Kinetic solvent effects on K+/K(Hg)electrodes in some dipolar aprotic solvent systems by cyclic voltammetry.
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概要
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The rate constants (<SUB>s</SUB><I>k</I><SUB>R</SUB>) of K<SUP>+</SUP>+e (Hg)\rightleftharpoonsK(Hg) in the dipolar aprotic solvents like propylene carbonate (PC), <I>N</I>, <I>N</I>-dimethylformamide (DMF), acetonitrile (AN), and their several binary mixtures have been determined at 25 °C on a hanging mercury drop electrode (HMDE) by cyclic voltammetric measurements. The observed nature of the cyclic voltammograms indicates that the reaction is quasi-reversible in the range of the sweep rates 1.0–0.01 V s<SUP>−1</SUP>. An insight to the composition profiles of the free energies of activation (Δ<I>G</I><SUP>≠</SUP>) relative to that in the chosen reference solvent (r) in the respective solvent (s) systems: −δΔ<I>G</I><SUP>≠</SUP>(=<I>RT</I>ln <SUB>s</SUB><I>k</I><SUB>R</SUB>⁄<SUB>r</SUB><I>k</I><SUB>R</SUB>) reveals that not only the solvation of K<SUP>+</SUP> but also that the transition state (TS) are responsible in dictating the rate constants. Also the solvation of TS is being guided by the dispersion interactions as well as the availability of the fraction of the free surfaces (1–θ<SUB>s</SUB>) for varying adsorption of the solvent molecules on the electrodes, all relative to that of the respective reference solvents.
- 公益社団法人 日本化学会の論文
著者
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Bhattacharya Swapan
Physical Chemistry Laboratories, Jadavpur University
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Kundu Kiron
Physical Chemistry Laboratories, Jadavpur University
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