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Supporting Information
Ionic liquids as Entrainers for Terpenes Fractionation and other Relevant Separation Problems
Sérgio M. Vilas-Boas1,2, Gabriel Teixeira1,3, Sabrina Rosini1,3, Mónia A. R. Martins2, Priscilla S. Gaschi3, João A. P. Coutinho2, Olga Ferreira1 and Simão P. Pinho1*
1Centro de Investigação de Montanha (CIMO), Instituto Politécnico de Bragança, Campus de Santa Apolónia, 5300-253 Bragança, Portugal
2CICECO – Aveiro Institute of Materials, Department of Chemistry, University of Aveiro, 3810-193 Aveiro, Portugal
3UTFPR – Departamento de Engenharia Química, Universidade Tecnológica Federal do Paraná, 84016-210 Ponta Grossa, Brazil
*Corresponding author: Simão P. Pinho, E-mail address: [email protected], Phone: +351 273303086, Fax: +351 273313051.
Section S1 – Experimental
Table S1. Chemical structure, supplier, normal boiling temperature (K) and purity (mass fraction) of the solutes.
Family
Compounds
Chemical structure
Supplier
Boiling temperature (K)
Purity (mass fraction)
water
-a
373.15b
-a
Alkanes
octane
Aldrich
398.77b
≥ 0.990
nonane
Aldrich
423.91b
≥ 0.990
decane
Aldrich
447.20b
≥ 0.990
Cycloalkanes
cyclohexane
Aldrich
353.90b
≥ 0.990
methylcyclohexane
Aldrich
374.00b
≥ 0.990
Ketones
propanone (acetone)
Aldrich
329.30b
≥ 0.999
2-butanone
Aldrich
353.00b
≥ 0.990
Ethers
ethoxyethane (diethyl ether)
Aldrich
307.70b
≥ 0.999
Cyclic Ethers
oxolane (THF)
Aldrich
339.00b
≥ 0.999
1,4-dioxane
Aldrich
374.30b
≥ 0.998
Aromatic Hydrocarbons
benzene
Aldrich
353.22b
≥ 0.998
toluene
Aldrich
383.75b
≥ 0.998
ethylbenzene
Aldrich
409.35b
≥ 0.998
p-xylene
Aldrich
411.51b
≥ 0.990
Esters
methyl acetate
Aldrich
330.00
≥ 0.998
vinyl acetate
Riedel-de-Häen
345.70
≥ 0.990
ethyl acetate
Aldrich
350.20
≥ 0.998
Alcohols
methanol
Aldrich
337.80b
≥ 0.999
ethanol
Aldrich
351.50b
≥ 0.998
1-propanol
Aldrich
370.30b
≥ 0.999
2-propanol
Fluka
355.50b
≥ 0.999
2-methyl-1-propanol (isobutanol)
Aldrich
380.80b
≥ 0.995
1-butanol
Aldrich
390.60b
≥ 0.998
2-butanol
Aldrich
372.00b
≥ 0.995
2-methyl-2-propanol (tert-butanol)
Aldrich
355.50b
≥ 0.997
acetonitrile
Fluka
355.15b
≥ 0.999
pyridine
Aldrich
388.15b
≥ 0.998
thiophene
Aldrich
357.15b
≥ 0.990
Terpenes
α-pinene
Aldrich
430.00b
≥ 0.980
β-pinene
Aldrich
439.20b
≥ 0.990
R(+)-limonene
Aldrich
449.65b
≥ 0.970
p-cymene
Aldrich
450.28b
≥ 0.990
Terpenoids
(−)-menthone
Fluka
490.79b
≥ 0.990
(1R)-(−)-fenchone
Aldrich
466.65c
≥ 0.980
α-pinene oxide
Aldrich
447.15c
≥ 0.970
eucalyptol
Aldrich
449.55c
≥ 0.990
Terpenoids
linalool
Aldrich
471.65c
≥ 0.970
geraniol
Aldrich
502.15c
≥ 0.980
DL-citronellol
Aldrich
497.65c
≈ 0.950
(1R)-(+)-camphor
Aldrich
480.55c
≥ 0.980
(S)-(+)-carvone
Merck
503.65c
≥ 0.980
L(-)-menthol
Acros
488.55c
≥ 0.997
(-)-isopulegol
SAFC
470.15c
≥ 0.980
(−)-borneol
Fluka
485.15c
≥ 0.990
aUltrapure water (resistivity of18.2MΩ·cm, free particles ≥ 0.22 μm and total organic carbon < 5 μg·dm−3) was used all the experiments involving this solute.
bThe boiling temperature was obtained from Yaws [1].
cThe boiling temperature was obtained from ChemSpider [2,3].
Table S2. Summary of all the parameters used in the calculations of the vapor pressures and density of the pure terpenes and terpenoids.
Solute
Vapor pressure (Pa)a,b
Density (kmol⸱m-3)c
A
B
C
References
A
B
C
References
α-pinene
9.482
1719.099
-41.920
[4,5]
-2.001E-06
-4.866E-03
7.905E+00
[6]
β-pinene
9.612
1824.816
-38.019
[4,5]
-1.446E-06
-5.050E-03
7.996E+00
[6]
R(+)-limonene
9.574
1825.747
-47.977
[7,8]
-8.224E-07
-5.293E-03
7.822E+00
[6]
p-cymene
14.380
3741.421
66.761
[9]d
7.333E-07
-6.876E-03
8.358E+00
[6,10]
(−)-menthone
6.710
3386.390
214.095
[11]
-4.033E-07
4.810E-03
7.240E+00
[6]
(1R)-(−)-fenchone
9.137
1891.303
-33.614
[11,12]
-5.096E-07
5.228E-03
7.784E+00
[6]
α-pinene oxide
7.758
975.321
-127.321
[13]
-9.571E-07
-4.906E-03
7.861E+00
[6]
eucalyptol
9.157
1618.031
-59.920
[7,8]
-9.128E-07
-5.033E-03
7.550E+00
[6]
linalool
9.288
1606.944
-95.404
[14,15]
-3.680E-06
-3.230E-03
6.852E+00
[6]
geraniol
10.985
2542.520
-60.792
[16]
-3.161E-06
-2.790E-03
6.796E+00
[6]
DL-citronellol
10.985
2487.039
-64.114
[16]
-3.210E-06
-2.545E-03
6.512E+00
[6]
(1R)-(+)-camphor
12.987
3944.412
43.689
[12]
0
-1.79E-02
1.389 E+01
[1]e
S(+)-carvone
9.192
1864.966
-69.488
[17]
-4.877E-07
-5.046E-03
7.922E+00
[6]
L-(-)-menthol
8.543
1279.023
-133.227
[8,18]
-5.486E-06
-1.239E-03
6.578E+00
[6]
(-)-isopulegol
10.196
2144.688
-55.388
f
-9.100E-07
-4.831E-03
7.393E+00
[6]
(−)-borneol
10.021
1971.530
-90.643
[16]
6.425E-07
-7.641E-04
6.455E+00
g
aThe vapor pressures were calculated using the Antoine equation: , ,
bThe constants of the Antoine equation were obtained by multilinear regression (Origin 8.5) of vapor pressure data available in the literature.
cThe literature density data were fit using following second order polynomial equation: , ρ,
dThe vapor pressures of p-cymene were calculated using the following modified form of Antoine equation: , ,
e For (1R)-(+)-camphor, the density data were calculated by the following equation: ρ, (n = 0.286).
f Unpublished data.
gThe density data were obtained by using COSMO-RS with BP_TZVP_C30_1701 parametrization. The input cosmo file was generated TmoleX 3.3 program package using the COSMO-BP-TZVP template.
Table S3. Summary of all the critical properties, acentric factor and dipole moments of the pure terpenes and terpenoids.
Solute
Critical properties (Pa)a
Acentric factor
Dipole moment
References
Tc (K)
pc (MPa)
Vc (cm-3⸱mol)
ω
μ (C⸱m-1)b
α-pinene
630.8
2.89
484.50
0.326
1.16E-30
[6,19]
β-pinene
646.0
2.88
482.50
0.320
4.02E-30
[6,19]
R(+)-limonene
658.9
2.76
496.50
0.318
2.23E-30
[6,19]
p-cymene
652.0
2.80
497.00c
0.374c
2.64E-31
[1]
(−)-menthone
689.7
2.60
528.50
0.412
1.45E-29
[6,19]
(1R)-(−)-fenchone
679.2
3.08
503.50
0.388
1.47E-29
[6,19]
α-pinene oxide
716.4
3.09
489.50
0.369
9.76E-30
[6,19]
eucalyptol
661.05
2.45
509.50
0.339
8.03E-30
[6,19]
linalool
633.3
2.58
565.40
0.755
9.67E-30
[6,19]
geraniol
671.7
2.57
576.50
0.820
1.18E-29
[6,19]
DL-citronellol
657.9
2.45
589.50
0.848
7.86E-30
[6,19]
(1R)-(+)-camphor
700.2
3.08
503.50
0.388
1.53E-29
[19]
S(+)-carvone
724.8
28.60
503.50
0.419
1.78E-29
[6,19]
L-(-)-menthol
661.6
2.66
539.50
0.716
7.84E-30
[6,19]
(-)-isopulegol
656.8
2.77
527.50
0.698
9.70E-30
[6,19]
(−)-borneol
670.2
3.17
514.50
0.698
7.21E-30
[19]
aFor all the terpenes and terpenoids, the critical properties were reported by Martins and co-authors [6,19] and were calculated using the Joback group contribution approach [20], excepting for p-cymene.
bThe dipole moments were estimated using TURBOMOLE 6.1 program package applying the BP-86 density functional theory level with a triple-zeta valence (TZVP) basis set.
cFor p-cymene, the critical properties and acentric factor used in this work were reported by Yaws [1].
