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.