J. Chem.

Thermodynamics 57 (2013) 76–81

Contents lists available at SciVerse ScienceDirect

J. Chem. Thermodynamics
journal homepage: www.elsevier.com/locate/jct

(Liquid + liquid) equilibria for the ternary (water + acetic acid + toluene) system
at different temperatures: Experimental data and correlation
Javad Saien ⇑, Maryam Mozafarvandi, Shabnam Daliri, Mahdi Norouzi
Department of Applied Chemistry, Bu-Ali Sina University, Hamedan 65174, Iran

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

Article history: (Liquid + liquid) equilibrium (LLE) of the ternary (water + acetic acid + toluene) system was investigated
Received 20 July 2012 at temperatures of (288.2, 298.2, and 313.2) K, under atmospheric pressure. This chemical system is fre-
Received in revised form 21 August 2012 quently used in liquid–liquid extraction investigations. The results show that the distribution coefficient
Accepted 22 August 2012
of acetic acid between organic and aqueous phases rises with increasing temperature, but the separation
Available online 4 September 2012
factor decreases within the temperature range covered. Meanwhile, a maximum extraction factor (about
100) was achieved for the solute aqueous phase mass fraction around 0.27 at T = 288.2 K. The tie line data
Keywords:
for this system were sufficiently correlated by Othmer–Tobias and Hand equations. The experimental
LLE
Toluene-water
results were used to obtain binary interaction parameters as predicted by the non-random two liquid
Separation factor (NRTL) and universal quasi chemical (UNIQUAC) equation models using the Aspen Plus simulator. Root
Distribution coefficient mean square deviation (RMSD) values as low as 0.0119 and 0.0139 were obtained for these models,
Modelling respectively; indicating excellent correlation results for the provided experimental solubility data.
Ó 2012 Elsevier Ltd. All rights reserved.

1. Introduction
Separation of carboxylic acids from aqueous solutions resulting
from fermentation processes or synthetic methods is an important
process that has many supplications from different industries.
Accordingly, the recovery of acetic acid from aqueous solutions
has been investigated extensively [1–4] due to its wide
consumption.
Many solvents have been tried to improve the recovery of or-
ganic acids from dilute solutions. There are practical concerns
when choosing extraction solvents, toluene can be considered as
a suitable solvent for extraction of carboxylic acids from water,
having low vapour pressure, capability to form two phases, and ra-
pid phase separation due to its low density (0.8669 kg  m3 at
T = 298.2 K) and low viscosity (5.90  104 Pa  s at T = 298.2 K)
[5,6].
In extraction process, exact liquid–liquid equilibrium data and
accurate modelling are demanded. Activity coefficient models,
such as the non-random two liquid (NRTL) [7] and the universal
quasi chemical (UNIQUAC) [8] models have been frequently used
for the predicting different (liquid + liquid) systems. The binary
interaction parameters of models have been obtained by regression
with experimental data.
It is noteworthy that previous LLE data for the extraction of ace-
tic acid from water using toluene solvent have been reported in
⇑ Corresponding author.
E-mail address: saien@basu.ac.ir (J. Saien).
two articles. In 1973, Dakshinamurty et al. [9] just reported the
experimental data for this system at temperatures of (303.2,
313.2, and 333.2) K, and in 1985 Badakhshan et al. [10] compared
experimental data with the predicted values by the universal func-
tional activity coefficient (UNIFAC) model at temperatures of
(278.2, 283.2, 293.2, 303.2, and 323.2) K. Considering wide use of
this system in liquid–liquid extraction investigations [4,11], the
objective of this research is to provide a new series of LLE data
for the ternary {water (1) + acetic acid (2) + toluene (3)} system
at three specified temperatures of (288.2, 298.2, and 313.2) K. Then
NRTL and UNIQUAC models are examined for regression of exper-
imental data and obtaining binary interaction parameters, using
Aspen Plus simulator. Also, distribution coefficient and separation
factor for acetic acid were determined at different temperatures
for the purpose of process design and simulation applications. No
attempt has been made so far, for correlating LLE data of this sys-
tem with NRTL and UNIQUAC models.
2. Experimental
2.1. Materials
All materials were purchased from Merck Company. Toluene
and acetic acid were with mass fraction purities >0.995 and were
used without further purification. Standard 0.1 mol  dm3
(±0.2%) sodium hydroxide solutions were used for titration. Deion-
ized water with ionic conductivity <0.08 lS  cm1 was produced
from a deionizer (Hastaran Teb. Co.) and used in all experiments.

