Solvent Extraction Research and Development, Japan, Vol.

21, No 1, 71 76 (2014)

Notes



Salting-out Phase Separation System of WaterTetrahydrofuran
with Co-using 1-Butyl-3-methylimidazolium Chloride and Sodium Chloride
for Possible Extraction Separation of Chloro-complexes

Naoki HIRAYAMA,
1,2
* Takaaki HIGO,
3
and Hisanori IMURA
4

1
Department of Chemistry, Faculty of Science, Toho University,
Miyama 2-2-1, Funabashi 274-8510, J apan
2
Research Center for Materials with Integrated Properties, Toho University,
Miyama 2-2-1, Funabashi 274-8510, J apan
3
Division of Material Chemistry, Graduate School of Natural Science and Technology,
Kanazawa University, Kakuma-machi, Kanazawa 920-1192, J apan
4
Division of Material Sciences, Graduate School of Natural Science and Technology,
Kanazawa University, Kakuma-machi, Kanazawa 920-1192, J apan
(Received September 1, 2013; Accepted October 2, 2013)

The salting-out phase separation behavior of the watertetrahydrofuran (THF) homogeneous system with
co-adding a hydrophilic ionic liquid, 1-butyl-3-methylimidazolium chloride ([C
4
mim]Cl), and NaCl was
investigated. In the waterTHF/[C
4
mim]Cl biphasic system, the lower phase showed a relatively large
volume and low polarity compared with that in the waterTHF/NaCl system, because of the coexistence of
THF and [C
4
mim]Cl. In the waterTHF/[C
4
mim]ClNaCl mixed salting-out agent system, the lower phase
polarity depended on the composition of the salting-out agents. Furthermore, the distribution behavior of
Fe(III) and Zn(II)chloro complexes in the mixed salting-out agent system was investigated to show the
potential for application of the system for the extraction separation of metals as their chloro-complexes.


1. Introduction
In solvent extraction, the distribution behavior of solutes depends mainly on the difference in the
polarities of the two phases. Hydrophobic organic solvents have relatively low polarities and, therefore, it is
clearly not easy to extract polar or ionic solutes from the aqueous phase into the extraction (organic) phase
without the use of a hydrophobic reagent.
Although high-polar organic solvents such as lower alcohols, acetonitrile and tetrahydrofuran (THF)
are water-miscible, it is well known that adding large amount of salts, including inorganic chlorides [13]
and tetramethylammonium chloride [4], to the waterhigh-polar organic solvent mixture results in phase
separation based on salting-out. Although the aqueous biphasic system has some superiority in the
extraction of polar or ionic species, the combination of organic solvent and salt to form the biphasic system
is limited.
Recently, use of hydrophobic ionic liquids (ILs) as the extraction phase in solvent extraction has
widely been investigated [57]. ILs are salts with low melting points and can act as high-polar solvents.
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Some researchers reported that waterhydrophilic IL mixtures can form immiscible separate phases in the
presence of some inorganic salts [8]. In contrast, hydrophilic ILs can be also used as salting-out agents. In
previous work, Hu et al. reported the phase separation behavior of waterTHF using an atypical IL,
1-(2-hydroxyethyl)-3-methylimidazolium chloride [9]. Recently, we reported preliminary research on the
possible use of more popular hydrophilic IL, 1-butyl-3-methylimidazolium chloride ([C
4
mim]Cl) as the
salting-out phase separation agent for the waterTHF system as a rapid communication [10]. Although pure
[C
4
mim]Cl is solid at room temperature, it liquefies with a small amount of water and is miscible to water
at arbitrary ratio. In other words, high concentration aqueous solutions of [C
4
mim]Cl can be easily
prepared.
In this paper, we report on the possible use of [C
4
mim]Cl together with NaCl as salting-out phase
separation agents. Concretely, phase separation behavior in the waterTHF/[C
4
mim]Cl system and that in
the waterTHF/[C
4
mim]ClNaCl mixed salting-out agent system were investigated. Furthermore, the
possible application of the latter system for the extraction separation of metals as their chloro-complexes
was investigated.

