Desorption kinetics of surfactants at fluid interfaces by novel coaxial capillary pendant drop experiments

Abstract

Abstract Surfactants appear in multiphase fluid systems in which the interface and the adjacent bulk phase have been removed from equilibrium. Here, a new method is described for the measurement of rate constants of desorption of surface-active materials from fluid/fluid interfaces and the extent to which adsorption is reversible: the coaxial capillary pendant drop experimental technique. Kinetic constants are determined by desorption experiments in pendant drops in which the interface adjacent to a surfactant solution is removed from equilibrium by replacing the subphase of the drop with pure water. Further, we demonstrate that although the rate of subphase exchange is comparatively slow with respect to the desorption timescale, it is possible to resolve desorption processes which occur under local equilibrium with the adjacent bulk phase from those that are determined in part by sorption kinetics. Experiments which measure the desorption kinetic coefficient, α, using a homologous series of n-alkyl (C8, C10, C12, C14) dimethyl phosphine oxides are presented.