bLiquid-liquid Ternary Equilibrium in Water (A) -Butyl Acetate (B) -Acetic Acid

(C) System
Mow Wei Keat KIL160043
Abstract
In the industrial practices, liquid-liquid extractor had been widely used to extract desired
components from liquid phase like acetic acid by using suitable solvent. Thus, this experiment
was conducted to study liquid-liquid equilibrium of water-butyl acetate-acetic acid system and
determine the tie lines and plait point from the ternary diagram drawn. Besides, M-UNIFAC
model was applied and compared for its ability to predict the LLE system. Basically, the
experiment was carried out firstly by obtaining the refractive index of the mixture solution after
the cloud point was reached to obtain calibration curves for both organic and aqueous phase.
Next, another set of three component mixtures prepared were analyzed by a refractometer after
the mixing and separation process to develop the tie lines. After data analysis and
interpretation, a ternary diagram with tie lines and plait point is obtained. Besides, M-UNIFAC
model was found to be inaccurate with respect to the experimental data in LLE system
prediction.

1.0 Introduction
Liquid-liquid extraction (LLE) is one of the oldest separation technique practiced which
involves the distribution of solutes in two immiscible liquid phase (Frederick F, 2002)and
transfer of particles desired into another liquid phase by introducing an appropriate solvent
(Müller, 2000). In the past decades, this technique had been widely used in various industries
as it performed well in separating components with small boiling point difference, separate
azeotropic mixtures and suitable for temperature sensitive components (Müller, 2000). Due to
large available organic solvent literature and experimental data and high linear sample capacity,
the liquid-liquid extraction becomes one of the main methods to prepare a sample from the
liquid solutions. (Frederick F, 2002). Besides, recovery of organic acid from some
manufacturing processes like fermentation is also one of the main application of this separation
method. In this case, the acetic acid recovered from the water by introducing different types of
solvent which is our research focus is very useful in various manufacturing processes such as
polyethylene terephthalate for the making of soft drink bottles, cellulose acetate as the main
material to produce photographic film and polyvinyl acetate which is the material for wood
glue (Song Hu, 2010). Basically, the fundamental of liquid-liquid extraction technique is the
mass transfer between the liquid components. Diffusion of the molecules is driven by the
chemical potential difference for neutral molecules and electrochemical potential for ionic
compound until equilibrium is achieved whereby the composition for the two resulting liquids
remain the same. This is main reason for the installation of stirrer or mixing instruments in the
liquid-liquid extractor as the mass transfer can be maximized through the formation of small
droplets amongst the two liquids. (Frederick F, 2002). Hence, upon its significance and variety
in the real lives application, research value is increasing and various models are developed to
exhibit better prediction and of the behavior and the control of the result specified. One of the
model that had been vigorously discussed in the literature is the M-UNIQUAC that is highly
recognized for its performance and accuracy in estimating the activity coefficient of the
components in the system. In theory, M-UNIFAC method which is a modified version of
UNIFAC operates by involving the mutual interaction between the functional groups of the
compounds present and capable to develop a very large group of molecules from small
structural units of molecules through concept of group contribution (Romain Richard, 2013).
Thus, this experiment was carried out to study the ternary equilibrium of the water-acetic acid-
butyl acetate system comprising the tie lines, plait point and binomal curves. On the other sied,
M-UNIFAC model is employed to estimate the equilibrium of this liquid-liquid system and
made comparison with our experimental data for credibility examination.

2.0 Methodology
2.1 Materials and Apparatus
The materials used in this experiment were distilled water, acetic acid and butyl acetate.
Meanwhile, the refractive index of the mixture solution was measured by using a refractometer.
For preparation of the solution with different components fraction, different sizes of beakers,
measuring cylinder, conical flask and corks were utilized. Furthermore, a burette was used for
titration purpose. Lastly, an mechanical shaker was used to enhance mixing of the solution and
separating funnel was also utilized for separation of liquid.

