Fluid Phase Equilibria 289 (2010) 72–79

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Fluid Phase Equilibria

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Solubility and density measurements of palmitic acid in supercritical carbon

dioxide + alcohol mixtures
Lars Brandt a,b , Octavio Elizalde-Solis b , Luis A. Galicia-Luna b,∗ ,
Jürgen Gmehling a
a
Carl-von-Ossietzky Universität Oldenburg, Technische Chemie, D-26111 Oldenburg, Germany
b
Laboratorio de Termodinámica, ESIQIE, Instituto Politécnico Nacional, UPALM, Edif. Z, Secc. 6, 1ER piso,
Lindavista, C.P. 07738, México, D.F., Mexico

a r t i c l e i n f o a b s t r a c t

Article history: Solubility data of palmitic acid (hexadecanoic acid) in supercritical carbon dioxide were measured in the
Received 1 August 2009 pressure range from 10 to 25 MPa at temperatures of 313 and 318 K. Densities for this binary mixture in
Received in revised form 3 November 2009 the homogeneous phase and at saturation conditions were measured in the same range of temperature.
Accepted 5 November 2009
The influence of 3 and 6 mol% ethanol and 2-propanol as co-solvent on the solubility and density data
Available online 10 November 2009
for the CO2 + palmitic acid mixture was also determined at 313 K. Measurements were carried out in a
static-synthetic sapphire cell coupled to a vibrating-tube densitometer. The self-consistency of the data
Keywords:
was tested according to the density-based models proposed by Mendez-Santiago and Teja.
Palmitic acid
Co-solvent © 2009 Elsevier B.V. All rights reserved.
Densitometer
Solubility

1. Introduction
In food and pharmaceutical industry, it is necessary to warrant
the total removal of the undesirable solvents from the product
without exposing it to high temperatures. In this case extrac-
tion with supercritical carbon dioxide (SCCO2 ) is an interesting
separation process, because of the advantageous properties, like
non-toxicity, non-flammability and low price. However, for the
design a reliable knowledge of the phase equilibrium behavior is
required.
Palm oil is one of the most common natural vegetable oils;
it consists of free fatty acids as well as triglycerides. For the
design of an industrial process, knowledge of the phase equilibrium
behavior and solubility in supercritical components are required.
Palmitic acid, one of the main components in palm oil, is one
of the most commonly used oils in the food and pharmaceutical
industry. Measurements about solubility of fatty acids in super-
critical fluids have been published previously, but these data are
often not consistent. The solubility of palmitic acid in SCCO2 at
313 K has been reported by Bamberger et al. [1], Cho et al. [2],
and Ohgaki et al. [3]. Besides, Gordillo et al. [4], Kramer and Tho-
dos [5], and recently Garlapati and Madras [6] have published
solubility data above 318 K. These literature data are shown in
∗ Corresponding author. Tel.: +52 55 5729 6000x55133; fax: +52 55 5586 2728.
E-mail address: lgalicial@ipn.mx (L.A. Galicia-Luna).
Fig. 1. It can be seen that especially at 318 and 328 K high differ-
ences are observed between the data published by the different
authors.
Garlapati and Madras [6] have reported the influence of adding
an alkanol (ethanol or 3-methyl-1-butanol) as co-solvent on the
solubility of palmitic acid in SCCO2 at 308 and 318 K. Ethanol
increased the solubility of palmitic acid in CO2 compared to 3-
methyl-1-butanol. Finally Koga et al. [7] reported data for different
compositions of ethanol at 9.9 and 19.7 MPa at a temperature of
308.2 K.
In this paper, a static-synthetic set-up was used to study the
solubility of palmitic acid in supercritical carbon dioxide with and
without the presence of a co-solvent (ethanol or 2-propanol). The
alkanol is expected to enhance the solubility of palmitic acid due to
its polarity. The main advantage of the experimental apparatus is
that no analytical equipment like HPLC is necessary. Densities of the
investigated systems were quasi-simultaneously determined via a
vibrating-tube densitometer at pressures up to 25 MPa. No density
data for these systems have been reported previously.
The prediction of solubility of solids in supercritical fluids
using thermodynamic models presents some difficulties. Semi-
empirical correlations such as the density-based models proposed
by Mendez-Santiago and Teja [8,9] are commonly used to inter-
polate the solubility of solids in supercritical fluids. This model
was used to test the self-consistency of the measured data. For the
ternary system, a modification of the model proposed by the same
authors was used.

