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Fluid Phase Equilibria 316 (2012) 66–73

Contents lists available at SciVerse ScienceDirect

Fluid Phase Equilibria

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

Implementation of PC-SAFT and SAFT + Cubic for modeling thermodynamic

properties of haloalkanes. I. 11 halomethanes
Ilya Polishuk ∗ , Maxim Katz, Yulia Levi, Helena Lubarsky
Department of Chemical Engineering & Biotechnology, Ariel University Center of Samaria, 40700 Ariel, Israel

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

Article history: In the current study the widely implemented theoretically based model PC-SAFT and the recently pro-
Received 13 October 2011 posed SAFT + Cubic have been applied for correlating and predicting various thermodynamic properties
Received in revised form of 11 halomethanes. It has been found that thanks to the correct estimation of the experimental critical
28 November 2011
temperatures and pressures, SAFT + Cubic exhibits a superior robustness and reliability in modeling both
Accepted 1 December 2011
pure compounds under consideration and their mixtures. In addition, SAFT + Cubic has a clear advantage
Available online 9 December 2011
in predicting sound velocities and isochoric heat capacities. However PC-SAFT is more accurate in mod-
eling certain kinds of data, such as the isobaric heat capacities of saturated liquids and vapor pressures
Keywords:
Equation of state
away from the critical points.
Statistical association fluid theory © 2011 Elsevier B.V. All rights reserved.
Refrigerants
Density
Sound velocity

1. Introduction
Haloalkanes present a very important family of compounds
widely used as refrigerants, solvents, propellants, and fumigants. In
addition, haloalkanes are particularly interesting from the thermo-
dynamic viewpoint since their densities might substantially exceed
the typical values characteristic for most organic compounds. The
practical importance of haloalkanes has initiated numerous exper-
imental studies. The significant amount of experimental data on
these compounds has allowed derivation of accurate empirical
models for interpolating their thermodynamic properties (see for
example [1–11]).
The theoretically based Equation of State (EoS) models such as
different variations of Statistical Association Fluid Theory (SAFT)
might be less precise than the above empirical equations in their
prescribed P–V–T ranges of applicability. However the theoretically
based models have certain doubtful advantages. In particular, they
are not supposed to be restricted by the applicability ranges, require
less adjustable parameters and might be more easily applied for
predicting data in mixtures.
Thus far different theoretically based models have been imple-
mented for modeling data of pure and mixed haloalkanes (see
for example [12–21]). The current series of studies aims a com-
prehensive description of their various thermodynamic properties
∗ Corresponding author. Tel.: +972 3 9066346; fax: +972 3 9066323.
E-mail addresses: polishuk@ariel.ac.il, polishyk@bgumail.bgu.ac.il (I. Polishuk).
using of two equations of state, namely PC-SAFT and SAFT + Cubic.
The present work considers 11 halomethanes: carbon tetrachlo-
ride (R10), trichlorofluoromethane (R11), dichlorodifluoromethane
(R12), chlorotrifluoromethane (R13), carbon tetrafluoride (R14),
chlorodifluoromethane (R22), trifluoromethane (R23), difluo-
romethane (R32), methyl chloride (R40), methyl fluoride (R41)
and bromotrifluoromethane (R13B1). Previously [22], SAFT + Cubic
has been implemented for modeling data of chloroform (R20) and
dichloromethane (R30). Therefore these compounds have not been
considered in the current study. In further studies we intend to con-
sider the thermodynamic properties of haloethanes, halopropanes
and mixtures of haloalkanes.
2. Theory
Being based on analytical solution of the Percus–Yevick molec-
ular approximation, PC-SAFT [23] is currently one of the most
successful and widely used theoretically based approaches [24]. We
have found that in the case of haloalkanes the previously detected
numerical pitfalls characteristic for PC-SAFT [25–27] take place far
below the measured and the estimated solidification lines of both
pure compounds and mixtures, and, therefore, are not expected to
affect the performance of the model.
Detailed description of PC-SAFT EoS is provided in the original
Ref. [23]. Similarly to other versions of SAFT, PC-SAFT is expressed

0378-3812/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.fluid.2011.12.003
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I. Polishuk et al. / Fluid Phase Equilibria 316 (2012) 66–73 67

Table 1 Table 2
Pure compound adjustable parameters of PC-SAFT EoS. Pure compound parameters of SAFT + Cubic EoS.

