J.

of Supercritical Fluids 33 (2005) 7–14

High-pressure density and vapor–liquid equilibrium for the binary

systems carbon dioxide–ethanol, carbon dioxide–acetone
and carbon dioxide–dichloromethane
Matteo Stievano, Nicola Elvassore∗
Dipartimento di Principi e Impianti di Ingegneria Chimica, Università di Padova Via Marzolo 9, 35131 Padova, Italy
Received in revised form 5 April 2004; accepted 21 April 2004

Abstract

An apparatus for the measurement of vapor–liquid equilibrium (VLE, P–T–x) data and density of saturated-liquid and high-pressure liquid
phase of compressed gas-organic solvent systems was designed, built and tested. A synthetic method, with recirculation of the liquid phase
through a high-pressure densimeter by a magnetic driven centrifugal pump, was used. The thermodynamic equilibrium was reached in a visual
cell with variable volume ranging between 30 and 60 cm3 . The compositions of the phases were evaluated by external gravimetric method.
The estimated accuracy of the measured data was ±0.02 K for temperature, ±0.05 MPa for pressure, ±0.005 in mole fraction for liquid
compositions and ±0.05 g/L for liquid density. Vapor–liquid equilibrium data and saturated-liquid density were obtained for the following
systems: carbon dioxide–ethanol and carbon dioxide–acetone at 291.15, 303.15, 313.15 and 323.15 K and carbon dioxide–dichloromethane
at 291.15, 303.15 and 311.15 K. For the latter system, high-pressure liquid density data were measured up to 18 MPa. The experimental data
were correlated by both Peng–Robinson and SAFT equation of state. SAFT EOS gives better correlations of vapor–liquid data and accurate
predictions of high-pressure density of the liquid phase.
© 2004 Elsevier B.V. All rights reserved.

Keywords: Experimental data; Vapor–liquid equilibrium; Density; Carbon dioxide; Ethanol; Acetone; Dichloromethane; SAFT

1. Introduction a number of carbon dioxide–organic solvent system are

Supercritical fluid processes are merging as important
alternative to conventional methods in many of fields,
such as extraction, particle micronization, material pro-
cessing, chromatography or crystallization/purification [1].
Equilibrium and volumetric properties of binary mixtures
containing organic solvent and supercritical fluids (espe-
cially carbon dioxide) play an fundamental role in de-
termining the success of many of these applications. In
particular, vapor–liquid equilibria and liquid density are
necessary data for properly design gas antisolvent pre-
cipitation/recrystallization processes. This technique was
successfully applied for production of micro- and nano-
particulate powder for pharmaceutical, biomedical, cos-
metic, alimentary or electronic application [2–4]. Even if
∗ Corresponding author. Tel.: +39 049 827 5469;
fax: +39 049 827 5461.
E-mail address: nicola.elvassore@unipd.it (N. Elvassore).
already reported in open literature [5–9] there is still a
lacking of experimental equilibrium and density data, es-
pecially for dichloromethane, that is one of the most used
solvent for production of poly(lactide acid) and poly(lactide
glicolide) biodegradable micro-particles [4–10]. In addi-
tion, despite density data are important to establish so-
lute precipitation [11] and to determine the swelling and
shrinking regime in the mass transfer simulation [12–13]
of gas anti-solvent process, density data published for car-
bon dioxide–organic solvent binary systems are scarce and
controversy.
In this work, vapor–liquid equilibrium and saturated-liquid
density were measured for two well known systems car-
bon dioxide–ethanol and carbon dioxide–acetone at 291.15,
303.15, 313.15 and 323.15 K. Vapor–liquid equilibrium
and high-pressure liquid density were measured for carbon
dioxide–dichloromethane at 291.15, 303.15 and 311.15 K.
These temperatures are close to that typically used in gas
antisolvent processes [10].

