We examine an electric double layer containing an antagonistic salt in an aqueous mixture, where the cations are small and hydrophilic but the anions are large and hydrophobic. In this situation, a strong coupling arises between the charge density and the solvent composition. As a result, the anions are trapped in an oil-rich adsorption layer on a hydrophobic wall. % while the cations are expelled from it. We then vary the surface charge density $\sigma$ on the wall. For $\sigma>0$ the anions remain accumulated, but for $\sigma<0$ the cations are attracted to the wall with increasing $|\sigma|$. Furthermore, the electric potential drop $\Psi(\sigma)$ is nonmonotonic when the solvent interaction parameter $\chi(T)$ exceeds a critical value $\chi_c$ determined by the composition and the ion density in the bulk. This leads to a first order phase transition between two kinds of electric double layers with different $\sigma$ and common $\Psi$. In equilibrium such two layer regions can coexist. The steric effect due to finite ion sizes is crucial in these phenomena.
Categories: cond-mat.soft cond-mat.mtrl-sci cond-mat.stat-mech physics.chem-ph