Basics of Thermodynamics

Preface
Thermodynamics often confuses a beginner. And, there are valid

reasons for it. Let us, for instant, consider how the fundamental laws of
thermodynamics are introduced to an absolute beginner. Many texts
introduce the rst law by the statement When any closed system is
taken through a cycle, the net work delivered to the surroundings is
proportional to the net heat taken from the surroundings. And, the
second law is introduced by the Kelvin-Plank and the Clausius state-
ments, that are about the limits placed in physically realizing engines
whose working uids operating in cyclic processes.
Such an introduction to thermodynamics and teaching of the result-
ing corollaries, I realized, only made the young people grew indierent
to thermodynamics. Majority of them wrote in their course-teacher
evaluation sheets that they found it hard to relate to thermodynam-
ics. They, the students, made one thing very clear to me that, if they
were to like the subject thermodynamics, the subject matter should be
presented in a simple-and-easy-to-understand style.
I took up the challenge. I let go the historical approach to teach-
ing thermodynamics. I introduced the rst law as an expression of the
Conservation of Energy Principle. It is very neat to start with the
conservation of energy principle because the students nd it easy to
relate to conservation principles. With that simple tool, it is straight
forward to obtain the mathematical expressions for the rst law of ther-
modynamics applied to closed and open systems. Such approach, as I
realized, was very appealing to the young minds.
I also introduced each and every feature related to the rst law
of thermodynamics, even those that might seem obvious to many, in
great detail. I taught them what heat is and what it is not. Entropy, I
introduced, as yet another property without making the students attach
any unnecessary importance to that. The second law is introduced,
following the style of the great thermodynamic teacher, Professor H.C.
Van Ness, by the most general, yet the simplest, statement based on the
property entropy, which the students have already got familiar with.
Slowly, to my surprise, thermodynamics became the favourite sub-
ject among the majority of the engineering students. Thermo found
its way to the hearts of even those who were head to foot in love with
the electronic chips. The beginners, well at least a majority of them,
fell in love with thermodynamics. And, I started to enjoy teaching
thermodynamics.
This book on thermodynamics, written in an unconventional
and a student-friendly style, is the outcome of that fantas-
tic experience of people from two very dierent generations
coming to a meeting point in enjoying Thermodynamics to-
gether.
My sincere thanks are due to Mr. V. Shanmugaratnam of the De-
partment of Mechanical Engineering, University of Peradeniya, for read-
ing through the draft manuscripts at its dierent stages, and for his
encouraging feedbacks on the subject matter as well as on the style in
which it is presented.
I am indebted to Prof. S. Sivasegaram, former Head, Department
of Mechanical Engineering, University of Peradeniya, for providing me
the luxury of constructive criticism on the draft manuscript.
I gratefully acknowledge Prof. C.L.V. Jayathilake, former Dean,
Faculty of Engineering, and former Vice-Chancellor, University of Per-
adeniya, for his positive comments on the draft manuscript.
The nal revision of this book was carried out to accommodate the
suggestions and the comments made by Prof. Nihal E. Wijeysundera
of the National University of Singapore, and the other reviewer, the
identity of whom is unknown to me, assigned by the publisher of this
book.
I am extremely grateful to both of you for the positive inuence your
suggestions and comments had in nalizing the book to my satisfaction,
for the content of which I take full responsibility.
The chapter on Power Plants owes its existence to the Training
Programme on Thermodynamics for AES Kelanitissa Plant Engineers,
that I conducted for the plant engineers at the Combined Gas Turbine
- Steam Turbine Power Plant, AES Kelanitissa (Pvt) Ltd., Sri Lanka.
I thank Mr. Ravi Chandran, Plant Manager, for the opportunity pro-
vided.
I am also pleased to acknowledge my indebtedness to Dr. A.A.
Shelton Perera, Director, Science Education Unit, Faculty of Science,
x
University of Peradeniya, and to the other honourable members of the
Unit for getting the manuscript critically reviewed and for publishing
this book.
My warm thanks are to you, Mr. Suranga Manohara, Civil Engi-
neering & Graphic Design Consultant, for making my book a beauty
with your cover design, and for your valuable time.
And, my thanks are also due to my colleagues at the department,
for their generosity in letting me have that TIME that I badly needed
to nish this book, and for their steady support.
Finally, dear Kirthi, you have your ways in making me contribute
in the uncompromising ways that I always do and always want to do.
Thanks dear. I also thank all the other dear ones of my life, Katherina
and Maggie in particular, for wanting, so very badly, to see this book
going to print.
R. Shanthini
www.rshanthini.com
xi
Contents
Preface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ix
Symbols Used . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xii
Units Used . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xiv
1. The First Law . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
2. Thermodynamic Terminology . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
2.1 System, Surroundings & Boundary 8
2.2 Open, Closed & Isolated Systems 10
2.3 Property 11
2.4 State 13
2.5 Equilibrium State 13
2.6 Process 15
2.7 Simple Compressible System 17
2.8 State Postulate 18
2.9 Property Diagram 19
3. The First Law Applied To Closed Systems . . . . . . . . . . 21
3.1 Energy Balance for a Closed System 22
3.2 A Word of Caution 26
3.3 Worked Example 27
3.4 Summary 28
4. Internal Energy & Enthalpy . . . . . . . . . . . . . . . . . . . . . . . . . 29
4.1 Internal Energy 30
4.2 Enthalpy 32
4.3 Summary 34
5. Working with Ideal Gas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
5.1 Denition of an Ideal Gas 36
5.2 Absolute Temperature Scale 37
5.3 Dierent Forms of the Ideal Gas Equation of State 37
5.4 Internal Energy and C
v
38
5.5 Enthalpy and C
p
41
5.6 Relating Ideal Gas Specic Heats 42
5.7 Data on Ideal Gas Specic Heats 43
5.8 Evaluation of U for an Ideal Gas 46
5.9 Worked Examples 49
5.10 Summary 66
6. Working with Real Gases & Steam . . . . . . . . . . . . . . . . . . . 69
6.1 Real Gas Behaviour 70
6.2 Phase Change: Gas to Liquid 71
6.3 P-v diagram for Phase Change 78
6.4 P-T diagram for Phase Change 80
6.5 The Steam Table 81
6.7 Summary 108
7. Boundary Work . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109
7.1 Boundary Work in Real Life 110
7.2 Evaluation of Boundary Work 110
7.3 Quasistatic Process 114
7.4 Boundary Work in Real Processes 116
7.5 Units for Boundary Work 117
7.6 Path Dependence of Boundary Work 117
7.7 Other Forms of Work 119
7.9 Summary 158
8. All About Heat . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 161
8.1 What is Heat? 162
8.2 Heat Supply and Common Sense 163
vi
8.3 Heat Supplied to Increase the Temperature 164
8.4 Heat Supplied to Do Work 165
8.5 Temperature Increase without Heat Supply 166
8.6 Direct Evaluation of Q
in
167
8.7 Zeroth Law of Thermodynamics 168
8.8 Heat and Enthalpy 169
8.9 Heat and Internal Energy 170
8.10 Heat and Specic Heat 171
8.12 Summary 188
9. The First Law Applied To Open Systems . . . . . . . . . . . 189
9.1 Example of an Open System 190
9.2 Mass Balance for an Open System 192
9.3 Energy Balance for an Open System 193
9.5 Summary 208
10. The First Law Applied To Steady Flow Processes 211
10.1 What is Steady? 212
10.2 What is a Steady Flow Process? 212
10.3 Characteristics of a Steady Flow Process 213
10.4 Mass Balance for a Steady Flow Process 214
10.5 Energy Balance for a Steady Flow Process 215
10.6 Steady Flow Engineering Devices 217
10.8 Summary 247
11. Entropy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 249
11.1 Reversible Processes 250
11.2 Denition of Entropy 252
11.3 Evaluation of Entropy Change for any Process 253
11.4 Isentropic Process 255
vii
11.6 Summary 270
12. Thermodynamic Analyses Of Power Plants . . . . . . . . 273
12.1 Gas Turbine for Electric Power Generation 274
12.2 Gas Turbine for Jet Propulsion 281
12.3 Steam Turbine for Electric Power Generation 286
12.4 Gas Turbine - Steam Turbine Combined Power Plant 298
12.5 Minimizing the Heat Loss from Power Plants 303
13. Introduction To The Second Law . . . . . . . . . . . . . . . . . . . 305
13.1 The Second Law 306
13.2 Evaluation of Total Entropy Change 307
13.4 Summary 332
Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 335
viii
Chapter 1
THE FIRST LAW
If you were asked to prove that two and two made four, you might
nd some diculty, and yet you are quite sure of the fact.
Sherlock Holmes
Sir Arthur Conan Doyle (A Study in Scarlet)
Thermodynamics is a subject that gives us
the foundation needed to deal with energy.
One of the fundamental laws in thermody-
namics is the rst law of thermodynamics,
which states energy is conserved. Intro-
ducing the rst law to absolute beginners
is the objective of this chapter.
_
_
_
2 Chapter 1
Conservation of Energy
Conservation of energy means energy cannot be created or destroyed,
but energy can change from one form of energy to another. The rst law
of thermodynamics is simply the principle of conservation of energy. An
object falling from a tall building gains speed as it comes down, which could
be explained by the principle of conservation of energy as follows. A falling
object losses its potential energy, and the loss in potential energy gets
converted into a gain in kinetic energy. The gain in kinetic energy accounts
for the increase in the speed of the object falling through a height.
Similarly, water falling through a height as in a waterfall attains high
speed. The high speed water, when directed to the blades of a turbine (as
shown in the simplied diagram of Figure 1.1), sets the turbine blades in
motion, which in turn set the turbine shaft supporting the blades in rotary
motion. The rotating shaft can be used to do useful work. The potential
energy lost by water as it falls through a height is therefore converted into
useful work. We, of course, know that not all the potential energy lost
gets converted into useful work. A part of the potential energy lost, for
example, gets converted into work needed to overcome friction.
turbine blade
turbine shaft
Figure 1.1 A simplied diagram showing how a turbine shaft
is set in motion.
-
-
water
_
,
,
,
, ,
,
,
,
,
,
,,
Electricity can be generated in an electric generator in which a coil is

spun between the north and south poles of a magnet or an electromagnet.
To spin the coil, we require the rotation of a shaft, which can be provided by
water falling through a height as discussed above. This is the basic principle
behind hydroelectric power generation. Part of the potential energy lost by
water as it falls through a height is thus converted into electrical energy in
hydroelectric power generation.
The First Law 3
Conversion of heat energy into electrical energy can be achieved using
a steam turbine, the basic working principle of which is shown in Figure
1.2. Water from a water source, such as a river, is pumped into a boiler
operating at a high pressure. The water in the boiler is heated by burning
a fuel, such as furnace oil, in the furnace of the boiler. Steam at high
pressure, generated in the boiler-furnace arrangement, is further heated in
a superheater and directed to strike the turbine blades so as to set them is
motion. The turbine blades are attached to a turbine shaft such that the
moving blades set the shaft in rotary motion. The rotating shaft spins a coil
between the poles of an electromagnet and thereby electricity is produced.
Part of the heat energy released by the fuel burning in the furnace is thus
converted into electrical energy, which is yet another example of conversion
of energy from one form to another.
river
pump
_
boiler
furnace
water
steam
fuel
Figure 1.2 Basic working principle of a steam turbine.
turbine
blade
turbine
shaft
superheated
superheater
steam
What is Energy?
We spoke of potential energy, kinetic energy and electrical energy, and
we are very familiar with all these forms of energy. However, if we are
asked to dene energy in a clear and simple way, we nd it dicult to do
so. For example, we can write an equation to calculate potential energy,
but we cannot describe in simple words what potential energy is. We can
write an equation to calculate kinetic energy, but we cannot describe what
4 Chapter 1
kinetic energy is. It is the same with all other forms of energy as well. Even
though, it is dicult to dene energy in a simple way, one could look at
energy as some entity which possesses the capacity to do work.
Why is Energy Conserved?
Nobody really knows the answer to the question why energy is con-
served. Yet, we believe in conservation of energy because our experience
has shown us that energy is always conserved. That is, energy can be
neither created nor destroyed, but energy changes from one form to an-
other. Conservation of energy is therefore taken as a fundamental law, and
is named as the First Law of Thermodynamics.
What is a Fundamental Law?
A law that is in use because nobody has disproved it, is known as a
fundamental law. The rst law of thermodynamics has never been proved.
Even though the rst law has never been proved, we use it because no-
body has disproved it either. The rst law of thermodynamics is therefore
a fundamental law. We will believe in the rst law of thermodynamics and
continue to use it until someday, someone nds out that the rst law of
thermodynamics fails to describe some particular event.
Student: Teacher, you said that we cant prove the rst law of thermodynam-
ics, and that we shall have to believe in it. Do you really mean that I
should simply believe that the rst law of thermodynamics is true?
Teacher: Yes, if you want to continue with learning thermodynamics, you
should take the rst law of thermodynamics to be a true statement about
how the nature works, until the day someone disproves it.
Student: Please, permit me to ask another question. I am familiar with the
principle of conservation of mass, which states that mass cannot be cre-
ated or destroyed. Can the principle of conservation of mass be proved?
The First Law 5
Teacher: No, the principle of conservation of mass cannot be proved. There is
also the principle of conservation of momentum which cannot be proved
either. They are all fundamental laws.
Student: I have one more question, Teacher. We talk of mass, momentum
and energy as though they are distinctly dierent things like mangoes,
bananas and grapes. I have read something about the Einsteins theory
of relativity which says, I believe, that mass can be converted into energy.
If Einstein had it right then how could we treat mass and energy as two
separate things?
Teacher: It is perfectly alright for a beginner in thermodynamics to treat mass
and energy as two distinctly dierent things, and to use the principle of
conservation of mass and the principle of conservation of energy as two
separate principles. When we get interested in learning more about the
sun, the stars or the formidable nuclear reactors, in all of which mass is
being converted into energy, then it would be the right time for us to nd
out how to apply the conservation principles to such systems. We may
nd the books listed below to be of great help to us in our quest then.
Born, Max 1951 The Restless Universe. Dover Publications, Inc., New
York.
Feynman, R.P., Leighton, R.B. & Sands, M. 1997 The Feynman Lec-
tures on Physics, Volumes 1, 2 & 3. Narosa Publishing House, New
Delhi.
Venkataraman, G. 1994 At the Speed of Light. Universities Press (India)
Limited.
Application of the First Law
This book will show you how to apply the rst law, that is, the princi-
ple of conservation of energy, to thermodynamic systems as they go from
one state to another executing a process, during which the properties of
the system change. I am sure that you are familiar with the words such
as system, state, process and properties, and you know what these words
mean in everyday life. In thermodynamics, however, these words have very
specic meanings as described in the next chapter. Getting familiar with
6 Chapter 1
thermodynamic terminology in the next chapter is essential to learn ther-
modynamics with ease.
First Law of Thermodynamics
says that
ENERGY IS CONSERVED.
(That is, energy cannot be created or destroyed
but it can change from one form of energy to another.)
_ _
g g
_
Nooooo..., I am not talking about this kind of
energy conservation . . . . . . . . .

`
_
, ,
, ,
Chapter 2
THERMODYNAMIC TERMINOLOGY
There is nothing so strange in a strange land
than the stranger that visits it.
Anonymous
Even though thermodynamics is a subject that is very easy to learn,
some students nd it dicult because they get confused with the meaning
of the terms used in thermodynamics. In order to avoid such confusion,
the thermodynamic meaning of the frequently used terms are clearly stated
in this chapter. One can use this chapter as one uses a dictionary, coming
back to it to refer to the thermodynamic meaning of a term, whenever
there is a need for doing so.
8 Chapter 2
2.1 System, Surroundings & Boundary
System In thermodynamics, a system is either a quantity of
matter or a region of space selected for study.
Surroundings Everything that is outside the system is known as the
surroundings.
Boundary The closed surface that separates the system from its
surroundings is known as the system boundary. Mat-
ter and/or energy are exchanged between the system
and its surroundings across the boundary of the sys-
tem.
Let us say we want to study the behaviour of air contained in a piston-
cylinder device, the cross-section of which is shown in Figure 2.1. We
consider the air within the piston-cylinder device as the system. Surround-
ings consists of the piston, the cylinder, and the environment outside the
piston-cylinder device. The cross-section of the boundary is shown by the
dashed line in Figure 2.1, and it is an imaginary surface that separates the
air from the inner surfaces of the piston and the cylinder. Note that the
shape and size of the boundary of the system are changed when the piston
is moved by applying a force on the piston. Such a boundary is known as
a movable boundary.
Figure 2.1 Cross-section of a piston-cylinder device containing air.

cylinder
boundary
air
piston
Another example of a system is the gas trapped in a closed tank shown
in Figure 2.2. Its surroundings consists of the tank and the environment
outside the tank. The boundary is shown by the dashed line in Figure 2.2.
Thermodynamic Terminology 9
If the tank is made up of rigid walls then the shape and size of the boundary
cannot be changed when a force is applied on it. Such a boundary is known
as a rigid boundary.
boundary
.
tank
Figure 2.2 Cross-section of a closed tank containing gas.
gas
Yet another example of a system is shown in Figure 2.3. We want to

investigate the behaviour of the water contained in the tank. The problem
here is that the mass of water within the tank does not remain the same
throughout the investigation since water enters and leaves the tank through
the inlet and outlet, respectively. Therefore, all what we could investigate
is the behaviour of the mass of water within the tank at any given time. In
such a situation, we choose the region in space that contains the mass of
water within the tank as the system. The boundary of the system is marked
by the dashed line shown in Figure 2.3. Everything outside the boundary
is the surroundings.
.
.
.
.
.,
water
water inlet
-
water outlet
Figure 2.3 Cross-section of a tank containing water.
.
boundary
10 Chapter 2
2.2 Closed, Open & Isolated Systems
A system can be a closed system, an open system or an isolated system
depending on what can pass through its boundaries.
Closed System A closed system contains the same matter within
the system throughout the investigation. There-
fore, no matter crosses the boundary of a closed
system. However, energy can cross the boundary
of a closed system.
Open System An open system allows both matter and energy to
enter or leave the system.
Isolated System In an isolated system, neither matter nor energy
enters or leaves the system.
Air trapped in the piston-cylinder device shown in Figure 2.1 is an ex-
ample of a closed system since no air enters or leaves the system crossing
the boundary. Another example of closed system is the gas contained in the
tank shown in Figure 2.2 since the mass of gas remains the same throughout
the investigation.
The system of Figure 2.1 has a movable boundary, and therefore work
can be delivered to air by pushing the piston so as to decrease the volume
of air. The system of Figure 2.2 has a rigid boundary, and therefore no
work can be delivered to the gas contained within the rigid tank by moving
the boundary. Heat could enter or leave the closed systems of Figure 2.1
and Figure 2.2 through the boundaries, provided the walls are made up of
heat conducting materials.
The example of Figure 2.3 is an open system since matter, that is water,
enters and leaves the system during the investigation. Heat can be supplied
to the system through the walls of the container. Work, for example, can
be provided to the system using a stirrer to stir water. An open system
is also known as control volume, and its boundary known as control
surface.
It should be borne in mind that one very seldom comes across an iso-
lated system in real life. Nevertheless, in some cases, certain real systems
are approximated to isolated systems when carrying out thermodynamic
analyses.
2.3 Property
A property is any characteristic of a system which can be measured or
calculated. Temperature and pressure are examples of properties that can
be measured. Internal energy, enthalpy (see Chapter 4) and entropy (see
Chapter 11) are examples of properties that can be calculated. Properties
can be either intensive properties or extensive properties, the denitions of
which are given below.
Extensive Property Any property that relates to the quantity of all
matter present in the system is an extensive
property.
Extensive properties can be added up. Volume and energy of the entire
system are examples of extensive properties. We, in general, use upper case
symbols to denote extensive properties, such as V for the total volume of
the system, E for total energy, U for internal energy, H for enthalpy and
S for entropy.
Intensive Property Any property that is denable at a point in the
system is an intensive property, and its value
may change from one point of a system to an-
other.
Intensive properties cannot be added up. Temperature is an example of
an intensive property, and we know that a thermometer inserted at dierent
points in a system may register dierent temperatures. Pressure and density
are also examples of intensive properties. We, in general, use lower case
symbols to denote intensive properties. There are exceptions however, like
the symbols T and P used for the intensive properties temperature and
pressure, respectively.
Dividing an extensive property of a system by the total mass of the
system, we get a property known as specic property. An example of
specic property is specic volume, which is the total volume divided by
the mass, and it takes the unit m
3
/kg. Specic internal energy, specic
enthalpy and specic entropy are all specic properties.
Dividing an extensive property of a system by the amount of substance
present in a system, we get a property known as molar property. Molar
volume, which is the total volume divided by the amount of substance, is
12 Chapter 2
an example of molar property. In this textbook, we use the unit m
3
/kmol
for molar volume. Molar internal energy, molar enthalpy and molar entropy
are all molar properties.
Both the specic and molar properties are intensive properties. In this
textbook, we choose to denote them by the same lower case symbol. For
example, v is used to denote both the specic and molar volumes, u for
specic and molar internal energies, h for specic and molar enthalpies,
and s for specic and molar entropies. Such a usage is acceptable since the
respective units of v, u, h and s will clarify what the symbols represent.
Student: Teacher, what do you mean by amount of substance?
Teacher: You know that a quantity of matter can be measured by its mass.
What you may not know is that the quantity of matter can also be mea-
sured in terms of the amount of substance. The unit of amount of
substance is the mole, abbreviated mol. The number of elementary en-
tities in one mole of any substance is equal to the Avogadros number,
which is 6.022 10
23
. Here elementary entities mean atoms, molecules,
ions, electrons, etc.
Student: Teacher, you have not used the unit mol for the amount of substance.
You have used kmol. What is kmol then?
Teacher: One kilomole is equivalent to 1000 moles, and therefore the number
of elementary entities in one kilomole is equal to 6.022 10
26
. When
using kg as the unit for mass, it is convenient to use kilomole, abbreviated
kmol, as the unit for the amount of substance.
Student: Teacher, now I know that the amount of substance is a way to quan-
tify matter, and its unit is mole or kilomole. I also know that one kmol
of matter contains 6.022 10
26
elementary entities. In some textbooks,
however, I have seen the unit kgmol. Is kgmol the same as kmol?
Teacher: Yes, it is. Consider a substance with molar mass M. We know
that M grams of this substance is equivalent to one mole. If we take M
kilograms of this substance then we have one kilogram-mole, abbreviated
kgmol. Using these facts, let us work out the following:
1 kgmol = M kg = 1000 M g = 1000 mol = 1 kmol
Student: Okay. I see that one kgmol is the same as one kmol. Teacher, I want
to know one more thing. What is molar mass?
Teacher: The ratio between the mass of a substance m and the amount of
substance n is known as the molar mass, denoted by M. Therefore, M
= m/n. For example, the molar mass of carbon
12
, which is a particular
form of carbon, is exactly 12 kg/kmol. The common unit for molar mass
is g/mol, which is equivalent to kg/kmol, which is the unit used in this
textbook.
Student: Thank you, Teacher. I have one more question. Is molar mass the
same as molecular weight?
Teacher: The molecular weight is numerically equal to the molar mass taken
in the unit g/mol or kg/kmol. However, unlike the molar mass, molecular
weight is dimensionless. By the way, molecular weight is also known as
relative molecular mass.
2.4 State
State The condition at which a system exists is called the state of
a system. The state of a system is identied or described by
its properties.
It is straight forward to describe the state of a system by its extensive
properties such as the total volume of the systems. Describing a state
of a system by its intensive properties, however, is a dicult task since
intensive properties of a state may change from one point in the system
to another. If we are to describe the state of a system by the intensive
property temperature, for example, we need to measure the temperature at
numerous points across the entire system using a very, very large number
of thermometers. That would, of course, be an extremely dicult task to
perform.
2.5 Equilibrium State
Equilibrium State An equilibrium state is a state at which all in-
tensive properties remain uniform throughout
the system.
14 Chapter 2
When an intensive property remains uniform throughout the system, it
has one and the same value at each and every point in the system.
For example, a thermometer would register identical values of tem-
peratures at all points in a system at an equilibrium state. Therefore, a
single value of temperature is enough to describe the entire system at an
equilibrium state.
Similarly, pressure gauge would register the same value of pressure at
any point in a system at an equilibrium state. Therefore, a single value of
pressure is enough to describe the entire system at an equilibrium state.
In a system containing more than one component, chemical composi-
tion would be the same at any point in a system at an equilibrium state.
Therefore, a single value of chemical composition is enough to describe the
entire system at an equilibrium state.
It is the same with any other intensive property, such as specic volume,
specic enthalpy or any other specic property, of a system at an equilibrium
state. It is therefore an equilibrium state is a very convenient state to work
with.
ALL INTENSIVE PROPERTIES
REMAIN UNIFORM IN A SYSTEM
AT AN EQUILIBRIUM STATE.
Let us now consider the ideal gas equation of state P V = nRT, where
P is the pressure, V is the volume, n in the amount of substance, R is the
universal gas constant, and T is the temperature. It is interesting to note
that when we use the ideal gas equation of state, we use a single value of P
and a single value of T to represent the state, which is justied only if the
given state is an equilibrium state. It is important to note that properties
of a system can be interrelated using the ideal gas equation of state, only
if the state concerned is an equilibrium state.
2.6 Process
When a system changes from one state to another, it is said to execute
a process. The continuous series of states that a system passes through
during a process is called the path of the process. The following are a
few processes that one frequently comes across in thermodynamics:
Constant Pressure Process: It is a process during which the pres-
sure remains constant, while the other properties of the system may
change.
Constant Volume Process: During a constant volume process, vol-
ume remains constant while the other properties may change from
one state to another.
Isothermal Process: It is a constant temperature process. Even
though the temperature remains constant in an isothermal process,
heat may be transferred between the system and its surroundings. It
is common to supply heat to a system to maintain its temperature
constant.
Adiabatic Process: It is a process taking place while the system re-
mains thermally insulated from its surroundings. That is, no heat is
transferred between the system and its surroundings.
Student: Teacher, isnt an adiabatic process the same as an isothermal process.
Teacher: No, it is not. What makes you think that an adiabatic process is the
same as an isothermal process?
Student: You said that no heat is transferred between the system and the
surroundings of an adiabatic process. That means the temperature of the
system could not change during the process. You also said that a process
taking place at constant temperature is an isothermal process. Therefore,
these two processes are the same. Arent they?
Teacher: No, dear Student, they are not the same. I see that you are thinking
that a temperature of a system must remain constant if the system does
not exchange heat with its surroundings.
Student: Yes, Teacher. I think that.
16 Chapter 2
Teacher: Dear Student, it is wrong to think that a temperature of a system
does not change if the system does not exchange heat with its surround-
ings.
Student: Is it? Umm... Teacher, forgive me. I cant think of a system under-
going an adiabatic process where the temperature of the system changes.
Could you please help me with an example of such a process?
Teacher: Yes, I could. Consider a gas contained in a piston-cylinder device.
Let us take the gas as the system. Assume that the piston and the cylinder
are made up of heat resistant material. As a result, no heat is exchanged
between the system and the surroundings. Therefore, any process that this
system undergoes is an adiabatic process. Could you agree with that?
Student: Yes, I could.
Teacher: Now, let us imagine that a force is applied on the outer face of the
piston, as shown in Figure 2.4.
initial state
nal state
Figure 2.4 No heat is supplied, but a force is applied on the piston.
_ , ,
,
,
,
,
_ , ,
,
,
,
,
gas
If the force applied is large enough for the piston to overcome friction, it
would move such that the volume of the gas would be decreased. That is,
the gas is compressed by applying a force. As you know, compressing a gas
increases its pressure. Increasing the pressure increases its temperature.
Therefore, we have just seen an example where the work done to compress
the gas is responsible for increasing the temperature of the gas. So you
see the temperature of the gas could be increased by compressing the gas
during an adiabatic process.
Student: Teacher, I think that I am beginning to see the dierence between
an adiabatic process and an isothermal process.
Teacher: That is good. Let us then continue with the thermodynamic termi-
nology.
2.7 Simple Compressible System
As absolute beginners in thermodynamics, let us restrict ourselves to
studying the behaviour of simple compressible systems. These are
systems comprising pure substances uninuenced by surface tension eects,
motion, and gravitational, electrical and magnetic elds.
Student: Teacher, what do you mean by pure substance?
Teacher: A pure substance is a substance with uniform chemical composition.
Water is a pure substance since its chemical composition is the same
everywhere.
Student: Water is one single chemical compound, and therefore it has uniform
chemical composition. Air, which is a mixture of more than one chemical
compound, is not a pure substance. Am I correct?
Teacher: Remember that uniform chemical composition is the keyword
in dening a pure substance. Thus, air can be treated as a pure substance
as far as the chemical composition of air remains uniform. For that matter,
any mixture with a uniform chemical composition can be treated as a pure
substance.
Student: I think I have got it. Any substance can be treated as a pure sub-
stance as far as its chemical composition remains uniform.
As we have seen above simple compressible systems are uninuenced
by surface tension eects and external force elds, and therefore work of
changing surface area, electrical work, magnetic work, and the likes are
absent in such systems. Thus, properties, such as surface tension, electrical
charge, and magnetic dipole moment, have no signicance when dealing
with simple compressible systems.
The only form of work that we come across when working with simple
compressible systems is boundary work, that is the work done to com-
press (or expand) the volume of the system. And, the properties used to
characterize a state of a simple compressible system are pressure, volume,
temperature, internal energy, enthalpy and entropy. We already have some
18 Chapter 2
idea about pressure, volume and temperature. Internal energy and enthalpy
are introduced in Chapter 4, and entropy is introduced in Chapter 11.
It is common in the thermodynamic literature to refer to the simple
compressible system as simple system.
2.8 State Postulate
Even though a state of a system can be characterized by a number of
properties, repeated observations and experiments have shown that only two
intensive properties of a simple compressible system can be independently
chosen. That is to say the following:
Two independent, intensive properties are adequate
to completely specify an equilibrium state of a sim-
ple compressible system,
which is a simplied version of what is known as the state postulate.
The above version of the state postulate is sometimes referred to as a
two-property rule.
Once the two independent, intensive properties that specify the equi-
librium state are chosen, any other intensive property at that equilibrium
state is uniquely determined by these two properties.
Take, for example, air at 1 bar pressure and 27
C temperature. As-
suming that air behaves as an ideal gas, the molar volume of air shall be
calculated using the ideal gas equation of state as follows:
v =
V
n
=
RT
P
=
(8.314 kJ/kmol K) (300 K)
100 kPa
= 24.94 m
3
/kmol
In this case, we take P and T as the independent intensive properties.
Then, the third intensive property, molar volume v, is automatically xed.
2.9 Property Diagram
Let us choose the independent, intensive properties as pressure P and
specic volume v, and make a diagram of properties as in Figure 2.5.
Consider point I in the property diagram, it has coordinates (P
o
,v
o
). Since,
according to the state postulate, two independent, intensive properties are
adequate to x an equilibrium state of a simple compressible system, point I
in the P-v diagram represents an equilibrium state of a simple compressible
system.
Pressure
Specic volume
I
F
Figure 2.5 Equilibrium states I and F are shown on a property diagram.
,
,
v
f
v
o
P
o
P
f
Once (P
o
,v
o
) is specied, all the other intensive properties, such as T,
u, h and s, at that equilibrium state are automatically xed as functions of
P
o
and v
o
. Therefore, the state represented by point I on a P-v diagram
can as well be represented by a point on a h-s diagram, etc. That is to
say an equilibrium state of a simple system is xed by two of its intensive
properties just in the same way as a point in space is xed by its coordinates.
Let us now consider the equilibrium state represented by point F having
the coordinate (P
f
,v
f
) in Figure 2.5. We know that all the other intensive
properties at that equilibrium state are functions of P
f
and v
f
alone.
Let us consider a gas contained in a piston-cylinder device, say, at
the equilibrium state I shown in Figure 2.5. Let us imagine that the gas
undergoes a process, during which the gas expands and its pressure falls,
until it reaches the equilibrium state F shown in Figure 2.5. It is important
to note that whatever path is followed by the process to reach point F, the
properties at F remain the same since they are functions only of P
f
and
v
f
.
20 Chapter 2
Suppose we need to determine the total change in the pressure of the
system during the process considered. Since pressure is a property which
depends on the state, and not on how the system reaches that state, the
total change in pressure between the two equilibrium states I and F is
given by
P
f
Po
dP = P
f
P
o
where P
f
and P
o
represent the respective values of the property P at states
F and I.
In general, for any one of the properties P, v, T, u, h or s, represented
by the notation , say, we could write

f
o
d =
f

o
where
f
and
o
represent the respective values of the property at states
F and I.
`
_
_
_ _
`
_
dont run away........., come back
Chapter 3
THE FIRST LAW
APPLIED TO
CLOSED SYSTEMS
One only ever understands what one tames. People no longer have
the time to understand anything.
Antoine De Saint-Exupery (The Little Prince)
Chapter 1 stated that the rst law of thermodynamics is simply the
law of conservation of energy, and Chapter 2 introduced us to the ther-
modynamic meaning of terms such as system, property, and others. This
chapter demonstrates how to apply the rst law of thermodynamics to
closed systems.
22 Chapter 3
3.1 Energy Balance for a Closed System
The rst law of thermodynamics states that energy is conserved, which
means energy cannot be created or destroyed, but it may change its form.
Applying the rst law to a closed system involves accounting for energy,
that is simply writing an energy balance over the closed system as follows:
change in total energy content of the system =
energy that entered the system
energy that left the system.
Let us choose the closed system comprising a gas trapped within the
piston-cylinder device shown in Figure 3.1. The dashed line of Figure 3.1
shows the cross-section of the boundary that separates the system from
its surroundings, which includes the piston, the walls of the cylinder, and
everything outside the piston and the cylinder. One may ignore the parts
of the surroundings that have no inuence on the system, or are not inu-
enced by the system.
Figure 3.1 A closed system.

cylinder
boundary
gas
-
piston
Initially, let us say that the closed system, that is the gas, contains
an amount of energy E
o
. The gas is compressed by pushing the piston,
and W
in
amount of energy is provided to the gas as work. The walls of
the cylinder allow heat to pass through, and Q
out
amount of energy is lost
to the surroundings. Because of these work and heat energy interactions
The First Law applied to Closed Systems 23
between the system and its surroundings, the energy content of the system
changes to a new value, say E
f
. Energy balance for the closed system then
gives the following:
E
f
E
o
= W
in
Q
out
Using Q
out
= Q
in
, the energy balance could be rewritten as
E
f
E
o
= W
in
+ Q
in
which could be rearranged to give
Q
in
+ W
in
= E (3.1)
where the notation E is used to represent the change in the total energy
content of the system (E
f
E
o
). Note that the value of E depends on
the initial and nal states alone, and E, the energy content of the system,
is a property of the system.
Q
in
+ W
in
= E
is the First Law of Thermodynamics
applicable to closed system.
g g

The total energy content of the system, denoted by E, is made up
of internal energy, gravitational potential energy, kinetic energy, electrical
energy, magnetic energy, surface energy, etc. Chapter 4 attempts to give
an insight into the internal energy, denoted by U. For the time being, it is
adequate to know that changes in the thermodynamic properties, such as
temperature, pressure, and volume, are accounted for by the change in in-
ternal energy, denoted by U. Changes in electrical, magnetic, and surface
24 Chapter 3
energy are not considered in this text since these changes are insignicant
for most engineering systems.
Consequently, we write
E = U + (mg z) +
m
c
2
2
(3.2)
where the rst term on the right hand side of (3.2) represents the change
in internal energy U. The second term on the right hand side represents
the change in gravitational potential energy, where m is the mass, g is
the acceleration due to gravity, and z is the elevation of the system above
a reference level. The last term of (3.2) represents the change in kinetic
energy of the system owing to the motion of the system, where c is the
speed at which the system is moving as a whole.
A closed system which does not experience any change in its gravita-
tional potential energy or kinetic energy during a process is known as a
stationary system. For a stationary system experiencing no change in
electrical, magnetic or surface energy, (3.2) reduces to
E = U (3.3)
which, in turn, transforms the rst law of thermodynamics applied to a
closed system, given by (3.1), to
Q
in
+ W
in
= U (3.4)
This is the rst law of thermodynamics applied to closed stationary
systems for which changes in electrical, magnetic and surface energy are
insignicant. Such a system is known as the simple compressible system
(see Section 2.7), and for which internal energy U is the sole representative
of the total energy content of the system E.
The rst law given by (3.4) can be presented in dierential form as
dQ
in
+ dW
in
= dU (3.5)
Since the internal energy U is a property of state, integration of dU
from an initial state (o) to a nal state (f) gives
U
f
Uo
dU = U
f
U
o
= U (3.6)
which is the total change in the internal energy of the system.
Since Q
in
and W
in
are not properties of state, they depend on the path
of the process. Therefore, integration of dQ
in
and dW
in
gives
f
o
dQ
in
= Q
in
(not Q
in
) (3.7)
and
f
o
dW
in
= W
in
(not W
in
) (3.8)
where Q
in
and W
in
are the quantities of energy transfers between the
system and the surroundings in the form of heat and work, respectively,
when the system goes from state (o) to state (f) executing a process.
Thus, we see that integration of (3.5) yields (3.4).
_
_ _

Aa...
Ca...
_
Xv...
Zk...
Cb...
Wy...
|=

,,,
,
, ,
Q
in
+W
in
= U
26 Chapter 3
3.2 A Word of Caution
In this textbook, we write the rst law applied to closed simple com-
pressible systems in the form given by (3.4). Since W
in
= W
out
, (3.4)
can also be written as
Q
in
W
out
= U (3.9)
If the subscripts in (3.9) are omitted, we get
QW = U (3.10)
which is how some textbooks present the rst law of thermodynamics ap-
plied to closed simple compressible systems. The apparent confusion in
using dierent forms of the rst law of thermodynamics applied to closed
simple compressible systems vanishes if we learn to look at the equation
concerned with proper subscripts, as shown in Figure 3.2.
Q + W = U is the same as Q
in
+ W
in
= U
QW = U is the same as Q
in
W
out
= U
Figure 3.2 Dierent forms of the rst law applied to closed systems.
One can choose whichever the form that one prefers from Figure 3.2
to represent the rst law of thermodynamics applied to closed simple com-
pressible systems. There is absolutely no problem with it as far as one uses
consistent set of signs for work and heat transfers in and out of the systems
through the boundary.
It is important to keep in mind that for anyone of the four equations
of Figure 3.2 to be valid, internal energy U alone must solely represent the
total energy content E of the closed system considered. For such systems,
changes in gravitational potential energy, kinetic energy, and electrical,
magnetic and surface energy are all either completely absent or negligibly
small.
3.3 Worked Example
Example 3.1
It is reported that a closed system undergoes
a 3-step process in such a manner that the internal energy of the system
at its initial state is identically the same as the internal energy at its nal
state. In the rst step, the system absorbs 300 kJ of heat and performs 200
kJ of work on the surroundings. In the second step, the system loses 100
kJ of heat while it neither receives nor does any work. In the third step,
there is 100 kJ of work done on the system and it looses 50 kJ of heat.
Can you say whether this report is correct or not? Explain your answer.
Solution to Example 3.1
The system is said to undergo a 3-step process in such a manner that the
internal energy of the system at its initial state is identically the same as the
internal energy at the nal state. Since internal energy is a property of a system,
we have
U = U
at nal state
U
at initial state
= 0
The rst law of thermodynamics applied to the closed system undergoing
the given 3-step process therefore yields
Q
in
+W
in
= 0
Let us check this out by calculating Q
in
+ W
in
for the 3-step process from
the data provided as follows:
28 Chapter 3
Q
in
= 300 kJ 100 kJ 50 kJ = 150 kJ
W
in
= 200 kJ + 0 + 100 kJ = 100 kJ
Therefore, Q
in
+ W
in
= 150 kJ 100 kJ = 50 kJ = 0
There is something wrong here. One possibility is that there are errors in the
experimental observations. The other possibility is, of course, that there may
have been changes in some other modes of the energy of the system although
the net change in the internal energy U of the system is zero.
Remember that the most general form of the rst law of thermodynamics
applied to a closed system is Q
in
+ W
in
= E, where E, the total energy
change of the system, is given not only by U but also by changes in the
kinetic and potential energy, as given by (3.2). It is therefore possible that, even
though there is no change in the internal energy of the system, the potential
or the kinetic energy of the system as a whole could have undergone a change
giving rise to E = 50 kJ, and thereby explaining why Q
in
+W
in
= 50 kJ for
the given process even though U = 0.
That is, the given system may not be a stationary system.
3.4 Summary
First law applied to closed, simple compressible
systems:
Q
in
+W
in
= U (3.4)
First law in dierential form:
dQ
in
+dW
in
= dU (3.5)
Chapter 4
INTERNAL ENERGY & ENTHALPY
There the eye goes not, speech goes not, nor the mind.
We know not, we understand not
How one would teach it.
Maitri Upanishad, 6.17
This chapter gives a brief introduction to the properties internal energy
and enthalpy, that are extensively used in the rst law analyses of engines.
Internal energy is a property used in the rst law analyses of closed systems,
and enthalpy is a property used in the rst law analyses of open systems.
30 Chapter 4
4.1 Internal Energy
Internal energy U represents the total of all the microscopic modes of
energy associated with the random motion and the internal structure of
molecules. By microscopic modes of energy, we mean, for example, the
energy associated with the translational, rotational and vibrational motion
of individual molecules and the energy associated with the intermolecular
forces. The energy associated with the position, motion and spin of the
electrons, with the nucleus-electrons interactions in an atom, and with the
nucleus-nucleus interactions also contribute towards the microscopic modes
of energy.
These dierent microscopic modes of energies are strongly related to
macroscopic properties such as the temperature T, pressure P, volume V ,
electrical charge, magnetic dipole-moment, surface tension, etc. Internal
energy U, which represents the total of all the microscopic modes of energy
in a system, can therefore be taken as a function of all the macroscopic
properties, and can be expressed as
U = U(P, T, V, electrical charge, magnetic dipole-moment, etc.)
When dealing with simple compressible systems, as we do here, there is
no need for us to consider properties, such as electrical charge and magnetic
dipole-moment. The properties that are relevant to simple compressible
systems, apart from the internal energy, are pressure, temperature, volume,
enthalpy, and entropy.
The state postulate says that an equilibrium state of a simple com-
pressible system can be determined by specifying two independent, inten-
sive properties alone (see Section 2.8). Let us choose these two intensive
properties as specic (or molar) volume v and temperature T, then the
specic (or molar) internal energy is described as
u = u(v, T) at an equilibrium state of a simple compressible system.
Student: Teacher, I have a question. Property is any characteristic of a system
which can be measured or calculated. We can measure the temperature
of a system with a thermometer and the pressure by a barometer or by a
pressure gauge. What is the meter that we use for measuring the internal
energy?
Internal Energy & Enthalpy 31
Teacher: Internal energy cannot be measured, dear Student. For that matter,
no energy can ever be measured by any meter. You know very well what
kinetic energy is. Is there a meter to measure kinetic energy?
Student: Let me think about it. Hm..... No teacher, I have never used any
meter to measure kinetic energy. Well..., there is no meter to measure
potential energy, either. I have just calculated them from formulas de-
scribing these energies. Well...then there must be a formula to calculate
the internal energy. What is that formula?
Teacher: Oh.. dear Student, we cannot give a formula for internal energy in
classical thermodynamics.
Student: What is classical thermodynamics? Why cannot we give a for-
mula for internal energy in classical thermodynamics?
Teacher: Classical thermodynamics deals only with macroscopic proper-
ties such as T, P and V . I say temperature is a macroscopic property
since a thermometer inserted in a gas does not record the kinetic en-
ergy of each molecule, but the average kinetic energy of the molecules.
Pressure, for example, results from the bombardment of molecules. Even
though each molecule would bombard dierently from the other, pressure
probe measures only the local average value of all those bombardments.
Therefore, pressure is a macroscopic property. Classical thermodynamics,
which deals only with macroscopic properties, cannot provide a formula
for internal energy that represents the total of all microscopic forms of
energy. To have a formula for internal energy, one shall study statisti-
cal thermodynamics which deals with microscopic properties, such as
the kinetic energy of an individual molecule, the spin of an electron in an
atom, etc.
Student: Teacher, are you going to teach me statistical thermodynamics?
Teacher: No, I am not going to teach you statistical thermodynamics, because
the rst law analyses of most engineering systems can satisfactorily be
carried out with what we will learn in classical thermodynamics.
Student: Teacher, there is no meter to measure the internal energy. There is
no formula to calculate the internal energy in classical thermodynamics.
How are we then going to know the value of internal energy at a given
state of a system?
Teacher: Ah.. we are lucky there. We need not know the value of internal
energy at a given state for the successful application of the rst law of
32 Chapter 4
thermodynamics. Take a look at the rst law applied to a closed system,
which is Q
in
+ W
in
= U, where U is simply the internal energy
dierence between two given states of a system. Chapters 5 and 6 will
show you how to evaluate the internal energy dierence U between two
given states, without knowing the absolute value of U at either of the two
states.
Internal energy U takes the unit of energy which, in SI units, is the joule,
abbreviated J. We could also use multiples of this unit, such as kilojoule and
megajoule, abbreviated kJ and MJ, respectively. Internal energy per unit
mass is known as specic internal energy, and it is usually given the
unit J/kg. Internal energy content of a substance divided by the amount of
substance is known as molar internal energy, and it is usually given the
unit J/mol. Note that, internal energy is an extensive property, whereas
specic and molar internal energies are intensive properties.
In this textbook, we use the unit kJ for internal energy, kJ/kg for spe-
cic internal energy, and kJ/kmol for molar internal energy. We use U to
denote the internal energy, and the notation u to denote both the specic
and molar internal energies.
4.2 Enthalpy
Enthalpy, denoted by H, is dened as follows:
H U +PV (4.1)
Since U, P and V are properties, H is also a property. The unit of enthalpy
is the same as that of internal energy, which in general is the joules. The
unit of PV , pressure multiplied by volume, is also joules provided P is in
pascals (which is equivalent to N/m
2
) and V is in m
3
.
Dividing (4.1) by the mass of the substance, we get the specic en-
thalpy h as
h = u +Pv (4.2)
where u is the specic internal energy and v is the specic volume. Common
unit of specic enthalpy is J/kg.
Internal Energy & Enthalpy 33
Had we divided (4.1) by the amount of substance, we would have got
the molar enthalpy. Then u would have been the molar internal energy
and v the molar volume. Common unit of molar enthalpy is J/mol. Note
that enthalpy is an extensive property. Specic and molar enthalpies are
intensive properties.
In this textbook, we use the unit kJ for enthalpy, kJ/kg for specic
enthalpy, and kJ/kmol for molar enthalpy. We use H to denote enthalpy,
and the notation h to denote both the specic and molar enthalpies.
Student: Teacher, is enthalpy the same as heat?
Teacher: No. Enthalpy is very dierent from heat, and you will learn about
the dierence between enthalpy and heat in detail in Chapter 8. Now, let
me tell you that the enthalpy of a system may be increased by supplying
heat to the system.
Student: Teacher, forgive me for asking. What is enthalpy?
Teacher: My dear Student, there is only one answer for that question. Enthalpy
is a property dened by H = U +P V .
Student: Teacher, I want the physical meaning of enthalpy.
Teacher: Forgive me, dear Student, I am unable to give you a physical meaning
of enthalpy. All what I can tell you is we frequently encounter the combi-
nation of properties U + PV , particularly when applying the rst law to
open systems. For the sake of convenience, U + PV is dened as a new
property enthalpy. However, let me assure you that you will appreciate the
signicance of the property enthalpy when dealing with uids in motion,
as we will do with open systems in Chapters 9 and 10.
We know that a state of a simple compressible system can be described
completely by two independent, intensive properties (see Section 2.8). If the
properties are chosen as the specic (or molar) volume v and temperature
T, then the specic (or molar) enthalpy can be written as
h = h(v, T) at an equilibrium state of a simple compressible system.
34 Chapter 4
Student: Teacher, you have chosen v and T as the independent, intensive
properties, and expressed u and h as functions of v and T. Why dont we
choose, for example, P and T as the independent, intensive properties,
and express u and h as functions of P and T.
Teacher: Yes, we could also choose the independent, intensive properties to
be P and T, which are in fact easier to measure and control. However, it
is important to note that P and T can be independent of each other only
when the substance is in a single phase. When a substance exists in two
phases, like boiling water in a closed vessel, T cannot be changed without
aecting P, or P without aecting T. Therefore, we can write u =
u(P, T) or h = h(P, T) for an equilibrium state of a simple compressible
system only when the system remains in a single phase.
4.3 Summary
Internal energy is a property of a system that represents the sum of all
microscopic modes of energy in the system.
Enthalpy, H, is dened as
H U +P V (4.1)
and the specic (or molar) enthalpy is therefore given by
h = u +P v (4.2)
Specic (or molar) internal energy for a simple compressible system at an
equilibrium state can be written as a function of temperature and specic
(or molar) volume.
Specic (or molar) enthalpy for a simple compressible system at an equi-
librium state can be written as a function of temperature and specic (or
molar) volume.
For a simple compressible system at an equilibrium state u and h can also
be written as functions of T and P provided the system remains in a single
phase.
Chapter 5
WORKING WITH
IDEAL GAS
In thinking about the world we are xed with the same kind of
problems as a cartographer who tries to cover the curved face of
the earth with a sequence of plane maps. We can only expect an
approximate representation of reality from such a procedure and all
rational knowledge is therefore necessarily limited.
Fritjof Capra (The Tao of Physics)
In this chapter, we will learn to apply the rst law of thermodynamics
to closed, simple compressible systems containing ideal gas, which is indeed
an imaginary gas. However, the behaviour of real gases at low pressures
are often approximated to the behaviour of an ideal gas, the properties of
which are related to each other in a very special way. We will also learn
about these relationships in this chapter.
36 Chapter 5
5.1 Denition of an Ideal Gas
The volume occupied by the molecules of an ideal gas is assumed to be
negligibly small compared to the total gas volume. Also, molecules of an
ideal gas are assumed to have no inuence on each other. Hence, an ideal
gas satises the following two conditions:
An ideal gas at an equilibrium state can be described by the ideal gas
equation of state,
P V = nRT (5.1)
where P is the absolute pressure, V is the volume, n is the
amount of gas present, R is the universal gas constant, and T is
the absolute temperature. Absolute pressure is the actual pres-
sure at a point. When we measure the pressure at a point using
most pressure-measuring devices which read zero in the local atmo-
sphere, what we get is the gauge pressure. Absolute pressure is
then obtained by adding the local atmospheric pressure to the gauge
pressure. For a description on absolute temperature, see Section 5.2.
For information on the universal gas constant R, see Section 5.3.
The specic internal energy of an ideal gas is a function of tempera-
ture only. That is to say
u = u(T) for an ideal gas. (5.2)
In other words, the internal energy of an ideal gas experiences abso-
lutely no change when the volume occupied by an ideal gas or the
pressure exerted on an ideal gas is varied so as to change the in-
termolecular distances, while maintaining the temperature constant.
It should not be surprising, because we know that intermolecular
phenomena are totally absent in an ideal gas, and thus altering the
distances among the molecules of an ideal gas shall have absolutely
no inuence on the internal energy content of an ideal gas. How-
ever, changing the temperature of an ideal gas alters the behaviour
of the individual gas molecules, and therefore the internal energy is
changed.
The behaviour of real gases at low pressures can be approximated by
(5.1) and (5.2). It is therefore, a real gas at low pressures may be considered
an ideal gas.
Working with Ideal Gas 37
5.2 Absolute Temperature Scale
The scales of temperature in the SI units are the Celsius scale (
C),
which is also known as centigrade scale, and the Kelvin scale (K). Temper-
atures in these scales are related to each other by
T
K
= T
C
+ 273.15
where T
K
is the temperature in the Kelvin scale and T
C
is its equivalent
in the Celsius scale.
Kelvin scale is an absolute temperature scale, which implies the
lowest attainable temperature in the scale is zero. There are no negative
temperatures on an absolute temperature scale. The concept of absolute
temperature is one of the most confusing point in the subject of thermody-
namics for a beginner of this subject. The concept of absolute temperature
will become clear when one goes on to learn the second law of thermo-
dynamics. For now, let us accept the concept of an absolute temperature
scale without further elaboration and proceed.
5.3 Dierent Forms of
the Ideal Gas Equation of State
When using the ideal gas equation of state in the form given by
(5.1), we take P in kPa, V in m
3
, and T in K. The amount of gas
present, denoted by n, is taken in kmol. And, R takes the value 8.314
kJ/kmol K for any gas, and therefore it is known as the universal
gas constant.
The ideal gas equation of state is also used in the form
P V = mRT (5.3)
where P is in kPa, V is in m
3
, and T is in K. The mass of gas present,
denoted by m, is taken in kg. Therefore R takes the unit kJ/kg K.
When R is in kJ/kg K, it is known as the specic gas constant.
38 Chapter 5
We could also write the ideal gas equation of state in the form
P v = RT (5.4)
where P is in kPa, and T is in K. If v = V/n is the molar volume
in m
3
/kmol, then R is the universal gas constant, taking the value
8.314 kJ/kmol K for all gases. If v = V/m is the specic volume in
m
3
/kg, then R is the specic gas constant in kJ/kg K.
Combining (5.1) and (5.3), we relate the universal gas constant and the
specic gas constant by
n universal gas constant = m specic gas constant
which gives
specic gas constant =
universal gas constant
M
where M = m/n is known as the molar mass, and it takes the unit
kg/kmol. The universal gas constant takes the value 8.314 kJ/kmol K for
all gases, and the value of molar mass is specic to the gas. Therefore, the
numerical value of the specic gas constant, which depends on the molar
mass of the gas, is specic to the gas and its value changes from one gas
to the other. Please note it is common to use the same symbol R for both
the universal gas constant and the specic gas constant, since the units
will determine which one is in use.
Keep in mind that the numerical value of molar mass is the same as that
of the relative molecular mass, whereas molar mass takes the unit g/mol
or kg/kmol and the relative molecular mass is dimensionless.
5.4 Internal Energy and C
v
The change in the specic internal energy of any substance with
respect to temperature while the volume is maintained constant can be
expressed as
C
v
= lim
T0
u(v, T +T) u(v, T)
T
= lim
T0
u(T +T) u(T)
T
at constant volume
=
du
dT
v
(5.5)
which is the denition of C
v
known as the specic heat at constant
volume. It is one of the most extensively used specic heats in thermo-
dynamics.
Since u of an ideal gas is a function of T only, u is independent of its
volume. Therefore, the denition of C
v
given by (5.5) simplies to
C
v
= lim
T0
u(T +T) u(T)
T
=
du
dT
for an ideal gas. (5.6)
A visual representation of the specic heat at constant volume is given
in Figure 5.1, which shows a typical plot of u versus T for an ideal gas.
We know that the slope of the tangent to the u versus T curve at point A,
shown by the dashed line in Figure 5.1, represents an innitesimal change
in u with T at point A. This slope quanties the specic heat at constant
volume at the temperature represented by point A. Since the slope may
vary from one temperature to another, it is obvious that C
v
may also vary
with temperature. Since u is a function of T alone for an ideal gas, C
v
of
an ideal gas is a function only of T.
p
A
u
T
H
HY
u versus T curve
tangent at A
Z Z}
r
Figure 5.1 An example of u versus T curve.
40 Chapter 5
The unit for C
v
used in this textbook is kJ/kg K if u in (5.6) is taken
as the specic internal energy. The unit for C
v
used is kJ/kmol K if u
in (5.6) is taken as the molar internal energy. Since a unit change in the
Kelvin scale (K) is the same as a unit change in the Celsius scale (
C),
the numerical value of C
v
in kJ/kg K is identical to that in kJ/kg
C.
Similarly, the numerical value of C
v
in kJ/kmol K is the same as that in
kJ/kmol
C.
Equation (5.6) for an ideal gas can be rearranged to give
du = C
v
dT (5.7)
which is also applicable for any substance undergoing a constant-volume
process, see (5.5). Integrating (5.7) between the initial and nal equilibrium
states of a process, we get
u
f
uo
du =
T
f
To
C
v
dT
where u
o
and u
f
are the respective specic (or molar) internal energies at
the initial and the nal equilibrium states of the process, and T
o
and T
f
are
the respective temperatures at the initial and the nal equilibrium states of
the process.
Since u is a property, the above reduces to
u = u
f
u
o
=
T
f
To
C
v
dT (5.8)
which can be used to evaluate u for an ideal gas undergoing any process,
constant-volume or not, or for any substance undergoing a constant-volume
process.
If C
v
of (5.8) is in kJ/kg K, then
U = mu = m
T
f
To
C
v
dT
where m is the mass of the substance in kg. If C
v
of (5.8) is in kJ/kmol K,
then
U = nu = n
T
f
To
C
v
dT
where n is the amount of the substance in kmol.
5.5 Enthalpy and C
p
The change in the specic enthalpy of any substance with respect to
temperature while the pressure is maintained constant is expressed as
C
p
= lim
T0
h(P, T +T) h(P, T)
T
= lim
T0
h(T +T) h(T)
T
at constant pressure
=
dh
dT
P
(5.9)
which is the denition of C
p
known as the specic heat at constant
pressure. It is another extensively used specic heat in thermodynamics.
The specic enthalpy h given by (4.2) becomes
h = u +RT for an ideal gas, (5.10)
when the Pv term of (4.2) is eliminated using (5.4). Since u at an equi-
librium state of an ideal gas is a function of temperature alone and R is a
constant, it is obvious from (5.10) that h of an ideal gas is also a function
of temperature alone. That is to say
h = h(T) for an ideal gas.
Since h of an ideal gas is a function of T only, it is independent of its
pressure. Therefore, C
p
of (5.9) simplies to
C
p
= lim
T0
h(T +T) h(T)
T
=
dh
dT
Like C
v
, C
p
may also vary with temperature. The variation of C
p
with
temperature would, of course, be dierent for dierent substances. Since
h is a function of T alone for an ideal gas, C
p
of an ideal gas is a function
of T only. The units of C
p
is the same as that of C
v
(discussed in Section
5.4.)
Equation (5.11) for an ideal gas can be rearranged to give
dh = C
p
dT (5.12)
42 Chapter 5
which is also applicable for any substance undergoing a constant-pressure
process, see (5.9). Integrating (5.12) between the initial and nal equilib-
rium states of a process, we get
h
f
ho
dh =
T
f
To
C
p
dT
where h
o
and h
f
are the respective specic (or molar) enthalpies at the
initial and the nal equilibrium states of the process, and T
o
and T
f
are the
respective temperatures at the initial and the nal equilibrium states of the
process.
Since h is a property, the above reduces to
h = h
f
h
o
=
T
f
To
C
p
dT (5.13)
which can be used to evaluate h for an ideal gas undergoing any pro-
cess, constant-pressure or not, or for any substance undergoing a constant-
pressure process.
If C
p
of (5.13) is in kJ/kg K, then
H = mh = m
T
f
To
C
p
dT
where m is the mass of the substance in kg. If C
p
of (5.13) is in
kJ/kmol K, then
H = nh = n
T
f
To
C
p
dT
where n is the amount of the substance in kmol.
5.6 Relating Ideal Gas Specic Heats
The specic heats of an ideal gas are related to each other in a very
simple manner. Let us now see how to obtain this relationship. Take the
expression for the specic enthalpy of an ideal gas, h = u + RT, given by
(5.10), and dierentiate it with respect to temperature T. Since both h
and u are functions of temperature alone for an ideal gas, we get
dh
dT
=
du
dT
+R for an ideal gas.
Substituting C
v
= du/dT of (5.6) and C
p
= dh/dT of (5.11) in the
above expression, we get
C
p
= C
v
+R for an ideal gas. (5.14)
If the specic heats are in kJ/kmol K then R is the universal gas con-
stant. If the specic heats are in kJ/kg K then R is the specic gas
constant.
The ratio between the specic heats is known as the specic heat
ratio , and is dened as

