Fluid Phase Equilibria 344 (2013) 5964

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Fluid Phase Equilibria

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Vapourliquid equilibria in binary and ternary systems composed of

2,3-dimethylbutane, diisopropyl ether, and 3-methyl-2-butanone at 313.15,
323.15 and 313.15 K
Ivan Wichterle
Jan Pavlcek, Adla Andresov, Grozdana Bogdanic,
Institute of Chemical Process Fundamentals v.v., Academy of Sciences of the Czech Republic, Rozvojov 135, 165 02 Praha 6, Czech Republic

a r t i c l e

i n f o

Article history:
Received 10 December 2012
Received in revised form 18 January 2013
Accepted 30 January 2013
Available online 9 February 2013
Keywords:
Vapourliquid equilibrium
Experimental data
Prediction
Hydrocarbon
Ether
Ketone

a b s t r a c t
This article reports vapourliquid equilibrium data in three binary systems, namely 2,3dimethylbutane + diisopropyl ether, 2,3-dimethylbutane + 3-methyl-2-butanone, and diisopropyl
ether + 3-methyl-2-butanone and in one ternary system, 2,3-dimethylbutane + diisopropyl ether + 3methyl-2-butanone. The data were measured isothermally at 313.15, 323.15, and 333.15 K covering
the pressure range of 13108 kPa. The binary vapourliquid equilibrium data were correlated using
the Wilson and NRTL equations by means of a robust algorithm for processing all isotherms together.
The resulting parameters were then used to calculate phase behaviour in the ternary system and to
comparison the calculated with experimental data.
2013 Elsevier B.V. All rights reserved.

1. Introduction
This paper reports new results of a continuing project dealing
with phase equilibria in mixtures belonging to distinct families
of organic compounds. Here we determined the vapourliquid
equilibria (VLE) for three binary and one ternary system containing
hydrocarbon, ether, and ketone. In a series of our earlier papers,
we have already investigated systems having a common alkyl
group (isopropyl or tert-butyl), namely 2-propanol + diisopropyl
[1],
tert-butanol + 2,2,4ether + 2,2,4-trimethylpentane
trimethylpentane + 1-tert-butoxy-2-propanol
[2],
tert-butyl
methyl ether + tert-butanol + 2,2,4-trimethylpentane [3], 2propanol + diisopropyl ether + 1-methoxy-tert-butyl methyl ether
[4], 2-propanol + diisopropyl ether + 4-methyl-2-pentanone [5], 2methylpentane + 3-methyl-2-butanone + 3-methyl-2-butanol [6],
2-propanol + 3-methyl-2-butanone + 2,2,4-trimethylpentane [7],
tert-butyl
methyl
ether + 3,3-dimethyl-2-butanone + 2,2[8],
and
2,2,4-trimethylpentane +
dimethyl-1-propanol
2-methyl-1-propanol + 4-methyl-2-pentanone [9]. The next in
the series of experiments aimed at completing our database
are systems containing compounds that share the alkyl group
[isopropyl (CH3 )2 CH ], ether group O , and carbonyl group

Corresponding author. Tel.: +420 220 390 289; fax: +420 220 920 661.
E-mail address: wi@icpf.cas.cz (I. Wichterle).
0378-3812/$ see front matter 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.uid.2013.01.020

C O with the already investigated systems. The compounds used

in this experiment were 2,3-dimethylbutane, diisopropyl ether,
and 3-methyl-2-butanone. The new data were measured at three
isothermal levels: 313.15, 323.15, and 333.15 K.
2. Experimental
2.1. Apparatus and procedure
Experimental VLE data were measured in an all-glass circulation still chargeable with 150 ml of liquid phase. Essentially, it was
the generic DvorkBoublk type used in our previous research (e.g.
[7]). Pressure was measured indirectly via the boiling point of water
in an ebulliometer connected in parallel to the still; the uncertainty
was 0.1% of the measured value. The equilibrium temperature was
determined with a digital thermometer F250 (ASL, United Kingdom) calibrated against a Pt-resistance thermometer traceable to
the NBS (Washington, DC, USA) certicate (1962). The basic resistance was regularly re-checked by the triple point of water and the
absolute uncertainty of temperature measurement (on the ITS-90
scale) was estimated to 0.02 K. Samples taken for gas chromatography (GC) were kept in a desiccator lled with silica gel because of
their hygroscopicity. Liquid-phase and vapour-phase compositions
in all systems were determined using a gas chromatograph HP6850
(Hewlett-Packard) with thermal conductivity detection. The estimated uncertainty of the composition measurement was less than

