BACHELOR OF ENGINEERING (HONS) CHEMICAL

CHE 465 CHEMICAL ENGINEERING LABORATORY I

VAPOR-LIQUID EQUILIBRIUM UNIT

PREPARED BY
EH2202B
HAFIZAH BINTI OSMAN (2013686936)
ILI NADIA ISMAIL (2013212084)
JAILANI BIN ZULKIFLI (2013450328)
JEALONOVIER SAYAS ANAK JEMON (2013886766)
MARLISSA BINTI AZEMI (2013815618)

PREPARED FOR
MISS SITINOOR ADEIB BINTI IDRIS
VAPOR-LIQUID EQUILIBRIUM UNIT
CHE 465-MISS SITINOOR ADEIB IDRISPage 1

ABSTRACT
Experiment of liquid vapour equilibrium (VLE) unit is used to study about the binary
system. The mixture used is methanol-water mixture. The first objective of this experiment is
to construct the equilibrium curve for the methanol-water system at atmospheric pressure.
Secondly, the objective is to investigate the relationship between vapour and liquid at
equilibrium and thirdly, to determine the composition of methanol at liquid and vapour phase.
The quantity of methanol is added for a few times until the quantity of methanol is 5liters and
water is 1litres. The mixture is heated until it boiled. The constant temperature is taken and at
constant temperature, the liquid vapour sample is drain and the refractive index is read by
using the refractometer.

INTRODUCTION
In industry, the most of the separation process used the vapour liquid equilibrium
concept that applicable for the binary system. It used the concept based on the differences of
the boiling point. In the experiment of liquid vapour equilibrium (VLE) unit the pressure used
may be constant (at atmospheric pressure) or at differences pressure. In this experiment, the
pressure used is atmospheric pressure and it means that the pressure is constant. The mixture
used is methanol-water mixture.
For the separation process between methanol and water, the substance with low boiling
point will vaporised first. In this mixture, water has high boiling point compare to methanol.
This is because water has the molecule that attract with the strongest hydrogen bond. Thus,
methanol will vaporise first.
There are a few laws that can be used to relate with this experiment. Raoults Law state
that the vapour pressure of a solution depends on the mole fraction of a solute added to the
solution. This law only used for the ideal mixture and for the ideal solution. Then, Daltons
Law state that the total pressure exerted by the mixture of non-reactive gas is equal to the
sum of the partial pressure of the partial pressure of gases itself. For this experiment, Antoine
equation is used to describe the relation between vapour pressure and temperature for pure
components.
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The vapour liquid equilibrium unit is used for any binary system and used the concept
of boiling point. In this experiment, the mixture of methanol-water of unknown composition
is fed into the evaporator. When the heater is switch on, the mixture started to boil until it
vaporised. The condenser is placed at the top of the evaporator. It is used to cooled down the
vaporised mixture and prevent the mixture from further vaporised. As the vapour start to
condensed, the liquid will fall back into the evaporator. At constant temperature reaches, the
system will stabilized and reached equilibrium. At this point, the sample is taken to determine
the refractive index by using the refractometer. The composition is obtained by using the
refractive index.

OBJECTIVES
The objectives of this 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; and to study the effect of initial mixture composition upon boiling
temperature and vapor-liquid phase compositions.

THEORY
In vapor liquid equilibrium, there are two laws related to the experiment which is
Raoults law and Daltons law. Besides, Antoine equation is also used in finding the vapor
pressure. After getting the vapor pressure from Antoine equation, used the equation from
Raoults law to find the mole fraction.
Raoults law is usually used for predicting the vapor liquid equilibrium for an ideal
solution in equilibrium with an ideal gas mixture from the pure component vapor pressure. It
states that the vapor pressure of a solvent above a solution is equal to the vapor pressure of
the pure solvent at the same temperature scaled by the mole fraction of the solvent.
Psolution=XsolventPosolvent

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Where

Psolution = equilibrium partial pressure

Posolvent = vapor pressure of solvent in pure state
Xsolvent = mole fraction

Meanwhile, Daltons law states that the total pressure of a gas or vapor mixture in a
container is the sum of the partial pressures of the individual gases or vapor mixture in the
container. It can be stated as
Ptotal = P1 + P2 + P3 + ... Pn
Antoine equation is a vapor pressure equation and describes the relation between the
vapor pressure and temperature for pure components. The basic form of the equation is:

Where

P = the absolute vapor pressure of a substance

T = the temperature of the substance
A, B, C = substance specific coefficient (i.e. constants or parameters)

Temperature versus x and y diagram (Txy) and x versus y diagram are the VLE
diagrams used to represent the data for binary systems. X represents the liquid composition
and Y represents the vapor composition where both are in mole fraction.

