Subject : UEMK2411 Chemical Engineering Laboratory 1

Experiment No. :4

Experiment Title : Vapour Liquid Equilibrium (VLE)

Date of Experiment : 25th Jan 2017

Name of Lecturer : Dr.Yap Yeow Hong

Group No. : 20

Name of Group Members :

Year and Trimester

Name Student ID
Y2S3
Chang Kai Yan 1403527
Y3S2
Vinod A/L Muneesesparan 1301462
Y2S3
Ooi Swee Sean 1401662

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 TITLE

Experiment 4- Vapour Liquid Equilibrium (VLE)

OBJECTIVE

1) To find VLE relationship for binary mixture.

2) To plot the equilibrium curve.

INTRODUCTION

The most important process in the chemical industry is the separation of

azeotropic mixtures based on differences of boiling point as it cannot use
conventional separation methods. (Botia et al., 2010) This method can be applied to
the vapor-liquid equilibrium experiment.

Equilibrium is a static condition in which no changes happens in the macroscopic

properties of a system of time. Vapor-liquid equilibrium is in the condition where a
liquid and its vapor are in equilibrium with each other, or on the other hand a
condition where the rate of evaporation is same to the rate of condensation one a
molecular level such that there is no overall vapor liquid inter-conversion. (Sakshat
Virtual Labs, 2011). The aim of this experiment is construct an equilibrium curve for
an ethanol-water system in a static condition.

In this experiment, the ethanol-water mixture is fed through a vessel into a

evaporator and the heater is turned on. When reaching the equilibrium state, the vapor
will rise up and cooled down by the condenser on top of the evaporator whereas the
liquid will flow back into the evaporator. The system is said to be in equilibrium state
when the temperature is constant. After that, the samples of vapor and liquid are
collected separately to determine their compositions or theirs refractive index (RI) by
using a refractometer. All the data are recorded and the composition of mixture in the
vapor phase is labelled as y where the composition of the mixture in the liquid phase
is labelled as x in equilibrium state.

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 MATERIAL AND EQUIPMENT

1) Vapour Liquid Equilibrium Unit

2) 40 v/v % ethanol-water mixture

3) 0 v/v % ethanol-water stock solution

4) 20 v/v % ethanol-water stock solution

5) 40 v/v % ethanol-water stock solution

6) 60 v/v % ethanol-water stock solution

7) 80 v/v % ethanol-water stock solution

8) 100 v/v % ethanol-water stock solution

9) Refractometer

10) Dropper

11) Beaker (100 mL)

Apparatus set up:

Figure 1: Vapour Liquid Equilibrium Apparatus.

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 RESULT

Table 1: Refractive index of sample at different temperature

(Obtained from experiment)

Temperature(C) Refractive index of condensate Refractive index of bottom

feed
75 13.6 13.7 13.6 8.0 8.2 8.2
80 13.7 13.7 13.8 8.4 8.5 8.5
85 13.4 13.5 13.6 8.1 8.1 8.1
90 13.2 13.7 13.8 7.8 7.6 7.7

Table 2: Average value of sample at different temperature.

(Through calculation)

Temperature (C) Average value of Average value of

refractive index of refractive index of bottom
condensate feed
75 13.63 8.13
80 13.73 8.47
85 13.50 8.10
90 13.57 7.70

Table 3: Refractive index of samples with different ethanol-water percentage.

Percentage of Refractive Refractive Refractive Average value

ethanol in the index index index of the
ethanol-water (1st result) (2nd result) (3rd result) refractive
stock solution index
(v/v %)
0 0.1 0.1 0.1 0.10
20 4.5 4.5 4.3 4.43
40 9.5 9.7 9.7 9.63
60 12.3 12.4 12.4 12.37
80 12.7 12.8 12.6 12.70
100 9.3 9.4 9.6 9.43

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 Table 4: Experimental value of percentage of ethanol in the sample in different
temperature (Extrapolated result)

Temperature (C) composition of ethanol in composition of ethanol in

condensate bottom feed
75 0.749 0.417
80 0.755 0.438
85 0.74 0.415
90 0.745 0.391
CALCULATION

Example 1: Calculation to obtain average value of refractive index of sample at

different temperature:

Values of refractive index of sample o

Average value of refractive index of sample at 80 C (condensate)=
Number of results obtain

13.7+ 13.7+13.6
= 3

=13.73

Example 2: Calculation to obtain average value of refractive index of sample at

different ethanol-water percentage:

Average value of refractive index of sample at 80% ethanolwater percentage

Values of refractive index of sample obtained at 80% ethanol - water percentage
Number of results obtained
=
12.7 12.8 12.6
3
=
= 12.70
12.70

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Example 3: Calculation to obtain experimental value of composition of ethanol in the
sample (either in condensate or bottom feed)

First, we have to obtain the linear equation of the calibration curve (plotted with the
data from Table 3) from the trend line. (For the trend line of the calibration curve,
please refer to Graph 3)

From the graph, the linear equation:

Y=0.1657x + 1.218

From table 2, when temperature = 80, refractive index of condensate =13.73

Substitute the refractive index from table 2 into Y, temperature from table 2 into x:

13.73=0.1657x + 1.218

X= 75.5

Convert into composition by dividing x by 100, thus x = 0.755

DISCUSSION

The vapour -liquid equilibrium (VLE) experiment was conducted to find the VLE
relationship for binary mixture and to plot the equilibrium curve. The experiment was
conducted under a condition where the vapour phase and liquid are in equilibrium
with each other.

Before starting the experiment, the first action to consider is to close the liquid
sampling and drain valve. The evaporator in this experiment have been poured with
ethanol-water mixture. All the valve of the evaporator have been closed before
starting the experiment. The temperature was first set at 75c and connected to the
drain by cooling water. The heater then switched on and the water supply have been

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connected to the condenser. After the temperature was raised, 5 minutes of stopwatch
time had set to record down the temperature and pressure after the system have
reached equilibrium. A small portion of samples from the liquid and vapour valve
were taken to measure the refractive index number. The valves are then closed after
collecting the samples to conduct the experiment for 80, 85 and 90c. All the data
have been measured 3 times using refractometer to get the average reading of the
index numbers.

As the second part of the experiment, refractometer have been used again to get
the index numbers values of the ethanol water itself from 0 % to 100% by increasing
the percentage by 20%. All the data have been recorded and tabulated in the result.

From the data we obtained from the experiment, we compiled the values obtained
into Table 1, and after some simple calculation, we rearranged the new value for the
refractive index of the sample and the temperature into Table 2. Based on Table 2, we
plotted a graph to show the relationship between the refractive index of the sample
and the temperature of the sample, as shown in Graph 1.

Graph 1: Relationship between the temperature and refractive index of

sample

Relationship between the temperature and refractive index of sample

15
13.63 13.73 13.5 13.57
14
13
12

Index 11
RefractiveTemperature(Condensate) Temperature(Bottom feed)
10
9 8.13 8.47
8.1
7.7
8
7
74 76 78 80 82 84 86 88 90 92

Temperature (C)

Besides, with the data recorded in the Table 3, we plotted a calibration curve in
order to calculate the composition of the ethanol in both condensate and bottom feed
of the sample based on the sample. The calibration curve is shown in Graph 2. From
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the curve, we failed to obtain a curve which supposed to show a linear increasing
relationship instead of a second degree polynomial curve that shows decreasing trend.
The most important thing is, we are not able to get a valid result by using the equation
provided by the trend line of this curve, which is y = 0.106x + 2.81. If we insist to
using this equation to evaluate the composition of ethanol in sample, we will obtain
that is greater than 1, which is not applicable for the composition.

Graph 2: A graph of refractive index against percentage of ethanol-water

solution

A graph of refractive index against percentage of ethanol-water solution

14 12.7
12.37
f(x) = 0.11x + 2.81
12
9.63 9.43
10

8
Refractive index
6
4.43
4

2
0.1
0
0 20 40 60 80 100 120

Percentage of ethanol (%)

In order to amend this problem, our group had decided to extrapolate the
calibration curve by removing the refractive index of the sample at 100% percentage

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of ethanol in sample, to ensure that the curve is showing the increasing trend. The
extrapolated curve is shown in Graph 3.

Graph 3: A graph of refractive index against percentage of ethanol-water

solution (Extrapolated).

A graph of refractive index against percentage of ethanol-water solution

15 12.37 12.7
f(x) = 0.17x + 1.22
9.63
10
Refractive index 4.43
5
0.1
0
0 10 20 30 40 50 60 70 80 90

Percentage of ethanol (%)

In Graph 3, the curve shown an increasing trend and provided a linear equation that
is suitable for the evaluation of the composition of the ethanol in the sample. The
linear equation obtained from the graph is y = 0.1657x + 1.218. With this equation,
we managed to find out the composition of the ethanol in the sample at different
temperature through calculation. For the method of calculation, please refer to the
Example 3 under Calculation session.

