J. Chem.

Thermodynamics 54 (2012) 293–301

Contents lists available at SciVerse ScienceDirect

J. Chem. Thermodynamics
journal homepage: www.elsevier.com/locate/jct

High-pressure density measurements for choline chloride: Urea deep eutectic

solvent and its aqueous mixtures at T = (298.15 to 323.15) K and up to 50 MPa
Rhoda B. Leron, Meng-Hui Li ⇑
R&D Center for Membrane Technology and Department of Chemical Engineering, Chung Yuan Christian University, Chung Li 32023, Taiwan, ROC

a r t i c l e i n f o a b s t r a c t

Article history: New measurements are reported for the densities of choline chloride: urea (REL) deep eutectic solvent
Received 24 March 2012 and its aqueous mixtures over the temperature range (298.15 to 323.15) K and pressures up to
Received in revised form 28 April 2012 50 MPa. The experimental data were used to derive other properties such as isothermal compressibility,
Accepted 8 May 2012
isobaric expansivity and excess molar volume. A Tait-type equation was used to correlate accurately the
Available online 16 May 2012
high-pressure density data to temperature, T, pressure, P, and composition, x. The excess molar volumes
of {REL (1) + H2O (2)} mixtures were also investigated and represented as a function of all three variables,
Keywords:
T, P, x, using an empirical equation. Results indicate that the correlations used in this work can be satis-
Deep eutectic solvent
Excess molar volume
factorily used to predict the densities of the studied systems at different conditions of temperature, pres-
High-pressure density sure and composition.
Isobaric expansivity Ó 2012 Elsevier Ltd. All rights reserved.
Isothermal compressibility
Reline

1. Introduction
Ionic liquids (ILs) are being hailed as green replacements to vol-
atile organic compounds (VOCs) for a wide range of electrochemi-
cal, synthetic, analytical and engineering processes [1]. This is due
to the unique combination of properties that they possess such as
negligible vapour pressure, wide liquid range, thermal and chemi-
cal stability, high solvation capacity, high ionic conductivity and
non-flammability. Many ILs are excellent media for electrochemi-
cal applications due to their ability to dissolve many organic and
inorganic compounds [2,3]. They can be thermally stable up to
400 °C making them potential solvents in thermal storage and heat
transfer applications and even gas treating processes [4–7]. They
are also being considered as promising green solvents for gas sep-
aration and purification because of their capacity to dissolve
important gases such as CO2 [8–11]. Due to their non-volatility
and thermal stability, ILs can be used at high process temperatures
without evaporation and degradation [11].
Although ILs posses numerous exceptional characteristics, there
are still some disadvantages inherent to their use. At present, ILs
are generally expensive and some of them i.e. imidazolium-based
ILs are toxic and non-biodegradable [12–14]. Thus, researchers
are in the continued search for new and greener alternatives to
these ILs that may overcome their limitations. Among such are
the deep eutectic solvents (DES) which have been shown to have
⇑ Corresponding author. Tel.: +886 3 265 4109; fax: +886 3 265 4199.
E-mail address: mhli@cycu.edu.tw (M.-H. Li).
similar solvent properties to conventional ILs but are less expen-
sive and many of them are biodegradable [15,16].
DES is a new type of ionic liquid that is made by mixing a
substituted quaternary ammonium salt and metal halide or a
hydrogen bond donor (HBD) forming a eutectic mixture of sub-
stantially low melting point; hence, it is termed deep eutectic sol-
vent [17,18]. An example is the mixture formed between
hydroxyethytrimethylammonium or choline chloride and urea
(trade name: Reline). When mixed at the correct molar ratio of
1:2, a eutectic occurs at a freezing point of 12 °C which is signifi-
cantly lower than the freezing points of its original precursors
(choline chloride tfus = 302 °C and urea tfus = 133 °C) [19]. DESs
have been shown to have interesting properties that are similar
to those of ILs including negligible volatility, high conductivities,
non-flammability and other unusual solvent properties. But unlike
ILs DESs are easy to manufacture at high purity and relatively
cheap cost. They can be prepared by simple mixing of the two com-
ponents with gentle heating. They are also generally less moisture
sensitive compared to ILs [17] and many of them are made from
biodegradable components which exhibit low toxicities. Choline
chloride, for example, is used as a vitamin in chicken feeds while
urea is a common fertilizer [20].
Due to their unusual characteristics, the possibility of using
DESs for different applications has been extensively explored.
Certain types of DESs have been found useful in a variety of
electrochemical process such as electro deposition of metals, elec-
tro polishing of stainless steel and even the electro deposition of
metal films [21–23]. Similar to ILs, they are also being considered

