PC - Saft

J.
of Supercritical Fluids 42 (2007) 126
Modeling of critical lines and regions for binary and ternary

mixtures using non-cubic and cubic equations of state
Pedro Arce, Martn Aznar
School of Chemical Engineering, State University of Campinas, UNICAMP, P.O. Box 6066, 13081-970,
Campinas SP, Brazil
Received 1 November 2006; received in revised form 1 February 2007; accepted 1 February 2007
Abstract
In this work, two non-cubic equations of state, Perturbed Chain Statistical Association Fluid Theory (PC-SAFT) and Simplified Perturbed Hard
Chain Theory (SPHCT) were used to predict critical lines and regions for several binary and ternary systems, by fitting one binary interaction
parameter (ij ) for each binary system. Results were compared with experimental critical data, which included inorganic gases, hydrocarbons (light
and heavy paraffins, non-saturated olefins and aromatics), alcohols, carbon monoxide and carbon dioxide. These experimental data covered wide
ranges of temperatures and pressures which are commonly used in industry. For comparison, the data were also modeled using two cubic equations
of state: the well-known PengRobinson equation (PR) and the PatelTejaValderrama equation (PTV). PC-SAFT and SPHCT pure-component
parameters were obtained by regression, adjusting pure-component data such as vapor pressure and saturated liquid molar volume (taken from
DIPPR 1.2.0). Excellent results were obtained with the PC-SAFT EoS, while the SPHCT, PR and PTV EoS did not have a good performance. The
Heidemann and Khalil algorithm, with two nested single-variable iteration loops (an internal loop for volume and an external loop for temperature),
was used for locating a single liquidliquid or vaporliquid critical point.
2007 Elsevier B.V. All rights reserved.
Keywords: Liquidliquid equilibria; Vaporliquid equilibria; Critical lines; Equation of state; Cubic; Non-cubic
1. Introduction
In high-pressure phase equilibrium, the determination of critical lines (a critical line is a set of critical points) of mixtures
is important for several practical and theoretical reasons (especially in hydrocarbon production and processing). For example,
the determination of critical lines provides us with an orientation about the location of that region in temperature, pressure
and compositions where retrograde phenomena can occur. Also,
the knowledge of critical states can also be used in schemes
for classifying the overall phase behavior of mixtures, such as
the scheme by van Konynenburg and Scott [1]. On the other
hand, the measurement of critical phenomena is often difficult and expensive; thus, the computation of critical points of
Part of this work was presented at the VI Iberoamerican Conference on Phase
Equilibria and Fluid Properties for Process Design, EQUIFASE, Foz de Iguacu
(2002), and at the XV Brazilian Congress on Chemical Engineering, COBEQ,
Curitiba (2004)
Corresponding author. Tel.: +55 19 35213962; fax: +55 19 35213965.
E-mail address: maznar@feq.unicamp.br (M. Aznar).
0896-8446/$ see front matter 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.supflu.2007.02.001
a binary system is a sensitive test to explore the quality of

any thermodynamic model, especially equations of state, due to
the complex behavior that binary mixtures may present in this
region.
Vaporliquid and liquidliquid critical points in mixtures
of close-member hydrocarbons and other simple systems are
usually well predicted by traditional methods [2]. In complex
systems, such as aqueous solutions, critical lines can be very
diverse and often discontinuous [3]. Critical points in mixtures
containing carbon dioxide and water as solvents are of great
importance for the development of supercritical processes [4].
A number of researchers have demonstrated the ability of various EoS to correlate critical loci of highly non-ideal systems
[59]. Sadus [10] also applied conformal solution theory to predict critical properties of a number of binary mixtures containing
non-polar or weakly polar components.
In a previous work, the authors concluded that, in the critical region, a cubic EoS is not as accurate as a non-cubic EoS
[11]; therefore, in this work the performance of cubic and noncubic EoS to model critical lines of several binary and ternary
systems which include inorganic gases, hydrocarbons (light
P. Arce, M. Aznar / J. of Supercritical Fluids 42 (2007) 126
Nomenclature
List of symbols
a
energy parameter in cubic EoS
a
dimensionless Helmholtz free energy
A
Helmholtz free energy
b
first critical condition, volume parameter in cubic
EoS
c
Prigogine parameter, second critical condition,
volume parameter in cubic EoS
d
temperature-dependent segment diameter, third
critical condition
D
thermodynamic stability
f
fugacity
g
radial pair distribution function; gas phase
k
Boltzmann constant
m
segment number, parameter which depends on
acentric factor in cubic EoS
m
average segment number

MW
molecular weight
n
mole number
N
total number of molecules
NC
component number
NP
experimental point data
P
system pressure
q
normalized surface area per molecule
R
ideal gas constant
s
number of segments per molecule
T
absolute temperature
T*
characteristic temperature for intermolecular
interactions
v
molar volume
v
characteristic volume per mole
V
volume
w
acentric factor
x
mole fraction in liquid phase
XAi
fraction of A-sites on molecule i that do not form
associating bonds with other active sites
Y
auxiliary function
Z
compressibility factor
Zm
close-packed coordination number
Greek letters
deviations for the critical properties, perturbation

in mole number
constant in cubic EoS

AiBj variable which measures the associating strength
between site A on molecule i and site B on
molecule j
interaction energy parameter, associating energy

parameter
fugacity coefficient
reduced density
adjustable binary interaction parameter, associating volume parameter
chemical potential
constant
total number density of molecules; system density
segment diameter
auxiliary parameter
Superscripts
assoc associating
calc
calculated
exp
experimental
hc
hard chain
hs
hard sphere
pert
perturbation
sat
saturated condition
T
total
*
molar close-packed volume, temperature reduced
Subscripts
calc
calculated
C
critical property
exp
experimental
i,j,k,l
components
ij
interaction between components i and j
R
reduced property
Abbreviations
EoS
equation of state
LCEP lower critical end point
LL
liquidliquid
LV
liquidvapor
PC-SAFT Perturbed Chain-Statistical Associating Fluid
Theory
PR
PengRobinson
PTV
PatelTejaValderrama
PTx
pressuretemperature-composition
PVT
pressurevolumetemperature
SPHCT Simplified Perturbed Hard Chain Theory
UCEP upper critical end point
VDW van der Waals
Notation
<>
averaged mixture property
or heavy and lineal and branched paraffins, olefins and aromatics), alcohols, carbon monoxide and dioxide is studied. The
thermodynamic models used are two non-cubic EoS, PC-SAFT
[12] and SPHCT [13] and two cubic EoS, PTV [14] and PR [15].
The algorithm of Heidemann and Khalil [16], with two nested
single-variable iteration loops (an internal loop for volume and
an external loop for temperature) is used for locating a single
liquidliquid and vaporliquid critical point. In the SPHCT EoS,
the volume is calculated using the algorithm given by Topliss et
al. [17].
to association (aassoc ), which is given by:

nc

1
1
assoc
a
ln XAi XAi +
=
xi
2
2
2. Thermodynamic models
2.1. Perturbed-chain statistical uid theory, PC-SAFT
PC-SAFT EoS [12,18] has two terms, one for a reference
hard-sphere chain and another for a perturbation contribution,
a = a hc + a pert
(1)
where a = A/NkT , T is the absolute temperature, A the

Helmholtz free energy, N the total number of molecules, k Boltzmanns constant, and hc and pert denote the hard-sphere chain
reference and perturbation contribution terms, respectively. The
Hard chain contribution is based on the first-order thermodynamic perturbation theory in according with Chapman et al.
[19] who developed an EoS which includes m segments for
hard-sphere chains. This contribution is determined by:
a hc a ideal = m
a hs
NC
xi (mi 1)ln giihs (ii )
(2)
where x is the mole fraction of chains, m the number of segments in a chain, NS the Avogadro number, ghs the radial pair
distribution function for segments in the hard-sphere system and
m
the mean segment number in the systems. The Helmoholtz
free energy of the hard-sphere fluid, a hs , and the radial pair distribution function of the hard-sphere fluid depend on the total
number density of molecules, , and the temperature-dependent
segment diameter of component i, di , in according with:

ii
di = ii 1 0.12 exp 3
.
(3)
kT
By other hand, the second-order perturbation theory was
extended to chain molecules. The perturbation contribution [20]
is:
a pert = a 1 + a 2
(4)
where a 1 and a 2 depend on the integrals of power series of

sixth-order in density, compressibility factor, the total number
density of molecules and the Van der Waals one-fluid mixing
rule represented as (xi xj mi mj kij ijl = xi xj mi mj (ij /kT )k ijl )
which contains the conventional combination rules, used to
determine the cross terms between one pair of different segments:
1
(ii + jj )
2
ij = ii jj (1 ij )
ij =
(5)
where XAi is the fraction of A-sites on molecule i that do not form

associating bonds with others active sites. This number is found
through of the solution of a system of non-linear equations:
XAi =
2.2. Associating contribution [19]

When associating compounds are used, it is necessary to
add to Eq. (1) a term to take in account the contribution due
1 + NA
1

Ai Bj
j=1 j Bj XBj
nc
(8)
where j is the molar density of component j and AiBj is a

function of the associating volume, kAiBj , the associating energy,
AiBj , and the radial distribution function, ghs (d+) , and is defined
as follows:

Ai Bj

Ai Bj = ij3 ghs Ai Bj exp
1
(9)
kT
where AiBj measures the associating strength between site A
on molecule i and site B on molecule j.
2.3. Simplied perturbed hard chain theory, SPHCT
Kim et al. [13] developed a simplified version of the PHCT
EoS [21,22] substituting the PHCT EoS attractive term with
a theoretical, simpler expression based on a local composition
model by Lee et al. [23]. This simplified PHCT, called SPHCT,
is given by

RT
< c > RT 4 22
P=
+
VV(1 )3
Zm RT
< cV Y >
(10)
V- [V- + < cV Y > / < c >]
where Zm is the close-packed coordination number
(Zm = 18.0),
= < V > /V- the reduced density, = 2/6 the closepacking volume, P the pressure, T the temperature and V- the
molar volume. Terms between angular brackets represent mixture properties. Mixing rules were derived by Donohue and
Prausnitz [22] and proposed by Kim et al. [13]:
< V >=
NC
xi Vi
(11)
i=1
< c >=
NC
(12)
x i ci
i=1
(6)
where ij is the binary interaction parameter. In according with

this thermodynamic model, there are three pure-component
parameters per molecule: the segment diameter, ; the segment
number, m, and the interaction energy parameter, .
(7)
Ai
i=1
< cV Y >=
NC
NC
xi xj ci Vji Yij
(13)
i=1 j=1
where
Yij = exp
3
sj ji
Vji =
2
ij qi
2ci kT
(14)
(15)
and q is the normalized surface area per molecule, s the number of segments for a given molecule (s = 1 for monomers),
the hard-core diameter of a segment, the characteristic energy
per unit external surface area of a molecule and k Boltzmann
constant. Cross-terms ij and ij are given by
1
(ii + jj )
2
ij = ii jj (1 ij )
ij =
(16)
(17)
where ij is the binary interaction parameter.

Kim et al. [13] suggested that si and qi may be obtained from
the slopes of graphs of V* and cT* against the number of carbon
atoms, namely
qi =
si =
ci Ti
62.5
(18)
Vi
(19)
0.008667
where ci , Vi and Ti are the pure-component parameters,

Prigogine flexibility parameter, close-packed volume and characteristic temperature, respectively.
Table 1
Constants and parameters of a general cubic EoS
EoS
PR
PTV
c
a
b
c
m
b
0.4572
0.0778
0.3746 + 1.5423 0.26992
c
0.6612 0.7611(ZC )
0.0221 + 0.2087(ZC )
0.5777 1.8708(ZC )
0.4628 + 3.5823(ZC )
8.1942(ZC )2
is the acentric factor and ZC the critical compressibility factor.
Heidemann and Khalil [16] showed a derivation of the critical

criteria starting from the condition of thermodynamic stability.

