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Liquid−Liquid Equilibrium Study of the Water + Acetic Acid +

Kerosene Ternary System at 293.2, 298.2, and 308.2 K
Farnaz Jafari and Javad Saien*
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ABSTRACT: The chemical system of water + acetic acid + kerosene is

frequently used in different liquid−liquid extraction studies. Accordingly, a
comprehensive knowledge about this system is essential. The present study
reports the capabilities of kerosene in extracting acetic acid from aqueous
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solutions at conventional temperatures of 293.2, 298.2, and 308.2 K and

under an ambient pressure of 81.5 kPa. The cloud point method and
refractive index measurement were employed in experiments. The
distribution coefficient of the solute was within (0.0536−0.1161) and the
important separation factor was within (5.07−82.84). The upper limit values
in the ranges of the latter parameter were 1.36−8.80 times of those with other
solvents. The distribution coefficient increased with temperature, but the
separation factor diminished. The provided data were reproduced with the
nonrandom two-liquid and universal quasichemical activity coefficient
models, and the corresponding binary interactions were determined at each
temperature. In this regard, a surrogate of kerosene, consisting of 80 wt % n-decane and 20 wt % 1,2,4-trimethylbenzene, was
considered. The root mean square deviations of, respectively, (0.0035−0.0057) and (0.0056−0.0067) and also other criteria
revealed good agreements between experimental and predicted values.

1. INTRODUCTION Table 1. Recent Investigations on the Liquid−Liquid

Although reaction is the key step in a chemical plant, Extraction Process Using the Chemical System of Water +
separation and purification of materials are important and Acetic Acid + Kerosene
may involve 60−80% of the capital investment and operating experimental setup research alternate year/ref
costs.1 Separation techniques are roughly categorized into impinging stream disk speed and flow rate 20015
major groups of mass transfer and physical-based methods.2 contactor
Among the various mass transfer methods, liquid−liquid single drop extraction surfactant (ABS) and column height 20076
extraction has broad applications in petrochemical, hydro- column
metallurgy, pharmaceutical, and biochemical industries. It is pulsed regular packed nanoparticle (SiO2) 20177
column
based on transferring of a solute from a feed to a rather
pulsed sieve plate nanoparticle (SiO2) 20148
immiscible solvent.3 column
To simulate and design the extraction process, it is required pulsed sieve plate pulsation intensity and dispersed phase 20179
to know about phase equilibrium, hydrodynamics, and mass column flow
transfer bases. In this regard, liquid−liquid equilibrium (LLE) rotating disk contactor disk speed 201010
gives the required knowledge about the miscibility gap, solute rotating disk contactor nanoparticle (SiO2) 201611
distribution coefficient, and selectivity of the used chemical slug flow microchannel flow rate, capillary diameter, and flow 200712
system.4 ratio
A lot of studies have been devoted to the LLE of different slug flow microchannel surfactant (CTAB) and flow velocity 201013
ternary/quaternary systems. The target system of water + slug flow microchannel residence time, channel diameter, and 201614
slug length
acetic acid + kerosene has been widely used in the liquid−
liquid extraction process studies as single/swarm of drops in
columns or slugs in microchannels. The recent investigations Received: June 17, 2021
by using this chemical system are listed in Table 1. Accepted: August 9, 2021
Different investigations have been conducted with different
ternary systems in which a petroleum product has been one of
the constituent components. For instance, the water + alcohols
+ gasoline system has been utilized by Stephenson15 using the

