JOURNAL OF CHEMICAL PHYSICS VOLUME 115, NUMBER 3 15 JULY 2001

Equations of state for fluids: The Dieterici approach revisited

Richard J. Sadusa)
Centre for Molecular Simulation and School of Information Technology,
Swinburne University of Technology, P.O. Box 218, Hawthorn, Victoria 3122, Australia
共Received 18 January 2001; accepted 1 May 2001兲
In 1873, van der Waals proposed a simple equation of state that qualitatively described the phase
behavior of fluids. Since then, the principles behind the van der Waals equation have been used and
refined countless times in the quest for an accurate equation of state. Despite the enormous amount
of work reported, the goal of a simple and accurate equation of state for even relatively simple
systems, such as monatomic or polyatomic gases, has proved elusive. Therefore, the analysis of
phase equilibria with equations of state is more often than not an exercise in data fitting rather than
genuine prediction. In this work, we revisit the early work of Dieterici. When coupled with modern
developments in equations of state, this little used approach has the potential of generating useful
equations of state. To illustrate the usefulness of the Dieterici formula, we use it to derive a simple
equation of state based on the Carnahan–Starling hard-sphere term and van der Waals interactions.
This simple approach yields more accurate predictions of the phase co-existence of fluids than the
traditional additive approach used to develop equations of state. © 2001 American Institute of
Physics. 关DOI: 10.1063/1.1380711兴

I. INTRODUCTION
An equation of state for fluids provides a relationship
between pressure (p), temperature 共T兲 and volume 共V兲. Such
a relationship is of considerable scientific and practical im-
portance because it enables us to predict many useful ther-
modynamic properties such as phase equilibria. The van der
Waals1 equation of state is:
RT a tions of state. Dieterici’s equation provides an alternative
p⫽ ⫺ 2, 共1兲
V⫺b V
where R is the universal gas constant, b accounts for the
volume occupied by the molecules and a represents attrac-
tion arising from dispersion forces. The first term of Eq. 共1兲
represents the repulsion of hard-spheres, whereas the remain-
ing term accounts for the effect of attraction due to disper-
sion forces. To this day, almost all equations of state devel-
oped subsequently2–5 have followed the van der Waals
approach of simply adding together contributions from repul-
sion and attraction. Therefore, most commonly used equa-
tions of state follow the ‘‘repulsion⫹attraction’’ formula,
i.e.,
p⫽p rep⫹p attr . 共2兲
Despite the enormous amount of work reported using this
conceptual framework, the goal of a universally accurate
equation of state has proved elusive. The aim of this work is
to show that an alternative approach first suggested by
Dieterici,6 coupled with a modern understanding of intermo-
lecular interactions, has the potential to improve the accuracy
of equations of state for fluids.
II. GENERALIZATION OF DIETERICI’S APPROACH
In 1899, Dieterici6 proposed an alternative theoretically
based equation of state involving an exponential term:
a兲
Electronic mail: RSadus@swin.edu.au
RT ⫺a/RTV
p⫽ e . 共3兲
V⫺b
The advantages of this equation, such as a more realistic
critical compressibility factor (Z c ⫽0.2706), are
6 –9
documented. However, in contrast to the important role of
the van der Waals equation, the Dieterici equation has not
contributed significantly to the development of modern equa-
framework to Eq. 共2兲 for the development of new equations
of state. Equation 共3兲 can be generalized as:
p⫽ p repe ⫺attractive term/RTV
. 共4兲
In contrast to the traditional method for obtaining equations
of state, Eq. 共4兲 provides an alternative way of handling the
contributions from repulsion and attraction.
In the past few decades, considerable progress has been
achieved in understanding the importance of intermolecular
repulsion on both the structure and physical properties of
fluids.2 Many alternative models of intermolecular repulsion
have been proposed.4 In particular, the formula proposed by
Carnahan and Starling10 is an accurate and relatively simple
representation of the repulsion of hard-spheres. We observe
that simply using the Carnahan–Starling expression and van
der Waals term 共a兲 for repulsion and attraction, respectively,
in Eq. 共4兲, yields a potentially useful equation of state:
RT 共 1⫹y⫹y 2 ⫺y 3 兲 ⫺a/RTV
p⫽ e , 共5兲
V 共 1⫺y 兲 3
where y⫽b/4V. Applying the conventional criteria for a
critical point5 to the above equation, we can obtain the equa-
tion of state parameters in terms of the critical properties of
the fluid 共a⫽2.996 79RT C V C and y c ⫽0.357 057兲. The criti-
cal compressibility factor predicted by Eq. 共5兲 (Z c
⫽0.2705) is in good agreement with the experimental values
typically reported for monatomic gases.11

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 J. Chem. Phys., Vol. 115, No. 3, 15 July 2001 Equations of state for fluids 1461

FIG. 1. Comparison of the experimental phase behavior of argon 共䊉兲 共Ref. FIG. 2. Comparison of the experimental phase behavior of argon 共䊉兲 共Ref.
16兲 with equation of state predictions. 16兲 with equation of state predictions from the triple point 共tp兲 to the critical
point 共cp兲.

