MODULE - 3 Thermodynamics

Thermal Physics

11
Notes

THERMODYNAMICS

You are familiar with the sensation of hotness and coldness. When you rub your
hands together, you get the feeling of warmth. You will agree that the cause of
heating in this case is mechanical work.This suggests that there is a relationship
between mechanical work and thermal effect. A study of phenomena involving
thermal energy transfer between bodies at different temperatures forms the subject
matter of thermodynamics, which is a phenomenological science based on
experience. A quantitative description of thermal phenomena requires a definition
of temperature, thermal energy and internal energy. And the laws of
thermodynamics provide relationship between the direction of flow of heat, work
done on/by a system and the internal energy of a system.
In this lesson you will learn three laws of thermodynamics : the zeroth law, the
first law and the second law of thermodynamics. These laws are based on
experience and need no proof. As such, the zeroth, first and second law introduce
the concept of temperature, internal energy and entropy, respectively. While the
first law is essentially the law of conservation of energy for a thermodynamic
system, the second law deals with conversion of heat into work and vice versa.You
will also learn that Carnot’s engine has maximum efficiency for conversion of
heat into work.

OBJECTIVES
After studying this lesson, you should be able to :
z draw indicator diagrams for different thermodynamic processes and show
that the area under the indicator diagram represents the work done in the
process;
z explain thermodynamic equilibrium and state the Zeroth law of
thermodynamics;

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z explain the concept of internal energy of a system and state first law of
thermodynamics;
z apply first law of thermodynamics to simple systems and state its limitations;
z define triple point;
z state the second law of thermodynamics in different forms; and
z describe Carnot cycle and calculate its efficiency. Notes

11.1 CONCEPT OF HEAT AND TEMPERATURE

11.1.1 Heat
Energy has pervaded all facets of human activity ever since man lived in caves. In
its manifestation as heat, energy is intimate to our existence. The energy that
cooks our food, lights our houses, runs trains and aeroplanes originates in heat
released in burning of wood, coal, gas or oil. You may like to ask : What is heat?
To discover answer to this question, let us consider as to what happens when we
inflate the tyre of a bicycle using a pump. If you touch the nozzle, you will observe
that pump gets hot. Similarly, when you rub you hands together, you get the
feeling of warmth. You will agree that in these processes heating is not caused by
putting a flame or something hot underneath the pump or the hand. Instead, heat
is arising as a result of mechanical work that is done in compressing the gas in the
pump and forcing the hand to move against friction. These examples, in fact,
indicate a relation between mechanical work and thermal effect.
We know from experience that a glass of ice cold water left to itself on a hot
summer day eventually warms up. But a cup of hot coffee placed on the table
cools down. It means that energy has been exchanged between the sysem – water
or coffee – and its surrounding medium. This energy transfer continues till thermal
equilibrium is reached. That is until both – the system and the suroundings – are
as the same temperature. It also shows that the direction of energy transfer is
always from the body at high temprature to a body at lower temperature. You
may now ask : In what form is energy being transferred? In the above examples,
energy is said to be transfered in the form of heat. So we can say that heat is the
form of energy transferred between two (or more) systems or a system and its
surroundings because of temperature difference.
You may now ask. What is the nature of this form of energy? The answer to this
question was provided by Joule through his work on the equivalence of heat and
mechanical work : Mechanical motion of molecules making up the system is
associated with heat.
The unit of heat is calorie. One calorie is defined as the quantity of heat energy
required to raise the temperature of 1 gram of water from 14.5oC to 15.5oC. It is
denoted as cal.

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Kilocalorie (k cal) is the larger unit of heat energy :
1 kcal = 103 cal.
Also 1 cal = 4.18 J

11.1.2 Concept of Temperature

Notes While studying the nature of heat, you learnt that energy exchange between a
glass of cold water and its surroundings continues until thermal equilibrium was
reached. All bodies in thermal equilibrium have a common property, called
temperature, whose value is same for all of them. Thus, we can say that temperature
of a body is the property which determines whether or not it is in thermal
equilibrium with other bodies.

