C H A P T E R

16
Elements of
Thermodynamics

16.1 INTRODUCTION
The various efforts of converting heat to obtain mechanical work led to the development
of steam engine in the eighteenth century. Initially, the steam engine was developed to
pump water out of deep coal mines which were flooded with water. These steam engines
were developed by practical inventors who followed trial and error methods rather than any
scientific principles. In 1765, James Watt invented a superior steam engine with a separate
condenser. It stimulated the development of engines that could do many kinds of jobs and
marked the beginning of industrial revolution. In subsequent years, many ambitious inventors
claimed to have invented perpetual motion machines which could do work without any input.
The analysis of these false claims and the genuine efforts to improve the efficiency of heat
engines resulted in the birth of thermodynamics as a separate branch of physics. The laws
of thermodynamics comprise the essence of 200 years of experimentation and theoretical
interpretation.
The works of Julius Robert Mayer (1814-1878), James Prescott Joule (1818-1889) and
Herman von Helmholtz (1821-1894) established the law of equivalence of heat and work.
Rudolf Clausius (1822-1888) formulated the second law of thermodynamics mathemati-
cally. Ludwig Boltzmann (1844-1906) gave the statistical interpretation of the second law
of thermodynamics in 1877. Josiah Willard Gibbs (1839-1903) generalized the methods of
Boltzmann.
Thermodynamics is the science that deals with the rules according to which bodies
exchange energy. In the early stages, thermodynamics was concerned with the relationship
between mechanical and heat energy. Further developments turned thermodynamics into a
science that is concerned with the relationships between heat and all other kinds of energy
such as chemical, electrical etc. The entire structure of thermodynamics rests on two laws
known as first and second laws of thermodynamics. The first law of thermodynamics
embodies the law of conservation of energy which encompasses all the fields of science and
engineering. The second law of thermodynamics expounds the idea that it is impossible to
convert a given amount of heat fully into work. The second law is also known as the law of
increasing entropy, on the basis of its interpretation at molecular level.
16.2 CONCEPT OF TEMPERATURE
The concept of temperature originated from our subjective sense of hot and cold. We use
these words to denote the degree of heating to which a body is subjected. The quantity that
404
Elements of Thermodynamics 405

characterizes the degree of heating to which a body is subjected is termed the temperature of
that body.
Experience shows that when a hot body is placed in contact with a cold body, their
temperatures change. The body with the higher temperature always gets cooler and the body
with the lower temperature always gets hotter. It indicates that energy exchange takes place
between the two bodies. Such an exchange of energy is called heat exchange. Eventually,
the temperature of the bodies become equal and the change in temperature stops. In technical
terms, the bodies are said to be in thermal equilibrium. Thus, if the temperatures of two
bodies are equal, no heat exchange takes place between them and the energy of each body
remains constant. We may therefore define temperature as a quantity indicating the direction
of heat exchange.
The concept of thermal equilibrium leads us to the zeroth law of thermodynamics. It
may be stated formally as follows:
“Two bodies, A and B, each in thermal equilibrium with a third body C are in thermal
equilibrium with each other”.
This law implies that equality of temperature is necessary and sufficient to ensure thermal
equilibrium. This law is really the basis of temperature measurements, for numbers can be
marked on the thermometer and every time a body has equality of temperature with the
thermometer, we can say that the body has the temperature we read on the thermometer.
According to kinetic theory of gases, temperature is a quality characterizing the average
kinetic energy of translational motion of the molecules of an ideal gas. It implies that the
temperature of every body is closely related to the energy of motion of its molecules.
The greater the average kinetic energy per molecule of a body, the higher its temperature.
Therefore, to heat a body, energy must be supplied to it, and to cool the body energy must be
taken away from it.

16.3 HEAT
In the eighteenth century, heat was considered to be a massless and invisible substance
called caloric. According to the caloric theory, every body contains an amount of caloric that
depends on the temperature of the body. Thus, a hot body contains more caloric than a cold
body. This theory could explain a number of observations concerning heat and temperature
effects. Count Rumford (Benjamin Thompson, American – British Physicist, 1753-1814) was
observing in 1798 the drilling of artillery gun barrels in Munich Armory. Every object was
supposed to contain a definite amount of caloric, but Rumford noticed that heat continued
to be generated as long as the boring tool scraped away at the barrel. Further, blunt drills
generated more heat than sharpened ones. He observed that drilling was somehow capable of
generating an almost unlimited amount of heat. He concluded that the generation of heat was
due to the mechanical work done in the process of boring and continued as long as this work
was being done.
Julius Robert Mayer (1814-1878), a German doctor serving as a physician on a ship, conceived
on 1842 the idea of the equivalence of heat and work. He hypothesized that heat is a form of
energy. However, the relationship between work and heat was established in 1850 experimentally
by James Joule (1818-1989), the British Physicist. He conducted a long series of experiments that
conclusively demonstrated the equivalence of mechanical energy and heat energy.
According to the modern view, heat is the energy that is transferred from a hot body to
a cold body. For example, let us consider the case of a beaker of hot water (hot body) left on
the table in an environment at room temperature (cold body). The hot water gets colder as
its temperature tends to approach the room temperature. It suggests that there is some sort of
406 A Textbook of Engineering Physics

exchange of energy between water (the system) and the surroundings. We now define heat in
a more general way.
Heat is energy that flows from one body or system to another solely as the result of a
temperature difference between them.
Thus, heat is not an intrinsic property of a body. A statement that a body contains a
certain amount of heat is meaningless. On the other hand, we can say that a body can transfer
a certain amount of energy as heat under certain specified conditions.
16.4 THERMODYNAMICS
The conversion of mechanical energy into heat and the reverse process of obtaining mechanical
work at the expense of heat are of the greatest interest in engineering. For example, in a
thermal power station, thermal energy in the form of steam at high temperature and pressure
drives a turbine (Fig.16.1) and is converted into mechanical energy. The turbine in its turn
drives the rotor of a generator which produces electricity.
Steam
Electrical
power
Turbine
+

Generator

Condenser
Source
of heat
Pump

Warm water out Cold water in

Fig. 16.1: Schematic diagram of an electrical power plant

Thermodynamics is the science that deals with work and heat, and those properties
of substances related to heat and work. Many of the properties of a substance and many
phenomena can be studied either from a microscopic or macroscopic point of view. For
instance, let us consider the familiar example of a monoatomic gas confined in a small
container. Quantities, characteristic of the atoms, such as the energy of an atom, its velocity,
its mass etc can be used to describe the properties of the gas. These quantities can be
computed from theoretical analysis but cannot be measured. All such quantities are said to be
microscopic. We may also describe the properties of the gas using quantities whose values
can be directly measured. Such quantities are called macroscopic quantities. Temperature,
pressure and volume are examples of macroscopic quantities. These are the quantities the
gas as a whole has, but have no meaning when applied to individual atoms. Thus, we cannot
speak of the pressure or temperature of one molecule. It is possible to develop the principles
of thermodynamics from a microscopic point of view. Historically, the central concepts
of thermodynamics were developed from a macroscopic view point without reference to
microscopic models and details of the structure of matter. We study here the principles of
thermodynamics from the macroscopic point of view.
Elements of Thermodynamics 407