C
p
C
v
(5.15)
The specic heat ratio is also known as the isentropic exponent,
and is sometimes denoted by k.
Combining (5.14) and (5.15) so as to eliminate C
p
, we get
C
v
=
R
1
Combining (5.15) and (5.16) so as to eliminate C
v
, we get
C
p
=
R
1
5.7 Data on Ideal Gas Specic Heats
Ideal gas specic heats are sensitive to changes in temperature. How-
ever, the eect of temperature is negligibly small on the specic heats of
monoatomic gases. Therefore, for monoatomic gases, such as argon, he-
lium, etc., C
v
= 12.5 kJ/kmol K and C
p
= 20.8 kJ/kmol K could be
used independent of temperature. Specic heats change rather slowly with
44 Chapter 5
temperature for diatomic gases, such as O
2
, H
2
, and N
2
. For polyatomic
gases, such as CO
2
, CH
4
, C
2
H
6
, etc, specic heats vary signicantly with
temperature.
Data obtained for C
p
of a gas at dierent temperatures while maintain-
ing low pressures, can be tted using algebraic equations such as the one
given below as a function of temperature:
C
p
= a +b T +c T
2
+d T
3
where the constants a, b, c and d take dierent values for dierent gases
as shown in Table 5.1. Algebraic expressions for C
p
are available in the
literature
for a large number of gases that are assumed to behave as ideal

gas. Substituting the algebraic equation describing C
p
in (5.14), we can
get the algebraic equation for C
v
as a function of T.
Gas a b 10
2
c 10
5
d 10
9
Hydrogen 29.11 -0.1916 0.4003 -0.8704
Oxygen 25.48 1.520 -0.7155 1.312
Air 28.11 0.1967 0.4802 - 1.966
Carbon dioxide 22.26 5.981 -3.501 7.469
Water vapour 32.24 0.1923 1.055 -3.595
Table 5.1 Values of the constants in C
p
= a +b T +c T
2
+d T
3
for a few
selected gases valid in the temperature range 273 K to 1800 K, where C
p
is in
kJ/kmol K and T is in K.
Table 5.2 shows the values of ideal gas specic heats of few selected
gases at 300 K. Specic heats are given both in kJ/kg K and in kJ/kmol K.
Multiplying the specic heat given in kJ/kg K by the molar mass, we get
the specic heat given in kJ/kmol K. The last column of Table 5.2 shows
the values of the specic heat ratio .
This table also shows that the specic heats of monoatomic gases are
almost the same, when taken in the unit of kJ/kmol K, and the specic
heats of diatomic gases are also nearly the same. It is common to assume
that air also falls into the group of diatomic gases. For polyatomic gases,
See, for example, Table A-2 of Cengel, Y.A. & Boles, M.A. 1998 Thermody-
namics: an engineering approach, 3
rd
Edition, McGraw-Hill International Editions.
specic heats dier from gas to gas. Note that specic heats of ideal gases
are also known as zero-pressure specic heats, and are sometimes
denoted by C
vo
and C
po
, since all real gases approach ideal-gas behaviour
at low (or near zero) pressures.
GAS C
p
C
v
C
p
C
v

molar mass (in kJ/kg K) (in kJ/kmol K)
(in kg/kgmol)
Argon
39.950 0.5203 0.3122 20.786 12.472 1.666
Helium
4.003 5.1930 3.1159 20.788 12.473 1.666
Hydrogen
2.016 14.3230 10.1987 28.875 20.561 1.404
Nitrogen
28.013 1.0400 0.7432 29.134 20.819 1.399
Air
28.97 1.005 0.718 29.105 20.793 1.400
Carbon monoxide
28.010 1.0410 0.7442 29.158 20.845 1.399
Carbon dioxide
44.010 0.8457 0.6568 37.219 28.906 1.288
Ethane
30.070 1.7668 1.4903 53.128 44.813 1.186
Table 5.2 Ideal gas specic heats at 300 K for a few selected gases.
It should be borne in mind that for real gases, the specic heats depend
not only on the temperature but also on the pressure or volume, and for in-
compressible substances, such as liquids and solids, both constant-pressure
and constant-volume specic heats are approximately the same, and thus
C
p
C
v
.
46 Chapter 5
5.8 Evaluation of U for an Ideal Gas
In this section we will learn to evaluate U, the internal energy dier-
ence, of an ideal gas in three dierent ways.
5.8.1 Using an Expression for C
v
Suppose you are asked to evaluate the specic internal energy change
of nitrogen when its temperature is increased from 300 K to 600 K at low
pressures given the expression
C
p
/R = a +bT +cT
2
+dT
3
+eT
4
where a = 3.675, b = 1.20810
3
, c = 2.32410
6
, d = 0.63210
9
,
e = 0.22610
12
, C
p
takes the unit of R, and T is in K.
Since nitrogen is held at low pressure, it is assumed to behave as an
ideal gas. Substituting the algebraic equation describing C
p
in (5.14), we
get
C
v
= (a +b T +c T
2
+d T
3
+e T
4
) R R
= (a 1) R +b RT +c RT
2
+d RT
3
+e RT
4
Substituting it in (5.8) and integrating the resulting expression from 300
K to 600 K, we get
u = (a 1) R(600 300)
+b R
600
2
300
2
2
+c R
600
3
300
3
3
+d R
600
4
300
4
4
+e R
600
5
300
5
5
Using the given numerical values of a, b, c, d and e, and R = 8.314

kJ/kmol K in the above, we get u = 6345.5 kJ/kmol.
The accuracy of the result obtained depends, of course, on the ac-
curacy of the algebraic equation used. This method is, however, a very
inconvenient method for hand calculations.
5.8.2 Using the Ideal-Gas Property Table
Alternatively, we can use the ideal-gas property tables, similar to
Table 5.3, to evaluate u of nitrogen as
u = u
at 600 K
u
at 300 K
= 12574 kJ/kmol 6229 kJ/kmol = 6345 kJ/kmol
In the above calculations, u is evaluated using the u values obtained
from ideal-gas property tables that are compiled by integrating (5.7) with
the help of computers using very accurate algebraic equations describing
C
v
as a function of temperature. This method therefore gives accurate
values of u. Also, it is very easy to use.
T h u
0 0 0
220 6,391 4,562
230 6,683 4,770
240 6,975 4,979
250 7,266 5,188
300 8,723 6,229
- - -
- - -
600 17,563 12,574
- - -
- - -
Table 5.3 Ideal gas enthalpy and internal energy for N
2
, where T is in K,
and h and u are in kJ/kmol K.
An important aspect of the ideal gas property tables, such as Table 5.3
and others
, is that the entries do not include pressure as an entry. It is
See, for example, the following tables:

Table A-17 to Table A-25 of Cengel, Y.A. & Boles, M.A. 1998 Thermodynamics:
an engineering approach, 3
rd
Edition, McGraw-Hill International Editions
Table A-5M to Table A-11M of Wark, K. 1989 Thermodynamics, 5
th
Edition,
McGraw-Hill International Editions.
48 Chapter 5
because data on ideal gas properties of gases are meaningful only at low
pressures since ideal gas behaviour is imitated by real gases only at low
pressures.
Another aspect of the individual entries of internal energy and enthalpy
in the ideal gas property tables is that individual entries of u and h depend
on the respective reference states chosen as described below. Let us set
the reference temperature as T
ref
, and the corresponding u and h values
are, say, u
ref
and h
ref
, respectively. Integrating (5.7) and (5.12) between
T
ref
and T, we get
u = u
ref
+
T
T
ref
C
v
dT
h = h
ref
+
T
T
ref
C
p
dT
The reference state chosen may dier from one thermodynamic property
table to the other. For example, the reference state chosen in Table 5.3 is
0 K, and the h and u values at this reference state are set to zero. The
individual entries of u and h at a chosen T may dier from one table to
another, since the individual entry depends on the reference state. However,
the change in internal energy or enthalpy calculated using individual entries
from a particular table is independent of the reference state, as shown below
for the case of u as
u = u
2
u
1
=
u
ref
+
T
2
T
ref
C
v
dT
u
ref
+
T
1
T
ref
C
v
dT
T
2
T
1
C
v
dT
5.8.3 Using an Average Value for C
v
Yet another, but an approximate method for the evaluation of u is to
take C
v
as a constant about an average value, (C
v
)
av
, over the temperature
range of our interest, which reduces (5.8) to the following approximate
relationship:
u (C
v
)
av
(T
f
T
o
) (5.18)
Similarly, if C
p
is assumed to be a constant about an average value,
(C
p
)
av
, over the temperature range of our interest, then (5.13) reduces to
the following approximate relationship:
h (C
p
)
av
(T
f
T
o
) (5.19)
Suppose (C
v
)
at 300 K
and (C
v
)
at 600 K
are given as 0.743 kJ/kg K and
0.778 kJ/kg K, respectively. Since these values are somewhat close, we
can evaluate the algebraic mean of the C
v
values given at 300 K and 600
K, which gives (C
v
)
av
= 0.761 kJ/kg K. Using this value in (5.18), we
get
u = 0.761 (600 300) kJ/kg
= (228.3 kJ/kg) (28.013 kg/kmol)
= 6395 kJ/kmol
Since u is evaluated using the average value for C
v
, the result is
only an approximate result. Yet, this method is widely used owing to its
simplicity, particularly when hand calculations are carried out. However,
the above method may give inaccurate results if the temperature interval
considered is very large.
5.9 Worked Examples
The following tools are useful in working out thermodynamic problems
on closed simple compressible systems containing ideal gas:
Tool 1: The rst law of thermodynamics applied to closed simple com-
pressible systems, given by Q
in
+ W
in
= U, which is also the
principle of conservation of energy.
Tool 2: Evaluation of U using data on specic heats, or data on internal
energy itself.
Tool 3: The ideal gas equation of state that interrelates pressure, tem-
perature, volume and mass (or amount of substance) of an ideal gas.
50 Chapter 5
Example 5.1
A closed rigid container, shown in Figure 5.2,
with negligible heat capacity has a volume of 1 m
3
. It holds air at 300 kPa
and 303 K. Heat is supplied until the tem-
perature of air reaches 500 K. Take C
v
for
air as 0.718 kJ/kg K. The molar mass of
air is 29 kg/kmol. Determine the amount
of heat supplied to air assuming air behaves
as an ideal gas.
Figure 5.2
air
container

The amount of heat supplied to the air, denoted by Q
in
, should be found.
Air in the closed container is taken as a closed system. The rst law applied to
the closed system, that is air, gives Q
in
+ W
in
= U. The container is rigid
and therefore the shape and size of its boundary cannot be changed. Thus, no
work is done at the boundary of the system in changing its shape or size and
thereby compressing or expanding the air contained in the container. There is
also no other forms of work involved, and therefore W
in
= 0. Thus, the rst
law gives
Q
in
= U (5.20)
If we can evaluate U by some means, then Q
in
will be known from (5.20).
Since air is assumed to behave as an ideal gas, (5.8) is used to evaluate u as
u =
500 K
303 K
(0.718 kJ/kg K) dT
= (0.718 kJ/kg K) (500 K 303 K) = 141.5 kJ/kg
Therefore,
U = 141.5 m kJ (5.21)
where m is the mass of air in the closed tank in kg, and the value of m is not
known.
There is only one way to calculate m, which is to use the ideal gas equation of
state in the form PV = mRT, in which R is the specic gas constant calculated
as
R =
8.314 kJ/kmol K
29 kg/kmol
= 0.287 kJ/kg K
We know the values of P, V and T at the initial state of the system, and
therefore we work out the value of m as
m =
P V
R T
=
(300 kPa) (1 m
3
)
(0.287 kJ/kg K) (303 K)
= 3.45 kg (5.22)
Substituting m of (5.22) in (5.21), we get
U = 141.5 3.45 = 488 kJ (5.23)
Combining (5.20) and (5.23) so as to eliminate U, we get Q
in
= 488 kJ
which is the amount of heat supplied to the air to increase its temperature from
303 K to 500 K.
Example 5.2
If the closed rigid container of Example 5.1
weighs 10 kg and is made of steel having the specic heat 0.5 kJ/kg
C,
determine the amount of heat supplied to increase the temperature of air
to 500 K.
The closed rigid container of Example 5.1 is made of a material with negli-
gible heat capacity, and therefore the container absorbs a negligible amount of
heat as we heat the air to reach 500 K. Thus, we ignored the amount of heat
supplied to the container, and evaluated only the amount of heat supplied to
the air to increase its temperature to 500 K.
In this example, the container is said to be made of steel. So, as we heat
the air to 500 K, the container also is heated to 500 K absorbing part of the
heat supplied. We, therefore, have to take the closed system to include both the
air and the container. Let us denote the amount of heat supplied to the closed
system as Q
in
, and we need to evaluate the value of Q
in
.
Since there are no work modes involved in the process, W
in
= 0. Thus, the
rst law applied to the closed system gives
Q
in
= U (5.24)
52 Chapter 5
where U is made up of the following components:
U = U
air
+ U
container
(5.25)
Since air in this example undergoes the same property changes as the air in
Example 5.1, U
air
is evaluated following the same steps as in Example 5.1.
Therefore, we get
U
air
= 488 kJ
U
container
is evaluated as
U
container
= mass specic heat temperature increase
= (10 kg) (0.5 kJ/kg
C) (500 K 303 K)
= 985 kJ
Substituting the above in (5.25), we get
U = 488 kJ + 985 kJ = 1473 kJ
which is used in (5.24) to obtain
Q
in
= 1473 kJ
which is the amount of heat supplied to increase the temperature of the air
from 303 K to 500 K when the air is contained in a steel container of 10 kg
mass and 0.5 kJ/kg
C specic heat.
Let us closely examine the equation
U
container
= mass specic heat temperature increase
which was used to determine the internal energy increase of the container
in Example 5.2. The term specic heat used here can be either C
v
or
C
p
, since C
p
C
v
for incompressible substances, such as liquids and solids.
Since specic heats are sometimes referred to as the heat capacities, the
statement container with negligible heat capacity in Example 5.1 sim-
ply means the specic heat of the material of construction of the container
is negligibly small. So U
container
is negligibly small for a container with
negligible heat capacity.
Example 5.3
Helium gas is contained in a rigid vessel of 0.5
m
3
at 500 kPa. The gas is agitated violently by a stirrer that transfers 250
kJ of work to the gas. Assuming that the system undergoes an adiabatic
process, determine the nal pressure of the gas. Assume that C
v
for helium
is a constant at 12.46 kJ/kmol K.
The nal pressure of helium, denoted by P
f
, could be calculated only in
one way, that is, by using the ideal gas equation of state at the nal state as
P
f
V
f
= nRT
f
. Since the vessel is rigid, the volume of the vessel remains a
constant. Therefore, V
f
= 0.5 m
3
. Substituting the known values in the above
equation, we get
P
f
0.5 = 8.314 nT
f
(5.26)
where P
f
is in kPa, n is in kmol and T
f
is in K. Calculation of P
f
from (5.26)
is possible only if we know the values of n and T
f
.
Let us calculate the value of n using the ideal gas equation of state at the
initial state as P
o
V
o
= nRT
o
, in which P
o
= 500 kPa, V
o
= 0.5 m
3
, and T
o
is
not known. Therefore, we get
500 0.5 = 8.314 nT
o
(5.27)
where n is in kmol as told already, and T
o
is in K.
There are two independent equations (5.26) and (5.27), and there are four
unknowns which are P
f
, T
o
, T
f
and n. We require two more independent
equations to solve for the unknowns.
We have been told at the beginning of this section that we can use three
tools. And, we have so far used only one which is the ideal gas equation of state.
Let us examine the problem statement to see if the rst law of thermodynamics
can be used in this example.
It is said that the system undergoes an adiabatic process, and therefore Q
in
= 0. It is also said that the system has rigid boundary and that 250 kJ of stirring
work is done on the system. Therefore, W
in
= 250 kJ. The rst law applied to
closed system, Q
in
+W
in
= U, thus gives
U = 250 kJ (5.28)
Now, there are three independent equations (5.26), (5.27) and (5.28), and
ve unknowns P
f
, T
o
, T
f
, n and U. We still require two more independent
equations to solve for the unknowns.
54 Chapter 5
Out of the three tools, we have so far used two which are the ideal gas
equation of state and the rst law of thermodynamics. The remaining tool is
the evaluation of U using data on specic heats, or data on internal energy
itself.
Since the value of C
v
is given in the problem statement and since helium
behaves as an ideal gas, we evaluate U using (5.8) as
U = (n kmol)
T
f
K
To K
(12.46 kJ/kmol K) dT
= 12.46 n(T
f
T
o
) kJ (5.29)
Eliminating U from (5.28) and (5.29), we get
12.46 n(T
f
T
o
) = 250 (5.30)
Now, there are three independent equations (5.26), (5.27) and (5.30), and
four unknowns P
f
, T
o
, T
f
and n. We require one more independent equation
to solve for the unknowns.
We have used all the three tools available, and there are no other means
to get that missing equation from the data available in the problem statement.
Therefore, we have to work with what is available to determine the value of P
f
.
There is a way to do so. Let us eliminate T
f
and T
o
from (5.30) using (5.26)
and (5.27), respectively, as below.
12.46 n
0.5 P
f
8.314 n

500 0.5
8.314 n
= 250
which gives P
f
= 833.6 kPa.
Example 5.4
An unidentied gas of mass 6 g is contained in
a piston-cylinder device of negligible heat capacity. The pressure of the gas
is 1.7 bar, its volume 0.002 m
3
, and its temperature 27
C. The gas expands

receiving 445 J of heat. The temperature of the gas becomes 115
C, its
pressure reduced, and its volume increased. The work done by the gas on
its surroundings is 100 J. Determine the values of C
v
, C
p
, and the molar
mass of the gas, assuming ideal gas behaviour.
Since ideal gas behaviour is assumed, we use (5.8) to determine the value
of C
v
. Taking C
v
as a constant, we get from (5.8)
u = C
v
(T
f
T
o
) (5.31)
Since T
o
= 27
C and T
f
= 115
C, we get (T
f
T
o
) = 88
C, which is
equivalent to 88 K since a unit change in

C is the same as a unit change is K.
Therefore, (5.31) gives
C
v
= u/(88 K) (5.32)
Now we need to calculate the internal energy change. The gas receives 445
J of heat and do 100 J of work. Taking the gas as the closed system, the rst
law of thermodynamics is applied as
U = Q
in
+W
in
= 445 J + (100 J) = 345 J
The mass of the gas is 6 g, and thus
u = U/m = 345 J/6 g = 57.5 J/g (5.33)
Eliminating u from (5.32) and (5.33), we get
C
v
=
57.5 J/g
88 K
= 0.653 J/g K = 0.653 kJ/kg K (5.34)
It is possible to determine the value of C
p
using C
p
= C
v
+R given by (5.14)
for an ideal gas, provided we know the values of C
v
and R. We, of course, know
the value of C
v
in kJ/kg K from (5.34), and therefore we need the value of R
in kJ/kg K.
Since the values of pressure, volume, mass and temperature at the initial
state of the gas is given in the problem, we nd R using the ideal gas equation
of state given by (5.3) as
R =
(1.7 100 kPa) (0.002 m
3
)
(0.006 kg) (273 + 27) K
= 0.189 kJ/kg K (5.35)
which is the specic gas constant.
Substituting the value of C
v
from (5.34) and R from (5.35) in (5.14), we
get the value of C
p
as
C
p
= C
v
+R
= 0.653 kJ/kg K + 0.189 kJ/kg K = 0.842 kJ/kg K
56 Chapter 5
The molar mass could be found as
M =
universal gas constant
specic gas constant
=
8.314 kJ/kmol K
0.189 kJ/kg K
= 43.99
kg
kmol
44
kg
kmol
Going through Table 5.2, we see that the numerical values of C
v
, C
p
and
M evaluated above match with those of carbon dioxide.
Example 5.5
A thermally insulated rigid box of negligible
heat capacity contains two compartments of equal volume. Initially, one
compartment contains air at 5 bar and 25
C, and the other is evacuated.

The dividing partition of negligible mass, is then raptured. Calculate the
nal air temperature and pressure. It is a common assumption that air at
low or moderate pressures behaves like an ideal gas. The value C
v
for air
at room temperature is 718 J/kg K.
As shown in Figure 5.3, compartment A contains air initially, and compart-
ment B contains nothing, that is vacuum. When the partition is raptured, air in
compartment A rushes into compartment B. Because air rushes to occupy the
entire box, the pressure and temperature of air occupying the entire box have
highly nonuniform distributions. If we allow a considerable length of time to
pass, then it is possible for air occupying the entire box to reach an equilibrium
state, having a nal temperature T
f
and a nal pressure P
f
uniformly distributed
everywhere within the box. We need to nd the numerical values of T
f
and P
f
.
To be able to work out this problem, it is important to choose the system
with care. Let us choose the closed system to include air in compartment A,
compartment B, partition, and the rigid vessel. The boundary of the system
chosen is represented by the dashed line in Figure 5.3.
initial state, nal state,
A B
air at
P
A
=5 bar
T
A
=298 K
vacuum
P
f
= ?
T
f
= ?
(V
A
= V
B
)
with partition without partition
Figure 5.3 The initial and nal states of the system of Example 5.5.
Since no heat or no work crosses the boundary, the rst law applied to the
chosen closed system yields
U = 0 (5.36)
which means there is no change in the total internal energy of the closed system.
The total internal energy change of the chosen closed system is made up of the
following components:
U = U
air in A
+ U
vessel
+ U
partition
where compartment B makes no contribution towards the total internal energy
change of the system since it contains nothing. The vessel has negligible heat
capacity and the partition has negligible mass, and therefore their contributions
to the total internal energy change of the system are negligible. Thus, we get
U = U
air in A
= 0 (5.37)
which means the internal energy of air that was initially occupying compartment
A remains a constant.
Since the mass of this air remains the same, we conclude that the specic
internal energy of air that was occupying compartment A remains a constant,
which means
u
air in A
= 0 (5.38)
Air is assumed to behave as an ideal gas, and C
v
of air is taken a constant.
Therefore, with the help of (5.8), we expand (5.38) to give
C
v
[T
f
T
A
] = 0 (5.39)
58 Chapter 5
where T
A
is the temperature of air occupying compartment A at the initial state,
and T
f
is the temperature of air occupying the entire box at the nal state.
Equation (5.39) gives
T
f
= T
A
= 298 K = 25
C (5.40)
That is to say the temperature of air has not changed even though the volume
occupied by air has doubled. This should not come as a surprise since the specic
internal energy of air, taken as an ideal gas, is a function of temperature alone.
There was no change in the specic internal energy of air according to (5.38),
and therefore there is no change in its temperature, either.
Now, we have to nd the nal pressure P
f
. Note that we have already used
two of the three tools mentioned at the beginning of this section. We are left
with only one tool which is the ideal gas equation of state. Application of the
ideal gas equation of state to air at its initial and nal states gives the following
respective equations:
P
A
V
A
= nRT
A
and (5.41)
P
f
(V
A
+V
B
) = nRT
f
(5.42)
where P
A
, V
A
and T
A
are the respective pressure, volume and temperature of
air at its initial state, and P
f
, (V
A
+ V
B
) and T
f
are the respective pressure,
volume and temperature of air at its nal state. The amount of air occupying
compartment A at the initial state is the same as that occupying the entire box
at the nal state, and is denoted by n.
Eliminating the term (nR) from (5.41) and (5.42), we get
P
f
(V
A
+V
B
)
T
f
=
P
A
V
A
T
A
(5.43)
Compartments A and B are of equal volume, and therefore V
A
= V
B
. We
also know from (5.40) that T
f
= T
A
. Using the above facts and the information
that the pressure of air in compartment A at the initial state, P
A
, is 5 bar in
(5.43), we get
P
f
= 2.5 bar
Example 5.6
A thermally insulated, rigid vessel with negligi-
ble heat capacity is divided into two compartments A and B by a non heat
conducting partition of negligible mass such that V
A
= 4 V
B
. Each con-
tains nitrogen which behaves ideally. Compartment A is at 1 bar and 300
K, and compartment B is at 4 bar and 600 K. Determine the equilibrium
temperature and the equilibrium pressure reached after the removal of the
partition. The value C
v
for nitrogen may be assumed a constant at 0.743
kJ/kg K.
This problem is similar to that of Example 5.5, except for the fact that
compartment B is not vacuum but has nitrogen in it. The system boundary
shown by the dashed line of Figure 5.4 clearly denes the system, which consists
of nitrogen in both compartments A and B, the partition and the rigid vessel.
Since neither heat nor work crosses the system boundary, the rst law applied
to closed systems yields
U = 0 (5.44)
which means that there is no change in the total internal energy of the system.
initial state,
nal state,
A B
1 bar
300 K
4 bar
600 K
nal pressure P
f
= ?
nal temperature T
f
= ?
(V
A
= 4 V
B
)
with partition
without partition
60 Chapter 5
Ignoring the internal energy changes of the partition and the vessel, the total
internal energy change of the system is written as
U = U
N
2
in A
+ U
N
2
in B
= m
A
u
N
2
in A
+m
B
u
N
2
in B
where m
A
and m
B
are the respective masses of nitrogen in compartments A
and B at the initial state.
Since nitrogen contained in both the compartments A and B behaves as
an ideal gas, and since nitrogen has constant C
v
, we may expand the above
expression as
U = m
A
C
v
(T
f
T
A
) + m
B
C
v
(T
f
T
B
) (5.45)
where T
f
is the temperature of nitrogen at the nal state, T
A
is the temperature
of nitrogen in compartment A at the initial state, and T
B
is the temperature of
nitrogen in compartment B at the initial state.
Combining (5.44) and (5.45), we get
m
A
C
v
(T
f
T
A
) + m
B
C
v
(T
f
T
B
) = 0
Substituting the respective temperatures of nitrogen in compartments A and
B at the initial state in the above equation and eliminating C
v
, we get
m
A
(T
f
300 K) + m
B
(T
f
600 K) = 0 (5.46)
The respective masses of nitrogen in A and in B at the initial state are
evaluated using the ideal gas equation of the form P V = mRT as
m
A
=
(1 bar) V
A
R(300 K)
and m
B
=
(4 bar) V
B
R(600 K)
(5.47)
Substituting m
A
and m
B
of (5.47) in (5.46), we get
(1 bar) V
A
R(300 K)
(T
f
300 K) +
(4 bar) V
B
R(600 K)
(T
f
600 K) = 0 (5.48)
Since V
A
= 4 V
B
, (5.48) gives T
f
= 400 K.
Now, we have to determine P
f
, the pressure at the nal state. Note that
we have already used all the three tools mentioned at the very beginning of
this section. And, therefore, it may seem impossible to nd the value of P
f
.
However, there is a fundamental law known as the principle of conservation of
mass, which we have not used.
Application of the principle of conservation of mass to the given closed sys-
tem yields
total mass of nitrogen in the vessel at the nal state
= total mass of nitrogen in the vessel at the initial state
which gives
m
final
= m
A
+m
B
(5.49)
where m
final
is the total mass of nitrogen in the vessel at the nal state, and it
is related to P
f
by the ideal gas equation of state according to
m
final
=
P
f
(V
A
+V
B
)
RT
f
(5.50)
Substituting m
A
, m
B
and m
final
from (5.47) and (5.50), respectively, in
(5.49), we get
P
f
(V
A
+V
B
)
RT
f
=
(1 bar) V
A
R(300 K)
+
(4 bar) V
B
R(600 K)
(5.51)
Since V
A
= 4 V
B
and T
f
= 400 K, (5.51) gives P
f
= 1.6 bar.
Example 5.7
heat capacity is divided into two compartments having a volume of 0.5
m
3
each by a piston that is kept from moving by a pin. The piston does
not permit the gases to leak into each other. Initially, one compartment
contains nitrogen at 5 bar and the other compartment contains hydrogen
at 2 bar. The entire system is at 300 K. The mass of the piston is 2 kg and
it is made up of copper of specic heat 0.386 kJ/kg
C. The pin holding

the piston is removed and the piston is allowed to reach an equilibrium
position. The piston is assumed to move without friction. Determine the
pressures, temperatures and volumes of the gases at the nal equilibrium
state. Assume ideal gas behaviour. Take C
v
as 0.743 kJ/kg K for nitrogen,
and C
v
as 10.199 kJ/kg K for hydrogen. Molar mass of nitrogen is 28
kg/kmol and that of hydrogen is 2 kg/kmol.
62 Chapter 5
The system boundary shown by the dashed line of Figure 5.5 clearly denes
the system, which consists of nitrogen in compartment A, hydrogen in compart-
ment B, the piston and the rigid vessel.
initial state nal state
A
nitrogen
P
A
=5 bar
T
A
=300 K
V
A
=0.5 m
3
B
hydrogen
P
B
=2 bar
T
B
=300 K
V
B
=0.5 m
3
(piston is held by a pin) (piston is free to move)
l
A B
nitrogen
P
f
bar
T
f
K
V
Af
m
3
hydrogen
P
f
bar
T
f
K
V
Bf
m
3
pin
h
q
q
q q
q
q q
q
q
q
p
q q
qq
q
q
q
q pp
q
q
q
q q
"
"
b
b
Once the pin holding the piston is removed, the piston is free to move until
the net force acting on the piston becomes zero. The force balance on the piston
in the absence of friction is written as follows:
pressure in compartment A x cross-sectional area of the piston =
pressure in compartment B x cross-sectional area of the piston,
which gives that, at the nal equilibrium state, the pressures in the two
compartment on either side of the piston equal each other. Let us denote this
pressure as P
f
(see Figure 5.5).
Since the piston is made up of copper, which is a good heat conductor, the
temperatures of the gases as well as the piston are all the same; 300 K at the
initial state and T
f
at the nal state (see Figure 5.5). The respective volumes of
nitrogen and hydrogen at the nal state are given by V
Af
and V
Bf
(see Figure
5.5). We are to determine the numerical values of P
f
, T
f
, V
Af
and V
Bf
.
Since neither heat nor work crosses the system boundary, the rst law applied
to closed systems yields U = 0, which means that there is no change in the
total internal energy of the system. Ignoring the internal energy change of the
vessel of negligible heat capacity, the total internal energy change of the system
is written as
U = U
A
+ U
B
+ U
p
= 0 (5.52)
where the subscript A denotes the nitrogen in compartment A, B denotes the
hydrogen in compartment B, and p denotes the piston.
Expanding (5.52) in terms of masses and specic heats, we get
m
A
(C
v
)
A
(T
f
300)+m
B
(C
v
)
B
(T
f
300)+m
p
(specic heat)
p
(T
f
300) = 0
(5.53)
in which the initial temperatures of hydrogen, nitrogen and piston are all 300 K,
and the nal temperatures are all T
f
K. When rearranged, (5.53) gives
[m
A
(C
v
)
A
+m
B
(C
v
)
B
+m
p
(specic heat)
p
] [T
f
300 K] = 0 (5.54)
Since [m
A
(C
v
)
A
+m
B
(C
v
)
B
+m
p
(specic heat)
p
] of (5.54) takes a nite
value, we get
T
f
= 300 K (5.55)
Now, we go on to determine P
f
, which is the nal pressure in both the
compartments, using the ideal gas equation of state and the principle of con-
servation of mass as follows. The masses of gases in compartments A and B
remain constant during the process. Therefore, applying the ideal gas equation
of state to the gases in compartments A and B at the initial and nal states
yields the following equations, with reference to Figure 5.5:
P
f
V
Af
T
f
=
(5 bar) (0.5 m
3
)
300 K
(5.56)
and
P
f
V
Bf
T
f
=
(2 bar) (0.5 m
3
)
300 K
(5.57)
Substituting the value of T
f
from (5.55) in (5.56) and (5.57), we get
P
f
V
Af
= (5 bar) (0.5 m
3
) and (5.58)
P
f
V
Bf
= (2 bar) (0.5 m
3
) (5.59)
which has three unknowns P
f
, V
Af
and V
Bf
.
There are no other equations except (5.58) and (5.59) that are in terms of
the unknowns. We therefore need one more independent equation in terms of one
or more of the three variables P
f
, V
Af
and V
Bf
, to solve for the unknowns. We
have indeed used up all three of our tools along with the principle of conservation
64 Chapter 5
of mass. The situation seems hopeless except for the fact that the total volume
of the system remains a constant. Therefore, we get
V
Af
+V
Bf
= 1 m
3
(5.60)
Substituting V
Af
from (5.58) and V
Bf
from (5.59) in (5.60), we get
(5 bar) (0.5 m
3
)
P
f
+
(2 bar) (0.5 m
3
)
P
f
= 1 m
3
(5.61)
and thus
P
f
= 3.5 bar (5.62)
Substituting the value of P
f
from (5.62) in (5.58), we get
V
Af
=
(5 bar) (0.5 m
3
)
3.5 bar
= 0.714 m
3
(5.63)
Substituting the value of V
Af
from (5.63) in (5.60), we get V
Bf
= 0.286 m
3
.
In working out thermodynamic problems on closed simple compressible
systems with ideal gases, we started out with the following three tools:
in
+ W
in
Tool 2: Evaluation of U using data on specic heats, or data on internal
energy itself.
perature, volume and mass (or amount of matter) of an ideal gas.
However, while solving the problems we realized that the following two
tools must be added to the list:
Tool 4: Principle of conservation of mass.
Tool 5: Any other constraint stated in the problem, such as the total
volume remains constant.
Example 5.8
Show that we require more information about
the problem to solve for the unknowns of Example 5.7 if the heat con-
ducting copper piston is replaced by a piston that is a perfect heat insulator.
The problem of this example diers from that of Example 5.7 in the aspect
that the piston of this example does not allow heat to pass from one compartment
to the other. Therefore, the nal temperatures in the two compartments cannot
be considered the same, as was in the Solution to Example 5.7.
The unknowns of the problem are P
f
, which denotes the equal nal pressures
of gases in both the compartments, T
Af
and T
Bf
, which are the unequal nal
temperatures of gases in both the compartments, and V
Af
and V
Bf
, which are
the unequal nal volumes of the gases in both the compartments. To solve for
the ve unknowns, P
f
, T
Af
, T
Bf
, V
Af
and V
Bf
, we require ve independent
equations in terms of one or more of the unknowns alone. Let us see how to get
the equations required.
Using Tool 1 and Tool 2 we get
m
A
(C
v
)
A
(T
Af
T
Ao
) +m
B
(C
v
)
B
(T
Bf
T
Bo
) = 0 (5.64)
where m
A
, (C
v
)
A
, T
Ao
and T
Af
are the respective mass, C
v
, initial temperature
and nal temperature of nitrogen in one compartment, and m
B
, (C
v
)
B
, T
Bo
and T
Bf
are the respective mass, C
v
, initial temperature and nal temperature
of hydrogen in the other compartment.
Substituting whatever is known from the problem statement in (5.64), we
get
m
A
(0.743 kJ/kg K) (T
Af
300 K)+m
B
(10.199 kJ/kg K) (T
Bf
300 K) = 0
(5.65)
The masses of the gases are found using Tool 3 as follows:
m
A
=
(5 bar 100 kPa/bar) (0.5 m
3
)
(8.314/28 kJ/kg K) (300 K)
= 2.81 kg (5.66)
m
B
=
(2 bar 100 kPa/bar) (0.5 m
3
)
(8.314/2 kJ/kg K) (300 K)
= 0.08 kg (5.67)
Substituting m
A
of (5.66) and m
B
of (5.67) in (5.65), we get
2.81 0.743 (T
Af
300) + 0.08 10.199 (T
Bf
300) = 0 (5.68)
66 Chapter 5
which is one of the ve equations in terms of the unknowns alone.
Since the masses of gases in compartments A and B stay the same during
the process, use of Tool 4 gives
m
Af
= m
Ao
and m
Bf
= m
Bo
(5.69)
Using Tool 3, (5.69) can be expanded to
P
f
V
Af
T
Af
=
(500 kPa) (0.5 m
3
)
300 K
and (5.70)
P
f
V
Bf
T
Bf
=
(200 kPa) (0.5 m
3
)
300 K
(5.71)
which are two more independent equations in terms of the unknowns alone.
Tool 5 gives
V
Af
+V
Bf
= 1 m
3
(5.72)
which is yet another independent equation in terms of the unknowns alone.
We now have four independent equations (5.68), (5.70), (5.71) and (5.72)
to solve for the ve unknowns P
f
, T
Af
, T
Bf
, V
Af
and V
Bf
. From the problem
statement, it is impossible to get one more independent equation in terms of
one or more of the unknowns. Therefore, more information about the problem
should be provided in order to solve for the unknowns, if the heat conducting
copper piston of Example 5.7 is replaced by a piston that is a perfect heat
insulator.
5.10 Summary
The ideal gas equation of state is given by
P V = nRT (5.1)
or by
P V = mRT (5.3)
where P is the absolute pressure in kPa, V is the total volume in m
3
, and
T is the absolute temperature in K. In (5.1), n is the amount of gas in
kmol, and therefore R is the universal gas constant which takes the value
8.314 kJ/kmol K for all gases. In (5.3), m is the mass of gas in kg, and
therefore R is the specic gas constant in kJ/kg K, the numerical value
of which depends on the gas concerned.
Specic gas constant is related to the universal gas constant by
specic gas constant =
8.314 kJ/kmol K
M (in kg/kmol)
where M = m/n, is the molar mass.
The ideal gas equation of state is also given by
P v = RT (5.4)
where P is the absolute pressure in kPa and T is the absolute temperature
in K. If v is the molar volume in m
3
/kmol, then R is the universal gas
constant. If v is the specic volume in m
3
/kg, then R is the specic gas
constant.
For an ideal gas, properties u, h, C
v
and C
p
depend only on temperature.
For an ideal gas, specic (or molar) enthalpy is given by
h = u +RT (5.10)
Specic heat at constant volume for an ideal gas is dened as
C
v
=
du
dT
(5.6)
Specic (or molar) internal energy change of an ideal gas undergoing any
process can be evaluated using
u =
T
f
To
C
v
dT (5.8)
Note that (5.8) could also be used to evaluate u for substances other
than ideal gas provided the process is executed at constant volume.
To evaluate u using (5.8), C
v
must be known either as a function of
T or be approximated to a constant. It is also common to obtain u as
(u
f
- u
o
), where u
f
and u
o
are obtained from ideal-gas (or zero-pressure)
property tables.
68 Chapter 5
Specic heat at constant pressure for an ideal gas is dened as
C
p
=
dh
dT
(5.11)
Specic (or molar) enthalpy change of an ideal gas undergoing any process
can be evaluated using
h =
T
f
To
C
p
dT (5.13)
Note that (5.13) could also be used to evaluate h for substances other
than ideal gas provided the process is executed at constant pressure.
To evaluate h using (5.13), C
p
must be known either as a function of
T or be approximated to a constant. It is also common to obtain h as
(h
f
- h
o
), where h
f
and h
o
are obtained from ideal-gas (or zero-pressure)
property tables.
Specic heats of an ideal gas is related to each other by
C
p
= C
v
+R (5.14)
Specic heat ratio (or the isentropic exponent) is dened as
= C
p
/C
v
(5.15)
Specic heats of an ideal gas are given in terms of and R as follows:
C
v
=
R
1
(5.16)
C
p
=
R
1
(5.17)
In working out thermodynamic problems on closed simple compressible
systems with ideal gases, the following tools are used:
in
+ W
in
perature, volume and mass (or amount of matter) of an ideal gas.
Tool 4: Evaluation of U using data on specic heats, or data on in-
ternal energy itself.
Tool 5: Any other constraint stated in the problem.
Chapter 6
WORKING WITH
REAL GASES & STEAM
Ones ideas should be as broad as nature if they are to interpret
nature.
Sherlock Holmes
Sir Arthur Conan Doyle (A study in Scarlet)
We have now learned to apply the rst law to closed systems containing
ideal gas. Ideal gas, which is an imaginary gas used to approximate real
gas behaviour, is always in gas phase, but a real gas used in an engineering
device may turn into a liquid at appropriate pressures and temperatures. It
is therefore necessary that we learn to work with real gases and liquids. In
this chapter, we will learn in particular about working with water, which is
either in gas phase as steam, or in liquid phase, or in a mixed state of liquid
and gas phases.
70 Chapter 6
6.1 Real Gas Behaviour
The intermolecular distances prevailing among the molecules of a real
gas at low pressures, are large enough to approximate the behaviour of the
real gas by that of the ideal gas. At medium and high pressures, however,
the molecules of real gases are brought so close together that the volume
occupied by the gas molecules become a considerable fraction of the total
gas volume, and the intermolecular forces and their inuence on molecular
collision processes are no longer negligible. The real gas behaviour therefore
deviates signicantly from the ideal gas behaviour at high and medium
pressures.
Since the ideal gas equation of state cannot be used to satisfactorily
describe the behaviour of a real gas, many attempts have been made to
modify the ideal gas equation of state to represent the experimental data
obtained with real gases. Listed below are few of the many equations avail-
able for describing real gas behaviour
. The predictability of these equations

is found to be remarkably good when the gas is not too close to the tem-
perature and pressure at which it becomes a liquid.
van der WAALS EQUATION OF STATE:
Considering the intermolecular attraction forces and the volume occu-
pied by the gas molecules themselves, van der Waals equation of state is
written down as

P +
a
v
2
(v b) = RT
where a is the van der Waals constant that takes account of the molecular
interactions, and b is the van der Waals constant that compensates for the
volume occupied by the molecules. Constants a and b take dierent values
for dierent substances. Air, for example, has a = 135.7 kPa m
6
/kmol
2
and b = 0.037 m
3
/kmol.
For a complete description, see the following sources:

Chapter 2 of Cengel, Y.A. & Boles, M.A. 1998 Thermodynamics: an engineering
approach, 3
rd
Chapter 3 of Rao, Y.V.C. 1997 Chemical Engineering Thermodynamics, Universi-
ties Press Limited.
Working with Real Gases & Steam 71
REDLICH-KWONG (RK) EQUATION OF STATE:
It is one of the widely used equation of state in engineering calculations
and is given by
P =
RT
(v b
)

a
v (v + b
T
where a
and b
are constants specic to the substance concerned.

VIRIAL EQUATION OF STATE:
P v
RT
= 1 +
B
v
+
C
v
2
+
D
v
3
+
where the virial coecients B, C, D, etc. are functions of temperature
alone. Although it is a very complicated procedure to calculate the virial
coecients, once it is done, the virial equation of state predicts the P-v-T
behaviour of a real gas with a remarkable accuracy over a wide range.
We have learned in Chapter 5 that, for an ideal gas, u and h are func-
tions of T alone. For real gases, however, u and h depend not only on T,
but also on another property such as v or P. It is therefore important to
know that changes in u and h for a real gas cannot be evaluated using the
methods described for an ideal gas in Chapter 5. However, if the states of
the real gas considered is not too close to the temperature and pressure
at which it becomes liquid then it is possible to approximate the real gas
behaviour to ideal gas behaviour, and use the methods described in Chapter
5 to evaluate the changes in u and h for that real gas.
6.2 Phase Change: Gas to Liquid
A real gas behaviour is such that it could be converted into liquid by
decreasing the temperature at appropriate pressures, or by increasing the
pressure at appropriate temperatures.
72 Chapter 6
The T-v diagrams of Figure 6.1 shows the phase change behaviour of a
pure substance. Water is chosen as the pure substance. Point A of Figure
6.1(a) represents water at 1 bar and 700
C, at which condition water is in

gas phase, and is known as steam. From A to B, water remains in the form
of steam at 1 bar but at dierent temperatures. The dashed line of Figure
6.1(a) represents the T-v relationship of steam described by the ideal gas
equation of state as T = Pv/R at the given pressure. Note that circles
representing the real gas behaviour in the region A to B of Figure 6.1(a)
lie almost on the dashed line of Figure 6.1(a). It means that the ideal gas
behaviour of steam adequately describes the real gas behaviour of steam
at 1 bar for temperatures above the temperature represented by the point
B.
At point B, steam starts to condense, that is, steam begins to convert
itself into liquid water. The horizontal line BD represents the transforma-
tion of steam into liquid water at a constant pressure of 1 bar and at a
constant temperature of 99.6
C. As steam transforms into liquid water at

constant pressure and constant temperature, the specic volume of steam
reduces considerably. At point D, all steam is condensed into liquid water.
Note that point D can also be seen as a point at which water in liquid
phase starts its transformation into gas phase, and point B as a point at
which all water in liquid phase completes its transformation into gas phase.
It is therefore, the constant temperature represented by the horizontal lines
BD is known as the boiling point. The boiling point temperature of a
substance is therefore the temperature at which a liquid converts itself into
a gas, or a gas converts itself into a liquid, at a given pressure.
From D to E of Figure 6.1(a), water remains in liquid form at 1 bar
but at dierent temperatures. Since the specic volume of liquid water
experiences very little change with changing temperature, DE remains al-
most a vertical line. Behaviour of water in the range of B to E cannot be
described by ideal gas behaviour since water is no longer in gas phase alone
in this region.
The circles of Figure 6.1(b), (c) and (d) represent the actual T-v be-
haviour of water at 100, 200 and 500 bars, respectively, and the dashed
lines represent the behaviour of water predicted by the ideal gas equation.
As can clearly be seen in Figure 6.1, the higher is the pressure, the larger
is the dierence between the actual behaviour and the ideal gas behaviour.
It is because the real gas behaviour deviates from ideal gas behaviour at
medium and high pressures.
Figure 6.1 The real gas behaviour of a pure substance, represented by circles
on a T-v diagram, at (a) = 1 bar, (b) = 100 bar, (c) = 200 bar, and (d) = 500
bar. The dashed line on each of the four plots represents the ideal gas behaviour
of the substance, given by T = Pv/R. (The numerical values used represent
water.)
74 Chapter 6
Figure 6.2 T-v diagram of a pure substance describing the gas phase to liquid
phase transformation. (a) T-v relationships at constant pressures, represented
by dashed lines. (b) Important characteristics of phase-change. (The numerical
values used represent water.)
The boiling point temperature, corresponding to the horizontal line BD
of Figure 6.1, takes dierent values at dierent pressures. It is 99.6
C at
1 bar, 311.0
C at 100 bar, and 365.7
C at 200 bar. The horizontal line

BD of Figure 6.1, which represents the phase change of water at constant
pressure and constant temperature, is present in Figure 6.1(a), (b) and (c),
and is not present in Figure 6(d). The reason for this peculiar behaviour of
water at 500 bar is discussed at the end of this section.
We have seen that point B in Figure 6.1 represents the point at which
real gas starts to transform into a liquid. If we take the point B at each
pressure, and connect them together, we get the curve CG shown in Figure
6.2(a). Point D in Figure 6.1 represents the point at which the gas just
completes its transformation into a liquid. If we take the point D at each
pressure, and connect them together, we get the curve LC shown in Figure
6.2(a). The curve LCG is of considerable importance as it separates the
area of the T-v diagram into a gas phase region, a liquid phase region, and
a liquid-gas phase region, as labelled in Figure 6.2(b). Note that we use
the word vapour in place of gas in Figure 6.2(b), the reason for which is
given at the end of this section.
The important characteristics of the gas to liquid phase change, shown
in Figure 6.2(b), are described below:
Superheated vapour region:
The temperature at any state represented by a point in this region is
always above the boiling point temperature at the corresponding pressure.
A point in this region therefore represents the state of vapour that is not
about to condense, which means not about to become a liquid. It is there-
fore the vapour in this region is known as the superheated vapour, and
the region is known as the superheated vapour region.
Saturated vapour line:
The vapour at any state represented by a point along this line (repre-
sented by the curve CG in Figure 6.2), is at its boiling point temperature.
Any heat loss from a vapour at its boiling point temperature, no matter
how small, will cause some of the vapour to condense. Since the vapour at
a state along the curve CG is about to condense, it is known as the sat-
urated vapour, and the curve CG is known as the saturated vapour
76 Chapter 6
line. The pressure at a state along the saturated vapour line is known as the
saturation pressure. And, the corresponding temperature, which is the
boiling point at that pressure, is known as the saturation temperature.
Saturated liquid line:
Any point along this line (represented by the curve LC in Figure 6.2),
gives the state of liquid that is at its boiling point. Any addition of heat to
a liquid at this state, no matter how small, will cause some of the liquid to
vapourise. It is therefore the liquid at a state along the curve LC is known
as the saturated liquid, and the curve LC is known as the saturated
liquid line. The pressure of a saturated liquid is the saturation pressure,
and its temperature is the saturation temperature.
Saturated liquid-vapour region:
At any state represented by a single point in this area, what we get is a
mixture of saturated liquid and saturated vapour. Therefore, this region is
known as the saturated liquid-vapour region, or the wet region. Note that
it is only in this region that the vapour and the liquid phases exist together.
Along any horizontal line in this region, as any one of the lines BD shown
in Figure 6.2(a), the temperature and the pressure remain constants at the
saturation values. The specic (or molar) volume would, of course, changes
from one point to another along any horizontal line in this region.
Compressed liquid region:
Any point in this region describes the state of liquid that is not about
to vapourise. That is, the temperature of the compressed liquid is always
below the boiling point corresponding to the given pressure. Compressed
liquid is also known as subcooled liquid.
Critical point:
Point C on the curve LCG of Figure 6.2 is known as the critical
point. At the critical point, the saturated vapour phase is the same as
the saturated liquid phase, and therefore their properties are identical. The
critical point represents the highest pressure and temperature at which the
liquid and vapour phases coexist in equilibrium. The respective pressure
and temperature at the critical point are known as the critical pressure,
denoted by P
c
, and the critical temperature, denoted by T
c
.
Dierent pure substances have dierent critical pressures and critical
temperatures. The critical constants of some selected substances are listed
below:
Substance T
c
C P
c
MPa
Argon -122.3 4.9
Carbon dioxide 31.0 7.4
Ethane 32.2 4.9
Helium -268.0 0.23
Hydrogen -240.0 1.3
Nitrogen -147.0 3.4
Oxygen -118.6 5.05
Water 374.15 22.120
The critical temperature and the critical pressure are very crucial prop-
erties of a pure substance, and they have many use. For example, the van
der Waals constants are dened in terms of P
c
and T
c
as
a =
27 R
2
T
2
c
64 P
c
and b =
RT
c
8 P
c
with R as the gas constant. The constants of Redlich-Kwong equation of
state are also dened in terms of P
c
and T
c
as
a
=
0.42748 R
2
T
2.5
c
P
c
and b
=
0.08664 RT
c
P
c
Student: Teacher, I still have no feeling for what a critical point is all about.
Would you please tell me more about the critical point?
Teacher: Yes, I will. Let us carry out an experiment in a variable volume
vessel, in which we hold steam at 500 bar and 700
C, which are above the

critical pressure and the critical temperature for water. Now, let us reduce
the temperature of steam slowly to room temperature while holding the
pressure at 500 bar. The path of this experiment can be seen in the
T-v diagram of Figure 6.1(d). The path, as seen in this diagram, has
no horizontal line at constant temperature, along which steam transforms
into liquid water.
78 Chapter 6
Student: Does that mean that steam does not become liquid water if the
pressure is held above the critical pressure?
Teacher: No, it does not mean that. Even if the pressure is larger than the
critical pressure, if the temperature is reduced to a low enough value then
what we will have is liquid water. You could see in Figure 6.2(a) that,
at low temperatures, the path of water at 500 bar is nearly the same as
the paths at other pressures which are lower than the critical pressure. All
these paths lie almost on the saturated liquid line LC.
Student: What exactly is the dierence then?
Teacher: The dierence is, for pressures below the critical pressure, we know
exactly when the gas phase transforms into the liquid phase. We could
see the transformation occurring at a constant temperature, with our own
eyes. For pressures above the critical pressure, on the other hand, we will
not be able to tell exactly when the gas phase transformed into the liquid
phase. It is because this transformation occurs gradually.
Student: I think I am beginning to see what a critical point is all about.
Teacher, would you please tell me what is the dierence between a vapour
and a gas?
Teacher: Vapour is a word used to describe a substance in gas phase at tem-
peratures below critical temperature, and gas is used for the same at
temperatures above critical temperature. Except for this dierence, the
gas and vapour states are identical to each other.
Student: I got it. The critical temperature of water is 374.15
C. That is why
we refer to water in gaseous phase at room temperature, or even at 100
C,
as vapour. Whereas, we refer to oxygen at room temperature as gas since
its critical temperature is -118.6
C.
Teacher: Yes, that is correct.
6.3 P-v diagram for Phase Change
The P-v behaviour of water at four dierent temperatures are shown
in Figure 6.3(a), and its characteristics are labeled on Figure 6.3(b).
Figure 6.3 P-v diagram of a pure substance describing the gas phase to liquid
phase transformation. (a) P-v relationships at constant temperatures, repre-
sented by dashed lines. (b) Important characteristics of phase-change. (The
numerical values used represent water.)
80 Chapter 6
Let us take a look at the path of water at 300
C. Point E in Figure
6.3(a) represents the state of liquid water at 350 bar and 300
C. When
the pressure is reduced, while maintaining the temperature constant at
300
C, the specic volume of liquid water increases slightly until point D

is reached. At this point, the pressure is 85.93 bar.
Any further reduction in pressure is not possible until all the liquid
water is transformed into water vapour at 300
C. During the vaporization

process, which is described by the path DB, the specic volume increases
considerably at constant pressure and temperature. At point B all the
liquid water is transformed into water vapour. Any further reduction in
pressure beyond point B at 300
C results in considerable increase in the

specic volume of water vapour, as shown in Figure 6.3(a).
Similar behaviour is repeated by water at 100
C, as well. For water at

400
C and at 500
C, which are temperatures above the critical temperature

374.15
C, the transformation of water from liquid phase to gas phase is so

gradual, as shown in Figure 6.3(a), that it is not possible to tell exactly
when the liquid water turns into water vapour. By the way, as we have
already seen, the gaseous phase of water at temperatures above critical
temperature is referred to as gas, not as vapour, even though the gas and
vapour states are identical to each other.
The curve LCG shown in Figure 6.3(a) separates the area on the P-v
diagram into a vapour phase region, a liquid phase region, and a liquid-
vapour phase region. These regions are labelled in Figure 6.3(b). The T-v
diagrams of Figure 6.2 and the P-v diagrams of Figure 6.3 are very similar
to each other except for the orientation of the constant pressure lines of
the T-v diagrams in comparison with the orientation of the constant tem-
perature lines of the P-v diagrams.
6.4 P-T diagram for Phase Change
The saturated liquid-vapour regions on the respective T-v and P-v
diagrams of Figure 6.2(b) and Figure 6.3(b), reduce to a curve on a P-T
diagram, since the liquid to vapour, or the vapour to liquid, phase change
occurs at a constant temperature for a chosen pressure. This curve is known
as the vaporization curve, and is shown in Figure 6.4. Each point along
this curve gives the pressure-temperature set at which the liquid and vapour
phases remain in equilibrium.
One end of the vaporization curve is the critical point, which represents
the highest pressure and temperature at which the liquid and vapour phases
coexist in equilibrium. The other end of the vaporization curve is the triple
point, which represents the state at which it is possible to maintain an
equilibrium mixture of all three phases, solid, liquid and vapour. For water,
the triple point is at a pressure of 0.006112 bar and a temperature of
0.01
C.
Figure 6.4 also shows the melting curve (or fusion curve), along
which the solid and liquid phases are in equilibrium. The sublimation
curve of Figure 6.4 represents the pressure-temperature sets at which a
direct phase change between the solid phase and the gas phase exists. Note
that the fusion, vaporization and sublimation curves of the P-T diagram
meet at the triple point.
q
r
r
P
T
Sublimation curve
Q Qk
Vapourization curve
}
VAPOUR
SOLID
LIQUID
Melting curve
H
Hj
Critical point 9
Q Qk
Triple point
Figure 6.4 P-T diagram for phase changes (not drawn to scale).
6.5 The Steam Table
Ideal gas relationships developed in Chapter 5 can be used to describe
the real gas behaviour when the state of the real gas is not too close to
either the critical point or the saturated vapour line. In many real life
82 Chapter 6
situations, however, a more accurate representation of the thermodynamic
properties than the use of ideal gas relationships is demanded. In such
cases, thermodynamics properties are obtained from thermodynamic
property tables.
Thermodynamic property tables contain data derived from a combina-
tion of extensive and precise experiments and calculations. Let us here
concentrate on the thermodynamic properties of liquid water and steam,
which are tabulated in a table known as the Steam Table. There are
many versions of the steam table. Each version dier from the other in
some aspects, but all of them have a common basic structure.
A Steam Table is usually divided into three parts, which are Saturated
Water and Steam Table, Superheated Steam Table and Compressed Water
Table. A detail account of how the data are presented in these three parts
of the Steam Table, and the manner in which the data could be extracted
from the table are discussed below.
6.5.1 Saturated Water and Steam Table
Saturated Water and Steam Table, also referred to as Saturated Steam
Table, lists the data corresponding to point B and point D shown in Figure
6.5. Point B represents the saturated steam state that lies on the saturated
vapour line, represented by the curve CG of Figure 6.2(b) or Figure 6.3(b).
Point D represents the saturated water state that lies on the saturated liquid
line, represented by the curve LC of Figure 6.2(b) or Figure 6.3(b).
The pressure of saturated water or steam is the saturation pressure,
denoted by P
sat
or simply by P
s
. And, the corresponding temperature is
the saturation temperature, denoted by T
sat
or simply by T
s
. (It is also
common to use the symbols p
s
and t
s
for saturation pressure and satura-
tion temperature, respectively.) The saturation pressure and temperature
are related to each other, and this relationship is represented by the vapor-
ization curve shown in Figure 6.4. In the saturated water and steam region,
therefore, either the pressure or temperature can be chosen with complete
freedom, not both.
In some Saturated Water and Steam Tables, temperature is chosen as
the independent property, and is entered as the rst entry in the table in
regular steps. And, all the other properties of saturated steam and water
that depend on the temperature are listed against the corresponding tem-
perature entry. In some other tables, pressure is chosen as the independent
property, and is entered as the rst entry in regular steps, and the other
properties are listed against it. Many tables contains both.
v
P
D B
r r
Figure 6.5 Points B and D represent typical entries of the saturated
steam state and the saturated liquid water state, respectively,
on the Saturated Water and Steam Table.
The entries in the Saturated Water and Steam Table begin with the
pressure of 0.006112 bar and 0.01
C, which is the triple point, and ends

with the pressure of 221.2 bar and 374.15
C, which is the critical point.

