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Melting Point Depression of Ionic Liquids with CO

2
: 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.

Institut fur Technische und Makromolekulare Chemie.

University of Kansas.

School of Chemical and Biomolecular Engineering, Georgia


Institute of Technology.
|
Specialty Separations Center, Georgia Institute of Technology.

School of Chemistry and Biochemistry, Georgia Institute of


Technology.
#
Max-Planck-Institut fur Kohlenforschung.
493 Ind. Eng. Chem. Res. 2008, 47, 493-501
10.1021/ie070312b CCC: $40.75 2008 American Chemical Society
Published on Web 09/28/2007
by the dashed SLV curves labeled I and II. Solid-liquid-vapor
(SLV) equilibria for a binary system is obtained by starting with
higher molar loading of the compressed gas and maintaining
temperature (1a to 2 in Figure 1) or pressure (1b to 2 in Figure
1) and varying the other variable until the very first instance
that a solid, liquid, and vapor coexist in equilibria. The melting
point depression (T
m
) is thus T
m
minus T
SLV
. For nonionic
organic systems, the SLV line emanates from the triple point
of the solute and terminates at the upper critical endpoint
(UCEP). The SLV can proceed directly (curve I, e.g., naphtha-
lene and ethane
33
) to the UCEP, or the SLV curve can have a
minimum in temperature on a PT projection (curve II, e.g.,
naphthalene and carbon dioxide
34-36
). This implies that increas-
ing pressure along certain isotherms will first melt the solid
(SLV curve II) to produce vapor-liquid equilibrium and then
at higher pressures solidify the liquid phase, returning to solid-
fluid equilibrium. However, some gaseous components do not
induce much or any melting point depression and can actually
increase the melting point beyond that of the pure component.
This phenomenon is observed when naphthalene is exposed to
helium.
36
Solid-liquid-vapor equilibrium can also occur at
lower temperatures near the vapor pressure of the less volatile
component, as shown in Figure 1; however, this transition is
primarily the boiling point elevation of the liquefied gas in
the presence of the solute. At lower gas loading (moles gas:
solute) and pressures above the SLV pressure, the melting point
depression will be represented by solid-liquid equilibrium
(SLE). The inset in Figure 1 illustrates in a pressure-
composition plot for the phase behavior regions of both SLV
and SLE (P
2
represents point 2 (SLV) in the larger plot).
The melting point of naphthalene (T
m
) 80.1 C) has been
determined in the presence of a variety of gases: methane,
37
ethane,
33
ethylene,
38
carbon dioxide,
35
and xenon.
39
The largest
melting point depression was found in the presence of super-
critical xenon (T
m
) 37.5 C at 124 bar). Large melting point
depressions with CO
2
and inorganic minerals have also been
discovered, however at conditions in excess of 1000 K and 1000
bar.
40
CO
2
has been known for several decades to lower the
glass transition temperature of polymers.
41
Only more recently
has CO
2
been shown to lower the melting temperature of poly-
mers. Zhang and Handa
42
report that CO
2
lowers the melting
point of syndiotactic polystyrene (T
m
) 277 C) by approxi-
mately 12 C at 72 bar. Kishimoto and Ishii
43
found that CO
2
depressed the melting point of isotactic polypropene (T
m
)
180 C) by 11 C at 94 bar. Weidner and co-workers
44
deter-
mined the melting point depression of polyethylene glycol (PEG,
MW 1500, T
m
) 44.9 C) of approximately 16 C at 150 bar.
In attempt to perform electrochemistry in wet supercritical
carbon dioxide, Wightman and co-workers
45-47
used the ionic
solids tetrahexylammonium nitrate and hexafluorophosphate
([THexAm][PF
6
]) to aid in electrochemical oxidation. They
found that the CO
2
/H
2
O mixture induced a melting point in the
ionic solid (T
m
) 131 C of [THexAm][PF
6
]) to 40 to 50 C at
about 90 bar. This is not surprising considering the highly
hygroscopic nature of most quaternary ammonium salts. Ka-
zarian et al.