© XXXX American Chemical Society https://doi.org/10.1021/acs.jced.1c00474

A J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data
Table 2. CAS Registry Number, Mass Fraction Purity, Supplier, Refractive Index, and Density of the Used Liquid Chemicals at
a Temperature of T = 298.2 K and under an Ambient Pressure of p = 81.5 kPaa
a
component CAS reg. no. mass fraction supplier
water 7732-18-5 ultrapure Hastaran
acetic acid 64-19-7 ≥0.99 Merck
kerosene 8008-20-6 ≥0.95 Sigma-Aldrich
a
Standard average uncertainties are u(T) = 0.1 K, u(nd) = 0.0007, ur(ρ) = 0.001, and u(p) = 0.3 kPa.
synthetic gasoline with a surrogate mixture of aromatic and
aliphatic hydrocarbons. It was reported that alcohols tend to be
more in the organic phase. In a similar study, Silveira et al.16
performed a research on the diesel + biodiesel + alcohol
system at 293.15 and 313.15 K. Furthermore, Santos et al.17
worked on the ternary system of biodiesel + methanol + water
and reproduced data based on nonrandom two-liquid (NRTL)
and universal quasichemical (UNIQUAC) models at temper-
atures of 298.15, 308.15, and 318.15 K. In a recent study, Chen
et al.18 made a comprehensive study on the surrogate kerosene
+ ethanol + water system at four temperatures and compared
the experimental data with the predicted values by the
UNIQUAC functional-group activity coefficient (UNIFAC)
model. More recently, olefins were separated from catalytic
cracking of naphtha based on the LLE data from aromatics/
sulfide (naphtha) + olefin + dimethyl sulfoxide systems and
employing the NRTL and UNIQUAC models for theoretical
investigations.19 Subsequently, the ability of propylene
carbonate to separate olefins from naphtha was assessed
through an investigation on the ternary LLE of the propylene
carbonate + aromatics/sulfides (naphtha) + olefin system, and
the NRTL and UNIQUAC thermodynamic models were
employed to reproduce the experimental data.20
Utilizing the distillation process for separating acetic acid
and water components necessitates a column with many stages
and a great reflux ratio, thus entailing high running costs.21 In
turn, liquid−liquid extraction, due to the lower energy cost, is
widely used to separate acetic acid from aqueous solutions, and
in this respect, many solvents have been tried. In this regard,
Ghanadzadeh et al.22 evaluated the 2-ethyl-1-hexanol as an
organic solvent to determine LLE data for the ternary system
of water + acetic acid +2-ethyl-1-hexanol. Furthermore, ethyl
heptanoate has been introduced as an adequate organic solvent
for the extraction of these acids from aqueous solutions
through investigating the phase behavior of the ternary system
of water + acetic acid + ethyl heptanoate.23 Relevantly,
kerosene is a desired solvent with low toxicity and availability
as well as can be easily separated from an aqueous phase.
Meanwhile, as the next step of the extraction process,
separation of kerosene with a significantly high boiling point
range (446.2−542.2) K24 and acetic acid with a boiling point
of 391.0 K is feasible.25
Despite a wide study on the liquid−liquid extraction process,
no investigation has been performed on the equilibrium
behavior of the water + acetic acid + kerosene system and
correlating the LLE data. Here, the capabilities of kerosene in
extracting acetic acid from an aqueous phase are investigated.
The corresponding LLE data are provided at conventional
temperatures of 293.2, 298.2, and 308.2 K and under a
dominant ambient pressure of 81.5 kPa. From LLE data, the
important solute distribution coefficient and the separation
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nd ρ/g cm−3
exp. lit. exp. lit.
1.33250 1.332526,27 0.99709 0.9970428
0.9969329
1.37045 1.3704630,31 1.04395 1.0439232
1.0439533
1.44232 1.4423034 0.81025 0.81012
factor are determined. Meanwhile, the NRTL and UNIQUAC
activity coefficient models are employed for reproducing the
data and determining the binary interaction parameters.
2. MATERIALS AND METHODS
2.1. Materials. Kerosene (CAS Registry No. 8008-20-6)
was a reagent grade product supplied by Sigma-Aldrich. Acetic
acid (purity of 99.8%) was a Merck product. Fresh deionized
water (conductivity of less than 0.08 μS·cm−1) was produced
by a deionizer apparatus for preparing the solutions. The major
information of the used chemicals, compared to literature
values, are listed in Table 2. In this regard, the refractive index
and density of liquids were, respectively, measured by means of
an Abbe AR4 Kruss refractometer (Germany), uncertainty
0.0007, and an Anton-Paar DMA4500 oscillating U-tube