Compound m ε/k (K)  (Å) Compound Adjustable parameters Parameters obtained solving
the critical point conditions
R10 2.51900 280.700 3.71079
R11a 2.34570 244.680 3.66220 m c (L/mol) a (bar-mol2 /L2 )  (Å) ε/k (K)
R12a 2.27650 202.810 3.53570
R13a 2.22230 160.780 3.35210 R10 2.08000 0.153170 16.9703 4.05354 403.788
R14b 2.24740 120.360 3.10600 R11 2.02000 0.149295 12.5046 3.93335 346.541
R22a 2.54660 185.470 3.10920 R12 1.95000 0.137109 8.69634 3.81586 283.631
R23a 2.95990 140.910 2.74040 R13 1.80000 0.123107 5.46185 3.67817 221.021
R32c 2.76400 173.158 2.75400 R14 1.56000 0.133124 3.12233 3.58630 168.350
R40 1.93600 241.090 3.20701 R22 1.86000 0.114640 6.76849 3.51420 269.776
R41 2.01300 184.230 2.91358 R23 1.69000 0.110412 4.69908 3.34585 217.277
R13B1 2.53900 169.870 3.31702 R32 1.50000 0.104441 5.40866 3.31525 244.658
R40 1.40000 0.121820 5.56144 3.60316 296.178
a
From Ref. [19]. R41 1.25000 0.117502 4.53533 3.38329 219.009
b
From Ref. [20]. R13B1 1.95000 0.124226 7.01135 3.71260 250.229
c
From Ref. [21].

generating artificial unrealistic phase equilibria. Another advan-

in terms of the following contributions to the residual Helmholtz
free energy:
Ares = Ahs + Achain + Adisp + Aassoc
where the superscripts hs, chain, disp and assoc correspond to
the hard sphere, chain, dispersion and association contributions,
respectively. These contributions, in turn, are functions of the fol-
lowing adjustable parameters: m – effective number of segments,
 – Lennard–Jones temperature-independent segment diameter,
ε/k – segment energy parameter divided by Boltzmann’s constant,
kAB – volume of interaction between the association sites and
εAB /k – interaction of association energy. Thus, for the associating
polar compounds the model requires five adjustable parameters.
In the case of the non-associating compounds the association con-
tribution is deleted and the model stays with three adjustable
parameters. Swaminathan and Visco [13] have discussed imple-
mentation of the association contribution for modeling haloalkanes
using SAFT of Variable Range (SAFT-VR). They have concluded that
for compounds having a nonzero dipole moment, irrespective of
their molecular structure, the two sites association scheme should
be assumed. At the same time, the references implementing PC-
SAFT for modeling haloalkanes [18–21] have preferred reducing
the number of the adjustable parameter by neglecting the possible
association. This approach has been adopted by the current study as
well (the PC-SAFT pure compound adjustable parameters are listed
in the Table 1).
The mean idea of the recently proposed SAFT + Cubic EoS is
attaching SAFT by the attractive term of cubic EOS as follows:
a 80
Ares = Ares,SAFT −
v+c
tage of SAFT + Cubic is the smaller number of the pure compound
adjustable parameters (two for the compounds treated as non-
(1) associative). More details concerning this model can be found in
Ref. [28]. It should only be pointed out that similarly to other
small molecules, the critical volume displacement factor for 9
halomethanes considered in the present study has been set to 1.065.
The latter factor has been set to unity for R40 and R41. The pertinent
parameter matrix of SAFT + Cubic is given in Table 2.
All the calculations (including the fitting of parameters) have
been performed in the Mathematica 7® software. Implementation
of both models under consideration usually requires similar com-
putation times. The pertinent routines can be obtained from the
corresponding author by request.
3. Results
Fig. 1 depicts the vapor pressures, data that together with densi-
ties have been used for the parameter fitting of both models. Having
more adjustable parameters, PC-SAFT exhibits a higher flexibil-
ity that SAFT + Cubic. This fact might explain the somewhat better
results of PC-SAFT away from the critical points. In particular, it
can be seen that SAFT + Cubic slightly overestimates the vapor pres-
sures of R32 and underestimates them in the cases of R10, R11 and
R22. Nevertheless, it should be recognized that the overall accuracy
of SAFT + Cubic is superior due to the correct estimation of the crit-
ical points. As seen, PC-SAFT overestimates the critical constants
of halomethanes with different degrees of extend. In particular,
(2) 100
R4
1
R4
0
R41 R32 R40
4

