Nonequilibrium Phase Transformations at the Air−Liquid Interface

Abstract

A theoretical model is presented for the formation of an ordered phase close to the air-liquid interface of an open binary aqueous solution. The chemical potential of water in the liquid phase is, in general, not equal to the chemical potential of water in the ambient atmosphere. There are therefore nonequilibrium conditions close to the air-liquid interface. There is also a gradient in the chemical potential of water, which could lead to the formation of a new interfacial phase. The formation of an interfacial phase is analyzed in terms of the equilibrium phase behavior corresponding to the local water chemical potential. The possibility of forming an interfacial phase is strongly dependent on the ambient conditions, bulk composition, and diffusive transport properties of the phases in question. Explicit calculations are presented for the formation of a lamellar liquid-crystalline phase close to the air-liquid interface of an isotropic surfactant solution with parameters chosen from the sodium bis(2-ethylhexyl)sulfosuccinate (AOT)/water system. We consider the relevance of the model to neutron reflectivity studies of the interface between air and surfactant/water systems, as well as to surfactant/polymer/water systems.