Fluid Phase Equilibria 330 (2012) 2435

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Fluid Phase Equilibria
j our nal homepage: www. el sevi er . com/ l ocat e/ f l ui d
The iPRSV equation of state
T.P. van der Stelt
a,
, N.R. Nannan
b
, P. Colonna
a
a
Process and Energy Department, Delft University of Technology, Leeghwaterstraat 44, 2628 CA Delft, The Netherlands
b
Mechanical Engineering Discipline, Anton de KomUniversity of Suriname, Leysweg 86, PO Box 9212, Paramaribo, Suriname
a r t i c l e i n f o
Article history:
Received 3 April 2012
Received in revised form5 June 2012
Accepted 9 June 2012
Available online 21 June 2012
Keywords:
Equation of state
PengRobinson
PRSV
-Function
Discontinuity
iPRSV
a b s t r a c t
The PengRobinson cubic equation of state with the StryjekVera modication (PRSV) is widely adopted
in scientic studies and engineering. However, it is affected by a discontinuity in all the properties, which
is caused by a discontinuity of the -function. Aside of being non-physical, this discontinuity causes
robustness and accuracy issues in numerical simulations. The discontinuity in thermodynamic proper-
ties is eliminated here without affecting the overall accuracy of the model. In addition, the functional
form of (T) is optimized in such a way that it is not required to change the values of the uid-dependent
parameters stored in the many available databases. The performance of the improved equation of state
(iPRSV) is assessed by comparing calculated properties with those obtained with the original PRSV equa-
tionof state, the Gasem et al. equation of state (PRG), which is also continuous in temperature, a reference
multiparameter equation of state, and experimental data. It is shown that the accuracy of the new model
approaches the accuracy of the original equation of state and that it performs better than the PRG equa-
tion of state. The modied PRSV equation of state solves the issue of the articial discontinuity in the
calculation of properties relevant to scientic and industrial applications, at the cost of a small decrease
in overall accuracy.
2012 Elsevier B.V. All rights reserved.
1. Introduction
In order to obtain a better correlation of vapor pressures
for a wide variety of uids, Stryjek and Vera [1,2] proposed to
use the Peng-Robinson [4] cubic equation of state (EoS), com-
plemented by the Soave [3] -function, but with a different
temperature and acentric factor dependence. However, as a result,
the PengRobinson EoS with the StryjekVera modication (PRSV)
features a discontinuity in all the properties in correspondence of
the absolute critical temperature, T
c
, of water and of alcohols, and
at T =0.7 T
c
for other uids.
Over the last few decades, numerous modications to the -
function of Soave have been proposed, most of them with the
aim of obtaining a more accurate estimate of the pure-compound
vapor pressure. In particular, better performance has been sought
for reduced temperatures, T
r
T/T
c
, lower than 0.7, for substances
with an acentric factor greater than 0.5, and for polar uids
like alcohols. Some of the proposed modications accomplish this
goal by introducing one or more component-dependent parame-
ters [1,2,5,6]. Other modications involve changing the functional
formof in terms of either or T
r
, or both. The -function depen-
dency can be either linear [7], exponential [8], quadratic [6], or a
combination of the aforementioned [5,9].

Corresponding author. Tel.: +31 15 2785412.

E-mail address: T.P.vanderStelt@TUDelft.nl (T.P. van der Stelt).
Because in most cases the proposed modications are aimed
at improving only vaporpressure predictions, merely a handful
of researchers investigated the effect of their proposed modi-
cation of the -function on the prediction of all thermodynamic
properties, especially those dependent upon rst or higher-order
derivatives of in the supercritical region.
A number of thermodynamic models [1,7,9] suffer from the
reliance on the use of switching functions below and above the
critical temperature. These switching functions can cause large dis-
continuities in the -function and its derivatives. Gasem et al. [8]
addressed the problem of switching functions and proposed an
exponential and continuous -function. They determined the rst
and second-order derivative of the -function with respect to the
temperature and compared values of heat capacities predicted by
their model withexperimental data, for temperatures spanning the
range fromT
r
0.5 up to values well above the critical point tem-
perature for methane and nitrogen, and up to T
r
= 1.14 for propane.
They obtained a signicant improvement of the predicted heat
capacities with respect to the results from earlier models [3,5,7].
Neau et al. [10,11] analyzed in detail the inuence of the functional
relation of the EoS and the rst and second-order temperature
derivatives of the -function on the modeling of enthalpies and
heat capacities for reduced temperatures as high as about 3.5. They
found that the second-order temperature derivative of the general-
ized models for of Twu et al. [7] and Boston and Mathias [12] also
features abnormal extrema and inconsistent break points at the
critical temperature, due to the use of different sets of parameters
0378-3812/$ see front matter 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.uid.2012.06.007
T.P. van der Stelt et al. / Fluid Phase Equilibria 330 (2012) 2435 25
Nomenclature
a attractive termof the PengRobinson EoS, Eq. (2)
A, B, C coefcients of the -function of the iPRSV EoS, Eq.
(7)
D, E coefcients of the -function of the iPRSV EoS, Eq.
(7)
b co-volume parameter of the PengRobinsonEoS, Eq.
(3)
c speed of sound
C
0
, C
1
coefcients for the ideal gas C
P
polynomial, Eq. (4)
C
2
, C
3
coefcients for the ideal gas C
P
polynomial, Eq. (4)
C
P
isobaric heat capacity
C
v
isochoric heat capacity
h enthalpy
P pressure
R universal gas constant
s entropy
T absolute temperature
v specic volume
Greek symbols
functionof reducedtemperatureandacentric factor,
Eq. (4)
functionof reducedtemperatureandacentric factor,
Eq. (5)

0
function of the acentric factor in the -function, Eq.
(6)

