On the virial expansion of model adsorptive systems

Published

November 9, 2021

Author(s)

William P. Krekelberg, Vincent Shen

Abstract

We investigate super critical adsorptive properties of various model systems of variable fluid- solid attractive strengths using the confined-density virial expansion, with coefficients calculated using the Mayer-sampling Monte Carlo method up to fifth order. We find that the virial expansion converges for adsorptive systems over a density range corresponding approximately to the film-formation regime. Beyond this regime, higher order effects become increasingly important. The virial expansion of the density profile is also investigated. It is determined that this expansion gives insight into the structure associated with adsorption. We also find that weakly attractive systems have a more negative second virial coefficient than strongly attractive systems. This runs counter to the usual interpretation of bulk fluid virial coefficients. This is due to the infinite-dilution limit being very different for adsorbed fluids compared to bulk fluids.

Citation

Molecular Physics

Volume

120

Issue

4

Pub Type

Journals

Download Paper

https://doi.org/10.1080/00268976.2021.2000056

Local Download

Keywords

adsorption, molecular simulation, statistical mechanics, thermodynamics, virial expansion

Citation

Krekelberg, W. and Shen, V. (2021), On the virial expansion of model adsorptive systems, Molecular Physics, [online], https://doi.org/10.1080/00268976.2021.2000056, https://tsapps.nist.gov/publication/get_pdf.cfm?pub_id=931551 (Accessed October 9, 2025)