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1603
REVIEWS
The State of the Cubic Equations of State
Jose O. Valderrama*
Faculty of Engineering, University of La Serena, Casilla 554, and Center for Technological Information (CIT),
Casilla 724, La Serena, Chile
The development of van der Waals cubic equations of state and their application to the correlation
and prediction of phase equilibrium properties is presented and analyzed. The discussion starts
with a brief account of the contributions to equation of state development during the years before
van der Waals. Then, the original equation proposed in the celebrated thesis of van der Waals
in 1873 and its tremendous importance in describing fluid behavior are analyzed. A chronological
critical walk through the most important contributions during the first part of the 1900s is
made, to arrive at the proposal that I consider to be the most outstanding since van der Waals:
the equation proposed by Redlich and Kwong in 1949. The contributions after Redlich and Kwong
to the modern development of equations of state and the most recent equations proposed in the
literature are analyzed. The application of cubic equations of state to mixtures and the
development of mixing rules is put in a proper perspective, and the main applications of cubic
equations of state to binary and multicomponent mixtures, to high-pressure phase equilibria,
to supercritical fluids, to reservoir fluids, and to polymer mixtures are summarized. Finally,
recommendations on which equations of state and which mixing rules to use for given applications
are presented.
Contents
Introduction
van der Waals Proposal
Redlich-Kwong (RK) Proposal
From Redlich-Kwong to Soave
Modifications to the SRK and PR
Equations
Modifications to r(TR)
Volume-Translated Equations
Three-Parameter Equations of
State
Application to Mixtures
Classical Mixing Rules
Volume-Dependent Mixing Rules
Nonquadratic Mixing Rules
EoS + Gibbs Free Energy
Models
Mixing Rules of Mansoori and
Co-workers
Applications of Cubic EoS to
Reservoir Fluids
Mixtures Containing
Supercritical Components
Cubic EoS Applied to Polymer
Solutions
Recommendations
Conclusions
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Introduction
Since van der Waals proposed the first version of his
celebrated equation of state (EoS) more than a century
* E-mail: citchile@entelchile.net, jvalderr@userena.cl.
P)
RT
- Patt(T,V)
V-b
Patt(T,V) )
a
V(V + d) + c(V - d)
(1)
(2)
1604
disadvantages
b
c
d
e
simulations. There are several reasons for this popularity but also several disadvantages of cubic equations,
which have encouraged many researchers to look for
different approaches such as those mentioned above.
Table 1 summarizes some of these advantages and
disadvantages of cubic EoS.
To clarify the limits and scope of this paper, a
convenient classification is shown in Figure 1. This
paper is limited to those aspects that the author finds
relevant in the development of the group called cubic
empirical equations. The paper starts with a short
review of the history of cubic EoS, leading to an
assessment of which EoS might be most useful for
several applications. Because of the enormous amount
of literature on the subject of EoS, one can always
quarrel with which publications to include in a review
like the present one. Thus, the publications included
here represent what the author considers most relevant
for the practitioners in the field of fluid properties and
phase equilibria using cubic EoS.
A recent book published by IUPAC8 reviews the main
advances of EoS for fluids and fluid mixtures. The
Figure 1. Classification of various type of equations of state, with a selection of equations for each group. In this classification, van der
Waals EoS are those cubic and noncubic equations that consider the compressibility factor as Z ) Zrep + Zatt.
P+
a
(V - b) ) R(1 + Rt)
V2
(3)
RT
a
P)
- 2
(V - b) V
(4)
The parameters, or so-called equation of state constants, a and b were first calculated using PVT data
but were later related to critical properties by applying
the condition of continuity of the critical isotherm at the
critical point. This requirement allows the constants to
be related to the critical pressure and temperature, Pc
and Tc, respectively, and also gives a constant value for
the critical compressibility factor (zc ) 0.375).
van der Waals equation of state and his ideas on
intermolecular forces have been the subjects of many
P)
RT
a/T
(V - b) (V + c)2
(5)
1606
P)
R(T) ) a/T0.5
acR(T)
RT
V - b V(V + b)
(6)
ac ) aR2Tc2.5/Pc
a ) 0.4278
b ) bRTc/Pc
b ) 0.0867
This equation did not have a strong theoretical background but proved to give good results for many gaseous
systems. It should also be mentioned that, when Redlich
and Kwong proposed their celebrated equation of state,
they were interested in developing a good equation for
gases only. Not a single application to liquids can be
found in Redlich and Kwongs original paper.
During the period 1960-1980, the interest in RedlichKwong-type equations was so high that the RK equation
can be considered the most modified EoS ever. A
complete account of all such equations is not easy to
provide; however, following some good review articles
and our own findings, it is not adventurous to estimate
that there must be about 150 RK-type equations and a
total of 400 cubic EoS proposed to date in the literature.