11.1.3 Thermodynamic Terms

(i) Thermodynamic system : A thermodynamic system refers to a definite
quantity of matter which is considered unique and separated from everything
else, which can influence it. Every system is enclosed by an arbitrary surface,
which is called its boundary. The boundary may enclose a solid, a liquid or a
gas. It may be real or imaginary, either at rest or in motion and may change
its size and shape. The region of space outside the boundary of a system
constitutes its surroundings.
(a) Open System : It is a system which can exchange mass and energy
with the surroundings. A water heater is an open system.
(b) Closed system : It is a system which can exchange energy but not mass
with the surroundings. A gas enclosed in a cylinder fitted with a piston
is a closed system.
(c) Isolated system : It is a system which can exchange neither mass nor
energy with the surrounding. A filled thermos flank is an ideal example
of an isolated system.
(ii) Thermodynamic Variables or Coordinates : In module–1, we have studied
the motion of a body (or a system) in terms of its mass, position and velocity.
To describe a thermodynamic system, we use its physical properties such on
temperature (T), pressure (P), and volume (V). These are called
thermodynamic variables.
(iii) Indicator diagram : You have learnt about displacement–time and velocity–
time graphs in lesson 2. To study a thermodynamic system, we use a pressure-
volume graph. This graph indicates how pressure (P) of a system varies with
its volume (V) during a thermodynamic process and is known as an indicator
diagram.

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The indicator diagram can be used to obtain an expression for the work done. It
is equal to the area under the P-V diagram (Fig. 11.1). Suppose that pressure is P
at the start of a very small expansion ΔV. Then, work done by the system.
ΔW = P ΔV (11.1)
= Area of a shaded strip ABCD
Now total work done by the system when it expands from V1 to V2 = Area of Notes
P1P2V2V1P1 Note that the area depends upon the shape of the indicator diagram.
The indicator diagram is widely used in P
calculating the work done in the process
of expansion or compression. It is found P1
more useful in processes where P.DV
D P2
relationship between P and V is not known. A
The work done on the system increases
its energy and work done by the system
reduces it. For this reason, work done on V
V1 B C V2
the system is taken as negative. You must
Fig. 11.1 : Indicater Diagram
note that the area enclosed by an isotherm
(plot of p versus V at constant temperature) depends on its shape. We may conclude
that work done by or on a system depends on the path. That is, work does not
depend on the initial and final states.

11.2 THERMODYNAMIC EQUILIBRIUM

Imagine that a container is filled with a liquid (water, tea, milk, coffee) at 60º C.
If it is left to itself, it is common experience that after some time, the liquid attains
the room temperature. We then say that water in the container has attained thermal
equilibrium with the surroundings.
If within the system, there are variations in pressure or elastic stress, then parts of
the system may undergo some changes. However, these changes cease ultimately,
and no unbalanced force will act on the system. Then we say that it is in mechanical
equilibrium. Do you know that our earth bulged out at the equator in the process
of attaining mechanical equilibrium in its formation from a molten state?
If a system has components which react chemically, after some time, all possible
chemical reactions will cease to occur. Then the system is said to be in chemical
equilibrium.
A system which exhibits thermal, mechanical and chemical equilibria is said to be
in thermodynamic equilibrium. The macroscopic properties of a system in this
state do not change with time.