0378-3812/$ – see front matter © 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.fluid.2009.11.007
 L. Brandt et al. / Fluid Phase Equilibria 289 (2010) 72–79 73

Fig. 1. Solubility of palmitic acid in carbon dioxide reported in literature—313 K: (䊉) Fig. 2. Solubility of palmitic acid in SCCO2 at 313 K: (䊉) Bamberger et al. [1]; ()
Bamberger et al. [1]; () Cho et al. [2]; () Ohgaki et al. [3]. 318 K: () Gordillo et al. Cho et al. [2]; () Ohgaki et al. [3]; (♦) this work.
[4]; () Kramer and Thodos [5]; () Garlapati and Madras [6]. 328 K: () Gordillo et
al. [4]; () Kramer and Thodos [5].
for the density measurements. The visual sapphire cell (Armines,
Table 1 France) had a volume of ∼10 cm3 and the vibrating U-tube densito-
Characteristics of materials. meter (DMA 60/512P, Anton Paar, hastelloy C-276) had an internal
Chemicals CAS number Purity Supplier volume of ∼1 cm3 . The vibrating period was displayed in the uni-
versal counter (53131A, Hewlett-Packard). The equilibrium cell
Carbon dioxide [124–38–9] 99.995% Infra, Mexico
Nitrogen [7727–37–9] 99.998% Infra, Mexico
temperature was regulated by an air bath (Spame, France), while
Palmitic acid [57–10–3] 99% Sigma, USA the vibrating-tube densitometer (VTD) was thermo-regulated by
Ethanol [64–17–5] 99.8% Merck, Germany a liquid bath (PolyScience). Two platinum probes (Pt100, Specitec)
2-Propanol [67–63–0] 99.5% Aldrich, USA were immersed in the thermometric wells, one located at the top of
the cell body and the second inside the vibrating-tube densitome-
ter. These platinum probes were connected to a digital indicator
2. Experimental
(F250, Automatic Systems Laboratories) to monitor the tempera-
ture. The calibration for the temperature probes was performed
2.1. Materials
using a calibration system (F300S, Automatic Systems Laboratories)
fitted with a 25- reference probe (162CE, ±0.005 K certified accu-
Purities of the chemical substances used for the experimen-
racy, Rosemount). The temperature uncertainty for the platinum
tal measurements are presented in Table 1. Gases were used as
probes was estimated to be ±0.03 K.
received. Palmitic acid was carefully degassed before use. The
Pressure measurements were performed with a pressure trans-
critical properties [10,11] and acentric factors required for the cal-
ducer (250, Sedeme) placed above the equilibrium cell and
culation are given in Table 2.
connected to a digital multimeter (34401A, HP). Pressure trans-
ducer was calibrated against a dead weight balance (Model 5304
2.1.1. Static-synthetic set-up class S2) from Desgranges and Huot in the range of 313–333 K. The
A description of this equipment was published previously by estimated uncertainty for pressure measurements were found to be
Zúñiga-Moreno et al. [12]. Mixtures were loaded in a static- within 0.008 MPa. A cathetometer equipped with a camera allowed
synthetic cell which is coupled to the vibrating-tube densitometer an enlarged visualization of the sapphire tube.

Table 2
Critical properties and acentric factors of the pure compounds [10,11].

MW Tc (K) pc (MPa) ω

CO2 44.01 304.12 7.374 0.225

Palmitic acid 256.429 776.00 1.510 0.215
Ethanol 46.069 513.92 6.148 0.649
2-Propanol 60.096 508.30 4.762 0.665

Table 3
Experimental solubility of palmitic acid (2) in carbon dioxide (1).

T (K) = 313 T (K) = 318

−4
p (MPa) y2 × 10 p (MPa) y2 × 10−4

12.11 3.534 10.14 1.436

12.88 3.912 15.56 6.078
14.57 4.968 18.41 8.400
15.52 5.624 23.35 11.120
17.07 6.302
20.15 7.923
Fig. 3. Solubility of palmitic acid in SCCO2 at 318 K: () Gordillo et al. [4]; ()
22.93 8.981
Garlapati and Madras [6]; () this work.
74 L. Brandt et al. / Fluid Phase Equilibria 289 (2010) 72–79

Table 4
Experimental densities of carbon dioxide (1) + palmitic acid (2) mixtures at 313 K.

