Post on 31-Jan-2021
Supporting Information
Thermodynamic Characterization of Deep Eutectic Solvents at High Pressures
Emanuel A. Crespo,a João M. L. Costa,a André M. Palma,a Belinda Soares, a M. Carmen Martín,b José J. Segovia,b Pedro J. Carvalho, a and João A. P. Coutinho,a*
aCICECO – Aveiro Institute of Materials, Department of Chemistry, University of Aveiro, 3810-193 Aveiro, Portugal;
bBioEcoUVa, Research Institute on Bioeconomy, TERMOCAL Research Group, University of Valladolid, Escuela de Ingenierías Industriales, Paseo del Cauce 59, 47011 Valladolid, Spain
*Corresponding author: jcoutinho@ua.pt, Phone: +351 234401507 Fax: +351 234370084
Figure S1. Prediction of high-pressure densities of pure ethylene glycol. Symbols represent experimental data from Crespo et al.1 while the solid lines depict the PC-SAFT predictions using the parameters from: A) Atilhan et al.2 B) Reschke et al.3 C) Liang et al.4
Figure S2. High-pressure densities for the DES: [Ch]Cl + glycerol (1:2). Symbols represent experimental data from Leron et al.5 while the solid lines represent the experimental data measured in this work.
Figure S3. Viscosity of pure ethylene glycol. Symbols represent experimental data from literature6 while the solid lines represent the FVT fitting to the experimental data.
Figure S4. Viscosity of pure glycerol at atmospheric pressure. Symbols represent experimental data from DIPPR database7 while the solid line depict the FVT fitting to the experimental data.
Figure S5. Viscosity of [Ch]Cl-based DES at atmospheric pressure. Symbols represent experimental data measured in this work using the falling body viscometer while the solid lines depict the PC-SAFT + FVT results.
Figure S6. Viscosity of [Ch]Cl + urea (1:2) at atmospheric pressure. Symbols represent experimental data measured in this work while the solid line depict the PC-SAFT + FVT results.
Table S1. Density as a function of temperature and pressure of the DES [Ch]Cl:EG (1:2)
ρ/g·cm⁻³
T/K
p/MPa
283.15
293.15
303.15
313.15
323.15
333.15
343.15
353.15
363.15
0.1
1.1260
1.1200
1.1143
1.1086
1.1031
1.0975
1.0921
1.0865
1.0806
1.0
1.1263
1.1203
1.1147
1.1090
1.1030
1.0979
1.0924
1.0868
1.0808
2.0
1.1266
1.1206
1.1150
1.1093
1.1033
1.0983
1.0928
1.0872
1.0810
5.0
1.1276
1.1217
1.1159
1.1103
1.1048
1.0994
1.0938
1.0884
1.0826
7.0
1.1282
1.1222
1.1166
1.1109
1.1055
1.1000
1.0945
1.0891
1.0833
10.0
1.1291
1.1232
1.1176
1.1119
1.1064
1.1011
1.0955
1.0901
1.0843
12.0
1.1298
1.1238
