The kinetics of oxidations of two aliphatic α-amino acids (AA), namely, alanine and valine by platinum (IV) has been investigated spectrophotometrically in perchloric and sulfuric acids solutions in the presence of silver (I) catalyst at a constant ionic strength of 1.0 mol dm-3 and at 25°C. The reactions were very slow to be measured in the absence of the catalyst. The reactions in both acids showed a first order dependence on both [PtIV] and [AgI], and less than unit order dependences with respect to both [AA] and [H+]. Increasing ionic strength was found to decrease the oxidation rates. Under comparable experimental conditions, the oxidation rates of alanine and valine in perchloric acid solutions were found to be about five times higher than those obtained in sulfuric acid solutions and the oxidation rates of alanine in both acids were found to be higher than those recorded with respect to valine. A plausible oxidations mechanism has been proposed and the rate law expression has been derived. Both spectral and kinetic evidences revealed formation of 1:1 intermediate complexes between AA and AgI in both acids before the rate-controlling step. Then the formed complexes react with the oxidant (PtIV) by an inner-sphere mechanism to give rise to the oxidation products of the amino acids which were identified as the corresponding aldehyde, ammonium ion and carbon dioxide. The activation parameters of the second order rate constants were evaluated and discussed.
| Published in | American Journal of Physical Chemistry (Volume 5, Issue 3) |
| DOI | 10.11648/j.ajpc.20160503.13 |
| Page(s) | 65-73 |
| 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 |
α-Amino Acids, Platinum (IV), Kinetics, Mechanism, Oxidation, Silver (I) Catalyst
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APA Style
Ahmed Fawzy, Ishaq A. Zaafarany, Fahd A. Tirkistani, Ismail Althagafi, Jabir Alfahemi. (2016). A Comparative Kinetic Study of Silver(I)-Catalyzed Oxidations of Alanine and Valine by Platinum (IV) in Perchloric and Sulfuric Acids Solutions. American Journal of Physical Chemistry, 5(3), 65-73. https://doi.org/10.11648/j.ajpc.20160503.13
ACS Style
Ahmed Fawzy; Ishaq A. Zaafarany; Fahd A. Tirkistani; Ismail Althagafi; Jabir Alfahemi. A Comparative Kinetic Study of Silver(I)-Catalyzed Oxidations of Alanine and Valine by Platinum (IV) in Perchloric and Sulfuric Acids Solutions. Am. J. Phys. Chem. 2016, 5(3), 65-73. doi: 10.11648/j.ajpc.20160503.13
AMA Style
Ahmed Fawzy, Ishaq A. Zaafarany, Fahd A. Tirkistani, Ismail Althagafi, Jabir Alfahemi. A Comparative Kinetic Study of Silver(I)-Catalyzed Oxidations of Alanine and Valine by Platinum (IV) in Perchloric and Sulfuric Acids Solutions. Am J Phys Chem. 2016;5(3):65-73. doi: 10.11648/j.ajpc.20160503.13
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Download@article{10.11648/j.ajpc.20160503.13,
author = {Ahmed Fawzy and Ishaq A. Zaafarany and Fahd A. Tirkistani and Ismail Althagafi and Jabir Alfahemi},
title = {A Comparative Kinetic Study of Silver(I)-Catalyzed Oxidations of Alanine and Valine by Platinum (IV) in Perchloric and Sulfuric Acids Solutions},
journal = {American Journal of Physical Chemistry},
volume = {5},
number = {3},
pages = {65-73},
doi = {10.11648/j.ajpc.20160503.13},
url = {https://doi.org/10.11648/j.ajpc.20160503.13},
eprint = {https://article.sciencepublishinggroup.com/pdf/10.11648.j.ajpc.20160503.13},
abstract = {The kinetics of oxidations of two aliphatic α-amino acids (AA), namely, alanine and valine by platinum (IV) has been investigated spectrophotometrically in perchloric and sulfuric acids solutions in the presence of silver (I) catalyst at a constant ionic strength of 1.0 mol dm-3 and at 25°C. The reactions were very slow to be measured in the absence of the catalyst. The reactions in both acids showed a first order dependence on both [PtIV] and [AgI], and less than unit order dependences with respect to both [AA] and [H+]. Increasing ionic strength was found to decrease the oxidation rates. Under comparable experimental conditions, the oxidation rates of alanine and valine in perchloric acid solutions were found to be about five times higher than those obtained in sulfuric acid solutions and the oxidation rates of alanine in both acids were found to be higher than those recorded with respect to valine. A plausible oxidations mechanism has been proposed and the rate law expression has been derived. Both spectral and kinetic evidences revealed formation of 1:1 intermediate complexes between AA and AgI in both acids before the rate-controlling step. Then the formed complexes react with the oxidant (PtIV) by an inner-sphere mechanism to give rise to the oxidation products of the amino acids which were identified as the corresponding aldehyde, ammonium ion and carbon dioxide. The activation parameters of the second order rate constants were evaluated and discussed.},
year = {2016}
}
TY - JOUR T1 - A Comparative Kinetic Study of Silver(I)-Catalyzed Oxidations of Alanine and Valine by Platinum (IV) in Perchloric and Sulfuric Acids Solutions AU - Ahmed Fawzy AU - Ishaq A. Zaafarany AU - Fahd A. Tirkistani AU - Ismail Althagafi AU - Jabir Alfahemi Y1 - 2016/05/10 PY - 2016 N1 - https://doi.org/10.11648/j.ajpc.20160503.13 DO - 10.11648/j.ajpc.20160503.13 T2 - American Journal of Physical Chemistry JF - American Journal of Physical Chemistry JO - American Journal of Physical Chemistry SP - 65 EP - 73 PB - Science Publishing Group SN - 2327-2449 UR - https://doi.org/10.11648/j.ajpc.20160503.13 AB - The kinetics of oxidations of two aliphatic α-amino acids (AA), namely, alanine and valine by platinum (IV) has been investigated spectrophotometrically in perchloric and sulfuric acids solutions in the presence of silver (I) catalyst at a constant ionic strength of 1.0 mol dm-3 and at 25°C. The reactions were very slow to be measured in the absence of the catalyst. The reactions in both acids showed a first order dependence on both [PtIV] and [AgI], and less than unit order dependences with respect to both [AA] and [H+]. Increasing ionic strength was found to decrease the oxidation rates. Under comparable experimental conditions, the oxidation rates of alanine and valine in perchloric acid solutions were found to be about five times higher than those obtained in sulfuric acid solutions and the oxidation rates of alanine in both acids were found to be higher than those recorded with respect to valine. A plausible oxidations mechanism has been proposed and the rate law expression has been derived. Both spectral and kinetic evidences revealed formation of 1:1 intermediate complexes between AA and AgI in both acids before the rate-controlling step. Then the formed complexes react with the oxidant (PtIV) by an inner-sphere mechanism to give rise to the oxidation products of the amino acids which were identified as the corresponding aldehyde, ammonium ion and carbon dioxide. The activation parameters of the second order rate constants were evaluated and discussed. VL - 5 IS - 3 ER -
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