0021-9614/$ - see front matter Ó 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.jct.2012.08.017
 J. Saien et al. / J. Chem. Thermodynamics 57 (2013) 76–81 77

Table 1 summarizes relevant information on sample material 3. Results and discussion

purities.
3.1. Tie-lines, distribution coefficients and separation factor
2.2. Apparatuses
The experimental tie line data for the {water (1) + acetic acid
The two phase (liquid + liquid) equilibrium was established in (2) + toluene (3)} ternary system at different used temperatures
special glass cells. Cells were placed inside a shaking water bath are presented in table 2. Results at T = 313.2 K in this work were
(N–BIOTEK–304) with adjustable shaking speed and temperature compared to the published data by Dakshinamurty et al. [9]. Differ-
with an associated uncertainty of ±0.1 K. The set up was calibrated ence between these two data sources (solute weight fraction in the
once with deionized water and an accurate thermometer (Amadi- organic phase) varied from 12 to 24%. The lower difference is for
git, ad 3000th, Percisa, Germany). An electronic Ohaus balance lower solute concentration. The procedure used in this work is
(Adventurer, Pro AV264, Switzerland) with the uncertainty of based on utilizing the results of the direct analysis of components
±0.0001 g was used for weighting. Karl Fisher titrator (831 KF Cou- as well as the mass balance equation, as is conventionally used
lometer, Metrohm, Switzerland) with the uncertainty of [2,12,13].
±0.0001 g  kg1 was used to measure water content in organic The data are illustrated in figure 1 typically by plotting the mass
phase. All experiments were performed under atmospheric pres- fraction of acetic acid in the organic phase versus that of the aque-
sure. The applied temperatures in this work were (288.2, 298.2, ous phase at different temperatures. There is no obvious influence
and 313.2) K. of temperature on the distribution coefficient with low amounts of
acetic acid. However, at high solute amounts (w23 more than about
2.3. Procedure 0.02), a higher distribution coefficient is achieved while the influ-
ence of temperature is also remarkable. Similar results have been
Ternary mixtures with known overall compositions were pre- previously reported for other chemical system of (cumene + isobu-
pared by weighing in the special glass cells. These cells were sha- tyric acid + water) [12].
ken for 5 h at the temperature desired, then allowed to remain at The ability of the solvent to extract acetic acid was demon-
rest for 14 h until phase separation was complete. Afterward, sam- strated by the separation factor, S and distribution coefficients,
ples were taken from each phase (the upper layer solvent-rich D1 and D2. These parameters were calculated as:
phase and the lower layer water-rich phase) for analysis.
D2
For the analysis of acetic acid in aqueous and organic phases, S¼ ; ð5Þ
D1
samples taken from each phase were weighed and titrated with