The properties of saturated vapour, other than the pressure and tempera-
ture, are identied by the subscript
g
in the steam table. Specic volume
of the saturated vapour is denoted by v
g
, specic internal energy by u
g
,
specic enthalpy by h
g
, and specic entropy by s
g
. The properties of sat-
urated liquid are identied by the subscript
f
in the steam table. Specic
volume of the saturated liquid is denoted by v
f
, specic internal energy by
u
f
, specic enthalpy by h
f
, and specic entropy by s
f
. Some Saturated
Water and Steam Tables also contains entries for u
fg
, h
fg
and s
fg
, where
u
fg
= u
g
u
f
, h
fg
= h
g
h
f
and s
fg
= s
g
s
f
.
Student: Teacher, what is specic entropy?
Teacher: Well, entropy divided by the mass of the substance gives the specic
entropy.
Student: What is entropy, then?
84 Chapter 6
Teacher: Oh...Yes. You have not been formally introduced to entropy yet.
Chapter 11 is dedicated to entropy, where you will be formally introduced
to entropy. You will learn to work out problems using entropy in that
chapter. Now, let me tell you that entropy is a property just as pressure,
temperature, internal energy and enthalpy are. And, we will learn here
how to refer to the property specic entropy from a Steam Table in the
same way as we learn to refer to other specic properties from the Steam
Table. Is that okay?
Student: Yes, its okay.
Example 6.1
Determine the specic volume, specic internal
energy, specic enthalpy and the specic entropy of saturated water vapour
at 100 kPa.
A typical entry for saturated steam in a Saturated Water and Steam Table
at 100 kPa (= 1 bar) is shown below where the subscript
g
refers to properties
of saturated vapour.
p t
s
v
g
u
f
u
g
h
f
h
fg
h
g
s
f
s
fg
s
g
bar

C m
3
/kg - kJ/kg - - kJ/kg - - kJ/kg K
0.90 96.7 1.869 - 2502 - - 2671 - - 7.394
0.95 98.2 1.777 - 2504 - - 2673 - - 7.376
1.00 99.6 1.694 - 2506 - - 2675 - - 7.359
1.10 102.3 1.549 - 2510 - - 2680 - - 7.327
1.20 104.8 1.428 - 2512 - - 2683 - - 7.298
The specic volume of the saturated vapour at 1 bar is given by the third
entry in the third row, the specic internal energy by the fth entry, the specic
enthalpy by the eighth entry, and the specic entropy by the eleventh entry.
Taking the units used in that particular table, we can write v
g
= 1.694 m
3
/kg,
u
g
= 2506 kJ/kg, h
g
= 2675 kJ/kg and s
g
= 7.359 kJ/kg K. The second entry
yields the saturation temperature. That is, the saturated vapour is at 99.6
C.
Example 6.2
Determine the specic volume, specic internal
energy, specic enthalpy and the specic entropy of saturated liquid water
at 100 kPa.
A typical entry for saturated water in a Saturated Water and Steam Table at
100 kPa (= 1 bar) is shown below where the subscript
f
refers to the properties
of saturated liquid.
p t
s
v
g
u
f
u
g
h
f
h
fg
h
g
s
f
s
fg
s
g
bar

C - kJ/kg - kJ/kg - - kJ/kg K - -
0.90 96.7 1.869 405 - 405 - - 1.270 - -
0.95 98.2 1.777 411 - 411 - - 1.287 - -
1.00 99.6 1.694 417 - 417 - - 1.303 - -
1.10 102.3 1.549 429 - 429 - - 1.333 - -
1.20 104.8 1.428 439 - 439 - - 1.361 - -
The fourth entry in the third row gives the specic internal energy, the sixth
entry the specic enthalpy and the ninth entry the specic entropy. Therefore,
u
f
= 417 kJ/kg, h
f
= 417 kJ/kg and s
f
= 1.303 kJ/kg K. The saturated
liquid is at 99.6
C.
The entry for specic volume of the saturated liquid is not available on the
table above. Therefore, make use of h = u + pv to calculate the specic volume
of the saturated liquid as v
f
= (h
f
u
f
)/p = 0. This impossible result is a
consequence of the manner in which the entries for u and h are rounded o in
the Saturated Water and Steam Table concerned.
For a realistic value of v
f
, therefore, we must search for steam tables con-
taining tabulated values of v
f
. Such entry found in a Saturated Water and
Steam Table
is reproduced below:
t p
s
v
f
10
2
C
pf
C
pg
- - - - - -
C bar m
3
/kg kJ/kg K kJ/kg K - - - - - -
90 0.7011 0.1036 4.208 1.97 - - - - - -
95 0.8453 0.1040 4.213 1.99 - - - - - -
100 1.01325 0.1044 4.219 2.01 - - - - - -
105 1.208 0.1048 4.226 2.03 - - - - - -
See, for example, page 10 of Mayhew, Y.R. and Rogers, G.F.C. 1972 Thermo-
dynamics and Transport Properties of Fluids, SI Units, 2
nd
Edition, Oxford, Basil
Blackwell.
86 Chapter 6
As you can see, the entry for 1 bar pressure is not available in the above
tabulation, but entries for 0.8453 bar and 1.01325 bar are available. A linear
interpolation between the entries corresponding to 0.8453 bar and 1.01325 bar
would yield the specic volume required at 1 bar as follows:
v
f
10
2
0.1040
0.1044 0.1040
=
1 0.8453
1.01325 0.8453
which gives v
f
= 0.1043710
2
m
3
/kg at 1 bar. This volume can be approxi-
mated to 0.001 m
3
/kg.
That means v of saturated liquid at 1 bar (1/1000) m
3
/kg = (1/density
of water). At pressures that are not so high, it is a general practice to take the
volume of saturated and subcooled (compressed) waters to be (1/1000) m
3
/kg.
That is why most of the steam tables do not carry the values of v
f
at low
and moderate pressures.
6.5.2 Dryness Fraction
In the previous section, we have learned to determine the properties
of saturated steam and saturated water from the Saturated Water and
Steam Table. That is to say, we have learned to determine the properties
at any state along the curve LCG of Figure 6.2(b) or Figure 6.3(b). In
this section, we will learn to determine the property of a state represented
by any point in the saturated liquid-vapour region bounded by the curve
LCG.
One such state is represented by point F in Figure 6.6. At this state,
we know that a pure substance exists as part liquid and part vapour. That
is, it is a mixture of saturated liquid and saturated vapour. Under ideal
mixing conditions, the properties of the saturated liquid and the saturated
vapour in this mixture are represented by points D and B, respectively.
To analyze such a mixture properly, we need to know the portions of the
saturated liquid and saturated vapour phases present in the mixture. This
is done by introducing a quantity known as dryness fraction, denoted by
x. Dryness fraction, which is also known as quality, is dened as the mass
fraction of saturated vapour in a saturated vapour-liquid mixture. That is,
x =
m
g
m
T
(6.1)
with
m
T
= m
g
+ m
f
(6.2)
where m
f
, m
g
and m
T
are the respective masses of the saturated liquid,
saturated vapour and the saturated vapour-liquid mixture.
v
P
D
F
B
r r r
Figure 6.6 Point F represents a typical saturated liquid-vapour mixture.
If the given mixture lies on the saturated liquid line, as in the case of
point D, then it contains no vapour. Therefore, x = 0. If the given mixture
lies on the saturated vapour line, as in the case of point B, then it contains
only vapour. Therefore, x = 1. For any mixture that lies in between these
two extremes, as in the case of point F, x takes a value between 0 and 1.
Note that dryness fraction has signicance only for saturated mixtures.
Since a saturated mixture can be treated as a combination of saturated
liquid and saturated vapour, the property such as the specic volume of a
saturated mixture can be found as follows:
v =
V
Total
m
T
=
V
f
+ V
g
m
T
=
m
f
v
f
+ m
g
v
g
m
T
(6.3)
where v
g
and v
f
are the respective specic volumes of the saturated vapour
and the saturated liquid in the mixture.
Combining (6.1), (6.2) and (6.3) to eliminate the masses, we get
v = (1 x) v
f
+ xv
g
= v
f
+ x(v
g
v
f
) = v
f
+ xv
fg
(6.4)
where v
fg
v
g
v
f
. The expression for v in (6.4) can be interpreted as
follows. The mixture has at least the volume of the saturated liquid, but has
in addition the volume gained by vaporization of the fraction represented
by x.
88 Chapter 6
The analysis given above can be repeated for specic internal energy,
specic enthalpy and specic entropy of the saturated mixture with the
following results:
u = u
f
+ x(u
g
u
f
) = u
f
+ xu
fg
(6.5)
h = h
f
+ x(h
g
h
f
) = h
f
+ xh
fg
(6.6)
s = s
f
+ x(s
g
s
f
) = s
f
+ xs
fg
(6.7)
Another quantity that is used to represent the portions of the liquid and
vapour phases in the mixture is moisture, which is dened as
moisture =
mass of saturated liquid
total mass of the mixture
=
m
f
m
T
(6.8)
Therefore, moisture can be related to dryness fraction (or quality) as fol-
lows:
moisture =
m
T
m
g
m
T
= 1 x = 1 dryness fraction (6.9)
Example 6.3
Determine v, u and h of water at 150 kPa and
10% dryness fraction (or quality).
It is a mixture of saturated steam and water at 150 kPa with the dryness
fraction of x = 0.10. Therefore, (6.4), (6.5) and (6.6) must be used to determine
v, u and h, respectively. A typical entry in a Saturated Water and Steam Table
at 150 kPa (= 1.5 bar) is shown below:
p t
s
v
g
u
f
u
g
h
f
h
fg
h
g
- - -
bar

C m
3
/kg kJ/kg kJ/kg kJ/kg kJ/kg kJ/kg - - -
1.4 109.3 1.236 458 2517 458 2232 2690 - - -
1.5 111.4 1.159 467 2519 467 2226 2693 - - -
1.6 113.3 1.091 475 2521 475 2221 2696 - - -
From the third entry in the second row of the table above we get v
g
=
1.159 m
3
/kg. The value of v
f
may be evaluated in a method similar to the one
discussed in the Solution to Example 6.2, or may be approximated to 0.001
m
3
/kg. Then
v = 0.001 + 0.1 (1.159 0.001) = 0.117 m
3
/kg
We can calculate u and h using similar procedure as follows:
u = u
f
+x(u
g
u
f
) = 467 + 0.1 (2519 467) = 672.2 kJ/kg
h = h
f
+xh
fg
= 467 + 0.1 2226 = 689.6 kJ/kg
The mixture is at its saturated temperature of 111.4
C.
6.5.3 Superheated Steam Table
Superheated Steam Table lists the data corresponding to any state rep-
resented by a point in the superheated vapour region of Figure 6.2(b) or
Figure 6.3(b). One such state is represented by point A of Figure 6.7. In
the superheated vapour region, two properties can be chosen with com-
plete freedom. Pressure and temperature are used as the two independent
properties in the Superheated Steam Table.
v
P
D
F
B
r r r
Figure 6.7 Point A represents a typical entry of the superheated vapour
state on the Superheated Steam Table.
A
r
Example 6.4
Determine v, u, h and s of water at 4 MPa
and 350
C.
90 Chapter 6
First of all, we must nd out if the given state is a saturated state or a
superheated state or a compressed state. A typical entry corresponding to the
pressure of 4 MPa (or 40 bar) found from a Saturated Water and Steam Table
is reproduced below:
p t
s
v
g
u
f
u
g
h
f
h
fg
h
g
s
f
s
fg
s
g
bar

C m
3
/kg kJ/kg kJ/kg - - - - - -
40 250.3 0.04977 1082 2602 - - - - - -
The saturated temperature at 40 bar is 250.3
C. This means that water

boils at 250.3
C at 40 bar. Therefore, steam at 350
C at 40 bar is at the
superheated state. Typical entries corresponding to superheated steam at 40
bar in a Superheated Steam Table are reproduced below:
p
(t
s
)
t 200 250 300 350 400 -
v
g
0.0498 v 0.0588 0.0664 - -
40 u
g
2602 u 2728 2828 - -
(250.3) h
g
2801 h 2963 3094 - -
s
g
6.070 s 6.364 6.584 - -
where the units used for p, t, v, u, h and s are bar,

C, m
3
/kg, kJ/kg, kJ/kg
and kJ/kg K, respectively.
The rst column of the entry shows the pressure 40 bar and the corresponding
saturated temperature 250.3
C given within the brackets. The second column

gives the saturated vapour properties as v
g
= 0.0498 m
3
/kg, u
g
= 2602 kJ/kg,
h
g
= 2801 kJ/kg and s
g
= 6.070 kJ/kg K.
The rest of columns shows the superheated steam properties in the order v,
u, h and s at 200
C, 250
C, 300
C, 350
C, etc. at 40 bar pressure. Note that

the columns corresponding to the temperatures of 200
C and 250
C are empty
since these temperatures are below the saturated temperature 250.3
C.
The entry corresponding to 350
C would give the properties of superheated

steam at 40 bar and 350
C as v = 0.0664 m
3
/kg, u = 2828 kJ/kg, h = 3094
kJ/kg and s = 6.584 kJ/kg K.
Example 6.5
Determine v, u, h and s of water at 100 bar
and 320
C.
It can be seen from any Saturated Water and Steam Table that the saturated
temperature at 100 bar is 311.0
C. Therefore, steam at 100 bar and 320
C is at
superheated state and the corresponding entry found in a Superheated Steam
Table is shown below:
p
(t
s
)
t 350 375
100 v
g
0.01802 v 10
2
2.241 2.453
(311.0) h
g
2725 h 2926 3017
s
g
5.615 s 5.947 6.091
where the units used for p, t, v, h and s are bar,

C, m
3
/kg, kJ/kg and
kJ/kg K, respectively.
Superheated steam properties at the required temperature of 320
C are not
available in the entries shown above. Therefore, we must use the method of linear
interpolation between the saturated steam entries at 311
C and the superheated

steam entries at 350
C to obtain v, h and s at 100 bar and 320
C as follows:
v 0.01802
0.02241 0.01802
=
320 311
350 311
gives v = 1.90310
2
m
3
/kg. Similarly,
h 2725
2926 2725
=
s 5.615
5.947 5.615
=
320 311
350 311
gives h = 2771 kJ/kg and s = 5.692 kJ/kg K.
Since the entry for u is not found at the given state, let us use the following
procedure to determine u:
u = h pv
= (2771 kJ/kg) (100 bar)(1.903 10
2
m
3
/kg) = 2581 kJ/kg
Therefore, for superheated steam at 100 bar and 320
C, v 1.903 10
2
m
3
/kg, u 2581 kJ/kg, h 2771 kJ/kg and s 5.692 kJ/kg K. The ap-
proximate signs are introduced to show that use of linear interpolation may give
approximate results only. We have assumed that the properties of steam change
linearly with temperature between 311
C and 350
C at 100 bar, which is not

necessarily true, and therefore the results obtained may only be approximate.
92 Chapter 6
Example 6.6
Determine v, u, h and s of water at 430 bar
and 680
C.
The given pressure and temperature are well above the critical pressure and
temperature for water, and therefore the given state is a superheated state. The
corresponding entries found in a steam table are reproduced below:
p t - - 600 700 -
400 v 10
2
- - 0.809 0.993 -
h - - 3348 3677 -
s - - 6.014 6.371
450 v 10
2
- - 0.698 0.870 -
h - - 3299 3644 -
s - - 5.914 6.290
The units used for p, t
s
, v, u, h and s are bar,

C, m
3
/kg, kJ/kg, kJ/kg and
kJ/kg K, respectively.
We have to rst interpolate between the pressures 400 bar and 450 bar to
obtain the corresponding entries at 430 bar pressure. Then we have to interpolate
between 600
C and 700
C to get the results required at 680
C. Interpolating
between the pressures 400 bar and 450 bar entries corresponding to 600
C as
v 10
2
0.809
0.698 0.809
=
h 3348
3299 3348
=
s 6.014
5.914 6.014
=
430 400
450 400
gives v = 0.74210
2
m
3
/kg, h = 3319 kJ/kg and s = 5.954 kJ/kg K at
600
C. Interpolating between the pressures 400 bar and 450 bar entries corre-
sponding to 700
C as
v 10
2
0.993
0.870 0.993
=
h 3677
3644 3677
=
s 6.371
6.290 6.371
=
430 400
450 400
gives v = 0.91910
2
m
3
/kg, h = 3657 kJ/kg and s = 6.322 kJ/kg K at 430
bar and 700
C.
The results can be tabulated as follows:
p t - - 600 700 -
430 v 10
2
- - 0.742 0.919 -
h - - 3319 3657 -
s - - 5.954 6.322
Interpolating between 600
C and 700
C to get the values for 680
C as
v 10
2
0.742
0.919 0.742
=
h 3319
3657 3319
=
s 5.954
6.322 5.954
=
680 600
700 600
gives v = 0.88410
2
m
3
/kg, h = 3589 kJ/kg, s = 6.248 kJ/kg K at 680
C
and 430 bar.
To get u, let us use
u = h pv
= (3589 kJ/kg) (430 bar)(0.884 10
2
m
3
/kg) = 3209 kJ/kg
Therefore, for superheated steam at 430 bar and 680
C, v 0.88410
2
m
3
/kg, u 3209 kJ/kg, h 3589 kJ/kg and s 6.248 kJ/kg K. The approx-
imate signs are introduced to show that use of linear interpolation gives only
approximate results.
6.5.4 Compressed Water Table
Compressed Water Table lists the data corresponding to any state rep-
resented by a point in the compressed water region of Figure 6.2(b) or
Figure 6.3(b). One such state is represented by point E of Figure 6.8. In
the compressed water region, two properties can be chosen with complete
freedom.
v
P
D
F
B
r r r
Figure 6.8 Point E represents a typical compressed water state
on a Compressed Water Table.
A
r
E
r
94 Chapter 6
Example 6.7
Determine v, u, h and s of water at 7.5 MPa
and 100
C.
It can be seen from any Saturated Water and Steam Table that the saturated
temperature at 7.5 MPa (= 75 bar) is 290.5
C. This means that water boils at

290.5
C at 75 bar. Therefore at the given temperature of 100
C, the water is at
subcooled (or compressed) state. Typical entries for compressed water at 100
C
found in a Compressed Water Table
at 50 bar and 100 bar are reproduced below:

P v u h s
bar m
3
/kg kJ/kg kJ/kg kJ/kg K
50 0.0010410 417.52 422.72 1.3030
100 0.0010385 416.12 426.50 1.2992
The pressure of interest is 75 bar and the above entries are at 50 bar and 100
bar, and therefore we use the method of linear interpolation to get the values at
the pressure specied as follows:
v 0.0010385
0.0010410 0.0010385
=
75 100
50 100
gives v 0.0010398 m
3
/kg at 75 bar and 100
C. Similarly,
u 416.12
417.52 416.12
=
h 426.50
422.72 426.50
=
s 1.2992
1.3030 1.2992
=
75 100
50 100
gives u 416.82 kJ/kg, h 424.61 kJ/kg and s 1.3011 kJ/kg K at 75 bar
and 100
C.
Example 6.8
Determine v, u, h and s of water at 6 bar and
50
C.
Table A-7 of Cengel, Y.A. & Boles, M.A. 1998 Thermodynamics: an engineering
approach, 3
rd
It can be seen from any Saturated Water and Steam Table that the satu-
rated temperature at 6 bar is 158.8
C. Therefore, 6 bar and 50
C represent a
compressed water state, and the properties at this state are to be found.
Entries in many Compressed Water Tables, however, start at about 50 bar
since compressed water properties are relatively independent of the pressure at
relatively low pressures such as 6 bar. It is therefore we shall use the general
approximation, that is to treat compressed liquid as saturated liquid
at the given temperature. This is because the compressed water (or liquid)
properties depend on temperature more strongly than they do on pressure.
Thus, in the absence of compressed liquid data, it can be assumed that the
respective values of v, u, h and s required at a given pressure and temperature
are approximately equal to v
f
, u
f
, h
f
and s
f
at the given temperature, which
are the properties of the saturated liquid at that temperature.
The saturated liquid at 50
C, as we can nd from a a Saturated Water and

Steam Table, is at 0.1233 bar. At that state, v
f
= 0.1012 10
2
m
3
/kg, h
f
= 209.3 kJ/kg, and s
f
= 0.704 kJ/kg K. The specic internal energy could be
worked out using
u
f
= h
f
P v
f
= 209.3 (0.1233 10
2
)(0.1012 10
2
) = 209.29 kJ/kg
Therefore, the properties at 6 bar and 50
C may be given as v 0.1012

10
2
m
3
/kg, u 209.29 kJ/kg, h 209.3 kJ/kg and s 0.704 kJ/kg K.
Example 6.9
Determine h of water at 6 bar and 50
C using
C
p
for saturated liquid water as 4.182 kJ/kg K at 50
C and 4.35 kJ/kg K

at 160
C.
Let us imagine that we heat water from the subcooled water state at 6
bar and 50
C to the saturated water state at 6 bar and 158.8
C at a constant
pressure of 6 bar. For a constant-pressure process of water, we can apply (5.13)
as
h = h
f
h
50
o
C
=
ts
50
o
C
C
p
dT
96 Chapter 6
which is applicable for water since it is in one single phase during the heating
process from 50
C to the saturation temperature t

s
= 158.8
C at 6 bar. The
saturated liquid enthalpy at 6 bar is h
f
= 670 kJ/kg. Therefore
670 h
50
o
C
=
158.8+273
50+273
C
p
dT
The specic heat at constant volume C
p
changes with temperature and
pressure. We can ignore the dependence of C
p
on pressure. We are given that
C
p
for saturated liquid water is 4.182 kJ/kg K at 50
C and 4.35 kJ/kg K

at about 160
C. Taking an average value for C

p
as (4.182+4.35)/2, we can
calculate h as
h
50
o
C
= 670
(4.182 + 4.35)
2
(158.8 50) = 205.9 kJ/kg
Comment: Note that the Solution to Example 6.8 and the Solution
to Example 6.9 exhibit two dierent ways of nding an approximate value of
the enthalpy of compressed water at pressures for which the compressed water
properties are not readily available in Compressed Water Tables.
6.6 Worked Examples
Example 6.10
Methane gas stored in a 10 m
3
rigid tank is
at 2.0 MPa pressure and 300 K temperature. Owing to undetected leakage,
the pressure in the tank is reduced to 1 bar while the temperature remained
at 300 K. Determine the mass of methane lost due to leakage, assuming
ideal gas behaviour.
Amount of methane lost due to the leakage can be found if we know the
amounts of methane in the tank before and after the development of the leak.
Before the leak developed, methane in the tank is at 2.0 MPa pressure and 300
K temperature, and the volume of the tank is 10 m
3
. Therefore, the amount of
methane in the tank before the leak, denoted by n
o
, can be calculated using the
ideal gas equation of state as follows:
n
o
=
(2.0 MPa 10
3
kPa/MPa) (10 m
3
)
(8.314 kJ/kmol K) (300 K)
= 8.02 kmol
from which the mass of methane before the leak is found as
m
o
= (8.02 kmol) (16 kg/kmol) = 128.3 kg
After the leak, the pressure is 1 bar and the temperature is 300 K. The
volume of the tank remains the same at 10 m
3
since the tank is rigid. The
amount of methane in the tank after the leak, denoted by n
f
, can be calculated
using the ideal gas equation of state as follows:
n
f
=
(1 bar 10
2
kPa/bar) (10 m
3
)
(8.314 kJ/kmol K) (300 K)
= 0.40 kmol
from which the mass of methane before the leak is found as
m
f
= (0.40 kmol) (16 kg/kmol) = 6.4 kg
The mass of methane lost due the leakage is therefore
= m
o
m
f
= 128.3 kg 6.4 kg = 121.9 kg.
Example 6.11
Redo Example 6.10 considering the real
gas behaviour of methane.
Before the leak, methane is at 2.0 MPa and 300 K and it occupies 10 m
3
volume. Table A.7.2SI of Van Wylan, Sonntag & Borgnakke
lists the real gas
Van Wylan, G., Sonntag, R. & Borgnakke, C. 1994 Fundamentals of Classical

Thermodynamics, 4
th
Edition, John Wiely & Sons.
98 Chapter 6
properties of methane. From which we get the specic volume of methane at
2.0 MPa and 300 K as 0.0751 m
3
/kg. The mass of methane before the leak is
therefore given by
m
o
=
total volume
specic volume
=
10 m
3
0.0751 m
3
/kg
= 133.2 kg
After the leak, methane is at 1 bar and 300 K and it still occupies 10 m
3
volume. Table A.7.2SI of Van Wylan, Sonntag & Borgnakke lists the specic
volume of methane at 1 bar, which is 0.1 MPa, and 300 K as 1.5521 m
3
/kg.
The mass of methane after the leak is therefore given by
m
f
=
total volume
specic volume
=
10 m
3
1.5521 m
3
/kg
= 6.44 kg
The mass of methane lost due the leakage is therefore
= m
o
m
f
= 133.2 kg 6.44 kg = 126.8 kg.
Note that the mass of methane after the leak, calculated assuming
ideal gas behaviour (Example 6.10) is nearly the same as that calculated
considering the real gas behaviour of methane (Example 6.11). It is
because methane is at 1 bar after the leak, and 1 bar can be considered
as low pressure. At low pressures, real gases imitate ideal gas behaviour.
Thus, calculating the mass of methane at 1 bar pressure assuming ideal gas
behaviour does not introduce any signicant error in the calculation.
The mass of methane before the leak is 128.3 kg when ideal gas
behaviour is assumed (Example 6.10), and 133.2 kg when real gas be-
haviour is considered (Example 6.11). It is because methane is at 2.0
MPa before the leak, which is nearly 20 times the atmospheric pressure,
and therefore does not fall in the category of low pressure. Calculating the
mass of methane at 2.0 MPa assuming ideal gas behaviour introduces an
error of about 3.7%.
The estimated mass of methane lost due to leakage assuming ideal
gas behaviour, therefore, introduces an error of about 3.9%. The result
obtained assuming ideal gas behaviour is, however, acceptable as a rst
estimation of the mass of methane lost due to the leakage.
Example 6.12
Extracted values from a Steam Table is given
below:
p t v
g
u
f
u
g
(bar) (
C) (m
3
/kg) (kJ/kg) (kJ/kg)
1.013 100.0 1.673 - -
5 151.8 0.3748 639 2562
7 165.0 0.2728 696 2573
h
f
h
g
s
f
s
g
(kJ/kg) (kJ/kg) (kJ/kg K) (kJ/kg K)
419.1 2675.8 1.307 7.355
640 2749 1.860 6.822
697 2764 1.992 6.709
Using the above table, determine the following:
(a) Condition of water/steam at 6 bar and s = 8.3 kJ/kg K
(b) Condition of water/steam at 5 bar and u = 2500 kJ/kg
(c) Specic internal energy at 1.013 bar and v = 0.72 m
3
/kg
(d) Specic enthalpy and specic internal energy at 7 bar and 100
C
(a) The table above shows that s = 8.3 kJ/kg K is greater than s
g
= 6.822
kJ/kg K at 5 bar, and s
g
= 6.709 kJ/kg K at 7 bar. From the values of
s
g
at 5 bar and 7 bar, we can conclude that the saturated vapour specic
entropy, s
g
, at 6 bar lies in between 6.709 and 6.822, and therefore s =
8.3 kJ/kg K is greater than s
g
at 6 bar. That means we have superheated
steam at 6 bar and s = 8.3 kJ/kg K.
(b) The table above shows, at 5 bar, u
f
= 639 kJ/kg and u
g
= 2562 kJ/kg.
Since u = 2500 kJ/kg at 5 bar lies between the saturated water specic
internal energy u
f
and the saturated vapour specic internal energy u
g
at
5 bar, we have a mixture of saturated steam and saturated water at 5 bar
and u = 2500 kJ/kg.
(c) The table above shows, at 1.013 bar, the given specic volume v = 0.72
m
3
/kg is less than the saturated vapour specic volume v
g
= 1.673 m
3
/kg.
100 Chapter 6
The saturated water specic volume v
f
is not given but may be approxi-
mated to 1/1000 m
3
/kg. The given specic volume v = 0.72 m
3
/kg lies
between v
f
and v
g
, and therefore what we have is a mixture of saturated
steam and saturated water. Using (6.4), we can calculate the dryness
fraction x at the given state as follows:
x =
v v
f
v
g
v
f
=
0.72 0.001
1.673 0.001
= 0.43
The specic internal energy u at the given state could have been deter-
mined using (6.5), u = u
f
+x(u
g
u
f
), had we known u
f
and u
g
. Since
these values are not given in the table above, let us evaluate the specic
enthalpy h at the given state using (6.6) as follows:
h = h
f
+x(h
g
h
f
) = 419.1 +0.43 (2675.8 419.1) = 1389.5 kJ/kg
The specic internal energy at the given state can now be evaluated as
follows:
u = h p v = 1389.5 kJ/kg 1.013 bar 0.72 m
3
/kg = 1316.5 kJ/kg
(d) The table above shows, at 7 bar, the saturation temperature is 165.0
C,
therefore we have compressed water at 7 bar and 100
C. Since the prop-

erties of compressed water is relatively insensitive to the pressure, the
compressed water specic enthalpy h at 7 bar and 100
C can be approx-
imated to h
f
, the saturated water specic enthalpy, at 100
C. The table
above shows that h
f
at 100
C is 419.1 kJ/kg, and therefore h at 7 bar

and 100
C can be approximated to 419 kJ/kg. Similarly, the compressed

water specic internal energy u at 7 bar and 100
C can be approximated
to u
f
at 100
C, which is in fact not provided in the table above. Let

us rst calculate u
f
at 100
C using u
f
= h
f
p v
f
, where h
f
= 419.1
kJ/kg, p = 1.013 bar and v
f
may be taken as 1/1000 m
3
/kg, which gives
u
f
419 kJ/kg. Therefore, u at 7 bar and 100
C can be approximated
to 419 kJ/kg.
Example 6.13
Specify the condition of water/steam at the fol-
lowing states along with its dryness fraction wherever applicable, and determine
the specic internal energy at that state:
(a) At 0.05 bar and 50
C
(b) At 0.75 bar and s = 7.75 kJ/kg K
(c) At 3 bar and 120
C
(d) At 1 bar and h = 2000 kJ/kg
(a) Saturated Water and Steam Table shows that the saturation temperature
at 0.05 bar is 32.9
C. Therefore, 0.05 bar and 50
C is a superheated
vapour state. Superheated Steam Table gives u = 2445 kJ/kg at that
state. Dryness fraction has no meaning at a superheated vapour state.
(b) Saturated Water and Steam Table shows that, at 0.75 bar, s
f
= 1.213
kJ/kg K and s
g
= 7.456 kJ/kg K. The given value of s = 7.75 kJ/kg K
is greater than s
g
, which corresponds to saturated steam. Therefore,
the given state is a superheated vapour state. Superheated Steam Table
shows the entry 0.75 bar and s = 7.75 kJ/kg K at 150
C, and the cor-

responding entry for u as 2585 kJ/kg. Dryness fraction has no meaning
at a superheated vapour state.
(c) Saturated Water and Steam Table shows that the saturation temperature at
3 bar is 133.5
C. Therefore, 3 bar and 120
C is a compressed water state.

Using the approximate method provided in the Solution to Example
6.8, the compressed water specic internal energy u at 3 bar and 120
C
can be approximated to the saturated water specic internal energy u
f
at
120
C, which is about 505 kJ/kg as can be read from Saturated Water

and Steam Table. Dryness fraction has no meaning at a compressed water
state.
(d) Saturated Water and Steam Table shows that, at 1 bar, h
f
= 417 kJ/kg
and h
g
= 2675 kJ/kg. The given value of h = 2000 kJ/kg lies in between
h
f
and h
g
. Therefore, the given state is a mixture of saturated water and
saturated steam. The dryness fraction x at that state can be calculated
using (6.6) as follows:
x =
h h
f
h
g
h
f
=
2000 417
2675 417
= 0.70
The specic internal energy u at the given state is determined using (6.5)
as follows:
u = u
f
+x(u
g
u
f
) = 417 + 0.70 (2506 417) = 1879 kJ/kg
102 Chapter 6
Example 6.14
With the help of a Steam Table, ll in the blank
spaces in the following table:
Property Set 1 Set 2 Set 3 Set 4 Set 5
t,

C 280.8 500
p, bar 7 80 100
m, kg 1 2 1.3 3.5 3
v, m
3
/kg 0.3714
V , m
3
Moisture, % 20
h, kJ/kg 2779
u, kJ/kg 3077
s, kJ/kg K 5.100
Set 1 gives the temperature as 280.8
C but does not give the pressure.

Each entry on the Steam Table is determined by two properties, and the second
property in the case of Set 1 is h = 2779 kJ/kg. When searching for the entry
at t = 280.8
C and h = 2779 kJ/kg in a Saturated Water and Steam Table, we

will nd that it is an entry corresponding to saturated vapour at 65 bar. Other
properties for Set 1 could be determined from the entries for saturated vapour
at 65 bar and 280.8
C in the Saturated Water and Steam Table.

For Set 2, we can nd from any Saturated Water and Steam Table that
the specic volume of the saturated steam at 7 bar is 0.2728 m
3
/kg. The
specic volume that we require is 0.3714 m
3
/kg, which is much greater than
the specic volume of the saturated steam. This means that the state of Set 2
is a superheated steam state. Any Superheated Steam Table would show that
the required entry is at 7 bar and 300
C. Other properties for Set 2 could be

determined from the entries at corresponding superheated vapour at 7 bar and
300
C in the Superheated Steam Table.

In case of Set 3, search any Steam Table for an entry that shows the pair
500
C and u = 3077 kJ/kg. It is possible that we nd from a Superheated

Steam Table that the required entry lies in between the entries corresponding
to 60 bar and 500
C, with u = 3081 kJ/kg, and 70 bar and 500
C, with u =
3073 kJ/kg. By appropriate interpolation, we could nd the properties required
at 500
C and u = 3077 kJ/kg to ll the column for Set 3.

Set 4 has 80 bar and 20% moisture, which is 80% dryness fraction. And,
therefore what we have is a mixture of saturated water and saturated steam
with x = 0.8. The saturation temperature for 80 bar could be found from a
Saturated Water and Steam Table as 295.0
C. The properties of saturated water

and saturated steam could be read from the Saturated Water and Steam Table
at 80 bar, and then (6.4), (6.5), (6.6) and (6.7) can be used to calculate the
respective values of v, u, h and s at that state.
For Set 5, the entries corresponding to 100 bar in a Saturated Water and
Steam Table would show that the saturated water entropy s
f
= 3.360 kJ/kg K
and the saturated steam entropy s
g
= 5.615 kJ/kg K. The given value of s =
5.100 kJ/kg K in Set 5 lies between s
f
and s
g
, and therefore what we have is a
mixture of saturated water and saturated steam. Using the values of s, s
f
and
s
g
in (6.7), we can calculate the dryness fraction x. and then (6.4), (6.5) and
(6.6) can be used to calculate the respective values of v, u and h. Temperature
required is the saturation temperature at 100 bar.
The duly lled table of Example 6.14 is as follows:
Property Set 1 Set 2 Set 3 Set 4 Set 5
t,

C 280.8 300 500 295.0 311.0
p, bar 65 7 65 80 100
m, kg 1 2 1.3 3.5 3
v, m
3
/kg 0.02972 0.3714 0.0524 0.0191 0.0143
V , m
3
0.02972 0.7428 0.0681 0.0668 0.0428
Moisture, % 0 - - 20 22.8
h, kJ/kg 2779 3060 3415.5 2470 2425
u, kJ/kg 2586 2800 3077 2317 2282
s, kJ/kg K 5.851 7.298 6.8375 5.237 5.100
Example 6.15
Fill in the blank spaces of the following table
with the help of a Steam Table:
Property Set 1 Set 2 Set 3 Set 4 Set 5 Set 6
t,

C 425 200
p, bar 160 20 70 5
v, m
3
/kg 0.1
x, % 65
h, kJ/kg 2100
u, kJ/kg 2008 2940
s, kJ/kg K 7.4
104 Chapter 6
Property Set 1 Set 2 Set 3 Set 4 Set 5 Set 6
t,

C 425 200 285.8 284.1 212.4 404
p, bar 160 20 70 5 20 30
v, m
3
/kg 0.01573 0.001 0.0158 0.5073 0.0651 0.1
x, % - - 55.35 - 65 -
h, kJ/kg 3051 852 2100 3032 2137.5 3240
u, kJ/kg 2799 850 1990 2779 2008 2940
s, kJ/kg K 5.968 2.331 4.612 7.4 4.978 6.934
Example 6.16
A rigid container of 0.1 m
3
and negligible heat
capacity contains steam at 500 kPa and 400
0
C. If the container is cooled, deter-
mine the pressure and temperature at which steam starts to condense. Determine
also the amount of heat removed during the cooling process.
The initial state of steam is given by P
initial
= 500 kPa, and T
initial
=
400
0
C. It is found from a Saturated Water and Steam Table that the saturation
temperature at 500 kPa (that is, 5 bar) is 151.8
C. Therefore, we have super-

heated steam at the initial state, which is cooled until it starts to condense,
which means until it reaches the saturated vapour state. We have to determine
the pressure and temperature of steam at this nal state.
To be able to locate the nal state, which is a saturated vapour state, we
need to know at least one property at the nal state. Since the container is
rigid, the total volume remains a constant during the process. Since the given
system is a closed one, the total mass remains a constant as well. Therefore,
the specic volume remains a constant during the cooling process.
It is found from a Superheated Steam Table that v
initial
= 0.6172 m
3
/kg
at 5 bar and 400
C, so that the specic volume of the saturated vapour at the

nal state is 0.6172 m
3
/kg. That is, v
g
= 0.6172 m
3
/kg. We need to nd the
corresponding saturation pressure and saturation temperature at this nal state.
From a Saturated Water and Steam Table we found the following:
v
g
= 0.6253 m
3
/kg at 2.9 bar and 132.4
C.
v
g
= 0.6057 m
3
C.
Interpolating between the two states above for v
g
of 0.6172 m
3
/kg, we get
the saturation values as follows:
0.6172 0.6057
0.6253 0.6057
=
P
sat
3.0
2.9 3.0
=
T
sat
133.5
132.4 133.5
which gives T
sat
= 132.9
C, and P
sat
= 2.94 bar. The superheated steam at 5
bar and 400
C, when cooled, starts to condense at 2.94 bar and 132.9
C.
To determine the amount of heat removed from the system, we shall use the
rst law. Since the container is rigid and since no other form of work is done on
the system, the rst law applied to the given system yields
Q
in
= U = m
steam
(u
final
u
initial
)
Superheated Steam Table gives u
initial
= 2963 kJ/kg at 5 bar and 400
C.
We need to carry out an interpolation to determine u
final
, which is u
g
at 2.94
bar and 132.9
C.
Referring to a Saturated Steam and Water Table for u
g
values, we got the
following:
u
g
= 2543 kJ/kg and v
g
= 0.6253 m
3
C.
u
g
= 2544 kJ/kg and v
g
= 0.6057 m
3
C.
Interpolating between the two states yields the following:
0.6172 0.6057
0.6253 0.6057
=
u
final
2544
2543 2544
which gives u
final
= 2543.4 kJ/kg.
The mass of the steam can be found as follows:
m
steam
=
total volume
specic volume
=
0.1 m
3
0.6172 m
3
/kg
= 0.1620 kg
Therefore,
Q
in
= (0.1620 kg) (2543.4 2963) kJ/kg = 67.975 kJ
That is, the heat removed during the cooling process is about 68 kJ.
106 Chapter 6
Example 6.17
A rigid tank with negligible heat capacity, is per-
fectly insulated and divided into two unequal compartments A and B separated
by a partition. Compartment A, having 0.05 m
3
volume, contains steam at 1.5
bar and 250
C. Compartment B, having 0.15 m

3
volume, contains steam at 8
bar and 250
C. The partition is removed and the system is allowed to reach

equilibrium. Determine the pressure and the temperature at the new equilibrium
state.
Application of the rst law of thermodynamics to the entire system would
give
U = 0
since no heat or work transfers occur between the entire system and the sur-
roundings. Neglecting the internal energy changes of the tank and the partition,
we shall write the above as
U
final
= U
initial
(6.10)
for the steam present in the tank.
We shall determine U
initial
as follows:
U
initial
= m
A
u
A
+m
B
u
B
=
0.05 m
3
v
A
u
A
+
0.15 m
3
v
B
u
B
(6.11)
of which v
A
and u
A
are the respective specic volume and specic internal
energy at 1.5 bar and 250
C, and v
B
and u
B
are the respective specic volume
and specic internal energy at 8 bar and 250
C.
Saturated Water and Steam Table would show that the saturation tempera-
ture is 111.4
C at 1.5 bar and 170.4
C at 8 bar. It is therefore we conclude that

the steam in each of the two compartments are at superheated state. Using the
Superheated Steam Table, we can get the following:
v
A
= 1.601 m
3
/kg and u
A
= 2733 kJ/kg at 1.5 bar and 250
C.
v
B
= 0.2933 m
3
/kg and u
A
= 2716 kJ/kg at 8 bar and 250
C.
Using these values in (6.11), we get U
initial
= 1474 kJ. Substituting it in
(6.10), we get U
final
= 1474 kJ.
The specic internal energy at the nal state is therefore
u
final
=
U
final
m
A
+m
B
=
1474 kJ
[(0.05/1.601) + (0.15/0.2933)] kg
= 2716 kJ/kg
We need one more property at the nal state to completely specify the
nal state. The other property is in fact the specic volume at the nal state
determined as follows:
v
final
=
V
total
m
A
+m
B
=
[0.05 + 0.15] m
3
[(0.05/1.601) + (0.15/0.2933)] kg
= 0.3686 m
3
/kg.
Searching for an entry with u = 2716 kJ/kg and v = 0.3686 m
3
/kg all over
the Steam Table, we come across these adjacent entries for the superheated
steam at 6 bar.
v = 0.3522 m
3
/kg and u = 2640 kJ/kg at 6 bar and 200
C.
v = 0.3940 m
3
C.
Interpolating for u at v = 0.3686 m
3
/kg gives
u 2640
2722 2640
=
0.3686 0.3522
0.3940 0.3522
u = 2672 kJ/kg
which is less than 2716 kJ/kg. Thus, this entry does not give the state required.
Let us now try the adjacent entries for the superheated steam at 7 bar.
v = 0.3001 m
3
C.
v = 0.3364 m
3
C.
Interpolating for u at v = 0.3686 m
3
/kg gives the following:
u 2636
2720 2636
=
0.3686 0.3001
0.3364 0.3001
u = 2795 kJ/kg
which is more than 2716 kJ/kg. Thus, this entry does not give the state required.
108 Chapter 6
Searching between 6 bar and 7 bar in the range of 200
C to 250
C by inter-
polation, we get the required v-u combination at 6.4 bar and 247
C.
6.7 Summary
In working out thermodynamic problems on closed systems with water/steam,
the following tools are used:
Tool 2: The rst law of thermodynamics applied to closed simple compressible
systems, given by Q
in
+W
in
= U, which is the principle of conservation
of energy.
Tool 3: When two properties at an equilibrium state are known, the remaining
properties at that state may be obtained from the Steam Table.
Tool 4: Evaluation of U using data on internal energy at the initial and nal
states obtained from the Steam Table.
Tool 5: Any other constraint stated in the problem.
Chapter 7
BOUNDARY WORK
Frank is struck - as if for the rst time - by how much civilization
depends on not seeing certain things and pretending others never
occurred.
Francine Prose (Amateur Voodoo)
In this chapter we will learn to evaluate W
in
, which is the work term
in the rst law of thermodynamics. Work can be of dierent types, such
as boundary work, stirring work, electrical work, magnetic work, work of
changing the surface area, and work to overcome friction. In this chapter,
we will concentrate on the evaluation of boundary work.
110 Chapter 7
7.1 Boundary Work in Real Life
Boundary work is done when the boundary of the system moves, causing
either compression or expansion of the system. A real-life application of
boundary work, for example, is found in the diesel engine which consists of
pistons and cylinders as the prime component of the engine.
In a diesel engine, air is fed to the cylinder and is compressed by the
upward movement of the piston. The boundary work done by the piston
in compressing the air is responsible for the increase in air temperature.
Onto the hot air, diesel fuel is sprayed, which leads to spontaneous self
ignition of the fuel-air mixture. The chemical energy released during this
combustion process would heat up the gases produced during combustion.
As the gases expand due to heating, they would push the piston downwards
with great force. A major portion of the boundary work done by the gases
on the piston gets converted into the energy required to rotate the shaft
of the engine.
The rotating shaft of the diesel engine is responsible for turning the
wheels of an automobile. The rotating shaft could also be used to spin a
coil between the north and south poles of an electromagnet thus generating
electricity as in the generators.
7.2 Evaluation of Boundary Work
Consider, for example, compression of the gas contained in the piston-
cylinder device shown in Figure 7.1.

dx
gas
. ., piston
/
/-
cylinder
. . . . .
. . . . . .
. . . . . .
. . . . .
. . . .
. . .
. . . .
. . . . .
. . . . . .
. . . . .
. . . . . .
. . . . .
.
.
Figure 7.1 A compression process during which boundary work is
done on the system by its surroundings.
F
. .
. .
. .
. .
. .
. .
. .
. .
. .
. .
. .
. .
.
.
.
.
.
.
.
. .
. .
.
. .
.
. .
.
. .
.
. .
.
.
.
.
.
.
.
Boundary Work 111
Take the gas contained in the piston-cylinder device as the system. The
inner surfaces of the piston and cylinder dene the boundary of the system.
Everything outside the boundary is the surroundings. During compression,
the boundary is moved by the surroundings so as to reduce the volume of
the system.
If at a certain state during the process, say, the boundary of the system
is displaced by an innitesimal (that is, a very tiny) distance dx by the
application of force F as shown in Figure 7.1. The dashed line shown in
the gure indicates the new position of the boundary (note that the dis-
placement is exaggerated.) Boundary work is evaluated by determining the
product between the displacement of a system boundary and the force caus-
ing the displacement in the direction of the displacement. The innitesimal
amount of boundary work done by the surroundings to compress the gas is
therefore
dW = F dx (7.1)
The external force F acting on one side of the piston, as shown in
Figure 7.1, tries to compress the gas. On the other side of the piston, the
gas pressure applies a force to resist the compression. If we assume that
the compression process is almost fully resisted then the forces acting
on either side of the piston become almost equal to each other. It follows
then,
F = P A (7.2)
where P is the gas pressure that is assumed to be uniformly distributed
everywhere within the gas at any state during the compression, and A is
the cross-sectional area of the piston on which the gas pressure acts.
The change in the volume of the gas, designated by dV , is related to
dx by the following:
dV = Adx (7.3)
since the gas has experienced a reduction in its volume, we know that dV is
a negative quantity. It is therefore a negative sign is placed in front of dV
in (7.3) to be able to equate it to the product of two positive quantities,
A and dx.
Eliminating F and dx from (7.1) using (7.2) and (7.3), respectively, we
get
dW = (P A)
_
dV
A
_
= P dV (7.4)
112 Chapter 7
which is the innitesimal amount of boundary work done on the system
by its surroundings. In other words, this amount of boundary work enters
the system. Incorporating this information as a subscript on dW, (7.4) is
rewritten as
dW
in
= P dV (7.5)
If the process considered were an expansion process, then the system
would have moved the boundary so as to increase the volume of the system.
The innitesimal amount of boundary work done by the system on its
surroundings (that is, the work leaving the system) would therefore be
given by
dW
out
= P dV (7.6)
Integrating (7.5) or (7.6) between the initial state with volume V
o
, and
the nal state with volume V
f
, we get
W
out
= W
in
=
_
V
f
Vo
P dV (7.7)
The total boundary work is therefore expressed in terms of system properties
P and V by (7.7). It is important to observe that (7.7) can be applied
to evaluate the boundary work for any substance, solid, liquid, gas or any
mixture of phases, provided that the expansion or compression process
occurs under almost fully resisted condition.
Student: Teacher, one of the assumptions you made to derive at equation
(7.7) is that the system pressure P is uniformly distributed every-
where within the system at any state during the compression process. I
dont feel comfortable with that assumption. It is because I think, dur-
ing compression, the gas close to the face of the piston gets compressed
more than the gas away from the face of the piston leading to nonuniform
pressure distribution?
Teacher: Yes, if the compression process were sudden, the gas close to the
face of the piston would get compressed more than the gas away from the
face of the piston. The resulting pressure distribution within the system
would then be far from uniform. On the other hand, if the compression
or the expansion process is carried in such a manner that it is almost
fully resisted while taking place, then it will be possible to maintain an
almost uniform pressure distribution within the system as it undergoes
the compression or expansion process.
Boundary Work 113
Student: Teacher, could you please explain me how exactly a process is carried
out under almost fully resisted condition?
Teacher: Yes, I will. Take a look at Figure 7.2. Let us imagine that the lit-
tle unhappy faces shown in the gure represent the gas contained in the
cylinder, trapped by the piston represented by the black solid bar shown
in the gure. The force exerted by the gas pressure on the piston pushes
the piston upwards thus causing expansion of the gas. The total weight
of the piston, the person standing on the piston and the basket of tiny
stones carried by him causes the piston to move downwards compressing
the gas. When these two forces balance each other, the system is in equi-
librium. Let us now remove a single tiny stone from the basket. Since
the mass of the tiny stone removed is extremely small, the force exerted
by the gas molecules on the piston to move it upwards becomes slightly
larger than the force exerted to prevent the expansion of gas. The piston
thus moves upwards by a very small distance allowing the gas to expand
slightly. Such an expansion process is an almost fully resisted expan-
sion, since it is carried out with a very small dierence (an innitesimal
dierence) between the force causing the expansion and the force resist-
ing the expansion. An almost fully resisted compression process
would be the reverse of the above process.
Figure 7.2 Almost fully-resisted expansion of a gas in a piston-cylinder device.
, ,
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, _ ,
, _ ,
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,

tiny stones of extremely
small mass each
piston
gas molecules
cylinder
.
114 Chapter 7
Student: I see that the forces acting on either side of the piston almost equal
each other in an almost fully resisted process. I understand very well now
how you got equation (7.2). If we had removed the stones in the basket
that the person is carrying all at once, then the piston would have risen
rapidly causing the gas to experience sudden expansion. Or, if we had
loaded the basket with a lot more stones all at once then the piston would
have moved rapidly downwards causing sudden compression of the gas.
Am I right, Teacher?
Teacher: Yes, you are. Note that the external force F is related to a gas
pressure P by (7.2) which is a property of the system, only because the
compression is assumed to be almost fully resisted. If the process were
not an almost fully resisted expansion or compression then the relationship
given by (7.2), in general, would not hold.
Student: Yes, I see that. However, I still do not see how it is possible to
maintain a uniform pressure distribution during such a process.
Teacher: Since there is only an innitesimal dierence between the force caus-
ing the expansion (or compression) and the force resisting the expansion
(or compression) in an almost fully resisted process, the pressure under-
goes only an innitesimal change at a time. Any temperature change
created by the expansion (or compression) would also be innitesimal in
its magnitude. An almost fully resisted process such as the one discussed
above could progress only very slowly so that it would allow enough time
for the innitesimal changes experienced by the properties of the system,
such as pressure, temperature, and specic volume, to be distributed al-
most uniformly across the system.
Student: Thank you, Teacher. I understand now how the uniform distribution
of properties, I mean, the almost uniform distribution of properties, is
maintained in a system when the expansion or compression process is
carried out under almost fully resisted condition.
7.3 Quasistatic Process
As beginners, we will mostly be working with the special kind of pro-
cess known as the quasistatic process, which is dened as a process
Boundary Work 115
whose path is composed of near equilibrium states. The initial and nal
states of any quasistatic process are equilibrium states, and all the states
that a system passes through along the path of a quasistatic process are
almost equilibrium states. A quasistatic process is also known as a quasi-
equilibrium process.
We have seen in Section 2.9 that an equilibrium state can be repre-
sented by a point on a property diagram. Therefore, it is acceptable to
represent the path of a quasistatic process, which is made up of near equi-
librium states, by a curve on a property diagram, as shown in Figure 7.3.
initial state
nal state
path of a quasistatic process
Pressure
Specic volume
,
I
,
F
.
>
>.
Figure 7.3 A quasistatic process with its initial state I, its nal state F,
and its path shown on a P-v diagram.
.
.,
Consequently, it is possible to describe the path of a quasistatic process
by an equation, such as P = f(v) on a P-v diagram, T = f(v) on a T-v
diagram, and P = f(T) on a P-T diagram. Moreover, since each state is
almost an equilibrium state along a quasistatic process, the properties at
a state along the path of a quasistatic process can be interrelated by, for
example, the ideal gas equation of state.
The path followed by a non-quasistatic process consists of states that
may or may not be equilibrium states, and therefore the path of a non-
quasistatic process cannot be represented by a curve on a property diagram.
The fully resisted expansion or compression process, which we were in-
troduced to in the section above, is an example of a quasistatic process
since each state along a fully resisted expansion or compression is almost
an equilibrium state.
116 Chapter 7
7.4 Boundary Work in Real Processes
Boundary work can be evaluated using (7.7) only for processes that
approximate a quasistatic process. Strictly speaking, boundary work asso-
ciated with many real systems, such as the piston-cylinder arrangements
of diesel engines described in Section 7.1, cannot be evaluated using the
work integral of (7.7). It is because the uniform nature of the properties
within the system at each and every state along the path of the process is
not maintained in such systems owing to the very high speeds at which the
piston moves.
Moreover, in the piston-cylinder device, for example, friction occurs
between the surface of contact of the piston and cylinder. The resulting
friction force on the piston acts in a direction opposite to the motion of
the piston, and therefore work is done to overcome the eect of friction.
The problem here, however, is the evaluation of the exact amount of work
done against the friction force, which is not an easy task.
Besides, friction forces acting on the piston has the capacity to hold
the piston in place until the dierence between the forces acting on either
side of the piston reaches a nite value. At this point, the friction could be
overcome and the piston would undergo a sudden movement, which in turn
would cause sudden expansion or compression of the gas contained in the
piston-cylinder device. The movement of the piston caused by a nite force
and the resulting sudden expansion or compression of the gas destroy the
quasistatic nature of the process. Therefore, we simplify our calculation of
boundary work in many real systems by making the assumption that the
piston is free to move within the cylinder without friction.
If the process is not quasistatic then there is no direct way of calculating
the work done by the system, or on the system. Since it is next to impossible
to do calculations with non-quasistatic processes, we assume, wherever
possible, that the given process is quasistatic. This assumption makes it
possible for us to carry out calculations with real thermodynamic processes.
Owing to the assumptions that friction forces are absent and that the
properties are almost uniformly distributed within the system, a quasistatic
process sets a limit for the best performance that is expected of a real
process. A device producing work produces the maximum amount of work
and a device requiring work requires the minimum amount of work when
they undergo quasistatic processes.
Boundary Work 117
7.5 Units for Boundary Work
Since work is a form of energy, the unit for work is the same as the unit
for energy. If P takes the unit Pa and V takes the unit m
3
in the work
integral of (7.7), then the unit of W
in
becomes
Pam
3
= (N/m
2
)m
3
= Nm = J.
In this textbook, we will use the unit kPa for P. And, therefore, the
unit of W
in
will be kJ.
When the total volume V of (7.7) is replaced by the specic volume v,
we get
w
in
=
_
v
f
vo
P dv (7.8)
in which w
in
takes the unit kJ/kg provided v is in m
3
/kg. If v were the
molar volume, taken in m
3
/kmol, w
in
would be in kJ/kmol. In both these
cases P is in kPa.
7.6 Path Dependence of Boundary Work
Consider the gas contained in the piston-cylinder device of Figure 7.1
once again. Imagine that we could push the piston slowly to decrease the
volume occupied by the gas while maintaining the quasistatic nature of
the process. Let us say that we measured the volume occupied by the
gas and the corresponding pressure of the gas at certain times during the
compression process, and the data so gathered were plotted on a P-V
diagram as shown by the dots of Figure 7.4. Connect the data points by a
smooth curve as in the gure. The curve so obtained represents the path
of the process between its initial state (o) and its nal state (f) on the P-V
diagram. The equation describing the curve will provide the relationship
between P and V along the path of the process.
Integrating along the path of the process on the P-V diagram of Figure
7.4 in the increasing direction of V , we get
_
Vo
V
f
PdV
118 Chapter 7
The value of the above integral is simply the area of the shaded region
shown in Figure 7.4. Interchanging the limits in the above integral, we get
_
V
f
Vo
PdV
which, according to (7.7), is W
in
. That is, the area under the curve rep-
resenting the path of a compression process on a P-V diagram gives W
in
,
which is the boundary work done on the system by its surroundings.

P
V

(f)
(o)
V
f V
o
Figure 7.4 When the process takes place in the direction of decreasing
volume (that is, compression), the area of the shaded region gives W
in
.
W
in
. . . . .
. . . . . .
. . . . . .
. . . . .
. . . .
. . .
. . . .
. . . . .
. . . . . .
. . . . .
. . . . . .
. . . . .
.
.
-
gas is compressed
from V
o
to V
f
If the process considered is an expansion process, then the volume of
the system increases from V
o
to V
f
as shown in Figure 7.5. Integrating
along the path of the process on the P-V diagram in Figure 7.5, we get
_
V
f
Vo
PdV
which, according to (7.7), gives W
out
. That is, the area under the curve
Boundary Work 119
representing the path of an expansion process on a P-V diagram gives
W
out
, which is the boundary work done by the system on its surroundings.