Section S2 – Results and discussion
Activity coefficients at infinite dilution:
Temperature conditions selected for the GC experiments
The activity coefficients at infinite dilution measured in this work at different temperatures are listed in Table S4. For hydrocarbons (alkanes, cycloalkanes, and aromatic compounds), ethers, esters, ketones, acetonitrile, pyridine, and thiophene, the GC measurements were performed in the temperature interval (333.15 – 383.15) K. For alcohols, terpenes, terpenoids, and water, higher temperatures were selected due to the long retention times required to be performed the GC experiments. Even if values at lower temperatures are better for separation factor analysis, a fair compromise between the retention times and the column temperature was needed to make it possible to collect reliable data.
For alcohols and water, experiments were carried out between 383.15 K to 403.15 K in [C4mim][OAc], whereas the temperature range was larger (363.15 – 413.15) K for the less polar [P6,6,6,14]Cl and [P6,6,6,14][(C8H17)2PO2] ILs. No experiments could be performed for water in [C4mim][OAc], once no response was observed in the above-mentioned temperature interval (within 200 minutes timeframe).
For terpenes and terpenoids, different temperature intervals were chosen for each ionic liquid, depending on the solute volatility. Consequently, for less volatile terpenoids, high temperatures were selected to avoid long retention times and its precipitation inside the column. Even so, for some terpenoids in [P6,6,6,14][(C8H17)2PO2], the number of experimental data obtained is much less than in [P6,6,6,14]Cl. Excepting linalool, the major oxygenated terpene in many essential oils [21–24], in the [C4mim][OAc] IL, no attempt was made to measure at temperatures higher than 403.15 K, because of the low thermal stability of imidazolium-based ionic liquids containing the acetate anion [25].
In the case of (1R)-(+)-camphor, L-(-)-menthol and (−)-borneol, which are solid at room temperature, small amounts of solutes were dissolved in ethanol or 2-propanol (with known retention times) before the injections.
Table S4. Activity coefficients at infinite dilution () of water and organic solutes in [P6,6,6,14]Cl, [P6,6,6,14][(C8H17)2PO2] and [C4mim][OAc] at different temperatures.
Different organic solutes
[P6,6,6,14]Cl
[P6,6,6,14][(C8H17)2PO2]a
[C4mim][OAc]b
333.15
343.15
353.15
363.15
373.15
383.15
333.15
343.15
353.15
363.15
373.15
383.15
333.15
343.15
353.15
363.15
373.15
383.15
octane
1.755
1.733
1.698
1.670
1.658
1.649
0.851
0.851
0.855
0.853
0.867
0.858
85.54
79.37
71.61
68.35
65.10
58.27
nonane
1.891
1.857
1.825
1.773
1.770
1.764
0.914
0.918
0.919
0.921
0.923
0.910
108.56
102.38
96.27
90.83
86.71
82.85
decane
2.098
2.032
2.013
1.955
1.931
1.892
0.997
0.997
0.996
0.998
1.001
0.986
149.94
139.66
130.48
123.73
117.34
110.92
cyclohexane
1.087
1.048
1.032
0.977
0.992
0.943
0.542
0.544
0.537
0.536
0.542
0.536
20.27
19.56
18.27
17.48
16.79
15.16
methylcyclohexane
1.144
1.115
1.105
1.075
1.076
1.064
0.597
0.586
0.585
0.608
0.611
0.597
27.55
26.23
25.13
24.18
23.38
22.38
benzene
0.494
0.493
0.497
0.500
0.501
0.508
0.474
0.474
0.471
0.466
0.460
0.454
2.57
2.60
2.62
2.62
2.64
2.67
toluene
0.593
0.595
0.599
0.607
0.605
0.603
0.526
0.524
0.526
0.520
0.526
0.513
4.09
4.22
4.11
4.13
4.11
4.07
ethylbenzene
0.705
0.704
0.698
0.707
0.706
0.711
0.593
0.591
0.597
0.587
0.588
0.574
6.07
6.06
6.05
6.03
6.04
6.05
p-xylene
0.727
0.731
0.732
0.740
0.733
0.740
0.596
0.597
0.607
0.596
0.597
0.585
6.43
6.44
6.45
6.44
6.45
6.46
diethyl ether
1.283
1.254
1.235
1.145
1.076
1.091
0.671
0.670
0.671
0.682
0.689
0.691
10.12
9.91
9.86
9.67
9.58
9.66
THF
0.626
0.617
0.610
0.598
0.585
0.595
0.438
0.440
0.436
0.432
0.436
0.427
3.04
2.91
2.89
2.86
2.84
2.86
1,4-dioxane
0.794
0.782
0.769
0.757
0.736
0.738
0.810
0.787
0.765
0.745
0.732
0.702
2.25
2.28
2.28
2.28
2.26
2.16
methyl acetate
1.090
0.991
1.021
0.975
0.939
0.941
0.895
0.864
0.839
0.818
0.805
0.789
2.88
2.85
2.87
2.84
2.83
2.87
ethyl acetate
1.108
1.071
1.050
1.019
0.987
0.993
0.842
0.821
0.803
0.788
0.781
0.757
4.24
4.19
4.19
4.15
4.14
-
vinyl acetate
0.997
0.963
0.948
0.923
0.896
0.899
0.920
0.894
0.865
0.843
0.832
0.817
-
-
-
-
-
-
acetone
0.795
0.774
0.768
0.744
0.719
0.729
0.899
0.868
0.836
0.810
0.793
0.766
2.07
2.04
2.08
2.05
2.03
1.91
2-butanone
0.730
0.720
0.721
0.716
0.720
0.714
0.752
0.738
0.724
0.707
0.700
0.675
2.25
2.27
2.29
2.27
2.26
2.28
acetonitrile
0.563
0.556
0.556
0.554
0.550
0.553
1.046
1.018
0.985
0.954
0.934
0.901
0.91
0.95
0.94
0.95
0.94
0.96
pyridine
0.421
0.419
0.420
0.427
0.421
0.429
0.589
0.576
0.563
0.555
0.543
0.524
1.26
1.27
1.29
1.29
-
1.31
thiophene
0.356
0.362
0.369
0.378
0.381
0.390
0.526
0.524
0.526
0.520
0.526
0.513
1.23
1.29
1.33
1.36
1.40
1.45
Alcohols/water
363.15
373.15
383.15
393.15
403.15
413.15
363.15
373.15
383.15
393.15
403.15
413.15
363.15
373.15
383.15
393.15
403.15
413.15
methanol
0.033
0.036
0.039
0.042
0.046
0.050
0.023
0.025
0.028
0.032
0.034
-
-
-
0.04
0.05
0.05
-
ethanol
0.043
0.046
0.050
0.054
0.059
0.065
0.034
0.037
0.040
0.046
0.049
-
-
-
0.08
0.08
0.09
-
1-propanol
0.038
0.041
0.046
0.051
0.056
0.061
0.030
0.033
0.037
0.043
0.047
-
-
-
0.10
0.12
0.13
-
2-propanol
0.052
0.056
0.062
0.068
0.075
0.082
0.049
0.054
0.058
0.068
0.067
-
-
-
0.12
0.14
0.15
-
1-butanol
0.037
0.040
0.044
0.049
0.054
0.060
0.028
0.032
0.035
0.042
0.045
-
-
-
0.12
0.14
0.16
-
2-butanol
0.049
0.054
0.060
0.067
0.075
0.083
0.047
0.052
0.057
0.066
0.075
-
-
-
0.15
0.18
0.19
-
isobutanol
0.033
0.036
0.041
0.045
0.049
0.055
0.026
0.030
0.030
0.036
0.042
-
-
-
0.12
0.14
0.15
-
tert-butanol
0.066
0.074
0.081
0.092
0.102
0.113
0.080
0.089
0.089
0.102
0.126
-
-
-
0.23
0.28
0.31
-
water
0.204
0.205
0.199
0.203
0.202
0.200
0.141
0.141
0.124
0.134
0.127
-
-
-
-
-
-
-
Terpenes/terpenoids
383.15
393.15
403.15
413.15
423.15
433.15
363.15
373.15
383.15
393.15
403.15
413.15
353.15
363.15
373.15
383.15
393.15
403.15
α-pinene
1.162
1.167
1.153
1.130
1.132
1.124
0.690
0.689
0.677
0.672
0.673
33.643
33.248
32.013
26.680
24.844
23.696
β-pinene
1.046
1.035
1.012
1.013
0.990
1.004
0.653
0.648
0.636
0.622
0.631
0.630
25.006
23.893
23.505
19.845
18.816
17.781
R(+)-limonene
1.166
1.146
1.132
1.124
1.114
1.111
0.749
0.743
-
-
0.724
-
27.270
26.528
26.043
25.514
24.78
23.96
p-cymene
1.214
1.193
1.181
1.176
1.160
1.156
0.783
0.779
-
-
0.743
-
16.338
15.894
15.590
15.138
-
14.758
(−)-menthone
0.844
0.846
0.867
0.913
0.972
1.025
0.705
0.673
-
-
0.667
0.696
9.186
9.318
9.473
9.836
10.000
10.125
(1R)-(−)-fenchone
1.299
1.327
1.339
1.384
1.373
1.415
-
-
-
-
0.998
-
12.288
12.406
12.456
12.573
12.715
12.872
α-pinene oxide
0.832
0.894
0.905
0.963
1.009
1.054
0.316
0.336
-
0.401
0.431
-
21.103
20.733
20.425
-
-
16.333
eucalyptol
1.052
1.069
1.060
1.069
1.081
1.080
0.687
0.689
-
-
0.704
12.288
12.406
12.456
12.573
12.715
12.872
linalool
-c
0.095
0.111
0.127
0.145
0.165
-
-
-
-
0.122
-
-d
-
-
-
-
-
S(+)-carvone
-
-
-
-
-
-
-
-
-
-
0.898
0.882
-
-
-
-
4.533
4.452
Low volatile terpenoids
433.15
438.15
443.15
448.15
453.15
458.15
geraniol
0.086
0.091
0.094
0.096
0.099
0.101
DL-citronellol
0.072
0.076
0.079
0.082
0.083
0.086
(1R)-(+)-camphor
0.473
0.449
0.428
0.405
0.404
0.373
S(+)-carvone
1.009
1.044
1.055
1.063
1.049
1.098
L-(-)-menthol
0.132
0.143
0.154
0.163
0.171
0.185
(-)-isopulegol
0.164
0.170
0.177
0.185
0.185
0.196
(−)-borneol
0.089
0.094
0.096
0.100
0.103
0.107
aNo measurements of the activity coefficients the low volatile terpenoids (geraniol, DL-citronellol, (1R)-(+)-camphor, S(+)-carvone, L-(-)-menthol, (-)-isopulegol and (−)-borneol) in [P6,6,6,14][(C8H17)2PO2] could be performed due to long retention times of the solute in the IL.
