Hydrogen Bonding Effects in Adsorption of Water−Alcohol Mixtures in Zeolites and the Consequences for the Characteristics of the Maxwell−Stefan Diffusivities

This work highlights a variety of peculiar characteristics of adsorption and diffusion of polar molecules such as water, methanol and ethanol in zeolites. These peculiarities are investigated with the aid of configurational-bias Monte Carlo (CBMC) simulations of adsorption isotherms, and molecular dynamics (MD) simulations of diffusivities in FAU, MFI, DDR, and LTA zeolites. Because of strong hydrogen bonding, significant clustering of the guest molecules occurs in all investigated structures. Because of molecular clustering, the inverse thermodynamic factor 1/Γ i ≡ (d[ln c i ])/(d[ln f i ]) exceeds unity for a range molar concentrations c i within the micropores. The degree of clustering is lowered as the temperature is increased. For the concentration ranges for which 1/Γ i > 1, the Fick diffusivity, D i , for unary diffusion is often lower than both the Maxwell−Stefan, Đ i , and the self-diffusivity, D i,self. For water−alcohol mixtures, the hydrogen bonding between water and alcohol molecules is much more predominant than for water−water, and alcohol−alcohol molecule pairs. Consequently, the adsorption of water−alcohol mixtures shows significant deviations from the predictions of the ideal adsorbed solution theory (IAST). The water−alcohol bonding also leaves its imprint on the mixture diffusion characteristics. The Maxwell−Stefan diffusivity, Đ i , of either component in water−alcohol mixtures is lower than the corresponding values of the pure components; this behavior is distinctly different from that for mixtures of nonpolar guest molecules. The binary exchange coefficient Đ 12 for water−alcohol mixtures is also significantly lower than either self-exchange coefficients Đ 11 and Đ 22 of the constituent species. This implies that correlation effects are significantly stronger in water−alcohol mixtures than for the constituent species. Correlation effects are found to be significant for water−alcohol mixture diffusion in DDR and LTA zeolites, even though such effects are negligible for the pure constituents. The major conclusion to emerge from this investigation is that, unlike mixtures of nonpolar molecules, it is not possible to estimate water−alcohol mixture adsorption and diffusion characteristics on the basis of pure component data.