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Fluid Phase Equilibria 298 (2010) 67–74

Contents lists available at ScienceDirect

Fluid Phase Equilibria


journal homepage: www.elsevier.com/locate/fluid

About the numerical pitfalls characteristic for SAFT EOS models


Ilya Polishuk ∗
Department of Chemical Engineering & Biotechnology, Ariel University Center of Samaria, 40700 Ariel, Israel

a r t i c l e i n f o a b s t r a c t

Article history: This study demonstrates that SAFT EOS models might exhibit the practically unrealistic and even non-
Received 30 May 2010 physical predictions due to the two factors, namely the temperature dependencies of a segment packing
Received in revised form 3 July 2010 fraction and the very high-polynomial orders by volume. The first factor is responsible for predicting
Accepted 5 July 2010
the negative values of the heat capacities at very high pressures and the intersections of isotherms at
Available online 13 July 2010
high densities. The very high-polynomial orders of several SAFT EOS models result in prediction of the
additional stable unrealistic critical points and the pertinent fictive phase equilibria. It is demonstrated
Keywords:
that the unrealistic phase splits might present the globally stable states established by the models, while
Equation of state
Statistical association fluid theory
the VLE matching the experimental data might be in fact metastable. In addition, the excessive complexity
Phase equilibria of certain SAFT models might result in wrong prediction of auxiliary thermodynamic properties of the
Global stability experimentally available fluid phases. The undesired predictions discussed in the present study arise
queries regarding the robustness and the over-all physical validity of the models under consideration in
their present forms. This study discusses the ways of removing the numerical pitfalls.
© 2010 Elsevier B.V. All rights reserved.

1. Introduction compounds. However the reasons of this behavior have not been
investigated with great details.
The EOS models based on the Statistical Association Fluid The- The comprehensive studies of Yelash et al. [12,13] have demon-
ory (SAFT) are among the most important approaches for modeling strated that the predictions of PC-SAFT [14] are affected by crossing
thermodynamic properties of pure substances and their mix- of isotherms, attributed to the temperature dependence of hard-
tures. The comprehensive reviews of different SAFT EOS models sphere diameter, and by appearance of practically unrealistic phase
are available elsewhere [1–5]. Based on the advanced molecular equilibria, attributed to the polynomial expression of the dispersion
approaches, the SAFT EOS models are expected to be robust and term. It has been concluded that the unrealistic phase behavior can
reliable in the entire thermodynamic phase space. However, thus be a problem when the model is applied to polymer solutions and
far several studies have reported some worrying results. polymer blends. The predictions of the excessive phase equilibria
In particular, Koak et al. [6] have investigated the effect of the for large variety of pure compounds exhibited by PC-SAFT have
Chen–Kreglewski (CK) [7] dispersion term on the pressure–volume been recently discussed in great details by Privat et al. [15].
behavior of two non-associating pure components predicted by the The aim of the present study was detection and investigation of
CK-SAFT of Huang and Radosz [8]. It has been demonstrated the P–v the numerical pitfalls exhibited by several popular SAFT EOS mod-
isotherms exhibit multiple volume roots at low temperatures and els necessary for further development of their consistent versions.
volumes, while the smallest practically unrealistic root is more sta-
ble than the realistic ones. It has been concluded that this behavior 2. Theory
appears to be inconsistent with the intention of the original theories
and it needs to be resolved (see also [9]). The SAFT EOS models treat the compressibility factor as a
In the paper discussing the numerical pitfalls introduced by the combination of terms representing different inter-molecular inter-
Soave-type ␣-functions in Cubic Equations of State [10] it has been actions:
demonstrated that the theoretically based models such as the SAFT
version of Huang and Radosz [8] and Johnson–Zollweg–Gubbins Z = Z repulsive + Z attractive + Z associative (1)
approach for the Lennard–Jones fluids [11] exhibit the practically In most of the cases the first two terms are the polynomial expres-
unrealistic predictions, namely the multiple critical points for pure sions by volume, which makes their general analytical investigation
relatively easy. The associative term includes logarithmical expres-
sions for the volume, which substantially hinders its analytical
∗ Tel.: +972 3 9066346; fax: +972 3 9066323. investigation. Hence the question of an over-all consistence of this
E-mail addresses: polishuk@ariel.ac.il, polishyk@bgumail.bgu.ac.il. term has been left outside the scope of the present study and it

0378-3812/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.fluid.2010.07.003
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68 I. Polishuk / Fluid Phase Equilibria 298 (2010) 67–74

Table 1
Phenomena of the multiple critical points generated by the non-associative SAFT
EOS models considered in the present study.

