J. Chem.

Thermodynamics 40 (2008) 16661670

Contents lists available at ScienceDirect

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

Liquid phase equilibria of (water + phosphoric acid + 1-butanol

or butyl acetate) ternary systems at T = 308.2 K
H. Ghanadzadeh a,b, A. Ghanadzadeh a,*, Kh. Bahrpaima a
a
Department of Chemistry, Faculty of Science, University of Guilan, Rasht, Iran
b
Department of Chemical Engineering, University of Guilan, Rasht, Iran

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

Article history: (Liquid + liquid) equilibria and tie lines for the ternary systems of (water + phosphoric acid + 1-butanol)
Received 6 May 2008 and (water + phosphoric acid + butyl acetate) were measured at T = 308.2 K. The experimental ternary
Received in revised form 27 June 2008 (liquid + liquid) equilibrium data were correlated with the UNIQUAC model. The reliability of the exper-
Accepted 1 July 2008
imental tie lines was conrmed using OthmerTobias correlation. The average root-mean-square devia-
Available online 9 July 2008
tion (RMSD) values of (water + phosphoric acid + 1-butanol) and (water + phosphoric acid + butyl
acetate) systems were 2.17% and 2.16%, respectively. Distribution coefcients and separation factors were
Keywords:
measured to evaluate the extracting capability of the solvents. The results show that butyl acetate may be
LLE data
Ternary systems
considered as a reliable organic solvent for the extraction of phosphoric acid from aqueous solutions.
UNIQUAC model 2008 Elsevier Ltd. All rights reserved.
Extraction processes

1. Introduction
The precise (liquid + liquid) equilibrium (LLE) data of multi-
component mixtures are important to design many chemical pro-
cesses and separation operations. The LLE investigations of ternary
systems have been the subject of much interest in the recent years
[17].
Phosphoric acid is a widely used acid, which has many indus-
trial applications. The pure phosphoric acid is extensively used as
and additive in the food industry. Therefore, the separation and
purication of phosphoric acid from aqueous solutions by solvent
extraction technique are of economic importance in the chemical
industry [810].
Liquid phase equilibrium data of (water + phosphoric acid) with
organic solvents (extractants) are important and needed for the de-
sign of an efcient separation operation. Many organic solvents
have been investigated and reported in the literature as extractants
for the extraction and purication of phosphoric acid from water.
Heavy alcohols, ketones and ethers have mainly been used for
extraction of phosphoric acid from aqueous solutions [1118].
The type of solvent is one of the most important factors that inu-
ences the equilibrium characteristics of the extraction of acid from
aqueous solutions [1922]. From practical and economical aspects,
the search for new and suitable organic solvents for the separation
of phosphoric acid from water is a current study. In this research,
1-butanol and butyl acetate were tested as organic solvents for
* Corresponding author. Tel./fax: +98 131 3233262.
E-mail address: aggilani@guilan.ac.ir (A. Ghanadzadeh).
recovery of phosphoric acid from water. The 1-butanol and butyl
acetate have been used as organic solvents for the determination
of LLE data for many ternary mixtures [2325].
The focus of this study is placed on the phase behaviour of LLE
for the mixtures of (water + phosphoric acid) with 1-butanol and
butyl acetate at T = 308.2 K. The LLE data were correlated with
the solution model of UNIQUAC, and the values of the interaction
parameter were obtained. Distribution coefcients and separation
factors were determined from the tie line data to establish the
extracting capability of the solvents and the possibility of using
these solvents for the separation of (water + phosphoric acid).
2. Experimental
2.1. Materials
Analytical grade phosphoric acid, 1-butanol and butyl acetate
(mass fraction purity > 0.99) were supplied by Merck. Bi-distilled
water was used throughout all the experiments.
2.2. Procedure
The equilibrium between liquid phases was studied in a trans-
parent water thermostat at T = 308.2 K. The temperature was con-
trolled within 0.1 K. A glass cell which can contain a solution of
volume from (50 to 200) cm3 was designed. The cell was lled with
known masses of heterogeneous mixtures of (water + phosphoric
acid + solvent). The prepared mixtures were placed in the extrac-
tion vessel, stirred for 4 h, and then left to settle for 4 h.

