Adsorption kinetics of ionic surfactants after a large initial perturbation. Effect of surface elasticity

This theoretical study is devoted to the relaxation of surface tension of an ionic surfactant solution for submicellar concentrations. The effects of added nonamphiphilic electrolyte and counterion binding are taken into account. We consider a large initial deviation from equilibrium, which is defined as the formation of a new interface: there is no adsorbed surfactant and electric double layer at the initial moment. Next, the surfactant solution and its interface are allowed to relax without any subsequent perturbation. The electrodiffusion equations, which describe the adsorption kinetics, are nonlinear, and it is impossible to find a general analytical solution, especially in the case of large initial deviations. Nevertheless, the problem can be linearized in the asymptotic case of long times. The derived theoretical expressions show that the relaxation times in the cases of large and small initial perturbations are numerically close to each other. For that reason the relaxation time can be considered as a general kinetic property of the adsorption monolayer. The theory predicts also the slope of the experimental plot of dynamic surface tension vs inverse square root of time; this makes the theory useful for interpretation of experimental data. The theoretical expressions involve the surface (Gibbs) elasticity, whose definition for adsorption monolayers of soluble ionic surfactants is discussed in detail. The Gibbs elasticity of such monolayers is found to increase strongly with the rise of salt concentration. The derived asymptotic expressions are verified against an exact computer solution of the electrodiffusion problem, and excellent agreement is found.