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J. Chem. Thermodynamics
journal homepage: www.elsevier.com/locate/jct
Departamento de Qumica Fsica, Facultad de Ciencias, Universidad de Zaragoza, 50009 Zaragoza, Spain
Technische Chemie, Universitt Oldenburg, D-26111 Oldenburg, Germany
a r t i c l e
i n f o
Article history:
Received 6 February 2012
Received in revised form 26 February 2012
Accepted 28 February 2012
Available online 9 March 2012
Keywords:
Density
Isothermal (vapour + liquid) equilibrium
Isomeric chlorobutane
Butyl ethyl ether
VTPR model
a b s t r a c t
Densities of the binary systems containing an isomer of chlorobutane (1-chlorobutane, 2-chlorobutane,
2-methyl-1-chloropropane, or 2-methyl-2-chloropropane) and butyl ethyl ether have been measured
over the temperature range (283.15 to 313.15) K. Moreover, isothermal (vapour + liquid) equilibria have
also been determined at three temperatures (T = (288.15, 298.15, and 308.15) K). Excess properties have
been obtained from the experimental data and correlated. Finally, the VTPR model has been used to predict densities and (vapour + liquid) equilibria of the binary systems studied.
2012 Elsevier Ltd. All rights reserved.
1. Introduction
In many chemical engineering areas such as process design and
purication techniques, a reliable estimation of thermodynamic
properties as a function of composition, temperature and pressure
is particularly important. In the last years our research group has
made a considerable effort on the measurement of thermodynamic
properties of liquid mixtures containing ethers and halogenated
compounds [14]. In this contribution, we report densities over the
temperature range (283.15 to 313.15) K and isothermal (vapour +
liquid) equilibrium data at T = (288.15, 298.15 and 303.15) K for
the four binary mixtures formed by an isomeric chlorobutane
and butyl ethyl ether. From these experimental properties, excess
volumes and excess Gibbs energies have been obtained at different
temperatures.
In addition, the reliability of the predictions of the densities and
(vapour + liquid) equilibria of the volume translated PengRobinson
group contribution equation of state (VTPR model) [57] was
checked by comparing the experimental information with the model predictions. This model that combines the UNIFAC model [8,9]
with the volume translated PengRobinson equation of state
[10,11], is a useful way for predicting the thermodynamic properties
of complex mixtures. It has been successfully applied to predict a
variety of properties of nonpolar, polar, sub-critical, supercritical,
Corresponding author.
E-mail address: celadi@posta.unizar.es (C. Lafuente).
0021-9614/$ - see front matter 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.jct.2012.02.039
151
Source
Initial mass
fraction purity
1-Chlorobutane
2-Chlorobutane
1-Chloro-2-methylpropane
2-Chloro-2-methylpropane
Butyl ethyl ether
Aldrich
Aldrich
Fluka
Aldrich
Aldrich
0.99
0.99
0.99
0.99
0.99
Purication
method
Final mass
fraction
purity
Analysis
method
0.99
0.99
0.99
0.99
0.99
TABLE 2
Properties of the pure compounds and comparison of densities and vapour pressures with literature data at T = 298.15 K.
Compound
T/K
qexp(g cm3)
1-Chlorobutane
283.15
288.15
293.15
298.15
303.15
308.15
313.15
0.897339
0.891855
0.886335
0.880705
0.875204
0.869585
0.863882
283.15
288.15
293.15
0.884340
0.878756
0.873130
298.15
303.15
308.15
313.15
0.867474
0.861779
0.856044
0.850266
283.15
288.15
293.15
0.888845
0.883211
0.877539
298.15
303.15
308.15
313.15
0.871833
0.866096
0.860319
0.854502
283.15
288.15
293.15
298.15
0.855249
0.849243
0.843191
0.837096
303.15
308.15
313.15
283.15
288.15
293.15
0.830958
0.824772
0.818536
0.759632
0.754838
0.750018
298.15
303.15
308.15
313.15
0.745173
0.740300
0.735393
0.730451
2-Chlorobutane
1-Chloro-2-methylpropane
2-Chloro-2-methylpropane
of reading [18]. The composition of both phases (liquid and condensed vapour) has been determined by means of a densitometric
analysis. The estimated error in the determination of liquid and
vapour mole fractions is estimated to be 0.0002.
