THERMODYNAMICS AND CHEMICAL ENGINEERING DATA

Chinese Journal of Chemical Engineering, 19(4) 565ü569 (2011)

Salt Effect on the Liquid-Liquid Equilibrium of (Water + Propionic

Acid + Cyclohexanol) System at T (298.2, 303.2, and 308.2) K

Bahram Ghalami-Choobar*, Ali Ghanadzadeh and Shahram Kousarimehr

Department of Chemistry, Faculty of Science, University of Guilan, P.O. Box: 19141, Rasht, Iran

Abstract Effects of salt and temperature on the liquid phase equilibrium of the (water + propionic acid + cyclo-
hexanol) system were investigated. The liquid-liquid equilibrium data in the presence of KCl for various salt ionic
strength of 0.5, 1.0, 1.5, 2.0, and 2.5 mol·dm3 and in absence of the salt at T (298.2, 303.2, and 308.2) K were
determined. The experimental results were correlated based on the Othmer-Tobias equation and Pitzer ion-interaction
model. Thermodynamic properties such as distribution coefficients and activity coefficients of propionic acid in
water + cyclohexanol were determined. In addition, the separation factor, S, of the chosen solvent was obtained for
the investigated system.
Keywords liquid-liquid equilibrium, salt effect, propionic acid, distribution coefficient

1 INTRODUCTION data of water + propionic acid + cyclohexanol system

Separation of carboxylic acids from dilute aque-
ous solutions is an important operation in many indus-
trial processes [1]. Propionic acid is one of the impor-
tant carboxylic acid widely used as mold inhibitor in
baking and esterifying agent in the production of
thermoplastics and in the manufacture of flavors and
perfume bases [2, 3]. Liquid-liquid extraction is one of
the practical separation processes. Liquid-liquid ex-
traction using aqueous two-phase systems (ATPS) has
been demonstrated to be a highly efficient separation
technique for small organic species [4, 5]. The addition
of a salt or a non-volatile solute in a solvent mixture
and temperature can significantly change two-phase
equilibrium composition. Adding salt to an aqueous
solution of an organic acid can result in either a de-
crease (salting out) or an increase (salting in) in solu-
bility of the organic acid. The concentration of a
component in a liquid-liquid system increases if the
component is salted-in and decreases if it is salted out
of the liquid phase [68]. This salt effect has been ad-
vantageously used in distillation, separation and sol-
vent extraction. The salt effect is also important in
biological separation processes such as purification of
proteins, enzymes, nucleic acids, and others [9].
In recent years, the liquid-liquid equilibrium
(LLE) [10] and salt effect on the liquid-liquid equilib-
rium systems [11, 12] have been studied. The LLE data
of (water + propionic acid + solvents) ternary systems
are important in chemical industry. Propionic acid
obtains by chemical reactions or by fermentation with
bacteria of the genus propionibacterium. Several sol-
vents have been tested to improve the recovery of
propionic acid from aqueous solutions [1316]. How-
ever, salt effect on the thermodynamic data of our inves-
tigated system (water + propionic acid + cyclohexanol)
has not been reported in literature. In this work, effects
of salt and temperature on the liquid-liquid equilibrium
were investigated.
To obtain LLE data, the most common methods
include titration, Karl-Fisher titration and gas chro-
matograghy methods. In this work, the experimental
measurements were performed with the potetiometric
titration and Karl-Fisher methods. The experimental
results were correlated based on the Othmer-Tobias
equation and the Pitzer ion-interaction model, in
which a small number of adjustable parameters were
applied. The Pitzer parameters represent the measure
of the interactions between ions and solvent molecules.
In addition, separation factor value, S, of the chosen
solvent was evaluated for the investigated system.
2 EXPERIMENTAL
2.1 Materials
Propionic acid, cyclohexanol, and potassium
chloride were purchased from Merck. The mass frac-
tion purities of the compounds were 0.99, 0.99, and
0.995, respectively. The chemicals were used without
further purification. Double distilled water was used
throughout all experiments.
2.2 Apparatus and procedure
A 0.02 dm3 of aqueous solution of potassium
chloride, for adjusting the ionic strength at the desired
value, was shaken with 0.02 dm3 of cyclohexanol and
the known amount of propionic acid at constant tem-
perature T (298.2, 303.2, and 308.2) K and then were
stirred vigorously for at least 2 h, then it was settled
down for 4 h. All these procedures were completed in
a double-wall container thermostated with water from
a Model GFL circulation system. After that propionic
acid concentration in each phase was determined by

Received 2010-08-01, accepted 2011-04-27.

