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Ie 050071 C
Ie 050071 C
The Perturbed-Chain SAFT (PC-SAFT) equation of state is applied to model phase equilibria
and the thermodynamic properties of ethers and esters. A systematic study of these two
homologous series is conducted, and the performance of two different approaches for including
the dipolar interactions in the equation of state is evaluated. Although both Polar PC-SAFT
[dipolar contribution due to Jog and Chapman, Mol. Phys. 1999, 97, 307-319] and PC-SAFT
+ Fischer [dipolar contribution by Saager and Fischer, Mol. Simul. 1991, 6, 27-49] yield similar
results for the considered systems, the parameters of Polar PC-SAFT are more physically
meaningful than those of PC-SAFT + Fischer. Consequently, Polar PC-SAFT is considered to
be more suitable for extrapolations, and for application to components that have multiple polar
groups in the chain.
1. Introduction
A molecules electrostatic moment has a strong effect
on the phase behavior of the macroscopic system. In this
work, we are concerned with dipolar interactions, which
influence the phase behavior of numerous systems of
industrial importance, such as mixtures containing
ketones, ethers, and esters, as well as polar polymers
and copolymers. Mixtures containing one polar and one
nonpolar component often exhibit strong, positive deviation from ideality, resulting in azeotropic behavior. We
can cite the mixture of 2-butanone with n-heptane as
an example.1 The deviation from ideality is due to
differences in intermolecular interactions. Dipolar interactions become increasingly important at low temperatures. For instance, in the polyethylene-dimethyl
ether (PE-DME) system, the two-phase region extends
to much higher pressures at low temperatures, where
DME-DME polar interactions are favored over PEDME interactions.2 The phase behavior of polar polymer
and copolymer solutions is determined by interactions
of the multiple dipole moments present in the polymer
chain.
The effect of dipolar interactions on the phase behavior is difficult to model and predict accurately. In
conventional equations of state (EOSs), the polar interactions are not taken into account explicitly. The nonideal behavior is modeled by fitting a large binary
interaction parameter, which often is dependent on the
temperature and composition of the system. Therefore,
the predictive abilities of such models are often weak,
because of the inability to extrapolate accurately with
temperature and to multicomponent systems.
Three methods could be considered for the incorporation of the polar contribution to the Helmholtz free
* To whom correspondence should be addressed. Tel.: 713348-4900. Fax: 713-348-5478. E-mail: wgchap@rice.edu.
Ind. Eng. Chem. Res., Vol. 44, No. 17, 2005 6929
2. Theory
The molar residual Helmholtz free energy is given in
terms of a perturbation expansion:
(1)
apolar )
a2
1 - a3/a2
(2)
a2 ) -
9 (kT)2
i j
i2j2
xixjmimjxpixpj
I2,ij
dij2
(3)
a3 )
5
162
F2
i j k
(kT)3
xixjxkmimjmkxpixpjxpk
i2j2k2
I3,ijk
dijdjkdik
(4)
6930
j)
I2,ij ) I2(,m
(5)
j)
I3,ijk ) I3(,m
(6)
where
i ximi
m
j )
(7)
and
i ximidi3
(8)
apolar )
i j
28
xixjmimjxpixpj
( ) ()
[ ( )]
T
cq 1.13T
q)1
nq/2
lq/2
F0
F0
(9)
with
( )
R + (1 - R) T
F