16.5 TERMINOLOGY
There are certain terms in thermodynamics which are used with specific connotation. It is
necessary for us to acquaint with these terms before we embark on the study of thermodynamics.
16.5.1 System
The principles of thermodynamics are usually
stated with reference to a well defined system.
A system is defined in thermodynamics as a
quantity of matter of fixed mass and identity.
A familiar example of a thermody-
namic system is a quantity of gas enclosed
in a cylinder fitted with a movable piston
(Fig.16.2). The system and its environment Insulating
material
are distinctly identified by drawing a definite Gas
boundary between them. The system can Fig. 16.2. A gas in cylinder fitted with
interact with its environment, mainly in two a movable piston is an example of a
ways – by way of transfer of heat or by way thermodynamic system
of doing work.
16.5.2 State
The thermodynamic state of a system is described with the macroscopic quantities such
as pressure and volume. The physical quantities which unambiguously determine the state
of a body are called thermodynamic variables. The variables that are needed to define
completely the state of the system, illustrated in Fig.16.2, are the temperature T, the pressure
P, the volume V, and the mass, m. Two states of a body are considered to be different if the
value of even one of the thermodynamic variables is different for them.
16.5.3 Thermodynamic Equilibrium
In mechanics, equilibrium means a state of rest. In thermodynamics the concept is somewhat
broader. A system is said to be in thermodynamic equilibrium if none of the thermodynamic
variables determining its state changes with time. Thermodynamic equilibrium is easily
understood in the case of a monoatomic gas confined in a cylinder, as illustrated in Fig.16.2.
If the temperature of the gas in the cylinder is the same at all points in the cylinder and the
temperature of the walls of the cylinder is also the same, then the gas is in thermal equilibrium
with the cylinder. The heat of the gas does not flow from one part of the cylinder to another.
Further, when neither the pressure nor chemical composition of the gas changes, it is said
to be in thermodynamic equilibrium. Thus, a system will be in a state of thermodynamic
equilibrium if it satisfies the conditions for mechanical, thermal and chemical equilibrium.
A Cartesian coordinate system is used to plot sets of values of P, V, and T to indicate
equilibrium states of a system, as in Fig.16.3. Different points on the graph correspond to
different equilibrium states of the gas.
An isolated system always reaches a state of thermodynamic equilibrium in course of
time but can never depart from it spontaneously.
16.5.4 Process
Any change in the state of a system is called a thermodynamic process. In a thermodynamic
process one or more of the thermodynamic variables change. For instance, an increase in the
pressure exerted on a gas causes a decrease in its volume. The path of the succession of states
408 A Textbook of Engineering Physics

through which the system passes is called P

a process.
Different thermodynamic processes are
1 (P1, V1, T1)
studied and compared by depicting them
graphically. Such graphs are called process
charts and thermodynamic diagrams. Two
varying parameters of state, for example 2
the pressure P and volume V are laid off
along the axes of a two – dimensional
Cartesian coordinate system. It is called a 3
PV-diagram. The dependence of P on V 4
V
shows the given thermodynamic process. T
Fig. 16.3: Different equilibrium states of a gas
16.5.5 Quasistatic Process can be represented by points specified
If a thermodynamic process can be by values of pressure, volume and temperature
represented as a continuous succession of
P
equilibrium states of the system, it is termed
to be an equilibrium process or a quasistatic
process. Therefore, a quasistatic process is 1 (P1, V1, T1)
a thermodynamic process in which a system
passes through a series of equilibrium states.
Geometrically, a quasistatic process can be
represented by a curve that joins the initial 2
and final equilibrium states by a succession of
intermediate equilibrium states, as in Fig.16.4.
Only equilibrium states and quasistatic 3
processes can be depicted graphically. 4 V
T
If a system, which is originally in an
Fig. 16.4: The curve connecting the
equilibrium state, is momentarily disturbed equilibrium states of a system represents the
and then left alone, it passes on to equilibrium path of the process.
state spontaneously. The process of transition
to equilibrium is called relaxation. The time
needed for the transition is known as the relaxation
time. If a process is to be quasistatic, it must take
place during a time that is longer than the relaxation
time. During such a slow process the system can
be considered to pass through an infinitely large
number of equilibrium states.
A quasistatic process is illustrated in Fig. 16.5. A
cylinder filled with a gas has piston at one end. There
is no friction between the piston and the cylinder
walls. Initially, the gas is in the state of equilibrium.
Now, if we drop sand, grain by grain on the piston,
it moves down slowly through infinitesimally small
distances. The gas is compressed slightly near the Fig. 16.5: A gas in a cylinder is
piston each time a grain is added and its pressure, compressed slowly by adding grains of
density and temperature are increased. In other sand onto the piston
Elements of Thermodynamics 409

parts of the gas, the variables have not had sufficient time to change. After a time, equal to
relaxation time, equilibrium is restored. It means that the thermodynamic variables take new
values, but again the same throughout the gas. If the grains of sand are added slowly such that
the time of each micro-compression is greater than the relaxation time of the gas, then the
time will be sufficient for restoration of the equilibrium. Each added grain of sand takes the
system into a new equilibrium state. Then, the whole process of compression can be regarded
as the sum of a large number of micro-compressions and the thermodynamic process as the
totality of transitions through a large number of equilibrium states.
16.5.6 Reversible and Irreversible Processes
Suppose a perfectly elastic ball drops in a vacuum onto a perfectly elastic surface. As the ball
1 2
travels down, its potential energy (mgh) transforms into kinetic energy  mυ  . At the
 2 
instant when the ball touches the surface, its kinetic energy exactly equals to the initial
1 2 
potential energy  mυ = mgh  . Upon the impact elastic forces appear due to deformation
2 
of the ball and the surface. These forces will make the ball begin reverse motion upward. The
energy of deformation will transfer into the kinetic energy of the motion of the ball and it will
rise to the same height from which it began to drop. This process repeats many times. The
upward motion of the ball is a process that is reverse of downward motion. The ball when
rising passes through the same intermediate states determined by its coordinates and velocities
as in falling, but in the reverse sequence. Consequently, this mechanical process is a reversible
process.
Basing on the above example, we may define a reversible process as a process that
satisfies the following conditions:
i. The process can be carried out with equal facility in two opposite directions.
ii. In each direction the system passes through the same intermediate states; and
iii. After the completion of the process, the system and its environment return to their
initial state.
Any process which does not satisfy even one of these conditions is irreversible.
In thermodynamics a reversible process is a quasistatic process that can be reversed by an
infinitesimal change in the surroundings. Thus, a thermodynamic process is reversible if the
system passes from the initial state to final state through a succession of equilibrium states. A
reversible thermodynamics process may be understood with the help of the example given in
Fig. 16.5.
In the example cited there, adding or removing a grain of sand constitutes an infinitesimal
change in the surroundings. If the sand is added grain by grain, the gas is compressed
quasistatically and the gas passes through a series of equilibrium states to reach the final
equilibrium state. Now, if the sand is removed by grain by grain, the gas passes through the
same sequence of equilibrium states during the expansion, and reaches the initial state.
Since a reversible process is defined by a succession of equilibrium states, it can be
represented by a line on a PV diagram, as in Fig. 16.6. The line represents the path of the
process. Each point on the curve represents one of the intermediate equilibrium states. On
the other hand, an irreversible process passes from the initial state to the final state through a
series of nonequilibrium states. In this case, only the initial and final equilibrium states can be
represented on the PV diagram. The intermediate nonequilibrium states are not characterized
by uniquely defined sets of values for thermodynamic parameters. Hence, an irreversible
process cannot be represented by a line on a PV diagram.
410 A Textbook of Engineering Physics