Model Polynomial order Appearance of the


by volume phenomena

SSAFT [19] m = 1 5 No
SSAFT [19] m =/ 1 6 No
Original SAFT [21] m = 1 8 No
Original SAFT [21] m =/ 1 9 No
CK-SAFT [8] m = 1 13 Yes
CK-SAFT [8] m = / 1 14 Yes
Simplified PC-SAFT [24] m = 1 19 Yes
Simplified PC-SAFT [24] m =/ 1 24 Yes
Soft-SAFT [25] m = 1 Non-applicable, Yes
exponential
expression
Soft-SAFT [25] m =
/ 1 Non-applicable, Yes
exponential
expression
Fig. 3. CV of ethane predicted by SSAFT [19]: 100 bar, solid line; 9000 bar, dashed
line;  and 䊉, experimental data [20].

where uo /k and Voo are the positive compound-specific parameters,


 = 0.74048 and C = 0.12. The numerator of Eq. (2) is the model’s
covolume, or the volume at the infinite pressure. It can be seen that
Eq. (2) results in decrease of covolume with temperature. In other
words, as the temperature rises, the infinite pressure is approached
at the smaller values of volume. As a result, at high-pressures
volume will decrease with temperature and the isotherms will

Fig. 1. Intersection of isotherms predicted by SSAFT [19] for ethane; ,, and ,
experimental data [20].

should be considered in future studies, after formulating the appro-


priate approaches for its general analysis.
The numerical pitfalls of the repulsive term are generated by the
temperature dependence of the reduced density . For example,
according to CK-SAFT of Huang and Radosz [8] it is given as:
3
V oo (1 − C exp[−3(uo /k)/T ]) Fig. 4. Intersection of isotherms predicted by SAFT of Chapman et al. [21] for ethane;
= (2)
V ,, and , experimental data [20].

Fig. 2. Lines of zero CV predicted by several versions of SAFT for ethane. Fig. 5. The 120 K isotherm of nitrogen predicted by CK-SAFT [8].
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I. Polishuk / Fluid Phase Equilibria 298 (2010) 67–74 69

Table 2
Critical points predicted by CK-SAFT [8] for several pure compounds.

Compound Tc1 (K) Pc1 (bar) Tc2 (K) Pc2 (bar)

Nitrogen 127.04 35.33 159.95 23870.1


Argon 151.56 50.28 191.74 34125.4
Methane 192.17 48.15 242.85 32643.7
Carbon monoxide 136.45 39.16 146.75 26131.9
Ethane 320.61 60.24 254.59 46646.7
Carbon dioxide 320.71 92.50 311.20 63525.7
Water 725.95 422.88 682.38 166350.8

Fig. 6. The 120 K isotherm of nitrogen predicted by CK-SAFT [8] at high densities.

Fig. 9. The 150 K isotherm of nitrogen predicted by CK-SAFT [8].

as recently demonstrated by Kalikhman et al. [16]. In particular, it


has been proven that any temperature dependency of the covol-
ume necessarily results in infinite negative value of the isochoric
heat capacity at the infinite pressure. It should be pointed out
that although CV < 0 is mathematically possible, it cannot actually
occur, since the mechanical stability limit will be violated before
Fig. 7. Two vapor pressure curves of pure nitrogen predicted by CK-SAFT [8]; 䊉, the thermal limit. This is because the mechanical limit represents
experimental data [23]. a response of higher-order than the thermal limit [17,18]. Con-
sidering a fact that the models with the temperature-dependent
intersect in contradiction with experimental facts. The same effect covolumes exhibit the negative CV under conditions of mechanical
is characteristic for other expressions of covolume exhibiting sim- stability, such predictions should be considered as non-physical.
ilar behavior. The latter phenomena might affect different models with the
Another serious drawback of the temperature-dependent covol- different degree of extend. While some models, such as the CK-
umes is the description of the caloric properties at high pressures, SAFT of Huang and Radosz [8], exhibit the negative isochoric heat
capacities at the extremely high pressures (the reason will be dis-

Fig. 8. Two-phase envelopes of pure nitrogen predicted by CK-SAFT [8]; 䊉, experi- Fig. 10. Departure Gibbs energy – pressure projection of nitrogen generated by
mental data [21]. CK-SAFT [8] at 150 K.
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70 I. Polishuk / Fluid Phase Equilibria 298 (2010) 67–74

Table 3
Critical points predicted by CK-SAFT [8] with D29 = 0.