densimeter (Austria), having a relative uncertainty of 0.001.
2.2. Measurements. The well-known cloud point method
and refractometry were used for determining the components
of mass fraction in each aqueous/organic phase.35 At the first
step, a miniature cell surrounded by a jacket and with a
magnetic stirrer inside was used. A circulation of water
conducted from a thermostat (Julabo, Germany) through the
cell jacket and a refractometer was established to adjust a
constant temperature. To ensure of thermostating, the
temperature was checked by means of an Amadigit, Percica
thermometer (Germany) with an accuracy of 0.01 K. Initially,
the known binaries of water + acetic acid or kerosene + acetic
acid were weighted using a 0.0001 g Ohaus balance (AXIS,
BTA2100 D, Poland) and then each phase was gradually
titrated with a third component (kerosene or pure water) until
a cloudy solution appeared. Consequently, the refractive index
of the known mass fraction samples was measured and thus the
related calibration curve became available for a certain
temperature.
The refractive indices and corresponding mass fractions of
each phase together with the calibration curves are given in the
Supporting Information. Consistently, the ith component mass
fractions are represented with the symbols wi1 and wi3 for the
aqueous and organic phases, respectively. The index i could be
1 for water, 2 for acetic acid, and 3 for kerosene. Calibration
curves show an increasing trend of the refractive index with the
acid content in the aqueous phase, attributed to the higher
inherent refractive index of this component compared to water.
Meanwhile, by increasing acetic acid concentration in
kerosene, the lower refractive index of acid causes a decreasing
trend of variation. A similar phenomenon is observed for
kerosene in the aqueous and organic phases.
In the next step, to generate the tie-line data, a known
quantity of water was loaded in the equilibrium cell, and
certain amounts of kerosene and acetic acid were added until
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Table 3. Experimental Tie-Line Mass Fractions (W), Water Distribution Coefficient (D1), Solute Distribution Coefficient (D2),
and Separation Factor (S) for the System of Water (1) + Acetic Acid (2) + Kerosene (3) at Temperatures of T = 293.2, 298.2,
and 308.2 K and under an Ambient Pressure of p = 81.5 kPaa
aqueous phase organic phase
w11 w21 w31 w13 w23 w33 D1 D2 S
T = 293.2 K
0.8809 0.1152 0.0039 0.0006 0.0065 0.9929 0.0007 0.0564 82.84
0.8516 0.1435 0.0049 0.0007 0.0078 0.9915 0.0008 0.0544 68.07
0.8095 0.1810 0.0095 0.0008 0.0097 0.9895 0.0010 0.0536 56.40
0.7053 0.2733 0.0214 0.0010 0.0154 0.9836 0.0014 0.0562 39.65
0.6114 0.3561 0.0325 0.0013 0.0214 0.9774 0.0021 0.0600 29.11
0.5415 0.4182 0.0402 0.0016 0.0271 0.9713 0.0028 0.0649 22.85
0.4583 0.4915 0.0502 0.0021 0.0342 0.9637 0.0040 0.0695 17.39
0.3545 0.5843 0.0612 0.0024 0.0441 0.9535 0.0068 0.0755 11.15
0.2713 0.6573 0.0714 0.0030 0.0551 0.9419 0.0111 0.0839 7.58
0.2431 0.6816 0.0752 0.0032 0.0596 0.9372 0.0132 0.0874 6.64
0.2062 0.7124 0.0814 0.0035 0.0662 0.9303 0.0170 0.0930 5.48
T = 298.2 K
0.8892 0.1083 0.0025 0.0008 0.0074 0.9918 0.0009 0.0683 75.95
0.8584 0.1384 0.0032 0.0010 0.0099 0.9891 0.0012 0.0713 61.22
0.8170 0.1755 0.0074 0.0012 0.0129 0.9859 0.0015 0.0732 49.86
0.7221 0.2584 0.0195 0.0015 0.0195 0.9789 0.0021 0.0756 35.83
0.6278 0.3426 0.0295 0.0019 0.0258 0.9723 0.0030 0.0754 25.28
0.5777 0.3867 0.0356 0.0021 0.0298 0.9681 0.0036 0.0771 21.21
0.4729 0.4785 0.0486 0.0027 0.0394 0.9579 0.0057 0.0823 14.36
0.3781 0.5623 0.0596 0.0032 0.0485 0.9483 0.0085 0.0863 10.20
0.2968 0.6346 0.0686 0.0038 0.0584 0.9378 0.0128 0.0920 7.19
0.2534 0.6724 0.0742 0.0041 0.0654 0.9305 0.0162 0.0972 6.01
0.2192 0.7003 0.0805 0.0044 0.0712 0.9244 0.0201 0.1017 5.07
T = 308.2 K
0.9013 0.0962 0.0025 0.0010 0.0076 0.9914 0.0011 0.0790 71.20
0.8816 0.1152 0.0032 0.0013 0.0101 0.9886 0.0015 0.0877 59.46
0.8352 0.1578 0.0070 0.0017 0.0142 0.9841 0.0020 0.0902 44.30
0.7564 0.2264 0.0172 0.0021 0.0204 0.9775 0.0028 0.0900 32.40
0.6702 0.3027 0.0271 0.0026 0.0271 0.9703 0.0039 0.0897 23.12
0.6015 0.3642 0.0343 0.0029 0.0333 0.9638 0.0048 0.0913 18.94
0.4914 0.4623 0.0463 0.0035 0.0433 0.9532 0.0071 0.0936 13.14
0.4112 0.5326 0.0562 0.0039 0.0512 0.9449 0.0095 0.0962 10.14
0.3363 0.5974 0.0662 0.0043 0.0608 0.9349 0.0128 0.1018 7.96
0.2614 0.6653 0.0733 0.0050 0.0742 0.9208 0.0191 0.1116 5.83
0.2365 0.6854 0.0781 0.0053 0.0796 0.9151 0.0224 0.1162 5.19
a
Standard uncertainties are: u(T) = 0.1 K, u(nd) = 0.0007, u(p) = 0.3 kPa, and u(w) = 0.0003.

