BS318 PHY-E

B.Sc.

SECOND YEAR SEMESTER - 3

PHYSICS
COURSE - 3: THERMODYNAMICS

“We may forgo material benefits of civilization, but we cannot

forgo our right and opportunity to reap the benefits of the
highest education to the fullest extent…”
Dr.B.R.Ambedkar

Dr. B.R. AMBEDKAR OPEN UNIVERSITY

HYDERABAD
2018
 COURSE TEAM
Course Development Team (OLD) Course Development Team
(CBCS)
Editor
Editor
Prof. K Rama Reddy
Prof. G. Pushpa Chakrapani
Associate Editors
Writers
Dr. K. Gnana Prasuna
Prof. Gnana Prasuna
Writers
Prof. G. Pushpa Chakrapani
Prof. K. Mutha Reddy
Dr. M. Purnanandam
Dr. K. Narsimha Reddy
Course Coordinator
Dr. V. Rama Murthy
Mrs. U. Vijaya Ushasree
Dr. D V N Sharma
Cover Design
Dr. K. V. Siva Kumar
G. V. Swamy
Dr. K. Somaiah

First Edition : 2018

(c) 2018, Dr. B.R. Ambedkar Open University, Hyderabad, A.P.

All rights reserved. No part of this book may be reproduced in any form without the permission
in writing from the University.

The text forms part of Dr. B.R.Ambedkar Open University Programme.

Further information on Dr. B.R.Ambedkar Open University courses may be obtained from
the Director (Academic), Dr. B.R.Ambedkar Open University, Road No. 46, Prof. G. Ram
Reddy Marg, Jubilee Hills, Hyderabad - 500033.

Web: www.braou.ac.in

E-mail: info@braou.ac.in

Printed on behalf of Dr. B.R.Ambedkar Open University, Hyderabad by the Registrar.

Lr. No. _____________________________________________________________

Printed at : ___________________________________________________________

II
 PREFACE

This book is for the first semester of 3 years B.Sc. degree course offered by
Dr. B. R. Ambedkar Open University. It deals with the topics Thermodynamics. These topics
cover the core area of the subjects to be studied in the third semester of the three year degree
corse in Science. The syllabus is divided into blocks, for sake of convenience and ecah block
comprises a number of units. Each unit generally covers a specific area of teh subject. The
units are prepared by experts in accordance with a format so designed as to enable the students
read and understand them without much difficulty. Each unit begins with a statement of its
objectives to be achieved after going through the unit. There are in between some questions
under the name check your progresses to assess the learner’s understanding of the subject.
The technical terms with which the student may not be familiar are given at the end of each
block under the head Glossary. Model examination questions are also given at the end of each
unit.

The university hopes this course material will help the students to get acquainted with
the concepts and principles of physics in general and thermodynamics in particular.

III
 CONTENTS

BLOCK/UNIT TITLE PAGE

Block-I: Laws of Thermodynamics - 1 1

Unit - 1 : Kinetic Theory of Gases 2-29

Unit - 2: Zeroth Law and First Law of Thermodynamics 30-39

Unit - 3: Reversible and Irreversible Processes 40-45

Unit - 4: Carnot’s Engine 46-58

Block-II: Laws of Thermodynamics - 2 59

Unit - 5: Second Law of Thermodynamics 60-68

Unit - 6: Entropy 69-81

Block-III: Thermodynamics Potentials 82

Unit - 7: Thermodynamic Potentials 83-89

Unit - 8: Maxwell’s Thermodynamic Equations & Applications 90-97

Block-IV: Quantum Thoery of Radiation 98

Unit - 9: Low Temperature Physics 99-115

Unit - 10: Applications of Low Temperature Physics 116-127

Unit - 11: Block Body Radiation (Classical Concepts) 128-139

Unit - 12: Block Body Radiation (Quantum Concepts) 140-155

Model Examination Question Paper 156-159

IV
 BLOCK - I

LAWS OF THERMODYNAMICS - 1
This block deals with thermodynamics-1. In this block learner are exposed to know
the kinetic theory of gases. Also they understand the zeroth law & first law of of
thermodynamics. They also learn about reversible & irreversible processes, Carnot’s cycle
and Carnot’s theorem.

In this block contains the following units.

Unit - 1: Kinetic Theory of Gases

Unit - 2: Zeroth Law and First Law of Thermodynamics

Unit - 3: Reversible and Irreversible Processes

Unit - 4: Carnot’s Engine

1
UNIT 1 : KINETIC THEORY OF GASES
Contents

1.0 Objectives

1.1 Introduction

1.2 Assumptions of Kinetic Theory of Gases

1.3 Mean Free path

1.4 Graphical Representation of Velocity Distribution of Gases

1.5 Maxwell’ s Law of Distribution of Molecular Speeds

1.6 Transport Phenomena

1.6.1 Viscosity of Gases

a) Define of Visosity

b) Equation for Coefficient of Viscosity (  )

1.6.2 Thermal conductivity of Gases

1.6.3 Diffusion of gases

1.7 Check Your Progress - Answers

1.8 Summary

1.9 Model Examination Questions

1.10 Books for Further Reading

1.0 OBJECTIVES

After going through this unit, you will be able to

 Define Mean free path.

 Explain the distribution of molecular speeds of a gas.

 Describe the transport phenomenon of gases.

Further with help of transport phenomenon you will be able to describe viscosity, thermal
conductivity and diffusion.

2
1.1 INTRODUCTION

With the advancement of experimental equipment or techniques it became possible to

acheive low temperatures and high pressures. Hence there is a need to make necessary changes
in theory. To explain the behaviour of perfect gases kinetic theory of gases was developed by
Maxwell & Clausius and others. Gases are made up of molecules. The molecules are considered
to be rigid, perfectly elastic and identical in all aspects. Molecules move in all directions with all
possible speeds. During their motion molecules collide with each other and with the walls of
vessel in which they are kept. The inter molecular forces between the molecules are neglected.
There will be no loss of kinetic energy during collision are perfectly elastic. Only a change in
momentum occurs. The molecules thus exert pressure on the walls. Between two successive
collisions, a molecule moves in a straight line. The distance is called the free path of the molecule.
Between two collisions the average distance travelled by a molecule will be its mean free path.
Molecule takes more time to cover mean free path than the time spent in a collision, which is
negligible.

1.2 ASSUMPTION OF KINETIC THEORY OF GASES

Let us consider the following before actually writing the assumptions.

The pressure exerted by the gas according to the kinetic theory is given by

1
mn v 2
1M 2 1 2
P 3  v  v ... 1.1
v 3V 3

Where V is the volume of the container, n is number of molecules, each of mass m and
M
mn = M = mass of the gas, is the density of  of the gas. v 2 is the mean square speed of
V
the molecules.

v12  v 22  ...  v n2
v2  ... 1.2
n

We can write equation 1.1 as

2 1 2
P . v
3 2

2
 kinetic energy of molecule ... 1.3
3

3
 Equation 1.3 shows that the pressure is two thirds of the total translational kinetic
energy of the molecules per unit volume.

Kinetic energy of translatory molecule of molecules of an ideal gas is directly proportional

to its absolute temperature. On this assumption the concept of temperature was introduced into
the kinetic theory on this basis we can show

1 3
mv 2  kT .. 1.4
2 2

here k = Boltzmann’s constant (1.38 1023 Jmol1kg1 ).

R
k . R being universal gas constant (8.314 J mol K-1) and N is Avagadro’s number..
N

3
Hence the mean kinetic energy of translation per molecule of a perfect gas is kT
2

If we put T = 0 in the equation 1.4

v2  0

We can infer that the absolute temperature is the temperature at which the molecules
ceases to move. This is not true, as the molecules do have some energy known as zero point
energy according to quantum mechanics.

Consider a dynamical system having a large number of particles. The total inter molecular
energy of the system will be distributed equally among its various degrees of freedom on the
basis of law of equitation of energy. The average kinetic energy of the molecule in each translation
1
degree of freedom is kT . k is Boltzmann’s constant and T is the absolute temperature.
2

We know that molecules of gas will be in random motion and collide with each other
and with the walls of the containing vessel. Hence there will be continuous change in magnitude
and direction of their velocities. So the velocities of the molecules of the gas vary from zero to
very high value. But the kinetic energy of the molecules remains the same at the same temperature.

The average velocity of the gas molecules was analysed by Maxwell. He used statistical
method to estimate the velocities. He assumed that

1. The number of molecules in a certain volume of a gas is very large. The velocity of
these molecules can be from zero to very high value.

2. Density will be same at every part of the volume of the gas at all times.

4
3. Although the velocity of individual molecules may change continuously but in equilibrium
and at a fixed temperature the number of molecules having certain range of velocity is
constant.

4. The components of the velocity of a molecule in three mutually perpendicular directions

are considered to be independent of each other.

5. Every segment in the volume of the gas can have molecules with all possible velocities
with the help of Maxwell law of velocity distribution, the number of molecules in some
velocity range can be determined.

1.3 MEAN FREE PATH

Molecules of a gas move continuously with large velocities according to kinetic theory
of gases. They collide with each other. At each collision the speed and direction of the molecules
changes. The molecule moves in a straight line between two successive collisions. This distance
is called free path. Let a, b, c, d be the free paths. The average distance  travelled between
two collisions is

a  b  c  d  ...

n

Where n is the number of collisions suffered by the molecule and  is called as mean
free path.

We can define mean free path as the average distance travelled by a molecule between
two successive collisions.

Check Your Progress:

Note: (a) Space is given below for writing your answer.

(b) Compare your answer with the one given at the end of this unit.