0896-8446/$ – see front matter © 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.supflu.2004.04.003
8 M. Stievano, N. Elvassore / J. of Supercritical Fluids 33 (2005) 7–14
2. Experimental
Ethanol (purity better than 99.8% mass fraction), ace-
tone (purity better than 99.9% mass fraction) and dichloro-
methane (purity better than 99.9% mass fraction) were sup-
plied by Sigma–Aldrich (Milano, Italy). 99.998% purity
CO2 was provided by Sapio (Padova, Italy). The organic
solvent samples were saturated with CO2 by fluxing the gas
at room temperature and pressure for 1 h. They were used
without further purification.
2.1. VLE apparatus
Fig. 1 shows a schematic representation of the VLE appa-
ratus. A vapor–liquid equilibrium (VLE) cell with variable
volume (NWA, Lorrach, Germany) was made of stainless
steel (corresponding to AISI316) and equipped with two
sapphire windows for observing the sample during measure-
ments. O-rings were used to seal the glass windows onto
the stainless steel body of the VLE cell. The rear window
can be moved by an accurate external hydraulic pressuriza-
tion systems. The internal VLE cell volume can be varied
between 60 and 30 cm3 with a precision of 0.05 cm3 .
The apparatus is equipped with a recirculation loop for
the liquid phase in order to ensure both intensive mixing and
measurement of liquid density. Magnetic driven centrifugal
pump, appositely designed for this apparatus, ensures a cir-
culation of about 50 cm3 /min of liquid phase and generated
0.050 kPa hydraulic charge. 1/8 in. stainless steel tubes (Nor-
Fig. 1. Schematic diagram of the apparatus. Broken line contains the thermostated apparatus components.
dival, Erbusco, Italy) were used. In order to eliminate stag-
nant zone and reduce the internal volumes of the recircula-
tion loop special connector was design for the manometer.
Three-way valve (Swagelok, Milan, Italy), located at the
bottom of the apparatus, enables the closure of the recir-
culation loop and to isolate the equilibrium cell during the
sample addition to the VLE cell.
The VLE cell and the recirculation loop were fully im-
mersed in a glass thermostatic vessel of about 0.03 m3 ca-
pacity. Mixing is ensured by a submerge centrifugal pump
with 40 L/min flow rate. The density was measured by a
densimeter (Anton-Paar, Grazz, Austria) placed outside on
the thermostat and connected by well insulated 1/8 in. stain-
less steel tube. The densimeter is equipped with an internal
temperature sensor.
The magnetic pump was designed and made by the me-
chanical laboratory of Department of Chemical Engineering
of University of Padova, Italy.
2.2. Measurement and control of temperature,
pressure and density
The VLE cell and the recirculation loop was immersed in
a thermostatic bath that enabled the temperature to be sta-
bilized within ±0.01 K throughout the measurements. Tem-
perature control was achieved by a PID-controller (Lauda,
Genova, Italy) governing a heating element immersed in the
thermostatic bath. Temperature was measured by means of
a calibrated PT100
resistance thermometer connected to a
 M. Stievano, N. Elvassore / J. of Supercritical Fluids 33 (2005) 7–14
electronic transducer. The overall accuracy of the tempera-
ture measurement was estimated to be within ±0.02 K.
Pressure was measured using a membrane transducer
(Endress-Hauser, Rheinh, Germany) with a precision of
0.5% FS. The pressure transducer was calibrated using
dead-weight gauge. The overall accuracy of the pressure
measurement was estimated to be within ±0.08 MPa includ-
ing errors due to pressure gauge and pressure fluctuation
during VLE measurements.
Density was measured using a vibrating tube densime-
ter. The difference between the temperature recorded in the
densimeter and that of the VLE cell was lower than 1 K.
The overall accuracy of the density measurement including
errors due to temperature fluctuation was estimated to be
within ±0.05 g/L.
Video acquisition system allows to visualize on external
video the phase transition in the VLE cell. Data acquisition
system (IRS, Padova, Italy) record on personal computer
pressure, temperature and video signal.
2.3. Gravimetric composition measurements
Liquid sample were prepared in glass syringe (Vetrotec-
nica, Padova, Italy) and they were weighted with a standard
