Kinetic studies of the electron transfer reactions in iron(II) and iron(III) systems. XI. Electron transfer reaction between aquairon(II) and tris(1,10-phenanthroline)iron(III) in water mixed with methanol, ethanol, 1-propanol, and ethylene glycol.
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概要
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The electron transfer reaction Fe<SUP>2+</SUP><SUB>aq</SUB>+Fe(phen)<SUB>3</SUB><SUP>3+</SUP>→Fe<SUP>3+</SUP><SUB>aq</SUB>+Fe(phen)<SUB>3</SUB><SUP>2+</SUP> has been investigated in order to find out the influence of the dielectric nature of media on the reaction rates, by the method of stopped-flow spectrophotometry. As the reaction media, were used aqueous mixtures with various alcohols, such as methanol, ethanol, 1-propanol, and ethylene glycol at their various mole fractions <I>x</I>. The second-order rate constant <I>k</I> grows larger approximately linearly with the increase in <I>x</I>, in a sequence: methanol<ethylene glycol<ethanol<1-propanol. When In <I>k</I> is plotted against <I>D</I><SUP>−1</SUP> (the reciprocal dielectric constant), all points come together on a single straight line with a positive slope, indifferent to the kinds of the alcohols used. This fact suggests that the reaction proceeds through three successive elementary processes, Fe<SUP>2+</SUP><SUB>aq</SUB>+Fe(phen)<SUB>3</SUB><SUP>3+</SUP>\overseti→[Fe(H<SUB>2</SUB>O)<SUB>6</SUB><SUP>2+</SUP>·Fe(phen)<SUB>3</SUB><SUP>3+</SUP>]\oversetii→[Fe(H<SUB>2</SUB>O)<SUB>6</SUB><SUP>3+</SUP>·Fe(phen)<SUB>3</SUB><SUP>2+</SUP>]\oversetiii→Fe<SUP>3+</SUP><SUB>aq</SUB>+Fe(phen)<SUB>3</SUB><SUP>2+</SUP>, in which Process i is the formation of an outer-sphere ion-pair between two reacting ions, Process ii the intramolecular electron transfer in the intermediate complex, and Process iii the separation of the ion-pair into the product ions, the last being the rate-determining step. The reaction scheme is compared with that of the reaction Fe<SUP>2+</SUP><SUB>aq</SUB>+Fe(OH)<SUP>2+</SUP>→Fe(OH)<SUP>2+</SUP>+Fe<SUP>2+</SUP><SUB>aq</SUB>, where the first step of the ion-pair formation is rate-determining.
著者
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Wada Goro
Department of Chemistry, Nara Women s University
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Takahashi Kumiko
Department of Chemistry, Faculty of Science, Nara Women's University
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Isobe Masako
Department of Chemistry, Faculty of Science, Nara Women's University
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Wada Goro
Department of Chemistry, Faculty of Science, Nara Women s University
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