0.1 mol  dm3 sodium hydroxide solutions, in the presence of phe- where D1 and D2 are the distribution coefficients of water and acetic
nolphthalein as the indicator. The sodium hydroxide volumes were acid between organic and aqueous phases, respectively; according
added by titration with volumes between (722 and 1324) mm3 for to equations:
samples of mass between (0.0169 and 0.1341) g. These volumes
were obtained from a mircrolitre syringe with the uncertainty of
0.5 mm3. For each phase in the sample, the titration was repeated
four times, and the average was used. The sample taken from or-
ganic phase was also analyzed using the Karl Fisher titration meth- TABLE 2
od. To calculate the mass fraction of toluene (component 3) in the Tie line data (mass fraction) for the ternary {water (1) + acetic acid (2) + toluene (3)}
system at different temperatures.a
organic phase (w33), the mass fraction of the water and acetic acid
was subtracted. The standard uncertainty for the mass fractions Aqueous phase Organic phase
measured is estimated as u(w) = 0.0008. w11 w21 w31 w13 w23 w33
Simultaneous solving equations (1) and (2) gives the mass of or-
T = 288.2 K
ganic (morg) and aqueous (maq) phases in equilibrium: 0.7875 0.2098 0.0027 0.0005 0.0123 0.9871
0.7472 0.2505 0.0023 0.0006 0.0181 0.9813
morg  w23 þ maq  w21 ¼ m2 ; ð1Þ
0.6885 0.3086 0.0029 0.0006 0.0269 0.9725
0.6552 0.3376 0.0072 0.0007 0.0323 0.9670
morg þ maq ¼ m1 þ m2 þ m3 : ð2Þ 0.6034 0.3875 0.0090 0.0010 0.0411 0.9579
0.5446 0.4450 0.0104 0.0012 0.0534 0.9454
Generally, wi1 and wi3 represent the mass fraction of compo- 0.5252 0.4636 0.0113 0.0018 0.0580 0.9402
nents i (=1, 2, 3) in the aqueous and organic phases, respectively. 0.4448 0.5370 0.0182 0.0025 0.0765 0.9210
Also, mi (i = 1, 2, 3) represents the total mass of each component T = 298.2 K
used. Accordingly the mass fraction of water and toluene in the 0.7921 0.2064 0.0015 0.0009 0.0124 0.9868
aqueous phase can be calculated from equations: 0.7321 0.2657 0.0022 0.0010 0.0220 0.9770
0.6898 0.3068 0.0034 0.0012 0.0281 0.9707
m3  ½morg  w33  0.6227 0.3682 0.0091 0.0017 0.0396 0.9587
w31 ¼ ; ð3Þ 0.6055 0.3853 0.0092 0.0017 0.0427 0.9556
maq
0.5317 0.4559 0.0125 0.0024 0.0586 0.9390
0.5049 0.4822 0.0129 0.0027 0.0664 0.9308
w11 ¼ 1  w31  w21 : ð4Þ 0.4452 0.5355 0.0193 0.0034 0.0816 0.9150
T = 313.2 K
0.7857 0.2124 0.0019 0.0012 0.0160 0.9828
TABLE 1 0.7354 0.2568 0.0073 0.0013 0.0239 0.9748
Suppliers and purities of the used chemicals. 0.6904 0.3028 0.0068 0.0016 0.0313 0.9671
0.6334 0.3598 0.0067 0.0023 0.0417 0.9560
Chemical Supplier State Mass fraction puritya
0.5988 0.3939 0.0073 0.0029 0.0488 0.9483
Toluene Merck Co. Liquid P0.995 0.5322 0.4587 0.0091 0.0043 0.0657 0.9300
Acetic acid Merck Co. Liquid P0.995 0.5030 0.4847 0.0123 0.0042 0.0734 0.9224
Sodium hydroxide Merck Co. Solution Standard 0.4490 0.5361 0.0149 0.0057 0.0909 0.9034
a a
The purities refer to the mass fraction (informed by supplier). Standard uncertainties: u(T) = 0.1 K, u(w) = 0.0008.
78 J. Saien et al. / J. Chem. Thermodynamics 57 (2013) 76–81

