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Effect of Silver(I) Catalyst on the Oxidation of L-asparagine by Alkaline Hexacyanoferrate(III): A Kinetic and Mechanistic Approach

Received: 28 January 2016     Accepted: 8 February 2016     Published: 25 February 2016
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Abstract

The kinetics of oxidation of L-asparagine (Asn) by hexacyanoferrate(III) (HCF) has been investigated in alkaline medium in the absence and presence of silver(I) catalyst at a constant ionic strength of 0.5 mol dm−3 and at 20°C. The progress of both uncatalyzed and silver(I)-catalyzed oxidations was followed spectrophotometrically. Both reactions showed a first order dependence with respect to [HCF], whereas the orders with respect to [Asn] and [OH] were less than unity. The catalyzed reaction exhibited a first order dependence in [AgI]. Increasing both ionic strength and dielectric constant of the reaction medium increased the rate of uncatalyzed reaction and did not affect significantly the rate of catalyzed reaction. Addition of the reaction product, HCF(II) to the reaction mixture had no affect on the rate. Appropriate reaction mechanisms for both uncatalyzed and catalyzed oxidations explaining all of the observed kinetic results has been proposed. The catalyzed reaction has been shown to proceed via formation of a silver(I)-asparagine intermediate complex, which reacted with the oxidant by an inner-sphere mechanism leading to decomposition of the complex in the rate-determining step to yield the final oxidation products which were identified as α-formyl acetamide, ammonia, and carbon dioxide. The rate law expressions associated with the reaction mechanisms were derived.

Published in Modern Chemistry (Volume 4, Issue 1)
DOI 10.11648/j.mc.20160401.12
Page(s) 6-15
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

Keywords

L-asparagine, Hexacyanoferrate(III), Silver(I), Kinetics, Mechanism, Oxidation

References
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    Ahmed Fawzy, Ishaq Zaafarany, Ameena Al-Bonayan, Zakiya Al-Mallah, Reem Shah. (2016). Effect of Silver(I) Catalyst on the Oxidation of L-asparagine by Alkaline Hexacyanoferrate(III): A Kinetic and Mechanistic Approach. Modern Chemistry, 4(1), 6-15. https://doi.org/10.11648/j.mc.20160401.12

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    ACS Style

    Ahmed Fawzy; Ishaq Zaafarany; Ameena Al-Bonayan; Zakiya Al-Mallah; Reem Shah. Effect of Silver(I) Catalyst on the Oxidation of L-asparagine by Alkaline Hexacyanoferrate(III): A Kinetic and Mechanistic Approach. Mod. Chem. 2016, 4(1), 6-15. doi: 10.11648/j.mc.20160401.12

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    AMA Style

    Ahmed Fawzy, Ishaq Zaafarany, Ameena Al-Bonayan, Zakiya Al-Mallah, Reem Shah. Effect of Silver(I) Catalyst on the Oxidation of L-asparagine by Alkaline Hexacyanoferrate(III): A Kinetic and Mechanistic Approach. Mod Chem. 2016;4(1):6-15. doi: 10.11648/j.mc.20160401.12

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  • @article{10.11648/j.mc.20160401.12,
      author = {Ahmed Fawzy and Ishaq Zaafarany and Ameena Al-Bonayan and Zakiya Al-Mallah and Reem Shah},
      title = {Effect of Silver(I) Catalyst on the Oxidation of L-asparagine by Alkaline Hexacyanoferrate(III): A Kinetic and Mechanistic Approach},
      journal = {Modern Chemistry},
      volume = {4},
      number = {1},
      pages = {6-15},
      doi = {10.11648/j.mc.20160401.12},
      url = {https://doi.org/10.11648/j.mc.20160401.12},
      eprint = {https://article.sciencepublishinggroup.com/pdf/10.11648.j.mc.20160401.12},
      abstract = {The kinetics of oxidation of L-asparagine (Asn) by hexacyanoferrate(III) (HCF) has been investigated in alkaline medium in the absence and presence of silver(I) catalyst at a constant ionic strength of 0.5 mol dm−3 and at 20°C. The progress of both uncatalyzed and silver(I)-catalyzed oxidations was followed spectrophotometrically. Both reactions showed a first order dependence with respect to [HCF], whereas the orders with respect to [Asn] and [OH−] were less than unity. The catalyzed reaction exhibited a first order dependence in [AgI]. Increasing both ionic strength and dielectric constant of the reaction medium increased the rate of uncatalyzed reaction and did not affect significantly the rate of catalyzed reaction. Addition of the reaction product, HCF(II) to the reaction mixture had no affect on the rate. Appropriate reaction mechanisms for both uncatalyzed and catalyzed oxidations explaining all of the observed kinetic results has been proposed. The catalyzed reaction has been shown to proceed via formation of a silver(I)-asparagine intermediate complex, which reacted with the oxidant by an inner-sphere mechanism leading to decomposition of the complex in the rate-determining step to yield the final oxidation products which were identified as α-formyl acetamide, ammonia, and carbon dioxide. The rate law expressions associated with the reaction mechanisms were derived.},
     year = {2016}
    }
    

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  • TY  - JOUR
    T1  - Effect of Silver(I) Catalyst on the Oxidation of L-asparagine by Alkaline Hexacyanoferrate(III): A Kinetic and Mechanistic Approach
    AU  - Ahmed Fawzy
    AU  - Ishaq Zaafarany
    AU  - Ameena Al-Bonayan
    AU  - Zakiya Al-Mallah
    AU  - Reem Shah
    Y1  - 2016/02/25
    PY  - 2016
    N1  - https://doi.org/10.11648/j.mc.20160401.12
    DO  - 10.11648/j.mc.20160401.12
    T2  - Modern Chemistry
    JF  - Modern Chemistry
    JO  - Modern Chemistry
    SP  - 6
    EP  - 15
    PB  - Science Publishing Group
    SN  - 2329-180X
    UR  - https://doi.org/10.11648/j.mc.20160401.12
    AB  - The kinetics of oxidation of L-asparagine (Asn) by hexacyanoferrate(III) (HCF) has been investigated in alkaline medium in the absence and presence of silver(I) catalyst at a constant ionic strength of 0.5 mol dm−3 and at 20°C. The progress of both uncatalyzed and silver(I)-catalyzed oxidations was followed spectrophotometrically. Both reactions showed a first order dependence with respect to [HCF], whereas the orders with respect to [Asn] and [OH−] were less than unity. The catalyzed reaction exhibited a first order dependence in [AgI]. Increasing both ionic strength and dielectric constant of the reaction medium increased the rate of uncatalyzed reaction and did not affect significantly the rate of catalyzed reaction. Addition of the reaction product, HCF(II) to the reaction mixture had no affect on the rate. Appropriate reaction mechanisms for both uncatalyzed and catalyzed oxidations explaining all of the observed kinetic results has been proposed. The catalyzed reaction has been shown to proceed via formation of a silver(I)-asparagine intermediate complex, which reacted with the oxidant by an inner-sphere mechanism leading to decomposition of the complex in the rate-determining step to yield the final oxidation products which were identified as α-formyl acetamide, ammonia, and carbon dioxide. The rate law expressions associated with the reaction mechanisms were derived.
    VL  - 4
    IS  - 1
    ER  - 

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Author Information
  • Chemistry Department, Faculty of Applied Science, UmmAl-Qura University, Makkah, Saudi Arabia

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

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

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

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

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