Kinetics of Oxidation of Substituted Phenols by Potassium Bromate | Chapter 02 | Theory and Applications of Chemistry Vol. 3
Kinetic methods of analysis are now
accepted as standard analytical procedures for several of reactions, especially
oxidation types. Though the reaction of phenols and substituted phenols by
potassium bromate is well understood as an oxidative type, there was a need to
understand and more evidence required against the participation of Br2 in the
increasing rate of reaction with increasing acetic acid composition in the
bromate oxidation of phenols. Present work explains the strange behaviour on
the basis of formation of HBrO3 that is favoured in acidic medium.
Kinetics of oxidation of 3, 4-Dimethyl phenol, 4-sec-butyl phenol and
4-tert-butyl phenol in aqueous acetic acid - water medium in the temperature
range of 308K to 321K were investigated. The reaction obeys first order
kinetics with respect to [oxidant], [substrate] and [H+]. The active oxidising
species was found to be HBrO3. A suitable mechanism in conformity with the
kinetic observation has been proposed. Various activation parameters such as
energy of activation (58.59, 61, 43, 65.38 KJ/mol), enthalpy change [56.03,
58.87, 62.82 KJ/mol], free energy change (73.19, 77.17, 77.82 KJ/mol) and
entropy of activation (-55.7, -59.45 and -48.78 J/mol/deg) for 3: 4-dimethyl
phenol, 4-sec-butyl phenol, 4-tert-butyl phenol at 308K, were obtained. A rate
law has been derived on the basis of the data. The order of reactivity among
the methyl substituted phenols is 3, 4-dimethyl phenol > p-cresol >
phenol. The order of reactivity among higher alkyl substituted phenols is
4-tert-butyl phenol 4-sec-butyl phenol > 4-ethyl phenol >phenol.
Author(s) Details
Dr. Asha Mathew
Department of Chemistry,
S.I.W.S. College, Wadala, Mumbai 400031, India.
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