Effects of confinement on critical adsorption: absence of critical depletion for fluids in slit pores.

The adsorption of a near-critical fluid confined in a slit pore is investigated by means of density functional theory and by Monte Carlo simulation for a Lennard-Jones fluid. Our work was stimulated by recent experiments for SF6 adsorbed in a mesoporous glass, which showed the striking phenomenon of critical depletion, i.e., the adsorption excess Gamma first increases but then decreases very rapidly to negative values as the bulk critical temperature T(c) is approached from above along near-critical isochores. By contrast, our density functional and simulation results, for a range of strongly attractive wall-fluid potentials, show Gamma monotonically increasing and eventually saturating as the temperature is lowered toward T(c) along both the critical (rho=rho(c)) and subcritical isochores (rho<rho(c)). Such behavior results from the increasingly slow decay of the density profile away from the walls, into the middle of the slit, as T-->T(+)(c). For rho<rho(c) we find that in the fluid the effective bulk field, which is negative and which favors desorption, is insufficient to dominate the effects of the surface fields which favor adsorption. We compare this situation with earlier results for the lattice gas model with a constant (negative) bulk field where critical depletion was found. A qualitatively different behavior of the density profiles and adsorption is found in simulations for intermediate and weakly attractive wall-fluid potentials, but in no case do we observe the critical depletion found in experiments. We conclude that the latter cannot be accounted for by a single pore model.