2
0
2017
tri
gon
0
journal
Original
Tristan, C. A.[Cristina Alonso]
Gonzalez, J. A.[Juan Antonio]
Hevia, F.[Fernando]
De La Fuente, I. G.[Isaias Garcia]
Cobos, J. C.[Jose Carlos]
J. Chem. Eng. Data
2017
2020-09-29
Liquid Liquid Equilibria for Systems Containing 4-Phenylbutan-2-one or Benzyl Ethanoate and Selected Alkanes
Liquid liquid equilibrium (LLE) phase diagrams have been determined, by means of the critical opalescence method with a laser scattering technique, for the mixtures 4-phenylbutan-2-one + CH3(CH2)nCH3 (n = 10,12,14) and for benzyl ethanoate + CH3(CH2)nCH3 (n = 12,14). The systems are characterized by having an upper critical solution temperature (UCST), which increases with n. The corresponding LLE curves show a rather horizontal top and become skewed toward higher mole fractions of the polar compound when n is increased. Calorimetric and LLE measurements show that, for mixtures with molecules with a given functional group, interactions between aromatic molecules are stronger than those between homomorphic linear molecules (aromaticity effect). This has been ascribed to proximity effects arising from the presence of the polar group and the aromatic ring within the same molecule. Proximity effects become weaker in the sequence 1-phenylpropan-2-one greater than4-phenylbutan-2-one greater than1-phenylethanone and are more important in benzyl ethanoate than in ethyl benzoate molecules. Values of the critical compositions and temperatures calculated with the DISQUAC group contribution model are in good agreement with the experimental results. Accordingly, the shape of the LLE curves is also correctly described by DISQUAC.
LLE
aromatic polar compound
proximity effecs
DISQUAC
10.1021/acs.jced.6b00803
3
62
988-994
1
InChI=1S/C10H12O/c1-9(11)7-8-10-5-3-2-4-6-10/h2-6H,7-8H2,1H3
AKGGYBADQZYZPD-UHFFFAOYSA-N
4-phenyl-2-butanone
benzylacetone
C10H12O
1
Commercial source
1
98
2
Stated by supplier
2
0.07
1
Karl Fischer titration
2
InChI=1S/C9H10O2/c1-8(10)11-7-9-5-3-2-4-6-9/h2-6H,7H2,1H3
QUKGYYKBILRGFE-UHFFFAOYSA-N
benzyl ethanoate
acetic acid, benzyl ester
benzyl acetate
ethanoic acid, benzyl ester
ethanoic acid, phenylmethyl ester
C9H10O2
1
Commercial source
1
99
2
Stated by supplier
2
0.035
2
Karl Fischer titration
3
InChI=1S/C12H26/c1-3-5-7-9-11-12-10-8-6-4-2/h3-12H2,1-2H3
SNRUBQQJIBEYMU-UHFFFAOYSA-N
dodecane
n-dodecane
C12H26
1
Commercial source
1
98
2
Stated by supplier
2
0.0025
2
Karl Fischer titration
4
InChI=1S/C14H30/c1-3-5-7-9-11-13-14-12-10-8-6-4-2/h3-14H2,1-2H3
BGHCVCJVXZWKCC-UHFFFAOYSA-N
tetradecane
n-tetradecane
C14H30
1
Commercial source
1
99
2
Stated by supplier
2
0.0025
2
Karl Fischer titration
5
InChI=1S/C16H34/c1-3-5-7-9-11-13-15-16-14-12-10-8-6-4-2/h3-16H2,1-2H3
DCAYPVUWAIABOU-UHFFFAOYSA-N
hexadecane
cetane
n-hexadecane
C16H34
1
Commercial source
1
99
2
Stated by supplier
2
0.0033
2
Karl Fischer titration
1
1
1
Principal objective of the work
EP
EP
2/10/2017
1
Mass density, kg/m3
Vibrating tube method
Liquid
Direct value, X
1
Data file compiler
Propagation of evaluated standard uncertainties
95
Liquid
1
Temperature, K
Liquid
2
