1

ABSTRACT

The Vapor Liquid Equilibrium Unit experiment was conducted to identify the
relationship between the vapor and liquid at equilibrium. In this experiment also, the main
aim is to construct an equilibrium curve for the methanol-water system at atmospheric
pressure. Besides that, the experiment was conducted to study the effect of initial mixture
composition upon the boiling temperature and vapor liquid phase compositions. A mixture of
methanol and water with known composition is fed into the evaporator through the valve and
the mixture will start to boil when the heater is switched on. Next, the mixture vapor will rise
up and will be cooled down by the condenser at the top of the evaporator. The liquid will fall
back into the evaporator as the vapor starts to condense. After a few minutes, the system will
stabilize and finally achieve an equilibrium state when temperature remains constant. After
that, the sample of vapor of methanol and the sample of liquid that contains methanol and
water are collected. Based on the composition of the samples, the refractive index was
determined by using refractometer. Then, we determined the relationship between the vapor
and liquid at equilibrium by drawing a graph of mole fraction of vapor against mole fraction
of liquid and a graph of temperature against mole fraction of liquid and vapor. It can be said
that from the graphs, due to high volatility of methanol than water, the composition of
methanol in vapor is higher than liquid. The experiment was successfully conducted as all the
aims were achieved.








2

INTRODUCTION

Vapor Liquid Equilibrium can be defined as a condition where a liquid and its vapor
are in equilibrium with each other. This is a condition where the rate of evaporation equals
the rate of condensation. The experiment is conducted by using Vapor Liquid Equilibrium
(VLE) unit. Pressure and temperature are very important in this experiment because they will
influence the equilibrium of vapor and liquid. In order to set and adjust the temperature to
achieve equilibrium, a temperature controller is used. There is an insulator for this unit to
minimize heat losses.
In the VLE unit experiment, two main substances used are methanol and water. Both
of them have different characteristics, therefore we need to characterize the fluids based on
their refractive index by using refractometer. Refractive index is the ratio of the velocity of
light in a vacuum to its velocity in a specified medium. The refraction occurs in the
refractometer due to the change in the speed of light as it travels through a material of one
density to one of different density.
One of the properties of methanol is the volatility of methanol is higher than water.
This is because methanol is less polar than water. Higher polarity of water means a water
molecule sticks to other water molecules more tightly, thus it tends to stay in the liquid phase.
Therefore, lots of energy and higher boiling point needed to break these attractions.
Meanwhile, methanol is less sticky and easy to enter the gaseous phase, thus it is more
volatile than water.
There are several equipments that applied the vapor liquid equilibrium concept in
industrial process such as vapor-liquid separator and distillation. Vapor-liquid separator is a
vessel which a liquid and vapor mixture is fed where the liquid is separated by gravity and
falls to the bottom of the vessel while the vapor travels upward as it exits the top of the vessel.
For distillation, a reboiler is used to provide the necessary vaporization for the distillation
process while a condenser is used to cool and condense the vapor leaving the top of the
column.


3

AIM

The objectives of the experiment are:

- To investigate the relationship between vapor and liquid at equilibrium

- To construct an equilibrium curve for the methanol and water system at
atmospheric pressure.


- To study the effect of initial mixture composition upon boiling temperature and
vapor-liquid phase compositions.











4

THEORY


Vapour-liquid equilibrium is a condition of where the liquid and vapour are in equilibrium
with each other, by means it is a condition of where the rate of evaporation is equals to the
rate of condensation.

There are theories or laws that are related to Vapor Liquid Equilibrium which are Raoults
law, Daltons law and Antoines law.

According to Gavhane, Raoults law is commonly used for predicting the vapor liquid
equilibrium for an ideal solution in equilibrium with an ideal gas mixture from the pure
component vapor pressure. Raoults law states that the equilibrium partial pressure of a
constituent or component in a solution at a given temperature is equal to the product of its
vapor pressure in the pure state and its mole fraction in the liquid phase.

