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
Volume 5, Issue 3, June 2016, Pages: 65-73
Received: Apr. 17, 2016;
Accepted: Apr. 25, 2016;
Published: May 10, 2016
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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
Fahd A. Tirkistani, Chemistry Department, Faculty of Applied Science, Umm Al-Qura University, Makkah, Saudi Arabia
Ismail Althagafi, Chemistry Department, Faculty of Applied Science, Umm Al-Qura University, Makkah, Saudi Arabia
Jabir Alfahemi, Chemistry Department, Faculty of Applied Science, Umm Al-Qura University, Makkah, Saudi Arabia
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.
Ishaq A. Zaafarany,
Fahd A. Tirkistani,
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.
Vol. 5, No. 3,
2016, pp. 65-73.
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