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    Electrochemical behaviour of dissolved proton species in room temperature ionic liquids.

    118709_Electrochemical%20%20behaviour%20DebbieCOIL3.pdf (1.731Mb)
    Access Status
    Open access
    Authors
    Silvester, Debbie
    Compton, R.
    Date
    2009
    Type
    Conference Paper
    
    Metadata
    Show full item record
    Citation
    Silvester, Debbie and Compton, Richard. 2009. Electrochemical behaviour of dissolved proton species in room temperature ionic liquids, 3rd International Conference on Ionic Liquids, Jun 1 2009. Cairns, Queensland: Australia
    Source Title
    Electrochemical Behaviour of Dissolved Proton Species in Room Temperature Ionic Liquids
    Source Conference
    3rd International Conference on Ionic Liquids COIL
    Faculty
    Department of Applied Chemistry
    School of Science
    Faculty of Science and Engineering
    School
    Nanochemistry Research Institute (Research Institute)
    URI
    http://hdl.handle.net/20.500.11937/25164
    Collection
    • Curtin Research Publications
    Abstract

    Understanding the nature of dissolved species in ionic liquids is important, particularlywhen using them as reaction media to replace volatile organic solvents. Electrochemicaltechniques such as cyclic voltammetry and potential-step chronoamperometry are verypowerful tools used to study electrochemical reactions, elucidate mechanisms andquantify diffusion parameters. These techniques have been used in various studies on thebehaviour of dissolved species in ionic liquids. Particularly, the behaviour of hydrogen or?protic? species in ionic liquids can give some insight into the hydrogen bondingcharacteristics of the ionic liquids (individual cation/anion combination) and eventuallythe pH properties of the solvents. We have looked 1,2 at the direct oxidation of hydrogengas in ten ionic liquids with various cation/anion combinations. The mechanism involvesthe two-electron oxidation of hydrogen to the electrogenerated proton, which is thoughtto then combine with the anion (A-) of the ionic liquid. The appearance and position ofthe reverse (reduction) peak on the voltammogram is thought to depend on three factors:(1) the stability of the solvated proton, HA, (2) the position of equilibrium of theprotonation reaction HA = H+ + A-, and (3) any follow-up chemistry e.g. dissociation orreaction of the solvated proton, HA. This is discussed for all ten ionic liquids studied.Solubilities of hydrogen gas are found to be in the range ca. 3-10 mM and diffusioncoefficients are calculated to be of the order 10-10 m2 s-1, with no evidence that the Stokes-Einstein law applies for the diffusion of hydrogen gas in ionic liquids.

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