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Bulletin of the Korean Chemical Society (BKCS)

ISSN 0253-2964(Print)
ISSN 1229-5949(Online)
Volume 17, Number 2
BKCSDE 17(2)
February 20, 1996 

Channel Electrode Voltammetric and In Situ Electrochemical ESR Studies of Comproportionation of Methyl Viologen in Acetonitrile
Chi-Woo Lee*, John C. Eklund, Robert A. W. Dryfe, Richard G. Compton
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 × 10-5 cm2/s and D+=3.0 × 10-5 cm2/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 1.3×10-1 ≥ vf ≥ 2.7×10-3 cm3/s. Backward implicitfinite difference method was employed to simulate the electrochemical kinetic problem of two sequential electron transfers (MV+2 + e ↔ MV+, MV+ + e ↔ MV0) coupled with reversible comproportionation (MV+2 + MV0 kf↔kb 2MV+). kf was found to be greater than 106M-1s-1.
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