Reactions of Phosphate Radicals with Monosubstituted Benzenes. A Mechanistic Investigation

JANINA A. ROSSO; PAULA CAREGNATO; VERÓNICA C. MORA; MÓNICA C. GONZALEZ; DANIEL O. MÁRTIRE

HELVETICA CHIMICA ACTA

Wiley.

Lugar: Zurich. Suiza.; Año: 2003 vol. 86 p. 2509 - 2524

0018-019X

The kinetics and reaction mechanism of phosphate radicals with substituted benzenes, PhX (X = HO, Me, H, Cl, MeO, and CHO), were studied by flash photolysis and continuous irradiation of aqueous solutions containing potassium peroxodiphosphate (K4[(PO3)2O2]). The rate constants for the reactions of phosphate radicals with the aromatic contaminants PhX were measured and the reaction intermediates and products detected. A correlation between the logarithm of the rate constant for every substrate with H2PO4., HPO4.-, and PO4.2- and the logarithm of the dissociation constant Ka for H3PO4, H2PO4- and HPO42- was found. A general mechanism is proposed (Scheme 1), which accounts for the experimental results. winDirVariable="C:/WINDOWS"