4254 Ind. Eng. Chem. Res.

2009, 48, 4254–4265

Understanding Biphasic Ionic Liquid/CO2 Systems for Homogeneous Catalysis:

Hydroformylation
Azita Ahosseini, Wei Ren, and Aaron M. Scurto*
Department of Chemical & Petroleum Engineering and NSF-ERC Center for EnVironmentally Beneficial
Catalysis, UniVersity of Kansas, Lawrence, Kansas 66045

A biphasic ionic liquid (IL) and compressed carbon dioxide system has a number of advantages for
efficient homogeneous catalysis. The hydroformylation of 1-octene to nonanal catalyzed by a
rhodium-triphenylphosphine complex was used as a model reaction to illustrate the effects of carbon
dioxide in a biphasic ionic liquid/CO2 system using the model ionic liquid, 1-hexyl-3-methyl-imidazolium
bis(trifluoromethylsulfonyl)amide ([HMIm][Tf2N]). Detailed phase equilibrium studies were conducted
to determine volume expansion of the IL phase and the multiphase equilibria and mixture critical points
between the reactant, product, and IL with CO2 and syngas (CO/H2). These data ultimately affect the
concentration of the reactant and, thus, the apparent reaction rate. The viscosity of the IL with CO2
pressure was measured and demonstrates the dramatic decrease with increasing CO2 pressure. The self-
diffusion coefficient of the ionic liquid and 1-octene were measured and indicate a large increase with
CO2 pressure (solubility). With an understanding of the kinetics, phase behavior, and mass transport,
biphasic IL/CO2 reaction systems may be properly understood and designed.

1. Introduction modern “green”/sustainable chemistry and engineering.3,4 A

biphasic ionic liquid and compressed carbon dioxide system
Homogeneous catalysis with organometallic complexes has
may solve these important issues. As will be demonstrated
been utilized for efficient chemical transformations with high
in this contribution, phase equilibrium, mass transport, and
chemo-, regio-, and enantioselectivity.1,2 In most cases, the
kinetic parameters are needed to fully exploit this tunable
practical feasibility of a catalytic system is determined by
system.
the activity, selectivity, and, equally important, by the ability
to separate and recycle the often costly catalyst and ligands.
A variety of scenarios have been developed to address this 2. Background
issue including reaction in a single fluid phase followed by 2.1. Ionic Liquids and Compressed/Supercritical CO2.
separation, multiple fluid phases for reactant delivery and Compressed, dense-phase, or supercritical (SC) carbon dioxide
selective extraction, or solid support of the metal complex. has been shown as an environmentally benign solvent with
In multiphase systems, one phase immobilizes or sequesters tunable physicochemical properties for enhancing reactions and
the catalyst and the other phase acts as a mobile phase to catalysis.5 CO2 can become miscible with liquids and, impor-
deliver reactants and to remove products. The idealized tantly, “permanent” and reaction gases (viz. H2, CO, O2, etc.),
biphasic system would have complete immiscibility between thus eliminating gas-liquid phase boundaries and their inherent
phases (no cross contamination); no catalyst partitioning mass transfer limitations. Many researchers have demonstrated
(leaching); and reactants would partition into the catalytic the improved catalytic performance in CO2 systems; for recent
phase, and products would partition out of the catalytic phase. reviews, see the work of Jessop6 and Leitner.7 However, often
While solid-support or “heterogenizing” the metal complexes high pressure and elaborate ligand systems are required to render
would result in the most facile separations of the catalyst enough catalyst soluble in the supercritical CO2 for high-
from the products, often the solid support decreases the throughput production.
activity and, importantly, selectivity of the catalyst. In Ionic liquids (ILs) are organic salts that are liquid at or
addition, catalyst processing and ultimate recovery of these near room temperature (Tm < 100 °C). There are a myriad of
materials requires complete shutdown of a reactor. One of cation/anion combinations that can yield an organic salt.
the largest examples of biphasic homogeneous catalysis is Several of the most common cation classes of ionic liquids
the Ruhrchemie/Rhône-Poulenc2 process for short-chain are quaternary ammonium, imidazolium, pyridinium, and
olefin hydroformylation, which uses water to sequester and phosphonium. The IL, 1-hexyl-3-methyl-imidazolium bis-
recycle a rhodium catalyst with sulfonate-modified triph- (trifluoromethylsulfonyl)amide ([HMIm][Tf2N]) has been
enylphosphine ligands. However, its application to higher chosen by IUPAC (Committee on the Thermodynamics of
olefins is limited by the solubility of the olefin (<C5). Ionic Liquids, Ionic Liquid Mixtures, and the Development
Multiphase methods may suffer from thermodynamic (solu-
of Standardized Systems) to be a reference IL for worldwide
bility) issues, mass transfer limitations, catalyst separation,
study8 and is shown in Figure 1. [HMIm][Tf2N] will be used
and cross-contamination problems. Innovative and generic
in this work for studies in catalysis, phase equilibrium, and
methodologies for catalyst immobilization for continuous
mass transport. Ionic liquids can be molecularly engineered
reactions are fundamental for process development. Any
for specific physicochemical properties through various “R-”
new process should also be based around the principles of
groups and cation/anion selection, e.g. viscosity, solubility
* To whom correspondence should be addressed. Phone: +1 (785) properties, density, acidity/basicity, co-ordination properties,
864-4947. Fax: +1 (785) 864-4947. E-mail: ascurto@[Link]. stereochemistry, etc. It has been estimated that ∼1014 unique
10.1021/ie801871k CCC: $40.75  2009 American Chemical Society
Published on Web 03/31/2009
 Ind. Eng. Chem. Res., Vol. 48, No. 9, 2009 4255

