Effect of Water on Interfacial Chemical Properties of Nonionic Surfactants in Hydrophobic Ionic Liquid bmimPF6

We studied the effect of water addition on interfacial properties and aggregate behavior of nonionic surfactants (polyoxyethylene alkyl ether; CnEm) in an ionic liquid (1-butyl-3-methylimidazolium hexafluorophosphate; bmimPF(6)). When a small amount of water was added to mixtures of CnEm and bmimPF(6), two breaking points (cad, cac2) were observed in the surface tension/CnEm concentration plots, suggesting the formation of two kinds of aggregates. This two-step aggregate formation was also confirmed by the fluorescence probe method using pyrene. The particle size of the aggregates measured by dynamic light scattering (DLS) was around 200 nm at cad, and decreased to 4 nm above cac2. These results, together with freeze-fracture TEM observations, showed that the aggregate formed at cad was water in bmimPF(6) emulsions, which then transformed to micelles solubilizing water in the palisade layer above cac2. This concentration-dependent aggregate formation was supported thermodynamically by studying the dependence of cacs on temperature and alkyl and POE chain lengths of the surfactant.