60

J. Pavlcek et al. / Fluid Phase Equilibria 344 (2013) 5964

Table 1
Sample description.
Compound

Source

Purity by supplier
(mass fraction)

Final purity (mass

fraction)

Analysis method

2,3-Dimethylbutane
Diisopropyl ether

SigmaAldrich
Fluka

0.9968
0.9976

GCa
GC

3-Methyl-2-butanone

Fluka

0.98
puriss. p. a., >0.990
<0.1% of H2 O
puriss., 0.985

0.9934

GC

Gas liquid chromatography.

0.001 mole fraction. Density was measured with a vibrating tube

densimeter DMA 58 (A. Paar, Austria) and the refractive index was
determined using a precise Abbe type refractometer (Bellingham &
Stanley, UK).
2.2. Materials
Chemicals were purchased from Fluka and SigmaAldrich
with initial purity declared by manufacturer. All chemicals were
stored above 4 A molecular sieve to remove water traces and
used without further purication. Analyses were performed by
gas chromatographic method. The complete specications are
summarised in Table 1.
Properties of pure components, namely the density and refractive index and their comparison with literature data are presented
in Table 2. Saturated vapour pressures at normal boiling point were
not determined.
3. Results
Table 3 shows direct experimental xyP values together with
the activity coefcients,  1 ,  2 , and GE (evaluated from the NRTL
correlation) for the binary systems. All three binary systems are
zeotropic. The data were correlated using the Wilson and NRTL
equations in the following forms (expressions for ln  2 can be easily
obtained after interchanging indices 1 and 2):
(1) The Wilson equation
ln 1 = 1 ln(x1 + x2 A12 )

x1
x2 A21

,
x1 + x2 A12
x2 + x1 A21

Vapour phase imperfection and variation of the Gibbs energy of

pure liquid components with pressure were accounted for in terms
of the second virial coefcients and molar volumes under saturation pressure estimated by the method of Hayden and OConnell
[13] and of Hougen and Watson, respectively [14]. The adjustable
parameters for the binary systems were evaluated using an algorithm modied by Pavlcek and Wichterle [15], which is based
on the maximum likelihood procedure [16]. This robust algorithm
makes it possible to correlate VLE isotherms or isobars together
and get one set of universal parameters valid in the experimental
pressure and temperature range. It can be applied to any correlation equation with temperature-independent parameters such as
the Wilson or NRTL equations.
For VLE correlation of isothermal data, it is generally recommended to use the experimental vapour pressure of pure
components instead of a vapour pressure equation. This can easily
be achieved by adjusting the parameter A in the Antoine equation to the experimental value of vapour pressure at the particular
temperature. An analogous procedure cannot be used for simultaneous correlation of more isotherms. Pavlcek and Wichterle [15]
used an average value for all A parameters, individually adjusted
for every isotherm as above. In this case, however, the resulting
vapour pressures of a pure component do not necessarily agree
with experimental data. To eliminate this problem, we evaluated
necessary input parameters for the Antoine equation beforehand
using ad hoc correlation of experimental vapour pressures of pure
components at every isotherm. Consequently, we obtained a better
correlation of vapourliquid equilibrium data.

(1)
110

where A12 = (V1 /V2 ) exp[ (12 11 )/RT], A21 = (V2 /V1 ) exp[
(21 22 )/RT] and Vi is liquid molar volume of pure component i.
The concentration dependence of the activity coefcient contains
two adjustable parameters: (12 11 ) and (21 22 ).
(2) The NRTL equation
ln 1 =

21

G21
x1 + x2 G21

2

12 G12

(2)

(x1 + x2 G12 )2

where G12 = exp[ 12  12 ], G21 = exp[ 21  21 ],  12 = (g12 g22 )/RT,

and  21 = (g21 g11 )/RT. The equation contains three adjustable
parameters, namely (g12 g22 ), (g21 g11 ), and 12 = 21 .
Table 2
Properties of pure components.
d4298.15 (g cm3 )

Reference

n298.15
D

Reference

2,3-Dimethylbutane

0.65710
0.65702
0.71823
0.71838
0.7182
0.71854
0.79955
0.7982
0.8061

This work
[10]
This work
[4]
[10]
[11]
This work
[10]
[12]

1.37237
1.37231
1.36550
1.36508
1.3655

This work
[10]
This work
[1]
[10]