31
have used attenuated total reflection-infrared
(ATR-IR) to detect the formation of a liquid crystal phase
transition under 70 bar of pure CO
2
of a long-chain (C
16
) methyl-
imidazolium PF
6
; at ambient pressure, the ionic solid forms a
smectic A phase at 75 C and an isotropic liquid phase at
125 C. They also inferred from the IR spectra that the CO
2
has preferential interactions with the fluorinated anion in the
liquid crystal phase. However, the general trend or magnitude
of the melting point depression with compressed gases for the
vast majority of ionic solids has not been elucidated.
Thermodynamics and Modeling
Thermodynamic modeling of solid-liquid equilibria gives
the relationship for the mole fraction of the solid (2) in terms
of the melting point (T
m
), the triple point temperature (T
t
), the
enthalpy of fusion (h
fus
), the enthalpy of any solid-solid
transition (h
trans
), the temperature of that transition (T
trans
), and
the activity coefficient
2
. Neglecting second-order corrections,
the solid-liquid equilibrium is given by eq 1
48
This relationship can be used to make predictions of the
melting point curve, where the liquid may be either ideal or
nonideal, modeled by an expression for Gibbs excess free
energy/activity (g
EX
/). Deviations from Raoults law may be
both positive or negative, but unless there is a reasonably strong
compound formed (e.g., liquid metals), this procedure will give
a single eutectic and the predictions of the melting point curve
are generally quite accurate.
48-51
For ideal solutions, the activity
coefficient,
i
, is set equal to one. Modeling procedures are
discussed below.
Experimental Section
Materials. Naphthalene, [TBAm][BF
4
] and [THexAm][Br]
were purchased from Sigma-Aldrich at a purity of 99% or
greater. The solids were then further purified by drying at room
temperature under vacuum of 10
-3
Torr for 48 h and stored at
room temperature under a nitrogen atmosphere. Tetrabutylphos-
phonium bromide >99% ([TBP][Br]), tetrabutylammonium
bromide >99% ([TBAm][Br]), tetrabutylammonium tosylate
>99% ([TBAm][Tosyl]), tetrabutylammonium tetrafluoroborate
>99% ([TBAm][BF
4
]), tetrabutylammonium hexafluorophos-
phate >99% ([TBAm][PF
6
]), tetrapentylammonium bromide
>99% ([TPAm][Br]), tetrahexylammonium bromide >99%
([THexAm][Br]), tetraheptylammonium bromide ([THepAm]-
[Br]), tetraoctylammonium bromide >99% ([TOAm][Br]),
methyltrioctylammonium bromide >97% ([MTOAm][Br]), ben-
zyldodecyldimethylammonium bromide >99% ([BDMDDAm]-
[Br]), and 1-hexadecylpyrdinium chloride >98% ([HDPy][Cl])
were purchased from Sigma-Aldrich (Fluka). 1-Butyl-3-methyl-
imidazolium chloride 98% ([C
4
MIm][Cl]), 1-butyl-3-methyl-
imidazolium methanesulfonate 98% ([C
4
MIm][CH
3
SO
3
]), and
1-butyl-3-methyl-imidazolium tosylate 98% ([C
4
MIm][Tosyl])
Figure 1. Typical PT diagram of a highly asymmetric system for an organic
compound and compressed gas.
ln
1
x
2
)
h
fus
R
(T
m
- T)
T
t
T
+
h
trans
R
(T
trans
- T)
T
trans
T
- ln
2
(1)
494 Ind. Eng. Chem. Res., Vol. 47, No. 3, 2008
were generously donated by Solvent Innovation. 1,5-Diethyl-
2-methylpyridinium ethylsulfate ([EEMPy][EtSO
4
]), tetrabutyl-
ammonium trifluorotris(perfluoroethyl)phosphate ([TBAm]-
[TFEPF
3
]), (1S,2R)-1-hydroxy-N,N,N-trimethyl-1-phenylpro-
pan-2-ammonium triflate ([EP][Tfo]), (S)-1-hydroxy-N,N,N-
trimethylbutan-2-ammonium triflate ([AB][Tfo]), (S)-N-(1-hy-
droxybutan-2-yl)-N,N-dimethylbutan-1-ammonium +menthol-
sulfate ([MTOA][+MS]), (R)-1-methoxy-N,N,N-trimethylbutan-
2-ammonium bis(trifyl)imide ([IHETMAm][Tf
2
N]), methyl-
trioctylammonium triflate ([MTOAm][Tfo]), trimethylsulfonium
bis(trifyl)imide ([TMSfn][Tf
2
N]), tetraethylammonium bis(tri-
fyl)imide 99% ([TEAm][ Tf
2
N]), and methyl-tributylphospho-
nium triflate ([TBMP][Tfo]) were generously donated by Prof.
