BSc Physics Textbook on Kinetic Theory and Thermodynamics

TEXT BOOK
B.Sc. First Year Second Paper
st
(for B.Sc. I year students of All Colleges affiliated to Universities in Uttar Pradesh)
As per U.P. UNIFIED Syllabus
By
R.K. Agrawal
M.Sc., M.Phil., Ph.D.
Reader, Dep’t. of Physics
S.D. (P.G.) College, Muzaffarnagar (U.P.)
Garima Jain Rekha Sharma

M.Sc., M.Phil., Ph.D. M.Sc., M.Phil., Ph.D.
Reader, Dep’t. of Physics Associate Professor
D.A.V. College, Muzaffarnagar (U.P.) Department of Physics
Meerut College Meerut (U.P.)
KRISHNA Prakashan Media (P) Ltd.

KRISHNA HOUSE, 11, Shivaji Road, Meerut-250 001 (U.P.), India
470 Kinetic Theory and Thermodynamics (E) Binder2.pdf 1 7/30/2018 3:47:50 PM

Jai Shri Radhey Shyam
Dedicated
to
Lord
Krishna
Authors & Publishers

ast year U.P. State universities adopted Unified Syllabus suggested by
L M.H.R.D. New Delhi, U.G.C. and U.P. Government. So a great need was
being felt to suit the requirement of B.Sc. students.
We are happy to present this book which fulfils the requirements entitled ''Kinetic
Theory & Thermodynamics''.
Efforts are made to make the language of the book. Simple, fluent, lucid and rather
comprehensive. Some salient features of the book are as follows:
1. The book has been written strictly according to the unified syllabus of U.P. state
universities. The complete syllabus has been divided into Four Units.
2. According to the unified paper pattern, each unit has been divided into three sections
i.e., Section A: Descriptive part, Section B: Short part & Section C: Very short
part.
3. In section A, the complete syllabus of concerned unit is described in details and after
each article, some simple numerical examples are given based upon it, So that the
student may understand the concept well.
4. In each unit, Miscellaneous Problems are given which are based on different articles
of that unit.
5. At of the end of each unit, Some Probable Questions are given which have been or
may be asked in the university examination in a different manner.
We are thankful to our near and dear ones for their blessings, good wishes and
cooperation due to which the implementation of this project could become possible. It is
God who has blessed us to complete this work in time.
We are also thankful to Mr. S.K. Rastogi M.D. and Mr. Sugam Rastogi E.D.,
Krishna Prakashan Media (P) Ltd., and entire KPM team for taking keen interest in
getting the book published.
In spite of great care, some misprints and omissions might have crept in. We will be
grateful to teachers and students who will point out the same and give suggestions for
further improvement of the book.
It is hoped that present edition of the book will be found useful and fulfill a genius
need.
—Authors
(v)

Syllabus
Kinetic Theory &
Thermodynamics
B.Sc. I st Year Paper- II
U.P. UNIFIED (w.e.f. 2011-12)
Code. B-117 M.M. – 50
UNIT-I
Ideal Gas: Kinetic model, Deduction of Boyle's law, Interpretation of temperature, Estimation
of r.m.s. speeds of molecules. Brownian motion, Estimate of the Avogadro number.
Equipartition of energy, Specific heat of monatomic gas, Extension to di- and triatomic gases,
Behaviour at low temperatures. Adiabatic expansion of an ideal gas, Applications to
atmospheric physics.
Real Gas: Van der Waals gas, Equation of state, Nature of Van der Waals forces, Comparison
with experimental P-V curves. The critical constants, Gas and vapour. Joule expansion of ideal
gas, and of a Van der Waals gas, Joule coefficient, estimates of J-T cooling.
UNIT II
Liquefaction of Gases: Boyle temperature and inversion temperature. Principle of regenerative
cooling and of cascade cooling, Liquefaction of hydrogen and helium. Refrigeration cycles,
meaning of efficiency.
Transport Phenomena in Gases: Molecular collisions, mean free path and collision cross
sections. Estimates of molecular diameter and mean free path. Transport of mass, momentum
and energy and interrelationship, dependence on temperature and pressure.
UNIT III
The Laws of Thermodynamics: The Zeroth law, various indicator diagrams, Work done by
and on the system, First law of thermodynamics, Internal energy as a state function and other
applications. Reversible and irreversible changes, Carnot cycle and its efficiency, Carnot
theorem and the second law of thermodynamics. Different versions of the second law, Practical
cycles used in internal combustion engines. Entropy, principle of increase of entropy. The
thermodynamic scale of temperature; its identity with the perfect gas scale.
Impossibility of attaining the absolute zero; Third law of thermodynamics. Thermodynamic
relationships: Thermodynamic variables; Extensive and intensive, Maxwell's general
relationships, Application to Joule-Thomson cooling and adiabatic cooling in a general system,
Van der Waals gas, Clausius-Clapeyron heat equation. Thermodynamic potentials and
equilibrium of thermodynamical systems, relation with thermodynamical variables. Cooling
due to adiabatic demagnetization, production and measurement of very low temperatures.
UNIT IV
Blackbody Radiation: Pure temperature dependence, Stefan-Boltzmann law, Pressure of
radiation, Spectral distribution of Black body radiation, Wien's displacement law, Rayleigh-
Jean's law, Plank's law the ultraviolet catastrophy.
(vi)

Brief Contents
Dedication........................................................................ (iii)
Preface............................................................................(v)
Syllabus..........................................................................(vi)
Brief Contents.................................................................(vii)
Detailed Contents...................................................... (viii-xii)
Unit-I
Kinetic Theory of Matter.............................................................01-62
Unit-II
Liquefaction of Gases and Transport
Phenomena in Gases................................................................63-94
Unit-III
Thermodynamics...................................................................95-216
Unit-IV
Black Body Radiation............................................................217-246
(vii)

Detailed Contents
Unit-I
Kinetic Theory of Matter ....................................................01-62
1.1 Kinetic Theory of Matter 03
1.1.1 Solids 04
1.1.2 Liquid 04
1.1.3 Gases 04
1.2 Kinetic Theory of Gases 05

1.2.1 Pressure of a Gas 05
1.3 Deduction of Gas Laws from Kinetic Theory 08

1.3.1 Boyle's Law 08
1.3.2 Charle's Law 09
1.3.3 Avogadro's Law 09
1.3.4 Dalton's Law of Partial Pressures 10
1.3.5 Graham's Law of Diffusion 10
1.4 Interpretation of Temperature on the Basis of Kinetic Theory 11
1.5 Root Mean Square Speed of Molecules 13

1.5.1 Relation between v rms and Molecular Weight 13
1.6 Brownian Motion 17
1.7 Estimation of Avogadro's Number 18
1.8 Degrees of Freedom of a Particle or System 19
1.9 Law of Equipartition of Energy 21
1.10 Specific Heat of Gases 23

1.10.1 Two Specific Heats of a Gas 23
1.10.2 Difference between C P and CV 23
1.11 Ratio of Specific Heats of an Ideal Gas 24
1.12 Ratio of Molecular Specific Heats for Monoatomic,

Diatomic and Triatomic Gases 25
1.12.1 Behaviour of Specific Heat of Gases at Low Temperature 26
1.13 Adiabatic Expansion of an Ideal Gas 27
1.14 Application of Kinetic Theory to Atmospheric Physics 28

1.14.1 The upper atmosphere is cold while its kinetic temperature is of the order
of 1000K 28
(viii)

1.14.2 Moon has no Atmosphere 29
1.15 Van der Waal's Equation of State for Real Gases 29

1.15.1 Correction for the Finite Size of Molecules 29
1.15.2 Correction for Intermolecular Attraction 30
1.15.3 Nature of Van der Waal's Forces 30
1.15.4 Comparison of Van der Waal's Equation with Experimental p-V Curves
(Andrew Curves) 31
1.15.5 Drawbacks of Van der Waal's Equation 31
1.16 Critical Constants of a Gas 32

1.16.1 Critical Temperature 32
1.16.2 Critical Pressure 32
1.16.3 Critical Volume 32
1.16.4 Critical Constants in terms of 'a' and 'b' 32
1.16.5 Difference between a Gas and Vapour 34
1.17 Joule's Law 36

1.17.1 Joule's Expansion Experiment 36
1.18 Joule-Thomson (Kelvin) Effect 38

1.18.1 Porous Plug Experiment 38
1.18.2 Results 39
1.18.3 Explanation of Results 39
1.19 Joule Thomson Expansion for an Ideal Gas 40
1.20 Joule-Thomson (Kelvin) Effect 42

1.20.1 Expression for Joule Thomson Effect in a Van der Waal’s Gas 42
1.20.2 Relation between Critical Temperature and Temperature of Inversion 44
$ Miscellaneous Problems 47
$ Exercise 56
$ Answers 61
Unit-II
Liquefaction of Gases and Transport Phenomena in Gases....63-94
2.1 Liquefaction of Gases 65
2.2 Boyle Temperature 66

2.2.1 Inversion Temperature 67
2.2.2 Relation between Temperature of Inversion & Critical Temperature 67
2.3 Principle of Regenerative Cooling 67

2.3.1 Principle of Cascade Cooling 67
2.4 Principle of Liquefaction of Hydrogen 68

2.4.1 Method 68
2.5 Liquefaction of Helium 69
(ix)

2.6 Refrigeration Cycle 70
2.7 Efficiency 71
2.8 Molecular Collision 72

2.8.1 Mean Free Path 72
2.8.2 Collision Cross-Section 72
2.9 Expression for Mean Free Path 73

2.9.1 Variation of Mean Free Path with Temperature and Pressure 74
2.10 Transport Phenomena in Gases 75
2.11 Transport of Mass 76
2.12 Transport of Momentum 79
2.13 Transport of Energy 82
2.14 Relation between Thermal Conductivity and Viscosity of a Gas 84

$ Exercise 90
$ Answers 93
Unit-III
Thermodynamics ............................................................95-216
3.1 System and Surroundings 97
3.2 Macroscopic System and Microscopic System 97

3.2.1 Relation between Macroscopic and Microscopic Properties 98
3.3 Temperature 98
3.3.1 Thermal Equilibrium 98
3.3.2 Zeroth Law of Thermodynamics 98
3.4 Thermodynamic System 99

3.4.1 Thermodynamical Equilibrium 99
3.4.2 Quasi-static process 99
3.5 p –V or Indicator Diagram 100

3.5.1 Thermodynamic Processes 100
3.5.2 Work Done During an Isothermal Process 100
3.5.3 Work Done During an Adiabatic Process 101
3.6 Work done depends upon on the Path between initial and final States 105
3.7 First Law of Thermodynamics 106

3.7.1 Physical Significance of First Law of Thermodynamics 107
3.7.2 Applications of the First Law of Thermodynamics 107
3.8 Internal Energy of a System 111
3.9 Reversible Process 112

(x)

3.9.1 Irreversible Process 112
3.9.2 Necessary Condition for Reversible Process/Engine 112
3.10 Carnot's Cycle 112

3.10.1 Efficiency of engine in terms of temperature of the source T1 and sink T2 K 115
3.11 Carnot's Theorem 118
3.12 Second Law of Thermodynamics 120

3.12.1 Equivalence of Kelvin and Calusius Statement 120
3.13 Internal Combustion Engine 121
3.14 Entropy 123

3.14.1 Physical Significance 124
3.15 Change of Entropy in Reversible Process 125

3.15.1 Change of Entropy in an Irreversible Process 126
3.15.2 Principle of Increase of Entropy 126
3.16 Entropy of a perfect gas in terms of its pressure, volume and specific heat 128
3.17 Absolute or Kelvin's or Thermodynamic Scale of Temperature 129

3.17.1 Absolute Zero 131
3.18 Thermodynamic Scale and Perfect Gas Scale 132
3.19 Practical Realization of Absolute Scale 133

3.19.1 Impossibility of Attaining the Absolute Zero 133
3.19.2 Third Law of Thermodynamics 134
3.20 Extensive and Intensive Variables 134
3.21 Maxwell's General Thermodynamic Relations 134
3.22 Heat Transfer in Isothermal Compression of a Liquid 137
3.23 Heat Transfer in Isothermal Expansion in Van der Waal's Gas 138
3.24 Temperature Change in Adiabatic Compression of a Liquid 139
3.25 Internal Energy of a Gas 140

3.25.1 For an Ideal Gas 140
3.25.2 For Van der Waal's Gas 141
3.26 Joule's Law for Perfect Gas 142

3.26.1 Cooling Due to Joule Free Expansion in Van Der Waal's Gas 142
3.27 Joule-Thomson Effect 142

3.27.1 Expression for Joule Thomson Cooling 143
3.27.2 Joule Thomson Coefficient for a Perfect Gas 144
3.27.3 Joule Thomson Coefficient for a Van der Waal's Gas 144
3.28 Effect of Increase in Pressure on Heated Body 146
3.29 The difference between two Specific heat for Homogeneous Fluid 147
3.29.1 For Perfect Gas 148
3.29.2 For Van der Waal's Gas 148
(xi)

3.30 Ratio of Adiabatic to Isothermal Elasticity 149
3.31 Clausius-Clapeyron Heat Equation 150
3.31.1 Effect of Pressure on Melting Point of Solids 152
3.31.2 Effect of Pressure on Boiling Point of Liquids 152
3.32 Specific Heat of Saturated Vapour 155

3.32.1 Clausius Second Latent Heat Equation 155
3.32.2 Explanation of the Negative Specific Heat of Saturated Water Vapour 157
3.33 Thermodynamic Potentials (Functions) 158

3.33.1 Internal Energy (U) 158
3.33.2 Helmholtz Function (F) 159
3.33.3 Enthalpy or Total Heat Content (Function) H 160
3.33.4 Gibb's Potential (G) 161
3.33.5 Importance of These Potentials 162
3.34 Thermodynamic Potential U (Internal Energy) & F (Free Energy) 163
3.34.1 Gibb's Helmholtz Equation 163
3.34.2 Importance 164
3.35 Cooling Due to Adiabatic Demagnetisation 165
3.35.1 Expression for the Adiabatic Cooling 165
3.36 Production of Very Low Temperatures 167
3.36.1 Principle 167
3.36.2 Measurement of Temperature 168
$ Exercise 189
$ Answers 201
Unit-IV
Black Body Radiation ....................................................217-246
4.1 Radiation Dependent on Temperature Only 220
4.2 Pressure of Radiation 221
4.3 Stefan Law 222
4.3.1 Stefan–Boltzmann Law 223
4.3.2 Thermodynamic Proof of Stefan's Law 223
4.4 Spectral Distribution of Black Body Radiation 227

4.4.1 Explanation of Curves 228
4.5 Planck's Quantum Hypothesis 231

4.5.1 Average Energy of Planck's Oscillator 231
4.5.2 Planck's Radiation Formula 232
4.5.3 Wien's Law and Rayleigh-Jeans Law are Special Case of Planck's Law 233
4.6 Ultra Violet Catastrophe 233

$ Exercise 239
$ Answers 243 rrr
(xii)

UNI T I
Kinetic Theory of Matter
Ideal Gas: Kinetic Theory of Matter
Kinetic Theory of Gases
Deduction of Important Gas Laws
Interpretation of Temperature
Estimation of Root mean Square Speed of Molecules
Brownian Motion, Estimation of Avogadro Number
Degrees of Freedom of a Particle or System
Law of Equipartition of Energy
Specific Heat of Gases
Ratio of Specific Heats of an Ideal Gas
Ratio of Molecular Specific Heats for Monoatomic, Diatomic & Triatomic Gases
Behaviour of Specific Heat of Gases at Low Temperature
Adiabatic Expansion of an Ideal gas
Application of Kinetic Theory to Atmospheric Physics
Real Gas: Van der Waal's Gas Equation of State of Real Gas
Nature of Van der Waal's Forces
Comparison of Van der Waal's Equation with Experimental p-V (Andrew)Curves
The Critical Constants
Difference between a Gas and Vapour
Joule's Law, Joule Expansion Experiment
Joule-Thomson Effect and Porous Plug Experiment
Joule-Thomson Expansion for an Ideal Gas, Joule Coefficient
Joule-Thomson Expansion for an Van Der Waal's Gas
Estimations of J-T Cooling

3
Kinetic Theory of Matter
T h e gas which strictly obeys the gas laws (Boyle's laws, Charle's law etc.), at all
temperatures and pressures, remaining as a gas, is known as perfect or ideal gas. The
molecules of an ideal gas do not exert force of attraction on one another. Therefore, its
molecules have only kinetic energy which depends on temperature. The gas equation for
1 mole of an ideal gas is,
pV = RT
where all symbols have their usual meanings.

All real gases deviate from these gas laws to a smaller or greater extent. The general
nature of the deviations is small at low pressure and high temperature, but large at high
pressure and low temperatures. Also they can be liquified (even solidified) under
appropriate conditions of temperature and pressure.
1.1 Kinetic Theory of Matter

There is a close relationship between heat and mechanical energy. The nature of this
relationship is given by the kinetic theory of matter. Because it explains the nature of heat,
so may be called as kinetic theory of heat. It is based on following two postulates :
(i) Matter is not continuous but consists of very small particles in large number, called
molecules. Even if molecules are in contact with each other there are interspaces in
between them. A molecule is the smallest part of the substance having all of its
characteristic properties and can have an independent existence.

4
(ii) The molecules are in a state of continuous motion. i.e., they move haphazardly with great
speeds in all directions. The freedom of movement of the molecules is different in
three states of matter. i.e., solid, liquid and gas.
On the basis of kinetic theory, three states of matter are explained in the following
way:
1.1.1 Solids
In solids, molecules are densely packed and exert a large cohesive force on each other.
In this way molecules are nearly fixed in their position and can only oscillate about
their mean (fixed) positions. This explains why a solid has a definite shape and volume.
When a solid is heated, its molecules gain energy and the distance between their
equilibrium positions increases. It causes the solid body to expand and is known as
thermal expansion. On heating it further, the distance between the molecules becomes
so large that the forces of attraction become negligibly small. The molecules are free to
move inside the solid which now turns into liquid. This is known as melting of solid.
The temperature of this liquid remains as that of the solid because the heat taken by
the solid in melting is used up in over coming the force of attraction between the
molecules and pull them apart. It is called the latent heat of the fusion of the solid.
1.1.2 Liquid
The molecule in a liquid are farther apart than in a solid and attract each other with
smaller force of cohesion. They cannot easily leave the liquid but they are free to move
about anywhere within the liquid, which explains why a liquid has a definite volume
but not the shape.
In the interior of the liquid, the molecule is attracted equally in all directions, therefore
no resultant force acts on it. But the molecules near the surface experience a net force of
attraction on them due to the molecules below it. On account of this inward directed
force, the surface of the liquid behaves like a stretched membrane which is the
explanation of surface tension.
1.1.3 Gases
In a gas, molecules are very much farther apart and the cohesive force of attraction is
almost negligible. So, the molecules are free to move about over the entire space
available. This is why a gas has neither a shape nor volume of its own.
The fundamental concept of kinetic theory i.e., the existence of molecules in random
motion explains several thermal properties of three states of matter such as expansion,
change of state, melting and boiling point, cooling due to evaporation and temperature
rise on compression etc.

5
1.2 Kinetic Theory of Gases

The fundamental assumptions of the kinetic theory of gases are as follows:
(i) All gases are made up of small particles called molecules. The molecules of a gas
are identical (i.e., in size and shape) to each other and are perfectly rigid and
elastic spheres.
(ii) These molecules are continuously moving in all direction with all possible
velocities.
(iii) During this motion, molecules collide with each other and also with the walls of
the containing vessel. Consequently there is a change in direction and magnitude
of their velocities at each collision. However, this does not affect the molecular
density of the gas i.e., the number of molecules per unit volume of the gas remains
the same.
(iv) The collisions are perfectly elastic and there are no forces of attraction and
repulsion between the molecules. It means that all the energy of gas is kinetic in
form.
(v) The duration of a collision is negligibly small in comparison to the time spent by a
molecule between the collisions.
(vi) The molecules move in straight lines with uniform velocity between any two
collisions. The distance between two collisions is called the free path of molecule and its
average value (i.e., the average distance travelled by a molecule between successive
collisions) is called mean free path. It depends on the temperature and pressure of
the gas.
1.2.1 Pressure of a Gas

The molecules in random motion not only collide with one another but also collide and
exert pressure on the walls of the vessel. As the molecule collides with the walls, it
suffers a change in momentum. The rate of change of momentum is equal to the force
exerted on the wall. Since the number of such impacts which the molecules are making
with the walls is very great, the walls experience an almost continuous force. This force
measured per unit area is known as the pressure of the gas.
Thus, according to kinetic theory, the pressure exerted by a gas is the total momentum
transmitted to the walls of the vessel, per second per unit area due to the impacts of the
gas molecules. The expression for the pressure exerted by a gas can be derived as
follows:
Let there be a gas enclosed in a cubical vessel of side l with its perfectly elastic walls
(Fig. 1.1). Let the number of molecules present in the vessel be n and mass of each
molecule be m. These molecules are moving in all directions with different velocities.
Consider one molecule moving with velocity v in any direction. Its velocity can be

6
resolved into three components v x , v y , vz parallel to three co-ordinate axes X, Y and Z

which are assumed parallel to sides of the cube. Then
v2 = v x2 + v y2 + vz 2 ...(1)
F B
Let this molecule moves along X-axis and strikes
elastically the face ABCD which is perpendicular to A
E Vy
X-axis. By this motion, only the v x component of V
velocity will be affected while the v y and vz remain Vx
l
unaltered. The momentum of the molecule in X G Vz
I C
direction before collision is mv x . When it collides
with the face ABCD, as the collision is perfectly H D
elastic, it rebounds with the same velocity but Fig. 1.1
reversed in direction. So the momentum of the
molecule now becomes − mv x . Therefore, change in momentum,
= mv x − (− mv x ) = 2 mv x
After recoil the molecule moves towards opposite face EFHG and collides with it. Here
again it rebounds and travels back to face ABCD after covering a distance 2l. The time
taken between two successive collisions on ABCD = (2 l / v x ).
So, the number of collisions in one second = (v x / 2 l)
The rate of change of momentum = Change of momentum in one collision × Number
of collisions per second.
v mv2x
= 2 mv x × x =
2l l
But, according to Newton's second law of motion, the rate of change of momentum is
equal to force. Therefore, this is the force exerted by the molecules on the wall ABCD.
Thus,
mv2x
fx =
l
mv2x
To obtain total force on the wall ABCD due to all molecules, we have to sum up
l
for all particles. Let v x , is the x component of velocity of particle 1, v x is that of
1 2
particle 2, then total force on wall ABCD,
Fx = ( f x + f x + f x + .... f x )
1 2 3 n
n
m
= (m / l) (v2x + v2x + .... v2x ) = ∑ v2x ...(2)
1 2 n l i
i =1

7
force Fx
and the pressure on wall ABCD = =
area l2
n
m
⇒ px = ∑ v2x
l3 i =1 i
...(3)
Similarly, the pressures on the walls perpendicular to Y and Z-axis respectively are
given by,
n
m
v2
3 ∑ y
py = ...(4)
i
l i =1
n
m
and pz = ∑ v2z
l3 i = 1 i
...(5)
Since, the pressure exerted by the gas is same in all directions, so we have
px = p y = pz = p (say) and total pressure, px + p y + pz = 3 p
n n n
m m m
∴ 3p = ∑ v2x + ∑ v2y + ∑ v2z
l3 i =1 1
l3 i =1 1
l3 i =1 1
m
or p= [(v2x + v2x + v2x + .... v2x ) + (v2y + v2y + .... + v2y )
3 1 2 3 n 2 2 n
3l
+ (v2z + v2z + ..... + v2z )]

1 2 n
m
= [(v2x + v2y + v2z ) + (v2x + v2y + v2z 2 ) + .... + (v2x + v2y + v2z )]
3 l3 1 1 1 2 2 n n n
m m
= [(v12 + v22 + v32 .... + v2n )] = [(v2 + v22 + ..... v2n )] ...(6)
3l3 3V 1
Since, l3 = V = (Volume of the cube)
v12 + v22 + .... + v2n –2

Also, =v
n
–
where v2 is known as mean square velocity of the molecules. Its square root is known as
root mean square velocity (vrms ). Thus, the pressure exerted by the gas in all directions,
mn –2
p= v
3V
If M be the total mass of the gas, then M = mn
1 –2
or p= ρv ...(7)
3
where ρ = mn / V = density of the gas i. e., mass per unit volume.

8
2 1 – 
We may write it as, p=  ρ v2  ...(8)
3 2 
 
1 –2
and ρ v is the kinetic energy per unit volume of the gas. Hence, the pressure of the
2
gas is numerically equal to two third of the total translational kinetic energy of
the molecules per unit volume. If the gas is compressed, the kinetic energy of
translation of its molecules increase. Hence, the temperature of the gas increases.
Example 1: Compute the number of molecules in 1 meter3 of an ideal gas at 27°C and
a pressure of 10 mm of Hg. The average translational kinetic energy of a molecule at
27°C is 6.2 × 10 −21 joule. The density of mercury is 13.6 × 10 3 Kg/meter3 and
g = 9.8 nt/Kg.
Solution: We know that the pressure exerted by an ideal gas is given by,
2 1 –  2
p=  ρ v2  = (K.E. per unit volume)
3 2  3
 
2 3
or pV = K.E. or K.E. = pV
3 2
Here, p = 10 −2 meter of Hg = 10 −2 × 13.6 × 103 × 9. 8 = 1.33 × 103 nt/m2 and V =1 meter3 .
Thus, the kinetic energy for the whole gas = (3 / 2) × 1. 33 × 103 × 1 = 1. 995 × 103 joule
But the average kinetic energy per molecule = 6 . 2 × 10 −21 joule,
1. 995 × 103
∴ No of molecules = = 3. 2 × 10 23 .
−21
6 . 2 × 10
1.3 Deduction of Gas Laws from Kinetic Theory

1.3.1 Boyle's Law
All gases law can be deduced from the kinetic theory of gases as follows:
According to Boyle's law, at constant temperature, the product of pressure and volume of a given
mass of gas is constant.
From the kinetic theory of gases, the pressure p of a gas is given by,
1 mn –2
p= v
3 V
1 –
or pV = mn v2
3

9
At a constant temperature, the mean square velocity is constant. Hence, for a given
mass (i.e., mn constant) of gas, and at constant temperature
pV = constant which is Boyle's law.
1.3.2 Charle's Law

Charle's law, can be stated in two ways:
At constant pressure, the volume of a given mass of gas is directly proportional to its absolute
temperature, or at constant volume, pressure of a gas is directly proportional to its absolute
temperature.
1 mn –2
According to kinetic theory of gas, p = v
3 V
1 – 2 1 – 
or pV = mn v2 = n  m v2 
3 3  2 

–
and we know that, (1 / 2) m v2 = (3 / 2) kT = mean kinetic energy of a molecule.
2 3 
∴ pV = n  kT  , where k is Boltzman constant and T is absolute temperature.
3 2 
= nkT = RT (nk = R ), where R is the gas constant

or pV = RT
Thus, at constant pressure, V ∝ T , which is Charle's law
or at constant volume, p ∝ T , which is also Charle's law.
1.3.3 Avogadro's Law

According to this law, at the same temperature and pressure equal volumes of all gases contain
equal number of molecules.
To deduce it from kinetic theory, let us consider unit volume (1 c.c.) of two different
gases which are at the same pressure ( p) and temperature (T ). Suppose n1 and n2 are the
– –
numbers of molecules per c.c. of two gases m1 and m2 their masses and v12 and v22 their
mean square velocities respectively. Since the pressure exerted by the two gases is same.
So,
1 – 1 –
p= m n v2 = m n v 2 ...(1)
2 111 2 2 2 2
(Q Volume V =1 c.c)
If the gases are at the same temperature, their average kinetic energies of translation
per molecule must be equal. Thus,

10
1 – 1 –
m1 v12 = m2 v22 ...(2)
2 2
Putting eq. (2) in eq. (1), n1 = n2
i.e., the number of molecules per c.c. in both the gases are equal. This is Avogadro's
hypothesis.
1.3.4 Dalton's Law of Partial Pressures

This law states that the total pressure exerted by a mixture of gases or vapours (having no
chemical reaction with each other) is equal to the sum of their individual (or partial) pressures.
Let a number of non-reacting gases or vapours having densities ρ1, ρ2 , ρ3 , K and mean
– – –
square velocities v12 , v22 , v32 .... respectively be mixed together in the same volume.
Then, the resultant pressure p is given by,
1 – 1 – 1 –
p= ρ v 2 + ρ1 v22 + ρ3 v32 + ...
3 1 1 3 3
[Q ρ = mn / V = mass per unit volume]
1 – 1 –
But, ρ1 v12 , ρ2 v22 ..... are the individual or partial pressures of the different gases or
3 3
vapours respectively. Let us denote them by p1, p2 , p3,.... then
p = p1 + p2 + p3 + ....
This is Dalton's law of partial pressures.
1.3.5 Graham's Law of Diffusion

This law states that the rate of diffusion of a gas is inversely proportional to the square root of its
density.
Let us consider, a gas of density ρ1 diffusing into another gas of density ρ2 . In the steady
– –
state of diffusion, the pressures of both the gases are same. If v12 and v22 be the mean
square velocities of the molecules of two gases, respectively, then
1 – 1 –
p= ρ v2= ρ v 2
3 1 1 3 2 2
–
v1 ρ (vrms )1 ρ
or = 2 or = 2
– ρ1 (vrms )2 ρ1
v2
and their rates of diffusion must be proportional to their rms velocities, so

γ1 (vrms )1 ρ 1
= = 2 or γ ∝ vrms ∝
γ2 (vrms )2 ρ1 ρ
where γ1 and γ2 represents their rates of diffusion. This is Graham's law of diffusion.

11
1.4 Interpretation of Temperature on the Basis of

Kinetic Theory
According to kinetic theory of gases, the pressure exerted by 1 gm mole of gas is given by,
–
1 – 1 mN v2 1 –
p = ρ v2 = or pV = m N v2
3 3 V 3
where V is the volume occupied by a gram molecule of the gas N is avogadro number
and mN = M (molecular weight)
1 –
Hence, M v2 pV = ...(1)
3
Using the gas equation for one mole of an ideal gas,
pV = RT ...(2)
1 – – 3R
∴ RT = M v2 or v2 = T = constant × T ...(3)
3 M
–
Equation (3) shows that the mean square velocity v2 is directly proportional to the
absolute temperature T.
– –
When T = 0, v2 = 0 or v = 0
This means that, the absolute zero of temperature is that temperature at which the translational
velocities of the molecules of a gas are reduced to zero.
1 –2 3
Further from eq. (3), M v = RT ...(4)
2 2
Dividing both sides of the equation by N, Avogadro's number i.e., the number of
molecules in one gram molecule (1 mole) of the gas, then equation (4) becomes,
1 M –2 3 R
v = T
2 N 2 N
But, M / N = m and R / N = a constant k called Boltzman constant
1 –2 3
∴ m v = kT ...(5)
2 2
Hence, the average kinetic energy of translation of the molecules of an ideal gas is
directly proportional to its absolute temperature. It means a uniform temperature
corresponds to a uniform distribution of kinetic energy. This is known as kinetic
interpretation of temperature.
Example 2: Given: Avogadro's number N = 6 . 02 × 10 23 and Boltzmann's constant

k = 1. 38 × 10 −23 joule/molecule K. Calculate
(a) The average kinetic energy of translation of the molecules of an ideal gas at 0°C and
at 100°C.
(b) Also calculate the corresponding energies per mole of the gas.

12
Solution:
(a) We know that the average kinetic energy of translation for molecule of an ideal
gas = (3 2)kT
where T is temperature in Kelvin and k is Boltzmann constant. At 0°C, T = 273 K
The kinetic energy of translation of the molecules at 0°C
= 3 / 2 kT = (3 / 2) × (1. 38 × 10 −23 ) × 273 = 5 . 65 × 10 −21 joule/molecule
At 100°C, T = 373,
The translational kinetic energy of the molecules = (3 / 2) × 1. 38 × 10 −23 × 373
= 7 . 72 × 10 −21 joule/molecule
(b) 1 mole of gas has N = 6 . 02 × 1023 molecules. Hence, the kinetic energy of
translation of 1 mole of gas at 0°C,
= 5 . 65 × 10 −21 × 6 . 02 × 1023 ≈ 3400 joule/mole
and translational kinetic energy of 1 mole of gas at 100°C
= 7 . 72 × 10 −21 × 6 . 02 × 1023 ≈ 4646 joule/mole
Example 3: The translational kinetic energy of a molecule of hydrogen at 0°C is

5 . 64 × 10 −21 joules and the gas constant R = 8 . 32 joule/mole-K. Calculate Avogadro's
number N.
Solution: The average kinetic energy of translation a per molecule of a gas,

3 3 R
kT = T
2 2 N
where N is Avogadro's number.
Given that, at 0 ° C, or T = 273 K the translational kinetic energy of a molecule
= 5 . 64 × 10 −21 joules and R = 8 . 32 joule/mole-K
3 8 . 32
∴ 5.64 × 10 −21 = × × 273
2 N
3 8 . 32 × 273
or N= × = 6.02 ×10 23
2 5 . 64 × 10 −21
Example 4: Find the molecular kinetic energy of 1 gram of helium at N.T.P. What will
be the energy at 100 ° C.
Solution: The kinetic energy of 1 gram of helium,
1 – 1 –
= M v2 = × 1 × v2 [∴ M = 1 gm]
2 2
But we have that,

13
– 3 RT
2
v =
M
where M is the molecular weight of the gas.
∴ Molecular K.E. of 1 gram of He at N.T.P.
1 3 RT 3 RT
× =
2 M 2M
At N.T.P., T = 273 K, M = 4, R = 8 . 31 joules/mole-K

3 8 . 31 × 273
∴ Molecular K.E. = × = 85.73 joule
2 4
At T = 373 K, the molecular K.E.,
3 8 . 31 × 373
= × = 1162.36 joule
2 4
1.5 Root Mean Square Speed of Molecules

According to kinetic theory, molecule of a gas are moving constantly in straight lines in
all directions. All these molecules do not move with the same speed, but the speeds are
distributed about an average value depending upon the temperature of the gas. If
v1, v2 , v3 , ..... vn be the speeds of n molecules of a gas, then the square root of the mean
of the squares of these speeds is called the root mean square speed vrms of the
molecules. Thus,
– v12 + v22 + .... + vn2
vrms = v2 =
n
Evidently it is not the same as the mean of the velocities of the different molecules.
According to kinetic theory, the pressure exerted by an ideal gas is,
1
p = ρ v 2 where ρ is the density of the gas.
3
– 3p – 3p
2
∴ v = or vrms = v2 =
ρ ρ
Further, we know that the speed of sound in a gas is given by,
γ p p
vs = = γ
ρ ρ
v
= γ rms or vs = constant × vrms
3
Hence, the speed of sound in a gas is proportional to root mean square speed of its molecules.
1.5.1 Relation between v rms and Molecular Weight

The mean square speed of gas molecules is given by,
– 3p mn – 3 pV
2
v = but ρ = ∴ v2 =
ρ V mn

14
where mn is the mass of the gas which occupies the volume V. Using the general gas
equation,
pV = nRT
– 3 n RT 3 RT
2
so that, v = =
mn M
where M is the molecular weight of the gas (for one mole of gas n =1, so m = M). Thus,
3 RT
vrms =
M
i.e., the rms speed of perfect gas molecules is inversely proportional to the square root of the
molecular weight of the gas.
If m be the mass of a single molecule and N be Avogadro's number then, M = mN
3 RT 3 kT 1  R 
∴ vrms = = or vrms ∝ Q = k
mN m m  N 
if two gases have molecules of mass m1 and m2 their respective rms speeds are
(vrms )1 and(vrms )2
(vrms )1 m2
then, =
(vrms )2 m1
It means that the lighter gas whose molecules have a larger rms speed would escape faster than the
heavier gas. Due to this fact the diffusion process can be used to separate lighter isotopes
from a normal specimen of a material. For example ordinary. Uranium has two isotopes
i.e., U235 (0.7%) and U238 (99.3%). The lighter isotope U235 is used in construction of
atom bomb, because its nucleus can be comparatively much easily fissioned. If U235 can
be separated from U238 by allowing a gaseous compound of Uranium to diffuse through
the porous walls of a container, the gas which is diffused earlier will be of U235 . This
process is repeated by using a number of diffusion stages but the diffusion time in each
stage must be small. If the time would be large, both gases will ultimately diffuse out
and it would not be possible to separate them. The enriched uranium is utilized to
make an atomic bomb.
Example 5: Find the rms velocity of the molecules of nitrogen at 20°C. Molecular
weight of nitrogen is 28 and R = 8 . 31 × 10 3 joule/kilomole-degree.
Solution: At temperature T, the rms velocity of the molecules of a gas is given by,
3 RT
vrms =
M
where M is molecular weight of gas.
Here T = 20 ° C = 293 K, R = 8 . 31 × 103 joule/kilomole-K
and M = 28 Kg/kilomole

15
3 × 8 . 31 × 103 × 293
∴ vrms = = 510 meter/sec.
28
Example 6: At a temperature of 273 K and a pressure of 1.01 × 10 −2 atm, a gas has a

density of 1. 24 × 10 −2 kg/mt3 . Calculate the rms speed of molecules of the gas. Identify
the gas. ( R = 8 . 31 joule/mole-K).
Solution: We know that the rms speed of the molecules of a gas at pressure p is given by,
3p
vrms =
ρ
where ρ is the density of the gas.
Here, p = 1.01 × 10 −2 atm = 1. 02 × 103 nt/mt2 (Q1 atm pressure = 1. 01 × 105 nt/mt2 )
3 × 1. 02 × 103
∴ vrms = = 494 m/sec.
1. 24 × 10 −2
This is the rms speed of gas molecules at a temperature T = 273K.

The relation between rms speed and molecular weight M is given by,
3 RT 3 RT 3 × 8 . 31 × 273
vrms = or M = =
M (vrms )2 (494)2
= 0 . 0279 Kg/mole = 27.0 gm/mole ≈ 28 gm/mole
Hence, the gas is nitrogen whose molecular weight is 28.
Example 7: At what temperature the rms speed of a gas molecule will be double of its
value at N.T.P. while the pressure remains unchanged.
3 KT
Solution: We know that, vrms =
m
At N.T.P., T = 0 °C = 273 K
3 k × 273
vrms = ...(1)
m
Let at TK, vrms becomes double of its value at N.T.P.
3 kT
∴ 2 vrms =
m
from equations (1) and (2),

T
2= or T = 4 × 273
273
or T = 1092K = 819 °C

16
Example 8: The root mean square speed of oxygen moleule is 460 meters/sec at 0°C.
Calculate the rms speeds of helium and argon at 40°C. The molecular weights of
oxygen, argon and helium are 32, 40 and 4 gm/mole respectively.
Solution: The root mean square speed vrms of a gas is proportional to square root of its
temperature (in Kelvin). Let us calculate vrms for oxygen at 40°C, then
(vrms )40 273 + 40 313
= =
(vrms )0 273 273
313 313
∴ (vrms )40 = (vrms )0 × = 460 × = 492 . 5 m/sec
273 273
3RT
Further, by using vrms = (M is the molecular weight) we can calculate the rms
M
speeds of helium and argon at same temperature. So,
(vrms )O MHe M0
= or (vrms )He = (vrms )0 ×
(vrms )He M0 MHe
32  M0 32 
(vrms )He = 492 . 5 × = 1393 m/sec Q = 
4  MHe 4 
32  M0 32 
Similarly, (vrms )Ar = 492 . 5 × = 440 m/sec Q = 
40  MAr 40 
Example 9: Calculate the temperature at which rms speed of nitrogen molecules will
become half of the roms speed of hydrogen molecules at 200 K. Molecular weights of
N2 and H2 are 28 and 2 respectively.
Solution: For hydrogen and nitrogen molecules we may write,

3 R TN 3 R TH
(vrms )N = and (vrms )H =
2 MN 2 MH
( M is the molecular weight)

(vrms )N TN MH
2
Dividing, = ×
(vrms )H MN TH
2
1
Given that, for TH = 200 K, (vrms )N = (v )
2 2 rms H 2
1 TN × 2
∴ =
2 200 × 28
1 T
or = N or TN = 700 K =427 ° C
4 2800

17
Example 10: The density of nitrogen gas at N.T.P. is 1.25 gm/litre. Calculate the root
mean square speed of its molecules at 0°C and at 20°C.
Solution: We know that at pressure p the root mean square speed of a molecule,
3p
vrms =
ρ
where ρ is the density of the gas.
Here, at N.T.P., p = 1. 013 × 105 Newton/meter2 and ρ = 1. 25 gm/litre =1. 25 Kg/mt3 .
Therefore, rms speed at (normal temperature) 0°C is,
3 × (1. 013 × 105 )

vrms = = 493 m/sec
1. 25
Further, we know that rms speed is proportional to square root of temperature, i. e.,
vrms ∝ T ,
(vrms )0 ° C T0 273
Thus, = =
(vrms )20 °C T20 293
293 293
or (vrms )20 = (vrms )0 × = 493 × = 510 m/sec
273 273
Example 11: Calculate the rms speed of the hydrogen molecules at room temperature.
Given that 1 litre of the gas at room temperature and normal pressure weighs
0 . 086gm.
3p
Solution: We know that, vrms =
ρ
0 . 086
Here, p = 76 ×13 . 6 ×981 dynes/cm2 and ρ= = 86 ×10 −6 gm/c.c.
1000
3 × 76 × 13 . 6 × 981
∴ vrms = = 1. 88 × 105 cm/sec
−6
86 × 10
= 1. 88 × 10 2 m/sec
1.6 Brownian Motion

This phenomenon was discovered in 1827 by an English botanist Brown. He found that
pollen suspended in water shows a continuous random motion when examined
microscopically. This phenomenon was most clear in case of colloidal solution. The
suspended particles were observed moving to and fro, rising and sinking rapidly and
continuous in a random way. This irregular motion of particles is named as ‘Brownian
Motion’. This type of motion can also be observed in smoke particles in air. It is found

18
that smaller the particle, greater is the motion. Also the motion was independent of
shaking the vessel and smaller viscosity of liquid favours the faster motion. The size of
the particles in colloidal solution is of the order of 10 −4 cm. Thus, their size is about ten
thousand times larger than the size of molecules themselves.
Einstein gave an explanation of the Brownian motion on the basis of kinetic theory.
Einstein assumed that the particles suspended in a fluid take part in the thermal motion
of the molecules of the fluid. These particles are continuously bombarded on all sides by
the molecules of the fluid. Since the particles are of very small size (although much
larger as compared to the size of the molecules), the number of bombardments from all
sides are not equal and do not always balance each other exactly. Hence, a particle
always experiences an unbalanced force and is continuously driven about in random
directions. Thus, these particles behave as large molecules of the fluid.
1.7 Estimation of Avogadro's Number

French chemist Perrin made a thorough study of the (p+dp)A
Brownian motion of the colloidal suspension. The colloidal dh
particles suspended in a liquid behave like molecule of a gas
pA
which is in equilibrium under the influence of gravity.
h
Therefore, their density varies with height in the liquid (in
the same way as the pressure of the atmosphere varies with
altitude). Sea level
Fig. 1.2
Consider a small element of the gas at a height h from the
bottom (sea level) as shown in fig. 1.2. Let A be the face
area, and dh the thickness of the element. The mass of the element is ρAdh and its
weight is ρAdhg, where ρ is the density of the gas at the height h.
Let p be the pressure (upwards) on the lower face and p + dp (downward) the pressure
on the upper face of the element. The upward force acting an the element is pA, and the
downward force is ( p + dp) A plus the weight of the element. Since the element is in
equilibrium, so, the resultant force on it must be zero i. e.,
pA = ( p + dp) A + ρgAdh
or dp = − ρgdh ...(1)
Now, for 1 mole of an ideal gas, we have
pV = RT
But also we have, V = M / ρ, where M is the molecular weight of the gas.
If m be the mass of a particle of gas and N and the Avogadro's number, then M = mN .
Therefore,
V = mN / ρ

19
mN
∴ p = RT
ρ
ρRT
or p= ...(2)
mN
From equation (1) and (2), we have
dp ρ g dh m N mN g
=− =− dh
p ρRT RT
If n represents the number of particles per unit volume in the liquid, then
dn / n = dp / p
dn mN g
∴ =− dh
n RT
Let, at the bottom, the number of particles is n0 i.e.,
at h = 0, n = n0
Integrate the above express from h = 0 to h = h and n = n0 to n = n, we have
n h
dn mN g
∫ n
=−
RT ∫dh
n0 0
n mN g
or log =− h
n0 RT
mN gh
−
or n = n0 e RT ...(3)
If we consider the buoyancy effect of the liquid on the suspended particles, then the
effective mass m of the particle would be V (ρ − ρ' ), where V is the volume of a particle, ρ
the density of particle and ρ' density of the liquid. So by putting this value, equation (3)
becomes,
gh
− N V (ρ − ρ')
RT
n = n0 e
Perrin tested this equation on different molecules and determine the value of the
Avogadro's number N, as
RT n
N= log 0
V (ρ − ρ' ) g h n
Perrin measured the number of given particles suspended at different heights in a liquid
drop and determined the mass and density of the particles. He estimated the values of
N = 6.08 × 1023 particle/mole.
1.8 Degrees of Freedom of a Particle or System

The degree of freedom of a system is the number of independent variables required to describe
its state or position completely. For example, the position of a simple mass point in space

20
can be defined completely by the three cartesian co-ordinates x, y, z. It is therefore, said

to possess three degrees of freedom.
If we consider a dynamical system i. e., a body in motion (let point mass) then, the degree of
freedom of a dynamical system is the number of independent motions which the system or particle
can perform or the number of independent methods of exchanging energy or the number of
independent co-ordinates required to specify its dynamical position.
The molecules of a monoatomic gas (like He, Ar, Ne etc.) consists of a single atom and
it can be represented by a point in space, without assigning any internal structure to it.
Therefore, it can undergo only translatory motion in any direction in space which can
easily be resolved along three co-ordinate axes (Fig. 1.3a). Thus, it can have three
independent motions and hence three degrees of freedom. A monoatomic molecule can
also rotate about its own axis. But its moment of inertia is so small that its rotational
kinetic energy is negligible. Therefore, its K.E. of translation is significant only.
The molecule of a diatomic gas like (H2 , N2 , O2 etc.), consists of two atom connected
to each other by a rigid bond like a dumb bell (Fig. 1.3b). Such molecule can perform
not only translatory motion, but also rotate about any three mutually perpendicular
axes. But its moment of inertia about the axis joining the two atoms is negligibly small
as compared to that about the other two axes. Hence, it can have only two rotational
motions. Therefore, a diatomic molecule has five degrees of freedom, three of
translatory motion and two of rotatory motion.
Y Y Y
X X X
Z Z Z
Monoatomic Molecule Diatomic molecule Triatomic molecule
(a) (b) (c)
Fig. 1.3
A polyatomic molecule, like CO2 , CS2 can rotate about any of the three co-ordinate
axes if the three atoms are placed at the vertices of a triangle (fig. 1.3c). Thus, it has six
degrees of freedom in all, three of which are translational and three are rotational.
The number of degrees of freedom increases if the atoms of molecule could vibrate with
respect to each other.

21
1.9 Law of Equipartition of Energy

This law is about the distribution of thermal energy among the molecules of a gas or
any other system like it. It states that the total energy of a dynamical system in thermal
equilibrium is distributed equally among its various degrees of freedom and the energy associated
1
per molecule per degree of freedom kT, where k is Boltzmann's constant and T is temperature of
2
thermal equilibrium.
This law was first deduced by Maxwell in 1859 for energy of translation. Later on
Boltzmann showed that it was equally applicable to the energies of rotation and vibration.
Note: The principle of equipartition of energy is applicable to those degrees of

freedom, for which energy is expressed in terms of the square of a position co-ordinate
(x, y, z) or a velocity co-ordinate (v x , v y , vz ).
To prove it, we consider one mole of a gas at absolute temperature T. As the molecules
are in random translatory motion, the velocity v of a molecule may be resolved into
three components v x , v y , vz along three co-ordinate axes or the three degrees of
freedom. So,
v2 = v2x + v2y + v2z
Averaging over all the molecules in the gas, we have
– – – –
v = v2x + v2y + v2z
2
– – – –
where v2 is the mean square velocity of the molecules and v2x , v2y and v2z are the squares
of average component velocities along three axes.
As the molecules do not prefer any particular direction to move, therefore,
– – – –
v2x = v2y = v2z = (1 / 3) v2
Now, we know that the average kinetic energy of the molecule of a gas is given by,
–
(1 / 2) m v2 = (3 / 2) kT [k = Boltzmann's constant]
So that, the average kinetic energy of a molecule per degree of freedom is,
1 –2 1 –2 1 –2 1 –
1 3 1
m v x = m v y = m vz = m (v2 / 3) = . k T = kT
2 2 2 2 3 2 2
1
Thus, the average kinetic energy of a molecule per degree of freedom = kT.
2
Example 12: Given that, Avogadro number N = 6 . 02 × 10 23 and Boltzmann's constant

k = 1. 38 × 10 −23 joule/(molecule-K). Calculate (a) the average kinetic energy of
translation of an oxygen molecule at 27°C (b) the total kinetic energy of an oxygen
molecule at 27°C (c) the total kinetic energy of a gram-molecule of oxygen at 27°C.

