Fluid Phase Equilibria 338 (2013) 7886

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Fluid Phase Equilibria

journal homepage: www.elsevier.com/locate/fluid

Experimental data for liquidliquid equilibrium of fatty systems with emphasis

on the distribution of tocopherols and tocotrienols
Marina Ansolin, Rodrigo Corra Basso, Antonio Jos de Almeida Meirelles,
Eduardo Augusto Caldas Batista
ExTrAE, Department of Food Engineering, Faculty of Food Engineering, University of Campinas, UNICAMP, 13083-862 Campinas, SP, Brazil

a r t i c l e

i n f o

Article history:
Received 20 March 2012
Received in revised form
16 September 2012
Accepted 24 September 2012
Available online 2 October 2012
Keywords:
Degummed soybean oil
Rened rice bran oil
Tocopherols
Tocotrienols
Liquidliquid equilibrium

a b s t r a c t
The present paper reports liquidliquid equilibrium data for systems composed of degummed soybean oil + commercial linoleic acid + anhydrous ethanol, degummed soybean oil + commercial linoleic
acid + ethanol + water, rened rice bran oil + commercial oleic acid + anhydrous ethanol and rened rice
bran oil + commercial oleic acid + ethanol + water at 298.15 K, 313.15 K and 323.15 K. , ,  and tocopherol and tocotrienol contents in both phases were analyzed. The parameters of the NRTL model were
adjusted to the experimental data. For higher temperatures and the free fatty acid contents, higher are
distribution coefcients of tocopherols and tocotrienols, due to the increase in solubility among the systems components. In contrast, the distribution coefcients of tocopherols and tocotrienols decrease when
water is added to ethanol, which represents the increase in retention of tocopherols and tocotrienols in
the oil phase. The NRTL model represented well the experimental data, and the global deviations between
calculated and experimental data were 1.02% and 0.95% for systems composed of degummed soybean
oil and rened rice bran oil, respectively.
2012 Published by Elsevier B.V.

1. Introduction
Crude vegetable oils are constituted mainly of triacylglycerols
(around 95%) and of minor compounds, such as free fatty acid, tocopherols, tocotrienols, carotenoids, phosphatides, peroxides, and
others compounds [1].
Tocopherols and tocotrienols are associated with a preventive
action against free radicals in biological systems, inhibiting the oxidation of low density lipoproteins (LDL) and preventing cancer;
tocotrienols protect the nervous system [2].
When intended for human consumption, most oils must to
be rened in order to remove impurities. The deacidication or
removal of free fatty acid (FFA) is the most important step due to
its impact on oil production. This method can be carried out either
by chemical or physical methods. The chemical method is not recommended for oils with high acidity, resulting in high neutral oil
losses. The physical method uses reduced pressures and high temperatures, which degrade desirable thermosensitive compounds.
Furthermore, chemical rening removes about 20% of the tocopherols in the oil and physical rening is responsible for tocopherol
losses of 3060% [3]. Tasan and Demirci [4] and Alpaslan et al. [5]

Corresponding author at: ExTrAE, Department of Food Engineering, Faculty of

Food Engineering, State University of Campinas, UNICAMP, 13083-862 Campinas,
SP, Brazil.
E-mail address: eacbat@fea.unicamp.br (E.A.C. Batista).
0378-3812/$ see front matter 2012 Published by Elsevier B.V.
http://dx.doi.org/10.1016/j.uid.2012.09.033

studied the losses of tocopherols of sunower oil during steps of

chemical and physical rening and found that the highest loss of
tocopherols occurs during the step of degummed deacidication in chemical rene and in the physical rening the highest loss
occurs during the steam distillation. Verleyen et al. [6] studied the
losses of tocopherol during step of chemical and physical rening
of soybean, palm and corn oil.
An alternative to deacidication is liquidliquid extraction or
solvent rening. This process is based on the difference in solubility of free fatty acids and triacylglycerols in the appropriate
solvent [7]. The deacidication of vegetable oil has been studied
by many authors, Bollman [8], was the rst author that use the
solvent extraction for deacidication of vegetable oils. Trkay and
Civelekoglu [9,10] studied the liquidliquid equilibrium of sulfur
olive oil miscella in hexane with aqueous ethanol solution.
The liquidliquid extraction is carried out ambient temperature
and atmospheric pressure, reducing energy costs [11]. The resulting
oil presents reduction of minor compounds losses, such as tocopherols and tocotrienols that confer desirable characteristics to the
oil [12,13].
Ethanol is the best solvent for the deacidication by
liquidliquid extraction, because it presents good selectivity and
the distribution coefcients of free fatty acid is greater than one
[1416]. Pure ethanol, which can be considered a food grade solvent, is used in the formulation of some alcoholic beverages, as the
extraction medium for natural products, and in many other applications in industry processing goods for direct human consumption.

