On the improvement of SPT2 approach in the theory of a hard sphere fluid in disordered porous media

TL;DR

This paper enhances the SPT2 theoretical approach for modeling hard sphere fluids in disordered porous media, improving accuracy at high densities by incorporating a new porosity parameter and validating with Monte Carlo simulations.

Contribution

The authors introduce improved SPT2b2* and SPT2b3* approximations that account for maximal adsorption porosity, leading to better predictions of fluid behavior in porous media.

Findings

SPT2b3* outperforms previous models in describing chemical potential.

Incorporating porosity * improves high-density accuracy.

Validated results with Monte Carlo simulations.

Abstract

The SPT2 approach is based on the scaled particle theory and developed for the description of thermodynamic properties of hard sphere (HS) fluids in disordered porous media. Using this approach a porous medium is modelled as a quenched matrix of hard spheres (HS) or overlapping hard spheres (OHS). A hard sphere fluid immersed in a matrix can move in a void between matrix particles. A number of approximations were previously proposed within the SPT2 approach. Among these approximations, the SPT2b1 has been considered as the most successful and accurate one in a large range of fluid densities and for different matrix parameters. However, at high densities, it can lack accuracy, since it does not take into account that the maximum packing fraction of a HS fluid in a matrix is limited, not by the geometrical porosity of a matrix $\phi_{0}$ and the probe particle porosity $\phi$, but by another type of porosity $\phi^{*}$ introduced in our previous studies. The porosity $\phi^{*}$ is related to the maximal adsorption capacity of a matrix and it is lower than $\phi_{0}$ and larger than $\phi$. This can be crucial for a fluid in matrices of low porosities and at high fluid density, especially in the region near close-packing conditions. Therefore, the approximations SPT2b2 and SPT2b3 taking into account this feature were suggested, although they still needed a correction because of their poor accuracy. In the present study, we improved the versions of these approximations, named as SPT2b2$^*$ and SPT2b3$^*$. We compare these different approximations with the results of computer simulations performed in the Monte Carlo grand-canonical ensemble. We test the SPT2 approach both for the one- and three-dimensional cases. We show that the SPT2b3$^*$ provides a very good description of the chemical potential of a confined fluid, which is better than others.