III. RESULTS AND DISCUSSION systems illustrated in Figs. 1, 3 and 4. Although the agree-
ment with experiment reported in Table I is not perfect, con-
To test the accuracy of Eq. 共5兲, we report calculations for ventional equations of state could be expected to perform
the phase behavior of argon in Figs. 1 and 2. Results for the poorly in this region. These results are good when it is con-
van der Waals 共vdW兲,1 Dieterici6 and Carnahan–Starling van sidered that absolutely no attempt has been made to fit theory
der Waals 共CSvdW兲12 equations of state are also given for to experiment. It is also noteworthy that molecular simula-
comparison. At each temperature, the pressure and co- tion results13,14 for the noble gases using accurate two-body
existing densities were determined by using the conventional and three-body intermolecular potentials typically result in
Maxwell procedure10 to satisfy the conditions for phase AADs of 10–30% for the vapor phase densities and about
co-existence.5 The calculations represent genuine predictions 2% for the liquid phase densities.
with the equation of state parameters determined solely from Encouraged by the results for argon, we applied Eq. 共5兲
the experimental critical temperature and volume.11 to predict the phase behavior of noble gases 共Fig. 3兲, poly-
Argon is the de facto standard test fluid for equations of atomic molecules 共Fig. 4兲 and normal alkanes 共Fig. 5兲. It is
state involving hard-sphere repulsion and dispersion interac- apparent that there is very good agreement for all of the
tions because it is both spherical and nonpolar. It is apparent noble gases 共Fig. 3兲. We would expect polyatomic molecules
from Fig. 1 that Eq. 共5兲 predicts the co-existing densities of to pose a greater challenge for Eq. 共5兲 because the effect of
argon with remarkable accuracy. In particular, the liquid molecular shape and other complicating factors are not in-
phase densities are predicted to a typical accuracy of 1 to cluded. However, it is evident from Fig. 4 that Eq. 共5兲 can
2%. In contrast, the other equations of state are very inaccu- adequately predict the co-existing densities of every nonpo-
rate for both liquid and vapor phase properties. In particular, lar polyatomic molecule investigated. In Fig. 4, we have also
the improved accuracy of Eq. 共5兲 compared with the CSvdW included a comparison of theory with experiment for ammo-
equation is significant because both equations have the same nia and water. The phase behavior of these systems is diffi-
repulsion and attraction terms. The difference between these cult to predict because of the influence of dipole interactions
equations can be attributed solely to a difference between the
‘‘repulsion⫹attraction’’ and generalized Dieterici frame-
works. The pressure-temperature predictions for argon are TABLE I. Percentage average absolute deviations 共AAD %兲 between the
predictions obtained using Eq. 共5兲 and experiment for vapor and liquid
compared with experiment in Fig. 2. It is apparent that Eq.
phase densities and pressure at temperatures in the vicinity of the critical
共5兲 accurately predicts the pressure at temperatures from the point (0.98⭐T/T c ⭐1).
critical point to midway to the triple point. It is also in better
overall agreement with experiment than results from the Molecule Density 共liquid兲 Density 共vapor兲 Pressure
other equations of state. Argon 1.6 2.5 4.5
The prediction of fluid-phase co-existence in the vicinity Xenon 4.1 14.2 3.8
of the critical point is a severe test for an equation of state. Hydrogen 5.0 9.2 4.6
The nonanalytic nature of this region means that mean-field Nitrogen 1.3 1.5 2.4
Oxygen 0.8 2.5 3.0
equations can be expected to fail. In Table I, values of the
Carbon dioxide 7.0 3.3 2.1
average absolute deviation between theory and experiment in Water 2.0 6.2 9.7
the vicinity of the critical point are reported for some of the

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 1462 J. Chem. Phys., Vol. 115, No. 3, 15 July 2001
FIG. 3. Comparison of the experimental phase behavior of the noble gases
共䊉兲 共Ref. 16兲 with the predictions of Eq. 共5兲 共 兲.
and hydrogen bonding. Although the results for both ammo-
nia and water are not quantitatively accurate, the results are
nonetheless reasonable in view of the fact that Eq. 共5兲 is not
designed for dipolar systems. The comparison of theory with
experiment in Fig. 5 for the normal alkanes tests the ability
of Eq. 共5兲 to handle molecular complexity. Reasonable agree-
ment with experiment is obtained for n-alkanes up to
n-pentane. For n-alkanes from n-octane onwards, Eq. 共5兲 be-
comes progressively less reliable. Nonetheless, this is an en-
FIG. 4. Comparison of the experimental phase behavior of diatomic
and polyatomic molecules 共䊉兲 共Refs. 16,17兲 with the predictions of
Eq. 共5兲 共 兲.
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Richard J. Sadus
FIG. 5. Comparison of the experimental phase behavior of normal alkanes
共䊉兲 共Ref. 16兲 with the predictions of Eq. 共5兲 共 兲.
couraging result for an equation, which assumes spherical
symmetry.
IV. CONCLUSIONS
The generally good results obtained from Eq. 共5兲, indi-
cate that the generalized Dieterici formula 关Eq. 共4兲兴 can be
used as the basis for equation of state development. For ex-
ample, it is conceivable that further improvement could be
achieved by using the density-dependent attractive term pro-
posed by Dohrn and Prausnitz.15 The significance of the gen-
eralized Dieterici formula is that it has the potential to pro-
vide a better alternative to the conventional and widely used
‘‘repulsion⫹attraction’’ framework for equation of state de-
velopment.
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