0021-9614/$ - see front matter Ó 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.jct.2012.05.008
294 R.B. Leron, M.-H. Li / J. Chem. Thermodynamics 54 (2012) 293–301
as a potential gas i.e. CO2 absorption media. In a recent study, Li
et al. [24] reported the absorption of CO2 in a variety of mixtures
of choline chloride and urea under pressures up to 13 MPa and
temperatures (303.15 to 333.15) K. Su et al. [25] later measured
the solubility of CO2 in Reline + H2O mixtures at atmospheric pres-
sure from temperature (303 to 313) K. They investigated the effect
of water on the solubility of CO2 in Reline and reported that water
can serve as an anti-solvent to drive out CO2 dissolved in the DES.
Therefore, to complement the data presented in these studies, it is
important to know the thermophysical properties (including den-
sity) of the DES Reline and its aqueous mixtures. In recent works,
the atmospheric densities and isobaric heat capacities of Reline
and its mixtures with water were reported [25,26]. However, to
the best of our knowledge, data on the high-pressure density is
yet available for such systems.
In this work, we report new measurements for the densities of
the deep eutectic solvent 1 mole choline chloride: 2 mole urea
(REL) and its aqueous mixtures over the temperature range
(298.15 to 323.15) K and up to 50 MPa. A Tait-type equation was
used to correlate the high-pressure density data to temperature,
pressure and composition. Values of the isothermal compressibil-
ity, isobaric expansivity and excess molar volume were also calcu-
lated from experimental data. For the {REL (1) + H2O (2)} mixtures,
the excess molar volumes were represented as a function of tem-
perature, pressure and composition using an empirical equation
proposed by Lugo et al. [27].
2. Experimental
2.1. Chemicals
The deep eutectic solvent Reline 200 (mass fraction pur-
ity > 0.98) used this work was obtained from Scionix LtdÒ. It is a
TABLE 1
Description of the chemicals used in this study.
Chemical
1-butyl-3-methylimidazolium tetrafluoroborate [Bmim][BF4]
Reline 200 (REL)(1 mole choline chloride: 2 mole urea)
Sodium chloride(ACS reagent Baker analyzed)
P
4
5
1
N2
6
FIGURE 1. Schematic diagram of the density meter installation: (1) sample vessel; (2) pressure generator; (3) DMA HP densitometer; (4) pressure gauge; (5) cold trap; (6)
vacuum pump; (7) DMA HP interface; (8) DMA 5000 M master instrument; (9) computer interface.
mixture of 1 mole choline chloride and 2 mole urea (REL). The so-
dium chloride used in the preparation of the calibration solutions
was American Chemical Society (ACS) – certified grade and was
purchased from J.T. Baker. The IL 1-butyl-3-methylimidazolium
tetrafluoroborate, [Bmim][BF4], (mass fraction purity > 0.98) was
supplied by Tokyo Chemical Co., Ltd. A summary of the chemical
used, their purities and sources are also summarized in table 1.
The REL and [Bmim][BF4] samples were used without further
purification except for drying. The samples were separately dried
at T = 343 K for at least 48 h in an evacuated oven in order to re-
move any volatile impurities and reduce the water contents. The
water contents of the samples after drying were measured using
a Mettler Toledo Karl-Fischer (model DL31) titrator and were
<0.005 and 0.0004 (mass fraction) for REL and [Bmim][BF4], respec-
tively. Distilled deionised water (Type I reagent-grade; resistiv-
ity = 18  3 MX  cm), processed in a Barnstead Thermolyne
(model Easy Pure 1052) water system, was used in all the experi-
ments. All aqueous solutions were prepared from degassed sam-
ples and weight measurements were done using a Mettler Toledo
(model AL204) digital balance with an accuracy of ±1  104 g.
2.2. Density measurements
The density measurements were performed using an Anton
Paar (model DMA HP) vibrating tube density meter connected to
a model DMA 5000 M master instrument. DMA HP measures the
period of harmonic oscillation of a built-in U-tube containing the
sample. The measurement and control of the temperature (by an
integrated Peltier thermostat) are built-in to the measuring sys-
tem. The accuracy of the temperature measurement was ±0.05 K.
The pressure was created using a pressure generator from High
Pressure Equipment Company (HIP model #62-6-10) and was
monitored with a GE Druck pressure gauge (model DPI 104,
Mass fraction purity Source
>0.98 Tokyo Chemical Industry Co., Ltd.
>0.98 Scionix Ltd.
1.002 (NaCl) J.T. Baker
3
7
9
8
 R.B. Leron, M.-H. Li / J. Chem. Thermodynamics 54 (2012) 293–301
0–100 MPa) having an accuracy of 0.05% FS. The period of oscilla-
tion, cell temperature and pressure were recorded using the DMA
5000 M master instrument which was connected to the DMA HP
via the DMA HP interface. All high pressure valves and fittings were
supplied by High Pressure Equipment Company (USA) and Nova
Swiss (Switzerland). The schematic diagram of the apparatus is
shown in figure 1.
Before each experiment, the system was rinsed with deionised
water and ethanol, dried with nitrogen gas and slowly evacuated
for at least 3 h. Then, the inlet valve was opened to fill the system
and the pressure generator cell with the sample and the valve was
closed. To avoid any trapped air in the system, the outlet valve was
slightly opened and a few cm3 of the sample were allowed to flow
out by moving the pressure generator piston forward. The outlet
valve was then closed and the system was brought to the desired
temperature and pressure. The temperature was allowed to stabi-
lize for at least 30 min for a 5 K interval. Upon thermal and
mechanical equilibrations, the period of oscillation was recorded
using the DMA 5000 M master instrument which was then con-
verted to the density.
The density meter was calibrated using deionised distilled
water and various molalities (1 m, 3 m) of NaCl (aq). The use of
NaCl (aq) solutions as high-density calibration fluids for high pres-
sure density meters has been recommended by several authors
[28–30]. The calibration was carried out for the temperature range