y2 = 8.981 × 10−4 y2 = 8.682 × 10−4 y2 = 7.923 × 10−4 y2 = 6.348 × 10−4

p (MPa)  (kg/m )3
p (MPa)  (kg/m )
3
p (MPa)  (kg/m )3
p (MPa)  (kg/m3 )

22.93 864.8a 21.70 855.0 20.15 843.3a 17.61 816.9

23.28 867.3 22.02 857.3 20.30 844.6 17.81 819.0
23.57 869.5 22.47 861.0 20.54 846.7 18.01 821.0
23.81 871.1 23.07 865.7 20.74 848.5 18.18 823.1
24.01 872.6 23.55 869.1 20.94 850.2 18.30 824.3
24.78 877.9 24.04 872.7 21.12 851.7 18.40 825.2
24.46 875.8 21.30 853.3 18.51 826.4
21.52 855.0 18.60 827.4
21.71 856.7 18.70 828.4
21.97 858.7 18.79 829.4
22.23 860.8 18.91 830.6
22.65 864.0 19.07 832.2
22.91 865.9 20.09 841.8
23.52 868.9 21.01 849.8
24.02 871.6 22.02 858.2
23.05 866.0
23.79 871.5

y2 = 6.302 × 10−4 y2 = 5.357 × 10−4 y2 = 4.968 × 10−4 y2 = 3.534 × 10−4

p (MPa)  (kg/m )3
p (MPa)  (kg/m )
3
p (MPa)  (kg/m )3
p (MPa)  (kg/m3 )
a a
17.07 809.1 14.94 780.5 14.57 774.5 12.11 724.5a
17.50 814.3 16.02 795.7 14.96 780.9 12.15 725.8
17.97 819.5 16.23 798.5 15.97 795.6 12.36 731.2
18.99 830.2 16.43 801.3 17.12 810.0 12.53 735.3
19.99 839.7 16.61 803.4 17.62 815.9 12.77 741.0
21.00 848.7 16.82 806.0 18.05 820.6 12.93 744.7
22.05 857.5 17.03 808.5 19.00 830.5 13.15 749.3
23.00 864.9 18.07 820.0 19.96 839.8 13.33 753.0
24.00 872.3 19.07 830.9 21.02 849.3 13.68 759.8
24.74 877.4 20.06 840.4 22.02 857.5 13.94 764.4
21.05 849.1 22.79 863.5 14.12 767.7
22.03 857.3 24.01 872.7 14.41 772.7
23.03 865.1 25.03 879.6 14.65 776.6
23.99 872.2 15.03 782.7
24.64 876.7 15.57 790.5
16.05 797.0
17.04 810.1
18.03 821.3
19.04 831.8
20.05 841.4
21.04 850.3
21.98 858.0
22.99 866.0
24.05 873.7
a
Saturation density.

The densitometer calibration was carried out following the clas- 2.1.2. Procedure
sical method described elsewhere [12,13]. Water and nitrogen were Measurements were basically performed in three steps. The
used as reference fluids. Densities for water and nitrogen were cal- first one was the cell loading, the second one was the adjustment
culated with the equations of state proposed by Wagner and Pruß of the measurement conditions and the last step was the mea-
[14], and Span et al. [15], respectively. Experimental densities were surement of density and solubility as described by Zúñiga-Moreno
obtained using the following equation et al. [12].
The loading of the cell began with the assembly of the cell. After
that, the empty cell was evacuated in order to get its dead weight.
F (p, T ) Weightings were performed in a mass comparator balance (MCA
   1200, Sartorius) within an uncertainty of (3 × 10−7 kg). Then the
2F (p, T ) − 2H (p, T ) H2 O (p, T ) − N2 (p, T )
2O cell was opened for the loading of palmitic acid (2). While stir-
= H2 O (p, T ) +
2H (p, T ) − 2N (p, T ) ring the solid, the air was removed again to determine the mass of
2O 2
(1) palmitic acid. Next, if required, the co-solvent (3) was added into
the cell and was degassed and weighed again. After that, the cell
was loaded with liquid carbon dioxide (1) by means of a syringe
where F (p,T) is the studied fluid density, H2 O (p, T ) and N2 (p, T ) pump (Model 100D, Isco). With the loaded liquid carbon dioxide the
are the reference fluid densities, in kg m−3 , i (p,T) are the vibrating cell was weighed again to determine the amount of carbon dioxide
periods in s−1 for each fluid at the same conditions of temperature and consequently the final composition of each mixture. The esti-
and pressure. The estimated uncertainty of experimental densities mated uncertainties according to the law of propagation errors for
is ±0.20 kg m−3 . It was calculated with the law of propagation of compositions in terms of mole fraction were found to be less than
errors, as described previously [16]. y2 = 7 × 10−6 for the solubility of palmitic acid (2) in carbon dioxide
 L. Brandt et al. / Fluid Phase Equilibria 289 (2010) 72–79 75

