Thermodynamic Properties of Ternary Mixtures Containing Ionic

Article pubs.acs.org/jced

Thermodynamic Properties of Ternary Mixtures Containing Ionic Liquid and Organic Liquids: Excess Molar Volume and Excess Isentropic Compressibility V. K. Sharma,* S. Solanki, and S. Bhagour Department of Chemistry, M. D. University, Rohtak-124001, India ABSTRACT: Densities, ρ123, and speeds of sound, u123, of 1-ethyl3-methylimidazolium tetrafluoroborate (1) + 2-methylaniline (2) + pyridine or α-, β-, or γ-picoline (3) ternary mixtures have been measured over the entire range of composition at 293.15 K, 298.15 K, 303.15 K, and 308.15 K using density and speed of sound analyzer (Anton Paar DSA 5000). The heat capacity, Cp, of pure liquids pyridine and α-, β-, and γ-picoline have also been measured at 293.15 K, 298.15 K, 303.15 K, and 308.15 K using differential scanning calorimeter. The measured data have been employed to E determine excess molar volumes, V123 and excess isentropic E E compressibilities,(κS )123. The V123 and(κES )123 data have been fitted to Redlich−Kister equation to calculate ternary adjustable parameters and standard deviations. The thermodynamic properties of the ternary mixtures have been analyzed in terms of Graph (which deals with the topology of the constituent of mixtures) and Prigogine-Flory-Patterson (PFP) theories. It has been observed that Graph theory describes well VE123 and (κES )123 data of the studied ternary ionic liquid mixtures. However, PFP theory correctly predicts the sign of VE123 and (κES )123 data of the studied mixtures.

1. INTRODUCTION Ionic liquids (ILs) are characterized by the coexistence of polar and apolar moieties. The different nature of interactions between these moieties leads to a complex morphology. The ionic liquids or their mixtures with organic liquids are gaining more and more appeal in the field of chemistry and electrochemistry because of their well nonflammability, thermal stability,1,2 and electrochemical stability.3−6 Due to their high thermal stability, which is often correlated to electrochemical stability, ionic liquids are interesting substance for electrolyte of lithium ion and other novel types of batteries.7−9 ILs initially studied for their physical and thermodynamic properties are now seen as having applicability in many areas such as material science, home products, cell engineering, lunar mirrors, etc. The emphasis on the physical and thermodynamic properties of ILs has been recently upstaged by an increasing interest in the tunable chemical properties of their ions. The combination of physical, thermodynamic, and chemical properties represented by ILs has led to a boom in patent applications, where the unanticipated nature or properties of ILs can be transferred to new technologies. Despite an overwhelming amount of literature in the field of thermodynamic properties of ionic liquids and their binary mixtures with organic liquids,10−13 there is surprising little known on the thermodynamic properties of ternary ionic liquid mixtures.14−16 The knowledge of these properties is of great value in understanding the nature of molecular interactions which give rise to the peculiar properties of ionic liquids. In recent studies,17,18 we have reported densities, speed of sound, excess molar volumes, © 2014 American Chemical Society

excess molar enthalpies, and excess isentropic compressibilities data of 1-ethyl-3-methylimidazolium tetrafluoroborate (1) + aniline, N-methyl aniline, 2-methylaniline, pyridine, or α-, β-, γpicoline (2) binary ionic liquid mixtures and the same have analyzed successfully in terms of graph theory. In continuation of our work, we report here densities, ρ123, speed of sound, u123, excess molar volumes,VE123, and excess isentropic compressibilities, (κES )123 of 1-ethyl-3-methylimidazolium tetrafluoroborate (1) + 2-methylaniline (2) + pyridine or α-, β-, or γ-picoline (3) ternary mixtures at 293.15 K, 298.15 K, 303.15 K, and 308.15 K. It would be of great interest to see how Graph and Prigogine-Flory-Patterson (PFP) theory describes the VE123 and (κES )123 of the investigated ternary mixtures.

2. EXPERIMENTAL SECTION 1-Ethyl-3-methylimidazolium tetrafluoroborate [emim][BF4] (Fluka, 0.98 GC) was used without further purification. The content of water in the ionic liquid was regularly checked using Karl Fischer titration19 and found to be less than 330 ppm. 2Methylaniline (2MA) (Fluka, 0.99 GC), pyridine (Py) (Fluka, 0.99 GC), α-picoline (Fluka, 0.98 GC), β-picoline (Fluka, 0.99 GC), and γ-picoline (Fluka, 0.99 GC) were purified by standard methods.20 The source of liquids, their purification methods, and their final purities are recorded in Table 1. The densities Received: May 24, 2013 Accepted: February 28, 2014 Published: March 14, 2014 1140

dx.doi.org/10.1021/je4004965 | J. Chem. Eng. Data 2014, 59, 1140−1157

Journal of Chemical & Engineering Data

Article

Densities, ρ, and speeds of sound, u, values of the pure liquids and their ternary mixtures, ρ123 and u123, were measured using a commercial density and sound analyzer apparatus (Anton Paar DSA 5000) in the manner as described elsewhere.29,30 The apparatus was calibrated with double distilled deionized water. The mole fraction of each mixture was obtained with standard uncertainty of 1 × 10−4 from the measured apparent masses of the components. All the measurements were performed on an electric balance. The density and speed of sound can be measured to ± 10−3 kg·m−3 and 10−2 m·s−1, respectively. The standard uncertainties in the density and speed of sound measurements are 0.5 kg·m−3 and 0.1 m·s−1, respectively. Further, the standard uncertainty in VE values predicted from density results is 0.1 %. The heat capacities, Cp, of the pure liquids at 293.15 K, 298.15 K, 303.15 K, and 308.15 K were measured by high sensitivity differential scanning calorimeter (model μDSC 7 Evo, manufactured by M/S SETARAM instrumentation, France) in the manner described elsewhere.31 The heat capacity of sample liquid was measured in standard batch cell (Hastalloy C276) composed of a cylinder of 6.4 mm of internal

and speed of sound values for the purified liquids are recorded in Table 2 and compare well with their literature values.20−28 Table 1. Details of Chemical Source, Purification Method, Final Purity, and Analysis Method chemical name

source

purification method

final purity

analysis method

1-ethyl-3-methyl imidazolium tetrafluoroborate 2-methylaniline

Fluka

used as such

0.98

GCa

Fluka

0.99

GC

Pyridine

Fluka

0.99

GC

α-picoline

Fluka

0.98

GC

β-picoline

Fluka

0.99

GC

γ-picoline

Fluka

fractional distillation fractional distillation fractional distillation fractional distillation fractional distillation

0.99

GC

a

GC = Gas chromatography.

Table 2. Comparison of Density, ρ, Speed of Sound, u, Thermal Expansion Coefficient, α, and Molar Heat Capacity, CP, of Pure 1-Ethyl-3-methylimidazolium Tetrafluoroborate, 2-Methylaniline, Pyridine, and α-, β-, and γ-Picoline with Literature Values at T/K = (293.15, 298.15, 303.15, and 308.15) and p = 0.1 MPaa ρ/kg·m−3

u/m·s−1

α/(·103) K−1

CP/J·K−1 mol−1

liquids

T/K

exptl.

lit.

exptl.

exptl.

lit.

1-ethyl-3-methyl imidazolium tetrafluoroborate

293.15 298.15

1283.89 1279.91

1631.1 1619.4

0.615 0.596

303.73 305.35

303.232 304.932

303.15

1276.26

1607.6

0.614

306.16

306.632

308.15

1272.07

1284.321 1279.622 1280.0723 1276.521 1275.722 1271.922 1272.4823

1596.3

0.648

308.94

308.432

2-methyl Aniline

pyridine

α-picoline

β-picoline

γ-picoline

293.15 298.15

998.431 994.358

303.15 308.15 293.15 298.15

990.230 986.064 983.191 978.249

303.15 308.15 293.15 298.15

973.224 968.166 944.401 939.802

303.15 308.15 293.15 298.15

935.117 930.414 956.581 952.002

303.15 308.15 293.15 298.15

947.449 942.831 955.099 950.179

303.15 308.15

945.413 940.821

lit.

exptl.

lit.

1622.16 1602.35

1602.5724

0.818 0.826

978.2420

1577.67 1558.18 1442.0 1417.8

1577.8224 1558.3824 1436.7725 1418.0626

0.836 0.840 1.012 1.029

1397.0225

939.8120

1398.0 1377.1 1400.5 1380.1

1379.1827

1.036 1.043 0.978 0.997

1423.0828

1.003 1.011 0.955 0.956

1.00437 1.01137

951.9720

1361.0 1339.9 1445.9 1424.0

1431.8926

0.968 0.977 1.022 1.003

0.69837 0.97737

950.2024

1404.1 1384.0 1451.1 1431.5

1.00337

160.83 160.96 155.88 158.52

1.008 1.013

1.00837 1.01337

160.84 160.83

994.35124 990.22424 986.06924

1410.7 1389.9

0.83037 0.83637 0.84037

0.99737

0.95737

215.96 217.16 218.43 219.52 130.49 131.74 132.71 133.82 157.07 158.86 160.14 160.66 156.05 158.75

217.433 218.4534 219.133 131.5535 132.7236

159.237 158.4038

159.037 158.7039

158.937 158.9840

The standard uncertainty in temperature is ±0.01 K; The standard uncertainty in density value is 0.5 kg.m−3; The standard uncertainty in speed of sound value is 0.1 m·s−1; The standard uncertainty in heat capacity is ±0.3 %.

a

1141



Article

Table 3. Measured Densities, ρ123, Excess Molar Volumes, VE123, Speeds of Sound, u123, Isentropic Compressibilities, (κS)123, and Excess Isentropic Compressibilities, (κES )123, Data Compared with Graph and Prigogine−Flory−Patterson (PFP) Theories for the Various (1 + 2 + 3) Mixtures As a Function of Mole Fraction, x1, of Component (1) and, x2, of Component (2) at T/K = (293.15, 298.15, 303.15, and 308.15) and p = 0.1 MPaa VE123/cm3·mol−1 x1

x2

0.1595 0.1799 0.1936 0.2026 0.2218 0.2442 0.2603 0.2875 0.3015 0.3269 0.3478 0.3642 0.3891 0.4032 0.4121 0.4329 0.4453 0.4691 0.4845 0.5027 0.5278 0.5451 0.5774 0.5822 0.5974 0.6214 0.6464 0.6531 0.6894 0.7129

0.7681 0.7347 0.7081 0.6871 0.6542 0.6148 0.5861 0.5481 0.5245 0.4903 0.4658 0.4458 0.4208 0.4067 0.3976 0.3802 0.3671 0.3495 0.3332 0.3201 0.3014 0.2854 0.2608 0.2554 0.2432 0.2282 0.1932 0.1894 0.1698 0.1645

0.1595 0.1799 0.1936 0.2026 0.2218 0.2442 0.2603 0.2875 0.3015 0.3269 0.3478 0.3642 0.3891 0.4032 0.4121 0.4329 0.4453 0.4691 0.4845 0.5027 0.5278 0.5451 0.5774

0.7681 0.7347 0.7081 0.6871 0.6542 0.6148 0.5861 0.5481 0.5245 0.4903 0.4658 0.4458 0.4208 0.4067 0.3976 0.3802 0.3671 0.3495 0.3332 0.3201 0.3014 0.2854 0.2608

ρ123/kg·m

−3

u123/m·s

−1

exptl.