analytical balance of 110 g capacity and 0.0001 g resolu-
tion (Sartorius, Padova, Italy). Gas samples were prepared
in 75 cm3 stainless steel cylinder with a low-weight me-
tering valve. The overall tare weight of the cylinder, valve
and connectors was 398 g and the maximum pressure
was 12 MPa. This characteristics enable sample prepara-
tion by weighing with a standard analytical balance of
500 g capacity and 0.001 g resolution (Gibertini, Padova,
Italy).
The liquid samples were first added into the VLE cell pre-
viously filled with CO2 at room pressure and temperature.
The weight was recorder and the evaluated instrumental un-
certainty in liquid sample added to the cell was ±0.0003 g.
The gas samples were added into the cell connecting the
cylinder with the apparatus inline. The amount of the gas
added in the apparatus was measured by weighting the gas
cylinder before and after the loading operation. The gas,
remained between the valve of the cylinder and the valve
of the apparatus inline, was volumetrically measured in a
1 cm3 resolution graduate glass cylinder filled with water.
The final amount of gas added in the VLE cell was ob-
tained as difference between the gas introduced in the ap-
paratus and the one remained in the inline section. The
amount of gas introduced in the VLE cell was varied by
controlling the difference between the temperature of the
VLE cell and the gas cylinder and the charging time. The
evaluated uncertainty in gas sample added to the cell was
±0.005 g.
The estimated accuracy of mixture composition data is
usually better then ±0.001 in mole fraction. In the worst
cases, depending on the composition the mixture, accuracy
of mixture composition data is ±0.005.
9
2.4. Method of VLE measurements
The samples were loaded after the cleaning procedure.
The recirculation loop and the magnetic driven pump were
evacuated for 12 h. The VLE cell, that cannot withstand with
vacuum, was purged with 10 cm3 /min CO2 flow rate for 12 h.
The entire apparatus was filled and discharged for five times
with CO2 at CO2 -saturated pressure at ambient condition.
The samples were added to the cell in a desiderated amount
in order to obtain completely liquid-filled apparatus reducing
the volume of the VLE cell.
Expanding the volume of the liquid-filled cell, pressure,
temperature, window displacement (by a calibrated device
with 0.1 mm precision) and density were reordered. The
density and window displacement versus pressure varia-
tion were analyzed. Because vapor and liquid phases have
different compressibilities, the slope of curves should sig-
nificantly changes at the VLE equilibrium point. The equi-
librium point can be evaluated intersecting two gas-like and
liquid-like correlations obtained for either density–pressure
or window displacement-pressure profile reported. These
results are confirmed by visual observation of small vapor
bubble formation in the VLE cell at equilibrium conditions.
In order to evaluate the accuracy of the method, the mea-
surements were repeated decreasing and increasing VLE
cell volume; same results were obtained. However, the
method that requires to expand the liquid phase guarantee
a better homogeneity and mixing in the VLE apparatus.
In this work, to speed up the measurement, the equi-
librium conditions were obtained expanding liquid-filled
VLE cell and using both density–pressure profile anal-
ysis and visual observations. Temperature, pressure and
saturated-liquid density were recorded at equilibrium con-
dition. High-pressure liquid density was measure increasing
the pressure of the system by reducing the VLE cell volume
at pressure over mixture bubble point.
3. Modelling
The binary vapor–liquid equilibria was correlated by a
simple cubic Peng–Robinson (PR) equation of state (EOS)
and using a more physical based statistical associating fluid
theory (SAFT). In particular, a modification of original
SAFT by Huang and Radosz [14–16] presented by Pfohl
Table 1
SAFT EOS pure-component segment parameters
CO2 Ethanol Acetone DCM
u0 /k (K) 216.08 213.87 209.50 218.13
v00 (mL/mol) 13.578 12.449 12.320 13.732
m 1.417 2.438 2.282 2.572
ǫA /k (K) – 2791.1 – –
102 kA – 2.5819 – –
k is the Boltzmann’s constant.
10 M. Stievano, N. Elvassore / J. of Supercritical Fluids 33 (2005) 7–14

