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An entropy scaling demarcation of gas- and liquid-like fluid behaviors.

Authors :
Bell IH
Galliero G
Delage-Santacreu S
Costigliola L
Source :
The Journal of chemical physics [J Chem Phys] 2020 May 21; Vol. 152 (19), pp. 191102.
Publication Year :
2020

Abstract

In this work, we propose a generic and simple definition of a line separating gas-like and liquid-like fluid behaviors from the standpoint of shear viscosity. This definition is valid even for fluids such as the hard sphere and the inverse power law that exhibit a unique fluid phase. We argue that this line is defined by the location of the minimum of the macroscopically scaled viscosity when plotted as a function of the excess entropy, which differs from the popular Widom lines. For hard sphere, Lennard-Jones, and inverse-power-law fluids, such a line is located at an excess entropy approximately equal to -2/3 times Boltzmann's constant and corresponds to points in the thermodynamic phase diagram for which the kinetic contribution to viscosity is approximately half of the total viscosity. For flexible Lennard-Jones chains, the excess entropy at the minimum is a linear function of the chain length. This definition opens a straightforward route to classify the dynamical behavior of fluids from a single thermodynamic quantity obtainable from high-accuracy thermodynamic models.

Details

Language :
English
ISSN :
1089-7690
Volume :
152
Issue :
19
Database :
MEDLINE
Journal :
The Journal of chemical physics
Publication Type :
Academic Journal
Accession number :
33687260
Full Text :
https://doi.org/10.1063/1.5143854