There are many factors that make P

processes irreversible. There are no strictly
quasistatic processes in nature because all Irreversible
thermal processes occur at a finite rate and process
not infinitely slowly. Consequently, all real
processes in nature are irreversible. Let us F
consider three examples that demonstrate the
irreversibility of real thermal processes.
I
(i) Free expansion of a gas:
Consider the example of a gas separated from Reversible
a vacuum by a membrane, as in Fig. 16.7 process
(a). If the membrane breaks, the gas fills the V
entire vessel (Fig.16.7 b). The system cannot Fig. 16.6. A reversible process between the
be restored to its initial state unless the gas initial state and final state can be represented
is compressed and the resulting heat is taken by a line on PV diagram. An irreversible
process passes through a series of nonequi-
away. This, however, causes a change in the
librium state and cannot be represented by a
surroundings. Therefore, at the end of the line on PV diagram.
process, the surroundings are not restored to
their initial state. For this reason, the free expansion of a gas is an irreversible process.
System
boundary

Gas Vacuum Gas

Initial state Reverse Process

(a) (b)
Fig. 16.7: Free expansion of a gas. When the partition separating the gas from the evacuated
space is ruptured, the gas expands freely and irreversibly.
(ii) Diffusion: Let us consider the case of two different gases, oxygen and hydrogen,
separated by a membrane, as in Fig.16.8 (a). If the membrane breaks, diffusion of gases
takes place spontaneously and a homogeneous mixture of oxygen and hydrogen fill the entire
volume, as in Fig.16.8 (b). But the process will never reverse itself. The mixture of gases will
never divide by itself into the initial components.
In practice, a mixture of gases can be divided into its initial components. But first, it
involves application of energy. Secondly, the system will not pass again through the same
intermediate states it passed through in the diffusion process. Thirdly, the system cannot be
returned to its initial state without substantially altering the properties of the surroundings.
(iii) Heat Exchange: Experience shows that heat exchange, like diffusion, is a one-way
process. In heat exchange energy is always transmitted from a body at a higher temperature
to another body at a lower temperature. Consequently, heat exchange is always accompanied
by an equalization of temperatures. The reverse process of transferring energy in the form of
heat from cold bodies to hot bodies never occurs by itself. For example, a hot cup of coffee
cools by virtue of heat transfer to the surroundings, but heat will not flow from the cooler
surroundings to the hot cup of coffee.
Elements of Thermodynamics 411

O2 H2 O2 + H2

(a) (b)
Fig. 16.8: (a) Oxygen and hydrogen gases separated by a partition.
(b) Removal of partition leads to the irreversible mixing of the two gases

16.5.7 Cycle
When a system in a given initial state passes through a number of different changes of state or
processes and eventually returns to its original equilibrium state, then the system is said to have
undergone a thermodynamic cycle. The steps P
that constitute the cycle may be reversible or
irreversible. If the system consists of a single
homogeneous substance and if all the steps are
reversible, the cycle can be represented by a
closed curve in a PV diagram, as in Fig.16.9.

16.5.8 Heat Reservoir

A heat reservoir is a body from (or to) which
heat can be transferred without causing a
change in the temperature of the reservoir. O V
Such a heat reservoir remains at constant
Fig.16.9: The PV diagram for an arbitrary
temperature always. For example, the cyclic process. The net work done in the
atmosphere is a good heat reservoir. A heat process equals the area enclosed by the
reservoir from which heat is extracted by a curve.
body is called a high-temperature reservoir.
A heat reservoir to which heat is ejected from a body is called a low-temperature reservoir.

16.6 WORK
The mechanical work performed by a force is the most familiar form of work. In mechanics,
work is said to have been performed when a force acting on a body displaces it through a
distance, the displacement being in the direction of force. That is,
W = F·x (16.1)
When mechanical work is done on a body, its mechanical energy changes. Therefore,
it serves as the measure of transfer of mechanical energy from one body to another. In
general, we say work is a form of energy. Work is not stored in the body. Work is a form of
transferring energy and is a measure of the transferred energy.
Now let us examine the work done in a thermodynamic process. Consider a thermody-
namic system such as a gas contained in a cylinder fitted with a movable piston, as in
412 A Textbook of Engineering Physics

Fig.16.10 (a). In equilibrium the gas occupies a volume V and exerts a uniform pressure P on
the piston and the walls of the cylinder. If the cross-sectional area of the piston is A, the force
exerted by the gas on the piston is
A

dy

P V V + dV

(a) (b)
Fig.16.10: (a) Gas contained in a cylinder at a pressure P does work on the piston. (b) As the
piston moves the system expands from a volume V to a volume V + dV.

F = PA
Now, let us assume that the gas expands quasistatically. As the piston moves up a distance
(Fig.16.10 b), the work done by the gas on the piston is
dW = F dy = PA dy
But A dy = dV, the increase in the volume of the gas. Therefore,
dW = P dV (16.2)
The relation (16.2) expresses the work solely in terms of the thermodynamic variables
of the system. The nature of the external
P
force and other characteristics of the
surroundings do not appear in this
1
relation. The work dW = P dV is often P1
called thermodynamic work. In practice,
we refer to it simply as work. Work = Area under curve
The convention is that the work
done by a system is regarded as positive
and the work done on a system is
negative. Thus, the work done by the gas
expanding against a piston is positive and
2
the work done by a piston compressing a P
2
gas is negative.
The total work done by the gas as
its volume changes from V1 to V2 can be V1 V2 V
found by integrating equ.(16.2). Thus, Fig. 16.11: A gas expands from an initial state 1 to
final state 2. The work done by the gas equals the
area under the PV curve.
Elements of Thermodynamics 413

2 V2
1W2 = ∫ δW = ∫ P dV (16.3)
1 V1
The above integration can be performed only if we know the relationship between P and
V during the process. In general, the pressure P
is not constant but depends on the volume and
temperature. If the pressure and volume are
I
known at each step of the process, the work
C
done can be obtained graphically from the PV
diagram (Fig.16.11). The work done during B
the process is given by the area V1-1-2-V2-V1
under the curve 1-2 on Fig.16.11. Therefore, A
the total work done during the expansion of the 2
gas from the initial state to final state is the area
under the curve in a PV diagram.
It is possible to go from the initial state 1 to b d
V
the final state 2 along many different paths such
as A, B or C, as depicted in Fig.16.12. Since, Fig. 16.12: Three different paths connecting
the same initial and final states. The work
the area underneath each curve represents the done by the gas is a maximum for the path
work for each process, it is evident that the marked C which encloses the largest area.
amount of work performed in each case is a
function of the end states of the process and also it is dependent on the path that is followed in
going from one state to another. To illustrate this important point, we consider three different
paths (Fig.16.13) connecting initial and final states.
In the process represented in Fig.16.13 (a) the pressure of the gas is first reduced from P1
to P2 by cooling it at a constant volume V1. Next, the gas is allowed to expand from V1 to V2
at constant pressure P2. The work done along this path is WA = P2(V2 – V1)
P P P

P1 P1 1 P1
1

P2
P2 2 P2 2

V1 V2 V1 V2 V1 V2

(a) (b) (c)

Fig. 16.13: The work done by an ideal gas as it is taken from an initial state 1 to final state 2
depends on the path between these states 1 & 2.

