Article

pubs.acs.org/jced

Solvent Eects on VaporLiquid Equilibria of the Binary System

1Hexene + nHexane
Beatriz Marrufo, Ben Rigby, Jordi Pla-Franco, and Sonia Loras*,

Departamento de Ingeniera Qumica Basica, Universidad del Zulia, 4011, Maracaibo, Venezuela
Departamento de Ingeniera Qumica, Escuela Tecnica Superior de Ingeniera, Universitat de Valencia, 46100 Burjassot, Valencia,
Spain

ABSTRACT: In order to study the separation of 1-hexene and n-hexane, two solvents, 2-pentanol and ethyl-butyrate, are tested as possible entrainers for an extractive
distillation. In this way, isobaric vaporliquid equilibrium (VLE) data at 100 kPa
have been measured for the two ternary systems formed by the initial mixture and
one of the mentioned solvents: 1-hexene + n-hexane + ethyl butyrate and 1-hexene +
n-hexane + 2-pentanol. VLE data for the four constituent binary systems have also
been measured. These systems are 1-hexene + ethyl butyrate, n-hexane + ethyl butyrate,
1-hexene + 2-pentanol, and nally n-hexane + 2-pentanol. All binary systems show
moderate positive deviations from the ideal behavior and do not form an azeotrope.
The well-known local composition models Wilson, UNIQUAC, and NRTL have been
used for correlating VLE data. Prediction with the UNIFAC method has been also
obtained.

INTRODUCTION
Olens and parans have very similar boiling points and are only
separated by a few degrees in temperature. When this occurs,
conventional distillation is not a recommended technique due its
expensive cost, as a consequence of the high reux ratios and
large number of stages required for carrying out the separation. In these cases, one alternative is extractive distillation, which
uses a third component called an entrainer to alter the relative
volatility of the components to be separated. However, only a
few specic solvents allow an ecient and economical extractive
distillation process; thus, entrainer selection is a crucial step during the design stage. The choice of entrainer can be carried out
correctly with complete and accurate vaporliquid equilibrium
(VLE) data of the systems formed by the components to be
separated and the possible solvent.
The present work tackles a part of thermodynamic research on
the separation of paran and olen mixtures using dierent
solvents. In this work, the initial mixture is formed by 1-hexene
and n-hexane, and ethyl butyrate and 2-pentanol are the entrainer
candidates due to certain alcohols and esters being recommended
as entrainers for separation of hydrocarbons.1 An ideal entrainer
will increase the relative volatility considerably between the 1-hexane
and hexane and it will be very selective. Another important characteristic that makes an entrainer more suitable is that it is one of the
so-called ecofriendly solvents. In the present paper, both proposed
compounds can be considered green solvents.
In this work, we measured isobaric VLE data for the two ternary
systems 1-hexene (1) + n-hexane (2) + ethyl butyrate (3) and 1hexene (1) + n-hexane (2) + 2-pentanol (3) and four constituent
binary systems 1-hexene (1) + ethyl butyrate (3), n-hexane (2) +
ethyl butyrate (3), 1-hexene (1) + 2-pentanol (3), and n-hexane
(2) + 2-pentanol (3) at 100 kPa. In a previous paper,2 we reported
2012 American Chemical Society

VLE data for the binary system 1-hexene (1) + n-hexane (2).
Isobaric VLE data of binary hexane + 2-pentanol system was
obtained by Linek et al.3 at dierent pressures but none was
recorded at 100 kPa. However, for the other binary systems and for
the ternary systems, no VLE data have been previously published.

EXPERIMENTAL SECTION
Chemicals. The chemicals 1-hexene (99+ % mass), ethyl
butyrate (100 w 99.5, puriss. p.a.) and 2-pentanol (100 w 99)
were supplied by Sigma-Aldrich and the chemical n-hexane
(99.5+ % mass) was supplied by Fluka. Purity grade of 2-pentanol
was increased to 99.99 % after being treated in a batch multistage
rectication process in a Fischer SPALTROHR HMS-500 column.
The other reagents were used without further purication since
impurities are smaller than the detection limit of the analytical
method used. The specications of the used chemicals are summarized in Table 1.

Table 1. Specications of Chemical Samples

chemical
name
n-hexane
1-hexene
ethyl butyrate
2-pentanol
a

source

initial mass
fraction
purity

purication
method

Fluka
Aldrich
Aldrich
Aldrich

0.9950
0.9900
0.9900
0.9900

none
none
none
distillation

nal mass
fraction
purity

analysis
method

0.9999

GCa
GCa
GCa
GCa

Gasliquid chromatography.

