Separation and Purification Technology 72 (2010) 56–60

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Separation and Purification Technology

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

Transport and separation of iron(III) from nickel(II) with the ionic liquid
trihexyl(tetradecyl)phosphonium chloride
Daniel Kogelnig a,∗,1 , Anja Stojanovic a,1 , Franz Jirsa a , Wilfried Körner b , Regina Krachler a ,
Bernhard K. Keppler a
a
University of Vienna, Institute of Inorganic Chemistry, Waehringerstrasse 42, 1090-Vienna, Austria
b
University of Vienna, Department of Environmental Geosciences, Althanstrasse 14 (UZAII), 1090-Vienna, Austria

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

Article history: Iron(III) was efficiently extracted from a 6 M hydrochloride solution with the ionic liquid tri-
Received 1 December 2009 hexyl(tetradecyl)phosphonium chloride, Cyphos® IL101, dissolved in chloroform. Spectroscopical data
Accepted 28 December 2009 revealed that iron exists as tetrachloroferrate species in the organic phase. In contrast, nickel(II) was not
extracted under experimental conditions. Satisfying back extraction of Fe(III) was achieved with a 0.5 M
Keywords: HCl solution.
Liquid–liquid extraction
Consequent time-dependent transport studies with Cyphos IL101 as ionic liquid carrier in chloroform
Bulk liquid membrane
(0.01 M), showed a successful quantitative transport of 0.1 M Fe(III) from a 6 M hydrochloride source
Cyphos IL101
Iron(III)tetrachloroferrate
phase to a 0.5 M hydrochloride receiving phase and a favorable separation from Ni(II). The transport of
Transport kinetic Fe(III) through the bulk liquid membrane (BLM) was assumed to follow a nonsteady kinetic regime with
two consecutive and irreversible first-order reactions. With an initial Fe(III)/Cyphos IL101 concentration
ratio of 10, an apparent rate constant ks of 31.4 × 10−3 min−1 was obtained for the Fe(III) transport from
the membrane- to the receiving phase, whereas the rate constant kf for the Fe(III) transport from the
source- to the membrane phase was 11.8 × 10−3 min−1 .
© 2010 Elsevier B.V. All rights reserved.

1. Introduction IL101 dissolved in chloroform has not been reported so far. It is

Ionic liquids (ILs) are generally defined as salts with a melt-
ing point below 100 ◦ C, whereas the majority of these salts are
already liquid at room temperature. They consist entirely of ions
and due to the almost unlimited amount of possible cation–anion
combinations, their physico-chemical properties can be adequately
tuned for a desired application [1,2]. It is therefore not surprising
that water-immiscible ILs have already been designed for their task
specific applicability as extracting agents for metals from aqueous
solutions [3–5].
The use of the hydrophobic long-chain quaternary phospho-
nium IL trihexyl(tetradecyl)phosphonium chloride (Cyphos® IL101
or [PR6,6,6,14 ][Cl], Fig. 1), has recently been investigated as potential
new ionic liquid extracting agent dissolved in toluene for the elimi-
nation of zinc and palladium from aqueous phases or, immobilized
in biopolymers, for the sorption of the metals platinum, palladium,
bismuth, gold and mercury from hydrochloride solutions [6–8].
To the best of our knowledge, the extraction and separation of
iron(III) from nickel(II) from hydrochloride solutions with Cyphos
∗ Corresponding author. Tel.: +43 1 4277 52625; fax: +43 1 4277 52620.
E-mail address: daniel.kogelnig@univie.ac.at (D. Kogelnig).
1
These authors contributed equally to this work.
well known that Fe(III) forms a series of complexes in acidic chlo-
ride media with a distinct distribution of the species FeCl2+ , FeCl2 + ,
FeCl3 and FeCl4 − depending on the HCl concentration, whereas at a
molarity of 6 the predominant species is FeCl3 followed in decreas-
ing concentrations by FeCl2 + and FeCl4 − [9]. Under these conditions,
FeCl3 may be extracted by an ion association mechanism with the
chloride anion of Cyphos IL 101, as it has already been shown for
Hyamine 1622 (a long-chain quaternary ammonium chloride com-
pound), while FeCl4 − is thought to be exchanged by the chloride
anion of the IL [10,11]. The positive FeCl2 + complex is not expected
to show any affinity for ion association or ion exchange with the
Cyphos IL101. However, regarding the species FeCl3 and FeCl4 − , in
both cases Fe(III) should exist as tetrachloroferrate complex in the
organic phase. In contrary, Ni(II) should retain its hexacoordina-
tion also in high chloride concentrations [12]. The difference in this
complex behavior depending on the HCl concentration was already
used to separate these two metals from HCl solutions by El-Wakil
et al. [13] using Aliquat® 336 (a long-chain quaternary ammonium
chloride compound) or by Lee et al. [14] with the tertiary amine,
Alamine® 336.
The aim of this work was to evaluate the suitability of the
phosphonium-based IL Cyphos IL101 as extracting agent for the
elimination and separation of Fe(III) from Ni(II) in hydrochloride
solutions. Based on liquid–liquid batch extractions, Cyphos IL101

