Article

pubs.acs.org/jced

Formation of Deep Eutectic Solvents by Phenols and Choline

Chloride and Their Physical Properties
Wujie Guo,† Yucui Hou,‡ Shuhang Ren,† Shidong Tian,† and Weize Wu*,†
†
State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029, China
‡
Department of Chemistry, Taiyuan Normal University, Taiyuan 030031, China
*
S Supporting Information

ABSTRACT: Novel deep eutectic solvents (DES) based on three different

hydrogen-bond donors (HBD), namely phenol, o-cresol, and 2,3-xylenol,
and choline chloride (ChCl) were successfully synthesized with different
mole ratios of HBD to ChCl. Melting temperature of these DES were
measured. Compared with an ideal mixture of the two components, the
freezing temperature of the DES depresses greatly from (120 to 127) K. The
physical properties, such as density, viscosity, and conductivity of phenol-
based and o-cresol-based DES were determined at atmospheric pressure and
temperatures from (293.2 to 318.2) K at an interval of 5 K. The results show
that the type of HBD, the mole ratio of HBD to ChCl, and temperature have
great influences on the physical properties of DES. Densities and viscosities
of DES formed by phenol and ChCl decrease with increases of temperature
and phenol content. The conductivities of the DES are from (1.40 to 7.06)
mS·cm−1, similar to that of room temperature ionic liquids. The
conductivities of the DES increase with an increase of temperature, and reach the highest values at phenol to ChCl mole
ratios of 4.00 to 5.00. The temperature dependence of densities and conductivities for these DES were correlated by an empirical
second-order polynomial with relative deviations less than 0.91 %, and the viscosities were fitted to the VTF equation with
relative deviations less than 0.52 %.

■ INTRODUCTION
Phenols, one kind of the major industrial organic chemicals, are
used to produce phenolic resins, bisphenol A, adipic acid, and
so on.1 It is well-known that phenols are produced from
petroleum, coal tar, coal liquefaction oil, and biomass pyrolysis
oil.2−4 Phenols are first separated from these phenol-containing
oils, and then the obtained phenols mixtures are refined for
further applications. The present industrial method to separate
phenols from oils mixtures is chemical extraction using aqueous
alkaline solutions (such as aqueous NaOH) and then
acidification of the extract by mineral acids (such as aqueous
H2SO4) to recover the phenols. The disadvantages of this
process are the use of large amounts of both strong alkalis and
acids and the production of excessive amounts of wastewater
containing phenols. The separation approach based on forming
reversible chemical complexations is of high efficiency and high
selectivity for separating polar organic solutes in dilute
solutions.5 However, researches on extraction of phenolics
from coal liquefaction oil and purification of crude phenol have
not been reported on reversible chemical complexation because
the chemical complexations are miscible with oil. Therefore,
alternative methods to separate phenols from oil mixtures using
a nonaqueous and oil-immiscible solvent were necessary.
A deep eutectic is a eutectic mixture formed by compounds
(usually solids) mixed together in proper ratios where the
eutectic temperature is considerably lower, often by several 100
K, than would be predicted from the known enthalpies of
fusion of the pure compounds using ideal solution theory. As
early as 2003, Abbott et al. reported that the mixtures of amides
with quaternary ammonium salts could form low melting point
eutectics that had unusual solvent properties.6 Later, the
research group7,8 indicated that deep eutectic solvents (DES)
could be formed between hydrogen bond donors (HBD) such
as carboxylic acids as well as alcohols besides amides and a
variety of quaternary ammonium salts. Formation and
characterization of DES based on choline chloride and
resorcinol, levulinic acid, and sugar-based polyols were also
described.9,10 DES show good mediums for deposition of
metals, such as Ag, Cu, Cr, Sn, and Zn, which have potential
applications for electro-plating of metals.11,12 In addition, DES
have been used as a reaction media in the process of synthesis
of lanthanide-organic frameworks as well as polymer and
related materials.13,14 Recently, DES have been used in
separation process, because they are nontoxic, nonreactive
with water, biodegradable, and easy to prepare.7,15 DES based
on methyltriphenyl phosphunium bromide were used for the
separation of glycerol from palm oil-based biodiesel, where
glycerol is a HBD.16 The uses of DES as extraction agents for
Received: September 1, 2012
Accepted: March 5, 2013
Published: March 15, 2013

