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Extraction of iridium(IV) from aqueous solutions using

hydrophilic/hydrophobic ionic liquids

Article in RSC Advances · September 2014

DOI: 10.1039/C4RA06991A

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Extraction of iridium(IV) from aqueous solutions

using hydrophilic/hydrophobic ionic liquids
Cite this: RSC Adv., 2014, 4, 48260
Nicolas Papaiconomou,*abc Isabelle Billardde and Eric Chainetbc

Anionic complexes of iridium(IV) were extracted from acidic solutions of HCl using ionic liquids (IL). The
influence of the cationic structure of IL and of the aqueous phase pH on the distribution coefficients of
IrCl62
was investigated. Liquid–-liquid extraction and precipitation of iridium(IV) were studied. Iridium(IV)
was precipitated from aqueous solutions using water-soluble ionic liquids by forming a water-insoluble
salt composed of two cations from the ionic liquid. Pyridinium cations appear to be the most efficient at
precipitating iridium(IV). Iridium(IV) was found to be efficiently extracted using simple hydrophobic ionic
Received 11th July 2014
Accepted 22nd September 2014
liquids, exhibiting D values ranging up to 71. Investigations on the extraction mechanism tend to show
that iridium(IV) is exchanged with two [NTf2]
anions from the IL phase. Finally, elution of iridium(IV) from
DOI: 10.1039/c4ra06991a
ionic liquids towards aqueous solutions was carried out from [BMIM][NTf2], [OMIM][NTf2] or [OdMIM]
www.rsc.org/advances [NTf2] into solutions containing high amounts of hydrochloric acid or nitric acid.

extraction of negatively charged metal complexes appears to be

Introduction mainly due to some anion exchange between the anion from the
Iridium is a rare and precious metal found in the earth's crust in ionic liquid (such as bis(triuoromethanesulfonyl)imide) and
extremely low concentrations, typically 2 ppb. It is found in the metal complex.9–14 Removal of metal from water is also
primary ores of platinum, such as those found in South Africa. possible by forming a water-insoluble ion pair formed with one
In such ores, iridium can be found in various proportions, or more cations of the IL and a negatively charged metal
ranging from above 25% down to less than 1%. It is however complex.11,14
generally low, typically below 1% in weight of the overall Aer having recently reported results on the extraction of
precious metal content, an amount similar to that of gold.1–3 gold(III) and platinum(IV) and their subsequent separation,11,12,14
Iridium, platinum and other platinum group metals, so- we focus here on the extraction of iridium(IV) from acidied
called PGMs, are generally present together in ores and are aqueous solutions using ionic liquids.
difficult to separate because they are very similar elements. Ir Such a study is justied for several reasons. First, iridium is a
and Pt are neighbours in the periodic table and exhibit oxida- precious metal with a high price (approximately 103 V per kg),
tion states of II and IV. Both Pt(IV) and Ir(IV) are able to form which confers a signicant added-value to any alternative
octahedral complexes such as PtCl62
or IrCl62
. For the latter extraction and purication process of the metal. Second,
anions, a typical extraction process involves ternary amines iridium is used in several industrial and high technology
such as trioctylamine or phosphate compounds as extracting applications such as electronics and telecommunications. It is
agents and kerosene as the extracting phase.4–7 also used in several other applications including alloys with
Ionic liquids are now well-known organic salts melting at or platinum to yield highly resistant anodes,15 high temperature
near room temperature. The diversity of available cations and crucibles,16 specic catalysts in organic chemistry17 and even
anions confers them very specic physicochemical properties. more recently catalysts for the electrocatalytic reduction of
Used as extracting phases, with or without extracting agents, carbon dioxide.18 It is also used as electrodes together with
ionic liquids have proven to be promising phases for the platinum in spark plugs in internal combustion engines. Such
selective extraction of numerous metallic ions.8 Even though spark plugs electrodes usually range between 5 to 15% in mass
the extraction mechanism are still subject to discussions, the of iridium, the rest being composed of platinum.19 Third, effi-
cient and selective extraction of iridium from ores or wastes
such as spark-plug electrodes is difficult using current
a
Univ. Savoie, LEPMI, F-73000, Chambéry, France. E-mail: nicolas.papaiconomou@ processes. Fourth, on a more fundamental level, studying the
lepmi.grenoble-inp.fr extraction of iridium and its separation from gold or platinum,
b
Univ. Grenoble-Alpes, LEPMI, F-38000, Grenoble, France its immediate neighbour in the periodic table, is useful for
c
CNRS, LEPMI, F-38000, Grenoble, France gaining better insight into the extraction abilities of ionic
d
Univ. Strasbourg, IPHC, 23 rue du Loess, 67037, Strasbourg, France liquids towards negatively charged metallic complexes. Our
e
CNRS, UMR 178, 67037 Strasbourg, France

