Fluid Phase Equilibria 306 (2011) 181189

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Fluid Phase Equilibria
j our nal homepage: www. el sevi er . com/ l ocat e/ f l ui d
JouleThomson coefcients and JouleThomson inversion curves for pure
compounds and binary systems predicted with the group contribution
equation of state VTPR
Rima Abbas
a,b
, Christian Ihmels
c
, Sabine Enders
b
, Jrgen Gmehling
a,
a
Lehrstuhl fr Technische Chemie, Carl von Ossietzky Universitt Oldenburg, 26111 Oldenburg, Germany
b
Fachgebiet Thermodynamik und Thermische Verfahrenstechnik, Institut fr Prozess- und Verfahrenstechnik, Technische Universitt, Berlin, Germany
c
Laboratory for Thermophysical Properties (LTP GmbH), Marie-Curie-Str. 10, 26129 Oldenburg, Germany
a r t i c l e i n f o
Article history:
Received 28 April 2010
Received in revised form 29 March 2011
Accepted 31 March 2011
Available online 8 April 2011
Keywords:
JouleThomson coefcient
JouleThomson inversion curve
Group contribution equation of state VTPR
Throttling processes
a b s t r a c t
In this work the accuracy of the prediction of JouleThomson coefcients for the gases CO
2
and Ar
and the binary systems CO
2
Ar and CH
4
C
2
H
6
was examined using the group contribution equation
of state VTPR. Furthermore the experimental and correlated data of JouleThomson inversion curves
of a few compounds including carbon dioxide, nitrogen, benzene, toluene, methane, ethane, ethylene,
propyne, and SF
6
were compared with the results of the group contribution equation of state VTPR,
the SoaveRedlichKwong (SRK), the PengRobinson (PR) and the Helmholtz equation of state (HEOS).
Moreover, JouleThomson inversion curves for pure uids, binary (CH
4
C
2
H
6
, N
2
CH
4
, CO
2
CH
4
), and
ternary systems (CO
2
CH
4
N
2
, CH
4
C
2
H
6
N
2
, CO
2
CH
4
C
2
H
6
) were calculated with VTPRand compared
to the results of SRK, PR, HEOS and the molecular simulation results of Vrabec et al. It was found that the
calculated values for the JouleThomson coefcients and JouleThomson inversion curves are in good
agreement with the experimental ndings.
2011 Elsevier B.V. All rights reserved.
1. Introduction
The reliable knowledge of JouleThomson coefcients
JT
and
the JouleThomson inversion curve are important for the design
and operation of throttling and refrigeration processes, e.g. for
cryogenic processes (e.g. air separation (Linde process)). One con-
sequence of the effect may be the cooling of natural gas in pipelines
under pressure drop, which can lead to undesirable glaciations of
pipelines TheJouleThomsoninversioncurveis denedas thelocus
of the points where the JouleThomson coefcient becomes zero
and separates the region of positive
JT
from negative
JT
. This
curve is important in refrigeration and liquefaction processes since
the sign of the JouleThomson coefcient determines whether the
temperature of a real gas increases or decreases by isenthalpic
expansion. The JouleThomson coefcient is dened as the isen-
thalpic derivative of temperature T, with respect to pressure P at
constant enthalpy:

JT
=

T
P

h
(1)

Corresponding author. Tel.: +49 441 798 3831; fax: +49 411 798 3330.
E-mail address: gmehling@tech.chem.uni-oldenburg.de (J. Gmehling).
URL: http://www.uni-oldenburg.de/tchemie (J. Gmehling).
When
JT
is positive, throttling results in a temperature
decrease. For negative values a temperature increase is observed. In
order to express Eq. (1) in a more practical form the following pro-
cedure may be followed. The total differential for the enthalpy of a
pure substance (which is a function of temperature and pressure)
is dened as follows:
dh =

h
T

P
dT +

h
P

T
dP (2)
The molar heat capacity at constant pressure c
p
is dened as the
isobaric derivative of the enthalpy, with respect to the temperature
T:
c
p
=

h
T

P
(3)
From Eqs. (2) and (3) the JouleThomson coefcient can be
dened as follows:

JT
=

T
P

h
=

(h/P)
T
c
p

(4)
0378-3812/$ see front matter 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.uid.2011.03.028
182 R. Abbas et al. / Fluid Phase Equilibria 306 (2011) 181189
0
40
80
120
160
200
1 0.8 0.6 0.4 0.2 0
P

[
b
a
r
]
x
1
, y
1
(1) Ar
(2) CO
2
244.45 K
233.32K
Fig. 1. Experimental and calculated vaporliquid equilibria for Ar (1)CO
2
(2), ()
VTPR, (-) PR, (.......) SRK, experimental [34], [35].
0
80
160
240
320
1 0.8 0.6 0.4 0.2 0
P

[
b
a
r
]
x
1
, y
1
(1) N
2
(2) CO
2
270 K
220 K
Fig. 2. Experimental and predicted vaporliquid equilibria for N
2
(1)CO
2
(2), ()
VTPR, (-) PR, (.......) SRK, experimental [36], [37].
For mixtures, the JouleThomson coefcient
JT
is dened as
the derivative of the temperature T with respect to the pressure at
constant enthalpy h and constant composition x.

JT
=

T
P

h,x
=

(h/P)
T,x
c
p

(5)
The term (h/P)
T
can be dened with the help of the
fundamental equation and the Maxwell relations as follows:

h
P

T
= v T

v
T

P
(6)
Since v =zRT/P, this equation can be also written as:

h
P

T
=
RT
2
P

z
T

P
(7)
where z is the compressibility factor. Substitutioninto Eq. (5) gives:

JT
=
RT
2
c
p
P

z
T

P
(8)
The curve connecting all state points for which the derivative:

z
T

P
= 0 (9)
or the JouleThomson coefcient is 0 is called JouleThomson
inversion curve:
The reliable measurement of the JouleThomson inversion
curve is difcult because of the severe experimental condi-
tions involved (up to 5 times critical temperature and 12 times
critical pressure). Therefore the accurate prediction of
JT
and
JouleThomson inversion curves for working uids is of great
importance. In various papers the results of cubic equations of
state (EOS) for the prediction of JouleThomson inversion curves
for pure uids have been reported [13]. Particularly at high tem-
peratures poor predictions for the JouleThomson inversion curves
were obtained using cubic equations of state. Inthe paper of Vrabec
et al. [4], it was proved that molecular simulation delivers good
results in predicting JouleThomson inversion curves for natural
gas and its pure compounds. Furthermore, JouleThomson inver-
sion curves were calculated for pure uids with molecular-based
models and presented in the work of Colina [5]. Results obtained by
molecular simulation were compared to the results of molecular-
based models and cubic equations of state. Generally, it was shown
that molecular based methods are superior compared to classical
cubic EOS for the prediction of JouleThomson inversion curves.
The reliable knowledge of the behavior of supercritical uids
or solutions is required to develop processes, such as super-
critical extraction, the RESS (Rapid Expansion of Supercritical
Solution) technique for the production of amorphous ne pow-
ders or thin lms or gas-antisolvent crystallization [6]. A powerful
group contribution equation of state VTPR for engineering applica-
tions was developed by Ahlers and Gmehling [711]. The group
contribution equation of state VTPR was already successfully
applied for the reliable prediction of vaporliquid equilibria, excess
enthalpies, azeotropic data, solidliquid equilibria, gas solubilities.
Table 1
VTPR group interaction parameters taken from DDB.
n/m anm (K) bnm cnm (K
1
) amn (K) bmn cmn (K
1
)
CO
2
/CH
4
88.186 0 0 200.73 0 0
CH
2
/CO
2
941.82 3.618 0.003429 6.4843 0.022 0.00098
CH
4
/N
2
69.493 0 0 4.484 0 0
CH
2
/N
2
162.63 0.39962 0 51.147 0.50797 0
CH
2
/CH
4
177.41 1.045 0.000016 82.636 0.24879 0.0022776
Table 2
VTPR group interaction parameters tted in this work.
n/m anm (K) bnm cnm (K
1
) amn (K) bmn cmn (K
1
)
CO
2
/N
2
24.646 0.67499 0.00029204 453.53 1.6352 0.00002
CO
2
/Ar 215.08 1.5072 0 551.13 1.9153 0
R. Abbas et al. / Fluid Phase Equilibria 306 (2011) 181189 183
-0.1
0.3
0.7
1.1
600 450 300 150
T [K]
P = 60 atm
P = 100 atm
P = 140 atm
P = 200 atm
CO
2

