Separation and Purification Technology 72 (2010) 70–76

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Separation and Purification Technology

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Ionic liquid extraction of heavy metal ions by 2-aminothiophenol in

1-butyl-3-methylimidazolium hexafluorophosphate and their
association constants
Ratthaya Lertlapwasin, Nakara Bhawawet, Apichat Imyim, Saowarux Fuangswasdi ∗
Department of Chemistry, Faculty of Science, Chulalongkorn University, Phayathai Road, Pathumwan, Bangkok 10330, Thailand

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

Article history: The ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate, [BMIM]PF6 , was synthesized and
Received 17 August 2009 characterized by Fourier transform infrared spectroscopy and nuclear magnetic resonance spectroscopy.
Received in revised form The optimum conditions for the extraction of Ni2+ , Cu2+ and Pb2+ in water by liquid–liquid extraction
30 December 2009
method were investigated using the synthetic ionic liquid combined with 2-aminothiophenol ligand.
Accepted 8 January 2010
The results showed that while the optimum pH for the extraction of Ni2+ and Pb2+ was 4–6 and 5, respec-
tively; the extraction of Cu2+ was independent of the pH of solution. The extraction equilibria of Ni2+ ,
Keywords:
Cu2+ and Pb2+ were reached within 120, 30 and 30 min, respectively. The existence of sodium, calcium,
Ionic liquid
Liquid–liquid extraction
magnesium, sulfate and chloride ions did not significantly affect the extraction efficiency of all metal
2-Aminothiophenol ions. The stoichiometries of complexes between Ni2+ , Cu2+ and Pb2+ and the ligand are 1:3, 1:2 and 1:2,
Heavy metal ions respectively. The extracted Ni2+ in ionic liquid phase could be back-transferred into 3% H2 O2 in 0.5 M
Association constant HNO3 at 20 min of contact time and the extracted Cu2+ and Pb2+ could be stripped with 1 M HNO3 at the
contact time of 20 and 10 min, respectively, with the percentage stripping higher than 95%. The extraction
efficiency of all metal ions with the ligand in the ionic liquid was higher than that obtained in chloroform
using the same conditions. The association constants of complexes between Ni2+ and Pb2+ and the ligand
in ionic liquid are 2.26 × 107 and 2.97 × 102 , respectively.
© 2010 Elsevier B.V. All rights reserved.

1. Introduction
The environmental damage is the global problem in the present
days and many organizations are alert to solve it. Some of the
concerning environmental issues are green house effect, water–air
pollution and hazardous waste generation of which one major
cause is wastewater containing heavy metal ions. A lot of wastew-
ater is disposed to the environment as a result of the growing
economy, therefore its treatment is necessary especially to min-
imize the amount of heavy metals.
A liquid–liquid extraction (LLE) is one of the efficient techniques
to separate and concentrate metal ions from industrial wastewater.
However, traditional LLE involves the use of organic solvents which
generally are toxic and hazardous to organisms and environment.
The focus of recent researches thus has been on the replacement of
traditional organic solvents by alternative green ones such as ionic
liquids.
∗ Corresponding author. Tel.: +66 2 218 7640; fax: +66 2 254 1309.
E-mail addresses: iapichat@chula.ac.th (A. Imyim), saowarux.f@chula.ac.th
(S. Fuangswasdi).
Ionic liquids (ILs) are eutectic molten salts consisting of bulky
asymmetry organic cation and either organic or inorganic anion
whose melting point is below 100 ◦ C. More specifically, if their
melting point is below room temperature, they are known as room
temperature ionic liquids (RTILs). Their unique properties such as
negligible volatility, thermal stability and non-flammability have
been accepted as a new green solvent. Because of this friendly
environment perception, they have been increasingly investigated
worldwide as alternative reaction media to replace traditional
organic solvents in organic syntheses [1–3], catalytic reactions
[2–6], electrochemical applications [7–9], separation [10–15], bio-
chemistry [3,16,17] and material engineering [18]. Rogers and
collaborators were first to propose utilization of ionic liquid for LLE
processing in the study of substituted-benzene derivatives parti-
tioning between water and [BMIM]PF6 [19]. It was reported that
ionic liquids may be suitable for replacement of organic solvents.
Subsequently, the utilization of dye thymol blue indicator in the
reversible pH-dependent liquid–liquid partitioning of the system
containing IL was investigated [20].
The differences in solvent behavior of ionic liquids, espe-
cially hydrophobic ones, and conventional organic solvents
have been manifested. Large distribution coefficients for the
extraction of metal ions from aqueous solution to ionic liq-