2. Experimental
2.1 Apparatus
The IL, [C
4
mim]Cl, was synthesized from 1-methylimidazole and 1-chlorobutane according to
reported procedure [11]. Other chemicals and solvents were of reagent-grade and were used without further
purification. Distilled deionized water was used throughout.
The absorption spectra of the solutions were recorded on a J ASCO U-best 30 UV-Visible
spectrophotometer with a 1.0 cm quartz cell. The concentrations of metals, iron and zinc, in solution were
determined using a Hitachi Z-6100 polarized Zeeman atomic absorption spectrometer.

2.2 Evaluation of salting-out phase separation behavior
The salting-out phase separation behavior was investigated at 25C as follows. Into a stoppered
graduated cylinder, 2.0 cm
3
(2.0 g, 0.11 mol) of water, 3.4 cm
3
(3.0 g, 0.042 mol) of THF (or other
hydrophilic organic solvent) and weighed amount of the salting-out agents ([C
4
mim]Cl and/or NaCl) were
added. After mixing using a Vortex mixer to dissolve the agents completely, the cylinder was left standing
for several minutes until completion of the phase separation, and the volume of each phase (V
upper
and
V
lower
) was measured.
The polarity of each phase was evaluated using the E
T
N
value [12,13]. The value was determined
from
max
for Reichardts Dye (2,6-diphenyl-4-[(2,4,6-triphenylpyridinium)-1-yl]phenolate) as follows:
E
T
N

{28591/ (
max
/ nm)}30.7
32.4
(1)
where E
T
N
(water) and E
T
N
(tetramethylsilane) are defined as 1 and 0, respectively.

2.3 Distribution of metals
The distribution behavior of Fe(III) and Zn(II) was investigated at 25C as follows. Into a stoppered
centrifuge tube, 2.0 cm
3
of 2.0 mol dm
3
HNO
3
containing 1.0 mg cm
3
of metal, 3.4 cm
3
of THF and 8.5
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mmol in total of the salting-out agents ([C
4
mim]Cl and/or NaCl) were added. The tube was shaken for 10
min using a mechanical shaker. After the two phases were completely separated by centrifugation, their
volumes were measured and the concentration of the metal in each phase (C
upper
and C
lower
) was determined
using FAAS after suitable dilution. The distribution ratios (D, upper phase/lower phase) and extractabilities
(%E, into the upper phase) for the metals were calculated using the following equations:
D
C
upper
C
lower
(2)
%E 100
C
upper
V
upper
C
upper
V
upper
C
lower
V
lower
(3)

3. Results and Discussion
3.1 Preliminary research
At first, we examined whether the addition of [C
4
mim]Cl results in salting-out phase separation for
several waterhydrophilic organic solvent systems. The hydrophilic solvents used were methanol (E
T
N
=
0.762 [13]), ethanol (0.654), 2-propanol (0.546), acetonitrile (0.460), acetone (0.355), pyridine (0.302) and
THF (0.207). When NaCl was used as the salting-out agent, all the solvents except for ethanol showed
phase separation. In contrast, when using [C
4
mim]Cl, only acetone and THF showed phase separation.
Although [C
4
mim]Cl is solid at room temperature, many ILs have similar polarities to hydrophilic alcohols.
(The E
T
N
values for general C
4
mim
+
-type ILs range from 0.64 to 0.68 [14].) The above-mentioned results
seem to be consistent with the nature of ILs. Since THF showed a higher phase-separation ability, we
selected the waterTHF system.
Dissolution of Reichardts Dye is necessary to obtain the E
T
N
value for the solvent. In the waterTHF
mixture containing more than 7 mol % THF, Reichardts Dye was soluble. For the 7 mol % THF mixture,
the E
T
N
value was determined as 0.783. From these results, it was found that the E
T
N
value for the
Reichardts Dye-insoluble mixture can be estimated as >ca. 0.8.

