| Abstract: | A recently elucidated aspect of adsorption, compression in confined phases, is discussed. Grand Canonical Monte Carlo simulations were performed for the adsorption of Lennard–Jones molecules and new details of intermolecular interactions in adsorbed layers are analysed. It is shown that a strong attraction to a surface can cause adsorption compression not only in the first layer, but also in higher layers. Compression of the first layer creates a pattern of active sites; the second layer tends to be commensurate with this pattern and has density higher than that of a ‘free’ layer. This pattern propagates to higher layers. However, there is a wide range of chemical potentials where the first layer is compressed and the second layer is not yet formed. It was found that transition to adsorption compression results in oscillations of the isosteric heat of adsorption. These oscillations are determined by a combination of (a) changes in adsorbed layers’ structure and (b) exchange of molecules between layers. In particular, at high affinity to adsorbent, the adsorption isotherm for the first layer has a slight maximum because an increase of the chemical potential causes molecules to leave the compressed first layer and move to the second layer. For this reason, the isosteric heat of adsorption decreases and can become negative. Analysis of adsorption compression mechanisms in the context of theory and emerging experimental results indicates that the significance of this phenomenon is not limited to fundamental aspects of adsorption and capillarity. These mechanisms play a crucial role in various applications, such as heterogeneous catalysis, membrane separations, and self-assembly on surfaces. Results are discussed in a broader context of theory, experiments and previous simulations. |