1.38568
1.38599
1.38620
1.3857

This work
[12]
[6]
[10]

3-Methyl-2-butanone

70

50

Component

Diisopropyl ether

P (kPa)

x22

90

30
0.0

0.2

0.4

0.6

0.8

1.0

mole fraction of 2,3-dimethylbutane

Fig.
1. Isothermal
vapourliquid
equilibrium
in
the
2,3dimethylbutane + diisopropyl ether system (xyP plot). Experimental data:
313.15 K (, ), 323.15 K (, ), 333.15 K (, ); (solid points) liquid phase; (open
points) vapour phase; () NRTL correlation.

J. Pavlcek et al. / Fluid Phase Equilibria 344 (2013) 5964

Table 3
Vapourliquid equilibrium experimental data, calculated
coefcients and excess Gibbs energy in binary systems.a
x1

y1

P (kPa)

1

2

Table 3 (Continued)
(NRTL)

1.000
1.001
1.003
1.006
1.014
1.026
1.035
1.044
1.052
1.062
1.072
1.082
1.091
1.095

0.0
22.0
31.4
42.5
50.2
50.9
47.5
42.4
36.8
29.3
20.2
11.4
3.4
0.0

T = 323.15 K
0.0000
0.1355
0.2095
0.3163
0.4506
0.5882
0.6689
0.7336
0.7900
0.8450
0.9017
0.9486
0.9863
1.0000

0.0000
0.1938
0.2866
0.4077
0.5410
0.6701
0.7379
0.7915
0.8369
0.8807
0.9252
0.9611
0.9897
1.0000

54.14
58.06
60.03
62.89
66.23
69.54
71.36
72.76
73.92
75.04
76.17
77.04
77.80
78.12

1.071
1.056
1.048
1.038
1.026
1.015
1.010
1.007
1.005
1.003
1.001
1.000
1.000
1.000

1.000
1.001
1.003
1.006
1.013
1.025
1.034
1.042
1.050
1.059
1.070
1.079
1.088
1.092

0.0
22.4
31.9
42.8
50.6
51.2
47.7
42.8
37.0
29.8
20.6
12.1
3.7
0.0

T = 333.15 K
0.0000
0.2116
0.3174
0.4518
0.5898
0.6702
0.7343
0.7893
0.8455
0.9027
0.9484
0.9863
1.0000

0.0000
0.2823
0.4020
0.5346
0.6648
0.7340
0.7876
0.8340
0.8778
0.9238
0.9601
0.9894
1.0000

76.90
84.58
88.30
92.59
96.92
99.25
101.04
102.57
103.98
105.47
106.61
107.57
107.99

1.069
1.047
1.037
1.025
1.015
1.010
1.007
1.004
1.003
1.001
1.000
1.000
1.000

1.000
1.003
1.006
1.013
1.024
1.033
1.041
1.049
1.057
1.068
1.077
1.085
1.089

0.0
32.1
43.0
50.7
51.4
48.0
43.1
37.3
30.1
20.8
12.1
3.8
0.0

2,3-Dimethylbutane (1) + 3-methyl-2-butanone (2)

T = 313.15 K
0.0000
13.73
2.664
0.0000
0.0277
14.11
2.648
0.0029
0.0750
14.79
2.620
0.0088
0.1532
16.07
2.566
0.0183
0.2707
18.46
2.466
0.0394
0.4210
22.21
2.307
0.0754
0.4829
24.56
2.207
0.0994
0.5799
28.87
2.022
0.1532
0.6330
31.62
1.904
0.1874
0.6905
35.44
1.739
0.2557
0.7503
40.04
1.540
0.3536
0.7883
43.45
1.394
0.4424
0.8224
46.61
1.261
0.5504
0.8533
49.30
1.157
0.6520
51.10
1.092
0.7417
0.8812
0.8256
0.9089
52.67
1.044
0.9341
53.77
1.019
0.8893
1.0000
55.13
1.000
1.0000

1.000
1.000
1.000
1.000
1.002
1.006
1.010
1.023
1.036
1.064
1.122
1.200
1.327
1.518
1.743
2.059
2.408
3.387

0.0
7.4
20.8
46.3
95.5
177.0
229.9
331.4
398.1
490.9
593.8
649.4
663.4
618.6
536.1
413.3
286.9
0.0

