The kinetics of adsorption and desorption to the air/water surface in submicellar surfactant solutions has been studied by means of a dynamic technique in which the surface is subjected to small amplitude sinusoidal compression and expansion. In all cases studied so far a diffusion controlled mechanism was found, characterised by a frequency dependent surface tension variation and a phase difference between applied area change and resulting surface tension change of at most 45°. When such experiments are carried out above the critical micellar concentration a characteristically different behaviour is observed with a much steeper frequency dependence of the surface tension change and with phase differences between 45 and 90°.

Experiments of this type, carried out for solutions of some nonionic surfactants can be quantitatively interpreted on the basis of a model in which the diffusional exchange of monomers between surface and bulk and the exchange between monomers in the intermicellar solution and micelles are consecutive processes. It is shown that establishment of micellar equilibrium under certain conditions can be a fairly slow process with relaxation times of the order of seconds, although the actual exchange of monomers with micelles could well be several orders of magnitude faster.

Some implications of the presence of micelles on the general nature of dissipative processes near a surface are discussed.