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EXPERIMENT 3

TERNARY SYSTEM
A Laboratory Report in Partial Fulfilment of the Requirements in Chem117 Laboratory

DAGONDON, VANESSA OLGA


CAGAMPAN, JOHN SULUMOR
(Group 1, Cluster 1)
With
Blyth Angela Balgos
Christine Debbie Shanne Angeles
(Group 2, Cluster 1)

Chem117 Laboratory Physical Chemistry II


Section 1

Performed on March 7, 2016


Submitted on March 28, 2016

Mr. Arnold Gaje, RCh


Laboratory Instructor

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ABSTRACT

The ternary phase diagram of partially miscible liquids: water acetic acid chloroform
was constructed and examined. Water and chloroform are immiscible liquids. Addition of acetic
acid increases the mutual solubility of these two liquids. The solubility curve generated in the
ternary phase diagram shows the transition of the system from a one phase to a two phase
system. A tie line in a ternary phase diagram connects the two phases existing in equilibrium. All
points along a tie line have the same ration of water and chloroform. The length of a tie line
decreases as it approaches the plait point or the point at which three phases exist in equilibrium.
Determination of the tie lines and the plait point were attempted. However, failed due to a
deficient data, the anticipated tie lines and plait point gave an estimate of the actual values. It is
recommended to review the procedures thoroughly to avoid lacking and loss of data.

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INTRODUCTION
Mutual solubility between component liquids of a particular mixture is an essential
knowledge applicable in many fields of science including metallurgy, petrology, mineralogy,
pharmaceuticals, and etc. For example in making a pharmaceutical formulation, multiple
components are needed to be mixed in homogeneous form. This can be done by knowing the
exact ratio of each component to be mixed in accordance to conditions (i.e. temperature, pressure
and composition) such that the resulting formulation is homogenous (Sinko and Singh, 2006). In
this experiment, the three component mixture of water acetic acid chloroform will be
examined.
According to the Gibbs phase rule, information regarding phase equilibria can be
predicted as follows:
(1)

f =c p+2
where f is the variance or the number of variables needed to be specified to describe a

particular system, c is the number of components and p is the number of phases. The number 2
represents the variables temperature and pressure. At constant temperature and pressure,
f =c p
(2)
In a three component system at constant temperature and pressure,
f =3 p
(3)
Where the phase can be 1 if all components are completely miscible with one another and
2 if only 2 of the 3 components are completely miscible with each other and other component is
only partially miscible with either of the two components. If the phase is 1, then the variance is 2
which represent the compositions of the two components needed to describe the system.
Consequently, if there 2 phases present in the system then the variance would result to 1 which
indicates the composition of one of the components needed to describe the system. This
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information can be obtained from a phase diagram of a three component system or ternary
system (Atkins, 2010).
The phase diagram for ternary systems is represented using an equilateral triangle (Fig.
1). The compositions of the three components are showed in this diagram such that each apex
represents 100% of each of the component in the system. These diagrams are based on the three
properties of equilateral triangles: (1) the sum of the perpendicular distances from any point to
each side of the diagram is a constant equal to the length of any of the sides; (2) mixtures lying
on any line connecting a corner with the opposite side contain a constant ratio of the components
at the ends of the side; (3) mixtures of any two compositions lie on a straight line connecting the
two points on the ternary diagram. Compositions represented on a ternary diagram are usually
expressed in mole fraction, mass fraction and weight or volume percentages (Reamer, et. al,
1949).
One of the features of a ternary phase diagram is a solubility curve. When a system
contains two immiscible components, the third component, which is miscible with all the other
components, increases the mutual solubility of the two immiscible components. A solubility
curve is the point of transition from a two-phase to a one-phase system. A tie line is the line
connecting the points signifying solutions of two different phases existing in equilibrium with
each other. These solutions are called as conjugate solutions. As the amount of the third miscible
component increases in the system, the tie lines becomes shorter and shorter until it approaches a
critical point on the curve called the plait point. At this point, the conjugate solutions are of
identical composition and the tie line appears to be a point in the boundary of the solubility curve
(Chua, et. al., 1996).
The main purpose of this experiment is to construct a ternary phase diagram including the
solubility curve for the water acetic acid chloroform system. This experiment has four main
objectives: (1) to construct the solubility curve by preparing mixtures of different compositions
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and titrating them with water or chloroform; (2) to draw the anticipated tie lines inside the
solubility curve and to select points on the tie lines that correspond to the mixtures; (3) to prepare
these mixtures and determine each of their compositions; (4) to determine the experimental tie
lines and plait point.

