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Computational Study of the Mechanism of the Oxidation of Hydrazine / Hydrazinium Ion by Iodine in the Gas Phase

Received: 24 March 2015     Accepted: 8 April 2015     Published: 7 May 2015
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Abstract

The reaction mechanisms of the oxidation of hydrazine / hydrazinium ion by iodine have been studied using 6311+G** basis set of the density functional theory (DFT) method at the B3LYP level of computation. The study shows that the oxidation reactions can proceed via four independent routes or pathways that can be separately monitored. Two of the proposed pathways involved a two-step reaction mechanism each, in which two transition states were produced while each of the other two routes involved three-step reaction mechanism in which three activated complexes were produced. The results obtained were based on the analyses of the computational energetics of the optimized reactants, intermediates, transition states and products of the reaction of iodine with hydrazine / hydrazinium ion. The study showed that all the four proposed routes were possible by comparing the enthalpies of reactions of the four proposed pathways as well as the activation barriers of the respective rate determining steps which were found to be reasonably acceptable. Rate laws, which were consistent with the written mechanisms, were also derived for each of the proposed mechanisms.

Published in International Journal of Computational and Theoretical Chemistry (Volume 3, Issue 2)
DOI 10.11648/j.ijctc.20150302.11
Page(s) 6-18
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), 2015. Published by Science Publishing Group

Keywords

DFT Calculations, Reaction Mechanisms, Rate Laws, Iodine, Hydrazine, Transition States

