Global Phase Behavior of Imidazolium Ionic Liquids and Compressed 1,1,1,2-Tetrafluoroethane (R-134a)

Novel processes involving ionic liquids with refrigerant gases have recently been developed. Here, the complete global phase behavior has been measured for the refrigerant gas, 1,1,1,2-tetrafluoroethane (R-134a) and 1-n-alkyl-1-3-methyl-imidazolium ionic liquids with the anions hexafluorophosphate [PF6], tetrafluoroborate [BF4] and bis(trifluoromethylsulfonyl)imide [Tf2N] from -0 degrees C to 105 degrees C and to 33 MPa. All of the systems studied were Type V from the classification scheme of Scott-van Konynenburg with regions of vapor-liquid equilibrium, miscible/critical regions, vapor-liquid-liquid equilibrium, and upper and lower critical endpoints (UCEP and LCEP). The effect of the alkyl chain length has been investigated, for ethyl-([EMIm]), n-butyl-([BMIm]), and n-hexyl-([HMIm]). With increasing chain length, the temperature of the lower critical end points increases and pressure at the mixture critical points decrease. With a common cation, the temperature of the LCEP increased and the mixture critical point pressures decreased in the order of [BF4], [PF6], and [Tf2N]. (c) 2008 American Institute of Chemical Engineers AIChE J, 55: 486-493, 2009