Figure 1. Structure of 1-hexyl-3-methyl-imidazolium bis(trifluoromethyl-

sulfonyl)amide ([HMIm][Tf2N]).
cation/anion combinations are possible.9 As most ILs have
no measurable vapor pressure, and, thus, no air pollution
potential, they have been touted as “green” solvents; however,
toxicity in soil and water eco-systems must be carefully Figure 2. Phase behavior of the IL, [HMIm][Tf2N], and CO2 at 70 °C. The
understood. Novel ILs and processes are continually being solid line is smoothed data.
developed for extractions, reactions, and material processing.
2.2. Hydroformylation in ILs. Several studies exist in the 40% mol CO2 at 50 bar, 65% mol at 100 bar, and only marginal
literature which perform hydroformylation reactions in ionic increase in solubility beyond 100 bar. In contrast, the ionic liquid
liquid systems;10-12 for a recent review, see the work of is immeasurably insoluble in the pure CO2 phase (i.e., no dew
Haumann and Riisagers.13 Olivier-Bourbigou and co-workers11 point) and does not become miscible (critical) even at hyperbaric
found that the reaction rate (TOF) in ILs was similar to organic pressures, e.g. 3.1 kbar.25 This is unlike CO2 with most organic
solvents and directly correlated with the solubility of the olefin solvents (CXLs), which become miscible (critical; one phase)
in the different ionic liquids. Mehnert et al.12 studied hydro- at more moderate pressures (100-200 bar).23,24 Few biphasic
formylation of 1-hexene with catalysts dissolved in ionic liquids systems, except for those involving solid phases, can achieve
on solid supports. Wasserscheid and co-workers10 employed such lack of cross-contamination as with ILs and CO2.
ionic phosphine ligands for the rhodium catalyzed hydroformy- CO2 can dramatically decrease the viscosity of ILs to that of
lation of 1-octene and found high catalyst activity, high common solvents, which increases the diffusivity of compounds
selectivity to the linear product, and no detectable catalyst in IL. As will be shown below, the viscosity of the IL,
leaching. Several groups have investigated various ligands for [HMIm][Tf2N], decreases approximately 60+% with up to 100
hydroformylation focusing their effect on catalyst leaching, for bar of CO2 at 70 °C. This decrease in viscosity has been used
example, Jin et al.14 to predict the diffusivity in the ionic liquid with approximately
2.3. Challenges with Ionic Liquids. Upon closer inspection, a 3-fold improvement over the same pressure range. The groups
ILs can present a number of challenges for their use in of Leitner26 and Brennecke27 found that the presence of CO2
catalysis. ILs often have a lower solubility of reaction can even increase the solubility of reaction gases (H2 and O2)
gases15,16 (H2, CO, O2, etc.) than organic solvents which can into the IL phase. Scurto et al.28,29 have demonstrated the ability
hinder reaction throughput. Separating substances from ionic to separate ILs from organics or water using CO2 pressure which
liquids can often be difficult, as common separation and can induce immiscibility and extraction. Scurto, Leitner, and
fractionation techniques, such as distillation are no longer co-workers30,31 have demonstrated that CO2 can dramatically
possible for the nonvolatile IL solvent. While, the theoretical decrease the melting point of many ionic solids, even inducing
number of ionic liquids is astonishing (e.g., ∼1014),9 the vast melting over 100 °C below their normal melting points. This
majority are actually solids with melting points, Tm, above new technique with CO2 now allows many more of the estimated
100 °C. Most ionic liquids are more viscous than their 1014 ionic liquids/solids to be usable in a process as they have
organic-solvent counterparts,17,18 which can lead to lower shown for a variety of catalytic reactions.
diffusivity and lower mass transfer (lower reaction rates, 2.4. Catalyzed Reactions in Biphasic IL/CO2 Systems. The
extraction efficiency, etc.). Several groups working in various combination of compressed CO2 and ionic liquids offers a
fields have indicated the importance or limitation of mass number of benefits for catalyzed reactions, where the ionic
transfer for IL systems for gas solubility,15 base-catalyzed liquid phase is employed to sequester the organometallic
epoxidation,19 electrochemistry,20 three-phase heteroge- catalyst and the CO2 phase becomes the mobile phase for
neously catalyzed oxidations,21 enzyme catalysis,22 etc. reactants and products. A variety of reactions have been
2.4. Biphasic Ionic Liquids/CO2 Advantages. However, performed in biphasic IL/CO2 systems. However, the effect
coupling ionic liquids with CO2 may overcome many of these of CO2 on catalyzed reactions in ionic liquids is not consistent
limitations. A biphasic ionic liquid/CO2 system draws on the throughout the literature sources. Some indicate that CO2
advantages of each of the respective technologies and helps increases activity, while others demonstrate a decrease in
overcome their challenges. IL/CO2 systems are a unique subset activity with CO2 pressure. This contribution will attempt to
of, what are now called, gas or CO2 expanded liquids (GXLs/ resolve these literature discrepancies. Regardless, most studies
CXLs), which are organic solvents with large amounts of consistently find an increase in selectivity (chemo-, regio-,
dissolved CO2 as pioneered by the groups of Subramaniam, and enantioselectivity).
Jessop, Eckert, Foster, and others; for recent reviews, see the One of the first examples of an IL/CO2 biphasic system was
work of Jessop and Subramaniam23 and Scurto et al.24 GXLs/ olefin hydrogenation by Tumas and co-workers.32 They com-
CXLs have been used as a tunable media for reactions, pared the results in a biphasic IL/CO2 and IL/hexane system
extractions, and materials processing. and found little difference in the reaction rate with pressurized
Ionic liquids have unique phase behavior with CO2 as CO2 or hexane. Jessop, Eckert, and co-workers33 performed
illustrated in Figure 2 for [HMIm][Tf2N] and CO2 at 70 °C as asymmetric Ru-catalyzed hydrogenations in an ionic liquid/CO2
measured in this study (see below for experimental details). CO2 biphasic system with enantioselectivity that was tunable with
is very soluble in the ionic liquid and reaches approximately the pressure of CO2. Leitner and co-workers26 found for iridium
4256 Ind. Eng. Chem. Res., Vol. 48, No. 9, 2009

catalyst (acetylacetonatodicarbonylrhodium, [Rh(CO)2Acac)]

