Vapor Liquid Equilibria: Experiment No: 1

Experiment No: 1
VAPOR LIQUID EQUILIBRIA

Aim:
To determine the vapor-liquid equilibrium curve for the ethanol-water mixture and
compare it with the VLE data.
Introduction:
Several chemical engineering processes which have mass transfer operations
taking place between different phases. The desired outcome is usually a change
in composition and hence the composition of a phase is the key parameter of
interest.
An equilibrium is said to be established in a system when no changes occur to the

macroscopic properties of a system with time. This implies a balance of all the
potentials which can cause a change. An isolated system of liquid and vapor will
initially show some changes in composition; this is because some molecules in a
phase will have sufficiently high velocities near the interface to enter the other
phase. Eventually both these fluxes will become equal and equilibrium will be
established.
Theory:
In this experiment, we consider liquid vapor system with two components. From
the Equilibrium Phase rule, the equilibrium state will be completely determined
when two independent variables are fixed. Hence at any given temperature and
pressure, the compositions of the components in the two phases will be fixed.
Examples of equilibrium curves for such a system are shown in Figure 1. The
curves shown are plotted at a constant pressure at different temperatures 𝑡 and
compositions of component 1 in the liquid and vapor phase as 𝑥 and 𝑦
respectively. The upper line in each represents the saturated vapor line also called
the bubble line and the lower line represents the saturated liquid line also called
the dew line.
Figure 2 shows the variation of 𝑦 with 𝑥 when one of the values is fixed at a
constant pressure. This xy behavior is theoretically modelled by laws such as
Raoult’s Law and Henry’s law.
-1-
-2-
Figure SEQ Figure \* ARABIC 2: xy diagrams at 1 atm: (a) (a)
tetrahydrofuran(1)/carbon tetrachloride(2); (b) chloroform(1)/tetrahydrofuran(2);
(c) furan(1)/carbon tetrachloride(2); (d) ethanol(1)/ toluene(2) [1]
Models:
Raoult’s Law:
This law states that the partial pressure (P1) of a component in the vapor phase is
equal to the vapor pressure (P1,vap) times the mole fraction (x1) of the component
in the liquid phase. That is,
𝑃 =𝑃, 𝑥
Using this with the Dalton’s Law of partial pressure yields
𝑦 𝑃 =𝑃, 𝑥
Where 𝑃 is the total pressure in the vapor phase.

Hence this gives a linear relationship between the two compositions at equilibrium.
-3-
Henry’s Law:
Henry’s law states that –
𝑃 = 𝑥 𝐻
Where H is Henry's constant.

With the Dalton’s Law, this gives-
𝑦 𝑃 =𝑥 𝐻
Experimental Setup:
● The apparatus consists of a round bottom flask with three way open at the
top and opened at the bottom.
● A heating mantle of 1 liter capacity is provided to heat the reboiler
● A vapor rising and reflux and reflux tube with condensate and sampling is
connected to the reboiler
● A spiral glass tube condenser is provided to condense the vapor
● A overhead tank is provided to circulate condenser cooling water
● Two thermocouples are provided to measure the liquid and vapor
temperatures.
-4-
Requirements:
● Ethanol
● Water
● Digital Refractometer
Experimental Procedure:
1. Preparation of Calibration Chart :-
● Measure 10 mole % of Water and 90 mole % of Ethanol and mix the
contents well. Find the refractive index of the mixture.
● Now prepare a mixture of 30 mole % of Water and 70 mole % of Ethanol
and find the refractive index.
● Thus change the concentration of mixture and estimate the refractive index
for various concentrations and tabulate them in Table No. 1
● The calibration chart once prepared can be used repeatedly.
2. Prepare a mixture of Water and Ethanol containing a 50 mole % of ethanol
with a volume of approximately 500 ml and feed it to the vapor liquid
equilibrium apparatus.
3. Heat the mixture gently to distill it. Recycle the vapor for at least half an hour
before any samples are taken, to allow equilibrium between liquid and vapor
phases to be obtained.
4. Then the liquid and vapor samples are taken at noted temperatures and
cooled to room temperature and their refractive index is found.
5. Add 100 ml of Water to the VLE apparatus and again allow equilibrium to
be attained (indicated by constant temperature) before the next set of
samples are taken.
6. Find the refractive index of the samples.
7. Tabulate them in table No. 2
Procedure to use the Refractometer:
1. Calibrate the refractometer by filling its sample well with a few drops of
distilled water and then pressing the zero button.
2. Now take a sample in a dropper and put 1-2 drops on the sample well of the
refractometer.
3. Close the cover of the sample well.
4. Now press the read button to get the reading of the refractive index.
-5-
Precautions:
● Close the mixture inlet valve before switching on the heater.
● Clean the sample well of the digital refractometer with dry tissue paper to
remove dust particles.
Observations:
Table No: 01. Calibration Chart.
S. No. Mole % of Water Mole % of Ethanol Refractive Index
Table No. 2
S. No. Vapor Temperature Refractive Index

Vapor sample Liquid sample
(°C)
Table No. 3
-6-
S. No. Refractive Index Mole fraction of Ethanol
Vapor Liquid Vapor Liquid
Table No.4
S. No. Temperature yc xc
T (oC)
Results:
Draw the graph for y1 vs x1 for experiment and compare with the original data from
literature.
Sources of errors:
Report the possible sources of error found in the experiment and the
observations. Discuss exactly how these affect the experimental data (i.e. will
the readings be larger or will they be smaller due to the presence of a particular
source).
Discussions:
-7-
The following topics need to be discussed in detail in the report.
1. What is the conclusion of the experiment? Is the objective fulfilled?

2. Give a physical interpretation of your results.
3. Compare your results with those obtained from theory/literature. Justify
the differences in these, if any.
4. What is the Equilibrium Phase rule? What are the free and the dependent
variables in this experiment?
5. Define bubble point and dew point.
6. Describe in brief how the interactions between the components affect the
vapor liquid equilibrium.
7. Is it always possible to obtain a pure component using a distillation
process? Why/why not?
References:
J M Smith, H C Van Ness and M M Abbott, Introduction to Chemical Engineering
Thermodynamics, 7th Edition Tata McGraw Hill, pp. 276-317,
-8-

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Experiment No: 1

VAPOR LIQUID EQUILIBRIA

An equilibrium is said to be established in a system when no changes occur to the

Where 𝑃 is the total pressure in the vapor phase.

Where H is Henry's constant.

Procedure to use the Refractometer:

S. No. Mole % of Water Mole % of Ethanol Refractive Index

S. No. Vapor Temperature Refractive Index

1. What is the conclusion of the experiment? Is the objective fulfilled?

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