Fluid Phase Equilibria 299 (2010) 141–147

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Fluid Phase Equilibria

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Liquid–liquid equilibria for systems composed of refined soybean oil, free fatty
acids, ethanol, and water at different temperatures
Cristina Chiyoda a , Elaine C.D. Peixoto b , Antonio J.A. Meirelles b , Christianne E.C. Rodrigues a,∗
a
LES, Department of Food Engineering (ZEA-FZEA), University of São Paulo (USP), P.O. Box 23, Zip Code 13635-900, Pirassununga, SP, Brazil
b
EXTRAE, Department of Food Engineering (DEA-FEA), University of Campinas (UNICAMP), P.O. Box 6121, Zip Code 13083-862, Campinas, SP, Brazil

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

Article history: Soybean oil can be deacidified by liquid–liquid extraction with ethanol. In the present paper, the
Received 31 May 2010 liquid–liquid equilibria of systems composed of refined soybean oil, commercial linoleic acid, ethanol
Received in revised form 9 September 2010 and water were investigated at 298.2 K. The experimental data set obtained from the present study (at
Accepted 14 September 2010
298.2 K) and the results of Mohsen-Nia et al. [1] (at 303.2 K) and Rodrigues et al. [2] (at 323.2 K) were
Available online 18 September 2010
correlated by applying the non-random two liquid (NRTL) model. The results of the present study indi-
cated that the mutual solubility of the compounds decreased with an increase in the water content of
Keywords:
the solvent and a decrease in the temperature of the solution. Among variables, the water content of the
Liquid–liquid extraction
Deacidification
solvent had the strongest effect on the solubility of the components. The maximum deviation and average
Linoleic acid variance between the experimental and calculated compositions were 1.60% and 0.89%, indicating that
Solvent extraction the model could accurately predict the behavior of the compounds at different temperatures and degrees
NRTL of hydration.
© 2010 Elsevier B.V. All rights reserved.

1. Introduction sification of triacylglycerols, which lead to the loss of neutral oil

In 2009, the total world production of major oilseeds was 395.2
million metric tons, and soybeans were the most commonly pro-
duced oilseed, representing 53% of the total crop. The largest
soybean producer was the United States of America (38%), followed
by Brazil (27%), and Argentina (15%) [3]. Among oilseeds, the pro-
duction of soybeans is high because the byproducts obtained from
the processing of soybean oil are more valuable than that of other
oilseeds, especially protein [4].
Crude oil extracted from oilseeds contains a mixture of triacyl-
glycerols, partial acylglycerols, free fatty acids (FFA), phospholipids,
sterols, tocopherols and hydrocarbons. To comply with safety leg-
islation governing the food industry, all vegetable oils must be
treated to remove undesirable compounds such as FFAs [5].
From an economic point of view, FFA removal (deacidification)
is the most important stage in the purification of vegetable oils [5].
The deacidification of soybean oil is often achieved by neutralizing
free fatty acids with an aqueous alkaline solution. This procedure
is commonly referred to as chemical, alkali or caustic refining, and
requires large volumes of water to remove residual soap from neu-
tral oil [4]. Moreover, for oils with a high concentration of free
fatty acids, caustic refining results in the saponification and emul-
∗ Corresponding author. Tel.: +55 19 3565 4354; fax: +55 19 3565 4343.
E-mail address: chrisrodrigues@usp.br (C.E.C. Rodrigues).
[4,5].
Moreover, during the refinement of highly acidic oils, a pro-
cess similar to steam deodorization (physical refining) is typically
conducted if the phosphorus concentration of the oil is low [4].
New methods for the deacidification of vegetable oils, such
as supercritical fluid extraction [6,7], membrane processing [8,9],
biological deacidification [10], chemical reesterification [11],
molecular distillation [12] and solvent (or liquid–liquid) extrac-
tion [1,2,13], have been proposed to replace traditional methods.
Liquid–liquid extraction (LLE) is based on the differences in the sol-
ubility of FFA and triacylglycerols in a given solvent. Compared to
chemical deacidification, the effluent output, water consumption
and energy consumption of LLE is relatively low because the pro-
cedure is conducted under mild conditions (low temperature and
pressure [14]).
Ethanol has been considered the best solvent for LLE since it
presents low toxicity, it is easily recovered and it presents good
selectivity values and distribution coefficient for FFA. Moreover,
with ethanol, the loss of nutraceutical compounds during LLE is
relatively low [2,15].
In the present paper, equilibrium data for systems composed of
soybean oil (1), commercial linoleic acid (2), ethanol (3) and water
(4) are reported. Experimental data were collected at 298.2 K, and
the alcoholic solvents presented water contents of up to 30% by
mass. In addition, the experimental data obtained in the present
study and the results presented in the literature [1,2] were cor-