(298.15 to 323.15) K over the pressure range (0.1 to 50) MPa and a
total of 198 data points were used. The reference data reported by
Wagner and Pruss [31] for water and by Archer [32] for NaCl (aq)
were used to correlate the density with the temperature and pres-
sure using the equation recommended by the manufacturer for the
calibration of the instrument
X over the pressure range (0.1 to 50) MPa and temperatures from
i j k
q¼ aijk p T P ;
i;j;k
where q is the reference density in g  cm3; p is the oscillation per-
iod in ls; T is the temperature in °C; P is the pressure in bar; and i, j,
k are fitting parameters, with i = 0, 2; j = 0, 1, 2; and k = 0, 1, 2. The
average absolute deviation (AAD) of the fit between the reference
and calculated data was 0.003% based on the following equation
1XN
jqi;ref  qi;cal j
AAD% ¼ 100  ; ð2Þ
N i qi;ref
where qi,ref is the ith reference density data and qi,cal is the density
calculated by equation (1). The calibration was tested by measuring
the densities NaCl (aq) solutions at varied concentrations (2 m and
4.5 m) within the considered temperature and pressure ranges and
comparing them with the reference data taken from Archer [32].
The AAD between the measured and reference data is less than
0.02% which is well within the error of the experiment. This is a
confirmation of the correct calibration of the apparatus, accuracy
of the method as well as the operation of the equipment and the
validity of the reported measurements. Our measurements were
further validated by measuring the densities of the ionic liquid 1-
butyl-3-methylimidazolium tetrafluoroborate, [Bmim][BF4], at the
temperature and pressure ranges considered. This IL has been
extensively studied and the densities at varied ranges of tempera-
tures and pressures are well-reported in the literatures. Upon com-
parison, good agreements were obtained between our measured
values and those reported by Zafarani-Moattar and Shekaari [33],
Sanmamed et al. [34] and Soriano et al. [35] at 1 atm with AAD%
of 0.01%, 0.06% and 0.02%, respectively. Our results were also close
to the data reported by Gardas et al. [36] and the calculated values
from the correlation proposed by Matkowska and Hofman [37] for
different ranges of temperatures and pressures with AAD of 0.04%
and 0.02%, respectively. The measured densities were in between
295
the values calculated from the correlations proposed by Jacquemin
et al. [30] (AAD% = 0.16) and those calculated from Rebelo et al. [38]
(AAD% = 0.28) and Abdulagatov et al. [29] (AAD% = 0.74). These
deviations, which are typical to ILs, may be mainly due to the differ-
ences in the purities of the samples used. In our case, the observed
deviations were consistent with the differences in the water con-
tents of the samples used in each study. Compared to our IL sam-
ple’s, the water content of the IL used by Jacquemin et al. [30]
was higher and those of the samples used by Rebelo et al. [38]
and Abdulagatov et al. [29] were much lower.
Anton Paar DMA HP does not possess a built-in correction sys-
tem for viscosity effects [39]. Such correction has been recom-
mended by many authors for density measurements obtained by
vibrating-tube density meters to account for the differences be-
tween the viscosity of the samples and those of the calibrating flu-
ids [40–42]. Several authors used an empirical approach to account
for such effect using information provided by the manufacturer (i.e.
for Anton Paar DMA 512P and DMA HPM). Unfortunately, there is
no general correlation available for the DMA HP model. Anton Paar
provides a graphical representation of the influence of viscosity on
the density measured by the instrument which includes a rather
few data points [39]. The correction of the density using such re-
quires viscosity data which are not available for the studied sys-
tems. Thus, no corrections on the measured densities have been
performed and raw density data were reported. The overall uncer-
tainty in the density measurements is estimated to be within
±0.1%.
3. Results and discussion
The densities of REL and its aqueous mixtures were measured
ð1Þ
(298.15 to 323.15) K. The data are presented in table 2 as a function
of temperature, pressure and composition. As expected, the densi-
ties decrease with an increase in temperature (at constant pres-
sure) due to thermal expansion and increase with an increase in
pressure (at constant temperature) because of volume compres-
sion. It can also be observed that the values increase with increas-
ing DES mole fraction which can be explained by the higher density
of the DES than that of water. For representation, the variation of
density as a function of temperature and pressure for REL is shown
in figure 2. Within the ranges of the temperature and pressure con-
sidered, the effect of temperature on the density is relatively more
important than the effect of pressure. For all the compositions con-
sidered, the densities decrease by a maximum of 1.2% from
T = (298.15 to 323.15) K while the values increase only by a maxi-
mum of 1.6% from (0.1 to 50) MPa.
The measured data from this work for {REL (1) + H2O (2)} mix-
tures were compared to those predicted by the equation proposed
by Su et al. [25] for the densities of aqueous Reline mixtures at
P = 0.1 MPa. Their measurements were carried out using an Anton
Paar (model SVM3000) density meter and reported with no viscos-
ity correction. Our results are systematically lower than but still in
agreement with the literature data [25] with an AAD of 0.28%. This
deviation which is only slightly higher than the reported accuracy
of the proposed equation (AAD = 0.22%) could be attributed to sev-
eral factors such as the purity and initial water content of the DES,
the uncertainty of the measurements and the accuracy of the cor-
relation used.
A Tait-type equation was adjusted to the experimental densities
to correlate the density to the temperature and pressure for each
composition
q0ðTÞ
qðT; PÞ ¼ BðTÞþP
; ð3Þ
1  C ln BðTÞþPref
296 R.B. Leron, M.-H. Li / J. Chem. Thermodynamics 54 (2012) 293–301