2.2 Procedures
6 sets of 50 ml mixture solution containing distilled water and acetic acid with different
compositions were prepared using measuring cylinders. After that, the solutions were titrated
using a burette containing butyl acetate until the solution turned cloudy. The volume of the
butyl acetate used to reach the cloud point was recorded. On the other hand, the refractive index
of the mixture after titration was measured by using the refractometer and recorded. These
steps from the beginning of the experiment were repeated by titrating a mixture of butyl acetate
and acetic acid using water to form organic rich phase calibration curve. For determination of
tie lines experiment, 6 sets of 175 ml solutions were formed by mixing the acetic acid, distilled
water and butyl acetate in different composition. Then, the solutions were put onto a
mechanical shaker for 30 mins at the speed of 170 rpm. After that, the solutions were let to
settle down in the separating funnel until two distinct layers were formed. The refractive index
of the liquid layers extracted were measured and recorded.

2.3 Assumptions
It was assumed that the equilibrium point was reached when a cloudy solution was formed after
the titration. Besides, the solution mixture was assumed to mix well through the help of the
mechanical shaker. Meanwhile, the experiments were carried out in the air-conditional room
with temperature set as 27 C. Thus, the assumption that the surrounding temperature was
constant at 300 K was made. The specify gravity of the acetic acid is 1.049 and butyl acetate
is 0.9.

2.4 Data Analysis

Firstly, the mole fractions of each components in the solution mixture were calculated by using
the volume of the butyl acetate, distilled water and acetic acid recorded by applying the
equation below.
Then, a graph of the mole fraction of each component in each set of solution mixture collected
from experiment one and two was plotted against the refractive index to develop reference line
for tie lines determination. Besides, the mole fractions calculated are also used to plot organic
rich and aqueous rich curve and develop a ternary diagram. Plait point was determined from
the diagram. For experiment 3, the mole fractions of each components were determined by
referring the reference trend plotted from the data of Experiment 1& 2. After that, the mole
fractions obtained were plotted on the ternary diagrams and connected with its respective set
of data to form tie lines on the ternary diagram. The credibilityof the tie lines calculated was
verified by applying Othmer Tobias equation as listed below.

3.0 Discussion
3.1 Determination of Aqueous Rich Phase Calibration Curve
Table 1 The volume and the mole fraction of water (A), butyl acetate (B) and acetic acid (C) in
aqueous rich solution at different refractive index

Refractive Index Volume, ml Mole Fraction

A B C A B C
1.3712 24.8 13.1 25.2 0.7535 0.0058 0.2407
1.3615 29.8 4.3 20.2 0.8200 0.0052 0.1748
1.3514 34.3 1.8 15.7 0.8700 0.0048 0.1252
1.3475 39.9 1.3 10.1 0.9223 0.0043 0.0734
1.3393 44.6 1.2 5.4 0.9595 0.0040 0.0365
1.3330 50.0 0.9 0.0 0.9963 0.0037 0.0000
 1.2

1 y = -6.4051x + 9.538
R² = 0.9903 A

0.8 c
B
Mole Fraction

0.6
Linear (A)

0.4 Linear (c)

Linear (B)
0.2 y = 6.3496x - 8.4677
R² = 0.9902
0
1.33 1.34 1.35 1.36 1.37 1.38
-0.2 y = 0.0555x - 0.0703
Refractive Index R² = 0.9911

