J. Chem. T ech. Biotechnol.

1997, 68, 351356

Review
Ionic Liquids for Clean Technology*
Kenneth R. Seddon
School of Chemistry, The Queens University of Belfast, Stranmillis Road, Belfast BT9 5AG, UK
(Received 20 June 1996 ; accepted 5 August 1996)

Abstract : The use of room-temperature chloroaluminate(III) ionic liquids, specically 1-butylpyridinium chloridealuminium(III) chloride and 1-ethyl-3-methylimidazolium chloridealuminium(III) chloride, as solvents for clean synthesis and
catalytic processes, particularly those applicable to clean technology, is becoming
widely recognised and accepted. The design principles for room-temperature
ionic liquids, some of their properties, and the rationale for using these neoteric
solvents, are discussed here, and an indication of the scope of these solvents for
future industrial processes is given.
Key words : ionic liquids, molten salts, clean technology, clean synthesis, neoteric
solvents, chloroaluminates(III)

1 PREAMBLE

ous support from BP Chemicals, Unilever, ICI, BNFL,

IRTU and EPSRC (ROPA and Clean Synthesis
awards), combined with the blood, sweat and tears of
dozens of graduate students and postdoctoral fellows,
we believe that the initial concepts and speculation have
been vindicated, and that the industrial relevance of
ionic liquids, especially for clean synthesis and clean
catalysis, has been demonstrated (vide infra).
The purpose of this brief review is to give an introduction to the nature and properties of roomtemperature ionic liquids, with particular emphasis
being placed upon their potential as solvents for industrially relevant catalytic reactions, and (more generally)
for clean technology. This account is neither comprehensive nor exhaustive, but is intended to whet the
appetite of the reader, and perhaps encourage further
interest in a subject that, until recently, had been generally considered as rather esoteric. This account centres
around the use of room-temperature chloroaluminate
ionic liquids as solvents, especially the systems 1butylpyridinium
chloridealuminium(III)
chloride,
[NBupy]ClAlCl
and 1-ethyl-3-methylimidazolium
3
chloridealuminium(III) chloride, [emim]ClAlCl (see
3
Scheme 1) : these are by no means the only systems
which may be used for catalytic studies, but they are
undoubtedly the archetypal systems. Much greater

Ionic liquids ? Neoteric solvents ? Molten salts for clean

technology and catalysis ? Are you serious ? ? Well, yes, I
am serious, but yes there are questions to be answered.
In 1982, I submitted a proposal to the then SERC
which concerned the use of room-temperature ionic
liquids to study catalytic processes which might have
some industrial application. The proposal was rejected :
referee 1 stated that the systems were far too complicated, and therefore would never have any application,
referee 2 thought that the systems were far too simple,
and the work was not worth doing, and referee 3
(clearly not having the correct proposal in front of him)
wondered why we wanted to study the neutron diraction patterns of vanadium bronzes ! ! Fortunately, the
BP Venture Research Unit (headed by Prof. Don
Braben) was more imaginative, and shortly afterwards
awarded us a substantial grant to enable us to investigate the chemistry of ionic liquids. In 1996, thanks to
this crucial grant, and with subsequent extremely gener* This paper is dedicated to the memory of Prof. Gleb
Mamantov, whose recent death has deprived the ionic liquids
community of its most respected, and best loved, expert.
Presented in part at Clean Tech 96, London, 1921 June
1996.

351
J. Chem. T ech. Biotechnol. 0268-2575/97/$17.50 ( 1997 SCI. Printed in Great Britain

K. R. Seddon

352

3 RATIONALE : WHY USE IONIC LIQUIDS ?

Scheme 1.

detail concerning these solvents may be discovered in

two exceptional reviews by Hussey.1,2 An excellent
review of the chemistry in the related pyrophoric
system, [bmim]ClAlEtCl
([bmim]` \ 1-butyl-32
methylimidazolium cation), has recently been published
by Chauvin and Olivier-Bourbigou3 and the same
group has just reported some novel catalytic reactions
in air-stable ionic liquids,4 derived from those developed by Wilkes and Zaworotko.5

