American Journal of Physical Chemistry

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Chromic Acid Oxidation of Methylaminopyrazole Formamidine in Sulfuric Acid Medium: A Kinetic and Mechanistic Approach

Received: 01 January 2016    Accepted: 08 January 2016    Published: 25 January 2016
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Abstract

The kinetics of chromic acid oxidation of one of aminopyrazole formamidine derivatives, namely N,N-dimethyl-N’ -(5-methyl-1H-pyrazol-3-yl) formamidine (MAPF)in sulfuric acid solutions has been investigated at constant ionic strength and temperature. The progress of the reaction was followed spectrophotometrically. The reaction showed a first order dependence on [chromic acid] and fractional-first order dependences with respect to [MAPF] and [H+]. Increasing ionic strength and solvent polarity of the reaction medium had no significant effect on the oxidation rate. Addition of AgI, PdII and RuIII catalysts was found to enhance the reaction rate and the order of catalytic efficiency is: AgI > RuIII > PdII. The final oxidation products of MAPF are identified by spectral and elemental analysis as methylaminopyrazole, dimethylamine and carbon dioxide. A spectral evidence for the formation of chromium(III) product was obtained. A reaction mechanism adequately describing the observed kinetic behavior is proposed, and the reaction constants involved in the different steps of the mechanism have been evaluated. The activation parameters with respect to the rate-determining step of the reaction, along with thermodynamic quantities of the equilibrium constants, are presented and discussed.

DOI 10.11648/j.ajpc.20160501.11
Published in American Journal of Physical Chemistry (Volume 5, Issue 1, February 2016)
Page(s) 1-9
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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

Kinetics, Mechanism, Oxidation, Chromic Acid, Methylaminopyrazole Formamidine

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 Science, Cairo University, Cairo, Egypt

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

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    Ahmed Fawzy, Ismail Althagafi, Fahd Tirkistani, Mohamed Shaaban, Moataz Morad. (2016). Chromic Acid Oxidation of Methylaminopyrazole Formamidine in Sulfuric Acid Medium: A Kinetic and Mechanistic Approach. American Journal of Physical Chemistry, 5(1), 1-9. https://doi.org/10.11648/j.ajpc.20160501.11

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    Ahmed Fawzy; Ismail Althagafi; Fahd Tirkistani; Mohamed Shaaban; Moataz Morad. Chromic Acid Oxidation of Methylaminopyrazole Formamidine in Sulfuric Acid Medium: A Kinetic and Mechanistic Approach. Am. J. Phys. Chem. 2016, 5(1), 1-9. doi: 10.11648/j.ajpc.20160501.11

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    AMA Style

    Ahmed Fawzy, Ismail Althagafi, Fahd Tirkistani, Mohamed Shaaban, Moataz Morad. Chromic Acid Oxidation of Methylaminopyrazole Formamidine in Sulfuric Acid Medium: A Kinetic and Mechanistic Approach. Am J Phys Chem. 2016;5(1):1-9. doi: 10.11648/j.ajpc.20160501.11

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  • @article{10.11648/j.ajpc.20160501.11,
      author = {Ahmed Fawzy and Ismail Althagafi and Fahd Tirkistani and Mohamed Shaaban and Moataz Morad},
      title = {Chromic Acid Oxidation of Methylaminopyrazole Formamidine in Sulfuric Acid Medium: A Kinetic and Mechanistic Approach},
      journal = {American Journal of Physical Chemistry},
      volume = {5},
      number = {1},
      pages = {1-9},
      doi = {10.11648/j.ajpc.20160501.11},
      url = {https://doi.org/10.11648/j.ajpc.20160501.11},
      eprint = {https://download.sciencepg.com/pdf/10.11648.j.ajpc.20160501.11},
      abstract = {The kinetics of chromic acid oxidation of one of aminopyrazole formamidine derivatives, namely N,N-dimethyl-N’ -(5-methyl-1H-pyrazol-3-yl) formamidine (MAPF)in sulfuric acid solutions has been investigated at constant ionic strength and temperature. The progress of the reaction was followed spectrophotometrically. The reaction showed a first order dependence on [chromic acid] and fractional-first order dependences with respect to [MAPF] and [H+]. Increasing ionic strength and solvent polarity of the reaction medium had no significant effect on the oxidation rate. Addition of AgI, PdII and RuIII catalysts was found to enhance the reaction rate and the order of catalytic efficiency is: AgI > RuIII > PdII. The final oxidation products of MAPF are identified by spectral and elemental analysis as methylaminopyrazole, dimethylamine and carbon dioxide. A spectral evidence for the formation of chromium(III) product was obtained. A reaction mechanism adequately describing the observed kinetic behavior is proposed, and the reaction constants involved in the different steps of the mechanism have been evaluated. The activation parameters with respect to the rate-determining step of the reaction, along with thermodynamic quantities of the equilibrium constants, are presented and discussed.},
     year = {2016}
    }
    

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  • TY  - JOUR
    T1  - Chromic Acid Oxidation of Methylaminopyrazole Formamidine in Sulfuric Acid Medium: A Kinetic and Mechanistic Approach
    AU  - Ahmed Fawzy
    AU  - Ismail Althagafi
    AU  - Fahd Tirkistani
    AU  - Mohamed Shaaban
    AU  - Moataz Morad
    Y1  - 2016/01/25
    PY  - 2016
    N1  - https://doi.org/10.11648/j.ajpc.20160501.11
    DO  - 10.11648/j.ajpc.20160501.11
    T2  - American Journal of Physical Chemistry
    JF  - American Journal of Physical Chemistry
    JO  - American Journal of Physical Chemistry
    SP  - 1
    EP  - 9
    PB  - Science Publishing Group
    SN  - 2327-2449
    UR  - https://doi.org/10.11648/j.ajpc.20160501.11
    AB  - The kinetics of chromic acid oxidation of one of aminopyrazole formamidine derivatives, namely N,N-dimethyl-N’ -(5-methyl-1H-pyrazol-3-yl) formamidine (MAPF)in sulfuric acid solutions has been investigated at constant ionic strength and temperature. The progress of the reaction was followed spectrophotometrically. The reaction showed a first order dependence on [chromic acid] and fractional-first order dependences with respect to [MAPF] and [H+]. Increasing ionic strength and solvent polarity of the reaction medium had no significant effect on the oxidation rate. Addition of AgI, PdII and RuIII catalysts was found to enhance the reaction rate and the order of catalytic efficiency is: AgI > RuIII > PdII. The final oxidation products of MAPF are identified by spectral and elemental analysis as methylaminopyrazole, dimethylamine and carbon dioxide. A spectral evidence for the formation of chromium(III) product was obtained. A reaction mechanism adequately describing the observed kinetic behavior is proposed, and the reaction constants involved in the different steps of the mechanism have been evaluated. The activation parameters with respect to the rate-determining step of the reaction, along with thermodynamic quantities of the equilibrium constants, are presented and discussed.
    VL  - 5
    IS  - 1
    ER  - 

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