F/QAP/021/001

College of Engineering
Name of the programme BEng Process Operations and Maintenance
Name of Module with Code Chemical Engineering Thermodynamics and Reaction
Kinetics, M3H824741
Level/Semester & AY Level 3, Semester B, 2021 - 2022
Course coordinator Dr Saravanan A M
Coursework Type Assignment
Assessment weightage 30%
Type and date of submission Online submission on 2nd May 2022

Aim To provide an understanding of the underlying principles of

Thermodynamics and reaction kinetics required for a
process engineer.
Learning Outcomes 1. Explain and analyse isothermal, isobaric, isochoric,
isentropic and cyclic processes for an ideal gas.
2. Analyse steam power and refrigeration cycles.
3. Analyse the reaction kinetics and behaviour of
reactors under various operating conditions to find
the rate expression.
4. Explain suitable applications of chemical reactors
relevant to process industries and analyse the
appropriate criteria for reactor selection.

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Solution 01:

Data Given:
Specific Heat Capacity (Cp): 29.3 kJ/kmol K
Required: Heat and Work Effect
Consider the following diagram showing the three thermodynamic processes:

1 3

a) Heating at Constant Volume

Since the process occur at constant volume (isochoric), then

P
= Constant
T

P 1 P2
= , where by P2 = 2bar, T1 = 300K and P1 = 1bar
T 1 P2

P 2 ×T 1 ( 2 ×30 0 )
T 2= = =600 K
P1 1

From Energy Equation

∆U = Q – W where ∆U = m ˙c p ∆T

W = ∫ PdV , since volume is constant then

W=0

Q = ∆U = m˙c p ∆T

Q
=c p ∆ T =c p × ( T 2 −T 1 )
ṁ
˙ ) × ( 600−30 0 ) K
Q̇= (29.3 kJ /kmolK

Q=8790˙ kJ /kmol

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Therefore, heat is 8790 kJ /kmol and workdone is 0 kJ/kmol

b) Adiabatic Expansion
Since the process is adiabatic, then there is no heat change. From energy equation:

∆Q = 0 kJ/kmol

From PV k =constant

cp
But k =
cv

Also, cp – cv = R where universal gas constant (R) is gas constant = 8.314 kJ/kmol K

cv = cp – R

cv = 29.3 – 8.314 = 20.986 kJ/kmol K

29.3
k= =1.396
20.986

From:

PV = RT

RT 8.314 ×600 3
V2 = = =0.02 49 m
P2 2× 100000

From an adiabatic relation for an ideal gas

k k
P2 V 2=P3 V 3

V 3=( V 2 )
√
k P2
P3
=( 0.02 49 ) ×
√
1.396 2
1
=0.0409 m
3

From W = ∫ PdV

P 2 V 2−P3 V 3 ( 2× 100000× 0.02 49 )−( 1 ×100000 ×0.0 409 )

W= = =2022.7273 J /mol
k −1 1.396−1

W = 2022.7273 kJ/kmol

Therefore, heat is 0 kJ/kmol and work done is 2247.4747 kJ/kmol

c) Cooling at Constant Pressure

Since the process occurs at constant pressure (isobaric process),

From W = ∫ PdV = P∆V

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W = P × (V 3−V 1)

But V 1=V 2 = 0.0249 m 3, V3 = 0.0409 m3

W = (1 × 100000) × (0.0409 – 0.0249) = 1600 kJ/kmol

Heat transfer for an isobaric process is given by the formula below:

Q = nCp∆T

Q = nCp(T3 – T1)

( )
( k−1)

( )
V2 0.02 49 ( 1.396−1 )
From process – 2 above, T 3=T 2 = ( 600 ) × =4 92.951 K
V3 0.0 409

Q = 29.3 × (492.951 - 300) = 5653.4646 kJ/kmol

Therefore, heat is 5653.4646 kJ/kmol and work done is 1600 kJ/kmol

Solution 02:
A process plant can be defined as a complete set of several process units, usually two or more,
and a direct supporting infrastructure or accessories required to provide a complete operation
function to produce or refine product(s). The extent of process units and process equipments
involved in a particular process plant depends entirely on the product under production and the
quality of the product intend. The size of process units and process equipments defines the size
the of the product that will be produced and vice versa. Small process plant for minor production
can be found at domestic level, while majority of process plants are found at industrial scale,
where products are produced at large quantities. (Moran, 2016)