Table 5
Experimental densities of carbon dioxide (1) + palmitic acid (2) mixtures at 318 K.

y2 = 1.436 × 10−4 y2 = 11.12 × 10−4 y2 = 18.28 × 10−4

p (MPa)  (kg/m )3
p (MPa)  (kg/m )3
p (MPa)  (kg/m3 )

10.14 535.9a 23.35 845.5a 21.72 831.3

10.29 551.9 23.92 849.8 21.99 833.9
10.55 577.8 24.05 850.8 22.51 838.4
10.89 604.2 24.09 851.1 23.01 842.7
11.23 626.2 24.27 852.5 23.52 846.9
11.52 641.2 24.43 853.7 24.05 850.9
11.87 657.3 24.51 854.2 24.56 854.7
12.19 670.6 24.61 855.0
12.48 680.9 24.77 856.3
12.82 692.0 24.93 857.5
13.11 700.3 25.04 858.3
13.39 708.3
13.73 716.8
14.03 723.9
14.52 734.8
14.99 744.0
16.05 762.8
17.01 777.4
17.69 786.8
18.08 791.8
18.99 802.8
19.75 811.4
a
Saturation density.

(1). In the case of the solubility of palmitic acid (2) in CO2 (1) with
the presence of ethanol of 2-propanol (3), it was found to be y2 = ±
1.5 × 10−5 .
Once the cell was connected to the VTD, the tubing was evacu-
ated and the system was checked for leaks. Pressure was raised
to 25 MPa. After the solid was completely dissolved in SCCO2
the charging valve, connected between the cell and the VTD was
opened to feed the VTD and the temperature was raised to the
desired temperature. After the adjustment of isothermal conditions
(at least 2.5 h) the measurements were started with recording the
temperatures of the air bath and the VTD, the vibrating period of the
mixture in the densitometer, and the initial pressure of the system.
Then the pressure was slightly decreased until precipitation of the
solid was observed (solid–gas equilibrium at a fixed composition).
Pressure was first reduced to appr. 1 MPa, and then it was done
with lower intervals of about 0.5, 0.3 and 0.15 MPa, depending on
the distance to the saturation pressure. Temperature, pressure and
the vibrating period was recorded at each pressure decrease. The
measurements were finished when the saturation vapor pressure
was reached in the cell [12].
3. Results and modeling
3.1. Carbon dioxide (1) + palmitic acid (2) mixtures
Isothermal solubility data of palmitic acid in supercritical car-
bon dioxide were measured at 313 and 318 K. These results are
presented in Table 3. An increase of the solubility of palmitic acid
in SCCO2 was reached with increasing pressure at isothermal con-
ditions. An increase of the solubility is observed when going from
313 to 318 K.
The experimental results were compared with literature data.
Agreement was found between the solubility data obtained in this
work and the data reported by Bamberger et al. [1], Cho et al. [2]
and Ohgaki et al. [3] at 313 K as shown in Fig. 2. Moreover the solu-
bilities obtained in this work agrees with the data sets reported by
Gordillo et al. [4] and Garlapati and Madras [6] at 318 K (see Fig. 3).

Fig. 4. Solubility of palmitic acid (2) in carbon dioxide (1) as a function of density:
() Bamberger et al. [1]; () Cho et al. [2]; () Ohgaki et al. [3]; () Gordillo et al. [4]; Fig. 5. Solubility of palmitic acid (2) in carbon dioxide (1) + alkanol (3) mix-
() Garlapati and Madras [6]; () this work. The solid line represents the calculated tures reported in this work: () x3 = 0; (䊉) xethanol = 0.03; () x2-propanol = 0.03; ()
data using the Mendez-Santiago and Teja correlation [8]. xethanol = 0.06; () x2-propanol = 0.06.
76 L. Brandt et al. / Fluid Phase Equilibria 289 (2010) 72–79

Table 6
Solubility of palmitic acid (2) in different CO2 (1) + alkanol (3) mixtures.