For a binary system which means, a system consist of two components, if p
A
is the
equilibrium partial pressure of A, p
A
is the vapor pressure of A in the pure state and x
A
is the
mole fraction of A in the liquid phase, so we have

p
A
= p
A
x
A

p
B
= p
B
x
B

=p
B
(1-x
A
), as x
A
+ x
B
= 1

Where p
B
= equilibrium partial pressure of B
x
B
= mole fraction of B in liquid phase
= vapour pressure of pure B

Daltons law states that the total pressures exerted by a gas or vapor mixture is equal to the
sum of the partial pressure of the components present in the gas or vapor mixture. Therefore,
mathematically for binary system which is :

P = P
A
+ P
B
Where P is the total pressure.
5


Another law that is related to vapour liquid equilibrium is Antoines Law. The Antoine
equation is a vapor pressure equation. It describes the relation between vapor pressure and
temperature for pure components. The Antoine equation is derived from the Clausius
Clapeyron relation.
P
A

where P is the vapor pressure, T is temperature and A, B and C are component-specific
constants.


There are two types of diagram curve that represents the binary system, which Txy and xy
curve. Txy curve is a diagram of temperature against x and y composition, while xy curve is
x against y. X represents the liquid composition where in this experiment we use their mole
fraction, while Y is the vapour composition.





6


The above diagram shows Txy diagrams. Saturated liquid is the lower curve that gives the
mole fraction of benzene in liquid phase, x. The upper curve is the saturated vapour, that
gives the mole fraction of benzene in the vapor phase y.


The curved line is called the equilibrium line. It is defined as the compositions of the liquid
and vapor in equilibrium at a fixed pressure. For the straight line according to the figure
above, Y is equals to X.

X = Y

Where
x = mole fraction of more volatile component in liquid
y = mole fraction of more volatile component in vapour








7

APPARATUS AND MATERIALS

1) Methanol.
2) Distilled water.
3) SOLTEQ Vapour Liquid Equilibrium Unit.
4) Refractometer.
5) Sample collectors.
6) Dropper.
7) 500mL, 1000 mL and 2000 mL beakers.
8) 50 mL and 500 mL measuring cylinders.











8


PROCEDURE
General start up procedures.
1. A calibration curve of refractive index vs composition plot for the binary system was
prepared.
2. The evaporator and condenser were checked to make sure the units are empty of liquid.
3. All valves were initially closed and the heater power switch was turned off.
4. The main power on the control panel was switched on.All sensors and indicators were
checked to ensure functioning properly.
General experiment procedures.
1. The general start-up as described was performed.
2. About 12-L methanol and 5-L deionized water were prepared.
3. Valve V8 was opened.
4. 0.1-L methanol and 3-L water were poured into the evaporator through valve V1.Then,
valve V1 was closed.
5. Valves V13 and valve V14 were opened at the level sight tube.It was ensured that the
liquid level was above the safety line on the level sight tube.Then,valves V13 and V14 were
closed.
6. Valve V10 was opened and adjusted to allow about 5 L/min of cooling water to flow
through the condenser.
7. The temperature controller TIC-01 was set to about 100C.The heater was switched on.
8.The temperature rise in TIC-01 was observed.The liquid in the evaporator had started to
boil when the temperature at TIC-02 started to increase sharply.The pressure at P1-01 was
observed.All temperatures and pressure were let to stabilized at a steady state value.
9. The evaporator pressure and liquid and vapour temperatures were recorded.
9