D = A A0
i0 ni
>0
(24)
i
T0 ,V0
Expanding the Helmholtz energy A in a Taylor series of the

compositional changes ni = ni ni0 , we have:

NC NC
NC NC NC
1 2 A
3 A
1
D=
n +
n
2!
3!
ni nj
ni nj nk
J I
i
k j

b
2.4. Cubic equations of state: PR and PTV

+
A general formula for a cubic EoS [14,15] can be written as:

RT
a
(20)
V- b V- (V- + b) + c(V- b)
The mixture EoS parameters a, b and c are calculated with the
following mixing rules:

NC NC NC NC
4 A
1
n + . . .
ni nj nk nl
4!
i
l
k j

P=
a=
NC
NC
xi xj aij ,
b=
i=1 j=1
NC
xi bi ,
c=
i=1
NC

i=1
n=
(22)
bi = b
RTC,i
,
PC,i
The two first terms correspond to the following critical criteria:

NC NC
1
1 2 (A/RT )
b = Qn =

2!
2
ni nj
i=1 j=1
where ij is the binary interaction parameter. Pure-component

parameters ai , bi and ci are calculated from pure-component
critical properties:
(RTC,i )2
,
PC,i
(21)
xi c i
The cross term, aij, is
aij = ai aj (1 ij )
ai = a a(TR )
(25)
ci = c

NC NC
1 ln f i
2
(23)
nj
(26)
n

NC NC NC
1 3 (A/RT )
c=
3!
ni nj nk
i=1 j=1 k=1
n =
RTC,i
PC,i

NC
NC
NC
2
1
ln fi
6
nj nk
(27)
n
2
where a(TR ) = [1 + m(1 TR )] and TR is the reduced temperature. The constants a , b , c and the parameter m are
described in Table 1 for each cubic EoS.
where n is a unit vector of the perturbed mole numbers,

nT n = 1. In these equations, NC is the number of components.
The fugacity is calculated with the fundamental thermodynamic relationships:
3. Determination of critical points
f i = xi i P
The critical point criteria can be stated in terms of the

Helmholtz energy A = A(n,T,V), which is the natural thermodynamic function for pressure-explicit EoS, P = P(n,T,V) [24].
(28)

RT ln i =
P
ni
T,V ,nj
RT
V

dV RT ln(Z)
(29)
P
ni

= f (EoS)
(30)
T,V ,nj
where fi is the fugacity, i the fugacity coefficient, n the mole

number, P the pressure, T the temperature, x the mole fraction, Vthe molar volume and Z the compressibility factor. The fugacity
coefficient and the Helmholtz free energy, A, are related by:

(nA)
ln i =
+ (Z 1) ln Z
(31)
ni ,T,nj=i
The first critical condition b = 0, Eq. (26), defines the limit of
stability (spinodal curve). The critical point is then defined as
such a point on the spinodal curve where the curve form of Eq.
(27) also vanishes, c = 0.
4. Computation of critical points
The algorithm by Heidemann and Khalil [16] solves the set
of Eqs. (26) and (27) in two nested loops for the liquidliquid
and vaporliquid critical volume (VC ) and critical temperature
(TC ). To locate a critical point in a NC component mixture with
mole fraction x = [x1 ,x2 ,. . .,xNC ]T is a normal problem in modeling binary or ternary systems. This is solved by developing the
following steps:
(i) Initialize the mixture critical temperature (TC ) and volume
(VC ). Each one can be initialized by means an arithmetic average of its component critical properties; thus
TC = xi TC,i and VC = xi VC,i . In case of not having Vc, the
critical pressure can be used PC = xi PC,i and then calculate
VC by using PC and TC in the ideal gas equation.
(ii) Find the limit of stability by satisfying the first critical condition (Eq. (26)). This is done by fixing the mixture critical
temperature (TC ) and iterating for mixture critical volume
(VC ) at which the determinant of the matrix Q reaches
zero (the determinant of the matrix Q is evaluated as the
product of diagonal elements after Gauss elimination). The
Helmholtz energy (A) is calculated (numerically) in terms
of fugacity from Eq. (31). The mixture critical volume
(VC ) on the stability limit is found by a NewtonRaphson
procedure.
(iii) Evaluate the eigenvector (n) by Gauss back substitution
[25] using the matrix Q obtained in step (i) and then normalize by
ni
ni =
NC
2
j=1 (nj )
(i = 1, 2, . . . , NC)
(32)
in order to obtain the vector n of a unit length, nT n = 1.

(iv) Compute the cubic form c (Eq. (27)) and test its value within
a given tolerance (c < 106 ).
In this work, the critical coefficient c is calculated numerically (see Appendix A). If the tolerance is not satisfied,
the mixture critical temperature (TC ) is corrected by another
NewtonRaphson scheme and the calculation is repeated. Otherwise, having obtained TC and VC , the mixture critical pressure
(PC ) is evaluated from the EoS. A fluxogram describing these

steps is shown in Appendix B.
5. Stability tests of critical points
The thermodynamic description of phase behavior should
always be completed by testing phase stability. Classical thermodynamics provides the following tests for critical points [8]:
(i) Test of mechanical stability. For a critical phase to be
mechanically stable, the calculated critical pressure must
be positive and its first partial derivative with respect to
volume must be negative.

P
PC > 0;
<0
(33)
V n,TC
(ii) Test of local diffusion stability. In a critical phase, coefficients b and c in Eqs. (26) and (27) are equal zero.
The critical phase will be stable with respect to small
fluctuations of compositions if the fourth-order stability
coefficient d is positive.

NC NC NC NC
1
4 A
d=
n
(34)
4!
ni nj nk nl
i
In this work, the critical coefficient d is calculated numerically (see Appendix C).
(iii) Test of global stability. A calculated critical point will be
stable if there is no additional phase with lower Gibbs
energy at a given temperature and pressure [26]. In this
work, the global stability criterion by the search method
proposed by Michelsen [27] was used.
6. Results and discussion
6.1. Pure-component parameters
In this work, several binary and ternary systems, which
include inorganic gases, hydrocarbons (light and heavy paraffins, olefins and aromatics), alcohols, carbon monoxide and
dioxide, were selected for studying. The compounds are listed
in Table 2. Critical experimental data are taken from literature
and are shown in Table 3 .
The PC-SAFT and SPHCT pure-component parameters were
obtained by fitting pure-component data. Data for vapor pressure
and liquid molar volumes were considered. The minimization
function used in the modified likelihood maximum [74] is:
OF =

NP
sat P sat |

|Pexp
calc
i=1
sat
Pexp
sat sat |
|exp
calc
sat
exp

(35)
where NP is the number of experimental point data for a given

system. The fitted characteristic parameters are then used to calculate the average deviation from the experimental saturated
Table 2
Components used in this work
Component
Symbol
Molecular weight (MW)
Component
Symbol
Molecular weight (MW)
Methane
Ethane
Propane
n-Butane
n-Pentane
n-Hexane
2,2-Dimethylbutane
n-Heptane
n-Octane
2,2,4-Trimethylpentane
n-Nonane
n-Decane
n-Undecane
n-Dodecane
n-Tridecane
n-Tetradecane
n-Pentadecane
n-Hexadecane
n-Heptadecane
n-Octadecane
n-Hexatriacontane
Cyclopentane
Cyclohexane
Cycloheptane
Cyclooctane
Ethylene
C1
C2
C3
nC4
nC5
nC6
2,2DimetC4
nC7
nC8
2,2,4TrimetC5
nC9
nC10
nC11
nC12
nC13
nC14
nC15
nC16
nC17
nC18
nC36
cC5
cC6
cC7
cC8
C2
16.043
30.070
44.096
58.123
72.150
86.177
86.177
100.204
114.231
114.231
128.258
142.285
156.312
170.338
184.365
198.392
212.419
226.446
240.473
254.500
506.984
70.134
84.161
98.188
112.215
28.054
Propylene
Hex-1-ene
Methanol
Ethanol
1-Propanol
2-Propanol
2-Methyl-2-propanol
1-Butanol
2-Butanol
3-Methyl-1-butanol
1-Pentanol
2-Pentanol
1-Hexanol
1-Octanol
1-Decanol
Benzene
Toluene
Ethylbenzene
Naphthalene
o-Xylene
Hydrogen sulfur
Sulfur hexafluoride
Hydrogen
Dinitrogen monoxide
Carbon monoxide
Carbon dioxide
C3
C6
C1 OH
C2 OH
1C3 OH
2C3 OH
2Met2C3 OH
1C4 OH
2C4 OH
3Met1C4 OH
1C5 OH
2C5 OH
1C6 OH
1C8 OH
1C10 OH
BNZ
TOL
C2 BNZ
NAP
oXYL
H2 S
SF6
H2
N2 O
CO
CO2
42.081
44.161
32.042
46.069
60.096
60.096
74.123
74.123
74.123
88.150
88.150
88.150
102.177
130.230
158.284
78.114
92.141
106.167
128.174
106.167
34.082
146.046
2.016
44.013
28.010
44.010
liquid molar volume and saturated vapor pressure:

P =
NP
sat P sat |
1 |Pexp
calc
100
sat
NP
Pexp
(36)
i=1
L
1 |vL
exp vcalc |
100
v =
NP
vL
exp
NP
(37)
i=1
In these equations, exp refers to vapor pressure and liquid

molar volume data obtained from DIPPR (1.2.0) [75]. Since
the accuracy of the fitting is better over a restricted data range,
and since often data and thermodynamic functions at only low
and moderate pressures are needed for engineering work, the
characteristic parameters are adjusted over an adequate pressure
and temperature range. The computational subroutines which
calculate EoS pure-component parameters have been written
considering the possibility of multiple solutions by searching
for the optimum parameters over a wide interval of feasible
solutions. This method was applied in previous works and the
results were very satisfactory [11,76,77]. In Table 4, the optimum characteristic parameters of PC-SAFT and SPHCT EoS
for the compounds listed in Table 3 are shown.
6.2. Binary interaction parameters
The binary interaction parameter, ij is obtained from data
regression. The regression program used in this work uses the
modified likelihood maximum principle [74] and an objective
function which includes the critical pressure and critical tem-
perature of both components:

NP
calc P exp
calc T exp

Pc,i
Tc,i
c,i
c,i
+
OF =
exp
exp
Pc,i
Tc,i
i=1
(38)
where NP is the number of experimental critical point data for a

given system. The optimized binary interaction parameters are
shown in Table 5.
The deviations of critical pressure and temperature were calculated using Eqs. (39) and (40), where NP is the number of
experimental critical points. The results are shown in Table 6 .

NP
exp
100 Pci Pcicalc
PC =
(39)

