Fluid Phase Equilibria 307 (2011) 6671

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Fluid Phase Equilibria

journal homepage: www.elsevier.com/locate/fluid

Isothermal vapourliquid equilibria in the binary and ternary systems

composed of 2,2,4-trimethylpentane, 2-methyl-1-propanol, and
4-methyl-2-pentanone
Svatoslava Bernatov, Jan Pavlcek, Ivan Wichterle
Institute of Chemical Process Fundamentals v.v.i., 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 27 February 2011
Received in revised form 13 May 2011
Accepted 16 May 2011
Available online 26 May 2011
Keywords:
Vapourliquid equilibrium
Experimental data
Prediction
Hydrocarbon
Alcohol
Ketone

a b s t r a c t
Vapourliquid equilibrium data in the three binary 2,2,4-trimethylpentane + 2-methyl-1-propanol, 2methyl-1-propanol + 4-methyl-2-pentanone, 2,2,4-trimethylpentane + 4-methyl-2-pentanone systems,
and in the ternary 2,2,4-trimethylpentane + 2-methyl-1-propanol + 4-methyl-2-pentanone system are
reported. The data were measured isothermally at 333.15, 348.15 and 364.15 K covering the pressure
range 12100 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; resulting parameters
were then used for calculation of phase behaviour in the ternary system and for subsequent comparison
with experimental data.
2011 Elsevier B.V. All rights reserved.

1. Introduction
New results of a continuing project dealing with phase equilibria (VLE) in mixtures belonging to distinct families of organic
compounds are reported in this paper. Vapourliquid equilibria are determined for three binary and one ternary systems
containing alcohol, hydrocarbon and ketone. Within the series
of papers, the systems of components 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]
and tert-butyl methyl ether + 3,3-dimethyl-2-butanone + 2,2dimethyl-1-propanol [8] have already been investigated.
Compounds used in this paper contain also both ketone, and
alcohol, and isobutyl groups, namely, 2,2,4-trimethylpentane,
2-methyl-1-propanol, and 4-methyl-2-pentanone. The new

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 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.uid.2011.05.011

data were measured at the three constant temperature levels,

particularly at 333.15, 348.15 and 364.15 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 DvorakBoublk type which is quoted in our previous papers
(e.g. [7]). The pressure was measured indirectly via the boiling
point of water in an ebulliometer connected in parallel to the
still; the uncertainty is 0.1% of the measured value. The equilibrium temperature was determined with the digital thermometer
F250 (ASL, United Kingdom) calibrated against a Ptresistance thermometer traceable to the NBS (Washington DC, USA) certicate
(1962), however, the basic resistance is regularly re-checked by
the triple point of water; the absolute uncertainty of temperature
measurement (on ITS-90 scale) was estimated as 0.02 K. Samples withdrawn for gas chromatographic (GC) analysis 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 (HewlettPackard)
with thermal conductivity detection. The estimated uncertainty of
the composition measurement is better than 0.001 mole fraction.
Density was measured with a vibrating tube densimeter DMA 58

S. Bernatov et al. / Fluid Phase Equilibria 307 (2011) 6671

(A. Paar, Austria); the refractive index was determined using the
precise Abbe type refractometer (Bellingham & Stanley, UK).

2,2,4-Trimethylpentane [isooctane] (Fluka AG), puriss. p.a.

ACS material (>99.5 mass%) was used as received after being
dried (and stored) over 4A molecular sieve. The purity determined by GC was 99.95 mass%; d4298.15 = 0.68779 g cm3 ,
= 1.38894. Literature data are: d4298.15 = 0.68781 g cm3
n298.15
D
[9], 0.687730.68778 g cm3
[10]; n298.15
= 1.38898 [9],
D
1.388931.38915 [10].
2-Methyl-1-propanol [isobutanol] (Fluka, Buchs, Switzerland),
puriss, p.a. ACS grade, declared purity of 99.5 mass%, was used
without further purication. Molecular sieve 4A was used to
remove water. Purity determined by GC was 99.77 mass%; the
=
density d4298.15 = 0.79779 g cm3 , and refractive index n298.15
D
1.39378. Literature data are: d4298.15 = 0.7982 g cm3 [9], 0.7978
= 1.39389 [9].
[11]; n298.15
D
4-Methyl-2-pentanone [isobutyl methyl ketone] (Fluka AG,
Buchs, Switzerland), puriss. p.a., ACS, declared purity 99.0 mass%,
was used as received after storage over 4A molecular sieve.
The purity determined by GC was 99.80 mass%. Density measured at 298.15 K was 0.79650 g cm3 , and refractive index
n298.15
= 1.39362. There are not many values for compariD
=
son: 0.79600.7965 g cm3 [10,12,13], 0.7963 g cm3 [9]; n298.15
D
1.39361 [9].
3. Results
The direct experimental xyP values together with the activity
coefcients,  1 ,  2 , and GE (evaluated from the NRTL correlation)
for the binary systems are given in Table 1. All three binary systems
are azeotropic. The data were correlated using the Wilson and NRTL
equation in the forms as follows (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

