Electrical double layers at the oil/water interface

This review presents the historical development and current status of the theory of the electrical double layer at a liquid/liquid interface. It gives rigorous thermodynamic definitions of all basic concepts related to liquid interfaces and to the electrical double layer. The difference between the surface of a solid electrode and the interface of two immiscible electrolyte solutions (ITIES) is analyzed in connection to their electrical properties. The most important classical relationships for the electrical double layer are presented and critically discussed. The generalized adsorption isotherm is derived. After a short review of the classical Gouy-Chapman and Verwey-Niessen models, more recent developments of the double layer theory are presented. These include effects of variable dielectric permittivity, nonlocal electrostatics, hydration forces, the modified Poisson-Boltzmann equation and the ion-dipole plasma. The relative merits of different theories are estimated by comparing them with computer simulation of the ITIES and electrical double layer. Special attention is given to the structure of ITIES and its variation due to adsorption of ions and amphiphilic molecules.