Journal of Molecular Liquids 199 (2014) 208–214

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Journal of Molecular Liquids

journal homepage: www.elsevier.com/locate/molliq

Effects of existence form and concentration of PbO on the conductivity of

choline chloride–urea deep eutectic solvent
Juanjian Ru, Yixin Hua ⁎, Jian Li, Cunying Xu, Yan Li, Ding Wang, Cancan Qi, Yafei Jie
Faculty of Metallurgical and Energy Engineering, Kunming University of Science and Technology, Kunming 650093, PR China
State Key Lab of Complex Nonferrous Metal Resources Clean Utilization, Kunming 650093, PR China

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

Article history: The effects of existence form and concentration of lead oxide (PbO) on the conductivity and viscosity of choline
Received 4 June 2014 chloride (ChCl)-urea deep eutectic solvent (DES) were investigated. The ESI-MS and FT-IR analyses indicated that
Received in revised form 27 August 2014 three-coordinated complexes are presented in the form of {[PbO∙CO(NH2)2]∙Cl−}−. It is deduced that the complex
Accepted 8 September 2014
anions are formed through sp3 hybrid orbitals of Pb2+ ion and three sp hybrid orbitals are all filled with lone pair
Available online 11 September 2014
electrons which are donated by Cl−, O2− and O atoms of urea respectively. The raising of temperature leads to the
Keywords:
electrical conductivity increases. With PbO concentration, however, the conductivity increases firstly and then
Lead oxide decreases. The viscosity has an opposite change trend compared with the conductivity. These experimental phe-
Deep eutectic solvents nomena can be explained by the formation of PbO-containing complexes and oligomers.
Electrical conductivity © 2014 Elsevier B.V. All rights reserved.
Existence form
MS

1. Introduction purity can be deposited in ZnO–[Amim]Cl–urea and ZnO–ChCl-urea so-

Deep eutectic solvents (DESs) are a unique class of multicomponent
solvent systems formed through hydrogen bond interactions [1,2]. Be-
cause of their low melting points, nontoxicity, chemical inertness with
water, and ease of preparation, DESs have been applied in many fields
including biological catalysis [3], organic synthesis [4], dissolution and
extraction processes [5,6], material chemistry [7–9] and electrochemis-
try [10,11]. In addition, DESs are capable of dissolving the various metal
oxides [12–16] (including PbO2, Cu2O, CuO and ZnO) which are found to
be insoluble in common room temperature ionic liquids [17]. The differ-
ence of solubility between these metal oxides has been successfully ap-
plied for the selective recovery of oxides from wasted materials [18]. On
the other side, the DESs dissolving metal oxides can also be used as elec-
trolytes to recover metals through electrowinning. This method is valu-
able not only from the point view of low capital investment and
operational costs, but also for the easy operation and high purity of
the deposits. Hussey et al. [14] systematically studied the electrochem-
istry of Cu2O in choline chloride (ChCl)–urea DES based on its relatively
high solubility in the DES and found that pure quality Cu films could be
electrodeposited on glassy carbon and Ni substrate. Lu et al. [15] have
reported that bright, dense and well adherent zinc coatings with good
⁎ Corresponding author.
E-mail address: huayixin@gmail.com (Y. Hua).
lutions at 323.2–343.2 K. In our previous study [19], sub-micrometer
lead wires can be electrodeposited from PbO–ChCl–urea solution on
stainless steel substrate. In particular, the electrical conductivity of elec-
trolyte has a significant effect on current efficiency during the deposi-
tion process. Therefore, it is necessary to find suitable experiment
conditions, which can enhance the electrical conductivity, for attaining
higher current efficiency and lower specific energy consumption. How-
ever, a thorough understanding about the solvation process and exis-
tence form of metal oxide in DES is lacking. More recently, much more
attempts about this field have been made by a few researchers. The re-
search by Abbott et al. [16] implied that when ZnO dissolves in DESs, the
oxygen remains attached to the metal center and urea acts as a ligand
with the formula [ZnClO·urea]−. It also shows that most metal oxides
dissolve with no change in the oxidation state of the metal except for
PbO2. Hussey et al. [14] also assumed that after the dissolution of Cu2O
in the melt, the complexes of {[Cu2O·m(NH2)2CO]·nCl−}n− were
generated.
In this paper, for further studying the deposition process of lead from
PbO–ChCl–urea solution with higher current efficiency and lower spe-
cific energy consumption, the effects of temperature and PbO concen-
tration on electrical conductivity and viscosity of PbO–ChCl–urea
solution have been investigated. In addition, the existence form and
complexing mechanism of PbO in ChCl–urea DES were also examined
by ESI-MS and hybrid orbital theory with the aim of explaining the facile
dissolution of PbO in this system.

