J. Chem.

Thermodynamics 40 (2008) 1666–1670

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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
Department of Chemistry, Faculty of Science, University of Guilan, Rasht, Iran
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 confirmed using Othmer–Tobias 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 coefficients and separation factors were
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 Ó 2008 Elsevier Ltd. All rights reserved.
Extraction processes

1. Introduction recovery of phosphoric acid from water. The 1-butanol and butyl
acetate have been used as organic solvents for the determination
The precise (liquid + liquid) equilibrium (LLE) data of multi- of LLE data for many ternary mixtures [23–25].
component mixtures are important to design many chemical pro- The focus of this study is placed on the phase behaviour of LLE
cesses and separation operations. The LLE investigations of ternary for the mixtures of (water + phosphoric acid) with 1-butanol and
systems have been the subject of much interest in the recent years butyl acetate at T = 308.2 K. The LLE data were correlated with
[1–7]. the solution model of UNIQUAC, and the values of the interaction
Phosphoric acid is a widely used acid, which has many indus- parameter were obtained. Distribution coefficients and separation
trial applications. The pure phosphoric acid is extensively used as factors were determined from the tie line data to establish the
and additive in the food industry. Therefore, the separation and extracting capability of the solvents and the possibility of using
purification of phosphoric acid from aqueous solutions by solvent these solvents for the separation of (water + phosphoric acid).
extraction technique are of economic importance in the chemical
industry [8–10]. 2. Experimental
Liquid phase equilibrium data of (water + phosphoric acid) with
organic solvents (extractants) are important and needed for the de- 2.1. Materials
sign of an efficient separation operation. Many organic solvents
have been investigated and reported in the literature as extractants Analytical grade phosphoric acid, 1-butanol and butyl acetate
for the extraction and purification of phosphoric acid from water. (mass fraction purity > 0.99) were supplied by Merck. Bi-distilled
Heavy alcohols, ketones and ethers have mainly been used for water was used throughout all the experiments.
extraction of phosphoric acid from aqueous solutions [11–18].
The type of solvent is one of the most important factors that influ- 2.2. Procedure
ences the equilibrium characteristics of the extraction of acid from
aqueous solutions [19–22]. From practical and economical aspects, The equilibrium between liquid phases was studied in a trans-
the search for new and suitable organic solvents for the separation parent water thermostat at T = 308.2 K. The temperature was con-
of phosphoric acid from water is a current study. In this research, trolled within ±0.1 K. A glass cell which can contain a solution of
1-butanol and butyl acetate were tested as organic solvents for volume from (50 to 200) cm3 was designed. The cell was filled with
known masses of heterogeneous mixtures of (water + phosphoric
* Corresponding author. Tel./fax: +98 131 3233262.
acid + solvent). The prepared mixtures were placed in the extrac-
E-mail address: aggilani@guilan.ac.ir (A. Ghanadzadeh). tion vessel, stirred for 4 h, and then left to settle for 4 h.

0021-9614/$ - see front matter Ó 2008 Elsevier Ltd. All rights reserved.