In the process represented in Fig.16.13 (b), the gas is first allowed to expand from V1 to
V2 at constant pressure P1 and then the pressure is reduced to P2 at constant volume V2. The
work done along this path is WB = P1(V2 – V1).
Finally in the process described in Fig.16.13 (c), both P and V change continuously. To
compute the work in this case, the shape of the PV diagram must be known unambiguously.
414 A Textbook of Engineering Physics

It is clear from the PV diagrams in Fig.16.13 that WA is smaller than WB and WC has a
value intermediate between WA and WB. This example amply demonstrates that the work done
by a system depends on how the system goes from the initial to the final state. For this reason,
thermodynamic work is not a point function but is a path function. dW cannot be therefore
treated as exact differential in the mathematical sense.

16.7 HEAT IN THERMODYNAMICS

If a hot body is immersed in cold water, we know from experience that the hot body cools
down and the water warms up until the body and water attain the same temperature. It
suggests a transfer of energy from the hot body to the water. Such a process of transfer of
energy without work being done is called heat exchange. We may define heat as a form of
energy that is transferred from a system at
Insulating
a given temperature to another system at a wall Insulating
Vacuum
lower temperature solely by virtue of the wall

temperature difference between the two Membrane

systems. Thus, heat is energy in transit.
Heat transferred to a system is considered Gas at T1
Gas at T1
positive and heat transferred from a system
is negative. Heat reservoir
Like work, heat also is a path function. at T1 (b)
(a)
The heat transferred to or from a system
depends on the process. We illustrate Fig. 16.14: (a) A gas at temperature T1 expands
this point with the help of the following slowly by absorbing heat from a reservoir at the
examples. Let us consider the case of a gas same temperature. (b) A gas expands rapidly into
the evacuated region due to the rupture of the
of volume V1 which is in thermal contact
membrane.
with a heat reservoir (Fig.16.14a). If the
pressure of the gas is infinitesimally greater than atmospheric pressure, the gas will expand
and pushes up the piston. Ultimately the gas expands to a final volume V2. The heat required
to maintain the gas at a constant temperature T, during the process of expansion, is supplied
from the reservoir to the gas. Work is done by the gas in this case.
In the second case, illustrated in Fig.16.14 (b), a gas of the same volume V1 is thermally
insulated. It can neither receive nor give away heat. When the membrane is broken, the gas
freely and rapidly expands into the vacuum until it occupies a volume V2. No work is done
in this case. Further, no heat is transferred through the walls. The initial and final states of
both processes are identical but the paths followed are different. We conclude that heat, like
work, depends on how the system goes from its initial state to final state. Therefore, it is path
function. Like dW, dQ is an inexact differential.

16.8 COMPARISON OF HEAT AND WORK

In thermodynamics, work includes all forms of energy except heat. When a battery is
charged, electrical work was performed and stored in chemical form. When a piece of steel is
magnetized, magnetic work is performed.
Any kind of energy in the course of transformations may pass through many forms but
invariably ends in the form of heat energy. In the process of mechanical motion, the kinetic
energy of a body decreases owing to the action of friction forces and gets transformed into heat.
Similarly, the energy of an electric current, and of chemical reactions transform into heat.
Elements of Thermodynamics 415

Both work and heat are transient phenomena. Systems never contain work or heat. Heat
and work exist only in a process of energy transfer, and their numerical value depends on the
kind of this process. Either work or heat or both are transferred when a system undergoes a
change of state. In real conditions, both ways of transferring energy to a system accompany
each other. For instance, when a metal rod is heated, heat exchange takes place and at the
same time thermal expansion of rod occurs. The latter implies that the work of expansion is
done.
Heat and work are not equivalent forms of energy transfer from a qualitative viewpoint.
The energy of ordered motion is transferred in the form of work. The energy of chaotic motion
of particles constituting the body is increased when energy is transferred to a body in the form
of heat.
Work can be completely converted into heat. On the other hand, heat cannot be fully
converted into work. Hence work is said to be high grade energy and heat as low grade
energy.
Both heat and work are path functions and inexact differentials. Since they depend on the
path, neither quantity is independently conserved during a thermodynamic process.
16.9 INTERNAL ENERGY
The total energy ET of a system consists of (i) the kinetic energy of its macroscopic motion as
a whole (ii) the potential energy due to the presence of external fields and (iii) internal energy,
U. Thus,
ET = K.E. + P.E. + U (16.4)
The internal energy U of the system depends on the nature of the motion and interaction
of the particles in the system. It consists of (a) the kinetic energy of random thermal motion
of molecules (b) the potential energy of molecules due to intermolecular interactions, (c) the
kinetic and potential energies of atoms and electrons, and (d) the nuclear energy. In thermody-
namics, we do not concern ourselves with the form of internal energy.
Experiments have shown that the internal energy is determined by the thermody-
namic state of the system and does not depend on how the system acquired the given state.
Consequently, the internal energy is not related to the process of a change in the state of the
system. For example, the internal energy of a given amount of gas depends on its pressure
and temperature. It makes no difference how the gas achieved a particular pressure and
temperature. All processes leading to a particular pressure and temperature leave the gas with
the same internal energy. Keeping this in view, we may define internal energy as the energy
stored in a system.
The internal energy is not of practical interest. The change in internal energy DU, when a
system changes from one state to another, is of actual interest. It is generally assumed that the
internal energy of a system is zero at 0K.
16.10 LAW OF CONSERVATION OF ENERGY
In a closed mechanical system, the sum of kinetic energy and potential energy is constant.
The total energy can neither be created nor destroyed. It means that energy is conserved.
This is the law of conservation of mechanical energy. This law is applicable only in situation
where there is no transformation of mechanical energy into heat energy. In real systems the
mechanical motion is in general accompanied with heating. When the engine of a running car
is switched off, it gradually slows down and ultimately stops. Apparently, its kinetic energy
has disappeared. In fact, its kinetic energy is transformed into heat energy by the friction
416 A Textbook of Engineering Physics

forces. Both the tire of the car and the ground are heated up. As a result, the random motion
of particles constituting the interacting tires and road acquired more velocity. To sum up,
the mechanical energy (K.E. of car) is transformed into the internal energy of the interacting
bodies. If we take into account the internal energy, the law of conservation of energy can be
extended to include thermodynamic systems also. The first law of thermodynamics generalizes
the law of consideration of mechanical energy.

