Thermophysical Properties of Imidazolium-Based Ionic Liquids

Abstract

Ionic liquids (ILs) are salts that are liquid at low temperatures, usually including the region around room temperature. They are under intense investigation, especially as replacement solvents for reactions and separations, since they exhibit negligible vapor pressure and would not, therefore, contribute to air pollution. Clearly, basic thermophysical properties are vital for design and evaluation for these applications. We present density as a function of temperature, melting temperatures, glass-transition temperatures, decomposition temperatures, and heat capacities as a function of temperature for a series of 13 of the popular imidazolium-based ILs. The ionic liquids investigated here are 1-butyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium hexafluorophosphate, 1-butyl-3-methylimidazolium chloride, 1-butyl-3-methylimidazolium bromide, 1-butyl-3-methylimidazolium dicyanamide, 1-butyl-3-methylimidazolium trifluoromethanesulfonate, 1-butyl-3-methylimidazolium tris(trifluoromethylsulfonyl)methide, 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, 2,3-dimethyl-1-ethylimidazolium bis(trifluoromethylsulfonyl)imide, 2,3-dimethyl-1-propylimidazolium bis(trifluoromethylsulfonyl)imide, 1-butyl-2,3-dimethylimidazolium tetrafluoroborate, and 1-butyl-2,3-dimethylimidazolium hexafluorophosphate. The properties follow quite reasonable trends. For instance, density decreases as the length of the alkyl chain on the cation increases. For a given cation, the density increases as the molecular weight of the anion increases for the anions studied here. Many of the ILs tend to subcool easily, forming glasses at very low temperatures rather than exhibiting crystallization or melting transitions. The thermal stability increases with increasing anion size, and heat capacities increase with temperature and increasing number of atoms in the IL.