Figure 1.

Example of

Ternary Phase

Diagram

which includes a

solubility

curve and a tie line

connecting

two boundary points

in the
solubility curve (Sinko and Singh, 2006).

METHODOLOGY
The method adapted in this experiment compromises of two major parts: (1) construction
of the solubility curve; (2) the determination of the experimental tie lines and plait point. The
experiment is done by clusters. Group 1 and group 2 are adjoined in cluster 1. The work load is
divided within the members of the cluster.
The reagents used in this experiment are the following: glacial acetic acid, distilled water,
chloroform and standardized 0.25M NaOH. Prior to the experiment, an approximate of 0.25M
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NaOH was prepared and was standardized with KHP with phenolphthalein as an indicator.
Preparation and standardization of the NaOH was done by the monitor.
The first part of the experiment is the construction of the solubility curve of the water acetic acid chloroform system. Prior to the experiment, densities of water, acetic acid and
chloroform at 25oC were obtained from the CRC Handbook (Table 1).
Table 1. Density Data obtained from the CRC Handbook
Reagent

Density (g/ml)
0.997048

Water
Acetic Acid

1.484

Chloroform

1.0492

These values were used to prepare 25 grams of each of the 8 runs indicated in Table 2.
The following formulas were used to calculate the volume of chloroform/water and acetic acid to
be mixed:

ml water chloroform=

25

( 100n +1) (

water / chloroform

where n=

w
Acetic acid
w

ml acetic acid=25 mlml water chloroform


Table 2. Runs prepared in the construction of a solubility curve
Runs

Composition (by weight of HOAc)

A1

10% in water

A2

25 % in water

A3

40 % in water
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A4

60 % in water

B1

10 % in chloroform

B2

20% in chloroform

B3

40% in chloroform

B4

60% in chloroform

The preparation of the run was done using a buret for accurate measurements. Of these 8
runs, 4 were mixtures of acetic acid and water (Run A) and the other 4 were mixtures of acetic
acid and chloroform (Run B). The mixtures in Run A were titrated against chloroform and those
in Run B were titrated against water. The mixtures were titrated slowly with vigorous shaking
until the first appearance of turbidity in the mixtures. The volume of water and chloroform used
were recorded. The volume of water, acetic acid and chloroform in each mixture were
transformed into weight fractions using the following formula:
Wt . Fraction(component )=

vol . of component component

vol. of eahc component eahc component

These compositions expressed in weight fractions were plotted in a ternary diagram using free
software ProSim Ternary Diagram.
The next part of the experiment was the determination of the experimental tie lines. Five
anticipated tie lines were drawn inside the solubility curve. The midpoints of these tie lines were
obtained along the compositions of acetic acid, water and chloroform. 50 ml of the five mixtures
corresponding to the five chosen midpoints obtained from each tie line were prepared (Table 4).
The volume of each component of the mixture was computed using the formula:

ml component =

wt . of mixture wt . of component
component
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wt . of mixture=
where

50

((

wt . H 2 O
wt . CHCl 3
wt . HOAc
+
+
H 2O
CHCl3
HOAc

)(

)(

))

Each mixture was prepared in a separatory funnel. The mixture was mixed thoroughly until the
two layers separate completely. The two layers were separated into an Erlenmeyer flask and
weighed using the SHIMADZU Analytical Balance available in the laboratory. Two ml of each
layer were pipetted out and was titrated against the standardized NaOH solution. The 2ml aliquot
from each layer should have been weighed but due to some misdirection, it wasnt weighed and
therefore resulted to a loss of data. Nevertheless, the amount of acetic acid in the 2ml aliquot of
each layer was calculated using the formula:

( Molarity of HCl )

Wt . FractionHOAc =

HOAc
60.05 g
( volume of HCl used ) (
( 11mol
)
mol NaOH
mol HOAc )
Total wt . of layer

The clusters data obtained from the first part was discarded because the data from the
second cluster was used instead in the second part of the experiment. Therefore, the data
gathered in this experiment is of the second cluster. The workload on the second part of the
experiment was divided in the clusters of the class.
RESULTS
The following figures and tables shows the results obtained to achieve each the listed
objectives of this experiment:
Table 3. Summary of the mixtures prepared to construct the solubility curve
RUN

Water

HOAc

Chloroform

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1A
2A
3A
4A
1B
2B
3B
4B

Volume

Weight

Weight

Volume

Weight

Weight

Volume

Weight

Weight

(mL)

(g)

fraction

(mL)

(g)

fraction

(mL)

(g)

fraction

22.6
18.8
15
10
0.1
0.6
2.9
7.6

22.5333
18.7445
14.95572
9.97048
0.099705
0.598229
2.891439
7.577565

0.801
0.704
0.540
0.320
0.00397
0.0234
0.104
0.234

2.4
6
9.5
14.3
2.4
4.8
9.5
14.3

2.51808
6.2952
9.9674
15.00356
2.51808
5.03616
9.9674
15.00356

0.0896
0.236
0.360
0.480
0.100
0.197
0.357
0.461

2.1
1.1
1.8
4.2
15.2
13.5
10.1
6.7

3.1164
1.6324
2.6712
6.2328
22.5568
20.034
14.9884
9.9428

0.111
0.0613
0.0965
0.199
0.899
0.783
0.537
0.305

Table 3 shows the two runs, each with four mixtures, along with their corresponding
composition in the mixtures expressed in volume, weight and mass fraction. The mass fractions
of each of the component in the mixture (water acetic acid chloroform) are used to construct
the solubility curve shown in Figure 2.

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Figure 2. Experimental Ternary phase diagram of water acetic acid chloroform system
(created from ProSim Ternary Diagram)
Figure 2 shows the solubility curve of the system which shows the restricted solubility of
water and chloroform. Manually, anticipated tie lines are drawn below the solubility curve.
Figure 3 shows the manual ternary diagram constructed from the data obtained. Mixtures
corresponding to midpoints of these anticipated tie lines were prepared. The chosen points are
connected vertically until such point on the boundary of the curve. This point corresponds to the
mixture of plait point which is 44.8% HOAc, 20.8% water and 34.3% chloroform.

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Figure 3. Manual Ternary Phase Diagram: Solubility curve including the anticipated tie lines and
plait point (Acasio, 2016)
Table 4. Summary of the chosen mixtures corresponding to the points on the anticipated tie lines

Water

HOAc

Chloroform

Mixture
No.

1
2
3
4
5

Volume

Weight

Weight

Volume

Weight

Weight

Volume

Weight

Weight

(mL)

(g)

fraction

(mL)

(g)

fraction

(mL)

(g)

fraction

20.6

20.5

0.342

9.60

10.1

0.168

19.8

29.4

0.490

18.1

18.1

0.301

13.1

13.8

0.228

18.8

27.9

0.464

24.2

24.1

0.431

14.9

15.7

0.280

10.9

16.7

0.289

14.7

14.7

0.251

19.8

20.8

0.355

15.5

23.0

0.394

12.5

12.5

0.215

23.5

24.6

0.425

14.1

20.1

0.360

Table 4 shows the composition of the chosen points in the lines. The volume, weight and
mass fraction of each 6 mixtures chosen were indicated in the table. As shown in Table 4, five
mixtures were prepared. Each of this mixture corresponds to a point chosen on the tie line.
During the experimentation, however, it is important to take note that a wrong mixture was
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prepared on mixture 3. The mass fraction of water and chloroform were exchanged. Due to this
error, the experimental tie line to be constructed based on mixture 3 will be considered
erroneous. After these mixtures were prepared, they were let to separate into layers. These layers
were weighed and titrated with standard 0.25 M NaOH. Table 5 shows the summary of data for
the determination of the amount of HOAc to construct experimental tie lines and plait point.
Table 5. Summary of Data for the determination of the amount of HOAc to construct
experimental tie lines and plait point
Mixture
1
2
3
4
5

