Descripción: A simple model based on an approximation of the dropletlike model is formulated for studying adsorption of fluids into cylindrical pores. This model yields a nearly universal description of capillary condensation transitions for noble gases confined by alkali metals. The system’s thermodynamical behavior is predicted from the values of two dimensionless parameters: [formula presented] (the reduced asymptotic strength of the fluid-adsorber interaction, a function of temperature) and [formula presented] (the reduced radius of the pore). The phenomenon of hysteresis inherently related to capillary condensation is discussed. The connection to a previously proposed universality for cylindrical pores is also established. © 2002 The American Physical Society.

Descripción: Molecular dynamics simulations of water in cylindrical hydrophilic pores with diameters of 1.5 and 3 nm were performed to explore the phase behavior and the nucleation dynamics of the confined fluid as a function of the percentage of volume filled f. The interactions of water with the pore wall were considered to be identical to the interactions between water molecules. At low water contents, all the water is adsorbed to the surface of the pore. A second phase consisting of a liquid plug appears at the onset filling for capillary condensation, fonset =27% and 34% for the narrow and wide pores, respectively. In agreement with experimental results for silica pores, the liquid phase appears close to the equilibrium filling feq in the 1.5 nm pore and under conditions of strong surface supersaturations for the 3 nm pore. After condensation, two phases, a liquid plug and a surface-adsorbed phase, coexist in equilibrium. Under conditions of phase coexistence, the water surface density Tcoex was found to be independent of the water content and the diameter of the pore. The value of Tcoex found in the simulations (∼3 nm-2) is in good agreement with experimental results for silica pores, suggesting that the interactions of water with silica and with itself are comparable. The surface-adsorbed phase at coexistence is a sparse monolayer with a structure dominated by small water clusters. We characterize the density and structure of the liquid and surface phases, the nucleation mechanism of the water plug, and the effect of surface hydrophilicity on the two-phase equilibrium and hysteresis. The results are discussed in light of experiments and previous simulations. © 2010 American Institute of Physics.

Descripción: A simple model, previously used to explore wetting transitions, is evaluated for the case of a slab geometry in which adsorption occurs between two semi-infinite solids, with parallel faces separated by a distance L. The model yields a universal description of possible wetting and capillary condensation (CC) transitions. The system’s thermodynamic behavior is predicted from the values of two dimensionless parameters: [Formula Presented] (the reduced gas-surface interaction strength, a function of temperature) and [Formula Presented] (the reduced separation). If [Formula Presented] negligible adsorption occurs at all pressures below saturated vapor pressure (SVP). For somewhat larger values of [Formula Presented] CC occurs for sufficiently small [Formula Presented] close to SVP. For very large values of [Formula Presented] an additional prewetting transition (formation of a film) is predicted for large [Formula Presented] this is accompanied by a CC transition close to SVP. The model is generally consistent with limited results of density-functional calculations for the He liquids at zero temperature. © 1999 The American Physical Society.

Descripción: The confinement of Ar in planar slits of two identical parallel semi-infinite walls of alkali metals, alkaline-earth metal Mg, and CO 2 is investigated within the framework of the density functional theory. It is assumed that (1) the fluid atoms interact via a recently proposed effective attractive pair potential with strength, εff, which reproduces the experimental data of the surface tension of the liquid-vapor interface at the bulk coexistence curve, and (2) the adsorption on the walls is described by ab initio potentials characterized by a well depth, Wsf. In this way the systems were studied in the framework of a realistic approach. We found that for small coverages, the slit is always filled by forming two symmetric vapor films, one at each wall. For increasing coverage the behavior depends on the ratio Wsf/εff and the temperature T. In the case of alkali metals, we found at the triple point, Tt, of the adsorbate a regime of average density ρ*av in which the ground state exhibits asymmetric density profiles, leading to the so-called spontaneous symmetry breaking (SSB) effect. The SSB appears at an average density ρ*sb1 and disappears at a higher average density ρ*sb2 . When T is increased, the range of densities ρ*sb1≤ρ*av≤ ρ* sb2 diminishes and eventually the SSB disappears at a critical temperature, Tsb, which coincides with the critical prewetting temperature Tcpw observed in the adsorption on a single wall. For T>Tcpw the slit is filled symmetrically up to the phase transition to capillary condensation. All these features are examined as a function of the strength of the substrate and the width of the slit. Furthermore, no SSB effect was found for Mg and CO2. © 2010 American Institute of Physics.