Fluid Phase Equilibria, 60 (1990) 327-332 327

Elsevier Science Publishers B.V., Amsterdam

Short Communication

ON A TEMPERATURE DEPENDENCE OF THE VAN DER WAALS

VOLUME PARAMETER IN CUBIC EQUATIONS OF STATE

LUBOMiR HNBDKOVSK+ and IVAN CIBULKA *

Department of Physical Chemistry, Institute of Chemical Technology,
I66 28 Prague 6 (Czechoslovakia)
(Received November 8, 1989; in final form May 20, 1990)

ABSTRACT

HnGdkovsky, L. and Cibulka, I., 1990. On a temperature dependence of the van der Waals
volume parameter in cubic equations of state. Fluid Phase Equilibria, 60: 327-332.

A dependence of the van der Waals volume parameter on temperature in cubic equations
of state is analysed from the point of view of a consistency in the description of the
compressed liquid region. The analysis shows that there may, be a region in a PpT space
where the thermal pressure coefficient and the isobaric thermal expansion coefficient are
negative if the van der Wards volume parameter decreases with increasing temperature. The
results of the analysis are illustrated with a volume-translation method, which is the special
case of the temperature dependence of the van der Waals volume parameter.

INTRODUCTION

Cubic equations of state are popular tools for descriptions of properties of

fluids such as saturation pressures, phase equilibria in mixtures, etc. In a
pure fluid system a temperature dependence of the van der Waals parame-
ter, a, alone is sufficient to obtain a satisfactory description of saturation
pressures. However, saturated liquid densities (volumes) are not predicted
correctly by most cubic equations of state, especially by those with fewer
than three adjustable parameters. A description of saturated liquid densities
can be improved if the volume parameter, b, is also allowed to vary with
temperature. However, this may bring an inconsistency into a description of
the compressed liquid region, as is discussed in this paper.

* Author to whom correspondence should be addressed.

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GENERAL CONSIDERATIONS

One of the possible general forms of cubic equations of state may be

written as:
2
PRT
p=iqy$) (1)
where p = l/V, a and b are adjustable parameters and F(p) is a poly-
nomial function of up to second order in density that may comprise two
more adjustable parameters (usually independent of temperature). Pressure
in eqn. (1) is given as the difference between two positive terms, the first one
representing repulsive forces and the second one attractive forces between
molecules. A density range in which the pressure given by eqn. (1) has a
physical significance (except for the two-phase region at sub-critical temper-
atures) is limited by the value p = l/b, for which the pressure approaches
plus infinity owing to the repulsion term, while the attraction term is finite
for all densities p d l/b. This implies that a selected isotherm approaches
asymptotically the limit p = l/b. If the parameter b decreases with increas-
ing temperature, i.e. if db/dT < 0 holds, the limit for a certain isotherm lies
at a higher density than the limit of any isotherm for an arbitrarily chosen
lower temperature. Therefore, the two isotherms must cross each other in a
P-p diagram and AP/AT < 0 holds for density higher than that corre-
sponding to the crossing point. This inconsistent behaviour of cubic equa-
tions of state with a temperature-dependent volume parameter, b, has been
mentioned by Trebble and Bishnoi (1986) and is discussed in a broader
context elsewhere (Hnedkovsky et al 1990).
The qualitative considerations given above can be made more precise. It
can be derived from eqn. (1) that
l+p(Tb’-b) _p2u’F(p)-aF’(p)
(1 _ bp)* (2)
F(P12
where b’ = db/dT, a’ = du/dT and F’(p) = [8F( p)/aT],. Then

1 -- 1 u’F(l/b) - uF’(l/b)
=b’F fim (3)
P-l/b [ (1 -‘bpj2 b* F(l/bj2
The limit in eqn. (3) approaches minus infinity for any finite values of a’
and F’ if b’ < 0 holds. Since (tlP/i?IT), is a continuous function of density
for all densities lower than l/b, there must be a density range where
(aP/aT), is negative. Consequently, the isobaric thermal expansion coeffi-
cient, (Y,,= - p-‘( ap/i3T),, is negative in this density range because the
condition (aP/ap), > 0 must be fulfilled by any equation of state in a
 329

Ir
Fig. 1. P,-T,diagram for methane obtained by the volume-translation method by Watson et
al. (1986): -, isochores; -. -. -, vapour-liquid saturation curve; - - -, line along which
(W/aT), = 0 holds; C.P., gas-liquid critical point.