The question as to why use ionic liquids at all has

recently been addressed in detail elsewhere, in a companion review,8 which has been made available on a
World-Wide Web site,9 as a section of a dedicated ionic
liquids database.10 The relative merits of using ionic
liquids, instead of the more common molecular solvents,
are rehearsed there, and will not be repeated here.
Moreover, the case for using room-temperature ionic
liquids rather than high-temperature ionic liquids is
also argued. To briey summarise, ionic liquids
suppress conventional solvation and solvolysis phenomena, and provide media capable of dissolving a vast
range of inorganic molecules to very high concentrations. The low (i.e. ambient) temperatures suppress dissociation,
disproportionation
and
degradation
reactions, and the ionic environment tends to signicantly extend the lifetimes of species (such as
[RuCl ]3~)11 which are unstable in conventional
6
molecular solvents.

4 ROOM TEMPERATURE IONIC LIQUIDS

2 TERMINOLOGY
Ionic liquids are, quite simply, liquids that are comprised entirely of ions. Thus, molten sodium chloride is
an ionic liquid : a solution of sodium chloride in water
(a molecular solvent) is an ionic solution. The term ionic
liquids was selected with care, as it is my belief that the
more commonly used phrase molten salts (or simply
melts) is referential, and invokes a awed image of these
solvents as being high-temperature, corrosive, viscous
media (cf. molten cryolite). The reality is that roomtemperature ionic liquids can be uid at temperatures
as low as [ 96C, and are colourless, have low viscosities, and are easily handled. To use the term molten
salts to describe these novel systems is as archaic as
describing a car as a horseless carriage.
The abstract of this review includes a term new to
chemistry : neoteric solvents. The word neoteric is well
established in the English language. It is used here to
indicate a class of novel solvents that have remarkable
new properties, that break new ground, and that oer
a huge potential for industrial application. It is applied
not only to ionic liquids, but also to supercritical
uids,6,7 another type of solvent that shows huge
promise for clean synthesis. Thus the term neoteric solvents covers both ionic liquids and supercritical uids,
and brings together under one banner the two most
promising solvent systems for cleaning up the modern
chemical industry.

Neoteric is dened in the Oxford English Dictionary as

meaning : recent, new, modern.

4.1 Lowering the melting point

The melting points of the Group 1 chlorides are given
in Table 1.12 As can be seen, these are signicantly
above room temperature, and far too high to form a
generic medium for reactive chemistry. However, the
eutectic compositions of mixed ternary systems do melt
at signicantly lower temperatures than either binary
component (see Fig. 1). Applying the understanding of
lattice energies gained from the Kapustinskii equation,13 the eect of increasing the size of the anion can
be seen in Table 2. The melting points of these simple
tetrachloroaluminate(III) salts are in the range of the
boiling points of high-boiling organic solvents. Furthermore, as the sodium chloridealuminium(III) chloride
system shows compound formation at the 1 : 1 composition (viz. Na[AlCl ]), the idealised phase diagram (Fig.
4
2) now exhibits two eutectic points. However, as these
represent the lowest temperatures at which these
TABLE 1
Selected Melting Points of the Group 1 Chlorides
System

Mole%

m.p. (C)

LiCl
NaCl
KCl
CsCl
LiClCsCl
NaClKCl
CsClKCl

100
100
100
100
6040
5050
3565

610
803
772
646
355
658
610

Ionic liquids for clean technology

353
4.2 Tetrachloroaluminate(III) ionic liquids

Fig. 1. An idealised simple binary phase diagram (e.g. for

watersodium chloride mixtures), illustrating the eutectic
point.

systems are liquids, it is necessary to bring the melting

point down even further. This has been done by increasing the size of the cations : replacing the simple inorganic cations with unsymmetrical organic cations
depresses the melting point to temperatures at or below
room temperature, as illustrated in the following
section.
TABLE 2
Melting Points of Selected Tetrachloroaluminate(III) Salts
System

Mole%

m.p. (C)

