ABSTRACT

Immiscible substances are caused by the solubility properties of liquid. In most

cases for liquids, two immiscible liquids cannot mix even with the addition of a
tertiary component. But the addition of a highly polar substance demonstrates a
change in its solubility.
In this experiment, we used butanol, acetic acid and water as tertiary components.
We created fourteen (14) mixtures of butanol and acetic acid with different
compositions and then they were allowed to achieve thermal equilibrium. Each of
them was then titrated with water (at 25C) until permanent turbidity appeared.
Refractive indexes were then measured by a refractor and then recorded. Water was
then added to the mixture and the mixture was allowed to form separate layers.
Refractive
indexes
were
then
recorded
again
for
each
layer.
Using a ternary plot and the gathered data from the earlier parts, we draw the
boundary between two-phase and one-phase systems and the corresponding tie
lines.
INTRODUCTION
Extraction of constituents by solvent is a very common practice in chemical
processing where a mixture containing separable components is treated with a
solvent in which one or more of the desired components are preferentially soluble.
This type of extraction is called liquid-liquid extraction in which a solution is brought
into contact with a second liquid (solvent) essentially immiscible with the first one in
order to bring about transfer of one or more components from the solution into the
second solvent. It is an effective alternative process to distillation process. Liquidliquid extraction process is the most useful method for purification, enriching and
separation of components of very close volatility and of heat sensitive.
In many cases, butanol is found in its aqueous form. Butanol is an important
laboratory reagent, thus, the study of butanol extraction from its aqueous solution is
fascinating all the time. In this study, in order to find out the proper solvent for the
separation of butanol from aqueous solution, phase equilibrium data and mutual
solubility data were therefore obtained experimentally by using solvents. Separation
factor which is a quantitative index of effectiveness of separation has been
computed from these data.
Separation process in which a solute in a feed stream is extracted by contacting the
feed with a solvent is called solvent extraction. The solute has to be soluble in both
the feed and solvent in order for the extraction to take place. The solvent and the
feed for industrial extraction operations are normally partially soluble in one
another. A ternary system will be formed consists of the feed, solvent and solute.
The composition of such a system can be conveniently represented on an
equilateral triangle plot with each corner of the triangle presenting one of the three
components.
The purpose this experiment was carried out was to determine the bimodal curve
and the typical tie lines of the water-water-butanol acid system. The points on the
bimodal curve was determined using the mass fractions of water, butanol and the
other solvent of mixtures after the it was slowly added until a single phase clear
solution is obtained. The tie line is drawn using the mass fractions of butanol, water
and the other component of mixtures S, with also their mass ratios using trial and
error method. Three phase diagram will be drawn in this experiment.
Page 1 of 11

METHODOLOGY
A. CHEMICALS & APPARATUS

curve, the chemicals involve were distilled water, butanol and acetic acid. Standard glass wares were used (bea

water and 1.0M NaOH. Same apparatus were used as in first part. Separation of phases had been done by mean

of the waste of chemicals had to be followed in the end of the experiment. When doing the titration, it had to be

B. EXPERIMENTAL PROCEDURE
Part 1.
Determined solubility curve had been done by starting with determining the first
two points in the curve which lies on the horizontal axis of the curve. These two
points were the solubility of butanol in water and the solubility of water in
butanol. The cloudy appearance had been the evidence for both solubility. The
other points on the curve were then determined by adding acetic acid in the twophase mixture until it turns back into one phase. The transition could be
observed by the disappearance of turbidity in the stirred solution.

20ml of butanol was placed in an empty Erlenmeyer flask which was

weighed before using. It was weighed again once the butanol was poured
into it. This had been titrated with distilled water giving a cloudy
appearance. Knowing the density of the butanol and water, the mass of
butanol and water could be identified. The mass percentages had been
used to determine the first point in the curve.
This process had been repeated but this time 20ml of water was used. The
second point on the curve could now been determined.

Page 2 of 11

Starting from 20ml of butanol and 5ml of water placed in a 200ml

parafilm-covered Erlenmeyer flask. Acetic acid had been added until
turbidity disappears. The volume of acetic acid added was then recorded.
Addition of 5ml aliquot of water had been done to the mixture from the
previous step and it had been titrated again with acetic acid. It had been
continued until 30 ml water had been added.
Addition of 10ml of aliquot of water was now used and it had been kept
titrated until a total of 110 ml of water had been added.
Volume of acetic acid used in every stage had been recorded.
Knowing the volume and density of the three liquids, their masses could
be computed. Hence, their mass percentages in each stages could be
determined.
Trial 2 had been done to get the average composition of ternary mixtures.
The average composition was then used to plot the points in the curve.

