CHAPTER ONE

INTRODUCTION TO THERMODYNAMICS
Thermodynamics is defined as a branch of science that deals with the relationship between
properties of systems and the quantity of ‘work’ and ‘heat’. Since work and heat are forms of
energy, thermodynamics is thus the science of energy of fluid. Energy plays a very important
role in almost all engineering activities. Hence, the principles of thermodynamics play a vital
role in the design of all engineering equipment such as internal combustion engines, rockets, jet
engines, thermal and nuclear power plants, refrigerators etc.

Thermodynamics stems from two Greek words, namely, thermos meaning heat and dynamis
meaning power. Thus, it deals with energy conversion and the direction of change. The
principles of thermodynamics are summarized into four laws known as Zeroth, first, second and
third laws of thermodynamics. The Zeroth law of thermodynamics deals with thermal
equilibrium and provides a means of measuring temperature. The first law of thermodynamics
deals with the conservation of energy and introduces the concept of internal energy. The second
law of thermodynamics dictates the limits on the conversion of heat into work and provides the
yardstick to measure the performance of various processes. It also tells whether a particular
process is feasible or not and specifies the direction in which a process will proceed. As a
consequence it also introduces the concept of entropy. The third law defines the absolute zero of
entropy. These laws are universally valid; they cannot be circumvented. In summary,
thermodynamics focuses largely on how heat is transferred to various energy changes within a
physical system undergoing a thermodynamic process. Such processes usually result in work
being done by the system and are guided by the laws of thermodynamics.

BASIC CONCEPT AND DEFINITIONS OF VARIOUS TERMINOLOGIES IN

THERMODYNAMICS
Thermodynamics System
A thermodynamics system is arbitrarily defined as any collection of matter that can be separated
from everything else by a well-defined surface, such that changes in everything else need not
affect the condition of the collection. The system is surrounded by the boundary and the area
beyond the boundary is called the surroundings. The boundary of the system can be fixed or
movable. Between the system and its surrounding the exchange of mass or energy or both can

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occur. Consider the engine of a motor car, which consist of different components like radiator,
carburetor or injector, alternator etc, if one of this is to be worked on (say the radiator), then this
is considered as the system, other components are the surroundings and the ‘space’ between the
system and the surroundings is the boundary of the system. Fig 1-1 shows a typical
thermodynamic system showing the system, boundary and the surroundings.

Fig 1-1: A Typical Thermodynamic System

There are three main types of system: open system, closed system and isolated system.

1) Open system this is a system in which the transfer of mass as well as energy can take
place across its boundary to its surroundings (fig 1-2). For instance, in boiling water in
an open pot on a stove, energy and matter are being transferred to the surroundings
through steam. The pot is an open system because it allows transfer of heat as well as
mass in form of steam to take place between the pot and its surrounding.

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 Fig 1-2: Open system

2) Closed system is a system that exchanges only energy with its surroundings, no transfer
of mass takes place (fig. 1-3). The closed system is fixed mass system. By putting a lid on
the pot, matter can no longer transfer because the lid prevents matter from entering the
pot and leaving the pot, but the pot allows energy transfer when heated on a stove.

Fig. 1-3: A closed system

3) Isolated system this is a system that does not exchange energy or mass with its
surroundings. For example, if the piston and cylinder arrangement in which the fluid like
air or gas is being compressed or expanded is insulated, it becomes an isolated system.

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 An isolated system is more restrictive than a closed system as it does not interact with its
surroundings in any way. Mass and energy remain constant within the system, and no
energy or mass transfer takes place across the boundary. As time passes in an isolated
system, internal differences in the system tend to even out and pressures and temperatures
tend to equalize, as do density differences. A system in which all equalizing processes
have gone practically to completion is in a state of thermodynamics equilibrium.