0.100 0.18 0.014

0.090 0.16
0.012
0.080
0.14

0.070 0.010
0.12
D1
0.060
0.10 0.008
W 23

D1
D2
0.050

0.08 0.006
0.040
D2
0.06
0.030
0.004

0.020 0.04

0.002
0.010 0.02

0.000
0.00 0.000
0.000 0.100 0.200 0.300 0.400 0.500 0.600
0.15 0.20 0.25 0.30 0.3
35 0.40 0.45 0.50 0.55 0
0.60
W21
W21

FIGURE 1. Mass fraction of acetic acid in organic phase plotted versus its mass FIGURE 2. Water (D1) and acetic acid (D2) distribution coefficients plotted versus
fraction in the aqueous phase at the desired temperatures: 288.2 K ( ), 298.2 K ( ) acetic acid mass fraction in the aqueous phase at different temperatures: 288.2 K
and 313.2 K ( ). ( ), 298.2 K ( ) and 313.2 K ( ).

w13
D1 ¼ ; ð6Þ
w11 100

90

w23
D2 ¼ : ð7Þ 80
w21
70
The distribution coefficients and separation factors for different
60
temperatures are listed in table 3. Meanwhile, figures 2 and 3 show
S

the variations of D2, D1 and S versus mass fraction of solute in the 50

aqueous phase. The results show that the use of toluene for the 40
extraction of acetic acid from its aqueous solution provides a distri-
30
bution coefficient ranging from 0.0587 to 0.1696 and separation
factor from 13.36 to 99.02 within the temperature range of this 20

study. These observations reveal the general capability of toluene 10

0.150 0.200 0.250 0.300 0.350 0.400 0.450 0.500 0.550
to extract acetic acid from the aqueous phase at different
W21
temperatures.
As figure 2 shows D2 varies linearly with acetic acid concentra- FIGURE 3. Separation factor of acetic acid plotted versus its mass fraction in the
tion; however, a non linear variation is relevant for D1. This varia- aqueous phase at different temperatures: 288.2 K ( ), 298.2 K ( ) and 313.2 K ( ).
tion is due to significant increase of water content in organic phase
when the solute mass fraction increases. Acetic acid and water of 288.2 K. This temperature effect is more moderate at low con-
form hydrogen bonds; therefore, with the higher percentage of centrations of acetic acid. The highest separation (about 100) is
acid in the organic phase, higher amounts of water will be associ- achieved when its aqueous phase mass fraction is about 0.27. A
ated. As a consequence, S decreases with solute concentration, as is similar variation can be deduced from the data presented by Daks-
evident from figure 3. hinamurty et al. [9] or from the literature [14,15]. These results
The effect of temperature is most noticeable. As temperature in- indicate that a high separation can be achieved when there is an
creases, a significant shift toward higher values of distribution acetic acid aqueous phase mass fraction of about 0.27 at the lower
coefficient is achieved. But at lower solute concentrations, the ef- temperatures. Generally, toluene has a negligible miscibility with
fect is moderate especially for the water distribution coefficient. water, and provides a suitable separation factor for extraction of
These sorts of variation with temperature provide a separation fac- acetic acid from dilute water solutions.
tor that decreases with increase of temperature so that the highest Figures 4 to 6 show the ternary diagram of (water + acetic
level of the separation factor is achieved at the lowest temperature acid + toluene) at temperatures (288.2, 298.2, and 313.2) K, respec-
tively. To ascertain the reliability of the experimental tie-line re-
sults, the Othmer–Tobias [16] and the Hand [17] equations were
TABLE 3 used. These correlations respectively are:
Distribution coefficients of water (D1) and acetic acid (D2) and separation factors (S) at    
different temperatures. 1  w33 1  w11
ln ¼ a þ b ln ; ð8Þ
T = 288.2 K T = 298.2 K T = 313.2 K w33 w11
D1 D2 S D1 D2 S D1 D2 S    
w21 w23
0.0007 0.0587 84.52 0.0011 0.0600 55.83 0.0016 0.0754 48.42 ln ¼ A þ B ln ; ð9Þ
0.0008 0.0725 90.39 0.0014 0.0826 59.84 0.0018 0.0930 52.53 w11 w33
0.0009 0.0873 99.02 0.0017 0.0917 54.22 0.0023 0.1035 44.62
0.0011 0.0958 89.31 0.0027 0.1076 40.04 0.0036 0.1160 32.24 where a and b are the parameters of the Othmer–Tobias correlation
0.0016 0.1062 65.29 0.0028 0.1107 39.16 0.0049 0.1238 25.43 and A, and B the parameters of the Hand correlation. The values of
0.0023 0.1200 52.33 0.0046 0.1285 28.08 0.0081 0.1432 17.68 these parameters, together with the coefficients of determination
0.0034 0.1251 37.03 0.0054 0.1378 25.35 0.0083 0.1515 18.16
(R2) are listed in table 4. The R2 is approximately unity and the lin-
0.0055 0.1425 25.75 0.0076 0.1524 20.14 0.0127 0.1696 13.36
ear variation of the data in their plots according to above parame-
 J. Saien et al. / J. Chem. Thermodynamics 57 (2013) 76–81 79

Acetic acid TABLE 4

Parameters of the Othmer–Tobias and the Hand correlations at different
0.0 1.0 temperatures.