During the 15 years after Redlich and Kwongs proposal,
the equation seemed to be one more of the already many
modifications to the vdW equation, with the ChaoSeader correlation being the only major application of
this EoS. The works of Wilson,23 Barner et al.,24 and
Chueh and Prausnitz25 attracted renewed interest in
exploring Redlich and Kwongs equation.
From Redlich-Kwong to Soave
Wilson23 made a major contribution to the attempts
at generalizing the RK equation. He was able to consider
the variations in behavior of different fluids at the same
reduced pressure and reduced temperature by introducing Pitzers acentric factor () into the attractive term.
Wilsons equation was largely ignored during the rest
of the 1960s and until 1972, the time of Soaves proposal.
Soave26 proposed a new improved version of Wilsons
idea. He redefined the R(TR,) function and kept the
RK volume functionality, giving what became, in a short
period, one of the most popular EoS in the hydrocarbon
industry. Computer simulation packages became popular during the late 1960s, and there was great need for
a simple, generalized, and reasonably accurate EoS for
the many repetitive calculations required in process
simulations. Soaves EoS, commonly known as the SRK
equation, satisfied the need at that time. Also, in the
mid 1970s, optimization of industrial processes became
extremely important, because of the so-called oil crisis,
and Soaves equation was again of great help for the
type of calculations required in optimization algorithms.
The SRK equation can be summarized as follows
P)
RTc2.5
ac ) 0.427 47
Pc
RTc
b ) 0.086 64
Pc
acR(TR,)
RT
V-b
V(V + b)
(7)
P)
ac) 0.45724
acR(TR,)
RT
V - b V(V + b) + b(V - b)
RTc2.5
Pc
(9)
b ) 0.07780
RTc
Pc
m ) 0.37464 - 1.54226 - 0.269922
ref
1/xTr
Tr(1 + mTr-1)
m/Tr + n/Tr2
[1 + m(1 - xTr)]2
1 + m(Tr - 1)2(1 - xTr)2
R(Tr) ) 1 + (1 - Tr)(m + n/Tr)
exp[C(1 - Trm)]
[1 + m(1 - xTr) + nx1 - Tr/0.7]2
m1 + m2/Tr + m3/Tr2
exp[C(1 - Trd)]
[1 + m(1 - xTr) - p(1 - Tr)(0.7 - Tr)]2
1 + m1(1 - xTr) + m2(1 - xTr)2 + m3(1 - xTr)3
[1 + m(1 - xTr)]2/Tr
m1 + m2/Tr + m3/Tr2 + m4/Tr3
1 + m1(Tr - 1) + m2(xTr - 1)
[1 + m(1 + Trn)]2
[1 + m(1 - xTr) + n(1 - Tr)(0.7 -Tr)]2
[1 + m(1 - xTr)]2 + n(Tr - 0.6)2
[1 + m(1 - xTr) - p(1 - Tr)(q - Tr)]2
{[1 + n exp(-k)]/[1 + nexp(-kTr2m)]}Tr2m-1 exp[(1 - Tr2m)k]
exp[m(1 - Tr) + n(1 - xTr)2]
exp[p(1 - Tr)|1 - Tr|-1 + q(T-1 - 1)]
[1 + m(1 - xr)]2, ) (T - Tpt)/(Tc - Tpt)
P)
RT
a
V + t - b (V + t)2
(12)
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ln i ) -ln(Z - B) +
A/2
BC +
Pv
,
RT
ai P
R2T2
)[
B+C
2
Ai )
Ai
+1A
Ai )
Bi )
biP
,
RT
( )
nA
ni
Ci )
][
ci P
,
RT
A)
aP
,
R2T2
B)
bP
,
RT
C)
B+C
B+C
BC + (
(
2 ) x
2 )
ln
) Z + (B +2 C) + xBC + (B +2 C)
R/4
B+C
BC +
2
a
RT
V - b V(V + b) + c(V - b)
a ) 0.661 21 - 0.761 057zc
b ) 0.022 07 - 0.208 68zc
c ) 0.577 65 - 1.870 80zc
F ) 0.462 83 + 3.582 30zc + 8.194 17(zc)2
Z+
Bi )
T,V,nj
( )
nB
ni
1
4
T,V,nj
Ci )
( )
nC
ni
cP
RT
ZR +
B+C
BC +
2
Bi
(1 - Z -1 B) + Z - B
T,V,nj
Expressions for the partial derivatives included in the above equations are obtained for each mixing rule to be employed.