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Figure 1: Boiling Point Diagram for Methanol/Water

Figure 2 : Equilibrium Diagram

The curved line is called the equilibrium line and describes the compositions of the
liquid and vapor in equilibrium at some fixed pressure.

MATERIALS
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Distilled water and methanol

APPARATUS
Refractometer; SOLTEC Vapor Liquid Equilibrium Unit ( Model : BP16); Sample collector;
Dropper; 1000 mL and 2000 mL beaker; 500 mL and 50 mL measuring cylinder

EXPERIMENTAL PROCEDURE
1
2
3
4

The general start-up procedures were performed.

About 12 L of pure methanol and 5 L deionized water were prepared.
Valve V8 was opened.
0.1 L methanol and 3 L water were poured into the evaporator through valve V1 and

Valve V1 was closed.

Valve V13 and V14 were opened at the level sight tube. The liquid level was ensured

above the safety line on the level sight tube. Valve V13 and V14 were then closed back.
Valve V10 was opened and adjusted to allow 5 L/min of cooling water to flow through

the condenser.
The temperature controller TIC-01 was set to about 100C and the heater was switched

on.
Temperature rise in TIC-01 was observed. The liquid in the evaporator begins to boil
when the temperature at TI-02 starts to increase sharply. The pressure at PI-01 was

observed. All temperature and pressure were left to stabilize to a steady state value.
9 The evaporator pressure and the liquid and vapour temperatures were recorded.
10 A liquid and vapour samples from the unit were collected using the standard collection
procedure. The samples were analysed to determine their composition.
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 TI-02 was observed until it drops significantly to signify that boiling
has stopped. Valve V11 was closed.
13 An additional 0.2 L methanol was poured into the evaporator through valve V1. Valve
V1 was closed. There was now 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 into the evaporator through valve V1. Valve
V1 was closed. There was now about 0.5 L methanol and 3 L water in the evaporator.
Steps 5 to 12 above were repeated.

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15 An additional 0.5 L methanol was poured into the evaporator through valve V1. Valve
V1 was closed. There was now about 1 L methanol and 3 L water in the evaporator.
Steps 5 to 12 above were repeated.
16 An additional 1-L methanol was poured into the evaporator through valve V1. Valve V1
was closed. There was now about 2-L methanol and 3-L water in the evaporator. Steps
5 to 12 above were repeated.
17 An additional 1-L methanol was poured into the evaporator through valve V1. Valve V1
was closed. There was now about 3-L methanol and 3-L water in the evaporator. Steps
5 to 12 above were repeated.
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. Valve
V1 was closed. Steps 5 to 12 above were repeated.
20 An additional 1-L methanol was poured into the evaporator through valve V1. Valve V1
was closed. There was now about 3-L methanol and 1-L water in the evaporator. Steps
5 to 12 above were repeated.
21 An additional 2-L methanol was poured into the evaporator through valve V1. Valve V1
was closed. There was now about 5-L methanol and 1-L water in the evaporator. Steps
5 to 12 were repeated.
22 The general shut-down procedures were performed.

RESULTS
Table 1 : Calibration Table for Methanol-Water

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Water
(ml)

Methanol
(ml)

Mol
Water

Mol
Methanol

Mol
Total

10

0.556

0.556

Methanol
Mol
Fraction
0

0.500

0.025

0.525

0.048

1.3349

0.444

0.049

0.493

0.100

1.3385

0.389

0.074

0.463

0.160

1.3410

0.333

0.099

0.432

0.229

1.3417

0.278

0.123

0.401

0.307

1.3420

0.222

0.148

0.370

0.400

1.3412

0.167

0.173

0.340

0.509

1.3401

0.111

0.198

0.309

0.641

1.3361

0.056

0.222

0.278

0.799

1.3350

10

0.247

0.247

1.000

1.3341

Refractive
Index
1.3308

Table 2 : Vapor-Liquid Equilibrium Table

Component

Temperature (C)