(1)

A12 = (V1 /V2 )exp[ (12 11 )/RT],

A21 = (V2 /V1 )
where
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 = x22 21

Table 1
Vapourliquid equilibrium experimental data and calculated (NRTL) activity coefcients with excess Gibbs energy in binary systems.a
x1

2.2. Materials

G21
x1 + x2 G21

2

12 G12
(x1 + x2 G12 )2

(2)

where
G12 = exp[ 12  12 ],
G21 = exp[ 21  21 ]
and
 12 = (g12 g22 )/RT,  21 = (g21 g11 )/RT. The equation contains
three adjustable parameters, namely (g12 g22 ), (g21 g11 ), and
12 = 21 .
Vapour phase imperfection and variation of the Gibbs energy
of the pure liquid components with pressure were accounted for
in terms of the second virial coefcients and the molar volumes
under saturation pressure estimated, respectively, by the method
of Hayden and OConnell [14] and of Hougen and Watson [15]. The
adjustable parameters for binary systems were evaluated with use
of the programme based on the maximum likelihood procedure
[16] which was recently modied by Pavlcek et al. [17]. This new
robust algorithm makes it possible to correlate VLE isotherms or
isobars together resulting in one set of universal parameters valid in
the experimental pressure and temperature range. It can be applied

67

y1

P (kPa)

1

2

2,2,4-Trimethylpentane (1) + 2-methyl-1-propanol (2)

T = 333.15 K
0.0000
12.38
5.860
1.000
0.0000
0.2347
15.83
5.200
1.002
0.0269
0.3483
18.34
4.705
1.005
0.0507
0.5134
23.12
3.717
1.026
0.1114
27.98
2.655
1.099
0.2138
0.6234
0.3683
0.6878
31.10
1.947
1.259
0.7196
32.39
1.622
1.457
0.4969
0.7410
33.05
1.411
1.734
0.6059
0.7055
0.7613
33.42
1.249
2.194
0.7857
33.46
1.130
3.003
0.8041
32.67
1.027
5.537
0.9263
0.8388
0.9828
0.9262
30.36
1.002
9.043
28.64
1.000
11.006
1.0000
1.0000
T = 348.15 K
26.07
5.263
1.000
0.0000
0.0000
0.0308
0.2053
31.98
4.631
1.002
0.3150
36.39
4.145
1.007
0.0595
0.4537
43.24
3.356
1.028
0.1206
0.5683
50.58
2.460
1.101
0.2304
55.30
1.846
1.258
0.3818
0.6355
0.5089
0.6717
57.30
1.542
1.464
0.6152
0.6987
58.19
1.356
1.737
0.7162
0.7242
58.52
1.218
2.161
0.7554
58.28
1.114
2.882
0.8130
0.8276
55.82
1.021
5.229
0.9304
0.9281
51.33
1.002
7.803
0.9819
48.29
1.000
9.210
1.0000
1.0000
T = 364.15 K
52.69
4.756
1.000
0.0000
0.0000
0.0352
0.1788
62.39
4.162
1.002
0.2809
69.69
3.700
1.009
0.0694
0.3948
78.94
3.089
1.029
0.1269
0.5115
90.00
2.309
1.100
0.2478
96.58
1.793
1.240
0.3993
0.5835
0.5225
0.6258
99.31
1.522
1.418
0.6242
0.6568
100.35
1.344
1.664
0.7268
0.6900
100.23
1.169
2.238
0.7307
98.92
1.075
3.094
0.8231
0.9323
0.8228
92.66
1.013
5.092
0.9810
0.9304
84.61
1.001
6.913
1.0000
1.0000
80.03
1.000
7.813
2,2,4-Trimethylpentane (1) + 4-methyl-2-pentanone (2)
T = 333.15 K
0.0000
14.45
2.314
1.000
0.0000
0.0217
14.68
2.296
1.000
0.0049
0.0771
15.40
2.240
1.000
0.0184
0.1850
16.88
2.123
1.002
0.0503
0.2677
18.22
2.015
1.006
0.0852
0.3741
20.21
1.850
1.018
0.1427
0.4910
22.72
1.634
1.048
0.2368
0.5625
24.45
1.479
1.091
0.3263
0.6301
26.05
1.331
1.166
0.4329
0.6923
27.36
1.206
1.285
0.5487
0.7380
28.13
1.131
1.415
0.6407
0.7972
28.77
1.065
1.633
0.7531
0.8353
28.99
1.037
1.801
0.8174
0.8696
29.06
1.021
1.962
0.8674
0.9132
28.99
1.007
2.192
0.9208
1.0000
28.64
1.000
2.634
1.0000
T = 348.15 K
0.0000
26.31
2.219
1.000
0.0000
0.0212
26.75
2.199
1.000
0.0056
27.88
2.148
1.000
0.0200
0.0737
0.0549
0.1737
30.27
2.037
1.002
0.2568
32.52
1.931
1.007
0.0913
0.3603
35.62
1.782
1.018
0.1489
0.4689
39.36
1.594
1.046
0.2427
42.18
1.446
1.088
0.3331
0.5449
0.4397
0.6153
44.79
1.305
1.162
0.6797
46.79
1.191
1.274
0.5554
47.96
1.122
1.396
0.6456
0.7280
0.7905
48.91
1.060
1.600
0.7558
49.19
1.034
1.753
0.8188
0.8308