48260 | RSC Adv., 2014, 4, 48260–48266 This journal is © The Royal Society of Chemistry 2014
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previous works dealing with Au(III) and Pt(IV) reported extraction adding Li[NTf2] to aqueous phases containing K2IrCl6 prior to
of chloro-, bromo-, or thiocyanocomplexes of these metals.11,14 the extraction experiments.
However, the formation of IrBr62
starting from IrCl62
salt is Back extraction studies were carried out starting from several
the subject of contradictory reports in the literature. We were ionic liquid phases containing IrCl62
and several leaching
not able to obtain such hexabromoiridate(IV) complexes in phases containing either HCl or HNO3.
water, even aer heating a solution containing K2IrCl6 and an
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excess of KBr for a week at 60  C. On the other hand, iridium(IV)

Experimental
was reported to oxidize thiocyanate anion in water leading to
the formation of cyanide anion.20 Therefore, the study reported Materials
in this article focussed on the extraction of IrCl62
in aqueous K2IrCl6 was provided by Johnson Matthey 39, 37% Ir titration,
solutions containing 10
2 to 12 M HCl, using two ways of and used as is. 37% HCl solution was purchased by Sigma
removing IrCl62
, namely liquid–liquid extraction or Aldrich and used as is. Ionic liquids were synthesized using
precipitation. bromooctane (purity 99%), 1-methylimidazole (purity 99%) and
Liquid–liquid extraction experiments were carried out using 1,2-dimethylimdazole (purity 99%) provided by Alfa Aesar and
hydrophobic ionic liquids 1-butyl-3-methylimidazolium bis(tri- used without further purication. Lithium bis(tri-
uoromethanesulfonyl)imide [BMIM][NTf2], 1-octyl-3-methyl- uoromothanesulfonyl)imide was provided by Solvionic and
imidazolium bis(triuoromethanesulfonyl)imide [OMIM][NTf2], used as is. Ionic liquids were synthesized using reported
1-octyl-2,3-dimethylimidazolium bis(triuoromethylsulfonyl) procedure.11 Purity was checked using silver nitrate tests and
imide [OdMIM][NTf2], 1-octyl-1-methylpyrrolidinium bis(tri- NMR.
uoromethanesulfonyl)imide [MOPYRRO][NTf2] or 1-octyl-3,5-
dimethylpyridinium bis(triuoromethanesulfonyl)imide Instrumentation
[O35PYR][NTf2] as extracting phases. Structures and abbrevia-
Experiments were carried out using an orbital shaker with a
tions of the ions used in this study are presented in Fig. 1.
rotation speed of 260 rpm.
[BMIM]+ and [OMIM]+ cations are based on the same unsatu-
Centrifugation was carried out on 3–10 centrifuge from
rated heterocycle containing a delocalised positive charge, and
Sigma.
two different alkyl chain lengths. [OdMIM]+ cation includes a
UV-Vis spectra were recorded on a Cary 50 from Varian using
methyl group on the carbon bound to the two nitrogens, which
a 1 cm quartz cell.
replaces the labile hydrogen present on the [BMIM]+ and 1
H NMR spectra were recorded on a 400 MHz spectrometer
[OMIM]+ cations. These three cations were chosen because they
from Brucker. Deuterated DMSO was used as solvent.
belong to the family of ionic liquids studied the most in the
The pH of the aqueous solutions prior and aer the extrac-
literature. [O35PYR]+ is a six-membered unsaturated hetero-
tion experiments carried out at 0.01 and 0.1 M HCl were
cycle containing a delocalised positive charge. On the other
measured using a HI221 pH meter from Hanna Instruments
hand, [MOPYRRO]+ cation is a saturated ve-membered
and a HI1131 pH electrode.
heterocycle embedding a localized positive charge, as opposed
to the unsaturated imidazolium cation.
