The analysis of dynamic surface tension of sodium alkyl sulphate solutions, based on asymptotic equations of adsorption kinetic theory

Abstract

We analysed existing and newly derived asymptotic solutions of the adsorption kinetic equations for the liquid phase interface in the regions of infinitely small and infinitely great surface lifetimes ( t) for the cases of one and of a few surfactants, on non-deforming and deforming surfaces, under non-stationary, stationary and quasi-stationary conditions, assuming either the diffusion adsorption mechanism or mixed adsorption mechanism. It was proved that in the region t → ∞, the adsorption barrier does not influence the dynamic surface tension σ, but the role of surface-active contaminants is significant. In contrast, in the region t → 0, the role of contaminants is small, but the adsorption barrier influences the dynamic surface tension substantially. The dynamic surface tension of sodium alkyl sulphate solutions was measured by the maximum bubble pressure method, in the t range 0.001–10 s. In the region t → ∞ we obtained good agreement of experimental results with asymptotic formulae. The diffusion adsorption mechanism of the surfactant solutions studied was confirmed and we also estimated the concentration values of the surfactant admixtures. Small additions of the more active surfactant sodium tetradecyl sulphate to sodium dodecyl sulphate substantially influences the shape of the σ— t curve in the region t → ∞, increasing (in full accordance with theoretical considerations) the tangent value of the curve inclination of the dependence of σ on t −1/2. In the regions t → 0, long-chained high molecular weight sodium alkyl sulphates adsorb according to the diffusion mechanism, whereas for sodium decyl and dodecyl sulphates the existence of the adsorption barrier was confirmed. We corroborated experimentally the absence of any influence of surfactant admixtures on the values of dynamic surface tension at t → 0.