* To whom correspondence should be addressed. E-mail: B-Ghalami@guilan.ac.ir
566 Chin. J. Chem. Eng., Vol. 19, No. 4, August 2011

titration with a standard solution of sodium hydroxide.

Then, acid analysis was checked according to mass
balance equations. The potassium chloride concentra-
tion in the organic and aqueous phases was evaluated
by potentiometric titration method using Cl indicator
electrode. All of the potentiometric measurements
were made using digital multimeter (Martini instru-
ments Mi180) with 0.1 mV resolution. The output of
the multimeter was connected to a personal computer
by the RS232 connector for data acquisition. The
Mi5200 software and Microsoft Excel (Office 2007)
software were used for data acquisition and calcula-
tions. The water mole fractions in the organic phase
were also measured by Karl-Fisher (Dl-18 model met- Figure 1 Phase diagram of water + propionic acid + cyclo-
tler Toledo) method. The solubility curves were de- hexanol ternary system at T 298.2 K
termined by using the method based on detection of
the cloud point. Table 1 Experimental solubility data for water (1) +
propionic acid (2)+ cyclohexanol (3) ternary system
at T 298.2 K
3 RESULTS AND DISCUSSION
x1 x2 x3
3.1 LLE measurements
0.0040 0.0000 0.9961
0.0098 0.0499 0.9404
Figure 1 shows the binodal curve prior to addi-
tion of salt for ternary system of (water + propionic 0.0116 0.0565 0.9319
acid + cyclohexanol) at 298.2 K. The composition of 0.0184 0.0658 0.9158
mixtures on the binodal curve and the mutual binary 0.0390 0.0954 0.8656
solubility of water and the alcohol are given in Table 1,
where xi denotes the mole fraction of the ith compo- 0.0630 0.1202 0.8167
nent. After salt addition, the experimental results 0.0919 0.1508 0.7573
(tie-lines) for various ionic strength (0.5, 1.0, 1.5, 2.0, 0.1249 0.1637 0.7114
and 2.5 mol·dm3) were evaluated and are presented in
0.1729 0.1878 0.6393
Tables 2 to 4 at T (298.2, 303.2, and 308.2) K, re-
spectively. Although the data deal with quaternary 0.2348 0.1871 0.5782
system, use of free-salt mole fractions makes the rep- 0.3485 0.1630 0.4885
resentation easier. 0.5391 0.1197 0.3412
Distribution coefficient, D2, of propionic acid,
and separation factor, S, of the chosen solvent were 0.6742 0.0000 0.3259
calculated as follows [17]:
x23
D2 (1)
x21 x13 and x11 are the water mole fractions in solvent-rich
x and water-rich phases, respectively. The values of dis-
S D2 11 (2) tribution coefficient and separation factor for each aque-
x13 ous solution containing potassium chloride are sum-
where x23 and x21 are propionic acid mole fractions in marized in Table 5 at T (298.2, 303.2, and 308.2) K.
solvent-rich and water-rich phases, respectively, and Figs. 2 to 4 show the distribution coefficients for

Table 2 Experimental tie-line data of (water + propionic acid + cyclohexanol) ternary system
in the presence of salt at T 298.2 K
Aqueous phase Organic phase
I/mol·dm3
x11 x21 x31 x13 x23 x33
0 0.9599 0.0013 0.0388 0.3680 0.0188 0.6131
0.5 0.9742 0.0012 0.0246 0.3245 0.0199 0.6557
1 0.9806 0.0011 0.0182 0.3087 0.0213 0.6700
1.5 0.9833 0.0010 0.0156 0.3018 0.0237 0.6745
2 0.9852 0.0010 0.0014 0.2973 0.0231 0.6796
2.5 0.9599 0.0013 0.0388 0.3680 0.0188 0.6131
 Chin. J. Chem. Eng., Vol. 19, No. 4, August 2011 567