exp

NP
Pci
i

NP
exp
100 Tci Tcicalc
TC =

exp

NP
Tci
(40)
6.3. Modeling of uid phase behavior of binary and ternary

systems
The fluid-phase behavior obtained with the four thermodynamic models (PC-SAFT, SPHCT, PTV and PR) is represented
in graphical form for several binary and ternary systems through
Figs. 117. The correlated critical lines, using one binary interaction parameter for each thermodynamic model (Table 5), were
compared to the experimental critical points available, in terms
of critical pressure and temperature deviations (Table 6). All
critical points reported have passed the local and global stability
tests.
Table 3
Main physical characteristics of binary and ternary systems used in this work
System number
Binary system
NP
Tc (K)
Pc (MPa)
Reference
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62
63
C1 + C2
C1 + C3
C1 + nC4
C1 + nC5
C1 + nC6
C1 + nC7
C1 + nC8
C1 + nC9
C1 + nC10
C2 + C3
C2 + nC4
C2 + nC5
C2 + nC6
C2 + nC7
C2 + nC10
C3 + nC4
C3 + nC5
C3 + nC6
C3 + nC7
C3 + nC8
C3 + nC10
nC4 + nC5
nC4 + nC6
nC4 + nC7
nC4 + nC8
nC4 + nC10
nC5 + nC6
nC5 + nC7
nC5 + nC8
nC5 + nC9
nC5 + nC10
nC6 + nC7
nC6 + nC8
nC6 + nC10
nC7 + nC8
cC5 + nC5
cC5 + nC7
cC5 + nC8
cC5 + nC9
cC6 + C1
cC6 + C2
cC6 + nC5
cC6 + nC6
cC6 + nC7
cC6 + nC8
cC6 + nC9
cC6 + nC10
C2 + CO2
C3 + CO2
nC4 + CO2
nC10 + CO2
nC11 + CO2 b
nC12 + CO2 c
nC13 + CO2 c
nC14 + CO2 c
nC15 + CO2 c
nC16 + CO2 b
nC17 + CO2 b
nC18 + CO2 c
nC36 + CO2 b
cC6 + CO2
C2 + N2 O
C3 + N2 O
17
29
10
5
5
12
2
4
7
16
18
7
3
15
8
11
9
11
5
7
5
9
9
14
9
3
5
3
6
12
7
9
9
9
9
9
9
9
9
5
8
5
9
9
9
9
9
17
18
18
9
9
13
16
15
16
19
10
12
13
9
10
10
192.4302.0
192.3364.2
210.9394.2
310.9444.3
263.0423.2
277.6510.9
298.2323.2
273.2348.2
277.6510.9
310.9366.5
315.6422.0
338.7422.0
338.7449.8
322.3515.5
310.9510.9
375.0418.6
387.5460.2
387.6496.3
400.7521.2
390.0548.0
377.6510.9
430.7466.1
437.4502.0
436.3533.4
451.2561.1
444.3510.9
473.3499.4
492.2526.2
487.2558.9
493.4587.8
507.0602.9
511.4537.5
515.8564.5
524.4609.6
543.5566.4
474.3507.6
516.5538.8
521.9565.9
527.6590.3
294.3444.3
362.7537.3
491.6541.2
512.4549.1
541.8552.5
556.5568.3
560.9592.0
565.1614.3
291.0305.4
304.4366.2
311.1415.9
310.9510.9
153.0673.0
256.0267.3
256.0279.0
270.0311.2
275.0309.4
283.2413.3
303.0393.0
396.6673.2
344.0573.3
373.2535.2
299.1309.5
309.5369.7
4.726.76
4.7510.16
7.1713.26
7.0716.93
12.1620.80
8.3124.88
26.6527.34
31.7032.30
20.0637.00
4.475.19
4.075.81
5.846.78
6.477.90
4.708.87
5.3611.82
3.944.40
3.714.62
3.534.99
3.615.39
3.545.96
4.676.81
3.443.78
3.183.90
2.974.11
2.784.32
4.254.92
a
3.063.32
a
2.503.66
a
2.803.03
2.603.05
2.313.19
2.552.74
3.494.39
2.914.33
2.704.38
2.524.46
20.0628.19
5.229.21
a
3.133.96
2.873.91
2.643.90
2.443.92
2.313.98
4.887.40
4.977.05
4.898.17
8.0018.84
10.00300.00
2.112.88
2.133.93
3.118.26
3.608.02
4.4425.60
10.00100.00
1.026.19
1.0228.98
6.7014.00
4.887.24
4.257.24
[2]
[2]
[2]
[2]
[2]
[2]
[2]
[2]
[2]
[2,28,29]
[2,29]
[2]
[2]
[2]
[2]
[2,28]
[2]
[2]
[2]
[2]
[2]
[2]
[2]
[2]
[2]
[2]
[2]
[2]
[2]
[2]
[2]
[2]
[2]
[2]
[2]
[2]
[2]
[2]
[2]
[2]
[2]
[2]
[2]
[2]
[2]
[2]
[2]
[2,30]
[2,28]
[2,28]
[2,31,32]
[33,34]
[3537]
[34,3840]
[39,41,42]
[39,43,44]
[34,4345]
[46]
[46,47]
[4850]
[2]
[29]
[29]
Table 3 (Continued )
System number
Binary system
64
65
66
67
68
69
70
71
72
73
74
75
76
77
78
79
80
81
82
83
84
85
86
87
88
89
90
91
92
93
94
95
96
97
98
99
100
101
102
103
104
105
106
107
108
109
110
111
112
113
114
115
116
117
118
119
120
121
122
123
124
125
126
127
128
C2 + BNZ
C3 + BNZ
nC5 + BNZ
nC6 + BNZ
nC7 + BNZ
nC8 + BNZ
nC9 + BNZ
nC10 + BNZ
nC5 + TOL
nC6 + TOL
nC5 + C2 BNZ
nC6 + C2 BNZ
nC7 + C2 BNZ
nC8 + C2 BNZ
cC5 + cC6
cC5 + cC7
cC5 + cC8
cC6 + cC7
cC6 + cC8
C2 OH + 2,2dimetC4
C2 OH + 2,2,4trimetC5
C2 OH + nC6
C2 OH + nC7
C2 OH + nC8
1C3 OH + 2,2dimetC4
1C3 OH + 2,2,4trimetC5
1C3 OH + cC6
2C3 OH + 2,2dimetC4
2C3 OH + nC8
2met2C3 OH + 2,2dimetC4
2met2C3 OH + nC6
2met2C3 OH + nC8
2met2C3 OH + nC9
2C4 OH + nC6
2C4 OH + nC8
3met1C4 OH + nC6
3met1C4 OH + nC8
3met1C4 OH + cC6
1C5 OH + nC6
1C5 OH + nC8
1C5 OH + cC6
2C5 OH + 2,2dimetC4
2C5 OH + nC5
2C5 OH + nC6
2C5 OH + nC8
2C5 OH + nC10
2C5 OH + nC12
2C5 OH + cC6
C1 OH + CO2 b
C2 OH + CO2 c
1C3 OH + CO2 c
2C3 OH + CO2 b
1C4 OH + CO2 c
2met2C3 OH + CO2 c
1C5 OH + CO2 c
1C6 OH + CO2 c
1C8 OH + CO2 c
1C10 OH + CO2 c
BNZ + cC5
BNZ + cC6
TOL + cC6
BNZ + TOL
BNZ + oXYL
BNZ + C2 BNZ
TOL + oXYL
NP
6
4
5
9
9
5
9
9
4
6
9
9
9
9
9
6
7
6
9
6
8
8
8
8
8
8
8
7
8
8
8
8
8
8
8
9
9
9
8
8
9
8
7
10
7
8
8
9
12
13
15
12
16
12
13
12
12
12
12
17
4
20
9
9
9
Tc (K)
326.1540.8
377.6477.6
474.4528.4
511.0554.5
540.8557.3
561.0567.8
566.0591.9
570.1614.4
489.7563.2
523.5567.6
488.7605.7
519.4606.8
547.3608.2
572.5610.4
517.4550.5
557.4583.9
536.1621.5
565.7589.7
566.9635.7
479.3513.9
506.0544.0
488.7513.9
504.3540.3
512.8568.9
487.8536.8
524.0544.0
527.9553.5
481.7508.3
508.3568.9
485.3506.5
496.8507.7
506.5568.9
506.5594.6
505.8536.1
535.2568.9
507.7579.4
562.7579.4
551.9579.4
507.7587.7
565.6587.7
553.5587.7
488.8560.4
469.7560.4
507.7560.4
555.1568.9
560.4617.7
560.4658.2
547.5560.4
291.2491.7
291.2373.0
313.4333.4
293.2394.2
303.2428.2
299.0353.2
314.3337.5
227.2312.9
255.2309.1
275.2307.2
516.4556.9
552.6558.7
561.0585.0
566.6593.7
572.4625.3
570.6613.5
597.0627.0
Pc (MPa)
5.999.52
4.415.98
a
3.174.66
2.894.58
2.684.55
2.494.55
2.364.60
a
3.543.95
3.644.09
3.173.65
2.853.56
2.593.49
4.154.51
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
0.5614.75
0.4814.35
0.5210.82
1.0312.41
7.0617.41
0.6412.12
5.2811.98
0.808.41
2.097.97
3.667.76
4.574.90
4.154.80
a
4.204.84
3.884.87
3.774.82
3.774.10
Reference
[2]
[2]
[2]
[2]
[2]
[2]
[2]
[2]
[2]
[2]
[2]
[2]
[2]
[2]
[2]
[2]
[2]
[2]
[2]
[51]
[51]
[51]
[51]
[51]
[51]
[51]
[51]
[51]
[51]
[51]
[51]
[51]
[51]
[51]
[51]
[51]
[51]
[51]
[51]
[51]
[51]
[51]
[51]
[51]
[51]
[51]
[51]
[51]
[5254]
[5557]
[55,58,59]
[57,60,61]
[6264]
[65,66]
[55,67,68]
[44,69]
[69]
[69]
[2]
[2]
[2]
[2]
[2]
[2]
[2]
System number
Binary system
129
130
131
132
133
134
135
136
137
138
139
140
141
TOL + C2 BNZ
oXYL + C2 BNZ
nC5 + H2 S
NAP + C2
N2 O + CO2
N2 O + SF6
C2 + BNZ + C2 BNZ
C1 OH + CO + CO2
C3 + CO + CO2
C3 + H2 + CO2
C6 + CO + CO2
C6 + H2 + CO2
SF6 + C2 + CO2
a
b
c
NP
9
9
14
9
9
10
10
26
4
2
5
3
54
Tc (K)
Pc (MPa)
Reference
596.0615.5
618.8628.7
377.6469.6
325.3540.2
304.2309.5
302.6318.7
282.8572.3
293.3327.8
299.2303.3
305.0305.4
308.6316.9
312.4320.6
289.1312.1
3.674.07
3.633.71
4.238.98
17.6324.72
7.247.37
3.757.24
5.0211.92
8.1412.98
7.527.98
8.369.06
8.0410.20
8.8910.98
3.757.40
[2]
[2]
[2]
[2]
[29]
[29]
[70]
[71]
[72]
[72]
[72]
[72]
[73]
Experimental critical pressure not available.