The phase.0000 0.6330 0.3339 0. H.5399 0.3741 ture in order to calculate the combinatorial contribution term. Correlation of LLE using the UNIQUAC method pared.4740 0.827 4. The water con- tent of the organic phase was measured by the Karl-Fisher method 3.0820 0. respec- and separation factor of phosphoric acid as a function of the mole tively. Results and discussion in the presence of phenolphthalein as an indicator. distri- Here.0383 0.4690 0.28].1970 0. The compositions of the conjugated phases allowed are presented in table 1.052 Butyl acetate 4.1192 0.0130 0.0985 0.3030 0. 0. The concentrations of phosphoric acid in both the phases were obtained by potentiometric NaOH titration 3.454 3.1240 0. 0. Thermodynamics 40 (2008) 1666–1670 1667 After separation. 2 0 13 ! 6 X c X c B C7 ln cRi ¼ qi 6 hj sji B hj sij C7.196 parameters Ui (segment fraction). using the universal quasi-chemical model (UNIQUAC) [27. respectively.7150 0.6110 0.7987 0.5085 0.0328 0. The values of r and q used in the UNIQUAC equation and analyzed.0398 0.3302 0.0147 0. xEi ¼ xRi ¼ 1: ð2Þ In order to indicate and compare the ability of the solvents bu- tyl acetate or 1-butanol in the recovery of phosphoric acid.0880 0. In the figures.0200 0. butanol or butyl acetate at T = 308. The estimated uncertainties in the (water + phosphoric acid + butyl acetate) systems are plotted and mole fractions were about 0.2 K are presented in table 2.0163 0.098 0.4777 0.28].5310 lated from the group contribution data reported previously [15.9800 0.4275 surface area and volume parameters for each molecule in the mix- 0. the observed and cal- culated tie lines for the ternary systems at T = 308.0001 g. Experimental LLE data [26] using a Mettler Toledo DL 38 Karl-Fischer titrator. / J. and sij are given by the following equations: xi r i xi r i Ui ¼ and hi ¼ c . All weighing was carried out with an analytical balance LLE phase diagrams for (water + phosphoric acid + 1-butanol) and accurate to within ±0.3272 0. cEi and cRi are the corresponding activity coefficients of compo- bution coefficients for water (D1 = x13/x11) and phosphoric acid nent (i) in the extracted (solvent) phase and raffinate (aqueous) (D2 = x23/x21) and the separation factors.920 1.0960 0.0000 0.0530 0.6620 0. The parameters obtained 0. 41  ln  @Pc A5 ð4Þ j¼1 j¼1 hk skj TABLE 1 k¼1 The UN1QUAC structural parameters     Ui z hi / X C Components r q ln cCi ¼ ln þ qi ln þ ii  i xj ij : ð5Þ xi 2 Ui xi j¼1 Water 0.1945 0.1150 0. The area and volume 0.000 Here sij is the adjustable parameter in the UNIQUAC equation.3811 distances and the van der Waals radii.0024 0. The ance [15].0640 0.8480 0. The combinational and residual parts of the coefficient can fraction of the acid in aqueous phase for both the ternary systems be written as follows: is shown in figures 3 and 4.0860 0.0033 0. respectively. The distribu- tion coefficients and separation factors for both ternary systems The combinatorial and residual parts of the activity coefficient are are given in table 3.3. The UNIQUAC equation for the liquid-phase x13 and x23 are the mole fractions of water and acid in the organ- activity coefficient is represented as follows: ic-rich phase. The r 0.0044 0.0295 0.0000 0.5080 The above equations clearly show that the UNIQUAC model requires 0.000 4.0141 0. The x11 and x21 are the mole fractions ln ci ¼ ln ci ðcombinatorialÞ þ ln ci ðresidualÞ: ð3Þ of water and acid in the aqueous phase.2850 0. were calculated.1920 0.30]. The variation of the distribution coefficient due to the difference in size and energy of the molecules.898 0.0180 0. hi (area fraction). S = D2/D1. both the ternary systems investi- The experimental LLE data of a ternary system can be correlated gated behave as type-1 of the LLE. Chem.4477 0. The The effectiveness of phosphoric acid extraction done using the mole fractions xEi and xRi of LLE phases (extracted phase and raffi.2 K are com- 2. Because (water + 1-butanol or butyl acetate) is the only pair that is partially miscible.0005.7366 0. which is a measure of the ability of solvent to separate the and mass balance equation: acid from water.2860 and q parameters can be computed using the van der Waals volume 0.2221 using CHEMCAD are in very good agreement with the literature . The experimental LLE data of (water + phosphoric acid) with 1- vents in both the phases were determined by using a material bal.0165 0.2 K    a  Duij ij sij ¼ exp  ¼ exp  : ð7Þ 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.1365 0.0068 0. ð6Þ Pc P TABLE 2 xi r i xi qi The experimental LLE date for {water (1) + phosphoric acid (2) + 1-butanol or butyl i¼1 i¼1 acetate (3)} at T = 308. respectively. the aqueous and organic phases were weighed values [15].8510 volume and surface area of phosphoric acid.9554 0.0879 0.9350 0.8852 0.2487 0. Ghanadzadeh et al.0130 0. 0. The surface area and vol- ume are characteristic properties of a molecule and can be derived Water + phosphoric acid + butyl acetate 0.0313 0.7870 parameters were calculated by the geometric method using bond 0.8955 The values of r and q were also computed from the molecular 0.9180 from the molecular structure.1140 0. The 1-Butanol 3.0151 0.8716 0.9654 0. The water content in the aqueous phase and the amount of the organic sol.0350 0.9125 0.6000 0. solvent butyl acetate or 1-butanol is given by their separation fac- nate phase) can be determined using the thermodynamic principle tor (S). are shown in figures 1 and 2.0520 0.0745 0. ð1Þ X X the water (1).4840 0. S.1.9976 0.0000 0. us to construct the tie lines. 400 Phosphoric acid 3.1485 and surface area of the molecule [29. The separator factor is defined as the ratio of dis- tribution coefficient of the acid (2) to the distribution coefficient of ðci xi ÞE ¼ ðci xi ÞR .