M. Ansolin et al. / Fluid Phase Equilibria 338 (2013) 7886

This product is known as extra ne or natural alcohol [17]. Ethanol

presents low toxicity and the loss of nutraceutical compounds
during the liquidliquid equilibrium is relativity low [18]. The addition of water in the solvent reduces capacity of extracting FFA,
but improves it is selectivity, reducing neutral oil losses [19]. The
greater the amount of water in the solvent, lower is the capacity for
extraction of minor compound, such as tocopherols, tocotrienols
and carotenoids [20].
The present paper reports experimental data for liquidliquid
equilibrium of systems composed by degummed soybean
oil + commercial linoleic acid + ethanol, degummed soybean
oil + commercial linoleic acid + ethanol + water, rened rice
bran oil + commercial oleic acid + ethanol, and rened rice bran
oil + commercial oleic acid + ethanol + water, at 298.15 K, 313.15 K
and 323.15 K, with emphasis on distribution of tocopherols and
tocotrienols. The experimental data was correlated by the nonrandom two-liquid (NRTL) model for description of the liquidliquid
equilibrium phases.
2. Experimental
2.1. Materials

79

detection and a mobile phase consisting of hexane and isopropanol

(99.5:0.5), performed on a Shimadzu chromatograph series LC20AT (Japan) equipped with a quaternary pump, autosampler
(SIL-20AT), degasser and uorescence detector. Chromatographic
separations of the compounds were achieved at 293.15 K, using
the normal-phase column LiChrosper Si 60 (Merck; 250 4.6 mm
i.d.; 5 m particle size) with a guard column LiChroCART 254
LiChrosper Si 60 (Merck; 5 m particle size). Fluorescence detection of tocopherols and tocotrienols was carried out with 290 nm
for excitation and 330 nm for emission. Calibration curves were
made with standards of tocopherols (Calbiochem, USA) to determine their concentrations. The concentrations of tocotrienols,
which are tocopherol isomers, were calculated similarly to
tocopherols.
In the present work all analyses were performed in triplicate. To
verify the quality of the results, the procedure developed by Marcilla et al. [25] and previously applied to fatty systems by Rodrigues
et al. [26] was utilized. According to Marcilla et al. [25], values
of global mass balance deviation less than 0.5 % ensure the good
quality of the experimental data. The global mass balance deviation is the difference between the sums of the calculated mass in
both liquid phases with the actual value for total mass used in the
experiment.

The solvents used in this work were anhydrous ethanol, from

Merck, with purity greater than 99.5%, and aqueous ethanol solvent
with water contents of approximately 4%, prepared by the addition
of deionized water (Milli-Q, Millipore) to the anhydrous ethanol.
All fatty reagents used in this study consisting of commercial
linoleic acid (Fluka), commercial oleic acid (Merck), degummed
soybean oil (Cargil) and rened rice bran oil (Irgovel) were analyzed by gas chromatography for fatty acid methyl esters in order
to determine the fatty acid composition according to the ofcial
method Ce 162 of the American Oil Chemists Society (AOCS) [21].
All vegetables oils were analyzed to quantify the tocopherol and
tocotrienol contents, water content and free fatty acid content.

The obtained experimental data was used to adjust the parameters of the NRTL model. Parameter adjustments were made by
treating the systems as pseudoquaternary, composed by a single
triacylglycerol, a representative fatty acid, ethanol and water. The
molar masses Mi of the representative triacylglycerol and fatty acid
were, respectively, determined from the molar composition of the
vegetable oil and the commercial fatty acid.
In the NRTL model, the activity coefcient assumes the presented form:

2.2. Experimental procedure

ln i =

The liquidliquid equilibrium experiments were performed in

glass liquidliquid equilibrium cells, those described by Silva et al.
[22]. Components were weighed on an analytic balance (Precisa,
model XT220A, Sweden), accurate to 0.0001 g, with the help of
syringes. After addition of all components in the cell, they were
sealed and connected to a thermostatic bath with temperature
control (Cole Parmer, model 12101-55, Chicago, USA), accurate to
0.01 K. A digital thermometer (Alla, model 223.15 K to 473.15 K,
France) was used to monitor the temperature inside the cell. This
mixture was then vigorously agitated for 20 min with a magnetic
stirrer (Ika Werke, model RH-KT/C, Staufen, Germany) and left rest
for approximately 24 h, this led to the formation of two clear and
transparent phases, with a well-dened interface. Samples of both
phases were carefully collected with syringes with the observation of phases for quantication of the components. Concentration
of the free fatty acid was performed by titration according to the
ofcial method 2201 of the IUPAC [23], with an automatic titrator (Metrohm, model Titrando 808, Herisan, Switzerland). Water
content was quantied according to the AOCS method Ca 2e-84 by
Karl Fisher titration [21]. Oven (Marconi, model MA 035/3, Piracicaba/SP, Brazil) operating at atmospheric pressure and 353.15 K
was utilized for determination of solvent content, until constant
mass. The quantity of triacylglycerols was then found by calculating
the difference.
The method used for analysis of tocopherols and tocotrienols
content was adapted from a procedure previously optimized by Silva et al. [24]. This method utilizes uorescence

2.3. Thermodynamic modeling

C

 G w /Mj
j=1 ji ji j

C

G w /Mj
j=1 ji j

C

j=1

j
M

C

wj Gij

G w /Mk
k=1 kj k

ij

C

 G w /Mk
k=1 kj kj k
C
k
G w /M
k=1 kj k



(1)
where:

Gij = exp ij ij

ij =

Aij

T
ij = ji

(2)
(3)
(4)

Aij , Aji , and ij are the adjustable binary parameters between the
pair of components i and j, C is the number of components and T is
the absolute temperature.
The NRTL binary parameters can also be adjusted as function of
the absolute temperature, as dened by the expression:
Aij = A0 + A1 T

(5)

The non randomness parameters of the NRTL model are therefore

dened by:
ij = 0 + 1 T

(6)

According to the procedure developed by Stragevitch and dvila

[27], the binary parameters were calculated using the modied
simplex method by the minimization of the composition objective

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M. Ansolin et al. / Fluid Phase Equilibria 338 (2013) 7886

14

1,0

12

0,8

k - tocopherol

10

100w 2

8
6
4

0,6

0,4

2
0

20

40

60

80

0,2
290

100

300

310

320

330

Temperature (K)

100w5+100w6
Fig. 1. System of degummed soybean oil (1) + commercial linoleic acid
(3) + anhydrous ethanol (5) + water (6) at 313.15 K: () experimental; ()
NRTL model.

