Statistical Thermodynamics of Phase Transitions in Surfactant Monolayer Films

Abstract

ABSTRACTA lattice statistical mechanical method has recently been developed and used to predict structural and thermodynamic properties of fluid phases of surfactant monolayer films of uniform chain length. This mean-field approach is extended here to examine films of mixed chain length. As in the earlier work, a fluid-fluid (LC-LE) phase transition is predicted to occur at high surface densities. This transition is found to exhibit non-ideal mixing behavior, ranging from positive azeotropy to phase separation (in the LC phase) as the difference in chain lengths increases. In contrast, the phase diagram in the liquid-gas (LEG) transition region is predicted to exhibit almost ideal behavior, with a nearly linear bubble-point curve.