1383-5866/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.seppur.2009.12.028
 D. Kogelnig et al. / Separation and Purification Technology 72 (2010) 56–60
Fig. 1. Structure of the ionic liquid trihexyl(tetradecyl)phosphonium chloride
(Cyphos® IL101, [PR6,6,6,14 ][Cl]).
was further evaluated as potential ionic liquid Fe(III)-carrier in a
bulk liquid membrane (BLM) for the continuous transport of Fe(III)
from a source- to a receiving phase and a possible separation from
Ni(II).
2. Experimental
2.1. Reagents
Iron(III)chloride hexahydrate, nickel(II)chloride tetrahy-
drate, chloroform and Cyphos® IL101 were purchased from
Sigma–Aldrich (Austria) and used as-received. Hydrochloride
stock solutions were prepared using analytical grade HCl (purum,
p.a.; 37%, Aldrich). Ultra pure water was obtained from a Millipore
SynergyUV Ultrapure water system (Molsheim, France). Working
metal solutions were prepared by properly diluting the metal
stock solutions (0.1 M Fe(III) and 0.1 M Ni(II), respectively). 59 Fe
tracer was purchased from Perkin-Elmer, Germany.
2.2. Synthesis of [PR6,6,6,14 ][FeCl4 ]
The ionic liquid trihexyl(tetradecyl)phosphonium tetrachlo-
roferrate ([PR6,6,6,14 ][FeCl4 ]) was synthesized according to the
literature [15] and revealed characteristic visible absorptions of the
tetrachloroferrate anion (Fig. 4). For visible spectroscopy a Perkin-
Elmer Lambda 25 spectrometer was used. Droplets of the magnetic
ionic liquid in water could also be easily attracted and manipulated
by an external magnet.
2.3. Liquid–liquid batch extraction experiments
Batch extraction experiments were conducted using 10 mL vials.
Unless otherwise stated, same volumes of metal solutions and
Cyphos® IL101 dissolved in CHCl3 were shaken using a Vortex
Fig. 2. Glass cell used in transport studies (diameter source phase-membrane and membrane-receiving phase: 1.3 cm).
57
(VF2, IKA® - Labortechnik, Germany) for 3 min to ensure equilib-
rium. Samples were further centrifuged (5 min, 3500 rpm) to obtain
a complete phase separation and the upper aqueous phase was
then separated from the ionic liquid containing phase. No third
phase formation during the batch extractions was observed under
applied experimental conditions. Reference experiments were con-
ducted using the same experimental setup but without the ionic
liquid. The aqueous phase was properly diluted and the metal
content was measured using inductively coupled plasma-optical
emission spectrometry (ICP-OES) (Optima 5300 DV, Perkin-Elmer).
The extraction efficiency (E, %) was calculated using the relation:
c0 − cf
E (%) = × 100
c0
whereas c0 is the concentration of the metal in the aqueous phase
before extraction and cf is the metal concentration in aqueous phase
after extraction (RSD <8%).
The extraction isotherm was obtained using a radiotracer-
method giving the advantage that the metal content can be
measured in both phases [11]. For this purpose, a small amount
(<10−6 M) of a 59 Fe radioactive tracer was added to a distinct Fe(III)
solution, and vigorously vortexed to ensure equilibrium. After-
wards, 0.01 M Cyphos IL101 was added in an equal volume. After