a)
i j xixjaij
b)
i j xixjbij
c)
i j xixjcij
(13)
(14)
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Table 4. Selected Mixing Rules and Combining Rules Used in Two-Constant Cubic Equations of State
mixing/combining rule
formulas
x x a
x x b
a)
Panagiotopoulos-Reid (PR)
two parameters: kij, kji
three parameters: kij, kji, lj
b)
i j ij
i j ij
1
bij ) (bi + bj)(1 - lij)
2
1
bij ) (bi + bj)(1 - lij)
2
aij ) xaiaj(1 - kij)
Kwak-Mansoori (KM)
three parameters: kij, ij, lij
x x (a a ) - ( - )g
1
b ) x x b , b ) (b + b )
2
E
RES/ln[(b
0.5
a)
i j
i j
i j ij
Wong-Sandler
one parameter: kij
two parameters: kij, li (one solute)
ij
- )/(b - )]
E
gRES
) RTx1x2[1 + 2(x1 - x2) + 3(x1 - x2)2]
bm )
xixj(b - a/RT)ij/
[1 - xiai/biRT - AE(x)/RT]
(16)
xiai/bi + AE(x)/
am ) bm[
system
naphthalene
phenanthrene
anthracene
2,3-dimethylnaphthalene
2,6-dimethylnaphthalene
caffeine
SRK
PR
PTV
PTV
T (K) WS/KTK WS/KTK WS/KTK MRS
308
313
318
318
328
338
303
323
343
308
318
328
308
318
328
313
333
353
% average
deviation
1.3/1.1
1.1/2.3
1.0/3.9
1.5/1.2
1.3/2.4
1.1/4.1
2.4/2.6
1.9/5.3
1.5/5.3
7.9/7.6
7.3/5.7
6.3/7.1
8.3/7.3
5.5/7.0
3.4/7.8
8.3/8.4
7.1/6.5
6.3/8.4
6.6/10.7 5.9/19.3 5.2/8.1
15.7/7.2 16.2/18.6 19.1/9.5
9.2/9.9
8.4/21.3 7.1/11.2
2.5/2.5
2.3/11.8 2.4/5.2
7.1/2.6
5.3/8.8
4.3/4.5
2.7/4.3
4.3/6.7
3.7/1.8
6.6/4.9
5.5/2.4
5.4/6.4
6.4/5.1
4.0/3.5
3.1/7.2
15.7/5.5
5.6/5.2
4.2/8.8
4.4/15.3 2.2/15.6 2.0/15.5
4.3/22.8 2.5/24.2 2.8/22.9
6.3/20.1 4.1/20.9 4.1/19.9
6.5/7.7
5.0/10.4 4.6/8.7
1.2
2.1
2.6
5.7
2.4
6.4
2.6
6.4
9.5
3.3
2.8
5.2
4.2
2.8
5.0
2.4
2.3
7.7
4.1
gE ) gERS + gERES
(17)
P)
am + RTdm - 2xamdmRT
RT
V - bm
V(V + bm) + bm(V - bm)
am )
i j xixj(aiiajj)
am )
bm )
xixjaij
i)1 j)1
xixjbij
i)1 j)1
n
0.5
dm )
(19)
(20)
xixjdij
i)1 j)1
The combining rules for aij, bij, and dij given by Kwak
and Mansoori (KM) are
bi1/3 + bj1/3 3
(1 - ij)
2
(21)
di1/3 + dj1/3 3
(1 - ij)
2
ai ) a(Tci)(1 + mi)2
bi )
0.077 80RTci
Pci
di )
(22)
a(Tci)mi2
RTci
Figure 3 shows results for the vapor-phase concentration for the system 2-methyl-1-pentanol + CO2 at high
pressure and 453 K using the PR equation with the
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Equations of state are usually employed for highpressure phase equilibria such as systems containing
supercritical components. The first efforts to model the
phase behavior in systems containing supercritical
fluids were made using the virial EoS,125 but these
attempts were not successful. The best results have been
obtained using cubic EoS such as SRK and PR.126,127
Several combinations between cubic EoS and mixing
rules have been employed and have been presented in
the literature. These included different applications and
modifications of the PR and SRK equations with mixing
rules such as van der Waals, Panagiotopoulos-Reid,
Kwak-Mansoori, Huron-Vidal, Kurihara et al., and
Wong-Sandler, among others.128-139 The book by Sadus140 includes a chapter dedicated to cubic equations
applied to phase equilibria in multicomponent mixtures.
However, none of these works represents a thorough
study on the problem of phase equilibrium in systems
containing a supercritical fluid. Thus, the problem is
not yet exhausted, and there is ample room for research
on different aspects of phase equilibrium modeling.
Literature information and our own research indicate
that, with the present state of knowledge, it is necessary
to include more than one interaction parameter, even
in complex models such as the Kurihara et al. and
Wong-Sandler mixing rules.