P
V

(o)
(f)
V
o
V
f
Figure 7.5 When the process takes place in the direction of increasing
volume (that is, expansion), the area of the shaded region gives W
out
.
-
W
out
. . . . .
. . . . . .
. . . . . .
. . . . .
. . . .
. . .
. . . .
. . . . .
. . . . . .
. . . . .
. . . . . .
. . . . .
.
.
gas expands
from V
o
to V
f
It is important to note that boundary work given by the area of the
shaded region in Figure 7.4 or in Figure 7.5 will change if the path of the
process, described by the curve on the P-V diagram, changes. This means
that even if the initial and nal states of a process are xed, the bound-
ary work would be dierent for the dierent paths followed by a process.
Therefore, we say that boundary work is path dependent.
7.7 Other Forms of Work
Boundary work is just one mode of work transfer between the system
and its surroundings. There are also other modes of work, such as shaft
120 Chapter 7
work, surface work, electrical work, magnetic work, electrical polarization
work, etc. Shaft work is a form of work associated with a rotating shaft
which is a prime component in stirrers, pumps, compressors, turbines, diesel
and petrol engines. Shaft work per unit time is given by 2 n, where n
is the number of revolutions made by the shaft per unit time and is the
constant value of the torque applied to the shaft. When takes the unit
N m and n takes the unit revolutions per second, shaft work takes the unit
J/s, which is W.
In this book we deal only with simple compressible systems (dened in
Section 2.7). Since such systems do not experience electrical, magnetic and
surface tension eects, we will not get into details of how the work needed
to change surface area, electrical work, magnetic work or electrical polar-
ization work are evaluated. For details of the evaluation of these modes of
work, please refer to the following textbooks on thermodynamics: (i) Hol-
man, J.P. 1988 Thermodynamics, 4
th
Edition, McGraw-Hill International
Editions. (ii) Wark, K. 1989 Thermodynamics, 5
th
Edition, McGraw-Hill
International Editions.
7.8 Worked Examples
Example 7.1
The following statements are incorrect. Find
the error in each statement.
(a) For a gas contained in a closed system changing from one state to
another state,
_
f
o
PdV is the same along any path as long as the
process is quasistatic.
(b) Boundary work is always given by
_
f
o
PdV .
(c) All forms of work transfer are zero for a constant volume process.
(d) A closed, adiabatic system of gas expanding from an initial pressure
P
o
to a nal pressure P
f
against a constant force applied by its
surroundings is a quasistatic process.
Boundary Work 121
(a) The boundary work done in a quasistatic process is evaluated using
_
f
o
PdV .
But the value of
_
f
o
PdV , and thus the amount of boundary work, change de-
pending on the path of the chosen process. Therefore, even if the process is
quasistatic, the value of
_
f
o
PdV depends on the path of the quasistatic process
considered.
(b) Boundary work of a quasistatic process is given by
_
f
o
PdV . Boundary work
associated with a non-quasistatic process is nearly impossible to calculate, since
such a process could have a nonuniform distribution of the properties within the
system. Therefore, boundary work is not always given by
_
f
o
PdV .
(c) The boundary work associated with a constant volume quasistatic process is
zero, since dV is identically zero in the work integral
_
f
o
PdV used to determine
the boundary work of a quasistatic process. Even if the given constant volume
process is not a quasistatic process, there is neither boundary work nor frictional
work involved with the process, since the boundary does not move in a constant
volume process. However, a constant volume process may receive stirring work,
and therefore it is incorrect to assume that all forms of work transfer are zero
for a constant volume process.
(d) For the given adiabatic expansion process to qualify as a quasistatic process,
it should have been carried out under conditions of innitesimal dierence in the
force causing the expansion and the force resisting the expansion. In the given
process, the force resisting the expansion remains constant, whereas the force
causing the expansion changes from P
o
A to P
f
A, where A is the cross-sectional
area on which the pressure acts. Therefore, the expansion is carried out under
nite dierence between the force causing the expansion and the force resisting
the expansion. Therefore, the given process is not quasistatic.
Example 7.2
Determine the boundary work (a) for a qua-
sistatic constant-pressure process, and (b) for a quasistatic constant-volume
process. Pressures and volumes at the initial and the nal states of the pro-
cess are given by (P
o
, V
o
) and (P
f
, V
f
), respectively.
122 Chapter 7
(a) A quasistatic constant-pressure process: We employ (7.7) to eval-
uate the boundary work since the given process is quasistatic. Since it is also a
constant pressure process, P
o
= P
f
= P, say. Therefore, we get from (7.7)
W
out
= W
in
=
_
V
f
Vo
P dV = P
_
V
f
Vo
dV = P (V
f
V
o
) (7.9)
for a quasistatic constant-pressure process.
In case we deal with ideal gases, then the ideal gas equation of state gives
P
o
V
o
= nRT
o
and P
f
V
f
= nRT
f
, where n is the amount of gas in the closed
system, R is the universal gas constant, and T
o
and T
f
are the temperatures at
the initial and the nal states, respectively. Therefore, (7.9) yields
W
out
= W
in
= nR (T
f
T
o
) (7.10)
for a quasistatic constant-pressure process of an ideal gas.
(b) A quasistatic constant-volume process: Since the given process is
quasistatic, (7.7) is employed to evaluate the boundary work. Since it is also a
constant volume process, dV = 0 always. Therefore, (7.7) gives
W
out
= W
in
=
_
V
f
Vo
P dV = 0 (7.11)
That is to say the boundary work for a quasistatic constant-volume process is
zero, since dV of a constant volume process is identically zero.
Example 7.3
The piston-cylinder device of Figure 7.1 con-
tains hydrogen, say, which expands from an initial state given by (500 kPa,
0.10 m
3
) to a nal state given by (230 kPa, 0.18 m
3
) in two steps. In the
rst step, the gas is expanded to the volume of 0.18 m
3
while maintaining
the pressure constant at 500 kPa. In the second step, the gas pressure is
decreased to 230 kPa while maintaining the volume constant at 0.18 m
3
.
Determine the work done by hydrogen gas.
Boundary Work 123
Analytical method: Let us assume that the given process takes place qua-
sistatically. Boundary work done by the gas along the constant-pressure qua-
sistatic process is given by (7.9) as
W
out
P
= P (V
f
V
o
)
Substituting, P = 500 kPa, V
o
= 0.10 m
3
and V
f
= 0.18 m
3
, we get
W
out
P
= 500 (0.18 0.10) kPam
3
= 40.0 kJ
Boundary work done by the gas along the constant-volume quasistatic pro-
cess is given by (7.11) as
W
out
V
= 0
The total boundary work done by the gas in the two-step process is, therefore,
W
out
= W
out
P
+W
out
V
= 40.0 kJ + 0 = 40.0 kJ
Graphical method: Figure 7.6 shows the path of the process, represented by
the curve IEF on a P-V diagram. The initial state and the nal state are marked
by points I and F, respectively. The intermediate state where the process switches
from a constant-pressure process to a constant-volume process is marked by point
E. The area under the curve IEF is
500 KPa(0.18-0.10) m
3
= 40 kJ,
which is the work done by hydrogen (see Figure 7.5). Observe that the work
evaluated by the graphical method is the same as the work evaluated by the
analytical method, which is how it should be.
Figure 7.6 Path of the process of Example 7.3, shown on a P-V diagram.
,
,
200
300
400
500
P (in kPa)
V (in m
3
) 0.10 0.18
I
F
E
,
124 Chapter 7
Example 7.4
Hydrogen in the piston-cylinder device of Ex-
ample 7.3, let us say, expands by pushing the piston in a way that the
pressure of the gas decreases continuously while the volume of the gas in-
creases continuously. The data collected during the expansion process are
tabulated below. Determine the boundary work done by hydrogen.
Pressure (in kPa) 500 393 320.5 268.6 230
Volume (in m
3
) 0.10 0.12 0.14 0.16 0.18
The boundary work done by hydrogen could be evaluated using the work
integral of (7.7) if we know how P changes with V along the path of the
process. Let us plot the pressure-volume data collected during the expansion
process on a P-V diagram. The data are represented by dots marked I, E
1
, E
2
,
E
3
and F in Figure 7.7.
Figure 7.7 Path of the process of Example 7.4, shown on a P-V diagram.
,
,
,
,
,
200
300
400
500
P (in kPa)
V (in m
3
) 0.10
I
E
1
E
2
E
3
F
0.18
The area under the curve IE
1
E
2
E
3
F represents the boundary work done by
hydrogen (see Figure 7.5). It is therefore possible to determine this area by
plotting the curve IE
1
E
2
E
3
F on a graph sheet and then by counting the squares
under the curve on the graph sheet.
Alternatively, the equation of the curve that best ts the data points in
Figure 7.7 would give us the equation describing the path of the process. Let us
rst try the equation
P V
k
= C (7.12)
Boundary Work 125
where k and C are constants to be determined from the experimental data using
the procedure outlined below. Taking the natural logarithm of (7.12) yields
ln P = k ln V + ln C
which shows that a plot of ln P versus ln V gives a straight line having a slope
-k and an intercept ln C.
Now let us go back to the experimental data on P and V , nd the natural
logarithms of P and V , and plot the data on a ln P versus -ln V diagram, as
shown in Figure 7.8. We see in Figure 7.8 that the data points are well tted
by a straight line. Therefore, we conclude that (7.12) accurately describes the
path of the process.
Figure 7.8 lnP versus -ln V plot of the data in Example 7.4.
,
,
,
,
5.40
6.20
ln P
-ln V 1.70
I
E
1
E
2
F
2.30
,
E
3
Substituting P from (7.12) in (7.7), we get
W
out
=
_
V
f
Vo
_
C
V
k
_
dV
which can be integrated, for cases in which k = 1, to yield
W
out
= C
_
V
k+1
k + 1
_
V
f
Vo
= C
_
V
k+1
f
V
k+1
o
k + 1
_
(7.13)
From the slope and the intercept of the straight line in Figure 7.8, we can
nd that k = 1.32 and C = 23.9 when P is in kPa and V in m
3
. Substituting
these values and the data V
o
= 0.10 m
3
and V
f
= 0.18 m
3
in (7.13), we get
W
out
= 23.9
_
0.18
0.32
0.10
0.32
0.32
_
= 26.8 kJ
126 Chapter 7
Teacher: Note that both the processes of Example 7.3 and Example 7.4
have the same initial and nal states. The path of the processes, of course,
are dierent from each other as shown in Figure 7.6 and Figure 7.7. The
work done by hydrogen also diers exhibiting the path-dependence of the
work integral given by (7.7).
Student: Yes, I noted that. Teacher, I have a question. Suppose that the
data points on the ln P versus -ln V plot of the Solution to Example
7.4 could not have been tted by a straight line, How could we solve the
problem then?
Teacher: We should have then tried another form of equation in place of (7.12).
However, it is sometimes impossible to describe the path of the process
by an equation. In such cases, the work transfer is determined from
evaluating the area under the path of the process on a P-V diagram
plotted on a graph sheet.
Example 7.5
The initial volume V
o
of a cyclic process is
the same as the nal volume V
f
. Therefore, your friend argues, the work
integral (7.7) used to evaluate the boundary work of a quasistatic process
reduces to zero owing to the upper and the lower limits of the integral of
(7.7) becoming one and the same. Consequently, your friend concludes
that the boundary work associated with a quasistatic cyclic process of a
closed system is always zero. Explain to your friend, using an appropriate
example, why he is wrong.
For a constant-volume process, boundary work is zero since dV of a constant
volume process is identically zero throughout the entire process. The process
of this example is not a constant volume process having dV = 0 always, but a
cyclic process which has identically the same volumes at the initial and the nal
Boundary Work 127
states of the process. An example of a quasistatic cyclic process is shown on the
P-V diagram of Figure 7.9 by the path A B C D A.
Figure 7.9 An example of a quasistatic cyclic process.
,
,
P
V
A
C
B
D
E F
,
,
Since the constant-pressure quasistatic process A B occurs in the direc-
tion of increasing volume, the area under the path A B in Figure 7.9, enclosed
by the rectangle ABFE, gives (W
out
)
AB
(see Figure 7.5). Therefore,
(W
out
)
AB
= P
A
(V
B
V
A
)
The constant-pressure quasistatic process C D occurs in the direction of
decreasing volume, and therefore the area under the path C D in Figure 7.9,
enclosed by the rectangle CDEF, gives (W
in
)
CD
(see Figure 7.4). Therefore,
(W
in
)
CD
= P
C
(V
C
V
D
)
Since B C and D A are constant-volume quasistatic processes,
(W
out
)
BC
= 0 and (W
out
)
DA
= 0
as in (7.11). Note that the constant-volume quasistatic paths B C and
D A have zero areas under them on the P-V diagram of Figure 7.9.
Putting all the information above together, we calculate the net work transfer
as follows:
(W
out
)
net
= (W
out
)
AB
+ (W
out
)
BC
+ (W
out
)
CD
+ (W
out
)
DA
= P
A
(V
B
V
A
) + 0 P
C
(V
C
V
D
) + 0
From Figure 7.9, we see that V
A
= V
D
and V
B
= V
C
, and therefore we
reduce the above to the following:
(W
out
)
net
= (P
A
P
C
) (V
B
V
A
)
128 Chapter 7
which is in fact the area enclosed by the rectangle ABCD in Figure 7.9. It is
obvious therefore that the work transfer in a process with identical initial and
nal volumes, as in a cyclic process, need not always be zero.
Teacher: The above example shows that the work exchange between the sys-
tem and its surroundings in a quasistatic cyclic process is given by the area
enclosed by the path of the process on the P-V diagram. Please note that
the cyclic process shown in Figure 7.9 is in the clockwise direction, and
that the area enclosed by the path of the process represents the work done
by the system on its surroundings, i.e. W
out
,
Student: Yes, Teacher. I have noted that.
Teacher: If the cyclic process considered were in the anti-clockwise direction
on the P-V diagram then the area enclosed by the path of the process
would have represented the work done on the system by its surroundings,
i.e. W
in
.
Student: Okay, Teacher. I will work that out myself.
Example 7.6
Determine the boundary work associated with
a quasistatic isothermal process of an ideal gas. Pressures and volumes at
the initial and the nal states of the process concerned are given by (P
o
,
V
o
) and (P
f
, V
f
), respectively.
In an isothermal process, the temperature remains constant. An ideal gas
satises the ideal gas equation, P V = nRT. Therefore, an isothermal process
of an ideal gas satises the following condition:
P V = nRT = C (7.14)
where C is a constant since T is a constant. In this process P changes hyper-
bolically with V . Since the process is taken as a quasistatic process, we evaluate
Boundary Work 129
the work done on the system using (7.7) as follows:
W
in
=
_
V
f
Vo
P dV =
_
V
f
Vo
_
C
V
_
dV = C ln
V
f
V
o
Applying PV = constant for the initial and nal states, that is P
o
V
o
= P
f
V
f
,
we get
W
in
= C ln
_
V
f
V
o
_
= C ln
_
P
o
P
f
_
(7.15)
for a quasistatic isothermal process of an ideal gas. The value of C in
(7.15) is determined using (7.14) as follows:
C = P
o
V
o
= P
f
V
f
= nRT (7.16)
Example 7.7
One kmol of an ideal gas originally at 300 K
and 1 bar is heated at constant pressure to a temperature of 400 K and then
compressed isothermally to a volume equal to its initial volume. Show this
two-step process on a P-V diagram, and calculate the net work exchange
of the system with its surroundings. State your assumptions clearly.
During the rst step of the process, the ideal gas at 300 K and 1 bar is
heated at constant pressure to a temperature of 400 K. Since the temperature
increases at constant pressure, the volume of the gas increases as well. If we
take this constant pressure process to be quasistatic, then it can be shown on
the P-V diagram of Figure 7.10 by the path A B. Point A represents the
initial state having P
A
= 1 bar and T
A
= 300 K, and point B represents the
intermediate state having P
B
= 1 bar and T
B
= 400 K.
During the second step, the gas is compressed isothermally to a volume equal
to its initial volume. That is, the temperature remains constant at 400 K and
the volume decreases to its initial value, V
A
. Since the volume decreases at
constant temperature, the pressure of the gas increases. Taking this isothermal
process to be quasistatic, its path, described by the hyperbola PV = nRT =
130 Chapter 7
constant, can be shown by the curve B C on the P-V diagram of Figure
7.10. Point C represents the nal state of the process having T
C
= 400 K and
V
C
= V
A
.
P
V
C
B
D E
Figure 7.10 The two-step process of Example 7.7 shown on a P-V diagram,
where the shaded area shows the net work done on the system.
A
Since path A B is in the direction of increasing volume, the area ABED
under path A B gives W
out
(see Figure 7.5). Therefore, we get
(W
out
)
AB
= P
A
(V
B
V
A
)
where we know that P
A
= 1 bar, but we do not know the volumes at A and
B. Since the temperatures at A and B are known, the volumes at A and B can
be eliminated from the above equation using the ideal gas equation of state as
follows:
(W
out
)
AB
= P
B
V
B
P
A
V
A
= nR(T
B
T
A
)
in which we have used the fact that P
A
= P
B
. Since n = 1 kmol, T
A
= 300
K and T
B
= 400 K, we get
(W
out
)
AB
= (1 kmol) (8.314 kJ/kmol K) (400 K 300 K)
= 831.4 kJ (7.17)
Since path B C is in the direction of decreasing volume, the area BCDE
under path B C gives W
in
(see Figure 7.4). Since B C is a quasistatic
isothermal process, we could calculate the work exchange using (7.15) as follows:
(W
in
)
BC
= C ln
_
V
C
V
B
_
= C ln
_
P
B
P
C
_
(7.18)
To determine the volume ratio (V
C
/V
B
) or the pressure ratio (P
B
/P
C
) of
(7.18), let us use the fact that the mass of ideal gas contained satises the
Boundary Work 131
ideal gas equation of state at the states represented by points A, B and C. We
therefore get
P
A
V
A
T
A
=
P
B
V
B
T
B
=
P
C
V
C
T
C
which becomes
(1 bar) V
A
300 K
=
(1 bar) V
B
400 K
=
P
C
V
A
400 K
The above yields P
C
= 4/3 bar. Substituting the values of P
C
and P
B
in
(7.18), we get
(W
in
)
BC
= C ln (3/4) (7.19)
where C is calculated using (7.16) as follows:
C = nRT
B
= (1 kmol) (8.314 kJ/kmol K) (400 K) = 3326 kJ
Thus, (7.19) gives
(W
in
)
BC
= 3326 ln (3/4) kJ = 956.8 kJ (7.20)
Combining (7.17) and (7.20), we get the net work done on the system by
the surroundings as follows:
(W
in
)
net
= (W
out
)
AB
+ (W
in
)
BC
= (831.4 + 956.8) kJ = 125.4 kJ
Example 7.8
Obtain an expression for the boundary work
associated with steam undergoing a quasistatic isothermal process.
In the case of an ideal gas undergoing a quasistatic isothermal process, the P-
V path of the process can be described by the simple equation PV = constant.
And, therefore the boundary work associated can be given by the simple and
straight forward expression (7.15), as proved in the Solution to Example
7.6.
132 Chapter 7
In the case of steam undergoing a quasistatic isothermal process, however,
the P-V path of the process cannot be described by a simple equation. And,
therefore the boundary work associated cannot be given by a simple and straight
forward expression. However, if the path of the process could be sketched on a
P-V diagram then it would be possible to graphically determine the area under
the path between the initial and the nal states of the process, and hence the
work required.
Example 7.9
Determine the boundary work associated with
an adiabatic process executed by a closed system.
There is no heat transfer in an adiabatic process, and thus Q
in
= 0 . The
rst law of thermodynamics applied to closed system therefore gives
(W
in
)
adiabatic
= U (7.21)
which is one instant in which the work transfer W
in
, a path dependent function,
is equated to U, change in a system property.
Whether the given adiabatic process is quasistatic or not, (7.21) can be used
to determine the boundary work associated with a closed system containing ideal
gas or steam or any other substance. The work given by (7.21) is known as adi-
abatic work. It is important to note that the adiabatic work can be evaluated
without knowing the P-V path of the process concerned.
Example 7.10
An ideal gas of 0.1 kmol expands adiabatically
such that its temperature reduces from 400
C to 150
C. Calculate the
boundary work done by the gas assuming to be 1.4.
Boundary Work 133
Since the given process is adiabatic, the work transfer can be calculated
using the expression for adiabatic work given by (7.21). Since we are dealing
with ideal gas, (7.21) becomes
(W
in
)
adiabatic
= n
_
T
f
To
C
v
dT (7.22)
Since C
v
is a constant and since C
v
= R/( 1), (7.22) reduces to the
following:
(W
in
)
adiabatic
= nC
v
(T
f
T
o
) = n (R/ 1) (T
f
T
o
) (7.23)
= 0.1 (8.314/0.4) (150 400) kJ
= 519.6 kJ
The boundary work done by the ideal gas is 519.6 kJ.
Example 7.11
Superheated steam of 0.1 kmol expands adi-
abatically from 5 bar and 400
C to 1 bar and 150
C. Calculate the boundary

work done by the steam.
Since the given process is adiabatic, the work transfer can be calculated
using the expression for adiabatic work given by (7.21). Since we are dealing
with steam, (7.21) should be expanded to
(W
in
)
adiabatic
= m(u
f
u
o
)
where m = 0.118 kg, and u
f
and u
i
are the specic internal energies of steam
at the nal state at 1 bar 150
C and at the initial state at 5 bar and 400
C,
respectively.
From a Superheated Steam Table, we can nd that u
f
= 2583 kJ/kg and
that u
i
= 2963 kJ/kg. Therefore,
(W
in
)
adiabatic
= 1.8 (2583 2963) kJ = 684.0 kJ
The boundary work done by steam is 684.0 kJ.
134 Chapter 7
Example 7.12
Develop a pressure-volume relationship de-
scribing the path of a quasistatic adiabatic process of an ideal gas.
Consider a mass of ideal gas undergoing a quasistatic adiabatic process. Let
us suppose that this mass of gas receives dW
in
amount of boundary work. Since
the process is quasistatic, the boundary work shall be given by (7.5) as
dW
in
= P dV (7.24)
The work entering this adiabatic system increases the internal energy of the
system. And, the dierential increase in the specic or molar internal energy of
an ideal gas is given by (5.7) as du = C
v
dT . The dierential increase in the
internal energy of the system is therefore
dU = mC
v
dT (7.25)
Since no heat is transferred between the system and its surroundings in an
adiabatic process, the rst law applied to an adiabatic closed system relates
dW
in
to dU by
dW
in
= dU (7.26)
Combining (7.24), (7.25) and (7.26), we get
P dV = mC
v
dT (7.27)
for an ideal gas undergoing a quasistatic adiabatic process.
Using the ideal gas equation of state, T in (7.27) can be replaced by
(P V/mR), as follows:
P dV = mC
v
d
_
P V
mR
_
=
C
v
R
_
P dV +V dP
_
The above can be rearranged to give
(R +C
v
) P dV = C
v
V dP (7.28)
Since C
p
= C
v
+R for an ideal gas, (7.28) becomes
C
p
P dV = C
v
V dP
Boundary Work 135
which, using = C
p
/C
v
, can be rearranged to give
dP
P
=
dV
V
Integrating the above assuming that remains a constant, we get
ln P = ln V + constant
which can be rearranged to give
P V
= C (7.29)
where C is a constant. Equation (7.29) describes the path of a quasistatic
adiabatic process of an ideal gas on a P-V diagram.
To nd the equation describing the path of the quasistatic adiabatic process
of an ideal gas on a T-V diagram, substitute P = mRT/V in (7.29). We get
mRT
V
V
= C
which yields the required equation as follows:
T V
(1)
=
C
mR
= constant (7.30)
To nd the equation describing the path of the quasistatic adiabatic process
of an ideal gas on a P-T diagram, substitute V = mRT/P in (7.29). That
gives
P
_
mRT
P
_
= C
which yields the required equation as follows:
T
P
(1)/
=
C
1/
(nR)
= constant (7.31)
Example 7.13
Twenty moles of an ideal gas undergoes a
quasistatic process in which the gas expands adiabatically from P
o
= 10
bar and T
o
= 425 K to P
f
= 1 bar and T
f
= 220 K. Determine the
isentropic exponent , and evaluate the work done by the system.
136 Chapter 7
Since the given process is a quasistatic adiabatic process of an ideal gas,
the process shall be described by (7.29). Since the initial and nal states of the
process are identied by P and T, not by P and V , we shall describe the process
by (7.31). Since the initial and the nal states of the process satisfy (7.31), we
get
T
o
P
(1)/
o
=
T
f
P
(1)/
f
Since P
o
= 10 bar, T
o
= 425 K, P
f
= 1 bar and T
f
= 220 K, we get
425
10
(1)/
=
220
1
(1)/
from which the numerical value of could be evaluated as follows:
10
(1)/
= 425/220
1
=
ln (425/220)
ln (10)
1
= 1 0.286
= 1.4
Since the process is an adiabatic process of an ideal gas with constant C
v
,
(7.23) is used to determine the work transfer as follows:
W
in
=
nR
1
(T
f
T
o
) =
0.02 8.314
1.4 1
(220 425) kJ = 85.2 kJ
Thus, the work done by the ideal gas is 85.2 kJ.
Example 7.14
A quasistatic polytropic process process
of a simple compressible gaseous system is described by PV
k
= constant,
where k is known as the polytropic constant. Obtain an expression for
the work done by the system undergoing a quasistatic polytropic process
in terms of the pressures and volumes at the initial and nal states of the
process.
Boundary Work 137
Starting from (7.7), the work done on the system during a quasistatic poly-
tropic process may be given by
W
in
=
_
V
f
Vo
_
C
V
k
_
dV
= C
_
V
k+1
f
V
k+1
o
k + 1
_
for k = 1 (7.32)
The constant C in (7.32) is removed by the following procedure. Since
P V
k
= C is applicable at both the initial and the nal states of the process,
we get
C = P
o
V
k
o
= P
f
V
k
f
(7.33)
Using (7.33) in (7.32), we get
W
in
=
C V
k+1
f
C V
k+1
o
k 1
for k = 1
=
P
f
V
k
f
V
k+1
f
P
o
V
k
o
V
k+1
o
k 1
for k = 1
=
P
f
V
f
P
o
V
o
k 1
for k = 1 (7.34)
which can be used to evaluate the boundary work in a quasistatic polytropic
process.
If the substance contained in the system were an ideal gas then the ideal gas
equation PV = nRT could be used to simplify (7.34) to
W
in
=
nR(T
f
T
o
)
k 1
for k = 1 (7.35)
which can be used to evaluate the boundary work in a quasistatic polytropic
process of an ideal gas.
138 Chapter 7
Example 7.15
A frictionless piston-cylinder device contains
0.1 kg of superheated steam at 6 bar and 450
C. Steam is now expanded

quasistatically along a quasistatic polytropic path until the pressure and
temperature fall to 1 bar and 200
C, respectively. Determine the work

done by the steam.
Since the steam undergoes a quasistatic polytropic process, we can use (7.34)
to determine the work transfer during the process. Since 0.1 kg of steam is
expanded from 6 bar and 450
C to 1 bar and 200
C, (7.34) becomes
W
in
= (0.1 kg)
_
(100 kPa) v
f
(600 kPa) v
o
k 1
_
(7.36)
where v
f
and v
o
are the specic volumes at the nal and initial states, respec-
tively, and k is the polytropic constant.
From a Superheated Steam Table, we can nd that v
o
= 0.5528 m
3
/kg and
v
f
= 2.173 m
3
/kg, and therefore (7.36) becomes
W
in
=
11.44
k 1
kJ (7.37)
where k is an unknown.
There is only one way to nd k which is to use the fact that the properties
at the initial and the nal states of the process satisfy the equation describing
the path of the process, which is P V
k
= constant. That leads to the following:
P
o
V
k
o
= P
f
V
k
f
P
o
v
k
o
= P
f
v
k
f
6 (0.5528)
k
= 1 (2.173)
k
_
2.173
0.5528
_
k
= 6
k =
ln 6
ln (2.173/0.5528)
= 1.31
Using k = 1.31 in (7.37), we get W
in
= 38.1 kJ. The work done by steam
during the quasistatic polytropic expansion is 38.1 kJ.
Boundary Work 139
Example 7.16
Consider a quasistatic expansion process de-
scribed by P = aV + b, where a and b are constants. The pressure is 100
kPa and the volume is 0.2 m
3
at the initial state of the process, and the
pressure is 900 kPa and the volume is 1 m
3
at the nal state. Calculate
the work done by the gas during the process.
Since the given process is quasistatic, the boundary work can be evaluated
using (7.7). Since the process is described by P = aV + b, (7.7) gives
W
out
=
_
V
f
Vo
(aV +b) dV = a
_
V
2
f
V
2
o
2
_
+b (V
f
V
o
)
The problem statement gives V
o
= 0.2 m
3
and V
f
= 1 m
3
, and therefore
the above expression reduces to
W
out
= a
_
(1 0.04) m
6
2
_
+b [1 0.2] m
3
= a (0.48 m
6
) +b (0.8 m
3
) (7.38)
The values of the constants a and b are not given, and there is only one way
to evaluate the constants a and b, which is to use the fact that the initial state
given by (100 kPa, 0.2 m
3
) and the nal state given by (900 kPa, 1 m
3
) should
satisfy the process described by P = aV + b. Therefore, we get the following
two equations:
100 kPa = a (0.2 m
3
) +b and 900 kPa = a (1 m
3
) +b
solving which we nd a = 1000 kPa/m
3
and b = 100 kPa. Substituting the
values of a and b in (7.38), we get
W
out
= 1000 kPa/m
3
_
0.48 m
6
_
+ (100 kPa) (0.8) m
3
= 400 kJ
The work done by the gas during the process is 400 kJ.
Student: Teacher, the expansion process of Example 7.16 is described by
P = aV + b, which means pressure increases as the volume increases. I
would expect the pressure to decrease with increasing volume......
140 Chapter 7
Teacher: It is not surprising that you expect the pressure to decrease with
increasing volume. Because thats what happens in most cases. However,
there are situations in which pressure increases with increasing volume.
One such case is discussed in Example 7.17 where the expansion of a
gas is restrained by the force exerted by a spring.
Example 7.17
A frictionless piston-cylinder device initially
contains air at 150 kPa and 0.2 m
3
. At this state, a linear spring (that is, a
spring for which the force F is proportional to displacement x) is touching
the piston but exerts no force on it. The air is now heated slowly to a
nal state of 0.5 m
3
and 600 kPa. Plot the process on a P-V diagram.
Hence, or otherwise, determine the work done by the air stating clearly all
the assumptions made.
Of the total work done by air, nd the work done against the variable
force exerted by the spring, and the work done against the constant force
due to the weight of the piston and the atmospheric pressure. Neglect the
weight of the spring in comparison to the weight of the piston.
The initial, intermediate, and the nal states of the process are shown in
Figure 7.11. At the initial state, the spring just touches the piston and exerts no
force on the piston. As the air in the piston-cylinder device is heated slowly, it
expands slowly pushing the piston against the spring to compress it. This way, the
expansion of air is almost fully resisted by the spring provided that the frictional
eects are negligible, and can therefore be approximated to a quasistatic process.
The work done by air can thus be evaluated using the work integral given by
(7.7), provided we know how the pressure of air (P) changes with volume of air
(V ) in the given process.
Since the expansion of air is almost fully resisted by the spring, the forces
acting on the piston are almost in balance according to
P A P
o
A + M g + k x (7.39)
where A is the cross-sectional area of the piston on which the pressure P of air
Boundary Work 141
acts, P
o
is the atmospheric pressure, M g is the weight of the piston, k x is the
force exerted by the spring when the spring is compressed by a length x, and k
is the spring constant. The above force balance is written at the intermediate
state shown in Figure 7.11. Since the compressed length of the spring is x and
the volume of air is V at the intermediate state, as shown in Figure 7.11, we get
volume increase = V V
o
= Ax (7.40)
air
initial state
V
o
= 0.2 m
3
P
o
= 150 kPa
nal state
V
f
= 0.5 m
3
P
f
= 600 kPa
air
intermediate state
V m
3
P kPa
`
x
P
o
P
o
P
o
Figure 7.11 The initial, intermediate and the nal states of the process
given in Example 7.17.
, , , , , ,
, , , , , ,
, , , ,
air
,
, , ,
,
, ,
, , , ,
, , , , , , , , , ,
, , , ,
, , , ,
, , , ,
, , ,
, , , ,
, ,
, , ,
, , , ,
, ,
P = P
o
+
M g
A
+
k
A
_
V V
o
A
_
(7.41)
Equation (7.41) can be readily rearranged to give
P = mV + c (7.42)
which describes a straight line on a P-V diagram since the slope m and intercept
c, given by
m =
k
A
2
and c = P
o
+
M g
A

k
A
2
V
o
are constants. If m and c are known, the straight line of (7.42) describing the
process can be sketched on a P-V diagram. We do not know k, A, P
o
and M,
and therefore are unable to calculate m and c.
142 Chapter 7
We do however know the coordinates of the initial state (o) and the nal
state (f) of the process, and they are shown on the P-V diagram of Figure 7.12.
A straight line drawn through the initial and the nal states, as shown in Figure
7.12, gives the path of the process given by (7.42) on the P-V diagram.
P(kPa)
V (m
3
)
(o)
(f)
0.2 0.5
600
150
Figure 7.12 Process given in Example 7.17 shown on a P-V diagram.
The boundary work done by air is the area under the straight line and is
calculated as follows:
W
out
=
_
150 + 600
2
_
(0.5 0.2) kPa m
3
= 112.5 kJ (7.43)
Here, we used a graphical method to calculate the work done by air. Alterna-
tively, we can directly evaluate the work integral of (7.7) using P of (7.42) once
we know the slope m and intercept c, which of course can readily be obtained
from the P-V diagram of Figure 7.12.
Of the total work done by air, we must now nd out how much is against
the spring and how much is against the constant force exerted by the weight of
the piston and the atmospheric pressure, which is (P
o
A+M g). The work done
by air to push against this constant force can be evaluated as follows:
Work done by air against the constant force
= (constant force) (distance moved)
= (P
o
A+M g)
_
V
f
V
o
A
_
=
_
P
o
+
M g
A
_
(V
f
V
o
)
=
_
P
o
+
M g
A
_
(0.5 0.2) m
3
Boundary Work 143
We now need to know the value of (P
o
A+M g). Let us get back to (7.41)
and substitute the properties at the initial state, which are P = P
o
= 150 kPa
and V = V
o
= 0.2 m
3
. Then, we get
P
o
+
M g
A
= 150 kPa
Thus, the work done by air against the force exerted by the weight of the
piston and the atmospheric pressure = (150 kPa 0.3 m
3
) = 45 kJ.
The work done by air against the variable force exerted by the spring is
therefore the dierence between the total work done by air and the work done
by air against the constant force. Thus, the work done by air to push the spring
is (112.5 - 45) kJ = 67.5 kJ.
Example 7.18
Rework Example 7.17 with a nonlinear
spring for which F x
2
. Measurements taken at an intermediate point of
the expansion process showed that the pressure of air is 500 kPa when its
volume is 0.4 m
3
. Determine the total work done by air.
For a nonlinear spring, we get
P A P
o
A + M g + k x
2
, (7.44)
in the notation used in the Solution to Example 7.17. Using the fact that
the volume increase is (V V
o
) = Ax in (7.44), we get
P = P
o
+
M g
A
+
k
A
_
V V
o
A
_
2
(7.45)
Equation (7.45) can be rearranged to give
P = a V
2
+ b V + c (7.46)
which takes a parabolic shape on a P-V diagram with a, b and c as constants.
Even though we do not know k, A, P
o
and M to nd the constants a, b
and c, we know that the curve represented by (7.46) on the P-V diagram passes
144 Chapter 7
through the initial state (0.2 m
3
, 150 kPa), the intermediate state (0.4 m
3
, 500
kPa), and the nal state (0.5 m
3
, 600 kPa). Forcing (7.46) to satisfy these three
points, we get a = 2500 kPa/m
6
, b = 3250 kPa/m
3
, and c = 400 kPa.
The work done by air is evaluated by substituting (7.46) in the work integral
of (7.7) as follows:
W
out
=
_
V
f
Vo
(a V
2
+ b V + c) dV
= a
_
V
3
f
V
3
o
3
_
+ b
_
V
2
f
V
2
o
2
_
+ c (V
f
V
o
)
Substituting the numerical values of a, b and c along with V
f
= 0.5 m
3
and
V
o
= 0.2 m
3
, we get W
out
= 124 kJ.
Example 7.19
A piston-cylinder device initially contains
steam at 200 kPa, 150
C, and 0.10 m
3
. At this state, a linear spring
for which F x is touching the piston but exerts no force on it. Heat
is now slowly added to the steam, causing the pressure and the volume to
rise to 300 kPa and 0.12 m
3
, respectively. Determine the work done by the
steam and the heat supplied to the steam.
Whether the system contains ideal gas or steam, it could be proven using the
method discussed in the Solution to Example 7.17 that the P-V relationship
of the given process is given by
P = mV + c (7.47)
Since the initial and the nal states of the steam satises (7.47), we get the
following equations:
200 kPa = m(0.10 m
3
) +c and 300 kPa = m(0.12 m
3
) +c
which gives m = 5000 kPa/m
3
and c = 300 kPa. The P-V relationship
of (7.47) therefore becomes
P = 5000V 300 (7.48)
Boundary Work 145
where P is in kPa and V is in m
3
.
The work done by steam is evaluated by substituting (7.48) in the work
integral of (7.7) as follows:
W
out
=
_
0.12 m
3
0.10 m
3
(5000V 300) dV
= 5000
_
0.12
2
0.10
2
2
_
300 (0.12 0.10) = 5 kJ
Heat supplied to the steam, denoted by Q
in
, is found by applying the rst
law of thermodynamics to the steam as follows:
Q
in
= U W
in
= U +W
out
= U + 5 kJ (7.49)
of which U is not yet known.
Since we deal with steam, we could expand U as
U = m(u
f
u
o
) (7.50)
where m is the mass of steam and u
o
and u
f
are the specic internal energies
at the initial and nal states.
The initial state of steam is at 200 kPa and 150
C, and it could be found

from a Superheated Steam Table that v
o
= 0.9602 m
3
/kg and u
o
= 2578 kJ/kg.
Since the initial volume of steam is 0.10 m
3
, we can calculate the mass of steam
as follows:
m =
0.10 m
3
0.9602 m
3
/kg
= 0.1041 kg
The nal state of steam is at 300 kPa. Since the nal volume is 0.12 m
3
,
we can calculate the specic volume of steam at the nal state as follows:
v
f
=
0.12 m
3
0.1041 /kg
= 1.153 m
3
/kg
From a Superheated Steam Table, it could be found that at 300 kPa and
1.153 m
3
/kg, the specic internal energy u
f
= 3093 kJ/kg.
Substituting the numerical values of m, u
o
and u
f
in (7.50), we get
U = (0.1041 kg) (3093 2578) kJ/kg = 53.6 kJ
Substituting the value of U in (7.49), we get Q
in
= 53.6 kJ + 5 kJ =
58.6 kJ. Thus, the heat supplied to the steam is 58.6 kJ and the work done by
the steam is 5 kJ.
146 Chapter 7
Example 7.20
The container shown in Figure 7.13 contains
10 kg of oxygen at a temperature of 350
C. A constant force of 20 kN is
applied on the face of the piston having a cross-sectional area of 0.05 m
2
.
The atmospheric pressure is 101.3 kPa. Heat is added slowly to oxygen
until its temperature rises to 400
C. Determine the work done by oxygen,

and the amount of heat delivered to oxygen. Assume that the piston is
free to move. The average value of C
v
for oxygen can be taken as 0.66
kJ/kg K, and the molar mass be taken as 32 kg/kmol.
`
oxygen
F = 20 kN
P
atm
= 101.3 kPa
piston with A = 0.05 m
2
Figure 7.13 Oxygen contained in the piston-cylinder device.
Let the oxygen in the container be the closed system. We need to determine
the work done by the oxygen, and the amount of heat delivered to it. Owing to
heat addition, the temperature of oxygen increases from 350
C to 400
C. The
temperature increase causes the volume of oxygen to increase pushing the piston
away, and we need to evaluate the boundary work associated with the volume
change. Since heat is added slowly, let us assume that the oxygen pushes the
piston slowly enough for the process to be assumed quasistatic. The boundary
work can then be evaluated using the work integral of (7.7), provided we nd
out how the pressure P of oxygen varies with its volume V .
Since the piston moves freely, the pressure force acting on the inner face
of the piston will almost be balanced by the applied force of 20 kN and the
atmospheric pressure acting on the outer face of the piston. Thus, a force
balance on the piston gives
P =
20 kN
0.05 m
2
+ 101.3 kPa = 501.3 kPa = a constant
This means that the process is a constant pressure process, and the work integral
Boundary Work 147
of (7.7) becomes
W
out
= P (V
f
V
o
)
in which P = 501.3 kPa, but V
f
and V
o
are unknowns. Since oxygen is assumed
to behave as an ideal gas, the above expression for work can be converted to
W
out
= mR (T
f
T
i
)
=
_
10 kg
32 kg/kmol
_
(8.314 kJ/kmol K) (400 350) K = 130 kJ
The amount of heat delivered to oxygen, given by Q
in
, is found by applying
the rst law of thermodynamics to oxygen as follows:
Q
in
= U W
in
= U +W
out
= U + 130 kJ (7.51)
of which U is unknown. Assuming that the oxygen behaves like an ideal gas,
we get
U = m C
v
(T
f
T
o
) = (10 kg) (0.66 kJ/kg K) (400 350) K = 330 kJ
Substituting the value of U in (7.51), we get
Q
in
= 330 kJ + 130 kJ = 460 kJ
Thus, the heat supplied to oxygen in the container is 460 kJ and the work
done by oxygen is 130 kJ.
Example 7.21
The piston-cylinder device shown in Figure 7.14,
contains 0.1 kg of air (molar mass = 29 kg/kmol; C
v
= 0.717 kJ/kg K).
Initially, air is at 100 kPa and 27
C, and
the piston rests on stops. Air is heated
until its volume increases by 20% of the
initial volume. An air pressure of 200 kPa
is required to raise the piston. Stating the
assumptions made, mark the path of the
process on a P-V diagram, and determine
the total work done by air and the total
heat supplied to air.
Figure 7.14
air
piston
-
-
-
-
-
--
-
stops
148 Chapter 7
The initial pressure of air is 100 kPa, and the air pressure required to raise
the piston is 200 kPa. Thus, the piston will rest on the stops maintaining the
volume of air constant until the pressure of air becomes 200 kPa. This part of
the process is therefore a constant volume process, during which the pressure
and temperature of air increase. Assuming the process to be quasistatic, the
path of the process is shown on the P-V diagram of Figure 7.15 by the constant
volume line A B. Point A represents the initial state of the process with P
A
= 100 kPa and T
A
= 27
C = 300 K. Point B represents the state at which the

air pressure becomes 200 kPa at constant volume, and P
B
= 200 kPa and V
B
= V
A
.
The air pressure required to raise the piston is 200 kPa. This means that the
weight of the piston and the atmospheric pressure acting on the piston together
exert a net force of 200 kPa which keeps the piston resting on the stops until the
air pressure reaches 200 kPa. A small increase in the air pressure at this point
would cause the piston to rise. The consequent volume increase would help to
maintain the pressure of the air to remain at 200 kPa, provided the piston rises
quasistatically. The air pressure would then remain at 200 kPa, and the volume
and temperature of air would increase as the air continues to receive heat at
constant pressure, until the volume becomes 1.2 times its initial value. The path
of this process is shown in Figure 7.15 by the constant pressure line B C.
Point C represents the nal state of the process, at which P
C
= P
B
= 200 kPa
and V
C
= 1.2 V
B
.
The path of the combined process is given by A B C.
Figure 7.15 The process of Example 7.21 shown on a P-V diagram.
,
P
V
B
C
A
E D
,
,
Boundary Work 149
The total work done by air on its surroundings is represented by the shaded
area BCDE since the process is in the direction of increasing volume (see Figure
7.5). Therefore, we get
(W
out
)
total
= P
B
(V
C
V
B
) = (200 kPa) (1.2 V
B
V
B
) (7.52)
where V
B
is unknown.
Of the states represented by A, B and C, we know the pressure and tem-
perature only at A. We also know that the mass of air in the piston-cylinder
device is 0.1 kg. Therefore, volume V
A
is found by applying P V = mRT to
state A as follows:
V
A
=
mRT
A
P
A
=
(0.1 kg) (8.314/29 kJ/kg K) (300 K)
100 kPa
= 0.086 m
3
Since V
B
= V
A
, we get V
B
= 0.086 m
3
. Thus, (7.52) gives
(W
out
)
total
= (200 kPa) (0.2 0.086 m
3
) = 3.44 kJ
We have yet to determine the total heat supplied to air, which can be done
by applying the rst law of thermodynamics to the entire process as follows:
(Q
in
)
total
= (U)
total
(W
in
)
total
= mC
v
(T
C
T
A
) + (W
out
)
total
= 0.1 0.717 (T
C
300) kJ + 3.44 kJ (7.53)
where T
C
is unknown.
Temperature T
C
is found by applying the ideal gas equation of state at states
A and C as follows:
P
C
V
C
T
C
=
P
A
V
A
T
A
(200 kPa) (1.2 V
B
)
T
C
=
(100 kPa) V
B
300 K
T
C
= 720 K (7.54)
(Q
in
)
total
= (0.1) (0.717) (720 300) kJ + 3.44 kJ = 33.55 kJ
150 Chapter 7
Example 7.22
A rigid box made of thermally non-conducting
material is divided into two compartments of volume 0.5 m
3
each by a thin,
strong, thermally non-conducting diaphragm. Initially, one compartment
contains nitrogen at 5 bar and 300 K and the other is a vacuum. When the
diaphragm is raptured, the nitrogen will rush to ll the entire box. Deter-
mine the temperature and the pressure of nitrogen at the nal equilibrium
state, and the boundary work done by nitrogen.
The initial and the nal equilibrium states are shown in Figure 7.16. At the
initial state, nitrogen exerts a pressure force equivalent to 5 bar on one side of
the diaphragm. The other side experiences no force on it since it faces a vac-
uum. Once the diaphragm is raptured, nitrogen expands to ll the entire box.
The expansion of nitrogen is unrestrained since there is no force acting on the
moving part of the boundary of the nitrogen. At the nal equilibrium state, the
nitrogen occupies the entire box.
initial state, nal state,
nitrogen
5 bar
nitrogen
diaphragm
.
.
vacuum >>
T
f
= ?
P
f
= ? 300 K
-
Choose the system as the entire rigid box and all of its content. Since the
rigid box is made up of non-conducting material, no heat enters or leaves the
system. Since the box is rigid, no work enters or leaves the system. Thus, by
the rst law, the internal energy content of the system remains a constant.
Boundary Work 151
The contribution of the box and the diaphragm towards the internal energy
change is negligible, and the vacuum makes no contribution, and therefore the
internal energy of nitrogen remains a constant. If we assume that the nitrogen
behaves as an ideal gas, then the temperature of nitrogen remains a constant.
Therefore, the nal equilibrium temperature of nitrogen is the same as its initial
temperature. That is, T
f
= 300 K.
The nal equilibrium pressure of nitrogen can be found by the application
of the ideal gas equation of state at the initial and nal states of nitrogen as
follows:
P
f
(1 m
3
)
300 K
=
(5 bar) (0.5 m
3
)
300 K
which gives P
f
= 2.5 bar.
To evaluate the boundary work done by nitrogen, let us take the nitrogen
as the system, and apply the rst law of thermodynamics to it. The nitrogen
is enclosed by non-conducting material and vacuum, and therefore no heat has
entered or left the nitrogen during the process. The internal energy of nitrogen
has been shown to remain constant. Therefore, the rst law of thermodynamics
applied to nitrogen gives that no work is done by nitrogen.
Student: Teacher, a part of the boundary of nitrogen in Example 7.22 has
moved all the way to the opposite wall of the box. How could then the
boundary work done by nitrogen be zero?
Teacher: We have just proved that the boundary work done by nitrogen is zero.
Havent we?
Student: Yes, Teacher, we have. But, please, could we evaluate the boundary
work done by nitrogen using (7.7), instead of using the rst law as we
have just done?
Teacher: Well, as stated above, nitrogen has undergone an unrestrained expan-
sion. That is, the expansion did not take place under almost fully-resisted
conditions. Therefore, the expansion of nitrogen is not quasistatic, and
we cannot use (7.7) to evaluate the boundary work done by the nitrogen.
Student: Teacher, the boundary of nitrogen has moved during the expansion
of nitrogen. Therefore, nitrogen should have done some boundary work.
I am very sure of that. How did we get zero? Oh... Teacher, I am going
crazy.
152 Chapter 7
Teacher: Cool down, dear Student. I agree that the boundary of nitrogen
has moved during the expansion of nitrogen. But, the boundary has
moved with absolutely no force resisting its movement since nitrogen has
expanded into a vacuum. It is, therefore, I say that nitrogen does not do
any work when it expands into a vacuum. It is as simple as that.
Student: Yes, I see the point now. It is simple indeed, but very strange.
Teacher: It might appear strange, but very true. Remember, boundary work
is always done against a force. By the way, you know that it is more
dicult to climb a mountain than to walk a at land. It is because we go
against the gravitational force when climbing the mountain. If there were
no gravitational force acting on us, we would have oated to the top of
Mount Everest with ease. Wouldnt we?
Student: Yes, we would.
Example 7.23
The piston-cylinder device in Figure 7.17 con-
tains 0.2 kmol of helium. The weight of the piston and the atmospheric
pressure acting on it exerts a constant force
equivalent to 3 bar pressure on helium. The
stops shown prevent the piston from being
pushed out by helium at 300 K and 8 bar. With
the stops removed, helium expands adiabati-
cally to 3 bar. The molar mass of helium is
taken as 4 kg/kmol and its as 1.667. Deter-
mine the work transfer and the change in the
internal energy of the system.
helium
Figure 7.17
piston
\
\
\
\
stops
First, let us see if the given process can be assumed to be quasistatic. Recall
that we have learned that the force causing the expansion and the force resisting
the expansion should dier only by a very small amount at any given time in a
process that is quasistatic. In the given process, helium gas expands from 8 bar
Boundary Work 153
pressure to 3 bar pressure against a force that is constant at 3 bar. The large
dierence between the force causing the expansion and the force resisting the ex-
pansion makes the process non-quasistatic. Since the process is not quasistatic,
we cannot use (7.7) to evaluate the boundary work.
However, since the given process is adiabatic,
W
in
= U = nC
v
(T
f
T
o
) (7.55)
can be used to evaluate the work transfer for helium, which behaves as an ideal
gas. The amount of helium n is 0.2 kmol, C
v
can be evaluated according to C
v
= R/( 1) = 8.314/(1.667 1) = 12.5 kJ/kmol K. The initial temperature
T
o
is 300 K, and the nal temperature T
f
is to be found.
Ideal gas equation of state applied to the nal state gives
P
f
V
f
= nRT
f
,
where the nal pressure P
f
, the amount of helium n, and the gas constant R
are known. Had we known the nal volume V
f
, we could have found T
f
. Since
we do not know the nal volume, the ideal gas equation of state is of no help
to nd T
f
.
We know the initial pressure P
o
, the initial temperature T
o
and the nal
pressure P
f
. Therefore, it is tempting to use the relationship, derived from
(7.31),
T
f
P
(1)/
f
=
T
o
P
(1)/
o
to determine T
f
. We should NOT do that because the given process is not
quasistatic even though it is an adiabatic process of an ideal gas.
At this point it appears that the work transfer involved in this problem
cannot be found, which is however not true. Let us now try an approach that is
very dierent from those discussed above. Let us neglect the friction and other
dissipative eects involved in the process. Then, we can say that the work done
by the expanding helium is done only to push the piston and the atmospheric
pressure acting on the piston. Since the piston and the atmospheric pressure
acting on the piston exert a constant force equivalent to 3 bar pressure on
helium, we can say that the helium works against a constant force, given by the
3 bar pressure multiplied by the cross-sectional area of the piston.
The work done by the helium can therefore be calculated using
W
out
= (3 bar) (cross-sectional area of the piston)
(the distance moved by the piston)
= (3 bar) (the increase in the volume of helium)
= (3 bar) (V
f
V
o
)
154 Chapter 7
Since we do not know the initial and the nal volumes of the above expres-
sion, replace these volumes by pressures and temperatures using the ideal gas
equation of state as
W
out
= (3 bar) nR
_
T
f
P
f
T
o
P
o
_
(7.56)
of which we once again do not know the value of T
f
.
Even though work transfer cannot be evaluated using either (7.55) or (7.56),
because we do not know T
f
, these two equations can be combined to nd T
f
as follows:
nC
v
(T
f
T
o
) = (3 bar) nR
_
T
f
P
f
T
o
P
o
_
Substituting all known numerical values, we get
n
R
1.667 1
(T
f
300 K) = (3 bar) nR
_
T
f
3 bar

300 K
8 bar
_
which can be solved to give T
f
= 225 K. Using this in (7.55), we get
W
in
= (0.2 kmol)
8.314 kJ/kmol K
1.667 1
(225 300) K = 187 kJ
The work done by the system on its surroundings is therefore 187 kJ. Since
the system is adiabatic, the change in internal energy of the system is 187 kJ.
The internal energy of the system has decreased because the system has done
work on its surroundings under adiabatic conditions.
Example 7.24
A rigid cylinder contains a oating piston.
Initially, it divides the cylinder in half, and on each side of the piston the
cylinder holds 0.01 kmol of the same ideal gas at 200
C and 100 kPa. Using

an electrical heater installed on side A of the cylinder, heat is added slowly
until the pressure in side A reaches 150 kPa. The piston and the cylinder
are perfect thermal insulators with negligible heat capacity. Determine
(a) the nal volume of gas on side B,
(b) the work done by the piston on the gas on side B, and
(c) the amount of heat supplied by the electrical heater.
Boundary Work 155
The specic heats of the gas are constant and have the values C
v
= 12.56
kJ/kmol K and C
p
= 20.88 kJ/kmol K.
The oating piston is assumed to be free to move within the cylinder with-
out friction. Therefore, the forces acting on either side of the piston equal each
other when the piston is in equilibrium. Thus, at the initial and nal states of
the system, the pressure on side A equals the pressure on side B, as shown in
Figure 7.18, which shows all the data for the problem. Heat added to side A
causes the gas on side A to expand pushing the piston outwards to compress the
gas on side B. Since, heat is added slowly to side A, the piston moves slowly.
In addition, the oating piston is assumed to have friction-free movement. It
is therefore safe to assume that both the expansion of gas on side A and the
compression of gas on side B are quasistatic processes. Since the piston and the
cylinder are perfect heat insulators, the gas on side B shall undergo an adiabatic
process.
A
100 kPa
473 K
0.01 kmol
B
100 kPa
473 K
0.01 kmol
V
o
V
o
A
150 kPa
T
A
K
B
150 kPa
T
B
K
V
A
V
B
_ _ _ _
Figure 7.18 Initial and nal states of Example 7.24.
(a) Determine the nal volume of the gas on side B.
To determine V
B
, the volume of the gas on side B at the nal state, we
could use the fact that the gas on side B is an ideal gas, and that it undergoes
a quasistatic adiabatic process. We then know that the pressure of the gas on
side B changes with its volume according to (7.29). Therefore, we get
(100 kPa) V
o
= (150 kPa) V
B
156 Chapter 7
Using = C
p
/C
v
= 20.88/12.56 = 1.66, the above expression can be
simplied to
V
B
V
o
=
_
100
150
_
1/1.66
= 0.78 (7.57)
We can evaluate the initial volume V
o
with the help of the ideal gas equation
of state as follows:
V
o
=
(0.01 kmol) (8.314 kJ/kmol K) (300 K)
(100 kPa)
= 0.249 m
3
(7.58)
V
B
= (0.78) (0.249 m
3
) = 0.194 m
3
(7.59)
which is the volume of the gas on side B at the nal state.
(b) Determine the work done by the piston on the gas on side B.
To determine the work done by the piston on the gas on side B, that is
(W
in
)
B
, let us apply the rst law of thermodynamics to the gas on side B as
(Q
in
)
B
+ (W
in
)
B
= (U)
B
Since the gas on side B is an ideal gas that undergoes an adiabatic process,
the above equation simplies to
(W
in
)
B
= n
B
C
vB
(T
B
473 K) = 0.01 12.56 (T
B
473) kJ (7.60)
To determine T
B
, let us apply the ideal gas equation of state to the gas on
side B as follows:
(100 kPa)(V
o
)
473 K
=
(150 kPa)(V
B
)
T
B
which gives
T
B
=
_
150
100
__
V
B
V
o
_
(473 K)
Substituting V
B
/V
o
from (7.57) in the above, we get
T
B
=
_
150
100
_
(0.78) (473 K) = 553 K (7.61)
B
in (7.60), we get
(W
in
)
B
= 0.01 12.56 (553 473) kJ = 10 kJ (7.62)
which is the work done by the piston on the gas on side B.
Boundary Work 157
(c) Determine the amount of heat supplied by the electrical heater.
Let us say that the amount of heat supplied to the gas on side A by the
electrical heater is (Q
in
)
A
. To determine this, we may apply the rst law of
thermodynamics to the gas on side A as
(Q
in
)
A
+ (W
in
)
A
= (U)
A
which can be rewritten as
(Q
in
)
A
= (U)
A
+ (W
out
)
A
(7.63)
Since the piston is assumed to move without friction, the work done by the
gas on side A in pushing the piston outwards is exactly the same as the work
done by the piston on the gas on side B to compress it. Therefore,
(W
out
)
A
= (W
in
)
B
which converts (7.63) to
(Q
in
)
A
= (U)
A
+ (W
in
)
B
(7.64)
The gas on side A is 0.01 kmol of an ideal gas with C
v
= 12.56 kJ/kmol K
and (W
in
)
B
is known from (7.62). When this information is used in (7.64), we
get
(Q
in
)
A
= [0.01 12.56 (T
A
473) + 10] kJ (7.65)
To nd T
A
, let us apply the ideal gas equation of state to the gas in side A
as
T
A
=
_
150
100
__
V
A
V
o
_
(473 K) (7.66)
We can determine V
A
in the following manner. Since the total volume of
gases at the nal state is the same as the total volume of gases at the initial
state, we get
V
A
+V
B
= 2 V
o
Using V
B
/V
o
from (7.57), the above equation can be rearranged to give
V
A
/V
o
= 2 V
B
/V
o
= 2 0.78 = 1.22
Substituting the above in (7.66) gives T
A
= 866 K, and using this value of
T
A
in (7.65), we get
(Q
in
)
A
= 0.01 12.56 (866 473) + 10 = 59 kJ
which is the heat supplied by the electrical heater.
158 Chapter 7
In summary, we conclude that the 59 kJ of heat supplied slowly by the elec-
trical heater to the gas in side A is used to raise the temperature of the gas in
side A to 866 K and for the gas in side A to push the piston outwards by doing
10 kJ of work on the piston. The piston moves without friction to use the 10
kJ of work to adiabatically compress the gas in side B. The work done on the
gas on side B raises the temperature of the gas in side B to 553 K.
7.9 Summary
Dierential boundary work is given by
dW
in
= P dV (7.5)
for a quasistatic compression process, and by
dW
out
= P dV (7.6)
for a quasistatic expansion process.
The total boundary work in a quasistatic process is given by
W
out
= W
in
=
_
V
f
Vo
P dV (7.7)
Equations (7.5), (7.6) or (7.7) can be applied to evaluate the boundary
work for any substance; solid, liquid, gas or any mixture of phases.
Boundary work takes the unit J, when P is in Pa and V is in m
3
, and it
takes the unit kJ, when P is in kPa and V is in m
3
.
Boundary work can also be evaluated using the expression,
w
in
=
_
V
f
Vo
P dv (7.8)
in which v is the specic (or molar) volume, and therefore w
in
takes the
unit kJ/kg (or kJ/kmol), provided P is in kPa, and v is in m
3
/kg (or
m
3
/kmol).
Boundary Work 159
The boundary work done by a system when executing a process depends
on the path followed by the process.
The area under the curve describing the path of a quasistatic process on a
P-V diagram provides the amount of boundary work done by the system
if the process is an expansion, and the boundary work done on the system
if the process is a compression.
The area enclosed on a P-V diagram by the path of a quasistatic cyclic
process gives the work exchange between the system and its surroundings.
This area represents the work done by the system if the process is in a
clockwise direction, and the work done on the system if the process is
anti-clockwise.
Boundary work done by a quasistatic constant-pressure process is given
by
W
out
= W
in
=
_
V
f
Vo
P dV = P (V
f
V
o
) (7.9)
If the system comprises an ideal gas as the working uid, (7.9) becomes
W
out
= W
in
= nR(T
f
T
o
) (7.10)
If the system comprises water/steam as the working uid, (7.9) becomes
W
out
= W
in
= mP (v
f
v
o
)
A constant-volume process does not do any boundary work since the
boundary of a system executing a constant-volume process does not ex-
pand or contract.
A quasistatic isothermal process of an ideal gas is described by
P V = nRT = C (7.14)
where C is a constant. Boundary work done on a system undergoing a
quasistatic isothermal process is given by
W
in
= C ln
_
V
f
V
o
_
= C ln
_
P
o
P
f
_
. (7.15)
The constant C may be determined using
C = P
o
V
o
= P
f
V
f
= nRT (7.16)
160 Chapter 7
Boundary work done on a closed system executing an adiabatic process is
given by
(W
in
)
adiabatic
= U (7.21)
The adiabatic work therefore does not depend on the path of the process,
but on the initial and the nal states of the process only.
If the system comprises an ideal gas, (7.21) becomes
(W
in
)
adiabatic
= n
_
T
f
To
C
v
dT (7.22)
If the system comprises water/steam, (7.21) becomes
(W
in
)
adiabatic
= m(u
f
u
o
)
The path of a quasistatic adiabatic process of an ideal gas with constant
specic heats is described by
P V
= constant on a P-V diagram. (7.29)