single-phase region. Further, compressed liquid isochores start from the

saturation line where (W/U), > 0. Then there should be a temperature
where (W/W), = 0 and (W/W), < 0 would hold for higher temperatures
along the isochore. Thus the isochore is a concave curve in a P-T diagram
and therefore (ti*P/aT*), is negative (see Fig. 1).
From this analysis it follows that the sign of the derivative db/dT should
always be checked, especially in those cases when equation-of-state parame-
ters obtained by fitting saturation PpT data are to be used for calculations
in a compressed liquid region. The above-mentioned inconsistencies in the
PpT space manifest themselves in derived thermodynamic quantities and
might also be discussed in the light of classical thermodynamics (for a
discussion on heat capacities see for example Trebble and Bishnoi (1986)).
A VOLUME-TRANSLATION METHOD

A volume-translation method, widely employed for cubic equations of

state, improves the prediction of saturated liquid densities while the descrip-
tion of saturation pressures remains unchanged when compared with the
respective equation of state with no translation in volume (Martin, 1979;
Peneloux et al., 1982). The method is based on the translation in volume,
defined as
t = V(EOS) - V(act) (4)
330

where V(EOS) represents the molar volume obtained from the respective
equation of state with no volume translation and V(act) is the actual volume
of a fluid. The volume coordinate may be shifted by a constant value, t
(Peneloux et al., 1982), but an allowance for temperature dependence can
improve significantly the description of densities in a given temperature
range. A dependence of t on temperature is then usually obtained by fitting
saturated liquid densities.
The method fits to the general form of eqn. (1) with
b=b,,,--t (5)
and, when applied to the van der Waals equation,

F(f) = 0 + d2 (6)
The parameter b, is the original van der Waals volume parameter which is
independent of temperature and therefore b’ = db/dT = -d t/dT. Watson
et al. (1986) presented generalized formulae for t and it can be derived from
their equations that dt/dT > 0, which implies that b’ < 0. Thus the volume-
translation method of Watson et al. (1986) shoqld yield an inconsistent
description of the compressed liquid region.
The results obtained for methane are shown in Fig. 1. Here, the gener-
alized relations for dependences of t and a (eqn. (1)) on temperature
obtained by Watson et al. (1986) were used for sub-critical temperatures.
There are maxima on compressed liquid isochores where aP/aT), = 0
holds. The line going through these maxima divides a compressed liquid
region into two parts, one below the line where (aP/aT), is positive, and
the other, above the line, where (iW/aT), is negative. These lines are shown
for several substances in Fig. 2. Pressures at which (U/aT)p is zero are
surprisingly low, especially for near-to-critical temperatures. Thrs may play a
role even in current calculations for chemical engineering. However, the
consistency along the saturation curve is not affected.
A word should be said about the supercritical region. A part of the
diagram for T, > 1 is also depicted in Fig. 1, but here the values of t and a
corresponding to the critical temperature were used, as is often recom-
mended for the use of the same equation of state for both sub-critical and
supercritical temperatures. An extrapolation from the sub-critical range is
always unreliable and with the volume-translation method it has no physical
significance. As can be easily verified, the values of t obtained from
Watson’s generalized relations increase sharply with increasing temperature
above the critical temperature and consequently pressure would decrease
along the isochores in the supercritical region. However, even with t and a
being constant at temperatures above critical, there are discontinuities in
(aP/aT), at the critical temperature, as can be seen from Fig. 1. Moreover,
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0.8 0.9 1.0

5

Fig. 2. The lines of zero value of @P/U),, for several substances as obtained from the
volume-translation method of Watson et al. (1986).

the entire PpT space comprises inconsistencies in the sense that some
sub-critical compressed liquid isotherms may cross the isotherms for super-
critical temperatures in a P-p diagram.

LIST OF SYMBOLS

a, b, b, parameters of equation of state

a’, b’, F’ derivatives of a, b, F with respect to temperature
F(P) polynomial function of density
p, pr pressure, reduced pressure
R universal gas constant
T, T, temperature, reduced temperature
t translation in volume
V molar volume
(YP isobaric thermal expansion coefficient
P, Pr molar density (l/V), reduced density

REFERENCES

HnedkovskL, L., Cibulka, I. and Holub, R., 1990. How cubic equations of state describe PVT
behaviour of single component liquid phase. Sci. Pap. Prague Inst. Chem. Technol., NlO:
201-266.
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Martin, J.L., 1979. Cubic equation of state - which? Ind. Eng. Chem. Fundam., 18: 81-97.
Peneloux, A., Rauzy, E. and F&e, R., 1982. A consistent correction for Redlich-Kwong-
Soave volumes. Fluid Phase Equilibria, 8: 7-23.
Trebble, M.A. and Bishnoi, P.R., 1986. Accuracy and consistency comparisons of ten cubic
equations of state for polar and non-polar compounds. Fluid Phase Equilibria, 29:
465-474.
Watson, P., Cascella, M., May, D., Salerno, S. and Tassios, D., 1986. Prediction of Vapor
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