1383-5866/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.seppur.2010.01.004
 R. Lertlapwasin et al. / Separation and Purification Technology 72 (2010) 70–76
uid containing complexing extractants have been observed.
Dai et al. reported a very highly efficient procedure for the
extraction of a fission product, Sr(NO3 )2 , from aqueous phase
into disubstituted imidazolium-based hexafluorophosphates and
bis(trifluoromethyl)sulfonylamides ionic liquids by dicyclohexano-
18-crown-6 [21]. Visser et al. studied the extraction of alkaline
and alkaline earth metal ions from aqueous solution using crown
ethers such as 18-crown-6, 4,4 -(5 )-di-(tertbutylcyclohexano)-
18-crown-6 and dicyclohexano-18-crown-6 in room temperature
ionic liquid 1-alkyl-3-methylimidazolium hexafluorophosphate
([Cn MIM]PF6 , n = 4, 6, 8) [12]. The extraction of heavy metals, Cd2+ ,
Co2+ , Ni2+ and Fe2+ , to [Cn MIM]PF6 (n = 4, 6) using both organic and
inorganic anion extractants was studied [22].
Chelating agent or organic extractant is an important part when
used in coupling with organic solvent to extract metal ions from
water. The extraction efficiency and selectivity can be affected by
size of the chelate ring and type of its donor atoms, oxidation state
and size of the metal ion, and pH of the solvent system [23]. 2-
Aminothiophenol is a bidentate ligand containing nitrogen and
sulfur atoms as active sites for effective coordination with metal
ions. It is also able to act as monoanion and dianion by depro-
tonation of the thio- and amino-groups [24–26] and form charge
transfer complex [27].
In this research, the synthetic room temperature ionic liquid, 1-
butyl-3-methylimidazolium hexafluorophosphate combined with
2-aminothiophenol ligand was used for the extraction of Ni2+ , Cu2+
and Pb2+ in water. The optimum condition of metal extraction and
stripping was studied and the association constant between the
ligand and each metal ion in ionic liquid was calculated.
2. Experimental
2.1. Apparatus
Infrared spectra were recorded on a Fourier transform infrared
spectrometer (FT-IR) model 410 (Nicolet Impact) with the neat
film in NaCl plate technique. NMR spectra of ionic liquids in CDCl3
were recorded on a nuclear magnetic resonance spectrometer
(NMR) model Varian Mercury + 400. A mechanical shaker model
SA-31 (Yamato shaker) was used for agitation of solution. pH mea-
surements were made on a digital pH meter (Hanna instruments
Model pH211). A flame atomic absorption spectrometer (FAAS)
model AAnalyst 100 (PerkinElmer) was used for the determination
of metal concentration using an air–acetylene flame. The instru-
mental parameters were as follows: wavelengths 232.0, 324.8
and 283.3 nm with the lamp current 25, 15 and 10 mA for Ni,
Cu and Pb, respectively, slit width 0.2 nm for Ni and 0.7 for Cu
and Pb.
2.2. Materials and reagents
All reagents and solvents were of standard analytical grade and
used without further purification. De-ionized (DI) water whose
conductivity was less than 4 ␮S cm−1 was obtained from cation and
anion exchange resin columns.
2.3. Synthesis of ionic liquid 1-butyl-3-methylimidazolium
hexafluorophosphate ([BMIM]PF6 )
The ionic liquid [BMIM]PF6 was synthesized from 1-butyl-3-
methylimidazolium chloride ([BMIM]Cl) and hexafluorophospho-
ric acid as previously reported [28]. The synthetic [BMIM]PF6 was
characterized with 1 H NMR (CDCl3 ) and infrared spectroscopy and
compared to the starting material and the commercial [BMIM]PF6 .
71
2.4. Liquid–liquid extraction of metal ions in ionic liquid (IL) or
chloroform