T = 323.15 K
0.0000
0.0036
0.0096
0.0206
0.0436
0.0756
0.1106

1.000
1.000
1.000
1.000
1.002
1.005
1.011

0.0
9.2
24.5
51.3
104.9
175.2
242.2

21.09
21.73
22.78
24.59
28.09
32.51
36.56

2.568
2.550
2.520
2.468
2.367
2.239
2.121

activity

GE (J mol1 )

2,3-Dimethylbutane (1) + diisopropyl ether (2)

T = 313.15 K
0.0000
37.09
1.072
0.0000
39.99
1.057
0.1350
0.1989
0.2075
0.2918
41.46
1.050
0.4130
43.65
1.039
0.3131
0.5412
46.14
1.027
0.4443
48.73
1.016
0.5888
0.6759
0.6669
0.7412
50.05
1.011
51.14
1.007
0.7336
0.7965
0.8397
51.98
1.005
0.7880
0.8837
52.85
1.003
0.8447
0.9270
53.69
1.001
0.9017
54.37
1.000
0.9486
0.9622
54.91
1.000
0.9862
0.9900
1.0000
55.13
1.000
1.0000

0.0000
0.0309
0.0778
0.1506
0.2749
0.3926
0.4756

61

1

2

GE (J mol1 )

41.42
46.54
50.40
56.82
61.56
66.15
70.02
72.54
74.73
76.22
78.12

1.979
1.828
1.715
1.525
1.386
1.256
1.151
1.090
1.044
1.019
1.000

1.021
1.039
1.059
1.114
1.186
1.306
1.492
1.699
1.989
2.302
3.208

325.4
415.0
482.1
585.6
642.6
659.8
615.5
535.8
415.3
292.4
0.0

31.43
33.93
36.47
41.44
46.57
52.74
58.13
65.98
70.20
78.83
85.42
91.68
97.08
100.49
103.47
105.46
107.99

2.482
2.432
2.380
2.279
2.175
2.049
1.938
1.776
1.688
1.510
1.375
1.249
1.147
1.088
1.043
1.019
1.000

1.000
1.000
1.001
1.002
1.005
1.011
1.020
1.040
1.056
1.107
1.176
1.289
1.466
1.657
1.924
2.215
3.052

0.0
27.5
56.0
113.5
175.0
251.3
320.1
421.6
476.1
578.4
637.4
656.2
613.5
536.4
418.6
295.7
0.0

Diisopropyl ether (1) + 3-methyl-2-butanone (2)

T = 313.15 K
13.73
1.564
0.0000
0.0000
0.0300
0.1096
14.94
1.533
0.1910
16.11
1.502
0.0593
0.3315
18.36
1.443
0.1143
0.4937
21.83
1.349
0.2171
0.6284
25.58
1.245
0.3526
0.7271
28.80
1.156
0.4930
31.17
1.094
0.6188
0.7950
0.7195
0.8466
32.99
1.052
34.79
1.020
0.8324
0.9030
0.9289
0.9555
36.21
1.004
0.9818
36.75
1.001
0.9759
1.0000
37.09
1.000
1.0000

1.000
1.000
1.001
1.005
1.019
1.052
1.111
1.191
1.287
1.437
1.619
1.720
1.790

0.0
32.5
63.3
122.4
208.9
287.3
325.3
318.4
279.7
199.0
94.6
37.9
0.0

T = 323.15 K
0.0000
0.0329
0.0596
0.1153
0.2213
0.3581
0.4965
0.6210
0.7184
0.8323
0.9290
0.9757
1.0000

0.0000
0.1117
0.1929
0.3188
0.4859
0.6200
0.7176
0.7884
0.8399
0.8924
0.9544
0.9839
1.0000

21.09
22.92
24.59
27.63
32.75
38.04
42.54
45.98
48.38
50.84
52.91
53.76
54.14

1.548
1.515
1.486
1.430
1.335
1.234
1.150
1.089
1.051
1.020
1.003
1.000
1.000

1.000
1.000
1.001
1.005
1.019
1.053
1.110
1.190
1.278
1.417
1.596
1.700
1.758

0.0
35.2
66.7
123.4
213.9
291.3
327.5
318.7
281.4
203.4
95.2
33.5
0.0

T = 333.15 K
0.0000
0.0327
0.0624
0.1159
0.2291
0.3638
0.5032
0.6253
0.7180
0.8344
0.9303
0.9768
1.0000

0.0000
0.1100
0.1910
0.3083
0.4776
0.6106
0.7097
0.7805
0.8331
0.8979
0.9537
0.9833
1.0000

