INDIAN INSTITUTE OF TECHNOLOGY KANPUR

Department of Chemical Engineering

Unit Operation Lab

Experiment Name: Vapor Liquid Equilibrium Set Up

Group Number: 8

Batch: Monday

TA’s Name: Lovely

Name and Roll numbers:

S.No Name Roll Number

1) Aditya Gupta 220066
2) Jay Jain 220476
3) Kushagra Tiwari 220574
4) Mitesh Gulpariya 220649
5) Divyansh patil 210359

1. Objective:
To study about the vapor liquid equilibrium curve

2. Aim:
To plot the Vapor-Liquid Equilibrium Curve for Ethyl acetate-Acetonitrile system.

3. Introduction:
The design of distillation and other contacting equipment requires reliable VLE data. It shows the
relationship between the composition of the vapor and that of liquid in equilibrium with the vapor
for a binary mixture at constant pressure or constant temperature. Although relatively few ideal
solutions are known whose equilibrium relations can be calculated from vapor pressure –
temperature data of the pure components, by far the larger numbers of systems of industrial
importance are non-ideal; and attempts to predict the equilibrium compositions of such mixtures
from theoretical considerations alone have not proved to be successful. It has been the practice to
determine such data experimentally under various conditions.

4. Theory:
Vapor liquid diagram shows relationship between the composition of the vapor and that of liquid
in equilibrium with the vapor for a binary mixture at constant pressure or constant temperature.
The basic data of any distillation problem are the equilibrium between the liquid and Vapour
phases of the system subjected to distillation. Hence it is of great importance to study the Vapour-
liquid equilibrium. If liquid and vapor behave ideally, such curves are calculated as follows:

From Raoult’s law:

Where p1 and p2 are partial pressures of components 1 and 2 in the mixture

From Dalton’s law of partial pressures:
p1 and p2 are vapor pressure of pure components at the same temperature as mixture.

y1 and y2 are the mole fractions of components in vapor

From these equations we have:

Theoretical VLE curve can thus be calculated by choosing various boiling points of the mixture
and calculate x and y as shown above. Carbon tetrachloride – toluene system closely follows ideal
behavior.
Boiling Point of Ethyl-Acetate = 77.2∘ 𝐶
Boiling Point of Acetonitrile = 82 ∘ 𝐶

Temperatur Mole Mass Volume

e Fraction Fraction (g/g) Fraction
(mL/mL)
(C) Liqui Vapo Liqui Vapo Liqui Vapo
d (x) ur (y) d (x) ur (y) d (x) ur (y)
95.5 0.01 0.170 0.04 0.343 0.05 0.399
9 72 7 91 0
89 0.07 0.389 0.16 0.619 0.20 0.673
2 57 6 12 6
86.7 0.09 0.438 0.21 0.665 0.25 0.716
7 47 4 73 0
85.3 0.12 0.470 0.26 0.694 0.31 0.742
4 54 3 41 2
84.1 0.16 0.509 0.33 0.726 0.39 0.770
6 74 0 23 5
82.7 0.23 0.545 0.43 0.753 0.49 0.794
4 81 5 71 8
 82.3 0.26 0.558 0.47 0.763 0.53 0.803
1 43 5 34 6
81.5 0.32 0.583 0.55 0.781 0.61 0.818
7 44 1 19 9
80.7 0.39 0.612 0.62 0.801 0.68 0.836
7 69 4 04 5
79.8 0.50 0.656 0.72 0.830 0.76 0.860
8 52 1 98 9
79.7 0.52 0.660 0.73 0.832 0.77 0.862
0 46 2 82 8
79.3 0.57 0.684 0.77 0.847 0.81 0.875
3 45 0 32 3
78.74 0.67 0.739 0.84 0.878 0.87 0.901
6 23 4 13 5
78.24 0.74 0.782 0.88 0.901 0.90 0.920
7 31 4 55 6
78.15 0.89 0.894 0.95 0.955 0.96 0.964
4 58 8 48 8

T vs x,y Curve

x vs y Curve
5. Description:
The set-up consists of distillation still with a heating element. An electrical Dimmer stat is
connected to heating element for varying heat input. The vapour form the top of column is
condensed in the concentric tube type condenser by circulating cooling water. The condensate is
feedback to column as reflux. A tank with pump is provided to circulate cold water to condenser.
Flow rates can be regulated through control valve fitted. Instrumentation is done to measure the
temperatures at different points.