1. Define mean free path.

_____________________________________________________________________
_____________________________________________________________________
_____________________________________________________________________
_____________________________________________________________________
______________________________________________________________________

5
Let us derive an expression for mean free path. Let us assume

1. Only one molecule is in motion under consideration while all other molecules of the gas
are at rest.

2. The molecule under consideration will collide with all those molecules whose centres lie
with in a distance d from its centre fig (a) we may describe the collision by taking the
diameter of the molecule under consideration be 2d and all other molecules as point
mass particles (b).

Fig. 1.1

Let us consider a gas consisting molecules of point mass particles. Let us now think that
a molecule of equivalent diameter 2d is moving with a velocity v through the gas considered. Let
us assume the molecule under consideration and point mass particles of the gas exert no force
on each other.

In a time t, the moving molecule travels a cylinder of length vt and cross sectional area
 d as shown in figure (c). In addition to this in time t this moving molecule will collide all the
2

molecules whose centres lie within the cylinder whose axis is the line of motion of its centres
and radius ‘d’ as shown in figure (d).

Fig. 1.2

6
 2
The volume of the cylinder =  d v .

Let n be the number of molecules per unit volume.

2
The number of molecules in the cylinder =  d vn .

1
 The average time between two successive collisions =
 d 2 vn

The average distance between two successive collisions

distance travelled by molecule in one second

total number of collisions made per sec ond

v 1
2
 2
 d vn  d n

1
 mean free path   .
 d 2n

If m is the mass of the molecule then mn   .

 is the density of the gas.

m
 
 d 2

m
is constant
d2

1
  .


It means mean free path is inversely proportional to the density of the gas. We also
know density of gas varies directly as the pressure and inversely as the absolute temperature.

In deriving the equation for mean free path we have assumed that only one molecule
under consideration is moving where as all the other are at rest. But in reality always the
molecules will be moving with their velocities randomly.

By considering this reality, Maxwell by applying his molecular velocity distribution formula
arrived at the following formula for mean free path as

1
 .
2 d 2 n

7
1.4 GRAPHICAL REPRESENTATION OF VELOCITY
DISTRIBUTION OF GASES

In figure Maxwell distribution of speeds for molecules of a gas at different temperatures

is shown. The number of molecules per unit speed interval has been plotted against the speed c.
It is observed the number of molecules in a given speed interval in creases upto maximum and
then decreases asymptotically towards zero at any temperature. The number of molecules in a
given speed range is obtained by the area under the curve shown by shaded area.

Fig. 1.3

The speed located directly under the peak is the most probable speed v p . Since it is the
most likely be found for a molecule in a gas.

Fig. 1.4

8
 The average speed Vav of a molecule in the gas is actually located a bit to the right of
the peak. It is due to the reason of longer ‘tail’ on the right side of the distribution graph.

Another useful quantity is known as the root mean square speed Vrms . It will be more
than average speed of the molecule. The total area under the entire curve is equal to the total
number of molecules in the gas. If we heat the gas to high temperature, the peak of the graph
will shift to the right because the average molecular speed will increase. As the graph shifts to
the right, the height of the graph has to decrease inorder to maintain the same total area under
the curve. As gas cools to a lower temperature, the peak of the graph shifts to left. As the graph
shifts to the left, the height of the graph has to increase in order to maintain the same area under
the curve. This can be seen in the figure. In graph a gas at different temperatures is shown.

(b) (c)

Fig. 1.5

As the gas gets colds the graph becomes taller & more narrow. As the gas gets hotter
the graph becomes shorter & wide. This is required to keep the total number of molecules
constant.

The distribution curve at any temperature is not symmetrical about its peak.

So instead of asking about any one particular gas molecule, we ask questions like,
‘What is the distribution of speeds in a gas at a certain temperature?” In the mid to late 1800s,
James Clerck Maxwell and Ludwig Boltzmann figured out the answer to this question. Their
result is referred to as the Maxwell - Boltzmann distribution, because it shows how the speeds
of molecules are distributed for an ideal gas. The Maxwell - Boltzmann distribution is often
represented with the following graph.

9
1.5 MAXWELL’S LAW OF DISTRIBUTION OF MOLECULAR
SPEEDS

Let us consider a gas. Let us suppose the molecules are present in a velocity diagram.
Let O be the origin and 0X, OY, OZ as the coordinate axes as shown in figure 1.l. Let us
represent the velocity a molecule by the vector C. Further let u, v, w be the projections of this
vector in X, Y, Z directions. In the element of volume du all the molecules whose velocity
components lie in the range u and (u+du), v and (v+dv), w and (w + dw) will be present as
shown in the figure 1.6.

Fig. 1.6

The probability of a molecule is purely function of u and du whose velocity lies in the
range of u and u+du. This may written as f(u)du where f(u) is a function velocity u. Similarity
the probability of the molecule in the velocity range v and (v+dv) is f(v) dv and in the velocity
range w and (w+dw) is f(w)dw. The probability of composite event is given by the product of
the probabilities of individual events hence the probability of a molecule is

f(u) f(v) f(w) dw.dv.dw

The resultant velocity of the molecules is vector C. The probability of this single velocity
of value C lies in the volume element dudvdw. The probability may be expressed as
  C 2  du dv dw.  denotes some function.

2
 f  u  f  v  f  w  du dv dw    c  du dv dw ... 1.5

or f  u  f  v  f  w     u  v  w 
2 2 2

Where c2  u 2  v2  w 2

10
 To solve the equation 1.5 we have to choose value of c such that   c  is constant. It
2

means that the differential   c  must be equal to zero or   c  = 0.

2 2

 c2  = 0 ... 1.6

After differentiating 1.5 equation we get

d f  u  f  v  f  w    d   c 2    0

or f ' uf  v  fw du  fuf '  v  f  w  dv  f  u  f  v  f '  w  dw  0 ... 1.7

f '  u  f '  v  & f '  w  are derivatives.

By dividing equation 1.7 by f  u  f  v  f  w 

we get

f ' u  f ' v f ' w 

du  dv  dw  0 ... 1.8
f u f  v f w

As c2  u 2  v2  w 2

After differentiation we get

2u du  2vdv  2wdw  0

u du  vdv  wdw  0 ... 1.9

Multiply equation 1.9 with  we get

 u du   v dv   wdw  0 ... 1.10

Where  is a constant quantity..

After adding equations 1.8 and 1.10 we get

 f ' u    f ' v    f ' w  

   u  du     v  dv     w  dw  0 ... 1.11
 f u   f  v   f w 

As u, v, w are independent of each other equation 1.11 will be satisfied if each term is
seperately equal zero.

11
  f ' u    f ' v   f ' w 
   u  du  0 ,    v  dv  0 ,   w  dw  0 ... 1.12
 f u    f  v   f  w 

Let us solve the equations of 1.12 one by one. First consider

 f 'u  
   u  du  0
 f u  

f ' u 
  u du
f u 

After integration we get

u 2
log e f  u     log e a
2

log e a is constant of integration.

 f  u    u 2
log e  
 a  2

u2
f u  
2
e
a


u2 2
or f  u   ae 2  ae bu ... 1.13


where b 
2

Similarly we can write for other two components as

2
f  v   e  bv ... 1.14

2
f  w   ae  bw ... 1.15

From equations 1.13, 1.14, 1.15 we can write

f  u  f  v  f  w   a 3e

 b u 2  v2  w 2  ... 1.16

12
 In the above equations a is a integration constant and b is a constant. By integrating and
applying the boundary conditions we can find the constants. Let N be the number of molecules
per cc. of the gas. Let the velocities of these molecules vary from  to  .

From the definition of probability


n   f  u  f  v  f  w  du dv dw  n




   f  u  f  v  f  w  du dv dw  1


From equation 1.16


3 
 b u 2  v 2  w2  du dv dw  1


a e

The value of the definitely integral is


 bu 2 
  e

du 
b

      
 a3  
 
   1
 b  b  b 

3/ 2
 
3
or a   1
b

1/ 2
b
or a   
 

value of b

According to kinetic theory

1 2 3
mc  kT
2 2

3kT
c2 
m

3
c2 
2b

13
 3kT 3
then 
m 2b

m
b
2kT

m
As b  , where m is the mass of the molecule k is Boltzmann constant and T is
2kT
absolute temperature of the gas.

1/ 2 1/ 2
b  m 
Thus a     
   2 kT 

1/ 2
m  m 
b  and a    ... 1.17
2kT  2 kT 

the probable number of molecules dn having velocity components lying between u and
u + du, v and v + dv, w and w+dw is given by

dn  nf  u  f  v  f  w  dudvdw

substitute the value of f(u)f(v)f(w) from equation 1.16

dn  na 3 e  b  u 2  v 2  w 2 

Substituting values of a and b from 1.17 equation

we get

3/ 2  m  2 2 2
 m    u  v  w 
 2kT  
dn  n   e du dvdw ... 1.18
 2 kT 

This is Maxwell’s distribution law.

The total number of molecules that lie in a speed range c and c + dc will be obtained by
taking the volume element as the space between two concentric spheres of radii c and c + dc
drawn from a common origin. The volume of annulus is given by

4  3
  c  dc   c 3   4 c 2 dc
3  

(neglecting smaller terms)

14
 This is the same as the so called velocity volume du dvdw . Hence substituting 4 2 cdc
for du dv dw , and c2  u 2  v2  w 2 in equation 1.18 we get

3/ 2
 m    m  2 kT  c 2
dnc  n   e 4 c 2 dc
 2 kT 

3/ 2
dnc  m  
 mc 2 / 2 kT  c 2 dc
 4   e ... 1.19
n  2 kT 

This equation is called Maxwell’s law of distribution of molecular speeds in a gas. This
equation does not give the velocity of an individual molecule but only the probability of molecular
velocities lying between u, u  du, v, v  dv, w, w  dw .

