Abstract

Isobaric vaporliquid equilibrium (VLE) data for the quaternary system sec-butyl
alcohol + sec-butyl acetate + N, N-dimethyl formamide (DMF) + dimethyl sulfoxide
(DMSO) and the constituent binary system DMF + DMSO were determined at
101.3 kPa with a modified Othmer still. The measured experimental data of binary
and quaternary systems were certified to be thermodynamically consistent
according to the Van Ness method. And the experimental binary data were
correlated by Wilson, NRTL and UNIQUAC activity coefficient models. The rest of
binary interaction parameters have been obtained in our previous work. Then, the
binary and quaternary vaporliquid equilibrium were predicted by the models with
the correlated parameters. The results show that the three models yield a good
prediction for the binary and quaternary systems. But NRTL model performed
better than the other two models in predicting VLE of the quaternary system.

Keywords

sec-Butyl alcohol;
sec-Butyl acetate;
N, N-Dimethyl formamide;
Dimethyl sulfoxide;
Vapor-liquid equilibrium

1. Introduction
sec-Butyl alcohol is widely used in industry, such as pharmaceutical intermediates,
spices, dyes, flotation agents, polymerization additives, rubber additives, the
solubilizers of nitrocellulose lacquer and nitrocellulose lacquer thinner and so on.
But by now, it is mainly used to produce methyl ethyl ketone [1] and [2]. The
traditional methods of producing sec-butyl alcohol are indirect and direct hydration
of butylene. The method of indirect hydration of butylene has two serious
drawbacks: first, serious corrosion to equipment because of sulfuric acid as
catalyst; second, low selectivity. Although the process of direct hydration of
butylenes has overcome the drawback of corrosion, it requires high purity of raw
material and has low conversion ratio [3] and [4]. Recently, a novel method of
producing sec-butyl alcohol by transesterifying sec- butyl acetate with alcohols was

exploited by some researchers, which is superior to traditional method by the

hydration of butylenes. In this new process, sec-butyl alcohol and sec-butyl acetate
form a pseudo-azeotrope, in which the vapor and liquid composition is so close
that it should be ignored nearly [5]. Extractive distillation as a special distillation is
suitable to separate this type of systems. And Extractive agent selection is
important aspect for a process of extractive distillation.
In our previous work, DMF (3) and DMSO (4) were certified to be effective
extractive solvents for separation of sec-butyl alcohol (1) and sec-butyl acetate (2)
and DMSO performed better than DMF [5] and [6]. But the boiling point of DMSO is
so high that it is likely to decompose when recovering extractive agent by
distillation at 1 atm and even can cause explosion. If DMSO and DMF are mixed as
extractive agent, the temperature of tower bottom can be reduced. At same time,
DMF can inhibit the dissociation of DMSO at high temperature [7]. Consequently,
the mixed solvent as extractive agent to separatesec-Butyl alcohol (1) and secButyl acetate (2) is better than a single agent such as DMF (3) or DMSO (4) in
industrial applications. So, it is necessary to measure isobaric VLE data for the
quaternary system sec-Butyl alcohol (1) + sec-Butyl acetate (2) + DMF (3) + DMSO
(4) and the constituent binary systems. The binary interactive parameters of the
five systems: sec-butyl alcohol (1) + sec- butyl acetate (2) [8], sec-butyl alcohol
(1) + DMF (3) [5], sec-butyl alcohol (1) + DMSO (4) [6], sec-butyl acetate
(2) + DMF (3) [5],sec-butyl acetate (2) + DMSO (4) [6] have been obtained in our
previous work. Guo L. et al. measured vapor pressure of the binary system of DMF
(3) + DMSO (4) at various temperature and concentrations by using a quasi-static
ebulliometer method [7]. But there is no isobaric VLE data for DMF (3) + DMSO (4)
system and sec-butyl alcohol (1) + sec-butyl acetate (2) + DMF (3) + DMSO (4)
system in open literatures. Thus, the absent isobaric VLE data for the two systems
were explored experimentally in this work to supply basic data for the separation
of sec-butyl alcohol (1) + sec-butyl acetate (2) by extractive distillation using the
mixed solvent of DMF (3) and DMSO (4) as extractive agent.

