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2,3 Dimethylbutane2
2,3 Dimethylbutane2
2,3 Dimethylbutane2
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
60
Table 1
Sample description.
Compound
Source
Purity by supplier
(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
x1
x2 A21
,
x1 + x2 A12
x2 + x1 A21
(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
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
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
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 )
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
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
Table 4
Parameters of the Wilson equation valid between 313 and 333 K, and evaluated standard deviations.
12 11 (J mol1 )
V1 (ml mol1 )
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 )
12
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
110
90
P (kPa)
70
50
30
10
0.0
0.2
0.4
0.6
0.8
1.0
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
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.
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
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)
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
64
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
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