Thermal expansion and stability limits of generalized van der Waals fluids
Abstract
Generalized van der Waals equations of state can exhibit density anomalies, as characterized by a negative thermal expansion coefficient in some region of the phase diagram, when either the hard core volume, b, or the mean field attractive parameter, a, are made temperaturedependent. If b decreases as the temperature increases, negative thermal expansion occurs at all temperatures. At a given temperature, the liquid becomes anomalous when the pressure is increased; hence the PT projection of the locus of density maxima has positive slope. The locus of density maxima extends to zero temperature when b is finite at T = 0, and it terminates at a minimum temperature if b diverges at T = 0. If, on the other hand, a increases with temperature while the core volume remains constant, generalized van der Waals fluids exhibit density anomalies that disappear at high pressure. Hence, in this case the locus of density maxima has a negative slope in the PT plane. The liquid spinodal is reentrant both when a increases as the temperature increases and when b increases as the temperature decreases, becoming infinite at T = 0. 38 refs., 20 figs., 1 tab.
 Authors:

 Princeton Univ., NJ (United States)
 Boston Univ., MA (United States)
 Publication Date:
 OSTI Identifier:
 7243350
 DOE Contract Number:
 FG0287ER13714
 Resource Type:
 Journal Article
 Journal Name:
 Journal of Physical Chemistry; (United States)
 Additional Journal Information:
 Journal Volume: 98:27; Journal ID: ISSN 00223654
 Country of Publication:
 United States
 Language:
 English
 Subject:
 36 MATERIALS SCIENCE; 99 GENERAL AND MISCELLANEOUS//MATHEMATICS, COMPUTING, AND INFORMATION SCIENCE; 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; LIQUIDS; EQUATIONS OF STATE; THERMAL EXPANSION; THERMODYNAMIC PROPERTIES; VAN DER WAALS FORCES; HEAVY WATER; MATHEMATICAL MODELS; SILICA; WATER; CHALCOGENIDES; EQUATIONS; EXPANSION; FLUIDS; HYDROGEN COMPOUNDS; MINERALS; OXIDE MINERALS; OXIDES; OXYGEN COMPOUNDS; PHYSICAL PROPERTIES; SILICON COMPOUNDS; SILICON OXIDES; 360606*  Other Materials Physical Properties (1992); 990200  Mathematics & Computers; 661300  Other Aspects of Physical Science (1992)
Citation Formats
Chakravarthi, A S, Debenedetti, P G, Yeo, S D, and Sastry, S. Thermal expansion and stability limits of generalized van der Waals fluids. United States: N. p., 1994.
Web. doi:10.1021/j100078a034.
Chakravarthi, A S, Debenedetti, P G, Yeo, S D, & Sastry, S. Thermal expansion and stability limits of generalized van der Waals fluids. United States. https://doi.org/10.1021/j100078a034
Chakravarthi, A S, Debenedetti, P G, Yeo, S D, and Sastry, S. Thu .
"Thermal expansion and stability limits of generalized van der Waals fluids". United States. https://doi.org/10.1021/j100078a034.
@article{osti_7243350,
title = {Thermal expansion and stability limits of generalized van der Waals fluids},
author = {Chakravarthi, A S and Debenedetti, P G and Yeo, S D and Sastry, S},
abstractNote = {Generalized van der Waals equations of state can exhibit density anomalies, as characterized by a negative thermal expansion coefficient in some region of the phase diagram, when either the hard core volume, b, or the mean field attractive parameter, a, are made temperaturedependent. If b decreases as the temperature increases, negative thermal expansion occurs at all temperatures. At a given temperature, the liquid becomes anomalous when the pressure is increased; hence the PT projection of the locus of density maxima has positive slope. The locus of density maxima extends to zero temperature when b is finite at T = 0, and it terminates at a minimum temperature if b diverges at T = 0. If, on the other hand, a increases with temperature while the core volume remains constant, generalized van der Waals fluids exhibit density anomalies that disappear at high pressure. Hence, in this case the locus of density maxima has a negative slope in the PT plane. The liquid spinodal is reentrant both when a increases as the temperature increases and when b increases as the temperature decreases, becoming infinite at T = 0. 38 refs., 20 figs., 1 tab.},
doi = {10.1021/j100078a034},
url = {https://www.osti.gov/biblio/7243350},
journal = {Journal of Physical Chemistry; (United States)},
issn = {00223654},
number = ,
volume = 98:27,
place = {United States},
year = {1994},
month = {7}
}