2. Experimental
2.1. Chemicals
In this work, Analytical reagents (AR), sec-butyl alcohol, sec-butyl acetate and
DMF and DMSO were used. The molecular formula, CASRN, source, grade and
mass fraction are listed in Table 1. The physical properties of the pure components
are listed in Table 2, which are used to calculate fugacity coefficients. Purity of all

these chemicals were checked by a gas chromatography (GC) equipped with a

flame ionization detector (FID) and no appreciable peak of impurity was detected.
And the water contents were detected by Karl Fischer titration and no appreciable
water was detected. In additional, the boiling points of the pure components were
measured with the modified Othmer still at 101.30 kPa with an uncertainty of
0.01 K, which are shown in Table 3, together with the corresponding literature
values. The measured normal boiling points are basically consistent with literature
values. Therefore, all of the chemicals were used without further purification.
Table 1.
Experimental chemicals.
sec-Butyl
Component
alcohol
Molecular
C4H10O
formula
CASRN
78-92-2
Source
YuanLi,china
Purity grade
AR
w a(mass
0.999
fraction)

sec-Butyl
acetate
C6H12O2

DMF
C3H7NO

DMSO
C2H6OS

105-46-4
YuanLi,china
AR
0.999

68-12-2
YuanLi,china
AR
0.999

67-68-5
YuanLi,china
AR
0.999

Uncertainties: u(w) = 0.001.

Table options

Table 2.
Physical properties of the components.a
Component sec-Butyl alcohol sec-Butyl acetate
M/g mol1
74.1228
116.1601
Tc/K
535.90
561.00
Pc/kPa
4188.50
3170.00

0.5808
0.3954
Zc
0.2540
0.2640
3
1
Vc/m kmol
0.2700
0.3890

DMF
73.0947
649.60
4420.00
0.3177
0.2140
0.2620

DMSO
78.1350
729.00
5650.00
0.2806
0.2120
0.2270

Taken from Aspen Plus V7.2 physical properties databanks.

Table options

Table 3.
Comparison of the boiling points (Tb) at 101.3 kPa of the pure components with literature
data.

Tb/K

Component
sec-Butyl alcohol

This work
372.61

sec-Butyl acetate

385.31

DMF

425.10

DMSO

463.99

Literature
372.55 [9]
372.604 [10]
372.66 [11]
372.90a
385.35 [12]
385.15a
425.65 [13]
425.15 [14]
425.15a
463.15 [15]
464a

Taken from Aspen Plus V7.2 physical properties databanks.

Table options

2.2. Apparatus and procedures

In this work, a modified Othmer still was used to measure VLE data. A detailed
description of the apparatus has been previously reported [16]. The experimental
method and the test of the instrument reliability were reported by our previous
work [17]. In each experiment, the solution with a certain concentration prepared in
advance was measured. The equilibrium state was assumed to be established
when the fluctuation in equilibrium temperature was within 0.1 K in an about 0.5 h
and the vapor and liquid samples were withdrawn simultaneously with syringes.
A Fisher M101 pressure control system was used to measure and control the
pressure. The pressure in the still was maintained at 101.3 0.1 kPa during the
measurement process. And the equilibrium temperature was measured with a PT1000 connected to a digital temperature meter (AMETEK DTI-1000) with an
uncertainty of 0.01 K [18].
2.3. Sample analysis
All the samples were analyzed with a gas chromatograph (GC) (SP-2100, supplied
by Beijing Beifen Ruili Analysis Instrument Ltd.). The instrument was equipped with
a flame ionization detector (FID) and a silica capillary column (0.25 mm
(i.d.) 30 m 0.25 m) packed with PEG-20M. Nitrogen was used as the carrier

gas at a constant flow of 30 mL/min. The temperatures of vaporizer and detector

were set at 473.15 K and 493.15 K, respectively. The column temperature was
programmed at 363.15 K for 5 min, then increased to 463.15 K at 20 K min1, finally
was maintained at 463.15 K for 5 min.