and Brunner [17] was used. Pure component parameters for Table 3
organic solvents and CO2 used in this work are reported in P–T–x and saturated-liquid density experimental data for the carbon
dioxide–ethanol system
Table 1 for SAFT EOS only.
For our systems two interaction parameters, kij and λij , T (K) xCO2 P (MPa) ρ (g/cm3)
were used for both equation of states. Quadratic mixing rule 291.15 0.241 3.30 0.82852
was used for interaction parameter and linear mixing rule 0.364 4.18 0.84377
was used for volume parameter [17]. The binary interaction 0.486 4.73 0.85556
parameters were obtained by fitting both EOSs to our exper- 303.15 0.241 3.60 0.81139
imental data by minimizing the relative pressure deviation 0.364 4.67 0.82152
objective function: 0.486 5.62 0.82870
Np   313.15 0.241 4.38 0.80012
P 2

0.364 5.89 0.81010


obf = δ (1)
P 0.486 6.96 0.81721
i=1
323.15 0.241 4.93 0.78921
where Np is the number of isothermal data points considered 0.364 6.79 0.79832
and the residuals on pressure δ(P/P) are given by: 0.486 8.11 0.80404
 
P Pcalculated
δ = − 1. (2)
P Pexperimental
Table 4
The values of saturated-liquid density and high-pressure P–T–x and saturated-liquid density experimental data for the carbon
liquid density are predicted using the interaction parameters dioxide–acetone system
obtained from the VLE fitting. All calculation reported in T (K) xCO2 P (MPa) ρ (g/cm3)
this work were performed using a “Phase Equilibria” soft-
291.15 0.120 0.70 0.80441
ware (Technical University of Hamburg-Harbug, Germany).
– 0.212 1.12 0.82077
– 0.364 1.86 0.83888
0.530 2.78 0.85815
4. Results and discussion
303.15 0.120 0.73 0.79203
– 0.212 1.28 0.80536
Table 2 reports the summary of statistical errors and inter- – 0.364 2.25 0.82437
action parameter values used for both vapor–liquid equilibria 0.530 3.39 0.84011
and saturated-liquid density calculation performed by SAFT 313.15 0.120 0.78 0.77853
EOS. The PR EOS does not give satisfactory description of – 0.212 1.48 0.79412
both volumetric and equilibrium properties, especially for – 0.364 2.64 0.80872
associating molecules such as ethanol. – 0.530 3.85 0.82365
Tables 3–5 show the P–T–x and saturated-liquid den- 323.15 0.120 1.06 0.76956
sity experimental values for carbon dioxide–ethanol, car- – 0.212 1.88 0.74760
– 0.364 3.19 0.79540
bon dioxide–acetone and carbon dioxide–dichloromethane.
– 0.530 4.02 0.80931
Table 6 shows high-pressure liquid density experimental

Table 2
Summary of statistical errors and interaction parameters obtained from the fitting of vapor–liquid experimental data and from the prediction of
saturated-liquid density using the SAFT EOS
T (K) Data number P/P (%) |P|P (%) ρ/ρ (%) |ρ|ρ (%) kij λij

Carbon dioxide–ethanol
291.15 3 −0.63 1.2 −0.29 0.5 0.081 0.048
303.15 3 −0.49 1.0 −0.57 1.1 0.070 0.060
313.15 3 −0.43 1.1 −0.65 1.3 0.079 0.058
323.15 3 −0.46 0.9 −0.61 1.2 0.078 0.059
Carbon dioxide–acetone
291.15 4 −0.12 1.5 0.49 0.8 0.041 0.024
303.15 4 −0.01 1.2 0.4 9.7 0.040 0.030
313.15 4 0.23 1.1 0.46 1.0 0.045 0.029
323.15 4 −0.31 0.8 0.82 1.7 0.042 0.029
Carbon dioxide–diclhoromethane
291.15 5 0.36 0.6 −0.57 1.1 0.041 0.024
303.15 5 0.08 0.4 −0.55 1.2 0.040 0.030
311.15 5 −0.01 0.5 −0.71 1.5 0.045 0.029
 M. Stievano, N. Elvassore / J. of Supercritical Fluids 33 (2005) 7–14 11