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11.2.1 Thermodynamic Process
If any of the thermodynamic variables of a system change while going from one
equilibrium state to another, the system is said to execute a thermodynamic process.
For example, the expansion of a gas in a cylinder at constant pressure due to
heating is a thermodynamic process. A graphical representation of a thermodynamic
process is called a path.
Notes Now we will consider different types of thermodynamic processes.
(i) Reversible process : If a process is executed so that all intermediate stages
between the inital and final states are equilibrium states and the process can
be executed back along the same equilibrium states from its final state to its
initial state, it is called reversible process. A reversible process is executed
very slowly and in a controlled manner. Consider the following examples :
• Take a piece of ice in a beaker and heat it. You will see that it changes to
water. If you remove the same quantity of heat of water by keeping it
inside a refrigerator, it again changes to ice (initial state).
• Consider a spring supported at one end. Put some masses at its free end
one by one. You will note that the spring elongates (increases in length).
Now remove the masses one by one. You will see that spring retraces
its initial positions. Hence it is a reversible process.
As such, a reversible process can only be idealised and never achieved
in practice.
(ii) Irreversible process : A process which cannot be retraced along the same
equilibrium state from final to the initial state is called irreversible process.
All natural process are irrerersible. For example, heat poduced during friction,
sugar dissolved in water, or rusting of iron in the air. It means that for
irrerersible process, the intermediate states are not equilibrium states and
hence such process can not be represented by a path. Does this mean that
we can not analyse an irrerersible process? To do so, we use quasi-static
process, which is infinitesimally close to the equilibrium state.
(iii) Isothermal process : A thermodynamic process that occurs at constant
temperature is an isothermal process. The expansion and compression of a
perfect gas in a cylinder made of perfectly conducting walls are isothermal
processes. The change in pressure or volume is carried out very slowly so
that any heat developed is transferred into the surroundings and the
temperature of the system remains constant. The thermal equilibrium is always
maintained. In such a process, ΔQ, ΔU and ΔW are finite.
(iv) Adiabatic process : A thermodynamic process in which no exchange of
thermal energy occurs is an adiabatic process. For example, the expansion

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and compression of a perfect gas in a cylinder made of perfect insulating
walls. The system is isolated from the surroundings. Neither any amount of
heat leaves the system nor enters it from the surroundings. In this process,
therefore ΔQ = 0 and ΔU = –ΔW.
The change in the internal energy of the system is equal to the work done on
the system. When the gas is compressed, work is done on the system. So,
ΔU becomes positive and the internal energy of the system increases. When Notes
the gas expands, work is done by the system. It is taken as positive and ΔU
becomes negative. The internal energy of the system decreases.
(v) Isobaric process : A thermodynamic process that occurs at constant pressure
is an isobaric process. Heating of water under atmospheric pressure is an
isobaric process.
(vi) Isochoric process : A thermodynamic process that occurs at constant volume
is an isochoric process. For example, heating of a gas in a vessel of constant
volume is an isochoric process. In this process, volume of the gas remains
constant so that no work is done, i.e. ΔW = 0. We therefore get ΔQ = ΔU.
In a Cyclic Process the system returns back to its initial state. It means that there
is no change in the internal energy of the system. ΔU = 0.
∴ ΔQ = ΔW.

11.2.2 Zeroth Law of Thermodynamics

Let us consider three metal blocks A, B and C. Suppose block A is in thermal
equilibrium with block B. Further suppose that block A is also in thermal
equilibrium with block C. It means the temperature of the block A is equal to the
temperature of block B as well as of block C. It follows that the temperatures of
blocks B and C are equal. We summarize this result in the statement known as
Zeroth Law of Thermodynamics :
If two bodies or systems A and B are separately in thermal equilibrium with a
third body C, then A and B are in thermal equilibrium with each other.

Phase Change and Phase Diagram

You have learnt that at STP, matter exists in three states : solid, liquid and
gas. The different states of matter are called its phases. For example, ice
(solid), water (liquid) and steam (gas) are three phases of water. We can
discuss these three phases using a three dimensional diagram drawn in
pressure (P), temperature (T) and volume (V). It is difficult to draw three
dimensional diagram. Thus, we discuss the three phases of matter by drawing
a pressure-temperature diagram. This is called phase diagram.

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B

Ice
D e
lin

lin
m
ea

e
C St
e A
P t lin P
fr os
ar
Ho E
F
Notes T
Fig. 11.2: Phase diagram of water

Refer to Fig. 11.2, which shows phase diagram of water. You can see three
curves CD; AB and EF. Curve CD shows the variation of melting point of
ice with pressure. It is known as a fusion curve. Curve AB shows variation
of boiling point of water with pressure. It is known as vaporization curve.
Curve EF shows change of ice directly to steam. It is known as a sublimation
curve. This curve is also known as Hoarfrost Line.