Dr. Peter Wasserscheidt and were all of 98%+ purity (NMR).
Methyl tributylammonium triflate ([TBMAm][Tfo]) and methyl-
tris(2-methyl-propyl)ammonium triflate ([TiBMAm][TFo]) were
synthesized by direct metathesis of the tributyl (isobutyl) amine
by dropwise addition of methyltriflate in dichloromethane as a
solvent. The reaction was allowed to finish overnight and was
evaporated and then dried under vacuum. Purity was confirmed
by NMR. All samples, regardless of source, were dried under
vacuum and stored under argon in Schlenk tubes. In addition,
each sample was dynamically extracted with supercritical CO
2
prior to measurement.
Two different methods were used: one to determine the
pressure and temperature at the SLV and the other to determine
solely the solid-liquid equilibrium (concentrations) at pressures
slightly above the SLV pressure, to prevent the formation of a
vapor phase. The melting point depressions (SLV) and the PT
projection of binary systems of ionic solid and compressed gas
were measured using a static high-pressure view cell. The so-
called first melting method was used here, where the solid
sample was slowly heated at constant pressure and visually
observed for the first signs of melting. This method is opposed
to the so-called first freezing method where the sample is
liquefied, cooled, and crystallization is observed.
The apparatus consists of a high-pressure view cell (autoclave)
and a compressor. Figure 2a is a diagram of the apparatus. An
air-operated compressor with back-pressure regulator was built
in-house for the compression of the gases. The autoclave design
is similar to that used by Leitner and co-workers
52
for reactions,
except using view-cell glass (KDH, GmbH, PN400.4462 B 02-
47) with a 400 bar pressure rating. Pressure was measured with
a pressure transducer (Wika, GmbH, ECO-1) with a maximum
pressure rating of 400 bar, with a nominal accuracy of 2 bar.
The temperature was maintained by a heating plate (Ika Werke,
GmbH, PN: RET Basic C) with electronic temperature control
(Ika Werke, GmbH, PN: IKATRON ETS-d4-fuzzy) using a
Pt-1000 RTD placed through the wall of the autoclave. The
precision is 0.1 C and was calibrated to an ice-bath and boiling
water adjusted for atmospheric pressure for a resultant accuracy
of approximately 0.2 C.
All samples were dried in vacuo (0.1 mbar) for ap-
proximately 48 h. Approximately 200 mg of the sample (most
were powders) were placed into a small sample vial capable of
fitting into the autoclave. The sample vial was placed in the
autoclave while under argon and sealed. The autoclave was
connected with the compressor and then purged with the desired
gas. For the CO
2
systems, the autoclave was then charged to
supercritical conditions (40-60 C and 150-200 bar) and
allowed to equilibrate for about 10 min. The system was then
dynamically extracted for about 5 min. This was to ensure
removal of any residual organic contaminants or water. The
system was depressurized and allowed to rest for approximately
10 min. After this purging process, the autoclave was pressurized
to the desired pressure and heated slowly. With the aid of a
background light, the solid sample was observed for any sign
of phase change while heating at a rate of roughly 2 C/min.
Once the first sign of melting occurred, the heating was stopped
and the autoclave depressurized to cool below this melting point.
