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J. of Supercritical Fluids 43 (2008) 421429
Phase behavior of 1,3,5-tri-tert-butylbenzenecarbon
dioxide binary system
Cerag Dilek, Charles W. Manke

, Esin Gulari
Department of Chemical Engineering and Material Science, Wayne State University, Detroit, MI 48202, USA
Received 16 February 2007; received in revised form 13 July 2007; accepted 20 July 2007
Abstract
1,3,5-tri-tert-butylbenzene (TTBB) is solid at ambient conditions, and has substantial solubility in liquid and supercritical carbon dioxide. We
present the phase behavior of TTBBCO
2
binary system at temperatures between 298 and 328 K and at pressures up to 20 MPa. Phase diagrams
showing the liquidvapor, solidliquid and solidvapor equilibrium envelopes are constructed by pressurevolumetemperature measurements in
a variable-volume sapphire cell. TTBB is highly soluble in CO
2
over a wide range of compositions. Single-phase states are achieved at moderate
pressures, even with very high TTBBconcentrations. For example, at 328 K, a binary systemcontaining TTBBat a concentration of 95%by weight
forms a single-phase above 2.04 MPa. TTBB exhibits a signicant melting-point depression in the presence of CO
2
, 45 K at 3.11 MPa, where the
normal melting point of 343 K is reduced to 298 K. With its high solubility in carbon dioxide, TTBB has potential uses as a binder or template in
materials forming processes using dense carbon dioxide.
2007 Elsevier B.V. All rights reserved.
Keywords: Solidliquidvapor equilibrium; Liquidvapor equilibrium; Pressure induced crystallization; Melting-point depression; Isothermal compressibility
1. Introduction
In sand casting and powder injection molding of metal
and ceramic parts, binders used in the molding processes are
removed by methods such as solvent extraction, combustion,
thermal and catalytic debinding. These binder removal methods
produce signicant amounts of solid and liquid wastes, as well as
air pollutants [1]. Therefore innovations in material forming pro-
cesses using dense gas and supercritical CO
2
(scCO
2
) for binder
extraction and recovery have great potential to improve envi-
ronmental problems associated with traditional binder removal
processes [26].
Compounds that are solid at ambient temperature and are
soluble in dense carbon dioxide have potential uses in casting
and molding processes as CO
2
-extractable binders and tem-
plates. For designing a supercritical CO
2
extraction process,
solubility and phase behavior studies are needed to determine
the technical and economic feasibility of the process, and to
dene and optimize processing conditions. Solubility and phase

Corresponding author. Tel.: +1 313 577 3849; fax: +1 313 577 3810.
E-mail addresses: cdilek@chbe.gatech.edu (C. Dilek),
cmanke@eng.wayne.edu (C.W. Manke), egulari@ces.clemson.edu
(E. Gulari).
behavior of various materials, includingspeciallydesignedCO
2
-
philic compounds, in near critical and supercritical CO
2
have
been investigated extensively [714]. As a category of possible
binder materials, sugar acetates are solids at room temperature,
and have high solubilities in dense carbon dioxide, which is
attributed to the Lewis acidbase interaction between CO
2
and
the carbonyl group [1518]. We recently investigated the phase
behavior of -d-galactose pentaacetate with CO
2
at tempera-
tures and pressures representative of possible binder extraction
processes [19].
Here, we continue our investigationof carbondioxide-soluble
solids for possible binder candidates with a symmetrical tri-
alkylbenzene, 1,3,5-tri-tert-butylbenzene (TTBB), the structure
of which is shown in Fig. 1. In our preliminary studies, we
observed high solubility of TTBB in carbon dioxide. In the
literature, early studies on TTBB include its synthesis, spec-
tral characteristics, physical properties and its reactions with
other components yielding higher molecular weight hydrocar-
bons and other derivatives [2025]. Later studies investigate
different methods of synthesis, its reactions with metal ions and
its physical and thermochemical properties [2630]. It is inter-
esting to note that one of the TTBB synthesis methods involves
palladium-catalyzed cyclotrimerization of tert-butylacteylene in
supercritical carbon dioxide in the presence of MeOH [31].