0378-3812/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.fluid.2010.09.024
142 C. Chiyoda et al. / Fluid Phase Equilibria 299 (2010) 141–147

related using the NRTL equation. The adjustment of interaction oil or the alcoholic phase was determined by weighing the sample
parameters enabled the simulation of liquid–liquid extractors in every 60 min until a constant mass was achieved. The water content
the deacidification of vegetable oils. was determined by Karl–Fischer titration with a KF Titrino titrator
(Metrohm, model 701, Herisan, Switzerland), according to AOCS
2. Experimental method Ca 23–55 [16]. The triacylglycerol content was determined
by difference.
2.1. Materials In the present study, all measurements were performed in tripli-
cate, and type A standard uncertainties [19] in the equilibrium data
Absolute ethanol (>99.5% pure) was purchased from Merck varied within the following ranges: 0.06–0.67 mass% for vegetable
(Darmstadt, Germany), and aqueous solvents with different water oil, 0.02–0.41 mass% for commercial linoleic acid, 0.03–0.55 mass
contents (5.45, 18.35 and 30.15 mass%) were prepared by diluting % for ethanol, and 0.06–0.28 mass% for water. In the aforemen-
absolute ethanol with deionized water (Millipore, Milli-Q, Bedford, tioned data set, the lowest values were obtained from the lowest
MA, USA). concentrations.
To determine the fatty acid methyl ester (FAME) composition of To evaluate the validity of the results, the procedure developed
fatty reagents, commercial linoleic acid (Fluka, Switzerland) and by Marcilla and coworkers [20] was employed. In the aforemen-
refined soybean oil (Cargill, Brazil) were analyzed by gas chro- tioned procedure, the mass of each phase (MOP and MAP ) was
matography, according to the official method of the AOCS (1–62) calculated by applying a least-squares fitting to the experimental
[16]. Prior to chromatographic analyses, fatty samples were con- values of wiOP and wiAP .
verted to FAME, according to the official method of the AOCS Deviations (ı) between the MOC (the mass of the initial mixture)
(2–66) [16]. A gas chromatograph equipped with a flame ion- and the sum of MOP and MAP were calculated according to Eq. (1).
ization detector (HP, model 5890, Palo Alto, USA) and a fused  
(M OP + M AP ) − M OC 
silica–cyanopropylsiloxane column with dimensions of 0.25 ␮m, ı= × 100 (1)
60 m × 0.32 mm i.d. was used under the following experimental M OC
conditions: hydrogen carrier gas at a rate of 2.5 mL/min; injection
temperature of 548.2 K; column temperature of 448.2–498.2 K at In the equilibrium experiments, the relative deviation of the
a ramp rate of 1.3 K/min; and detection temperature of 578.2 K. mass balance of each compound i (ıi ) was calculated according to
The FAME content of the fatty reagents was compared to external Eq. (2).
standards purchased from Nu Check Inc. (Elysian, USA).    
 M OP wOP + M AP wAP − M OC wOC 
i i i
ıi = × 100 (2)
2.2. Experimental procedure M OC wiOC

