Kinetics and Mechanistic Study of Permanganate Oxidation of L-Citrulline in Acidic and Basic Media

Ismail I. Althagafi; Ahmed Fawzy

doi:doi:10.11648/j.ajpc.20160506.11

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Kinetics and Mechanistic Study of Permanganate Oxidation of L-Citrulline in Acidic and Basic Media

Ismail I. Althagafi, Ahmed Fawzy

Published in American Journal of Physical Chemistry (Volume 5, Issue 6)

Received: 29 August 2016 Accepted: 17 October 2016 Published: 29 November 2016

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Abstract

Kinetics of oxidation of L-citrulline (Cit) by permanganate ion in both acidic and basic media has been investigated spectrophtometrically at constant ionic strengths and at 25°C. In both media the reactions exhibited first order dependence in [permanganate] and less than unit order dependences in L-citrulline concentration. A fractional-second order dependence with respect to [H ⁺] and a fractional-first order dependence with respect to [OH^-] were revealed in acidic and basic media, respectively. Increasing ionic strength in basic medium increased the oxidation rate of L-citrulline, whereas it had a negligible effect on the oxidation rate in acidic medium. The rate-determining step in both media is suggested to involve a one-electron change, but the stoichiometry (L-citrulline: permanganate) was different, being 5:2 in acidic medium and 1:2 in basic medium. The proposed oxidation mechanisms involve formation of 1:1 intermediate complexes between kinetically active species of both L-citrulline and permanganate ion in pre-equilibrium steps. The final oxidation products of L-citrulline were identified in both acidic and basic media as the corresponding aldehyde (4-(carbamoylamino) butyraldehyde), ammonia and carbon dioxide. The appropriate rate laws are deduced.

Published in	American Journal of Physical Chemistry (Volume 5, Issue 6)
DOI	10.11648/j.ajpc.20160506.11
Page(s)	99-107
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

L-Citrulline, Permanganate, Oxidation, Kinetics, Mechanism

References

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Ismail I. Althagafi, Ahmed Fawzy. (2016). Kinetics and Mechanistic Study of Permanganate Oxidation of L-Citrulline in Acidic and Basic Media. American Journal of Physical Chemistry, 5(6), 99-107. https://doi.org/10.11648/j.ajpc.20160506.11

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ACS Style

Ismail I. Althagafi; Ahmed Fawzy. Kinetics and Mechanistic Study of Permanganate Oxidation of L-Citrulline in Acidic and Basic Media. Am. J. Phys. Chem. 2016, 5(6), 99-107. doi: 10.11648/j.ajpc.20160506.11

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AMA Style

Ismail I. Althagafi, Ahmed Fawzy. Kinetics and Mechanistic Study of Permanganate Oxidation of L-Citrulline in Acidic and Basic Media. Am J Phys Chem. 2016;5(6):99-107. doi: 10.11648/j.ajpc.20160506.11

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@article{10.11648/j.ajpc.20160506.11,
  author = {Ismail I. Althagafi and Ahmed Fawzy},
  title = {Kinetics and Mechanistic Study of Permanganate Oxidation of L-Citrulline in Acidic and Basic Media},
  journal = {American Journal of Physical Chemistry},
  volume = {5},
  number = {6},
  pages = {99-107},
  doi = {10.11648/j.ajpc.20160506.11},
  url = {https://doi.org/10.11648/j.ajpc.20160506.11},
  eprint = {https://article.sciencepublishinggroup.com/pdf/10.11648.j.ajpc.20160506.11},
  abstract = {Kinetics of oxidation of L-citrulline (Cit) by permanganate ion in both acidic and basic media has been investigated spectrophtometrically at constant ionic strengths and at 25°C. In both media the reactions exhibited first order dependence in [permanganate] and less than unit order dependences in L-citrulline concentration. A fractional-second order dependence with respect to [H +] and a fractional-first order dependence with respect to [OH-] were revealed in acidic and basic media, respectively. Increasing ionic strength in basic medium increased the oxidation rate of L-citrulline, whereas it had a negligible effect on the oxidation rate in acidic medium. The rate-determining step in both media is suggested to involve a one-electron change, but the stoichiometry (L-citrulline: permanganate) was different, being 5:2 in acidic medium and 1:2 in basic medium. The proposed oxidation mechanisms involve formation of 1:1 intermediate complexes between kinetically active species of both L-citrulline and permanganate ion in pre-equilibrium steps. The final oxidation products of L-citrulline were identified in both acidic and basic media as the corresponding aldehyde (4-(carbamoylamino) butyraldehyde), ammonia and carbon dioxide. The appropriate rate laws are deduced.},
 year = {2016}
}

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TY  - JOUR
T1  - Kinetics and Mechanistic Study of Permanganate Oxidation of L-Citrulline in Acidic and Basic Media
AU  - Ismail I. Althagafi
AU  - Ahmed Fawzy
Y1  - 2016/11/29
PY  - 2016
N1  - https://doi.org/10.11648/j.ajpc.20160506.11
DO  - 10.11648/j.ajpc.20160506.11
T2  - American Journal of Physical Chemistry
JF  - American Journal of Physical Chemistry
JO  - American Journal of Physical Chemistry
SP  - 99
EP  - 107
PB  - Science Publishing Group
SN  - 2327-2449
UR  - https://doi.org/10.11648/j.ajpc.20160506.11
AB  - Kinetics of oxidation of L-citrulline (Cit) by permanganate ion in both acidic and basic media has been investigated spectrophtometrically at constant ionic strengths and at 25°C. In both media the reactions exhibited first order dependence in [permanganate] and less than unit order dependences in L-citrulline concentration. A fractional-second order dependence with respect to [H +] and a fractional-first order dependence with respect to [OH-] were revealed in acidic and basic media, respectively. Increasing ionic strength in basic medium increased the oxidation rate of L-citrulline, whereas it had a negligible effect on the oxidation rate in acidic medium. The rate-determining step in both media is suggested to involve a one-electron change, but the stoichiometry (L-citrulline: permanganate) was different, being 5:2 in acidic medium and 1:2 in basic medium. The proposed oxidation mechanisms involve formation of 1:1 intermediate complexes between kinetically active species of both L-citrulline and permanganate ion in pre-equilibrium steps. The final oxidation products of L-citrulline were identified in both acidic and basic media as the corresponding aldehyde (4-(carbamoylamino) butyraldehyde), ammonia and carbon dioxide. The appropriate rate laws are deduced.
VL  - 5
IS  - 6
ER  -

