Fluid Phase Equilibria 295 (2010) 7692

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Fluid Phase Equilibria

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

Are safe results obtained when the PC-SAFT equation of state is applied to
ordinary pure chemicals?
Romain Privat a,b, , Raqul Gani a , Jean-Nol Jaubert b
a
CAPEC, Department of Chemical and Biochemical Engineering, Technical University of Denmark, Building 227, DK-2800 Lyngby, Denmark
b
Nancy-Universit, cole Nationale Suprieure des Industries Chimiques, Laboratoire Ractions et Gnie des Procds - UPR 3349, 1 rue Grandville,
BP 20451, Nancy cedex 9, France

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

Article history: The PC-SAFT equation of state is a very popular and promising model for uids that employs a compli-
Received 18 December 2009 cated pressure-explicit mathematical function (and can therefore not be solved analytically at a specied
Received in revised form 26 March 2010 pressure and temperature, contrary to classical cubic equations). In this work, we demonstrate that in
Accepted 30 March 2010
case of pure uids, the PC-SAFT equation may exhibit up to ve different volume roots whereas cubic
Available online 9 April 2010
equations give at the most three volume roots (and yet, only one or two volume roots have real signi-
cance). The consequence of this strongly atypical behaviour is the existence of two different uiduid
Keywords:
coexistence lines (the vapour-pressure curve and an additional liquidliquid equilibrium curve) and two
Equation of state
Inconsistent predictions
critical points for a same pure component, which is obviously physically inconsistent. In addition to n-
Artefact alkanes, nearly 60 very common pure components (branched alkanes, cycloalkanes, aromatics, esters,
PC-SAFT gases, and so on) were tested out and without any exception, we can claim that all of them exhibit this
SRK undesired behaviour. In addition, such similar phenomena (i.e. existence of more than three volume
Vapour pressure roots) may also arise with mixtures. From a computational point of view, most of the algorithms used
Liquidliquid equilibrium for solving equations of state only search for three roots at the most and are thus likely to be inefcient
Pure-component parameters when an equation of state gives more than three volume roots. To overcome this limitation, a simple
Critical point
procedure allowing to identify all the possible volume roots of an equation of state is proposed.
Resolution of an equation of state
2010 Elsevier B.V. All rights reserved.
Density calculation
Alkane

1. Introduction thermodynamic models, the SoaveRedlichKwong EoS [10] (SRK),

Actual representation of uid phase behaviour is an important
issue in chemical engineering. Since the pioneering work of Van der
Waals [1,2], many equations of state (EoS) for uids have emerged.
They are capable of accounting for both liquid and vapour phases
and allow to represent the thermodynamic behaviour of pure com-
ponents and mixtures. The quality of such models is generally
assessed through their ability to describe physical phenomena
(changes of state, criticality, azeotropy and so on) as well as their
capacity to accurately calculate PVT properties and phase equilib-
ria. However, beyond qualitative and quantitative efciency, the
knowledge of the limitations of the models is of major importance
and must be necessarily taken into account to avoid erroneous cal-
culations. In this paper, we essentially focus on the drawbacks of
the EoS which lead to inconsistent predictions of phase behaviour.
In recent papers [39], some deciencies of three very popular
Corresponding author. Tel.: +33 383175128; fax: +33 383175152.
E-mail address: Romain.Privat@ensic.inpl-nancy.fr (R. Privat).
the original SAFT EoS [11] (Statistical Associating Fluid Theory)
from Huang and Radosz and the PC-SAFT EoS [12] (Perturbed-
Chain-SAFT), were pointed out and discussed. The main conclusions
reached by the authors are the following:
Regarding the cubic SRK EoS [10], Segura et al. [35] have shown
that, for a pure component, in addition to the ordinary vapour-
pressure curve ended by a mechanically stable critical point, a
second vapour-pressure curve connected to a second mechan-
ically stable critical point is likely to arise at extremely high
temperatures (typically at Tr > 10, outside of the temperature
range of practical interest). This atypical behaviour results from
an unphysical behaviour of the Soave alpha function, as pointed
out by many authors [13]. As an illustration, let us consider a c-
titious molecule M (in order to enlarge the phenomena) having
the following properties:

 Tc,M = Tc,ethane = 305.5 K

 Pc,M = Pc,ethane = 48.8 bar

 M = 1.0

0378-3812/$ see front matter 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.uid.2010.03.041
 R. Privat et al. / Fluid Phase Equilibria 295 (2010) 7692
Fig. 1. Representation of three isothermal curves of a pure ctive molecule M at
Tr = 0.95, Tr = 2 and Tr = 12 with the SRK EoS in the (Pr ; vr )-plane.
One subcritical and two supercritical isotherms of molecule M
obtained by using the SRK EoS are plotted in Fig. 1. Whereas
the isotherm Tr = 2 exhibits the classical shape of a supercrit-
ical isotherm, it is noticeable that the supercritical isotherm
Tr = 12 has surprisingly the same shape as the subcritical
isotherm Tr = 0.95. That is: the pressure rst decreases, then
increases and decreases again when the molar volume increases.
A vapourliquid equilibrium can thus be calculated for both these
temperatures (Tr = 0.95 and Tr = 12) even though the SRK EoS
does not predict any phase equilibrium at Tr = 2. More gener-
ally, as mentioned above, it is possible to calculate for M two
vapour-pressure curves, two spinodals (locus of the points ver-
ifying (P/v)T = 0) and two critical points, as shown in Fig. 2.
Note that the additional vapour-pressure curve (at very high tem-
peratures) exhibits a negative slope which involves, according to
Fig. 2. Representation of two vapour-pressure curves (continuous lines), two spinodals (dashed lines) and two critical points (C1 and C2 ) of the pure ctive molecule M using
the SRK EoS. Number 1 refers to low-temperature ordinary curves and number 2 refers to high-temperature additional curves. Tr = T/Tc,1 and Pr = P/Pc,1 .
77
the Clapeyrons equation, a negative enthalpy of vapourization.
Critical coordinates of the additional critical point are found at
Tc,2 = 3293 K = 10.8 Tc,M and Pc,2 = 526.3 bar = 10.8 Pc,M .
Although the original SAFT model [11] is acknowledged as pow-
erful and accurate, some cases of inconsistent calculations using
this model have been reported by Koak et al. [6]. Indeed, con-
sidering pure methane and pure poly(ethylene-propylene), the
authors demonstrated that the EoS could predict up to ve dif-
ferent volume roots at given temperatures and pressures, yet
belonging to ranges of practical interest. They also found con-
ditions where one of the ve volume roots occurring at a reduced
density greater than the theoretical close-packed density was
surprisingly the most stable root. According to Gross and Sad-
owski [7], the PC-SAFT EoS does not seem to suffer from this
drawback.
In addition, Segura et al. [3] briey mentioned that original SAFT
[11] was likely to predict two JouleThomson inversion curves
and two pure-component critical points as well (for example, the
additional critical point of n-butane arises at Tr = 0.59).
In 2005, Yelash et al. [8,9] mentioned that the PC-SAFT EoS may
exhibit articial multiple criticality and phase equilibria. To
illustrate their statement, they only considered ctitious poly-
mers.
In this work, according to the papers of Yelash et al. [8,9], the
inconsistencies of the popular PC-SAFT EoS [12] are pointed out on
real pure chemicals. It is demonstrated that for any n-alkane and
for many other chemicals (branched alkanes, alkenes, cycloalkanes,
aromatic compounds, ethers, esters, permanent gases, halogenated
hydrocarbons) it is possible to nd at very low temperatures, a
pressure range for which the EoS gives four or ve volume roots.
As a consequence of this atypical behaviour, a low-temperature
uiduid equilibrium line connected to a low-temperature critical
point can be calculated in addition to the ordinary ones. This kind
of unusual behaviour is also rather similar to the ones described by
Segura et al. [35] with cubic EoS and original SAFT.
This study also highlights that when solving an EoS, it is nec-
essary to use an algorithm capable of detecting more than three
molar volume roots. To do so, a simple algorithm is proposed.
78 R. Privat et al. / Fluid Phase Equilibria 295 (2010) 7692
2. Short presentation of the PC-SAFT EoS
The Pertubed Chain-Statistical Associating Fluid Theory (PC-
SAFT) EoS has been developed in 2001 by Gross and Sadowski
[12] at the Technical University of Dortmund. Applying a perturba-
tion theory for chain molecules inspired from two papers of Barker
and Henderson [14,15], Gross and Sadowski derived a dispersion
expression for chain molecules and used a hard-chain reference
uid. Let us notice that other classical SAFT models [11,16] use
a hard-sphere reference uid meaning that the dispersion term
accounts for attraction between spherical segments, not for attrac-
tion between hard chains [17].
In its original formulation, the PC-SAFT EoS is applicable to
non-associating components only. The reduced residual molar
Helmholtz energy is then obtained from the following expression:
ares ahs achain adisp
= + + (1)
RT RT RT RT
   other words, existence of multiple uiduid saturation pressures
aref /(RT )
The reference term (i.e. the hard-chain term) represents the global
Helmholtz energy of an elementary chain formed from elementary
segments (hard spheres) and is obtained by adding a hard-sphere
term to a chain term that accounts for the formation of the chain.
The third term of the right hand side of Eq. (1) is a dispersion contri-
bution which reects interactions between hard chains. The molar
compressibility factor z of a pure uid is given by:
Pv
z(T, v) = = 1 + z ref (T, v) + z disp (T, v) (2)
RT
For a pure uid: z ref = mz hs + z chain , where m represents the aver-
age number of segments (hard spheres) in a hard chain. In addition
to m, two other parameters (occurring in the expression of a mod-
ied square-well potential for the segment of a chain) are used to
dene a pure component. These are the temperature-independent
segment diameter  and the depth of pair potential characterizing
the dispersion forces.
Nowadays, the Perturbed-Chain-SAFT EoS is probably one of the
most attractive SAFT models among the academic and industrial
communities. Due to its popularity, some authors have extensively
worked on its application to associating and polar uids [1823].
For the purposes of this work, we will only consider the original
version of the PC-SAFT EoS [12].
Concerning the calculation of PVT properties, Eq. (2) clearly indi-
cates that the PC-SAFT EoS employs a pressure-explicit function (i.e.
expresses explicitly the pressure as a function of T and v). Due to the
complexity of the mathematical formulation, it seems necessary
to solve numerically this EoS at a xed pressure and temperature.
This feature makes the PC-SAFT EoS quite different from classical
cubic EoS which are pressure-explicit too but which can easily be
solved analytically using a Cardanos method [24], for instance. In
Appendix A, the PC-SAFT model is given and equations are sorted
in order to make their resolution easier at a specied temperature
and pressure, following the study by Gani et al. [25]. The rst and
second derivatives of the pressure with respect to the molar vol-
ume are also provided. These two derivatives are very useful to
solve numerically the EoS or to calculate a critical point, as shown
in Appendix B.
3. Thermodynamic consistency vs. physical reality
The calculation of pure-component vapour-pressure curves (or
in the general case, the calculation of uiduid equilibrium lines)
from pressure-explicit EoS is a well-known application of chemical
engineering thermodynamics. To do so, a set of three equations has
to be solved:
sat
sat
P = P(T, vuid phase 1 )
P sat = P(T, vsat ) (3)
ln f (T, vsat
uid phase 2
uid phase 1
) = ln f (T, vsat
uid phase 2
)
The four variables involved in these equations are the temperature
of the uid T, its saturation pressure P sat and the molar volumes of
the rst and of the second uid phases in equilibrium, respectively
vsat and vsat . The variance of the system (also called
uid phase 1 uid phase 2
number of degrees of freedom), which is the difference between
the number of variables and the number of equations, is equal to
one (this result is also conrmed by Gibbs phase rule). One variable
among the four previous ones (T, P sat , vsat and vsat )
uid phase 1 uid phase 2
has thus to be specied to make the system solvable. It is important
to note that specifying a number of variables equal to the vari-
ance does not guarantee uniqueness of the solution of Eq. (3). In
at xed temperature is theoretically not in disagreement with the
Gibbs phase rule. Reciprocally, the calculation of several phase-
equilibrium temperatures at a given pressure does not violate this
rule. This is why, it is neither absurd, nor thermodynamically incon-
sistent to calculate two uid-phase-equilibrium lines using the SRK
EoS, as pointed out in Section 1 of this paper. However, from a
practical point of view, real uids exhibiting such a behaviour have
never been reported.
Consequently, even though some thermodynamic models are
able to predict existence of multiple vapour-pressure curves (e.g.
SRK EoS) or more generally, of multiple uiduid coexistence lines
(e.g. original SAFT EoS, PC-SAFT EoS), this feature appears actu-
ally physically unrealistic or inconsistent. In the title of their paper,
Segura et al. [3] also speak about the pitfalls of such models.
The same arguments apply for pure-component critical points
the variance of which is null. These points verify three critical spec-
ications, that are:
P(T , v ) P = 0
c c  c
(P/v)T  =0 (4)
Tc ,vc
(2 P/v2 ) 
=0
T Tc ,vc
Three critical variables, Tc , Pc and vc , are involved in Eq. (4). Here
again, thermodynamic consistency does not theoretically prevent
a model from calculating several critical points that are practically
unrealistic. It can be pointed out that most of the cubic EoS that
give more than one pure compound critical point exhibit an invari-
ant value for the critical molar volume vc (this is the case of the
SoaveRedlichKwong EoS, of the PengRobinson EoS, etc.). As an
example, the two critical points shown in Fig. 2 have different criti-
cal temperature and pressure values (Tc,1 = / Tc,2 and Pc,1 =
/ Pc,2 ) but
have the same molar volumes (vc,1 = vc,2 ). The calculation of mul-
tiple critical points is thus quite easily performed in such cases:
according to Eq. (4), critical points are located at the common inter-
section of the curves (P/v)T vs. Tr and (2 P/v2 )T vs. Tr , when the
two derivatives are zero at constant molar volume equal to vc .
In Fig. 3, the rst and the second derivatives of the pressure with
respect to the molar volume along the isochoric path v = vc , are
represented as reduced-temperature functions for two molecules:
M, the ctitious molecule previously dened and pure ethane. Note
that the only difference between both these molecules is the value
of the acentric factor (M = 1.0 and ethane = 0.0995).
One observes that the SRK EoS classically predicts one critical
point C1 for pure ethane (see Fig. 3a), and two critical points C1
and C2 (see Fig. 3b) for pure molecule M. This example also empha-
sizes that prediction of multiple critical points is not systematic
with the SRK EoS and occurs for heavy enough molecules (in the n-
 R. Privat et al. / Fluid Phase Equilibria 295 (2010) 7692 79

Fig. 3. Observation of single (C1 ) and multiple critical points (C1 and C2 ) with the cubic SRK EoS: representation of the derivatives (P/v)T and (2 P/v2 )T along the isochoric
path v = vc , as functions of Tr = T/Tc,1 . () Pure-component critical points. (a) Ethane. (b) Fictive molecule M.

alkanes homologous series, existence of additional critical points
starts from n-heptane).
4. Shape of isotherms according to the PC-SAFT EoS
In this section, pure n-decane is considered for illustration and
values of the three pure-component PC-SAFT parameters (m,  and
/kB ) are taken from Gross and Sadowski [12].
Experimental shapes of Pv isotherms of uids are very well
known since Andrews famous work [2] in the 19th century.
Some years after, Van der Waals [1] was the rst one to pro-
pose a reliable mathematical way to model the experimental
pure-component uid-phase behaviours discovered by Andrews.
In order to explain liquidvapour phase transition, the theory of
Van der Waals assumes existence of metastable and unstable states
(i.e. non-stable states) on subcritical isotherms. Subsequently,
all the EoS developed for the representation of liquid and gas
phases, including PC-SAFT, involve the same kind of non-stable
states on pure-component isotherms. In most cases, when solv-
ing the PC-SAFT EoS at a specied pressure and temperature,
three molar-volume roots at the most are likely to be calcu-
lated. This feature is a common characteristic to all the existing
EoS aimed at modelling both liquid and vapour phases. As an
example, a Pv diagram of n-decane, calculated with the PC-SAFT
EoS, is represented in Fig. 4a which shows three isotherms at a
subcritical temperature T1 < Tc,decane , at the critical temperature
T2 = Tc,decane and at a supercritical temperature T3 > Tc,decane . It
is noticeable that two local extrema (a maximum and a mini-
mum) arise on the non-stable part of isotherm T1 . In panel 4b,
a fP diagram is shown (f being the fugacity of the pure com-
ponent) including the same three isotherms. It is interesting to
note that the two extrema previously observed on isotherm T1
in the Pv plane correspond to two cusps, located in the non-
stable region. The stable parts of isotherm T1 (i.e. liquid part
and gas part) are joining at a salient point which marks the
liquidvapour equilibrium. Historically, this kind of curve was