1.1182
1.1125
1.1071
1.1017
1.0963
1.0907
1.0851
16.0
1.1309
1.1250
1.1194
1.1137
1.1085
1.1030
1.0975
1.0922
1.0865
20.0
1.1322
1.1263
1.1208
1.1151
1.1097
1.1043
1.0988
1.0936
1.0880
25.0
1.1337
1.1278
1.1224
1.1167
1.1114
1.1061
1.1005
1.0953
1.0895
30.0
1.1352
1.1294
1.1238
1.1183
1.1129
1.1077
1.1021
1.0970
1.0912
35.0
1.1365
1.1308
1.1252
1.1197
1.1145
1.1093
1.1037
1.0985
1.0930
40.0
1.1381
1.1324
1.1268
1.1212
1.1160
1.1105
1.1054
1.1002
1.0946
45.0
1.1395
1.1339
1.1283
1.1227
1.1174
1.1121
1.1069
1.1016
1.0962
50.0
1.1408
1.1354
1.1294
1.1242
1.1190
1.1137
1.1085
1.1032
1.0978
55.0
1.1421
1.1368
1.1309
1.1256
1.1205
1.1153
1.1100
1.1046
1.0995
60.0
1.1436
1.1379
1.1323
1.1270
1.1219
1.1168
1.1116
1.1063
1.1009
65.0
1.1450
1.1394
1.1338
1.1285
1.1235
1.1183
1.1130
1.1078
1.1024
70.0
1.1465
1.1408
1.1351
1.1299
1.1250
1.1198
1.1146
1.1095
1.1041
75.0
1.1479
1.1421
1.1366
1.1312
1.1265
1.1212
1.1160
1.1110
1.1056
80.0
1.1492
1.1434
1.1379
1.1326
1.1279
1.1227
1.1174
1.1124
1.1070
85.0
1.1504
1.1449
1.1392
1.1341
1.1289
1.1242
1.1188
1.1137
1.1086
90.0
1.1517
1.1462
1.1407
1.1355
1.1305
1.1257
1.1203
1.1154
1.1102
95.0
1.1530
1.1475
1.1419
1.1369
1.1318
1.1270
1.1218
1.1167
1.1117
Standard uncertainties u are u(T)=0.1 K, u(p)=0.2% and u(ρ)=5·10-4 g·cm⁻³
Table S2. Density as a function of temperature and pressure of the DES - [Ch]Cl:glycerol (1:2).
ρ/g·cm⁻³
T/K
p/MPa
283.15
293.15
303.15
313.15
323.15
333.15
343.15
353.15
363.15
0.1
1.2022
1.1968
1.1912
1.1856
1.1803
1.1744
1.1693
1.1637
1.1581
1.0
1.2025
1.1970
1.1915
1.1859
1.1806
1.1746
1.1696
1.1640
1.1585
2.0
1.2026
1.1973
1.1918
1.1863
1.1808
1.1748
1.1699
1.1644
1.1589
5.0
1.2037
1.1982
1.1928
1.1872
1.1818
1.1759
1.1709
1.1654
1.1599
7.0
1.2042
1.1988
1.1933
1.1878
1.1824
1.1769
1.1715
1.1660
1.1606
10.0
1.2051
1.1997
1.1941
1.1885
1.1832
1.1778
1.1724
1.1670
1.1615
12.0
1.2056
1.2001
1.1948
1.1889
1.1839
1.1783
1.1729
1.1676
1.1621
16.0
1.2068
1.2013
1.1960
1.1902
1.1850
1.1796
1.1742
1.1689
1.1634
20.0
1.2078
1.2023
1.1969
1.1914
1.1862
1.1807
1.1753
1.1700
1.1646
25.0
1.2092
1.2036
1.1984
1.1928
1.1876
1.1822
1.1769
1.1715
1.1661
30.0
1.2106
1.2052
1.1999
1.1943
1.1890
1.1835
1.1784
1.1730
1.1677
35.0
1.2119
1.2063
1.2013
1.1959
1.1906
1.1851
1.1797
1.1746
1.1691
40.0
1.2128
1.2076
1.2025
1.1973
1.1917
1.1866
1.1812
1.1761
1.1703
45.0
1.2143
1.2089
1.2038
1.1986
1.1932
1.1879
1.1826
1.1774
1.1718
50.0
1.2156
1.2101
1.2051
1.1997
1.1943
1.1892
1.1839
1.1786
1.1734