Graph

1-ethyl-3-methylimidazolium tetrafluoroborate (1) + T/K = 293.15 1072.41 1669.36 −1.3283 −1.3020 1080.44 1672.58 −1.3869 −1.3868 1085.67 1672.70 −1.4105 −1.4186 1089.08 1670.84 −1.4207 −1.4207 1096.24 1670.84 −1.4472 −1.4689 1104.51 1668.19 −1.4765 −1.5085 1110.46 1664.34 −1.5027 −1.5281 1120.21 1661.74 −1.5442 −1.5919 1125.38 1656.35 −1.5791 −1.6024 1134.39 1650.90 −1.6332 −1.6457 1141.57 1647.75 −1.6724 −1.6848 1147.21 1644.02 −1.7092 −1.7069 1155.34 1641.59 −1.7454 −1.7480 1159.87 1639.91 −1.7659 −1.7659 1162.72 1638.59 −1.7798 −1.7748 1169.00 1638.03 −1.7924 −1.7999 1172.90 1635.65 −1.8126 −1.8045 1179.65 1636.06 −1.8102 −1.8223 1184.33 1632.97 −1.8319 −1.8196 1189.25 1633.21 −1.8219 −1.8219 1195.91 1633.01 −1.8061 −1.8143 1200.62 1631.21 −1.8058 −1.8014 1208.71 1630.81 −1.7681 −1.7704 1210.01 1630.11 −1.7686 −1.7652 1213.71 1629.93 −1.7462 −1.7462 1219.08 1630.99 −1.6872 −1.7067 1225.69 1630.21 −1.6715 −1.6942 1227.06 1630.56 −1.6483 −1.6816 1234.21 1632.29 −1.5119 −1.5969 1238.27 1633.34 −1.4069 −1.4991 T/K = 298.15 1068.72 1645.88 −1.3859 −1.3456 1076.59 1649.66 −1.4302 −1.4264 1081.70 1650.27 −1.4424 −1.4510 1085.03 1648.79 −1.4450 −1.4450 1092.07 1649.68 −1.4597 −1.4874 1100.23 1648.22 −1.4793 −1.5194 1106.14 1645.33 −1.5026 −1.5338 1115.85 1644.15 −1.5404 −1.5981 1121.04 1639.60 −1.5794 −1.6063 1130.10 1635.36 −1.6388 −1.6522 1137.32 1633.07 −1.6824 −1.6959 1143.02 1630.01 −1.7252 −1.7214 1151.19 1628.35 −1.7672 −1.7699 1155.77 1627.02 −1.7920 −1.7920 1158.65 1625.92 −1.8090 −1.8035 1164.98 1625.83 −1.8258 −1.8351 1168.93 1623.60 −1.8518 −1.8435 1175.73 1624.38 −1.8537 −1.8679 1180.48 1621.38 −1.8827 −1.8704 1185.45 1621.77 −1.8771 −1.8771 1192.18 1621.64 −1.8679 −1.8752 1196.95 1619.73 −1.8742 −1.8682 1205.14 1619.18 −1.8451 −1.8450 1142

(κES )123/TPa−1 PFP

(κS)123/TPa

−1

exptl.

Graph

PFP

2-methylaniline (2) + pyridine (3) −0.6458 −0.7089 −0.7568 −0.7935 −0.8431 −0.8963 −0.9308 −0.9643 −0.9850 −1.0037 −1.0094 −1.0126 1.0061 −1.0006 −0.9967 −0.9807 −0.9738 −0.9483 −0.9371 −0.9144 −0.8820 −0.8625 −0.8169 −0.8121 −0.7903 −0.7494 −0.7291 −0.7167 −0.6470 −0.5918

334.61 330.85 329.20 328.90 326.75 325.34 325.09 323.28 323.89 323.44 322.64 322.51 321.19 320.59 320.32 318.82 318.68 316.70 316.64 315.24 313.56 313.02 311.08 311.01 310.13 308.37 307.00 306.52 304.10 302.71

−39.86 −43.24 −45.08 −45.89 −47.84 −49.13 −49.33 −49.93 −49.13 −48.30 −47.66 −46.74 −45.88 −45.24 −44.75 −44.06 −43.18 −42.40 −41.20 −40.45 −39.23 −38.11 −36.38 −36.09 −35.31 −33.99 −34.25 −33.82 −31.24 −28.59

−42.05 −44.42 −45.51 −45.89 −46.90 −47.47 −47.55 −47.82 −47.52 −47.17 −46.82 −46.39 −45.72 −45.24 −44.91 −44.05 −43.52 −42.25 −41.58 −40.45 −38.81 −38.02 −36.02 −36.04 −35.31 −33.34 −36.47 −36.02 −33.08 −28.01

−33.24 −32.51 −31.96 −31.48 −30.83 −29.94 −29.29 −28.36 −27.81 −26.99 −26.40 −25.93 −25.34 −25.02 −24.82 −24.42 −24.14 −23.76 −23.43 −23.16 −22.77 −22.47 −21.99 −21.90 −21.67 −21.37 −20.82 −20.75 −20.37 −20.19

−0.7131 −0.7755 −0.8341 −0.8924 −0.9278 −0.9855 −1.0228 −1.0592 −1.0814 −1.1015 −1.1075 −1.1107 −1.1035 −1.0973 −1.0930 −1.0755 −1.0678 −1.0400 −1.0274 −1.0026 −0.9671 −0.9455 −0.8954

345.41 341.32 339.45 339.02 336.47 334.57 333.95 331.52 331.82 330.87 329.69 329.28 327.61 326.85 326.48 324.74 324.53 322.34 322.23 320.73 318.97 318.45 316.50

−39.78 −43.48 −45.57 −46.56 −48.91 −50.70 −51.28 −52.42 −51.93 −51.53 −51.17 −50.46 −49.81 −49.25 −48.81 −48.20 −47.33 −46.56 −45.33 −44.53 −43.19 −41.94 −39.96

−41.42 −44.21 −45.76 −46.56 −48.10 −49.34 −49.89 −50.64 −50.67 −50.68 −50.53 −50.23 −49.68 −49.25 −48.94 −48.14 −47.60 −46.39 −45.64 −44.53 −42.89 −41.92 −39.73

−34.11 −33.33 −32.75 −32.26 −31.57 −30.64 −29.95 −28.97 −28.39 −27.52 −26.89 −26.40 −25.77 −25.43 −25.21 −24.79 −24.50 −24.08 −23.73 −23.44 −23.03 −22.70 −22.19



Article

Table 3. continued VE123/cm3·mol−1 x1

x2

ρ123/kg·m−3

u123/m·s−1

exptl.

0.5822 0.5974 0.6214 0.6464 0.6531 0.6894 0.7129

0.2554 0.2432 0.2282 0.1932 0.1894 0.1698 0.1645

1206.46 1210.19 1215.62 1222.19 1223.58 1230.81 1234.97

1618.38 1617.99 1618.90 1616.79 1617.11 1618.64 1619.99

−1.8472 −1.8284 −1.7745 −1.7549 −1.7328 −1.6035 −1.5078

0.1595 0.1799 0.1936 0.2026 0.2218 0.2442 0.2603 0.2875 0.3015 0.3269 0.3478 0.3642 0.3891 0.4032 0.4121 0.4329 0.4453 0.4691 0.4845 0.5027 0.5278 0.5451 0.5774 0.5822 0.5974 0.6214 0.6464 0.6531 0.6894 0.7129

0.7681 0.7347 0.7081 0.6871 0.6542 0.6148 0.5861 0.5481 0.5245 0.4903 0.4658 0.4458 0.4208 0.4067 0.3976 0.3802 0.3671 0.3495 0.3332 0.3201 0.3014 0.2854 0.2608 0.2554 0.2432 0.2282 0.1932 0.1894 0.1698 0.1645

1065.26 1073.11 1078.20 1081.50 1088.51 1096.63 1102.50 1112.18 1117.34 1126.37 1133.58 1139.28 1147.48 1152.08 1154.97 1161.36 1165.33 1172.23 1177.01 1182.06 1188.90 1193.75 1202.09 1203.43 1207.24 1212.79 1219.48 1220.90 1228.28 1232.54

1626.61 1630.88 1631.85 1630.65 1631.92 1630.88 1628.33 1627.51 1623.23 1619.36 1617.33 1614.48 1613.06 1611.88 1610.87 1610.91 1608.86 1609.75 1606.92 1607.42 1607.46 1605.73 1605.38 1604.62 1604.37 1605.39 1603.55 1603.89 1605.67 1607.14

−1.4685 −1.5112 −1.5211 −1.5210 −1.5331 −1.5486 −1.5679 −1.6027 −1.6377 −1.6937 −1.7365 −1.7784 −1.8225 −1.8487 −1.8669 −1.8884 −1.9163 −1.9259 −1.9584 −1.9598 −1.9607 −1.9735 −1.9589 −1.9629 −1.9511 −1.9087 −1.9009 −1.8816 −1.7660 −1.6784

0.1595 0.1799 0.1936 0.2026 0.2218 0.2442 0.2603 0.2875 0.3015 0.3269 0.3478 0.3642 0.3891 0.4032 0.4121 0.4329 0.4453 0.4691 0.4845

0.7681 0.7347 0.7081 0.6871 0.6542 0.6148 0.5861 0.5481 0.5245 0.4903 0.4658 0.4458 0.4208 0.4067 0.3976 0.3802 0.3671 0.3495 0.3332

1061.74 1069.54 1074.57 1077.82 1084.75 1092.77 1098.58 1108.18 1113.29 1122.27 1129.46 1135.13 1143.34 1147.94 1150.84 1157.24 1161.23 1168.16 1172.97

1609.28 1613.79 1614.92 1613.82 1615.26 1614.46 1612.07 1611.50 1607.38 1603.74 1601.88 1599.15 1597.90 1596.82 1595.87 1596.02 1594.07 1595.07 1592.36

−1.5599 −1.5978 −1.6025 −1.5976 −1.6030 −1.6101 −1.6236 −1.6517 −1.6830 −1.7350 −1.7759 −1.8169 −1.8612 −1.8881 −1.9068 −1.9302 −1.9597 −1.9728 −2.0083

Graph T/K = 298.15 −1.8427 −1.8284 −1.7911 −1.8108 −1.7990 −1.7148 −1.5989 T/K = 303.15 −1.4446 −1.5203 −1.5365 −1.5210 −1.5545 −1.5752 −1.5816 −1.6424 −1.6468 −1.6931 −1.7398 −1.7684 −1.8228 −1.8487 −1.8629 −1.8988 −1.9124 −1.9397 −1.9510 −1.9598 −1.9616 −1.9652 −1.9518 −1.9568 −1.9511 −1.9128 −2.0204 −2.0091 −1.9205 −1.7522 T/K = 308.15 −1.5442 −1.6153 −1.6230 −1.5976 −1.6221 −1.6307 −1.6281 −1.6837 −1.6827 −1.7264 −1.7737 −1.8030 −1.8604 −1.8881 −1.9036 −1.9421 −1.9582 −1.9872 −2.0034 1143


(κS)123/TPa−1

exptl.