31.43
34.00
36.40
40.39
47.71
54.93
61.15
65.86
69.03
72.67
75.28
76.41
76.90

1.533
1.501
1.470
1.419
1.322
1.225
1.143
1.085
1.050
1.018
1.003
1.000
1.000

1.000
1.000
1.001
1.005
1.020
1.053
1.110
1.187
1.270
1.414
1.578
1.676
1.729

0.0
36.3
69.5
124.1
218.4
294.4
329.5
319.4
283.0
197.6
93.9
32.5
0.0

x1

y1

0.1516
0.2033
0.2472
0.3471
0.4395
0.5455
0.6576
0.7431
0.8260
0.8883
1.0000

0.5551
0.6222
0.6652
0.7304
0.7726
0.8102
0.8457
0.8728
0.9038
0.9317
1.0000

T = 333.15 K
0.0000
0.0111
0.0224
0.0475
0.0765
0.1114
0.1496
0.2079
0.2544
0.3472
0.4413
0.5484
0.6592
0.7440
0.8256
0.8895
1.0000

0.0000
0.0797
0.1504
0.2700
0.3713
0.4588
0.5273
0.6016
0.6451
0.7070
0.7525
0.7988
0.8354
0.8652
0.8974
0.9286
1.0000

P (kPa)

a
Experimental uncertainties: <0.001 mole fraction in composition, 0.02 K in temperature, 0.1% of the pressure value.

62

J. Pavlcek et al. / Fluid Phase Equilibria 344 (2013) 5964

Table 4
Parameters of the Wilson equation valid between 313 and 333 K, and evaluated standard deviations.
12 11 (J mol1 )

21 22 (J mol1 )

V1 (ml mol1 )

2,3-Dimethylbutane (1) + diisopropyl ether (2)

496.41
133.9137.7
224.91
2,3-Dimethylbutane (1) + 3-methyl-2-butanone (2)
2867.58
133.9137.7
328.06
Diisopropyl ether (1) + 3-methyl-2-butanone (2)
2232.92
145.0149.1
720.16

V2 (ml mol1 )

No. of points

x

y

P (kPa)

T (K)

145.0149.1

35

0.0017

0.0022

0.002

0.02

109.7112.2

47

0.0055

0.0044

0.003

0.02

109.7112.2

33

0.0020

0.0028

0.002

0.01

Table 5
Parameters of the NRTL equation valid between 313 and 333 K, and evaluated standard deviations.
g12 g22 (J mol1 )

g21 g11 (J mol1 )

12

2,3-Dimethylbutane (1) + diisopropyl ether (2)

285.974
48.024
2,3-Dimethylbutane (1) + 3-methyl-2-butanone (2)
1245.34
852.085
Diisopropyl ether (1) + 3-methyl-2-butanone (2)
325.174
1220.94

No. of points

x

y

P (kPa)

T (K)

1.998

35

0.0027

0.0030

0.003

0.01

1.3042

47

0.0032

0.0039

0.002

0.01

0.7984

33

0.0019

0.0027

0.002

0.01

Standard deviations for input data were estimated to 0.0030 for

a mole fraction of the phases, 0.01 K for temperature, and 0.01 kPa
for pressure. The evaluated parameters for the Wilson and NRTL
equations are presented in Tables 4 and 5, respectively, together
with standard deviations for all variables (x, y, P, T). Approximate molar volumes of pure components required for the Wilson
equation are given in Table 4. The true values were evaluated at
estimated temperature during the iteration process. The experimental data are illustrated as xyP plots in Figs. 13. Solid lines
represent smoothed values based on the optimised NRTL equation
parameters.
Table 6 shows the experimental data for the ternary system,
determined under the same isothermal conditions as the binary
systems. Overall compositions of mixtures in the equilibrium still
were obtained by adding diisopropyl ether to several initial 2,3dimethylbutane + 3-methyl-2-butanone mixtures. In such a way,
the experimental points were regularly arranged over the ternary

110

90

P (kPa)

70

50

30

10
0.0

0.2

0.4

0.6

0.8

1.0

mole fraction of 2,3-dimethylbutane

Fig. 2. Isothermal vapourliquid equilibrium in the 2,3-dimethylbutane + 3methyl-2-butanone system (xyP plot). Experimental data: 313.15 K (, ),
323.15 K (, ), 333.15 K (, ); (solid points) liquid phase; (open points) vapour
phase; () NRTL correlation.

