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The large scale synthesis of pure imidazolium and pyrrolidinium ionic

liquids
Anthony K. Burrell,*a Rico E. Del Sesto,a Sheila N. Baker,b T. Mark McCleskeya and Gary A. Bakerb
Published on 16 February 2007. Downloaded by National Chemical Laboratory, Pune on 26/08/2016 17:36:48.

Received 2nd November 2006, Accepted 18th January 2007

First published as an Advance Article on the web 16th February 2007
DOI: 10.1039/b615950h

Ionic liquids are being employed in almost all areas of chemistry and materials, yet there are
inherent issues which arise if the utmost care is not taken in the preparation and purification of
these materials. They are not easily synthesized and purified using the existing methods. We
describe a reliable method for producing large quantities of high quality ionic liquids.
Additionally, we show that imidazoliums are not ‘special’ due to their ‘inherently fluorescent’
nature, that spectroscopically clean imidazoliums are attainable, and most classes of ionic liquids
do exhibit fluorescent backgrounds when extreme care is not taken during their synthesis and
purification.

Introduction
Ionic liquids have become solvents of choice in many
applications,1 being used for purposes as diverse as electro-
chemiluminescence2 and lubrication.3 The required purity of
any solvent varies with its application. In many cases the
purity of the ionic liquid is not important. However, in
applications such as biology, electrochemistry, catalysis,
electron transfer and spectroscopy, the highest purity materials
are desirable and necessary. It is unfortunate that the ionic
liquids that can currently be purchased and those prepared
using the synthetic procedures found in the literature are not of
particularly high quality. Here we report simple and reliable
methods for producing high quality ionic liquids which can be
carried out on large scales (.1 kg).
Few publications provide sufficient information that can be
used to judge the purity of the ionic liquids being employed.
We have been interested in the properties of ionic liquids and
more importantly their use as solvents for electrochemistry and
spectroscopy.4 Our initial samples were either prepared using
the standard procedures or were purchased from commercial
sources. However, these materials were almost always slightly
yellow. More recent attempts to produce spectroscopic grade
ionic liquids report that the materials can be cleaned, but limit
their descriptions to only a few ionic liquids.5 In addition, the
papers that describe synthetic routes to ionic liquids often do
not describe any data related to the purity of the materials
obtained. Even the recent synthesis of 1-butyl-3-methylimida-
zolium tetrafluoroborate described in Organic Synthesis,
the gold standard for organic synthesis, describes the product
as ‘colourless to pale yellow’.6 The colour issue is shown in
Fig. 1, where the sample on the left is a commercially
purchased sample of 1-ethyl-3-methylimidazolium
a
Materials Chemistry, Materials Physics and Applications, Los Alamos
National Laboratory, Los Alamos, NM 87545, USA.
E-mail: Burrell@LANL.GOV; Fax: +1-505-667-9905;
Tel: +1-505-667-9342
b
Chemical Sciences Division, Oak Ridge National Laboratory, Oak
Ridge, TN 37831-6110, USA
Fig. 1 Commercial quality 1-ethyl-3-methylimidazolium bis(trifluor-
omethanesulfonyl)amide (left) and a sample made in our laboratory
(right).
bis(trifluoromethanesulfonyl)amide and the right sample is
prepared in our laboratory.
In general the commercial sources of ionic liquids are of
dubious quality. Almost all commercial ionic liquids are
coloured and often have strong odours. Merck currently
describes most of their commercial ionic liquids as foul
smelling coloured materials. However, ionic liquids are
odourless and most are colourless!
The presence of colour in colourless materials is a clear
indication of impurities. It is likely that the data obtained from
employing impure ionic liquids may not be reliable and can
lead to incorrect conclusions. For example, imidazolium-based
ionic liquids have been described as possessing an inherent
fluorescence.7 This is simply not true. When pure ionic liquids
with imidazolium as the cation are prepared, they possess no
inherent fluorescence.
Experimental
Commercial ionic liquids were purchased from Merck, Aldrich
and Acros. All other reagents were purchased from Aldrich
and used as received or purified as described.
UV-Vis measurements were carried out using an HP Model
8453. Fluorescent measurements were carried out using a PTI
GL-3300 fluorimeter with an R955 photomultiplier. Nuclear
Magnetic Resonance (NMR) spectra were measured at
400 MHz (1H), on a Bruker Avance 400 Ultrashield spectro-
meter. All NMR spectra were recorded in deuterochloroform
unless otherwise stated, with reference to tetramethylsilane.