http://dx.doi.org/10.1016/j.molliq.2014.09.014
0167-7322/© 2014 Elsevier B.V. All rights reserved.
 J. Ru et al. / Journal of Molecular Liquids 199 (2014) 208–214 209

2. Experimental

2.1. Chemicals

All the chemicals used in this work were purchased commercially

with analytical grade (purity N 99.90%) from Chemical Reagent Co.,
Shanghai, China. ChCl (C5H14NOCl) and urea (CO(NH2)) were recrystal-
lized twice and dried under vacuum. PbO was dried under vacuum for
48 h at 353 K.

2.2. Synthesis of ChCl–urea DES

The ChCl–urea DES was synthetized by mixing ChCl and urea (mole
ratio 1:2) together at 353 K until a homogeneous, colorless liquid
formed, as Abbott et al. [16] reported. Then different amounts of PbO
were added into ChCl–urea DES under dry argon atmosphere. The re-
sulted suspension was heated in an oil bath and the accuracy of temper-
ature was ± 1 K. The complete dissolution of PbO was within 4 h
at 353 K.

2.3. Measurement and characterization

The viscosities of PbO–ChCl–urea solution were measured by a vis-

cosity meter (SNB-2 model) from 303 to 353 K and the concentration
of PbO was varied in the range of 10 mM to 120 mM. In the same con-
centration range, the electrical conductivities of PbO–ChCl–urea solu-
tion were measured by a conductivity meter (DDSJ-30A model). The
existence form of PbO in ChCl–urea DES was examined by electrospray
ionization mass spectrometry (ESI-MS, Micromass Q-TOF model). The
FT-IR spectra of ChCl–urea DES and PbO–ChCl–urea solution were re-
corded in KBr medium using a spectrometer (Vertex-70 model).

3. Results and discussion

3.1. Existence form of PbO in ChCl–urea DES

According to recently reported references [12,16], the facile dissolu-

tion of oxides in DESs is a result of the formation of complexes
consisting of metal oxides and urea with the possible incorporation of
chloride as well. In particular, for investigating the existence form of
PbO in ChCl–urea DES, the ESI-MS spectra of ChCl–urea DES and PbO–
ChCl–urea solution in the negative ion mode are shown in Fig. 1. The
peaks are identified and their positions are marked in the figure.
The two groups of peaks at m/z 175.05 and 315.12 correspond to
[C5H14NOCl2]− and [(C5H14NO)2Cl3]−, respectively (Fig. 1a and b).
After PbO dissolution, only a new group of peaks are observed at
about m/z 318.97 (Fig. 1c). The calculated result shows that complex
anions {[PbO∙CO(NH2)2]∙Cl−}− are formed among PbO, urea and Cl−
anions. The complexation reaction may be interpreted as Eq. (1).

