Connecting Entropy Scaling and Density Scaling

TL;DR

This paper establishes a direct link between residual entropy and density scaling, showing how the residual entropy relates to the effective interaction hardness in molecular models, with implications for understanding fluid behavior.

Contribution

It identifies the residual entropy as the key variable in density scaling and clarifies the limitations of two-body residual entropy as a surrogate for total residual entropy.

Findings

Residual entropy correlates with density scaling variables.

Two-body residual entropy is insufficient for total residual entropy in gases.

Density scaling exponent relates to molecular interaction hardness.

Abstract

It is shown that the residual entropy (entropy minus that of the ideal gas at the same temperature and density) is mostly synonymous with the independent variable of density scaling, identifying a direct link between these two approaches. The two-body residual entropy is demonstrated to not be a suitable surrogate for the total residual entropy in the gas phase. The residual entropy and the effective hardness of interaction (itself a derivative at constant residual entropy) are studied for the Lennard-Jones monomer and dimer as well as a range of rigid molecular models for carbon dioxide. It is observed that the density scaling exponent is related to the two-body interactions.