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

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

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

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