title: Mechanism of Kinetically Controlled Capillary Condensation in Nanopores: A Combined Experimental and Monte Carlo Approach.
abstract: We find the rule of capillary condensation from the metastable state in nanoscale pores based on the transition state theory. The conventional thermodynamic theories cannot achieve it because the metastable capillary condensation inherently includes an activated process. We thus compute argon adsorption isotherms on cylindrical pore models and atomistic silica pore models mimicking the MCM-41 materials by the grand canonical Monte Carlo and the gauge cell Monte Carlo methods and evaluate the rate constant for the capillary condensation by the transition state theory. The results reveal that the rate drastically increases with a small increase in the chemical potential of the system, and the metastable capillary condensation occurs for any mesopores when the rate constant reaches a universal critical value. Furthermore, a careful comparison between experimental adsorption isotherms and the simulated ones on the atomistic silica pore models reveals that the rate constant of the real system also has a universal value. With this finding, we can successfully estimate the experimental capillary condensation pressure over a wide range of temperatures and pore sizes by simply applying the critical rate constant.
authors.affiliation: Department of Chemical Engineering, Kyoto University , Katsura, Nishikyo, Kyoto 606-8501, Japan.
authors.forename: Tatsumasa
authors.initials: T
authors.lastname: Hiratsuka
authors.affiliation: Department of Chemical Engineering, Kyoto University , Katsura, Nishikyo, Kyoto 606-8501, Japan.
authors.forename: Hideki
authors.initials: H
authors.lastname: Tanaka
authors.affiliation: Department of Chemical Engineering, Kyoto University , Katsura, Nishikyo, Kyoto 606-8501, Japan.
authors.forename: Minoru T
authors.identifier: 0000-0001-8883-5851
authors.initials: MT
authors.lastname: Miyahara
keywords: free energy barrier; molecular simulation; nucleation; rate constant; transition state theory