T V
(1)
= constant on a T-V diagram. (7.30)
T
P
(1)/
= constant on a P-T diagram. (7.31)
A quasistatic polytropic process is described by P V
k
= constant, where
k is the polytropic constant. Boundary work done on a system undergoing
a polytropic process is given by
W
in
=
P
f
V
f
P
o
V
o
k 1
for k = 1 (7.34)
For a system comprising an ideal gas, (7.34) becomes
W
in
=
nR(T
f
T
o
)
k 1
for k = 1 (7.35)
For a system comprising water/steam, (7.34) becomes
W
in
=
m(P
f
v
f
P
o
v
o
)
k 1
for k = 1
In order to evaluate boundary work using (7.6) to (7.8), the system has
to undergo an almost fully resisted expansion or compression. If the ex-
pansion (or compression) is not almost fully resisted throughout the entire
process then the above equations cannot be used to evaluate boundary
work (see Example 7.23).
It is important to remember that a system expanding into a vacuum does
not do any work at all (see Example 7.22).
Chapter 8
ALL ABOUT HEAT
Hot water and cold water contain the same amount of heat: none
at all.
J.P. Holman (Thermodynamics)
A beginner in thermodynamics may think that a hot object contains
more heat than what a cold object contains. The truth is none of them
contains any heat at all since heat does not reside in an object. The
beginner may also think that the temperature of an object cannot be raised
unless heat is provided to the object, which is a wrong notion. Even one with
a fair knowledge of thermodynamics, often confuses heat with enthalpy.
This chapter is presented to give a clear idea about what heat is, and what
heat is not.
162 Chapter 8
8.1 What is Heat?
We know heat is energy. In the past, even scientists and engineers did
not know that. They thought heat was a uid. Almost 50 years after
the construction of the rst successful steam engine in 1712 by Thomas
Newcomen, Professor Joseph Black founded a theory on heat. This theory
is known as caloric theory, and it said heat was a colourless, weightless uid
known as caloric, and it was conserved. That means caloric, or heat, could
not be created or destroyed, but it could transfer itself from one object to
another. If a metal was heated using re, it was explained, then the uid
caloric was transferred from the re to the metal. James Watt, associated
with Professor Blacks laboratory, modied Thomas Newcomens engine in
1765 and made the rst ecient steam engine. In a steam engine, heat
generated from burning the coal is converted into work required to do a
job, such as rotating the wheels of a train.
In 1824, a French engineer named Sadi Carnot, a believer in the caloric
theory, presented on paper an ideal engine that could provide the maximum
amount of work for a specic amount of heat given to the engine. Carnot
theorized that the work was obtained from an engine because of heat,
which he believed as uid, falling from a high temperature source to a low
temperature source. He showed that the thermal eciency of his ideal
engine depended only on these two temperatures. No real engine can be
more ecient than the Carnot engine, and this result, very interestingly, is
still valid, even though Carnot believed that heat was uid.
James Prescott Joule, in 1840s, performed a series of experiments where
falling wights stirred a liquid and heated it up. He showed that the heat
produced had always the same quantitative relationship to the energy lost
by the falling weights, and concluded that heat was just another form of
energy. Joules ideas and those of Carnot were reconciled, simply and
eectively, by Rudolf Julius Emanuel Clausius in 1850 who wrote down
the First law of Thermodynamics as the total energy of the system is a
constant. William John Macquorn Rankine, a Scottish engineer, dened
thermodynamic eciency of a heat engine in 1853 when applying the theory
of thermodynamics to heat engines, and wrote the rst thermodynamics
textbook in 1859.
All about Heat 163
Our world is full of heat engines where heat is converted into useful
work. Car engines and jet engines, for example, are powered by the heat
generated from burning a fuel. The source of electricity generation in coal,
thermal and nuclear power stations is heat. Heat released from the burning
of coal, petroleum and natural gas accounts for about 85% of the global
energy consumption, which is in the order of hundreds of exajoules.
Without the recognition of the exact nature of heat and its relationship
to work, the world would not have gone so far in its utilization of heat to
provide for the gigantic amount of energy consumed by the human race to-
day. This colossal amount of energy consumption has resulted in pollution
of all kinds. One of the consequences of which is global warming, and the
resulting life-threatening climate change.
8.2 Heat Supply and Common Sense
We know that heat ows from a hot object to a cold object when the
two touch each other. Thus, we have a tendency to believe that a hot
object contains more heat than a cold object does. The truth is heat does
not reside in an object, and there is no such thing as the heat content of
an object. The thermal energy that resides in an object is not heat, but
internal energy. When a hot object comes into contact with a cold object,
the internal energy content of the hot object decreases and the internal
energy content of the cold object increases, until the temperatures of both
become the same. The energy that is transferred between the two objects
during such a process, driven by the temperature gradient between the two
objects, is called heat. This means, we can refer to a form of energy as
heat only when it is being transferred from one object to the other because
of the temperature dierence existing between the two objects.
When heat is supplied to water, the temperature of water increases.
Such familiar everyday experiences have made some of us to conclude that
when heat is provided to a substance, its temperature should necessarily
increase. Is that really true? If so, how could we explain the following
observations?
164 Chapter 8
Heat provided to ice at its melting point turns ice to water at the
temperature of the melting point. That is, the temperature remains
constant but there is change of phase.
When heat is added to water at its boiling temperature, the temper-
ature does not change until all water is turned into steam. That is,
there is phase change at constant temperature.
Now, some may conclude that when a substance is heated either the
temperature of the substance should increase or the phase of the substance
should change. Is that true? No. The following sections are designed to
give us an insight into what else may happen when heat is supplied to a
substance.
8.3 Heat Supplied to
Increase the Temperature
Take air in a cylindrical container with enough force applied to the pis-
ton to keep the air volume constant, as in Figure 8.1. Insulate the walls
of the cylinder and the piston so that heat is not lost to the surroundings.
Supply heat to air using a heating coil.
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
initial state
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
nal state
Figure 8.1 Heat supplied at constant volume.
p
p
Since no work transfer occurs, the heat supplied to air goes to increase
the internal energy of air in accordance with the rst law of thermodynamics
Q
in
= U
All about Heat 165
Assuming ideal gas behaviour, the increase in the specic internal energy
of air may be accounted for by
u =
T
f
To
C
v
dT
Combining the two equations above, we get
Q
in
= m
T
f
To
C
v
dT
which says that the heat supplied to a substance increases its temperature.
It is a very familiar experience for us, and therefore we have no problem
recognizing it, and accepting it.
8.4 Heat Supplied to Do Work
Consider air in the set up shown in Figure 8.2, and let us carry out the
following thought experiment. Allow the piston to move away by a tiny dis-
tance such that the volume occupied by the air in the cylinder is increased
by a tiny amount. Do not supply heat to the air during this step. The tiny
increase in the volume of air would cause a tiny decrease in the air pressure
and hence the temperature of air would drop by a tiny amount. Let us now
hold the volume of the air in the cylinder constant at its new value, and
supply heat to the air such that the temperature of air is brought back to
its original value.
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
initial state
nal state
Figure 8.2 Heat supplied maintaining temperature constant.
By continuing this procedure, it is possible to supply heat to the air
while maintaining its temperature about a constant value. Here we have
166 Chapter 8
a process in which the heat supplied neither increases the temperature nor
changes the phase of a substance. We may ask then what happened to the
heat supplied to air. The answer to the question shall be found as follows.
First law of thermodynamics applied to the air assumed to behave as
an ideal gas, gives
Q
in
= W
in
+ U = W
out
+m
T
f
To
C
v
dT
Since T is maintained a constant, the above becomes Q
in
= W
out
.
That is, all the heat supplied to the ideal gas maintained at a constant
temperature is used by the ideal gas to do work in pushing the piston away.
8.5 Temperature Increase without
Heat Supply
Consider air in the set up shown in Figure 8.3. Insulate the system so
that heat does not cross the system boundary. Push the piston slowly to
compress the air. Since no heat is transferred across the system boundary,
the rst law of thermodynamics applied to air yields
W
in
= U = m
T
f
To
C
v
dT
if ideal gas behaviour is assumed. The above expression clearly shows that
the work done on the air is responsible for increasing the temperature. That
is, the temperature of air increases with no heat supplied to it.
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
p
initial state
nal state
Figure 8.3 No heat is supplied, but force is applied on the piston.
x s r
r
q
q
p
p
p
r
x s r
r
q
q
p
p
p
r
All about Heat 167
Summarizing what we have learnt so far in this chapter, we could say
that changes in the properties, such as the temperature, pressure or volume
of a system, may alter the internal energy of the system. Remember that
temperature, pressure, volume and internal energy are all properties of a
system, and are related to each other. Any change in the internal energy of
a closed system, in turn, is related to heat and/or work transfers between
the system and its surroundings by the rst law of thermodynamics applied
to a closed system, which is
Q
in
+W
in
= U
Let us once again state that heat is dened as the form in which energy
crosses the boundary of a system owing to a temperature dierence between
the system and its surroundings. Any other form of energy transfer across
the boundary of a system is in the form of work, such as the boundary
work.
8.6 Direct Evaluation of Q
in
In the examples that we have so far worked out, the system was either
taken as an adiabatic system, for which Q
in
= 0, or the numerical value of
Q
in
or Q
out
was given. Whenever we were asked to determine how much
heat was transferred to or from the system, we calculated the value of Q
in
by use of the rst law of thermodynamics. In this section, we will explore
how else Q
in
could be evaluated.
Suppose a system is heated by a heat source, such as an electric heater.
The amount of heat added to the system from the heat source can be
evaluated using
Q
in
=
t
f
to
t
where

is the rate at which heat is added to the system from the heat
source, and t
o
and t
f
are the initial and nal times, respectively.
If

is a constant then we have
Q
in
=

(t
f
t
o
)
168 Chapter 8
where, if

is in kW and t
f
and t
o
are in in seconds, Q
in
will be in kJ.
Consider a system heated by heat transferred to it from its surround-
ings. We know that heat ows into or out of a system, only if there is a
temperature dierence between the system and surroundings. Let us say
that the system is at temperature T
sys
, and the surroundings is at temper-
ature T
surr
, which is higher than T
sys
. The heat transfer dQ
in
during a
very short time dt to the system from the surroundings is then given by
dQ
in
= A(T
surr
T
sys
) dt
where is the overall heat transfer coecient in kJ/m
2
K s, and A
is the surface area in m
2
across which heat enters the system from the
surroundings.
If the surroundings are at a lower temperature than the system, then
T
surr
is less than T
sys
. Consequently, dQ
in
of the above expression takes
a negative value. It means that the heat ows from the system to its
surroundings.
To determine the total heat transfer, the above equation is integrated
to obtain
Q
in
=
t
f
to
A(T
surr
T
sys
) dt
To evaluate the above integral we need to know how the temperature
of the system and the temperature of its surroundings vary with time.
Owing to the complex nature of the evaluation of Q
in
using the above
expression, beginners in thermodynamics are seldom expected to evaluate
Q
in
using the above described method.
8.7 Zeroth Law of Thermodynamics
Let us now look at something that is seemingly obvious to us. We know
that heat ows from a hot object to a cold object when they are brought
into contact. If no heat ows between them when they are brought into
contact, then the two objects should be at the same temperature. These
two objects are then in thermal equilibrium with each other.
The zeroth law of thermodynamics, formulated in 1931, states that if
a system A is in thermal equilibrium with a system C and another system
All about Heat 169
B is also in thermal equilibrium with the system C, then the systems A and
B will be in thermal equilibrium with each other.
Let us consider systems A and B as liquids in two dierent containers
which are not in contact, and system C as a thermometer. Let us suppose
that the two systems A and B are in thermal equilibrium with the ther-
mometer C, which means that systems A and B give the same temperature
reading. According to the zeroth law, the two systems A and B are in ther-
mal equilibrium even if they are not in contact since they have the same
temperature reading.
The zeroth law, like the rst law of thermodynamics, is not provable,
even though it seems obvious and trivial.
8.8 Heat and Enthalpy
Even one with a fair knowledge of thermodynamics often confuses heat
with enthalpy. This section would help us to see clearly the relationship
between heat and enthalpy.
Enthalpy dened by (4.1) as H = U + PV , when dierentiated, takes
the form
dH = dU +P dV +V dP (8.1)
Substituting dU from (3.5), which is the dierential form of the rst
law applied to closed simple compressible systems, in (8.1), we get
dH = dQ
in
+dW
in
+P dV +V dP
which could be rearranged to yield
dQ
in
= dH dW
in
P dV V dP (8.2)
On integration of (8.2), we get
Q
in
= H W
in
V
f
Vo
P dV
P
f
Po
V dP (8.3)
which relates the heat provided to a closed simple compressible system to
the enthalpy increase of the system. Remembering (8.3) would keep us
away from confusing heat with enthalpy.
170 Chapter 8
If the closed system undergoes a quasistatic process then dW
in
given
by (7.5) will be used to reduce (8.2) to
dQ
in
= dH V dP (8.4)
If the given process is a constant-pressure process then dP = 0. Thus,
(8.4) becomes
dQ
in
= dH (8.5)
which upon integration yields
Q
in
= H (8.6)
Equation (8.6) is applicable to a a closed system undergoing
a quasistatic constant-pressure process involving no forms of
work transfer other than boundary work.
It is important to note that enthalpy is a property of a system, and
therefore the enthalpy change H is the dierence between the enthalpies
at the initial and the nal states. The amount of heat entering the system
Q
in
depends on the path that the system takes between the initial and the
nal states of the system. And, these two very dierent entities equal each
other only under special circumstances such as the one above.
8.9 Heat and Internal Energy
The circumstances under which heat exchanged with a system could be
related to the internal energy change of a system is explored in this section.
Let us consider a closed system undergoing a constant-volume process. The
rst law, given by (3.4), applied to this process becomes
Q
in
= U (8.7)
provided there is no other forms of work transfer associated with the closed
system.
It is important to note that the internal energy change U is the dif-
ference between the internal energies at the initial and the nal states.
The amount of heat entering the system Q
in
depends on the path that
the system takes between the initial and the nal states of the system.
All about Heat 171
And, these two very dierent entities equal each other only under special
circumstances such as the one above.
8.10 Heat and Specic Heat
We have learned about the specic heat at constant volume (C
v
) in
Section 5.4, and about the specic heat at constant pressure (C
p
) in Section
5.5. Nowhere in these sections, however, we nd any reference to the
quantity heat. Then, why do we call C
v
and C
p
specic heats? It is a
question asked by many beginners in thermodynamics. In this section, we
shall see how to relate the specic heats to the quantity heat.
First, let us deal with specic heat at constant pressure. From the
expression for C
p
given by (5.9), we get
C
p
=
dh
dT
P
=
1
m
dH
dT
P
(8.8)
When using (8.5) applicable to a quasistatic constant-pressure process
involving only boundary work, (8.8) becomes
C
p

1
m
dQ
in
dT
P
(8.9)
Therefore, C
p
is the heat required to raise the temperature of a unit
mass of a substance by one degree in a quasistatic constant-pressure process
involving no forms of work transfer other than boundary work.
From the expression for C
v
given by (5.5), we get
C
v
=
du
dT
v
=
1
m
dU
dT
v
(8.10)
For a constant-volume process, the boundary work is zero, and therefore
the rst law yields dQ
in
= dU provided no other forms of work transfer is
involved. Thus, (8.10) becomes
C
v

1
m
dQ
in
dT
v
(8.11)
172 Chapter 8
Therefore, C
v
is the heat required to raise the temperature of a unit
mass of a substance by one degree in a constant-volume process involving
no forms of work transfer.
Note that some textbooks introduce C
p
and C
v
in terms of (8.9) and
(8.11), respectively. Upon integration of (8.9) and (8.11), we get the
following two very useful expressions for the direct evaluation of heat in the
following processes:
For a quasistatic constant-pressure process involving no forms of work
transfer other than boundary work:
Q
in
= m
T
f
To
C
p
dT (8.12)
For a constant-volume process involving no forms of work transfer:
Q
in
= m
T
f
To
C
v
dT (8.13)
Note that (8.12) and (8.13) are applicable for any simple compressible
substance.
8.11 Worked Examples
Example 8.1
An ideal gas (C
v
= 0.744 kJ/kg K) in a piston-
cylinder arrangement is compressed such that 93 kJ/kg of work is done on
the gas. Assuming adiabatic condition prevails, nd out what happens to
the work provided to the system.
The rst law of thermodynamics applied to the given adiabatic system gives
W
in
= U = mC
v
T. Therefore,
T =
W
in
mC
v
=
93
0.744
= 125 K
All about Heat 173
That is, the work provided to the system has increased the temperature of
the system. Note that the temperature of the system has increased without
receiving any heat.
Example 8.2
The piston-cylinder device in Figure 8.4 con-
tains 0.2 kg of air with a molecular weight of 29, C
v
of 0.718 kJ/kg K and
C
p
of 1.005 kJ/kg K. The initial pressure of air is 1 MPa, and it is just
enough to balance the weight of the piston
and the atmospheric pressure acting on the
piston. The initial temperature is 127
C.
Heat is transferred to air until the piston,
assumed to be frictionless, reaches the stops.
Further heat is transferred to air until the
air reaches 2 MPa and 927
C. Sketch the
path of the process on a P-V diagram, and
determine the amount of heat supplied to
the air.
air
piston
.
`
`
stops
Figure 8.4
.
At the initial state A, P
A
= 1 MPa and T
A
= 400 K. Heat is transferred to
air so that it expands until the piston reaches the stops shown in Figure 8.4. This
intermediate state is denoted by B. During process AB, the expansion of air
is at a constant pressure of 1 MPa, since this pressure just balances the weight
of the piston and the atmospheric pressure acting on the piston. Thus P
B
=
P
A
= 1 MPa. Assume this constant-pressure process to be quasistatic. After
the piston reaches the stops, further heat is added to the air until the process
reaches its nal state, denoted by C, at which P
C
= 2 MPa and T
C
= 1200 K.
During process BC, the volume of air is a constant. The path ABC on
the P-V diagram of Figure 8.5 describes the entire process.
To evaluate the total amount of heat transferred to air during the entire
process, let us determine the heat transfers separately for the processes AB
and BC. Since AB is a quasistatic constant-pressure process, we can use
(8.12) to determine the heat transfer as
(Q
in
)
AB
= mC
p
(T
B
T
A
) (8.14)
174 Chapter 8
Since BC is a constant-volume process of a simple compressible closed
system, we can use (8.13) to determine the heat transfer as
(Q
in
)
BC
= mC
v
(T
C
T
B
) (8.15)
P(MPa)
V (m
3
)
A
C
V
A
V
B
=V
C
2
1
Figure 8.5 The path of the process given in Example 8.2.
B
r r
r
Adding (8.14) and (8.15), we get
(Q
in
)
ABC
= mC
p
(T
B
T
A
) +mC
v
(T
C
T
B
)
Substituting all the numerical values that we already know, we get
(Q
in
)
ABC
= 0.21.005(T
B
400) + 0.20.718(1200T
B
) (8.16)
where the unknown T
B
can be found using
T
B
=
P
B
T
C
P
C
=
1 1200 K
2
= 600 K,
at states B and C along the constant-volume path BC. Using the numerical
value of T
B
in (8.16), we get (Q
in
)
ABC
= 126.4 kJ.
Example 8.3
An ideal gas of 0.01 kmol is taken through a
cyclic process consisting of the following four processes: Process A to B
is an isothermal expansion at 800 K from 8 bar to 6 bar; Process B to C
is an adiabatic expansion to 3 bar; Process C to D is a constant-pressure
cooling; Process D to A is a constant-volume heating. Sketch the cyclic
All about Heat 175
process on a P-V diagram. Assuming that all processes are quasistatic and
taking to be 1.38, determine the temperatures at states C and D, and
calculate the heat and work transfers for the entire cyclic process.
The cyclic process sketched on a P-V diagram is shown in Figure 8.6.
P
V
D
Figure 8.6 The path of the cyclic process of Example 8.3.
A
C
B
r
r
r r
.
. .,
.
isothermal expansion at 800 K
adiabatic expansion
(a) Determination of the temperatures at states C and D:
Table 8.1 shows the data at states A, B, C and D. Since B C is a quasistatic
adiabatic expansion of an ideal gas, (7.31) can be used to nd T
C
as
T
C
=
P
C
P
B
(1)/
T
B
=
3
6
(1.381)/1.38
800 K = 661 K
Since D A is a constant-volume process of an ideal gas, the ideal gas equation
of state can be used to nd T
D
as
T
D
=
P
D
P
A
T
A
=
3
8
800 K = 300 K
A P
A
= 8 bar T
A
= 800 K V
A
= ?
B P
B
= 6 bar T
B
= 800 K V
B
= ?
C P
C
= 3 bar T
C
= ? V
C
= ?
D P
D
= 3 bar T
D
= ? V
D
= V
A
= ?
Table 8.1 Data at states A, B, C and D of the cyclic process.
176 Chapter 8
(b) Calculation of the heat and work transfers:
Process A B is a quasistatic isothermal expansion of an ideal gas at 800
K, and therefore the work transfer is calculated using
(W
in
)
AB
=
V
B
V
A
P dV = nRT
A
ln
P
A
P
B
= 0.01 8.314 800 ln
8
6
kJ = 19.1 kJ
and the heat transfer is calculated using
(Q
in
)
AB
= (W
in
)
AB
= 19.1 kJ,
since there is no internal energy change for an isothermal process of an ideal
gas.
Process B C is a quasistatic adiabatic expansion of an ideal gas, and
therefore the heat transfer becomes (Q
in
)
BC
= 0, and the work transfer is
calculated using
(W
in
)
BC
= (U)
BC
= nC
v
(T
C
T
B
) = n
R
1
(T
C
T
B
)
= 0.01
8.314
1.38 1
(661 800) kJ = 30.4 kJ
Process C D is a quasistatic constant-pressure cooling of an ideal gas,
and therefore the heat transfer is calculated using (8.12) as
(Q
in
)
CD
= nC
p
(T
D
T
C
) = n
R
1
(T
D
T
C
)
= 0.01
1.38 8.314
1.38 1
(300 661) kJ = 109.0 kJ
and the work transfer is calculated using
(W
in
)
CD
= (U)
CD
(Q
in
)
CD
= = nC
v
(T
D
T
C
) nC
p
(T
D
T
C
) = nR(T
D
T
C
)
= 0.01 8.314 (300 661) kJ = 30.0 kJ
Process D A is a constant-volume heating of an ideal gas, and therefore
the work transfer becomes (W
in
)
DA
= 0, and the heat transfer is calculated
using (8.13) as
(Q
in
)
DA
= = nC
v
(T
A
T
D
) = n
R
1
(T
A
T
D
)
= 0.01
8.314
1.38 1
(800 300) kJ = 109.4 kJ
All about Heat 177
The net heat transfer for the entire cyclic process therefore becomes
(Q
in
)
net
= (19.1 + 0 109.0 + 109.4) kJ = 19.5 kJ
and the net work transfer for the entire cyclic process becomes
(W
in
)
net
= (19.1 30.4 + 30.0 + 0) kJ = 19.5 kJ
Comment: Note that we have (Q
in
)
net
+ (W
in
)
net
= 0. It is because in a
cyclic process the net internal energy change is zero owing to the initial and the
nal states being the same.
Example 8.4
An ideal gas enclosed in a piston-cylinder as-
sembly is compressed adiabatically to increase its temperature from T
L
K
to T
H
K. Heat is then supplied to the ideal gas such that it expands isother-
mally at T
H
K. The heat supply is cut o and the ideal gas is allowed to
continue expanding adiabatically until its temperature drops to T
L
K. Fi-
nally, the ideal gas is compressed isothermally until it returns to its initial
state during which heat is rejected to the surroundings. Sketch the cyclic
process on a P-V diagram. Assuming that all processes are quasistatic,
obtain an expression, in terms of T
L
and T
H
, for the thermal eciency of
the cycle,
th
, dened as the net work output of the cycle per unit of heat
added to the cycle.
If T
L
= 300 K and T
H
= 1500 K, determine the amount of heat added
to the ideal gas to produce 100 kJ of net work output. Also, determine the
amount of heat rejected to the surroundings by the ideal gas.
The cyclic process sketched on a P-V diagram is shown in Figure 8.7, where
A B is the quasistatic adiabatic compression, B C is the quasistatic isother-
mal heating at the temperature T
H
, C D is the quasistatic adiabatic expansion,
and D A is the quasistatic isothermal cooling at the temperature T
L
.
178 Chapter 8
P
V
A
B
D
C
s
s
s
s
adiabatic
expansion
isothermal
cooling at T
L
adiabatic
compression
isothermal
heating at T
H
The thermal eciency of the cycle,
th
, is dened as the net work output of
the cycle, W
net
, per unit of heat added to the cycle, Q
in
, and therefore we have
th

W
net
Q
in
(8.17)
In a cyclic process, the net change in the internal energy is zero, and therefore
the rst law applied to the cyclic process gives
W
net
= Q
in
Q
out
(8.18)
where Q
in
is the heat added to the ideal gas during the isothermal heating B
C and Q
out
is the heat removed from the ideal gas during the isothermal cooling
D A. No heat is added or removed during the adiabatic processes A B and
C D.
th
=
Q
in
Q
out
Q
in
= 1
Q
out
Q
in
(8.19)
Since the internal energy remains constant for an isothermal process of an
ideal gas, isothermal heat addition during B C may be expressed using the
rst law as
Q
in
= W
in
= n
V
C
V
B
P dV = nRT
H
ln
V
C
V
B
(8.20)
where T
H
in the temperature of the ideal gas during the isothermal heating
process. Isothermal heat rejection during D A may be expressed using the
All about Heat 179
rst law as
Q
out
= W
in
= n
V
A
V
D
P dV = nRT
L
ln
V
A
V
D
= nRT
L
ln
V
D
V
A
(8.21)
where T
L
in the temperature of the ideal gas during the isothermal cooling
process.
Combining (8.19), (8.20) and (8.21), we have
th
= 1
T
L
ln (V
D
/V
A
)
T
H
ln (V
C
/V
B
)
(8.22)
Since A B is a quasistatic adiabatic expansion of an ideal gas, (7.30) can
be used to get
T
A
T
B
=
V
B
V
A
1
(8.23)
Since C D is a quasistatic adiabatic expansion of an ideal gas, (7.30) can
be used to get
T
C
T
D
=
V
D
V
C
1
(8.24)
Combining (8.23) and (8.24) using T
B
= T
C
= T
H
and T
D
= T
A
= T
L
, we
have
V
B
V
A
=
V
C
V
D
V
D
V
A
=
V
C
V
B
(8.25)
Using (8.25), we can reduce (8.22) to
th
= 1
T
L
T
H
The above expression for thermal eciency is known as the Carnot eciency,
and therefore we write it as follows:
Carnot
1
T
L
T
H
(8.26)
If T
L
= 300 K and T
H
= 1500 K, then (8.26) gives
Carnot
= 1
300
1500
= 0.80 = 80%
180 Chapter 8
Since the thermal eciency of the cycle is 80%, using (8.17), we can calculate
the amount of heat to be added to the cycle to produce 100 kJ of net work output
from the cycle as,
Q
in
=
W
net
Carnot
=
100 kJ
0.8
= 125 kJ
The amount of heat rejected to the surroundings from the cycle can be
calculated using (8.18) as
Q
out
= Q
in
W
net
= 125 kJ 100 kJ = 25 kJ
Comment: Carnot eciency is a very important concept in thermodynamics.
It is because the thermal eciency of no engine, that converts heat to work
operating in a cyclic process between the maximum temperature T
H
K and the
minimum temperature T
L
K, can be higher than the Carnot eciency (the proof
of which is given in Chapter 13), which Sadi Carnot presented in 1824, while
not knowing for sure that heat is energy.
Example 8.5
In a cyclic process, air initially at 1 bar and
300 K is compressed adiabatically to reduce its volume to one eighth of
the initial value. The compressed air is heated at constant volume to 1500
K. The air in then expanded adiabatically and nally cooled at constant
volume to its initial state. Sketch the cyclic process on a P-V diagram.
Assume that all processes are quasistatic and that air behaves as as ideal
gas with =1.4. Determine the thermal eciency of the cycle and the
amount of heat added to the air to produce 100 kJ of net work output.
Determine the numerical values of the pressures at the end of each
process in the cycle.
The cyclic process sketched on a P-V diagram is shown in Figure 8.8, where
A B is the quasistatic adiabatic compression, B C is the constant-volume
heating, C D is the quasistatic adiabatic expansion, and D A is the
constant-volume cooling.
All about Heat 181
P
V
A
B
C
D
Let us rst determine the thermal eciency of the cycle,
th
, the denition
of which is given by (8.17). For the given cyclic process, we can calculate
th
using (8.19), where Q
in
is the amount of heat added during the constant-volume
heating B C, and Q
out
is the amount of heat rejected during the constant-
volume cooling D A. No heat is added or removed during the adiabatic
processes A B and C D.
Constant-volume heat addition can be calculated using (8.13) as
Q
in
= mC
v
(T
C
T
B
) (8.27)
Constant-volume heat rejection can be calculated using (8.13) as
Q
out
= mC
v
(T
A
T
D
) = mC
v
(T
D
T
A
) (8.28)
th
= 1
mC
v
(T
D
T
A
)
mC
v
(T
C
T
B
)
= 1
T
D
T
A
T
C
T
B
(8.29)
where T
A
= 300 K, T
C
= 1500 K and T
B
and T
D
are unknown. To determine
T
B
and T
D
, let us tabulate all the known data at the states A, B, C and D as
in Table 8.2.
A P
A
= 1 bar T
A
= 300 K V
A
= ?
B P
B
= ? T
B
= ? V
B
= V
A
/8
C P
C
= ? T
C
= 1500 K V
C
= V
B
= V
A
/8
D P
D
= ? T
D
= ? V
D
= V
A
= ?
182 Chapter 8
Since A B is a quasistatic adiabatic compression of an ideal gas, (7.30)
can be used to nd T
B
as
T
B
=
V
A
V
B
(1)
T
A
= 8
0.4
300 K = 689 K
be used to nd T
D
as
T
D
=
V
C
V
D
(1)
T
C
=
1
8
0.4
1500 K = 653 K
Substituting the numerical values of the temperatures in (8.29), we get
th
= 1
653 300
1500 689
= 0.565 = 56.5%
Since the thermal eciency of the cycle is 56.5%, using (8.17), we can
calculate the amount of heat to be added to the cycle to produce 100 kJ of net
work output from the cycle as,
Q
in
=
W
net
th
=
100 kJ
0.565
= 177 kJ
The amount of heat rejected to the surroundings from the cycle can be
Q
out
= Q
in
W
net
= 177 kJ 100 kJ = 77 kJ
We know P
A
= 1 bar, and we are to nd P
B
, P
C
and P
D
. Since A B is
a quasistatic adiabatic compression of an ideal gas, (7.29) can be used to nd
P
B
as
P
B
=
V
A
V
B
P
A
= 8
1.4
1 bar = 18.4 bar
Since B C is a constant-volume process of an ideal gas, ideal gas equation
of state can be used to nd P
B
as
P
C
=
T
C
T
B
P
B
=
1500
689
18.4 bar = 40.1 bar
be used to nd P
D
as
P
D
=
V
C
V
D
P
C
=
1
8
1.4
40.1 bar = 2.2 bar
All about Heat 183
Comment: The cycle studied in this problem is known as the ideal Otto cycle.
It is an idealized cycle used to understand the working of an engine in which the
fuel-air mixture contained in a piston-cylinder arrangement is rst compressed
and then ignited using a spark, as in a 4-stroke car engine fueled by petrol. Also,
notice that the eciency of the ideal Otto cycle operating between 1500 K and
300 K is only 56.5%, where as the Carnot eciency for the same temperature
extremes is 80% (see Example 8.4).
Example 8.6
In a cyclic process, air initially at 1 bar and 300
K is compressed adiabatically to reduce its volume to one twentieth of the
initial value. The compressed air is heated at constant pressure to 1500
K. The air in then expanded adiabatically and nally cooled at constant
volume to its initial state. Sketch the cyclic process on a P-V diagram.
Assuming that all processes are quasistatic and that air behaves as as ideal
gas with =1.4, determine the thermal eciency of the cycle,
th
.
Determine the quantity of heat added and the net work output per kg
of air, taking the molar mass of the air as 29 kg/kmol.
The cyclic process sketched on a P-V diagram is shown in Figure 8.9.
P
V
B
A
C
D
184 Chapter 8
A B is the quasistatic adiabatic compression, B C is the constant-
pressure heating, C D is the quasistatic adiabatic expansion, and D A is
the constant-volume cooling.
The thermal eciency of the cycle,
th
, is dened by (8.17). For the given
cyclic process, we can calculate
th
in
is the amount of
heat added during the constant-pressure heating B C, and Q
out
is the amount
of heat rejected during the constant-pressure cooling D A. No heat is added
or removed during the adiabatic processes A B and C D. Constant-pressure
heat addition can be calculated using (8.12) as
Q
in
= mC
p
(T
C
T
B
) (8.30)
Constant-volume heat removal can be calculated using (8.13) as
Q
out
= mC
v
(T
A
T
D
) = mC
v
(T
D
T
A
) (8.31)
th
= 1
1
T
D
T
A
T
C
T
B
(8.32)
where T
A
= 300 K, T
C
= 1500 K and T
B
and T
D
are unknown. To determine
T
B
and T
D
, let us tabulate all the known data at the states A, B, C and D as
in Table 8.3.
A P
A
= 1 bar T
A
= 300 K V
A
= ?
B P
B
= ? T
B
= ? V
B
= V
A
/20
C P
C
= P
B
= ? T
C
= 1500 K V
C
D P
D
= ? T
D
= ? V
D
= V
A
= ?
can be used to nd T
B
as
T
B
=
V
A
V
B
(1)
T
A
= 20
0.4
300 K = 994 K (8.33)
be used to nd T
D
as
T
D
=
V
C
V
D
(1)
T
C
=
V
C
V
A
0.4
1500 K (8.34)
All about Heat 185
where the unknown V
C
/V
A
can be found, using the fact that B C is a
constant-pressure expansion of an ideal gas, as follows:
V
C
T
C
=
V
B
T
B
V
C
V
B
=
T
C
T
B
V
C
V
A
/20
=
T
C
T
B
V
C
V
A
=
T
C
20 T
B
=
1500
20 994
= 0.076 (8.35)
T
D
= 0.076
0.4
(1500 K) = 535 K
Substituting the numerical values of the temperatures and in (8.32), we
get
th
= 1
1
1.4
535 300
1500 994
= 0.668 = 66.8%
Quantity of heat added per kg of air can be calculated using (8.30) as
Q
in
m
= C
p
(T
C
T
B
) =
R
1
(T
C
T
B
)
=
1.4 8.314
29 0.4
(1500 994) kJ/kg = 507.7 kJ/kg
The net work output per kg of air can be calculated as
W
net
m
=
th
Q
in
m
= 0.668 507.7 kJ/kg = 339.2 kJ/kg
Comment: The cycle studied in this problem is known as the ideal Diesel
cycle. It is an idealized cycle used to understand the working of an engine in
which air contained in a piston-cylinder arrangement is compressed to a high
temperature and ignited by injecting the fuel into the hot air, as in a 4-stroke
car engine fueled by diesel. Also, notice that the eciency of the ideal Diesel
cycle operating between 1500 K and 300 K is only 66.8%, where as the Carnot
eciency for the same temperature extremes is 80% (see Example 8.4).
186 Chapter 8
Example 8.7
In a cyclic process, air initially at 1 bar and
300 K is compressed adiabatically to reduce its volume to one tenth of
the initial value. The compressed air is then heated at constant volume
until its pressure increased by 50% of the value at the end of adiabatic
compression. The air in then expanded adiabatically and nally cooled at
constant pressure to its initial state. Sketch the cyclic process on a P-V
diagram. Assuming that all processes are quasistatic and that air behaves
as as ideal gas with =1.4, determine the thermal eciency of the cycle.
The cyclic process sketched on a P-V diagram is shown in Figure 8.10,
where A B is the quasistatic adiabatic compression, B C is the constant-
volume heating, C D is the quasistatic adiabatic expansion, and D A is
the constant-pressure cooling.
P
V
A
B
C
D
We can calculate
th
in
is the amount of heat added
during the constant-volume heating B C, and Q
out
is the amount of heat re-
jected during the constant-pressure cooling D A. No heat is added or removed
during the adiabatic processes A B and C D.
Constant-volume heat addition can be calculated using (8.13) as
Q
in
= mC
v
(T
C
T
B
) (8.36)
All about Heat 187
Constant-pressure heat removal can be calculated using (8.12) as
Q
out
= mC
p
(T
A
T
D
) = mC
p
(T
D
T
A
) (8.37)
th
= 1
T
D
T
A
T
C
T
B
(8.38)
where T
A
= 300 K, and T
B
, T
C
and T
D
are unknown.
To determine T
B
, T
C
and T
D
, let us tabulate all the known data at the
states A, B, C and D as in Table 8.4.
A P
A
= 1 bar T
A
= 300 K V
A
= ?
B P
B
= ? T
B
= ? V
B
= V
A
/10
C P
C
= 1.5 P
B
= ? T
C
= ? V
C
= V
B
= V
A
/10
D P
D
= P
A
= 1 bar T
D
= ? V
D
= ?
can be used to nd T
B
as
T
B
=
V
A
V
B
(1)
T
A
= 10
0.4
300 K = 753.6 K
Since B C is a constant-volume process of an ideal gas, ideal gas equation
can be used to nd T
C
as
T
C
=
P
C
P
B
T
B
= 1.5 753.6 K = 1130.4 K
be used to nd T
D
as
T
D
=
P
D
P
C
(1)/
T
C
=
P
A
1.5 P
B
(1)/
T
C
=
1 bar
1.5 P
B
(1.41)/1.4
1130.4 K
where the unknown P
B
could be found as
P
B
=
V
A
V
B
P
A
= 10
1.4
1 bar = 25.1 bar
188 Chapter 8
since A B is a quasistatic adiabatic process of an ideal gas.
Therefore, we have
T
D
=
1
1.5 25.1
(1.41)/1.4
1130.4 K = 400.9 K
Substituting the numerical values of the temperatures in (8.38), we get
th
= 1 1.4
400.9 300
1130.4 753.6
= 0.625 = 62.5%
8.12 Summary
Heat does not reside in an object. Heat is simply the energy that transfers
from one object to the other, driven by a temperature dierence.
It is not always necessary to provide heat to increase the temperature of a
system. Work done on a system could also result in temperature increase
of the system (see Example 8.1).
Heat provided to a simple compressible closed system is related to the
enthalpy increase of the system by the following:
Q
in
= H
P
f
Po
V dP
V
f
Vo
P dV W
in
(8.3)
For a simple compressible closed system undergoing a constant-pressure
quasistatic process:
Q
in
= H = m
T
f
To
C
p
dT
For a simple compressible closed system undergoing a constant-volume
process:
Q
in
= U = m
T
f
To
C
v
dT
Chapter 9
THE FIRST LAW
APPLIED TO
OPEN SYSTEMS
When the innity of space and universe was rst revealed he was
terried; he felt lost and humbled - he was no longer the central
point of all but an insignicant, innitely small grain of dust.
Nicholas Berdyaev (Man and Machine)
So far, we have learned to apply the rst law of thermodynamics to solve
various kinds of thermodynamic problems associated with closed systems.
In this chapter, we will learn to apply the rst law of thermodynamics to
open systems. An open system, like a closed system, allows heat and work
to enter and/or leave the system. In addition, an open system allows mass
to enter and/or leave the system. Study of open systems is important,
since a large number of engineering applications involve open systems.
190 Chapter 9
9.1 Example of an Open System
Consider a container to which water at room temperature is supplied
from one end, and hot water is drawn from the other end, as shown in
Figure 9.1. A heating coil is placed within the container to heat the water
owing through the container. A stirrer is used to stir the water, and thus
does stirring work on the water.
Choose the open system to be the water present within the container.
We may consider the dashed line of Figure 9.1 as the boundary of the sys-
tem. It is however not correct. The boundary of the system should enclose
only the water in the system, and should exclude the stirrer and the heating
coil. The stirrer and the heating coil are part of the surroundings.
stirrer
heater
.
.
.
.,
water
water inlet
-
water outlet
Figure 9.1 An example of an open system.
An open system is therefore best represented by a block diagram, as
shown in Figure 9.2. The system comprises only the water in the container,
marked by the boundary of the system, given by the dashed line of Figure
9.2, but excludes the heater and the stirrer.
Let the rate at which heat enters the system from the heater be

Q
in
,
and the rate at which work enters the system from the stirrer be

W
in
. Let
the rates at which mass enters and leaves the system be m
i
and m
e
, re-
spectively. Let the mass of the system at time t be m
s
, and the rate of
increase in mass within the system can be given by dm
s
/dt. The energy of
The First Law applied to Open Systems 191
the system at time t is represented by E
s
, and the rate of energy accumu-
lation within the system is represented by dE
s
/dt.
m
i
Q
in
m
e
W
in
_
dm
s
dt
_
_
dE
s
dt
_

Figure 9.2 A block digram representing the open system of Figure 9.1.
Student: Teacher, permit me to ask you a question. You put a dot over Q
in
,
a dot over W
in
, and dots over many other variables. You did not do that
in the eight chapters that we have so far covered. Why are you doing that
now? Why do you put dots over some of the variables?
Teacher It is good that you asked that question. Let me answer your question
considering one variable, say, heat entering the system. When dealing
with closed system, we considered the total amount of heat entering the
system during the entire process, which we represented simply by the
notation Q
in
. In the open system presented above, we are considering
the rate at which heat entering the system, that is, the heat entering
the system per unit time. We choose to designate the rate at which an
entity entering or leaving the system by putting a dot over the entity,
and therefore the rate at which heat entering the system is designated by
the notation

Q
in
. Note that Q
in
takes the unit kJ, and

Q
in
takes the
unit kJ/s, or kJ/hour, or kJ/day, or even kJ/year.
Student: I see now why you put dots over certain variables. Teacher, may I
ask another question?
192 Chapter 9
Teacher: Please, go ahead.
Student: What do you mean by the rate of increase in energy within the sys-
tem?
Teacher: Consider the system shown in Figure 9.1 or in Figure 9.2. Let us
suppose the temperature of the water in the tank increases with time,
which means the internal energy of water increases with time. The rate
at which the energy of the system increases is what we refer to as the rate
of increase in energy within the system, and it is denoted by dE
s
/dt. Note
that the unit of dE
s
/dt may be kJ/s, or kJ/hour, or kJ/day, or kJ/year.
Student: Thanks, Teacher.
9.2 Mass Balance for an Open System
The law of conservation of mass applied to the open system of Figure
9.2 yields the following:
rate of increase in mass within the system
= rate at which mass entering the system
rate at which mass leaving the system,
which is equivalent to
dm
s
dt
= m
i
m
e
(9.1)
where (dm
s
/dt) represents the rate of increase in mass within the system,
and m
i
and m
e
represent the respective rates at which mass entering and
leaving the system.
Note that if m
i
is larger than m
e
then dm
s
/dt will be positive denoting
that mass accumulates within the system. If m
e
is larger than m
i
then
dm
s
/dt will be negative denoting that the mass within the system is de-
creased. If m
i
is the same as m
e
then dm
s
/dt is zero so that the mass of
the system remains a constant with time.
Integrating (9.1) over a time interval t (= t
f
t
o
), we get
_
m
sf
mso
dm
s
=
_
t
f
to
m
i
dt
_
t
f
to
m
e
dt
which can be written as
m
sf
m
so
= m
i
m
e
(9.2)
where m
so
is the mass of the system at the initial time t
o
, m
sf
is the mass
of the system at the nal time t
f
, m
i
is the total mass entering the system
during the time interval t, and m
e
is the total mass leaving the system
during the time interval t.
Equations (9.1) and (9.2) are applicable for open systems with one inlet
and one exit. If an open system has many inlets and exits for the mass to
ow then (9.1) must be expanded to
dm
s
dt
= m
i1
+ m
i2
+ m
i3
+ m
e1
m
e2
m
e3

and (9.2) must be expanded to
m
sf
m
so
= m
i1
+ m
i2
+ m
i3
+ m
e1
m
e2
m
e3

where the subscripts
i1
,
i2
,
i3
,

stand for inlet 1, inlet 2, inlet 3, etc., and
e1
,
e2
,
e3
,

stand for exit 1, exit 2, exit 3, etc.
9.3 Energy Balance for an Open System
The energy of a closed system is changed only by heat and work in-
teractions between the system and its surroundings. In an open system,
however, an additional mechanism is seen to change the total energy of the
system: that is, the ow of matter in and out of the system. When matter
enters a system, it brings in some energy with it. Likewise, when matter
leaves the system, it takes out some energy with it.
194 Chapter 9
Therefore, the law conservation of energy, that is the rst law, applied
to the open system of Figure 9.2 yields the following:
rate of increase in energy within the system
= rate at which heat enters the system
+ rate at which work enters the system
+ rate at which energy enters the system with the mass owing in
rate at which energy leaves the system with the mass owing out,
which is equivalent to
dE
s
dt
=

Q
in
+

W
in
+

E
i

E
e
(9.3)
where (dE
s
/dt) is the rate of increase in energy within the system,

Q
in
is
the rate at which heat enters the system,

W
in
is the rate at which work
enters the system,

E
i
is the rate at which energy is brought in by the mass
entering the system, and

E
e
is the rate at which energy is removed by the
mass leaving the system.
Integrating (9.3) with respect to time over the time interval t yields
E
s
= Q
in
+ W
in
+
_
t
f
to
E
i
dt
_
t
f
to
E
e
dt (9.4)
where E
s
is the change in total energy content of the system during t, and
Q
in
and W
in
are the respective amounts of net heat and net work entering the
system during that period. The third and the fourth terms on the right hand
side of (9.4) represent the energy entering and leaving the system with the mass
entering and leaving the system, respectively. These terms are absent if the
given system were a closed system, so that we get
E
s
= Q
in
+ W
in
which is the familiar form of the rst law of thermodynamics applied to closed
systems, see equation (3.1).
Let us return to the rst Law of thermodynamics applied to an open
system, expressed by (9.3), and take a close look at each of the ve terms
given in (9.3).
The dE
s
/dt term
For simple compressible systems, the total energy of the system, E
s
,
is only the internal energy of the system, U
s
. If the system as a whole
undergoes a change in its elevation then we will add in the gravitational
potential energy term. If the velocity of the whole system changes then
we will add in the translational kinetic energy term. As beginners in ther-
modynamics, we will not consider systems that could possess any forms
of energy other than the internal energy, the gravitational potential energy
and the translational kinetic energy.
The

Q
in
term
If there is a temperature dierence between the system and the sur-
roundings, then heat will be transferred across the system boundary. If the
system is adiabatic, there will be no heat transfer across the boundary, and
Q
in
= 0.
The

W
in
term
Three of the work forms that we often come across with open systems
are discussed below.
Boundary Work (

W
boundary
):
It is a work that results when the system boundary moves. We have
learned about this work in detail in Chapter 7.
Shaft Work (

W
shaft
):
It is a form of work that is realized when a shaft is given a motion by
the uid owing through an open system, or when the motion of a
shaft is used to do work on the uid owing through an open system.
Flow Work (

W
ow
):
Work associated with a uid mass owing into or out of an open
system is called ow work, and is relevant only to an open system.
Let us consider an opening through which mass ows into a system
as shown in Figure 9.3. The dashed box shows the volume dV of a
very small mass dm that is being pushed into the system in time dt.
196 Chapter 9
'
&
P
dl
A
system
Figure 9.3 Schematic for ow work.

`
dm
The uid mass dm is taken to be suciently small for the properties
within the uid mass to be considered uniformly distributed. The
pressure force acting on the uid mass dm to push it into the system
is given by the pressure P multiplied by the cross-sectional area A.
The distance across which the uid mass is pushed is given by dl.
The work done in time dt to push the uid mass dm into the system
across the inlet is given by
dW
flow
= (P A) (dl) = P dV = P v dm
since Adl = dV and since dV = v dm, where v is the specic
volume. Dividing the above expression by dt, we get the following:
dW
flow
dt
=
P v dm
dt
which can be written as
W
flow
= mP v (9.5)
The above equation gives the rate at which ow work is done to
maintain a mass ow rate m at the inlet concerned. Flow work
enters the system when matter ows into the system, and leaves the
system when matter ows out of the system.
Any other form of Work (

W
other
):
There can be other forms of work such as work done to overcome
uid friction, electrical work, and so on. We shall not get into the
details of all these types of work here. For our purposes, let us neglect
any forms of work other than the three discussed above. Thus, we
set

W
other
= 0.
Expanding the work term in (9.3) in accordance with the discussion
above, we get
dE
s
dt
=

Q
in
+ (

W
boundary
)
in
+ (

W
shaft
)
in
+ (

W
flow
)
i
(

W
flow
)
e
+

E
i

E
e
When substituting in the above equation the ow work expressed by
(9.5), we get
dE
s
dt
=

Q
in
+ (

W
boundary
)
in
+ (

W
shaft
)
in
+ ( mP v)
i
( mP v)
e
+

E
i

E
e
(9.6)
The term

E at the inlet and at the exit
The total energy carried by a uid in ow is made up of internal, kinetic
and gravitational potential energies. Therefore, the energy ow rate,

E,
can be expressed as
E = mu + m
c
2
2
+ mg z (9.7)
where m is the mass ow rate of the uid, u the specic internal energy
of the uid, c the speed of the uid, g the gravitational acceleration, and
z the elevation at which the uid ows. The uid that enters/leaves the
system may as well have of electrical, magnetic and other forms of energy,
which we ignore since we deal mostly with simple compressible systems.
198 Chapter 9
Substituting from (9.7) for the energy entering and leaving the system
with the owing uid in (9.6), we get
dE
s
dt
=

Q
in
+ (

W
boundary
)
in
+ (

W
shaft
)
in
+ ( mP v)
i
( mP v)
e
+
_
mu + m
c
2
2
+ mgz
_
i
_
mu + m
c
2
2
+ mgz
_
e
which can be regrouped as
dE
s
dt
=

Q
in
+ (

W
boundary
)
in
+ (

W
shaft
)
in
+
_
mP v + mu + m
c
2
2
+ mgz
_
i
_
mP v + mu + m
c
2
2
+ mgz
_
e
Using h = u + Pv from (4.2) in the above equation, we get
dE
s
dt
=

Q
in
+ (

W
boundary
)
in
+ (

W
shaft
)
in
+
_
mh + m
c
2
2
+ mgz
_
i
_
mh + m
c
2
2
+ mgz
_
e
(9.8)
Equation (9.8) uses enthalpy which includes both the internal energy
and the energy associated with pushing the uid into or out of the open
system. It is therefore the energy of a uid stream owing into or out of an
open system is represented by enthalpy, kinetic energy and potential energy,
and no reference will be made to ow work.
Equation (9.8) is the rst law of thermodynamics applicable to open
systems at any given time, and each term in this equation is a rate term
having the unit of energy per time. Equation (9.8) is, however, inadequate
to completely describe the open systems. We need to use the mass balance
given by (9.1), along with (9.8), to solve problems involving open systems.
Integrating (9.8) over the time interval t (= t
f
t
o
), we get
_
E
sf
Eso
dE
s
=
_
t
f
to
Q
in
dt +
_
t
f
to
(

W
boundary
)
in
dt +
_
t
f
to
(

W
shaft
)
in
dt
+
_
t
f
to
_
mh + m
c
2
2
+ mgz
_
i
dt
_
t
f
to
_
mh + m
c
2
2
+ mgz
_
e
dt
which can be rewritten as
E
sf
E
so
= Q
in
+ (W
boundary
)
in
+ (W
shaft
)
in
+
_
t
f
to
_
mh + m
c
2
2
+ mgz
_
i
dt
_
t
f
to
_
mh + m
c
2
2
+ mgz
_
e
dt (9.9)
where E
so
is the energy of the system at the initial time t
o
, E
sf
is the energy
of the system at the nal time t
f
, and Q
in
, (W
boundary
)
in
and (W
shaft
)
in
are the respective amounts of net heat, net boundary work and net shaft
work entering the system during the time interval t.
Equation (9.9) is the rst law of thermodynamics applicable to open
systems over a chosen time interval, such as t
f
t
o
, and each term in this
equation takes the unit of energy. Equation (9.9) is used together with the
mass balance given by (9.2) to solve problems involving open systems.
Equations (9.8) and (9.9) are applicable for open systems with not
more than one inlet and one exit. If an open system has many inlets
and exits then we must include
_
mh + m
c
2
2
+ mgz
_
-term in (9.8), and
_
t
f
to
_
mh + m
c
2
2
+ mgz
_
dt-term in (9.9), at the respective inlets and exits
with appropriate signs; positive sign for inlet and negative sign for outlet.
200 Chapter 9
9.4 Worked Examples
Example 9.1
Nitrogen at 6 bar and 350 K is supplied to an
insulated, rigid tank of volume 3 m
3
. The tank initially contains nitrogen
at 1 bar and 300 K. Determine the nal temperature of nitrogen in the
tank when its pressure reaches 6 bar. Calculate also the mass of nitrogen
that has entered the tank. Assume that nitrogen behaves as an ideal gas,
and that for nitrogen is a constant at 1.4. Molar mass of nitrogen is 28
kg/kmol.
Figure 9.4 shows the rigid tank which is supplied with nitrogen at a constant
inlet pressure of P
i
= 6 bar and a constant inlet temperature of T
i
= 350 K.
nitrogen at 6 bar & 350 K

Figure 9.4 Charging of a rigid tank with nitrogen at 6 bar and 350 K.
g
valve
The nitrogen in the tank is taken as the open system. Initially, it comprises
nitrogen at P
so
= 1 bar and T
so
= 300 K, and is supplied with nitrogen until
the nal pressure in the tank becomes P
sf
= 6 bar. The nal temperature of
nitrogen, that is T
sf
, is to be found. Note that the subscripts
so
and
sf
denote
the initial and the nal states, respectively, of the nitrogen in the tank.
The tank is insulated and therefore no heat interaction occurs between the
system and the surroundings. There is no shaft work. Since the tank is rigid,
there is no boundary work either. The system has only one inlet which is the
nitrogen supply line and no exit. Therefore, (9.9) applied to the system for the
entire charging period becomes
E
sf
E
so
=
_
t
f
to
_
mh + m
c
2
2
+ mg z
_
i
dt
Since the system is stationary, the kinetic energy of the system does not
change. The potential energy of the system changes with nitrogen entering the
system. Let us however ignore the change in potential energy, and take the
change in total energy E
s
of the system be the change in internal energy U
s
alone. Also, by neglecting the kinetic and potential energies at the inlet, the
above equation is reduced to
U
sf
U
so
=
_
t
f
to
( mh)
i
dt (9.10)
where U
sf
and U
so
are the internal energies of the nitrogen in the tank at time
t
f
and t
o
, respectively.
Pressure and temperature in the nitrogen supply line remain constant through-
out the charging process, and therefore enthalpy at the inlet of the system also
remains constant at h
i
. Using this information, (9.10) can be simplied to
U
sf
U
so
= h
i
_
t
f
to
m
i
dt = h
i
m
i
where m
i
is the total mass of nitrogen entering the tank during the entire
charging process.
Replacing the internal energies of the above equation by specic internal
energies, we get
m
sf
u
sf
m
so
u
so
= h
i
m
i
(9.11)
where m
sf
and m
so
are the mass of the nitrogen in the tank at time t
f
and t
o
,
respectively, and u
sf
and u
so
are the specic internal energies of the nitrogen
in the tank at time t
f
and t
o
, respectively, which are assumed to be uniform
throughout the system.
The mass balance given by (9.2), when applied to the given system, reduces
to
m
sf
m
so
= m
i
(9.12)
Combining (9.11) and (9.12) to eliminate m
i
, we get
m
sf
u
sf
m
so
u
so
= h
i
(m
sf
m
so
) (9.13)
In classical thermodynamics, the absolute values of u and h are not known.
Only the changes in u and h are known. Therefore, (9.13) is transformed to a
202 Chapter 9
convenient form using the following standard procedure. Replacing the h-term
in (9.13) using h = u + Pv, we get
m
sf
u
sf
m
so
u
so
= (u + P v)
i
(m
sf
m
so
)
m
sf
(u
sf
u
i
) m
so
(u
so
u
i
) = (P v)
i
(m
sf
m
so
) (9.14)
Since nitrogen is assumed to behave as an ideal gas, the dierences in spe-
cic internal energies of (9.14) can be expressed in terms of the dierences in
temperatures using u =
_
C
v
dT. Taking C
v
as a constant and using the ideal
gas equation of state Pv = RT, (9.14) can be rewritten as
m
sf
C
v
(T
sf
T
i
) m
so
C
v
(T
so
T
i
) = RT
i
(m
sf
m
so
)
which can be rearranged, using the ideal gas relationship C
p
= C
v
+ R and
the denition of = C
p
/C
v
, to give the following:
m
sf
(C
v
T
sf
C
v
T
i
RT
i
) = m
so
(C
v
T
so
C
v
T
i
RT
i
)
m
sf
(C
v
T
sf
C
p
T
i
) = m
so
(C
v
T
so
C
p
T
i
)
m
sf
(T
sf
(C
p
/C
v
) T
i
) = m
so
(T
so
(C
p
/C
v
) T
i
)
m
sf
(T
sf
T
i
) = m
so
(T
so
T
i
) (9.15)
Since the masses m
sf
and m
so
are unknown, they can be expressed using
the ideal gas equation of state by
m
sf
=
P
sf
V
sf
RT
sf
and m
so
=
P
so
V
so
RT
so
(9.16)
Since the tank is rigid, its volume remains a constant throughout. Therefore
V
sf
= V
so
(9.17)
Using (9.16) and (9.17), we can rewrite (9.15) as follows:
P
sf
T
sf
(T
sf
T
i
) =
P
so
T
so
(T
so
T
i
) (9.18)
Substituting the numerical values known from the problem statement in
(9.18), we determine the value of T
sf
as follows:
6 bar
T
sf
(T
sf
1.4 350 K) =
1 bar
300 K
(300 K 1.4 350 K)
6
_
1 1.4
350 K
T
sf
_
=
_
1 1.4
350
300
_
T
sf
= 443 K
The mass of nitrogen that entered the tank can be found using (9.16) as
follows:
m
sf
m
so
=
P
sf
V
sf
RT
sf
P
so
V
so
RT
so
=
_
600 3
(8.314/28) 443

100 3
(8.314/28) 300
_
kg
= (13.7 3.4) kg = 10.3 kg
Example 9.2
Rework Example 9.1 assuming that the tank
was empty at the initial state.
Since the tank was empty at the initial state, m
so
= 0, and therefore (9.13)
reduces to
u
sf
= h
i
which can be rewritten, using h = u + Pv, as
u
sf
= (u + P v)
i
Assuming ideal gas properties for nitrogen with constant specic heats, the
above equation can be worked out as follows:
u
sf
= u
i
+ RT
i
u
sf
u
i
= RT
i
C
v
(T
sf
T
i
) = RT
i
C
v
T
sf
= (C
v
+ R) T
i
T
sf
=
C
p
C
v
T
i
= T
i
= 1.4 350 K = 490 K
Substituting the numerical value of T
sf
in the ideal gas equation of state at
the nal state, the mass of nitrogen that entered the tank can be found as
m
sf
=
600 3
(8.314/28) 490
kg = 12.4 kg
204 Chapter 9
Example 9.3
Air at 15 bar and 500 K is supplied to a rigid
tank of volume 1 m
3
containing air initially at 1 bar and 300 K, until the
air in the tank reaches 10 bar and 450 K. Determine the mass of air fed to
the tank and the heat interaction between the tank and the surroundings.
Assume that air behaves as an ideal gas, and that R and for air are 287
J/kg K and 1.4, respectively.
Initially the air in the tank is at 1 bar and 300 K, and therefore the initial
mass of air in the tank is
m
so
=
(10
5
Pa) (1 m
3
)
(287 J/kg K (300 K)
= 1.16 kg (9.19)
Finally the air in the tank is at 10 bar and 450 K, and therefore the nal
mass of air in the tank is
m
sf
=
(10
6
Pa) (1 m
3
)
(287 J/kg K (450 K)
= 7.74 kg (9.20)
Therefore, the mass of air added to the tank is 6.58 kg.
To determine the heat interaction between the system and the surroundings,
let us use the following procedure. The problem to be solved here is similar to the
problem of Example 9.1, except for the heat interaction between the system
and the surroundings. Therefore, (9.9) applied to the given system becomes
E
sf
E
so
= Q
in
+
_
t
f
to
_
mh + m
c
2
2
+ mgz
_
i
dt
Neglecting the potential and kinetic energy changes of the system and of
the inlet stream, the above equation is reduced to
U
sf
U
so
= Q
in
+
_
t
f
to
( mh)
i
dt
which can be rewritten, in terms of the specic internal energies, as
m
sf
u
sf
m
so
u
so
= Q
in
+ h
i
m
i
(9.21)
where h
i
is the specic enthalpy of the incoming nitrogen taken as a constant,
and m
i
is the mass of nitrogen entering the tank during the entire charging
process, given by
_
t
f
to
m
i
dt.
Mass balance (9.2) applied to the system yields
m
sf
m
so
= m
i
(9.22)
i
and rearranging the resulting
equation, we get
Q
in
= m
sf
u
sf
m
so
u
so
h
i
(m
sf
m
so
) (9.23)
Replacing the specic enthalpy h
i
in (9.23) by (u
i
+ RT
i
) applicable for an
ideal gas, we get
Q
in
= m
sf
(u
sf
u
i
RT
i
) m
so
(u
so
u
i
RT
i
)
= m
sf
[C
v
(T
sf
T
i
) RT
i
] m
so
[C
v
(T
so
T
i
) RT
i
]
= m
sf
(C
v
T
sf
C
p
T
i
) m
so
(C
v
T
so
C
p
T
i
)
= m
sf
C
v
(T
sf
T
i
) m
so
C
v
(T
so
T
i
) (9.24)
in which m
so
and m
sf
are known from (9.19) and (9.20), T
so
= 300 K, T
sf
=
450 K and T
i
= 500 K. We can calculate C
v
using R/( 1) as 717.5 J/kg K.
Substituting these numerical values in (9.24), we get Q
in
= 1055 kJ, which is
to say that about 1055 kJ of heat is lost to the surroundings during the entire
charging process.
Example 9.4
A tank contains 0.25 kg of nitrogen at 300 kPa
and 300 K. It is discharged until its pressure becomes 100 kPa. If the tank is
well insulated, what will be the nal temperature in the tank? Determine the
amount of nitrogen discharged from the tank. Assume ideal gas behaviour, and
for nitrogen to be 1.4.
Figure 9.5 shows discharging of nitrogen from a tank. Initially the tank is
lled with m
so
= 0.25 kg of nitrogen at P
so
= 300 kPa and T
so
= 300 K. It is
206 Chapter 9
discharged until its pressure becomes P
sf
= 100 kPa. We need to determine the
nal temperature T
sf
of the nitrogen remaining in the tank, and the amount of
nitrogen discharged from the tank.
Figure 9.5 Discharging of nitrogen from a tank.
nitrogen leaving the tank
h
valve
`
Arguments very similar to those presented in the Solution to Example
9.1 reduces (9.9) applied to the discharging process to
E
sf
E
so
=
_
t
f
to
_
mh + m
c
2
2
+ mgz
_
e
dt
which can be simplied, by neglecting the potential and kinetic energy changes,
to
U
sf
U
so
=
_
t
f
to
m
e
h
e
dt (9.25)
Unlike in the charging process considered in the previous examples, the spe-
cic enthalpy h
e
at the discharging point is a variable, and is equal to the specic
enthalpy of the nitrogen in the tank, that is h
s
. Thus, h
e
varies from h
so
to
h
sf
which are the respective initial and nal specic enthalpies of the nitrogen
in the tank. Integrating (9.25) would therefore not be possible unless the exact
variation of h
e
, or h
s
, as a function of time is known. Since we do not know
that, we need to approximate h
e
to a constant. The most suitable approach
would be to consider h
e
as the average value between its initial and nal values.
That would be
h
e
=
h
so
+ h
sf
2
= constant (9.26)
Substituting h
e
of (9.26) in (9.25), we get
U
sf
U
so
=
_
h
so
+ h
sf
2
_
m
e
(9.27)
where m
e
is the mass of nitrogen leaving the tank during the entire discharging
process, given by
_
t
f
to
m
e
dt.
Rewriting (9.27) in terms of specic internal energies, we get
m
sf
u
sf
m
so
u
so
=
_
h
so
+ h
sf
2
_
m
e
(9.28)
Applying (9.2) to the discharging process, we get
m
sf
m
so
= m
e
(9.29)
e
, we get
m
sf
u
sf
m
so
u
so
=
_
h
so
+ h
sf
2
_
(m
sf
m
so
) (9.30)
m
sf
(2 u
sf
h
so
h
sf
) = m
so
(2 u
so
h
so
h
sf
)
Using u = h - Pv, the above equation can be written as
m
sf
(h
sf
h
so
2 P
sf
v
sf
) = m
so
(h
so
h
sf
2 P
so
v
so
)
Now, transform the dierences in specic enthalpies into dierences in tem-
peratures using h =
_
C
p
dT, with the assumption that nitrogen behaves as
an ideal gas. Taking C
p
as a constant, and using the ideal gas equation of state
Pv = RT in the above equation, we get
m
sf
[C
p
(T
sf
T
so
) 2 RT
sf
] = m
so
[C
p
(T
so
T
sf
) 2 RT
so
]
Substituting m
so
= 0.25 kg, T
so
= 300 K, = 1.4, R = (8.314/28) kJ/kg K,
and therefore C
p
= R/( 1) = 1.039 kJ/kg K, we get
m
sf
(0.445 T
sf
311.7) = 33.4 0.260 T
sf
(9.31)
We need to determine T
sf
from (9.31), but we do not know m
sf
. Therefore,
we need to look for another independent equation containing T
sf
and m
sf
.
Applying the ideal gas equation of state at the nal state, we get
m
sf
=
P
sf
V
sf
RT
sf
(9.32)
of which we know P
sf
= 100 kPa, but V
sf
is unknown.
208 Chapter 9
Since the tank is rigid, its volume remains a constant throughout. Therefore
V
sf
= V
so
(9.33)
Applying the ideal gas equation of state at the initial state, we get
m
so
=
P
so
V
so
RT
so
(9.34)
Combining (9.32), (9.33) and (9.34), we get
m
sf
=
_
P
sf
RT
sf
_