Received: September 3, 2012

Accepted: October 25, 2012
Published: November 12, 2012
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Table 2. Experimental Vapor Pressure (P0i ) of Ethyl Butyratea

Apparatus and Procedure. The VLE data and the vapor

pressure of the pure compounds were determined using a
dynamic-recirculating still (Pilodist VLE 100 D) equipped with a
Cottrell circulation pump. This still is capable of handling pressures from 0.25 to 400 kPa, and temperatures up to 523 K.
The equilibrium temperature was measured with a digital Hart
Scientic thermometer, model 1502A, and a Hart Scientic Pt 100
probe, model AlB0888, calibrated at the Spanish Instituto Nacional
de Tecnica Aeroespacial. The uncertainty is estimated to be 0.02 K.
A Pilodist M101 pressure control system was used to measure and
control the pressure and the heating power. The pressure is kept
constant by means of a vacuum pump with and an electrovalve.
The manometer was calibrated using the vapor pressure of
ultrapure water. The uncertainty is estimated to be 0.05 kPa.
In each VLE experiment, rst step was to x and hold the
pressure using a vacuum pump, and then turn on the heating and
stirring systems of the liquid mixture. The experiment was running at constant pressure until equilibrium was reached. Equilibrium conditions were assumed when no changes in temperature and pressure were recorded. Then, samples of liquid and
condensate vapor were taken for analysis. To verify equilibrium
conditions, the vapor and liquid were continuously analyzed until
a value less than 0.001 of the variation of the mole fraction of
both liquid and vapor phase was reached. The sample extractions
were carried out with special syringes which allowed the withdrawal of small volume samples.
Analysis. Compositions of the liquid and condensed phases
were determined using a Varian CP-3800 gas chromatograph
(GC), after calibration with gravimetrically prepared standard solutions. A ame ionization detector was used together with a 30 m,
0.25 mm i.d. capillary column CP-Wax 52 CB. The GC response
peaks were treated with Varian Star No. 1 for MS Windows. The
column, injector, and detector temperatures were (353.15, 473.15,
and 493.15) K, respectively, for all systems. Very good peak
separation was achieved under these conditions, and calibration
analyses were carried out to convert the peak area ratio to the
mass composition of the sample. The average absolute deviation in the mole fraction was usually less than 0.001.

RESULTS AND DISCUSSION

Pure Component Vapor Pressures. The pure component
vapor pressures for ethyl butyrate and the pure component vapor
pressures for 2-pentanol, P0i , were determined experimentally
using the same equipment as that used to obtain the VLE data.
The pertinent results appear in Table 2 for ethyl butyrate and
in Table 3 for 2-pentanol. The measured vapor pressures were
correlated using the Antoine equation:
Bi
T /K + Ci

P/kPa

T/K

P/kPa

22.50
25.00
27.50
30.03
32.51
35.02
37.52
40.04
42.51
45.03
47.51
50.01
52.51
55.03
57.52
60.00

379.48
380.68
381.82
382.96
384.07
385.13
386.19
387.22
388.21
389.17
390.12
391.06
391.95
392.83
393.71
394.13

65.03
67.53
70.00
72.52
75.01
77.51
79.99
82.52
85.02
87.54
89.98
92.53
94.92
97.45
100.01
101.31

u(T) = 0.02 K, and u(p) = 0.05 kPa.

Table 3. Experimental Vapor Pressure (P0i ) of 2-Pentanola

ln Pi0/kPa = Ai

T/K
348.97
351.83
354.39
356.76
359.00
361.08
363.04
364.86
366.66
368.24
369.87
371.44
372.86
374.31
375.67
376.95

T/K

P/kPa

T/K

P/kPa

354.47
356.60
358.86
360.81
362.76
364.38
366.00
367.49
369.03
370.52
371.77
373.05
374.33
375.51
376.68
377.81
378.95

22.55
25.05
27.47
30.03
32.55
35.08
37.56
40.03
42.51
45.07
47.54
50.02
52.58
55.03
57.48
60.03
62.45

379.97
381.01
381.96
382.90
383.88
384.79
385.64
386.56
387.35
388.19
389.00
389.76
390.55
391.31
392.07
392.26

65.05
67.58
70.03
72.56
75.05
77.59
80.03
82.58
85.01
87.55
90.09
92.52
95.02
97.55
100.03
101.38

u(T) = 0.02 K, and u(p) = 0.05 kPa.