bNo measurements of the activity coefficients the low volatile terpenoids (geraniol, DL-citronellol, (1R)-(+)-camphor, S(+)-carvone, L-(-)-menthol, (-)-isopulegol and (−)-borneol) in [C4mim][OAc] could be performed due to thermal instability of the IL.
cThe activity coefficients at infinite dilution of linalool in [P6,6,6,14]Cl could not be measured at 383.15 K due to the long retention time. Instead, was measured at 443.15 K, and 0.191 was the found value.
dThe activity coefficients of linalool in [C4mim][OAc] were measured between (413.15-438.15) K and the results are: = 0.791 (T = 413.15 K); = 0.857 (T = 418.15 K); = 0.979 (T = 428.15 K); = 1.056 (T = 433.15 K); = 0.791 (T = 438.15 K).
Comparison with literature data
In Figure S1, the infinite dilution activity coefficients obtained in this work were compared to the data reported in previous studies [26–28]. The data found in literature comprise mostly hydrocarbons (octane, decane, cyclohexane, and benzene) and alcohols (methanol, ethanol, and 1-butanol), and some studied in different temperature intervals. For all the systems, the measured here presented the same order of magnitude of the data found in the literature. In the case of [P6,6,6,14][(C8H17)2PO2], the values published by Letcher et al. [27] are in high consistency with the data obtained in this work. Regarding [C4mim][OAc], the values reported by Stark et al.[28] are always higher than those found in this work, being the deviations more pronounced for decane and 1-butanol. Although lower temperatures were investigated by Banerjee and Khanna [26] for [P6,6,6,14]Cl (between 308.15 K and 328.15 K), the activity coefficients follow similar trends with temperature, matching the results obtained in this work for hydrocarbons (octane, cyclohexane, and benzene). However, the measured for methanol and ethanol are considerably lower than the values found by Banerjee and Khanna [26] (Figure S1a), which very unexpectedly show higher in alcohols than in hydrocarbons. Globally this short comparison gives excellent indications about the consistency of the data measured in this work.
Figure S1. Comparison between the experimental activity coefficients at infinite dilution obtained in this work and reported in literature for: a) [P6,6,6,14]Cl [26]; b) [P6,6,6,14][(C8H17)2PO2] [27]; c) [C4mim][OAc] [28].
Densities
A complete overview of the density data found in literature is given in Table S5, while the density data measured in this work for [P6,6,6,14]Cl and [P6,6,6,14][(C8H17)2PO2] are presented in Table S6. As expected, for both ionic liquids, the density decreases as temperature increases. To the best of our knowledge, the density data of [P6,6,6,14]Cl and [P6,6,6,14][(C8H17)2PO2] at 368.15 K and 373.15 K are reported here for the first time. In addition, no density data at 278.15 K was found in literature for [P6,6,6,14][(C8H17)2PO2]. Whenever possible, the experimental data obtained in this work were compared with the data available in literature, and the results are presented in Figure S2.
The density generally agrees with the literature data, presenting ARD (calculated as the ratio between the absolute value of the difference between the density data obtained in this work and the average value from literature, with the average value from literature) inferior to 0.6% for [P6,6,6,14]Cl and inferior to 0.7% for [P6,6,6,14][(C8H17)2PO2] (relative to the average literature values). In fact, the literature values are generally close, with the exception of the density reported by Carrera et al. [29] at 298.15 K (0.918 ± 0.003 ), which is slightly higher than the literature average value (0.899 ± 0.010 ).
Figure S2. Comparison between the density data obtained in this work and available in literature for: a) [P6,6,6,14]Cl [29–36]; b) [P6,6,6,14][(C8H17)2PO2] [30,31,36–42].
Table S5. Overview of the density data of pure [P6,6,6,14]Cl and pure [P6,6,6,14][(C8H17)2PO2] available in literature.
Ionic Liquid
Temperature range (K)
Pressure range (MPa)
Density range at atmospheric pressure (g cm-3)
NP
Reference
[P666614]Cl
298.15
0.1
0.918 ± 0.003
1
[29]
298.15
0.1
0.89182
1
[30]
298.15
0.1
0.89182
1
[31]
273.15 – 318.15
0.1 – 25.0
0.90727 – 0.87892
72
[32]
298.15 – 343.15
0.1
0.8826 – 0.8644
8
[33]
290.15 – 323.15
0.1
0.8975 – 0.8780
9
[34]
283.15 – 333.15
0.1 - 45.0
0.894 – 0.8689
87
[35]
278.15 – 363.15
0.1
0.9016 – 0.8523
18
[36]
298.13 – 333.14
0.19 – 65.00
-
134
[43]
283.15 – 373.15
0.1
0.8997 – 0.8460
19
this work
[P66614][(C8H17)2PO2]
298.15
0.1
0.88643
1
[30]
298.15
0.1
0.88643
1
[31]
298.15 – 363.15
0.1
0.9073 – 0.8631
14
[36]
298.15
0.1
0.88643
1
[37]
288.15 – 363.15
0.1
0.89086 – 0.84656
16
[38]
298.15 – 308.15
0.1
0.88524 – 0.87329
3
[39]
298.15 – 363.15
0.1
0.8893 – 0.8508
14
[40]
293.15 – 363.15
0.1
0.8921 – 0.8525
8
[41]
293.15 – 328.15
0.1
0.8940 – 0.8723
8
[42]
278.15 – 373.15
0.050 – 0.183
0.903 – 0.8453
20
this work
Table S6. Experimental densities of pure [P6,6,6,6,14]Cl and pure [P6,6,6,14][(C8H17)2PO2] measured in this work.
[P6,6,6,14]Cl
[P6,6,6,14][(C8H17)2PO2]
278.15
-
0.9033
283.15
0.8997
0.9001
288.15
0.8967
0.8970
293.15
0.8936
0.8939
298.15
0.8906
0.8907
303.15
0.8876
0.8876
308.15
0.8845
0.8845
313.15
0.8815
0.8814
318.15
0.8785
0.8783
323.15
0.8755
0.8753
328.15
0.8725
0.8723
333.15
0.8696
0.8692
338.15
0.8666
0.8662
343.15
0.8636
0.8632
348.15
0.8607
0.8602
353.15
0.8577
0.8572
358.15
0.8548
0.8542
363.15
0.8518
0.8512
368.15
0.8489
0.8482
373.15
0.8460
0.8453
aStandard uncertainties, u, are u(ρ) = ± 5 ⸱ 10-4 g ⸱cm-3, u(T) = 0.02 K and ur(p) = 0.05.
Gas liquid partition coefficientsTable S7. Gas-liquid partition coefficients () of water and organic solutes in [P6,6,6,14]Cl, [P6,6,6,14][(C8H17)2PO2] and [C4mim][OAc] at different temperatures.