Part2.

In order for the diagram to be completed, a tie lines had been obtained.
For this, preparation of two-phase mixtures was needed. These phases
had to be separated using separatory funnel. These separated mixtures
had to be titrated in order to determine the amount of acid the solutions
contained. The prepared 1.0M NaOH was the base used to titrate the
aqueous acid containing solutions.
The two-phase mixture which had been assigned to our group was
prepared by mixing 30ml distilled water, 15ml butanol and 2ml acetic
acid. This mixture had been placed in the separatory funnel and it had
been allowed to settle for a while.
The two separated mixture had been labeled TP2(Top Phase) and
LP2(Bottom Phase) respectively.
After obtaining two separate mixtures, both had been titrated with 1.0M
NaOH. An indicator had been used; Phenolphthalein to see the color
change right when the mixtures had been titrated. A pale pink color
solution was expected.
The volume of the base which had been used to titrate the mixtures were
the volume of the acid the mixtures contained. Thus, knowing the volumes
and densities of the three liquids involve, the masses of each could now
be determined.
The mass of the two phases could also be computed which was then used
to determine the points for the tie lines.
Trial 2 had also been done.

Page 3 of 11

RESULTS AND DISCUSSIONS

Ternary phase diagrams are 3 component
systems. To construct a ternary diagram it is
necessary to know the three binary systems for
the three components. In this experiment the
three components are butanol, water, and
acetic acid. The sides of the triangle
corresponds to the mole percent of each of the
components with respect to the other two . The
objective of this activity is to be able to come
up with a curve which will show the
concentration
of
each
components
at
equilibrium provided that the amount of
butanol remains constant.
To obtain this, the activity was divided into two parts, the first one was to determine
the two ends of the the curve on the side of the butanol and that of water. No acetic
acid was present during this time. The points on the curve was determined by
titrating the butanol-water system with acetic acid.
A. Solubility of Immiscible Liquids
Table 2-1a Solubility of Butanol in Water
Volume
of Volume
of Mass
of
Butanol
Added
Butanol
Water
20 ml
3.2 mL
16.2 g
Table 2-1b Solubility of Water in Butanol
Volume
of Volume
of Mass
of
Water
Added
Water
Butanol
20 ml
3.7 mL
20 g

Mass
Added
Water
3.2 g

of

Mass
Added
Butanol
3.0 g

of

%
Mass
Butanol

%
Mass
Water

83.51

16.49

%
Mass
Water

%
Mass
Butanol

86.96

13.04

B. Determination of Cloud Point

Table 2-2a: Trial 1
Mixtur Volume Data (mL)
Butan
Water Acetic
e #
ol
Acid
1
20
5
1.4 mL
2
20
10
4.0 mL
3
20
15
5.4 mL
4
20
20
6.2 mL
5
20
25
7.1 mL
6
20
30
7.9 mL
7
20
40
9.4 mL
8
20
50
10.5
mL

Mass (g)
Butan
Water
ol
16.2
3.0
16.2
10.0
16.2
15.0
16.2
20.0
16.2
25.0
16.2
30.0
16.2
40.0
16.2
50.0

Acetic
Acid
1.47
4.20
5.67
6.51
7.46
8.30
9.87
11.03

Mass Percent (%)

Butan
Water Acetic
ol
Acid
71.46
22.06 6.48
53.29
32.89 13.82
43.94
40.68 15.38
37.93
46.83 15.24
33.29
51.38 15.33
29.72
55.05 15.23
24.52
60.54 14.94
20.98
64.74 14.28

Page 4 of 11

20

60

10

20

70

11

20

80

12

20

90

13

20

100

14

20

110

11.5
mL
12.6
mL
13.6
mL
14.4
mL
15.2
mL

Table 2-2b: Trial 2

Mixture Volume Data (mL)
Butan Water Acetic
#
ol
Acid
1
20
5
1.1
mL
2
20
10
3.9
mL
3
20
15
5.3
mL
4
20
20
6.3
mL
5
20
25
7.1
mL
6
20
30
7.8
mL
7
20
40
9.3
mL
8
20
50
10.3
mL
9
20
60
11.5
mL
10
20
70
12.6
mL
11
20
80
13.4
mL
12
20
90
14.1
mL
13
20
100
14.8
mL
14
20
110
15.2
mL

