Journal of Food Engineering 70 (2005) 579587

www.elsevier.com/locate/jfoodeng

Application of the GCA-EoS model to the supercritical

processing of fatty oil derivatives
Olga Ferreira a, Eugenia A. Macedo

a,*

, Esteban A. Brignole

LSRELaboratory of Separation and Reaction Engineering, Departamento de Engenharia Qumica,

Faculdade de Engenharia da Universidade do Porto, Rua Dr. Roberto Frias, 4200-465 Porto, Portugal
b
PLAPIQUI, UNSCONICET, CC 71, Km 7, Camino La Carrindanga, 8000 Baha Blanca, Argentina
Received 2 February 2004; accepted 7 October 2004
Available online 13 December 2004

Abstract
The group-contribution with association equation of state (GCA-EoS) is applied to represent high-pressure phase equilibria in
mixtures of supercritical gases (carbon dioxide, propane) with fatty oil derivatives, such as mono- and di-glycerides, fatty acids and
fatty acid esters.
Association eects in these mixtures are described by a group-contribution approach using three dierent association groups: the
hydroxyl group, the acid group and the ester group.
Satisfactory predictions of vaporliquid equilibria, liquidliquid equilibria and c1 of binary and ternary mixtures of high-molecular weight triacyglycerides and their derivatives with carbon dioxide or propane are obtained.
It is shown that the GCA-EoS is a powerful engineering tool for the design and optimization of extraction and fractionation
processes of fatty oil derivatives with supercritical uids.

2004 Elsevier Ltd. All rights reserved.
Keywords: Fatty oils; Phase equilibria; Thermodynamic modelling; Association; Group-contribution

1. Introduction
The design of extraction, fractionation and purication processes involving fatty oils and their derivatives,
using near critical or supercritical uids as solvents, requires the existence of thermodynamic models that are
able to represent these highly complex mixtures that include high-molecular weight triglycerides and their
derivatives with low-molecular weight solvents.
Usually, these natural products mixtures are described using cubic equations of state like Peng and
Robinson (1976) or Soave (1972). Some authors (Yu,
Zou, Bhaskar, Rizvi, & Zollweg, 1993) used the Peng
*

Corresponding author. Tel.: +351 222041653; fax: +351

222041674.
E-mail address: eamacedo@fe.up.pt (E.A. Macedo).
0260-8774/$ - see front matter
2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jfoodeng.2004.10.012

Robinson EoS with the Panagiotopoulos and Reid mixing rules to correlate vapourliquid equilibria (VLE) of
ternary mixtures of CO2 + methyl oleate + oleic acid.
Two interaction parameters for each pair of components
were estimated. Other researchers (Fuente, Fornari,
Brignole, & Bottini, 1997) have applied the SRK-EoS
with quadratic mixing rules to correlate vapourliquid
and liquidliquid equilibria (LLE) data for mixtures
containing sunower oil with ethane and propane. In
order to predict the appearance of a liquidliquid split,
binary interaction parameters for both the attractive energy parameter and the co-volume were introduced.
However, it was not possible to describe quantitatively
both VLE and LLE using only one set of parameters
for the co-volume, which indicated the limitations of
the van der Waals repulsive term to describe these asymmetric mixtures. More recently, the PengRobinson EoS