Model fatty systems containing fatty acids and triacylglycerols The relative deviation (ı) of the results was less than 0.5%, indi-
were prepared by adding defined quantities of commercial linoleic cating that the precision and repeatability of the equilibrium data
acid to refined soybean oil, according to the published method- was high [2,15].
ology [2]. The model fatty systems were mixed with ethanolic
solvents in a 1:1 oil:solvent mass ratio at 298.2 ± 0.1 K to obtain 2.3. Modeling procedure
the liquid–liquid equilibrium data, which were used to adjust the
NRTL parameters. The experimental data were used to adjust the NRTL binary
Equilibrium cells similar to those used by Silva et al. [17] interaction parameters. Traditionally, mole fractions are used with
were employed to obtain the liquid–liquid equilibrium data. The the NRTL model, but mass fractions provide a more convenient unit
cell temperature was controlled with a thermostatic bath (Cole- due to the large differences in the molar masses of the components.
Parmer, model 12101-55, Chicago, USA, accuracy = ±0.01 K), and In several recent studies, mass fractions have been used with the
thermometers (Cole-Parmer, Chicago, USA) with a readability of NRTL model [2,13,15,21–27]. When using mass fractions, the NRTL
±0.1 K were used to monitor the temperature of the cell. Oil, free model for multicomponent mixtures is expressed as:
K 
K K
ji Gji wj /M j wj Gji kj Gkj wk /M k
j K + K ij − k=1
K
Gji wj /M j Mj G w /M k G w /M k
j j=1 k=1 kj k k=1 kj k
ln iw = K  (3)
Mi j=1
wj /M j

fatty acids and solvent were weighed on an analytical balance gij

ij = (4)
(Adam, model AAA200, Milton Keynes, UK) with a readability and RT
accuracy of 0.0001 g. The mixture was vigorously stirred with a gij
magnetic stirrer (Fisatom, model 752A, Brazil) for 20 min and was = A0,ij + A1,ij T (5)
R
allowed to stand for 24 h to obtain two clear and transparent phases
Gij = exp(−˛ij ij ) (6)
with a well-defined interface.
The free fatty acid content was determined by titration (IUPAC ˛ij = ˛ji (7)
official method 2201 [18]) with an automatic burette (Metrohm,
model Dosimat 715, Herisan, Switzerland). The total solvent com- where iw is the corresponding activity coefficient of component
position was determined by evaporating the oil to a constant mass i expressed as a mass fraction, M and w are the average molar
in a vacuum oven (inner absolute pressure = 126 mmHg) at 313.2 K mass and mass fraction of the pseudocomponents, gij and  ij are
(Napco, model 5831, USA). The temperature and pressure used to the molecular energy interactions between components i and j, ˛ij
determine the solvent composition were selected to prevent the is the non-randomness parameter of the mixture, T is the abso-
degradation/volatilization of fatty compounds in the samples. The lute temperature and A0,ij , A0,ji , A1,ij , and A1,ji are the characteristic
drying period required to completely remove the solvent from the energy parameters of the interactions between components i and j.
 C. Chiyoda et al. / Fluid Phase Equilibria 299 (2010) 141–147 143

Table 1
Fatty acid compositions of refined soybean oil and commercial linoleic acid.

Symbol Fatty acids Cx:ya Mb (g mol−1 ) Soybean oil Linoleic acid

100x 100w 100x 100w

P Hexadecanoic C16:0 256.43 12.53 11.55 8.30 7.63

S Octadecanoic C18:0 284.49 3.99 4.07 4.00 4.07
O Cis-octadec-9-enoic C18:1 282.47 23.67 24.01 16.82 17.03
Li Cis,cis-octadeca-9,12-dienoic C18:2 280.45 53.60 54.00 70.88 71.27
Le All-cis-octadeca-9,12,15-trienoic C18:3 278.44 5.46 5.45
Be Docosanoic C22:0 340.59 0.75 0.92
a
In Cx:y, x = number of carbons and y = number of double bonds.
b
M = molar mass.

