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We show that solubilization in microemulsion droplets is best described as a combination of interfacial adsorption and internal absorption. We progressively add solute to a Winsor type I system, and simultaneously measure the amount of solute at the oil–water interface and its effect on the interfacial curvature. We determine the relationship between the effective packing parameter and the amount of solute adsorbed at the oil–water interface. For four solutes, a significant amount of oil is co-extracted with solute into the interfacial film. Moreover, we show that solubilization in microemulsions can be characterized by two physical quantities with precise meaning: (1) the increase in interfacial area per molecule of adsorbed solute and (2) the number of oil molecules co-extracted with each solute molecule into the interfacial film. To quantify these effects, we introduce the constant interfacial thickness (CIT) model. It provides a general relationship between curvature, packing and interfacial composition in oil/water/surfactant/solute mixtures. Finally, we show that these results can be used to calculate the free energy of transfer of solute and oil from the droplet core to the interface.

Some general principles of surfactant self-assembly are rationalised in order to give a short introduction to the use of phase diagrams for binary (two components) and ternary (three components) systems. Finally models for solubilisation are considered to be understood within the frame of those general packing principles: volume, surface and curvature conservation.