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Done By

Group

: A0098214A

ERIC KHONG MUN KIT

A0097528N

RON SIM

A0105725L

ZHU KAI

: W7

Date of Experiment: 12/03/14

Demonstrators Signature :

Grade:

1.0 SUMMARY
The objective of this experiment is to determine the phase diagram for three-component liquid
system of Water-Butyl Acetate-Acetic Acid at room temperature and atmospheric pressure. The
experiment was conducted in 2 different parts to construct both the tie-lines and solubility curve
of the ternary phase diagram, which are plotted on the Gibbs triangle.
In the first part of the experiment, 4 samples with different composition of water, butyl acetate
and acetic acid were well agitated with a mechanical shaker for at least an hour and allowed to
attain equilibrium. Since acetic acid is soluble in water and butyl acetate, the amount of acetic
acid distributed in the aqueous and butyl acetate phase can be determined by separating the
aqueous and butyl acetate components before titrating with NaOH. The mass percentage of each
component was calculated and used to plot the tie-lines.
For the second part of the experiment, 11 sets of water-butyl acetate samples with 0% to 100%
concentration range of butyl acetate were prepared. These samples were then titrated with acetic
acid until a homogenous phase was obtained. The volume of acetic acid added was recorded. It
was used to determine the mass composition of each individual component in the mixture so that
the points can be plotted for the construction of the solubility curve.
The Plait Point, defined as the critical mixing point where the tie-lines converge, can be obtained
from the solubility curve and tie-lines. With the completed phase diagram, we are able to
determine the physical state of any Water- Butyl Acetate-Acetic Acid liquid systems, be it
homogeneous or not. From our data, the Plait Point was determined to be 17% butyl acetate,
42% water and 41% acetic acid by weight.

2.0 TABLE OF CONTENT


Section

Page(s)

1.0 Summary

2.0 Table of Contents

2
2

3.0 Tabulation and Calculations

3-5

4.0 Discussion

6-8

5.0 Source of Error

8-9

6.0 Conclusion

7.0 Notation

10

8.0 Reference

10

9.0 Appendix

11-14

3.0 TABULATION AND CALCULATION


The following are the combination of results obtained from the experiment and the tabulated data
for the construction of both solubility curve and tie lines on the ternary diagram of butyl acetatewater-acetic acid system.
(1) To determine the solubility curve of the system on triangular coordinate paper.
For this, we shall use the results from the series of 11 samples of selected composition of water
and butyl acetate:Table 1: Titration results for 10ml of Butyl Acetate-Water sample with Acetic Acid
Experimental Results

Sampl
e No.

Volume
of
Water
(mL)

Volume
of
Butyl
Acetate
(mL)

1
2
3
4
5
6
7
8
9
10
11

0.50
1.00
2.00
3.00
4.00
5.00
6.00
7.00
8.00
9.00
9.50

9.50
9.00
8.00
7.00
6.00
5.00
4.00
3.00
2.00
1.00
0.50

Calculated values
Volume
of
Acetic
Acid
required
(mL)
2.20
2.60
4.20
4.90
5.65
6.00
6.60
6.60
7.00
5.80
4.05

Mass
of
water
(g)

Mass
of
butyl
acetate
(g)

Mass
of
acetic
acid
(g)

Mass
faction
of
water

Mass
fraction
of butyl
acetate

Mass
fraction
of acetic
acid

0.50
1.00
2.00
3.00
4.00
5.00
6.00
7.00
8.00
9.00
9.50

8.36
7.92
7.04
6.16
5.28
4.40
3.52
2.64
1.76
0.88
0.55

2.31
2.72
4.41
5.14
5.93
6.29
6.92
6.92
7.34
6.08
4.25

0.045
0.086
0.149
0.210
0.263
0.319
0.365
0.423
0.468
0.564
0.665

0.748
0.680
0.523
0.431
0.347
0.281
0.214
0.159
0.103
0.055
0.038

0.207
0.234
0.328
0.359
0.390
0.400
0.421
0.418
0.429
0.381
0.297

Sample calculation for mass of a compound:Taking water for sample 1 as an example:3

mass of water ( g )=volume of water density ofwater (g cm1 )


mass of water ( g )=0.50 1.000=0.50 gram
Sample calculation for the mass fraction of each compound:Taking water for sample 1 as an example again:mass fraction of water =

mass of water the sample


total mass of the mixture

mass fraction of water =

0.50
=0.045
0.50+ 8.36+2.31

Then, the points were plotted to give the solubility curve of butyl acetate-water-acetic acid
ternary system as the following:-

