Liquid-liquid phase separation in solutions of ionic liquids: phase diagrams, corresponding state analysis and...

Phase diagrams of ionic solutions of the ionic liquid C(18)mim(+)NTF(2)(-) (1-n-octadecyl-3-methyl imidazolium bistrifluormethylsulfonylimide) in decalin, cyclohexane and methylcyclohexane are reported and compared with that of solutions of other imidazolium ionic liquids with the anions NTF(2)(-), Cl(-) and BF4(-) in arenes, CCl(4), alcohols and water. The phase diagrams are analysed presuming Ising criticality and taking into account the asymmetry of the phase diagrams. The resulting parameters are compared with simulation results for equal-sized charged hard spheres in a dielectric continuum, the restricted primitive model (RPM) and the primitive model (PM) that allows for ions of different size. In the RPM temperature scale the critical temperatures vary almost linearly with the dielectric permittivity of the solvent. The RPM critical temperatures of the solutions in non-polar solvents are very similar, somewhat below the RPM value. Correlations with the boiling temperatures of the solvents and a dependence on the length of the side chain of the imidazolium cations show that dispersion interactions modify the phase transition, which is mainly determined by Coulomb forces. Critical concentrations, widths of the phase diagrams and the slopes of the diameter are different for the solutions in protic and aprotic solvents. The phase diagrams of the solutions in alcohols and water get a lower critical solution point when represented in RPM variables.