Pressure, kPa
Liquid
1
298.15
5
2
101.325
6
1
984.742
6
1
4.009
2
2
1
Principal objective of the work
SAM
XXX
12/28/2016
1
Mass density, kg/m3
Vibrating tube method
Liquid
Direct value, X
1
Data file compiler
Propagation of evaluated standard uncertainties
95
Liquid
1
Temperature, K
Liquid
2
Pressure, kPa
Liquid
1
298.15
5
2
101.325
6
1
1051.1
6
1
4.21
3
3
1
Principal objective of the work
SAM
XXX
12/28/2016
1
Mass density, kg/m3
Vibrating tube method
Liquid
Direct value, X
1
Data file compiler
Propagation of evaluated standard uncertainties
95
Liquid
1
Temperature, K
Liquid
2
Pressure, kPa
Liquid
1
298.15
5
2
101.325
6
1
745.508
6
1
3.029
4
4
1
Principal objective of the work
SAM
XXX
12/28/2016
1
Mass density, kg/m3
Vibrating tube method
Liquid
Direct value, X
1
Data file compiler
Propagation of evaluated standard uncertainties
95
Liquid
1
Temperature, K
Liquid
2
Pressure, kPa
Liquid
1
298.15
5
2
101.325
6
1
759.275
6
1
3.045
5
5
1
Principal objective of the work
SAM
XXX
12/28/2016
1
Mass density, kg/m3
Vibrating tube method
Liquid
Direct value, X
1
Data file compiler
Propagation of evaluated standard uncertainties
95
Liquid
1
Temperature, K
Liquid
2
Pressure, kPa
Liquid
1
298.15
5
2
101.325
6
1
770.221
6
1
3.089
6
3
1
1
1
Principal objective of the work
EP
EP
2/10/2017
1
Liquid-liquid equilibrium temperature, K
VISOBS
Liquid mixture 1
Direct value, X
1
Data file compiler
Propagation of evaluated standard uncertainties
95
Liquid mixture 1
Liquid mixture 2
1
Pressure, kPa
Liquid mixture 1
100
1
1
Mole fraction
1
Liquid mixture 1
1
0.2232
4
1
279.3
4
1
0.3
1
0.2653
4
1
285.2
4
1
0.3
1
0.2833
4
1
286.4
4
1
0.3
1
0.2929
4
1
287.1
4
1
0.3
1
0.325
4
1
288.9
4
1
0.3
1
0.3431
4
1
289.6
4
1
0.3
1
0.3688
4
1
290.6
4
1
0.3
1
0.4059
4
1
291.4
4
1
0.3
1
0.4605
4
1
292.3
4
1
0.3
1
0.4775
4
1
292.4
4
1
0.3
1
0.4844
4
1
292.5
4
1
0.3
1
0.4853
4
1
292.5
4
1
0.3
1
0.5528
4
1
292.4
4
1
0.3
1
0.5673
4
1
292.4
4
1
0.3
1
0.5993
4
1
292.3
4
1
0.3
1
0.6316
4
1
292.2
4
1
0.3
1
0.6521
4
1
292.2
4
1
0.3
1
0.6695
4
1
291.9
4
1
0.3
1
0.6939
4
1
291.6
4
1
0.3
1
0.7211
4
1
291
4
1
0.3
1
0.7534
4
1
289.9
4
1
0.3
1
0.7684
4
1
289.1
4
1
0.3
1
0.7997
4
1
286.8
4
1
0.3
1
0.8176
4
1
285.5
4
1
0.3
1
0.8341
4
1
283.2
4
1
0.3
1
0.8683
4
1
278.3
4
1
0.3
7
4
1
1
1
Principal objective of the work
EP
EP
2/10/2017
1
Liquid-liquid equilibrium temperature, K
VISOBS
Liquid mixture 1
Direct value, X
1
Data file compiler
Propagation of evaluated standard uncertainties
95
Liquid mixture 1
Liquid mixture 2
1
Pressure, kPa
Liquid mixture 1
100
1
1
Mole fraction
1
Liquid mixture 1
1
0.2262
4
1
285.8
4
1
0.3
1
0.2421
4
1
287.3
4
1
0.3
1
0.2911
4
1
291.6
4
1
0.3
1
0.3173
4
1
293.4
4
1
0.3
1
0.3346
4
1
294.7
4
1
0.3
1
0.3524
4
1
295.5
4
1
0.3
1
0.3731
4
1
296.4
4
1
0.3
1
0.3958
4
1
297.4
4
1
0.3
1
0.4479
4
1
299
4
1
0.3
1
0.461
4
1
299.3
4
1
0.3
1
0.504
4
1
300
4
1
0.3
1
0.5259
4
1
300.1
4
1
0.3
1
0.5511
4
1
300.1
4
1
0.3
1
0.5826
4
1
300
4
1
0.3
1
0.5949
4
1
300
4
1
0.3
1
0.6374
4
1
299.9
4
1
0.3
1
0.6873
4
1
299.8
4
1
0.3
1
0.7021
4
1
299.7
4
1
0.3
1
0.7183
4
1
299.5
4
1
0.3
1
0.7218
4
1
299.4
4
1
0.3
1
0.7475