GE (J mol1 )

0.0
120.3
222.7
469.5
823.2
1102.3
1191.2
1177.7
1070.4
870.6
449.7
124.9
0.0
0.0
138.7
261.3
498.3
841.7
1103.7
1181.5
1153.3
1040.7
843.2
402.2
115.1
0.0
0.0
156.0
295.8
512.0
850.0
1089.0
1166.5
1145.1
975.4
727.5
329.8
92.7
0.0

0.0
10.7
44.1
116.0
184.0
290.1
428.8
520.0
584.9
596.5
560.0
461.8
378.4
298.4
189.2
0.0
0.0
12.9
46.6
120.5
193.1
297.6
426.9
519.0
583.0
591.4
553.7
454.4
372.1

68

S. Bernatov et al. / Fluid Phase Equilibria 307 (2011) 6671

Table 1 (Continued)
x1

y1

P (kPa)

1

0.8670
49.22
1.019
0.8676
0.9121
49.10
1.007
0.9210
48.29
1.000
1.0000
1.0000
T = 364.15 K
0.0000
46.64
2.131
0.0000
0.0203
47.33
2.113
0.0060
0.0677
49.14
2.064
0.0217
0.1650
53.00
1.958
0.0589
56.51
1.860
0.0960
0.2444
0.1562
0.3433
61.25
1.724
0.2503
0.4485
66.94
1.554
0.3420
0.5286
71.48
1.413
0.5963
75.31
1.288
0.4445
0.6665
78.43
1.181
0.5599
80.13
1.118
0.6475
0.7178
0.7575
0.7845
81.44
1.060
81.85
1.033
0.8198
0.8270
0.8647
81.83
1.017
0.8690
81.55
1.006
0.9213
0.9113
1.0000
1.0000
80.03
1.000
2-Methyl-1-propanol (1) + 4-methyl-2-pentanone (2)
T = 333.15 K
0.0000
14.45
1.772
0.0000
0.0432
14.62
1.722
0.0307
0.1076
14.87
1.640
0.0827
15.20
1.522
0.1603
0.1896
0.2650
0.2874
15.53
1.380
15.58
1.294
0.3490
0.3527
0.4518
0.4285
15.53
1.204
0.5344
0.4917
15.39
1.144
0.6225
0.5568
15.15
1.093
0.7245
0.6403
14.70
1.048
0.8136
0.7282
14.20
1.022
0.8866
0.8149
13.63
1.008
0.9349
0.8839
13.16
1.003
0.9715
0.9457
12.76
1.001
0.9833
12.50
1.000
0.9916
12.38
1.000
1.0000
1.0000
T = 348.15 K
26.31
1.612
0.0000
0.0000
0.0304
0.0452
26.68
1.575
0.1105
27.28
1.514
0.0817
0.1552
0.2013
28.02
1.429
0.2615
0.3057
28.75
1.324
0.3426
0.3759
29.25
1.246
0.4422
0.4562
29.48
1.175
29.45
1.125
0.5279
0.5213
0.6126