J
T
[
K
/
a
t
m
]
Fig. 3. Experimental [22] andpredictedJouleThomsoncoefcients using the group
contribution equation of state VTPR for CO
2
.
0.0
0.2
0.4
0.6
0.8
550 400 250 100
T [K]
P = 60 atm
P = 100 atm
P = 140 atm
P = 200 atm
Ar

J
T
[
K
/
a
t
m
]
Fig. 4. Experimental [23] andpredictedJouleThomsoncoefcients using the group
contribution equation of state VTPR for Ar.
Also other pure component and mixture properties such as den-
sities, enthalpies, heat capacities, entropies, heats of vaporization
and JouleThomson coefcients can directly be predicted.
The group contribution equation of state VTPR is a combina-
tion of the volume-translated PengRobinson equation of state
and the group-contribution method mod. UNIFAC (Do) [1214]. In
group-contribution methods it is assumed that the mixture does
not consist of molecules but of functional groups. The great advan-
tage of the group contribution concept is that the number of the
functional groups is much smaller than the number of possible
compounds.
2. The group contribution equation of state VTPR
The PengRobinson (PR) equation of state was selected as the
basis for the development of a new group contribution equation
of state, because liquid densities for pure compounds and mix-
tures are better described by the PR than the SRK equation of state.
By implementing the volume translation, which is given for the
PengRobinson equation of state by Peneloux et al. [15], the results
for liquid densities can be further improved. The VTPR equation of
state is given by the following equations:
P =
RT
(v +c b)

a(T)
(v +c)(v +c +b) +b(v +c b)
(10)
a(T) is the temperature dependent attractive parameter, b is the co-
volume, c is the translationparameter, Ris the general gas constant,
0
0.4
0.8
1.2
1.6
2
450 400 350 300 250 200

J
T
[
K
/
a
t
m
]
T[K]
P = 10 atm
(1) Ar
(2) CO2
Fig. 5. Experimental [24] and predicted JouleThomson coefcients for Ar (1)CO
2
(2), () VTPR, (-) PR, (.......) SRK, y
CO
2
= 0.464, y
CO
2
= 0.754.
-2
0
2
4
6
8
10
400 350 300 250
(
(

J
T
,
c
a
l
c
.
-

J
T
,

e
x
p
.
)
/

J
T
,

e
x
p
.
)
%
T [K]
VTPR
SRK
PR
P = 80 atm
Fig. 6. Deviations between experimental and predicted JouleThomson coefcients
for (ArCO
2
) at 80atm and y
CO
2
= 0.464.
T is the absolute temperature, v is the molar volume and P is the
pressure.
To improve the prediction for mixtures, especially asymmetric
systems, a modied g
E
mixing rule was developed by Chen et al.
[16], where only the residual part of the excess Gibbs energy is
used.
a
b
=

i
x
i

a
ii
b
ii
+
g
E
res
0.53087
P
ref
= 1 atm (11)
g
E
res
is the residual part of the mod. UNIFAC model. To calculate this
term, the following equation is used:
g
E
res
= RT

i
x
i
ln
res
i
(12)
in which
res
i
and x
i
are the activity coefcients and the mole
fractions in the liquid phase for compound i. The residual activity
coefcient is dened by the following equation (solution of groups
concept):
ln
res
i
=

k
v
(i)
k
(ln
k

(i)
k
) (13)
with:
ln
k
= Q
k

1 ln

mk

mk

nm

(14)
where v
(i)
k
is the number of subgroups k in compound i,
k
and

(i)
k
are the group activity coefcient in the mixture respectively
184 R. Abbas et al. / Fluid Phase Equilibria 306 (2011) 181189
0
0.5
1
1.5
2
2.5
600 500 400 300 200

