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The voltammetry for the reduction of 2-nitrotoluene at a gold microdisk electrode is reported in two ionic liquids: trihexyltetradecylphosphonium tris(pentafluoroethyl)trifluorophosphate ([P14,6,6,6][FAP]) and 1-ethyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide ([Emim][NTf2]). The reduction of nitrocyclopentane (NCP) and 1-nitrobutane (BuN) was investigated using voltammetry at a gold microdisk electrode in the ionic liquid [P14,6,6,6][FAP]. Simulated voltammograms, generated through the use of Butler–Volmer theory and symmetric Marcus–Hush theory, were compared to experimental data, with both theories parametrizing the data similarly well. An experimental value for the Marcusian parameter, λ, was also determined in all cases. For the reduction of 2-nitrotoluene, this was 0.5 ± 0.1 eV in both solvents, while for NCP and BuN in [P14,6,6,6][FAP], it was 2 ± 0.1 and 5 ± 0.1 eV, respectively. This is attributed to the localization of charge on the nitro group and the primary nitro alkyl’s increase...

The amperometric detection of oxygen under moist (humid) conditions via Clark cell type devices using Room Temperature Ionic Liquids (RTILs) as electrochemical solvents can be complicated, because the number of electrons transferred in the electrode reaction varies between one and two as a function of the humidity. The problem is avoided through the use of phosphonium cation based ionic liquids in which the alkyl group of the phosphonium cation has acidic protons which are rapidly abstracted by superoxide ions. Thus the reduction of O2 is to be trapped at the one electron level on the micro-electrode voltammetric timescale, allowing the amperometric detection of oxygen under humid conditions to be quantitatively viable. © 2014 Elsevier B.V.