AlCl
3
LiClAlCl
3
NaClAlCl
3
KClAlCl
3

100
5050
5050
5050

192
144
151
256

The development of ionic liquids that are uid at

room temperature by the groups of Osteryoung,14
Wilkes15 and Hussey16 has provided an ideal resolution
to all of the problems presented above. Although the
earlier work was based around the N-butylpyridinium
cation, [NBupy]`,14 research now is almost exclusively
based upon the 1-ethyl-3-methylimidazolium cation,
[emim]`, or simple derivatives thereof. Undoubtedly
the most studied system is 1-ethyl-3-methylimidazolium
chloridealuminium(III) chloride, [emim]ClAlCl , and
3
its experimental phase diagram is shown in Fig. 3.17
The unsymmetrical nature of the cation is crucial ;
[NBupy]` possesses a mirror plane missing from
[emim]`, which only has C symmetry (the ethyl group
1
is not co-planar with the imidazolium ring).18 The 1ethyl-3-methylimidazolium salts melt some 100C lower
than their N-butylpyridinium analogues.
These chloroaluminate systems are governed by the
following primary equilibrium, eqn (1) :19
2[AlCl ]~ H [Al Cl ]~ ] Cl~ ; K B 10~16.3
4
2 7

(1)

The chemical and physical properties of the liquids are

determined by the percentage of aluminium(III) chloride : those which have X(AlCl ) greater than 50 mol%
3
are referred to as acidic, whilst those with X(AlCl ) less
3
than 50 mol% are called basic. The exactly 50 mol%
composition is referred to as neutral. It should be

Fig. 3. The
experimental
phase
diagram
for
the
[emim]ClAlCl system, showing the formation of a com3
pound, [emim][AlCl ], with a congruent melting point.17
4

Fig. 2. An idealised phase diagram for a system showing the

formation of a compound with a congruent melting point.

In the older literature, this cation is almost exclusively

referred to (incorrectly) as 1-methyl-3-ethylimidazolium, and
represented by [MeEtim]`. Its full, correct, systematic name
is the 1-ethyl-3-methyl-1H-imidazolium cation.

K. R. Seddon

354
TABLE 3
Principal Anions Present in the [emim]ClAlCl Ionic Liquid System, as a Function of Composi3
tion
Basic ; X(AlCl ) \ 005
3
Cl~
[AlCl ]~
4

Acidic ; X(AlCl ) \ 05067

3

V ery acidic ; X(AlCl ) \ 067075

3

[AlCl ]~
4
[Al Cl ]~
2 7

emphasised here that the terms acid and base refer to

Franklin acidity and basicity, and not (as frequently
assumed) to Lewis acidity and basicity. The ionic composition of the [emim]ClAlCl system is displayed on
3
a logarithmic scale ( [ pX) in Fig. 4, and on a linear
scale in Fig. 5. There are three key features of note.
Firstly, a clear parallel (both quantitative and
qualitative) exists between the curves illustrated in Fig.
4, and standard pH curves in water. Secondly, the con-

[Al Cl ]~
2 7
[Al Cl ]~
3 10

centration of the tetrachloroaluminate(III) ion is

approximately constant, and very high, across the
whole compositional range. Finally, there is always
exactly 50 mol% of the 1-ethyl-3-methylimidazolium
cation present. Table 3 summarises the principal anions
present as a function of composition : denitive evidence
now exists for the existence of [Al Cl ]~ in very acidic
3 10
systems.20,21
There is not the space here to enlarge further on the
physical and chemical properties of these unique
systems : the interested reader is referred to Hussey.1,2

5 IONIC LIQUIDS FOR CLEAN CATALYSIS

Fig. 4. The concentration of anions (represented on a

logarithmic scale) present in the [emim]ClAlCl system, as a
3
function of composition.