1
pure compound parameter in the -function
density
acentric factor
Subscript
c critical
r reduced
Ref. EoS reference equations of state
tot total
Superscript
0 ideal gas state
below and above the critical temperature. They also pointed out
that the original -function of Soave has a non-physical minimum,
but that this minimum is in the range of 2.3< T
r
<9.5 and thus
far beyond the domain of current industrial applications. Conse-
quently they concluded that there are no theoretical reasons to
reject the Soave function. In their ndings, models also exhibit
totally different behavior with respect to, e.g., enthalpies and heat
capacities, while estimations for saturation properties may provide
similar results. Because of this, they put forward that a comparison
between various functional relations for (T) just based on their
inuence on the prediction of saturation properties is a meaning-
less test of the capabilities of the proposed modication.
Modern multi-parameter EoS and EoS based on the statisti-
cal associating uid theory (SAFT) have very promising features
with regard to accuracy of predictions and predictive capabilities.
Despite this, cubic equations of state (CEoS) are still widely adopted
in scientic andengineering applications. CEoS are attractive due to
their simplicity andthe linkto the most simple attractiverepulsive
molecular model. Furthermore, there is the possibility of extend-
ing the model to mixtures using robust and semi-empirical mixing
rules, and the availability of implementations in a large number
of computer programs linked to large databases of uid param-
eters for a large collection of compounds of industrial interest.
Even though a large number of cubic equation of state models are
available, the PRSV CEoS is still often chosen for scientic studies
and industrial applications ranging from process [1317], energy
[1821], and refrigeration [2224] systems modeling and simu-
lation, and uid dynamics simulations [2532]. The choice of the
PRSVmodel in these cases is due to its accurate estimation of vapor
pressures, the goodphase equilibriumcorrelationfor mixtures, and
its satisfactory performance for thermodynamic conditions other
than saturation, and for other thermodynamic properties. Further-
more, this equation of state provides a good trade-off between
simplicity of the model and accuracy, and the simplicity of the
formulation positively affects computational speed.
Besides the observation that the discontinuity in properties
caused by the discontinuity of the -function is not physical,
such a numerical artefact causes robustness and accuracy issues
in numerical simulations like, e.g., process and system simula-
tions or ow simulations, involving uid properties calculations.
Secondary thermodynamic properties are very relevant in these
computations.
The aimof this workis toeliminate fromthe PRSVmodel the dis-
continuity in the prediction of thermodynamic properties at either
T
r
= 1 or T
r
=0.7 (depending on the uid family), but without affect-
ing its overall accuracy. In addition, in order to prevent the need for
a change of the values of the uid parameters stored in the many
available databases, the solutionto the problemhas beensought by
optimizing the functional formof (T), but constraining the
0
and

1
parameters in Eqs. (5) and (6) and their values to be the same as
in the original PRSV model.
2. The PRSV model, the discontinuity in the -function and
its consequence for the computation of primary and
derived thermodynamic properties
The PRSV EoS is similar to the cubic formproposed by Peng and
Robinson [4],
P =
RT
v b

a
v
2
+ 2bv b
2
, (1)
where
a =

0.457235R
2
T
2
c
P
c

, (2)
and
b =
0.077796RT
c
P
c
. (3)
The -function,
= [1 +(1

T
r
)]
2
, (4)
is the same as the one proposed by Soave [3], where is a func-
tion of the acentric factor only. The modication introduced by
Stryjek and Vera [1], which increases the accuracy of predictions of
saturated properties, makes temperature-dependent as in
=
0
+
1
(1 +

T
r
)(0.7 T
r
), (5)
with

0
= 0.378893 + 1.4897153 0.17131848
2
+ 0.0196554
3
.(6)
The parameter
1
in Eq. (5) is a pure-component parameter.
Fromlowtemperatures uptoreducedtemperatures of T
r
=0.7, Stry-
jek and Vera recommend using values for
1
tabulated in their
papers [1,2]. Alternatively,
1
can also be obtained by regressing
experimental data. According to Stryjek and Vera, for water and
alcohols the tabulated values can be applied up to the critical point.
For other compounds, slightly better results are obtained with

1
=0 for 0.7< T
r
< 1. For super critical temperatures (T
r
1) they
26 T.P. van der Stelt et al. / Fluid Phase Equilibria 330 (2012) 2435
Table 1
The denition of the -function in the Stryjek and Vera formulation of the attractive
term in the PengRobinson equation of state.
(a) Water and alcohols: Tr <1 =
0
+
1
(1 +

Tr)(0.7 Tr)
Tr 1 =
0
(b) All other compounds: Tr 0.7 =
0
+
1
(1 +

Tr)(0.7 Tr)
Tr >0.7 =
0
T
r
= T / T
c

0
=
0
,

1
=
1
)
0.2 0.4 0.6 0.8 1 1.2 1.4 1.6
-0.8
-0.6
-0.4
-0.2
0
0.2
0.4
0.6
0.8
1
Fig. 1. -Parameter of the PRSV CEoS for alcohols and water ( ) and all other
compounds ( ).
recommend
1
= 0, because there would be no advantage in using
Eq. (5) in this region. The -function therefore introduces a discon-
tinuity in (T) either at T
r
=0.7 or at T
r
=1, and in thermodynamic
properties dependent upon and derivatives thereof.
The denition of the -function is summarized in Table 1. Fig. 1
shows the value of for
0
=0and
1
=1as a functionof the reduced
temperature for both water and alcohols and all other compounds.
Figs. 2 and 3 demonstrate exemplary anomalies in the selected
thermodynamic properties caused by the mentioned discontinu-
ities. Fig. 2 depicts a line of constant isochoric heat capacity C
v
v [m
3
/kg]
P
[
M
P
a
]
10
-2
10
-1
2
4
6
8
10
12
14
VLE
Fig. 2. Discontinuity of the PRSV model: Pv diagram of methanol displaying the
vaporliquid equilibrium region (VLE) and the non-physical discontinuity of an
exemplary iso-Cv line (Cv = 1.7kJ/kg-K) ( ) crossing the critical isotherm
( ).
Table 2
Coefcients of the equation of the iPRSV EoS.
A=1.1
B = 0.25
C= 0.2
D = 1.2
E =0.01
calculated withthe PRSVmodel, together withthe critical isotherm
and the saturated liquid and vapor lines in a Pv diagram for
methanol. By following the iso-C
v
line for increasing pressure and
decreasing specic volume, a non-physical discontinuity in the line
can be noted as it intersects the critical isotherm.
Fig. 3 shows a similar effect in the Ts diagram for methanol.
Together with the vaporliquid equilibrium region and the criti-
cal isotherm, exemplary isolines calculated with the PRSV model
are also shown. In order to illustrate the consequence of the
non-physical discontinuity, with reference to Fig. 3d, imagine the
expansion of the uid through a nozzle starting from P =1.5MPa
and T = 240