 sizes. The larger lobes of the sp3 hybrids are directed towards the four
− − −
PbO þ COðNH2 Þ2 þ Cl → PbO  COðNH2 Þ2  Cl ð1Þ
Urea, in spite of its three coordinating sites (including the carbonyl
oxygen and the two nitrogen atoms), usually acts as a monodentate li-
gand. There will be a preferential binding between Pb2+ ion and car-
bonyl oxygen or nitrogen of urea to form an oxygen–metal bond or a
nitrogen–metal bond. Referring to pertinent literature [20], for the un-
common transition metals (Ta, Os, Ir) and frontier or post-transition
metals (In, Pb, Bi, Po, Te, As, At), urea complexes should exhibit a
metal–oxygen bond, where urea is monodentate. Therefore, it can be in-
ferred that the oxygen atom of urea incorporates directly with Pb2+ ion
in ChCl–urea DES.
In order to explore the complexing mechanism of PbO in ChCl–urea
DES, the space structure of {[PbO∙CO(NH2)2]∙Cl−}− anion is discussed by
hybrid orbital theory [21–23] and the hybrid orbital schematic diagram
of Pb2+ ion in the complex is shown in Fig. 2. The sp3 hybrid orbitals of
Fig. 1. ESI-MS spectra of (a) ChCl-urea DES, (b) the partial magnification of (a), and
(c) PbO–ChCl–urea solution in the negative ion mode.
Pb2+ ion are formed from 6s and three p orbitals, including 6px, 6py and
6pz. These sp3 hybrid orbitals are oblong in shape, like the p orbitals of
which they are partially composed, and have two lobes of opposite
signs. However, unlike the p orbitals, the two lobes are of very different
corners of a tetrahedron. In this new electron configuration, three sp hy-
brid orbitals are all filled with lone pair electrons which are donated by
Cl−, O2− and O atoms of urea respectively. The three bonds can be pic-
tured as forming the base of a trigonal pyramid, and the fourth orbital
containing the lone pair forms the top of the pyramid. Therefore, it is
suggested that three-coordinated complexes of Pb2 + ion are formed
in ChCl–urea DES which is in good agreement with the detection result
of ESI-MS (Fig. 1). To further explain the structure of obtained com-
plexes, Fig. 3 shows the resonance structure of Cl− anion, O2 − anion
and a urea ligand bound to Pb2+ ion via donating lone pair electrons.
The oxidation state of Pb atom does not apparently change in the com-
plexes. Based on the above analysis, the formation of large complex an-
ions leads to the steady existence of Pb2+ ion in the system and this
explains why PbO can be dissolved easily in ChCl–urea DES.
The FT-IR spectra have been used as a powerful tool to verify the
presence of certain functional groups in material identification because
210 J. Ru et al. / Journal of Molecular Liquids 199 (2014) 208–214
Fig. 2. Hybrid orbital schematic diagram of Pb2+ in complex anion {[PbO∙CO(NH2)2]∙Cl−}−.
an individual chemical bond often shows a unique energy adsorption
band [24]. In the present study, the FT-IR spectra of ChCl–urea DES
and PbO–ChCl–urea solution are also performed to gain more informa-
tion about the occurrence state of PbO in this system. As Fig. 4 illustrates,
the dissolution of PbO in ChCl–urea DES gives rise to an intensive peak
at 2156 cm−1, whereas the intensity of other peaks basically un-
changed. Based on literatures [15,25], the similar phenomena are also
observed after the dissolution of ZnO in [Amim]Cl/urea and ZnCl2 in
urea. As is well known, the main factors that influence the peak intensi-
ty of FT-IR spectra are the variation degree of dipole moment in vibra-
tion and energy level transition probability [26]. When PbO is added
into ChCl–urea DES, because of a great difference of electronegativity
between oxygen atom of urea and Pb atom, the formation of the O–Pb
bond will result in dipole moment changing so that a relative enhance-
ment of peak intensity is induced. Moreover, the dipole moment is also
related to the structure symmetric property of groups. In Fig. 2, the gen-
eration of Pb–urea complexes destroys the original symmetry structure
of urea, which makes the peak intensity increasing. Combining the FT-IR
spectra with the ESI-MS data, therefore, it is appropriate to state that the
peak at 2156 cm−1 probably derives from the stretching vibration of
bond generated between Pb2 + and urea in [(PbO ∙CO(NH2)2]∙Cl−]−
anion.
3.2. Viscosity of PbO–ChCl–urea solution
The viscosity of the PbO–ChCl–urea solution is investigated against
temperature and PbO concentration, as shown in Table 1. For observing
the variation of viscosity with experiment conditions clearly, the three-
dimensional plots are shown in Fig. 5. The viscosity decreases
Fig. 3. Resonance structure of the complex anion {[PbO∙CO(NH2)2]∙Cl−}− in ChCl–urea
DES.
remarkably with an increase in temperature. Nevertheless, with in-
creasing PbO concentration, the viscosity decreases firstly and then in-
creases. Besides, temperature has a more significant effect on viscosity
than PbO concentration.
The viscosity of 40 mM PbO + ChCl–urea DES as a function of tem-
perature varying from 308 to 353 K is shown in Fig. 6. The viscosity de-
creases from 307.7 mPa · s at 308 K to 46.3 mPa · s at 353 K. This
indicates that the viscosity has a high sensitivity to temperature in this
solution. The viscosity values are fitted using an Arrhenius model as
shown below [27,28]:
Eη
ln η ¼ ln η0 þ ð2Þ
RT
where η is the viscosity, η0 is a pre-exponential constant, Eη is the acti-
vation energy, R is the gas constant, and T is the temperature in K. The
numerical relationship is obtained with the Origin software and the
plot is shown in Fig. 7. The activation energy is about 35.91 kJ·mol−1.
The viscosity as a function of PbO concentration in the range of 20 to
120 mM is shown in Fig. 8. At constant temperature 308 K, the viscosity
decreases firstly from 314.7 mPa·s at 20 mM to 241.1 mPa·s at 80 mM
and then increases to 286.7 S·m−1 at 120 mM. When the PbO concen-
tration is 90 mM and above, a turbid and viscous solution is formed. It
Fig. 4. FT-IR spectra of (a) ChCl–urea DES and (b) 40 mM PbO + ChCl–urea DES.
 J. Ru et al. / Journal of Molecular Liquids 199 (2014) 208–214 211