Table 4. Antoine Coecients, eq 1

(1)

whose parameters Ai, Bi, and Ci are reported in Table 4 together

with the Antoine parameters for n-hexane and 1-hexene obtained
in a previous work2 and were tted by a nonlinear optimization
method to minimize the average relative deviation in pressure
(ARDP). The vapor pressures of ethyl butyrate were correlated
with an ARDP of 0.07 %. A value for the ARDP equal to 0.18 %
was obtained for the case of 2-pentanol. For both compounds
experimental data are in good agreement to the equation reported
by Reid et al.4 since this equation gives a correlation of the
experimental vapor pressures reported in this work with a
ARDP = 0.39 % for the ethyl butyrate and a ARDP = 1.01 % for
the 2-pentanol.

compound

Ai

Bi

Ci

1-hexene (1)a
n-hexane (2)a
ethyl butyrate (3)
2-pentanol (3)

15.1210
12.8239
14.2846
14.1880

3433.84
2178.19
3234.24
2684.71

9.47
76.39
59.59
111.86

Parameters obtained in ref 2.

Binary Systems. The temperature T and the liquid-phase xi,

and vapor-phase yi mole fractions at 100.0 kPa for the systems
1-hexene (1) + ethyl butyrate (3), n-hexane (2) + ethyl butyrate (3),
1-hexene (1) + 2-pentanol (3), and n-hexane (2) + 2-pentanol
(3) are reported in Tables 58 and plotted in Figures 14.
The activity coecients (i) were calculated from the following equation5 assuming nonideality of both liquid and vapor
phases:
ln i = ln

yP
i
xiPi0

(Bii ViL)(P Pi0)

P
+
RT
2RT

yyi k (2ji jk)

(2)

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Table 5. Experimental VaporLiquid Equilibrium Data

for the Binary System 1-Hexene (1) + Ethyl Butyrate (3)
at 100.0 kPaa

T/K

x1

y1

389.91
384.16
378.87
374.16
370.93
366.17
362.24
359.78
356.05
353.79
351.38
349.22
347.45
345.55
343.80
342.17
340.51
339.04

0.027
0.069
0.112
0.160
0.198
0.256
0.318
0.351
0.426
0.468
0.525
0.573
0.630
0.679
0.735
0.804
0.851
0.905

0.133
0.300
0.433
0.535
0.603
0.686
0.749
0.779
0.825
0.850
0.876
0.896
0.916
0.931
0.943
0.960
0.970
0.984

1.224
1.225
1.227
1.185
1.167
1.155
1.123
1.128
1.087
1.084
1.064
1.060
1.036
1.032
1.016
0.992
0.995
0.992

0.991
0.988
0.983
0.987
0.979
0.977
0.973
0.981
1.002
1.006
1.017
1.029
1.026
1.045
1.119
1.132
1.193
1.059

Table 7. Experimental VaporLiquid Equilibrium Data for the

Binary System 1-Hexene (1) + 2-Pentanol (3) at 100.0 kPaa

u(T) = 0.02 K, u(p) = 0.1 kPa, and u(x2) = u(y2) = 0.001.

a

Table 6. Experimental VaporLiquid Equilibrium Data

for the Binary System n-Hexane (2) + Ethyl Butyrate (3)
at 100.0 kPaa

T/K

x2

y2

391.29
388.09
380.32
375.04
371.15
366.84
364.07
359.85
357.90
355.64
353.83
352.05
350.37
349.07
347.72
346.41
345.27
344.13
343.07
342.44

0.015
0.038
0.098
0.148
0.195
0.251
0.294
0.373
0.418
0.472
0.520
0.573
0.633
0.682
0.730
0.783
0.833
0.878
0.925
0.954

0.085
0.192
0.398
0.517
0.596
0.671
0.709
0.778
0.804
0.832
0.852
0.873
0.891
0.905
0.921
0.935
0.947
0.963
0.978
0.987

1.677
1.594
1.509
1.459
1.396
1.353
1.306
1.256
1.218
1.184
1.155
1.127
1.090
1.065
1.052
1.033
1.016
1.013
1.007
1.004

0.994
0.984
0.983
0.983
0.985
0.994
1.023
1.017
1.036
1.061
1.098
1.13
1.201
1.269
1.308
1.408
1.559
1.558
1.571
1.552

x1

y1

0.017
0.032
0.056
0.100
0.125
0.150
0.215
0.282
0.344
0.395
0.456
0.515
0.577
0.628
0.681
0.734
0.789
0.841
0.895
0.949
0.983

0.140
0.268
0.395
0.568
0.626
0.678
0.778
0.834
0.873
0.892
0.910
0.923
0.933
0.940
0.947
0.953
0.958
0.961
0.971
0.983
0.994

2.136
2.323
2.179
2.058
2.006
1.939
1.854
1.731
1.628
1.559
1.468
1.395
1.314
1.255
1.206
1.155
1.104
1.062
1.030
1.005
0.992

0.999
0.963
0.969
0.939
0.983
0.974
0.973
0.992
0.968
1.010
1.041
1.099
1.181
1.267
1.383
1.536
1.796
2.300
2.686
3.368
3.639

u(T) = 0.02 K, u(p) = 0.1 kPa, and u(x2) = u(y2) = 0.001.

