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

doi:10.1021/jp711897b

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

Chemistry

Research output: Contribution to journal › Article › peer-review

47 Citations (Scopus)

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 language	English
Pages (from-to)	7560-7565
Journal	JOURNAL OF PHYSICAL CHEMISTRY B
Volume	112
Issue number	25
DOIs	https://doi.org/10.1021/jp711897b
Publication status	Published - 26 Jun 2008

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Barnes, A. S., Rogers, E. I., Streeter, I., Aldous, L., Hardacre, C., & Compton, R. G. (2008). 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. JOURNAL OF PHYSICAL CHEMISTRY B, 112(25), 7560-7565. https://doi.org/10.1021/jp711897b

Barnes, Alexander S. ; Rogers, Emma I. ; Streeter, Ian et al. / 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. In: JOURNAL OF PHYSICAL CHEMISTRY B. 2008 ; Vol. 112, No. 25. pp. 7560-7565.

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title = "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",

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].",

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Barnes, AS, Rogers, EI, Streeter, I, Aldous, L, Hardacre, C & Compton, RG 2008, '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', JOURNAL OF PHYSICAL CHEMISTRY B, vol. 112, no. 25, pp. 7560-7565. https://doi.org/10.1021/jp711897b

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. / Barnes, Alexander S.; Rogers, Emma I.; Streeter, Ian et al.
In: JOURNAL OF PHYSICAL CHEMISTRY B, Vol. 112, No. 25, 26.06.2008, p. 7560-7565.

Research output: Contribution to journal › Article › peer-review

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AU - Aldous, Leigh

AU - Hardacre, Christopher

AU - Compton, Richard G.

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AB - 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].

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Barnes AS, Rogers EI, Streeter I, Aldous L, Hardacre C, Compton RG. 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. JOURNAL OF PHYSICAL CHEMISTRY B. 2008 Jun 26;112(25):7560-7565. doi: 10.1021/jp711897b