The process was then repeated at a much slower heating rate
of approximately 0.05 C per minute; this was determined to
be sufficient to allow adequate time for thermal equilibrium
for the whole system. This was repeated for a total of three
times to ensure that the temperature of this solid-liquid-vapor
transition was reproducible to approximately 0.5 C (usually to
0.2 C). After each induced melting, the autoclave was turned
upright and shifted to spread the liquid over the bottom of the
sample vial containing the substance in the autoclave and then
depressurized to crystallize the material as a thin film. Upon
return of the autoclave to a horizontal position, the film of
material is now vertical and directly within the plane of the
light path, which allows easier detecting of the melting point.
As the material changes from a crystalline state to a liquid state,
the film evolved from an opaque solid to a clear liquid
accompanied by downward flow due to gravity. Many of the
studied materials are known to have solid-solid transitions,
amorphous, and liquid crystal phases. At times, some of these
materials became more transparent but did not flow within a
reasonable time-scale (10 min). Others began to flow before
becoming completely transparent. Only when transparency and
Figure 2. Experimental apparatus used in these experiments: (a) autoclave
for melting point depression data (SLV) [(1) heater/stirrer, (2) windowed
autoclave vessel, (3) valve, (T) RTD, (P) pressure transducer]; (b) solubility
at the melting point depression (SLE).
Ind. Eng. Chem. Res., Vol. 47, No. 3, 2008 495
flow are observed is the solid-liquid-vapor temperature taken
unless otherwise noted.
Solid-Liquid Equilibrium. In a separate experiment, the
solid-liquid equilibrium was determined at known compositions
of the liquid phase. A modest hydrostatic overpressure was used
to ensure our knowledge of liquid composition, but the
overpressures (tens of bars) are too small to have any measurable
effect on the melting point depression observed. All of these
measurements of CO
2
were carried out in a variable-volume
windowed vessel (1.59 cm i.d., 20 cm
3
maximum volume)
similar to that used by McHugh
53
which was used previously
to measure liquid-liquid equilibrium (LLE) systems.
54
A
schematic of this vessel is located in Figure 2b. The vessel
window and variable-volume piston were sealed with Buna-N
O-rings. Phase boundaries were measured by visually observing
the freezing point through a 2.54 cm diameter sapphire window
(1.27 cm viewable area) with a charge-couple device (CCD)
camera (Sony) mounted on a 0.635 cm borescope (Olympus).
The borescope and video camera not only allowed for safe
observation of the phase equilibria but also provided a significant
magnification of the viewable area. The binary mixtures were
stirred with a Teflon-coated stir bar coupled with an external
magnet. The entire cell was placed in a thermostated air bath
(modified Varian 3400 gas chromatograph) with temperature
control better than (0.5 K. Precise temperature control was not
required as freezing points were induced and observed while
cooling the vessel. The temperature was measured with a hand-
held readout (HH-22 Omega) and thermocouple (Omega type
K) inserted into the center of the phase equilibria vessel. The
thermocouple response time was on the order of seconds. The
combination of thermocouple and readout was accurate to (0.2
K and calibrated for each experiment against a platinum RTD
(Omega PRP-4) with a DP251 precision RTD bench-top
thermometer (DP251 Omega) accurate to (0.025 K and
traceable to NIST. Back-pressure was applied to the piston with
a syringe pump (ISCO 100D) operated at constant pressure. To
avoid any vapor phase, the pressure was held constant at 210
bar measured with a Druck DPI 260 gauge with a PDCR 910
transducer accurate to (0.1 bar.
To ensure that this method would be applicable to melting
point depression measurements, experimental data were taken
to compare with literature. Cheong et al.
34
measured the
temperature composition of naphthalene-CO
2
using what they
called the first freezing point method. This method involved
observing the initial appearance of solid, followed by sampling
from a high-pressure view cell. An equation of state, paired
with pressure, temperature, and volume data, provided the gas-
phase composition. Gravimetric measurement of the solid phase
after dissolution and drying gave the other compositions. Figure
3 shows the comparison of our data to the literature, where the
two methods show excellent correlation. Thus, our novel
freezing point method was validated, where the composition
could be determined without sampling.