Vaporliquid equilibrium and high-pressure experimental data.
Liquidliquidvapor experimental data.
Fig. 1. PT and Tx projections of critical lines for C1 (1) + C3 (2) and C1 (1) + nC10
(2) systems.
Fig. 2. PT and Tx projections of critical lines for C3 (1) + nC4 (2) and C3
(1) + nC8 (2) systems.
10
Table 4
Pure-component parameters for the PC-SAFT and SPHCT models
Component
C1
C2
C3
nC4
nC5
nC6
2,2DimetC4
nC7
nC8
2,2,4TrimetC5
nC9
nC10
nC11
nC12
nC13
nC14
nC15
nC16
nC17
nC18
nC36
cC5
cC6
cC7
cC8
C2
C3
C6
C1 OH
C2 OH
1C3 OH
2C3 OH
2Met2C3 OH
1C4 OH
2C4 OH
3Met1C4 OH
1C5 OH
2C5 OH
1C6 OH
1C8 OH
1C10 OH
BNZ
TOL
C2 BNZ
NAP
o-XYL
H2 S
SF6
H2
N2 O
CO
CO2
PC-SAFT EoS
SPHCT EoS
(10+10
m/MW
(mol1 )
0.072380
0.048450
0.049710
0.039779
0.034090
0.034088
0.030120
0.033452
0.032850
0.031256
0.032132
0.031543
0.030856
0.031085
0.031459
0.030793
0.029354
0.029042
0.029023
0.028921
0.027846
0.031256
0.029946
0.028542
0.027366
0.056070
0.045892
0.034896
0.050304
0.049562
0.048592
0.048236
0.046382
0.036395
0.037412
0.033545
0.042099
0.042452
0.034654
0.033045
0.031252
0.032712
0.030984
0.030046
0.024613
0.030125
0.113165
0.028140
0.445230
0.107241
0.057112
0.048237
3.5129
3.6506
3.4984
3.7124
3.8729
3.8383
2.5812
3.8432
3.8484
3.7545
3.8165
3.7984
3.8805
3.8907
3.9020
3.9102
3.9312
3.9456
3.9545
3.9603
4.0931
3.8123
3.8399
3.8563
3.8636
3.4250
3.5274
3.7598
3.3521
3.2725
3.2996
3.2522
3.6212
3.6906
3.6425
3.7852
3.3830
3.3245
3.6140
3.7256
3.7356
3.5878
3.6869
3.7374
3.8685
3.7812
2.2706
2.8015
3.5023
2.1121
3.0417
2.7352
m)
/k (K)
kAB
AB /k
P
v (10+6 m3
mol1 )
T* (K)
P
140.92
201.42
197.61
223.18
240.11
239.57
4.0065
240.56
242.61
243.25
240.56
240.87
247.12
249.05
245.29
249.38
253.48
254.05
254.86
255.84
271.92
275.42
279.21
283.41
286.41
178.77
206.89
235.78
193.94
201.75
238.56
225.25
242.51
254.91
251.36
262.25
251.27
248.56
266.36
268.45
269.75
281.55
282.69
280.85
343.42
288.45
156.92
130.72
27.81
121.12
83.45
166.21
0.034563
0.032012
0.015045
0.023546
0.008432
0.006895
0.012365
0.003256
0.009845
0.012363
0.005543
0.002104
0.001145
2.8125
2.5842
2.2152
2.2452
2.3652
2.5123
2.4856
2.4562
2.2485
2.3832
2.5248
2.7136
2.9245
0.0011
0.0023
0.0022
0.0024
0.0008
0.0032
0.0030
0.0028
0.0021
0.0019
0.0023
0.0045
0.0068
0.0105
0.0154
0.0129
0.0098
0.0142
0.0236
0.0362
0.0196
0.0063
0.0036
0.0053
0.0050
0.0045
0.0056
0.0042
0.0178
0.0389
0.0362
0.0452
0.0854
0.0584
0.0456
0.0639
0.0645
0.0896
0.1023
0.1826
0.2320
0.0036
0.0017
0.0048
0.0042
0.0062
0.0046
0.0156
0.0320
0.0365
0.0035
0.0049
0.4225
0.4137
0.8048
0.3016
0.3187
0.2478
0.2845
0.2315
0.1943
0.1963
0.2152
0.2054
0.2685
0.3564
0.5318
0.3867
0.5633
0.8452
0.6630
0.4125
0.7856
0.2365
0.2265
0.2812
0.3221
0.4385
0.5965
0.6322
0.6945
0.8045
0.9633
0.6360
0.4039
0.4013
0.7852
0.9623
0.8502
0.7455
0.8220
0.8962
0.7854
0.2856
0.3545
0.3933
0.3276
0.4213
0.4275
0.3420
0.7582
0.3201
0.3376
0.2635
18.152
26.743
36.452
41.326
51.364
60.418
53.745
67.421
76.253
74.584
84.636
98.743
106.881
115.886
122.569
133.897
142.902
155.123
159.153
169.919
332.017
56.320
61.453
68.122
75.633
29.126
31.578
58.125
17.435
21.704
27.839
27.236
31.453
34.708
34.503
36.412
40.852
40.836
46.634
49.458
53.452
43.634
48.259
39.213
69.529
59.421
14.327
24.452
12.453
14.745
12.363
15.324
80.12
122.35
143.56
155.63
166.07
177.64
168.75
182.54
186.43
204.57
189.23
195.42
196.92
197.42
197.89
201.78
203.40
204.19
207.36
208.27
217.44
163.75
175.48
182.63
189.42
111.52
138.75
167.74
165.86
161.63
178.90
177.58
183.42
196.34
196.75
198.42
209.65
208.98
219.83
223.45
228.45
204.12
219.48
208.62
247.36
315.54
135.42
189.54
107.85
196.45
103.25
106.84
1.0000
1.2443
1.4036
1.6544
1.8569
1.9475
1.8856
1.2132
2.3572
1.6078
2.6323
3.0412
3.2160
3.3859
3.5645
3.7258
3.8954
4.0596
4.2362
4.4049
7.4621
1.8942
2.1140
2.3623
2.6354
1.2245
1.3989
2.0689
2.7048
3.1312
2.6475
2.6345
2.6042
2.3685
2.3665
2.3602
2.3492
2.3563
2.4643
2.4854
2.4965
1.6432
1.7004
2.2212
2.1142
2.1566
1.5842
1.6845
1.1236
1.8656
1.8315
1.8646
0.1326
0.2133
0.1546
0.3256
0.2458
0.1423
0.1636
0.1233
0.0945
0.1233
0.1363
0.1522
0.1866
0.1786
0.3265
0.3312
0.2588
0.3653
0.3042
0.3241
0.2863
0.2313
0.3652
0.3945
0.3021
0.3624
0.3952
0.2966
0.0896
0.1856
0.3260
0.2530
0.3896
0.3042
0.3785
0.4530
0.3560
0.4550
0.5123
0.4851
0.6856
0.1145
0.2415
0.3326
0.4526
0.5241
0.5484
0.6312
0.2856
0.3360
0.4511
0.4936
0.4892
0.4456
0.5483
0.3745
0.4187
0.3845
0.6532
0.3562
0.3612
0.6633
0.4452
0.4215
0.5863
0.7588
0.6990
0.8525
0.7856
0.8550
0.8890
0.7456
0.9636
0.4436
0.4632
0.4421
0.5203
0.5893
0.8042
0.7563
0.7315
0.6651
0.6841
0.7125
0.5963
0.7412
0.8963
0.9125
0.9563
0.8963
0.7452
0.8455
0.8541
0.4285
0.5982
0.4935
0.4563
0.6036
0.6840
0.8563
0.4130
0.6833
0.4865
0.4862
(103 K)
6.3.1. Binary systems

6.3.1.1. n-Alkane + n-alkane systems. These mixtures (systems 135) have been investigated experimentally by many
researchers and have been compared with experimental data
[2,28,29]. Critical pressure and temperature deviation ranges are
0.000.05% and 0.030.53% for PC-SAFT EoS; 0.983.50%
and 0.020.30% for SPHCT EoS; 3.025.81% and 0.020.30%

for PTV EoS; and 2.045.92% and 0.010.32% for PR EoS.
Fig. 1 shows the performance of each EoS in PT and Tx
projections for the C1 + C3 and C1 + nC10 systems. These mixtures seem to have a fluid phase behavior of Type I in the van
Konynenburg and Scotts classification [1]. In others words, the

Table 5
Binary interaction parameters (kij ) for the binary systems used in this work
System number
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62
System number
Equation of State
PC-SAFT
SPHCT
PTV
PR
0.0102
0.0215
0.0104
0.0025
0.0048
0.0059
0.0104
0.0115
0.0172
0.0143
0.0102
0.0047
0.0141
0.0104
0.0216
0.0045
0.0093
0.0109
0.0048
0.0102
0.0183
0.0114
0.0183
0.0104
0.0134
0.0221
0.0214
0.0145
0.0341
0.0283
0.0215
0.0013
0.0143
0.0103
0.0108
0.0019
0.0103
0.0095
0.0122
0.0211
0.0253
0.0103
0.0118
0.0145
0.0342
0.0211
0.0147
0.0085
0.0148
0.0383
0.0342
0.0301
0.0258
0.0265
0.0214
0.0207
0.0114
0.0085
0.0126
0.0247
0.0224
0.0145
0.0203
0.0421
0.0231
0.0356
0.0634
0.0335
0.0981
0.0423
0.0742
0.0038
0.0315
0.0423
0.0483
0.0231
0.0534
0.0085
0.0184
0.0213
0.0303
0.0283
0.0203
0.0036
0.0091
0.0293
0.0412
0.0542
0.0032
0.0105
0.0284
0.0074
0.0216
0.0019
0.0029
0.0326
0.0008
0.0065
0.0016
0.0063
0.0154
0.0184
0.0017
0.0255
0.0078
0.0056
0.0089
0.0017
0.0078
0.0015
0.0027
0.0643
0.0425
0.0401
0.0388
0.0381
0.0391
0.0301
0.0335
0.0245
0.0288
0.0315
0.0421
0.0315
0.0815
0.1021
0.0642
0.0077
0.0343
0.0411
0.0518
0.0041
0.0433
0.0042
0.0147
0.0169
0.0186
0.0215
0.0447
0.0015
0.0210
0.0143
0.0215
0.0275
0.0143
0.0128
0.0103
0.0011
0.0215
0.0426
0.0015
0.0018
0.0183
0.0242
0.0249
0.0192
0.0013
0.0144
0.0107
0.0008
0.0015
0.0143
0.0193
0.0281
0.0215
0.0183
0.0055
0.0109
0.0207
0.0048
0.0193
0.0018
0.0059
0.0695
0.0681
0.0605
0.0591
0.0545
0.0615
0.0415
0.0318
0.0215
0.0314
0.0385
0.0540
0.0451
0.0314
0.0242
0.0103
0.0087
0.0243
0.0143
0.0015
0.0241
0.0572
0.0083
0.0104
0.0103
0.0113
0.0174
0.0305
0.0011
0.0163
0.0193
0.0183
0.0141
0.0145
0.0083
0.0045
0.0187
0.0093
0.0168
0.0016
0.0058
0.0193
0.0283
0.0197
0.0093
0.0183
0.0218
0.0093
0.0018
0.0193
0.0219
0.0247
0.0118
0.0143
0.0122
0.0043
0.0027
0.0128
0.0143
0.0245
0.0012
0.0019
0.0725
0.0592
0.0501
0.0491
0.0392
0.0304
0.0383
0.0245
0.0145
0.0248
0.0215
0.0627
0.0315
11
63
64
65
66
67
68
69
70
71
72
73
74
75
76
77
78
79
80
81
82
83
84
85
86
87
88
89
90
91
92
93
94
95
96
97
98
99
100
101
102
103
104
105
106
107
108
109
110
111
112
113
114
115
116
117
118
119
120
121
122
123
124
125
Equation of State
PC-SAFT
SPHCT
PTV
PR
0.0108
0.0215
0.0018
0.0187
0.0305
0.0215
0.0286
0.0315
0.0218
0.0389
0.0322
0.0183
0.0103
0.0052
0.0041
0.0141
0.0083
0.0183
0.0143
0.0214
0.0211
0.0181
0.0015
0.0148
0.0103
0.0018
0.0025
0.0053
0.0101
0.0089
0.0124
0.0189
0.0204
0.0109
0.0214
0.0208
0.0211
0.0189
0.0103
0.0014
0.0008
0.0087
0.0184
0.0033
0.0121
0.0103
0.0109
0.0083
0.0014
0.0186
0.0163
0.0141
0.0122
0.0086
0.0104
0.0055
0.0153
0.0182
0.0173
0.0058
0.0103
0.0155
0.0143
0.0213
0.0315
0.0172
0.0241
0.0326
0.0152
0.0236
0.0213
0.0312
0.0452
0.0532
0.0196
0.0153
0.0096
0.0098
0.0075
0.0026
0.0088
0.0153
0.0263
0.0314
0.0210
0.0308
0.0249
0.0123
0.0214
0.0203
0.0283
0.0191
0.0015
0.0027
0.0101
0.0214
0.0135
0.0314
0.0303
0.0285
0.0215
0.0243
0.0340
0.0293
0.0343
0.0188
0.0214
0.0181
0.0143
0.0013
0.0148
0.0127
0.0343
0.0240
0.0183
0.0242
0.0281
0.0143
0.0283
0.0305
0.0285
0.0302
0.0156
0.0163
0.0136
0.0038
0.0540
0.0822
0.0845
0.0543
0.0143
0.0247
0.0318
0.0343
0.0415
0.0315
0.0450
0.0153
0.0250
0.0091
0.0188
0.0143
0.0240
0.0283
0.0041
0.0193
0.0145
0.0169
0.0013
0.0124
0.0108
0.0314
0.0318
0.0325
0.0215
0.0018
0.0021
0.0123
0.0089
0.0044
0.0143
0.0148
0.0015
0.0123
0.0018
0.0303
0.0253
0.0269
0.0283
0.0144
0.0108
0.0193
0.0089
0.0019
0.0109
0.0141
0.0243
0.0183
0.0208
0.0314
0.0309
0.0301
0.0389
0.0384
0.0402
0.0190
0.0181
0.0245
0.0013
0.0308
0.0455
0.0342
0.0414
0.0318
0.0213
0.0115
0.0018
0.0243
0.0211
0.0363
0.0093
0.0144
0.0218
0.0215
0.0096
0.0143
0.0241
0.0014
0.0215
0.0168
0.0114
0.0013
0.0122
0.0089
0.0288
0.0253
0.0269
0.0188
0.0013
0.0008
0.0015
0.0127
0.0189
0.0183
0.0201
0.0125
0.0127
0.0088
0.0214
0.0143
0.0204
0.0273
0.0205
0.0198
0.0086
0.0143
0.0240
0.0168
0.0193
0.0248
0.0215
0.0183
0.0384
0.0315
0.0343
0.0430
0.0456
0.0384
0.0076
0.0112
0.0142
0.0215
12
System number
126
127
128
129
130
131
132
133
134
Table 6
Average deviations in critical temperature and pressure for the systems studied
in this work
Equation of State
PC-SAFT
SPHCT
PTV
PR
0.0214
0.0187
0.0283
0.0314
0.0104
0.0342
0.0426
0.0315
0.0214
0.0085
0.0102
0.0023
0.0065
0.0028
0.0214
0.0332
0.0319
0.0366
0.0143
0.0121
0.0343
0.0215
0.0148
0.0132
0.0283
0.0513
0.0618
0.0187
0.0128
0.0014
0.0143
0.0248
0.0485
0.0622
0.0415
0.0601
0.0202
0.0321
0.0424
0.0245
0.0243
0.0332
0.0213
0.0402
0.0517
0.0252
0.0622
0.0440
0.0236
0.0215
0.0171
0.0545
0.0232
0.0315
0.0318
0.0452
0.0630
0.0347
0.0510
0.0331
0.0095
0.0140
0.0171
0.0308
0.0283
0.0315
0.0433
0.0212
0.0630
0.0331
0.0314
0.0331
0.0083
0.0042
0.0140
0.0292
0.0108
0.0283
0.0318
0.0309
0.0212
0.0289
0.0215
0.0314
0.0141
0.0015
0.0171
0.0343
0.0193
0.0315
0.0141
0.0247
0.0630
0.0218
0.0316
0.0331
0.0092
0.0015
0.0042
0.0415
0.0193
0.0108
0.0301
0.0247
0.0309
0.0293
0.0316
0.0215
0.0143
0.0113
0.0085
0.0343
0.0280
0.0015
0.0215
0.0340
0.0018
0.0319
0.0415
0.0012
135
C2 + BNZ
C2 + C2 BNZ
BNZ + C2 BNZ
136
C1 OH + CO
C1 OH + CO2
CO + CO2
137
C3 + CO
C3 + CO2
CO + CO2
138
C3 + H2
H2 + CO2
C3 + CO2
139
C6 + CO
C6 + CO2
CO + CO2
140
C6 + H2
C6 + CO2
H2 + CO2
141
SF6 + C2
SF6 + CO2
C2 + CO2
pure-component critical points are joined by a simple critical

