Studies of the ruthenium complexes. XIII. Kinetic studies of electron-transfer reactions between aquapentaammineruthenium(II) and halopentaammineruthenium(III) comlexes.
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概要
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Kinetic measurements of the electron-transfer reactions from Ru(OH<SUB>2</SUB>)(NH<SUB>3</SUB>)<SUB>5</SUB><SUP>2+</SUP> to RuX(NH<SUB>3</SUB>)<SUB>5</SUB><SUP>2+</SUP>, where X=Cl, Br, and I, have been made in aqueous solutions. The reaction rate is independent of the hydrogen-ion concentration, while it is greatly influenced by the ionic strength of the reaction solution. The rate constants were determined to be 147, 172, and 293 M<SUP>−1</SUP>s<SUP>−1</SUP> for the reaction systems of chloro- bromo- and iodopentaammineruthenium(III) ions respectively at 25 °C in a solution with an ionic strength of 0.0944 M. The activation parameters, (Δ<I>H</I><SUP>\neweq</SUP> kcal mol<SUP>−1</SUP>, Δ<I>S</I><SUP>\neweq</SUP> cal K<SUP>−1</SUP> mol<SUP>−1</SUP>), were (19.4, 16), (18.9, 15), and (11.2, −10) respectively, for the same systems. From the facts that the reaction rate decreases in the order of I>Br>Cl and that the ionic strength of the solution strongly affects the reaction rate, it may be concluded that the present electron-transfer reactions proceed by means of an outersphere-type mechanism.
- 公益社団法人 日本化学会の論文
著者
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SAKAKI Shigeyoshi
Department of Applied Chemistry & Biochemistry, Faculty of Engineering, Kumamoto University
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Yamashita Tomohisa
Department Of Chemistry Graduate School Of Science Tohoku University
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Ohyoshi Akira
Department Of Applied Chemistry Faculty Of Engineering Kumamoto University
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Yoshikuni Kenichiro
Department of Industrial Chemistry, Faculty of Engineering, Kumamoto University
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Yamashita Tomohisa
Department of Industrial Chemistry, Faculty of Engineering, Kumamoto University
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Ohtsuyama Hidetoshi
Department of Industrial Chemistry, Faculty of Engineering, Kumamoto University
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