T (K) = 313

x3 (ethanol) = 0.03 x3 (ethanol) = 0.06

p (MPa) y2 × 10−3 p (MPa) y2 × 10−3

8.21 1.01 10.41 5.81

9.04 2.07 12.73 8.27
12.03 3.45 15.13 10.9
14.07 4.26 17.19 13.5
18.32 5.70 22.76 15.7
24.61 5.90

T (K) = 313

x3 (2-propanol) = 0.03 x3 (2-propanol) = 0.06

p (MPa) y2 × 10−3 p (MPa) y2 × 10−3

11.28 3.51 10.90 8.06

12.98 4.30 12.87 10.6
Fig. 6. Saturation densities for the carbon dioxide (1) + palmitic acid (2) + alkanol 17.86 5.54 15.02 13.7
(3) mixtures at 313 K: (䊉) xethanol = 0.03; () x2-propanol = 0.03; () xethanol = 0.06; () 18.35 6.10 20.69 16.2
x2-propanol = 0.06. 18.76 6.22

But deviations are observed above 20 MPa when the solubility data
are compared with those reported by Gordillo et al. [4]. Larger devi-
ations were found for the solubilities reported in Refs. [4,6] and in
this work with the data reported by Kramer and Thodos [5] at 318 K,
thus in Fig. 3 our data are only compared with the data given in the
recent references [4,6].
One of the advantages of this static-synthetic apparatus is
the use of a sapphire tube cell where the present phases in
the mixture placed inside the view-cell can be observed visu-
ally. For the CO2 + palmitic acid mixtures gas and solid–gas phases
were observed for pressures above and at the saturation pressure,
respectively at 313 and 318 K. More solubility measurements were
performed at 323 and 328 K and a phase change occurred along both
temperatures. Therefore, gas and gas–liquid phases were observed
for pressures lower than 25 MPa and at the saturation pressure,
respectively. Since we were interested on the solid–gas region; the
exact conditions of this phase transition were not relevant for this
work, i.e. the data are not reported. This phenomena is congruent
with the exact data recently reported by Bertakis et al. [17], where
the solid–liquid–gas equilibrium was found to be between 319 and
322 K for pressures above 10 MPa.

Table 7
Experimental densities of carbon dioxide (1) + palmitic acid (2) with 3 mol% of ethanol (3) at 313 K.

y2 = 1.01 × 10−3 y2 = 2.07 × 10−3 y2 = 3.45 × 10−3 y2 = 4.26 × 10−3 y2 = 5.70 × 10−3 y2 = 5.90 × 10−3

p (MPa)  (kg/m3 ) p (MPa)  (kg/m3 ) p (MPa)  (kg/m3 ) p (MPa)  (kg/m3 ) p (MPa)  (kg/m3 ) p (MPa)  (kg/m3 )
a a a a a
8.21 618.4 9.03 661.9 12.03 755.7 14.07 791.5 18.32 832.8 4.61 881.2a
8.67 657.4 10.10 709.8 12.25 759.8 15.06 803.9 18.76 838.1 24.75 882.2
9.58 710.9 11.00 735.2 12.47 763.7 16.12 815.7 19.08 842.7 24.90 883.3
10.54 721.4 12.02 756.9 12.69 767.7 17.01 824.7 19.46 847.1 25.07 884.1
11.56 730.1 13.06 774.9 12.94 771.7 18.05 834.3 19.95 849.8
12.58 746.5 14.08 789.6 13.53 780.9 18.93 841.9 20.95 857.3
13.61 759.3 15.02 801.8 14.08 788.9 20.04 850.7 21.54 861.7
14.63 773.3 16.07 813.8 14.99 800.7 21.02 858.1 22.11 865.5
15.57 784.8 17.01 823.5 16.10 813.5 22.02 865.1 22.62 869.1
16.56 809.2 17.98 832.7 17.01 823.1 22.96 871.6 23.62 875.5
17.47 826.8 18.95 841.3 18.05 833.3 24.03 878.2 23.86 877.0
18.12 833.1 20.04 850.1 18.97 841.1 25.06 884.4 24.10 878.5
18.54 836.7 21.03 857.6 20.02 849.7 24.38 880.2
18.72 838.2 22.04 864.8 20.97 857.1 24.69 882.0
18.95 840.2 23.01 871.4 21.98 864.4 24.98 883.7
19.15 841.9 23.99 877.7 22.99 871.4
19.35 843.6 25.04 884.1 24.01 877.8
19.55 845.4 24.89 883.1
19.74 846.9
19.94 848.5
20.29 851.2
20.63 853.8
20.98 856.6
21.15 857.8
21.28 858.7
21.44 859.9
21.62 861.2
21.82 862.6
22.49 867.7
23.04 871.0
23.95 877.1
25.04 883.6
a
Saturation density.
 L. Brandt et al. / Fluid Phase Equilibria 289 (2010) 72–79 77