This journal is ß The Royal Society of Chemistry 2007 Green Chem., 2007, 9, 449–454 | 449

1-Ethyl-3-methylimidazolium chloride
Yellow 1-ethyl-3-methylimidazolium chloride (Aldrich) (50 g)
was dissolved in deionized water (250 mL). Decolourizing
charcoal (3 g) was added to the solution and the resulting
mixture heated at 65 uC for 24 h. The solution was cooled to
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room temperature and filtered. At this point the solution
should be completely colourless. However, in some cases
colour remained and the decolourizing charcoal step was
repeated. The water was then removed using a lyophilizer. The
resulting solid was then heated under high vacuum for 48 h at
65 uC. The material was cooled and the pure white solid was
obtained in essentially quantitative yield.
1-Ethyl-3-methylimidazolium bromide
1-Ethyl-3-methylimidazolium bromide (Aldrich) (50 g) was
treated as for 1-ethyl-3-methylimidazolium chloride to yield
the product as a white solid in quantitative yield.
1-Butyl-3-methylimidazolium chloride
n-Chlorobutane (600 g) was slowly added to freshly distilled
methylimidazole (500 g) in a 2 L two-necked round-bottom
flask fitted with a reflux condenser. This mixture was then
stirred with a magnetic stirrer at 70 uC for one week. During
the week a white solid formed, which slowly turned yellow.
The solution was allowed to cool to room temperature and any
remaining solution was separated by decanting. The yellow
solid was then washed with diethyl ether (3 6 200 mL) and
dried under vacuum for 24 h. The yellow solid was dissolved in
water (1.5 L) and decolourizing charcoal (30 g) was added.
This solution was heated to 70 uC for 24 h, cooled and filtered.
At this point the solution should be completely colourless.
However, in some cases colour remained and the decolourizing
charcoal step was repeated. The water was then removed using
a lyophilizer. The resulting solid was then heated under high
vacuum for 48 h at 65 uC. The material was cooled and the
pure white solid was obtained at 92% yield.
1-Butyl-3-methylimidazolium bromide
n-Bromobutane (860 g) was slowly added to freshly distilled
methylimidazole (500 g) in a 2 L two-necked round-bottom
flask fitted with a reflux condenser. Caution: this reaction is
exothermic and cooling is advisable for large scale reactions.
The addition was at such a rate that the temperature of the
solution did not get above 40 uC. This mixture was then stirred
with a magnetic stirrer at room temperature for one day.
During this time a yellow solid formed. The yellow solid was
then purified as for 1-butyl-3-methylimidazolium chloride to
give the product in 94% yield.
1-Butyl-1-methylpyrrolidinium chloride
n-Chlorobutane (570 g) was slowly added to freshly distilled
methylpyrrolidine (500 g) in a 2 L two-necked round-bottom
flask fitted with a reflux condenser. This mixture was then
stirred with a magnetic stirrer at 70 uC for one week. During
the week a white solid formed, which slowly turned yellow.
The solution was allowed to cool to room temperature and any
450 | Green Chem., 2007, 9, 449–454
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remaining solution was separated by decanting. The yellow
solid was then purified as for 1-butyl-3-methylimidazolium
chloride to give the product in 89% yield.
1-Butyl-1-methylpyrrolidinium bromide
n-Bromobutane (900 g) was slowly added to freshly distilled
methylpyrrolidine (500 g) in a 2 L two-necked round-bottom
flask fitted with a reflux condenser. Caution: this reaction is
exothermic and cooling is advisable for large scale reactions.
The addition was at such a rate that the temperature of the
solution did not get above 40 uC. This mixture was then stirred
with a magnetic stirrer for one day to give a yellow solid. The
yellow solid was then purified as for 1-butyl-3-methylimida-
zolium chloride to give the product in 91% yield.
1-Butyl-2,3-dimethylimidazolium chloride
n-Chlorobutane (55 g) was slowly added to 1,2-dimethylimi-
dazole (50 g) in a 200 mL two-necked round-bottom flask
fitted with a reflux condenser. This mixture was then stirred
with a magnetic stirrer at 70 uC for one week. During the week
a white solid formed, which slowly turned yellow. The yellow
solid was then purified as for 1-butyl-3-methylimidazolium
chloride (adjusted for scale) to give the product in 85% yield.
1-Butyl-2,3-dimethylimidazolium bromide
n-Bromobutane (80 g) was slowly added to 1,2-dimethylimi-
dazole (50 g) in a 200 mL two-necked round-bottom flask
fitted with a reflux condenser. Caution: this reaction is
exothermic and cooling is advisable for large scale reactions.
The addition was at such a rate that the temperature of the
solution did not get above 40 uC. This mixture was then stirred
with a magnetic stirrer for one day to give a yellow solid. The
yellow solid was then purified as for 1-butyl-3-methylimida-
zolium chloride (adjusted for scale) to give the product in 98%
yield.
1-Butyl-3-methylimidazolium tetrafluoroborate
n-Bromobutane (600 g) was slowly added to freshly distilled
methylimidazole (500 g) in a 2 L two-necked round-bottom
flask fitted with a reflux condenser. Caution: this reaction is
exothermic and cooling is advisable for large scale reactions.
The addition was at such a rate that the temperature of the
solution did not get above 40 uC. This mixture was then stirred
with a magnetic stirrer at room temperature for one day.
During this time a yellow solid formed. This solid was filtered
and washed with diethyl ether (3 6 200 mL) then dried under
vacuum. The yellow solid was then dissolved in deionized
water (1.5 L). Decolourizing charcoal (30 g) was added to the
solution and the resulting mixture heated at 65 uC for 24 h.
The mixture was then cooled to room temperature and filtered.
At this point the solution should be colourless. If any colour
remained the decolourizing charcoal step was repeated. The
clean 1-butyl-3-methylimidazolium bromide solution was then
poured into a solution of sodium tetrafluoroborate (680 g) in
1 L of deionized water. The solution was then stirred at
room temperature for 3 h. The solution was then transferred to
a continuous liquid–liquid extractor and extracted with
This journal is ß The Royal Society of Chemistry 2007

