A combined theoretical and experimental study on the oxidation of fulvic acid by the sulfate radical anion

被引：76

作者：

David Gara, Pedro M. ^{[2
]}

Bosio, Gabriela N. ^{[2
]}

Gonzalez, Monica C. ^{[2
]}

Russo, Nino ^{[1
]}

Michelini, Maria del Carmen ^{[1
]}

Pis Diez, Reinaldo ^{[3
]}

Martire, Daniel O. ^{[2
]}

机构：

[1] Univ Calabria, Dipartimento Chim, I-87030 Arcavacata Di Rende, Italy

[2] Univ Nacl La Plata, Fac Ciencias Exactas, Inst Invest Fisicoquim Teor & Aplicadas, RA-1900 La Plata, Argentina

[3] Univ Nacl La Plata, Fac Ciencias Exactas, CEQUINOR, CONICET, RA-1900 La Plata, Argentina

来源：

PHOTOCHEMICAL & PHOTOBIOLOGICAL SCIENCES | 2009年 / 8卷 / 07期

关键词：

MOLECULAR-WEIGHT; KINETICS; SOLVENTS; SO4;

D O I：

10.1039/b900961b

中图分类号：

Q5 [生物化学]; Q7 [分子生物学];

学科分类号：

071010 ; 081704 ;

摘要：

The kinetics of the reaction of sulfate radicals with the IHSS Waskish peat fulvic acid in water was investigated in the temperature range from 289.2 to 305.2 K. The proposed mechanism considers the reversible binding of the sulfate radicals by the fulvic acid. The kinetic analysis of the data allows the determination of the thermodynamic parameters Delta G degrees = -10.2 kcal mol(-1), Delta H degrees = -16 kcal mol(-1) and Delta S degrees = -20.3 cal K-1 mol(-1) for the reversible association at 298.2 K. Theoretical (DFT) calculations performed with the Buffle model of the fulvic acids support the formation of H-bonded adducts between the inorganic radicals and the humic substances. The experimental enthalpy change compares well with the theoretical values found for some of the investigated adducts.

引用

页码：992 / 997

页数：6

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