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

Ahmed Fawzy; Ishaq Zaafarany; Ismail Althagafi; Moataz Morad; Jabir Alfahmi

doi:doi:10.11648/j.ab.20160401.11

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

Ahmed Fawzy, Ishaq Zaafarany, Ismail Althagafi, Moataz Morad, Jabir Alfahmi

Published in Advances in Biochemistry (Volume 4, Issue 1)

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

Ahmed Fawzy

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

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
Moataz Morad

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

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

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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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