dichloromethane for 48 h. The dichloromethane solution was
filtered through a plug of silica (100 g), then the dichloro-
methane was removed under vacuum to give the neat 1-butyl-
3-methylimidazolium tetrafluoroborate. This material was
often contaminated with quantities of sodium bromide. A
simple silver test was used to determine the presence of the
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bromide ion. If a positive test for bromide was obtained, the
crude 1-butyl-3-methylimidazolium tetrafluoroborate was dis-
solved in deionized water (500 mL) and extracted in the liquid–
liquid extractor with dichloromethane for 48 h. The dichloro-
methane solution was filtered through a plug of silica and the
dichloromethane removed under vacuum. This process was
repeated until a negative bromide test was obtained. The
colourless, bromide-free 1-butyl-3-methylimidazolium tetra-
fluoroborate was obtained in .95% yield even with repeated
liquid–liquid extractions.
1-Ethyl-3-methylimidazolium tetrafluoroborate
1-Ethyl-3-methylimidazolium bromide (50 g) was dissolved in
deionized water (200 mL). Decolourizing charcoal (3 g) was
added to the solution and the resulting mixture heated at 65 uC
for 24 h. The mixture was then cooled to room temperature
and filtered. At this point the solution should be colourless. If
any colour remained the decolourizing charcoal step was
repeated. The clean 1-ethyl-3-methylimidazolium bromide
solution was then poured into a solution of sodium
tetrafluoroborate (30 g) in 200 mL of deionized water. The
solution was then stirred at room temperature for 3 h. The
1-ethyl-3-methylimidazolium tetrafluoroborate was then pur-
ified as for 1-butyl-3-methylimidazolium tetrafluoroborate.
The colourless, bromide-free 1-ethyl-3-methylimidazolium
tetrafluoroborate was obtained in .90% yield.
1-Ethyl-3-methylimidazolium triflate
1-Ethyl-3-methylimidazolium bromide (50 g) was dissolved in
deionized water (200 mL). Decolourizing charcoal (3 g) was
added to the solution and the resulting mixture heated at 65 uC
for 24 h. The mixture was then cooled to room temperature
and filtered. At this point the solution should be colourless. If
any colour remained, the decolourizing charcoal step was
repeated. The clean 1-ethyl-3-methylimidazolium bromide
solution was then poured into a solution of sodium triflate
(50 g) in 200 mL of deionized water. The solution was then
stirred at room temperature for 3 h. The 1-ethyl-3-methylimi-
dazolium triflate was then purified as for 1-butyl-3-methyli-
midazolium tetrafluoroborate. The colourless, bromide-free
1-ethyl-3-methylimidazolium triflate was obtained in .95%
yield.
1-Butyl-3-methylimidazolium triflate
n-Bromobutane (60 g) was slowly added to freshly distilled
methylimidazole (50 g) in a 2 L two-necked round-bottom
flask fitted with a reflux condenser. Caution: this reaction is
exothermic and cooling is advisable for large scale reactions.
The addition was added at such a rate that the temperature of
the solution did not get above 40 uC. This mixture was then
