CHEMICAL ENGG GROUP

VAPOUR LIQUID EQUILIBRIUM

 CHEMICAL ENGG GROUP

VAPOUR LIQUID EQUILIBRIUM

OBJECTIVE

To study and understand vapor liquid equilibrium curve.

AIM:

To determine the temperature (T), Liquid composition (X), Vapor composition (Y) at
equilibrium and to draw the vapor liquid equilibrium curve for the given system of liquids.

THEORY:

The phase rule is given by F=C-P+2 or F+P=C+2, where F is the number of degrees
of freedom, C is the number of components and P is the number of phases. For a system of
two miscible liquids it can be seen that the number of degrees of freedom is 2. Fixing either
the temperature or pressure we can define such a system and the pressure or temperature has
an influence over the concentration. Liquid A has a higher vapor pressure than B, at any value
of the total pressure P, the point L on the curve marked liquid gives the composition of the
liquid in equilibrium with the vapor. It can be seen from the figure that the vapor in
equilibrium with any liquid is relatively richer in the component having the higher vapor
pressure (more volatile component A in the figure). The curves for systems which behave
ideally or which show small deviation from the ideal can be represented as shown in the
figure, corresponding curves can be obtained for systems in which the total vapor pressures
has a maximum or minimum at the given temperature ( Non-ideal systems). In all the systems
the liquid and vapor curves are always related to one another in such a way so as to satisfy
the condition that the vapor of the shell contains relatively large properties of the more
volatile component. At the maximum and minimum pressures, however the liquid and the
vapor in equilibrium have the same composition (Azeotropic).

If a liquid mixture were to be distilled at a constant temperature (i.e. isothermally) the

vapor in equilibrium with the liquid could be determined from the curves as in figure
(Isothermal V-L-E or P-x-y data). It is more interesting however and it is closer agreement
with general practice to consider distillation at constant pressure, for example at 1 atm in this
case the boiling point of a mixture in the temperature at which the total pressure is 1 atm and
 CHEMICAL ENGG GROUP

hence the distillation is being carried out at boiling point. Vapour pressure and boiling point
varies with the composition of the mixture. Change of total pressure changes the vapor
pressure and also the boiling point will be changed and this is represented in the figure,
Isobaric

PROCEDURE:

1. Take 100 ml of more volatile (cyclohexane) in the round bottom flask.

2. Allow water to flow through the condenser.
3. Switch on the heater and wait for steady state temperature of vapors (top) and residue
(bottom).
4. Once steady state is obtained by the system, note the constant top and bottom
temperatures.
5. Switch off the heater. Collect minimum 10 ml of distillate (top product) and 10 ml of
residue (bottom product) in a beaker.
6. Cool down the collected samples to a temperature at which calibration curve has been
prepared and find out the refractive index for both the samples.
7. Use the calibration curve to calculate mole fraction of more and less volatile
component which will give you one (T-x-y) point.
8. Now add 50 ml of less volatile component (toluene) in round bottom flask and switch
on the heater.
9. Repeat steps 3 to 7 which will give you another (T-x-y) point.
10. Repeat steps 8 and 9 for five or six times to get sufficient data to plot VLE curve.
11. Plot the equilibrium curve.

OBSERVATION TABLE:

S. Vol. Of Vol. Of Temperature Refractive Index Mole fraction of

No. Cyclohexane Toluene (ml) (oC) cyclohexane
(ml) Distillate Residu X Y
e
1
2
3
4
5
 CHEMICAL ENGG GROUP

CALIBRATION CHART:
To prepare calibration curve, you should follow table below and make sure that all the
standard solution prepared are at 280C temperature.
S. Volume of Volume Moles of Moles of Refractiv Mole fraction of Mole fraction
No. Cyclohexane of Cyclohexa Toluene e Index Cyclohexane of toluene
(ml) Toluene ne
(ml)
1 50 0 1.4254
2 40 10 1.4374
3 30 20 1.4506
4 25 25 1.4558
5 20 30 1.4681
6 10 40 1.4826
7 0 50 1.4960
 CHEMICAL ENGG GROUP

Cyclohexane
Molecular weight: 84.16 g/mol

Where T is in 0C

Toluene:
Molecular weight: 92.14 g/mol

Where T is in 0C

CALCULATIONS:
S. Temperature , mm , mm
No. (oC) Hg Hg
1
2
3
 CHEMICAL ENGG GROUP

4
5

1
Conclusion :
0
Vapor-liquid
. equilibrium curve
9
0
.
8
0
X,Y .
Cyclo 7 V
0 a
hexa . p
ne 6 or
0
. Li
5 q
0 ui
. d
4
0
.
3
0
.
2
0
.
1
0
6 6 6 7 7 7 7 7
4 6 8 0 2 4 6 8
Temperature,
oC