line.
The C3 + nC4 and C3 + nC8 systems have the same fluid phase
behavior shown in the previous systems. Their critical behavior
is shown through Fig. 2 in PT and Tx projections. Reasonable
agreements between experimental data and predicted values for
the four thermodynamic models are noticed in critical pressure
and temperature deviations (Table 6). In this figure, due the similar properties between C3 and nC4 , their critical line is almost
linear, while the critical line of C3 + nC8 systems shows one
maximum critical point.
In Fig. 3, the LV phase behavior at critical conditions is shown for the nC4 + nC6 and nC4 + nC10 systems.
These systems have the same fluid phase behavior than
the systems shown in Figs. 1 and 2. PC-SAFT EoS is
capable of predicting the fluid phase behavior of these
systems with more precision than SPHCT, PTV and PR
System
number
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Equation of state
PC-SAFT
SPHCT
PTV
PR
PC
TC
PC
TC
PC
TC
PC
TC
0.00
0.01
0.00
0.01
0.00
0.01
0.01
0.02
0.05
0.00
0.01
0.00
0.03
0.01
0.01
0.00
0.01
0.02
0.01
0.01
0.03
0.00
0.01
0.00
0.01
0.01
a
0.01
a
0.00
a
0.01
0.02
0.00
0.01
0.00
0.02
0.01
0.03
0.02
0.02
a
0.02
0.00
0.01
0.02
0.01
0.02
0.01
0.00
0.01
0.01
0.00
0.02
0.01
0.01
0.02
0.00
0.01
0.01
0.23
0.53
0.35
0.38
0.42
0.33
0.14
0.28
0.12
0.08
0.10
0.09
0.14
0.18
0.03
0.15
0.18
0.09
0.20
0.25
0.30
0.23
0.24
0.28
0.21
0.36
0.43
0.31
0.18
0.29
0.40
0.38
0.19
0.28
0.23
0.14
0.22
0.45
0.37
0.26
0.14
0.20
0.18
0.26
0.35
0.40
0.42
0.40
0.35
0.04
0.12
0.25
0.31
0.40
0.28
0.15
0.21
0.20
0.18
0.20
2.45
2.86
3.18
2.15
2.08
1.86
0.98
2.11
2.88
2.58
2.98
2.05
3.08
2.25
3.36
1.88
2.15
2.20
2.85
3.08
2.92
3.10
2.95
3.20
2.91
3.28
a
3.50
a
3.20
a
2.95
2.82
2.86
2.49
3.15
3.20
3.03
2.98
3.44
3.88
a
3.02
4.05
4.15
3.02
3.80
3.15
2.85
3.16
3.14
2.90
2.95
3.20
3.15
4.50
3.89
3.25
3.45
3.15
0.12
0.08
0.15
0.12
0.09
0.25
0.30
0.21
0.07
0.12
0.25
0.18
0.20
0.10
0.09
0.02
0.12
0.18
0.20
0.06
0.10
0.10
0.08
0.12
0.13
0.04
0.08
0.05
0.15
0.11
0.05
0.10
0.08
0.13
0.08
0.04
0.11
0.08
0.15
0.08
0.10
0.05
0.08
0.12
0.15
0.13
0.04
0.21
0.18
0.04
0.02
0.12
0.18
0.20
0.15
0.22
0.12
0.25
0.20
0.11
4.85
5.81
4.80
4.63
4.95
4.30
5.02
4.50
4.52
4.95
3.89
3.45
4.15
4.20
4.38
3.15
3.08
3.89
4.09
3.43
3.29
3.45
3.02
3.89
3.47
3.82
a
4.09
a
3.54
a
4.55
4.92
4.88
4.54
4.59
4.37
4.08
5.14
5.33
4.89
a
5.19
5.46
4.51
4.79
4.82
4.15
4.20
3.18
4.60
4.13
4.01
4.18
3.95
3.80
3.89
4.01
4.15
4.06
0.08
0.04
0.10
0.12
0.15
0.08
0.12
0.07
0.06
0.05
0.02
0.10
0.12
0.13
0.04
0.05
0.12
0.25
0.29
0.09
0.30
0.02
0.12
0.15
0.12
0.08
0.12
0.10
0.08
0.24
0.21
0.10
0.12
0.25
0.20
0.08
0.10
0.22
0.09
0.14
0.10
0.08
0.12
0.15
0.22
0.18
0.30
0.23
0.19
0.06
0.01
0.15
0.12
0.23
0.18
0.25
0.21
0.18
0.21
0.13
3.89
2.04
3.47
2.89
5.81
5.92
4.87
3.59
4.11
5.14
4.89
4.12
4.86
5.02
3.94
4.15
4.08
3.19
4.01
3.38
3.69
4.15
4.02
3.89
4.07
3.18
a
4.98
a
4.88
a
5.83
5.89
5.71
5.89
5.22
6.15
6.29
5.89
7.38
6.43
a
5.93
6.82
5.80
5.88
6.15
5.55
5.10
3.26
3.21
4.58
5.16
4.65
3.25
4.15
3.92
4.13
4.33
5.30
0.02
0.08
0.12
0.15
0.09
0.08
0.04
0.06
0.08
0.10
0.12
0.11
0.09
0.08
0.02
0.01
0.12
0.08
0.07
0.10
0.06
0.20
0.22
0.14
0.12
0.08
0.30
0.24
0.32
0.08
0.14
0.10
0.08
0.21
0.08
0.13
0.21
0.23
0.11
0.28
0.32
0.10
0.11
0.09
0.22
0.21
0.17
0.20
0.18
0.09
0.10
0.12
0.15
0.11
0.25
0.20
0.18
0.12
0.20
0.18

System
number
System
number
61
62
63
64
65
66
67
68
69
70
71
72
73
74
75
76
77
78
79
80
81
82
83
84
85
86
87
88
89
90
91
92
93
94
95
96
97
98
99
100
101
102
103
104
105
106
107
108
109
110
111
112
113
114
115
116
117
118
119
120
121
122
Equation of state
PC-SAFT
SPHCT
PTV
PR
PC
TC
PC
TC
PC
TC
PC
TC
0.00
0.01
0.01
0.03
0.03
a
0.04
0.05
0.02
0.01
0.03
a
0.02
0.01
0.01
0.01
0.02
0.01
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
0.01
0.02
0.01
0.00
0.01
0.02
0.03
0.01
0.02
0.02
0.00
0.20
0.22
0.21
0.58
0.62
0.28
0.33
0.45
0.15
0.22
0.38
0.37
0.28
0.14
0.29
0.38
0.51
0.18
0.40
0.28
0.18
0.09
0.12
0.10
0.15
0.08
0.22
0.20
0.18
0.16
0.25
0.31
0.22
0.21
0.18
0.12
0.05
0.08
0.12
0.21
0.11
0.10
0.06
0.15
0.12
0.20
0.17
0.11
0.05
0.06
0.03
0.08
0.12
0.20
0.17
0.18
0.19
0.11
0.09
0.12
0.15
0.07
2.86
2.90
2.78
7.88
6.10
a
4.18
5.86
6.09
6.15
5.14
a
3.56
2.85
2.65
3.15
4.11
3.15
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
2.85
2.90
2.95
3.15
2.75
2.68
2.91
3.18
3.75
3.52
2.89
0.04
0.15
0.22
0.88
0.80
0.50
0.48
0.69
0.91
0.10
0.29
0.28
0.44
0.22
0.28
0.10
0.12
0.11
0.09
0.21
0.20
0.12
0.28
0.12
0.25
0.17
0.10
0.08
0.12
0.11
0.15
0.21
0.08
0.09
0.10
0.13
0.12
0.07
0.15
0.12
0.21
0.20
0.11
0.12
0.10
0.09
0.06
0.15
0.12
0.01
0.10
0.12
0.10
0.08
0.06
0.05
0.11
0.18
0.08
0.15
0.12
0.01
3.42
4.56
6.18
10.36
9.48
a
9.62
10.12
10.20
9.11
8.31
a
4.24
4.15
3.88
4.25
6.24
5.14
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
4.15
5.08
4.81
4.33
4.77
3.89
4.90
5.15
4.42
4.89
8.11
0.10
0.15
0.25
0.21
0.18
0.10
0.08
0.12
0.15
0.22
0.14
0.21
0.44
0.25
0.20
0.28
0.30
0.10
0.08
0.13
0.14
0.09
0.19
0.11
0.10
0.15
0.08
0.06
0.09
0.10
0.12
0.15
0.03
0.06
0.07
0.04
0.07
0.08
0.10
0.07
0.04
0.20
0.05
0.12
0.18
0.21
0.12
0.10
0.03
0.05
0.03
0.02
0.01
0.05
0.12
0.13
0.20
0.15
0.18
0.15
0.25
0.12
4.41
6.15
5.85
12.16
10.48
a
10.14
12.15
11.03
12.44
10.25
a
3.12
7.84
6.15
7.27
6.88
6.15
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
6.18
4.29
5.15
6.10
5.11
4.90
4.86
4.88
4.75
4.25
8.46
0.08
0.12
0.19
0.58
0.47
0.40
0.38
0.45
0.47
0.43
0.50
0.33
0.66
0.17
0.18
0.25
0.11
0.12
0.11
0.15
0.12
0.10
0.08
0.12
0.06
0.03
0.02
0.09
0.11
0.10
0.08
0.15
0.16
0.12
0.10
0.12
0.15
0.11
0.10
0.12
0.13
0.13
0.08
0.18
0.20
0.09
0.05
0.11
0.03
0.04
0.07
0.10
0.12
0.09
0.11
0.05
0.03
0.07
0.14
0.18
0.19
0.13
123
124
125
126
127
128
129
130
131
132
133
134
135
136
137
138
139
140
141
GMPropC
a
13
Equation of state
PC-SAFT
SPHCT
PTV
PR
PC
TC
PC
TC
PC
TC
PC
TC
0.02
a
0.02
0.01
0.01
0.01
0.01
0.01
0.00
0.01
0.01
0.02
0.00
0.00
0.01
0.00
0.02
0.03
0.02
0.01
0.13
0.06
0.12
0.15
0.21
0.10
0.09
0.18
0.14
0.28
0.21
0.23
0.26
0.46
0.40
0.43
0.29
0.21
0.25
0.22
3.42
a
2.53
2.89
2.96
3.15
3.06
3.89
4.05
4.68
4.50
4.93
3.83
3.16
3.28
3.05
3.15
2.89
4.01
3.29
0.08
0.05
0.08
0.01
0.09
0.12
0.10
0.18
0.03
0.06
0.12
0.10
0.08
0.06
0.12
0.09
0.05
0.12
0.09
0.14
6.48
a
7.46
4.89
4.58
4.53
4.80
3.85
4.95
5.04
6.15
5.83
3.44
15.24
12.14
9.10
8.84
6.75
9.15
5.21
0.15
0.09
0.15
0.01
0.17
0.10
0.15
0.09
0.12
0.10
0.09
0.11
0.01
0.08
0.12
0.09
0.06
0.03
0.07
0.13
7.21
a
9.12
6.15
6.26
7.25
6.50
5.88
5.81
6.98
5.14
6.43
3.47
11.46
10.11
7.14
8.02
6.15
4.92
5.74
0.10
0.18
0.07
0.12
0.16
0.08
0.21
0.14
0.08
0.10
0.09
0.03
0.08
0.16
0.05
0.12
0.10
0.11
0.04
0.14
Experimental critical pressure not available.
models, when one binary interaction parameter is just