3. Results and discussion

3.1. Experimental data
The experimental VLE data of the binary system of DMF (3) + DMSO (4) and the
quaternary system of sec-butyl alcohol (1) + sec-butyl acetate (2) + DMF
(3) + DMSO (4) were measured with a modified Othmer still mentioned above at
101.3 kPa. The experimental data are listed in Table 4 and Table 5.
Table 4.
Experimental VLE data the binary system of DMF (3) + DMSO (4) at 101.3 kPaa, together
with activity coefficients and fugacity coefficients.
T/K
425.10
427.25
429.03
430.14
431.35
433.01
434.74
436.51
438.04
439.64
440.93
442.55
445.44
447.12
449.06
451.35
454.55
456.85
461.24
463.99

x3
1.000
0.912
0.854
0.811
0.762
0.723
0.650
0.584
0.534
0.485
0.450
0.405
0.347
0.301
0.259
0.207
0.143
0.099
0.042
0.000

y3
1.000
0.973
0.950
0.933
0.911
0.892
0.853
0.813
0.778
0.741
0.711
0.671
0.612
0.562
0.510
0.438
0.334
0.252
0.119
0.000

3
1.000
1.004
1.000
1.005
1.013
1.003
1.022
1.038
1.047
1.056
1.059
1.069
1.064
1.083
1.093
1.115
1.147
1.189
1.204

0.851
0.899
0.900
0.915
0.908
0.929
0.944
0.956
0.964
0.971
0.975
0.966
0.973
0.973
0.980
0.987
0.992
0.981
1.000

0.971
0.971
0.972
0.972
0.972
0.973
0.973
0.973
0.974
0.974
0.974
0.974
0.975
0.975
0.975
0.976
0.976
0.977

0.970
0.970
0.971
0.971
0.971
0.971
0.972
0.972
0.972
0.973
0.973
0.973
0.974
0.974
0.974
0.975
0.975
0.976

Uncertainties: u(x3) = 0.001, u (y3) = 0.001, u (T) = 0.15 K, u (P) = 0.25 kPa.
Table options

Table 5.

Experimental VLE data for the quaternary system of sec-butyl alcohol (1) + sec-butyl
acetate (2) + DMF (3) + DMSO (4) at 101.3 kPa a, together with activity coefficients and
fugacity coefficients.
T/K
395
.77
395
.89
395
.91
395
.03
395
.73
395
.31
394
.79
395
.08
395
.91
396
.06
395
.89
395
.74
396
.02
397
.09
397
.11
397
.54
397
.92
399
.26
399
.65
400
.21

x1
0.0
39
0.0
61
0.0
78
0.0
98
0.1
22
0.1
43
0.1
58
0.1
81
0.2
01
0.2
23
0.2
37
0.2
61
0.2
79
0.3
03
0.3
18
0.3
42
0.3
61
0.3
78
0.3
90
0.3
91

x2
0.3
60
0.3
36
0.3
20
0.3
04
0.2
74
0.2
57
0.2
41
0.2
18
0.1
99
0.1
76
0.1
66
0.1
37
0.1
20
0.0
96
0.0
82
0.0
60
0.0
42
0.0
19
0.0
10
0.0
05

x3
0.3
01
0.3
02
0.2
99
0.3
00
0.3
03
0.2
98
0.2
99
0.3
01
0.2
99
0.3
03
0.2
98
0.3
01
0.3
03
0.3
02
0.3
00
0.2
97
0.2
98
0.3
02
0.3
01
0.3
03

y1
0.0
45
0.0
60
0.0
95
0.1
07
0.1
50
0.1
91
0.2
01
0.2
55
0.2
79
0.3
22
0.3
48
0.4
25
0.4
73
0.5
21
0.5
66
0.6
49
0.7
15
0.7
80
0.8
41
0.8
55

y2
0.8
03
0.7
91
0.7
61
0.7
56
0.7
15
0.6
72
0.6
72
0.6
20
0.6
01
0.5
51
0.5
24
0.4
52
0.4
09
0.3
54
0.3
15
0.2
42
0.1
79
0.0
95
0.0
55
0.0
26

y3
0.1
17
0.1
20
0.1
00
0.1
13
0.1
03
0.0
90
0.0
93
0.1
07
0.0
93
0.1
01
0.0
99
0.1
01
0.0
98
0.1
02
0.0
93
0.0
85
0.0
88
0.0
89
0.0
73
0.0
91

0.9
77
0.9
77
0.9
77
0.9
77
0.9
77
0.9
77
0.9
76
0.9
76
0.9
77
0.9
77
0.9
77
0.9
77
0.9
77
0.9
77
0.9
77
0.9
77
0.9
77
0.9
77
0.9
77
0.9
77

0.9
69
0.9
69
0.9
70
0.9
68
0.9
69
0.9
70
0.9
69
0.9
68
0.9
69
0.9
69
0.9
69
0.9
68
0.9
68
0.9
69
0.9
69
0.9
69
0.9
69
0.9
70
0.9
70
0.9
70