Table 8. Experimental VaporLiquid Equilibrium Data for the

Binary System n-Hexane (2) + 2-Pentanol (3) at 100.0 kPaa

u(T) = 0.02 K, u(p) = 0.1 kPa, and u(x1) = u(y1) = 0.001.

where T and P are the equilibrium temperature and pressure,

ViL is the molar liquid volume of component i, Bii and Bjj are the
second virial coecients of the pure gases, Poi is the purecomponent vapor pressure, Bij the cross second virial coecient
and

ij = 2Bij Bjj Bii

T/K
388.05
384.92
380.13
373.28
369.17
366.41
359.50
354.51
351.19
348.56
346.34
344.39
342.90
341.85
340.71
339.87
339.14
338.40
337.71
337.00
336.63

T/K

x2

y2

389.01
384.49
377.11
369.96
365.17
359.96
355.46
352.14
350.43
348.74
347.29
346.18
345.15
344.42
343.74
343.13
342.55
342.10
341.72
341.46

0.013
0.033
0.080
0.127
0.165
0.232
0.294
0.372
0.414
0.470
0.531
0.588
0.646
0.699
0.753
0.806
0.862
0.911
0.952
0.992

0.106
0.248
0.468
0.605
0.684
0.776
0.824
0.863
0.875
0.887
0.901
0.910
0.920
0.926
0.930
0.937
0.948
0.959
0.971
0.994

2.535
2.563
2.337
2.241
2.188
2.010
1.893
1.712
1.635
1.530
1.432
1.348
1.278
1.214
1.154
1.106
1.064
1.032
1.011
1.001

1.002
1.005
0.978
1.008
1.024
0.984
1.025
1.044
1.105
1.196
1.269
1.386
1.508
1.701
2.028
2.396
2.863
3.583
4.794
6.040

u(T) = 0.02 K, u(p) = 0.1 kPa, and u(x1) = u(y1) = 0.001.

coecient is adequate to describe the vapor phase of the pure

components and their mixtures, and liquid volumes of the
pure components are incompressible over the pressure range
under consideration. The molar virial coecients Bii and Bij
were estimated by the method of Hayden and OConnell6
using the molecular parameters suggested by Prausnitz et al.7
The critical properties of all components were taken from
DIPPR.8
According to the results, the binary systems show positive
deviations from ideal behavior and do not form any azeotrope.

(3)

The standard state for the calculation of activity coecients

is the pure component at the pressure and temperature of the
solution. Equation 2 is valid at low and moderate pressures
when the virial equation of state truncated after the second
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Figure 1. Experimental VLE data for the system 1-hexene (1) + ethyl
butyrate (3) at 100.0 kPa: , experimental data; solid line, smoothed
data using the NRTL model with the parameters given in Table 10;
dotteddashed line, predicted by UNIFAC method.

Figure 3. Experimental VLE data for the system 1-hexene (1) +

2-pentanol (3) at 100.0 kPa: , experimental data; solid line, smoothed
data using the NRTL model with the parameters given in Table 10,
dotteddashed line, predicted by UNIFAC method.

Figure 2. Experimental VLE data for the system n-hexane (2) +

ethyl butyrate (3) at 100.0 kPa: , experimental data; solid line,
smoothed data using the NRTL model with the parameters given
in Table 10; dotteddashed line, predicted by UNIFAC method.

Figure 4. Experimental VLE data for the system n-hexane (2) +

2-pentanol (3) at 100.0 kPa: , experimental data; solid line, smoothed
data using the NRTL model with the parameters given in Table 10,
dotteddashed line, predicted by UNIFAC method.