0896-8446/$ see front matter 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.supu.2007.07.009
422 C. Dilek et al. / J. of Supercritical Fluids 43 (2008) 421429
Fig. 1. 1,3,5-tri-tert-butylbenzene.
This study investigates the phase behavior of the TTBBCO
2
binary system to determine the solubility of TTBB in CO
2
and to construct the phase diagrams of the binary system
over a range of temperatures and pressures covering the
liquidvapor, solidvapor, and solidliquid equilibrium regions
and solidliquidvapor equilibrium line over the full concentra-
tion range.
2. Experimental
2.1. Materials
1,3,5-tri-tert-butylbenzene (TTBB), (SigmaAldrich Co.,
97% purity, M
W
=246.43 and T
m
=343 K) is used as-received
without further purication in phase behavior experiments. Car-
bon dioxide is obtained from Airgas with purity of 99.9%.
2.2. Experimental equipment
Phase equilibrium measurements of the TTBBCO
2
binary
system are performed in a high-pressure, variable-volume sap-
Fig. 2. Experimental apparatus for PVT measurements.
phire cell enclosed in a cabinet-style temperature controlled air
bath (see Fig. 2), which was described in our previous -d-
galactose pentaacetateCO
2
phase behavior study [19]. In the
TTBBCO
2
experiments reported here, a model 260D, Tele-
dyne ISCO pump is used to directly inject measured amounts
of liquid CO
2
into the sample chamber. The temperature and
pressure of the ISCO pump reservoir are measured to within
0.1

C and 0.05 MPa.

2.3. Experimental procedure
2.3.1. Sample loading
The sapphire cell is loaded with a weighed amount of TTBB,
before it is sealed and assembled in the air bath. The cell with
TTBB in place is repeatedly evacuated and ushed with CO
2
at
atmospheric pressure to purge air from the system. A specied
volume of liquid CO
2
is then injected into the cell to achieve
the desired overall mass concentration of TTBB in the sam-
ple. The volume of liquid CO
2
to be injected, corresponding
to the desired mass of CO
2
, is determined from the density of
carbon dioxide at the steady temperature and pressure of the
ISCO pump. Densities of pure carbon dioxide are determined
by reference uid properties (REFPROP) software by National
Institute of Standards and Technology (NIST) which uses Span
and Wagner EoS for CO
2
[32]. The mass of CO
2
injected by
the ISCO pump is controlled to within an accuracy of 0.3%,
giving overall sample compositions to within this accuracy.
2.3.2. Phase behavior measurements
The solidliquidvapor equilibrium curve, and the
vaporliquid equilibrium and the solidliquid equilibrium
boundaries are constructed to dene the regions of the
TTBBCO
2
phase diagram at xed temperature. The upper
boundaries of the liquidvapor envelope are determined by dew
and bubble-point measurements, using the procedures described
in our previous study of -d-galactose pentaacetateCO
2
binary
system phase behavior [19]. Dew points are detected by visual
turbidity measurements, whereas bubble points are determined
from pressurevolume measurements. Visual turbidity mea-
surements are also used to detect some points on the LV
boundary near critical mixture compositions. Fig. 3 shows the
PV plot of a typical compression experiment for determining
the bubble point. The discontinuity in the system compress-
ibility corresponds to the phase transition from a liquidvapor
phase equilibrium to a single-phase.
Solidliquidvapor equilibrium (SLV) is measured by
slow depressurization experiments while maintaining the
isothermal conditions. The depressurization is started at an over-
all composition point within the liquidvapor (LV) envelope,
and the pressure of the system is slowly decreased until crys-
tallization is observed. The pressure measured at the onset of
crystallization denes the pressure of the solidliquidvapor
equilibrium at that temperature, and is equal to the pressure at
which pure TTBB melts in the presence of CO
2
. This pressure
is independent of the overall composition, and the SLV pres-
sures measured at constant temperature and at different overall
concentrations form a horizontal SLV equilibrium line on a
C. Dilek et al. / J. of Supercritical Fluids 43 (2008) 421429 423
Fig. 3. Pressurevolume plot for bubble-point determination of 86 wt%of 1,3,5-
tri-tert-butylbenzene at 308 K.