6. Utilities Required:
6.1. Electrical supply: Single Phase, 220 V AC, 50 Hz, 5-15 Amps
socket with earth connection.
6.2. Water Supply (Initial Fill).
6.3. Drain required.
6.4. Floor Area Required: 1 m x 0.5 m.
6.5. Refractometer for analysis.
6.6. Chemicals Required: ethyl acetate and acetonitrile

7. Experimental Procedure:
7.1. Prepare solution of Toluene-CCl4 about 500 ml with low composition of CCl4.
7.2. Charge the feed solution in the vessel from the funnel provided at the top of the vessel.
7.3. Ensure that switches provided on the panel are at OFF position.
7.4. Switch ON the supply and then heater.
7.5. Gradually increase the dimmer stat and observe temperature T2.
7.6. When temperature T2 starts increasing switch ON the pump and allows cooling water to
pass through the condenser.
7.7. Maintain T2 above 70 and below 100 oC by adjusting the heat input from the dimmer stat.
7.8. After observing constant temperature T1 and T2 take sample of distillate and residue from
the valve provided at the bottom of condenser and still respectively.
7.9. Set the dimmer stat to zero and recharge the still with another feed mixture (Increase the
composition of CCl4).
7.10. Repeat step 6 to 10 for different feed mixtures.
7.11. Make a calibration chart for the feed solution with different composition of toluene.

8. Observations and Calculations:

.
Fitted Curve:

Equation Of line: Xa = -35.5687*RI + 48.8554 where Xa is the mole fraction of 𝑨𝒄𝒆𝒕𝒐𝒏𝒊𝒕𝒓𝒊𝒍, and
RI is the refractive index of the solution.

9. Nomenclature:
R.I Top = Refractive index of residue
R.I Bottom = Refractive index of distillate
T = Temperature of the vapour, oC
xA = Mole fraction of Acetonitrile in residue
xB = Mole fraction of Ethyl Acetate in residue
yA = Mole fraction of Acetonitrile in distillate
yB = Mole fraction of Ethyl Acetate in distillate.
10) Calculations:

Solution 1:

Solution 2:

Solution 3:
Sample Calculations:
Plots of Tx-y and VLE curve:
Result:
The dependence of refractive index w.r.t. the mole fraction of Acetonitrile is 𝑋𝐴 =
−35.568×𝑅.𝐼.+48.8554
● The T vs x,y graph obtained does not align with the theoretical obtained graph for
the binary mixture system thus the Acetonitrile-Ethyl Acetate mixture is a non-ideal
solution
● The theoretical plot of T vs x is expected to be concave upward and the theoretical
T vs y plot is expected to be concave downward but both the graphs obtained are
concave upwards.
● The x vs y plot is very close to the x=y line for lower values of x(>0.5) but shows
huge deviation from the x=y line for 1>x>0.5..
Laboratory Work:
Question and inferences:

10. Precaution and maintenance Instructions:

10.1. Fill the still atleast half of the capacity.
10.2. Drain the still and water tank after completion of the experiment.
10.3. Don’t run the pump before filling the tank with water.
10.4. Don’t start the heater before fill the chemical into the still.
.
11. Troubleshooting:
If electric panel is not showing the input on the mains light, Check the fuse and also check the
main supply.

12. References:
12.1. Coulson & Richardson, “Chemical Engineering Vol-2”, 4th ed, Asian Books Pvt.Lt, ND,
1991, Page 428-429.
12.2. Treybal, R.E, “Mass-Transfer Operations”, 3rd ed, McGraw-Hill, NY, 1981, Page 343-
348.