Extraction of electrode kinetic parameters from microdisc voltammetric data measured under transport conditions intermediate between steady-state convergent and transient linear diffusion as typically applies to room temperature ionic liquids

Alexander S. Barnes, Emma I. Rogers, Ian Streeter, Leigh Aldous, Christopher Hardacre, Richard G. Compton

    Research output: Contribution to journalArticlepeer-review

    Abstract

    The extraction of electrode kinetic parameters for electrochemical couples in room-temperature ionic liquids (RTILs) is currently an area of considerable interest. Electrochemists typically measure electrode kinetics in the limits of either transient planar or steady-state convergent diffusion for which the voltammetic response is well understood. In this paper we develop a general method allowing the extraction of this kinetic data in the region where the diffusion is intermediate between the planar and convergent limits, such as is often encountered in RTILs using microelectrode voltammetry. A general working surface is derived, allowing the inference of Butler-Volmer standard electrochemical rate constants for the peak-to-peak potential separation in a cyclic voltammogram as a function of voltage scan rate. The method is applied to the case of the ferrocene/ ferrocenium couple in [C2mim][N(Tf) 2] and [C4mim][N(Tf)2].

    Original languageEnglish
    Pages (from-to)7560-7565
    Number of pages6
    JournalThe Journal of Physical Chemistry Part B: Condensed Matter, Materials, Surfaces, Interfaces & Biophysical
    Volume112
    Issue number25
    DOIs
    Publication statusPublished - 26 Jun 2008

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