10
R1

P(bar) R1
0

where a and c are empirical correction parameters. Since 1

  60 .1 R22
RT ∂Ares
P= − (3) .01
V ∂V
R22

T .001
R11

R11 R10
the pressure is obtained as: 40
.0001

a R14 R23
P = P SAFT − 2
(4)
(V + c)

The theoretical basis of SAFT + Cubic is weaker in comparison with 20

PC-SAFT. Unlike PC-SAFT, SAFT + Cubic relies on generalizing the
regularities exhibited by experimental data rather than approx-
imating the results of molecular simulations. At the same time 0
it should be pointed out that the empirical part of SAFT + Cubic 90 250 410 570
has a relatively modest numerical contribution [28]. In addition, T(K)
SAFT + Cubic is free of the well-known disadvantages characteristic
Fig. 1. Vapor pressures.  – Pseudo-experimental (evaluated from the compound-
for several SAFT approaches, such as the inability to correlate the specific empirical EoS) data [8–11]. Predictions: SAFT + Cubic – solid lines, PC-SAFT
critical and subcritical pure compound data simultaneously and – dashed lines.
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68 I. Polishuk et al. / Fluid Phase Equilibria 316 (2012) 66–73

0 440
R4

R 23
R13

R 22

R41
H(J/g) 0
0 T(K)
-5000 R4 R12

320 R13B1
-10000
R1 3

R4

R1

R
13
R1

2
-15000

B1
3
R14
200

R 41
-20000
R1
4

-25000
0 26 P(bar) 52 78 80
0 800 (g/L) 1600 2400
0
S(J/g) 590
2 1 0
R2 R4 R4
3
T(K) R10
R1
490
R11

-50 390 R22

R40,R41
R32
290 R23 R2
2

190
-100
0 26 P(bar) 52 78 R32 R23
90
Fig. 2. Enthalpies and entropies of condensation.  – Pseudo-experimental data 0 600 (g/L) 1200 1800
[11]. Predictions: SAFT + Cubic – solid lines, PC-SAFT – dashed lines.
Fig. 3. Densities of saturated phases.  (liquid), 䊉 (vapor) – Pseudo-experimental
data [8–11]. Predictions: SAFT + Cubic – solid lines, PC-SAFT – dashed lines.
this overestimation is relatively small in the case of R14 and sig-
nificant in the case of R41. Unfortunately, our attempts to move 410
the PC-SAFT’s critical points closer to the experimental ones have T(K)
resulted in serious deterioration of accuracy in modeling densities.
In other words, due to the inability of PC-SAFT to fit the critical and
the sub-critical data simultaneously, the experimental critical con- 300
stants have to be sacrificed in order to obtain a reasonable over-all
accuracy of modeling.
Fig. 2 provides representative examples of predicting enthalpies
R4
R1

and entropies of condensation. As seen, an overestimation of the 190 1

2
R

critical points affects the capability of PC-SAFT to predict accurately

13

these practically very important data.

Fig. 3 depicts the phase envelop densities. As already pointed
out, these data have been used for the parameter fitting of both 80
models. Therefore their over-all satisfactorily accurate perfor- 0 600 1200 1800
W(m/s)
mance is not surprising. Nevertheless, some deviations from the
data should be noticed. In particular, SAFT + Cubic tends to under- 490
estimate the near-critical liquid densities and PC-SAFT exhibits the T(K)
relatively poor accuracy in the case of R32. It has been found that R1
R40 and R41 are the compounds uneasy for modeling with both 390 1