55.0
1.2169
1.2115
1.2064
1.2010
1.1958
1.1905
1.1854
1.1802
1.1749
60.0
1.2181
1.2128
1.2076
1.2024
1.1972
1.1919
1.1866
1.1816
1.1761
65.0
1.2192
1.2140
1.2089
1.2038
1.1987
1.1934
1.1879
1.1831
1.1777
70.0
1.2206
1.2153
1.2103
1.2050
1.1999
1.1947
1.1894
1.1845
1.1792
75.0
1.2219
1.2165
1.2115
1.2064
1.2010
1.1958
1.1908
1.1859
1.1806
80.0
1.2229
1.2178
1.2127
1.2077
1.2025
1.1973
1.1921
1.1874
1.1822
85.0
1.2241
1.2192
1.2141
1.2089
1.2038
1.1986
1.1936
1.1888
1.1835
90.0
1.2253
1.2204
1.2153
1.2099
1.2049
1.1999
1.1948
1.1901
1.1845
95.0
1.2266
1.2216
1.2167
1.2114
1.2063
1.2011
1.1961
1.1915
1.1856
Standard uncertainties u are u(T)=0.1 K, u(p)=0.2% and u(ρ)=5·10-4 g·cm⁻³
Table S3. Density as a function of temperature and pressure of the DES - [Ch]Cl:urea (1:2)
ρ/g·cm⁻³
p/MPa
T/K
293.15
303.15
313.15
323.15
333.15
343.15
353.15
363.15
0.1
1.2014
1.1961
1.1903
1.1852
1.1799
1.1747
1.1693
1.1638
1.0
1.2017
1.1964
1.1906
1.1856
1.1802
1.1750
1.1695
1.1642
2.0
1.2020
1.1967
1.1911
1.1859
1.1805
1.1753
1.1699
1.1645
5.0
1.2028
1.1974
1.1919
1.1868
1.1814
1.1761
1.1708
1.1655
7.0
1.2034
1.1980
1.1924
1.1871
1.1820
1.1767
1.1714
1.1661
10.0
1.2042
1.1987
1.1933
1.1881
1.1827
1.1775
1.1721
1.1669
12.0
1.2048
1.1994
1.1938
1.1885
1.1833
1.1781
1.1726
1.1675
16.0
1.2059
1.2005
1.1949
1.1899
1.1845
1.1792
1.1739
1.1688
20.0
1.2068
1.2016
1.1960
1.1909
1.1856
1.1803
1.1748
1.1699
25.0
1.2081
1.2029
1.1972
1.1921
1.1868
1.1816
1.1763
1.1712
30.0
1.2095
1.2041
1.1987
1.1935
1.1882
1.1830
1.1777
1.1727
35.0
1.2108
1.2054
1.2001
1.1947
1.1896
1.1844
1.1791
1.1742
40.0
1.2120
1.2067
1.2013
1.1961
1.1909
1.1858
1.1805
1.1755
45.0
1.2132
1.2078
1.2025
1.1974
1.1923
1.1870
1.1819
1.1770
50.0
1.2146
1.2092
1.2038
1.1987
1.1934
1.1884
1.1832
1.1782
55.0
1.2157
1.2104
1.2051
1.2000
1.1948
1.1896
1.1846
1.1795
60.0
1.2168
1.2117
1.2063
1.2014
1.1961
1.1910
1.1858
1.1807
65.0
1.2181
1.2129
1.2076
1.2025
1.1972
1.1923
1.1871
1.1819
70.0
1.2193
1.2142
1.2089
1.2038
1.1985
1.1936
1.1886
1.1833
75.0
1.2206
1.2153
1.2101
1.2050
1.1999
1.1948
1.1898
1.1846
80.0
1.2223
1.2166
1.2112
1.2063
1.2012
1.1961
1.1910
1.1860
85.0
1.2238
1.2177
1.2125
1.2075
1.2026
1.1975
1.1924
1.1871
90.0
1.2252
1.2189
1.2137
1.2089
1.2038
1.1989
1.1934
1.1885
95.0
1.2265
1.2201
1.2149
1.2101
1.2052
1.2001
1.1948
1.1899
Standard uncertainties u are u(T)=0.1 K, u(p)=0.2% and u(ρ)=5·10-4 g·cm⁻³
Table S4. Viscosity measurements at high pressures using the falling body viscometer.