Table 3 Experimental tie-line data of (water + propionic acid + cyclohexanol) ternary system
in the presence of salt at T 303.2K
Aqueous phase Organic phase
I/mol·dm3
x11 x21 x31 x13 x23 x33
0 0.9781 0.0014 0.0206 0.3683 0.0183 0.6133
0.5 0.9830 0.0012 0.0158 0.3465 0.0184 0.6352
1 0.9831 0.0011 0.0158 0.3243 0.0188 0.6569
1.5 0.9873 0.0010 0.0116 0.3013 0.0214 0.6773
2 0.9913 0.0010 0.0076 0.2830 0.0225 0.6946
2.5 0.9781 0.0014 0.0206 0.3683 0.0183 0.6133

Table 4 Experimental tie-line data of water + propionic acid + cyclohexanol) ternary system
in the presence of salt at T 308.2K
Aqueous phase Organic phase
I/mol·dm3
x11 x21 x31 x13 x23 x33
0.0 0.9784 0.0014 0.0202 0.3633 0.0189 0.6177
0.5 0.9896 0.0013 0.0091 0.3451 0.0199 0.6350
1.0 0.9916 0.0012 0.0072 0.3293 0.0206 0.6502
1.5 0.9955 0.0011 0.0034 0.3037 0.0216 0.6747
2.0 0.9861 0.0010 0.0129 0.3015 0.0215 0.6770
2.5 0.9784 0.0014 0.0202 0.3633 0.0189 0.6177

Table 5 The values of ionic strength, distribution coefficients for propionic acid, and
separation factor at T (298.2, 303.2, and 308.2) K
Concentration 298.2 K 303.2 K 308.2 K
/mol·dm3 I/mol·kg 1
D2 S I/mol·kg 1
D2 S I/mol·kg 1
D2 S
0.0 0 2.99 24.07 0 3.76 31.00 0 3.94 33.17
0.5 0.50 4.56 38.87 0.50 3.81 35.51 0.52 3.92 37.38
1.0 1.01 4.66 50.88 1.04 4.07 42.42 1.05 4.17 45.37
1.5 1.57 5.17 62.29 1.57 4.28 49.00 1.61 4.41 51.61
2.0 2.14 4.81 65.86 2.13 5.21 67.25 2.18 4.85 64.76
2.5 2.77 6.05 78.41 2.72 5.31 76.01 2.74 5.54 70.95

Figure 2 Distribution coefficient of propionic acid, D2, Figure 3 Distribution coefficient of propionic acid, D2,
plotted against the mole fraction of propionic acid in the plotted against the mole fraction of propionic acid in the
aqueous phase at T 298.2 K aqueous phase at T 303.2 K

propionic acid in different temperatures. It can be con-
cluded that propionic acid concentration in the aque-
ous phase decreases with increase of salt ionic strength.
The effectiveness of extraction of propionic acid by
the solvent is given by its separation factor, S, which
is an indication of the ability of solvent to separate
propionic acid from water. Fig. 5 shows the separation
factor for the propionic acid at T (298.2, 303.2, and
308.2) K. As it can be seen, separation of propionic
acid from water in the presence of the salt is possible.
568 Chin. J. Chem. Eng., Vol. 19, No. 4, August 2011

Table 6 Values of Othmer-Tobias parameters for

water + propionic acid + cyclohexanol system
at T (298.2, 303.2, and 308.2) K
T/K A B R2

298.2 0.4142 0.2821 0.9614

303.2 0.9287 0.3749 0.8932
308.2 0.1411 0.1590 0.9624
Figure 4 Distribution coefficient of propionic acid, D2,
plotted against the mole fraction of propionic acid in the
aqueous phase at T 308.2 K
3.3 Pitzer model

