Capillary coexistence and criticality in mesopores: Modification of the Kelvin theory

The classical model of capillary equilibrium in cylindrical pores is modified here by the introduction of molecular concepts and the solid fluid interaction potential. The new approach accurately predicts capillary coexistence and criticality, with results quantitatively matching those from density functional theory for nitrogen adsorption, while also predicting condensation pressures in agreement with reported experimental findings for MCM-41. The larger critical pore size for nitrogen adsorption in these materials, however, suggests a modification of the potential function parameters, evaluated here from data for hydroxylated silica.