If you extend the curve AB, CD and EF (as shown in the figure with dotted
lines), they meet at point P. This point is called triple point. At triple point,
all three phases co-exist.

When we heat a solid, its temperature increases till it reaches a temperature

at which it starts melting. This temperature is called melting point of the
solid. During this change of state, we supply heat continuously but the
temperature does not rise. The heat required to completely change unit mass
of a solid into its corresponding liquid state at its melting point is called
latent heat of fusion of the solid.

On heating a liquid, its temperature also rises till its boiling point is reached.
At the boiling point, the heat we supply is used up in converting the liquid
into its gaseous state. The amount of heat required to convert unit mass of
liquid in its gaseous state at constant temperature is called latent heat of
vaporization of the liquid.

11.2.3 Triple Point of Water

Triple point of a pure substance is a very stable state signified by precisely constant
temperature and pressure values. For this reason, in kelvin’s scale of thermometry,
triple point of water is taken as the upper fixed point.
On increasing pressure, the melting point of a solid decreases and boiling point of
the liquid increases. It is possible that by adjusting temperature and pressure, we
can obtain all the three states of matter to co-exist simultaneously. These values
of temperature and pressure signify the triple point.

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INTEXT QUESTIONS 11.1

1. Fill in the blanks
(i) Zeroth law of thermodynamics provides the basis for the concept of
.............
Notes
(ii) If a system A is in thermal equilibrium with a system B and B is in
thermal equilibrium with another system C, then system A will also
be in thermal equilibrium with P
system...............
P1 A
(iii) The unit of heat is
2. Fig. 11.3 is an indicator diagram of a P2 C
B
thermodynamic process. Calculate the work
done by the system in the process :
(a) along the path ABC from A to C
(b) If the system is returned from C to A V
V1 V2
along the same path, how much work
Fig. 11.3
is done by the system.
3. Fill in the blanks.
(i) A reversible process is that which can be ...................... in the opposite
direction from its final state to its initial state.
(ii) An ............................. process is that which cannot be retraced along
the same equilibrium states from final state to the initial state.
4. State the basic difference between isothermal and adiabatic processes.
5. State one characteristic of the triple point.

11.3 INTERNAL ENERGY OF A SYSTEM

Have you ever thought about the energy which is released when water freezes
into ice ? Don’t you think that there is some kind of energy stored in water. This
energy is released when water changes into ice. This stored energy is called the
internal energy. On the basis of kinetic theory of matter, we can discuss the
concept of internal energy as sum of the energies of individual components/
constituents. This includes kinetic energy due to their random motion and their
potential energy due to interactions amongst them. Let us now discuss these.
(a) Internal kinetic energy : As you now know, according to kinetic theory,
matter is made up of a large number of molecules. These molecules are in a
state of constant rapid motion and hence possess kinetic energy. The total

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kinetic energy of the molecules constitutes the internal kinetic energy
of the body.
(b) Internal potential energy : The energy arising due to the inter-molecular
forces is called the internal potential energy.
The internal energy of a metallic rod is made up of the kinetic energies of
conduction electrons, potential energies of atoms of the metal and the vibrational
Notes
energies about their equilibrium positions. The energy of the system may be
increased by causing its molecules to move faster (gain in kinetic energy by adding
thermal energy). It can also be increased by causing the molecules to move against
inter-molecular forces, i.e., by doing work on it. Internal energy is denoted by
the letter U.
Internal energy of a system = Kinetic energy of molecules + Potential energy of
molecules
Let us consider an isolated thermodynamic system subjected to an external force.
Suppose W amount of work is done on the system in going from initial state i to
final state f adiabatically. Let Ui and Uf be internal energies of the system in its
initial and final states respectively. Since work is done on the system, internal
energy of final state will be higher than that of the initial state.
According to the law of conservation of energy, we can write
Ui – Uf = – W
Negative sign signifies that work is done on the system.
We may point out here that unlike work, internal energy depends on the initial
and final states, irrespective of the path followed. We express this fact by saying
that U is a function of state and depends only on state variables P, V, and T. Note
that if some work is done by the system, its internal energy will decrease.