Different organic solutes
[P6,6,6,14]Cl
[P6,6,6,14][(C8H17)2PO2]
[C4mim][OAc]
333.15
343.15
353.15
363.15
373.15
383.15
333.15
343.15
353.15
363.15
373.15
383.15
333.15
343.15
353.15
363.15
373.15
383.15
octane
255.775
175.803
125.305
91.283
67.447
50.840
353.905
240.426
166.964
120.001
86.519
65.581
16.296
11.934
9.245
6.948
5.357
4.491
nonane
620.307
408.013
276.949
195.789
138.303
100.264
861.624
554.240
369.329
253.030
177.920
130.423
33.555
23.011
16.342
11.907
8.804
6.664
decane
1467.366
932.741
600.184
407.103
279.288
198.492
2073.545
1276.415
814.666
535.238
361.664
255.554
63.760
42.184
28.823
20.033
14.334
10.567
cyclohexane
84.601
64.617
49.425
40.133
30.946
25.891
113.969
83.548
63.751
49.070
38.001
30.563
14.086
10.767
8.691
6.987
5.701
5.029
methylcyclohexane
151.655
111.778
83.037
64.266
49.285
38.993
195.234
142.702
105.221
76.293
58.287
46.597
19.564
14.775
11.365
8.899
7.076
5.784
benzene
184.171
134.913
100.239
76.067
59.151
46.185
129.028
94.158
70.977
54.809
43.199
34.712
109.817
79.466
59.065
45.152
35.016
27.485
toluene
428.892
299.451
213.981
155.025
116.877
89.682
324.738
228.168
163.321
121.587
90.221
70.728
193.415
131.317
96.911
71.008
53.630
41.530
ethylbenzene
895.624
601.784
419.443
293.321
213.379
157.103
714.334
481.173
329.356
237.132
171.964
130.453
322.906
217.398
150.514
107.263
77.730
57.627
p-xylene
940.314
626.309
431.113
301.485
220.217
161.439
770.851
515.289
348.827
251.141
181.511
137.075
330.206
220.980
152.238
107.973
78.082
57.708
diethyl ether
16.931
13.559
10.978
9.606
8.421
6.940
21.733
17.032
13.564
10.822
8.822
7.352
6.669
5.335
4.278
3.544
2.948
2.447
THF
91.656
69.075
53.042
41.933
33.825
26.664
88.003
65.088
49.804
38.972
30.466
24.945
58.671
45.543
34.892
27.294
21.689
17.292
1,4-dioxane
246.448
175.824
128.678
96.335
74.368
56.804
162.150
117.268
86.817
65.696
50.205
40.050
270.357
187.372
134.915
99.746
75.545
60.470
methyl acetate
39.853
32.633
24.124
19.656
16.179
13.026
32.592
25.125
19.702
15.720
12.659
10.413
46.812
35.281
26.749
21.045
16.734
13.322
ethyl acetate
78.014
58.110
43.743
34.056
27.116
21.207
68.929
50.863
38.402
29.545
23.013
18.652
63.294
46.162
34.137
26.047
20.188
19.911
vinyl acetate
74.163
55.658
42.000
32.771
26.164
20.609
53.948
40.253
30.908
24.082
18.909
15.209
63.712
48.514
36.590
28.882
23.231
-
acetone
53.459
41.198
31.773
25.597
21.033
16.737
31.744
24.657
19.605
15.791
12.804
10.699
137.698
100.139
74.512
57.625
45.155
35.636
2-butanone
125.020
91.994
68.273
52.209
40.189
31.955
81.539
60.277
45.674
35.502
27.753
22.676
340.508
238.029
181.579
137.056
106.961
82.616
acetonitrile
177.345
131.306
98.350
75.188
58.750
46.131
64.059
48.174
37.217
29.308
23.225
19.007
780.476
529.848
369.103
265.029
0.000
144.950
pyridine
752.268
517.353
362.782
257.301
192.437
142.139
360.985
252.812
181.743
132.896
100.253
78.058
263.476
183.221
131.811
97.736
73.324
56.052
thiophene
294.094
209.295
152.599
112.934
86.733
66.756
166.742
120.592
89.586
68.624
52.284
41.707
16.296
11.934
9.245
6.948
5.357
4.491
Alcohols/water
363.15
373.15
383.15
393.15
403.15
413.15
363.15
373.15
383.15
393.15
403.15
413.15
363.15
373.15
383.15
393.15
403.15
413.15
methanol
625.990
430.887
298.479
213.651
155.319
114.444
609.282
411.219
284.108
188.768
142.282
-
-
-
852.638
624.257
427.127
-
ethanol
772.511
516.283
351.241
244.664
174.176
124.466
658.534
432.589
293.545
192.375
141.553
-
-
-
732.961
507.390
354.023
-
1-propanol
1777.415
1148.422
740.178
498.440
344.945
242.888
1522.768
965.394
620.675
394.105
273.354
-
-
-
1102.132
675.008
466.485
-
2-propanol
728.858
481.934
323.557
222.129
156.642
112.271
519.387
338.728
232.193
149.023
150.810
-
-
-
505.575
340.461
240.726
-
1-butanol
4029.385
2509.596
1577.907
1019.731
680.665
461.798
3533.389
2133.963
1345.223
811.363
544.493
-
-
-
1223.073
815.104
551.306
-
2-butanol
1502.101
956.014
619.899
411.998
282.044
197.003
1058.327
667.244
443.004
282.382
188.949
-
-
-
1825.511
1082.649
724.573
-
isobutanol
3056.291
1905.137
1202.985
790.284
534.953
367.147
2606.167
1566.344
1089.256
655.161
416.968
-
-
-
756.011
493.602
339.815
-
tert-butanol
588.883
380.768
256.844
174.610
122.771
88.611
324.193
210.300
158.017
105.497
66.408
-
-
-
287.739
180.376
126.939
-
water
350.869
246.547
183.738
133.149
100.493
77.742
339.592
240.365
197.400
135.142
106.965
-
-
-
-
-
-
-
Terpenes/terpenoids
383.15
393.15
403.15
413.15
423.15
433.15
363.15
373.15
383.15
393.15
403.15
413.15
353.15
363.15
373.15
383.15
393.15
403.15
α-pinene
162.912
119.535
90.755
70.683
54.762
43.398
361.510
255.506
187.527
139.267
104.284
49.757
34.750
25.514
22.401
17.513
12.927
β-pinene
286.743
176.673
134.113
101.295
79.703
61.358
518.979
364.768
264.663
197.076
144.277
109.235
92.196
65.742
46.633
39.437
30.325
22.273
R(+)-limonene
334.216
241.944
177.783
132.430
100.641
77.280
739.983
506.367
-
-
186.412
-
170.738
115.299
79.505
53.641
38.674
29.980
p-cymene
334.145
241.895
177.747
132.404
101.470
78.199
741.459
504.562
-
-
190.394
-
238.699
158.416
106.843
75.050
----
35.347
(−)-menthone
1307.088
901.470
633.976
448.811
323.631
241.784
2569.537
1671.143
-
-
552.741
394.451
610.160
403.690
275.679
189.963
136.865
102.016
(1R)-(−)-fenchone
751.841
531.120
387.145
280.077
214.495
160.388
-
-
-
-
348.083
-
1122.993
723.764
477.991
400.733
286.733
191.864
α-pinene oxide
719.652
491.948
365.204
263.349
196.650
149.918
1475.361
992.286
-
-
351.869
166.078
113.122
79.445
-
-
37.707
eucalyptol
350.691
249.737
186.012
138.741
105.078
81.743
741.195
507.483
-
-
187.800
144.802
718.310
478.691
326.400
228.764
162.759
121.721
linalool
-
7144.375
4199.595
2553.270
1603.682
1030.166
-
-
-
-
2548.345
-
-
-
-
-
-
-
S(+)-carvone
-
-
-
-
-
-
-
-
-
-
1004.078
716.651
-
-
-
-
928.319
663.404
Low volatile terpenoids
433.15
438.15
443.15
448.15
453.15
458.15
geraniol
4608.079
3577.977
2874.036
2318.031
1891.766
1544.214
DL-citronellol
4478.618
3513.168
2779.377
2236.575
1828.032
1496.280
(1R)-(+)-camphor
240.953
211.400
185.822
165.370
140.446
129.108
S(+)-carvone
488.331
405.922
346.981
298.596
263.565
220.220
L-(-)-menthol
2273.248
1810.977
1453.236
1191.775
989.642
802.808
(-)-isopulegol
1067.451
875.415
722.298
595.963
513.445
420.773
(−)-borneol
3476.988
2759.137
2256.677
1834.460
1501.934
1234.633
linalool
-
-
-
-
-
-
aThe gas-liquid partition coefficient of linalool in [P6,6,6,6,14]Cl could not be measured at 383.15 K due to the long retention time. Instead, was measured at 443.15 K, and 663.351 was the found value.
bThe (gas-liquid)-partition coefficients of linalool in [C4mim][OAc] were measured between (41315-438.15) K and the results are: = 1287.494 (T = 413.15 K); = 1002.506 (T = 418.15 K); 636.174 (T = 428.15 K); = 506.377 (T = 433.15 K); = 378.156 (T = 438.15 K).
Infinite dilution thermodynamic functions
In Figure S3 and Table S8, the calculated ,, and values are presented. For alkanes, cycloalkanes, aromatic hydrocarbons, esters, ethers, ketones, acetonitrile, pyridine, thiophene, alcohols, terpenes, and some terpenoids, the excess partial molar properties were calculated from the experimental data at 383.15 K. For some low volatile terpenoids, however, the activity coefficients at infinite dilution were measured at higher temperatures, and the thermodynamic functions, calculated at 433.15 K, are also included in Figure S3 and in Table S8. For polar protic solutes (alcohols and low volatile terpenoids), the three excess partial molar properties and the values were generally negative, which means these solutes fall into the region (IV) of Figure S3. For these cases, the affinity between the solute and the ionic liquid is strong, and the enthalpic effects dominate over the entropics, since the absolute values of the enthalpies are higher than the entropic values.