and the ligand (triphenylphosphine, TPP) were dissolved in the
ionic liquid and stirred for 30 min to allow complexation of
the ligand with the rhodium precursor (this time is in excess of
that observed by 31P NMR studies). The solution was then
Figure 3. Hydroformylation of 1-octene with syngas (H2:CO ) 1:1 by mole) diluted with pure IL to obtain the low catalyst loadings used in
with rhodium and triphenylphosphine as a ligand to n-nonanal (preferred)
and the branched 1-methyl-octanal. these studies. The solution was added to the reactor under argon
gas as an inert blanket. The argon was displaced with CO2 and
catalyzed hydrogenation of aromatic imines an increase in the reactant (1-octene) was injected into the reactor with a
reaction rate with the presence of CO2 compared with H2 syringe. The reactor was heated to 70 °C while stirring with a
pressure alone. From high-pressure NMR studies, the solubility small stir bar. Stirring was temporarily halted and syngas was
of H2 in the IL (as indicated by the size of the H2 peak) increases added to the reactor followed by CO2 using a high-pressure
with increasing CO2 pressure while maintaining constant H2 syringe pump (Teledyne-Isco, Inc. 260D). Stirring was im-
loading. mediately resumed and the reaction time started at a rate of
Hou et al.34 investigated the Wacker oxidation of 1-olefins 750 RPM with a 8 mm (0.31 in) × 13 mm (0.5 in) cylindrical
and found that increasing CO2 pressure significantly improved stirrer. At the end of the reaction, the autoclave was placed in
the selectivity of the 2-ketone over 3-ketone. They hypothesize an ice-bath to quench the reaction and the gas phase vented
that the increase in pressure increases the solubility of the olefin into a collection solution of n-hexane. This was necessary as
into the CO2 phase, thus creating lean conditions that prevented significant quantities of 1-octene and n-nonanal are soluble in
isomerization. Zhao and Jiang35 investigated the electro- the CO2 phase, especially at the higher pressures. The ionic
oxidation of benzyl alcohol and found that a large amount of liquid phase was extracted by ∼3 mL of hexane three times for
CO2 dissolved in IL can increase the ionic conductivity and quantitative extraction. Both the vent and extraction solutions
ion mobility of ionic liquids, which seems to improve the are combined and analyzed by gas chromatography (described
Faradic efficiency and selectivity over reactions without CO2. below).
However, the efficiency begins to decrease at higher pressure, 3.2. Phase Equilibrium. The high-pressure phase equilib-
which they attribute to the phase behavior of products and rium data were measured by a windowed autoclave reactor and
reactants in CO2 and IL media. Ballivet-Tkatchenko et al.36 used static vapor-liquid equilibrium (VLE) apparatus. The autoclave
[BMIm][BF4] and supercritical CO2 for the biphasic palladium- reactors were similar to those described above except with a
catalyzed dimerization of methyl acrylate. The turnover fre- high-precision pressure gauge, Omega DPG7000 with an error
quency (TOF) and selectivity was similar to the monophasic band of (0.05% of full scale (3000 psi). The static VLE
system. apparatus is described in detail by Ren and Scurto41 and will
2.4.1. Hydroformylation in Biphasic IL/CO2 Systems. be overviewed here. This apparatus consists of a high-pressure
Cole-Hamilton and co-workers37,38 investigated the hydroformy- equilibrium cell, high-pressure and precision syringe pump filled
lation reaction of long chain alkenes in a biphasic CO2/ with CO2, a water bath, and accessories to measure the
imidazolium IL system with rhodium catalysts with modified temperature and pressure. The solubility, density of the liquid
phosphine ligands. The conversion rate was slightly lower than solution, molar volume, volume expansion, and molarity are
those obtained in toluene or ILs alone, but they exhibited similar computed from the apparatus. These calculations are based on
or enhanced selectivity (linear to branched ratio, n:i). These the mass balance by determining the amount of CO2 delivered
systems were carried out in a continuous flow system where from the pump, the mole/mass of CO2 in the headspace above
the CO2 delivered the olefin and removed the aldehyde product the liquid and in the tubing/lines to the equilibrium cell. This
at high turnover frequencies. Scurto and Leitner30 illustrated apparatus yields a high resolution of solubility data (often better
the Rh-catalyzed hydroformylation of vinyl-naphthalene in a than (0.001), pressure with accuracy of (0.1 bar, temperature
biphasic IL/CO2 system, where CO2 was used to induce melting of (0.01 °C, density up to ( 0.4%, and volume expansion to
of a quaternary ammonium salt, tetra-n-butyl-ammonium tet- (0.05%. In addition, there is no need for analytical methods,
rafluoroborate, at a temperature over 100 °C below its normal nor calibration for each specific system of interest.
melting point. This platform was also used for hydrogenation
The liquid-liquid equilibrium envelope at ambient pressure
and hydroboration.
of 1-octene, n-nonanal, and ionic liquids was measured by a
2.5. Overview. This contribution will attempt to quantify
cloud point method, where one component is continuously added
the beneficial effects of CO2 and ILs for catalytic systems
to the other component (for binary mixtures) or a mixture at a
through a model example of hydroformylation of 1-octene
certain ratio (ternary mixtures), until the mixture becomes
with rhodium and a simple triphenylphosphine catalyst
cloudy. The amount of each component is measured with a
(Figure 3). Reaction rates, phase equilibrium thermodynam-
Mettler Toledo XS205 Dual Range Balance, with an accuracy
ics, and mass transport properties will be addressed to
of 0.01 mg for the range as maximum of 81 g and 0.1 mg for
understand these tunable biphasic systems and to engineer
the range as maximum of 220 g. A Branson Model 2510
efficient reactions and separations. These data will help to
Ultrasonic cleaner was used to mix the solutions.
explain the different trends reported in the literature for the
contribution of CO2. 3.3. High-Pressure Viscosity Measurements. The high
pressure viscosity of the ionic liquid and CO2 mixture was
measured with a Cambridge Applied Systems (currently
3. Experimental
Cambridge Viscosity) high pressure viscometer (ViscoPVT/
3.1. Catalytic Reaction. The biphasic IL/CO2 hydroformy- ViscoPro 2000 System 4-SPL-440 with Viscolab software).
lation reactions were carried out in a 10-cm3 316 stainless steel The apparatus was modified to include a high-pressure
high-pressure autoclave reactor similar to a design by Koch and equilibrium view cell, high-pressure syringe pump and
Leitner and co-workers39 and modified in our group; for fur- recirculation system. Details of the apparatus are found
ther details, see Schleicher.40 For the reaction experiments, the elsewhere,42,43 and an overview of the procedure will be given
 Ind. Eng. Chem. Res., Vol. 48, No. 9, 2009 4257
here. A volume of approximately 25 mL of the dried denser hydrophobic IL phase was decanted and washed with