11.4 FIRST LAW OF THERMODYNAMICS

You now know that the zeroth law of thermodynamics tells us about thermal
equilibrium among different systems characterised by same temperature. However,
this law does not tell us anything about the non-equilibrium state. Let us consider
two examples : (i) Two systems at different temperatures are put in thermal contact
and (ii) Mechanical rubbing between two systems. In both cases, change in their
temperatures occurs but it cannot be explained by the Zeroth law. To explain
such processes, the first law of thermodynamics was postulated.
The first law of thermodynamics is, in fact, the law of conservation of energy for
a thermodynamic system. It states that change in internal energy of a system
during a thermodynamic process is equal to the sum of the heat given to it and
the work done on it.

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Suppose that ΔQ amount of heat is given to the system and – ΔW work is done
on the system. Then increase in internal energy of the system, ΔU, according to
the first law of thermodynamics is given by
ΔU = ΔQ – ΔW (11.3 a)
This is the mathematical form of the first law of thermodynamics. Here ΔQ, ΔU
and ΔW all are in SI units.
Notes
The first law of thermodynamics can also be written as
ΔQ = ΔU + ΔW (11.3 b)
The signs of ΔQ, ΔU and ΔW are known from the following sign conventions :
1. Work done (ΔW) by a system is taken as positive whereas the work done on
a system is taken as negative. The work is positive when a system expands.
When a system is compressed, the volume decreases, the work done is
negative. The work done does not depend on the initial and final
thermodynamic states; it depends on the path followed to bring a change.
2. Heat gained by (added to) a system is taken as positive, whereas heat lost by
a system is taken as negative.
3. The increase in internal energy is taken as positive and a decrease in internal
energy is taken as negative.
If a system is taken from state 1 to state 2, it is found that both ΔQ and ΔW
depend on the path of transformation. However, the difference (ΔQ – ΔW) which
represents ΔU, remains the same for all paths of transformations.
We therefore say that the change in internal energy ΔU of a system does not
depend on the path of the thermodynamic transformations.

11.4.1 Limitations of the First Law of Thermodynamics

The first law of thermodynamics asserts the equivalence of heat and other forms
of energy. This equivalence makes the world around us work. The electrical energy
that lights our houses, operates machines and runs trains originates in heat released
in burning of fossil or nuclear fuel. In a sense, it is universal. It explains the fall in
temperature with height; the adiabatic lapse rate in upper atmosphere. Its
applications to flow process and chemical reations are also very interesting.
However, consider the following processes :
• You know that heat always flows from a hot body to a cold body. But first
law of thermodynamics does not prohibit flow of heat from a cold body to a
hot body. It means that this law fails to indicate the direction of heat flow.
• You know that when a bullet strikes a target, the kinetic energy of the bullet
is converted into heat. This law does not indicate as to why heat developed

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in the target cannot be changed into the kinetic energy of bullet to make it
fly. It means that this law fails to provide the conditions under which heat
can be changed into work. Moreover, it has obvious limitations in indicating
the extent to which heat can be converted into work.
Now take a pause and answer the following questions :

Notes

INTEXT QUESTIONS 11.2

1. Fill in the blanks
(i) The total of kinetic energy and potential energy of molecules of a
system is called its ....................
(ii) Work done = – W indicates that work is done .................... the system.
2. The first law of thermodynamics states that ....................

