Solvent Effect of Methanol on the Rate of Formation Reaction of Monochloroiron(III) Complex in Aqueous Solution
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概要
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The rate constants of the formation reaction of FeCl<SUP>2+</SUP> complex from Fe(III) and Cl<SUP>−</SUP> ion were measured in water-methanol mixed solvents by use of a stopped-flow spectrophotometer. The apparent rate constant <I>k</I> is dependent upon the acid concentration of the medium, indicating that the reaction can proceed through two parallel paths, Fe<SUP>3+</SUP>+Cl<SUP>−</SUP> (<I>k</I><SUB>1</SUB>) and Fe(OH)<SUP>2+</SUP>+Cl<SUP>−</SUP> (<I>k</I><SUB>H</SUB>). Both <I>k</I><SUB>1</SUB> and <I>k</I><SUB>H</SUB> increase with the increase in the mole fraction of methanol in the medium, <I>x</I><SUB>M</SUB>. Since <I>k</I><SUB>H</SUB> is much larger and is consequently much more accurately determined than <I>k</I><SUB>1</SUB> considerations were mainly made on the nature of <I>k</I><SUB>H</SUB>. According to the dependence of <I>k</I><SUB>H</SUB> on the dielectric constant of the medium, it was found that the activation free energy of the Fe(OH)<SUP>2+</SUP>+Cl<SUP>−</SUP> reaction consists of the electrical and non-electrical parts and that the dimension of the activated complex corresponds approximately to the distance of the outer-sphere approach between the reacting species. These facts are therefore in favor of an outer-sphere mechanism in the anation reactions of iron (III) by simple anions.
- 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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Kobayashi Yaeko
Department of Chemistry, Nara Women's University
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