Correlation analysis and effect of excess free energy of solvents for the kinetics of oxidation of benzhydrol by tetrabutylammoniumbromochromate

Research and Development Centre, Bharathiar University, Coimbatore-641 046, Tamilnadu, India
Department of Chemistry, Faculty of Applied Sciences, Umm Al-Qura University, P.O. Box 9569,
Makkah, Saudi Arabia
Department of Chemistry, C. Abdul Hakeem College (Autonomous), Melvisharam-632 509,
Tamilnadu, India
E-mail : mansoorcah@gmail.com
Manuscript received online 17 January 2018, accepted 13 February 2018

The oxidation of benzhydrol (BH) by tetrabutylammoniumbromochromate (TBABC) was studied
in the presence of perchloric acid, in water/organic solvent mixtures of varying excess molar free energy function.
The reaction is first order with respect to both TBABC and acid. The reaction rates were determined
at different temperatures and the activation parameters computed. A correlation of data with the Kamlet-
Taft solvatochromic parameters (α, β, π*) suggests that the specific solute-solvent interactions play a major
role in governing the reactivity. The reaction does not induce polymerization of acrylonitrile. The product of
oxidation is benzophenone. Based on the kinetic results and product analysis, a suitable mechanism has been
proposed for the reaction of TBABC with benzhydrol.