Thus, five adjustable parameters were used for each pair of compo-
nents. The parameters were estimated from the experimental data,
according to the following procedure [21].
Adjustments to the parameters were made by assuming that a
mixture of refined soybean oil, free fatty acids (commercial oleic or
linoleic acid) and anhydrous ethanol was pseudoternary, and that
a mixture of refined soybean oil, free fatty acids (commercial oleic
or linoleic acid), ethanol and water was pseudoquaternary.
During the adjustment process, soybean oil was considered to
be a single triacylglycerol with an average molar mass equal to
that of the oil, and the same approach was extended to the free
fatty acids. This approach is based on the assumption that differ-
ent triacylglycerols present in soybean oil behave similarly in the
proposed liquid–liquid system. Thus, the components of soybean
oil can be adequately replaced by a pseudocompound with aver-
age physical–chemical properties. The same assumption is valid
for mixtures of free fatty acids. The aforementioned approach has
been evaluated by Lanza et al. [28], who proved its veracity.
The experimental data obtained at 298.2 K (the results of the
present study) and 323.2 K (the results of Rodrigues et al. [2]) were
based on commercial linoleic acid as a fatty acid source. Alterna-
tively, the experimental data obtained at 303.2 K were based on
commercial oleic acid [1]. Despite the differences in the fatty acid
composition, all of the free fatty acids were assigned the same molar
mass, which was calculated according to the commercial linoleic
acid composition during behavior modeling studies [2].
The interaction parameter was estimated based on the min-
imization of the objective function of the composition (Eq. (8)),
according to the algorithm developed in FORTRAN language by
Stragevitch and d’Avila [29].
3. Results
As previously mentioned, the NRTL interaction parameters were
adjusted with the data set obtained from the present study (at
298.2 K) and the results of Mohsen-Nia et al. [1] (at 303.2 K) and
Rodrigues et al. [2] (at 323.2 K). The refined soybean oil and com-
mercial linoleic acid used in the work of Rodrigues et al. [2] was
identical to those used in the present study.
The fatty acid composition of refined soybean oil and com-
mercial linoleic acid are presented in Table 1. From the fatty acid
composition of refined soybean oil, the triacylglycerol composition
of the oil was estimated using the procedure proposed by Antoniosi
Filho et al. [30] (Table 2).
Among all possible isomers (with x carbons and y double bonds),
the triacylglycerol with the highest concentration was considered
to be the primary component of soybean oil. Thus, to fit the thermo-
dynamic model, vegetable oil was treated as a single triacylglycerol
with an average molar mass equal to that of the oil. For this reason,
the average molar mass of soybean oil was calculated according to
the estimated triacylglycerol composition (Table 2).
The calculated molar masses of refined soybean oil and com-
mercial linoleic acid were 872.93 and 278.96 g mol−1 , respectively.
The residual acidity of refined oil, expressed as linoleic acid, was
0.11 ± 0.01 mass% [2].
The results of Mohsen-Nia et al. [1] suggested that the molar
masses of commercial oleic acid and soybean oil were 282 g mol−1
and 875 g mol−1 , respectively. The molar masses obtained by
Mohsen-Nia et al. [1] were similar to those obtained in the
present study. Thus, in the modeling procedure, a molar mass of

  Table 2

D

N

K−1 OP,exp OP,calc
wi,n,m − wi,n,m
2 AP,exp AP,calc
wi,n,m − wi,n,m
2
Probable triacylglycerol (TAG) composition of refined soybean oil.
OF(w) = + (8)
wOP wOP
i,n,m i,n,m Group Main TAGb Mc (g mol−1 ) Refined Soybean Oil
m=1 n=1 i=1