Px diagram. Repetition of these measurements demonstrates
that the pressure at the onset of crystallization can be measured
to within a standard deviation of 0.2 MPa. At high TTBB con-
centrations (>85% by weight) crystallization is also observed
during the pressurization of the system above the LV bound-
ary. The nucleating crystals look like needles and disappear upon
depressurizing the system. To dene the solidliquid equilib-
rium envelope corresponding to this region, the crystallization
pressures are measured by slow, isothermal compression of the
single-phase binary systems. The details of the experiments for
the construction of the solidliquid equilibrium boundary are
described in Dileks PhD dissertation [33].
2.3.3. Density measurements at dew and bubble points
Prior to the phase behavior experiments, the initial height of
the piston is established and the corresponding total volume of
the cell is measured. The density of the system at the dew point
is determined from the total mass of the loading and the piston
height displacement, which is proportional to the change of the
system volume, neglecting the volume of the nucleating phase.
The density of the system at the bubble point is determined
directly from the system volume at the bubble point (See Fig. 3)
and the total mass of the system. These densities are determined
within 2% accuracy, which includes the accuracy in volume
calculation due to the piston height reading, and the accuracy of
the system mass measurement.
3. Results and discussion
The phase behavior of the 1,3,5-tri-tert-butylbenzenecarbon
dioxide binary system at high pressures is studied in a temper-
ature range of 298328 K by dening the solidliquidvapor
(SLV) equilibrium line, and liquidvapor equilibrium (LV),
solidliquid equilibrium (SL) and solidvapor equilibrium
(SV) envelopes. The phase diagrams, constructed as pressure
versus concentration (Px) plots at 298, 308, 318, and 328 K,
are shown in Figs. 47, respectively. The corresponding tem-
Fig. 4. Pressure-concentration plot of 1,3,5-tri-tert-butylbenzeneCO
2
binary
system phase diagram at 298 K. () Liquidvapor equilibrium boundary; ()
solidliquid equilibrium boundary; () solidliquidvapor equilibrium line.
Solid curves are trend lines. Estimated error bars are comparable to the size
of the symbols.
perature, pressure and composition data of the phase diagrams
are given in Table A1 in the appendix. Within the temperature
range investigated, the SV envelope is separated from the LV
envelope by the measured SLV equilibrium line as seen in
Figs. 47. The LV region is separated from the single-liquid or
uid phase region by an LVequilibriumboundary, constructed
from the measured dew points and bubble points. (At temper-
atures below the critical temperature of CO
2
, the single-phase
Fig. 5. Pressureconcentration plot of 1,3,5-tri-tert-butylbenzeneCO
2
binary
system phase diagram at 308 K. () Dew point on the liquidvapor equilib-
rium boundary; () bubble points on the liquidvapor equilibrium boundary;
() solidliquid equilibriumboundary; () solidliquidvapor equilibriumline.
Estimated error bars are comparable to the size of the symbols. Solid curves are
the trend lines.
424 C. Dilek et al. / J. of Supercritical Fluids 43 (2008) 421429
Fig. 6. Pressure-concentration plot of 1,3,5-tri-tert-butylbenzeneCO
2
binary
systemphase diagramat 318 K. () Dewpoints on the liquidvapor equilibrium
boundary; ( ) near-critical points on the liquidvapor equilibrium boundary
measured by the turbidity method; () bubble points on the liquidvapor equilib-
rium boundary; () solidliquid equilibrium boundary; () solidliquidvapor
equilibriumline. Estimated error bars are comparable to the size of the symbols.