4
1
298.9
4
1
0.3
1
0.774
4
1
297.1
4
1
0.3
1
0.7958
4
1
295.6
4
1
0.3
1
0.8233
4
1
293.6
4
1
0.3
1
0.8566
4
1
289.9
4
1
0.3
1
0.8629
4
1
289
4
1
0.3
1
0.892
4
1
285.7
4
1
0.3
8
5
1
1
1
Principal objective of the work
EP
EP
2/10/2017
1
Liquid-liquid equilibrium temperature, K
VISOBS
Liquid mixture 1
Direct value, X
1
Data file compiler
Propagation of evaluated standard uncertainties
95
Liquid mixture 1
Liquid mixture 2
1
Pressure, kPa
Liquid mixture 1
100
1
1
Mole fraction
1
Liquid mixture 1
1
0.2459
4
1
290.2
4
1
0.3
1
0.2521
4
1
290.8
4
1
0.3
1
0.2903
4
1
295.3
4
1
0.3
1
0.3035
4
1
296.2
4
1
0.3
1
0.3438
4
1
299.1
4
1
0.3
1
0.3533
4
1
299.8
4
1
0.3
1
0.3862
4
1
301.8
4
1
0.3
1
0.4053
4
1
302.9
4
1
0.3
1
0.4257
4
1
303.6
4
1
0.3
1
0.4397
4
1
304.1
4
1
0.3
1
0.4676
4
1
305.7
4
1
0.3
1
0.5174
4
1
306.4
4
1
0.3
1
0.5433
4
1
306.8
4
1
0.3
1
0.592
4
1
307
4
1
0.3
1
0.6483
4
1
307
4
1
0.3
1
0.6709
4
1
306.9
4
1
0.3
1
0.7028
4
1
306.7
4
1
0.3
1
0.7288
4
1
306.5
4
1
0.3
1
0.7457
4
1
306.4
4
1
0.3
1
0.776
4
1
306
4
1
0.3
1
0.7991
4
1
305.3
4
1
0.3
1
0.8161
4
1
304.4
4
1
0.3
1
0.8521
4
1
302
4
1
0.3
1
0.8714
4
1
299.3
4
1
0.3
1
0.8981
4
1
294.5
4
1
0.3
9
2
1
4
1
Principal objective of the work
EP
EP
2/10/2017
1
Liquid-liquid equilibrium temperature, K
VISOBS
Liquid mixture 1
Direct value, X
1
Data file compiler
Propagation of evaluated standard uncertainties
95
Liquid mixture 1
Liquid mixture 2
1
Pressure, kPa
Liquid mixture 1
100
1
1
Mole fraction
2
Liquid mixture 1
1
0.348
4
1
280
4
1
0.3
1
0.3762
4
1
281.9
4
1
0.3
1
0.4014
4
1
283.2
4
1
0.3
1
0.4429
4
1
285.1
4
1
0.3
1
0.4452
4
1
285.1
4
1
0.3
1
0.4756
4
1
286.2
4
1
0.3
1
0.5098
4
1
287
4
1
0.3
1
0.5244
4
1
287.3
4
1
0.3
1
0.5582
4
1
287.8
4
1
0.3
1
0.578
4
1
287.9
4
1
0.3
1
0.5898
4
1
288
4
1
0.3
1
0.6211
4
1
288.1
4
1
0.3
1
0.6501
4
1
288.3
4
1
0.3
1
0.6619
4
1
288.2
4
1
0.3
1
0.6909
4
1
288.2
4
1
0.3
1
0.7069
4
1
288.1
4
1
0.3
1
0.7088
4
1
288.1
4
1
0.3
1
0.7198
4
1
288.1
4
1
0.3
1
0.7213
4
1
288.1
4
1
0.3
1
0.7619
4
1
287.7
4
1
0.3
1
0.7887
4
1
287.1
4
1
0.3
1
0.7958
4
1
286.9
4
1
0.3
1
0.8243
4
1
285.6
4
1
0.3
1
0.8476
4
1
283.2
4
1
0.3
1
0.8721
4
1
280.2
4
1
0.3
10
2
1
5
1
Principal objective of the work
EP
EP
2/10/2017
1
Liquid-liquid equilibrium temperature, K
VISOBS
Liquid mixture 1
Direct value, X
1
Data file compiler
Propagation of evaluated standard uncertainties
95
Liquid mixture 1
Liquid mixture 2
1
Pressure, kPa
Liquid mixture 1
100
1
1
Mole fraction
2
Liquid mixture 1
1
0.3915
4
1
287.8
4
1
0.3
1
0.4011
4
1
288.2
4
1
0.3
1
0.4319
4
1
289.4
4
1
0.3
1
0.4512
4
1
290.5
4
1
0.3
1
0.4616
4
1
290.9
4
1
0.3
1
0.4634
4
1
290.9
4
1
0.3
1
0.511
4
1
292.9
4
1
0.3
1
0.5289
4
1
293.4
4
1
0.3
1
0.5609
4
1
294
4
1
0.3
1
0.5745
4
1
294.3
4
1
0.3
1
0.6006
4
1
294.7
4
1
0.3
1
0.6235
4
1
295
4
1
0.3
1
0.6463
4
1
295.1
4
1
0.3
1
0.6695
4
1
295.1
4
1
0.3
1
0.6952
4
1
295.1
4
1
0.3
1
0.7127
4
1
295
4
1
0.3
1
0.7487
4
1
295
4
1
0.3
1
0.7671
4
1
294.9
4
1
0.3
1
0.8052
4
1
294.3
4
1
0.3
1
0.8184
4
1
293.6
4
1
0.3
1
0.839
4
1
293.2
4
1
0.3
1
0.8676
4
1
291.2
4
1
0.3
1
0.8917
4
1
288.1
4
1
0.3
1
0.9109
4
1
285.4
4
1
0.3