Toward an Understanding of the Mechanisms behind the Formation of Liquid–liquid Systems formed by Two Ionic Liquids

Biphasic systems composed of aprotic ionic liquids (ILs) allow the development of new separation processes constituted only by nonvolatile solvents. Six pairs of cholinium- and phosphonium-based ILs were found to be able to form biphasic systems, and the respective liquid–liquid phase diagrams were determined. Although IL anions do not seem to control the phase separation phenomenon, they play an important role in defining the size of the biphasic region. A linear dependence of the ILs mutual solubilities with the IL anions volume was found, supporting the relevance of the entropy of mixing. With the exception of the system formed by ILs with a common anion, the remaining liquid–liquid systems display a significant ion exchange extent between the phases, which inversely depends on the ILs cohesive energy. It is finally shown that four-phase systems with a remarkable performance in the separation of mixtures of dyes can be prepared.