0021-9614/$ - see front matter 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jct.2008.07.001
 H. Ghanadzadeh et al. / J. Chem. Thermodynamics 40 (2008) 16661670 1667

After separation, the aqueous and organic phases were weighed values [15]. The values of r and q used in the UNIQUAC equation
and analyzed. The compositions of the conjugated phases allowed are presented in table 1.
us to construct the tie lines. The concentrations of phosphoric acid
in both the phases were obtained by potentiometric NaOH titration 3. Results and discussion
in the presence of phenolphthalein as an indicator. The water con-
tent of the organic phase was measured by the Karl-Fisher method 3.1. Experimental LLE data
[26] using a Mettler Toledo DL 38 Karl-Fischer titrator. The water
content in the aqueous phase and the amount of the organic sol- The experimental LLE data of (water + phosphoric acid) with 1-
vents in both the phases were determined by using a material bal- butanol or butyl acetate at T = 308.2 K are presented in table 2. The
ance [15]. All weighing was carried out with an analytical balance LLE phase diagrams for (water + phosphoric acid + 1-butanol) and
accurate to within 0.0001 g. The estimated uncertainties in the (water + phosphoric acid + butyl acetate) systems are plotted and
mole fractions were about 0.0005. are shown in gures 1 and 2. In the gures, the observed and cal-
culated tie lines for the ternary systems at T = 308.2 K are com-
2.3. Correlation of LLE using the UNIQUAC method pared. Because (water + 1-butanol or butyl acetate) is the only
pair that is partially miscible, both the ternary systems investi-
The experimental LLE data of a ternary system can be correlated gated behave as type-1 of the LLE.
using the universal quasi-chemical model (UNIQUAC) [27,28]. The The effectiveness of phosphoric acid extraction done using the
mole fractions xEi and xRi of LLE phases (extracted phase and raf- solvent butyl acetate or 1-butanol is given by their separation fac-
nate phase) can be determined using the thermodynamic principle tor (S), which is a measure of the ability of solvent to separate the
and mass balance equation: acid from water. The separator factor is dened as the ratio of dis-
tribution coefcient of the acid (2) to the distribution coefcient of
ci xi E ci xi R ; 1
X X the water (1), S = D2/D1.
xEi xRi 1: 2 In order to indicate and compare the ability of the solvents bu-
tyl acetate or 1-butanol in the recovery of phosphoric acid, distri-
Here, cEi and cRi are the corresponding activity coefcients of compo-
bution coefcients for water (D1 = x13/x11) and phosphoric acid
nent (i) in the extracted (solvent) phase and rafnate (aqueous)
(D2 = x23/x21) and the separation factors, S, were calculated. The
phase, respectively. The UNIQUAC equation for the liquid-phase
x13 and x23 are the mole fractions of water and acid in the organ-
activity coefcient is represented as follows:
ic-rich phase, respectively. The x11 and x21 are the mole fractions
ln ci ln ci combinatorial ln ci residual: 3 of water and acid in the aqueous phase, respectively. The distribu-
tion coefcients and separation factors for both ternary systems
The combinatorial and residual parts of the activity coefcient are
are given in table 3. The variation of the distribution coefcient
due to the difference in size and energy of the molecules, respec-
and separation factor of phosphoric acid as a function of the mole
tively. The combinational and residual parts of the coefcient can
fraction of the acid in aqueous phase for both the ternary systems
be written as follows:
is shown in gures 3 and 4.
2 0 13
!
6 X
c X
c B C7
ln cRi qi 6 hj sji B hj sij C7;
41  ln  @Pc A5 4
j1 j1 hk skj TABLE 1
k1 The UN1QUAC structural parameters
   
