Effect of Water on the Electrochemical Window and Potential Limits of Room-Temperature Ionic Liquids

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 [P(14,6,6,6)][NTf(2)], N-butyl-N-methyl-pyrrolidinium bis(trifluoromethylsulfonyl)imide [C(4)mpyrr][NTf(2)], 1-hexyl-3-methylimidazolium tris(perfluoroethyl)trifluorophosphate [C(6)mim][FAP], 1-butyl3-methylimidazolium bis(trifluoromethylsulfonyl)imide [C(4)mim][NTf(2)], 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [C(4)dmim][NTf(2)], N-hexyltriethylammonium bis(trifluoromethylsolfonyl)imide [N(6,2,2,2)][NTf(2)], 1-butyl-3-methylirnidazolium hexafluorophosphate [C(4)mim][PF(6)], F6], 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [C(2)mim][NTf(2)], 1-butyl-3-methylimidazolium tetrafluoroborate [C(4)mim][BF(4)], 1-hexyl-3-methylimidazolium iodide [C(4)mim][I], 1-butyl-3-methylimidazolium trifluoromethylsulfonate [C(4)mim][OTf], and 1-hexyl-3-methylimidazolium chloride [C(6)mim][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](-) > [NTf(2)](-) > [PF(6)](-) > [BF(4)](-) > 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.