Kindly refer to
appendix A for a
clearer and larger
ternary diagram

(2) To establish the tie-lines and estimate the plait point


In order to establish the tie lines, we shall use the results from the titration of 4 specified samples
with NaOH.
Table 2: Results for aqueous phase and BA phase titration with 0.501M sodium hydroxide
Aqueous Phase
Sample Total
Total mass Volume of
Concentration Number of Mass of
volume of
of
NaOH required of NaOH
mole of AA acetic acid
aqueous
aqueous
to neutralize
provided
in 2mL
in aqueous
phase (mL) phase (g)
2ml sample
sample
phase (g)
(mL)
(moles)
1
63.0
64.26
8.10
0.501M
4.05810-3 7.82

Mass fraction
of acetic acid
in aqueous
phase (%)
12.17
4

2
3
4

1
2
3
4

59.0
54.0
45.0

60.18
55.08
45.90

18.30
26.50
28.40

Total
volume of
BA phase
(mL)

Total mass
of BA
phase (g)

37.0
41.0
46.0
55.0

37.04
37.72
42.32
50.60

Volume of
NaOH required
to neutralize
5ml sample
(mL)
9.60
24.10
47.30
55.10

BA Phase
Concentration
of NaOH
provided

0.501M

9.1710-3
13.2810-3
14.2310-3

16.56
21.94
19.59

27.52
39.83
42.68

Number of
mole of AA
in 5mL
sample
(moles)
4.81010-3
12.0710-3
23.7010-3
27.6110-3

Mass of
acetic acid
in BA
phase (g)

Mass fraction
of acetic acid
in BA phase
(%)

2.136
5.938
13.08
18.22

5.76
15.74
30.91
36.00

Sample calculation for the total mass of aqueous/BA phase:Taking sample 1 in aqueous phase for example:mass of phase=density of phase ( provided ) volume of the phase
mass of aqueous phase=1.02

g
63 ml=64.26 g
ml

Then, for the calculation of number of mole of AA in the aqueous phase,


We first have to understand that one mole of NaOH is required to neutralize one mole of
CH3COOH. Therefore, their molar amount must be equal at the end point.
Number of mole of AA 2 ml aqueous phase , N AA=Number of mole of NaOH
Number of mole of AA 2 ml aqueous phase , N AA=0.501 M x 9.61 103 L=4.058 103
For the mass fraction of AA in aqueous/BA phase, we convert the number of mole of AA from
2mL of the sample into the mass fraction. Example is shown below
volume of phase
Mr AA
volume o f sample
mass fraction of AA aquous phase=
total mass of aqueous phase
N AA

Where NAA is the number of mole of AA in 2mL sample and MrAA = molecular weight of AA.
Volume of sample used for titration for the BA phase is 5ml while the aqueous phase is 2ml.
Taking aqueous phase of sample 1 for example:( 4.058 103 ) 63 ( 60 )
2
mass fraction of AA aqueous phase ( sample 1 )=
=12.17
64.26

( )

Using the mass fraction obtained from Table 1, we can construct the solubility curve, on the
other hand, the mass fraction of Table 2 can be used to make 4 separate tie lines on the same
ternary diagram. The resultant ternary diagram is as follows:-