Solid curves are the trend lines.
region is designated as liquid phase, while at temperatures above
the critical temperature of CO
2
, the single-upper-phase region is
designated as uid phase). The SLenvelope and the single-uid
phase regions are separatedfromeachother bythe measuredSL
equilibrium boundary.
Fig. 7. Pressureconcentration plot of 1,3,5-tri-tert-butylbenzeneCO
2
binary
systemphase diagramat 328 K. () Dewpoints on the liquidvapor equilibrium
boundary; ( ) near-critical points on the liquidvapor equilibrium boundary
measured by the turbidity method; () bubble points on the liquidvapor equilib-
rium boundary; () solidliquid equilibrium boundary; () solidliquidvapor
equilibriumline. Estimated error bars are comparable to the size of the symbols.
Solid curves are the trend lines.
At 298 K, the LV boundary is determined by bubble-point
measurements at eight different concentrations from 0.02 to
0.85 wt fraction of TTBB (Fig. 4). The bubble-point measure-
ments yield an LV equilibrium boundary wherein pressure
decreases monotonically, from 6.8 to 3.1 MPa, with increasing
TTBB concentration. Above the LV curve, the binary system
exists as a single-liquid phase. Since 298 K is less than the crit-
ical temperature of carbon dioxide, the LV curve intersects
the pressure axis at the vapor pressure of pure carbon diox-
ide. At 298 K, the SLV equilibrium pressure is measured as
3.1 0.16 MPa, at 0.38 and 0.72 wt fraction of TTBB in the
binary system, dening a horizontal SLV equilibrium line
that forms the lower boundary of the liquidvapor envelope.
Below the SLV equilibrium line, TTBB exists as a pure solid.
While the normal melting point of pure TTBB is 346 K, TTBB
melts at 298 K in the presence of CO
2
at 3.1 MPa, yielding a
48 Kdepression of the normal melting point. This melting-point
depression is caused by the decrease in the chemical potential of
TTBBin the liquid phase due to the dissolved CO
2
in TTBB. We
also observed signicant melting-point depressions in our previ-
ous study of -d-galactose pentaacetateCO
2
system (>100 K)
[19]. Volatile solids exhibit a continuous dew point and subli-
mation curve, as described in Refs. [34,18]. The vapor pressure
of TTBB is negligible compared to the pressures of the phase
equilibria measurements discussed here (at its melting point,
343 K, the vapor pressure of TTBB is 8 10
5
MPa, see Ref.
[29]). Therefore we do not measure the sublimation of TTBB in
the presence of CO
2
, and the phase diagrams do not include the
sublimation curve.
At 298 K, the bubble-point curve intersects the SLV line
and the SL equilibrium boundary at 0.91 wt fraction of TTBB.
The SL equilibrium boundary represents the solidliquid
phase-separation pressure as a function of concentration, when
TTBB-rich single-phase binary systems are compressed. A
small decrease in the concentration of TTBB increases the
solidliquid phase separation pressure signicantly. At 0.86 and
0.87 wt fraction of TTBB, crystal nucleation is observed at pres-
sures 15.2 and 13.5 MPa, respectively. These points dene the
solidliquidenvelope boundaryinFig. 4. (Similar crystallization
of naphthalene inCO
2
has beenreportedat temperature andpres-
sure ranges of 308318 and 820 MPa, respectively [3537].)
Overall, our measurements at 298 K show that TTBB exhibits
very high solubility, even at a temperature belowthe critical tem-
perature of carbon dioxide. The high solubility of TTBB in CO
2
is attributed to the low cohesive energy density of TTBB and
a Lewis acidbase interaction between CO
2
and TTBB, where
CO
2
is acting as a weak acid and TTBBis acting as a weak base.
These measurements demonstrate that the solubility of TTBB
in scCO
2
would be suitable for use as a CO
2
-extractable binder
material, and possibly in other supercritical-uid-aided materi-
als processing operations such as CO
2
-assisted pore inducers for
the production of porous materials [38].
