Abnormal salt effects on a cation/anion reaction. An interpretation based on the analysis of the components of the experimental rate constant

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Title:Abnormal salt effects on a cation/anion reaction. An interpretation based on the analysis of the components of the experimental rate constant
Creators:
Sánchez, Francisco
Perez-Tejeda, Pilar
Jimenez, Rafael
Villa, Isaac
Journal or Publication Title:
Collection of Czechoslovak Chemical Communications, 74, 4, pp. 627-641
Uncontrolled Keywords:Electron transfer, Thermodynamics, Marcus–Hush treatment, Kinetics, Abnormal salt effect, <i>T</i>-Jump measurements, Ferricyanide oxidation, Ruthenium complexes

Abstract

Salt effects (NaNO<sub>3</sub>) on the kinetics of the reactions [Fe(CN)<sub>6</sub>]<sup>3–</sup> + [Ru(NH<sub>3</sub>)<sub>5</sub>(pyz)]<sup>2+</sup> = [Fe(CN)<sub>6</sub>]<sup>4–</sup> + [Ru(NH<sub>3</sub>)<sub>5</sub>(pyz)]<sup>3+</sup> (pyz = pyrazine) were studied through <i>T</i>-jump measurements. An abnormal (positive) salt effect on the forward reaction was observed and a normal (negative) effect on the reverse one. These facts imply an asymmetric behavior of anion/cation reactions depending on the charge sign of the oxidant and reductant. The results can be rationalized by using the Marcus–Hush treatment for electron-transfer reactions after decomposition of the experimental rate constants into their components.

Title:Abnormal salt effects on a cation/anion reaction. An interpretation based on the analysis of the components of the experimental rate constant
Creators:
Sánchez, Francisco
Perez-Tejeda, Pilar
Jimenez, Rafael
Villa, Isaac
Uncontrolled Keywords:Electron transfer, Thermodynamics, Marcus–Hush treatment, Kinetics, Abnormal salt effect, <i>T</i>-Jump measurements, Ferricyanide oxidation, Ruthenium complexes
Divisions:Life and Chemical Sciences > Institute of Organic Chemistry and Biochemistry > Collection of Czechoslovak Chemical Communications
Journal or Publication Title:Collection of Czechoslovak Chemical Communications
Volume:74
Number:4
Page Range:pp. 627-641
ISSN:0010-0765
E-ISSN:1212-6950
Publisher:Institute of Organic Chemistry and Biochemistry
Related URLs:
URLURL Type
http://dx.doi.org/10.1135/cccc2008200UNSPECIFIED
ID Code:4190
Item Type:Article
Deposited On:14 Apr 2009 12:50
Last Modified:14 Apr 2009 10:50

Citation

Sánchez, Francisco; Perez-Tejeda, Pilar; Jimenez, Rafael; Villa, Isaac (2009) Abnormal salt effects on a cation/anion reaction. An interpretation based on the analysis of the components of the experimental rate constant. Collection of Czechoslovak Chemical Communications, 74 (4). pp. 627-641. ISSN 0010-0765

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