The Pitzer ion-interaction model was also used to

correlate and calculate the activity coefficients of
propionic acid. The Pitzer equation for the natural
logarithm of the activity coefficient of a neutral spe-
cies, N, is [19]:
ln J N 2¦ OcN mc  2¦ OcN ma  ¦¦ PcaN mc ma (4)
c c c c

where the sums are over cations c and over anions a,

Figure 5 Separation factor plotted against the mole frac-
tion of propionic acid in aqueous solution containing potas-
sium chloride at different temperatures
T/K: ƹ298.2;Ƶ303.2;Ʒ308.2
3.2 Othmer-Tobias correlation
The consistency of experimental tie-line data can
be determined by applying the Othmer-Tobias correla-
tion [1518] as shown in the following equation
1  x33 1  x11
ln A  B ln (3)
x33 x11
where x11 is the mole fraction of water in the water-
rich phase, x33 is the mole fraction of alcohol in the
solvent-rich phase. A and B are constant which depend
on the degree of immiscibility of components in sys-
tems. Fig. 6 shows the plot of ln[(1x33)/x33] versus
ln[(1x11)/x11]. The linearity of the plots indicates the
consistency of experimental data. The values of pa-
rameters A and B and the corresponding correlation
coefficient values (R2) are given in Table 6. It indi-
cates that Eq. (3) can be satisfactorily used to correlate
the tie-line data of the investigated system.
mi is the molality of species i, Ȝ the second virial coef-
ficient, and ȝ the triple virial interactions coefficients.
Besides, the experimental activity coefficients were
determined by the following equations [20]:
K
ln J N ln (5)
K0
morg
K (6)
maq
where K and K0 are the molality ratio of propionic
acid for the organic phase and the aqueous solution, in
the presence and in absence of the salt, respectively.
The Pitzer ion-interaction parameters (Ȝ and ȝ) were
obtained by combining Eqs. (4) and (5) using an itera-
tive minimization procedure employing the Microsoft
Excel (solver) program. The KCl second and triply
virial coefficients found for investigated system are
illustrated in Table 7. Fig. 7 shows the calculated ac-
tivity coefficients of propionic acid versus the ionic
strength of salt in aqueous solutions. It can be seen
that the activity coefficient of propionic acid increases
with ionic strength, but it decreases as temperature
increases. It can be concluded that the addition of
this salt decreases the solubility of propionic acid in
the aqueous phase. In addition, the salt effect on the
solubility of propionic acid is more important at lower
temperatures.