We also studied the phase behavior of TTBBCO
2
at tem-
peratures above the critical temperature of carbon dioxide. The
phase diagrams for TTBBCO
2
at 308 K, 318 K, and 328 K
show regions similar to Fig. 4. Unlike Fig. 4, however, the LV
curves for these temperatures exhibit maxima corresponding
C. Dilek et al. / J. of Supercritical Fluids 43 (2008) 421429 425
to mixture critical points. Experimentally, both dew point and
bubble-point measurements are necessary to construct the full
LVequilibriumboundary. The pressure and composition range
of the LV envelope expands with increasing temperature. The
bubble-point curve and the SLVline intersect at higher TTBB
concentrations with increasing temperature. The TTBBconcen-
tration at this intersection is the concentration of the TTBB-rich
liquid which forms at the SLV pressure. This concentration
increases from0.89 to 0.97 when the temperature increases from
298 to 328 K. The pressure and composition range of the SL
envelope shrinks with increasing temperature, because TTBB
has higher solubility in CO
2
, and the SL boundary is shifted
to higher TTBB concentrations. As temperature increases, the
slope of the SL equilibrium boundary becomes steeper, indi-
cating that the crystallization is less sensitive to pressure.
The mixture critical point exists at each temperature where
the saturatedvapor curve intersects the saturatedliquidcurve and
corresponds to the maximum pressure of the vaporliquid curve
[34]. In principle, the mixture critical points of the TTBBCO
2
system at 308, 318 and 328 K can be estimated from the max-
ima of the vaporliquid curve. However at 308 and 318 K the
vaporliquid curves form relatively at domes, and the critical
mixture compositions cannot be estimated accurately. At 328 K,
the critical dome exhibits greater curvature, and the mixture crit-
ical point appears to occur at about 12.6 MPa and 0.26 0.05
TTBB wt fraction.
The SLV lines in Figs. 47 represent conditions, where
TTBBCO
2
binary systems form a liquid phase in equilibrium
with solid and vapor phases below 343 K, which is the normal
melting temperature of pure TTBB. Higher binary system pres-
sure increases the amount of dissolved CO
2
in liquid TTBB,
generating a greater melting temperature depression. The melt-
ing temperature depression of TTBB is presented in Fig. 8, as a
Fig. 8. Melting-point depression of TTBB as a function of CO
2
concentration
dissolved in the liquid TTBB. Numerical values for melting point concentrations
are given in Table 1.
Table 1
Compositions of CO
2
-saturated liquids in equilibrium with solid TTBB at melt-
ing temperatures below the normal melting point
P (MPa) T
m
(K) x
CO
2
wt fraction
0 343 0
1.56 328 0.035
2.28 318 0.054
2.83 308 0.083
3.11 298 0.11
The values for x
CO
2
reported here are obtained by constructing second-order
polynomial curves to t the measured bubble points and then solving for the
compositions where these bubble-point curves intersect the SLV lines.
function of CO
2
dissolved in TTBB. The concentrations of CO
2
dissolved in TTBB at various melting temperatures are deter-
mined from the intersection of the LV and SLV curves on
the Px phase diagrams of the binary system. The melting-point
depression curve in Fig. 8 intersects the temperature axis at the
normal melting point of TTBB. Table 1 lists the composition
of CO
2
dissolved in TTBB and the system pressure required
to liquefy TTBB at the corresponding temperature. An increase
in pressure from 1.6 to 3.1 MPa decreases the melting point of
TTBB from 328 to 298 K, while the weight fraction of CO
2
dissolved in TTBB increases from 0.027 to 0.095.
The TTBBCO
2
saturated liquid densities at the bubble
points at 298 K, and the saturated vapor and the liquid densities
at the dewand the bubble points at 308328 Kare determined by
dividing the sample weight by the measured volume. Table A1
in the appendix reports these densities along the LV curves.
The solution densities are also measured during the isothermal
compression of the single-phase binary system. Single-phase
liquid and uid densities along with the corresponding system
concentration, temperature and pressure are listed in Table A2
in the appendix.