580

O. Ferreira et al. / Journal of Food Engineering 70 (2005) 579587

with the quadratic mixing rules coupled with several sets

of combining rules was used (Araujo & Meireles, 2000).
As expected, two or three molecular interaction parameters had to be estimated for each pair of molecules,
depending on the set of combining rules.
Due to the scarcity of experimental data available for
this kind of systems, it is desirable to use a group-contribution method. Following this approach, several equation of state-excess Gibbs (or Helmholtz) function
models (e.g. MHV1, LCVM) were applied for the prediction of the uidliquid equilibria of CO2 and sh
oil esters and acids (Coniglio, Knudsen, & Gani,
1996). New interactions between CO2 and the corresponding UNIFAC groups were determined. Satisfactory results were obtained, except in the critical region.
Other authors (Bottini, Fornari, & Brignole, 1999;
Espinosa, Foco, Bermudez, & Fornari, 2000; Espinosa,
Fornari, Bottini, & Brignole, 2002) showed the capability of the group-contribution equation of state (GCEoS) developed by Skjold-Jrgensen (1984, 1988) to
describe simultaneously, i.e. with the same set of parameters, the vapourliquid equilibria (VLE) and the
liquidliquid equilibria (LLE) observed in mixtures of
supercritical gases + vegetable oil mixtures.
The GC-EoS is suitable for the modelling of these
non-polar or slightly polar mixtures with large size differences containing carbon dioxide, propane and triglycerides. The GC-EoS model was compared to the MHV2
and PSRK equations. All three models perform similarly for non-polar systems of low-molecular weight
and similar size. However, the MHV2 and PSRK models present some limitations when they are extended to
very asymmetric mixtures. The CarnahanStarling
repulsive term of the GC-EoS allows a better description
of these non-ideal mixtures. Recently, the GC-EoS was
applied to describe the phase equilibria of the non-associating mixtures of triglycerides and fatty esters with
near critical uids (Espinosa et al., 2002). In these mixtures, no association eects are present.
Which should be the model used for the description
of mixtures containing not only highly size-asymmetric
mixtures but also, associating components?
The group-contribution with association equation of
state, GCA-EoS, (Gros, Bottini, & Brignole, 1996) constitutes a good option. It results from the addition of a
group-contribution association term to the GC-EoS
model.
Three important characteristics of these highly complex mixtures are explicitly taken into account by this
model:
Limited experimental information available. This
characteristic suggests the use of a group-contribution approach because a large number of natural
products can be described with a small number of
groups.

Size dierences between solvents and solutes.

Association eects.
In this work, the GCA-EoS is applied to mixtures of
fatty oils and their derivatives (fatty acids, fatty acids
esters, mono- and di-glycerides) with supercritical solvents like carbon dioxide or propane.

2. The group-contribution with association equation of

state
The GCA-EoS can be written as the sum of three different contributions to the residual energy of Helmholtz:
A Arep Aatt Aassoc

The repulsive term (rep) is given by the Carnahan

Starling term for hard spheres; the attractive term (att)
is a group-contribution version of a density dependent
local composition expression (NRTL) and, nally, the
association term (ass) which is a group-contribution approach (Gros et al., 1996) based on Wertheim Statistical
Association Fluid Theory (Wertheim, 1984a, 1984b;
Wertheim, 1986a, 1986b) as applied to the SAFT equation (Chapman, Gubbins, Jackson, & Radosz, 1990;
Huang & Radosz, 1990). A more detailed description
of the GCA-EoS is presented in Appendix A.
In previous work, (Gros et al., 1996) the GCA-EoS
was applied to mixtures containing alcohols, water and
any number of inert components by dening a single hydroxyl (OH) associating group to represent association
eects. Later, (Ferreira, Brignole, & Macedo, 2004)
extended the GCA-EoS model to mixtures containing
additionally carboxylic acids, aromatics, ketones and
esters.
The experimental database used to estimate all the
association and attractive parameters did not include
experimental information relative to fatty oil derivatives
mixtures with the exception of the interactions that
involve the triglyceride group. The interactions were
calculated using low-pressure vapourliquid equilibrium
data (LPVLE) and/or pure component vapour pressure
data of short-chain components (Pvap).
The interaction parameter between the triglyceride
and the acid groups, was calculated by tting innite
dilution activity coecients data (c1) of alkanes (hexane
and heptane) in several mixtures of tripalmitin and
palmitic acid (Ferreira & Foco, 2003).
In this work, it was necessary to estimate the CO2
COOH interaction. The interaction parameters between
the COOH group and CO2 were estimated by tting
high-pressure vapourliquid equilibrium data (HPVLE)
of binary mixtures of carbon dioxide and one organic
acid (acetic or butanoic acids), in the temperature
range from 40 to 100 C (Byun, Kim, & McHugh,
2000).