Compound Tc1 (K) Pc1 (bar) Tc2 (K) Pc2 (bar)

Nitrogen 125.54 33.26 16.54 36477.3


Argon 149.74 47.32 17.1 45041.2
Methane 189.87 45.32 22.53 44798.2
Carbon monoxide 135.78 38.27 16.02 43542.4
Ethane 320.29 59.97 29.15 86343.5
Carbon dioxide 319.87 91.31 45.87 144762.0
Water 721.06 409.18 60.88 260270.1

Fig. 1 depicts the intersection of isotherms predicted by SSAFT


[19] for ethane. Fig. 2 presents the zero values of CV predicted
by several versions of SAFT for ethane. It can be seen that SSAFT
starts to predict the non-physical negative values at the low-
est pressures, which are still very high (14,900 bars and above).
However it would not be surprising that these undesired phe-
Fig. 11. The minus departure Gibbs energy – pressure projection of nitrogen gen- nomena have an impact on modeling the experimentally available
erated by CK-SAFT [8] at 120 K. caloric data. In particular, Fig. 3 demonstrates that SSAFT substan-
tially underestimates the experimental CV data at 9000 bar, which
cussed below), irrelevant for most practical implementations, the should be explained by the behavior of the model at higher pres-
other ones might yield the non-physical predictions at much lower sures.
pressures [16].
The attractive terms of SAFT EOS models typically present poly- 3.2. SAFT of Chapman et al. [21]
nomials adjusted to the theoretical expressions, whose analytical
calculation is not always possible. As the polynomial order becomes Although this model has a relatively high-polynomial order (see
higher, the EOS models yield more solutions for the volume. The Table 1), the additional practically unrealistic solutions for the vol-
complex solutions and the solutions smaller than the covolume ume have not been detected. However the model is still affected by
should be considered as the “numerical noise” having no impact the temperature-dependent covolume. Fig. 4 depicts the intersec-
on the performance of the model. However, if the polynomial tion of isotherms predicted for ethane and Fig. 2 presents the zero
order and, consequently, the number of the solutions increases, values of CV .
the additional practically improbable real solutions bigger than
the covolume appear. Table 1 lists several popular SAFT EOS mod- 3.3. CK-SAFT of Huang and Radosz [8]
els, their polynomial order (when applicable) and appearance of
unrealistic volume solutions. In what follows let us consider the The polynomial order of this model is higher than in the previ-
particular models. ously considered cases (see Table 1) and analysis shows that it may
exhibit up to five real solutions for molar volume bigger than the
covolume. These multiple real solutions are not only excessive on
3. Results
the thermodynamic phase scene, but might also be dangerous like
the famous Chekhov’s gun (“If in Act I you have a pistol hanging on
3.1. Simplified SAFT (SSAFT) of Fu and Sandler [19]
the wall, then it must fire in the last act” [22]).
Fig. 5 depicts the isotherm predicted by the Huang and Radosz’s
This model has the lowest polynomial order among the SAFT
version of CK-SAFT [8] for nitrogen at 120 K. The points A, B and C
models (see Table 1) and it does not exhibit the additional practi-
represent the realistic phase envelope matching the experimen-
cally unrealistic solutions for the volume. However the temperature
tal data (A is the vapor and C is the liquid solution), and the
dependence attached to its covolume still affects its robustness.
extrema ˛ and ˇ represent the spinodal. At the volumes lower that
C the isotherm should approach the infinite pressure. However, as

Fig. 12. Two vapor pressure curves of pure ethane predicted by CK-SAFT [8]; , Fig. 13. Two-phase envelopes of pure ethane predicted by CK-SAFT [8]; , experi-
experimental data [20]. mental data [20].
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I. Polishuk / Fluid Phase Equilibria 298 (2010) 67–74 71

Fig. 15. Globally stable phase diagram of methane predicted by SOFT-SAFT [25]; ,
experimental data [26].