© 2013 American Chemical Society 866 dx.doi.org/10.1021/je300997v | J. Chem. Eng. Data 2013, 58, 866−872
Journal of Chemical & Engineering Data Article

glycerol from biodiesel based on rapeseeds and soybeans was Table 1. Compositions and Abbreviations for DES Used in
disclosed for the first time in 2007 by Abbott et al.8 In 2010, This Worka
Hayyan et al.17 reported that DES based on a quaternary
mole ratio of HBD to
ammonium salt and glycerol could be also applied to extract the salt HBD salt abbreviation water content/%
total glycerol from palm oil-based biodiesel. The physical
ChCl phenol 2.00 DES1 0.256
properties such as conductivity and viscosity of these DES were
ChCl phenol 3.00 DES2 0.358
similar to room temperature ionic liquids (ILs). At present,
ChCl phenol 4.00 DES3 0.130
many researchers have focused on the physicochemical
ChCl phenol 5.00 DES4 0.186
characterization of DES because of their promising applica-
ChCl phenol 6.00 DES5 0.094
tions.18
ChCl o-cresol 2.00 DES6 0.107
Lately, our research group found that choline chloride
ChCl o-cresol 3.00 DES7 0.098
(ChCl) could be used to efficiently separate phenolic ChCl o-cresol 3.91 DES8 0.090
compounds from model oils by forming DES.19,20 When ChCl o-cresol 5.00 DES9 0.097
ChCl with an equimolar amount to phenol were added to ChCl o-cresol 6.00 DES10 0.249
phenol containing model toluene oils at 293 K, phenol- a
extraction efficiency at an initial phenol concentration of 178 The standard uncertainty of mole ratio of HBD to Salt is 0.001, and
the standard uncertainty of water content is 0.010 %.
g·L−1 were found to be 93.4 % and the cresol-extraction
efficiencies at an initial phenol concentration of about 200 g·L−1
were found to be 92.5 % (o-cresol), 94.8 % (m-cresol), and 94.7 of the pycnometer was calibrated by distilled water at different
% (p-cresol), respectively. temperatures before experiment. Densities of the samples were
When the DES method is employed for separations of measured from (293.2 to 318.2) K at an interval of 5 K. All of
phenols from oils, it is very important to understand the the measurements were carried out in a constant-temperature
properties of DES phases for their significant influence on mass water bath, in which the temperature was maintained within ±
transfer, diffusion, phase separation efficiency, and so forth. 0.1 K by a temperature controller (model A2, Beijing Changliu
However, data on the DES phase properties during separations Scientific Instrument Co., Ltd.). The reproducibility of the
of phenols from oils have not been reported in the literature. measurements was better than ± 0.05 %, and it was estimated
Therefore, this work focused on the formation of DES between that the uncertainty of the density was not more than ± 0.1 %.
phenolic compounds and ChCl, and measurements of melting Viscosity Determination. The viscosities of the DES were
temperature, density, viscosity, and conductivity of ChCl-based determined using a traditional technique, Ubbelohde viscom-
DES as a function of temperature and composition. Phenol, o- eter that was based on Poiseuiele Law. The standard oils of
cresol and 2,3-xylenol are dominant phenolic compounds in different viscosities provided by National Standard Bureau of
coal tar or coal liquefaction oil, and our previous work19 China were used to calibrate the viscometer. 22 The
demonstrated that they could be extracted by ChCl by forming reproducibility of the measurements was better than ± 1 %,
DES. Hence they were selected as HBD in this work. and the uncertainty of the viscosity was less than ± 3 %.

■ EXPERIMENTAL SECTION
Materials. ChCl, o-cresol, and 2,3-xylenol were obtained
from Aladdin Chemical Co., Ltd. (Shanghai, China) with mass
fraction purities more than 0.99. Phenol with a mass fraction
purity of 0.98 was purchased from Beijing Chemical Plant
Conductivity Determination. Conductivities of the DES
were determined via a conductivity meter (DDSJ-308A,
Shanghai Leici Co., Ltd., Shanghai, China). The meter was
calibrated with aqueous solutions of KCl of known
conductivities at different concentrations. The reproducibility
of the measurements was no more than ± 0.5 %, and the
uncertainties of data were ± 1 %.