C. As the pressure and temperature decrease, at the

critical temperature, an non-physical jump in the entropy value
occurs (from0.119 to 0.1167 kJ/kg-K). Notice also, as an additional
example (Fig. 3c), that a state characterized by the same speed
of sound and entropy, features two values of temperature which
contravenes the phase rule of thermodynamics.
3. The iPRSV cubic equation of state
The improved PRSV EoS, iPRSV, is obtained by modifying the
equationfor thecalculationof the-value, suchthat it is continuous
with the temperature, but by keeping the same parameters
0
and

1
in the functional form, with the same values. The -function in
the iPRSV thermodynamic model is therefore
=
0
+
1

[A D(T
r
+B)]
2
+E + A D(T
r
+B)

T
r
+ C. (7)
This functional formwas obtained by matching it to the original
PRSV formulation as close as possible, except for the discontinuity
(see Fig. 4). The implementation of the iPRSV in computer codes,
relying on existing databases collecting the parameters for many
uids, is quite straightforward. No retting of data is necessary.
The coefcients A, B, C, D, and E are presented in Table 2. The
derivatives of with respect to the temperature necessary for
the implementation of a complete thermodynamic model into a
computer program are given in Appendix A. The continuity of the
equation assures the continuity in the rst and second derivative
of with respect to the temperature.
1
In order to prevent a sign change in the rst-order tempera-
ture derivative of , the newfunction follows as closely as possible
the original PRSV formulation (b) in Table 1. With reference to
Fig. 5ad, it can be noted that, by varying coefcient E, the cur-
vature of (T
r
) in correspondence of T
r
= 0.7 can be changed. The
smaller the value of E, the closer the values of the newfunction are
to the original formulation. However, the smaller the value of E, the
larger is the uctuation of the second-order derivative with respect
to the temperature. E comes therefore from a trade-off between
the counteracting need of approximating the original -value as
close as possible, and minimizing the variation of the second-order
temperature derivative.
Figs. 6 and 7 show a comparison between PRSV and iPRSV
related to the same exemplary diagrams reported in Figs. 2 and
3.
1
Note that physics prescribes that is a monotone functionof temperature, with-
out inection points, therefore both the original formulation and the one proposed
here violate this constraint.
T.P. van der Stelt et al. / Fluid Phase Equilibria 330 (2012) 2435 27
s [kJ/kg-K]
T
[

C
]
-2.5 -2 -1.5 -1 -0.5 0 0.5
0
50
100
150
200
250
VLE
e c d b
(a) T s diagram of methanol displaying the critical isotherm
( ), the vapor-liquid equilibrium region (VLE), and the
non-physical discontinuities in some exemplary isolines (iso-h,
iso-c, isobar, isochor)( ). Enlargements of areas b, c, d,
and e are shown in gures 3b, 3c, 3d, and 3e.
s [kJ/kg-K]
T
[

C
]
-1.6 -1.58 -1.56 -1.54 -1.52
230
235
240
245
250
h = -344.3 kJ/kg
h = -357.1 kJ/kg
h = -350 kJ/kg
(b) iso- h lines.
s [kJ/kg-K]
T
[

C
]
-0.22 -0.2 -0.18 -0.16
220
225
230
235
240
245
250
255
260
c = 346.4 m/s
c = 353.2 m/s
c = 350 m/s
(c) iso- c lines.
s [kJ/kg-K]
T
[

C
]
0.112 0.114 0.116 0.118 0.12
239
239.2
239.4
239.6
239.8
240
P = 1.511 MPa
P = 1.5 MPa
P = 1.489 MPa
(d) isobars.
s [kJ/kg-K]
T
[

C
]
0.424 0.425 0.426 0.427 0.428
239
239.2
239.4
239.6
239.8
240
v = 0.2493 m
3
/kg
v = 0.2507 m
3
/kg
v = 0.25 m
3
/kg
(e) isochors.
Fig. 3. Graphical representation of the non-physical discontinuities in some exemplary isolines in the Ts diagramof methanol calculated with the original PRSV CEoS.
4. Performance of the iPRSV model
The attraction parameter in the PRSV EoS was proposed in
order to improve the accuracy of the calculation of the satu-
ration pressures. Firstly, in order to evaluate the performance
of the iPRSV model, the results of saturation pressure calcula-
tions are compared for uids of different classes and molecular
complexity. Moreover, in order not to limit the evaluation to
the prediction of saturated properties, also PT data, spe-
cic enthalpies, and entropies are compared to values computed
28 T.P. van der Stelt et al. / Fluid Phase Equilibria 330 (2012) 2435
T
r
= T / T
c