Fromthe pressure versus volume data of the isothermal com-
pressions performed during the bubble-point measurements, the
isothermal compressibility of the single-phase system can be
calculated using Eq. (1), where K
t
is the isothermal compress-
ibility and Vand Pare the volume and the pressure of the system,
respectively. dV/dP is the slope of the compression isotherms in
the single-phase region.
K
t
=
1
V
dV
dP
(1)
The isothermal compressibility (K
t
) of the single-phase binary
system at four temperatures is calculated at 9 MPa to investi-
gate the dependence of K
t
on system temperature and TTBB
concentration. (This comparison is performed at 9 MPa because
most of the bubble-point constructions have a corresponding
measured volume at this pressure.) Fig. 9 shows the isothermal
compressibility as a function of concentration at various tem-
peratures at 9 MPa. Isothermal compressibility values for pure
CO
2
are calculated from the SpanWagner equation of state for
CO
2
. Dashed trend lines are constructed to connect the experi-
mentally determined K
t
values for CO
2
TTBBmixtures to those
of pure CO
2
. The isothermal compressibility falls precipitously
from K
t
of pure CO
2
as TTBB is added to CO
2
. Above TTBB
426 C. Dilek et al. / J. of Supercritical Fluids 43 (2008) 421429
Fig. 9. Isothermal compressibility of 1,3,5-tri-tert-butylbenzeneCO
2
at 9 MPa
vs. wt fraction of 1,3,5-tri-tert-butylbenzene in binary system at () 298 K, ()
308 K, () 318 K, and () 328 K. Solid curves are the trend lines of the measured
points, dashed curves are unmeasured sections of the plots, which connect the
measured points to K
t
values for pure CO
2
.
concentrations of 60%by wt, K
t
reaches a plateau value of about
0.003 MPa
1
.
4. Conclusions
Compounds that are solid at ambient temperature and
are soluble in dense carbon dioxide have potential uses
in casting and molding processes as CO
2
-extractable
binders and templates. In this work, we investigate the
phase behavior of a highly carbon dioxide-soluble binder-
candidate 1,3,5-tri-tert-butylbenzene and carbon dioxide
binary system by pressurevolumetemperature measurements.
Pressurecomposition diagrams at constant temperature are
constructed for the binary system mapping the solidvapor,
liquidvapor, and solidliquid regions. TTBB is highly soluble
in CO
2
, forming single-uid phases containing up to 90 +wt%
TTBB at moderate pressures, which makes it suitable for the
CO
2
-extractable binder applications discussed above. The LV
equilibriumboundaries separating the single-phase regions from
the vaporliquid equilibrium envelopes are determined by dew-
point and bubble-point measurements at various temperatures.
The pressure and composition range of the LV envelope
expands with increasing temperature, and the maxima of the
LV curve shifts to higher pressures with increasing tempera-
ture. The pressure and composition range of the SL envelope
shrinks with increasing temperature, because solubility of TTBB
in CO
2
increases, causing the SL boundary to shift to higher
TTBB concentrations.
TTBB exhibits melting-point depression in the presence of
CO
2
. An increase in pressure from 1.6 to 3.1 MPa decreases the
melting point of TTBB from 328 to 298 K, while the weight
fraction of CO
2
dissolved in TTBB increases from 0.027 to
0.095.
The isothermal compressibility of the binary system, K
t
in
the single-phase region is determined from the pressure vol-
ume scans during the bubble-point measurements at 9 MPa, a
pressure at which the bubble-point constructions have a cor-
responding measured volume. The K
t
values fall precipitously
from K
t
of pure CO
2
as TTBB is added, and above TTBB con-
centrations of 60% by wt, K
t
reaches a plateau value of about
0.003 MPa
1
.
