Review 1

Review
Solubility of organometallic complexes in supercritical carbon dioxide: A review

Wen Hui Teoh
a, b
, Raffaella Mammucari
b
, Neil R. Foster
b,
*
a
Department of Chemical Engineering, University of Malaya, 50603 Kuala Lumpur, Malaysia
b
School of Chemical Engineering, Chemical Science Building (F10), University of New South Wales, Sydney, NSW 2052, Australia
a r t i c l e i n f o
Article history:
Received 1 December 2010
Received in revised form
28 September 2012
Accepted 2 October 2012
Keywords:
Solubility
Organometallic
Supercritical uid
Carbon dioxide
Thermodynamic model
Ligands
a b s t r a c t
The solubility and solubility trends of organometallic complexes in supercritical carbon dioxide are
reviewed. The inuence of intermolecular forces, physical properties and the metal chelates on solubility
is explored. A number of thermodynamic models used to predict the solubility behavior of organome-
tallic complexes in supercritical carbon dioxide, and the advantages and limitations to these thermo-
dynamic models are also discussed.
2012 Elsevier B.V. All rights reserved.
Contents
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .102
2. Solubility and the factors affecting solubility in supercritical fluids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .104
2.1. The effects of intermolecular forces on solubility . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 104
2.2. The effects of the free volume difference on solubility . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105
2.3. Clustering and the solubility enhancement factor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105
2.4. The effects of pressure and temperature on solubility . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 106
2.5. The effects of organometallic complexes on solubility . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 106
3. Thermodynamic modeling of soluteeSCF solubility behavior . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .111
3.1. Solubility parameter, d and the regular solutions theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111
3.2. Empirical methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 112
3.3. Equations of state (EOSs) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 113
4. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 114
Acknowledgment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 114
Nomenclature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 114
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 114
1. Introduction
Asubstance above its critical temperature and pressure is known
as a supercritical uid (SCF). Supercritical uids exist in a single
homogenous phase where the liquid and gas phases are
indistinguishable. As such, SCFs have characteristics that are inter-
mediate to those of gases and liquids. Typically, a liquid substance is
changed to its gaseous phase by moving it through the vaporization
curve, given by path AeBeC in Fig. 1. This involves heating and/or
decompression which is accompanied by drastic or abrupt changes
to its physical properties. Ameniscus is observedas Ais changedtoC
through B. However, a liquid can also be changed to its gaseous form
without having to go through phase transition. This is carried out by
* Corresponding author. Tel.: 612 9385 4341; fax: 612 9385 5966.
E-mail address: n.foster@unsw.edu.au (N.R. Foster).
Contents lists available at SciVerse ScienceDirect
Journal of Organometallic Chemistry
j ournal homepage: www. el sevi er. com/ l ocat e/ j organchem
0022-328X/$ e see front matter 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jorganchem.2012.10.005
Journal of Organometallic Chemistry 724 (2013) 102e116
manipulating both temperature and pressure changes; allowing the
substance to pass through the supercritical region [path AeDeC]
where its physical properties are varied continuously.
The two most distinctive traits of a supercritical uid are its
enhanced mass transfer properties compared to liquids and its
variable density. The density of a SCF is highly tunable as it is
sensitive to changes in temperature and pressure. As density
contributes directly to the solvent strength of a given SCF, the
solvating power of a SCF is also easily manipulated. The easy
manipulation allows for the maneuvering of process designs to
facilitate separation, extraction and deposition of compounds. In
most cases, the ease of control and the tune-ability of the liquid-like
density of SCFs enable the need for toxic organic solvents to be
bypassed. The mass transport properties of SCFs are similar to those
of conventional gases and add to the desirability of SCF processes, as
their gas-like diffusivity and viscosity allow for faster penetration
into solid matrices and surfaces. These characteristics facilitate the
deposition of compounds into, and the extraction of compounds
from, matrices. In addition, the low operating temperatures typical
of SCF processes allows for the processing of thermally-labile
compounds, while the sterilizing ability of SCFs adds to the advan-
tages of using SCFs in biomedical and pharmaceutical applications.
Carbon dioxide is the most widely used SCF due to its mild
critical temperature (31.1