equations under consideration, and there was a price to pay for

their reasonably accurate fitting. In the case of PC-SAFT it was
R2
the substantial overestimation of the critical data and in the case 290 2
of SAFT + Cubic – cancellation of the critical volume displacement
factor used for the rest of the compounds. The latter might be con-
sidered as analogous to implementation of an additional adjustable 190
parameter.
Fig. 4 provides representative examples of predicting the sound
velocities in the saturated phases. The doubtless advantage of 90
SAFT + Cubic over PC-SAFT in modeling this property is evident. 0 500 1000 1500
Although both models are capable of its accurate description in W(m/s)
the vapor phase, only SAFT + Cubic yields acceptable predictions
Fig. 4. Sound velocities of saturated phases.  (liquid), 䊉 (vapor) – Pseudo-
of sound velocities in the saturated liquids. More details on these experimental data [11]. Predictions: SAFT + Cubic – solid lines, PC-SAFT – dashed
phenomena are given below. lines.
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I. Polishuk et al. / Fluid Phase Equilibria 316 (2012) 66–73 69

500 400
T(K) T(K)

380 300

260 200

R11 R12
140 100
.34 .48 C (J/g-K) .62 .76 .27 .43 CV(J/g-K) .59 .75
V

320 400
T(K) T(K)

260
300

200

200
140
R13 R22

80 100
.2 .4 CV(J/g-K) .6 .8 .3 .5 CV(J/g-K) .7 .9

Fig. 5. Isochoric heat capacities of saturated phases.  (liquid), 䊉 (vapor) – Pseudo-experimental data [11]. Predictions: SAFT + Cubic – solid lines, PC-SAFT – dashed lines.

500 400
T(K) T(K)

380 300

260 200

R11 R12

140 100
1 CP(J/g-K) 1 CP(J/g-K)

320 400
T(K) T(K)

260
300

200

200
140
R13 R22

80 100
1 CP(J/g-K) 1 CP(J/g-K)

Fig. 6. Isobaric heat capacities of saturated phases.  (liquid), 䊉 (vapor) – Pseudo-experimental data [11]. Predictions: SAFT + Cubic – solid lines, PC-SAFT – dashed lines.
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70 I. Polishuk et al. / Fluid Phase Equilibria 316 (2012) 66–73

600 1200
P (bar)
P(bar)
900
400

600

200
300

0 0
1300 1420 1540 1660 0 700 1400 2100
(g/L) (g/L)

Fig. 7. High pressure densities of carbon tetrachloride (R10). Experimental data Fig. 9. High pressure densities of carbon tetrafluoride (R14). Pseudo-experimental
[29]: 䊎 – 329.83 K, – 367.38 K, – 408.77 K. Predictions: SAFT + Cubic – solid data [31]: 䊎 – 120 K, – 220 K, – 320 K, – 420 K. Predictions: SAFT + Cubic –
lines, PC-SAFT – dashed lines. solid lines, PC-SAFT – dashed lines.

5400

The next properties to be considered, namely the isochoric heat P (bar)

capacities of the saturated phases (see Fig. 5) are difficult for accu-
rate prediction due to the inability of both analytical models under
3600
consideration to describe the critical exponents. Nevertheless, it
can be seen that SAFT + Cubic correctly estimates the patterns of
behavior of this property in saturated liquids, which is not a case
of PC-SAFT. At the same time, PC-SAFT is surprisingly precise in
1800
predicting the isobaric heat capacities of the saturated liquids (see
Fig. 6), exhibiting yet doubtless superiority over SAFT + Cubic. These
results might partially be explained by its overestimation of the
critical data, a disadvantage that in this particular case is turning 0
into advantage. Both models under consideration yield compara- 0 600 1200 1800
(g/L)
ble accuracy in predicting heat capacities of the saturated vapors,
which is satisfactorily good at low temperatures but deteriorates Fig. 10. High pressure densities of chlorodifluoromethane (R22). Experimental data
while approaching the critical points. [32]: 䊎 – 298.2 K, – 373.2 K, – 473.2 K, – 573.2 K. Predictions: SAFT + Cubic –
In the following discussion let us proceed to consideration of solid lines, PC-SAFT – dashed lines.
the single-phase properties at high pressures. Figs. 7–12 depict the
densities. As seen, in most of the cases SAFT + Cubic is more accurate results let us consider the typical example of R10. Sound velocity is
then PC-SAFT in modeling this property. Its advantage is most obvi- given as:
ous in the cases of R12 (Fig. 8) and R41 (Fig. 12). However in certain   
cases, such as the high pressure and high temperature density data CP v2 ∂P
of R22, PC-SAFT exhibits better accuracy than SAFT + Cubic. W= − (5)
CV Mw ∂v
T
Figs. 13–17 present the sound velocities at high pressure. As
seen, yet the advantage of SAFT + Cubic over PC-SAFT is unques- Fig. 18 depicts the ratios between SAFT + Cubic and PC-SAFT
tionable. In most of the cases PC-SAFT underestimates the data and in predicting the constituent parts of Eq. (5).As seen, the
these deviations increase with pressure. In order to analyze these differences between the models in predicting Cp /CV and v
are relatively small and nearly cancelling each other. Thus the