16.2

60.0

12.08

18.35

67.97

13.68

16.2

70.0

13.23

16.29

70.40

13.31

16.2

80.0

14.28

14.66

72.41

12.93

16.2

90.0

15.12

13.35

74.18

12.46

16.2

100.0

15.96

12.26

75.67

12.08

Mass (g)
Butan Water
ol
16.2
5.00

Acetic
Acid
1.155

Mass Percent (%)

Butan Water Acetic
ol
Acid
72.47 22.37 5.17

16.2

10.00

4.095

53.47

33.01

13.52

16.2

15.00

5.565

44.86

40.80

15.14

16.2

20.00

6.615

37.84

46.71

15.45

16.2

25.00

7.455

33.30

51.38

15.32

16.2

30.00

8.19

29.78

55.16

15.06

16.2

40.00

9.765

24.86

60.64

14.80

16.2

50.00

21.03

64.92

14.04

16.2

60.00

18.35

67.87

13.68

16.2

70.00

10.81
5
12.07
5
13.23

16.29

70.40

13.31

16.2

80.00

14.07

14.69

72.55

12.76

16.2

90.00

13.39

74.38

12.24

16.2

100

14.80
5
15.54

12.30

75.91

11.80

16.2

110

15.96

11.40

77.38

11.23

Table 2-3: Average Composition of Ternary Mixtures

Page 5 of 11

1
2
3
4
5
6
7
8
9
10
11
12
13
14

Mass Percent (Average of Two Trials)

Butanol
Water
71.965
22.215
53.380
32.95
44.0
40.77
37.885
46.77
33.293
51.38
29.75
55.105
24.54
60.59
21.005
64.83
18.35
67.97
16.29
70.40
14.675
72.48
13.37
74.28
12.28
75.79

acetic
5.825
13.67
15.26
15.345
15.325
15.145
14.87
14.16
13.98
13.31
12.845
12.35
11.94

Page 6 of 11

It is a common knowledge that alcohols such as butanol are miscible in water. Truth
is, It does at certain concentrations and this was proven by the addition of acetic
acid. Upon addition andwhen the solution was stirred, it came to a point that a
cloudy/turbid phase appears , this is the transition from one region to another can
be observed by appearance (or disappearance) of cloudiness or turbidity in the
solution. The turbidity results from scattering of light by the large number of very
small oily droplets of the second phase that are produced when the system is
stirred.
Sometimes it is
easier to see
this
when
stopping
the
stirring briefly.If
the
three
components are
mixed to give an
overall system
composition that
falls in the 2phase
region,
the system will
separate
into
two phases: a
phase rich in
water
and
Fig. 2-1. Mixture 2 composed of 30 mL water, 2 mL Acetic Acid, 15 mLButanol. another rich in
1-butanol. To determine the other points, water was added in 5 ml increment each
time turbidity appears. When water is added, the mixture goes back to the one
phase region, and each time the cloudiness appears, the point falls in the two-phase
region which is below the curve. 14 points was plotted, the end point of the last one
became to difficult to recognize, anyhow, those were enought to complete the
curve. On the second part of the experiment, tie lines were constructed to validate
the precision and accuracy of the curve. A mixture of water, acetic acid, and butanol
in different concentrations were prepared. This concentrations all resulted to twophase after a while. Each phase was then recovered, the lower phase being the
water-rich mixture, and the upper phase being the butanol rich mixture. The plot of
their -mole fractions fell on each side of the curve, the end point of the tie-line. The
mole fractions of each component prior to separating the two phases were also
plotted and as expected, it fell below the curve and passes along the tie-line.