C) and pressure (7.38 MPa). It is non-
ammable, non-toxic, the second least expensive solvent after
water, fairly miscible with a wide variety of organic solvents, easy to
recover after processing due to high volatility and is considered
environmentally friendly as it can be obtained from existing
industrial processes without adding to the greenhouse effect [1,2].
Reviewon the advantages of supercritical uids as green processing
medium can be found in Beckman [2]. Compared to conventional
large molecular-sized solvents, CO
2
with its small linear structure
diffuses more quickly [1].
Supercritical uid technologies have garnered the interest and
attention of researchers and industries alike since the late 1970s
due to their unique properties [3]. These green technologies have
been successfully employed in the decaffeination of coffee [3] and
the extraction of spices, hops, tobacco, aromas, essential oils,
acetone residues from antibiotics and pharmaceuticals from
botanicals [4e12]. In recent years, research efforts in SCF technol-
ogies have expanded from mere extractions to sterilizations,
micronizations, encapsulations and depositions for biomedical,
pharmaceutical, chemical, food, energy and agriculture applica-
tions. Current research includes fabrication of three-dimensional
porous scaffolds for tissue engineering applications [13], prepara-
tion of electrocatalysts for membrane fuel cells through supercrit-
ical uid deposition [14], extraction and in-situ chelation of metals
from aqueous and waste solutions [15e19], and encapsulation of
active pharmaceutical ingredients (APIs) for controlled delivery
purposes [20]. Chemical reactions, properties and applications in
SCFs are extensively reviewed in the literature and can be obtained
from Refs. [3,21e29].
The use of metallic, organometallic and inorganic compounds in
chemical and biomedical applications is not new. Metal-based
chemotherapeutic drugs such as Cisplatin have been used since
the late 1970s and have been proven to be effective in anticancer
treatments [30,31]. The success of Cisplatin, or cis-dia-
minedicholoroplatinum(II), has spawned a domino effect on the
development of platinum and palladium based anticancer drugs
[32e34]. The diverse and varying coordination numbers and
structures of organometallics, and the accessible redox states
provide many opportunities in the design and application of novel
medical therapeutics [35]. Moreover, the intrinsic properties of the
cationic metal and ligand allow for control over kinetic and ther-
modynamic characteristics through ligand design [35e38]. Thus,
recent years have seen concerted efforts focused toward the
development of metal-based compounds, particularly for diag-
nostic and therapeutic purposes. Recent developments include the
use of ruthenium, yttrium, indium, rhodium, osmium, gold, gallium
and cobalt in anticancer therapies [32,39e44] while cyclo-
pentadienyls, arene, carbonyl and carbene are typical classes of
ligands used in medicinal therapeutics [36]. Transition metals such
as technetium, manganese and iron are also increasingly used in
medical imaging as only low dosages are required of these highly
sensitive materials. The discovery of molecular targets and the
development of nanocarriers carrying metal-based anticancer
drugs that selectively target tumors are creating newopportunities
for a drug combination therapy where two or more types of therapy
(such as chemotherapy and radiotherapy), or two or more APIs, are
delivered toward a specic target [45,46]. The use of organometallic
compounds in medicinal therapeutics has been reviewed in
a number of publications and can be found in Refs. [34,36,47e50].
The signicant use of metal-based compounds in imaging,
therapeutics and catalysis, and the advantages of SCF technologies
have resulted in the initiation of numerous studies of SCF processing
of organometallics. These include the deposition of copper lms for
advanced interconnecting structures using copper(I)(1,1,1,5,5,5,-
hexauoro-2,4-acetylacetonate)(1,5-cyclooctadiene) [51], synthesis
of ultra high molecular weight polyethylene (UHMWPE)/silver
nanocomposites for total joint replacement components [52],
synthesis of gold nanoparticles from gold(I) peruorooctanoate in
supercritical carbon dioxide [53], copolymerization of carbon
monoxide and styrene in supercritical CO
2
with palladium
complexes as catalysts [54], and the mironization of titanocene
dichloride (a metallocene catalyst) via rapid expansion of super-
critical solvent (RESS) [55]. However, most SCF related studies on
organometallic compounds are heavily concentrated on catalysis
and waste metal extractions while researchin the area of processing
metal-basedtherapeutics has not receivedthe same level of interest.
The exploitations of SCF technologies for homogeneous and
heterogeneous catalysis have been reviewed and can be found in
Refs. [56e62]. Review on supercritical uid extraction of metals
from aqueous media can be obtained from Refs. [15,63].
While the use of SCFs to process metal-based compounds is
gaining ground, a limitation of the technology is a lack of funda-
mental data. The complexity, the non-ideality and the non-linearity
of SCF characteristics make it difcult to predict their behavior and
that of the compounds involved under supercritical conditions. The
lack of predictability hence, requires extensive, expensive and
time-consuming trial and error experimental studies [64]. Phase
behavior predictions of soluteeSCF systems also become more
challenging as the molecular complexity of the solutes increases
[65]. While the current thermodynamic models such as the Penge
Supercritical
region
solid
Critical
Temperature
Pressure
C
Triple
point
liquid
gas
Temperature
B
A
D
Critical
Pressure
Critical point
Vaporization
curve
Fig. 1. Phase diagram for a pure substance.
W.H. Teoh et al. / Journal of Organometallic Chemistry 724 (2013) 102e116 103
Robinson EOS (equation of state) and the SoaveeRedlicheKwong
EOS are highly regarded, limitations remain in their ability to
predict highly non-ideal thermodynamic behavior, particularly for
metal-based complexes, in the supercritical region. The challenges
involved in predicting solid-SCF phase equilibria include: (1) the
lack of vapor pressure data for relatively non-volatile solids, (2) the
extremely asymmetric sizes and energies of the components in SCF
solutions, and (3) the highly condensable solutions that lead to
solvent clustering around the solute [65]. Hence, accurate ther-
modynamic models for highly non-ideal and highly compressible
mixtures are essential.
In the present paper, the solubility of organometallic complexes
in supercritical carbon dioxide (SCCO
2
) and a number of thermo-
dynamic models used in organometallic-SCCO
2
systems are
reviewed. Solubility studies are fundamental to quantifying the
ability of a SCF to act as a solvent and consequently, the feasibility of
a particular process for a particular application [66,67]. Solubility
data inuences the type of a SCF process to be used e be it an anti-
solvent or a solvent based SCF technology. Solubility also shows the
limit to extraction or the maximum concentration available for
deposition, and provides the thermodynamic limit to a process
[68]. There is therefore, a need to investigate the factors that affect
solutes solubility in supercritical uids to allow for a continual
development in the many potential applications, design and scale
up of SCF processes. Reviews on the solubility and dissolution of
solutes in sub- and supercritical uids have been covered in varying
depths and degrees by various authors [3,69e73]. The experi-
mental methods for solubility determination generally involve
analytical or synthetic methods, and have been systematically
reviewed by several authors over the last fewdecades [74e79]. The
phase behavior of binary and ternary mixtures in supercritical
carbon dioxide warrant its own review, and can be found in Refs.
[3,22,80e83].
2. Solubility and the factors affecting solubility in
supercritical uids
Solubility is the analytical composition of a solution saturated
under equilibrium with one of the components of the solution at
a particular temperature and pressure [84,85]. It quanties the
dynamic equilibrium state achieved where the dissolution rate
equals that of the precipitation rate in a solideliquid system.
Solubility is very dependent on the intermolecular forces between
soluteesolvent, soluteesolute and solventesolvent [3]. For
a system consisting of a solute, i and a solvent, j, the ability of i to
dissolve in j is given by the strength of interactions between i and j.
If the attractive forces of iej are higher than that of iei and jej, then
the solute i would dissolve in the solvent j. The ancient heuristic of
like dissolves like is still applicable in many soluteesolvent
systems since intermolecular forces between similar chemical
compounds lead to smaller endothermic enthalpy of solution than
dissimilar compounds [86]. The factors that contribute to the
solubility of a given solute in a solvent are summarized in Fig. 2.
2.1. The effects of intermolecular forces on solubility
The fundamental source of most physical properties of a mole-
cule is its intermolecular forces [64]. Intermolecular forces in
operation between molecules are governed by the physical and
chemical forces existing between the molecules in the solution. The
physical forces of attraction between molecules are governed by
the momentary (induced) dipoleedipole potential energy and the
permanent dipoleedipole potential energy. In the momentary
dipoleedipole potential energy interaction, a molecule with
a momentary dipole causes a dipole in neighboring molecules,
producing net attractive forces between the molecules that
subsequently governs the solubility of a non-polar solute in a non-
polar solvent [3]. The momentary dipoleedipole potential energy
depends on the polarizability of a molecule and the distance
between two molecules. The polarizability of a solvent (which
increases with its molecular size) indicates the strength of the
solvent [3]. The momentary dipoleedipole potential energy is,
however, not affected by temperature changes.
The permanent dipoleedipole potential energy provides an
additional force of attraction between molecules. Large, complex
molecules generally have weakened dipole interactions due to the
large volume of the molecules [87]. A molecule with high polar
moments and high dielectric constant is considered polar. The
permanent dipoleedipole potential energy changes with inter-
molecular distance while it decreases with increasing temperature.
Hence, a polar liquid solvent (which generally has a high critical
temperature) exhibits non-polarity in the supercritical region [3].
At very high pressures and densities, repulsive intermolecular
forces could also dominate and reduce the solubility of a solute
[88]. Higher-order polar moments also affect the solvating power of
a solvent although these effects are less signicant than a dipole
moment [3]. A good example is carbon dioxide which has a large
quadrupole moment that plays an important role in its solvating
power [3,89] and greatly enhances the solubility of a number of
polar solutes in supercritical carbon dioxide [90].
Chemical forces of attraction such as hydrogen bonding and
electron acceptoredonor complexing also play an important role in
solubility, although these are harder to quantify [3]. The effects of
chemical forces in a solution are generally categorized as solvation,
where the molecules of the solutes and solvents tend to form
complexes [91]. In contrast to physical forces, chemical forces can
become saturated and are very dependent on temperature [91].
Chemical forces generally decrease with increasing temperature
such as the observed weaker H-bonds in sub-critical and super-
critical water [92,93]. Generally, H-bonds are easily broken at
higher temperatures when the molecules involved have sufcient
energy to break loose as the strength of H-bonds are lower than
that of covalent bonds [91].
Supercritical carbon dioxide is generally considered a solvent
comparable to dioxane, with solvation in carbon dioxide largely
attributed to its quadrupole moment [89,94]. In spite of its zero
dipole moment, carbon dioxide has partial negative charges on the
electronegative oxygen atoms and a large partial positive charge on
its electropositive carbon atom, allowing for the electron-decient
carbon atom to act as a Lewis acid (LA) and the oxygen atoms as
Lewis base (LB) moieties. Recent studies have shown that the
charge separation and electronic structure of CO
2
allow for a Lewis
acideLewis base (LAeLB) interaction between CO
2
with a carbonyl
[95e97]. Spectroscopy and theoretical studies also found weaker,
shorter CeH/O hydrogen bond [98,99] that interacts in
Factors that affect solubility
Intermolecular (attractive) forces
Physical forces
Momentary dipole-
dipole potential
energy
Permanent dipole-
dipole potential
energy
Chemical forces
Hydrogen bonding,
electron aceptor-
donor complexing
Free volume
difference
Density
Temperature and
pressure
Fig. 2. Factors affecting the solubility of a solute in a solvent. Extracted from Ref. [3].
cooperation with the LAeLB bond that further stabilizes the
soluteesolvent interactions [95,96]. A resultant of the LAeLB
interaction and the CeH/O hydrogen bond is the increased
polarization of one of the CaO bonds of CO
2
that subsequently
enhances the solubility of a number of polar solutes in SCCO
2
[96].
Recent
1
H,
13
C and
19
F NMR studies conducted on b-diketones and
UO
2
(b-diketonato)
2
dmso [dmso dimethyl sulfoxide] complexes
found that their solvations in SCCO
2
are attributed to a balance of
van der Waals, LAeLB and the CeH/O interactions [95,100].
Further reading on the polar attributes of CO
2
and their contribu-
tion to solvation can be obtained from Refs. [94e96].
Various other studies have alsofoundthat the presenceof inter- or
intra-molecular hydrogen bonds in a SCF can enhance solubility
[101e106]. The addition of a modier into a SCF that can form
hydrogenbonds witha solute, generally increases the solubilityof the
solute. Fig. 3 shows the solubility of benzoic acid inSCCO
2
, and SCCO
2
with methanol. The solubility of benzoic acid increases by almost an
order of magnitude with the addition of methanol as a co-solvent.
Anderson and Siepmann [102] attributed this effect to the hydrogen
bondformedbetweenbenzoic acidandmethanol. Hydrogenbonding
has also been found to occur between metal-containing and/or
organometallic complexes in SCFs [90,107] although the effects of
suchbonding onsolubilityare rarely quantied. Ina study conducted
by Tenorio et al. [108], the solubility of nickel hexa-
uoroacetylacetonate dehydrate [Ni(hfa)
2
$2H
2
O] was found to be
higher in SCCO
2
with ethanol as a modier than that in SCCO
2
alone.
The authors suggested that the better solvation of the nickel hexa-
uoroacetylacetonate dehydrate complex in CO
2
eethanol mixture
was due to a possible rupturing of the hydrogen bond network
between the Ni(hfa)
2
$2H
2
O molecules and the formation of new
hydrogen bonds between the nickel complex and ethanol [108].
2.2. The effects of the free volume difference on solubility
Free volume is dened as the total integral over the part of the
potential energy due to the thermal displacements of the center of
gravity of the molecule from its equilibrium [110]. It is the empty
volume available to the molecule after subtracting the hard-core
volume of the molecule itself [111]. Therefore, free volume
reects the compressibility or expansivity of a substance [3]. The
free volume difference between a solute and a solvent is related to
the density of the solvent as this affects the interaction level
between molecules in a solution. A solute in a SCF must be in close
enough proximity to interact with the solvent molecules to affect
solubility [3]. As the density of a SCF increases, so does the ability of
the SCF to solvate a compound. Therefore, the solubility of solutes
can be directly related to the density of the SCF [1,112] although
McHugh and Krukonis [3] cautioned that this heuristic is only true
to a rst approximation.
The solubility of a solute has been shown to increase directly
with the density of a SCF at constant temperature. In a study con-
ducted by Haruki et al. [113], the logarithms of solubility (log S) of
tris(2,2,6,6-tetramethyl-3,5-heptanedionato)cobalt(III) [Co(thd)
3
]
and tris(2,2,6,6-tetramethyl-3,5-heptanedionato)chromium (III)
[Cr(thd)
3
] were found to increase linearly with the logarithms of
reduced SCCO
2
density [logr
r
] at different isotherms, as shown in
Fig. 4. The increase in solute solubility with density, however,
cannot be oversimplied and generalized to the whole supercritical
region. A comparison between the solubilities and reduced densi-
ties of Cr(thd)
3
at various temperatures is shown in Table 1. It
demonstrates that while solubility increases with density at
a constant temperature, the solubility of a solute at a higher
temperature but lower solvent density, can be higher than the
solubility of a solute at a lower temperature but of higher solvent
density. Thus, other competing factors affected by the rise in
temperature may also inuence the solubility of a solute in a SCF.
The inuence of temperature on solubility is discussed further in
Section 2.4.
2.3. Clustering and the solubility enhancement factor
The solubility behavior of a solute in a SCF is also enhanced by
the clustering of solvent molecules around the solutes. Local cluster
structures have been observed in the lower density region of neat
SCCO
2
between 0.2 g/cm
3
and 0.6 g/cm
3
while at higher density
region of 0.6e0.9 g/cm
3
, cluster structures with increasing amount
of CO
2
were observed [95]. Since the solubility of a heavy solute in
a dense gas solution rarely exceeds a few mole percent [114,115],
the number of solvent molecules surrounding a solute molecule is
1.00
2.00
3.00
4.00
5.00
6.00
7.00
8.00
9.00
10.00
11.00
100 150 200 250 300
S
o
l
u
b
i
l
i
t
y
,

