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Interfacial Micro-heterogeneous Surface Phenomenon in the Oxidative Transformation of 2-Phenylethanol by Ce(IV)

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Abstract

Oxidative transformation of 2-phenylethanol have been executed in pure aqueous and surfactant medium using Ce(IV) as the oxidant. A comprehensive kinetic analysis for the electron transfer process was made to predict the mechanism of transformation. The reaction progress was monitored by recording the decrease in absorbance of the oxidant Ce(IV) at the λmax (wave length of maximum absorbance) value of 315 nm. Pseudo first order conditions was maintained in the medium and acidity of the reaction environment was regulated by perchloric acid. The plot of log (absorbance) vs time for the disappearance of Ce(IV) was observed to be cleanly linear for up to three half-lives of the reaction and the nature of the plot was independent of initial concentration of Ce(IV) species indicating first order dependence of rate with respect to oxidant. The observation of rate variation in substrate (2-phenylethanol) concentration indicate Michaelis–Menten type of mechanism suggesting complex formation between the substrate and oxidant before the rate determining step. Inverse dependence of rate on acid strength has been observed. The kinetic and mechanistic study in surfactant medium was performed by introducing sodium dodecyl sulphate (SDS) to the reaction. In presence of the surfactant, the rate initially increased till the critical micelle concentration (cmc) is reached and then falls generating a hump in the [SDS] vs rate constant profile. The rate alteration and the interfacial micro-heterogeneous catalytic behavior of the environment friendly SDS in the pre- and post-cmc is explained by Berezin model. The effect of temperature on the reaction was monitored in the temperature range of 303–312 K. Positive activation enthalpy and free energy was recorded while the activation entropy was found to be negative. Based on all the experimental observations, suitable kinetic model has been proposed for the oxidation both in the pure aqueous and surfactant medium.

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Authors and Affiliations

  1. Department of Chemistry, Centurion University of Technology and Management, Paralakhemundi, Orissa, 761211, India

    Sarita Sahu & Satya Prasad Nanda

  2. Department of Chemistry, NIST (Autonomous), Berhampur, Pallur Hills, Golanthara, Orissa, 761008, India

    Ranjan Kumar Padhy

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  1. Sarita Sahu
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Sahu, S., Nanda, S.P. & Padhy, R.K. Interfacial Micro-heterogeneous Surface Phenomenon in the Oxidative Transformation of 2-Phenylethanol by Ce(IV). Chemistry Africa 7, 1605–1617 (2024). https://doi.org/10.1007/s42250-023-00809-x

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