stirred with a magnetic stirrer at room temperature for one
This journal is ß The Royal Society of Chemistry 2007
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day. During this time a yellow solid formed. This solid was
filtered and washed with diethyl ether (3 6 20 mL) then dried
under vacuum. The yellow solid was then dissolved in
deionized water 100 mL. Decolourizing charcoal (3 g) was
added to the solution and the resulting mixture heated at 65 uC
for 24 h. The mixture was then cooled to room temperature
and filtered. At this point the solution should be colourless. If
any colour remained the decolourizing charcoal step was
repeated. The clean 1-butyl-3-methylimidazolium bromide
solution was then poured into a solution of sodium triflate
(110 g) in 200 mL of deionized water. The solution was then
stirred at room temperature for 3 h. The 1-butyl-3-methylimi-
dazolium triflate was then purified as for 1-butyl-3-methyli-
midazolium tetrafluoroborate. The colourless, bromide-free
1-butyl-3-methylimidazolium triflate was obtained in .95%
yield.
1-Butyl-2,3-dimethylimidazolium triflate
Prepared as for 1-butyl-3-methylimidazolium tetrafluorobo-
rate to give the product as a white solid in .90% yield.
1-Butyl-1-methylpyrrolidinium tetrafluoroborate
Prepared as for 1-butyl-3-methylimidazolium tetrafluorobo-
rate to give the product as a white solid in .90% yield.
1-Butyl-1-methylpyrrolidinium triflate
Prepared as for 1-butyl-3-methylimidazolium tetrafluorobo-
rate to give the product as a colourless liquid in .90% yield.
1-Ethyl-3-methylimidazolium
bis(trifluoromethanesulfonyl)amide
Yellow 1-ethyl-3-methylimidazolium chloride (Aldrich) (50 g)
was dissolved in deionized water (250 mL). Decolourizing
charcoal (3 g) was added to the solution and the resulting
mixture heated at 65 uC for 24 h. The solution was cooled to
room temperature and filtered. At this point the solution
should be completely colourless. However, in some cases
colour remained and the decolourizing charcoal step was
repeated. The clean 1-ethyl-3-methylimidazolium chloride
solution was then poured into a solution of lithium bis(tri-
fluoromethanesulfonyl)amide (115 g) in 200 mL of deionized
water. The solution was then stirred at room temperature for
3 h after which two layers had formed. The bottom layer was
separated and washed three times with deionized water
(100 mL). The 1-ethyl-3-methylimidazolium bis(trifluoro-
methanesulfonyl)amide was then heated at 65 uC under
vacuum for 48 h and then filtered through activated alumina
to give colourless clean dry material in 89% yield.
1-Butyl-1-methylpyrrolidinium
bis(trifluoromethanesulfonyl)amide
n-Bromobutane (900 g) was slowly added to freshly distilled
methylpyrrolidine (500 g) in a 2 L two-necked round-bottom
flask fitted with a reflux condenser. Caution: this reaction is
exothermic and cooling is advisable for large scale reactions.
The addition was added at such a rate that the temperature of
Green Chem., 2007, 9, 449–454 | 451