Ui z hi / X C
Components r q
ln cCi ln qi ln ii  i xj ij : 5
xi 2 Ui xi j1 Water 0.920 1. 400
Phosphoric acid 3.000 4.000
Here sij is the adjustable parameter in the UNIQUAC equation. The 1-Butanol 3.454 3.052
Butyl acetate 4.827 4.196
parameters Ui (segment fraction), hi (area fraction), and sij are given
by the following equations:
xi r i xi r i
Ui and hi c ; 6
Pc P TABLE 2
xi r i xi qi The experimental LLE date for {water (1) + phosphoric acid (2) + 1-butanol or butyl
i1 i1 acetate (3)} at T = 308.2 K
   a 
Duij ij
sij exp  exp  : 7 Aqueous phase Organic phase
RT T
x1 x2 x3 x1 x2 x3
The UNIQUAC structural parameters r (the number of segments per Water + phosphoric acid + 1-butanol
molecule) and q (the relative surface area per molecule) were calcu- 0.9800 0.0000 0.0200 0.4690 0.0000 0.5310
lated from the group contribution data reported previously [15,28]. 0.9554 0.0295 0.0151 0.4740 0.0180 0.5080
The above equations clearly show that the UNIQUAC model requires 0.9350 0.0520 0.0130 0.4840 0.0383 0.4777
0.9125 0.0745 0.0130 0.5085 0.0640 0.4275
surface area and volume parameters for each molecule in the mix-
0.898 0.0879 0.0141 0.5399 0.0860 0.3741
ture in order to calculate the combinatorial contribution term. The r 0.8852 0.0985 0.0163 0.6000 0.1140 0.2860
and q parameters can be computed using the van der Waals volume 0.8480 0.1192 0.0328 0.7150 0.1365 0.1485
and surface area of the molecule [29,30]. The surface area and vol-
ume are characteristic properties of a molecule and can be derived Water + phosphoric acid + butyl acetate
0.9976 0.0000 0.0024 0.0820 0.0000 0.9180
from the molecular structure. 0.9654 0.0313 0.0033 0.0880 0.0165 0.8955
The values of r and q were also computed from the molecular 0.8716 0.1240 0.0044 0.0960 0.0530 0.8510
volume and surface area of phosphoric acid. The area and volume 0.7987 0.1945 0.0068 0.1150 0.098 0.7870
parameters were calculated by the geometric method using bond 0.7366 0.2487 0.0147 0.1920 0.1970 0.6110
0.6620 0.3030 0.0350 0.3339 0.2850 0.3811
distances and the van der Waals radii. The parameters obtained
0.6330 0.3272 0.0398 0.4477 0.3302 0.2221
using CHEMCAD are in very good agreement with the literature
1668 H. Ghanadzadeh et al. / J. Chem. Thermodynamics 40 (2008) 16661670

Phosphoric acid 1.6

0.0 1.0
0.1 0.9 1.2
0.2 0.8
0.3 0.7

D2
0.8
0.4 0.6
0.5 0.5
0.6 0.4
0.4
0.7 0.3
0.8 0.2 0.0
0.00 0.10 0.20 0.30 0.40
0.9 0.1 x21
1.0 0.0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 FIGURE 3. Plot of the distribution coefcient (D2) of phosphoric acid as a function
of the mole fraction (x21) of phosphoric acid in aqueous phase, () 1-butanol, (M)
1-Butanol water butyl acetate experimental () and calculated (- - -) data.

FIGURE 1. Experimental () and correlated UNIQUAC (- - -) LLE data for

(water + phosphoric acid + 1-butanol) at T = 308.2 K.
10

Phosphoric acid 8
0.0 1.0
0.1 0.9 6
0.2
S

0.8
0.3 4
0.7
0.4 0.6
2
0.5 0.5
0.6 0.4 0
0.7 0 0.1 0.2 0.3 0.4
0.3
x21
0.8 0.2
FIGURE 4. Plot of the separation factor (S) of phosphoric acid as a function of the
0.9 0.1 mole fraction (x21) of phosphoric acid in aqueous phase, () 1-butanol, (N) butyl
acetate, experimental () and calculated (- - -) data.
1.0 0.0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Water The experimental results indicate that butyl acetate has a high-
Butyl acetate
er separation factor, thereby indicating the ability of butyl acetate
FIGURE 2. Experimental () and correlated UNIQUAC (- - -) LLE data for to extract phosphoric acid from water. This quantity for butyl ace-
(water + phosphoric acid + butyl acetate) at T = 308.2 K. tate is greater than one (separation factors varying between 1.865
and 5.783) for the system reported in this work, which means that

