Effects of the adsorbate-gas interface at the pore opening on the lower closure point in gaseous adsorption in porous solids

Abstract

The limit to the lower closure point (LCP) observed experimentally in the desorption isotherm of gases in porous solids has been commonly attributed to the homogeneous cavitation of the condensate in cavities. It was proposed recently that the experimental limit to LCP could be described in simulations with the ink-bottle pore, provided that the length of the uniformly sized conduit connecting the closed cavity to the surrounding is shorter than 2 nm, and the evaporation is by way of pore blocking mechanism, rather than homogeneous cavitation. To substantiate this assertion, that deviates from the commonly belief of homogeneous cavitation, we further investigated in this paper with cavities having wedge-like pore opening, that better mimics real solids, and offer further explanation on the limit of the LCP to the pore blocking as the mechanism of evaporation with simulations of argon and nitrogen adsorption over a range of temperatures that are commonly used experimentally. It was found that simulation results correctly captured the experimental observations for carbon-based materials and silica-based materials in that the limit of LCP shifts to higher reduced pressures for weaker adsorbing silica, compared to stronger adsorbing carbon and for a given adsorbent it also shifts to higher reduced pressure for higher temperatures.