3.2 Phase separation for the waterTHF/[C
4
mim]Cl system
The phase separation behavior for a mixture of 2.0 cm
3
of water and 3.4 cm
3
of THF on adding
different amounts of [C
4
mim]Cl or NaCl is shown in Figure 1, with the obtained E
T
N
value for each of the
separated phases [10] (1 mmol =0.059 g for NaCl, 0.175 g for [C
4
mim]Cl). The minimum amounts of
[C
4
mim]Cl and NaCl for the phase separation were ca. 3 mmol and ca. 0.8 mmol, respectively.
In the conventional NaCl system, the upper (THF-rich) phase volume (V
upper
) was similar to the
volume of THF used and the lower (water-rich) phase volume (V
lower
) was similar to that of water. In the
[C
4
mim]Cl system, in contrast, V
upper
was very small and V
lower
was relatively large. Although the two
systems showed similar behavior in upper phase polarity, the lower phase in the [C
4
mim]Cl system showed
a lower polarity than that in the NaCl system. Namely, the difference in the polarity between the two phases
in the [C
4
mim]Cl system was smaller than that in the NaCl system. From these results, it was suggested
that the low polarity of the lower phase in the [C
4
mim]Cl system arises because of THF and [C
4
mim]Cl
remained in the phase. In other words, [C
4
mim]Cl acts in the biphasic system not only as a salting-out
- 73 -


agent but also as a component of the mixed-solvent. (Actually, the V
upper
+V
lower
value increased with
adding [C
4
mim]Cl.)

3.3 Phase separation for the waterTHF/
[C
4
mim]ClNaCl mixed system
Although the upper phase polarity depends
on the amount of the salting-out agent to some
extent, the lower phase polarity shows a quite
low dependency, as seen in Figure 1. Therefore,
simultaneous use of a pair of salting-out agents,
[C
4
mim]Cl and NaCl, was investigated.
Figure 2(a) shows the phase separation
behavior for a mixture of 2.0 cm
3
of water and
3.4 cm
3
of THF on adding 8.5 mmol of
[C
4
mim]ClNaCl mixed salting-out agent at
different mole fractions. The volumes of both
phases varied linearly with the increase in the
[C
4
mim]Cl mole fraction. Figure 2(b) shows the
obtained E
T
N
value for each of the phases. This
suggests that the lower phase polarity changes
appreciably between 50 mol % and 75 mol % of
[C
4
mim]Cl fraction. (At a [C
4
mim]Cl fraction <

Figure 1. Effect of added amount of salting-out agent on volume (left) and E
T
N
(right) of each
phase in the waterTHF/[C
4
mim]Cl (circle) and waterTHF/NaCl (diamond) aqueous
biphasic systems [10]. Initial mixture; 2.0 cm
3
of water and 3.4 cm
3
of THF. Dotted lines
(left) show the initial THF volume (upper) and the initial water volume (lower).
0
2
4
6
V
u
p
p
e
r

(
c
m
3
)
0
2
4
6
0 2 4 6 8 10 12
V
l
o
w
e
r

(
c
m
3
)
[C
4
mim]Cl or NaCl (mmol)
0.3
0.4
0.5
0.6
0.7
U
p
p
e
r

p
h
a
s
e

E
T
N
0.3
0.4
0.5
0.6
0.7
0 2 4 6 8 10 12
L
o
w
e
r

p
h
a
s
e

E
T
N
[C
4
mim]Cl or NaCl (mmol)
NaCl
[C
4
mim]Cl
[C
4
mim]Cl
[C
4
mim]Cl
[C
4
mim]Cl
NaCl
NaCl
NaCl
L
o
w
e
r

p
h
a
s
e

E
T
N

U
p
p
e
r

p
h
a
s
e

E
T
N

V
l
o
w
e
r

V
u
p
p
e
r

Figure 2. Effect of the salting-out agent composi-
tion on the volume (a) and E
T
N
(b) of each phase
in the waterTHF/[C
4
mim]ClNaCl aqueous
biphasic system. Broken lines shown in (a) were
obtained by the linear least-square fitting. Initial
mixture; 2.0 cm
3
of water and 3.4 cm
3
of THF.
Total amount of the salting-out agents; 8.5 mmol.
0
2
4
6
V
o
l
u
m
e

(
c
m
3
)
0.3
0.4
0.5
0.6
0.7
0 20 40 60 80 100
E
T
N
[C
4
mim]Cl fraction (mol %)
Upper phase
Upper phase
Lower phase
Lower phase
(b)
(a)
E
T
N

- 74 -


50 %, E
T
N
value was estimated as >ca. 0.8 as mentioned in Section 3.1.) In the mixed salting-out agent
system, the difference in the two phase polarities varied as the composition of the agents was varied.