Truly, isolated physical systems do not exist in reality (except perhaps for the universe as
a whole), because, for example, there is always gravity between systems with mass and
masses elsewhere. However, real systems may behave nearly as an isolated system for
finite (possibly very long) times. The concept of an isolated system can serve as a useful
model in approximating many real-world situations. It is an acceptable idealization used
in constructing mathematical models of certain natural phenomena.

Thermodynamic State
At any instant, a system is in a condition called a state which encompasses all that can be said
about the results of any measurement or observation that can be performed on the system at that
time. The state at a given instance of time determines the properties of the system. For fluid
systems, typical properties are pressure, volume and temperature.

Thermodynamics Properties
Distinguishing characteristics of a system at any distance of time or at any location are known as
the properties of the system and the properties can be used to define the state of the system.
Properties may be described as extensive, intensive or specific. Extensive properties are
functions of the extent and size of the system and cannot be used to define a state. They are
additive. Thus, if the system is divided into a number of sub-systems, the value of the property
for the whole system is equal to the sum of the values for the parts. Mass, Volume and Total
Energy are some examples of extensive properties. Intensive properties are not dependent on
the size of the system and can be used to describe the state. Temperature and pressure are
intensive properties. Specific properties are extensive properties expressed per unit mass and

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 V
are denoted by lower case letters. Examples are specific volume v = , specific internal energy
m
U
u= etc.
m
Specific properties are treated as intensive properties and can be used to define a state. With
pure, compressible substances involving only one type of work, two fundamental properties
(internal or specific) are needed to define the state of a system.

Three fundamental thermodynamic properties are pressure, temperature and specific volume.
Other properties of interest are the specific internal energy (u), specific enthalpy (h) and the
specific entropy(s). Enthalpy is a property that was derived for convenience being the sum of the
internal energy and the product of the pressure and volume i.e. H = U + PV.

Thermodynamic processes
Thermodynamic equilibrium is a condition in which there are no unbalanced forces within a
system; so the properties themselves are not changing. A system undergoes a thermodynamic
process when there is some sort of energetic change within the system, generally associated with
changes in pressure, volume, internal energy (i.e. temperature), or any sort of heat transfer.
Process diagrams plotted by employing thermodynamic properties as coordinates are very useful
in visualizing the processes. Some common properties that are used as coordinates are
temperature T, pressure P, and volume V (or specific volume v). Fig 1-4 shows the P-V diagram
of a compression process of a gas.

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Fig. 1-4: The P-V diagram of a compression process

There are several specific types of thermodynamic processes that have special properties:

• Isochoric (or Isometric) process - a thermodynamic process during which the volume of
the closed system undergoing such a process remains constant. An isochoric process is
exemplified by the heating or the cooling of the contents of a sealed, inelastic container:
The thermodynamic process is the addition or removal of heat; the isolation of the
contents of the container establishes the closed system; and the inability of the container
to deform imposes the constant-volume condition. The work done by the isochoric
process is zero since the change in volume is equal to zero

∆W = ∫ PdV = P ∫ dV = P(V 2 − V1 ) = P (0 ) = 0 Since (V2=V1)

The P-V diagram for isochoric process is shown fig 1-5 below

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 Fig 1-5: P – V diagram for Isochoric Process

• Isobaric process - a process with no change in pressure. An isobaric process occurs at

constant pressure (P=constant). An example would be to have a movable piston in a
cylinder, so that the pressure inside the cylinder is always at atmospheric pressure,
although it is isolated from the atmosphere. In other words, the system is dynamically
connected, by a movable boundary, to a constant-pressure reservoir. The work done by
the isobaric process is

∆W = ∫ PdV = P ∫ dV = P(V 2 − V1 ) = P∆V

The P-V diagram for isobaric process is shown in fig 1-6 below. The area under the graph
represents the work done.

