On the Hysteresis of Adsorption on Solid Surfaces

Abstract

Hysteresis phenomena associated with the adsorption of gases on solid surfaces are usually explained in terms of three-dimensional capillary effects or with more or less unspecific reference to phase transitions. It is shown that hysteresis effects are to be expected when two dimensional phase transitions occur on solids. In the connection, the thermodynamic equation governing the equilibrium of small, incompressible two-dimensional phases is derived. Such phases can form on an imperfect solid surface in an irreversible manner and, as calculation shows, can contribute significantly to the hysteresis of adsorption. In some cases the phase change may be responsible for the whole effect. The diffuseness of first-order phase transitions may be due to the same mechanism.