Ionic phase transitions in non-ideal systems

Abstract

We construct an explicitly solvable Landau mean-field theory for volume phase transitions of confined or fixed ions driven by relative concentrations of divalent and monovalent counterions. Such phase transitions have been widely studied in ionic gels, where the mechanism relies on self-attraction or elasticity of a network. We find here that non-ideal behavior of ions in aqueous solution can in theory drive phase transitions without a self-attracting or elastic network. We represent non-ideality by a Debye-H\"uckel-like power-law activity, or correlation free energy, and retain a mechanical self-repulsion to avoid runaway collapse due to the non-ideal term. Within this model we find a continuous line of gas-liquid-type critical points, connecting a purely monovalent, divalent-sensitive critical point at one extreme with a divalent, monovalent-sensitive critical point at the other. An alternative representation of the Landau functional handles the second case. We include a formula for electrical potential, which may be a convenient proxy for critically varying volume. Our relatively simple mean-field formulation may facilitate explorations of tunable critical sensitivity in areas such as ion detection technology and biological osmotic control.