100x 100w
where D is the total number of data groups; N is the total number 50:1a POP 833.37 1.03 0.98
of tie lines in the data groups; K is the total number of components 50:2 PLiP 831.35 2.33 2.22
or pseudocompounds in data group m; w is the mass fraction; the 52:1 POS 861.45 0.66 0.65
52:2 POO 859.40 3.81 3.75
subscripts i, n and m represent the component, tie line and group
52:3 POLi 857.39 10.67 10.48
number, respectively; the superscripts OP and AP represent the oil 52:4 PLiLi 855.37 12.97 12.71
and alcoholic phases, respectively; exp and calc refer to the exper- 52:5 PLiLe 853.37 2.42 2.37
imental and calculated composition, respectively; and wOP and 54:2 SOO 887.46 0.98 0.99
i,n,m 54:3 SOLi 885.46 4.68 4.75
wAP are the standard deviation of the composition of the liquid 54:4 OOLi 883.43 13.03 13.19
i,n,m
54:5 OLiLi 881.41 21.81 22.03
phases, respectively.
54:6 LiLiLi 879.43 19.34 19.48
The average deviations between the experimental and calcu- 54:7 LiLiLe 877.38 4.85 4.87
lated compositions of both phases were calculated according to Eq. 58:3 OLiBe 941.57 0.64 0.69
(9). 58:4 LiLiBe 939.55 0.78 0.84
a
 x:y, x = number of carbons (except carbons of glycerol), y = number of double
N K  OP,exp OP,calc
2  AP,exp AP,calc
2  bonds.
wi,n − wi,n + wi,n − wi,n b
Groups with a total triacylglycerol (TAG) composition lower than 0.5% were
n=1 i=1
w = 100 (9) ignored.
2NK c
M = molar mass.
144 C. Chiyoda et al. / Fluid Phase Equilibria 299 (2010) 141–147

Fig. 1. Distribution diagram for systems containing refined soybean oil (1) + free fatty acids (2) + ethanol (3) + water (4): () 100w4S = 0%; () 100w4S = 5%; (䊉) 100w4S = 10%;
() 100w4S = 15%; () 100w4S = 18%; () 100w4S = 30%; (- - -) NRTL model. (a) 298.2 K, (b) 303.2 K, (c) 323.2 K.

278.96 g mol−1 and 872.93 g mol−1 was adopted for free fatty acid
and soybean oil, respectively.
Tables 3 and 4 present the composition of the alcoholic and
oil phases of the pseudoternary (absolute ethanol as solvent) and
pseudoquaternary (aqueous ethanol as solvent) model systems at
298.2 K, respectively. The compositions of the systems are reported
as mass percentages.
Liquid–liquid experimental data at 303.2 and 323.2 K were
obtained from the work of Mohsen-Nia et al. [1] and Rodrigues et
al. [2], respectively. These data sets and the data at 298.2 K were
correlated by applying the NRTL equation.
Fig. 1 shows the distribution of free fatty acids between the alco-
holic (AP) and oily (OP) phases. As shown in the figure, an increase
in the water content reduced the FFA extracting capacity of the sol-
vents. Moreover, an increase in temperature of the solution did not
affect the distribution of FFA between the two phases.
The ability of the NRTL model to accurately describe the parti-
tioning of free fatty acids is shown in Fig. 1. The adjusted interaction
parameters accurately described the effects of solvent hydration
and temperature on the distribution of free fatty acids between
oily and alcoholic phases (the adjusted parameters are shown in
Table 5).
Deviations between the experimental and calculated composi-
tion of both phases were calculated according to Eq. (9) and are
shown in Table 6.
The partitioning of free fatty acids at different temperatures
and degrees of solvent hydration during the deacidification of
degummed sunflower seed oil has been studied by Cuevas et al.
[22]. The results of the aforementioned study indicated that the
partitioning of free fatty acids was not significantly affected by the
temperature of the solution. Alternatively, an increase in the water
content of the solvent reduced the free fatty acid extracting capacity
of the solvent [22].
In fact, the effect of the water content of the solvent on the
FFA distribution coefficient and the mutual solubility of neutral oil
and solvent has been extensively studied in previous investigations
[13,15,22–27]. In the present work, the effect of temperature on
the phase equilibrium was evaluated, and a joint analysis of the
data obtained by Mohsen-Nia et al. [1] and Rodrigues et al. [2] was
performed.