1.6 TRANSPORT PHENOMENA

Gas molecules possess mass, momentum and energy. As the molecules move in a gas,
molecules carry mass, momentum or energy with them. On collision with another molecule, it
transfers one or the other physical quantities to the latter depending on the conditions available
at that time. This second molecule in turn repeat the same as it collide with the third molecule &
so on. Thus the molecules of the gas serve as carriers or the transporters of mass, momentum
or energy from one region to another through successive collisions.

In the steady state of gas the transport of any of these physical quantities in one direction
is just balanced by an equal transport of the same quantity in the opposite direction and thus
there will be no net transport in any direction. In non equilibrium state of a gas there will be
transport of the quantity concerned from the formed to the latter region to restore equilibrium.

Transport of momentum from one region to another gives rise to the phenomenon of
viscosity, thermal energy transportation gives thermal conduction and transfer of mass gives
rise to diffusion.

1.6.1 Viscosity of Gases

(a) Definition of Viscosity

Let us consider a gas flowing along a horizontal surface OX with a small velocity. Let
us suppose this velocity is smaller than thermal velocity of the molecules in the direction OX.
Then the velocity of the layer which is in contact with the surface is zero. As we move up from
O along Y direction (perpendicular to OX) the velocity of the gas increases at a uniform rate
du
. Consider a layer A at a certain distance from OX.
dy

15
 Fig. 1.7

Let u be the velocity of the gas with which gas flows in the layer A. Further, let us
consider two more layers B and C. One above (B) and one below (C) the layer A. Layers B and
C are at equal distance  from layer A. The layer above A i.e. B exerts a tangential force on
the layer below A i.e. C or the layer B exerts tangential force on C. The layer C exerts an equal
force on the layer B tending to retard it in backward direction. Hence there will be a difference
in velocities on the two sides of layer A. Due to this reason, a tangential force sets up between
the layers. This force opposes the motion of the gas. Such a force is called viscous force.
property is called as viscosity. From the definition the coefficient of viscosity  of a fluid is the
tangential force per unit area per unit velocity gradient between the layers of the gas.

du
F 
dy or

 F
du
.
dy

Let us try to explain viscosity on the basis of kinetic theory. Gas molecules above
surface A have greater velocity. Hence the average momentum of these molecules will be
more. Where as the molecules below the surface A have less velocity. Consequently, the average
momentum of these molecules will be lessthan the average momentum of the molecules above
A. Due to thermal agitation some of the molecules above A move downwards and molecules
below A move up. As there is no motion in Y direction due to the advancement of the gas the
number of molecules moving downwards must be equal to the molecules moving upwards. In
this way slower molecules below surface A gains momentum while faster molecules above

16
surface A lose momentum. According Newton’s law of motion the gain in momentum implies a
force in the forward direction and loss in momentum implies a force in the backward direction.
Therefore a retarding force acts on A in the backward direction, while on layer below A an
accelerating force acts in the forward direction. Hence the phenomenon of transport of momentum
explains the concept of viscosity.

Check Your Progress:

Note: (a) Space is given below for writing your answer.

(b) Compare your answer with the one given at the end of this unit.

2. Define the coefficient of viscosity  of a gas.

_____________________________________________________________________
_____________________________________________________________________
_____________________________________________________________________
_____________________________________________________________________
______________________________________________________________________

b) Equation for Coefficient of Viscosity  

Suppose we have a gas flowing from left to right over a solid horizontal surface, with a
velocity u less than average velocity c ; of the gas molecules. The velocity will be same
everywhere in the plane parallel to the horizontal surface XOY.

Z
u    du / dy 
B B'

A'
A
  u    du / dy 
C C'
O
X

Y Fig. 1.8

But the velocity changes from plane to plane which are parallel to XOY. The velocity of
the layer which is in contact with hard surface will be zero. Velocity increases as we move to

17
planes in the upward direction. As we move along positive Z direction velocity of the gas layer
du
increases. Let be the velocity gradient along positive Z-axis.
dz

Now let us imagine we are dividing the molecules of the gas into three distinct parts
moving parallel to three mutually perpendicular axes X, Y, Z in either direction. Thus the average
number of molecules moving in one direction along any one axis will be one sixth of the total
number of molecules in the gas.

Consider a layer AA ' parallel to XOY. Let u be the velocity of molecules in the layer
AA ' . Let us consider two more layers BB ' & CC ' parallel to AA ' . Each of the layers
( BB ' & CC ' ) are at a distance of  from AA ' one layer  BB ' will be above AA ' and
another layer  CC '  below AA ' ,  is the mean free path of the molecules. This will allow us
to consider that the molecules moving along Z direction will move between AB and AC without
collision.

du
Velocity of gas molecules in the layer BB ' = u  
dz

du
and velocity of gas molecules in the layer CC '  u  
dz

As the molecules of the gas move randomley in all directions, a continuous change of
the molecules between the layers BB ' & CC ' takes place. c is the average speed. It is the
speed of all the particles divided by the total number of particles.

If n is the number of molecules of the gas and c1 , c2 , c3 ,..., cn are their velocities then

c1  c2  c3  ...  cn
c .
n

Since the molecules from layer BB ' crossing layer AA ' downwards, with a velocity
du
u , the forward momentum carried by them per unit area of layer AA ' .
dz

= mass of molecule x velocity

 du 
= mu   
 dz 

18
 Let n be the number of molecules per unit volume of the gas, with each molecule mass
m and c as mean or average velocity of molecules crossing unit area of layer AA ' downward
nc mnc
in unit time  and is the total mass mass 
6 6

 The forward momentum carried downward by the molecules per unit area of AA '
per unit time

nc  du   c  du 
 m u     u   
6  dz  6  dz 

where mn =  in the density of the gas.

Above equation gives us the momentum lost by the fast moving layer BB ' per unit area
per unit time, in the direction of the flow.

The momentum carried upward per unit area of layer AA ' per unit time in the direction
of flow from the slow moving layer CC '

mnc  du   c  du 
 u     u   
6  dz  6  dz 

This is the momentum gained by the layer BB ' per unit time.

The net momentum lost per second by the layer BB '

c  du   c  du 
 u     u   
6  dz  6  dz 

1 du
 c 
3 dz

This same amount of momentum is gained by the layer CC ' . Thus the layer above
AA ' tends to accelerate its motion and that below AA ' tends to retard.

1 du
 Backward dragging force acting per unit area on AA '   c 
3 dz

Under steady state conditions of flow of the gas this must be equal to the tangential
du
force acting per unit area on layer AA '   .
dz

Here  is the viscosity of the gas.

19
 du 1 du
  c 
dz 3 dz

1 1
   c   mnc 
3 3

3 3
  
 c mnc

(using advanced theories and various other parameters we get  .

1 1
 is the mean free path  2 )
2 d n

we get

1
  mnc 
3

1 1
 mnc
3 2 d 2 n

1 mc

3 2 d 2

From this equation we can infer that the coefficient of viscosity of gas

1. is directly proportional to the average molecular velocity c .

2. is directly proportional to the square root of the absolute temperature of the gas since
c T

3. inversely proportional to the square of the diameter of the molecule.

4. Directly proportional to the mass of the molecule of the gas.

5. is independent of pressure or density as the equation is free of n.

At a constant temperature,  increases with P pressure, and  decreases in the

same ratio.  is quite independent of the pressure. This fact is sufficiently carried by
experiment and gave powerful support to the kinetic theory of gases.

20
Check Your Progress:

Note: (a) Space is given below for writing your answer.

(b) Compare your answer with the one given at the end of this unit.

3. Does the coefficient of viscosity of a gas depends on pressure?

_____________________________________________________________________
_____________________________________________________________________
_____________________________________________________________________
_____________________________________________________________________
______________________________________________________________________
1.6.2 Thermal conductivity of Gases

In this phenomenon the molecules are supposed to be carries of heat (energy)

Consider an area AA ' parallel to XOY. Let the temperature of gas in this plane be T..
dT
Let is the temperature gradient along the Z-direction. Consider two more layers BB ' & CC '
dz
at distance  above and below the layer AA ' .Then the temperature of the molecules in these
 dT   dT 
layers  BB ' & CC '  will be  T    and  T    respectively..
 dz   dz 

Z
T    dT / dz 
B B'

A'
A
  T    dT / dz 
C C'
O
X

Y Fig. 1.9

There will be a continuous interchange of molecules between layers BB ' & CC ' because
of random motion of the molecules. Let n be the number of molecules per unit volume of the gas
and m and c be the mass and average velocity of each molecule respectively. The mass of the
nmc
molecules crossing per unit area of AA ' either way per unit time is equal to .
6
21
  Heat carried by molecules from layer BB ' , crossing unit area of AA ' downwards
per unit time, is mass specific heat x temperature

mnc  dT 
Q1   Cv  T   
6  dz 

dT
-ve sign indicates that is really negative, representing the rate of fall of temperature
dz
in the direction of heat flows.

Similarly, heat carried by molecules from layer CC ' crossing unit area of AA ' upwards
per unit time is given by

nmc  dT 
Q2    Cv  T   
6  dz 

here Cv is the specific heat of the gas at constant volume.

 The net amount of heat transferred per unit area of AA ' per unit time is given

Q  Q1  Q2

mnc  dT   mnc   dT  
 Cv  T      Cv  T  
6  dz   6  dz  

mnc dT
 Cv  .
3 dz

c dT
 Cv  .
3 dz

where  = mn = density of the gas

The coefficient of thermal conductivity K of a gas is ‘the quantity of heat flowing per
unit area per unit temperature gradient’.

dT
Q  k
dz

On comparison with the above equation we get

c dT dT
Cv ..  K
3 dz dz

22
 c
K  Cv .
3

1
We know that   and   mn
2 nd 2

c 1
K  Cv .
3 2 nd 2

mnc 1
 Cv .
3 2 nd 2

mcCv
 .
3 2 d 2

Which is the equation for coefficient of thermal conductivity of a gas.