Precipitation experiments were carried out using hydrophilic Extraction protocols
ionic liquids [OMIM][Br], [OdMIM][Br] or [O35PYR][Br], Precipitation of Ir(IV). Precipitation of iridium(IV) complexes
accordingly. Since no reaction of IrCl62
and bromide anions was carried out using aqueous solutions containing various
were observed in our studies, the presence of bromide anions concentrations of water-soluble ionic liquids. To that end, a
did not modify the nature of the iridium(IV) complex during the stock solution containing 1 M HCl and 1.1 mM K2IrCl6 was rst
time of the investigation. prepared. Precipitation experiments were then carried out
The extraction mechanism for the liquid–liquid extraction of typically mixing 2 cm3 of the above mentioned aqueous solution
iridium(IV) using [OMIM][NTf2] was studied experimentally with 2 cm3 of a solution containing 1 M HCl and concentrations
of [OMIM][Br], [OdMIM][Br] or [MOPYRRO][Br] accordingly,
ranging from 10
3 to 2 10
2 M. The mixture was le on a shaker
for one hour. When a precipitate of a red-brownish colour was
observed, the tube was centrifuged for 15 min. The aqueous
phase was then analysed by UV-Vis spectroscopy as detailed
further.
Liquid–liquid extraction of IrCl62
. Stock solutions of
K2IrCl6 containing concentrations of HCl ranging from 10
2 to
12 M HCl accordingly, were prepared dissolving K2IrCl6 in
aqueous solutions of HCl.
Liquid–liquid extraction experiments were then carried out
contacting in a centrifuge tube, 3 g of each stock solution
mentioned above with a volume of ionic liquid yielding a
Fig. 1 Structures and abbreviations of ions used in this study. volume ratio Vw/VIL of 5. Densities of HCl solutions are available

This journal is © The Royal Society of Chemistry 2014 RSC Adv., 2014, 4, 48260–48266 | 48261
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RSC Advances Paper

in the literature.21 Densities of ionic liquids were assumed to be For the liquid–liquid extraction experiments, the distribu-
1.3  0.02 g cm
3 for all octyl-based ionic liquids. The density of tion coefficient (D) was calculated using the following formula.
[BMIM][NTf2] was taken as 1.40  0.02 g cm
3.  Init  Final
The tube was le on a shaker for 12 hours and then centri- IrCl6 2

IrCl6 2
Vw
D¼  Final (2)
fuged for 15 min. An aliquot of the aqueous phase was taken IrCl6 2
VIL
from the tube and the concentration of IrCl62
was measured
with Vw and VIL the volumes of water and ionic liquid, respec-
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with the help of UV-Vis spectroscopy as detailed below.

tively. The volume ratio Vw/VIL used in the extraction experi-
In addition, six aqueous solutions containing 0.01, 0.017,
ments is 5. The detection limit of our analytical method was set
0.024, 0.051, 0.074 and 0.1 M Li[NTf2] were prepared by
to 5  10
6 M. The maximum D value measurable in this study
adding the desired mass of Li[NTf2] into a solution at pH 1 and
was assumed to be 103. The relative uncertainty on D is 5%. All
10
3 M K2IrCl6. Then, 3 cm3 of each solution was mixed with
experiments are performed in duplicates
0.6 cm3 of [OMIM][NTf2]. Aer mixing and centrifuging as
detailed above, the aqueous phase was analysed using UV-Vis
spectroscopy.
Back-extraction of Ir(IV) ions. Elution experiments were Results and discussions
carried out starting from several ionic liquid phases obtained Precipitation of Ir(IV)
aer liquid–liquid extraction, thus containing IrCl62
. Typically,
0.5 cm3 of the ionic liquid was mixed with 4 mL of an aqueous Results show that no precipitation occurs when 1.1 mM IrCl62