the solution did not get above 40 uC. This mixture was then
stirred with a magnetic stirrer at room temperature for one
day. During this time a yellow solid forms. This solid was
filtered and washed with ether (3 6 200 mL) then dried under
vacuum. The yellow solid was then dissolved deionized water
(1 L). Decolourizing charcoal (30 g) was added to the solution
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and the resulting mixture heated at 65 uC for 24 h. The mixture
was then cooled to room temperature and filtered. At this
point the solution should be colourless. If any colour remains
repeat the decolourizing charcoal step. The clean 1-butyl-1-
methylpyrrolidinium bromide solution was then poured into a
solution of lithium bis(trifluoromethanesulfonyl)amide
(1800 g) in deionized water (2 L). The solution was then
stirred at room temperature for 3 h after which two layers had
formed. The bottom layer was separated and washed three
times with deionized water (500 mL). The 1-butyl-1-methyl-
pyrrolidinium bis(trifluoromethanesulfonyl)amide was then
heated at 65 uC under vacuum (0.1 mbar) for 48 h and then
filtered through activated alumina to give colourless clean dry
material (89% yield).
1-Butyl-3-methylimidazolium
bis(trifluoromethanesulfonyl)amide
n-Bromobutane (860 g) was slowly added to freshly distilled
methylimidazole (500 g) in a 2 L two-necked round-bottom
flask fitted with a reflux condenser. Caution: this reaction is
exothermic and cooling is advisable for large scale reactions.
The addition was added at such a rate that the temperature of
the solution did not get above 40 uC. This mixture was then
stirred with a magnetic stirrer at room temperature for one
day. During this time a yellow solid forms. This solid was
filtered and washed with diethyl ether (3 6 200 mL) then dried
under vacuum. The yellow solid was then dissolved deionized
water (1 L). Decolourizing charcoal (30 g) was added to the
solution and the resulting mixture heated at 65 uC for 24 h.
The mixture was then cooled to room temperature and filtered.
At this point the solution should be colourless. If any colour
remained the decolourizing charcoal step was repeated. The
clean 1-butyl-3-methylimidazolium bromide solution was then
poured into a solution of lithium bis(trifluoromethanesulfo-
nyl)amide (1850 g) in 2 L of deionized water. The solution was
then stirred at room temperature for 3 h after which two layers
had formed. The bottom layer was separated and washed three
times with deionized water (500 mL). The 1-butyl-3-methyli-
midazolium bis(trifluoromethanesulfonyl)amide was then
heated at 65 uC under vacuum for 48 h and then filtered
through activated alumina to give clean dry material in 89%
yield.
Results and discussion
In our work on electrochromic and electrochemical applica-
tions of ionic liquids, we initially purchased our materials.
Then we realised that the data we obtained from the
commercial liquids were dependent on both supplier and
the batch we used. The synthesis of ionic liquids using the
standard literature methods always resulted in yellow materi-
als. The most common organic ammonium cation-based
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liquids, including the imidazolium and pyrrolidinium cations,
should appear ‘water-white’ when pure.
A simple test is to place a vial of ionic liquid next to a vial of
water. These should be indistinguishable by the naked eye.
Recently, it has been demonstrated that it is possible to
distill ionic liquids.8 Unfortunately, this is a slow process and
is not currently suitable for the purification of large volumes of
material. The most commonly attempted method for purifying
ionic liquids utilizes activated carbon or decolourizing
charcoal.9 We examined these in the purification of synthe-
sized and commercial ionic liquids and discovered that they
did not significantly enhance the purity. Discussions with other
research groups confirmed that this is a general finding. We
therefore set about redesigning the synthesis of the ionic
liquids. It is hard to think of a simpler synthesis than the
preparation of salts by metathesis. Clearly there was little that
could be done to improve this reaction. However, there is
significant room for advancement in the purity of the
precursors, and this is the crux of the purification of ionic
liquids. It turns out that all of the reported preparations of
ionic liquids almost never discuss the purification of the
precursors. These precursors, when purchased commercially or
prepared using the literature methods, are almost all coloured.
However, it is clear that in the case of simple ammonium
chlorides or bromides the colour is an indication of the
presence of impurities.
We examined the synthesis of the ammonium chlorides and
bromides and discovered that if the temperature was con-
trolled very carefully the intensity of the yellow colour could be
minimized, but not completely excluded. As we were interested
in the large-volume synthesis of ionic liquids it was difficult to
limit local heating and the formation of colour. Therefore we
took the logical step and purified the ammonium chlorides and
bromides after preparing them.
High quality ionic liquids can be obtained if the precursors
are purified prior to the synthesis of the ionic liquid. This can
be simply achieved using decolourizing charcoal in water.
Either heating to reflux temperature for 3–5 min or heating at
65 uC for 24 h. We prefer the lower temperature with longer
times, but both methods produce clean materials.
This is a general method for the production of ionic liquids
based upon nitrogen cations and can be scaled to the limits of
your glassware. There is a clear difference in the properties of
the different classes of salts. The water-soluble materials can be
effectively cleaned using decolourizing charcoal in water. If the
salts are insoluble in water, we could find no solvent system
that enabled decolourizing of the salts. Clearly, the ability to
wet the decolourizing charcoal is a key issue and may explain
why the ionic liquids are so difficult to clean-up once prepared.
The only other issue we had was the difficulty in obtaining
useful yields in the synthesis of halide-free, water-miscible ionic
liquids. Extraction using dichloromethane is tedious using
simple extraction funnels. However, quantitative yields can be
obtained using liquid–liquid continuous extractors. This
straightforward modification to the extraction enables multi-
ple rewashing of the ionic liquid and the systematic removal of
the halide as determined by a silver halide test and mass
spectrometry. We also filter the liquid through silica, and it is
likely that the filtration through silica does more to remove the
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salts than the water washing. We employ both due to the