0.1 0.9 T/K Othmer–Tobias correlation Hand correlation

0.2 a b R2 A B R2
0.8
288.2 2.6453 1.2223 0.9924 2.6364 1.2466 0.9914
0.3 0.7 298.2 2.5769 1.2183 0.9919 2.5775 1.2546 0.9907
0.4
313.2 2.4474 1.1935 0.9981 2.4764 1.2024 0.9967
0.6

0.5 0.5

0.6 0.4 TABLE 5

NRTL and UNIQUAC binary intraction parameters for {water (1) + acetic acid
0.7 0.3 (2) + toluene (3)}.
0.8 0.2 Component i 3 3 1
Component j 1 2 2
0.9 0.1
NRTL
1.0 0.0 aij 247.87 0.0 0.0
Toluene 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 Water aji 627.05 0.0 0.0
bij/K 15246.92 234.15 1111.56
FIGURE 4. Ternary system diagram for (water + acetic acid + toluene) at T = 288.2 K bji/K 27224.65 638.94 684.46
(four tie lines for instance): ( ) and solid line, experimental tie lines; ( ) and dash cij 0.20 0.30 0.30
long line, NRTL tie lines; ( ) and dotted line, UNIQUAC tie lines. eij 35.58 0.0 0.0
eji 92.71 0.0 0.0
UNIQUAC
Acetic acid bij/K 1340.08 78.73 660.99
bji/K 396.58 20.53 79.77
0.0 1.0

0.1 0.9 ters, indicate the degree of dependability of the measured LLE val-
0.2 0.8
ues in this study.

0.3 0.7
3.2. Models application and evaluation
0.4 0.6
The experimental results obtained were correlated with NRTL
0.5 0.5
and UNIQUAC models. The relationship of the LLE can be repre-
0.6 0.4 sented by an activity coefficient model. In these models, the basic
0.7
relationships for each component i in two coexistent liquid phases
0.3
of a system at equilibrium are:
0.8 0.2
xIi cIi ¼ xIIi cIIi ; ð10Þ
0.9 0.1
X
1.0 0.0 xIi ¼ 1; ð11Þ
Toluene 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 Water i

FIGURE 5. Ternary system diagram of (water + acetic acid + toluene) at T = 298.2 K

X
xIIi ¼ 1; ð12Þ
(four tie lines for instance): ( ) and solid line, experimental tie lines; ( ) and dash
i
long line, NRTL tie lines; ( and dotted line, UNIQUAC tie lines.
where xIi , xIIi , cIi and cIIi are the mole fractions and activity coefficients
Acetic acid of component i in phases I and II, respectively. The NRTL activity
0.0 1.0 coefficient equation is [7]:
P P
j xj sji Gji
X xj Gij  
v xv sv j Gv j ;
0.1 0.9
ln ci ¼ P þ P sij  P ð13Þ
0.2 0.8 k xk Gki j k xk Gkj k xk Gkj

0.3 0.7 where x is the mole fraction, s and G are binary parameters for NRTL
0.4 0.6
model, and i, j, k and v are indices, each of them for all the three
components.
0.5 0.5 The binary interaction parameters can be calculated using the
0.6 0.4
following equations [18]:
0.7 bij
0.3
sij ¼ aij þ þ eij ln T; ð14Þ
0.8
T
0.2