Table 5
P–T–x and saturated-liquid density experimental data for the carbon
dioxide–dicholoromethane system
T (K) xCO2 P (MPa) ρ (g/cm3)

291.15 0.249 1.94 1.28971

– 0.450 2.99 1.93560
– 0.524 3.38 1.14655
– 0.645 3.95 1.09812
– 0.710 4.33 1.07683
303.15 0.249 2.24 1.27443
– 0.450 3.55 1.17092
– 0.524 4.01 1.13675
– 0.645 4.75 1.06841
– 0.710 5.22 0.96977
311.15 0.249 2.69 1.25653 Fig. 3. Comparison of saturated-liquid density measured in this work for
– 0.450 4.05 1.15127 carbon dioxide–ethanol with literature data: (䊉) this work at 291.15 K;
– 0.524 4.60 1.09989 (䊏) this work at 303.15 K; (䊐) Chang et al. [7] at 298.15 K; (䊊)
– 0.645 5.39 1.04851 Kordikowski et al. [6] at 298.15 K. Line is density prediction at 303.15 K
– 0.710 5.91 1.02581 obtained by SAFT equation of state using interaction parameters reported
in Table 2.

measurements for the carbon dioxide–dicholoromethane
system at 291.15, 303.15 and 311.15 K.
Fig. 2 shows an example of comparison of P–T–x ex-
perimental data measured in this work with those reported
in the literature for carbon dioxide–ethanol system. Our re-
sults shows a good agreement with other experimental data
at the higher temperature. However, for the lowest tempera-
ture data reported in the literature show singular behaviors.
Although our data was measured at 291.15 and 303.15 K,
our results seem to properly reproduce the behavior of the
data of Kordikowski et al. [6]
Fig. 3 that shows a good agreement between the P–T–x
experimental data measured in this work and those reported
in the literature for carbon dioxide–acetone system, con-
firming the reliability of the experimental setup and proce-
dure proposed. The SAFT EOS accurately correlates the ex-
perimental bubble pressure; statistical errors are reported in
Table 2.
Fig. 4 shows a comparison of saturated-liquid density
measured in this work for carbon dioxide–ethanol with liter-
ature data of two different investigator: Chang and coworkers
[6,7]. Although the temperature are not the same, our results
well agree with the density data presented by Kordikowski
et al. [6]. On the other hand, the data from Chang et al. [7]
shows a different and contradictory behaviour for both equi-
librium and volumetric properties. The SAFT EOS gives an
accurate density prediction for both temperature: the density
calculation were performed using the interaction parameters
fitted from bubble curve at same temperature. Statistical er-
rors for all calculation concerning the saturated-liquid den-
sity are reported in Table 2.

Fig. 2. Comparison of our experimental P–T–x measurements with liter-
ature data for carbon dioxide–ethanol: (䊉) in this work at 291.15 K; (䊏)
in this work at 303.15 K; (䉱) in this work at 313.15 K; (䉬) in this work
at 323.15 K; (䊐) Chang et al. [7] at 298.15 K; (䉫) Kordikowski et al.
[6] at 298.16 K; (*) Suzuki et al. [8] at 313.4 K; (+) Jennings et al. [9]
at 314.2 K; (䊊) Gonzalez et al. [5] at 314.45 K; (-) Jennings et al. [9] at
325.2 K. Lines are calculated by SAFT equation of state using interaction
parameters reported in Table 2 at 291.15, 303.15, 313.15 and 323.15 K.
Fig. 4. Comparison of bubble points measured in this work for carbon
dioxide–acetone with literature data: (*) Giacobbe et al. [19] at 303.15 K;
(䊊) Day et al. [20] at 313.13 K; (+) Adrian and Maurer [21] at 313.15 K;
(䊐) Bamberger et al. [22] at 323.2 K; (䊏) in this work at 303.15 K;
(䊉) in this work at 313.15 K; (䉬) in this work at 323.15 K. Lines
are calculated by SAFT equation of state using interaction parameters
reported in Table 2. Lines are calculated by SAFT equation of state using
interaction parameters reported in Table 2 at 303.15, 313.15 and 323.15 K.
12 M. Stievano, N. Elvassore / J. of Supercritical Fluids 33 (2005) 7–14