Kindly refer to
appendix A for a
clearer and larger
ternary diagram

4.0 DISCUSSION
(1) Define and discuss on the Plait Point on your phase diagram and explain the method of
construction.
For a 3-component liquid system, the Plait Point is the point where the 2 coexisting phases of
partially miscible components approaches each other in a same composition regarding to the
density, at which a single phase of the system starts to occur. This point is also called the critical
mixing point of the system.
From the definition, the plait point should locate at where the tie-lines converge to. And it is not
necessarily at the maximum point on the solubility curve. To prove the plait point attributes the
above properties, the analysis is started from Gibbs Phase Rule Equation. For a 3-component
liquid system, the equation is F = 5 P. For this experiment the temperature and pressure is
specified and the equation reduces to F = 3 P. On the solubility curve, 2 phases coexists, leading
to F = 1. At any point except plait point, by specifying the mass fraction of one component in
either the aqueous or the BA phase, the overall composition and the other phase can be
determined, by drawing a tie-line on the solubility curve. At the plait point, the tie-line becomes
only a single point, and this shows the two phases have the same composition.
To determine the plait point graphically, the 4 tie-lines obtained and discussed in the tabulation
and calculation part are needed. Referring to the figure in Appendix A, two lines parallel to the
opposite axis are drawn downwards, from the two ends of each tie-line. The intersection points
of these two lines are noted and form a new curve. Then the plait line can be determined at
which this curve intersects with the solubility curve (shown in the figure in Appendix A). And
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specifically, the point is at a composition of 41% for acetic acid, 17% for butyl acetate and 42%
for water.
(2) 100gm of mixture of 37% acetic acid and 63% butyl acetate are added to 60gm water
and shaken rigorously at temperature until equilibrium is attained. Determine the weights
and composition of the two phases using the phase diagram obtained.
From the information provided, we can construct a table to determine the mass fraction of each
component in the ternary system
Table 3: Tabulation of mas of components to solve for Discussion Question 2
Component
Mass of
Total mass of the
Mass fraction of each
component (g)
ternary system (g)
component
Acetic acid
37g
0.231
Butyl acetate
63g
160
0.394
Water
60g
0.375

We can then translate the mass fraction into points on the ternary diagram:-

Kindly refer to
appendix A for a
clearer and larger
ternary diagram

From reading of the ternary diagram, the compositions of the two phases are the following
BA phase (read from point A): 18% acetic acid 78% butyl acetate 4%water
Aqueous phase (read from point B): 29% acetic acid 3.5% butyl acetate 67.5% water
Using lever rule, it can be found that the ratio between line segments AC to CB is 21:19,
Therefore, we can also establish that
mass of BA phase
21
=
mass of aqueous phase 19

Then, we can find that the mass of BA phase = (21/19) (160-mass of BA phase) since mass of
both phase adds up to 160g
By solving the equation above, mass of BA phase = 76g while mass of aqueous phase = 84g
From these readings, we can also gauge the accuracy of the ternary diagram prepared.
Mass of butyl acetate in BA phase = 59.28g
Mass of butyl acetate in aqueous phase = 2.94
Supposed total mass of BA in the whole system = 63g
The deviation of expected value = 63 (59.28 + 2.94) = 0.78g
Percentage error = 0.78/63 100 = 1.24%
(3) Briefly discuss on the effect of the temperature and pressure on the phase diagram.
Temperature
Water and butyl acetate has very low solubility in each other and the addition of sufficient acetic
acid is required for the 2 phases to coalesce and form a homogenous phase. When temperature
increases, the kinetic energy of molecules increases. This allows for both liquids to overcome
their separation barrier and become more soluble. Therefore, with increase in temperature, lesser
amount of acetic acid will be required for the 2 phases to become homogenous. This will mean
that the solubility curve on the phase diagram will shift away from the axis of acetic acid with
increasing temperature.
In addition, with increase in temperature and solubility of water and butyl acetate, there is lesser
area in the phase diagram where the 2 phases can coexist. Hence, the area enclosed by the
solubility curve decreases with increasing temperature. As temperature continues to increase, it
will reach a point where phase separations would no longer occur. This is known as the Upper
Critical Solution Temperature. There will be complete miscibility of all 3 components from this
particular temperature onwards.
Pressure
Since liquids are considered incompressible, the thermodynamic property changes due to
pressure are negligible as this experiment involves a 3 component liquid system. For a very high
or low pressure system however, such changes can become significant, but for this experiment
which is conducted at atmospheric pressure, we can safely assume that variations in pressure will
cause negligible effects on the solubility curve on the phase diagram.

