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    Oxidation of Several p-Phenylenediamines in Room Temperature Ionic Liquids: Estimation of Transport and Electrode Kinetic Parameters

    Access Status
    Fulltext not available
    Authors
    Long, J.
    Silvester, Debbie
    Barnes, A.
    Rees, N.
    Aldous, L.
    Hardacre, C.
    Compton, R.
    Date
    2008
    Type
    Journal Article
    
    Metadata
    Show full item record
    Citation
    Long, J. and Silvester, D. and Barnes, A. and Rees, N. and Aldous, L. and Hardacre, C. and Compton, R. 2008. Oxidation of Several p-Phenylenediamines in Room Temperature Ionic Liquids: Estimation of Transport and Electrode Kinetic Parameters. Journal of Physical Chemistry C. 112 (17): pp. 6993-7000.
    Source Title
    Journal of Physical Chemistry C
    DOI
    10.1021/jp800235t
    ISSN
    1932-7447
    URI
    http://hdl.handle.net/20.500.11937/43925
    Collection
    • Curtin Research Publications
    Abstract

    The electrochemical oxidation of N,N,N‘,N‘-tetramethyl-p-phenylenediamine (TMPD) has been studied by cyclic voltammetry and potential step chronoamperometry at 303 K in five ionic liquids, namely [C2mim][NTf2], [C4mim][NTf2], [C4mpyrr][NTf2], [C4mim][BF4], and [C4mim][PF6] (where [Cnmim]+ = 1-alkyl-3-methylimidazolium, [C4mpyrr]+ = N-butyl-N-methylpyrrolidinium, [NTf2]- = bis(trifluoromethylsulfonyl)imide, [BF4]- = tetrafluoroborate, and [PF6]- = hexafluorophosphate). Diffusion coefficients, D, of 4.87, 3.32, 2.05, 1.74, and 1.34 × 10-11 m2 s-1 and heterogeneous electron-transfer rate constants, k0, of 0.0109, 0.0103, 0.0079, 0.0066, and 0.0059 cm s-1 were calculated for TMPD in [C2mim][NTf2], [C4mim][NTf2], [C4mpyrr][NTf2], [C4mim][BF4], and [C4mim][PF6], respectively, at 303 K. The oxidation of TMPD in [C4mim][PF6] was also carried out at increasing temperatures from 303 to 343 K, with an activation energy for diffusion of 32.3 kJ mol-1. k0 was found to increase systematically with increasing temperature, and an activation energy of 31.4 kJ mol-1 was calculated. The study was extended to six other p-phenylene-diamines with alkyl/phenyl group substitutions. D and k0 values were calculated for these compounds in [C2mim][NTf2], and it was found that k0 showed no obvious relationship with the hydrodynamic radius, r.

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