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Aqueous Phase Kinetic Studies Involving Intermediates of Environmental Interest: Phosphate Radicals and Their Reactions with Substituted Benzenes

This manuscript describes our research work devoted to the understanding of the aqueous phase reactions of phosphate and polyphosphate radicals. Inorganic phosphate and polyphosphate radicals were generated after photolysis of peroxo-diphosphate, tripolyphosphate and pyrophosphate ions. The reactions of SO4•-radicals with P2O74- and P3O105- are also discussed. The logarithm of the bimolecular rate constants for the reactions of the three phosphate radicals (H2PO4• HPO4•- PO4•2-) with substituted benzenes are discussed in terms of Hammett correlations and a reaction mechanism is proposed. Phenoxyl type radical formation from the reactions of H2PO4• and HPO4•- radicals with phenol, chlorobenzene, and α, α, α-trifluorotoluene (TFT) supports the contribution of an addition pathway yielding a phosphate adduct with the substituted benzene. Additional information on the absorption spectra and decay kinetics of the hydroxycyclohexadienyl radicals of chlorobenzene and TFT is also given.