The effects of extraction time and pH of solution were performed
in the same manner. Metal ion extractions were carried out in LLE
tube at 25.0 ± 0.01 ◦ C by the addition of 5.00 mL of metal solu-
tion (typical concentration 1 mM) to 1.00 mL of 2-aminothiophenol
(typical concentration 10 mM) in [BMIM]PF6 . The tube was shaken
at optimum extraction time for each metal ion (180 min for
Ni(NO3 )2 and 30 min for Cu(NO3 )2 and Pb(NO3 )2 ), and then cen-
trifuged for 5 min to completely separate the two phases. (Note that
the preliminary extractions were investigated by employing metal
solution at 5 mg L−1 .) Nitrate salts were selected due to their great
solubility in water, in addition nitrate ions should not interfere
the extraction and the determination by FAAS. The upper aqueous
phase was taken out to measure the remaining metal ion concentra-
tion by FAAS. The studies of interfering ions (Na+ , Ca2+ , Mg2+ , SO4 2− ,
Cl− ), extraction equilibria and slope analysis were performed by
varying the concentration of species of interest at optimum condi-
tion. Metal and proton distributions were conducted using solvents
saturated with the other phase. All experiments were done at least
in triplicates.
The back-transfer efficiency was studied by adding 5.00 mL of
stripping solution to the extracted IL phase. After shaking for 10,
20, 30, and 60 min and centrifuging, the upper stripping phase was
collected to determine the metal concentration.
The extraction efficiency of metal was represented in terms of
percentage extraction (%E) as defined in Eq. (1), and distribution
coefficient for extraction or the ratio of metal species in ionic liq-
uid, presumably in the form of complex, to that in aqueous can be
calculated from Eq. (2).
(Ci )aq − (Cf )aq
%E = × 100 (1)
(Ci )aq
(Ci )aq − (Cf )aq volume of aqueous phase
D= × (2)
(Cf )aq volume of IL phase
where (Ci )aq and (Cf )aq are the concentrations of metal ion in aque-
ous phase before and after extraction (mM), respectively.
3. Results and discussion
3.1. Effect of pH on metal extraction
The preliminary extractions of Ni2+ , Cu2+ and Pb2+ at 5 mg L−1
by 2-aminothiophenol at various pHs showed that the percentage
extraction of Ni2+ and Cu2+ could be attained at around 100% at pH
above 4 and 3, respectively, while that of Pb2+ gradually increased
to 80% when pH increased from 3 to 6 (Fig. 1). However, these
high values of percentage extraction obtained were not suitable
to investigate the extraction mechanism and higher metal ion con-
centrations (1 mM) were employed for further studies.
Fig. 1 also shows the comparison of extraction of metal ions
at 1 mM from aqueous phase to ionic liquid and to chloroform as
a function of pH. The higher percentage extraction in [BMIM]PF6
than in chloroform indicates that ionic liquid is a better receptor
phase for metal removal and the observation agrees with the data
in the literature [10,14,15]. Both systems showed similar extraction
behaviors, i.e. extraction of Ni2+ and Pb2+ depended on the pH of
solution. The optimum pHs for the extraction are at pH ≥4 for Ni2+
and pH 5 for Pb2+ . In contrast, extraction of Cu2+ was independent
of the pH. Moreover, the dark blue complex in ionic liquid phase
was observed. This complex might be the result of oxidation of the
ligand by Cu2+ ion to form electron transfer complex as reported
by Larkworthy et al. [25]. To elucidate this hypothesis, electron
spinning resonance spectroscopy (ESR) was used to identify the
72 R. Lertlapwasin et al. / Separation and Purification Technology 72 (2010) 70–76

