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Reactions of Phosphate Radicals with Monosubstituted Benzenes. A Mechanistic Investigation

✍ Scribed by Janina A. Rosso; Paula Caregnato; Verónica C. Mora; Mónica C. Gonzalez; Daniel O. Mártire

Publisher
John Wiley and Sons
Year
2003
Tongue
German
Weight
213 KB
Volume
86
Category
Article
ISSN
0018-019X

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✦ Synopsis

Abstract

The kinetics and reaction mechanism of phosphate radicals with substituted benzenes, PhX (X=OH, Me, H, Cl, MeO, and CHO), were studied by flash photolysis and continuous irradiation of aqueous solutions containing potassium peroxodiphosphate (K~4~[(PO~3~)~2~O~2~]). 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 H~2~PO~4~^.^, HPO~4~^.−^, and PO~4~^.2−^ and the logarithm of the dissociation constant K~a~ for H~3~PO~4~, $\rm{ H_2 PO_4^ -}$, and $\rm{ HPO_4^{2 - }}$ was found. A general mechanism is proposed (Scheme 1), which accounts for the experimental results.

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