Table 1
Effects of temperature and PbO concentration on viscosity of PbO–ChCl–urea solution.

CPbO/mM Viscosity (η/mPa·s)

308 K 313 K 323 K 333 K 343 K 353 K

0 402.8 228.0 105.6 73.8 62.1 53.3

20 314.7 189.1 101.3 71.0 57.9 46.3
40 307.7 181.7 99.7 69.5 55.7 46.3
60 265.9 164.7 91.9 66.8 54.0 41.0
80 241.1 144.3 79.1 56.0 44.8 36.2
100 283.4 164.8 84.4 57.9 45.8 36.8
120 286.7 194.1 123.3 97.8 72.7 56.7

becomes difficult for the further dissolution of PbO into the ChCl–urea
DES. These changes are mainly associated with the existence form of
PbO and the solution composition, which will be discussed in the later
part.
3.3. Electrical conductivity of PbO–ChCl–urea solution
The effects of temperature and PbO concentration on electrical
conductivity of PbO–ChCl–urea solution are studied. The conductivity
values measured are listed in Table 2. In order to observe the variation
of conductivity with experiment conditions clearly, the three-
dimensional plots are shown in Fig. 9. The electrical conductivity in-
creases remarkably with an increase in temperature and this effect is
more pronounced at a higher temperature. However, with increasing
PbO concentration, the electrical conductivity increases firstly and
then decreases. Besides, temperature has a more significant effect on
electrical conductivity than PbO concentration.
3.3.1. Effect of temperature on electrical conductivity
The electrical conductivity of 40 mM PbO + ChCl–urea DES as a
function of temperature varying from 303 to 353 K is shown in Fig. 6.
The electrical conductivity increases from 0.0997 S·m−1 at 303 K to
1.0199 S·m−1 at 353 K. This increase in conductivity can be attributed
to the fact that high temperatures enhance the migration rate of ions
in the solution [29]. In the region of low temperature, the migration
rate of ions is very slow due to strong ion–ion interactions. With rising
temperature, the viscosity decreases and then the migration rate of
ions speeds up remarkably, and this is reflected in the increase of
conductivity.
In addition, as observed in the past for many DESs and related liquids
[30–32], the dependence of electrical conductivity on temperature is
nonlinear. This implies that the ChCl–urea, like most DESs, is a glass-
forming liquid. In this case, the relationship between temperature and
Fig. 6. Viscosity and electrical conductivity of PbO–ChCl–urea solution as a function of
temperature T − T0 (T0 = 303 K).
electrical conductivity of PbO–ChCl–urea solution can be represented
with the Kohlraush empirical equation:
h i
2
κ ¼ κ 0 1 þ AðT−T 0 Þ þ BðT−T 0 Þ ð3Þ
where κ is specific conductivity in S·m−1, T is the temperature in K, κ0 is
the specific conductivity at T0 = 303 K, and A and B are temperature co-
efficients. The numerical relationship is obtained with the Origin soft-
ware as
h i
−3 2
κ ¼ 0:1014 1 þ 0:0903ðT−T 0 Þ þ 1:7487  10 ðT−T 0 Þ : ð4Þ
The fitting curve is shown in Fig. 6. The correlation coefficient deter-
mined by the least-squares method is 0.99 which indicates that Eq. (4)
is in good agreement with the experimental data.
3.3.2. Effect of PbO concentration on electrical conductivity
The electrical conductivity as a function of PbO concentration in the
range of 10 to 120 mM is shown in Fig. 10. At a constant temperature of
343 K, the conductivity increases firstly from 0.6340 S·m−1 at 10 mM to
0.7862 S·m− 1 at 80 mM and then decreases to 0.6970 S·m− 1 at
120 mM, indicating that there is a close relationship between the