shaking and centrifugation, aliquots of both phases were taken and
the activity in the aqueous and organic phase was measured with
a NaI gamma detector (Canberra Packard, Austria) at 1090 keV. The
molarity of Fe(III) in each phase was then calculated according to
the 59 Fe distribution. Experiments were done in duplicates. Esti-
mated error bars were <10%.
2.4. Transport studies
The transport cell used in transport studies was a self-made
glass cylinder holding a glass plate separating the aqueous phases
(Fig. 2). The volumes of the source- and receiving phase were 1.5 mL,
respectively. The volume of the bulk liquid membrane (BLM) con-
taining the ionic liquid carrier was 4 mL. The diameter of feeding-
and membrane phase as well as membrane- and receiving phase
was 1.3 cm.
The BLM was stirred at a temperature of 25 ± 0.5 ◦ C (Heidolph
Inkubator 1000) at a constant rate of 200 rpm. At distinct times,
samples of 150 ␮L from both aqueous phases were taken in order
to study the time-dependent transport. Volumes were adjusted by
adding 150 ␮L fresh metal- or stripping solution. Metal concen-
trations were measured using ICP-OES (method see Section 2.3) or
flame AAS (F-AAS). In case of F-AAS, an AAnalyst 300, Perkin-Elmer,
was used and Fe(III) was measured at 248.3 nm, whereas Ni(II)
was measured at 232 nm, respectively. Transport studies were con-
ducted twice. The relative standard deviation (RSD) was <10%.
58 D. Kogelnig et al. / Separation and Purification Technology 72 (2010) 56–60
Fig. 3. (a) Effect of the molar ratio Cyphos IL101IL/Fe(III) on the extraction effi-
ciency (E, %) for Fe(III) with increasing IL concentration (feed: 6 M HCl; 0.01 mol
Fe(III); RSD <8%). (b). Extraction isotherm of Fe(III) with Cyphos IL101 (feed: 6 M
HCl; 0.001–0.04 mol Fe(III); organic: 0.01 M Cyphos IL101).
3. Results and discussion
3.1. Liquid–liquid batch extraction experiments
Preliminary experiments revealed that the extraction efficiency
of Cyphos IL101 for Fe(III) depends on the hydrochloride con-
centration. Our results are in good agreement with results from
studies using quaternary ammonium chloride compounds, e.g.
Aliquat® 336 or Hyamine 1622, as Fe(III) was only poorly extracted
below 0.5 M HCl [11,13]. With increasing HCl molarity, the extrac-
tion efficiency increased and at 6 M HCl, 0.1 M Fe(III) could be
extracted nearly quantitatively with 0.1 M Cyphos IL101. Fig. 3a
reveals, when the IL concentration was increased at constant Fe(III)
concentration, the extraction efficiency also increased, reaching
a maximum of >99% at a molar ratio Cyphos IL101/Fe(III) >1.
The extraction isotherm presented in Fig. 3b was obtained from
tracer-experiments. Increasing the Fe(III) concentration at a con-
stant amount of 0.01 M Cyphos IL101 led to a maximum loading of
approx. 0.01 M Fe(III). These results strengthen our hypothesis that
Fe(III) is extracted in an equimolar ratio to Cyphos IL101 according
to Eq. (1):
FeCl3 + PR4 Cl → PR4 FeCl4o (1)
However, Bjerrum and Lukeš [9] have calculated from spec-
troscopic measurements that at a HCl molarity of 6 M, Fe(III)
predominantly forms the FeCl3 complex with a mole fraction of