The values of the properties of the pure compounds at work
temperatures are collected in table 2 together with literature
values of density and vapour pressure at T = 298.15 K [1926].
qlit(g cm3)
pexp/kPa
plit/kPa
8.400
0.88075 [19]
13.515
0.8671 [20]
1722
13.360
1815
20.969 [23]
1641
31.550
1492
13.000
1896
19.851 [24]
1691
30.450
1522
26.420
1209
40.130
0.7448 [21]
13.499 [22]
1560
20.350
0.8362 [21]
1914
21.035
20.905
0.8717 [21]
40.054 [25]
1140
59.520
1076
4.475
3190
7.550
12.240
7.51 [26]
2804
2490
V E x1 x2
n
P
Ai x1 x2 i ;
i0
152
FIGURE 1. Excess volumes for the binary mixture {1-chlorobutane (1) + butyl ethyl
ether (2)}: () experimental data; () RedlichKister correlation.
FIGURE 2. Excess volumes for the binary mixture {2-chlorobutane (1) + butyl ethyl
ether} (2): () experimental data; () RedlichKister correlation.
153
A0
283.15
288.15
293.15
298.15
303.15
308.15
313.15
283.15
288.15
293.15
298.15
303.15
308.15
313.15
283.15
288.15
293.15
298.15
303.15
308.15
313.15
283.15
288.15
293.15
298.15
303.15
308.15
313.15
A1
A2
A3
r (VE)
0.0676
0.0791
0.0845
0.1063
0.1162
0.1190
0.1232
0.0014
0.0013
0.0013
0.0013
0.0013
0.0013
0.0012
ether
0.5356
0.5275
0.5211
0.5150
0.5117
0.5065
0.5008
ether
0.1442
0.1652
0.2242
0.2346
0.2447
0.2491
0.2588
ethyl ether
0.0696
0.0637
0.0508
0.0582
0.0768
0.0783
0.0644
ethyl ether
0.0993
0.1204
0.1232
0.1455
0.1611
0.1832
0.2074
0.0018
0.0016
0.0007
0.0012
0.0013
0.0014
0.0015
0.0011
0.0010
0.0011
0.0009
0.0011
0.0010
0.0007
0.0014
0.0014
0.0013
0.0015
0.0016
0.0016
0.0018
The pressurecomposition diagrams, px1y1, are shown in gure 58. The Wilson equation [27] has been employed to correlate
the activity coefcients of the components in the liquid phase:
lnci ln
Kij
!
xj Kij
1
P xk Kki
P
;
k
j xj Kkj
V j
kij kii
exp
;
V i
RT
where ci and xi are the activity coefcient and mole fraction of component i in the liquid phase, (kijkij) are the Wilson parameters, V i is
the molar volume of component i in the liquid phase at T = 298.15 K,
R is the general gas constant and T is the absolute temperature.
The Wilson parameters have been tted by minimizing the following objective function [28]:
exp
2
n
P
p pcal
:
pexp
i1
i
FIGURE 5. px1y1 Diagrams for the binary mixture {1-chlorobutane (1) + butyl
ethyl ether (2)}: (h,j) experimental data at T = 288.15 K; (,) data at T = 298.15 K;
(D,N) data at T = 308.15 K; () Wilson correlation; ( ) VTPR prediction.
pcal
2
P
"
xi ci pi exp
i1
#
V i Bii p pi 1 yi 2 pdij
;
RT
being yi the vapour phase mole fractions, p the total pressure, pi the
vapour pressure of the pure compound i, Bii the second virial coefcient of component i that, for 1-chlorobutane, 2-chlorobutane
and 2-chloro-2-methylpropane were taken from TRC tables [20],
and for 1-chloro-2-methylpropane and butyl ethyl ether were estimated using the Tsonopoulos method [29,30], Bij the cross second
virial coefcient calculated using a suitable mixing rule [31], the
rest of the symbols have been previously dened.