the entire weight of the sample reached to (1 ± 0.0001) g.
Other similar mixtures were prepared with different
compositions. A water shaker bath (N-BIOTEK-304, Korea)
with an uncertainty of 0.1 K was utilized at 175 rpm for
agitating the glass cells at a certain temperature for 4 h while
the cells were tightly closed. To ensure the complete phase
separation of phases, the samples were then left to rest for 12 h.
On reaching such equilibria, a trace amount of the organic
phase was withdrawn from the top and bottom layers using a
microsyringe and analyzed by measuring their refractive index.
To ensure of results, the refractive index of each phase was
measured at least three times. After directly determining the
unknown compositions in each phase and considering the
relevant calibration curve, the tie-line data were established.
The uncertainty of mass fractions was calculated to be less than
0.0003. A similar method, for obtaining the LLE data, has
already been reported.36 The perfect tie-line data, the relevant
mass fractions and refractive indices, and calculation of the
C https://doi.org/10.1021/acs.jced.1c00474
uncertainty of mass fractions are given in the Supporting
Information.
3. RESULTS AND DISCUSSION
3.1. Experimental Data. The experimental data of the
water (1) + acetic acid (2) + kerosene (3) system are given in
Table 3, and the ternary diagram of the system is shown in
Figure 1. The tie-lines evidently show the tendency of the acid
to be more in the aqueous phase than in kerosene, which can
be attributed to the hydrogen bonding. Clearly, significant
enhancement of acid solubility in water is observed by
increasing the solute concentration. Binaries of water and
kerosene are immiscible, but a slight solubility of water in
kerosene is relevant at higher acid mass fractions. This
situation totally shows a Type-2 ternary system.37
Figure 2 represents the acetic acid distribution between
phases. Considering temperature, as the most dominant factor,
it can be concluded from tie-lines that the solubility of water
and kerosene is gradually increased. The influence of
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Figure 1. Ternary diagram for the water + acetic acid + kerosene system; circle and solid lines for T = 293.2 K; square and dashed lines for T =
298.2 K; and triangle and dash-dotted lines at a temperature of T = 308.2 K and under an ambient pressure of p = 81.5 kPa.

Figure 2. Equilibrium distribution of acetic acid between kerosene and water phases at temperatures of: T = 293.2 K, circle, T = 298.2 K, square,
and T = 308.2 K, triangle, and under an ambient pressure of p = 81.5 kPa. Error bars indicate the standard deviation of the mean of three
independent experiments.

temperature on the acid distribution was not sensible at low interactions, and the effect of temperature was not sensible
solute concentrations, though a significant temperature effect under the applied conditions.
was observed at high concentrations. These results are similar 3.2. Distribution Coefficient and Separation Factor.
to that previously reported for the water + isobutyric acid + The capability of a solvent in solute-carrying is represented
cumene38 and water + acetic acid + toluene39 systems. As with the solute distribution coefficient. Here, water and solute
depicted in Figure 3, the solubility of kerosene in water was distribution coefficients between the phases are, respectively, as
increased with the acetic acid concentration due to potential follows:
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Figure 3. Kerosene solubility in water versus acetic acid concentration in the aqueous phase at temperatures of: T = 293.2 K, circle, T = 298.2 K,
square, and T = 308.2 K, triangle, and under an ambient pressure of p = 81.5 kPa. Error bars indicate the standard deviation of the mean of three
independent experiments.