Table 3
Liquid–liquid equilibrium data for the system refined soybean oil (1) + commercial linoleic acid (2) + ethanol (3), at (298.2 ± 0.1) K.

OCa OPb APc

100w1 100w2 100w3 100w1 100w2 100w3 100w1 100w2 100w3

49.91 0.00 50.09 85.40 0.00 14.60 6.43 0.00 93.57

49.36 0.52 50.12 84.46 0.56 14.98 6.41 0.79 92.80
48.35 1.30 50.35 84.33 0.96 14.71 7.06 1.50 91.44
47.22 2.50 50.28 81.91 2.20 15.89 7.19 3.19 89.62
46.49 3.59 49.92 79.90 2.90 17.20 8.77 3.98 87.25
44.86 5.03 50.11 76.95 4.12 18.92 11.07 5.49 83.44
a
OC = overall composition.
b
OP = oil phase.
c
AP = alcoholic phase.
 C. Chiyoda et al. / Fluid Phase Equilibria 299 (2010) 141–147 145

Table 4
Liquid–liquid equilibrium data for the system refined soybean oil (1) + commercial linoleic acid (2) + ethanol (3) + water (4), at (298.2 ± 0.1) K.

100w4S a OCb OPc APd

100w1 100w2 100w3 100w4 100w1 100w2 100w3 100w4 100w1 100w2 100w3 100w4

49.96 0.00 47.31 2.73 92.84 0.00 6.59 0.57 1.13 0.00 93.25 5.62
48.99 0.56 47.70 2.75 92.12 0.50 7.13 0.25 1.16 0.62 92.16 6.06
48.62 1.30 47.35 2.73 91.00 1.14 7.17 0.69 1.37 1.30 91.00 6.33
47.59 2.42 47.27 2.72 88.65 2.15 8.64 0.56 2.04 2.48 89.94 5.54
5.45 46.35 3.82 47.11 2.72 86.32 3.44 9.64 0.60 2.25 3.98 88.27 5.50
44.93 5.04 47.30 2.73 84.27 4.56 10.38 0.79 2.73 5.19 87.03 5.05
39.90 10.02 47.35 2.73 76.11 9.33 13.54 1.02 4.38 10.28 80.27 5.07
34.98 15.04 47.26 2.72 67.32 14.08 17.60 1.00 7.15 15.56 72.25 5.04
29.96 20.11 47.21 2.72 54.72 19.19 24.39 1.70 13.24 20.22 61.99 4.55
49.92 0.00 40.89 9.19 96.29 0.00 3.18 0.53 0.14 0.00 79.54 20.32
49.43 0.58 40.82 9.17 94.95 0.92 3.82 0.31 0.14 0.53 79.10 20.23
47.56 2.41 40.85 9.18 92.04 3.26 3.69 1.01 0.01 0.87 78.59 20.53
18.35 45.56 5.12 40.27 9.05 87.12 6.81 5.15 0.92 0.21 2.98 76.28 20.53
42.45 7.51 40.86 9.18 83.40 9.78 6.08 0.74 0.23 4.38 74.94 20.45
40.02 10.05 40.77 9.16 78.74 13.02 6.97 1.27 0.42 5.99 76.30 17.29
35.42 14.68 40.74 9.16 69.84 18.97 9.45 1.74 0.56 9.47 71.82 18.15
30.02 20.06 40.76 9.16 59.46 25.31 13.28 1.95 1.48 14.05 67.26 17.21
49.84 0.00 35.04 15.12 97.24 0.00 2.27 0.49 0.10 0.00 69.98 29.92
48.52 0.57 35.56 15.35 96.21 0.76 2.72 0.31 0.05 0.21 69.04 30.70
47.39 2.42 35.06 15.13 92.24 3.74 3.14 0.88 0.17 0.61 71.51 27.71
30.15 44.79 5.02 35.06 15.13 86.60 7.84 4.93 0.63 0.07 1.27 68.36 30.30
42.38 7.51 35.00 15.11 80.53 13.16 5.59 0.72 0.32 2.12 68.43 29.13
40.91 10.18 34.16 14.75 73.42 18.81 6.87 0.90 0.02 3.05 62.67 34.26
34.95 14.97 34.98 15.10 65.27 23.96 9.25 1.52 0.12 3.96 66.47 29.45
30.07 19.98 34.89 15.06 54.84 31.16 11.90 2.10 0.19 5.22 65.98 28.61
a
100w4S = water mass percentage in the solvent.
b
OC = overall composition.
c
OP = oil phase.
d
AP = alcoholic phase.