TABLE 2 TABLE 2 (continued)

Experimental density data for RELa and its aqueous mixtures as a function of pressure,
temperature and concentration. P/MPa q/(gcm3)
T/K = 298.15 303.15 308.15 313.15 318.15 323.15
P/MPa q/(gcm3)
x1 = 0.6998
T/K = 298.15 303.15 308.15 313.15 318.15 323.15
0.1 1.1802 1.1775 1.1747 1.1718 1.1689 1.1660
x1 = 0.1001b 5.0 1.1816 1.1788 1.1760 1.1731 1.1703 1.1674
c
0.1 1.0635 1.0613 1.0589 1.0565 1.0540 1.0514 10.0 1.1829 1.1802 1.1773 1.1745 1.1716 1.1687
5.0 1.0651 1.0630 1.0607 1.0583 1.0558 1.0532 15.0 1.1842 1.1815 1.1787 1.1759 1.1730 1.1701
10.0 1.0670 1.0648 1.0624 1.0601 1.0576 1.0550 20.0 1.1856 1.1828 1.1800 1.1772 1.1744 1.1715
15.0 1.0687 1.0666 1.0643 1.0619 1.0594 1.0568 25.0 1.1869 1.1842 1.1814 1.1785 1.1757 1.1729
20.0 1.0704 1.0683 1.0660 1.0636 1.0611 1.0586 30.0 1.1882 1.1855 1.1827 1.1798 1.1771 1.1741
25.0 1.0722 1.0700 1.0678 1.0654 1.0629 1.0603 35.0 1.1894 1.1868 1.1840 1.1812 1.1783 1.1755
30.0 1.0739 1.0717 1.0695 1.0671 1.0646 1.0620 40.0 1.1907 1.1880 1.1853 1.1825 1.1796 1.1767
35.0 1.0756 1.0734 1.0712 1.0688 1.0663 1.0637 45.0 1.1919 1.1893 1.1865 1.1837 1.1808 1.1780
40.0 1.0773 1.0751 1.0728 1.0705 1.0680 1.0654 50.0 1.1932 1.1905 1.1877 1.1849 1.1821 1.1793
45.0 1.0789 1.0768 1.0745 1.0722 1.0697 1.0672 x1 = 0.7998
50.0 1.0806 1.0784 1.0761 1.0738 1.0714 1.0688 0.1 1.1872 1.1844 1.1815 1.1786 1.1757 1.1728
x1 = 0.2000 5.0 1.1886 1.1857 1.1829 1.1800 1.1771 1.1742
0.1 1.1030 1.1005 1.0980 1.0954 1.0927 1.0899 10.0 1.1899 1.1872 1.1842 1.1813 1.1785 1.1756
5.0 1.1045 1.1021 1.0996 1.0970 1.0943 1.0916 15.0 1.1912 1.1884 1.1856 1.1827 1.1798 1.1769
10.0 1.1061 1.1036 1.1011 1.0986 1.0959 1.0932 20.0 1.1926 1.1897 1.1869 1.1840 1.1812 1.1783
15.0 1.1077 1.1053 1.1028 1.1002 1.0975 1.0947 25.0 1.1938 1.1911 1.1882 1.1854 1.1825 1.1797
20.0 1.1092 1.1068 1.1043 1.1018 1.0991 1.0964 30.0 1.1951 1.1924 1.1896 1.1867 1.1839 1.1809
25.0 1.1108 1.1084 1.1059 1.1033 1.1006 1.0979 35.0 1.1964 1.1937 1.1908 1.1880 1.1851 1.1823
30.0 1.1123 1.1099 1.1074 1.1048 1.1022 1.0994 40.0 1.1976 1.1949 1.1921 1.1893 1.1864 1.1835
35.0 1.1138 1.1114 1.1089 1.1064 1.1037 1.1010 45.0 1.1988 1.1961 1.1933 1.1905 1.1876 1.1848
40.0 1.1153 1.1129 1.1104 1.1079 1.1053 1.1026 50.0 1.2000 1.1973 1.1944 1.1916 1.1888 1.1860
45.0 1.1167 1.1144 1.1118 1.1094 1.1068 1.1041 x1 = 0.9000
50.0 1.1182 1.1158 1.1133 1.1108 1.1083 1.1056 0.1 1.1931 1.1902 1.1873 1.1844 1.1815 1.1786
x1 = 0.3000 5.0 1.1944 1.1915 1.1887 1.1858 1.1829 1.1800
0.1 1.1291 1.1266 1.1239 1.1212 1.1184 1.1156 10.0 1.1957 1.1930 1.1900 1.1871 1.1843 1.1814
5.0 1.1304 1.1279 1.1254 1.1227 1.1200 1.1172 15.0 1.1970 1.1942 1.1914 1.1885 1.1856 1.1827
10.0 1.1319 1.1295 1.1268 1.1242 1.1215 1.1186 20.0 1.1984 1.1955 1.1927 1.1898 1.1870 1.1841
15.0 1.1334 1.1309 1.1284 1.1257 1.1229 1.1201 25.0 1.1997 1.1969 1.1940 1.1912 1.1883 1.1855
20.0 1.1349 1.1324 1.1298 1.1271 1.1244 1.1217 30.0 1.2010 1.1982 1.1954 1.1925 1.1897 1.1867
25.0 1.1364 1.1339 1.1312 1.1286 1.1258 1.1231 35.0 1.2022 1.1995 1.1966 1.1938 1.1909 1.1881
30.0 1.1378 1.1353 1.1327 1.1300 1.1273 1.1245 40.0 1.2034 1.2007 1.1979 1.1951 1.1922 1.1893
35.0 1.1392 1.1367 1.1341 1.1315 1.1287 1.1260 45.0 1.2046 1.2019 1.1991 1.1963 1.1934 1.1906
40.0 1.1406 1.1381 1.1355 1.1329 1.1302 1.1274 50.0 1.2058 1.2031 1.2002 1.1974 1.1946 1.1918
45.0 1.1419 1.1395 1.1369 1.1343 1.1315 1.1288 x1 = 1.000
50.0 1.1433 1.1409 1.1383 1.1357 1.1330 1.1303 0.1 1.1979 1.1951 1.1922 1.1893 1.1864 1.1835
x1 = 0.3997 5.0 1.1993 1.1964 1.1936 1.1907 1.1878 1.1849
0.1 1.1474 1.1448 1.1421 1.1394 1.1366 1.1337 10.0 1.2006 1.1979 1.1949 1.1920 1.1892 1.1863
5.0 1.1487 1.1461 1.1435 1.1408 1.1381 1.1352 15.0 1.2019 1.1991 1.1963 1.1934 1.1905 1.1876
10.0 1.1501 1.1476 1.1449 1.1422 1.1395 1.1366 20.0 1.2033 1.2004 1.1976 1.1947 1.1919 1.1890
15.0 1.1516 1.1490 1.1464 1.1436 1.1408 1.1380 25.0 1.2046 1.2018 1.1989 1.1961 1.1932 1.1904
20.0 1.1530 1.1504 1.1478 1.1450 1.1423 1.1395 30.0 1.2059 1.2031 1.2003 1.1974 1.1946 1.1916
25.0 1.1544 1.1519 1.1492 1.1465 1.1437 1.1409 35.0 1.2071 1.2044 1.2015 1.1987 1.1958 1.1930
30.0 1.1558 1.1532 1.1506 1.1479 1.1451 1.1422 40.0 1.2083 1.2056 1.2028 1.2000 1.1971 1.1942
35.0 1.1571 1.1546 1.1519 1.1493 1.1464 1.1437 45.0 1.2095 1.2068 1.2040 1.2012 1.1983 1.1955
40.0 1.1585 1.1559 1.1533 1.1506 1.1478 1.1450 50.0 1.2107 1.2080 1.2051 1.2023 1.1995 1.1967
45.0 1.1598 1.1573 1.1547 1.1520 1.1492 1.1464
a
50.0 1.1611 1.1586 1.1560 1.1533 1.1506 1.1478 REL = 1 choline chloride: 2 urea.
b
x1 = 0.5000 Uncertainty in x1 = ±104.
c
0.1 1.1611 1.1584 1.1557 1.1529 1.1501 1.1473 Uncertainty in q = ±0.1%.
5.0 1.1624 1.1597 1.1571 1.1543 1.1515 1.1487
10.0 1.1638 1.1612 1.1584 1.1556 1.1529 1.1501
15.0 1.1652 1.1625 1.1599 1.1571 1.1543 1.1514
where q is the density at T, P in g  cm3; q0 is the reference density
20.0 1.1666 1.1639 1.1612 1.1585 1.1557 1.1529
25.0 1.1679 1.1653 1.1626 1.1599 1.1571 1.1543 at T in g  cm3; Pref is the reference pressure (0.1 MPa); and C, B(T)
30.0 1.1693 1.1667 1.1640 1.1612 1.1585 1.1556 are adjustable parameters. The parameter C was assumed to be
35.0 1.1706 1.1680 1.1653 1.1626 1.1598 1.1570 temperature independent while B(T) was assumed to be dependent
40.0 1.1719 1.1693 1.1666 1.1639 1.1611 1.1582 on temperature according to the following equation
45.0 1.1732 1.1706 1.1679 1.1652 1.1624 1.1596
50.0 1.1745 1.1719 1.1691 1.1664 1.1637 1.1609
BðTÞ ¼ b0 þ b1 T: ð4Þ
x1 = 0.5995
0.1 1.1716 1.1689 1.1661 1.1633 1.1605 1.1576
5.0 1.1730 1.1702 1.1675 1.1647 1.1619 1.1590 The densities at the reference pressure were fitted to linear equa-
10.0 1.1743 1.1717 1.1688 1.1660 1.1633 1.1604 tion of the form
15.0 1.1757 1.1730 1.1703 1.1675 1.1646 1.1617
20.0 1.1771 1.1743 1.1716 1.1688 1.1660 1.1632 q0 ðTÞ ¼ a0 þ a1 T: ð5Þ
25.0 1.1784 1.1757 1.1730 1.1702 1.1674 1.1646
30.0 1.1797 1.1770 1.1743 1.1715 1.1688 1.1658 The parameters a0 and a1 were obtained by a linear least
35.0 1.1810 1.1784 1.1756 1.1729 1.1701 1.1673 squares fitting procedure while b0, b1 and C were determined by
40.0 1.1822 1.1796 1.1769 1.1741 1.1713 1.1684 the Levenberg–Marquardt method. The values of the fitted param-
45.0 1.1835 1.1809 1.1782 1.1754 1.1726 1.1698
eters for equations (3)–(5) along with the corresponding AAD% for
50.0 1.1848 1.1822 1.1794 1.1767 1.1739 1.1711
each composition are presented in table 3. For each composition,
 R.B. Leron, M.-H. Li / J. Chem. Thermodynamics 54 (2012) 293–301 297