Majority of process plants involves the transfer of heat into or from one process unit to another
of from a process unit or process equipment into the surrounding or from surrounding into the
process unit or process equipment. Majority of process plants usually require the maintenance
of process parameters such as temperature and pressure. Too low temperature or too higher
temperature can disrupt a particular plant process, and hence it is necessary to maintain the
temperature at particular set value. One of the important process units used for the control and
monitoring of temperature of process plant is Refrigeration process or refrigeration unit. This
process unit has a very wide range of applications from domestic applications, in
pharmaceutical to the industrial scale applications.

Refrigeration process can be defined as the process of removing heat from an enclosed unit or
an enclosed space or from a substance whose temperature is above the required level; and

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rejecting the removed heat into other spaces or into surrounding depending on the particular
design of the process plant. The main purpose of refrigeration process is to lower temperature
of the process unit or process equipment and maintain it at the set level of temperature. At
domestic level, refrigeration has been applied for cooling various domestic foods, medicines and
other substances that need low temperature storage. Refrigeration has been used in various
transportation vehicles for the storage of products that change or decomposed under certain
temperatures. Refrigeration has also been used in pharmaceutical industry for the storage of the
medicines, and in industrial scale for cooling of various products, process units or process
equipments.

Refrigeration plays an important role in daily life of human beings. Whether it occur under
natural force or under forced conditions, refrigeration is very useful in lowering the temperature
of a substance or bodies to satisfy the lower temperature requirements. In other words,
refrigeration is used to produce coldness to substances or bodies, which is the absence of heat.
(Ashrae, 2019)

The basic reason for the refrigeration is the removal of heat and maintenance of cold conditions
for a particular process unit or process equipment. Refrigeration is important at homes as it is
used to keep foods at good conditions and prevent the decay of foods. This is because, the
lowering of temperature slows down the bacterial activity within foods and hence prolong their
period for decay. Refrigeration is important in industrial processes as it is used to cool down
various industrial activities that involve heating process or industrial process whose chemical
reactions results into the generation of heat. Hence, refrigeration process is used to reject the
generated heat during industrial processes either into the surrounding or into other process
units that require heat input. In oil and Gas industry, refrigeration is used at mega scales for the
liquefication of natural gas or produced gas into liquefied petroleum products such as liquefied
natural gas (LNG) and liquefied petroleum gas (LPG). In pharmaceutical industry, refrigeration
is used to maintain the lower temperatures for the storage of medicines and pharmaceutical
equipments, in order to prevent microorganism activities such as bacterial activity that could
infect the pharmaceutical processes. Refrigeration process is also important in the storage of
highly vaporized products. These products tend to vaporized upon minor temperature rise,
hence needs the temperature to be kept as low as possible. The storage and transportation of
fishing products requires the effective refrigeration unit, as the products are likely to start
decaying with very small rise in temperature. Refrigeration is also applicable in hot climate
regions or during hot climatic seasons, to keep homes and offices at low comfortable
temperatures. (Bartley, 2022)

Refrigeration cools down the temperature of process units or products through the circulation of
a fluid medium called refrigerant, whose change in phase results into the lowering of the

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temperature. This refrigerant acts as the medium through which heat is transferred from the
units which needs to be cooled into the unit where heat is rejected. This circulation is referred to
as refrigeration cycle as shown in figure 1 below.

Figure 1: Basic Refrigeration Cycle (SRC, 2021)

The major thermodynamic feature of the refrigeration process or refrigeration unit is the
thermodynamic cycle. This cycle is characterized with major two levels of pressure namely,
condensation pressure which is high pressure and the evaporation pressure which is low
pressure. Thermodynamic cycle of refrigeration unit is comprised of a total of four
thermodynamic processes namely, heating at constant volume also known as isochoric
process, expansion which occurs at constant heat also known as adiabatic expansion,
compression and cooling at constant pressure also known as isobaric process. These four
processes occur in evaporator, expansion valve, compressor and condenser respectively, as
shown in figure 2 below. (SRC, 2021)

Figure 2: Ideal Vapor-Compression Refrigeration Cycle (SRC, 2021)

