal = {Science Journal of Chemistry},
volume = {4},
number = {5},
pages = {53-60},
doi = {10.11648/j.sjc.20160405.11},
url = {https://doi.org/10.11648/j.sjc.20160405.11},
eprint = {https://article.sciencepublishinggroup.com/pdf/10.11648.j.sjc.20160405.11},
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.},
year = {2016}
}
TY - JOUR T1 - Kinetics and Mechanism of Ruthenium(III)-Catalyzed Oxidation of L-citrulline by Hexachloroplatinate(IV) in Perchloric Acid AU - Ahmed Fawzy AU - Ishaq A. Zaafarany AU - Ismail I. Althagafi AU - Hatem M. Altass AU - Moataz H. Morad AU - Fahd A. Tirkistani Y1 - 2016/09/24 PY - 2016 N1 - https://doi.org/10.11648/j.sjc.20160405.11 DO - 10.11648/j.sjc.20160405.11 T2 - Science Journal of Chemistry JF - Science Journal of Chemistry JO - Science Journal of Chemistry SP - 53 EP - 60 PB - Science Publishing Group SN - 2330-099X UR - https://doi.org/10.11648/j.sjc.20160405.11 AB - 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. VL - 4 IS - 5 ER -
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