0
=
0
,

1
=
1
)
0.2 0.4 0.6 0.8 1 1.2 1.4 1.6
-0.8
-0.6
-0.4
-0.2
0
0.2
0.4
0.6
0.8
1
Fig. 4. as function of Tr (with
0
= 0 and
1
=1) for the original PRSV CEoS (alco-
hols and water , all other compounds: ), and the newiPRSV CEoS
( ).
with reference multiparameter equations of state. Such a more
extensive evaluation is limited to methanol and propane as exem-
plary uids.
In order to obtain a complete thermodynamic model, the iPRSV
equation of state is complemented with a polynomial function for
the calculation of the ideal gas isobaric heat capacity, i.e.,
C
0
P
R
= C
0
+C
1
T +C
2
T
2
+ C
3
T
3
,
v [m
3
/kg]
P
[
M
P
a
]
10
-2
10
-1
2
4
6
8
10
12
14
VLE
Fig. 6. Pv diagram of methanol displaying the non-physical discontinuity of an
exemplary iso-Cv line (Cv =1.7kJ/kg-K) calculated with the PRSV model () in cor-
respondence of the critical isotherm ( ), the same iso-Cv line calculated by the
iPRSV EoS ( ), and the vaporliquid equilibriumregion (VLE).
where C
0
, C
1
, C
2
and C
3
are uid-specic coefcients. Table 3 lists
the input data for the complete iPRSV model of the selected uids.
The results of saturation pressure calculations performed with
the iPRSV EoS are compared with those obtained with the origi-
nal PRSV EoS, with the PRGEoS (PengRobinsonGasem), and with
accurate measurements. The PRG EoS is a PR-type EoS implement-
ing the -function proposed by Gasem et al. [8]. The PRG EoS is
T
r
= T / T
c

0
=
0
,

1
=
1
)
0.2 0.4 0.6 0.8 1 1.2 1.4 1.6
0
0.2
0.4
0.6
0.8
(a)
T
r
= T / T
c
T
c 2
.
d
2

/
d
T
2
(

0
=
0
,

1
=
1
)
0.2 0.4 0.6 0.8 1 1.2 1.4 1.6
-6
-4
-2
0
2
4
(b)
T
r
= T / T
c

0
=
0
,

1
=
1
)
0.2 0.4 0.6 0.8 1 1.2 1.4 1.6
0
0.2
0.4
0.6
0.8
(c)
T
r
= T / T
c
T
c 2
.
d
2

/
d
T
2
(

0
=
0
,

1
=
1
)
0.2 0.4 0.6 0.8 1 1.2 1.4 1.6
-10
0
10
20
30
40
50
(d)
Fig. 5. Curvature of the -functionof the iPRSVEoS near the intersectionwithx-axis (a andc) andits non-dimensional second-order derivative withrespect to the temperature
T
2
c
(d
2
/dT
2
) (b and d) for E= 0.1 (a and b) and E=0.001 (c and d).
T.P. van der Stelt et al. / Fluid Phase Equilibria 330 (2012) 2435 29
(b) iso-h lines. (c) iso-c lines.
(d) isobars . (e) isochors.
(a) Ts diagram of methanol displaying the critical isotherm
( ), the vapor-liquid equilibrium region (VLE), some ex-
non-physical discontinuities calculated with the PRSV model,
and the same, but continuous, isolines calculated by the iPRSV
model. Enlargeme nts of areas b, c, d, and e are shown in g-
ures 7b, 7c, 7d, and 7e.
emplary isolines (iso-h,iso-c, isobar, isochor) displaying the
Fig. 7. Graphical representation of the non-physical discontinuities in some exemplary isolines in the Ts diagram of methanol calculated with the original PRSV CEoS
( ) together with the continuous isolines calculated with the iPRSV CEoS ( ).
included in this evaluation because its attractive parameter is a
continuous function of the temperature, much like in the iPRSV
model. It is therefore an alternative to the iPRSV EoS, if model
consistency is a concern. However, this thermodynamic model has
not been widely adopted in scientic and engineering applications
as testied by the lack of literature referring to the use of the PRG
model for practical purpose.
Fig. 8 shows charts displaying the percentage absolute devia-
tions (AD%) of the saturation pressures calculated by the iPRSV,
PRSV, and the PRG EoS with respect to experimental values.
The considered exemplary uids are dodecane, methanol, water,
andMDM octamethyltrisiloxane,[(CH
3
)
3
SiO]
2
Si(CH
3
)
2
. TheiPRSV
model applied to dodecane (Fig. 8a) is somewhat less accurate in
predicting the saturated pressure than the PRSV for 0.65< T
r
<0.75
while for T
r
> 0.75 the iPRSVperforms slightly better. The PRGis the
least accurate for T
r
>0.7 and the deviation increases for increas-
ing temperature, while it is the most accurate of the three in
the temperature interval 0.55< T
r
<0.65. For lower temperatures
30 T.P. van der Stelt et al. / Fluid Phase Equilibria 330 (2012) 2435
T
r
= T / T
c
|
P
s
a
t
,
e
x
p
-
P
s
a
t
,
c
a
l
c
|
/
P
s
a
t
,
e
x
p
*
1
0
0
%
0.4 0.5 0.6 0.7 0.8
0
0.5
1
1.5
2
2.5
3
3.5
4
(a) dodecane
T
r
= T / T
c
|
P
s
a
t
,
e
x
p
-
P
s
a
t
,
c
a
l
c
|
/
P
s
a
t
,
e
x
p
*
1
0
0
%
0.6 0.7 0.8 0.9 1
0
2
4
6
8
10
12
14
(b) methanol
T
r
= T / T
c
|
P
s
a
t
,
e
x
p
-
P
s
a
t
,
c
a
l
c
|
/
P
s
a
t
,
e
x
p
*
1
0
0
%
0.4 0.5 0.6 0.7 0.8
0.9 1
0
1
2
3
4
5
(c) water
T
r
= T / T
c
|
P
s
a
t
,
e
x
p
-
P
s
a
t
,
c
a
l
c
|
/
P
s
a
t
,
e
x
p
*
1
0
0
%
0.4 0.5
0.6 0.7 0.8 0.9 1
0
1
2
3
4
5
6
7
8
(d) MDM
Fig. 8. Percentage absolute deviation between experimental data for the vapor pressure (data marked accepted in the DIPPR [33] database taken as a reference), and values
calculated with the iPRSV ( ), PRSV ( ), and the PRG EoS ( ).
deviations are larger for all the models, with the PRG EoS being the
least accurate. It is noticeable that at very low pressure the accu-
racy of the measurements could be comparatively lower and the
percentage absolute deviation is inherently larger. Fig. 8b and c
show analogous trends for methanol and water. The lower accu-
racy of the iPRSV model for methanol and water for T
r
>0.7 can be
expected, becausethelargest differencebetweenthediscontinuous
-function of the PRSV model and the continuous -function
of the iPRSV occurs in this temperature range (see Fig. 4). For
MDM and dodecane this effect is less pronounced. Furthermore,
Fig. 8d shows that the performance of the iPRSV model with
respect to PRSV, PRG, and experimental values in the case of
MDM cannot be clearly inferred. The PRG model is less accurate
for T
r
>0.75.
Table 3
Main uid thermodynamic data for the iPRSV EoS of some uids selected for the evaluation of its performance.
Name Tc [K] Pc [MPa]
1
Reference Coefcients for the ideal gas CP polynomial function
C
1
C
2
10
3
C
3
10
6
C
4
10
9
Reference
Inorganic
Ammonia 405.55 11.28952 0.25170 0.00100 [1] 27.31 23.83 17.07 11.85 [34]
Carbon dioxide 304.21 7.38243 0.22500 0.04285 [1] 19.80 73.44 56.02 17.15 [34]
Oxygen 154.77 5.090 0.02128 0.01512 [1] 28.11 3.680 10
3
17.46 10.65 [34]
Water 647.286 22.08975 0.34380 0.06635 [1] 32.24 1.924 10.55 3.596 [34]
Alkanes
Propane 369.82 4.24953 0.15416 0.03161 [1] 4.224 306.3 158.6 32.15 [34]
Dodecane 658.2 1.82383 0.57508 0.05426 [1] 9.328 1.149 634.7 135.9 [34]
Ketones
Acetone 508.1 4.696 0.30667 0.00888 [1] 6.301 260.6 125.3 20.38 [34]
Alcohols
Methanol 512.58 8.09579 0.56533 0.16816 [1] 21.15 70.92 25.87 28.52 [34]
Ethanol 513.92 6.148 0.64439 0.03374 [1] 9.014 214.1 83.90 1.373 [34]
2-Propanol 508.40 4.76425 0.66372 0.23264 [1] 32.43 188.5 64.06 92.61 [34]
1-Butanol 562.98 4.41266 0.59022 0.33431 [1] 3.266 418.0 224.2 46.85 [34]
1-Octanol 684.8 2.86 0.32420 0.82940 [1] 6.171 760.7 379.7 62.63 [34]
Ethers
Dimethyl ether 400.1 5.240 0.18909 0.05717 [1] 17.02 179.1 52.34 1.918 [34]
Refrigerants
R134a 374.21 4.056 0.3259 0.0048 [39]
a
16.7813 286.357 227.336 113.312 [39]
R245fa 427.2 3.640 0.3724 0.0060 [40,41]
a
28.1594 335.454 144.213 0
b
Siloxanes
MDM 564.09 1.41516 0.5314 0.06195
a
97.3376 863.971 250.057 95.1544 [43]
c
D5 619.15 1.16 0.6658 0.03885
a
90.9707 1564.41 1091.37 340.099 [43]
c
a