0.9
70
0.9
70
0.9
70
0.9
70
0.9
70
0.9
69
0.9
69
0.9
70
0.9
69
0.9
70
0.9
70
0.9
70
0.9
70
0.9
70
0.9
70
0.9
70
0.9
70
0.9
70
0.9
70
0.9
71

0.9
67
0.9
67
0.9
67
0.9
67
0.9
67
0.9
67
0.9
67
0.9
67
0.9
67
0.9
67
0.9
67
0.9
67
0.9
67
0.9
67
0.9
67
0.9
67
0.9
67
0.9
68
0.9
68
0.9
68

1
0.5
49
0.4
67
0.5
77
0.5
31
0.5
86
0.6
45
0.6
23
0.6
84
0.6
58
0.6
81
0.6
96
0.7
76
0.8
01
0.7
87
0.8
14
0.8
57
0.8
85
0.8
87
0.9
17
0.9
15

2
1.6
49
1.7
34
1.7
53
1.8
74
1.9
31
1.9
59
2.1
17
2.1
40
2.2
23
2.2
95
2.3
25
2.4
39
2.5
00
2.6
29
2.7
38
2.8
41
2.9
71
3.3
68
3.5
94
3.4
14

3
0.9
00
0.9
17
0.7
71
0.8
93
0.7
88
0.7
09
0.7
42
0.8
41
0.7
17
0.7
65
0.7
66
0.7
78
0.7
43
0.7
50
0.6
88
0.6
27
0.6
39
0.6
12
0.4
97
0.6
06

4
0.9
42
0.7
75
1.1
67
0.6
69
0.8
60
1.2
79
0.9
43
0.4
97
0.7
21
0.6
97
0.7
80
0.5
91
0.5
37
0.5
92
0.6
66
0.6
03
0.4
49
0.8
50
0.7
27
0.6
39

Uncertainties: u(xi) = 0.001, u(yi) = 0.001, u(T) = 0.15 K, u(P) = 0.25 kPa.
Table options

3.2. Vapor-liquid equilibrium model

For low pressure and considering vapor non-ideality, the flowing
Equation (1)[19] and [20] is valid to describe VLE,
equation(1)
Turn MathJaxon

where i is the activity coefficient of component i in liquid phase; xi, yi are the liquid
and vapor mole fractions of component i, respectively; P is the pressure of the
vaporliquid equilibrium system;
and
are the fugacity coefficient of pure
vapor i and component i in vapor phase, respectively, which were calculated by
the Soave-Redlich-Kwong (SRK) equation. And the results of
are listed
in Table 4 and Table 5; is the saturation vapor pressure of component i at the
equilibrium temperature Tand was calculated by the following extended Antoine
equation,
equation(2)
Turn MathJaxon

where the temperature T ranges from Tmin to Tmax. The extended Antoine
coefficientC1,i C7,i for the pure components were obtained from Aspen Plus V7.2
physical properties databanks together with Tmin and Tmax, which are presented
in Table 6. Thus, i can be calculated from Equation (1), and the results are
presented inTable 4 and Table 5
Table 6.
The parameters of extended Antoine equation.a
Component sec-Butyl alcohol sec-Butyl acetate
C1
115.6422
45.6932
C2
10,236.0000
6097.9000
C3
0.0000
0.0000
C4
0.0000
0.0000
C5
14.1250
4.2398
17
C6
2.3559 10
2.1506 1018
C7
6.0000
6.0000
Tmin/K
158.45
174.15
Tmax/K
535.90
561.00

DMF
75.8542
7955.5000
0.0000
0.0000
8.8038
4.2431 106
2.0000
212.72
649.60

DMSO
49.3652
7620.6000
0.0000
0.0000
4.6279
4.3819 107
2.0000
291.67
729.00

Taken from Aspen Plus V7.2 physical properties databank.