used.
6.3.1.2. Cycloalkane + n-alkane systems. For the critical
behavior of cycloalkane + n-alkane mixtures (systems 3647),
similar comments to those given for the n-alkane + n-alkane
mixtures apply. In Fig. 4, the comparison between the experimental critical data and the predicted critical lines obtained
by the PC-SAFT, SPHCT, PTV and PR EoS is shown for
the cC6 + C1 , cC6 + nC6 , and cC6 + nC10 systems. Only for
the cC6 + C1 system the critical line is concave (maximum)
between the two critical points of pure components, while for
the cC6 + nC6 and cC6 + nC10 systems, their critical lines are
almost linear. The thermodynamic models are able to predict
the fluid phase behavior of these systems, which are of Type I
in the van Konynenburg and Scotts classification [1]. Critical
pressure and temperature deviations ranges are 0.000.03% and
0.140.45% for PC-SAFT EoS; 2.984.15% and 0.040.15%
for SPHCT EoS; 4.085.46% and 0.080.30% for PTV EoS;
and 5.227.38% and 0.090.32% for PR EoS.
6.3.1.3. CO2 + n-alkane systems. Fig. 5 shows the predicted
critical lines for mixtures of CO2 with light aliphatic hydrocarbons (C2 and nC4 ), systems 4860. The PT and Tx projections
of critical lines are compared with experimental data; from these
projections it is easy to notice that the critical lines are continuous from the CO2 critical point to the light aliphatic hydrocarbon
critical point. These binary systems present a fluid phase behavior of Type I in the van Konynenburg and Scotts classification
[1]. These results show that the PC-SAFT model is able to predict
more accurately the critical temperature and, specially, the critical pressure than the others EoS. The critical pressure deviations
14
Fig. 3. PT and Tx projections of critical lines for nC4 (1) + nC6 (2) and nC4
(1) + nC10 (2) systems.
Fig. 4. PTx projection of critical lines for cC6 (2) + C1 (1); cC6 (2) + nC6 (1)
and cC6 (2) + nC10 (1) systems.
Fig. 5. PT and Tx projections of critical lines for C2 (2) + CO2 (1) and nC4
(2) + CO2 (1) systems.
shown in Table 6 are 0.010.02% for PC-SAFT, 2.854.50% for

SPHCT, 3.184.60% for PTV, and 3.215.55% for PR.
Figs. 6 and 7 show more complex behaviors as the alkane
carbon number increases. For CO2 + n-alkane mixtures, Peters
and Gauter [78] established that mixtures with a carbon number
up to 12 (nC12 ) have Type II fluid phase behavior, mixtures with
carbon number 13 (nC13 ) have Type IV and mixtures with carbon
number greater than 13 show Type III fluid phase behavior. The
same evolution in types of phase behavior for the CO2 + n-alkane
series is predicted by any of the four models considered in this
work, when using the interaction parameters obtained from the
correlation of critical points. In Fig. 6, the critical points of pure
components are connected by a continuous line of liquidvapor
critical points (LV), as in the previous case (Type I). At low
temperatures, another line of critical points of liquidliquid equilibria (LL) appears. Phase diagrams of this type were classified
as Type II by van Konynenburg and Scott. It is noticed that the
binary system CO2 + nC13 (for comparison, experimental data
were taken from [40]) presents a UCEP (L1 = L2 + V), a characteristic of mixtures that have Type IV fluid phase behavior in the
15
Fig. 6. PT and Tx projections of critical lines for nC10 (1) + CO2 (2) system.
Fig. 8. PT and Tx projections of critical lines for cC6 (1) + CO2 (2) system.
Fig. 7. PTx projection of critical lines for nC13 (2) + CO2 (1) and nC14 (2) + CO2
(1) systems.
Fig. 9. PTx projection of critical lines for C2 (1) + BNZ (2); nC6 (1) + BNZ (2)
and nC10 (1) + BNZ (2) systems.
16
Fig. 10. PT and Tx projections of critical lines for nC5 (1) + C2 BNZ (2) and nC8
(1) + C2 BNZ (2) systems.
Fig. 11. PT and Tx projections of critical lines for cC5 (1) + cC6 (2) and cC5
(1) + cC8 (2) systems.
van Konynenburg and Scotts classification, while the binary system CO2 + nC14 (for comparison, experimental data were taken
from [41]) presents a UCEP (L1 + L2 = V), Type III in the van
Konynenburg and Scotts classification. It is important to stand
out that the systems with Type III fluid phase behavior have just
one critical endpoint (one UCEP), while systems with Type IV
fluid phase behavior present up to three critical endpoints (two
UCEPs and one LCEP).
6.3.1.4. Cycloalkane + CO2 system. The critical behavior
showed by the binary system cC6 + CO2 (system 61 in Table 3)
is of Type I, since the phase diagram has a simple continuous
critical LV PT locus. Fig. 8 shows the critical loci of cC6 + CO2
system obtained for each EoS and the experimental critical data.
The deviations in critical pressure and temperature obtained by
the four models are 0.00 and 0.20% for PC-SAFT; 2.86 and
0.04% for SPHCT; 3.42 and 0.10% for PTV; and 4.41 and 0.08%
for PR. From these results, it can be seen that the deviation for
the critical temperature is almost the same for all models and
that the efficiency of each thermodynamic model can be com-
Fig. 12. PTx projection of critical lines for 1C6 OH (2) + CO2 (1) system.
17
pared only through the deviation in the critical pressure. In this

way, the PC-SAFT EoS is able to model with the best accuracy this binary system when compared with the other three
thermodynamic models.
6.3.1.5. n-Alkane + N2 O systems. Both N2 O + n-alkane systems (systems 62 and 63) show a fluid phase behavior of Type
I, because their critical lines are continuous between the two
pure-component critical points. The critical line of the N2 O + C2
system has a minimum in the critical temperature in critical
PT locus; on the other hand, the critical line is almost linear for the N2 O + C3 system. The ranges of critical pressure
and temperature deviations obtained between the experimental
and calculated critical data are 0.01 and 0.210.22% for PCSAFT; 2.782.90 and 0.150.22% for SPHCT; 4.566.18 and
0.150.25% for PTV; and 5.856.15 and 0.120.19% for PR.
6.3.1.6. n-Alkane + aromatic hydrocarbon systems. The LV
critical behavior of several benzene + n-alkane mixtures (systems 6471) was studied, predicting results in terms of critical
Fig. 15. PT and Tx projections of critical lines for BNZ (1) + cC5 (2) systems.
pressures and temperatures which were compared with experimental critical data. The ranges of critical pressure and
temperature deviations for these systems were 0.010.05%
and 0.150.62% for PC-SAFT; 4.187.88% and 0.100.91%
for SPHCT; 8.3110.36% and 0.080.22% for PTV; and
10.1412.44% to 0.380.58% for PR. All these systems have
a fluid phase behavior of Type I in the van Konynenburg and
Scotts classification [1]. In Fig. 9, the experimental critical data
and the predicted critical lines obtained for each EoS for the
C2 + benzene, nC6 + benzene, and nC10 + benzene systems are
shown. The critical line for the C2 + benzene system has a fluid
phase behavior of Type I. This line has a concave shape, with a
maximum in the critical pressure, while the others systems show
critical lines that appear to be linear. Other two systems (72 and
73) involving nC5 and nC6 with toluene show a similar Type I
fluid phase behavior.
In the same way that for the binary systems of nalkane + benzene and n-alkane + toluene, the systems formed by
n-alkane and ethylbenzene studied in this work also present a
continuous critical line between the two critical points of the
18
Fig. 16. PT and Tx projections of critical lines for BNZ (1) + TOL (2) and BNZ
(1) + C2 BNZ (2) systems.
n-alkane and ethylbenzene, so their fluid phase behavior is also

Type I. In Fig. 10, the fluid phase behavior of nC5 + ethylbenzene
and nC8 + ethylbenzene systems (systems 7477) is shown in PT
and Tx projections for the four thermodynamic models. Each
EoS is able to predict the fluid phase behavior of these systems,
even when the nC5 + ethylbenzene system has a critical line with
a maximum concavity and the nC8 + ethylbenzene systems has
a critical line with a minimum concavity. In terms of critical
pressure and temperature deviations for these systems, the deviations in critical temperature are similar for the four EoS, while
the PC-SAFT EoS shoes the lower deviations in critical pressure
(0.010.02%) when compared with the deviations obtained for
the other EoS (2.654.11% for SPHCT; 3.886.24% for PTV;
and 6.157.84% for PR).
Fig. 17. PTx projection of critical lines for C1 OH (1) + CO (2) + CO2 (3) system at different molar relations: (a) x1 /x2 = 1/3, (b) x1 /x2 = 1/1, (c) x1 /x2 = 3/1.
Experimental data were taken from [71].
6.3.1.7. Cycloalkane + cycloalkane systems. The critical lines

of several cycloalkane + cycloalkane systems were also correlated. The results in terms of critical pressures and temperatures
were compared with critical experimental data found in literature. The critical behavior shown for five binary systems
involving cycloalkanes with five to eight carbons (systems

7882) was of Type I; as cited above, this means that the critical
line of each binary system is continuous between the purecomponent critical points. In Fig. 11, the fluid phase behavior
of two binary systems cC5 + cC6 and cC5 + cC8 is shown. It
is important to notice that both critical lines are almost linear,

with a slight maximum concavity in pressure. In relation to the
deviations between experimental data and results obtained for
the four EoS for the five cycloalkane + cycloalkane systems, the
critical pressure and temperature deviations range 0.01% and
0.090.40% for PC-SAFT; 3.15% and 0.090.21% for SPHCT;
5.14% and 0.080.14% for PTV; and 6.15% and 0.100.15% for
PR. From these results, it can be seen that the critical temperature deviations are about the same for the four models, while
the PC-SAFT EoS has the lower deviations in critical pressure.
6.3.1.8. Alkanol + alkane systems. There are a number of factors that account for the fluid phase behavior in the critical
region. They include the difference between unlike molecules
and the relative strength of the interaction between pairs of unlike
molecules compared with the interaction between pairs of like
molecules in the mixture. For instance, in alkane + alkane mixtures, dispersion forces alone are responsible for the strength
of interaction between both like and unlike molecules, while
in alkanol + alkane mixtures, there also dipole and hydrogen
bonding forces operating between alkanol molecules, which
significantly enhance the attractive forces between alkanol
molecules. It is important to notice that the contribution of
dipole and hydrogen bonding to the overall strength of interaction between alkanol molecules decreases as the carbon chain
length increases [51]. According to Morton et al. [51], systems
83111 should display interrupted LV critical lines. Their conclusions were corroborated when those systems were correlated
by using the PC-SAFT, SPHCT, PTV, and PR EoS. In other
words, the critical behavior of all these binary systems modeled
here show either Type I or Type II fluid phase behavior. The
ranges of critical temperature deviations corresponding for alkanol + alkane systems are 0.030.31% for PC-SAFT; 0.010.28%
for SPHCT; 0.030.21% for PTV; and 0.020.20% for PR. For
these binary systems, there are not available critical pressures in
the literature.
6.3.1.9. Alkanol + CO2 systems. Arce [76] presented the compositions of CO2 of two liquid phases in equilibrium with vapor
phase (which was formed practically of pure CO2 ) obtained by
modeling the multiphase equilibria of a binary system composed
of CO2 and 1C6 OH. At certain temperature and pressure, the
L1 L2 V equilibria starts with two phases in equilibrium, a liquid
phase, L1 , and the other one is formed by the critical state of two
phases, L2 and V, in a UCEP, resulting that the mole fraction of
CO2 in the UCEP is 0.7403 in L1 and 0.9645 in L2 and V. Fig. 12
shows the PTx projection, where the two compositions for CO2
for both liquid phases are obtained by the four EoS as well as
also the UCEP obtained with the PC-SAFT EoS.
Multiphase behavior of CO2 + 1C8 OH system was modeled
by searching some critical condition. In the same way that for
the CO2 + 1C6 OH system, for this systems a UCEP (L1 + L2 = V)
was found at 309.12 K and 7.97 MPa, and the mole fraction of
CO2 in phase L1 was 0.6745 and 0.9890 in phases L2 and V. Arce
[76] shows complete results of temperatures, pressures and mole
fraction of both liquid phases. Fig. 13 presents the comparison
between the experimental data and the results obtained by the
19
PC-SAFT, SPHCT, PTV and PR EoS. In this figure we can also