Graph

PFP

−0.8900 −0.8659 −0.8212 −0.7972 −0.7837 −0.7078 −0.6482

316.47 315.64 313.88 313.00 312.53 310.10 308.54

−39.61 −38.66 −37.12 −36.82 −36.33 −33.40 −30.63

−39.59 −38.66 −36.65 −37.81 −37.30 −34.21 −30.08

−22.09 −21.84 −21.52 −20.94 −20.87 −20.45 −20.25

−0.7041 −0.7659 −0.8240 −0.8821 −0.9170 −0.9742 −1.0112 −1.0472 −1.0692 −1.0891 −1.0951 −1.0983 −1.0910 −1.0849 −1.0807 −1.0632 −1.0556 −1.0280 −1.0156 −0.9910 −0.9558 −0.9345 −0.8849 −0.8796 −0.8558 −0.8115 −0.7881 −0.7747 −0.6995 −0.6405

354.80 350.36 348.29 347.74 344.96 342.84 342.08 339.45 339.67 338.56 337.25 336.75 334.93 334.08 333.66 331.81 331.52 329.21 329.03 327.42 325.52 324.90 322.78 322.73 321.81 319.93 318.91 318.40 315.78 314.12

−43.26 −47.17 −49.38 −50.45 −52.90 −54.76 −55.38 −56.52 −56.02 −55.58 −55.18 −54.43 −53.71 −53.11 −52.64 −51.95 −51.05 −50.18 −48.89 −48.02 −46.58 −45.27 −43.15 −42.78 −41.78 −40.12 −39.78 −39.25 −36.14 −33.21

−44.99 −47.98 −49.61 −50.45 −52.07 −53.35 −53.91 −54.69 −54.70 −54.68 −54.50 −54.17 −53.57 −53.11 −52.78 −51.91 −51.33 −50.02 −49.22 −48.02 −46.24 −45.22 −42.88 −42.75 −41.78 −39.60 −41.16 −40.62 −37.27 −32.63

−35.37 −34.57 −33.98 −33.47 −32.76 −31.81 −31.11 −30.10 −29.51 −28.62 −27.98 −27.47 −26.83 −26.48 −26.26 −25.83 −25.53 −25.10 −24.74 −24.44 −24.02 −23.68 −23.16 −23.06 −22.81 −22.48 −21.89 −21.81 −21.38 −21.18

−0.6438 −0.7007 −0.7552 −0.8104 −0.8423 −0.8960 −0.9309 −0.9646 −0.9856 −1.0046 −1.0104 −1.0137 −1.0072 −1.0017 −0.9979 −0.9817 −0.9750 −0.9492 −0.9382

363.68 359.01 356.83 356.24 353.34 351.09 350.27 347.48 347.66 346.45 345.04 344.49 342.55 341.64 341.18 339.23 338.90 336.46 336.22

−45.79 −49.88 −52.20 −53.33 −55.88 −57.84 −58.50 −59.69 −59.20 −58.76 −58.34 −57.56 −56.79 −56.16 −55.67 −54.92 −53.99 −53.04 −51.71

−47.54 −50.70 −52.44 −53.33 −55.04 −56.41 −57.01 −57.83 −57.84 −57.83 −57.64 −57.29 −56.65 −56.16 −55.81 −54.89 −54.28 −52.88 −52.04

−36.52 −35.73 −35.14 −34.63 −33.93 −32.98 −32.29 −31.28 −30.70 −29.81 −29.17 −28.67 −28.04 −27.69 −27.47 −27.05 −26.75 −26.33 −25.98



Article


x2

0.5027 0.5278 0.5451 0.5774 0.5822 0.5974 0.6214 0.6464 0.6531 0.6894 0.7129

0.3201 0.3014 0.2854 0.2608 0.2554 0.2432 0.2282 0.1932 0.1894 0.1698 0.1645

0.1131 0.1231 0.1404 0.1637 0.1817 0.2044 0.2245 0.2411 0.2623 0.2837 0.3007 0.3129 0.3338 0.3451 0.3601 0.3733 0.3911 0.4104 0.4325 0.4549 0.4897 0.5038 0.5363 0.5612 0.5943 0.6284 0.6445 0.6647 0.6881 0.6993

0.7887 0.7819 0.7642 0.7404 0.7173 0.6816 0.6621 0.6404 0.6187 0.5881 0.5697 0.5533 0.5308 0.5133 0.4781 0.4381 0.4025 0.3711 0.3524 0.3345 0.3122 0.3045 0.2813 0.2657 0.2433 0.2216 0.2113 0.1986 0.1835 0.1763

0.1131 0.1231 0.1404 0.1637 0.1817 0.2044 0.2245 0.2411 0.2623 0.2837 0.3007 0.3129 0.3338 0.3451

0.7887 0.7819 0.7642 0.7404 0.7173 0.6816 0.6621 0.6404 0.6187 0.5881 0.5697 0.5533 0.5308 0.5133

ρ123/kg·m−3

u123/m·s−1

exptl.

Graph


(κS)123/TPa−1

exptl.

T/K = 308.15 1178.05 1592.94 −2.0132 −2.0132 −0.9154 334.53 −50.77 1184.95 1593.10 −2.0197 −2.0168 −0.8828 332.52 −49.23 1189.84 1591.46 −2.0370 −2.0268 −0.8635 331.83 −47.86 1198.27 1591.27 −2.0308 −2.0191 −0.8178 329.58 −45.61 1199.62 1590.56 −2.0363 −2.0289 −0.8132 329.50 −45.24 1203.48 1590.38 −2.0288 −2.0288 −0.7914 328.52 −44.18 1209.09 1591.52 −1.9925 −1.9894 −0.7503 326.52 −42.41 1215.86 1590.03 −1.9931 −2.1581 −0.7310 325.31 −42.16 1217.29 1590.42 −1.9753 −2.1474 −0.7186 324.77 −41.60 1224.76 1592.31 −1.8669 −2.0559 −0.6486 322.03 −38.26 1229.06 1593.74 −1.7831 −1.8503 −0.5927 320.32 −35.09 1-ethyl-3-methylimidazolium tetrafluoroborate (1) +2-methylaniline (2) + α-picoline (3) T/K= 293.15 1050.43 1629.55 −1.2969 −1.2831 −0.6724 358.50 −27.82 1055.22 1630.91 −1.3921 −1.3951 −0.6913 356.29 −28.65 1063.27 1630.58 −1.5673 −1.5918 −0.7331 353.73 −29.75 1074.08 1629.22 −1.8142 −1.8658 −0.7805 350.75 −30.76 1082.19 1625.20 −2.0109 −2.0567 −0.8244 349.85 −30.89 1091.92 1616.03 −2.2484 −2.2484 −0.8911 350.68 −30.14 1100.99 1613.28 −2.4660 −2.4728 −0.9125 348.98 −29.98 1107.98 1608.08 −2.6260 −2.6145 −0.9416 349.02 −29.29 1117.06 1604.34 −2.8328 −2.8287 −0.9585 347.80 −28.73 1125.14 1596.52 −2.9745 −2.9502 −0.9939 348.69 −27.42 1131.76 1593.31 −3.0935 −3.0859 −1.0036 348.05 −26.79 1135.98 1589.87 −3.1408 −3.1408 −1.0171 348.26 −26.18 1143.46 1586.70 −3.2361 −3.2783 −1.0232 347.37 −25.49 1146.59 1583.42 −3.2167 −3.2754 −1.0381 347.85 −25.00 1148.64 1577.64 −3.0168 −3.0997 −1.0827 349.78 −24.97 1148.81 1575.82 −2.7042 −2.8108 −1.1353 350.54 −27.32 1151.79 1578.79 −2.5079 −2.5959 −1.1619 348.32 −30.81 1156.14 1584.23 −2.3944 −2.3944 −1.1727 344.63 −34.73 1162.71 1587.71 −2.3839 −2.3561 −1.1523 341.18 −35.70 1169.25 1591.46 −2.3697 −2.3113 −1.1273 337.68 −36.52 1179.40 1595.93 −2.3515 −2.3150 −1.0746 332.90 −36.25 1183.45 1597.37 −2.3424 −2.3424 −1.0496 331.16 −35.73 1192.13 1602.90 −2.2852 −2.2610 −0.9984 326.49 −36.07 1198.64 1606.41 −2.2360 −2.2378 −0.9533 323.30 −35.59 1206.87 1611.73 −2.1513 −2.1316 −0.8937 318.98 −35.30 1215.03 1616.50 −2.0491 −2.0369 −0.8275 314.97 −34.34 1218.75 1617.36 −1.9951 −1.9795 −0.7955 313.67 −33.30 1223.31 1621.15 −1.9222 −1.9069 −0.7544 311.04 −32.96 1228.44 1623.96 −1.8316 −1.7903 −0.7067 308.67 −31.95 1230.84 1625.17 −1.7858 −1.7294 −0.6835 307.61 −31.39 T/K = 298.15 1046.40 1608.26 −1.3193 −1.3104 −0.7427 369.48 −28.00 1051.25 1610.61 −1.4223 −1.4274 −0.7641 366.70 −29.31 1059.36 1612.31 −1.6051 −1.6286 −0.8108 363.12 −31.33 1070.20 1614.19 −1.8574 −1.9051 −0.8639 358.61 −33.74 1078.29 1613.09 −2.0538 −2.0963 −0.9126 356.41 −35.11 1087.98 1602.68 −2.2888 −2.2888 −0.9863 357.84 −33.72 1097.00 1601.26 −2.5036 −2.5112 −1.0105 355.52 −34.05 1103.96 1597.12 −2.6613 −2.6522 −1.0427 355.12 −33.75 1112.98 1593.15 −2.8634 −2.8627 −1.0618 354.00 −32.97 1121.05 1587.50 −3.0058 −2.9848 −1.1007 353.95 −32.54 1127.64 1584.80 −3.1233 −3.1178 −1.1115 353.08 −32.05 1131.88 1582.53 −3.1732 −3.1732 −1.1263 352.77 −31.92 1139.37 1580.60 −3.2698 −3.3077 −1.1332 351.31 −31.69 1142.58 1577.45 −3.2583 −3.3085 −1.1494 351.72 −31.25 1144

Graph

PFP

−50.77 −48.89 −47.81 −45.34 −45.21 −44.18 −41.88 −43.56 −42.98 −39.44 −34.51

−25.68 −25.27 −24.94 −24.43 −24.32 −24.08 −23.76 −23.17 −23.09 −22.68 −22.48

−21.50 −24.03 −26.72 −29.10 −29.90 −30.14 −30.20 −29.84 −28.84 −27.99 −26.79 −26.18 −24.46 −24.32 −26.09 −29.09 −31.71 −34.73 −35.96 −37.01 −36.68 −35.73 −35.69 −34.35 −33.51 −31.59 −30.73 −29.46 −28.49 −28.06

−35.27 −34.91 −34.28 −33.46 −32.83 −32.01 −31.39 −30.85 −30.23 −29.54 −29.06 −28.69 −28.14 −27.78 −27.14 −26.35 −25.57 −24.86 −24.47 −24.11 −23.67 −23.52 −23.06 −22.75 −22.31 −21.87 −21.66 −21.40 −21.09 −20.95

−23.51 −26.11 −29.05 −31.83 −33.00 −33.72 −34.19 −34.18 −33.65 −33.19 −32.33 −31.92 −30.59 −30.54

−36.28 −35.89 −35.22 −34.36 −33.69 −32.83 −32.17 −31.59 −30.93 −30.21 −29.70 −29.31 −28.72 −28.34



Article


x2

ρ123/kg·m−3

u123/m·s−1

exptl.