J
T
[
K
/
M
P
a
]
T[K]
CH
4
-C
2
H
6
Fig. 7. Experimental [25] and predicted JouleThomson coefcients for (CH
4
C
2
H
6
)
at x
CH
4
= 0.85, () VTPR, (-) PR, (.......) SRK, at 15MPa, at 20MPa.
pure compound i, Q
k
is the relative van der Waals surface area of
subgroup k and
nm
describes the interactions between the main
groups n and m.
The group area fraction and the group mole fraction X
m
for
the group m are given by the following equations:

m
=
Q
m
X
m

n
Q
n
X
n
(15)
X
m
=

j
v
(i)
m
x
j

n
v
(i)
n
x
j
(16)
In order to correctly describe the temperature dependence of
the residual excess Gibbs energy used in the VTPR mixing rule,
temperature-dependent group interaction parameters are used for
the large temperature range covered (often 250300K):

nm
= exp

a
nm
+b
nm
T +c
nm
T
2
T

(17)
The required temperature-dependent VTPR group interaction
parameters a
nm
, b
nm
and c
nm
are simultaneously tted to a compre-
hensive database of reliable experimental vaporliquid equilibria,
gas solubilities, solidliquid equilibria of simple eutectic sys-
tems, excess enthalpies and activity coefcient at innite dilution
0
4
8
12
6 4 2 0
P
r
P
r
T
r
T
r
N
2
0
4
8
12
16
6 4 2 0
CO
2
Fig. 8. Experimental (+ [30], [31]), correlated data ( [33]) and molecular sim-
ulation together with predicted JouleThomson inversion curve ( [4]), () VTPR,
() HEOS, (-) PR, (.......) SRK.
(

). The required temperature-dependent VTPR group inter-

action parameters of the compounds investigated are listed in
Tables 1 and 2.
The pure component parameters a
ii
and b
ii
can be determined
from the critical temperature T
c,i
and critical pressure P
c,i
.
a
ii
(T) = 0.45724
R
2
T
2
c,i
P
c,i

i
(T) (18)
Table 3
PR and SRK binary interaction parameters tted in this work.
System o
ij
p
ij
(K
1
] q
ij
(K
2
]
PR SRK PR SRK PR SRK
CO
2
/N
2
0.0136 0.028 0 0 0 0
CO
2
/CH
4
0.06453 0.09827 0.0001486 0 0 0
CO
2
/C
2
H
6
0.134 0.14067 0 0 0 0
CH
4
/N
2
0.0389 0.0377 0 0 0 0
CH
4
/C
2
H
6
0.00445 0.000817 0 0 0 0
N
2
/C
2
H
6
0.0706 0.149 0.000196 0.00137 0 0.00000374
CO
2
/Ar 0.1181 0.1216 0 0 0 0
Table 4
Average absolute relative deviations (AARDs) between experimental and predicted JouleThomson coefcients for ArCO
2
.
Equation P=10atm
T range (K) 233.15383.15
P=40atm
T range (K) 273.15383.15
P=80atm T range (K)
273.15383.15
x
CO
2
0.464 x
CO
2
0.754 x
CO
2
0.464 x
CO
2
0.754 x
CO
2
0.464 x
CO
2
0.754
VTPR (AARD) % 2.68 3.55 1.38 0.79 1.37 2.79
SRK (AARD) % 2.39 4.59 0.49 1.88 1.31 5.22
PR (AARD) % 7.46 6.48 7.2 2.9 5.74 7.73
R. Abbas et al. / Fluid Phase Equilibria 306 (2011) 181189 185
Table 5
Average absolute relative deviations (AARDs) between experimental and predicted JouleThomson coefcients for a mixture of 0.85 CH
4
0.15 C
2
H
6
.
Equation 0.85 CH
4
0.15 C
2
H
6
T range 250350 (K)
P=3MPa P=5MPa P=15MPa P=20MPa
VTPR (AARD) % 1.52 1.48 4.17 5.23
SRK (AARD) % 1.2 0.51 3.07 4.85
PR (AARD) % 8.71 6.63 4.99 8.97
Table 6
Average absolute relative deviations (AARDs) of the predicted JouleThomson inversion curves for selected pure substances from molecular simulation data.
Compound VTPR AARD % HEOS AARD % PR AARD % SRK AARD %
CO
2
T range (K) 3001050 9.67 8.75 12.43 18.76
N
2
T range (K) 125500 6.23 4.06 18.56 14.83
C
2
H
6
T range (K) 2751000 7.00 4.18 11.66 23.84
CH
4
T range (K) 178.3891.3 5.42 4.86 19.3 14.58
0
4
8
12
16
6 5 4 3 2 1 0
T
r
T
r
CH
4
0
3
6
9
12
15
6 4 2 0
P
r
P
r
C
2
H
6
Fig. 9. Experimental (* [32], correlated data [33]) and molecular simulation
together with predicted JouleThomson inversion curve ( [4]), () VTPR, ()
HEOS, (-) PR, (.......) SRK.
The -function proposed by Twu et al. [17] is used:

i
(T) = T
N
i
(M
i
1)
r,i
exp[L
i
(1 T
N
i
M
i
r,i
)] (19)
where T
r,i
is the reduced temperature for compound i, and N
i
, M
i
,
and L
i
the TwuBluckCunninghamCoon -function parameters,
which have been determined by regression of the vapor pressure
data of the pure components. If no experimental data are available,
the
i
(T) value can be calculated as function of the acentric factor
(
i
) using the following generalized expressions [9,18]:

i
(T) =
(0)
+
i
(
(1)

(0)
) (20)
If T <T
c,i
:

(0)
= T
0.1883273
r,i
exp[0.1048767(1 T
2.1329765
r,i
)] (21)
-75
-50
-25
0
25
950 750 550 350 150
(
(
P
i
,
c
a
l
c
.
-
P
i
,

M
S
)
/
P
i
,

M
S
)
%
T [K]
CH
4
Fig. 10. Deviations between molecular simulation and predicted JouleThomson
inversion curve, () VTPR, () HEOS, (-) PR, (.......) SRK.

(1)
= T
0.6029386
r,i
exp[0.5113343(1 T
2.2059312
r,i
)] (22)
If T >T
c,i
:

(0)
= T
0.792651
r,i
exp[0.401219(1 T
0.992615
r,i
)] (23)

(1)
= T
1.984711
r,i
exp[0.024955(1 T
9.98471
r,i
)] (24)
The pure component parameter b
ii
can be calculated from criti-
cal data:
b
ii
= 0.0778
R T
c,i
P
c,i
(25)
A quadratic mixing rule is used, to calculate the parameter b for
the mixture:
b =

j
x
i
x
j
b
ij
(26)
where the cross parameter b
ij
is calculated using the following
combination rule:
b
3/4
ij
=
b
3/4
ii
+b
3/4
jj
2
(27)
The volume translation parameter c is dened by the linear
mixing-rule:
c =