In the case of the less polar solutes such as aliphatic and aromatic hydrocarbons, terpenes, ethers, esters, and ketones, the partial molar properties in [P6,6,6,14]Cl or [P6,6,6,14][(C8H17)2PO2] present similar behavior, but different from [C4mim][OAc]. Excepting alcohols, most of the solutes in [P6,6,6,14][(C8H17)2PO2] present positive values for both and , whereas the is always negative. The low polar solutes are placed in region (I) of Figure S3 (b), where entropic effects are dominant. For [P6,6,6,14]Cl, a similar behavior is observed for ethers, esters and ketones and aromatic hydrocarbons, but since some aliphatic hydrocarbons and terpenes show positive deviations from ideality ( > 1), some are located in regions (II) and (III).
The highly polar nature of [C4mim][OAc] leads to larger values for low polar solutes in comparison with the phosphonium-based ionic liquids. For this imidazolium-based IL, apart from the alcohols, and of most organic solutes are located in region (II) and region (III) of Figure S3 (c), respectively. For those, is positive, meaning weak affinity between the solute and the ionic liquid, and eventually even phase segregation.
Figure S3. Excess partial molar properties as function of the activity coefficients at infinite dilution for water and organic solutes in: a) [P6,6,6,14]Cl; b) [P6,6,6,14][(C8H17)2PO2]; c) [C4mim][OAc]. is the solid line (at 383.15 K) and dashed line (at 433.15 K); is shown by ● (at 383.15 K) and ● (at 433.15 K); is represented by ■ (at 383.15 K) and ■ (at 433.15 K).
Table S8. Thermodynamic functions at infinite dilution, namely the partial molar excess Gibbs free energies (/ kJ·mol-1), partial molar excess enthalpies (/kJ·mol-1) and partial molar excess entropies (/kJ·mol-1) of water and organic solutes in [P6,6,6,14]Cl, [P6,6,6,14][(C8H17)2PO2] and [C4mim][OAc] obtained in this work.
Solutes
[P6,6,6,14]Cl
[P6,6,6,14][(C8H17)2PO2]
[C4mim][OAc]
TRef = 383.15 K
octane
1.59
1.41
-0.19
-0.49
-0.29
0.20
12.95
7.76
-5.19
nonane
1.81
1.59
-0.22
-0.30
0.00
0.30
14.07
5.80
-8.28
decane
2.03
2.12
0.09
-0.04
0.12
0.16
15.00
6.33
-8.67
cyclohexane
-0.19
2.82
3.01
-1.99
0.21
2.20
8.66
5.90
-2.76
methylcyclohexane
0.20
1.52
1.32
-1.64
-0.49
1.15
9.90
4.32
-5.58
benzene
-2.16
-0.58
1.58
-2.52
0.95
3.46
3.13
-0.72
-3.85
toluene
-1.61
-0.45
1.16
-2.13
0.37
2.50
4.47
0.29
-4.19
ethylbenzene
-1.09
-0.18
0.90
-1.77
0.58
2.34
5.73
0.09
-5.64
p-xylene
-0.96
-0.33
0.63
-1.71
0.32
2.03
5.94
-0.08
-6.02
diethyl ether
0.28
4.07
3.80
-1.18
-0.74
0.44
7.23
1.09
-6.14
THF
-1.65
1.33
2.98
-2.71
0.49
3.20
3.35
1.21
-2.14
1,4-dioxane
-0.97
1.71
2.68
-1.13
2.90
4.03
2.45
0.66
-1.79
methyl acetate
-0.19
2.88
3.08
-0.75
2.64
3.40
3.36
0.16
-3.20
ethyl acetate
-0.02
2.51
2.53
-0.89
2.13
3.01
4.51b
0.59
-3.91
vinyl acetate
-0.34
2.32
2.66
-0.64
2.55
3.19
-
-
-
acetone
-1.01
2.09
3.10
-0.85
3.35
4.20
2.06
1.27
-0.79
2-butanone
-1.07
0.36
1.44
-1.25
2.18
3.44
2.63
-0.14
-2.77
acetonitrile
-1.89
0.39
2.28
-0.33
3.14
3.47
-0.13
-0.76
-0.63
pyridine
-2.70
-0.37
2.32
-2.06
2.34
4.40
0.86
-0.82
-1.68
thiophene
-3.00
-1.92
1.08
-2.13
0.37
2.50
1.18
-3.31
-4.50
methanol
-10.33
-10.28
0.05
-11.39
-12.52
-1.13
-10.25
-14.45
-4.19
ethanol
-9.54
-10.27
-0.73
-10.25
-11.53
-1.28
-8.05
-7.50
0.55
1-propanol
-9.81
-12.13
-2.32
-10.50
-14.14
-3.63
-7.34
-16.90
-9.56
2-propanol
-8.86
-11.55
-2.70
-9.07
-10.46
-1.39
-6.75
-14.37
-7.62
1-butanol
-9.95
-12.18
-2.23
-10.68
-14.86
-4.18
-6.75
-18.48
-11.73
2-butanol
-8.96
-13.28
-4.32
-9.13
-14.24
-5.11
-6.04
-15.25
-9.20
isobutanol
-10.18
-12.73
-2.55
-11.17
-13.82
-2.65
-6.75
-14.37
-7.62
tert-butanol
-8.01
-13.46
-5.45
-7.71
-12.60
-4.90
-4.68
-19.22
-14.53
water
-5.14
0.44
5.59
-6.65
3.20
9.85
-
-
-
α-pinene
0.48
1.09
0.62
-1.18
1.01
2.20
10.46
9.45
-1.01
β-pinene
0.14
1.34
1.20
-1.36
1.13
2.49
9.52
8.73
-0.79
R(+)-limonene
0.49
1.33
0.84
-0.92
1.15
2.08
10.32
2.94
-7.38
p-cymene
0.62
1.32
0.70
-0.78
1.85
2.63
8.66
2.44
-6.21
(−)-menthone
-0.54
-5.62
-5.08
-1.11
0.41
1.52
7.28
-2.49
-9.77
(1R)-(−)-fenchone
0.83
-2.22
-3.05
-
-
-
8.06
-1.06
-9.13
α-pinene oxide
-0.59
-6.34
-5.75
-3.67
-10.74
-7.07
-
-
-
eucalyptol
0.16
-0.68
-0.85
-1.20
-0.86
0.34
8.06
-1.06
-9.13
linaloola
-7.98
-19.43
-11.44
-
-
-
-
-
-
Solute
Tref = 433.15 K
geraniol
-8.84
-10.19
-1.35
-
-
-
-
-
-
DL-citronellol
-9.48
-11.25
-1.77
-
-
-
-
-
-
(1R)-(+)-camphor
-2.70
14.71
17.41
-
-
-
-
-
-
S(+)-carvone
0.03
-4.20
-4.23
-
-
-
-
-
-
L-(-)-menthol
-7.29
-21.52
-14.23
-
-
-
-
-
-
(-)-isopulegol
-6.51
-11.22
-4.71
-
-
-
-
-
-
(−)-borneol
-8.71
-11.66
-2.95
-
-
-
-
-
-
linalool
-
-
-
-
-
-
0.20
-24.42
-24.62
aThe excess partial molar properties of linalool at 383.15 K were extrapolated using data obtained in the temperature interval between (393.15 – 443.15) K.
bThe excess partial molar properties of ethyl acetate at 383.15 K were extrapolated using data obtained in the temperature interval between (333.15 – 373.15) K.
Selectivities and capacities
Separation of aromatics from aliphatic hydrocarbons.
In addition to the cases addressed in the body of the article, the activity coefficients at infinite dilution obtained in this work can be used to evaluate the potential of the studied ionic liquids for the removal of benzene compounds from aliphatic hydrocarbons. Table S9 compares the selectivities and capacities of octane/benzene and cyclohexane/benzene mixtures in [P6,6,6,14]Cl, [P6,6,6,14][(C8H17)2PO2] and [C4mim][OAc] (at 333.15 K) obtained in this work (experimentally and predicted using COSMO-RS) and calculated from experimental found in literature [26,27].
Table S9. Overview of the experimental and predicted and of octane/benzene and octane/cyclohexane mixtures in [P6,6,6,14]Cl, [P6,6,6,14][(C8H17)2PO2] and [C4mim][OAc] (at 333.15 K) obtained in this work and calculated from literature data [26,27].
Ionic liquid
/
Reference
octane/benzene
cyclohexane/benzene
[P6,6,6,14]Cl
3.55 /2.02a
2.20 /2.02a
[26]
2.05/2.51
1.57/2.51
this workb
2.65/1.71
1.59/1.71
this workc
[P6,6,6,14][(C8H17)2PO2]
1.70/1.81
1.10/1.81
[27]
1.80/2.11
1.14/2.11
this workb
1.64/1.91
1.13/.1.91
this workc
[C4mim][OAc]
33.28/0.39
7.89/0.39
this workb
11.89/0.71
3.73/0.71
this workc
aExtrapolated using the data reported by the authors.
bExperimental data.
cPredicted using COSMO-RS.
The experimental selectivities and capacities obtained in this work are quite close to the literature data for [P6,6,6,14]Cl [26] and [P6,6,6,14][(C8H17)2PO2] [27], being the larger deviations observed for octane/benzene in [P6,6,6,14]Cl. No selectivity and capacity data were found in literature for octane/benzene and cyclohexane/benzene mixtures in [C4mim][OAc].
