UNIVERSITI TEKNOLOGI MARA

FAKULTI KEJURUTERAAN KIMIA

THERMOFLUIDS LABORATORY
(CGE 536)
GROUP MEMBERS

: AMIRA BINTI KORMAIN (2014851022)

FARHAN HAIRI BIN KASSIM (2014204678)
MOHD ZAIDI BIN MOHD RADZALI (2014678172)
NURULTHAQIFAH BINTI BAHARUM (2014870248)

EXPERIMENT
DATE PERFORMED
SEMESTER
PROGRAMME
GROUP

:
:
:
:
:

No.
1
2
3
4
5
6
7
8
9
10
11
12
13

Title
Abstract/Summary
Introduction
Aims/Objectives
Theory
Apparatus
Procedures
Result
Calculations
Discussion
Conclusion
Recommendations
References
Appendices
TOTAL MARKS

VAPOUR LIQUID EQUILIBRIUM

13TH MARCH 2015
3
EH 243
GROUP 8
Allocated Marks (%)
5
5
5
5
5
10
10
10
20
10
5
5
5
100

Marks

Remarks:
Checked by:
Date:
LIST OF TABLES
TABLES

TITLE

PAGE

Vapor Liquid Equilibrium Data

10

Temperature and mole fraction of methanol

11

Mole fraction of methanol

16

Composition of methanol in mole fraction

17

FIGURE

TITLE

PAGE

Pxy diagram

Txy diagram

Txy diagram at different total pressure

Refractometer

Vapour Liquid Equilibrium Unit

LIST OF FIGURES

TABLE OF CONTENT
No.

Title

Pages

Abstract

Introduction

Aims/Objectives

Theory

Apparatus

Procedures

Results

10

Calculations

13

Discussion

18

10

Conclusion

19

11

Recommendations

19

12

References

20

13

Appendices

21

ABSTRACT
The experiment was conducted to construct an equilibrium curve for the methanol-water
system at atmospheric pressure. The experiment was carried out by using SOLTEQ Vapour
Liquid Equilibrium (VLE) unit. A mixture of methanol-water with known composition is at
first bolstered into the evaporator. At the point when the heater is exchanged on, the mixture
2

will begin to boil. The mixture vapor will ascend and will be chilled off by the condenser at
the top of the evaporator. As the vapor begins to consolidate, the liquid falls once more into
the evaporator. The system would achieve a balance state when the temperature stays
consistent. Vapor and liquid samples are taken to determine their composition. Toward the end
of the investigation, a graph of mole fraction of vapor against mole fraction of liquid and a
chart of temperature against mole fraction of liquid and vapor were plotted. This equilibrium
curves at atmospheric pressure for binary system specifically methanol and water obviously
demonstrates the relationship between vapor and liquid at equilibrium and at atmospheric
pressure. It can be said that from the graphs, the relationship between vapor and liquid at
equilibrium and at atmospheric pressure is linear. The experiment was viewed as a success as
all the objectives were accomplished.

1.0

INTRODUCTION

The understanding of phase equilibrium, and vapor-liquid equilibrium in particular is

important for many process engineering applications. These processes usually involve a
3

combination of two immiscible liquids of combination of liquid and gas. The ability to be able
to recognize when these phases are in equilibrium with each other and also calculating the
variables is especially useful for real life applications.
2.0

OBJECTIVES

The objective of this experiment is to construct an equilibrium curve for the methanol-water
system at atmospheric pressure.
3.0 THEORY
3.1 Introduction of Vapor-Liquid Equilibrium
A vapor/liquid mixture of two components could be considered and placed in a closed
container and the system is hold at constant temperature. For instance, a mixture of methanol
and water were introduced into the system for the analysis. The composition of the two phases
will slowly change as they distribute themselves between liquid and vapor phases through
vaporization and diffusion, and eventually the system will approach equilibrium state
(Sandler, 1999). This state can be determined or verified when successive readings of
temperature, liquid, liquid and vapor mol fractions are identical. The composition of the liquid
and vapor phases and the pressure of the system are fixed at this point and producible
according to the phase rule. If the 2-phase system is considered to be ideal, the composition of
both phases at thermodynamic can be given by Raoults law (Oremusov, 2007):
0

pi= pi xi

(1)