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Thermodynamically, a refrigeration cycle is the reverse of Carnot cycle, hence referred to as a

reversed Carnot cycle. For an ideal refrigeration cycle, the refrigerant fluid enters the
compressor as saturated vapor, and then cooled to the saturated liquid state in the condenser,
after which it is throttled to the evaporator pressure and vaporizes in the evaporator as it
absorbs heat from the chamber than needs to be cooled, and the cycle continues until when the
temperature of the refrigerated chamber or space is at the set value. Several types of
compressors can be used for the compression of the refrigerant including reciprocating
compressors, scroll compressors and rotary compressors. The main function of the expansion
valve is to cause a drop in pressure which enable the quick boiling of the refrigerant, creating a
two-phase mixture. Figure 2 shows the thermodynamic cycle of a refrigeration process.

The production of liquefied natural gas utilizes the refrigeration process. Liquefied natural gas
(LNG) can be defined as the natural gas whose temperature has been decreased down to -
162oC or -260oF, in order to shrink its volume by about 600 times the original volume, for the
purpose of easier and safe storage and transportation. At liquid state, natural gas will not ignite
hence ensuring the safety. Upon reaching its destination, a liquefied natural gas is degasified at
regassification plants. (Shell, 2022)

For a single-stage refrigeration process of natural gas, the refrigeration system is made up of
major four components namely chiller, compressor, condenser and surge tank as shown in
figure 3 below. The chiller is used to cool the hot natural gas coming from the production line or
from the processing units through the evaporation of the refrigerant.

Figure 3: Refrigeration Cycle for Natural Gas

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Numerical Problem (Nijella, 2021):

A particular refrigeration unit use R-12 as a refrigerant, operates between the pressures of 2.5
bar and 9 bar. The compression process is isentropic and there is no undercooling in the
condensing component. At the beginning of the compression, the vapor is in dry saturated
condition. You are required to estimate the theoretical coefficient of performance (COP). Given
actual coefficient of performance is 0.65 of theoretical value, you are required to calculate the
net cooling produced per hour. Assumes the refrigerant is flowing at 5 kg/min, and the specific
heat capacity (Cp) for superheated vapor at 9 bar is 0.64 kJ/kg K. The properties of the
refrigerant and the T-s and p-h diagrams are given below:

T1=T3=36OC=36+273=309K, T1=T4=-7oC=-7+273=266K, hf3=h4=29.62kJ/kg, h2=201.8kJ/kg,

h1=184.5kJ/kg, s2’=0.6836kJ/kgK, s1=s2=0.7001kJ/kgK

Pressure (bar) Saturation Temp (oC) Enthalpy (kJ/kg) Entropy of Saturated

Liquid Vapor Vapor
9.0 36 70.55 201.8 0.6836
2.5 -7 29.62 184.5 0.7001

Solution to Numerical Problem:

The temperature at point 2 (T2) is calculated from the following equation:

We know that entropy at point 2 (s2)
s2 =s′2 + 2.3cp log(T2/T′2)
0.7001 = 0.6836+2.3 × 0.64 log(T2/309)
log(T2/309) = (0.7001−06836)/(2.3×0.64) = 0.0112(T2/309) = 1.026 (The antilog of 0.0112)

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Then:
T2 = 1.026309 = 317K
From the enthalpy of superheated vapor at point 2,
h2 = h′2 +cp (T2 −T′2) = 201.8+0.64(317−309) = 206.92kJ/kg
Then, the theoretical coefficient of performance (COP)th can be calculated as follows:
(COP)th = (h1 − hf3)/(h2 − h1)
= (184.5 – 70.55)/(206.92 – 184.5)
= 5.1

Net cooling produced per hour can be calculated as follows:

(COP)actual = 0.65(COP)th
= 0.65×5.1
= 3.315
From actual work done
Wactual = h2 −h1
= 206.92 − 184.5
= 22.42 kJ/kg
Net cooling produced per kg of refrigerant can be calculated as:
Wactual × (COP)actual = 22.42×3.315
= 74.3kJ/kg
Then, net cooling produced per hour can be calculated as:
m × 74.3 = 5×74.3
= 371.5kJ/min

Solution 03:

A reactor is a vessel which allow substances or compounds to react chemically for the purpose
of experimentation or manufacturing processes. There are three major types of reactors used in
chemical reactions, namely; batch reactors, continuous stirred tank reactor and plug flow
reactor. These types of reactors have different characteristics and used for different forms of
reactions; however, the major distinction is based on the flow of reactants and products into and
out of the reactor.
Batch Reactor is an ideal reactor which has neither inflow nor outflow of reactants or products
which the reaction is being carried out. In this category, the reactants are initially charged into a
container, are well mixed and are left to react for a certain period of time and the resultant
mixture is discharged following the completion of chemical reaction. This type of reactor has low
capital cost but with high labor cost and generally it is used for small scale processes such as

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fine chemical and pharmaceutical manufacturing. In laboratory scale, it is commonly used to

obtain homogeneous kinetic data. (Levenspiel, 1999)

Figure 4:Simple Batch Reactor (Chen et al., 2013)

Design Equations:

The following assumptions are considered for the design of batch reactor:

i. It is perfectly mixed; thus, it has uniform concentrations.

ii. There is no variation in the rate of reaction throughout the reactor volume
iii. The temperature remains uniform throughout the reactor; however, it may change with
time.
iv. It is an unsteady-state operation where composition changes with time. (Schartl, 2014)

Reaction Kinetics of Batch Reactor:

Consider a simple elementary reaction A → B. In this reaction a reactant A will be decreasing
while a product B will be formed.

r=
1 dN
=
( V ) dC
N
i
=
d
i

i
i
V dt dt dt

p
If an ideal gas is used where C =
RT

1 d pi
r i=
RT dt

Thus, the rate of reaction of any component within batch reactor is given by the rate of change
of its concentration or partial pressure. If fractional conversion terms ( X A ) are used, then rate
equation can be written as shown below;

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NA
N A 0 −N A V CA
X A= =1− =1−
N A0 N A0 CA 0
V

−d C A
dX A =
C A0

Where N A 0 is the initial amount of reactant A, and N A is the amount present at time t in the
batch reactor. Rate reaction can also be represented as shown below. (Levenspiel, 1999)

n
-−r A =k C A where k is the rate constant and n A is the order of reaction relative to reactant A.
A

Reaction Velocity can be given as

−1 d C A 1 d C B
v= =
n A dt nB dt

For a batch reactor:

Consider an ideal batch reactor whose fluid volume remains constant. From material balance
equation
Input = output + disappearance + accumulation

( )( )(
rate of rate of

)(
rate
reactant reactant rate of reactant accumu
flow into = flow out + loss due ¿ chemical reaction ¿ within theelement ¿ of volume ¿ +
¿ of reactant∈
element of of element
volu
volume of volume

For a batch reactor, input = 0, output = 0

Rate of disappearance = - rate of accumulation

dN A
d [ N A 0 ( 1−X A ) ] d XA
(−r A ) V = dt = dt
=−N A 0
dt

d XA
(−r A ) V =N A 0 or
dt

XA
d XA
t=N A 0∫
0 (−r A ) V

Where t is the time required to achieve a conversion X A for either isothermal or non-isothermal
operation.
If density of the fluid remains contact, then

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XA CA
d XA d CA
t=C A 0 ∫ =− ∫
0 (−r A ) C (−r A ) A0

Space time (τ):

1 C A0 V V
τ= = =
s F A0 v0

This is the time required to process one reactor volume of feed measured at specified
conditions, where by V is reactor volume and v0 is the volumetric feed rate.

Space Velocity:

1
S=
τ

This is the number of reactor volumes of feed at specified conditions which can be treated in
unit time. (Levenspiel, 1999)

Pros and Cons of Batch Reactor

Batch reactor has several advantages over other types of reactors used for chemical reactions
in manufacturing processes or experimental processes. Some of these advantages include the
following:

 Batch reactor is ideal for multi-product processes. Unlike other types of chemical
reactors, batch reactors can be used to process variety of reactants and products.
Hence providing the flexibility of different products.
 Batch reactors have high conversion per unit volume for one pass of the reactants.
 Batch reactors are easy to use as they are simple with minimum instrumentations. Once
the products are input into the reactor, the products are left to react until the completion
of a chemical reaction.
 Batch reactors can be used to produce different reactors at different times. Unlike other
types of reactors, batch reactor is multi-purpose. A single reactor can be used to
produce or process different types of products.
 As compared to other types of reactors, batch reactors are easy to clean and repair or
maintenance. This is due to the easy access to the interior of the reactor.