22
Solution: From the law of equipartition of energy we know that the average kinetic
1
energy of a gas molecule per degree of freedom is kT.
2
Here, T = 273 + 27° C = 300K

(a) An oxygen molecule has 3 degrees of freedom with respect to translation.
Therefore, the average kinetic energy of translation per molecule,
1 3
=3 × = kT
kT 2
= (3 / 2) × (1. 38 × 10 −23 ) × 300 = 6.21 × 10 –21 joule/molecule.
(b) As the oxygen molecule is diatomic, it has 2 degrees of freedom with respect to
rotation also. So the total degrees of freedom is 5. Hence, the total kinetic energy
of the molecule,
1 5
=5 × kT = × (1. 38 × 10 −23 ) × 300
2 2
= 10 . 35 × 10 −21 joule/molecule.
(c) One gm-molecule of oxygen consists of N molecules. Hence, total kinetic energy of
1 gm-molecule of the gas = N × (5 / 2) kT
= 6 . 02 × 1023 × 10 . 35 × 10 −21
= 6231 joule/mole
Example 13: At what temperature will the kinetic energy of an atom be 1. 0 eV. (k =
1.38 × 10 −23 joule/molecule-K)
[Meerut 2003, 2002]

Solution: An atom consists of only 3 degrees of freedom which are translational and
from the law of equipartition of energy average kinetic energy per degree of freedom at
1
any kelvin temperature T is kT.
2
1
Therefore, average kinetic energy of an atom = 3 × kT
2
Here, (3 / 2)kT = 1. 0 eV = 1. 6 × 10 −19 joule
−19
2 1. 6 × 10
∴ T= × = 7730 K
3 1. 38 × 10 −23

23
1.10 Specific Heat of Gases

The specific heat of a substance is defined as “the quantity of heat required to raise the
temperature of unit mass through 1°C”. But this definition is not quite accurate because any
substance when heated, expands in volume and pushes back the surrounding air. So it
does some mechanical work against atmospheric pressure and the energy given to it is
used up in doing this external work. If, however the expansion of substance is prevented
by applying an external pressure on it, the heat required to raise the temperature will be
less. In the first case, the volume of the substance increases, its pressure remaining
constant while in the second case, the volume of the substance increases, its pressure
remaining constant while in the second case, pressure on the substance increases, its
volume remaining constant. In case of solids and liquids, this change in volume and
hence the external work done during heating is very small and can be neglected. But in
case of gases, large changes of volume and pressure occurs due to change in
temperature. Therefore, while defining the specific heat, it is necessary to state the
conditions under which gas is heated.
1.10.1 Two Specific Heats of a Gas

Depending on heating conditions, there are two specific heats of a gas e. g., the specific
heat at constant volume (CV ) and the specific heat at constant pressure (C p).
The specific heat at constant volume (CV ) is the amount of heat required to raise the temperature
of one gram gas through 1°C when the volume is kept constant.
The specific heat at constant pressure (C p) is the amount of heat required to raise the temperature
of one gram gas through 1°C when its pressure is kept constant.
When a gas is heated at constant volume, the whole heat supplied to gas is used up in
raising its temperature. While in the second case, since the gas is allowed to expand
under constant pressure, heat supplied is used up in raising the temperature as well as
in doing external work against expansion. Therefore, the specific heat of a gas at constant
pressure is greater than the specific heat at constant volume (C p > CV ) by an amount equal to the
thermal equivalent of external work done by the gas. The units of specific heat in C.G.S.
System is calory per gram per °C.
1.10.2 Difference between C p and C V

To derive a relation in between specific heat at constant pressure C p and specific heat at
constant volume CV , let us consider unit mass of an ideal gas at pressure p, temperature
T and volume V.
Let the gas be heated at constant volume, due to which temperature rises by dT. The
amount of heat supplied will be CV dT . At constant volume, the external work done will
be zero. So, from the first law of thermodynamics,
dQ = dU + dW

24
where dQ = heat supplied, dU = increase in internal energy, dW = work done

CV dT = dU ...(1)
If the gas is heated at constant pressure, so that the same temperature rise takes place,
then the heat supplied will be C pdT . Now, as the pressure remains constant, the gas
expands and external work against pressure p will be done. Let dV be the change in
volume, then external work done will be p dV. From the first law of thermodynamics,
C pdT = dU + pdV ...(2)
From equation (1) and (2),
(C p − CV ) dT = pdV
But for an ideal gas, pV = RT
or pdV = RdT
∴ (C p − CV ) dT = RdT
or Cp − CV = R ...(3)
where C p and CV are in calories and R in joules/(mole-K)
Expressing R in calories,
R
Cp − CV = ...(4)
J
This relation was derived by Mayer and is strictly true for ideal gases while it holds
good in case of permanent gases like H2 , He etc.
1.11 Ratio of Specific Heats of an Ideal Gas

The specific heats of gases can be readily calculated on the basis of Maxwell's law of
equipartition of energy and Boltzmann theorem of degrees of freedom.
Let us have 1 gram molecule of an ideal gas at absolute temperature T. Since in an ideal
gas, there are no forces of attraction between the molecules, there is no internal
potential energy. i. e., the internal energy of an ideal gas is entirely kinetic: If n be the degrees
of freedom, then average kinetic energy per molecule of an ideal gas is (1 / 2)nkT .
Therefore total energy U of one mole of an ideal gas is given by,
1 1
U = nkT × N = nRT ...(1)
2 2
where N is Avogadro's number and R is gas constant per gram molecule (R = k. N )
Differentiating equation (1) w.r.to T,
dU 1
= nR ...(2)
dT 2
Let at constant volume increase in temperature be dT. If CV be the molecular specific
heat at constant volume i. e., the quantity of heat required to raise the temperature of
one gram molecule through one degree, then

25
dU = CV . dT
[Q dU = dQ − dW as dW = 0, no external work as V = constant]
or CV = dU / dT ...(3)
1
Combining equation (2) and(3), CV = nR ...(4)
2
It is the molar specific heat of the gas at constant volume and the molar specific heat at
constant pressure will be,
C p = CV + R [Q C p − CV = R ]
nR n
or = + R =  + 1 R ...(5)
2 2 
Hence, the ratio of two specific heats of a gas would be,

n 
C p  2 + 1 R 2
γ= = =1 + ...(6)
CV n n
R
2
Thus, we see that γ decreases if degrees of freedom, n increases.
1.12 Ratio of Molecular Specific Heats for Monoatomic,

Diatomic and Triatomic Gases
For monoatomic gas, a molecule has only 3 degrees of freedom i. e., n = 3, then
1 3
CV = nR = R = 2 . 98 Calories ...(1)
2 2
[Using R = 8 . 32 × 107 ergs]
and C p = (n / 2 + 1) R = (5 / 2)R ≈ 4 . 96 Calories ...(2)

2 2 5
∴ γ = 1 + = 1 + = = 1.66 ...(3)
n 3 3
Form relations given in equations (1), (2) and (3) it is clear that molar specific heats
CV , C p and γ for monoatomic gases are constants, independent of temperature and
nature of the gas. These predictions agree with experimental results. For argon, vapours
of mercury and zinc, and other inert gases like helium, neon, krypton which are
monoatomic, CV ≈ 3 over a wide range of temperature.
For diatomic gases, a molecule has five degrees of freedom, 3 translational and 2
rotational.
1 5
Therefore, CV = nR = R or CV = 4 . 96 Calories
2 2
 n 7
and C p = 1 +  R = R or C p = 6 . 94 Calories
 2 2
2 2 7
∴ γ =1 + = 1 + = = 1.40
n 5 5

26
These theoretical results agree with experimental results for diatomic gases like
H2 , O2N2 , CO, NO etc.,but for some gases like Cl2 , Br2 , I2 etc., the value of CV and C p
are found to be greater than (5/2) R and (7 / 2)R and value of γ lower than the
theoretical values.
For triatomic gases, atoms may have two different arrangements corresponding to 6 to 7
degrees of freedom. Taking former case,
CV = (n / 2). R = 3 R ≈ 5 . 96 Calories
C p = (n / 2 + 1)R = 4 R ≈ 7 . 95 Calories
2 2 4
and γ =1 + = 1 + = = 1.33
n 6 3
But these theoretical results are not found to be in good agreement with experimental
results. The experimental specific heats are found to be larger than these values while γ
is smaller.
1.12.1 Behaviour of Specific Heat of Gases at Low Temperature

It has been observed experimentally that the specific heat of gases (diatomic) like
hydrogen (H2 ) chlorine (Cl2 ), Nitrogen (N2 ) and hydrogen chloride (HCl) etc., increases
with increase of temperature and decreases with decrease of temperature and finally
approaching the limiting value (3 / 2)R, which is the specific heat of monoatomic gases
at all temperatures. It means that at sufficiently low temperatures all diatomic gases
have the same value of specific heat and equal to of monoatomic gas.
Example 14: The specific heat of a monoatomic gas at constant volume is 0.75
cal/gm-K. Calculate the atomic weight and mass of a gas atom. Given that, R = 2
Cal/mole-K and N = 6 × 10 23 .
Solution: For a monatomic gas, atomic weight = molecular weight

If M be the atomic weight of the gas then
CV = MCV = 0 . 75 M-cal/mole-K [1 mole = M-gm]
From the law of equipartition of energy, CV for a monoatomic gas = (3 / 2)R
cal 3 3 cal
Hence, 0 . 75 M = R = ×2
mole − K 2 2 mole − K
3
∴ M= =4
0 . 75
One mole of a gas has 6 × 1023 molecules and mass of one mole of the gas is 4 gm.
Thus, mass of one gas atom,
4
= = 6 . 7 × 10 −24 gms
23
6 × 10

27
1.13 Adiabatic Expansion of an Ideal Gas

During an adiabatic process the gas is perfectly insulated from its surroundings i. e., the
gas can neither give heat not take heat from the surroundings. When the gas expands
adiabatically, it has to do work against some external pressure at the expense of its
internal energy. As the internal energy of a gas is a function of its temperature. So
during adiabatic expansion of the gas, its temperatures must fall. If a highly compressed
gas is suddenly allowed to expand adiabatically, it has to do a large amount of external
work and so, the cooling effect will be large.
Consider one gm mole of an ideal gas thermally insulated from its surroundings. Let it
suffer a very small adiabatic expansion doing some work at the expense of its own
internal energy. If the volume of the gas increases by an infinitesimal amount dV
against an external pressure p then the work done by the gas in its expansion will be,
dW = p . dV ...(1)
Since in a ideal gas, the molecules do not attract each other, so the internal energy
depends only upon its temperature. Hence, the decrease in internal energy of the gas
leads to a fall dT in its temperature which is equal to the heat drawn from it, i. e.,
dU = 1 × CV × dT ...(2)
where CV is the specific heat for one gm mole of the gas at constant volume.
Now, applying the first law of thermodynamics,
dQ = dU + dW
(where dQ is the change in heat energy. dQ , dU and dW all are in the same units).
Since, in an adiabatic change, no transfer of heat takes place. So, dQ = 0
Therefore, dU + dW = 0
from equation (1) and (2), we have
CV dT + p. dV = 0 ...(3)
Also for one gm mole of an ideal gas, we have
pV = RT
On differentiation it gives,
p. dV + Vdp = R . dT
p dV + V dp
or dT =
R
Putting this value in equation (3), we have
 p dV + V dp
CV   + p dV = 0
 R 
CV ( pdV + Vdp) + R ( p. dV ) = 0
But we have,
C p − CV = R
∴ CV ( pdV + Vdp) + (C p − CV ) ( p. dV ) = 0

28
or CV . Vdp + C p p. dV = 0
Dividing by CV . pV , we get
dp C p dV
+ =0
p CV V
But again we have that, C p / CV = γ
dp dV
So, +γ =0
p V
On integration we get,
log p + γ log V = constant
or log pV γ = constant
or pV γ = constant
This is the equation for adiabatic process of a real gas.
Example 15: A monoatomic ideal gas of volume 1 litre and pressure 8 atmosphere
undergoes adiabatic expansion until the pressure drops to 1 atmosphere. what is final
volume ? Given that, 1 atm = 10 6 dyne/cm2 .
Solution: Using adiabatic process, we have that

p1V1γ = p2V2γ
1
γ
 V2  p V2  p γ
or   = 1 or =  1
V
 1 p2 V1  p2 
Given that, p1 = 8 atm = 8 × 106 dyne/cm2
p2 = 1 atm = 1 × 106 dyne/cm2
V1 = 1 litre =1000 c.c.

and for a monoatomic gas the specific heat ratio, γ = 1. 66
Putting these values, we get
1
V2  8 × 106  1.66
= 
1000  1 × 106 
or V2 = 1000 × (8)1 /1.66 = 3 . 47 × 103 c.c. = 3470 c.c.
1.14 Application of Kinetic Theory to Atmospheric Physics

1.14.1 The upper atmosphere is cold while its kinetic temperature
is of the order of 1000 K
The quantity of heat of an individual molecule in the upper atmosphere is increased
about 3.5 times than that at the earth's surface. Kinetic temperature on earth's surface
is about 300 K while in the upper atmosphere it is of the order of 1000K. But the

29
pressure and hence the density in the upper atmosphere is very low i. e., in the upper
atmosphere the number of molecules per c.c. is very small. Thus, obviously the total
heat content in the upper atmosphere is very small as compared to the heat content on
the earth in the same volume of the gas. Due to this, the temperature of the upper
atmosphere is very low.
1.14.2 Moon has no Atmosphere

The escape velocity on earth is 11.2 km/sec, whereas on the moon it is only 2.38
km/sec. The average speed of the molecule of atmospheric gases at the moon's
temperature is larger than that of 2.38 km/sec. Hence, these molecules cannot stay at
moon and there is no atmosphere.
1.15 Van der Waal's Equation of State for Real Gases

The equation of state for ideal gases ( pV = RT ) was deduced theoretically from the
kinetic theory of gases and does not properly represent the behaviour of real gases. In
kinetic theory, it was assumed that gas molecules are infinitesimally small and they do
not exert forces of attraction on one another. But the molecules of real gases possess
finite size and do attract one another. That is why the equation of state of an real gas is
different from an ideal gas and these gases are known as Van der Waal gas.
In order to derive new equation, the two basic assumptions of kinetic theory should be
revised and the effect of finite size of molecules and intermolecular attraction should be
taken into account.
1.15.1Correction for the Finite Size of Molecules

Let us consider the molecules of a gas to be hard D C
elastic spheres of finite radius and they are moving d
within the container ABCD (Fig.1.4). Suppose a
molecule is moving parallel to AB travels between
the walls AB and CD, to and fro. If AB = l, then Q
distance travelled in one complete cycle (from wall P
d
AD to BC and back to AD) is not 2l but (2 l − 2 d),
where d is the diameter of the molecule. In this way A B
the effective volume available for the molecules to Fig. 1.4
move is less than the total volume of the container.
At very high pressures total volume of all the molecules is not negligible in comparison
to volume of the gas. Hence the volume in ideal gas equation must be replaced by a less
volume (V − b), where b is a constant and represents total volume of the molecules.

30
1.15.2 Correction for Intermolecular Attraction

The molecules of a real gas attract one another. D C
Consider a molecule at point P in the interior of the
gas as shown in (Fig.1.5). It remains unaffected by
intermolecular attractions because it is attracted
equally in all directions and forces cancel out one
another. But a molecule at point Q near the wall of P Q
the container is subjected to an inward pull due to
unbal anced m olecul ar forces. Due t o thi s A B
unbalanced force of attractions, this molecule strikes Fig. 1.5

the wall with smaller momentum and when the
momentum is less, the pressure exerted by the gas is also reduced.
It is observed that decrease in pressure is proportional to the number of inward

attracting molecules per unit volume and to the number of attracted molecules that
strike unit area of the wall per unit time. Each of these two factors is proportional to
the number of molecules per unit volume or the density of the gas. Hence,
Decrease in pressure ∝ (density of gas)2

1 a
∝ =
2
V V2
where a is constant of proportionality for 1 gm mole of gas.
Let the pressure of a perfect gas be pi and decrease in pressure be β, then the pressure of
a real gas, p = pi − β or pi = p + β and β = a / V 2
 a 
∴ pi =  p + 
 V2 
 a 
Thus, we must replace pressure pi in perfect gas equation by  p +  i. e., sum of
 V2 
observed pressure p and decrease in pressure due to such attractive forces.
Hence, including these two corrections, the perfect gas equation is modified as,
 a 
 p + 2  (V − b) = RT ...(1)
 V 
It is known as Van der Waal's equation or Van der Waal's gas equation.
1.15.3 Nature of Van der Waal's Forces

The matter is formed of atoms and molecules and has the tendency to occupy minimum
space at low temperature through transforming into liquid and solid states. From this
we may conclude that the atoms or molecules must exert a force of attraction to each other. As
the atoms or molecules do not lose their identity inspite of this attractive force, it
means there must be a repulsive forces at short inter-molecular distances.

31
1.15.4 Comparison of Van der Waal's Equation with Experimental

p-V Curves (Andrew Curves)
To check the validity of Van der Waal's equation, we compare it with experimental p -V
curve (Andrew's curve). Let us re-write Van der Waal's equation in the form,
RT a
p= − ...(2)
(V − b) V 2
Substituting the values of R, and those of a and b for carbon dioxide, we can plot
isothermals curves between p and V for CO2 at different temperatures. The curves obtained
are of the form shown in fig. 1.6(a).
We see that for large values of V , p is small and as p → 0, V → ∞; again when V is small,
p is large, so that as V → b, P → ∞. Hence, the curves must be concave upwards. Also V cannot
be less than b, because for V < b, p will be negative which is meaningless.
At higher temperatures theoretical curves for CO2 [Fig. 1.6(a)] are similar to Andrew's
experimental curves for CO2 as shown in fig 1.6(b). Below the critical temperature Van
der Waal's curves show smooth variations with maximum and minimum points whereas
Andrew's curves show a straight horizontal portion. This discrepancy has been
explained by James Thomson. According to him maximum point represent unstable
supercooled vapour and minimum point represent superheated liquid of substance.
D
110
p 48.1°C H Air curves
D
100 1°C
Pressure (in atm.)
48. 48.1°C
35.5
31.1°C
90 5°C
°C
35. 13.1°C
L S
80
31.1°C N
70 M
C
.5°
21
b G 21.5°C F .1 °C
60 V 31
13.1°C
C
B 50 13.1°C B E
A C A
c
V Volume
(a) (b)
Fig. 1.6
1.15.5 Drawbacks of Van der Waal's Equation

Although Van der Waal's equation is applicable generally over a wide range for a variety
of substances but it has its own limitations. It's main drawbacks are as follows:

32
(i) Values of 'a' and 'b' are not constant for a gas. Their values obtained
experimentally (even by a single method) vary with temperature.
(ii) Average experimental value of critical volume is found to be 2b, varying from 1. 4 b
for argon to 2 . 8b for hydrogen while its value was found 3b according to Van der
Waal's equation. Hence, Van der Waal's equation is not exactly obeyed by any gas
near its critical point.
(iii) The value of critical co-efficient RTc / pcVc (= 1 for perfect gas) is found to be 3.7
on the average, varying from 3.28 for hydrogen to 4.99 for acetic acid while it
should be (8/3) = 2.67 for all gases according to Van der Waal's equation. Therefore,
it seems to depend on molecular structure of the gas.
Thus, we can say that Van der Waal's equation explains successfully the deviations of
real gas from ideal gas behaviour but fails to explain the differences between various
gases.
1.16 Critical Constants of a Gas

There are three critical constants of a gas viz. critical temperature, critical pressure and
critical volume.
1.16.1 Critical Temperature

It is the highest temperature for a gas at which the gas can be liquified by increasing
pressure only, above this no liquefaction is possible.
1.16.2 Critical Pressure

The pressure required to liquefy the gas at critical temperature is called critical pressure.
1.16.3 Critical Volume

The volume occupied by one gram molecule of the gas at the critical temperature and
the critical pressure is called the critical volume.
1.16.4 Critical Constants in terms of 'a' and 'b'

According to Van der Waal's equation,
 a 
 p + 2  (V − b) = RT ...(1)
 V 

33
RT a
p= −
V − b V2
when a graph between p and V is plotted D

for different constant values of T, a set of p 48.1°C
isothermals is obtained as shown in fig.
35.5
1.7. The isothernal at critical
°C
temperature is horizontal at point R.
Therefore, at R, (dp / dV ) must be zero. R 31.1°
pc C
21
.5°
Also, we see that curvatures of this C
b
isothermal are opposite in two sides of 13.1°C
C
point R. This point is called point of B
A
inflexion or critical point. The critical
c
temperature and corresponding values of Vc V
pressure and volume at critical point (R )
Fig. 1.7
are called critical constants. Therefore at R,
d2 p
=0
dV 2
Using these two conditions we can obtain the for critical constants in terms of
' a ' and' b '. Thus, differentiating equation (1),
dp − RT 2a
= + ...(2)
dV (V − b)2 V 3
dp
At the critical point, = 0, T = Tc , V = Vc ,
dV
− RTc 2a
∴ + =0
2 V3
(Vc − b) c
2a RTc
or = ...(3)
Vc3 (Vc − b)2
Again differentiating equation (2),

d2 p 2 RT 6a
= − ...(4)
2 3
dV (V − b) V4
d2 p
At the critical point, = 0, T = Tc , V = Vc ,
dV 2
2 RTc 6a
∴ − =0
(Vc − b)3 Vc4
6a 2 RTc
or = ...(5)
Vc4 (Vc − b)3
Dividing equation (3) by equation (5), we get

34
Vc (Vc − b)
=
3 2
or 2Vc = 3Vc − 3 b
or Vc = 3b ...6(i)
Substituting VC = 3 b in equation (3),
2a RTc
=
3
27b 4 b2
8a
or Tc = ...6(ii)
27 b R
substituting equation 6(i) and (ii) in equation (1),
R × 8a a
pc = −
27 b R (2 b) 9 b2
a
pc = ...6(iii)
27b2
RTc R . 8a  27 b2  1 8
Further, = × × = = 2 . 66
pcVc 27 b R  a  3 b 3
RTc
The expression is known as “critical co-efficient” and is same for all the gases.
pcVc
For a perfect gas it is equal to unity.
Constants 'a' and 'b' in Terms of Critical Constants

Eliminating b from equation 6(ii) and 6(iii),
2
Tc2  8 a  27 b2
=  .
pc  27 b R  a
27 R 2  T2
or a=  c ...7(i)
64 p 
 c
Now eliminating a from 6(ii) and 6(iii),
Tc 8a 27b 2
= ×
Pc 27 b R a
R  Tc 
or b=   ...7(ii)
8  Pc 
If ' pc and Tc ' are known, then ' a' and' b ' can be determined.
1.16.5 Difference between a Gas and Vapour

Gas is a state of matter, which has no fixed shape or volume. Gases expand
spontaneously to fill the container and are easily compressed. The molecules of gas are
almost in free random motion. The vapour also a state of matter. These two states are
distant stages of the same continuous phenomenon. These two states have distinct

35
boundary which is governed by a particular temperature, called the critical temperature.

Above the critical temperature, the substance is in the gaseous state and below the
critical temperature it is in the vapour state.
A gas cannot be liquefied by mere application of very high pressure. A vapour can be
liquefied by applying pressure only. Therefore to liquefy a gas, first its temperature is
reduced to a temperature below the critical temperature, (i. e., gaseous state is converted
into vapour state) then by applying high pressure the vapours get liquefied.
Example 16: Calculate the critical temperature of a gas for which,a = 0 . 00874,
b = 0 . 0023 and the gas constant is given by 273 R = 1. 00646
8a
Solution: We know that, Tc =
27 b R
1. 00646
Given that, 273 R = 1. 00646 or R =
273
and a = 0 . 00874, b = 0 . 0023
8 × 0 . 00874 × 273
∴ Tc =
27 × 0 . 0023 × 1. 00646
Tc = 305 K = (305 − 273) = 32°C
Example 17: Calculate Van der Waals constants a and b for dry air; given that,
Tc = 132 K, pc = 37 . 2 atmospheres, R per mole = 82 . 07 cm3 atm K −1.
[Meerut 2007B]
2 2
27 R Tc
Solution: We have, a= .
64 p c
2 2
27 (82 . 07) (132)
Substituting the values, a= × = 13 . 31 × 10 6 atm-cm6
64 37 . 2
RTc 82 . 07 × 132
and b= = = 36.41 cm3
8 pc 8 × 37 . 2
Example 18: Calculate the critical temperature of CO2 , given that, a =0 .00717,
b =0 .00191, the unit of pressure being one atmosphere and the unit of volume, the
volume of gas at NTP.
Solution: With the help of Van der Waal's equation of state, first we determine the
value of R.
 a 
 p + 2  (V − b) = RT ...(1)
 V 

36
Since, unit of pressure and volume are the pressure and volume of gas at N.T.P. so, we
have,
V =1 litre and p = 1 atmosphere at T = 0 °C or 273 K
Substituting these values in equation (1),
 0 . 00717
1 +  (1 − 0 . 00191) = R × 273
 
 (1)2 
or 1. 005 = 273 R or R = 1.005/273
8a
Thus, critical temperature Tc for CO2 =
27 R b
8 × 0 . 00717 × 273
= = 302 . 2 K
27 × 1. 005 × 0 . 00191
= (302 . 2 − 272) = 29.2°C
Example 19: The critical pressure and temperature of a gas are 73 atmosphere and
31°C respectively. Calculate Van der Waal's constants. Given that, R = 8 . 31
joule/mole-K.
Solution: The critical temperature,

Tc = 31°C = 31 + 273 = 304 K
and Pc = 73 atm = 73 × 1. 013 × 105 = 73 . 9 × 105 nt/mt2
2 2
27 R 2Tc2 27 × (8 . 31) × (304)
Now a= × = = 0.36 Nt-mt4 /mole
64 Pc 64 × 73 . 9 × 105
R Tc 8 . 31 × 304
and b= × = = 42.7 × 10 −6 mt3 /mole
8 Pc 8 × 73 . 9 × 105
1.17 Joule's Law

Joule's law states that the internal energy (U ) of an ideal gas depends only on its
temperature and is independent of the volume (V ), i. e.,
 ∂U 
  =0
 ∂V  T
But real gases do not obey this law because they have intermolecular attraction.
1.17.1 Joule's Expansion Experiment

According to kinetic theory of gases the intermolecular attraction is not present there. If
the molecules really attract each other, there must be some work done against this force
of attraction when the gas is allowed to expand even in vacuum. Since, the work can
only be done at the expense of the internal energy of the gas, the gas must show a

37
cooling effect. In order to study the intermolecular attraction between molecules of a

gas Joule performed an experiment. Joule used apparatus which consists of two thin
copper cylinders A and B connected by a tube and fitted with a stop-cock S (Fig. 1.8a).
The cylinder A was filled with dry air at high pressure (≈ 22 atmosphere) while B was
evacuated. Both cylinders A and B were just fully immersed in a water bath whose
temperature was noted by a sensitive thermometer.
When the stop-cock S was opened, the air in A was expanded rapidly into vacuum
(cylinder B) until the pressure in the two cylinders became the same. Since air expanded
into vacuum so, no external work was done. But if the work was done against
intermolecular attraction present among molecules of air in A, the air must be cooled.
The water was then stirred and the temperature observed. But no difference in the
temperature was recorded.
Now, joule performed this experiment by taking separate water baths (Fig. 1.8b). Again
by opening the stop-cock S, the air in A was expanded rapidly into cylinder B. Initially
the air expands into vacuum of B so, no work is done. But when some air has reached
into B, the rest of air entering B, from A, does external work in compressing the air
already reached there. This work would be done at the cost of internal energy of air in
A. So, the air in A is cooled and there is a slight fall in temperature of water bath A.
Further this work is done on air in B (also in S). So, the air in B is heated and
temperature of water bath B rises slightly. Thus, loss of heat in A must be equal to gain
of heat in B (and also in S). But the loss of heat in A due to work done against
intermolecular attraction will further reduce the temperature of bath A. But joule found
that heat lost by A was just equal to heat gained by B. It indicates that intermolecular
attractions do not exist.
This experiment led to the conclusion that internal molecular attractions do not exist in
a gas. In other words, the energy of a gas is entirely kinetic, depending only on its
temperature and not on the volume of the gas. But Joule felt that due to large heat
capacity of water as compared to air, small change in temperature may not be detected.

38
So, Joule and Willium Thomson (Lord Kelvin) performed the famous porous plug
experiment which showed clearly the presence of molecular attraction in real gases.
1.18 Joule-Thomson (Kelvin) Effect

In 1852 Joule and Lord Kelvin (Thomson) demonstrated that when a gas, at high constant
pressure is passed through an insulated porous plug to a region of lower constant pressure, the gas
shows a change in temperature. This is called Joule-Thomson or Joule-Kelvin effect.
1.18.1 Porous Plug Experiment

The porous plug simply consists of a material like cotton, wool, silk etc., having a
number of fine holes or pores and is thus equivalent to a number of narrow orifices in
parallel.
The apparatus used by Joule and Thomson is shown in fig. 1.9. It consists of a porous
plug P of cotton wool or silk; kept in between two perforated brass plates (P1 and P2 )
and enclosed in a boxwood tube BB' to get thermal isolation. The boxwood tube BB′ is
further surrounded by a brass case CC′ full of cotton wool. It provides good thermal
isolation and protects BB′ from water as whole apparatus is placed in a water bath to
ensure constant temperature. The box-wood tube BB′ is fitted with copper tubes DD′
on both sides. The lower copper tube (D’) is connected to a compression pump through
a copper spiral S. It is also dipped in water bath to maintain constant temperature of
gas, before it reaches the plug.
The compressed gas flows through

the spiral tube and becomes
cooled upto temperature of water
bath. Then it is allowed to flow T2 D
(upward) through the porous plug C C'
and escaped into the atmosphere. B P1
The gas is allowed to flow for P
about an hour in order to obtain P2 B'
steady state. The temperature of Perforated
brass plates T1 D'
the gas entering the plug was Copper tubes
measured by sensitive thermometer T
T1 and that of gas emerging from Water bath
plug by another thermometer T2
placed just above the plug. The S
experiment is repeated for various Compression
pressure differences on two sides pump
of porous plug. The initial Fig. 1.9

pressure of the gas was measured
by a manometer attached to lower copper tube (not shown in fig. 1.9) and its final
pressure is that of atmosphere. Joule and Thomson investigated various gases like air,

39
oxygen, nitrogen and carbon dioxide, over a wide range of temperature (between 4° to
100°C) and initial and final pressure keeping 4.5 and 1 atmosphere respectively.
Later on some scientists used a hollow cylindrical porous plug and flowed the gas from
outside to inside, to secure better thermal insulation.
1.18.2 Results
The results of these experiments can be stated as follows:
1. All gases show a change in temperature (or the Joule Thomson effect) in passing
through porous plug.
2. At sufficiently low temperature of water bath all gases show cooling effect.
3. At ordinary temperatures, most gases show a cooling effect while hydrogen and
Helium show a heating effects e.g. at 0°C air shows a cooling of 0.275°C while
hydrogen shows a heating of 0.04°C per atmospheric pressure difference.
4. The fall in temperature is proportional to the difference of pressure on two sides of
porous plug. The greater the difference pressure, greater is the fall in temperature
and vice-versa.
5. The fall in temperature decreases as the initial temperature of the gas is raised and
it becomes zero at a particular temperature. Above this temperature, there is no
more fall in temperature but rises in temperature occurs. The temperature at
which Joule Thomson effect changes sign i.e., cooling effect becomes heating
effect, is called temperature of inversion. This is different for different gases. It is
192.5 K for H2 , and about 30 K for He. For most common gases it lies well above
the ordinary temperature.
Thus, it becomes established that any gas below its inversion temperature will get cooled on
passing through a narrow orifice.
1.18.3 Explanation of Results

Porous plug
The above results can be A B
1 2
explained by the following p1V1
theory of experiment. Let Piston Piston
Initial state
us replace the porous plug (a)
experiment by a simple Porous plug
A B
equivalent arrangement as 1 2
p2V2
shown in fig. l.10. Let A
Piston Piston
and B be two chambers of Final state
(b)
along cylinder fitted with
smoothly moving insulated Fig. 1.10
pistons, having a porous

40
plug (small hole) between them, both the chambers being thermally insulated. Let a
certain (unit) mass of gas be filled in chamber A at pressure P1 and volume V1 and it is
flowing to chamber B through porous plug where pressure and volume of gas changes to
p2 and V2 (V2 > V1). Both the pistons are moved in a way to the right that the pressures
p1 and p2 in two chambers remain the same throughout. i.e., the gas is expanded at
constant pressure difference. In this process, the work is being done on the gas by
piston1 and is equal to,
0
∫ p1dV = – p1V1
V1
Also in chamber B, the work is done by the gas on the piston 2 and is equal to
V2
∫ p2 dV = p2V2
0
∴ net external work done by the gas = p2V2 – p1V1
Since, no heat is allowed to enter or leave the chambers (from surroundings) so, this
external work must have been done by the gas at the cost of its internal energy. Let U1
and U2 be the internal energies of unit mass of gas in chambers A and B, then loss in
its internal energy is passing from A to B = U1 – U2 . Therefore,
p2V2 – p1V1 = U1 – U2 or p1V1 + U1 = p2V2 + U2
Hence, total heat (U + pV ) remains constant during Joule Thomson effect (a throttling
process). The quantity (U + pV ) is known as enthalpy and is denoted by H. Due to this,
Joule-Thomson effect is known as enthalpic effect.
1.19 Joule Thomson Expansion for an Ideal Gas

For an ideal gas, we know that, the internal energy U and the product pV, both
depends on temperature only (from Boyle’s law, pV = RT and Joule’s law, U = K. E.
+ P. E.) and for perfect gas P. E. = 0 and K. E. is proportional to Temp.). So, enthalpy
H = U + pV must also depend on temperature only. Since, U + pV is the same on the
two sides of the plug, the temperature must also be the same. It means Joule Thomson
Kelvin) effect is zero for a perfect gas. It can be proved as follows;
We know that, dS = Q / T
where Q is the heat absorbed by a system at a constant temperature T and dS is the
increase in entropy of the system. So,

41
Q = T . dS ...(1)
If dU be the increase in the internal energy of the gas and dV the increase in its volume
at constant pressure p, then we also have,
Q = dU + pdV
From equation (1) we can write,
TdS = dU + pdV ...(2)
For Joule Thomson effect, the enthalpy, H = (U + pV ) remains constant, then
dH = d(U + pV ) = 0
or dU + pdV + Vdp = 0
From equation (2), this can be written as,
TdS + Vdp = 0 ...(3)
Equation (3) can be written in partial differentiation,
 ∂S   ∂S 
T  dT + T   dp + Vd p = 0 [Since T and p are independent variables]
 ∂T  p  ∂P  T
 ∂S   ∂Q   ∂Q
Now, T  = T  =  = Cp [Thermodynamical relation]
 ∂T  p  T∂T  p  ∂T  p
 ∂S   ∂V 
and   =–   [Thermodynamical relation]
 ∂P  T  ∂T  p
So, equation (3) is reduced to,
 ∂V 
C p(dT )H – T   (d P)H + V (d p)H = 0
 ∂T  p
 ∂V 
or C p(dT )H = T   (d P)H – V (d p)H
 ∂T  p
  ∂V  
= T   – V  (d p)H
  ∂T  p 
 ∂T  1   ∂V  
or   = T   –V ...(4)
 ∂p  H C p   ∂T  p 

42
This quantity ( ∂T / ∂p)H represents the change in temperature due to a change in

pressure at constant enthalpy and it is known as Joule Thomson coefficient. It is
denoted by µ.
 ∂T  1   ∂V  
∴ µ=  = T   –V ...(5)
 ∂p  H C p   ∂T  p 
For an ideal gas, pV = RT ,
 ∂V   ∂V  R
so, p  = R or   =
 ∂T  p  ∂T  p p
R V
But =
p T
 ∂V  V  ∂V 
∴   = or V = T  
 ∂T  p T  ∂T  p
putting this value in equation (5), we get

µ =0
Thus, for an ideal gas joule Thomson effect (coefficient) is zero.
1.20 Joule-Thomson (Kelvin) Effect

When a gas at high constant pressure is passed through an insulated porous plug to a
region at lower pressure, it shows a change in temperature. This is known as Joule
Thomson (Kelvin) effect. The change in temperature is proportional to the difference in
pressure on two sides of the plug.
1.20.1 Expression for Joule Thomson Effect in a Van der Waal’s Gas
Porous plug
Let there be a long cylinder having
A B
porous plug P and fitted with two 1 2
non-conducting pistons I and 2 (Fig. Piston
Piston
1.1l). Let us move the piston 1 towards p1 V1 p p2 V2
the porous plug P and a certain mass of Initial state Final state
gas is transferred from compartment A to Fig. 1.11

compartment B which are thermally
insulated. Both the pistons are so moved that high pressure in left compartment are
kept constant.
Let us consider unit mass of gas. If p1, V1 and T1 be its pressure, volume and temperature
on left side and p2 , V2 and T2 on right side such that p1 > p2 . Then,
The work done on the gas by the piston 1 = p1V1
The work done by the gas on the piston 2 = p2V2

43
Net amount of work done by the gas = p2V2 – p1V1. In addition to this external work,
the gas has to do some internal work in expanding from V1 to V2 , against
intermolecular attractions. As the real gases obey Van der Waal’s equation
 a  
 p + 2  (V – b) = RT , so the attractive forces between the molecules are equivalent to
 V  
internal pressure (a / V 2 ) of gas, where a is a constant. Hence, the internal work done
against the force of attraction in expansion of the gas from volume V1 to V2 will be,
V2
a a a
∫ V 2 dV = V1 – V2
V1
Therefore, the total work done by the gas,
a a
W = p2 V2 – p1V1 + – ...(1)
V1 V2
 a 
Now, expanding Van der Waal’s gas equation  p +  (V – b) = RT and neglecting
 V2 
ab
second order term ,
V2
a
pV + – pb = RT
V
a
or pV = RT +  pb –  ...(2)
 V
 a
Thus, p1V1 = RT1 +  p1b –  ...(3a)
 V1
 a
p2V2 = RT2 +  p2 b –  ...(3b)
 V2 
substituting equation 3(a) and equation 3(b) in equation (1), we get
a a a a
W = RT2 + p2 b – – RT1 – p1 b + + –
V2 V1 V1 V2
 a a
= R (T2 – T1) + 2  –  – b ( p1 – p2 ) ...(4)
 V1 V2 
As ' a,' and ' b ' are very small, we may use approximately, pV = RT or V = RT / p. Using
V = RT / p in equation (4),
ap a p2 
W = R (T2 – T1) + 2  1 –  – b ( p1 – p2 )
RT
 1 RT 2
2 a  P1 p2 
= R (T2 – T1) +  –  − b ( p1 – p2 )
R  T1 T2 
Since, difference in T1 and T2 is very small so, we may write, T1 – T2 = dT and
T1 = T2 = T , then
2a
W = – R dT + ( p – p ) – b ( p1 – p2 )
RT 1 2
 2a 
or W = ( p1 – p2 )  – b – R dT ...(5)
 RT 

44
As the chambers are thermally isolated, so this work is done at the expense of internal
energy of gas and the temperature of gas falls. Let this fall in temperature be dT. If CV is
the specific heat of gas at constant volume, then the heat absorbed from itself to
perform work W will be CV dT (in cal). Thus,
 2a 
CV dT = ( p1 – p2 )  – b – R dT
 RT 
 2a 
or CV dT + R dT = ( p1 – p2 )  – b
 RT 
 2a 
or C p dT = ( p1 – p2 )  – b (Q C p – CV = R )
 RT 
p –p   2a 
or dT =  1 2
 – b ...(6)
 C   RT 
 p 
This is the expression for cooling, produced. Two important conclusions drawn clearly
from equation (6) are as follows:
(i) At any temperature T, cooling is directly proportional to pressure difference
( p1 – p2 ) across the porous plug.
(ii) For the given pressure difference ( p1 – p2 ) across the plug, lower is the initial
temperature T, greater is the cooling produced.
In equation (6), we know that p1 > p2 so ( p1 – p2 ) is always positive. The quantity
 2a 
 – b may be positive, negative or zero.
 RT 
 2a  2a 2a
If  – b is positive i.e., > b or T < , then dT is positive (T1 > T2 ), or the gas
 RT  RT Rb
will be cooled.
 2a  2a 2a
If  – b is negative i.e., < b or T > , then dT is negative (T1 < T2 ), or the gas
 RT  RT Rb
will show heating effect.
 2a  2a
If  – b is zero, i.e., T = , then dT will be zero (T1 = T2 ), there will be no change in
 RT  Rb
2a
temperature of gas. This temperature is known as temperature of inversion Ti = . The
Rb
temperature at which Joule Thomson effect is zero is known as temperature of inversion.
All the gases above temperature of inversion would show a heating effect. For Hydrogen
and Helium the temperature of inversion are – 80°C and –240°C respectively.
Therefore, Hydrogen and Helium show heating effect at ordinary temperatures.
1.20.2 Relation between Critical Temperature and Temperature

of Inversion
8a
We know that critical temperature, TC = ...(1)
27 b R

45
where a and b are Van der Waals constants, and the temperature of inversion is given by,
2a
Ti − ...(2)
Rb
T 2 a 27 b R 27
Dividing equation (2) by equation (1), i = × =
TC Rb 8a 4
27 Ti 27
or Ti = T or =
4 C TC 4
Thus, the ratio of temperature of inversion and critical temperature is a constant and is
independent of nature of the gas.
Example 20: What will be the change in temperature when Helium gas suffers Joule
Thomson expansion at –173° C, the pressure difference on the two sides of the porous
plug being 20 atmospheres. Does Helium show heating effect or a cooling effect in
expansion at –173° C. Given that, R = 8.3 Joules/mole-K, a =0.0341 atm-litre2 /
mole2 , b = 0.0237 litre/mole.
Solution: The change in temperature in Joule Thomson effect is given by,

∆ p  2a 
∆T =  – b
C p  RT 
Given that, . × 106 dynes / cm 2

∆p = 20 atm = 20 × 101
T = –173 ° C = (273 – 173) K = 100 K
a = 0.0341 litres2 atm/mole2=0.0341 × 1012 dynes cm 4 / mole2
b = 0.0237 litre/mole = 23.7cm 3 /mole
For a monoatomic gas, . × joules/mole-K
C p = (5 / 2)R = (5 / 2) × 83
. joule/mole-K = 5 × 415
= 5 × 415 . × 107 ergs/mole-K
20.2 × 106  2 × 0.0341 × 1012 
∴ ∆T = – 23.7
7  7
5 × 4 .15 × 10  83
. × 10 × 100 
2.02  68.2 
=  – 23 .7
20.75  8.3 
= 0 .096 × (8.22 – 23 .7) = –0 .096 × 15 .48
= –1.486 K = – 1.5 K
Negative sign shows that T1 – T2 = ∆T is negative i.e., T1 < T2
It means that there is a rise of 1.5 K in temperature or the Helium shows heating
effect in expansion at –173°C.
Example 21: The van der Wall's constants for a gas are a = 1.328 × 1012 dynes -
cm 4 /mole2 and b= 32 cm 3 /mole. Upto what maximum temperature will the
Joule-Thomson expansion produce cooling? (Given that, R = 8.3 joule/mole-K).
Solution: The gas shows cooling effect only upto its temperature of inversion Ti. In
Joule-Thomson expansion, the temperature of inversion is given by,

46
2a
Ti =
Rb
Given that, a = 1.328 × 1012 dynes cm4/ mole2
b = 32 cm3/mole
R = 8.3 × 107 ergs/mole-K
2 × 1.328 × 1012 2 .656 × 103

∴ Ti = = = 999K
8 .3 × 107 × 32 2 .6592
or Ti = 999 – 273 = 726 °C
Example 22: The Van der Waal's constants for one mole of hydrogen are a = 0 .247
atm litre2/mole2 and b = 2.65 × 10 –2 litre/mole. Calculate temperature of inversion and
Joule Thomson cooling for 2 atmosphere fall of pressure; if the initial temperature was
100 K. (Given that, R=22.4/273 atmosphere litre/mole-K, and one atm = 106
dynes/cm2).
Solution: The temperature of inversion is given by,

2a
Ti =
Rb
Here, a = 0 .247 atmosphere-litre2/mole2, b = 2.65 × 10 –2 litre/mole
22.4
and R= atm-litre/mole-K
273
Putting the value we get
2 × 0 .247 0.494 × 273 × 102
Ti = = = 227K
22.4 22.4 × 2.65
× 2.65 × 10 –2
273
or Ti = (227 – 273)° C = – 46°C
The Joule Thomson cooling is given by,
( p – p )  2a 
∆Τ = 1 2  – b
C p  RT 
Here, ( p1 – p2 ) = 2 atmosphere =2 ×106 dynes/ cm 2

for Hydrogen, C p = (7 / 2)R = (7 / 2) × 8 .3 × 107 ergs/mole-K
2 × 106  2 × 0 .247 × 1012 

∴ ∆T =  – 26 .5
7  7 
. × 7 × 10  8.3 × 10 × 100
415 
[Q a = 0 .247 atm-litre2/mole2 = 0 .247 × 106 × 106 dynes cm4/mole and b = 2 .65 × 10 –2 litre/mole
= 26.5 cm3/mole.
2  494 
=  – 26. 5
290. 5  8.3 
2
= (59. 52 – 26. 5) = 0. 227 K
290. 5
∆T = 0 . 23 K
This is Joule-Thomson Cooling.

47
Miscellaneous Problems
Problem 1: The best vacuum attainable so far in the laboratory is 10 –10 mm of Hg.
Calculate the number of molecules per c..c. at 27°C in this vacuum. Given that,
Avogadro's number, N = 6 × 10 23 /mole.
Solution: We know that at N.T.P.

p = 76 cm of Hg = 76 × 13.6 × 980 dyne/cm 2
V = 22400 c.c, T = 273 K
In problem it is given that, p1 = 10 –10 mm of Hg = 10 –11cm of Hg
= 10 –11 × 13.6 × 980 dyne/cm 2 , T1 = 300°K and V1 = ?

For pressure p1, temperature T1 and volume V1, the gas equation is,
p1V1 = RT1
R can be determined with the help of p, V and T at N.T.P.
 pV 
∴ p1V1 =  T
 T  1
pV T1
or V1 =
p1T
76 × 13.6 × 980 × 22400 × 300 76 × 22400 × 300
Putting the values, we get, V1 = =
–11
10 × 13.6 × 980 × 273 10 –11 × 273
= 1.87 × 1017 c. c.
6 × 1023
So, the number of molecule per c.c. = = 3 . 2 × 10 6
1. 87 × 107
Problem 2: An evacuated chamber has a pressure of 10 –10 mm Hg. Calculate the

number of molecules per cm 3 at 27°C in the chamber. Gas constant, R = 8.31 × 10 7
erg/ (Mole-K) and Avogadro's number = 6.02 × 10 23 /mole.
Solution: The equation of state for n moles of air is,

pV = nRT
pV
or n=
RT
Given that, p = 10 –10 mm =10 –11 cm =10 –11 × 13.6 × 980 dyn/cm 2
V = 1 cm 3 and T = 27° C=300K
Putting the values, we get
10 –11 × 13.6 × 980 × 1
n= = 5 . 35 × 10 –18 mole
8 . 31 × 107 × 300
Now, according to Avogadro's number, 1 mole contains = 6.02 × 1023 molecules, then
5 . 35 × 10 –18 mole contains = 6 .02 × 1023 × 5 . 35 × 10 –18 molecules = 3. 2 × 10 6 molecules

48
Problem 3: An ideal monoatomic gas at temperature 27°C and pressure 10 6 N / m 2

occupies 10 litre volume. 10000 cal of heat is added to the system without changing the
volume. Compute the final temperature of the gas. Given that, R = 8.31 Joule /
(mole-K) and J= 4.18 Joule/ Calorie.
Solution: The gas equation for n moles of a gas is given by,

pV = nRT
pV
or n=
RT
Given that, p = 106 N / m 2 , V = 10 litre = 10 –2 m 3 , R = 8. 31 Joule / (mole-K)
(Q 1 litre = 1000 C.C. = 10 –3 m 3 )

and T = 27° C = 300 K
106 × 10 –2
∴ n= = 4. 0
8. 31 × 300
For a monoatomic gas, CV = (3 / 2)R

Thus, CV = (3 / 2) × 8.31 = 12. 465 Joule / (mole-K)
12. 465
= ≈ 3 cal / (mole − K)
4.18
Let ∆T be the rise in temperature when n mole of the gas are given, Q (10000) cal of
heat at constant volume, then
Q = nCV ∆T
Q 10000
or ∆T = = = 833 K
nCV 4 ×3
∴ Final temperature of the gas is = T + ∆T = 300 + 833 = 1133K = 860 ° C
Problem 4: 10 litres of air at 17°C and 76 cm Hg pressure is compressed adiabatically

to a volume of 0.5 litre. Assuming γ = 141
. , calculate the final pressure attained.
Solution: For a gas, in adiabatic change, pV γ = constant
If pi, Vi be the initial and p f , V f the final pressure and volume respectively, then
piViγ = pf Viγ
γ
pf V 
or = i
pi  V f 
Given that, pi = 76 cm, Vi = 10 litre, Vf = 0 .5 litre and γ = 141

.
pf 141
.
 10 
Putting the values, we get, =  = (20)141
.
76  0. 5 

49
or p f = 76 × (20)141
.
or logp f = log 76 + 141

. log 20 = 18808
. + (141
. ) × 13010
. = 18808
. + 185441
. = 3.71521
∴ p f = 5190 cm of H g
Problem 5: Calculate the molecular translational energy of a mole of gas at 0°C .

Given that, R = 8.31 Joule/mole - K. Is it same for all gases ? What about the total
energy of all gases ?
Solution: The translational kinetic energy per molecule of an ideal gas at Kelvin
temperature T is (3/2) kT. Since 1 mole of gas contains N (Avogadro's number)
molecules so, the translational kinetic energy per mole will be,
(3 / 2) kT × N = (3 / 2) RT [Q k × N = R ]
Thus, for 1 mole of a gas at 0°C (273 K) the translational kinetic energy
= (3 / 2) × 8. 31 × 273 =3.4 × 10 3 Joule.
Yes, It is same for all the gases as it does not depend upon the molecular weight of the
gas. The total kinetic energy for all gases is not same because it depends upon the
atomicity of the gas.
Problem. 6: What is the energy of thermal motion of 20 gm of oxygen at 10°C? What

part of this energy falls to the share of translational motion and what of rotational
motion?
Solution: The average kinetic energy of thermal motion of an oxygen molecule at the
temperature T, is given by, 5 × (1/2) kT as oxygen molecule has 5 degree of freedom (3
translational and 2 rotational) and k is Boltzman’s constant.
Here, T = 10 ° C = 283 K
= (5 /2) × 1.38 × 10 –23 Joule / K×283 K=9.76 ×10 –21 Joule
The molecular weight of oxygen is 32 i.e., the mass of 6.02 ×1023 molecules of oxygen
is 32 gm
6.02 × 1023 × 20
Therefore, the no. of molecules in 20 gm of oxygen is = 3.76 × 1023
32
Hence, the total energy of 20 gm of gas,
= 9.76 ×10 –21 × 3.76 × 1023 = 3670 Joule
The translational energy = (3 / 5) × 3670 = 2202 Joule
The rotational energy = (2/5) × 3670 = 1468 Joule

50
Problem 7: Calculate the rms speed and the most probable speed of the molecules of a
gas whose density is 1.4 gm/litre at a pressure of 10 6 dyne/cm 2 .
Solution: According the kinetic theory, the rms speed of the molecules of a gas having
density ρ is given by,
3p
v rms =
ρ
Here, p = 106 dyne/cm 2 and ρ = 1.4 gm/litre 1.4 ×10 –3 gm/cm 3
3 × 106
v rms = = 4.63 × 104 cm/sec
. × 10 –3
14
Most probable speed v p means that the speed possessed by the maximum number of
molecules and the relation between v rms and v p is given by,
2
vp = v = 0 .816 × 4.63 × 10 4 = 3.78 × 10 4 cm/sec.
3 rms
Problem 8: Calculate the rms speed of a hydrogen molecule at NTP. The Boltzman’s constant
is k = 1.38 × 10 –16 erg/molecule -K and Avogadro’s number is N = 6 ×10 23 /mole.
Solution: The rms speed of a gas molecule of mass m at absolute temperature T is given
by,
3 kT
v rms =
m
Given that, k = Boltzman’s constant = 1.38 ×10 –16 erg/(molecule-K), T = 0 + 273 = 273 K
and for hydrogen molecule,
M (molecular weight of hydrogen gas) 2 1
m= = = × 10 –23 gm
N (Avogadro' s number) 23 3
6. 023 × 10
3 × 1.38 × 10 –16 × 273 × 3

v rms = = 1.84 × 10 5cm/sec
1 × 10 –23
Problem 9: Calculate the root mean square speed of smoke particle at N.T.P. Assume
the mass of a particle is 5 × 10 –14 gm and k = 1.38×10 –16 erg/(molecule-K).
Solution: The smoke particles suspended in the atmosphere behave as large molecules
of the atmospheric gases and have on the average a translational kinetic energy (3/2)kT,
where k is Boltzman’s constant and T is the Kelvin temperature . Thus, if v rms is root
mean square speed of the smoke particle, then
1 3
m (v rms )2 = k T
2 2

51
3 kT
or v rms =
m
Here, k = 1.38 × 10 –16 erg/(molecule-K)
T = 0 ° C = 273 K and m = 5 × 10 –14 gm

Putting the values, we get ‘
3 × 1.38 × 10 –16 × 273

v rms = =1.5 cm/sec.
5 × 10 –14
Problem 10: Calculate the root mean square speed of an argon atom at 27°C. At what
temperature will the root mean square speed be (a) half (b) thrice its value at 27°C ?
Atomic weight of Argon is 40.
3RT
Solution: We have, v rms = ...(1)
M
Here, T= 27°C = 300 K, M= 40
( Q Argon is monoatomic, so atomic weight = molecular weight)
and R = 8.3 × 107 erg/mole-K
3 × 8.3 × 107 × 300
v rms = =4.32×104 cm/sec
40
(a) From equation (1), we have
v rms ∝ T
v rms T
or 1
= 1 ...(2)
v rms T2
2
v rms
1
Given that, v rms = ,T1 = 300
2 2
v rms 300
1
then, = or T2 =150K
v rms T2
1
2
(b) Now, v rms = 3 v rms
2 1
v rms 300
1
∴ = , T2 =900K
3 v rms T2
1
Problem 11: A particle under Brownian motion at 27°C has a speed of 1 cm/sec. Find
the mass of the particle. Boltzman’s constant, k = 1.38 × 10 –16 erg/molecule-K.
Solution: The translational kinetic energy of a particle is (3/2) k T, where k is

Boltzman’s constant and T is Kelvin temperature. If v rms is root mean square speed of
the particle, then
1 3
m (v rms )2 = kT
2 2

52
3 kT
or m=
(v rms )2
Given that, k =1.38×10 –16 erg/K, T = 27°C 300 K and v rms = 1 cm/sec
3 × 1.38 × 10 –16 × 300
m= = 1. 24 × 10 –13 gm
(1)2
Problem 12: Particles of an inorganic substance, each having a mass of 1.55 ×10 –14
gm are suspended in a liquid at 300 K having a root mean square speed 2.8 cm/sec.
Compute Avogadro’s number.
Solution: The suspended particles behave like gas molecules and have an average
translational kinetic energy (3/2) kT. If m is the mass and v rms is the rms speed of the
particle, then,
1 3
m (v rms )2 = kT
2 2
m
or k= (v )2
3T rms
Given that, m = 1.55 × 10 –14 gm, T = 300K and vrms =2.8 cm / sec
1.55 × 10 –14 × (2 .8)2
k= = 1.35 × 10 –16 erg/ (molecule-K)
3 × 300
Therefore, Avogadro number, N = R / k
8.31 × 107 erg / (mole - K)
=
1.35 × 10 –16 erg / (mole - K)
= 6 .15 × 10 23 molecules / mole
Problem 13: Find out the rms speed of colloidal particles of molecular weight 3.2×10 5,
if that of an hydrogen molecule is 1000 m/sec.
3 kT
Solution: We have, v rms =
M
1 v1rms M2
or v rms ∝ or =
M v 2 rms M1
Here, M1 = 3 .2 × 105 , M2 = 2 (Hydrogen molecular weight)
v 2 rms = 1000 m/sec

v 2 1
Putting the values, we get, 1rms = =
1000 5 400
3 .2 × 10
or v1rms = (1000 / 400) = 2.5m/sec

53
Problem 14: The Van der Waal's constants of oxygen are, a= 1.32 litre2 - atm /mole2
and b = 3 .12 × 10 –2 litre/mole. The gas is stored at 300 K and has volume 1.2
litre/mole. Find the pressure of the gas. Given, R = 8.31 Joule/mole - K .
[Meerut 2002]
Solution: The Van der Waal's gas equation is,
 a 
 p + 2  (V – b) = RT
 V 
RT a
or p= –
V – b V2
Given that, R = 8.31 Joule/mole-K, T = 300 K
and V = 1.2 litre/mole = 1.2×103 cm3 /mole=1.2×10 –3 m3 /mole
a = 1.32 litre2 -atm/mole2 = 1.32 × 10 –6 m6 atm/mole2
= 1.32 × 10 –6 × 1.013 × 105 m4 - Newton/ mole2
[Q 1 atm = 1.013 × 105 Newton/ m2 ]

= 0 .134 m4 -N/mole2
b = 3 .1. 2 × 10 –2 litre/mole = 312

. × 10 –5 m 3 /mole
8.31 × 300 0 .134
Putting the values, we get p= –
(1.2 – 0 .0312) × 10 –3 (1.2 × 10 –3 )2
2493 0 .134
= – . × 106 – 0.09 × 106
= 213
–3
117
. × 10 1.44 × 10 –6
= 2 .04 × 106 N/m2 =20 atmospheres
Problem 15: The Van der Waal's gas constants for hydrogen are, a = 0 .245
atm-litre2 /mole2 and b = 2.67 × 10 –2 litre/mole. Calculate the critical temperature of
the gas.
Solution: The critical temperature of a Van der Waal's gas is given by,
8a
Tc =
27 b R
where R is gas constant and is equal to 8.31 Joule/mole-K
Given that, a = 0 . 245 atm-litre2 = 0 .245 × 10 –6 m6 atm/mole2
= 0 .245 × 10 –6 × 1.013 × 105 Newton m4 /mole2

(Q 1 atm = 1.013 × 105 Newton/m2 )
= 0.0248 Newton m4 /mole 2
and b = 2.67 × 10 –2 litre/mole = 2.67 × 10 –5 m3 /mole
8 × 0 .0248 0 .1984
Tc = = = 33K= –240°C
–5
27 × 2 .67 × 10 × 8.31 5 .99 × 10 –3

54
Problem 16: Calculate the critical temperature for helium gas. Given that, a = 6.15 ×
10 –5, b= 9.95 ×10 –4 , the unit of pressure being 1 atmosphere and the unit of
volume being the volume of one mole of gas at N.T.P.
Solution: The critical temperture is given by,

8a
Tc = ...(1)
27 b R
a and b are given.
The Van der Waal's equation for 1 mole of gas is given by,
 a 
 p + 2  (V – b) = RT
 V 
In terms of given units, we have a N.T.P.
p = 1, V = 1, t = 273K
Putting the value we get
 615 –5 
1 + . × 10  (1 – 9.95 × 10 –4 ) = R × 273
 
 (1)2 
(1.0000615) (1 – 0 .000995) = R × 273
1.0000615 × 0 .999005
or R= = 3 .66 × 10 –3
273
Putting the values, in equation (1) we get,
8 × 6 .15 × 10 –5 49 .2 × 10 –5
Tc = = = 5K = –268°C
–4 –3
27 × 9 .95 × 10 × 3 .66 × 10 9 .83 × 10 –5
Problem 17: Calculate the Van der Waal's constants a and b for 1 K mole of helium.
Given that, Tc = 5.3 K, pc = 2.2 × 10 5N/m2 and R = 8.3 × 10 3 Joule/mole-K.
Solution: We have 8a
Tc = ...(1)
27 b R
a
and pc = ...(2)
27b2
Squaring equation (1) and dividing it by equation (2), we get
Tc2 64 a2 27 b 2 64 a
= × =
pc 27 × 27b 2 R 2 a 27 R 2
27 R 2  T2 
or a=  c 
64  p 
 c
27 × (8 .3 × 103 )2 (5 .3)2
a= × = 3 .7 × 10 3 N-m4 /K mole2
64 2 .2 × 105
Again dividing equation (1) by equation (2) we have,

55
Tc 8 a2 27 b2 a
= × =
pc 27 b R a R
R  Tc 
or b=  
8  pc 
Again putting the values, we have
8.3 × 103 5 .3
b= × = 0.025m3 /K-mole
8 2 .2 × 105
Problem 18: Calculate the temperature of inversion of helium gas. Given that, a =
0.0341 atm-litre2 / mole2 , b = 0.0237 litre/mole and R = 8.31 Joule/mole -K.
Solution: The temperature of inversion of a gas is given by,

2a
Ti =
Rb
where a and b are Van der Waal's constants for one mole of the gas and R is universal
gas constant.
Given that, a = 0. 0341 atm litre2 /mole2 = 0.0341 × 10 –6 m6 atm/mole2
= 0 . 0341 × 10 –6 × 1.01 × 105 Nm4 /mole2
and b = 0.0237 litre/mole = 0.0237 ×10 –3 m3 /mole
R = 8.31 Joule mole -K
2 × 0 .0341 × 10 –6 × 1.01 × 105 0 .0069
Putting the values, we get Ti = =
–3
8 .31 × 0 .0237 × 10 0 .19 × 10 –3
= 36 K = 36 –273 = –237°C
Problem 19: For one mole of hydrogen, Van der Waal's constants are, a = 0.245
litre2 -atm/mole2 , b=2.67×10 –2 litre/mole. Calculate the temperature of inversion of
hydrogen gas. Given that R = 2 cal/mole-K and 1 atmosphere pressure =10 6
dyne/cm2 .
Solution: The temperature of inversion of any gas is given by,

2a
Ti =
Rb
Given that, a = 0 .245 litre2 -atm/mole2 = 0 .245 × 106 cm6 -atm/mole2
= 0 .245 × 106 × 106 cm4 dyne/mole2
b = 2.67 × 10 –2 litre/mole = 2.67 × 10 –2 × 103 cm3 /mole
R = 2cal/mol-K = 2 ×4.18 × 107 ergs/mole-K

2 × 0 .245 × 1012
Putting the values, we get Ti =
. × 107 × 26.7
2 × 418
=219.5 K

56
Exercise
(A) Descriptive Type Questions
1. What is kinetic theory of matter? Explain the general properties of three states of
matter by the kinetic theory.
2. What is Kinetic Theory of Matter ? Show how the general properties of the Three
States of Matter are accounted for by the Kinetic Theory of Matter ?
3. Give the basic assumptions of the Kinetic Theory of an ideal gas. Show that the
pressure exerted by an ideal gas is equal to two third of Kinetic Energy of its
molecules in unit volume [Meerut 2007B]
4. Deduce the important gas laws from Kinetic Theory. [Meerut 2007B]
5. Give the interpretation of temperature on the basis of Kinetic Theory of gases

and calculate the average Kinetic Energy of translation of an ideal gas.
[Meerut 2012]
6. What do you understand by Root-Mean square speed of the Molecules of a gas.