Table options

3.3. Consistency tests for the binary experimental data

The point to point test of Van Ness [21] is used to check the thermodynamic
consistency of the experimental data of the binary system DMF (3) + DMSO (4).
The method can be described by the following equations,
equation(3)

Turn MathJaxon

where yi is the mean absolute deviation of vapor composition i; n is the number of

experimental data; the superscripts cal and exp denote the calculated values
and experimental data. The test suggests that if the value of yi is less than 0.01,
the isobaric VLE data are thermodynamically consistent. In this test, NRTL activity
coefficient model with its parameter regressed were used to calculate the mole
fractions yi in vapor phase. The checking results are listed in Table 7.
Table 7.
Thermodynamic consistency check results of Van Ness test for the systems of DMF
(3) + DMSO (4) andsec-Butyl alcohol (1) + sec-butyl acetate (2) + DMF (3) + DMSO (4).
y1
y2
y3
y4
Systems
Results
DMF(3) + DMSO (4)

0.0004 0.0004 Passed

sec-Butyl alcohol (1) + sec-butyl
0.0073 0.0061 0.0065 0.0055 Passed
acetate (2) + DMF (3) + DMSO (4)
Table options

3.4. Correlation of binary vaporliquid equilibrium

The experimental VLE data for the binary system of DMF (3) + DMSO (4) were
correlated with Wilson, NRTL and UNIQUAC models by Aspen Plus V7.2 [22]. The
following maximum likelihood objective function obtained from Aspen Plus V7.2
was adopted in the regression of the binary VLE data of DMF (3) + DMSO (4)
equation(4)

Turn MathJaxon

where P and T are the equilibrium pressure and temperature, respectively; is

the standard deviation of the corresponding physical property. The standard
deviations of pressure ( P ), temperature ( T ), liquid composition ( x 1 ) and vapor
composition ( y 1 ) used in this VLE data correlation are 0.1013 KPa, 0.1 K, 0.001
and 0.001, respectively.
The correlated binary interaction parameters are shown in Table 8, together with
the root-mean-square deviations (RMSD) in temperature, pressure, liquid and
vapor phase mole fraction. While the rest of binary interaction parameters were
taken from literatures[5] and [6], which are also shown in Table 8. The
comparisons between experimental and calculated data are shown in Fig. 1.
Table 8.
The correlated binary interaction parameters and RMSD for the binary systems.
Correlation parameters
RMSD

aij
aji
bij/K
bij/K
Model
sec-Butyl alcohol (1) + sec-butyl acetate (2) [5]
Wilsone
0.14
4.991
189.55
1606.5
98
5
5
NRTLf
5.398
0.2840
1634.
341.0
15
1
QUNIQUA 0.90
0.222
246.44
144.30
Cg
78
9
sec-Butyl alcohol (1) + DMF (3) [5]
Wilsone
0.93
4.2602
656.98
1866.
45
11
f
NRTL
4.51
1.7584
2000.7
1031.
55
2
04
UNIQUAC 0.44
0.7293
37.25
69.41
g
14
sec-Butyl acetate (2) + DMF (3) [5]
Wilsone
3.27
5.1340
1020.5
2034.
43
2
39
f
NRTL
4.73
2.8251
1819.4
790.8
47
8
8
UNIQUAC 1.7414 0.792
791.9
329.69
e
7
4
sec-Butyl alcohol (1) + DMSO (4) [6]
Wilsonc
7.2661 0.775
3970.
788.87
8
54

x1

T c(
K)

P d(kP
a)

0.011
1
0.010
6
0.011
1

0.341
8
0.340
9
0.341
5

0.007
4
0.007
2
0.007
3

0.731
9
0.759
6
0.789
2

0.009
6
0.008
9
0.008
7

0.357
0
0.362
2
0.364
3

0.004
3

0.693
1

y1

Correlation parameters

Model
NRTLd

aij
0.0171

aji
3.334
5
3.0451

RMSD

bij/K
624.7
5
560.08

0.49
16
sec-Butyl acetate (2) + DMSO (4) [6]
Wilsone
3.3933 6.878
1711.
6
57
NRTLf
3.1645 2.746
1108.
6
75
UNIQUAC 0.22
0.1710
149.9
g
67
2
DMF (3) + DMSO (4)
Wilsone
1.62
12.06
1084.3
93
86
5
f
NRTL
5.1402 2.8405
1511.
17
UNIQUAC 4.95
0.2377
1721.5
g
14
8
UNIQUAC
g

bij/K
2373.2
6
1865.
71

x1 a

2494.3
4
1508.2
9
32.93

4564.7
5
1726.
27
187.22

0.001
0
0.000
8
0.000
9

y1 b
0.003
5
0.004
3

T c(
K)
0.445
2
0.605
3

P d(kP
a)