Where pi is the partial pressure of the component i above the solution surface, pi0 are the
pressures of the pure component, and x i is the molar fraction of component i. The total
pressure of the gaseous phase is given by Daltons Law (Oremusov, 2007):
p= p A + p B= p 0A + p0B
x A + x B=1

(2)
(3)

The intensive properties of and relationships between them is heavily concerned when
applying thermodynamics to phase equilibrium, and therefore the condition necessary to
determine the equilibrium state is specified by the phase rule.
3.2 Pxy and Txy Diagram
4

There are four intensive variables which is our concern in studying vapor-liquid equilibrium
in a binary system; temperature, pressure, a single liquid mol fraction, and a single vapor mol
fraction. The composition of a phase in a binary system can be determined with only a single
mol fraction due to the condition that the total mol fraction must equal to one. The maximum
numbers of intensive variable that can be specified are only two and occurs only when a
single phase is present .when phase rule is applied to binary system.
By holding one variable constant, the representation of phase behavior on a two-dimensional
plot can be accomplished as three variables are required to describe the state of a single phase.
As such, three different type plots are possible for the binary system. The Pxy diagram places
x and y as functions of pressure at constant temperature while in Txy diagram, x and y are
functions of temperature at constant pressure. The xy diagram puts x versus y at constant
pressure with temperature as parameter along the curve. The span of entire range of fractions
are found to be enveloped on Txy and Txy diagrams, thus rendering the PT plot to be of little
use unless we are concerned with the equilibrium near the critical region (Saad Al-Shahrani).

Figure 1: Pxy diagram

Figure 2: Txy diagram

Based on Figure 1, at equilibrium, the pressure P1 is equal for each phase and the liquid and
vapor curves are tied together by the tie line. Thus, the equilibrium and composition of x 1 and
y1 are obtained from the intersection of the phase by the line. By specifying two variables for
the two- component, two-phase system as per the phase rule, the other variable can be
determined by choosing either one. If the pressure is increased at constant temperature to P DP,
called the dew point, the composition z will begin to form liquid phase (Saad Al-Shahrani). In
Figure 2, the Txy diagram is characterized by temperature instead of pressure.

Figure 3: Txy diagram at different total pressure

In Figure 3, the Txy diagram shows that for the same system, the p 2 will be greater than p1.
The vapor liquid equilibrium temperatures are higher at p 2 than at p1 and the phase
equilibrium lines at higher pressure are usually closer together (Saad Al-Shahrani).

4.0 APPARATUS
SOLTEQ Vapour Liquid Equilibrium Unit, refractometer, beaker, measuring cylinder,
methanol, deionized water.

Figure 4 Refractometer

1
7

8
2

3
4
1

5
Figure 5 Vapour Liquid Equilibrium Unit

1. Condenser

6. Pressure Relief Valve

2. Evaporator

7. Control Panel

3. Bottom Sample Collector

8. Top Sample Collector

4. Cooling Water Supply

9. Rotameter

5. Cooling Water Drain

5.0 PROCEDURE
1)
2)
3)
4)

10. Hetaer

The general start-up procedure was performed.

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

Valve V1 was closed.

5) Valve V13 and V14 were opened at the level sight tube. The liquid level was make
sure to be above the safety line on the level sight tube. Valve V13 and V14 were closed
back.
6) Valve V10 was opened and adjusted to allow about 5 L/min of cooling water to flow
through the condenser.
7