Table 6
High-pressure liquid density experimental data for the carbon dioxide–dicholoromethane system
xCO2 P (MPa) ρ (g/cm3) P (MPa) ρ (g/cm3) P (MPa) ρ (g/cm3)

T = 291.15 K T = 303.15 K T = 311.15 K

0.249 16.9 1.31108 16.9 1.2984 17.0 1.27995

– 15.1 1.30802 14.9 1.29527 14.8 1.27567
– 13.6 1.3055 12.9 1.29241 13.1 1.27308
– 11.4 1.30185 11.1 1.29002 10.3 1.26892
– 8.58 1.29745 9.21 1.28655 8.59 1.26652
– 6.42 1.2936 6.12 1.28145 6.24 1.26281
– 4.28 1.29079 4.22 1.27841 4.17 1.25914
– 3.21 1.28971 2.68 1.27526 3.32 1.25752
0.450 17.4 1.22504 17.1 1.20531 17.4 1.18713
– 15.3 1.22119 15.1 1.20062 14.9 1.1808
– 13.4 1.21734 13.1 1.19579 12.6 1.17497
– 11.2 1.21275 11.4 1.19177 10.4 1.16933
– 8.2 1.2062 9.55 1.18713 8.8 1.16504
– 5.9 1.20138 6.12 1.17842 7.43 1.16132
– 4.0 1.19679 4.95 1.17533 5.71 1.15659
– 3.2 1.10475 4.15 1.17287 4.44 1.15324
0.524 17.1 1.17902 17.0 1.17428 17.1 1.14072
– 15.3 1.17527 15.0 1.16907 14.8 1.13351
– 13.2 1.17002 13.0 1.16358 13.0 1.12791
– 11.0 1.16485 11.3 1.15876 10.3 1.11903
– 8.5 1.15925 9.38 1.15314 8.66 1.1133
– 7.2 1.15573 6.12 1.14422 7.62 1.10989
– 5.5 1.15128 5.18 1.14106 6.07 1.10471
– 4.1 1.14837 4.52 1.1384 5.06 1.10138
0.645 16.8 1.139 16.64 1.11222 16.9 1.09431
– 15.5 1.13536 14.69 1.10597 14.8 1.08623
– 13.4 1.12918 12.8 1.09917 13.3 1.08086
– 11.2 1.12265 10.91 1.09274 10.2 1.06874
– 9.4 1.11695 8.87 1.08516 8.52 1.06156
– 7.3 1.11016 6.56 1.07644 7.80 1.05846
– 5.1 1.10279 5.63 1.07252 6.42 1.05284
– 4.3 1.09979 4.93 1.06948 5.67 1.04952
0.71 17 1.12097 16.94 1.00954 16.9 1.07468
– 14 1.11187 15.01 1.00387 14.6 1.0659
– 11 1.10208 12.9 0.99769 12.1 1.05587
– 8.67 1.109394 11.23 0.99186 10.0 1.04624
– 6.78 1.08691 9.25 0.98498 8.37 1.03859
– 5.52 1.08204 7.23 0.97706 7.59 1.03465
– 4.99 1.07979 6.32 0.9735 6.79 1.03019
– 4.41 1.07735 5.85 0.97174 6.11 1.02644