_
m
so
RT
so
P
so
_
=
P
sf
T
so
m
so
P
so
T
sf
which gives
m
sf
= 25/T
sf
(9.35)
Eliminating m
sf
from (9.31) using (9.35), we get
0.260 T
2
sf
22.3 T
sf
7792.5 = 0
which gives
T
sf
= 221.2 K
sf
in (9.35), we get
m
sf
= 0.113 kg
The amount of nitrogen discharged from the tank is therefore given by
m
so
m
sf
= 0.25 kg 0.113 kg = 0.137 kg
9.5 Summary
Mass balance for an open system is given by
dm
s
dt
= m
i
m
e
(9.1)
where the subscript
s
stands for system,
i
for inlet, and
e
for exit.
Mass balance for an open system applied over a time interval t (=
t
f
t
o
) is given by
m
sf
m
so
= m
i
m
e
(9.2)
where m
sf
is the mass of the system at the nal time t
f
, m
so
is the mass
of the system at the initial time t
o
, m
i
is the total mass entering the
system during the time interval t, and m
e
is the total mass leaving the
system during the time interval t.
Equations (9.1) and (9.2) are applicable for open systems with not more
than one inlet and one exit. If an open system has many inlets and exits
for the mass to ow then (9.1) must be expanded to
dm
s
dt
= m
i1
+ m
i2
+ m
i3
+ m
e1
m
e2
m
e3

and (9.2) must be expanded to
m
sf
m
so
= m
i1
+ m
i2
+ m
i3
+ m
e1
m
e2
m
e3

where the subscripts
i1
,
i2
,
i3
,

stand for inlet 1, inlet 2, inlet 3, etc.,
and
e1
,
e2
,
e3
,

stand for exit 1, exit 2, exit 3, etc.
Energy balance (that is, the rst law of thermodynamics) for an open
system is given by
dE
s
dt
=

Q
in
+ (

W
boundary
)
in
+ (

W
shaft
)
in
+
_
mh + m
c
2
2
+ mgz
_
i
_
mh + m
c
2
2
+ mgz
_
e
(9.8)
Energy balance for an open system applied over a time interval t (=
t
f
t
o
) is given by
E
sf
E
so
= Q
in
+ (W
boundary
)
in
+ (W
shaft
)
in
+
_
t
f
to
_
mh + m
c
2
2
+ mgz
_
i
dt
_
t
f
to
_
mh + m
c
2
2
+ mgz
_
e
dt (9.9)
210 Chapter 9
where E
sf
is the energy of the system at the nal time t
f
, E
so
is the
energy of the system at the initial time t
o
, and Q
in
, (W
boundary
)
in
and
(W
shaft
)
in
are the respective amounts of net heat, net boundary work
and net shaft work entering the system during the time interval t.
Equations (9.8) and (9.9) are applicable for open systems with not more
than one inlet and one exit. If an open system has many inlets and
many exits then we must include
_
mh + m
c
2
2
+ mgz
_
-term in (9.8),
and
_
t
f
to
_
mh + m
c
2
2
+ mgz
_
dt-term in (9.9), at the respective inlets
and exits with appropriate signs; positive sign for inlet and negative sign
for outlet.
Chapter 10
THE FIRST LAW
APPLIED TO
STEADY FLOW PROCESSES
It is not the sun to overtake the moon, nor doth the night outstrip
the day. They oat each in an orbit.
The Holy Qur-an
In many engineering applications, devices such as turbines, pumps, com-
pressors, heat exchangers and boilers are operated under steady ow con-
ditions for long periods of time. A steady ow process is a process in which
matter and energy ow in and out of an open system at steady rates. More-
over, an open system undergoing a steady ow process does not experience
any change in the mass and energy of the system. Application of the rst
law of thermodynamics to steady ow processes is discussed in this chapter.
212 Chapter 10
10.1 What is Steady?
The term steady implies no change with time. We say that a person
is running at a steady speed of 5 km per hour, as shown in Figure 10.1, if
the speed does not change with time.
`
_

, ,
-
5 km per hour
Figure 10.1 A person running at a steady speed of 5 km per hour.
10.2 What is a Steady Flow Process?
A steady ow process is one in which matter and energy ow steadily
in and out of an open system. In a steady ow process, the properties of
the ow remain unchanged with time, that is, the properties are frozen in
time. But, the properties need not be the same in all points of the ow.
It is very common for a beginner to confuse the term steady with the
term equilibrium. But, they are not the same. When a system is at a
steady state, the properties at any point in the system are steady in time,
but may vary from one point to another point. The temperature at the inlet,
for example, may dier from that at the outlet. But, each temperature,
whatever its value, remains constant in time in a steady ow process.
When a system is at an equilibrium state, the properties are steady in
time and uniform in space. By properties being uniform in space, we mean
that a property, such as pressure, has the same value at each and every
point in the system.
An example of steady ow of water through a pipe is shown in Figure
10.2. Pressure measurements taken along the pipe at two dierent times
The First Law applied to Steady Flow Processes 213
of a day, shown in the gure, remain the same since the ow is steady.
But, observe that the values of pressure vary along the pipe illustrating the
nonuniform nature of the steady ow.
? ? ?
2.3 bar 2.0 bar 1.7 bar
-
water ows at a
(b) measurements taken at 2.00 pm
steady rate of 0.3 kg/s
Figure 10.2 An example of steady ow.
?
1.4 bar
?
1.1 bar
? ? ?
2.3 bar 2.0 bar 1.7 bar
-
water ows at a
(a) measurements taken at 10.00 am
steady rate of 0.3 kg/s
?
1.4 bar
?
1.1 bar
10.3 Characteristics of a
Steady Flow Process
A steady ow is one that remains unchanged with time, and therefore
a steady ow has the following characteristics:
Characteristic 1:
No property at any given location within the system boundary changes
with time. That also means, during an entire steady ow process, the
total volume V
s
of the system remains a constant, the total mass m
s
214 Chapter 10
of the system remains a constant, and that the total energy content
E
s
of the system remains a constant.
Characteristic 2:
Since the system remains unchanged with time during a steady ow
process, the system boundary also remains the same.
Characteristic 3:
No property at an inlet or at an exit to the open system changes
with time. That means that during a steady ow process, the mass
ow rate, the energy ow rate, pressure, temperature, specic (or
molar) volume, specic (or molar) internal energy, specic (or molar)
enthalpy, and the velocity of ow at an inlet or at an exit remain
constant.
Characteristic 4:
Rates at which heat and work are transferred across the boundary of
the system remain unchanged.
10.4 Mass Balance for a
Steady Flow Process
Since a steady ow process can be considered as a special process expe-
rienced by the open system discussed in Chapter 9, we may start from the
mass balance for open systems, which is given by (9.1). Characteristic 1 of
the steady ow process is that the mass of the open system experiencing
a steady ow process remains constant. This is achieved if the mass ow
rate at the inlet equals the mass ow rate at the exit. Therefore, (9.1)
reduces to
m
i
= m
e
(10.1)
where the subscript i denotes the inlet and the subscript e denotes the exit.
10.5 Energy Balance for a
Steady Flow Process
Since a steady ow process can be considered as a special process ex-
perienced by the open system discussed in Chapter 9, let us start with
(9.8) which is the energy balance applicable to open systems. According
to Characteristic 1 of the steady ow process, the total energy content E
s
of the system remains constant during the process. Therefore
dE
s
dt
= 0
According to Characteristic 2 of the steady ow process, the boundary
remains unchanged with time, so that no boundary work is done during a
steady ow process, and therefore
(

W
boundary
)
in
= 0
According to Characteristic 3, all properties at the inlet and the exit
of the system remain unchanged with time. Therefore, h, c and z are
constants.
Applying all the above characteristics of a steady ow process to (9.8),
we get
Q
in
+ (

W
shaft
)
in
+
_
mh + m
c
2
2
+ mgz
_
i
_
mh + m
c
2
2
+ mgz
_
e
= 0
which may be organised as
Q
in
+ (

W
s
)
in
= m
e
_
h
e
+
c
2
e
2
+ gz
e
_
. .
for exit
m
i
_
h
i
+
c
2
i
2
+ gz
i
_
. .
for inlet
(10.2)
where W
s
is shaft work, and the subscripts i and e denotes the inlet and
exit, respectively.
216 Chapter 10
It is important to note that each of the rates in (10.2) is a constant for
a steady ow process as pointed out in Characteristics 3 and 4 of steady
ow processes.
Equation (10.1) states that m
i
is the same as m
e
. Let us represent
these two equal mass ow rates by the symbol m, which can be considered
as the constant mass ow rate through the steady ow process. Using the
above in (10.2), we get the energy balance, that is the rst law of thermo-
dynamics applied to a steady ow process with a single inlet and a single
exit, as
Q
in
+ (

W
s
)
in
= m
_
h
e
h
i
+
c
2
e
c
2
i
2
+ g (z
e
z
i
]
_
(10.3)
which is the steady ow energy equation (abbreviated to SFEE) ap-
plicable to a single-stream steady ow process. The rate at which heat
enters the system is constant at

Q
in
. The rate at which shaft work enters
the system is constant at (

W
s
)
in
. The mass ow rates of the single stream
entering and leaving the system are constant at m. The specic enthalpy
of the stream at the inlet, the velocity of the stream at the inlet and the
elevation of the inlet are constant at h
i
, c
i
, and z
i
, respectively, and those
at the exit are constant at h
e
, c
e
, and z
e
, respectively. The acceleration
due to gravity is denoted by g.
For a multiple-stream steady ow process, that is a system with several
inlets and exits for mass to ow, the steady ow energy equation (SFEE)
becomes
Q
in
+ (

W
s
)
in
=
_
m
e1
_
h
e1
+
c
2
e1
2
+ gz
e1
__
+
_
m
e2
_
h
e2
+
c
2
e2
2
+ gz
e2
__
+
_
m
i1
_
h
i1
+
c
2
i1
2
+ gz
i1
__
_
m
i2
_
h
i2
+
c
2
i2
2
+ gz
i2
__
(10.4)
which is solved together with the mass balance for a multiple-stream steady
ow process,
m
e1
+ m
e1
+ = m
i1
+ m
i2
+ (10.5)
where the subscripts e1, e2, denote exit 1, exit 2, and so on, respec-
tively, and the subscripts i1, i2, denote inlet 1, inlet 2, and so on,
respectively.
10.6 Steady Flow Engineering Devices
Many engineering devices operate essentially under unchanged condi-
tions for long periods. For example, the industrial appliances such as tur-
bines, compressors, heat exchangers and pumps may operate nonstop at
steady state for months before they are shut down for maintenance. In this
section, we will deal with devices such as nozzles, turbines, compressors,
heat exchangers, boilers, and condensers. The emphasis will, however, be
on the overall functions of the devices, and the steady ow energy equation
will be applied to these devices treating them more or less like black boxes.
Nozzles & Diusers
Nozzles and diusers are properly shaped ducts which are used to in-
crease or decrease the speed of the uid owing through it. Schematics of
a typical nozzle and a typical diuser are shown in Figure 10.3. Nozzles are
used for various applications such as to increase the speed of water through
a garden hose, and to increase the speed of the gases leaving the jet engine
or rocket. Diusers are used to slow down a uid owing at high speeds,
such as at the entrance of a jet engine.
Since no shaft work is involved in a nozzle or a diuser, and since the
potential energy dierence across a nozzle or a diuser is usually negligible,
the steady ow energy equation (10.3) for ow through a nozzle or a diuser
becomes
Q
in
= m
_
h
e
h
i
+
c
2
e
c
2
i
2
_
(10.6)
218 Chapter 10
- -
nozzle
Figure 10.3 Schematics of a nozzle and a diuser.
i e
- -
diuser
i e
The ow through nozzles and diusers are often considered adiabatic,
so that the rate of heat transfer is neglected. Therefore (10.6) reduces to
c
2
e
c
2
i
2
= h
i
h
e
(10.7)
for adiabatic nozzles and diusers. It can be clearly seen in (10.7) that
an increase in the speed of the ow is accompanied by a decrease in its
enthalpy, as in the case of ow through an adiabatic nozzle. And, a decrease
in the speed of the ow is accompanied by an increase in its enthalpy, as
in the case of ow through an adiabatic diuser.
Turbines
A turbine is a device with rows of blades mounted on a shaft which
could be rotated about its axis (see Figure 1.1). In some water turbines
used in hydroelectric power stations, water at high velocity is directed at
the blades of the turbine to set the turbine shaft in rotation. The work
delivered by the rotating shaft drives an electric generator to produce elec-
trical energy. In steam turbines, steam at high pressure and temperature
enters a turbine, sets the turbine shaft in rotation, and leaves at low pres-
sure and temperature. In gas turbines, gaseous products of combustion
at high pressure and temperature set the turbine shaft in rotation. The
rotating shaft of a turbine is not always used for electric power generation.
It is also an essential part of a jet engine in an aircraft which generates the
thrust required to propel the aircraft. The schematic of a turbine is shown
in Figure 10.4.
-
-
Figure 10.4 Schematic of a turbine.
i
e
Since the uid owing through a turbine usually experiences negligible
change in elevation, the potential energy term is neglected. Work always
leaves the turbine, and therefore the (

W
s
)
in
term in (10.3) is negative. The
steady ow energy equation for ow through a turbine may therefore be
written as
Q
in
(

W
s
)
out
= m
_
h
e
h
i
+
c
2
e
c
2
i
2
_
(10.8)
The uid velocities encountered in most turbines are large, and the
uid experiences a signicant change in its kinetic energy. However, if this
change is small compared to the change in enthalpy then the change in
kinetic energy may be neglected. If the uid owing through the turbine
undergoes an adiabatic process, which is usually the case, then

Q
in
= 0.
Under such conditions, (10.8) reduces to
(

W
s
)
out
= m(h
i
h
e
) (10.9)
which clearly shows that the shaft work delivered by an adiabatic turbine is
derived from the enthalpy loss by the uid owing through the turbine.
Compressors
A compressor is a device used to increase the pressure of a gas owing
through it. The rotating type compressor functions in a manner opposite
to a turbine. To rotate the shaft of a compressor, work must be supplied
from an external source such as a rotating turbine shaft. The blades that
are mounted on the shaft of the compressor are so shaped that, when
the compressor shaft rotates, the pressure of the uid owing through the
220 Chapter 10
compressor increases. The rotating type compressors are used to raise the
pressure of the air owing through it in the electricity generation plants and
in the jet engines. In a reciprocating type compressor, a piston moves within
the cylinder, and the work needed to move the piston is generally supplied
by the electricity obtained from a wall socket. Household refrigerators use
the reciprocating type of compressors to raise the pressure of the refrigerant
owing through them. A schematic of a compressor is shown in Figure 10.5.
-
-
Figure 10.5 Schematic of a compressor.
i
e
The potential energy dierence across a compressor is usually neglected,
and the steady ow energy equation for ow through it becomes
Q
in
+ (

W
s
)
in
= m
_
h
e
h
i
+
c
2
e
c
2
i
2
_
(10.10)
A pump works like a compressor except that it handles liquids instead
of gases. Fans and blowers are compressors which impart a very small rise
in the pressure of the uid owing through them, and are used mainly to
circulate air. Equation (10.10) may be used to describe the ows through
pumps, fans and blowers.
The velocities involved in these devices are usually small to cause a
signicant change in kinetic energy, and often the change in kinetic energy
term is neglected. If the compressor, pump, fan or blower is operated under
adiabatic conditions, then

Q
in
= 0.
Under such conditions, (10.10) reduces to
(

W
s
)
in
= m(h
e
h
i
) (10.11)
which clearly shows that the shaft work provided to an adiabatic compressor,
pump, fan or blower is used to increase the enthalpy of the uid owing
through.
Throttling Valves
A throttling valve is a device used to cause a pressure drop in a owing
uid. It does not involve any work. The drop in pressure is attained by
placing an obstacle such as a partially open valve, porous plug or a capillary
tube in the path of the owing uid. The pressure drop in the uid is usu-
ally accompanied by a drop in temperature, and for that reason throttling
devices are commonly used in refrigeration and air-conditioning applica-
tions where a drop in the temperature of the working uid is essential. A
schematic of a throttling valve is shown in Figure 10.6.
Figure 10.6 Schematic of a throttling valve.
i e
Throttling valves are compact devices, and the ow through them is
eectively adiabatic. There is no shaft work involved. The change in
potential energy is neglected. The steady ow energy equation applied to
ow through an adiabatic throttling valve becomes
h
e
+
c
2
e
2
= h
i
+
c
2
i
2
(10.12)
Since the kinetic energy in many cases is insignicant when compared
to the enthalpy, the kinetic energy terms are neglected. So that Equation
(10.12) becomes
h
e
h
i
(10.13)
which shows the enthalpies at the inlet and the exit of a throttling valve
are nearly the same.
If the enthalpy terms in (10.13) are expanded using (u + Pv), we get
u
e
+ P
e
v
e
= u
i
+ P
i
v
i
which means that the summation of internal energy u and the ow work
Pv remains constant in a ow through a throttling valve.
If the ow work, Pv, increases during throttling, then internal energy,
u, will decrease, which often means a decrease in temperature. On the
222 Chapter 10
contrary, if Pv decreases then u will increase, resulting in probable temper-
ature increase. It means that the properties such as P, T and v of the uid
owing through the throttling valve may change even though the enthalpy
remains unchanged during throttling.
However, if the behaviour of the working uid approximates that of an
ideal gas then no change in enthalpy means no change in temperature as
well.
Mixing Chambers
Mixing chamber refers to an arrangement where two or more uid
streams are mixed to form one single uid stream as shown in the schematic
in Figure 10.7. Mixing chambers are very common engineering applications
in process industries.
-
-
Figure 10.7 Schematic of a mixing chamber.
-
i1
i2
e
Since a mixing chamber has more than one inlet, we use the steady
ow energy equation given by (10.4) to describe the ow through a mixing
chamber. For the mixing chamber of Figure 10.7 with two inlets and one
exit, (10.4) becomes
Q
in
= m
e
h
e
( m
i1
h
i1
+ m
i2
h
i2
) (10.14)
Note that there is no shaft work in a mixing chamber, and the changes
in kinetic and potential energies of the streams are usually neglected.
For the conservation of mass across the mixing chamber of Figure 10.7,
we can write
m
e
= m
i1
+ m
i2
which transforms (10.14) to
Q
in
= m
i1
(h
e
h
i1
) + m
i2
(h
e
h
i2
) (10.15)
Mixing chambers are usually well insulated, so that the process can be
treated as adiabatic. For an adiabatic mixing chamber, (10.15) reduces to
m
i1
(h
e
h
i1
) = m
i2
(h
i2
h
e
) (10.16)
Heat Exchangers
In the industries, there is often a need to cool a hot uid stream before
it is let out into the environment. The heat removed from cooling of a hot
uid can be used to heat another uid that has to be heated up. This can
be achieved in a heat exchanger, which in general is a device where a hot
uid stream exchanges heat with a cold uid stream without mixing with
each other. The simplest type is the double-pipe heat exchanger which has
two concentric pipes of dierent diameters. One uid ows in the inner pipe
and the other in the annular space between the two pipes. The schematic
of a double-pipe heat exchanger is shown in Figure 10.8.
Figure 10.8 Schematic of a double-pipe heat exchanger.

?
-
-
?
Bi Be
Ai
A
e
Since a heat exchanger has two inlets and two exits, we use (10.4).
There is no work transfer, and the changes in kinetic and potential energies
are neglected. Therefore, (10.4) reduces to
Q
in
= [ m
Ae
h
Ae
+ m
Be
h
Be
] [ m
Ai
h
Ai
+ m
Bi
h
Bi
] (10.17)
Since the mass ow rate of uid A is the same at the inlet and at the
exit, m
Ae
= m
Ai
, which may be represented by m
A
. Since the mass ow
224 Chapter 10
rate of uid B is the same at the inlet and at the exit, m
Be
= m
Bi
, which
may be represented by m
B
Thus, (10.17) becomes
Q
in
= m
A
[h
Ae
h
Ai
] + m
B
[h
Be
h
Bi
] (10.18)
Where a heat exchanger is insulated, it is adiabatic and the heat transfer
term may be neglected. So that (10.18) reduces to
m
fluid A
m
fluid B
=
(h
e
h
i
)
fluid B
(h
i
h
e
)
fluid A
(10.19)
Boilers and Condensers
A liquid is converted into vapour in a boiler by supplying heat to it.
A boiler, for example, is used to heat water at room temperature to its
boiling temperature so that water may be converted into steam. Heat may
be supplied to the boiler by burning a fuel in the boiler. In a condenser, a
vapour is condensed to liquid by removing heat from it. Schematics of a
boiler and a condenser are shown in Figure 10.9.
_
heat in
vapour out
liquid in
6
-
boiler
Figure 10.9 Schematics of a boiler and a condenser.
_
heat out
vapour in
liquid out
?
condenser
There is no shaft work involved in a boiler or a condenser. The potential
and kinetic changes across these devices are negligible in comparison to
the change in enthalpy. So that the steady ow energy equation for ow
through a boiler becomes
Q
in
= m(h
e
h
i
) (10.20)
and the steady ow energy equation for ow through a condenser be-
comes
Q
out
= m(h
i
h
e
) (10.21)
Example 10.1
Gases produced during the combustion of a
fuel-air mixture, enter a nozzle at 200 kPa, 150
C and 20 m/s and leave

the nozzle at 100 kPa and 100
C. The exit area of the nozzle is 0.03 m

2
.
Assume that these gases behave like an ideal gas with C
p
= 1.15 kJ/kg K
and = 1.3, and that the ow of gases through the nozzle is steady and
adiabatic. Determine (i) the exit velocity and (ii) the mass ow rate of the
gases.
(i) Determination of the exit velocity
The given ow may be satisfactorily described by (10.7). Since the behaviour
of the gases is approximated to that of an ideal gas with constant C
p
, (10.7)
can be rewritten as
c
2
e
c
2
i
2
= C
p
(T
i
T
e
) (10.22)
Substituting the values given in the problem statement in (10.22), we get
c
2
e
2
=
20
2
2
_
m
s
_
2
+
_
1.15
kJ
kg K
_
(423 K 373 K)
= 200
_
m
s
_
2
+ 57.5
_
kJ
kg
_
.
226 Chapter 10
We cannot add a quantity in kJ/kg to a quantity in (m/s)
2
. But, we can add
a quantity in J/kg to a quantity in (m/s)
2
since they are equivalent as shown
below:
J
kg
=
N m
kg
=
kg m
s
2
m
kg
=
_
m
s
_
2
Therefore,
c
e
=
2
_
200
_
m
s
_
2
+ 57.5 1000
_
J
kg
__
= 339.7 m/s
Note that the speed of the gases owing through the nozzle is increased
from 20 m/s to 339.7 m/s, which is achieved at the cost of the reduction in the
gas pressure from 200 kPa to 100 kPa.
(ii) Determination of the mass ow rate of the gases
Assume that the gas ows perpendicular to a cross sectional area A at a
uniform speed c and at a uniform density . The mass ow rate of the gases
through the given cross-section is then
m = A c = Ac/v (10.23)
where v is the specic volume.
Since we assume ideal gas behaviour, the ideal gas equation of state may be
used to express v as
v =
RT
P
Thus, the mass ow rate of an ideal gas through the cross-sectional area A
can be written as
m =
Ac P
RT
(10.24)
As we know the exit area, exit pressure, exit velocity and exit temperature,
and the gas constant R, calculated using R = ( 1) C
p
/ = 0.265 kJ/kg K,
m =
(0.03 m
2
) (339.7 m/s) (100 kPa)
(0.265 kJ/kg K) (373 K)
= 10.31 kg/s
Example 10.2
Rework Example 10.1 assuming that the
expansion of the gases owing through the nozzle from 200 kPa, 150
C
and 20 m/s at the inlet to 100 kPa at the exit takes place quasistatically.
(i) Determination of the exit velocity
Since the ow through the nozzle is assumed to be a quasistatic adiabatic
ow of an ideal gas, P and T of the ow can be related using (7.31), which
gives
T
e
= T
i
_
P
e
P
i
_
(1)/
= 423 K
_
100
200
_
(1.31)/1.3
= 360.5 K
Substituting the values of c
i
, T
i
and T
e
in (10.22), we get
c
e
=
2
_
200
_
m
s
_
2
+ 1.15 (423 360.5) 1000
_
J
kg
__
= 379.7 m/s
Note that the speed of the gases owing through the nozzle, expanding from
200 kPa to 100 kPa, is increased from 20 m/s to 379.7 m/s when the ow is
assumed to be quasistatic.
(ii) Determination of the mass ow rate of the gases
The mass ow rate of the gases through the nozzle is given by
m =
(0.03 m
2
) (379.7 m/s) (100 kPa)
(0.265 kJ/kg K) (360.5 K)
= 11.92 kg/s
Student: Teacher, for an expansion or a compression process to be quasistatic,
it must take place under fully restrained condition. Is that correct?
228 Chapter 10
Student: It is stated in Example 10.2 that the expansion of the ow through
the nozzle is assumed to be quasistatic. How could that be when there is
nothing to restrain the expansion of the gases owing through the nozzle?
Teacher: Yes, you are right about that. The ow through a nozzle is far from
quasistatic. However, we assume the ow to be quasistatic in order to
determine the maximum possible speed that could be attained by the
gases owing through the nozzle. Observe that the speed of the gases
at the exit is 379.7 m/s under quasistatic adiabatic condition, which sets
the maximum possible speed attainable by the gases owing through the
nozzle under the same inlet conditions and exit pressure.
Student: Oh... I see.
Teacher: It would be interesting to take look at the ratio between the actual
kinetic energy change per kg of ow and the ideal kinetic energy change
per kg of ow achievable with quasistatic adiabatic ow under the same
pressure dierence between the inlet and the outlet of the nozzle and the
same inlet temperature.
The required ratio =
[(c
2
e
c
2
i
)/2]
actual
[(c
2
e
c
2
i
)/2]
ideal
=
(339.7
2
20
2
)
(379.7
2
20
2
)
= 0.8
That is, the nozzle of Example 10.1 achieves only about 80% of the ki-
netic energy increase per kg of ow achievable under ideal ow conditions.
This way we determine the eciency at which a nozzle operates.
Student: Okay, I see now why the ow is assumed to be quasistatic in Ex-
ample 10.2. However, I have a question. How do you know that a
quasistatic ow gives the maximum possible speed attainable by the gas
ow through the nozzle?
Teacher: You are wrong. It is not the quasistatic ow, but the quasistatic
adiabatic ow that gives the maximum possible speed attainable by the
gas ow through the nozzle?
Student: Okay, Teacher. I still have a question. How do you know that a
quasistatic adiabatic ow gives the maximum possible speed attainable by
the gas ow through the nozzle?
Teacher: When learning the second law, you will see that it could be proved
that a quasistatic ow sets the limit for the best performance that could
be expected of an engineering device operated under adiabatic conditions.
Example 10.3
Rework Example 10.1 with steam owing
through the nozzle.
(i) The given ow can be described by (10.7), of which h
i
and h
e
are the specic
enthalpies of the steam at the inlet (2 bar and 150
C) and at the exit (1 bar

and 100
C). From a Steam Table, we nd that h

i
= 2770 kJ/kg and h
e
= 2676
kJ/kg. Substituting these values in (10.7) along with c
i
= 20 m/s, we get
c
e
=
2
_
200
_
m
s
_
2
+ (2770 2676) 1000
_
J
kg
__
= 434 m/s
(ii) The mass ow rate of the steam may be calculated using (10.23) of which
the specic volume v cannot be expressed as RT/P since the behaviour of
steam may not be approximated by the ideal gas behaviour. However, it is not
a problem because v for steam can be obtained from a Steam Table. We know
the cross-sectional area and the speed of steam at the exit. We can get v at the
exit at 1 bar and 100
C from the Steam Table as 1.696 m

3
/kg. Substituting
these values in (10.23), we get
m =
(0.03 m
2
) (434 m/s)
1.696 m
3
/kg
= 7.68 kg/s
230 Chapter 10
Example 10.4
Steam entering a nozzle at 7 bar and 250
C
with a velocity of 10 m/s, leaves it at 3 bar 200
C with a velocity of 262

m/s. Determine the heat lost by the steam owing through the nozzle.
If the mass ow rate of the steam owing through the nozzle is 2.5 kg/s,
determine the inlet area of the nozzle.
The given ow can be described by (10.6), of which h
i
and h
e
are the specic
enthalpies of the steam at the inlet (7 bar and 250
C) and at the exit (3 bar

and 200
C). From a Steam Table, we nd that h

i
= 2955 kJ/kg and h
e
= 2866
kJ/kg. Substituting these values in (10.6) along with c
i
= 10 m/s and c
e
= 262
m/s, we get
Q
in
= 2.5
kg
s

_
(2866 2955) 1000
_
J
kg
_
+
262
2
10
2
2
_
m
s
_
2
_
= 136.8 kJ
The heat lost by the steam owing through the nozzle is 136.8 kJ.
The inlet area of the nozzle can be calculated using (10.23) as follows:
A
i
=
mv
i
c
i
where m = 2.5 kg/s, c
i
= 10 m/s and v
i
= v at 7 bar and 250
C = 0.3364
m
3
/kg. The inlet area of the nozzle is therefore 0.0841 m
2
.
Example 10.5
Air (C
p
= 1.005 kJ/kg K; = 1.4) enters
an adiabatic diuser at 85 kPa and 250 K at a steady speed of 265 m/s and
leaves it at 15 m/s. Assuming ideal gas behaviour for air with constant
specic heats, determine the pressure and temperature of the air at the
diuser exit.
Equation (10.7) applied to the air ow through the adiabatic diuser assum-
ing ideal gas behaviour gives (10.22). Substituting the given numerical values
known from the problem statement in (10.22), we get
T
e
= 250 K
_
15
2
265
2
2 1005
_
(m/s)
2
J/kg K
= 284.8 K (10.25)
which gives the temperature of air at the diuser exit.
To determine the pressure at the exit, there is not enough data provided.
However, if we assume quasistatic ow through the diuser then, since the ow
is adiabatic and since ideal gas behaviour is assumed, P and T of the ow can
be related using (7.31), which gives
P
e
= P
i
_
T
e
T
i
_
/(1)
= 85 kPa
_
284.8
250
_
1.4/(1.41)
= 134 kPa
which gives the pressure of air at the diuser exit under ideal conditions.
That is, under quasistatic adiabatic ow conditions, the air owing through
the diuser is compressed from 85 kPa to 134 kPa, which is achieved at the cost
of the reduction in the air speed from 265 m/s to 15 m/s.
Example 10.6
A mixture of gases enter a nozzle at 2.5 bar
and 237
C with a speed of 20 m/s. The inlet diameter of the nozzle is

0.45 m. We are required to achieve an exit velocity of 340 m/s. Assuming
quasistatic ow conditions through the nozzle, determine (i) the pressure
that should be maintained at the nozzle exit and (ii) the exit diameter.
Take C
p
= 1.15 kJ/kg K and = 1.3 for the gases. Assume ideal gas
behaviour and steady adiabatic ow through the nozzle.
(i) Since the ow is assumed to be a quasistatic adiabatic ow of an ideal gas
232 Chapter 10
(7.31) could be used to determine the pressure at the nozzle exit as follows:
P
e
= 2.5 bar
_
T
e
510
_
1.3/(1.31)
(10.26)
where the exit temperature T
e
is unknown.
For the ow of gases, assumed to behave as an ideal gas, through an adiabatic
nozzle, (10.7) is applicable. Substituting the values known from the problem
statement in (10.7), we get
1.15
_
kJ
kg K
_
(T
e
510 K) +
_
340
2
20
2
2
_
_
m
s
_
2
= 0
which gives T
e
= 460 K.
Substituting this value of T
e
in (10.26) we get P
e
= 1.6 bar. That is, an
exit pressure of about 1.6 bar should be maintained for the combustion gases to
be able to reach the speed of 340 m/s
2
at the exit.
(ii) To determine the exit area, we use (10.24) as follows:
m =
_
Ac P
RT
_
inlet
=
_
Ac P
RT
_
exit
which gives
A
e
= A
i
_
P
i
P
e
__
c
i
c
e
__
T
e
T
i
_
= A
i
_
2.5
1.6
__
20
340
__
460
510
_
= 0.083A
i
Since A
i
= (/4)(0.45 m)
2
= 0.159 m
2
, the exit area of the nozzle is about
0.013 m
2
, and the exit diameter of the nozzle is about 0.13 m.
Example 10.7
A gas turbine is operated with gases (C
p
=
0.992 kJ/kg K and = 1.29) entering it at 10 bar and 1025
C, and
leaving it at 1 bar and 550
C. Assuming adiabatic ow through the turbine,

calculate the power output of the turbine (in MW) for each kg per second
of gases owing through the turbine.
If 120 MW of power is to be produced by the turbine, determine the
mass ow rate of gases owing through the turbine.
Equation (10.9) can be used to describe the behaviour of the gases owing
through the adiabatic turbine for which

Q
in
= 0. Since ideal gas behaviour is
assumed (10.9) becomes
(

W
s
)
out
= mC
p
(T
i
T
e
)
Substituting the known numerical values in the above equation, we get
(

W
s
)
out
= m 0.992
kJ
kg K
(1025 550) K = m 471.2 kJ/kg
which gives
(

W
s
)
out
m
= 471.2
kJ
kg
= 471.2
kJ/s
kg/s
= 471.2
kW
kg/s
= 0.4712
MW
kg/s
The power output of the turbine is therefore 0.4712 MW for each kg per
second of gases owing through the turbine.
Mass ow rate of gases required to produce 120 MW of power is calculated
as follows:
m =
120 MW
0.4712 MW/kg/s
= 254.7 kg/s
Example 10.8
Rework Example 10.7 under quasistatic
adiabatic conditions, where the gases are supplied to the turbine at 10
bar and 1025
C, and they leave it at 1 bar.

Ideal gas ow through the turbine under quasistatic adiabatic condition can
be described by (7.31) so that
T
e
= (1025 + 273) K
_
1
10
_
(1.291)/1.29
= 773.5 K = 500.5
C
234 Chapter 10
Therefore
(

W
s
)
out
m
= 0.992
kJ
kg K
(1025 500.5) K
= 520.3 kJ/kg
which gives that the power produced by the turbine under quasistatic adiabatic
ow condition is 0.5203 MW for each kg per second of gases owing through
the turbine.
Mass ow rate of gases required to produce 120 MW of power is calculated
as follows:
m =
120 MW
0.5203 MW/kg/s
= 230.6 kg/s
Observe that the turbine operating under quasistatic adiabatic condition
produces more power, as in Example 10.8, which is 0.5203 MW, than the
power produced by the turbine working under adiabatic but non-quasistatic
condition, as in Example 10.7, for the same inlet condition and the exit
pressure. The eciency of the turbine in Example 10.7, can therefore
be calculated as 0.4712/0.5203 = 90.6%.
Also, observe that the mass ow rate of the gas required to produce the
same power output from the turbine operating under the same inlet condi-
tion and the exit pressure is less for the quasistatic adiabatic ow through
the turbine, as in Example 10.8, than for the non-quasistatic adiabatic
ow through the turbine, as in Example 10.7.
Example 10.9
A steam turbine producing 55 MW power is
fed with steam at 70 bar and 500
C. Steam leaves the turbine at 0.08 bar

with a dryness fraction of 0.90. Determine the mass ow rate of steam
through the adiabatic turbine.
Equation (10.9) can be used to describe the behaviour of steam owing
through the adiabatic turbine, where (

W
s
)
out
= 55 MW, and h
i
is the enthalpy
at 70 bar and 500
C and h
e
is the enthalpy at 0.08 bar for a dryness fraction of
0.90. From a Superheated Steam Table, we nd that h
i
= 3410 kJ/kg. From a
Saturated Water and Steam Table, we nd that
h
i
= h
f
+x (h
g
h
f
) at 0.08 bar and x = 0.90
= 174 kJ/kg + 0.90 (2576 174) kJ/kg = 2336 kJ/kg
Substituting the known numerical values in (10.9), we get
55 10
3
kJ
s
= m (3410 2336)
kJ
kg
which gives m, which is the mass ow rate of steam through the adiabatic
turbine, as 51.2 kg/s.
Example 10.10
A steam turbine is fed with 53 kg/s of high
pressure steam at 70 bar and 500
C and with 10 kg/s of low pressure

C. The steam leaving the turbine is at 0.07 bar

with the dryness fraction of 0.92. Determine the power produced by the
steam turbine considering the fact that the heat loses from the turbine is
equivalent to 2% of the power production.
The schematic of the steam turbine given is shown in Figure 10.10. Since the
turbine has two inlets and one exit, we must use the steady ow energy equation
applied for a multiple-stream steady ow process given by (10.4). Neglecting
the changes in potential and kinetic energies reduces (10.4) applied to the given
system to
(

Q)
in
+ (

W
s
)
in
= m
e
h
e
m
i1
h
i1
m
i2
h
i2
236 Chapter 10
Since the power output is positive for a turbine and since heat is lost to the
surroundings, the above equation can be rewritten as
(

Q)
out
+ (

W
s
)
out
= m
i1
h
i1
+ m
i2
h
i2
m
e
h
e
(10.27)
where (

Q)
out
is given as 2% of (

W
s
)
out
.
-
Figure 10.10 Schematic of the turbine of Example 10.10.
e
-
i2
i1
i2 is low pressure steam at 6 bar and 250
C
i1 is high pressure steam at 70 bar and 500
C
e is steam at 0.07 bar and x = 0.92
-
From a Superheated Steam Table, we can nd that the enthalpy of the high
pressure steam h
i1
= 3410 kJ/kg and the enthalpy of the low pressure steam
h
i2
= 2958 kJ/kg. From a Saturated Water and Steam Table, we can nd that
the enthalpy of the steam leaving the turbine h
e
= 163 kJ/kg + 0.92 2409
kJ/kg = 2379 kJ/kg. The mass ow rates are given as m
i1
= 53 kg/s and m
i2
= 10 kg/s.
The mass balance applied for a multiple-stream steady ow process is given
by (10.5), which for the given system becomes
m
e
= m
i1
+ m
i2
= (53 + 10) kg/s = 63 kg/s
Substituting the known numerical values in (10.27), we get
0.02 (

W)
out
+ (

W
s
)
out
= (53 3410 + 10 2958 63 2379) kJ/s
= 60433 kW
which gives
(

W)
out
=
60433 kW
1.02
= 59248 kW = 59.25 MW
That is, the steam turbine power output is 59.25 MW, and the heat lost to
the surroundings is about 1.18 MJ/s.
Example 10.11
Air at 100 kPa and 300 K with a mass ow
rate of 0.05 kg/s is to be compressed to 800 kPa using any one of the
following methods:
Method 1: Quasistatic adiabatic compression from 100 kPa to 800 kPa
in a single compressor.
in one compressor followed by quasistatic adiabatic compression from
250 kPa to 800 kPa in a second compressor.
in one compressor followed by constant pressure cooling to 300 K at
250 kPa, and then quasistatic adiabatic compression from 250 kPa
to 800 kPa in a second compressor.
Determine the method in which the total power requirement is the lowest.
Method 1:
Applying (10.11) to the rst compressor operated adiabatically, assuming
that air behaves as an ideal gas, we get
(

W
s
)
in
= mC
p
(T
e
T
i
) (10.28)
Substituting the numerical data in the problem and the properties of air from
Table 5.2 in (10.28), we get
(

W
s
)
in
=
_
0.05
kg
s
__
1.005
kJ
kg K
_
(T
e
300) K
where T
e
is unknown. Since the ow is taken to be quasistatic adiabatic, we
can use (7.31) to determine T
e
as follows:
T
e
= T
i
_
P
e
P
i
_
(1)/
= 300 K
_
800
100
_
(1.41)/1.4
= 543.4 K
Therefore,
(

W
s
)
in
= 12.23 kJ/s = 12.23 kW
That is, the power requirement of a single compressor to adiabatically and
quasistatically compress air at 100 kPa and 300 K to 800 kPa is 12.23 kW.
238 Chapter 10
Method 2:
Here, air is compressed to 250 kPa in one compressor, and the hot air
leaving it is compressed in a second compressor to 800 kPa. Both compressions
are quasistatic adiabatic. The power requirement of the rst compressor can be
worked out in a manner similar to that is described under Method 1, except for
the fact that the exit pressure is now 250 kPa, not 800 kPa. Therefore, we get
the exit temperature as
T
e
= T
i
_
P
e
P
i
_
(1)/
= 300 K
_
250
100
_
(1.41)/1.4
= 389.8 K
Substituting the numerical value of T
e
in (10.28), we get (

W
s
)
in
= 4.51 kW.
The second compressor works in a way very similar to the rst, except for
that the inlet pressure is 250 kPa, the inlet temperature is 389.8 K, and the
exit pressure is 800 kPa. Therefore, we get the exit temperature of the second
compressor as
T
e
= 389.8 K
_
800
250
_
(1.41)/1.4
= 543.5 K
The power requirement of the second compressor, evaluated using (10.28),
is (

W
s
)
in
= 7.72 kJ/s = 7.72 kW.
The total power requirement of the two compressors is obtained by adding
4.51 kW to 7.72 kW, which is 12.23 kW.
Method 3:
The rst compressor here is similar to the rst compressor in Method 2, and
its power requirement is 4.51 kW. The second compressor here has an inlet
temperature of 300 K, and
T
e
= 300 K
_
800
250
_
(1.41)/1.4
= 418.3 K
and the power consumption, evaluated using (10.28), is 5.94 kW.
The total power requirement of the two compressors is obtained by adding
4.51 kW to 5.94 kW, which is therefore 10.45 kW.
The total power consumptions are the same for Method 1 and for Method
2. The total power consumption is the lowest for Method 3, in which the hot
air exiting the rst compressor is cooled to 300 K before it is fed to the second
compressor. Method 3 uses the practice known as multi-stage compression
with intercooling in order to decrease the work required to compress the gas
between two specied pressures.
Example 10.12
An ideal gas is compressed by an adiabatic
compressor in a steady-ow process, and cooled to its initial temperature.
The potential and kinetic energy changes are negligible. Compare the heat
removed from the gas in the cooler with the work done on the gas by the
compressor.
The schematic of the given system is shown in Figure 10.11.
cooler
T
1
T
2
T
1
Figure 10.11 Schematic for Example 10.12.
`
_
(

W
s
)
in
Q
out
Equation (10.11) applied to the ideal gas ow through the adiabatic com-
pressor becomes
(

W
s
)
in
= mC
p
(T
2
T
1
) (10.29)
where T
1
and T
2
are the respective inlet and exit temperatures of the gas owing
through the compressor, as shown in Figure 10.11.
The term (

W
s
)
in
is a positive quantity since work is always done on the gas
by the compressor. Consequently, the gas temperature T
2
at the compressor
exit is always larger than the temperature T
1
at the inlet. The gas leaving the
compressor at T
2
is cooled to its initial temperature T
1
in a cooler. The steady
ow energy equation (10.3), when applied to the cooler becomes
Q
in
= m(h
e
h
i
)
since there is no work exchange and since the potential and kinetic energy
changes are neglected.
For an ideal gas, the above equation becomes

Q
in
= mC
p
(T
1
T
2
). Since
the cooler exit temperature T
1
is less than the inlet temperature T
2
, the above
240 Chapter 10
equation can be rewritten as
Q
out
= mC
p
(T
2
T
1
) (10.30)
which is a positive quantity.
Combining (10.29) and (10.30), we get (

W
s
)
in
=

Q
out
. That is, the work
done on the gas by the compressor equals the heat removed from the gas in the
cooler under the conditions stated in the problem.
Example 10.13
A pump is used to increase the pressure of
25 kg/s of saturated water at 0.07 bar entering the pump to 100 bar and
40
C. Determine the power input to the pump assuming adiabatic ow

through the pump.
Neglecting the potential and kinetic energy changes, the power input to
the adiabatic pump can be determined using (10.11), where h
i
is the specic
enthalpy of saturated water at 0.07 bar and h
e
is the specic enthalpy at 50
bar and 40
C. From a Saturated Water and Steam Table, we nd h

i
= 163
kJ/kg. The water leaving the pump is at compressed state at 100 bar. From a
Compressed Water Table
, we nd h
e
= 176 kJ/kg. Substituting the numerical
values known in (10.11), the power input of the pump can be calculated as
W
in
= 25 (176 163) kJ/s = 325 kW.
Example 10.14
Wet steam at 7 bar is throttled adiabatically
to 1 bar and 110
C. Determine the dryness fraction of the wet steam at 7

bar.
Table A-7 of Cengel, Y.A. & Boles, M.A. 1998 Thermodynamics: an engineering
approach, 3
rd
Steam ow through the adiabatic throttling valve can be expressed by (10.13)
which states that the specic enthalpies at the inlet h
i
and at the exit h
e
are
nearly the same. The value of h
e
at 1 bar and 110
C can be obtained from a

Superheated Steam Table as 2696 kJ/kg. According to (10.13), the value of h
i
at 7 bar is the same as 2696 kJ/kg. At 7 bar, a Saturated Water and Steam
Table gives h
f
= 697 kJ/kg and h
g
= 2764 kJ/kg. Therefore, the dryness
fraction of the wet steam at 7 bar can be calculated as
x =
h
e
h
f
h
g
h
f
=
2696 697
2764 697
= 0.967 = 96.7%
Example 10.15
Water owing at 5 bar and 120
C is mixed
with superheated steam owing at 10 bar and 200
C in an adiabatic mixing
chamber to produce saturated water at 8 bar. Determine the ratio of the
mass ow rates of water and the superheated steam, neglecting the changes
in kinetic and potential energies.
The steady ow energy equation applied to the adiabatic mixing chamber
shown in Figure 10.7, neglecting the changes in potential and kinetic energies, is
given by (10.16), where i1 denotes the water entering the mixing chamber at 5
bar and 120
C, i2 denotes the superheated steam entering the mixing chamber

at 10 bar and 200
C, and e denotes the saturated steam leaving the mixing

chamber at 8 bar.
The water at 5 bar and 120
C is at compressed state. Since the pressure is

5 bar, we use the approximate method discussed in the Solution to Example
(6.8) to determine h
i1
. In this method, we approximate h
i1
to the saturated
water specic enthalpy at 120
C, which is 504 kJ/kg as read from a Saturated

Water and Steam Table.
The superheated steam specic enthalpy h
i2
is directly read from a Super-
heated Steam Table as 2829 kJ/kg at 10 bar and 200
C. The saturated water

242 Chapter 10
specic enthalpy h
e
is directly read from a Saturated Water and Steam Table as
721 kJ/kg at 8 bar.
Substituting the known numerical values in (10.16), we can determine the
ratio of the mass ow rate of water to the mass ow rate of superheated steam
as
m
i1
m
i2
=
h
i2
h
e
h
e
h
i1
=
2829 721
721 504
= 9.7
Example 10.16
A gas ( = 1.3) fed to a turbine at 10
bar and 370
C, is assumed to expand quasistatically and adiabatically to 4

bar as it ows through the turbine. The gas stream exiting the turbine is
mixed with a second stream of the same gas owing at 4 bar and 38
C, in
an adiabatic mixing chamber. The mass ow rate of the gas through the
turbine is 4 times the mass ow rate of the second gas stream. Determine
the temperature of the gas leaving the mixing chamber at 4 bar, neglecting
the changes in kinetic and potential energies and assuming that the gas
concerned behaves as an ideal gas.
The schematic of the given system is shown in Figure 10.12. The tem-
perature of the gas leaving the mixing chamber is to be found, which is the
temperature of the gas stream labeled 4 in Figure 10.12.
2 4
1
``

``

``

Figure 10.12 Schematic of the system given in Example 10.16.
!
!
a
a
`
_
BB
3 gas at 10 bar & 643 K
gas at 4 bar & 311 K
The steady ow energy equation applied to the gas ow through an adiabatic
mixing chamber with negligible changes in the potential and kinetic energies,
given by (10.16), becomes
m
2
(h
4
h
2
) = m
3
(h
3
h
4
)
which is written in accordance with the stream labels shown on Figure 10.12.
Since the gas is assumed to behave as an ideal gas, the above equation
becomes
m
2
C
p
(T
4
T
2
) = m
3
C
p
(T
3
T
4
)
which yields
T
4
=
m
2
T
2
+ m
3
T
3
m
2
+ m
3
(10.31)
To nd T
4
, we need the value of each and every term on the right-hand side
of (10.31).
First of all note that m
2
is the mass ow rate through the turbine, and that
m
3
is the mass ow rate of the second gas stream. It is given that the mass
ow rate of the gas stream through the turbine is 4 times the mass ow rate of
the second gas stream. Therefore, m
2
= 4 m
3
, which reduces (10.31) to
T
4
=
4 T
2
+T
3
5
=
4 T
2
+ 311 K
5
(10.32)
since T
3
= 311 K.
We need to nd T
2
, which is the temperature of the exit gas stream from the
turbine. The ow through the turbine is assumed to be quasistatic adiabatic,
and therefore (7.31) can be used to nd T
2
as follows:
T
2
= T
1
_
P
2
P
1
_
(1)/
= 643 K
_
4
10
_
(1.31)/1.3
= 520.5 K = 247.5
C
Substituting T
2
= 520.5 K in (10.32), we get T
4
= 478.6 K = 205.6
C.
Note that the second gas stream is heated from 38
C to 205.6
C by mixing
it with the turbine exit at 247.5
C.
Example 10.17
Air (C
p
= 1.005 kJ/kg K and = 1.4) is
heated as it ows steadily through a pipe of uniform cross-sectional area
150 cm
2
. It enters at 300 kPa and 345 K with a velocity of 25 m/s and
244 Chapter 10
leaves at 200 kPa and 800 K, and may be assumed to behave as an ideal
gas. Determine the amount of heat added per kilogram of air.
If this amount of heat is supplied to 1 kg of air in a closed rigid container
at 300 kPa and 345 K, what will be the nal temperature and pressure of
air in the container?
The steady ow energy equation (10.3) applied to the pipe ow yields
Q
in
= m
_
h
e
h
i
+
c
2
e
c
2
i
2
_
since there is no work exchange or potential energy change.
Substituting the given numerical values in the above equation with the as-
sumption that air behaves as an ideal gas, we get
Q
in
m
=
_
1005
J
kg K
(800 345) K +
c
2
e
25
2
2
_
m
s
_
2
_
(10.33)
where the exit velocity c
e
is unknown.
To determine the exit velocity, let us use the fact that the ow is steady, and
therefore the mass ow rate is the same at the inlet and the exit. Thus (10.24)
gives
c
e
=
_
A
i
A
e
__
P
i
P
e
__
T
e
T
i
_
c
i
=
_
150
150
__
300
200
__
800
345
_
25 m/s = 87 m/s
Substituting c
e
= 87 m/s in (10.33), we get

Q
in
= 460.75 kJ per kg of air
owing through the pipe.
The second part of the problem states that 460.75 kJ/kg of heat is supplied
to air in a closed rigid container at 300 kPa and 345 K. Suppose the mass of air
in the close container is m, then Q
in
= 460.75 m kJ. Therefore, the rst law
applied to the given closed system yields,
460.75 m = U
since no work is supplied to the air in the closed rigid container. Since air is
taken as an ideal gas, we get
U = mC
v
(T
f
T
i
)
Therefore,
460.75 m = m0.718 (T
f
345)
which gives T
f
= 986.7 K.
The pressure in the closed container can be obtained using the ideal gas
equation of state for the given closed system as follows:
m =
P
f
V
f
RT
f
=
P
i
V
i
RT
i
Since V
f
= V
i
for the closed rigid container, we get
P
f
= P
i
_
T
f
T
i
_
= 300 kPa
_
986.7
345
_
= 858 kPa
Note that when the same amount of heat is provided, the temperature and
pressure increases in the closed system are far greater than those in the open
system. You may try to gure out why it is so as an exercise.
Example 10.18
Compressed air is preheated in a shell-and-
tube heat exchanger, shown in Figure 10.13, before it enters the combustion
chamber.
Figure 10.13 Schematic of a heat exchanger of Example 10.18.
air at T
e
C
air at 200
C
gases at 550
C
gases at 250
C
-
-
-
-
-
-
-
-
?
6
6
?
It enters the heat exchanger at 9 bar and 200
C with a mass ow rate of

16 kg/s. It gains heat from the exhaust gases leaving a turbine. Exhaust
246 Chapter 10
gases enter the heat exchanger at 1.4 bar and 550
C and leave at 1.2 bar

and 250
C at a mass ow rate of 17 kg/s. Assume that C

p
for the exhaust
gases are the same as that for air and that the heat exchanger operates
under adiabatic conditions. Determine the exit temperature of the air and
the amount of heat transferred from the exhaust gases to the air.
For an adiabatic heat exchanger with two uid streams, (10.19) can be used.
Taking the exhaust gases as A and the compressed air as B and assuming ideal
gas behaviour, (10.19) can be rewritten as
m
exhaust gases
m
air
=
(h
e
h
i
)
air
(h
i
h
e
)
exhaust gases
=
(T
e
T
i
)
air
(T
i
T
e
)
exhaust gases
since C
p
for the exhaust gases is assumed to be the same as that for the air.
Substituting the numerical values known in the above equation, we get
17
16
=
T
e
200
550 250
(10.34)
which gives the exit temperature of air T
e
as 519
C.
To determine the heat transferred from the exhaust gases to the air, let us
apply the steady ow energy equation (10.3) to one of the streams. For air,
Q
in
= mC
p
(T
e
T
i
) = 16 1.005 (519 200) kJ/s = 5.13 MJ/s
Example 10.19
Rework Example 10.18 with a mass ow
rate of air taken as of 14 kg/s, and comment on your results.
Replacing 16 in (10.34) by 14, we get
17
14
=
T
e
200
550 250
(10.35)
which gives the exit air temperature T
e
as 564
C.
The exit air temperature of 564
C is greater than the temperature of the

exhaust gases entering the heat exchanger, which is 550
C. Since the air leaving

the heat exchanger is receiving heat from the exhaust gases entering the heat
exchanger, the exhaust gas temperature must always be greater than the air
temperature. Therefore, the answer we got is unrealistic. Thus, we conclude
that the mass ow rate of air should not be as low as 14 kg/s.
10.8 Summary
A steady ow process with a single-stream owing through the system is
described by
m
i
= m
e
(10.1)
and by
Q
in
+ (

W
s
)
in
= m
_
h
e
h
i
+
c
2
e
c
2
i
2
+g (z
e
z
i
]
_
(10.3)
which is the steady ow energy equation (abbreviated to SFEE) for a
single-stream process.
For a multiple-stream steady ow process, that is, a system with many
inlets and many exits for mass to ow in and out of the system, the steady
ow energy equation (SFEE) becomes
Q
in
+ (