compound was transferred into the high-pressure Jerguson water for 6-8 times. The IL was then dried under vacuum. 1H
view-cell from a Schlenk flask under argon using a stainless NMR chemical shifts (relative to TMS internal standard) and
steel high pressure metering pump (Eldex Laboratories, Inc., coupling constants J/Hz: δ ) 8.65 (s, 1H), 7.39 (d, 2H, J )
Model 1020 BBB-4). A ∼30 cm3 Jerguson view-cell is 4.19), 4.17 (q, 2H, J ) 7.4), 3.93 (s, 3H), 1.87 (m, 4H), 1.32
utilized as an equilibrium cell which holds the ionic liquid (m, 6H) 0.87 (t, 3H, J ) 6.53). Analysis calculated for
and CO2. A Teledyne-Isco, Inc. syringe pump (model 260D) C12H19N3F6S2O4: C, 32.2; H, 4.28; N, 9.39; S, 14.33. Found:
is used to administer and maintain CO2 pressure. A Micro- C, 32.21; H, 4.27; N, 9.25; S, 14.19. From NMR and elemental
pump, Inc. (model 415A) recirculation pump is used to draw analysis, the estimated purity is 99+%. The water content is
ionic liquid from the viewcell, transport it through the less than 100 ppm, and the Br content is lower than 8 ppm.
viscometer, and then back to the top of the viewcell where 3.6. Analysis. Elemental analysis was performed by Desert
the material falls through the vapor (CO2) phase back to the Analytics Transwest Geochem. H NMR spectra were recorded
liquid layer. This recirculation allows for a rapid approach on a Bruker 400 NMR spectrometer using TMS as a reference
to equilibrium, while being able to monitor the change in for 1H chemical shifts. Gas chromatography analyses of the
viscosity over time. Equilibrium is usually achieved in product mixtures were carried out on a Varian CP-3800 Series
approximately 30 min at each pressure. However, at low gas chromatograph equipped with a flame ionization detector
temperatures and pressures (highest viscosity), up to 60 min (GC-FID for quantitative analyses) and a chrompack capillary
or more is allowed. column CP-Sil 5 CB (25 m, 0.32 mm, 1.2 µm). The water
The nominal accuracy of the pressure gauge is 0.07% full- content was determined by a Mettler Toledo DL32 Karl Fisher
scale (FS ) 30 000 psig); but the NIST traceable calibration coulometer, and the Br content was measured by a Cole Parmer
was accurate to 0.0084% full-scale. The maximum and average Bromide Electrode (27502-05) read with an Oakton Ion 510
fluctuation of temperature throughout an isothermal run is 0.1 series meter.
and 0.07 °C, respectively. The error in viscosity is reported at 3.7. Materials. Coleman Instrument grade CO2, argon (extra
each point based upon the sampling average of 20 measure- dry grade, 99.998%), syngas (H2/CO 0.98% purity, H2 99.999,
ments. The viscosity data have been reported with an estimated CO 99.5%, certified standard) were obtained from Airgas, Inc.
uncertainty of less than (2.0%. 1-Octene (CAS 111-66-0) 98%, acetylacetonato dicarbonyl-
3.4. Diffusion Measurements. Diffusivities in the reaction rhodium (CAS 14874-82-9) 98%, triphenylphosphine (CAS 603-
mixture were measured using a nuclear magnetic resonance 35-0) 99%, hexane (CAS 110-54-3) HPLC grade g95%,
(NMR) technique. Details of the technique are found else- 1-methylimidazole, (CAS 616-47-7) 99+%, lithium bis(trifluo-
where,40 and an overview will be given here. The pulse sequence romethylsulfonyl)amide (CAS 90076-65-6) 99.95%, and aceto-
selected for calculating the diffusion coefficients was a bipolar nitrile (CAS 75-05-8) g99.9% were purchased from Sigma-
longitudinal eddy decay (BPP-LED) sequence. All diffusion Aldrich. 1-Bromohexane (CAS 111-25-1) 99+% was obtained
measurements where conducted using a Bruker Avance 400 from Acros. The [Rh(CO)2Acac] was placed in a Schlenk tube
MHz Ultrashield NMR equipped with a standard BBO probe. and stored under dry argon. 1-Methyl-imidazole and 1-bromo-
Nondeuterated components were used in these experiments by hexane were vacuum-distilled and used immediately.
proper shimming. The field gradient was calibrated using the
known diffusion rate of ethanol in water at xEtOH ) 0.68; D 4. Results and Discussion
equal to 7.52 × 10-10 m2 s-1 at 25 °C44,45 and was determined
to be 51.8 G m-1 at maximum current. For moderate pressure The Rh-catalyzed hydroformylation of 1-octene with triph-
measurements (<13 bar), a specialized NMR tube was utilized enylphosphine ligands was chosen as a model reaction in the
from Wilimad Glass, Inc. (Model PV-ANV Pressure/Vacuum biphasic ionic liquid [HMIm][Tf2N] and CO2 system. Focus was
NMR Valve). placed on the effect of phase equilibria on the reaction rate.
3.5. Synthesis of Ionic Liquid. 1-Hexyl-3-methylimidazo- Elements of mass transport properties are also measured and
lium bis(trifluoromethylsulfonyl)amide ([HMIm][Tf2N]) was discussed in relation to their effect on biphasic catalyzed
prepared by anion exchange from the corresponding bromide reactions.
salt of the imidazolium cation ([HMIm][Br]) with lithium 4.1. Effect of Pressure on Reaction Rates. From the
bis(trifluoromethylsulfonyl)amide (Li[Tf2N]) in deionized water literature, the effect of pressure on reaction rates in biphasic
as described in the literature.46,47 The bromide salt of the IL/CO2 reaction systems is somewhat inconsistent: some report
imidazolium cation was prepared from a quaternization reaction that CO2 pressure increases the reaction rate others say that it
of 1-methylimidazole with a slight excess amount of the decreases the rate. The hydroformylation of 1-octene with
corresponding 1-bromohexane in acetonitrile at 40 °C under an Rh-TPP catalytic system was conducted at constant loading
argon atmosphere with stirring for three days. Caution! This of IL, 1-octene, 1:1 CO/H2, and catalyst with pressure of CO2
reaction can be highly exothermic and adequate solVent Volumes varied. As shown in Figure 4, the apparent reaction rate seems
and/or cooling must be proVided during the reaction. The to decrease with increasing CO2 pressure. Table 1 illustrates
bromide salt of 1-hexyl-3-methyl-imidazolium was purified with that the selectivity to the linear aldehyde, which is most often
activated charcoal (10%) stirring for 24 h. Acetonitrile was the industrially desired product, increases slightly with increasing
added to reduce the viscosity of the ionic liquid, and the mixture pressure. These results are despite the perceived increase in
was filtered. The mixture was then passed through a plug of mass-transport properties in the presence of CO2 and several
Celite (depth ) 7 cm, diameter ) 3 cm) and through a short reports of increased reaction rate with CO2 pressure. This leads
column (height ) 20 cm, diameter ) 2.5 cm) of acidic alumina. to a number of questions: Why does CO2 decrease the apparent
The solvent was removed on a rotary evaporator under reduced reaction rate? How does the CO2 pressure change the thermo-
pressure at 40 °C and then connected to a high vacuum (<10-4 dynamic properties, such as phase behavior, volume expansion,
torr) at 50 °C for at least 48 h. [HMIm][Tf2N] was synthesized concentrations, etc.? What are the quantitative changes in mass
by anion exchange between the [HMIm][Br] and Li[Tf2N]. The transport properties?
4258 Ind. Eng. Chem. Res., Vol. 48, No. 9, 2009

