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Reactions of Phosphate Radicals with Monosubstituted Benzenes. A Mechanistic Investigation
Author(s) -
Rosso Janina A.,
Caregnato Paula,
Mora Verónica C.,
Gonzalez Mónica C.,
Mártire Daniel O.
Publication year - 2003
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/hlca.200390203
Subject(s) - chemistry , radical , reaction rate constant , flash photolysis , dissociation (chemistry) , aqueous solution , phosphate , dissociation constant , kinetics , photodissociation , photochemistry , medicinal chemistry , reaction mechanism , hammett equation , organic chemistry , catalysis , biochemistry , physics , receptor , quantum mechanics
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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