Figure 4. Distribution coefficients of water versus its mass fraction at temperatures of: circle, T = 293.2 K; square, T = 298.2 K; and triangle, T =
308.2 K and under an ambient pressure of p = 81.5 kPa.

w13 The separation factors higher than unity indicate a

D1 =
w11 (1) satisfactory selectivity of a solvent. The higher this value, the
better extraction performance would be.40
w23 Results indicate the potential ability of kerosene for
D2 = extracting acetic acid from aqueous solution with the
w21 (2) distribution coefficient (D2) and the separation factor,
respectively, within (0.0536−0.1161) and (5.07−82.84)
Higher values of (D2) would be desirable due to a lower under the applied temperatures (Table 3). Figures 4 and 5
required amount of solvent for a separation. Another important show the variation of D1 and D2 against the acid concentration
criterion is the separation factor, S, which examines the in the aqueous phase. Nonlinear variations are observed for
capability and selectivity of a solvent for extracting a solute, is both the cases. By increasing the acid concentration, the
given as: accompanied water will also be increased in kerosene as a
D2 consequence of the hydrogen bond between water and acetic
S= acid. The distribution coefficient is considerably dependent on
D1 (3) temperature at high solute concentrations; however, with low
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Figure 5. Distribution coefficients of acetic acid versus its mass fraction at temperatures of: circle, T = 293.2 K; square, T = 298.2 K; and triangle, T
= 308.2 K and under an ambient pressure of p = 81.5 kPa.

Figure 6. Separation factor of acetic acid versus its mass fraction at different temperatures of: circle, T = 293.2 K; square, T = 298.2 K; and triangle,
T = 308.2 K and under an ambient pressure of p = 81.5 kPa.

solute mass fractions, the influence of temperature is
nonsignificant, particularly for the water distribution coef-
ficient, D1. The contribution of distribution coefficients in the
separation factor gives a decreasing trend of variation for the
separation factor with the concentration of acetic acid and
temperature (Figure 6) revealing that the higher separation
factor is achieved with low solute concentrations and
synthesized ionic liquids, low price, availability, and low
toxicity of kerosene are distinctive. As pointed above, recovery
of kerosene through the distillation process is feasible due to
significant difference in boiling points.25
3.3. Verification of the Data Consistency. The
consistency of the obtained tie-lines at different temperatures
was verified based on the following equations
ij 1 − w33 yz i y

lnjjj zz = A + B lnjjj 1 − w11 zzz

j w33 zz 1 j zz
predominately at the lower temperature.
j w
k { k 11 {
For a precise evaluation of the kerosene capability in acetic
1
acid separation, a comparative list of separation factors is (4)

ij w yz ij w yz
presented in Table 4. As it is obvious, kerosene has great

lnjjj 21 zzz = A 2 + B2 lnjjj 23 zzz

jw z j w33 z
potential for extracting acetic acid from water with the upper

k 11 { k {
limit in the ranges, much higher than alcohol, ether, and ionic
liquid solvents (1.36−8.80 times). In comparison to (5)

