Bulletin of the Korean Chemical Society

  • 제17권2호
  • /
  • Pages.162-167
  • /
  • 1996
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  • 0253-2964(pISSN)
  • /
  • 1229-5949(eISSN)
대한화학회 (Korean Chemical Society)
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Channel Electrode Voltammetric and In Situ Electrochemical ESR Studies of Comproportionation of Methyl Viologen in Acetonitrile

  • Lee, Ji U ;
  • John C. Eklund ;
  • Robert A. W. Dryfe ;
  • Richard G. Compton
  • 발행 : 19960200
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초록

Two redox processes of methyl viologen (+2/+, +/0) in acetonitrile were investigated by using channel electrode voltammetric and in situ electrochemical ESR methods. Two separated unequal plateau currents of the first (+2/+) and second (+/0) redox processes of the viologen were observed in the channel electrode voltammograms and showed a cube-root depedndence on the electrolyte flow rate, respectively. The simple Levich analysis resulted in two different diffusion coefficients of $D_{+2}=2.2{\times}10^{-5}\;cm^2/s$ and $D_+=3.0{\times}10^{-5}cm^2/s$ from the limiting currents. In situ electrochemical ESR studies were performed for the monocation radicals generated at the potentials of the two plateau currents in the electrolyte flow range $1.3{\times}10^{-1}{\geq}v_f{\geq}2.7{\times}10^{-3}\;cm^3/s$. Backward implicitfinite difference method was employed to simulate the electrochemical kinetic problem of two sequential electron transfers ($MV^{+2}+e{\leftrightarrows}MV^+,\;MV^{+}+e{\leftrightarrows}MV^0$) coupled with reversible comproportionation ($MV^{2+}+MV^0{{\leftrightarrows}^{k_f}_{k_b}}2MV^+$). $k_f$ was found to be greater than ($10^6M^{-1}s^{-1}.

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참고문헌

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피인용 문헌

  1. ESR and ENDOR investigations of the degenerate electron exchange reactions of various viologens in solution. Solvent dynamical effects vol.30, pp.2, 1996, https://doi.org/10.1007/bf03166715
  2. 산화환원 화학 종이 단 분자 층으로 화학 흡착된 전극에서의 전기화학적 정류 vol.10, pp.1, 2007, https://doi.org/10.5229/jkes.2007.10.1.043