Kinetics of microwave-enhanced oxidation of phenol by hydrogen peroxide

Abstract

Aqueous solutions of phenol were oxidized by hydrogen peroxide assisted by microwave (MW) irradiation. A simple kinetic model for the overall degradation of phenol in the presence of excess H₂O₂ is proposed in which the degradation rate of phenol is expressed as a linear function of the concentrations of phenol and H₂O₂. A detailed parametric study showed that the degradation rate of phenol increased with increasing [H₂O₂] until saturation was observed. Phenol degradation followed apparent zero-order kinetics under MW radiation or H₂O₂ oxidation. However, after 90 min of irradiation, the observed kinetics shifted to pseudo first order. The overall reaction rates were significantly enhanced in the combined MW/H₂O₂ system, mainly because microwave could accelerate H₂O₂ to generate hydroxyl radical (^·OH) and other reactive oxygen intermediates. The observed synergetic effects of the MW/H₂O₂ process resulted in an increased in the net reaction rate by a factor of 5.75. When hydrogen peroxide is present in a large stoichiometric excess, the time required to achieve complete mineralization is reduced significantly.

Keywords

microwave (MW) irradiation / hydrogen peroxide / phenol / synergetic effects / kinetic model

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Acknowledgements

This work was supported by the China Postdoctoral Science Foundation Funded Project (Grant No. 20100471716), Zhejiang Provincial Natural Science Foundation of China (Grant No. Y5100075), and the 3M Corporation. D Zhao was on sabbatical leave at Caltech during the 2008–2009 academic year with support provided by China Scholarship Council and Zhejiang University of Technology.

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