Confinement effects and deviations from ideality of vapours at the adsorbed phase/gas interface

In the present work, confinement effects are evidenced both from the side of the adsorbed phase as well as from the gas phase of the same fluid. A generalization of these confinement effects is proposed by using the corresponding states principle as a classical tool to compare adsorption phenomena. The lowest closure point of hysteresis loop has been chosen because of the ease with which its position can be determined. On the gas side of confinement effects, deviations of the Clausius–Clapeyron curves in reduced coordinates are interpreted in terms of polarisability and those are perfectly correlated using analogous of Pitzer acentric factors in confined environments. On the adsorbed phase side of confinement effects, enthalpic excesses are demonstrated during capillary condensation phenomena and are perfectly fitted by a predictive macrothermodynamical model.