Table 9. Consistency Test Statistics for the Binary Systems

1-Hexene (1) + Solvent (3) and n-Hexane (2) + Solvent (3)

The thermodynamic consistency of the VLE data, for each

binary system, has been veried with the Fredenslund test.9
Pertinent consistency details and statistics are presented in Table 9,
and it can be seen that the consistency criteria (AADy < 0.01) was
achieved using a two parameter Legendre polynomial for the
binary systems with ethyl butyrate and three parameters for the
binary sytems with 2-pentanol.
The VLE data for each binary system have been correlated using
local composition models (Wilson, NRTL, and UNIQUAC) and
predicted by the UNIFAC contribution method.9,10 For the
Wilson model, molar liquid volumes of pure components have
been estimated with the Rackett equation,11 and for UNIQUAC
model, volume and surface parameters were taken from DECHEMA.12

system i + solvent (j)

A1a

A2a

1 + ethyl butyrate (3)

2 + ethyl butyrate (3)
1 + 2-pentanol (3)
2 + 2-pentanol (3)

0.1643
0.4726
1.0054
1.2294

0.0120
0.0845
0.3577
0.4009

A3a

100AAD yib

AAD
Pc/kPa

0.0610
0.0941

0.625
0.529
0.872
0.270

0.635
0.176
0.539
0.837

Legendre polynomial parameters. bAverage absolute deviation in

vapor-phase composition. cAverage absolute deviation in pressure.

The parameters of these models have been determined minimizing the following objective function (OF)
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Table 10. Parameters and Correlation Statistics for Dierent GE Models for the Ternary Systems 1-Hexene (1) + n-Hexane (2) +
Solvent (3)
model
Wilsonc

NRTL

UNIQUACf

UNIFACg

Wilsonc

Aij

Aji

system i + j

Jmol1

Jmol1

1 + 2d
1+3
2+3
1 + 2 + 3e
1 + 2d
1+3
2+3
1 + 2 + 3e
1 + 2d
1+3
2+3
1 + 2 + 3e
1 + 2d
1+3
2+3
1+2+3

171.69
200.90
30.68

1+3
2+3
1 + 2 + 3e
1+3
2+3
1 + 2 + 3e
1+3
2+3
1 + 2 + 3e
1+3
2+3
1+2+3

NRTL

UNIQUACf

UNIFAC

154.16
549.21
1992.99
78.87
188.21
625.83

343.44
15.18
4933.42
5239.21
2457.76
2644.33

bubble point
ij

Ethylbutyrate (3)
131.00
502.90
1744.60
195.66
148.65
237.06

0.2
0.3
0.3

88.58
380.77
201.10

2-Pentanol (3)
4984.29
5618.24
682.15
260.36
1042.08
1024.92

0.3
0.3

ARDTa/%

100AADy1b

0.056
0.191
0.054
0.218
0.056
0.190
0.054
0.217
0.056
0.189
0.054
0.225
0.062
0.230
0.518
0.290

0.115
0.651

0.138
0.136
0.164
0.151
0.270
0.258
0.132
0.242
0.225
1.395
0.970
1.051

0.885

0.473
0.116
0.654
0.473
0.116
0.653
0.486
0.072
0.752
0.487

0.338
0.951
0.341
0.897
0.368
1.141
0.879

100AADy2b

0.571
0.254

0.578
0.254

0.582
0.259

1.002
0.357

0.295
0.585
0.331
0.599
0.292
0.597
0.484
0.841

a
Average relative deviation in temperature. bAverage absolute in vapor phase composition. cMolar liquid volumes of pure components have been
estimated with the Rackett equation.11 dReference 2. eTernary estimation from binary parameters. fVolume and surface parameters from DECHEMA.12
g
Calculations based on UNIFAC.9,10

OF =

T expt T calc

i
i
expt
calc
y
y
+
|

i
i
Tiexpt

100
i=1

(4)

and are reported in Table 10, together with the obtained

average deviations of the correlation. An inspection of the
results given in that table shows that the three composition
models are adequate for the description of the VLE of the
binary systems, without any signicant dierence between
them. However, it must be pointed out that the deviations
obtained for the prediction with UNIFAC are larger.
Ternary Systems. VLE data for the ternary system 1-hexene
(1) + n-hexane (2) + ethyl butyrate (3) are reported in Table 11 and
Figure 5 and VLE data for the ternary system 1-hexene (1) +
n-hexane (2) + 2-pentanol (3) are reported in Table 12 and Figure 6.
The activity coecients (i) were calculated from eq 2, and the molar
virial coecients were estimated as well as for the binary systems.
The ternary data were found to be thermodynamically consistent by
the Wisniak and Tamir13 modication of the McDermottEllis
test.14 The test requires that D < Dmax for every experimental point,
where the local deviation D is given by

Figure 5. Diagram of VLE for the ternary system 1-hexene (1) +

n-hexane (2) + ethyl butyrate (3) at 100.0 kPa: , liquid-phase mole
fractions; , vapor-phase mole fractions.