557 1.8 0.9 1.2 K. / J.261 3.8 0.2 0.0 1.0 0. tate is greater than one (separation factors varying between 1.496 1.1 0. FIGURE 1.30 0. which means that TABLE 3 Distribution coefficients 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 = 308.3 0.082 0.8 0.2 FIGURE 4.4 0.2 0. (N) butyl acetate.2 0.9 0.7 0 0.6 0.0 FIGURE 3.6 0.783 0.358 0.7 0.1 0. 1.783) for the system reported in this work.6 0. thereby indicating the ability of butyl acetate FIGURE 2.1668 H.6 0.9 0.678 1.9 6 0.8 0.5 0.978 0.504 1.-) data.6 0.00 0.7 0.091 5.1 0.3 x21 0.2 0. Ghanadzadeh et al. This quantity for butyl ace- (water + phosphoric acid + butyl acetate) at T = 308.039 1.5 0..0 0..9 1.2 S 0.1 x21 1.5 0.0 1.4 0. 10 Phosphoric acid 8 0.4 0.8 0.0 0..0 0.859 0.504 0.5 0.2 K Water (1) + phosphoric acid (2) + 1-butanol (3) Water (1) + phosphoric acid (2) + butyl acetate (3) D2 D1 S D2 D1 S 0.423 0. () 1-butanol.230 0.0 0.4 0 0.610 0.792 0.4 0.9 1.941 0.3 0.499 1.843 1.0 0.2 0.2 0.1 mole fraction (x21) of phosphoric acid in aqueous phase.7 D2 0. Experimental (—) and correlated UNIQUAC (.542 0.627 0.0 0.10 0.8 0. () 1-butanol. experimental (—) and calculated (.4 0.8 0.20 0.648 0.865 and 5.2 K.40 0.-) LLE data for to extract phosphoric acid from water.145 0.0 0. Chem. Experimental (—) and correlated UNIQUAC (.865 .881 0.6 2 0.427 0. Thermodynamics 40 (2008) 1666–1670 Phosphoric acid 1.4 0.0 0.3 4 0.7 0. Plot of the distribution coefficient (D2) of phosphoric acid as a function of the mole fraction (x21) of phosphoric acid in aqueous phase.1 0.0 Water The experimental results indicate that butyl acetate has a high- Butyl acetate er separation factor. (M) 1-Butanol water butyl acetate experimental (—) and calculated (.144 3.527 0.5 0.518 1.3 0.4 0.601 1.3 0.117 0.6 0.3 0. Plot of the separation factor (S) of phosphoric acid as a function of the 0.-) LLE data for (water + phosphoric acid + 1-butanol) at T = 308.1 0.7 0.-) data.5 0..110 3.737 0.