Show that the speed of sound in a gas is proportional to the Root-Mean square
speed of the Molecules of the gas. Also show that Root-Mean square speed of an
ideal gas is inversely proportional to the square Root of its molecular weight.
[Meerut 2012]
7. What do you understand by Brownian Motion ? Explain it from Kinetic Theory.

How we estimate the Avogadro's number with the help of Brownian Motion ?
[Meerut 2012, 04, 03, 02]
8. What do you mean by degree of freedom of a particle. A particle in translatory

motion has three degrees of freedom, but if it is rotating also, then it has five to
six degrees of freedom. Explain it.
9. State the law of equipartition of energy. Prove that the energy associated with
each degree of freedom is (12) kT. [Meerut 2008B, 06B, 05B, 05, 03, 01]
10. Define the Specific Heat of a gas ? Explain why the Specific Heat of a gas at
constant pressure is greater than at constant volume? Obtain an expression for
the difference between these two Specific Heats.
11. Prove that for a perfect gas whose Molecules have n degrees of freedom, the Ratio
of Specific Heats of a gas is given by,
Cp 2
γ= =1 +
CV n [Meerut 2007B, 07,06B, 05 B, 04, 03, 02, 01]
12. Obtain the Ratio of Molecular Specific Heat for monoatomic, diatomic and
triatomic gases. Also explain the behaviour of specific heat of gases at low
temperature. [Meerut 2007 B, 05, 03, 01]

57
13. What is meant by degree of freedom? State the law of equipartition of energy.
Prove that for a gas whose molecules have n degree of freedom
Cp 2
γ= = 1+
CV n
Hence show that for monoatomic gas γ = 1.66, for a diatomic gas, γ = 1.4 and for
triatomic, γ = 1.33
14. Discuss the adiabatic expansion of an ideal gas.
15. Give some application of Kinetic Theory to atmospheric physics.
16. Deduce Van Der Waal's equation of state for a real gas and discuss nature of Van
der Waal's forces. Also compare it with the experimental p-V curves (Andrews
curves). Write draw backs of Van der Waal's equation
[Meerut 2012, 011, 09, 08 B, 07, 06B, 05 B, 05, 02 B, 02, 01,]
17. Draw Andrew's curves for carbondioxide at different temperatures and explain
them. [Meerut 2006B]
18. Define critical constants of a gas. Express these critical constants in terms of Van
der Waal's constants a and b. differentiate between gas and vapour
[Meerut 2012, 011, 07 B, 07, 06, 05B, 2000]
19. Deduce Van der Waall's equation of state. Obtain expressions for the critical
constants of a gas in terms of a and b of Van der Waal's equation. Further,
calculate the critical coefficient and explain its importance. [Meerut 2006]
20. Write Joule's Law. Describe Joule's experiment.

21. Define Joule-Thomson effect. Describe the porous plug experiment and discuss
the result obtained.
22. What is Joule-Thomson (Kelvin) effect ? Describe their Porous Plug experiment
and explain the results obtained [Meerut 2006B, 05, 01]
23. Describe Joule Thomson effect for an ideal gas. Define Joule Coefficient also
24. Deduce the expression for Joule-Thomson cooling produced in a Van der Waal's
gas.
25. Define Joule Thomson effect. Obtain an expression for the J – T cooling produced
in a Van der Waal's gas, hence, explain why Hydrogen and Helium show heating
effect at ordinary Temperature while other gases do not
[Meerut 2010, 09, 08, 07, 05 04, 03, 02, 01]

58
(B) Short Answer Type Questions

1. Explain the cooling of liquid by evaporation taking account kinetic theory of gas.
2. How would you distinguish between the internal energy of a body and its temperature?
3. The gas kinetic temperature in the upper atmosphere is much higher than that on
the earth but even then it is quite cold there. Why? [Meerut 2008]
4. From the kinetic theory, show that the velocity of sound in a gas is independent of
the pressure and density. Also show that the ratio of the square of the velocity of
γ
sound and mean square velocity of a gas is .
3
5. Calculate the temperature at which rms speed of H2 molecule will become equal
to rms speed of N2 molecule at 35°C. Given that, M N = 14MH .
6. At constant volume, equal quantities of heat are supplied to equal masses of
monoatomic and diatomic gases. In which gas the temperature rise will be greater
and why?
7. At ordinary temperature and pressure the experimentally observed value of CV
for some gases like SO2 , CS2 etc is found to be greater than theoretical values,
explain why?
8. How will you differentiate between thermal capacity and specific heat of a
substance?
9. What is the difference in between Joule expansion and Joule-Thomson
expansion? Also explain how Joule Thomson effect is different from adiabatic
expansion? [Meerut 2009B, 09, 06]
RTc 8
10. Show that for a gas obeying Van der WaaI’s equation, = , where the
pc Vc 3
symbols have their usual meanings.
11. How critical constants are determined experimentally?
12. Prove that the ratio of temperature of inversion and the critical temperature does
not depend upon the nature of the gas. [Meerut 2010]
(C) Very Short Answer Type Questions

1. Define ideal gas.
2. Define real gas or Van der Waal’s gas.
3. Define Avogadro’s law.
4. Define root mean square speed of a gas molecule. [Meerut 2009, 07B]
5. Define degree of freedom of a particle. [Meerut; 2006B, 05B, 05, 03]
6. State law of equipartition of energy. [Meerut 2005B]
7. Write Joule’s expansion law.

8. Why does the temperature rise in compression of a gas ?
9. Define temperature of inversion.

59
(D) Multiple Choice Questions

1. At constant temperature, the product of pressure and volume of a given mass of
gas is constant. This is known as:
(a) Boyle’s law (b) Charle’s law
(c) Avogadro’s law (d) None
2. At constant pressure, the volume of a given mass of gas is directly proportional to
its absolute temperature.This law is stated as:
(a) Boyle’s law (b) Charle’s law
(c) Dalton’s law (d) None
3. The correct relation between v rms and molecular weight is:

M 3M
(a) v rms = (b) v rms =
3RT RT
3RT
(c) v rms = (d) None
M
4. The best example of Brownian motion is :

(a) N.C.C. parade (b) Smoke particle in air
(c) Flow of liquid in a tube (d) None
5. The ratio of two specific heats of a gas is given by :

(a) γ = 1 + 2 / n (b) γ = 2 + 1 / n
(c) γ = 1 + 2n (d) None
6. For a triatomic gas, the value of γ becomes :

(a) 1.40 (b) 1.33
(c) 1.66 (d) None
7. The correct equation for a Van der Waal’s gas is :

a  a 
(a)  p +  (V – b) = RT (b)  p +  (V + b) = RT
 V  V2 
 a 
(c)  p +  (V – b) = RT (d) None
 V2 
where all symbols have their usual meaning.
8. Under Joule Thomson effect, the change in temperature is given by :

∆ p  2a  ∆ p  2a 
(a) ∆T =  – RT  (b) ∆T =  – b
CV  b  CV  R T 
∆ p  2 ab 
(c) ∆T =  – T (d) None
CV  R 
9. The relation among all critical constants is given by :

RTc 8 RVc 8
(a) = (b) =
pcVc 3 Tc pc 3
R pc 8
(c) = (d) None
TcVc 3

60
(E) Fill in the Blanks

1. According to kinetic theory of gases, if the gas is compressed then its
temperature.......................... .
2. The rate of diffusion of a gas is inversely proportional to the square root of its
density. This law is known as ............................... .
3. According to kinetic theory of gases, the temperature at which the translational
velocities of the molecules of a gas are reduced to zero, is known as
............................... .
4. The speed of sound in a gas is proportional to .................................. speed of its
molecules.
5. The rms speed of a perfect gas molecules is inversely proportional to the square
root of the .....................of the gas.
6. For a monoatomic gas, the degrees of freedom are ................................. .
7. For a diatomic gas, the degrees of freedom are .............................. .
8. At sufficiently low temperature, all diatomic gases have the same values of the
specific heat as that of ............................... .
9. For a perfect gas, Joule Thomson effect is ................................ .
10. The ratio of temperature of inversion and critical temperature is .......................... .
(F) True/False
1. The pressure exerted by an ideal gas is equal to two third of kinetic energy of the
molecules per unit volume.
2. According to Avogadro's law at the same temperature and pressure, equal volumes
of all gases contain equal number of molecules.
3. The average kinetic energy of the molecules of an ideal gas is not proportional to
its absolute temperature.
4. The rms speed of an ideal gas molecule is directly proportion to the square root of
its molecular weight.
5. A diatomic molecule has five degree of freedom.
6. 3
The average kinetic energy of the molecule of a gas is kT.
2
a
7. The Van der Wall's gas equation is  p +  (V – b2 ) = RT .
 V
8. Critical temperature of a gas is the highest temperature at which the gas can be
liquified by increasing pressure only.
9. For an ideal gas joule-Thomson effect is zero.
10. The temperature at which Joule Thomson effect is zero is known as temperature
of inversion.

61
Answers
(Hints & Solutions)
4. The speed of sound in a gas at pressure p is given by,
γp
v = ...(1)
ρ
where ρ is the density of gas.
From the kinetic theory, the pressure exerted by a gas is,
1 —2 p 1 —2
p= ρv or = v ...(2)
3 ρ 3
where v 2 is the mean square speed of the gas molecules.
According to the kinetic interpretation of temperature, v 2 remains constant if the
temperature is constant. Therefore, ( p / ρ)[from eq. (2)] will also be constant at
 p
constant temperature and velocity of sound in a gas  γ  will also be constant.
 ρ
Hence at constant temperature the speed of sound is independent of pressure and density of the gas
γ p γ —2
Squaring equation (1) v 2 = = v [using equation (2)]
ρ 3
v2 γ
or =
— 3
v2
which is to be proved.
3RT
5. As we have, v rms =
M
3 R TH
∴ v rms for H2 =
MH
3 R TN
and v rms for N2 =
MN
Given that, v rms for H2 = v rms for N2

3 R TH 3 R TN
Therefore, =
MH MN
MH TN
or TH =
MN
Putting the values, MN = 14 MH and TN = 35 + 273 = 308 K
308 M H
TH = = 22K
14 M H

62
6. As we have, Vc = 3 b
8 a
Tc = and pc =
27 R b 27 b 2
Tc 8a × 27b2 8
∴ = =
pcVc 27 Rb × 3 b × a 3 R
R Tc 8
or =
p c Vc 3
8a
12. We know that critical temperature, TC = ...(1)
27 b R
where a and b are Van der Waals constants, and the temperature of inversion is
given by,
2a
Ti = ...(2)
Rb
Ti 2 a 27 b R 27
Dividing equation (2) by equation (1), = × =
TC Rb 8a 4
27 T 27
or Ti = T or i =
4 C TC 4
Thus, ratio of temperature of inversion and critical temperature is a constant and is


1. (a) 2. (b) 3. (c) 4. (b) 5. (a) 6. (b) 7. (c) 8. (b) 9. (a)

1. increases 2. Graham's Law of diffusion 3. absolute zero temperature
4. root mean square 5. Molecular weight 6. three
7. five 8. monoatomic gas 9. zero
10. constant
(F) True/False
1. T 2. T 3. F 4. F 5. T 6. T 7. F 8. T 9. T
10. T
❍❍❍

I
UN T II
Liquefaction of Gases &
Transport Phenomena in Gases
Liquefaction of Gases
Boyle Temperature and Inversion Temperature
Principle of Regenerative Cooling
Principle of Cascade Cooling
Principle of Liquefaction of Hydrogen
Principle of Liquefaction of Helium
Refrigeration Cycle
Efficiency
Transport Phenomena in Gases: Molecular Collision
Mean Free Path and Collision Cross Section
Estimates of Mean Free Path and Molecular Diameter
Transport of Mass and Variation on Temperature and Pressure
Transport of Momentum & Variation on Temperature & Pressure
Transport of Energy and Variation on Temperature and Pressure
Relation between Conductivity and Viscosity of a Gas

65
II
Liquefaction of Gases &
2.1 Liquefaction of Gases

Substances which are in gaseous state at ordinary temperatures may be converted into
the liquid state if they are sufficiently cooled and simultaneously a large pressure is
applied to gas. The liquefaction of gases first began in 1823 when Faraday, liquefied
chlorine, hydrogen sulphide etc., by cooling them below room temperature and applying
pressure. He however, entirely failed to liquefy the gases such as oxygen, nitrogen and
hydrogen even at a very low temperature (−110 ° C). Hence it was concluded that these
gases could not be liquefied at all and were called as permanent gases.
The famous experiment of Andrews on CO2 , performed in 1863 led to the discovery
that a gas must be cooled first below its critical temperature before it could be liquefied
under pressure. The critical temperature of oxygen, nitrogen, hydrogen and helium are
−118° C, −147° C, −240 ° C and −268° C respectively. Taking it into account, Pictet, in
1877 succeeded in liquefying oxygen. Pictet, however adopted a cascade process in
which the necessary cooling was obtained step by step by evaporation of suitable
volatile liquid under reduced pressure. The cascade process failed to liquefy neon,
hydrogen and helium as their critical temperature are too low. But after the discovery of
Joule-Kelvin effect in 1853, it became easy to liquefy gases like hydrogen. At last, in
1908 Kamerlingh, succeeded in extending the process to liquefy helium using liquid
hydrogen evaporating under reduced pressure as the pre-cooling agent. Thus, all the
known gases have been obtained in liquid state.

66
2.2 Boyle Temperature

For an ideal gas, we have the gas equation, pV = RT i.e., the product of p and V for a
given gas must remain constant at a particular temperature. But real gases do not obey
this law. For a real gas pV varies as p increases. This variation is different at different
temperatures. However, at a particular temperature, pV remains constant over a
sufficient range of p provided p is not too large. This temperature is known as Boyle
temperature and is represented by TB . It is different for different gases.
For a real (Van der Wall's) gas the gas equation is,
 a 
 p + 2  (V − b) = RT
 V 
where a and b are Van der Wall's constants
a ab
or pV = RT + pb − +
V V2
Since, at Boyle temperature pV remains constant i.e. RT, so by making substitution of
1 P
= we get,
V RT
ap abp2
pV = RT + pb − +
RT R 2T 2
a  abp2
or pV = RT + p b − + 2 2
 RT  R T
At low pressure, the term abp2 R 2 T 2 is negligible since a and b are very small.
Therefore, above equation may be written as,
a 
pV = RT + P  b −  ...(1)
 RT 
Differentiating equation (1) with respect to p, we get
d( pV ) a 
= 0 +  b −  ...(2)
dp  RT 
By the definition of Boyle temperature, the product pV remain constant over a
sufficient range of p at Boyle temperature i.e., at T = TB ,
d ( pV )
=0
dp
So, equation (2) becomes,
a
b− =0
RTB
TB = a /bR
We also have that the critical temperature of a Van der Wall's gas is given by,
8a
Tc =
27 b R
Then combining both, we get
TB = (27 / 8 ) Tc
This is the relation between Boyle temperature and critical temperature.

67
2.2.1 Inversion Temperature

For a gas, the temperature at which Joule-Thomson effect is zero is known a temperature of
inversion, i.e., all the gases above temperature of inversion show a heating effect.
2.2.2 Relation between Temperature of Inversion & Critical Temperature

We have that critical temperature,
8a
Tc = ...(3)
27 b R
and the temperature of inversion,
2a
Ti = ...(4)
Rb
Ti 2 a 27bR 27
= × =
Tc Rb 8a 4
Ti 27 27
or = or Ti = T
Tc 4 4 c
Thus, ratio of temperature of inversion and critical temperature is a constant and is
2.3 Principle of Regenerative Cooling

Modern methods for the liquefaction of gases are based on the principle of regenerative
cooling (Joule-Kelvin effect). According to Joule-Kelvin effect when a compressed gas,
initially below its temperature of inversion, is expanded through a fine orifice or nozzle,
its temperature falls. The fall temperature is increased as the initial temperature is
decreased.
Therefore, a portion of the gas emerging from the orifice which first obeys Joule-Kelvin
expansion and becomes cooled is made to flow back over the tube containing the
incoming gas. The incoming gas is thus cooled and on expanding through the orifice
becomes still more cooled. As this process is continued, the gas emerging from the
orifice is progressively cooled. Ultimately a temperature is reached at which the gas is
liquefied under the pressure available there. This is known as principle of regenerative
cooling. In 1895 Hampson in England and Linde in Germany developed air liquefiers
based on this principle.
2.3.1 Principle of Cascade Cooling

The cascade principle for producing temperature low enough to liquefy a particular gas
by compression was devised by Pictet. As we know that a gas cannot be liquefied until it
is cooled below its critical temperature. But once this temperature has been reached,
then it is sufficient to apply only necessary pressure, In this process low temperature is
obtained in steps by employing the cooling produced from rapid evaporation of suitable
volatile liquids. First of all, a liquid at room temperature is evaporated under reduced

68
pressure so that cooling is produced. This cooling is employed to liquefy a suitable gas
which in turn, evaporates at a lower temperature.This process is continued until a
temperature is attained which is below the critical temperature of the gas to be
liquefied. The gas is then liquefied under pressure.
2.4 Principle of Liquefaction of Hydrogen

Hydrogen could not be liquefied for a long time. Its critical temperature is −240 ° C.
No independent cooling agent can cool it to below this temperature. Hence the cascade
process cannot be applied for hydrogen liquefaction. The discovery of Joule-Kelvin
effect opened a new field for the liquefaction of gases. Any compressed gas, initially below
its temperature of inversion, is cooled when expanded through a fine orifice or nozzle. The cooling
effect is increased as the initial temperature of the gas is decreased. It is remarkable that the
temperature of inversion for a gas is much higher than its critical temperature. For
hydrogen it is −80 ° C. Above this temperature, it will show a heating effect instead of a
cooling one. In actual practice,
appreciable cooling by Joule-Thomson H2 Compressor
effect is produced only when the gas is
cooled down to its Boyle temperature, 150 atm A 1 atm
−177° C by using liquid air or liquid
nitrogen.
Liquid air
2.4.1 Method
Travers designed an apparatus to —170°C
produce large quantities of liquid To exhaust B
hydrogen. The essential parts of the pump
Liquid air under
apparatus are shown in fig. 2.1. C.P. is reduced pressure
a compression pump which compresses
the gas to a pressure of about 150 –208°C
atmospheres. The compressed gas is C
then passed through a cold water bath

to remove the heat generated by
compression. After this it passed
through KOH and some dehydrating N 1 atm
—253°C
agent (CaCl2 ) to remove CO2 and
water vapours. It is essential because
at low temperatures they will solidify
and block the system. These parts are Liquid hydrogen
not shown in figure.
Fig. 2.1

69
Thus, the gas which is cooled, compressed and free of CO2 and water vapour, enters
into a spiral coil A, immersed in liquid air where it is cooled to −170 ° C. It is then
passed through another spiral coil B surrounded by liquid air evaporating under reduced
pressure with the help of exhaust pump E.P. By this process the temperature of the
hydrogen on leaving B is reduced to −208° C. The gas now passes through the spiral coil
C from which it expands through the nozzle N to a pressure of 1 atmosphere and
suffers Joule-Kelvin cooling. This expanded and cooled gas passes up around coil C and
passes over the coils B and A, thereby cooling the coils and incoming gas and returns to
the compressor. As the process continues, the hydrogen expanded through the nozzle is
cooled progressively more and more and ultimately liquefies at −253 ° C at 1 atmospheric
pressure. The liquefied hydrogen is collected in a Dewar flask F.
2.5 Liquefaction of Helium

Helium could not liquified for a long time because of its critical temperature. The
critical temperature of helium is −268° C. Hence it was necessary to cool it below
−268° C but it was not possible to attain this temperature by using cascade process. At
last, K. Ones in 1908 proceeded in his efforts very systematically and succeeded in
liquefying helium by the Joule-Kelvin process. He point out that the temperature of
inversion of helium is −240 ° C and it was possible to cool it below this temperature by
means of liquid hydrogen evaporating under reduced pressure. The actually developed a
helium liquefaction in which he precooled helium to Boyle's temperature (−258° C) and
subjected it to Joule-Kelvin He
expansion and obtained liquid
C.P. A
helium.
In 1934 Kapitza, liquefied B

helium by using combined action
of adiabatic exp ansion and To E.P.
Joule-Kelvin effect. The
arrangement of Kapitza app- C1 C2
aratus is shown in fig. 2.2. Pure
helium gas is first compressed to C
36 atmosphere by means of a
F G
compression pump (C.P.) and D
made to enter into tube AB. This
tube is divided into two portions
C3 C4
at B, and gas passes through spiral
coils C1 and C2 . These two
portions of spiral coils reunite at C E
H
N
and again break-up into two at D. Liquid Boiling
Helium again flows through coils helium liquid
C3 and C4 . Coils C1 & C3 are hydrogen
Fig. 2.2

70
enclosed in double walled vessel F, and C2 and C4 in another similar vessel G. The coils
C1 and C3 are cooled by helium vapour and coils C2 and C4 are cooled by hydrogen
vapour from the liquid hydrogen in vessel G, which is kept boiling under reduced
pressure. The helium gas is thus, cooled in two stages in vessel F and G. Now, the
temperature of helium is sufficiently low and both portion of coils reunite at E.
The cooled gas is then passed through a Nozzle N in vessel F. At N cooling takes place
due to Joule-Kelvin effect. The cooled helium vapour rising up in vessel greatly helps in
cooling the down coming gas in coils C1 and C3 . Again Joule-Kelvin expansion takes
place at N giving the lowered temperature of the gas. As a result, after a few cycles
liquefied helium is obtained and collected in the Dewar flask. The whole apparatus is
surrounded by Dewar flasks top provide prefect heat insulations.
2.6 Refrigeration Cycle

A refrigerator is a machine that operates in a manner opposite to that of a heat engine.
In it the working substance absorbs heat from low temperature source (the space to be
refrigerated), then some work is performed on it and finally rejects heat to a high
temperature source (the surrounding atmosphere). It is the refrigeration cycle.
The working substance which

goes under cyclic changes in
the refrigerator is called the Hot reservoir
refrigerant and the process is

known as refrigeration. The
Condenser
schematic arrangement of a
refrigerator is shown in fig.
2.3. The refrigerant in the
form of a liquid is stored in
Liquid
t h e l i q ui d s t o ra g e a t a storage Compressor
temperature to that of the Throttling
condenser whose temperature valve
is equal to that of the hot
source. The refrigerant from Evaporator
the liquid storage passes
through throttling valve
suffering an adiabatic or Cold reservoir
Joule-Thomson expansion
and is cooled to a lower Fig. 2.3
temperature. Then it passes

through the evaporator and evaporates at constant temperature and pressure, absorbing
required latent heat from the object to be cooled. These vapours then pass through the

71
compressor where they are compressed adiabatically by a compression pump. The heat
of compression is rejected at constant pressure by passing the vapours through the
condenser maintained at low temperature. So that the working substance or refrigerant
leaves the condenser as saturated or sub-cooled liquid and the fresh cycle of operations starts.
2.7 Efficiency
In any machine, the working substance absorbs heat from the source, converts a part of
it into external work and gives out the rest to the sink and return to its initial state.
This series of operation is known as a cycle.
Let Q1 be the amount of heat absorbed by the working substance from the source, Q2
that given out by it to the sink and W net amount of work done by it. The net amount
of heat absorbed by the substance is then Q1 − Q2 . Since the working substance returns
to its initial state, the change in internal energy dU is zero. So, by the application of
first law of thermodynamics,
Q1 − Q2 = W
The efficiency η is defined as the ratio of the net work done to the heat absorbed by the
working substance from the source i,e,.
Work done
η=
Heat absorbed by the working substance
Q − Q2 Q
= 1 = 1− 2
Q1 Q1
But, we have
Q1 T
= 1 (where T1 and T2 are absolute temperatures of source and sink)
Q2 T2
T
So, η = 1− 2
T1
It is clear from this equation that the maximum value of η is unity, if Q2 = 0. In other
words, no heat is rejected by the working substance in a cycle i.e., hundred percent
conversion of heat into work. But, it is not possible in actual.
Example 1: An ideal refrigerator is operating between two reservoirs at −20 ° C and

40 ° C respectively. Calculate its efficiency.
T
Solution: Efficiency of a refrigerator, η = 1 − 2
T1
Here, T1 = 40 + 273 = 313 K
and T2 = −20 + 273 = 253 K
Putting the valves, we get

72
253 60
η = 1− = = 019
.
313 313
= 19%
2.8 Molecular Collision

According to kinetic theory of gases, the molecules of a gas move with very large
velocities even at room temperature (the speed of air to room temperature is about 400
m/sec.) It means that with such large velocities, the gaseous mass contained in a vessel
should disappear in a very short time, but in practice we find that a cloud of smoke
holds together for hours i.e., it does not disappear at once. Clausius suggested that we
should not consider the molecules merely as geometrical points but they have got
certain dimensions and hence molecules should be treated as particles having finite size
(though very small).So, molecules (due to finite size) moving in the space of vessel
containing it, collides with each other. The collision between the molecules of a matter is
known as molecular collision. However, the collisions are supposed to be elastic.
2.8.1 Mean Free Path

According to the kinetic theory, the
molecules of a gas are constantly moving
in all directions with various speeds. They
frequently collide with one another and
their speeds and direction change. Since,
the molecules exert no force upon one
another except at collision therefore, they
move in straight lines with constant speed
between two successive collisions. So, the
path of a single-molecule is a series of
short zig-zag paths of different lengths
(Fig 2.4). These are called the free paths
of the molecule and their mean is called mean free path. Hence, the mean free path is the
average distance travelled by a molecule between two successive collisions with other molecules. If
the total distance travelled after N collisions is S, then the mean free path λ is given by
λ = S N.
2.8.2 Collision Cross-Section

If a molecule of diameter d is moving with average speed v, then its sphere of influence sweeps out a
cylinder of base area πd2 and length v in one second. The quantity πd2 is known as the collision
cross section.

73
2.9 Expression for Mean Free Path

Let us assume that all the molecules d
except one molecule A are at rest. Let
d be the diameter of the molecule. A
collision between two molecule will 2d
take place if the distance between
centres of the two molecules is d as
shown in fig. 2.5(a). Collision will also d
occur if the colliding molecule has a (a) (b)
diameter 2d and all other molecules
Fig. 2.5
are point particles as shown in fig.
2.5(b).
Now, we imagine a typical molecule of

equivalent diameter 2d moving with
average speed v through a gas of
equivalent point particles. We further
assume that the molecule and point vt
particles exert no forces on each other.
In time t, the moving molecule will
sweep out a cylinder of length vt and cross sectional area πd2 (Fig. 2.6). In time t this
molecule will collide with every other molecule whose centre lies in this cylinder. Thus,
if there are n molecule per unit volume, the number of collisions made in time t by the
equivalent molecule is equal to n × volume of the cylinder or n × πd 2 vt
The mean free path is the average distance between the collision. Hence,
Total distance covered in time t

λ=
Number of collision in time t
vt 1
or λ= =
2
nπd vt πnd2
If we assume that all other molecules are not at rest, the mean free path will be as,
1
λ= ...(1)
2 πnd2
or λ ∝ 1 d2 and λ ∝ 1 n
It means that the mean free path is inversely proportional to the square of the diameter of the
molecules. Also the mean free path is inversely proportional to the number of molecules
per unit volume i.e., n, which measures the density of the gas. Thus, the mean free path is
inversely proportional to the density of the gas.

74
2.9.1 Variation of Mean Free Path with Temperature and Pressure

For one mole of a gas, we have
pV = RT = NkT
where N is the number of molecules in volume V of a mole of a gas and k is Boltzmans
constant.
NkT
or p= = nkT
V
where n = N V = number of molecules per unit volume
p
or n=
kT
Putting this value in equation (1), we get
kT
λ=
2 πpd2
It means that the mean free path of a molecule is directly proportional to the absolute temperature
of the gas and inversely proportional to the pressure of the gas.
Example 2: Given that, the effective molecular diameter, d = 2 . 0 × 10 −8 cm and the

average speed of the molecules of the gas at a given temperature is 1. 0 × 10 5 cm/sec. The
number of molecules is 3 × 1019 per cm3 . Calculate (i) the mean free path of the
molecules (ii) the corresponding collision frequency.
Solution: (i) The mean free path of a molecule is given by,

1
λ=
2πnd2
Here, effective molecular diameter, d = 2.0 × 10 −8 cm
Number of molecules/unit volume, n = 3 × 1019 / cm 3

1
Putting the values, we get λ = = 1.88 × 10 −5cm
2 × 3 .14 × 3 × 1019 × (2 × 10 −8 )2
(ii) The corresponding collision frequency, f = v λ
Given that, v = 1.0 × 105 cm/sec
Putting the values, we get f = 1.0 × 105 /1.88 × 10 −5
= 5 . 3 × 10 9 /sec

75
Example 3: Calculate the diameter of a molecule of benzene if the mean free path,
λ = 2.2 × 10 −6 cm and n=2.79 × 1019 molecule/cm3 at normal temperature and
pressure.
[Meerut 2008 B]
Solution: The mean free path of a molecule is given by,
1
λ=
2πnd2
Where d is the diameter of molecule.
Given that, λ = 2 .2 × 10 −6 cm and n = 2 .79 × 1019 /cm 3

1
2 .2 × 10 −6 =
. × 2.79 × 1019. d2
2 × 314
1
d2 =
141 . × 2.79 × 1019 × 2 .2 × 10 −6
. × 314
= 36 .80 × 10 −16
o
d = 6.06 × 10 −8cm = 6.06A
Example 4: The molecular diameter of nitrogen is 3 .5 × 10 −8 cm. Calculate the mean

free path at temperature 27°C and pressure 1 atmosphere.
Solution: At temperature T and pressure p, the mean free path is given by,
kT
λ=
2 πd2 p
Here, Boltzman's constant k = 1.38 × 10 −16 erg/K, T = 27° C =300 K
d = 3.5 × 10 −8 cm and p=1 atmosphere=76×13.6×980 dyne / cm 2

1.38 × 10 −16 × 300
λ=
1.41 × 3 .14 × (3 .5 × 10 −8 )2 × 76 × 13 .6 × 980
= 7. 5 × 10 −6 cm
2.10 Transport Phenomena in Gases

According to the kinetic theory of gases, the molecules of a gas are moving constantly in
all direction with various speeds. If the gas is not in an equilibrium state, we may have
any of the following cases:
1. The different layers of the gas may have different speed. It means, there will be a
relative motion between layers of the gas with respect to one another. In such a

76
case the layers moving faster impart momentum to the slower moving layers to
bring the equilibrium state. This gives rise to the phenomenon of viscosity.
2. The temperature of the gas may not be the same throughout. In such case, the
molecules of the gas will carry thermal (kinetic) energy from regions of higher
temperature to the regions of lower temperature to bring the equilibrium state.
This gives rise to the phenomenon of conduction.
3. The number of molecules per c.c. i.e., the number of molecules per unit volume
may not be the same throughout the volume of the gas. If so, the molecules of the
gas will carry the mass from regions of higher concentration to lower
concentrations to bring the equilibrium state. This gives rise to the phenomenon
of diffusion.
Thus, we see that, viscosity, conduction and diffusion represent the transport of
momentum, energy and mass respectively. Hence, these phenomena are called transport
phenomena.
2.11 Transport of Mass

Suppose, a mass of the gas is moving in
parallel layers between parallel planes AB dn
u+λ dz
and CD. Also consider an intermediate C D
plane MN. (Fig. 2.7). Suppose, the
λ
concentration (number of molecules per n
M N
C.C.) increases as we go from AB to CD
through the plane MN. It means that the λ
concentration of gas above the plane MN A B
is greater than that of the gas below MN. dn
n–λ
dz
In order to bring the equilibrium, the
molecules of gas will cross plane MN from Fig. 2.7
AB to CD and vice-versa, unit the
concentration in every region becomes the same. This crossing (diffusion) of gas
molecules through the intermediate plane can be considered as the transport of mass.
dn
Let n be the concentration at the plane MN and be the rate of change of
dz
concentration in an upward direction perpendicular to MN, called concentration
gradient. Let each of the planes AB and CD be at a distance λ from MN, where λ is the
mean free path. Then,
dn
concentration at plane CD = n + λ
dz
dn
and the concentration at plane AB = n − λ
dz

77
As molecules are moving in all possible directions due to thermal agitation. It may be
supposed that one third of the molecules are moving in each of the three directions
parallel to cartesian coordinate axes. So, on the average one sixth of the molecules move
parallel to any one axis in one particular direction. Then, the number of molecules
coming from the plane CD and crossing the plane MN downwards per unit area per sec.
1  dn
= v n+ λ 
6  dz 
and the number of molecules coming from plane AB and crossing the plane MN
upwards per unit area per sec.
1  dn
= v n − λ 
6  dz 
where v is the average molecular velocity.
Therefore, the net number of molecules crossing unit area of the plane
MN downwards per sec
1  dn 1  dn
= v n + λ  − v n − λ 
6  dz  6  dz 
1 dn
= vλ ...(1)
3 dz
If m be the mass of a molecule, then the transported mass M will be,
1 dn 1 dρ
M = mλ v = λv ...(2)
3 dz 3 dz
d ρ mdn
where = is the mass concentration gradient.
dz dz
Thus, mass transported per unit area per second is proportional to the mass
concentration gradient. Hence,
dρ
M∝
dz
dρ
or M=D ...(3)
dz
1
From equation (2) and (3), D = v λ and is called coefficient of diffusion.
3
The coefficient of diffusion D is defined as the ratio of the number of molecules

crossing unit area in one second to the concentration gradient i.e.,
Number of molecules crossing unit area sec
D=
concentration gradient
1 dn
vλ
∴ D= 3 dz = 1 v λ ...(4)
dn 3
dz

78
1 ρv λ η
= =
3 ρ ρ
1
where η = ρ v λ is coefficient of viscosity of the gas and ρ is the density of gas.
3
From equation (4), we can deduce the dependence of D on pressure and temperature.
As we known that, λ ∝ T p and v ∝ T , therefore,
T T3 2
D∝ T or D ∝
P p
Thus, coefficient of diffusion, D varies inversely proportional to pressure p and directly
proportional to T 3 2 .
Example 5: The co-efficient of diffusion and viscosity of oxygen are 1. 22 × 10 −5 m2 /sec

and 1. 95 × 10 −5 Kg/m-sec respectively at a temperature at which the average velocity of
molecule is 440 m/sec. Calculate the density of oxygen and mean free path of its molecules.
Solution: We have,
η
Diffusion coefficient, D = η ρ or density of gas, ρ =
D
Here, coefficient of viscosity, η = 1.95 × 10 −5 Kg / m – sec,
coefficient of diffusion D = 1.22 × 10 −5 m 2 / sec
and velocity of molecule v = 440 m/sec

putting the values of D and η, we get
1.95 × 10 −5
Density of gas, ρ= = 1.59 Kg / m3
1.22 × 10 −5
1
Also, we have D= vλ
3
Again putting the values, of D and v, we get
1
1.22 × 10 −5 = × 440 × λ
3
3 × 1.22 × 10 −5
or λ= = 8 . 32 × 10 −8 m
440
Example 6: The coefficient of self diffusion of oxygen at 273K and 1 atmospheric

pressure is 0 .18 cm2 /sec. Estimate mean free path. The gas constant is 8.3 × 10 7
erg/mole K and molecular weight of oxygen is 32.
Solution: The diffusion coefficient is given by,

1
D= λv ...(1)
3

79
—
Where λ is mean free path and v is the average speed of molecule. Also we have the
average speed at absolute temperature T,
— 3RT
v =
M
where M is the molecular weight of the gas.
Here, R = 8 .3 × 107 erg/mole-K, T = 273 and M = 32
3 × 8 .3 × 107 × 273
v = = 4 .60 × 104 cm /sec
32
Now, putting the value of v and D in eq. (1), we have
1
0 .18 = λ × 4 .60 × 104
3
or λ = 1 .17 × 10 −5cm
2.12 Transport of Momentum

Let us consider a mass of the gas flowing dn
u+λ
dz
in parallel layers between two parallel C D
planes AB and CD. Also consider the
λ
intermediate plane MN. Suppose the
M N
velocity of the layer of the gas in contact
with the plane AB is zero and increases λ
as we go from AB to CD through plane A B
MN. It means that the gas above the u–λ dn
dz
plane MN is moving faster than the
layer of the gas below MN (Fig. 2.8). Fig. 2.8
The faster moving layers exert a
tangential force on the plane MN tending to accelerate its velocity, while at the same
time the layers below MN exert an equal force on the layer MN in opposite direction.
Thus, a tangential force is set up in the plane MN whose tendency is to reduce the
difference in velocities of the layers on the two sides of the plane MN. This property of
the gas is called viscosity. On the basis of kinetic theory this viscosity is due to the
transport of momentum. We can explain it as the layers of the gas above the plane MN
have greater horizontal velocities on the average and hence the greater momentum in a
horizontal direction than the layers below MN. Some of the molecules above MN will
move downwards across MN due to thermal agitation while the others below MN,
having smaller average momentum will be moving up wards. As there is no mass motion
perpendicular to MN, so the number of molecules moving upwards must be equal to the
number of molecules moving downwards. Hence the slower moving layers below MN

80
gain momentum while faster moving layers above MN lose momentum. Thus, viscosity
may be considered due to the phenomenon of transport of momentum.
Let n be the number of molecules per unit volume and v is their average speed. Since
the molecules are moving due to thermal agitation, in all possible directions, it may be
supposed that one third of the molecules are moving in each of three directions parallel
to three cartesian coordinate axes. So on the average, one sixth of the molecules move
parallel to any one axis in one particular direction. Therefore, the number of molecules
crossing the plane MN upwards or downwards per unit area per second are is nv / 6. If m
be the mass of molecule, then, the total mass crossing unit area of MN per second on
either side is (1 6) mnv.
du
Let u be the velocity of flow of the gas along MN and the velocity-gradient in the
dz
upward direction perpendicular to MN. Then the velocities of the gas along the plane
 du  du
CD and AB will be  u + λ  and  u − λ  respectively, where λ is distance of CD or
 dz   dz 
AB from MN and equal to mean free path.
Now, the momentum carried downwards by the molecules crossing unit area of MN per
second from the plane CD is,
1  du
= Mass × Velocity =
mnv  u + λ 
6  dz 
1  du
Similarly, the momentum carried upwards= mnv  u − λ 
6  dz 
Hence, net momentum transferred per second downwards
1  du 1  du
= mnv  u + λ  − mnv  u − λ 
6  dz  6  dz 
1 du
= mnv λ
3 dz
According to Newton's law, the force is defined as the rate of change of momentum.
Therefore, the above expression gives tangential force (or tangential stress the area is
unity) exerted on the plane MN by the upper layers.
The coefficient of viscosity (η) is defined as the ratio of tangential force per unit area
(tangential stress) to the velocity gradient i.e.,
tangential stress
Coefficient of viscosity, η =
velocity gradient
1 du
mnv λ
3 dz 1
or η= or η = mnv λ ...(1)
du 3
dz
1
But, we have that mean free path, λ = , where d is molecular diameter
2 πnd2

81
1 1 mv
∴ η= ...(2)
3 2 π d2
As this expression does not consist of p, so the coefficient of viscosity of a gas is

independent of pressure. But the expression consists of v which is proportional to √ T.
So the coefficient of viscosity of a gas varies directly proportional to the square
root of the absolute temperature of the gas i.e.,
η∝ T
Example 7: The viscosity of oxygen at a temperature 27°C is 200 micropoise. Calculate

the diameter of molecule of the gas, Avogadro number, N = 6.02 × 10 23 and molecular
weight of oxygen is 32, k = 1. 38 × 10 −16 erg/K.
Solution: The coefficient of viscosity is given by,

1 mv
η=
3 2 π d2
Where d is the diameter of molecule of gas

mv
or d2 =
3 2π η
8kT
Also, we have, v=
πm
m 8kT
∴ d2 =
3 2 πη mπ
1 8mkT
=
3 2 ηπ π
Given that, η = 200 micropoise = 200 × 10 −6 poise

32
m = 32 a. m. u. = gm
6 .02 × 1023
k = 1.38 × 10 −16 erg/K, T = 27° C = 300 K
1 . × 10 −16 × 32 × 300
8 × 138
d2 = ×
−6
3 2 × 3.14 × 200 × 10 6 .02 × 1023 × 3 .14
= 375 .32 × 237 × 10 −18 , or d = 2 .98 × 10 −8cm

82
Example 8: In an experiment the viscosity of the gas was found to be 2.25 × 10 −4 CGS
units. The rms velocity of the molecules is 4.5 × 10 4 cm/sec. The density of the gas is 1 gm/litre.
Calculate the mean free path of the molecules.
Solution: We have, the mean free path of the molecules,

1
λ= ...(1)
2 π n d2
1 mv
and viscosity of the gas, η = . ...(2)
3 2 π d2
By using equation (1), equation (2) becomes,

mv λ n ρ v λ
η= = (mn = ρ)
3 3
3η
or λ=
ρv
Given that, η = 2 . 25 × 10 −4 CGS units, ρ = 1 gm/litre = 1 × 10 −3 gm /c.c.
and v = 4.5 × 104 cm/sec

3 × 2 . 25 × 10 −4
λ= = 1.5 × 10 −5cm
10 −3 × 4.5 × 104
2.13 Transport of Energy

Let us consider a mass of the gas at rest in parallel layers between parallel planes AB
and CD. Also consider an intermediate plane MN. Suppose, the temperature increases
as we go from a plane AB to CD through MN (Fig. 2.9). It means that the gas above the
plane MN on average is at higher temperature that the gas below MN. Consequently,
the molecules of the gas coming from
CD and passing downwards across dT
T+λ
dz
MN will have greater kinetic energy (of C D
thermal agitation) than the molecules
λ
coming from AB and passing upwards T
M N
across the plane MN. Therefore, the
average energy of the molecules below λ
MN is continuously increasing while the A B
average energy above MN is continuously T–λ dT
dz
decreasing and hence, the temperature of
Fig. 2.9
the gas below MN is continuously
increasing while the temperature above

83
MN is continuously decreasing. Therefore, the gas is conducting heat from CD to AB

causing inequality of temperature through the whole mass. Thus, the phenomenon of
thermal conduction may be regarded as transport of energy.
Consider a layer MN of the gas at a temperature T and let the temperature gradient be
dT dZ in upward direction perpendicular to the plane. Let each of the plane AB and
CD be at a distance λ from MN, where λ is the mean free path. Then, the temperature
dT dT
of CD plane = T + λ and the temperature of plane AB = T − λ
dZ dZ
As molecules are moving in all possible directions due to thermal agitation, it may be
supposed that one third of the molecules are moving in each of the directions parallel to
the cartesian coordinate axes. So, on average, one sixth of the molecules move parallel
to any one axis in one particular direction. If n is the number of molecules per unit
volume of the gas and v their average velocity, then the number of molecules crossing
the plane upwards or downwards per unit area per second = (1 6)nv. Thus, if m be the
mass a molecules, the total mass crossing unit area of MN per second on either way is
= (1 6)mnv. Now, total heat (energy) carried by the molecules crossing unit area of plane
MN per second in downward direction,
= Mass×Specific heat×Temperature
1  dT 
= m n v × Cv  T + λ 
6  dZ 
Similarly, total heat carried by molecules moving upward and crossing per unit area of
plane MN per second,
1  dT 
= m n v × Cv  T – λ 
6  dZ 
Hence, the net heat (energy) transferred per second,
1  dT  1  dT 
Q= m n v × Cv T + λ  − m n v × Cv T − λ 
6  dZ  6  dZ 
1 dT
= m n Cv v λ ...(1)
3 dZ
The coefficient of thermal conductivity K of a gas is defined as the quantity of heat that
flows per unit area per unit time per unit temperature gradient and is given by,
Q
K=
dT d Z
dT
or Q= K ...(2)
dZ

1
K= mnC v vλ ...(3)
3

84
1
But we know that, λ = , where d is the molecular diameter,
2 nπ d2
1 mC v v
∴ K= ...(4)
3 2 πd2
This is the required expression for coefficient of thermal conductivity of a gas.
From equation (4), we can deduce the dependence of K on pressure and temperature.
The expression is independent of p. Hence, for a given temperature, the coefficient of
thermal conductivity of a gas is independent of pressure. The expression consists of
the average speed v of a molecule, which is proportional to √ T. So, the coefficient of
thermal conductivity varies directly proportional to the square root of absolute
temperature of the gas i.e.,
K ∝ √T
2.14 Relation between Thermal Conductivity and

Viscosity of a Gas
According to kinetic theory, the thermal conductivity and viscosity of a gas are given
by,
1
K= mn v Cv λ ...(1)
3
1
and η = mn v λ ...(2)
3
K K
= C v or C v =
η η
This is required relation.
Example 9: Calculate the radius of an oxygen molecule if its coefficient of thermal

conductivity, K = 24 × 10 −3 Joule m-sec-K at 0°C and specific heat at constant
volume, C v = 20 .9 × 10 3 Joule/kilomole–K. Boltzman constant, k =1.38 × 10 −23
Joule/°C and mass of an oxygen molecule=5.31 × 10 −26 Kg.
Solution: We have thermal conductivity,

1 mvCv
K= ...(1)
3 2 πd2
where v is the average velocity and is given by,

8kT
v=
πm
Given that, k = 1.38 × 10 −23 Joule/K, T=0°C=273K and m = 5 .31 × 10 −26 Kg

85
8 × 1.38 × 10 −23 × 273

v= = 424 m / sec
3 .14 × 5 .31 × 10 −26
From equation (1),

1 m v Cv
d2 =
3 2 πK
where Cv is the specific heat at constant volume and d is the diameter of molecule.
Here, m = 5 .31 × 10 −26 Kg, v=424 m/sec, K = 24 × 10 −3 Joule m-sec – K
20 .9 × 10 −3
and Cv = 20.9 × 103 Joule/kilomole – K = Joule/kg –K
molecular weight of oxygen
20 .9 × 103
= = 0 .653 × 103 Joule/Kg-K
32
1 5 .31 × 10 −26 × 424 × 0 .653 × 103

d2 = ×
3× 2 3 .14 × 24 × 10 −3
= 4 .6 × 10 −20
or d = 2 .14 × 10 −10 = 2 .14 Å
∴ r = 1. 07 Å

86
Problem 1: A refrigerator has to transfer an average of 200 Joules of heat per sec from
temperature −10°C to +27°C. Calculate the average power consumed, assuming no
other losses.
Solution: For an ideal reversible cycle, the efficiency,

T Q
η =1 − 2 =1 − 2
T1 Q1
T2 Q2
or =
T1 Q1
or Q1 = Q2 (T1 T2 )
Given that, Q2 = 200 Joule/sec, T1 = 27° C = 300 K and T2 = −10 ° C = 263 K
300
∴ Q1 = 200 × = 228 .1 Joule/sec
263
Hence, the average power consumed,
W = Q1 − Q2 = 2281 . Joule/sec
. − 200 = 281
= 28.1 watt
Problem 2: The mean free path of nitrogen at 0°C and 1 atm is 0 . 80 × 10 −5 cm. At
this temperature and pressure the number of molecules per cm3 is 2 . 7 × 1019 .
Calculate the diameter of the molecules.
Solution: The mean free path is given by,

1
λ=
2 π n d2
where n=number of molecule per c.c., d=diameter of molecule

1
∴ d2 =
2 π nλ
Here, n = 2 .7 × 1019 per c.c., λ = 0 .80 × 10 −5 cm
Putting the values, we get,

1
d2 =
1.41 × 3 .14 × 2 .7 × 1019 × 0 .80 × 10 −5
= 10 .46 × 10 −16
or d = 3 . 23 × 10 −8 cm

87
Problem 3: Calculate the mean free path of argon molecules at 25°C and 1 atmosphere
o
pressure. Given that, d = 2.56 A and k =1.38 × 10 −23 joule/K.
Solution: Let us first calculate the number of molecules per unit volume of argon gas.
For 1 mole of gas, the equation of state is,
pV = RT
But, R = Nk ,where N is number of molecules in 1mole of gas (Avogadro's number).
Thus,
pV = N kT
The number of molecules per unit volume is no change, therefore,
N p
n= =
V kT
Here, p = 1 atm = 1.013 × 105 newton / meter2 and T = 25 ° C = 298 K
1.013 × 105 N /m 2
∴ n= = 2 .46 × 1025 / m 3
−23
(1.38 × 10 joule /K) × 298 K
Now, the mean free path is,

1
λ=
2 π n d2
Putting the value of n and given value of d (= 2 .56 Å = 2 .56 × 10 −10 m), we get
1
λ=
1.41 × 3 .14 × (2 .46 × 1025 ) × (2 .56 × 10 –10 )2
= 1. 4 × 10 −7 meter
Problem 4: Calculate the mean free path of gas molecules at normal temperature and
pressure. Given that, d=2 × 10 −8cm and k=138
. × 10 −16 erg/K.
Solution: The number of gas molecules per unit volume is given by,
p
n=
kT
Here, p = 1013
. × 106 dyne / cm 2 (normal) ans T=0°C=273K (normal).
1.013 × 106 dyne /cm 2

∴ n= = 2 .69 × 1019 /cm 3
(1.38 × 10 −6 erg /K ) × 273 K
The mean free path,

1
λ=
2 πnd2
1
=
19
1.41 × 3 .14 × (2 .69 × 10 / cm 3 ) × (2 × 10 −8 cm)2
= 2 .1 × 10 −5 cm

88
o
Problem 5: The diameter of an oxygen molecule is roughly 3A . Estimate the mean free
path and mean time between collisions for oxygen gas at N.T.P. The number of
molecules per cm3 at N.T.P. is 3 × 1019 . Avagadro number, N = 6 . 02 × 10 23 per
mole, Boltzman constant, k = 1.38 × 10 −16 erg/K and molecular weight (M) of
oxygen=32 gm/mole.