Clean technology is concerned with reducing the waste

from an industrial chemical process to zero. Its implementation will lead to a cleaner environment, and more
cost-eective use of starting materials. It requires, in the
majority of cases, the rethinking and redesign of many
chemical processes that we currently think of as the
industrial norm. Catalysis clearly has a central role to
play in this process, with its potential for both high
yields and high specicity.
The E-factor of a process is the ratio (by weight) of
the by-products to the desired product(s).22 Table 4
illustrates that, contrary to popular perception, the
dirty end of the chemical industry, oil rening and
bulk chemicals, is remarkably waste conscious. It is,
surprisingly, the ne chemicals and pharmaceutical
companies that are using inefficient, dirty, processes,
albeit on a much smaller scale, and there will be
increasing demand (political, economic, social and
environmental) for the introduction of new clean technology. Industries that do not respond will die.
TABLE 4
By-products as a Proportion of Production for the Chemical
Industry22

Fig. 5. The concentration of anions (represented on a linear

scale) present in the [emim]ClAlCl system, as a function of
composition.3

Industry

Production (tons p.a.)

E-factor

Oil rening
Bulk chemicals
Fine chemicals
Pharmaceuticals

106108
104106
102104
101103

01
15
550
25100

Ionic liquids for clean technology

Volatile organic solvents are the normal media for
the industrial synthesis of organic chemicals
(petrochemical and pharmaceutical), with a current
worldwide usage estimated at 4 000 000 000 p.a.
However, the environmental impact of these solvents is
signicant, and the Montreal Protocol has resulted in a
compelling need to re-evaluate many chemical processes
that have proved otherwise satisfactory for much of this
century. A conspicuous example is the recent closure of
one of the DuPont Hypalon' plants in Northern
Ireland, which had been operating with chlorinated
hydrocarbon solvents. There appear to be four main
alternative strategies :
(1)
(2)
(3)
(4)

solvent-free synthesis
the use of water as a solvent
the use of supercritical uids as solvents
the use of ionic liquids as solvents

It is the purpose of this review to stimulate interest in

option (4), and to incite enough activity in this area to
allow a meaningful evaluation. Ionic liquids possess,
inter alia, the following desirable properties :
1. They have a liquid range of 300C (cf. water, which
has a liquid range of 100C, and ammonia, with a
liquid range of only 44C), allowing tremendous
kinetic control.
2. They are outstandingly good solvents for a wide
range of inorganic, organic and polymeric materials
(but, fortunately, they do not dissolve polythene,
PTFE or glass !) : high solubility implies small reactor
volumes.
3. They exhibit Brnsted, Lewis and Franklin acidity,
as well as superacidity.23,24
4. They have no eective vapour pressure.
5. Their water sensitivity does not restrict their industrial applications.
6. They are thermally stable up to 200C.
7. They are relatively cheap, and easy to prepare.
Unlike water and other hydroxylic solvents, they will
dissolve a wide range of organic molecules to an appreciable extent (benzene, for example, will form up to 50%
(v/v) solutions), meaning much lower volumes of solvent
are required for a given process. Exploratory work in
our own laboratories (carried out in collaboration with
BP Chemicals and Unilever Port Sunlight Research
Laboratory) has demonstrated that a wide range of
catalysed organic reactions (including oligomerisations,
polymerisations, alkylations and acylations) occurs in
room-temperature ionic liquids, and that these are
serious candidates for commercial processes.25,26 For
example, the oligomerisation of butenes to polyisobutene in a chloroaluminate(III) ionic liquid25 is a strong
competitor for the Cosden process, which uses a supported or liquid phase aluminium(III) chloride catalyst.27

355
The reactions we have observed represent the tip of
an icebergall the indications are that roomtemperature ionic liquids are the basis of a new industrial technology. They are truly designer solvents : either
the cation26 or the anion5 can be changed, if not at will,
then certainly with considerable ease, in order to optimise such phenomena as the relative solubilities of the
reactants and products, the reaction kinetics, the liquid
range of the solvent, the cost of the solvent, the intrinsic
catalytic behaviour of the media, and air-stability of the
system. For the rst time, it is possible to design a
solvent to optimise a reaction (with control over both
yield and selectivity), rather than to let the solvent
dictate the course of the reaction. For example, we have
just reported upon a new series of ionic liquids that are
also liquid crystals, with a phenomenal liquid range (up
to 188C) of smectic A phase stability, which oer a signicant new ionic medium for studying the stereocontrol of reactions (e.g. polymerisation reactions) in liquid
crystals.28 This, quite literally, revolutionises the methodology of synthetic organic chemistry : it will never be
the same again !