0.3601 0.3733 0.3911 0.4104 0.4325 0.4549 0.4897 0.5038 0.5363 0.5612 0.5943 0.6284 0.6445 0.6647 0.6881 0.6993

0.4781 0.4381 0.4025 0.3711 0.3524 0.3345 0.3122 0.3045 0.2813 0.2657 0.2433 0.2216 0.2113 0.1986 0.1835 0.1763

1144.88 1145.35 1148.46 1152.84 1159.45 1166.04 1176.27 1180.38 1189.13 1195.72 1204.04 1212.30 1216.07 1220.69 1225.87 1228.30

1571.12 1568.35 1567.23 1574.72 1577.39 1581.56 1586.39 1588.72 1593.94 1596.71 1600.58 1605.30 1607.18 1611.46 1613.37 1614.71

−3.0849 −2.8021 −2.6204 −2.5104 −2.5035 −2.4929 −2.4840 −2.4796 −2.4300 −2.3885 −2.3124 −2.2202 −2.1705 −2.1029 −2.0175 −1.9739

0.1131 0.1231 0.1404 0.1637 0.1817 0.2044 0.2245 0.2411 0.2623 0.2837 0.3007 0.3129 0.3338 0.3451 0.3601 0.3733 0.3911 0.4104 0.4325 0.4549 0.4897 0.5038 0.5363 0.5612 0.5943 0.6284 0.6445 0.6647 0.6881 0.6993

0.7887 0.7819 0.7642 0.7404 0.7173 0.6816 0.6621 0.6404 0.6187 0.5881 0.5697 0.5533 0.5308 0.5133 0.4781 0.4381 0.4025 0.3711 0.3524 0.3345 0.3122 0.3045 0.2813 0.2657 0.2433 0.2216 0.2113 0.1986 0.1835 0.1763

1042.70 1047.58 1055.69 1066.52 1074.57 1084.19 1093.21 1100.14 1109.16 1117.19 1123.78 1128.01 1135.50 1138.69 1140.90 1141.25 1144.34 1148.74 1155.43 1162.10 1172.49 1176.65 1185.56 1192.28 1200.77 1209.19 1213.04 1217.75 1223.03 1225.49

1586.74 1589.11 1590.83 1592.54 1591.21 1585.69 1586.03 1585.37 1582.76 1577.66 1576.53 1574.21 1573.01 1570.14 1563.08 1558.19 1558.87 1562.50 1566.13 1569.92 1574.98 1576.75 1582.07 1585.58 1590.52 1594.89 1596.83 1599.03 1601.43 1602.47

−1.3795 −1.4844 −1.6679 −1.9203 −2.1145 −2.3439 −2.5588 −2.7143 −2.9165 −3.0552 −3.1727 −3.2210 −3.3178 −3.3035 −3.1196 −2.8241 −2.6381 −2.5299 −2.5293 −2.5263 −2.5304 −2.5317 −2.4962 −2.4659 −2.4052 −2.3283 −2.2856 −2.2263 −2.1496 −2.1098

0.1131 0.1231 0.1404 0.1637 0.1817 0.2044 0.2245 0.2411 0.2623 0.2837

0.7887 0.7819 0.7642 0.7404 0.7173 0.6816 0.6621 0.6404 0.6187 0.5881

1038.89 1043.82 1051.98 1062.90 1071.00 1080.63 1089.75 1096.71 1105.82 1113.83

1569.42 1572.23 1574.77 1577.80 1577.60 1573.55 1575.30 1573.72 1572.57 1569.52

−1.4389 −1.5499 −1.7413 −2.0056 −2.2067 −2.4397 −2.6671 −2.8276 −3.0412 −3.1791

Graph T/K = 298.15 −3.1496 −2.8848 −2.6908 −2.5104 −2.4817 −2.4457 −2.4539 −2.4796 −2.4044 −2.3802 −2.2765 −2.1794 −2.1209 −2.0458 −1.9280 −1.8664 T/K = 303.15 −1.3224 −1.4552 −1.6713 −1.9634 −2.1577 −2.3439 −2.5730 −2.7118 −2.9238 −3.0383 −3.1695 −3.2210 −3.3520 −3.3480 −3.1781 −2.9020 −2.7057 −2.5299 −2.5110 −2.4846 −2.5037 −2.5317 −2.4646 −2.4430 −2.3440 −2.2482 −2.1900 −2.1146 −1.9974 −1.9360 T/K = 308.15 −1.3467 −1.4973 −1.7339 −2.0521 −2.2562 −2.4397 −2.6873 −2.8289 −3.0547 −3.1628 1145


(κS)123/TPa−1

exptl.

Graph

PFP

−1.1977 −1.2543 −1.2828 −1.2941 −1.2717 −1.2442 −1.1864 −1.1590 −1.1026 −1.0531 −0.9874 −0.9143 −0.8790 −0.8337 −0.7810 −0.7555

353.85 354.96 354.50 349.80 346.63 342.86 337.81 335.65 331.00 328.03 324.19 320.09 318.36 315.47 313.39 312.25

−31.09 −33.22 −34.98 −39.89 −40.42 −41.34 −41.04 −40.81 −40.86 −39.94 −38.89 −37.72 −36.98 −36.72 −35.22 −34.64

−32.18 −34.84 −37.19 −39.89 −41.04 −42.01 −41.68 −40.81 −40.63 −39.28 −38.25 −36.18 −35.22 −33.81 −32.61 −32.06

−27.67 −26.87 −26.05 −25.30 −24.88 −24.49 −24.02 −23.85 −23.35 −23.01 −22.53 −22.06 −21.83 −21.55 −21.21 −21.05

−0.7314 −0.7524 −0.7982 −0.8504 −0.8983 −0.9707 −0.9944 −1.0260 −1.0447 −1.0830 −1.0936 −1.1081 −1.1148 −1.1308 −1.1783 −1.2342 −1.2622 −1.2733 −1.2512 −1.2240 −1.1670 −1.1399 −1.0844 −1.0356 −0.9709 −0.8989 −0.8642 −0.8196 −0.7678 −0.7426

380.92 378.01 374.30 369.70 367.54 366.82 363.64 362.56 359.90 359.62 358.03 357.74 355.92 356.22 358.75 360.89 359.60 356.56 352.86 349.14 343.83 341.84 336.99 333.62 329.20 325.12 323.30 321.17 318.82 317.77

−30.06 −31.39 −33.40 −35.69 −36.88 −37.50 −38.52 −38.77 −39.35 −39.01 −39.10 −38.86 −38.81 −38.41 −37.81 −38.91 −41.43 −44.57 −45.42 −46.07 −45.67 −45.11 −45.03 −44.26 −43.44 −41.90 −41.07 −39.85 −38.37 −37.59

−25.45 −28.04 −31.22 −34.49 −36.15 −37.50 −38.59 −39.06 −39.25 −39.32 −39.01 −38.86 −38.14 −38.16 −39.31 −41.06 −42.67 −44.57 −45.47 −46.18 −45.84 −45.11 −44.66 −43.34 −42.04 −39.84 −38.78 −37.26 −35.78 −35.07

−37.59 −37.19 −36.51 −35.62 −34.94 −34.05 −33.38 −32.79 −32.11 −31.37 −30.85 −30.45 −29.84 −29.46 −28.78 −27.95 −27.11 −26.35 −25.92 −25.52 −25.03 −24.86 −24.35 −24.01 −23.52 −23.03 −22.80 −22.51 −22.17 −22.00

−0.6761 −0.6945 −0.7357 −0.7825 −0.8262 −0.8933 −0.9142 −0.9433 −0.9599 −0.9956

390.79 387.56 383.32 377.92 375.16 373.73 369.78 368.17 364.75 363.99

−32.32 −33.88 −36.31 −39.25 −40.97 −42.27 −43.92 −44.64 −45.84 −45.92

−27.81 −30.65 −34.31 −38.30 −40.46 −42.27 −44.03 −44.90 −45.76 −46.15

−38.75 −38.35 −37.67 −36.79 −36.12 −37.24 −34.57 −33.99 −33.32 −32.58



Article


x2

0.3007 0.3129 0.3338 0.3451 0.3601 0.3733 0.3911 0.4104 0.4325 0.4549 0.4897 0.5038 0.5363 0.5612 0.5943 0.6284 0.6445 0.6647 0.6881 0.6993

0.5697 0.5533 0.5308 0.5133 0.4781 0.4381 0.4025 0.3711 0.3524 0.3345 0.3122 0.3045 0.2813 0.2657 0.2433 0.2216 0.2113 0.1986 0.1835 0.1763

0.1151 0.1301 0.1524 0.1746 0.1923 0.2156 0.2388 0.2512 0.2833 0.3082 0.3241 0.3412 0.3795 0.3902 0.4097 0.4241 0.4429 0.4612 0.4853 0.5068 0.5231 0.5422 0.5614 0.5834 0.6011 0.6245 0.6432 0.6614 0.6843 0.7034

0.7811 0.7574 0.7325 0.7152 0.6954 0.6759 0.6645 0.6452 0.6051 0.5521 0.5374 0.5166 0.4691 0.4012 0.3754 0.3632 0.3469 0.3331 0.3183 0.3021 0.2905 0.2781 0.2654 0.2504 0.2371 0.2216 0.2091 0.1965 0.1843 0.1719

0.1151 0.1301 0.1524 0.1746 0.1923

0.7811 0.7574 0.7325 0.7152 0.6954

ρ123/kg·m−3

u123/m·s−1

exptl.

Graph


(κS)123/TPa−1

exptl.

T/K = 308.15 1120.46 1568.76 −3.3013 −3.2993 −1.0051 361.94 −46.37 1124.65 1568.39 −3.3470 −3.3470 −1.0188 361.47 −46.27 1132.15 1566.23 −3.4456 −3.4817 −1.0248 359.26 −46.49 1135.24 1563.04 −3.4211 −3.4669 −1.0400 359.64 −46.00 1137.06 1556.54 −3.1959 −3.2558 −1.0860 362.99 −44.66 1136.88 1549.17 −2.8434 −2.9253 −1.1403 366.51 −44.55 1139.62 1548.12 −2.6202 −2.6926 −1.1680 366.13 −46.21 1143.82 1550.54 −2.4897 −2.4897 −1.1795 363.64 −48.78 1150.50 1554.15 −2.4882 −2.4702 −1.1589 359.85 −49.54 1157.19 1558.01 −2.4863 −2.4436 −1.1336 356.00 −50.13 1167.59 1563.56 −2.4910 −2.4714 −1.0802 350.33 −49.74 1171.88 1565.53 −2.5054 −2.5054 −1.0548 348.17 −49.20 1180.88 1571.04 −2.4773 −2.4383 −1.0033 343.10 −49.04 1187.68 1574.80 −2.4554 −2.4206 −0.9578 339.51 −48.23 1196.28 1579.99 −2.4054 −2.3210 −0.8978 334.86 −47.33 1204.84 1584.71 −2.3413 −2.2266 −0.8310 330.50 −45.72 1208.74 1586.80 −2.3048 −2.1684 −0.7988 328.56 −44.85 1213.53 1589.20 −2.2533 −2.0932 −0.7575 326.28 −43.57 1218.90 1591.85 −2.1853 −1.9744 −0.7095 323.76 −42.03 1221.41 1592.99 −2.1495 −1.9122 −0.6863 322.64 −41.21 1-ethyl-3-methylimidazolium tetrafluoroborate (1) +2-methylaniline (2) + β-picoline (3) T/K= 293.15 1052.56 1634.34 −1.3374 −1.3205 −0.6323 355.69 −27.22 1059.28 1634.05 −1.4828 −1.4663 −0.6871 353.56 −29.07 1069.34 1637.32 −1.6862 −1.6682 −0.7419 348.83 −32.15 1079.38 1644.09 −1.8831 −1.8707 −0.7727 342.74 −35.70 1087.12 1646.94 −2.0417 −2.0286 −0.8042 339.13 −38.01 1097.30 1654.21 −2.2446 −2.2446 −0.8251 333.04 −41.60 1107.41 1666.72 −2.4402 −2.4928 −0.8204 325.06 −46.13 1112.37 1665.42 −2.5404 −2.5739 −0.8465 324.12 −46.81 1124.96 1666.74 −2.7674 −2.7987 −0.8836 319.98 −49.08 1132.95 1648.89 −2.8293 −2.8293 −0.9515 324.64 −45.59 1138.75 1650.95 −2.9028 −2.9267 −0.9518 322.18 −46.51 1144.44 1648.56 −2.9438 −2.9938 −0.9598 321.51 −46.12 1156.18 1639.88 −2.9582 −3.0837 −0.9713 321.62 −43.74 1155.32 1599.44 −2.6528 −2.6933 −1.0594 338.35 −32.91 1160.86 1596.02 −2.6322 −2.6322 −1.0484 338.17 −32.12 1165.17 1596.56 −2.6303 −2.6249 −1.0469 336.70 −32.07 1170.65 1597.26 −2.6210 −2.6004 −1.0307 334.83 −31.99 1175.91 1598.70 −2.6080 −2.5848 −1.0106 332.73 −31.94 1182.70 1601.62 −2.5832 −2.5908 −0.9775 329.61 −31.83 1188.48 1603.38 −2.5486 −2.5486 −0.9500 327.29 −31.63 1192.76 1604.95 −2.5172 −2.5166 −0.9271 325.48 −31.45 1197.66 1607.10 −2.4745 −2.4891 −0.8977 323.28 −31.17 1202.45 1609.21 −2.4248 −2.4496 −0.8674 321.15 −30.84 1207.77 1611.51 −2.3606 −2.3849 −0.8320 318.82 −30.40 1211.94 1613.25 −2.3056 −2.2971 −0.8043 317.04 −30.10 1217.30 1615.85 −2.2233 −2.2092 −0.7640 314.63 −29.51 1221.46 1617.89 −2.1522 −2.1253 −0.7312 312.77 −28.99 1225.41 1619.84 −2.0799 −2.0223 −0.6992 311.01 −28.48 1230.19 1622.30 −1.9714 −1.9801 −0.6536 308.86 −27.34 1234.10 1624.15 −1.8820 −1.8751 −0.6178 307.18 −26.54 T/K = 298.15 1048.64 1612.15 −1.3720 −1.3399 −0.6895 366.91 −27.10 1055.40 1612.75 −1.5236 −1.4914 −0.7494 364.29 −29.41 1065.60 1617.25 −1.7429 −1.7098 −0.8100 358.80 −33.14 1075.82 1625.13 −1.9603 −1.9377 −0.8450 351.95 −37.29 1083.67 1629.02 −2.1318 −2.1106 −0.8799 347.74 −40.11 1146