S
1
0
3
(
m
o
l
e

f
r
a
c
t
i
o
n
)
Pressure (bar)
Supercritical carbon dioxide Supercritical carbon dioxide + methanol
Fig. 3. Solubilities of benzoic acid in SCCO
2
and SCCO
2
with 3.5 mol% methanol as a co-
solvent at 308 K. Data extracted from Ref. [109].
-4.50
-4.00
-3.50
-3.00
-2.50
-2.00
-1.50
-0.150 -0.100 -0.050 0.000 0.050 0.100 0.150 0.200 0.250 0.300
l
o
g

S
log
r
313 K - Cr(thd)3 323 K -Cr(thd)3 343 K - Cr(thd)3
313 K - Co(thd)3 323 K - Co (thd)3 343 K - Co(thd)3
Fig. 4. Linear relationships between the logarithms solute solubility with the loga-
rithms of reduced SCCO
2
density at various temperatures for Co(thd)
3
and Cr(thd)
3
.
Data extracted from Haruki et al. [113].
Table 1
Solubility of Cr(thd)
3
in SCCO
2
at various temperatures and reduced densities. Data
extracted from Haruki et al. [113].
Reduced density, r Solubility, S 10
3
(mole fraction) Temperature (K)
1.47 3.23 313
1.35 3.44 323
1.20 5.24 343
1.20 5.24 343
1.09 2.18 343
0.975 1.14 343
i
n
c
r
e
a
s
e
s
i
n
c
r
e
a
s
e
s
i
n
c
r
e
a
s
e
s
i
n
c
r
e
a
s
e
s
i
n
c
r
e
a
s
e
s
c
o
n
s
t
a
n
t

in excess. As a SCF solution is more compressible, and has a larger
free volume, attractive forces can induce molecules into energeti-
cally favorable locations to form clusters [65]. Since the solvente
solute net attractive forces in a solution are stronger than that of
a solventesolvent or soluteesolute attractive forces, excess solvent
molecules form clusters around a solute molecule. Cluster forma-
tion has been shown to enhance the solubility of a solute in dilute
binary dense gas mixtures [114,116]. The high enhancement factor
(ratio of actual to ideal gas mixture predicted solubility) of dense
gas systems is typically in the range of 10
2
e10
5
[114]. In a binary
system consisting of a solid solute and a SCF, the enhancement
factor, E is given by
E y
2
P
P
sat
2
(1)
where y
2
is the mole fraction of the solute, P is the pressure of the
system, and P
sat
2
is the vapor pressure of the pure solvent. The
enhancement factor can be equated to the fugacity coefcient of the
pure solid through equation (2)
E
f
s
2
f
2
exp
_
v
s
2
_
P P
sat
2
_
RT
_
(2)
where f
2
s
is the fugacity coefcient of the pure solute, 4
2
is the
fugacity coefcient of the solute in the solution, and n
2
s
is the molar
volume of the solid solute. Since vapor pressure of pure solids are
usually very low, P[P
sat
2
and f
2
s
is generally near unity [117],
equation (2) can be simplied into
E
1
f
2
exp
_
v
s
2
P
RT
_
(3)
An alternative approach to correlating the enhancement factor
is via the density of a SCF. Since linearity is often observed between
the logarithm of solubility with density along isotherms, equation
(1) has been used to correlate the enhancement factor into
empirical equations that conform with equation (4) [118]
E expA B$r (4)
where A and B are temperature dependent, empirical constants and
r is the density of the SCF. Further discussion on the solubility
enhancement factor can be found in Refs. [112,117e120].
2.4. The effects of pressure and temperature on solubility
The isothermal solubility of solids in SCFs is not a direct function
of pressure where the solubility initially decreases with increasing
pressure, reaches a minimum, and followed by a steep increase in
the critical pressure region [121]. However, as the pressure
increases further from the critical point, the increase in the
solvating power of the SCF diminishes. Fig. 5 shows the effects of
pressure and temperature on solubility.
Solubility is primarily affected by vapor pressures of the solutes
while other soluteesolvent interactions play secondary roles in SCF
mixtures [65]. Since vapor pressure is determined from the temper-
ature of a system, the effect of temperature on solubility is more
complicated, as temperature affects both the density of the super-
critical solvent and the vapor pressure of the solute [73]. In the
retrograde region, i.e. the region between the lower crossover pres-
sure (P
L
) and the upper crossover pressure (P
U
), the solubility of
a solute decreases withincreasedtemperature. The decreaseinsolute
solubility inthe retrograde region is attributed to the dominant effect
of a rapid decrease in density. At P
L
and P
U
, the solubility of various
isotherms intersect and the competing effects of solvent density and
solute vapor pressure balance each other out [121]. Above and below
the retrograde region, solubility increases with temperature as the
vapor pressure of a solute dominates. Hence, in the regions above P
U
and below P
L
, the solubility of a solute in a SCF increases with
temperature. In the work of Haruki et al. [113], measured solubilities
of Co(thd)
3
and Cr(thd)
3
in a relatively lower pressure region were
found to decrease with increased temperature while at a relatively
higher pressure region, the solubilities of Co(thd)
3
and Cr(thd)
3
were
found to increase with temperature. Such observations commensu-
rate with the behavior of a solute in the retrograde region, and the
region above the upper crossover pressure, P
U
.
2.5. The effects of organometallic complexes on solubility
The metal and ligand side-chains as well as the crystal structure
of a metal chelate are factors that contribute to the solubility of
metal chelates in SCCO
2
[70,122e125]. The contributing effects of
the organometallic complexes to their solubilities in SCFs are
summarized in Fig. 6.
2.5.1. The effects of ligand side-chains on the solubility of
organometallic complexes in SCCO
2
Ligands and ligand design are important in optimizing the
electronic characteristics and the solubility of metal chelates in
Pressure
S
o
l
u
b
i
l
i
t
y
R
e
t
r
o
g
r
a
d
e