Table 8
Experimental densities of carbon dioxide (1) + palmitic acid (2) with 6 mol% of ethanol (3) at 313 K.

y2 = 5.81 × 10−3 y2 = 8.27 × 10−3 y2 = 10.9 × 10−3 y2 = 13.5 × 10−3 y2 = 15.7 × 10−3

p (MPa)  (kg/m ) 3
p (MPa)  (kg/m )3
p (MPa)  (kg/m )3
p (MPa)  (kg/m )3
p (MPa)  (kg/m3 )

10.41 748.8a 12.73 792.1a 15.13 820.7a 17.19 838.2a 22.76 874.3a
11.05 766.0 12.87 794.0 15.24 821.7 17.31 839.3 22.99 875.4
12.05 781.9 13.05 796.3 15.38 823.2 17.48 840.6 23.52 878.5
13.02 794.8 13.50 801.8 15.64 825.4 17.95 844.1 24.50 883.8
14.04 806.5 13.99 807.3 15.86 827.5 18.46 847.9 24.73 884.9
15.03 816.8 15.02 818.0 16.04 828.9 18.96 851.5 24.91 886.0
16.06 826.3 16.05 827.4 16.52 833.1 19.46 854.9 25.07 886.6
16.99 834.4 17.01 835.5 17.02 837.2 20.02 858.7
18.04 842.6 18.06 844.1 18.06 845.3 20.97 864.8
19.02 850.0 19.03 850.8 19.00 852.0 22.10 871.5
20.00 856.7 19.99 853.5 20.01 858.7 22.98 876.5
21.10 863.9 20.96 863.9 20.97 864.9 23.99 882.3
22.02 869.6 22.01 870.3 22.10 871.6 25.09 887.9
23.01 875.5 23.01 876.1 22.97 876.7
24.00 881.1 23.98 881.6 23.99 882.4
25.11 887.0 25.00 887.1 25.03 887.8
a
Saturation density.

The density-based correlation proposed by Mendez-Santiago
and Teja [8] given in Eq. (2) was used to check for the consistency
of the experimental and literature solubilities of palmitic acid in
SCCO2
T ln(y2 p) = A + B m + C  T
The parameters A , B , and C were obtained by correlating the
data (313–318 K) from this work together with the literature data
with the exception of those from Ref. [5] by a minimum square algo-
rithm to minimize the deviation between the experimental and
calculated enhancement factor. The solid solubility in the super-
critical solvent y2 in Eq. (2) is considered to be low. Therefore, the
solvent density l can be used instead of the density of the mixture
m [18]. The resulting temperature-independent parameters were
the following: A = −8526.6 K, B = 2.955 K m3 kg−1 , C = 15.174. The
correlation results are shown in Fig. 4. The absolute average devia-
tion (AAD) between experimental and calculated values for y2 was
26%. On the other hand our experimental data were found to have a
lower AAD of about 13% and from Fig. 4 can be seen that these data
collapse in the single solid line even at low density where the data
reported by Bamberger et al. [1] presents higher deviations, so that
our experimental data would be internally consistent [8]. Exper-
imental densities for the system carbon dioxide + palmitic acid in
the homogeneous phase region at different compositions were also
(2) determined from 313 to 318 K and are listed in Tables 4 and 5. As can
be seen, densities increase with increasing pressure, and decrease
with rising temperature. Differences in density between palmitic
acid + SCCO2 mixtures and carbon dioxide are lower than 2 kg/m3 at
pressures above 15 MPa, and increase as pressure decreases below
15 MPa to appr. 10 kg/m3 .
3.2. Carbon dioxide (1) + palmitic acid (2) alkanol (3) mixtures
Solubility and density measurements of palmitic acid in carbon
dioxide in the presence of a co-solvent with 3 and 6 mol% were
also investigated at 313 K. Solubility and density data are listed
in Table 6 and Tables 7–10, respectively. A gradual increase on
the solubility of palmitic acid was reached when the pressure was
increased.