Fig. 4. Representation of three isotherms of pure n-decane using the PC-SAFT EoS at the subcritical temperature T1 = 590.0 K, at the calculated critical temperature T2 =
Tc,decane  630.6 K and at the supercritical temperature T3 = 750.0 K. Bold continuous lines: isotherms (stable parts). Thin continuous lines: saturation curves (bubble and
dew curves). Dashed lines: non-stable parts of subcritical isotherms. () Critical points. (a) Pv plane. (b) fP plane.
80 R. Privat et al. / Fluid Phase Equilibria 295 (2010) 7692

Fig. 6. Stable and non-stable parts of isotherms of pure n-decane in the P

Fig. 5. Representation of three isotherms of pure n-decane in the P plane using the
PC-SAFT EoS at temperatures T1 = 590.0 K, T2 = Tc,decane  630.6 K and T3 = 750.0 K.
Bold continuous line: isotherm. Thin continuous line: saturation curve. Dashed line:
non-stable part of subcritical isotherm. () Critical point.
shown for the rst time by Van der Waals in his Ph.D. thesis
manuscript [1].
An equivalent representation of Pv isotherms lies in using a
P plane, where  represents a reduced density. This quantity is
dened by the following relationship:
 (metastable and unstable) were removed (this is the real isotherm).
vlim = NAv md3
plane using the PC-SAFT EoS at ve temperatures T1 = 135.0 K, T2 = 158 K, T3 =
300.0 K, T4 = 600.0 K and T5 = 800.0 K. The dashed line materializes the close-
packed reduced density   0.74048.
sical shape like, for instance, subcritical isotherms T3 and T4 and
supercritical isotherm T5 . For a better understanding of the sin-
gularities on low-temperature isotherms, the isotherm T1 = 135 K
is specically investigated from now on. In Fig. 7, two isothermal
curves are shown: the dashed line is a plot of isotherm T1 without
testing the mechanical stability; the continuous bold line repre-
sents the same isotherm but in this case, all the non-stable parts
For the later, two different plateaux appear indicating the presence
vlim 6 

= , with: (5)
v d(T ) =  1 0.12 exp 3 of two different uiduid phase equilibria at 135 K. In other words,
kB T two saturation pressures can be calculated in these conditions:
sat = 2 1016 bar corresponds to the rst plateau (i.e. to the
PFFE
NAv and kB are respectively the Avogadro constant and the Boltz- 1
rst uiduid equilibrium FFE 1, which is actually a liquidvapour
mann constant. sat = 802.9 bar corresponds to the second one
equilibrium) and PFFE 2
The molar volume vlim has no physical relevance [12] and is
(i.e. FFE 2). An enlargement of the isotherm in the vicinity of the
associated to  = 1 or equivalently, to an innite pressure of the
rst plateau is proposed in Fig. 8. Logarithmic scales are used to see
uid. Theoretically, the closest packing of segments is obtained
simultaneously both the local maximum on the isotherm and the
for  =   0.74048. Let us notice that v = vlim / is therefore the
liquidvapour equilibrium (FFE 1). In Fig. 9, isotherm T1 = 135 K is
smallest volume which can be taken up by one mole of a given
represented in a ln f P plane. From a rapid overview, it seems
molecule (it is the excluded molar volume). The PC-SAFT EoS can
obvious that its shape strongly contrasts with those shown in
however be extrapolated to values of  greater than the theoreti-
Fig. 4b. The dashed curve, plotted without testing for mechanical
cal close-packed limit. Allowing to emphasize phenomena in liquid
region,  is thus a useful variable ranging from 0 to 1. The rep-
resentation of the three previous isotherms T1 , T2 and T3 in the
(P, )-plane is given in Fig. 5.
All the curves previously shown are quite classical and refer
to well known uid-phase behaviours. However, as mentioned in
Section 1, some unexpected phenomena are likely to arise at very
low temperature when using the PC-SAFT EoS. This observation
is illustrated in Fig. 6. Whereas, classical isotherms exhibit at the
most two local extrema (or equivalently, at given temperature and
pressure, the resolution of the EoS leads to three molar-volume
roots at the most), low-temperature isotherm T1 = 135 K exhibits
no less than four extrema (note that a local maximum close to
 = 0 but not visible from Fig. 6, also exists as will be shown later
on). As a consequence, the resolution of the PC-SAFT EoS may lead
to four or ve molar-volume roots (and among these, only one or
two are stable) which is a rather unusual situation generally not
handled by classical algorithms for EoS-resolution. Another sur-
prising feature is that the isotherm T2 = 158 K exhibits an inexion
point with a horizontal tangent, which is theoretically the char-
acteristics of a critical point, while the ordinary liquidvapour
critical point is found around 630.6 K according to the PC-SAFT Fig. 7. Isotherm T1 = 135 K of pure n-decane in the P plane using the PC-SAFT
model. When increasing the temperature, isotherms show a clas- EoS. Continuous bold line: stable parts. Dashed line: metastable and unstable parts.
 R. Privat et al. / Fluid Phase Equilibria 295 (2010) 7692
Fig. 8. Highlight of the low-pressure vapourliquid equilibrium (FFE1) on isotherm
T1 = 135 K of pure n-decane in the ln Pln  plane using the PC-SAFT EoS. Continuous
bold line: stable parts. Dashed line: metastable and unstable parts.
stability, exhibits no less than four cusps, whereas only two cusps
arise on classical isotherms shown in Fig. 4b. Let us remind that
the stable parts of the isotherm are those with minimum fugacity
for positive pressures. All the cusps belong to non-stable parts of
the isotherm (and actually all of them mark the transition between
metastable states and unstable states). In addition, by looking at
the stable isotherm (bold continuous line), one may clearly observe
two salient points indicating the existence of the two uiduid
equilibria (FFE 1 and FFE 2) at the same temperature T1 .
5. Existence of multiple uiduid coexistence lines and
multiple pure-component critical points with the PC-SAFT
EoS
The work of Yelash et al. [8,9] and the previous sections of this
study put in evidence the possible existence of multiple uiduid
saturation pressures at a given temperature. Starting from a suit-
able initial guess, it is possible to trace out the complete set
of uiduid coexistence lines (i.e. the ordinary vapour-pressure
curve and the additional uiduid coexistence line arising at very
low temperature) using exactly the same solution procedure as for
Fig. 9. Representation of isotherm T1 = 135 K of pure n-decane in the ln fP plane
calculated with the PC-SAFT EoS. Continuous bold line: stable parts. Dashed line:
metastable and unstable parts. () Fluiduid equilibria.
81
Fig. 10. Fluid phase diagram of pure n-decane in the PT plane using the PC-SAFT
EoS. Continuous bold lines: phase-equilibrium lines (P1sat , vapour-pressure curve and
P2sat , liquidliquid equilibrium locus). Dashed lines: spinodals. () Critical points.
the ordinary vapour-pressure curve. These two curves (the ordi-
nary one, noted P1sat (T ) and the additional one, noted P2sat (T )) end
at two mechanically stable critical points (resp. noted C1 and C2 ). In
Appendix B, a method is proposed to calculate these points using a
PC-SAFT-like model. For n-decane, critical calculations lead to:
 
 Tc,1 = 630.575 K  Tc,2 = 158.003 K
 
C1  Pc,1 = 25.894 bar and C2  Pc,2 = 5139.772 bar (6)
 c,1 = 0.3048  c,2 = 0.6998
The two uiduid coexistence lines of n-decane (i.e. P1sat (vapour-
pressure curve) and P2sat ), and the two corresponding critical points,
C1 and C2 as well, are represented in Fig. 10 (PT plane) and in Fig. 11
(P plane). In both of them, the spinodals are represented (dashed
lines) giving some indications about the location of the extrema on
isotherms P(). Contrary to most of the cubic EoS, PC-SAFT predicts
two different critical molar volumes. In addition, note that both
uiduid coexistence lines increase with temperature.
In the P plane, we observe that reduced densities along the
additional P2sat (T )-saturation curve get typical orders of magnitude
of liquid-phase reduced densities (indeed,  > 0.50 for both phases
Fig. 11. Fluid phase diagram of pure n-decane in the P plane using the PC-SAFT
EoS. Continuous bold lines: phase-equilibrium lines (P1sat , vapour-pressure curve and
P2sat , liquidliquid equilibrium locus). Dashed lines: spinodals. () Critical points.
The continuous thin vertical line materializes the close-packed reduced density  
0.74048.
82 R. Privat et al. / Fluid Phase Equilibria 295 (2010) 7692