Fig. 2. Plots of log D vs pH of solution after extraction ([L]IL = 10 mM, 1.0 mL,
[M] = 1.0 mM, 5.0 mL, 25 ◦ C, n = 3).

overall extraction reaction,

Mn+ (n+y−2b)+
aq + bH2 LIL  (MLb H2b−y )IL + yH+
aq (3)

yielding the extraction equilibrium constant Kex (complex’s charge

omitted):
y
[MLb H2b−y ]IL [H+ ]aq
Kex =
[Mn+ ]aq [H2 L]bIL

Substitution of Kex gives D:

Kex [H2 L]bIL

D= y
[H+ ]aq

Thus, the following linear relationship can be obtained:

log D = log Kex + b log [H2 L]IL − y log [H+ ]aq (4)
−
As previously reported that PF6 could decompose to HF and
PO4 3− in the presence of water or nitric acid in ionic liquid [12,28],
the pH of blank extraction was taken into account by plotting the
values of log D against pH which was the difference in pH val-
ues of extracted metal solution and blank extraction (Fig. 2). It was
found from the slopes that the number of released protons from
2-aminothiophenol was close to 2 for the cases of Ni2+ and Pb2+
(slopes y = 1.769 and 2.373, respectively), whereas insignificant dis-
sociation of proton upon Cu2+ extraction was observed (y = 0.214).
Meanwhile, the slope of Cu+ is significantly higher (y = 0.752).

Fig. 1. Effect of pH on extraction of Ni2+ , Cu2+ and Pb2+ ([L] = 10 mM, 25 ◦ C, n = 3) in
different solvents: () ionic liquid (5 mg L−1 ), ( ) ionic liquid (1.0 mM) and ( )
CHCl3 (1.0 mM).
3.2. Extraction time
The results of each metal extraction as a function of time pre-
sented in Fig. 3 showed that the extraction efficiency of Pb2+ was

species of Cu–2-aminothiophenol complex. The resulting inactive

ESR indicated that copper ion in the complex had no unpaired elec-
tron, confirming that Cu2+ was changed to Cu+ ([Ar]3d10 ) upon
extraction. In addition, the extraction of Cu+ was performed. From
the assumption that Cu2+ is oxidized to Cu+ upon extraction, the
extraction of Cu+ salt should be different from that of Cu2+ . The
results obtained confirm the assumption since the colors of ionic
liquid phase after extraction were obviously different (dark blue for
Cu2+ and greenish yellow for Cu+ ), and the extraction of Cu+ is pH
dependent.
Confirmation of the metal ion extraction dependence on pH was
done by considering the extraction of Eq. (3) which leads to the
relationship between log D and proton concentration in Eq. (4), with
subscripts aq and IL referring to aqueous and ionic liquid phases,
respectively. Plotting of distribution ratio as a function of proton
concentration adjusted by HNO3 yields a straight line with slope Fig. 3. Effect of extraction time on metal ion extraction ([L]IL = 10 mM, 1.0 mL,
y which is equal to the number of hydrogen ions released in the [M] = 1.0 mM, 5.0 mL, pH 5, 25 ◦ C, n = 3).
 R. Lertlapwasin et al. / Separation and Purification Technology 72 (2010) 70–76 73

Table 1
Effect of interfering ions on Ni2+ , Cu2+ and Pb2+ extraction ([L]IL = 10 mM, 1.0 mL, [M] = 1.0 mM, 5.0 mL, pH 5, 25 ◦ C, n = 3).

Metal ion Interfering ions concentration (mM) % Extractiona

0 1 10 100 1000

Ni2+ Na+ 58 ± 1 59 ± 1 59 ± 1 59 ± 1 58 ± 1
Ca2+ 58 ± 1 61 ± 2 60 ± 2 59 ± 1 58 ± 1
Mg2+ 55 ± 1 57 ± 1 58 ± 1 57 ± 2 54 ± 1
SO4 2− 58 ± 1 59 ± 2 59 ± 2 58 ± 2 60 ± 1
Cl− 55 ± 1 57 ± 1 57 ± 2 56 ± 2 54 ± 2