Fig. 7. Plot of logarithm of the viscosity (ln η) against the reciprocal value of the absolute
Fig. 5. Three-dimensional plot of viscosity: effects of temperature and PbO concentration. temperature (T−1).
212 J. Ru et al. / Journal of Molecular Liquids 199 (2014) 208–214

Fig. 9. Three-dimensional plot of electrical conductivity: effects of temperature and PbO

concentration.

Fig. 8. Viscosity of PbO–ChCl–urea solution as a function of PbO concentration at different
temperatures.
conductivity and PbO concentration. The conductivity of a liquid salt can
be described as below [33]
eF X 2
κ¼ jz i j c i ð5Þ
6πηr i
where κ is the electrical conductivity in S·m− 1; e is the electronic
charge, 1.6022 × 10−19C; F is the Faraday constant; zi is the number
of charges; ci is the molar concentration of charged body in mol · m−3;
η is the viscosity of solution in Pa·s; r is the radius of charged body in
m; and π is the circumference ratio. The conductivity can thus, to a rea-
sonable degree of approximation, be related to its molar concentration,
viscosity, the number of charges, and radius of charged body, following
Eq. (5).
According to the above ESI-MS discussion, the existence of
[C5H14NOCl2]− and [(C5H14NO)2Cl3]− anions illustrates that oligomers
are formed by Ch+ (C5H14NO+) cation and Cl− anion without the addi-
tion of PbO in ChCl–urea DES (pattern I). The oligomer is a kind of chain
polymer composed of cations alternating with anions. Its chain length
depends on many factors mainly involving ionic species, strength of hy-
drogen bonding and interactions among ions. Although the interaction
between anion and cation is week, it is sufficient to make ions lose inde-
pendence then form positive, negative or neutral oligomers. In particu-
lar, the smaller the volume of the ions is, the higher the oligomerization
degree and the longer the chain of the oligomers are. In ChCl–urea DES,
owing to the small volume of the Cl− ion and strong association effects
between Ch+ and Cl−, the oligomers with high oligomerization degree
are produced, and this leads to the reduction of the charge number and
the increasing of viscosity. Therefore, the electrical conductivity of
ChCl–urea DES is relatively low.
With the content of PbO increased, the electrical conductivity
increases progressively at first and this change is more significant at a
higher temperature (Fig. 10). The viscosity has an opposite change
trend compared with the electrical conductivity as mentioned
above. The reason can be explained as follows. The complex anions
{[PbO∙CO(NH2)2]∙Cl−}− are formed with the dissolution of PbO in
ChCl–urea DES, and the concentration of which is increased while that
of Cl− ion and urea are both decreased, as shown in Fig. 11. Because
the volume of the complex is larger than that of Cl− anion, low oligo-
merization degree polymers (patterns II and III) are formed so that the
viscosity decreases and the electrical conductivity has an increasing
trend along the rising charge number accordingly. However, in the re-
gion of CPbO N 80 mM, the conductivity decreases remarkably with
PbO concentration. This decrease can be attributed to the fact that
large radius of the complexes leads to the decreasing mobility of the so-
lution and then the viscosity increases. When the change in mobility
and viscosity plays a dominant role compared to the increase in the
charge number, the reduction in conductivity is induced. It is noticeable
that there is a peak conductivity point at 80 mM. Therefore, a higher
temperature and a suitable PbO concentration, which can enhance the
conductivity of solution, are very necessary for the subsequent electro-
deposition of lead from PbO–ChCl–urea solution to increase current
efficiency.

