TY - JOUR
T1 - About the physical validity of attaching the repulsive terms of analytical EOS models by temperature dependencies
AU - Kalikhman, Vladimir
AU - Kost, Daniel
AU - Polishuk, Ilya
N1 - Funding Information:
Ilya Polishuk acknowledges the Donors of the American Chemical Society Petroleum Research Fund for support of this research, grant N° PRF#47338-B6 .
PY - 2010/6/25
Y1 - 2010/6/25
N2 - This study demonstrates that any temperature dependency introduced in the term describing the inter-molecular repulsive forces of analytical EOS models leads to prediction of the infinite value for the isochoric heat capacity at the density limit conditions. The temperature-dependent hard sphere diameters and co-volumes necessarily result in the non-physical negative infinite values of this property at the infinite pressure, which in turn leads to the non-physical predictions of other properties, such as the sound velocities. In addition, this study demonstrates that the inconsistency existing at the imaginary state of infinite pressure may have a very strong negative impact on predicting the data of real fluids at the experimentally available pressures. Therefore making the repulsion compressibility factor temperature-dependent seems highly non-recommended.
AB - This study demonstrates that any temperature dependency introduced in the term describing the inter-molecular repulsive forces of analytical EOS models leads to prediction of the infinite value for the isochoric heat capacity at the density limit conditions. The temperature-dependent hard sphere diameters and co-volumes necessarily result in the non-physical negative infinite values of this property at the infinite pressure, which in turn leads to the non-physical predictions of other properties, such as the sound velocities. In addition, this study demonstrates that the inconsistency existing at the imaginary state of infinite pressure may have a very strong negative impact on predicting the data of real fluids at the experimentally available pressures. Therefore making the repulsion compressibility factor temperature-dependent seems highly non-recommended.
KW - Effective hard sphere diameter
KW - Equation of state
KW - Isochoric heat capacity
KW - Thermodynamic consistency
UR - http://www.scopus.com/inward/record.url?scp=77953132852&partnerID=8YFLogxK
U2 - 10.1016/j.fluid.2010.03.003
DO - 10.1016/j.fluid.2010.03.003
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AN - SCOPUS:77953132852
SN - 0378-3812
VL - 293
SP - 164
EP - 167
JO - Fluid Phase Equilibria
JF - Fluid Phase Equilibria
IS - 2
ER -