phase containing either 5 M HCl, 12 M of HCl or 5 M HNO3. and 2.2 mM of [OMIM][Br] or [OdMIM][Br] are mixed accord-
Aer mixing and centrifuging as detailed above, the aqueous ingly. Precipitation was observed using concentrations of ionic
phase was analysed using UV-Vis spectroscopy. liquid of 0.01 M and above.
Measurements. The nal concentration of Ir(IV) was deter- [O35PYR][Br] is the most efficient ionic liquid for precipi-
mined by UV-Vis spectrophotometry, applying the Beer– tating IrCl62
out from a 1 M HCl solution. With this cation,
Lambert's law at the maximum absorption wavelength (lmax ¼ iridium was removed so efficiently from the aqueous phase that
489 nm) of iridium and using calibration solutions ranging the remaining concentration was below the detection limit of
from 10 to 100 mM. In all cases, a correlation factor of 0.999 and our analytical method. Such results are in agreement with those
above for the Beer–Lambert's law was obtained. Values for the reported for Au(III) precipitation, which had shown that 1-
molecular extinction coefficients of 3400, 3900, 6380 and 1900 octylpyridinium bromide was more efficient at removing
mol L
1 cm
1 were calculated for iridium(IV) dissolved in AuBr4
complexes from water than [OMIM][Br].
aqueous solutions containing 0.1, 1, 4 and 7.8 M HCl, respec- Replacing the labile hydrogen of the imidazolium cation by a
tively. Fig. 2 presents a typical UV-Vis spectra of iridium(IV) methyl group yielded lower extraction percentages of IrCl62
.
dissolved in an acidic phase. For instance, using 0.01 M of [OMIM][Br] or [OdMIM][Br],
For the precipitation experiments, the extraction efficiency of extraction percentages of 81 or 23% for IrCl62
were obtained
iridium from water (Irextr%) is calculated as following: accordingly. Increasing the concentration of ionic liquid in the
solution leaded to a higher extraction efficiency. Values of 98 and
 Init  Final
IrCl6 2

IrCl6 2
71% were obtained using 0.02 M of [OMIM][Br] or [OdMIM][Br].
Irextr % ¼ 100   Init (1)
IrCl6 2
As reported previously for Au(III) or Pt(IV) in HCl media, these
results fully support the assumption that precipitation of
where [IrCl62
] refers to the concentration of Ir2Cl62
in water, IrCl62
in presence of cations of ionic liquids yields the
and the superscripts Init and Final refer to the values measured formation of an insoluble ionic liquid containing IrCl62
anion.
prior or aer the extraction experiment, respectively. The value The reaction of precipitation can then be written as following
of Irextr% is calculated within 0.2.
2[OMIM]+ + IrCl62
/ [OMIM]2[IrCl6]solid (3)

and the solubility product is then calculated as

Ks ¼ [OMIM]2[IrCl6] (4)

A sample of the powder obtained mixing [OMIM][Br] or

[OdMIM][Br] with K2IrCl6 in 1 M HCl solution was collected and
1
H NMR spectrum was recorded. As expected, the spectrum
obtained was similar to that of [OMIM][Br] cation, conrming
the presence of [OMIM]+ cation in the precipitate and the
formation of [OMIM]2[IrCl6] as shown in eqn (4). The UV-visible
spectrum of a sample of the precipitated salt dissolved in DMSO
showed absorption bands similar to those recorded for K2IrCl6
Fig. 2 UV-Vis absorption spectrum for IrCl62
dissolved in a 1 M HCl in water. Since the cations of the ionic liquids do not exhibit any
solution (–) or in DMSO (-- --). absorption band in the visible region, the absorption bands