Fig. 3. Average distribution coefcient of Tocopherol () in systems composed

of degummed soybean oil (1) + commercial linoleic acid (3) + anhydrous ethanol (5)
and () the systems composed of degummed soybean oil (1) + commercial linoleic
acid (3) + anhydrous ethanol (5) + water (6).

function dened as:

The deviations between experimental and calculated compositions in both phases were calculated according to:

OF(w) =

D
N C1



m


2
AP,exp
AP,calc
wi,n,m wi,n,m


 
 
   
 N C wAP,exp wAP,calc 2 + wOP,exp wOP,calc 2
 n i
i,n
i,n
i,n
i,n

wAP

i,n,m

w =

2
OP,exp
OP,calc
wi,n,m wi,n,m

+


(8)
(7)

wOP

i,n,m

3. Results

where D is the total number of data groups, N is the total number of

tie-lines, and C the total number of components in the data group m.
The subscripts i, n and m dene the component, tie-line and group
number, respectively. Subscript AP and OP stand for alcoholic phase
and oil phase, respectively, exp and calc refer to experimental and
calculated mass composition. wAP and wOP are the standard
i,n,m

i,n,m

deviations observed in the composition of the two liquid phases.

14
12

100w4

10
8
6
4
2
0

20

2NC

40

60

80

100

100w5+100w6
Fig. 2. System of rened rice bran oil (2) + commercial oleic acid (4) + anhydrous
ethanol (5) + water (6) at 298.15 K: () experimental; () NRTL model.

In the present work the following notations were given to the

components utilized: degummed soybean oil (1), rened rice bran
oil (2), commercial linoleic acid (3), commercial oleic acid (4), anhydrous ethanol (5) and water (6).
The fatty acid composition of the vegetable oils and commercial
fatty acids utilized in this work are presented in Table 1, from which
the probable triacylglycerol compositions of the degummed soybean oil and rened rice bran oil were determined by the algorithm
suggested by Antoniossi Filho et al. [28]. For this, it was considered that the principal triacylglycerol represents the component of
greatest concentration in the isomer set with x carbons and y double bonds. Table 2 shows the probable triacylglycerol composition
of the degummed soybean oil and rened rice bran oil, the groups
with a total triacylglycerol concentration less than 0.5 % were
ignored.
According to Table 2, it was possible to calculate the average
molar mass of the degummed soybean oil and the rened rice bran
oil. The obtained values were 872.35 g mol1 and 865.94 g mol1 ,
respectively. Average molar mass of the commercial linoleic acid
and commercial oleic acid were determined from their fatty acid
composition presented in Table 1. The obtained values were
280.06 g mol1 and 280.73 g mol1 , respectively.
The total contents of tocopherols and tocotrienols of the
degummed soybean oil and the rened rice bran oil were
1991.56 mg kg1 and 1089.20 mg kg1 , respectively.
Tables 3 and 4 present the overall composition and the
corresponding tie lines for the pseudoternary systems composed of degummed soybean oil (1) + commercial linoleic
acid (3) + anhydrous ethanol (5) and rened rice bran oil
(2) + commercial oleic acid (4) + anhydrous ethanol (5) at 298.15 K,
313.15 K and 323.15 K.

M. Ansolin et al. / Fluid Phase Equilibria 338 (2013) 7886

81

Table 1
Fatty acid composition of degummed soybean oil, rened rice bran oil, commercial linoleic acid and commercial oleic acid.
Fatty acid

Symbol

Dodecanoic
Tetradecanoic
Pentadecanoic
Hexadecanoic
Cis-hexanadec-9-enoic
Heptadecanoic
Cis-heptadec-9-enoic
Octadecanoic
Cis-octadec-9-enoic
trans-9-octadecanoic
Cis,cis-octadec-9,12-dienoic
trans, trans- octadec-9,12-dienoic
All-cis-octadec-9,12,15-trienoic
All-trans-octadeca-9,12,15-trienoic
Icosanoic
Cis-icos-9-enoic
Docosanoic
Tetracosanoic

L
M

P
Po
Ma
Mg
S
O

Li

Ln

A
Ga
Be
Lg

a
b

C12:0a
C14:0
C15:0
C16:0
C16:1
C17:0
C17:1
C18:0
C18:1
C18:1 Tb
C18:2
C18:2 Tb
C18:3
C18:3 Tb
C20:0
C20:1
C22:0
C24:0

Rened rice bran oil

100wi

Degummed soybean oil

100wi

Commercial linoleic acid

100wi

Commercial oleic acid

100wi

0.04
0.26
0.04
19.65
0.16
0.06
0.03
1.87
39.36

34.42

1.9

0.83
0.62
0.29
0.47

0.05
0.10
0.03
11.03
0.09
0.10
0.06
4.04
28.83

48.55

5.71

0.42
0.27
0.53
0.19

0.18
0.15

4.69
0.10

1.79
23.49

68.43
0.55
0.11

0.14
0.15
0.22

0.35
0.38

6.50

1.72
77.05
0.87
11.84
0.60

0.21
0.48

In Cx:y, x = number of carbons and y = number of double bonds.

Trans isomers, wi = mass fraction.

