Liquid chromatography of polyoxyethylenes under critical conditions: A thermodynamic study

Polyethylene glycols (PEG), fatty alcohol ethoxylates (FAE) and fatty acid polyglycol esters were analyzed by liquid chromatography under critical conditions (LCCC) on typical reversed phase columns in mobile phases consisting of methanol–water and acetone–water in the region of the critical adsorption point (CAP) for the oxyethylene unit. Critical conditions can be adjusted by varying the mobile phase composition or temperature. In methanol–water the temperature dependence is almost negligible, while it is much more pronounced in acetone–water. Critical conditions for the oxyethylene unit were realized on octadecyl phases in methanol–water containing 85.8 wt.% methanol and in acetone–water at 89.6 wt.% acetone. In the van’t Hoff plots the logarithm of the distribution coefficient was plotted versus the reciprocal temperature. In all plots straight lines were found, from slope and intercept of which the entropy and enthalpy changes were calculated. The relation of the thermodynamic parameters −ΔG/RT, −ΔH/RT, and ΔS/R to the numbers of A and B chain units in block copolymers AB and BAB at the CAP for A is studied both theoretically and experimentally. Various approaches for obtaining the critical temperature are discussed.