0.9 0.1 aij ¼ aji ¼ cij ; ð15Þ

1.0
Toluene 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
0.0
Water
Gij ¼ expðaij sij Þ; ð16Þ

FIGURE 6. Ternary system diagram of (water + acetic acid + toluene) at T = 313.2 K

where a is the non-random parameter and aij, bij and cij are NRTL
(four tie lines for instance): ( ) and solid line, experimental tie lines; ( ) and dash coefficients of the equations for binary interaction parameters.
long line, NRTL tie lines; ( ) and dotted line, UNIQUAC tie lines. The binary interaction parameters can be obtained from LLE data
80 J. Saien et al. / J. Chem. Thermodynamics 57 (2013) 76–81

TABLE 6
a
Calculated NRTL and UNIQUAC tie lines in mass fraction for {water (1) + acetic acid (2) + toluene (3)} system.

w11 w21 w13 w23

NRTL UNIQUAC NRTL UNIQUAC NRTL UNIQUAC NRTL UNIQUAC
T = 288.2 K
0.7690 0.7641 0.2287 0.2337 0.0005 0.0006 0.0146 0.0135
0.7514 0.7501 0.2459 0.2474 0.0005 0.0007 0.0165 0.0152
0.7139 0.7205 0.2825 0.2762 0.0006 0.0008 0.0210 0.0194
0.6434 0.6623 0.3506 0.3320 0.0009 0.0011 0.0316 0.0303
0.5975 0.6258 0.3945 0.3665 0.0011 0.0014 0.0403 0.0392
0.5633 0.5978 0.4269 0.3926 0.0014 0.0016 0.0477 0.0474
0.5275 0.5718 0.4605 0.4166 0.0018 0.0018 0.0564 0.0563
0.4603 0.5132 0.5228 0.4691 0.0027 0.0026 0.0759 0.0811
298.2 K
0.8065 0.7913 0.1919 0.2070 0.0007 0.0007 0.0128 0.0121
0.7506 0.7442 0.2467 0.2530 0.0009 0.0009 0.0188 0.0182
0.7018 0.7050 0.2942 0.2909 0.0010 0.0011 0.0253 0.0248
0.5981 0.6231 0.3937 0.3687 0.0017 0.0017 0.0440 0.0447
0.5921 0.6182 0.3993 0.3732 0.0017 0.0017 0.0453 0.0462
0.5304 0.5697 0.4572 0.4180 0.0024 0.0023 0.0603 0.0634
0.5127 0.5554 0.4737 0.4309 0.0026 0.0025 0.0652 0.0693
0.4560 0.5085 0.5256 0.4725 0.0036 0.0032 0.0828 0.0919
313.2 K
0.8000 0.7815 0.1982 0.2164 0.0014 0.0010 0.0163 0.0159
0.6742 0.6787 0.3204 0.3158 0.0021 0.0017 0.0344 0.0357
0.6679 0.6712 0.3265 0.3229 0.0021 0.0017 0.0355 0.0376
0.6408 0.6480 0.3524 0.3448 0.0023 0.0020 0.0407 0.0442
0.6138 0.6263 0.3780 0.3651 0.0026 0.0022 0.0464 0.0511
0.5545 0.5800 0.4337 0.4078 0.0033 0.0029 0.0608 0.0686
0.5232 0.5563 0.4627 0.4292 0.0038 0.0033 0.0696 0.0793
0.4722 0.5168 0.5091 0.4642 0.0047 0.0041 0.0858 0.0998
a
Standard uncertainties: u(T) = 0.1 K, u(w) = 0.0008.