5.0 SOURCES OF ERROR


(1) When the calculation being done, the density of each phased used was assumed to a fixed
number. And this differs to the real situation. Even if it is in the same phase, when the
compositions change, the density would also change. This point would cause an error on plotting
the tie-line, solubility curve and the successive Plait Point.

(2) In the 3rd step of the experimental procedure, it is difficult for one to determine the end point
of the titration. By naked eyes, it is imperceptible whether the single homogeneous phase is
formed among each single drop. Therefore, the results would involve certain degree of
estimation. This also results in an inaccuracy of the diagram.
(3) For the titration part, another error can come from the methyl red indicator. As the indicator is
also in an aqueous phase, some water would be added in by using the indicator. The water added
in would influence the composition of the original liquid to be tested.
(4) The reagents used in the experiment such as BA and acetic acid are highly volatile and could
have evaporated. The amount measured of the reagents could be different from the beginning.
To minimize this error, the conical flasks were kept stoppered when not in use. However, a small
amount of evaporation could not be avoidable.
(5) Parallax error might have been introduced when reading off from the burette due to the
restriction from the experimental set-up in the fumehood. This could introduce some errors in the
titration results obtained, and affect the position of tie-lines and plait point.

(6) The separating funnels were used to separate the aqueous phase from the butyl acetate phase
which could introduce significant error in the volume of each phase obtained. More accurate
electronic separating device should be used to minimize this source of error so that the 2 phases
can be better separated and reflect a more accurate result for acetate composition calculation
during the titration process.
(7) The three mixtures were only assumed to have reached equilibrium after agitation for an hour
when this might not be the case. More time should be given for the mixing of the mixtures such
that equilibrium can be more accurately assumed. An equilibrium point has to be achieved in
order to obtain accurate results for the tie-line.

6.0 CONCLUSION
The objectives of the experiment were mainly achieved by plotting the solubility curve of the 3component liquid system of water, butyl acetate and acetic acid (at 1.008 bar and 296.15 K) on
the triangular phase diagram. Tie-lines corresponding to the 4 mixtures of varying composition
and the plait point were also determined by using the experimental data. The plait point was
defined to be at a mass composition of 41% acetic acid, 17% butyl acetate and 42% water. The
literature value of this plait point found in an experiment conducted by Hirata & Hirose at
303.15K is 38.23% acetic acid, 33.24% butyl acetate and 25.53% water. This literature value
seems much different from the one obtained from the experiment. While one factor causing the
difference could be the different temperatures, it is likely to be accrued to a great extent to the
inherent experimental errors discussed in Source of Error section.
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7.0 NOTATION
AA Acetic Acid
BA butyl- acetate

8.0 REFERENCES
Hirata, M., Hirose, Y., Physical Properties of Ternary System Acetic acid-Water-Butyl acetate,
Chemical engineering 407-414, 1963. Retrieved from
https://www.jstage.jst.go.jp/article/kakoronbunshu1953/27/6/27_6_407/_pdf
Ince E & Kirbaslar, 2002. Brazilian Journal of Chemical Engineering, Vol 19, No 2, pp 243-254,
Retrieved from http://www.scielo.br/pdf/bjce/v19n2/10666.pdf
University of Vermont, Equilibrium V. Vermont, 2005. Retrieved from
http://www.uvm.edu/~dsavin/courses/chem162/lectures/eqm5.pdf

9.0 APPENDICES
Appendix A Ternary diagrams
Appendix B Lab T3 Experiment Datasheet
Appendix C Experiment T3 Risk Assessment Form

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APPENDIX A- Ternary Diagrams

Figure 1: Ternary diagram with tie lines plotted based on experimental results

Figure 2: Ternary diagram with points used for Discussion Question 2

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Figure 3: Ternary diagram with constructed lines for determination of plait point.

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