Refractive Index (nD)

Water

Methanol

Vapor

Liquid

Vapor

Liquid

3.0

0.1

95.3

99.0

1.3349

1.3345

3.0

0.3

90.1

95.4

1.3390

1.3350

3.0

0.5

87.6

92.8

1.3405

1.3354

3.0

1.0

83.9

86.3

1.3410

1.3375

3.0

2.0

80.1

83.5

1.3379

1.3390

3.0

3.0

78.3

78.9

1.3362

1.3410

1.0

2.0

73.0

73.5

1.3349

1.3416

1.0

3.0

71.8

72.0

1.3333

1.3407

1.0

5.0

70.1

70.0

1.3320

1.3382

Figure 3 : Graph of Refractive Index Versus Mole Fraction

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Refractive Index

1.34
1.34
1.34
1.34
1.34
1.33
1.33
1.33
1.33
1.33
1.32

Mol Fraction

Figure 4: Graph of Vapor-Liquid Equilibrium

0.04
0.03
0.03
0.02
Vapor mol fraction (x)

0.02
0.01
0.01
0
0

0.01 0.01 0.02 0.02 0.03 0.03 0.04 0.04

Liquid mol fraction (y)

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Figure 5: T-XY Diagram of Methanol-Water System

120
100
80
60
40
Temperature (C)

20
0

Vapor/Liquid mol fraction

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Vapor
Liquid

CALCULATIONS
*Note that the vapor pressure of methanol is 97.658 mmHg.
From Antoines Law: PA

10 A

B
T +C

From Raoults Law: PA x . P A

where x (vapor mol fraction) can be

written as y (liquid mol fraction)

Therefore,
( A

x=

10

B
)
T +C

Antoines Constant:
Temperature
(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

Calculation of Methanol Mol Fraction in Vapor State.

When T = 95.3.0C (368.3 K)

{
10

5.20409

x=

1581.341
369.3+ (33.50 )

97.658

= 0.032

When T = 90.1C (363.1 K)

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{
10

5.20409

x=

1581.341
363.1+ ( 33.50 )

97.658

= 0.026

When T = 87.6 C (360.6 K)

{
10

5.20409

x=

1581.341
360.6 + (33.50 )

97.658

= 0.024

When T = 83.9C (356.9 K)

{
10

5.20409

x=

1581.341
356.9+ (33.50 )

97.658

= 0.021

When T = 80.1C (353.1 K)

{
10

5.20409

x=

1581.341
353.1+ ( 33.50 )

97.658

= 0.018

When T = 78.3C (351.3 K)

{
10

5.20409

x=

1581.341
351.3+ (33.50 )

97.658

= 0.017

When T = 73.0C (346.0 K)

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{
10

5.20409

x=

1581.341
346.0+ (33.50 )

97.658

= 0.014

When T = 71.8C (344.8 K)

x=

10

5.20409

1581.341
344.8+ (33.50 )

97.658

= 0.014

When T = 70.1C (343.1 K)

{
10

5.20409

x=

1581.341
343.1+ ( 33.50 )

97.658

= 0.013

Calculation of Methanol Mol Fraction in Liquid State.

When T = 99.0C (372.0 K)

{
10

5.20409

y=

1581.341
372.0+ ( 33.50 )

97.658

= 0.035

When T = 95.4C (368.4 K)

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{
10

5.20409

y=

1581.341
368.4+ ( 33.50 )

97.658

= 0.031

When T = 92.8C (365.8 K)

{
10

5.20409

y=

1581.341
365.8+ ( 33.50 )

97.658

= 0.029

When T = 86.3C (359.3 K)

{
10

5.20409

y=

1581.341
359.3+ ( 33.50 )

97.658

= 0.023

When T = 83.5C (356.5 K)

{
10

5.20409

y=

1581.341
356.5+ ( 33.50 )

97.658

= 0.021

When T = 78.9C (351.9 K)

{
10

5.20409

y=

1581.341
351.9+ ( 33.50 )

97.658

= 0.018

When T = 73.5C (346.5 K)

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{
10

5.20409

y=

1581.341
346.5+ ( 33.50 )

97.658

= 0.015

When T = 72.0C (345.0 K)

{
10

5.20409

y=

1581.341
345.0+ ( 33.50 )

97.658

= 0.014

When T = 70.0C (343.0 K)

{
10

5.20409

y=

1581.341
343.0+ ( 33.50 )

97.658

= 0.013

Sample Calculation of Methanol Mol Fraction from Calibration Table.