(Beijing, China). All reagents were of analytical reagent grade
and used for the synthesis of DES with no further purification.
Synthesis of DES. In this work, novel DES based on ChCl
and three HBD, namely phenol, o-cresol, and 2,3-xylenol, were
synthesized with several mole ratios of ChCl to HBD. A 250
cm3 jacketed glass vessel with a mechanical stirrer was used to
mix ChCl with HBD in different mole ratios at 40 rpm and
353.2 K until a homogeneous liquid appeared. The water
contents of DES, detected by a Karl Fischer titration (ZDJ-
400S, Beijing Xianqu Weifeng Technology Development Co.,
Ltd.), were less than 0.4 % mass fraction. The compositions of
the DES synthesized in this work along with their abbreviations
and water contents are shown in Table 1.
Freezing Point Determination. The freezing point of
each DES was determined by a differential scanning calorimeter
(Netzsch DSC 204 F1) in a temperature range of (150.2 to
353.2) K. A sample was sealed in an aluminum pan, and then it
was heated and cooled at a scan rate of 10 K min−1 under a flow
of nitrogen. The thermal data were collected during the second
heating−cooling scan.21 It was estimated that the uncertainty of
the freezing point was 8.1 K.
Density Determination. The densities of the DES were
determined via a pycnometer of 5 cm3 in volume. The volume
867
■
RESULTS AND DISCUSSION
Deep Eutectic Solvents. The freezing temperatures for
DES of ChCl with phenolic compounds as a function of
composition are shown in Table 2 and graphically in Figure 1.
As can be seen from Figure 1, a deep eutectic is formed at
about 75 % of phenolic compounds. Compared with an ideal
mixture of the two components, the freezing temperature of the
DES depresses largely, for example, 127 K for the phenol−
ChCl system, 123 K for the phenol−o-cresol system and 120 K
for the 2,3-xylenol−ChCl system. The depression of freezing
point is not as large as the ChCl−oxalic acids (212 K)7 and the
ChCl-ZnCl2 system (272 K),23 possibly because of the covalent
bonds existing in the ChCl−oxalic acids and ChCl−ZnCl2. The
crystal structure of ChCl, oxalic acids and ZnCl2 collapsed to a
great extent when the covalent bonds were formed, resulting in
the decrease of lattice energies for the DES with ChCl and
oxalic acid as well as ZnCl2.
Like conventional ILs, the formation of liquid phase for DES
is governed by the freezing point of ionic compounds. The
lattice energies of the quaternary ammonium salt and HBD as
well as the entropy changes forming a liquid have a significant
dx.doi.org/10.1021/je300997v | J. Chem. Eng. Data 2013, 58, 866−872
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Table 2. Freezing Points of DES Based on ChCl and Three transition temperature indicated that the crystal structure of
Different HBD at Pressure p = 0.101 MPa for Different HBD ChCl and phenol collapsed resulting from the strong hydrogen
to ChCl Mole Fractionsa bonding between phenol and ChCl. Interestingly, for some
phenol-based DES, it is difficult to decide freezing temperatures
DES (ChCl + 2,3-
DES (ChCl + phenol) DES (ChCl + o-cresol) xylenol) from DSC traces, as shown in Figure S1 in the ESI; however,
the freezing temperatures of DES with a variety of salts and
xHBD/% Tf/K xHBD/% Tf/K xHBD/% Tf/K
HBD have been widely reported.6,18,26 We also observed that
0.0b 577.2 0.0 577.2 0.0 577.2 some solid materials appeared and were suspended in the
54.6 335.2 54.6 348.3 60.0 330.5 phenol-based DES liquid (such as CP1:1.5) with the decrease
60.0 294.2 60.1 321.8 66.8 323.6 of temperature in the tested range. Therefore, the freezing
75.0 253.1 64.3 295.3 75.0 290.8 temperatures of some phenol-based DES were measured by
80.0 260.2 75.0 249.4 80.0 316.3 gradual cooling until the first solid appeared. Both o-cresol-
83.3 255.6 79.7 250.3 83.3 325.0 based DES and 2,3-xylenol-based DES produced the character-
88.1 279.3 83.4 251.4 90.0 339.8
istic broad single peaks at the deep eutectic composition and
90.0 297.5 85.7 279.5 100.0c 348.2
the characteristic double peaks at the other composition, which
100.0c 313.8 90.9 283.0
is similar to published eutectic systems.27,28 According to the
100.0c 304.1
a
literature,27 the broad single peaks could be illustrated by the
Standard uncertainties u are u(x) = 0.001, u(p) = 1 kPa, and the characteristic peaks of deep eutectic composition. Systems with
combined expanded uncertainty Uc is Uc(Tf) = 8.1 K. bThe Tf of ChCl compositions beyond the eutectic point can be viewed as a
was obtained from ref 18. cThe Tf of phenols was obtained from the
mixture of a eutectic composition and HBD or ChCl. The left
NIST Chemistry WebBook.
peaks for eutectic systems (such as CD1:2) at either side of the
deep eutectic composition resulted from the eutectic
composition. The right peaks derived from HBD dissolved in
the eutectic composition.
Density. The densities of DES formed between ChCl and
phenol are listed in Table 3 and graphically shown in Figure 2a.