The predicted and values are in excellent agreement with the average experimental data for the phosphonium-based ionic liquids, presenting ARDs inferior to 25%. For [C4mim][OAc], COSMO-RS predictions presented larger deviations from the experimental values obtained in this work, which is similar to the results obtained for the desulfurization and denitrification problems. Once again, the presence of the high polar acetate anion can lead to the formation of strong hydrogen-bond interactions between the solvent molecules, which might not be properly described in the COSMO-RS calculations. Nevertheless, the model is still capable of predicting the correct order of magnitude of the and values for the studied ionic liquids without the necessity of any experimental data, being a powerful tool to do a preliminary screening of the potential candidates to be tested by experimental approaches.
From all the cases presented in Table S9, the highest selectivities were obtained for [C4mim][OAc], whereas [P6,6,6,14]Cl presents the highest capacity values for benzene. Although both selectivity and capacity play relevant roles in the selection of an entrainer for a separation process, the poor selectivities obtained for the phosphonium-based ILs limits their use in the removal of benzene from mixtures with aliphatic hydrocarbons, once no significant differences between the affinities of the aliphatic hydrocarbon/IL and aromatic hydrocarbon/IL are observed. On the other hand, the high selectivity values observed for [C4mim][OAc], in particular for the octane/benzene mixture, suggest this ionic liquid interacts more intensely with one of the solutes (benzene), but further investigations, such as liquid-liquid equilibrium studies, are required to evaluate whether the low capacity of benzene restricts the use of [C4mim][OAc] at industrial scale.
Fractionation of terpenic mixturesTable S10. Experimental selectivities () and capacities () of the of terpenic mixtures in [P6,6,6,14]Cl at 403.15 K.
Solute
(1R)-(−)-fenchone
p-cymene
α-pinene
R(+)-limonene
eucalyptol
α-pinene oxide
S(+)-carvone
β-pinene
(−)-menthone
(1R)-(+)-camphor
(-)-isopulegol
linalool
L-(-)-menthol
(−)-borneol
geraniol
DL-citronellol
(1R)-(−)-fenchone
0.75
1.00
p-cymene
0.85
1.13
1.00
α-pinene
0.87
1.16
1.02
1.00
R(+)-limonene
0.88
1.18
1.04
1.02
1.00
eucalyptol
0.94
1.26
1.11
1.09
1.07
1.00
α-pinene oxide
0.99
1.32
1.17
1.14
1.12
1.05
1.00
S(+)-carvone
1.07
1.43
1.26
1.23
1.21
1.13
1.08
1.00
β-pinene
1.10
1.48
1.30
1.27
1.25
1.17
1.12
1.03
1.00
(−)-menthone
1.15
1.54
1.36
1.33
1.31
1.22
1.17
1.08
1.04
1.00
(1R)-(+)-camphora
1.57
2.10
1.85
1.81
1.77
1.66
1.59
1.46
1.42
1.36
1.00
(-)-isopulegola
7.67
10.27
9.06
8.84
8.68
8.13
7.76
7.17
6.94
6.65
4.90
1.00
Linaloola
9.01
12.06
10.64
10.39
10.20
9.55
9.12
8.42
8.15
7.81
5.75
1.17
1.00
L-(-)-menthol
11.72
15.70
13.84
13.52
13.27
12.43
11.86
10.96
10.61
10.16
7.48
1.53
1.30
1.00
(−)-borneola
14.15
18.94
16.71
16.31
16.01
14.99
14.32
13.22
12.80
12.26
9.03
1.84
1.57
1.21
1.00
geraniola
14.20
19.02
16.77
16.38
16.08
15.06
14.37
13.27
12.85
12.31
9.07
1.85
1.58
1.21
1.00
1.00
DL-citronellola
17.30
23.16
20.43
19.94
19.58
18.33
17.50
16.16
15.65
15.00
11.04
2.25
1.92
1.48
1.22
1.22
1.00
aThe selectivity and capacity values were calculated using the extrapolated infinite dilution activity coefficients (at 403.15 K) using data obtained in the temperature interval between (433.15 – 458.15) K.
Table S11. Experimental selectivities and capacities of the of terpenic mixtures in [P6,6,6,14][(C8H17)2PO2] at 403.15 K.
Solute
(1R)-(−)-fenchone
S(+)-carvone
p-cymene
R(+)-limonene
eucalyptol
α-pinene
(−)-menthone
β-pinene
α-pinene oxide
linalool
(1R)-(−)-fenchone
1.00
1.00
S(+)-carvone
1.11
1.11
1.00
p-cymene
1.35
1.34
1.21
1.00
R(+)-limonene
1.38
1.38
1.24
1.03
1.00
eucalyptol
1.42
1.42
1.28
1.06
1.03
1.00
α-pinene
1.49
1.48
1.33
1.10
1.08
1.05
1.00
(−)-menthone
1.50
1.50
1.35
1.11
1.09
1.06
1.01
1.00
β-pinene
1.58
1.58
1.42
1.18
1.15
1.12
1.07
1.06
1.00
α-pinene oxide
2.32
2.32
2.08
1.72
1.68
1.63
1.56
1.55
1.46
1.00
linalool
8.20
8.18
7.36
6.09
5.93
5.77
5.52
5.47
5.17
3.53
1.00
Table S12. Experimental selectivities and capacities of terpenic mixtures in [C4mim][OAc] at 403.15K.
Solute
R(+)-limonene
α-pinene
β-pinene
α-pinene oxide
p-cymene
(1R)-(−)-fenchone
eucalyptol
(−)-menthone
S(+)-carvone
linalool
R(+)-limonene
0.04
1.00
α-pinene
0.04
1.01
1.00
β-pinene
0.06
1.35
1.33
1.00
α-pinene oxide
0.06
1.47
1.45
1.09
1.00
p-cymene
0.07
1.62
1.61
1.20
1.11
1.00
(1R)-(−)-fenchone
0.08
1.86
1.84
1.38
1.27
1.15
1.00
eucalyptol
0.08
1.86
1.84
1.38
1.27
1.15
1.00
1.00
(−)-menthone
0.10
2.37
2.34
1.76
1.61
1.46
1.27
1.27
1.00
S(+)-carvone
0.22
5.38
5.32
3.99
3.67
3.31
2.89
2.89
2.27
1.00
linalool
1.26
30.29
29.96
22.48
20.65
18.66
16.27
16.27
12.80
5.63
1.00
Table S13. Predicted selectivities and capacities of terpenic mixtures in [P6,6,6,14]Cl at 403.15 K obtained using COSMO-RS model.
SoluteS
α-pinene
β-pinene
R(-)-Limonene
p-cymene
eucalyptol
α-pinene oxide
(−)-menthone
(1R)-(−)-fenchone
(1R)-(+)-camphor
S(+)-carvone
L-(-)-menthol
(−)-borneol
(-)-isopulegol
linalool
geraniol
DL-citronellol
α-pinene
1.05
1.00
β-pinene
1.18
1.12
1.00
R(-)-Limonene
1.20
1.14
1.01
1.00
p-cymene
1.36
1.29
1.15
1.14
1.00
eucalyptol
1.38
1.31
1.17
1.15
1.01
1.00
α-pinene oxide
1.44
1.37
1.22
1.20
1.06
1.05
1.00
(−)-menthone
1.56
1.48
1.32
1.30
1.15
1.13
1.08
1.00
(1R)-(−)-fenchone
1.62
1.54
1.38
1.36
1.19
1.18
1.13
1.04
1.00
(1R)-(+)-camphor
1.63
1.55
1.38
1.36
1.20
1.19
1.13
1.05
1.00
1.00
S(+)-carvone
1.81
1.72
1.53
1.51
1.33
1.31
1.26
1.16
1.11
1.11
1.00
L-(-)-menthol
3.80
3.61
3.22
3.18
2.79
2.76
2.64
2.44
2.34
2.33
2.10
1.00
(−)-borneol
3.81
3.62
3.22
3.18
2.80
2.77
2.64
2.44
2.34
2.33
2.11
1.00
1.00
(-)-isopulegol
3.99
3.80
3.39
3.34
2.94
2.90
2.77
2.56
2.46
2.45
2.21
1.05
1.05
1.00
linalool
4.29
4.08
3.64
3.59
3.16
3.12
2.98
2.75
2.64
2.63
2.38
1.13
1.13
1.07
1.00
geraniol
5.09
4.84
4.31
4.25
3.74
3.70
3.53
3.26
3.13
3.12
2.81
1.34
1.34
1.27
1.18
1.00
DL-citronellol
5.50
5.23
4.66
4.60
4.04
4.00
3.82
3.53
3.39
3.37
3.04
1.45
1.44
1.38
1.28
1.08
1.00
Table S14. Predicted selectivities and capacities of the of terpenic mixtures in [P6,6,6,14][(C8H17)2PO2] at 403.15 K obtained using COSMO-RS model.
