Effect of Silver(I) Catalyst on the Oxidation of L-asparagine by Alkaline Hexacyanoferrate(III): A Kinetic and Mechanistic Approach

Ahmed Fawzy; Ishaq Zaafarany; Ameena Al-Bonayan; Zakiya Al-Mallah; Reem Shah

doi:doi:10.11648/j.mc.20160401.12

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Effect of Silver(I) Catalyst on the Oxidation of L-asparagine by Alkaline Hexacyanoferrate(III): A Kinetic and Mechanistic Approach

Ahmed Fawzy, Ishaq Zaafarany, Ameena Al-Bonayan, Zakiya Al-Mallah, Reem Shah

Published in Modern Chemistry (Volume 4, Issue 1)

Received: 28 January 2016 Accepted: 8 February 2016 Published: 25 February 2016

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Abstract

The kinetics of oxidation of L-asparagine (Asn) by hexacyanoferrate(III) (HCF) has been investigated in alkaline medium in the absence and presence of silver(I) catalyst at a constant ionic strength of 0.5 mol dm⁻³ and at 20°C. The progress of both uncatalyzed and silver(I)-catalyzed oxidations was followed spectrophotometrically. Both reactions showed a first order dependence with respect to [HCF], whereas the orders with respect to [Asn] and [OH⁻] were less than unity. The catalyzed reaction exhibited a first order dependence in [Ag^I]. Increasing both ionic strength and dielectric constant of the reaction medium increased the rate of uncatalyzed reaction and did not affect significantly the rate of catalyzed reaction. Addition of the reaction product, HCF(II) to the reaction mixture had no affect on the rate. Appropriate reaction mechanisms for both uncatalyzed and catalyzed oxidations explaining all of the observed kinetic results has been proposed. The catalyzed reaction has been shown to proceed via formation of a silver(I)-asparagine intermediate complex, which reacted with the oxidant by an inner-sphere mechanism leading to decomposition of the complex in the rate-determining step to yield the final oxidation products which were identified as α-formyl acetamide, ammonia, and carbon dioxide. The rate law expressions associated with the reaction mechanisms were derived.

Published in	Modern Chemistry (Volume 4, Issue 1)
DOI	10.11648/j.mc.20160401.12
Page(s)	6-15
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), 2024. Published by Science Publishing Group

Keywords

L-asparagine, Hexacyanoferrate(III), Silver(I), Kinetics, Mechanism, Oxidation

References

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APA Style

Ahmed Fawzy, Ishaq Zaafarany, Ameena Al-Bonayan, Zakiya Al-Mallah, Reem Shah. (2016). Effect of Silver(I) Catalyst on the Oxidation of L-asparagine by Alkaline Hexacyanoferrate(III): A Kinetic and Mechanistic Approach. Modern Chemistry, 4(1), 6-15. https://doi.org/10.11648/j.mc.20160401.12

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ACS Style

Ahmed Fawzy; Ishaq Zaafarany; Ameena Al-Bonayan; Zakiya Al-Mallah; Reem Shah. Effect of Silver(I) Catalyst on the Oxidation of L-asparagine by Alkaline Hexacyanoferrate(III): A Kinetic and Mechanistic Approach. Mod. Chem. 2016, 4(1), 6-15. doi: 10.11648/j.mc.20160401.12

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AMA Style

Ahmed Fawzy, Ishaq Zaafarany, Ameena Al-Bonayan, Zakiya Al-Mallah, Reem Shah. Effect of Silver(I) Catalyst on the Oxidation of L-asparagine by Alkaline Hexacyanoferrate(III): A Kinetic and Mechanistic Approach. Mod Chem. 2016;4(1):6-15. doi: 10.11648/j.mc.20160401.12