References
[1] G. A. Shallangwa, A. Uzairu, V. O. Ajibola, H. Abba, ISRN Physical Chemistry Volume 2014, Article ID 592850, 8 pages.
[2] G.A. Shallangwa, A. Uzairu, V. O. Ajibola, H. Abba, Aceh Int. J. Sci. Technol., 2014, 3(2), pp.106-116.Doi: 10.13170/AIJST.0302.06.
[3] Y. I. Cao Xue, X. M. Jiang, A. Kareem, Z. H. Dou, M. A. Rakeman, M. L. Zhan and G. R. Dulong, The Lancet. 1994, 344, pp.107-109.
[4] B. Mallet, P. Lejeune, N. Baudry, P. Niccoli, P. Carayon and J. Franc, J. Biol. Chem., 1995, 270(50) , pp.29881-29888.
[5] P. M. Yen, Phys. Rev., 2001, 81, pp.1097-1142.
[6] B. S. Hetzel, B. J. Potter and E. M. Dulberg, World Rev. Nutr. Diet., 1990, 62, pp.59-79.
[7] M. S. Mshelia, F. Iyun, A. Uzairu and S. Idris, J. Am .Sci.,2010, 6(9), pp.293-296.
[8] S. Agarwal, K. Gopal, and B. Kumar, Int. J. Dermatol., 2008, 47, pp.367-371.
[9] U. Arora, I. A. Aggarwa and R. K. Arora, Indian J. Pathol. Microbiol., 2003,46, pp.442-443.
[10] A. Bonifaz, A. Saúl, V. Paredes-Solis, L. Fierro, A. Rosales, C. Palacios, et al, PediatrDermatol, 2007, 24, pp.369-372.
[11] C. Cabezas, B. Bustamante, W. Holgado and R. E.Begue, Pediatr Infect Dis J., 1996,15(4), pp.352-354.
[12] V. K. Mahajan, N.L. Sharma, V. Shanker, G. Poonam, M. Kavita, Indian J. Dermatol. Venereol.Leprol.,2010, 76:276-278.
[13] L. Patrick, ALTERN MED REV, 2008,13, pp.116-127.
[14] J. Apelqvist, T. L. G. Ragnarson, Acta Derm. Venereologica, 1996, 76, pp.231-235.
[15] C. Loncle, J. M. Brunel, N. Vidal, M. Dherbomez and Y. Letourneux, Eur. J. Med. Chem., 2004, 39(12), pp. 1067- 1071. Doi:10.1016/j.ejmech.2004.07.005.
[16] S. K. Sridhar, S. N. Pandeya, J. P Stable and A. Ramesh, Eur. J. Pharm. Sci., 2002, 16(3), pp. 129-132. Doi: 1016/S0928-0987(02)00077-5.
[17] M. A. Gaston, L.A. Dias, A.C. Freitas, A.L. Miranda and P. Barreiro, Pharmaceutica Acta Helvetiae, 1996, 71(2), pp.213-219. Doi: 10.1016/0031-6865(96)00012-X.
[18] R. Maccari, R. Ottana and M. G. Vigorita, Bioorg. Med. Chem. Lett., 2005,15(10), pp.2509-2513. Doi:10.1016/j.bmcl.2005.03.065.
[19] K. J. Laidler, Physical Chemistry with Biological Applications, Benjamin Cummings, Menlo Park, NC, 1978, pp. 365-426.
[20] I. A. Funai and M. A. Blesa, Can. J. Chem., 1984, 62, pp.2923 – 2928.
[21] S. M. Sultan, I. Z. Alzamil, A. M. Al-Hajjaji, S. A. Al-Tamrah and A. M. Aziz Al-Rahman, J. Chem. Soc. Pakistan., 198b5,7(2), pp.93-99.
[22] T. S. Rao and P. S.Dalvi, Proceeding Indian national Science Academy, 1990, 56(2), pp. 153-160.
[23] G. A. Shallangwa, A. Uzairu, V. O. Ajibola, H. Abba, Biointerface research in applied chemistry, 2014, 4(2), pp.712-720.
[24] D. A. Palmer and M. H. Lietzke. M. H. RadiochimActa, 1982, 31, pp.37–44.
[25] S. E. King, J. N. Cooper and R. D. Crawford, Inorg. Chem., 1978 , 17(11), pp.3306–3307. DOI:10.1021/ic50189a073
[26] R. M. Smith and A. E. Martell, Critical stability constant,Vol. 4. Plenum Press, New York. 1976, p.43.
[27] R. A. Hasty, Zeitschriftfür Physikalische Chemie, 1975, 94(1-3), pp.53-61.
[28] S. J. Klebanoff, J. Exp. Med., 1967, 126(6), pp.1063 -1078.
[29] M. Aghaie, M. Mirzaie, K. Zare, M. Monajjemi and H. Aghaie, Asian J. Biochem., 2008, 3(5), pp.290-296.
[30] P. Bhatnagar, R. K. Mittal and Y. K.Gupta, Journal of the Chemical Society, Dalton Transactions, 1990, 3669-3673.
[31] M. R. Goyal , P. Bhatnagar, R. K. Mittal and Y.K. Gupta, IJC-A, 1989, 28(5), pp.382-387.
[32] K. Ayub and T. Mahmood, J. Chem. Soc. Pakistan, 2013, 35, pp.617-821.
[33] J. Zhang and W. L. Hase, Journal of Physical Chemistry. Section A, 2010, 114, pp.9635–9643.
[34] F. Jensen, Introduction to Computational Chemistry, J. Wiley & Sons, Chichester, 1999, p.171.
[35] G. A. Shallangwa, A. Uzairu, V. O. Ajibola, H. Abba, Int. J. Modern Chem., 2014, 6(2), pp. 96-109
[36] W. J. Hehre, L. Random, P. V. R. Schleger and J. A. Pople, Ab Initio Molecular Orbital Theory, Wiley, New York, USA, 1986, section 62-63.
[37] M. Izadyara, M. R. Gholami, M. Haghgu, Journal of Molecular Structure: (THEOCHEM), 2004, 686, pp.37–42.
[38] K. Kahn and T. C. Bruice, J. Amer. Chem. Soc., 2000, 12(10), pp. 46–51.
[39] H. H. Sisler, G. M. Omietanski and B. Rudner, Chem. Rev., 1957, 57(6), pp.1021–1047.
[40] R. Barca, J. Ellis, M. S. Tsao and W. K. Willmarth, Inorg. Chem., 1967, 6(2), pp.243–248.
[41] Z. Jia, M. G. Salaita and. W. Margerum, Inorg. Chem., 39(9), 1974–197, pp2000.
[42] T. Engel and P. Reid, Physical Chemistry, Pearson Prentice Hall, Upper saddle River, NJ, 2006. p.924.
[43] J. W. Ochterski , Thermochemistry in Gaussian, Technical Support Information, gaussian.com, 2000, pp.1 -19.
[44] A. J. Mee, Physical Chemistry,6th edition, English Language Book Society & Heinemann Educational Books Ltd, London, 1971, pp.583.
[45] C. E. Housecroft and A. G. Sharpe, Inorganic Chemistry,3rd edition, Pearson Prentice Hall, Milan, 2008, pp.882-883.
[46] R. P. Szajewski and G. M.Whiteside, J. Amer. Chem. Soc., 1980, 102(6), pp.2011-2026.
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  • APA Style

    Gideon Adamu Shallangwa, Adamu Uzairu, Victor Olatunji Ajibola, Hamza Abba. (2015). Computational Study of the Mechanism of the Oxidation of Hydrazine / Hydrazinium Ion by Iodine in the Gas Phase. International Journal of Computational and Theoretical Chemistry, 3(2), 6-18. https://doi.org/10.11648/j.ijctc.20150302.11