7) The temperature controller TIC-01 was set to about 100 . The heater was
switched on.
8) The temperature rise in TIC-01 was observed. The liquid in the evaporator has begun
to boil when the temperature at TI-02 started to increase sharply. The pressure at PI-01
was observed. All temperature and pressure were waited to stabilize at a steady state
value.
9) The evaporator pressure and the liquid and vapour temperatures was recorded.
10) A liquid and vapour sample from the unit were collected. The samples were analysed
to determine their compositions.
11) The heater was switch 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 waited to drop significantly to signify that boiling has
sopped. Valve V11 was closed.
13) An additional 0.2L methanol was poured into the evaporator through valve V1. Valve
V1 was closed. There is now about 0.3L methanol and 3-L water in the evaporator.
Steps 5 to 12 above was repeated.
14) An additional 0.2-L methanol was poured into the evaporator through valve V1. Valve
V1 was closed. There is now about 0.5-L methanol and 3-L water in the evaporator.
Steps 5 to 12 above was repeated.
15) An additional 0.5-L methanol was poured into the evaporator through valve V1. Valve
V1 was closed. There is now about 1-L methanol and 3-L water in the evaporator.
Steps 5 to 12 above was repeated.
16) An additional 1-L methanol was poured into the evaporator through valve V1. Valve
V1 was closed. There is now about 2-L methanol and 3-L water in the evaporator.
Steps 5 to 12 above was repeated.
17) An additional 1-L methanol was poured into the evaporator through valve V1. Valve
V1 was closed. There is now about 3-L methanol and 3-L water in the evaporator.
Steps 5 to 12 above was repeated.
18) Valves V2 and V3 were opened to drain all liquid from the evaporator.
19) 2-L methanol and 1-L water was poured into the evaporator through valve V1. Valve
V1 and V8 were closed. Steps 5 to 12 above was repeated.
20) An additional 1-L of methanol was poured into the evaporator through valve V1.
Valves V1 and V8 were closed. There is now about 3-L methanol and 1-L water in the
evaporator. Steps 5 to 12 above was repeated.
21) An additional 2-L of methanol was poured into the evaporator through valve V1.
Valves V1 and V8 were closed. There is now about 5-L methanol and 1-L water in the
evaporator. Steps 5 to 12 above was repeated.
22) The general shut-down procedures was performed.
8

Sampling Procedures
1) Vapour sampling from the condenser.
i.
Vent valve V6 was ensure to be opened and drain valve V7 was closed.
ii.
Valve V5 was slowly open to allow some condensed vapour from condenser to flow
iii.
iv.

into the top sample collector. Valve V5 was closed.

Valve V7 was opened to collect the sample in a sampling vial.
The cap on the vial was immediately closed and the vial was immersed in cold

water.
2) Liquid sampling from the evaporator.
i.
Vent valve V4 was ensure to be opened and drain valve V3 was closed.
ii.
Valve V12 was opened to allow cooling water to flow through the bottom sample
iii.

collector.
Valve V2 was slowly open to allow liquid from evaporator to flow into the sample

iv.
v.

collector. Valve V2 was closed.

Valve V3 was opened to collect the sample in a sampling vial.
The cap on the vial was immediately closed and the vial was immersed in cold
water.

6.0 RESULTS
Volume

Volume of

Temperature (C)
Liquid
Vapor

RI (nD)
Liquid
Vapor

of Water

Methanol

(L)
3.0
3.0
3.0
3.0
3.0
3.0

(L)
0.1
0.3
0.5
1.0
2.0
3.0

93.0
89.3
87.5
83.3
79.9
77.8

98.3
94.3
92.2
86.2
82.8
78.1

1.3337
1.3345
1.3352
1.3379
1.3394
1.3410

1.0
1.0
1.0

2.0
3.0
5.0

72.7
71.0
69.3

73.7
72.0
70.1

1.3415
1.3407
1.3371

(X)

(Y)

1.3349
1.3407
1.3418
1.3410
1.3387
1.3364

0.0195
0.0567
0.0920
0.1725
0.3058
0.4122

0.0195
0.0570
0.0925
0.1729
0.3056
0.4108

1.3348
1.3333
1.3326

0.6308
0.7657
0.9218

0.6276
0.7614
0.9187

Table 1: Vapor Liquid Equilibrium Data

Mole Fraction
Liquid
Vapor

Temperature (C)
Liquid (X)
Vapor (Y)
93.0
98.3
89.3
94.3
87.5
92.2
83.3
86.2
79.9
82.8
77.8
78.1
72.7
73.7
71.0
72.0
69.3
70.1

Mole Fraction
Liquid (X)
Vapor (Y)
0.0195
0.0195
0.0567
0.0570
0.0920
0.0925
0.1725
0.1729
0.3058
0.3056
0.4122
0.4108
0.6308
0.6276
0.7657
0.7614
0.9218
0.9187

Table 2: Temperature and mole fraction of methanol

10

T-xy Diagram for Methanol-Water System

100
95
90
85
80

emperature Liquid (C)

Temperature T(C)

Temperature Vapor (C)

