Ionic liquid modified electrodes. Unusual partitioning and diffusion effects of Fe(CN)64-/3- in droplet and thin layer deposits of 1-methyl-3-(2,6-(S)-dimethylocten-2-yl)-imidazolium tetrafluoroborate

J. D. Wadhawan, U. Schröder, A. Neudeck, S. J. Wilkins, R. G. Compton, F. Marken, C. S. Consorti, R. F. De Souza, J. Dupont

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141 Citations (SciVal)

Abstract

Room temperature ionic liquids exhibit unusual and, for electrochemical applications, promising properties such as ionic conductivity and non-volatility. Microdroplet and thin film deposits of an ionic liquid, 1-methyl-3-(2,6-(S)-dimethylocten-2-yl)-imidazolium tetrafluoroborate (MDIM+BF4-) on electrode surfaces are studied in order to assess the ability of aqueous ions to partition into the ionic liquid. Two complementary methodologies, deposition of ionic liquid onto a 4.9 mm diameter basal plane pyrolytic graphite electrode followed by voltammetric analysis and casting of an ionic liquid film onto a random array of 7 μm diameter carbon microelectrodes (RAM™ electrode) followed by chronoamperometry, are employed. The ability of hydrophilic ions to partition from the water phase into the ionic liquid phase is unexpected and is shown to depend strongly on (i) the type of ion, (ii) specific interaction of the ion with the ionic liquid, and (iii) the concentration of the supporting electrolyte. Voltammetric responses obtained for the reduction of Fe(CN)63- partitioned into microdroplet and thin film deposits of MDIM+BF4- indicate selective uptake of ferricyanide into the ionic liquid phase. Chronoamperometric experiments at RAM™ electrodes are used to quantify both the concentration of Fe(CN)63- in the ionic liquid and the diffusion coefficient.

Original languageEnglish
Pages (from-to)75-83
Number of pages9
JournalJournal of Electroanalytical Chemistry
Volume493
Issue number1-2
DOIs
Publication statusPublished - 10 Nov 2000

Funding

F.M. thanks the Royal Society for the award of a University Research Fellowship and New College for a Stipendiary Lectureship. U.S. acknowledges support from the Alexander von Humboldt foundation and S.J.W. thanks Glaxo-Wellcome and BBSRC for support via a CASE award. J.D.W. thanks Jon Ball and James Davis for helpful discussion. Further, Steven D. Bull is gratefully acknowledged for support with NMR experiments and Stephen Fletcher (CSIRO, Melbourne) for the generous loan of RAM TM electrodes.

Keywords

  • Diffusion
  • Ionic liquids
  • Liquid|liquid electrochemistry
  • Modified electrodes
  • Partitioning

ASJC Scopus subject areas

  • Analytical Chemistry
  • General Chemical Engineering
  • Electrochemistry

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