0.003
6
0.003
6
0.007
2

0.337
2
0.337
2
0.526
9

0.000
5
0.000
8
0.000
4

0.269
0
0.236
8
0.242
4

0.1585

0.1544
0.1588

.
c

.
d

.
e

Wilson,

NRTL, i j = a i j + b i j / T , the value of ij was fixed at 0.3 for the binary systems.
g

UNIQUAC, i j = e xp ( a i j + b i j / T ) .
Table options

Fig. 1.
T vs. x3, y3 diagram for the DMF (3) + DMSO (4) system at 101.3 kPa (, experimental data;
solid line, calculated with Wilson model; dot line, calculated with NRTL model; short dot
line, calculated with UNIQUAC model).
Figure options

3.5. Prediction of quaternary vaporliquid equilibrium

The Wilson, NRTL and UNIQUAC models with the binary parameters
in Table 7 were used to predict the VLE data for the quaternary system sec-butyl
alcohol (1) + sec-butyl acetate (2) + DMF (3) + DMSO (4). The predictive
deviations of the equilibrium temperatures and the vapor-phase compositions for
the Wilson, NRTL and UNIQUAC models are displayed in Table 9 respectively. It is
obvious that the deviations of the equilibrium temperatures and the vapor phase
mole fractions are reasonably small. So, all of the models can predict the VLE data
of the quaternary system very well. But NRTL performs better than Wilson or
UNIQUAC model.
Table 9.
Predicted deviations by the Wilson, NRTL and UNIQUAC for the quaternary system of secbutyl alcohol (1) + sec-butyl acetate (2) + DMF (3) + DMSO (4).

Maximum average
absolute deviation

Mod
el
Wils
on

Average absolute
deviation

max
T/K

m
axy

m
axy

m
axy

m
axy

e
1

e
2

e
3

e
4

1.5
3

0.
04
5
0.
01
1
0.
03
7

0.
04
5
0.
01
3
0.
04
0

0.
02
0
0.
02
0
0.
01
4

0.
01
4
0.
01
5
0.
01
7

NRT
L

0.7
9

UNI
QUA
C

1.4
4

T/
Ka
0.
65
0.
40
0.
60

y
1

0.
02
0
0.
00
7
0.
01
6

y
2

0.
02
3
0.
00
6
0.
01
5

RMSD

y
3

0.
00
6
0.
00
7
0.
00
6

y
4

0.
00
6
0.
00
6
0.
00
5

T/
Kc
0.
75
0.
47
0.
74

y
1

0.
02
4
0.
00
8
0.
01
9

y
2

0.
02
6
0.
00
7
0.
01
8

y
3

0.
00
8
0.
00
8
0.
00
7

y
4

0.
00
7
0.
00
7
0.
00
7

.
d

.
e

maxT and maxyi are the maximum average absolute deviation of temperature and vapor
composition, respectively.
Table options

The mole fraction difference of sec-butyl alcohol (y1 x1) between vapor and liquid
phase in the binary system sec-butyl alcohol (1) + sec-butyl acetate (2) [8] and that
excluding extractive solvent in the sec-butyl alcohol (1) + sec-butyl acetate
(2) + DMF (3) + DMSO (4) system are shown in Fig. 2. Inspection of the upper
portion of Fig. 2shows that the values of (y1 x1) at terminal region of the solid line
are very close to 0, which is pseudo-azeotropic phenomenon mentioned above.
But at the same region, the dot line at lower portion of Fig. 2 is obviously far away
from X-axis. This illustrates that the mixed solvent of DMF (3) and DMSO (4) can
eliminate the pseudo-azeotrope.

Fig. 2.
y1 x1 vs. x1 diagram for the VLE data of sec-butyl alcohol (1) + sec-butyl acetate (2) with
or without extractive solvent (, without any extractive solvent [8]; , mixed solvent of DMF
and DMSO as extractive solvent and calculated from Table 5; the solid line, connecting line;
the dot line, fitted by a quartic polynomial).
Figure options

