Accepted Manuscript

Determination of liquid–liquid equilibria data for

(water+propanoic acid+3-methylbutan-1-ol) ternary mixture at
293.15K to 313.15K

Mahboobe Behroozi, Parisa Armozd, Marjan Mohhamadi Sarab

Badieh

PII: S0167-7322(17)32430-3
DOI: doi: 10.1016/j.molliq.2017.08.021
Reference: MOLLIQ 7729
To appear in: Journal of Molecular Liquids
Received date: 2 June 2017
Revised date: 30 July 2017
Accepted date: 6 August 2017

Please cite this article as: Mahboobe Behroozi, Parisa Armozd, Marjan Mohhamadi Sarab
Badieh , Determination of liquid–liquid equilibria data for (water+propanoic
acid+3-methylbutan-1-ol) ternary mixture at 293.15K to 313.15K, Journal of Molecular
Liquids (2017), doi: 10.1016/j.molliq.2017.08.021

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 ACCEPTED MANUSCRIPT

Determination of liquid–liquid equilibria data

for (water + propanoic acid + 3-methylbutan-
1-ol) ternary mixture at 293.15 K to 313.15K
Mahboobe Behroozia, Parisa Armozda , Marjan Mohhamadi Sarab Badiehb
a
Faculty of Science, Department of Chemistry, University of Zanjan, Zanjan, Iran

b
Department of Applied Chemistry, Bu-Ali Sina University, Hamedan, Iran

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ABSTRACT

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Liquid–liquid equilibrium (LLE) data for the ternary mixture of water + propanoic
acid + 3-methylbutan-1-ol were determined within the temperature range (293.15 to

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313.15) K and atmospheric pressure. The phase diagrams containing solubility and
tie-line data show the type-1 behavior of LLE. Refractive index measurements were
performed to determine the binodal curves and the tie-line compositions of the
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equilibrium phases. It has been found that the relative mutual solubility of propanoic
acid was higher in solvent phase than aqueous phase. For evaluation of the capability
of solvent for extraction of propanoic acid from aqueous solutions, distribution
coefficients and separation factors were measured. The high values of separation
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factors confirm that 3-methylbutan-1-ol is a suitable choice for this purpose. The
reliability of the experimental tie-lines was checked through the Othmer–Tobias
correlation equation. The NRTL and UNIQUAC models were used to correlate the
tie-line data.
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Keywords: LLE; NRTL; UNIQUAC; Propanoic Acid; 3-methylbutan-1-ol

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1. Introduction
Propanoic acid is an organic acid with many industrial applications [1-4]. It can be
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produced by chemical synthetic or fermentation processes [2,4]. The recovery of

propanoic acid from dilute solutions is very important and holds considerable interest
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due to its widespread use in industrial as well as economic point of view [5-6].
Knowledge of phase behavior of ternary mixtures containing propanoic acid and
(liquid + liquid) equilibrium data is required for the design of liquid propanoic acid
extraction processes [7]. Generally, information about phase equilibrium data is very
important in recovery and separation processes [8-10]. The selection of the extraction


Corresponding author. Tel./fax: +98 024 33052477.
E-mail address: behroozi.m@znu.ac.ir (M. Behroozi).
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solvent is very important for suitable extraction of propanoic acid from aqueous
solutions. In order to choice a suitable solvent, selectivity, recoverability and
distribution coefficient of the solvent must be considered. Many solvents have been
tested to improve extraction efficiency [2,5,11-13].
In this paper, 3-methylbutan-1-ol (isoamyl alcohol) was used as an extraction solvent
for aqueous solution of propanoic acid. The high boiling point of the solvent and very
low solubility in water, make it suitable for this purpose. The OH group in the

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alkanols has two sites (electron donor and electron acceptor) that make them
hydrogen-bond acceptor and hydrogen-bond donor. Linear chains of alcohol can be
constructed by association of the molecules. Propionic acid and 3-methylbutan-1-ol

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are self-associated and also there are cross association between different species.