75
70
65
60
0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

0.8

0.9

Liquid/Vapor Mol Fraction

Graph 1: T-xy diagram for methanol-water system

X-Y Equilibrium

Vapor Mol Fraction

1
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
0

0.1

0.2

0.3

0.4

0.5

0.6

Liquid Mol Fraction

Graph 2: X-Y equilibrium

11

0.7

7.0 CALCULATIONS
Density of water (H2O) = 1 g/ml
Molecular weight of water (H2O) = 18 g/mol
Density of methanol (CH3OH) = 0.79 g/ml
Molecular weight of methanol (CH3OH) = 32.04 g/ mol

Number of mole =

Density
)
MW

Moles of Water (H2O)

Volume of 3 L (3000 mL)
Number of moles

1 g /ml
)
18 gmol (3000 ml)

= 166.667 mol
Volume of 1 L (1000 mL)
Number of moles

1 g /ml
)
18 gmol (1000 ml)

= 55.556 mol

12

[Volume]

Moles of Methanol (CH3OH)

Volume of 0.1 L (100 mL)
Number of moles

0.79 g /ml
)
32.04 gmol (100 ml)

= 2.466 mol
Volume of 0.3 L (300 mL)
Number of moles

0.79 g /ml
)
32.04 gmol (300 ml)

= 7.397 mol
Volume of 0.5 L (500 mL)
Number of moles

0.79 g /ml
)
32.04 gmol (500 ml)

= 12.328 mol
Volume of 1 L (1000 mL)
Number of moles

0.79 g /ml
)
32.04 gmol (1000 ml)

= 24.657 mol

13

Volume of 2 L (2000 mL)

Number of moles

0.79 g /ml
)
32.04 gmol (2000 ml)

= 49.313 mol
Volume of 3 L (3000 mL)
Number of moles

0.79 g /ml
)
32.04 gmol (3000 ml)

= 73.970 mol
Volume of 5 L (5000 mL)
Number of moles

0.79 g /ml
)
32.04 gmol (5000 ml)

= 123.283 mol

14

Mole Fraction of Methanol (CH3OH)

Volume

Volume of

Mole of

Mole of

Moltotal

Mole

Mole

of Water

Methanol

Water (mol)

Methanol

(mol)

fraction of

fraction of

(L)
3.0
3.0
3.0
3.0
3.0
3.0
1.0
1.0
1.0

(L)
0.1
0.3
0.5
1.0
2.0
3.0
2.0
3.0
5.0

166.667
166.667
166.667
166.667
166.667
166.667
55.556
55.556
55.556

(mol)
2.466
7.397
12.328
24.657
49.313
73.970
49.313
73.970
123.283

169.133
174.064
178.995
191.324
215.980
240.637
104.869
129.526
178.839

Water
0.985
0.958
0.931
0.871
0.772
0.693
0.530
0.429
0.311

Methanol
0.0146
0.0425
0.0689
0.1289
0.2283
0.3074
0.4702
0.5711
0.6894

Table 3: Mole fraction of methanol

15

Composition of Methanol (CH3OH) in mole fraction

Temperature (C)

Mole Fraction

Refractive Index, RI

Mole Fraction

(nD)
Water

Methanol

Methanol

Methanol

Liquid

Vapor

(H2O)

(CH3OH)

Liquid

Vapor

(Liquid)

(Vapor)