Figure 1 Variation of the mole fraction of water (A), butyl acetate (B) and acetic acid (C) in
aqueous rich solution at different refractive index
In overall, the trends for all three components exhibited good credibility and consistency as the
data fit well with R2 bigger than 0.90. Based on the interpretation of the trends of each
component as shown in the graph above, when the refractive index increases, both the mole
fraction of butyl acetate and acetic acid increases. However, mole fraction of water is dropping
with the increase of refractive index. This phenomenon occurs because the theoretical
refractive index for pure water is 1.333 at 300K which is the same as our experimental result
as shown in the A trend. This indicates that the decrease of mole fraction of the water will result
in more deviation of the refractive index value of pure water. In this case, both acetic acid and
butyl acetate increases the refractive index of the water under aqueous rich solution mixture.
Besides, from the experimental results, it can be said that acetic acid is soluble in water as only
one phase was formed when 6 set of the solution mixture were prepared initially. This is mainly
due to the same polar nature of both water and acetic acid that enhance attraction and solubility
of acetic acid in water. On the other hand, as cloudy solution was formed when a certain amount
of butyl acetate was added, it can be said that butyl acetate only dissolves slightly in aqueous
solution dominated by water molecules. This is because butyl acetate is organic compound
while water is inorganic compound. No bond can be formed between the C atoms in the butyl
acetate and the water molecules, thus result in poor solubility. Meanwhile, it was observed that
when the concentration of acetic acid increases, the solubility of butyl acetate in aqueous
improves as demonstrated by the mole fraction trends of each component.

3.2 Determination of Organic Rich Phase Calibration Curve

Table 2 The volume and the mole fraction of water (A), butyl acetate (B) and acetic acid (C) in
organic rich solution at different refractive index

Refractive Index Volume, ml Mole Fraction

A B C A B C
1.3927 2.3 50.0 0.0 0.2480 0.7520 0.0000
 1.3870 2.5 44.6 5.4 0.2400 0.5970 0.1630
1.3811 4.2 39.8 10.2 0.3241 0.4284 0.2475
1.3786 6.0 34.8 15.2 0.3838 0.3105 0.3057
1.3741 11.7 29.7 20.3 0.5264 0.1864 0.2872
1.3687 18.8 24.6 25.4 0.6222 0.1135 0.2643

0.8

0.7 y = 28.01x - 38.266

R² = 0.9837
0.6
A
Mole Fraction

0.5
y = -16.918x + 23.744 C
0.4 R² = 0.8982
B
0.3 Linear (A)

0.2 Linear (C)

y = -11.091x + 15.521 Linear (B)

0.1
R² = 0.7015
0
1.365 1.37 1.375 1.38 1.385 1.39 1.395
Refractive Index

Figure 2 Variation of the mole fraction of water (A), butyl acetate (B) and acetic acid (C) in
organic rich solution at different refractive index
Based on the R2 of each trend, it can be said that the butyl acetate and water showed a high
consistency with the R2 exceeds 0.9. Nevertheless, the data obtained for the acetic acid is less
satisfactory. Thus, to improve its credibility, its mole fraction is calculated from other 2
components to compensate the errors occurred. After data analysis is carried out on this graph,
it shows that when refractive index increases, only butyl acetate exhibits an increasing trend,
while water and acetic acid are decreasing. In theory, the refractive index of pure butyl acetate
is 1.3941. In relation to this, there is only 0.1% deviation of our data obtained which is 1.3927.
This argument further verified the credibility of this calibration curve in expressing the
relationship between the refractive index and the corresponding mole fractions of each
component. For the decreasing trend of water over the increase of butyl acetate, it can be
understood water only dissolve slightly in butyl acetate which is an organic solvent. This
observation tallies with the results obtained from the previous experiment as discussed above.
Besides, it can be said that water is soluble in acetic acid as the increase of the concentration
of acetic acid accompanies with the increase of the mole fraction of water in the solution. This
is because hydrogen bonds are formed between the water and acetic acid molecules, thus
improve its solubility.