1
λ=
2 π n d2
Here, n = 3 × 1019 / c. c. and d = 3 Å = 3 × 10 −8 cm

1
λ= = 8 .37 × 10 −6 cm
. × 3 .14 × 3 × 1019 × (3 ×10 −8 )2
141
Now, if v is the average speed of molecule, then mean time interval between collisions,
Τ = λ / v. Also, we have
8k T
v =
πm
where m is the mass of the molecule and is given by,

M 32
m= = = 5 .31 × 10 −23 g
N 6 .02 × 1023
Here, T = 273 K at N.T.P., putting the values, we get
8 × 1.38 × 10 −16 × 273

v = = 4 .25 × 104 cm /sec
−23
3 .14 × 5 .31 × 10
Therefore, the mean time interval between collision is,

−6
λ 8 .37 × 10
Τ= = = 1. 97 × 10 −10 sec
v 4 .25 × 104
Problem 6: The mean free path of the molecules of a gas at 25°C is 2.63 × 10 −5meter.
If the radius of the molecule is 2.56 × 10 −10 meter, find the pressure of the gas.
k =1.38 × 10 -23 joule/degree.

1
λ=
2 π n d2
1
∴ n=
2 π λ d2
Given that, λ = 2 .63 × 10 −5 m and d = 5 .12 × 10 −10 m (as d = 2 r )
89

1
n=
−5
1.41 × 3 .14 × (2 .63 × 10 m) × (5 .12 × 10 −10 m)2
= 3 .28 × 1022 /m 3
We know that the number of molecules per unit volume of the gas is given by,
p
n= or p = nkT
kT
Putting the above value of n and T=25°C=298K, then we have
p = (3 .28 × 1022 / m 3 ) (1.38 × 10 –23 joule / k) (298 k)
= 135 newton /meter2

Now, we find the height of mercury,
135 N /m 2
h=
(13.6 × 103 kg / m 3 ) (9. 8 N /kg)
= 1.0 × 10 −3 meter
= 1. 0 mm of mercury
Problem 7: Calculate the frequency of sound at which the wave length of sound wave
become equal to the mean free path of oxygen at °C and 1.0 atmospheric pressure.
Given that, diameter of oxygen molecule = 3 × 10 −8cm.

1
λ=
2 π n d2
where d is diameter of molecule and n is the number of molecule per c.c. At 0°C and 1
atmospheric pressure
i.e., at N.T.P., the no. of molecules,
6 × 1023
n= = 2 .6 × 1019 and d = 3 × 10 −8 cm
22400

1
λ=
1.41 × 3 .14 × 2 .6 × 1019 × (3 × 10 −8 )2
= 9 . 56 × 10 −6 cm
According to the problem the mean free path is equal to the wavelength of sound wave.
Also we have the speed of sound = 332m/sec.
v
∴ frequency of sound, f =
λ
332 × 100 cm /sec

= = 3.47 × 10 9 / sec
9 .56 × 10 −6
90
Exercise
1. What do you mean by Liquefaction of gases ? [Meerut 2002]
2. Explain Boyle temperature and obtain relation between Boyle temperature and
Critical temperature. Also define Inversion temperature [Meerut 2010]
3. Explain the principle of regenerative cooling and principle of cascade cooling
[Meerut 2012, 03]
4. Explain the principle of regenerative cooling in Joule-Thomson expansion. [Meerut 2006]
5. Describe the principle and method of Liquefaction of Hydrogen [Meerut 2012]
6. Discuss the method of Liquefaction of helium [Meerut 2003]
7. Explain why early attempts to liquify Helium gas were unsuccessful. Give a brief
account of one method of liquefying this gas. [Meerut 2006]
8. Discuss the refrigeration cycle
9. What do you mean by efficiency ?
10. Define the term molecular collision, mean free path and collision cross section.
[Meerut 2008 B]
11. Deduce expression for mean free path and estimate the molecular diameter. Also
explain the variation of mean free path with temperature and pressure. [Meerut 2008B]
12. What do you understand by transport phenomena in gases
[Meerut 2012, 09, 07, 06, 03, 01]
13. Discuss transport of Mass i.e., diffusion of gases. How does the diffusion constant
depend upon temperature and pressure. [Meerut 2008, 03]
14. Derive on the basis of kinetic theory an expression for the coefficient of diffusion
D for a gas and show that it increase with temperature as T 3 2 . Also show that
D = η / ρ where η is the coefficient of viscosity and ρ is the density of the gas.
[Meerut 2003, 02B]
15. On the basis of kinetic theory obtain an expression for the coefficient of viscosity
of a gas and show that it is independent of pressure and varies directly as square
root of absolute temperature. [Meerut 2006B, 06, 04, 02]
16. Discuss the transport of momentum i.e., viscosity of gases. How does the viscosity
depend upon the temperature and pressure [Meerut 2009, 06 B, 02]
17. Apply the kinetic theory to obtain an expression for the coefficient of thermal
conductivity of a gas. [Meerut 2001]
18. Discuss the transport of energy. How does the transport of energy depends on
temperature and pressure ? [Meerut 2001]
19. Explain the thermal conduction on the basis of kinetic theory of gases. Show that
the coefficient of conductivity of a gas is independent of its pressure. [Meerut 2003]
20. Write short note on Helium I and Helium II. [Meerut 2001]
21. Explain what do you mean by liquid Helium I and liquid Helium II. [Meerut 2004, 02]
91

1. Explain,why there is a time lag between opening an ammonia bottle in one corner
of a room and smelling it in the other corner?
2. A gas can transmit only those sound waves whose wavelength is longer than the
mean free path of the gas molecule, explain why?
3. If a gas is filled in a box whose opposite walls are maintained at different
temperatures, explain that the heat conduction takes place through the gas.
4. Establish relation between diffusion coefficient and coefficient of viscosity.
5. Establish the relation between coefficient of thermal conductivity and coefficient of viscosity.
6. Distinguish between liquid helium I and liquid helium II.
[Meerut 2006 B, 05B, 05B, 05, 04, 03, 02, 01]

1. Define inversion temperature.
2. What is Boyle temperature?
3. Define Joule Thomson (Kelvin) effect.
4. Define efficiency of a engine.
5. Define molecular collision.
6. Define mean free path of molecules.
7. Define collision cross section.
8. What must be transported, if gas is not in equilibrium?

1. If cooling of a gas is obtained step by step evaporation of suitable volatile liquid
under reduced pressure, then this process is known as:
(a) Cascade process (b) Regenerative cooling
(c) Adiabatic process (d) None of the above
2. The ratio of temperature of inversion and critical temperature is a constant and is

equal to:
(a) 27/2 (b) 27/8
(c) 27/4 (d) 27×2
3. Liquefaction of hydrogen is obtained with the help of:

(a) Joule-Kelvin effect (b) Adiabatic expansion
(c) Isothermal effect (d) None of the above
4. Liquefaction of helium is obtained with the help of:

(a) Joule-Kelvin effect (b) Adiabatic expansion
(c) Combination of (a) and (b) (d) None of the above
92
5. The efficiency of a engine is always:

(a) Unity (b) Greater than unity
(c) Lesser than unity (d) All the above possible
6. The efficiency of a engine is given by :
T T
(a) 1 − 1 (b) 1 − 2
T2 T1
T
(c) 2 (d) None of the above
T1
7. According to kinetic theory of gases, the molecules of a gas move in:

(a) Only one fixed direction (b) All possible directions
(c) Along three axis (d) None of the above
8. Mean free path of a molecule depends upon:

(a) Square of the diameter of the molecule
(b) The number of molecules per unit volume
(c) Both (a) and (b)
(d) None of the above
9. The mean free path of a molecule depends upon:

(a) Absolute temperature of the gas (b) Pressure of the gas
(c) Volume of the gas (d) (a) and (b) only
10. Transportation of any quantity in a gas occurs only when:

(a) Gas is in equilibrium (b) Gas is in in equilibrium
(c) Gas is in any state (d) None of the above
(E) Fill in the Blank(s)

1. The ratio of Boyle's temperature and critical temperature is ................ .
2. The hydrogen gas liquefies at ...................... at 1 atmospheric pressure.
3. Mean free path of a molecule is the .................... distance travelled by a molecule
between two successive collisions with other molecules.
4. The mean free path of a molecule is inversely proportional to ................ of the gas.
5. The relation between diffusion coefficient (D) and viscosity (η) is given by ........... .
6. Diffusion coefficient is directly proportional to ......................... .
7. Coefficient of viscosity is proportional to the ............... of absolute temperature of
the gas
8. Coefficient of thermal conductivity is proportional to the ................... of absolute
temperature of the gas.
93
(F) True /False

1. Transport of mass means diffusion.
2. Transport of momentum means viscosity.
3. Transport of energy means thermal conductivity.
4. The ratio of temperature of inversion and critical temperature is 27/8.
5. 1
The mean free path is given by, λ =
2 nd2
6. Mean free path of a molecule is directly proportional to the temperature of the
gas.
7. The mean free path of a molecule is inversely proportional to the square of the
diameter of molecule.
8. Diffusion coefficient is directly proportional to the pressure of the gas.
9. Coefficient of viscosity is directly proportional to the pressure of gas.
10. Coefficient of thermal conductivity is independent of pressure.
11. Ratio of thermal conductivity and viscosity gives specific heat of a gas at constant
volume.
Answers
(Hints & Solutions)
6. Helium I and II: Helium gas liquefies at a pressure of 1 atmosphere and 4.2K. A
new phenomenon is observed
when the temperature of
liquid helium is lowered by
boiling it under decreasing
pressure. When the
Specific heat
temperature falls from 4.2 K Helium I
to 2.19 K, the boiling stops Helium II

and the liquid becomes quite.
This shows that below
2.19K, a new liquid phase of
helium is formed. This is 1 2 3
Temperature (K)
called liquid helium II. The
temperature 2.19 is called λ Fig. 2.10
point. The liquid helium
above λ point is called liquid helium I.
94
The transition from liquid helium I to liquid helium II is marked by sudden

discontinuities in certain properties such as density, viscosity, specific-heat and
thermal conductivity. It was observed when the temperature of liquid helium falls
from 4.2K to 2.19 K, the density increases, but with further drop in temperature,
the density suddenly begins to decrease. Similarly, the specific heat of liquid
helium first decreases and then increases up to 2.19 K and at this temperature
there is a sudden and abnormal increase in the specific heat. Below 2.19 K, the
specific heat decreases further (Fig. 2.10).
Viscosity of liquid helium I decreases with decreases in temperature and it is

contrary to the property of a liquid but it resembles that of gas. The viscosity of
helium II is practically zero and it can flow rapidly through narrow capillary
tubes.
The thermal conductivity of liquid helium I is of the same order as for gases at
ordinary temperature. But the thermal conductivity of helium II is about 800
times than that of copper and silver at room temperature.

1. (a) 2. (c) 3. (a) 4. (c) 5. (c)
6. (b) 7. (b) 8. (c) 9. (d) 10. (b)

1. 27/8 2. –253°C 3. average 4. pressure 5. D = η / ρ
6. mean free path 7. square root 8. square root
(F) True/False
1. T 2. T 3. T 4. F 5. F
6. T 7. T 8. F 9. F 10. T
11. T
❍❍❍
I
UN T III
Thermodynamics
Temperature, Zeroth Law
Various Indicator Diagram
Work done by and on the System
First Law of Thermodynamics and its Applications
Internal Energy of a System
Reversible and Irreversible Process
Carnot Cycle and its Efficiency
Carnot Theorem
Second Law of Thermodynamics, Different Versions of Second Law.
Practical Cycle used in Internal Combustion Energy
Entropy, Change of Entropy, Principle of Increase of Entropy
Absolute Thermodynamic scale of Temperature
Thermodynamics Scale is identical with the Perfect Gas Scale
Impossibility of Attaining the Absolute Zero
Third Law of Thermodynamics
Extensive and Intensive Variables
Maxwell's General Relationship
Its Applications to Joule-Thomson Cooling in a General System, Van
der Waal's Gas
Its Applications to Adiabatic Cooling in a General System, Van der
Waal's Gas
Clausius Clapeyron Heat Equation
Specific Heat of Saturated Water
Thermodynamic Potentials and Equilibrium of Thermodynamical
Systems, Relation with Thermodynamic Variables
Cooling due to Adiabatic Demagnetization
Production and Measurement of Very Low Temperatures
97
III
Thermodynamics
3.1 System and Surroundings

E x periments have significant role in the study of science. Such experiments are
performed on some portion of matter. Such a portion of matter which is considered as
separated from its surrounding for the observation is called “system’’. Everything outside
the system which influence its behaviour is known as “surroundings” of the system e.g.
The gas filled in a cylinder fitted with a piston and heated by a burner. Here, the system
is gas and the piston, burner are the surroundings.
3.2 Macroscopic System and Microscopic System

A system can be studied in two different ways called macroscopic and microscopic ways.
Macroscopic means, the properties which describe the grass characteristics of the
system (large scale properties) and can be measured directly in the laboratory e.g. the
chemical composition, pressure, volume, temperature, mass, entropy etc. Of course
these are not concerned with the structure of the system. While microscopic means,
the nature and properties of the system determined by studying the behaviour of the
individual particles comprising the system and cannot be measured directly in the
laboratory. For example, the pressure of the gas can be obtained by giving the
description of the position and velocity of each molecule comprising the system. The
98
variables such as position, velocity, energy, momentum of different molecules of a gas

are called microscopic properties of gases.
3.2.1 Relation between Macroscopic and Microscopic Properties

From the above discussion it is clear that the same state of the system can be described
either macroscopically or microscopically and both give the same result. The pressure of
the gas (a macroscopic property) is related to the average rate of change of momentum
due to impact of gas molecules on the walls of container on a unit area (microscopic
property). Similarly, the temperature of the gas (macroscopic property) can be
expressed in terms of average kinetic energy of translation of gas molecules (microscopic
property). So, macroscopic variable which depend upon microscopic variables i.e., upon
the internal structure of the system are called thermodynamic variables e.g.,pressure,
volume, temperature of the gas.
3.3 Temperature
The temperature of a body is a measure of the hotness or coldness of the body.
3.3.1 Thermal Equilibrium

The state of the system is determined by the variables of the system like temperature,
volume, pressure, etc. If any two of the variables (independent properties) describing
the state of the system remain constant as long as surrounding conditions remain
unchanged, the system is said to be in thermal equilibrium with the surroundings. For
example, if a gas enclosed in a vessel has a pressure p and volume V at the temperature
of the surroundings, the value of p and V will remain constant as long as the
temperature of the surroundings remains unchanged.
Similarly, when two systems A and B having different states (pressure, volume,
temperature etc.), are brought in contact with each other, then it is found that there is a
change in their independent properties (pressure, volume, temperature, etc.), and finally
a state is reached, after which there is no change in any property. Such state is called
equilibrium state and the systems are said to be in thermal equilibrium with each other
and also with the surroundings.
Thus, thermal equilibrium is the state attained by two (or more) systems in thermal contact with one
another and characterised by constant values of the properties (pressure, volume, temperature etc.) of
the system.
3.3.2 Zeroth Law of Thermodynamics

According to it, if two systems A and B separately are in thermal equilibrium with a third
system C, then A and B will be in thermal equilibrium with each other.
99
It implies that a property of all the three systems attain the same value that ensure their
being in thermal equilibrium with one another. This property is known as temperature.
We may, therefore define the temperature of a system as the properly that determine whether or
not the system is in thermal equilibrium with the neighbouring systems. So it is obvious
that if two systems are not in thermal equilibrium, they will be at different
temperatures.
3.4 Thermodynamic System

A thermodynamic system may be defined as a definite quantity of matter bounded by
some closed surfaces, the state of which is described in terms of thermodynamic
variables like pressure p, volume V and Temperature T. A thermodynamic system may
be solid, liquid or gas.
System which can exchange energy and matter with the surroundings are known as
open systems. On the other hand, systems which can exchange energy only, not matter
with the surroundings are known as closed systems. A system, which is not influenced
in any way by its surrounding, is said to be an isolated system.
3.4.1 Thermodynamical Equilibrium

For a system, we have following three types of equilibrium:
1. Thermal Equilibrium: Thermal equilibrium means the temperature of every part
of the system must be the same as that of the surroundings.
2. Mechanical Equilibrium: Mechanical equilibrium means the force exerted by the
system must be uniform throughout the system and must be just balanced by the
external force on the system.
3. Chemical Equilibrium: Chemical equilibrium means there should be no change
in the internal structure of the system due to chemical reaction or diffusion etc.
When the conditions for all the three types of equilibrium, thermal, mechanical and chemical,
are satisfied, the system is said to be in thermodynamic equilibrium.
However, if the conditions for any one of the three types of equilibrium are not
satisfied, the system will be in a thermodynamic non equilibrium state.
3.4.2 Quasi-static process

May be defined as one in which the system is always infinitesimally far away from the
thermodynamic equilibrium, so that the successive states through which the system passes may be
regarded as equilibrium states and may be expressed in thermodynamic coordinates of
the system, as a whole e.g., if we decrease the pressure on a gas enclosed in a cylinder in
small gradual steps by moving the piston up extremely slowly, the process of expansion
100
may will be regarded as quasi-static. On the other hand, if we suddenly raise the piston
up, the gas expands all at once. This process, is not quasi-static process.
3.5 p –V or Indicator Diagram

The work done in a quasi-static (thermodynamic) process (e.g., changing the volume of
a gaseous system) can be easily obtained with the help of pressure, p and volume, V
graph, which is called p – V or indicator diagram. These diagrams can be drawn with the
help of a device called the indicator, which directly records the changes in the volume
and pressure.
3.5.1 Thermodynamic Processes

A change in the thermodynamic coordinates (pressure, volume, temperature etc.), of a
thermodynamic system brings about a change in the state of the system and is called a
thermodynamic process or simply a process.
3.5.2 Work Done During an Isothermal Process

If the change in pressure and volume of a gas p1 A
(system) takes place in such a manner that its

temperature remains the same throughout, it
is called an isothermal process.
Pressure, ρ
p2 B
Let a gas be filled in a cylinder with a piston
at room temperature under atmospheric
G H
pressure. If the piston be pushed down a little
V1 dV V2
to compress the gas (i.e., the work is done on
Volume, V
the gas) its internal energy will increase and
its temperature will rise a little. If the Fig. 3.1
temperature is to be maintained constant, the

extra heat must at once be conducted away to the surroundings. Similarly, if the gas is
allowed to expand (push the piston up a little) i.e., work is done by the gas, its internal
energy decreases and its temperature falls a little. Again to maintain its temperature
constant, heat must at once be conducted to it from the surroundings.
Let 1 gm mole of a perfect gas be allowed to expand under isothermal conditions. Let its
initial volume V1 and pressure p1 is represented by point A and its final volume V2 and
pressure p2 by the point B on p – V indicator diagram (Fig. 3.1) although its
temperature remaining constant.
Suppose a small increase dV in the volume of the gas at pressure p. Then, the work
done by the gas,
101
dW = p dV (shaded strip in the figure).

Therefore, the total work done by the gas during the whole expansion from volume V1
at A to volume V2 at B (Fig. 3.1) i.e.,
V2
W=
∫ dW = ∫ p dV ...(1)
V1
= area under the curve AB

Since, for a perfect gas pV = RT , where R is the gas constant for 1 gm mole of the gas. So,
T
p=R
V
Putting the value of p in equation (1), we get
V2
dV V 
= RT log e  2 
W = RT
∫ V  V1 
V1
V2
or W = 2.3026 RT log10 ...(2)
V1
Since, the temperature remains constant and Boyle's law is obeyed, therefore
V2 p
p1V1 = p2V2 or = 1 [Q pV = RT ]
V1 p2
Hence, equation (2) becomes,
p1
W = 2 . 3026 RT log10 ...(3)
p2
If we take 1 gm of the gas in place of 1 gm mole then the gas constant will be r and
equation (2) and (3) then becomes,
W = 2.3026 r T log10 (V2 / V1)
and W = 2.3026 r T log10 ( p2 / p1)
3.5.3 Work Done During an Adiabatic Process

Adiabatic means heat does not go out or come p1 A
in the system. So adiabatic process means a

p2 B
process in which heat is neither allowed to
Pressure, ρ
enter nor leave the system. Thus, it is a process

which takes place in complete thermal isolation
from the surroundings.
G H
Let, a gas be filled in a cylinder with a piston at V1 dV V2
the room temperature and under atmospheric Volume, V
pressure. Also the cylinder and piston are of a Fig. 3.2
perfectly insulating material. If the piston be
pushed down a little to compress the gas i.e., the work is done on the gas, its internal
102
energy will increase and its temperature will rise a little. Since the heat developed
cannot possibly escape out to the surroundings. Similarly, if the gas be allowed to
expand (push the piston up a little) i.e., work is done by the gas, its internal energy
decreases and its temperature falls a little. Again no heat can possibly enter the cylinder
from out side.
Let 1 gm mole of perfect gas be allowed to expand adiabatically from an initial volume
V1 to a final volume V2 , the pressure changing from p1 to p2 (p – V diagram shown in
fig. 3.2). Then, work done by the gas,
V2
W=
∫ p dV ...(1)
V1
Since, for a perfect gas, in an adiabatic process,

pV γ = K(constant)
K
or p=
Vγ
Putting the value of p in equation (1), we get
V2 V2
K dV
W
∫ Vγ
dV = K
∫ Vγ
V1 V1
V
V1– γ  2 K
= K  = [ V21– γ – V11– γ ]
 1 – γ V 1 – γ
1
K  1 1 
or W=  –  ...(2)
γ – 1 V γ –1 V γ –1 
 1 2 
Also in adiabatic expansion, we have
p1V1γ = K = p2V2γ
Putting the value of K in equation (2), we have


1  p1 V1
γ p2 V2γ 
W= – 
(γ – 1)  V γ –1 V γ –1 
 1 2 
1
or W= [ p V – p2 V2 ] ...(3)
(γ – 1) 1 1
It can be shown that the work done by the gas during adiabatic expansion from volume
V1 at pressure p1 to volume V2 at pressure p2 is given by the area under the p – V curve
for the gas i.e.,
V2
1
W=
∫ p dV = ( p V – p2V2 )
(γ – 1) 1 1
V1
103
= area under the curve AB
Again, we have p1V1γ = p2V2γ = K,
So, V1 = ( K / p1)1 / γ and V2 = ( K / p2 )1 / γ
 1/ γ 1/ γ 
1   K  K

Thus, W= p1   – p2  
(γ – 1)   p1   p2  
 
 γ –1 γ –1 
( K )1/ γ 
or W = ( p1) γ – ( p2 ) γ  ...(4)
(γ –1)  
 
As the temperature of the gas changes from T1 to T2 and also we have, p1V1 = RT1 and
p2V2 = RT2 (where R is gas constant for 1 gm mole gas). Putting these values in
equation (3), we get
R
W = (T –T2 ) ...(5)
(γ –1) 1
If we take 1 gm of the gas in place of 1 gm mole then the gas constant will be r and eq.
(5) becomes,
r
W = (T –T2 ) ...(6)
(γ –1) 1
Since, in an adiabatic process, heat is not allowed to enter or leave the system, the
external work W is done by the gas at the expense of its own internal energy.
So, work done by the gas during adiabatic process = decrease in internal energy of the gas.
Example 1: Calculate the work done when one gram molecule of a gas expands isothermally
at 27°C to double its original volume. (Given that, R = 8.3 Joule/ °C mol).
[Meerut 2003]
Solution: The work done during an isothermal process,
V V
W = RT log e 2 = 2 . 3026 RT log10 2
V1 V1
Here, T = 27° C = 273 + 27 = 300 ° K, V1 = V , V2 = 2V and R = 8 . 3
Putting the values, we have
2V
W = 2 . 3026 × 8 . 3 × 300 log10
V
= 2. 3026 × 8. 3 × 300 log10 2
= 5733.47 × 0. 3010 = 1725 Joule
104
Example 2: Air is compressed adiabatically to half of its volume. Calculate the change in
its temperature.
Solution: Since process is adiabatic. So,

γ –1
 V1  T 
T1V1γ –1 = T2V2γ –1 or   =  2 
 V2   T1 
Here, V1 = V and V2 = V / 2 and for air γ = 14
.
14
. –1
 V  T
∴   = 2
 V / 2 T1
or T2 = T1(2)0 . 4 = 1.319T1
∴ Change in temperature, T2 – T1 = 1.319T1 – T1 = 0 . 319T1K
Example 3: 1 gram of molecule of a monoatomic perfect gas at 27°C is adiabatically

compressed in a reversible process from an initial pressure of 1 atmosphere to a final
pressure of 50 atmosphere. Calculate the change in temperature.
Solution: For an adiabatic process,

γ –1 γ
p  T 
 1 =  1 
p   T2 
 2
Here, p1 = 1 atmosphere, p2 = 50 atmosphere
T1 = 27° C = 300 K and for monoatomic gas γ = 5 / 3
5 5
–1  300  3
 1 3
  =  
 50   T2 
2 5
 T2  3
or (50)3 =  
 300 
or (2 / 3) log 50 = (5 / 3) [log T2 – log 300] = (5 / 3)[log T2 – 2.4771]
or (2 / 3) × 1.6990 = (5 / 3) log T2 – (5 / 3) × 2 .4771
(5 / 3) log T2 = 1.1327 + 4 .1285
log T2 = 3 .1567
T2 = 14 34 K
or T2 – T1 = 1434 – 300 = 1134° C
105
Example 4: A monoatomic ideal gas of volume 1 litre and pressure 8 atmosphere undergoes
adiabatic expansion until the pressure drops to 1 atmosphere. What is the final volume
and how much work is done? Given that, 1 atm. = 10 6 dyne/cm2 .
[Meerut 2008]
p1V1γ = p2V2γ
γ
p1 V 
or =  2 
p2  V1 
Here, p1 = 8 atm., p2 = 1 atm., V1 = 1 litre and for a monoatomic gas γ = 5 / 3 = 1.66
1 . 66
 8  V2 
  = 
 1  1 
or V2 = (8)1(1. 66 )
1 0 .9031
log V2 = log 8 = = 0 .54
1.66 1.66
or V2 = 3 . 467 litre = 3 . 47 × 10 3 c . c .
The work done during the adiabatic process is given by,
1
W= [ p V – p2V2 ]
γ –1 1 1
1
= [8 × 106 × 103 – 1 × 106 × 3 . 47 × 103 ]
1.66 – 1
4 .53 × 109
= = 6 . 86 × 10 9 ergs
0 .66
3.6 Work done depends upon on the Path between

initial and final States
Let a thermodynamic system (gas in a cylinder) with
insulating walls and conducting base is fitted with a
movable piston which carries weights upon it as shown
in fig. 3.3. Suppose, initially the system (gas) is in
equilibrium with its surroundings having a pressure pi
volume V1 and temperature T1. It is then made to
interact with the surroundings (quasi-static process)
such as, changing the volume by slightly decreasing
weight on the piston. Let it (gas) expands and reaches a
final equilibrium state with pressure p2 , volume V2 and
temperature T2 .
106
Let p be the instantaneous pressure of the gas while expanding against the piston, then
instantaneous force on the piston = p A.
where A is the cross sectional area of the piston.
If the piston moves through an infinitesimal distance δx, then an infinitesimal amount
of work done by the gas will be,
δW = pA δx [W = F × d]
= p δV
where δV = Aδx is the infinitesimal increase in volume of the gas.
So, the total work done by the gas during the whole expansion from volume V1 at A to
V2 at B (Fig. 3.4) will be,
B V2
A
W=
∫ δW = ∫ p δV p1
A V1
= the entire area of graph under the curve.
Now, clearly the area under the curve will

Pressure, p
p2 B
depend upon the shape of the curve and p
will be different for different curves with
the same end points A and B. It means that
G
the work done by or on a system depends not V1 dV V2
only on the initial and final states but also on Volume, V
intermediate states i.e., on the path along which Fig. 3.4
the change occurs. In other words, work is a path
function and not a point function.
If the gas was compressed along the same path from a volume V2 at B to a volumeV1 at
A, work done on the gas would be the same numerically, but opposite in sign i.e., equal
to –W. Hence, for convenience, work done by the system (gas) is represented as
positive and work done on the system (gas) is represented as negative.
3.7 First Law of Thermodynamics

The first law of thermodynamics is simply the principle of conservation of energy
applied to a thermodynamic system. This jaw can be explained as follows:
If a quantity of heat dQ is supplied to a body, then in general it is spent in three ways:

(i) Partially, it is spent in raising the temperature of the body i.e., increasing its
internal kinetic energy dU k .
(ii) Partially, it is spent in doing internal work against molecular attraction i.e.,
increasing the internal potential energy dU p.
107
(iii) And rest is spent in expanding the body against the external pressure i.e., in doing
external work dW.
So, above statement can be written as,
dQ = dU k + dU p + dW
But, dU k + dU p = dU (the increase in total internal energy of the body)

∴ dQ = dU + dW
or ∆Q = ∆U + ∆W ...(1)
Therefore, In all transformations, the energy due to heat units supplied must be balanced by the
external work done plus the increase in its internal energy.
Regarding equation (1) it is worthy to note that:
(i) ∆Q, ∆U and ∆W are to be measured in the same unit i.e., all the three either in
Joules or in calories.
(ii) If the heat is taken by the body then ∆Q is positive and if it is given by the body
then ∆Q is negative.
Similarly, if the work is done by the system then ∆ W is positive and if the work is done
on the system then ∆W is negative.
3.7.1 Physical Significance of First Law of Thermodynamics

The mathematical formulation of the first law contains three important features :
(i) Heat is a form of energy.
(ii) Energy is conserved in a thermodynamic system.
(iii) Every thermodynamic system in equilibrium state possesses internal energy and
this internal energy is a function of the state only.
3.7.2 Applications of the First Law of Thermodynamics

(i) Isobaric Process: A process, in which pressure of the system remains constant, is
known as isobaric process. The boiling of water to steam or the freezing of water
to ice are the example of isobaric process.
Let m gm of water is changed into steam at constant pressure and temperature

also. If Vl is the volume of the water in the liquid state and VV is the volume of
water in vapour state, then work done by the system (in expanding from V1 to VV
against the constant pressure p) will be,
Vv Vv
W=
∫ p dV = p
∫ dV
Vl Vl
= p (Vv – Vl )
108
and the heat absorbed by the mass m during the change of state is,
Q = mL
where L is latent heat of vaporisation.
If ∆U be the change in the internal energy, then from the first law of
thermodynamics,
∆U = Q – W
∴ ∆U = mL – p(Vv – Vl )
It is the expression for the change in the internal energy of the system during
vaporisation (isobaric process).
Similarly, we can determine the expression for the change in the internal energy of
the system during freezing (isobaric process),
∆U = mL – p(Vice – Vl )
Here L is the latent heat of ice.

(ii) Isochoric Process: The process, in which volume of the system remains constant,
is called isochoric process. If volume remains constant, then work done W by the
system ( pdV ) will be zero. So, by the first law of thermodynamics,
∆U = Q – W
Now, we have ∆U = Q
Hence, in an isochoric process, the heat taken or lost by the system is entirely used
in increasing or decreasing the internal energy of the system.
(iii) Isothermal Process: The process, in which temperature of the system remains
constant, is known as isothermal process. The temperature remains constant only
in the change of state i.e., liquid to vapour or liquid to ice as in the case of isobaric
process. So, we have
∆U = mLv – p(Vv – Vl )
and ∆U = mLi – p(Vice – Vl )
(iv) Adiabatic Process: The process, in which the total heat of the system remains
constant, (It means no heat flows into or out of the system) is called adiabatic
process i.e., the system is thermally insulated from the surroundings and heat can
neither enter into the system nor can leave it. So, for a such process Q = 0, and by
the first law of thermodynamics, ∆U = Q – W , we have
∆U = –W
Thus, in an adiabatic process the change in internal energy of a system, is equal to the
absolute magnitude to the work. Negative sign means that work is –ve i.e. work is
done on the system and the internal energy is increased. If work is +ve i.e., work is
done by the system, then the internal energy is decreased. When a gas is suddenly
109
compressed (adiabatic process), the work done on the gas is added to its internal
energy so that its temperature rises. This is why the bicycle pump becomes hot when
the air in it is compressed into the cycle tube. Similarly, when a gas is suddenly
expanded, the work done by it against the surroundings is drawn from its internal
energy, due to which its internal energy decreases and temperature of the gas falls.
This is why a motor car tyre bursts, the sudden expansion of its air into the
atmosphere is adiabatic and the tyre is cooled.
(v) Free Expansion: If a system expands in such a way that no heat enters or leave
the system (adiabatic process) and also no work is done by or on the system, then
this expansion is known as free expansion, i.e., in an adiabatic expansion no work
is done by or on the system.
Let us consider an asbestos covered vessel (adiabatic) with rigid walls and divided into
two parts, one containing a gas and the other evacuated. When the partition is suddenly
broken, the gas rushes into the vacuum and expands freely. If U i and U f be the initial
and final internal energies of the gas, then by the first law of thermodynamics,
∆U = Q – W , we have
Q = 0, W = 0 So, ∆U = 0
i.e., Ui – U f = 0
or Ui = U f
Thus, in the free expansion, the initial and final internal energies are equal.
(vi) Cyclic Process: In the cyclic process, the system after passing from initial state to
final state comes back to its initial state. So, in this process the net change in the
internal energy of the system is zero (∆U = 0). Hence, by the first law of
thermodynamics, ∆U = Q – W , we have
∆U = 0 so, Q – W = 0 or Q = W
It means, in the cyclic process the heat taken by the system is equal to the work
done by the system. In the differential form, we may write
∫ d Q = ∫ dW
Thus, for a closed system undergoing a cycle of processes, the cyclic integral of
heat is equal to the cyclic integral of work.
Example 5: The temperature of 5 gm of air is raised from 10°C to 12°C at constant

volume. Compute the increase in its internal energy. Specific heat of air at constant
volume is 0.172 cal/gm-°C and J = 4.18 Joule/cal.
Solution: From first law of thermodynamics the change in the internal energy,
∆U = Q – W
110
where Q is the heat absorbed by the system and W is the external work done by the
system. Here, since the air is heated at constant volume. So, dV = 0 and W = 0
∴ ∆U = Q
The heat absorbed by the air will be,
Q = m × CV × ∆t
where CV = specific heat at constant volume. Given that,
m = 5 gm, CV = 0 .172 cal /gm– ° C and ∆t = 2 ° C
∴ Q = 5 × 0 .172 × 2 = 1.72 cal
So, the change in its internal energy,

∆U = Q = 1.72 cal = 1.72 × 4 .18 Joule = 7. 2 Joule
Example 6: At atmospheric pressure, 1.0 gm of water having volume, 1.0 cm3 becomes 1671
c m3 of steam when boiled. Calculate the external work and the change in internal energy. The
heat of vaporisation of water (latent heat) is 539 cal/gm. (J = 4.18 Joule/ cal and 1
atmospheric pressure = 1. 013 × 10 6 dyne/ c m2 ).
Solution: The external work against the atmospheric pressure p is,
W = pdV
=1 atm. pressure × (1671 – 1.0)
= 1.013 × 106 dyne / c m 2 × 1670 c m 3
= 1629.7 × 106 = 169.27 × 107 ergs = 169.2 Joule
The heat taken by the water to become steam is given by,

Q = mL = 1 × 539 = 539 cal
= 539 × 4 .18Joule = 2253.0 Joule
From the first law of thermodynamics change in internal energy,

∆U = Q −W
= (2253 – 169.2) = 2083.8 Joule
Example 7: A system absorbs 1000 cal of heat and does 1675 Joules of external work. The
internal energy of the system increases by 2515 Joule. Compute the value of J.
Solution: According to first law of thermodynamics,

Q = W + dU
Given that, Q = 1000 cal = 1000 J Joules, W = 1675 Joule
111
and dU = 2515 Joule

1000 J = 1675 + 2515
1675 + 2515 4190
or J= = = 4.19 Joules / cal
1000 1000
3.8 Internal Energy of a System

Every thermodynamic system may seem to have no apparent mechanical energy but
may still be capable of doing work. For example- a mixture of hydrogen and oxygen gas
explode providing mechanical energy. This store of energy, which is not apparently
shown by the system but capable of doing work, is called the internal energy of the system.
According to kinetic theory of matter, matter is made up of large number of tiny

particles called molecules which are in a state of constant rapid motion and hence
possess kinetic energy. The total kinetic energy of the molecules is called the internal
kinetic energy, while the potential energy arising due to the intermolecular attractions is
called the internal potential energy. The sum of the kinetic and potential energies of the
molecules of a system is called its internal energy and is denoted by U. Thus, internal
energy may be defined as the energy possessed by a system by virtue of its molecular constitution
and the position of the these molecules.
Let a thermodynamic system interact with its surrounding and passes from an initial
equilibrium state i to a final equilibrium state f through a certain process. Let Q be the
absorbed heat by the system and W the work done by the system during this process.
The quantity (Q − W ) can be computed. It is experimentally found that if the system be
carried from the state i to f through different processes, the quantity (Q − W ) is found
to be the same, although Q and W may be different for different paths. This quantity
(Q − W ) is defined as the change in internal energy of the system. Thus, if U i and U f
are the internal energies of he system in the initial and final states respectively, then we
have U f − U i = Q − W
This equation is used to measure the change in internal energy of the system and the
internal energy of a system is the function of states only and does not depend upon the path
(process) by which the state has been acquired.
112
3.9 Reversible Process

A reversible process is one which can be reversed in such a way that all the changes taking place in
the direct process are exactly repeated in the reverse order, with no change in any of bodies taking
part in the process or in the surroundings. An engine in which the working substance
performs a reversible process (cycle) is called reversible engine.
Examples of Reversible Process: A given mass of ice melts when a certain amount of
heat is supplied to it and the same mass of ice is formed when the same quantity of heat
is taken from it. All isothermal and adiabatic processes are reversible when performed
slowly i.e., when gas is compressed isothermally slowly, its volume decreases and on
decreasing the pressure (expansion), the gas attains its original volume, if no energy is
wasted in overcoming friction. A reversible process is thus, an ideal limit since the
frictional influences cannot be avoided in actual practice.
3.9.1 Irreversible Process

An irreversible process is one which cannot be reversed exactly. All practical processes
such as Joule- Thomson expansion, electric heating of wire, diffusion of liquids and
gases and free expansion process etc., are irreversible processes. Also all natural
processes- conduction, radiation, radioactive decay etc., are irreversible.
3.9.2 Necessary Condition for Reversible Process/Engine

An engine/process can be reversible only when it satisfies the following conditions:
1. All dissipative forces such as friction, viscosity etc., must be completely absent.
2. The process must be quasi-static.
These conditions are never realised in practice. Hence, a reversible process/engine
is only an ideal one.
3.10 Carnot's Cycle

If a system (working substance) is subjected to a cycle of four operations, consisting of
two isothermal operations and two adiabatic operations, such a cycle is known as
Carnot's cycle. When a heat engine follows Carnot cycle, is called Carnot engine. Sadi
Carnot conceived an ideal theoretical engine free from all imperfections of actual
engines. Carnot engine consists of :
(i) A cylinder with perfectly non-conducting walls but perfectly conducting base
containing a gas (working substance) and fitted with a perfectly insulating and
frictionless piston upon which some weight can be placed.
(ii) A hot body of infinitely large heat capacity at a constant high temperature T1 K as
the source of heat.
(iii) A cold body of infinitely large heat capacity at a constant low temperature T2 K as the sink.
113
(iv) A perfectly insulating stand.
All the components of Carnot's

engine are shown in fig. 3.5 Now,
the working substance is subjected
to go through a cycle of four
processes i.e., Carnot's cycle. Let the
cylinder contain one gm mole of
working substance and the initial
state of the substance is represented
by point A on the p − V indicator
diagram as shown in fig. 3.6.
Process 1: The cylinder is placed

on the source and gas is allowed
to expand by decreasing weights
(pressure) on the piston in infinitely small steps from the initial equilibrium state. The
working substance thus expends infinitely
slowly, doing work in raising the piston. A (p1 ,V1)
During this process substance's temperature (p2 , V2)
T1
falls, but as it is in contact with the source,
B
it takes sufficient heat by conduction
p
through the base to make this process
isothermal at the constant temperature T1 of T2
D C
the source. This process is represented by
(p4 , V4 ) (p3 , V3)
the isothermal curve AB on the indicator
diagram. Let at B the equilibrium state is
represented by ( p2 , V2 , T1) . During this E F V G H
process if heat energy Q1 is absorbed by the Fig. 3.6

gas through the conducting base, then in
accordance with first law of thermo-
dynamics, Q1 must be equal to the work done W1 by the gas in expanding isothermally
from A to B. Hence,
V2
Q1 = W1 =
∫ p dV [Q W = Pressure × Change in volume]
V1
V2
dV
= RT1
∫V [Q pV = RT1]
V1
= RT1 log (V2 / V1) = Area ABGEA ...(1)
114
Process 2: The cylinder is now removed from the source and put on the non
conducting stand and the gas is allowed to expand (by decreasing weight on the piston)
slowly. This expansion is adiabatic because no heat can enter or leave the system. The
system(gas) performs work W2 in raising the piston at the expense of its internal energy
and its temperature therefore falls to T2 K. This process is represented by the adiabatic
curve BC on the indicator diagram. Let at C the equilibrium state is represented by
( p3 , V3 , T2 ) . The work done W2 by the gas in expanding adiabatically from B to C will be,
V3 V3
dV
[ Q pV γ = K]
W2 =
∫ p d V = K ∫ Vγ
V2 V2
K 1
= [V 1 − γ − V21 − γ ] = [ p V − p2V2 ]
1− γ 3 1− γ 3 3
[Q p3 V3 γ = p2 V2 γ = K]
1
= [RT2 − RT1] [Q p2V2 = RT1 and p3V3 = RT2 ]
1− γ
R (T2 − T1) R (T1 − T2 )

= = ...(2)
1− γ γ −1
= Area BCHGB
Process 3: The cylinder is now removed from the stand and put on the sink (temperature
T2 K) and the gas is compressed (by increasing weights on the piston) slowly. During this
process substance's temperature rises, but as it is in contact with the sink, it gives sufficient
heat to the sink through conducting base to make this process isothermal at the constant
temperature T2 . This process is represented by the isothermal curve CD on the indicator
diagram. Let at D the equilibrium state is represented by ( p4 , V4 , T2 ) . During this process
if heat energy Q2 is transferred from the gas to the sink, then this amount of heat must be
equal to the work done W3 on the working substance (gas) in compressing it isothermally
from C to D. Hence,
V4
Q2 = W3 =
∫ p dV
V3
V4
dV
= RT2
∫V [Q pV = RT2 ]
V3
V V
= RT2 log 4 = − RT2 log 3
V3 V4
= Area CHFDC ...(3)
Process 4: Again the cylinder is removed from the sink and placed on the non-
conducting stand and gas is compressed (by increasing weights on the piston) slowly.
115
This compression is adiabatic because no heat can enter or leave the system. Thus, work
W4 is done on the system (gas) and its temperature rises upto T1 and the system comes
back to its original equilibrium state, ( p1, V1 , T1) . This process is represented by the
isothermal curve DA on the indicator diagram. The work done W1 on the gas during this
adiabatic compression from D to A will be,
V1
R (T1 − T2 )
W4 =
∫ pdV =+ 1− γ
...(4)
V4
= Area DFEAD
Hence, the net work done by the gas,
W = W1 + W2 + W3 + W4 = W1 + W3 [Q W2 = − W4 ]
= Area ABCD ...(5)
Thus, the work done in one Carnot cycle is represented by the area of the cycle on a
p −V diagram.
Similarly, the net amount of heat absorbed by the gas = Q1 − Q 2 ...(6)
∴ W = Q1 − Q 2 [Q initial and final states of the gas is same]
The efficiency of the engine is given by,
Heat converted into work
η=
Heat drawn from the source
Q − Q2 Q
η= 1 = 1− 2
Q1 Q1
3.10.1 Efficiency of engine in terms of temperature of the

source T1 and sink T2 K
The net work done by the gas
W = W1 + W2 + W3 + W4
Using equation (1), (2), (3), (4), we have
V R (T1 − T2 ) V R (T1 − T2 )
= RT1 log 2 + − RT2 log 3 −
V1 γ −1 V4 γ −1
V V
or W = RT1 log 2 − RT2 log 3 ...(7)
V1 V4
Now, since point A and D lie on the same adiabatic curve DA. So, we have
T1V1γ − 1 = T2V4 γ − 1 ...(8)
Similarly, B and C lie on the same adiabatic curve BC, we have

T1 V2 γ − 1 = T2V3 γ − 1 ...(9)
Dividing equation(8) by equation (9), we get
γ −1 γ −1
 V1  V 
  =  4 
 V2   V3 
116
V1 V V2 V
or = 4 or = 3
V2 V3 V1 V4
Substituting it in equation (7), we get

V V
W = RT1 log 2 − RT2 log 2
V1 V1
= R (T1 − T2 ) log (V2 / V1) ...(10)
The net amount of heat absorbed by the gas in the cycle is (Q1 − Q2) and since initial
and final states of the system (gas) are the same, it means that its internal energy does
not change i.e., remains the same and hence using first law of thermodynamics,
Q1 − Q 2 = W [Q ∆ U = 0]
∴ W = Q1 − Q2 = R (T1 − T2 ) log (V2 / V1) ...(11)
The efficiency of engine is given by,
Heat converted into work
η=
Heat taken in from the source
V
R (T1 − T2 ) log 2
Q − Q2 V1
= 1 = [Using equation (11) and (1)]
Q1 V2
RT1 log
V1
T − T2 T
= 1 = 1− 2
T1 T1
This expression shows that the efficiency of an engine depends upon the temperature of
the source and sink and it is always less then 1 (100%) as T1 > (T1 − T2 ) .
For any engine to have 100% efficiency, T2 must be zero. Since, we cannot obtain a
sink at absolute zero, so an engine with 100% efficiency is not practically possible.
Example 8: Calculate the efficiency of a Carnot engine working between the temperatures
27 o C and 127 o C.
[Meerut 2007B, 05]

Solution: The efficiency of carnot engine is given by
T
η =1 – 2
T1
Here, T1 = 127 + 273 = 400 K and T2 = 27 + 273 = 300 K
300 100 1
∴ η =1− = = = 0 . 25 = 25%
400 400 4
117
Example 9: Calculate the efficiency of a Carnot's engine between 1000K and 500K.
[Meerut 2012]
Solution: The efficiency of carnot engine is given by
T
η =1– 2
T1
Here, T1 = 1000 K and T2 = 500 K

500 500
∴ η = 1– = = 0 .50 =50%
1000 1000
Example 10: A Carnot engine takes in 100 cal of heat from the source at temperature 400 K
and gives up 80 cal to the sink. What is the temperature of the sink and efficiency of the
engine?
Solution: For a Carnot engine, we have

Q1 T
= 1
Q2 T2
Here, Q1 = 100 cal , Q 2 = 80 cal , T1 = 400 K

100 400 400 × 80
∴ = or T2 = = 320 K
80 T2 100
Τ 320 4 1
The efficiency of engine, η = 1 − 2 = 1 − = 1 − = = 0 . 2 = 20%
Τ1 400 5 5
Example 11: A Carnot engine has the same efficiency between 1000K and 500K and
between x K and 1000K. Calculate x.
Solution: The efficiency of Carnot engine is given by,

Τ
η =1 − 2
Τ1
For the first case, T1 = 1000 K and T2 = 500 K

500 1 1 1
∴ η =1 − = 1 − = = × 100 = 50%
1000 2 2 2
1
Now, for the second case, efficiency is same. So again here, η = , T = x K , T2 = 1000 K
2 1
1 1000 1000 1
∴ =1 − or = or x = 2000K
2 x x 2
118
3.11 Carnot's Theorem

This theorem states that no engine working between two given temperatures can be more efficient
than a reversible engine working between the same two temperatures and that all reversible engines
working between the same two temperatures have the same efficiency, whatever be the working substance.
Hot body
Suppose, there are two engines H and H′ operating source
between the temperatures T1 and T2 . Let engine H be T1
reversible and H′ be irreversible (Fig. 3.7). Let the Q1 Q′1
quantities of working substance used in two engines be
H H′
such that they perform equal work per cycle. Let the
engine H absorbs (taken in) heat Q1from the source (at Q2 Q′2
temperature T1K), performs work W and heat given out T2
to sink (at temperature T2 K) is Q2 = (Q1 − W ) . The Cold body
Sink
efficiency of this engine H will be, ηH = W / Q 1 .
Similarly, let the engine H′ takes - in heat Q1′ from the Fig. 3.7
source (at temperature T1K), performs work W and
gives out Q 2 ′ = (Q 1′ − W ) heat to the sink (at temperature T2 K). The efficiency of H′
will be,
W
ηΗ ′ =
Q1′
Let us assume that efficiency of irreversible engine H′ is greater than that of reversible
engine H. i.e.,
ηΗ ′ > ηΗ
W W
or > or Q 1′ < Q 1 ...(1)
Q 1′ Q
Thus, (Q1 − Q1′ ) is a + ve quantity.