1
tted to experimental data.
b
Coefcients tted to ideal-gas heat capacity values obtained froma reference thermodynamic model implemented in a widely adopted computer code [42].
c
C
1
, C
2
, C
3
, C
4
tted to experimental data.
T.P. van der Stelt et al. / Fluid Phase Equilibria 330 (2012) 2435 31
Table 4
Percentage average absolute deviations (AAD%) for the vapor pressures calculated
with the PRSV, PRG and the iPRSV EoS with respect to the experimental values
marked as accepted in the DIPPR [33] database.
Fluid PRSV PRG iPRSV nPoints Range Tr
Ammonia 0.45 1.13 0.44 73 Tr > 0.48
Carbon dioxide 0.59 0.24 0.73 44 Tr > 0.71
Oxygen 0.35 1.08 0.36 74 Tr > 0.37
Water 0.12 7.62 0.72 51 Tr > 0.42
Propane 0.71 0.53 0.76 35 Tr > 0.35
Dodecane 1.14 2.60 1.28 65 0.44< Tr <0.8
Acetone 1.08 1.99 1.08 113 Tr > 0.40
Methanol 0.60 3.95 1.63 66 Tr > 0.57
Ethanol 0.91 1.03 0.72 89 Tr > 0.57
2-Propanol 6.38 4.34 8.12 105 Tr > 0.37
1-Butanol 0.70 8.29 3.42 81 Tr > 0.52
1-Octanol 0.65 171 4.86 72 Tr >0.42
Dimethyl ether 0.86 3.02 0.95 39 Tr > 0.44
R134a 0.40 0.85 0.40 151 Tr > 0.56
R245fa 0.92 0.49 0.95 32 Tr > 0.68
MDM 1.12 1.82 1.15 29 Tr >0.46
D5 3.39 2.74 3.51 22 0.51< Tr <0.8
Average 1.20 2.61
a
1.83
a
AAD of 1-octanol was left out of the calculation of this average value.
The estimates of saturatedpressures for all the other uids listed
in Table 3 have been compared to experimental data in a similar
way and the results are summarized in Table 4. No general trend
or relation to a particular class of uids can be detected from this
comparison.
In terms of the overall average absolute deviation (AAD), the
original PRSVcorrelates the experimental values the best, followed
by the iPRSV, which is slightly worse, and by the PRG, which shows
higher values for the AAD. Note however, that the AAD limited to
saturated pressure values cannot be used as merit parameter as it
does not show the accuracy in relation to the temperature range.
For most uids the PRG equation of state is considerably less accu-
rate than the iPRSV for T
r
< 0.7 (see for example Fig. 8). The fact
that some of the uids in this assessment are different fromthe 27
uids that Gasem et al. used to t the parameters for their equa-
tion of state does not inuence the outcome of the evaluation.
2
Consequently this cannot be the reason for the higher values
of the AAD.
In more detail, for uids featuring small
1
-values, uids with
large values of , and for alcohols, the following observations for
the iPRSV EoS with respect to the original PRSV hold.

