Thermodynamically Consistent Methodology for Estimation of Diffusivities of Mixtures of Guest Molecules in Microporous Materials

[Image: see text] The Maxwell–Stefan (M–S) formulation, that is grounded in the theory of irreversible thermodynamics, is widely used for describing mixture diffusion in microporous crystalline materials such as zeolites and metal–organic frameworks (MOFs). Binary mixture diffusion is characterized by a set of three M–S diffusivities: Đ(1), Đ(2), and Đ(12). The M–S diffusivities Đ(1) and Đ(2) characterize interactions of guest molecules with pore walls. The exchange coefficient Đ(12) quantifies correlation effects that result in slowing-down of the more mobile species due to correlated molecular jumps with tardier partners. The primary objective of this article is to develop a methodology for estimating Đ(1), Đ(2), and Đ(12) using input data for the constituent unary systems. The dependence of the unary diffusivities Đ(1) and Đ(2) on the pore occupancy, θ, is quantified using the quasi-chemical theory that accounts for repulsive, or attractive, forces experienced by a guest molecule with the nearest neighbors. For binary mixtures, the same occupancy dependence of Đ(1) and Đ(2) is assumed to hold; in this case, the occupancy, θ, is calculated using the ideal adsorbed solution theory. The exchange coefficient Đ(12) is estimated from the data on unary self-diffusivities. The developed estimation methodology is validated using a large data set of M–S diffusivities determined from molecular dynamics simulations for a wide variety of binary mixtures (H(2)/CO(2), Ne/CO(2), CH(4)/CO(2), CO(2)/N(2), H(2)/CH(4), H(2)/Ar, CH(4)/Ar, Ne/Ar, CH(4)/C(2)H(6), CH(4)/C(3)H(8), and C(2)H(6)/C(3)H(8)) in zeolites (MFI, BEA, ISV, FAU, NaY, NaX, LTA, CHA, and DDR) and MOFs (IRMOF-1, CuBTC, and MgMOF-74).