Graph

PFP

−46.26 −46.27 −46.00 −45.97 −46.37 −46.95 −47.68 −48.78 −49.52 −50.05 −49.78 −49.20 −48.54 −47.24 −45.72 −43.37 −42.20 −40.56 −38.82 −37.97

−32.07 −31.67 −31.07 −30.69 −30.01 −29.18 −28.34 −27.58 −27.16 −26.77 −26.29 −26.12 −25.63 −25.29 −24.81 −24.33 −24.10 −23.82 −23.48 −23.32

−21.72 −23.99 −28.64 −34.09 −37.01 −41.60 −47.25 −47.50 −49.35 −45.59 −46.76 −46.73 −45.56 −33.73 −32.12 −32.12 −31.84 −31.79 −32.16 −31.63 −31.22 −30.86 −30.29 −29.37 −28.23 −27.02 −25.90 −24.63 −23.73 −22.38

−34.81 −34.18 −33.36 −32.66 −32.06 −31.36 −30.76 −30.34 −29.36 −28.36 −27.96 −27.48 −26.42 −25.02 −24.44 −24.19 −23.86 −23.59 −23.32 −23.02 −22.81 −22.58 −22.34 −22.07 −21.83 −21.54 −21.31 −21.08 −20.83 −20.60

−22.66 −25.16 −30.00 −35.70 −39.02

−35.74 −35.07 −34.20 −33.46 −32.82



Article


x2

ρ123/kg·m−3

u123/m·s−1

exptl.

0.2156 0.2388 0.2512 0.2833 0.3082 0.3241 0.3412 0.3795 0.3902 0.4097 0.4241 0.4429 0.4612 0.4853 0.5068 0.5231 0.5422 0.5614 0.5834 0.6011 0.6245 0.6432 0.6614 0.6843 0.7034

0.6759 0.6645 0.6452 0.6051 0.5521 0.5374 0.5166 0.4691 0.4012 0.3754 0.3632 0.3469 0.3331 0.3183 0.3021 0.2905 0.2781 0.2654 0.2504 0.2371 0.2216 0.2091 0.1965 0.1843 0.1719

1094.03 1104.37 1109.37 1122.12 1129.98 1135.85 1141.55 1153.19 1151.46 1156.89 1161.20 1166.67 1171.95 1178.81 1184.62 1188.93 1193.88 1198.72 1204.10 1208.30 1213.72 1217.94 1221.94 1226.80 1230.76

1637.44 1650.70 1650.35 1653.74 1638.64 1641.49 1640.15 1631.42 1589.44 1585.16 1586.58 1587.84 1589.83 1591.60 1593.24 1595.57 1597.23 1599.77 1601.60 1602.67 1604.20 1606.19 1608.09 1610.58 1612.20

−2.3553 −2.5751 −2.6810 −2.9255 −2.9761 −3.0572 −3.0989 −3.1046 −2.7092 −2.6761 −2.6739 −2.6636 −2.6522 −2.6336 −2.6010 −2.5723 −2.5340 −2.4887 −2.4294 −2.3775 −2.3012 −2.2350 −2.1671 −2.0660 −1.9811

0.1151 0.1301 0.1524 0.1746 0.1923 0.2156 0.2388 0.2512 0.2833 0.3082 0.3241 0.3412 0.3795 0.3902 0.4097 0.4241 0.4429 0.4612 0.4853 0.5068 0.5231 0.5422 0.5614 0.5834 0.6011 0.6245 0.6432 0.6614 0.6843 0.7034

0.7811 0.7574 0.7325 0.7152 0.6954 0.6759 0.6645 0.6452 0.6051 0.5521 0.5374 0.5166 0.4691 0.4012 0.3754 0.3632 0.3469 0.3331 0.3183 0.3021 0.2905 0.2781 0.2654 0.2504 0.2371 0.2216 0.2091 0.1965 0.1843 0.1719

1044.96 1051.56 1061.55 1071.59 1079.25 1089.40 1099.59 1104.43 1116.85 1124.46 1130.26 1135.91 1147.58 1146.32 1151.96 1156.36 1161.98 1167.39 1174.40 1180.40 1184.85 1189.96 1194.97 1200.55 1204.92 1210.56 1214.93 1219.09 1224.10 1228.19

1591.62 1592.95 1598.60 1607.76 1612.77 1622.81 1637.86 1638.40 1643.91 1628.79 1632.38 1631.32 1624.49 1579.08 1574.98 1575.63 1576.26 1577.78 1581.10 1582.69 1584.15 1586.26 1588.23 1590.26 1591.00 1593.77 1595.49 1597.08 1599.45 1601.00

−1.4318 −1.5684 −1.7667 −1.9652 −2.1173 −2.3190 −2.5233 −2.6123 −2.8233 −2.8477 −2.9212 −2.9571 −2.9627 −2.6165 −2.6037 −2.6105 −2.6143 −2.6155 −2.6109 −2.5967 −2.5818 −2.5589 −2.5300 −2.4907 −2.4564 −2.4007 −2.3505 −2.2981 −2.2116 −2.1399

Graph T/K = 298.15 −2.3553 −2.6477 −2.7305 −2.9744 −2.9761 −3.0874 −3.1591 −3.2507 −2.7517 −2.6761 −2.6691 −2.6428 −2.6286 −2.6438 −2.6010 −2.5695 −2.5454 −2.5079 −2.4427 −2.3482 −2.2582 −2.1709 −2.0611 −2.0282 −1.9182 T/K = 303.15 −1.2925 −1.4381 −1.6692 −1.9140 −2.0816 −2.3190 −2.5919 −2.6599 −2.8637 −2.8477 −2.9428 −3.0004 −3.0712 −2.6511 −2.6037 −2.6098 −2.6029 −2.6030 −2.6236 −2.5967 −2.5747 −2.5549 −2.5226 −2.4670 −2.3921 −2.3125 −2.2360 −2.1435 −2.0893 −1.9895

1147


(κS)123/TPa−1

exptl.

Graph

PFP

−0.9040 −0.9008 −0.9290 −0.9695 −1.0410 −1.0417 −1.0502 −1.0620 −1.1524 −1.1505 −1.1380 −1.1203 −1.0985 −1.0629 −1.0329 −1.0081 −0.9762 −0.9433 −0.9049 −0.8746 −0.8308 −0.7950 −0.7601 −0.7108 −0.6718

340.91 332.32 330.95 325.86 329.58 326.74 325.64 325.81 343.77 344.00 342.12 339.97 337.59 334.88 332.55 330.38 328.32 325.96 323.76 322.21 320.16 318.26 316.47 314.24 312.60

−44.27 −49.20 −50.27 −53.37 −50.86 −52.06 −52.02 −49.42 −37.69 −36.42 −36.68 −36.75 −36.84 −36.12 −35.76 −35.81 −35.23 −34.97 −34.22 −33.56 −32.42 −31.78 −31.16 −29.89 −28.89

−44.27 −50.95 −51.54 −54.48 −50.86 −52.58 −52.98 −52.50 −38.41 −36.42 −36.36 −35.94 −35.84 −36.40 −35.76 −35.31 −35.00 −34.45 −33.45 −31.97 −30.64 −29.29 −27.66 −27.13 25.51

−32.08 −31.44 −31.00 −29.96 −28.90 −28.48 −27.97 −26.85 −25.40 −24.78 −24.52 −24.16 −23.88 −23.58 −23.25 −23.02 −22.78 −22.52 −22.22 −21.97 −21.66 −21.41 −21.16 −20.89 −20.64

−0.6812 −0.7403 −0.7999 −0.8342 −0.8685 −0.8920 −0.8885 −0.9163 −0.9562 −1.0272 −1.0278 −1.0362 −1.0478 −1.1380 −1.1363 −1.1239 −1.1064 −1.0848 −1.0494 −1.0198 −0.9952 −0.9637 −0.9312 −0.8932 −0.8633 −0.8200 −0.7847 −0.7502 −0.7014 −0.6630

377.77 374.77 368.62 361.02 356.23 348.56 339.01 337.30 331.32 335.22 332.03 330.81 330.20 349.85 349.96 348.34 346.37 344.10 340.62 338.20 336.31 333.98 331.75 329.37 327.65 325.21 323.34 321.60 319.33 317.65

−29.61 −32.20 −36.40 −41.09 −44.33 −49.12 −54.76 −56.09 −59.82 −57.01 −58.41 −58.36 −56.23 −42.90 −41.61 −41.47 −41.18 −40.99 −40.80 −40.32 −39.93 −39.44 −38.85 −38.07 −37.41 −36.42 −35.57 −34.72 −33.25 −32.10

−25.75 −28.56 −33.76 −39.80 −43.44 −49.12 −56.33 −57.12 −60.59 −57.01 −58.94 −59.48 −59.14 −43.89 −41.61 −41.45 −40.86 −40.64 −41.15 −40.32 −39.74 −39.33 −38.66 −37.46 −35.72 −34.12 −32.58 −30.68 −30.13 −28.27

−37.05 −36.37 −35.48 −34.71 −34.06 −33.30 −32.64 −32.19 −31.13 −30.04 −29.62 −29.09 −27.94 −26.46 −25.83 −25.56 −25.20 −24.90 −24.60 −24.27 −24.03 −23.78 −23.52 −23.21 −22.95 −22.63 −22.38 −22.12 −21.85 −21.59



Article


x2

0.1151 0.1301 0.1524 0.1746 0.1923 0.2156 0.2388 0.2512 0.2833 0.3082 0.3241 0.3412 0.3795 0.3902 0.4097 0.4241 0.4429 0.4612 0.4853 0.5068 0.5231 0.5422 0.5614 0.5834 0.6011 0.6245 0.6432 0.6614 0.6843 0.7034

0.7811 0.7574 0.7325 0.7152 0.6954 0.6759 0.6645 0.6452 0.6051 0.5521 0.5374 0.5166 0.4691 0.4012 0.3754 0.3632 0.3469 0.3331 0.3183 0.3021 0.2905 0.2781 0.2654 0.2504 0.2371 0.2216 0.2091 0.1965 0.1843 0.1719

0.1163 0.1315 0.1531 0.1718 0.1904 0.2131 0.2319 0.2507 0.2711 0.2953 0.3104 0.3293 0.3416 0.3597 0.3687 0.3811 0.4055 0.4311 0.4619 0.5094 0.5326 0.5630 0.5933 0.6226 0.6535 0.6629

0.7821 0.7635 0.7444 0.7228 0.7011 0.6712 0.6524 0.6329 0.6063 0.5726 0.5514 0.5332 0.5089 0.4662 0.4365 0.4039 0.3721 0.3514 0.3304 0.3008 0.2841 0.2645 0.2447 0.2251 0.2054 0.1997

ρ123/kg·m−3

u123/m·s−1

exptl.

