Reactions of phosphate radicals with monosubstituted benzenes.: A mechanistic investigation

被引：24

作者：

Rosso, JA ^{[1
]}

Caregnato, P ^{[1
]}

Mora, VC ^{[1
]}

Gonzalez, MC ^{[1
]}

Mártire, DO ^{[1
]}

机构：

[1] Natl Univ La Plata, Fac Ciencias Exactas, INIFTA, RA-1900 La Plata, Argentina

来源：

HELVETICA CHIMICA ACTA | 2003年 / 86卷 / 07期

关键词：

D O I：

10.1002/hlca.200390203

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

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[(PO3)(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 H2PO4(.), HPO4.-, and PO4.2- and the logarithm of the dissociation constant K-a for H3PO4, H2PO4-, and HPO42- was found. A general mechanism is proposed (Scheme 1), which accounts for the experimental results.

引用

页码：2509 / 2524

页数：16

共 32 条

[1] Kinetic study of the reactions of chlorine atoms and Cl2•- radical anions in aqueous solutions.: 1.: Reaction with benzene [J].

Alegre, ML ;

Geronés, M ;

Rosso, JA ;

Bertolotti, SG ;

Braun, AM ;

Mártire, DO ;

Gonzalez, MC .

JOURNAL OF PHYSICAL CHEMISTRY A, 2000, 104 (14) :3117-3125

[2] The phenoxy radical: UV spectrum and kinetics of gas-phase reactions with itself and with oxygen [J].

Berho, F ;

Lesclaux, R .

CHEMICAL PHYSICS LETTERS, 1997, 279 (5-6) :289-296

[3] AROMATIC HYDROXYLATION .8. A RADIATION CHEMICAL STUDY OF THE OXIDATION OF HYDROXYCYCLOHEXADIENYL RADICALS [J].

BUXTON, GV ;

LANGAN, JR ;

SMITH, JRL .

JOURNAL OF PHYSICAL CHEMISTRY, 1986, 90 (23) :6309-6313

[4] Reactions of phosphate radicals with substituted benzenes. A structure-reactivity correlation study [J].

Cencione, SS ;

Gonzalez, MC ;

Martire, DO .

JOURNAL OF THE CHEMICAL SOCIETY-FARADAY TRANSACTIONS, 1998, 94 (19) :2933-2937

[5] PULSE RADIOLYSIS STUDIES .1. TRANSIENT SPECTRA AND REACTION-RATE CONSTANTS IN IRRADIATED AQUEOUS SOLUTIONS OF BENZENE [J].

DORFMAN, LM ;

BUHLER, RE ;

TAUB, IA .

JOURNAL OF CHEMICAL PHYSICS, 1962, 36 (11) :3051-&

[6] Formation of nitroaromatic compounds in advanced oxidation processes: Photolysis versus photocatalysis [J].

Dzengel, J ;

Theurich, J ;

Bahnemann, DW .

ENVIRONMENTAL SCIENCE & TECHNOLOGY, 1999, 33 (02) :294-300

[7] RADIATION-INDUCED HOMOLYTIC AROMATIC-SUBSTITUTION .2. HYDROXYLATION AND PHENYLATION OF BENZENE [J].

EBERHARDT, MK .

JOURNAL OF PHYSICAL CHEMISTRY, 1974, 78 (18) :1795-1797

[8] 2,2-DIMETHOXY-2-PHENYLACETOPHENONE - PHOTOCHEMISTRY AND FREE-RADICAL PHOTOFRAGMENTATION [J].

FISCHER, H ;

BAER, R ;

HANY, R ;

VERHOOLEN, I ;

WALBINER, M .

JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2, 1990, (05) :787-798

[9]

GOULD ES, 1959, MECH STRUCTURE ORGAN, P113

[10] ANISOLE RADICAL CATION REACTIONS IN AQUEOUS-SOLUTION [J].

HOLCMAN, J ;

SEHESTED, K .

JOURNAL OF PHYSICAL CHEMISTRY, 1976, 80 (14) :1642-1644

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