Salt and solvent effects on the kinetics of the oxidation of the excited state of the [Ru(bPY)3]2+ complex by S2O82-

被引：12

作者：

Lopes-Costa, T ^{[1
]}

Lopez-Cornejo, P ^{[1
]}

Villa, I ^{[1
]}

Perez-Tejeda, P ^{[1
]}

Prado-Gotor, R ^{[1
]}

Sanchez, F ^{[1
]}

机构：

[1] Univ Seville, Fac Quim, Dept Quim Fis, E-41012 Seville, Spain

来源：

JOURNAL OF PHYSICAL CHEMISTRY A | 2006年 / 110卷 / 12期

关键词：

D O I：

10.1021/jp055189l

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

The title reaction was studied in different reaction media: aqueous salt solutions (NaNO3) and water-cosolvent (methanol) mixtures. The observed rate constants. k(obs), show normal behavior in the solutions containing the electrolyte, that is, a negative salt effect. However, the solvent effect is abnormal, because a decrease of the rate constant is observed when the dielectric constant of the reaction medium decreases. These effects (the normal and the abnormal) can be explained using the Marcus-Hush treatment for electron transfer reactions. To apply this treatment, the true, unimolecular, electron-transfer rate constants, k(et), have been obtained from kobs after calculation of the rate constants corresponding to the formation of the encounter complex from the separate reactants, k(D), and the dissociation of this complex, k(-D). This calculation has been carried out using an exponential mean spherical approach (EMSA).

引用

页码：4196 / 4201

页数：6

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