48262 | RSC Adv., 2014, 4, 48260–48266 This journal is © The Royal Society of Chemistry 2014
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Paper RSC Advances

shown in Fig. 2 are due to the IrCl62
anion. Due to the DMSO, a Interestingly, [O35MPYR]2[IrCl6] exhibits a Ks value below
small bathochromic shi was observed. 4  10
10, which is two orders of magnitude lower than that
Solubility products calculated according to eqn (4) are obtained with [OMIM][Br]. Because similar observations had
reported in Table 2. The values are found to be below 10
8, and been reported with AuCl4
, our results conrm that the pyr-
are in the range of the Ks values reported previously for plati- idinium cation generally interacts in a stronger way with poly-
num(IV) at 1 M HCl. According to eqn (4), values of 1.35  10
8, halogenometallate anions than imidazolium. Such a result
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0.62  10
8 and 1.16  10
8 for Ks were calculated from the might be explained by the important electron delocalisation on
results obtained using 0.01, 0.02 or 0.04 M [OMIM][Br], the pyridinium ring, which yields interactions between the p
respectively. These values are close from one another and are electrons and the electron pairs of the chloride anions from the
within the experimental error of our analysis method. There- anionic metal complex.
fore, an average value of 1.04  10
8 was assigned to the Ks (see Industrial extraction processes regularly use selective
Table 1). Similarly, an average value of 8.40  10
8 was calcu- precipitation procedures using ammonium chloride in order to
lated for [OdMIM]2[IrCl6]. precipitate iridium(IV) or platinum(IV) out from water under the
form of (NH4)2IrCl6 or (NH4)2PtCl6, accordingly. The solubility
of ammonium hexachloroiridate(IV), reported to be 7.7 or 12.1
g kg
1 water at 20 and 30  C respectively,22 corresponds to Ks
Table 1 Precipitation of IrCl62
in 1 M HCl solutions using water- values of 9  10
6 and 3.5  10
5 respectively. In order to
soluble ionic liquids
extract iridium(IV), typical concentrations of 0.5 M or 1 M NH4Cl
Ionic liquid [IL]/mol L
1 Irextr% 108 Ks are therefore used in the process. The Ks values of (NH4)2IrCl6
are therefore up to ve orders of magnitude higher than those
[OMIM][Br] 0.0022 0 1.04  0.42 reported in this study. This implies that iridium(IV) could be
0.0101 81.3 precipitated out from water using a concentration of water-
0.0194 98.6
0.0400 99.4
soluble ionic liquid one or two orders of magnitude lower
[O35PYR][Br] 0.0100 >99.9 <0.04 than that of ammonium chloride classically used.
0.0200 >99.9 Overall, these results tend to conrm that water-soluble ionic
[OdMIM][Br] 0.0022 0 8.40  1.06 liquids are promising alternative salts for the precipitation of
0.0100 22.7 iridium(IV) dissolved in an aqueous solution containing HCl.
0.0195 71.5

Liquid–liquid extraction of IrCl62

All results are reported in Table 2. For comparison reasons,
Table 2 Extraction efficiency (Irextr%) and distribution coefficients (D)
for IrCl62

