The effect of water content on room-temperature ionic liquids (RTILs) was studied by Karl Fischer titration and cyclic voltammetry in the following ionic liquids: tris(P-hexyl)tetradecylphosphonium trifluorotris(pentafluoroethyl)phosphate [P14,6,6,6][NTf2], N-butyl-N-methyl-pyrrolidinium bis(trifluoromethylsulfonyl)imide [C4mpyrr][NTf2], 1-hexyl-3-methylimidazolium tris(perfluoroethyl)trifluorophosphate [C6mim][FAP], 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [C4mim][NTf2], 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [C4dmim][NTf2], N-hexyltriethylammonium bis(trifluoromethylsolfonyl)imide [N6,2,2,2][NTf2], 1-butyl-3-methylimidazolium hexafluorophosphate [C4mim][PF6], 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [C2mim][NTf2], 1-butyl-3-methylimidazolium tetrafluoroborate [C4mim][BF4], 1-hexyl-3-methylimidazolium iodide [C4mim][I], 1-butyl-3-methylimidazolium trifluoromethylsulfonate [C4mim][OTf], and 1-hexyl-3-methylimidazolium chloride [C6mim][Cl]. In addition, electrochemically relevant properties such as viscosity, conductivity, density, and melting point of RTILs are summarized from previous literature and are discussed. Karl Fisher titrations were carried out to determine the water content of RTILs for vacuum-dried, atmospheric, and wet samples. The anion in particular was found to affect the level of water uptake. The hydrophobicity of the anions adhered to the following trend: [FAP]− > [NTf2]− > [PF6]− > [BF4]− > halides. Cyclic voltammetry shows that an increase in water content significantly narrows the electrochemical window of each ionic liquid. The electrochemical window decreases in the following order: vacuum-dried > atmospheric > wet at 298 K > 318 K > 338 K. The anodic and cathodic potentials vs ferrocene internal reference are also listed under vacuum-dried and atmospheric conditions. The data obtained may aid the selection of a RTIL for use as a solvent in electrochemical applications.

Ferrocene, Fc, and cobaltocenium hexafluorophosphate, CcPF6, have been recommended for use as internal reference redox couples in room-temperature ionic liquids (RTILs), as well as in more conventional aprotic solvents. In this study, the electrochemical behavior of Fc and CcPF6 is reported in eight commonly used RTILs; [C2mim][NTf2], [C4mim][NTf2], [C4mim][BF4], [C4mim][PF6], [C4mim][OTf], [C4mim][NO3], [C4mpyrr][NTf2], and [P14,6,6,6][FAP], where [C n mim]+ = 1-butyl-3-methylimidazolium, [NTf2]- = bis(trifluoromethylsulfonyl)imide, [BF4]- = tetrafluoroborate, [PF6]- = hexafluorophosphate, [OTf]- = trifluoromethylsulfonate, [NO3]- = nitrate, [C4mpyrr]+ = N-butyl-N-methylpyrrolidinium, [P14,6,6,6 ]+ = tris(n-hexyl)-tetradecylphosphonium and [FAP]- = trifluorotris(pentafluoroethyl)phosphate, over a range of concentrations and temperatures. Solubilities and diffusion coefficients, D, of both the charged and neutral species were determined using double potential-step chronoamperometry, and CcPF6 (36.5−450.0 mM) was found to be much more soluble than Fc (27.5−101.8 mM). It was observed that classical Stokes−Einstein diffusional behavior applies for Fc and CcPF6 in all eight RTILs. Diffusion coefficients of Fc and CcPF6 were calculated at a range of temperatures, and activation energies calculated. It was also determined that D for Fc and CcPF6 does not change significantly with concentration. This supports the use of both Fc and CcPF6 to provide a well-characterized and model redox couple for use as a voltammetric internal potential reference in RTILs contrary to previous literature reports in the former case.

A review of electrochemistry in ionic liquids is presented, highlighting some particular examples, with the aim to compare any similarities and differences observed in RTILs to that observed in conventional solvents. The presence of impurities such as halide and water on the electrochemical window and viscosity of RTILs is discussed. Some fundamental electrochemical studies relating to mass transport, heterogeneous electron transfer kinetics and double-layer capacitance are compared to similar studies in conventional solvents, and the suitability of RTILs as solvents in electrochemical experiments is considered. The application of RTILs as replacements for conventional solvents in gas sensors is reviewed, focussing on the electrochemistry observed in RTILs for the following gases: oxygen, a mixture of oxygen and carbon dioxide, and ammonia. The low volatility and high thermal stability of RTILs renders them advantageous for the development of robust sensors under extreme conditions. Finally, the possibility for use of RTILs as solvents in electrosynthesis is discussed, focussing on two examples: the reactivity of electrogenerated bromine with cyclohexene, and the reduction of 4-nitrophenol. It is obvious that RTILs have the ability to offer many advantages over traditional solvents in the field of electrochemistry.

