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Salty solvents ionic really

Ionic compounds are usually high melting point solids. But mix together a powdered organic salt with
aluminium chloride, warm gently, and the result is a clear, colourless, ionic liquid. Such liquids are
potential green alternatives to volatile organic solvents and are showing promise in a host of
applications, from chemical syntheses, through catalysis, to metal finishing.
Solvents, in particular volatile organic compounds (VOCs), are used in the manufacturing and
processing of almost every product we use. By their nature they are relatively small molecules that have
weak intermolecular forces between them, making them highly volatile. They are also flammable and
often toxic. Each year the UK emits about half a million tonnes of VOCs into the lower atmosphere from
solvent use alone and these become involved in the ozone cycle, leading to a destruction of the
protective ozone layer in the atmosphere. With the current emphasis on greening the chemical industry
ie making its operations safer and environmentally acceptable there has been much interest in
finding non-volatile solvents as replacements.
What about ionic compounds?
In contrast to their molecular counterparts, ionic compounds are neither volatile nor flammable and not
particularly toxic, making them potentially safer to work with as solvents. But classically we are taught
that ionic compounds are high melting point solids there are strong interactions between ions, which
easily organise themselves into stable lattices. So their use as solvents in the liquid state seems
counterintuitive. In fact, salts have been used in their liquid state for centuries in the extraction of such
metals as sodium, magnesium and aluminium. Salts are also excellent solvents because they have
large potential fields around the ions, which interact strongly with a wide range of solutes. This is why
you put salt on a red wine stain the sodium and chloride ions coordinate to the tannins in the wine and
stop them interacting with fibres in the cloth.
The key barrier facing chemists to the development and widespread use of salts as solvents seems,
therefore, to be their melting points. To a first approximation, the melting point of an ionic compound is
related to the lattice enthalpy, which in turn is related to the size and charge of the ions; the larger the
ions and the smaller the charge, the less energy is required to break the ionic bonds (see Table 1). So,
organic cations with quaternary ammonium groups (R4N+) have low lattice energies and much lower
melting points than their alkali metal analogues. For example, tetrabutylammonium bromide melts at
104C whereas NaBr melts at 747C. The symmetry of the ions is also important: non-symmetrical ions
are more difficult to fit into a lattice and so the lattice energy and melting point will be lower. Thus most
attempts to make low melting point salts, or ionic liquids, have used bulky anions such as (F3CSO2)2N,
BF4, PF6 and F3CSO3, and cations such as butylmethylimidazolium and butyl pyridinium:
There is some dispute in the literature about which ionic liquid was the first, but this seems to depend on
whether the authors worked on metal- or non-metal-containing anions.
Metal-based ionic liquids
The main consensus seems to be that the first major studies of ambient temperature salts (the term
ionic liquid has been used to describe salts that melt below 100C) were in the 1940s by a group, led by
Frank Hurley and Tom Weir, at Rice University. They were looking for a cheaper and easier way to
electroplate aluminium. When they mixed and gently warmed powdered pyridinium halides with
aluminium chloride, the powders reacted, giving a clear, colourless liquid.1 The resulting mixtures
contain complex chloroaluminate anions such as AlCl4 and Al2Cl7 that are large and hence reduce the
charge density, and bulky asymmetric organic cations, which cannot pack neatly, thus lowering the
lattice energy. Similar ionic liquids have been made using a wide variety of quaternary ammonium salts,
most notably imidazolium cations.2 Aluminium chloride, however, reacts readily with water, which has
limited the use of these types of ionic liquids to the electrodeposition of aluminium metal and some