extracted from water using several ionic liquids distribution coefficients have been plotted as a function of HCl
concentration in Fig. 3.
Ionic liquid [HCl]/mol L
1 D Because [BMIM][NTf2] has been used in several articles
dealing with the extraction of metallic ions with ionic liquids,
[OMIM][NTf2] 0.01 71.4
this IL was used for the extraction of IrCl62
in water. Results
0.1 68.5
1 33.7 show that [BMIM][NTf2] is a poor extracting phase for iridiu-
4 13.7 m(IV), yielding D values below 3 whatever the pH of the aqueous
7.8 9.57 phase.
12 10.6
[OdMIM][NTf2] 0.01 7.98
0.1 5.67
1 3.40
4 1.98
7.8 1.41
12 0.88
[MOPYRRO][NTf2] 0.1 25.3
1 11.9
4 4.10
[O35PYR][NTf2] 0.01 19.6
0.1 19.5
1 11.9
4 5.52
7.8 4.96
12 6.12
[BMIM][NTf2] 0.01 3.25
1 1.44
4 0.42
7.8 0.34 Fig. 3 Distribution coefficients for IrCl62
as a function of HCl
12 0.28 concentration in water. (C): [OMIM][NTf2]. ( ): [MOPYRRO][NTf2]. ( ):
[O35PYR][NTf2]. ( ): [OdMIM][NTf2]. ( ): [BMIM][NTf2].

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RSC Advances Paper

Replacing butyl with octyl yields higher distribution coeffi- with the solvation energy of the cation in water, hence with the
cients. At the same pH, the D values obtained with [OMIM][NTf2] charge density of metal complex. The distribution coefficients
are systematically 20 to 30 times higher than those obtained with obtained with [OMIM][NTf2] for IrCl62
is higher than those for
[BMIM][NTf2]. Compared to other ionic liquids based on pyr- PtCl62
but lower than those obtained for PtBr62
. This trend is
idinium, pyrrolidinium or dimethylimidazolium cations, consistent with the thermochemical radius of IrCl62
(3.35 Å),
[OMIM][NTf2] yields highest D values reported in this study. compared to that of PtCl62
(3.13 Å) and PtBr62
(3.42 Å).23
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[OdMIM][NTf2] corresponds to [OMIM][NTf2] with an addi-

tional methyl group replacing the labile hydrogen on the imi-
dazolium ring. Using this IL, distribution coefficients towards Mechanism of liquid–liquid extraction
iridium(IV) appear to be one order of magnitude lower than Because the values for the molecular extinction coefficients at
those obtained using [OMIM][NTf2], whatever the pH of the 489 nm calculated for iridium(IV) dissolved in water containing
aqueous phase. various concentrations of HCl vary signicantly, the metallic
Obviously, the absence of a labile hydrogen reduces the ion is present under different forms in solution. In addition,
interaction between IrCl62
and the imidazolium ring. This is since D decreases with the concentration of HCl in water, one
most probably due to the fact that the labile hydrogen binds can assume that the iridium(IV) complex is extracted under
somehow with the iridium(IV) complex such as Im/H+/ different protonated forms, namely IrCl62
, HIrCl6
or H2IrCl6.
IrCl62
, either weakly or strongly, the hydrogen moving thus In the UV region, a weak absorption band was found to slightly
towards the IrCl62
anion. Because such an interaction does not shi from 303 to 301 nm with [HCl] and the shape of the peak
occur in the case of [OdMIM][NTf2], IrCl62
is less attracted changed from a distinct peak to a shoulder. This might also be
towards the imidazolium ring. an insight into the formation of different protonated forms of
Using a different cation such as [O35PYR]+ or [MOPYRRO]+ the IrCl62
complex.
yields extraction efficiencies that are lower than that obtained Plotting log(D) vs. log([HCl]) yielded linear regressions with
with [OMIM][NTf2], but higher than that for [OdMIM][NTf2]. all ionic liquids studied here. Slopes ranged from
0.4 and
Surprisingly, the D values measured here using [O35PYR][NTf2]
0.6. Such a behaviour has already been reported previously for
and [MOPYRRO][NTf2] are of similar values. Even though this metals in ILs or organic solvents.7,12 This was generally attrib-
proves the inuence of the structure of the cation ring (imda- uted to the simultaneous and competitive extraction of Cl
or
zolium vs. other cation ring) on the extraction efficiency of iri- HCl2
anions towards the organic phase. Nevertheless, in the
dium(IV), there appears to be no signicant difference between a absence of any pKa data for H2IrCl6, and without additional
pyridinium or a pyrrolidinium with regards to their extraction experiments, it is not possible at this point to elaborate further
efficiency towards iridium(IV). The relatively low D values on the subject.
obtained with [O35PYR][NTf2] are surprising because, as seen in Extraction mechanism was thus further investigated by
the preceding section dealing with the precipitation of Ir(IV), measuring the distribution coefficients for IrCl62
from an
[O35PYR]+ cation appears to associate in a stronger way to aqueous phase containing various amounts of Li[NTf2] salt.
IrCl62
anion than [OMIM]+ cation does in order to form a Experiments were carried out using [OMIM][NTf2] and aqueous
neutral pair insoluble in water. The interactions involved in the solutions at pH 1, because a high value for D (68) was obtained
liquid–liquid extraction of IrCl62
using ionic liquids are not under these conditions. Furthermore, the maximum concen-
necessarily the same as those involved in the precipitation of tration of Li[NTf2] used in these experiments is 0.1 M, because
IrCl62
. above that concentration, no signicant extraction of IrCl62