Table 9
Experimental densities of carbon dioxide (1) + palmitic acid (2) with 3 mol% of 2-propanol (3) at 313 K.

y2 = 3.51 × 10−3 y2 = 4.30 × 10−3 y2 = 5.54 × 10−3 y2 = 6.10 × 10−3 y2 = 6.22 × 10−3

p (MPa)  (kg/m ) 3
p (MPa)  (kg/m )3
p (MPa)  (kg/m )3
p (MPa)  (kg/m )3
p (MPa)  (kg/m3 )
a a a a
11.28 744.1 12.98 775.3 17.86 830.9 18.35 834.8 18.76 835.9a
11.49 748.6 13.14 777.6 18.04 833.0 18.48 835.9 18.99 837.9
11.62 751.3 13.32 780.2 18.52 837.1 18.64 837.1 19.50 842.3
11.80 754.7 13.51 782.9 18.97 840.7 18.99 840.2 20.01 846.3
12.03 758.9 14.03 790.1 19.44 844.8 19.51 844.4 20.50 850.2
12.98 774.7 14.39 794.6 20.07 849.4 20.01 848.3 20.99 853.9
14.02 789.4 14.96 801.5 20.53 852.9 20.45 851.6 21.49 857.6
14.96 801.1 15.55 808.1 21.02 856.5 20.97 855.5 22.01 861.2
15.94 812.3 16.02 813.2 21.56 860.3 21.49 859.2 22.48 864.5
17.03 823.0 17.04 823.4 21.99 863.4 22.01 862.8 22.97 867.8
18.05 832.4 18.03 832.5 22.58 867.1 22.49 866.0 23.49 871.1
19.06 841.0 19.05 841.2 22.78 868.6 22.97 869.2 23.93 873.8
20.06 848.9 20.08 849.2 22.96 869.6 23.49 872.4 24.50 877.4
20.93 855.3 20.99 856.0 23.02 870.3 23.97 875.4 25.14 881.3
22.00 862.9 21.99 862.9 23.14 870.7 24.49 878.6
23.02 869.5 23.01 869.7 23.28 871.7 25.14 882.2
24.02 875.9 23.99 875.7 23.48 872.9
25.00 881.9 24.96 881.7 23.65 874.1
23.96 875.8
24.01 876.1
24.98 882.2
25.03 882.2
a
Saturation density.
78 L. Brandt et al. / Fluid Phase Equilibria 289 (2010) 72–79

Table 10
Experimental densities of carbon dioxide (1) + palmitic acid (2) with 6 mol% of 2-propanol (3) at 313 K.

y2 = 8.06 × 10−3 y2 = 10.6 × 10−3 y2 = 13.7 × 10−3 y2 = 16.2 × 10−3

p (MPa) ␳ (kg/m )3
p (MPa) ␳ (kg/m )3
p (MPa) ␳ (kg/m )3
p (MPa) ␳ (kg/m3 )

10.90 764.8a 12.87 792.6a 15.02 820.5a 20.69 863.3a

11.05 767.2 12.97 793.9 15.19 821.5 20.81 863.9
11.22 769.8 13.26 797.0 15.31 822.6 20.93 864.6
11.53 774.4 13.50 799.9 15.53 824.4 21.21 866.2
11.85 778.9 14.00 805.4 16.06 828.8 21.50 867.7
12.03 781.3 14.49 810.3 16.52 832.5 22.05 870.9
12.53 787.9 15.05 815.8 17.02 836.3 22.97 875.9
13.05 794.1 16.08 825.2 18.04 843.7 23.94 880.9
13.99 804.6 17.05 833.3 18.98 850.1 25.08 886.5
15.04 815.2 18.02 840.8 20.04 856.9
16.06 824.5 18.95 847.3 20.96 862.4
17.03 832.5 20.03 854.8 22.03 868.6
18.04 840.4 21.01 861.1 22.97 873.7
18.94 846.8 22.05 867.4 24.06 879.4
19.99 854.1 23.01 872.9 25.09 884.6
20.97 860.4 24.06 878.7
22.01 866.8 25.09 884.0
23.02 872.7
24.01 878.3
25.08 883.9
a
Saturation density.