Fig 1-6: P – V diagram for Isobaric Process

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 • Isothermal process - a change of a system, in which the temperature remains constant:
∆T = 0. This typically occurs when a system is in contact with an outside thermal
reservoir (heat bath), and the change occurs slowly enough to allow the system to
continually adjust to the temperature of the reservoir through heat exchange. In an
isothermal process, the value ∆T = 0 and therefore ∆U = 0 (only for an ideal gas) but Q ≠
0. The P-V diagram for isothermal process is shown in fig 1-7 below. The area under the
graph represents "work" for this isothermal change

Fig 1-7 P – V diagram for Isothermal Process

In thermodynamics, the work involved when a gas changes from state A to state B is simply

VB

W A− B = ∫ pdV
VA

pV = nRT

nRT
p=
V

VB
nRT
W A− B = ∫
VA
V
dV

VB
1
W A− B = nRT ∫ dV
VA
V

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 VB
W A− B = nRTIn
VA (1-1)

• Adiabatic process - a process that occurs without the transfer of heat or matter between a
system and its surroundings. Adiabatic processes are primarily and exactly defined for a
system contained by walls that are completely thermally insulating and impermeable to
matter; such walls are said to be adiabatic. The P-V diagram for an adiabatic process is
shown in fig 1-8 below.

Fig 1-8: P – V diagram for Adiabatic Process

The mathematical equation for an ideal gas undergoing an adiabatic process is

PV γ = cons tan t

PV γ = C

C
P=
Vγ

Cp
γ=
Cv

VB

W A− B = ∫ pdV
VA

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 VB
C
W A− B = ∫Vγ
VA
dV

VB B V
1
W A− B = C ∫ γ dV = C ∫ V −γ dV
VA V VA

VB
 V −γ +1 
W A− B = C 
 − γ + 1 V A

V −γ +1 − V A−γ +1 
W A− B = C  B 
 − γ +1 

 P V − PAV A 
W A− B =  B B 
 − γ +1 
 P V − PAV A 
W A− B =  B B 
 1− γ  (1-2)

A polytropic process is a thermodynamic process that obeys the relation:

PV n = C
Finally, a polytropic process is one in which the P-V relationship is such that PVn is a constant,
where P is the pressure, V is volume, n the polytropic index, any real number, and C is a constant. The
polytropic process equation is particularly useful for characterizing expansion and compression
processes which includes heat transfer. This equation can accurately characterize a very wide range of
thermodynamic processes, that range from n=0 to n=∞ which covers, n=0 (isobaric), n=1 (isothermal),
n=γ (isentropic), n=∞ (isochoric) processes and all values of n in between. Hence the equation is
polytropic in the sense that it describes many lines or many processes.

The mathematical equation for an ideal gas undergoing a polytropic process is

pV n = cons tan t = C

1
W2 = ∫ pdV
1

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 2
C
= ∫V
1
n
dV

2
−n
= C V dV ∫
1

2
 V − n +1 
= C  
 − n + 1 1
2
 CV − n +1 − CV1 − n +1 
=  2 
 − n +1 1

 p 2V2 nV2 − n +1 − p1V1 nV1 − n +1 

=   since C = p1V1n = p2Vn2
 − n +1 

 p 2V2 − p1V1 
=   (1-3)
 − n +1 

The polytropic relationship among P, V and T can be useful in ideal gas analysis and can be
written as

n −1
n −1
T2  P2  n V 
=  =  1 
T1  P1   V2 

An isentropic process is one that is both internally reversible and adiabatic. So the entropy
remains constant. All the processes are reversible, irreversible or impossible.

A totally reversible process is a process in which the system and surroundings can be restored
to the initial state from the final state without producing any changes in the thermodynamics
properties of the universe. Suppose a system has undergone a change from state A to state B. If
the system can be restored from state B to state A, and there is no change in the universe, then
the process is said to be a reversible process. The reversible process can be reversed completely
and there is no trace left to show that the system had undergone thermodynamic change. For the
system to undergo reversible change, it should occur infinitely slowly due to infinitesimal
gradient. During reversible process all the changes in state that occur in the system are in

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thermodynamic equilibrium with each other. If during the reversible process the heat content of
the system remains constant, i.e. it is adiabatic process, then the process is also isentropic
process, i.e. the entropy of the system remains constant.