observe the compositions of the three-phase behavior (L1 L2 V)
in relation to the temperature and pressure, as well as the experimental UCEP and the value of this critical state calculated by
the PC-SAFT EoS. In a similar way to the fluid phase behavior
presented by the binary system: CO2 + 1C6 OH, this binary system also presents a Type III behavior in the van Konynenburg
and Scotts classification [1]. The UCEP is located at higher
temperatures and pressures regarding the conditions where the
multiphase equilibria exists (L1 L2 V).
Modeling of multiphase equilibria of CO2 + 1C10 OH system
was made keeping in mind the fluid phase behavior presented
by the two previous binary systems. Arce [76] shows the results
in function of temperatures and pressures versus the mole fractions of CO2 in both liquid phases (L1 and L2 ). It is also noticed
that a UCEP of Type L1 + L2 = V (whose CO2 mole fractions are
0.6312 in phase L1 and 0.9895 in phases L2 and V) was found,
which corroborates the sequence that is obtained in modeling the
binary systems CO2 + 1-alkanol (starting from the 1C6 OH, all of
the binary systems involving CO2 and 1-akanols present a fluid
phase behavior of Type III in the van Konynenburg and Scotts
classification [1]). In Fig. 14, temperatures and pressures are represented against the mole fraction of CO2 in two liquid phases
(L1 and L2 ). Although the compositions in liquid phase L2 are
next to the unit, PC-SAFT EoS can model the phase behavior
of this binary system relatively well, while the other thermodynamic models do not have a good performance in modeling this
binary system.
From these results, it can be deduced that temperatures
and pressures of UCEPs in binary systems CO2 + 1C6 OH,
CO2 + 1C8 OH, and CO2 + 1C10 OH, decrease when the carbon
number of 1-alcanols increases. Peters and Gauter [78] affirmed
that was recently accepted that binary mixtures of CO2 and 1alkanols show a fluid phase behavior of Type II (L1 = L2 + V)
for 1-alkanols up to 5 carbons (1C5 OH), while mixtures with
higher carbon number (starting from 1C6 OH) have a fluid phase
behavior of Type III (L1 + L2 = V).
There were studied several alkanol + CO2 systems (systems
112121 in Table 3) which critical pressure and temperature
deviation ranges are 0.000.03% and 0.080.20% for PCSAFT, 2.683.75% and 0.050.18% for SPHCT, 3.895.15%
and 0.010.25% for PTV, and 4.256.18% and 0.030.19% for
PR EoS, respectively. As it can be appreciate in those results,
the critical temperature deviations are similar for all thermodynamic models, while the PC-SAFT EoS has the lower deviations
in critical pressures when compared with the other EoS.
6.3.1.10. Cycloalkane + aromatic
hydrocarbon
systems.
Binary systems of cycloalkanes and aromatic hydrocarbons
present a fluid phase behavior of Type I, since their critical lines
that join the pure-component critical points are continuous.
This can be perceived in Fig. 15, where the phase behavior for
the cC5 + BNZ system has been represented. From this figure,
it can be observed that the critical line is almost linear, and all
thermodynamic models can describe the fluid phase behavior,
even when the PC-SAFT EoS has the best performance in
relation to the deviations in critical properties. Comparing
20
in quantitative terms for the four thermodynamic models,

deviations for the cycloalkane + cycloalkane systems (systems
122124 in Table 3) obtained for the critical pressure and
temperature are 0.000.02% and 0.060.13% for PC-SAFT,
2.893.42% and 0.010.08% for SPHCT, 6.489.47% and
0.090.15% for PTV, 5.528.46% and 0.100.18% for PR. The
main difference is in the critical pressure deviations, where the
PC-SAFT EoS has the lowest critical pressure deviations.
6.3.1.11. Aromatic hydrocarbon + aromatic hydrocarbon systems. Fluid phase behavior of aromatic hydrocarbon + aromatic
hydrocarbon systems is of Type I in the van Konynenburg and
Scotts classification [1], since these binary systems have a continuous critical line between the two pure-component critical
points. Fig. 16 shows the fluid phase behavior of BNZ + TOL
and BNZ + C2 BNZ systems modeled by the PC-SAFT, SPHCT,
PTV, and PR EoS and compared with critical experimental data.
This plot indicates a reasonable agreement between the results
obtained for the thermodynamic models and those in the literature. In quantitative terms in function of critical pressure
and temperature deviation ranges for modeling aromatic hydrocarbon + aromatic hydrocarbon systems (systems 125130 in
Table 3), PC-SAFT EoS has good performance in modeling
these systems (0.010.02% and 0.090.21%) when compared
with those critical pressure and temperature deviation ranges of
SPHCT (2.533.89% and 0.010.18%), PTV (3.857.46% and
0.010.17%), and PR EoS (5.889.12% and 0.080.21%).
6.3.1.12. Other binary systems. These systems are nC5 + H2 S,
NAP + C2 , N2 O + CO2 , and N2 O + SF6 and correspond to systems 131134. The fluid phase behavior of nC5 + H2 S system
is of Type 1. Its critical line is continuous and almost linear
when is plotted as critical P locus against mole fraction of
nC5 . The critical behavior of NAP + C2 system is more complex. It presents a continuous critical line at mole fractions of
NAF from 0.17 to 0.29, while at higher concentrations there
are no experimental critical data to compare. According to the
obtained results, this binary system probably presents a fluid
phase behavior of Type V, due to the presence of a critical line
that joins an UCEP and a LCEP. N2 O + CO2 and N2 O + SF6
systems have a continuous critical line between their critical
points of pure component (Type I in the van Konynenburg and
Scotts classification [1]). N2 O + CO2 system has an almost linear critical line, while the N2 O + SF6 system has a minimum
critical temperature in a critical PT locus, lower than the purecomponent critical temperatures. For these systems, in terms
of the range of critical pressure and temperature deviations,
PC-SAFT EoS obtained 0.000.02% and 0.140.28%, SPHCT
EoS obtained 4.054.93% and 0.030.12%, PTV EoS obtained
4.956.15% and 0.090.12%, and PR EoS obtained 5.146.98%
and 0.030.10%.
6.3.2. Ternary systems
The methodology used for modeling the critical behavior
of ternary systems consisted in the use of the adjusted interaction parameters obtained from the three binary systems and
then the prediction of the critical points of the ternary mixture.
Binary interaction parameters were calculated in a similar form

as was explained in Section 6.2. The fluid phase behavior of
seven ternary systems (systems 135141 in Table 3) was studied, whose results in terms of critical pressure and temperature
deviation range are 0.000.03% and 0.210.46% for PC-SAFT,
2.894.01% and 0.050.12% for SPHCT, 3.4415.24% and
0.010.12% for PTV, and 3.4711.46% and 0.040.16% for PR.
Some works were carried out to classify the fluid phase behavior of ternary systems [79,80]. For instance, Bluma and Deiters
[79] proposed a classification of phase diagrams of ternary systems based on the fluid phase behavior of their binary subsystems
using the Types I, II and III in the van Konynenburg and Scott
classification.
6.3.2.1. C1 OH + CO + CO2 system. Fluid phase behavior of
C1 OH + CO + CO2 system was studied at three C1 OH/CO mole
ratios. Table 5 contains the binary interaction parameters for the
C1 OH + CO, C1 OH + CO2 , and CO + CO2 systems for all EoS.
Results obtained for this ternary system (system 136 in Table 3)
in terms of critical pressure and temperature deviations are 0.02
and 0.46% for PC-SAFT, 3.16 and 0.06% for SPHCT, 15.24
and 0.08% for PTV, and 11.46 and 0.16% for PR EoS. As it
can be deduced from the deviations, PC-SAFT EoS has the best
performance, while SPHCT EoS has larger deviations in critical
pressure. The results obtained by cubic EoS are much worse and
there are not in agreement with the experimental data.
Fig. 17 shows the critical pressure and temperature of the
ternary mixture C1 OH + CO + CO2 against different compositions of C1 OH at different mole ratios of C1 OH and CO, 1/3,
1/1 and 3/1. In Fig. 17(a) it is noticed that the critical temperature decreases rapidly when the mole fraction of C1 OH
increases slowly, while in Fig. 17(b), the critical temperature
increases slowly with C1 OH concentration at the beginning and
then decreases, whereas in Fig. 17(c), the critical temperature
increases with the C1 OH mole fraction in the ternary mixture,
especially at higher C1 OH concentrations. This behavior is probably due to the concentration-dependency of the temperature
in relation to the pure-component critical temperatures and the
intermolecular interactions in mixture [71]. It is important to
notice that the critical temperature of CO is lower when compared of that of C1 OH. Thus C1 OH/CO mole ratio is one of
the main factors that can affect the critical temperature of this
ternary mixture.
Fig. 17(a) and (b) show also that, when the critical pressure
increases, the critical temperature decreases at C1 OH/CO ratios
of 1/1 and 1/3. The influence of mole fraction of C1 OH in mixture
critical pressure was also analyzed, and it was found that the
critical pressure increases with the C1 OH concentration at a
fixed C1 OH/CO ratio. From Fig. 17(a)(c), it is noticed that
critical pressure is more sensitive to the C1 OH concentration at
lower C1 OH/CO ratios.
In this work, the binary system C1 OH + CO2 has a fluid phase
behavior of Type V in the van Konynenburg and Scott classification, conclusion that was also made by Kolar and Kojima [81]. In
this way, since Bluma and Deiters [79] used only the first three
types of phase behavior of binary systems to classify the fluid
phase behavior of ternary systems, it is not possible to determine
the classification of the C1 OH + CO + CO2 system according to

the Bluma and Deiters classification.
6.3.2.2. SF6 + C2 + CO2 system. Binary interaction parameters
for C2 + CO2 , C2 + SF6 and CO2 + SF6 systems were fitted to
experimental critical binary data. These parameters are listed
in Table 5, system 48 corresponding to C2 + CO2 system and
system 141 corresponding to C2 + SF6 and CO2 + SF6 systems
for PC-SAFT, SPHCT, PTV, and PR EoS. These binary interac-
21
tion parameters were used to predict the critical behavior of the

ternary system CO2 + C2 + SF6 , whose results were compared to
those in the literature, with the following deviations in the critical pressure and temperature: 0.02 and 0.25% for PC-SAFT,
4.01 and 0.09% for SPHCT, 9.15 and 0.07% for PTV and 4.92
and 0.04% for PR. In Fig. 18(a) and (b), the critical temperature
and pressure of this ternary system are represented against the
compositions of each component obtained by the PC-SAFT EoS
and the experimental critical data. In this figure, a minimum in
the critical temperature is noticed, which is located at a lower
temperature than the binary minimum. The PC-SAFT model can
predict this behavior in good agreement when compared with the
experimental critical data.
This ternary system is composed by three binary subsystems:
C2 + CO2 , C2 + SF6 and CO2 + SF6 . In this work, the fluid phase
behavior of the C2 + CO2 system was of Type I. Horstmann et
al. [73] measured and calculated the fluid phase behavior of
the C2 + SF6 and CO2 + SF6 systems, and they also concluded
that those systems presented the fluid phase behavior of Type I.
Thus, since the three binary subsystems have a phase behavior
of Type I in the van Konynenburg and Scott classification, the
ternary system SF6 + C2 + CO2 has a phase behavior of Type I
according to the Bluma and Deiters classification.
In all the discussions above, the deviations in critical pressure
and temperature were calculated for each EoS by
NS
NP(i) Pr opC(i)
GM Pr opC = i NS
(41)
i NP(i)
where NP represents the number of experimental points, PropC
is the critical property deviation and NS the number of binary
and ternary systems. These deviations are shown in Table 6.
From these final results it can be noticed that the global mean
deviation in critical temperature is almost the same for the four
thermodynamic models, while in terms of the global mean deviation in critical pressure, the performance of the PC-SAFT EoS
is in good agreement at modeling the critical phase behavior of
the binary and ternary systems listed in Table 3 (0.01%). The
SPHCT, PTV, and PR EoS did not have a good performance
(3.29, 5.21 and 5.74%, respectively) in modeling of critical phenomena of these binary and ternary systems; even when they
were able to predict the fluid phase behavior, the accuracy was
always minor than that reached by the PC-SAFT EoS.
7. Conclusions
Fig. 18. Experimental and predicted critical points for ternary system CO2
(1) + C2 (2) + SF6 (3) where (a) critical temperature against mole fraction and
(b) critical pressure against mole fraction. Experimental critical data were taken
from [73].
The phase behavior at critical conditions was studied for