93.0
89.3
87.5
83.3
79.9
77.8
72.7
71.0
69.3

98.3
94.3
92.2
86.2
82.8
78.1
73.7
72.0
70.1

0.985
0.958
0.931
0.871
0.772
0.693
0.530
0.429
0.311

0.0146
0.0425
0.0689
0.1289
0.2283
0.3074
0.4702
0.5711
0.6894

1.3337
1.3345
1.3352
1.3379
1.3394
1.3410
1.3415
1.3407
1.3371

1.3349
1.3407
1.3418
1.3410
1.3387
1.3364
1.3348
1.3333
1.3326

X
0.0195
0.0567
0.0920
0.1725
0.3058
0.4122
0.6308
0.7657
0.9218

Y
0.0195
0.0570
0.0925
0.1729
0.3056
0.4108
0.6276
0.7614
0.9187

Table 4: Composition of methanol in mole fraction

16

8.0 DISCUSSION
Vapor-liquid equilibrium (VLE) undergirds the bulk of industrial separation processes,
particularly in the distillation processes. It will be consider only binary (two components)
mixture for simplicity. The composition of the liquid phase will be designated by the mole
fraction of the more volatile component (lower boiling point), represented by X meanwhile
the mole fraction of the vapor represented by Y. When the liquid is heated to its boiling point,
the vapor will produce, in general, have a different composition than the liquid. Thus, boiling
the mixture produces a partial separation of the component. If the vapor is collected, it can be
condensed and boil again to further change the composition.
The T-xy diagram represents the data for two-component (binary) system. T-xy
diagram is convenient for analysis the binary distillation system. There are two main factors
that make the vapor and liquid compositions different at equilibrium which are the pure
component vapor pressures and the no idealities in the liquid phase. The refractive index for
vapor and liquid is recorded. The composition of methanol in the liquid and vapor is
determined based on the refractive index.
The mole fraction for methanol and water are determined by calculation by using the
density of each compound. The density of methanol is 0.79 g/ml whilst the density of water is
1 g/ml. From the volume of methanol and water that had been used, the mass of the methanol
and water can be calculated by using the density of the methanol and water.
In the experiment, the volume of the water is kept constant at 3.0L and then being
mixed with different volume of methanol of 0.1L, 0.3L, 0.5L, 1.0L, 2.0L and 3.0L. The
temperature of the liquid methanol is decreased from 93.0C to 77.8C whereas the
temperature of the vapor methanol also decreased from 98.3C to 78.1C. The refractive
index for liquid methanol is decreased from 1.3337 to 1.3410 while the refractive index for
vapor methanol also decreased from 1.3349 to 1.3364. In addition to that, the mole fraction of
the liquid methanol is increased from 0.0195 to 0.4122 meanwhile the mole fraction for vapor
methanol also increased from 0.0195 to 0.4108.
On the other hand, in the second experiment, the volume of the water is kept constant
at 1.0L before being mixed with different volume of methanol of 2.0L, 3.0L and 5.0L. The
temperature of liquid methanol dropped from 72.7C to 69.3C and the temperature of vapor
methanol also dropped from 73.7C to 70.1C. The refractive index for liquid methanol is
decreased from 1.3415 to 1.3371 while the refractive index for vapor methanol also decreased
from 1.3348 to 1.3326. Moreover, the mole fraction of liquid methanol is elevated from
17

0.6308 to 0.9218 and the mole fraction of vapor methanol also elevated from 0.6276 to
0.9187.
Through the X-Y equilibrium graph, the mole fraction of liquid methanol is directly
proportional to the mole fraction of vapor methanol as it is both increased. The mole fraction
that had been used in the graph is calculated using the mole fraction formula
Methanol is a volatile liquid. During the experiment, putting the methanol in the
beaker without closing the beaker can cause the methanol to vaporize slowly. The methanol is
added before the temperature of the heater is lower than 50C. This will cause error to the
experiment and lead to inaccurate readings.

9.0 CONCLUSION
The conclusion for this experiment is the experiment is successfully carried out. The
relationship between vapour and liquid methanol at the normal pressure can be determined
successfully. The maximum mole fraction that can be achieved in this experiment is 0.6894.
The objective of this experiment is construct the equilibrium curve for the methanol-water
system at atmospheric pressure. From the result of this experiment, the composition of
methanol in liquid is higher than in vapour. The composition of methanol in liquid and vapour
is increase as the volume of methanol in mixture is increase. When the objective of this
experiment is achieved, it can be concluded that this experiment is successfully done.

10.0 RECOMMENDATION

Make sure that the heater is operating correctly before running the experiment.
Before starting the experiment, make sure that the water level is enough or at least fill

half of the evaporator.

Make sure that the cooling water is open when running the experiment.
Always cool down the sample before test it by using refractometer.

18

11.0 REFERENCES
S. I. Sandler. (1999). Chemical and Engineering Thermodynamics, John Wiley &Sons, Third
Edition.
Saad Al-Shahrani. (n.a.). Separation Process. Retrieved 18th March 2015 from
http://www.kau.edu.sa/Files/0008595/Files/59993_Lecture%206.ppt
J. Oremusov. (2007). Manual for laboratory practice in physics for students of pharmacy,
Department of Physical Chemistry, Faculty of Pharmacy, Comenius University, Bratislava.

19