pure compounds. Table 2 lists these critical points for certain pure
compounds.
Fig. 9 depicts the isotherm at 150 K of nitrogen. It can be seen
that this time it takes a conventional form (three solutions and
two extrema), although in total disagreement with experimental
facts. Fig. 10 presents the excess Gibbs energy – pressure projec-
tion for this isotherm. It can be seen that the stable, the metastable
(A = E −  and A = E − ı) and the unstable (ı − D − ) parts exhibit
a robust behavior characteristic for phase equilibria in pure com-
pounds. Thus, there are no doubts regarding the stability of VLE-2
above the critical point 1.
However at the coexisting of two-phase equilibria the picture
Fig. 14. Departure Gibbs energy – pressure projection of ethane generated by CK-
SAFT [8]. becomes complicated (see Fig. 11; −G is used for creating the
logarithmic scale). Three facts can be observed:

noticed, SAFT exhibits five real solutions bigger than its covolume. 1. The VLE-2 take place at the conditions closer to the ideal gas state
It can be seen that the two excessive solutions (E and D) deform and, therefore, at the GE closer to zero than the VLE-1.
the thermodynamic phase space established by the model. As a 2. There are no phase equilibria between the liquid phases.
result, two practically unrealistic extrema  and ı appear (addi- 3. The liquid-2 (solution E) is more stable than the liquid-1 (solu-
tional details are shown in Fig. 6). Thus, two spinodal loci and tion C) and the VLE-1 at the pertinent pressure.
two-phase equilibria are generated simultaneously: the saturation
pressure 1 in the vicinity of experimental datum and the unrealistic The interpretation of Fig. 11 is not trivial because the prac-
saturation pressure 2 located at the deep vacuum. tically unrealistic phase behavior generated by the model under
Figs. 7 and 8 depict two vapor pressure lines and two-phase consideration cannot be explained by experimental facts. Let us
envelopes predicted by the CK-SAFT [8] for nitrogen. As discussed consider nitrogen at some point along VLE-1. As noticed, at such
previously [10], the model exhibits at least two critical points for conditions the liquid-2 (solution E) presents the most stable phase.
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72 I. Polishuk / Fluid Phase Equilibria 298 (2010) 67–74

Fig. 16. Thermodynamic properties of methane [26] at high pressures as predicted by SOFT-SAFT [25]; 䊉, 100 bar; , 200 bar; , 500 bar; , 1000 bar; , 2000 bar; , 5000 bar;
, 10,000 bar.

Thus, according to CK-SAFT [8], at the conditions of VLE-1 and in be seen that yet at least some part of the realistic phase equilibria
the varying-volume vessel nitrogen is supposed to shrink into this (VLE-1 above LLVE) is globally stable. An explanation is provided in
highly compressed liquid. However even the microscopic increase Fig. 14.
of the vessel’s volume should result in a drastic fall of pressure In particular, it can be seen that at the T > TLLVE both VLE-1 and
(see Figs. 5 and 6) until appearance of VLE-2 at the deep vacuum. LLE do not face other phases with lower G at the pertinent pres-
Thus, the realistic VLE-1 is actually metastable and the unrealistic sures, and therefore both are globally stable. However, at T < TLLVE
VLE-2 represents the globally stable phase diagram established by the situation gets different. Yet vapor has lower G than LLE and
CK-SAFT [8]. liquid-2 has lower G than VLE-1. Thus, only the unrealistic VLE-
Table 2 shows that for some compounds CK-SAFT [8] gener- 2 is now globally stable. Remarkably, similar behavior has been
ates the realistic critical points at the temperatures higher than described by Privat et al. [15] for PC-SAFT. However it should be
the unrealistic ones. Figs. 12 and 13 depict the globally stable parts noticed that in the present case the numerical pitfalls significantly
of the ethane’s phase diagram as predicted by CK-SAFT [8]. It can affect the accuracy of the model.
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I. Polishuk / Fluid Phase Equilibria 298 (2010) 67–74 73

