Kinetic Studies of the Electron Transfer Reaction in Iron(II) and Iron(III) Systems. VI. Reaction in <I>N</I>,<I>N</I>-Dimethylformamide
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概要
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The electron transfer reaction between Fe(II) and Fe(III) in <I>N</I>,<I>N</I>-dimethylformamide (DMF) was found to be influenced by the presence of perchloric acid, chloride ion, and water in the reaction system. This suggests that the reaction involves chemical species such as partially hydrated iron, its deprotonated iron, and FeCl<SUP>2+</SUP> and FeCl<SUB>2</SUB><SUP>+</SUP>. The individual rate constants in DMF, containing a small amount of water, are <I>k</I><SUB>0</SUB>=33.6 M<SUP>−1</SUP>s<SUP>−1</SUP> for Fe<SUP>2+</SUP>–Fe<SUP>3+</SUP>, <I>k</I><SUB>1</SUB>=1.2×10<SUP>2</SUP> M<SUP>−1</SUP>s-<SUP>−1</SUP> for Fe<SUP>2+</SUP>–FeCl<SUP>2+</SUP>, and <I>k</I><SUB>2</SUB>=∼10<SUP>3</SUP> M<SUP>−1</SUP>s<SUP>−1</SUP> for Fe<SUP>2+</SUP>–FeCl<SUB>2</SUB><SUP>+</SUP> at μ=0.20 M and 25°C. The formation constant for FeCl<SUP>2+</SUP> was determined to be <I>K</I><SUB>1</SUB>=(2.0±0.3)×10<SUP>4</SUP> M<SUP>−1</SUP> at μ=0.20 M and 25°C. In the mixed solvents of DMF and water, the apparent rate constant exhibited a minimum at a certain water concentration. The activation parameters for the reactions Fe<SUP>2+</SUP>–Fe<SUP>3+</SUP> and Fe<SUP>2+</SUP>–FeCl<SUP>2+</SUP> are <I>ΔH</I><SUB>0</SUB><SUP>\neweq</SUP>=8.3 kcal/mol, <I>ΔS</I><SUB>0</SUB><SUP>\neweq</SUP>=−24 cal/deg·mol, <I>ΔH</I><SUB>1</SUB><SUP>\neweq</SUP>=4.5 kcal/mol, and <I>ΔS</I><SUB>1</SUB><SUP>\neweq</SUP>=−34 cal/deg·mol, respectively. The results are compared with those in H<SUB>2</SUB>O, D<SUB>2</SUB>O, and DMSO.
- 公益社団法人 日本化学会の論文
著者
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Wada Goro
Department of Chemistry, Faculty of Science, Nara Women s University
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Ohsaki Kyoko
Department of Chemistry, Nara Women's University
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Sahira Yoshiko
Department of Chemistry, Nara Women's University
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Shinoda Fusako
Department of Chemistry, Nara Women's University
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Shinoda Fusako
Department of Chemistry, Nara Women's University
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Sahira Yoshiko
Department of Chemistry, Nara Women's University
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