Graph


(κS)123/TPa−1

exptl.

T/K = 308.15 1040.89 1575.25 −1.4627 −1.3003 −0.6266 387.17 −32.08 1047.51 1576.95 −1.6026 −1.4489 −0.6808 383.89 −34.90 1057.56 1583.11 −1.8095 −1.6935 −0.7347 377.29 −39.42 1067.69 1592.71 −2.0193 −1.9580 −0.7647 369.22 −44.40 1075.39 1598.11 −2.1771 −2.1344 −0.7956 364.10 −47.87 1085.61 1608.58 −2.3889 −2.3889 −0.8159 355.99 −52.92 1095.92 1623.90 −2.6065 −2.6859 −0.8107 346.02 −58.75 1100.75 1624.81 −2.6959 −2.7526 −0.8365 344.12 −60.24 1113.19 1631.10 −2.9117 −2.9613 −0.8731 337.65 −64.29 1120.68 1616.80 −2.9251 −2.9251 −0.9406 341.35 −61.69 1126.51 1620.68 −3.0021 −3.0260 −0.9408 337.96 −63.18 1132.15 1619.94 −3.0376 −3.0842 −0.9487 336.59 −63.19 1143.77 1613.70 −3.0392 −3.1530 −0.9600 335.75 −61.10 1142.09 1568.17 −2.6482 −2.6818 −1.0481 356.05 −47.41 1147.68 1564.19 −2.6313 −2.6313 −1.0472 356.12 −46.07 1152.10 1564.96 −2.6398 −2.6403 −1.0357 354.41 −45.91 1157.75 1565.75 −2.6458 −2.6363 −1.0196 352.33 −45.60 1163.19 1567.43 −2.6507 −2.6402 −0.9996 349.92 −45.39 1170.27 1570.97 −2.6530 −2.6677 −0.9666 346.24 −45.18 1176.32 1572.73 −2.6436 −2.6436 −0.9393 343.69 −44.66 1180.81 1574.32 −2.6328 −2.6237 −0.9166 341.69 −44.24 1185.98 1576.59 −2.6153 −2.6069 −0.8874 339.22 −43.71 1191.04 1578.69 −2.5919 −2.5768 −0.8573 336.88 −43.07 1196.68 1580.90 −2.5586 −2.5226 −0.8222 334.36 −42.24 1201.11 1582.33 −2.5288 −2.4472 −0.7948 332.53 −41.54 1206.80 1584.75 −2.4796 −2.3680 −0.7549 329.95 −40.49 1211.23 1586.61 −2.4344 −2.2912 −0.7224 327.97 −39.58 1215.43 1588.34 −2.3865 −2.1975 −0.6907 326.12 −38.68 1220.51 1590.87 −2.3058 −2.1446 −0.6455 323.74 −37.11 1224.63 1592.56 −2.2380 −2.0432 −0.6102 321.96 −35.89 1-ethyl-3-methylimidazolium tetrafluoroborate (1) + 2-methylaniline (2) + γ-picoline (3) T/K= 293.15 1053.56 1632.43 −1.4024 −1.4976 −0.6803 356.18 −26.07 1061.11 1633.48 −1.6112 −1.6878 −0.7274 353.19 −28.12 1072.14 1637.71 −1.9269 −1.9945 −0.7693 347.76 −31.37 1081.58 1639.18 −2.2166 −2.2737 −0.8113 344.10 −33.72 1090.95 1640.35 −2.5131 −2.5571 −0.8486 340.66 −35.89 1102.13 1639.65 −2.8709 −2.8709 −0.8967 337.49 −37.90 1111.49 1641.98 −3.1703 −3.1845 −0.9167 333.70 −40.04 1120.62 1643.82 −3.4582 −3.4940 −0.9345 330.24 −41.93 1129.82 1642.04 −3.7226 −3.7365 −0.9638 328.26 −42.84 1139.71 1637.64 −3.9514 −3.9449 −0.9984 327.17 −42.92 1145.29 1634.24 −4.0410 −4.0410 −1.0174 326.93 −42.54 1152.91 1635.19 −4.2067 −4.2978 −1.0184 324.39 −43.34 1155.48 1626.92 −4.1048 −4.1776 −1.0465 326.97 −41.08 1156.68 1611.24 −3.7112 −3.7984 −1.0975 333.02 −36.31 1155.01 1600.95 −3.3024 −3.4067 −1.1358 337.80 −33.15 1154.49 1594.21 −2.9015 −2.9905 −1.1677 340.82 −31.40 1159.84 1593.64 −2.7061 −2.7061 −1.1688 339.48 −31.45 1167.37 1595.80 −2.6871 −2.6283 −1.1451 336.38 −31.73 1176.61 1598.96 −2.6962 −2.6193 −1.1057 332.43 −31.84 1190.35 1604.19 −2.6976 −2.6976 −1.0319 326.45 −31.56 1196.33 1606.73 −2.6443 −2.6164 −0.9964 323.79 −31.42 1204.17 1610.17 −2.5886 −2.5998 −0.9435 320.31 −30.97 1211.59 1613.58 −2.5113 −2.5390 −0.8887 317.00 −30.39 1218.42 1616.83 −2.4184 −2.4096 −0.8345 313.96 −29.73 1225.42 1620.10 −2.3157 −2.3037 −0.7738 310.91 −28.76 1227.51 1621.06 −2.2833 −2.2894 −0.7545 310.01 −28.40 1148

Graph

PFP

−28.03 −31.09 −36.63 −43.01 −46.90 −52.92 −60.50 −61.40 −65.21 −61.69 −63.76 −64.39 −64.17 −48.42 −46.07 −45.90 −45.29 −45.05 −45.55 −44.66 −44.03 −43.57 −42.82 −41.51 −39.64 −37.90 −36.23 −34.16 −33.52 −31.48

−38.21 −37.52 −36.64 −35.88 −35.24 −34.49 −33.84 −33.39 −32.33 −31.26 −30.83 −30.31 −29.17 −27.68 −27.06 −26.79 −26.43 −26.14 −25.85 −25.52 −25.29 −25.04 −24.79 −24.49 −24.23 −23.92 −23.67 −23.43 −23.15 −22.90

−22.74 −25.66 −30.35 −33.28 −35.79 −37.90 −40.07 −41.81 −42.58 −42.72 −42.54 −43.22 −41.79 −38.48 −35.56 −32.69 −31.45 −31.57 −31.78 −31.56 −30.86 −29.89 −28.61 −27.10 −25.37 −24.82

−35.06 −34.48 −33.73 −33.07 −32.43 −31.65 −31.07 −30.51 −29.87 −29.10 −28.62 −28.14 −27.67 −26.83 −26.20 −25.44 −24.71 −24.29 −23.89 −23.33 −23.01 −22.63 −22.24 −21.86 −21.47 −21.35



Article


x2

ρ123/kg·m−3

u123/m·s−1

exptl.

0.6821 0.7011 0.7131 0.7284

0.1874 0.1759 0.1681 0.1594

1231.65 1235.67 1238.13 1241.25

1622.95 1624.67 1625.71 1627.04

−2.2096 −2.1340 −2.0821 −2.0147

0.1163 0.1315 0.1531 0.1718 0.1904 0.2131 0.2319 0.2507 0.2711 0.2953 0.3104 0.3293 0.3416 0.3597 0.3687 0.3811 0.4055 0.4311 0.4619 0.5094 0.5326 0.5630 0.5933 0.6226 0.6535 0.6629 0.6821 0.7011 0.7131 0.7284

0.7821 0.7635 0.7444 0.7228 0.7011 0.6712 0.6524 0.6329 0.6063 0.5726 0.5514 0.5332 0.5089 0.4662 0.4365 0.4039 0.3721 0.3514 0.3304 0.3008 0.2841 0.2645 0.2447 0.2251 0.2054 0.1997 0.1874 0.1759 0.1681 0.1594

1049.69 1057.30 1068.44 1077.93 1087.34 1098.55 1107.95 1117.12 1126.33 1136.25 1141.84 1149.49 1152.06 1153.24 1151.52 1150.93 1156.26 1163.84 1173.15 1187.02 1193.06 1200.98 1208.48 1215.39 1222.47 1224.59 1228.77 1232.84 1235.32 1238.46

1611.72 1613.72 1619.51 1622.60 1625.55 1627.20 1631.53 1633.39 1632.68 1628.78 1626.73 1627.45 1619.76 1603.59 1591.74 1584.65 1584.24 1586.34 1589.68 1595.18 1597.39 1600.53 1603.50 1606.18 1608.89 1611.10 1613.11 1614.47 1615.10 1616.22

−1.4469 −1.6638 −1.9927 −2.2901 −2.5934 −2.9575 −3.2630 −3.5561 −3.8247 −4.0580 −4.1502 −4.3198 −4.2186 −3.8225 −3.4079 −2.9990 −2.8008 −2.7853 −2.8010 −2.8146 −2.7661 −2.7181 −2.6484 −2.5624 −2.4669 −2.4367 −2.3668 −2.2947 −2.2444 −2.1792

0.1163 0.1315 0.1531 0.1718 0.1904 0.2131 0.2319 0.2507 0.2711 0.2953 0.3104 0.3293 0.3416 0.3597 0.3687 0.3811 0.4055 0.4311 0.4619 0.5094 0.5326 0.5630

0.7821 0.7635 0.7444 0.7228 0.7011 0.6712 0.6524 0.6329 0.6063 0.5726 0.5514 0.5332 0.5089 0.4662 0.4365 0.4039 0.3721 0.3514 0.3304 0.3008 0.2841 0.2645

1045.75 1053.21 1064.13 1073.37 1082.52 1093.37 1102.49 1111.38 1120.32 1130.01 1135.52 1143.05 1145.75 1147.40 1146.17 1146.11 1151.84 1159.62 1169.14 1183.35 1189.61 1197.79

1591.50 1594.09 1600.63 1604.46 1608.18 1610.80 1615.87 1620.44 1621.53 1619.94 1617.88 1618.83 1610.38 1594.60 1581.62 1572.14 1570.47 1572.97 1576.88 1583.40 1586.09 1589.93

−1.4818 −1.6850 −1.9923 −2.2655 −2.5423 −2.8716 −3.1497 −3.4160 −3.6584 −3.8692 −3.9536 −4.1110 −4.0214 −3.6705 −3.3036 −2.9478 −2.7898 −2.7944 −2.8300 −2.8745 −2.8482 −2.8253

Graph T/K= 293.15 −2.1889 −2.1386 −2.0430 −2.0464 T/K = 298.15 −1.5350 −1.7339 −2.0565 −2.3451 −2.6367 −2.9575 −3.2793 −3.5957 −3.8421 −4.0530 −4.1502 −4.4117 −4.2888 −3.9023 −3.5038 −3.0823 −2.8008 −2.7296 −2.7281 −2.8146 −2.7355 −2.7205 −2.6599 −2.5292 −2.4206 −2.4051 −2.3021 −2.2485 −2.1508 −2.1508 T/K = 303.15 −1.4823 −1.6858 −2.0191 −2.2983 −2.5751 −2.8716 −3.1712 −3.4611 −3.6816 −3.8680 −3.9536 −4.1876 −4.0767 −3.7328 −3.3790 −3.0119 −2.7898 −2.7545 −2.7784 −2.8745 −2.8138 −2.8024 1149


(κS)123/TPa−1

exptl.