We know coefficient of viscosity of a gas is given by the equation

mc

3 2 d 2

On comparing coefficient of viscosity and coefficieint of thermal conductivity equations

we get k   C v

the coefficient of thermal conductivity of a

1. gas is independent of its pressure.

2. Since the variation of Cv is small, the thermal conductivity also varies directly as the
square root of the absolute temperature of the gas.

3. At low pressures both viscosity and thermal conductivity of a gas are proportional to the
pressure.

4. At pressure below 102 mm of mercury when the mean free path of the gas molecules
is of the same order of magnitude as the diameter of the containing vessel, the thermal
conductivity is proportional to the pressure K  f  p  . This is the basis for the Pirani
resistance gauge. At extremely low pressures, the conductivity decreases and the
mechanism assumes a different aspect.

5. The kinetic theory explains that the velocity and the temperature gradients no longer
remain continuous on a account of the large increase in the mean free path of molecules.
This explanation seems to be quite satisfactory.

23
6.
M
We know that m  
 , where M is molecular weight and N is Avagadros number..

N 
1 c M 
Substituting this value we get K  .2   Cv
3 2 d  N 

8kT
7. We know c 
m

where k = Boltzmann constant. Substituting this value we get

1 Cv M 8kT
K 2
3 2 d N m

Thus we find that the coefficient of thermal conductivity is inversely proportional to the
square root of mass of molecules of the gas.

Check Your Progress:

Note: (a) Space is given below for writing your answer.

(b) Compare your answer with the one given at the end of this unit.

4. Coefficient of thermal conductivity of a gas depends on the mass of the gas and how?

_____________________________________________________________________
_____________________________________________________________________
_____________________________________________________________________
_____________________________________________________________________
______________________________________________________________________
The thermal conductivity for most gases range between 0.01 & 0.03 w/mk at room
temperature. Notable exceptions are He (0.15) and hydrogen (18). As the pressure increase so
too loes the thermal conductivity.

1.6.3 Diffusion of gases

Let us consider different parts of the gas which have different molecular concentrations.
It means the density (number of molecules in unit volume) is different in different parts of the
gas. Let us assume that there is gas density gradient along Z axis. Due to the density gradient
molecules move to the places of lower concentration from the places where there is a high
concentration of molecules. This process of mass redistribution will continue till the concentration
of the molecules is the same every where with in the container in which gas.

24
 dn
Let us imagine gas is flowing along X - direction. Further concentration gradient
dz
along Z direction. Here n is the concentration of the molecules in the layer AA ' . Let us suppose
layers BB ' & CC ' are parallel and at equidistant  from AA ' . The concentration of molecules
dn dn
in BB ' will be n   and in CC ' will be n   respectively..
dz dz

Z
u    dn / dy 
B B'

A'
A
  u    dn / dy 
C C'
O
X

Y Fig. 1.10

Due to random motion of molecules, three will be interchange of molecules continuously

1 1 1
between BB ' & CC ' , along X, Y, Z axis , , of molecules will be distributed. Along +X and
3 3 3
1 1 1 1 1
-X axis distribution will be   and . On an average of molecules moving in a
3 2 6 6 6
certain direction. Thus the number of molecules passing down through unit area per unit time
from BB ' to CC ' through AA ' will be

1 dn 
  n   c
6 dz 

Number of molecules passing up from CC ' to BB ' through AA ' will be

1 dn 
  n   c
6 dz 

where c is the average velocity of molecules due to thermal energy..

 Net number of molecules passing through the layer AA ' per unit area per second

25
 1  dn   dn  
 c  n      n    
6  dz   dz  

1 dn
 c  2
6 dz

1 dn
 c .
3 dz

Now the diffusion coefficient D is given by

D = No. of molecules crossing unit area per sec concentration gradient

dn
c
1 dz  1 c 

3 dn / dz 3

1 cP n
 
3  

1
where   c  P = coefficient of viscosity
3

As

1 T
  &c  T
n P

D  P1T 3/ 2
We can infer from this equation diffusion coefficient will be directly proportional to
T 3/ 2 and inversly proportional to the pressure.
Check Your Progress:

Note: (a) Space is given below for writing your answer.

(b) Compare your answer with the one given at the end of this unit.

5. With the transport of mass what phenomena you can explain?

_____________________________________________________________________
_____________________________________________________________________
_____________________________________________________________________
_____________________________________________________________________
______________________________________________________________________

26
1.7 CHECK YOUR PROGRESS - ANSWERS

1. Average distance travelled by a molecule between two successive collisions.

2. The coefficient of viscosity  of a gas in the tangential force per unit area per unit
vescosity gradient between the layers of gas.

3. No

4. Yes, the coefficient of thermal conductivity is inversly proportional to the square root of
mass of molecules of a gas.

5. With the transport of mass we can explain of coefficient of gases.

1.8 SUMMARY

Clerk Maxwell first solved the problem of the most probable distribution of speeds in a
large number of molecules of a gas using statistical mechanics. Maxwell Boltzmann’s distribution
law does not give the velocity of an individual molecule but only the probability of its velocity
lying between velocity ranges.

Transport phenomenon which can be explained on the basis of movement of atoms or

molecules of a gas. A molecules posseses mass, momentum and energy . A moving gas can be
treated as carrier of these three physical quantities. With the help of transport of momentum we
can explain viscosity. Similarly with the transport of energy - Thermal conductivity and transport
of mass - diffusion can be explained.

1 mc
Coefficient of viscosity is given by  
3 2 d 2

Where d is the radius of the molecule.

From this equation we can infer coefficient of viscosity is proportional to the average
molecular velocity c and to the square root of the temperature and mass of the molecule.
Coefficient of viscosity is indirectly proportional to radius (d) of molecule and independent of
pressure as the equation is free of n (number of molecules).

The coefficient of thermal conductivity is given by

1 Cv M 8kT  8kT 
K 2  c  
3 2 d N m  m 

The coefficient of thermal conductivity of a gas is independent of its pressure and

inversely proportional to the square root of mass of the molecules of the gas.

27
 The coefficient of diffusion D is defined as the ratio of the number of molecules per unit
area per second to the concentration gradient.

Diffusion coefficient

1
D  c
3


or D 


1 T
As    and c  T
n P

Coefficient of diffusion D  P1T 3/ 2

Coefficient of diffusion indirectly proportional to T 3/ 2 and inversely proportional to the

pressure P.

1.9 MODEL EXAMINATION QUESTIONS

I. Answer the following questions in about 30 lines

1. Derive the expression for the Maxwell’s distribution of molecular speeds of a gas.

2. On the basis of kinetic theory of gases, deduce an expression for the coefficient of
viscosity of a gas.

3. Obtain an expression for coefficient of thermal conductivity on the basis of kinetic

theory of gases.

4. Derive an expression for coefficient of diffusion of gas on the basis of kinetic theory of
gases.

5. Derive expressions for coefficient of thermal conductivity and viscosity of a gas on the
basis of kinetic theory of gasses. hence obtain the relation between the two.

II. Answer the following questions in about 10 lines.

1. Explain transport phenomena in gases.

2. What are the fundamental assumptions or postulates of kinetic theory of gases?

28
1.10 BOOKS FOR FURTHER READING

1. Heat & Thermodynamics by D.S. Mathur, Sultan Chand & Sons, New Delhi.

2. Unified Physics Vol 2, Dr. S.C.Gupta and Sanjeev Gupta, Jaiprakashnath & Co. Meerut.

29
UNIT-2 : ZEROTH AND FIRST LAW OF THERMO
DYNAMICS
Contents

2.0 Objectives

2.1 Introduction

2.2 Thermal Equilibrium of a system

2.3 Adiabatic and Diathermic Walls

2.4 Thermal Equilibrium between two systems

2.5 Zeroth Law of Thermodynamics

2.6 Concept of Temperature

2.7 Measurement of Temperature

2.8 Different Types of Thermometers

2.9 Nature of Heat

2.10 First Law of Thermodynamics

2.11 Work done by a gas as its expands

2.12 Summary

2.13 Check Your Progress - Answers

2.14 Model Examination Questions

2.15 Glossary

2.16 Further Reading

2.0 OBJECTIVES

After going through this unit you will be able to:

 Define zeroth and first law of thermodynamics.

 Explains the conditions under which a thermodynamic system will be in equilibrium.

 Describe the measurements of temperatures using various methods.

 Evaluate the amount of work done by a gas while expanding

30
2.1 INTRODUCTION

In recent times we have studied, in case of a flow of energy into a system, when system
is working, that means heat energy converting into mechanic energy by means of this a thermal
phenomena is taking place. In daily life we come across so many thermal phenomena. In modern
time due to usage of coal heat energy is seen. Not only steam engine but also petrol and diesel
engine’s produce energy. All these led to the development of thermodynamics. About all these
we will learn in this chapter.

Conversion of heat energy into mechanical energy is dome following some rules. To
know the working principle of heat engines we have to study the laws pertaining to
thermodynamics. By studying these laws we know about the phenomena taking place in the
universe in which we are living, that is why by studying about the analyzing the and applying
them becomes necessary.

2.2 THERMAL EQUILIBRIUM OF A SYSTEM

If the thermodynamic variables which specify a system are constant in time then the
system is said to be in a state of thermal equilibrium. For a thermodynamic system of constant
mass like an amount of gas. There are two thermodynamic variables. Say, pressure and volume,
which specify the thermodynamic state of the system. If the pressure and volume of a gas
reamain constant in time then the gas is said to be in a state of thermal equilibrium.