Table 7 The values of Pitzer ion-interaction parameters

at different temperatures
T/K Ȝ ȝ

298.2 0.7417 0.2249

303.2 0.0420 0.0382
Figure 6 Othmer-Tobias plots of water + propionic acid +
cyclohexanol ternary system at T 298.2 K 308.2 0.0092 0.0411
 Chin. J. Chem. Eng., Vol. 19, No. 4, August 2011
Figure 7 The plot of activity coefficients for propionic acid
versus total ionic strength of salt in aqueous solution con-
taining potassium chloride at T (298.2, 303.2, and 308.2) K
ƹ298.2 K;Ƶ303.2 K;Ʒ308.2 K
4 CONCLUSIONS
The LLE results for the system of (water + propi-
onic acid + cyclohexanol) were reported at T (298.2,
303.2 and 308.2) K. The distribution coefficients and
activity coefficients of the propionic acid were deter-
mined in different media. It was found that the addi-
tion of potassium chloride decreases the solubility of
propionic acid in the aqueous phase for the investi-
gated system. Also, the solubility of water in cyclo-
hexanol decreases as the salt concentration increases.
It can be concluded from the distribution coefficient
and selectivity data that it is possible to separate
propionic acid from water in the presence of salt by
extraction with cyclohexanol.
ACKNOWLEDGEMENTS
We gratefully acknowledge the graduate office of
University of Guilan for supporting this work.
REFERENCES
1 Wang, Y., Li, Y., Li, Y., Wang, L.Z., Dai, Y., “Extraction equilibria of
monocarboxylic acids with trialkylphosphine oxide”, J. Chem. Eng.
Data, 46, 831837 (2001).
2 Lee, L.L., Molecular Thermodynamics of Electrolyte Solutions,
World Scientific Publishing, USA (2008).
3 Cehreli, S., Tatli, B., Bagman, P., “Liquid + liquid equilibria of (water +
propionic acid + cyclohexanone) at several temperatures”, J. Chem.
569
Thermodyn, 37, 12881293 (2005).
4 Docherty, H., Galindo, A., “Galindo investigation of the salting out
of methane from aqueous electrolyte solutions using computer
simulations”, J. Phys. Chem. B., 111, 89939000 (2007).
5 Taboada-Pan, C., Brandariz, I., Barriada, J.L., Vilarino, T., Vicente,
M.E., “The salting coefficient and size of alkylamines in saline me-
dia at different temperatures: Estimation from Pitzer equations and
the mean spherical approximation”, Fluid Phase Equilibria, 180,
313325 (2001).
6 Gorgenyi, M., Dewulf, J., Langenhove, H.V., Heberger, K., “Aqueous
salting-out effect of inorganic cations and anions on non-electrolytes”,
Chemosphere, 65, 802810 (2006).
7 Pinho, S.P., Macedo, E.A., “Experimental measurement and model-
ling of KBr solubility in water, methanol, ethanol, and its binary
mixed solvents at different temperatures”, J. Chem. Thermodyn., 34,
337360 (2002).
8 Ji, Y.H., Ji, X.Y., Feng, X., Liu, C., Lü, L.H., Lu, X.H., “Progress in
the study on the phase equilibria of the CO2-H2O and CO2-H2O-NaC1
systems”, Chin. J. Chem. Eng., 15, 439448 (2007).
9 Aznar, M., Araujo, R.N., Romanato, J.F., Santos, G.R., Vila, S.G., “Salt
effects on liquid-liquid equilibrium in water + ethanol + alcohol + salt
systems”, J. Chem. Eng. Data, 45, 10551059 (2000).
10 Ghanadzadeh, H., Ghanadzadeh, A., Bahrpaima, K.H., “Liquid phase
equilibria of (water + phosphoric acid + 1-butanol or butyl acetate)
ternary systems at T 308.2 K”, J. Chem. Thermodyn., 40, 16661670
(2008).
11 Chen, J.T., Chen, M.C., “Salting effect on the liquid-liquid equilibria
for the ternary system water + N-methyl-2-pyrrolidone + 1-pentanol”,
Fluid Phase Equilibria, 266, 17 (2008).
12 Millero, F., “The activity coefficients of non-electrolytes in sea-
water”, Marine Chemistry, 70, 522 (2000).
13 Ghanadzadeh, H., Ghanadzadeh Gilani, A., Bahrpaima, Kh., Sariri,
R., “Liquid + liquid equilibria for ternary mixtures of (water +
propionic acid + organic solvent) at T 303.2 K”, J. Chem. Ther-
modyn., 42, 267273 (2010).
14 Vakili-Nezhaad, G.R., Mohsen-Nia, M., TaghikhaniM, V., Behpoor,
M., Aghahosseini, M., “Salting-out effect of NaCl and KCl on the
ternary LLE data for the systems of (water + propionic acid + iso-
propyl methyl ketone) and of (water + propionic acid + isobutyl
methyl ketone)”, J. Chem. Thermodyn., 36, 341348 (2004).
15 Ghanadzadeh, H., Ghanadzadeh, A., Bahrpaima, K.H., Saadat, S.,
“(Liquid + liquid) equilibria of (water + propionic acid + 2-ethyl-1-
hexanol): Experimental data and correlation”, J. Chem. Thermodyn.,
40, 879884 (2008).
16 Cehreli, S., Tatli, B., Bagman, B., “(Liquid + liquid) equilibria of
(water + propionic acid + cyclohexanone) at several temperatures”, J.
Chem. Thermodynamics., 37, 12881293 (2005).
17 Uslu, H., Gok, A., Kırbaslar, S., “Phase equilibria of (water + levunilic
acid + alcohol) ternary systems”, Fluid Phase Equilibria, 273, 2126
(2008).
18 Othmer, D.F., Tobias, P.E., “Tie line correlation”, Ind. Eng. Chem.,
34, 690692 (1942).
19 Pitzer, K.S., Activity Coefficients in Electrolyte Solutions, CRC
Press, Boca Raton (1991).
20 Sandler, S.I., Chemical and Engineering Thermodynamics, John
Wiley, New York (1977).