16.11 FIRST LAW OF THERMODYNAMICS

Thermodynamics is concerned with three general forms of energy, namely heat, work and
internal energy. Heat is the energy transferred by virtue of temperature difference, thermody-
namic work is energy (exclusive of heat) transferred between a system and surroundings, and
internal energy is energy stored within a system.
If the state of a system such as the one described in Fig.16.2 changes as a result of
supplying a quantity of heat Q to it, and as a consequence the system does the work W, then
the law of conservation of energy states that the quantity of heat supplied to the system will
be equal to the sum of the work performed by the system and the change in the internal
energy of the system. That is,
Net heat transfer = Work + Change in internal energy
Or mathematically, Q = W + DU (16.5)
This is known as the first law of thermodynamics. It is in effect a statement of the
conservation of energy. The net change in the internal energy of the system is always equal to
the net transfer of energy as heat and work across the boundary of the system.
While the quantities Q and W are path-dependent, the internal energy does not depend on
the path of the process.
Suppose a thermodynamic system undergoes a change from an initial state 1 to a final
state 2 in which Q units of heat are absorbed (or removed) and W is the work done by (or on)
the system. Expressing both Q and W in the same units (either thermal or mechanical) the
difference (Q – W) can be calculated. If now we carry out this calculation for different paths
between the same states 1 and 2, the quantity (Q – W) will be the same for all paths connecting
the states 1 and 2. It follows that the internal energy change of a system is independent of the
path. If U1 is the internal energy in state 1 and U2 is the internal energy in state 2, then the
relation (16.5) can be rewritten as
U2 – U1 = DU = Q – W (16.6)
When a thermodynamic process proceeds smoothly, it can be treated as a continuous sequence
of small changes. Mathematically, we write equ.(16.5) in the differential form as
dQ = dU + dW (16.7)
It is important to note that expressing heat and work as dQ and dW does not imply the
existence of properties Q and W that measure the heat and work content of a system. dQ and
dW denote small amounts of heat and work but they are not true differentials.
There is a serious limitation on the first law of thermodynamics. The law tells us whether
energy considerations permit a particular process to take a system from one equilibrium state
to another. But it does not tell us whether this process will actually occur or not. A certain
process might be entirely consistent with the principle of energy conservation but still it will
not take place.
16.12 APPLICATIONS OF THE FIRST LAW
Let us now study some special processes and the application of the first law to them.
Elements of Thermodynamics 417

1. Isolated system: An isolated system does not interact with its surroundings. Therefore,
there is no heat flow and the work done is zero. That is, Q = 0 and W = 0. It follows from equ.
(16.6) that DU = 0.
\ U2 – U1 = 0
or U2 = U1 Isolated system   (16.8)
Equ.(16.8) means that the internal energy of an isolated system remains constant.
2. Cyclic process: In a cyclic process, the initial and final states of the system are the
same. Thus,
U2 = U1
\ DU = 0
It allows from equ.(16.5) that
Q–W = 0
\ Q=W Cyclic process   (16.9)
Equ.(16.9) means that the net work done by the system over a cycle equals the net heat
absorbed over the cycle.
3. Adiabatic process: A process in which no heat is absorbed or ejected by the system is
called an adiabatic process. Thus, Q = 0.
\ DU = – W Adiabatic process   (16.10)
Thus, the change in the internal energy of a system is equal in magnitude to the work
done by the system. Heat flow into the system from the surroundings may be prevented in
two ways – (i) by surrounding the system with a thick layer of insulating material or (ii)
by performing the process quickly. The flow of heat requires finite time. So any process
performed quickly enough will be adiabatic.
4. Isochoric process: When a substance undergoes a process in which the volume remains
unchanged, the process is called isochoric. If the volume of a system remains constant, it can
do no work. Thus, W = 0 and the first law gives
DU = Q Isochoric process   (16.11)
In this case, the heat that entered the system is stored as internal energy.
5. Isothermal process: A process taking place at constant temperature is said to be
isothermal. In an isothermal process, the quantities, Q, W and DU are in general nonzero. The
first law does not assume any special form for an isothermal process.
6. Isobaric process: A process taking place at constant pressure is called an isobaric
process. As in the case of an isothermal process, Q, W and DU are all nonzero. The work
done by a system that expands or contracts isobarically has a simple form. As the pressure is
constant,
2
W= ∫ P dV = P(V2 – V1) Isobaric Process   (16.12)
1
7. Isothermal expansion of an ideal gas: Let an ideal gas be allowed to expand quasistat-
ically at constant temperature by placing the gas in good thermal contact with a heat reservoir
at the same temperature. Since the gas is ideal, and the process is quasistatic, we can apply the
ideal gas equation, namely PV = nRT for each point on the path.
V2 V2
n RT
\ W= ∫ P dV = ∫ V
dV
V1 V1
418 A Textbook of Engineering Physics

At T is constant in the process, we can write

V2
dV
W = nRT ∫ V
V1

V 
or W = nRT ln  2  (16.13)
 V1 
8. Adiabatic expansion of an ideal gas: Let us find the relation between P and V for
an adiabatic process carried out on an ideal gas. According to equ.(16.10), DU = – W in an
adiabatic process.
For an ideal gas DU = nCυdT   (at constant volume)
The work done during the process is given by W = P dV.
\ PdV = – nCυdT (16.14)
We can write the equation of the state of the gas in differential form as
d(PV) = d(nRT)
\ PdV + V dP = nR dT (16.15)
Using equ.(16.14) into equ.(16.15), we get
V dP = nCυdT + nRdT = ndT(Cυ + R)
But Cυ + R = Cp
\ V dP = nCpdT (16.16)
Taking the ratio between equ.(16.16) and equ.(16.14), we get
V dP Cp
= − = −γ
P dV Cυ
dP dV
\ = −γ
P V
Integrating on both sides of the above equation, we get
P2 2V
dP dV
∫ P
= −γ ∫
V
P1 V 1

P2 V
or ln = − γ ln 2
P1 V1
γ γ
\ PV
1 1 = P2V2 (16.17)

or PV g = Constant (16.18)
16.13 HEAT ENGINE
A heat engine is a device that converts heat energy to work. The automobile engines and
steam turbines are examples of heat engines. Basically, they all operate on the same principle.
For theoretical purposes, any heat engine can be conveniently represented by a diagram, as
shown in Fig.16.15, regardless of its particular design and features.
Any heat engine consists of three main parts: the working medium, the high-temperature
reservoir and the low-temperature reservoir. The working medium is some gas (or steam)
which receives a certain quantity of heat QH from the high-temperature reservoir, some of
which is used to do useful work W and the remainder QL is transferred to the low-temperature
reservoir.
Elements of Thermodynamics 419

For example, in an actual engine the energy

produced in the combustion of fuel is transmitted High temperature reservoir
TH
by heat exchange to some gas. As a result the gas
expands and the expanding gas does work on a
piston that is coupled to a crankshaft to produce heat in
useful work output. The unused heat is rejected to the
surroundings through an exhaust system. However,
the gas cannot continue to expand without any limit
because the engine is of finite size. Secondly, in Heat Work out
engine
practical applications we want an engine to deliver
work continuously. For these reasons, the gas must
be compressed, after expansion, so that the gas
and all the parts of the engine return to their initial
state. Again the expansion and compression can
be repeated. This implies that a heat engine must TL
operate in cycles so that we have work output Low temprature reservoir
during each cycle. As mentioned above, in the real
heat engine, the gas is discharged at the exhaust. A
new portion of the gas is admitted and compressed Fig.16.15. Schematic representation of
instead. It is called an open cycle operation. a heat engine. The engine absorbs heat
QH from the high temperature reservoir,
However, we assume, for the sake of simplicity, expels heat QL to low temperature
a closed cycle in which the same portion of gas reservoir and does work W.
expands and is compressed as it does not influence
the thermodynamics of the process.
We understand the necessity of the low-temperature reservoir as follows. For an engine
to do useful work during a cycle, it is P
necessary that the work done in expansion
by the gas must be greater than the work T1
P1
required to compress the gas. Then only
we obtain more mechanical energy. From
PV diagram, Fig.16.16, it is seen that the
work in expansion will be larger than that
in compression only if the pressure in the
Co

compression process is lower than that in

mp
r

expansion for all intermediate states. This

es

on
si

is possible only when the temperature cu

rve
of the gas is lower in compression than
P2 T2
in expansion at all intermediate points.
Therefore, an engine will do useful work
if the temperature of the gas is lower in
compression than in expansion. V1 V2
Fig. 16.16
16.13.1 Thermal Efficiency
Efficiency is a measure of how economical an engine is. We express cost efficiency in terms
of fuel economy. In the case of a mechanical device,
Work output
Mechanical efficiency = (16.19)
Work input
420 A Textbook of Engineering Physics

It is the fraction or percent of useful work done by a machine.

