Water adsorption in ion-bearing nanopores

• Published in: The Journal of chemical physics Vol. 126; no. 2; p. 024703
• Main Authors: Lakatos, G, Patey, G N
• Format: Journal Article
• Language: English
• Published: United States 14-01-2007
• Subjects: Adsorption; Computer Simulation; Electrolytes - chemistry; Ions - chemistry; Models, Chemical; Models, Molecular; Nanostructures - chemistry; Nanostructures - ultrastructure; Water - chemistry
• ISSN: 0021-9606
• DOI: 10.1063/1.2400857

Grand canonical Monte Carlo simulations are used to examine the adsorption of water into cylindrical nanopores containing single ions. The isotherms for water adsorbing into nanopores with radii of 0.44, 0.54, 0.64, and 0.74 nm and containing Na+, K+, Ca2+, Cl-, or F- at 298 K are computed. In all cases the nanopores are found to fill at reservoir chemical potentials below the chemical potential of saturated water vapor at 298 K. The threshold chemical potential is found to be sensitive to both the size of the channel and the ion species, with the anion-bearing pores filling at lower chemical potentials. Additionally, the filling threshold chemical potential is found to decrease as the radius of the pores is decreased. Pores with K+ and Cl- are compared, and the Cl- pores are found to exhibit higher water densities in the filled states and a more energetically favorable water structure while yielding lower per particle entropies. Sample simulation configurations are also examined and indicate that at low chemical potentials, the adsorbed water forms a cluster around the ion. Finally, the influence of the choice of water model on the adsorption isotherms is examined.