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Binary mixture of propanoic acid and 3-methylbutan-1-ol may be used for production
of isoamyl propionate in esterification reactions [14].
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The LLE data for (water + propanoic acid + 3-methylbutan-1-ol) ternary mixture were
obtained at temperatures from (293.15 to 313.15) K and atmospheric pressure. The
solubility and tie line data were obtained by cloud point method. In this method, the
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relationship between the composition and refractive index of the cloudy samples is
determined and then it will be used for tie line determination. The use of low sample
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size as well as the simplicity of this method has given it superiority. In order to
determine reliability of the tie line data the Othmer−Tobias equation [15] was used.
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The NRTL [16] and UNIQUAC [17] activity coefficient models were applied for
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correlation of the experimental LLE data.

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2. Experimental

2.1. Materials
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High-purity grade chemicals, propanoic acid (Merck, ≥9 9%), 3-methylbutan-1-ol

(Merck, ≥99%) were used without further purification. Bidistilled water was used
throughout all experiments. The refractive indices of the pure substances were
measured at 293.15 K and given in Table 1 along with the corresponding literature
values [18-19].
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2.2. Apparatus and procedure

The cloud point method [20] was applied to determine the solubility curve for the
ternary mixtures at (293.15 to 313.15) K. The ternary mixtures were prepared in an
equilibrium glass cell with about 10 cm3 volume, equipped with a magnetic stirrer and
also water jacket in order to prepare isothermal conditions. The temperature in the
jacket was kept constant by a thermostat (RE 104, LAUDA, Germany) with an
accuracy of ±0.1 K. The experimental setup was represented in Fig. 1 schematically.

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For solubility curve, two regions were considered: water-rich and solvent-rich
regions. For every region, binary mixtures of known compositions either (water +
propanoic acid) or (3-methylbutan-1-ol + propanoic acid) were prepared

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gravimetrically by a Mettler AB 204-N balance with uncertainty of ±0.1 mg and

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introduced to the cell and stirred at constant temperature. At each temperature, the
binary mixtures were titrated with the tired component (water or 3-methylbutan-1-ol)
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until the transition from homogeneous to a heterogeneous mixture was observed. The
appearance of turbidity determines the end point. The uncertainty in the mass fraction
was estimated to be less than  1 10 -4 . Similar procedure was performed by other
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researchers [21-22].
Refractive indexes of the cloudy samples were measured with an Abbe
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refractometer (AR2008, Kruss, Germany) with an accuracy of 0.0002 at the same

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temperature of the mixtures. These data were used for the construction of calibration
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curves. Figure 2 represents typical standard curves for water and propanoic acid in
aqueous and organic phases at 293.15 K.
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In order to obtain the tie-line data, different known compositions of water,

propanoic acid and 3-methylbutan-1-ol were prepared in the extraction cell and were
shaken sufficiently. After that, the samples were putted inside a water bath and
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allowed rest for 12 h to settle into two layers (raffinate and extract layers) at the
desired temperature. After separation the phases, samples were withdrawn from each
phase by glass syringes with a capacity of 5 mL carefully and analyzed to determine
the compositions of each layer. Refractive indices measurements were performed for
the two phases at equilibrium and the calibration curves were applied to determine the
unknown compositions [21-23].
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3. Results and discussions

3.1 Experiments
The solubility data and the compositions of the equilibrium phases for the (water +
propanoic acid + 3-methylbutan-1-ol) ternary mixture at temperatures from (293.15 to
313.15) K are collected in Tables 2‒3, for which wi denotes the mass fraction of the
ith component (i =1, 2, 3). Graphical representation of the triangle diagrams
containing binodal curves and tie-lines for the ternary mixture is shown in Figs. 3-5. It

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can be seen from the figures, the phase behavior of the studied mixture is type one
because there are only one partially miscible binary mixture (water + 3-methylbutan-

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1-ol ) and two completely miscible binary mixtures (water + propanoic acid) and

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(propanoic acid + 3-methylbutan-1-ol ). From the slope of tie lines for the ternary
mixture can be found that propanoic acid is more soluble in organic phase than in
aqueous phase. The effect of temperature on LLE data for the studied mixture is small
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at the studied temperature range. The following equations were applied for calculating
the distribution coefficient (D) and the separation factor (S) that determine the ability
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of 3-methylbutan-1-ol to separate propanoic acid from water.