simple nature of the whole process.
We produce our own cations from alkylation using alkyl
bromides and alkyl chorides. This gives more control over the
process. However, even commercial cation sources produce
excellent ionic liquids when they are purified using this
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method. The purity of the ionic liquids can be judged using

a variety of spectroscopic techniques.
UV-Vis spectroscopy is the simplest method to determine
optical purity in the ionic liquids. Fig. 2 shows the UV-Vis
spectrum for 1-butyl-1-methylpyrrolidinium bis(trifluoro-
methanesulfonyl)amide. This spectrum was performed using
a neat sample (1 cm pathlength) and it is apparent that in the
pure material there is no absorbance above 300 nm as shown in
Fig. 2. This is the same for all of the ionic liquids described
here. The solids can be examined using saturated aqueous
solutions. If there is significant absorption above 350 nm the
ionic liquid is impure.
Fluorescence spectroscopy is perhaps the most sensitive
method for determining the purity of an ionic liquid. The
fluorescence spectra of two commercial samples of 1-butyl-1- Fig. 3 Fluorescence spectra of 1-butyl-1-methylpyrrolidinium bis(tri-
methylpyrrolidinium bis(trifluoromethanesulfonyl)amide (A fluoromethanesulfonyl)amide, commercial samples (A and B) and a
and B), and a sample prepared using our synthesis (C) are sample prepared in our laboratory (C).
shown in Fig. 3. We have observed that it is possible to reduce
the fluorescence of the ionic liquids to effectively zero by syste- employ a platinum working electrode, a platinum counter
matic purification of the precursor salts. For the lowest electrode and a silver wire as the reference electrode. All we are
fluorescence response it is necessary to take particular care interested in is the electrochemical window and the current
with all aspects of the synthesis. For example, we initially therein. Fig. 4 shows the cyclic voltammogram of clean
filtered the aqueous solutions through Celite to remove the 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)
charcoal. However, we found that we obtained materials with amide.
lower fluorescence background when we do not use Celite Nuclear magnetic resonance spectroscopy is the most
– filter paper is sufficient. For convenience it is possible to common method for characterizing ionic liquids. It is,
judge the level of fluorescence impurity in the ionic liquid by however, the least useful for judging purity. Spectra of dark
exposing a sample to UV light from a hand scanner at 380 nm. yellow ionic liquids generally look as clean as those which have
If the ionic liquid has significant impurities it will fluoresce no UV-Vis absorbance as seen in Fig. 5. It should be
visibly. remembered that NMR cannot readily identify compounds
The simple electrochemistry of ionic liquids provides a very present at less than 1%. So while NMR is a useful
quick indicator of the general purity. It is not necessary to even characterization tool, it is not an appropriate method for
use an accurate reference electrode since a cyclic voltammo- judging anything but gross purity.
gram scan provides the information required. We generally