Whether a system will be in thermal equilibrium or not will depend upon the proximity of
other systems and the nature of the wall between this system and the other systems.

2.3 ADIABATIC AND DIATHERMICAL WALLS

Let us suppose that we have system A (which is a certain amount of some gas) with
thermodynamic variables P, V. Let us suppose that we have another system B (which is again a
different amount of some other gas) with thermodynamic variables P ' V ' . Now let us suppose
we go on changing of P, V of system A. If this produces other words the values of P ', V ' of
system B are determined by the P, V values of system A and Vice-versa if the wall is diathermic.
If on the other hand changes in the values of P, V of system A do not produce any changes in the
value of P ', V ' of system B, then the wall of contact is said to be an adiabatic. Thus with an
adiabatic wall in between them the values of P, V of system A and the value of P ', V ' of system
B are independent of each other. Thin metal of diathermic wall. Thick layers of wood concrete
asbestos etc are examples of adiabatic wall.

31
 Fig. 2.1

If two systems are brought into contact through a diathermic wall, normally the
thermodynamic variables of the two systems are not compatiable and they will go on changing
till they become compatiable. After compatible values are reached there will be no further
change and the values of the thermodynamic variables will remain constant in time. The two
systems will be in thermal equilibrium with each other.

2.4 THERMAL EQUILIBRIUM BETWEEN TWO SYSTEMS

Two systems are said to be in thermal equilibrium with each other when they are in
contact with diathermic wall in between them and their thermodynamic variables are constant in
time.

2.5 ZEROTH LAW OF THERMODYNAMICS

Let us suppose we have two systems A and B with an adiabatic wall in between them.
Let A and B are in contact with system C through a diathermic wall. The whole assembly is
surrounded by an adiabatic wall (fig. 2.2). After sometime systems A between A and B and put
a diathermic one, there will be no further change. In other words A and B will be in thermal
equilibrium with each other even if we first allow A and C to come to thermal equilibrium with
each other and then allow B and C to come to thermal equilibrium with each other (Provided the
state of C is unaltered through out).

Fig. 2.2

32
 These results are stated in the form of a law which says ‘Two systems in thermal
equilibrium with a third one are in thermal equilibrium with each other”. R.H.Fowler called this
as the Zeroth law of thermodynamics.

2.6 CONCEPT OF TEMPERATURE

When two systems come into thermal equilibrium with each other, Some property of
both the systems attains the same value. Thus when A is in thermal equilibrium with C and C is
in turn in thermal equilibrium with B, the said property of three system will have the same value
so that when A and B are brought into contact they will be in thermal equilibrium.

That property of the thermodynamic system which determines whether two systems
are in thermal equilibrium or not is called the temperature. Therefore, equality of temperature
will be necessary and sufficient condition for two systems to be in thermal equilibrium with each
other.

This identification of temperature is in agreement with our experience in daily life. We

know that two systems which have the same degree of hotness when touched, will be thermal
equilibrium with each other when they are brought into diathermic of touch they will not be in
thermal equilibrium with each other when they are brought into diathermic contact. The degree
of hotness to sense of touch is the origin and basis to the scientific concept of temperature.

2.7 MEASUREMENT OF TEMPERATURE

System process many physical properties which vary as our physiological feeling of
temperature varies. Therefore the variation of any one of these properties can be used to
measure temperature of a system. Such property of a system, which varies with out physiological
feeling of temperature is called a thermometric property and the system is called a thermometer.

Let X be the thermometric property with which we wish to set up a temperature scale.
Let us suppose temperature T is a linear function of X.

T(X) = aX ... 2.1

Where ‘a’ is constant. The linear relationship between T and X implies equal changes in
X for equal temperature differences. It also means that the ratio of two temperatures of the
system is equal to the ratio of the values of X at those temperatures.

T  X1  X1
 ... 2.2
T  X2  X2

In order to determine the constant ‘a’ we specify a standard fixed point at which all the
thermometers must give the same temperature T. This point is chosen as the triple point of

33
water. (The point where water vapour, water and ice coexist). The temperature of this point is
arbitrarily assigned as 273.16 degrees Kelvin (written as 273.160K. Then for any thermometer.

TX X
 ... 2.3
T  X tr  X tr

where subscript ‘tr’ indicates that the values are at the triple point. Now since for all
thermometers.

T(Xtr) = 273.160K ... 2.4

We get

X
T(X) = 273.160K X ... 2.5
tr

2.8 DIFFERENT TYPES OF THERMOMETERS

If we use as a thermometer a system with two thermodynamic variables, for example,

an amount of gas, it will be necessary to keep one of them constant and only allow the other to
vary. Therefore x in case of a gas we can construct two types of thermometers. The first is the
constant volume thermometer in which only pressure varies and we can measure temperature
by the equation

P
T  P   273.160 K ... 2.6
Ptr

The second is the constant pressure thermometer in which only the volume is allowed to vary
and we get temperature from the equation.

V
T  V   273.160 K ... 2.7
Vtr

In addition to these there are systems in which the variation of a single physical property
can be used to measure the temperature. Thus the volume expansion of a liquid is used to
measure the temperature in the case of liquid in glass thermometers like the mercury thermometer.
The change in electrical reisistance of a wire is used to measure temperature in the platinum
resistance thermometer. The increase in the length of rod used to measure temperature. The
thermo e.m.f. generated by a thermocouple is used to measure temperature in thermopiles. The
variation in spectral composition (colour) of the light emitted by a body is used to measure
temperature in pyrometers.

34
2.9 NATURE OF HEAT

We assume that when two systems at different temperatures are brought together,
something flows from the system at higher temperature to the system at a lower temperature.
This flow will continue till thermal equilibrium is established. We call the thing that flows from
one system to the other because of temperature difference at heat.

In the early days people thought that heat was some sort of fluid. They called this fluid
as calorie. A body which is at a higher temperature has this fluid at a higher pressure and a body
which is at lower temperature has this fluid at a lower pressure. Thus when two bodies which
are at different temperatures are brought into diathermic contact, the calorie fluid flows from
the body in which it is at higher pressure to the body in which it is at lower pressure till the
pressures equalise.

In order to explain the production of heat by friction they said when bodies are rubbed
together the caloric fluid contained in them is squeezed out and we fell therefore heat to be
generated.

But this theory did not hold water for a long time. Count Raumford who was the founder
of the Royal Society of London, showed that inexhaustible amount of heat can be produced by
continuously turning a blunt drill bit in the bore hole of a canon. This is not in agreement with the
caloric theory. Once this amount is squeezed out by friction there should be no further production
of heat. Thus the generation of inexhaustible amount of heat by friction does not support caloric
theory.

We know that we have to supply heat in order to convert ice into water. Thus water
should contain more calorie than ice. Sir Humphrey Davy showed that two blocks of ice when
rubbed together are melted to produce water. If caloric theory were correct by rubbing we will
be squeezing out calorie out of ice and the product which is produced in this process must
contain less calorie than ice. Thus water must contain less calorie than ice. This is against the
fact that we mentioned earlier.

Count Rumford has shown further that, there is a relationship between the amount of
work done by the drill bit and the quantity of hat generated. From this he came to the conclusion
that heat is a form of motion and whenever motion disappears heat is generated. This leads us
to the conclusion that heat is a form of energy because whenever motion disappears it is the
kinetic energy of the body that disappears. Since heat appears in its place this is a case of
conversion of mechanical energy to heat. Hence heat is a form of energy.

There must be a rate of conversion between mechanical and heat energy. If W is the
mechanical energy in h joules and H is the heat energy in calories, then there must be an
equation.

H = W/J ... 2.8

35
 Where J is the conversion factor called the mechanical equivalent of heat. Its value
was first determined by joule. The present value is

J = 4.186 joules/calorie.

We have already said that when we add heat to a system we are actually adding energy
to it. This must be stored in the form of internal energy of the system. Let us now suppose that
we have an amount of gas in a cylinder with a movable piston. Let us suppose that we surround
this system by adiabatic walls on all sides so that no heat can enter or leave the system. Let us
now suppose that some work is done on the system by moving the piston down. Let us suppose
as a result of this the system goes from some initial state i to some final state. It has been found
experimentally that as long as the initial - final states of the gas remain the same, you have to do
the same amount of work irrespective of the path by which you go from the initial state to the
final state. Since the amount of work we have done must be stored, as the internal energy of the
system, the amount of work we have done must be equal to the increase in the internal energy
in the system. Since we have found that this is independent of the path by which we reach the
final state from the initial state, we conclude that the internal energy of the system is a function
of the state of the system, so that the difference between the internal energies in the initial and
final states remain constant as long as the initial and final states are the same. If dw i represents
the work done by the system as the system goes from the initial state to the final state in a
process no heat supplied to or taken out from the system and U f and U i are the internal
energies of the system in the final and initial states respectively, we have

dU  U f  U i   dWi  f ... 2.9

where dU is increase in the internal energy of the system.

2.10 FIRST LAW OF THERMODYNAMICS

Nowe let us suppose that do not surround the system by adiabatic walls but permit heat
to enter or leave the system. Let us suppose an amount of heat dQ enters the system. Then dQ
must be equal to the increase in the internal energy of the system plus the external work done by
the system.

dQ  U f  U i  dWi  f ... 2.10

or

dQ = dU + dW ... 2.11

This is called the first law of thermodynamics

36
2.11 WORK DONE BY A GAS AS IT EXPANDS

Let us suppose that we have a cylinder containing a gas with a piston which can move
freely (fig 2.3) . The work done by the gas when the piston is pushed up by a distance dx is
equal to

Fig 2.3

dW = F.dx = P Adx = PdV ... 2.12

where A is the area of cross section of the cylinder and dv is the increase in volume . In
general, as the volume of a gas increases its pressure does not remain constant. Therefore in
order to calculate the total work done by a gas as it expands we have to integrate Pdv.