equation is an integrated form of an empirical equation that repre-

sents the isothermal compressibility against pressure [44]. There-
1.21 fore, jT can be conveniently derived from equation (3) using (5)
together with the parameters given in table 3. The resulting
expression for jT is
 
C q
jT ¼ : ð8Þ
1.20 BðTÞ þ P q0
The calculated values of jT are presented in table 4. It can be ob-
served that for each composition, the values increased as the tem-
-3
ρ/ g⋅cm

perature increased and decreased as the pressure increased. Such

1.19 behaviour is consistent with those observed for some ILs reported
in the literatures [30,44–46]. It was also observed that water tends
to increase the compressibility of the DES mixtures as indicated by
the decreasing values of jT as the mole fraction of REL increases in
1.18
the mixtures. The calculated isothermal compressibility values are
estimated to have an uncertainty of 2%.
The isobaric thermal expansivities can also be obtained analyt-
0 10 20 30 40 50
ically by differentiating the Tait-type equation. However, some
authors argued [45,47,48] that the estimated value of aP depends
P/ MPa
greatly on the applied temperature-dependent functions for B(T)
FIGURE 2. Density of REL as a function of pressure at different temperatures: d, and q0(T) leading to different values of aP. Thus, they recommend
298.15 K; j, 303.15 K; N, 308.15 K; ., 313.15 K; J, 318.15 K; , 323.15 K; and lines, deriving the isobaric expansivity numerically from the density val-
calculated using equation (3). ues at constant pressure. In this work, the dependence of the den-
sities with temperature at constant pressure for each composition
the parameter B(T) was found to be a decreasing function of tem-
could be described by a linear relation. Thus, the derivative
perature – a behaviour that has been observed for many liquid sys-
ð@ q=@TÞP in equation (7) was taken as the slope of each isobar
tems [43]. The Tait-type equation accurately correlated the
and the expansivities were hence calculated. The values of aP are
densities as functions of temperature and pressure as indicated
presented in table 5. For each composition, the aP slightly in-
by the low values of AAD% between the calculated and experimen-
creased with temperature but decreased with increasing pressure.
tal data. The agreement between the two sets of data is also de-
It was also observed that the expansivities generally increase at
picted in figure 2.
higher concentrations of the DES in the mixtures. The estimated
The experimental densities were used to derive other important
uncertainty of the calculated isothermal expansivities is 0.5%.
properties such as isothermal compressibility and isobaric expan-
The excess molar volumes of the {REL (1) + H2O (2)} mixtures
sivity which can give valuable information on the dependence of
were also investigated. For each mixture at each temperature
the volumetric properties on temperature and pressure. The iso-
and pressure, VE was calculated using the equation
thermal compressibility, jT, can describe the effect of pressure on
   
the density based on the equation V E ¼ x1 M 1 q1  q1
1 þ x2 M 2 q1  q1
2 ; ð9Þ
 
1 @q E 3 1
where V is in cm  mole ; q is the density of the mixture in
jT ¼ ; ð6Þ
q @P T;x1 g  cm3; q1, q2, x1, x2, M1, M2 represent the density, mole fraction
and molar mass of components 1 and 2, respectively. The molar
where q is the density and P is the pressure at constant temperature mass of the REL (86.58) was calculated from its individual compo-
T. On the other hand, the isobaric expansivity, aP, is related to the nents based on the method suggested by Abbott et al. [49]. For rep-
variation of the density with the temperature (at constant pressure) resentation, the excess molar volumes were plotted as a function of
which is described as mole fraction in figures 3 and 4. For all the mixtures, the excess mo-
  lar volumes were found to be negative over the entire composition
1 @q
aP ¼  : ð7Þ range at all temperatures and pressures with minima occurring at
q @T P;x1
x1  0.30. Such results imply increased densities of the mixture
In this work, the values of the isothermal compressibility of the compared with the ideal solution which has been observed for
systems studied at different sets of temperature and pressure were many IL-solvent systems [50,51]. The variation of the VE with com-
calculated by taking the derivative of equation (3). The Tait position for various isotherms at P = 0.1 MPa is shown in figure 3. As