Fig. 4 Cyclic voltammogram of neat 1-butyl-1-methylpyrrolidinium

Fig. 2 UV-Vis spectrum of neat 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)amide (blue is commercial, red is pre-
bis(trifluoromethanesulfonyl)amide (the upper trace is commercial pared in our laboratory), platinum working electrode, platinum
high purity grade, the lower trace is prepared in our laboratory). counter electrode and a silver reference electrode scanned at 50 mV s21.

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Fig. 5 1H NMR spectra of 1-butyl-3-methylimidazolium bis(trifluor-
omethanesulfonyl)amide, colourless sample (a) and yellow sample (b).
In the materials we have examined the issue of quantifying
the levels of impurities is always problematic. Without a clear
understanding of the nature of the impurity it is impossible to
accurately determine the level of impurities in any given
sample. In the material prepared in this report we have
determined the levels of water to be less than 20 ppm. We
estimate the levels of coloured impurities at less than 25 ppm,
based upon a scenario of a highly coloured dye impurity with
an e = 50 000 L mol21 cm21. It is even more difficult to predict
the levels of fluorescence impurities but we estimate that they
will not be greater than the coloured impurities at 25 ppm.
Halide impurities are generally present at less than 20 ppm.
Conclusions
The purity of ionic liquids has been the bane of many chemists
and materials scientists almost since their discovery. In many
cases the impurities present at the sub 1% level are not a cause
454 | Green Chem., 2007, 9, 449–454
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for concern. However, with more specialized applications, such
as spectroscopy, electrochemistry, catalysts and where reaction
kinetics are an issue, this is not the case. We have seen
examples where incorrect assumptions have been derived from
data collected from impure ionic liquids. How many other
cases where negative data were obtained for reactions
involving ionic liquids are due to the impurities? We would
recommend that those who are doing research where the purity
of ionic liquids may be important should at least examine
the UV-Vis spectroscopy and quote those data in their
publications.
Acknowledgements
This work was supported by the Department of Energy
Buildings Technology Program. G. A. B. acknowledges
generous support by a Frederick Reines Fellowship. R. E. D.
S. wishes to acknowledge the LANL Director’s Fellowship for
support.
References
1 Ionic Liquids, Industrial Applications for Green Chemistry, ed. R. D.
Rogers and K. R. Seddon, American Chemical Society, Washington
DC, 2002; T. Welton, Chem. Rev., 1999, 99, 2071–2083.
2 B. M. Quinn, Z. Ding, R. Moulton and A. J. Bard, Langmuir, 2002,
18, 1734–1742.
3 J. Qu, J. J. Truhan, S. Dai, H. Luo and P. J. Blau, Tribology Lett.,
2006, 22, 207–214.
4 R. E. Del Sesto, G. A. Baker, S. N. Baker, B. L. Scott, T. S. Keizer,
A. K. Burrell and T. M. McCleskey, Chem. Commun., 2006,
272–274; B. P. Warner, T. M. McCleskey, A. Agrawal, J. P. Cronin,
J. C. L. Tonazzi and A. K. Burrell, US Pat., 2005, 6,853,472.
5 P. Nockemann, K. Binnemans and K. Driesen, Chem. Phys. Lett.,
2005, 415, 131–136.
6 X. Creary and E. D. Willis, Org. Synth., 2005, 82, 166.
7 A. Paul, P. K. Mandal and A. Samanta, Chem. Phys. Lett., 2005,
402, 375–379.
8 M. J. Earle, J. M. S. S. Esperanca, M. A. Gilea, J. N. Canongia
Lopes, L. P. N. Rebelo, J. W. Magee, K. R. Seddon, R. Kenneth
and J. A. Widegren, Nature, 2006, 439, 831–834.
9 V. Farmer and T. Welton, Green Chem., 2002, 4, 97.
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