Layer
Lower
Upper
Lower
Upper
Lower
Upper
Lower
Upper
Lower
Upper

Mass(g)
25.5047
30.194
26.3118
30.5391
16.0329
24.5760
21.9121
34.4813
12.8673
39.6547

Volume for Titration (ml)

Amount HOAc

14.8
39.3
18.3
50
16.05
48.3
31.95
70.5
51.8
76.2

(Weight fraction)
0.00839
0.0188
0.0101
0.0237
0.0145
0.0284
0.0211
0.0296
0.0582
0.0278

This includes the weight of each of layers separated in each mixture; the volume of the
standard NaOH used; and the composition of acetic acid in each layer expressed in weight or
mass fraction. As seen in Table 5, the weight fractions of acetic acid obtained in each layer are
very low values. This is because these values are the composition of acetic acid on the 2 ml
aliquot taken from the original separated layers. Therefore, a factor must be multiplied to these
values to take account the whole layer and not just the 2 ml aliquot. This factor should include
the weight of the 2 ml aliquot but because it was not weighed during the experimentation, the
factor cannot be calculated and the real composition of acetic acid in each layer cannot be
determined. Thus, the experimental tie lines and plait point cannot be determined.
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DISCUSSION
The system of water acetic acid chloroform involves partially miscible liquids. Water
and chloroform are almost completely immiscible with each other at room temperature. When
mixed, these two components form two layers: an aqueous layer containing small portions of
chloroform and a chloroform layer containing small portions of water. Acetic acid, on the other
hand, is miscible with water and chloroform. The addition of acetic acid to a heterogeneous
mixture of water and chloroform will increase the mutual solubility of water and chloroform
such that the aqueous layer will contain more of chloroform and the chloroform layer will
contain more of water.
This behaviour can be explained by the fact that acetic acid behaves as an amphipilic
solvent. The molecules of acetic acid contain a hydrophilic moiety, the carboxylic group,
COOH, and the alcoholic one, OH, and a hydrophobic one, the CH 3 and the CH3CH2 one.
Acetic acid can interact with water through its hydrophilic constituents, and also with chloroform
through its hydrophobic constituents. This results to a mutual solubility of water and chloroform
(de Moura et. al., 2013).
In the experiment, Run A which composed of acetic acid and chloroform and Run B
which composed of acetic acid and water were titrated with water and chloroform, respectively
until the first appearance of turbidity. This procedure provides us with the composition of the
system entering the two phase system. This transition from a one-phase to a two-phase system is
depicted in the solubility curve in figures 2 and 3. The area inside the solubility curve indicates a
two phase system. Outside the curve indicates a single phase system wherein the three
components are miscible with one another.
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The tie lines drawn in figure 3 connect two compositions in each phase of the system
existing in equilibrium. The relative amounts of the two phases can be estimated by using the
lever rule. It is shown in figure 3 that the tie lines decrease in length as it approaches the plait
point. However, it should be noted that these values are anticipated values and yet to be
verified experimentally. This was done by taking account the fact that all points lying in a tie line
correspond to chloroform and water present in the same ratio. In order to determine the
composition of each phase connecting a tie line, a mixture which corresponds to a point from the
anticipated tie line was prepared. Since this mixture was taken from a point below the
solubility curve, the mixture prepared will be of two phases. These phases are let to separate
from each other: the lower layer contains more of the chloroform because it is denser than water;
the upper layer contains more of water. The acetic acid compositions of each of the layers were
determined to know the composition of the two phases in equilibrium and thus constructing a tie
line. Take note that only the composition of the acetic acid is needed to define the system
because the phase below the solubility curve is 2 and therefore the variance or degrees of
freedom according to the Gibbs phase rule is 1.
In the experiment, however, the tie lines were not determined because of the lack of data.
The 2 ml aliquot in each phase wasnt weighed and therefore the acetic acid composition in the
mass of the total phase collected wasnt taken account of. Only the acetic acid composition in the
2 ml aliquot can be determined. However, a few observations pertaining to the acetic
compositions can be deduced. (1) The amount of acetic acid is not the same in the two phases.
This means that the tie lines are not straight lines parallel to one another. (2) The composition of
acetic acid in the lower and upper layer increases as it approaches the anticipated plait point. (3)
The upper and lower layers of mixture 4 have almost the same composition of acetic acid. This
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signifies that the experimental plait point has a composition near to the composition of that of
mixture 4. Take note that when the acetic acid composition of the two layers will be equal, that
mixture corresponds to the mixture at the plait point where the three phases are present in
equilibrium. The plait point is also the boundary point between the two phases of the solubility
curve. The left side of the solubility curve corresponds to the upper layer phase which is
abundant in water and the right side is of the lower layer phase which is abundant in chloroform.
Figure 4 shows the ternary phase diagram of the same system obtained experimentally by
Othmer, et. al, 1960. The plait point in this study was determined to be: Acetic acid: 36.5%,
Chloroform: 52.2% and water: 11.3% (Othmer et. al., 1960). Since there was no plait point
determined in the experiment, this composition for the plait can only be compared to the
anticipated plait point which is 44.8% Acetic acid, 34.3% chloroform and 20.8% water. As
expected, the anticipated tie line differs from the actual plait point.

