CH 2016: Chemical Engineering Thermodynamics Laboratory, January-May 2018

Liquid-Liquid Equilibrium

Marks:
Experiment done on: 22/02/2018

100
Report submitted on: 01/03/2018

For Instructors use only:

No Section Max. Marks Marks

1 Introduction / background theory -

2 Experimental details: materials and methods -

3 Experimental observations; Raw data 20

4 Sample calculations 20

5 Results, discussion and conclusions 40

7 Suggestions for improvement 10

8 Overall formatting & References 10

Total 100

Batch: B
Group: B9
Name (in alphabetical order) Roll Number

A.Siddharth CH16B106
Chakane Mangesh Rajendra CH16B109
Mohd Faisal CH16B110
Navneeth Suresh CH16B111

1
 CH 2016: Chemical Engineering Thermodynamics Laboratory, January-May 2018

1. INTRODUCTION / BACKGROUND THEORY

When like interactions between two liquids are significantly stronger than unlike interactions,
liquids can split into two different partially miscible phases. They form separate phases to lower
the total Gibbs energy of the system. In this case, each species tends to equilibrate between the
two phases, leading to liquid–liquid equilibrium (LLE). These separate phases are stable for range
of temperature and composition. Outside this range the solution exists as clear solution. In this
experiment when phenol and water are mixed two separate phases viz. water rich phase and
phenol rich phase exists are formed initially. When this solution is heated, above a certain
temperature the two solutions become completely miscible in all proportions. This temperature is
known as Critical Solution Temperature(CST).

UPPER CRITICAL SOLUTION TEMPERATURE:

When the graph of temperature vs. mole fraction is a downward parabola, the system of liquid
has a temperature above which the liquids are miscible for all compositions. This temperature is
called upper critical solution temperature. Example: methanol-cyclohexane.

LOWER CRITICAL SOLUTION TEMPERATURE:

When the graph of temperature vs. mole fraction is an upward parabola, the system of liquid has
a temperature below which the liquids are miscible for all compositions. This temperature is called
lower critical solution temperature. Example: triethylamine-water

There exists some species which show both LCST and UCST. Example: 1,4-epoxybutane -water.

1.1 Aim

To find the upper critical solution temperature of phenol-water system and to analyse the results
to calculate Van Laar constants. Study the dependence of these parameters on temperature.

2. EXPERIMENTAL DETAILS

2.1 Materials
• Large test tube
• Thermometer
• Stirrer
• Pipette attached with a filler
• 10ml calibrated cylinder
• Cooling jacket
• Hot- plate -heater

Chemicals Required
• Phenol
• Water
• Ethanol

2
 CH 2016: Chemical Engineering Thermodynamics Laboratory, January-May 2018

2.2 Experimental Setup & Procedure

A thermometer and a stirrer are fitted into a cylindrical test tube through a two-holed rubber
cork. The test tube is placed in a glass jacket to slow down the cooling process. A hot plate
heater is used to heat the solution.
Procedure
• Before starting the experiment, wash the relevant equipment (test tubes, beakers, pipette etc.)
with ethanol.
• Heat the phenol (originally, in solid phase) to around 45℃ so that it starts melting to form liquid
phase
• Take 5.4 grams of phenol and 2 ml of water in a test tube.
• Initially we can observe the turbidity which shows that the two liquids are immiscible.
• The solution is heated slowly using a hot-plate heater. At a certain temperature the turbidity
disappears (existence of single phase) and this temperature is labelled as T1.
• Now the solution is cooled until the turbidity reappears. The turbidity reappearance temperature
is noted as T2.
• The solution is continuously stirred during the heating and cooling to ensure uniform temperature
throughout the solution.
• The experiment is repeated a certain number of times with subsequent addition of 2 ml and then
4ml of water.
• The average of temperatures T1 and T2 is taken as T(mean) and is plotted against mole fraction
of water.

2.3 PRECAUTIONS
• Extreme precaution should be exercised when handling phenol. Safety gloves are to be worn to
avoid contact with skin. Phenol can cause first degree burns.
• Lab coat, shoes and goggles should be worn all the time.
• Before starting the experiment all the equipment’s should be washed well to make sure there are
no impurities in apparatus
• Stirring should be done carefully so that thermometer does not get damaged.
• Parallax error must be avoided while the temperatures readings are taken.