) Fd 3
F0 6 ij
0.1617 T0
(10)
and
T0 )
()
ij
1.268
k
(11)
/2
i )
i2
idi3
(12)
Ind. Eng. Chem. Res., Vol. 44, No. 17, 2005 6931
study are from the Daubert and Danner pure-component data compilation.34
EOS parameters are usually regressed by fitting
vapor pressure and liquid density data, applying a
Levenberg-Maquart minimization algorithm. The objective function Fobj is defined as
nexp
obj
i)1
fexp
- fcalc
i
i
fexp
i
(13)
6932
xp
temperature
range [K]
Monoethers
215.98
220.59
236.19
235.89
236.95
217.84
230.20
237.92
240.24
231.49
221.35
0.4977
0.3474
0.2947
0.2322
0.1931
0.4007
0.3639
0.3276
0.2900
0.3248
0.2966
200-400
200-466
250-520
300-580
350-610
280-420
220-460
200-500
250-530
300-490
250-500
0.80
0.72
0.47
0.63
0.36
0.35
0.92
0.28
0.36
0.75
3.32
3.5850
3.5973
3.5556
3.5319
Diethers
234.98
239.59
221.20
223.34
0.8602
0.9451
0.5955
0.6806
250-470
350-520
300-510
300-520
4.6265
6.6346
7.8270
3.5194
3.4077
3.4184
Polyethers
225.62
214.38
225.24
0.9078
0.7401
0.7082
44.05
58.08
58.08
72.11
72.11
1.4953
2.0105
1.9227
2.1875
2.2846
methyl formate
ethyl formate
propyl formate
butyl formate
methyl acetate
ethyl acetatef
propyl acetate
butyl acetate
methyl propionate
ethyl propionate
propyl propionate
60.053
74.08
88.11
102.13
74.08
88.11
102.13
116.16
88.11
102.13
116.16
1.8742
2.2246
2.4498
2.9234
2.3967
2.7481
3.1606
3.6600
2.7813
3.1522
3.4836
3.5425
3.6793
3.8039
3.7940
3.5477
3.6511
3.6866
3.6751
3.5969
3.6463
3.7476
acetone
2-butanone
2-pentanone
3-pentanone
2-hexanone
3-hexanone
2-heptanone
4-heptanone
2-octanone
3-octanone
2-nonanone
5-nonanone
2-undecanone
6-undecanone
2-tridecanone
58.078
72.1
86.13
86.13
100.16
100.16
114.19
114.19
128.22
128.22
142.24
142.24
170.3
170.3
198.35
2.221
2.418
2.826
2.812
3.232
3.202
3.704
3.651
4.002
4.134
4.55
4.448
5.441
5.399
6.25
component
molecular weight,
Mw [g/mol]
dimethyl ether
diethyl etherf
di-n-propyl ether
di-n-butyl ether
di-n-pentyl ether
methyl ethyl ether
methyl n-propyl ether
methyl n-butyl ether
methyl n-pentyl ether
ethyl n-propyl ether
diisopropyl ether
46.069
74.123
102.177
130.23
158.28
60.1
74.123
88.15
102.177
88.15
102.177
2.0090
2.8787
3.3930
4.3064
5.1782
2.4953
2.7480
3.0529
3.4480
3.0791
3.3721
3.4343
3.5549
3.7425
3.7429
3.7474
3.4580
3.6183
3.6801
3.7199
3.7021
3.7856
dimethoxymethane
1,2-dimethoxyethane
diethoxymethanef
1,2-diethoxyethane
76.095
90.122
104.149
118.17
2.4994
2.9626
3.6103
4.1143
DEG DMEb,f
TRG DMEc
TEG DMEd
134.17
178.23
222.282
ethylene oxide
1,2-propylene oxidef
1,3-propylene oxide
1,2-butene oxide
tetrahydrofuran
a [D]
xpm
0.90
0.90
1.14
0.71
2.06
1.30
1.12
1.28
0.67
1.30
1.84
1.3
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
0.98
0.38
0.25
0.56
0.43
1.92
1.86
1.30
1.2
1.2
1.2
1.2
2.15
2.8
2.15
2.8
350-600
300-620
400-680
2.32
0.39
0.30
1.36
2.18
3.66
1.2
1.2
1.2
4.2
4.91
5.54
170-455
310-470
260-510
200-510
200-530
3.01
2.21
2.37
1.66
0.44
1.55
1.87
1.68
2.62
1.40
1.7
2.0
1.8
1.7
1.75
0.8
0.8
0.8
0.8
0.8
Esters
232.19
251.54
252.77
249.41
238.87
236.99
238.87
237.43
240.92
236.76
241.51
0.8004
0.6743
0.6123
0.5131
0.6259
0.5458
0.4746
0.4098
0.5393
0.4759
0.4306
200-470
210-495
215-550
215-550
200-480
215-485
200-530
230-560
200-515
215-545
260-560
1.66
2.06
1.91
2.25
1.29
1.13
1.41
0.78
1.41
0.32
2.09