synthetic reactions requiring very strong Lewis acid catalysts. The principle can be extended to other
metal-containing salts such as zinc(ii), tin(ii) and iron(iii) halides.3
Non-metal-containing ionic liquids
The preparation of ethylammonium nitrate (C2H5N+H3 NO3) by P. Walden in 1914 is recognised by many
as the first ionic liquid.4 This compound has a melting point of 12C but has not really found a use, owing
to its high reactivity. More recent studies have concentrated on inert, non-metal-containing anions such
as triflamide (F3CSO2)2N and hexafluorophosphate.2,5 Liquids with these anions are less reactive and
more air stable than the chloroaluminate based ionic liquids and some are even water immiscible.
Possibly the most studied one is 1-butyl-3-methylimidazolium hexafluorophosphate, which is liquid at
room temperature and only freezes at 40C. These particular ionic liquids have been studied for a wide
range of synthetic applications. They are, however, quite difficult to make, very expensive, and their
toxicity has not yet been ascertained. Accordingly, none of these compounds has been registered and
this currently limits their wide-scale use.
Nevertheless, several companies are developing industrial processes based on ionic liquids. BASF, for
example, is currently scaling up a process using alkyl imidazoles as a base for the synthesis of
alkoxyphenylphosphines. These are precursors for the synthesis of photoinitiators used in the
manufacture of printing inks, glass fibres and wood coatings. The phosphines are prepared by the
reaction of phenyl-chlorophosphines with alcohols, as shown in Scheme 1. To drive the reaction a base
is required, but separating the salt produced is difficult for the majority of tertiary amines. The use of
imidazoles, as shown in Scheme 1, is interesting because the quaternary ammonium salt forms as a
liquid in a separate phase, making separation easier.
Scheme 1 BASFs ionic liquid process

Scheme 1 BASFs ionic liquid process

Deep eutectic solvents


An alternative approach to making large non-symmetric ions is to take a simple organic halide salt and
complex the anion with something that will form a hydrogen bond. The complexing agent interacts with
the anion, increasing its effective size. This in turn decreases the interaction with the cation and so
decreases the freezing point of the mixture. The major advantage of this approach is that common, nontoxic components can be used and the properties of the liquid can be changed with each hydrogen bond
formed and each halide salt. This approach has numerous possibilities. Consider how many quaternary
ammonium salts are available and the wide variety of amides, amines, carboxylic acids and alcohols
which could be used to provide hydrogen bonds. These liquids are similar to the metal-containing ionic
liquids, but to differentiate them from the wide range of ionic liquids that are available they have been
given the name deep eutectic solvents. Best of all, they are easy to make simply take the two solids,
mix them together with gentle heating, until they melt, and when they cool they remain liquid (see Box
1).

Work to date has focused on choline (2-hydroxyethyl-trimethylammonium) chloride as the quaternary


ammonium salt.6 This is vitamin B4 and is produced on the Mtonne per annum scale as an additive for
chicken feed and a wide range of other applications. Thus choline chloride is not only cheap and easy to
make, but it is non-toxic and even biodegradable. Ionic liquids based on choline chloride have,
therefore, the potential to be used on a large scale.
One simple hydrogen bond donor that has been used is urea ((NH2)2C=O), which is a common fertiliser.
Urea mixed with choline chloride in a 2:1 ratio produces a colourless liquid that freezes at ca 12C,
which is remarkable given the melting points of the constituents (choline chloride melts at 303C and
urea at 134C). Figure 1 (a) shows a schematic diagram of how the urea molecules complex the
chloride ion and Fig 1 (b) shows the freezing point of the liquid as a function of composition. The lowest
melting point of these mixtures (termed the eutectic composition) occurs when the ratio of salt to
hydrogen bond donor is 1:2. The depression of freezing point and the eutectic composition changes with
the nature of the molecule providing the hydrogen bonds, eg oxalic acid (HOOCCOOH): choline chloride
has a eutectic composition of 1:1 and a depression of freezing point of 212C.
Fig 1 Ureacholine chloride

Fig 1 Ureacholine chloride

The phenomenon of mixing two solids to make a liquid is not new; every winter this principle is used
when salt is added to ice on roads. With deep eutectic solvents, however, the magnitude of the freezing
point depression is over 10 times greater than with ice and salt. This approach works best if both the salt
and the compound containing the hydrogen bond are solid at ambient temperature. Since the formation
of the liquid is endothermic, the driving force for the formation is entropy taking two highly ordered
solids and changing them into a liquid causes a large increase in the degree of disorder of the system.
Applications
Probably the most exciting aspect of deep eutectic solvents research is that a whole host of applications
is available because of the ease of manufacture and environmental advantages.7 Ionic liquids dissolve a
wide range of solutes in high concentrations (see Table 2). As bulk solvents they can be used in
applications like cleaning. They can also dissolve a wide range of metal oxides, owing to their high
chloride content (see Fig 2).