r
e
g
i
o
n
T
3
T
1
T
2
T
4
>T
3
>T
2
>T
1
P
L
P
U
T
4
Fig. 5. Plot of solubility versus pressure at different temperatures.
Organometallic
complex
Metal
Distance between ligand and centre atom
Oxidation state : M
+
< M
2+
< M
3+
Ligand
Phenyl-substituted < aliphatic-
substituted < fluorinated
Heteroleptic < homoleptic
Sterical hindrances
Fig. 6. Factors within an organometallic complex that affect solubility in SCFs.
SCCO
2
[58]. A number of solubility studies has been conducted on
2
in which the inuence of
ligands on solubility has been systematically studied. A list of
ligands and their acronyms is given in Table 2 while the solubility
studies conducted on metal complexes in supercritical carbon
dioxide by various authors are shown in Table 3. While a number of
studies is available for various classes of ligands, b-diketonates are
the most extensively studied ligands in SCCO
2
. A number of ligands
that were systematically studied and their inuence on the order of
solubility in metal complexes are shown in Table 4.
Generally, metal complexes containing uorinated ligands are
relatively more soluble, and these are followed by aliphatic- and
phenyl-substituted systems. Rows (a) and (c) in Table 4, illustrate
the higher solubility of uorinated species such as hfa and fddc, in
comparison to their non-uorinated species. The higher solubility
observed for uorinated organometallic complexes are also
observed in other studies [70,122,123,125,134]. The observation
that uorination of a solute increases the CO
2
-philicity of the solute
is not new, and the mechanism by which solvation occurs for
uorinated compounds has been a source of various theoretical and
spectroscopic studies. It has been suggested that the higher vola-
tility of the uorinated chelates causes the observed higher solu-
bility in SCCO
2
[131]. Another possible reason is the reduction in the
polarity of the complexes with the addition of uorine [123]. UVe
VIS and FTIR spectra conducted on fddc and edc metal complexes in
SCCO
2
conrmed the polarity reduction in the fddc complex, in
which the shift of charge transfer bands to lower energies in uo-
rinated metal chelates reected the high electron withdrawing
nature of the uorinated methyl groups [122].
Several other spectroscopic and theoretical studies have also
been conducted to elucidate the mechanism surrounding the
solvation of uorinated solutes in SCCO
2
, although conicting
results were reported. Evidence of van der Waals interactions
betweena uorinatedsolute (1,1-dihydroperuorooctylpropionate)
andCO
2
was rst observedina
1
Hand
19
F NMRchemical shifts study
by Dardin et al. [146]. The higher solubility observed in uorinated
solute was attributed to the magnetic shielding originating fromvan
der Waals interactions [146]. The ndings by Dardin and Samulski
were in agreement with a number of other authors [95,140,147e
149]. A specic intermolecular interaction between uorine and
CO
2
was also observed in an NMR study on uorinated and non-
uorinated hydrocarbons in CO
2
. Excess chemical shift effects
were observed in
19
F NMR for uorinated compounds in CO
2
, in
contrast with the bulk susceptibility-dominated
1
H NMR observed
for hydrocarbons [146]. Similarly, IR spectroscopy of polymers with
CO
2
indicated interactionbetween the dipole of CeF bonds withCO
2
[150] which point to a possible causality to the higher solubility of
uorinated organometallic compounds.
Enhanced interaction between hexauoroethane and carbon
dioxide interactionwas also calculated ab initio, inwhich it was found
that the positively charged carbon atomhas a strong attraction to the
negatively charged uorine atom [151]. However, the ab initio calcu-
lation brought about comments in which the use of a restricted
HartreeeFock level of calculationwas questioned [152]. Recalculation
by Diep et al. [153] found that the hydrocarboneSCCO
2
interactions
are stronger than the uorocarboneSCCO
2
interactions. Yee et al. [90]
used various FTIR techniques to probe the molecular interactions of
heptauoro-1-butanol where they found no evidence of a specic
interaction of carbon dioxide with the peruorinated portion of the
solute. Further investigations byYonker andPalmer [154,155] using
1
H
and
19
F high pressure NMR chemical shifts and NMR relaxation
techniques corroborate the lackof specic CO
2
/uorine interactions in
solution.
While the exact solvating mechanism of a uorinated complex
in SCCO
2
is still under debate and constant study, the presence of
uorine generally increases the solubility of organometallic
complexes. The exception to the rule was observed by Laintz et al.
[123] inwhich the solubility of Bi(fddc)
3
was found to be lower than
that of Bi(edc)
3
at 323 K and 100 atm. The cause for the lower
solubility observed in the uorinated Bi(fddc)
3
complex was
attributed to a possible conformational difference between the two
complexes [123]. At a higher pressure of 230 atm, the order of
solubility was observed to revert to edc < fddc [123].
The solubility of organometallic complexes also increases with
increasing alkyl chain lengths substitution of the ligands, as illus-
trated in part (b) of Table 4. The increasing solubility trend of
copper complexes with progressive alkyl substitution of the edc
ligand shown in Table 4(b) was also observed in the increasing
solubility of Cu(acac)
2
, Cu(dmhd)
2
and Cu(thd)
2
[124]. The methyl
group in the acac ligand was progressively substituted by tert-butyl
groups, with the structures of Cu(acac)
2
and Cu(thd)
2
shown in
Fig. 7. The higher solubility of the thd ligand in comparison to the
acac ligand, was also observed in the work of other authors
[113,130,134]. All three Cu(acac)
2
, Cu(dmhd)
2
and Cu(thd)
2
crys-
tallize into square planar structure [156]. While the similar crystal
structures of the three complexes do not provide additional infor-
mation as to the causality of the order of solubility, it has been
suggested that the additional alkyl group in the thd ligand provides
a better shielding of the center atom that subsequently increases
the solubility of the metalethd complexes [130,136]. It has been
further suggested that the addition of the alkyl reduces the cohe-
sional energy density, and hence, increases the solubility of the thd
complexes [130,134].
In a recent study, the solubilities and charge densities of
Co(acac)
3
, Cr(acac)
3
, Co(thd)
3
and Cr(thd)
3
were estimated by
quantum chemical calculation and COSMO-RS to determine the
effect of molecular structure of organometallic complexes on the
afnity of CO
2
. In the work of Haruki et al. [113], the solubilities of
Co(thd)
3
and Cr(thd)
3
were found to be between 50 and 70 times
more soluble than that of Co(acac)
3
and Cr(acac)
3
. The lower
solubilities of Co(acac)
3
and Cr(acac)
3
were attributed to the
hydrocarbon part in the acac ligand that were too small to cover up
the high charge density of the metal and oxygen atoms. In contrast,
Table 2
Acronyms of ligands.
Acronym Ligands
acac Acetylacetonate
acac-Br 3-Bromopentane-2,4-dionato
bzac 1-Phenylpentane-1,3-dionato
bdc Dibutyldithiocarbamate
CO Carbonyl
cod 1,5-Cyclooctadiene
cp Cyclopentadienyl
dc Dithiocarbamate
dctp Dichlorobis(triphenylphosphine)
dfh 4H,4H-Devauoroheptane-3,5-dionate
dibm 2,6-Dimethylheptane-3,5-dionato
dmhd 1,1-Dimethylhexane-3,5-dionato
DMSO Dimethyl sulfoxide
edc Diethyldithiocarbamate
hdc Dihexyldithiocarbamate
hfa Hexauoroacetylacetonate
fddc (Triuoroethyl)dithiocarbamate
me Methyl
pdc Pyrrolidinedithiocarbamate
p3dc Dipropyldithiocarbamate
p5dc Dipentyldithiocarbamate
thd 2,2,6,6-Tetramethyl-3,5-heptanedionato
tfa 1,1,1-Triuoropentane-2,4-dionato
tfbzm 1,1,1-Triuoro-4-phenylbutane-2,4-dionato
tod 2,2,7-Trimethyl-3,5-octanedionato
Table 3
Solubility studies conducted on a number of organometallic complexes in supercritical carbon dioxide.
Substance Temperature range (
C) Pressure (bar) or density (kg/m

3
)
range [density denoted r]
Solubility range
(in mole fraction
unless stated
otherwise)
Ref
Li(acac) 60 98e294 0.01 mg/L
a
[126]
Ag(acac) 40 103e300 (0.89e3.46) 10
7
[127]
UO
2
(acac) 40 100e250 (4.18e26.7) 10
4
M [100]
Co(acac)
2
40 160 0.53 10
5
kg/m
3
[128]
40 161e300 (3.91e8.59) 10
5
[129]
Cu(acac)
2
60 100e300 (0e3) 10
5
mol/mol [130]
150e170 120e220 (6.20e155) 10
4
[131]
40 103.4e344.7 0.750e2.307 [124]
35e55 r: 652.0e902.3 (0.508e9.126) 10
5
[68]
60 98e294 0.21 mg/L
a
[126]
40 160 7.3 10
5
kg/m
3
[128]
40e70 143e300 (0.997e4.74)) 10
5
[129]
Fe(acac)
2
40e60 100e201 (0.108e5.97) 10
4
[132]
Mn(acac)
2
$2H
2
O 60 98e294 0.40 mg/L
a
[126]
Ni(acac)
2
60 100e300 (0e6) 10
5
mol/mol [130]
40 160 3.4 10
5
kg/m
3
[128]
Pd(acac)
2
60 100e300 (0e6) 10
5
mol/mol [130]
40 100e300 (0.93e5.75) 10
5
[127]
Pt(acac)
2
40 105e290 (0.93e5.75) 10
5
[127]
Zn(acac)
2
60 98e294 1.01 mg/L
a
[126]
60 101e232 (9.5e90) 10
4
mol/L [122]
40 160 7.2 10
5
kg/m
3
[128]
Co(acac)
2
$2H
2
O 60 98e294 0.25 mg/L
a
[126]
Co(acac)
3
60 98e294 0.62 mg/L
a
[126]
40e60 97e40 (0.830e10.669) 10
5
[133]
Cr(acac)
3
40 103.4e344.7 (1.716e19.09) 10
5
[124]
60 203e405 (2.0e3.5) 10
3
mol/L [125]
Fe(acac)
3
40e60 98.2e353.7 (0.06e0.30) 10
3
[134]
40e60 90.1e275.8 (8.75e576) 10
6
[135]
40e60 101e176 (0.0509e2.89) 10
4
[132]
Ga(acac)
3
60 98e294 3.01 mg/L
a
[126]
In(acac)
3
60 98e294 2.63 mg/L
a
[126]
Mn(acac)
3
60 98e294 1.26 mg/L
a
[126]
Rh(acac)
3
40 100e298 (3.32e10.30) 10
5
[127]
Ru(acac)
3
40 100e300 (1.70e9.50) 10
5
[127]
Y(acac)
3
150e170 120e220 (0.47e3.40) 10
5
[131]
Cu(bdc)
2
60 101e232 (1.3e72) 10
5
mol/L [122]
Hg(bdc)
2
60 101e232 (5.6e56) 10
5
mol/L [122]
Zn(bdc)
2
60 101e232 (8.2e69) 10
5
mol/L [122]
55 240.5 12.42 10
6
g/ml [136]
Co(cp)
2
60 100e175 (26e222) 10
5
mol/mol [130]
Cr(cp)
2
60 100e175 (19e206) 10
5
mol/mol [130]
Fe(cp)
2
60 100e175 (24e250) 10
5
mol/mol [130]
40e70 97.5e366.3 (2.22e240) 10
4
[137]
35e50 80.2e403.4 (0.098e3.986) 10
3
[133]
40e60 100e200 (0.233e2.41) 10
3
[132]
Mn(cp)
2
60 100e300 (8e9) 10
5
mol/mol [130]
Ni(cp)
2
60 100e175 (18e218) 10
5
mol/mol [130]
Os(cp)
2
60 100e250 (1e13) 10
5
mol/mol [130]
Ru(cp)
2
60 100e170 (4e29) 10
5
mol/mol [130]
Ti(cp)
2
Cl
2
64 179e300 (0.86e3.39) 10
5
mol/mol [138]
Na(edc) 50 101 1.5 10
4
mol/L [123]
Ni(edc)
2
50 101 8.5 10
7
mol/L [123]
Cu(edc)
2
50 101 1.1 10
6
mol/L [123]
60 101e232 (1.4e11) 10
6
mol/L [122]
35e55 r: 759.93e898.45 (1.95e13.9) 10
7
[68]
Hg(edc)
2
50 152 8.2 10
6
mol/L [123]
60 101e132 (6.8e53) 10
6
mol/L [122]
35e55 100e300 4.086e7.181 mg/L [139]
Bi(edc)
3
50 101 6.0 10
6
mol/L [123]
Co(edc)
3
50 101 2.4 10
6
mol/L [123]
Zn(edc) 55 240.5 0.59 10
6
g/ml [136]
Na(fddc) 50 101 4.7 10
4
mol/L [123]
Ni(fddc)
2
50 101 7.2 10
4
mol/L [123]
Cu(fddc)
2
50 101 9.1 10
4
mol/L [123]
60 101e232 (9.1e10) 10
4
mol/L [122]
Hg(fddc)
2
50 152 5.0 10
3
mol/L [123]
60 101e232 (3.0e14) 10
3
mol/L [122]
Bi(fddc)
3
50 101 7 0.3 10
4
mol/L [123]
Co(fddc)
3
50 101 8.0 10
4
mol/L [123]
Cu(hdc)
2
60 101e232 (2.1e28) 10
4
mol/L [122]
Table 3 (continued)
Substance Temperature range (
C) Pressure (bar) or density (kg/m

