Effect of Convection on Formation of Adsorbed Surfactant Film under Dynamic Change of Solution Surface Area

The dynamics of the formation of a surface phase in aqueous solutions of surfactants in a tray with the Langmuir barrier system during one compression–expansion cycle of the interface boundary is investigated both experimentally and theoretically. Organic salts of fatty acids such as potassium laurate, caprylate, and acetate, which are members of the same homologous series, were used as surfactants. It is experimentally determined that the dependence of the surface pressure increment measured under the maximum compression of the surface on the volume concentration has a maximum, the position of which is different for all the studied surfactant solutions. It is shown that the position of the maximum corresponds to the concentration value at which a saturated monolayer of surfactant molecules is formed at the interface boundary. A theoretical model that considers the effect of the forced convection arisen in the bulk of the solution upon changing the surface area is proposed for the interpretation of the experimental results. The model allows one to render the main kinetic characteristics of the adsorption/desorption processes involving the compounds under study. A good agreement between the theoretical and experimental results is observed, but there is a discrepancy between them when diffusion is considered to be the only way surfactant molecules are transferred into the bulk phase. Based on the data, a new method for determination of the Langmuir–Shishkovsky constant is proposed.