0.5884
29.30
1.083
0.6731
28.93
1.045
0.7142
0.7570
28.34
1.020
0.8049
0.8377
27.66
1.008
0.8795
0.9006
27.10
1.003
0.9308
0.9534
26.54
1.001
0.9693
0.9859
26.19
1.000
0.9910
1.0000
26.07
1.000
1.0000
T = 364.15 K
0.0000
46.64
1.478
0.0000
0.0463
47.42
1.451
0.0306
0.1140
48.65
1.407
0.0804
0.2064
50.26
1.345
0.1549
0.3167
52.37
1.256
0.2549
0.3921
53.39
1.203
0.3402
0.4784
54.31
1.148
0.4346
0.5485
54.82
1.108
0.5185
0.6178
55.05
1.073
0.6059
0.7013
55.08
1.040
0.7063
54.78
1.019
0.7971
0.7823
0.8744
0.8574
54.28
1.007
0.9132
53.75
1.003
0.9271
0.9599
53.18
1.001
0.9675
0.9880
52.82
1.000
0.9905
52.68
1.000
1.0000
1.0000

2

GE (J mol1 )

1.899
2.098
2.495

293.0
189.2
0.0

1.000
1.000
1.000
1.003
1.007
1.018
1.045
1.086
1.152
1.257
1.365
1.546
1.699
1.849
2.022
2.369

0.0
13.2
48.2
125.5
198.7
301.2
426.4
519.6
578.5
587.4
552.9
460.0
370.7
282.4
183.5
0.0

1.000
1.000
1.003
1.013
1.040
1.070
1.123
1.181
1.257
1.373
1.495
1.616
1.709
1.785
1.832
1.853

0.0
44.1
114.2
212.0
318.4
371.7
408.5
413.0
392.0
332.3
254.1
169.2
102.9
48.3
14.9
0.0

1.000
1.000
1.003
1.010
1.030
1.057
1.098
1.144
1.205
1.294
1.395
1.494
1.568
1.635
1.675
1.689

0.0
37.2
98.3
180.2
270.7
325.0
358.1
364.5
349.0
301.7
231.9
156.1
97.0
43.6
11.5
0.0

1.000
1.000
1.002
1.008
1.026
1.045
1.077
1.113
1.160
1.232
1.312
1.391
1.452
1.507
1.540
1.552

0.0
32.4
83.8
152.7
238.6
279.6
309.2
316.6
306.2
267.5
208.1
142.6
88.8
40.1
11.0
0.00

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

Fig. 1. Isothermal vapourliquid equilibrium in the 2,2,4-trimethylpentane + 2methyl-1-propanol system (xyP plot). Experimental data: 333.15 K (, ), 348.15 K
(, ), 364.15 K (, ); solid points liquid phase, open points vapour phase; ()
NRTL correlation.