11.5 SECOND LAW OF THERMODYNAMICS

You now know that the first law of thermodynamics has inherent limitations in
respect of the direction of flow of heat and the extent of convertibility of heat into
work. So a question may arise in your mind : Can heat be wholly converted into
work? Under what conditions this conversion occurs? The answers of such
questions are contained in the postulate of Second law of thermodynamics. The
second law of thermodynamics is stated in several ways. However, here you will
study Kelvin-Planck and Clausius statements of second law of thermodynamics.
The Kelvin-Planck’s statement is based on the experience about the performance
of heat engines. (Heat engine is discussed in next section.) In a heat engine, the
working substance extracts heat from the source (hot body), converts a part of it
into work and rejects the rest of heat to the sink (environment). There is no
engine which converts the whole heat into work, without rejecting some heat to
the sink. These observations led Kelvin and Planck to state the second law of
thermodynamics as
It is impossible for any system to absorb heat from a reservoir at a fixed
temperature and convert whole of it into work.
Clausius statement of second law of thermodynamics is based on the
performance of a refrigerator. A refrigerator is a heat engine working in the opposite
direction. It transfers heat from a colder body to a hotter body when external
work is done on it. Here concept of external work done on the system is important.
To do this external work, supply of energy from some external source is a must.
These observations led Clausius to state the second law of thermodynamics in
the following form.

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It is impossible for any process to have as its sole result to transfer heat from
a colder body to a hotter body without any external work.
Thus, the second law of thermodynamics plays a unique role for practical devices
like heat engine and refrigerator.

11.5.1 Carnot Cycle

You must have noticed that when water is boiled in a vessel having a lid, the Notes
steam generated inside throws off the lid. This shows that high pressure steam
can be made to do useful work. A device which can convert heat into work is
called a heat engine. Modern engines which we use in our daily life are based on
the principle of heat engine. These may be categorised in three types : steam
engine, internal combustion engine and gas turbine. However, their working can
be understood in terms of Carnot’s reversible engine. Let us learn about it now.

A (P1,V1)
T1
H1, T1
B (P2,V2)
T2
D
P (P4,V4) T1

H2, T2 C (P3,V3)

T2

E F G H
V

Fig. 11.4 : Indicator diagram of Carnot cycle

Fig. 11.5 : The cylinder with working substance

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In Carnot cycle, the working substance is subjected to four operations : (a)
isothermal expansion, (b) adiabatic expansion, (c) isothermal compression and
(d) adiabatic compression. Such a cycle is represented on the P-V diagram in Fig.
11.4. To describe four operations of Carnot’s cycle, let us fill one gram. mol. of
the working substance in the cylinder (Fig. 11.5). Original condition of the
substance is represented by point A on the indicator diagram. At this point, the
substance is at temperature T1, pressure P1 and volume V1.
Notes
(a) Isothermal expansion : The cylinder is put in thermal contact with the
source and allowed to expand. The volume of the working substance increases
to V2. Thus working substance does work in raising the piston. In this way,
the temperature of the working substance would tend to fall. But it is in
thermal contact with the source. So it will absorb a quantity of heat H1
from the source at temperature T1. This is represented by the point B. At B,
the values of pressure and volume are P2 and V2 respectively. On the indicator
diagram (Fig. 11.4), you see that in going from A to B, temperature of the
system remains constant and working substance expands. We call it
isothermal expansion process. H1 is the amount of heat absorbed in the
isothermal expansion process. Then, in accordance with the first law of
thermodynamics, H1 will be equal to the external work done by the gas
during isothermal expansion from A to B at temperature T1. Suppose W1 is
the external work done by the gas during isothermal expansion AB. Then it
will be equal to the area ABGEA. Hence
W1 = Area ABGEA
(b) Adiabatic expansion : Next the cylinder is removed from the source and
placed on a perfectly non-conducting stand. It further decreases the load on
the piston to P3. The expansion is completely adiabatic because no heat can
enter or leave the working substance. Therefore, the working substance
performs external work in raising the piston at the expense of its internal
energy. Hence its temperature falls. The gas is thus allowed to expand
adiabatically until its temperature falls to T2, the temperature of the sink. It
has been represented by the adiabatic curve BC on the indicator diagram.
We call it adiabatic expansion. If the pressure and volume of the substance
are P3 and V3, respectively at C, and W2 is the work done by the substance
from B to C, then
W2 = Area BCHGB.
(c) Isothermal compression : Remove the cylinder from the non-conducting
stand and place it on the sink at temperature T2. In order to compress the
gas slowly, increase the load (pressure) on the piston until its pressure and
volume become P4 and V4, respectively. It is represented by the point D on
the indicator diagram (Fig. 11.4). The heat developed (H2) due to compression
will pass to the sink. Thus, there is no change in the temperature of the
system. Therefore, it is called an isothermal compression process. It is shown