Table 6
Vapourliquid equilibrium experimental data for the 2,3-dimethylbutane
(1) + diisopropyl ether (2) + 3-methyl-2-butanone (3) system.a
x1

x2

y1

y2

P (kPa)

T = 313.15 K
0.3839
0.3522
0.3224
0.2995
0.2690
0.2442
0.2153
0.1911
0.1655
0.1351
0.1101
0.0897
0.0709
0.0539
0.0946
0.0934
0.0875
0.0843
0.0826
0.0756
0.0685
0.0595
0.7218
0.6533
0.6013
0.5196
0.4328
0.3528

0.0516
0.1235
0.1988
0.2613
0.3297
0.4058
0.4816
0.5453
0.6179
0.6934
0.7576
0.8080
0.8531
0.8923
0.0369
0.0940
0.1485
0.2241
0.3180
0.4246
0.5153
0.5953
0.0551
0.1452
0.2125
0.3182
0.4347
0.5412

0.7274
0.6673
0.6030
0.5501
0.4946
0.4357
0.3799
0.3310
0.2818
0.2273
0.1825
0.1478
0.1154
0.0871
0.4386
0.3842
0.3357
0.2875
0.2413
0.1933
0.1584
0.1290
0.8527
0.7911
0.7432
0.6656
0.5726
0.4834

0.0510
0.1224
0.1968
0.2606
0.3272
0.4018
0.4743
0.5376
0.6058
0.6793
0.7426
0.7924
0.8390
0.8801
0.0759
0.1776
0.2629
0.3616
0.4610
0.5588
0.6332
0.6952
0.0404
0.1096
0.1629
0.2511
0.3565
0.4573

41.56
40.93
40.43
40.06
39.66
39.38
39.16
38.92
38.74
38.49
38.33
38.19
38.02
37.87
25.08
26.44
27.52
28.90
30.47
32.00
33.16
34.03
50.71
49.51
48.56
47.10
45.55
44.11

T = 323.15 K
0.3782
0.3509
0.3241
0.2993
0.2697
0.2432
0.2168
0.1929
0.1663
0.1355
0.1112
0.0908
0.0713
0.0539
0.0943
0.0939
0.0904
0.0903
0.0867

0.0514
0.1235
0.1978
0.2599
0.3275
0.4055
0.4804
0.5479
0.6186
0.6930
0.7580
0.8074
0.8538
0.8925
0.0364
0.0939
0.1488
0.1484
0.2242

0.7093
0.6488
0.5873
0.5349
0.4783
0.4211
0.3703
0.3185
0.2725
0.2198
0.1765
0.1436
0.1116
0.0846
0.4143
0.3667
0.3225
0.3200
0.2756

0.0521
0.1240
0.1992
0.2624
0.3291
0.4061
0.4771
0.5418
0.6099
0.6822
0.7455
0.7942
0.8411
0.8811
0.0747
0.1754
0.2593
0.2596
0.3573

59.11
58.38
57.93
57.50
57.03
56.78
56.56
56.37
56.16
55.86
55.70
55.52
55.34
55.16
36.60
38.57
40.15
40.01
42.17

J. Pavlcek et al. / Fluid Phase Equilibria 344 (2013) 5964

Table 6 (Continued)

80
x2

y1

y2

P (kPa)

0.0830
0.0760
0.0689
0.0602
0.7217
0.6513
0.6005
0.5222
0.4344
0.3561

0.3166
0.4237
0.5158
0.5974
0.0550
0.1456
0.2125
0.3175
0.4340
0.5391

0.2295
0.1851
0.1518
0.1230
0.8457
0.7799
0.7345
0.6548
0.5634
0.4718

0.4559
0.5543
0.6295
0.6918
0.0413
0.1126
0.1666
0.2577
0.3619
0.4650

44.40
46.68
48.42
49.69
72.04
70.42
69.19
67.34
65.25
63.38

T = 333.15 K
0.3798
0.3533
0.3242
0.3004
0.2704
0.2347
0.2186
0.1939
0.1674
0.1369
0.1123
0.0913
0.0722
0.0545
0.0967
0.0943
0.0902
0.0859
0.0830
0.0693
0.0604
0.7207
0.6529
0.6019
0.5216
0.4341
0.3560

