Please enter verification code
Confirm
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
Volume 3, Issue 2, March 2015, Pages: 6-18
Received: Mar. 24, 2015; Accepted: Apr. 8, 2015; Published: May 7, 2015
Views 4915      Downloads 152
Authors
Gideon Adamu Shallangwa, Department of Chemistry, Ahmadu Bello University, Zaria, Kaduna State, Nigeria
Adamu Uzairu, Department of Chemistry, Ahmadu Bello University, Zaria, Kaduna State, Nigeria
Victor Olatunji Ajibola, Department of Chemistry, Ahmadu Bello University, Zaria, Kaduna State, Nigeria
Hamza Abba, Department of Chemistry, Ahmadu Bello University, Zaria, Kaduna State, Nigeria
Article Tools
Follow on us
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.
Keywords
DFT Calculations, Reaction Mechanisms, Rate Laws, Iodine, Hydrazine, Transition States
To cite this article
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, International Journal of Computational and Theoretical Chemistry. Vol. 3, No. 2, 2015, pp. 6-18. doi: 10.11648/j.ijctc.20150302.11
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.
ADDRESS
Science Publishing Group
1 Rockefeller Plaza,
10th and 11th Floors,
New York, NY 10020
U.S.A.
Tel: (001)347-983-5186