title: Temperature effects on phase equilibrium and diffusion in mesopores.
abstract: The equilibrium and dynamic properties of fluids confined to mesoporous material have been studied using nuclear magnetic resonance (NMR) methods. Molecular diffusion of n -pentane in Vycor porous glass within closed sample tubes has been measured by means of the pulsed field gradient (PFG) NMR method for temperatures notably exceeding the boiling point of the neat liquid. It is found that the temperature dependence of the diffusivity dramatically depends on the state of the fluid surrounding the mesoporous monoliths. In an oversaturated sample, i.e., in a sample containing some amount of the liquid also outside of the porous material, the diffusivity in the mesopores followed the Arrhenius dependence. In samples with only the mesopores saturated by the liquid, i.e., without any excess fluid, with increasing temperature the diffusivity notably deviated from the Arrhenius dependence towards higher diffusivities. The analysis of the intensities of the respective NMR signals from the fluid within the porous material and in the surrounding phase has revealed that this anomaly is accompanied by the formation of a space free of liquid within the pore system. With the measured pore filling factors, the resulting overall diffusivity is estimated by a two-region approach with diffusion occurring in either the liquid phase or the free space within the pore volume. It is shown that this procedure, free of any fitting parameters, yields excellent agreement with the experimental data.
authors.affiliation: Fakultät für Physik und Geowissenschaften, Universität Leipzig, 04103 Leipzig, Germany.
authors.forename: Muslim
authors.initials: M
authors.lastname: Dvoyashkin
authors.forename: Rustem
authors.initials: R
authors.lastname: Valiullin
authors.forename: Jörg
authors.initials: J
authors.lastname: Kärger