Solute
α-pinene
R(+)-limonene
β-pinene
p-cymene
eucalyptol
α-pinene oxide
S(+)-carvone
(−)-menthone
(1R)-(−)-fenchone
linalool
α-pinene
1.60
1.00
R(+)-limonene
1.73
1.08
1.00
β-pinene
1.74
1.08
1.00
1.00
p-cymene
1.81
1.13
1.05
1.04
1.00
eucalyptol
1.95
1.22
1.13
1.12
1.08
1.00
α-pinene oxide
1.97
1.23
1.14
1.13
1.09
1.01
1.00
S(+)-carvone
1.98
1.23
1.14
1.14
1.09
1.01
1.00
1.00
(−)-menthone
2.03
1.27
1.17
1.17
1.12
1.04
1.03
1.03
1.00
(1R)-(−)-fenchone
2.10
1.31
1.21
1.21
1.16
1.07
1.07
1.06
1.03
1.00
linalool
7.27
4.54
4.21
4.19
4.02
3.73
3.70
3.68
3.58
3.47
1.00
Table S15. Predicted selectivities and capacities of terpenic mixtures in [C4mim][OAc] at 403.15K obtained using COSMO-RS model.
Solute
α-pinene
β-pinene
R(+)-limonene
eucalyptol
p-cymene
α-pinene oxide
(−)-menthone
(1R)-(−)-fenchone
S(+)-carvone
linalool
α-pinene
0.13
1.00
β-pinene
0.16
1.22
1.00
R(+)-limonene
0.17
1.29
1.06
1.00
eucalyptol
0.20
1.50
1.23
1.16
1.00
p-cymene
0.23
1.76
1.44
1.37
1.18
1.00
α-pinene oxide
0.23
1.77
1.45
1.38
1.19
1.01
1.00
(−)-menthone
0.26
1.96
1.61
1.52
1.31
1.11
1.11
1.00
(1R)-(−)-fenchone
0.30
2.29
1.88
1.78
1.53
1.30
1.29
1.17
1.00
S(+)-carvone
0.47
3.58
2.94
2.78
2.40
2.03
2.02
1.83
1.56
1.00
linalool
1.99
15.28
12.52
11.85
10.21
8.67
8.61
7.79
6.66
4.26
1.00
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a
Octane - this work333.15343.15353.15363.15373.15383.151.75499999999999991.73300000000000011.6981.671.65799999999999991.649Octane - [34]308.14999999999998318.14999999999998328.150.846999999999999980.830999999999999960.82099999999999995Cyclohexane - this work333.15343.15353.15363.15373.15383.151.0871.0481.0320.976999999999999980.991999999999999990.94299999999999995Cyclohexane - [34]308.14999999999998318.14999999999998328.150.631000000000000010.6270.625Benzene - this work333.15343.15353.15363.15373.15383.150.493999999999999990.492999999999999990.4970.50.5010.50800000000000001Benzene - [34]308.14999999999998318.14999999999998328.150.407999999999999970.403000000000000020.4Methanol - this work363.15373.15383.15393.15403.15413.153.3000000000000002E-23.5999999999999997E-23.9E-24.2000000000000003E-24.5999999999999999E-20.05Methanol - [34]308.14999999999998318.14999999999998328.150.887000000000000010.8790.873Ethanol - this work363.15373.15383.15393.15403.15413.154.2999999999999997E-24.5999999999999999E-20.055.3999999999999999E-25.8999999999999997E-26.5000000000000002E-2Ethanol - [34]308.14999999999998318.14999999999998328.150.740.736999999999999990.73499999999999999
1/T
𝛾13∞
b
Octane - this work333.15343.15353.15363.15373.15383.150.850999999999999980.850999999999999980.854999999999999980.852999999999999980.866999999999999990.85799999999999998Octane - [35]298.14999999999998303.14999999999998308.14999999999998313.14999999999998318.149999999999980.770.790.820.850.86Cyclohexane - this work333.15343.15353.15363.15373.15383.150.542000000000000040.544000000000000040.537000000000000030.536000000000000030.542000000000000040.53600000000000003Cyclohexane - [35]298.14999999999998303.14999999999998308.14999999999998313.14999999999998318.149999999999980.490.510.520.540.56000000000000005Benzene - this work333.15343.15353.15363.15373.15383.150.473999999999999980.473999999999999980.470999999999999970.466000000000000030.460.45400000000000001Benzene - [35]298.14999999999998303.14999999999998308.14999999999998313.14999999999998318.149999999999980.420.440.470.480.49
1/T
𝛾13∞
c
Decane - this work333.15343.15353.15363.15373.15383.1585.5479.3771.6168.34999999999999465.09999999999999458.27Decane - [36]313.14999999999998323.14999999999998333.15338.15343.152151971911851771,4 - dioxane - this work333.15343.15353.15363.15373.15383.152.252.27999999999999982.27999999999999982.27999999999999982.25999999999999982.161,4 - dioxane - [36]353.15358.15363.15368.15373.15378.15383.153.173.113.093.053.022.992.96toluene - this work333.15343.15353.15363.15373.15383.154.094.224.11000000000000034.134.11000000000000034.07toluene - [36]333.15338.15343.15353.15358.15363.15368.15373.155.65.65.65.65.61-butanol - this work 383.15393.15403.150.120.140000000000000010.161-butanol - [36]373.15378.15383.15393.15403.15413.150.228000000000000010.241999999999999990.2550.269000000000000020.28100000000000003
1/T
𝛾13∞
a
Carrera et al. [37]293.14999999999998298.14999999999998303.14999999999998308.14999999999998313.14999999999998318.14999999999998323.14999999999998328.15333.15338.15343.15348.15353.15358.15363.15368.15373.150.91800000000000004Hwang et al. [38]273.14999999999998278.14999999999998283.14999999999998288.14999999999998293.14999999999998298.14999999999998303.14999999999998308.14999999999998313.14999999999998318.14999999999998323.14999999999998328.15333.15338.15343.15348.15353.15358.15363.15368.15373.150.89181999999999995Choi et al. [39]283.14999999999998288.14999999999998293.14999999999998298.14999999999998303.14999999999998308.14999999999998313.14999999999998318.14999999999998323.14999999999998328.15333.15338.15343.15348.15353.15358.15363.15368.15373.150.89181999999999995Goncalves et al. [40]273.14999999999998278.14999999999998283.14999999999998288.14999999999998293.14999999999998298.14999999999998303.14999999999998308.14999999999998313.14999999999998318.14999999999998323.14999999999998328.15333.15338.15343.15348.15353.15358.15363.15368.15373.150.907270000000000020.903750000000000050.900900000000000030.897449999999999970.894370.891150.884800000000000030.87892000000000003Kilaru et al. [41]273.14999999999998278.14999999999998283.14999999999998288.14999999999998293.14999999999998298.14999999999998303.14999999999998308.14999999999998313.14999999999998318.14999999999998323.14999999999998328.15333.15338.15343.15348.15353.15358.15363.15368.15373.150.882600000000000050.880099999999999990.877900000000000010.875399999999999960.873099999999999990.869399999999999950.86690.86439999999999995McAtee and Heitz [42]273.14999999999998278.14999999999998283.14999999999998288.14999999999998293.14999999999998298.14999999999998303.14999999999998308.14999999999998313.14999999999998318.14999999999998323.14999999999998328.15333.15338.15343.15348.15353.15358.15363.15368.15373.150.898399999999999980.892399999999999970.886499999999999950.880600000000000050.874800000000000020.86890000000000001Tomé et al. [43]273.14999999999998278.14999999999998283.14999999999998288.14999999999998293.14999999999998298.14999999999998303.14999999999998308.14999999999998313.14999999999998318.14999999999998323.14999999999998328.15333.15338.15343.15348.15353.15358.15363.15368.15373.150.898399999999999980.892399999999999970.886499999999999950.880600000000000050.874800000000000020.86890000000000001Neves et al. [44]273.14999999999998278.14999999999998283.14999999999998288.14999999999998293.14999999999998298.14999999999998303.14999999999998308.14999999999998313.14999999999998318.14999999999998323.14999999999998328.15333.15338.15343.15348.15353.15358.15363.15368.15373.150.901600000000000070.898600000000000070.895700000000000050.892799999999999930.889900000000000020.887000000000000010.884000000000000010.881099999999999990.878200000000000090.875299999999999970.872299999999999960.869500000000000050.866600000000000040.863700000000000020.860800000000000010.857999999999999980.855099999999999970.85229999999999995This work283.14999999999998288.14999999999998293.14999999999998298.14999999999998303.14999999999998308.14999999999998313.14999999999998318.14999999999998323.14999999999998328.15333.15338.15343.15348.15353.15358.15363.15368.15373.150.899700000000000060.896700000000000050.893599999999999950.890599999999999950.887599999999999940.884499999999999950.881499999999999950.878499999999999950.875499999999999940.872500000000000050.869600000000000040.866600000000000040.863600000000000030.860700000000000020.857700000000000020.85480.85180.848899999999999990.84599999999999997
Temperature (K)
Density (g cm-3)
b
