Charge Regulation in Liquid Films Stabilized by Ionic Surfactants: Change in Adsorption with Film Thickness and Phase Transitions

When a liquid film is thinning, the charge and the potential of its surfaces change simultaneously due to the interaction between the two surfaces. This phenomenon is an example for charge regulation and has been known for half a century for systems featuring aqueous solutions in contact with metals, salts, biological surfaces covered by protolytes, etc. Few studies, however, investigated regulation in foam and emulsion films, where the charge is carried by soluble ionic surfactants. This work presents an analysis of the phenomenon for surfactants that follow the classical Davies adsorption isotherm. The electrostatic disjoining pressure <i>Π</i>_el was analyzed, and the Davies isotherm was shown to lead to <i>Π</i>_el ∝ <i>h</i>^-1/2 behavior at a small film thickness <i>h</i>. As usual, the charge regulation regime (constant chemical potential of the surfactant) corresponded to a dependence of <i>Π</i>_el on <i>h</i> between those for constant charge and constant electric potential regimes. The role of the background electrolyte was also studied. At the water-air interface, many ionic surfactants exhibit a surface phase transition. We show that the interaction between the two surfaces of a foam film can trigger the phase transition (i.e., the film changes its charge abruptly), and two films of different <i>h</i> values can coexist in equilibrium with each other-one covered by surfactant in the 2D gaseous state and another in the 2D liquid state.