The recent literature is surveyed to explore the nature of voltammetry in room temperature ionic liquids. The extent of similarities with conventional electrochemical solvents is reported and some surprising differences are noted.

The electrochemical oxidation of dissolved hydrogen gas has been studied in a range of room-temperature ionic liquids (RTILs), namely [C(2)mim][NTf(2)], [C(4)mim][NTf(2)], [N(6,2,2,2)][NTf(2)], [P(14,6,6,6)][NTf(2)], [C(4)mpyrr][NTf(2)], [C(4)mim][BF(4)], [C(4)mim][PF(6)], [C(4)mim][OTf], and [C(6)mim]Cl on a platinum microdisk electrode of diameter 10 microm. In all cases, except [C(6)mim]Cl, a broad quasi-electrochemically reversible oxidation peak between 0.3 to 1.3 V vs Ag was seen prior to electrode activation ([C(6)mim]Cl showed an almost irreversible wave). When the electrode was pre-anodized ("activated") at 2.0 V vs Ag for 1 min, the peak separations became smaller, and the peak shape became more electrochemically reversible. It is thought that the electrogenerated protons chemically combine with the anions (A-) of the RTIL. The appearance and position of the reverse (reduction) peak on the voltammograms is thought to depend on three factors: (1) the stability of the protonated anion, HA, (2) the position of equilibrium of the protonation reaction HA<==> H+ + A- , and (3) any follow-up chemistry, e.g., dissociation or reaction of the protonated anion, HA. This is discussed for the five different anions studied. The reduction of HNTf(2) was also studied in two [NTf(2)]- -based RTILs and was compared to the oxidation waves from hydrogen. The results have implications for the defining of pKa in RTIL media, for the development of suitable reference electrodes for use in RTILs, and in the possible amperometric sensing of H2 gas.

Ionic Liquids are salts that are liquid at (or just above) room temperature. They possess several advantageous properties (e.g. high intrinsic conductivity, wide electrochemical windows, low volatility, high thermal stability and good solvating ability), which make them ideal as non-volatile electrolytes in electrochemical sensors. This mini-review article describes the recent uses of ionic liquids in electrochemical sensing applications (covering the last 3 years) in the context of voltammetric sensing at solid/liquid, liquid/liquid interfaces and carbon paste electrodes, as well as their use in gas sensing, ion-selective electrodes, and for detecting biological molecules, explosives and chemical warfare agents. A comment on the future direction and challenges in this field is also presented.

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a b s t r a c tThe oxidation of hydrogen was studied at an activated platinum micro-electrode by cyclic voltammetry in the following ionic liquids: [C 2 mim][NTf 2 ], [C 4 mim][NTf 2 ], [N 6,2,2,2 ][NTf 2 ], [P 14,6,6,6 ][NTf 2 ], [C 4 mim][OTf], [C 4 mim][BF 4 ], [C 4 mim][PF 6 ], [C 4 mim][NO 3 ], [C 6 mim]Cl and [C 6 mim][FAP](where ½C n mim þ ¼ 1-alkyl-3-methylimidazolium, ½N 6;2;2;2 þ ¼ n-hexyltriethylammonium, ½P 14;6;6;6 þ ¼ trisðn-hexyltetradecylÞ phosphonium; ½NTf 2 À ¼ bisðtrifluoromethylsulfonylÞamide, ½OTf À ¼ trifluoromethlysulfonate and ½FAP À ¼ trisðperfluoroethylÞtrifluorophosphate). Activation of the Pt electrode was necessary to obtain reliable and reproducible voltammetry. After activation of the electrode, the H 2 oxidation waves were nearly electrochemically and chemically reversible in ½C n mim½NTf 2 ionic liquids, chemically irreversible in [C 6 mim]Cl and [C 4 mim][NO 3 ], and showed intermediate characteristics in OTf À , ½BF 4 À , ½PF 6 À , [FAP] À and other ½NTf 2 À -based ionic liquids. These differences reflect the contrasting interactions of protons with the respective RTIL anions. The oxidation peaks are reported relative to the half-wave potential of the cobaltocenium/cobaltocene redox couple in all ionic liquids studied, giving an indication of the relative proton interactions of each ionic liquid. A preliminary temperature study (ca. 298-333 K) has also been carried out in some of the ionic liquids. Diffusion coefficients and solubilities of hydrogen at 298 K were obtained from potential-step chronoamperometry, and there was no relationship found between the diffusion coefficients and solvent viscosity. RTILs possessing ½NTf 2 À and [FAP] À anions showed the highest micro-electrode peak currents for the oxidation in H 2 saturated solutions, with[C 4 mim][NTf 2 ] being the most sensitive. The large number of available RTIL anion/cation pairs allows scope for the possible electrochemical detection of hydrogen gas for use in gas sensor technology.