Table 2. Viscosity of [HMIm]]Tf2N] with CO2 Pressure/

Concentration at 70 °C
P [bar] viscosity, ηmixture [mPa s] viscosity, ηILa [mPa s] % ∆ηb
1 13.37b 0
10 12.45 13.62 -9
32 10.27 13.90 -26
49 9.83 14.11 -30
69 7.69 14.37 -46
98 5.03 14.75 -66
112 3.79 14.93 -75
125 3.58 15.11 -76
a
Viscosity of pure IL at the pressure of the saturated mixture
interpolated from the data of Ahosseini and Scurto. b % ∆η ) (ηmixture -
ηIL(P))/ηIL(P) × 100.

Figure 4. Reaction of the hydroformylation of 1-octene with total pressure

CO2. The line is of smoothed data.

Table 1. Effect of CO2 Pressure on the Apparent Reaction Rate for

the Hydroformylationa of 1-Octene in [HMIm][Tf2N]
P [bar] TOF (SD) regioselectivity (linear/branch)
30 64.6 (0.1) 2.7
60 64.6 (0.8) 2.7
96 64.1 (0.4) 2.7
120 62.5 (1.7) 2.7
147 57.4 (0.9) 2.8
194 48.0 (2.8) 2.8
a
Reaction conditions: Psg ) 30 bar, 70 °C; 1 h catalyzed by
Rh-TPP (1:4); standard deviation with n g 3.

From the literature, one of the most common generalized rate

equations for olefin hydroformylation with rhodium/phosphine Figure 5. Viscosity of [HMIm][Tf2N] at 70 °C with pressure of CO2.
catalysts48-52 is

( )
[olefin][H2][CO][Rh] the TOF reached an asymptotically constant value. Thus, the
-rrxn ) k (1) CO2 pressure increased the apparent reaction rate presumably
(1 + KH2[H2])a(1 + KCO[CO])b due to increased mass transport of H2. Solinas et al.26 observed
similar finding for Ir-catalyzed imine hydrogenation in IL
where a and b (b > a) are adjusted for the olefin (ethylene, without stirring and with CO2 pressure. While these results seem
1-hexene, 1-dodecene, etc.) and solvent of the reaction. For a to indicate that increased mass transport properties increased
more recent review of hydroformylation kinetics, see the work the apparent reaction rate under mass-transport limited condi-
of Chaudhari et al.53 From the work of Purwanto and Delmas,52 tions, the possibility exists that CO2 increased the solubility of
the Rh-catalyzed hydroformylation of 1-octene in toluene, the H2, which might also increase the reaction rate. This will be
parameters for the rate expression are a ) 1 and b ) 2. This examined below.
implies that the rate should be first order with 1-octene and 4.2.1. Viscosity. The hydroformylation reaction is much
have an overall negative order in CO at certain ranges of KH2. slower than the hydrogenation reaction discussed above and is
From this general expression, there are two main ways that an often in the kinetically limited regime with proper stirring.
inert component such as CO2 can affect the reaction rate: However, similar phenomena in mass transfer are believed to
modifying the concentrations and/or changing the intrinsic occur. These results directed us to quantify the mass transport
kinetic constant (k). Alternatively, if the reaction is diffusion effects under the reaction conditions of interest. The mixture
controlled then the mass transport properties will also affect viscosity of the IL phase with CO2 was measured at 70 °C with
the apparent rate. The issues of mass transport (section 4.2) and a high-pressure viscometer. The results are presented in Table
phase equilibrium (section 4.3) will be systematically addressed. 2 and Figure 5. As shown, the viscosity significantly decreases
Section 4.4 will then use these data to elucidate the phenomena with increasing CO2 pressure. More precisely, the viscosity
illustrated above and in the literature. decreases as the mole fraction of CO2 dissolved in the IL phase
4.2. Mass Transfer Effects Biphasic IL/CO2 Systems: increases (see Figure 2). The mole fraction was determined by
Viscosity and Diffusivity. In a concurrent study, the Rh- interpolating the phase equilibrium data. The viscosity of pure
catalyzed hydrogenation of 1-octene in a similar biphasic ionic [HMIm][Tf2N] with hydrostatic pressure has recently been
liquid/CO2 system was investigated.54 As Rh-catalyzed hydro- measured in our laboratory.43 These data have been used to
genation of olefins is a relatively rapid reaction, the H2 determine the percentage of viscosity reduction with CO2
availability often becomes a limiting factor. In order to study pressure using pure IL viscosity at the corresponding pressure
the effect of CO2 on the mass transport rate and reaction rate, and are listed in Table 2. At 70 bar, the viscosity reduction
interfacial mass-transfer limitations were intentionally estab- approaches 43+%. After approximately 100 bar, the viscosity
lished by eliminating agitation and reducing the interfacial area. decrease with pressure becomes more marginal. This corre-
Under these conditions with a constant molarity of 1-octene, sponds to the solubility behavior shown in Figure 2, which
the reaction rate (turnover frequency (TOF)) increased with indicates that the incremental CO2 solubility increase with
additional pressure of CO2 until approximately 40 bar where pressure after ∼100 bar also becomes smaller. Han and co-
 Ind. Eng. Chem. Res., Vol. 48, No. 9, 2009 4259
Table 3. Diffusivity of 1-Octene and [HMIm][Tf2N] at 70 °C
1-octene in
T ) 70 °C [HMIm][Tf2N] 1-octene [HMIm][Tf2N] (0.2 M)
D [cm2/s] × 10-6 0.96 59.4 5.59

workers55 investigated the viscosity of IL/methanol/CO2 systems

and report the viscosity of [BMIm][PF6] with CO2 pressure for
three isotherms at elevated pressures. Eckert and co-workers56
utilized a spectroscopic method to estimate the “microviscosity”
of a probe molecule the IL/CO2 mixture. Tomida et al.57
measured the viscosities of 1-butyl-3-methylimidazolium tet-
rafluoroborate ([BMIm][BF4])/CO2 mixtures using a rolling ball
viscometer from 293.15 to 353.15 K and pressures of up to
200 bar. Figure 6. Viscosity and experimental and predicted diffusivity (cation) of
4.2.2. Diffusivity. Dissolved CO2 reduces viscosity which [HMIm][Tf2N] with pressure of CO2.
also increases diffusivity. The self-diffusivity of 1-octene,
[HMIm][Tf2N], and mixtures of 1-octene in [HMIm][Tf2N] at
ambient pressure and 70 °C have been measured using an NMR
method as shown in Table 3. For the IL, the method can follow
the diffusivity of the cation and anion independently. From Table
3, [HMIm][Tf2N] has over 1 order of magnitude slower diffusion
coefficient than 1-octene, and consequently reduces the diffu-
sivity of 1-octene in the 0.2 M solution in [HMIm][Tf2N] by
approximately an order of magnitude over pure 1-octene. Thus,
any improvement in the IL viscosity will ultimately improved
the diffusivity of the reactant, 1-octene, in the mixture.
The self-diffusivity of pure components and mixtures are
often correlated with the Stokes-Einstein58 equation for the
diffusivity, D:

kBT
D)
nπaη Figure 7. Volume expansion (% ∆V/V0 ) (V - V0)/V0 × 100; pure IL
volume, V0) of [HMIm][Tf2N] with CO2 pressure with/without CO/H2 at
where, n is often 4 for smooth spherical object (slip-boundary 70 °C; molar ratio of syngas:IL in the system is 0.3 at Psyngas ) 6 bar and
at 30 bar, it is 0.8.
condition) and 6 for a rough one; a is the hydrodynamic radius
characteristic of the diffusing object; T is temperature; η is the CO2 pressure as seen in our previous studies of hydrogenation
viscosity; and kB is the Boltzmann constant. If a diffusion in a mass-transport limited regime54 and several reports in the
coefficient is known at a given temperature and viscosity of literature.
the solvent, then the diffusivity can be approximated at other 4.3. Phase Equilibria of IL, CO2, and Reactants/Prod-
conditions (viz. other viscosities) by ucts. The phase behavior of the reactants, product, CO2, and
the ionic liquid was investigated. The various equilibria will
D0 be presented and connected to the apparent reaction rate.
D)
η/η0 4.3.1. Volume Expansion of the Ionic Liquid. CO2 is highly
soluble in ionic liquids as shown for the IL, [HMIm][Tf2N], at
where the subscript 0 indicates the diffusivity and viscosity of 70 °C in Figure 2. As CO2 begins to dissolve into the IL phase,
the pure IL at ambient conditions. This equation is used to the total volume increases. This can have large effects on
predict the diffusivity of the IL in mixtures with CO2 by reactions in biphasic IL/CO2 systems as will be discussed below.
knowing the IL/CO2 viscosity. As shown in Figure 6, the The volume expansion of the [HMIm][Tf2N] with CO2 and with
predicted diffusivity increases by approximately 290% from a mixture of CO2 and syngas (H2:CO ) 1:1 by mole) have been
ambient conditions to 125 bar. Of course, actual diffusivities measured at 70 °C and shown in Figure 7. The IL phase expands
are not just a function of the viscosity, but also the chemical by approximately 25.0% at 119.8 bar with pure CO2. Figure 7
composition which is changing throughout the pressure range. The volume expansion with the IL was also measured under
Regardless, this approximation does allude to the large increase similar reaction conditions with different pressures of syngas
with the presence of CO2. High-pressure diffusivity measure- (CO/H2). The system with syngas (H2, CO), IL, and CO2 is a
ments at these conditions are planned for the future. There are quaternary system and technically requires the specifications
several reports of the Fickian diffusion of CO2 into the IL at of the initial and final concentrations or molar ratios of all
low pressures (infinitely dilute conditions) in the literature,59-63 components according to the Gibbs phase rule, to adequately
but this would be quite different at these larger pressures/ characterize the thermodynamic properties (including volume
compositions of CO2. For the hydroformylation reaction under expansion). For instance, syngas loaded into a reaction cell could
study, these results indicate that 1-octene and syngas will diffuse be fixed at 6.11 bar, but without knowledge of the amount of
more rapidly with increasing CO2 pressure/composition and thus IL and the amount in the vapor phase, the loaded amount (moles)
allow the reaction to proceed more easily into the kinetically of syngas would be unknown. However, as the solubility of
controlled regime. The lower viscosity and higher diffusivity syngas is much lower than CO2, the volume expansion with
may help to explain the increase in apparent reaction rate with the mixed gases should change little whether loaded at a given
4260 Ind. Eng. Chem. Res., Vol. 48, No. 9, 2009

Figure 8. Phase behavior of 1-octene and n-nonanal and CO2 as percent of

initial amount of nonanal (CO2-free basis). This figure can also be read as Figure 9. Ambient pressure phase behavior of 1-octene, n-nonanal, and
the phase behavior as a function of the conversion. [HMIm][Tf2N] at 22 °C.

pressure with a syngas to IL ratio of 0.5 or 1, for instance. The the points, a one phase mixture exists and below the points,
majority of the loaded syngas will reside in the gas (CO2) phase. two-phase vapor-liquid equilibrium exists. This change in
Thus, the volume expansion at other conditions will be nearly concentration can also be considered the conversion for the
similar to these reported data. hydroformylation reaction. As seen in the figure, the mixture
With an initial pressure of approximately 6.11 bar of syngas, critical pressure increases with concentration of nonanal from
the volume expansion decreases at a given pressure over that pure 1-octene (0% conversion) to pure n-nonanal (100%
of just pure CO2, which would be expected as the solubility of conversion). Thus in order to maintain a single phase throughout
H2 and CO is much less than CO2.64-67 By reducing the partial the reaction, the phase behavior throughout the entire composi-
pressure or, more appropriately, increasing the fugacity of CO2 tion (conversion) range must be known. For reactions in
in the vapor phase, the solubility of CO2 at a given pressure in supercritical fluids, a single phase is usually desired, but simply
the liquid phase will be lower. If the volume expansion of the choosing a pressure just above the critical point of the reactant
CO2/H2/CO mixture were linearly related to the partial pressure (1-octene)/CO2 system may yield two phases during the reaction.
of the CO2 in the vapor phase, then the volume expansion of Similar conclusions were reached by Han, Poliakoff, and co-
the mixture would be equal when the total pressure in the pure workers,68 when studying the effect of the mixture critical point
CO2 case is equal to the partial pressure in the mixed gas case. on reactions in initially single-phase supercritical fluids. The
However, the volume expansion with 30 bar initially of syngas figure also demonstrates that the addition of syngas increases
is equal to the pure CO2 case at approximately 22 bar lower, the mixture critical pressure beyond the initial syngas pressure
not 30 bar lower as given by the partial pressures. Thus, simply (i.e., 30 bar). This is in an analogous manner to the volume
knowing the volume expansion at a certain pressure of pure expansion differences as discussed above. With an initial loading
CO2 does not yield the exact volume expansion with the gaseous of 30 bar of syngas, the mixture critical pressure increases from
mixture of interest for reactions. 32 to 51 bar over the pure CO2 conditions.
4.3.2. Phase Behavior of the Reactants/Product and 4.3.3. Phase Behavior of the H2/CO in IL with CO2. It
CO2. The phase behavior of the reactants and products with has been indicated in the literature that the presence of CO2
CO2 (without the IL) also yield valuable insight into the effect may enhance the solubility of permanent gases, such as CO,
of pressure on the biphasic IL/CO2 reaction system. Organic H2, O2, CH4, in ionic liquids over the pure gases as similar
liquids, such as 1-octene and n-nonanal, can become miscible pressures. Brennecke and co-workers69 indicate moderate to no
with CO2 at conditions (temperature, pressure, and composition) enhancement for O2 and CH4. However, Solinas et al.26,70
above the bubble point (solubility of the CO2 in the liquid phase) indicate significant enhancement of H2 in ionic liquids as
or at conditions beyond the mixture critical point. The mixture observed from proton NMR. This phenomenon has been well-
critical point is the highest pressure and composition at a given established for the CO2-enhanced solubility of gases in organic
temperature in which a vapor and liquid phase can coexist. The solvents (CXLs).71-73
system of syngas, CO2, 1-octene and n-nonanal is a 5-component 4.3.4. Phase Behavior of the Reactant/Product, IL, and
system, and, as such, the initial concentrations (or molar ratios) CO2. In addition, the phase behavior of the ionic liquid, reactant,
must be established according to the Gibbs phase rule to product, and CO2 can yield insight in the reaction phenomena
adequately specify the thermodynamic system. For liquid as well as illustrate potential advanced separation techniques.
mixtures with two or more components, the mixture critical Scurto et al.28,29 and other researchers74-78 have indicated that
points can change with composition. The mixture critical points CO2 at certain conditions can be used to induce phase splitting
of the reactant and/or product with CO2 will have direct and separation into an IL-rich phase and an organic-rich phase.
implications on the biphasic IL/CO2 system. As the ionic liquid This is especially significant at large reactant to IL (catalytic
is immeasurably insoluble in the CO2 phase under the conditions phase) loading, which would be desirable for large-scale or
studied here, the fluid phase is directly tied to the phase behavior continuous hydroformylations.
of the reactants, product, and CO2; this will be further discussed The ambient pressure phase behavior of 1-octene, n-nonanal,
below. Figure 8 illustrates the mixture critical pressure at 70 and [HMIm][Tf2N] is illustrated in Figure 9. As shown, the
°C as the proportion of 1-octene to n-nonanal is varied between product is miscible with the IL phase, but the reactant, 1-octene,
pure 1-octene and pure n-nonanal (on a CO2-free basis); above is only partially miscible. Thus, as conversion increases, the
 Ind. Eng. Chem. Res., Vol. 48, No. 9, 2009 4261