A process is said to be an irreversible process if it cannot return the system and the
surroundings to their original conditions when the process is reversed. The irreversible process is
not at equilibrium throughout the process. For example, when a car is driven uphill, it consumes
a lot of fuel and this fuel is not returned when it’s driven downhill. Many factors contribute in
making any process irreversible. The most common of these are:

1) Friction
2) Unrestrained expansion of a fluid
3) Heat transfer through a finite temperature difference
4) Mixing of two different substances.

Irreversible process is also called the natural process because all the processes occurring in
nature are irreversible processes. The natural process occurs due to the finite gradient between
the two states of the system. For instance, heat flow between two bodies occurs due to the
temperature gradient between the two bodies; this is in fact the natural flow of heat. Similarly,
water flows from high level to low level, current moves from high potential to low potential etc.
Therefore, for an irreversible process:

1) The initial state of the system and surroundings cannot be restored from the final state.
2) During the process the various states of the system on the path of change from initial state to
final state are not in equilibrium with each other.
3) During the process the entropy of the system increases decisively and it cannot be reduced
back to its initial value.

An internally irreversible process is an actual process in which the lost work is not equal to zero
and is positive. An impossible process is one that violates the second law (lost work is negative)

Forms of Energy
In defining a system and its surroundings, words like energy and matter are used very often. As a
result, one's understandings of a system and its surroundings can increase by understanding

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energy and matter. Energy is the ability to do work. Work is defined as the product of the force
(F) and the distance (L), through which it acts and in differential form, it can be written as:

δW = FdL (1-4)

δW indicates an inexact differential which means it cannot be integrated directly i.e. the
integration of δW from state 1 to state 2 is not equal to W2 - W1( δW ≠ W2 – W1 but δW = 1W2 or
W12). Therefore work is known as a path function; it is a form of energy that cannot be stored
and whose value in going from one point (state) to another is dependent on how the change was
made. That is which path was travelled in going from one point to the other.

On the other hand, the integration of the exact integral, dL, is independent of the path and is
simply the linear distance between the two points. If we consider a gas in a closed system
composed of a cylinder and a frictionless piston, the force on the piston is the product of the
pressure and the piston cross-sectional area A. Therefore equation 1 becomes

δW = PAdL (1-5)

But AdL is change in volume of the cylinder dV, therefore equation 2 becomes

δW = PdV = mPdv (1-6)

Since V = mv, the total work (W12) involved in going from state 1 to state 2 is obtained by
integrating the right hand side of equation 3. To perform this integration, it is necessary to know
the relationship between the pressure and the (specific) volume which is equivalent to knowing
the path travelled between the two states. One obvious path is the constant pressure path, so that
the total work is simply the pressure times the change in volume. Another obvious path is the one
in which the volume is constant (V1 = V2) in which case there is no work done (W12 = 0).

Work is a transient quantity which appears at the boundary when a system changes its state due

to the movement of a part of the boundary under the action of a force.

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Sign convention:

If the work is done by the system on the surroundings, e.g., when a fluid expands pushing

a piston outwards, the work is said to be positive. i.e., Work output of the system = + W

If the work is done on the system by the surroundings, e.g., when a force is applied to a

rotating handle, or to a piston to compress a fluid, the work is said to be negative. i.e.,

Work input to system = – W

Heat and Specific heat

Heat is defined as energy transferred to (or from) a system because of temperature differences
between the system and a heat source (sink). Within a system not in equilibrium the energy
transferred is proportional to the temperature difference between two states. Heat is a path
function as work; so it cannot be stored and must be expressed as an inexact differential.

