With concern about emerging contaminants increasing, aqueous phase advanced oxidation processes (AOPs) have become attractive technologies for water purification. Although there is a great diversity of chemical structure within emerging contaminants, and various innovative technologies are being developed, HO� induced radical involved reaction mechanisms are common among AOPs. Peroxyl radical (ROO�) formation and degradation during AOP treatments are important in understanding the fates of intermediates and byproducts. Here we investigated peroxyl radical formation that results from an addition of molecular oxygen to a carbon-centered radical by considering both diffusion and chemical reactions. We successfully predicted associated overall reaction rate constants based on both experimentally obtained temperature-dependent rate constants and theoretically calculated aqueous phase free energies of activation. Investigations on the aqueous phase free energies of activation for subsequent uni-/bi-molecular degradation of peroxyl radicals revealed the favorable reaction pathways and quantitative insights in formation of intermediates and byproducts.

Mechanistic insights in peroxyl radical formation and degradation and associated reaction rate constants prediction in aqueous phase advanced oxidation processes

245th National Meeting (2013)

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