134 binary systems and seven ternary systems involving
aliphatic hydrocarbons (linear and branched alkanes, nonsaturated alkanes, and cycloalkanes), aromatic hydrocarbons,
alcohols (primary and secondary), hydrogen, nitrous oxide,
carbon monoxide, carbon dioxide and sulfur hexafluoride. In
general, binary systems with light hydrocarbons show a fluid
phase behavior of Type I in the van Konynenburg and Scott classification. Binary systems that contain aliphatic hydrocarbons
with a higher number of carbons show a fluid phase behavior of
Type II or III, while alkane + alkanol systems show either Type
22
I or Type II phase behavior according to the van Konynenburg

and Scott classification. Binary systems which contain aromatic
hydrocarbons show a phase behavior of Type I. On the other
hand, most of the ternary systems studied in this work show
a fluid phase behavior of Type I according to the Bluma and
Deiters classification. Deviations, mainly in critical pressure,
corroborate that the PC-SAFT EoS presents the best performance on the vicinities of critical region when compared with
the SPHCT, PTV and PR EoS. The cubic models present higher
deviations in the mixture critical pressure, even when the deviation in the mixture critical temperature is similar than those
obtained with the non-cubic models.
The financial support of Fundaca o de Amparo a` Pesquisa do

Estado de Sao Paulo, FAPESP (Brazil), through grant 01/138221, is gratefully acknowledged.
Appendix A. Connecting the HeidemannKhalil
method with the program to calculate phase equilibrium
The second and third stability parameters, b and c, were found
numerically. For the first derivative (Eq. (26)), if the perturbation
of mole number of component j is nj , we have:
NC
ni
nk + (nj + nj ) xi = ,
nT
k=1
V
V- =
nT
(A.1)
NC
ni
nk + (nj nj ) xi = ,
nT
k=1
V
V- =
nT
(A.2)
For the second derivative in Eq. (27), if the perturbations of mole

numbers of component j and k are nj and nk , respectively,
we have:
l=1
j = l
nl + (nj + nj ) + (nk + nk ) xi =
ni
,
nT
NC
ni

nl + (nj + nj ) + (nk nk ) xi = ,
nT
l=1
j = l
k=l
(A.6)
NC
ni

nl + (nj + nj ) + (nk nk ) xi = ,
nT
l=1
j = l

nT =
k=l
V
V- =
nT
(A.7)
Before the perturbation, we had: V = nT V- . Thus, the second

derivative of the logarithm of fugacity of component i with the
mole numbers of components j and k is:
2 ln f i
nj nk
ln f i (T, V- , x ) ln f i (T, V- , x )

ln f i (T, V- , x ) + ln f i (T, V- , x )
=
4 nj nk
(A.8)
f i = xi i P ln f i = ln i + ln(xi P)
1
ln i =
RT

P
ni
P
ni

T,V,ni=j
RT

= f (EoS) EoS
T,V,ni=j
(A.9)

dV ln(Z)

cubic
non-cubic
(A.10)
PR
PTV
SPHCT
PC-SAFT
(A.11)
Resolving Eq. (A.11) and defining the perturbation of mole

number of component i in the mixture as ni , we have:
nT =
k=l
V
V- =
nT

nT =
(A.5)
where:
Before the perturbation, we had: V = nT V- . Thus, the derivative

of the logarithm of fugacity of component i with the mole number
of component j is:

ln f i
ln f i (T, V- , x ) ln f i (T, V- , x )
=
(A.3)
nj
2 nj
nT =
V
V- =
nT
The fugacity can be calculated from the fundamental thermodynamic relationships:
j=k
NC
ni
nl + (nj nj ) + (nk + nk ) xi = ,
nT
l=1
j = l
k=l
j=k
nT =
NC
V
V- =
nT
Acknowledgement
nT =
nT =
NC
nj + (ni + ni ) xi =

j=1
ni + ni
,
nT
j=i
(A.4)
V
V- =
nT
(A.12)
nT =
NC
nj + (ni ni ) xi =

j=1
Applying the definition of partial derivatives, we have:

2 ln f i
ln f i
3 ln f i
=
=
nj nk nl
nl nj nk
nl nk
nj
ni ni
,
nT
j=i
V
V- =
nT
23
(C.3)
(A.13)
The pressure variation with the mole number of component i is

also calculated numerically, avoiding the necessity of knowing
the form of the function:

P
P(x , T, V- ) P(x , T, V- )
=
(A.14)
ni T,V
2 ni
By substituting Eq. (A.14) in Eq. (A.10), we have:

P(x , T, V- ) P(x , T, V- )
RT
1
ln I =
dV
RT V
2 ni
V
ln(Z)
(A.15)
thus:

ln f i
nl nk
nj
=
[/nk ( ln f i /nj )]nl +nl [/nk ( ln f i /nj )]nl nl

2 nl
(C.4)
The second derivatives in Eq. (C.4) can be calculated as:

ln f i
nk
The integral in Eq. (A.15) is resolved numerically using the

Simpsons method (3/8).
nj
nl +nl
( ln f i /nj )nk +nk ,nl +nl ( ln f i /nj )nk nk ,nl +nl
2 nk
Appendix B. Fluxogram for one critical point

calculation
(C.5)

nk
=
ln f i
nj

nl nl
( ln f i /nj )nk +nk ,nl nl ( ln f i /nj )nk nk ,nl nl
2 nk
(C.6)
where the first derivatives can be calculated as:

ln f i
nj
nk +nk ,nl +nl
(ln f i )nj +nj ,nk +nk ,nl +nl (ln f i )nj nj ,nk +nk ,nl +nl
2 nj
(C.7)

Appendix C. Numerical calculation of coefcient d
According to Eq. (25), the fourth stability coefficient is:

d=
NC NC NC NC
1
4!
l=1 k=1 j=1 i=1
4 A
ni nj nk nl

nk nk ,nl +nl
(ln f i )nj +nj ,nk nk ,nl +nl (ln f i )nj nj ,nk nk ,nl +nl
2 nj
(C.8)
ni nj nk nl

(C.1)
In terms of fugacity, we have:

NC NC NC NC
1 3 ln f i
d=
ni nj nk nl
4!
nj nk nl
l=1 k=1 j=1 i=1
ln f i
nj
(C.2)
ln f i
nj
=

nk +nk ,nl nl
(ln f i )nj +nj ,nk +nk ,nl nl (ln f i )nj nj ,nk +nk ,nl nl
2 nj
(C.9)
24
ln f i
nj
=

nk nk ,nl nl
(ln f i )nj +nj ,nk nk ,nl nl (ln f i )nj nj ,nk nk ,nl nl
2 nj
(C.10)
where nj , nk and nl are perturbations of mole numbers of

components j, k and l, respectively. With these perturbations we
have to calculate the new total mole number and with this recalculate the new mole fractions and then the new molar volume.
With these new data, can be calculated the fugacity (Eq. (A.9))
by means of fugacity coefficient (Eq. (A.10)) with the numerical
form (Eq. (A.15)).
Thus, supposing that we want to calculate:
(ln f i )nj +nj ,nk nk ,nl nl
Before the perturbations, we had the molar volume, V- , taking
a base of total mole number as nT , then the absolute volume
is V = nT V- and nT = n1 + n2 + . . . + ni + nj + nk + nl + . . . + nNC .
Mole numbers of components j, k and l have new values because
its perturbations: nj = nj + nj , nk = nk nk , nl = nl
nl . Thus, the new total mole number is: nT = n1 + n2 +
. . . + ni + nj + nk + nl + . . . + nNC , the new molar volume is:
V- = V/nT and the new mole fractions are: xj = nj /nT , xk =
nk /nT , xl = nl /nT and so on.
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J.

of Supercritical Fluids 42 (2007) 126

Modeling of critical lines and regions for binary and ternary

a binary system is a sensitive test to explore the quality of

P. Arce, M. Aznar / J. of Supercritical Fluids 42 (2007) 126

average segment number

deviations for the critical properties, perturbation

constant in cubic EoS

interaction energy parameter, associating energy

adjustable binary interaction parameter, associating volume parameter

P. Arce, M. Aznar / J. of Supercritical Fluids 42 (2007) 126

to association (aassoc ), which is given by:

where a = A/NkT , T is the absolute temperature, A the

xi (mi 1)ln giihs (ii )

where a 1 and a 2 depend on the integrals of power series of

where XAi is the fraction of A-sites on molecule i that do not form

2.2. Associating contribution [19]

where j is the molar density of component j and AiBj is a

where ij is the binary interaction parameter. In according with

P. Arce, M. Aznar / J. of Supercritical Fluids 42 (2007) 126

where ij is the binary interaction parameter.

where ci , Vi and Ti are the pure-component parameters,

0.3746 + 1.5423 0.26992

is the acentric factor and ZC the critical compressibility factor.

Heidemann and Khalil [16] showed a derivation of the critical

Expanding the Helmholtz energy A in a Taylor series of the

2.4. Cubic equations of state: PR and PTV

A general formula for a cubic EoS [14,15] can be written as:

The two first terms correspond to the following critical criteria:

where ij is the binary interaction parameter. Pure-component

The cross term, aij, is

where n is a unit vector of the perturbed mole numbers,

3. Determination of critical points

The critical point criteria can be stated in terms of the

P. Arce, M. Aznar / J. of Supercritical Fluids 42 (2007) 126

where fi is the fugacity, i the fugacity coefficient, n the mole

in order to obtain the vector n of a unit length, nT n = 1.

(PC ) is evaluated from the EoS. A fluxogram describing these

where NP is the number of experimental point data for a given

P. Arce, M. Aznar / J. of Supercritical Fluids 42 (2007) 126

Molecular weight (MW)

Molecular weight (MW)

liquid molar volume and saturated vapor pressure:

In these equations, exp refers to vapor pressure and liquid

perature of both components:

where NP is the number of experimental critical point data for a

6.3. Modeling of uid phase behavior of binary and ternary

P. Arce, M. Aznar / J. of Supercritical Fluids 42 (2007) 126

P. Arce, M. Aznar / J. of Supercritical Fluids 42 (2007) 126

P. Arce, M. Aznar / J. of Supercritical Fluids 42 (2007) 126

Experimental critical pressure not available.

P. Arce, M. Aznar / J. of Supercritical Fluids 42 (2007) 126

6.3.1. Binary systems

and 0.020.30% for SPHCT EoS; 3.025.81% and 0.020.30%

P. Arce, M. Aznar / J. of Supercritical Fluids 42 (2007) 126

P. Arce, M. Aznar / J. of Supercritical Fluids 42 (2007) 126

pure-component critical points are joined by a simple critical

P. Arce, M. Aznar / J. of Supercritical Fluids 42 (2007) 126

Experimental critical pressure not available.

models, when one binary interaction parameter is just

P. Arce, M. Aznar / J. of Supercritical Fluids 42 (2007) 126

shown in Table 6 are 0.010.02% for PC-SAFT, 2.854.50% for

P. Arce, M. Aznar / J. of Supercritical Fluids 42 (2007) 126

where n is a unit vector of the perturbed mole numbers,

in order to obtain the vector n of a unit length, nT n = 1.

nl + (nj + nj ) + (nk + nk ) xi =

ln f i (T, V- , x ) ln f i (T, V- , x )

nj + (ni + ni ) xi =

nj + (ni ni ) xi =

[/nk ( ln f i /nj )]nl +nl [/nk ( ln f i /nj )]nl nl

where nj , nk and nl are perturbations of mole numbers of