TABLE 3
Fitting parameters for the Tait-type equation for REL and its aqueous mixtures.

x1a a0/gcm3 104a0/gcm3  K1 b0/MPa b1/MPa  K1 C 102AAD/%b

0.1001 1.2081 4.8457 522.9 0.5086 0.1253 1.1
0.2000 1.2590 5.2286 545.8 0.6108 0.1058 0.8
0.3000 1.2908 5.4171 666.9 0.7839 0.1140 0.8
0.3997 1.3107 5.4743 706.3 0.6857 0.1250 0.7
0.5000 1.3259 5.5257 521.2 0.4531 0.0940 0.5
0.5995 1.3386 5.6000 474.0 0.4560 0.0810 0.5
0.6998 1.3501 5.6943 499.6 0.5055 0.0814 0.4
0.7998 1.3593 5.7714 408.8 0.4817 0.0620 0.4
0.9000 1.3659 5.7977 407.2 0.5106 0.0594 0.4
1.0000 1.3700 5.7714 383.6 0.4344 0.0592 0.4
a
x1 denotes the mole fraction of REL.
P jqi;exp qi;cal j
b
AAD% ¼ 100  N1 N i q .
i;exp
298 R.B. Leron, M.-H. Li / J. Chem. Thermodynamics 54 (2012) 293–301

TABLE 4
Calculated isothermal compressibility of REL and its aqueous mixtures.

P/MPa 103jT/GPa1
T/K = 303.15 308.15 313.15 318.15 303.15 308.15 313.15 318.15

x1 = 0.1001 x1 = 0.5995
5.0 0.328 0.331 0.333 0.336 0.236 0.238 0.240 0.241
10.0 0.324 0.326 0.329 0.332 0.233 0.235 0.236 0.238
15.0 0.320 0.322 0.325 0.327 0.230 0.231 0.233 0.235
20.0 0.316 0.318 0.321 0.323 0.227 0.228 0.230 0.232
25.0 0.312 0.314 0.317 0.319 0.224 0.226 0.227 0.229
30.0 0.308 0.311 0.313 0.315 0.221 0.223 0.224 0.226
35.0 0.304 0.307 0.309 0.311 0.218 0.220 0.222 0.223
40.0 0.301 0.303 0.305 0.308 0.216 0.217 0.219 0.220
45.0 0.297 0.300 0.302 0.304 0.213 0.215 0.216 0.218

x1 = 0.2000 x1 = 0.6998
5.0 0.301 0.304 0.306 0.308 0.230 0.232 0.234 0.235
10.0 0.297 0.300 0.302 0.304 0.227 0.229 0.230 0.232
15.0 0.293 0.296 0.298 0.300 0.224 0.226 0.227 0.229
20.0 0.290 0.292 0.294 0.297 0.221 0.223 0.224 0.226
25.0 0.286 0.288 0.291 0.293 0.218 0.220 0.221 0.223
30.0 0.283 0.285 0.287 0.289 0.215 0.217 0.219 0.220
35.0 0.279 0.281 0.283 0.285 0.213 0.214 0.216 0.217
40.0 0.276 0.278 0.280 0.282 0.210 0.212 0.213 0.215
45.0 0.273 0.275 0.277 0.279 0.207 0.209 0.211 0.212

x1 = 0.3000 x1 = 0.7998
5.0 0.278 0.281 0.283 0.285 0.228 0.230 0.232 0.234
10.0 0.275 0.277 0.279 0.282 0.225 0.227 0.229 0.230
15.0 0.271 0.274 0.276 0.278 0.222 0.224 0.226 0.227
20.0 0.268 0.270 0.272 0.274 0.219 0.221 0.223 0.224
25.0 0.264 0.267 0.269 0.271 0.216 0.218 0.220 0.221
30.0 0.261 0.263 0.265 0.267 0.214 0.215 0.217 0.219
35.0 0.258 0.260 0.262 0.264 0.211 0.213 0.214 0.216
40.0 0.255 0.257 0.259 0.261 0.208 0.210 0.212 0.213
45.0 0.252 0.254 0.256 0.257 0.206 0.207 0.209 0.210

x1 = 0.3997 x1 = 0.9000
5.0 0.260 0.262 0.264 0.266 0.230 0.232 0.234 0.236
10.0 0.257 0.259 0.261 0.263 0.227 0.229 0.231 0.233
15.0 0.253 0.255 0.257 0.259 0.224 0.226 0.228 0.230
20.0 0.250 0.252 0.254 0.256 0.221 0.223 0.225 0.227
25.0 0.247 0.249 0.251 0.253 0.219 0.220 0.222 0.224
30.0 0.244 0.246 0.248 0.249 0.216 0.218 0.219 0.221
35.0 0.241 0.243 0.245 0.246 0.213 0.215 0.217 0.218
40.0 0.238 0.240 0.242 0.243 0.211 0.212 0.214 0.215
45.0 0.235 0.237 0.239 0.240 0.208 0.210 0.211 0.213

x1 = 0.5000 x1 = 1.000
5.0 0.246 0.248 0.250 0.252 0.237 0.239 0.241 0.243
10.0 0.242 0.245 0.247 0.248 0.234 0.236 0.238 0.240
15.0 0.239 0.241 0.243 0.245 0.231 0.233 0.235 0.236
20.0 0.236 0.238 0.240 0.242 0.228 0.230 0.232 0.233
25.0 0.233 0.235 0.237 0.239 0.225 0.227 0.229 0.230
30.0 0.230 0.232 0.234 0.236 0.222 0.224 0.226 0.227
35.0 0.228 0.229 0.231 0.233 0.219 0.221 0.223 0.224
40.0 0.225 0.227 0.228 0.230 0.217 0.218 0.220 0.221
45.0 0.222 0.224 0.225 0.227 0.214 0.216 0.217 0.219