An artificial attempt of decreasing the polynomial order of CK- The very high-polynomial orders of several SAFT EOS mod-
SAFT [8] by considering the zero value for D29 might improve the els result in prediction of the additional stable unrealistic critical
situation (see Table 3). Remarkably, this practice does not affect the points and the pertinent fictive phase equilibria. It is demonstrated
CK dispersion term radically. that the unrealistic phase splits might present the globally sta-
Finally, it should be pointed out that CK-SAFT [8] unavoidably ble states established by the models, while the VLE matching the
exhibits the numerical pitfalls characteristic for the previously con- experimental data might be in fact metastable. In addition, the
sidered simpler versions of SAFT. However since approaching the excessive complexity of certain SAFT models might result in non-
infinity pressure at low temperatures is yet hindered by the unusual physical prediction of auxiliary thermodynamic properties of the
forms of its isotherms, CK-SAFT [8] generates the negative isochoric experimentally available fluid phases. Thus, some SAFT EOS models
heat capacities at much higher pressures (see Fig. 2). should be re-evaluated while using fewer coefficients. Investiga-
tion of the maximal equation orders free of the numerical pitfalls
3.4. PC-SAFT [14] is essential for further progress of SAFT.
In addition, it seems highly recommendable to make the seg-
The case of PC-SAFT [14] has been already investigated with ment packing fraction of SAFT models temperature-independent.
great details in the previous studies [12,13,15]. It should only be It could be argued that the temperature-dependent covolumes
noticed that the rescaled simplified PC-SAFT [24] does not exhibit result in numerical pitfalls outside the range of the model’s appli-
an improvement in comparison with the original version. Never- cability (extremely high pressures). However the very concept of
theless the fact that PC-SAFT, in spite of its very high-polynomial the model’s applicability is characteristic for empirical correlations
order, typically generates the unrealistic phase equilibria at rela- rather than theoretically based approaches. The latter ones are sup-
tively low temperatures [15] should not be neglected. Hence, the posed to be robust and reliable in the entire thermodynamic phase
undesired predictions yielded by PC-SAFT [14] are not expected to space. Moreover, it does not seem possible to cancel the numeri-
affect most of its practical implementations. One might anticipate cal contribution of the repulsive term to the residual isochoric heat
for problems just in certain cases [12,13]. In addition, the unre- capacity at high pressures by other model’s terms.
alistic phase equilibria could interrupt the high-pressure LLE in
asymmetric mixtures at high pressures. Moreover, the probability List of symbols
of numerical problems might increase with increasing the number C integration constant of CK-SAFT [8]
of compounds in a mixture. CV isochoric heat capacity
k Boltzmann’s constant
3.5. Soft-SAFT [25] P pressure
R universal gas constant
The Soft-SAFT [25] EOS is based on the T temperature
Johnson–Zollweg–Gubbins approach for the Lennard–Jones fluids uo /k temperature-independent dispersion energy of interac-
[11]. The latter approach typically exhibits the additional artificial tion between segments
phase equilibria at the temperatures higher than CK-SAFT [8] (see V molar volume
for example [10]). The same could be concluded regarding the Voo temperature-independent segment volume of CK-SAFT
Soft-SAFT [25]. For example, for methane it predicts: Tc1 = 193.27 K, [8]
Pc1 = 50.97 bar, Tc2 = 320.64 K and Pc2 = 24371.8 bar. Fig. 15 depicts W speed of sound
the globally stable phase equilibria yielded by Soft-SAFT [25] for Z compressibility factor
methane. A total disagreement with the experimental facts is
evident. Greek letters
Fig. 16 demonstrates that Soft-SAFT [25] could be an incredi-  reduced density
bly accurate model for describing the high-pressure densities, heat  segment molar volume in a closed-packed arrangement
capacities and sound velocities. However it can be seen that the sig-
nificant part of the Soft-SAFT’s [25] fluid phase diagram is actually Subscripts
metastable because the artificial high-pressure phase split takes c critical state
place above the compound’s solidification temperatures. In addi- r reduced property
tion, it predicts the negative values for the heat capacities and, as a
consequence, wrong results for the sound velocities below 100 K. It Abbreviations
would be tempting to find a relation these two facts [17,18]. How- EOS equation of state
ever it can be seen (Fig. 16a) that Soft-SAFT’s [25] still predicts the SAFT statistical association fluid theory
mechanical stability at the experimentally available fluid range.
Thus, the current non-physical results could rather be explained Acknowledgment
again by the excessive complexity of the model under considera-
tion. Acknowledgment is made to the Donors of the American Chem-
ical Society Petroleum Research Fund for support of this research,
4. Conclusions Grant No. PRF#47338-B6.

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