O. Ferreira et al. / Journal of Food Engineering 70 (2005) 579587

581

Table 1
GCA-EoS pure group and binary interaction parameters used in this work
Group

Ti* (K)

g**

g0

Pure group parameters

CH3
CH2
CH3COO
CH2COO
COOH
CH2OH
TG
CO2

600
600
600
600
600
512.6
600
304.2

0.848
0.540
1.728
1.420
1.224
1.124
3.948
1.261

316910
356080
831400
831400
999600.5
787954.0
346350.0
531890.0

0.9274
0.8755
1.0930
1.0930
0.0
0.3634
1.3460
0.578

Group i

Group j

kij

k 0ij

aij

aji
0.0
0.0
0.0
3.0382

Binary interaction parameters

COOH
CH3/CH2
CH3COO/CH2COO
TG
CO2

g00

0.8520
1.0000
1.1000
0.9592

0.0
0.0
0.0
0.0

0.0
0.0
0.0
3.0382

0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0

CH2OH

CH3/CH2
COOH

0.8500
1.0383

0.0
0

11.90
0

1.62
0

CO2

CH3
CH2
CH3COO/CH2COO
TG

0.898
0.874
1.115
1.094

0.0
0.0
0.094
0.1120

0.0
0.0
1.615
1.651

0.0
0.0
1.615
1.651

CH2COO

CH3/CH2
CH2OH

0.8690
1.0000

0.0
0.0

0.0
0.0

0.0
0.0

TG

CH3/CH2

0.8600

0.0

0.0

0.0

Table 2
GCA-EoS self and cross-association parameters
Groups

Self-association

COOH
OH

eij/k (K)

jij (cm3/mol)

6300.0
2700.0

0.0200
0.8621

Cross-association
i

eij/k (K)

jij (cm3/mol)

COOH

COOR
OH
COOR

3248.8
4500.0
2105.3

0.7786
0.1313
0.9916

OH

The GCA-EoS parameters used in this work (Espinosa et al., 2000; Ferreira et al., 2004; Gros et al., 1996)
are given on Tables 1 and 2.
2.1. Repulsive term
The critical diameter of components where the group
described in the attractive term coincides with the molecule (H2O, CH3OH, CO2) is given, rigorously, by the
equation (Skjold-Jrgensen, 1988):


dc

0:08943

RT c
Pc

13
2

For the remaining cases, the critical diameter is tted

to a point of the vapour pressure curve, usually the normal boiling point.
The repulsive molecular parameter (the critical hard
sphere diameter, dc) for the high-molecular weight triglycerides was obtained from innite dilution activity
coecient data of alkanes in these triglycerides, since
critical properties or vapor pressure data cannot be used
due the low-volatility and thermal liability of triglycerides. A correlation between the critical diameter and
the van der Waals molecular volume of high-molecular
weight compounds was obtained (Espinosa et al., 2002):
logd c 0:4152 0:4128 logrvdw
3
2.2. Attractive term
The group-contribution attractive term has ve puregroup parameters (T*, q, g*, g 0 and g00 ) and four binary
interaction parameters (the symmetrical k
ij and k 0ij and
the asymmetrical non-randomness parameters aij and
aji). The GCA-EoS parameters from the attractive term
are presented on Table 1 (Espinosa et al., 2000; Ferreira
et al., 2004; Gros et al., 1996; this work).
2.3. Association term
In the associating term of the GCA-EoS, each
self-associating group (e.g. the acid and the hydroxyl

O. Ferreira et al. / Journal of Food Engineering 70 (2005) 579587

associating groups) is characterized through two parameters: volume j and energy of association e/k. In some
cases where there is more then one associating group
present in the mixture, cross-association can occur
(e.g. acidhydroxyl; acidester). For these cases it is also
necessary to dene the cross-association parameters.
From the association point of view, the fatty oil mixtures considered in this work contain at least one of
three groups that can hydrogen bond: the ester, the alcohol and the acid group. The corresponding self-and
cross-association parameters used in this work are presented on Table 2 (Ferreira et al., 2004).