10. Liquid and vapour sample were collected from the unit according to the sampling
procedure.The samples were analyzed to determine their compositions.
11. The heater was switched off and valve V11 was opened to allow cooling water to flow
through the cooling coil in the evaporator.
12. The temperature at T1-02 was let to drop significantly to signify that the boiling had
stopped.Valve V11 was closed.
13. An additional 0.2-L methanol was poured into the evaporator through valve
V1.Then,valve V1 was closed.There was about 0.3-L methanol and 3-L water in the
evaporator.Steps 5 to 12 above were repeated.
14. An additional 0.2-L methanol was poured again into the evaporator through valve
V1.Then valve V1 was closed.There was about 0.5-L methanol and 3-L water in the
evaporator.Steps 5 to 12 were repeated again.
15. An additional 0.5-L methanol was poured into the evaporator through valve V1.Then
valve V1 was closed.There was about 1-L methanol and 3-L water in the evaporator.Steps 5
to 12 were repeated again.
16. An additional 1-L methanol was poured into the evaporator through valve V1.Then valve
V1 was closed.There was about 2-L methanol and 3-L water in the evaporator.Steps 5 to 12
were repeated again.
17. An additional 1-L methanol was poured into the evaporator through valve V1.Then valve
V1 was closed.There was about 3-L methanol and 3-L water in the evaporator.Steps 5 to 12
were repeated again.
18. Valve V2 and V3 were opened to drain all liquid from the evaporator.
19. 2-L methanol and 1-L water were poured into the evaporator through valve V1.Then
valve V1 was closed.Steps 5 to 12 were repeated.
20. An additional 1-L methanol was poured into the evaporator through valve V1.Then valve
V1 was closed.There was about 3-L methanol and 1-L water in the evaporator.Steps 5 to 12
were repeated.
10

21. An additional 2-L methanol was poured into the evaporator through valve V1.Then valve
V1 was closed.There was about 5-L methanol and 5-L water in the evaporator.Steps 5 to 12
were repeated.
22. The general shut-down procedures were performed.
General shut-down procedures.
1. The heater was switched off.
2. Valve V10 was opened to increase cooling water flow rate through the condenser.
3. Valve V11 was opened to allow cooling water to flow through the cooling coil in the
evaporator.
4. Valve V8 was opened slowly to depressurize the unit.
5. Wait for the temperature of the unit to drop below 50C.
6. Valves V2 and V3 were opened to drain all liquid from the evaporator.
7. Valves V5 and V7 were opened to drain all liquid accumulated at the condenser.
8. All valves were closed and the main power of the control panel was switched off.









11

RESULTS

a) Vapor-Liquid Equilibrium Data

Component Temperature (C) Refractive Index (nD)
Water Methanol Vapor Liquid Vapor Liquid
3.0 0.1 86.0 96.0 1.34060 1.33470
3.0 0.3 85.4 92.9 1.33903 1.33412
3.0 0.5 84.5 90.1 1.34078 1.37506
3.0 1.0 80.5 84.6 1.34430 1.33564
3.0 2.0 76.3 78.2 1.34126 1.33581
3.0 3.0 74.7 76.0 1.34127 1.33590

Component Temperature (C) Refractive Index (nD)
Water Methanol Vapor Liquid Vapor Liquid
1.0 2.0 70.7 72.4 1.34081 1.34197
1.0 3.0 69.0 70.2 1.33997 1.34201
1.0 5.0 67.2 68.8 1.33924 1.34211

b) Calibration Table

Water
(ml)
Methanol
(ml)
Mol
Water
Mol
Methanol
Mol
Total
Methanol
Mol
Fraction
Methanol
wt%
Refractive
Index
10 0 0.556 0 0.556 0 0 1.33300
8 2 0.444 0.0494 0.4934 0.1001 16.49 1.33692
6 4 0.333 0.0986 0.4316 0.2285 34.50 1.34167
4 6 0.222 0.1481 0.3701 0.4002 54.23 1.34226
2 8 0.111 0.1975 0.3085 0.6409 75.96 1.33660
0 10 0 0.2466 0.2466 1.0000 100.00 1.33299




12








1.332
1.334
1.336
1.338
1.34
1.342
1.344
0 0.2 0.4 0.6 0.8 1 1.2
R
e
f
r
a
c
t
i
v
e

I
n
d
e
x

Mol Fraction
Graph of RI vs Mol Fraction
0
0.005
0.01
0.015
0.02
0.025
0.03
0 0.005 0.01 0.015 0.02 0.025 0.03 0.035
V
a
p
o
r

m
o
l

f
r
a
c
t
i
o
n

(
x
)

Liquid mol fraction (y)
X-Y Equilibrium Diagram
13




















0
20
40
60
80
100
120
0 0.005 0.01 0.015 0.02 0.025 0.03 0.035
T
e
m
p
e
r
a
t
u
r
e

(

C
)

Vapor/Liquid mol fraction
T- xy Graph of Methanol-Water System
Vapor
Liquid
14

CALCULATIONS

*Note that the vapor pressure of methanol is 97.658 mmHg.