Interesting results were observed for the solubility of palmitic

acid in carbon dioxide + alkanol mixtures (in Fig. 5). These data were
compared with the solubility measurements of palmitic acid in
SCCO2 at 313 K. The addition of the alkanol enhances the solubility
of palmitic acid in SCCO2 , resulting that the highest solubility of this
solid was found at an alkanol composition at 6 mol%. 2-Propanol is a
slightly better co-solvent than ethanol for the solubility of palmitic
acid in carbon dioxide. A comparison with published data could not
be carried out because the data reported in Ref. [6] were measured
at higher temperature.
Experimental densities for the carbon dioxide (1) + palmitic acid
(2) + alcohol (3) system at different compositions were also deter-
mined, and are given in Tables 7–10. Densities reported for the
ternary mixture at 3 mol% of alkanol compared with carbon dioxide
densities vary from 3 to 20 kg/m3 at pressures higher than 15 MPa.
At lower pressure, differences in densities increase up to 300 kg/m3 .
In the case of the densities for the ternary mixtures reported for
6 mol% of the alcohol, the differences against carbon dioxide den-
Fig. 7. Solubility of palmitic acid (2) in carbon dioxide (1) + alcohol (3) mixtures
sities are from 10 to 90 kg/m3 as pressure decreases in the range at 313 K as a function of CO2 density: (䊉) xethanol = 0.03; () x2-propanol = 0.03; ()
of 10–22 MPa. Saturation densities of these mixtures are shown in xethanol = 0.06; () x2-propanol = 0.06; the solid line represents the calculated data using
Fig. 6. The saturation densities increase with increasing pressure. the Mendez-Santiago and Teja correlation [9].
Density differences for these ternary systems and carbon dioxide
are higher than 50 kg/m3 at pressures lower than 15 MPa. These For fitting the parameters, the experimental solubilites of
differences decrease as pressure increases from that pressure up to palmitic acid in different carbon dioxide + ethanol or 2-propanol
25 MPa in the range of 50–4 kg/m3 . mixtures were used. The obtained parameters were G = 3474.5 K,
The solubility of palmitic acid in carbon dioxide + alkanol H = 2.879 m3 kg−1 and J = 8545.7 K. The best-fit is shown for each
mixtures was correlated with the equation proposed by Mendez- composition of co-solvent, x3 in Fig. 7. It can be seen that all the sol-
Santiago and Teja [9] which is based on the theory of diluted ubility isotherms collapse in a single trend line depending on the
solutions. For co-solvent systems (ternary mixtures) the following composition of the co-solvent. The ADD between the experimental
equation has to be applied: and the correlated solubilities using the parameters given above
are about 8.5%.
T ln E = G + H  1 + J  x3 (3)
4. Conclusions
with
y2 p The solubility of palmitic acid in supercritical carbon diox-
E= (4)
psub
2
ide has been determined at 313 and 318 K in the pressure
range of 10–25 MPa. The solubilities are in the range of
where the parameters G , H and J are independent of temperature, y2 = 1.43 × 10−4 − 11.12 × 10−4 . The solubilities were found to be in
E is the enhancement factor, which includes the solubility y2 , the agreement with those reported in the literature. Gas–liquid equi-
pressure p and the sublimation pressure psub
2
, which was correlated libria were observed at temperatures higher than 323 K, therefore
with the Antoine equation. l is the density of carbon dioxide and no more solid solubility measurements in SCCO2 were performed.
x3 is the co-solvent mole fraction. The exact phase transition data was not the aim of this work. The
 L. Brandt et al. / Fluid Phase Equilibria 289 (2010) 72–79 79

influence of a co-solvent on the solubility of palmitic acid in CO2 Acknowledgments

was studied at 313 K. It was found that the solubility of palmitic acid
in carbon dioxide was enhanced at 6 mol% of the alkanol, whereby The authors wish to express their gratitude to Consejo Nacional
2-propanol is a slightly better co-solvent than ethanol. The exper- de Ciencia y Tecnologia and Instituto Politécnico Nacional (MEX-
imental solubilities of the different mixtures were correlated with ICO) for the financial support of this research.
the density-based models proposed by Mendez-Santiago and Teja. L. Brandt thanks Stipendien-Fond des Verbandes der Chemis-
Solubility data were internally consistent because they collapsed chen Industrie e.V. (FCI) for the PhD fellowship. O. Elizalde-Solis
in a single straight line for each system with good agreement. specially acknowledges Director of E.S.I.Q.I.E. Prof. J.S. Meza-
Densities for these systems were quasi-simultaneously Espinoza for the Ph.D. fellowship.
obtained at different compositions via a vibrating-tube den-
sitometer in the same pressure range up to 25 MPa. Densities of References
these systems have not been reported previously.
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2 solid component
3 co-solvent

Superscripts
sub sublimation condition