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@article{10.11648/j.mc.20160401.12,
  author = {Ahmed Fawzy and Ishaq Zaafarany and Ameena Al-Bonayan and Zakiya Al-Mallah and Reem Shah},
  title = {Effect of Silver(I) Catalyst on the Oxidation of L-asparagine by Alkaline Hexacyanoferrate(III): A Kinetic and Mechanistic Approach},
  journal = {Modern Chemistry},
  volume = {4},
  number = {1},
  pages = {6-15},
  doi = {10.11648/j.mc.20160401.12},
  url = {https://doi.org/10.11648/j.mc.20160401.12},
  eprint = {https://article.sciencepublishinggroup.com/pdf/10.11648.j.mc.20160401.12},
  abstract = {The kinetics of oxidation of L-asparagine (Asn) by hexacyanoferrate(III) (HCF) has been investigated in alkaline medium in the absence and presence of silver(I) catalyst at a constant ionic strength of 0.5 mol dm−3 and at 20°C. The progress of both uncatalyzed and silver(I)-catalyzed oxidations was followed spectrophotometrically. Both reactions showed a first order dependence with respect to [HCF], whereas the orders with respect to [Asn] and [OH−] were less than unity. The catalyzed reaction exhibited a first order dependence in [AgI]. Increasing both ionic strength and dielectric constant of the reaction medium increased the rate of uncatalyzed reaction and did not affect significantly the rate of catalyzed reaction. Addition of the reaction product, HCF(II) to the reaction mixture had no affect on the rate. Appropriate reaction mechanisms for both uncatalyzed and catalyzed oxidations explaining all of the observed kinetic results has been proposed. The catalyzed reaction has been shown to proceed via formation of a silver(I)-asparagine intermediate complex, which reacted with the oxidant by an inner-sphere mechanism leading to decomposition of the complex in the rate-determining step to yield the final oxidation products which were identified as α-formyl acetamide, ammonia, and carbon dioxide. The rate law expressions associated with the reaction mechanisms were derived.},
 year = {2016}
}

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TY  - JOUR
T1  - Effect of Silver(I) Catalyst on the Oxidation of L-asparagine by Alkaline Hexacyanoferrate(III): A Kinetic and Mechanistic Approach
AU  - Ahmed Fawzy
AU  - Ishaq Zaafarany
AU  - Ameena Al-Bonayan
AU  - Zakiya Al-Mallah
AU  - Reem Shah
Y1  - 2016/02/25
PY  - 2016
N1  - https://doi.org/10.11648/j.mc.20160401.12
DO  - 10.11648/j.mc.20160401.12
T2  - Modern Chemistry
JF  - Modern Chemistry
JO  - Modern Chemistry
SP  - 6
EP  - 15
PB  - Science Publishing Group
SN  - 2329-180X
UR  - https://doi.org/10.11648/j.mc.20160401.12
AB  - The kinetics of oxidation of L-asparagine (Asn) by hexacyanoferrate(III) (HCF) has been investigated in alkaline medium in the absence and presence of silver(I) catalyst at a constant ionic strength of 0.5 mol dm−3 and at 20°C. The progress of both uncatalyzed and silver(I)-catalyzed oxidations was followed spectrophotometrically. Both reactions showed a first order dependence with respect to [HCF], whereas the orders with respect to [Asn] and [OH−] were less than unity. The catalyzed reaction exhibited a first order dependence in [AgI]. Increasing both ionic strength and dielectric constant of the reaction medium increased the rate of uncatalyzed reaction and did not affect significantly the rate of catalyzed reaction. Addition of the reaction product, HCF(II) to the reaction mixture had no affect on the rate. Appropriate reaction mechanisms for both uncatalyzed and catalyzed oxidations explaining all of the observed kinetic results has been proposed. The catalyzed reaction has been shown to proceed via formation of a silver(I)-asparagine intermediate complex, which reacted with the oxidant by an inner-sphere mechanism leading to decomposition of the complex in the rate-determining step to yield the final oxidation products which were identified as α-formyl acetamide, ammonia, and carbon dioxide. The rate law expressions associated with the reaction mechanisms were derived.
VL  - 4
IS  - 1
ER  -

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Author Information

Ahmed Fawzy

Chemistry Department, Faculty of Applied Science, UmmAl-Qura University, Makkah, Saudi Arabia; Chemistry Department, Faculty of Science, Assiut University, Assiut, Egypt
Ishaq Zaafarany

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

Chemistry Department, Faculty of Applied Science, UmmAl-Qura University, Makkah, Saudi Arabia
Zakiya Al-Mallah

Chemistry Department, Faculty of Applied Science, UmmAl-Qura University, Makkah, Saudi Arabia
Reem Shah

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

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Ahmed Fawzy, Ishaq Zaafarany, Ameena Al-Bonayan, Zakiya Al-Mallah, Reem Shah. (2016). Effect of Silver(I) Catalyst on the Oxidation of L-asparagine by Alkaline Hexacyanoferrate(III): A Kinetic and Mechanistic Approach. Modern Chemistry, 4(1), 6-15. https://doi.org/10.11648/j.mc.20160401.12

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ACS Style

Ahmed Fawzy; Ishaq Zaafarany; Ameena Al-Bonayan; Zakiya Al-Mallah; Reem Shah. Effect of Silver(I) Catalyst on the Oxidation of L-asparagine by Alkaline Hexacyanoferrate(III): A Kinetic and Mechanistic Approach. Mod. Chem. 2016, 4(1), 6-15. doi: 10.11648/j.mc.20160401.12

