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Kinetic and Mechanism of Oxidation of Methylaminopyrazole Formamidine by Alkaline Hexacyanoferrate(III) and the Effect of Divalent Transition Metal Ions

Received: 16 January 2016    Accepted: 25 January 2016    Published: 01 February 2016
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Abstract

In aqueous alkaline medium, the kinetics of oxidation of methylaminopyrazole formamidine (MAPF) by hexacyanoferrate(III) (HCF)has been studied spectrophotometrically under the conditions, MAPF >> HCF at a constant ionic strength of 0.1 mol dm-3 and at 25°C. The reaction showed first order dependence on [HCF] while it exhibited fractional-first order kinetics with respect to [MAPF] and [OH-]. The oxidation rate increased with increasing ionic strength and dielectric constant of the reaction medium. Addition of small amounts of some divalent transition metal ions accelerates the oxidation rate and the order of catalytic efficiency was: Cu(II) > Ni(II) > Zn(II) > Co(II) > Cd(II). The suggested mechanism involves formation of a 1: 1 intermediate complex between HCF and the deprotonated MAPF species in a pre-equilibrium step. The final oxidation products were identified as methylaminopyrazole, dimethylamine and carbon dioxide. The appropriate rate law was deduced. The reaction constants involved in the mechanism were evaluated. The activation and thermodynamic parameters were determined and discussed.

DOI 10.11648/j.sjc.20160401.11
Published in Science Journal of Chemistry (Volume 4, Issue 1, February 2016)
Page(s) 1-8
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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.

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Copyright © The Author(s), 2024. Published by Science Publishing Group

Keywords

Kinetics, Mechanism, Oxidation, Hexacyanoferrate(III), 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 Applied Science, Umm Al-Qura University, Makkah, Saudi Arabia

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    Ahmed Fawzy, Ishaq Zaafarany, Naeema Yarkandi, Ameena Al-Bonayan, Zakiya Almallah. (2016). Kinetic and Mechanism of Oxidation of Methylaminopyrazole Formamidine by Alkaline Hexacyanoferrate(III) and the Effect of Divalent Transition Metal Ions. Science Journal of Chemistry, 4(1), 1-8. https://doi.org/10.11648/j.sjc.20160401.11

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    Ahmed Fawzy; Ishaq Zaafarany; Naeema Yarkandi; Ameena Al-Bonayan; Zakiya Almallah. Kinetic and Mechanism of Oxidation of Methylaminopyrazole Formamidine by Alkaline Hexacyanoferrate(III) and the Effect of Divalent Transition Metal Ions. Sci. J. Chem. 2016, 4(1), 1-8. doi: 10.11648/j.sjc.20160401.11

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    AMA Style

    Ahmed Fawzy, Ishaq Zaafarany, Naeema Yarkandi, Ameena Al-Bonayan, Zakiya Almallah. Kinetic and Mechanism of Oxidation of Methylaminopyrazole Formamidine by Alkaline Hexacyanoferrate(III) and the Effect of Divalent Transition Metal Ions. Sci J Chem. 2016;4(1):1-8. doi: 10.11648/j.sjc.20160401.11

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  • @article{10.11648/j.sjc.20160401.11,
      author = {Ahmed Fawzy and Ishaq Zaafarany and Naeema Yarkandi and Ameena Al-Bonayan and Zakiya Almallah},
      title = {Kinetic and Mechanism of Oxidation of Methylaminopyrazole Formamidine by Alkaline Hexacyanoferrate(III) and the Effect of Divalent Transition Metal Ions},
      journal = {Science Journal of Chemistry},
      volume = {4},
      number = {1},
      pages = {1-8},
      doi = {10.11648/j.sjc.20160401.11},
      url = {https://doi.org/10.11648/j.sjc.20160401.11},
      eprint = {https://download.sciencepg.com/pdf/10.11648.j.sjc.20160401.11},
      abstract = {In aqueous alkaline medium, the kinetics of oxidation of methylaminopyrazole formamidine (MAPF) by hexacyanoferrate(III) (HCF)has been studied spectrophotometrically under the conditions, MAPF >> HCF at a constant ionic strength of 0.1 mol dm-3 and at 25°C. The reaction showed first order dependence on [HCF] while it exhibited fractional-first order kinetics with respect to [MAPF] and [OH-]. The oxidation rate increased with increasing ionic strength and dielectric constant of the reaction medium. Addition of small amounts of some divalent transition metal ions accelerates the oxidation rate and the order of catalytic efficiency was: Cu(II) > Ni(II) > Zn(II) > Co(II) > Cd(II). The suggested mechanism involves formation of a 1: 1 intermediate complex between HCF and the deprotonated MAPF species in a pre-equilibrium step. The final oxidation products were identified as methylaminopyrazole, dimethylamine and carbon dioxide. The appropriate rate law was deduced. The reaction constants involved in the mechanism were evaluated. The activation and thermodynamic parameters were determined and discussed.},
     year = {2016}
    }
    

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  • TY  - JOUR
    T1  - Kinetic and Mechanism of Oxidation of Methylaminopyrazole Formamidine by Alkaline Hexacyanoferrate(III) and the Effect of Divalent Transition Metal Ions
    AU  - Ahmed Fawzy
    AU  - Ishaq Zaafarany
    AU  - Naeema Yarkandi
    AU  - Ameena Al-Bonayan
    AU  - Zakiya Almallah
    Y1  - 2016/02/01
    PY  - 2016
    N1  - https://doi.org/10.11648/j.sjc.20160401.11
    DO  - 10.11648/j.sjc.20160401.11
    T2  - Science Journal of Chemistry
    JF  - Science Journal of Chemistry
    JO  - Science Journal of Chemistry
    SP  - 1
    EP  - 8
    PB  - Science Publishing Group
    SN  - 2330-099X
    UR  - https://doi.org/10.11648/j.sjc.20160401.11
    AB  - In aqueous alkaline medium, the kinetics of oxidation of methylaminopyrazole formamidine (MAPF) by hexacyanoferrate(III) (HCF)has been studied spectrophotometrically under the conditions, MAPF >> HCF at a constant ionic strength of 0.1 mol dm-3 and at 25°C. The reaction showed first order dependence on [HCF] while it exhibited fractional-first order kinetics with respect to [MAPF] and [OH-]. The oxidation rate increased with increasing ionic strength and dielectric constant of the reaction medium. Addition of small amounts of some divalent transition metal ions accelerates the oxidation rate and the order of catalytic efficiency was: Cu(II) > Ni(II) > Zn(II) > Co(II) > Cd(II). The suggested mechanism involves formation of a 1: 1 intermediate complex between HCF and the deprotonated MAPF species in a pre-equilibrium step. The final oxidation products were identified as methylaminopyrazole, dimethylamine and carbon dioxide. The appropriate rate law was deduced. The reaction constants involved in the mechanism were evaluated. The activation and thermodynamic parameters were determined and discussed.
    VL  - 4
    IS  - 1
    ER  - 

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