Table 2
Probable triacylglycerol compositions of degummed soybean oil and rened rice bran oil.
Triacylglycerol

Group

Molar mass (g mol1 )

POP
POS
PLiP
OOP
OOS
PLiO
OOO
LiLiP
OLiO
PLnLi
LiOLi
LiLiLi
LiLnLi

50:1a
52:1
50:2
52:2
54:2
52:3
54:3
52:4
54:4
52:5
54:5
54:6
54:7

833.37
861.42
831.35
859.41
887.46
857.39
885.44
855.38
883.43
853.36
881.41
879.40
877.38

Degummed soybean oil

Rened rice bran oil

100xi

100wi

100xi

100wi

1.21
0.80
2.05
4.78
1.13
11.62
6.27
11.23
15.62
2.33
21.94
16.82
4.20

1.26
0.81
2.15
4.85
1.11
11.82
6.17
11.45
15.42
2.38
21.71
16.68
4.19

6.01
1.03
5.25
13.06
1.05
21.24
7.98
9.28
16.92

14.08
4.10

6.24
1.04
5.47
13.15
1.02
21.45
7.80
9.39
16.58

13.83
4.03

In X:Y, X = number of carbons (except for carbons of glycerol); Y = number of double bonds. wi = mass fraction; xi = molar fraction.

Table 3
Experimental (liquidliquid) equilibrium data for the system degummed soybean oil (1) + commercial linoleic acid (3) + anhydrous ethanol (5) in mass percentage at
temperature T/K = (298.15, 313.15, 323.15) and pressure P/mmHg = 710.76.a
T (K)

Overall composition

Oil phase

Alcohol phase

100w1

100w3

100w5

100w1

100w3

100w5

100w1

100w3

100w5

298.15

50.51
46.83
46.54
42.94
45.54

1.23
3.10
4.22
5.55
7.02

48.26
50.07
49.24
51.51
47.44

81.20
77.41
75.02
71.31
63.79

1.11
2.70
3.75
4.94
6.54

17.69
19.89
21.23
23.75
29.68

8.45
10.01
11.81
14.28
17.33

1.48
3.55
4.89
6.51
7.97

90.07
86.44
83.30
79.21
74.7

313.15

49.26
46.42
48.12
46.39
47.01

1.19
2.04
2.86
3.23
4.09

49.55
51.54
49.02
50.38
48.90

74.87
72.59
70.75
68.97
64.9

1.14
1.90
2.64
2.98
3.86

23.99
25.51
26.61
28.05
31.24

13.26
14.59
14.50
16.43
20.9

1.42
2.33
3.16
3.65
4.58

85.32
83.08
82.35
79.92
74.52

323.15

46.93
46.93
44.29
43.15
41.26
41.07

1.14
1.14
1.56
2.09
2.48
3.01

51.93
51.93
54.15
54.76
56.26
55.92

67.72
67.72
66.37
65.2
64.05
59.58

1.09
1.09
1.49
1.95
2.32
2.87

31.19
31.19
32.14
32.85
33.63
37.55

16.9
16.91
17.23
18.69
19.32
22.56

1.31
1.30
1.74
2.25
2.70
3.20

81.79
81.79
81.03
79.06
77.98
74.24

Standard uncertainties u are u(T/K) = 0.1 K, u(P/mmHg) = 2.21, combined u(w) = 0.0062.

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M. Ansolin et al. / Fluid Phase Equilibria 338 (2013) 7886

Table 4
Experimental (liquidliquid) equilibrium data for the system rened rice bran oil (2) + commercial oleic acid (4) + anhydrous ethanol (5) in mass percentage at temperature
T/K = (298.15, 313.15, 323.15) and pressure P/mmHg = 710.76.a
T (K)

Overall composition

Oil phase

Alcohol phase

100w2

100w4

100w5

100w2

100w4

100w5

100w2

100w4

100w5

298.15

44.05
42.39
42.01
40.58
38.39

0.00
2.39
3.49
5.12
7.1

55.95
55.22
54.5
54.3
54.51

85.65
82.9
80.64
77.02
72.34

0.00
1.97
2.89
4.29
6.04

14.35
15.13
16.47
18.69
21.62

6.06
7.66
8.21
10.17
12.79

0.00
2.67
3.86
5.59
7.67

93.94
89.67
87.93
84.24
79.54

313.15

43.79
43.11
44.44
43.80
38.69

0.00
0.61
1.24
2.52
3.97

56.21
56.28
54.32
53.68
57.34

80.90
79.90
78.47
76.85
72.27

0.00
0.49
1.10
2.29
3.49

19.1
19.61
20.43
20.86
24.24

10.65
10.87
11.53
13.13
15.43

0.00
0.76
1.51
2.93
4.3

89.35
88.37
86.96
83.94
80.27

323.15

44.60
42.25
43.71
43.30
41.98

0.00
0.41
1.13
1.69
2.31

55.4
57.34
55.16
55.01
55.71

75.82
75.64
72.8
71.31
68.81

0.00
0.40
1.01
1.57
2.17

24.18
23.96
26.19
27.12
29.02

11.75
13.79
13.24
15.4
19.53

0.00
0.48
1.22
1.91
2.55

88.25
85.73
85.54
82.69
77.92

Standard uncertainties u are u(T/K) = 0.1 K, u(P/mmHg) = 2.21, combined u(w) = 0.0074.