Table 3. Densities of the DES at Different Phenol to ChCl

Mole Ratios and at Pressure p = 0.101 MPa and
Temperature T = (293.2 to 318.2) Ka
ρ/g·cm−3
T/K DES1 DES2 DES3 DES4 DES5
293.2 1.0995 1.0948 1.0918 1.0898 1.0885
298.2 1.0967 1.0921 1.0893 1.0870 1.0852
Figure 1. Freezing points Tf of ChCl with phenol (■), o-cresol (●), 303.2 1.0930 1.0890 1.0860 1.0838 1.0818
and 2,3-xylenol (▲) as a function of composition xHBD. The melting
308.2 1.0901 1.0858 1.0819 1.0803 1.0782
point of pure ChCl (at xHBD = 0) is 577.2 K.
313.2 1.0873 1.0829 1.0795 1.0761 1.0745
318.2 1.0843 1.0795 1.0763 1.0736 1.0717
effect on the freezing temperature of DES.4 The larger the ion a
Standard uncertainties u are u(T) = 0.1 K, u(p) = 1 kPa, u(x) = 0.001,
size and the smaller the ion charge, the less energy is needed to and the combined expanded uncertainty Uc is Uc(ρ) = 0.0010 g·cm−3.
break the bond, resulting in a depression of the freezing point.24
Due to the low lattice energy of such DES, they may exist as
liquids at room temperature. It can be inferred that to form the Table 4 shows the density of the DES with different ChCl to o-
eutectic, phenol molecules are required to complex each cresol mole ratios and at pressure p = 0.101 MPa and
chloride ion. Hence, we conclude that the chloride ion is temperature T = 298.2 K. The density of DES is expected to
complexed by the associated phenol in a manner analogous to decrease with an increase of temperatures at a fixed mole ratio
the urea/ChCl system reported previously.6 of phenol to ChCl. At a given temperature, the density of DES
Figure 1 also indicates that the freezing points of phenol- decreases with an increase of phenol composition in the DES
based DES and o-cresol-based DES are lower than those of 2,3- mixture. Phenol interacts with the anion of ChCl to form DES,
xylenol-based DES. Phenol and o-cresol may form more stable which has the potential to decrease the DES density.
complex anions with chloride anions of ChCl than 2,3-xylenol, Figure 2b shows the density of DES of phenol and ChCl as a
due to steric hindrance of 2,3-xylenol. Phenolic compounds can function of HBD to ChCl mole ratio compared with that of o-
serve as HBD to interact with chloride anions, but produce cresol and ChCl. The density of 3-xylenol-based DES was not
different lattice energy of DES, resulting in different freezing measured due to their high freezing temperature. Obviously the
points. Glass transition temperatures (Tgs) of the selected DES density of DES of ChCl and phenol is greater than that of ChCl
with phenols and ChCl could be also found in the and o-cresol. The reason is possibly that the molecule of phenol
representative DSC curves, showed in Figure S1 in the ESI. is smaller than that of o-cresol, and phenol has the smaller
Tgs are significantly lower compared with the freezing stereohindrance effect than o-cresol.
temperatures of the starting materials, so Tgs are called ultralow The densities as a function of temperature were fitted using
glass transition temperatures. The Tgs of phenol-based DES the following polynomial eq 1 according to the literature.29
were obvious and similar to low transition temperature
mixtures described in the literature.25 The ultralow glass ρ = k 0 + k1T + k 2T 2 (1)