in equilibrium). In addition, in the PT plane, it is also noticeable

that the P2sat (T )-curve is nearly vertical (far from the critical point)
and runs from extremely low pressures ( 1015 bar) to very high
pressures (> 5000 bar); this means that the phase-equilibrium
temperature is very few affected by changes in pressure on a
very wide pressure range. As a consequence, since the two phases
in equilibrium exhibit a thermodynamic behaviour remembering
those encountered with liquid phases, the P2sat (T )-curve will be
called liquidliquid equilibrium line from now on. In other words, at a
xed temperature, pure n-decane is likely to exhibit two uiduid
equilibria: a low-pressure liquidvapour equilibrium and a high-
pressure liquidliquid equilibrium.
From a computational point of view, since the P2sat (T )-curve
is nearly vertical in the PT plane; it is thus preferable to specify
the pressure instead of the temperature to trace out this line. The
two uiduid coexistence lines P1sat (vapour-pressure curve) and
P2sat (liquidliquid equilibrium line) intersect at a point T such
that TT  130.3 K and PT  1016.7 bar, as shown in Fig. 12. This
Fig. 12. Phase diagram of pure n-decane in the vicinity of the liquidliquidvapour
intersection point T is very similar to a pure-component triple triple point (T) calculated with the PC-SAFT EoS. Continuous lines: uiduid coex-
point, since it is a point where three phases are coexisting: two istence lines. (C2 ) Liquidliquid critical point. LLE = liquidliquid equilibrium locus,
liquid phases and one vapour phase. This liquidliquidvapour LVE = liquidvapour equilibrium locus.
triple point T is thus the starting point of the liquidvapour
P1sat -curve and of the liquid-liquid P2sat -curve. Both these curves For a better understanding of these phenomena, four ln fP dia-
run monotonously until their critical points (C1 and C2 ). For tem- grams are considered in Fig. 13. Four cusps arise on all of these
peratures below TT , pure n-decane exhibits a unique liquidvapour diagrams and two distinct loops may be observed. These two loops
saturation pressure (noted P0sat (T )). clearly appear when looking at isotherm T = 145 K. At this tem-

Fig. 13. Representation of four isotherms of pure n-decane in the ln fP plane at 125 K, 130.3 K (TT ), 135 K and 145 K using the PC-SAFT EoS. Continuous bold lines: stable
parts. Dashed lines: non-stable parts. () Fluiduid equilibrium (LVE or LLE). T: triple point (liquidliquidvapour equilibrium).
 R. Privat et al. / Fluid Phase Equilibria 295 (2010) 7692 83

Table 1
Additional mechanically stable critical points of n-butane predicted by the PC-SAFT
and the SAFT EoS (critical reduced coordinates of the additional critical points are
normed by the coordinates of the ordinary critical points).

Model Tr Pr vr Source

PC-SAFT 0.2762 178.5160 0.4328 This work

SAFT a 0.5864 1127.4552 0.1461 [3]
a
Original SAFT version of Huang and Radosz [11].

EoS are not limited to the number of components of a system, this

example also points out the necessity to dispose of an algorithm
for EoS-resolution able to manage more than three molar-volume
roots at a given temperature, pressure and composition.

6. PC-SAFT undesirable features along the n-alkane

homologous series

The molecule of n-decane which was the only considered in the

Fig. 14. Isotherm T = 135 K of the mixture ethane(1)/n-decane(2) (x1 = 0.15 and
x2 = 0.85) calculated with the PC-SAFT EoS.
perature, the two salient points located on the stable isotherm,
characterize the presence of two uiduid equilibria FFE 1 and
FFE 2. Decreasing the temperature, these two loops come closer one
another (see for instance isotherm T = 135 K). At T = TT = 130.3 K
(triple point temperature) the two salient points merge in a unique
triple point (T). This point is common to both uiduid coexis-
tence lines P1sat and P2sat in the PT plane and in the fP plane (since
in this case, both uiduid equilibria FFE 1 and FFE 2 are charac-
terized by the same temperature, the same pressure and the same
fugacity). Let us notice that the triple point T lies at the intersection
between three different lines of the same isotherm in the fP plane.
For any temperature lower than 130.3 K, only one vapour pressure
can be calculated (see for instance isotherm T = 125 K) associated
to a unique salient point on the stable isotherm.
It is important to be aware that this kind of behaviour is not spe-
cic to pure components and may also extend to mixtures. As an
example, Fig. 14 represents the isotherm T = 135 K of a binary sys-
tem ethane/n-decane. It may be observed that the isotherm of the
binary system has exactly the same shape as the pure-component
isotherms previously shown. Since the drawbacks of the PC-SAFT
previous section, is far from being an isolated example of PC-SAFT
inconsistencies. Using the sets of pure-component PC-SAFT param-
eters proposed by Gross and Sadowski [12], multiple uiduid
coexistence lines and critical points have been observed for any
pure linear alkane.
Remark: The reduced critical coordinates,
Tc,additional crit. point Pc,additional crit. point
Tr = , Pr =
Tc,ordinary crit. point Pc,ordinary crit. point
vc,additional crit. point
and vr =
vc,ordinary crit. point
of n-butane additional liquidliquid critical point, calculated with
two different SAFT-like models are reported in Table 1. The origi-
nal SAFT EoS predicts a reduced critical temperature of additional
critical point close to 0.6 whereas with the PC-SAFT EoS, this
reduced temperature is calculated around 0.3. PC-SAFT, which is
often claimed as more powerful than original SAFT, seems there-
fore to lead to inconsistent predictions far from the temperature
range of practical interest, contrary to the SAFT EoS. It may be
noted that for both models, critical pressures of additional criti-
cal points are completely outside the range of experimental values
exp
(> 100Pc,butane ).
Critical temperature and pressure of additional critical points
provide a useful information about the temperature and pressure

Table 2
Numerical values of critical temperatures, pressures and reduced densities of ordinary and additional critical points for the rst 20 linear alkanes, calculated with the PC-SAFT
EoS.

Carbon number Additional critical point Ordinary critical point

n Tc (K) Pc (bar) c Tc (K) Pc (bar) c

1 50.96 9198.22 0.7559 191.40 46.75 0.1429

2 87.40 9743.64 0.7329 308.96 51.63 0.1335
3 105.11 8368.31 0.7239 375.14 46.08 0.1321
4 119.47 7531.09 0.7184 432.50 42.19 0.1309
5 130.17 6794.56 0.7137 479.29 38.25 0.1294
6 138.63 6334.43 0.7099 519.33 35.43 0.1278
7 144.62 5917.27 0.7064 552.10 32.49 0.1257
8 150.65 5610.81 0.7041 583.06 30.19 0.1241
9 155.10 5365.49 0.7019 609.28 28.06 0.1222
10 158.00 5139.77 0.6998 630.57 25.89 0.1201
11 162.81 4933.59 0.6987 654.91 24.32 0.1190
12 165.38 4765.09 0.6973 673.26 22.65 0.1172
13 167.72 4586.22 0.6961 690.05 21.02 0.1156
14 171.70 4517.21 0.6955 710.38 20.29 0.1147
15 173.33 4371.31 0.6945 723.97 18.91 0.1132
16 175.14 4292.00 0.6936 737.64 17.91 0.1118
17 176.98 4201.19 0.6929 750.78 16.97 0.1106
18 178.50 4149.36 0.6923 762.57 16.20 0.1094
19 179.53 4065.77 0.6916 772.73 15.27 0.1080
20 181.50 4008.38 0.6912 785.03 14.67 0.1071
84 R. Privat et al. / Fluid Phase Equilibria 295 (2010) 7692

Fig. 15. Critical points of pure n-alkanes in the PT plane, according to the PC-SAFT EoS. () Critical points of the rst 20 real n-alkanes calculated using the set of pure-
component PC-SAFT parameters as published by Gross and Sadowski [12]. Continuous line: critical points of pseudo n-alkanes (n [1; 700]), calculated using a correlation to
estimate pure-component PC-SAFT parameters (see Eq. (7)). (a) Additional critical points. (b) Ordinary critical points.

ranges in which PC-SAFT may lead to inconsistent predictions.
Indeed, as a general case and as illustrated above for n-decane,
additional uiduid saturation curves arise at pressures between
zero and the critical pressure of the additional critical point, and at
temperatures belonging to a small range whose upper bound is the
critical temperature of the additional critical point. Numerical val-
ues of critical pressures and temperatures of the two critical points
(i.e. the ordinary and the additional ones) are reported in Table 2
for the rst 20 n-alkanes. All these critical points are represented
with circles in Fig. 15.
In addition, in order to observe continuous phenomena, we did
not only consider real n-alkanes but we also dealt with pseudo
n-alkanes (with non-integer carbon-atom number n), the proper-
ties of which (i.e. the pure-component PC-SAFT parameters) were
estimated using a correlation proposed by Gross and Sadowski [12]:
to nite values when n tends to innity. Regarding ordinary pure-
component critical points, this issue has been widely addressed
through the open-literature [26] and particularly by some authors
of group-contribution methods [27,28]. Such values can obviously
be predicted by the PC-SAFT EoS from an appropriate correlation
to estimate the PC-SAFT parameters. Using Eq. (7), PC-SAFT yields:
Tc, = 1440 K
Ordinary critical points: Pc, = 0 bar (8)
c, = 0
These results look physically quite realistic and in agreement with
the conclusions of Nikitin et al. [26]. It is however surprising to
observe that for alkanes with very long chains, PC-SAFT predicts
a negative critical pressure which slowly vanishes as n-alkanes
become longer.

n [1; +[ A similar study can be carried out with additional critical points.