Batch reactors have several disadvantages as compared to continuous stirred tank reactor and
plug flow reactors. Some of the advantages include the following:

 Batch reactors have high operating costs.

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 The quality of products manufactures by batch reactors have variable and lower quality
than the quality of the products produced by continuous stirred tank reactor (CSTR)
 Batch reactors are limited to batch processes only. Continuously flowing reactants and
products can not be processes by this type of reactor. As a results, batch processes can
only be used for small scale operations. Large volume manufacturing processes can not
be operated by batch reactors.

Pros and Cons of Continuous Stirred Tank Reactor (CSTR)

Continuous stirred tank reactor is the type of reactor which is characterized with the steady state
continuous flow of reactants and products, with the products having same composition as the
tank composition. Liquid phase, gas-liquid phase and solid-liquid phases can exist during the
reaction in these types of reactors. Some of the advantages of the continuous stirred tank
reactor include the following:

 CSTR allows continuous operation as reactants are continuously input while the
products are continuously removed from the reactor. As a results, large volume of
reactants can be processed per unit time.
 CSTR offers good control of process temperature, particularly for chemical reactions that
involve the generation of heat. In CSTR heat will be continuously controlled as reactants
and products are continuously flowing.
 As compared to batch reactor, CSTR are capable of adapting to two phases more easily.
 Continuous stirred tank reactors are simple to construct.
 Continuous stirred tank reactors have lower operating costs, as there is no need for the
periodic removal and separation of products and reactants.
 The interior parts of the continuous stirred tank reactor can easily be accessed, and the
reactor offers large volume capacity. Hence preferred for application that involves large
volumes of reactants and products.

Continuous stirred tank reactors have also several disadvantages over other types of chemical
reactors. Some of these cons are as follows:

 Continuous stirred tank reactor (CSTR) has lower conversion per unit volume. This is
due to the fact that, CSTR have lower retention time, as reactants and products stay for
a short period of time within the reactor during the continuous flow.
 When there is poor agitation, continuous stirred reactor can be faced with problems such
as channeling and by-passing of reactants. As a results, these reduce the conversion
per unit volume.
 Compared to tubular flow reactor, the continuous stirred tank reactors are easy to clean
and repair.

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 The size of the continuous stirred tank reactor is limited to the size of the motor used for
stirring, weight and the length of the motor shaft.
 Continuous stirred tank reactors are also faced with the existence of dead zones.
(Linquip, 2021)

Pros and Cons of Plug Flow Reactor

Plug flow reactor also known as tubular flow reactor is the tubular chemical reactor in which
reactants are introduced continuously at one end of the reactor, and the products are removed
at the other end of the reactor. Some of the advantages of plug flow reactor (PFR) include the
following:

 Plug flow reactors have high conversion per unit time. This is due to improved retention
time for reactants to reacts to produced products.
 Plug flow reactors have low operating costs than batch reactors and offers continuous
operation. The continuous operation increases the volume of the reactants and products
processed per unit time.
 Plug flow reactors offers good heat transfer.

Despite having various advantages, plug flow reactors have several disadvantages as
compared to continuous stirred tank reactor (CSTR) and batch reactor. Some of the
disadvantages of plug flow reactors include the following:

 Plug flow reactors are usually faced with the undesired thermal gradients and poor
control of temperature. The distribution of temperature along the reactor length can vary
and show undesired trends which may affect the chemical reaction of the reactants and
products. Hence, plug flow reactors cannot be used for processes that need high
thermal sensitivity.
 The cleaning and shutdown of plug flow reactors is more difficult and expensive as
compared to continuous stirred tank reactor.

Ethanol Production:

Ethanol can be produced from either petroleum-based product mainly through catalytic
hydration of ethylene or through a fermentation which is a biological process. Majority of the
ethanol used worldwide is produced through fermentation, while ethylene is used to produce
ethanol in small extents usually for laboratory or experimental purposes. The production of
ethanol through fermentation is typically biological process in which ethanol is produced as
sugar like glucose, fructose and sucrose is converted into cellular energy. Ethanol and carbon
dioxide are produced as by-products of the reaction. Yeast is usually used to perform
fermentation process in the absence of oxygen, hence considered as anerobic process.