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    ACS Style

    Gideon Adamu Shallangwa; Adamu Uzairu; Victor Olatunji Ajibola; Hamza Abba. Computational Study of the Mechanism of the Oxidation of Hydrazine / Hydrazinium Ion by Iodine in the Gas Phase. Int. J. Comput. Theor. Chem. 2015, 3(2), 6-18. doi: 10.11648/j.ijctc.20150302.11

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    AMA Style

    Gideon Adamu Shallangwa, Adamu Uzairu, Victor Olatunji Ajibola, Hamza Abba. Computational Study of the Mechanism of the Oxidation of Hydrazine / Hydrazinium Ion by Iodine in the Gas Phase. Int J Comput Theor Chem. 2015;3(2):6-18. doi: 10.11648/j.ijctc.20150302.11

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  • @article{10.11648/j.ijctc.20150302.11,
      author = {Gideon Adamu Shallangwa and Adamu Uzairu and Victor Olatunji Ajibola and Hamza Abba},
      title = {Computational Study of the Mechanism of the Oxidation of Hydrazine / Hydrazinium Ion by Iodine in the Gas Phase},
      journal = {International Journal of Computational and Theoretical Chemistry},
      volume = {3},
      number = {2},
      pages = {6-18},
      doi = {10.11648/j.ijctc.20150302.11},
      url = {https://doi.org/10.11648/j.ijctc.20150302.11},
      eprint = {https://article.sciencepublishinggroup.com/pdf/10.11648.j.ijctc.20150302.11},
      abstract = {The reaction mechanisms of the oxidation of hydrazine / hydrazinium ion by iodine have been studied using 6311+G** basis set of the density functional theory (DFT) method at the B3LYP level of computation. The study shows that the oxidation reactions can proceed via four independent routes or pathways that can be separately monitored. Two of the proposed pathways involved a two-step reaction mechanism each, in which two transition states were produced while each of the other two routes involved three-step reaction mechanism in which three activated complexes were produced. The results obtained were based on the analyses of the computational energetics of the optimized reactants, intermediates, transition states and products of the reaction of iodine with hydrazine / hydrazinium ion. The study showed that all the four proposed routes were possible by comparing the enthalpies of reactions of the four proposed pathways as well as the activation barriers of the respective rate determining steps which were found to be reasonably acceptable. Rate laws, which were consistent with the written mechanisms, were also derived for each of the proposed mechanisms.},
     year = {2015}
    }
    

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    T1  - Computational Study of the Mechanism of the Oxidation of Hydrazine / Hydrazinium Ion by Iodine in the Gas Phase
    AU  - Gideon Adamu Shallangwa
    AU  - Adamu Uzairu
    AU  - Victor Olatunji Ajibola
    AU  - Hamza Abba
    Y1  - 2015/05/07
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    DO  - 10.11648/j.ijctc.20150302.11
    T2  - International Journal of Computational and Theoretical Chemistry
    JF  - International Journal of Computational and Theoretical Chemistry
    JO  - International Journal of Computational and Theoretical Chemistry
    SP  - 6
    EP  - 18
    PB  - Science Publishing Group
    SN  - 2376-7308
    UR  - https://doi.org/10.11648/j.ijctc.20150302.11
    AB  - The reaction mechanisms of the oxidation of hydrazine / hydrazinium ion by iodine have been studied using 6311+G** basis set of the density functional theory (DFT) method at the B3LYP level of computation. The study shows that the oxidation reactions can proceed via four independent routes or pathways that can be separately monitored. Two of the proposed pathways involved a two-step reaction mechanism each, in which two transition states were produced while each of the other two routes involved three-step reaction mechanism in which three activated complexes were produced. The results obtained were based on the analyses of the computational energetics of the optimized reactants, intermediates, transition states and products of the reaction of iodine with hydrazine / hydrazinium ion. The study showed that all the four proposed routes were possible by comparing the enthalpies of reactions of the four proposed pathways as well as the activation barriers of the respective rate determining steps which were found to be reasonably acceptable. Rate laws, which were consistent with the written mechanisms, were also derived for each of the proposed mechanisms.
    VL  - 3
    IS  - 2
    ER  - 

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Author Information
  • Department of Chemistry, Ahmadu Bello University, Zaria, Kaduna State, Nigeria

  • Department of Chemistry, Ahmadu Bello University, Zaria, Kaduna State, Nigeria

  • Department of Chemistry, Ahmadu Bello University, Zaria, Kaduna State, Nigeria

  • Department of Chemistry, Ahmadu Bello University, Zaria, Kaduna State, Nigeria

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