D

(1)
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(2)
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where and are mass fractions of the component i in the water-rich and
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solvent-rich phases, respectively.

The values of distribution coefficients and separation factors are given in Table 4
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and graphically represented in Figs. 6-7. As can be seen, the separation factors for 3-
methylbutan-1-ol are greater than 1 in all temperatures. This means that isoamyl
alcohol is a suitable candidate for the extraction of propanoic acid from water.

3.2 Correlations
Othmer–Tobias [4] correlation equation was applied to determine the reliability of
experimental data of tie-line as follows:
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(3)

where and are mass fractions of water in water-rich phase and 3-

methylbutan-1-ol in solvent-rich phase, respectively; A and B are the parameters of
the Othmer–Tobias equation that are given in Table 5 at different temperatures. The
correlations are shown graphically in Fig. 8
.
Furthermore, two activity coefficient models, NRTL [4] and UNIQUAC [4], was

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applied to correlate the liquid–liquid equilibrium data. The binary interaction
parameters of the models were obtained by Aspen Plus simulator and collected in

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Table 6. The graphical representation of the correlated results is shown in Figs. 2-4.

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The equations and parameters of the models have been described in detail in the
literature frequently. NU
The agreement between the experimental data and the results of correlation
equations was determined by the root-mean-square deviation (RMSD) calculations as
following:
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(4)
D

where i, m and n refer to components (i= 1, 2, 3), phases (m=I, II) and tie-lines (n=1,
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2,….., N) respectively; are experimental and calculated mass fractions.

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The RMSD values are given in Table 6.

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4. Conclusion

The solubility and tie-line data for (water + propanoic acid + 3-methylbutan-1-ol)
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ternary mixture were determined at (293.15 to 313.15) K temperatures range. For the
mixture, there is only one partially miscible pair (water + 3-methylbutan-1-ol ) that is
indicative of type 1 phase behavior. Since the separation factor for 3-methylbutan-1-ol
is greater than 1 it would be a suitable solvent to extract propanoic acid from its dilute
aqueous solutions. In order to confirm the reliability of experimental data, Othmer–
Tobias correlation equation was applied. In addition, two local composition models,
NRTL and UNIQUAC, were used to correlate the phase behavior of the studied
mixture. The root mean square deviation between the experimental and calculated
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data was 0.0125 and 0.0100 for the models respectively. The agreement between the
correlation results and experimental data was satisfactory.

Acknowledgment
The authors would like to thank University of Zanjan for providing the necessary

facilities to carry out the research.

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References

[1] S.L. Clifford, D. Ramjugernath, J.D. Raal, Fluid Phase Equilibria 237 (2005)
89-99.
[2] D. Özmen, Fluid Phase Equilibria 250 (2006) 70-75.
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[4] B. Başlıoğlu, S. Çehreli, Fluid Phase Equilibria 312 (2011) 85-92.
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[7] D. Özmen, S. Çehreli, U. Dramur, The Journal of Chemical Thermodynamics
37 (2005) 837-842.

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[8] N. Sunsandee, M. Hronec, M. Štolcová, N. Leepipatpiboon, U. Pancharoen,
Journal of Molecular Liquids 180 (2013) 252-259.
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Phase Equilibria 338 (2013) 217-223.
[10] Y .Hu, X. Jiang, W. Yang, Z. Chen, X. Meng, F. Shen, Journal of Molecular