i
x
i
c
i
(28)
This parameter improves the prediction of the liquid densities
signicantly. If experimental liquid densities at reduced temper-
186 R. Abbas et al. / Fluid Phase Equilibria 306 (2011) 181189
0
4
8
12
16
6 4 2 0
Benzene
0
3
6
9
12
15
5 4 3 2 1 0
P
r
P
r
T
r
T
r
Toluene
Fig. 11. ( [33]) correlated data and predicted JouleThomson inversion curve,
() VTPR, () HEOS, (-) PR, (.......) SRK.
ature T
r,i
=0.7 are available, the translation parameter of the pure
compound is dened by the following equation:
c
i
= v
calc,i
v
exp,i
(T
r,i
= 0.7) (29)
When liquid density data are not available, c
i
can be estimated
from the critical data and the compressibility factor at the critical
point of compound i (z
c,i
) by using the following correlation:
c
i
= 0.252
R T
c,i
P
c,i
(1.5448z
c,i
0.4024) (30)
Three pure component parameters (T
c
, P
c
, v
c
) are needed in the
VTPR equation, when the general -function is used, as in SRK
or PR (T
c
, P
c
, ). In addition to the pure parameters, 26 binary
mixture parameters are used in VTPR to describe the phase equi-
librium behavior and the excess properties in a wide temperature
and pressure range (see Tables 1 and 2).
In this work, Eq. (5) is used to determine the JouleThomson
coefcient for pure compounds and for mixtures using VTPR.
3. Results and discussion
VTPR is a well established group contribution equation of state
(GCEOS) for the prediction of phase equilibria and other thermody-
namic properties. Figs. 1and2showthat theVTPRequationdelivers
a better prediction of the vaporliquid equilibrium behavior of the
systems ArCO
2
and N
2
CO
2
at different temperatures than SRK or
PR [19,20].
Therequiredparameters for PRandSRKfor predictingthebinary
or ternary systems are listed in Table 3. The binary temperature
0
4
8
12
16
6 4 2 0
P
r
P
r
P
r
T
r
T
r
T
r
Ethylene
0
4
8
12
16
6 4 2 0
Propyne
0
4
8
12
16
6 4 2 0
SF
6
Fig. 12. Experimental (x [38], correlated data [33]) and predicted JouleThomson
inversion curve, () VTPR, () HEOS, (-) PR, (.......) SRK.
dependent interaction parameter k
ij
for the quadratic mixing rule
of PR and SRK is given by the following equation:
k
ij
= o
ij
+p
ij
.T +q
ij
.T
2
(31)
where o
ij
=o
ji
, p
ij
=p
ji
, q
ii
=q
jj
.
The required parameters are tted simultaneously to all reliable
experimental vaporliquid equilibria for these systems stored in
the Dortmund Data Bank (DDB) [21].
The JouleThomson coefcients for the pure compounds, i.e.
CO
2
, N
2
and Ar; and for mixtures CH
4
+C
2
H
6
and CO
2
+Ar were
calculated using VTPR and compared with the published data.
Fig. 3 shows the predicted JouleThomson coefcients using VTPR
together with the experimental data for carbon dioxide at differ-
ent pressures and temperatures, which were published by Roebuck
et al. [22]. It can be seen that a good agreement between the pre-
dicted and experimental data is obtained. In Fig. 4 the estimated
JouleThomson coefcients for Ar using VTPR are shown together
withtheexperimental datapublishedin[23] andstoredintheDort-
R. Abbas et al. / Fluid Phase Equilibria 306 (2011) 181189 187
0
20
40
60
80
100
1200 800 400 0
P


[
M
P
a
]
T [K]
CO
2
-CH
4
0
20
40
60
800 600 400 200 0
P

[
M
P
a
]
T [K]
N
2
-CH
4
0
20
40
60
80
1200 800 400 0
P

[
M
P
a
]
T [K]
CH
4
-C
2
H
6
Fig. 13. ([4]) molecular simulation and predicted JouleThomson inversion curve,
() VTPR, () HEOS, (-) PR, (.......) SRK.
mundData Bank(DDB) [21]. Ingeneral, goodagreement is observed
for the whole temperature and pressure range.
In Fig. 5 calculated JouleThomson coefcients for carbon
dioxideargon mixtures at different compositions using VTPR, SRK
and PR are shown together with the available experimental values
[24]. Within the temperature range of 233.15383.15K at different
pressures and compositions, the deviations between experimental
and predicted JouleThomson coefcients for the ArCO
2
system
increases up to 3.77% for the VTPR in comparison up to 5.22% for
the SRK and up to 7.73% for the PR equation of state. The average
absolute relative deviations (AARDs) are listed in Table 4, where
AARD is dened as follows:
AARD =
1
n
n

i=1

JT
i,calc

JT
i,exp

JT
i,exp

(32)
It can be seen that the lowest deviations are obtained by VTPR,
whereas PR yields signicantly higher deviations. Fig. 6 reects
0
20
40
60
80
1200 900 600 300 0
P

