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

Ahmed Fawzy; Ismail Althagafi; Fahd Tirkistani; Mohamed Shaaban; Moataz Morad

doi:doi:10.11648/j.ajpc.20160501.11

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

Ahmed Fawzy, Ismail Althagafi, Fahd Tirkistani, Mohamed Shaaban, Moataz Morad

Published in American Journal of Physical Chemistry (Volume 5, Issue 1)

Received: 1 January 2016 Accepted: 8 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 Ag^I, Pd^II and Ru^III catalysts was found to enhance the reaction rate and the order of catalytic efficiency is: Ag^I > Ru^III > Pd^II. 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.

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

Kinetics, Mechanism, Oxidation, Chromic Acid, Methylaminopyrazole Formamidine

References

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APA Style

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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ACS 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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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://article.sciencepublishinggroup.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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Author Information

Ahmed Fawzy

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

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

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

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

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

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APA Style

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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ACS 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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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://article.sciencepublishinggroup.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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