Since the heat transferred is directly proportional to the temperature difference between two
states, it can be expressed as

δQ = mC X dT (1-7)

where CX is a generalized specific heat whose value depends on the substance and the path
followed and which is a function of the temperature and pressure.

Two paths (processes) of interest that lead to specialized and useful specific heats are the
constant volume process and constant pressure process. In the constant volume process, all the
energy added to a closed system in the form of heat is devoted to increasing the internal energy
of the system and the constant volume specific heat can be described mathematically as the
partial derivative of the specific internal energy ‘u’ with respect to the temperature ‘T’ and is
given the symbol Cv. In the constant pressure process, some of the heat added to a closed system
may be used to do work as well as increase the internal energy. So the constant specific heat can
be described mathematically as the partial derivative of the specific enthalpy ‘h’ with respect to
the temperature ‘T’ and is given the symbol ‘Cp’.

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“Heat is ‘something’ which appears at the boundary when a system changes its state due to a
difference in temperature between the system and its surroundings”. Heat, like work, is a
transient quantity which only appears at the boundary while a change is taking place within the
system.
Sign convention:
If the heat flows into a system from the surroundings, the quantity is said to be positive and,
conversely, if heat flows from the system to the surroundings it is said to be negative. In other
words:

Heat received by the system = + Q

Heat rejected or given up by the system = – Q.

Other forms of Energy

In addition to work and heat, engineering thermodynamics deals with internal energy and
enthalpy and generally to a lesser degree with kinetic and potential energies. Internal energy may
be defined simply as the energy within the molecular structure of the substance that is associated
with the potential energy and kinetic energy of the molecular and atomic structures. The internal
energy of matter is measured by its temperature. Hot water has more internal energy than the
same amount of cold water. Internal energy is a measure of kinetic energy of the molecules and
atoms that make up the substance. Since each atom or molecule is acting on its own accord, this
internal energy is different from the bulk kinetic energy associated with the movement of the
entire solid. The internal energy of matter is exhibited by molecular motion. The molecules of a
gas at high temperature zip around their container constantly colliding with walls and other
molecules. The molecules of a high temperature solid also move around a lot; however, since
they are stuck together with other molecules, the most they can do is vibrate in place.

Enthalpy is a derived property being the sum of the internal energy and the flow work and
represents an energy in the case of processes involving flow. The flow work is the work required
to move mass into and out of a system and is equal to the product of the pressure and volume and
is identified and combined with the internal energy so that the term ‘work’ can be reserved to
describe the useful work down by or on the system. Potential energy is "stored energy," energy
that contains the potential to do work when released. Any object that is stationary contains
potential energy. For example, if someone is standing in a baseball field holding a ball in his

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hand, the ball has potential energy. Note that the ball is stationary. Kinetic energy on the other
hand is known as the energy created by movement. Now imagine that someone is still holding
that same baseball in his hand (and) by throwing the baseball, potential energy is transformed to
kinetic energy, because the ball is now moving and is not stationary anymore. The Kinetic
1
energy of the system is given by the expression, K .E = mv 2 . The Potential Energy of the
2
system arises from the combination of the weight of the system and its elevation above a
reference datum often the surface of the earth, and the expression is, P.E = mgz .

Thermodynamic Cycles
A thermodynamic cycle consists of a series of thermodynamic processes transferring heat and
work, while varying pressure, temperature, and other state variables, eventually returning a
system to its initial state. In the process of going through this cycle, the system may perform
work on its surroundings, thereby acting as a heat engine. State quantities depend only on the
thermodynamic state, and cumulative variation of such properties add up to zero during a cycle.
Process quantities (or path quantities), such as heat and work are process dependent, and
cumulative heat and work are non-zero. The repeating nature of the process path allows for
continuous operation, making the cycle an important concept in thermodynamics.

A procedure or arrangement in which one form of energy such as heat at an elevated temperature
from combustion is in part converted to another form such as mechanical energy on a shaft and
the remainder is rejected to a lower temperature sink as low grade heat.