Graph

PFP

−0.7157 −0.6758 −0.6512 −0.6174

308.25 306.60 305.59 304.33

−27.67 −26.78 −26.24 −25.39

−23.61 −22.39 −21.57 −20.53

−21.11 −20.86 −20.71 −20.51

−0.7257 −0.7768 −0.8236 −0.8693 −0.9099 −0.9615 −0.9838 −1.0035 −1.0345 −1.0704 −1.0899 −1.0914 −1.1194 −1.1696 −1.2069 −1.2375 −1.2369 −1.2117 −1.1703 −1.0928 −1.0551 −0.9993 −0.9413 −0.8837 −0.8195 −0.7991 −0.7580 −0.7157 −0.6896 −0.6540

366.74 363.20 356.85 352.36 348.04 343.79 339.07 335.52 333.07 331.74 330.95 328.45 330.84 337.21 342.76 346.00 344.59 341.44 337.31 331.07 328.49 325.04 321.83 318.93 316.02 314.60 312.75 311.20 310.33 309.11

−26.43 −28.96 −32.98 −36.07 −39.02 −42.02 −44.98 −46.85 −48.15 −48.36 −48.48 −49.12 −47.04 −41.98 −38.11 −36.16 −36.19 −36.34 −36.39 −35.99 −35.61 −34.89 −33.98 −32.95 −31.60 −31.68 −30.89 −29.75 −28.98 −27.96

−25.15 −28.29 −33.27 −36.55 −39.44 −42.02 −44.60 −46.76 −47.93 −48.46 −48.48 −49.53 −48.04 −44.42 −41.12 −37.82 −36.19 −36.12 −36.22 −35.99 −35.12 −34.08 −32.66 −30.92 −29.00 −28.42 −27.05 −25.73 −24.76 −23.72

−35.93 −35.31 −34.51 −33.81 −33.14 −32.31 −31.69 −31.10 −30.41 −29.60 −29.09 −28.58 −28.08 −27.20 −26.54 −25.74 −24.97 −24.52 −24.09 −23.48 −23.14 −22.74 −22.32 −21.92 −21.50 −21.38 −21.12 −20.86 −20.70 −20.49

−0.7141 −0.7643 −0.8102 −0.8551 −0.8949 −0.9456 −0.9674 −0.9867 −1.0171 −1.0524 −1.0715 −1.0729 −1.1004 −1.1498 −1.1865 −1.2166 −1.2159 −1.1911 −1.1502 −1.0738 −1.0367 −0.9817

377.54 373.65 366.80 361.90 357.19 352.49 347.39 342.67 339.47 337.23 336.45 333.01 335.72 342.76 348.78 353.02 352.00 348.53 343.98 337.06 334.15 330.26

−29.04 −31.80 −36.12 −39.46 −42.66 −45.93 −49.11 −51.99 −53.87 −54.83 −54.83 −56.24 −53.78 −47.98 −43.64 −40.67 −40.11 −40.34 −40.50 −40.30 −40.01 −39.42

−26.68 −30.10 −35.58 −39.36 −42.76 −45.93 −49.13 −51.93 −53.61 −54.60 −54.83 −56.47 −54.76 −50.42 −46.34 −42.24 −40.11 −39.97 −40.17 −40.30 −39.37 −38.43

−37.22 −36.58 −35.77 −35.05 −34.36 −33.51 −32.88 −32.27 −31.57 −30.74 −30.22 −29.70 −29.19 −28.28 −27.60 −26.79 −26.00 −25.54 −25.10 −24.48 −24.13 −23.71



Article


x2

ρ123/kg·m−3

u123/m·s−1

exptl.

0.5933 0.6226 0.6535 0.6629 0.6821 0.7011 0.7131 0.7284

0.2447 0.2251 0.2054 0.1997 0.1874 0.1759 0.1681 0.1594

1205.55 1212.72 1220.03 1222.21 1226.53 1230.69 1233.24 1236.45

1593.61 1596.99 1600.45 1601.45 1603.44 1605.16 1606.32 1607.57

−2.7817 −2.7211 −2.6489 −2.6249 −2.5677 −2.5059 −2.4619 −2.4024

0.1163 0.1315 0.1531 0.1718 0.1904 0.2131 0.2319 0.2507 0.2711 0.2953 0.3104 0.3293 0.3416 0.3597 0.3687 0.3811 0.4055 0.4311 0.4619 0.5094 0.5326 0.5630 0.5933 0.6226 0.6535 0.6629 0.6821 0.7011 0.7131 0.7284

0.7821 0.7635 0.7444 0.7228 0.7011 0.6712 0.6524 0.6329 0.6063 0.5726 0.5514 0.5332 0.5089 0.4662 0.4365 0.4039 0.3721 0.3514 0.3304 0.3008 0.2841 0.2645 0.2447 0.2251 0.2054 0.1997 0.1874 0.1759 0.1681 0.1594

1041.93 1049.25 1059.91 1068.86 1077.68 1088.09 1096.83 1105.34 1113.92 1123.30 1128.70 1136.01 1138.91 1141.25 1140.71 1141.30 1147.37 1155.21 1164.73 1178.90 1185.21 1193.40 1201.19 1208.38 1215.71 1217.89 1222.20 1226.37 1228.92 1232.12

1573.65 1576.38 1583.16 1587.23 1591.18 1594.09 1599.41 1604.26 1605.62 1604.31 1602.43 1605.64 1597.28 1579.60 1566.69 1557.43 1556.29 1560.42 1563.90 1571.44 1574.68 1579.26 1583.65 1587.77 1591.90 1593.10 1595.44 1597.60 1598.89 1600.35

−1.5396 −1.7297 −2.0125 −2.2576 −2.5021 −2.7888 −3.0296 −3.2583 −3.4655 −3.6468 −3.7210 −3.8560 −3.7868 −3.5062 −3.2091 −2.9205 −2.7974 −2.8077 −2.8428 −2.8832 −2.8608 −2.8387 −2.7964 −2.7372 −2.6647 −2.6402 −2.5823 −2.5193 −2.4745 −2.4139

Graph T/K = 303.15 −2.7469 −2.6287 −2.5223 −2.5031 −2.4041 −2.3432 −2.2519 −2.2352 T/K = 308.15 −1.4913 −1.6917 −2.0140 −2.2727 −2.5240 −2.7888 −3.0514 −3.3010 −3.4898 −3.6485 −3.7210 −3.9139 −3.8250 −3.5469 −3.2595 −2.9639 −2.7974 −2.7817 −2.8094 −2.8832 −2.8303 −2.8078 −2.7461 −2.6325 −2.5215 −2.4965 −2.3993 −2.3291 −2.2445 −2.2096


(κS)123/TPa−1

exptl.

Graph

PFP

−0.9247 −0.8680 −0.8048 −0.7848 −0.7444 −0.7028 −0.6771 −0.6422

326.63 323.32 319.99 319.02 317.12 315.37 314.26 312.96

−38.63 −37.71 −36.46 −36.00 −35.07 −33.93 −33.28 −32.18

−37.02 −35.14 −33.13 −32.56 −31.05 −29.71 −28.58 −27.61

−23.29 −22.88 −22.45 −22.33 −22.06 −21.80 −21.63 −21.42

−0.6580 −0.7036 −0.7445 −0.7851 −0.8212 −0.8675 −0.8869 −0.9041 −0.9321 −0.9650 −0.9829 −0.9838 −1.0103 −1.0580 −1.0938 −1.1233 −1.1235 −1.1004 −1.0626 −0.9909 −0.9566 −0.9056 −0.8528 −0.8004 −0.7420 −0.7235 −0.6862 −0.6478 −0.6241 −0.5918

387.57 383.53 376.43 371.36 366.50 361.67 356.40 351.52 348.23 345.88 345.03 341.45 344.15 351.18 357.16 361.23 359.85 355.51 351.04 343.50 340.27 335.98 331.95 328.26 324.59 323.53 321.44 319.48 318.30 316.89

−30.89 −33.72 −38.13 −41.54 −44.78 −48.09 −51.30 −54.22 −56.11 −57.07 −57.08 −58.51 −56.05 −50.31 −46.09 −43.34 −43.04 −43.93 −43.74 −43.72 −43.56 −43.10 −42.43 −41.63 −40.44 −39.99 −39.07 −37.96 −37.27 −36.13

−27.90 −31.54 −37.37 −41.32 −44.84 −48.09 −51.37 −54.19 −55.86 −56.84 −57.08 −58.68 −57.01 −52.78 −48.82 −44.88 −43.04 −43.13 −43.50 −43.72 −42.85 −41.89 −40.44 −38.52 −36.40 −35.77 −34.19 −32.72 −31.55 −30.41

−38.36 −37.74 −36.93 −36.22 −35.53 −34.69 −34.07 −33.46 −32.77 −31.94 −31.42 −30.91 −30.40 −29.49 −28.81 −27.99 −27.21 −26.76 −26.33 −25.73 −25.38 −24.98 −24.57 −24.16 −23.75 −23.62 −23.36 −23.10 −22.94 −22.73

a The standard uncertainty in mole fraction value is 1.10−4. The standard uncertainty in temperature is ±0.01 K. The standard uncertainty in density value is 0.5 kg·m−3. The standard uncertainty in speed of sound value is 0.1 m·s−1. The standard uncertainty in VE value is 0.1 %.

at 293.15 K, 298.15 K, 303.15 K, and 308.15 K (recorded in Table 3) were utilized to determine excess molar volumes, VE123 and isentropic compressibilities, (κS)123, by using

diameter and 19.5 mm height and had a capacity of containing one cm3 of a liquid. The calibration of equipment was done by Joule effect method which in turn is controlled by SETARAM software and checked by measuring heat of fusion of naphthalene (147.78 J·g−1). The reference experimental cell was filled with water (equivalent to the mass of sample liquid in standard batch cell). For a scanning sequence initial and final temperature were supplied along with heating rate of 0.4 K· min−1. The standard uncertainty in measuring heat capacity is ± 0.3 %. The heat capacities of the [emim][BF4], 2MA, Py, and α-, β-, or γ-picoline are recorded in Table 2 and compared with literature value.32−40

3 E V123 =

3

∑ xiM i(ρijk )−1 − ∑ xiM i(ρi )−1 i=1

i=1

(κS)123 = (ρ123 u1232)−1

(1) (2)

where xi, Mi, and ρi are the mole fraction, molar mass, and density of component (i) (i = 1, 2, or 3) and ρ123 and u123 are the densities and speeds of sound of ternary mixtures. The excess isentropic compressibilities, (κSE)123, for the various mixtures were determined by eq 3

3. RESULTS The densities, ρ123, and speeds of sound, u123, of [emim][BF4] (1) + 2MA (2) + Py or α-, β-, or γ-picoline (3) ternary mixtures

(κSE)123 = (κS)123 − κSid 1150

(3)



Article

E Table 4. Ternary Adjustable Parameters, X(n) 123 (X = V or κS; n = 0−2) of eq 5 along with Their Standard Deviations, σ(X ) (X = V or κS), of VE123 and (κES )123 at T/K = (293.15, 298.15, 303.15, and 308.15)

T/K parameters V(0) V(1) V(2) σ(VE)/cm3·mol−1 κ(0) S κ(1) S κ(2) S σ(κES )/TPa−1 V(0) V(1) V(2) σ(VE)/cm3·mol−1 κ(0) S κ(1) S κ(2) S σ(κES )/TPa−1 V(0) V(1) V(2) σ(VE)/cm3·mol−1 κ(0) S κ(1) S κ(2) S σ(κES )/TPa−1 V(0) V(1) V(2) σ(VE)/cm3·mol−1 κ(0) S κ(1) S κ(2) S σ(κES )/TPa−1

293.15

298.15

κidS values for ternary mixtures were calculated in the manner as suggested by Benson and Kiyohara41 using relation

308.15 −5.5947 112.5068 1111.0372 0.0020 132.95 8626.19 −78763.72 0.12 9.9473 362.9294 −5233.0876 0.0034 133.61 12966.41 −49718.18 0.09 −7.3357 370.1185 −3680.9969 0.0029 343.30 9713.76 −92960.67 0.12 15.2861 87.8870 −4545.2409 0.0037 261.48 12719.31 −98199.67 0.11