one can see, at a constant pressure, the values of VE decreased (more where T0 = 273.15 K. The pressure-dependent function follows the
positive) as the temperature increased. This may be probably due to equation
the weakening of the hydrogen bonds in the solutions resulting
from increased temperatures. Figure 4 illustrates the variation of 1
f ðPÞ ¼ ð11Þ
VE with composition for various isobars at T = 298.15 K. Clearly, d0 þ d1 P þ d2 P 2
the VE decreases (more positive) as the pressure increases at con-
The parameters d0, d1, d2 and Dij were obtained by applying the
stant temperature. Such observation could be attributed to the de-
Levenberg-Marquardt method and the values are summarized in
crease in the molecular distance and the free-volume of the
table 6 together with the AAD%. A good agreement was obtained
mixtures and the pure samples which may have occurred upon
between the experimental and calculated values using equation
compression [52].
(10) with only 12 fitting parameters for 594 VE data. Such agree-
The experimental values of VE were then represented as a func-
ment is indicated by the AAD% of 2.4% and also illustrated by the
tion of temperature, pressure and composition using the equation
smooth fitted curves in figures 3 and 4.
proposed by Lugo et al. [27]
Lastly, to obtain a general correlation for the densities of the
X
3 X
3 {REL (1) + H2O (2)} mixtures as a function of the three variables
V E ¼ f ðPÞx1 x2 Dij ð2x1  1Þi1 ðT  T 0 Þj1 ; ð10Þ temperature, pressure and mole fraction, the Tait-type equation
i¼1 i¼j
earlier presented as equation (3) was modified according to
 R.B. Leron, M.-H. Li / J. Chem. Thermodynamics 54 (2012) 293–301 299

TABLE 5
Calculated isobaric expansivity of REL and its aqueous mixtures.

P/MPa 103aP/K1
T/K = 303.15 308.15 313.15 318.15 303.15 308.15 313.15 318.15

x1 = 0.1001 x1 = 0.5995
5.0 0.457 0.458 0.459 0.460 0.480 0.481 0.481 0.483
10.0 0.449 0.450 0.451 0.452 0.478 0.479 0.479 0.480
15.0 0.450 0.451 0.452 0.453 0.477 0.478 0.478 0.479
20.0 0.447 0.448 0.449 0.450 0.476 0.478 0.478 0.479
25.0 0.444 0.445 0.446 0.447 0.474 0.475 0.475 0.476
30.0 0.444 0.445 0.446 0.447 0.471 0.472 0.472 0.474
35.0 0.444 0.445 0.446 0.447 0.472 0.473 0.473 0.474
40.0 0.443 0.444 0.445 0.446 0.467 0.468 0.468 0.469
45.0 0.442 0.443 0.444 0.445 0.470 0.471 0.471 0.472
x1 = 0.2000 x1 = 0.6998
5.0 0.475 0.476 0.477 0.479 0.484 0.485 0.486 0.487
10.0 0.469 0.470 0.471 0.473 0.483 0.484 0.486 0.487
15.0 0.467 0.468 0.469 0.470 0.482 0.483 0.485 0.486
20.0 0.469 0.470 0.471 0.472 0.478 0.479 0.480 0.481
25.0 0.468 0.469 0.470 0.471 0.476 0.477 0.478 0.479
30.0 0.467 0.468 0.469 0.470 0.475 0.476 0.477 0.478
35.0 0.464 0.465 0.467 0.468 0.476 0.477 0.478 0.479
40.0 0.461 0.462 0.463 0.464 0.471 0.472 0.473 0.474
45.0 0.456 0.457 0.458 0.459 0.471 0.472 0.474 0.475
x1 = 0.3000 x1 = 0.7998
5.0 0.481 0.482 0.483 0.484 0.487 0.488 0.490 0.491
10.0 0.468 0.469 0.470 0.471 0.485 0.486 0.487 0.488
15.0 0.471 0.472 0.473 0.474 0.483 0.485 0.486 0.487
20.0 0.470 0.471 0.472 0.473 0.482 0.483 0.484 0.485
25.0 0.468 0.469 0.470 0.471 0.480 0.481 0.482 0.483
30.0 0.471 0.472 0.473 0.474 0.475 0.476 0.477 0.478
35.0 0.469 0.470 0.471 0.472 0.476 0.477 0.479 0.480
40.0 0.466 0.467 0.468 0.469 0.473 0.474 0.475 0.476
45.0 0.463 0.464 0.466 0.467 0.472 0.474 0.475 0.476
x1 = 0.3997 x1 = 0.9000
5.0 0.478 0.479 0.480 0.482 0.487 0.488 0.490 0.491
10.0 0.470 0.471 0.472 0.473 0.483 0.485 0.486 0.487
15.0 0.471 0.472 0.473 0.474 0.481 0.483 0.484 0.485
20.0 0.471 0.472 0.473 0.474 0.479 0.481 0.482 0.483
25.0 0.470 0.471 0.472 0.473 0.478 0.479 0.480 0.481
30.0 0.470 0.471 0.472 0.474 0.476 0.477 0.478 0.479
35.0 0.471 0.472 0.473 0.474 0.476 0.478 0.479 0.480
40.0 0.466 0.467 0.468 0.470 0.472 0.473 0.474 0.476
45.0 0.467 0.468 0.469 0.470 0.470 0.471 0.472 0.474
x1 = 0.5000 x1 = 1.000
5.0 0.478 0.479 0.479 0.480 0.483 0.484 0.485 0.486
10.0 0.474 0.475 0.475 0.476 0.481 0.482 0.483 0.484
15.0 0.474 0.476 0.476 0.477 0.479 0.481 0.482 0.483
20.0 0.474 0.475 0.475 0.476 0.478 0.479 0.480 0.481
25.0 0.471 0.473 0.473 0.474 0.476 0.477 0.478 0.479
30.0 0.468 0.469 0.469 0.471 0.474 0.475 0.476 0.477
35.0 0.471 0.472 0.472 0.473 0.472 0.473 0.474 0.475
40.0 0.467 0.468 0.468 0.469 0.470 0.471 0.472 0.474
45.0 0.469 0.470 0.470 0.471 0.468 0.469 0.470 0.472