regression using Aspen Plus (Version 11.1). This software employs where aij, bij, cij and dij are UNIQUAC coefficients of the equations for
an objective function, called ‘‘maximum likelihood’’ and an algo- binary interaction parameters. The UNIQUAC structural parameters
rithm, called ‘‘Britt–Luecke’’ to correlate model parameters [12]. r (volume parameter) and q (surface parameter) have been previ-
The equation of UNIQUAC activity coefficient model is in fact ously calculated from the number of molecular groups and the indi-
sum of two terms: a combinatorial term and a residual term, rep- vidual values of the van der Waals volume and area of the molecule
resented as [19]: by the Bondi method [20,21]. The detailed description of the mean-
ing of parameters and equations is expressed in the literature [22].
lnci ¼ lncCi ðcombinatorialÞ þ lncRi ðresidualÞ; ð17Þ
The values of r and q used in the UNIQUAC model for this system are
where the combinatorial and residual terms of the activity coeffi- given in literature [23,24].
cient are due to the difference in shape and energy of the molecules, The coefficients that were retrieved from the Aspen Plus simu-
respectively. These terms can be given as: lator, based on the above equations to calculate the binary interac-
    tion parameters for the NRTL and UNIQUAC models, are listed in
Ui z hi Ui Xc
table 5. It is noted that sij in equation (21) is a function only of
lncCi ¼ ln þ qi ln þ li  xj lj ; ð18Þ
xi 2 Ui xi j¼1 its second term and the parameters aij, cij and dij are set to zero.
The estimated tie lines for the system used are given in table 6.
2 0 13
The ternary diagrams that represent the experimental results to-
6 !
6 Xc Xc BB hj sij C7
C7 gether with the correlated results for the used system at tempera-
lncRi ¼ qi 6
61  ln hj sji  B
BXc
C7;
C7 ð19Þ tures (288.2, 298.2 and 313.2) K are shown in figures 4 to 6,
4 j¼1 @ A5 respectively. As is obvious, correlation using both models exhibits
j¼1
hk skj
k¼1 acceptable agreement, particularly with the NRTL model which is
consistent for all solute concentrations and temperatures.
where i, j and k are indices, c is the number of components, sij is the To represent the capability of the used models, the root-mean
adjustable parameter and hj andUi the surface area and volume square deviation (RMSD) between experimental and calculated
fractions used in UNIQUAC model. The parameters of UNIQUAC data was determined using the following equation:
are calculated by the following equations:
P PP exp 2
!1=2
z k j i ðwijk  wcal
ijk Þ
li ¼ ðr i  qi Þ  ðri  1Þ; ð20Þ RMSD ¼ ; ð24Þ
2 6N

bij where N is the number of tie-lines, wexp

sij ¼ aij þ þ cij ln T þ dij T; ð21Þ ijk indicates the experimental
T mass fraction, wcal ijk is the calculated mass fraction, and the subscript
i, j and k = 1, 2, . . . , N index components, phases and tie lines, respec-
x ri
Ui ¼ Pc i ; ð22Þ tively. For all data, the RMSD values in the correlation based on
j¼1 xj r j NRTL and UNIQUAC models are 0.0119 and 0.0223, respectively.
These reasonable errors confirm the reliability of the results and
xi q
hi ¼ Pc i ; ð23Þ that both the NRTL and UNIQUAC models give excellent correlation
j¼1 xj qj results for the experimental solubility data.
 J. Saien et al. / J. Chem. Thermodynamics 57 (2013) 76–81
4. Conclusions
The LLE for the ternary systems of (water + acetic acid + tolu-
ene) was studied at temperatures of (288.2, 298.2, and 313.2) K
and under atmospheric pressure.
The efficiency of the extraction of acetic acid from water by tol-
uene was evaluated by the criteria of the distribution coefficient
and separation factor. It was revealed that the acetic acid distribu-
tion coefficient was increased, while, the separation factor de-
creased with temperature. Meanwhile, a maximum extraction
factor (about 100) is relevant for solute aqueous phase mass frac-
tion around 0.27 at T = 288.2 K. The reliability of experimental tie
line data was examined by the Othmer–Tobias and Hand equa-
tions. Results show a high degree of consistency with the coeffi-
cient of determinations (R2) with values within 0.9907–0.9981.
The UNIQUAC and NRTL models were used to correlate the
experimental LLE data and for demonstrating in trigonal phase dia-
grams from binary data. The NRTL and UNIQUAC models with the
estimated molecular interaction coefficients obtained with the aid
of Aspen Plus simulator, yield tie lines very close to those from the
experiments. In general, the NRTL model provides better results
than the UNIQUAC model for the system investigated.
Acknowledgement
We express thanks to the university authorities for providing
the financial support to carry out this work.
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JCT 12-412