320

palmitic acid, 100 C

240

P (bar)

582

lauric acid, 60 C
caproic acid, 35 C

160

80

0
0.0

0.2

0.4

0.6

0.8

1.0

CO mole fraction
2

Fig. 2. Binary VLE of CO2 and fatty acids. Exp. data: n d (Bharath
et al., 1993); (Byun et al., 2000); GCA-EoS prediction.

The scarce experimental information available for

these systems supports the importance of using a predictive group-contribution model as the GCA-EoS.
The parameters obtained previously (Espinosa et al.,
2000; Ferreira et al., 2004; Gros et al., 1996) and in this
work are now used to predict the behaviour of highpressure phase equilibria for mixtures containing fatty
oils and derivatives with solvents like propane and carbon dioxide.

320

240

P (bar)

3. Predictions

40 C
60 C
80 C
160

80

3.1. Binary systems of CO2 and fatty acids

0

Figs. 14 show some of the GCA-EoS predictions for

the solubility of CO2 in several fatty acids. Good results
are obtained for the solubilities of carbon dioxide in the
saturated fatty acids (Figs. 1 and 2). From Fig. 3, it can
be observed that the model predictions, for the unsaturated oleic acid, only present a qualitative agreement
for the CO2 solubility change with temperature.
The model is also able to qualitatively distinguish between the oleic acid (9-octadecenoic acid) and linoleic

0.0

0.2

0.4

0.6

0.8

1.0

CO mole fraction
2

Fig. 3. Binary VLE of CO2 and oleic acid: exp. (Bharath et al., 1992);
GCA-EoS prediction.

360

300

oleic acid
linoleic acid

P (bar)

240
60

180

120
100 C
150 C
200 C

P (bar)

40

60

0
0.0

20

0
0.0

0.1

0.2
0.3
CO mole fraction

0.4

0.5

0.6

0.2

0.4
0.6
CO 2 mole fraction

0.8

1.0

Fig. 4. Binary VLE of CO2 and unsaturated fatty acids at 40 C. Exp.
data: d oleic acid (Bharath et al., 1992); s linoleic acid (Chen et al.,
2000); GCA-EoS predictions.

Fig. 1. Binary VLE of CO2 and palmitic acid: Exp. data (Yau et al.,
1992); GCA-EoS predictions.

acid (9,12-octadecadienoic acid), as can be seen from

Fig. 4.

O. Ferreira et al. / Journal of Food Engineering 70 (2005) 579587

3.2. Binary systems of propane and fatty acids

583

60
98 C

Pressure (bar)

At high pressures, these asymmetric systems present a

complex multi-phase behaviour, dicult to model. A review on the multiphase equilibria for systems containing
near critical solvents (from methane to butane and ethylene) and less volatile solutes, based on experimental
results was presented (Peters, 1994). Amongst the solutes studied are n-alkanes, triglycerides, n-carboxylic
acids and n-alkanols.
And what is the inuence of the presence of functional groups like the acid group in the solute? Acids
present a LLG curve, corresponding to a Type V behaviour (Konynenburg & Scott, 1980), for lower carbon
numbers when compared to the n-alkanes series. This
can be ascribed to the formation of dimers in the acids.
For example, n-octadecanoic acid (C18H36O2) is expected to have a similar behaviour to the n-hexatriacontane (C36H74).
Similarly to the propane + triglycerides systems, the
GCA-EoS model is able to predict the three phase
LLV equilibrium for propane + fatty acids systems.
The fact that association is taken into account, i.e., that
fatty acids are capable of forming dimers, allows the
model to predict the existence of liquidliquid equilibria
in a range of temperatures similar to the one predicted
for an alkane with double size. For example, Fig. 5 presents the VLE and LLE predictions for the binary mixture of propane and oleic acid. The LCEP is estimated at