Figure 4. Ternary Phase Diagram of Water Acetic acid Chloroform system (Othmer, 1960)
CONCLUSION
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The ternary phase diagram the ternary system of water acetic acid chloroform was
constructed and examined. Water and chloroform are immiscible liquids. The mutual solubility
of these two liquids is increased by adding a third component, acetic acid which is soluble in
both liquids. In the experiment, the solubility curve of this system was constructed by preparing
two sets of mixtures: A, mixtures of acetic acid and chloroform and B, mixtures of acetic acid
and water. Run A mixtures were titrated against water and Run B against chloroform until the
mixture becomes turbid. Plotting these compositions in a triangular diagram will give the
solubility curve of the system. The solubility curve acts as the boundary between regions where
the system exists in two phases and one phase. Below the solubility curve, the system exists in
two phases. Consequently, outside the curve means that the system exists only in one phase.
Another features of a ternary phase diagram are the tie lines and plait point. Tie lines are
the lines connecting the composition of the two phases existing in equilibrium. The relative
amounts of the phases in a tie line can be determined using the lever rule. All the points on a tie
line correspond to chloroform and water present in the same ratio. Plait point, on the other hand,
is the point at which three phases exists in equilibrium. This is also the point that margins the left
and right curves that represent the two phases existing in equilibrium. Tie lines and the plait
point can be determined experimentally by preparing mixtures that correspond to the midpoint of
the anticipated tie line drawn inside the solubility curve. It is observed that the length of the tie
line decreases as it approaches the tie line. These mixtures were let to separate into layers: lower
layer rich in chloroform and an upper layer rich in water. Since these mixtures are all present in
two phases, only one composition is needed to describe the system. The acetic acid compositions
of each of the layers were determined. However, this wasnt done successfully in the experiment

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because of the lack of data, particularly the weight of the 2 ml aliquots which the acetic acid
composition was determined.
Since not all the objectives of the experiment were met accordingly, this experiment is
considered to be unsuccessful. To avoid instance as such, procedures must be thoroughly
examined and reviewed to avoid misdirections and thereby avoid any lacking and loss of data.
REFERENCES
Atkins, P.; de Paula, J. Physical Chemistry Ninth Edition; Oxford University Press: Great Britain,
2010; pp. 176-181.
Chua et. al. Energetics of Aerobic and Anaerobic Reactions. In Experiments in Physical
Chemistry Part One. Institute of Chemistry: University of the Philippines-Diliman, 1996;
pp. 55-59.
De Moura, S. L., dos Santos, J. A. V., da Silva, F. C. M. Thermodynamic study of the liquidliquid equilibrium water chloroform acetic acid. American Journal of Physical
Chemistry. November 2013; 2(6): 17-121.
Othmer, D. F., Ku, P. L. Solubility Data for Ternary Liquid Systems: Acetic Acid and Formic
Acid Distributed Between Chloroform and Water. Journal of Chemical and Engineering
Data.1960, 96, 42-46.
Reamer, H.H., Fiskin, J.M., and Sage, B.H. 1949. Phase Equilibria in Hydrocarbon Systems. Ind.
Eng. Chem. 41 (12): 2871-2875.
Sinko, P. J.; Singh, Y. Martins Physical Pharmacy and Pharmaceutical Sciences; Lippincott
Williams & Wilkins: Philadelphia, PA 19106, 2006; pp 182-184.
Page 17 of 20