Figure 10. Diagram of the phase behavior as seen in the autoclave reactors with increasing temperature and pressure for mixtures of the organic reactants/
products with the IL and CO2 pressure.

Table 4. Percent Volume Expansiona of [HMIm][Tf2N] with CO2 Table 5. Mixture Critical Points of Different Initial Ratios of 1-Octene
and CO2 with Syngas (CO/H2) and n-Nonanal with CO2 and with CO2 and CO/H2 at 70 °C
CO2 with initially 6.11 CO2 with initially 30.06 CO2 CO2 with initial 30 bar CO/H2 pressuresc
pure CO2
barb CO/H2 (1:1) barc CO/H2 (1:1)
mole fraction critical mole fraction critical
P [bar] % ∆V/V0 P [bar] % ∆V/V0 P [bar] % ∆V/V0 of n-nonanala pressure [bar] of n-nonanalb pressure [bar]
16.86 1.74 16.27 1.16 60.59 6.61 0.00 115.30 0.00 147.13
28.44 3.86 39.76 5.20 95.98 12.79 0.10 121.90 0.25 159.41
39.97 6.44 59.88 10.26 117.91 18.72 0.33 124.31 0.50 166.39
58.44 10.91 79.57 15.03 153.96 25.85 0.50 130.50 0.75 176.46
70.80 13.92 94.24 18.97 195.55 31.08 0.67 132.75 1.00 188.30
94.65 19.64 107.59 21.92 0.90 133.80
119.78 24.95 120.70 24.17 1.00 136.10
a
% ∆V/V0 ) [V(P) - V(P ) 1 bar)]/V(P ) 1 bar) × 100. b
Molar a
CO2-free basis. b
CO2/syngas free basis. c
Initial molar ratio of
ratio of syngas: IL in the system is 0.293. c Syngas: IL ) 0.809. syngas: IL ) 0.81:1.

reaction could proceed from a two-phase region to a single Table 6. Phase Transition of n-Nonanal, [HMIm][Tf2N], with CO2
miscible phase depending on the initial concentration of at 70 °C
1-octene. From a separations perspective, immiscible products initial loading VLE to VLLE (V-L f V-L1-L2) K-point
would be preferred, as they would naturally separate. However, ILa [mol %] [bar] phase split pressure (L-L ) V) [bar]
with CO2 there are other possibilities and regions of behavior 0 136.1
that must be understood for efficient reactions and separations 10 117.3 136.2
of the biphasic IL/CO2 reactions. 25 124.2 136.3
With CO2 pressure the organic liquids (reactant and product) 31 no split
50 no split
may be induced to separate from the IL mixture. Figure 10
illustrates the qualitative phase behavior of loading of <30% of
a
CO2-free basis.
[HMIm][Tf2N] with the product n-nonanal or mixtures with Table 7. Phase Behavior of Mixtures of 1-Octene and n-Nonanal
1-octene. As shown, the mixture is homogeneous at ambient with 10% mol [HMIm][Tf2N] with CO2 at 70 °C
conditions. When CO2 pressure is applied, the transition from
VLE to VLLE K-point
VLE to vapor-liquid-liquid equilibrium (VLLE) (V-L f initial loading of (V-L f V-L1-L2) (L-L ) V)
V-L1-L2) is encountered, this is the first instance of liquid 1-octene [mol %]a [bar] [bar]b
instability leading to two liquid phases in equilibrium with a
octene (90%) LLE @ 1 bar 115.5 (115.3)
vapor phase (VLLE). As pressure is increased, the relative nonanal (30%) + octene (60%) LLE @ 1 bar 124.1 (124.3)
volume of the organic-rich phase increases until it reaches the nonanal (45%) + octene (45%) 32.0 131.0 (130.5)
“K-point” where the organic-rich phase and CO2 phase become nonanal (60%) + octene (30%) 87.4 132.5 (132.8)
critical and miscible to each other leaving an IL-rich phase and nonanal (90%) 117.3 136.2 (136.1)
a vapor (fluid) phase. Above the K-point pressure, more of the a
With 10% IL. b Critical pressure without IL in parentheses.
remaining amount of organic in the IL phases partitions to the
upper fluid phase, similar to supercritical fluid extraction from the IL. The K-point of these two mixtures was nearly identical
ionic liquids.79 The K-point pressures have been observed to at 136 bar. When the concentration of the IL was further
be identical within experimental accuracy to the mixture critical increased in the initial mixture, phase splitting did not occur.
points of the binary organic and CO2 system without the IL. However, under these conditions, the nonanal would partition
This is due to the lack of IL in the CO2 vapor phase and in the between the CO2 phase and the IL phase, with a rapid increase
middle organic-rich phase near the K-point as confirmed in in the partition occurring in the regime near the binary
similar systems by Aki et al.74 Often multiphase situations are nonanal/CO2 mixture critical point conditions of 136 bar of
avoided in reactions systems due to the interfacial mass transfer pressure (see above).
limitations. However, as the dissolved CO2 significantly in- For the case of incomplete conversion, mixtures of 1-octene
creases the mass transport properties of the IL phase, multiphase and n-nonanal will exist and this will change the condition
scenarios may not necessarily lead to mass-transport limited of the transition (V-L f V-L1-L2) and K-point. Various
reaction kinetics. ratios of 1-octene to n-nonanal were mixed with 10% mol
The pressure of the transition to VLLE (V-L f V- of the IL. The VLE to VLLE transition and K-points are
L1-L2) and back to VLE behavior (K-point) for mixtures of compared in Table 7. As large loadings of 1-octene are only
the IL with the product n-nonanal with CO2 are illustrated partially miscible with the IL, two phases occur at ambient
in Table 6. As shown, the mixture splits into two liquid pressures to the K-point. The mixture critical point without
phases at approximately 117 bar of pressure with an initial the ionic liquid (in parentheses in the table) is within
concentration of IL of 10% mol and 124 bar at 25% mol of experimental accuracy of the case with the IL. The mixtures
4262 Ind. Eng. Chem. Res., Vol. 48, No. 9, 2009