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Table 4. Comparison of the Kerosene Separation Factor carbon atoms per molecule and that in addition to saturated
Ranges with Other Reported Solvents in Extracting Acetic hydrocarbons, there are evidences of the presence of benzene
Acid Form the Aqueous Phase at Different Temperatures and naphthalene derivatives.52 Owing to this complexity,
correlating the phase equilibrium of such fuels is difficult.53
T (K) solvent range of S
Thus, an approach has been adopted to test and evaluate
293.2 2-octanol 3.81−17.7241
surrogate fluids of known mixtures, which can be easily
cyclopentyl methyl ether 4.08−62.7842
characterized. In 2009 and 2014, different compositions were
diisopropyl ether 4.71−32.0043
[C4mim] [NTf2] ionic liquid 2.05−14.5844
tested and a surrogate made up of (n-decane 80 wt % and
[C6mim] [NTf2] ionic liquid 1.97−26.9544
1,2,4-trimethylbenzene 20 wt %) was proposed with the closest
[C8mim] [NTf2] ionic liquid 2.69−23.8444 physicochemical properties to simulate kerosene behavior.18,54
[C10mim] [NTf2] ionic liquid 1.97−34.4244 Very close to unity values of the activity coefficients of the
kerosene 5.48−82.84 (present work) hydrocarbons in kerosene make it reasonable to consider this
298.2 diethyl succinate 3.95−15.4245 surrogate mixture as a pseudo single component, to be
diethyl glutarate 3.21−15.1545 considered instead of kerosene.55 This mixture was considered
diethyl adipate 5.35−17.0345 here in correlating the experimental data.
butyl acetate 2.23−17.8946 Accordingly, the LLE data at different temperatures were
cyclopentyl methyl ether 2.22−37.9342 reproduced based on the classical NRTL and UNIQUAC
dimethyl carbonate 3.98−12.4347 models of the activity coefficient via the Aspen Plus simulator
2-ethyl hexyl acetate 3.05−18.4121 (Version 8.4). The nonrandomness parameter (αij) in the
toluene 20.14−55.8339 NRTL model was considered as 0.2 and 0.3.56 For the
kerosene 5.07−75.95 (present work) UNIQUAC model, the r and q structural parameters are,
303.2 butyl acetate 2.08−16.3146 respectively, 0.92 and 1.40 for water,57 2.20 and 2.07 for acetic
2-octanol 5.00−8.0941 acid,58 and 7.66 and 6.30 for the surrogate of kerosene.18 The
2-heptanol 5.68−18.5425 NRTL and UNIQUAC interaction parameters are summarized
308.2 butyl acetate 2.04−15.7046
in Table 6. Details of describing parameters are given in the
cyclopentyl methyl ether 1.85−26.1942
literature.59 For comprehensive insight, the ternary phase
dimethyl carbonate 3.75−8.2347
diagram including the experimental data and the predicted
2-ethyl hexyl acetate 2.91−14.3421
values by the models, at 298.2 K, are shown in Figure 7. A very
kerosene 5.19−71.20 (present work)

ij w yz
close agreement is observed. In the Supporting Information,

w33 = A3 + B3jjj 33 zzz

jw z
k 11 {
(6)
where A1 and B1, A2 and B2, and A3 and B3 are parameters of
the Othmer-Tobias,48 the Hand,49 and the Bachman50
correlations, respectively. In Table 5, the corresponding slope
and intercept values are listed. The coherent consistency of
data is confirmed with the close to unity regression coefficients
(R2) based on the applied correlations.
In addition to the above cases, validity of the LLE data was
evaluated according to the procedure developed by Marcilla et
al.,51 where the calculated masses in both the phases are
compared with the total applied mass in the experiment. As
proposed in the method, the overall mass balance deviations
less than 0.5% ensure good quality of the data. Details of
corresponding calculations and obtained deviations per each
tie-line, based on the provided data are given in the Supporting
Information. The maximum revealed deviation for tie-lines is
0.0078%. The combined deviations are 0.0076, 0.0083, and
0.0102 at %, respectively, 293.2, 298.2, and 308.2 K, totally
indicating validity of the data.
3.4. Data Correlation. Kerosene is made up of hundreds
of aliphatic and aromatic hydrocarbons mostly with 8−18
the triangular figures of the experimental data together with
those predicted by the models are provided at the other
temperatures.
For the precise representation of the models, the root mean
square deviation (RMSD) was obtained from ref 60
∑i ∑m ∑n (w exp cal 2
imn − w imn)
RMSD =
6N (7)
cal
where wexpimn and wimn are the experimental mass fractions and
those correlated by a model. Here, i = 1, 2, and 3 stands for the
components, m = I and II for the aqueous and organic phases,
and n = 1, 2, ..., N represents the tie-lines number. The
thermodynamic models were satisfactory for correlating the
data, and there is very low RMSD values for the NRTL and
UNIQUAC models, within (0.0035−0.0057) and (0.0056−
0.0067), respectively (Table 6). Accordingly, the NRTL model
is more appropriate for reproducing the LLE data.
Fitting data with the NRTL and UNIQUAC models was
also evaluated, for each component and for each of the phases,
based on the average absolute deviation (AAD) and root mean
square error (RMSE) criteria, specified by the following
equations61