Fluids featuring small

1
-values (<0.01): these are uids like
ammonia, acetone, R134a, and R245fa. As it is expected the cor-
relation of the saturation pressures of the iPRSV EoS is almost as
good as that of the PRSV EoS (mean AAD = 0.71 % for PRSV and
0.72 % for iPRSV), because the more
1
approaches zero, the more
the values of the -function of the iPRSV EoS approach the values
of the -function of the original PRSV EoS.

Fluids with large values of (>0.5): these are siloxanes like MDM
and D
5
and larger alkanes like dodecane. Also for these uids the
iPRSV EoS performs almost as good as the PRSV EoS (1.88 % for
PRSV and 1.98 % for iPRSV).

Alcohols: the correlation of saturated pressures provided by

the iPRSV model is worse than what is obtained for non-polar
molecules (mean AAD = 1.85 % for PRSV and 3.75 % for iPRSV),
except for ethanol.
2
Fluids 2-propanol, 1-butanol, 1-octanol, dimethyl ether, R134a, R245fa, MDM,
and D5 were not used for tting the parameters of the PRGEoS. Omitting these uids
fromthe comparison leads to a mean AAD% of 0.66, 0.86, and 2.24 for respectively
PRSV, iPRSV, and PRG. This compares well with the results reported in Table 4.
[
k
g
/
m
3
]
10
-2
10
-1
10
0
10
1
10
2
10
-1
10
0
10
1
10
2
10
3
VLE
c

r
10
-3
10
-2
10
-1
10
0

A
D
[
%
]
0
5
10
P [MPa]
Fig. 9. P diagram of propane displaying the VLE region (calculated with a ref-
erence EoS for propane [35]), several exemplary isotherms calculated with the
reference EoS ( ), the same isotherms calculated with the iPRSV model
(symbols), and the corresponding percentage absolute deviation between the tem-
peratures calculated with the reference equation of state and the iPRSV model (,
T = 223.15K; , T = 263.15K; , T = 303.15K; , T = T
c,ref.EoS
=369.89K; , T =443.15K;
, T = 543.15K; , T = 650K).
The performance of the PRG EoS, as far as saturated pressures
predictions are concerned, is worse than that of the iPRSV EoS. In
particular, the PRG EoS applied to 1-octanol predicts unreasonable
values for T
r
< 0.7. The
1
-value of 2-propanol has beenrecalculated
by tting the vapor pressures of the PRSV EoS to 105 experimental
data points in a temperature range fromT
r
= 0.37 up to 1 (these are
also used in Table 4), because the PRG EoS performs much bet-
ter than the PRSV and the iPRSV EoS with the original value of

1
in Table 3. A reason for this outlier could be that Stryjek and
Vera tted the vapor pressure estimations to only a small num-
ber of experimental points in a very limited temperature range
(17 data points, 0.64< T
r
<0.71). The outcome of the new tting
is
1
=0.04920 (which is much smaller compared to the original
value of 0.23264) and the AADs are 3.77 and 3.96 % for respectively
the PRSV and the iPRSV EoS. As a result the PRSV and the iPRSV
EoS with the retted vapor pressures performbetter than the PRG
EoS, with an AAD of 4.34 %, while the AAD obtained with original
values for
1
are 6.38 and 8.12 % for PRSV and iPRSV respectively
(see Table 4).
As also claimed by others [10,11], the evaluation of an EoS is not
complete, if only the estimation of saturation pressures is consid-
ered. For this reason, other properties are taken into account in this
assessment. Inorder toprovide anindicationof the overall accuracy
of the iPRSV model, several isotherms for propane and methanol
are compared to those obtained with reference equations of state
[35,38]. The density is calculated as a function of T and P, and the
resulting density is assessed in terms of percentage deviation. In
addition, also several isenthalpic lines are computed, whereby T is
calculated as a function of enthalpy and entropy.
3
In this case the
percentage deviation of temperature with respect to reference val-
ues is considered. Figs. 912 show the results of these evaluations
for propane and methanol.
It is generally known that the liquid densities are not repre-
sented accurately by a CEoS. This applies also to the iPRSV model,
which becomes immediately clear from observing the calculated
densities in the liquid region in Figs. 9 and 11. As expected the
3
Note that a small difference in the values of T is introduced by a difference in
the model of C
0
P
with respect to the reference equations of state. This difference,
however, is not relevant for engineering applications.
32 T.P. van der Stelt et al. / Fluid Phase Equilibria 330 (2012) 2435
A
D
[
%
]
0
2
4
s [kJ/kg-K]
T
[

C
]
1 1.5 2 2.5 3
0
50
100
150
200
VLE
Fig. 10. Ts diagram of propane displaying the VLE region (calculated with a ref-
erence EoS for propane [35]), several exemplary constant enthalpy lines calculated
with the reference EoS ( ), the same lines of constant enthalpy calculated
with the iPRSV model (), and the percentage absolute deviation between data
calculated with the reference equation of state and the iPRSV model ().
[
k
g
/
m
3
]
10
-3
10
-2
10
-1
10
0
10
1
10
2
10
-2
10
-1
10
0
10
1
10
2
10
3
VLE
c

r
10
-4
10
-3
10
-2
10
-1
10
0

A
D
[
%
]
10
-2
10
-1
10
0
10
1
P [MPa]
Fig. 11. P diagramof methanol displaying the VLE region (calculated with a ref-
erence EoS for methanol [38]), several exemplary isotherms calculated with the
reference EoS ( ), the same isotherms calculatedwiththe iPRSVmodel (),
and the percentage absolute deviation between data calculated with the reference
EoS and the iPRSV EoS ().
A
D
[
%
]
0
2
4
6
s [kJ/kg-K]
T
[

