American Journal of Physical Chemistry

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A Comparative Kinetic Study of Silver(I)-Catalyzed Oxidations of Alanine and Valine by Platinum (IV) in Perchloric and Sulfuric Acids Solutions

Received: 17 April 2016    Accepted: 25 April 2016    Published: 10 May 2016
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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.

DOI 10.11648/j.ajpc.20160503.13
Published in American Journal of Physical Chemistry (Volume 5, Issue 3, June 2016)
Page(s) 65-73
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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), 2024. Published by Science Publishing Group

Keywords

α-Amino Acids, Platinum (IV), Kinetics, Mechanism, Oxidation, Silver (I) Catalyst

References
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Author Information
  • Chemistry Department, Faculty of Applied Science, Umm Al-Qura University, Makkah, Saudi Arabia; Chemistry Department, Faculty of Science, Assiut University, Assiut, Egypt

  • Chemistry Department, Faculty of Applied Science, Umm Al-Qura University, Makkah, Saudi Arabia

  • Chemistry Department, Faculty of Applied Science, Umm Al-Qura University, Makkah, Saudi Arabia

  • Chemistry Department, Faculty of Applied Science, Umm Al-Qura University, Makkah, Saudi Arabia

  • Chemistry Department, Faculty of Applied Science, Umm Al-Qura University, Makkah, Saudi Arabia

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    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

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    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

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    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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  • @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://download.sciencepg.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}
    }
    

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  • 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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