By applying temperature increments of 2 K and the adjusted Table 6

Mean deviations in phase compositions.
parameters of the NRTL, flash calculations were performed for
model systems containing soybean oil, solvent and different con- Temperature (K) 100w4S a 100w
centrations of water at an oil to solvent mass ratio of 1:1. The overall 298.2 0 1.60
compositions represent the base lines of the systems (tie lines that 5 0.84
correspond to mixtures devoid of free fatty acids). In addition, the 18 0.66
adjusted parameters were used to predict the LLE pseudo-binary 30 0.87
303.2 5 0.88
data for the refined soybean oil and ethanol systems studied by
10 0.88
Follegatti-Romero et al. [31]. 15 0.55
Figs. 2 and 3 present the solubility of the solvent (ethanol and 298.2 0 1.60
water) in the oil phase and the solubility of the neutral oil in the 5 0.96
18 0.61
alcoholic phase, respectively, as a function of the solution temper-
30 0.51
ature. In these figures, the solubility data presented refers to the tie Global deviation of the correlation 0.89
lines of the mixtures devoid of free fatty acids (see line of Table 3 Global deviation of the prediction (298.2–333.2)b 0 2.62
and lines of Table 4 where the mass fraction of fatty acid is null, a
100w4S = water mass percentage in the solvent.
for each value of water content in the solvent). Thus, these figures b
Folegatti-Romero et al. [31].
show how the mutual solubility of oil and solvent is affected by the
temperature of the solution.
The figures show that the water content increase in the sol-
vent results in reduced mutual solubility, for all temperatures soybean oil and absolute ethanol improved as the temperature of
studied. the solution increased. This observation is in accordance with the
As shown in both figures, the effect of temperature on the results of Silva et al. [21].
mutual solubility of the compounds was only significant for sol- In systems with solvents containing large amounts of water, the
vents with low water contents. In other words, the miscibility of mutual solubility of the compounds was slightly affected by tem-

Table 5
NRTL parameters.