1800 4400
P(bar)
P (bar)
3300
1200

2200

600
1100

0 0
1180 1380 (g/L) 1580 1780 0 420 840 1260
(g/L)

Fig. 8. High pressure densities of dichlorodifluoromethane (R12). Experimental Fig. 11. High pressure densities of methyl chloride (R40). Experimental data [33]:
data [30]: 䊎 – 253.15 K, – 273.15 K, – 293.15 K, – 313.15 K. Predictions: 䊎 – 298 K, – 373 K, – 473 K, – 573 K. Predictions: SAFT + Cubic – solid lines,
SAFT + Cubic – solid lines, PC-SAFT – dashed lines. PC-SAFT – dashed lines.
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I. Polishuk et al. / Fluid Phase Equilibria 316 (2012) 66–73 71

3200 600

P(bar) P (bar)
2400
400

1600

200
800

0 0
0 400 800 1200 400 600 800 1000
(g/L) W (m/s)

Fig. 12. High pressure densities of methyl fluoride (R41). Experimental data [34]: Fig. 15. High pressure sound velocities in chlorodifluoromethane (R22). Experimen-
䊎 – 298.15 K, – 373.15 K, – 448.15 K, – 573.15 K. Predictions: SAFT + Cubic – tal data [36]: 䊎 – 283.15 K, – 303.15 K, – 323.15 K. Predictions: SAFT + Cubic –
solid lines, PC-SAFT – dashed lines. solid lines, PC-SAFT – dashed lines.

1500 800
P(bar)
P (bar)
600
1000

400

500
200

0 0
400 700 W (m/s) 1000 1300 0 450 900 1350
W (m/s)
Fig. 13. High pressure sound velocities in carbon tetrachloride (R10). Experimental Fig. 16. High pressure sound velocities in difluoromethane (R32). Experimental data
data [29]: 䊎 – 283.86 K, – 350.55 K, – 454.97 K. Predictions: SAFT + Cubic – solid [37]: 䊎 – 248.2 K, – 278.12 K, – 313.19 K, – 343.29 K. Predictions: SAFT + Cubic
lines, PC-SAFT – dashed lines. – solid lines, PC-SAFT – dashed lines.


difference in estimating −(∂P/∂v)T has the major impact on
the final result. As seen (Fig. 7), PC-SAFT slightly underesti-
mates the slopes of isotherms in the density–pressure projection.
Consequently, this model underestimates (∂P/∂)T , overestimates
 Figs. 19 and 20 depict the isothermal compressibilities of R14
(∂P/∂v)T and, lastly, underestimates −(∂P/∂v)T and −(∂P/∂v)T
(see Fig. 18). These results explain the characteristic for PC-SAFT
under-prediction of sound velocities (see Fig. 13). In other words,
even relatively minor deviations in the density–pressure projection
might substantially affect the accuracy in predicting auxiliary prop-
erties. At the same time it should be emphasized that the attempts
to improve the accuracy of PC-SAFT in modeling sound velocities
by rescaling its parameters result in substantial deterioration in
estimation of all other properties.
and the isentropic compressibilities of R22. Yielding the compara-
ble predictions for the high pressure densities of R14, both models
estimate the isothermal compressibilities of this compound with
the similar degree of accuracy as well. However since SAFT + Cubic
is a better estimator of sound velocities, it is also advantageous in
predicting isentropic compressibilities.