1.36
1.46
2.75
3.69
1.66
1.64
1.41
0.53
2.70
0.71
2.78
1.75
1.96
1.91
1.90
1.7
1.84
1.86
1.86
1.7
1.75
1.79
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
Ketonese
3.607908253 259.99
3.689051518 270
3.710210701 264.97
3.705656195 265.83
3.730568917 263.8
3.732817265 262.1
3.731131258 259.17
3.745135035 255.72
3.752375796 257.07
3.720417659 254.12
3.743460108 256.81
3.765670418 256.25
3.742901466 253.8
3.745693011 251.65
3.762355566 253.34
0.2258
0.2074
0.177
0.1774
0.1543
0.156
0.136
0.135
0.1254
0.12
0.1101
0.1125
0.0919
0.0924
0.0799
253-463
270-374
282-353
285-347
299-332
299-324
306-416
275-384
319-420
316-360
340-422
301-356
309-427
303-352
341-427
4.726
0.647
0.235
0.137
0.025
0.036
0.556
0.864
1.523
0.327
0.099
0.053
0.047
0.183
0.022
1.338
0.498
0.033
0.197
0.013
0.01
0.638
9.703
12.33
3.671
0.155
0.013
0.144
1.305
0.177
2.7
2.7
2.7
2.7
2.7
2.7
2.7
2.7
2.7
2.7
2.7
2.7
2.7
2.7
2.7
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
[]
/k [K]
a Values of the segment dipole moment used in the calculations. In the case of monofunctional molecules, it is the experimental value
of the molecular dipole moment. b Diethylene glycol dimethyl ether. c Triethylene glycol dimethyl ether. d Tetraethylene glycol dimethyl
ether. e Parameters for ketones taken from ref 22. f The following binary systems were used in the fitting procedure: diethyl ether +
n-hexane (from ref 47), diethoxymethane + n-heptane (from refs 45 and 46); 1,2-propylene oxide + n-hexane (from ref 38); DEG DME +
n-decane (from ref 45); and ethyl acetate + n-heptane (from ref 42).
Ind. Eng. Chem. Res., Vol. 44, No. 17, 2005 6933
Table 2. Pure-Component Parameters for Ethers and Esters Obtained for PC-SAFT + Fischer
AAD%
Pvap
xp
temperature
range [K]
Monoethers
3.5652
223.76
3.6768
230.82
3.7797
241.81
3.4899
223.44
3.6414
211.26
0.7550
0.6145
0.5170
0.8545
0.5749
200-450
250-520
300-580
280-420
250-500
0.29
0.35
2.71
0.46
2.18
3.1970
Diethers
3.4819
225.81
0.6397
300-500
134.175
222.282
4.7104
7.9200
Polyethers
3.4839
225.81
3.3661
227.43
0.6397
0.325
1.2-propylenoxide
1.3-propylenoxide
tetrahydrofuran
58.08
58.08
72.12
2.1341
1.9754
2.2631
methyl formate
ethyl formate
propyl formate
ethyl acetate
n-propyl acetate
n-butyl acetate
methyl propionate
ethyl propionate
propyl propionate
60.053
74.08
88.11
88.11
102.13
116.16
88.11
102.13
116.16
2.3829
2.5818
2.9067
3.1878
3.2563
3.6102
3.0235
3.4309
3.7225
component
diethyl ether
di-n-propyl ether
di-n-butyl ether
methyl ethyl ether
diisopropyl ether
1,2-dimethoxyethane
DEG DMEb
TEG DMEc
molecular weight,
Mw [g/mol]
74.12
102.177
130.23
60.1
102.177
2.8311
3.5577
4.0882
2.4254
3.6883
90.122
a [D]
xpm
1.43
1.47
5.04
1.47
3.28
1.22
1.21
1.2
1.22
1.26
2.14
2.17
2.11
2.07
2.12
1.04
1.21
1.71
2.73
300-500
410-680
0.8
2.73
1.18
2.63
1.97d
2.45d
3.00
2.57
310-470
280-510
250-500
3.92
2.68
0.78
1.62
0.18
0.75
2
1.8
1.75
1.95
1.85
1.95
Esters
239.57
233.64
241.65
221.85
237.44
240.05
238.65
231.56
234.61
180-480
200-500
220-520
190-510
263-548
200-560
220-520
200-540
260-560
1.13
0.67
0.38
0.43
1.86
0.8
0.84
0.67
2.5
0.99
1.85
1.61
1.72
1.44
2.65
1.96
0.97
2.52
1.75
1.96
1.91
1.84
1.86
1.86
1.7
1.75
1.79
2.01
2.32
2.44
2.68
2.78
2.95
2.59
2.85
2.93
[]
3.2219
3.4424
3.5409
3.4284
3.5692
