The photo-generated transient species carbonate radical and triplet excited state natural organic matter mediate the oxidation of pollutants in natural and engineered irradiated systems. In this work, one-electron oxidation potentials for various pollutants, including pesticides and pharmaceuticals, were computed, and literature data were used to develop linear free energy relationships (LFERs) for prediction of the second order reaction rate constants with these two reactive intermediates. For carbonate radical, separate relationships were necessary for compounds with and without resonance stabilization of the resulting radical. The predicted rate constants were, on average, within a factor of three of experimental values. Although the data set for triplet excited states was more limited, the results suggest that the one-electron oxidation potential is a viable descriptor variable for predictions of rate constants with triplet excited states as well.

One electron oxidation potential as a predictor of rate constants of organic pollutants with carbonate radical and triplet excited state organic matter

248th National Meeting (2014)

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