Kinetics of adsorption from micellar solutions

Previous studies on surfactant adsorption mostly deal with dilute systems without aggregation in the bulk phase. At the same time, micellar solutions can be more important from the point of view of applications. If one attempts to estimate the equilibrium adsorption, neglecting the influence of micelles can lead to reasonable results. The situation differs for non-equilibrium systems when the adsorption rate can increase by an order of magnitude at the increase of the surfactant concentration beyond the CMC. A critical survey of various models describing the influence of micelles on adsorption kinetics at the liquid–gas interface is given and the theoretical results are compared with existing experimental data. The theories proposed for the case of large deviations from the equilibrium are usually based on some unjustifiable assumptions and can describe the kinetic dependencies of adsorption in only a limited number of situations. Consequently, only rough estimates of the kinetic coefficients of micellization can be obtained from experimental data on dynamic surface tension. More rigorous equations can be derived if the system only deviates slightly from equilibrium. In the latter case, the agreement between theoretical and experimental results is essentially better and measurements of the dynamic surface elasticity of micellar solutions allow us to study the micellization kinetics.