D=

(xia + xib)(ln ia ln ib)

i=1

and N is the number of components. The maximum deviation

Dmax is given by

(5)
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Table 11. Experimental VaporLiquid Equilibrium Data for

the System 1-Hexene (1) + n-Hexane (2) + Ehtyl Butyrate (3)
at 100.0 kPaa
T/K

x1

x2

y1

y2

382.56
365.54
353.97
345.33
337.54
339.34
342.39
345.34
349.26
352.96
357.80
363.28
373.80
364.85
357.52
352.65
349.17
345.36
340.59
338.70
340.72
343.66
346.23
350.02
353.71
361.02
353.67
349.98
346.66
343.31
339.31
341.56
344.66
347.70
352.46
347.60
344.86
340.33
342.67
347.64
342.52
342.37

0.046
0.224
0.424
0.643
0.912
0.807
0.702
0.600
0.486
0.392
0.294
0.199
0.087
0.104
0.203
0.305
0.398
0.506
0.676
0.739
0.585
0.490
0.411
0.301
0.200
0.056
0.108
0.210
0.306
0.420
0.553
0.395
0.293
0.213
0.057
0.105
0.198
0.357
0.195
0.050
0.102
0.051

0.045
0.043
0.050
0.051
0.051
0.097
0.096
0.094
0.097
0.102
0.097
0.104
0.090
0.198
0.208
0.209
0.206
0.204
0.199
0.206
0.305
0.295
0.301
0.289
0.296
0.298
0.397
0.403
0.396
0.399
0.401
0.499
0.490
0.478
0.495
0.609
0.601
0.600
0.701
0.674
0.821
0.895

0.175
0.563
0.762
0.865
0.945
0.884
0.851
0.813
0.755
0.692
0.611
0.473
0.261
0.246
0.407
0.523
0.613
0.680
0.767
0.793
0.664
0.616
0.556
0.471
0.349
0.126
0.184
0.312
0.415
0.511
0.604
0.460
0.377
0.287
0.098
0.145
0.252
0.402
0.237
0.068
0.123
0.061

0.174
0.116
0.091
0.068
0.047
0.096
0.107
0.119
0.143
0.171
0.197
0.248
0.279
0.475
0.409
0.340
0.292
0.251
0.203
0.194
0.309
0.333
0.378
0.423
0.506
0.640
0.662
0.576
0.505
0.442
0.383
0.512
0.567
0.630
0.770
0.777
0.694
0.584
0.732
0.856
0.854
0.921

1.126
1.109
1.071
1.020
0.989
0.990
1.001
1.028
1.054
1.082
1.118
1.110
1.084
1.062
1.087
1.060
1.048
1.019
0.988
0.989
0.985
1.001
1.000
1.040
1.048
1.114
1.024
0.988
0.991
0.979
0.989
0.986
0.995
0.956
1.068
0.982
0.979
0.989
0.996
0.966
0.993
0.989

1.384
1.417
1.282
1.191
1.035
1.053
1.084
1.130
1.179
1.213
1.294
1.323
1.342
1.281
1.262
1.187
1.137
1.098
1.046
1.021
1.034
1.058
1.093
1.146
1.212
1.261
1.183
1.121
1.097
1.048
1.017
1.022
1.053
1.101
1.140
1.069
1.045
1.005
1.007
1.062
1.007
1.001

0.985
1.031
0.986
1.068
1.438
1.288
1.138
1.084
1.027
0.991
0.970
1.017
1.006
0.964
0.970
1.044
1.011
1.159
1.411
1.499
1.435
1.235
1.080
1.055
1.025
0.995
1.109
1.183
1.244
1.370
1.749
1.494
1.292
1.196
1.098
1.219
1.335
1.934
1.613
1.229
1.627
1.826

Figure 6. Diagram of VLE for the ternary system 1-hexene (1) +

n-hexane (2) + 2-pentanol (3) at 100.0 kPa: , liquid-phase mole fractions; , vapor-phase mole fractions.

in eq 6. For each experimental point reported in this work the

value of D was always smaller than the value of Dmax.
VLE data for both ternary systems have been estimated by
using the Wilson, NRTL, and UNIQUAC models with the
binary interaction parameters obtained from the regression of
binary data and also are predicted by the UNIFAC method.
Table 10 lists the average deviations between experimental and
calculated temperatures and vapor phase mole fractions of the
components. The three models represent the data successfully.
Thus, these models can be used to calculate boiling points
from liquid phase compositions at the system pressure. As an
example, boiling isotherms calculated for both ternary systems
with the aid of the NRTL model are presented in Figure 7
when ethyl butyrate is the solvent and Figure 8 for the case of
2-pentanol.

u(T) = 0.02 K, u(p) = 0.1 kPa, and u(x1) = u(x2) = u(y1) = u(y2) =
0.001.