Once the calculation done, we group up the calculated value into Table 4. A graph
of vapour composition (condensate, y) against liquid composition (bottom feed, x) is
plotted and shown in Graph 4.

Graph 4: A graph of composition of ethanol in condensate against composition

of ethanol in bottom feed

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 A graph of composition of ethanol in condensate against composition of ethanol in bottom feed
0.76

0.76

0.75

Composition of ethanol in condensate 0.75

0.74

0.74

0.73
0.38 0.39 0.4 0.41 0.42 0.43 0.44 0.45

Composition of ethanol in bottom feed

As the values of the composition of ethanol are fluctuating without a constant

pattern, we are not able to find out the direct relationship between composition of
ethanol in condensate and composition of ethanol in bottom feed. Theoretically,
ethanol and water should be in an equilibrium state at certain temperature or time,
therefore the graph should show an increasing trend when either value of x or y is
increased. Therefore, they are some inaccuracy in the result due to few reasons which
will be mentioned later on.

T-x-y diagram represents a binary mixture in temperature x against y. As all the

compositions are labelled as mole fractions of the more volatile component (lower
boiling point), x in the liquid phase or y in the vapour phase. The composition of each
phase of the ethanol-water mixture can be known by the T-x-y diagram in the given
temperature. A T-x-y diagram is plotted based on the result obtained and calculated.
The T-x-y diagram is shown in Graph 5.

Graph 5: T-x-y diagram of the sample

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 T-x-y diagram of sample
95

90

85

Temperature (C) 80

75

70

65
0.35 0.4 0.45 0.5 0.55 0.6 0.65 0.7 0.75 0.8

compositon of ethanol

Condensate (Vapour) Bottom feed (Liquid)

Based on the theory, there will be a corresponding equilibrium composition

for both condensate and bottom feed at a specific temperature. The T-x-y
diagram plotted based on the experimental values should have a similar Curry
puff shaped curve with the T-x-y diagram depicted in Figure 1. However in
the T-x-y diagram in Graph 5, the vapour and liquid composition failed to
show the curry puff shaped curve. In other words, the T-x-y diagram in not
showing the corresponding equilibrium composition of vapour and liquid
phase, as mentioned in the theory.

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 Temperature

vapour

liquid

x1 y1

Figure 2: Theoretical shape of T-x-y diagram

From the results we obtained from the experiment, we had found that our result is
far apart from what is expected based on the vapour liquid equilibrium theory. These
inaccuracy are mainly due to the incapability of fulfilling the criteria to ensure that the
experiment in run under an ideal condition. According to the theory, equilibrium of
vapour and liquid can be accomplished within a closed system and under steady-state.
However, the experiment environment is unable to fulfil this criteria. During this
experiment, we are facing an issue that the temperature control is not working as well
as expected. It will facing an electricity break down if we change the temperature and
switch on the temperature switch. This break down made the VLE apparatus not able
to carry on the experiment under a steady-state condition, as the thermal supply is
considered inconsistent. Besides, ethanol is a highly volatile chemical substance.
Some of the portion of ethanol might vaporized when we filling in the condensate or

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bottom feed into the beaker. To make it worse, we are forced to let the beaker that
containing ethanol-water mixture remain exposed to the environment directly due to
the breakdown of the refractometer as we need time to get a new refractometer to
carry on the experiment. This might be one of the reason of the fluctuating refractive
index obtained through experiment.

As a precaution for this experiment, always measure the index number of the
ethanol more than 3 times to get the average reading. Secondly, always clean the
refractometer after measuring each of the samples to avoid errors in the reading.
CONCLUSION

In conclusion, the experiment was carried out successfully. From the calculation,
we found the average value of refractive index of sample art different temperature is
13.73 where the average value of refractive index of sample at different ethanol-water
percentage is 12.70. By doing this experiment, we are able to construct and plot a
graph of composition of ethanol in condensate versus composition of ethanol in
bottom feed to study VLE relationship between binary mixture. Theoretically, ethanol
and water should be in equilibrium at certain temperature. Due to some error in the
experiment, our result is far apart from the VLE theory.

REFERENCES

1. Botia, D., Riveros, D., Ortiz, P., Gil, I. and Sanchez, O. (2010). VaporLiquid
Equilibrium in Extractive Distillation of the Acetone/Methanol System Using Water
as Entrainer and Pressure Reduction. Industrial & Engineering Chemistry Research,
49(13), pp.6176-6183.

2. Sakshat Virtual Labs. (2011). Binary vapor liquid equilibrium. [online] Available
at: http://Binary vapor liquid equilibrium [Accessed 2 Feb. 2017].

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