Cu2+ Na+ 76 ± 1 76 ± 1 75 ± 2 77 ± 2 74 ± 3
Ca2+ 79 ± 2 78 ± 1 80 ± 1 79 ± 1 80 ± 1
Mg2+ 79 ± 2 77 ± 2 78 ± 3 80 ± 1 83 ± 1
SO4 2− 76 ± 1 76 ± 2 77 ± 2 77 ± 1 80 ± 1
Cl− 76 ± 1 75 ± 1 73 ± 1 66 ± 2 46 ± 2

Pb2+ Na+ 20 ± 1 21 ± 1 20 ± 1 18 ± 1 9±1

Ca2+ 20 ± 1 23 ± 1 21 ± 1 18 ± 1 8±1
Mg2+ 20 ± 1 20 ± 1 21 ± 1 15 ± 1 11 ± 1
a
Mean value ± SD, n = 3.

the lowest among three metal ions studied. However, it reached phase. However, the fact that the trends of percentage extraction
the equilibrium in a very short time (within 10 min). In contrast, in the presence of [BMIM]Cl in aqueous solution into ionic liquid
the extraction efficiency of Ni2+ increased along the extraction and chloroform are similar suggests the cation exchange mecha-
time and the extraction equilibrium required a relatively long time nism is improbable (Fig. 4). The decreasing of Cu2+ extraction at
(120 min). For Cu2+ , the extraction efficiency is maximum in less 100 mM [BMIM]Cl was probably due to the formation of CuCl+
than 30 min then reduced over time. The decrease of Cu2+ extrac- which would decrease the concentration of Cu2+ before extraction.
tion might be a result of a dissolution of Cu complexes into aqueous. At 1 M of [BMIM]Cl, the concentration of Cu2+ increased presum-
ably due to the generation of new extractable species as the color
3.3. Extraction mechanism and extraction stoichiometry of solution changed from colorless to green. The new species might
be the interaction of Cu(II) chloride with [BMIM]Cl as the interac-
The presence of two opposite charge species of the ionic liquid tion of Cu(II) chloride with 1-ethyl-3-methylimidazolium chloride
makes the metal ion separation in aqueous/IL biphasic system a in ethanol to yield a yellow solution was previously reported [32].
much more complex process than in traditional solvents. In fact, For the extraction of Pb2+ , the extraction efficiency decreased due
many studies have demonstrated the difference of metal extraction to the PbCl2 precipitate which suspended in the solution.
mechanism between ionic liquid and convenient organic solvents The slope analysis was carried out to examine the stoichiom-
[10,29,30]. For example, the metal extraction mechanism changed etry of metal complex and to determine the extraction constant
from ion-pair mechanism in organic solvent (denoted by org, Eq. Kex . According to Eq. (4), the number of ligands incorporated in
(5).) to cation exchange in ionic liquid (Eq. (6)). the extractable metal complex and the extraction constant can be
found from the slope and the intercept of the plot of log D against
(Mn+ )aq + x(L)org + m(NO3 − )aq  (MLx (NO3 )m )org (5) log concentration of the free ligand at equilibrium in ionic liquid at
constant pH. Because [H2 L]IL depends on the stoichiometry of the
(Mn+ )aq + (L)IL + ([BMIM]+ )IL  (ML)n+ +
IL + n([BMIM] )aq (6)
extracted species, thus b and D, the slope analysis was performed in
The ion-pair mechanism can be proved by comparing the extrac- an iterative fashion using program SigmaPlot (v.5, Systat Software
tion efficiency in the presence of different counter ions because Inc.). The slopes for extraction of Ni2+ , Cu2+ and Pb2+ are 2.998,
ion-pair complex depends on the type of counter ion [10,31]. 1.951 and 1.705, corresponding to M to L complex stoichiometries
Table 1 shows that changing of counter ions did not affect the
extraction of Ni2+ and Cu2+ except in the presence of a very high
concentration of Cl− (1 M) which might form CuCl+ in the solution.
(Note that the effect of different counter ions in Pb2+ extraction was
not performed due to the precipitation of PbSO4 and PbCl2 .) From
this finding, the ion-pair complex mechanism is therefore unlikely.
The results in Table 1 also demonstrate that the effect of interfer-
ing ions (Na+ , Ca2+ , Mg2+ ) on metal ion extraction was insignificant
except in the case of Pb2+ at high concentration.
As for the ion-association mechanism, the amount of nitrate
ions in aqueous phase should decrease as they must associate with
the extracted metal species into ionic liquid phase. The insignifi-
cant loss of nitrate ions (investigated by ion chromatography) upon
extraction of all three metal ions suggests that the ion-association
mechanism is also unlikely.
The effect of [BMIM]Cl at various concentrations on the metal
extraction in ionic liquid and in chloroform was studied to examine
the cation exchange mechanism. Increasing of [BMIM]Cl in aque-
ous solution should drive the extraction equilibrium in Eq. (6) to the
left, resulting in a lower extraction efficiency. In contrast, the trans-
Fig. 4. Effect of [BMIM]Cl in aqueous phase on Ni2+ , Cu2+ and Pb2+ extraction
fer of Ni2+ , Cu2+ and Pb2+ into chloroform via ion-pair mechanism ([L]IL = 10 mM, 1.0 mL, [M] = 1.0 mM, 1.0 mL, pH 5, 25 ◦ C, time = 120, 30, 10 min for
should be independent of the concentration of [BMIM]Cl in aqueous Ni2+ , Cu2+ and Pb2+ , n = 3).
74 R. Lertlapwasin et al. / Separation and Purification Technology 72 (2010) 70–76