In heat engines, the work input is the heat input. The work output equals the heat in
minus the heat out.
Let us consider a heat engine operating in a cycle over and over again. Let QH and QL, be
the heat received and heat rejected by the working substance per cycle. The net heat absorbed is
Q = QH – QL (16.20)
The useful output of the engine is the net work W done by the working substance. Since
the working substance returns to its initial state after the cycle is completed, its internal energy
remains unchanged. That is, DU = 0. It follows from the first law that
W = Q = QH – QL (16.21)
Basing on the definition (16.19), we can define
W Q − QL
Thermal efficiency, h= = H (16.22)
QH QH
QL
\ h = 1− Ideal engine   (16.22 a)
QH
In practice, the useful work delivered by an engine is less than the work W owing to
friction losses. Therefore, the overall efficiency is less than the thermal efficiency. Thus,
Q
h ≤ 1− L Real engine   (16.23)
QH
where the less-than sign refers to real engines and the equal sign to an ideal engine in which
there are no losses.
Equation (16.23) points out that even an ideal engine has efficiency less than 100%. It
could be 100% only if heat is not delivered (QL = 0) during the compression. But this is
impossible, because the gas must be cooled in compression. Therefore, a certain amount of
heat (QL ≠ 0 ) must be delivered to the low temperature reservoir. It means that η < 100%.
A good automobile engine works at an efficiency of about 20% and diesel engines have
efficiencies ranging from 35% to 40%.
16.14 THE CARNOT CYCLE
If the efficiency of all heat engines is less than 100%, what is the most efficient cycle we can
have? Let us consider the case of a heat engine that receives heat from a high-temperature
reservoir and rejects heat to a lower temperature reservoir. In 1824 a French engineer, Sadi
Carnot (1796-1832) showed that a heat engine operating in a reversible cycle between the
two heat reservoirs would be the most efficient engine possible. Such an ideal heat engine
operates in a cycle in which every process is reversible. If every process is reversible, the
cycle is also reversible and if the cycle is reversed, the heat engine becomes a refrigerator.
Such a cycle is now called a Carnot cycle. The ideal engine is called the Carnot Engine
which establishes an upper limit on the efficiencies of all engines. That is, the net work done
by working substance taken through the Carnot cycle is the largest possible for given amount
of heat supplied to the substance.
The Carnot cycle is an idealization of the cycle of a real heat engine. It is assumed that
there are no losses of energy by heat exchange with the environment, that there is no friction
in the machine and that processes of gas expansion and compression are quasistatic and
therefore reversible.
Elements of Thermodynamics 421

To describe the Carnot cycle, we shall assume that the working substance is an ideal gas
contained in a cylinder with a movable piston at one end. Fig.16.17 (a) is a schematic diagram
of a Carnot engine and Fig.16.17 (b) shows the plot for a Carnot cycle.
1. The cycle begins at the equilibrium state A [Fig.16.17(b)] with the cylinder in
contact with high-temperature reservoir at a temperature TH (Fig.16.17. a). We
assume that the base of the cylinder is diathermic (i.e. perfectly conducting) and
that the walls and the piston are ideally nonconducting. The working substance (the
ideal gas) undergoes a slow quasistatic isothermal expansion to state B. During this
part of the cycle A → B, the temperature and hence the internal energy of the gas are
constant. Let the total amount of heat absorbed by the gas from the reservoir during
the process be QH. This heat energy input is converted directly to the work WAB done
in moving the piston.

P
QH
Working A
substance CD
AB

B
BC DA TH
W

D
High Non- Low
temperature conducting temperature
reservoir stand reservoir
C TL
Q1
V
TH TL
(a) (b)

Fig. 16.17: The Carnot cycle (a) In process A → B the gas expands isothermally while in contact
with a heat reservoir TH. In process B → C, the gas expands adiabatically. In process C → D,
the gas is compressed isothermally while in contact with a reservoir at TL. In process D → A, the
gas is compressed adiabatically. (b) The PV diagram for the Carnot Cycle. The net work W done
equals the net heat received in one cycle.
2. With the system at B, the cylinder is removed from contact with the high temperature
reservoir and placed on the nonconducting stand. The gas expands adiabatically
along the path B → C to the state C. During this part of the cycle B → C no heat
enters or leaves the system. However, work WBC is done at the expense of reducing
the internal energy. Consequently, the temperature falls from TH to TL.
3. Next the cylinder is placed in contact with the low temperature reservoir at a
temperature TL. The gas is now slowly compressed (by an external agency) isother-
mally to a predetermined volume VD at point D. During this part of cycle C → D,
the temperature and hence the internal energy of the working substance are constant.
During this process C → D, the gas expels heat to the reservoir and the work done
on the gas by the external agent is WCD.
4. In the final part D → A, the cylinder is removed from contact with the low-
temperature reservoir and again placed on the non-conducting stand. The gas is
compressed adiabatically and brought to the initial state A. The adiabatic compression
is also the result of work WDA done on the gas by an external energy. Consequent to
the adiabatic compression, the system temperature increases from TL to TH.
422 A Textbook of Engineering Physics

This step completes the Carnot cycle and returns the system to its initial condition.
The net work done in this reversible cyclic process is equal to the area enclosed by the
path ABCDA of the PV-diagram (Fig.16.17b). In a reversible cycle, the change in internal
energy is zero. It follows from first law that the net work done in one cycle equals the net heat
transferred into the system. For a system that undergoes a Carnot cycle, no heat is supplied to
or rejected by the system during the adiabatic paths, BC and DA (Fig.16.17b). An amount of
heat QH is supplied to the system during the isothermal expansion AB, and an amount QL is
rejected during the isothermal compression CD. Thus, the first law can be written as
W = QH – QL All heat engines   (16.24)
Equ.(16.24) is applicable for a complete cycle of any heat engine. The thermal efficiency
is given by equ.(16. 22).
W Q − QL Q
h= = H = 1− L
QH QH QH
16.14.1 Efficiency
For a Carnot engine, the heat exchanges take place during the isothermal processes. During
the isothermal expansion A → B, the heat absorbed from the high temperature reservoir is
given by
V
QH = WAB = n RTL ln B (16.25)
VA
In a similar manner, the heat rejected to the low temperature reservoir during the
isothermal compression C → D is given by
V
QL = WCD = n RTL ln C (16.26)
VD
Dividing these expressions, we get
QL T ln (VC / VD )
= L (16.27)
QH TH ln(VB / VA )
This can be further simplified by use of the temperature-volume relation for an adiabatic
process. For an adiabatic process, the pressure and volume are related by
PVg = Constant
During any reversible process, the ideal gas must also obey the equation of state,
PV = nRT (16.28)
Eliminating pressure between the above equations, we get
T V g–1 = Constant (16.29)
Applying this result to the adiabatic processes B → C and D → A, we get
TH VBg–1 = TL VCg–1 (16.30)
and g–1
TH VA = TL VD g–1 (16.31)
Dividing equ.(16.30) by equ.(16.31) we get
γ−1 γ−1
 VB  V 
  =  C
 VA   VD 
 VB   VC 
\   =   (16.32)
 VA   VD 
Elements of Thermodynamics 423