to any correlation equation with temperature independent parameters such as, e.g. the Wilson or NRTL equations.
Within the correlation procedure [16], the experimental vapour
pressures of the pure components were used instead of a vapour
pressure equation for calculations, which is a procedure generally
recognised and recommended for isothermal data. It can be realized by adjustment of the parameter A in the Antoine equation to
the experimental value of vapour pressure at the particular temperature. Naturally, this is not applicable to the new procedure
[17], and to keep the experimental pressures unchanged for pure
components, the measured vapour pressures of pure component
were used for functional correlation of Antoine parameters for this
purpose only.
The standard deviations necessary for computation input were
estimated as 0.0030 for mole fraction of phases, 0.01 K for temperature and 0.01 kPa for pressure. Parameters for the Wilson and NRTL
equations are presented in Tables 2 and 3, respectively, together
with resulting standard deviations for all variables (x, y, P, T). The
approximate values of molar volumes of pure components required
for the Wilson equation are given in Table 2, however, they have
always been evaluated at given temperature. The experimental
data are illustrated in Figs. 13 as xyP plots. Solid lines represent
the smoothed values based on optimised NRTL equation parameters.
Azeotropic behaviour was found in all systems studied.
Experimental data for azeotropes were obtained by plotting x
versus xy and x versus P; numerically smoothed curves in
these simple plots provide values which are summarised in
Table 4. Comparison with literature is not reliable; for each of
the 2,2,4-trimethylpentane + 2-methyl-1-propanol and 2-methyl1-propanol + 4-methyl-2-pentanone systems there is only one very
obsolete value (in the collection [18]), although showing fair agreement in Taz versus Paz plots. However, azeotropic compositions
differ of about 0.03 and 0.09 in mole fraction, in the two respective
systems. A larger difference for the second system could be due to
a very at xyP plot (see Fig. 3). Additionally, one data point was
found in [19], which is in a good agreement with presented data.

S. Bernatov et al. / Fluid Phase Equilibria 307 (2011) 6671

69

Table 2
Parameters of the Wilson equation valid between 333 and 364 K, and evaluated standard deviations.
12 11 (J mol1 )

21 22 (J mol1 )

V1 (ml mol1 )

2,2,4-Trimethylpentane (1) + 2-methyl-1-propanol (2)

356.05
6492.61
173.4180.4
2,2,4-Trimethylpentane (1) + 4-methyl-2-pentanone (2)
2658.76
173.4180.4
78.616
2-Methyl-1-propanol (1) + 4-methyl-2-pentanone (2)
147.83
95.999.7
1655.50

V2 (ml mol1 )

No. of points

x

y

P

T

95.999.7

33

0.0310

0.0091

0.061

0.10

131.0136.0

42

0.0066

0.0044

0.014

0.02

131.0136.0

42

0.0158

0.0126

0.088

0.09

Table 3
Parameters of the NRTL equation valid between 333 and 364 K, and evaluated standard deviations.
g12 g22 (J mol1 )

g21 g11 (J mol1 )

ij

2,2,4-Trimethylpentane (1) + 2-methyl-1-propanol (2)

1.4008
1430.91
1947.12
2,2,4-Trimethylpentane (1) + 4-methyl-2-pentanone (2)
1158.32
1.1205
832.30
2-Methyl-1-propanol (1) + 4-methyl-2-pentanone (2)
49279.11
0.0056
46342.4

No. of points

x

y

P (kPa)

T (K)

33

0.0086

0.0039

0.011

0.03

42

0.0032

0.0026

0.007

0.01

42

0.0033

0.0033

0.012

0.01

Table 4
Experimental azeotropic data.a
System

Taz (K)

x1az

Paz (kPa)

2,2,4-Trimethylpentane (1) + 2-methyl-1-propanol (2)

333.15
348.15
364.15
333.15
348.15
364.15
333.15
348.15
364.15

0.7782
0.7263
0.6708
0.8775
0.8645
0.8439
0.3620
0.5024
0.6713

33.50
58.51
100.45
29.06
49.23
81.88
15.58
29.48
55.10

2,2,4-Trimethylpentane (1) + 4-methyl-2-pentanone (2)

2-Methyl-1-propanol (1) + 4-methyl-2-pentanone (2)

Uncertainties: 0.01 K in experimental T, 0.001 in evaluated composition, 0.04 kPa in evaluated P.

Fig. 2. Isothermal vapourliquid equilibrium in the 2,2,4-trimethylpentane + 4methyl-2-pentanone system (xyP plot). Experimental data: 333.15 K (, ),
348.15 K (, ), 364.15 K (, ); solid points liquid phase, open points vapour
phase () NRTL correlation.

The experimental data for the ternary system were determined at the same isothermal conditions as the binary systems
and are presented in Table 5. Overall compositions of mixtures in the equilibrium still were formed approximately by
subsequent addition of 2-methyl-1-propanol to several initial

Fig. 3. Isothermal vapourliquid equilibrium in the 2-methyl-1-propanol + 4methyl-2-pentanone system (xyP plot). Experimental data: 333.15 K (, ),
348.15 K (, ), 364.15 K (, ); solid points liquid phase, open points vapour
phase; () NRTL correlation.