3.3 Determination of Tie Lines

Table 3 The mole fraction of water (A), butyl acetate (B) and acetic acid (C) in organic rich
phase and aqueous rich phase and y-value and x-value for the Othmer Tobias Correlation after
the mixing and separation of 6 different combination set of mole fraction of solution mixture.
 Mole Fraction At Equilibrium Point Othmer Tobias
Correlation
Aqueous Rich Organic Rich x y
A B C A B C
0.9183 0.0043 0.0773 0.2584 0.6175 0.1241 -1.384 -1.885
0.9049 0.0044 0.0907 0.2855 0.5727 0.1418 -1.194 -1.564
0.8927 0.0045 0.1027 0.2889 0.5671 0.1441 -1.038 -1.528
0.8818 0.0046 0.1135 0.2973 0.5531 0.1496 -0.908 -1.442
0.8677 0.0048 0.1275 0.3109 0.5307 0.1585 -0.749 -1.314
0.8556 0.0049 0.1396 0.3329 0.4942 0.1729 -0.618 -1.124

After conducting the experiment and obtaining the data as shown above, water shows the
highest composition in an aqueous phase while butyl acetate shows the highest mole fraction
in the organic phase of the solution. All the data above will be plotted in the ternary diagram
shown in the discussion below and tie lines that represent each row of data in the table above
will be determined. In this case, Othmer Tobias equation is applied to examine the data’s
reliability in developing the tie lines.

0.1

0
-3 -2.5 -2 -1.5 -1 -0.5 0
𝐼𝑛((1−𝑊_𝐵𝐵)/𝑊_𝐵𝐵 )

-0.1

y = 0.6937x + 1.2151 -0.2

R² = 0.9478
-0.3

-0.4

-0.5

-0.6
𝐼𝑛((1−𝑊_AA)/𝑊_AA )

Figure 3 Othmer Tobias plot at 300K

From the graph above, there is a linear trend plotted based on the equilibrium data obtained
after two phases are formed. The distribution of data is satisfactory with a R2 of about 0.95.
Meanwhile, the gradient of the trend denoted as A is 0.6937 while the y-intercept also the B in
the equation stated above is 1.2151. The linearization of the graph obtained above indicates
that the data is consistent and credible in forming tie lines closer to the real lives situation.
3.4 Liquid-liquid Ternary Diagram

Figure 4 Plot of ternary diagram for water-butyl acetate-acetic acid system at 300K based on
experimental results

From the diagram plotted above, a type 1 liquid-liquid extraction system is shown. In theory
or some literature review, water is immiscible to butyl acetate or in other words, insoluble in
butyl acetate in any proportional. However, from the experimental data, it can only be
concluded that water is insoluble in butyl acetate when added into pure butyl acetate. Besides,
this ternary diagram also shows that there is only slight solubility of water in high concentrated
butyl acetate. This result obtained is approximately tallying with the theory. However, on the
right side of the diagram, it is shown that one phase occurs when the mole fraction of distilled
water is bigger than 0.75 compared to butyl acetate in the absence of acetic acid. Hence, butyl
acetate is soluble in distilled water when the mole fraction of the water exceeds 0.75 based on
the experimental results which is violating the theory stated previously. This inaccuracy arises
mainly due to some technical and surroundings errors present thorough the experiment. These
errors and its respective precaution or improvements will be discussed later.

Furthermore, from this diagram, acetic acid is proven to be miscible and soluble in water and
butyl acetate in all proportion. This is because all the points on the butyl acetate axis and water
axis are located outside the binodal curves drawn using our experimental data. In relation to
this, theory is obeyed as acetic acid exhibits organic properties and capable to form hydrogen
bond with distilled water molecules. Apart from the solubility, the tie lines drawn are located
on the equilibrium data on the curves, thus can be used to determine the equilibrium
composition of the raffinate phase and aqueous phase after the mixing processes. The plait
point whereby the organic rich curve and the aqueous rich phase meets is estimated and plotted
in the ternary diagram above. The value of the plait point is 0.3 mol% acetic acid 0.55 mol%
distilled water and 0.15 mol% butyl acetate.