First, a known mass of organic solid was loaded into a
variable-volume high-pressure view cell, and the pure solid
melting point was confirmed before adding any CO
2
. Then, the
cell with a known quantity of CO
2
from a syringe pump was
loaded and allowed to reach equilibrium with temperature and
pressure such that there was a single liquid phase. Next, the
mixture was cooled isobarically until the first crystal formed.
Generally, the entire contents froze quickly thereafter. The
composition of the single liquid phase is known since there are
only two components and one phase. The first crystal of pure
solid has a negligible impact on the overall composition, and
thus, the composition at the freezing point is known.
After one freezing point is measured, the system was reheated
back into one phase, and the process was repeated until two
consecutive data points were identical to ensure the system was
at equilibrium, which can take up to 24 h, depending on the
solid.
The high-pressure cell was also loaded under nitrogen
atmosphere, thus preventing air contamination of the solids.
After secondary purification, the ionic solids were tested for
water content. Samples were prepared by dissolving 1 g of solid
in 0.5 mL of methanol. Methyl alcohol, extra dry with molecular
sieves, <50 ppm water, was purchased from Acros Organics.
The water contents of both the methanol and the dissolved solids
were measured using a Karl Fisher titrator, model DL31 from
Mettler Toledo. Aquastar Combititrant 1 from EMD chemicals
was used for the titrant. Physical properties and modeling
parameters are listed in Table 1.
Results and Discussion
Initially, the melting point depression with CO
2
was measured
with common imidazolium and pyridinium cation classes. As
shown in Table 2, only moderate melting point depression data
were obtained for these compounds; the relative magnitude of
which is consistent with most organic compounds, e.g., naph-
thalene with CO
2
, etc. Interestingly, the long-alkyl chain
pyridinium compound, [HDPy][Cl], experiences a broader range
of melting point depression, consistent with solid-solid or
liquid-crystal transitions as observed by Kazarian et al.
31
Considerably larger and very pronounced melting point de-
pressions were observed for salts based on tetraalkyl ammonium
cations. Table 3 illustrates the profound influence of the anion
on the melting point depression with tetrabutylammonium
cations. [TBAm][BF
4
] has one of the largest melting point
depressions at 120 C of any organic compounds with CO
2
known to the authors. This is in contrast to the bromide, which
Figure 3. Temperature-composition (T-x) diagram for naphthalene-
CO2: experimental data compared to literature values (ref 34), ideal
solubility, and modeling.
Table 1. Physical and Model Properties of Select Ionic Solids
ionic solid
Tm
[C]
Hfus
[kJ/mol]
Ttrans
[C]
Htrans
[kJ/mol]
naphthalene
a
80.2 18.8
[TBAm][BF4]
b
160 10.5 68 2.5
[THexAm][Br]
b
100 15.9 32 2.5
a
Reference 34.
b
Reference 65.
496 Ind. Eng. Chem. Res., Vol. 47, No. 3, 2008
has only a moderate depression of roughly 20 C, and the
tosylate, with a depression of 34 C. The highly fluorinated
trifluorotris(perfluoroethyl)phosphate anion produces a tetrabu-
tylammonium compound with a normal melting point of 54 C
and T
m
of 37 C at only 35 bar of CO
2
pressure. Table 3 also
indicates that analogous phosphonium compounds (tetrabutyl
phosphonium vs ammonium bromides) seem to have larger
melting point depressions with CO
2
.
Table 2. Melting Point Depression of Imidazolium and Pyridinium Solids
a
Reference 32.
Table 3. Tetrabutyl Ammonium and Phosphonium Compounds
a
Refernce 32.
b
TSLV is beyond the upper temperature limitation of equipment (>100 C).
Table 4. Melting Point Depression of Quaternary Ammonium Bromide Compounds with CO2
a
Reference 32.
b
Possible solid-solid/liquid crystal transitions.