Fig. 5. Plots of log D as a function of log concentration of free ligand in ionic liquid
(VIL = 1.0 mL, VM = 1.0 mL, [M] = 1.0 mM, pH 5, 25 ◦ C, time = 120, 30, 10 min for Ni2+ ,
Cu2+ and Pb2+ , n = 3).

of 1:3, 1:2 and 1:2, respectively (Fig. 5). According to Eq. (4), the
Kex of Cu2+ extraction can be calculated from the intercept of the
graph. For Ni2+ and Pb2+ extraction, Kex values were calculated by
subtraction of the intercept with two times of pH values of the
extraction without ligand (0.054 and 0.160, respectively). The cal-
culated Kex values of Ni2+ , Cu2+ and Pb2+ are 1.22 × 108 , 3.77 × 106
and 1.60 × 103 , respectively.
The stoichiometry of extracted complex was also investigated by
an adaptation of Job’s plot method in two phases by varying mole
fraction of metal ion in aqueous phase to ligand in IL phase. The
results from this imitation of Job’s plots, illustrated in Fig. 6, clearly
show that the concentration of extracted Ni2+ , Cu2+ and Pb2+ into
ionic liquid reached a maximum at the mole fraction of the metal,
XM , of 0.25, 0.33 and 0.33, corresponding to a M to L complex of 1:3,
1:2 and 1:2, respectively. These results are in excellent agreement
with the slope analysis mentioned above.
The results from effects of pH and interfering ions in combi-
nation with the slope analyses indicate that Ni2+ and Pb2+ were
extracted into ionic liquid via proton transfer mechanism as ML3
and ML2 species, respectively. The 2-aminothiophenol ligand losts
two protons to aqueous phase upon extraction in both cases. As
for Cu2+ , the inactive ESR suggests that the extracted species is
ML2 complex of Cu+ with the radical form of deprotonated 2-
aminothiophenol.

