Langmuir, Vol.20, No.6, 2503-2511, 2004
Modeling of the adsorption kinetics of surfactants at the liquid-fluid interface of a pendant drop
This paper presents a theoretical model for simulating the adsorption kinetics of a surfactant at the liquid-fluid interface of a pendant drop. The diffusion equation is solved numerically by applying the semidiscrete Galerkin finite element method to obtain the time-dependent surfactant concentration distributions inside the pendant drop and inside the syringe needle that is used to form the pendant drop. With the obtained bulk surfactant concentration distributions, the adsorption at the interface is determined by using the conservation law of mass. It should be noted that the theoretical model developed in this study considers the actual geometry of the pendant drop, the depletion process of the surfactant inside the pendant drop, and the mass transfer of the surfactant from the syringe needle to the pendant drop. The present pendant-drop model is applied to study the adsorption kinetics of surfactant C10E8 (octaethylene glycol mono n-decyl ether) at the water-air interface of a pendant drop. The numerical results show that the Ward and Tordai equation, which was derived for adsorption from a semi-infinite surfactant solution to a planar interface, is unsuitable for interpreting the dynamic surface or interfacial tension data measured by using the pendant-drop-shape techniques, especially at low initial surfactant concentrations. The spherical-drop model, which assumes the pendant drop to be a perfectly spherical drop with the same drop volume, can be used to interpret the dynamic surface or interfacial tension data for pendant drops either with high initial surfactant concentrations or with low initial surfactant concentrations in short adsorption durations only. For pendant drops with low initial surfactant concentrations in long adsorption durations, the theoretical model developed in this study is strongly recommended.