From Antoines Law: P
A

From Raolts Law: P
A
. P
A
where x (vapor mol fraction) can be
written as y (liquid mol fraction)


Therefore,

Antoines Constant:

Temperature
(C)
A B C Reference

80.5- 293.63

5.15853


1569.613


-34.846

Ambrose,
Sprake, et al.,
1975

15.1-103.83
5.20409 1581.341 -33.50
Ambrose and
Sprake, 1970
80-210
5.31301 1676.569 -21.728
Hirata and
Suda, 1967


15

Calculation of methanol mol fraction in vapor state.


When T = 86.0C (359 K)

0.0260

When T = 85.4C (358.4 K)

0.0222

When T = 84.5C (357.5 K)

0.0216

When T = 80.5C (353.5 K)

0.0187





16

When T = 76.3C (349.3 K)

0.0161


When T = 74.7C (347.7 K)

0.0152

When T = 70.7C (343.7 K)

0.0131

When T = 69.0C (342 K)

0.0123

When T = 67.2C (340.2 K)

0.0114

17

Calculation of methanol mol fraction in liquid state.


When T = 96.0C (369 K)

0.0317

When T = 92.9C (365.9 K)

0.0286

When T = 90.1C (363.1 K)

0.0246

When T = 84.6C (357.6 K)

0.0216





18

When T = 78.2C (351.2 K)

0.0173
When T = 76.0C (349 K)

0.0160

When T = 72.4C (345.4 K)

0.0139

When T = 70.2C (343.2 K)

0.0128

When T = 68.8C (341.8 K)

0.0122



19

Sample calculation of methanol mol fraction from calibration table.

Water : 2mL
Methanol : 8mL

Mole of water :

Mole of methanol :

Therefore,

0.6408





20


DISCUSSION
The VLE data of binary mixtures (methanol and water) of this experiment is
presented in the x-y equilibrium diagram. The y and x axis are represented by the vapor and
liquid mol fraction of the mixture respectively at different temperature. The VLE diagram
shows the bubble point and dew point of the binary mixture at constant pressure which is at 1
atmospheric pressure. Bubble point is the point at which the first drop of liquid of mixture
begins to vaporize whereas dew point is the point at which the first drop of gaseous mixture
begins to condense. The diagonal y=x serves for determination of azeotropic mixture. Based
on the plot,a curve is obtained. The curve also known as the equilibrium line represents the
compositions of vapor and liquid of the mixture at equilibrium.

By comparing the experiments equilibrium line with that of the ideal equilibrium line,
our group only managed to obtained a slightly curve equilibrium line. Human error might had
occurred, such as recording the non-steady temperature reading of the vapor and liquid unit
from TIC-01 and TIC-02 when we were supposed to get the steady temperature. These affect
the value of the vapor and liquid mol fraction calculated by using the obtained temperature
and also affect the x-y equilibrium diagram in which the ideal equilibrium line is not obtained.


An equilibrium diagram with ideal equilibrium line,using literature values of vapor
and liquid compositions(mol fractions).
21

Source: http://lorien.ncl.ac.uk/ming/distil/distilvle.htm
However, the obtained equilibrium curve from this experiment does not cross the
diagonal line to obtain azeotropic points where azeotropes occur. Azeotrope is a liquid
mixture which when vaporized, produces same composition as the liquid. Hence, the
methanol and water system is non azeotropic as the vapor does not produce same
composition as liquid when vaporized. The x-y equilibrium diagram follow Raoults
Law .Thus, we can say that the methanol-water mixture is an ideal solution.