Chem. Res. D. 37 (2005) 837. J. Recent Advances in Liquid-Liquid Extraction.k Þ Therefore. j indicates the phases. 1 (1971) 93. Othmer–Tobias equation constants for (water + phosphoric acid + 1-butanol) and [20] C. J.L. Ayedi.0 1–2 431. Caro. Chem. Bilgin. R. Data. Boluda. 72 (1994) acid) with 1-butanol and butyl acetate.967 [24] H. Ghanadzadeh. 3 (1985) 345. J. Ghanadzadeh. A. Hanson. I.0 1–3 109. Dramur. 38 (2006) 1503. 4 (1986) 771. ^x indicates the experimental [8] C.0 ij aij aji Ln((1-x23)/x23)) Water (1) + phosphoric acid (2) + 1-butanol (3) 4. where n is the number of tie lines. J. N. Ancheta.2 K [21] F. Marco. 66 (1988) 248. Fluid Phase Equilibr. 11 (1993) 445.M. Roquero. Wu. J. Chem. [14] S.207 0. Agric.I. ð9Þ [5] H.81 495. New York. The experi- water in the aqueous phase. M. Vidal. Eng. [18] R. (M) butyl The root-mean-square deviation (RMSD) between the values acetate.j. [11] J. Chem. Marco. Chem. F. Ghanadzadeh. [16] F. Y. 2.K. E. meaning that 1-butanol is not a suitable solvent for the and calculated data. Ion Exch.52 36. Fluid Phase Equilibr.F. Feki. and the subscript 1971. Özmen. [22] J. U. Senol.49 -2. Harrison. S.J. binary interaction parameters were determined by minimizing [15] A. 1-Butanol 1. Galán. Fourati. M. LLE correlation tract phosphoric acid from water. J. J.M. M. (water + phosphoric acid + butyl acetate) at T = 308. Galán. Costa. H. ing the following objective function (OF): [2] A. Solvent Extr. was calculated from the difference in the experimental and calcu- lated mole fractions according to the following equation: sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi the extraction of phosphoric acid using butyl acetate is possible. / J.F. is shown in figure 5. Li.M. acid + butyl acetate) were determined at T = 308. The 6n separation factor for 1-butanol is near one (between 1. C. 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. Chem.2 K. Fluid Phase Equilibr. Galan. M. TABLE 4 [19] A. J. Solvent Extr. Eng. Çehreli.I. Zhu. The corresponding sets of 939. Gómez-Siurana. M. Sariri. Food Chem. A. 74 (1978) 41. Thermodyn. Eng.670 1. ð8Þ (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. (water + phosphoric acid + 1-butanol) at T = 308. Fluid Phase Equilibr. Souza. and x11 is the mole fraction of tems exhibited type-1 (liquid + liquid) phase diagram. H. [3] _ Sß . . respectively. . Eng. 263 (2008) 223. Haghi. McCullough.F. A. A. Shen. Eng. QUAC model [27]. Ghanadzadeh. .0 Optimized UNIQUAC binary interaction parameters aij (K) for the (water + phosphoric acid + 1-butanol or butyl acetate) ternary systems at T = 308. Ayedi. Wu. Ghanadzadeh et al. Chaabouni. Chem.k Þ2 . Chem. Can.12 533. n (tie lines).j. 227 (2005) 87. Ruiz. Othmer–Tobias plots of (water + phosphoric acid + butyl acetate) and fractions for each of the components over all the tie lines. phosphoric acid from aqueous solutions. k = 1. P. J. The linearity of Othmer–Tobias plots mental LLE data were satisfactorily fitted by the UNIQUAC model. Rev. x23 is the mole fraction of phos. Marci. K. Chem. Eng. J.j. Pergamon. Fang. mined using the Othmer–Tobias correlation [31] for the ternary systems 4. Butyl acetate 1. 