3
)
range [density denoted r]
Solubility range
(in mole fraction
unless stated
otherwise)
Ref
Hg(hdc)
2
60 101e232 (1.6e38) 10
4
mol/L [122]
Zn(hdc)
2
60 101e232 (3.2e58) 10
4
mol/L [122]
UO
2
(hfa) 40 100e250 (1.21e3.73) 10
2
M [100]
Ni(hfa)
2
60 203e405 (8.0e9.9) 10
3
mol/L [125]
Ni(hfa)
2
$2H
2
O 40e60 94e251 (2.95e20.23) 10
5
[108]
Ba(hfa)
2
150e170 120e220 (1.30e24.0) 10
5
[131]
Cu(hfa)
2
60 203e405 (8.0e9.9) 10
3
mol/L [125]
40 103.4e344.7 (6.173e74.15) 10
5
[124]
40 100 0.029 mol/dm
3
[140]
Cu(hfa)
2
$H
2
O 40 103.4e344.7 (152.0e414.0) 10
5
[124]
UO(hfa)
2
$H
2
O 40 100 0.040 mol/dm
3
[140]
VO(hfa)
2
$H
2
O 40 100 0.025 mol/dm
3
[140]
Cr(hfa)
3
60 203e405 (8.0e9.9) 10
3
mol/L [125]
40 100 0.03 mol/dm
3
[140]
Y(hfa)
3
150e170 120e220 (1.30e24.0) 10
5
[131]
Zr(hfa)
4
40 100 0.044 mol/dm
3
[140]
Cu(pdc)
2
60 101e232 (4.1e40) 10
7
mol/L [122]
Hg(pdc)
2
60 101e232 (3.5e34) 10
7
mol/L [122]
Zn(pdc)
2
60 101e232 (3.2e90) 10
7
mol/L [122]
Cu(p3dc)
2
60 101e232 (6.3e120) 10
6
mol/L [122]
Hg(p3dc)
2
60 101e232 (1.2e23) 10
5
mol/L [122]
Zn(p3dc)
2
60 101e232 (7.9e150) 10
6
mol/L [122]
Cu(p5dc)
2
60 101e232 (0.90e18) 10
4
mol/L [122]
Hg(p5dc)
2
60 101e232 (1.0e20) 10
4
mol/L [122]
Zn(p5dc)
2
60 101e232 (1.6e32) 10
4
mol/L [122]
Ag(thd) 60 100e300 0 [130]
K(thd) 60 100e200 0 [130]
Rb(thd) 60 100e200 0 [130]
Co(thd)
2
40e70 100e159 (2.10e12.8) 10
4
[129]
Cu(thd)
2
60 100e175 (1e82) 10
5
[130]
40 103.4e344.7 (6.173e74.15) 10
5
[124]
40e70 119e280 (2.71e33.9)) 10
4
[129]
Ni(thd)
2
60 100e250 (0e28) 10
5
[130]
Zn(thd)
2
60 100e150 (7e>500) 10
5
[130]
Co(thd)
3
60 100e170 (2e213) 10
5
[130]
40e70 100e190 (0.368e2.83) 10
3
[113]
Cr(thd)
3
60 100e150 (4e>500) 10
5
[130]
40 103.4e344.7 (400e604.9) 10
5
[124]
40e70 101e163 (0.233e5.24) 10
3
[113]
Fe(thd)
3
60 100e150 (3e>500) 10
5
[130]
40e60 94.8e306.7 (1.64e10.13) 10
3
[134]
Mn(thd)
3
60 100e150 (3e>500) 10
5
[130]
Ru(thd)
3
60 100e150 (1e174) 10
5
[130]
Tb(thd)
3
40e60 124.6e352.3 (0.07e2.34) 10
3
[134]
Ti(thd)
3
60 100 >500 [130]
Ce(thd)
4
40e60 101.2e350.9 (0.05e0.62) 10
3
[134]
Zn(thd)
4
60 100e175 (1e109) 10
5
[130]
Cu(tod)
2
40 103.4e344.7 (26.03e269.7) 10
5
[124]
Fe(tod)
3
40e60 90.6e177.4 (1.39e12.67) 10
3
[134]
Tb(tod)
3
40e60 124.3e318.4 (0.53e3.45) 10
3
[134]
Ce(tod)
4
40e60 98.0e243.0 (1.53e7.84) 10
3
[134]
Cu(acac-Br)
3
40 103.4e344.7 (1.70e9.50) 10
5
[124]
Rh(acac)(cod) 60 100e200 (0e23) 10
5
[130]
Cu(bzac)
2
40 103.4e344.7 (0.179e1.047) 10
5
[124]
Pt(cod)(me)
2
60 100e200 (3e132) 10
5
[130]
40e80 125.9e296.4 (6.453e34.36) 10
4
[141]
Zn(dc)
2
55 240.5 0.089 10
6
g/ml [136]
Cu(dibm)
2
40 103.4e344.7 (9.17e88.41) 10
5
[124]
Cu(dmhd)
2
40 137.9e344.7 (3.696e36.21) 10
5
[124]
Cu(tfa)
2
40 103.4e344.7 (29.60e59.38) 10
5
[124]
UO(tfa) 40 100e250 (2.20e13.7) 10
3
M [100]
Cu(tfbzm)
2
40 137.9e344.7 (0.702e4.269) 10
5
[124]
trans-Cr(tfa)
3
40 103.4e344.7 (147.9e272.1) 10
5
[124]
Ru(thd)
2
(cod) 60 100e150 (1e56) 10
5
[130]
cis-Cr(tfa)
3
40 103.4e344.7 (67.30e190.8) 10
5
[124]
Mo(CO)
6
40e60 76.5e113.9 (9.5e145.1) 10
4
[142]
Ni(dctp)
2
Cl
2
35e55 108e279 (1.32e5.33) 10
6
[143]
Ti(Oi-Pr)
2
(dpm)
2
40e60 60e200 (0.025e1.1) 10
2
[144]
UO
2
(dfh)
2
DMSO 40 100 0.12 mol/dm
3
[140]
trans-Co
2
(CO)
6
[3,5-bis(CF
3
)C
6
H
3
P(i-C
3
H
7
)
2
] 40e70 100e260 (0.8e16.7) 10
3
M [145]
a
Numerical solubility values were provided only at 294 bar.
thd ligand has larger surface area and was found to have lower
charge densities; hence, higher solubilities.
Low solubility trends were observed in studies involving
aromatic substituted ligands such as that observed for Cu(bzac)
2
,
Cu(pdc)
2
and Ni(dctp)
2
Cl
2
[122,124,143]. In the work of Wai et al.
[122] where the solubilities of various metal in a number of
dithiocarbamate ligands were compared, metal chelates with the
ring structure of pdc exhibit the lowest solubility. Typically, such
structures also exhibit very high melting point [122].
Comparisonbetweenhfaandits hydratedligand[rows (a) and(d)
in Table 4] shows reduced solubility effect on the hydrated metal
complexes. The results obtained are in agreement with other
experimental observations [108,126]. Tenorio et al. [108] suggested
that the lower solubility values observed for Ni(hfa)
2
$2H
2
O could
possibly be due to the formation of intermolecular hydrogen bonds
between the hydrated complex molecules. In terms of the higher
solubility of Cu(hfa)
2
than its monohydrated ligand, Lagalante et al.
[124] suggestedthat the ve-coordinate, squarepyramidal structure
of the monohydrated Cu(hfa)
2
complex (as opposed to the four-
coordinate square planar of Cu(hfa)
2
) as the cause of the difference
in solubility. Investigation by Kanakubo et al. [157] also found
apparent sensitivity of the solvent densities to solute molecular
structure that affects the solubility of the solute in SCCO
2
.
Changing homoleptic ligands with another class of ligand into
heteroleptic ligands also inuences the solubility of a metal
complex. The solubility of heteroleptic Rh(acac)(cod) complex is
observed to be one order of magnitude higher than a number of
acac metal complexes, as shown in Fig. 8. The increase shielding of
the metal center through the substitution of the cod ligand was
suggested as the reason for the increase solubility of Rh(acac)(cod)
[130]. On the other hand, the solubility of the homoleptic Ru(thd)
3
was found to be higher than the heteroleptic Ru(thd)
2
(cod). No
reasons were provided by the authors as to the causality of the
lower solubility observed for Ru(thd)
2
(cod).
The solubility of the metal complex is generally lower than pure
ligands although such inuence is usually neglected in thermody-
namic models [15,70,122,124]. The inuence of ligands on metal
complexes solubility has been predicted via calculated solubility
parameter of the free ligand. Generally, an increase in the solubility
parameter of a free ligand corresponds to a decrease in the complex
solubility [122,124]. However, the calculated solubility parameter
couldnot offer anaccuratepredictiononthe order of solubility for all
investigated free ligands. In a study conducted by Lagalante et al.
[124], the solubility parameters of a number of free ligands were
calculated in the order of: acac < dmhd < dibm < tod < thd. Exper-
imentally, copper complex of tod exhibits a higher solubility than
thd, as shown in row(a) of Table 4. One possible explanation for the
discrepancy is the existence of a small permanent dipole moment in
the Cu(tod)
2
complex due to its cis square planar conguration that
is not accounted for in the calculation of the solubility parameter of
the free ligands [124]. While both thd and tod are isomers, thd is
sterically rigid whereas tod is more exible and provides a better
shielding of the metal atom compared to thd [134]. Thus, higher
solubility is experimentally observed in Cu(tod)
2
.
2.5.2. The effects of the central metal atom on the solubility of
2
The solubilities of organometallic complexes with identical
valence electron conguration generally decrease with increasing
atomic numbers [130], as illustrated by the solubilities of Fe(cp)
2
,
Ru(cp)
2
and Os(cp)
2
(Table 5). The decreasing solubilities of the
three metal cyclopentadienyl complexes from Group 8 of the
Periodic Table with increasing molecular weights are shown in
Table 5. Aschenbrenner et al. [130] attributed the decrease in
solubility to increased intermolecular cohesion and increased
Table 4
A number of organometallic complexes and the inuence of ligands on their solu-
bility in supercritical carbon dioxide.
Solubility of organometallic
complexes in increasing order
Reference
(a) Cu(bzac)
2
< Cu(acac)
2
< Cu(tfbzm)
2
< Cu(dmhd)
2
< Cu(tfa)
2
< Cu(thd)
2
< Cu(dibm)
2
< Cu(tod)
2
< Cu(hfa)
2
$H
2
O < Cu(hfa)
2
[124]
(b) Cu(pdc)
2
< Cu(edc)
2
< Cu(p3dc)
2
< Cu(bdc)
2
< Cu(p5dc)
2
< Cu(hdc)
2
[122]
(c) Cu(edc)
2
< Cu(fddc)
2
[123]
(d) Ni(hfa)
2
$2H
2
O < Ni(hfa)
2
[108]
(e) Ru(thd)
3
< Ru(thd)
2
(cod) [130]
(f) Rh(acac)
2
< Rh(acac)(cod) [130]
(g) Co(acac)
3
< Co(thd)
3
; Cr(acac)
3
< Cr(thd)
3
[113]
(h) Fe(acac)
3
< Fe(acac)
2
< Fe(cp)
2
[132]
Fig. 7. Molecular structures of cobalt (III) acetylacetonate [Co(acac)
3
], and tris(2,2,6,6-
tetramethyl-3,5-heptanedionato)chromium (III) [Cr(thd)
3
].
0
20
40
60
80
100
120
140
160
180
200
250 350 450 550 650 750 850
S
o
l
u
b
i
l
i
t
y
,