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AMA Style

Ahmed Fawzy, Ishaq Zaafarany, Ameena Al-Bonayan, Zakiya Al-Mallah, Reem Shah. Effect of Silver(I) Catalyst on the Oxidation of L-asparagine by Alkaline Hexacyanoferrate(III): A Kinetic and Mechanistic Approach. Mod Chem. 2016;4(1):6-15. doi: 10.11648/j.mc.20160401.12

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@article{10.11648/j.mc.20160401.12,
  author = {Ahmed Fawzy and Ishaq Zaafarany and Ameena Al-Bonayan and Zakiya Al-Mallah and Reem Shah},
  title = {Effect of Silver(I) Catalyst on the Oxidation of L-asparagine by Alkaline Hexacyanoferrate(III): A Kinetic and Mechanistic Approach},
  journal = {Modern Chemistry},
  volume = {4},
  number = {1},
  pages = {6-15},
  doi = {10.11648/j.mc.20160401.12},
  url = {https://doi.org/10.11648/j.mc.20160401.12},
  eprint = {https://article.sciencepublishinggroup.com/pdf/10.11648.j.mc.20160401.12},
  abstract = {The kinetics of oxidation of L-asparagine (Asn) by hexacyanoferrate(III) (HCF) has been investigated in alkaline medium in the absence and presence of silver(I) catalyst at a constant ionic strength of 0.5 mol dm−3 and at 20°C. The progress of both uncatalyzed and silver(I)-catalyzed oxidations was followed spectrophotometrically. Both reactions showed a first order dependence with respect to [HCF], whereas the orders with respect to [Asn] and [OH−] were less than unity. The catalyzed reaction exhibited a first order dependence in [AgI]. Increasing both ionic strength and dielectric constant of the reaction medium increased the rate of uncatalyzed reaction and did not affect significantly the rate of catalyzed reaction. Addition of the reaction product, HCF(II) to the reaction mixture had no affect on the rate. Appropriate reaction mechanisms for both uncatalyzed and catalyzed oxidations explaining all of the observed kinetic results has been proposed. The catalyzed reaction has been shown to proceed via formation of a silver(I)-asparagine intermediate complex, which reacted with the oxidant by an inner-sphere mechanism leading to decomposition of the complex in the rate-determining step to yield the final oxidation products which were identified as α-formyl acetamide, ammonia, and carbon dioxide. The rate law expressions associated with the reaction mechanisms were derived.},
 year = {2016}
}

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TY  - JOUR
T1  - Effect of Silver(I) Catalyst on the Oxidation of L-asparagine by Alkaline Hexacyanoferrate(III): A Kinetic and Mechanistic Approach
AU  - Ahmed Fawzy
AU  - Ishaq Zaafarany
AU  - Ameena Al-Bonayan
AU  - Zakiya Al-Mallah
AU  - Reem Shah
Y1  - 2016/02/25
PY  - 2016
N1  - https://doi.org/10.11648/j.mc.20160401.12
DO  - 10.11648/j.mc.20160401.12
T2  - Modern Chemistry
JF  - Modern Chemistry
JO  - Modern Chemistry
SP  - 6
EP  - 15
PB  - Science Publishing Group
SN  - 2329-180X
UR  - https://doi.org/10.11648/j.mc.20160401.12
AB  - The kinetics of oxidation of L-asparagine (Asn) by hexacyanoferrate(III) (HCF) has been investigated in alkaline medium in the absence and presence of silver(I) catalyst at a constant ionic strength of 0.5 mol dm−3 and at 20°C. The progress of both uncatalyzed and silver(I)-catalyzed oxidations was followed spectrophotometrically. Both reactions showed a first order dependence with respect to [HCF], whereas the orders with respect to [Asn] and [OH−] were less than unity. The catalyzed reaction exhibited a first order dependence in [AgI]. Increasing both ionic strength and dielectric constant of the reaction medium increased the rate of uncatalyzed reaction and did not affect significantly the rate of catalyzed reaction. Addition of the reaction product, HCF(II) to the reaction mixture had no affect on the rate. Appropriate reaction mechanisms for both uncatalyzed and catalyzed oxidations explaining all of the observed kinetic results has been proposed. The catalyzed reaction has been shown to proceed via formation of a silver(I)-asparagine intermediate complex, which reacted with the oxidant by an inner-sphere mechanism leading to decomposition of the complex in the rate-determining step to yield the final oxidation products which were identified as α-formyl acetamide, ammonia, and carbon dioxide. The rate law expressions associated with the reaction mechanisms were derived.
VL  - 4
IS  - 1
ER  -

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