title: Gas solubility in hydrophobic confinement.
abstract: Measured forces between apolar surfaces in water have often been found to be sensitive to exposure to atmospheric gases despite low gas solubilities in bulk water. This raises questions as to how significant gas adsorption is in hydrophobic confinement, whether it is conducive to water depletion at such surfaces, and ultimately if it can facilitate the liquid-to-gas phase transition in the confinement. Open Ensemble molecular simulations have been used here to determine saturated concentrations of atmospheric gases in water-filled apolar confinements as a function of pore width at varied gas fugacities. For paraffin-like confinements of widths barely exceeding the mechanical instability threshold (spinodal) of the liquid-to-vapor transition of confined water (aqueous film thickness between three and four molecular diameters), mean gas concentrations in the pore were found to exceed the bulk values by a factor of approximately 30 or approximately 15 in cases of N2 and CO2, respectively. At ambient conditions, this does not result in visible changes in the water density profile next to the surfaces. Whereas the barrier to capillary evaporation has been found to decrease in the presence of dissolved gas (Leung, K.; Luzar, A.; and Bratko, D. Phys. Rev. Lett. 2003, 90, 065502), gas concentrations much higher than those observed at normal atmospheric conditions would be needed to produce noticeable changes in the kinetics of capillary evaporation. In simulations, dissolved gas concentrations corresponding to fugacities above approximately 40 bar for N2, or approximately 2 bar for CO2, were required to trigger expulsion of water from a hydrocarbon slit as narrow as 1.4 nm. For nanosized pore widths corresponding to the mechanical instability threshold or above, no significant coupling between adsorption layers at opposing confinement walls was observed. This finding explains the approximately linear increase in gas solubility with inverse confinement width and the apparent validity of Henry's law in the pores over a broad fugacity range.
authors.affiliation: Department of Chemistry, Virginia Commonwealth University, Richmond, Virginia 23284, USA. aluzar@vcu.edu
authors.forename: Alenka
authors.initials: A
authors.lastname: Luzar
authors.forename: Dusan
authors.initials: D
authors.lastname: Bratko
mesh_terms: D000327:Adsorption; D002245:Carbon Dioxide / Q000737:chemistry*; D057927:Hydrophobic and Hydrophilic Interactions; D009584:Nitrogen / Q000737:chemistry*; D012995:Solubility; D013499:Surface Properties; D014867:Water / Q000737:chemistry
chemical_list: D014867:Water; D002245:Carbon Dioxide; D009584:Nitrogen