Adsorption-desorption kinetics of surfactants at liquid surfaces.

The paper discusses adsorption and desorption energy barriers for macroscopic interfaces of surfactant solutions. Literature data suggest that adsorption and desorption are not always fully diffusion controlled. Apart from electrostatic barriers that lead to strong deviations, other types of barriers are less easy to identify, because smaller deviations from diffusion controlled mechanisms are evidenced. Complete models involving both diffusion and sorption barriers are very complex and involve many adjustable parameters, making the data analysis frequently unreliable. Empirical equations of state are used in most cases, although they are inaccurate, especially close to the cmc. The variation of sorption energies with surface concentration is not accurately described in the models. Finally, convection can mask the effect of sorption energy barriers. Experiments are presented to illustrate the main difficulties encountered.