Role of cation size on swelling pressure and free energy of mica pores

The ion exchange capacity of clay plays an important role in many industrial applications ranging from radioactive waste disposal to cosmetics. However, swelling or shrinking of clay platelets due to water and ions adsorption in the interstitial zone is also a well-known phenomenon. For their applications, it is crucial to understand the stability of these layered materials, especially after exchange of interstitial ions with surrounding ions having different properties. Here, we probed the role of cation size on swelling pressure and free energy profile. We used molecular simulations to investigate the stability of mica pore, having K⁺, Rb⁺, and Cs⁺ ions. We performed a series of grand canonical Monte Carlo simulations at various pore widths. We probed water adsorption in mica pores from which disjoining pressure, grand potential (swelling free energy), and structural properties of confined water and ions were calculated. While the behavior of these three systems is similar qualitatively because of similar hydration properties of ions, significant differences are observed at the quantitative level due to changes in the hydration structure of cations. The global minimum in swelling free energy is found to be at the smaller pore widths (first minimum) for Rb- and K-mica and at bigger pore widths (second minimum) for Cs-mica pores. We find that ±0.1 Å change in the interstitial cation size leads to a -15 to 5% change in equilibrium loading of adsorbed water and -2 to 35% change in swelling. Our thermodynamic analysis reveals an intricate interplay between enthalpic and entropic contributions caused by the structural change of water in the pores due to the hydration of interstitial cations.