There is a basic pattern or process common to power producing cycles. There is a compression
process where in the working substances undergo an increase in pressure and therefore density.

There is an addition of thermal energy from a source such as fossil fuel or solar radiation. There
is an expansion process during which work is done by the system on the surroundings.

There is a rejection process where thermal energy is transferred to the surroundings. The basic
processes of the cycle either open or close are heat addition, heat rejection, expansion and
compression. These processes are always present in a cycle even though there may be difference

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in the working substance, the individual processes, pressure ranges, temperature ranges, the
mechanism and heat transfer (arrangement).

Reversibility
When a system changes state in such a way that at any instance during the process, the state
point can be located on the diagram, the process is said to be reversible. A reversible process
between 2 states can be drawn as a line on any diagram of properties. An irreversible process is
usually represented by dotted lines joining the end states
Reversibility means when a fluid undergoes a reversible process, both the fluid and its
surroundings can always be restored to their original states. The criteria of reversibility are as
follows:

1) The process must be frictionless, the fluid itself must have no internal friction and there
must be no mechanical friction.
2) The difference in pressure between the fluid and its surroundings during the process must
be infinitesimally small i.e. the process must take place very slowly since the force to
accelerate the boundaries of the system is very small.
3) The difference in temperature between the fluid and its surroundings during the process
must be infinitesimally small. This means that the heat supplied or rejected to or from the
fluid must be transferred very slowly.

ZEROTH’S LAW OF THERMODYNAMICS

The Zeroth’s Law of Thermodynamics states that if two systems are in thermodynamic
equilibrium with a third system, the two original systems are in thermal equilibrium with each
other. Basically, if system A is in thermal equilibrium with system C and system B is also in
thermal equilibrium with system C, system A and system B are in thermal equilibrium with each
other. It is called the "zeroth" law because it came to light after the first and second laws of
thermodynamics had already been established and named, but was considered more fundamental
and thus was given a lower number — zero.

The zeroth’s law of thermodynamics is the assurance of the existence of a property called the
temperature. The zeroth’s law is used to compare the temperatures of two objects, A and B.
This can be achieved using a thermometer, C and placing it against object A; it reaches thermal

23
equilibrium with object A and measure the temperature of A. Placing the thermometer against
object B until thermal equilibrium is reached, it measures the temperature of object B. If they are
the same temperature then they will be in thermal equilibrium with each other.

Fig 1-9: A thermometer

To measure temperature, we can use any property of matter that changes when heat is absorbed
or emitted (e.g. resistance of a platinum wire, the volume (and hence length) of liquid mercury in
a glass tube, the pressure of a given quantity of gas in a fixed volume, etc.). Such devices can be
used to verify the zeroth’s law experimentally. They are called thermoscopes (since no scale is
yet involved, they are not yet thermometers).

A thermometer is just a calibrated thermoscope. Any thermoscope can be used to define a

numerical temperature scale over some range by using two fixed points (e.g., the ice freezing
point and steam boiling point of water). However, thermoscopes based on the volume of gases
finally led to the notion of an absolute scale based on a single fixed point. This is the ideal gas
temperature scale, measured in Kelvin (K), agreed upon universally in 1954 to be 273.16K at the
triple point of water (the single fixed point of the scale). (Note: The freezing (ice) point of water
is some 0.01 K lower (273.15 K) in temperature than the triple point (273.16 K)). Hence, by
definition
 PV 
T = lim   * 273.16 K
P →0 
 ( PV )triple  (1-7)
in the Kelvin scale. This scale is based on the ideal gas law and low pressure (P → 0) limit is
taken because all real gases approach ideal behavior in that limit. The (otherwise strange and
arbitrary) value of 273.16 K was simply chosen so that the new Kelvin scale matched the earlier
Celsius scale as closely as possible (i.e., so that 1 K = 10C). Unlike earlier scales with 2 fixed

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