Ind. Eng. Chem. Res., Vol. 47, No. 3, 2008 497
For quaternary ammonium compounds, the cation may also
have a large effect on the SLV behavior. With a common
bromide anion, symmetric tetra-alkyl compounds (four equal
substituents) have rather similar normal melting points at
approximately 98 C (see Table 4), from tetrabutyl- to tetraoctyl-
ammonium bromide. However, the maximum T
m
occurs with
tetra-hexyl-ammonium bromide and CO
2
with a decrease of
71 C, while smaller and larger alkyl chains produce signifi-
cantly less-pronounced T
m
values at similar pressures. Replac-
ing one of the alkyl chains with a methyl group (methyl-trialky-
ammonium) seems to simultaneously decrease the normal
melting point and increase the degree of T
m
(see [MTOAm]-
[Br], [BDMDDAm][Br], and [MTOA][Br] in Table 4).
Table 5 illustrates various cations with fluorinated sulfonate
or bis(trifluorylmethysulfonyl)imide [Tf
2
N] anions. These cat-
ions include chiral ionic solids ([EP][Tfo], [AB][Tfo], [MTOA]-
[+MS], and [IHETMAm][Tf
2
N]) for potential use in chiral
reactions
55
and separations. Of special note is the relatively
simple ionic solid, tetraethylammonium [Tf
2
N]. This compound
has a normal melting point of 102 C but melts at 20 C with
only 35 bar of gaseous CO
2
. This T
m
at 82 C would probably
represent the largest melting point depression of all of the
compounds tested if cryogenic equipment were available to
permit measurement and comparison at 150 bar. This represents
an approximately 2.4 C depression per bar of CO
2
pressure.
Overall, several trends can be established to increase the
melting point depression with CO
2
and organic ionic solids.
Fluorinated anions universally increase the melting point
depression. This follows the observation of Kazarian et al.,
31
who found enhanced CO
2
interaction with fluorinated anions
by ATR-IR. Bis(trifyl)imide ([Tf
2
N]) anions always seem to
yield the highest melting point depressions, even considering
the usually lower normal melting points. Asymmetric am-
monium cations which have more nonequal substituents (e.g.,
methytributyl ammonium [TBMAm], trimethyl-hydroxyisobutyl
ammonium [AB][Tfo], etc.) tend to have lower melting points
with CO
2
pressure compared with equal substituents. Straight
chain alkyl groups tend to have lower T
m
values to a greater
extent than similar branched salts, e.g., [TBMAm][Tfo] vs
[TiBMAm][Tfo] in Table 5. For the more planar cations, i.e.,
imidazolium and pyridinium, the anion seems to have a much
greater effect than the cation.
SLV with Pressure and Temperature. The melting point
depression of several ionic solids was taken over larger pressure
ranges. Figure 4 and Table 6 illustrate the global phase behavior
of four ionic solids to 350 bar of CO
2
pressure. As seen from
Table 5. Various Cations with Sulfates or Bis(trifyl)imide Anions
a
Reference 32.
498 Ind. Eng. Chem. Res., Vol. 47, No. 3, 2008
the figure, the change in the SLV temperature of the ionic solids
with pressure is extremely large and negative in the lower
pressure range, i.e., P < 150 bar. [TBAm][BF
4
] shows the most
dramatic decrease, while [TOAm][Br] shows much more
moderate depression. At higher pressures, the increase in melting
point depression is minimal with added pressure. The melting
point depression of [TBAm][BF
4
] was also measured with
ethylene and found to be large compared with most nonionic
organics (naphthalene
35
and octacosane
34
with CO
2
), but still
much lower than the same salt with CO
2
. This difference is
almost surely due to variations in the solution behavior. The
phase behavior of CO
2
and the long-chain wax, octacosane (C
28
),
from the work of Cheong et al.
34
and the polyaromatic,
naphthalene, from the work of McHugh and Yogan
35
are shown
for comparison. Initially, both of the solids undergo moderate
melting point depression but not nearly to the same magnitude
as the ionic solids. Octacosane and naphthalene both have a
minimum in T
SLV
with pressure between 100 and 150 bar. After
this minimum, the trend reverses and the melting point increases
rather than decreases. At approximately 650 bar in the octa-
cosane/CO
2
system,
34
the T
SLV
equals T
m
, i.e., no melting point
depression, followed by a melting point elevation at higher
pressures. For the ionic solids, the largest rate in depression
occurs between 0 and 150 bar. After which, the depression
seems to level off approaching some asymptotic value. Whether
these ionic solids experience a minimum in T
SLV
similar to
octacosane and naphthalene is uncertain. This study was limited
to 400 bar.