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The conversion of sugar into cellular energy does not involve the continuous flow of neither
reactants nor products, hence considered as a batch process. In order to prevent the intake of
air (oxygen) into the reactor which will cause complete conversion of sugar into carbon dioxide
with little ethanol, the reactors must be air sealed, hence the continuous flow will likely cause
the entrance of air. Therefore, for the production of ethanol through fermentation, batch reactors
are mostly preferred.

Solution 04:

a) A reversible process can be defined as the process in which the system and the
environmental can be restored to exactly the same original or initial states that was before
the occurrence of the process, if we go bac along the path taken by the process. In practice,
a reversible process does not exist. For a process to be reversible, it must be performed
quasi-statically and must not be accompanied with any dissipative effects. In a real world, it
is impossible to attain complete reversible process, they can only be approximated by
different actual devices or equipments. This is due to the presence of irreversibilities that
exist in a real world. Irreversibilities are factors that render irreversible process, hence
preventing the occurrence of reversible process. Some of these factors include the
following:
 Friction
 Mixing of gases
 Unrestrained expansion
 Heat transfer across a finite temperature difference
 Electric resistance
 Chemical reactions
 In elastic deformation of solids
The presence of these irreversibilities impose the going back of process to exactly same
original state. For instance, in the unrestrained expansion of gas in a piston increase the
entropy of the system, hence enhancing the irreversibility of the process. In real life systems
the finite temperature difference is required to make a finite heat transfer rate possible, while
for reversible process, an infinitely small temperature difference leads to an infinitely slow
rate of heat transfer. A system condition can be restored to its original states, the

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impossibility usually arise in restoring the surroundings into original state. For a process to
be reversible, it must satisfy quasi-static requirement, that cannot be attained in actual
processes. (Niekerk, 2020)

b) Consider the second set of data:

T = 378K, PAS = 125.3kPa, PBS = 55.6kPa
From:
101.3 = 55.6 + xA (125.3 – 55.6)
XA = 0.656
From:
yA = 0.656 × 125.3/101.3 = 0.811

Repeating same procedures for T=383K, 388K, 393K and 398.6K, the results are shown in
table 1 below

T (K) 371.4 378 383 388 393 398.6

xA 1.000 0.656 0.487 0.312 0.157 0
yA 1.000 0.811 0.674 0.492 0,279 0

Boiling Point Diagram:

Boiling point diagram is created with the aid of Microsoft excel as the function of temperature
versus mole fraction

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Boiling Point Diagram

405
T-y
400 T-x
395

390
Temperature (K)
385

380

375

370

365

360

355
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1

Mole Fraction

Equilibrium Diagram:

The equilibrium curve is created by using the liquid and vapor mole fractions with the aid of
Microsoft excel.

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Equilibrium Diagram
1

0.8

y Mole Fraction 0.6

x-y
0.4

0.2

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

x Mole Fraction

References:

Ashrae, 2019. How refrigeration works. Available at:

https://www.newworldencyclopedia.org/entry/Refrigeration

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Bartley, 2022. Importance of Refrigerators. Available at:

https://www.bartleby.com/essay/Importance-And-Importance-Of-Refrigerators-PJJY9YZT3U

Levenspiel, O., 1999. Chemical Reaction Engineering. 3rd Edition. New York: John Wiley & Sons
Publishers

Moran, S., 2016. Process Plant Layout-Becoming a lost art. Available at:
https://www.chemengonline.com/process-plant-layout-becoming lostart/#:~:text=A%20process
%20plant%20is%20defined,Plot%20layout.

Niekerk, W., 2020. Understanding Thermodynamics: Course Notes. Available at:

https://bookdown.org/asvn90/Understanding-Thermodynamics/preface.html

Nijella, N., 2022. Problems on Vapor Compression. Available at:

https://www.ques10.com/p/394155/problems-on-vapour-compression-cycle/?

Schart, W., 2014. Basic Physical Chemistry. First Edition.

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