Page 7 of 11

Figure 2-2: Ternary phase diagram of wateacetic acid-butanol and tie line constructed from 30 mL water, 2 m

As mentioned earlier, the points along the curve shows the mass percentage of the
three components at equilibrium, information regarding phase equilibria can be
predicted by a simple rule (Gibbs phase rule):
f=cp+2

Page 8 of 11

where c is the number of components and p is the number of phases present in the
system. The degrees of freedom f, or variance, gives the number of variables (e.g.,
pressure, temperature, composition, etc.) that must be given to completely describe
the system, or to locate the state of the system on the phase diagram. In this
experiment there were 3 components, and creates a two-phase system which gives
the value f=3, however the+ 2 in the equation already corresponds to pressure and
temperature, so aside from those 2, the other variable that helped in locating the
mixture in the diagram is the concentration.
SAMPLE CALCULATIONS
Solubility of Immiscible Liquids
Solubility of Butanol in water
Mbutanol = (0.81 g/mL)(20mL) = 16.20
gbutanol
MH20 = (1.0 g/mL)(3.2mL) = 3.20 gH2O
%Butanolmass=

16.2
x 100
16.2+3.2

83.51%
%H2Omass = 100% - 83.51% = 16.49%
Determination of Cloud point
Trial 1, Mixture #1
Mbutanol = (0.81 g/mL)(20.0mL) = 16.20
gbutanol
MH2O = (1.0 g/mL)(5.0mL) = 5.0 gH2O
Macetic = (1.05 g/mL)(1.4mL) = 1.47
gacetic
-Mass Percent
%butanol =
71.46%
%H2O

16.2
x 100
16.2+5.0+1.47

5.0
x 100
16.2+5.0+1.47

22.06%
%acetic =

1.47
x 100
16.2+5.0+1.47

Composition

%butanol =

of

%acetic =

Determination of Tie-Lines
(Relative
Masses
of
Two-phase
systems)
Trial 1, Mixture #2
Mbutanol = (0.81 g/mL)(15mL) = 12.15
gbutanol
MH2O = (1.0 g/mL)(30.0mL) = 30.0 gH2O
Macetic = (1.05 g/mL)(2.0mL) = 2.10
gacetic
Solubility of Water in Butanol
Mbutanol = (0.81 g/mL)(3.7mL) = 3.0
gbutanol
MH20 = (1.0 g/mL)(20mL) = 20.0 gH2O
%Butanolmass=

3.0
x 100
3.0+ 20

Ternary

Trial 2, Mixture #1
Mbutanol = (0.81 g/mL)(20.0mL) = 16.20
gbutanol
MH2O = (1.0 g/mL)(5.0mL) = 5.0 gH2O
Maa = (1.05 g/mL)(1.1mL) = 1.155 gaa
-Mass Percent
%butanol =

71.46 +72.47
=71.965
2

6.48 +5.17
=5.825
2

13.04%
%H2Omass = 100% - 13.04% = 86.96%

6.48%
Average
Mixtures
Butanol:

Acetic Acid:

16.2
x 100
16.2+5.0+1.155

72.47%

Page 9 of 11

%H2O

5.0
x 100
16.2+5.0+1.155

22.37%
%acetic =

1.155
x 100
16.2+5.0+1.155

5.17%
Water:
%H2O =

22.06 +22.37
=22.215
2

(Titration Data: Composition of Two

Phases)
Trial 1, Mixture #2

m ol
L )(0.0158 L) =

nacetic = nNaOH = (1

mol
(0.025L) =
L

nacetic = nNaOH = (
0.0158 mol

0.025 mol
%wtacetic,TP2=

0.0158mol (60
Determination of Tie-Lines

13.925 g

g
)
mol

x 100 =6.79

Page 10 of 11

CONCLUSION
Through the experiment, the students were able to learn how to determine
the bimodal curve and tie lines in checking the composition of the water-butanolacetic acid system. Based on the results of the experiment, the percentages
obtained can be considered accurate and precise due to the closeness of the values.
However, certain errors were also present, such as the not so perpendicular eye
level on measuring the volumes of liquids, overruns during titration, and differing
temperature of the room. It is a wondrous experience to actually prove what is only
learned theoretically.
REFERENCES
(9th Edition). Physical Chemistry. Sa P. Akins, & J. de Paula, Physical Chemistry. New
York: WH Freeman and Company.
Feigenson, G. W., & Buboltz, J. T. (June 6, 2001). Ternary Phase Diagram of
Dipalmitoyl-PC/Dilauroyl-PC/Cholesterol: Nanoscopic Domain Formation
Driven by Cholesterol. Biophysical Journal, 27752788.
(7th Edition). Sa J. M. Smith, H. C. Van Ness, & M. M. Abbott, Introduction to
Chemical Engineering THermodynamics. McGraw Hill.