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: Phase Equilibria
Aaron M. Scurto,*
,,
Elizabeth Newton,
,|
Ross R. Weikel,
,|
Laura Draucker,
,|
Jason Hallett,
,|
Charles L. Liotta,
,|,
Walter Leitner,
,#
and Charles A. Eckert
,|,
Institut fur Technische und Makromolekulare Chemie, RWTH Aachen, Worringerweg 1,
D-52074 Aachen, Germany, Department of Chemical & Petroleum Engineering and NSF-ERC Center for
EnVironmentally Beneficial Catalysis, UniVersity of Kansas, Lawrence, Kansas 66045, School of Chemical and
Biomolecular Engineering, Georgia Institute of Technology, Atlanta, Georgia 30332, School of Chemistry and
Biochemistry, Georgia Institute of Technology, Atlanta, Georgia 30332, Specialty Separations Center,
Georgia Institute of Technology, Atlanta, Georgia 30332, and Max-Planck-Institut fur Kohlenforschung,
Mulheim an der Ruhr, Germany
Development of ionic liquids for specific tasks is currently being pursued by many researchers as numerous
cation/anion combinations are theoretically possible. However, only a small fraction of these combinations
melt below 100 C. Recently, large melting point depressions of several ionic solids with compressed carbon
dioxide have been reported. This investigation details the melting point depression of a large number of ionic
organic compounds (ionic liquids) with gaseous, liquid, and supercritical CO
2
. Large and previously unreported
depressions were observed for some of the ionic solids. This methodology greatly expands the numbers of
compounds and functional groups that can be employed in an ionic liquid/compressed gas system for various
applications. Thermodynamic analysis indicates that even small amounts of CO
2
can lead to substantial melting
point depression, due to its very low melting temperature and negative deviations to Raoults law.
Introduction
Room-temperature ionic liquids (ILs) have been the subject
of intense focus due to their demonstrated usefulness as solvents
for extractions,
1
reactions,
2,3
and materials processing.
4,5
Pre-
liminary toxicology studies of ILs
6-8
indicate low to moderate
toxicity on average, and most ILs have no measurable vapor
pressure, thus eliminating air emissions; an advantage over any
other organic solvent. Due to these advantageous properties,
ILs have been touted as green solvents. In addition, biphasic
systems with ILs can be utilized for advanced reactions and
extractions. In particular, there has been significant research in
pairing CO
2
with ionic liquids.
9-11
Carbon dioxide is frequently
used in green processing due to its benign characteristics.
12
CO
2
has excellent solubility in many ILs, while ILs have little to no
solubility in CO
2
.
9
In addition, Scurto et al.
13,14
have used CO
2
pressure as a separation switch, to induce immiscibility in
ionic liquid solutions with organics and water. Brown et al.
15
have used supercritical CO
2
to extract products of a homoge-
neously catalyzed reaction from an IL. Leitner and co-workers
have performed a variety of reactions in CO
2
/IL biphasic
systems where the ionic liquid immobilizes a homogeneous
catalyst in a continuous process.
10,16,17
Sellin et al.
18,19
have also
used the IL to immobilize a homogeneous catalyst in an IL/
CO
2
biphasic system for hydroformylation reactions. Catalytic
reactions using enzymes have also been carried out in such
biphasic media.
11,20,21
A detailed overview of biphasic catalysis
in IL/CO
2
systems is available in the literature.
22,23
The present definition of an ionic liquid is an organic salt
that has a melting point below 100 C.
24
There are a myriad of
cation/anion combinations that can be molecularly engineered
with specific physical or chemical properties. However, design-
ing organic salts with particular properties and functional groups
that are also liquid near room-temperature is not a trivial task.
Of the estimated 10
18
possible cation-anion combinations (10
14
unique cations and anions),
25
only a very small fraction actually
melt below 100 C. Often useful functional groups yield solid
salts, such as those shown with metal-extracting ionic com-
pounds by Visser et al.,
26
chiral ionic liquids,
27,28
an IL that is
both solvent and catalyst,
29
etc. A methodology or process to
increase the range of ionic compounds for use as solvents would
be highly useful.
It has been long known that organic solids can undergo
melting below their normal melting points (melting point
depression) in the presence of a number of compressed gases.
30
Kazarian et al.
31
observed liquid-crystal transitions induced by
CO
2
for surfactant-like imidazolium salts. Recently, Scurto and
Leitner
32
have demonstrated that CO
2
can induce unprecedented
melting point depressions in some types of ionic salts. Moreover,
the induced melts can serve as an advantageous platform for
metal-complex catalysis. This contribution will present the
results for a larger variety of ionic solids and demonstrate the
effect of temperature, pressure, and composition on the melting
point. The melting point with composition data will be modeled
using an ideal and advanced activity-coefficient model.
Phase Behavior
Melting point depression is a thermodynamic condition that
can be represented by two different equilibria: solid-liquid and
solid-liquid-vapor (SLV). Figure 1 illustrates the phase
transitions with pressure and temperature of a typical highly
asymmetric system of a common organic solid with an ambient
gaseous component: naphthalene and ethane or carbon dioxide,
for example. In the presence of a second gaseous component,
the melting curve of the pure solute can be lowered as shown
* To whom correspondence should be addressed. E-mail: ascurto@
ku.edu. Phone: +1 (785) 864-4947. Fax: +1 (785) 864-4967.
University of Kansas.
)
V
2
RT
[
(
1
-
2
)
2
+
q
1
2
q
2
2
(
1
-
2
)
2
1
+
(R
1
- R
2
)(
1
-
2
)
1
]
+ ln
(
V
2
V
1
)
aa
+ 1 -
(
V
2
V
1
)
aa
(2)
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ReceiVed for reView March 1, 2007
ReVised manuscript receiVed May 18, 2007
Accepted May 24, 2007
IE070312B
Ind. Eng. Chem. Res., Vol. 47, No. 3, 2008 501