A common practice in several applications of cubic
EoS to mixtures containing supercritical fluids has been
to analyze the results in terms of the concentration of
the supercritical solvent in the gas phase, y1. Some
optimistic statements and conclusions found in the
literature are usually drawn by analyzing the vaporphase concentration of the solvent only (usually carbon
dioxide) and not the concentration of the solute, y2, as
should be done to accurately test the capabilities of an
2-methyl-1pentanol
lauric acid
palmitic acid
oleic acid
limonene
R-pinene
phenanthrene
benzoic acid
caffeine
anthracene
naphthalene
2,6-dimethylnaphthalene
2,3-dimethylnaphthalene
-cholesterol
T (K)
P (MPa)
EoS
403
453
348
403
453
348
403
453
423
473
423
473
313
333
313
323
313
323
328
318
328
338
318
328
338
313
333
353
303
323
343
308
313
318
308
318
328
308
318
328
313
323
333
6.5-18.4
6.5-19.0
7.0-19.0
6.0-19.0
6.5-19.0
6.5-11.9
6.5-15.4
6.5-17.9
9.1-5.1
9.1-5.1
9.1-5.1
9.1-5.1
7.2-28.2
7.1-28.6
5.9-7.9
4.9-10.3
3.3-7.9
4.5-9.6
4.8-9.5
11.9-27.7
11.9-27.7
11.9-27.7
11.9-27.7
11.9-27.7
11.9-27.7
19.7-29.7
19.7-29.6
19.7-29.6
10.3-41.0
9.0-41.0
11.7-20.6
10.4-29.7
9.9-34.6
10.1-31.1
9.6-27.7
9.6-27.7
9.5-27.7
9.8-27.7
9.8-27.7
9.8-27.7
9.9-24.8
9.9-24.8
12.9-24.8
PTV
PTV
PTV
PR
SRK
PR
PTV
PTV
PR
PR
PR
SRK
PR
PTV
PTV
PR
PR
PTV
PR
PTV
PTV
PTV
SRK
SRK
PTV
PTV
PTV
PR
PTV
SRK
PTV
PTV
PTV
PTV
PTV
PTV
PTV
PTV
PTV
SRK
PR
PR
PR
5.2
8.1
12.4
10.5
3.4
12.3
7.3
1.1
15.5
13.1
14.3
17.8
15.1
17.1
11.6
19.3
6.1
9.6
15.3
4.5
3.0
6.7
7.1
4.0
0.9
1.5
2.7
3.5
2.6
6.4
7.8
1.1
2.1
2.6
4.2
2.4
4.3
2.4
3.2
1.8
4.4
4.5
5.5
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Table 7. Recommendations on Generalized Equations of State to Use for Several Pure-Fluid Properties
property
gas volume at moderate/
high pressure
gas volume at low temperature,
moderate/high pressure
saturated vapor volume
saturated liquid volume
for nonpolar fluids
saturated liquid volume
for polar fluids
compressed liquid volume
volume near the critical point
vapor pressure for
nonpolar fluids
vapor pressure for polar fluids
vapor pressure for
associating fluids
enthalpy and entropy of liquids
enthalpy and entropy
of gases at low pressure
enthalpy and entropy
of gases at moderate/
high pressure
comments
recommendations
SRK, PR
SRK, PR, PT
PTV, PT, but empirical correlations
should be preferred
PT, but empirical correlations should be preferred
empirical correlations or specific equations
for a given fluid should be used
PTV or other three-parameter EoS with
parameters adjusted using near-critical data
SRK, PR, PTV, but prefer R(T) with specific
parameters for polar fluids, such as Soave-polar28
PR, PTV with complex R(T) function,
such as that of Twu169
noncubic equations specially developed for this
type of fluid should be preferred
specific equations, usually polynomial, should be
preferred
SRK, PR, PTV, but prefer R(T) with specific
parameters
PR and PTV with R(T) with specific parameters;
noncubic equations are also good
Table 8. Recommendations on Generalized EoS and Mixing Rules for Different Types of Liquid-Vapor Mixturesa
type of mixture
EoS
temp function
mixing rule
nonpolar + nonpolar
nonpolar + polar
polar + polar
asymmetric mixtures
polymer solutions
P&R, WS
P&R, WS
WS
P&R, MWS-1P
HV, MWS-1P, ZM
nonpolar + nonpolar
nonpolar + polar
polar + polar
nonpolar + nonpolar
reservoir fluids
polymer solutions
one supercritical component
vdW-1 or -2
vdW-1 or -2
vdW-2, P&R
vdW-1 or -2
vdW-1 or -2
WS, ZM
P&R, WS-2P, WS-3P
Notation for mixing rules as indicated in Table 4. Also ZM is Zhong-Masuoka, HV is Huron-Vidal, and SWP is Sako-Wu-Prausnitz.
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