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

Ahmed Fawzy; Ishaq Zaafarany; Naeema Yarkandi; Ameena Al-Bonayan; Zakiya Almallah

doi:doi:10.11648/j.sjc.20160401.11

| Peer-Reviewed

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

Ahmed Fawzy, Ishaq Zaafarany, Naeema Yarkandi, Ameena Al-Bonayan, Zakiya Almallah

Published in Science Journal of Chemistry (Volume 4, Issue 1)

Received: 16 January 2016 Accepted: 25 January 2016 Published: 1 February 2016

Views: Downloads:

Download PDF

Share This Article

Twitter
Linked In
Facebook

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.

Published in	Science Journal of Chemistry (Volume 4, Issue 1)
DOI	10.11648/j.sjc.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

Kinetics, Mechanism, Oxidation, Hexacyanoferrate(III), Methylaminopyrazole Formamidine

References

[1]	Leung VSK, Chan TYK, Yeung VTF (1999) Ami-traz poisining in humans, Clinical Toxicol. 37: 513-514.
[2]	Nakayama A, Sukekawa M, Eguchi Y (1997) Stereo-chemistry and active conformation of a novel insecticide Acetamiprid. Pesticide Sci. 51: 157-164.
[3]	Beeman RW, Matsumura F (1973) Chlordimeform: a pesticide acting upon amine regulatory mechanisms. Nature. 242: 273-274.
[4]	Aziz AA, Knowles CO (1973) Inhibition of monoamine oxidase by the pesticides chlordimeform and related compounds. Nature 242: 417-418.
[5]	Saweczko P (2001) Interaction of ferrocenoyl-dipeptides with 3-aminopyrazole derivatives: beta-sheet models: A synthetic, spectroscopic, structural, and electrochemical study. Inorg. Chem. 40: 4409-4419.
[6]	Kelson EP, Phengsy PP (2000) Kinetic study of 2-propanol and benzyl alcohol oxidation by alkaline hexacyanoferrate(III) catalysed by a terpyridyl ruthenium complex. Int. J. Chem. Kinet. 32: 760–770.
[7]	Vovk AI, Muraveva IV, Kukhar VP, Baklan VF (2000) Kinetics of oxidation of vitamin B1 and its Oacyl analogs with ferricyanide. A mechanistic model of thiamin-binding protein. Russ. J. Gen. Chem. 70: 1108–1112.
[8]	Speakman PT, Waters WA (1955) Kinetic features of the oxidation of aldehydes, ketones and nitroparaffins with alkaline ferricyanide. J. Chem. Soc. 40–50.
[9]	Jose TP, Nandibewoor ST, Tuwar SM (2006) Kinetics and mechanism of oxidation of vanillin by hexacyanoferrate(III) in aqueous alkaline medium. J. Solution Chem. 35: 51–62.
[10]	Singh VN, Singh MP, Saxena BBL (1970) Kinetics and mechanism of alkaline ferricyanide oxidation of acetone and ethyl methyl ketone. Indian J. Chem. 8: 529–532.
[11]	Leal JM, Garcia B, Domingo PL (1998) Outer-sphere hexacyanoferrate(III) oxidation of organic substrates. Coord. Chem. Rev. 173: 79–131.
[12]	Jose TP, Angadi MA, Salunke MS, Tuwar SM (2008) Oxidative study of gabapentin by alkaline hexacyanoferrate(III) in room temperature in presence of catalytic amount of Ru(III). A mechanistic approach. J. Mol. Struct. 892: 121–124.
[13]	Sharanabasamma K, Angadi MA, Salunke MS, Tuwar SM (2009) Osmium(VIII) catalysed oxidative cleavage of pyrrolidine ring in L-proline by hexacyanoferrate(III) in alkaline media. Ind. Eng. Chem. Res. 48: 10381–10386.
[14]	Goel A, Sharma S (2010) Mechanistic study of the oxidation of L-phenylalanine by hexacyanoferrate (III) catalyzed by iridium(III) in aqueous alkaline medium, Transition Met. Chem. 35: 549-554.
[15]	Devra V, Yadav MB (2012) Kinetics and mechanism of osmium(VIII) catalyzed oxidation of valine by hexacyanoferrate in alkaline medium, Rassian J. Chem. 5: 67-73.
[16]	Upadhyay SK, MC agrawal (1977) Kinetics of Os (VIII)-catalyzed alkaline hexacyanoferrate (III) oxidation of some α-amino acids in presence of excess of ferricyanide, Ind. J. Chem., 15A: 709-712;
[17]	Jose TP, Nandibewoor ST, Tuwar SM (2006) Osmium(VIII) catalyzed oxidation of a sulfur containing amino acid – A kinetic and mechanistic Approach. J. Sulfur Chem., 27: 25-36.
[18]	Farokhi SA, Nandibewoor ST (2003) Kinetic, mechanistic and spectral studies for the oxidation of sulfanilic acid by alkaline hexacyanoferrate(III). Tetrahedron 59: 7595-7601.