4. Conclusion
The VLE data of binary system of DMF (3) + DMSO (4) and quaternary sec-butyl
alcohol (1) + sec-butyl acetate (2) + DMF (3) + DMSO (4) were measured with a
modified Othmer still. The experimental VLE data have passed the Van Ness
thermodynamic consistency test. Then the binary VLE data were correlated with
Wilson, NRTL and UNIQUAC models and obtained their binary interaction
parameters. And the VLE data for the binary and quaternary systems were
predicted by the three models with these binary interaction parameters. The results
show that the experimental data are in agreement with correlation data well when
predicting the binary system DMF (3) + DMSO (4). When using them to predict the
quaternary system, NRTL model is superior to Wilson and UNIQUAC models.
When the mole fraction of the mixed extractive agent of DMF (3) and DMSO (4)
(x3: x4 = 1) is 0.6, the pseudo-azeotropic phenomenon is eliminated. Consequently,
the mixed solvent of DMF (3) and DMSO (4) is certified to effective for separation
of the binary pseudo-azeotrope of sec-butyl alcohol and sec-butyl acetate in
extractive distillation.

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2.

Alexis :3

Thermodynamics metastable phase equilibria of

aqueous quaternary system LiCl + KCl + RbCl + H2O at
323.15 K

Zhongquan Lia,
Xudong Yub,
Qinghong Yinb,
Ying Zengb, c, ,
Show more
doi:10.1016/j.fluid.2013.08.011
Get rights and content

Abstract
The solubilities and physicochemical properties (densities and refractive indices) in
the aqueous quaternary system LiCl + KCl + RbCl + H2O were investigated at
323.15 K using an isothermal evaporation method. The stereo phase diagram, the
projected diagram, the water content diagram and the physicochemical properties
versus composition diagrams were plotted based on the measured data. There are
two invariant points, five univariant curves and four crystallization fields
corresponding to single salts potassium chloride (KCl), rubidium chloride (RbCl),
lithium chloride monohydrate (LiClH2O) and a solid solution of potassium and
rubidium chloride [(K, Rb)Cl] in the projected diagram. No double salt was formed.
Comparisons between the metastable phase diagrams at 298.15 K and 323.15 K
show that the crystallization zones of solid solution [(K, Rb)Cl] decreased at
323.15 K, while the crystallization zones of single salts KCl, RbCl, and LiClH2O
enlarged at 323.15 K. The calculated refractive indices using empirical equations
have a maximum relative error less than 0.008.

Keywords

Metastable phase equilibrium;

Solid solution;

Potassium;

Rubidium;

Solubility

1. Introduction
Rubidium is rare and scattered in nature; its applications are widely in the fields of
electronics, nuclear energy and space technologies [1]. Thus the international
demand for rubidium has increased dramatically over the last years. Compared
with the traditional process of extracting rubidium and lithium from solid ore, it is
more economical to extract them from liquid minerals. It is well known that phase
diagram is the basis and guidance of utilization of liquid mineral resources and
separation techniques of salts. Therefore, the phase equilibria of rubidium
containing system are essential.
Up to now, some researches about the phase equilibria aimed at the rubidium
system had been done. These work mainly concentrated in two types, one is
focused on saltwater system, and the other is focused on mixed solvent system.
1.1. Phase equilibria in mixed solvent system
Norio et al. studied RbCl + 1-buatanol + H2O system at 298.15 K [2], it was found
that the solubility of rubidium chloride decreased with the increasing of the 1buatanol content; Gao et al. completed system RbCl + EtOH + H2O at 298.15 K
and 323.15 K [3], Rb2CO3 + EtOH + H2O at 313.15 K [4], Rb2SO4 + EtOH + H2O at
273.15 K 333.15 K[5], RbNO3 + EtOH + H2O at 298.15 K and 323.15 K [6]. The
results shown that the salting out technique is possibility to be used to increase the
yield of rubidium compounds from an aqueous solution by adding ethyl alcohol; Hu
et al. studied RbCl/CsCl + amide (acetamide, propanamide, and nbutanamide) + H2O system at 298.15 K [7], RbCl + EtOH + H2O at 308.15 K [8], in
all case, the presence of ethyl alcohol reduced the solubility of rubidium chloride.
1.2. Phase equilibria in saltwater system
M. Kalink et al. [9] studied ternary system K2SO4 + Rb2SO4 + H2O at 298.15 K, the
system is of complex type with the continuous solid solutions between K 2SO4 and
Rb2SO4 formed at 298.15 K. Feit et al. [10] investigated the quaternary system
KCl + RbCl + MgCl2 + H2O at 293.15 K, 298.15 K, and 373.15 K, however the
author only gave partial experimental data. A. Merbach et
al. [11] and [12] completed the quaternary system of KCl + RbCl + CsCl + H2O and
its sub system at 298.15 K, results shown that there was only solid solution [(K,
Rb) Cl] was formed in the KCl + RbCl + H2O system. J. DAns et al. [13] studied the