Modeling Discussion Solid-Liquid Equilibrium. A number
of differences in the results can be shown to be a function of
solution nonideality. For example, the melting point depressions
observed for [TBAm][BF
4
] with ethylene were far less than
those for the same salt with CO
2
. Moreover, the melting point
depression for naphthalene in CO
2
is substantially less profound
than that of the ionic liquids in CO
2
. The reason is almost surely
due to specific interactions. Naphthalene interacts with CO
2
almost entirely by dispersion (van der Waals) forces, as does
ethylene with the ionic liquid. Such interactions always give
positive deviations from Raoults law ( > 1), and this term
would become important in eq 1. Conversely, CO
2
would
interact with the ionic liquids in a different way, with strong
unlike pair specific attractions due to the chemistry of CO
2
,
probably due to weak Lewis acid-Lewis base interactions of
the acidic carbon in CO
2
with basic moieties of the saltsand
similar interactions have been observed often in other situa-
tions.
56-58
These would give negative deviations from Raoults
law ( < 1), and this term would also become important
in eq 1.
As previously mentioned, Figure 3 shows a comparison of
literature results to model predictions for the composition versus
Figure 4. Experimental and modeling of the SLV of several ionic solids
and naphthalene (ref 35) and octacosane (ref 34) [smoothed data].
Table 6. SLV Equilibrium for Several Ionic Solids
[TBAm][BF4]/CO2 [TBAm][BF4]/Ethylene
TSLV [C] PSLV [bar] T [C] TSLV [C] PSLV [bar] T [C]
27.2 335 128.8 73 250 83
30.0 250 126 81.1 200 74.9
33.4 200 122.6 89.8 150 66.2
36.1 150 119.9 109 100 47
40.5 100 115.5 156.0 1 0
87.3 85 68.7
100.0 78 56
156.0 1 0
[TOAm][Br]/CO2 [TBMPhos][Tfo]/CO2
TSLV [C] PSLV [bar] T [C] TSLV [C] PSLV [bar] T [C]
59.4 350.0 38.1 33.1 350.0 85.9
60.3 300.0 37.2 35.0 300.0 84.0
61.3 250.0 36.2 36.7 250.0 82.3
61.6 200.0 35.9 38.8 200.0 80.2
61.8 150.0 35.7 40.4 150.0 78.6
64.3 125.0 33.2 44.3 125.0 74.7
66.8 100.0 30.7 52.5 100.0 66.5
71.7 86.0 25.8 68.0 90.0 51.0
75.5 75.0 22.0 77.5 80.0 41.5
97.5 1.0 0.0 119.0 1.0 0.0
Table 7. T-P-Composition Data of Melting Point Depression with
CO2
system
with CO2
T
[C]
P
[bar] xCO2
system
with CO2
T
[C]
P
[bar] xCO2
naphthalene -56.6 1 1 [TBAm][BF4] -56.6 1 1
55.5 172.4 0.838 28.1 102.9 0.539
59.0 181.3 0.556 45.6 239.3 0.504
59.4 222.6 0.549 59.5 232.7 0.458
59.7 241.3 0.536 73.9 102.9 0.393
60.0 195.2 0.498 120.1 198.4 0.244
60.1 77.6 0.438 140.1 116.9 0.145
60.8 215.8 0.528 144.1 168 0.097
61.6 195.1 0.448 160 1 0
63.2 137.9 0.365 [THexAm][Br] -56.6 1 1
63.7 174.6 0.371 34.7 231.8 0.569
66.1 139.9 0.311 50.4 177.5 0.412
67.2 105.0 0.262 64.8 136.8 0.286
68.5 105.1 0.239 79.2 202.9 0.171
69.5 153.8 0.239 100 1 0
69.7 105.1 0.239
70.8 105.1 0.203
73.3 84.3 0.143
73.5 105.3 0.154
74.3 77.1 0.098
76.1 77.2 0.062
77.1 181.3 0.096
80.3 1 0
Figure 5. T-x diagram for tetrabutyl ammonium tetrafluoroborate-CO2
with ideal solubility prediction.