Dmax =

(xia + xib) 1

xia

i=1

(xia + xib) P
i=1
N

1
1
1
+
+ x
yia
xib
yib
N

+ 2 |ln b ln ia|x
i=1

(xia + xib)Bj{(Ta + Cj)2 + (Tb + Cj)2 }T

i=1

(6)

Figure 7. Boiling isotherms (K) for the ternary system 1-hexene (1) +
n-hexane (2) + ethyl butyrate (3) at 100.0 kPa calculated with NRTL
model with the parameters given in Table 10.

The errors in the measurements x, P, and T were as

previously indicated. The rst and fourth are the dominant terms
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Table 12. Experimental VaporLiquid Equilibrium Data for

the System 1-Hexene (1) + n-Hexane (2) + 2-Pentanol (3)
at 100.0 kPaa

Figure 8. Boiling isotherms (K) for the ternary system 1-hexene (1) +
n-hexane (2) + 2-pentanol (3) at 100.0 kPa calculated with NRTL
model with the parameters given in Table 10.

Solvent Eects. The solvent eects in the VLE of the mixture 1-hexene + n-hexane will be discussed taking into account
two aspects: analysis of the residue curve map,15 and changes in
relative volatility. Furthermore, both solvents will be compared
with each other in order to recommend the most suitable
entrainer for the separation of the mixture 1-hexene + n-hexane
by extractive distillation.
In Figure 9 and Figure 10, residue curves simulated by Aspen
properties v7.3 using the NRTL model with the experimental

VT/K

x1

x2

y1

y2

377.02
353.23
344.42
340.56
337.17
338.06
339.45
340.99
342.96
345.32
348.90
352.35
353.65
358.48
351.95
346.86
343.90
341.54
340.04
338.36
338.03
339.63
341.43
343.70
345.72
349.55
350.51
345.42
342.75
341.03
338.80
339.96
341.63
343.07
346.69
343.53
341.97
339.86
340.95
343.40
341.54
341.40

0.044
0.252
0.454
0.646
0.900
0.794
0.696
0.590
0.487
0.392
0.305
0.225
0.209
0.111
0.127
0.247
0.364
0.493
0.580
0.711
0.727
0.540
0.434
0.318
0.235
0.138
0.098
0.176
0.295
0.382
0.546
0.399
0.293
0.210
0.051
0.103
0.203
0.344
0.208
0.057
0.104
0.056

0.038
0.052
0.064
0.059
0.054
0.106
0.102
0.100
0.096
0.099
0.100
0.095
0.092
0.127
0.240
0.226
0.207
0.205
0.210
0.200
0.211
0.316
0.297
0.289
0.291
0.281
0.288
0.383
0.387
0.411
0.405
0.498
0.491
0.491
0.488
0.613
0.600
0.599
0.696
0.698
0.798
0.895

0.267
0.691
0.804
0.868
0.930
0.866
0.842
0.812
0.774
0.730
0.671
0.591
0.569
0.368
0.303
0.474
0.601
0.677
0.719
0.775
0.775
0.627
0.577
0.496
0.417
0.289
0.228
0.301
0.423
0.483
0.593
0.460
0.376
0.299
0.093
0.146
0.265
0.385
0.246
0.079
0.128
0.066

0.250
0.160
0.118
0.079
0.051
0.104
0.114
0.131
0.149
0.183
0.220
0.258
0.256
0.433
0.569
0.420
0.322
0.264
0.234
0.193
0.199
0.330
0.363
0.424
0.493
0.584
0.657
0.615
0.509
0.466
0.384
0.503
0.566
0.634
0.809
0.787
0.683
0.585
0.714
0.854
0.834
0.906

2.035
1.668
1.379
1.172
0.998
1.025
1.090
1.185
1.291
1.413
1.508
1.637
1.638
1.753
1.503
1.394
1.305
1.163
1.098
1.015
1.003
1.041
1.130
1.240
1.331
1.410
1.525
1.294
1.172
1.087
0.998
1.023
1.084
1.153
1.331
1.133
1.092
0.997
1.020
1.112
1.043
1.003

2.654
2.211
1.691
1.374
1.073
1.085
1.185
1.327
1.484
1.652
1.778
1.998
1.977
2.135
1.763
1.590
1.448
1.284
1.161
1.057
1.044
1.101
1.222
1.373
1.497
1.650
1.763
1.430
1.265
1.147
1.025
1.055
1.146
1.231
1.425
1.207
1.120
1.023
1.040
1.155
1.041
1.013