3.4. Extraction equilibria and association constant in ionic liquid

Normally, the separation efficiency of metal ions in solvent

extraction is reported in terms of distribution ratio or percent-
age extraction which can be predicted from a set of equilibrium
constants. Association constant is another value that can fore-
cast the efficiency of metal extraction and can be calculated from
the relation between extraction constant and other equilibrium
constants such as the distribution constants of metal ion and of pro-
ton. Combining all the results obtained in this study, the possible
assumption of extraction equilibria of metal ions studied with 2-
aminothiophenol in ionic liquid [BMIM]PF6 could be proposed as in
the following Schemes 1 and 2 (H2 L denoting 2-aminothiophenol)
Fig. 6. Imitation of Job’s plots of the complexation between metal ions and 2-
for the cases of Ni2+ and Pb2+ , respectively, with the calculated
aminothiophenol in ionic liquid ([L] + [M] = 15 mM, VIL = 1.0 mL, VM = 1.0 mL, pH 5,
association constants displayed in Table 2. 25 ◦ C, time = 120, 30, 10 min for Ni2+ , Cu2+ and Pb2+ ).
Please note, however, that no detailed mechanism is proposed
for the case of Cu2+ at this stage. Although proton transfer to
aqueous phase was not observed in the case of Cu2+ , a hypoth-
esis that copper ion is transferred into ionic liquid as Cu(OH)2
yielding H2 O after extraction is not very likely because there is
no formation of Cu(OH)2 in the pH range studied. It could only be
 R. Lertlapwasin et al. / Separation and Purification Technology 72 (2010) 70–76 75

Table 2
Summary of values of extraction equilibria of Ni2+ and Pb2+ with 2-aminophenol in ionic liquid.

Metal ion %E Kex DH DM Kass Kass (value)

Ni 2+
57 1.22 × 10 8
0.13 0.0911 Kex DH
2
/DM 2.26 × 107
Pb2+ 20 1.60 × 103 0.13 0.0909 Kex DH
2
/DM 2.97 × 102
Cu2+ 76 3.77 × 106 0.13 0.0894 – –

Association : (Pb2+ )IL + 2(H2 L)IL  (Pb(HL)2 )IL + 2(H+ )IL ;

2
[Pb(HL)2 ]IL [H+ ]IL 2
Kex,Pb DH (8)
Kass,Pb = =
[Pb 2+
]IL [H2 L]2IL DM

3.5. Stripping study

Stripping is a recovery of extracted metal ions from the extrac-

Scheme 1. Diagram of extraction of Ni 2+
with 2-aminothiophenol (H2 L).
tant phase to the stripping phase. Since the previous results showed
that the extraction of metal ions depended on the pH of solu-
tion, acid solution was used as stripping solution. The stripping
efficiency after 60 min of Ni2+ , Cu2+ and Pb2+ with nitric acid at
stated from evidence that Cu2+ was reduced to Cu+ that the mech-
various concentrations is illustrated in Fig. 7(a). The results show
anism involves an oxidation–reduction reaction. It is possible that
that around 100% of Cu2+ and Pb2+ could be stripped using nitric
two 2-aminothiophenols are oxidized by Cu2+ to a disulfide RSSR
acid of at least 0.5 M. For the stripping of Ni2+ , the stripping effi-
form as previously reported [25,33]. The different number of pro-
ciency increased gradually along with acid concentration. The high
ton released upon extraction of Cu2+ and Cu+ indicates that their
percentage stripping at 100% could be obtained using nitric acid
extraction mechanisms are not similar.
of at least 3 M. However, this high acidic condition required is not
suitable because of the possible decomposition of PF6 − as reported
3.4.1. Extraction of Ni2+ earlier [28].
Extraction from aqueous to ionic liquid: On the account that 2-aminothiophenol can undergo an oxi-
dation reaction, an alternative way for stripping Ni2+ is by using
(Ni2+ )aq + 3(H2 L)IL  (Ni(HL)2 (H2 L))IL + 2(H+ )aq ; a reducing agent. H2 O2 was chosen due to their dual proper-
2 ties of reducing and oxidizing agent in acidic and basic medium,
[Ni(HL)2 (H2 L)]IL [H+ ]aq respectively. The stripping study showed in Fig. 7(b) that more
Kex,Ni =
[Ni2+ ]aq [H2 L]3IL than 98% of Ni2+ was stripped using 3% H2 O2 in 0.5 M and 1.0 M
HNO3 within 60 min. In contrast, using 3% H2 O2 in 0.1 M NaOH
Association of metal ion and ligand in ionic liquid:

(Ni2+ )IL + 3(H2 L)IL  (Ni(HL)2 (H2 L))IL + 2(H+ )IL ;

2
[Ni(HL)2 (H2 L)]IL [H+ ]IL 2
Kex,Ni DH (7)
Kass,Ni = =
[Ni 2+
]IL [H2 L]3IL DM

where

[Mn+ ]IL [H+ ]IL

DM = n+ and DH = .
[M ]aq [H+ ]aq

3.4.2. Extraction of Pb2+

Extraction : (Pb2+ )aq + 2(H2 L)IL  (Pb(HL)2 )IL + 2(H+ )aq ;
2
[Pb(HL)2 ]IL [H+ ]aq
Kex,Pb = 2+
[Pb ]aq [H2 L]2IL

Fig. 7. (a) Effect of HNO3 concentration on the stripping efficiency of each metal
(VIL = 1.0 mL, VHNO3 = 5.0 mL, 25 ◦ C, time = 60 min, n = 3) and (b) effect of time and
type of stripping agent on the stripping efficiency of each metal (VIL = 1.0 mL,
Scheme 2. Diagram of extraction of Pb2+ with 2-aminothiophenol (H2 L). Vstripping agent = 5.0 mL, 25 ◦ C, n = 3).
76 R. Lertlapwasin et al. / Separation and Purification Technology 72 (2010) 70–76
was unable to strip Ni2+ . A possible explanation for this obser-
vation is that in acidic medium H2 O2 can reduce the coordinated
2-aminothiophenol which probably forms less stable complex with
Ni2+ leading to a higher stripping efficiency.
The stripping efficiency as a function of time was also investi-
gated. The results showed in Fig. 7(b) that more than 95% stripping
of Pb2+ and Cu2+ by 1 M HNO3 occurred rapidly within 10 and
20 min, respectively. For Ni2+ , the kinetic studies of three types of
stripping agents, 3 M HNO3 , 3% H2 O2 in 0.5 M and 1 M HNO3 , were
compared. The stripping by H2 O2 occurred in a shorter time than
by HNO3 . More than 95% stripping of Ni2+ by 3 M HNO3 , 3% H2 O2
in 0.5 M and 3% H2 O2 in 1 M HNO3 occurred at 30, 20 and 10 min,
respectively.
4. Conclusion
A room temperature ionic liquid, 1-butyl-3-methylimidazolium
hexafluorophosphate ([BMIM]PF6 ) was synthesized via the reac-
tion of anion metathesis between 1-butyl-3-methylimidazolium
chloride ([BMIM]Cl) and hexafluorophosphoric acid. The charac-
terization of viscous yellow liquid product with FT-IR and 1 H
NMR showed that the synthesis of ionic liquid was successful. The
comparison of the extraction efficiency of Ni2+ , Cu2+ and Pb2+ by
2-aminothiophenol in two mediums, ionic liquid and chloroform,
showed that ionic liquid was a medium with higher metal extrac-
tion efficiency. The competitive ions such as Na+ , Ca2+ , Mg2+ , SO4 2−
and Cl− did not significantly affect the extraction efficiency of the
metal ions studied. Ni2+ and Pb2+ were extracted via proton trans-
fer mechanism with a stoichiometry of ML3 and ML2 , respectively,
while Cu2+ was extracted through redox mechanism yielding Cu+
complex of ML2 stoichiometry. The values of association constant of
metal complex in ionic liquid are 2.26 × 107 for Ni2+ and 2.97 × 102
for Pb2+ . The stripping of Pb2+ and Cu2+ could be done by HNO3
while Ni2+ could be stripped by H2 O2 in HNO3.
Acknowledgements
The success of this research can be attributed to Environmen-
tal Analysis Research Unit (EARU) and was financially supported
by the Grant for Research Unit (GRU51-017-23-008), and the 90th
Anniversary of Chulalongkorn University Fund (Ratchadaphisek-
somphot Endowment Fund), Chulalongkorn University. The Center
of Excellence for Petroleum, Petrochemicals, and Advanced Mate-
rials, Chulalongkorn University, is also acknowledged.
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