Now, suppose that the two engines H and H′ are Hot body
source
coupled together by a belt in such a way that H ′
T1
works forward and H in backward direction as shown
Q1 Q′1
in fig. 3.8 Engine H now works as a refrigerator
driven by H′, taking in heat (Q1 − W ) from the sink, W H′ W
(at temperature T2K). The work W is done on it and R H
Q1 – W Q′1– W
heat Q, is given out to the source (at temperature
T1 , K). The work W required to be done on H is T2
directly supplied by H′, working forward. In this way Cold body
Sink
the engine H′ and H are coupled together to form a
self acting device. For the complete system as shown
in 3.8, in a complete cycle, the net heat taken in from Fig. 3.8
the sink at T2 K will be,
119
= heat taken in by H– heat given out by H′

= (Q1 − W ) − (Q1′ − W ) = (Q1 − Q1′ )
which is positive since Q1′ < Q1 [eq. (1)]. Also this is the net heat given to the source.
Thus the coupled device is transferring an amount of heat (Q1 − Q1′ ) in each cycle from
the sink (lower temperature T2 K) to the source (higher temperature T1 K) without the
aid of any external energy. But this transference of heat from lower to higher
temperature without any external work is contrary to the second law of
thermodynamics and it is impossible. Therefore, our supposition that the irreversible
engine H′ is more efficient than that of reversible engine H is wrong. Hence, we have to
write,
ηΗ ′ < ηΗ
i.e., The Carnot reversible engine is the most efficient engine and no engine can be more efficient
than a Carnot's engine working between the same two temperatures.
In order to prove the second part of the theorem suppose both engine H and H′ are
reversible engines, working between the same source and sink. If we suppose that H
drives H′ backward, then H cannot be more efficient than H ' (as above proved).
Similarly, if we suppose that H' drives H backward, then H′cannot be more efficient
than H. Hence H and H′ are equally efficient. Thus, The efficiency of all reversible engines,
working between the same two temperatures, is the same irrespective of the nature and properties of
working substance. In other words the efficiency of a reversible engine depends upon the
temperatures of the source and sink and is independent of the nature of the working substance.
Example 12: A refrigerator has to transfer an average of 200 joules of heat per sec from
temperature − 10 oC to + 27 oC Calculate the average power consumed, assuming ideal
reversible cycle and no other losses.
Solution: For an ideal reversible cycle the efficiency,

Τ Q2 T2 Q2
η =1 − 2 =1 − ⇒ =
Τ1 Q1 T1 Q1
Given that, Q2 = 200 Joule/sec, T1 = 27o C = 273 + 27 = 300 K
and T2 = − 10 o C = 273 − 10 = 263 K

T 200 × 300
∴ Q1 = Q2 1 = = 228 .1 Joule/sec.
T2 263
Hence, the average power consumed,

W = Q1 − Q2
. − 200 = 28 .1 Joule/sec = 28.1 watt
= 2281
120
3.12 Second Law of Thermodynamics

As we know that, the working substance in a heat engine takes in heat from a source,
converts a part of it into work and gives out rest heat to the sink at a lower
temperature. From it, it is clear that to convert heat into work, a difference of
temperature is essential. So, no engine has ever been designed which converts all the
absorbed heat from the source into work without rejecting a part of it to the cold body
(sink). This experience led Kelvin and Planck to state that:
It is impossible to construct an engine which operating in a cycle will take heat from a hot body and
convert it completely into work without leaving any change anywhere.
Also, we know know that a refrigerator is also a heat engine working in the backward
direction, i.e., the working substance takes in heat from a cold body, a certain amount
of work is done on it by an external agency and gives out a larger amount of heat to a
hotter body. Thus, a refrigerator transfers heat from a cold body to a hot body with the
aid of an external agency. No refrigerator has ever been constructed which can run
without supply of external energy. This experience led Clausius to state that:
It is impossible to construct a device, which operating in cycle, will transfer heat from a cold body to
a hot body without expenditure of work by an external energy source or in other words heat cannot
flow spontaneously from a colder to a hotter body.
These statements are the statements of the second law of thermodynamics and both
statements are also equivalent.
3.12.1 Equivalence of Kelvin and Calusius Statement
Hot body Hot body

Source Source
T1 T1
Q1 Q1 + Q2
Q2 Q1
R E E R
W = Q1 – Q2 W (= Q1)
Q2
Q2 Q2
T2 T2
Cold body Cold body
Sink Sink
Fig. 3.9 Fig. 3.10
121
Suppose, a refrigerator R transfers an amount of heat Q2 from a cold body to a hot

body (Fig. 3.9) without having any supply of external energy. It is thus, against the
clausius statement. Let us, now suppose an engine E working between the same hot and
cold bodies takes in heat Q1 from the hot body and gives up the heat Q2 to the cold
body and converts a part into work (= Q1 − Q2 ). This engine E alone does not violate
any law, but if the refrigerator R and the engine E are combined together they form a
device in which the cold body is giving out heat Q2 and receiving back the same
amount and thus there is no change in its heat contents. On the other hand, the hot
body receives a heat Q2 while gives out heat Q1 and thus in each cycle it loses an
amount of heat Q1 − Q2 which is completely converted into work without delivering
any heat to the cold body. This is clearly against the Kelvin–Planck's statement.
Similarly, we can show that a violation of the Kelving-Planck's statement leads to the
violation of clausius statement. Let us suppose an engine takes in an amount of heat Q1
from a hot body and converts all into work without giving any heat to the cold body. It
is against the Kelving-Planck's statement. Now suppose a refrigerator R, also working
between the same hot and cold bodies, takes in heat Q2 from the cold body, has an
amount of work W ( = Q1) done upon it by an external agency and gives out heat
Q1 + Q2 to the hot body. This refrigerator R alone does not violate any law, but if the
engine E and refrigerator R are combined together (Fig. 3.10) , they form a device in
which, heat Q2 is drawn from the cold body and transferred to the hot body with no
external source of energy. This is clearly against the clausius statement.
Thus, we see that the violation of the Kelvin-Planck's statements also means violation
of the clausius statement and vice-versa.
3.13 Internal Combustion Engine

The heat engine, in which combustion (of the fuel) takes place inside the cylinder itself
is called the internal combustion engine. e.g., Otto engine, diesel engine and Petrol
engine etc. If combustion occurs outside the cylinder, in a separate furnace, then engine
is called external combustion engine. e.g., steam engine.
The internal combustion engine consists of a cylinder with air tight piston. It has two
valves. I is the inlet valve, the petrol vapour and air from the carburettor are admitted
into cylinder through this valve I. O is the outlet or exhaust valve for the spent up gases
or the exhaust. The valves are kept closed by means of strong springs and get opened
automatically at the proper time by a suitable mechanism. A magneto sparking plug S is
arranged to generate a spark at the appropriate time. Practical cycles of a internal
combustion engine are as following:
122
I O I O I O I O
S S S S
(i) Charging (ii) Compression (iii) Working (iv) Exhaust
Fig. 3.11
1. The Charging Stroke: During this stroke, the inlet valve (I) is open and outlet
valve (O) is closed. The mixture of petrol vapours and air enters in the cylinder.
The piston moves down [Fig. 3.11 (i)].
2. The Compression Stroke:
(p2 , T2) B C (p2 , T3)
The inlet valves is also closed
Ad
and the piston moves up.

iaba
The mixture is compressed to

Ad
tic
iab
ex
a high pressure and the

pa
ati
ns
cc
ion
temperature rise to about

om
p
D (p3 , T4)
600 o C [Fig. 3.11 (ii)].
pre
ssio
n
3. Working Stroke: A spark is E A (p1 , T1)

S
produced at sparking plug
and compressed mixture of
petrol and air ignites. The V2 V3 V1
temperature rises to about V
o
2000 C and a high pressure
of about 15 atmospheres is Fig. 3.12
developed inside the

cylinder. This explains why the cylinder must be kept surrounded by a water
jacket. Now the piston is pushed down and the shaft rotates [Fig. 3.11 (iii)]. Only
in this stroke, work is done by the piston.
4. Exhaust Stroke: The outlet valve opens and the burnt and unburnt gases are
exhausted out to the atmosphere [Fig. 3.11(iv)].
123
The cycle is repeated and the engine works. It is important to note that, the working
substance of the engine is air, not the petrol vapour. The function of the petrol vapour is merely
that of a fuel, to heat up the air.
The indicator diagram of the engine may be taken. In the indicator diagram as shown in
fig. 3.12.
1. SA represents the charging stroke, in which the mixture of petrol vapour and air
enters in the cylinder at the atmospheric pressure in an isobaric operation. At A,
let the volume and temperature of the working substance (air) be V1 and T1
respectively.
2. A to B represents the compression stroke. Air is compressed adiabatically. The
temperature changes from T1 to T2 and the volume changes from V1 to V2 . The
temperature rises to about 600 o C and the pressure about 2 atmospheres.
3. B to C represents the stage, at which the mixture is exploded by a spark. The oil burns
immediately. The temperature of the working substance suddenly shoots up from T2 to
T3 (2000 o C) . The pressure is maintained and the volume changes form V2 to V3 .
4. C to D represents the working stroke, the mixture of air and petrol vapour expand
adiabatically to its original volume V1 with temperature falling from T3 to T4 .
5. At point D, the exhaust valve opens and pressure and temperature drop to the
point A. The volume remains constant.
6. A to E represents the exhaust stroke. Again this is an isobaric operation in which the
unburnt gases are exhausted out of the cylinder. Now the volume is reduced from
V1 to zero, as at the start of the cycle and temperature remains constant at T1 .
3.14 Entropy
The concept of entropy was first introduced by
Clausius in 1854. The meaning of entropy is Q1
A
transformation. B
Consider a number of isothermals at temperature Q2 T1

T1 , T2 , T3 etc., on an indicator diagram (Fig. 3.13). p C
T2
Let there are two adiabatics which intersect these Q3
isothermal in point A and B, C and D and E and F F
E T3
etc.
V
Let ABCD and DCEF represent the Carnot Fig. 3.13
reversible cycle. In the cycle ABCD , let Q1 be the
heat absorbed at temperature T1 and Q2 be the heat rejected at T2 , then from the theory
of a Carnot engine,
124
Q1 Q2
=
T1 T2
Similarly, considering the Carnot cycle DCEF, if Q2 be heat taken at temperature T2

and Q3 be the heat rejected at temperature T3 , then
Q2 Q3
=
T2 T3
Q1 Q2 Q3 Q
or in general we can write, = = ....... = = constant
T1 T2 T3 T
The quantity Q / T is a definite thermal property of the working substance and is called
change in entropy. If the substance takes in heat, then the entropy increases and if
substance gives up heat, then the entropy decrease. The change in entropy is denoted
by ∆S. Thus, ∆S = Q / T .
If the temperature of the substance does not remain constant during the process, we
may consider the heat to be taken in or given up in successive small elements such that
the temperature remains sensibly constant for each element. The small change in
entropy for a small element dQ will be, dS = dQ / T .
dQ
The total change in entropy for the process, ∆S =
∫T
3.14.1 Physical Significance
The entropy of a substance is a real physical quantity like energy, pressure, temperature
that can be measured in laboratory. It provides an alternative statement of the second
law of thermodynamics, according to which, only those processes are possible for a system in
which the entropy of the system plus surroundings increases.
Q Heat energy
By the definition, the change in entropy = =
T Temperature
or Heat energy = Change in entropy × Temperature
From above relation, we can say that the dimensions of heat energy are the same as that
of the product of entropy and absolute temperature. Since the gravitational potential
energy of a body α mass × height (above some zero level). Hence, if we take temperature
(measured above absolute zero) equivalent to height, then entropy corresponds to mass
or inertia. Therefore, entropy may be thought as thermal inertia which has the same
relation with heat motion as mass bears to linear motion or moment of inertia bears to
rotational motion. The unit of entropy is Joule/K.
125
3.15 Change of Entropy in Reversible Process

Let us consider a reversible Carnot cycle ABCD A
shown in fig. 3.14. Initially let the working Q1
substance be in state A. During the isothermal B
expansion AB, the working substance absorbs a p
quantity Q1 of heat from the source at a constant C
temperature T1. As heat is absorbed by the system, D
Q2
Q1 is positive and hence entropy increases by
Q1 / T1 . (This is also decreases in the entropy of V
Fig. 3.14
the source). During the adiabatic expansion BC,
there is no heat taken in or given up so, the
entropy remains unchanged. During the isothermal compression CD, the working
substance gives out an amount of heat Q2 to the sink at constant temperature T2 , so
that its entropy decreases by Q2 / T2 (This is also increase in the entropy of the sink).
Again, during adiabatic compression DA there is no heat taken in or given out and
hence entropy remains unchanged. Thus, for the whole cycle ABCD, the net change in
entropy of the working substance,
Q1 Q2
∆S = −
T1 T2
Q1 Q2
But, by the definition of Carnot reversible cycle, =
T1 T2
Q1 Q2
Therefore, ∆S = − =0
T1 T2
Thus, the net change in the entropy of the working substance in a complete cycle
of a reversible process is zero. This statement is known as Clausius theorem. The
change in entropy of the combined system of the source and sink is also zero. Thus, in a
cycle of reversible process, the entropy of the system remains unchanged or the change in entropy of
the system is zero i.e.,
Q1 Q2 Q
∫ dS =
T1
−
T2
= ∑ T =0
where the integral sign with a circle refers to a complete cycle.
A reversible process, during which the entropy of the system remains constant, is
known as isentropic process.
126
3.15.1 Change of Entropy in an Irreversible Process

Let us suppose the working substance in an engine follows an irreversible process. It
absorbs an amount of heat Q1 at temperature T1 from the source and gives out the
quantity of heat Q2 at temperature T2 to the sink. Then, the efficiency of this cycle is
given by,
Q1 − Q2 Q2
η= =1 −
Q1 Q1
According to Carnot theorem, this efficiency is less than that of a reversible cycle
working between the same temperature T1 and T2 , for which
T2
η =1 −
T1
Q2 T2
Thus, 1− <1 −
Q1 T1
Q2 T2 Q2 Q1
or > or >
Q1 T1 T2 T1
Q2 Q1
or − >0
T2 T1
Considering the whole system, the source loses the entropy by an amount Q1 / T1 and
the sink gains an entropy Q2 / T2 . The net change in entropy for the whole system is,
Q2 Q1
−
T2 T1
which is positive. Thus, there is an increase in entropy of the system during an irreversible
process or in other words, the entropy of a system increases in all irreversible processes. This is
known as the principle of increase of entropy.
3.15.2 Principle of Increase of Entropy

We know that the entropy of a system remains constant in reversible processes but
increases in all irreversible processes. Since all processes are inherently irreversible (no
ideally reversible process is possible). So, the entropy of the system increases in each
cycle and tends to maximum value. This is the principle of increase of entropy and may
be stated as "The entropy of an isolated or self contained system either increases
or remains constant according to irreversible or reversible process respectively".
Analytically it may be written as dS ≥ 0 , where equality sign refers to reversible
processes and the inequality sign refers to irreversible processes.
127
Example 13: Calculate the change in entropy when a body of mass 5gm is heated from 100 K to
300 K. The specific heat of the body is 0.1 cal/gm-K.
Solution: The increase in the entropy of a body of mass m heated from T1 to T2 is
given by,
T2
dQ
∆ S=
∫ T
T1
T2 T2
m×C ∆T dT
=
∫ T
= mC
∫ T
T1 T1
[Q dQ = m × C ∆ Τ where C is specific heat of the body]
= mC log e T2 / T1 = 2 .3026 mC log 10 T2 / T1
Given that, m = 5 gm, C = 0 .1 cal / gm − K, T2 = 300K and T1 = 100 K
Putting the values, we get ∆S = 2 . 3026 × 5 × 0 .1 log 300 / 100
= 1.151 [log 10 300 − log 10 100]
= 1.151[2 . 4771 − 2 . 000] = 1.151 × 0 . 4771 = 0.549 cal / K
Example 14: 10 gm of oxygen is heated from 50 o C to 150 o C at constant volume. Find the
change in entropy. Given that, CV = 5 cal/mole-K
Solution: The increase in the entropy of gas in heating from T1 to T2 is,
T2 T2 T2
dQ m CV ∆Τ dT
∆S=
∫ T
=
∫ T
= m CV
∫ T
T1 T1 T1
= m CV log e T2 / T1 = 2 . 3026 m CV log 10 T2 / T1
Here, m = 10 / 32 gm/mole, CV = 5 cal/mole-K, T2 = 423 K, T1 = 323 K

[Q 1 mole = m/M where m is the mass of gas and M is the molecular mass of the gas]
Putting the values, we get ∆ S = (10 / 32) × 5 × 2 . 3026 [log 423 − log 323]
= 0.42 cal/K
128
Example 15: Calculate the change in entropy if 10 gm of water at 0 o C is heated and

transformed to 10 gms of steam at 100 o C. The latent heat of vaporisation at 100 o C is
538 cal/gm.
[Meerut 2009, 05]
Solution: First of all the change in entropy of 10gm water when the temperature
increases from 0 o C to 100 o C.
T2 T2 T2
dQ m C dT dT
∆S=
∫ T
=
∫ T
= mC
∫ T
T1 T1 T1
373
 T2 
= m C log e 
 T1 
  273
= 10 × 1 × 2 . 3026 × log10 (373 / 273) = 23 . 026 [2 .5717 − 2 . 4362] = 3 .12 cal/K
Now, the change in entropy when 10gm water at 100 o C is converted into 100 o C steam.
Q m L 10 × 538
dS= = = = 14 . 42 cal/K
T T 373
Hence, the total change in entropy = 3 .12 + 14 .42 = 17.54 cal/K
3.16 Entropy of a perfect gas in terms of its pressure,

volume and specific heat
Suppose one mole of a perfect gas at pressure p, temperature T and volume V. When an
infinitesimal amount of heat is given to it, the increase in entropy is,
dQ
dS= ...(1)
T
Let d U be the increase in the internal energy of the gas and dW be the external work
done, then according to first law of thermodynamics,
d Q = dU + dW . ...(2)
If CV be the molar specific heat of the gas at constant volume and the rise in
temperature dT and the change in volume is dV, then
dV
d U = CV d T and d W = pd V = RT [Q pV = RT ]
V
So, equation (2) becomes,
dV
dQ = CV dT + R T
V
129
By using this expression, equation (1) becomes,

dT dV
d S = CV +R ...(3)
T V
If the gas passes from an initial state having p i , V i and T i to a final state with p f , V f
and T f for the corresponding quantities, then the change in entropy is,
f f f
dT dV
∆S =
∫dS = CV
∫ T
+R
∫V
i i i
Tf Vf
∆ S = CV log e + R log e
Ti Vi
This is the expression for the change in entropy in terms of temperature, volume and
specific heat. Again, we have
p iV i p fV f Tf p fV f
= or = and R = C p − CV
Ti Tf Ti p iV i
pf Vf
then, ∆ S = CV log e + C p log
pi Vi
This is the entropy change in terms of pressures, volumes and specific heats.
If the entropy of the gas measured from an arbitrary zero, then the entropy of the gas is
given by,
S = CV log e p + C p log e V
[Q log e ( p f / pi) = log e p f − log e p i = log e p]
This is the expression for the entropy of a perfect gas in terms of its pressure, volume
and specific heats.
3.17 Absolute or Kelvin's or Thermodynamic Scale of

Temperature
According to Carnot's theorem, the efficiency of a reversible engine depends only upon
the two temperatures between which it is working and is independent of the working
substance. Thus, there is a property which absolutely depends on temperature and
nothing else. Lord Kelvin defined a temperature scale which is independent of the properties of
any particular substance and is called an absolute scale of temperature or Kelvin's absolute
thermodynamical scale of temperature.
Suppose a reversible engine takes in heat Q1 from a source at temperature t1 and gives
out heat Q2 to a sink at temperature t 2 , where t1 and t 2 temperatures have been
measured on any arbitrary scale. Also, we have the efficiency of Carnot's engine,
130
Q2
η =1 − = f (t 1 , t 2 ) ...(1)
Q1
i.e., the efficiency is a function of above said (t1 , t 2 ) temperatures.

Q1 1
or = F (t 1 , t 2 ) = ...(2)
Q2 1 − f (t 1 , t 2 )
where F is some other function of t1 and t 2 .
Similarly, for a reversible engine which takes in heat Q2 at temperature t 2 and gives out
heat Q3 at temperature t 3 , then we have,
Q2 / Q3 = F(t2 , t 3 ) ...(3)
The heat Q2 given out by the first engine is taken in by the second. Thus, both engines
working together, form a third engine which takes in heat Q1 at temperature t1 and
gives out heat Q3 at temperature t 3 , then
Q1 / Q3 = F(t1 , t3 ) ...(4)
From equation (2), (3), we have

Q1 Q2 Q1
× = = F (t 1 , t 2 ) × F (t 2 , t 3 )
Q2 Q3 Q3
Comparing with equation (4), we have,

F (t1 , t 3 ) = F (t1, t 2 ) × F (t 2 , t 3 ) ...(5)
This equation is called the functional equation. It does not contain t 2 on the left hand
side. It means that the function F must be such that t 2 disappears from the right hand
side also. This is possible,
φ(t1) φ (t 2 )
if F(t1 , t 2 ) = and F(t2 , t 3 ) =
φ(t 2 ) φ (t 3 )
where φ is another function of temperature.
Substituting the values of F(t1, t 2 ) and F (t 2 , t 3 ) in equation (5), we get

φ (t1) φ (t 2 ) φ (t1)
F(t1, t 3 ) = × = ...(6)
φ (t 2 ) φ (t 3 ) φ (t 3 )
So, equation (2) can be written as,

Q1 φ (t1)
=
Q2 φ (t 2 )
131
We know that Q1 > Q2 . Hence the function φ (t1) > φ (t 2 ) where t1 > t 2 . It means that
the functionφ (t) is an linear function of t [or φ (t) increases as the temperature t rises].
Hence, it can be used to measure temperatures. If we suppose that φ (t) denotes a
temperature θ (some multiple of t) on a new scale, then
Q1 θ1
= ...(7)
Q2 θ2
This equation defines the Kelvin's absolute thermodynamic scale of temperature. The
ratio of any two temperatures on this scale is equal to the ratio of quantities of heat taken in and
given out by a Carnot reversible engine working between these temperatures. It is independent of
the properties of any particular substance.
Now, for a Carnot engine working between a source at temperature θ and a sink at
temperature θ tr , with the help of equation (7) we can write,
θ Q
=
θ tr Q tr
Q
or θ= θ ...(8)
Q tr tr
To define kelvin's absolute scale, we assign any arbitrary value to reference temperature
and let this arbitrary value be the temperature of the triple point of water i.e.
θ tr = 273 .16 K
Q
θ= × 273 .16 K ...(9)
Q tr
On comparision equation (8) with the corresponding equation for ideal gas temperature,
which is as,
PT
T = 273 .16 lim→
Ptr 0 P
tr
We conclude that on Kelvin's absolute scale, θ acts as a thermometric property.
3.17.1 Absolute Zero

It is clear from equation (8) that the heat Q transferred isothermally between two given
adiabatic process decreases as the temperature θ decreases. On the other hand, the
smaller the value of Q, The lower is corresponding temperature θ. The smallest possible
value of Q is zero. The corresponding value of θ is 0 K and is known as absolute zero.
Thus, the absolute zero is the temperature at which a reversible isothermal
process takes place without transfer of heat. It means that at absolute zero, the
isothermal and abiabatic processes are identical.
132
3.18 Thermodynamic Scale and Perfect Gas Scale

Consider one gram mole of a perfect gas
(working substance) follows the Carnot A (p1 , V1)
cycle ABCD as shown in fig. 3.15. Let T1 Isotherm
al (p2 , V2)
and T2 be the temperatures of the source B
p
Adia
Adia
and sink respectively on perfect gas scale
bati
and θ 1 and θ 2 on the absolute thermo-
batic
c
dynamic scale. If Q1 is the quantity of heat D C
(p4 , V4) Isothermal (p3 , V3)
absorbed during the isothermal expansion
AB and Q2 the quantity of heat given out V
to the sink during isothermal compression Fig. 3.15
CD, then by definition of absolute scale,
Q1 θ
= 1 ...(1)
Q2 θ2
Now, we calculate Q1 and Q2 in terms of T1 and T2 . Since, the working substance is an

ideal gas, its internal energy, depending upon the temperature only, will remain
unchanged during isothermal expansion AB. Therefore, the heat absorbed by the gas
will be equivalent only to external work done by the gas in expanding from A to B at
temperature T1 i.e.,
V2 V2
dV V2
Q1 =
∫ pdV = RT1 ∫ V = R T1 [log e V ]
V1
[Q pV = RT ]
V1 V1
= RT1 log e (V2 / V1) ...(2)
Similarly, Q2 will be equivalent to the work done on the gas during isothermal
compression from C to D at temperature T2 i.e.,
V4
Q2 = −
∫ pdV = RT2 log e (V3 / V4) ...(3)
V3
negative sign indicates that the work is done on the gas.

From equation (2) and (3), we get
V2 V2
Q1 RT1 log e T1 log e
V1 V1
= = ...(4)
Q2 V3 V3
RT2 log e T2 log e
V4 V4
Since, the points B and C lie on the same adiabatic process, therefore
γ –1
γ−1 γ −1 T V 
T1 V = T2V3 or 1 =  3  ...(5)
2 T2  V2 
133
Similarly, the points D and A lie on the same adiabatic process.

γ −1
γ −1 γ −1
T1  V4 
So, T1V1 = T2V4 or =  ...(6)
T2  V1 
On comparing, equation (5) and (6), we get

V3 V V2 V3 V2 V3 log (V2 / V1)
= 4 or = or log = log or =1
V2 V1 V1 V4 V1 V4 log (V3 / V4 )
Hence, from equation (4), we have

Q1 T1
= ...(7)
Q2 T2
Comparing equation (1) and (7), we have

θ 1 T1
=
θ 2 T2
i.e., the ratio of any two temperatures on the absolute scale is the same as the ratio on the perfect
gas scale. If θ and T be the temperatures of a given body on the absolute and perfect gas
scales respectively and θ tr and T tr the respective temperature of the triple point of
water, then we have
θ T
=
θ tr T tr
since, θ tr = T tr = 273 .16 K, then we have θ = T
Hence, numerically θ and T are also the same. Thus, perfect gas scale and absolute scale are
identical in all respects.
3.19 Practical Realization of Absolute Scale

The absolute scale cannot be directly realised in practice. It is however, exactly identical
to an ideal gas scale. Hence, the temperature can be measured by a constant volume (or
constant pressure) gas thermometer filled with as ideal gas and it is exactly same as the
temperature measured on an absolute scale. But, in practice no gas is ideal. Hence, we
cannot have an ideal gas thermometer. However, the constant volume hydrogen
thermometer is the closest to an ideal gas thermometer.
3.19.1 Impossibility of Attaining the Absolute Zero

Absolute zero temperature is defined as the temperature at which a system undergoes a
reversible isothermal process without any transfer of heat. The efficiency of a Carnot
reversible engine working between temperatures T1 and T2 is given by,
134
Τ2
η =1 − If T2 = 0 , η = 1 i.e., 100%
T1
It means if the temperature of the sink be zero, complete conversion of heat into work
is possible. But, it is impossible. So, to attain T2 = 0 i.e., absolute zero is impossible.
Now, let the value of T2 is negative i.e., T2 = – x, then
(− x) x
η =1 − =1 +
T1 T1
Thus, η >1
It means engine converts more work than absorbing heat. But, it is impossible. So,
negative temperature on absolute scale is not possible.
3.19.2 Third Law of Thermodynamics

The third law of thermodynamics is based on the unattainability of absolute zero. It
states that, "For any system, even in ideal case, it is impossible by any procedure, to reduce its
temperature to absolute zero in a finite numbers of operations".
3.20 Extensive and Intensive Variables

A system, which can be described in terms of thermodynamic coordinates, is known as
thermodynamic system. The coordinates of a thermodynamic system can be specified
by any pair of variables (quantities). In the case of a gas, the variables are, pressure (p),
volume (V), temperature (T), entropy (S) and internal energy (U). These variables are
known as thermodynamic variables. Variables, which are proportional to mass (or the
number of moles present) are called extensive variables. Volume (V) and internal energy
(U) are the examples of extensive variables. The variables, which do not depend on mass
(or number of moles present) are known an intensive variables. Pressure (p) and
temperature (T) are the examples of intensive variables.
3.21 Maxwell's General Thermodynamic Relations

Maxwell deduced six important relational by using two laws of thermodynamics. As we
know that, a thermodynamic system may be described fully in terms of thermodynamic
variables or coordinates, i.e. pressure (p) volume (V), temperature (T), internal energy
(U) and entropy (S). Any two quantities can be chosen independently and when these
are known, then others can be determined.
Now, according to first law of thermodynamics, we have
dQ = dU + p . dV ...(1)
and second law of thermodynamics gives,
dQ = T . dS ...(2)
135
T . dS = dU + p . dV
or dU = T . dS − p . dV ...(3)
Considering S,U and V to be functions of two independent variables x and y (here x
and y can be any two variables out of p,V,T and S), then we have
∂U ∂U
dU =   d x +   d y
 ∂x y  ∂ y x
 ∂ S  ∂ S
d S =   d x +   d y
 ∂ x  y  ∂ y x
 ∂V  ∂V
and d V =   d x +   d y
 ∂ x y  ∂ y x
Putting the values of dU, dS and dV in equation (3), we get

         
 ∂ U  d x +  ∂ U  d y = T  ∂ S  d x +  ∂ S  d y
 ∂ x   ∂ y
 x   ∂ x   ∂ y
 x 
 y   y 
 
∂V  ∂V
− p   d x +   d y
 ∂ x   ∂ y x 
 y 
Equating the coefficients of dx and dy on both sides respectively, we have

∂U  ∂ S  ∂V
  = T   − p   ...(4)
 ∂x y  ∂ x y  ∂ x y
∂U  ∂ S  ∂V
and   = T   − p   ...(5)
 ∂ y x  ∂ y x  ∂ y x
Differentiating equation (4) with respect to y and equation (5) with respect to x, we get
∂2 U ∂T ∂ S ∂2 S ∂ p ∂V ∂2 V
= +T − −p
∂ y∂x ∂ y∂x ∂ y ∂x ∂ y ∂x ∂ y ∂x
∂2 U ∂T ∂ S ∂2 S ∂ p ∂V ∂2 V
and = + T − −p
∂x∂ y ∂x ∂ y ∂x∂ y ∂x ∂ y ∂x∂ y
But we know that,

∂2 U ∂2 U ∂2 S ∂2 S ∂2 V ∂2 V
= , = and =
∂x∂ y ∂ y ∂x ∂x ∂ y ∂x ∂ y ∂x ∂y ∂y ∂x
[Q dU, dS and dV all are perfect differentials]

Hence, we get
∂ T ∂ S ∂ p ∂V ∂T ∂ S ∂ p ∂V
− = − ...(6)
∂ y ∂x ∂y ∂x ∂x ∂ y ∂x ∂ y
136
It is Maxwell's general thermodynamic relationship.
Now, for the independent variables x and y, we may take any pair of the variables out
of p, V, T and S.
If we take x = T and y = V i.e., taking T and V as independent variables, then we have,

∂T / ∂x =1, ∂V / ∂ y = 1 and ∂T / ∂ y = 0, ∂V / ∂x = 0
Substituting these values in equation (6), we get

 ∂ S  ∂ p
  =  ...(7A)
 ∂V  T  ∂ T  V
∂ Q  ∂ p
or   =T   [Q ds = dQ/T] ...(7B)
 ∂ VT  ∂ T V
Similarly, If x = T and y = p i.e., taking T and p as independent variables, then we have

∂T ∂p ∂T ∂ p
= 1, = 1 and = =0
∂x ∂ y ∂ y ∂x
Substituting these values in equation (6), we get.

 ∂ V  ∂ S
–  =  ...(8A)
 ∂ T p  ∂ p
T
∂ Q  ∂ V
or   = −T   [Q dS = dQ/T] ...(8B)
 ∂ p T  ∂ T p
Similarly, If x = S and y = V i.e., taking S and V as independent variables, then we have

∂ S ∂V ∂ S ∂V
= = 1 and = =0
∂x ∂ y ∂ y ∂x

 ∂ T  ∂p 
  =−  ...(9)
 ∂ VS  ∂S  V
Similarly, If x = S and y = p, i.e., taking S and p as independent variables, then we have

∂S ∂ p ∂S ∂ p
= = 1 and = =0
∂x ∂ y ∂ y ∂x

 ∂ T  ∂ V
  =  ...(10)
 ∂ p S  ∂ S  p
Similarly, If x = T and y = S i.e., taking T and S as independent variables, then we have

∂T ∂S ∂T ∂ S
= 1, = 1 and = =0
∂x ∂ y ∂ y ∂x
Substituting these values in equation (6), we have
137
 ∂ p  ∂V  ∂ p  ∂V
−     = 1 −    
 ∂ S T  ∂T S  ∂T S  ∂ S T
 ∂p   ∂ V  ∂ p  ∂ V
or     −     =1 ...(11)
 ∂T  S  ∂ S  T  ∂ S T  ∂T S
Similarly, If x = p and y = V, i.e., taking p and V as independent variables, then we

have,
∂ p ∂V ∂ p ∂V
= = 1 and = =0
∂x ∂ y ∂ y ∂x

 ∂T  ∂ S  ∂T  ∂ S
    =     − 1
 ∂V p  ∂ p V  ∂ p  V  ∂V p
 ∂ T  ∂ S   ∂ T  ∂ S
or     −    =1 ...(12)
 ∂ p V  ∂ V  p  ∂ V  p  ∂ p V
Equation (7), (8), (9), (10), (11) and (12) are Maxwell's thermodynamical equations.
The first four Maxwell's equations are extremely useful in solving various
problems .
3.22 Heat Transfer in Isothermal Compression of a Liquid

Let dQ be the heat transferred when a liquid is compressed isothermally from a pressure
p1 to p2 , then
dQ =
∫ TdS
p2
 ∂V
∫
= Cp d T − T
∫  ∂ T  p dp
p1
 
Q T d S = C d T − T  ∂V
p   d p
  ∂T p 
 
Since, the compression is isothermal (dT = 0). So, we have

p2
 ∂V
dQ = − T
∫  ∂ T  p d p ...(1)
p1
Also we have, the coefficient of thermal expansion α is defined as the increases in

volume per unit volume per unit increase in temperature at constant pressure i.e.,
138
1  ∂V
α=  
V  ∂T p
 ∂V
∴   = V α
 ∂T p
By using this expression, equation (1) becomes,

p2
dQ = − T
∫V α d p
p1
p2
= −T V α
∫d p
p1
(Q V and α are independent of pressure for any solid or liquid)

= − TVα ( p2 − p1)Joule
T Vα
=− (p2 − p1) cal
J
The negative sign shows that if the pressure is increased isothermally, heat will given
out by the liquid for positive α and heat will be absorbed by the liquid for negative α.
3.23 Heat Transfer in Isothermal Expansion in Van der

Waal's Gas
The Van der Waal's equation for 1 mole of gas is,
 a 
 p + 2  (V − b) = RT
 V 
RT a
or p= −
V − b V2
 ∂ p R
or   = ...(1)
 ∂T V V − b
Also , we have
 ∂ p
Td S = CV d T + T   dV
 ∂T V
Using equation (1), we get

R
T d S = CV dT + T dV
V −b
Integrating on both sides, we get
dV
∫ T d S = CV ∫ d T + RT ∫ V − b
Let dQ be the heat transferred when the gas undergoes reversible isothermal expansion
or compression (dT = 0) from V1 to V2 , then
139
V2
dV
dQ =
∫T d S = R T ∫ V − b [Q dT = 0]
V1
V2
= R T [log (V − b)]
V1
V −b
dQ = R T log e 2
V1 − b
3.24 Temperature Change in Adiabatic Compression of

a Liquid
If a liquid is compressed or expanded adiabatically, then the heat absorbed or evolved in
the liquid does not go outside of the system (dQ = 0) but this heat would cause a
change in internal energy and hence a change in temperature. Let dQ be the heat
absorbed or evolved for getting a change in temperature ∆T, when the liquid is
compressed or expanded adiabatically from pressure p1 to p2 , then
dQ = TdS
∫
p2
 
 ∂V  ∂V
 d p Q T d S = C d T − T  d p
=C
∫ dT −T
∫ 
 ∂T p 


 ∂T p 

p1
Since the compression or expansion is adiabatic, there will be no heat transfer (dQ = 0).
So, we have
p2
 ∂V
∫
C dT =T
∫  ∂ T  pd p ...(1)
p1
∫ dT = ∆T and the coefficient of thermal expansion α is defined as the increase in
volume per unit volume per unit increase in temperature at constant pressure i.e.,
1  ∂V  ∂V
α=   or   = V α
V  ∂T  ∂T p p
By using this expression, equation (1) may be written as,
p2
C ∆T =TV α
∫ d p = T V α ( p2 − p1) joule
p1
T V α ( p2 − p1) T V α (p2 − p1)
or ∆T = Joule = cal
C JC
This expression shows that an adiabatically increase in pressure (compression) will
raise the temperature for a positive coefficient of thermal expansion α while the
adiabatically decrease in pressure will decrease the temperature. It means that an
adiabatic expansion will cool down the liquid under positive coefficient of thermal
expansion.
140
3.25 Internal Energy of a Gas

Let a thermodynamic system undergoes an infinitesimal reversible process between two
equilibrium states. Its general behaviour may be expressed by the first and second law of
thermodynamics, i.e.,
dQ = dU + pdV
and dQ = TdS
Combining both, we get
TdS = dU + pdV
dU + pdV
or dS=
T
Also, we have Maxwell's relation,
 ∂ S  ∂ p
  =  
 ∂ V  T  ∂T V
1  ∂ U + p∂V   ∂ p
So,   =  
T  ∂V T  ∂T V
∂U  ∂ p
or   + p = T  
 ∂V T  ∂T
V
 ∂ U  ∂ p
or   = T   − p ...(1)
 ∂ V T  ∂ V V
It is the required relation.

Now, it is applied to gases,
3.25.1 For an Ideal Gas

For 1 mole of an ideal gas, we have
pV = RT or p = RT/V
 ∂ p R
or   =
 ∂T V V
 ∂ p RT
or T   = =p
 ∂T V V
So from equation (1), we have

∂U  ∂ p
  = T   −p
 ∂V T  ∂T V
=p–p=0
141
Thus, the internal energy of an ideal gas is independent of its volume at constant temperature. It is
known as Joule's law.
3.25.2 For Van der Waal's Gas

For 1 mole of Van der Waal's gas, we have
 
 p + a  (V − b) = RT

 V 2 
RT a
or p= −
(V − b) V 2
 ∂ p R
or   =
 ∂T V V − b
∂U  ∂ p
So,   = T   −p
 ∂V T  ∂T V
RT a
= − p=
V −b V2
∂U a
∴   =
 ∂ V  T V2
This expression shows that the internal energy of a Van der Waal's gas depends on the volume at
constant temperature. Let dU be a perfect differential of T and V, then we have
∂U ∂U
d U =   d T +   d V ...(2)
 ∂T  V  ∂V T
At constant volume, pdV = 0, so dQ = dU (by the first law of thermodynamics)

∂ U  ∂ Q
∴   =   = CV
 ∂ T V ∂ T V
∂ U a
and   = (for Van der Waal's gas)
 ∂ V  T V2
By putting these values in equation (2), we have

dU = C V dT + (a / V 2 ) dV
Integrating on both sides, we get

a
U =
∫ C V dT − V + U0 (constant)
It means that the internal energy of Van der Waal's gas increases as the volume increases at
constant temperature.
142
3.26 Joule's Law for Perfect Gas

According to this law, the internal energy of a perfect gas is independent of the volume of the gas
at constant temperature i.e.,
(∂ U / ∂ V ) T = 0
3.26.1 Cooling Due to Joule Free Expansion in Van Der Waal's Gas
Suppose 1 mole of real (Van der Waal's) gas undergoes free expansion. Let ∆ Τ be the
change in temperature corresponding to a change in volume ∆V. Then by reciprocity
theorem, we have
 ∂T  ∂T ∂ U
  = −     ...(1)
 ∂ V U ∂ U V  ∂ V T
Also we have, the molar specific heat at constant volume, C V = (∂ Q / ∂ T ) V

But, ∂ Q = ∂ U + p∂V
= ∂U (Q at constant volume, dV = 0)
∂ U
∴ C V =  
∂T V
By using this expression, equation (1) can be written as,

∂ T 1 ∂ U
  = −  
 ∂ VU CV  ∂ V T
Also we have for a Van der Waal's gas,

∂ U a
  =
 ∂ V  T V2
∂ T −1 a
∴   =
 ∂ V  U C V V2
Hence, for a finite change in volume, the change in temperature is given by,
1 a
∆ T=− ∆V
C V V2
3.27 Joule-Thomson Effect

When a gas under high constant pressure is passed through an insulated porous plug to a region of
lower constant pressure, the gas shows a change in temperature. This effect is called Joule Thomson
(Joule-kelvin) effect. The change in temperature is directly proportional to the difference in pressures
on both the sides of the porous plug. At ordinary temperatures, all gases (except hydrogen and
helium) show a cooling effect, so it is called Joule Thomson cooling effect.
143
3.27.1 Expression for Joule Thomson Cooling

Consider 1 mole of a gas. Let p1 , V1 and T1, be its pressure, volume and temperature
respectively before entering the porous plug and p2 , V2 and T2 , the pressure, volume
and temperature respectively after passing through the porous plug. Let U 1 and U 2 be
the internal energies of the gas before and after passing through porous plug. The net
external work done by the gas in passing through the plug = p2V2 − p1V1 . Since there is
no heat exchange between the gas and surroundings (as the system is thermally
insulated), so, according the first law of thermodynamics,
U 1 − U 2 = p2V2 − p1V1
or U 1 + p1V1 = U 2 + p2 V 2
or U + pV = Constant
Hence, the quantity (U + pV ) remains constant during the process. This quantity
(U + pV ) is known as enthalpy (H) or heat function of the gas. If the symbol ∆
indicates the change in any quantity, then we may write,
∆H = ∆(U + pV ) = 0
or ∆U + p∆V + V∆p = 0
or dU + pdV + Vdp = 0 ...(1)
But, we have
dU + pdV = dQ (First law of thermodynamics)
and dQ = TdS (Second law of thermodynamics)
Using these law, equation (1) becomes,
TdS + Vdp = 0 ...(2)

Let, entropy S is a function of variable p and T. Since dS is a perfect differential, so we have
 ∂ S  ∂ S
dS =   d T +   d p ...(3)
 ∂ T  p  ∂ p T
By using equation (3), equation (2) becomes,

 ∂ S  ∂ S
T   d T + T   d p+ V d p=0 ...(4)
 ∂ T p  ∂ p T
But, again we have TdS = dQ

 ∂ S  ∂ Q
So, T   =   = C p
 ∂ T p  ∂ T p
where C p is the molar specific heat at constant pressure.
144
 ∂ S  ∂ V
and   = −   (Maxwell's second relation)
 ∂ p T ∂ T p
Therefore, equation (4) becomes,

 ∂ V
C p d T − T   d p + V d p = 0
∂ T p
 
 ∂ V
or C p d T − T   − V  d p = 0
 ∂ T p 
 
 
T  ∂ V
  − V 
 ∂ T p 
dT  
or = ...(5)
d p C p
This is the required expression, giving the change in temperature dT of a gas (during
throttling process), with change in pressure on both sides of porous plug. Since the enthalpy
d T  d T
H remains constant, so we may write =  and it is called Joule Thomson
d p  d p 
H
coefficient, represented by µ. Thus,
 d T 1   ∂ V 
∴ µ =  = T   − V ...(6)
 d p H C p   ∂ T  p 
3.27.2 Joule Thomson Coefficient for a Perfect Gas

For one mole of a perfect gas, pV = RT
 ∂ V R
or   =
∂ T p p
 ∂ V T R
or T   = =V [Q pV = RT]
 ∂ T  p p
 ∂ V
or T   − V = 0
∂ T p
Putting this result in equation (6), we get
µ =0
Thus, the Joule Thomson coefficient (effect) is zero for a perfect gas.
3.27.3 Joule Thomson Coefficient for a Van der Waal's Gas

For one mole of a Van der Waal's gas, we have
145
( p + a / V 2 ) (V − b) = RT
Differentiating it w.r.t., T, taking p as constant, we get

 a   ∂ V 2a  ∂ V
 p + 2    −
3
  (V − b) = R
 V  ∂ T ∂ T p
  p V
 ∂ V R
or   =
 ∂ T  p  a  2a
 p + 2  − 3 (V − b)
 V  V
R R (V − b)
= =
 R T  2a 2a 2
  − (V − b) RT − 3 (V − b)
 V − b V 3 V
 ∂ V RT (V − b)
or T   =
∂ T p 2
2a  b
RT − 1 − 
V  V
Since b << V, so, the term [1 − (b / V )]2 can be neglected. Thus, we have
 ∂ V R T (V − b) (V − b)
T   = =
∂ T p 2 a 2a
RT − 1−
V V RT
−1
 2a   2a 
= (V − b) 1 −  = (V − b) 1 + 
 V R T   V R T 
2a 2 ab 2a
=V − b + − =V − b + (Neglecting 2ab/ VRT)
RT V RT RT
 ∂ V 2a
∴ T   − V = −b
 ∂ T  p R T
Putting this result in equation (6), we get

dT 1  2a 
µ= = − b
d p C p R T 
This expression shows that if (2a/RT> b) i.e., (T< 2a/Rb) then (dT/dp) will be positive.
As dp is necessarily negative (since pressure is greater on entering side), then dT will be
negative i.e., the gas will be cooled. If (T> 2a/Rb) then, dT will be positive and the gas
will be warmed. At T = 2a/Rb, (dt/dp = 0) i.e., there is no change in temperature of the
gas on passing through the porous plug and this temperature is known as temperature of
inversion Ti .
146
Thus, at inversion temperature, the Joule Thomson coefficient, µ = 0 and T i = (2 a / Rb).

For most gases, T i > T i . e . , temperature of inversion is greater than ordinary
temperature. Hence most of the gases show a cooling effect. But for hydrogen and helium,
the inversion temperatures are much below the ordinary temperature, hence these gases
show a heating effect.
3.28 Effect of Increase in Pressure on Heated Body

Let a thermodynamic system undergoes a reversible change from one equilibrium state to
another. Its behaviour may be represented by a Maxwell's thermodynamic relation i.e.,
 ∂ S  ∂ V
  = −  
 ∂ p  T ∂ T p
Multiplying on both side by T, we get

 ∂ S  ∂ V
T   = – T  
 ∂ p  T ∂ T p
∂ Q  ∂ V
or   =− T  ...(1) [Q ∂ Q = T∂S ]
 ∂ p T  ∂ T p
Further, (∂Q / ∂p) T can be expressed in terms of the coefficient of thermal expansion.
The coefficient of thermal expansion α is defined as the increase in volume per unit
1  ∂ V
volume per unit increase in temperature at constant pressure i.e., α =  
V  ∂ T 
p
 ∂ V
or   = α V
∂ T p
So equation (1) can be written as,

 ∂ Q
  = −T α V
 ∂ p T
This is required relation.

Case I: When α is positive, i.e., body expands on heating, then (∂Q / ∂p) T will be
negative. It means that with increase of pressure under constant temperature, heat must
be withdrawn from the body and if heat is not withdrawn, then it will cause a rise in
temperature. In other words, the increase in pressure will heat up a body which
expands on heating.
Case II: When α is negative, i.e., body contracts on heating, then (∂Q / ∂p) T will be
positive. It means that with increase of pressure under constant temperature, heat must
be added to the body. In other words, the increase in pressure will cool down a
body which contracts on heating.
147
3.29 The difference between two Specific heat for

Homogeneous Fluid
We know that specific heat at constant pressure C p and specific heat at constant
volume C V of a thermodynamic system are expressed as,
 ∂ Q  ∂ Q
C p =   and C V =  
∂ T p ∂ T V
 ∂ Q  ∂ Q
∴ C p − C V =   −  
∂ T p ∂ T V
Also we have that , dQ = TdS

 ∂ S  ∂ S
∴ C p − C V = T   − T   ...(1)
 ∂ T p  ∂ T V
Now, let the entropy S is a function of T and V and dS is a perfect differential, then, we
have
 ∂ S  ∂ S
dS =   dT +   dV
 ∂ T V  ∂ V T
 ∂ S  ∂ S  ∂ S  ∂ V
or   =   +    
 ∂ T  P  ∂ T  V  ∂ V T ∂ T p
Multiplying T on both sides, we get

 ∂ S  ∂ S  ∂ S  ∂ V
T   − T   =T    
 ∂ T p  ∂ T V  ∂ V T ∂ T p
 ∂ S  ∂ V
or C p − C V = T     ...(2)
 ∂ V T ∂ T p
[using equation (1)]

But, from Maxwell's relation,
 ∂ S  ∂ p
  =  
 ∂ V  T  ∂ T V
Using this relation, equation (2) becomes,

 ∂ p  ∂ V
C p − C V = T    ...(3)
 ∂ T V  ∂ T  p
It is the required relation.

Also, we have TdS = dU + pdV (First and Second law of thermodynamics)
 ∂ S ∂ U
or T =   =   + p
 ∂ V  T  ∂ V T
Using this expression, equation (2) becomes,
148
  ∂ U    ∂ V 
Cp – C V =  p +     ...(4)
 ∂ V T ∂T p
 
It is also a relation between C p − C V .
3.29.1 For Perfect Gas

For one mole of a perfect gas, we have
pV = RT
 ∂ p R  ∂ V R
or   = and   =
 ∂ T  V V  ∂ T  p p
Putting these values in equation (3), we have

R R R 2T R 2T
C p − CV =T = = =R
V p pV RT
∴ Cp−CV =R
3.29.2 For Van der Waal's Gas

For one mole of a Van der Waal's gas, we have
 a 
 p + 2  (V − b) = R T
 V 
 a  RT
or  p + 2 =
 V  V −b
Differentiating it w.r.t., T at constant pressure, we get,
 ∂ p R
  =
 ∂ T  V V −b
Now differentiating w.r.t. T. at constant pressure, then we have,

−2 a  ∂ V  –R T  ∂ V R
  =   +
3 ∂ T 2  ∂ T  V −b
V (V − b) p p
 ∂ V  RT 2a  R
or    − =
∂ T p (V − b)2 V 3  V − b
R
 ∂ V V −b
or   =
∂ T p RT 2a
−
2
(V − b) V3
 ∂ p  ∂ V
Putting the values of   and   in equation (3) we have
 ∂ T  V ∂ T p
149
R R
T .
V −b V −b R
Cp−CV = =
RT 2a 2 a (V − b)
2
− 1−
2 3
(V − b) V V3 R T
Since b << V , then V − b ≈ V , then we get
R R
C p−CV = =
2  2a 
2a V
1− . 1 − 
V3 R T  V R T 
−1
 2a 
= R 1 − 
 V R T 
 2a 
or C p − C V = R 1 + 
 R T V
[Q a is small and applying binomial theorem]
3.30 Ratio of Adiabatic to Isothermal Elasticity

Four important Maxwell's thermodynamic relations for a homogeneous system are given as,
∂ T  ∂ p
  = −   ...(1)
 ∂ V  S  ∂ S V
 ∂ S  ∂ p
  =   ...(2)
 ∂ V T  ∂ T V
 ∂ T  ∂ V
  =   ...(3)
 ∂ p S  ∂ S  p
 ∂ S  ∂ V
and   = −   ...(4)
 ∂ p  T ∂ T p
The coefficient of volume elasticity E is defined as,

∂ p ∂ p
E=− = −V
∂V / V ∂V
The isothermal elasticity E T (elasticity at constant temperature) and the adiabatic

elasticity ES (elasticity at constant entropy), may be expressed as,
 ∂ p
E T = − V  
 ∂ V T
 ∂ p
and E S = − V  
 ∂ V S
The ratio of adiabatic to isothermal elasticity is,
150
 ∂ p  ∂ p ∂ T  ∂ p  ∂ T
   .     
ES  ∂ V S  ∂ T ∂ V S  ∂ T S  ∂V S
= = =
ET  ∂ p  ∂ p ∂ S  ∂ p  ∂ S
   .     
 ∂ V T  ∂ S ∂ V T  ∂ S T  ∂ V T
Using equation (1), (2), (3) and (4), we get

 ∂ S   ∂ p
   –   ∂ S  ∂ p
ES  ∂ V  p  ∂ S V    
∂V  ∂ S
= =
ET  ∂ T   ∂ p ∂T  ∂ p
 −       
 ∂ V p  ∂ T V  ∂ V  p ∂T V
 ∂ S
 
 ∂ S  ∂ T   ∂ T p
=     =
 ∂ T  p  ∂ S V
 ∂ S
 
 ∂ T V
 ∂ S  ∂ Q
T    
 ∂ T  p ∂ T p
= = [Q TdS = dQ]
 ∂ S  ∂ Q
T    ∂ T 
 ∂ T  V  V
 ∂ Q  ∂ Q
But, we have   = C p and   = CV
∂ T p ∂ T V
ES Cp
∴ =
ET CV
3.31 Clausius-Clapeyron Heat Equation

This equation was deduced by Clapeyron E A
in 1834 and then, by Clausius in 1850,
which describes the conditions
p
governing change of states i.e., melting
of solids or boiling of liquids.
p B T C
To deduce Clausius Clapeyron equation, ∆p
p – ∆p D
consider two isothermal processes ABCD F T – ∆T G
and EFGH (Fig 3.16) at temperatures T H
and T − dT respectively for unit mass of a V1 V V2
substance below its critical temperature Fig. 3.16
151
(i.e., when it is changing state). Along the section AB and EF the substance is in the liquid
state, along BC and FG, the liquid and vapour states coexist in equilibrium. At B and F,
the substance is purely in the liquid state while at C and G, the substance is purely in the
gaseous state. Along CD and GH, the substance is in the gaseous state. Let p and p − dp be
the pressures of the liquid at temperature T and T − dT respectively. Let V1 and V2 be the
specific volumes (volume per unit mass) of the substance at B and C respectively. Join B
to F and C to G by dotted lines. Now, the cycle BCGF represents a Carnot's cycle.
Suppose a Carnot engine, with Carnot cycle BCGFB, contains 1 gm of the liquid in the
state represented by the point B. The liquid undergoes the following processes:
(i) A reversible isothermal expansion along BC. In this process, the liquid is converted into
vapour(at point C), and the amount of heat absorbed at temperature T is Q1 = L .
(ii) A reversible adiabatic expansion along CG .
(iii) A reversible isothermal compression along GF . In this process the vapour gets
converted into liquid (at point F) and the amount of heat is given up at
temperature T − dT is Q2 .
(iv) A reversible adiabatic compression along FB.
The efficiency of the Carnot engine is,
W (work done by the substance during the cycle)

η= ...(1)
Q1 (heat taken in at temperature T )
During a Carnot cycle, the work done will be the area of the curve BCGFB. As the
adiabatics are very small, they can be taken straight and parallel. Thus, the curve
BCGFB is a parallelogram.
So, work done, W = area of BCGFB
= BC × (Perpendicular distance between BC and FG)
= (V2 − V1) × dp
Now, during the process BC, the unit mass of the substance is changed completely from
liquid state to gaseous state at constant temperature T. Then, the heat Q1 taken in by
the substance during the process BC will be its latent heat (L) i.e., Q1 = L.
Substituting these values of W and Q1 in equation(1), we get

(V 2 − V1) dp
η= ...(2)
L
Also, by the thermodynamic scale of temperature, the efficiency of a Carnot engine

working between temperatures T and T − dT is given by,
Q1 − Q2 T1 − T2 T − (T − dT )
η= = = ...(3)
Q1 T1 T
Equating the equation (2) and (3), we have
152
(V 2 − V1) dp dT
=
L T
dp L
or =
dT T (V2 − V 1)
This is Clausius Clapeyron equation. It is applicable equally well to the change of

state from liquid to vapour or that from solid to liquid .
3.31.1 Effect of Pressure on Melting Point of Solids

The Clausius Clapeyron equation is,
d p L
=
d T T (V 2 − V1)

For the substances like, wax, sulphur, etc . which expand on melting, the quantity
(V2 − V1) is positive . In such a case (dp / dT ) is positive i.e., the melting point rises with
increase in pressure. For substance like ice, which contracts on melting, (V2 − V1) is
negative . In this case (dp / dT ) is negative i.e., melting point is lowered with increase in
pressure .
3.31.2 Effect of Pressure on Boiling Point of Liquids