quaternary system KCl + RbCl + (CsCl) + MgCl2 + H2O and its sub systems at
298.15 K, results shown that there were single salts KCl, RbCl, and solid solution
[(K, Rb) Cl] formed in the KCl + RbCl + H2O system.
In conclusion, most of efforts focused on the rubidium system in mixed solvent or
stable phase equilibria in watersalt system, researches on metastable phase
equilibria of rubidium system are rarely reported. Aiming at understanding the
thermodymics behavior of the rubidium system, some metastable phase equilibria
at different temperatures have been done by our research group, such as ternary
system LiCl + RbCl + H2O at 298.15 K [14]; the metastable phase diagram of
ternary system KCl + RbCl + H2O at 298.15 K [15], 323.15 K [16],
348.15 K [17] have been plotted in our previous researches. Compared with the
previous researches about the ternary system KCl + RbCl + H2O [12] and [13], we
found that besides solid solution [(K, Rb)Cl], the single salts KCl and RbCl are also
formed at research temperature.
The quaternary system LiCl + KCl + RbCl + H2O at 298.15 K has also been
focused in our earlier study [18]. The metastable phase diagram of this quaternary
system consists of four crystallization fileds corresponding to single salts LiClH2O,
KCl, RbCl, and solid solution [(K, Rb)Cl]. As we known, the crystallization zone and
crystallization form of solid solution and hydrate salt depend on coexist ion and
temperature [19]. To figure out the crystallization form and crystallization area of
the solid solution and hydrated salt of the quaternary system
LiCl + KCl + RbCl + H2O changes with the temperature, researches focuses on the
metastable phase equilibria about the system LiCl + KCl + RbCl + H2O at multitemperature are necessary. Accordingly, the metastable phase equilibria of the
quaternary system LiCl + KCl + RbCl + H2O at 323.15 K is reported; meanwhile
comparisons between the metastable phase diagrams at 298.15 K and 323.15 K
are presented in this paper.

2. Experimental
2.1. Apparatus and reagents
All inorganic salts, LiCl, KCl, and RbCl, were supplied by the Chengdu Kelong
Chemical Reagent Plant or the Jiangxi Dongpeng New Materials Co., Ltd. with
purities higher than 99.0% (w/w). The deionized water, with an electrical
conductivity less than 1 104 S m1 and pH 6.60, was used to prepare the phase
equilibria experimental samples and for chemical analysis.

2.2. Experimental method

The isothermal evaporation method was employed for the solubility
experiments [18]. The SHH-250 type thermostatic evaporator with the temperature
range (258.15373.15 K) and temperature controlling precision 0.1 K was
employed in the isothermal evaporation experiments. The 2WAJ Abbe
refractometer with a precision of 0.0001 and a gravity bottle method with a
precision of 0.0002 g cm3 were used for the determination of physicochemical
properties (refractive index and density) of equilibrated solution. The specific
gravity bottle method with correction of air buoyancy was used [20].
2.3. Analytical methods
The composition of the liquid phase was determined by chemical or instrument
analysis. The concentration of chloride was analyzed by volumetric method with a
precision of 0.3%; the total amount of potassium and rubidium was analyzed by
sodium tetraphenylborate(STPB)hexadecyl trimethyl ammonium bromide(CTAB)
back titration with a precision of 0.5%; the concentration of rubidium and lithium
were analyzed by ICPOES method with a precision of 0.5% [21]. Each analysis
was repeated three times with triplicate samples prepared for each data point, and
the average value of three measurements was considered as the final value of the
analysis.

3. Results and discussion

The composition of liquid phase of the quaternary system LiCl + KCl + RbCl + H2O
at 323.15 K are listed in Table 1. The solubility data corresponding to the invariant
points in the binary and ternary subsystems of this quaternary system are
tabulated in Table 2. The experimental and calculated values of refractive indices
of the quaternary system at 323.15 K are presented in Table 3. In Table
1 and Table 2, the ion concentration values were expressed in mass
fraction w(B). J(B) is the Jnecke index values of B,
withJ(KCl) + J(RbCl) + J(LiCl) = 100. The Jnecke index, that is the mole
percentage, can be calculated according to the following correlations,