Table 5
Experimental (liquidliquid) equilibrium data for the system degummed soybean oil (1) + commercial linoleic acid (3) + anhydrous ethanol (5) + water (6) in mass percentage
at temperature T/K = (298.15, 313.15, 323.15) and pressure P/mmHg = 710.76.a
T (K)

Overall composition

Oil phase

Alcohol phase

100w1

100w3

100w5

100w6

100w1

100w3

100w5

100w6

100w1

100w3

100w5

100w6

298.15

43.99
42.45
40.39
36.24
36.43

1.05
3.25
6.90
8.71
11.61

52.5
51.87
50.35
52.59
50.18

2.46
2.43
2.36
2.46
1.78

87.96
84.43
78.29
73.85
66.45

1.00
2.93
6.13
7.74
10.23

10.81
12.33
15.12
17.68
22.72

0.23
0.31
0.46
0.73
0.6

3.31
3.93
5.66
6.65
8.63

1.14
3.47
7.29
9.15
11.96

91.31
88.4
83.13
80.51
76.86

4.24
4.20
3.92
3.69
2.55

313.15

46.06
41.89
41.09
36.45
36.46
36.15

1.13
3.41
5.04
6.68
8.89
11.47

51.00
52.3
51.51
54.38
52.25
50.08

1.81
2.40
2.36
2.49
2.40
2.30

86.23
81.00
78.46
74.82
70.42
57.75

1.01
3.10
4.63
6.02
8.18
11.00

12.41
15.5
16.46
18.51
20.6
30.32

0.35
0.40
0.45
0.65
0.80
0.93

6.08
6.59
7.67
8.34
11.33
15.81

1.36
3.63
5.40
6.98
9.46
12.1

89.06
86.01
83.27
81.22
75.33
68.41

3.50
3.77
3.66
3.46
3.88
3.68

323.15

43.96
41.83
40.84
36.99
34.98

1.06
3.24
5.12
6.58
8.21

52.57
52.52
51.67
53.96
54.27

2.41
2.41
2.37
2.47
2.54

81.68
77.3
73.14
69.47
64.8

1.01
3.09
4.9
6.13
7.56

16.86
18.94
21.03
23.54
26.48

0.45
0.67
0.93
0.86
1.16

5.46
7.68
8.69
10.61
12.84

1.24
3.54
5.51
6.98
8.38

89.28
85.14
82.30
78.96
75.54

4.02
3.64
3.50
3.45
3.24

Standard uncertainties u are u(T/K) = 0.1 K, u(P/mmHg) = 2.21, combined u(w) = 0.0062.

Table 6
Experimental (liquidliquid) equilibrium data for the system rened rice bran oil (2) + commercial oleic acid (4) + anhydrous ethanol (5) + water (6) in mass percentage at
temperature T/K = (298.15, 313.15, 323.15) and pressure P/mmHg = 710.76.a
T (K)

Overall composition

Oil phase

Alcohol phase

100w2

100w4

100w5

100w6

100w2

100w4

100w5

100w6

298.15

43.26
40.21
40.00
38.97
36.19

0.00
2.18
4.39
6.72
9.11

54.38
55.22
53.30
52.06
52.43

2.36
2.39
2.31
2.25
2.27

92.23
91.63
87.36
82.42
78.8

0.00
2.01
4.09
6.19
8.30

7.53
6.05
8.19
10.96
12.38

313.15

43.43
42.04
40.46
37.04
35.10
34.12

0.00
2.38
4.56
6.66
8.66
10.18

54.22
53.27
52.7
53.97
53.91
53.39

2.35
2.31
2.28
2.33
2.33
2.31

89.33
85.99
82.35
77.71
72.65
68.84

0.00
2.31
4.32
6.22
8.06
9.58

323.15

44.43
41.11
40.54
37.79
35.1

0.00
2.20
4.47
6.77
8.66

2.31
2.35
2.28
2.30
2.33

53.26
54.34
52.71
53.14
53.91

86.38
82.95
78.28
73.06
68.3

0.00
2.08
4.19
6.37
8.18

Standard uncertainties u are u(T/K) = 0.1 K, u(P/mmHg) = 2.21, combined u(w) = 0.0074.

100w2

100w4

100w5

100w6

0.24
0.31
0.36
0.43
0.52

3.93
4.23
4.97
6.4
8.11

0.00
2.34
4.70
7.10
9.50

92.01
89.49
86.48
82.77
78.74

4.06
3.94
3.85
3.73
3.65

10.35
11.25
12.89
15.57
18.69
20.87

0.32
0.45
0.44
0.5
0.6
0.71

5.54
6.08
6.71
8.29
9.43
9.53

0.00
2.40
5.02
7.12
9.25
10.88

90.42
87.53
84.42
80.35
77.58
75.92

4.04
3.99
3.85
4.24
3.74
3.67

13.23
14.5
16.93
19.84
22.65

0.39
0.47
0.60
0.73
0.87

6.06
6.08
7.68
8.37
12.02

0.00
2.38
4.77
7.28
9.02

89.75
87.3
83.53
80.63
75.4

4.19
4.24
4.02
3.72
3.56

M. Ansolin et al. / Fluid Phase Equilibria 338 (2013) 7886

83

Table 7
Parameters of the NRTL model for the system composed of degummed soybean oil (1) + commercial linoleic acid (3) + anhydrous ethanol (4) + water (5) and rened rice bran
oil (2) + commercial oleic acid (4) + anhydrous ethanol (5) + water (6).
Oil

Par ij

A0ij (K)

Degummed soybean oil

13
15
16
35
36
56

741.25
1317.2
2111.2
20.844
31212
5060.2

Rened rice bran oil

24
25
26
45
46
56

10.590
200.60
43627
101.91
335.60
482.63

A0ji (K)
900.00
1623.4
2754.2
16370
237.85
871.27
225.01
2309.9
210.24
1530.0
11020
3.0529