Acknowledgements
The authors acknowledge Roger Marentis of Supercritical
Solutions for suggesting tertbutylated compounds as extraordi-
narily soluble materials in scCO
2
. We also thank Bob Enick,
University of Pittsburgh, Jeffery Potoff and Sandro da Rocha,
Wayne State University, Mark Thies, Clemson University, and
Richard Elliott of University of Akron, for their useful dis-
cussions and suggestions. The authors gratefully acknowledge
support from the U.S. Environmental Protection Agency, Grant
EPA-RD-83150401-1.
Appendix A
Numerical values for the phase behavior data reported in the
text are given in the tables (Tables A1 and A2).
Table A1
Temperature, pressure and concentration data of the VL equilibrium bound-
ary (dew and bubble points), SLV and SL equilibrium boundary of the
TTBBCO
2
binary system. The LVequilibriumboundary data includes the sat-
uration density of the TTBBCO2 binary systemat the corresponding conditions
298 K 308 K
TTBB wt
fraction
P (MPa) (g/cm
3
) TTBB wt
fraction
P (MPa) (g/cm
3
)
Liquidvapor equilibrium boundary (dewbubble points)
0.02 6.85 0.76 0.02 8.35 0.52
0.10 6.58 0.74 0.10 8.44 0.69
0.21 6.83 0.81 0.21 8.41 0.74
0.40 6.62 0.83 0.40 8.26 0.81
0.49 6.25 0.83 0.49 7.75 0.82
0.59 5.97 0.83 0.59 7.24 0.82
0.70 5.36 0.83 0.70 6.36 0.82
0.85 3.62 0.82 0.86 4.01 0.77
0.90 3.14 0.80
318 K 328 K
TTBB wt
fraction
P (MPa) (g/cm
3
) TTBB wt
fraction
P (MPa) (g/cm
3
)
Liquidvapor equilibrium boundary (dewbubble points)
0.02 9.85 0.44 0.02 11.35 0.41
0.10 10.30 0.62 0.10 12.17 0.60
0.21 10.29 0.65 0.21 12.17 0.64
0.40 10.07 0.74 0.40 12.34 0.73
0.49 9.43 0.80 0.49 11.20 0.78
0.59 8.62 0.79 0.59 10.11 0.78
0.70 7.47 0.80 0.70 8.62 0.78
0.86 4.45 0.80 0.86 5.02 0.74
0.93 2.69 0.78 0.95 2.04 0.78
C. Dilek et al. / J. of Supercritical Fluids 43 (2008) 421429 427
Table A1 (Continued )
298 K 308 K
TTBB wt fraction P (MPa) TTBB wt fraction P (MPa)
Solidliquidvapor equilibrium
0.38 3.11 0.38 2.83
0.72 3.11 0.72 2.83
318 K 328 K
TTBB wt fraction P (MPa) TTBB wt fraction P (MPa)
Solidliquidvapor equilibrium
0.38 2.28 0.38 1.56
0.72 2.28 0.72 1.56
298 K 308 K
TTBB wt fraction P (MPa) TTBB wt fraction P (MPa)
Solidliquid equilibrium boundary
0.86 15.20 0.89 18.09
0.87 13.54 0.90 9.05
318 K 328 K
TTBB wt fraction P (MPa) TTBB wt fraction P (MPa)
Solidliquid equilibrium boundary
0.92 16.15 0.94 19.19
0.93 10.76 0.95 10.48
Table A2
Single-phase density of the TTBBCO
2
binary system at various temperatures and pressures
298 K