ACKNWLEDGEMENTS
We would like to express our deepest gratitude to our laboratory classmates and
especially to our cluster for working with us diligently, to our instructor for guiding us during the
experiment, and to the chemistry department for providing us the materials for the experiment.
CONTRIBUTION OF AUTHORS
Dagondon authored this laboratory report including the data analysis. Cagampan was in
charge with the laboratory report for Experiment 4. Work load on both experiments (i.e. writing
the laboratory report and doing the experiment) were divided fairly between Dagondon and
Cagampan.
APPENDICES
APPENDIX A: Tables and Figures
Table 6. Standardization Data of HCl

Trial

Mass of KHP (g)

Volume used for


Titration (ml)

Molarity (M)

0.8000

16.25

0.241067326

0.8002

16.25

0.241127592

0.8002

16.30

0.240387937

Average

0.240860952 M

APPENDIX B: Sample Calculations

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Volume of acetone and water/chloroform (Refer Table __ on Appendix: A)


25
w
ml water chloroform=
where n= Acetic acid
w
n
+1 ( water / chloroform )
100

ml acetic acid=25ml water chloroform


For Run 1A
ml water =

25

10
+ 1 ( 0.9970480 )
100

=22.6

ml acetic acid=2522.6=2.4
For Run 1B
ml chloroform=

25

10
+ 1 ( 1.484 )
100

=15.2

ml acetic acid=2515.2=9.8
Weight fractions of acetic acid, chloroform and water (Refer Table __ on Appendix: A)
For Run 1A
22.6 0.997048
X water =
=0.801492
( 22.6 0.997048 ) + ( 2.4 1.049 ) + ( 2.1 1.484 )

X HOAc=

2.4 1.049
=0.0895591
( 22.6 0.997048 )+ ( 2.4 1.049 ) + ( 2.1 1.484 )

X CHCl =

2.1 1.484
=0.110839
( 22.6 0.997048 ) + ( 2.4 1.049 ) + ( 2.1 1.484 )

Volume of acetic acid, chloroform and water for the mixtures in a tie line
For Mixture 1
HOAc = 16.8%
Water = 34.2%
Chloroform = 49.0%
50
wt . of mixture=
=60.000726 g
16.8
34.2
49.0
+
+
1.0492
0.997048
1.484

((

ml HOAc=

)(

)(

))

60.000726 16.8
=9.61 ml
1.0492
Page 19 of 20

ml Water=

60.000726 34.2
=20.6 ml
0.997048

ml CHCl 3=

60.000726 49.0
=19.8 ml
1.484

Standardization of 0.25 NaOH


Trial 1
1 mol KHP 1 mol NaOH
( 0.8000 g )
204.2 g
1 mol KHP
M NaOH =
=0.241 M
0.01625 L

)(

Average M NaOH =0.241 M


Amount of Acetic Acid
For Mixture 1
Upper Layer
Wt . FractionHOAc

25.5047 g

30.194 g

mol NaOH 1 mol HOAc


60.05 g
0.241
( 0.0148 L ) (
(
)(
L
1mol NaOH )
mol HOAc )
=
=0.008393071

Lower Layer
Wt . FractionHOAc

mol NaOH 1 mol HOAc


60.05 g
0.241
( 0.0393 L ) (
(
)(
)
L
1mol NaOH
mol HOAc )
=
=0.018825708

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