A1ij ()

A1ji ()

0ij ()

1ij (K1 )

15.392
5.3923
0.8318
2.4800
177.48
35.031

4.7544
0.1442
0.5440
18.585
0.1800
0.9940

0.11820
0.07384
0.29110
0.21892
0.10011
0.56999

0.00001
0.00154
0.00001
0.00001
0.00001
0.00001

0.9962
3.1999
8.4000
2.8799
40.000
0.0080

0.41800
0.85479
0.20000
0.27442
0.39000
0.41000

0.0001
0.0046
0.0001
0.0001
0.0001
0.0001

0.74327
1.1001
154.32
0.0800
0.0800
0.0800

Table 8
Deviation between the experimental and the calculated compositions in both phases (w), for systems composed of degummed soybean oil and rened rice bran oil.
System

T (K)

w (%)

Degummed soybean oil (1) + linoleic acid (3) + anhydrous ethanol (5)

298.15
313.15
323.15
298.15
313.15
323.15

0.69
1.12
1.08
1.14
1.03
0.35

Degummed soybean oil (1) + linoleic acid (3) + ethanol (5) + water (6)

Global

0.95
a

Rened rice bran oil (2) + anhydrous ethanol (5)

298.15
313.15
323.15
298.15
313.15
323.15
298.15
313.15
323.15
298.15
313.15
323.15

Rened rice bran oil (2) + ethanol (5) + water (6) a

Rened rice bran oil (2) + oleic acid (4) + anhydrous ethanol (5)

Rened rice bran oil (2) + oleic acid (4) + ethanol (5) + water (6)

1.07
0.25
1.07
1.01
1.53
1.04
1.01
0.56
1.06
1.19
1.10
1.03
1.04

Global
a

Base line.

Table 9
Content of tocopherol of the system composed of degummed soybean oil (1) + commercial linoleic acid (3) + anhydrous ethanol (5) at temperature T/K = (298.15, 313.15,
323.15) and pressure P/mmHg = 710.76.a
T (K)

Oil phase

Alcohol phase

Total

mg kg1

Total

mg kg1

298.15

114.51
107.47
94.87
84.47
65.97

24.86
26.39
24.31
21.59
22.66

1083.30
967.13
926.77
830.55
837.06

152.29
144.75
135.49
120.87
129.23

1374.96
1245.74
1181.44
1057.48
1054.92

59.27
58.49
51.33
64.19
70.34

14.66
17.03
14.99
13.20
17.22

656.09
640.22
619.36
633.92
696.04

121.83
121.12
117.22
107.92
122.25

851.85
836.86
802.90
819.23
905.85

313.15

113.73
109.79
101.98
96.87
76.48

42.06
39.48
29.66
29.78
27.04

1070.59
1022.18
983.43
941.93
876.45

155.74
148.66
146.01
141.16
138.12

1382.12
1320.11
1261.08
1209.74
1118.09

69.55
66.45
70.00
60.96
55.66

24.82
24.49
24.16
22.30
23.45

719.98
689.55
732.70
674.96
664.20

129.10
120.84
126.90
120.94
123.44

943.45
901.33
953.76
879.16
866.75

323.15

128.56
110.19
107.83
75.67
83.29

42.58
30.88
33.13
27.95
31.25

1142.09
1011.12
989.67
820.56
838.91

172.08
156.18
150.59
134.33
130.50

1485.31
1308.37
1281.22
1058.51
1083.95

80.19
77.84
73.51
67.31
57.96

23.67
25.39
21.19
21.46
21.62

786.88
768.89
732.14
708.11
654.71

141.70
135.49
128.64
123.24
116.38

1032.44
1007.61
955.48
920.12
850.67

Standard uncertainties u are u(T/K) = 0.1 K, u(P/mmHg) = 2.21, combined u(w) = 0.0058.

84

M. Ansolin et al. / Fluid Phase Equilibria 338 (2013) 7886

Table 10
Content of tocopherols and tocotrienols in the system composed of rened rice bran oil (2) + commercial oleic acid (4) + anhydrous ethanol (5) at temperature T/K = (298.15,
313.15, 323.15) and pressure P/mmHg = 710.76.a
T (K)

