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ISRN Physical Chemistry
Volume 2014 (2014), Article ID 592850, 8 pages
http://dx.doi.org/10.1155/2014/592850
Research Article

MNDO and DFT Computational Study on the Mechanism of the Oxidation of 1,2-Diphenylhydrazine by Iodine

Department of Chemistry, Ahmadu Bello University, Zaria 810006, Nigeria

Received 3 February 2014; Accepted 2 March 2014; Published 27 March 2014

Academic Editors: W. B. Davis, H. Luo, H. Pal, and E. B. Starikov

Copyright © 2014 Gideon A. Shallangwa et al. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

Abstract

The reaction mechanisms of the oxidation of 1,2-diphenylhydrazine by iodine have been examined using semiempirical and density functional theory methods, the oxidation proceeded via two independent pathways that can be separately monitored. One pathway involved the chain multistep mechanism. The other pathway occurred via a one-step mechanism in which a “cyclic” activated complex was formed which on disproportionation gave the products. The one-step “cyclic” activated complex mechanism proceeds more rapidly than the chain multistep mechanism. The results were explained by analyses based on computational energetics of the optimised reactants, intermediates, transition states, and products of the reaction of iodine with 1,2-diphenylhydrazine.