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by the curve CD (Fig. 11.4). The quantity of heat rejected (H2) to the sink
during this process is equal to the work done (say W3) on the working
substance. Hence
W3 = Area CHFDC
(d) Adiabatic compression : Once again place the system on the non-conducting
stand. Increase the load on the piston slowly. The substance will under go an
adiabatic compression. This compression continues until the temperature Notes
rises to T1 and the substance comes back to its original pressure P1 and
volume V1. This is an adiabatic compression process and represented by the
curve DA on the indicator diagram (Fig. 11.4). Suppose W4 is the work
done during this adiabatic compression from D to A. Then
W4 = Area DFEAD
During the above cycle of operations, the working substance takes H1 amount of
heat from the source and rejects H2 amount of heat to the sink. Hence the net
amount of heat absorbed by the working substance is
ΔH= H1 – H2
Also the net work done (say W) by the engine in one complete cycle
W = Area ABCHEA – Area CHEADC
= Area ABCD
Thus, the work done in one cycle is represented on a P-V diagram by the area of
the cycle.
You have studied that the initial and final states of the substance are the same. It
means that its internal energy remains unchanged. Hence according to the first
law of thermodynamics
W = H1 – H2
Therefore, heat has been converted into work by the system, and any amount of
work can be obtained by merely repeating the cycle.

11.5.2 Efficiency of Carnot Engine

Efficiency is defined as the ratio of heat converted into work in a cycle to heat
taken from the source by the working substance. It is denoted as η:
Heat converted into work
η =
Heat taken from source

H1 - H 2 H
or η = H1
= 1- 2
H1

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It can be shown that for Carnot’s engine,
H 2 T2
=
H1 T1

T2
Hence, η =1– T
1

Notes Note that efficiency of carnot engine does not depend on the nature of the working
substance. Further, if no heat is rejected to the sink, η will be equal to one. But
for H2 to be zero, T2 must be zero. It means that efficiency η can be100% only
when T2 = 0. The entire heat taken from the hot source is converted into work.
This violates the second law of thermodynamics. Therefore, a steam engine can
operate only between finite temperature limits and its efficiency will be less than
one.
It can also be argued that the Carnot cycle, being a reversible cycle, is most
efficient; no engine can be more efficient than a Carnot engine operating between
the same two temperatures.

11.5.3 Limitation of Carnot’s Engine

You have studied about Carnot’s cycle in terms of isothermal and adiabatic
processes. Here it is important to note that the isothermal process will take place
only when piston moves very slowly. It means that there should be sufficient time
for the heat to transfer from the working substance to the source. On the other
hand, during the adiabatic process, the piston moves extremely fast to avoid heat
transfer. In practice, it is not possible to fulfill these vital conditions. Due to these
very reasons, all practical engines have an efficiency less than that of Carnot’s
engine.

INTEXT QUESTIONS 11.3

1. State whether the following statements are true or false.
(i) In a Carnot engine, when heat is taken by a perfect gas from a hot
source, the temperature of the source decreases.
(ii) In Carnot engine, if temperature of the sink is decreased the efficiency
of engine also decreases.
2. (i) A Carnot engine has the same efficiency between 1000K and 500K
and between TK and 1000K. Calculate T.
(ii) A Carnot engine working between an unknown temperature T and ice
point gives an efficiency of 0.68. Deduce the value of T.