3.6721
3.4717
3.5421
3.5877
/k [K]
0.8431
0.8988
0.8399
0.8406
0.8537
0.8169
0.8561
0.8297
0.787
a Molecular dipole moments used in the calculations. Values taken from ref 49. b Diethylene glycol dimethyl ether. c Tetraethylene
glycol dimethyl ether. d Values taken from ref 50. e The following binary systems were used in the fitting procedure: diisopropyl ether +
n-heptane (from ref 45); 1,2-dimethoxyethane + n-heptane (from ref 45); 1,2-propylene oxide + n-hexane (from ref 38); DEG DME +
n-decane (from ref 45); TEG DME + n-heptane (from ref 43); and ethyl acetate + n-heptane (from ref 42).
Figure 1. Vapor-liquid equilibrium for the 1,2-propylene oxidehexane system. The solid line represents Polar PC-SAFT, and
the dashed line represents PC-SAFT + Fischer; the binary
interaction parameter was set to zero in both cases. Symbols are
experimental data by Bougard and Jadot.38
Figure 2. Vapor-liquid equilibrium for the butyl acetatecyclohexane system. The solid line represents Polar PC-SAFT,
and the dashed line represents PC-SAFT + Fischer; the binary
interaction parameter was set to zero in both cases. Symbols are
experimental data from the Dechema compilation.39
set to zero. This is not the case for the original PCSAFT, which again does not capture the nonideal
behavior of the mixture.
The case of mixtures containing two polar components
was also examined, and good results were observed with
both polar terms. Such mixtures show almost-ideal
behavior, because of the similarity of both components;
therefore, they are not as challenging a test for the polar
terms as the strongly nonideal mixtures that contain
polar and nonpolar components.
6934
polar sites (2,4-pentadione) has been previously considered in the framework of Polar PC-SAFT. The results
obtained by Sauer and Chapman22 for the 2,4-pentadione + cyclohexane system were very good, but applying the model to only one system that contains a
component with more than one polar site is not sufficient for proposing a methodology for modeling systems that contain components with multiple polar
groups. In this work, parameters were obtained for two
difunctional and several polyfunctional ethers (see
Tables 1 and 2). The results obtained from both models
for systems including polyethers reveal the differences
between Polar PC-SAFT and PC-SAFT + Fischer.
Figure 5. Vapor-liquid equilibria of the di-n-propyl etherheptane and diethoxymethane-heptane systems from Polar PCSAFT. Binary interaction parameters set to zero. Symbols are
experimental data from Treszczanowicz et al.45,46
Figure 6. Vapor-liquid equilibria of the 1,2-dimethoxyethaneheptane and 1,2-diethoxyethane-heptane systems from Polar PCSAFT. Binary interaction parameters set to zero. Symbols are
experimental data from Treszczanowicz et al.45,46
Ind. Eng. Chem. Res., Vol. 44, No. 17, 2005 6935
Figure 7. Vapor-liquid equilibrium of the 1,2-dimethoxyethaneheptane system from PC-SAFT + Fischer. Binary interaction
parameters set to zero. Dashed line: segment dipole moment of
1.2 D used in the calculations. Solid line: experimental molecular
dipole moment of 1.71 D used in the calculations. Symbols are
experimental data from Treszczanowicz and Lu.45
6936
Ind. Eng. Chem. Res., Vol. 44, No. 17, 2005 6937
6938