M = 14n + 2 The corresponding results are illustrated by Fig. 16 giving the

changes in critical temperature, pressure and reduced density for
M MCH4 M MCH4 M 2MCH4
X =q + q + q2i (7) n-alkanes the molecular weight of which varies between MCH4 and

i 0i
M 1i
M M

 = X1 ; m = X2 M; /kB = X3 108 g mol1 . As with ordinary critical points, the critical properties

1 of additional critical points exhibit asymptotic behaviour when the

MCH4 = 16.04 g mol
Numerical values of parameters qji are given in Table 3.
Using this correlation, two continuous critical loci (for ordinary
and additional critical points) were calculated (Nota Bene: in this
context, we name critical locus, the locus formed by all the critical
points of pure n-alkanes). These ones are plotted with continu-
ous lines in Fig. 15. The shape of the ordinary critical point locus
looks very classical. It is interesting to notice that the additional
critical point locus exhibits exactly the same shape as the ordinary
one: both the critical curves rst increase then decrease when criti-
cal temperature increases; in addition, a maximum arises between
methane and ethane in both cases.
The use of Eq. (7) also allows the prediction of asymptotic val-
ues of critical properties (Tc, , Pc, and c, ) for innite-length
n-alkanes. Note that, according to Eq. (7), m/M,  and /kB converge
Table 3
Numerical values of qji parameters in Eq. (7).
j=0 j=1
i=1 3.7039 0.3226
i=2 0.06233 0.02236
i=3 150.03 80.68
n-alkane size becomes innite. However, it is noticeable that the
critical pressure and the critical reduced density do not tend to
zero but to nite values:
Tc,  215 K
Additional critical points: Pc,  2860 bar (9)
c,  0.68
7. What about other pure chemicals?
In order not to limit the existence of multiple critical points
and multiple uiduid coexistence lines to n-alkanes, many other
chemicals were also tested out. The pure-component PC-SAFT
parameters of the investigated compounds originate from Gross
and Sadowski [12]. In addition to the n-alkanes, eight other chem-
ical families were also tested. As a conclusion, we can state that
without any exception, all the chemicals exhibit two critical points
and two uiduid coexistence lines. As a proof, results are pro-
vided in Table 4. Fig. 17 graphically illustrates these results by
j=2 plotting critical properties of ordinary critical points against critical
0.6907 properties of additional critical points. This gure emphasizes the
0.01563 very different orders of magnitude of Tc and Pc between the ordi-
38.96
nary liquidvapour critical point and the additional liquidliquid
 R. Privat et al. / Fluid Phase Equilibria 295 (2010) 7692 85

Table 4
Numerical values of critical temperatures, pressures and reduced densities of ordinary and additional critical points for various chemicals, calculated with the PC-SAFT EoS.

Compounds Additional critical point Ordinary critical point

Tc (K) Pc (bar) c Tc (K) Pc (bar) c

Branched alkanes
Isobutane 114.766 7173.904 0.7195 414.133 40.084 0.1312
Isopentane 127.853 6677.203 0.7153 467.894 37.578 0.1300
Neopentane 121.408 6249.089 0.7181 439.967 35.031 0.1308
2-Methylpentane 136.241 6180.002 0.7111 507.411 34.681 0.1283
2,2-Dimethylbutane 135.603 6108.272 0.7148 497.177 34.385 0.1298
2,3-Dimethylbutane 138.473 6286.329 0.7138 509.75 35.39 0.1295
3-Methylpentane 138.406 6331.854 0.7116 514.354 35.567 0.1286
2-Methylhexane 142.547 5756.619 0.7074 541.003 31.828 0.1264

Cycloalkanes
Cyclopentane 143.246 8880.336 0.7179 519.379 49.797 0.1308
Cyclohexane 153.446 7981.546 0.7157 560.706 44.904 0.1301
Methylcyclopentane 147.867 7606.178 0.7146 542.456 42.819 0.1298
Methylcyclohexane 158.462 7006.664 0.7140 582.734 39.447 0.1296
Ethylcyclopentane 156.026 6947.081 0.7114 580.405 39.007 0.1285
Ethylcyclohexane 168.153 6522.712 0.7122 623.15 36.676 0.1288

Alkenes
Ethylene 80.224 9647.046 0.7333 283.568 51.035 0.1336
Propylene 103.706 9060.807 0.7248 369.56 49.732 0.1322
1-Butene 118.146 8012.936 0.7191 426.81 44.815 0.1311
1-Pentene 129.185 7142.633 0.7148 473.64 40.208 0.1298
1-Hexene 137.691 6538.959 0.7106 514.093 36.647 0.1281
1-Octene 150.082 5779.131 0.7046 579.13 31.249 0.1245
Cyclopentene 142.661 9459.85 0.7190 515.536 52.921 0.1311

Aromatic compounds
Benzene 157.129 9851.674 0.7165 572.395 55.373 0.1304
Toluene 163.186 8549.117 0.7123 604.437 48.077 0.1289
Ethylbenzene 168.597 7662.142 0.7097 632.241 42.823 0.1277
m-Xylene 168.222 7679.501 0.7088 633.881 42.758 0.1271
o-Xylene 171.65 7915.34 0.7092 645.341 44.153 0.1274
p-Xylene 167.894 7559.57 0.7089 632.254 42.112 0.1272
n-Propylbenzene 172.938 7085.936 0.7075 656.231 39.185 0.1264
Tetralin 194.629 7841.038 0.7077 737.546 43.423 0.1265
n-Butylbenzene 175.081 6406.502 0.7045 676.246 34.588 0.1243
Biphenyl 204.034 7632.233 0.7037 791.88 40.871 0.1237

Permanent gases
Carbon monoxide 37.599 6910.351 0.7422 134.011 35.332 0.1356
Nitrogen 35.242 6842.309 0.7463 126.878 34.65 0.1370
Argon 39.137 9493.219 0.7599 150.967 49.093 0.1467
Carbon dioxide 86.69 14574.589 0.7226 310.277 80.64 0.1319
Sulfur dioxide 117.886 16192.134 0.7118 437.598 90.993 0.1287
Chlorine 119.147 15852.418 0.7344 421.179 83.443 0.1338
Carbon disulde 156.809 15146.326 0.7307 554.755 81.046 0.1332

Halogenated hydrocarbons
Methyl chloride 119.617 13952.752 0.7254 425.81 76.398 0.1323
Chloroethane 130.132 10814.378 0.7194 469.625 60.43 0.1312
2-Chloropropane 136.518 8947.486 0.7172 496.136 50.238 0.1306
1-Chlorobutane 148.448 8152.13 0.7119 550.98 45.814 0.1287
Chlorobenzene 176.491 9491.181 0.7142 648.564 53.435 0.1296
Bromobenzene 187.253 9442.159 0.7142 688.016 53.159 0.1296

Ethers
Dimethylether 112.7 10640.885 0.7188 407.52 59.558 0.1310
Diethylether 127.757 7555.664 0.7107 476.635 42.363 0.1282
Methyl n-propylether 129.801 7975.825 0.7104 485.162 44.672 0.1280