0.0512
0.1228
0.1977
0.2592
0.3269
0.4067
0.4798
0.5470
0.6170
0.6927
0.7567
0.8071
0.8519
0.8920
0.0363
0.0931
0.1466
0.2228
0.3158
0.5153
0.5953
0.0545
0.1449
0.2116
0.3180
0.4325
0.5384

0.6917
0.6312
0.5708
0.5222
0.4645
0.4068
0.3593
0.3123
0.2646
0.2120
0.1726
0.1391
0.1088
0.0821
0.3950
0.3439
0.3070
0.2612
0.2179
0.1457
0.1184
0.8389
0.7733
0.7268
0.6456
0.5534
0.4648

0.0530
0.1259
0.2013
0.2642
0.3336
0.4104
0.4797
0.5440
0.6123
0.6834
0.7462
0.7967
0.8414
0.8826
0.0733
0.1728
0.2550
0.3528
0.4501
0.6261
0.6898
0.0423
0.1148
0.1693
0.2621
0.3672
0.4703

82.18
81.38
80.94
80.55
80.00
79.82
79.64
79.44
79.28
78.97
78.81
78.64
78.42
78.18
52.02
54.66
56.85
59.94
63.09
68.83
70.63
99.88
97.79
96.36
93.84
91.21
88.81

a
Experimental uncertainties: <0.001 mole fraction in composition, 0.02 K in temperature, 0.1% of the pressure value.

concentration region; altogether 74 experimental points were

measured.
The parameters obtained from the correlation of the three binary
VLE data were used to predict ternary data using the Wilson equation that expresses the activity coefcient  i (i = 1, 2, 3) as

 3



xs Ais

+1

s=1

3

r=1

xr Ari

(3)

xA
s=1 s rs

70

60

50

P (kPa)

x1

ln i = ln

63

40

30

20

10
0.2

0.0

0.4

0.6

0.8

1.0

mole fraction of diisopropyl ether

Fig. 3. Isothermal vapourliquid equilibrium in the diisopropyl ether + 3-methyl-2butanone system (xyP plot). Experimental data: 313.15 K (, ), 323.15 K (, ),
333.15 K (, ); (solid points) liquid phase; (open points) vapour phase; () NRTL
correlation.

where Aij = (Vj /Vi ) exp[ (ij ii )/RT], and using the NRTL equation

3
ln i =

 G x
r=1 ri ri r
3
G x
s=1 si s

3

r=1

xr Gir

G x
s=1 sr s

ir

 G x
t=1 tr tr t
3
G x
s=1 sr s

(4)

where Gij = exp[ ij  ij ];  ij = (gij gjj )/RT;  ii = 0; ij = ji ; Gii = 1. The

necessary molar volumes were estimated using the method of
Hougen and Watson [14].
For computation we used a method described by Hla et al.
[16], which makes it possible to calculate the closest solution by
minimising standard deviations of all involved variables (temperature, pressure, and vapour and liquid compositions). The resulting
absolute deviations are averaged and summarised in Table 7.
4. Discussion and conclusions
We have found no vapourliquid equilibrium data for the studied systems in the bibliography covering the period 18882007 [17]
and in the Web of Knowledge since 2008 to be able to compare
them. However, we believe that the obtained standard deviations
in our calculations, which are approximately proportional to the

Table 7
Prediction of vapourliquid equilibrium in the 2,3-dimethylbutane + diisopropyl ether + 3-methyl-2-butanone system at temperatures from 313 to 333 K using the binary
parameters of the Wilson and NRTL equations.
T (K)

x1

x2

x3

xall

y1

y2

y3

yall

P (kPa)

T (K)

Wilson equation
0.0065
313.15
0.0040
323.15
0.0032
333.15
0.0046
Mean

0.0015
0.0010
0.0009
0.0011

0.0067
0.0044
0.0035
0.0048

0.0049
0.0031
0.0025
0.0035

0.0036
0.0029
0.0028
0.0031

0.0012
0.0009
0.0010
0.0010

0.0027
0.0023
0.0023
0.0024

0.0025
0.0020
0.0020
0.0022

0.01
0.01
0.01
0.01

0.08
0.05
0.04
0.06

NRTL equation
313.15
323.15
333.15
Mean

0.0014
0.0010
0.0009
0.0011

0.0046
0.0032
0.0030
0.0036

0.0034
0.0023
0.0021
0.0026

0.0029
0.0026
0.0028
0.0028

0.0013
0.0010
0.0010
0.0011

0.0020
0.0021
0.0023
0.0021

0.0021
0.0019
0.0020
0.0020

0.01
0.01
0.01
0.01

0.05
0.04
0.04
0.04

0.0041
0.0027
0.0026
0.0031

 is an absolute average deviation of calculated and experimental data.