ACKNOWLEDGEMENT
I am indebted to all my co-workers, but especially to
my past and present postdoctoral assistants (Drs J. E.
Turp, A. K. Abdul-Sada, T. Welton, A. C. Lees, M.
Earle, C. J. Bowlas, C. M. Gordon, Y. Patell and T. A.
Evans), graduate students (D. Appleby, L. Dutta, A.
Elaiwi, L. Agocs and S. A. Boyle) and structural characterisation colleagues (Dr P. B. Hitchcock, Dr A. J. Dent
and M. Nieuwenhuyzen), without whose hard labour
this research would not have been possible. I am particularly grateful to Prof. D. W. Braben and Dr D. Ray
(Venture Research International), Prof. C. J. Adams
(Unilever Port Sunlight Research Laboratory), Dr C.
Sell (Quest International) and Prof. M. J. Green and
Drs M. P. Atkins and B. Ellis (all BP Chemicals) for
both their nancial and intellectual input to this eld,
and especially for their support when ionic liquids were
not as well accepted as they are now. Finally, the active
collaboration and friendship of Prof. C. L. Hussey
throughout this period is warmly appreciated.

REFERENCES
1. Hussey, C. L., Room temperature molten salt systems.
Adv. Molten Salt Chem., 5 (1983) 185230.
2. Hussey, C. L., Room-temperature haloaluminate ionic
liquidsnovel solvents for transition-metal solution
chemistry. Pure Appl. Chem., 60 (1988) 176372.
3. Chauvin, Y. & Olivier-Bourbigou, H., Nonaqueous ionic
liquids as reaction solvents. CHEMT ECH, 25(9) (1995)
2630.

K. R. Seddon

356
4. Chauvin, Y., Mussmann, L. & Olivier, H., A novel class of
versatile solvents for 2-phase catalysishydrogenation,
isomerization, and hydroformylation of alkenes catalyzed
by rhodium complexes in liquid 1,3-dialkylimidazolium
salts. Angew. Chem. Int. Edit. Engl., 34 (1996) 2698700.
5. Wilkes, J. S. & Zaworotko, M. J., Air and water stable
1-ethyl-3-methylimidazolium based ionic liquids. J. Chem.
Soc., Chem. Commun., (1992) 9657.
6. Poliako, M. & Howdle, S., Supercritical chemistry
synthesis with a scanner. Chem. Brit., 31 (1995) 11821.
7. Poliako, M., Howdle, S. M. & Kazarian, S. G., Vibrational spectroscopy in supercritical uidsfrom analysis
and hydrogen-bonding to polymers and synthesis. Angew.
Chem. Int. Edit. Engl., 34 (1995) 127595.
8. Seddon, K. R., Room-temperature ionic liquids : neoteric
solvents for clean catalysis. Kinet. Katal., (1997) (in press).
9. http ://www.ch.qub.ac.uk/resources/ionic/review/review.html.
10. http ://www.ch.qub.ac.uk/resources/ionic/ionic.html.
11. Hussey, C. L., Barnard, P. A., Sun, I. W., Appleby, D.,
Hitchcock, P. B., Seddon, K. R., Welton, T. & Zora, J. A.,
An electrochemical study of the ruthenium(III) and
ruthenium(IV) hexachlorometallates in a basic roomtemperature chloroaluminate molten salt. J. Electrochem.
Soc., 138 (1991) 25904.
12. Lide, D. R. (ed.) CRC Handbook of Chemistry and Physics,
73rd edn. CRC Press, Boca Raton, 1992.
13. Kapustinskii, A. F., Lattice energy of ionic crystals. Quart.
Rev., 10 (1956) 28394.
14. Robinson, J. & Osteryoung, R. A., An electrochemical and
spectroscopic study of some aromatic hydrocarbons in the
room temperature molten salt system aluminum chloride
n-butylpyridinium chloride. J. Am. Chem. Soc., 101 (1979)
32327.
15. Wilkes, J. S., Levisky, J. A., Wilson, R. A. & Hussey, C. L.,
Dialkylimidazolium chloroaluminate meltsa new class
of room-temperature ionic liquids for electrochemistry,
spectroscopy and synthesis. Inorg. Chem., 21 (1982) 1263
4.
16. Sanders, J. R., Ward, E. H. & Hussey, C. L., Aluminum
bromide-1-methyl-3-ethylimidazolium
bromide
ionic
liquids. 1. Densities, viscosities, electrical conductivities,
and phase-transitions. J. Electrochem. Soc., 133 (1986)
32530.
17. Fannin, A. A., Floreani, D. A., King, L. A., Landers, J. S.,
Piersma, B. J., Stech, D. J., Vaughn, R. L., Wilkes, J. S. &
Williams, J. L., Properties of 1,3-dialkylimidazolium chlo-