Vf

W   PdV ... 2.13

Vi

This integral is graphically the area under the curve along which the system moves in
the P-V diagram between the limits Vi and V V f (fig 2.4)

limits Vi and V V f (fig 2.4)

Fig 2.4

37
 If the pressure acting on the piston remains constant as the gas expands, the work done
by the gas is easy to find and is equal to

Vf

W   P dV  P V f  Vi  ... 2.14
Vi

If the gas in the cylinder is expanding at constant temperature (we call such a process
 RT
isothermal process) using ideal gas equation we can substitute P  where  is the
V
number of moles of gas pressure, and we get

Vf Vf
dv
W  pdV  RT  V
Vi Vi

Vf
  RT ln ... 2.15
Vi

Check Your Progress:

Note: (a) Space is given below for writing your answer.

(b) Compare your answer with the one given at the end of this unit.

First law of thermodynamics ____

_____________________________________________________________________
_____________________________________________________________________
_____________________________________________________________________

2.12 SUMMARY

A system will be in thermal equilibrium of the thermodynamic variables of the system

are constant in time. When two systems are in contact through a wall and if altering the
thermodynamic variables of one-system results in the change of thermodynamic variables of
the second system the wall is said to be diathermic. If there is no such change in the
thermodynamic variables of the second system when the thermodynamic variables of the first
system are changed, the will is said to be adiabatic. The zeroth law of thermodynamics states
that ‘two systems in thermal equilibrium with a third one are in thermal equilibrium with each
other’. Temperature is the property of a thermodynamic system whose equality determines the
thermal equilibrium. Temperature can be determined with the help of other different properties
of the system, like volume, length, electrical resistance and thermo emf.

38
 The first law of thermodynamics states

dQ = dU + dW

When dQ is the heat energy supplied to the system, dU is the increase in the internal
energy of the system and dW is the work done by the system, work done by the gas as it
expands at pressure is

W  PC  V f  Vi

2.13 CHECK YOUR PROGRESS - ANSWERS

dQ  U f  U i  dWi  f (or) dQ = dU + dW

2.14 MODEL EXAMINATION QUESTION

I. Answer the following questions in about 30 lines.

1. State Zeroth law of thermodynamics. Explain how the temperature of a body is related
to its physical properties.

2. Write a brief note on the measurement of temperature of a body.

3. State first laws of thermodynamic and discuss some of its applications.

2.15 GLOSSARY

Thermal Equilibrium: If the thermodynamic variable which specify a system are constant
in time then the system is said to be in a state of thermal equilibrium.

2.16 FURTHER READING

1. Heat and Thermodynamics by Zemanski

2. Text book of heat by Sahas Srivatsava

39
UNIT - 3: REVERSIBLE AND IRREVERSIBLE PROCESSES
Contents

3.0 Objectives

3.1 Introduction

3.2 Reversible and Irreversible Process

3.3 Summary

3.4 Check Your Progress - Answers

3.5 Model Examination Questions

3.6 Glossary

3.7 Further Reading

3.0 OBJECTIVE

After going through this unit, you will be able to:

 Describe reversible and irreversible processes.

3.1 INTRODUCTION

A change in the physical r chemical state of a system can be brought about by a variety
of processes. If the system does not interact with the surroundings, it is called a closed system.
A process is said to be cyclic if the system returns to its original state after undergoing through
a series of operations. Any actual process however complicated it is, may be considered to be
equivalent to a sequence of simple processes. Simple process may be classified as (1) isothermal
(change in temperature is zero) (2) isobaric (change in pressure is zero) (3) isochoric (change
in volume is zero) and (4) adiabatic (no heat transfer between the system and its surroundings).
These simple processes may be reversible or irreversible. In this Unit we study in detail what is
meant by reversible and irreversible processes.

3.2 REVERSIBLE AND IRREVERSIBLE PROCESS

The characteristics of reversible and irreversible processes can be understood well by

considering a typical thermodynamic system. Let us consider a real gas of mass M confined in
a cylinder-piston arrangement of volume V. Let the pressure and temperature of the gas he P
and T respectively. When this system is in an equilibrium state, the thermodynamic, variables
namely P, T, V n remain constant with time. Let the cylinder m, whose walls are ideal heat
insulators with the base being a good conductor be placed or a large heat reservoir maintained

40
at temperature T as illustrated in Fig 3. 1. Let us now try to change the system to another
equilibrium state in which the temperature T is the same as that of the initial state but the
volume is reduced to half of its original volume. Out of many ways of achieving this two ways
are quite important.

Fig. 3.1

Process I: The piston is moved very rapidly. After some time the system comes into equilibrium
with the reservoir. During the process the gas is turbulent and hence we cannot well define the
pressure and temperature. The process cannot be represented as a continuous line on a P - V
diagram since we do not know what pressure the system would have had at a given volume.
The system passes from one equilibrium state: to another equilibrium state f as illustrated in
Fig 3.2 through a series of new equilibrium states.

Fig 3.2

41
Process II: The piston is moved very slowly say by adding sand to the top of the piston. In this
process the pressure, volume and temperature at all times could be well defined. Let a few
grains of sand be added on the piston which is considered to be friction less. As a result the
volume of the system reduces by a small amount leading to a small raise in temperature. The
system departs from equilibrium state slightly. There will be transfer of heat from the system to
the reservoir but within a short period the system will reach a new equilibrium state, its
temperature being of the reservoir. Let a few grains of sand be again added on to the piston.
The volume of the gas in the system reduces. After some time the system comes to a new
equilibrium state. By repeating the process in succession we can reduce the volume to half its
value at the initial state. During this entire process the system is always in equilibrium with the
reservoir. If the entire process is carried out with elemental changes in pressure, the intermediate
state will depart from equilibrium even less. By indefinitely increasing the number of elemental
changes the size of each elemental change can be reduced correspondingly. This will lead to an
ideal process in which the system passes through a continuous succession of equilibrium states.

These changes can be represented as a continuous line on a P-V diagram shown in Fig
3.2b. In this process a certain amount of heat Q will be transferred from the system to the
reservoir.

Process I is called irreversible process. This is because it is difficult to trace back the process.
To illustrate this aspect more clearly consider a gas confined at pressure P0 with in a volume V0
of a thermally insulated enclosure as shown in Fig 3.3. The gas is confined to a volume V0 by
means of the diaphragm D. The rest of the volume in the system (V1-V0) is evacuated. When
the diaphragm is broken the gas undergoes free expansion. When equilibrium is established its
volume will be V1. This is a spontaneous process. It is irreversible since the gas would never
return to its original volume V0 by itself. All processes, which do occur in nature are called
spontaneous irreversible or natural processes. Spontaneous process always proceed towards
equilibrium, terminating when equilibrium is established. Referring to Fig 2. 1 suppose the piston
is suddenly brought to its original position. The process rapidly runs its course terminating with
the establishment of equilibrium. Even though the initial and final states are equilibrium state
and hence the process even if it be cyclic is called an irreversible process. The following
spontaneous processes are irreversible processes.

Fig. 3.3

42
1. Degradation of mechanical energy into heat by friction.

2. Flow of heat from a warm body to a cooler body.

3. Inter diffusion of two gases.

4. Freezing of super cooled liquid.

5. Reaction of a mixture of H 2 & F2

6. Atomic explosion

It is impossible to think of the above processes to occur spontaneously in reverse.

Betrand Russel’s statement “you cannot unscramble eggs” is the best example of an irreversible
process.

Process II illustrated in Fig 3.2b is called a reversible process. A thermodynamically

reversible process is defined as a process whose direction can be reversed by an infinitesimal
change in one of the properties of the system. No actual process is reversible, but reversibility
is a limit which actual processes can be made to approach more or less closely by a choice of
experimental conditions. Thus in the process II let the piston be moved slowly downward by
removing a few grains of sand on the piston. The external pressure will then be less than the
internal pressure by dP. The gas expands and the system goes to an equilibrium state, which it
had earlier while contracting. By successive elemental decrement of external pressure on the
system by dP. we can trace back the equilibrium states through which the system has passed
through earlier.

Process II is no only reversible but also isothermal because the temperature of the gas
differs at all times by only a differential amount dT from the temperature of the reservoir on
which the cylinder rests. In other words we can say that the process takes place at constant
temperature.

The volume of the gas in the system can also be reduced adiabatically by keeping the
cylinders on a non-conducting platform say sand. In an adiabatic process no heat is allowed to
enter or leave the system. An adiabatic process can be either reversible or irreversible. In a
reversible adiabatic process the piston is moved exceedingly slowly by employing the sand-
loading technique. In the irreversible adiabatic process the piston is pushed down quickly.

In an adiabatic compression the temperature of the gas increases, because as per the
First law of thermodynamics, the work W done in pushing down the piston must appear as an
increase dU in the internal energy of the system. W will have different values for different
rates of pushing down the piston. Hence dU and the corresponding change dT will not be the
same for reversible and irreversible adiabatic processes.

A process whether reversible or irreversible depends upon the state of the system and
the nature of the process. Only reversible processes cart be mathematically described in
thermodynamics or represented by means of graphs like Fig 3.2b. It is a matter of concern to
know why all naturally occurring processes in thermodynamics are irreversible. Particularly

43
when in dynamical processes reversibility can be at least progressively attained as a final limit
by eliminating friction in elasticity etc. As per Boltzmann. irreversibility is confined to the behavoiur
of the complex structure like a gas treated as a whole and is not to be expected in the behaviour
of the individual molecules and arises from our inability to deal with individual molecules. It is
also worthwhile to note here that in the irreversible process. reversibility is not impossible. but
is almost infinitely improbable.