a lower temperature (T CALC
LCEP 84 C) than the experi
mental one (T EXP

91:1
C).
LCEP
It should be mentioned that all the parameters were
estimated using vapour pressure data of n-carboxylic
acids (from acetic to heptanoic acid) and binary lowpressure VLE data for small acids with alkanes (heptane

91 C
98 C

92 C

40
84 C
20

0
0.6

0.7

0.8
propane mole fraction

0.9

1.0

Fig. 5. Binary VLE and LLE for propane and oleic acid. Exp. data
(Hixson and Hixson, 1941); GCA-EoS predictions.

and octane). And, due to this, it is reasonable that the

predictions at these high pressures are less accurate.
3.3. Innite dilution activity coecients
In this section, the GCA-EoS model is used to predict
innite dilution activity coecients of alkanes in palmitic
acid and mono- and di-palmitin. The dc values of the fatty
compounds were obtained from a vapour pressure data
point (Formo, Jurgemann, Norris, & Sonntag, 1982).
Table 3 shows a comparison between the model predictions and experimental data (Foco, Bermudez, & Bottini,
1996). Predictions are quite satisfactory, taking into account the lack of vapour pressure data which is necessary
to estimate the dc value for the fatty oil derivatives.
3.4. Ternary systems of propane + oleic acid + cottonseed
oil
The use of liqueed propane to extract fatty acids
from natural oils, by selecting a temperature above the

Table 3
Innite dilution activity coecients of n-heptane and ethyl acetate in palmitic acid, mono-, di- and tri-palmitin: comparison between experimental
data and model predictions
Solvents

T (K)

Solutes
n-Heptane

Ethyl acetate

Exp.

GCA-EoS

Error (%)

Exp.

GCA-EoS

Error (%)

Palmitic acid

355
366
374

1.51
1.54
1.59

1.20
1.21
1.21

20
21
24

1.36
1.32
1.34

1.25
1.23
1.21

8
7
10

Monopalmitin

355
365
375

2.07
2.02
2.02

1.72
1.68
1.64

17
17
19

1.33
1.28
1.15

1.17
1.17
1.18

12
9
3

Dipalmitin

355
365
375

0.99
0.96
0.96

0.95
0.91
0.88

4
5
9

0.72
0.69
0.68

0.91
0.87
0.85

26
27
25

Tripalmitin

351
361
368

0.61
0.61
0.61

0.63
0.63
0.63

3
3
3

1.23
1.06
1.11

1.37
1.34
1.31

11
26
18

584

O. Ferreira et al. / Journal of Food Engineering 70 (2005) 579587

Table 4
Glycerides composition (xi) and correspondent aliphatic groups (nCH2
and nCH@CH) decomposition for cottonseed oil

Oleic acid
0.00 1.00
0.25

0.75

0.50

0.50

Cottonseed oil
0.75

1.00
0.00

0.50

0.75

nCH2

nCH@CH

0.25
0.30
0.45

42
42
36

0
3
6

39.3

3.60

3.5. Ternary system of CO2 + oleic acid + methyl oleate

0.00
1.00

Propane

xi

Palmitic acid
Oleic acid
Linoleic acid
Average value

0.25

0.25

Fatty acid

Cottonseed oil

Fig. 6. LLE of C3H8oleic acidcottonseed oil at 98.5 C and 44 bar

(compositions in weight fractions): jexp. (Hixson and Bockelmann,
1942); GCA-EoS.