Interestingly, Tables 3–5 and Fig. 4 show that the
saturated-liquid density at constant temperature increases
with carbon dioxide molar fraction up to a maximum for
the systems containing acetone and ethanol, whereas, it de-
creases with carbon dioxide molar fraction for the system
containing dichloromethane. The saturated-liquid density
behavior of the carbon dioxide–organic solvent binary mix-
ture is governed by two contrasting phenomena: the liquid
compression due to the high pressure of the system and the
solubilization of the CO2 in the saturated-liquid phase. The
first phenomena is dominant when the CO2 is not highly
soluble in the organic solvent, and in this case, the density of
the saturated-liquid phase raises by increasing the pressure
of the system. On the other hand, when the solubilization
of the CO2 in the saturated-liquid phase is favored, the
value of the saturated-liquid density shift towards the value
of the pure CO2 density. This value is generally lower than
that of organic solvents. However, for all binary systems,
the expansion of the saturated-liquid phase by the carbon
dioxide solubilization predominates at high pressure.
Fig. 5 shows new experimental data at temperature of
291.15 and 303.15 K for carbon dioxide–dicholoromethane
system. These temperature conditions are close to those typ-
ically used in the particle production by gas antisolvent pre-
cipitation. Our results shows a good agreement with experi-
mental data from Gonzalez et al. [5] at 311.15 K. The SAFT
give accurate prediction for all temperatures presented in
Fig. 5.
 M. Stievano, N. Elvassore / J. of Supercritical Fluids 33 (2005) 7–14
Fig. 5. Comparison of bubble points measured in this work for carbon
dioxide–dicholoromethane with literature data: (䉫) Gonzalez et al. [5] at
311.15 K; (䊉) in this work at 291.15 K; (䊏) in this work at 303.15 K;
(䉬) in this work at 311.15 K. Lines are calculated by SAFT equation of
state using interaction parameters reported in Table 2.
Fig. 6. Prediction of high-pressure density data measured in this work for
carbon dioxide–dicholoromethane at different liquid molar fractions and
311.15 K: (䉫) xCO2 = 0.249; (䊊) xCO2 = 0.450; (䊐) xCO2 = 0.524; (+)
xCO2 = 0.645; (*) xCO2 = 0.710. Lines are calculated by SAFT equation
of state using interaction parameters reported in Table 2.
Fig. 6 shows an example of the high-pressure liq-
uid density data measured in this work for carbon
dioxide–dicholoromethane at different molar fractions and
at temperature of 311.15 K. It is possible to note that, in-
creasing the amount of CO2 increases the compressibility of
the carbon dioxide–dicholoromethane mixture. The SAFT
EOS accurately predicts the volumetric behaviour of carbon
dioxide–dicholoromethane liquid mixtures at high pressure.
This results is particularly interesting for rational under-
standing and simulating the mass transfer of gas antisolvent
process, in which the density plays a fundamental role in
determining the solute precipitation [10,12,13].
5. Conclusions
A new experimental setup and procedure to measure
P–T–x data, saturated-liquid density and high-pressure
liquid density for carbon dioxide–organic solvent binary
13
system is proposed. Although some experimental mea-
surements reported in the literature shows controversial
behavior, it was demonstrated that our method stands in
the same range of the experimental measurements ob-
tained by other authors for carbon dioxide–ethanol and
carbon dioxide–acetone systems. Saturated-liquid density
data are presented for carbon dioxide–ethanol and carbon
dioxide–acetone systems. Experimental P–T–x data are pre-
sented for the carbon dioxide–dicholoromethan system at
291.15 and 303.15 K. High-pressure liquid density data for
carbon dioxide–dicholoromethane at different molar frac-
tions at 291.15, 303.15 and 311.15 K are presented. It was
shown that the SAFT EOS fairly correlates bubble curve
and predicts the high-pressure volumetric behaviour of the
carbon dioxide–organic solvent systems.
Acknowledgements
This work was financed by the Italian Ministry for the
University and for Scientific and Technological Research
(MURST) and by the University of Padova. The authors are
grateful to the group of Prof. Brunner (Technical University
of Hamburg-Harbug, Germany) to provide a free copy of
the program “Phase Equilibria” [18].
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