W
s
)
in
=
_
m
e1
_
h
e1
+
c
2
e1
2
+gz
e1
__
+
_
m
e2
_
h
e2
+
c
2
e2
2
+gz
e2
__
+
_
m
i1
_
h
i1
+
c
2
i1
2
+gz
i1
__
_
m
i2
_
h
i2
+
c
2
i2
2
+gz
i2
__
(10.4)
which is solved together with the mass balance for a multiple-stream
steady ow process,
m
e1
+ m
e1
+ = m
i1
+ m
i2
+ (10.5)
248 Chapter 10
where the subscripts e1, e2, denote exit 1, exit 2, and so on, respec-
tively, and the subscripts i1, i2, denote inlet 1, inlet 2, and so on,
respectively.
We can add a quantity in J/kg to a quantity in (m/s)
2
since they are
equivalent as shown below:
J
kg
=
N m
kg
=
kg m
s
2
m
kg
=
_
m
s
_
2
Assume that a uid ows perpendicular to a cross section with a cross-
sectional area A, at a uniform speed c and at a uniform density . The
mass ow rate of the uid through the cross-sectional area A is then
m = A c =
Ac
v
(10.23)
where v is the specic volume.
If the uid were steam or a mixture of water and steam, v could be found
from the Steam Table.
If the uid were assumed to behave as an ideal gas, then the ideal gas
equation of state would give v = RT/P. Therefore, the mass ow rate
of an ideal gas through the cross-sectional area A is
m =
Ac P
RT
(10.24)
Chapter 11
ENTROPY
There is nothing like looking, if you want to nd something. You
certainly usually nd something, if you look, but it is not always
quite the something you were after.
J.R.R. Tolkien (The Hobbit)
In the preceding chapters, we have learnt many aspects of the rst law
applications to various thermodynamic systems. We have also learnt to
use the thermodynamic properties, such as pressure, temperature, internal
energy and enthalpy, when analysing thermodynamic systems. In this chap-
ter, we will learn yet another thermodynamic property known as entropy,
and its use in the thermodynamic analyses of systems.
250 Chapter 11
11.1 Reversible Process
The property entropy is dened for an ideal process known as the re-
versible process. Let us therefore rst see what a reversible process
is all about. If we can execute a process which can be reversed without
leaving any trace on the surroundings, then such a process is known as the
reversible process. That is, if a reversible process is reversed then both the
system and the surroundings are returned to their respective original states
at the end of the reverse process. Processes that are not reversible are
called irreversible processes.
Student: Teacher, what exactly is the dierence between a reversible process
and a cyclic process?
Teacher: In a cyclic process, the system returns to its original state. Thats
all. We dont bother about what happens to its surroundings when the
system is returned to its original state. In a reversible process, on the
other hand, the system need not return to its original state. However, the
path of the reversible process must be such that if the process is reversed
so as to return the system to its original state then its surroundings must
also return to its original state, as though the process has never occurred
in the rst place.
Student: How to carry out a process such that, when reversed, no trace is left
to indicate that the process has ever occurred?
Teacher: If a process is carried out in such a manner that no irreversibilities take
place within or outside the boundaries of the system then it is possible to
reverse the system and the surroundings to their respective original states
as though the process has never occurred.
Student: Is it possible to realize such a process?
Teacher: Of course, it is not possible to realize a reversible process in real life
situations. But, if we can minimize the irreversibilities occurring within
and outside the boundary of a system during a process then such a process
can be said to approach a reversible process.
Student: What do you mean by irreversibilities, Teacher?
Entropy 251
Teacher: Friction is an irreversibility. During a process, some amount of work
may be done to overcome friction force. If such a process is reversed, we
will not be able to take back the energy used as work to overcome friction
force. As a matter of fact, some more work has to be done to overcome
friction during the reversal of the process as well. Such a process is far
from a reversible process. If we are to approach a reversible process then
the process taking place must experience very little or no friction forces.
Student: Okay, Teacher. I see that friction is an irreversibility. That, I must
say, is very easy to understand and accept. Are there any other forms of
irreversibilities, Teacher?
Teacher: Yes, there are. Unrestrained expansion or compression is another
form of irreversibility. A reversible expansion or compression process is
imagined to take place under innitely small pressure dierence between
the system and its surroundings, without destroying the uniform distribu-
tion of the properties within the system. That means, during a reversible
expansion or compression process, the system passes through a series of
equilibrium states. Therefore, it is possible to reverse it at any time during
the process without leaving a trace on the surroundings.
Student: Oh.. you are talking about the quasistatic process that we have learnt
in Chapter 7.
Teacher: Yes, a quasistatic process carried out under certain conditions is an
example of a reversible process.
Student: What are those conditions, Teacher?
Teacher: A quasistatic process carried out under adiabatic conditions is indeed
a reversible process.
Student: Why do we require the adiabatic condition, Teacher?
Teacher: Because heat transfer between a system and its surroundings is always
an irreversible process. You know that heat is transferred from a system
to its surroundings only if the temperature of the system is higher than
the temperature of the surroundings. If you are to reverse this process,
then heat must be transferred from the low temperature surroundings to
the high temperature system, which is impossible.
Student: Okay, Teacher. Are you saying that a reversible process must always
be an adiabatic process?
252 Chapter 11
Teacher: Well, we can always imagine a non-adiabatic process where the heat
transfer between the system and its surroundings takes place under the
condition of extremely small temperature dierence between the system
and its surroundings. Such a process may be said to approach a reversible
process even though it is not an adiabatic process.
Student: Okay, Teacher. Let me see. If there is a non-adiabatic quasistatic
process, then heat is transferred between the system and the surroundings
under conditions of extremely small temperature dierences between the
system and the surroundings. Is that correct?
Student: Teacher, dont you think it would be very hard to transfer heat across
extremely small temperature dierences?
Teacher: Yes, it would be impractical since it would take a very long time
to transfer heat across very small temperature dierences between the
system and its surroundings.
Student: Teacher, I understand from what you are saying that a reversible
process is a highly idealized process, and that it is next to impossible to
execute a reversible process in reality. Why do we study it then?
Teacher: We study about reversible processes for two reasons. First, they
are easy to analyze since a system passes through a series of equilibrium
states during a reversible process. Second, they give the Natures limit
imaginable for the corresponding real processes. Reversible processes can
be viewed as theoretical limits for the corresponding irreversible ones.
11.2 Denition of Entropy
The property entropy is dened in terms of change in entropy as
dS
dQ
in
T
rev
(11.1)
where the label rev stands for reversible process.
Entropy 253
Integrating the above, we get
S =
S
f
So
dS =
f
o
(dQ
in
)
rev
T
(11.2)
which could be used for the evaluation of entropy change for a reversible
process between state o and state f.
In this textbook, we use S to denote entropy, and s to denote both the
specic and molar entropies. The unit kJ/K is used for entropy, kJ/kg K
for specic entropy, and kJ/kmol K for molar entropy.
11.3 Evaluation of Entropy Change
for Any Process
Entropy change could be evaluated using (11.2) provided the process
concerned is a reversible process. In this section, we will obtain expressions
that could be used to evaluate the entropy changes of both reversible and
irreversible processes.
Let us start from (11.1), which could be rearranged to give
TdS = (dQ
in
)
rev
(11.3)
Using the rst law, the dQ
in
term in (11.3) can be replaced to give
TdS = (dU dW
in
)
rev
(11.4)
Since the internal energy change dU is independent of the path of the
process, but dW
in
depends on the path of the process, (11.4) can be written
as
TdS = dU (dW
in
)
rev
(11.5)
The work term in a reversible process of a simple compressible system
is the boundary work only. Since the path of a reversible process consists
of a series of equilibrium states, the boundary work involved in a reversible
process shall be given by (7.5). Using (7.5) in (11.5), we get
TdS = dU +P dV (11.6)
254 Chapter 11
which can be written in terms of specic (or molar) properties as
Tds = du +P dv (11.7)
Using h = u + Pv in (11.7) to eliminate du, we get
Tds = dh v dP (11.8)
Equations (11.7) and (11.8) are the most general equations applicable
to evaluate the entropy change of any system undergoing any process,
reversible or irreversible.
Upon rearranging and integrating (11.7), we get
s =
u
f
uo
du
T
+
v
f
vo
P dv
T
(11.9)
Upon rearranging and integrating (11.8), we get
s =
h
f
ho
dh
T

P
f
Po
v dP
T
(11.10)
Equations (11.9) and (11.10) could be used to determine the entropy
change of any process between state o and state f for any substance.
Student: Teacher, could you tell me why you dropped the subscript
rev
from
(11.6) which you derived from (11.5), which is valid only for a reversible
process. Is that a mistake?
Teacher: No, it is not a mistake. Observe that each term in (11.6) is a prop-
erty, and the dierential of a property depends only on the values of the
properties at the initial and the nal states, not on the path of the pro-
cess. Therefore, (11.6), (11.7) and (11.8) are applicable for any process,
reversible or not. But, dW
in
in (11.5) is a path dependent function, and
therefore it is necessary to specify the nature of the process for which
(11.5) can be applied. The same can be said about (11.3) where the path
dependent function dQ
in
is equated to a combination of properties, T dS.
Student: Teacher, I cant agree with what you say.
Teacher: Why not?
Entropy 255
Student: Take the rst law of thermodynamics given by dQ
in
+dW
in
= dU, in
which the summation of two path dependent functions dQ
in
and dW
in
are
equated to the dierential in the property U. But, we know that we can
apply dQ
in
+dW
in
= dU to any process as far as the system concerned
is a closed system.
Teacher: When adding two path dependent functions, it is possible that the
summation becomes independent of the path as in the case of the rst
law. So that the rst law is applicable for any process. But, in (11.3) or in
(11.5), there is only one path dependent function against a combination
of properties, which can be equated to each other only under special
circumstances, such as a reversible process.
Teacher: It is also of interest to note that even though (11.7), and (11.8) are
obtained using the rst law applied to closed system, these equations are
applied to uid owing through open systems as well since these equations
contain only properties.
11.4 Isentropic Process
For an adiabatic process, dQ
in
= 0. If the adiabatic process considered
is a reversible process then (11.1) will give dS = 0. That is to say entropy
remains constant for a reversible, adiabatic process. Such a process
is therefore known as an isentropic process.
11.4.1 Isentropic Process of an ideal gas
For an isentropic process, dS = 0. Therefore, (11.6) reduces to
dU +P dV = 0 (11.11)
Since dU = mC
v
dT for an ideal gas, (11.11) can be rewritten as
mC
v
dT +P dV = 0 (11.12)
256 Chapter 11
which gives
P dV = mC
v
dT (11.13)
which is the same as (7.27), the equation from which (7.29), (7.30) and
(7.31) describing the quasistatic adiabatic process, which is indeed an isen-
tropic process, of an ideal gas are derived. So, whenever we use (7.29),
(7.30) or (7.31) to describe a process of an ideal gas, we in fact are using
the information that entropy remains constant for that process.
We have already worked out problems involving the quasistatic adiabatic
processes of ideal gas (that is, isentropic processes of ideal gas) in the
preceding chapters. We made use of (7.29), (7.30) or (7.31) to work out
such problems.
11.4.2 Isentropic Process of
Steam/Water Systems
Entropy of a given mass of steam/water remains constant throughout
an isentropic process. We will therefore use the information that the spe-
cic entropy of a system remains constant when it undergoes an isentropic
process to refer to the steam table to determine the required equilibrium
state of the system along the isentropic process considered.
In this chapter, we shall work out problems involving the isentropic pro-
cesses of steam/water systems which we have not dealt with so far in this
book.
Example 11.1
Based on equation (11.1), is it reasonable to
conclude that the entropy of a closed system remains constant during an
adiabatic process?
Entropy 257
Equation (11.1) is applicable for a reversible process only. If the given adi-
abatic process is reversible then dS = 0, which means that entropy remains
constant for a reversible adiabatic process.
But, if the given adiabatic process is not a reversible process, then (11.1) is
not applicable for that process. Therefore, dS may not be equal to zero. And,
thus, we cannot say that entropy remains constant for such a process.
Example 11.2
Is the numerical value of the integral
2
1
dQ/T
the same for all processes between states 1 and 2?
For a reversible process,
2
1
dQ/T = S = S
2
S
1
Since the dierence (S
2
- S
1
) depends only on the states 1 and 2,
2
1
dQ/T
remains the same for all reversible processes between states 1 and 2.
If the process considered is not a reversible one, then
2
1
dQ/T cannot be
equated to (S
2
- S
1
), and therefore we cannot expect the numerical value of the
integral
2
1
dQ/T to be the same for all processes between states 1 and 2.
Example 11.3
Show that, for a reversible isothermal pro-
cess, the net heat supply to the system from its surroundings can be eval-
uated using Q
in
= T S.
258 Chapter 11
For a reversible process, (11.2) can be applied. If the given process is a
reversible isothermal process, then T is a constant in (11.2) and therefore T can
be taken out of the integral sign in (11.2). Thus, we get
S =
1
T
f
o
(dQ
in
)
rev
=
Q
in
T
(11.14)
where Q
in
is the net heat supplied to the system undergoing a reversible isother-
mal process between states o and f. Equation (11.14) can be rearranged to
give
Q
in
= T S for a reversible isothermal process. (11.15)
Example 11.4
Saturated steam at 40 bar expands reversibly
and isothermally to 5 bar in a piston-cylinder assembly. The mass of steam
is 5 kg. Determine the heat and work exchanges of the steam with its
surroundings.
Temperature of saturated steam at 40 bar can be found from the Satu-
rated Steam Table as 250.3
C. Since the expansion is reversible and isothermal,

(11.15) could be used to determine the heat exchange between steam and its
surroundings.
Initially, steam is at saturated vapour state at 40 bar. Specic entropy at
the initial state can therefore be found from the Steam Table as 6.070 kJ/kg K.
Since the expansion process takes place isothermally, temperature at the nal
state remains at 250.3
C. Pressure at the nal state is 5 bar. Specic entropy at

the nal state can therefore be found from the Steam Table as 7.271 kJ/kg K.
The total entropy dierence of the given isothermal process is then given by
S = (5 kg) (7.271 6.070) kJ/kg K = 6.005 kJ/K
Using the above in (11.15), we get
Q
in
= (273 + 250.3) K 6.005 kJ/K = 3142.4 kJ
Entropy 259
The work output could be calculated using the rst law as
W
out
= Q
in
U = 3142.4 kJ (5 kg) (u
f
u
o
)
where u
f
= u for steam at 5 bar at 250.3
C 2725 kJ/kg and u

o
= u for
saturated steam at 40 bar = 2602 kJ/kg.
Therefore, we get
W
out
= 3142.4 kJ (5 kg) (2725 2602) kJ/kg = 2527.4 kJ
Example 11.5
If the working uid of Example 11.4 were
an ideal gas instead of steam, then the heat supplied to the working uid
would be the same as the work done by the working uid during the ex-
pansion. Why is this not so for steam as seen in Solution to Example
11.4?
For an ideal gas, internal energy is a function of temperature alone. There-
fore, U = 0 for the isothermal process of an ideal gas. Thus, the rst law
would give that the heat supplied to the ideal gas is the same as the work done
by the ideal gas during the expansion.
For steam, internal energy is not a function of temperature alone. Therefore,
U could take a nite value for an isothermal process of steam, as seen in the
Solution to Example 11.4. Owing to the nite value that U takes, heat
supplied to steam cannot be the same as the work done by steam during its
expansion.
Example 11.6
Starting fromT ds =dhv dP, show that for
a constant-pressure process, s = C
p
ln (T
f
/T
o
) where C
p
is the specic
heat at constant-pressure, taken as a constant.
260 Chapter 11
Since dP = 0 for a constant-pressure process, T ds = dh v dP reduces to
T ds = dh for a constant-pressure process. (11.16)
The enthalpy change for any substance can be written as dh = C
p
dT for a
constant-pressure process of any substance (see Section 5.5). Equation (11.16)
therefore becomes
T ds = C
p
dT for a constant-pressure process,
which upon integration gives
s =
T
f
To
C
p
T
dT for a constant-pressure process. (11.17)
When C
p
is taken as a constant, (11.17) reduces to
s = C
p
ln
T
f
T
o
for a constant-pressure process. (11.18)

Equations (11.17) and (11.18) are applicable for both the reversible and
irreversible constant-pressure processes of any substance.
Example 11.7
Starting from T ds = du + P dv, show that
for a constant-volume process, s = C
v
ln (T
f
/T
o
) where C
v
is the specic
heat at constant-volume, taken as a constant.
Since dv = 0 for a constant-volume process, T ds = du +P dv reduces to
T ds = du for a constant-volume process. (11.19)
The internal energy change for any substance can be written as du = C
v
dT
for a constant-volume process of any substance (see Section 5.4). Equation
(11.19) therefore becomes
T ds = C
v
dT for a constant-volume process,
Entropy 261
which upon integration gives
s =
T
f
To
C
v
T
dT for a constant-volume process. (11.20)
When C
v
is taken as a constant, (11.20) reduces to
s = C
v
ln
T
f
T
o
for a constant-volume process. (11.21)

Equations (11.20) and (11.21) are applicable for both the reversible and
irreversible constant-volume processes of any substance.
Example 11.8
Show that S = mC ln (T
f
/T
o
) for an in-
compressible substance undergoing any process, where m is the mass of
substance and C is the specic heat, taken as constant.
An incompressible substance does not experience any volume change, and
therefore dv = 0. The internal energy change for any substance undergoing
no volume change can be written as du = C
v
dT, where C
v
is the specic
heat at constant-volume (see Section 5.4). These facts about incompressible
substance are the same as those for the constant-volume process considered in
the Solution to Example 11.7. Therefore, (11.20) is applicable also for an
incompressible substance undergoing any process.
For an incompressible substance, C
p
and C
v
take nearly the same value
and we denote that value as C. Taking C as a constant, we could obtain an
expression for the total entropy change, staring from (11.20), as
S = mC ln
T
f
T
o
(11.22)
for an incompressible substance undergoing any process.
262 Chapter 11
Example 11.9
The temperature of a metal block of 500 kg
and 0.42 kJ/kg K specic heat is reduced from 800 K to 450 K. Determine
the total entropy change of the metal block.
Assuming the metal block to be an incompressible substance, we could use
(11.22) to evaluate the entropy change of the metal block as follows:
S = (500 kg) (0.42 kJ/kg K) ln
450
800
= 120.8 kJ/K
Example 11.10
Starting from Tds = du+P dv, show that
an ideal gas (with constant C
v
and C
p
) undergoing any process satises
the following equations:
s = C
v
ln (T
f
/T
o
) +R ln (v
f
/v
o
)
= C
p
ln (T
f
/T
o
) R ln (P
f
/P
o
)
= C
p
ln (v
f
/v
o
) +C
v
ln (P
f
/P
o
)
For an ideal gas, du = C
v
dT and P = RT/v. Substituting these in Tds =
du +P dv and integrating, we get
s =
T
f
To
C
v
dT
T
+
v
f
vo
RT dv
v T
= C
v
ln
T
f
T
o
+R ln
v
f
v
o
(11.23)
Using h = u +P v in Tds = du +P dv, we can get Tds = dh v dP as in
Section 11.3. For an ideal gas, dh = C
p
dT and v = RT/P. Substituting these
Entropy 263
in Tds = dh v dP and integrating, we get
s =
T
f
To
C
p
dT
T

P
f
Po
RT dP
P T
= C
p
ln
T
f
T
o
R ln
P
f
P
o
(11.24)
Multiplying (11.23) by C
p
and (11.24) by C
v
and subtracting one from the
other, we get
(C
p
C
v
) s = C
p
R ln
v
f
v
o
+C
v
R ln
P
f
P
o
Since C
p
C
v
= R, the above reduces to
s = C
p
ln
v
f
v
o
+C
v
ln
P
f
P
o
(11.25)
Example 11.11
Air is compressed from 1 bar and 300 K to
7 bar at a steady ow rate of 9 kg/s. Determine the power required if the
ow through the compressor is reversible and adiabatic.
Work input to the adiabatic compressor can be calculated using (10.11)
provided the potential energy and kinetic energy changes across the compressor
are neglected. Assuming air behaves as an ideal gas with constant C
p
, (10.11)
can be written as
(

W
s
)
in
= mC
p
(T
e
T
i
)
= (9 kg/s) (1.005 kJ/kg K) (T
e
300 K) (11.26)
where T
e
is not known.
Since the ow is reversible and adiabatic (that is, isentropic), (7.31) could
be used to determine T
e
as follows:
T
e
= T
i
P
e
P
i
(1)/
= 300 K
7
1
(1.41)/1.4
= 523 K
Therefore, (11.26) gives (

W
s
)
in
= 2.0 MW.
264 Chapter 11
Comment: Note that we could have also calculated T
e
using (11.24) in which
s = 0 since the process is reversible and adiabatic, that is, isentropic.
Example 11.12
Air is compressed from 1 bar and 300 K to
7 bar at a steady ow rate of 9 kg/s. Determine the power required if the
ow through the compressor is reversible and isothermal.
Work input to a non-adiabatic compressor can be calculated using (10.10)
provided the potential energy change across the compressor is negligible. When
also the kinetic energy change across the compressor is neglected, (10.10) re-
duces to
Q
in
+ (

W
s
)
in
= m(h
e
h
i
) (11.27)
Since the ow through the compressor is assumed to be reversible and
isothermal, we could use (11.15), which for a uid owing steadily at a mass
ow rate of m becomes
Q
in
= mT s = mT (s
e
s
i
) (11.28)
(

W
s
)
in
= m[(h
e
h
i
) T (s
e
s
i
)] (11.29)
for a reversible isothermal ow through a compressor.
Integrating (11.8) for an isothermal process, we get
T (s
e
s
i
) = (h
e
h
i
)
Pe
P
i
v dP (11.30)
(

W
s
)
in
= m
Pe
P
i
v dP (11.31)
for a reversible isothermal ow through the compressor.
Entropy 265
If we assume that air behaves as an ideal gas then we get
(

W
s
)
in
= mRT ln
P
e
P
i
(11.32)
for reversible isothermal ow of an ideal gas through a compressor.
Substituting the known values in (11.32), we get
(

W
s
)
in
= (9 kg/s)
8.314
29
kJ/kg K 300 K ln
7
1
= 1.5 MW
Example 11.13
Show that if the ow through a pump is
assumed to be reversible then the power input to the pump can be deter-
mined, neglecting potential and kinetic energy changes across the pump,
using
(

W
s
)
in
mv
i
(P
e
P
i
)
where i and e denote inlet and exit, respectively.
Work input to a pump can be calculated using (10.10) provided the potential
energy change across the pump is negligible. When also the kinetic energy
change across the pump is neglected, (10.10) reduces to
Q
in
+ (

W
s
)
in
= m(h
e
h
i
) (11.33)
Since the ow through the pump is assumed to be reversible, we could use
(11.3), which for a uid owing steadily at a mass ow rate of m becomes
d(

Q
in
)
rev
= mT ds
Upon integration, it gives
(

Q
in
)
rev
= m
se
s
i
Tds (11.34)
266 Chapter 11
For a reversible ow through the pump, the heat input term in (11.33) can
be substituted by the heat input term given by (11.34). We then get
(

W
s
)
in
= m
h
e
h
i
se
s
i
Tds
(11.35)
Upon integration, (11.8) gives
se
s
i
Tds = h
e
h
i
Pe
P
i
vdP (11.36)
Using (11.36), we can reduce (11.35) to
(

W
s
)
in
= m
Pe
P
i
vdP (11.37)
which is applicable for a reversible ow through a pump.
Since only liquids are compressed using pumps and since the specic volume
of a liquid varies only slightly from the inlet to the exit of the pump, (11.37) can
be approximated to
(

W
s
)
in
mv
i
(P
e
P
i
) (11.38)
Example 11.14
A pump is used to increase the pressure of
12 kg/s of saturated water at 0.07 bar entering the pump to 15 bar with
only a slight temperature increase. Determine the power input to the pump
assuming reversible ow through the pump.
Since the ow through the pump is assumed to be reversible, (11.38) may be
used to evaluate the power input to the pump. The specic volume of saturated
water at 0.07 bar entering the pump v
i
is 0.0010074 m
3
/kg. The mass ow rate
is 12 kg/s, P
i
= 0.07 bar and P
e
is 15 bar. Substituting the known numerical
values in (11.38), we get
(

W
in
)
pump
12 kg/s 0.0010074 m
3
/kg (1500 7) kPa = 18.05 kW
Entropy 267
Example 11.15
Steam enters a turbine at 70 bar and 450
C
and leaves it as wet steam at 0.08 bar. Steam ow rate through the turbine
is 50 kg/s. Assuming the ow through turbine as reversible adiabatic,
determine the work output of the turbine.
At the turbine inlet, we have superheated steam at 70 bar and 450
C. The
specic enthalpy found from a Superheated Steam Table at the turbine inlet
condition is h
i
= 3287 kJ/kg.
At the turbine outlet, we have wet steam at 0.08 bar. Since the ow through
the turbine is assumed to be reversible adiabatic, the entropy of the ow remains
constant. That is,
s
e
= s
i
= s at 70 bar and 450
C = 6.632 kJ/kg K
The dryness fraction at the turbine outlet can be calculated using
x
e
=
s
e
s
f
s
fg
=
6.632 0.593
7.634
= 0.7911
The specic enthalpy at the turbine outlet is then
h
e
= h
f
+x
e
h
fg
= 174 + 0.7911 2402 = 2074 kJ/kg
The work output of the turbine is calculated, using (10.9) applicable for ow
through an adiabatic turbine, as follows:
(

W
s
)
out
= m(h
i
h
e
) = 50 (3287 2074) kJ/s = 60.65 MW
Example 11.16
A rigid cylinder contains a oating piston.
Initially, it divides the cylinder in half, and on each side of the piston the
cylinder holds 0.01 kmol of steam at 200
C and 100 kPa. Using an electrical

heater installed on side A of the cylinder, heat is added slowly until the
268 Chapter 11
pressure in side A reaches 150 kPa. The piston and the cylinder are perfect
thermal insulators with negligible heat capacity. Determine the following:
(a) Final volume of steam on side B.
(b) Work done by the piston on steam on side B.
(c) Amount of heat supplied by the electrical heater.
Heat added slowly to side A causes the steam on side A to expand pushing
the oating piston outwards to compress the steam on side B. Both the
expansion of steam on side A and the compression of steam on side B may
be assumed to be quasistatic processes. Since the piston and the cylinder are
perfect heat insulators, the steam on side B is assumed to undergo an adiabatic
process.
Taking the molar mass of the steam as 18 kg/kmol, we nd that the mass
of steam in each side is m = 0.18 kg. Figure 11.1 shows all the data for the
problem.
Note that this example is very similar to Example 7.24, except for the
dierence the working uid is ideal gas in Example 7.24 and it is steam in this
example. Since the behaviour of steam in general may not be approximated to
ideal gas behaviour, we cannot use (7.29), or its equivalent (7.30) or (7.31), to
describe the quasistatic adiabatic process executed by steam on side B, as we did
in the Solution to Example 7.24. Instead we shall use the fact the entropy
remains constant for a quasistatic adiabatic (that is, an isentropic) process.
A
1 bar
200
C
0.18 kg
B
1 bar
200
C
0.18 kg
V
Ai
V
Bi
A
1.5 bar
T
Af
C
B
1.5 bar
T
Bf
C
V
Af
V
Bf
m m m m
Figure 11.1 Initial and nal states of Example 11.16.
(a) Determine the nal volume of steam on side B.
Initially, steam on side B is at 1 bar and 200
C. From a Steam Table, we can

nd that the steam is at superheated vapour state with the following properties:
Entropy 269
v
Bi
= 2.173 m
3
/kg, u
Bi
= 2659 kJ/kg and s
Bi
= 7.834 kJ/kg K.
At the nal state, the steam on side B is at 1.5 bar. Since the entropy and
the mass of steam on side B remain constant, the specic entropy of steam on
side B at the nal state is the same as s
Bi
given above.
From a Steam Table, we can nd that the nal state of steam on side B at
1.5 bar 7.834 kJ/kg K specic entropy is also a superheated vapour state with
the following properties:
v
Bf
= 1.594 m
3
/kg, u
Bf
= 2729 kJ/kg and T
Bf
= 248
C.
Since the mass of steam on side B is 0.18 kg, we get the nal volume of the
steam on side B as V
Bf
= 0.287 m
3
.
(b) Determine the work done by the piston on steam on side B.
Since the steam on side B undergoes an adiabatic process, the rst law of
thermodynamics applied to it gives
(W
in
)
B
= (U)
B
= m(u
Bf
u
Bi
)
= 0.18 (2729 2659) kJ = 12.6 kJ (11.39)
(c) Determine the amount of heat supplied by the electrical heater.
Following the discussion on part (c) of the Solution to Example 7.24,
we can write the heat supplied by the heater as
(Q
in
)
A
= (U)
A
+ (W
in
)
B
(11.40)
in which (U)
A
must be determined using
(U)
A
= m(u
Af
u
Ai
) = 0.18 (u
Af
2659) kJ
since u
Ai
= u
Bi
.
In order to nd u
Af
, we know one property of the steam on side A at the
nal state, which is the pressure 1.5 bar, and we require another property which
could only be the specic volume expressed as
v
Af
=
V
Af
0.18 kg
=
V
Ai
+V
Bi
V
Bf
0.18 kg
270 Chapter 11
in which we know V
Bf
= 0.287 m
3
. Since V
Ai
= V
Bi
and since v
Bi
= 2.173
m
3
/kg, the above equation gives
v
Af
=
2 0.18 2.173 0.287
0.18 kg
= 2.752 m
3
/kg
It can be found from a Steam Table that steam at 1.5 bar and 2.752 m
3
/kg
specic volume is at a superheated vapour state, and the corresponding proper-
ties are
u
Af
= 3332 kJ/kg and T
Af
= 618
C.
Using the above value of u
Af
and the value of (W
in
)
B
from (11.39) in
(11.40), we get
(Q
in
)
A
= [0.18 (3332 2659) + 12.6] kJ = 133.7 kJ
which is the heat supplied by the electrical heater.
In summary, we conclude that the 133.7 kJ of heat supplied by the electrical
heater to the steam on side A, while maintaining the quasistatic nature of the
process on side A, is used to raise its temperature to 618
C and for this steam

to push the piston outwards by doing 12.6 kJ of work on the piston. The piston
moves without friction to use the 12.6 kJ of work to quasistatically and adia-
batically compress the steam on side B. The work done on this steam raises its
temperature to 248
C.
11.6 Summary
If we can execute a process which can be reversed without leaving any
trace on the surroundings, then such a process is known as the reversible
process. That is, if a reversible process is reversed then both the system
and the surroundings are returned to their respective original states at the
end of the reverse process. Processes that are not reversible are called
irreversible processes.
Entropy 271
Entropy is dened as
dS
dQ
in
T
rev
(11.1)
For any system undergoing any process,
T ds = du +P dv (11.7)
T ds = dh v dP (11.8)
Entropy remains a constant for a reversible adiabatic process, which is
also known as an isentropic process.
The path of an isentropic process of an ideal gas can be described by
(7.29), (7.30) and (7.31).
The path of an isentropic process of a water/steam system may be traced
by using the fact that entropy remains constant along such a path.
For a reversible isothermal process of any substance,
Q
in
= T S (11.15)
For both the reversible and irreversible constant-pressure processes of any
substance,
s =
T
f
To
C
p
T
dT (11.17)
which, when C
p
is taken as a constant, reduces to
s = C
p
ln
T
f
T
o
(11.18)
For both the reversible and irreversible constant-volume processes of any
substance,
s =
T
f
To
C
v
T
dT (11.20)
which, when C
v
is taken as a constant, reduces to
s = C
v
ln
T
f
T
o
(11.21)
For an incompressible substance, with constant specic heat C, undergo-
ing any process,
s = C ln
T
f
T
o
(11.22)
where C = C
v
C
p
for an incompressible substance.
272 Chapter 11
For an ideal gas, with constant C
p
and C
v
, undergoing any process,
s = C
v
ln
T
f
T
o
+R ln
v
f
v
o
(11.23)
= C
p
ln
T
f
T
o
R ln
P
f
P
o
(11.24)
= C
p
ln
v
f
v
o
+C
v
ln
P
f
P
o
(11.25)
For reversible ow through a compressor, pump, fan or blower
(

W)
in
= m
Pe
P
i
v dP (11.37)
For reversible liquid ow through a pump
(

W)
in
mv
i
(P
e
P
i
) (11.38)
since the specic volume of a liquid varies only slightly when it ows
through a pump.
Chapter 12
THERMODYNAMIC ANALYSES
OF POWER PLANTS
It sounded an excellent plan, no doubt, and very neatly and simply
arranged; the only diculty was that she had not the smallest idea
how to set about it.
Lewis Carrol (Alice in Wonderland)
Power plants are where power is produced such as in the electricity gen-
erating stations and turbojet engines. The workings of these power plants
are complicated. In this chapter, however, we will learn about the basic
working principles governing a few simple power plants and about carrying
out thermodynamic analyses of simplied power plants to determine vital
parameters such as the overall thermal eciency. This chapter is written
to make the students of this book appreciate some real life applications of
what they have so far learned in thermodynamics.
274 Chapter 12
12.1 Gas Turbine for
Electric Power Generation
Water, as we have seen in Chapter 1, is used to rotate the shaft of a
turbine in a hydroelectric power station. In a gas turbine used for electric
power generation, the shaft of the turbine is rotated by the gases produced
in the burning of a fuel with air. The basic working principle of a simple
gas turbine used for electric power generation is explained below with the
help of the ow diagram shown in Figure 12.1.
combustion
chamber
compressor
turbine
exhaust gases released
into the atmosphere
shaft
fuel
shaft power
for generation
of electricity
atmospheric
air
Figure 12.1 Flow diagram of a simple gas turbine power plant.
gases
compressed
air
Air is drawn from the atmosphere and is compressed to a high pressure
in a compressor. The high pressure air enters a combustion chamber, in
which fuel is sprayed onto the compressed air, and the fuel-air mixture is
burned at constant pressure. The gases leaving the combustion chamber
at high pressure and high temperature are directed towards the turbine
blades so as to rotate the turbine shaft. In general, nearly half of the work
output of the rotating turbine shaft is used to rotate the compressor shaft,
and the rest is used to produce electricity by spinning a coil between the
poles of a magnet or an electromagnet. Thus, part of the heat generated
in burning the fuel in the combustion chamber is converted into useful
electrical energy.
Thermodynamic Analyses of Power Plants 275
The gases leaving the turbine are released into the atmosphere. These
gases contain carbon dioxide, nitrous oxides, sulfur oxides and particulate
matter. The temperature of the exhaust gases can also be very high. Be-
fore releasing these gases into the atmosphere, therefore, it is essential to
make sure that the polluting potential of these exhaust gases is reduced to
the level set by the environmental authority of the country concerned. Even
though there is absolutely nothing one could do about the carbon dioxide,
a product of complete combustion of the fuel used, into the atmosphere.
Example 12.1
Consider the gas turbine power plant shown
in Figure 12.1. Atmospheric air at 1 bar and 300 K is drawn into a com-
pressor at a mass ow rate of 350 kg/s, and is compressed to 5 bar. The
compressed air is heated at constant pressure in the combustion chamber
by burning the fuel injected onto the air owing through the combustion
chamber. The gases leave the combustion chamber at 1200 K, and en-
ter the turbine of the power plant, rotate the turbine shaft, and leave the
turbine at 1 bar.
(a) Determine the power input to the compressor, power production of
the turbine, and the power available for electricity generation. Also,
determine the back work ratio, dened as the ratio of the compressor
work to the turbine work.
(b) Calculate the heat input to the combustion chamber. Also, determine
the thermal eciency of the power plant, dened as the ratio of the
net work output to the heat input.
(c) Determine the air-fuel ratio, assuming the heating value of the fuel
as 42 MJ/kg.
(d) Discuss the validity of the solutions obtained above.
The block diagram of the given problem is shown in Figure 12.2.
276 Chapter 12
_
`
_
`
_
XX

XX

XX

XX

1 2 3 4
1 bar
300 K
5 bar
T
2
=?
5 bar
1200 K
1 bar
T
4
=?
[(W
s
)
in
]
comp
[(W
s
)
out
]
turb
[Q
in
]
comb
compressor
chamber
combustion
turbine
T
T
T
T
T
T
Figure 12.2 Block diagram for Example 12.1.
Let us work out the problem under ideal conditions making the following
assumptions:
Assumption 1: Assume that the ows through the compressor and the turbine
are adiabatic and reversible. Then, (7.31) could be used to relate the pres-
sure and the temperature at the inlet to the pressure and the temperature
at the exit.
Assumption 2: Neglect the increase in the mass ow rate of gases leaving the
combustion chamber as a result of fuel injection. That is, the mass ow
rates through the compressor, combustion chamber and the turbine are
all 350 kg/s.
Assumption 3: Assume C
p
as 1.005 kJ/kg K and as 1.4 for both the air and
the combustion gases.
Assumption 4: Assume that all the gases involved in the problem behave like
ideal gases, with constant specic heats.
Assumption 5: Neglect the potential and kinetic energy changes.
(a) First, let us determine the power input to the compressor. Using (10.11),
we have
[(

W
s
)
in
]
comp
= mC
p
(T
2
T
1
) = 350 1.005 (T
2
300) kJ/s
of which T
2
is unknown. Since the ow through the compressor is assumed to
be reversible and adiabatic, (7.31) gives
T
2
= T
1
P
2
P
1
(1)/
= 300 K
5
1
0.4/1.4
= 475.2 K
Therefore, [(

W
s
)
in
]
comp
= 61.63 MJ/s. That is, the power requirement of
the compressor is 61.63 MW.
Let us now determine the work output of the turbine. Using (10.9), we have
[(

W
s
)
out
]
turb
= mC
p
(T
3
T
4
) = 350 1.005 (1200 T
4
) kJ/s
of which T
4
is unknown. Since the ow through the turbine is assumed to be
reversible and adiabatic, (7.31) gives
T
4
= T
3
P
4
P
3
(1)/
= 1200 K
1
5
0.4/1.4
= 757.7 K
Therefore, [(

W
s
)
out
]
turb
= 155.58 MJ/s. That is, the power output of the
turbine is 155.58 MW.
The power available for electricity generation is the dierence between the
power output of the turbine (= 155.58 MW) and the power requirement of the
compressor (= 61.63 MW), which is 93.95 MW.
The back work ratio is calculated as
bwr =
compressor work input
turbine work output
=
61.63 MW
155.58 MW
= 39.6%
Comment: About 39.6% of the work produced by the turbine is consumed by
the compressor to compress the ambient air to 5 bar pressure. Only the remain-
ing 60.4% is available for electricity generation. One of the major drawbacks in
using a gas turbine power plant for electricity generation is the relatively large
part of the turbine work output being consumed by the compressor.
(b) Heat input to the combustion chamber can be calculated by applying (10.3)
to the air owing through the combustion chamber as
[

Q
in
]
comb
= mC
p
(T
3
T
2
)
= 350 1.005 (1200 475.2) kJ/s = 254.95 MW
where the fuel ow rate through the combustion chamber is neglected.
The thermal eciency of the gas turbine plant is calculated as
th
=
net work output of the gas turbine plant
heat input to the gas turbine plant
=
155.58 MW61.63 MW
254.95 MW
=
93.95
254.95
= 36.9%
278 Chapter 12
Comment: Only 36.9% of the 254.95 MW heat input to the combustion cham-
ber is available for electricity generation. The remaining 63.1%, which is about
161 MW, ends up in the atmosphere with the exhaust gases released into the
atmosphere at 757.7 K by the turbine. Note that for each MW of electric power
generation there is at least 1.7 (=161/93.95) MW of power wasted. All this
waste energy reaching the environment is a source of thermal pollution.
(c) Since the heating value of the fuel is assumed to be 42 MJ/kg, the mass
ow rate of fuel supplied to the combustion chamber can be calculated as
mass ow rate of the fuel =
[

Q
in
]
comb
heating value of the fuel
=
254.95 MJ/s
42 MJ/kg
= 6.07 kg/s
Comment: The fuel-air mass ratio is therefore about 0.017. In other words,
the fuel mass ow rate is only about 1.7% of the air mass ow rate.
(d) The solutions obtained above are valid only under the ve assumptions made.
In reality, Assumption 1 hardly holds. That is, the ow through the compressor
and the ow through the turbine are far from reversible and adiabatic in reality.
Therefore, the actual exit temperatures of the air leaving the compressor and
the gases leaving the turbine would be very dierent from those calculated in
part (a). It will cause the actual amount of work input to the compressor to
increase and the actual amount of work produced by the turbine to decrease.
These dierences will cause the back work ratio to increase and the thermal
eciency to decrease.
Assumption 2 is also not valid since the mass ow rate through the turbine
is greater than the mass ow rate through the compressor, and the dierence is
the mass ow of the fuel added to the combustion chamber. However, since the
fuel mass ow rate is only about 1.7% of the air mass ow rate, as calculated
in part (c), Assumption 2 would not have introduced any appreciable error. For
the same reason, treating the combustion gases as air, as per Assumption 3,
would not have introduced any appreciable error, either. Assumptions 4 and 5,
however, would introduce some bias in the solutions obtained.
Nevertheless, the solutions obtained above under ideal conditions certainly
give a very good idea about the performance of the gas turbine. For example,
the eciency of the gas turbine in reality will always be less than, and never
more than, 36.9%. And, more than 63.1% of the heat input to the combustion
chamber will be lost to the environment, causing thermal pollution.
Example 12.2
Rework Example 12.1 with a regenerator
unit included in the gas turbine power plant as shown in Figure 12.3.
combustion
chamber
compressor
turbine
gases
shaft
fuel
atmospheric
air
Figure 12.3 Flow diagram of a gas turbine power plant with regeneration.
regenerator
T
1
T
2
T
5
T
3
T
4
T
6
exhaust
gases
A regenerator is used to recover part of the energy lost to the envi-
ronment with the exhaust gases leaving the turbine at high temperatures.
It is simply a heat exchanger in which the compressed air is preheated by
the hot gases leaving the turbine as shown in the gure. Let us assume
that adiabatic conditions prevails at the regenerator and that there is no
pressure drop across it.
(a) Determine the power input to the compressor, power production of
the turbine, and the power available for electricity generation. De-
termine also the back work ratio.
(b) Calculate the heat input to the combustion chamber, and the thermal
eciency of the gas turbine plant.
(a) The pressure and the temperature of the air entering the compressor, the
pressure of the air leaving the compressor, the temperature of the gases entering
the turbine, and the pressure of the gases leaving the turbine are all the same as in
Example 12.1. Hence, the exit temperature of the air leaving the compressor,
280 Chapter 12
the work input to compressor, the exit temperature of the gases leaving the
turbine and the work produced by the turbine are all the same as those calculated
in the Solution to Example 12.1.
That is, T
2
= 475.2 K, [(

W
s
)
in
]
comp
= 61.63 MW, T
4
= 757.7 K, and
[(

W
s
)
out
]
turb
= 155.58 MW. Therefore, the power available for electricity gener-
ation and the back work ratio are the same as those calculated in the Solution
to Example 12.1, which are 93.95 MW and 36.9%, respectively.
(b) The use of regenerator would cause the heat input to the combustion cham-
ber to be lower than that was calculated in the Solution to Example 12.1,
since the compressed air is preheated by the hot gases leaving the turbine in the
regenerator before it enters the combustion chamber.
Since the regenerator is a heat exchanger, assuming adiabatic condition,
(10.19) can be used to get
m
gases
m
air
=
(C
p
)
air
(T
5
T
2
)
(C
p
)
gases
(T
4
T
6
)
Since the mass ow rate of the gases is assumed to be the same as that of
the air, C
p
is assumed to be the same for both air and gases, T
2
= 475.2 K and
T
4
= 757.7 K, we get
T
5
475.2 K = 757.7 K T
6
where T
5
and T
6
are unknown.
For the heat to ow from the gases to the air within the heat exchanger,
T
6
should be higher than T
2
(= 475.2 K). If, for example, we take T
6
to be
500 K then T
5
would be 732.9 K. The heat input to the air owing through the
combustion chamber can then be determined as
[

Q
in
]
comb
= mC
p
(T
3
T
5
)
= 350 1.005 (1200 732.9) kJ/s = 164.30 MJ/s
which is about 90.65 MW less than the heat input to the combustion chamber
without a regenerator as in the Example 12.1.
The thermal eciency of the gas turbine plant is calculated as
th
=
net work output of the gas turbine plant
heat input to the gas turbine plant
=
155.58 MW61.63 MW
164.30 MW
=
93.95
164.30
= 57.2%
Comment: When using a regenerator to preheat the compressed air by the hot
gases leaving the turbine, the heat requirement of the combustion chamber is
reduced. So that the thermal eciency of the gas turbine power plant increases
to 57.2% from 36.9%, obtained without the regenerator in the Solution to
Example 12.1. That is, about 57.2% of the 164.30 MW heat input to the
combustion chamber is available for electricity generation. The remaining 42.8%
of the heat input, which is about 70 MW, reaches the atmosphere with the ex-
haust gases released into the atmosphere at 500 K by the regenerator. Note that
for each MW of electric power generation there is about 0.75 (=70/93.95) MW
of power wasted into the environment. Thermal pollution caused by the gas
turbine power plant with a regenerator is therefore considerably lower than the
thermal pollution caused by the gas turbine power plant without a regenerator.
12.2 Gas Turbine for Jet Propulsion
Gas turbine is an essential part of a turbojet engine commonly used for
aircraft propulsion. A turbojet engine consists of a diuser, compressor,
combustion chamber, turbine and a nozzle, as shown in the schematic of a
turbojet engine in Figure 12.4.
diuser compressor
combustion
chamber
tur-
bine nozzle
Figure 12.4 Schematic of a turbojet engine.
1
2
3 4
5
6
- - - - -
282 Chapter 12
The inlet of a turbojet engine is shaped into a diuser in which the
ambient air entering the turbojet engine is slowed down to near zero speed.
Reduction in the speed of the air owing through the diuser is accom-
panied by increase in the air pressure. The slightly compressed air enters
the compressor in which it is compressed to a high pressure. The exit
pressure of the compressor can be 7 to 25 times higher than the inlet pres-
sure. The high pressure air leaving the compressor enters the combustion
chamber, where fuel is sprayed onto the compressed air and the resultant
mixture is burned. The hot products of combustion at a high pressure and
a temperature enter the turbine, and sets the turbine shaft on rotation.
The compressor-combustion chamber-turbine combination of the tur-
bojet engine functions in a manner very similar to that of the gas turbine
power plant discussed in Section 12.1. In the turbojet engine, however, tur-
bine produces just enough power to drive the compressor shaft and some
other devices such as a small generator. Therefore, almost all the work
output of the turbine can be considered as being consumed by the com-
pressor in the turbojet engine, unlike in the case of the gas turbine power
plant in which a good portion of the turbine power output is used for the
generation of electricity.
The gases leaving the turbine of the turbojet engine enter a nozzle, and
attain high speed as they ow through the nozzle which is accompanied
by a pressure reduction. The high speed gases leaving the turbojet engine
imparts a thrust on the aircraft so as to propel the aircraft forward. The
thrust equation for a turbojet engine can be derived from the Newtons
second law, for the case where the inlet pressure is the same as the exit
pressure, as
Net Thrust = m
air
(V
exit
V
inlet
) (12.1)
where V
exit
is the exit velocity of the gases leaving the nozzle relative to
the aircraft and V
inlet
is the inlet velocity of the air entering the diuser
relative to the aircraft. In Figure 12.4, the inlet is marked by 1 and the exit
is marked by 6. In deriving (12.1), we have omitted the fact that the mass
ow rate of the gases leaving the turbojet engine diers from the mass ow
rate of air entering the engine by the mass ow rate of the fuel supplied to
the combustion chamber. Since the fuel-air mass ratio used in the turbojet
engine is usually very small, the above omission does not introduce any
appreciable error in the calculation of the net thrust.
Example 12.3
Air enters a diuser of the turbojet engine
of an aircraft ying at a speed of 300 m/s at an altitude where the pressure
is 0.95 bar and the temperature is 10
o
C. Air leaving the diuser with a
negligibly small speed enters the compressor which has a pressure ratio of
9:1. Each kg of compressed air entering the combustion chamber receives
about 650 kJ of heat as it passes through the combustion chamber at
constant pressure. The gases leaving the combustion chamber enter the
turbine at a high temperature and a pressure, set the turbine shaft on
rotation, and leave the turbine. The gases leaving the turbine pass through
the nozzle where they achieve high speeds. The turbojet engine is so
designed that the pressure of the gases at the exit of the nozzle falls back
to 0.95 bar. Assume that the ow within the turbojet engine except in
the combustion chamber is reversible and adiabatic and that all the work
output of the turbine is used to drive the compressor. Neglect the speed
of the ow through the turbojet engine except at the inlet and the exit of
the engine. Also, neglect the eect of fuel ow rate.
(a) Determine the pressures and the temperatures at the inlets and the
outlets of the diuser, compressor, combustion chamber, turbine and
the nozzle of the turbojet engine.
(b) Determine the speed of the gases at the nozzle exit.
(c) Compute the forward thrust imparted on the turbojet engine per kg
of the air owing through the engine.
Let us use the schematic of the turbojet engine shown in Figure 12.4 and the
labels 1, 2, 3, 4, 5 and 6 on it to mark the states of the uid entering/leaving
the diuser, compressor, combustion chamber, turbine and the nozzle of the
turbojet engine.
Flow through the Diuser:
At the diuser inlet, P
1
= 0.95 bar, T
1
= 283 K and c
1
= 300 m/s, where
c
1
denotes the speed of the air at the diuser inlet. At the diuser exit, c
2
= 0,
where c
2
denotes the speed of the air at the diuser exit.
The steady ow energy equation applicable for the adiabatic ow through a
284 Chapter 12
diuser is used to determine T
2
as
T
2
= T
1
+
c
2
1
c
2
2
2 C
p
= 283 K +
300
2
m
2
/s
2
2 1005 J/kg K
= 327.8 K
Since the ow through the diuser is assumed to be reversible and adiabatic,
(7.31) gives
P
2
= P
1
T
2
T
1
/(1)
= 0.95 bar
327.8
283
1.4/0.4
= 1.59 bar
P
2
= 1.59 bar and T
2
= 327.8 K at the diuser exit, which is also the
compressor inlet. The speed of the ow is assumed to be negligible at this cross-
section.
Flow through the Compressor:
The compressor has a pressure ratio of 9:1, so that
P
3
= 9 P
2
= 9 1.59 bar = 14.31 bar
Since the ow through the compressor is assumed to be reversible and adi-
abatic, (7.31) gives
T
3
= T
2
P
3
P
2
(1)/
= 327.8 K
9 P
2
P
2
0.4/1.4
= 614.1 K
P
3
= 14.31 bar and T
3
= 614.1 K at the compressor exit, which is also the
combustion chamber inlet. The speed of the ow is assumed to be negligible at
this cross-section.
Flow through the Combustion Chamber:
The ow through the combustion chamber is assumed to be at constant
pressure. So that
P
4
= P
3
= 14.31 bar
Each kg of compressed air entering the combustion chamber receives about
650 kJ of heat as it passes through the combustion chamber. Neglecting the
eect of fuel ow rate, applying the steady ow energy equation to the ow
through the combustion chamber gives
650 kJ/kg = C
p
(T
4
T
3
)
from which T
4
can be found as
T
4
= T
3
+
650 kJ/kg
C
p
=
614.1 +
650
1.005
K = 1260.9 K
P
4
= 14.31 bar and T
4
= 1260.9 K at the combustion chamber exit, which
is also the turbine inlet. The speed of the ow is assumed to be negligible at
this cross-section.
Flow through the Turbine:
Since all the work output of the turbine is assumed to be used to drive the
the compressor, we have
[(

W
s
)
out
]
turbine
= [(

W
s
)
in
]
compressor
Using the steady ow energy equation to both the turbine and the compres-
sor, we can expand the above equation to
m
gases
(C
p
)
gases
(T
4
T
5
) = m
air
(C
p
)
air
(T
3
T
2
)
Since the eect of fuel ow rate is ignored, the mass ow rates of the gases
and of air can be taken as equal. The values of C
p
for air and for the gases can
be taken as equal as well. Therefore, we can calculate T
5
using
T
5
= T
4
T
3
+T
2
= (1260.9 614.1 + 327.8) K = 974.6 K
Since the ow through the turbine is assumed to be reversible and adiabatic,
(7.31) gives
P
5
= P
4
T
5
T
4
/(1)
= 14.31 bar
974.6
1260.9
1.4/0.4
= 5.81 bar
P
5
= 5.81 bar and T
5
= 974.6 K at the turbine exit, which is also the nozzle
inlet. The speed of the ow is assumed to be negligible at this cross-section.
Flow through the Nozzle:
The pressure of the gases at the exit of the nozzle falls back to 0.95 bar.
Therefore
P
6
= 0.95 bar
Since the ow through the nozzle is assumed to be reversible and adiabatic,
(7.31) gives
T
6
= T
5
P
6
P
5
(1)/
= 974.6 K
0.95
5.81
0.4/1.4
= 580.9 K
Steady ow energy equation is applied to the ow through the nozzle to
determine c
6
as
c
6
=
2 C
p
(T
5
T
6
)
=

2 1005 (974.6 580.9) J/kg = 890 m/s
286 Chapter 12
P
6
= 0.95 bar and T
6
= 580.9 K at the nozzle exit. The speed of the ow
at the nozzle exit is 890 m/s.
Comment: Such high speed at the nozzle exit is achieved under the assumed
ideal conditions, such as the ow within the turbojet engine except in the com-
bustion chamber being reversible and adiabatic.
Forward thrust imparted on the turbojet engine:
Since the exit pressure is the same as the inlet pressure, the forward thrust
imparted on the turbojet engine per kg of the air owing through the engine is
Net Thrust
m
air
= (c
6
c
1
) = (890 300) m/s = 590 N per kg/s
12.3 Steam Turbine for
Electric Power Generation
In a gas turbine used for electric power generation, the shaft of the
turbine is rotated by the gases produced in the burning of a fuel with air.
In a steam turbine used for electric power generation, superheated steam
is used to rotate the shaft of the turbine. The basic working principle of a
simple steam turbine used for electric power generation is explained below
with the help of the ow diagram shown in Figure 12.5.
Saturated water entering the pump is compressed to a high pressure and
the compressed water is fed to the steam generator, which is sometimes
referred to as the boiler. The compressed water is heated to superheated
steam state in the steam generator, which is a large heat exchanger where
the heat is transferred from the hot combustion gases to the water. The
superheated steam leaving the steam generator at a high pressure and a
temperature enters the turbine, where it expands rotating the turbine shaft.
The work output of the rotating turbine shaft is used to produce elec-
tricity by spinning a coil between the poles of a magnet or an electromagnet.
Thus, part of the heat transferred from the hot combustion gases to the
water in the steam generator is converted into useful electrical energy. The
wet steam leaving the turbine is condensed to saturated water state in a
condenser, which is also a large heat exchanger where the heat is trans-
ferred from the steam to cooling water. The saturated water leaving the
condenser enters the pump, thus making a cyclic ow through the pump,
steam generator, turbine and condenser.
The combustion gases leaving the steam generator, rich in pollutants
such as the greenhouse gas carbon dioxide, enter the atmosphere. The
cooling water leaving the condenser at an elevated temperature is cooled
in the cooling towers, by transferring considerable amount of heat to the
atmosphere, and thereby causing thermal pollution.
turbine
pump
2
4
Figure 12.5 Flow diagram of a simple steam turbine power plant.
steam generator
condenser
cooling water
3
hot gases
1
_
Example 12.4
In the steam turbine power plant, shown in
Figure 12.5, assume that saturated water at 0.08 bar owing at a rate of
50 kg/s is compressed by the pump to 70 bar. The compressed water is
fed to the steam generator where it is converted to superheated steam at
450
C at the same pressure. The superheated steam expanding through

the turbine, leaves the turbine as wet steam at 0.08 bar. The wet steam is
288 Chapter 12
condensed to saturated water state in the condenser, thus completing the
cycle.
(a) Determine the enthalpies of the ow at the inlets and the outlets
of the turbine and the pump, assuming reversible adiabatic ows
through the turbine and the pump.
(b) Determine the power production at the turbine, power requirement
of the pump, and the back work ratio, dened as the ratio of the
pump work to the turbine work.
(c) Determine the heat input at the steam generator, and the thermal
eciency of the steam turbine plant, dened as the ratio of net work
out to heat in.
(d) Determine the heat rejected at the condenser.
(e) Calculate the cooling water mass ow rate if the cooling water tem-
perature is raised from 32
C to about 2.5
C less than the temperature

of the wet steam condensing in the condenser. Take cooling water
C
p
as 4.2 kJ/kg K.
(a) Let us use the ow diagram of the simple steam turbine power plant shown in
Figure 12.5 and the labels 1, 2, 3 and 4 on it to mark the states of water/steam
entering or leaving the components of the steam turbine power plant.
At state 3, which is the turbine inlet, we have superheated steam at 70
bar and 450
C. The specic enthalpy found from a Superheated Steam Table is

h
3
= 3287 kJ/kg.
At state 4, which is the turbine outlet, we have wet steam at 0.08 bar. Since
the ow through the turbine is assumed to be reversible adiabatic, s
4
= s
3
=
s at 70 bar and 450
C = 6.632 kJ/kg K.
For state 4 at 0.08 bar and s
4
= 6.632 kJ/kg K, the dryness fraction can
be calculated using
x
4
=
s
4
s
f
s
fg
=
6.632 0.593
7.634
= 0.7911
The specic enthalpy is then
h
4
= h
f
+x
4
h
fg
= 174 + 0.7911 2402 = 2074 kJ/kg
At state 1, which is the pump inlet, we have saturated water at 0.08 bar.
The specic enthalpy is h
1
= 174 kJ/kg.
At state 2, which is the pump outlet, we have compressed water at 70
bar. Since the ow through the pump is assumed to be reversible adiabatic,
s
2
= s
1
= s
f
at 0.08 bar = 0.593 kJ/kg K.
State 2 at 70 bar and s
2
= 0.593 kJ/kg K is a compressed water state since
s
f
at 70 bar is 3.122 kJ/kg K. We should therefore be able to nd h
2
using
a Compressed Water Table. However, since data for compressed water is not
easily found, let us use the following convenient but an approximate method to
nd h
2
.
The work input to a pump with adiabatic ow is expressed by (10.11). The
work input to a pump with reversible ow is approximated by (11.28). Since the
given ow is reversible adiabatic, we combine (10.11) and (11.28) to get h
2
as
follows:
m(h
2
h
1
) mv
1
(P
2
P
1
)
h
2
h
1
+v
1
(P
2
P
1
) (12.2)
where h
1
is known, v
1
= v
f
at 0.08 bar = 0.0010084 m
3
/kg, P
1
= 0.08 bar and
P
2
= 70 bar. Therefore, we have
h
2
174 kJ/kg + 0.0010084 m
3
/kg (7000 8) kPa = 181 kJ/kg
Summarizing the results obtained above, we have
State 1 2 3 4
Condition saturated compressed superheated wet
water water steam steam
P (in bar) 0.08 70 70 0.08
T (in

C) 41.5 - 450 41.5
h (in kJ/kg) 174 181 3287 2074
x 0 - - 79.11%
(b) The power production of the turbine must be determined. Using (10.9) for
the ow through an adiabatic turbine, we have
[(

W
s
)
out
]
turb
= m(h
3
h
4
) = 50 (3287 2074) kJ/s = 60.65 MW
The power requirement of the pump must be determined. Using (10.11) for
the ow through an adiabatic pump, we have
[(

W
s
)
in
]
pump
= m(h
2
h
1
) = 50 (181 174) = 0.35 MW
bwr =
pump work input
turbine work output
=
0.35 MW
60.65 MW
= 0.6%
290 Chapter 12
Comment: The power consumption of the pump to compress water from 0.08
bar to 70 bar is only about 0.6% of the power production of the turbine. That is,
almost all the work produced by the turbine is available for electricity generation.
It is an advantage that a steam turbine power plant has over a gas turbine power
plant.
(c) Heat input to the steam generator is calculated by applying (10.3) to the
uid owing through the steam generator as
[

Q
in
]
steam generator
= m(h
3
h
2
)
= 50 (3287 181) kJ/s = 155.30 MW
The thermal eciency of the steam turbine plant is calculated as
th
=
net work out
heat in
=
60.65 MW0.35 MW
155.30 MW
=
60.30
155.30
= 38.8%
Comment: Only about 38.8% of the 155.30 MW heat input to the steam
generator is available for electricity generation.
(d) Heat rejected at the condenser is calculated by applying (10.3) to the uid
owing through the condenser as
[

Q
out
]
condenser
= m(h
4
h
1
)
= 50 (2074 174) kJ/s = 95.00 MW
Comment: The percentage of the heat input in the steam generator that is
rejected by the condenser is calculated using (95.00/155.30)100, which equals
61.2%. In other words, for each MW of electric power generation there is at
least about 1.6 (=95.00/60.30) MW of power is wasted. All this waste energy
reaching the environment is a source of thermal pollution.
(e) Steam condenses in the condenser at the saturated temperature at 0.08 bar,
which is 41.5
C. The cooling water temperature is therefore raised from 32
C to
39
C. Assume that the cooling water absorbs all that 95.00 MW of heat rejected
at the condenser. The mass ow rate of the cooling water is calculated as
m
cooling water
=
95.00 MW
4.2 (39 32) kJ/kg
= 3231 kg/s = 11.63 10
6
kg/h
Example 12.5
Consider the schematic of the steam turbine
power plant shown in Figure 12.6. Saturated water at 0.08 bar owing at
a rate of 50 kg/s is compressed reversibly and adiabatically by a pump to
70 bar. The compressed water is fed to a steam generator where it is con-
verted to superheated steam at 450
C at the same pressure. The steam

ows reversibly and adiabatically through a HP (high pressure) turbine,
and leaves the turbine at 7 bar. The steam leaving the turbine is reheated
to 425
C, and fed to the LP (low pressure) turbine. The steam owing

reversibly and adiabatically through the LP turbine, leaves it as wet steam
at 0.08 bar. The wet steam is condensed to saturated water state in the
condenser, thus the cycle is completed.
pump
2
6
Figure 12.6 Flow diagram of a steam turbine with a reheater.
steam generator
condenser
cooling water
3
reheater
hot gases
hot gases
1
_
HP
turbine
LP
turbine
5
4
(a) Determine the enthalpies of the ow at the inlets and the outlets of
the turbines and the pump.
(b) Determine the combined power production at the HP and the LP
turbines, power requirement of the pump, and the back work ratio.
(c) Determine the total heat input to the steam generator and the re-
heater, and the thermal eciency of the steam turbine plant.
(d) Determine the heat rejected at the condenser.
292 Chapter 12
At state 1, which is the pump inlet, we have saturated water at 0.08 bar.
Therefore, h
1
= 174 kJ/kg.
At state 2, which is the pump outlet, we have compressed water at 70 bar.
Since the ow through the pump is reversible adiabatic, we get h
2
181 kJ/kg,
as worked out in the Solution to Example 12.4.
At state 3, which is the HP turbine inlet, we have superheated steam at 70
bar and 450
C. Therefore, h
3
= 3287 kJ/kg.
At state 4, which is the HP turbine outlet, we have steam at 7 bar. Since the
ow through the turbine is reversible adiabatic, s
4
= s
3
C =
6.632 kJ/kg K. For a state at 7 bar and s
4
= 6.632 kJ/kg K, the dryness frac-
tion can be calculated using
x
4
=
s
4
s
f
s
fg
=
6.632 1.992
4.717
= 0.9837
h
4
= h
f
+x
4
h
fg
= 697 + 0.9837 2067 = 2730 kJ/kg
At state 5, which is the LP turbine inlet, we have superheated steam at 7
bar and 425
C. Therefore, h
5
= 3322 kJ/kg.
At state 6, which is the LP turbine outlet, we have wet steam at 0.08
bar. Since the ow through the turbine is reversible adiabatic, s
6
= s
5
=
s at 7 bar and 425
C = 7.710 kJ/kg K. For a state at 0.08 bar and s