η/cP – [Ch]Cl + EG (1:2)
p/MPa
T/K
313.15
333.15
353.15
373.15
0.1
27.64
15.47
9.41
6.31
1
29.87
15.16
9.51
6.43
5
30.59
15.60
9.57
6.56
12
31.72
16.01
9.76
6.66
20
32.93
16.53
10.06
6.81
40
35.87
17.91
10.89
7.30
60
39.58
20.85
11.76
8.28
70
8.69
80
43.39
22.92
12.57
8.88
100
24.53
14.20
9.45
η/cP – [Ch]Cl + Glycerol (1:2)
p/MPa
T/K
313.15
333.15
353.15
373.15
0.1
165.7
65.53
31.60
17.05
1
169.8
65.06
31.83
17.26
5
66.71
31.85
12
173.6
67.68
31.87
17.75
20
32.83
40
189.3
72.75
34.25
18.46
60
212.4
81.69
37.61
20.35
70
238.9
90.95
41.39
22.13
80
270.2
101.3
45.23
23.76
100
305.02
110.9
49.24
25.96
η/cP – [Ch]Cl + Urea (1:2)
p/MPa
T/K
313.15
333.15
353.15
373.15
0.1
74.17
30.26
14.90
1
74.54
30.38
15.96
5
75.44
31.17
15.94
12
79.15
32.08
16.53
20
83.50
33.34
17.08
40
95.36
37.05
18.56
60
106.1
40.93
20.23
70
80
121.5
44.71
22.14
100
146.4
46.72
23.95
Table S5.Viscosity measurements at atmospheric pressure using the SVM3000.
η/Cp – [Ch]Cl +
T/K
EG
Glycerol
Urea
293.15
59.144
561.40
1696.1
298.15
47.742
386.33
1014.9
303.15
39.101
290.87
635.48
308.15
32.423
216.81
414.61
313.15
27.439
161.33
280.75
318.15
23.034
125.20
196.38
323.15
19.697
98.890
141.98
328.15
16.994
78.730
105.16
333.15
14.760
63.508
80.074
338.15
12.946
51.973
61.916
343.15
11.418
43.037
49.072
348.15
10.132
36.024
39.556
353.15
9.0139
30.469
32.470
358.15
8.1121
26.001
26.865
363.15
7.3123
22.372
22.605
368.15
6.6135
19.407
19.335
373.15
6.0130
16.929
16.651
References
(1) Crespo, E. A.; Costa, J. M. L.; Hanafiah, Z. B. M. A.; Kurnia, K. A.; Oliveira, M. B.; Llovell, F.; Vega, L. F.; Carvalho, P. J.; Coutinho, J. A. P. New Measurements and Modeling of High Pressure Thermodynamic Properties of Glycols. Fluid Phase Equilib. 2017, 436, 113–123.
(2) Atilhan, M.; Aparicio, S. PρT Measurements and Derived Properties of Liquid 1,2-Alkanediols. J. Chem. Thermodyn. 2013, 57, 137–144.
(3) Reschke, T.; Brandenbusch, C.; Sadowski, G. Modeling Aqueous Two-Phase Systems: I. Polyethylene Glycol and Inorganic Salts as ATPS Former. Fluid Phase Equilib. 2014, 368, 91–103.
(4) Liang, X.; Yan, W.; Thomsen, K.; Kontogeorgis, G. M. Modeling the Liquid–liquid Equilibrium of Petroleum Fluid and Polar Compounds Containing Systems with the PC-SAFT Equation of State. Fluid Phase Equilib. 2015, 406, 147–155.
(5) Leron, R. B.; Wong, D. S. H.; Li, M.-H. Densities of a Deep Eutectic Solvent Based on Choline Chloride and Glycerol and Its Aqueous Mixtures at Elevated Pressures. Fluid Phase Equilib. 2012, 335, 32–38.
(6) Sagdeev, D. I.; Fomina, M. G.; Mukhamedzyanov, G. K.; Abdulagatov, I. M. Experimental Study of the Density and Viscosity of Polyethylene Glycols and Their Mixtures at Temperatures from 293K to 465K and at High Pressures up to 245MPa. Fluid Phase Equilib. 2012, 315, 64–76.
(7) Daubert, T. E.; Sibul, H. M.; Stebbins, C. C.; Danner, R. P.; Rowley, R. L.; Adams, M. E.; Wilding, W. V; Marshall, T. L. Physical and Thermodynamic Properties of Pure Chemicals: DIPPR: Data Compilation: Core + Supplements 1-10; Taylor & Francis, 2000.