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Liquids 169 (2012) 74-79.
[11] S. Çehreli, Fluid Phase Equilibria 248 (2006) 24-28.
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[13] E. İnce, Y.S. Aşçı, Fluid Phase Equilibria 370 (2014) 19-23.
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[14] F. Leyva, A. Orjuela, D.J. Miller, I. Gil, J. Vargas, G. Rodríguez, Industrial &
Engineering Chemistry Research 52 (2013) 18153-18161.
[15] D.F. Othmer, P.E. Tobias, Industrial & Engineering Chemistry 34 (1942) 690-
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692.
[16] H .Renon, J.M. Prausnitz, AICHE Journal 14 (1968) 135-144.
[17] D.S. Abrams, J.M. Prausnitz, AICHE Journal 21 (1975) 116-128.
[18] M. Bilgin, Ş. İsmail Kırbaşlar, Ö. Özcan, U. Dramur, The Journal of Chemical
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Thermodynamics 37 (2005) 297-303.

[19] J. Wisniak ,A. Tamir, Journal of Chemical and Engineering Data 21 (1976)
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88-90.
[20] F. Ruiz Bevia, D. Prats Rico, V. Gomis Yagües, Fluid Phase Equilibria 23
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(1985) 269-292.
[21] D. Laiadi, A. Hasseine, A. Merzougui, Fluid Phase Equilibria 313 (2012) 114-
120.
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[22] N. Deenadayalu, K.C. Ngcongo, T.M. Letcher, D. Ramjugernath, Journal of

Chemical and Engineering Data 51 (2006) 988-991.
[23] M. Timedjeghdine, A. Hasseine, H. Binous, O. Bacha, M. Attarakih, Fluid
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Phase Equilibria 415 (2016) 51-57.

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Captions of Figures

Fig 1. The experimental setup. 1. Thermostate 2. Water bath 3. Glass cell. 4. Magnetic stirrer 5.
Stirrer.

Fig 2. Dependency of samples compositions (water or propanoic acid) on the refractive index of
cloudy solutions in (a) , aqueous and (b) ▲, organic phases at 303.15 K.

Fig 3. LLE data for water + propanoic acid + 3-methylbutan-1-ol ternary system at T = 293.15 K:)○)
experimental solubility curve; (●) experimental tie-line data; () calculated NRTL tie-line data; (□)

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calculated UNIQUAC tie-line data.

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Fig 4. LLE data for water + propanoic acid + 3-methylbutan-1-ol ternary system at T = 303.15 K:)○)
experimental solubility curve; (●) experimental tie-line data; () calculated NRTL tie-line data; (□)

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calculated UNIQUAC tie-line data.
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Fig 5. LLE data for water + propanoic acid + 3-methylbutan-1-ol ternary system at T = 313.15 K:)○)
experimental solubility curve; (●) experimental tie-line data; () calculated NRTL tie-line data; (□)
calculated UNIQUAC tie-line data.
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Fig 6. Distribution coefficients of water (D1) and propanoic acid (D2) against the concentration of
propanoic acid in aqueous phase (w21) at different temperatures: 293.15 K (), 303.15 K () and
313.15 K (▲).
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Fig 7. Separation factor, s, versus concentration of propanoic acid in aqueous phase (w21) at different
temperatures: 293.15 K (), 303.15 K () and 313.15 K (▲).
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Fig 8. Othmer–Tobias plot for LLE data of the water + propanoic acid + 3-methylbutan-1-ol ternary
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system at different temperatures: 293.15 K (), 303.15 K () and 313.15 K (▲).
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Fig. 1
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DE
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Fig. 2
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Propanoic acid

0.0
1.0

0.1
0.9

0.2
0.8

0.3
0.7

0.4
0.6

0.5
0.5

0.6
0.4

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0.7
0.3

0.8
0.2

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0.9
0.1

1.0
0.0

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Water 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 3-Methyl-1-butanol

Fig. 3
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Propanoic acid

0.0
1.0

0.1
0.9

0.2
0.8

0.3
0.7

0.4
0.6

0.5
0.5

0.6
0.4

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0.7
0.3

0.8
0.2

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0.9
0.1

1.0
0.0

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Water 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 3-Methyl-1-butanol