6
= 7.710
kJ/kg K, the dryness fraction can be calculated using
x
6
=
s
6
s
f
s
fg
=
7.710 0.593
7.634
= 0.9323
h
6
= h
f
+x
6
h
fg
= 174 + 0.9323 2402 = 2413 kJ/kg
State 1 2 3 4 5 6
Condition sat. comp. super. wet super. wet
water water steam steam steam steam
P (in bar) 0.08 70 70 7 7 0.08
T (in

C) 41.5 - 450 165 425 41.5
h (in kJ/kg) 174 181 3287 2730 3322 2413
x 0 - - 98.37% - 93.23%
Note: sat. stands for saturated, comp. for compressed, and super. for superheated.
(b) Using (10.9) for the ow through the adiabatic HP turbine, we have
[(

W
s
)
out
]
HPturbine
= m(h
3
h
4
) = 50 (3287 2730) kJ/s
= 27.85 MW
Using (10.9) for the ow through the adiabatic LP turbine, we have
[(

W
s
)
out
]
LPturbine
= m(h
5
h
6
) = 50 (3322 2413) kJ/s
= 45.45 MW
The combined power production at the HP and the LP turbines is the sum-
mation of the power productions of the HP and the LP turbines, which is 73.30
MW.
Using (10.11) for the ow through an adiabatic pump, we have
[(

W
s
)
in
]
pump
= m(h
2
h
1
) = 50 (181 174) = 0.35 MW
bwr =
pump work input
combined turbine work output
=
0.35 MW
73.30 MW
= 0.5%
(c) Heat input to the steam generator is calculated by applying (10.20) to the
[

Q
in
]
steam generator
= m(h
3
h
2
)
= 50 (3287 181) kJ/s = 155.30 MW
Heat input to the reheater is calculated by applying (10.20) to the uid
owing through the reheater as
[

Q
in
]
reheater
= m(h
5
h
4
)
= 50 (3322 2730) kJ/s = 29.60 MW
The total heat input to the steam generator and the reheater is the summa-
tion of the heat inputs to the steam generator and the reheater, which is 184.90
MW.
th
=
net work out
heat in
=
73.30 MW0.35 MW
184.90 MW
=
72.95
184.90
= 39.5%
294 Chapter 12
Comment: Only about 39.5% of the 184.90 MW combined heat input to the
steam generator and the reheater is available for electricity generation.
(d) Heat rejected at the condenser is calculated by applying (10.21) to the uid
[

Q
out
]
condenser
= m(h
6
h
1
)
= 50 (2413 174) kJ/s = 111.95 MW
Comment: The percentage of the combined heat input that is rejected by
the condenser is calculated using (111.95/184.90)100, which equals 60.5%. In
other words, for each MW of electric power generation there is at least about
1.5 (=111.95/72.95) MW of power is wasted. All this waste energy reaching
the environment is a source of thermal pollution.
Example 12.6
Consider the schematic of the steam turbine
power plant shown in Figure 12.7. saturated water at 7 bar owing at a
rate of 50 kg/s is compressed adiabatically by a pump to 70 bar, and is fed
to a steam generator where it is converted to superheated steam at 450
C
at the same pressure. The superheated steam ows adiabatically through
the 1
st
stage turbine, and leaves it at 7 bar. A part of the steam leaving
the 1
st
stage turbine is fed to an open feedwater heater operated at 7 bar.
(An open feedwater heater is simply a mixing chamber in which a hot uid
stream and a cold uid stream mix with each other to form a uid stream
at intermediate temperature.) The remaining steam is fed to the 2
nd
stage
turbine, through which it ows adiabatically, and leaves it as steam at 0.08
bar. It is condensed to saturated water state at the same pressure in the
condenser, compressed adiabatically by a second pump to 7 bar, and fed
to the open feedwater heater, thus the cycle is completed.
(a) Determine the enthalpies of the ow at the inlets and the outlets of
the turbines and the pumps. Assume reversible ows through the
pumps and the turbines.
(b) Determine the mass ow rate of the steam diverted to the open
feedwater heater from the exit of the 1
st
stage turbine, assuming
adiabatic conditions at the open feedwater heater.
(c) Determine the combined power production at the turbines, combined
power requirement of the pumps, and the back work ratio.
(d) Determine the total heat input to the steam generator, and the ther-
mal eciency of the steam turbine plant.
(e) Determine the heat rejected at the condenser.
1
st
pump
2
5
Figure 12.7 Flow diagram of a steam turbine with an open
feedwater heater.
steam generator
condenser
cooling water
3
hot gases
_
1
st
turbine
2
nd
turbine
4
4
2
nd
pump
6
_
open
feedwater
heater
4
7 1
At state 1, which is the inlet of the rst pump, we have saturated water at
7 bar. Therefore, h
1
= 697 kJ/kg.
At state 2, which is the outlet of the rst pump, we have compressed water
at 70 bar. Since the ow through the pump is assumed to be reversible adiabatic,
h
2
is calculated using (12.2) as
h
2
h
1
+v
1
(P
2
P
1
) = 697 + 0.0011082 (7000 700) = 704 kJ/kg
At state 3, which is the inlet of the 1
st
stage turbine, we have superheated
C. At state 4, outlet of the 1

st
stage turbine, we
have steam at 7 bar. The ow through the turbine is assumed to be reversible
296 Chapter 12
adiabatic. Therefore, as found in the Solution to Example 12.5, h
3
= 3287
kJ/kg, x
4
= 0.9837, and h
4
= 2730 kJ/kg.
The wet steam leaving the 1
st
stage turbine is divided into two streams, one
entering the 2
nd
stage turbine and the other entering the open feedwater heater.
All these streams are assumed to be at state 4.
At state 5, which is the outlet of the 2
nd
stage turbine, we have steam at
0.08 bar. Since the ow through the 2
nd
stage turbine is reversible adiabatic,
s
5
= s
4
= s
3
C = 6.632 kJ/kg K. For state 5 at 0.08

bar and s
5
= 6.632 kJ/kg K, the dryness fraction can be calculated using
x
5
=
s
5
s
f
s
g
s
f
=
6.632 0.593
7.634
= 0.7911
h
5
= h
f
+x
5
h
fg
= 174 + 0.7911 2402 = 2074 kJ/kg
At state 6, which is the inlet of the second pump, we have saturated water
at 0.08 bar. Therefore, h
6
= 174 kJ/kg.
At state 7, which is the outlet of the second pump, we have is compressed
water at 7 bar. Since the ow through the pump is assumed to be reversible
adiabatic, h
2
is calculated using (12.2) as
h
7
h
6
+v
6
(P
7
P
6
) = 174 + 0.0010084 (700 8) = 174.7 kJ/kg
State 1 2 3 4 5 6 7
Condition sat. comp. super. wet wet sat. comp.
water water steam steam steam water water
P (in bar) 7 70 70 7 0.08 0.08 7
T (in

C) 165 - 450 165 41.5 41.5 -
h (in kJ/kg) 697 704 3287 2730 2074 174 174.7
x 0 - - 98.37% 79.11% 0 -
(b) Take the mass ow rate of the steam diverted to the open feedwater heater
from the exit of the 1
st
stage turbine as m
o
kg/s. The steam entering the 2
nd
stage turbine is therefore (50 - m
o
) kg/s, which is of course the same amount
pumped into the open feedwater heater by the second pump.
Energy balance over the adiabatic open feedwater heater, which in eect is
an adiabatic mixing chamber, is expressed by (10.16). Applying (10.16) to the
adiabatic open feedwater heater of Figure 12.7, we have
(50 m
o
) (h
1
h
7
) = m
o
(h
4
h
1
)
which gives
m
o
=
h
1
h
7
h
4
h
7
50 kg/s
Substituting the known enthalpies, we get
m
o
=
697 174.7
2730 174.7
50 kg/s = 0.2044 50 kg/s = 10.22 kg/s
(c) Using (10.9) for the ow through the adiabatic 1
st
stage turbine, we have
[(

W
s
)
out
]
1
st
stage turbine
= m(h
3
h
4
)
= 50 (3287 2730) kJ/s
= 27.85 MW
Using (10.9) for the ow through the adiabatic 2
nd
stage turbine, we have
[(

W
s
)
out
]
2
nd
stage turbine
= m(h
4
h
5
)
= (50 m
o
) (2730 2074) kJ/s
= 26.10 MW
The combined power production of the two turbines is the summation of the
power productions of the 1
st
stage and the 2
nd
stage turbine, which is = (27.85
+ 26.10) MW = 53.95 MW.
Using (10.11) for the ow through an adiabatic rst pump, we have
[(

W
s
)
in
]
1
st
pump
= m(h
2
h
1
)
= 50 (704 697) = 0.35 MW
Using (10.11) for the ow through an adiabatic second pump, we have
[(

W
s
)
in
]
2
nd
pump
= m(h
7
h
6
)
= (50 m
o
) (174.7 174) = 0.03 MW
bwr =
combined pump work input
=
(0.35 + 0.03) MW
53.95 MW
= 0.7%
(d) Heat input to the steam generator is calculated by applying (10.20) to the
[

Q
in
]
steam generator
= m(h
3
h
2
)
= 50 (3287 704) kJ/s = 129.15 MW
298 Chapter 12
th
=
net work out
heat in
=
combined turbine work - combined pump work
heat in
=
53.95 MW(0.35 + 0.03) MW
129.15 MW
=
53.57
129.15
= 41.5%
(e) Heat rejected at the condenser is calculated by applying (10.21) to the uid
[

Q
out
]
condenser
= m(h
5
h
6
)
= (50 m
o
) (2074 174) kJ/s = 75.58 MW
Comment: For each MW of power produced by the turbine, about 1.4 MW
of power is wasted. All this waste energy reaching the environment is a source
of thermal pollution.
12.4 Gas Turbine - Steam Turbine
Combined Power Plant
One of the major drawbacks in using a gas turbine power plant for
electric power generation in comparison to a steam turbine power plant is
the back work ratio of the gas turbine plant (see, Example 12.1) being
considerably higher than the back work ratio of the steam turbine power
plant (see, Example 12.4). Nearly half of the power produced by the
gas turbine is consumed by the compressor, which is used to compress the
atmospheric air to a high pressure. In the steam turbine power plant, the
pump, which is used to compress the water at a vacuum pressure to a
high pressure, consumes less than about 1% of the power produced by the
turbine.
Besides, in a gas turbine power plant, the gases produced in the burning
of a fuel with air, after expanding through the turbine, are emitted into the
atmosphere at a high temperature. Also, the mass ow rate of these hot
exhaust gases is large owing the high air-fuel ratio used in the gas turbine.
In a steam turbine power plant, on the other hand, hot gases produced
by the combustion is used to superheat steam (see, Figure 12.5), which
expands through the turbine causing the turbine shaft to rotate.
It is therefore advisable to combine the gas turbine and the steam tur-
bine such that the hot exhaust gases leaving the gas turbine power plant
can be used to generate the superheated steam required by the steam tur-
bine power plant. Such is practised in power plants known as the combined
gas turbine - steam turbine power plants, and the demand for which is
increasing dramatically worldwide over the recent years. The basic working
principle of a combined simple gas turbine - steam turbine power plant used
for electric power generation is shown in the ow diagram of Figure 12.8.
combustion
chamber
compressor
gas
turbine
gases
shaft
fuel
shaft power
for generation
of electricity
air
Figure 12.8 Flow diagram of a simple gas turbine - steam turbine
combined power plant.
steam
turbine
shaft power
for generation
of electricity
`
_
HRSG
pump
cooling water
exhaust gases
to stack
1
2 3
4
5
6
7
8
9
condenser
300 Chapter 12
The crucial feature of a combined power plant is the heat recovery
steam generator, abbreviated HRSG, shown in Figure 12.8. HRSG is basi-
cally a heat exchanger in which the hot gases leaving the gas turbine heats
the compressed water supplied by the pump to superheated steam required
by the steam turbine. Since the heat input to the HRSG is the heat that
would have otherwise been lost to the environment, the overall thermal
eciency of a combined plant in general is high.
Example 12.7
Combine the gas turbine power plant of Ex-
ample 12.1 and the steam turbine power plant of Example 12.4 using
a heat recovery steam generator as shown in Figure 12.6. The mass ow
rate of air through the gas turbine is 350 kg/s and the mass ow rate of
water through the steam turbine is 50 kg/s. The properties at the states
marked 1 to 9 in the gure are as tabulated below:
State 1 2 3 4 5 6 7 8 9
Condition air air gases gases gases sat. comp. super. wet
water water steam steam
P (in bar) 1 5 5 1 1 0.08 70 70 0.08
T (in

C) 27 202.2 927 484.7 T
5
41.5 41.8 450 41.5
Assume adiabatic conditions at the HRSG and reversible adiabatic ows
through the compressor, pump and the turbines. Ignore the fuel ow rate.
Take C
p
and for air and the gases as 1.005 kJ/kg K and 1.4, respectively.
(a) Determine the combined power production at the turbines, combined
power requirement of the compressor and the pump, and the back
work ratio.
(b) Determine the heat input to the combined power plant, and the
overall thermal eciency of the plant.
(c) Determine the net energy rejection to the environment by the com-
bined power plant.
(d) Determine the heat rejection by the condenser and the loss of energy
to the environment with the exhaust leaving the HRSG.
(e) Determine the temperature of the exhaust gases.
(a) Data for the gas turbine power plant are the same as in Example 12.1, and
for the steam turbine power plant are the same as in Example 12.4. The ows
through the compressor, pump and the turbines are assumed to be reversible and
adiabatic.
The compressor work input and the gas turbine power output are, therefore,
the same as that are evaluated in the Solution to Example 12.1, which are
61.63 MW and 155.58 MW, respectively.
The pump work input and the steam turbine power output are, therefore,
the same as that are evaluated in the Solution to Example 12.4, which are
0.35 MW and 60.65 MW, respectively.
The combined power production at the turbines is the summation of the
power produced at the gas and the steam turbines, which is (155.58 + 60.65)
MW = 216.23 MW
The combined power requirement of the compressor and the pump is the
summation of the power inputs to the compressor and the pump, which is (61.63
+ 0.35 ) MW = 61.98 MW.
The back work ratio is calculated using
bwr =
pump work input + compressor work input
=
61.98 MW
216.23 MW
= 28.7%
Comment: About 28.7% of the combined power production of the turbines is
consumed by the compressor and the pump. The remaining 71.3% is available
for electricity generation. That is, the back work ratio is reduced when a gas
turbine is used combined with the steam turbine.
(b) Heat is supplied to the combined power plant of Figure 12.8 only at the
combustion chamber. Therefore, the heat input to the combined power plant
is the same as that is evaluated in the Solution to Example 12.1, which is
254.95 MW.
302 Chapter 12
The overall thermal eciency of the combined power plant is calculated
using
th
=
net work output of the combined power plant
heat input to the combined power plant
=
216.23 MW61.98 MW
254.95 MW
=
154.25
254.95
= 60.5%
Comment: The thermal eciency of the combined power plant, 60.5%, is
much higher than the thermal eciency of the gas turbine power plant, 36.9%,
or the steam turbine power plant, 38.8%, when operated separately. It is the
principal feature for which the combined power plant is becoming popular as a
mode of electricity generation.
(c) The total heat supply to the combined power plant is 254.95 MW. The net
work output of the plant is 154.25 MW. The net energy rejection to the environ-
ment by the plant is therefore calculated as (254.95 MW - 154.25 MW), which
is 100.70 MW.
Comment: That is, 39.50% of the heat input to the combined power plant is
lost to the environment. In other words, for each MW of power produced, there
is about 0.65 (=100.70/154.24) MW of power wasted. This amount is far less
than the amount of power wasted per MW of power produced in the cases where
the gas turbine and the steam turbine are operated separately. It is yet another
favourable feature that promotes the use of combined power plant for electricity
generation.
(d) Energy rejection at the condenser is the same as that is evaluated in the
Solution to Example 12.4, which is 95.00 MW. The loss of energy to the en-
vironment with the exhaust leaving the HRSG is therefore calculated as (100.70
MW - 95.00 MW), which is 5.7 MW.
(e) To determine the temperature of the exhaust gases leaving the HRSG, which
is T
5
, let us redraw the HRSG part of the combined power plant as in Figure
12.9, with the pressure and temperature data displayed on it.
Treating the HRSG as an adiabatic heat exchanger, we can write the steady
ow energy equation over it to get
m
gases
(C
p
)
gases
(T
4
T
5
) = m
water/steam
(h
8
h
7
)
Substituting the known numerical values in the above expression, we get
350 1.005 (484.7 T
5
) = 50 (3287 181)
where h
8
= 3287 kJ/kg for superheated steam at 70 bar at 450
C and h
7
=
181 kJ/kg for compressed water at 70 bar at 41.8
C. Therefore, we get T
5
=
43
C.
Figure 12.9 HRSG unit of the combined power plant.
exhaust gases
to stack
4
5
7
8
from the
gas turbine
to the
steam turbine from the
pump
1 bar
T
5
1 bar
484.7
C
70 bar
450
C
70 bar
41.8
C
Comment: Note that, in the HRSG, for the heat to ow from the hot gases to
the water/steam mixture, T
4
must be greater than T
8
and T
5
must be greater
than T
7
, and these conditions are satised in the case considered. However, in
reality, it is impractical to reduce the temperature of the exhaust gases leaving
the HRSG to such low values as 43
C.
12.5 Minimizing the Heat Loss
from Power Plants
It is of importance to note that none of the power plant studied in this
chapter succeeds in converting all heat supplied to the power plant into
work. That is, the thermal eciency of no engine is 100%. Ideally, we
would have liked to reach 100% thermal eciency, since it would result in
no waste of the precious heat energy, which we obtain mostly by burning
304 Chapter 12
the fossil fuels that generates carbon dioxide and other greenhouse gases
that are responsible for global warming and the resulting climate change.
Besides, the heat that is lost to the environment from the power plants
causes thermal pollution.
We could have reached 100% thermal eciency, if all heat gained by
the working uid were converted into net work. According to the rst law,
it is possible to convert all heat into work, since the rst law states that
energy cannot be created or destroyed but it can be changed from one form
to another.
But, centuries of experience has shown that it is impossible to convert
all heat into work in engines of the kinds studied in this chapter. This
observation has been generalized into a fundamental law, which, indeed, is
the second law of thermodynamics, an introduction to which is given in the
next chapter.
Chapter 13
INTRODUCTION TO
THE SECOND LAW
There is good reason for wanting to violate the Second Law, for
if it could be done, all of mans energy requirements could forever
be met without any depletion of resources or pollution of his sur-
roundings.
H.C. Van Ness (Understanding Thermodynamics)
Learning thermodynamics even at an introductory level cannot be con-
sidered complete without being told what the second law is all about. This
chapter introduces the second law to a beginner in an unconventional way.
The objective of this chapter is to make the students know why it is impor-
tant to learn the second law, and what role it has in the thermodynamic
analyses of engineering systems.
306 Chapter 13
13.1 The Second Law
In this book, we adopt the most general approach to present the Second
Law of Thermodynamics, which is that of Clausius. He made the following
statement of the second law in 1865:
Total entropy change of any system and its sur-
roundings is positive for a real process, and it ap-
proaches zero when the real process approaches a
reversible process.
The mathematical equivalence of the above statement of the second
law is as follows:
S
total
> 0 for a real (irreversible) process

= 0 for a reversible process
< 0 for an impossible process
(13.1)
The second law is a fundamental law, which means nobody has either
proved or disproved the second law yet. It contains in it information that
has been gathered over several hundred years of observations and experi-
mentations with what is possible and what is not possible in reality.
Student: Teacher, the rst law states energy is conserved. It is easy to under-
stand what the rst law is all about, and therefore to accept it as true.
But, the second law does not make any sense.
Teacher: Well, let me put it this way. The second law of thermodynamics
states that the total entropy of a system and its surroundings together
is conserved for a reversible process, and it increases for a real, I mean
physically realizable, process.
Student: Why should the total entropy of a system and its surroundings to-
gether increases for a real process? What is that physical entity that we
measure using this entropy?
Teacher: It is a bit dicult to answer that question since it is impossible to
relate entropy to a single physical entity. Let me only tell you that entropy
is a property that provides a measure of the molecular disorder.
Introduction to the Second Law 307
Student: What is the connection between molecular disorder and the second
law?
Teacher: The Nature, it appears, prefers the direction of increasing molecular
disorder. Entropy could be used to measure the degree of molecular dis-
order. Thus, we could say that for any thermodynamic process to occur
in real life, the total entropy change of the system and its surroundings,
which is the measure of the total molecular disorder of the system and its
surroundings, must increase.
13.2 Evaluation of Total Entropy Change
Since the value of S can be used to determine whether a process is
real, reversible or impossible, we need to learn about how to determine S.
We shall do that in this section.
For a closed system,
S
total
= S
sys
+ S
surr
(13.2)
where the label sys stands for system and the label surr stands for
surroundings.
Since S is a property, S
sys
can be evaluated using the following:
S
sys
= m
sys
s
sys
= m
sys
(s
f
s
o
)
sys
(13.3)
where the subscript f stands for the nal state and the subscript o stands
for the initial state.
If the surroundings has a nite mass then the entropy dierence between
the nal and the initial states of this nite mass would give the entropy
change of the surroundings. We could therefore use
S
surr
= m
surr
s
surr
= m
surr
(s
f
s
o
)
surr
(13.4)
Expressions developed in Chapter 11 for s of various substances could
be used to evaluate s
sys
and s
surr
of (13.3) and (13.4), as will be
demonstrated in the worked examples of this chapter.
308 Chapter 13
The surroundings is, however, often taken as a thermal reservoir of
innite heat capacity. A thermal reservoir is assumed to remain at a con-
stant temperature regardless of the heat transferred to or from the reser-
voir. It is also assumed that no irreversibilities occur within the reservoir.
With these assumptions, the entropy change of the surroundings taken as
a thermal reservoir is written as
S
surr
=
(Q
in
)
surr
T
surr
(13.5)
where (Q
in
)
surr
denotes the nite amount of heat transferred to the sur-
roundings from the system during the process, and T
surr
denotes the con-
stant temperature of the surroundings in the Kelvin scale.
If the system is thermally isolated from the surroundings during the
process, that is, in an adiabatic process, there is no heat exchange between
the system and the surroundings. Therefore,
S
surr
= 0
which simplies (13.2) to the following:
S
total
= S
sys
for an adiabatic process. (13.6)
Using (13.3), we could write (13.6) as
S
total
= m
sys
(s
f
s
o
)
sys
for an adiabatic process. (13.7)
If the given adiabatic process takes place reversibly then, of course, we
know that the entropy of the system remains a constant (see Section 11.4).
Therefore, (13.7) reduces to
S
total
= 0 for a reversible adiabatic process. (13.8)
To evaluate the entropy change for an open system, we need to incorpo-
rate the entropy of the matter that enters and leaves the system. Since we
will mostly be working with steady ow processes, let us get the expression
for the steady ow processes, which is the following:
d(S
total
)
dt
=
m
e
s
e
m
i
s
i
+
d(S
surr
)
dt
(13.9)
where the subscript e stands for the exit and the subscript i stands for the
inlet.
If the surroundings is taken as a thermal reservoir at a constant tem-
perature of T
surr
K, we get
d(S
surr
)
dt
=
(

Q
in
)
surr
T
surr
(13.10)
where (

Q
in
)
surr
denotes the rate at which heat is transferred from the
system to the surroundings during the process.
For an adiabatic steady ow process, the system does not thermally
interact with the surroundings. Therefore,
d(S
total
)
dt
=
m
e
s
e
m
i
s
i
(13.11)
Example 13.1
heat capacity is divided into equal halves by a partition of negligible mass.
Initially, one compartment contains air at 2 bar and 400 K, and the other is
evacuated. When the dividing partition is raptured, air will rush to ll the
entire box. Show that this process is a irreversible process. It is a common
assumption that air at low or moderate pressures behaves like an ideal gas.
Let us evaluate the total entropy change of the system and its surroundings
to determine if the given process is reversible or not. The system is isolated from
the surroundings, and therefore
S
total
= S
sys
= m
air
s
air
Since air is assumed to behave as an ideal gas and since air volume has doubled
during the process, we could use (11.23) or (11.25) to determine s
air
as follows:
s
air
= C
v
ln (T
f
/T
o
) +Rln (2) = C
v
ln (P
f
/P
o
) +C
p
ln (2)
310 Chapter 13
Let us now determine the temperature or pressure ratio between the nal
and the initial equilibrium states of the process. Since the entire system is
isolated from its surroundings, the internal energy of the system remains constant
throughout the process. Since air is assumed to behave as an ideal gas, and
since the internal energy of an ideal gas is a function of temperature alone, the
temperature at the nal equilibrium state is also 400 K. Thus, ln (T
f
/T
o
) = 0.
We therefore get
S
total
= m
air
s
air
= m
air
R ln (2) > 0
Thus, according to the second law given by (13.1), the given process is a
irreversible process. We, of course, know that the expansion of air into vacuum
is unrestrained, and therefore the expansion process is far from reversible. The
second law has just proven it.
Example 13.2
Hot gases leaving the turbine of a turbojet
engine is reported to enter the nozzle of the turbojet engine at 6 bar and
975 K and exit the nozzle at 0.9 bar and 925 m/s. Determine if such a ow
is possible in reality. Ignore the speed of the gases at the nozzle entrance.
Assume that the gases behave as ideal gas and that C
p
= 1.005 kJ/kg K
and = 1.4. Also, assume steady adiabatic ow through the nozzle.
Using the steady ow energy equation applied to the steady adiabatic ow
of an ideal gas through the nozzle, we get T
e
, the temperature at the nozzle
exit, as
T
e
= T
i
c
2
e
c
2
i
2 C
p
= 975 K
925
2
2 1005
K = 549.3 K
Since the ow through the adiabatic nozzle exchanges no heat with its sur-
roundings, using (13.11) and (11.24), we get
d(S
total
)
dt
= m(s
e
s
i
) = m
C
p
ln
T
e
T
i
Rln
P
e
P
i
= mR
1.4
1.4 1
ln
549.3
975
ln
0.9
6
= 0.11 mR < 0
Thus, according to the second law given by (13.1), the given process is an
impossible process.
Example 13.3
Determine the maximum possible speed re-
alizable at the nozzle exit of Example 13.2 for the given inlet condition
and exit pressure.
At the reversible limit, d(S
total
)/dt) = 0 for the ow through the adiabatic
nozzle. Therefore, we get the temperature at the nozzle exit, T
e
, as
mR
1.4
1.4 1
ln
T
e
975
ln
0.9
6
= 0
which gives T
e
= 567 K.
Using this exit temperature in the steady ow energy equation applicable for
the ow through adiabatic nozzle, we get the speed at the nozzle exit, c
e
, as
c
e
=
2 C
p
(T
i
T
e
) =
2 1005 (975 567) = 905.5 m/s

which is the maximum possible speed realizable at the nozzle exit for the given
conditions.
Example 13.4
A steady ow of steam enters an adiabatic
turbine at 60 bar and 400
C with negligible velocity. It is reported to leave

the nozzle at 3 bar as saturated steam. Is that possible?
The specic entropy of steam at the entrance of the turbine can be found
from a Steam Table as s
e
C = 6.541 kJ/kg K. The

312 Chapter 13
specic entropy of steam at the exit of the turbine is found from a Steam Table
as s
i
= s of saturated steam at 3 bar = 6.993 kJ/kg K.
Therefore, for steady ow through an adiabatic turbine,
d(S
total
)
dt
= m(s
e
s
i
) = m(6.541 6.993) < 0
Thus, according to the second law given by (13.1), the given process is not
possible in reality.
Example 13.5
Calculate the entropy change for the process
where 3 kg of liquid water at 30
C is cooled until it freezes at 0
C. Take
C
water
as 4.2 kJ/kg K, and the latent heat of freezing at 0
C as 333
kJ/kg.
Considering water as an incompressible substance, we could use (11.22) to
determine the entropy change for the process, in which the temperature of water
is reduced from 30
C to 0
C, as follows:
s = (4.2 kJ/kg K) ln (273/303) = 0.44 kJ/kg K
Conversion of water to ice occurs at a constant temperature of 0
C, during
which v changes but P remains constant. Thus, let us start with T ds = dh
v dP, which reduces to T ds = dh for a constant-pressure process such as the
one considered here. Therefore, we get
s =
dh
T
=
h
T
for the given constant-pressure and constant-temperature phase change process.
Since h for the process of water turning into ice at 0
C is the latent heat

of freezing, we get
s =
333 kJ/kg
273 K
= 1.22 kJ/kg K
The total change in the entropy for the given process is therefore
S
sys
= 3 kg (0.44 1.22) kJ/kg K = 4.98 kJ/K (13.12)
Student: Teacher, the total entropy change of the system is negative in the
above example. According the second law, it is then an impossible process.
How could that be? We know that water can be frozen to get ice. What
is wrong?
Teacher: Nothing is wrong, dear Student. Observe that it is the total en-
tropy change of the system that takes a negative value, not the total
entropy change of the system and the surroundings. The given system
has interacted with its surroundings during cooling, by losing heat to the
surroundings. Therefore, we need to evaluate the entropy change of the
surroundings, and add that value to the entropy change of the system to
get the total entropy change of the system and its surroundings. It is this
total that should take a positive value for the process to be a real process.
Example 13.6
Calculate the total entropy change of the sys-
tem and its surroundings for the process given in Example 13.5. Take
the surroundings to be a thermal reservoir at 20
C.
The entropy change of the system is calculated in the Solution to Exam-
ple 13.5, and is given by (13.12). Now, let us evaluate the entropy change of
the surroundings. Since the surroundings is assumed to be a thermal reservoir
at 20
C, we could use (13.5) to get S

surr
as follows:
S
surr
=
(Q
in
)
surr
253 K
(13.13)
where (Q
in
)
surr
is the heat lost by the system to the surroundings.
The heat lost by water when it is cooled from 30
C to 0
C is evaluated using
(3 kg) (4.2 kJ/kg K) (303 273) K, which becomes 378 kJ. Heat lost
during the conversion of water at 0
C to ice at 0
C is evaluated using (3 kg)

333 kJ/kg, which becomes 999 kJ.
314 Chapter 13
The total heat lost to the surroundings is therefore 1377 kJ. Substituting it
in (13.13), we get
S
surr
=
1377 kJ
253 K
= 5.44 kJ/K (13.14)
S
total
= 0.46 kJ/K > 0
Therefore, according to the second law, the process considered is a real
(irreversible) process.
Student: Teacher, you have assumed that the surroundings was at 20
C in
working out the above example. What if I take the surroundings to be at
the room temperature, say, 30
C. Will I still get S

total
> 0?
Teacher: You cant do that. How could the system, which is cooled from 30
C
to 0
C, lose heat to a surroundings that is at a higher temperature than

the system?
Student: Yes, that is true.... But, Teacher, it happens with the refrigerator.
Doesnt it?
Teacher: Yes, it does. Heat is transferred from the inside of the refrigerator,
which is at a much lower temperature than the atmospheric temperature,
to the surroundings, which is at atmospheric temperature. That is correct.
Student: How does that happen, Teacher?
Teacher: A refrigerator cannot lose heat to its surroundings unless we provide
work in the form of electricity to operate its compressor. Do you agree
with that?
Student: Yes, I do. I know about the compressor in the refrigerator. If the
compressor fails then refrigerator does not function. Well, how does a
refrigerator work?
Teacher: Each refrigerator has an engine, which consists of a uid known as
refrigerant. Are you familiar with that?
Student: I know about the refrigerant used in a refrigerator. I know that
CFCs, the chemicals that make a hole in the ozone layer, are used as
refrigerants. But, nowadays, it is being replaced by other chemicals that
does not damage the ozone layer.
Teacher: Its very good that you know so much about refrigerants. Now, let
me tell you about the cyclic process executed by the refrigerant in the
refrigerator. The schematic diagram of a typical refrigeration cycle is
given in Figure 13.1.
evaporator
condenser
reciprocating
compressor
throttling
valve
?
heat removed from the
refrigerated space at 10
C
?
Heat rejected to the
surroundings at 30
work input
as electricity
superheated vapour
at 1.2 bar & 20
C
superheated vapour
at 10 bar & 65
o
C
vapour-liquid
mixture at
1.2 bar & 25.8
C
subcooled
liquid at
10 bar & 40
C
Figure 13.1 Schematic of a typical refrigeration cycle.
Student: Teacher, the gure looks complicated except for the compressor,
throttling valve and the condenser. We have already learned about them
in Chapter 10. Havent we?
Teacher: Yes, you have. Let me explain the workings of the refrigeration
cycle shown in the gure. First of all, lets take the freezer compartment
of a refrigerator, which must be maintained, say, at 10
C. Heat must
be continuously removed from the freezer space to maintain such a low
temperature when the surrounding atmosphere is around 30
C. Do you
agree with that?
Student: Yes, I do.
Teacher: Let us send a liquid, the refrigerant, at a temperature much lower
than 10
C through the evaporator coil that is attached to the inner walls

of the freezer compartment. Tell me what happens to the refrigerant then.
316 Chapter 13
Student: Of course, heat will be transferred from the freezer space at 10
C
to the refrigerant at a temperature much lower than 10
C.
Teacher: Thats correct. The refrigerant entering the evaporator is usually
maintained as a mixture of saturated liquid and vapour at a temperature
at least 10 degrees below the freezer space temperature, and at a pressure
slightly above the atmospheric pressure. The heat transferred from the
freezer space to the refrigerant heats the refrigerant to a slightly super-
heated vapour state. This vapour is compressed to a pressure about 8 to
10 times the atmospheric pressure in a reciprocating type of compressor
powered by electricity.
Student: Why are we compressing the refrigerant, Teacher?
Teacher: When the refrigerant vapour is compressed, its temperature would
increase. We need to increase the temperature of the refrigerant well
above the temperature of the surroundings, so that the refrigerant could
lose all the heat that it has gained in the evaporator to the surroundings,
as it passes through the condenser coil that is exposed to the atmosphere.
Student: I see, that is why the air around the refrigerator is warm. It explains
why my cat loves to lie down on the refrigerator during the cold days.
Teacher: Yes, that is right.
Student: Okay, Teacher, I understand how the refrigeration cycle works. But,
tell me why there is a throttling valve in the cycle.
Teacher: The temperature of the refrigerant leaving the condenser could not
be reduced below the atmospheric temperature. Do you agree with that?
Student: Yes, I do. We could not lower the temperature of the refrigerant
below the temperature of the atmosphere to which it is losing heat.
Teacher: Thats correct. The refrigerant leaving the condenser at a temper-
ature above the atmospheric temperature is throttled using a throttling
valve to reduce the temperature of the refrigerant passing through it, to
a value that is much below the atmospheric temperature.
Student: Well, I see why a throttling valve is needed.
Teacher: The refrigeration cycle is so designed that the temperature and the
pressure reductions across the throttling valve, which is simply a capillary
tube, will bring the refrigerant to the temperature and the pressure at
which it enters the evaporator. In this way, the refrigeration cycle is
completed and the same refrigerant is used over and over again.
Student: Oh, I see. Thats neat. But... I have a question. It appears that the
refrigerant is used and reused. Then, how it enters the atmosphere and
destroys the ozone layer.
Teacher: Oh, well, the discarded refrigerators are the main culprits who let
the refrigerant into the atmosphere. Now, I want you to take note of the
fact that heat cannot be transferred from a lower temperature body to a
higher temperature body unless work is provided to the engine, as with
the refrigerators.
Student: Yes, I have noted that.
Teacher: In the following examples, we will prove that fact using the second
law given by (13.1).
Example 13.7
Is it possible for an engine, whose working
uid operating in a cyclic process as in the refrigeration cycle discussed
above, to transfer heat from a cooler reservoir to a hotter reservoir without
producing any other eects on the surroundings?
Let us consider the schematic of an engine shown in Figure 13.2, whose
working uid describe is said to describe a cyclic process. It receives Q
in
amount
of heat from the cold reservoir at T
L
K and rejects Q
out
amount of heat to the
hot reservoir at T
H
K, where T
H
> T
L
.
Since the system describes a cyclic process, the internal energy of the system
remains a constant. Therefore, according to the rst law, all heat removed from
the cold reservoir could be transferred to the hot reservoir. That is,
Q
in
= Q
out
(13.15)
Let us now calculate the total entropy change of the engine of Figure 13.2.
The system undergoes a cyclic process and entropy is a property, and therefore
the entropy of the system would not change. That is,
S
sys
= 0 (13.16)
318 Chapter 13
hot reservoir at T
H
K
cold reservoir at T
L
K
Q
out
Q
in
Figure 13.2 Heat transfer from a cooler reservoir to a hotter reservoir.
The surroundings consists of the hot reservoir at T
H
K and the cold reservoir
at T
L
K. The entropy change of the surroundings can therefore be evaluated
using (13.5) as follows:
S
surr
=
Q
out
T
H
Q
in
T
L
(13.17)
where the hot reservoir gains Q
out
amount of heat from the system and the cold
reservoir loses Q
in
amount of heat to the system.
Combining (13.16) and (13.17), we get the total entropy change of the
engine of Figure 13.2 as
S
total
=
Q
out
T
H
Q
in
T
L
(13.18)
Using (13.15), the above could be rewritten as
S
total
=
T
L
T
H
T
H
T
L
Q
in
< 0
since T
L
, the temperature of the cold reservoir, is less than T
H
, the temperature
of the hot reservoir.
According to the second law, given by (13.1), a process for which S
total
<
0 is an impossible process. Thus, no engine, whose working uid operating in a
cyclic process, could transfer heat from a cooler reservoir to a hotter reservoir,
without producing any other eects.
Example 13.8
Prove using the second law that it is possible
for an engine, whose working uid operating in a cyclic process, to remove
heat from a cooler reservoir and rejects heat to a hotter reservoir, if work
is supplied to the engine?
The engine given in this example is what is known as the refrigerator or,
as the heat pump in general, and the schematic of which is shown in Figure
13.3.
hot reservoir at T
H
K
cold reservoir at T
L
K
Q
out
Q
in
Figure 13.3 Schematic of a heat pump.
W
in
This example is similar to Example 13.7, except for the fact that the
system is provided with work. Therefore, according to the rst law,
Q
in
+W
in
= Q
out
(13.19)
The total entropy change of the heat pump of Figure 13.3 would be the
same as that is given by (13.18). Eliminating Q
out
from (13.18) using (13.19),
we get
S
total
=
Q
in
+W
in
T
H
Q
in
T
L
=
W
in
T
H
T
H
T
L
T
H
T
L
Q
in
(13.20)
320 Chapter 13
For S
total
to be a positive quantity,
W
in
>
T
H
T
L
T
L
Q
in
(13.21)
Thus, it is possible to construct an engine, whose working uid operating
in a cyclic process, capable of removing heat from a cooler reservoir and rejects
heat to a hotter reservoir, if the work done on the working uid of the engine
satises (13.21).
Comment: From Example 13.7 and Example 13.8, we shall conclude
that it is impossible to construct an engine, whose working uid operating in a
cyclic process, capable of transferring heat from a cooler body to a hotter body,
without producing no other eect. This is the famous Clausius Statement
of the Second Law.
The ratio of heat removed from the cooler reservoir by the heat pump
to the work supplied to the heat pump is known as the coecient of
performance, and is denoted by COP. From (13.21), we can determine
the upper limit of the COP as follows:
COP =
Q
in
W
in
<
T
L
T
H
T
L
(13.22)
Any heat pump that works at the upper limit of the COP will have
S
total
= 0, which means that such a heat pump operates as a reversible
heat pump. A reversible heat pump is known as the Carnot heat pump,
and its COP is known at the Carnot COP, given by
COP
Carnot
=
T
L
T
H
T
L
(13.23)
Example 13.9
Determine the minimum amount of work re-
quired to operate an air-conditioner which will maintain an indoor tem-
perature of 25
C. The atmospheric temperature is at 36
C, and the heat

generated indoor from the people and other heat generating devices are esti-
mated to be 26 MJ/h. Determine also the heat rejected to the atmosphere
by the air-conditioner.
The air-conditioner functions as a heat pump removing 26 MJ/h of heat from
the indoor space maintained at 25
C (which is the cooler reservoir) and rejecting

heat to the atmosphere at 36
C (which is the hotter reservoir). Combining

(13.22) and (13.23), we can write the coecient of performance of an air-
conditioner, as
COP =
Q
in
W
in
COP
Carnot
which gives
W
in
=
Q
in
COP

Q
in
COP
Carnot
The minimum work required by the air-conditioner is therefore given by
(W
in
)
min
=
Q
in
COP
Carnot
We can calculate the COP using (13.23) as
COP
Carnot
=
T
L
T
H
T
L
=
273 + 25
(273 + 36) (273 + 25)
= 27.1
It is given that Q
in
= 26 MJ/h, and therefore
(W
in
)
min
=
26 MJ/h
27.1
= 0.27 kW
The minimum amount of heat rejected to the atmosphere by the air-conditioner
is calculated as follows:
(Q
out
)
min
= Q
in
+ (W
in
)
min
= 26 MJ/h +
26
27.1
MJ/h 27 MJ/h
Comment: Note that making the living space cool and comfortable by air-
conditioning results in additional amount of heat being rejected into the envi-
ronment. At least 1 MJ/h of waste heat is added in the case considered in this
example.
322 Chapter 13
Example 13.10
Is it possible to convert all heat provided to
an engine, whose working uid operating in a cycling process, into useful
work?
Let us consider the engine shown in Figure 13.4. The working uid of the
engine, taken as the system, is said to operate a cyclic process. It receives Q
in
amount of heat from the surroundings and does W
out
amount of work on the
surroundings.
hot reservoir at T
H
K
Q
in
Figure 13.4 Schematic of an engine converting all heat into work.
W
out
Since the system describes a cyclic process, the internal energy of the system
remains a constant. Therefore, according to the rst law, all heat provided to
the system is converted into work. That is, W
out
= Q
in
.
Well, what does the second law says about such a 100% conversion of heat
into work? To answer this question, let us calculate the total entropy change of
the engine of Figure 13.4. Following the methods used in the previous examples,
we could write that S
sys
= 0, and S
surr
= (Q
in
/T
H
).
The total entropy change of the engine of Figure 13.4 is therefore
S
total
=
Q
in
T
H
< 0 (13.24)
since Q
in
and T
H
are positive quantities.
According to the second law, given by (13.1), a process for which S
total
< 0 is an impossible process. Therefore, it is not possible to convert all heat
provided to an engine, whose working uid operating in a cycling process, into
work.
Example 13.11
Prove using the second law that it is pos-
sible for an engine, whose working uid operating in a cyclic process, to
convert part of the heat that it receives from a hotter reservoir into work
done on the surroundings, provided the remaining heat is rejected to a
cooler reservoir.
The engine given in this example is what is known as the heat engine, and
the schematic of which is shown in Figure 13.5.
hot reservoir at T
H
K
cold reservoir at T
L
K
Q
in
Q
out
Figure 13.5 Schematic of a heat engine.
W
out
This example is similar to Example 13.10, except for the fact that the
system rejects heat into a cooler reservoir. Therefore, according to the rst law,
Q
in
= W
out
+Q
out
(13.25)
Let us calculate the total entropy change of the engine of Figure 13.5 fol-
lowing the methods used in the previous examples as follows: S
sys
= 0, and
S
surr
= (Q
in
/T
H
) + (Q
out
/T
L
).
The total entropy change of the engine of Figure 13.5 is therefore
S
total
=
Q
in
T
H
+
Q
out
T
L
(13.26)
324 Chapter 13
Eliminating Q
out
from (13.26) using (13.25), we get
S
total
=
Q
in
T
H
+
Q
in
W
out
T
L
=
T
H
T
L
T
H
T
L
Q
in
W
out
T
L
(13.27)
For S
total
to be a positive quantity,
W
out
<
T
H
T
L
T
H
Q
in
(13.28)
Thus, it is possible to construct an engine, whose working uid operating in
a cyclic process, to convert part of the heat it receives from a hotter reservoir
into work done on the surroundings, and to reject the remaining heat to a cooler
reservoir, provided (13.28) is satised.
Comment: From Example 13.10 and Example 13.11, we shall conclude
that it is impossible to construct an engine, whose working uid operating in a
cyclic process, capable of converting all heat it receives into useful work, without
producing no other eect in its surroundings. This is the famous Kelvin-Plank
Statement of the Second Law.
The ratio of work obtained from the heat engine to the heat provided to
the heat engine is known as the thermal eciency, and is denoted by .
From (13.28), we can determine the upper limit of the thermal eciency
as follows:
=
W
out
Q
in
< 1
T
L
T
H
(13.29)
Any heat engine that works at the upper limit of the thermal eciency
will have S
total
= 0, which means that such a heat engine operates as a
reversible heat engine. A reversible heat engine is known as the Carnot
heat engine, and its thermal eciency is known at the Carnot e-
ciency, denoted by
Carnot
= 1
T
L
T
H
(13.30)
No heat engine can have a thermal eciency higher than the Carnot
eciency, which is a function of the maximum and minimum temperatures
across which the heat engine operates.
Increasing the temperature of the hotter reservoir and/or decreasing the
temperature of the cooler reservoir are the only means by which the Carnot
eciency of a heat engine could be increased.
Example 13.12
Consider the steam turbine of Example
12.4, whose working uid (water/steam) operates in a cyclic process. Take
the hot gases providing heat to the steam generator as the hotter reservoir,
and assume that it remains at a constant temperature of 500
C throughout
the operation. Take the cooling water removing heat from the condenser
as the cooler reservoir at a constant temperature of 27
C. If the heat input

to the steam engine from the hotter reservoir is 155 MJ/s, determine the
maximum work output possible from the heat engine, and the amount of
heat rejected to the cooler reservoir.
Combining (13.29) and (13.30), we can write that the thermal eciency of
a heat engine as
=
W
out
Q
in

Carnot
which gives
W
out
= Q
in

Carnot
Q
in
The maximum work obtainable is therefore given by
(W
out
)
max
=
Carnot
Q
in
We can calculate
Carnot
using (13.30) as
Carnot
= 1
T
L
T
H
= 1
273 + 27
273 + 500
= 61.2%
It is given that Q
in
= 155 MJ/s, and therefore
(W
out
)
max
= 0.612 155 MJ/s = 95 MW
326 Chapter 13
The minimum amount of heat rejected by the heat engine can be calculated
using the rst law as follows:
(Q
out
)
min
= Q
in
(W
out
)
max
= 155 MJ/s 95 MW = 60 MJ/s
Comment: For any real heat engine working between the reservoirs at 500
C
and 27
C, the thermal eciency would be less than 61.2%, which is the Carnot
eciency, the work output would be less than 95 MW, and the heat rejected by
the engine would be more than 60 MJ/s.
Example 13.13
If the temperature of the cooler reservoir
of the heat engine of Example 13.12 is reduced to, say, 23
C, then
the work output of the heat engine could be increased for the same 155
MJ/s of heat that the heat engine receives from the reservoir at 500
C.
You therefore plan to use a cooler reservoir at 23
C for the heat engine.

To maintain the temperature at 23
C, you plan to use a heat pump that

operates between the 23
C reservoir and the original cooler reservoir of

the heat engine of Example 13.12 at 27
C. Assuming that all the heat

rejected by the heat engine to the reservoir at 23
C is removed by the heat

pump, determine the maximum net work output and the overall thermal
eciency of the combined system.
Figure 13.6 shows the combined system. The heat pump could be operated
only if we provide work to it, which is denoted as W
in
is the gure. The net
work output is therefore W
out
W
in
, where W
out
is the work output of the heat
engine.
For the heat engine, following the procedure adopted in the Solution to
Example 13.12, we get
Carnot
= 1
250
773
= 0.677
and therefore the maximum work obtainable from the heat engine is given by
(W
out
)
max
=
Carnot
Q
1
= 0.677 155 MJ/s = 105 MW
Q
1
= 155 MJ/s
Q
2
W
out
Q
4
Q
3
W
in
heat
engine
heat
pump
reservoir at 23
C
reservoir at 27
C
reservoir at 500
C
Heat rejected by the heat engine to the reservoir at 23
C is
Q
2
= Q
1
(W
out
)
max
= 155 MJ/s 105 MW = 50 MJ/s
This amount of heat is removed by the heat pump from the reservoir at
23
C, and therefore
Q
3
= Q
2
= 50 MJ/s
Combining (13.22) and (13.23), we can write the coecient of performance
of a heat pump as
COP =
Q
3
W
in
COP
Carnot
which gives
W
in
=
Q
3
COP

Q
3
COP
Carnot
The minimum work required by the heat pump is therefore given by
(W
in
)
min
=
Q
3
COP
Carnot
We can calculate the COP using (13.23) as
COP
Carnot
=
T
L
T
H
T
L
=
250
300 250
= 5
We know that Q
3
= 50 MJ/s, and therefore
(W
in
)
min
=
50 MJ/s
5
= 10 MW
328 Chapter 13
The net work output of the combined system is calculated as follows:
(W
out
)
net
= (W
out
)
max
(W
in
)
min
= 105 MW10 MW = 95 MW
which is the maximum net work output obtainable from the combined system.
The overall thermal eciency of the combined system is determined as fol-
lows:
overall
=
(W
out
)
net
Q
1
=
95 MW
155 MJ/s
= 61.2
Comment: Observe that the maximum net work output and the overall thermal
eciency of the combined system are the same as the maximum work output and
the thermal eciency of the heat engine alone in Example 13.12. Therefore,
it is of no advantage to use the combined system proposed in this example to
generate the work required.
Example 13.14
A metal block A of 70 kg is at 800 K and
a metal block B of 200 kg is at 300 K. A heat engine, the working uid of
which operating in a cyclic process, is to be operated using the two given
metal blocks as the heat source and heat sink, respectively. It is reported
that during a trial run, the temperature of the metal block A is reduced to
470 K and that of the metal block B is increased to 370 K. The specic
heat of the metal is given as 0.45 kJ/kg K. Verify the report by carrying
out a second law analysis.
If the system satises the second law, determine the work output and
the thermal eciency of the heat engine.
Consider the heat engine as the system and the metal blocks A and B as
the surroundings. Since the heat engine describes a cyclic process, S
sys
= 0.
Therefore,
S
total
= S
surr
= S
A
+ S
B
Taking the metal blocks to be incompressible substances, we could use
(11.15) to calculate the entropy changes of blocks A and B as follows:
S
A
= (70 kg) (0.45 kJ/kg K) ln
470
800
= 16.75 kJ/K
S
B
= (200 kg) (0.45 kJ/kg K) ln
370
300
= 18.88 kJ/K
Therefore,
S
total
= 16.75 kJ/K + 18.88 kJ/K = 2.12 kJ/K > 0
Since S
total
> 0, according to the second law, the given system is physically
realizable.
The work output of the engine, according to the rst law, is given by the
dierence between the heat received by the engine from block A and the heat
rejected by the engine to block B. Heat received by the engine from block A is
given by 70 0.45 (800 - 470) kJ = 10,395 kJ. Heat rejected by the engine
to block B is given by 200 0.45 (370 - 300) kJ = 6,300 kJ. The work output
of the engine is therefore 4,095 kJ. And, the thermal eciency of the engine is
39.4%.
Example 13.15
What should be the nal temperature of
block B of Example 13.14 for the work output of the heat engine to
reach its maximum? Assume all other data of Example 13.14 remains
unchanged. Determine also the value of the maximum work output and
the corresponding thermal eciency.
The maximum work output could be obtained, in theory, when the system of
Example 13.14 reaches its reversible limit. That is, when S
total
= S
A
+
S
B
= 0, which gives
70 0.45 ln
470
800
+ 200 0.45 ln
T
Bf
300
= 0
where T
Bf
is the nal temperature of block B.
330 Chapter 13
Solving the above, we get T
Bf
= 361.4 K. Therefore, heat rejected by the
engine to block B will become 200 0.45 (361.4 - 300) kJ = 5,526 kJ. Heat
received by the engine from block A remains the same as in the Solution to
Example 13.14, which is 10,395 kJ. The maximum work output will therefore
be 4,869 kJ, and the corresponding thermal eciency will be 46.8%.
Example 13.16
A reversible gas turbine, whose working
uid is considered to operate in a cyclic process, works between two thermal
reservoirs, say A and B. The reservoir A is at 1200 K and the reservoir B
is at 500 K. A reversible steam turbine is operated between the reservoir B
and the atmosphere at 300 K. Determine the overall thermal eciency of
this idealized combined gas turbine - steam turbine plant.
Compare this overall thermal eciency to the thermal eciency of a
reversible heat engine that would operate between the reservoirs at 1200 K
and 300 K.
The schematic of the combined power plant is shown in Figure 13.7. The
overall thermal eciency of the combined power plant would be
overall
=
(W
out
)
gt
+ (W
out
)
st
Q
1
From the data given for the reversible gas and steam turbines, we get
gt
= 1
500
1200
= 58.3% and (W
out
)
gt
= 0.583 Q
1
st
= 1
300
500
= 40.0% and (W
out
)
st
= 0.4 Q
3
Assuming that all the heat rejected by the gas turbine to the reservoir at
500 K is taken by the steam turbine, we get
Q
3
= Q
2
= Q
1
(W
out
)
gt
= Q
1
0.583 Q
1
= 0.417 Q
1
which gives
(W
out
)
st
= 0.4 0.417 Q
1
= 0.167 Q
1
The overall thermal eciency of the combined power plant therefore becomes
overall
=
0.583 Q
1
+ 0.167 Q
1
Q
1
= 75%
Q
1
Q
2
(W
out
)
gt
B: reservoir at 500 K
C: reservoir at 300 K
(W
out
)
st
Q
3
Q
4
gas turbine
steam turbine
A: reservoir at 1200 K
For a reversible heat engine operating between the reservoirs at 1200 K and
300 K, the thermal eciency is
= 1
300
1200
= 75%
The results show that regardless of whether we operate a single heat engine
or a combined power plant, the thermal eciency remains unchanged as far
as the temperatures of the hotter reservoir and the cooler reservoir remain the
same.
In reality, however, there are certain constraints in operating a gas turbine or
a steam turbine alone between the two given temperature extremes to reach the
kind of eciencies that could be achieved by the combined power plant. The
details of which is beyond the scope of this text book, and therefore will not be
discussed here.
332 Chapter 13
Example 13.17
The combined power plants are known for their
improved thermal eciency. The thermal eciency of a newly installed com-
bined power plant is about 48%. The plant operates between the maximum
temperature of 1000 K and the atmospheric temperature of 300 K. A company
that comes with foreign aid claims that they will be able to increase the thermal
eciency of the power plant to 70% by installing energy saving devices at a cost.
You have been asked to advice the Minister of Energy on that. What will be
your advice?
A single (or even a combined) reversible heat engine operating between 1000
K and 300 K will have the following Carnot eciency:
Carnot
= 1
300
1000
= 70%
No engine, however cleverly built, could have an eciency that is higher
than the Carnot eciency, which is 70% in this case, as long as it is operated
between the temperature extremes of 1000 K and 300 K.
Reaching the 70% thermal eciency means that the combined power plant
must be operated under reversible conditions. Even though, in theory, it is
possible to improve the thermal eciency to achieve the Carnot eciency, it
would be impossible to reach such eciency in real life situations.
My advice to the Minister of Energy would be that the companys claim is
not physically realizable.
13.4 Summary
The mathematical equivalence of the second law is as follows:
S
total
> 0 for a real (irreversible) process

= 0 for a reversible process
< 0 for an impossible process
(13.1)
For a closed system,
S
total
= S
sys
+ S
surr
(13.2)
where
S
sys
= ms
sys
= m(s
f
s
o
) (13.3)
If the surroundings has a nite mass,
S
surr
= m
surr
s
surr
= m
surr
(s
f
s
o
)
surr
(13.4)
A thermal reservoir is assumed to remain at a constant temperature
regardless of the heat transferred to or from the reservoir. It is also
assumed that no irreversibilities occur within the thermal reservoir.
If the surroundings is taken as a thermal reservoir at a temperature of
T
surr
K then
S
surr
=
(Q
in
)
surr
T
surr
(13.5)
where (Q
in
)
surr
denotes the nite amount of heat transferred to the sur-
roundings from the system during the process.
For an adiabatic process,
S
total
= S
sys
= m(s
f
s
o
) (13.7)
For a reversible adiabatic process,
S
total
= 0 (13.8)
For an open system,
d(S
total
)
dt
=
m
e
s
e
m
i
s
i
+
d(S
surr
)
dt
(13.9)
If the surroundings of the open system is taken as a thermal reservoir at
a constant temperature of T
surr
K, then
d(S
surr
)
dt
=
(

Q
in
)
surr
T
surr
(13.10)
where (

Q
in
)
surr
denotes the rate at which heat is transferred from the
system to the surroundings during the process.
334 Chapter 13
For an adiabatic steady ow process,
d(S
total
)
dt
=
m
e
s
e
m
i
s
i
(13.11)
A heat pump is a device, whose working uid operating in a cyclic process,
receives heat from a cooler reservoir and work from the surroundings, and
rejects all that it received, as heat to a hotter reservoir.
The coecient of performance of a heat pump is given by
COP =
Q
in
W
in
< COP
Carnot
(13.22)
where
COP
Carnot
=
T
L
T
H
T
L
(13.23)
No heat pump can have a coecient of performance higher than the
Carnot coecient of performance, which is a function of the maximum
and minimum temperatures across which the heat pump operates.
Heat engine is a device, whose working uid operating in a cyclic process,
receives heat from a hotter reservoir, does work on the surroundings, and
rejects the remaining heat to a cooler reservoir.
The thermal eciency of a heat engine is given by
=
W
out
Q
in
<
Carnot
(13.29)
where
Carnot
= 1
T
L
T
H
(13.30)
No heat engine can have a thermal eciency higher than the Carnot
eciency, which is a function of the maximum and minimum temperatures
across which the heat engine operates.

Basics of Thermodynamics

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Preface

Thermodynamics often confuses a beginner. And, there are valid

Electricity can be generated in an electric generator in which a coil is

Yet another example of a system is shown in Figure 2.3. We want to

for a large number of gases that are assumed to behave as ideal

Using the given numerical values of a, b, c, d and e, and R = 8.314

, is that the entries do not include pressure as an entry. It is

See, for example, the following tables:

Solution to Example 5.1

C. The gas expands

C, and the other is evacuated.

C. The pin holding

. The predictability of these equations

For a complete description, see the following sources:

are constants specic to the substance concerned.

C, at which condition water is in

C. As steam transforms into liquid water at

C at 100 bar, and 365.7

C at 200 bar. The horizontal line

C, which are above the

C, the specic volume of liquid water increases slightly until point D

C. During the vaporization

C results in considerable increase in the

C, as well. For water at

C, which are temperatures above the critical temperature

C, the transformation of water from liquid phase to gas phase is so

C, which is the triple point, and ends

C, which is the critical point.

C. This means that water

C at 40 bar. Therefore, steam at 350

C given within the brackets. The second column

C, etc. at 40 bar pressure. Note that

C would give the properties of superheated

C. Therefore, steam at 100 bar and 320

C and the superheated

C to obtain v, h and s at 100 bar and 320

C at 100 bar, which is not

C to get the results required at 680

C to get the values for 680

C. This means that water boils at

C at 75 bar. Therefore at the given temperature of 100

at 50 bar and 100 bar are reproduced below:

C. Therefore, 6 bar and 50

C, as we can nd from a a Saturated Water and

C may be given as v 0.1012

C and 4.35 kJ/kg K

C to the saturated water state at 6 bar and 158.8

C to the saturation temperature t

C and 4.35 kJ/kg K

C. Taking an average value for C

lists the real gas

Van Wylan, G., Sonntag, R. & Borgnakke, C. 1994 Fundamentals of Classical

C. Since the prop-

C is 419.1 kJ/kg, and therefore h at 7 bar

C can be approximated to 419 kJ/kg. Similarly, the compressed

C, which is in fact not provided in the table above. Let

C. Therefore, 0.05 bar and 50

C, and the cor-