2,2,4-trimethylpentane + 4-methyl-2-pentanone mixtures; then,

the region of ternary compositions was regularly covered; altogether 85 experimental points were measured. Since all three
binary systems are azeotropic, azeotropic behaviour was found also
in ternary system. Nevertheless, it is impossible the evaluate the
experimental value analogously as for binary systems.

70

S. Bernatov et al. / Fluid Phase Equilibria 307 (2011) 6671

Table 5
Vapourliquid equilibrium experimental data in the ternary 2,2,4-trimethylpentane
(1) + 2-methyl-1-propanol (2) + 4-methyl-2-pentanone (3) system.a
x1
T = 333.15 K
0.2601
0.2349
0.1959
0.0263
0.0124
0.0062
0.0550
0.0542
0.0487
0.0461
0.0253
0.0130
0.0060
0.0032
0.0004
0.0030
0.0024
0.0020
0.6797
0.6219
0.2197
0.1186
0.8601
0.7887
0.7177
0.6372
0.5445
T = 348.15 K
0.2650
0.2493
0.2063
0.0565
0.0296
0.0132
0.0068
0.0646
0.0594
0.0565
0.0529
0.0301
0.0139
0.0076
0.0038
0.0028
0.0060
0.0033
0.0020
0.6918
0.6312
0.2279
0.1240
0.8666
0.7934
0.7228
0.6427
0.5484
T = 364.15 K
0.2786
0.2610
0.0613
0.0326
0.0142
0.0074
0.0747
0.0683
0.0639
0.0591
0.0347
0.0161
0.0088
0.0024
0.0082
0.0042
0.0024

x2

y1

y2

P (kPa)

0.7009
0.6531
0.5560
0.2891
0.2039
0.1375
0.9327
0.9060
0.8604
0.7942
0.7194
0.6347
0.5485
0.4692
0.9758
0.9382
0.8894
0.8052
0.2875
0.2668
0.1364
0.0993
0.1021
0.0974
0.0921
0.0852
0.0756

0.6296
0.5877
0.5150
0.1152
0.0560
0.0284
0.3580
0.3418
0.3013
0.2696
0.1567
0.0798
0.0357
0.0188
0.0050
0.0303
0.0228
0.0119
0.7464
0.7187
0.4710
0.3314
0.8017
0.7728
0.7454
0.7144
0.6762

0.3457
0.3344
0.3151
0.2796
0.2224
0.1643
0.6266
0.6096
0.5912
0.5533
0.5553
0.5297
0.4849
0.4355
0.9491
0.8674
0.8034
0.7535
0.2301
0.2123
0.1202
0.0988
0.1684
0.1438
0.1233
0.1037
0.0844

28.65
27.65
25.78
17.04
16.00
15.45
18.57
18.61
18.36
18.26
16.91
16.10
15.76
15.65
12.75
13.55
13.94
14.20
32.97
32.18
23.74
19.64
32.59
31.78
31.02
30.03
28.79

0.6952
0.6378
0.5452
0.3593
0.2838
0.1991
0.1353
0.9225
0.8992
0.8495
0.7860
0.7082
0.6260
0.5376
0.4609
0.9692
0.9302
0.8819
0.7975
0.2753
0.2576
0.1340
0.0971
0.0955
0.0935
0.0887
0.0826
0.0732

0.5749
0.5385
0.4777
0.1944
0.1092
0.0515
0.0267
0.3284
0.3026
0.2790
0.2483
0.1482
0.0699
0.0372
0.0174
0.0162
0.0471
0.0231
0.0099
0.7121
0.6862
0.4486
0.3163
0.7864
0.7568
0.7296
0.6984
0.6578

0.3991
0.3871
0.3594
0.3340
0.2981
0.2348
0.1721
0.6583
0.6545
0.6263
0.5924
0.5905
0.5666
0.5137
0.4637
0.9511
0.8647
0.8245
0.7835
0.2668
0.2447
0.1318
0.1060
0.1831
0.1578
0.1350
0.1131
0.0918