2400 600
P(bar)
P (bar)

1600 400

800 200

0 0
400 700 1000 1300 200 360 520 680
W (m/s) W (m/s)

Fig. 14. High pressure sound velocities in trichlorofluoromethane (R11). Experi- Fig. 17. High pressure sound velocities in bromotrifluoromethane (R13B1). Experi-
mental data [35]: 䊎 – 353.25 K, – 373.12 K, – 393.23 K, – 413.19 K. Predictions: mental data [38]: 䊎 – 283.15 K, – 303.15 K, – 323.15 K. Predictions: SAFT + Cubic
SAFT + Cubic – solid lines, PC-SAFT – dashed lines. – solid lines, PC-SAFT – dashed lines.
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72 I. Polishuk et al. / Fluid Phase Equilibria 316 (2012) 66–73

1.15 60

P(bar)
1.10
P P 40
v T v T
SAFT Cubic PC SAFT
1.05

20
1.00 v SAFT+Cubic
/v PC-SAFT
CP CP
CV CV
.95
SAFT Cubic PC SAFT 0
0.0 .2 .4 .6 .8 1.0
0 1800
P(bar) 3600 5400 x1

Fig. 18. Differences between SAFT + Cubic and PC-SAFT in predicting the constituent Fig. 21. Bubble-points lines in the system R11(1)–R22(2). Experimental data [39]:
parts of Eq. (5) (R10 at T = 283.86 K.) 䊎 – 298.15 K, – 323.15 K, – 348.15 K, – 373.15 K. Modeling: SAFT + Cubic
(k12 = 0.08) – solid lines, PC-SAFT (k12 = 0.05) – dashed lines.

1000

P (bar)
800
750 P(bar)

600
500

400
250

200
0
1 10 100 1000
(GPa-1) 0
900 1200 1500 1800
Fig. 19. Isothermal compressibilities of carbon tetrafluoride (R14). Pseudo- (g/L)
experimental data [31]: 䊎 – 120 K, – 220 K, – 320 K, – 420 K. Predictions:
SAFT + Cubic – solid lines, PC-SAFT – dashed lines. Fig. 22. High pressure densities of the system R11(1)–R22(2) (x1 = 0.1664). Exper-
imental data [40]: 䊎 – 230 K, – 320 K, – 400 K. Predictions: SAFT + Cubic
(k12 = 0.08) – solid lines, PC-SAFT (k12 = 0.05) – dashed lines.
And, finally, let us consider several mixtures of the compounds
under consideration. Figs. 21 and 22 depict the bubble-points lines
and the high pressure densities of the system R11(1)–R22(2). The
binary adjustable parameter k12 has been fitted to the VLE data parameters are required for fitting the data at higher temperatures.
at 298.15 K for both models. As seen, SAFT + Cubic is a more accu- Once again, this result should be explained by the characteristic
rate estimator of densities than PC-SAFT. The latter model exhibits for PC-SAFT overestimation of pure compound critical tempera-
the characteristic under-prediction of the isotherms slopes in the tures and pressures (see Figs. 23 and 24). These figures demonstrate
density-pressure projection. In addition, it appears that unlike that thanks to the precise adjustment to the pure compound crit-
SAFT + Cubic, PC-SAFT is incapable of accurate correlation of vari- ical data, SAFT + Cubic has a doubtless superiority over PC-SAFT in
ous VLE isotherms with the same value of k12 ; smaller values of this correlating VLE in the symmetric mixtures under consideration.

600 66

P (bar) P(bar)

400 44

200 22

0 0
.6 2.2 -1 3.8 5.4 0.0 .2 .4 x1 .6 .8 1.0
S (GPa )

Fig. 20. Isentropic compressibilities of chlorodifluoromethane (R22). Experimental Fig. 23. VLE in the system R23(1)–R22(2). Experimental data [41]: 䊎 – 273.15 K,
data [36]: 䊎 – 283.15 K, – 303.15 K, – 323.15 K. Predictions: SAFT + Cubic – solid – 303.15 K, – 323.15 K, – 343.15 K, – 353.15 K. Modeling: SAFT + Cubic
lines, PC-SAFT – dashed lines. (k12 = 0.04) – solid lines, PC-SAFT (k12 = 0.02) – dashed lines.
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I. Polishuk et al. / Fluid Phase Equilibria 316 (2012) 66–73 73

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