critical solution temperature of the triglyceride and

below that of the fatty acid, was suggested (Hixson &
Bockelmann, 1942). Previous work had shown the capabilities of the GC-EoS model to describe with the same
set of parameters, the LLE and VLE observed in the systems propane-TAG.
Fig. 6 shows the satisfactory GCA-EoS predictions
for the ternary system of propane, oleic acid and cottonseed oil. The cottonseed oil is represented by a pseudotriacylglyceride molecule with the following group
composition: one triglyceride group and the average aliphatic group values given on the last row of Table 4.
After this, the correlation between the critical diameter
and the van der Waals molecular volume, given by Eq.
(3), is used to estimate the critical diameter for this rened cottonseed oil. The following value was obtained:
dc = 11.71.

The uidliquid equilibria of the ternary system supercritical carbon dioxide with several mixtures of oleic acid
and methyl oleate was studied (Yu et al., 1993). Fig. 7
shows the GCA-EoS predictions at the two temperatures
for which data are available: 40 and 60 C.
As can be seen, the GCA-EoS predicts the sharp increase in the solubility for both components as carbon
dioxide becomes supercritical: the solubilities for both
components decrease with temperature (at constant
pressure) and increase with pressure (at constant temperature). The model is also able to predict the higher
solubility of the ester relatively to the acid at a given
temperature and pressure. No additional parameters
were estimated for this system. For pressures higher
than 30 MPa, the GCA-EoS model predicts a curvature
on the solubility of oleic acid, which is not observed
experimentally.
3.6. Ternary system of CO2 + triolein + oleic acid
Carbon dioxide can be used as a solvent to remove
fatty acids from oil mixtures. With this purpose, some
researchers (Bharath, Inomata, Adschiri, & Arai, 1992)

R=1.00
R=0.75
R=0.50
R=0.25
R=0.00

30
20

40

T = 40 C

P(MPa)

P(MPa)

40

10

20

T = 40 C

R=1.0
0
R=0.7
5
R=0.5

10
0
0.97

0
0.0

0.2

0.4
0.6
0.8
CO2 mole fraction

40

1.0

10
0
0.0

P(MPa)

20

R=1.00
R=0.75
R=0.50
R=0.25
R=0.00
0.5
CO2 mole fraction

1.00

T = 60 C

30
20
10

1.0

0.98
0.99
CO2 mole fraction

40

T = 60 C

30
P(MPa)

30

0
0.97

R=1.00
R=0.75
R=0.50
R=0.25
R=0.00
0.98
0.99
CO2 mole fraction

1.00

Fig. 7. VLE for the system CO2 + methyl oleate + oleic acid for several mixtures with overall xed mole fractions (R = oleic acid mole fraction on a
CO2 free basis). Exp. data: h n (Yu et al., 1993); (Inomata et al., 1989); d (Bharath et al., 1992); GCA-EoS predictions.

O. Ferreira et al. / Journal of Food Engineering 70 (2005) 579587

585

Fig. 8. Ternary VLE of CO2, oleic acid and triolein at 250 bar: j exp. (Bharath et al., 1992); GCA-EoS prediction.

measured data on the systems CO2, oleic acid and triolein (OOO), which are shown on Fig. 8, together with
the GCA-EoS predictions at two temperatures.
Even though the CO2 solvent power predicted by the
model is lower than indicated by the measured data
(Bharath et al., 1992), the selectivity is correct, i.e., the
equation shows the higher anity of CO2 for the fatty
acid.
4. Conclusions
Phase equilibria of supercritical gases in fatty oil
derivatives (fatty acids, fatty acid esters, mono- and diglycerides) were predicted using the GCA-EoS model
that specically takes into account association eects.
The parameters obtained at low pressures (using binary mixtures of carboxylic acids, alcohols, esters, water
and alkanes) and at high pressures (CO2 and acids) were
used to model the phase behaviour of mixtures of fatty
oils and their derivatives with supercritical uids. A satisfactory comparison with experimental data was
achieved.
The GCA-EoS model shows great exibility to represent phase equilibrium behaviour in very asymmetric
mixtures with respect to size and energetic interactions
which suggest its use as an engineering tool to optimize
and design extraction and fractionation processes of
fatty oil derivatives with supercritical uids.
Acknowledgements
O. Ferreira acknowledges nancial support from the
PRAXIS program, FCT, Lisbon, Portugal (SFRH/BD/
879/2000). E.A. Brignole acknowledges nancial support from CONICET, Argentina and the Universidad
Nacional del Sur.