0.892
0.970
1.114
1.501
4.118
2.853
1.926
1.502
1.366
1.125
1.016
1.047
1.112
0.937
0.973
1.229
1.267
1.553
1.920
3.366
3.996
2.617
1.783
1.451
1.226
1.175
0.963
1.249
1.599
2.011
4.300
3.098
2.125
1.650
1.310
1.698
2.055
4.565
3.418
1.982
3.089
4.588

u(T)= 0.02 K, u(p) = 0.1 kPa, and u(x1) = u(x2) = u(y1) = u(y2) =
0.001.

node. Thus, 1-hexene could be obtained as an overhead product

and any of the two solvents will be the bottom product. This
behavior is consistent with the boiling points of the components
employed here. In this case the residue curve maps give little
valuable information.
A more useful tool to evaluate the inuence of adding a solvent
in a binary mixture is to calculate the change in the relative
volatility of the initial mixture. In this occasion, the value of the
relative volatility of 1-hexene to n-hexane is very close to unity
(12 = 1.177).2 In this sense, Table 13 provides values of mean
relative volatilities in the presence of the solvent (S12) for two
dierent solvents compositions (for x3 = 0.7 and 0.8). NRTL
model has been used in order to calculate the relative volatilities.

Figure 9. Residue curve map for the ternary system 1-hexene (1) +
n-hexane (2) + ethyl butyrate (3) at 100.0 kPa simulated by Aspen split
using the NRTL model with the parameters given in Table 10.

parameters reported in Table 10 are shown. As can be seen

in these gures, in both ternary systems there is only a one
distillation region with three singular points (nodes and saddles)
which correspond with the three pure component vertices.
1-Hexene is an unstable node; n-hexane is a saddle, and ethyl
butyrate in Figure 5 and 2-pentanol in Figure 6 are both a stable
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eect of adding solvent can be more appreciated. Data from both

the Table 13 and the Figure 11 imply that the two proposed
solvents show a poor behavior as extractive distillation entrainers
because the two values of mean relative volatility in the presence
of the solvents are closer to unity than the original solvent-free
value. Additionally, a reversal in the initial mixture volatility is
produced when ethyl butyrate is employed as entrainer.
This behavior implies the refusal of the candidate entrainers
for extractive distillation to separate 1-hexene from n-hexane.

CONCLUSIONS
In order to study the 1-hexene + n-hexane separation process,
two solvents, ethyl butyrate and 2-pentanol have been proposed
as possible entrainers in an extractive distillation process. Hence,
consistent VLE data at 100.0 kPa have been determined for the
binary systems formed by 1-hexene (1) or n-hexane (2) with each
proposed solvent. Also the two ternary systems constituted by
the initial binary mixture and the solvent have been measured.
Wilson, NRTL, and UNIQUAC models correlated well the binary
systems and yielded good estimation for the ternary system,
without any remarkable dierence.
From the results, it is observed that both solvents decrease the
relative volatility of 1-hexene to n-hexane, ethyl butyrate even
inverts this relative volatility for high compositions of this solvent.
So, these solvents are not good entrainers for extractive distillation
to separate 1-hexene from n-hexane.

Figure 10. Residue curve map for the ternary system 1-hexene (1) +
n-hexane (2) + ethyl butyrate (3) at 100.0 kPa simulated by Aspen split
using the NRTL model with the parameters given in Table 10.

Table 13. Mean Relative Volatility in the Presence of

the Solvent (S12) Calculated Using the NRTL Model for
the System 1-Hexene (1) + n-Hexane (2) + Solvent (3)
at 100.0 kPa

12S
solvent

x3 = 0.0

x3 = 0.7

x3 = 0.8

ethyl butyrate
2-pentanol

1.177
1.177

0.995
1.045

0.986
1.038

AUTHOR INFORMATION

Corresponding Author

*Tel.: +34 963544317. Fax: +34 963544898. E-mail: sonia.loras@

uv.es.
Funding

Financial support from the Ministerio de Ciencia e Innovacion of

Spain, through Project No. CTQ2010-18848, is gratefully
acknowledged. B.M. and J.P.-F. have been funded by a grant
from La Universidad del Zulia of Venezuela and from the
Ministerio de Economia y Competitividad of Spain (BES-201104636 6), respectively.
Notes

The authors declare no competing nancial interest.

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Figure 11. VLE data plotted on a solvent-free basis for the system
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2-pentanol.

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