243 (2006) 45. Frederick.03 2–3 366.M.16%. Both the sys- phoric acid in the organic phase. Blanco. Data 49 (2004) 783.10 1–3 245.2 K. Eng. .H.296 0. () 1-butanol. Fischer. Ruiz.2 K 6. Ruiz.80 341. Fluid Phase Equilibr. S. acid + butyl acetate) were 2. Eng. Eng. M. J.358). Thermodyn. Rico..979 [23] Y. Blumberg. Martinez-Pons.92 2–3 1796. x is the calculated mole fraction. The UNIQUAC model was optimized by minimiz. L.0 -4 -3 -2 -1 0 Ln((1-x11)/x11) the differences between the experimental and calculated mole FIGURE 5. Solvent Extr. J. 265 (2008) 1. mole fraction.M.k  xi.k  xi. Prog. Torregrosa-Fuerte. Data 49 (2004) 218. Ismail Kırbasßlar. Costa. 6 Solvent A B R2 (1988) 141. Stenström.40 503.I. Can. Ion Exch. Chen. A.0 Water (1) + phosphoric acid (2) + butyl acetate (3) 1–2 431. Data 47 (4) (2002) 861. 146 (1998) 175.17% and 2. P.j. Eng. The experimental results indicated that butyl acetate has a high separation factor.M. B. The average root-mean-square deviations for extraction of phosphoric acid from water. [7] H. J.-Y.80 341. P3 P2 Pn 2 i¼1 j¼1 ^ k¼1 ðxi. Data 33 (1988) 211. The correlated results together with the experi- mental data for (water + phosphoric acid + 1-butanol) and References (water + phosphoric acid + butyl acetate) systems are presented in figures 1 and 2. 3 X X 2 X n [4] D. which shows the ability of butyl acetate to ex- 3. R. A. [17] F. J. J. Chem. i indicates the indices of components.-W. Table 5 shows the UNIQUAC binary interaction parameters (aij [12] J. H. 36 (2004) i¼1 j¼1 k¼1 1001. Thermodynamics 40 (2008) 1666–1670 1669 TABLE 5 8.196 0. Chem. 24 (1) (1976) 180. A. Conclusions     1  x23 1  x11 ln ¼ A þ B ln . Dhouib-Sahnoun. and [9] R. A. OF ¼ ð^xi. Chem. Arce. Tamura. Chem. and aji) optimized for the ternary systems of (water + phosphoric [13] M. M. J. Solvent Extr. Ancheta. 40 (2001) 892. [6] H.230 and The RMSD is a measure of the agreement between the experimental 1. Ghanadzadeh. S ß ahin. Ind. Marcilla.10 0. Solvent Extr. Data 40 (1995) 225. Wingefors. [1] A. F. Chem. Bergdorf. J. Thermodyn.-L. S. [10] J. K. Ion Exch. The correlation parameters are listed in table 4.2. Fernández-Sempere.31 2. (water + phosphoric acid + 1-butanol) and (water + phosphoric The reliability of the experimental tie line data can be deter. Ruiz. Ruiz-Beviá. Feki. J. this solvent may be considered as a possible candidate RMSD% ¼ 100 : ð10Þ for the recovery of phosphoric acid from aqueous solutions. Marcilla.

New York.S.. 34 (1942) 690–700. Fr.P.M. Fluid Phase Equilibr. A. Banerjee.C. Ince. 19 (2002) 243. 234 (2005) 64. Kumar Sahoo. Reid. [26] J. Ind. Hsien. P. Chem. Englewood Cliffs. R. Khanna.1670 H.E. [28] D. T. Prausnitz. [31] D.M. 21 (1975) 116. J. NJ. AICHE J. Grens. Bull. Othmer. [30] R. / J. Prentice-Hall Inc. Chem. Prausnitz. Chim. Bizot. McGraw-Hill. Res. Eng. E. Chem. . Singh. B.A. Ismail Kirbaslar. The Properties of Gases and Liquid. J.E. Oconnell. Ghanadzadeh et al.F.K. J. Tobias. JCT 08-140 [29] T. Computer Calculations for Multi-Component Vapor–Liquid and Liquid–Liquid Equilibria. Anderson. Thermodynamics 40 (2008) 1666–1670 [25] E. [27] J. M.F. C. 1980. Poling. S. Soc. R. 1 (1967) 151.A.M. Prausnitz. J. Abrams. Braz. Eckert. Eng. 1988.