S

1
0
5
(
m
o
l
e
/
m
o
l
e

C
O
2
)
Density (kg/m
3
)
Rh(acac)(cod)
Pd(acac)2
Cu(acac)2
Ni(acac)2
Ru(thd)3
Ru(thd)2(cod)
Fig. 8. The solubilities of a number of homoleptic and heteroleptic organometallic

complexes at 333 K and various SCCO
2
densities. Data extracted from Ref. [130].
Table 5
Solubilities of various metal complexes in supercritical carbon dioxide at 333 K and
150 bar (in mole/mole CO
2
), and their corresponding molecular weights. Solubility
data extracted from Ref. [130].
Compound Molecular weight Solubility, S 10
5
Cr(cp)
2
182.18 77
Mn(cp)
2
185.12 9
Fe(cp)
2
186.03 176
Co(cps)
2
189.12 149
Ni(cp)
2
188.88 142
Ru(cp)
2
231.26 27
Os(cp)
2
320.42 9
distance between ligands and the center metal atom that result in
reduced shielding of the metal by the ligands.
Examinationof ve metal cpcomplexes (Cr
24
, Mn
25
, Fe
26
, Co
27
, and
Ni
28
) across Period4 of the Periodic Table indicated that their order of
solubilityvaries differently fromtheir molecular weights, as shownin
Table 5. The actual solubilities of the ve complexes were found to be
in the order of: Mn(cp)
2
< Cr(cp)
2
<Ni(cp)
2
<Co(cp)
2
< Fe(cp)
2
. The
low solubility of Mn(cp)
2
was attributed to its polymeric chain
structure where a Mn atomis linked with two other neighboring Mn
atoms by one bridging cyclopentadienyl ligand, resulting in a higher
polarity metaleligand bonds [130,158]. The other four metal cp
complexes are monomeric cyclopentadienyls. Aschenbrenner et al.
[130] suggested a causal relationship between the solubility of metal
complexes with their magnetic moment and the distance between
the ligand and the center atom, although further investigation is
requiredtosubstantiate thecausality. They further statedthat most of
the cp complexes have an electron deciency or electron excess that
contributes to the electron imbalance in the complex molecule. The
increasing electron imbalance causes decreasing strength between
metal andligand; thereby, increasingthe distancebetweenmetal and
ligand which reduces the shielding of the metal center [130].
A solubility study conducted by MHamdi et al. [131] on Cu(hfa)
2
,
Y(hfa)
3
and Ba(hfa)
2
shown in Table 6, also concur with the ndings
of Aschenbrenner et al. Of the three complexes, Ba(hfa)
2
has the
lowest solubility in SCCO
2
even though it has a similar planar
structure to Cu(hfa)
2
. It has been suggested that the high electro-
positivity of barium increases the ionic characteristic of the metale
ligand bond, subsequently rendering the interactions between the
non-polar SCCO
2
with Ba(hfa)
2
unfavorable [131]. Y(hfa)
3
on the
other hand, has a lower solubility than Cu(hfa)
2
due to its hex-
acoordinated structure with a closer ligand cage [131,159,160].
Metal-based complexes with higher oxidation states generally
show higher solubilities in SCCO
2
[126,130]. The solubility measure-
ment of a number of thd complexes shown in Fig. 9 was found to be
generally in the order of M(thd) < M(thd)
2
< M(thd)
3
[M metals]
[130]. Saito et al. [126] compared the solubilities of Mn(acac)
2
$2H
2
O,
Mn(acac)
3
, Co(acac)
2
$2H
2
O, and Co(acac)
3
with the conclusion that
higher oxidation states produce higher solubilities in SCCO
2
. Both the
trivalent Co and Mn complexes show higher solubilities than their
bivalent counterparts. The higher oxidation state in a metal also
corresponds with an increase in the number of ligands that subse-
quently, provides a better shielding of the center metal atom.
However, the increasing solubilities of metal complexes with
increasing oxidation states of the metals, and the number of ligands
surrounding the center atom, could be tapered by the subsequent
increase in molecular mass that result in a decrease in solubility
[130,161]. An example is the solubility of a tetravalent complex,
Zr(thd)
4
which was found to be of the same order of magnitude as its
bivalent complexes [130]. The lower than expected solubility was
reasonedto be causedby the increasedsteric hindrance of the ligands,
due to the large space required for four ligands [130].
3. Thermodynamic modeling of soluteeSCF solubility behavior
Classical thermodynamic models can generally be categorized
into three types, with the models being based on (a) the excess
Gibbs free energy or activity coefcient, (b) equations of state, and
(c) empirical methods. Generally, the solubility of metal chelates in
SCCO
2
is correlated either through equations of state (EOS) or
empirical models. While a number of thermodynamic models is
available, only a small number was utilized for organometallic
complexes-SCCO
2
systems. In the following sections, the thermo-
dynamic models used in a number of studies related to organo-
metallic complexes in SCCO
2
are reviewed.
3.1. Solubility parameter, d and the regular solutions theory
Hildebrand and Scott [162] rst introduced the solubility
parameter, d, to categorize soluteesolvent behavior in regular
solutions. The solubility parameters for the solute and solvent are
calculated individually, and are then compared. Heuristically,
a solute can be predicted to dissolve in a solvent when the differ-
ence between the solubility parameters of the solute and the
solvent is approximately 1. The solubility parameter is formulated
on the grounds that the soluteesolvent molecules mainly exhibit
dispersion forces with weak chemical interactions, and is given as
the square root of the cohesional energy density, given by the
equation
d
E
v
_
(5)
where E is the cohesive energy of the solute or solvent, and v is the
molar volume. E is essentially the energy of vaporization of liquid to
vapor at innite separation; representing the total energy holding
the molecules of the liquid together. Dissolution can occur when
the Gibbs free energy of mixing (DG
m
) is negative. The Gibbs free
energy of mixing is given by
DG
m
DH
m
TDS
m
(6)
where DH
m
is the energy change associated with intermolecular
interactions, and DS
m
is the energy change associated with a change
in the molecular arrangements. Mixing occurs if DH
m
is negative, or
less than TDS
m
. This reasoning forms the basis for the development
of the Hildebrand solubility parameter. While all heats of mixing in
the Hildebrand solubility parameter calculations were assumed to
Table 6
Solubility (in mole fraction) of various hfa complexes in supercritical carbon dioxide
at 170