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Figure 2. (a) Densities (ρ) of ChCl-based DES as a function of temperature (T) in the range of (293.2 to 318.2) K with the polynomial fit curves.
The mole ratio of phenol to ChCl: ■, 2.00; □, 3.00; ▲, 4.00; ○, 5.00; ●, 6.00. (b) Densities (ρ) of ChCl-based DES as a function of HBD to ChCl
molar ratio at 298.2 K. HBD: ■, phenol; □, o-cresol.

Table 4. Densities of the DES at Different o-Cresol to ChCl Table 6. Viscosities of the DES at Different Phenol to ChCl
Mole Ratios and at Pressure p = 0.101 MPa and Mole Ratios at Pressure p = 0.101 MPa and Temperature T
Temperature T = 298.2 Ka = (293.2 to 318.2) Ka
ρ/g·cm−3 η/mPa·s
T/K DES6 DES7 DES8 DES9 DES10 T/K DES1 DES2 DES3 DES4 DES5
298.2 1.0776 1.0707 1.0664 1.0631 1.0606 293.2 120.77 57.84 40.23 31.96 27.03
a 298.2 90.33 44.64 31.55 25.25 21.43
Standard uncertainties u are u(T) = 0.1 K, u(p) = 10 kPa, u(x) =
0.001, and the combined expanded uncertainty Uc is Uc(ρ) = 0.001 303.2 68.41 35.17 25.20 19.75 16.82
g·cm−3. 308.2 53.43 28.22 20.25 16.16 13.76
313.2 42.42 23.08 16.71 13.44 11.45
318.2 34.34 19.14 14.00 11.26 9.46
where ρ is the density in g·cm−3, k0, k1, and k2 are the fitting a
Standard uncertainties u are u(T) = 0.1 K, u(p) = 1 kPa, u(x) = 0.001,
parameters that depend on the type of DES, and T is the and the combined expanded uncertainty Uc is Uc(η) = 0.03η.
temperature in K. The values of k0, k1, and k2 of eq 1 are
instance, at 298.2 K, the viscosity of DES with 2.00 mol ratio of
Table 5. Fit Parameters k0, k1, k2 and Relative Deviation σ phenol to ChCl is 90.33 mPa·S; and it is as low as 21.43 mPa·S
for the Empirical Correlation of Density for the DES with 6.00 mol ratio of phenol to ChCl. Phenol
added to ChCl not only acts as a HBD to form a DES, but also
DES k0 103k1 106k2 σ/%
as an organic solvent to decrease DES viscosity, which is similar
DES1 1.45 −1.74 1.84 0.12 to adding solvents (such as water) to ILs. Viscosity reflects the
DES2 1.10 0.54 −1.88 0.01 molecular interaction in the solution. Phenol added to DES can
DES3 1.26 −0.55 −0.15 0.03
decrease the molecular interaction of DES, such as Coulomb
DES4 1.10 0.57 −2.02 0.07
attraction of cations and anions.
DES5 1.38 −1.26 0.94 0.07
In addition, the minimum of the viscosity for DES does not
necessarily appear at the deep eutectic temperature (DES of
obtained by correlation and shown in Table 5. The table also ChCl and phenol, 253.1 K; DES of ChCl and o-cresol, 249.4 K)
contains the relative deviation σ defined as30 as can be inferred from Figure 3. These results are similar to the
n |ρcalc, i − ρexp , i | one reported previously for the DES of ChCl with ethylene
1 glycol.31
σ (%) = ∑ × 100
n i
ρexp , i (2) Figure 3b shows viscosities of DES of phenol and ChCl at
different ChCl to HBD mole ratios compared with that of DES
where ρcalc,i is the value of the density calculated by eq 1, ρexp,i is of o-cresol and ChCl. Although o-cresol and phenol both can
the value of the density measurement, and n is the number of form DES with ChCl sharing almost the same freezing points,
experimental points. Table 5 shows that the relative deviations the viscosity of DES of phenol and ChCl is much lower than
are very small, not more than 0.12 %, which means that eq 1 that of o-cresol and ChCl. The viscosity of 2,3-xylenol-based
can be well correlated to the experimental data. DES could not be measured because of their high freezing
Viscosity. The viscosity of phenol-based DES is presented temperature.
in Table 6 and illustrated in Figure 3a. Table 7 shows the The Vogel−Tamman−Fulcher (VTF) equation, which is
viscosity of the DES with different ChCl to o-cresol mole ratios shown in eq 3,32 is used to fit the viscosities of DES as a
at pressure p = 0.101 MPa and temperature T = 298.2 K. The function of temperature.
viscosity values for these DES are found to cover a range from
(9 to 121) mPa·s. As expected, the viscosity of phenol-based ⎛ −k ⎞
DES decreases with an increase of temperature. The viscosity of η = AT 0.5 exp⎜ ⎟
⎝ T − T0 ⎠ (3)
the DES with a low content of phenol is more sensitive to
temperature. At a fixed temperature, the viscosity of the DES where k is the so-called pseudoactivation energy, T is the
decreases with an increase of phenol content in DES. For temperature and T0 the ideal glass transition temperature in K,
869 dx.doi.org/10.1021/je300997v | J. Chem. Eng. Data 2013, 58, 866−872
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Figure 3. (a) Viscosity (η) of ChCl-based DES as a function of temperature (T) at the range of (293.2 to 318.2) K with the VTF fit curves. Mole
ratio of phenol to ChCl: ■, 2.00; □, 3.00; ▲, 4.00; ○, 5.00; ●, 6.00. (b) Viscosities (η) of ChCl-based DES as a function of HBD to ChCl molar
ratio at 298.2 K. HBD: ■, phenol; □, o-cresol.