E (X = V or κS) X123 2 (n) )(x1 − x 2)n ] = x1x 2[ ∑ (X12

3 2 3 ⎡ (∑i = 1 ϕα Tviαi 2 ⎤ i) ⎢ ⎥ = ∑ ϕi κS, i + − T (∑ xivi) 3 i ⎢ Cp, i ⎥⎦ (∑i = 1 xiCp, i) i=1 ⎣ i=1 3

κSid

303.15

1-ethyl-3-methylimidazolium tetrafluoroborate (1) + 2-methylaniline (2) + pyridine (3) −6.5529 −5.8704 −5.7824 142.2460 86.1389 104.0109 869.8033 1410.9129 1143.5066 0.0018 0.0019 0.0020 85.86 139.54 136.35 9115.13 8196.58 8334.86 −81457.78 −75627.48 −76214.53 0.09 0.10 0.11 1-ethyl-3-methylimidazolium tetrafluoroborate (1) + 2-methylaniline (2) + α-picoline (3) 4.4335 5.9862 6.9865 406.7175 297.5495 320.1045 −4997.0055 −4332.7537 −4590.4438 0.0031 0.0032 0.0033 129.42 145.31 124.51 12124.73 12187.96 12148.99 −17002.46 −42193.66 −32312.60 0.06 0.07 0.08 1-ethyl-3-methylimidazolium tetrafluoroborate (1) + 2-methylaniline (2) + β-picoline (3) −12.6637 −11.3177 −10.3125 329.1929 335.1956 372.2486 −3124.8747 −3586.7894 −3497.1309 0.0029 0.0030 0.0029 297.76 311.52 375.61 10636.27 8663.14 9676.58 −81500.04 −73509.94 −89654.70 0.09 0.10 0.11 1-ethyl-3-methylimidazolium tetrafluoroborate (1) + 2-methylaniline (2) + γ-picoline (3) 14.2127 14.0390 14.3730 171.7444 141.3712 147.9787 −6293.2624 −6293.2290 −5740.8342 0.0041 0.0042 0.0041 162.25 239.79 260.26 11965.96 11419.96 12004.04 −78846.12 −89213.29 −95360.44 0.08 0.10 0.11

n=0 2 (n) )(x 2 − x3)n ] + x 2x3[ ∑ (X 23

(4)

n=0 2

where ϕi, κS,i, vi, αi, and Cp,i (i = 1, 2, or 3) are the volume fraction, isentropic compressibility, molar volume, thermal expansion coefficient, and molar heat capacity of the pure component (i) and T is the absolute temperature. The α values for [emim][BF4], 2MA, Py, or α-, β-, or γ-picoline were calculated using experimental density data using42 relation: α = −ρ−1(∂ρ/∂T), where ρ is the density of pure liquids. The α values for studied liquids are reported in Table 2 and also compared with literature values.37 The VE123 and (κES )123 values for the investigated mixtures (recorded in Table 3) were expressed by

(n) )(x1 − x3)n ] + x1x3[ ∑ (X13 n=0 2 (n) )(x 2 − x3)n x1n] + x1x 2x3[ ∑ (X123 n=0

(5)

(n) (n) where X(n) 12 , X23 , and X13 , (n = 0−2) are binary adjustable parameters of (1 + 2), (2 + 3), and (1 + 3) mixtures and were taken from the literature.17,18,29 The X(n) 123 (X = V or κS) (n = 0− 2) are parameters characteristic of a (1 + 2 + 3) mixture and were determined by fitting the measured VE123 and (κES )123 data to eq 5 by least-squares method. The resulting parameters along with standard deviations are recorded in Table 4. The

1151



Article

various surfaces generated by VE123 and (κES )123 values for the studied ternary mixtures at 298.15 K43 {evaluated by employing eq 5} are shown in Figures 1, 2, and 3 and 4, 5, 6, and 7 respectively.

Figure 4. Excess isentropic compressibilities, (κES )123, for 1-ethyl-3methylimidazolium tetrafluoroborate (1) + 2-methylaniline (2) + pyridine (3) ternary mixture at 298.15 K, the experimental data in front of the plane (); the experimental data behind the plane (---).

Figure 1. Excess molar volumes, VE123, for 1-ethyl-3-methylimidazolium tetrafluoroborate (1) + 2-methylaniline (2) + α-picoline (3) ternary mixture at 298.15 K, the experimental data in front of the plane ( ); the experimental data behind the plane (---).

Figure 5. Excess isentropic compressibilities, (κES )123, for 1-ethyl-3methylimidazolium tetrafluoroborate (1) + 2-methylaniline (2) + αpicoline (3) ternary mixture at 298.15 K, the experimental data in front of the plane (); the experimental data behind the plane (---).

Figure 2. Excess molar volumes, VE123, for 1-ethyl-3-methylimidazolium tetrafluoroborate (1) + 2-methylaniline (2) + β-picoline (3) ternary mixture at 298.15 K, the experimental data in front of the plane( ); the experimental data behind the plane (---------).

Figure 6. Excess isentropic compressibilities, (κES )123, for 1-ethyl-3methylimidazolium tetrafluoroborate (1) + 2-methylaniline (2) + βpicoline (3) ternary mixture at 298.15 K, the experimental data in front of the plane (); the experimental data behind the plane (---).

Figure 3. Excess molar volumes, VE123, for 1-ethyl-3-methylimidazolium tetrafluoroborate (1) + 2-methylaniline (2) + γ-picoline (3) ternary mixture at 298.15 K, the experimental data in front of the plane ( ); the experimental data behind the plane (---).

due to the higher molar volumes (at T/K = 298.15) of α(98.96 cm3.mol−1 ), β- (97.69 cm 3. mol−1 ), or γ-(97.88 cm3.mol−1) picolines as compared to Py (80.80 cm3.mol−1) which in turn should restrict their approach between the clathrates of [emim][BF4]:OT molecular entity18 as compared to Py. However, this is not true. It may be due to the presence of −CH3 group on aromatic ring of picolines. Due to this, electron pair on nitrogen atom of aromatic ring of picolines will be more easily available for intermolecular hydrogen bonding with [emim][BF4]:OT molecular entity. The VE123 values of [emim]BF4] (1) + 2MA (2) + γ-picoline (3) mixture are more

4. DISCUSSION We are not aware of any VE123 and (κES )123 data for the studied mixtures at 293.15 K, 298.15 K, 303.15 K, and 308.15 K in the literature with which to compare our result. The measured VE123 and (κES )123 values for the present mixtures are negative over entire composition range. The VE123 values of [emim]BF4] (1) + 2MA (2) + Py (3) mixture should be smaller than those of [emim]BF4] (1) + 2MA (2) + α-, β-, or γ-picoline (3) mixtures 1152



Article

respective monomers; (3) 1, 2, and 3 monomers then undergo interactions to form (i) 1:2 (ii) 2:3 and (iii) 1:3 molecular complexes. If χ12, χ23, and χ13 are molar volumes and molar compressibility interaction parameters for 1−2n, 2n−3n, and 1− 3n contacts, then change in thermodynamic properties ΔX(X = V or κS) due to processes (1) (i−iii) were expressed44−49 by ΔX1(X = V or κS) =

ΔX 2(X = V or κS) =

Figure 7. Excess isentropic compressibilities, (κES )123, for 1-ethyl-3methylimidazolium tetrafluoroborate (1) + 2-methylaniline (2) + γpicoline (3) ternary mixture at 298.15 K, the experimental data in front of the plane (); the experimental data behind the plane (---).

ΔX3(X = V or κS) =

negative than those of [emim]BF4] (1) + 2MA (2) + α- or βpicoline (3) mixtures due to the symmetrical γ-picoline molecule which in turn give relatively more closed packing in [emim][BF4]:OT molecular entity as compared to α- or βE picolines. The ∂(V 123 )/∂T and ∂((κSE) 123 )/∂T for the investigated mixtures are negative. The VE123 and (κES )123 data of the presented mixtures were next analyzed in terms of Graph and PFP theories. 4.1. Graph Theory. 4.1.1. Excess Molar Volumes and Excess Isentropic Compressibilities of Ternary Mixtures. On the basis of thermodynamic and topological investigation17,18 of [emim][BF4](1) + 2MA, Py, or α-, β-, or γ-picolines (2) mixtures it has been revealed that (i) while [emim][BF4] exist as monomer, 2MA, Py, or α-, β-, or γ-picolines exist as associated molecular entities; (ii) the [emim][BF4] (1) + 2MA (2) mixture is characterized by interactions between hydrogen and nitrogen atoms of 2MA with florine atom of [BF4]− anion and nitrogen atom of [emim]+ cation of ionic liquid; and (iii) [emim][BF4] (1) + Py or α-, β-, or γ-picolines (2) mixtures are characterized by interactions between nitrogen and electron deficient carbon atoms of Py or α-, β-, or γ-picoline with nitrogen atom of imidazolium ring of [emim]+ cation and florine atom of [BF4]− anion. The IR studies also lend support to the nature and extent of interactions among the constituent of mixtures.17,18 The excess molar enthalpies, HE, and excess isentropic compressibilities, κES , for (1 + 2) mixtures were then expressed by X E(X = H or κS) ⎡ x x (3ξ /3ξ ) ⎤ = ⎢ 1 2 13 32 ⎥[(1 + x1)χ12′ + xjχ12 ] ⎣ x1 + x 2( ξ1/ ξ 2) ⎦

x1x 2(3ξ1/3ξ 2) (x1 + x 23ξ1/3ξ 2)

[χ12 ]

x 2x3(3ξ 2/3ξ 3) (x 2 + x33ξ 2/3ξ 3) x3x1(3ξ 3/3ξ1) (x3 + x13ξ 3/3ξ1)

[χ23 ]

[χ13 ]

(7)

(8)

(9)

Further, if χ22 and χ33 and χ12 ′ , χ12 ″ , and χ12 ‴ are molar interaction parameter for rupture of associated molecular entities 2n and 3n and are interactions among the constituent of the mixtures, then change in thermodynamic properties, ΔX(X=V or κS) due to processes 2 (i−ii); and 3 (i−iii) were given44−49 by ΔX4(X = V or κS) =



ΔX 7(X = V or κS) =


x 2 2x3(3ξ 2/3ξ 3) (x 2 + x33ξ 2/3ξ 3) x32x1(3ξ 3/3ξ1) (x3 + x13ξ 3/3ξ1)

[χ33 ]

x1x 2 2(3ξ1/3ξ 2)

[χ12′ ]

(x1 + x 23ξ1/3ξ 2) x 2x32(3ξ 2/3ξ 3) (x 2 + x33ξ 2/3ξ 3) x3x12(3ξ 3/3ξ1) (x3 + x13ξ 3/3ξ1)

[χ22 ]

[χ12″ ]

[χ12‴]

(10)

(11)

(12)

(13)

(14)

where 3ξi and (3ξi)m (i = 1, 2, or 3) are connectivity parameters of third degree and are defined by50,51 (6)

3

ξ=

where χ 12 ′ and χ 12 are molar interaction and molar compressibility interaction parameter of unlike contacts and specific interactions between the components of the mixtures. The HE and κES values obtained by eq 6 were in good agreement17,18 with experimental data which in turn support assumptions made in deriving eq 6. The addition of third component Py or α-, β-, or γ-picoline (3) to [emim][BF4] (1) + 2MA (2) leads to [emim][BF4] (1) + 2MA (2) + Py or α-, β-, or γ-picoline (3) ternary mixtures. These mixtures formation may involve processes (1) establishment of unlike (i) 1−2n (n = degree of association); (ii) 2n−3n; (iii) 1−3n contacts (2) unlike contact formation then lead to rupture of associated entities (i) 2n; and (ii) 3n to form their

(δmνδnνδoνδpν)−0.5

∑ m

Thermodynamic Properties of Ternary Mixtures Containing Ionic

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