Oil phase
b

Alcohol phase
c

b

c

Total

b

c

Total

mg kg

mg kg

298.15

223.20
137.31
132.91
118.17
107.65

45.56
59.56
56.16
52.51
48.54

100.36
76.76
68.68
64.27
56.12

430.67
368.21
351.23
330.26
291.95

5.63
6.64
6.28
5.84
5.26

805.42
648.48
615.26
571.05
509.52

63.68
64.83
64.31
66.96
51.21

0.00
0.00
0.00
0.00
0.00

46.61
45.85
45.99
46.93
39.25

255.34
254.42
254.01
251.65
231.68

5.42
5.24
5.04
4.83
4.77

371.05
370.34
369.35
370.37
326.91

313.15

194.96
140.28
148.52
143.97
133.78

49.17
51.65
55.13
48.39
46.02

97.25
92.02
101.58
92.17
74.11

432.41
426.34
479.30
435.21
332.53

6.84
6.71
7.80
6.25
5.38

780.63
717.00
792.33
725.99
591.82

78.13
72.29
75.95
74.72
68.74

0.00
0.00
0.00
0.00
0.00

60.72
62.04
71.66
67.96
52.04

316.44
344.55
351.53
359.66
275.51

6.26
6.07
5.86
6.79
5.52

461.55
484.95
505.00
509.13
401.80

323.15

188.13
148.53
61.21
77.53
109.27

41.68
53.71
46.54
56.13
49.27

92.24
88.72
70.95
77.28
56.96

410.04
413.46
345.33
393.91
296.35

5.45
6.20
5.78
6.83
5.34

737.54
710.62
529.81
611.68
517.19

72.81
72.51
43.23
46.93
51.57

0.00
0.00
0.00
0.00
0.00

57.13
58.98
45.42
52.00
39.53

301.83
303.38
247.02
288.58
233.35

5.16
5.17
3.97
5.08
4.81

436.93
440.04
339.64
392.59
329.26

a
b
c

Standard uncertainties u are u(T/K) = 0.1 K, u(P/mmHg) = 2.21, combined u(w) = 0.0098.
Corresponds to tocopherols.
Correspond to tocotrienols.

Tables 5 and 6 present the overall composition and the

corresponding tie lines for the pseudoquaternary systems composed of degummed soybean oil (1) + commercial linoleic acid
(3) + anhydrous ethanol (5) + water (6) and rened rice bran oil
(2) + commercial oleic acid (4) + anhydrous ethanol (5) + water (6)
at temperature of 298.15 K, 313.15 K and 323.15 K.
From Tables 36 it can be noted that with the increase in temperature and free fatty acid concentration, solubility between the
system components increased. Addition of water increases two
phase region in the systems. The deviations of the global mass
balance for all systems studied were less than 0.5 %, ensuring the
quality of experimental data. Similar behavior was observed for
the systems composed of degummed soybean oil and rened rice
bran oil. Rodrigues et al. [29,30], Goncalves et al. [12], Chiyoda
et al. [31] and Batista et al. [14], observed the same behavior
found in the present study when water is added to the systems, although they are different systems composed of different
oils.

Table 7 presents the parameters of the NRTL model adjusted

to the experimental data. The deviation between the experimental and calculated composition for the systems composed of
degummed soybean oil and rened rice bran oil are shown in
Table 8.
Figs. 1 and 2 show the experimental points and calculated
tie lines for the systems composed of degummed soybean oil
(1) + commercial linoleic acid (3) + anhydrous ethanol (5) + water
(6) at 313.15 K and rened rice bran oil (2) + commercial oleic
acid (4) + anhydrous ethanol (5) + water (6) at 298.15 K, respectively. From these gures a good alignment can be observed the
experimental data, relative to both overall and phase compositions.
These gures also show that thermodynamic models are able to
accurately describe the phase composition for the systems studied
in this work.
Tables 9 and 10 present the content of tocopherols and
tocotrienols for the systems composed of degummed soybean
oil (1) + commercial linoleic acid (3) + anhydrous ethanol (5) and

Table 11
Content of tocopherols in the system composed of degummed soybean oil (1) + commercial linoleic acid (3) + anhydrous ethanol (5) + water (6) at temperature T/K = (298.15,
313.15, 323.15) and pressure P/mmHg = 710.76.a
T (K)

Oil phase

Alcohol phase

Total

mg kg1

Total

mg kg1

298.15

151.59
139.01
113.63
95.68
76.95

27.35
25.12
23.18
22.19
27.94

1282.01
1199.30
1061.83
909.04
1185.43

180.00
168.70
152.30
78.31
117.10

1640.95
1532.13
1350.94
1105.22
1407.42

41.66
41.28
42.32
40.89
41.32

13.54
14.55
12.92
14.05
11.53

441.22
463.17
479.59
466.42
465.15

93.69
93.86
94.18
36.78
85.37

590.11
612.86
629.01
558.14
603.37

313.15

102.92
118.01
118.89
101.74
93.85
76.22

26.66
29.91
37.83
23.36
21.22
21.55

917.55
1090.80
1091.90
924.11
887.51
749.02

138.01
151.31
148.72
130.44
127.48
110.48

1185.14
1390.03
1397.34
1179.65
1130.06
957.27

78.64
52.26
51.02
45.17
51.04
38.51

19.37
18.69
18.18
15.05
18.06
22.36

443.27
530.61
532.31
490.57
542.11
494.30

84.06
93.87
93.59
85.94
93.15
92.39

625.34
695.43
695.10
636.73
704.36
647.56

323.15

121.35
106.32
118.00
95.32
86.99

34.26
30.03
41.42
28.39
19.20

1171.28
1040.00
1084.87
914.24
844.01

165.74
147.68
143.43
128.77
128.70

1492.63
1324.03
1387.72
1166.72
1078.90

58.11
50.65
55.61
51.65
45.89

24.26
18.84
20.74
20.09
12.08

607.98
544.92
578.30
551.17
519.79

101.82
95.44
98.95
90.56
94.99

792.17
709.85
753.60
713.47
672.75

Standard uncertainties u are u(T/K) = 0.1 K, u(P/mmHg) = 2.21, combined u(w) = 0.0058.

