Pressure effects on both the curvature and phase behavior of water-in-oil microemulsions (swollen reverse micelles) are predicted with a unified classical and molecular thermodynamic theory developed by Peck et al. (this issue). The theory is used to identify quantitatively the roles of the intramicellar interfacial interactions and micelle-micelle interactions. A supplementary molecular model is used to calculate the strength of attractive intermicellar interactions over a wide range of conditions, based on previous small-angle neutron-scattering data. An important distinction is made between systems with a small water-to-oil ratio and those where the water-to-oil ratio is much larger, on the order of unity. In the latter the micelle radius is controlled primarily by intramicellar interfacial interactions, specifically the enthalpic propane-surfactant tail interactions. For a small water-to-oil ratio, the micelle radius is limited by attractive micelle-micelle interactions. As pressure increases, the radius increases but eventually reaches a maximum governed by the intramicellar interfacial interactions. There is good agreement between the predictions and experiments over a wide range of water-to-oil ratios.
Peck, dg johnston, kp