Abdulagatov et al. [29,53]. The adjustable parameter B(T) was as-
sumed to remain as a temperature-dependent parameter described
by equation (4) while C was assumed to depend on the concentra-
tion. The best results were obtained for the function
Cðx1 Þ ¼ c0 þ c1 x1 þ c2 x21
Here, the reference density data for the mixtures, q0(T, x1, P)
were predicted using the excess molar volumes obtained by equa-
tion (10). The calculated values of VE at 0.1 MPa were used to esti-
mate the reference densities using the equation
M 12
q0 ðT; x1 ; 0:1MPaÞ ¼  ;
E M1
V þ x1 ðq Þ þ x2 M2
0;1 q0;2
where M12 is the molar mass of the mixture; q0,1, q0,2 are the refer-
ence densities of components 1 and 2 which can be calculated from
equation (5); and M1, M2 are the values of the molar mass of the
components 1 and 2, respectively. The calculated density data at
0.1 MPa, which are shown as lines in figure 5, were found to be in
excellent agreement with the experimental data with an AAD of
0.004%.
ð12Þ The fitting parameters bi and ci for equations (4) and (12) are
presented in table 7. As expected, the parameter B(T) for the mix-
tures was also found to be a decreasing function of temperature.
The parameter C(x1) was found to generally decrease with DES mole
fraction. The calculated AAD between the experimental and
predicted values was <0.02% for a total of 540 data points which sug-
gests that the proposed correlation accurately represents the exper-
ð13Þ
imental density data as a function of temperature, pressure and
composition. Figure 6 illustrates the excellent agreement between
the experimental and calculated data for the densities of the {REL
(1) + H2O (2)} mixtures for a selected isotherm (T = 323.15 K).
300 R.B. Leron, M.-H. Li / J. Chem. Thermodynamics 54 (2012) 293–301

0.00

1.20

-0.05

1.15
V E / cm3⋅mol-1

-0.10

ρ/g⋅cm -3
1.10

-0.15

1.05
-0.20
0.0 0.2 0.4 0.6 0.8 1.0
x1 300 310 320
T/ K
FIGURE 3. Excess molar volume as a function of x1 for {REL (1) + H2O (2)} mixtures
at 0.1 MPa at different temperatures: d, 298.15 K; j, 303.15 K; N, 308.15 K; ., FIGURE 5. Density of {REL (1) + H2O (2)} mixtures as a function of temperature at
313.15 K; J, 318.15 K; , 323.15 K; and lines, calculated using equation (10). 0.1 MPa for different mole fractions: d, 0.1001; j, 0.2000; N, 0.3000; ., 0.3997; J,
0.5000; , 0.5995; , 0.6998; w, 0.7998; , 0.9000; and lines, calculated using
equation (13).

0.00
TABLE 7
Fitting parameters bi and ci for the modified form of
equation (3) for the density of {REL (1) + H2O (2)}
mixtures.
-0.05 Parameter
b0/MPa 481.2
b1/MPa  K1 0.4731
c0 0.1225
c1 0.1213
V E/cm3⋅mol-1

-0.10 c2 0.0835
AAD/% 0.02

-0.15

1.20
-0.20
0.0 0.2 0.4 0.6 0.8 1.0
x1

FIGURE 4. Excess molar volume as a function of x1 for {REL (1) + H2O (2)} mixtures 1.15
at T = 298.15 K and different pressures: d, 0.1 MPa; j, 10 MPa; N, 20 MPa; .,
30 MPa K; J, 40 MPa; , 50 MPa; and lines, calculated using equation (10).
ρ/ g⋅cm-3

1.10

TABLE 6
Fitting parameters for equation (10) for the excess molar volume of {REL (1) + H2O
(2)} mixtures.

i j Dij/cm3  mol1  K1j d0 d1/MPa1 102 d2/MPa2 AAD/% 1.05

1 1 13.02 20.99 0.2338 0.2448 2.4
2 8.931  102
3 1.946  104 0 10 20 30 40 50
2 1 12.97
2 0.1358
P/ MPa
3 6.887  104
3 1 15.62 FIGURE 6. Density of {REL (1) + H2O (2)} mixtures as a function of pressure at
2 0.4513 T = 323.15 K for different mole fractions: d, 0.1001; j, 0.2000; N, 0.3000; .,
3 3.454  103 0.3997; J, 0.5000; , 0.5995; , 0.6998; w, 0.7998; , 0.9000; and lines, calculated
using a modified form of equation (3).
 R.B. Leron, M.-H. Li / J. Chem. Thermodynamics 54 (2012) 293–301
4. Conclusions
The densities of the deep eutectic solvent 1 choline chloride: 2
urea (REL) and its aqueous mixtures over the temperature range
(298.15 to 323.15) K and up to 50 MPa were reported. The densi-
ties decrease with increasing temperature and increase with
increasing pressure and DES mole fraction. The values of the iso-
thermal compressibility and isobaric expansivity increased as the
temperature increased and decreased as the pressure increased.
The increasing concentration of water in the aqueous REL mixtures
resulted in increasing compressibility and decreasing expansivity
of the samples. A Tait-type equation with five fitting parameters
accurately correlated the density of the DES REL to temperature
and pressure at an AAD% of 0.004%. The excess molar volumes
were negative over the entire composition range at all tempera-
tures and pressures and the absolute values decreased with
increasing temperature (at constant pressure) and pressure (at
constant temperature). These could be attributed to the depen-
dence of the strength of hydrogen bonding in the liquid on temper-
ature and decrease in the molecular distance and the free-volume
of the mixtures and the pure samples. For the aqueous mixtures,
the high-pressure densities and the excess molar volumes were
accurately correlated to the three variables, temperature, pressure
and composition, by a modified Tait-type equation (AAD = 0.02%)
and an empirical equation based on Lugo et al. (AAD = 2.4%),
respectively. Thus, it can be concluded that the new measurements
and the correlations presented in this work can be accurately used
in engineering calculations.
Acknowledgements
This research was supported by Grant, NSC 101-3113-E-007-
005, of the National Science Council of the Republic of China.
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JCT-12-167