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Oxidation of Formamidines by Cerium(IV) in Aqueous Perchlorate Solutions: A Kinetics and Mechanistic Approach

Received: 6 March 2016     Accepted: 11 March 2016     Published: 24 March 2016
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Abstract

The kinetics of oxidation of one of the formamidine derivatives, namely, methylaminopyrazole formamidine (MAPF) by cerium(IV) has been investigated in aqueous perchlorate solutions at a constant ionic strength of 1.2 mol dm-3 and at 25°C. The progress of the reaction was followed spectrophotometrically. The reaction exhibited a first order kinetics with respect to [Ce(IV)], whereas the order with respect to [MAPF] was found to be less than unity. The reaction rate decreased with the increase in acid concentration with a negative less than unit order. The rate of reaction was not affected by increasing either ionic strength or dielectric constant of the medium. Furthermore, addition of cerium(III) product did not affect the reaction rate. The plausible oxidation mechanism involves formation of an intermediate complex between MAPF substrate and the kinetically active species of cerium(IV) in a pre-equilibrium step which decomposes in the slow step to give free radical derived from the substrate and Ce(III). The free radical is attacked by another Ce(IV) species to yield the final oxidation products which were identified by spectral and chemical analyses as methylaminopyrazole, dimethylamine and carbon dioxide. The activation parameters have been evaluated and discussed. The rate law associated with the reaction mechanism was derived.

Published in Advances in Biochemistry (Volume 4, Issue 1)
DOI 10.11648/j.ab.20160401.11
Page(s) 1-8
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

Oxidation, Methylaminopyrazole Formamidine, Cerium(IV), Kinetics, Mechanism

References
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  • APA Style

    Ahmed Fawzy, Ishaq Zaafarany, Ismail Althagafi, Moataz Morad, Jabir Alfahmi. (2016). Oxidation of Formamidines by Cerium(IV) in Aqueous Perchlorate Solutions: A Kinetics and Mechanistic Approach. Advances in Biochemistry, 4(1), 1-8. https://doi.org/10.11648/j.ab.20160401.11

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    ACS Style

    Ahmed Fawzy; Ishaq Zaafarany; Ismail Althagafi; Moataz Morad; Jabir Alfahmi. Oxidation of Formamidines by Cerium(IV) in Aqueous Perchlorate Solutions: A Kinetics and Mechanistic Approach. Adv. Biochem. 2016, 4(1), 1-8. doi: 10.11648/j.ab.20160401.11

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    AMA Style

    Ahmed Fawzy, Ishaq Zaafarany, Ismail Althagafi, Moataz Morad, Jabir Alfahmi. Oxidation of Formamidines by Cerium(IV) in Aqueous Perchlorate Solutions: A Kinetics and Mechanistic Approach. Adv Biochem. 2016;4(1):1-8. doi: 10.11648/j.ab.20160401.11

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  • @article{10.11648/j.ab.20160401.11,
      author = {Ahmed Fawzy and Ishaq Zaafarany and Ismail Althagafi and Moataz Morad and Jabir Alfahmi},
      title = {Oxidation of Formamidines by Cerium(IV) in Aqueous Perchlorate Solutions: A Kinetics and Mechanistic Approach},
      journal = {Advances in Biochemistry},
      volume = {4},
      number = {1},
      pages = {1-8},
      doi = {10.11648/j.ab.20160401.11},
      url = {https://doi.org/10.11648/j.ab.20160401.11},
      eprint = {https://article.sciencepublishinggroup.com/pdf/10.11648.j.ab.20160401.11},
      abstract = {The kinetics of oxidation of one of the formamidine derivatives, namely, methylaminopyrazole formamidine (MAPF) by cerium(IV) has been investigated in aqueous perchlorate solutions at a constant ionic strength of 1.2 mol dm-3 and at 25°C. The progress of the reaction was followed spectrophotometrically. The reaction exhibited a first order kinetics with respect to [Ce(IV)], whereas the order with respect to [MAPF] was found to be less than unity. The reaction rate decreased with the increase in acid concentration with a negative less than unit order. The rate of reaction was not affected by increasing either ionic strength or dielectric constant of the medium. Furthermore, addition of cerium(III) product did not affect the reaction rate. The plausible oxidation mechanism involves formation of an intermediate complex between MAPF substrate and the kinetically active species of cerium(IV) in a pre-equilibrium step which decomposes in the slow step to give free radical derived from the substrate and Ce(III). The free radical is attacked by another Ce(IV) species to yield the final oxidation products which were identified by spectral and chemical analyses as methylaminopyrazole, dimethylamine and carbon dioxide. The activation parameters have been evaluated and discussed. The rate law associated with the reaction mechanism was derived.},
     year = {2016}
    }
    

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  • TY  - JOUR
    T1  - Oxidation of Formamidines by Cerium(IV) in Aqueous Perchlorate Solutions: A Kinetics and Mechanistic Approach
    AU  - Ahmed Fawzy
    AU  - Ishaq Zaafarany
    AU  - Ismail Althagafi
    AU  - Moataz Morad
    AU  - Jabir Alfahmi
    Y1  - 2016/03/24
    PY  - 2016
    N1  - https://doi.org/10.11648/j.ab.20160401.11
    DO  - 10.11648/j.ab.20160401.11
    T2  - Advances in Biochemistry
    JF  - Advances in Biochemistry
    JO  - Advances in Biochemistry
    SP  - 1
    EP  - 8
    PB  - Science Publishing Group
    SN  - 2329-0862
    UR  - https://doi.org/10.11648/j.ab.20160401.11
    AB  - The kinetics of oxidation of one of the formamidine derivatives, namely, methylaminopyrazole formamidine (MAPF) by cerium(IV) has been investigated in aqueous perchlorate solutions at a constant ionic strength of 1.2 mol dm-3 and at 25°C. The progress of the reaction was followed spectrophotometrically. The reaction exhibited a first order kinetics with respect to [Ce(IV)], whereas the order with respect to [MAPF] was found to be less than unity. The reaction rate decreased with the increase in acid concentration with a negative less than unit order. The rate of reaction was not affected by increasing either ionic strength or dielectric constant of the medium. Furthermore, addition of cerium(III) product did not affect the reaction rate. The plausible oxidation mechanism involves formation of an intermediate complex between MAPF substrate and the kinetically active species of cerium(IV) in a pre-equilibrium step which decomposes in the slow step to give free radical derived from the substrate and Ce(III). The free radical is attacked by another Ce(IV) species to yield the final oxidation products which were identified by spectral and chemical analyses as methylaminopyrazole, dimethylamine and carbon dioxide. The activation parameters have been evaluated and discussed. The rate law associated with the reaction mechanism was derived.
    VL  - 4
    IS  - 1
    ER  - 

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Author Information
  • 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

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

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