Fluid Phase Equilibria 206 (2003) 287–311
Evaluation of the performance of cubic equations of state
in predicting the regularities in dense fluids
Ali Maghari
∗
, Leila Hosseinzadeh-Shahri
Department of Chemistry, University of Tehran, Tehran, Iran
Received 13 September 2002; accepted 25 December 2002
Abstract
This paper deals with the evaluation of 10 recent van der Waals type equations of state (EOS) for their ability
to predict the three important regularities. The studied regularities included: (i) the linearity of Zeno contour of
reduced temperature against reduced density from the Boyle temperature to the triple point, (ii) the common bulk
modulus point on the isotherms of the reduced bulk modulus versus reduced density, and (iii) the near linearity
of reduced isothermal bulk modulus as a function of reduced pressure (Tait–Murnaghan equation) over the vapor
pressure curve to the freezing line. The investigated equations of state are Kubic–Martin (KM), Adachi–Lu–Sugie
(ALS), Yu–Lu (YL), Trebble–Bishnoi (TB), Iwai–Margerum–Lu (IML), Twu–Coon–Cunningham (TCC), modi-
fied Patel–Teja (MPT), Nasrifar–Moshfeghian (NM), Peng–Robinson (PR) and Soave–Redlich–Kwong. The best
overall performance for Zeno contour is obtained based on the SRK, TB, KM and PR EOS, whilst the NM and ALS
EOS produce the worst performances. The Zeno line prediction using the SRK, TB, KM and PR EOS approach
the experimental reduced Boyle temperature at low-density, confirming their accuracy in supercritical region. The
low-density region of the isothermal bulk modulus of CH
4
, as a spherical molecule, is well matched by SRK and
KM EOS, but is closely matched by TB, IML and NM EOS. In compressed liquid, we observe that the slope and
curvature of the calculated bulk modulus of CH
4
obtained by SRK and KM EOS consistently performs better than
the other EOS. For C
2
H
6
,C
3
H
8
and n-C
4
H
10
the predictive ability of the isothermal bulk modulus obtained from
the cubic EOS are usually poor, especially at higher densities. We have also shown that the most accurate prediction
of Tait–Murnaghan regularity of CH
4
is KM, SRK, PR and MPT EOS for both subcritical and supercritical fluids
in a wide pressure range, while the TB and NM EOS predict the Tait–Murnaghan regularity for supercritical fluids.
© 2003 Elsevier Science B.V. All rights reserved.
Keywords: Van der Waals type equation of state; Thermodynamic regularities; Zeno line; Isothermal bulk modulus
1. Introduction
The accurate description of thermodynamic properties of fluids over the large intervals of temperatures
and densities with multiparameter equations of state (EOS) have been a subject of active research, which
∗
Corresponding author.
E-mail address: maghari@khayam.ut.ac.ir (A. Maghari).
0378-3812/03/$ – see front matter © 2003 Elsevier Science B.V. All rights reserved.
doi:10.1016/S0378-3812(03)00008-6