[19]	Padhye S, Kaufman GB (1985) Transition metal complexes of semicarbazones and thiosemicarbazones. Coord. Chem. Rev. 63: 127-160.
[20]	Asiri AM, Khan SA (2010) Palladium(II) complexes of NS donor ligands derived from steroidal thiosemicarbazones as antibacterial agents. Molecules 15: 4784-4791.
[21]	Jeffery GH, Bassett J, Mendham J, Denney RC (1996) Text Book of Quantitative Chemical Analysis, 5th ed.; ELBS Longman: Essex, pp. 384.
[22]	Fawzy A, Shaaban MR (2014) Kinetic and mechanistic investigations on the oxidation of N’-heteroaryl unsymmetrical formamidines by permanganate in aqueous alkaline medium. Transition Met. Chem. 39: 379-386.
[23]	Vogel AI (1973) Text book of practical organic chemistry including quantitative organic analysis, 3rd edn, 332 pp. ELBS, Longman.
[24]	Feigl F (1975) Spot tests in organic analysis, 195 pp. Elsevier, New York.
[25]	Leal JM, Domingo PL, Garcla B, Ibeas S (1993) Alkali metal ion catalysis of the oxidation of L-ascorbic acid by hexacyanoferrate(III) in strongly acidic media. J. Chem. Soc. Faraday Trans. 89: 3571–3577.
[26]	Frost AA, Person RG (1973) Kinetics and mechanism, 147 pp. Wiley Eastern, New Delhi.
[27]	Amis ES (1966) Solvent effect on reaction rates and mechanism, pp. 28, Academic Press, New York.
[28]	Michaelis L, Menten ML (1913) The kinetics of invertase action. Biochem. Z. 49: 333–369.
[29]	Hicks KW, Toppen DL, Linck RG (1972) Inner-sphere electron-transfer reactions of vanadium (II) with azidoamine complexes of cobalt(III). Inorg. Chem. 11 (1972) 310–315.
[30]	Sutin N (1968) Free energies, barriers, and reactivity patterns in oxidation-reduction reactions. Acc. Chem. Res. 1: 225–231.
[31]	Freeman F (1981) Permanganate ion oxidations. 13. Soluble manganese (IV) species in the oxidation of 2, 4(1H, 3H)-pyrimidinediones (uracils). J. Am. Chem. Soc. 103: 1154–1158.
[32]	Meier DJ, Garner CS (1952) The kinetics of the europium (II)-europium (III) exchange reaction. J. Phys. Chem. 56: 853–857.
[33]	Duke FR, Parchen RF (1956) The kinetics of the Ce(IV)-Ce(III) exchange reaction in perchloric acid. J. Am. Chem. Soc. 78: 1540–1543.
[34]	Taube H, Myers H, Rich RL (1953) The mechanism of electron transfer in solution. J. Am. Chem. Soc. 75: 4118–4119.
[35]	Taube H, Myer, H (1954) Evidence for bridged activated complex for electron transfer re- action. J. Am. Chem. Soc. 76: 2103–2111.
[36]	SheppardJC, Wahl AC (1957) Kinetics of the manganate-permanganate exchange reaction. J. Am. Chem. Soc. 79: 1020–1024.
[37]	Abdel-Zaher AE (2015) Synthesis of benzoazolyl-N, N-dimethylformamidines: complexation and biological activity, Eur. Int. J. Sci. Technol. 4: 88-99.
[38]	Sala R, Bokka AK, Kethavath BKN, Gollapalli NR (2012) Effect of dielectric constant of medium on chemical speciation of L-histidine complexes of Co(II), Ni(II) and Cu(II). Bull. Chem. Soc. Ethiopia 26: 227–238.

Cite This Article

Plain Text BibTeX RIS

APA Style

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

Copy | Download

ACS 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

Copy | Download

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

Copy | Download

@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://article.sciencepublishinggroup.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}
}

Copy | Download

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  -

Copy | Download

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
Naeema Yarkandi

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

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

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

Download PDF

Sections

Plain Text BibTeX RIS

APA Style

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

Copy | Download

ACS 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

Copy | Download

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

Copy | Download

@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://article.sciencepublishinggroup.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}
}

Copy | Download

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  -

Copy | Download