Nonwetting/Prewetting/Wetting Transition of Ammonia on Graphite

Simulations of ammonia adsorption on graphite were carried out over a range of temperatures to investigate the transition from nonwetting to wetting. The process is governed by a subtle interplay between the various interactions in the system and the temperature. At temperatures below the bulk triple point, the system is nonwetting; above the triple point, we observed continuous wetting, preceded by a prewetting region in which the so-called thin-to-thick film transition occurs. This system serves as an excellent example of wetting/nonwetting behavior in an associating fluid as a function of temperature because the heat of sublimation (or condensation) is greater than the isosteric heat of adsorption at zero loading. The nonwetting-to-wetting transition (NW/W) is also strongly affected by the adsorbate-adsorbate interaction, which becomes important when this contribution to the isosteric heat is of a similar magnitude to the heat of condensation. An appropriate indicator of a NW/W transition at a given loading is therefore the difference between the isosteric heat and the heat of sublimation (or condensation). Our simulation results show the "thin-to-thick" film transition in the temperature range between 195 and 240 K, which has not been previously explained. Above 240 K, continuous wetting occurs. This study provides a basis for a better understanding of adsorption in a range of systems because ammonia is an intermediate between simple molecules, such as argon, and strongly associating fluids, such as water.