Friday, 11 December 2015

Practical 3: Phase Diagram (Part A)

PART A
Determination of Phase Diagram foe Ethanol / Toluene / Water system Theory Three-Component System

DATE
2 November 2015
OBJECTIVE
To determine the phase diagram for Ethanol/ Toluene/ Water System

INTRODUCTION

For three-component systems at constant temperature and pressure, the compositions may be stated in the form of coordinates for a triangular diagram.

In the diagram above, each corner of the triangular diagram represent a pure component, which is 100% A, 100% B and 100% C. Meanwhile, each side represents two-component mixtures and within the triangular diagram itself represents ternary components. Any line parallel to a side of the triangular diagram shows constant percentage value for a component, for example: DE shoes 20% of A with varying amounts of B and C. So does line FG, showing all mixtures containing 50% of B. These lines intercept with each other at K, which definitely contains 20% A, 50% B as well as 30% C. Measurements can be made this way because in a triangular diagram, the sum of all distances from K which is drawn parallel to the three sides of the diagram is same and equals to the length of any one side of the triangular diagram.
The addition of a third component to a pair of miscible liquids can change their mutual solubility. If this third component is more soluble in one of the two different components the mutual solubility of the liquid pair is decreased. However, if it is soluble in both of the liquids the mutual solubility is decreased. However, if it is soluble in both liquids, the mutual solubility is increased. This, when ethanol is added to a mixture of benzene and water, the mutual solubility of the liquid pair increased until it reached a point whereby the mixture becomes homogenous. This approach is used in the formulation of solutions. Examples of three component systems that has been studied include castor oil/alcohol/water; peppermint oil/propylene glycol/water; peppermint oil/polyethylene glycol/water.
The benefits of preparing an oily substance as homogenous water in liquids are already clear. However what will happen to a system like this when it is diluted should also be known and this can be explained through the understanding of the triangular phase diagram. Figure 1 is also for the system containing components peppermint oilpolysorbate 20-water. A concentration of 7.5% oil, 42.5% polysorbate  20 and 50% water (point A in the diagram) can be diluted for 10 times with water giving a solution that is still clear (now containing 0.75% of oil, 4.25% polysorbate 20 and 95% water). However, when 1mL of water is added to 10mL of clear solution B (49% oil, 5% polysorbate 20, 1% water) the solution becomes cloudy, point B’ (44.55% oil, 45.45% polysorbate 20 and 10% water). If 1mL of water is further added, the solution becomes clear, point B” (40.5% oil, 41.3% polysorbate 20, 18.2% water) but if the original solution is diluted three times (16 1/3% water, 16 2/3% polysorbate 20, 67% water) the solution becomes cloudy.



CHEMICAL

Ethanol, toluene and distilled water

APPARATUS

Conical flask, conical flask stopper, retort stand and clamp, pipette, and burette.

PROCEDURE

1.      Each determination in the experiment has been done twice.
2.      A mixtures of ethanol and toluene were prepared in sealed containers measuring 100cm3 containing the following percentages of ethanol (in percent) : 10, 25,35, 50,65, 75, 90 and 95.
3.      20 mL of each mixtures was prepared by filling a certain volume using a burette (accurately).
4.      Each of the mixtures was titrated with water until cloudiness is observed due to existence of a second phase.
5.      Little amount of water was added and was shake well after each addition. The room temperature was measured.
6.      The percentage based on the volume of each component when the second phase starts to appear/separate was calculated.
7.      The points were plotted on the triangular paper to give a triple phase diagrams at the recorded temperature.
8.      A few more measurements were done if necessary.


 RESULTS


% ethanol
(v/v)

Total volume (x+20)mL
Water
Toluene
Ethanol
Volume used(mL)
%
Volume used(mL)
%
Volume used(mL)
%
10
20.95
0.95
4.53
18
85.92
2
9.55
25
21.30
1.30
6.10
15
70.42
5
23.47
35
22.05
2.05
9.30
13
58.96
7
31.75
50
22.65
2.65
11.70
10
44.15
10
44.15
65
23.55
3.55
15.07
7
29.78
13
55.20
75
24.15
4.15
17.18
5
20.70
15
62.11
90
31.20
11.2
35.90
2
6.41
18
57.70
95
37.10
17.1
46.09
1
2.70
19
51.21




DISCUSSION

Ternary phase diagram contains three components which are water, ethanol and toluene. In this experiment, the mixture of ethanol and toluene once sealed in measuring container containing various percentages of ethanol and toluene. The mixture is prepared into 20mL of each containing various percentages of ethanol such as (in percent) 10,25,35,50,65,75,90 and 95. The mixture is  titrated with water until cloudiness appear due to existence of second phase. Addition of water to the mixture of ethanol and toluene increases the mutual solubility of the liquid pair until at one point the mixture become homogenous.This means two phases present in this experiment is detected and the volume of water used until the cloudiness is appears is recorded.
            A phase diagram shows the phases existing in equilibrium at any given condition. According to the Phase Rule, a maximum of four intensive variables (intensive properties) must be specified to completely define the state of a three-component system. The intensive variables that are usually chosen are pressure, temperature and concentration.  According to the phase rule, a single phase in a three-component system may possess four degrees of freedom.