[
M
P
a
]
T [K]
CO
2
-CH
4
-C
2
H
6
0
20
40
60
900 600 300 0
P

[
M
P
a
]
T [K]
N
2
-CH
4
-C
2
H
6
0
20
40
60
80
900 600 300 0
P

[
M
P
a
]
T [K]
CO
2
-CH
4
-N
2
Fig. 14. ([4]) molecular simulation and predicted JouleThomson inversion curve,
() VTPR, () HEOS, (-) PR, (.......) SRK.
these ndings for this system at 10atm, 46.4mol% CO
2
at different
temperatures.
In Fig. 7 the JouleThomson coefcients for CH
4
C
2
H
6
(with a
methane composition of 85mol%) predicted by the VTPR equation,
SRK and PR are compared with the available data [25]. The AARD
between the predicted and experimental data is listed in Table 5.
While SRK yields the lowest average absolute relative deviation
for
JT
, VTPR delivers good results for this system.
Besidethepredictionof
JT
for purecompounds andbinarymix-
tures also the JouleThomson inversion curves are calculated with
the VTPR, HEOS [2629], SRK and PR equation of state for pure
uids, binary and ternary systems. Figs. 8 and 9 show a compar-
ison of the available experimental data [3032], NIST data [33] and
the molecular simulation data by Vrabec et al. [4] together with
predicted JouleThomson inversion curve calculated with the help
of VTPR, HEOS [26,29], SRK and PR equations of state for nitro-
gen, carbon dioxide, methane and ethane. It can be seen that VTPR
and HEOS can reproduce the experimental ndings over the entire
temperature range. The predicted values from VTPR and HEOS are
188 R. Abbas et al. / Fluid Phase Equilibria 306 (2011) 181189
Table 7
Average absolute relative deviations (AARDs) of the predicted JouleThomson inversion curves for selected mixtures from molecular simulation data.
System VTPR AARD % HEOS AARD % PR AARD % SRK AARD %
CH
4
C
2
H
6
T range (K) 275850 6.53 4.95 9.62 10.87
CH
4
CO
2
T range (K) 275775 4.20 2.61 10.45 19.12
CH
4
N
2
T range (K) 200550 5.82 5.10 19.22 18.06
CH
4
C
2
H
6
N
2
T range (K) 200700 5.58 6.68 14.51 21.78
CH
4
C
2
H
6
CO
2
T range (K) 275850 3.19 4.94 8.03 8.61
-80
-40
0
40
80
600 400 200
(
(
P
i
,

c
a
l
c
.
-
P
i
,

M
S
)
/
P
i
,

M
S
)

%
T [K]
N
2
-CH
4
-40
-20
0
20
800 500 200
(
(
P
i
,
c
a
l
c
.
-
P
i
,

M
S
)
/
P
i
,

M
S
)
%
T [K]
CO
2
-CH
4
-C
2
H
6
Fig. 15. Deviations between molecular simulation and predicted JouleThomson
inversion curves, () VTPR, () HEOS, (-) PR, (.......) SRK.
in good agreement with the available experimental and molecular
simulation data. With the aim of evaluating the ability of the VTPR
equationfor predictionJouleThomsoninversioncurves, acompar-
ison between the molecular simulation data [4] and the predicted
values by VTPR, HEOS, SRK and PR are reported in Table 6 which
shows the average absolute relative deviations in the tempera-
ture range covered by the molecular simulation data for nitrogen,
carbon dioxide, methane and ethane. It can be recognized that
the VTPR results are similar to the results of HEOS in predicting
JouleThomson inversion curves with acceptable AARD and much
better results than SRK and PR. For SRK in most cases high nega-
tive deviations particularly at high temperatures are obtained, as
shown in Fig. 10, for methane.
Figs. 11 and 12 showa comparison of the JouleThomson inver-
sion curves for two aromatics compounds (benzene and toluene)
and for three other compounds (ethylene, propyne and SF
6
) esti-
mated with VTPR, HEOS, SRK and PR with the available correlated
experimental data [33]. Excellent agreement between the pre-
dicted and experimental data is achieved for all investigated
models for benzene and toluene at low temperatures. At higher
temperature the models provide different results. Unfortunately
experimental data at high temperatures are not available.
In Figs. 13 and 14 comparisons between the predicted JT inver-
sion curve using VTPR, HEOS, SRK and PR for six equimolar binary
and ternary systems are shown together with the molecular simu-
lationdata[4]. All studiedequations deliver thecorrect shapeat low
temperatures; however signicant deviations are againobtained at
high temperature. In Table 7 the mean absolute relative deviations
AARD are reported for the calculated JouleThomson inversion
curves for these mixtures.
AARD =
1
n
n