Hwang et al. [38]273.14999999999998278.14999999999998283.14999999999998288.14999999999998293.14999999999998298.14999999999998303.14999999999998308.14999999999998310.14999999999998313.14999999999998318.14999999999998323.14999999999998328.15333.15338.15343.15348.15353.15358.15363.15368.15373.150.89181999999999995Choi et al. [39]283.14999999999998288.14999999999998293.14999999999998298.14999999999998303.14999999999998308.14999999999998310.14999999999998313.14999999999998318.14999999999998323.14999999999998328.15333.15338.15343.15348.15353.15358.15363.15368.15373.150.89181999999999995Neves et al. [44]273.14999999999998278.14999999999998283.14999999999998288.14999999999998293.14999999999998298.14999999999998303.14999999999998308.14999999999998310.14999999999998313.14999999999998318.14999999999998323.14999999999998328.15333.15338.15343.15348.15353.15358.15363.15368.15373.150.885299999999999980.882299999999999970.879299999999999970.876299999999999970.873399999999999950.870399999999999950.867500000000000050.864600000000000040.861700000000000020.85890.855999999999999980.853200000000000070.850299999999999940.84750000000000003Lee and Park [45]273.14999999999998278.14999999999998283.14999999999998288.14999999999998293.14999999999998298.14999999999998303.14999999999998308.14999999999998310.14999999999998313.14999999999998318.14999999999998323.14999999999998328.15333.15338.15343.15348.15353.15358.15363.15368.15373.150.88643000000000005Blahušiak and Schlosser [46]288.14999999999998293.14999999999998298.14999999999998303.14999999999998308.14999999999998310.14999999999998313.14999999999998318.14999999999998323.14999999999998328.15333.15338.15343.15348.15353.15358.15363.15368.150.890859999999999990.887720000000000060.884549999999999950.881539999999999990.878580000000000030.875619999999999950.872669999999999950.869720000000000050.866769999999999930.863870000000000030.860990000000000030.858099999999999970.855219999999999980.852330000000000030.849440000000000080.84655999999999998Marták and Schlosser [47]273.14999999999998278.14999999999998283.14999999999998288.14999999999998293.14999999999998298.14999999999998303.14999999999998308.14999999999998310.14999999999998313.14999999999998318.14999999999998323.14999999999998328.15333.15338.15343.15348.15353.15358.15363.15368.15373.150.885240000000000030.878059999999999950.87329000000000001Liu et al. [48]273.14999999999998278.14999999999998283.14999999999998288.14999999999998293.14999999999998298.14999999999998303.14999999999998308.14999999999998310.14999999999998313.14999999999998318.14999999999998323.14999999999998328.15333.15338.15343.15348.15353.15358.15363.15368.15373.150.889299999999999980.886299999999999980.883299999999999970.880299999999999970.877299999999999970.874299999999999970.871299999999999960.868399999999999950.865500000000000050.862600000000000030.859600000000000030.856700000000000020.85380.8508Ramdin et al. [49]273.14999999999998278.14999999999998283.14999999999998288.14999999999998293.14999999999998298.14999999999998303.14999999999998308.14999999999998310.14999999999998313.14999999999998318.14999999999998323.14999999999998328.15333.15338.15343.15348.15353.15358.15363.15368.15373.150.889299999999999980.886299999999999980.883299999999999970.880299999999999970.877299999999999970.874299999999999970.871299999999999960.868399999999999950.865500000000000050.862600000000000030.859600000000000030.856700000000000020.85380.8508Rabari et al. [50]293.14999999999998298.14999999999998303.14999999999998308.14999999999998310.14999999999998313.14999999999998318.14999999999998323.14999999999998328.150.894000000000000020.890800000000000040.887700000000000040.884600000000000050.881499999999999950.878399999999999960.875299999999999970.87229999999999996This work283.14999999999998288.14999999999998293.14999999999998298.14999999999998303.14999999999998308.14999999999998310.14999999999998313.14999999999998318.14999999999998323.14999999999998328.15333.15338.15343.15348.15353.15358.15363.15368.15373.150.900100000000000010.897000000000000020.893900000000000030.890700000000000050.887599999999999940.884499999999999950.881399999999999960.878299999999999970.875299999999999970.872299999999999960.869199999999999970.866199999999999970.863199999999999970.860199999999999960.857199999999999960.854199999999999960.851199999999999960.848199999999999950.84530000000000005
Temperature (K)
Density (g cm-3)
a
GE,∞ at 383.15 K0.500169043577461840.567583957584599560.63763447062968648-5.8688996348679613E-26.2035390919452697E-2-0.67727383140365516-0.50583808225495164-0.3410828491788962-0.301105092783921618.7094706850933734E-2-0.51919387343650736-0.30381145438166457-6.0812139396757475E-2-7.0246149369644663E-3-0.10647224451051676-0.31608154697347896-0.33687231664255274-0.5923972774598022-0.84629836005412007-0.94160853985844495-3.2441936328524905-2.9957322735539909-3.0791138824930422-2.7806208939370456-3.1235656450638758-2.8134107167600364-3.1941832122778293-2.5133061243096981-1.61445045425764460.150142658429719414.4973365642731196E-20.153579087928300580.19392069263730649-0.169602784386179980.26159473768846242-0.18392283816092855.0693114315518165E-21.59338349382529151.80814650764221652.0313057228181322-0.186964945655770540.19762552119790849-2.1575844359333423-1.611443293348191-1.0865842036551103-0.959227467012020330.27745673203451271-1.6539907030468333-0.9678490959463556-0.1937286211196505-2.2378245184828817E-2-0.33918755895038477-1.0069378065624039-1.0731707524834067-1.8871940513153822-2.6960441776177371-2.9996728592480753-10.33499504165075-9.5434741871652573-9.8091021405104026-8.8581960276772751-9.9507116736498471-8.962654236601832-10.175677347590812-8.0066140534442773-5.14313858173527190.478307957545383410.14327119880180930.489255356451900440.61777120101116012-0.540301885168341660.83335972598991781-0.585921136516193260.16149254464692939Enthalpies at 383.15 K0.500169043577461840.567583957584599560.63763447062968648-5.8688996348679613E-26.2035390919452697E-2-0.67727383140365516-0.50583808225495164-0.3410828491788962-0.301105092783921618.7094706850933734E-2-0.51919387343650736-0.30381145438166457-6.0812139396757475E-2-7.0246149369644663E-3-0.10647224451051676-0.31608154697347896-0.33687231664255274-0.5923972774598022-0.84629836005412007-0.94160853985844495-3.2441936328524905-2.9957322735539909-3.0791138824930422-2.7806208939370456-3.1235656450638758-2.8134107167600364-3.1941832122778293-2.5133061243096981-1.61445045425764460.150142658429719414.4973365642731196E-20.153579087928300580.19392069263730649-0.169602784386179980.26159473768846242-0.18392283816092855.0693114315518165E-21.40625410005630381.59218134840208592.12316195850965842.82435239867403311.5180653566029552-0.58172652053913243-0.45311180537823709-0.18490811521207498-0.329008090849625124.07486713172774981.32623195008694261.71151804595791492.88167383399893672.51024223827336272.31901165921175822.08974463995711360.362035296991989050.38794116524293354-0.37268979128876628-1.9213386066031723-10.280654226575859-10.27210990056291-12.132425834739587-11.55493193211993-12.182005670222289-13.283067713850119-12.728378335410047-13.4606092529516910.442575819389644851.0938265361817231.34428080788936221.32585121322881051.3200538033807196-5.619884599421292-2.2214695239832922-6.3356281434070771-0.68366711975471883-19.426665858364043Tref*S at 383.15 K0.500169043577461840.567583957584599560.63763447062968648-5.8688996348679613E-26.2035390919452697E-2-0.67727383140365516-0.50583808225495164-0.3410828491788962-0.301105092783921618.7094706850933734E-2-0.51919387343650736-0.30381145438166457-6.0812139396757475E-2-7.0246149369644663E-3-0.10647224451051676-0.31608154697347896-0.33687231664255274-0.5923972774598022-0.84629836005412007-0.94160853985844495-3.2441936328524905-2.9957322735539909-3.0791138824930422-2.7806208939370456-3.1235656450638758-2.8134107167600364-3.1941832122778293-2.5133061243096981-1.61445045425764460.150142658429719414.4973365642731196E-20.153579087928300580.19392069263730649-0.169602784386179980.26159473768846242-0.18392283816092855.0693114315518165E-2-0.18712939376898774-0.21596515924013069.1856235691526233E-23.01131734432980381.32043983540504661.57585791539420981.1583314879699540.901676088443035370.630219376162395213.79741039969323692.98022265313377592.67936714190427063.07540245511858722.53262048345819142.65819921816214323.09668244651951771.43520604947539582.27513521655831592.32335438632897071.07833425264490295.4340815074890969E-2-0.72863571339765265-2.3233236942291846-2.6967359044426544-2.2312939965724414-4.3204134772482874-2.5527009878192359-5.45399519950741415.58571440112491670.615518578636339521.20100960908755280.836595856776910060.70228260236955953-5.0795827142529504-3.0548292499732099-5.7497070068908842-0.84515966440164825-19.426665858364043Gibbs energies at 433.15 K-2.4534079827286295-2.6310891599660819-0.748659890490204098.9597413714718015E-3-2.0249533563957662-1.8078888511579385-2.4191189092499972-8.8357367448261463-9.4756401435404811-2.69623387155722543.2267733951042959E-2-7.2926944493618411-6.5109553996688883-8.7122476110929803Enthalpies at 433.15 K-2.4534079827286295-2.6310891599660819-0.748659890490204098.9597413714718015E-3-2.0249533563957662-1.8078888511579385-2.4191189092499972-10.186782211214025-11.24685655703570414.709753651408068-4.196615728848669-21.52013431527423-11.217838211775549-11.660125039827689Tref*S at 433.15 K-2.4534079827286295-2.6310891599660819-0.748659890490204098.9597413714718015E-3-2.0249533563957662-1.8078888511579385-2.4191189092499972-1.3510454663878786-1.7