0.68 and two further species FeCl4 − and FeCl2 + , each with a fraction
of 0.16, respectively. Therefore it is most likely that Eq. (2)
FeCl4 − + PR4 Cl → PR4 FeCl4o + Cl− aq (2)
Fig. 4. Visible spectrum of the organic Cyphos IL101/CHCl3 phase after
extraction of Fe(III) from 6 M HCl solution and the synthesized sample of tri-
hexyl(tetradecyl)phosphonium tetrachloroferrate (inset).
will compete with Eq. (1). Nevertheless, according to proposed
equations, in both cases the iron species in the organic phase should
be FeCl4 − . Fig. 4 illustrates the spectroscopic measurments of a
synthesized sample of trihexyl(tetradecyl)phosphonium tetrachlo-
roferrate, [PR6,6,6,14 ][FeCl4 ], in CHCl3 [15] as well as the organic
Cyphos IL101/CHCl3 phase after the extraction process. Both spec-
tra clearly show the characteristic absorption bands of the FeCl4 −
anion at 534, 619 and 688 nm [15]. These results lead to the conclu-
sion that Fe(III) occurs as tetrachloroferrate species in the organic
Cyphos IL101/CHCl3 phase.
The back extraction of Fe(III) from the ionic liquid was success-
fully achieved with HCl concentrations <0.5 M. About 80% of Fe(III)
could be back extracted in one step from the Fe(III) saturated ionic
liquid with an equal volume of a 0.5 M hydrochloride solution.
Further, Cyphos IL101 was evaluated as extracting agent for
Ni(II). However, Ni(II) was not extracted from a 6 M HCl solution.
It is well known that Ni(II) retains its hexacoordination also in
high chloride concentrations [12], and therefore the result is not
surprising itself.
3.2. Fe(III) transport through a BLM containing Cyphos IL101
ionic liquid
Based on liquid–liquid batch extraction- and back extraction
results, we evaluated Cyphos IL101 as potential ionic liquid car-
rier in bulk liquid membrane (BLM) experiments. First experiments
revealed that 0.1 M Fe(III) was transported nearly quantitatively
(>99%) within 24 h from a 6 M source- to a 0.5 M HCl receiving solu-
tion through 0.01 M Cyphos IL101 dissolved in CHCl3 . There was no
significant transport without the IL carrier (<5%). The results of a
further experiment evaluating a possible transport of Fe(III) from
a 0.5 M HCl source- to a 6 M HCl receiving phase again showed
no remarkable Fe(III) transport (<5%). This indicates that the HCl
molarity is an important factor for the formation of extractable
Fe(III)-chloride species [9]. Competitive transport studies of Fe(III)
and Ni(II) resulted in the expected non-transport of Ni(II) and there-
fore favorable separation from Fe(III). Generally, these results are
in agreement with our liquid–liquid batch experiments.
In order to elucidate the kinetic regime of the Fe(III) transport,
time-dependent studies were conducted. Generally, the transport
of Fe(III) from a 6 M HCl source solution (feed) through a Cyphos
IL101 containing bulk liquid membrane (BLM) to a 0.5 M HCl receiv-
ing solution (strip) was expected to obey the kinetic law of two
consecutive and irreversible first-order reactions:
kf ks
Fe(III)feed −→Fe(III)BLM −→Fe(III)strip
 D. Kogelnig et al. / Separation and Purification Technology 72 (2010) 56–60 59