Check Your Progress:

Note: (a) Space is given below for writing your answer.

(b) Compare your answer with the one given at the end of this unit.

What is closed system?

_____________________________________________________________________
_____________________________________________________________________
_____________________________________________________________________
_____________________________________________________________________
______________________________________________________________________

3.3 SUMMARY

A change in the physical or chemical state of a system can be brought about by a

variety of processes. lithe system does not interact with the surroundings it is called a closed
system. A process is cyclic if the system returns to its original state after undergoing through a
series of operations. The direction of thermodynamically reversible process can be reversed by
an infinite change in one of the properties of the system.

3.4 CHECK YOUR PROGRESS - ANSWERS

A change in the physical or chemical state of a system can be brought about by a

variety of processes. If the system does not interact with the surroundings, it is called a closed
system.

3.5 MODEL EXAMINATION QUESTIONS

I. Answer the following questions in about 30 lines.

1. Explain with suitable examples the reversible and irreversible processes.

44
3.6 GLOSSARY

Thermodynamically reversible process: A thermodynamically reversible process is

defined as a process who direction can be reversed by an infinitesimal change in one of the
properties of the system.

3.7 FURTHER READING

1. Heat & Thermodynamics - Zemanski

2. Text book of Heat by Sahas Srivatsava

3. Unified Physics - Vol II, Dr. S. L Gupta and Sanjeev Gupta

45
UNIT-4 : CARNOT’S ENGINE
4.0 Objectives

4.1 Introduction

4.2 Carnot’s Cycle

4.3 Reversibility of Carnot’s cycle

4.4 Efficiency of Heat Engines

4.5 Carnot’s Theorem

4.6 Summary

4.7 Check Your Progress - Answers

4.8 Worked Examples

4.9 Model Examination Questions

4.10 Glossary

4.11 Further Reading

4.0 OBJECTIVES

After going through this unit, you will be able to:

 Describe a Carnot cycle

 Explain the working principle of a refrigerator.

 Explain how the efficiency of heat engine depends on the temperatures of hot and cold
bodies and not on the working substances.

4.1 INTRODUCTION

The laws of thermodynamics have a negative quality which distinguishes them from
other laws of physics. The first law of thermodynamics may be stated as that energy cannot be
destroyed. The second law of thermodynamics also has this negative aspect wherein we can
state the law that the spontaneous tendency of a system to go towards thermodynamic equilibrium
cannot be reversed at the same time without changing some organised energy say work, into
disordered energy say heat. The discovery of heat engines and their application to various
industrial processes enabled the formulation of second law of thermodynamics. Heat engines
function on the principle of conversion of heat energy into mechanical energy. Modern steam

46
engines used in locomotive gas turbines employed in large electric power stations and in big
ships and internal combustion engines used in motor cars and aeroplanes all have the common
feature of conversion of heat energy into mechanical energy.

A heat engine generally consists of a hot body called source which can supply heat at
a higher temperature. a cold body called sink into which heat is rejected at a lower temperature
and working substance which can absorb heat from the source convert some of it into external
work by its expansion and reject the rest to the cold body. It is not possible to extract work from
heat without a source and a sink at different temperatures. The process occurring in the heat
engine is cyclic. These cyclic operations where heat energy is converted into mechanical energy
are called Carnot Cycles after the name of the scientist Sadi Carnot whose theoretical researches
on the ideal Reversible heat engine led to the recognition of the second law of thermodynamics
as a law of nature. In this Unit we shall study about the various processes involved in the
Carnot Cycle, factors that decide the maximum efficiency of heat engines and the Carnot’s
theorem.

4.2 CARNOT’S CYCLE

A gas confined to a cylinder - piston arrangement undergoes e:pansion and compression and if
the process involved is reversible and cyclic then certain amount of work will be done by or on
the system. As shown in fig 4.1.

Fig 4.1

If the cyclic process takes the path ABCDA the work W done by the system is positive.
If the cyclic process takes the path ADCBA the work W done by the system would he the
negative of the work done.

In order to have a system to do a net amount of work a more complicated cycle must
he used. The simplest of these cycles, which is the most ideal one, is the Carnot Cycle. Here
the system consists of a working substance such as a gas. The cycle consists of two isothermal
and two adiabatic reversible processes. The working substance, which is an ideal gas, is contained

47
in a cylinder with a heat conducting base and non-conducting walls and piston. The environment
also consists of two heat reservoirs of large heat capacity kept at temperatures T1 and T2 and
two non-conducting stands. The Carnot cycle is effected in four steps as detailed below and
schematically shown in Fig 4.2

Fig. 4.2

Step 1: To start with let the gas inside the cylinder be in an equilibrium state whose pressure,
volume and temperature represented are P1 ,V1 and T1 respectively. This state is represented
by the point A in the P-V diagram illustrated in Fig 4.3. Let the system be place on the heat
reservoir at temperature T1 as shown in Fig 4.2(a) and the gas be allowed to expand slowly..
The process is reversible isothermal expansion. Let the expansion take place for sometime
when the pressure, volume and temperature attain the values P2 ,V2 & T2 . This state is represented
by the point B in Fig 4.3. During this process heat energy Q1 is absorbed by the gas by conduction
through the base. Since the expansion is isothermal at T1 the gas does work in raising the piston
and its load.

48
 Fig. 4.3

Step 2: The system is put on a non-conducting stand and the gas is allowed to expand slowly
to PV
3 3T2 . This state is represented by the point C in Fig 4.3. The expansion is reversible

adiabatic process. The gas does work in raising the piston and hence its temperature falls from
T1 to T2 .

Step 3: Now we put the system on a heat reservoir at temperature T2 and the gas is compressed
slowly so that the pressure, volume, and temperature of the gas are P4V4 and T2. This state is
represented by the point D in Fig 4.3. During the process heat energy Q2 is transferred from
the gas to the reservoir by conduction through the base. The compression is isothermal at T2. In
this process work is done on the gas by the piston and its load.

Step 4: The system is placed on a non-conducting stand and the gas is compressed slowly to
the initial condition P1, V1 and T1. The compression is adiabatic since no heat can enter or leave
the system. Work is done on the gas and its temperature rises to T1.

The net work W done by the system during the cycle is given by the shaded area in
Fig 4.3 enclosed by the path ABCD. Since Qi is the heat energy absorbed by the system
isothermal expansion (step 1) and Q2 is the heat energy given out by the system in the isothermal
compression (step 3), the net amount of heat energy gained by the system in the cycle is given
by Q1 -Q2. Since that initial and final states of the system are identical there is no change in the
internal energy of the system. Hence the net heat energy gained by the system is converted
into work. Hence as per first law of thermodynamics

W = Q1 -Q2 .
.. 4.1

Where Q1 and Q2 are taken as positive quantities. The net effect of the Carnot cycle
on the system is that heat has been converted into work by the system. Any amount of required
work can be done by the system by repeating the Carnot Cycle. Thus the system works like a
heat engine.

49
 In the ideal Carnot engine the working substance is an ideal gas. The working substance
can be anyhing and in such cases the P-V diagrams will be different. Common heat engines
use steam or a mixture of fuels and or fuel and oxygen as their working substance. Heat may
be obtained from the combustion of a fuel such as gasoline or coal or from annihilation of mass
in nuclear fission process in nuclear reactors. Heat may be discharged at the exhaust or to a
condenser. Even though real heat engines do not operate on a reversible cycle the Carnot
Cycle which is reversible gives useful information about the behaviour of any heat engine.

4.3 REVERSIBILITY OF CARNOT’S CYCLE

Since the processes isothermal expansion, adiabatic expansion, isothermal compression

and adiabatic compression are reversible processes because of total absence of friction between
the piston and the cylinder, the Carnot Cycle can be made perfectly reversible. Starting from
the point A on the P-V diagram shown in Fig 4.3 the Carnot Cycle can be traced back in
succession along the line A D C B A. The sequence of processes are (1) adiabatic expansion
(A to D) (2) isothermal compression (D to C) (3) adiabatic compression (C to B) and (4)
isothermal compression (B to A). In this process an amount of heat Q2 is removed from the
reservoir kept at lower temperature T2 and an amount of heat Q1 is delivered to the reservoir
kept at higher temperature T1. In the reversed Carnot Cycle work must be done on the system
which extracts heat from the reservoir at low temperature. Any amount of heat can he removed
from the lower temperature reservoir by repeating the reverse cycle. Thus the system functions
as a refrigerator transferring from a body at a lower temperature that is freezing compartment
to one at high temperature that is the room by means of work supplied to it in the form of
electrical energy.

4.4 EFFICIENCY OF HEAT ENGINES

The efficiency of a heat engine Q can be defined as the ratio of the net work done by
the engine during one cycle to the heat taken in from the high temperature source in one cycle.

For the ideal Carnot engine we have

W Q1  Q2 Q
   1 2 ... 4.2
Q1 Q1 Q1

Since Q1 > Q2 the efficiency of a heat engine is less than 1 so long as the heat Q2
delivered to the exhaust is not zero. A study of all practical heat engine indicates that energy,
heat engine rejects some heat during the exhaust stroke. This is the amount of heat absorbed by
the engine, which is not converted into work in the process

The efficiency of Carnot engine can also be expressed in terms of the temperatures T1
and T2 of the source and sink.

Referring to Fig 4.3 when the system is taken through the path A B by reversible
isothermal expansion process, the temperature and internal energy of the ideal gas remains

50
constant. As per the first law of thermodynamics the heat Q absorbed by the exapansion must
be equal to the work W1 done in this expansion. Hence,

V 
Q1  W1  MRT1 log  2  ... 4.3
 V1 

Where M is the mass of the gas in moles and R is called gas constant. The value of R
is 8.314 Jmol 1 K 1 .