C and 170 bar.
Compound Solubility Crystal structure
Cu(hfa)
2
>0.1 Planar
Y(hfa)
3
4.20 10
4
Hexacoordinated
Ba(hfa)
2
8.60 10
6
Planar
0
50
100
150
200
250
300
350
400
200 300 400 500 600 700
S
o
l
u
b
i
l
i
t
y
,

S
1
0
5
(
m
o
l
e
/
m
o
l
e
)
Density (kg/m
3
)
Ag(thd)
K(thd)
Rb(thd)
Cu(thd)2
Ni(thd)2
Co(thd)3
Cr(thd)3
Fe(thd)3
Mn(thd)3
Fig. 9. Solubility of various metalethd complexes with different oxidation states. Data
extracted from Ref. [130].
be positive, in reality, DH
m
can be positive or negative [163,164].
Hence, given that DS
m
multiplied with temperature promotes
a more negative DG
m
, and that dissolution occurs when DG
m
is
negative, a low DH
m
is benecial to the dissolution process. Since
DH
m
f (d
1
d
2
)
2
, a low DH
m
can be attained by the difference
between the solubility parameters of the solute and solvent.
Therefore, the solubility of a solute in a solvent is maximized when
the solubility parameters are similar. The Hildebrand solubility
parameter is built upon the regular solutions theory [162] which
assume (1) no chemical effects between molecules, (2) that the
entropy of solution at constant volume is equal to an ideal solution,
and (3) that the interaction energy between two molecules of
different species is the geometric mean of their interaction energies
[165]. The regular solutions theory however, cannot be generalized
to supercritical uids since SCF solutions are highly compressible
and non-ideal with activity coefcients usually above 100 [65].
Supercritical solutions are also highly asymmetric due to the large
disparities in the sizes and energies of the solutes and SCF. As such,
the use of the geometric mean is an approximation at best [91].
Hence, the solubility parameter and the activity coefcient dened
in the Hildebrand solubility parameter are limited to temperatures
below the critical point of a component [165].
Giddings et al. [166] extended the Hildebrand solubility
parameters to supercritical uids on the condition that the solu-
bility parameter cannot be used for esters, ketones, alcohols and
other polar liquids. They assumed that (i) the solubility parameter
is relevant to the physical effect as well as the chemical
effect.and (ii) the gas obeys the van der Waals Equation of State
[3,166]. The solubility parameter formulated by Giddings et al.
[166] is given as
d 1:25
r
r
r
r;1
P
c
_
(7)
where d is the solubility parameter, P
c
is the critical pressure, r
r
is
the reduced density of the uid, and r
r,1
is the reduced density of
the uid at its normal boiling point. The term 1:25P
1=2
c
accounts for
the chemical effects and the term (r
r
/r
r,1
) accounts for the state
effects. The solubility parameter by Giddings was found to be
a good starting point for a qualitative forecast although its quan-
titative prediction was poor [64]. Over the years, a number of
extended and modied solubility parameters has also been devel-
oped through various modications by Prausnitz [165], Hansen
[167], Allada [64] and Fedors [168,169]. The utilization of the
solubility parameters on the order of solubility for free ligands has
been discussed in Section 2.5.1.
Solute solubility can be estimated via regular solutions theory
through the ScatchardeHildebrand equation, given by
RTlng
2
V
2
2
1
d
2
d
1
2
(8)
g
2
is the activity coefcient of the solute, y
2
is the mole fraction of
the solute, V is the molar volume, f
1
is the volume fraction of the
solvent and T is the temperature of the system. The activity coef-
cient of the solute is related to its fugacity through
f
S
2
f
L
2
g
2
y
2
(9)
where f
2
L
is the fugacity of pure liquid of the solute and f
2
S
is the
fugacity of the solid solute at system temperature. The fugacity
ratio of Equation (9) [91] can be expressed as
ln
_
f
S
2
f
L
2
_

DH
f
RT
m2
_
T
m2
T
1
_
lng
2
(10)
where DH
f
is the enthalpy of fusion, R is the gas constant and T
m2
is
the melting temperature of pure solute 2. The solubility of the
solute can therefore, be calculated from the expression
y
2
exp
_
DH
f
RT
m2
_
T
m2
T
1
_