According to phase rule:
P + F = C + 2, where
P is the number of phases in the system
C is the minimum number of chemical components required to constitute all the phases in the system
F is the number of degrees of freedom in the system (also referred to as the variance of the system).
                       The curve of the plotted graph is termed as binomial curve. The region under the curve shows that the presence of 2 phases that is water and toluene whereas the region above the curve boundary shows one phase of homogenous solution. Based on the results obtained, when there is a higher percentage of ethanol compared to the percentage of toluene in the mixture, the volume of water needed to titrate the mixture until cloudiness is observed is higher. The addition of water as the third component to a pair of miscible liquids of toluene and ethanol can change their mutual solubility. If the third component is more soluble in one of the two different component mixtures the mutual solubility of the liquid pair is decreased and thus two phases liquids will be appears.
          However, the binomial curve is incomplete. From the triangle above, the points are deviated a bit from theoretical points which are aligned in parallel line. So, there are some errors were occurs during conducting the experiment.
1)      The glass wares are contaminated.
2)      The eyes level of the observer was not perpendicular to the reading scales.
3)      The temperature during conducting the experiment was not consistent.

4)      The tendency of cloudiness for each mixture was not the same.

Hence, precaution steps must be concerned in the experiment.
1)      The glass wares must be rinsed before used.
2)      The eyes level of the observer must be perpendicular to the reading scale to avoid parallax error.
3)      The temperature of the surrounding must be fixed.
4)      The tendency of cloudiness for each mixture must be consistent to avoid the deviation of the final result.


QUESTIONS

1.      Does the mixture containing 70% ethanol, 20% water and 10% toluene (volume) appear clear or does it form two layers?
The mixture will remain clear and form one liquid phase.

2.     What will happen if you dilute 1 part of the mixture with 4 parts of (a) water (b) toluene (c) ethanol?
1 part mixture x 70% ethanol = 1 x 70/100 = 0.7 part of ethanol
1 part mixture x 20% water = 1 x 20/100 = 0.2 part of water
1 part mixture x 10% toluene = 1 x 10/100 = 0.1 part of toluene
Therefore, there are 0.7 part of ethanol; 0.2 part of water; 0.1 part of toluene in the mixture.

(a) Water: 1 part of mixture + 4 parts of water:
Ethanol = 0.7/5 x 100% =14%
Water = (0.2+4)/5 x 100% = 84%
Toluene = 0.1/5 x 100% =2%
Therefore, from the phase diagram, this mixture is outside the area of the binomial curve. Therefore, a clear single liquid phase of solution is formed.

(b) Toluene: 1 part of mixture + 4 parts of toluene
Ethanol = 0.7/5 x 100% =14%
Water = 0.2/5 x 100% = 4%
Toluene = 0.5/5 x 100% =82%
Therefore, from the phase diagram, this mixture is outside the area of the binomial curve. Therefore, a clear single liquid phase of solution is formed.


(c) Ethanol: 1 part of mixture + 4 parts of ethanol               
Ethanol = 4.7/5 x 100% =94%
Water = 0.2/5 x 100% = 4%
Toluene = 0.1/5 x 100% =2%
Therefore, from the phase diagram, this mixture is outside the area of the binodal curve. Therefore, a clear single liquid phase of solution is formed.

CONCLUSION
The experiment was done by mixing different proportion of ethanol and toluene. Then, water was titrated into the mixture. As the mixture turns cloudy, it indicates that two phase system were established. The reaction of water, ethanol and toluene will appears as two phase’s system due to the decreasing in solubility of the mixture. From the experiment, as the volume of toluene decrease, more water needed to break the homogeneity.

References :    Alexander T Florence, David Attwood, Physicochemical Principles of Pharmacy, Fifth Edition(2011)
Oxtoby, David W., H. P. Gillis, and Alan Campion. Principles of Modern Chemistry. Belmont, CA: Thomson Brooks Cole, 2008.
                        Robert G. Mortimer, Physical Chemistry, Third Edition(2008)
                        http://jchemed.chem.wisc.edu/Journal/Issues/2000/Apr/abs488A.html

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