Parameters of the Wilson equation together with average deviations in pressure, Dp and vapour phase composition, Dy, for each
binary system are gathered in table 4.
The thermodynamic consistency of the experimental results
was satisfactorily checked by means of the van Ness method
[32], described by Fredenslund et al. [33] using the Wilson equation for tting the excess Gibbs energies, the Dy values for all
the mixtures are given in table 4, all of them are less than 0.01.
The (vapour + liquid) equilibrium data together with the
activity coefcients and excess Gibbs energies calculated using
TABLE 4
Correlation parameters of the Wilson equation, average deviation in pressure, Dp, and average deviation in vapour phase composition, Dy.
System
k12k11/(J mol1)
k21k22/(J mol1)
Dp/kPa)
Dy
2025.50
74.12
1552.08
2601.70
1734.18
134.54
1432.90
1855.85
0.051
0.104
0.070
0.087
0.0033
0.0065
0.0062
0.0054
154
FIGURE 6. px1y1 Diagrams for the binary mixture {2-chlorobutane (1) butyl ethyl
ether (2)}: (h,j) experimental data at T = 288.15 K; (,) data at T = 298.15 K; (D,N)
data at T = 308.15 K; () Wilson correlation; ( ) VTPR prediction.
FIGURE 9. Plot of excess Gibbs energy, GE, against mole fraction for the binary
mixture {1-chlorobutane (1) + butyl ethyl ether (2)} from T = (288.15 to 308.15) K.
FIGURE 10. Plot of excess Gibbs energy, GE, against mole fraction for the binary
mixture {2-chlorobutane (1) + butyl ethyl ether (2)} at T = (288.15 to 308.15) K.
155
FIGURE 12. Plot of excess Gibbs energy, GE, against mole fraction for the binary
mixture {2-chloro-2-methylpropane (1) + butyl ethyl ether (2)} at T = (288.15 to
308.15) K.
The GE values are positive at the three temperatures in the systems containing 2-chlorobutane or 2-chloro-2-methylpropane,
while they are negative in the mixture with 1-chloro-2-methylpropane. Finally, GE values at T = 288.15 K are negative for the system
(1-chlorobutane + butyl ethyl ether) and at higher temperatures GE
curves for this system exhibit a sigmoidal shape, with positive GE
values located in the ether rich region. The temperature dependence of the excess Gibbs energies is small for all the mixtures,
GE values almost do not change for the mixture containing 2-chlorobutane, while they slightly increase when temperature rises for
the mixtures containing 1-chlorobutane, 1-chloro-2-methylpropane or 2-chloro-2-methylpropane.
The activity coefcients very close to unity and the small GE and
E
V values obtained for all the systems reveal a quasi-ideal thermodynamic behaviour that is due to the existence of a balance between two opposite energetic phenomena: the weakening of like
interactions and the formation of new ClO interactions between
unlike molecules, making that the studied properties show small
absolute values. This behaviour is similar to that of the mixtures
isomeric chlorobutane with methyl tert-butyl ether or diisopropyl
ether previously characterized.
4. VTPR model predictions
FIGURE 11. Plot of excess Gibbs energy, GE, against mole fraction for the binary
mixture {1-chloro-2-methylpropane (1) + butyl ethyl ether (2)} at T = (288.15 to
308.15) K.
We have used the volume translated PengRobinson group contribution equation of state (VTPR model) to predict simultaneously
the densities and (vapour + liquid) equilibria of the mixtures studied here. This model combines the VTPR-EoS with the UNIFAC
group contribution method.
The VTPR equation of state is:
RT
aT
;
V c b V cV c b bV c b
156
TABLE 5
Properties of the pure compounds: critical data acentric factor, translation parameter, and PR-Twu a-function parameters.