V
2
2
1
RT
d
2
d
1
2
_
(11)
Equation (11) was used by Lagalante et al. [124] to predict the
solubility of Cr(acac)
3
in SCCO
2
. While the solubility of Cr(acac)
3
at
pressures above 30 MPa was adequately predicted, the forecasted
solubility at pressures below 30 MPa deviated by one to two orders
of magnitude. The high deviation from experimental results
compelled Lagalante et al. [124] to conclude that the regular solu-
tions theory framework is a poor predictive model for organome-
tallic complexes in SCCO
2
.
3.2. Empirical methods
Empirical methods are used widely in the calculation of
organometallic complexes solubility in SCCO
2
. The popularity of the
empirical methods is due, chiey, to a lack of thermophysical data
for organometallic complexes required in EOS models. While
a number of empirical methods is available in the literature
[119,170e176], the Chrastil correlation [177] is the most widely
used correlation in organometallic-SCCO
2
systems. The Chrastil
correlation is a density-based model in which the solubility of
a solute is related to the density of SCFs based on the association
laws and the entropies of the solutes in SCFs given by
S r
k
exp
_
a
T
b
_
(12)
S is the solubility of the solute, r is the density of the SCF, k is the
association number, a DH/R, and b is a constant. DH represents
the total heat of solvation and heat of vaporizationwhile R is the gas
constant. A linear plot of log S against log r (as in Fig. 4) would yield
k, and b. The correlation by Chrastil is widely used in organome-
tallic-SCCO
2
, in part, due to its ease of use and accuracy
[70,108,127,133,134]. The absolute standard deviation (ASD)
between calculated and experimental data generally range from 2%
to 20%. Density-based models such as the Chrastil correlation
generally yield good results within 10e30 MPa (the conditions
where most processes are conducted) but fail at extreme density
regions [69,178]. However, the Chrastil correlation is limited in
scope in that its dependence on temperature allows only limited
extrapolation to a wider density range. While not rigorous, it
provides a way to compare the solubilities of organometallic
compounds over a range of densities [134].
Another empirical method used in organometallic-SCCO
2
systems is the density-based correlation proposed by Mendez-
Santiago and Teja [170]. The Mendez-Santiago and Teja (MST)
correlation, given by Equation (12), uses the enhancement factor, E,
to remove the effect of sublimation pressure with the constants, C
and D independent of temperature.
TlnE C Dr
1
(13)
Solubility data at various temperatures would fall into a straight
line when TlnE is plotted against solvent density, r
1
. The MST
correlation can also be used as a consistency test on experimental
data [170]. A number of authors correlated their experimental
solubility data with the MST correlation that yielded deviations
(ASD) that range from 2% to 19% [108,141].
3.3. Equations of state (EOSs)
Equations of state are used in engineering practice since these
equations can describe phase behavior of mixtures at wide range of
temperatures and pressure. Cubic EOSs are used widely in the
chemical industry for phase equilibria calculations due to their
simplicity, reliability and the large availability of data bases for pure
compounds. Although highly regarded, a limitation of cubic EOSs is
that these equations do not represent the behavior of pure uids
near their critical points [179]. The earliest notable cubic EOS is the
van der Waals EOS which is expressed as the summation of an
attraction pressure and a repulsion pressure, given as
P
RT
v b
a
v
2
(14)
where P is the pressure of the uid, R is the gas constant, T is the
absolute temperature and v is the specic volume of the system. RT/
v b accounts for the repulsion pressure while a/v
2
accounts for
the attraction pressure. Parameter a is regarded as a measure of the
intermolecular attraction force and treated as a constant. Parameter
b is temperature independent, is related to the size of the hard
spheres (molecules) and corrects for the nite volume occupied by
gas molecules. As opposed to real molecules that are neither hard
nor spheres, the van der Waals equation treated molecules as
elastic, impenetrable, free moving hard spheres that are attracted
to each other with weak, long-range forces [180]. While the van der
Waals EOS is a rst noteworthy attempt that accounts for the
deviation of a real gas from the ideal gas law, the simplicity of the
equation renders it inappropriate for rigorous calculations.
The more robust and common cubic EOS that is also used in
organometallic-SCCO
2
systems is the PengeRobinson EOS (PR-EOS)
[181]. The PR-EOS is a modication of the van der Waals EOS with
improvements made to the attractive pressure term, and the
inclusion of a temperature-dependent parameter a. The PR equa-
tions and parameters are dened in Table 7.
In the PR-EOS, parameters a and b are regularly calculated from
pure component parameters. The calculations of a and b presented
a problem for organometallic complexes as critical properties data,
as well as solutes sublimation pressure data, are rarely available.
Organometallic complexes usually degrade at temperatures around
the normal boiling point, preventing the measurement of ther-
mophysical data beyond those boiling points [135]. In order to
overcome the lack of thermophysical data, Cross et al. [68] used
mixture solubility data to regress for P
c
and T
c
. However, the use of
regressed P
c
, T
c
and k
ij
values left little condence for extrapolation
and interpolation [135]. The Jobacks group contribution method
[182] was used by Roggeman et al. [135] to estimate the critical
parameters of organometallic complexes. The contribution of the
metal center was neglected by the authors, resulting in deviations
between experimental and calculated data in the range of 5e28%.
In a mixture, the parameters a and b of both pure components
are combined into a
m
and b
m
[m mixture] with the use of mixing
rules. Mixing rules are employed as composition dependence laws
for both a
m
and b
m
while combination rules are used to relate
binary parameters, a
ij
and b
ij
. A number of mixing rules and
combination rules is available in the literature [91,183e190]
although in many cases, the classical van der Waals mixing rules
[equations (23)e(24)] are used. The van der Waals mixing rules
however, are limited to molecules of similar sizes and chemical
nature. For an organometallic complex-SCCO
2
system, the disparity
in the sizes, energies and component critical temperatures between
the solute and the solvent are so large that k
ij
, is required to account
for a huge correction to the geometric mean [191]. In addition, the
unlike-pair interaction parameter, k
ij
, is correlated from existing
data and corresponding states theory based on critical properties.
Thus, the variation in k
ij
is also unpredictable [191]. While a number
of mixing rules has been proposed for highly non-ideal mixtures,
these models either fail for simple mixtures or suffer from the
MichelseneKistenmacher syndrome where the mixing rule is not
invariant when dividing a component into a number of identical
subcomponents [183,192]. A detailed discussion on mixing rules
can be found in Refs. [183,187,189,193e195].
Johnston et al. [65] made it clear that a single model cannot be
usedtotreat all solubilitycases, andthat a lackof vapor pressuredata
means that thermodynamic models based onthe ideal gas reference
state are limited. The highly variable chemical potential of the
solutes in the dense gas region also makes predictions and correla-
tions challenging [65]. Many other thermodynamic models such as
the perturbed-hard sphere EOS, the augmented van der Waals
model, the mean eld lattice model, and the KirkwoodeBuff solu-
tion theory have been utilized in the dense gas regions for organic
compounds. While the applicability of these thermodynamic
Table 7
PengeRobinson EOS and its parameters.
PengeRobinson EOS
P
RT
v b
a
vv b bv b
(15)
can be rewritten in the form of
Z
3
1 BZ
2
_
A 3B
2
2B
_
Z
_
AB B
2
B
3
_
0 (16)
where
A
aP
R
2
T
2
(17)
B
bP
RT
(18)
Z
Pv
RT
(19)
aT ac
a 0:45724
R
2
T
2
c
Pc
a (20)
a
_
1 k
_
1
T
Tc
__2
(21)
k 0:37464 1:54226u 0:26992u
2
(22)
b bc 0:07780
RTc
Pc
(23)
Mixing rules:
am
j
x
i
x
j
a
ij
(24)
bm
j
x
i
x
j
b
ij
(25)
Note: T
r
reduced temperature; T
c
critical temperature; P
c
critical pressure;
u acentric factor; R gas constant; v volume; a cohesion energy parameter.
models to organometallic systems in SCCO
2
would be of interest to
many, a lack of thermophysical data will continue to prevent their
utilization.
4. Conclusion
The potential applications of supercritical uid technologies
(SFT) to process organometallic compounds for biomedical, phar-
maceutical and chemical purposes are extensive. The focus of
fundamental solubility studies however, has generally been geared
toward applications in catalysis and waste metal extractions. While
quite an extensive number of solubility studies has been conducted
on organometallic complexes in SCCO
2
, most of the ligands
involved in the studies are the b-diketonates which are not the
typical classes of ligands used in medicinal therapeutics. A lack of
fundamental thermodynamic studies on metal-based therapeutics
in supercritical uids will therefore, continue to impede the
development of SFT in the biomedical eld.
The solubility behavior of metal chelates in SCCO
2
is affected by
their ligand side-chains and the metal involved. Fluorinated ligands
in general, are more CO
2
-philic, showing higher solubility while
aromatic substituted ligands elucidate poor solubility in SCCO
2
.
Increasing alkyl chain lengths in the ligand side-chains also tend to
increase shielding of the metal center; thereby increasing the metal
chelates solubility. Metal chelates with higher oxidation states also
show higher solubility in SCCO
2
; partly due to an increased
shielding provided by the additional ligands. The polarity of the
metal chelates (in which the charge of the metal atom, their crystal
structure and the distance between the metal center and its ligands
contribute to their polarity) also affect their solubilities in SCCO
2
.
Challenges remain to accurately model the solubility behavior of
solutes at dense gas conditions given that the organometallic-
SCCO
2
system is highly complex due to the extremely compressible
SCF, the asymmetric sizes and energies of the solute and solvent,
and a lack of thermophysical data that will further impede the use
of available thermodynamic models.
Acknowledgment
This work was supported in part by the Ministry of Higher
Education, Malaysia.
Nomenclature
a, b parameters in SRK-EOS and PR-EOS
E enhancement factor
G
f
E
excess Gibbs energy at innite pressure
G
E
att
attractive excess Gibbs energy
DG
m
Gibbs free energy of mixing
DH
m
heat of mixing
k association number
k
ij
unlike-pair interaction parameter
P system pressure
P
c
critical pressure
P
sat
2
vapor pressure of pure solid solute
P
L
lower crossover pressure
P
U
upper crossover pressure
R gas constant
S solubility
DS
m
entropy of mixing
T absolute temperature
v specic volume
V
m
volume of mixture
x, y mole fraction
Greek symbols
d solubility parameter
4 volume fraction
l
ij
empirically determined, adjustable interaction parameter
r density
r
r
reduced density
f
2
s
fugacity coefcient of pure solute
4
2
fugacity coefcient of solute in solution
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Wen Hui Teoh B(Hons.) Chem. Eng. Universiti Kebangsaan
Malaysia, MPhil Cambridge.
Wen Hui Teoh is a fellow of the University of Malaya and is
currently a PhD student under Prof. Neil Foster and Dr.
Raffaella Mammucari.
Raffaella Mammucari B.E. University of Naples (Italy),
PhD University of New South Wales (Australia) Raffaella
Mammucari is a Senior Research Associate at the Univer-
sity of New South Wales, Australia. Her research eld is in
supercritical uids and gas expanded media technology.
Her research interests include particle engineering applied
to active pharmaceutical ingredients, polymer bio-blends
and scaffolds, the production of magnetically responsive
particles; the development of polymer vesicles for medical
applications, material processing by sub-critical water, and
biosynthesis in non-conventional media.
Neil R. Foster UNSW Scientia Professor, BSc PhD DSc FRACI
FIEAust FTSE Chart. Chem. CPEng NPER, Honorary
Professor (BUCT), PRC Qian Ren 1000 Talents Programme
Professor Neil Foster is a Scientia Professor at the Univer-
sity of New South Wales, Australia. He is also a Peoples
Republic of China Qian Ren 1000 Talents National
Professor based at Beijing University of Technology. He has
been involved in supercritical uids and dense gas
research for 30 years, more recently in the area of nano-
medicine and re-engineering of pharmaceuticals. He has
260 publications, 130 of which are in peer reviewed scien-
tic media. Neil is also a named inventor on 13 patent
applications, 4 of which have been granted. Neil is also
the founder and Director of Bioparticle Technologies P/L.

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Solubility of organometallic complexes in supercritical carbon dioxide: A review

C) Pressure (bar) or density (kg/m

C) Pressure (bar) or density (kg/m

Fig. 8. The solubilities of a number of homoleptic and heteroleptic organometallic

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