M. Ansolin et al. / Fluid Phase Equilibria 338 (2013) 7886

85

Table 12
Content of tocopherols and tocotrienols in the system composed of rened rice bran oil (1) + commercial oleic acid (3) + anhydrous ethanol (5) + water (6) at temperature
T/K = (298.15, 313.15, 323.15) and pressure P/mmHg = 710.76.a
T (K)

Oil phase
b

Alcohol phase
c

b

c

Total

b

c

Total

mg kg

mg kg

298.15

356.99
231.70
184.27
165.74
163.16

50.26
57.01
62.64
55.96
46.85

124.43
107.91
98.10
93.53
84.46

518.53
440.61
456.03
425.05
381.28

5.95
6.56
7.18
6.50
5.45

1056.16
843.79
808.22
746.78
681.20

48.69
50.13
41.99
59.06
51.41

0.00
0.00
0.00
0.00
0.00

42.76
41.69
28.07
43.09
40.70

253.16
261.57
208.54
300.01
275.99

5.41
5.57
4.70
6.82
5.46

350.02
358.96
283.30
408.98
373.56

313.15

289.01
259.46
141.63
131.33
128.09
88.02

53.61
45.59
54.57
49.33
44.90
41.71

120.77
111.96
100.44
87.01
86.91
74.97

510.00
466.57
412.78
396.10
379.40
349.05

6.50
5.58
6.62
6.14
5.60
5.16

979.89
889.16
716.04
669.91
644.90
558.91

55.63
54.53
53.82
51.41
57.80
61.34

0.00
0.00
0.00
0.00
0.00
0.00

46.87
45.09
45.65
45.19
45.01
46.53

279.40
273.77
279.40
276.63
321.64
337.81

5.47
5.36
5.05
5.21
6.99
7.96

387.37
378.75
383.92
378.44
431.44
453.64

323.15

264.81
138.58
74.68
80.11
67.25

52.05
45.70
50.14
51.67
43.78

115.14
100.78
85.73
83.27
73.58

483.81
405.84
373.21
387.88
347.90

6.38
5.21
5.47
6.33
5.57

922.19
696.11
589.23
609.26
538.08

52.70
40.26
40.15
44.89
39.30

0.00
0.00
0.00
0.00
0.00

44.47
41.22
39.92
43.54
41.16

296.85
248.18
261.17
285.82
262.55

6.76
4.98
5.26
5.89
5.10

400.78
334.64
346.50
380.14
348.11

a
b
c

Standard uncertainties u are u(T/K) = 0.1 K, u(P/mmHg) = 2.21, combined u(w) = 0.98.
Correspond to tocopherols.
Correspond to tocotrienols.

rened rice bran oil (2) + commercial oleic acid (4) + anhydrous
ethanol (5) at 298.15 K, 313.15 K and 323.15 K. Tables 11 and 12
present the contents of the tocopherols and tocotrienols for the systems composed of degummed soybean oil (1) + commercial linoleic
acid (3) + anhydrous ethanol (5) + water (6) and rening rice bran oil
(2) + commercial oleic acid (4) + anhydrous ethanol (5) + water (6)
at 298.15 K, 313.15 K and 323.15 K. It can be observed that there
is an increase in the distribution coefcient of tocopherols and
tocotrienols, calculated by Equation 9 with the increase in temperature and free fatty acid concentration. This occurs because of
increased solubility among system components. The addition of
water to the systems decreases the distribution coefcient of these
minor components. This can be best observed in Figs. 3 and 4 which
present the average distribution coefcient of -tocopherol for the
systems composed of degummed soybean oil and rened rice bran
oil, respectively. The same behavior was observed for , and
tocopherols for the systems composed of degummed soybean oil

and , and tocopherols and , and tocotrienols in the systems

composed of rened rice bran oil.
ki =

wiAP

wiOP

(9)

where wiAP corresponds to the content of each tocopherol in the

alcoholic phase and wiOP corresponds to content of each tocopherol
in the oil phase.
Rodrigues et al. [12,18] and Goncalves et al. [20]
systems
composed
of
rice
bran
oil + fatty
studied
acids + ethanol + water +  orizanol + tocols at 298.2 K, cottonseed oil + commercial linoleic acid + ethanol + water + tocopherol
at 298.2 K and palm oil + palmitic acid + oleic acid + ethanol + water
at 318.15 K, respectively, and observed the same behavior of the
distribution coefcients for the total tocols observed in the present
study, although they are derived from different oil and levels of
water added to the solvent.
4. Conclusions

1,0

k - tocopherol

0,8

0,6

0,4

0,2
290

300

310

320

330

From the results obtained, it was found that the solubility of

the systems and the distribution coefcients of tocopherols and
tocotrienols were affected by temperature, concentration of free
fatty acids and the presence of water in anhydrous ethanol. The
higher the temperature and free fatty acid content, greater is the
distribution coefcients of tocopherols and tocotrienols, due to
the increase in solubility among the system components. In contrast, the distribution coefcients of tocopherols and tocotrienols
decrease when water is added to anhydrous ethanol, which represents the increase in retention of these minor components in the
oil phase.
The adjustment of the binary parameters of the NRTL model
was representative to describe the liquidliquid equilibrium of the
systems studied, and this is can be proven by the average deviation
between the experimental and calculated values.

Temperature (K)
Fig. 4. Average distribution coefcient of tocopherol () in systems composed
of rened rice bran oil (1) + commercial oleic acid (3) + ethanol anhydrous (5) and
() the systems composed of rened rice bran oil (1) + commercial oleic acid
(3) + anhydrous ethanol (5) + water (6).

Acknowledgements
The authors wish to acknowledge CAPES (Coordenaco
de Aperfeicoamento de Pessoal de Nvel Superior, 304495/

86

M. Ansolin et al. / Fluid Phase Equilibria 338 (2013) 7886

2010-7+480992/2009-6) and FAPESP (Fundaco de Amparo a

Pesquisa do Estado de So Paulo, 2008/56258-8) for the nancial
support, and CARGILL S/A for kindly supplying the samples of soybean oil.
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