Lower consolute boundaries of the nonionic surfactant C8E5 in aqueous alkali halide solutions: an approach to reproduce the effects of alkali halides on the cloud-point temperature.

In the temperature-composition phase diagram of the nonionic surfactant n-octyl-hydroxypenta(oxyethylene), C(8)E(5), there are three principal curves; the one for the critical micelle concentration (cmc), the one delineating the existence of the hexagonal phase, and then the lower consolute boundary (lcb). In this work it is clarified how the presence of the alkali halides NaF, LiCl, NaCl, NaBr and NaI in the aqueous solutions, up to high molalities, change the lcb temperature-position and shape. The lcbs are obtained from measurements of cloud-point temperatures. Rather marked anion-controlled shifts are observed in the boundary temperature-position, and the order of the anions is in accordance with the prediction of the Hofmeister series. Also the shape of the boundary is affected in an anion-specific way, so that the largest changes are found with the strongest salting-out agent. The separation point varies in distinctly non-linear manners with the molality of the studied alkali halides. An approach is presented that can reproduce the effects of the alkali halides on the cloud-point temperature of C(8)E(5) and a poly(ethylene oxide) polymer, at low amounts of the macroentities. In this approach use is made of the known behaviour of the electrolytes at the air/water surface and the virial expansion, to account for the initial salting-out/-in effect and the variation of the effect with electrolyte molality.