51.43
49.73
46.59
34.41
31.52
29.46
28.36
36.79
36.11
35.89
35.51
32.79
30.91
30.23
29.72
26.91
28.28
28.37
28.48
57.66
56.12
41.69
35.81
55.98
54.59
53.29
51.56
49.41

0.6811
0.6252
0.3516
0.2780
0.1955
0.1332
0.9121
0.8892
0.8397
0.7736
0.6977
0.6176
0.5298
0.9746
0.9249
0.8759
0.7895

0.5213
0.4944
0.1820
0.1035
0.0476
0.0253
0.2953
0.2717
0.2493
0.2251
0.1373
0.0665
0.0352
0.0156
0.0473
0.0236
0.0089

0.4536
0.4345
0.3571
0.3150
0.2453
0.1791
0.6930
0.6903
0.6658
0.6304
0.6228
0.5967
0.5409
0.9560
0.8763
0.8430
0.8073

90.64
84.56
61.83
56.74
52.87
50.68
70.02
68.76
67.89
66.65
61.64
58.00
56.20
54.64
56.20
55.76
55.31

Table 5 (Continued)
x1

x2

y1

y2

P (kPa)

0.0044
0.0043
0.0041
0.7014
0.6403
0.4017
0.3084
0.1309
0.8712
0.7974
0.7263
0.6474
0.5538

0.7601
0.6997
0.6381
0.2657
0.2487
0.1762
0.1531
0.0949
0.0914
0.0899
0.0869
0.0805
0.0713

0.0220
0.0195
0.0181
0.6796
0.6564
0.5486
0.4882
0.3000
0.7757
0.7462
0.7162
0.6834
0.6415

0.7353
0.6892
0.6363
0.2993
0.2739
0.1861
0.1626
0.1124
0.1930
0.1655
0.1440
0.1211
0.0979

56.28
56.36
56.31
98.68
95.62
82.60
76.83
62.37
93.57
91.42
89.39
86.60
83.10

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

The parameters obtained from the correlation of the three binary

VLE data were exploited for prediction of ternary data using both
the Wilson and NRTL equations expressing the activity coefcient,
 i (i = 1, 2, 3) as
ln i = ln

 3



xs Ais

+1

s=1

3


xr Ari

r=1

(3)

xA
s=1 s rs

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

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;  ij = 0; ij = jj ; Gij = 1,

respectively. The necessary molar volumes were estimated with
use of the method of Hougen and Watson [15].
The computation was carried out by means of the method published in [16] enabling the calculation of the closest solution by
minimisation of standard deviations of all involved variables (temperature, pressure, and vapour and liquid compositions). Resulting
absolute deviations are averaged and summarised in Table 6.
4. Discussion and conclusions
No published vapourliquid equilibrium data for the studied systems were found in the bibliography covering the
period 18882007 [20]. One data set was found for the 2,2,4trimethylpentane + 2-methyl-1-propanol system in [19]; unfortunately, those data were measured at isobaric conditions, therefore
preventing from direct comparison. Nevertheless, the reliability of
both the data and correlation procedure is veried by the fact that
the resulting standard deviations are approximately proportional
to the magnitudes of input uncertainties. Generally, the inspection
of deviation distribution from smoothed data conrms that there
are only expectable, random and non-systematic errors. Thermodynamic test of consistency has been carried out with use of the
procedure proposed by Van Ness [21]. According to this test, for the
presented data, the consistency index in average equals largely
to 3 (ranging from 2 to 5 for all nine isothermal data sets) within
the ten-degree scale: 1 excellent, 10 non acceptable.
The experimental ternary data were compared with the data
predicted using binary parameters. The absolute average deviations presented in Table 6 indicate that both the Wilson and NRTL
equations predict ternary data within the near accuracy limits. Surprisingly, the prediction with use of Wilson equation is better that
with NRTL; in any case, the results are very good. It should be
pointed out that these results need not necessarily reect the quality of data. The experimental data are most likely better, because

S. Bernatov et al. / Fluid Phase Equilibria 307 (2011) 6671

71

Table 6
Prediction of vapourliquid equilibrium in the 2,2,4-trimethylpentane (1) + 2-methyl-1-propanol (2) + 4-methyl-2-pentanone (3) system at temperatures from 333 and 364 K
using the binary parameters of the Wilson and NRTL equations.
T (K)
Wilson equation
333.15
348.15
364.15
Mean
NRTL equation
333.15
348.15
364.15
Mean

x1

x2

x3

x

y1

y2

y3

y

P (kPa)