Substituting equ. (16.32) into equ.(16.27) , we obtain

QL T
= L Carnot Engine   (16.33)
QH TH
Using the result equ.(16.33) into equ.(16.23) we obtain the thermal efficiency of the
Carnot engine as
T T − TL
h = 1− L = H Carnot Engine   (16.34)
TH TH
This surprisingly simple result says that the efficiency of a Carnot engine depends only
on the temperatures of the two reservoirs. When (TH >> TL) the difference of the two tempera-
tures is large, the efficiency is nearly unity; when the difference is small the efficiency is
less than unity. Thus, the greater the temperature difference TH – TL, the greater will be the
efficiency of a Carnot engine.
We see from equ. (16.34) that all Carnot engines operating between the same two
temperatures in a reversible manner have the same efficiency.
It brings us to the important difference in principle between heat engines and mechanical
or electrical machines. In improving the design of mechanical or electrical machines we
try to make their efficiency as near as possible to the theoretical limiting value of 100%.
Though this limit is unattainable under real conditions, we can approach it by reducing losses.
When we improve heat engines, we do not try to bring their efficiency to 100%, but to that
of a Carnot engine operating in the same temperature interval. Naturally, the reduction of
all kinds of losses also raises the efficiency of a heat engine but the most effective measure
is to increase the temperature difference between the high temperature reservoir and low
temperature reservoir.
16.14.2 Carnot’s Theorem
The most important aspect of the Carnot engine is that it is the most efficient heat engine
operating between the two heat reservoirs. This is summarized in the Carnot’s theorem as
follows:
No heat engine operating between two heat reservoirs can be more efficient than a Carnot
engine operating between the same two reservoirs.
The Carnot’s theorem reveals a fundamental limitation on the conversion of heat into
work.

16.15 HEAT PUMP

A heat pump is a device that transfers heat from a low-temperature reservoir to a
high-temperature reservoir. This is the reverse function of a heat engine. A heat pump is
represented by a diagram as shown in Fig. 16.18. It requires work input, because the heat
transfer from low temperature reservoir to high-temperature reservoir will not take place
spontaneously.
The household refrigerator and air conditioner are examples of the most common heat
pumps. In an ordinary household refrigerator, the working substance is a liquid that circulates
within the system. It takes heat from the low temperature reservoir, which is the cold chamber
in which food articles are stored, and transfers it to the outside air in the room where the unit is
kept. The work is supplied by a compressor that uses electrical energy. The working substance
is a fluid that readily undergoes a liquid to gas phase change at the operating temperature.
The most common refrigerants are Freon – 12 (CC12F2) and ammonia.
424 A Textbook of Engineering Physics

A schematic diagram High temperature reservoir

of a refrigerator is shown TH

in Fig.16.19. Starting with

the gaseous refrigerant in
Heat out
the compressor, the gas is
compressed and emerges at a
high temperature and pressure. Work in
It then passes into the condenser, Heat
where it is cooled and liquefies, pump
and the heat from the refrigerant
Mechanical work input
is rejected to the surroundings.
The liquid refrigerant then goes
through a throttle valve. Work
Heat in
is done by the liquid in getting
through the valve at the expense
TL
of its internal energy. It leads Low temperature reservoir
to the drop in the temperature
of the liquid. The cooled liquid Fig. 16.18. Schematic representation of a refrigerator. It
absorbs heat QL from the low temperature reservoir and
flows through the evaporation expels and heat QH to the high temperature reservoir. Work
coils where it absorbs heat and W is done on the engine.
boils. The gaseous refrigerant
goes into the compressors and the cycle repeats.

QH
High temperature
reservoir
TH

P1

Oneway
flow valve

Liquid W
storage Condenser

Compressor
Oneway
flow valve
Evaporator

Throttle
P2

QL
TL
Low tempreture
reservoir

Fig. 16.19. Essential features of a common refrigerator.

Elements of Thermodynamics 425

The performance of a refrigerator is specified by a figure of merit Kr called the coefficient

of performance.
Q QL
Kr = L = (16.35)
W QH − QL
The quantity QL is the amount of heat absorbed from the cold compartment at the
temperature TL. The quantity QH is the heat rejected into the surroundings. QH is equal to the
heat absorbed QL plus the work done on the refrigerant by the compressor.
Thus, W = QH − QL. Assuming that the cycle is a reverse Carnot cycle, we can write.
TL
Kr =   Carnot cycle   (16.36)
TH − TL
For a house-hold refrigerator, typical temperatures are TH = 305 K (32° C) and TL = 260
K (= – 13° C) which give a typical value of 5.8 for Kr.
16.16 SECOND LAW OF THERMODYNAMICS
There are two classical statements of the second law of thermodynamics. They are known as
the Kelvin-Planck statement and the Clausius statement.
An analysis of operation of heat engines led William Thomson (later Lord Kelvin) and
Planck to arrive at the following conclusion:
It is impossible to construct a heat engine that will operate in a cycle and which will
receive a given amount of heat from a high-temperature reservoir and does an equal amount
of work. The only alternative is that some heat must be transferred from the working fluid to
a low temperature reservoir. Therefore, work can be done by the transfer of heat only if there
are two temperature levels involved.
The analysis of operation of heat pumps led Rudolf Clausius to conclude as follows:
It is impossible to construct a device that operates in a cycle and produces no effect other
than the transfer of heat from a cold body to a hot body. In effect, it is impossible to construct
a refrigerator that operates without an input of work.
The first law of thermodynamics is concerned with conservation of energy. As long as the
energy is conserved in a process, the first law is satisfied. A cycle in which a given amount
of heat is transferred from the system and an equal amount of work is done on the system
satisfies the first law but it does not ensure that the cycle will actually occur. The second
law emphasizes the fact that processes proceed in a certain direction but not in the opposite
direction. For instance, a hot cup of coffee cools by virtue of heat transfer to the surroundings
but heat will not flow from the cooler surroundings to the hot cup of coffee. Thus, real
processes proceed only in one direction. It is important to take note of the fact that a cycle
will occur only if both the first and the second laws of thermodynamics are satisfied.
The first law of thermodynamics is a general statement of the conservation of energy. It
makes no distinction between the different forms of energy. The second law of thermody-
namics asserts that thermal energy is different from all other forms of energy. Various forms
of energy can be converted into thermal energy spontaneously and completely, where as the
reverse transformation is never complete. The impossibility of converting heat completely
into mechanical energy forms the basis of Kelvin-Planck statement of second law. The fact
that work may be dissipated completely into heat whereas heat may not be converted entirely
into work expresses the essential one sidedness of nature.
426 A Textbook of Engineering Physics

The basis of second law lies in the difference between the nature of mechanical energy
and the nature of internal energy. Mechanical energy is the energy of ordered motion of a
body. Internal energy is the energy of random motion of molecules within the body. When
the body moves, the motion is due to the ordered motion of molecules within it as a whole
in the direction of velocity of the body. The energy associated with this ordered motion of
molecules is the kinetic energy. The kinetic and potential energies associated with the random
motion is the internal energy. When a moving body comes to rest due to friction, the ordered
portion of the kinetic energy becomes converted into energy of random molecular motion. It
is impossible to reconvert the energy of random motion completely to the energy of ordered
motion, since we cannot control the motions of individual molecules. We can convert only a
portion of it. That is what a heat engine does.