3. EXPERIMENTAL OBSERVATIONS AND DATA

S.No Volume of Turbidity Disappearance Turbidity Appearance Mean

Water (in mL) Temperature (℃) Temperature (℃) Temperature
(℃)
1. 1.5 19.6 19.5 19.55
2. 2 26.8 26.8 26.8
3. 6 63.9 63.9 63.9
4. 8 65.2 65 65.1
5. 10 64.7 64.8 64.75
6. 12 64.1 64.3 64.2
7. 14 64 64 64
8. 16 62.9 62.9 62.9
9. 20 61 60.9 60.95
10. 24 58.5 58.4 58.45
3
 CH 2016: Chemical Engineering Thermodynamics Laboratory, January-May 2018

11. 28 55.4 55.3 55.35

12. 32 53.4 53.6 53.5
13. 36 50 49.8 49.9
14. 40 45.5 45.6 45.55
15. 44 40.9 40.8 40.85
16. 48 35.4 35.5 35.45
17. 52 28.6 28.9 28.75

Weight of Phenol taken = 5.4 g

Complete disappearance of turbidity is at 28.9 ℃

4. SAMPLE CALCULATIONS

Let a and b denote phenol and water respectively in the following calculations.

Molecular weight of Phenol: M. Wa = 94.11 gm/mol

5.4
No. of moles of Phenol: na = = 0.0574 moles
94.11
Density of water: ρ𝑏 = 1gm/cc
Molecular weight of water: M. Wb = 18 gm/mol

ρ𝑏 ×𝑉𝑏
𝑛𝑏 M.Wb
Mole fraction of water: 𝑥𝑏 = (𝑛 = ρ𝑏 ×𝑉𝑏
𝑎 + 𝑛𝑏 ) ( +0.0574)
M.Wb

S.No Volume of Water (in mL) Mole Fraction of water (𝑥𝑏 ) Mean Temperature (℃)
1. 1.5 0.5921 19.55
2. 2 0.6594 26.8
3. 6 0.8531 63.9
4. 8 0.8856 65.1
5. 10 0.9064 64.75
6. 12 0.9207 64.2
7. 14 0.9313 64
8. 16 0.9393 62.9
9. 20 0.9509 60.95
10. 24 0.9587 58.45
11. 28 0.9644 55.35
12. 32 0.9687 53.5
13. 36 0.9721 49.9
14. 40 0.9748 45.55
15. 44 0.9771 40.85
16. 48 0.9789 35.45
17. 52 0.9805 28.75

4
 CH 2016: Chemical Engineering Thermodynamics Laboratory, January-May 2018

The fitted polynomial is :

−(0.3464 × 105 )𝑥 4 + (1.0371 × 105 )𝑥 3 − (1.1515 × 105 )𝑥 2 + (0.5634 × 105 )𝑥1 − 0.0997 = 0

And α (water rich phase) and β (phenol rich phase) denote the two liquid phases.

At a particular temperature, a tie line is drawn cutting the plot at two points. This gives the mole
fraction of water in α (water rich phase) and β (phenol rich phase).

S.No 𝑥𝑎𝛼 𝑥𝑎
𝛽 𝑥𝑏𝛼 𝑥𝑏
𝛽 T(℃) T(K)
1. 0.0166 0.2273 0.9834 0.7727 40 313
2. 0.0218 0.2072 0.9782 0.7928 45 318
3. 0.0275 0.1895 0.9725 0.8105 50 323
4. 0.0328 0.1761 0.9672 0.8239 54 327
5. 0.0372 0.1661 0.9628 0.8339 57 330
6. 0.0421 0.156 0.9579 0.844 60 333
7. 0.0479 0.1455 0.9521 0.8545 63 336
8. 0.0549 0.1339 0.9451 0.8661 66 339
9. 0.0576 0.1297 0.9424 0.8703 67 340

Equating fugacities of phenol in both phases:

5
 CH 2016: Chemical Engineering Thermodynamics Laboratory, January-May 2018

𝜷
𝒇̂𝜶𝒂 = 𝒇̂𝒂
𝛽 𝛽
𝛾𝑎𝛼 𝑥𝑎𝛼 𝑓𝑎 = 𝛾𝑎 𝑥𝑎 𝑓𝑎

Equating fugacities of water in both phases:

𝛽
𝑓̂𝑏𝛼 = 𝑓̂𝑏
𝛽 𝛽
𝛾𝑏𝛼 𝑥𝑏𝛼 𝑓𝑏 = 𝛾𝑏 𝑥𝑏 𝑓𝑏

Using Van Laar’s Activity Coefficient Model

Equation 1:

2 𝛽 2
𝐴 𝐵𝑥𝑏𝛼 𝛽 𝐴 𝐵𝑥
𝑥𝑎𝛼 exp [ ( 𝛼 𝛼 ) ] = 𝑥𝑎 exp [ ( 𝛽 𝑏 𝛽) ]
𝑅𝑇 𝐴𝑥𝑎 + 𝐵𝑥𝑏 𝑅𝑇 𝐴𝑥 + 𝐵𝑥
𝑎 𝑏
Equation 2:

2 𝛽 2
𝐵 𝐴𝑥𝑎𝛼 𝛽 𝐵 𝐴𝑥𝑎
𝑥𝑏𝛼 exp [ ( 𝛼 𝛼 ) ] = 𝑥𝑏 exp [ ( 𝛽 ) ]
𝑅𝑇 𝐴𝑥𝑎 + 𝐵𝑥𝑏 𝑅𝑇 𝐴𝑥 + 𝐵𝑥 𝛽
𝑎 𝑏
Equation 3:

𝑥𝑎𝛼 + 𝑥𝑏𝛼 = 1

Equation 4:

𝛽 𝛽
𝑥𝑎 + 𝑥𝑏 = 1

6
 CH 2016: Chemical Engineering Thermodynamics Laboratory, January-May 2018

Thermodynamic Consistency Test

𝟏
𝜸𝟏
∫ 𝐥𝐨𝐠 𝒆 ( ) 𝒅𝒙𝟏 = −𝟎. 𝟑𝟓
𝟎 𝜸𝟐

𝛾1 : Activity Coefficient of water in α phase

𝛾2 : Activity Coefficient of phenol in α phase

𝜸
Plot of 𝐥𝐨𝐠 𝒆 (𝜸𝟏 ) 𝐯𝐬 𝒙𝜶𝒃
𝟐

3.5

2.5
ln(ℽ1/ℽ2)

1.5

0.5

0
0 0.2 0.4 0.6 0.8 1
Mole fraction of Water in α-phase

7
 CH 2016: Chemical Engineering Thermodynamics Laboratory, January-May 2018

The area under graph is calculated using Excel, after the above data points are regressed in the
region 0-1(Mole fraction of water in α phase).
1 𝛾
Since, ∫0 log 𝑒 (𝛾1 ) 𝑑𝑥1 ≈ 0 . It proves the thermodynamic consistency.
2

5. RESULTS, DISCUSSION AND CONCLUSION

5.1 Results

Once the turbidity appearance and disappearance temperatures are tabulated, Tmean is calculated.
The graph Tmean vs mole fraction of water is plotted. We observe the plot is a downward parabola.
Hence, the solution exhibits UCST. At a particular temperature, a tie line can be drawn cutting
the plot at two points. This gives the mole fraction of water in α (water rich phase) and β (phenol
rich phase). Outside the curve, the solution exists as a clear solution irrespective of the
composition. The peak of the graph is called upper critical solution temperature which in our case
is 68.4℃.

1
𝐴 = 88.451 ( ) − 0.1838
𝑇
1
𝐵 = 6.3968 ( ) − 0.0057
𝑇
5.2 Conclusions
• Phenol-water system exhibit UCST nature with upper critical temperature equal to 68.4℃.
• A and B are the linear functions of 1/T.
• The thermodynamic consistency test is valid for the obtained data as the integration is almost
equal to 0.

6. SUGGESTIONS
• Phenol was given in a very large container and it took a long time to liquefy it. If phenol is
already taken out, in a small container it would make the task easier and quicker.
• While heating the solution, the turbidity disappears and the temperature shoots very rapidly
which results in faulty reading. We should be able to control the heating so that we can heat the
solution slowly to get proper readings.

7. REFERENCES
Referencing a book:
1. M. D. Koretsky, Engineering and Chemical Thermodynamics; 2nd Edition, Wiley: New
York, 2012.

8
CH 2016: Chemical Engineering Thermodynamics Laboratory, January-May 2018