Conformal Sites Theory for Adsorbed Films on Energetically Heterogeneous Surfaces

Abstract

We present a conformal sites theory for a solid substrate whose surface is both geometrically and energetically heterogeneous, and that interacts with an adsorbed film. The theory is based on a perturbation expansion for the grand potential of a real system with a rough surface about that of a reference system with an ideal reference surface, thus mapping the real system onto a much simpler interfacial system. The expansion is in powers of the intermolecular potential parameters, and leads to mixing rules for the potential parameters of the reference system. Grand canonical Monte Carlo (GCMC) simulations for the adsorption of argon at 87.3 K, carbon dioxide at 273 K and water vapor at 298 K on heterogeneous carbon surfaces are investigated to explore the limits of applicability of the theory. Simulation results indicate that the theory works well with typical asymmetry of the potential parameters in the force field. However, care should be taken when applying the theory to strongly associating fluids, and in the low-pressure region where the active surface sites play an important role. The conformal sites theory can be used to predict the adsorption properties, and to characterize the solid substrate by taking advantage of the corresponding states principle. Other possible applications are also discussed.