We know that specific volume of a substance in the vapour state is much larger than
that in the liquid state i.e., V2 > V1 or we can say that (V2 − V1) is always positive. Since
L and T are necessarily positive, then the value of (dp / dT ) will be positive, i.e., the
boiling point of every liquid rises with increase in pressure.
Example 16: Calculate the depression in the melting point of ice produced by one
atmosphere increase of pressure. Given that, latent heat of ice = 80 cal/gm and the
specific volumes of 1gm of ice and water at 0 o C are 1.091 cm3 and 1.000 cm3
respectively.
Solution: The decrease in melting point of ice with change in pressure is given by
Clausius Clapeyron equation,
d p L
=
d T T (V2 − V1)
Given that, L = 80 cal / gm = 80 × 4. 2 × 10 7 erg / gm, T = 0 o C = 273 K
V1 = 1 . 091 cm 3 and V2 = 1 . 000 cm 3
and dp = 1 atmosphere = 76 × 13 . 6 × 980 dyne /cm 2
Putting all the values, we get
153
76 × 13 . 6 × 980 80 × 4 . 2 × 10 7
=
dT 273 (1 . 000 − 1 . 091)
76 × 13 . 6 × 980 × 273 × 0 . 091
or dT =–
80 × 4 . 2 × 10 7
= – 74893 × 10 − 7 = − 0 . 0075K
Hence, the decrease in the melting point of ice with an increase of 1 atmosphere
pressure is
0.0075K = 0.0075 o C
Example 17: Find the increase in the boiling point of water at 100 o C when the
pressure is increased by 1 atmosphere. Latent heat of vaporisation of vaporisation of
steam is 540 cal / gm and 1gm of steam occupies a volume of 1677 cm3 .
Solution: The change in boiling point of water with change in pressure is given by
d p L
=
d T T (V2 − V1)
Here, L = 540 cal / gm = 540 × 4 . 2 × 10 7 erg / gm, T = 100 o C = 373 K,
V1 = 1 . 000 cm 3 , V 2 = 1677 cm 3 and dp = 1 atmosphere = 76 × 13 . 6 × 980 dynes / cm 2 .
76 × 13 . 6 × 980 540 × 4 . 2 × 10 7
=
dT 373 (1677 − 1)
76 × 13 . 6 × 980 × 373 × 1676
or dT = = 27. 92 K
540 × 4 . 2 × 10 7
Therefore, the increase in the boiling point of water with an increase of one atmosphere
pressure is
27.92 K = 27. 92 o C
Example 18: Calculate the change in the melting point of naphthalene for one
atmosphere rise in pressure. given that, its melting point is 80 o C. Latent heat of fusion is
4563 cal/mole and increase in volume of fusion is 18.7 cm3 per mole.
Solution: The change in melting point of a substance with change in pressure is given
by Clausius. Clapeyron equation,
154
d p L
=
d T T (V2 − V1)
Given that, L = 4563 cal / mole = 4563 × 4 . 2 × 10 7 ergs / mole, T = 80 o C = 353 K
V2 − V1 = 18 . 7 cm 3 / mol and dp = 1 atmosphere = 76 × 13 . 6 × 980 dyne / cm 2
76 × 13 . 6 × 980 4563 × 4 . 2 × 10 7
=
dT 353 × 18 . 7
76 × 13 . 6 × 980 × 353 × 18 . 7
or dT = = 0.003488 K
4563 × 4 . 2 × 10 7
Therefore, the increase in melting point of naphthalene with an increase in pressure of

one atmosphere is 0.003488 K = 0.003488 o C
Example 19: Calculate the change in boiling point of water when the pressure of steam on its
surface is increased from 1 atmosphere to 1.10 atmosphere. Given that, Latent heat of water
= 537 cal / gm and volume of one gram of steam = 1676 cm3 .
Solution: The change in boiling point of water with change in pressure is given by
d p L
=
d T T (V2 − V1)
Here, L = 537 cal / gm = 537 × 4 . 2 × 10 7 erge / gm , T = 100 o C = 373 K,
V2 = 1676 cm 3 , V1 = 1 . 00 cm 3 and dp = (1 . 10 − 1 . 0) atmosphere
= 0 . 10 atmosphere = 0 . 10 × 76 × 13 . 6 × 980 dyne / cm 2
0 . 10 × 76 × 13 . 6 × 980 537 × 4 . 2 × 10 7
=
dT 373 (1676 − 1)
0 . 10 × 76 × 13 . 6 × 980 × 373 × 1675

or dT = = 2.806 K
537 × 4 . 2 × 10 7
Therefore, the increase in the boiling point of water with an increase of 0 . 10 atmospheric
pressure is = 2.806 K = 2.806°C
155
3.32 Specific Heat of Saturated Vapour

The specific heat of a substance is defined as the quantity of heat required to raise the
temperature of its unit mass through 1o C. The requirement of heat depends upon the
conditions in which the heat is given to the substance for example, when heating takes
place under constant pressure, then it is the specific heat at constant pressure,
represented by C p and when volume remains constant, then it is called specific heat at
constant volume C V .
When the saturated vapour is heated under the conditions of varying pressure and volume in such
a way that the whole mass remains saturated, then the quantity of heat required to raise the
temperature of unit mass vapour through 1o C of is known as the specific heat of saturated vapour.
3.32.1 Clausius Second Latent Heat Equation

The equation, which represents the variation of latent heat with temperature is known
as second latent heat equation,
d L L
s 2 − s1 = −
dT T
E A
Let ABCD and EFGH represents
two isothermals at close temperature
T and T–dT respectively of 1gm
substance below its critical point (fig p
3.17). Section AB and EF
B T
corresponds to the liquid state of p C
the substance, section BC and FG ∆p
corresponds to saturated vapour in p – ∆p

G
D
F T – ∆T
contact of its liquid in equilibrium
H
and section CD and GH corresponds
to the unsaturated vapour state. The V1 V2 V ′2
V
dotted curve represents the
Fig. 3.17
boundary which separates the
different states. Also let p and p – dp
be the satureated vapour pressures of the liquid at temperatures T and T–dT
respectively. Let V 1and V 2 be the volumes of the unit mass of the substance at B
and C respectively.
Let one gm of the substance be taken round the cycle FBCGF. (It is not real Carnot
cycle because BF and CG are not adiabatic processes). Let the specific heats of the
substance in liquid state and saturated state be s 1 and s 2 respectively. If L be the latent
heat at temperature T, the following processes takes place:
(i) During the passage of liquid from F to B, its temperature is increased by dT, the
quantity of heat absorbed by it will be = s 1 dT
156
(ii) The quantity of heat absorbed, along BC in which substance changes from liquid
to vapour state at constant temperature will be = L (latent heat of the substance).
(iii) Along the path CG, the temperature of the substance falls by dT and hence the
quantity of heat given out = s 2 dT .
(iv) Finally, along the path GF, it changes from vapour to liquid state at constant
temperature (T − dT ) and gives out a quantity of heat ( L − dL).
Thus, the net amount of heat taken in during the complete cycle.
= (s 1 dT + L) − (s 2 dT + L − dL)
= (s 1 − s 2 ) dT + dL ...(1)
The amount of heat taken in, is equal to the amount of work done by the substance
during the cycle, which is equal to the area of the cycle BCGFB. Since, both the
isothermals are very close, so cycle BCGFB is practically a rectangle of area BC × δp.
Therefore,
W = BC × δp
= (V 2 − V 1)δp ...(2)
As we know that, at the end of the cycle, the substance returns to its initial state.
Therefore, its internal energy remains unchanged. Therefore, according first law of
thermodynamics, the net heat taken in = external work done W i.e.,
(s 1 − s 2 ) dT + dL = (V 2 − V 1) dp ...(3)
Also, we have Clausius Clapeyron's equation,
d p L
=
d T T (V 2 − V 1)
or dp (V 2 − V 1) = ( L / T ) dT ...(4)
(s 1 − s 2 ) dT + dL = ( L / T ) dT
or (s 1 − s 2 ) + (dL / dT ) = ( L / T )
dL L
or − = s2 − s1
dT T
This is the required Clausius second latent heat equation.
Specific Heat of Saturated Water Vapour

The second latent heat equation is given by,
d L L
s2 − s1 = −
dT T
We have, the specific heat of (liquid) water s 1 = 1 cal / gm-K and normal boiling point of
water i.e., T = 100 o C = 100 + 273 = 373 K and the latent heat of water vapour
= 540 cal / gm
157
Putting all values in the above equation, we have

d L 540
s2 − 1 = −
d T 373
d L d L
or s 2 =1 + − 1 . 45 = − 0 . 45 +
dT dT
We know that the latent heat of water decreases with increase in temperature i.e., dL / dT is
negative. Thus, the specific heat of saturated water vapour (s2 ) at 100 o C is negative.
3.32.2 Explanation of the Negative Specific Heat of Saturated

Water Vapour
The negative specific heat of saturated water vapour can be explained with the help of
fig. 3.17 in which ABCD and EFGH represent two isothermal processes of substance at
temperature T and T– dT respectively. At the point C the substance is in the saturated
vapour state at temperature T and at the point G it is again in the state of saturated
vapour but at temperature T– dT. The dotted curve passing through these points C and
G is known as curve of saturation. From the fig. 3.17 it is also clear that the volume V2 ′
of the saturated vapour at point G is greater than the volume V2 at point C. Consider
that a unit mass of the vapour is taken from the saturated state G to the saturated state
C along the saturated curve GC. As discussed above, the volume is decreased i.e., the
vapour must be compressed. Due to this compression, heat is generated which increases
the temperature of vapour above T. Hence, some heat is withdrawn from vapour to
maintain its temperature T. This means that the specific heat of a saturated water
vapour is negative.
Example 20: The latent heat of water decreases by 0.64 cal/gm for each º C rise in
temperature in the neighbourhood of 100º C and the latent heat of water vapour at
100º C is 540 cal/gm. Find the specific heat of saturated steam at 100º C. The specific
heat of water at 100º C is 1.01 cal/gm-º C.
Solution: The specific heat of saturated steam (s2 ) is given by Clausius second latent
heat equation,
d L L
s2 = s1 + −
dT T
dL
Given that, s1 = 1.01 cal/gm-ºC , L = 540 cal/gm, T = 100ºC=373 K and = − 0 . 64
dT
cal/gmºC
540
s2 = 1.01 − 0.64 − = 1 . 01 − 0 . 64 − 1. 448
373
= – 1.078 cal / gmº C
158
Example 21: Calculate the specific heat of saturated steam at 100º C . Given that, Latent
heat at 90º C = 545 . 25 cal/gm, at 100º C = 539 . 30 cal/gm and at 110º C = 533 . 17
cal/gm. The specific heat of water at 100º C is 1. 013 cal/gm-º C .
Solution: The specific het of saturated steam (s2 ) is given by Clausius second latent
heat equation,
d L L
s2 = s1 + −
dT T
Given that, s1 = 1 . 013 cal/gm-ºC, T = 100ºC = 373 K
L (at 100ºC) = 539.30 cal/gm
d L 533 . 17 − 545 . 25 12 . 08
and = =−
dT (383 − 363)K 20
= – 0.604 cal/gm-K
539 . 30
s2 = 1 . 013 − 0 . 604 − = 1 . 013 − 0 . 604 − 1 . 446
373
= – 1.037 cal/gm-K
3.33 Thermodynamic Potentials (Functions)

The thermodynamic variables such as pressure p, volume V, temperature T and entropy
S define the state of a thermodynamic system. There are two relations between them,
known as thermodynamic laws i.e.,
dQ = dU + pdV
and dQ = TdS
On combining both, we have
TdS = dU + pdV
or dU = TdS − pdV
If any two of these four variables are taken independent, then with the help of above
equation, the remaining variables can be determined. For the complete description of a
thermodynamical phenomenon, certain other relations among these variables are
required. These relations are termed as Thermodynamic potentials or Thermodynamic
functions. There are four such potentials (functions).
3.33.1 Internal Energy (U)

According to kinetic theory, the matter is made up of molecules which are in a state of
constant rapid motion and due to this, they possess internal kinetic energy. They also
possess intermolecular attraction due to which they possess internal potential energy.
The sum of these two energies is called total internal energy of the system. Suppose a system
159
undergoes an infinitesimal reversible change from one equilibrium state to another. The
internal energy changes by an amount,
dU = dQ − dW = dQ − pdV
where dQ is the amount of heat energy absorbed by the system and dW is the work
done by the system in going from one state to another.
Also, we have dQ = TdS
∴ dU = TdS − pdV ...(1)
Differentiating the internal energy partially w.r.t. variables V and S, we get,

 ∂U   ∂U 
  = − p and   =T ...(2)
 ∂V  S  ∂S  V
As dU is a perfect differential so, we can write,
∂  ∂U  ∂  ∂U 
  =  
∂S  ∂V  ∂V  ∂S 
 ∂p   ∂T 
∴   =−  ...(3)
 ∂S  V  ∂V  S
This equation establishes a relation among the four thermodynamical variables p,V,S and T. This
is the maxwell's first thermodynamical relation.
3.33.2 Helmholtz Function (F)

It is also known as "thermodynamic potential at constant volume" or "Helmholtz free
energy". Combining the first and second law of thermodynamics, for a thermodynamic
system,
dU = TdS − dW
Suppose, the temperature of the system remains constant, then
d(TS) = TdS
∴ dU = d(TS) − dW
or d(U − TS) = − dW
or dF = − dW , where F = U − TS ...(4)
This function F is called Helmholtz function or Helmholtz free energy. It represents

the work done by a system in a reversible isothermal process which is equal to the decrease in
Helmholtz free energy.
160
Differentiating equation (4), we get
dF = d(U − TS) = dU − TdS − SdT
But, we have dU = TdS − pdV
∴ dF = (TdS − pdV ) − TdS − SdT
= − pdV − SdT ...(5)
Taking partial differentials of F w.r.t. independent variables T and V, we get
 ∂ F  ∂ F
  = − S and   =−p ...(6)
 ∂ T  V  ∂ V T
As dF is a perfect differential so, we can write,
∂  ∂ F ∂  ∂ F
  =  
∂V  ∂ T  ∂ T  ∂ V
 ∂ S  ∂ p
∴   =  ...(7)
 ∂ V  T  ∂ T V
This equation establishes a relation among four thermodynamical variables p,V,S and T. This is
the maxwell's second thermodynamical relation.
3.33.3 Enthalpy or Total Heat Content (Function) H

It is also called thermodynamic potential at constant volume or heat function of the
system. It is given by,
H = U + pV ...(8)
For an infinitesimal reversible change, we get
dH = dU + pdV + Vdp
= (TdS − pdV ) + pdV + Vdp [Q dU = TdS − pdV ]
∴ dH = TdS + Vdp ...(9)
Since, process is carried at constant pressure (dp = 0)
∴ dH = TdS
Also, we have dQ = TdS (second law of thermodynamics)
∴ dH = dQ
It means that the enthalpy represents the quantity of heat given to the system from an external
source and hence, it is named as heat content.
161
Taking partial differentials of H (equations 9)w.r.t., independent variables S and p, we

have
 ∂H   ∂ H
  = T and   =V ...(10)
 ∂S  p  ∂ pS
As dH is a perfect differential, we can write,

∂  ∂ H ∂  ∂ H
  =  
∂S  ∂ p  ∂ p  ∂ S 
 ∂ V  ∂ T
∴   =  ...(11)
 ∂ S  p  ∂ p S
This equation establishes a relation among four thermodynamic variables V , S, p and T and it is the
maxwell's third thermodynamic relation.
3.33.4. Gibb's Potential (G)

It is also called thermodynamic potential at constant pressure or Gibb's free energy.
As we have, H = U + pV
dH = dU + pdV + Vdp
= (TdS − pdV ) + pdV + Vdp
dH = TdS + Vdp
If the thermodynamic process is isothermal and isobaric (dp = 0), then
dH = TdS = d (TS)
or d ( H − TS) = 0
or dG = 0
where G = H − TS
or G = U + pV − TS ...(12)
The function G is called Gibb's function or Gibb's free energy.
dG = d( H − TS) = dH − TdS − SdT
But dH = TdS + Vdp
∴ dG = TdS + Vdp − TdS – SdT = Vdp − SdT ...(13)
Taking partial differential of G w. r . t. independent variables p and T, we have

 ∂ G  ∂ G
  =V and   = −S ...(14)
 ∂ p T ∂ T p
162
As dG is a perfect differential, we can write,

∂  ∂ G ∂  ∂ G
  =  
∂ T  ∂ p ∂ p  ∂ T 
 ∂ V  ∂ S
∴   =−  ...(15)
∂ T p  ∂ p T
This equation establishes a relation among four thermodynamical variables p, V , S and T. This is
the maxwell's fourth thermodynamical relation.
3.33.5 Importance of These Potentials

Thermodynamic potentials (functions) are of practical importance in studying the
conditions of equilibrium of a system. For example, the condition of equilibrium for a
process in which the temperature (isothermal) and volume (isochoric) of the system
remain constant may be expressed as,
dF = 0 [ Q dF = − pdV − SdT ]
It means that out of the various states in which a system can have isothermal – isochoric
process, only those are stable in which the Helmholtz free energy F = (U − TS) is a
minimum.
Further, from equation (4),
F = U − TS
TS = U − F is known as latent energy or bound energy of the system. Therefore,

U = F + TS. We can write it in words as,
Intristic energy = Helmholtz energy + Latent energy
For a reversible isothermal process,

dU = dF + TdS
= dF + dQ
or dF = dU − dQ = − dW (from the first law of thermodynamics)
where dW is she work done by the system.
According to this relation, the free energy F is such that decrease in it (− dF) gives the
maximum amount of work done (dW ) by the system during an isothermal change from
its initial state to final state. Similarly, the condition of equilibrium for a process in
which the temperature (isothermal) and pressure (isobaric) remain constant may be
expressed as,
dG = 0 [Q dG = Vdp − SdT ]
It means that a system at constant temperature and pressure is in stable equilibrium

when the Gibb's potential (function) G is a minimum.
163
3.34 Thermodynamic Potential U (Internal Energy) & F

(Free Energy)
According to kinetic theory, the matter is made up of molecules which are in state of
constant rapid motion and due to this they possess internal kinetic energy. They also
possess intermolecular attraction due to which they possess potential energy. The sum of
these two energies is known as internal energy of the system. Hence, the internal energy U of a
system is the energy possessed by it due to its molecular constitution and motion.
The free energy of a system is defined as,
F = U − TS ...(1)
where T is the Kelvin temperature and S is the entropy of the system. Let, the system
undergoes an infinitesimal reversible change. Then, the change in F will be given by,
dF = d (U − TS) = dU − TdS − SdT
But, we have, dU = dQ − dW = TdS − dW
So, dF = TdS − dW − TdS − SdT = − dW − SdT ...(2)
If above said change is isothermal i.e., dT = 0 , Then
dF = – dW ...(3)
Thus, the work done is exactly equal to the change in free energy. It means that in a
reversible isothermal change, the external work dW is done at the cost of free energy of
the system. Hence, the free energy of a system is the energy which is available for work in
reversible isothermal change.
We can re-write equation (1) as,

U = F + TS ... (4)
This equation shows that the internal energy U of a system consists of (i) the free
energy, F which is available for work in reversible isothermal changes and (ii) the bound
(latent) energy TS which is unavailable for useful work.
3.34.1 Gibb's Helmholtz Equation

From equation (2) we have,
dF = − dW − SdT
= − pdV − SdT
Taking the partial differential of F at constant volume (dV = 0), we have
 ∂ F
  =−S
 ∂ T V
Substituting this value of S in equation (4), we get

 ∂ F
U= F− T  ...(5)
∂ T V
This is Gibb's-Helmholtz equation.
164
3.34.2 Importance
The Gibb's-Helmholtz equation does not consists of energy S (the calculation of S is
often difficult). Hence, it can be easily applied to study the thermodynamics of
isothermal changes in a chemical system.
Let a chemical system undergoes an isothermal change from state 1 to state 2 at
temperature T, then from Gibb's-Helmholtz equation, we have
 ∂ 
U2 − U1 = F2 − F1 − T  ( F2 − F1)
∂ T 
∂ ∆ F 
∆U =∆ F − T  
 ∆T V
But from equation (3), we have ∆ F = − ∆ W, which is the work obtainable from the
system during a reversible change and from the first law, − ∆ U = U r , where U r is the
heat of reaction at constant volume,
 ∂ 
∴ − Ur = − W − T  ( − W )
 ∂T 
dW
or W − Ur = T
dT
Thus, with the help of Gibb's Helmholtz equation, we can calculate the variation of W
with temperature.
Example 22: 1 gm water when converted into steam at atmospheric pressure occupies a
volume of 1671 cm3 . The latent heat of vaporisation at this temperature is 539 cal/gm.
Compute the increase in internal energy ( ∆U), entropy ( ∆S), enthalpy ( ∆H) and the
energy ( ∆G) at the evaporation temperature and pressure.
Solution: The heat taken in by 1gm of water in converting to steam at 100ºC is given by,
dQ = mL = 1 × 539 cal
= 539 × 4 . 18 × 107 = 22 . 53 × 109 erg
Since, the conversion takes place at constant pressure. So, the work done, dW = pdV
= 1 . 01 × 106 dyne / cm 2 × (1671 − 1) cm 3
= 1.69 × 109 erg

Therefore, the change in internal energy,
dU = dQ − dW = 22 .53 × 109 − 1.69 × 109
= 20.84 × 10 9 erg
d Q 22 . 53 × 109
The change in entropy, dS= =
T 373
= 6 . 04 × 10 7 erg / K
The change in enthalpy, dH = dU + pdV + Vdp
= dU + pdV [at constant pressure dp = 0]
165
= dU + dW = dQ
= 22 . 53 × 10 9 erg
The change in Gibbs free energy is given by,
dG = Vdp − SdT
= 0 [for an isothermal and isobaric process]
3.35 Cooling Due to Adiabatic Demagnetisation

When a paramagnetic substance is placed in magnetising field H, its elementary
magnetic dipoles becomes aligned in the direction of magnetic field. Certain amount of
external work is done in this process. This work is added to the internal energy of the
substance and hence its temperature rises. Conversely when a already magnetised substance
is suddenly demagnetised, there will be a fall in its temperature. This phenomenon is known as
magneto-caloric effect.
The magnetic moment per unit volume is called the "intensity of magnetisation" I.
Experiments show that the intensity of magnetisation I produced by a magnetic field H in
a substance (paramagnetic solid) at temperature T (Kelvin) is proportional to H / T . So,
I ∝ H /T
or I = C H /T
where C is a constant and known as Curie's constant. For 1 mole of substance, the
CV H
molar intensity of magnetisation will be, M = I V = ...(1)
T
where V is the molar volume (volume of 1 mole).
3.35.1 Expression for the Adiabatic Cooling

Let 1 mole of a substance (paramagnetic solid) be placed in a magnetising field H. The
thermodynamic behaviour of a system is expressed in terms of the variable p, V , S and T.
Here (− H) may be taken to play a role similar to that of p, and M that ov V [If p
increases then V decreases, similarly if H increases (− H decreases) M also increases].
Hence, from Maxwell's third thermodynamical relation,
 ∂ T  ∂ V
  = 
 ∂ P S  ∂ S  p
In terms of H and M, it can written as,

∂T  ∂ M
  =–  [If p → − H and V → M]
 ∂ H S  ∂ S H
 ∂ M  ∂ M
  T  
∂T  ∂T H  ∂T  H
or   =− =−
 ∂ H S  ∂ S  ∂ S
  T  
 ∂ T H  ∂ ΤH
166
 ∂ M
T  
 ∂T H
=− [Q TdS = dQ]
 ∂ Q
 
∂ T H
 ∂ M
−T  
∂T  ∂T  H
or   =
 ∂ H S CH
 ∂ Q
where, CH =   is the specific heat of the substance under constant magnetic
∂ TH
field. Thus, for an adiabatic change in the magnetic field (S constant) we may write the
above equation as,
T  ∂ M
dT =−   d H ...(2)
CH  ∂ T 
H
If Ti and T f be the initial and final temperatures of the substance corresponding to the
initial and final magnetic field H1 and H2 , then
Tf H2
T  ∂ M
∫ dT =−
CH ∫  ∂ T  H d H
Ti H1
Using equation (1) it becomes,

H2
T ∂  C V H
T f − Ti = −
CH ∫ ∂T

 T H
 d H
H1
H2
T  C V
=− − 
CH  T 2  ∫ H d H [Q C and V are constant w.r.t., T]
H1
H2
CV CV
∆T =
T CH ∫ Hd H=
2 T CH
(H22 − H12)
H1
Let the field be reduced from a value H to zero i.e., H1 = H and H2 = 0, then the
change in temperature is given by,
−CV
∆ T= . H2
2 CH T
This expression shows that if the field is adiabatically reduced, the temperature of
the substance falls (negative sign).
CV is the Curie constant per mole. If 1 gm of the substance is taken, then CV = Curie
constant per gm = k
167
k H2
∴ ∆T =−
2 CH T
From this expression, we have that if initial field is large and initial temperature is low, then
the drop in temperature will be larger.
3.36 Production of Very Low Temperatures

A magnetic method of cooling was proposed by " Gialeque" in 1933 to produce very low
temperature, known as "adiabatic demagnetisation".
3.36.1 Principle
When a paramagnetic salt is first magnetised by applying a magnetic field, its molecular
dipoles are aligned in the direction of the field. The work is done on the substance
which raises its temperature. When the magnetised salt is demagnetised adiabatically,
the necessary energy for the work is taken from the substance and therefore the temperature
falls. This phenomenon is known as " magneto calorie effect.
A paramegnetic salt (like saft iron) which gets highly magnetised so long as the field is
applied but gets demagnetised immediately the field is switched off(i.e. salt whose
susceptibility is very high and retentivity is very low) is suitable for it .
The Experimental arrangement for adiabatic demagnetisation is shown in fig. 3.18.
The salt A is placed in chamber R which is To Pump

immersed in the helium bath (Dewar flask Liquid
D 1) for isothermal magnetisation R is filled Helium
with helium gas to provide thermal contact
Liquid
with liquid helium bath. The temperature of Radiation
Nitrogen
chamber R lies between 1.2 K to 1.5 K. Shield
After magnetisation in a field of about Magnet
10,000 oersted, R is evacuated using

A
diffusion pump, so that the salt is thermally
N S
isolated. Chamber R is surrounded by
Dewar flasks D2 containing liquid hydrogen R
(or nitrogen). The entire assembly is placed

D1
in between the pole pieces N and S of a Exchange
D2 Measuring
Gas Salt
powerful electromagnet. Coils
Dewar
When the current in the electromagnet is Flasks
switched on, the magnetic field of the order
Fig. 3.18
104 oersted is applied to specimen and it
gets highly magnetised. The heat produced during the process is conducted away by
168
helium gas in R to liquid helium in D1. The helium gas in R is now pumped out by
diffusion pump and the cold and highly magnetised salt is now isolated from D1 and
D2 . The current in electromagnet is now switched off to reduce magnetic field to zero.
The salt gets instantaneously demagnetised adiabatically and its temperature falls.
3.36.2 Measurement of Temperature

The low temperature thus produced is measured through the solenoid coil C C arranged
co-axially around chamber R. The self inductance of the coil C C is measured with the
help of an alternating current bridge immediately before and after the experiment. The
self inductance is found to depend on the susceptibility of the salt contained in R. As
curie law is obeyed at these low temperatures, the temperature T of salt can be obtained
on curie or magnetic scale.
For susceptibility X being inversely proportional to absolute temperature T (Curie law

X = C / T ) if X and X′ be the susceptibilities of the specimen salt at the initial and final
temperatures Ti and T f then
X
Tf = Ti
X′
And expression for T f − Ti = ∆ T can be obtained as
2 2
k (B f − Bi )
∆ T = T f − Ti =
2 CBT
C  ∂ Q
Where k = = Curie's constant per unit mass, CB =   = specific heat of the salt
m ∂ T
under constant magnetic field, Bi = initial magnetic field for magnetisation and B f = final
magnetic field.
when the field is switched off i.e.B f = 0, then
k B2
i
∆T =−
2 CBT
–ive sign shows that temperature falls if magnetic field is adiabatically reduced to zero.
169
Problem 1: A gas occupying 1 litre at 80 cm pressure is expanded adiabatically to

1190 c.c. if the pressure falls to 60cm in the process, deduce the value of γ.

γ
 p  V 
p1V1γ = p2V2 γ or  1  =  2 
 p2   V1 
Given that, p 1 = 80 cm, p2 = 60 cm, V1 = 1 litre = 1000 c. c. and V2 = 1190 c. c.
γ
 80  1190 
  = 
 60  1000 
 80  1190 
log   = γ log  
 60  1000 
log 80 − log 60 1 . 9031 − 1 . 7782 0 . 1249
or γ= = = = 1.65
log 1190 − log 1000 3 . 0755 − 3 . 000 0 . 0755
Problem 2: A certain mass of gas at N.T.P. is expanded to three times its volume under
adiabatic conditions. Calculate the resulting temperature and pressure. Given: γ for gas = 1.4 .

p1V1γ = p2V2 γ
at N.T.P. means p 1 = 1 atmosphere,
T = 0 º C = 273 K, V1 = V , V2 = 3V and γ = 1 . 4
 1   3 V 1 . 4
Putting the values, we get   = 
 p2   V 
or p2 = (1 / 3)1 .4 = 0.215 atmosphere
Also, we have a relation, T1V1γ − 1 = T2V2 γ − 1

γ −1
 T1   V2 
or   = 
 T2   V1 
. −1
 273   3 V  14
 T2   V 
or T2 = 273(1 / 3)0 .4 = 176K = – 97ºC
170
Problem 3: A quantity of air at 27º C and atmospheric pressure is suddenly compressed

to half of its original volume. Find the final pressure and temperature.
Solution: For sudden compression the process is adiabatic. For an adiabatic process,
γ
p1 V 
p1V1γ = p2V2 γ or =  2
p2  V1 
Here, p 1 = 1 atmosphere, V1 = V , V2 = V / 2 and γ = 1. 4

14
.
1 V 
Putting the values,we get = 
p2  2V 
or p 2 = (2)14
. = 2.636 atmosphere
Also, we have a relation, T1V1γ − 1 = T2V2 γ − 1
Here, T1 = 27º C = 300 K, V1 = V , V2 = V / 2

14
. −1 0 .4
300  V   1
=  = 
T2  2V   2
T2 = 300(2)0 .4 = 395.9 K = 122.9º C
Problem 4: A motor car tyre has a pressure of 2 atmospheres at the room temperature of
27º C. If the tyre suddenly bursts, find the resulting temperature.
Solution: It is an adiabatic process. for an adiabatic process we have,

γ− 1 γ
p1γ − 1 p γ− 1  p1  T 
= 2 γ or   =  1
T1γ T2  p2   T2 
Here, p1 = 2 atmospheres, T1 = 27º C = 300 K, p2 = 1 atmospheres, and γ = 1 . 4
1.4 − 1 1.4
 2  300 
 1  T2 
1.4
 300 
(2)0 .4 =  
 T2 
or 0 .4 log 2 = 1.4 [log 300 − log T2 ]
0 .4 × 0 .3 010 = 1.4 [2 .4771 − log T2 ]
0 .1204 = 3 .468 − 1.4 log T2
1.4 log T2 = 3 .348
3 .348
or log T2 = = 2 .391
1.4
or T2 = 0 .2460 × 103 = 246 K = − 273 + 246 = – 27º C
171
Problem 5: A monoatomic ideal gas, initially at 27º C is suddenly compressed to one

tenth of its original volume. Calculate its temperature after compression. If the gas is
diatomic then what happens?

T1V1γ − 1 = T2V2 γ − 1
γ −1
 T1   V2 
or   = 
 T2   V1 
Here, T1 = 27ºC = 300 K, V1 = V , V2 = V / 10 and for monoatomic gas, γ = 5 / 3

5 2
−1
 300   V  3  1
∴   =  =  3
 T2   V . 10  10 
T2 = 300(10)2 /3
or log T2 = log 300 + (2 / 3) log 10 = 2 .4771 + 0 .66 × 1.00 = 3 .1371

or T2 = 1371 K = 1371 − 273 = 1098º C
If gas is diatomic, then γ = 1.4

∴ T2 = 300 (10)1.4–1 = 300 (10)0 .4
or log T2 = log 300 + 0 .4 log 10 = 2 .4771 + 0 .4 × 1.00 = 2 .8771

or T2 = 753 .6 K = 753 .6 − 273 = 480.6º C
Problem 6: A quantity of air ( γ = 1 . 4 ) at 27º C is compressed (i) slowly and (ii)

suddenly to one third of its volume. Find the change in temperature in each case.
Solution: (i) When the air is compressed slowly the heat generated conducts away to the
surroundings. Thus, it is an isothermal process. It means that temperature of the system
throughout remains constant i.e., there is no change in temperature.
(ii) When the air is compressed suddenly, the process is adiabatic. Hence,
T1V1γ − 1 = T2V2 γ − 1
Here, T1 = 27º C = 300 K, V1 = V , V2 = V / 3 and γ = 1.4

1 .4 − 1 0 .4
 300   V   1
  =  = 
 T2   3 V   3
or T2 = 300(3)0 .4 = 465 .5 K = 465 .5 – 273 = 192.5 ºC
So, change in temperature = T2 − T1 = 192 .5 ºC − 27 ºC = 165 .5 º C
172
Problem 7: Find the efficiency of the Carnot's engine working between the steam point
and the ice point.
[Meerut 2003]
Solution: The efficiency of Carnot engine,
T
η =1 − 2
T1
Given that, T2 = 273 + 0 = 273 K and T1 = 273 + 100 = 373 K
273 100
∴ η =1 − =
373 373
100 × 100
Efficiency in %, η= = 26 . 81 %
373
Problem 8: A Carnot engine whose temperature of the source is 400 K takes 200
calories of heat at this temperature and given out 150 calories to the sink. What is the
temperature of the sink. Also calculate the efficiency of the engine.
Solution: For a Carnot engine,

Q1 T1
=
Q2 T2
Here, Q1 = 200 cal, Q2 = 150 cal, T1 = 400 K
200 400
=
150 T2
400 × 150
or T2 == 300 K
200
Τ
Efficiency of a Carnot engine, η = 1 − 2
Τ1
300 1
1− = = 25%
400 4
Problem 9: A locomotive generates steam at a temperature of 190º C and rejects the

waste steam in the air (30º C). Calculate its thermal efficiency.
Solution: The efficiency of engine is given by,

Τ
η =1 − 2
Τ1
Here, T2 = 30 º C = 273 + 30 = 303 K, T1 = 190 º C = 273 + 190 = 463 K
303 463 − 303 160
η =1 − = =
463 463 463
= 0 .346 = 34 . 6%
173
Problem 10: One of the most efficient engines ever developed operates between 2100 K
and 700 K. Its actual efficiency is 40%. What percentage of its maximum possible
efficiency is this?
Solution: The maximum possible efficiency of an engine working between 2100 K and
700 K,
Τ 700 1400
η =1 − 2 =1 − =
Τ1 2100 2100
= 2 / 3 = 0. 66 = 66%
But given that the actual efficiency of this engine is 40%
actual efficiency
∴ % fraction of max. efficiency = × 100
maximum efficiency
40
= × 100 = 60 . 6%
66
Problem 11: Find the efficiency of a Carnot's engine working between 72º C and 187º C.
Solution: The efficiency of a Carnot engine is given by,

Τ
η =1 − 2
Τ1
Here, T2 = 72 ºC = 345 K, T1 = 187ºC = 460 K

345 115 1
∴ η =1 − = =
460 460 4
% Efficiency = (1 / 4) × 100 = 25%
Problem 12: A Carnot's engine is working between two reservoirs at temperature of

450 K and 350 K. If the engine receives 1000 cal. of heat from the source in each
cycle, calculate the amount of heat given out to the sink in each cycle. Calculate the
efficiency of the engine and the work done by the engine in each cycle.
Solution: For a Carnot engine,

Q1 T
= 1
Q 2 T2
Here, T1 = 450 K, T2 = 350 K and Q 1 = 1000 cal.

1000 450
∴ =
Q2 350
350 × 1000
or Q2 = = 777.77 cal
450
174
The efficiency of a Carnot engine,

Τ
η =1 − 2
Τ1
350 100
∴ η =1 − = = 0 . 222
450 450
% efficiency = 22. 2%
Work done in each cycle Q 1 − Q 2 = 1000 − 777. 77 = 222 .23 cal
= 222 . 23 × 4 .18 = 928.8 Joule [Q 1 cal = 4.18 Joule]
Problem 13: A Carnot engine works between the temperature 227º C and 27º C and
develops 100 H.P. Calculate (i) the heat supplied to the engine (ii) the heat rejected by
the engine.
Solution: The efficiency of an engine is given by,

Τ
η =1 − 2
Τ1
Here, T2 = 27º C = 273 + 27 = 300 K

T1 = 227º C = 273 + 227 = 500 K
300 200
∴ η =1 − = = 0 .4 = 40%
500 500
Now, given that the engine develops 100 H.P., it means work output = 100 H.P. 100
H.P. = 100 × 746 watt = 74600 Joule/sec
Also, we have 1cal = 4.2 Joule
74600
∴ 74600 Joule / sec = cal / sec
4 .2
work output (W)
(i) Also we have, η=
heat supplied to the engine (Q 1)
∴ Heat supplied to the engine,

W 74600
Q1 = = = 4 . 4 × 10 4 cal/sec =44000 cal/sec
η 4 .2 × 0.4
(ii) Again, we have the efficiency of Carnot engine,

Q2
η =1 −
Q1
Q2
or 0 .4 = 1 − or Q 2 = 0 . 6 × 4 .4 × 104
4 .4 × 104
= 2 .66 × 10 4 cal / sec = 26600 cal/sec
175
Problem 14: A reversible engine works between two temperatures whose difference is
100º C. If it absorbs 796 Joules of heat from the source and give 596 Joule to the sink,
calculate the temperatures of the source and the sink.
Solution: For a reversible engine we have,

Q1 T
= 1
Q 2 T2
Here, Q 1 = 796 Joule, Q 2 = 596 Joule

Also given that, T1 − T2 = 100 ºC ...(1)
where T1, T2 is temperature of the source and sink respectively.

796 T1
=
596 T2
or 796 T2 = 596 T1 = 596 (100 + T2 ) [T1 = 100 + T2 , from eq. (1)]

or 796 T2 = 596 × 100 + 596 T2
200 T2 = 596 × 100
596 × 100
T2 = = 298 K =25°C
200
and T1 = 100 + T2 = 398 K =125°C
Problem 15: A Carnot engine works between 100º C and 0º C. If the work done per cycle is
1200 kgm2 / s2 , then calculate the heat taken in from the source ( J = 4.18 joule/cal ).
Solution: For a Carnot engine the efficiency of the engine,

T
η =1 − 2
T1
Here, T1 = 0 º C = 273 K, T2 = 100 º C = 373 K

273 100
∴ η =1 − =
373 373
work done per cycle
Also, we have η=
input heat (Q 1)
Here, work done per cycle = 1200 kg- m 2 / s2

100 1200
∴ =
373 Q1
1200 × 373
or Q1 = = 4476 Joule
100
= 1070.8 cal (∴1cal = 4.18 Joule)
176
Problem 16: A Carnot engine working between an unknown temperature T and ice point
gives an efficiency of 0.68. Deduce the value of T.
Solution: The efficiency of Carnot engine,

Τ
η=1 − 2
Τ1
Here, η = 0 . 68, Τ2 = 0ºC = 273 K

273
∴ 0 . 68 = 1 −
T1
or (273 / T1) = 1 − 0 . 68 = 0 . 32
or T1 = (273 / 0 . 32) =853.1 K= 853 . 1 − 273 = 580.1º C
Problem 17: A reversible engine takes in heat from a reservoir of heat at 527º C and gives
out heat to the sink at 127º C. How many calories/sec must it take from the reservoir in
order to produce useful mechanical work at the rate of 750 watt?
Solution: The efficiency of reversible engine,

T
η = 1− 2
T1
Here, T2 = 127ºC = 273 + 127 = 400 K

T1 = 527ºC = 273 + 527 = 800 K
400 400 1
∴ η =1 − = =
800 800 2
The useful mechanical work produced, W = 750 watt = 750 Joule / sec
= (750 / 4 . 2) = 178. 57 cal / sec.
[Q 1 watt = 1 Joule/sec, 1 cal = 4.2 Joule]
work done W
Also, we have η= =
heat taken from the source Q 1
1 178 . 57
Putting the values, we get =
2 Q1
or Q 1 = 178 . 57 × 2 = 357 . 14 cal / sec
Problem 18: The efficiency of a Carnot engine is 1/6 . On reducing the temperatrue of
the sink by 65ºC, the efficiency becomes 1/3, find the initial and final temperatures
between which the cycle is working.
[Meerut 2005B, 05, 02, 01]

Solution: The efficiency of a Carnot cycle is,
177
T
η =1 − 2
T1
Given that, η1 =1 /6
η 2 = 1 / 3 If T2′ = T2 − 65
1 T T 1 5
∴ = 1 − 2 or 2 = 1 − = ...(1)
6 T1 T1 6 6
1 T′ (T − 65) T − 65 1 2
and =1 − 2 =1 − 2 or 2 =1 − =
3 T1 T1 T1 3 3
T2 65 2
or − = ...(2)
T1 T1 3
Using equation (1) we can write,

5 65 2 65 5 2 1
or − = or = − =
6 T1 3 T1 6 3 6
or T1 = 65 × 6 = 390 K = 390 − 273 = 117º C

From equation (1),
5 390 × 5
T2 = T1 = = 325 K = 325 − 273 = 52º C
6 6
Problem 19: A refrigerator is to extract heat from a freezing compartment at − 13º C

and deliver it to outer atmosphere at 27º C. Compute its coefficient of performance.
Solution: The Coefficient of performance of a refrigerator,

T2
K=
T1 − T2
Here, T1 = 27ºC = 300 K, T2 = − 13ºC = 260 K

260 260
∴ K= = = 6.5
300 − 260 40
Problem 20: A Carnot engine working as a refrigerator between 260 K and 300 K receives
500 cal of heat from the reservoir at the lower temperature. Calculate the amount of heat
rejected to the reservoir at the higher temperature. Also calculate the amount of work done
in each cycle to operate the refrigerator.
Solution: For a Carnot refrigerator,

Q1 T
= 1
Q2 T2
Given that, T1 = 300 K, T2 = 260 K and Q 2 = 500 cal

178
Q1 300
= or Q 1 = 576 . 92 cal
500 260
The work done, W = Q 1 − Q 2 = 76 . 92 cal

76 . 92 × 4 . 2 =323.08 Joule.
Problem 21: A refrigerator works between − 10º C and 27º C, while the other between
− 20º C and 17º C, both removing 2000 Joule heat from the freezer. Which one is
better through your calculations ?
Solution: A refrigerator, which runs with less energy input will be the best.
For a refrigerator, the energy (work done) W must be supplied to remove heat Q 2 from
the freezer at temperature T2 which is given by,
 Q1 
W = Q1 − Q 2 = Q 2  − 1
Q 
 2 
T   T − T2 
W = Q 2  1 − 1 = Q 2  1 
T
 2   T2 
where T1 is the temperature of the outer atmosphere for the first refrigerator.
T1 = 27 + 273 = 300 K, T2 = − 10 + 273 = 263 K
 300 − 263 
∴ W1 = 2000   = 281 Joule
 263 
For the second refrigerator,

T1 = 17 + 273 = 290 K, T2 = − 20 + 273 = 253 K
 290 − 253 
∴ W2 = 2000   = 292 Joule
 253 
Since, the first refrigerator runs at less energy input, hence it will be better.
Problem 22: Calculate the change in entropy when 10 gms of ice at 0º C is converted
into water at the same temperature. The latent heat is 80 cal/kg.
[Meerut 2012, 01]
Solution: We have that the change in entropy,
∆S = Q / T
Heat absorbed by 10 gm ice at 0ºC when it is converted into water at 0ºC
Q = mL = 10 × 80 = 800 cal (L is the latent theat of ice and m is the mass of ice)
So, Q = 800 cal, T = 0ºC = 273 K
∴ ∆S = 800 / 273 = 2.93 cal/K
179
Problem 23: Calculate the change in entropy when 5 kg of water at 100º C is

converted into steam at the same temperature
Solution: The change in entropy,

∆S = Q / T
Heat absorbed by 5 kg of water at 100ºC when it is converted into steam at 100°C
Q = mL = 5000 × 540
where m is the mass of water in gms and L is latent heat of steam.
∴ Q = 2700000 cal
Given that, T = 100ºC= 373 K
∴ The change in entropy, ∆S = Q / T
2700000
= = 7238 cal/K
373
Problem 24: Find the increase in entropy when 1 kg of ice at 0º C is converted into steam
at 100°C. Specific heat of water = 1.0 kcal/kg-K, latent heat of ice
= 3 . 4 × 105joule/kg, latent heat of steam = 22 . 68 × 105 joule/kg, J = 4 . 2 Joule/cal.
Solution: The increase in entropy when 1 kg of ice is melted into water at 0ºC (273 K) is,
5
Q mL 1 × 3 . 4 × 10
∆S 1 = = =
T T 273 K
= 1 . 245 × 103 Joule/K = 0. 296 × 103 cal/K
The increase in entropy when 1kg of water is heated from 0ºC (273 K) to 100ºC (373 K),
T2 T2 373
dQ m×C ∆T dT
∆S2
∫ T
=
∫ T
=1 ×1
∫ T
T1 T1 273
= 1 × log e (373 / 273) = 2 . 3026 [log 373 − log 273]

= 2.3026 × [2 .5717 − 2 .4362] = 2 . 3026 × 0 .1355
= 0 . 312 kcal/K = 0 . 312 × 103 cal/K
Now, the increase in entropy when 1 kg water at 100ºC is converted into steam at
100ºC (373 K),
5
Q m L 1 × 22 . 68 × 10
∆S3 = = =
T T 373
= 6 . 08 × 103 Joule/K = 1 . 448 × 103 cal/K
Hence, the total increase in entropy ∆S 1 + ∆S2 + ∆S3
= (0 . 296 + 0 . 312 + 1 . 448) × 103
= 2 .056 × 10 3 cal/K.
180
Problem 25: Calculate the change in entropy when 40 gm of water 50°C is mixed with
80 gm of water 20º C. Assume that the specific heat of water is 1 cal/gm-K at all
temperatures.
[Meerut 2002]
Solution: Let t be the temperature of mixture, then
Heat Given by 40 gm water at 50 º C = 40 × 1 × (50 − t) [ Q Q = mC∆t]
Similarly, heat taken by 80 gm water at 20ºC = 80 × 1 × (t − 20)
Q Heat given = Heat taken
∴ 40(50 − t) = 80 (t – 20)
or 2000 – 40 t = 80 t – 1600
or 120 t = 3600
t = 30 ° C
Now, change in entropy of 40 gm water in cooling from 50ºC (323 K) to 30ºC (303 K),
T2 303 303
dQ m×C ∆T 40 × 1 × dT
∆ S1 =
∫ T ∫ T
=
∫ T
T1 323 323
303  303 
= 40 [log e T ] = 4 0 × 2 . 3026 log 10 323 
323
= 40 × 2 . 3026 × [log 303 − log 323]

= 921
. × [2 . 4814 − 2 .5092]
= − 92 .1 × 0 .0278 = –2 .56 cal/K
Similarly, the change in entropy of 80 gm water in heating from 20º C (293 K) to 30º C
(303 K),
T2 303 303
dQ m×C ×∆T dT
∆ S2 =
∫ T
=
∫ T
= 80 × 1
∫ T
T1 293 293
303
= 8 0 [log e T ]293 = 8 0 × 2 .3026 × [log10 303 − log10 293]
= 184 .2 × [2 .4814 − 2 .4669]
= 184 .2 × 0.0145 = 2.67 cal/K
The net increase in entropy of the system

∆S1 + ∆S2 = – 2 .56 + 2 .67 = 0.11 cal/K
Problem 26: Calculate the change in temperature of boiling water when the pressure
is increased by 2.712 mm of Hg. The normal boiling point of water at atmospheric
pressure is 100º C. Given that, latent heat of steam 537 cal/gm and specific volume of
steam = 1674 cm3
181
Solution: The change in temperature of boiling water with change in pressure is given
by Clausius Clapeyron equation,
d p L
=
d T T (V2 − V1)
Givethat, L = 537 cal / gm = 537 × 4 . 2 × 107 erg / gm, T = 100 º C = 373 K,
V1 = 1 . 000 cm 3 , V2 = 1674 cm 3 and dp = 2 . 712 × 13 . 6 × 980 dyne / cm 2

2.712 × 13.6 × 980 537 × 4. 2 × 107
=
dT 373 × (1674 − 1)
2.712 × 13.6 × 980 × 373 × 1673
or dT =
537 × 4. 2 × 107
dT = 1 K = 1°C
Problem 27: Calculate the boiling point of benzene under a pressure of 80 cm of mercury.
The normal boiling point is 80°C. Latent heat of vaporization is 380 Joules/gm, density of
vapour at the boiling point is 4 gm/litre and that of the liquid 0.9 gm / cm3 .
Solution: The change in boiling point of a substance with change in pressure is given
dp L
=
d T T (V2 − V1)
Given that, L = 380 Joule / gm = 380 × 107 ergs / gm
dp = 80 − 76 = 4 cm of Hg = 4 × 13.6 × 980 dyne / cm 2
T = 80 °C =353 K
. cm 3
V1 = (1 / 0.9) = 111
and V2 = (1000 / 4) = 250 cm 3

4 × 13.6 × 980 380 × 107
=
dT 353 (250 − 111
. )
4 × 13.6 × 980 × 353 × 248.89
dT =
380 × 107
= 1.233 K = 1.223 °C
Hence, the boiling point of benzene at a pressure of 80 cm of mercury will be
= 80 + 1.233 = 81.233 °C
182
Problem 28: If sulphur has specific gravity of 2.05 just before and 1.95 just after
melting, the melting point being 115 °C and the latent heat of fusion = 9.3 cal/gm, find
the change in the melting point per atmosphere change of pressure.
Solution: The change in the melting point of a substance with change in pressure is
given by Clausius Clapeyron equation,
dp L
=
d T T (V2 − V1)
Here, L = 9.3 cal /gm = 9. 3 × 4 .2 × 107 erg /gm,

T = 115 °C =273+115 =388K
The specific volume of solid sulphur,
V1 = 1 / 2.05 = 0.4878 cm 3
and the specific volume of liquid sulphur,
. = 0 .5128 cm 3
V2 = 1 / 195
and dp = 1atmosphere = 1.013 × 106 dyne /cm 2

1013
. × 106 9. 3 × 4. 2 × 10 7
=
dT 388 (0 .5128 − 0 .4878)
388 × 0 .25 × 1.013 × 106

or dT = = 0.02516 K = 0.02516 °C
9 .3 × 4 .2 × 107
Problem 29: Calculate the change in the melting point of ice when it is subjected to a
pressure of 100 atmosphere. Given that, density of ice = 0.917 gm / cm3 and Latent
heat of ice = 336 Joule /gm
Solution: The change in the melting point of ice with change in pressure is given by

dp L
=
d T T (V2 − V1)
Given that, L = 336 Joule /gm = 336 × 107 ergs /gm
T = 0 °C =273 K
dp = (100 − 1) = 99 atmosphere
= 99 × 76 × 13.6 × 980 dyne/cm 2
V1 = (1 / 0.917) cm 3 = 109
. cm 3 and V2 = 1000
. cm 3
183
99 × 76 × 13.6 × 980 336 × 107

=
dT 273 (100
. − 109
. )
99 × 76 × 13.6 × 980 × 273 × 0.09
or dT =
336 × 107
= − 0.7332 K
Hence, the decrease in the melting point of ice with a pressure of 100 atmosphere is
0.7332 K = 0.7332 °C
Problem 30: Calculate the pressure required to lower the melting point of ice by 1 °C
(to make ice melt at – 1 °C ). Given that, L=79.6 cal/gm, specific volume of water at
0 °C =1.000 cm3 and specific volume of ice at 0 °C = 1.091 cm3 .
[Meerut 2001]
Solution: The change in pressure with change in temperature is given by Clausius
Clapeyron equation,
dp L
=
dT T (V2 − V1)
Given that, L = 79 .6 cal /gm = 79 .6 × 4 .2 × 107 ergs /gm ,
T = 0 °C =273 K, V1 = 1.091 cm 3 ,
V2 = 1.000 cm 3 and dT = − 1K

dp 79 .6 × 4 .2 × 107
=
− 1 273 × (1.000 − 1.091)
79 .6 × 4 .2 × 107
or dp= = 13 .45 × 107 dyne /cm 2
273 × 0 .091
13 .45 × 107
=
76 × 13 .6 × 980
(Q1atmosphere = 76 × 13.6 × 980 dyne / cm 2 )
dp =132.85 atmospheres.
So, pressure required = 132 .85 + 1 = 133.85 atmospheres
Thus, it means that water will melt at − 1 °C under a pressure of 133.85 atmospheres.
184
Problem 31: Water boils at a temperature of 101 °C at a pressure of 787 mm of Hg. 1

gm of water occupies 1601 cm3 on evaporation. Calculate the latent heat of steam
J = 4 .2 × 107 ergs / cal.
Solution: According to Clausius Clapeyron equation,

dp L
=
d T T (V2 − V1)
Given that, dp = (787 − 760) mm of Hg = 27 mm of Hg

= 2 .7 cm of Hg = 2 .7 × 13 .6 × 980 dyne / cm 2
dT = (101 − 100) °C =1 °C =1K

T = 100 °C =373 K
V2 = 1601 cm 3 and V1 = 1 cm 3

2 .7 × 13 .6 × 980 L
=
1 373 (1601 − 1)
or L = 2 .7 × 13 .6 × 980 × 373 × 1600 ergs /gm

2 .7 × 13 . 6 × 980 × 373 × 1600
= Joule / gm
107
2 .7 × 13 .6 × 980 × 373 × 1600
= cal / gm
4 .2 × 107
= 511.33 cal/gm
Problem 32: When lead is melted at atmospheric pressure, the melting point is 600
K. What is the melting point at a pressure of 100 atmosphere ? The density decreases
from 11.01 gm / cm 3 to 10.65 gm/cm3 and the latent heat of fusion is 24.5 Joule/gm.
Solution: The change in melting point of a substance with change in pressure is given

dp L
=
d T T (V2 − V1)
Given that,dp = (100 − 1) = 99 atmosphere = 99 × 76 × 13 .6 × 980 dyne / cm 2 ,
T = 600 K
V1 = (1 / 11.01) cm 3 = 0 .091 cm 3 , V2 = (1 / 10 .65) cm 3 = 0 .094 cm 3
185
and L = 24 .5 Joule / gm = 24 .5 × 10 7 ergs / gm
99 × 76 × 13 .6 × 980 24 .5 × 107
Putting all the values, we get =
dT 600 (0 .094 − 0.091)
99 × 76 × 13 .6 × 980 × 600 × 0 . 003

or dT = = 0 .7367 K
24 .5 × 107
So, the melting point of lead at 100 atmosphere will be,
600 + 0 .7367 = 600 .7367 K
Problem 33: Calculate under what pressure water will boil at 120 °C, if the change in
specific volume of 1 gm of water, converted into steam is 1676 cm3 . Given that, Latent
heat of steam = 540 cal /gm , J = 4 .2 × 107ergs/cal and 1 atmosphere pressure = 106
dyne/cm2 .
Solution: The change in pressure of a substance with change in temperature is given by

dp L
=
d T T (V2 − V1)
Given that, L = 540 cal /gm = 540 × 4 .2 × 107 ergs /gm
T = 100 °C =373 K
dT = (120 − 100) °C =(393 – 373) K =20 K
(V2 − V1) = 1676 cm 3
d p 540 × 4 .2 × 107
=
20 373 × 1676
20 × 540 × 4 .2 × 107
or d p= dynes /cm 2
373 × 1676
20 × 540 × 4 .2 × 107
or d p= atmosphere
373 × 1676 × 106
= 0 .7255 atmosphere
Pressure required =1+0.7255 =1.7255 atmosphere
186
Problem 34: Calculate the specific gravity of solid sulphur. Given that, melting point of
sulphur = 115 °C, latent heat of fusion for sulphur = 9.3 cal / gm, volume of 1 gm of
liquid sulphur = 0.513 cc, rate of change of melting point with pressure = 0.025 °C per
atmosphere, 1 atmospheric pressure = 106 dyne / cm2 and J = 4.18 × 107 erg / cal.
Solution: For melting of a solid substance, the Clausius Clapeyron equation is,
dp L
=
d T T (V2 − V1)
d p 1atmosphere 106 dyne / cm 2

Given that, = =
dT 0 .025 °C 0 .025 K
L = 9 .3 = 9 .3 × 4 .18 × 107 ergs / cal
T = 115 °C =273 + 115 = 388 K
Putting all the values in equation, we get
106 . × 107
9. 3 × 418
=
0.025 388(V2 – V1)
9. 3 × 4.18 × 0.025 × 107

or V2 – V1 = = 0.025 cm 3 /gm
6
388 × 10
Also given that the volume of liquid sulphur, V2 = 0 .513 c. c. / gm
∴ V1 = V2 – 0 .025 = (0 .513 – 0 .025) = 0 .488 c.c./gm
1 1
Thus, the specific gravity of solid sulphur = = = 2 .05 gm/c.c.
V1 0.488
Problem 35: The specific heat of a certain liquid is given by s1 = 0.53 + 0.0004 t and
its latent heat of vaporisation is given by, L = 95 − 0.05 t – 0.0006 t 2 where t is
temperature in °C. Calculate the specific heat of saturated vapour at 50 °C.
Solution: The specific heat of saturated vapour (s ) is given by Clausius second latent
2
dL L
heat equation, s2 = s1 + −
dT T
Given that, s1 = 0.53 + 0.0004 t, so s1 at 50 °C =0 .53+0 .0004 × 50 = 0 .55 cal / gm °C)
and L = 95 – 0.05 t – 0.0006 t2

so, L at 50 ° C =95 − 0 .05 ×50 −0 .0006 ×50 ×50 = 95 − 2 . 5 − 1. 5 = 91 cal /gm
187
dL dL
Then, = = – 0 .05 − 0 .0006 × 2 t
dT d t
[Q the change in °C = the change in K]
= – 0 .05 − 0 .0006 × 2 × 50 = − 0.05 − 0.06
= – 0 .11cal / gm K and T = 50 + 273 = 323 K
91
Putting all the values, we get s2 = 0 .55 + (− 0 .11) − = 0 .55 − 0 .11 − 0 .282
323
= 0 .158 cal / gm K
The specific heat of saturated vapour of the given liquid is positive.
Problem 36: 200 gm of saturated steam at 100 °C is compressed under the condition of
saturation till its temperature becomes 101 °C. How much heat will be added or
withdrawn in the process if the latent heat of steam varies with temperature according
to relation L t = 599.4 − 0.6t.
Solution: The specific heat of saturated steam is given by Clausius second latent heat
equation,
dL L
s2 = s1 + −
dT T
Here, s1 = 1.0 cal / gm °C (water at 100°C)

Lt = 599 .4 − 0 .6 t
The latent heat of steam at 100 °C is,

L = 599 .4 − 0 .6 × 100 = 539 .4 cal / gm
T = 100 °C =373 K
dL dL
Also, = = − 0 .6 [Q the change in °C = the change in K]
dT d t

539 .4
s2 = 1 + (− 0 .6) − = 1 − 0 .6 − 1.446 = − 1.05
373
Now, in the compression of 200 gm of saturated steam under condition of saturation
from 100 °C to 101 °C, the amount of heat added or withdrawn will be,
Q = m × s2 × ∆ t = 200 × (− 1.05) × (101 − 100)
= 200 × (− 1.05) × 1 = − 210 Calories
The negative sign indicates that 210 calories heat will be withdrawn.
188
Problem 37: Calculate the specific heat of saturated vapour (steam) at 100 °C, if the
latent heat L varies with temperature T according to the equation L = 800 − 0.705 T ,
and the specific heat of water at 100 °C is 1.0 cal/(g- °C).
[Meerut 2003, 02]

Solution: The specific heat of saturated vapour (s2 ) is given by the second latent heat
equation,
dL L
s2 = s1 + − ...(1)
dT T
Given that L = 800 − 0 .705 T at T = 100 °C =373 K
L=800 – 0 .705 × 373 = 537
and dL / dT = − 0 .705, s1 = 1.0 - °C

537
s2 = 1 + (− 0 .705) −
373
= 1 − 0 .705 − 1.44
s2 = − 1.145 cal/gm-°C
Hence, the specific heat of saturated steam is – 1.145 cal/gm-°C
189
Exercise
1. Define Macrscopic and Microscopic systems [Meerut 2003]
2. Explain the concept of temperature and thermal equilibrium. State and explain
the Zeroth law of thermodynamics. On the basis of zeroth law define the concept
of temperature. [Meerut 2008, 06, 01]
3. State and explain the Zeroth law of thermodynamics. [Meerut 2001]
4. Explain the concept of temperature on the basis of zeroth law of thermodynamics

[Meerut 2008, 06]
5. Explain thermodynamic system, thermodynamic equilibrium and quasi-static

process. [Meerut 2003]
6. Explain Quasi-static process. [Meerut 2003]
7. Explain p –V Indicator diagram. Determine the work done by a gas using p –V

diagram during (i) isothermal process (ii) adiabatic process [Meerut 2002]
8. If a thermodynamic system is taken from an initial state i to a final state f , then

show that the work done depends upon the path between i and f states.
9. State the first Law of thermodynamics and explain its Physical significance. Also
give its applications. [Meerut 2009, 05, 02, 01]
10. Explain the concept of internal energy of a system.