Table 2
Effects of temperature and PbO concentration on electrical conductivity of PbO–ChCl–urea
solution.

CPbO/mM Electrical conductivity (κ × 103/S·m−1)

303 K 313 K 323 K 333 K 343 K 353 K

0 35.3 111.5 264.9 448.5 622.6 820.9

20 67.5 155.9 315.8 493.3 687.7 922.7
40 99.7 213.3 359.9 536.6 742.9 1019.9
60 118.0 233.7 383.4 555.0 774.5 1068.0
80 124.2 240.7 391.9 557.9 786.2 1121.5
100 95.4 194.5 346.5 519.1 733.9 1047.1
Fig. 10. Electrical conductivity of PbO–ChCl–urea solution as a function of PbO concentra-
120 67.5 169.4 316.4 493.1 697.0 970.2
tion at different temperatures.
 J. Ru et al. / Journal of Molecular Liquids 199 (2014) 208–214 213

Fig. 11. The concentration of Ch+ cation, Cl− anion, urea and {[PbO∙CO(NH2)2]∙Cl−}−
anion as a function of PbO concentration in ChCl–urea DES.
Fig. 12. Experimental and estimated κ values obtained by Eq. (6).

The numerical relationship between electrical conductivity and PbO PbO concentration, the viscosity decreases firstly and then
concentration is obtained with the Origin software as Eq. (6), where A, B increases.
and D are concentration coefficients and they are listed in Table 3. The (4) The electrical conductivity of PbO–ChCl–urea solution increases
experimental and estimated conductivity values are illustrated in with the increasing of temperature and the relationship is
Fig. 12. The slight wave shape around the ideal 45° line indicates that obtained.
this estimation is in reasonable agreement. In order to observe the var- (5) The electrical conductivity increases firstly and then decreases
iation of concentration coefficients with temperature, values of A, B and with PbO concentration which is influenced strongly by the for-
D as a function of temperature are shown in Fig. 13. With the raising of mation of PbO-containing complexes and oligomers. In the
temperature, the variation of these coefficients are becoming more and meantime, the relationship between conductivity and PbO con-
more conspicuous, especially those of A and B. The primary reason centration is summarized.
is that higher temperature facilitates Pb2 + ion binding to Cl− anion,
O2− anion and urea to form complexes, thus a remarkable change in
electrical conductivity occurred and is reflected in the variation of con-
Acknowledgments
centration coefficients.
The authors acknowledge the financial support of the National Natural
2
κ ¼ AC PbO þ BC PbO þ D ð6Þ Science Foundation of China (Project No. 21263007, 51274108), the
National Basic Research Program of China (Project No. 2014CB643404)
and Applied Basic Research Foundation of Yunnan province (Project
4. Conclusions No. 2011FA009). The authors also thank to the Institute of Process
Engineering, Chinese Academy of Sciences for providing ESI-MS
(1) ESI-MS analysis indicates that the complex anions analysis.
{[PbO∙CO(NH2)2]∙Cl−}− are formed among Cl−, O2 − and urea
in PbO–ChCl–urea solution.
(2) Three-coordinated complexes {[PbO∙CO(NH2)2]∙Cl−}− are
formed through sp3 hybrid orbitals of Pb2+ ion and three sp hy-
brid orbitals are all filled with lone pair electrons which are do-
nated by Cl−, O2− and O atoms of urea respectively.
(3) The viscosity of PbO–ChCl–urea solution decreases remarkably
with an increase in temperature. Nevertheless, with increasing

Table 3
Effects of temperature on concentration coefficients A, B and D.

T/K A × 105 B × 103 D

303 −1.92 2.64 0.03

308 −2.10 2.75 0.05
313 −2.21 2.87 0.10
318 −2.30 2.91 0.17
323 −2.40 3.10 0.26
328 −2.50 3.33 0.35
333 −2.60 3.44 0.44
338 −2.80 3.83 0.52
343 −3.36 4.70 0.61
348 −4.11 5.99 0.70
353 −5.36 7.86 0.80
Fig. 13. Concentration coefficients A, B and D as a function of temperature.
214 J. Ru et al. / Journal of Molecular Liquids 199 (2014) 208–214
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