i=1

P
i,calc
P
i,MS
P
i,MS

(33)
The results show that the lowest deviations are obtained for
JouleThomson inversion curves predicted with the help of VTPR
compared to the other equations of state (HEOS, SRK, PR). AARD
values with respect to the molecular simulation data (see Table 7)
appear to suggest that the temperature-dependent group inter-
action parameters for VTPR have a relevant inuence on the
prediction results of the JT inversion curves and yield better results
than HEOS. The deviation plots are presented in Fig. 15 for the tem-
perature range covered by molecular simulation data. VTPR and
HEOS agree quite well with these data, whereas SRK show poor
results with negative deviation at the high temperature branch of
the JouleThomson inversion curve. The improved results for VTPR
compared to SRK and PR are mainly caused by the fact, that an
improved -function and at the time improved mixing rules for
the parameters a and b are used in VTPR.
4. Conclusion
Besides the excellent results of the VTPR group contribution
equation of state for the prediction of vaporliquid equilibria,
excess enthalpies, azeotropic data, activity coefcients at in-
nite dilution, solidliquid equilibria, gas solubilities, densities,
enthalpies of vaporization, etc., the group contribution equation of
stateVTPRwas examinedincomparisontoSRKandPRfor thecalcu-
lationof JouleThomsoncoefcients of purecompounds CO
2
, N
2
, Ar
andthe binary mixtures of CO
2
Ar andCH
4
C
2
H
6
. Goodagreement
is achieved between the predicted and the available experimental
data using VTPR not only for the pure compounds but also for the
mixtures in the whole temperature and pressure range. Further-
more the calculated results of VTPR for JouleThomson inversion
curves of CO
2
, N
2
, ethane, methane, benzene, toluene, ethylene,
propyne, and SF
6
are compared with available experimental and
correlateddata, andcomparedwiththeresults of HEOS, SRKandPR.
In all cases good agreement between the correlated experimental
and the calculated JouleThomson inversion curves equation was
found using VTPR. Moreover, the prediction of binary and ternary
systems using VTPR, HEOS, SRK and PR is compared to molecular
simulation data. The comparison shows that VTPR is competitive
with most equations of state for predicting JouleThomson inver-
sion curves.
List of symbols
VTPR volume translated PengRobinson equation of state
R. Abbas et al. / Fluid Phase Equilibria 306 (2011) 181189 189
PR PengRobinson equation of state
SRK SoaveRedlichKwong equation of state
HEOS Helmholtz equation of state
RESS Rapid Expansion of Supercritical Solution

JT
JouleThomson coefcient
DDB Dortmund Data Bank
AARD average absolute relative deviation
a attractive parameter of PengRobinson equation of state
and VTPR-equation
b volumetric parameter of PengRobinsonequationof state
and VTPR-equation
c temperature-independent volume correction for the
VTPR equation
h molar enthalpy
x liquid phase mole fraction
y vapor phase mole fraction
T absolute temperature
P pressure
v molar volume
c
p
isobaric heat capacity
a
nm
, b
nm
, c
nm
temperature-dependent group interaction parame-
ters
o, p, q temperature dependent interaction parameters of PR and
SRK
L, M, N TwuBluckCunninghamCoon -function parameters
g Gibbs energy from mod. UNIFAC method
R general gas constant
X group mole fraction
Z compressibility factor
Q relative van der Waals surface area of a subgroup
Greek letters
activity coefcient
temperature-dependent function in the residual part
temperature-dependent functionof the attractive param-
eter
v number of subgroups
group activity coefcient
group area fraction
Subscripts
i, j components i and j
m, n subgroup m, n
r reduced
res residual part
calc calculated
exp experimental
P isobaric
h isenthalpic
T isothermal
x at constant mole fraction
k subgroup
MS molecular simulation
Superscripts
E excess
at innite dilution
Acknowledgments
The authors thank the Arbeitsgemeinschaft industrieller
Forschungsvereinigungen (AIF: 13885N) for the nancial support
of this work. R. Abbas thanks the AL Baath University in Syria for
the fellowship.
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