11. Define Reversible and Irreversible Process. State clearly the conditions necessary
for reversible engine. [Meerut 2003]
12. Describe Carnot's Cycle and Carnot's reversible Heat engine. Also determine its
efficiency. [Meerut 2012, 011, 10, 09B, 09, 07B, 05B, 05, 03, 02, 01]
13. Describe Carnot's reversible heat engine and obtain an expression for its
efficiency from p-V diagram. [Meerut 2004, 03, 02]
14. Describe Carnot's reversible heat engine and find an expression for the network
done by the system in one cycle. [Meerut 2010]
15. State and Prove Carnot's Theorem.

[Meerut 2010, 08B, 08, 07, 06B, 06, 05B, 05, 04, 03, 02, 01]
16. Prove that no engine working between two given temperature can be more efficient
than a reversible engine working between the same two temperatures. [Meerut 2007]
17. State and explain second law of Thermodynamics. Give Kelvin-Planck and
Clausius statement of the law and show their equivalence.
[Meerut 08B, 07B, 05, 04, 02, 01]
18. What is the purpose of second law of thermodynamics ? [Meerut 2004, 02]
190
19. What do you mean by internal combustion engine? Give practical cycles used in
internal combustion engine.
20. What do you understand by the term Entropy? Give its physical significance.
[Meerut 2012, 11, 10, 09B, 08B, 06, 05B, 05, 03, 02, 01]
21. Write short notes on (i) Reversible and irreversible process (ii) Cannot theorem
(iii) Entropy. [Meerut 2003]
22. Deduce an expression for the change of entropy in reversible and irreversible
process. Also describe the principle of increases of entropy.
[Meerut 2012, 11, 10, 09, 06B, 06, 05B, 05, 03, 02, 01]
23. Show that the entropy remains constant in a reversible cycle but increases in
irreversible one. [Meerut 2011, 10, 06B, 06, 03]
24. Derive an expression for the entropy of a perfect gas in terms of its pressure,
volume and specific heat. [Meerut 2006, 05, 04, 02]
25. What is Thermodynamic scale of temperature? Define zero of absolute scale.

[Meerut 2010, 08, 07B, 06B, 05B, 04, 03, 02, 01]
26. Show that Thermodynamic scale is identical with the perfect gas scale.
[Meerut 2009, 07B, 06B]
27. How is Kelvin's scale realised in practice? Explain impossibility of attaining the
absolute zero. Is negative temperature possible on this scale ? Also state third law
of thermodynamics. [Meerut 2010, 08, 06B, 03]
28. What is Kelvin's absolute scale of temperature ? Show that the temperature
measured on the Kelvin's scale agree with those measured on the ideal gas scale.
How is Kelvin's scale realised in practice. [Meerut 2006B, 03, 02]
29. What is Kelvin's scale of temperature ? Discuss in detail whether a negative

temperature is possible on this scale? [Meerut 2010, 08, 06B]
30. Why the zero on absolute scale is considered to be the lowest possible temperature ?
Is a negative temperature possible on this scale ? [Meerut 2003]
31. Explain extensive and intensive variables.

32. Derive Maxwell's Thermodynamic Relations.
[Meerut 2012, 09B, 09, 08, 06B, 06, 05, 04, 03, 02, 00]
33. A liquid is compressed isothermally. How much heat would be transferred?

34. One mole of van der waal's gas suffers reversible isothermal expansion from a
volume V1 to V2 . How much heat has been transferred?
35. A liquid is compressed or expanded adiabatically. How much temperature would
be changed?
36. From the laws of thermodynamics, prove that,
191
∂ U  ∂ p
  = T  −p
 ∂ V T  ∂ T V
Hence, show that the internal energy of an ideal gas is independent of its volume
but is not so for Van der Waal's gas. Also show that for a van der wall's gas
a
U = ∫ CV d T − + U 0
V
where all symbols have their usual meanings
37. State joule's law for a perfect gas. Show that for a Van der Waal's gas, the cooling
due to joule's free expansion is given by [Meerut 2008]
1a
∆T = ∆V
CV V 2
38. What do you understand by Joule Thomson effect? Obtain thermodynamically an

expression for Joule Thomson cooling. Show that it is zero for a perfect gas. Explain
the existance of inversion temperature for a gas obeying Van der Waal's equation.
39. Establish the thermodynamical relation,
 ∂ Q  ∂ V
  = T  = − T Vα
 ∂ p ∂ T p
T
where α is the coefficient of thermal expansion. Hence show that the increases in
pressure, heats a body that expands with rise in temperature and cools the one
that contracts on heating. [Meerut 2007, 06]
40. Using Maxwell's relation, prove that for a homogeneous fluid,

 ∂p  ∂ V
C p − C V = T   
 ∂ T V  ∂ T p
Hence, prove that for a perfect gas C p − C V = R and for a Van der Waal's gas
 2a 
C p − C V = R 1 + 
 R T V [Meerut 2008B, 07B, 03, 02]
41. Using Maxwell's thermodynamic relations, show that the ratio of adiabatic to
isothermal elasticity is equal to C p / C V for all substances. [Meerut 2009, 03, 01]
42. Deduce Clausius Clapeyron latent heat equation

dp L
=
d T T (V2 – V1)
where all symbols have their usual meanings and give its applications. Also explain
the effect of pressure on the melting points of solids and boiling points of liquids.
43. Write Maxwell's four thermodynamic relations and derive the relation.
 ∂p  L
  =
 ∂T  T (V2 – V1) [Meerut 2011]
192
44. Deduce Clapeyron latent heat equation and explain the effect of pressure on the
melting point of ice and wax. [Meerut 2011]
45. Define specific heat of saturated vapour. Prove the second latent heat equation of
clausius,
dL L
s2 – s1 = –
dT T
where s1 and s2 are the specific heats of liquid and the saturated vapour
respectively and L is the latent heat of vaporisation at Kelvin temperature T. Also
show that the specific heat of saturated water vapour is negative.
[Meerut 2012, 08, 07, 05, 03, 02, 01]
46. Write short not on specific heat of saturated vapours. [Meerut 2001]
47. Prove the second latent heat equation of Clausius:

dL L
− =s −s
dT T 2 1
where all symbols have their usual meanings. How will you explain the negative
specific heat of saturated water vapour ? [Meerut 2008]
48. Show that the specific heat of saturated water vapour is negative. [Meerut 2012]
49. Explain thermodynamical potentials U,H,F and G. Deduce Maxwell's

thermodynamic relations from them. What is the importance of these potentials?
[Meerut 2008B]
50. What do you understand by thermodynamic potentials U (internal energy) and F

(free energy) of a system? Establish the Gibb's-Helmholtz equation,
 ∂F 
U = F –T  and give its importance.
 ∂T  V
51. Explain why cooling is produced by adiabatic demagnetization of a paramagnetic

substances? Obtain an expression for the cooling produced.
[Meerut 2006B, 03, 02, 01]
52. Explain the principle of magnetic cooling. Obtain an expression for the cooling
produced in adiabatic demagnetization of paramagnetic substances. [Meerut 2003]
53. What is adiabatic demagnetization ? How it is used to produce lower temperature ?
Obtain an expression for the cooling produced in this method ? [Meerut 2006B]
54. Give a method to produce and measure of very low temperature.

55. Explain the principal of adiabatic demagnetization and the method for reaching
temperature near absolute zero. How is such low temperature measured ?
[Meerut 2012, 09B]
193

1. Describe Joule's experiments which demonstrated the equivalence of heat and
work and establish that heat is energy.
2. Define Mechanical Equivalent (J) of heat.
3. Define External Work and Internal Work.
4. Give an example of a process in which no heat is transferred to and from a system
but the temperature of the system changes.
5. A combustion experiment is performed by burning a mixture of fuel and oxygen
in constant volume bomb surrounded by a water bath. During the experiment the
temperature of water rises. Considering the mixture of fuel and oxygen as the
system, explain (i) has heat been transferred (ii) has work been done (iii) internal
energy ∆U of the system decreases or increases.
6. A thermos bottle containing coffee is vigorously shaken and thereby the
temperature of coffee rises. Consider the coffee as the system (i) has heat been
transferred to coffee (ii) has work been done on coffee? (iii) internal energy of the
system decreases or increases.
7. Can heat be given to a substance without rising temperature? [Meerut 2012]
8. Heat is a form of potential energy, explain this statement.
9. Equal masses of a monoatomic and a diatomic gas at the same temperature are
given equal quantities of heat at constant volume. Which gas will undergo a
larger temperature rise and why?
10. 0.005 kg air is heated at constant volume from 2ºC to 7ºC. Find the change in
its internal energy. The specific heat of air at constant volume is 0.172 K cal/kg
ºC and J = 4.18 Joule/cal.
11. An ideal gas expands to double its volume isobarically, isothermally or
adiabatically. For which expansion are (i) largest and smallest changes in
temperature (ii) largest and smallest amount of work done (iii) largest and
smallest heat absorption by the gas.
12. A gas is filled in box whose opposite walls are maintained at different
temperatures. Explain heat conduction through the gas.
13. Classify the reversible and irreversible process with reasons. (i) Isothermal
expansion of a gas (ii) Adiabatic compression of a gas (iii) Diffusion of gases (iv)
Transfer of heat from a hot body to cold body (v) Transfer of heat by radiation.
14. Explain Joule expansion of a perfect gas is a irreversible process. What about
Joule Thomson effect?
15. What do you understand by a heat engine and its efficiency? [Meerut 2004]
16. Explain why a Carnot engine is not practically possible? [Meerut 2009B, 08B, 08]
17. Two Carnot engines are working in series. The first engine absorbs a quantity of
heat Q 1 at a temperature T1 and after doing work W1 rejects the remaining heat
194
Q2 at a lower temperature T2 . The second engine absorbs the heat Q2 at

temperature T2 and after doing work W2 rejects the remaining heat Q 3 at a still
lower temperature T3 . Compute the efficiency of the combination.
18. What do you understand by Carnot ideal refrigerator? Explain in detail.
19. If the door of a refrigerator remains open, then a room can not be cooled. Explain
your answer.
20. Explain why the islands and coastal areas of continents have a moderate
temperature variation.
21. Give the mathematical representation of the second law of thermodynamics.
[Meerut 2011, 10, 08B]
22. Show that the entropy of an isolated system never decreases. [Meerut 2008]
23. It is said that the cosmic rays falling on the earth "decreases" the entropy of the
earth. Does it violate the second law of thermodynamics?
24. Calculate the change in entropy when one mole of an ideal gas undergoes
reversible isothermal. [Meerut 2003]
25. Calculate the change in entropy of a Van der Waal's gas as it goes from one state
to another state.
26. Represent Carnot cycle on p-V and T-S diagram and show that area of the cycle
on T-S diagram represent available energy. Also calculate the efficiency of carnot
engine from T–S diagram. [Meerut 2009B, 05B, 03]
27. Obtain an expression for the change in entropy when the ice changes into steam.
[Meerut 2007B, 07, 03]
28. What are the limitations of first law of thermodynamics? What is the purpose of
second law of thermodynamics. [Meerut 2010, 07, 04, 02]
29. Explain the isochoric process on the basis of first law of thermodynamics.
[Meerut 2006]
30. Explain "Free Expansion" on the basis of 1st law of thermodynamics. Is it a reversible
process? Does the entropy increases in this process? [Meerut 2012, 10, 09B]
31. What is third law of thermodynamics? What is the need of it? [Meerut 2012, 11]
32. Explain adiabatic expansion and free expansion on the basis of first law of
thermodynamics. [Meerut 2011]
33. State and explain entropy on the basis of second law of thermodynamics.
[Meerut 2011]
34. Prove the thermodynamic relation,
 ∂ S  ∂ p
  =
 ∂ V  T  ∂ T  V
 ∂ p L
and hence prove that,  =
 ∂ T  T(V2 − V1 )
[Meerut 2012, 07B, 05, 04,02]
195
 ∂p   ∂S   ∂p 
35. Prove that     =− 
 ∂S  T  ∂T  p  ∂T  S
 ∂p   ∂V   ∂p 
36. Prove that     =− 
 ∂V  T  ∂T  p  ∂T  V
37.  ∂V 
Prove the thermodynamics relation, TdS = C p dT − T   dp.
 ∂T  p
 ∂p 
38. Prove the thermodynamics relation, TdS = CV dT + T   dV
 ∂T  V
[Meerut 2003]
 ∂C p   ∂ 2V 
39. By using Maxwell's relations, prove that,   = − T  
 
 ∂p  T  ∂T 2  p
 ∂C   ∂2 p 
40. Using Maxwell's relations, prove that,  V  = T  
 ∂V T 2
 ∂T  V
41.  ∂p   ∂V  2
Prove the relation, C p − CV = T     = TE α V where C p and C V are
 ∂T  V  ∂T  p
the molar specific heats at constant pressure and constant volume respectively. E is
bulk modulus of elasticity, α is the coefficient of thermal expansion. [Meerut 2001]
42. Calculate the change in the vapour pressure of water as the boiling point changes
from 100ºC to 102ºC. The specific volume of steam is 1671 cm 3 / gm . The latent
heat of steam is 540 cal/gm. Given that, J = 4.2 × 107 erg/cal and 1 atm = 1 × 106
dyne/cm 2 .
43. Calculate the latent heat of steam at 100ºC under atmospheric pressure. Given
that, specific volume of saturated steam and water = 1676 cm 3 / gm and
dp
1cm 3 / gm respectively, = 27.1 mm of Hg / ºC.
dT
44. Show that in porous plug experiment, the initial and final enthalpies of the gas
are equal.
45. Explain negative specific heat of saturated vapour. Also give the physical
significance and application of negative specific heat of saturated water vapour.
[Meerut 2009B]
46. Show that an isothermal curve for an ideal gas is isoenthalpic.
47. Define enthalpy. Show that during an isobaric process the change in enthalpy in
enthalpy equal to the heat transferred. [Meerut 2012]
 ∂G 
48. Define Gibbs free energy and show that, G = H + T  
 ∂T  P
196

1. Define temperature of a body.
2. Define zeroth law of thermodynamics. [Meerut 2009B]
3. What do you understand by indicator diagram?
4. State first law of thermodynamics [Meerut 2012, 09B, 08B, 05B]
5. Explain why the temperature of a gas drops in an adiabatic expansion?
6. If hot air rises, why is it cooler at the top of a mountain then near sea level?
7. What will happen when sealed rubber balloon containing a very little gas rises
high into the atmosphere?
8. Define a quasi-static process. [Meerut 2006B]
9. What is free expansion? [Meerut 2007]
10. Define adiabatic expansion. [Meerut 2009, 07]
11. In cold countries heat pumps are use in winter to transfer heat from some
source(pond of water) to the interior of houses. Do they violate the laws of
thermodynamics?
12. Define reversible and irreversible process. [Meerut 2011, 08B, 07B]
13. What are isentropic processes? [Meerut 2009B]
14. Define Carnot cycle and Carnot engine.
15. State Carnot's theorem. [Meerut 2009]
16. State second law of thermodynamics. [Meerut 2012, 09B]
17. What do you mean by internal combustion engine?
18. Write four different strokes of an engine.
19. Define entropy. [Meerut 2012]
20. When one mole of an ideal gas undergoes reversible adiabatic expansion, what
will be change in entropy of the gas?
21. State third law of thermodynamics. [Meerut 2006B]
22. Define thermodynamical variables. [Meerut 2012]
23. Define extensive variables.
24. Define intensive variables.
25. Write first and second law of thermodynamics in mathematical form. [Meerut 2008B]
26. Write down Maxwell's four thermodynamics relations. [Meerut 2010]
27. If the liquid is compressed adiabatically then temperature of the system increases,
explain why?
28. What do you understand by Joule Thomson effect? [Meerut 2011]
29. According to the Clausius Clapeyron equation, the melting point of ice type
(contract on melting) substances is lowered with increase in pressure, while that
of wax type (expand on melting) substance is increased. Can you say something
197
regarding the boiling point of liquids with the help of Clausius Clapeyron
equation. [Meerut 2011]
30. Write down the Clausius Clapeyron heat equation. [Meerut 2009]
31. Under what conditions the latent heat becomes zero?
32. Define specific heat of saturated water vapour. [Meerut 2005B]
33. Define cooling due to adiabatic demagnetisation. [Meerut 2011]
34. Write Gibbs Helmholtz equation.
35. Write any one Maxwell's thermodynamic relation.

1. Thermodynamical equilibrium means:
(a) Thermal equilibrium (b) Mechanical equilibrium
(c) Chemical equilibrium (d) All of the above
2. During an isothermal process, the quantity remains constant:

(a) Pressure (b) Volume
(c) Temperature (d) All of the above
3. During an adiabatic process, the quantity remains constant:

(a) Temperature (b) Internal energy
(c) Volume (d) None of the above
4. For the adiabatic process of an ideal gas, the relation between pressure and volume
is given by:
(a) pV= constant (b) pV γ = constant
(c) pγ V = constant (d) None of the above
5. In free expansion:
(a) No heat enters or leave the system (b) No work is done by or on the system
(c) Both (a) and (b) (d) None of the above
6. The efficiency of a Carnot engine is given by:

Work output T
(a) (b) 1 − 2
Heat input T1
Q2
(c) 1 − (d) All of above
Q1
7. For a Carnot engine:

Q1 T Q1 T
(a) = 1 (b) = 2
Q2 T2 Q2 T1
(c) Both (a) and (b) (d) None of the above
198
8. The change in entropy of a system is defined by:

(a) Q / T (b) VT
(c) p / V (d) None of the above
9. Maxwell's important thermodynamical relations are:

(a) Four (b) Two
(c) Eight (d) None
10. The internal energy of an ideal gas is independent of its volume at constant
temperature. This law is known as:
(a) Newton's law (b) Joule's law
(c) Stefan's law (d) Van der Waal's law
11. The quantity U + pV is known as:

(a) Entropy (b) Enthalpy
(c) Total energy (d) None
12. Joule Thomson effect for a perfect gas is:

(a) Infinity (b) Zero
(c) Indeterminate (d) None
13. Clausius Clapeyron heat equation is:

d p L d p L
(a) = (b) =
d T p (V2 − V1) d T V ( p2 − p1)
d p L d p L
(c) = (d) =
d T T (V2 − V1) d V T (V2 − V1)
14. Enthalpy of a system can be written as:

(a) H = U + Q (b) H = U + pV
(c) H = Q + pV (d) None
15. In a porous plug process the initial and final enthalpies of the system are:
(a) Equal (b) Different
(c) Zero (d) None

1. If two systems A and B are separately in thermal equilibrium with a third system C,
then A and B will be in ............................. with each other.
2. The p − V diagram is also known as ............................. diagram.
3. Work done by the system is represented by ............................. sign.
199
4. Work done on or by a system is a ............................. function.

5. In adiabatic process ∆U= ............................. .
6. A reversible process is one which can be reversed in such a way that all the
............................. taking place in the direct process are exactly repeated in the
reverse order.
7. The net change in entropy in a complete cycle of a reversible process is
........................... .
8. A temperature scale which is ............................. of the properties of any
particular substance is known as absolute scale of temperature.
9. The perfect gas scale and absolute scale are ............................. in all respects.
10. − 15ºC = ............................. K.
11. The thermodynamics variables, which do not depend on mass are known as
............................. .
12. Complete the Maxwell's thermodynamics relation.
 ∂S 
  = ............................. .
 ∂V  T
13. Complete the Maxwell's thermodynamics relation.

 ∂ Q
  = ............................. .
 ∂p  T
14. For a Van der Waal's gas, at constant temperature, the internal energy depends
upon its ............................. .
15. In porous plug experiment of Joule Thomson effect the change in temperature is
directly proportional to the ............................. on both sides of the porous plug.
16. Joule Thomson coefficient for a perfect gas is ............................. .
17. According to Clausius Clapeyron heat equation, the boiling point of every liquid
............................. with increase in pressure.
18. Specific heat of saturated water vapour is ............................. .
19. The change in enthalpy for an isobaric process is equal to the ............................. .
20. Can you get absolute zero temperature?
(F) True/False
1. Work done in isothermal process is equal to that in adiabatic process.
2. In adiabatic process for an ideal gas, the relation between volume and temperature
is TV γ − 1= constant.
3. Work done on a system is represented by negative sign.
4. Work done by or on the system depends only on initial and final states.
5. According the first law of thermodynamics, Q = W − dU
6. In isothermal process Q = W , dU = 0
200
7. Carnot cycle consists of two isothermal and one adiabatic operations.

8. The efficiency of a Carnot engine is always greater than one.
9. According to Carnot's theorem, no engine working between two given temperatures
can be more efficient than a reversible engine working between the same two
temperatures.
10. It is impossible to construct an engine which operating in a cycle will takes heat from
a body and convert it completely into work without leaving any change anywhere.
11. It is impossible by any procedure, no matter how idealised, to reduce any system
to absolute zero of temperature in a finite number of operations.
12. The thermodynamic variables, which depend upon mass (or the number of moles)
are known as intensive variables.
13. If a liquid is compressed adiabatically, then its temperature will rise.
14. For a perfect gas, C p− CV = R
15. For an ideal gas,at constant temperature, the internal energy depends on its volume.
16. For a Van der Waal's gas, at constant temperature, the internal energy depends on its volume.
17. Joule Thomson coefficient for an Van der Waal's gas is zero.
18. The ratio of adiabatic to isothermal elasticity is equal to the ratio of specific heats
at constant pressure to constant volume.
19. According to Clausius Clapeyron equation, the melting point of a substance (ice type)
increases with increase in pressure.
20. According to Clausius Clapeyron equation, the boiling point of a substance
increases with increase in pressure.
21. The specific heat of saturated vapour at 100ºC is positive.
22. Helmholtz free energy (function) represents the work done by the system in a
reversible isothermal process.
23. Enthalpy represents the quantity of heat given to the system from an external
source.
24. If a substance already magnetised is suddenly demagnetised, then there will be an
increase in temperature of the substance.
201
Answers
1. Joule's Experiments: Joule performed a number of experiments to establish
relation between work and heat. He tried to find the amount of heat produced by
a certain amount of work done. He rotated a brass paddle-wheel in water
contained in copper calorimeter. With the expenditure of a measured amount of
mechanical work, he measured the rise in temperature of the water. He found
that the amount of heat (thermal energy) produced was always proportional to the amount
of work done. Joule performed many more experiments to measure the heat
produced by measured amounts of mechanical work. In another experiment, he
stirred mercury contained in an iron vessel by an iron paddle and measured the
heat produced. In another one experiment, he rubbed two iron rings against each
other under mercury. All these experiment gave practically the same result. Thus,
Joule established that a given amount of mechanical work done in any way always
produces the same amount of heat and the disappearance of that amount of heat
always gives the same amount of mechanical work. This establishes the fact that
heat is a form of energy.
2. Mechanical Equivalent of Heat: When mechanical work is transformed into
heat, or heat into mechanical work, there is a constant ratio between the work
and amount of heat. This ratio is called mechanical equivalent of heat and is
denoted by J. Thus, if W be amount of work done and Q the amount of heat
produced then we have W / Q = J or W = JQ
If Q = 1 unit, then J = W , therefore J is numerically equal to the mechanical work

required to produce one unit of heat.
3. External Work and Internal Work: When a system undergoes a displacement
under the action of a force, work is said to be done, its magnitude is equal to
product of the force and the component of the displacement along the direction
of force. If the system "as a whole" exerts a force on its surroundings and a
displacement takes place, then the work done by the system is called external
work, e.g., when a gas contained in cylinder expands and pushes out the piston,
external work is done by the gas on the piston.
When the work is done by one part of a system on another part of the same
system, then it is called "internal work" e.g., the molecules of an actual gas attract
one another. Therefore, when a gas expands work is done against the mutual
attraction between its molecules. It is the internal work.
4. In all dynamic processes involving friction, heat is always produced causing
temperature rise, although no heat is transferred, e.g., when water is stirred by a
rotating paddle wheel the temperature of water increases.
202
5. (i) Yes, the heat has been transferred from the system to the water.
(ii) No, the work has not been done because the volume of the system remains
constant.
(iii) We have, ∆U = Q − W, here W = 0 and heat has been given out by the system i.e.,
Q = − ive, therefore ∆U is negative i.e., the internal energy of the system decreases.
8. The heat added to the melting ice is used in displacing the molecules from their
positions and making their order irregular, i.e., it is stored as the internal
potential energy of the molecules. Thus, heat can also be considered as a form of
potential energy.
10. According the first law of thermodynamics,

Q = W + ∆U
where Q is absorbed heat by the system and W is the external work done by
system. Here it is given that air is heated at constant volume i.e., dV = 0
∴ W =0 or Q = ∆U
the heat absorbed by the air will be,
Q = mass × sp. heat × change in temperature = m × C × ∆t
Given that, m = 0 . 005 kg, C = 0 . 172 Kcal / KgºC
= 172 cal / kgºC and ∆t = 5ºC
∴ Q = 0 . 005 × 172 × 5 = 4 . 300 cal
Thus, change in its internal energy, ∆U = Q = 4 . 3 cal = 4 .3 × 4 . 18 = 17 . 97 J
11. Fig. 3.19 (i), (ii), (iii) shows isobaric, Isobaric (i)
pi
isothermal and a diabtic expansions
respectively. (i) In isobaric process Iso
the
rm
pressure is constant, then temperature will Ad
al (
ii)
ia ba
rise, in isothermal expansion temperature tic
(ii
i)
will remain unchanged and in adiabatic
expansion the temperature falls. So, rise
in temperature is larger in isobaric
expansion than the temperature drop in Vi Vf
adiabatic expansion. (ii) The work done Volume, V

by the gas is largest in isobaric expansion Fig. 3.19
and smallest in adiabatic expansion.
(iii) According the first law of thermodynamics,

Q = W + ∆U
For isobaric expansion temperature rises, means internal energy ∆U increases. Also
work done is large, so heat absorption is largest. For isothermal expansion, ∆U = 0
∴ Q =W
203
For adiabatic expansion, Q = 0, i.e., heat absorbed by the gas is smallest.

15. Heat engine: Any cyclic device by which heat is converted into mechanical work is called a
heat engine.
There are three important parts in an engine, a hot body called source, a working
substance and a cold body called sink. The working substance takes in heat from
the source, converts a part of it into useful work and gives out rest heat to the
sink and the working substance returns to its original state. This series of
processes is called a cycle. It is shown in fig 3.20. By repeating the same cycle
over and over again, work can be continuously obtained.
Suppose, the working substance takes in an amount of Source

heat Q 1 from the source and gives out an amount of heat T1
Q 2 to the sink. Suppose W is the amount of work
Q1
obtained. The net amount of heat absorbed by the H
substance is Q 1 − Q 2 , which has been actually W
converted into work, i.e., Q 1 − Q 2 = W
Q2
Sink
Efficiency: The thermal efficiency of an engine is defined as the
T2
ratio of the work obtained to the heat taken in from the source,
Fig. 3.20
i.e.,
W Q1 − Q 2
η= =
Q1 Q1
Q 2
or η= 1−
Q 1
17. The total work by the combination in one cycle is,

W = W1 + W2 = (Q 1 − Q 2 ) + (Q 2 − Q 3 ) = Q 1 − Q 3
The heat absorbed by the combination is Q 1 therefore, the efficiency of the
combination is,
Total work done Q 1 − Q 3 Q3
η= = =1 −
heat absorbed Q1 Q1
Q3 T3 T3
But, = ∴ η =1 −
Q1 T1 T1
This is the same as the efficiency of a single engine working between T 1 and T 3 .
204
18. Carnot Ideal Refrigerator: Any device which takes

Hot body
in heat from a cold body and transfers it to a hotter
body is known as refrigerator. It is essentially a heat Q1
engine running backwards. In a heat engine, the
W
working substance takes in heat from a body at a
higher temperature, converts a part of it into Q2
mechanical work and gives out the rest heat to a body Cold body
at a lower temperature. In refrigerator, a working
substance takes in heat from a body at a lower
Fig. 3.21
temperature, has a net amount of work done on it by
an external agent and gives out a larger amount of
heat to a hot body (Fig. 3.21). Thus, refrigerator continually transfers heat from
a cold to a hot body at the cost of mechanical work supplied to it by an external
agent. Let Q 2 be the heat taken in (removed) from a cold body at temperature
T 2 , W is the net work done on the working substance (refrigerant) and Q 1 the
heat given out to the hot body at temperature T1, then we have
Q1 = Q 2 + W
 Q1 
or W = Q1 − Q 2 = Q 2  – 1
Q2 
 
Q1 T1
From Carnot engine, = [If refrigerant is an ideal gas]
Q2 T2
 T1 
∴ W= Q2  − 1
T 2 
 
This is the expression for the work that must be supplied to run the refrigerator.
Coefficient of performance of a refrigerator: The coefficient of performance
K is defined as the ratio of the heat taken in from the cold body to the work
required to run the refrigerator i.e.,
Q2 Q2 1
K= = =
W Q1 − Q 2 Q1
−1
Q2
Q1 T1
But, we have =
Q2 T2
1 T2
∴ K= =
T1 T1 − T 2
−1
T2
This is the expression for the coefficient of performance. Higher the coefficient of
performance, better will be refrigerator. Thicker and high insulation tends to
increase the coefficient of performance.
205
Relation between the efficiency of a Carnot engine and the coefficient of

performance of a Carnot refrigerator: Let a Carnot engine and a Carnot
refrigerator works between the same temperature T 1 and T 2 , then we have,
T2
The coefficient of performance, K =
T1 − T 2
T2 T 2 + T1 − T 2 T1
∴ K +1= + 1= =
T1 − T 2 T1 − T 2 T1 − T 2
1  T 2 T1 − T 2 
= Q η = 1 − = 
η  T1 T1 
 
1
where η is the efficiency of Carnot engine. So, η =
K +1
19. The refrigerator removes heat from its interior and gives it out into the
surrounding air, thus warming the air. For doing this, additional energy is supplied
to the refrigerator by an electric motor. The heat given out into the air is the sum
of the energy from the motor and that removed from the interior of the
refrigerator. So, we can say that the refrigerator adds more heat into the room
than it removes from its interior. On opening its door it will run continuously and
hence add even more heat to the room than when its door is closed.
21. Let Si and S f be the entropies of a system in an initial state i and final state f .
f
dQ
Then, the entropy change will be, ∆S = S f − fi =
∫ T
...(1)
i
This relation is applicable only for reversible paths. If two states are infinitesimally
close to each other, then equation (1) can be written as, dS = dQ / T
or dQ = TdS
This equation is the mathematical representation of the second law of
thermodynamics.
24. The change in entropy of the gas is, ∆S = Q / T
Let 1 mole of an ideal gas undergoes reversible isothermal compression
(expansion) from volume V1 to V2 , then ∆T = 0 i.e., dU = 0 and from the first law
of thermodynamics, Q = W + dU , Q = W and the work done on (by) the gas
during the compression (expansion),
V2 V2
RT
W=
∫ pd V = ∫ V
dV [ Q dV = RT ]
V1 V1
V2
dV V2
or W =RT
∫V = R T log e
V1
V1
206
V
R T log e 2
V1 V
So ∆S= = R log e 2
T V1
Since, V2 < V1 (compression), ∆S is negative which means that the entropy of the
gas decreases, whereas for V2 > V1 (expansion) ∆S will be positive, means the
entropy of the gas increases. It is important to note that an equal increase or
decrease in the entropy of the heat reservoir occurs which is placed in contact of
the gas to carry out the isothermal compression. Thus, the total entropy of the
universe (gas + surroundings) remains unchanged which is a characteristic of the
reversible process.
25. Entropy change in a Van der Waal's gas
The equation of state for one mole of Van der Waal's gas is given by,
 a 
 p + 2  (V − b) = RT
 V 
where a and b are Van der Waal's constant.When an infinitesimal amount of heat
dQ is given to the gas at temperature T, the increase in entropy is,
dQ
dS = ...(1)
T
But, from the first law of thermodynamics, we have
dQ = dU + dW ...(2)
If CV be the molar specific het of the gas at constant volume and the rise in
temperature is dT and the change in internal energy is dU, then
dU = CV dT
The work done including work against the molecular attraction is given by,
 a  RT
dW =  p + dV = dV
 2  V −b
V
Using these expression, equation (2) becomes,
RT
dQ = CV dT + dV
V −b
Using this expression, equation (1) becomes,
dT R
dS = CV + dV
T V −b
The change in entropy when the gas goes from one state (Vi, Ti, pi) to (V f , T f , p f ) is,
Tf Vf − b
∆S = CV log e + R log e
Ti Vi − b
This is the required expression.
26. Carnot Cycle on p-V and T-S Diagram: A Carnot cycle consists of two
reversible isothermal processes and two reversible adiabatic processes as shown in
fig. 3.22 (a). Thus, it forms a rectangle on a T-S diagram (for any working
substance) shown in fig. 3.22(b).
A
208
mL 1
∆S 1 =
T1
where L 1is the latent heat of ice.

The entropy change when water is heated from T1 to T2 is,
T
∆S2 = mC log e 2
T1
where C is the specific heat of water.
The entropy change when water is converted into steam is,
mL2
∆S3 =
T2
where L2 is the latent heat of vaporisation of water. Thus, the total change in
entropy is,
∆S = ∆S1 + ∆S2 + ∆S3
mL1 T mL2
= + m C log e 2 +
T1 T1 T2
30. If a system expands in such a way that no heat enters or leave the system
(adiabatic process) and also no work is done by or on the system, then this
expansion is known as free expansion, i.e., in an adiabatic expansion no work is
done by or on the system.
Let us consider an asbestos covered vessel (adiabatic) with rigid walls and divided
into two parts, one containing a gas and the other evacuated. When the partition
is suddenly broken, the gas rushes into the vacuum and expands freely. If U i and
U f be the initial and final internal energies of the gas, then by the first law of
thermodynamics, ∆U = Q − W, we have
Q = 0, W = 0 So, ∆U = 0
i.e., Ui − U f = 0
or Ui = U f
Thus, in the free expansion, the initial and final internal energies are equal.
Yes it is a reversible process. In this process entropy does not change as Q = 0.
33. Let Si and S f be the entropies of a system in an initial state i and final state f .
Then, the entropy change will be,
f
dQ
∆S = S f − fi =
∫ T
...(1)
i
This relation is applicable only for reversible paths. If two states are
infinitesimally close to each other, then equation (1) can be written as,
dS = dQ / T
or dQ = TdS
This equation is the mathematical representation of the second law of

thermodynamics.
209
34. According to first and second law of thermodynamics, we have

dQ = dU + pdV [Q dW = pdV ]
and dQ = TdS
We can write as, TdS = dU + pdV
or dU = TdS − pdV ...(1)

Let, U , S and V are the functions of two independent variable x and y , then, we have
∂U ∂U
dU = dx + dy
∂ x ∂ y
∂S ∂S
dS = dx + dy
∂ x ∂ y
∂V ∂V
and dV = dx + dy
∂ x ∂ y
Putting these values in equation (1), we get
∂U ∂U ∂ S ∂S  ∂ V ∂V 
dx + dy = T  dx + dy − p  dx + dy
∂ x ∂ y ∂ x ∂ y  ∂ x ∂ y 
Equating the coefficient of dx and dy on both sides, we get
∂U ∂S ∂V
=T −p ...(2)
∂ x ∂ x ∂ x
∂U ∂S ∂V
and =T −p ...(3)
∂ y ∂ y ∂ y
Differentiating equation (2) w.r.t. y and equation (3) w.r.t. x, we get

∂2U ∂T ∂S ∂2 S ∂p ∂V ∂2V
= +T − −p
∂y ∂x ∂y ∂x ∂y ∂x ∂y ∂x ∂y ∂x
∂2U ∂T ∂S ∂2 S ∂p ∂V ∂2V
and = +T − −p
∂x ∂y ∂ x ∂y ∂x ∂y ∂x ∂y ∂x ∂y
Since dU , dS and dV are all perfect differentials. So,

∂2U ∂2U ∂2 S ∂S ∂2V ∂2V
= , = and =
∂y ∂x ∂x ∂y ∂y ∂x ∂x ∂y ∂y ∂x ∂x ∂y
Hence, we get
∂T ∂S ∂p ∂V ∂T ∂S ∂p ∂V
− = − ...(4)
∂y ∂x ∂y ∂x ∂x ∂y ∂x ∂y
This is the general Maxwell's thermodynamic equation. Now, we put x = T and

y = V , then we have
∂T ∂V ∂T ∂V
= 1, = 1 and = 0, =0
∂x ∂y ∂y ∂x
Therefore, equation (4) becomes,
210
∂S ∂p
− =0
∂y ∂x
 ∂S   ∂p 
or   = [Q x = T and y = V ]
 ∂V  T  ∂T  V
This is the required relation.
Now, multiplying T on both sides, we get
 ∂S   ∂p 
T   =T  
 ∂V  T  ∂T  V
But, we know that, T∂S = ∂Q , therefore,

 ∂Q   ∂p 
  =T   ...(5)
 ∂V  T  ∂T  V
Here, ∂Q represents the amount of heat absorbed by the system at constant
temperature in changing its volume. This heat is known as latent heat. So, if L be
the latent heat of the unit mas of substance changing volume from V1 to V2 at
constant temperature, then
 ∂Q  L
  =
 ∂V  T (V2 − V1)
Hence, equation (5) can be written as,
L  ∂p 
=T  
(V2 − V1)  ∂T V
 ∂p  L
or   =
 ∂T V T (V2 − V1)
It is Clausius Clapeyron equation.
35. From Maxwell's thermodynamic relation, we have
 ∂S   ∂V 
  =− 
∂
 Tp  ∂T  p
 ∂p   ∂T 
or   = −   ...(1)
 ∂S  T ∂V  p
 ∂p   ∂S   ∂T   ∂S   ∂S 
∴     =−    =−  ...(2)
 ∂S  T ∂T  p  ∂V  p  ∂T  p  ∂V  p
Also from Maxwell's relations, we have

 ∂T   ∂V   ∂S   ∂p 
  =  or   =  ...(3)
 ∂p  S  
∂S p  
∂V p  ∂T  S
By using equation (3) and equation (2) becomes,

 ∂p   ∂S   ∂p 
    =− 
 ∂S  T  ∂T  p  ∂T  S
36. From Maxwell's relation, we have

 ∂V   ∂S 
  =− 
 ∂T  p  ∂p  T
211
 ∂p   ∂V   ∂p   ∂S   ∂S 
or     =−    = −  
 ∂V  T  ∂T  p  ∂V  T  ∂p  ∂V  T
T
We also have Maxwell's relation,
 ∂S   ∂p 
  =
 ∂V  T  ∂T  V
 ∂p   ∂V   ∂p 
∴     =− 
 ∂V  T  ∂T  p  ∂T  V
37. Let the entropy S of a thermodynamic system be a function of temperature and

pressure, i.e.,
S = f (T , p)
Since, dS is a perfect differential. So, we can write,
 ∂S   ∂S 
dS=  dT +   d p
 ∂T  p  ∂p  T
 ∂S   ∂S 
T d S =T   dT + T   d p
 ∂T  p  ∂p  T
Also, the specific heat of a substance at constant pressure is given by,
 ∂ Q  ∂S 
Cp =   =T   (Q ∂Q = T∂S)
 ∂T  p  ∂T  p
and from Maxwell's relation,

 ∂S   ∂V 
  =− 
 ∂p  T  ∂T  p
 ∂V 
∴ T d S = C p dT − T   dp
 ∂T  p
38. Let the entropy of a thermodynamics system be a function of temperature T and V, i.e.,
S = f (T , V )
Since, dS is a perfect differential. So, we can write,
 ∂S   ∂S 
dS=  dT +   dV
 ∂T  V  ∂V  T
 ∂S   ∂S 
T d S =T   dT +T   dV
 ∂T  V  ∂V  T
Also, the specific heat of a substance at constant volume is given by,
 ∂ Q  ∂S 
  = CV = T   (Q ∂Q = TS)
 ∂T  V  ∂T  V
and from Maxwell's relation,
 ∂S   ∂p 
  =
 ∂V  T  ∂T  V
 p
∴ TdS = C V dT + T  ∂  dV
 ∂T  V
212

 ∂S   ∂V 
  =− 
∂
  p  ∂T  p
T
Differentiating partially w.r.t., T at constant pressure, we get,
 ∂  ∂S    ∂2V 
    = −  2 
 ∂T  ∂P  T  p  ∂T  p
Multiplying T on both sides,

 ∂  ∂S    ∂2V 
T     = −T  
 2
 ∂T  ∂p  T   ∂T  p
p
 ∂  ∂S    ∂2V   ∂  ∂ ∂  ∂ 
or T     = −T   Q   =  
 2
 ∂p  ∂T  p   ∂T  p  ∂x  ∂y ∂y  ∂x  
T
But we have, T∂S = ∂Q, therefore
 ∂  ∂ Q   ∂2V 
    = −T  
 2
 ∂p  ∂T  p   ∂T  p
T
Also, we know that, at constant pressure the heat given to the substance to raise
its temperature by unity is the specific heat at constant pressure, i.e., C p
 ∂ Q
So,   = Cp
 ∂T  p
 ∂C p   ∂2 V 
∴   = − T  
 ∂p  T  ∂T 
 p

 ∂S   ∂p 
  =
 ∂V  T  ∂T  V
Differentiating partially w.r.t., T at constant volume, we get
 ∂  ∂S    ∂2 p 
    = 
 ∂T  ∂V  T  V  ∂T  V
2
Multiplying T on both sides,

 ∂  ∂S    ∂2 p 
T     =T  
 ∂T  ∂V  T V  ∂T 2 
 V
 ∂  ∂S    ∂2 p   ∂  ∂ ∂  ∂ 
or T     =T   Q   =  
 ∂V  ∂T  V T  ∂T 2   ∂ x ∂
 y ∂ y  ∂x  
 V
But we have, T∂S = ∂Q , therefore
 ∂  ∂ Q   ∂2 p 
   =T  
 ∂V  ∂T  V   ∂T 2 
 V
T
Also we have that, at constant volume the heat given to the substance to raise its
temperature by unity is the specific heat at constant volume, i.e., CV .
213
 ∂ Q
So,   = CV
 ∂T  V
 ∂C V   ∂2 P 
∴   = T 2 
 ∂V  T  ∂T  V
41. The molar specific heat at constant pressure C p and molar specific heat at
constant volume CV of a thermodynamic system are given as,
 ∂ Q  ∂ Q
Cp =   and CV =  
 ∂T  p  ∂T  V
 ∂ Q  ∂ Q
∴ C p − CV =   − 
 ∂T  p  ∂T  V
Also we have, TdS = dQ

 ∂S   ∂S 
∴ C p − CV = T   −T   ...(1)
 ∂T  p  ∂T  V
Now, let the entropy S, be a function of T and V and since, dS is a perfect

differential then, we have
 ∂S   ∂S 
dS =   dT +   dV
 ∂T  V  ∂V  T
 ∂S   ∂S   ∂S   ∂V 
or   =  +   
 ∂T  p  ∂T  V  ∂V  T  ∂T  p

 ∂S   ∂S   ∂S   ∂V 
T   −T   =T    
 ∂T  p  ∂T  V  ∂V  T  ∂T  p
 ∂S   ∂V 
or C p − CV = T     ...(2)[using equation (1)]
 ∂V  T  ∂T  p
But from Maxwell's relation,

 ∂S   ∂p 
  =
 ∂V  T  ∂T  V
By using this relation, equation (2) becomes,
 ∂p   ∂V 
Cp − CV = T     ...(3)
 ∂T  V  ∂T  p
Now, let p is a function of T and V and dp is a perfect differential, then we have
 ∂p   ∂p 
dp =   dT +   dV
 ∂T  V  ∂V  T
If the change takes place at constant pressure, then dp = 0
 ∂p   ∂p 
∴   dT = −   dV
 ∂T  V  ∂V  T
 ∂p   ∂p   ∂V 
or   =−   
 ∂T  V  ∂V  T  ∂T  p
Putting this value in equation (3), we have
 ∂p   ∂V   ∂V 
C p − CV = − T      
 ∂V  T  ∂T  p  ∂T  p
214
2
 ∂p   ∂V 
Cp − CV = − T    
 ∂V  T  ∂T  p
2
T  ∂p  2  ∂V / V 
or C p − CV = −   V  
V  ∂V / V  T ∂T  p
p   ∂V / V  2

= −T  ∂    .V
 ∂V / V  T  ∂T  p
Also, we have that,
 ∂p  ∂V / V
−  = E , the bulk modulus at constant temperature and = α , the
 ∂V / V  T ∂T
coefficient of thermal expansion, therefore.
C p − CV = TEα 2V
Significance of this Expression

(i)  p 
Since, the bulk modulus E =  − ∂  is always positive for all known
 ∂V / V 
substances and α 2 must be positive (α may be either positive or negative). Thus,
C p − CV will always be positive i.e., C p is always greater than CV .
(ii) As T → 0 , then C p → CV i.e., at absolute zero, both specific heats are equal.
42. The change in the pressure of vapour with change in temperature is given by
d p L
=
d T T (V2 − V1)
Given that, L = 540 cal / gm = 540 × 4 .2 × 1 07 erg / gm

T = 100 º C = 373 K, dT = 102 − 100 = 2 º C = 2 K
V2 = 1671 cm 3 , V1 = 1 cm 3
Putting the values in equation, we get
dp 540 × 4 . 2 × 107
=
2 373(1671 − 1)
or dp = 7 . 2 × 104 dyne / cm 2
= 0.072 atm [Q 1 atm = 106 dyne/ cm 2 ]

43. We have Clausius-Clapeyron equation,
d p L
=
d T T (V2 − V1)
Given that, (dp / dT ) = 27.1 mm of Hg /ºC=2.71cm of Hg/K
=2 . 71 × 13.6 × 980 dyne / cm 2 K
T = 100ºC = 273 + 100 = 373 K
(V2 − V1) = 1676 cm 3 − 1cm 3 = 1675 cm 3
Putting all the values in equation, we get
215
L
2 . 71 × 13 .6 × 980 =
373 (1675)
or L = 2 . 71 × 13 . 6 × 980 × 373 × 1675 erg /gm
= 2256 . 6 × 107 erg / gm
2256 . 6 × 107
= cal/gm = 537 cal/gm
4 . 2 × 107
44. Enthalpy in Porous Plug Experiment: In a porous plug experiment, a gas is

made to pass under high constant pressure through an insulated plug to a region
of lower constant pressure. Let pi and Vi be the pressure and volume of the gas
before passing through the plug and P f and V f the final pressure and volume of
the gas after passing through the plug. The net external work done by the gas is
p f V f − piVi. Since plug is insulated, so there is no heat exchange between the gas
and surroundings. By the first law, this work is done is at the cost of internal
energy of the gas. Thus, if U i and U f be the initial and final internal energies,
then we have
U i − U f = p f Vf − piVi
or U i + piVi = U f + p f Vf
But, U + pV is defined as enthalpy H of the system.
∴ Hi = H f
Thus, in a porous plug experiment, the initial and final enthalpies of the system
are equal.
47. Enthalpy: The enthalpy H of a thermodynamic system is defined as, H = U + pV .
When the system undergoes an infinitesimal process from an initial equilibrium
state to a final equilibrium state, then the change in enthalpy is,
dH = dU + pdV + Vdp
But, we have dU + pdV = dQ (first law of thermodynamics)
∴ dH = dQ + Vdp
For an isobaric (pressure remains constant) process, dp =0
So, dH = dQ
If Hi is the initial and H f is final enthalpy of the system, then we have
Hf − Hi = dQ where dQ is heat transferred to or from the system.
Thus, the change in enthalpy for an isobaric process is equal to the heat transferred.
48. Gibbs Free Energy or Gibbs Function

The Gibbs free energy G of a thermodynamics system is defined as,
G = H − TS ...(1)
where H is the enthalpy and S is the entropy of the system and T is Kelvin
temperature.
For an infinitesimal reversible process, the change in Gibbs energy (function)is,
dG = dH − TdS − SdT
But, we have dH = TdS + Vdp
216
∴ dG = Vdp − SdT ...(2)

For a process in which the temperature and pressure remains constant, i.e., dT = 0
and dp = 0, then
dG = 0
or G = Constant
Thus, for changes at constant pressure and constant temperature (isothermal and
isobaric process, like fusion, sublimation, vaporisation etc.), the Gibbs free energy
remains constant.
If the process is irreversible, then Gibbs function G falls (due to increase in
entropy). Hence, we can say that for changes at constant temperature and pressure, the
Gibbs energy falls or remains constant.
Now, taking the partial differential of G, at constant pressure(dp = 0), from
equation (2) we have
 dG
  =−S ...(3)
 dT  p
By using equation (3) and equation (1) can written as,

 ∂G 
G=H+ T  
 ∂T  p

1. (d) 2. (c) 3. (d) 4. (b) 5. (c) 6. (d) 7. (a) 8. (a)
9. (a) 10. (b) 11. (b) 12. (b) 13. (c) 14. (b) 15. (a)

1. Thermal equilibrium 2. Indicator 3. Positive
4. Path 5. W 6. Changes
7. Zero 8. Independent 9. Identical
  ∂p  
10. 258 11. Intensive variables 12.   
  ∂T  V 
  ∂V  
13. –T    14. Volume 15. Difference in pressure
 ∂T  p

16. Zero 17. Rises 18. Negative
19. Heat transferred 20. No
(F) True/False
1. F 2. T 3. T 4. F 5. F 6. T 7. F 8. F
9. T 10. T 11. T 12. F 13. T 14. T 15. F 16. T

17. F 18. T 19. F 20. T 21. F 22. T 23. T 24. F
❍❍❍
U N I T IV
BLack Body Radiation
Black Body Radiation: Radiation Dependent on Temperature Only

Pressure of Radiation
Stefan Law, Stefan-Boltzman Law
Spectral Distribution of Black Body Radiation
Wien's Displacement Law
Rayleigh- Jean's Law
Planck's Law
Planck's Quantum Hypothesis
Average Energy of Planck's Oscillator
Planck's Radiation Formula
Ultraviolet Catastrophe
219
IV
Black Body Radiation
In general, the term 'radiation' means the transference of energy without affecting the
medium. This energy may be in the form of light, thermal, etc. Here we are talking
about thermal radiation. Thus, the process by which heat is transferred directly from a hot body
to a cold body without affecting the intervening medium is called thermal radiation. To explain
the phenomenon of radiation, it is universally assumed that all bodies are continuously
emitting energy by virtue of their temperature. This energy is called radiant energy or
thermal radiation. It travels like visible light in the form of electro-magnetic waves with
the velocity of light. The thermal radiations can be transmitted through vacuum or
medium like air. When thermal radiations fall on a body which cannot transmit them, a
part of this is absorbed which appears in form of heat (energy converted into heat) and
the other is reflected.
The thermal radiation emitted by a body per unit time per unit surface area depends on
the nature of the surface and on its temperature. At low temperature, the rate of
radiation is small. As the temperature is increased, the rate of radiation increases
rapidly. Further the thermal radiation is a mixture of waves of different wave lengths. At
normal temperatures mostly longer waves (infra-red) are emitted while at very high
temperatures shorter waves (ultra voilet) are emitted. The properties of thermal
radiations are identical to light.
220
Prevost, in 1792 gave a ''theory of exchanges'' to explain the phenomenon of radiation.