3.4 Distribution behavior of chloro-complexes in the waterTHF/[C
4
mim]ClNaCl mixed system
In the recent communication [10], we reported that the distribution of a neutral molecule in the
mixed salting-out agent system changes with the composition, when using Thymol Blue as a probe.
Furthermore, in the waterTHF/[C
4
mim]ClNaCl mixed system, the polarity of both phases can be
controlled without changing the added amount of Cl

. Therefore, the distribution behavior of chloro-

complexes in the biphasic system was investigated with using Fe(III) and Zn(II) as probes. (To avoid their
hydrolysis, HNO
3
-acidic condition was selected.)
As is well known, many metal cations
form stable chloro-complexes in the presence of
high amounts of Cl

. In the present experimental

conditions, for example, it is estimated that
Fe(III) and Zn(II) forms mainly cationic FeCl
2
+

or nonionic FeCl
3
species, and anionic ZnCl
3

or
ZnCl
4
2
species, respectively. (In aqueous
solution, log
1
=1.48, log
2
=2.13, log
3
=
1.99 and log
4
=0.01 for Fe
3+
, and log
1
=0.43,
log
2
=0.61, log
3
=0.53 and log
4
=0.20 for
Zn
2+
[15].) Although the distribution behavior of
Cl

was not investigated in detail, it is considered

that these metals not only exist as the
chloro-complexes in the lower phase but also are
extracted as the same forms into the upper phase.
Figure 3 shows log D and %E for Fe(III) and
Zn(II) as a function of the mole fraction of
[C
4
mim]Cl for a fixed total amount of the
salting-out agents in the waterTHF/[C
4
mim]Cl
NaCl aqueous biphasic system. In the water
THF/[C
4
mim]Cl and waterTHF/NaCl single
salting-out agent systems, in addition, the
amount of the salt hardly affected the metal distribution. (For example, the log D value for Fe(III) in the
waterTHF/[C
4
mim]Cl system ranged from 0.55 to 0.60 on adding 8.014.0 mmol of [C
4
mim]Cl, and that
for Zn(II) in the waterTHF/NaCl system ranged from 0.48 to 0.51 on adding 4.08.5 mmol of NaCl.)
Namely, the distribution was controlled by changing the [C
4
mim]Cl:NaCl ratio under a fixed salt amount,
and the change in the lower phase polarity seems to contribute mainly to this behavior. From these results,
it was concluded that the mixed salting-out phase separation system using a hydrophilic IL can be a useful
tool in extraction separation chemistry.


Figure 3. The logarithmic distribution ratio (log D,
upper phase/lower phase (a)) and extractability
(%E, into the upper phase, (b)) for Fe(III)
(triangle) and Zn(II) (square) in the waterTHF/
[C
4
mim]ClNaCl aqueous biphasic system. Initial
mixture; 2.0 cm
3
of 2.0 mol dm
3
HNO
3
and 3.4
cm
3
of THF. Total amount of the salting-out
agents; 8.5 mmol.
-2
-1
0
1
2
3
l
o
g

D
Fe(III)
Zn(II)
0
50
100
0 20 40 60 80 100
%
E
[C
4
mim]Cl fraction (mol %)
(b)
(a)
Zn(II)
Fe(III)
l
o
g

D

%
E

- 75 -


Acknowledgements
This study was financially supported in part by a Grant-in-Aid for Scientific Research (No.
22550071) from the J apan Society for the Promotion of Science, MEXTSupported Program for the
Strategic Research Foundation at Private Universities (20122016) from the Ministry of Education, Culture,
Sports, Science and Technology, J apan, and the Basic Research Fund from Faculty of Science, Toho
University.

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