For all ionic liquids studied here, D values decrease monot- was observed and no reliable D values could be calculated. On
onously with the concentration of acid. This tends to show that the other hand, because the solubility product of [OMIM][NTf2]
the extraction mechanism is similar with all ionic liquids used in 0.1 M HCl was found to be 1.1 g L
1 (corresponding to 2.3
here. As explained in the following sub-section, no straightfor- 10
3 mol L
1 of [OMIM][NTf2] in water,) and because the
ward explanation was found so far for the decrease in D with concentration of [NTf2]
anion originating from Li[NTf2] added
HCl concentration. to the solution needs to be signicantly higher than that
Because platinum and iridium are neighbour atoms in the initially present (2.3 mM), a minimum concentration of Li[NTf2]
periodic table, because they are always present together in ores 0.01 mol L
1 was used.
and because they usually are extracted very similarly in classical Results are collected in Table 3 and show that extraction of
solvent extraction process,8 comparing the results reported here iridium(IV) decreases with the concentration of salt added in
with those previously obtained for platinum(IV) is relevant. First, water.
ionic liquids provide extracting phases which are more efficient Since Li[NTf2] can be regarded as a hydrophilic salt, Li+ and
at extracting Ir(IV) than Pt(IV) at low concentration of [HCl]. For NTf2
ions were assumed to remain in the aqueous phase during
instance, at a pH of 0.1 and using [OMIM][NTf2], D values of 68 the extraction experiment. Even though we are aware this
and 5.5 have been obtained for Ir(IV) and Pt(IV) respectively. At assumption is not completely true, it is valid as a rst approxi-
higher pH, this trend changes with [OMIM][NTf2].14 mation.24 The concentration of [NTf2]
anion was then calculated
Second, the results obtained here are consistent with the taking into account the solubility in water of [OMIM][NTf2]
assumption previously presented stating that the extraction of
such anionic metal complexes can be qualitatively correlated Ks ¼ x(x + [LiNTf2]) (5)

48264 | RSC Adv., 2014, 4, 48260–48266 This journal is © The Royal Society of Chemistry 2014
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Table 3 Distribution coefficients for IrCl62
obtained using [OMIM] iridium(IV) is extracted towards the ionic liquid phase, and one
[NTf2] and aqueous phase containing various concentrations of LiNTf2. aer [BMIM][NTf2] was contacted with a concentrated HCl
[HCl] ¼ 0.1 mol L
1
solution. Spectrophotometric analysis revealed that approxi-
LiNTf2/10
3 mol L
1 106 Ks [NTf2
]/10
3mol L
1 D mately 80% of the iridium(IV) was recovered from [BMIM][NTf2]
by this method. Because the distribution coefficients at 8 M HCl
10.02 5.36 10.53 3.354 are very close to those obtained at 12 M, similar results were
Published on 22 September 2014. Downloaded by Universite Joseph Fourier Grenoble 1 on 10/11/2014 10:15:54.