Esters
Methylmethanoate 136.423 13043.755 0.7138 502.04 73.434 0.1295
Ethylmethanoate 141.889 10282.563 0.7116 527.358 57.756 0.1285
n-Propylmethanoate 146.283 8821.512 0.7086 551.777 49.072 0.1270
Ethylethanoate 140.568 8649.117 0.7060 537.855 47.351 0.1254
n-Propylethanoate 146.003 7709.216 0.7043 564.383 41.568 0.1242
n-Butylethanoate 151.953 6980.698 0.7032 591.876 37.138 0.1233
Isopropylethanoate 141.949 7377.823 0.7055 544.752 40.226 0.1251
Methylpropanoate 142.498 8829.724 0.7064 543.895 48.495 0.1257
Ethylpropanoate 144.615 7693.709 0.7040 560.151 41.343 0.1240
n-Propylpropanoate 148.722 6998.557 0.7024 582.247 36.865 0.1227
Methylbutanoate 147.954 7838.731 0.7050 569.376 42.565 0.1248
86 R. Privat et al. / Fluid Phase Equilibria 295 (2010) 7692
Fig. 16. Evolution of three critical variables (Tc , Pc and c ) of additional critical points
along with the n-alkane molecular weight, according to the PC-SAFT EoS.
critical point. We can thus conclude that the artefacts of the PC-
SAFT model seem almost systematic and affect probably any real
pure component.
the validity range of these constants and can thus be responsible
for inconsistent results (this is however only a hypothesis).
8. A simple algorithm to solve EoS exhibiting more than
three real molar-volume roots
As pointed out through the previous sections, in some specic
cases, the resolution of the PC-SAFT EoS may lead to more than
three molar-volume roots. This situation is difcult to manage for
most of the resolution algorithms.
For pure-component EoS, at a specied pressure P0 and tem-
perature T0 , the equation of state to be solved writes: P0 = P(T0 , v),
where the molar volume v is the unknown. Similarly, the previous
equation may write: P0 = P(T0 , ), where the reduced density  is
the unknown. When dealing with classical EoS admitting only three
molar-volume roots at the most (like cubic EoS for instance), three
cases may be encountered:
1. The resolution of the EoS provides a unique solution. This situa-
tion is the simplest because there is no need to sort the solutions.
2. The resolution of the EoS gives exactly two solutions. Numerical
computations make this case very unlikely, if not impossible. It
has to be treated like the third case.
3. The resolution of the EoS gives three reduced-density roots. In
this case, only one or two roots among the smallest and the
largest ones are of interest. The smallest is a vapour-like root and
the largest is a liquid-like root. The medium root is always unsta-
ble. To discriminate the roots and to determine which one(s)
has(have) to be kept, their stabilities are then compared (the
most stable one has the smallest molar Gibbs energy).
In order to solve the EoS, a procedure employing a Newtons
method is generally used. Firstly, an initial estimate in the vapour
domain is given to the reduced density (typically [0] = 102 or
[0] = 103 ) followed by a Newtons iterative process. The reduced
density at iteration k + 1 is deduced from its value at iteration k
from the following relationship:
P0 P(T0 , [k] )
[k+1] = [k] + 
 (10)
At this point, we could wonder what is the possible source of 
inconsistent behaviour by the PC-SAFT model. This question is not
P
 
T T0 ,[k]
easy to address but we could probably incriminate the model con-
stants a0i , a1i , a2i , b0i , b1i and b2i (with i 0, 6) dened in Appendix Then, a second Newtons iterative process is run but using now
A. Indeed these parameters were determined by Gross and Sad- an initial estimate in the liquid domain for the reduced density
owski by varying  between 0 and 0.6 [29]. Phase-equilibrium (typically [0] [0.4; 0.9]). This kind of resolution methods applies
calculations resulting in a  value larger than 0.6 are thus beyond generally very well to classical cubic EoS and allow in most of the

Fig. 17. Comparison between the critical temperatures and pressures of the ordinary critical points and those of the additional critical points, for all the compounds referenced
in Tables 2 and 4. (a) Critical pressures. (b) Critical temperatures.
 R. Privat et al. / Fluid Phase Equilibria 295 (2010) 7692
cases to get proper convergence in all of the three cases previously
mentioned. Some more elaborate versions of this algorithm exist
that allow to make the resolution more robust or faster [30].
However, when more than three reduced-density roots exist,
the previous method cannot be used anymore. This kind of problem
has been reported by some authors concerning multiparameter EoS
like, for instance, the WagnerSetzmann EoS and some algorithms
exist that allow to calculate liquidvapour phase equilibria using
such EoS [31,32]. To properly solve an EoS likely to exhibit more
than three real roots, it is therefore necessary to start calculating
all the real roots of the EoS and then, to sort them according to their
mechanical stability. To do so, a resolution procedure is presented
here-after.
First step: Search of the extrema located on the isothermal curve
87
The main idea of this step is to run Nroot EoS-resolution
procedures using reduced-density initial estimates ensuring the
convergence.
Search of good initial estimates: using a dichotomic method in
an appropriate monotonous interval Ij , one searches a reduced
density whose corresponding pressure is nearly equal to P0 with
a relative error between 1 and 5 %. A good initial estimate of each
root is then obtained.
Search of the reduced-density roots: using the previous initial
estimates with Eq. (10), the EoS can be accurately solved in a few
iterations.
Remark: At this stage, it is possible to discard the roots that
violate the mechanical stability condition (i.e. the roots verifying
(P/v)T > 0).
Sorting of the solutions: the Nroot roots found are then sorted
in the P plane. 

 according to the value of the T, P-residual molar Gibbs energy
This step is aimed at solving the equation: P
  = 0 with
(residual Gibbs energy in specied variables T and P) or equiva-
T T0 ,
respect to . To do so, we divide the reduced-density interval lently, the logarithm of the fugacity coefcient. The most stable
[ ; 1 ] (with = 108 for instance) in N equidistant points root(s) has(have) the smallest value.
(N 5; 10). Each of these N reduced densities is an initial esti-
mate of the searched solutions, used for initializing a Newtons In order to illustrate the use of this algorithm, a short example
method: is presented. The PC-SAFT EoS applied to pure n-decane, is solved

 at T0 = 135 K and P0 = 102 bar. The T0 isotherm is plotted in Fig. 7.

P
  [k]

T0 ,
T
[k+1] = [k]  (11) Step 1. One nds Nextr = 4 extrema the coordinates of which are:
2 P 
2
 [k]
T T0 ,
extr
1
= 2.8107 103 and P(T0 , extr
1
) = 0.18626 bar
Let us remind that Newtons method is safe as long as there extr
2 = 0.38663 and P(T0 , extr ) = 1429.2 bar
2
are non-zero extrema between the trial value and the solu- extr = 0.63405 and P(T0 , extr ) = 2434.1 bar
3 3
tion. To improve the procedure, the Newtons method can
extr
4
= 0.76254 and P(T0 , extr
4
) = 3080.9 bar
obviously be replaced by any more sophisticated method (like
the Keplers method for instance). The expressions of the rst
Step 2. The two sequences (Pn ) and (Hn ) are dened:
and the second derivatives are given in Appendix A. From
now on, the reduced densities of the Nextr extrema are noted
(Pn ) = {0; 0.18626; 1429.2; 2434.1; 3080.9; +}
extr (i 1; Nextr ).
i (Hn )={0; 2.8107103 ; 0.38663; 0.63405; 0.76254; 1}
In case of failure of the Newtons method (this should be
extremely scarce), a slow alternative method can be used. The
reduced-density interval is then divided in one or two hun- The pressure P0 = 102 bar is contained within 5 ranges that are:
]P0 ; P1 [, ]P2 ; P1 [, ]P2 ; P3 [, ]P4 ; P3 [ and ]P4 ; P5 [. Thus: Nroot = 5.
dred 

equidistant points. For each of them, the rst derivative

P
  is evaluated. If the sign of this quantity changes Step 3. The complete resolution of the EoS leads to the following
T T0 ,
results:
between two points, a dichotomic method is employed to search
the reduced density cancelling the rst derivative. root = 7.5017 105 and g T,Pres /(RT0 ) = 1.4047 102
Second step: Calculation of the number Nroot of reduced-density 1
root
2
= 5.6560 103 and g T,Pres /(RT0 ) = 2.3228
roots of the EoS at a xed pressure P0 and temperature T0 .
Once known the location of the extrema on the isothermal root
3
= 0.51255 and g T,Pres /(RT0 ) = 31.568
curve, it is fairly easy to exactly determine the number of roots root
4
= 0.70870 and g T,Pres /(RT0 ) = 25.802
to be searched. The following sequences are then dened: root
5
= 0.79043 and g T,Pres /(RT0 ) = 27.841