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Author Information

Ismail I. Althagafi

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

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

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APA Style

Ismail I. Althagafi, Ahmed Fawzy. (2016). Kinetics and Mechanistic Study of Permanganate Oxidation of L-Citrulline in Acidic and Basic Media. American Journal of Physical Chemistry, 5(6), 99-107. https://doi.org/10.11648/j.ajpc.20160506.11

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ACS Style

Ismail I. Althagafi; Ahmed Fawzy. Kinetics and Mechanistic Study of Permanganate Oxidation of L-Citrulline in Acidic and Basic Media. Am. J. Phys. Chem. 2016, 5(6), 99-107. doi: 10.11648/j.ajpc.20160506.11

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AMA Style

Ismail I. Althagafi, Ahmed Fawzy. Kinetics and Mechanistic Study of Permanganate Oxidation of L-Citrulline in Acidic and Basic Media. Am J Phys Chem. 2016;5(6):99-107. doi: 10.11648/j.ajpc.20160506.11

Copy | Download

@article{10.11648/j.ajpc.20160506.11,
  author = {Ismail I. Althagafi and Ahmed Fawzy},
  title = {Kinetics and Mechanistic Study of Permanganate Oxidation of L-Citrulline in Acidic and Basic Media},
  journal = {American Journal of Physical Chemistry},
  volume = {5},
  number = {6},
  pages = {99-107},
  doi = {10.11648/j.ajpc.20160506.11},
  url = {https://doi.org/10.11648/j.ajpc.20160506.11},
  eprint = {https://article.sciencepublishinggroup.com/pdf/10.11648.j.ajpc.20160506.11},
  abstract = {Kinetics of oxidation of L-citrulline (Cit) by permanganate ion in both acidic and basic media has been investigated spectrophtometrically at constant ionic strengths and at 25°C. In both media the reactions exhibited first order dependence in [permanganate] and less than unit order dependences in L-citrulline concentration. A fractional-second order dependence with respect to [H +] and a fractional-first order dependence with respect to [OH-] were revealed in acidic and basic media, respectively. Increasing ionic strength in basic medium increased the oxidation rate of L-citrulline, whereas it had a negligible effect on the oxidation rate in acidic medium. The rate-determining step in both media is suggested to involve a one-electron change, but the stoichiometry (L-citrulline: permanganate) was different, being 5:2 in acidic medium and 1:2 in basic medium. The proposed oxidation mechanisms involve formation of 1:1 intermediate complexes between kinetically active species of both L-citrulline and permanganate ion in pre-equilibrium steps. The final oxidation products of L-citrulline were identified in both acidic and basic media as the corresponding aldehyde (4-(carbamoylamino) butyraldehyde), ammonia and carbon dioxide. The appropriate rate laws are deduced.},
 year = {2016}
}

Copy | Download

TY  - JOUR
T1  - Kinetics and Mechanistic Study of Permanganate Oxidation of L-Citrulline in Acidic and Basic Media
AU  - Ismail I. Althagafi
AU  - Ahmed Fawzy
Y1  - 2016/11/29
PY  - 2016
N1  - https://doi.org/10.11648/j.ajpc.20160506.11
DO  - 10.11648/j.ajpc.20160506.11
T2  - American Journal of Physical Chemistry
JF  - American Journal of Physical Chemistry
JO  - American Journal of Physical Chemistry
SP  - 99
EP  - 107
PB  - Science Publishing Group
SN  - 2327-2449
UR  - https://doi.org/10.11648/j.ajpc.20160506.11
AB  - Kinetics of oxidation of L-citrulline (Cit) by permanganate ion in both acidic and basic media has been investigated spectrophtometrically at constant ionic strengths and at 25°C. In both media the reactions exhibited first order dependence in [permanganate] and less than unit order dependences in L-citrulline concentration. A fractional-second order dependence with respect to [H +] and a fractional-first order dependence with respect to [OH-] were revealed in acidic and basic media, respectively. Increasing ionic strength in basic medium increased the oxidation rate of L-citrulline, whereas it had a negligible effect on the oxidation rate in acidic medium. The rate-determining step in both media is suggested to involve a one-electron change, but the stoichiometry (L-citrulline: permanganate) was different, being 5:2 in acidic medium and 1:2 in basic medium. The proposed oxidation mechanisms involve formation of 1:1 intermediate complexes between kinetically active species of both L-citrulline and permanganate ion in pre-equilibrium steps. The final oxidation products of L-citrulline were identified in both acidic and basic media as the corresponding aldehyde (4-(carbamoylamino) butyraldehyde), ammonia and carbon dioxide. The appropriate rate laws are deduced.
VL  - 5
IS  - 6
ER  -

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