64

J. Pavlcek et al. / Fluid Phase Equilibria 344 (2013) 5964

magnitudes of input uncertainties sufciently verify the reliability

of both the data and the correlation procedure. The distribution of
deviations from the smoothed data conrms that there are only
expectable, random, and non-systematic errors. To test data consistency, we used the thermodynamic test proposed by Van Ness
[18]. According to this test, the consistency index for the presented data is in average lower than 2 (ranging from 1 to 3 for all
the nine isothermal data sets) on a ten-degree scale: 1 excellent,
10 unacceptable.
The experimental ternary data were compared with the data
predicted using the binary parameters. The absolute average deviations presented in Table 7 indicate that both the Wilson and NRTL
equations accurately predict ternary data. Quite as expected, the
NRTL equation proved slightly better. It should be pointed out
that these results do not necessarily reect the quality of data;
the experimental data are most likely more accurate because the
imperfections of the models may also contribute to certain deviations in the calculated values.
It must be also taken into account that the 2,3dimethylbutane + diisopropyl ether system does not depart
much from ideal behaviour. It is well known that the correlation of such systems is always problematic when non-classical
equation is involved. On the other hand, every system measured
isothermally at three temperatures is described with the use of
only one set of parameters, regardless of the temperature. The
evaluated deviations and the results shown in Figs. 13 (where
solid lines represent the NRTL correlation) prove that the measurement of experimental data and calculations were carried out
properly.

Acknowledgements
The authors wish to acknowledge technical assistance of Ms S.
Bernatov and a partial support of the Institute of Chemical Process
Fundamentals (internal project).
References
[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
[9]
[10]

[11]
[12]
[13]
[14]
[15]
[16]
[17]

[18]

I. Wichterle, ELDATA: Int. Electron. J. Phys.-Chem. Data 5 (1999) 179189.

S. Bernatov, I. Wichterle, Fluid Phase Equilib. 189 (2001) 111118.
S. Bernatov, I. Wichterle, Fluid Phase Equilib. 180 (2001) 235245.
S. Psutka, I. Wichterle, Fluid Phase Equilib. 220 (2004) 161165.
S. Psutka, I. Wichterle, Fluid Phase Equilib. 235 (2005) 5863.
S. Psutka, I. Wichterle, J. Chem. Eng. Data 50 (2005) 13381342.
S. Psutka, I. Wichterle, Fluid Phase Equilib. 264 (2008) 5561.
S. Bernatov, J. Pavlcek, I. Wichterle, Fluid Phase Equilib. 278 (2009) 129134.
S. Bernatov, J. Pavlcek, I. Wichterle, Fluid Phase Equilib. 307 (2011) 6671.
TRC Thermodynamic Tables Hydrocarbons; TRC Thermodynamic Tables
Non-Hydrocarbons, Thermodynamic Research Center, College Station, TX,
1999.
J.A. Riddick, W.B. Bunger, T.K. Sakano, Organic Solvents Techniques of Chemistry, vol. 2, fourth ed., John Wiley & Sons, New York, 1986.
Beilstein Handbuch der Organischen Chemie, vol. I, Suppl. V, Springer, Berlin,
1974, p. 3288.
J.G. Hayden, J.P. OConnell, Ind. Eng. Chem., Proc. Des. Dev. 14 (1975) 209216.
O.A. Hougen, K.M. Watson, Chemical Process Principles, Part II, J. Wiley, New
York, 1947.
J. Pavlcek, I. Wichterle, Fluid Phase Equilib. 260 (2007) 7073.
E. Hla, K. Aim, T. Boublk, J. Linek, I. Wichterle, VaporLiquid Equilibrium at
Normal and Reduced Pressures, Academia, Prague, 1982 (in Czech).
I. Wichterle, J. Linek, Z. Wagner, J.-C. Fontaine, K. Sosnkowska-Kehiaian,
H.V. Kehiaian, LandoltBrnstein IV/13A. Part 2. VaporLiquid Equilibrium in
Mixtures and Solutions, Springer, Berlin, 2008, 575 pp. + CD-ROM, ISBN: 9783-540-70744-8.
H.C. Van Ness, Pure Appl. Chem. 67 (1995) 859872.