Table 5. Parameters of Othmer-Tobias and Hand Correlations and the Regression Coefficients Based on the Provided Data

Othmer-Tobias Hand Bachman

2 2
T (K) A1 B1 R A2 B2 R A3 B3 R2
293.2 −3.4561 0.6859 0.9956 4.6561 1.3401 0.9953 −0.0227 1.0144 0.9952
298.2 −3.2362 0.6362 0.9948 4.6699 1.4244 0.9938 −0.0238 1.0167 0.9944
308.2 −3.0773 0.6163 0.9946 4.5922 1.4817 0.9959 −0.0282 1.0192 0.9936

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Table 6. Binary Interaction Parameters of NRTL and UNIQUAC Models for the System of Water (1) + Acetic Acid (2) +
Kerosene (3) at Temperatures of T = 293.2, 298.2, and 308.2 K and under an Ambient Pressure of p = 81.5 kPa
NRTL UNIQUAC
T (K) i-j bij (K) bji (K) αij RMSD aij (K) aji (K) RMSD
293.2 1−2 211.00 26.26 0.2 0.0035 29.02 64.84 0.0056
1−3 2027.43 1441.89 0.3 14.75 −253.68
2−3 455.12 306.00 0.2 72.08 −83.30
298.2 1−2 190.37 129.74 0.3 0.0042 47.04 12.63 0.0060
1−3 2343.63 1371.19 0.2 −10.40 −113.56
2−3 390.64 343.05 0.3 83.48 −159.22
308.2 1−2 184.06 219.59 0.3 0.0057 54.77 −8.19 0.0067
1−3 2395.53 1279.50 0.2 −12.66 −53.94
2−3 372.68 366.83 0.3 96.62 −163.86

Figure 7. Ternary system diagram of water + acetic acid + kerosene at a typical temperature of T = 298.2 K and under an ambient pressure of p =
81.5 kPa; circle and solid lines experimental tie-lines, square and dashed lines predicted tie-lines with NRTL (a), and triangle and dash-dotted lines
predicted tie-lines with UNIQUAC (b) models.

N satisfactory prediction of the tie-lines. The remaining works

1
AAD = ∑ |wiexp − wical| rely on the behavior of actual industrial waters in the extraction
N (8)
n=1 process.

RMSE =
1
N
∑ (wiexp − wical)2
N n=1
(9)
The resulting values of AAD and RMSE are presented in the
Supporting Information. The acquired maximum AAD and
RMSE values of 0.0089 and 0.0092 again confirm that both the
models fit the experimental data with a high accuracy.
4. CONCLUSIONS
In this research the LLE of the widely used chemical system of
water + acetic acid + kerosene was investigated at different
temperatures. Precisely, the capability of kerosene with a high
separation factor was revealed. There was an ascending trend
of variation for the acetic acid distribution coefficient with its
concentration and with temperature; whereas, a descending
trend was relevant for the separation factor. The reliability of
tie-lines was confirmed with high levels of agreement.
In theoretical investigation, the experimental data were
reproduced by considering a confirmed surrogate of n-decane
and 1,2,4-trimethylbenzene for kerosene and using the well-
known NRTL and UNIQUAC models. Based on different
criteria, both the models, preferably the NRTL model, gave
H https://doi.org/10.1021/acs.jced.1c00474
■
*
ASSOCIATED CONTENT
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.jced.1c00474.
Table of refractive indices and the mass fraction of
phases at different temperatures, calculating the standard
deviation for mass fractions, validation of the exper-
imental data based on the Marcilla et al.51 method and
the corresponding table, table of AAD and RMSDE
values, and comparing figures of experimental and
predicted values for NRTL and UNIQUAC models at
different temperatures (PDF)
■ AUTHOR INFORMATION
Corresponding Author
Javad Saien − Department of Applied Chemistry, Bu-Ali Sina
University, Hamedan 65174, Iran; orcid.org/0000-0001-
5731-0227; Email: saien@basu.ac.ir
Author
Farnaz Jafari − Department of Applied Chemistry, Bu-Ali Sina
University, Hamedan 65174, Iran
J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data pubs.acs.org/jced Article

Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.jced.1c00474
Funding
The authors acknowledge the Bu-Ali Sina University author-
ities for the financial support of this work.
Notes
The authors declare no competing financial interest.
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