According to it all the bodies emit thermal radiations at all temperatures above the
absolute zero irrespective of their surroundings, the amount of radiation increasing with
temperature and there is a continuous exchange of radiation between a body and
surroundings. On the basis of above said theory, how a body hotter than its
surroundings cools down and a colder one warms up. The former radiates more heat to
the surroundings than it receives and the latter receives more heat than it radiates out.
This exchange of heat between the body and its surroundings goes on until the heat it
emits is just balanced by the heat it absorbs i.e., until a dynamic thermal equilibrium is
established between the two.
When radiant energy falls on a body, a part of it is reflected, a part of it is absorbed and
the remaining part is transmitted by the body. A body which absorbs all the radiations
of all wavelengths is called a black body. A black body is only an ideal conception and
Lamp black is the nearest approach to black body (reflects 1% of the incident
radiation). Platinum black is another example of black body.
4.1 Radiation Dependent on Temperature Only

The radiation energy density (energy per unit volume) inside a constant temperature
enclosure depends only upon its temperature and is quite independent of nature or
shape of its walls. It may be proved as follows:
Consider two uniform temperature enclosures A and B of different materials and shapes
maintained at the same constant temperature. The two enclosures are communicating
with each other through a screen transparent to all radiations. It is also supposed that
the energy density of the radiation in A is greater than that in B. Naturally, some
radiation will be transmitted through the screen from A to B. Now, the enclosures are
separated and allowed to regain equilibrium with their new radiation densities. Since
the energy density in A is now somewhat lower than its original value corresponding to
its temperature, its walls will radiate out heat to the space inside it and thus get cooled.
On the other hand, since the energy density inside B is greater, its walls receive
radiation from space in it and will thus get heated up. Thus, a difference of temperature
will be set up between the A and B without any expenditure of energy, which is a
violation of the second law of thermodynamics. Therefore, our supposition that the
energy density in A is greater than in B is wrong. It must be same in A and B at the
same temperature. This is true for each small band of wavelengths present in the
radiation. Thus, the energy density of the radiation energy in a uniform temperature enclosure
depends only on its temperature and is absolutely independent of the nature and shape of the
walls. Also the radiation inside an enclosure is uniform in respect of both quantity and
quality in each direction.
221
4.2 Pressure of Radiation

On the basis of electromagnetic theory, Maxwell showed that radiation exerts a pressure
on the surface on which it is incident. When radiation is incident normally on the
surface, the pressure is found to be equal to energy density. To prove it, let us have a
radiation beam incident normally on surface.
The radiation energy is given by,
E′ = hv = mc2 (Q radiations means photon)
hv
or m=
c2
where m is the mass of photon.
hv
Momentum of the photon = mass × velocity = .c
c2
hv E′
= =
c c
Then, the total momentum imparted to a surface per unit area per second,
E′ E
p=
c
=
c ∑ ...(1)
where E is the total energy incident on the surface per unit area per second.
If u is the energy density (energy per unit volume), the the total energy passing through
any area A of the surface, normal to the radiation per second = u × A × c
Therefore, energy radiated per unit area per second will be,
u× A × c
E= = uc ...(2)
A
p=u
The rate of change of momentum represents the pressure of radiation and it is equal to
the momentum per unit area per second absorbed by the surface. Thus, the pressure of
radiation for normal incidence is equal to its energy density.
In an enclosure at uniform temperature the radiation is isotropic i.e., the same in all
directions and is called diffuse radiation.
Now, suppose a diffused radiation is falling on a surface

OB at an angle θ with the normal (Fig. 4.1). Surface BC is
taken to be normal to the beam so that energy incident on
BC per second
= EA = ucA [from equation (2)]
where A is the surface area of BC.

From the fig. (4.1), A = A' cos θ
where A' is the surface area of surface OB.
222
The total energy (radiation) crossing surface BC is equal to the energy incident on the
surface OB per second.
Therefore, the energy incident on the surface OB per unit area per second
u c A u c A' cos θ
= = = u c cos θ
A' A'
Therefore, the momentum incident on the surface OB per unit area per unit time
u c cos θ
= = u cos θ and its normal component(in the direction normal to OB) will be
c
= (u cos θ) cos θ = u cos2 θ.
If all the radiation is absorbed, then this expression would represent the rate of change
of momentum per second per unit area normal to the surface OB i.e., pressure of
radiation experienced by the surface OB is,
p = u cos2 θ
Since, there is equal probability for the diffuse radiations to be incident on the surface
from all directions. So, the value of cos2 θ should be averaged over the surface. Therefore,
pressure of diffuse radiation = u cos2 θ
To determine the value of cos2 θ, we know that the solid angle subtended by a hollow
cone between angles θ and θ + dθ, at the center of enclosure is,
2 π Rsin θ R d θ
= 2 π sin θ d θ
R2
where R is radius of hemisphere.
π
2 2 π sin θ cos2 d θ 1
So, cos θ =
∫ 4π
=
3
0
Hence, pressure of radiation will be,

p= u /3
Therefore, pressure of diffuse radiation is equal to one third of its energy density.
4.3 Stefan Law

In 1879, Stefan proposed a law, based on the experimental study of the rate of emission
of heat energy by a hot body. According to this law, the total amount of heat radiated by a
perfect black body per second per unit area is directly proportional to the fourth power of its
absolute temperature, i.e., E ∝ T 4
or E = σ T4
where σ is called stefan's constant. This law is also known as Stefan's fourth power law.
223
If the body is not perfectly black body, then
E = σ eT4
where e is emissivity or relative remittance of the body. Thus, e varies between zero and
one depending upon the nature of the surface. For a perfect black body, e =1.
In 1884 Boltzmann gave the theoretical proof of Stefan's law on the basis of
thermodynamics. Therefore, this law is also called Stefan-Boltzmann law.
4.3.1 Stefan–Boltzmann Law

According to this law, the hot body will continue to emit heat upto the temperature
absolute zero, if the temperature of the surrounding is absolute zero. But in actual
practice, the hot body is surrounded by a wall at some lower temperature. Due to this
the body is continuously emitting and absorbing the heat radiations. Hence, if a
perfectly black body at temperature T is surrounded by a wall (surroundings ) at a
temperature T0 Then,
Amount of heat lost per second per unit area by black body = σT 4
Amount of heat absorbed by black body due to surroundings = σT04
Hence, the net loss of energy per second per unit area = σ (T 4 − T0 )
Hence, if a perfectly black body at temperature T is surrounded by a wall at a temperature T0 , the

net rate of loss of heat energy per unit area of the surface is given by,
E = σ (T 4 − T04 )
or E ∝ ( T 4 − T04)
This is known as Stefan-Boltzmann law.

If the body has an emissivity e, then
E = eσ (T 4 − T04 )
4.3.2 Thermodynamic Proof of Stefan's Law

Suppose the black body radiation is enclosed in an evacuated cylinder with perfectly
reflecting walls and perfectly reflecting moving piston (due to perfectly reflecting walls
and piston, there is no heat exchange between them. Hence, their thermal capacity is
not involved).
Let u = energy density (energy per unit volume) of the radiation inside cylinder is
independent of the material of the walls and depends on the temperature T only.
Let the radiation behave as a gas and we can assume it as a thermodynamic system. If
volume of the radiations is V, pressure of radiations is p and temperature of walls is T,
then the total energy of radiation,
224
= energy density × volume

or U = u× v ...(1)
Now, according to Maxwell's electromagnetic theory of radiation, the black body

radiation in an enclosure exerting a pressure p on the walls, is equal to the one third of
the energy density, i.e.,
1
p= u ...(2)
3
Let us suppose that an infinitesimal amount of heat dQ flows into the cylinder from
outside and at the same time the volume changes from Vto V + dV . If dU is the change
in the internal energy of radiation, dS the change in its entropy and dW the external
work done by the radiation in expanding through the volume dV, then according to
first law of thermodynamics,
dQ = dU + dW = dU + pdV
Also from second law of thermodynamics,

dQ = TdS
or TdS = dU + pdV
dU + pdv
or dS =
T
But we have,
 ∂S   ∂p 
  =  [Maxwell's second relation]
 ∂V  T  ∂T 
V
Therefore,
 ∂S  1  ∂U + p∂V   ∂p 
  =  =  ∂T 
 ∂V  T T  ∂V T V
 ∂U   ∂p 
or   + p =T   ...(3)
 ∂V  T  ∂T  V
Using equation (1) and (2), we get

 ∂ (u × V )  u T  ∂u 
 ∂V  + 3 = 3  
 ∂T  V
T
u T  ∂u 
or u+ =   [Q u is a function of T only]
3 3  ∂T 
4u T  ∂u  du dT
or =   or =4
3 3  ∂T  3 T
On integrating, we get
log u = 4 log T + log a
225
or u = aT 4 ...(4)
where a is constant of integration.
We know that, the energy E radiated per second per unit area from a perfect black body
at absolute temperature, T and the energy density of radiation u inside an enclosure at
the same temperature are related by the equation,
1
E= uc
4
where c is velocity of light.
Substituting the value of u in this expression, we get
1
E= ac T 4 = σ T 4
4
where σ = (1 / 4) ac and is called stefan's constant.
This is the Stefan law,
Example 1: Calculate the radiant energy by a black body at a temperature of (i)400 k

(ii) 4000 k [ σ = 5.672 × 10 −8 M.K.S. units].
Solution: The radiant energy by a black body is given by,
E = σT 4 where σ is Stefan's constant
(i) Here, T = 400 K and σ = 5 .672 × 10 −8 M.K.S. units
∴ E = 5 .672 × 10 −8 × (400)4 = 5 .672 × 256
=1452 watt / m2
(ii) Here, T = 4000 K

E = 5.672 × 10 −8 (4000)4 = 5.672 × 104 × 256
= 14520 × 10 3 watts / m2
= 1452 0 K − watts / m2
Example 2: A black body radiates heat per unit area at a rate of 10 5 watt at
300 °C . If sun radiates heat per unit area at a rate of 10 9 watts, then compute the
temperature of the sun.
Solution: According to Stefan's law,

E ∝ T4
226
E1T4
or = 1
E2 T 4
2
Here, E1 = 105 watt, T1 = 300 + 273 = 573 K, E2 = 109 watt
105 (573)4
∴ =
109 T24
109 (573)4
or T24 = = (573)4 (104 )
5
10
or T2 = 5730 K
Example 3: Two large closely spaced concentric spheres (black body radiators) are
maintained at temperatures of 200K and 300K respectively. The space in between the
two spheres is evacuated. Calculate the net rate of energy transfer between the spheres.
[ σ = 5.672 × 10 −8 M.K.S. units]
Solution: The net rate of energy transfer between the two spheres is given by,
E = (T 4 −T04 )
Given that, T = 300 K , T0 = 200 K and σ = 5 .672 × 10 −8 M.K.S. units.

E = 5 .672 × 10 −8 [(300)4 − (200)4 ]
= 5 .672 × 10 −8 [(3 × 100)4 − (2 × 100)4 ]
= 5 .672 × 10 −8 × 108 × (81 − 16) = 5 .672 × 65
= 368.68 watts / m2 .
Example 4: The relative emittance of tungsten is approximately 0.35. A tungsten sphere of

surface area 10 −3 m2 is suspended inside a large evacuated enclosure whose walls are at
300 K. What power input is required to maintain the sphere at a temperature of 3000 K?
The conduction of heat along the support is negligible. [ σ = 5.672 × 10 −8 M.K.S. units ]
Solution: The radiant energy per second is given by,
E = σ Ae[T 4 − T04 ]
where A is the area of surface = 10 −3 m 2 , e is relative emittance = 0 .35
σ is constant = 5 .672 × 10 −8 M.K.S. units.
Also, given that, T = 3000 K and T0 = 300 K

227
The power input = radiant energy per second

= 5 .672 × 10 −8 × 10 −3 × 0 .35 [(3000)4 − (300)4 ]
= 5.672 × 10 −11 × 0.35 × 108 [810000 − 81]
= 1607. 85 watts.
4.4 Spectral Distribution of Black Body Radiation

A body whose absorptivity is unity for all wavelengths is called an ideal black body or we can say
that a body, which absorbs all the incident radiations completely irrespective of wavelength, falling on
it, is known as black body. Lamp black and Platinum black are the example of black body.
It is found, that, if the temperature of a body is raised, it emits the waves of shorter
wavelength (i.e., the colour of radiations changes). For example, the colour of blackened
platinum appears dull red at about 525°C, cherry red about 900°C, orange red at
1100°C, yellow at 1250°C and white S1
at about 1600°C. The distribution of
energy among the wavelength
(spectral distribution) emitted by
black body was investigated by
Lummer and Pringsheim in 1899.
They used an electrically heated M2
Fluorspar prism M1
chamber with a small aperture as the
black body whose temperature was
measured by a thermocouple. S2
The experimental arrangement is
Bolometer
shown in fig. 4.2. It consists of a carbon
tube heated electrically. The radiations
Fig. 4.2
from this tube (black body) are allowed
to be incident on a reflector mirror M1
through a slit S1. The parallel reflected beam is incident on a fluorspar prism P, placed on
the turn table of spectrometer. The dispersed beam is focussed on the bolometer with
the help of another concave mirror M2 . The bolometer is connected to a sensitive
galvanometer. The turn table is rotated slowly so that each part of the spectrum is
focussed successively on the bolometer and deflection of the galvanometer gives
corresponding spectral intensity ( Eλ ) of each spectrum line.
228
The wavelength at different portion of the 1646 K
spectrum was calculated by the formula

for the dispersion of the material of the
prism. By determining the intensity of
radiations for various wavelengths in the
Eλ 1468 K
whole thermal spectrum, a graph is drawn
between intensity ( Eλ ) and wavelength λ
1259 K
at different temperatures (Fig. 4.3)
1095 K
The important features of these curves are
as follows: 904 K
1. At a given temperature, the energy is 0.4 0.8

1 2 3 4 5 6
not uniformly distributed in the λ in microns
radiation spectrum of a hot body. (1 µ = 10-6metres)
Fig. 4.3
2. At a given temperature, the intensity
of radiations increases with increase of wavelength until its value becomes
maximum. With further increase in wave length, the intensity of heat radiations
decreases.
3. With increase in temperature, the wavelength of maximum energy (λ m) shifts
towards the shorter wavelengths. This is called Wien's displacement law.
According to it,
λ m × T = constant
It means that if temperature (T) is raised, the maximum energy will be radiated at
shorter wavelength.
4. The total energy of radiation for a given temperature is represented by the area
between the curve and the horizontal axis. It is found that the area is directly
proportional to the fourth power of the absolute temperature of the body, i.e.,
E ∝ T 4 (Stefan's law).
4.4.1 Explanation of Curves

The explanation of these curves can be given by some classical laws:
1. Wien's Displacement Law: In 1896, Wien worked on distribution of energy
among the various wavelengths. He deduced thermodymically that the product of
the wavelength corresponding to the maximum energy and absolute temperature is constant
i.e., λ m × T = constant. This is called Wien's displacement law. It also shows that with
increase in temperature, λ m decreases.
Wien also showed that the energy, Eλ at wavelength λ in the spectrum of black
body at absolute temperature, T is given by,
229
1
E= f (λT )
λ5
where f (λT ) is a function of the product (λT ).
In order to determine the form of the function f , Wien made following

assumptions:
(i) Every molecule in the radiator emits a radiation of single wavelength only,
depending upon the velocity of molecule.
(ii) Intensity of radiation is a function of the velocity of the molecule.
(iii) The energy Eλ , lying between the wavelength range λ and λ + d λ is proportional
to the number of vibrating molecules with their time periods corresponding to
wavelengths within this range. On these basis, Wien found that,
f (λT ) = Ae – ( a / λT )
where A and a are constants. Hence, the distribution formula becomes
E λdλ = Aλ−5 e −(a / λT)dλ
This formula agrees with the experimental result in the shorter wavelength region
only.
2. Rayleigh and Jeans Law: Rayleigh and Jeans considered the black body radiator
(cavity)full of electromagnetic waves of all wavelengths between 0 and ∞ . They
applied the principle of statistical mechanics and obtained the energy distribution
in the thermal spectrum as given by the formula,
8π kT
Eλ d λ = dλ
λ4
where k is the Boltzmann's constant.
This formula is based on the following assumptions:

(i) Energy is equally distributed among the various degrees of freedom.
(ii) Radiation from a black body radiator (cavity) has degrees of freedom
corresponding the frequencies of the possible standing waves in the cavity.
Rayleigh-Jean's law was found to agree with the experimental results in the
longer wavelength region only.
As we move towards shorter wavelength (i.e., towards ultraviolet), the predicted

energy would increase without limit, thus diverging greatly from experimental value.
This completely incorrect prediction is known as the ultraviolet catastrophe.
3. Planck's Law: In 1990, Planck's introduced the revolutionary idea that the
radiations from the black body are not continuous but emit in the form of energy
packets, called quanta or photon. The amount of energy associated with each
230
photon is hv, where v is the frequency of radiation and h is the Planck's constant.
On this basis, Planck deduced the formula for the energy distribution in the
thermal spectrum as given by,
8π hc
Eλ =
λ (e h c / λkT −1)
5
where c is the velocity of light k is Boltzmann's constant and T is absolute

temperature.
Planck's formula was found to agree with the experimental results at all wavelengths.
Example 5: Using Wien's displacement law, estimate the temperature of the sun. Given
°
that, λ m = 4900 A and Wien's constant = 0 . 292 cm − K.
[Meerut 2005]
Solution: For a black body radiation, the Wien's displacement law is
constant
λ m T = constant or T =
λm
For the Sun, it is given that. λ m = 4900Å =4900 × 10 –8 cm
and Wien constant = 0.292 cm-K
Hence, the temperature of the Sun.
0 .292
T= = 5959 K.
4900 × 10 −8
Example 6: A body at 1500 K emits the maximum energy at a wavelength of

° If the Sun emits maximum energy at wavelength
20000 A. 5500 A,° what would be the
temperature of the Sun.
Solution: As we have that Wien's displacement law,

λ m T = constant
or λ m ' T ' = λ m ' ' T ''
° °
Here, λ m' = 2000 A , T ' = 1500 K and λ m' ' = 5500 A ,
Putting the values, we get 20000 × 1500 = 5500 × T ''

20000 × 1500
or T '' = = 5454 K
5500
Example 7: Calculate the surface temperature of the sun and moon, given that,
°
λ m = 4753 A and 14 µ respectively. Where λ m is the wave length of maximum intensity
of emission. Given that: Wien's constant =0.2898×10 –2 mK
Solution: According to Wien's displacement law,
231
λ m × T = constant = 0 .2898 × 10 −2 mK
(i) For sun, λ m = 4753Å =4753 × 10 –8 cm
0 .2898 × 10 −2
∴ Ts = K = 6097 K
4753 × 10 −10
(ii) For moon, λ m = 14µ = 14 × 10 −6 m
0 .2898 × 10 −2
∴ Tm = 207 K
14 × 10 −6
4.5 Planck's Quantum Hypothesis

Wien displacement law and Rayleigh-Jean's law could not explain the entire shape of
the curves giving the energy distribution in black body radiation. In 1900, Planck,
introduced entirely new idea to explain the distribution of energy among the various
wavelengths of the black body (cavity) radiation. He assumed that the atoms of the walls
of the cavity radiator behave as oscillators, each with a characteristic frequency of oscillation.
These oscillators emits electromagnetic energy into the cavity and also absorbs the same
from it, and maintain an equilibrium state. Planck gave two revolutionary postulates
regarding these atomic oscillators.
1. The oscillator can have only one discrete energy,
ε = nhv
where v is frequency of the oscillator, h is Planck's constant and n is an integer
known as quantum number . It means that the oscillator can have only quantised
energies hv, 2 hv, 3 hv......... . nhv and not any energy in between.
2. The oscillators do not emit or absorb energy continuously but only in certain multiples of the
fundamental frequency of oscillators, while jumping from one state to another,
∆ ε = (∆n)hv, ∆n=1, 2 ,......
4.5.1 Average Energy of Planck's Oscillator

The relative probability that an oscillator has the energy hv at temperature T is given By
Boltzmann factor e −( hv / kT ). Now, let N0 , N1 , N2 .... N r be the number of oscillators
having the energies 0, hv, 2 hv...... rhv respectively. Then, the number of oscillators having
energy rhv will be,
N r = N0 e − ( rhv / kT )
The total energy of oscillator is given by,

ε = (N0 × 0) + (N1 × hv) + (N2 × 2 hv) + ........
= (N0 e − ( hv / kT ) × hv) + (N0 e − (2 hv / kT ) × 2 hv) + ........
232
= N0 e − ( hv / kT ) × hv [1 + 2 e − ( hv / kT ) + 3 e − (2 hv / kT ) + ........]
e − ( hv / kT ) hv
= N0 [Q1 + 2 x + 3 x2 + ... = 1 / (1 − x)2 ] ...(1)
(1 − e − hv / kT )2
The total number of oscillators is given by,

N = N0 + N1 + N2 + ......
= N0 + N0 e − ( hv / kT ) + N0 e − (2 hv / kT ) + ......
= N0 + (1 + e − ( hv / kT ) + e − (2 hv / kT ) + ......)
N0
N= ...(2)
− hv / kT
(1 − e )
Dividing equation (1) by equation (2), we obtain the average energy of an oscillator,
− hv / kT
ε e (hv) hv
ε= = =
N 1 − e − hv / kT (e hv / kT
− 1)
4.5.2 Planck's Radiation Formula

The energy density belonging to frequency range dν can be obtained by multiplying the
average energy of Planck's oscillator by the number of oscillators (resonator) per unit
volume in the frequency range v + dv i. e.,
8 π v2 hv
Ev dv = dv ...(3)
3 hv / kT
c (e − 1)
8 π v2
is the number of oscillators (electromagnetic standing waves) per unit volume in
c3
the frequency range v and v + dv.
Equation (3) can be written as
8 π h v3 dv
E v dv =
c3 (e hv /kT) − 1)
This is Planck's radiation law in terms of frequency v. To express this law in terms of
wavelength λ, we use,
v = (c / λ ) and dv = (c / λ2 ) dλ
8 π  c2  hc / λ c
∴ E λ dλ =   dλ
3  2  hc / λkT
c  λ  (e − 1) λ 2
8 π hc dλ
or E λ dλ = ...(4)
5 hc / λkT)
λ (e − 1)
This is the Planck's radiation law in terms of wavelength.
233
4.5.3 Wien's Law and Rayleigh-Jeans Law are Special Case of

Planck's Law
Planck's law is found to be in complete agreement with experimental result for the
entire wavelength range at all temperatures. We can show that Wien's law and
Rayleigh-Jeans law are special cases of Planck's law.
1. When λ is very small, then e( hc / λkT ) >>1 i.e., 1 can be neglected in comparison of
e( hc / λkT ), hence from equation (4), we get

8 π hc
Eλ d λ = d λ e − hc / λkT
λ5
Putting A = 8πhc and B = (hc / k)
A − B / λT
Eλ d λ = e dλ ...(5)
λ5
This is Wien's law which agrees with experimental values at shorter wavelengths.
hc
2. When λ is very large, then e( hc / λkT ) ≈ 1 + , hence equation (4) can be written as,
λ kT
8 π hc dλ 8 π kT
Eλ d λ = = dλ ...(6)
5
λ  hc  λ4
1 + − 1
 λ kT 
This is Rayleigh-Jeans law which agrees with experimental values at longer

wavelengths.
4.6 Ultra Violet Catastrophe

The concept of UV catastrophe is an important conclusion of Raleighley Jean's law of
energy distribution. It means that if the thermal radiation (low freq)or large wavelength
be introduced into an enclosure it will convert itself into shorter wavelength or higher
frequency radiation i.e., into red, yellow etc to ultraviolet, x-ray and γ-ray radiation.
This is so because the electromagnetic waves inside the enclosure with perfectly
reflecting walls will suffer multiple reflection at walls and give rise to standing or
stationary waves of different radiation. The possible number of different waves
(modes of vibration) will be larger if λ be small. In this way, all the radiation
emanating from the interior of a furnace would be in the form of very small
wavelength (very high frequency) radiation. This terrifying prospect is called
''Ultraviolet Catastrophe" but such results deduced from Rayleigh's law are against
experimental evidences and absurd also.
234
Problem 1: Deduce the temperature at which a black body losses thermal energy at a
rate of 1 watt/ cm2 [σ = 56 × 10 − 5 erg – cm2 − sec − 1 ° C4 ].
Solution: The energy radiated per second per unit area is given by,
E = σ T4
1 /4
 E
or T = 
 σ
Here, E = 1 watt / cm 2 = 107 erg − sec −1 / cm 2 and
σ = 5.6 × 10 − 5 erg − cm 2 − sec −1 K 4 ] [Q per º C = per K]

1 /4
 107 
T =  = [01785
. × 1012 ]1 /4 = 650 K
−5
5.6 × 10 
Problem 2: Two bodies A and B at temperature 427 °C. and 227 °C. respectively are kept
in an evacuated vessel at 27 °C. Compare the rates at which heat is lost from A to B.
Solution: Let E1 and E2 represent the rates of net loss of heat per second per unit area
of the bodies A and B respectively. Then, according to Stefan Boltzmann's law,
E = σ (T 4 − T04 )
For body A, T = 427 + 273 = 700K and T0 = 300K
∴ E1 = σ [(700)4 − (300)4 ] ...(1)
For body B, T = 227 + 273 = 500K and T0 = 300K
∴ E2 = σ [(500)4 − (300)4 ] ...(2)
Dividing equation (1) and (2), we have
E1 (700)4 − (300)4
= = 4.265
E2 (500)4 − (300)4
Problem 3: A blackened platinum sphere of radius 3 cm is suspended in an exhausted

chamber. The walls of the chamber are maintained at 127 °C. At what rate, energy
must be supplied to the sphere so as to keep its temperature constant at 2 27 °C. Given
that: σ = 5.735 × 10 –12 in C.G.S. units
Solution: The energy lost due to radiation must be equal to the energy supplied.
The energy lost per second by the sphere, of surface area A, is given by,
E = σ A (T 4 − T04 )
235
Given that, σ = 5 .735 × 10 −12 in C.G.S units, T = 273 + 227 = 500 K

T0 = 127 + 273 = 400 K
and the area of the sphere, A = 4 π r 2 = 4 × 3 .14 × 32 = 113 .1 cm 2 .
E = 5 .735 × 10 −12 × 113 .1[(500)4 − (400)4 ]
= 5 .735 × 10 −12 × 113 .1 × 108 (625 − 256)
= 5 .735 × 113 .1 × 10 − 4 × 369

=23.93 ergs
So, energy must be supplied to the sphere to keep its temperature constant is 23.93
ergs.
Problem 4: Luminosity of regal star in iron constellation is 17000 times that of our sun. If
the surface temperature of the sun is 6000 K. Calculate the temperature of the star.
Solution: The energy radiated per second per unit area from the surface of a black
body at absolute temperature T is given by,
E = σ (T 4 − T04 )
where σ is Stefan's constant and T0 is temperature of the surrounding.
If the temperature T0 << T , then T04 can be neglected in comparison of T 4 , we have
E = σ T4
Let E1 and E2 be the luminosities of star and the sun respectively, then
E1 T4
= 1
E2 T 2
2
where T1 and T2 are the absolute temperatures of star and sun respectively.
Given that,
E1 / E2 = 17000 and T2 = 6000 °K
E1 T14
Then = 17000 =
E2 (6000)4
or T14 = (6000)4 (17000)
T1 = 6000(17000)1 /4 = 68512 K
Problem 5: Calculate the energy radiated per minute from the filament of an incandescent
lamp at 2000 K if the surface area is 5 × 10 − 5 m 2 and its relative emission e is 0.85.
Given that, σ = 5.7 × 10 − 8 M.K.S. units
Solution: According the Stefan's law, the energy radiated per second per unit area,
4
E = e σ (T 4 − T0 ) = e σT 4 if T >>> T0
236
Total energy radiated by the per second

= σ eT 4 × surface area
The total energy radiated by the body per minute
= σ eT 4 × surface area × 60
Here, σ = 5.7 × 10 − 8 M.K.S. units, e = 0.85, T = 2000 K and the surface area = 5 × 10 − 5 m 2
= 5 .7 × 10 − 8 × 0 .85 × (2000)4 × 5 × 10 − 5 × 60
= 2325.6 Joule
Problem 6: The operating temperature of the tungsten filament of a bulb is 3000 K. Its
surface area is 0 .25 cm 2 and the emittance is 0.35. Find the wattage of the bulb.
Given that, σ = 5.67 × 10 − 5erg – cm2 −sec − 1 °C- 4
Solution: The energy emitted per second per unit area from the filament (black body)
is given by,
E = σT 4
If emittance is e and surface area is A then, total radiated energy per second (power) is
given by,
Power, P = e σT 4 A
Here, e = 0 .35, σ = 5 .67 × 10 − 5 erg − cm − 2 − sec −1 ° K − 4 , [per °C = per K]
2
T = 3000 K and A = 0 .25 cm
P = 0 .35 × 5 .67 × 10 − 5 × (3000)4 × 0 .25
= 40 .2 × 107 erg /sec = 40 .2 Joule / sec ≈ 40 watt
. × 10 5 calories per hour through an opening of

Problem 7: An iron furnace radiates 153
cross section 10 − 4 m 2 . If the relative emittance of the furnace is 0.80, calculate the
. × 10 − 8 cal / m2 − s –1 − K4 .
temperature of the furnace. Given that, σ = 136
Solution: The energy radiated per second per unit area from a body is given by,
E = σ (T 4 − T04 )
then E = σ eT 4 [If T >> T0 and emittance of the body is e]
Given that, iron furnace radiates 1.53 × 105 calories per hour through an opening of
cross section 10 − 4 m 2 .
1. 53 × 105
i.e., E= calories per unit area per sec.
3600 × 10 − 4
237
1.53 × 105
∴ = 1.36 × 10 − 8 × 0 .80 × T 4
3600 × 10 − 4
1.53 × 105
or T4 = = 39 × 1012
3600 × 1.36 × 10 − 8 × 0 .80 × 10 − 4
or T = 2500 K
Problem 8: A black body is placed in an evacuated enclosure whose walls are blackened
and kept at constant temperature of 300 K. Compare the net amount of heat gained or
lost by the body when its temperature is (i) 600 K (ii) 100 K.
Solution: The net loss of heat energy per unit surface area from a black is given by,
E = σ (T 4 − T04 )
(i) Here, T1 = 600 K , T0 = 300 K
∴ E1 = σ [(600)4 − (300)4 ] = σ (1215 × 108 )
(ii) T1 = 100 K , T0 = 300 K
E2 = σ [(100)4 − (300)4 ]
It is negative, so it is gain in heat
∴ gain in heat E2 = σ [(300)4 − (100)4 ] = σ (80 × 108 )
E1 1215 243
on. comparing i.e., = =
E2 80 16
Problem 9: Calculate the maximum amount of energy which may be lost per second by
radiation from a sphere of 10 cm diameter at a temperature of 227 °C , when placed in
an enclosure at a temperature of 27 °C . Stefan's constant, σ = 5.7 × 10 − 12 watt / cm2 °C 4 .
Solution: The maximum amount of heat energy lost per second from surface area A of
a black body is given by,
E = σ (T 4 − T04 ). A ...(1)
−12
Here, σ = 5 .7 × 10 watt / cm 2 °C4 = 5 .7 × 10 −12 watt / cm 2 °K
T = 227 + 273 = 500 K , T0 = 27 + 273 = 300 K
and A = 4 π r 2 = 4 × 3 .14 × (5)2 × = 314 cm 2

E = 5 .7 × 10 −12 [(500)4 − (300)4 ] × 314
= 5 .7 × 10 −12 [544 × 108 ] × 314

= 97.36 Joule/sec
97.36
= = 23.29 cal /sec
4 .18
238
Problem 10: Estimate, the temperature at which a body would appear red and blue.
°
The corresponding wavelengths of maximum energy radiation are λ m ≈ 7500 A and
°
5000 A respectively, Given, Wien's constant = 0.3 cm-K.
Solution: From Wien's law,

Thus, for red appearance, the required temperature will be,
constant 0 .3 cm − K
T= = = 4000 K
λ mr 7500 × 10 − 8 cm
Similarly, for blue appearance, the temperature will be,

constant 0 .3 cm − K
T= = = 6000 K
λ mb 5000 × 10 − 8 cm
Problem 11: What is the wavelength of the maximum intensity radiation, radiated
from a source having temperature 3000 K. The Wien's constant is 0 .3 × 10 − 2 m-K.
Solution: Form Wien's law, λ m × T = constant

constant
or λm =
T
Here, constant = 0 .3 × 10 − 2 m-K and T = 3000 K
0 .3 × 10 − 2 m − K
∴ λm =
3000 K
°
= 1 × 10 − 6 m = 10000 A
hc
Problem 12: Wien's law states that, λ m T = = constant. Given that h = 6.63 ×
5k
10 − 34 J − s, c = 3.0 × 10 8 m / sec. k = 1.38 × 10 − 23 J /K. Find the value of constant.
°
Abbol's measurement shows that λ m for the solar radiation is 4753 A, find the temperature
of the surface of the photosphere of the sun.
hc
Solution: From Wien's law, λ m = constant
5k

6 .63 × 10 − 34 J − s × 3 × 108 m /sec
Wien's constant = = 2.88 × 10 − 3 m − K
− 23
5 × 1.38 × 10 J/K
°
For the solar radiation, λ m = 4753 A = 4753 × 10 −10 m
Again from Wien's law, λ m × T = constant
−3
constant 2.88 × 10 m − K
or T= = = 6059 K
λm 4753 × 10 −10
239
Exercise
1. Show that radiation energy is dependent purely on temperature. Also show that
radiation inside an enclosure is identical with black body radiation at the same
temperature.
2. Show that radiation exerts pressure. Also show that the Pressure of diffuse
Radiation is equal to one third of its energy density.
3. State Stefan's law and Stefan-Boltzmann law of black body radiation and prove
Stefan's law from the principle of thermodynamics.
[Meerut 2009B, 09, 08, 06, 05]
4. State Stefan's law for black body radiation. Prove it from the principle of
thermodynamics.
5. Describe the spectral distribution of black body radiation. How it has been
explained by Wien's displacement law, Rayleigh-Jeans law and Planck's law ?
[Meerut 2012, 11, 03, 02, 01]
6. State Wien's Displacement law of black body radiation. Prove it on the basis of
thermodynamic principles. [Meerut 2009 B]
7. Explain the energy distribution in the spectrum of black body radiation. Give the
important information obtained from Eλ − λ graph. [Meerut 2011]
8. Give Planck's quantum hypothesis and postulates of spectral distribution of

energy. Deduce an expression for the average energy of a Planck's oscillator. Also
derive Planck's radiation formula for black body radiation and show that Wien's
law and Rayleigh-Jean's law are special cases of Planck's law.
[Meerut 2012, 09B, 08B, 08, 07B, 07, 06, 05, 04, 03, 02, 01]
9. What is Planck's law of radiation ? Derive expression for it. Show that
Rayleigh-Jeans formula and Wien's formula are its special cases. [Meerut 2005]
10. Derive Planck's formula for the spectral distribution of energy in the black body
radiation. Show that the Rayleigh Jean's formula and Wien's formula are special
cases of Planck's formula. [Meerut 2006, 03, 02, 01]
11. Deduce Wien's displacement law and Stefan's law from Plack's radiation formula:
8π hc dλ
uλ dλ =
5 hc / λkT
λ (e − 1)
12. Define Ultra Violet Catastrophe. [Meerut 2010]
240

1. Give some properties of thermal radiation.
2. Write the analogy between black body radiation and a perfect gas.
3. Define a Perfectly black body. How it can be realised in practice ?
[Meerut 2005B, 05, 03]
4. A red and green glass piece are placed in a uniformly heated enclosure. What
colour will appear when seen through a tiny hole in the enclosure ?
5. An earthen jug is made red hot in a furnace. When it is removed from the
furnace, the hole in the mouth of the jug glow brightest. Explain Why ?
6. State Stefan – Boltzmann law of radiation. Show that for small differences of
temperature Newton law of cooling is just an approximation of above law.
7. Deduce Wien's displacement law from Planck's radiation formula. [Meerut 2010, 08B]
8. Deduce Stefan's Law from Planck's radiation formula. [Meerut 2010, 09]
9. The black body spectral energy distribution of radiation from moon shows two
°
wavelengths maxima at 14µ and 5000 A. What is the significance of such an
observation ? Calculate the corresponding temperature. Given, Wien's constant = 0.3

cm-K.
10. At what rate will energy be emitted from a bulb whose filament has a
temperature of 3600 K. Given that, at 1800 K, the energy is emitted at the rate
of 16 watt ?
11. Deduce the frequency corresponding to the maximum energy density in the
radiation emitted from a black body at temperature 1000 K. Given that,
k = 1.38 × 10 − 23 J / K and h = 6.6 × 10 − 34 Joule-sec.

1. Define a black body. [Meerut 2008B]
2. State Stefan – Boltzmann law. [Meerut 2009, 09, 08B, 06]
3. State Wien's displacement law. [Meerut 2009]
4. Define quanta.
5. Two iron pieces are heated in a furnace to the same temperature. One piece is then
taken out.Which piece will appear brighter just at this instant ?
6. Write Planck's radiation law with the meaning of the symbols used.
[Meerut 2012]
241

1. According to provost theory of exchange to explain the phenomenon of
radiation, the rate of radiation from a body depends on:
(a) The nature of radiating surface
(b) The temperature of the radiating body
(c) Both (a) and (b)
2. The pressure of diffuse radiation is equal to:

(a) One third of radiated energy density
(b) Two third of radiated energy density
(c) Four third of radiated energy density
3. According to Stefan's law the total amount of heat radiated by a perfect black
body per second per unit area is directly proportional to the:
(a) Square of its absolute temperature
(b) Fourth power of its absolute temperature
(c) Its absolute temperature
4. According to Stefan-Boltzmann's law, the net rate of loss of heat energy per
second per unit area of the surface of a black body at temperature T surrounded
by enclosure at a temperature T0 is given by:
(a) E = σ (T 4 − T04 ) (b) E = σ (T04 − T 4 )
T 4 − T04
(c) E = (d) None
σ
where σ is a constant.
5. A body whose absorptivity is unity for all wavelengths is called:

(a) Yellow body (b) White body
(c) Black body (d) Blue body
6. Wien's displacement law states that:

(a) λ m × T = constant (b) (λ m / T ) = constant
(c) (T / λ m) = constant (d) None
242
7. For giving energy distribution in thermal spectrum, Rayleigh and Jeans

considered:
(a) Dynamical mechanics (b) Statistical mechanics
(c) Quantum mechanics (d) All above
8. Wien's law is a special case of Planck's law for:

(a) Smaller wavelengths (b) Longer wavelengths
(c) All wavelengths (d) None of the above
9. Rayleigh-Jeans law is a special case of Planck's law for:

(a) Smaller wave lengths (b) Longer wave lengths
(c) All wavelengths (d) None of the above
10. A polished metallic ball with a black spot on it is heated to a high temperature and
taken into dark, then:
(a) The spot will appear brighter than the ball
(b) The spot will appear darker than the ball
(c) Both will appear equally bright

1. The radiation of energy form a body depends on its.................... .
2. The pressure of diffuse radiation is equal to the .................... of its energy density.
3. According to Stefan's law, E ∝.................... .
4. According to Wien's law λ m × T = .................... .
5. Wien's law agrees with the experimental results in the .................... wavelength
region only.
6. Rayleigh Jean's law agrees with the experimental results in the ....................
wavelength.
7. Planck assumed that radiated energy is in the form of .................... .
8. At low temperature the fall in the value of .................... for the gases is explained by
quantum theory.
9. At very low temperature the value of C v for all gases is .................... calorie.
(F) True/False
1. The rate of loss of heat by a body through radiation depends on the temperature
of the body.
2. The pressure of diffuse radiation is equal to two third of its energy density.
243
3. According to Stefan's law, E ∝ T 3 . Where E and T represent their usual

meanings.
4. According to Stefan-Boltzmann's law. E = σ (T 4 − T04 ), where all symbols
represent their usual meanings.
5. Energy emitted by a hot body is distributed equally among different
wavelengths.
6. The wavelength for which the energy of radiation emitted by the sun is
maximum, is less than the corresponding wavelength for the moon.
7. A black body is a poorer radiator of heat.
Answers
(Hints & Solutions)
6. Stefan-Boltzmann Law: According to Stefan's-Boltzmann law, the radiant
energy (heat) per second per unit area by a black body at absolute temperature
T surrounded by an enclosure at temperature T0 is given by,
E = σ (T 4 – T04 )
E = σ (T 2 – T02 ) (T 2 + T02 ) = σ (T – T0 ) (T + T0 ) (T 2 + T02 )
= σ (T – T0 ) (T 3 + TT02 + T0 T 2 + T03 )
If the temperature difference (T – T0 ) is small i.e., T is nearly equal to T0 , then
the above expression can be written approximately as,

= σ (T – T0 ) 4T03 )
= K(T – T0 )
where K = 4 σ T03 (T0 is assumed to be constant)
∴ E ∝ (T − T0 )
Thus, when the temperature of a body is slightly higher than the temperature of
its surroundings, the heat of lost per second by the body is proportional to the
difference in temperature of the body and that of the surroundings. It is
Newton's law of cooling.
7. Wien's displacement law from Planck's formula:
The Planck's radiation formula is,
244
8 π hc dλ
Eλ d λ =
5 hc / λ kT
λ (e − 1)
or Eλ = 8 π hc (λ− 5 ) (e hc / λkT − 1)−1

Now, we want to find the wavelength corresponding to the maximum energy i.e.,
the wavelength at which the spectral radiancy is maximum. For that, (dEλ / dλ )
must be zero.
  −hc 
So, 8 π h c − 5 (λ− 6 ) (e hc / λkT − 1) + (λ− 5 ) (− 1) (e hc / λkT − 1) −2 e hc / λkT .    =0
  λ2 k T  
 
5 h c hc / λkT hc / λkT
or = e (e − 1)−1
λ λ2 k T
hc e hc / λkT
or 5=
λ k T (e hc / λkT − 1)
For simplifying we put

hc / λ kT = x, then we get
ex x
5=x =
(e − 1) 1 − e − x
x
or ( x / 5) = 1 − e − x
x
or + e − x =1
5
This equation has a single root given by x = 4.965, and therefore x must be a
constant
hc
So, = 4.965
λ kT
Therefore, the wavelength corresponding to maximum energy (λ m) is given by,
hc
λm T= = constant
4.965 K
It is Wien's displacement law.
8. The Planck's radiation formula is,

8 π hc dλ
Eλ d λ =
5 hc / λkT
λ (e − 1)
In terms of frequency (v), the formula can be written as,
8 πh v3 d v
Ev d v =
c3 (e hv / kT − 1)
The total radiancy Ev over all frequencies is,
∞ ∞ ∞
8π h v3 d v 8π h v3 dv
E=
∫ Ev dv =
∫ c3 (e hv / kT − 1)
=
c3 ∫ (ehv / kT −1)
0 0 0
hv kT kT
Let = x or v = x and dv = dx then,
kT h h
245
∞ 3
8 π h k4 T 4 x dx
E=
c 3 h4 ∫ (e x −1)
0
∞ 3 4
x dx π
We have that,
∫ (e x −1) = 15
0
8 π 5 k4 T 4
Thus, E=
15 h3 c3
 8 π 5 k4 
or E = σ T4 where = = σ (a universal constant)
3 3
 15 h c 
This is Stefan's law.
9. The moon radiates two types of radiation (i) own radiation (ii) sun's radiation
reflected by moon's disc. So, the wavelength maximum at 14µ is due to moon's
own radiation, while the wavelength maximum at 5000 Å is due to the solar
radiation which is reflected from moon's disc.
Now, according to Wien's law,
constant
∴ Moon's temperature, Tm =
λm
Here, λ m =14µ and Wien's constant = 0.3 cm-K
0 .3 cm − K
∴ Tm = [Q1µ = 10 − 4 cm]
14 × 10 − 4 cm
= 214 K.
constant
For sun's temperature, TS =
λm
°
Here λ m = 5000 A
0 .3 × cm − K
∴ TS = = 6000 K
5000 × 10 − 8
10. According to Stefan's law, the rate of energy radiated from a black body at a
given temperature is,
E ∝ T4
E1 T4
or = 1
E2 T 4
2
Here, E1 = 16 watt, T1 = 1800 K and T2 = 3600 K
16 (1800)4 1 (1800)2
∴ = =
E2 (3600)4 16 (1800)2
or E2 = 256 watt.
246
11. hc
Wien's law, λ m × T = constant =
5k
c 5 kT
The frequency corresponding to λ m , vm = =
λm h
Here, k = 1.38 × 10 − 23 J / K , T = 1000 K , h = 6.6 × 10 − 34 Joule − sec
5 × 1.38 × 10 − 23 × 1000
Putting the values, we get vm = = 1.045 × 1014 /sec
6 .6 × 10 − 34

2. If a perfectly black body at temperature T is enclosed by a surrounding at a
temperature T0 , the net rate of loss of heat energy per second per unit area is
given by, E ∝ (T 4 − T04 )
or E = σ (T 4 − T04 )
where σ is universal constant.
3. Wien thermodynamically deduced that the product of the wavelength (λ m)

corresponding to maximum energy and absolute temperature (T) is a constant i.e.,
6. 8πhc dλ
Eλ dλ =
5 hc / λkT
λ (e – 1)
where Eλ is the energy in the wavelength range λ + dλ λ is the wave length, h

Planck's constant c is the velocity of light, k Boltzmann constant and T is
absolute temperature.

1. (c) 2. (a) 3. (b) 4. (a) 5. (c) 6. (a) 7. (b) 8. (a) 9. (b)
10 (a)

1. absolute temperature 2. one third 3. T4 4. constant 5. shorter
6. longer 7. quanta 8. CV 9. 2:98
(F) True/False
1. (T) 2. (F) 3. (F) 4. (T) 5. (F) 6. (T) 7. (F)
mmm

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TEXT BOOK

B.Sc. First Year Second Paper

As per U.P. UNIFIED Syllabus

Garima Jain Rekha Sharma

KRISHNA Prakashan Media (P) Ltd.

470 Kinetic Theory and Thermodynamics (E) Binder2.pdf 1 7/30/2018 3:47:50 PM

470 Kinetic Theory and Thermodynamics (E) Binder2.pdf 3 7/30/2018 3:47:50 PM

470 Kinetic Theory and Thermodynamics (E) Binder2.pdf 5 7/30/2018 3:47:51 PM

470 Kinetic Theory and Thermodynamics (E) Binder2.pdf 6 7/30/2018 3:47:51 PM

470 Kinetic Theory and Thermodynamics (E) Binder2.pdf 7 7/30/2018 3:47:51 PM

1.2 Kinetic Theory of Gases 05

1.3 Deduction of Gas Laws from Kinetic Theory 08

1.4 Interpretation of Temperature on the Basis of Kinetic Theory 11

1.5 Root Mean Square Speed of Molecules 13

1.6 Brownian Motion 17

1.7 Estimation of Avogadro's Number 18

1.8 Degrees of Freedom of a Particle or System 19

1.9 Law of Equipartition of Energy 21

1.10 Specific Heat of Gases 23

1.11 Ratio of Specific Heats of an Ideal Gas 24

1.12 Ratio of Molecular Specific Heats for Monoatomic,

1.13 Adiabatic Expansion of an Ideal Gas 27

1.14 Application of Kinetic Theory to Atmospheric Physics 28

470 Kinetic Theory and Thermodynamics (E) Binder2.pdf 8 7/30/2018 3:47:51 PM

1.15 Van der Waal's Equation of State for Real Gases 29

1.16 Critical Constants of a Gas 32

1.17 Joule's Law 36

1.18 Joule-Thomson (Kelvin) Effect 38

1.19 Joule Thomson Expansion for an Ideal Gas 40

1.20 Joule-Thomson (Kelvin) Effect 42

2.2 Boyle Temperature 66

2.3 Principle of Regenerative Cooling 67

2.4 Principle of Liquefaction of Hydrogen 68

2.5 Liquefaction of Helium 69

470 Kinetic Theory and Thermodynamics (E) Binder2.pdf 9 7/30/2018 3:47:51 PM

2.8 Molecular Collision 72

2.9 Expression for Mean Free Path 73

2.10 Transport Phenomena in Gases 75

2.11 Transport of Mass 76

2.12 Transport of Momentum 79

2.13 Transport of Energy 82

2.14 Relation between Thermal Conductivity and Viscosity of a Gas 84

3.2 Macroscopic System and Microscopic System 97

3.4 Thermodynamic System 99

3.5 p –V or Indicator Diagram 100

3.7 First Law of Thermodynamics 106

3.8 Internal Energy of a System 111

3.9 Reversible Process 112

470 Kinetic Theory and Thermodynamics (E) Binder2.pdf 10 7/30/2018 3:47:51 PM

3.10 Carnot's Cycle 112

3.11 Carnot's Theorem 118

3.12 Second Law of Thermodynamics 120

3.13 Internal Combustion Engine 121

3.14 Entropy 123

3.15 Change of Entropy in Reversible Process 125

3.17 Absolute or Kelvin's or Thermodynamic Scale of Temperature 129

3.18 Thermodynamic Scale and Perfect Gas Scale 132

3.19 Practical Realization of Absolute Scale 133

3.20 Extensive and Intensive Variables 134

3.21 Maxwell's General Thermodynamic Relations 134

3.22 Heat Transfer in Isothermal Compression of a Liquid 137

3.24 Temperature Change in Adiabatic Compression of a Liquid 139