Compound
Pc/kPa
Tc/K
Vc/(cm3 mol1)
c/(cm3 mol1)
1-Chlorobutane
2-Chlorobutane
1-Chloro-2-methylpropane
2-Chloro-2-methylpropane
Butyl ethyl ether
3688.23
3951.67
3989
3951.68
3039.750
542
520.6
527.05
507
531
312
305
305
295
390
0.218
0.3
0.2895
0.19
0.37710
7.8901
6.6453
4.2832
10.2783
7.5039
0.988925
0.947079
0.859223
0.109132
0.755636
0.75593
1.06718
1.00272
0.890767
0.726617
0.654863
0.870236
0.878194
3.52574
1.03005
TABLE 6
VTPR group interaction parameters.
n
anm/K
bnm
cnm/
K1
anm/K
bnm
cnm/
K1
1
1
2
2
3
3
439.8547
442.698
4.375
0.46183
0.52665
0
0
0
0
87.8717
112.4874
13.125
0.10659
0.22864
0
0
0
0
FIGURE 14. Plot of density against mole fraction for the binary mixture {2chlorobutane (1) + butyl ethyl ether (2)} from T = (283.15 to 313.15) K: ()
experimental data; ( ) VTPR prediction.
c
FIGURE 13. Plot of density against mole fraction for the binary mixture {1chlorobutane (1) + butyl ethyl ether (2)} from T = (283.15 to 313.15) K: ()
experimental data; ( ) VTPR prediction.
where the translation parameter, c, is dened as the difference between the volume calculated with the PengRobinson-EoS and the
experimental volume at a reduced temperature, Tr = 0.7 [13].
In the VTPR model, the following mixing rules for the parameters a and b, suggested by Chen et al. [34], are used:
a X aii GEres
xi
;
b
bii
A
PP
i
3=4
bij
xi xj bij ;
3=4
3=4
bii bjj
2
10
P
xi c i :
11
Properties of the pure compounds and group interaction parameters used in the VTPR calculations are collected in tables 5 and 6,
respectively, all these properties and parameters are directly taken
from Dortmund Data Bank [35].
In gures 1316, the predicted densities over the whole composition range together with the experimental densities are shown in
gures 58 the predicted pressure-composition diagrams along
with the experimental ones are graphically shown.
We have tested the accuracy of the VTPR predictions by comparing the densities, pressures and vapour-phase compositions obtained experimentally with the corresponding calculated values. In
table 7, the average deviations in density, pressure and vapour
phase composition are shown. The overall Dq average is
0.009466 g cm3, being the predictions more accurate in the chlorobutane rich region; the best results are obtained for the mixture
containing 1-chlorobutane with an average Dq of 0.006886 g cm3
while the less accurate predictions correspond to the mixture with
2-chlorobutane with an average Dq of 0.013312 g cm3. Taking
into account the difculty of predicting this property, the density
157
TABLE 7
Average deviation in density, Dq, in vapour pressure, Dp, and in vapour phase
composition, Dy. Differences calculated between experimental data and VTPR model
predictions.
System
Dq/
(g cm3)
Dp/
kPa
Dy
0.006886
0.013312
0.007985
0.077
0.173
0.120
0.0030
0.0039
0.0033
0.009679
0.309
0.0054
0.009466
0.170
0.0039
containing 1-chlorobutane with pressure and vapour-phase composition deviations 0.077 kPa and 0.0030 respectively, in this case,
the highest deviations between experimental and predicted values
are presented by the mixture 2-chloro-2-methyl-propane + butyl
ethyl ether with Dp = 0.309 kPa and Dy = 0.0054. These values
indicate that the VTPR model provides very satisfactory predictions
of the isothermal (vapour + liquid) equilibria of these systems.
5. Conclusions
FIGURE 15. Plot of density against mole fraction for the binary mixture {1-chloro2-methylpropane (1) + butyl ethyl ether (2)} from T = (283.15 to 313.15) K: ()
experimental data; ( ) VTPR prediction.
FIGURE 16. Plot of density against mole fraction for the binary mixture {2-chloro2-methylpropane (1) + butyl ethyl ether (2)} from T = (283.15 to 313.15) K: ()
experimental data; ( ) VTPR prediction.
predictions obtained with the VTPR model can be considered satisfactory. With respect to the VLE predictions, the overall Dp average
is 0.170 kPa and the corresponding overall average for Dy is
0.0039, the best predictions are obtained again for the mixture
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JCT-12-82