C
]
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5
0
50
100
150
200
250
300
VLE
Fig. 12. Ts diagramof methanol displaying the VLE region (calculated with a refer-
ence EoS for methanol [38]), several exemplary constant enthalpy lines calculated
with a reference EoS ( ), the same lines of constant enthalpy calculated
with the iPRSV model (), and the percentage absolute deviation between data
calculated with the reference EoS and the iPRSV EoS ().
Table 5
Percentage absolute deviations (AAD%) in PT and Ths data of the PRSV, PRG
and the iPRSV EoS with respect to reference equations of state for propane [35]
and n-butane [36], and technical equations of state for n-hexane, n-octane [37] and
methanol [38].
Fluid PT Ths
PRSV PRG iPRSV PRSV PRG iPRSV
Propane 2.46 2.46 2.47 0.69 0.68 0.73
n-Butane 40.0 39.9 40.0 0.35 0.41 0.33
n-Hexane 34.9 31.4 35.1 0.27 0.21 0.28
n-Octane 19.9 21.0 19.7 0.13 0.19 0.12
Methanol 9.60 9.74 9.56 0.64 1.16 0.91
Propane
a
0.43 0.42 0.42
n-Butane
b
0.47 0.52 0.46
n-Hexane
c
0.44 0.64 0.42
n-Octane
d
0.45 1.16 0.40
Methanol
e
1.38 1.35 1.30
a
Only r <1.4 were taken into account (c =220.48kg/m
3
[35]).
b
Only r <1.0 were taken into account (c =228 kg/m
3
[36]).
c
Only r <1.0 were taken into account (c =233.18 kg/m
3
[37]).
d
Only r <1.0 were taken into account (c =234.90 kg/m
3
[37]).
e
Only r <0.6 were taken into account (c =275.56 kg/m
3
[38]).
CEoS performs also quite better for propane than for methanol, as
it is known that the thermodynamic properties of polar molecules
cannot be estimated as accurately as those of non-polar com-
pounds with a CEoS. The densities of propane do not largely
deviate from experimental data for
r
< 1.4 (where
r
=/
c
, and

c
=220.48 kg/m
3
[35]). Above this value, deviations increase up
to 10%. For methanol deviations become unacceptably large for

r
> 0.6 (
c
=275.56 kg/m
3
[38]), with deviations up to 35%.
It can also be observed in Fig. 9 that the deviations of the cal-
culated densities for propane are less than 2% for
r
<1. For the
densities in the supercritical region, the differences go up to 5%
and for the liquid densities they are between 5 and 10%. Note also
that the uncertainties in densities of the reference EoS are one or
two orders of magnitude smaller.
In Fig. 10, lines of constant enthalpy are shown in a Ts chart
for propane, and are calculated with the iPRSV and a reference
equation of state for comparison. The chart reveals that the abso-
lute deviation of the calculated temperatures with respect to the
reference EoS for most of the points is less than 1.5%. There are
two outliers in the liquid region with an absolute deviation of
3.24% and 1.88%. The relatively large deviation of 3.24% can be
explained by the fact that for the iPRSV EoS the point is in the liq-
uid region, while for the reference EoS it is in the two phase VLE
region.
Fig. 11 shows a P diagramfor methanol with the percentage
absolute deviation compared to a reference EoS for methanol [38].
For
r
<0.6 the absolute deviations rise fromless than 0.01% at low
pressures up to 3% for pressures until 10MPa (while for the ref-
erence EoS the uncertainties in densities are in general less than
0.1%). At higher pressure some points feature a deviation between
5 and 10%. For reduced densities greater than 0.6 the deviations
are all greater than 10%, and increase up to values of 35%. In the
Ts chart of methanol most of the calculated temperatures have an
absolute deviation of less than 3%. Similarly to the Ts diagram of
propane, there are some outliers in the liquid region, close to the
saturated liquid line (maximum absolute deviation 5.13%). In the
vapor region, the largest deviations occur for two points, and these
are just a little greater than 3%, 3.28% and 4.12%.
In the same way as for the calculations of the saturated vapor
pressures, PT dataandThs dataarecomputedfor propaneand
methanol with the PRSV, the PRG and the iPRSV EoS. For all three
models, the same ideal gas heat capacity function was used (Eq.
(4)). Again the results are compared with a reference EoS [35,38],
T.P. van der Stelt et al. / Fluid Phase Equilibria 330 (2012) 2435 33
Fig. 13. Convergingdiverging nozzle (a) and the corresponding owpath in the Ts plane (b).
position
P
[
M
P
a
]
-0.2 0 0.2 0.4 0.6 0.8 1
3.3
3.4
3.5
3.6
3.7
3.8
3.9
(a) pressure
position
T
[