18.

19.

20.

21.

22.

23.

24.

25.
26.
27.
28.

ride aluminum chloride ionic liquids. 2. Phase-transitions,

densities, electrical conductivities, and viscosities. J. Phys.
Chem., 88 (1984) 261421.
Abdul-Sada, A. K., Greenway, A. M., Hitchcock, P. B.,
Mohammed, T. J., Seddon, K. R. & Zora, J. A., Upon the
structure of room-temperature halogenoaluminate ionic
liquids. J. Chem. Soc., Chem. Commun., (1986) 17534.
Hussey, C. L., Scheffler, T. B., Wilkes, J. S. & Fannin, A.
A., Chloroaluminate equilibria in the aluminum chloride1-methyl-3-ethylimidazolium chloride ionic liquid. J. Electrochem. Soc., 133 (1986) 138991.
Abdul-Sada, A. K., Greenway, A. M., Seddon, K. R. &
Welton, T., Upon the existence of [Al Cl ]~ in room3 10 Org. Mass
temperature chloroaluminate ionic liquids.
Spectrom., 24 (1989) 91718.
Abdul-Sada, A. K., Greenway, A. M., Seddon, K. R. &
Welton, T., A fast-atom-bombardment mass-spectrometric
study of room-temperature 1-ethyl-3-methylimidazolium
chloroaluminate(III) ionic liquidsevidence for the existence of the decachlorotrialuminate(III) anion. Org. Mass
Spectrom., 28 (1993) 75965.
Sheldon, R. A., The role of catalysis in waste minimization. In Precision Process T echnology : Perspectives
for Pollution Prevention, eds M. P. C. Weijnen & A. A. H.
Drinkenburg. Kluwer, Dordrecht, 1993, p. 12538.
Smith, G. P., Dworkin, A. S., Pagni, R. M. & Zingg, S. P.,
Brnsted
superacidity
of
HCl
in
a
liquid
chloroaluminateAlCl -1-ethyl-3-methyl-1H-imidazolium
chloride. J. Am. Chem.3Soc., 111 (1989) 52530.
Smith, G. P., Dworkin, A. S., Pagni, R. M. & Zingg, S. P.,
Quantitative study of the acidity of HCl in a molten chloroaluminate system (AlCl 1-ethyl-3-methyl-1H-imid3 of HCl pressure and melt
azolium chloride) as a function
composition (510664 mol% AlCl ). J. Am. Chem. Soc.,
3
111 (1989) 50757.
Abdul-Sada, A. K., Atkins, M. P., Ellis, B., Hodgson, P. K.
G., Morgan, M. L. M. & Seddon, K. R., World Patent,
WO 95/21806, 1995.
Abdul-Sada, A. K., Ambler, P. W., Hodgson, P. K. G.,
Seddon, K. R. & Stewart, N. J., World Patent, WO 95/
21871, 1995.
Weissermel, K. & Arpe, H.-J., Industrial Organic Chemistry, 2nd revised edn. VCH, Weinheim, 1993.
Bowlas, C. J., Bruce, D. W. & Seddon, K. R., Liquidcrystalline ionic liquids. J. Chem. Soc., Chem. Commun.,
(1996) 162526.