Table 7. Viscosities of the DES at Different o-Cresol to ChCl Table 10. Electrical Conductivity of the DES at Different o-
Mole Ratios and at Pressure p = 0.101 MPa and Cresol to ChCl Mole Ratios at Pressure p = 0.101 MPa and
Temperature T = 298.2 Ka Temperature T = 298.2 Ka
η/mPa·s κ/mS·cm−1
T/K DES6 DES7 DES8 DES9 DES10 T/K DES6 DES7 DES8 DES9 DES10
298.2 207.41 77.65 46.95 34.90 27.82 298.2 0.83 1.21 1.41 1.45 1.38
a a
Standard uncertainties u are u(T) = 0.1 K, u(p) = 1 kPa, u(x) = 0.001, Standard uncertainties u are u(T) = 0.1 K, u(p) = 1 kPa, u(x) = 0.001,
and the combined expanded uncertainty Uc is Uc(η) = 0.03η. and the combined expanded uncertainty Uc is Uc(κ) = 0.01κ.

and A the high-temperature viscosity limiting value. All the DES with different ChCl to o-cresol mole ratios and at
coefficients are listed in Table 8. pressure p = 0.101 MPa and temperature T = 298.2 K.These
DES have conductivities in the range from (1.40 to 7.06)
Table 8. Regression Parameters for Viscosity VTF Equation mS·cm−1 changing with composition and temperature. The
and Relative Deviation σ electrical conductivities of these DES are graphically shown in
Figure 4a, which as expected increases with the increase of
DES 103A k T0/K σ/% temperature. At fixed temperatures, the effect of phenol to
DES1 4.27 −869.03 175.93 0.20 ChCl mole ratio on the electrical conductivity is not monotone
DES2 5.71 −727.96 179.14 0.09 like on density and viscosity of the DES. The electrical
DES3 2.59 −882.76 163.59 0.26 conductivity of DES reaches a maximum at phenol to ChCl
DES4 5.27 −644.69 183.42 0.52 mole ratio of 4.00 or 5.00. The electrical conductivity of DES is
DES5 1.86 −874.04 163.60 0.49 influenced by its viscosity and ion concentration. As shown
above, the viscosity of the DES is decreased with the increase of
The correlated results are shown in Figure 3a as curves, and phenol to ChCl mole ratio, but the increase of phenol to ChCl
the relative deviations are shown in Table 8, which indicates mole ratio decreases the ion concentration supplied by ChCl.
that the relative deviations are less than 0.523 %. Therefore, at high phenol to ChCl mole ratios, such as phenol
Electrical Conductivity. Table 9 shows the electrical to ChCl mole ratio = 6.00, the decreases of the ion
conductivity of the DES with different ChCl to phenol mole concentration become the dominant effect, resulting in the
ratios and at pressure p = 0.101 MPa and different lower electrical conductivity of DES.
temperatures. Table 10 shows the electrical conductivity of Figure 4b shows that electrical conductivities of phenol-based
DES are larger than those of o-cresol-based DES, which results
Table 9. Electrical Conductivity of the DES at Different from the effect of viscosity of DES as shown in Figure 3b. The
Phenol to ChCl Mole Ratios at Pressure p = 0.101 MPa and electrical conductivities of 2,3-xylenol-based DES were not