P0 = 0
Finally, the most stable root is root which has the lowest residual
(Pn ) Pi = P(T0 , extr ) with i 1; Nextr (12) 3
i Gibbs molar energy g T,Pres .
PNextr +1 = +
 9. Conclusion
H0 = 0
(Hn ) Hi = extr
i
with i 1; Nextr (13)
In this paper, working with ordinary pure chemicals, some
HNextr +1 = 1
PC-SAFT inconsistent predictions were pointed out. Proof has
If, for j 0; Nextr , one has: Pj < P0 < Pj+1 or similarly Pj > been given that this EoS systematically predicts two uiduid
P0 > Pj+1 , then a reduced-density root exists in the range Ij = saturation curves (a vapour-pressure curve and a liquidliquid
]Hj ; Hj+1 [. coexistence line), two pure-component critical points and a
From now on, the number of roots Nroot is known. In addition, liquidliquidvapour triple point, which is obviously a non-
reduced-density intervals Ij containing each searched root, in realistic feature from an experimental point of view. The
which pressure is a monotonous function of , have been dened. liquidliquid equilibrium line generally exists on a short low-
They will be grandly useful for the next step. temperature range and on a very large pressure range. As an
Third (and last) step: Calculation of the reduced-density roots of example, this kind of phenomenon is exhibited by every linear
the EoS at a xed pressure P0 and temperature T0 . alkane at temperatures below 0.3T/Tc . It was also shown that for
88 R. Privat et al. / Fluid Phase Equilibria 295 (2010) 7692
an innite-size alkane, critical reduced density and pressure of
the additional critical point have nite non-zero values. Our cal-
culations performed on approximately 80 pure components also
demonstrate that the reduced density of the liquidliquid critical
point is always larger than 0.68.
Concerning computational aspects, these inconsistencies result
from the existence of multiple molar-volume roots (or equivalently,
reduced-density roots) when solving the EoS at a specied temper-
ature and pressure. With classical EoS (like cubic EoS) only three
solutions at the most can be found whereas with the PC-SAFT EoS,
four or ve solutions may exist. The resolution of the PC-SAFT EoS
thus involves to use an appropriate algorithm capable of dealing
with more than three molar-volume roots. Such an algorithm is
eventually proposed.
Finally, in order to get safe results when the PC-SAFT equation
of state is applied to ordinary pure chemicals, it is advised:
to solve the PC-SAFT EoS at a xed temperature and pressure
using an algorithm capable of detecting more than three molar-
volume roots,
to systematically reject any two-phase-equilibrium calculation
for which the reduced density of one of the two phases is larger
than 0.68.
List of symbols
a molar Helmholtz energy (J mol1 )
EoS equation of state
f fugacity of a pure component (bar)
res residual property in specied variables T and v
T, P-res residual property in specied variables T and P
Appendix A. Presentation of the original PC-SAFT model
and calculation of the rst and second isothermal
derivatives of the pressure with respect to the reduced
density
A.1. Calculation of the pressure of a uid with the
non-associating PC-SAFT model
In addition to the three pure-component input parameters
noted mi , i and i /kB for a pure-component i, some variables need
to be specied before starting the calculations. These are the abso-
lute temperature T of the mixture and the mole fractions xi of each
component i in the mixture (i 1; nC ). Let us notice that it is also
possible to use a binary interaction parameter kij to account for
strong interactions between two molecules i and j. This parameter
which is often tted on binary vapourliquid equilibrium data, is
generally set to zero when no information about it is available.
All the following equations stem from Gross and Sadowski [12];
they are ordered according to the method proposed by Gani et al.
[25] to allow an easy implementation in a computer program.
Temperature-dependent segment diameter:
FFE uiduid equilibrium   3

kB Boltzmann constant (kB = R/NAv  1.381 1023 J K1 ) di (T ) = i 1 0.12 exp i
, i 1, nC (14)
kB T
LVE liquidvapour equilibrium
m pure-component PC-SAFT parameter: number of seg-
ments (hard spheres) per chain Conventional combining rules for a pair of unlike segments:
NAv Avogadro constant  6.022 1023 (mol1 )
n carbon-atom number in real or pseudo-n-alkanes 1
P pressure (bar)
ij = 2 (i + j )
Pc critical pressure (bar)  , {i, j} 1, nC
2
(15)
Pr reduced pressure P/Pc ij
= i j
(1 kij )
R gas constant (J mol1 K1 ) kB kB kB
T absolute temperature (K)
Tc critical temperature (K)
Mean segment number in the mixture:
Tr reduced temperature T/Tc
v molar volume (m3 mol1 )
vc critical molar volume (m3 mol1 ) 
nc
vlim molar volume corresponding to  = 1 (m3 mol1 ) =
m xi mi (16)
vr reduced molar volume v/vc i=1
v molar volume corresponding to  =  (m3 mol1 )
xi mole fraction of component i
Denition of m2  3 and m2 2  3 :
Greek letters

 packing fraction (reduced density):  = vlim /v  
nC nC 

molar density of a uid (mol m3 ):
= 1/v
ij

m2  3 = xi xj mi mj ij3
 pure-component PC-SAFT parameter: temperature- kB T
i=1 j=1
independent segment diameter () (17)

 
nC nC  2
 close-packed reduced density.  = 2/6  0.74048
2 2  3 = xi xj mi mj
ij
ij3
/kB pure-component PC-SAFT parameter: depth of the poten-

m
kB T
i=1 j=1
tial well divided by the Boltzmann constant (K)

Subscripts and superscripts Expressions of coefcients ai and bi :

c pure-component critical point
disp contribution due to the dispersive attraction
extr extrema on the isotherm in the (P, )-plane ai = a0i + m 1 a1i + m 1 m 2 a2i

m
m
m , i 0, 6 (18)
hs residual contribution of hard-sphere system
ref residual contribution of hard-chain system (reference
b = b + m 1 b + m 1 m 2 b
i 0i 1i 2i

m
m
m
uid in PC-SAFT)
 R. Privat et al. / Fluid Phase Equilibria 295 (2010) 7692 89

with:

i a0i a1i a2i b0i b1i b2i

0 0.9105631445 0.3084016918 0.0906148351 0.7240946941 0.5755498075 0.0976883116

1 0.6361281449 0.1860531159 0.4527842806 2.2382791861 0.6995095521 0.2557574982
2 2.6861347891 2.5030047259 0.5962700728 4.0025849485 3.8925673390 9.155856153
3 26.547362491 21.4197936290 1.7241829131 21.003576815 17.215471648 20.6420759740
4 97.7592087840 65.25588533 4.1302112531 26.8556413630 192.6722644700 38.804430052
5 159.59154087 83.3186804810 13.7766318700 206.5513384100 161.82646165 93.6267740770
6 91.2977740840 33.74692293 8.6728470368 355.60235612 165.20769346 29.666905585

 
Number density of molecules: (I1 ) 2 3 (I2 )
z disp = 2

m  

m C1 + C2 I2 m2 2  3
n 1  
6 C
(27)
= 

xi mi di3 (19)
 Calculation of the residual contribution of the hard-sphere uid
i=1
z hs :
Denition of coefcients n :
3 31 2 323 3 23
z hs = + + (28)
 
nC
1 3 0 (1 3 ) 2
0 (1 3 )3
n =

xi mi din , n 0, 3 (20)
6
i=1 Calculation of the residual hard-chain contribution z hc to the
compressibility factor:
Note that the reduced density  is dened by:  = 3 .  
Denition of power series I1 and I2 :  
gijhs 3 32 62 3

= + dij +


6

(1 3 )2 (1 3 )2 (1 3 )3

1
I = ai i T,x
 
i=0
(21) 422 622 3
 + dij2 + (29)


6
(1 3 )3 (1 3 )4

bi i
I2 =
i=0

nC    hs 
mi 1 gij
Denition of coefcient C1 : z hc
= mz
hs
xi

(30)
giihs

 1 i=1 T,x
8 22 20 272 + 123 24
C1 = 1 + m
4
+ (1 m)
2 Compressibility factor:
(1 ) [(1 )(2 )]
(22) z = 1 + z hc + z disp (31)
Molar volume and molar density: Pressure P:

v = 1030 NAv (v in m3 mol1 ) 1030
P = zkB T
(P in Pa) (32)

(23)

= 1/v A.2. Calculation of (P/)T,x

Radial distribution function g hs of the hard-sphere uid: In this part, we assume that the temperature T, the mole frac-
ij
tions xi and the reduced density  of the mixture are known.
di dj The calculation of (P/)T,x is then straightforward and does not

dij = di + dj require to solve non-linear equations. We assume that all the quan-
222 tities calculated in the previous section are known.

gijhs =
1
+ dij
32
+ d 2
, {i, j} 1, nC
2
n 1
1 3 (1 3 )2
ij
(1 3 )3   C

6
(24) = xi mi di3 (33)
 
T,x
Denition of coefcient C2 : i=1

42 + 20 + 8 23 + 122 48 + 40
2 65) 6(m
Q 12m( 1)(4 + 83 482 + 80 44)
Q = m 5
+ (1 m)
3  = 6
+ 4 4
(1 ) [(1 )(2 )] (1) (1 ) (2 )
(25)



C2 = C1 = C12 Q
2
C2 = C21 = 2C1 C2 Q C12 Q
   
(34)
Calculation of the dispersion contribution z disp to the compress-
ibility factor: (the denition of Q is given by Eq. (25))