3.5 M-UNIFAC Model In Estimating the Liquid-liquid Ternary Diagram

CH3 CH2 CH3COOH CH3COO H2O Rk Qk
CH3 0 0 315.3 114.8 300 0.9011 0.8489
CH2 0 0 315.3 114.8 300 0.6744 0.5409
CH3COOH 663.5 663.5 0 660.2 -14.09 1.3013 1.2240
CH3COO 232.1 232.1 -256.2 0 72.87 1.9013 1.7280
H2O 1318 1318 -66.17 200.8 0 0.9200 1.4000

When comparing the ternary diagram predicted using M-UNIFAC and also experimental data,
although both exhibits type 1 liquid-liquid extraction, both diagram have obvious difference in
many ways. If viewing from theoretical perspective, the M-UNIFAC predicted diagram fits
well with the theory whereby the distilled water is immiscible to butyl acetate which violates
with the experimental results obtained. Besides, the area of the 1 phase region is generally
bigger in M-UNIFAC model than the experimental result. In term of plait point, M_UNIFAC
model has a value of 0.38 mol% acetic acid 0.38 mol% distilled water and 0.24 mol% butyl
acetate. If the experimental data which considers the real life variables is assumed to be correct,
the predicted model by M-UNIFAC is not satisfactory as it shows obvious deviation from the
experimental data. This statement is also supported by other literature research paper that
concluded that the M-UNIAFC group contribution model didn’t give a good prediction of the
LLE ternary diagram (E.İnce, 2002).
Figure 5Plot of ternary diagram for water-butyl acetate-acetic acid system at 300K based on
M-UNIFAC Model

3.6 Errors and Precaution

In this experiment, one of the main errors that affects the accuracy of the data obtained is
difficulty to identify the true cloud point occurred during titration. In this case, if agitation of
the conical flask is not vigorous, the liquid will turn cloudy although its real cloud point hadn’t
reach yet. Furthermore, the color of a clear and cloudy solution is almost the same, thus more
titrate is added beyond the cloud point for some sets of data and causes the experimental to
become inaccurate. Besides, the apparatus used like conical flask and beaker are reused after
simple washing for different set of experiment. As mole fraction of each component only vary
in a small range, thus the presence of additional distilled water or sample trace from the
previous set of experiment had affected our experimental results. Moreover, while transferring
the mixture, butyl acetate may vaporize easily due to its high vapor pressure compared to other
components. Thus, some of the butyl acetate molecules are lost into the air, causing the mole
fraction recorded to become bigger than the real value. During the sedimentation of the mixture
in the separating funnel to form 2 phases, some of the mixture liquid are agitated by the bubbles
formed from the air that flows into the funnel due to pressure difference. As a result, the mixture
is remixed in a certain extent, thus causing mass transfer between the two phases.

For precaution, each set of experiment should be repeated at least 3 times to obtain multiple
readings. The degree of the cloudiness of the mixture after titration should be observed and
compared between one another to obtain consistent experimental results. Meanwhile, to avoid
contamination of the samples prepared, all the glassware used for the preparation should be
cleaned with tap water, rinsed with distilled water and let it dry before reusing it. Furthermore,
to tackle with the loss of butyl acetate and acetic acid through vaporization, the opening of the
conical flask or any container holding the mixture should be covered. Besides, the distance
between the fume chamber and the refractometer should be reduced to reduce the time for the
mixture to expose to the surroundings. Lastly, to avoid entering of the air into the separating
funnel, the opening valve should be opened slightly to collect the sample needed. If agitation
occurs due to the formation of bubbles, more time should be used to wait for the equilibrium
to be re-established.

4.0 Conclusion
A liquid-liquid ternary diagram had been plotted using the experimental data obtained and the
organic rich and aqueous rich calibration curve. Plait point and tie lines are determined.
Linearization of Othmer-Tobias correlation verifies the credibility and consistency of the
experimental data in forming the tie lines. Based on ternary diagram, the water is found to
dissolve slightly in butyl acetate and vice versa in the absence of acetic acid. Meanwhile, acetic
acid is soluble in both butyl acetate and water. When comparing with the predicted curve using
M-UNIFAC, the M-UNIFAC model is not suitable to be used to predict the liquid-liquid
extraction ternary system.

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