tmax (min)

50
max
RLM

0.2
Jmax (×10−3 min−1 )

6.5
ks (mean) (×10−3 min−1 )

Fig. 5. Reduced concentrations of Fe(III) in feed phase (Rf ), membrane (RBLM ) and
stripping phase (Rstrip ) for the time dependence transport of Fe(III) through the
Cyphos IL 101 containing bulk liquid membrane (symbols: experimental data, lines:
model data; carrier: 0.01 M Cyphos IL101; feed: 0.1 M Fe(III) in 6 M HCl; strip: 0.5 M
HCl; stirring rate: 200 rpm).
31.1

where kf and ks are the apparent rate constants for the extrac-
tion and stripping process, respectively. Several authors already
addressed this mechanism for a series of metal ions [16–18]. To
simplify matters, reduced dimensionless concentrations Rfeed , RLM
and Rstrip were used for the Fe(III) concentration in the feed-,
ks strip (×103 min−1 )

membrane- and stripping phase

Cfeed
Rfeed = (3)
C0
Kinetic parameters for the transport of Fe(III) through the bulk liquid membrane containing the Cyphos IL101 ionic liquid.

30.9

CBLM
RBLM = (4)
C0
Cstrip
ks BLM (×10−3 min−1 )

Rstrip = (5)
C0
where C0 is the initial concentration of Fe(III) in the feed phase.
The mathematical description of this transport process is given
by the following differential equations [16]:
31.8

dRfeed
= −kf Rfeed (6)
dt
kf (×10−3 min−1 )

dRBLM
= kf Rfeed − ks RBLM (7)
dt
dRstrip
= ks Rstrip (8)
11.8

dt
whereas integration of Eqs. (6)–(8) gives

Rfeed = exp(−kf t)
Ratio Fe(III)/Cyphos

(9)
kf
RBLM = [exp(−kf t) − exp(−ks t)] (10)
ks − kf
1
Rstrip = 1 − [ks exp(−kf t) − kf exp(−ks t)] (11)
10

ks − kf
In Fig. 5 the time-dependent transport of 0.1 M Fe(III) through
c Fe(III) (M)

a 0.01 M Cyphos IL101 membrane is shown, indicating that Rfeed

and RBLM are tending to 0, while Rstrip is tending to 1. Whereas
Rfeed follows a mono-exponential curve, RBLM and Rstrip increase
0.1

bi-exponential with time. This strengthens the assumption that the

transport of Fe(III) from the source phase to the ionic liquid mem-
brane and from the ionic liquid membrane to the receiving phase
c Cyphos (M)

is apparently irreversible.
The model curves were calculated according to Eqs. (9)–(11) and
Table 1

0.01

are in good agreement with experimental data as it can be seen from

Fig. 5. The values for the rate constants kf and ks were determined
60 D. Kogelnig et al. / Separation and Purification Technology 72 (2010) 56–60
by nonlinear curve fitting [19]. Whereas kf was directly obtained
from Eq. (9), ks was either obtained from Eq. (10) or Eq. (11).
The maximum flux (Jmax ) was calculated according to [18],
assuming that RBLM has a maximum at dRBLM /dt = 0 with
 k −(ks /(kf −ks ))
max f
RBLM =
ks
and
ln(kf /ks )
tmax =
kf − ks
Differentiation of Eqs. (9)–(11) by introducing the expressions
of Eqs. (12) and (13) leads to:
 k −(kf /(kf −ks ))  k −(ks /(kf −ks ))
f f
Jmax = −kf = ks
ks ks
In Table 1 the apparent transport rate constants are pre-
sented together with the maximum flux. Under our experimental
conditions the apparent transport rate of Fe(III) from the bulk
liquid membrane into the receiving solution is much higher
(ks = 31.4 × 10−3 min−1 ) compared with the transport rate for
the transport from the source phase to the membrane phase
(kf = 11.8 × 10−3 min−1 ). Considering an initial Fe(III)/Cyphos IL101
concentration ratio of 10, it is clear that the carrier concentration in
the membrane is much lower than the Fe(III) concentration in the
source phase and that the membrane is not saturated. From this
fact it is reasonable to assume that the rate-controlling step is the
extraction reaction taking place at the feed–membrane interface.
Further, a release of the tetrachloroferrate species (decomplexa-
tion) from the ionic liquid membrane – at an initial Fe(III)/Cyphos
IL101 concentration ratio of 10 – seems to be more favorable than
the complexation. Generally, the transport of Fe(III) through the
ionic bulk liquid membrane follows a nonsteady first-order kinetic
regime.
In conclusion, we have shown that the quaternary phosphonium
ionic liquid Cyphos IL101 is suitable for the separation of Fe(III) and
Ni(II) from a 6 M hydrochloride solution via liquid–liquid extrac-
tion. Spectroscopic investigations revealed that extracted Fe(III)
exists as tetrachloroferrate complex in the organic ionic liquid
phase and a satisfying back extraction of Fe(III) could be achieved
with a 0.5 M hydrochloride solution. Ni(II) was not extracted at all.
Furthermore, BLM studies using Cyphos IL101 as ionic liq-
uid carrier have shown, that 0.1 M Fe(III) could be transported
quantitatively from a 6 M hydrochloride source phase to a 0.5 M
hydrochloride stripping phase associated with an efficient separa-
tion from Ni(II), which remained in the source phase.
(12) To get a deeper insight regarding the mechanism of the Fe(III)
transport through the Cyphos IL101 ionic liquid carrier, the influ-
ence of the carrier-, metal- as well as HCl concentration will be
evaluated in a further study.
(13)
Acknowledgement
The authors are grateful to the Austrian Federal Ministry of Agri-
culture, Forestry, Environment and Water Management (project
(14)
number A600702) for the financial support.
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