16.94 5.36 17.25 1.610 obtained when contacting [BMIM][NTf2] containing iridium(IV)
24.32 5.36 24.54 0.865
50.73 5.36 50.83 0.415
with a solution of 8 M HCl.
74.44 5.36 74.51 0.337 Similar experiments were carried out with [OdMIM][NTf2].
101.4 5.36 101.5 0.250 Results showed that approximately 56% of the iridium previ-
ously extracted in [OdMIM][NTf2] could be back extracted in an
8 M HCl solution.
Considering the distribution coefficients reported here for
with x the concentration of [OMIM]+ cation, and [LiNTf2] the iridium(IV) complexes with [OMIM][NTf2] are always above 9
concentration of Li[NTf2] salt added to the solution. Ks is the whatever the pH, back extraction of iridium(IV) from this ionic
solubility product of [OMIM][NTf2]. The concentration of liquid using HCl solutions was not possible. Instead, aqueous
[NTf2]
anion in the solution is here simply solutions containing HNO3 were used. In this case, 67% of
IrCl62
was back extracted in a 33% HNO3 solution. This is due
[NTf2
]aq ¼ x + [LiNTf2] (6) to the fact that nitrate anions are extracted more signicantly
towards the ionic liquid phase than chloride ions do.
Similarly to previous reports dealing with the extraction of
gold(III) and platinum(IV),11,14 such a behaviour is assumed to be
related to an ion exchange between the iridium complex and Conclusion
[NTf2]
anions. Due to electroneutrality during the extraction
process, this exchange can be described as following Five hydrophobic and three hydrophilic ionic liquids have been
used for removing IrCl62
from water containing various
2NTf 2
þ IrCl6aq 2
/2NTf 2aq
þ IrCl6 2
(7) concentrations of HCl.
where the subscript aq refers to the aqueous phase and the Precipitation of iridium(IV) using water-soluble ionic liquids
overline represents the ionic liquid phase. Following eqn (7), was carried out successfully starting from 1 mM IrCl62
and
one writes concentration of IL ranging from 2 to 40 mM. The precipitate
 2   was composed of two ionic liquid cations and one IrCl62

NTf 2
aq IrCl6 2
complex. Ks values obtained in this study were found to be up to
Kex ¼   2 (8)
IrCl6 2
NTf 2

where Kex is the equilibrium constant of eqn (6). Taking into Table 4 Back-extraction of IrCl62
from [BMIM][NTf2], [OdMIM][NTf2]
account eqn (2), one obtains or [OMIM][NTf2] into acidic solutions
 2
NTf 2
1 Ionic liquid Acid [H+]/mol L
1 %E
D¼  2 (9)
Kex NTf 2
aq [OMIM][NTf2] HNO3 5 67.3
[OdMIM][NTf2] HCl 7.8 56.4
[BMIM][NTf2] HCl 7.8 80.5
D is therefore expected to vary linearly with 1/[NTf2
]2.
Plotting D as a function of [NTf2
]2 as suggested in eqn (9) yields
a linear regression with a good correlation factor (r2 ¼ 0.997).
This conrms that the extraction of iridium follows an anion
exchange with ILs based on [NTf2] anions.

Back-extraction of Ir(IV) ions

Starting from the results provided in this study, simple back
extraction procedures were carried out as presented in Table 4.
First, aer extraction of iridium(IV) at 0.01 M HCl using
[BMIM][NTf2], the ionic liquid pregnant with iridium(IV) was
contacted with a 12 M HCl aqueous phase. The volume of water
was equal to ve times that of the ionic liquid. The ionic liquid
Fig. 4 Snapshots of back extraction of iridium(IV). First snapshot: iri-
lost its brown colour upon contact, and aer 2 minutes, most dium(IV) extracted in 0.7 g [BMIM][NTf2]. Second snapshot: back
iridium was back extracted in the aqueous phase. Fig. 4 pres- extraction of iridium(IV) after adding 4 cm3 of 37% HCl solution to the
ents two snapshots, one from [BMIM][NTf2] taken aer ionic liquid phase from the first snapshot.

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