TTBB wt fraction 0.02 TTBB wt fraction 0.1 TTBB wt fraction 0.21 TTBB wt fraction 0.40
P (MPa) (g/cm
3
) P (MPa) (g/cm
3
) P (MPa) (g/cm
3
) P (MPa) (g/cm
3
)
6.88 0.69 6.99 0.72 7.50 0.80 6.81 0.82
7.28 0.75 7.67 0.75 8.69 0.82 7.97 0.83
9.01 0.78 8.71 0.76 10.25 0.83 10.19 0.84
10.19 0.80 10.04 0.78 12.20 0.85 13.05 0.85
11.43 0.81
298 K
TTBB wt fraction 0.49 TTBB wt fraction 0.59 TTBB wt fraction 0.70 TTBB wt fraction 0.85
P (MPa) (g/cm
3
) P (MPa) (g/cm
3
) P (MPa) (g/cm
3
) P (MPa) (g/cm
3
)
6.51 0.81 6.10 0.80 5.48 0.80 4.59 0.81
7.34 0.83 6.44 0.81 5.97 0.82 5.31 0.82
10.45 0.84 6.90 0.82 7.13 0.83 5.95 0.82
13.29 0.85 8.89 0.83 10.58 0.84 7.44 0.82
11.22 0.83 13.89 0.84 8.49 0.82
14.70 0.84 19.46 0.84 10.18 0.83
12.90 0.83
308 K
TTBB wt fraction 0.10 TTBB wt fraction 0.21 TTBB wt fraction 0.40 TTBB wt fraction 0.49
P (MPa) (g/cm
3
) P (MPa) (g/cm
3
) P (MPa) (g/cm
3
) P (MPa) (g/cm
3
)
4.60 0.75 8.55 0.74 8.95 0.81 8.05 0.80
6.20 0.77 8.84 0.75 11.37 0.82 8.28 0.81
9.62 0.78 9.26 0.77 13.77 0.83 9.72 0.82
13.64 0.79 9.71 0.78 15.42 0.84 11.73 0.83
18.78 0.80 13.43 0.83
428 C. Dilek et al. / J. of Supercritical Fluids 43 (2008) 421429
Table A2 (Continued )
308 K
TTBB wt fraction 0.59 TTBB wt fraction 0.70 TTBB wt fraction 0.86 TTBB wt fraction 0.90
P (MPa) (g/cm
3
) P (MPa) (g/cm
3
) P (MPa) (g/cm
3
) P (MPa) (g/cm
3
)
7.68 0.79 6.70 0.80 4.60 0.75 4.50 0.80
8.01 0.81 7.10 0.81 6.20 0.77 5.95 0.81
9.09 0.82 7.66 0.81 9.62 0.78 7.08 0.81
11.14 0.82 8.76 0.82 13.64 0.79 8.50 0.81
14.47 0.83 10.88 0.83 18.78 0.80
16.61 0.83 15.90 0.83
318 K
TTBB wt fraction 0.49 TTBB wt fraction 0.59 TTBB wt fraction 0.70 TTBB wt fraction 0.86
P (MPa) (g/cm
3
) P (MPa) (g/cm
3
) P (MPa) (g/cm
3
) P (MPa) (g/cm
3
)
9.81 0.79 8.83 0.77 8.41 0.79 4.64 0.73
10.52 0.80 9.50 0.78 9.57 0.80 5.36 0.75
11.87 0.81 10.14 0.79 11.13 0.80 6.61 0.76
13.32 0.82 12.03 0.80 13.13 0.81 9.06 0.77
14.17 0.81 15.80 0.81 15.00 0.78
16.43 0.81 19.06 0.78
318 K 328 K
TTBB wt fraction 0.93 TTBB wt fraction 0.49 TTBB wt fraction 0.59 TTBB wt fraction 0.70
P (MPa) (g/cm
3
) P (MPa) (g/cm
3
) P (MPa) (g/cm
3
) P (MPa) (g/cm
3
)
3.22 0.78 11.81 0.78 10.96 0.77 9.09 0.77
5.26 0.79 12.54 0.78 11.91 0.79 9.86 0.78
7.63 0.80 13.26 0.79 13.41 0.79 10.70 0.79
14.92 0.80 15.34 0.80 11.67 0.79
18.20 0.81 14.23 0.80
16.58 0.80
328 K
TTBB wt fraction 0.86 TTBB wt fraction 0.95
P (MPa) (g/cm
3
) P (MPa) (g/cm
3
)
5.09 0.71 2.12 0.76
6.15 0.73 2.81 0.77
6.77 0.75 4.19 0.78
9.47 0.76 6.75 0.79
13.39 0.77 9.70 0.79
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