Curvature dependence of the electrolytic liquid-liquid interfacial tension

Abstract

The interfacial tension of a liquid droplet surrounded by another liquid in the presence of microscopic ions is studied as a function of the droplet radius. An analytical expression for the interfacial tension is obtained within a linear Poisson–Boltzmann theory and compared with numerical results from nonlinear Poisson–Boltzmann theory. The excess liquid-liquid interfacial tension with respect to the pure salt-free liquid-liquid interfacial tension is found to decompose into a curvature-independent part due to short-ranged interfacial effects and a curvature-dependent electrostatic contribution. Several curvature-dependent regimes of different scalings of the electrostatic excess interfacial tension are identified. Symmetry relations of the interfacial tension upon swapping droplet and bulk liquid are found to hold in the low-curvature limit, which, e.g., lead to a sign change of the excess Tolman length. For some systems a low-curvature expansion up to the second order turns out to be applicable if and only if the droplet size exceeds the Debye screening length in the droplet, independent of the Debye length in the bulk.