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Thermal Physics

WHAT YOU HAVE LEARNT

z Heat is a form of energy which produces in us the sensation of warmth.
z The energy which flows from a body at higher temperature to a body at lower
temperature because of temperature difference is called heat energy.
Notes
z The most commonly known unit of heat energy is calorie. 1 cal = 4.18 J and
1k cal = 103 cal.
z A graph which indicates how the pressure (P) of a system varies with its
volume during a thermodynamic process is known as indicator diagram.
z Work done during expansion or compression of a gas is PΔV = P(Vf – Vi).
z Zeroth law of thermodynamics states that if two systems are separately in
thermal equilibrium with a third system, then they must also be in thermal
equilibrium with each other.
z The sum of kinetic energy and potential energy of the molecules of a body
gives the internal energy. The relation between internal energy and work is Ui
– Uf = –W.
z The first law of thermodynamics states that the amount of heat given to a
system is equal to the sum of change in internal energy of the system and the
external work done.
z First law of thermodynamics tells nothing about the direction of the process.
z The process which can be retraced in the opposite direction from its final
state to initial state is called a reversible process.
z The process which can not be retraced along the same equilibrium state from
final to the initial state is called an irreversible process. A process that occurs
at constant temperature is an isothermal process.
z Any thermodynamic process that occurs at constant heat is an adiabatic
process.
z The different states of matter are called its phase and the pressure and
temperature diagram showing three phases of matter is called a phase diagram.
z Triple point is a point (on the phase diagram) at which solid, liquid and vapour
states of matter can co-exist. It is characterised by a particular temperature
and pressure.
z According to Kelvin-Planck’s statement of second law, it is not possible to
obtain a continuous supply of work from a single source of heat.

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 MODULE - 3 Thermodynamics

Thermal Physics
z According to Clausius statement of second law, heat can not flow from a
colder body to a hotter body without doing external work on the working
substance.
z The three essential requirements of any heat engine are :
(i) source from which heat can be drawn
Notes (ii) a sink into which heat can be rejected.
(iii) working substance which performs mechanical work after being
supplied with heat.
z Carnot’s engine is an ideal engine in which the working substance is subjected
to four operations (i) Isothermal expansion (ii) adiabatic expansion (iii)
isothermal compression and (iv) adiabatic compression. Such a cycle is called
a Carnot cycle.
z Efficiency of a Carnot engine is given only
H2
η=1– H1 , H1 = Amount of heat absorbed and H2 = Amount of heat
rejected.
T2
= 1 – T , T1 = Temperature of the source, and T2 = Temperature of the sink.
1

z Efficiency does not depend upon the nature of the working substance.

TERMINAL EXERCISE
1. Distinguish between the terms internal energy and heat energy.
2. What do you mean by an indicator diagram. Derive an expression for the
work done during expansion of an ideal gas.
3. Define temperature using the Zeroth law of thermodynamics.
4. State the first law of thermodynamics and its limitations.
5. What is the difference between isothermal, adiabetic, isobaric and isochoric
processes?
6. State the Second law of thermodynamics.
7. Discuss reversible and irreversible processes with examples.
8. Explain Carnot’s cycle. Use the indicator diagram to calculate its efficiency.
9. Calculate the change in the internal energy of a system when (a) the system
absorbs 2000J of heat and produces 500 J of work (b) the system absorbs
1100J of heat and 400J of work is done on it.

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Thermal Physics
10. A Carnot’s engine whose temperature of the source is 400K takes 200 calories
of heat at this temperature and rejects 150 calories of heat to the sink. (i)
What is the temperature of the sink. (ii) Calculate the efficiency of the engine.

ANSWERS TO INTEXT QUESTIONS

Notes
11.1
1. (i) Temperature (ii) C (iii) Joule or Calorie
2. (a) P2 (V2 – V1) (b) –P2 (V2 – V1)
3. (i) retrace (ii) irreversible
4. An isothermal process occurs at a constant temperature whereas an adiabatic
process occurs at constant heat.
5. At triple point all three states of matter i.e. solid, liquid and vapour can co-
exist.

11.2
1. (i) Internal energy (ii) on
2. It states that the amount of heat given to a system is equal to the sum of the
change in internal energy of the system and the external energy.

11.3
1. (i) False (ii) True
2. (i) 2000 K (ii) 8583.1K

Answers to Terminal Problems

9. (a) 1500 J (b) 1500 J.
10. 300K, 25%

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