Two VLE plots with two different azeotropic systems, one with a maximum boiling
point and one with a minimum boiling point. (non-ideal solutions)
Source: http://lorien.ncl.ac.uk/ming/distil/distilvle.htm

The graph of refractive index versus mol fraction is the calibration curve of this
experiment. The calibration curve is vital for the determination of the unknown mole
fractions of samples taken from the boiling mixtures. With the help of the curve, the T-xy
graph can be plot. However, Antoines Law can also be used to estimate the composition of
methanol in vapor and liquid state.

22

On the other hand, based on the T-xy graph of methanol- water system, the
composition (mol fraction) of liquid is higher than the composition of vapour at high
temperature. The extreme end of the graph represents the boiling point of the pure methanol
and boiling point of pure water water which is 86C and 96C respectively. Pure water has
lower vapour pressure than pure methanol. The vapour pressure of a pure substance is the
pressure exerted by the substance against the external pressure which is usually atmospheric
pressure. Vapour pressure is a measure of the tendency of a condensed substance to escape
the condensed phase. The larger the vapour pressure, the greater the tendency to escape.
When the vapour pressure of a liquid substance reaches the external pressure, the substance is
observed to boil.Hence,pure water has higher boiling point than that of methanol in the binary
system at 1 atm because it has lower vapor pressure.

















23




CONCLUSION

In conclusion, the experiment is conducted successfully with some error occur. The
relationship between the vapor and liquid at equilibrium is determined where the graph of
equilibrium has been drawn. Effect of initial mixture composition upon the boiling
temperature and vapor-liquid phase compositions are also can be determine where the higher
the composition of methanol at initial, the higher will be its composition in the vapor and
liquid. As mentioned in discussion part, Antoines Law has been used to estimate the
composition of methanol in vapor and liquid state. From the result of this experiment, it can
be concluded that the composition of methanol in vapor is higher than liquid due to the
volatility of methanol which is more volatile than water. Besides, the pressure is kept
constant during the experiment which is at atmospheric pressure 1atm. Also, water has higher
boiling point than that of methanol in the binary system at 1atm because it has lower vapor
pressure.











24



RECOMMENDATION

Before and during the experiment, there are a few criteria that should be kept in mind
to ensure that the overall experiment will proceed smoothly.

First, any leftover liquid from the previous use of the VLE unit should be removed as
this can reduce a significant amount of experimental error. All the valves should be open
beforehand and collected in a waste container.

Second, the heater temperature should less than 50C when pouring in the liquids so
that rapid evaporation will not occur. This will affect the composition values of the sample.

Third, the eye level should be perpendicular to the reading on the beaker when
measuring liquid to prevent parallax error.

Lastly, the refractometer should be cleaned each time when taking a reading by
wiping its surface with a clean paper towel. This is to ensure that the refractive index of the
sample taken is obtained correctly.






25


REFERENCE

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http://en.wikipedia.org/Antoine_equation [Accessed: 14 Apr 2014]
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http://webbook.nist.gov/cgi/cbook.cgi?ID=C67561&Mask=4&Type=ANTOINE&Plo
t=on [Accessed: 14 Apr 2014]
3. Raoult's Law. (2008). Mass Transfer-II. [online] Available at:
http://books.google.com.my/books?id=p7FYpSuY0R8C&source=gbs_navlinks_s
[Accessed: 15 Apr 2014].
4. Wikibooks.org.(2014)Introduction to Chemical Engineering
Process.[online]Retrieved
from:http://en.wikibooks.org/wiki/Introduction_to_Chemical_Engineering_Processes/
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5. Vapor Liquid Equilibrium in Binary System.[online]
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6. Distillation.[online] Retrieved from:
http://www.umsl.edu/~orglab/documents/distillation/dist.htm [Accessed: 14 Apr
2014]
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out08TL.pdf[Accessed: 14 Apr 2014]
8. Schmidt-haensch.com. 2014. What is refractometry? - Schmidt+Haensch. [online]
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[Accessed: 15 Apr 2014].
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2014].

26

APPENDIX



SOLTEQ VLE UNIT




Refractometer