(I1 )  2 (I1 ) 
6


6



= aj (j + 1)j
= aj j (j + 1)j1

 2
j=0 j=0
(35)
2 (I2 ) 
(26) 6

(I2 ) 
6


2 = bj j (j + 1)j1

 = bj (j + 1)j
j=0
j=0
90 R. Privat et al. / Fluid Phase Equilibria 295 (2010) 7692

            
z disp

(I1 ) 2 (I1 ) P z

= 2m2  3 +

= kB T 1030

+z (45)
   2   
T,x T,x T,x T,x T,x
   

(I2 )
mm
2 2  3 C1 + C2 I2

T,x
 A.3. Calculation of (2 P/2 )T,x
 
2 (I2 ) (I2 ) C2 As previously, we assume that T, xi (i 1; nC ) and  are known.
+

C1 + 2C2 + I2 (36)

2   In addition, all the quantities calculated in the two last sections are
assumed to be known.
2

Q 2 7 9)
48m( 1)(5 + 104 803 + 2002 220 + 92)
24(m
2 = 7
5 5
(1 ) (1 ) (2 )
(46)

2 2
C22 = 4C1 C2 Q C12 Q2 2QC22 2C1 Q C2
   

     3 (I1 ) 
6
n 

nC

= aj (j 1) j (j + 1)j2
n = = xi mi din , n 0, 3 (37)

 6  3 j=0
T,x T,x i=1 (47)

  3 (I2 ) 
6
3[1 2 0 + 1 2 0 1 2 0 ]


z hs 1
3 = bj (j 1) j (j + 1)j2
= +

T,x (1 )2 02 (1 )2 j=0
 
0 2 (61 22 ) + (3 )(30 2 2 0 )22 2 z disp
+ 2
02 (1 )3 T,x
   
323 (3 )

2 (I1 ) 3 (I1 )
+ (38) = 2m2  3 2 +

0 (1 )4  2 3
T,x
Let us note:     
 

2 (I2 ) (I2 ) C2
K0,ij gijhs 2
mm
2 2  3 2 C1 + 2C2 + I2
Kij = , with: K0,ij =

, {i, j} 1, nC (39) 
T,x
2  
gijhs

T,x  
3 (I2 ) C2 (I2 ) 2 C2 2 (I2 )
+

C1 3
+3 + I2 2
+ 3C2 (48)
    2

1 = 6[02 1 2 0 0 1 2 0 0 1 2 + 0 2 1 2 ]



2 2 2 3
2
2 = 2[2 ( 3)[32 0 (0 2 2 0 ) + (2 0 ) ] + 30 [2 2 21 2 21 2 ] + 0 0 2 (61 2 ) 0 ]

= 6 [ ( 3)(  3  ) +  (3  2 )]
3 2 2 2 0 0 2 0 1 2
(49)

4 = 1223 ( 3)

 



2 z hs 1 2 3 4
= + + +
2 
T,x 03 (1 )2 03 (1 )3 02 (1 )4 0 (1 )5

   
22 ( + 2) + 2 (1 2 ) 2 K0,ij 2( + 2) 32 ( + 3) 22 (2 +  2)

K0,ij 1+ K0,ij = = + 6dij
K0,ij = = + 3dij
 (1 )3 (1 )4
2
T,x (1 ) 4
(1 )5
T,x

32 ( + 3) 22 (2 +  2) 2 2 (3 3 + 2) + 62 2 (3 2 2 ) + 622 ( + 4)
+ 2dij2 2 with {i, j} 1, nC
2 + 4dij2
(1 )5 (1 )6
(40) 2
    with: {i, j} 1, nC (50)
 
gijhs gijhs

1 2
=

, {i, j} 1, nC (41)



T,x

    K  
T,x T,x 2 gijhs

K0,ij

, {i, j} 1, nC
2
 
0,ij
= (51)
  2 

2


Kij K0,ij K0,ij gijhs 2 T,x
T,x T,x

= 2
, {i, j} 1, nC (42)
 gijhs (gijhs ) 
T,x T,x  
     
      2 Kij K0,ij 1 2 gijhs gijhs
z hc z hs  nC
Kii = K0,ij
+2K0,ij
=m
xi (mi 1) (43) 2 gijhs (gijhs )
2 2 
T,x
   T,x T,x
T,x T,x T,x
    
i=1
   2
z z hc z disp 2K0,ij gijhs 2
= + (44) + 3
with: {i, j} 1, nC (52)
   (gijhs ) 
T,x T,x T,x T,x
 R. Privat et al. / Fluid Phase Equilibria 295 (2010) 7692 91

    
nC   F1 and F2 are calculated analytically (expressions are given
2 z hc 2 z hs 2 Kii
=m
xi (mi 1) (53) in Appendix A). The Jacobian matrix J, dened by Jij = Fi /Xj
2 2 2
T,x T,x i=1 T,x writes:
         
2 z 2 z hc 2 z disp 2 P 2 P
= + (54)
2 2 2 T 2
T,x T,x T,x J =    T (58)
          3 P 3
P
2 P 2 z

z T2 3
= kB T 1030

+2 (55) T
2 2  
T,x T,x T,x T,x
Except for J12 , derivatives Jij are calculated numerically using
central differences:   
P  P 
Appendix B. Procedure to calculate critical points with the
PC-SAFT EoS    
2
P   
T0 + ,0

T0 ,0
 =
Eq. (4) reminds a set of three specications characterizing a T 2
T0 ,0    
pure-component critical point. Using reduced density instead of 2 P  2 P 
   
molar volume, they write:
 2  2 
3 P  =
T0 ,0 + T0 ,0

P(Tc , c ) Pc = 0 3  2
 T0 ,0    
(P/)T  =0 2 P  2 P 

Tc ,c (56)
   
   
(2 P/2 )  =0 3 P 
2
T0 + ,0
2
T0 ,0
T Tc ,c
 =
T2 2
T0 ,0
These three equations can be solved with respect to the three Inversion of the Jacobian matrix leads to:
unknowns: Tc (critical temperature), Pc (critical pressure) and c  
(critical reduced density). To do so, the following procedure is pro- 1 J22 J12
J1 = (59)
posed: J11 J22 J12 J21 J21 J11

Initialization of the procedure:
In the general case (i.e. when the pure-component isotherms
in the (P; )-plane exhibit two local extrema at the most), it is
rather simple to nd proper initial values of Tc , Pc and c (noted
[0] [0] [0]
Tc , Pc and c ) allowing convergence of the resolution method.
For instance:
- Tc can be seen as the transition temperature at which the num-
ber of extrema passes from two to zero. By using the method
described in section 8 to calculate the exact number of local
extrema on an isotherm in a (P; )-plane, estimate (with a
dichotomic method for example) with an accuracy of around
10K, the temperature Tc at which the isotherm only exhibits
one local extremum (isotherms exhibit two extrema below Tc ,
[0]
one at Tc , and none above). The estimated value Tc of Tc must
[0] [0]
be such that Tc < Tc (i.e. at Tc , the isotherm must exhibit two
extrema).
[0]
- Tc is known. Let us note max and min respectively the reduced
densities of the local maximum and the local minimum on the
[0]
isotherm T = Tc in the (P; )-plane. The initial value of the
critical reduced density is taken such as:
[0] 1
c = (min + max )
2 [6] N. Koak, T.W. de Loos, R.A. Heidemann, Ind. Eng. Chem. Res. 38 (1999)
[0] [0] [0]
- lastly: Pc = P(Tc , c )
When the isotherm may exhibit four local extrema (as illus-
trated in this paper), specic initialization procedures are
required. For the additional critical point, Tc is the temperature at
which exactly three local extrema coexist on the isotherm in the
(P; )-plane. Tc is therefore the transition temperature at which
the number of extrema on the isotherm passes from four to two.
Resolution method:
Once proper initial values are provided, critical calculations can
be performed using a NewtonRaphson method.
- Step 1: calculation of Tc and c .
We dene F, the vector of equations to be solved and X, the
vector of unknowns:
   
(P/)T
F= and X =
(2 P/2 )T
Iterative Newton procedure, allowing to deduce values of vari-
ables at iteration k + 1 from those at iteration k, then writes:
 ![k]
= J1
[k]
X F[k]
(60)
[k]
X[k+1] = X[k] + X
The iterative Newtons scheme is repeated until convergence is
reached. Critical coordinates are then: Tc = X1 and c = X2 .
- Step 2: calculation of Pc .
Once c and Tc are obtained from Step 1, one has:
Pc = P(Tc , c )
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