Figure 11. Volume expansion and nominal molar concentration of 1-octene Figure 12. Hydroformylation results plotted versus nominal concentration
in the IL phase as a function of CO2 pressure. [molarity]. The solid line is smoothed data. The dotted line is approximate
linear behavior where volume expansion dominates. The dashed line is the
of equal portions of 1-octene and n-nonanal (45%:45%) with approximate point where the reactant and product are critical with respect
10% IL are initially miscible and form the two liquid phase to CO2.
condition at relatively low pressure (32 bar). With higher
proportion of n-nonanal, the VLE to VLLE transition pressure draw approximately in Figure 12. While the organic rich phase
increases. and the CO2 phase become critical to each other, the organic
These results would have significant effect in the design of compounds may still partition to some extent between the
high-throughput reactions in biphasic IL/CO2 systems. The resultant CO2 and IL phases. However, the majority of the
catalytic results presented above are performed below the organic compounds will be in the CO2-rich phase,74 and the
concentrations where phase splitting occurs. However, for higher driving force for partitioning of the 1-octene from the catalytic
loadings needed for realistic applications, the LLV and K-points IL phase to the CO2 phase increases as the CO2 pressure
must be known for proper engineering. increases. At higher pressures, the 1-octene and n-nonanal will
4.4. Effects of Phase Equilibrium on the Catalytic preferentially partition away from the catalytic IL phase into
Reaction Rate. The pressure/composition effect on the phase the CO2 phase. Thus, the low apparent reaction rate at the higher
behavior of this system has dramatic effects on the reaction pressures (low molarity) can be ascribed to the lower solubility
rates. From the reaction results, the apparent reaction rate and concentration of the 1-octene reactant. However, at lower
becomes lower with increases in pressures (Figure 4), while pressures of CO2, dilution rather than reactant partitioning will
the volume expansion increases with increasing pressure or be the dominant factor. To confirm this analysis, the reaction
CO2 composition (Figure 7). If one assumes that the 1-octene was performed at 120 bar total pressure with helium not CO2.
is found exclusively in the IL phase at all pressures, then The solubility of helium in the ionic liquid is estimated to be
the moles of 1-octene will be constant, but the volume of very small and orders of magnitude lower than CO2. The data
the liquid phase will continually increase with increasing indicates that hydrostatic pressure has little effect on the reaction.
pressure. This volume increase with constant moles of Zhao and Jiang35 observed a decreased rate of electro-oxidation
1-octene will decrease the molarity of the reactant as shown of benzyl alcohol at high pressures and also hypothesized that
in Figure 11 using the actual concentration loaded for the this was due to reactants partitioning into the CO2 phase.
reaction results. For instance, if the concentration of 1-octene The large decrease at the higher pressure may be hypothesized
in the IL without CO2 is approximately 45 mM, then at 160 to be due to the partitioning of the Rh-TPP complex or the
bar of total pressure (30 bar syngas and CO2), the concentra- excess TPP into the CO2 phase. Shimoyama et al.80 have
tion decreases to approximately 34 mM; a decrease of ∼25%. recently measured the solubility of both TPP and the Rh
This dilution is before the reaction occurs and the overall complex, [carbonylhydridotris(triphenylphosphine)-rhodium],
reaction rate should decrease according to its rate law/order; in supercritical CO2. They found that the solubility of each at
for instance, see eq 1. Using the volume expansion data from 60 °C and approximately 15 bar to be a mole fraction of 8.7 ×
Figure 7 to compute the molarity at each pressure, Figure 4 10-4 for TPP and 5.8 × 10-7 for the Rh complex. This low
is transformed from TOF versus pressure to TOF vs molarity solubility of the complex in CO2 indicates that little catalyst
and is shown in Figure 12. The apparent reaction rate will partition out of the IL phase during the reactions. Wagner
increases with increasing molarity as one would expect as et al.81 found similar solubilities for TPP in supercritical CO2.
shown by the dotted line. In this case, the highest molarity Thus, the ligands will have 3 orders of magnitude more
occurs at the lower pressures. However, as the volume solubility in the CO2 phase than the Rh complex. For the
expansion is relatively small and linear with pressure, the biphasic IL/CO2 system, selective partitioning may be an issue
dilution effect on reaction rate would also be relatively small at the higher pressures, but selective extraction of the excess
and linear as seen by the shallow slope of the higher molarity ligands (here Rh:TPP ) 1:4) would actually increase the
(lowest pressure) points. However, after approximately 120 turnover frequency not decrease it. In addition, the conditions
bar, a dramatic decrease is observed. that would induce catalyst partitioning would simultaneously
The concentration plotted in Figure 12 assumes that all of partition the 1-octene into the CO2 phase. Therefore, catalyst
the 1-octene is in the catalytic IL phase. However, the reactant, partitioning is not believed to have much of an effect in the
1-octene, will partition between the two phases depending on observed reaction trends.
the pressure. The pressure of the mixture critical point of the Thus, two major regions of behavior exist for the reaction
reactant and CO2 indicates a region of complete solubility/ rates with an increase in pressure: dilution of the reactant (from
miscible. As shown in Table 7, this point of miscibility with ∼0 bar CO2 to 100 bar total pressure) and partitioning
CO2 is the exact point (temperature and pressure) for the mixture (extraction) of the reactant from the IL phase. As shown for
of the reactant and product with the IL present. This point is constant loading of the reactant, 1-octene, CO2 pressure would
 Ind. Eng. Chem. Res., Vol. 48, No. 9, 2009 4263
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