Fig. 4
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Propanoic acid

0.0
1.0

0.1
0.9

0.2
0.8

0.3
0.7

0.4
0.6

0.5

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0.5

0.6
0.4

0.7
0.3

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0.8
0.2

SC
0.9
0.1

1.0
0.0
Water 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 3-Methyl-1-butanol
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Fig. 5
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0.25

a
0.20

D1 0.15

0.10

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0.05

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0.00
0 0.02 0.04 0.06 0.08 0.1 0.12

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w21
3
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2.5 b

2
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D2

1.5

1
D

0.5
E

0
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0 0.02 0.04 0.06 0.08 0.1 0.12

w21
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Fig. 6
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25

20

15

S 10

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0
0 0.02 0.04 0.06 0.08 0.1 0.12

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w21

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Fig. 7

-0.5
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-1
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-1.5
ln((1-w33)/w33)

-2
D

-2.5
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-3

-3.5
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-2.5 -1.5 -0.5 0.5

ln((1-w11)/w11)
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Fig. 8
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Table 1
Name, purity grade, supplier, CAS number, and refractive index n D20 , of the pure components at 293.15 K.
Purity
component
(mass fraction)
Supplier CAS number n D20
Expt. Lit.
3-Methylbutan-1-ol ≥ 99 Merck 123-51-3 1.4062 1.4070a
Propanoic acid ≥ 99 Merck 79-09-4 1.3863 1.3860b
Water bidistilled 1.3330 1.3330a
Standard uncertainties u is u(nD) = 2  10 and u(T) = 0.1 K.
-4

a
Ref. [15].
b
Ref. [16].

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Table 2
Experimental solubility curve data for water (1) + propanoic acid (2) + 3-methylbutan-1-ol (3) ternary system at
temperature range (293.15 to 313.15) K and atmospheric pressure.
w1 w2 w3 w1 w2 w3
293.15 K
0.9745 0.0000 0.0255 0.2055 0.3227 0.4718
0.9271 0.0442 0.0287 0.1880 0.2911 0.5209
0.8851 0.0911 0.0238 0.1732 0.2621 0.5647
0.8388 0.1333 0.0279 0.1584 0.2291 0.6125
0.7903 0.1728 0.0369 0.1394 0.1946 0.6660

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0.7330 0.2127 0.0543 0.1304 0.1560 0.7136
0.6695 0.2482 0.0823 0.1278 0.1171 0.7551
0.6050 0.2775 0.1175 0.1169 0.0769 0.8062

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0.5428 0.3058 0.1514 0.1084 0.0426 0.8490
0.4832 0.3290 0.1878 0.1028 0.0000 0.8972

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303.15 K
0.9729 0.0000 0.0271 0.2188 0.3166 0.4646
0.9293 0.0450 0.0257 0.1981 0.2887 0.5132
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0.8825 0.0903 0.0272 0.1762 0.2597 0.5641
0.8379 0.1308 0.0313 0.1639 0.2267 0.6094
0.7866 0.1732 0.0402 0.1483 0.1938 0.6579
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0.7261 0.2110 0.0629 0.1378 0.1571 0.7051

0.6594 0.2429 0.0977 0.1268 0.1177 0.7555
0.5934 0.2758 0.1308 0.1197 0.0799 0.8004
0.5349 0.3016 0.1635 0.1130 0.0403 0.8467
D

0.4718 0.3226 0.2056 0.1084 0.0000 0.8916

313.15 K
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0.9751 0.0000 0.0249 0.2321 0.3107 0.4572

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0.9294 0.0443 0.0263 0.2097 0.2849 0.5054

0.8867 0.0881 0.0252 0.1886 0.2551 0.5563
0.8357 0.1308 0.0335 0.1724 0.2241 0.6035
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0.7833 0.1716 0.0451 0.1572 0.1913 0.6515

0.7222 0.2093 0.0685 0.1455 0.1539 0.7006
0.6538 0.2425 0.1037 0.1352 0.1186 0.7462
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0.5867 0.2700 0.1433 0.1254 0.0770 0.7976

0.5254 0.2948 0.1798 0.1189 0.0426 0.8385
0.4675 0.3176 0.2149 0.1113 0.0000 0.8887
Standard uncertainties u are u(w) = 1 10 -4 and u(T) = 0.1 K.