16.17 ENTROPY
The differential form of the first law of thermodynamics is written as
dQ = dU + dW
The work dW done depends on the path of process and therefore it is not a function of
the state. The same is the case with dQ, the quantity of heat supplied or taken away. The work
dW can be expressed in terms of thermodynamic variables and their changes. For instance, we
have expressed dW in equ.(16.2) as
dW = P dV
It is found that dQ can also be expressed in a similar fashion, in case of reversible
processes. We write
dQ = T dS (16.37)
where dS is called the change in entropy and T is the temperature. Now, we define the change
in entropy as
dQ
dS = Reversible process   (16.38)
T
The change in entropy dS in the course of an infinitesimal change is equal to the quantity
of heat dQ divided by the absolute temperature T, where dQ is the heat absorbed (or rejected)
when the change is carried out in a reversible manner.
The total entropy change in a reversible process may be obtained by integrating equ.
(16.38). Thus,
2
dQ
DS = S2 – S1 = ∫ T
(16.39)
1
where S1 and S2 are the entropies of the initial and final states of the system.
The importance of the entropy S is that it is a function of state like the internal energy
U. Both these parameters depend only on the initial and final states of the system and not
on the path of the process that takes the system from the initial state to final state. Equation
(16.39) assumes a simpler form when the process is an isothermal process. As T is constant in
isothermal process, equ.(16.39) may be written as
2 2
dQ 1 Q
DS = ∫ T = T ∫ dQ = T
1 1
Elements of Thermodynamics 427

Q
Thus, DS = Isothermal Process   (16.40)
T
The units of entropy and entropy change are J/K.
In practice, the value of entropy S is not of much interest. We have to know the change in
entropy when the system changes from one state to another.
16.17.1 Entropy, Disorder and Second Law
When processes occur, in general, they are irreversible and the degree of disorder increases
as a result of these processes. As an example, let us take the case of isothermal expansion
of an ideal gas (Fig. 16.10). As the gas absorbs heat, it slowly expands. At the end of the
process the gas occupies a greater volume than at the beginning. The gas molecules are more
disordered now. The gas will not, by its own accord, give up its thermal energy and segregate
itself to confine to the initial volume. We, thus, observe that the flow of heat takes place in
the direction that increases the amount of disorder. The same type of order to disorder change
occurs when free expansion of gas occurs, when one gas diffuses into another, and in similar
other spontaneous processes.
Rudolf Clausius (1822-1888), the German physicist, introduced the quantity entropy
which is regarded as a measure of disorder in a system. An increase in disorder is equivalent
to an increase in entropy. Irreversible processes are processes for which entropy increases.
These considerations led Clausius to reformulate the second law of thermodynamics in
terms of entropy. According to it, the entropy of an isolate system always tends to increase.
Mathematically, it is expressed as
DSisolated system ≥ 0 (16.41)
16.17.2 Some Interesting Points
1. The net change in entropy in any reversible cycle is zero.
Let us take the case of Carnot cycle as an example. There is no change in entropy of the
working substance during the two adiabatic paths. Either during adiabatic expansion or
compression, Q = 0. Therefore, S = 0. However, there is an increase in entropy during
isothermal expansion, as heat QH is added at a constant temperature TH. The consequent
Q
increase in entropy DS1 = H . There is a decrease in entropy during the isothermal
TH
Q
compression in which heat QL is rejected at a temperature TL. Thus, DS2 = − L .
TL
\ The net change in entropy is given by
QH QL
DS = DS1 + DS2 = −
TH TL
QH Q
But = L
TH TL
\ DS = 0 Reversible Cycle   (16.42)
2. Entropy increases in all irreversible processes.
It is proved that there is a net increase in the entropy during irreversible processes. Since
all real processes taking place in the universe are irreversible, there is a continuous increase
428 A Textbook of Engineering Physics

in its entropy. For this reason, entropy is not conserved. In this respect entropy differs from
energy.
We can illustrate this by taking a simple example. Suppose a small quantity of heat dQ is
radiated away from a hot body A, at a temperature TH, to a cold body B at a temperature TC.
Let dQ be so small that TH and TC are not altered appreciably, due to the exchange of heat.
However, the entropy of A decreases by –dQ/TH where as that of B increases by dQ/TC in this
process.
dQ dQ
\ DS = −
TC TH
As TH > TC, DS > 0 (16.43)
3. Entropy indicates the direction in which processes proceed in nature.
All natural processes are irreversible. They proceed in the direction of increasing entropy.
4. Entropy represents the unavailability of energy.
In the thermodynamic sense, entropy is a measure of the capability to do work or transfer
heat. A system at a higher temperature will tend to do work on and/or transfer heat to its lower
temperature surroundings. In the process, the entropy of the system increases and the greater
the entropy the less available is the energy.
Let us consider the example of Carnot engine. The efficiency of Carnot engine is given
by
T
h = 1− L
TH
 T 
As QH is the heat input, heat converted into work = QH 1 − L 
 TH 

\ Heat unavailable for work = QH = TL

But QH / TH represents the increase in entropy ΔS during isothermal expansion.
\ Energy wasted = TL ΔS (16.44)
If TL is constant, the amount of energy wasted is proportional to the increase in entropy.

16.18 THIRD LAW OF THERMODYNAMICS

With a decrease in temperature, a greater degree of order prevails in any system. If we could
cool a system to 0K, the maximum conceivable order would be established in the system and
the minimum entropy would correspond to this state. Now, suppose we apply a pressure on
the system at 0K. What does happen to the entropy of the system? On the basis of experiments
conducted at low temperatures, W.Nernst concluded that “at 0K, any change in the state of a
system takes place without a change in the entropy”. This is called Nernst’s theorem. It is
also called the third law of thermodynamics. Third law of thermodynamics is sometimes
known as the principle of unattainability of absolute zero. It is stated as follows:
It is impossible to attain a temperature of 0K.
Elements of Thermodynamics 429

QUESTIONS
1. Show that work is a path function, and not a property.
2. State the first law for a closed system undergoing a change of state.
3. What is thermodynamics? State the first, second and third laws of thermodynamics and discuss
their significance. (Andhra Univ.)
4. What is a cyclic heat engine?
5. Define the thermal efficiency of a heat engine cycle. Can this be 100%?
6. Give the Kelvin-Planck statement of the second law.
7. Give the Clausius statement of the second law.
8. What is a reversible process? A reversible process should not leave any evidence to show that
the process had ever occurred. Explain.
9. All spontaneous processes are irreversible. Explain.
10. Distinguish between a reversible and an irreversible process. Illustrate your answer by some
examples. (Andhra Univ.)
11. What is a Carnot Cycle? What are the four processes which constitute the cycle?
12. Describe the different operations involved in a Carnot’s cycle. Derive the efficiency of a Carnot
engine in terms of source and sink temperatures. (Andhra Univ.)
13. What is a reversed heat engine?
14. Show that the efficiency of a reversible engine operating between two given constant
temperatures is the maximum.
15. How does the efficiency of a reversible engine vary as the source and sink temperatures are
varied? When does the efficiency become 100%?
16. What do you understand by the entropy principle?
17. Show that the transfer of heat through a finite temperature difference is irreversible.
18. Show that the adiabatic mixing of two fluids is irreversible.
19. What is the maximum work obtainable from two finite bodies at temperatures T1 and T2?
20. Why is the second law called a directional law of nature?
21. Give the Nernst statement of the third law of thermodynamics.