C
]
-0.2 0 0.2 0.4 0.6 0.8 1
236
238
240
242
244
246
248
250
T
c
(b) temperature
position
M
a
c
h
[
-
]
-0.2 0 0.2 0.4 0.6 0.8 1
0.2
0.25
0.3
0.35
0.4
0.45
0.5
0.55
0.6
(c) Mach number
number of iterations
l
o
g
(
r
e
s
i
d
u
a
l
L
1
-
n
o
r
m
)
0 20000 40000 60000 80000 100000
-12
-10
-8
-6
-4
-2
0
2
4
(d) residuals
Fig. 14. Visualisation of the simulation results of a subsonic uid ow of a superheated methanol vapor through a nozzle using an explicit Euler solver. The charts display
the non-converged, discontinuous results if the PRSV CEoS ( ) is used for the calculation of the thermodynamic properties, and the converged ones that result from
adopting the iPRSV CEoS ( ) instead.
and the average absolute deviations (AAD%) are summarized in
Table 5. The differences of the PT data and the Ths data of
propane between all models and the reference EoS are negligi-
ble. For methanol, if the calculated liquid densities are taken into
account, the PRG model performs slightly worse. If they are not
taken into account, then iPRSV performs best, closely followed by
the PRGandthe PRSV. The difference indeviations for the Ths cal-
culations is more substantial: the PRSVperforms 0.27%point better
than the iPRSV model, and 0.52% point better than PRG in terms of
AAD.
Similar calculations as for propane and methanol were carried
out for alkanes with increasing sizes (n-butane, n-hexane, and n-
octane). Just the calculation results are summarized in Table 5.
In general the deviations are decreasing for increasing compo-
nent sizes. For PT data in the vapor phase the deviations are
quite similar for the PRSV and iPRSV model, but increasing for
PRG EoS.
5. Results and conclusions
The PRSV equation of state is widely used in computer pro-
grams for scientic and industrial applications. It features a good
trade-off between accuracy and computational speed, and it pro-
vides the possibility of extending the model to mixtures. The PRSV
thermodynamic model, however, features a numerical discontinu-
ity in all thermodynamic properties at the critical temperature T
c
for water and alcohols and at T = 0.7 T
c
for other uids. The discon-
tinuity in the attractive termof this cubic equationof state has been
introducedinorder to improve the accuracy of computed saturated
properties. Such a discontinuity, besides being a non-physical phe-
nomenon, generates numerical problems in computer simulations
relyingonthecomputationof uidthermodynamic properties. This
issue is briey treated here using the canonical example of the sim-
ulation of a uid ow through a convergingdiverging nozzle (see
Figs. 13 and 14).
34 T.P. van der Stelt et al. / Fluid Phase Equilibria 330 (2012) 2435
The quasi-one dimensional inviscid ow through the noz-
zle is solved by means of the one-dimensional Euler equations
with source terms to mimic the convergingdiverging nozzle [44].
The conservation equations for mass, momentum and energy are
solved using a rst-order nite volume scheme and an explicit
time integration. The convective uxes are evaluated using the
approximate Riemann solver proposed by Liou [45]. Since the
approximate Riemann solver requires the evaluation of the speed
of sound, enthalpy and pressure, the solver is coupled to the PRSV
CEoS.
The conditions at the inlet and outlet of the nozzle (Fig. 13a) are
chosen in the superheated vapor phase slightly above the critical
temperature, such that the ow through the nozzle is acceler-
ated towards the throat and decelerated afterwards. A subsonic
ow develops, whereby at the throat the temperature has its
minimum, which is below the critical temperature. The ow
through the nozzle has therefore to cross the critical temperature
two times; slightly upstreamandslightly downstreamof the throat
location (Fig. 13b). The corresponding total conditions at the inlet
are T
1,tot
=253

C and P
1,tot
= 4MPa and the static pressure at the
outlet is set to be P
2
= 3.85MPa.
The results in Fig. 14 show the pressure, temperature, Mach
number through the nozzle and the normalized L
1
-norm residu-
als of the energy equation for the simulations. The results obtained
with the PRSV, containing the discontinuities in the CEoS, clearly
shownon-smooth proles for the pressure, temperature and Mach
number at the location where the critical temperature is crossed.
These discontinuities prevent the solution to converge to steady
state as seen in Fig. 14d by means of the normalized L
1
residual
of the energy equation as a function of the number of iteration
steps.
This paper presents a solution to this problem in the form
of a modication of the -function composing the temperature-
dependent attractive term of this van der Waals-type equation
of state. The continuous -function of the improved PRSV, iPRSV,
equation of state closely resembles the original function apart
from the discontinuity. The requirement of a close match to the
original function was specied as a constraint during the devel-
opment of the new function. The new formulation features the
additional and non-trivial advantage that the uid parameters
of the original model, and
1
are unchanged. If a computer
program already implements the PRSV EoS, the database pro-
viding the uid-specic input values need not to be modied,
and only changing few lines of code allows for a quick imple-
mentation. Fig. 14 shows that the iPRSV uid model solves the
robustness issues affecting the PRSV EoS in uid dynamics simu-
lations encompassing the critical point region. The solution for the
owthrough the nozzle converges to machine precision (Fig. 14d)
in case the iPRSV CEoS is used, leading to smooth proles for the
temperature, pressure and Mach number throughout the whole
nozzle.
The performance of the iPRSV model has been evaluated by
comparison with the original PRSV equation of state and with
the PRG equation of state. The latter is also consistent in the
entire thermodynamic space. Values computed with these cubic
equations of state have been compared, taking measurements of
saturated pressures and values calculated with reference equa-
tions of state as a reference for, respectively, saturated states,
and subcooled liquid and superheated vapor states for exemplary
uids.
The accuracy of the iPRSV model is comparable to the
original PRSV model and better than the PRG equation of
state, thus solving the issue of the articial discontinuity in
the calculation of properties relevant to scientic and indus-
trial applications, at the cost of a small decrease in overall
accuracy.
Acknowledgements
The authors would like to thank their colleague and friend Dr.
Rene Pecnik for his help with and his valuable comments about the
owsimulation calculations for the convergingdiverging nozzle.
Appendix A.
Derivatives of the equation of the iPRSV EoS with respect to
the temperature:
=
0
+
1
(T
x
+T
y
)T
z
d
dT
=

1
(T
x
+ T
y
)
T
c

1
2T
z

DT
z
T
y

d
2

dT
2
=

1
(T
x
+ T
y
)
T
2
c

D
T
y
T
z
+
1
4T
3
z
+
D
2
T
z
T
3
y
(T
x
T
y
)

d
3

dT
3
=
3
1
(T
x
+T
y
)
T
3
c

D
4T
y
T
3
z
+
1
8T
5
z

D
2
T
3
y
(T
x
T
y
)(
DT
x
T
z
T
2
y
+
1
2T
z
)

with:
T
r
=
T
T
c
T
x
= A D(T
r
+B)
T
y
=

T
2
x
+E
T
z
=

T
r
+C
A = 1.1
B = 0.25
C = 0.2
D = 1.2
E = 0.01
References
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