TABLE 3
Distribution coefcients of water (D1) and phosphoric acid (D2) and separation factors (S) for ternary systems of (water + phosphoric acid + 1-butanol) and (water + phosphoric
acid + butyl acetate) at T = 308.2 K

Water (1) + phosphoric acid (2) + 1-butanol (3) Water (1) + phosphoric acid (2) + butyl acetate (3)
D2 D1 S D2 D1 S
0.610 0.496 1.230 0.082
0.737 0.518 1.423 0.527 0.091 5.783
0.859 0.557 1.542 0.427 0.110 3.881
0.978 0.601 1.627 0.504 0.144 3.499
1.117 0.678 1.648 0.792 0.261 3.039
1.145 0.843 1.358 0.941 0.504 1.865
 H. Ghanadzadeh et al. / J. Chem. Thermodynamics 40 (2008) 16661670 1669

TABLE 5
8.0 Optimized UNIQUAC binary interaction parameters aij (K) for the (water + phosphoric
acid + 1-butanol or butyl acetate) ternary systems at T = 308.2 K
6.0 ij aij aji
Ln((1-x23)/x23))

Water (1) + phosphoric acid (2) + 1-butanol (3)

4.0 12 431.80 341.10
13 245.52 36.92
23 1796.81 495.31
2.0
Water (1) + phosphoric acid (2) + butyl acetate (3)
12 431.80 341.10
0.0 13 109.40 503.03
23 366.12 533.49

-2.0
-4 -3 -2 -1 0
Ln((1-x11)/x11)
the differences between the experimental and calculated mole
FIGURE 5. OthmerTobias plots of (water + phosphoric acid + butyl acetate) and fractions for each of the components over all the tie lines.
(water + phosphoric acid + 1-butanol) at T = 308.2 K, () 1-butanol, (M) butyl The root-mean-square deviation (RMSD) between the values
acetate. was calculated from the difference in the experimental and calcu-
lated mole fractions according to the following equation:
s
the extraction of phosphoric acid using butyl acetate is possible. P3 P2 Pn 2
i1 j1
^
k1 xi;j;k  xi;j;k
Therefore, this solvent may be considered as a possible candidate RMSD% 100 : 10
for the recovery of phosphoric acid from aqueous solutions. The 6n
separation factor for 1-butanol is near one (between 1.230 and The RMSD is a measure of the agreement between the experimental
1.358), meaning that 1-butanol is not a suitable solvent for the and calculated data. The average root-mean-square deviations for
extraction of phosphoric acid from water. (water + phosphoric acid + 1-butanol) and (water + phosphoric
The reliability of the experimental tie line data can be deter- acid + butyl acetate) were 2.17% and 2.16%, respectively.
mined using the OthmerTobias correlation [31] for the ternary
systems 4. Conclusions
   
1  x23 1  x11
ln A B ln ; 8 (Liquid + liquid) equilibrium data for two ternary mixtures
x23 x11
(water + phosphoric acid + 1-butanol) and (water + phosphoric
where A and B are the constants, x23 is the mole fraction of phos- acid + butyl acetate) were determined at T = 308.2 K. Both the sys-
phoric acid in the organic phase, and x11 is the mole fraction of tems exhibited type-1 (liquid + liquid) phase diagram. The experi-
water in the aqueous phase. The linearity of OthmerTobias plots mental LLE data were satisfactorily tted by the UNIQUAC model.
is shown in gure 5. The correlation parameters are listed in table 4. The experimental results indicated that butyl acetate has a high
separation factor, which shows the ability of butyl acetate to ex-
3.2. LLE correlation tract phosphoric acid from water. It can be concluded that butyl
acetate may serve as an adequate solvent for the extraction of
The raw experimental LLE data were correlated using the UNI- phosphoric acid from aqueous solutions.
QUAC model [27]. The correlated results together with the experi-
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