Ind. Eng. Chem. Res., Vol. 47, No. 3, 2008 499
melting temperature and pressure for the naphthelene-CO
2
system. The pressure, temperature, and composition data are
listed in Table 7. Also included on this figure are the ideal
solution prediction and the MOSCED (modified separation of
cohesive energy density) prediction.
59,60
It is clear that the ideal
prediction (eq 1, with
2
set at unity) for this system is a poor
predictor for this system due to the large positive deviation from
ideality, as one would expect for CO
2
-naphthalene interactions.
The MOSCED model (eq 2), which has been recently shown
to work well at predicting solid solubility,
59,61
fits four
parameters (hydrogen bond acidity and bascity, polarizability,
and dipolarity) to experimental data to calculate infinite dilution
activity coefficients.
The calculated activity coefficients were used in the Wilson
equation
48
to predict the solubility line shown in Figure 3.
Several different modeling techniques have been used to
predict the interaction between CO
2
and ionic liquids, including
the tPC-SAFT equation of state,
62
the irregular ionic lattice
model,
63
and molecular dynamic simulations.
64
However, as with
most thermodynamic models, some experimental solubility data
are needed for parameter tuning. For the tPC-SAFT model,
vapor pressure data is needed; for the irregular ionic lattice
model, solubility data is needed. MOSCED model parameters
have been successfully regressed for a few ionic liquids in
various solvents.
59
However, there is currently insufficient data
for any of the ionic solids studied here to allow MOSCED
prediction with CO
2
. Future work in the area of thermodynamic
modeling of ionic liquids will require an extensive solubility
study over a wide range of ionic liquid solutes. Although no
modeling is reported for our CO
2
-IL data, the results were
compared to the ideal solubility.
CO
2
Solubility at the Melting Point. The results for [TBAm]-
[BF
4
] are shown in Figure 5 and listed in Table 7. The ideal
solubility, shown for reference, is calculated from eq 1 with
each of the respective activity coefficients set equal to 1. The
low-temperature region is enlarged to show the simple eutectic
behavior expected in a melting point depression T-x diagram.
The results show a melting point depression of 130 C at a mole
fraction near 0.5. The results seem to agree with the work of
Scurto and Leitner
32
and elucidate the effect the CO
2
has on
[TBAm][BF
4
]. Figure 6 (Table 7) demonstrates the results for
[THexAm][Br] which are very similar to that of [TBAm][BF
4
].
The ideal solubility is again included and it is clear that for
both ionic liquids, the T-x curve falls well below the ideal
solubility. This is in stark contrast to the naphthalene/CO
2
data,
where there are strong positive deviations from Raoults law.
Conclusions
Here, the melting point depression of a large variety of ionic
solids was measured. Some compounds represent some of the
largest melting point depressions known in the literature. As
shown from ideal modeling, negative deviations to Raoults law
exist, indicating specific interactions of the CO
2
with the ionic
solid. Understanding and controlling this induced melting will
allow a much greater number of ionic liquids to be utilized in
these biphasic processes. This is especially important when
designing task-specific ionic liquids.
Acknowledgment
We would like to thank the National Science Foundation
(USA) for a postdoctoral fellowship (NSF-IRFP for A.M.S.).
The Georgia Tech group also acknowledges support from the
donors of the J. Erskine Love, Jr., Institute Chair. W.L. thanks
the BMBF (Grant Numbers 03X2008D and 03X2012A) as well
as the Fonds der Chemischen Industrie for financial support.
Solvent Innovation (Cologne, Germany) and Peter Wassersc-
heidt (University of Erlangen) are thanked for generous donation
of samples.
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)
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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