Temperature T = (293.2 to 318.2) Ka measured due to their high freezing temperature. The majority
of 2,3-xylenol-based DES was solid at low freezing temperature
κ/mS·cm−1 (< 303 K), therefore, the conductivity of DES based on 2,3-
T/K DES1 DES2 DES3 DES4 DES5 xylenol was not measured in the investigated temperatures.
293.2 1.40 2.38 2.75 2.81 2.73 Electrical conductivities of both phenol-based DES and o-
298.2 2.05 3.14 3.45 3.47 3.38 cresol-based DES have maximum values at a HBD to ChCl
303.2 2.65 3.88 4.21 4.25 4.09 mole ratio of about 5.
308.2 3.37 4.77 5.07 5.08 4.87 The ChCl-based DES are potential solvents in the electro-
313.2 4.16 5.76 6.02 5.99 5.74 chemical field due to their relatively high conductivities from
318.2 5.09 6.77 7.06 6.96 6.66 (1.40 to 7.06) mS·cm−1. The experimental conductivity (κ) was
correlated using33
a
Standard uncertainties u are u(T) = 0.1 K, u(p) = 1 kPa, u(x) = 0.001,
and the combined expanded uncertainty Uc is Uc(κ) = 0.01κ. κ = k 0 + k1(T − 273.2) + k 2(T − 273.2)2 (4)

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Figure 4. (a) Conductivity (κ) of ChCl-based DES as a function of temperature (T) at the range of (293.2 to 318.2) K with the polynomial fit
curves. Mole ratio of phenol to ChCl: ■, 2.00; □, 3.00; ▲, 4.00; ○, 5.00; ●, 6.00. (b) Conductivities (κ) of ChCl-based DES as a function of HBD
to ChCl molar ratio at 298.2 K. HBD: ■, phenol; □, o-cresol.

where κ is specific conductivity in mS·cm−1, T is the

temperature in K, k0, k1, and k2 are fitting parameters. All
■ AUTHOR INFORMATION
Corresponding Author
coefficients are listed in Table 11. The relative deviations of the
*Tel./Fax: +86 10 64427603. E-mail: wzwu@mail.buct.edu.cn.
Table 11. Fit Parameters k0, k1, k2 and Relative Deviation σ Funding
for the Empirical Correlation of Conductivity This work is financially supported by the National Basic
Research Program of China (2011CB201303) and Shanxi
DES k0 k1 103k2 σ/% Scholarship Council of China (2011−086).
DES1 −0.12 0.047 1.52 0.91 Notes
DES2 0.32 0.072 1.60 0.50
The authors declare no competing financial interest.

■
DES3 0.89 0.058 1.76 0.15
DES4 0.81 0.070 1.49 0.17
ACKNOWLEDGMENTS
DES5 0.86 0.065 1.42 0.10
We thank Professors Zhenyu Liu and Qingya Liu at Beijing
University of Chemical Technology for discussion and
suggestions.

■
correlated results are not more than 0.91 %. The correlated
results are shown in Figure 4a as curves, which indicate that eq
4 can correlate well the conductivity of DES. REFERENCES

■ CONCLUSIONS
A variety of DES were synthesized by mixing ChCl with
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temperature. Reasonable correlations of the temperature
dependence were achieved by fitting the viscosity to the VTF
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