Pair ij a A0,ij /K A0,ji /K A1,ij A1,ji ˛ij

12 −3262.30 −121.66 188.47 −92.87 0.46

13 3110.80 1587.20 −2909.05 −43.70 0.46
14 720.51 5496.10 210.33 10412.48 0.15
23 2000.00 −3142.60 23220.48 −144.77 0.21
24 −797.45 3719.80 −4.64 15031.44 −0.16
34 110.68 2000.00 −2851.69 7192.04 0.22
a
Refined soybean oil (1), free fatty acids (2), ethanol (3) and water (4).
146 C. Chiyoda et al. / Fluid Phase Equilibria 299 (2010) 141–147
Fig. 2. Solvent solubility in oil phase as function of temperature for systems con-
taining refined soybean oil (1) + free fatty acids (2) + ethanol (3) + water (4): (a) ()
100w4S = 0% (this work); () 100w4S = 0% (data from [31]); () 100w4S = 5%, (b) ()
100w4S = 10%; () 100w4S = 15%; (䊉) 100w4S = 18%; () 100w4S = 30%; (- - -) NRTL
model.
perature. In fact, the triacylglycerols in soybean oil have a very low
mutual solubility with water which decreases as the chain length
increases and as temperature decreases [21].
For systems containing solvents with high moisture contents, a
decrease in the mutual solubility should be analyzed from a differ-
ent perspective, as suggested by Cuevas et al. [22]. Namely, Cuevas
et al. suggested that molecular clusters originating from a variety of
hydrogen-bonding configurations between ethanol and water are
prevalent when the water content of the solvent is high, resulting
in a moderate temperature effect on the phase behavior of fatty
systems [22].
The results of several studies demonstrated that the diffusivity
of nonpolar molecules in ethanol, water and ethanol–water mix-
tures is temperature dependent [32,33]. For instance, in ethanol,
the temperature dependence of the diffusion coefficient of polar
and nonpolar molecules is variable. Alternatively, differences in the
temperature dependence of the diffusion coefficients of polar and
nonpolar molecules in water were minor [32]. Moreover, the diffu-
Fig. 3. Neutral oil solubility in alcoholic phase as function of temperature for sys-
tems containing refined soybean oil (1) + free fatty acids (2) + ethanol (3) + water (4):
(a) () 100w4S = 0% (this work); () 100w4S = 0% (data from [31]); () 100w4S = 5%,
(b) () 100w4S = 10%; () 100w4S = 15%; (䊉) 100w4S = 18%; () 100w4S = 30%; (- - -)
NRTL model.
sivities of nonpolar solutes decreased with an increase in the water
content of the solvent [33] because the degree of solvation of non-
polar molecules is higher in water (hydrophobic hydration) than
in ethanol [32]. Thus, solute molecules may become solvated in a
water-rich solvent via hydrophobic hydration because interactions
between water and nonpolar molecules increase with an increase
in the water content of ethanol [33].
Based on the aforementioned results, soybean oil, which con-
tains a variety of nonpolar compounds, can become solvated in
solvents with high water contents via hydrophobic hydration.
For systems containing water–solvent mixtures, the hydrophobic
hydration of soybean oil may be associated with weak temperature
effects on the solubility of oil in the alcoholic phase (see Fig. 3).
As shown in Fig. 2, the thermodynamic equation provided a rea-
sonable description of the solubility of the solvent (ethanol and
water) in the oil phase. These results are in agreement with the
overall deviation values, which were low (see Table 6). However,
as shown in Fig. 3, when the water content of the solvent was high,
the descriptive ability of the model decreased. For these types of
systems, the oil content of the alcoholic phase is very low, and rel-
atively high experimental uncertainty was observed. As a result,
greater deviation between the experimental and theoretical results
was observed.
Based on the data shown in Figs. 2 and 3 and Table 6, one can
conclude that the performance of the NRTL model in the descrip-
tion of pseudo binary-systems (Follegatti-Romero et al. [31]) was
excellent, even when the temperature of the extraction process
was extrapolated. Despite the differences in fatty acid composi-
tions and the method of analysis, the results of the present and
aforementioned studies are consistent.
4. Conclusions
The results presented in this article demonstrate that the dis-
tribution coefficient of commercial linoleic acid and the mutual
solubility of oil and solvent (ethanol and water) are affected by the
solvent water content and temperature of the system. The distribu-
tion coefficient of free fatty acids, the solubility of neutral oil in the
alcoholic phase and the solubility of the solvent (ethanol and water)
in the oil phase must be known to properly design liquid–liquid
extractors for oil deacidification processes and to engineer equip-
ment used for the recovery of solvent. The estimated parameters of
the NRTL model can be used to model and simulate LLE and recovery
processes.
List of symbols
A0,ij , A0,ji , A1,ij , and A1,ji NRTL interaction parameters
D total number of data groups
FAME fatty acid methyl esters
FFA free fatty acids
G total number of groups
K total number of components or pseudocompounds in the
data group m
LLE liquid–liquid extraction
M amount of the initial mixture, oil or alcoholic phases
M average molar mass
N total number of tie lines
NRTL non-random two liquid
OF objective function of composition
R universal gas constant
T temperature (K)
wi mass fraction of compound or pseudocompound i
w phase composition global deviation
gij molecular energy interactions between the components
i and j
 C. Chiyoda et al. / Fluid Phase Equilibria 299 (2010) 141–147 147

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