Water

: 9mL

Methanol : 1mL
mole=

density
x volume
molecular mass

Mole of water:
1
1 ml=0.056 mol
18
Mole of methanol:

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0.79
9 ml=0.222mol
32.04

Therefore,
mol fractionof methanol=

mole of methanol
mole of methanol +mole water

0.222
0.056 +0.222

= 0.799
DISCUSSIONS
Vapour-liquid equilibrium is commonly used in distillation process. This is involved of
binary mixture which is methanol and water for simplicity. X represented the mole fraction of
liquid and y represented the mole fraction of gas. This information is tabulated in a graft
which is equilibrium x-y diagram.
Two-component (binary) system can be represented by T-xy Diagram. Binary system is
easier to analysis by T-xy diagram. There are two main factors that make the vapour and
liquid compositions different at equilibrium which are the pure component vapour pressures
and the no ideal ties in the liquid phase. The refractive index for vapour and liquid is
recorded. The composition of methanol in the liquid and vaporise determined based on
Antoine equation.
For the first experiment, the volume of water is constant, which is 3L but the volume of
methanol is increased from 0.1L to 3L. Based on the experiments data, the temperature of
liquid mixture decrease from 95.3C to 78.3C and the temperature of vapour mixture
decreased from 99C to 83.5C.
By comparing the equilibrium line of experiment with the ideal equilibrium line, we
only got the slightly line compare to the literature line. This occur maybe due to the error like
putting the methanol in the beaker without closing and cause the methanol vaporise because
methanol is very volatile.

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The graph of refractive index versus mol fraction is the calibration curve of this
experiment. The calibration curve is very important to determine the unknown mole fraction
from the sample. T-xy diagram can be plot with help of the calibration curve. But, we use the
Antoine formula instead of this method.

CONCLUSION AND RECOMMENDATIONS

For the conclusion, the experiment was conducted successfully with some mistake or
error. The relationship of liquid and vapour at equilibrium is determined via the graft of
equilibrium. The composition of methanol is higher in the vapour compare to liquid and vice
versa for the water. This is because the methanol is volatile than the water, so methanol is
easy to vaporised compare to water. The experiment is conducted in a constant pressure
which is atmosphere pressure (1 atm). Water has higher boiling point than the methanol due
to lower vapour pressure. The objectives of the experiment are achieved, it can be concluded
that the experiment was successfully done.
On the other hand, to achieve more accurate and better results, some recommendations
have to be taken into account such as before starting the experiment makes sure that there is
no liquid inside the VLE unit and draw out all the liquid inside it if the liquid is still there.
Besides, ensure that the liquid is enough at all time to fully submerge the heater. Furthermore,
before started the draining always switch off the heater cool down the liquid. Also, make sure
to perform the general start up and shut down before and after the experiment is carried out.
Other than that, safety precaution should be taken seriously before entering the pilot plant.
For instance, lab coat with long sleeve as well as the safety cap should be worn before
entering the pilot plant and conduct the experiment. These are to avoid any unwanted
accidents inside the pilot plant.
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REFERENCES
i) Skoog, West, Holler & Crouch, Fundamentals of Analytical Chemistry, 8 th Ed,
Thomson Brooks/Cole, 2004.
ii) Raoults Law,
http://chemwiki.ucdavis.edu/Physical_Chemistry/Physical_Properties_of_Matter/Soluti
ons_and_Mixtures/Ideal_Solutions/Changes_In_Vapor_Pressure2C_Raoult's_Law,
accessed on 12th April 2014.
iii) Daltons Law of Partial Pressures,
http://chemistry.about.com/od/workedchemistryproblems/a/daltons-law-of-partialpressures.htm, accessed on 13th April 2014.
iv) Vapor-Liquid Equilibria, http://lorien.ncl.ac.uk/ming/distil/distilvle.htm, accessed on
12th April 2014.
v) Antoine Equation,
http://www.tau.ac.il/~tsirel/dump/Static/knowino.org/wiki/Antoine_equation.html,
accessed on 13th April 2014.
vi) Raoults Law, http://en.wikipedia.org/wiki/Raoult's_law, accessed on 12th April 2014.

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