Appendix A
The residual energy of Helmholtz can be written as a
sum of three terms: the repulsive term (rep), the attractive term (attr) and the association term (assoc):
 
 
 
AR AR rep AR attr AR assoc
A:1
The repulsive contribution is represented by the extended CarnahanStarling equation for mixtures of
hard spheres developed by Mansoori and Leland
(1972) and it is a function of the hard spheres diameter
per mol of component i(di):



 R

k1 k2
A =RT rep 3
Y  1
k3
!

k32  2
A:2

Y  Y  ln Y n ln Y
2
k3
PNC
3 1
and kk i1 ni d ki .
where Y 1  pk
6V
In these equations, n is the total number of moles, ni
is the number of moles of component i, V is the total
volume and NC is the number of components. The temperature dependence of the diameter di is given by
d i 1:066d c i1  0:12 exp2T ci =3T 

A:3

The critical diameter dci is the hard spheres diameter

value at the critical temperature of pure component i,
Tci.
The attractive term is similar to the van der Waals
expression for the attractive term combined with a
group-contribution version of an NRTL (Renon &
Prausnit, 1968) type equation. The interactions occur
through the functional groups surfaces:


AR =RT


attr

NG
^z X
n
j qj
2RTV j1

PNG

qgkj skj
k1 hk ~
PNG
l1 hl slj

A:4

586

O. Ferreira et al. / Journal of Food Engineering 70 (2005) 579587

where

nj

PNC
i

ni mij ;

~
q

PNC
j

nj qj ;

hj

nj qj


~
q

and

aij g g ~
q
exp jkRTV kk ij .

sjk
The surface area qi and the dispersive energy gii are
the pure group parameters. The attractive energy
parameter gjk quanties the attractive interactions between the segment groups j and k with the correspondent asymmetrical random parameter ajk. In the above
expressions

nj is the total number of moles of group j;
~q is the total number of surface segments; hj is the surface fraction of group j, mij is the number of groups of
type j in molecule i; ^z is the number of nearest neighbours to any segment (set equal to 10).
The attractive energy gij is calculated from the energy
between like-group segments through the following
combination rule:
gij k ij gii gjj

0:5

A:5

where the binary interaction parameter kij is symmetrical (kij = kji). Both, the attractive energy between like
segments and the binary interaction parameter are temperature dependent:


j

k
gjj g
jj 1 g0jj T =T
j  1 g00jj ln T =T
j
A:6
n
h
io
k ij k
ij 1 k 0ij ln 2T =T
i T
j

A:7

where T
j is an arbitrary, but xed reference temperature

for group j, g
jj , g0jj and g00jj are pure-group energy parameters and k
ij and k 0ij are binary group interaction
parameters.
The association contribution to the residual energy of
Helmholtz is a function of the number of association
groups NGA present in the mixture:
"
#

R

N
GA
X

X
A
X Ak
1


Ak

nk
ln X 
Mk
2
RT assoc
2
Ak
k1
A:8
where n
k is the number of moles of the association group
k. The mole fraction of group k not associated at site A,
X Ak is given by
X Ak

Mj
N
GA X
X
j1

!1
q
j X Bj D

Ak Bj

A:9

l1

where q
j is the mole density of group j. The association

strength (DAk Bj ) is a function of two association parameters between site A of group k and site B of group j:
the association energy e and the corresponding bonding
volume j.


Ak Bj 

e
DAk Bj jAk Bj exp
1
kT

A:10

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