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Table 3
Experimental tie-line data for water (1) + propanoic acid (2) + 3-methylbutan-1-ol (3) ternary system at
temperature range (293.15 to 313.15) K and atmospheric pressure.
Water-rich phase Solvent-rich phase
w11 w12 w13 w13 w23 w33
293.15 K
0.9541 0.0289 0.0170 0.1184 0.0791 0.8025
0.9347 0.0467 0.0186 0.1258 0.1047 0.7695
0.9140 0.0653 0.0207 0.1404 0.1559 0.7037
0.8933 0.0833 0.0234 0.1572 0.2144 0.6284
0.8674 0.1051 0.0275 0.1804 0.2948 0.5248

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303.15 K
0.9483 0.0286 0.0231 0.1125 0.0470 0.8405
0.9355 0.0430 0.0215 0.1245 0.0865 0.7890

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0.9197 0.0594 0.0209 0.1409 0.1402 0.7189
0.9039 0.0747 0.0214 0.1573 0.194 0.6487

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0.8765 0.0993 0.0242 0.1814 0.2728 0.5458
313.15 K
0.9503 0.0288 0.0209 0.1107 0.0266 0.8627
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0.9338 0.0477 0.0185 0.1266 0.0738 0.7996
0.9199 0.0621 0.0180 0.1323 0.0907 0.7770
0.8939 0.0865 0.0196 0.1562 0.1615 0.6823
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0.8731 0.1042 0.0227 0.1710 0.2053 0.6237

Standard uncertainties u are u(w) = 1 10 -4 and u(T) = 0.1 K.
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Table 4
Distribution coefficients for water (D1), propanoic acid (D2) and separation factor (S)
for water (1) + propanoic acid (2) + 3-methylbutan-1-ol (3) ternary system.

T/K D1 D2 S
293.15 K
0.1241 2.3770 22.06
0.1346 2.2420 16.66
0.1536 2.3874 15.54
0.1760 2.5738 14.63
0.2080 2.8049 13.49

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303.15 K
0.1186 1.6434 13.85
0.1331 2.0116 15.12

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0.1532 2.3603 15.41
0.1740 2.5971 14.92 Standard uncertainties u are u(w)

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= 1 10 -4 and u(T) = 0.1 K
0.2070 2.7472 13.27
313.15 K
0.1165 0.9236 7.93
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0.1356 1.5472 11.41
0.1438 1.4605 10.16
0.1747 1.8671 10.68
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0.1959 1.9702 10.06

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Table 5
The parameters of Othmer–Tobias equation at different temperatures.

T/K A B R2
293.15 0.8447 -1.7203 0.9543
303.15 0.6369 -1.8437 0.9996
313.15 0.7699 -1.5359 0.9920

Table 6

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The binary interaction parameters of NRTL and UNIQUAC models along with the RMSD values for water (1)
+ propanoic acid (2) + 3-methylbutan-1-ol (3) ternary system.
Component i 1 1 2
RMSD
Component j 3 2 3

RI
NRTL 0.0125
aij 8.68 0.00 0.00

SC
aji ‒2.68 0.00 0.00
bij ‒2778.49 2303.63 1128.67
bji 1887.32 185.48 1473.28
cij 0.20 0.30 0.30
NU
UNIQUAC 0.0100
aij 0.00 0.00 0.00
aji 0.00 0.00 0.00
MA

bij ‒36.65 ‒4082.98 ‒1222.58

bji ‒966.45 ‒641.28 ‒1414.76
E D
PT
CE
AC

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'Research highlights'
 LLE data of water + propanoic acid + 3-methylbutan-1-ol mixture were
determined.

 3-Methylbutan-1-ol is a suitable choice for extraction of propanoic acid.

 The tie-line compositions were determined from refractive index

measurements.

PT
 The tie-line data were correlated by NRTL and UNIQUAC models with good
agreement.

RI
SC
NU
MA
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PT
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AC