Fig 2 Dissolution of a range of metal oxides in ionic liquids

Fig 2 Dissolution of a range of metal oxides in ionic liquids

Further, since the liquids are ionic, they are good conductors of electricity and as such find use in
electrochemical applications. They are currently being developed for electroplating chromium, which is a
multi-billion pound worldwide industry. The traditional process uses chromic acid, which is not only
extremely hazardous to use but it is also very inefficient. The work to date shows that thick, adherent
and crack-free chromium can be obtained by using ionic liquids and this process is currently being
scaled-up.
Ionic liquids are also being applied to the electropolishing of stainless steels. The common industrial
process uses a mixture of sulphuric and phosphoric acids. Initial results have shown that not only is the
use of ionic liquids more benign, but they provide superior surface finishes than is obtained by using the
mixture of acids. Developing a process that uses clean chemistry is clearly desirable but the technology
will only be adopted if there are also economic benefits. In the case of the electropolishing process, the
power consumption when ionic liquids are used is approximately a quarter of that when aqueous acid
solutions are used, thus providing a significant economic driver.
Ionic liquids, and deep eutectic solvents in particular, are in their infancy but they have generated a
huge amount of academic interest over the past decade and are beginning to yield some industrial
potential. There are an almost limitless variety of liquids still to be discovered with a wide range of
possible applications. Thus for ionic liquids the future is bright and the future is green.
Drs Andrew Abbott and David Davies are senior lecturers in the department of chemistry at the
University of Leicester, Leicester LE1 7RH. They have also set up a spin-out company, Scionix, to
develop industrial applications for ionic liquids.
References
1. F. H. Hurley, US patent 4446331, 1948.
2. P. Wasserscheid and T. Welton, Ionic liquids in synthesis. Weinheim: Wiley-VCH Verlag, 2003.
3. A. P. Abbott et al, Chem. Comm., 2001, 2010.
4. P. Walden, Bull Acad. Imper. Sci. (St Petersburg), 1914, 1800.
5. T. Welton, Chem. Rev., 1999, 99, 2071.
6. A. P. Abbott et al, Chem. Comm., 2003, 70.
Box 1 Experiments

Ionic liquids are relatively easy to make. Simply mix together 0.01 moles (1.4g) of choline chloride with

0.02 moles (1.2g) of urea in a boiling tube and heat them to 80C on a hot plate or in a water bath. Stir
them constantly with a glass rod until a homogeneous liquid is formed. This should remain liquid down
to approximately 12C which is 122C below that of urea and 290C below that of choline chloride!

Two solids make one liquid

You could then try to see what types of compounds are soluble in this ionic liquid. Ionic liquids have
unusual solvent properties for example, they dissolve a wide variety of metal salts including AgCl,
metal oxides such as CuO, sugars and even cellulose (put in some filter paper and see if it dissolves).
You could also try to see which liquids are miscible with the ionic liquids. In general, if the compound
can form a hydrogen bond it will be soluble.

Table 1 Melting points of simple halide


salts
Anion/mp/C

Cation

Cl

Br

Na+

993

801

747

858

770

734

Rb+

795

718

693

Ca2+

1423

782

730

Table 2 Solubility of species in a 2:1 urea:choline chloride ionic liquid


Solute

Solubility/mol l1

Lithium chloride
Silver chloride
D-alanine
Benzoic acid

>2.5
>0.66
>0.38
>0.82

Copper(II) oxide
Calcium carbonate

>0.12
>0.21