T (K)

0.0051
0.0014
0.0056
0.0040

0.0057
0.0021
0.0065
0.0048

0.0058
0.0024
0.0078
0.0053

0.0055
0.0019
0.0066
0.0047

0.0086
0.0024
0.0079
0.0063

0.0055
0.0030
0.0051
0.0045

0.0062
0.0024
0.0081
0.0056

0.0068
0.0026
0.0071
0.0055

0.01
0.00
0.02
0.01

0.13
0.03
0.11
0.09

0.0260
0.0305
0.0252
0.0272

0.0434
0.0400
0.0358
0.0.397

0.0258
0.0359
0.0270
0.0296

0.0317
0.0355
0.0293
0.0322

0.0139
0.0172
0.0146
0.0152

0.0167
0.0185
0.0200
0.0184

0.0209
0.0257
0.0246
0.0237

0.0171
0.0205
0.0197
0.0191

0.02
0.04
0.08
0.05

0.24
0.26
0.31
0.27

 is an absolute average deviation of calculated and experimental data.

the imperfections of models also contribute to certain worsening

of calculated values.
It must be also taken into account, that the 2-methyl-1propanol + 4-methyl-2-pentanone systems does not depart much
from ideal behaviour. It is well known that correlation of slightly
nonideal systems makes always problems when non-classical correlation equation is involved. On the other hand, every system
measured isothermally at three temperatures is described with use
of only one set of parameters independent of temperature. The evaluated deviations together with results shown in Figs. 13 (where
solid lines represent the NRTL correlation) prove that measurement
of experimental data and numerical procedures were carried out in
a proper way.

[4]
[5]
[6]
[7]
[8]
[9]
[10]
[11]
[12]
[13]
[14]
[15]
[16]

Acknowledgement
The authors acknowledge the partial support of the Grant
Agency of the Czech Republic (grant no. 104/07/0444).

[17]
[18]
[19]
[20]

References
[1] I. Wichterle, ELDATA: Int. Electron. J. Phys. Chem. Data 5 (1999) 179189.
[2] S. Bernatov, I. Wichterle, Fluid Phase Equilib. 189 (2001) 111118.
[3] S. Bernatov, I. Wichterle, Fluid Phase Equilib. 180 (2001) 235245.

[21]

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.
J.A. Riddick, W.B. Bunger, T.K. Sakano, Organic Solvents Techniques of Chemistry, vol. 2, fourth ed., John Wiley & Sons, New York, 1986.
J. Timmermans, Physico-chemical Constants of Pure Organic Compounds, vol.
I, vol. II, Elsevier, Amsterdam, 1965/1950.
TRC Thermodynamic Tables-Hydrocarbons; TRC Thermodynamic Tables-NonHydrocarbons, Thermodynamic Research Center, College Station, TX, 1999.
CRC Handbook of Chemistry and Physics, 84th ed., CRC Press, Boca Raton FL,
USA, 2003.
Beilstein, Handbuch der Organischen Chemie, Springer, Berlin, 1972.
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.
E. Hla, K. Aim, T. Boublk, J. Linek, I. Wichterle, VaporLiquid Equilibrium at
Normal and Reduced Pressures, Academia, Prague, 1982 (in Czech).
J. Pavlcek, I. Wichterle, Fluid Phase Equilib. 260 (2007) 7073.
J. Gmehling, J. Menke, J. Krafczyk, K. Ficher, Azeotropic Data, VCH, Weinstein,
Germany, 1994.
V. Martnez-Soria, M. Pilar Pena, J.B. Montn, J. Chem. Eng. Data 44 (1999)
608612.
I. Wichterle, J. Linek, Z. Wagner, J.-C. Fontaine, K. SosnkowskaKehiaian, H.V.
Kehiaian, LandoltBrnstein IV/13A VaporLiquid Equilibrium in Mixtures and
Solutions, Part 2, Springer, Berlin, 2008, ISBN 978-3-540-70744-8, 575pp.
+CDROM.
H.C. Van Ness, Pure Appl. Chem. 67 (1995) 859872.