During the isothermic compression process along the path C, D the amount of work
W2 is done on the gas by the piston leading to a transfer of heat Q2 to the reservoir at temperature
T2 . Hence

3
Q2  W2  MRT2 log   ... 4.4
4

During Eq. 4.3 by Eq. 4.4 we get

Q1 T1 log V2 / V1 
 ... 4.5
Q2 T2 log V3 / V4 

For the isothermal process along the paths A B and C D we have the following relations
to hold good for an ideal gas

PT
1 1  P2T2 ... 4.6

PV
3 3  PV
4 4 ... 4.7

For the adiabatic processes along the Paths BC and DA we have

PV
2 2  PV
3 3 ... 4.8

and

PV
4 4  PV
1 1 ... 4.9

Multiplying Eq. 4.6, 4.7, 4.8 and 4.9 we get

PV
1 1 PV
3 3 P2V2 PV
4 4  P2V2 PV
4 4 PV
3 3 PV
1 1 ... 4.10

or V1V3V2V4  V2V4V1V3 ... 4.11

 1  1
or V2V4   VV
1 3
... 4.12

or V2V4  V1V3 ... 4.13

51
Substituting Eq. 4.14 in Eq. 4.15 we get

Q1 T1 log V3 / V4  T1
   ... 4.14
Q2 T2 log V2 / V3  T2

As per the definition of the efficiency of heat engine we have

Q2 T
v 1  1 2 ... 4.15
Q1 T1

T1 and T2 are in 00 K . ... 4.16

4.5 CARNOT’S THEOREM

From the study of practical heat engines and the analysis of the ideal, Carnot engines
Carnot proposed a theorem regarding the efficiency of heat engines. The Carnot’s theorem
may be stated as that the efficiency of reversible – engines operating between the same two
temperatures is the same and no irreversible engine working between the same two temperatures
can have a greater efficiency than the reversible engine. Clausius and Kelvin showed that the
above theorem was a necessary consequence of second law of thermodynamics. The efficiency
of a reversible engine is independent of the working substance and depends only on the
temperatures.

To prove the Carnot’s theorem let us consider two reversible engines E and E’ as
shown in Fig 4.5

The engines E E ' operate between the temperatures T1 and T2 where T1 > T2. The
engines may differ in their working substance, or in their initial pressures and lengths of stroke.
Let the engine E runs in the forward direction (direct Carnot Cycle of operation) and let the

Fig. 4.5

52
 Engine E ' runs in the backward direction (reverse Carnot cycle of operation). The
engine E takes heat Q1 at T1 and gives out heat energy Q2 at T2 . The backward running
engine E ' (say refrigerator) takes heat Q2 at T2 and give out heat Q1 at T1 . Let the engines E
and E ' be connected mechanically as shown in Fig. 4.5 and the stroke lengths be adjusted so
that the work done per cycle by E is just sufficient to operate E ' .

Let us assume that the efficiency of E say  be greater than the efficiency of E ' say
'.

  ' ... 4.17

Q1  Q2 Q1 ' Q2 '
Then  ... 4.18
Q1 Q1 '

Since the work done per cycle by one engine is equal to the work done per cycle by the
other engine. We have

W W ' ... 4.19

or Q1  Q2  Q '1  Q '2 ... 4.20

Since Q1  Q2  Q and from Eqs. 4.20 and 4.18 we have

1 1
 ... 4.21
Q2 Q '1

or

Q1  Q '1 ... 4.22

Since W  W ' we also have

Q2  Q '2 ... 4.23

Equations 4.22 and 4.23 indicate that the hot source gains heat Q '1  Q1 and the cool
source loses heat Q '2  Q2 . But not work is done in the process by the combined system.
E  E ' . That is heat has been transferred from a body at T2 (lower temperature) to a body at
T1 (higher temperature) without performing work. This behaviour is contrary to the second law
of thermodynamics. hence, we can conclude that v cannot be greater than  ' . If we consider
E ' to work in the forward in the forward direction and E to work in the backward direction we
can also prove on the same lines discussed above that v ' cannot be greater than  . The net
result is

  ' ... 4.24

there by providing the first part of the Carton’s theorem.

53
 To prove the second part of the Carnot’s theorem let us consider E to be an irreversible
engine and E ' . By following the same analysis mentioned earlier we can prove that v ' , cannot
be greater than vin . Since E now is irreversible we cannot reverse the cycle and hence we can
not prove that v ' cannot be greater than v . Hence vir is either equal to or less than v ' . since
v  v '  v reversible we get

v irreversible  v reversible ... 4.25

Thereby proving the second part of Carnot’s theorem.

Check Your Progress:

Note: (a) Space is given below for writing your answer.

(b) Compare your answer with the one given at the end of this unit.

1. Efficiency of heat enging  _____

_____________________________________________________________________
_____________________________________________________________________

4.6 SUMMARY

Carnot’s Cycle is useful in converting heat into energy. Carnot’s Cycle is a reversible
cycle consisting of four process namely (1) isothermal expansion (2) adiabatic compression
(3) isothermal compression (4) adiabatic expansion.

The work done by Carnot engine is given W  Q1  Q2 . Where Q1 is the heat gained
by the system from high temperature heat source and Q2 is the heat given out by the system to
lower temperature heat link. The efficiency of heat engine is given by

T1  T2 Q1  Q2
v 
T1 Ql 2 . The efficiency of heat engine depends on the temperature of
hot and cold bodies and is independent of working substance.

Carnot’s theorem may be stated as the efficiency of reversible engine operating between
the same two temperatures is the same and no irreversible engine working between the same
two temperatures can have a greater efficiency than the reversible engine.

4.7 CHECK YOUR PROGRESS - ANSWERS

T1  T2 Q  Q2
 or 1
T1 Q

54
4.8 WORKED EXAMPLES

Example 1:

Calculate the theoretic efficiency of a steam engine operating at 10 atmosphere at

which pressure water boils at 180 0 C . The temperature of the condenser is 30 0 C .

The efficiency of heat engine can be expressed as

T1  T2  273  180    273  30 

v 
T  273  180 

453  303
v  0.33
453

The efficiency of the heat engine is 33%.

Example 2:

A Carnot Cycle uses 1 mole of an ideal gas whose C = 25 J mole 1 K 0 1 as the working
substance. It operates from the most compressed stage of 10 atm. Pressures and 500 K. It
expands isothermally to a pressure of 1 atm and then adiabatically reaches a most expanded
stage at a temperature of 300 K. Determine the numerical values of heat and work done in
each stroke. Determine the efficiency of the system.

The data in the problem is presented in Fig. 4.4.

Fig. 4.4

The work done by the gas when the system goes from A to B in the isothermal
compression process.

V2
dV V
W1   PdV   RT1    RT1 log 2
V1 V V1

55
 Since the gas contained in the cylinder is one mole  = 1. For the isothermal process
we have

V2 P1
PV  P V . Hence 
1 1 2 2 V1 P2

Therefore

P1 P
W1  RT1 log10  2.303 RT1 log10 1
P2 P2

As per the data given in the problem

T1  500 K 0 P1  1 atm P2  1atm

1
Since R = 8.314 J mole  K 
1 0
we get

10
Q1  W   8.314 J mole 1 K 1  1 mol  500 K  2.303 log10
1

Q1  W1   8.314 1 500  2.303 1 J  9547 J

Since the working substance is an ideal gas and the expression being adiabatic no heat
enters or leaves the system. The work done by the gas in pushing the piston leading to the path
BC shows in Fig 4.4 comes as a result of conversion of heat energy when the system’s
temperature changes from T1 to T2 . Since CV is the specific heat we have

1
W2  Cv T1  T2   25 J mole 1  K 0  1mole  500  300  K 0

W2  5000 J

In the process isothermal compression shown by the path C D the quantity of heat
given out by the gas to the sink is given by

V4  dV V4
Q2  W3   PdV   RT2   RT2 log
V3
V V3

Since the working substance is an ideal gas of 1 mol mass we have

V2 V3 P1
 
V1 V4 P2

56
 P2
 Q2  W3  2.303 RT2 log10
P1

1
 2.303 8.314  300 log10  
 10 

 2.303  8.314  300log10 10

Q2  W3  5744 J

In the adiabatic compression on the path of the process is D. A. When work is one on
the gas the system’s temperature changes from T2 to T1 . Hence

W4   C V  T2  T1   1 25 300  500   5000J

The efficiency of the heat engine is given by

Q1  Q2 9754  5744
v   0.41  41%
Q1 9754

v can also be obtained as

T1  T2 500  300
v   0.4  4% .
T1 500

Example 3:

A steam engine takes steam from the boiler at 2000 C at 10 atm pressure and exhausts
directly into air at 1 atm pressure at 1000 C . Calculate the maximum efficiency of the steam
engine.

The maximum efficiency of the steam engine according to Carnots theorem depends
on the temperatures of hot and cold bodies and is given by

T1  T2  200  273  100  273 100

v    0.211 or v = 21.1%.
T1  200  273 473

The actual efficiency of the heat engine is less than the maximum efficiency, which is
possible only under ideal conditions. Energy is lost by friction, turbulence and heat conduction.
In steam engines the usual efficiency attainable is above 15% Lower exhaust temperatures or
more complicated steam engines may raise the maximum efficiency attainable to 35% and
actual efficiency realizable to 20% The actual efficiency of ordinary automobile engine attainable
is about 22%. In the case of large diesel oil engine actual efficiency realizable is about 40%.

57
4.8 MODEL EXAMINATION QUESTIONS

I. Answer the following questions in about 30 lines.

I. Show that in a Carnot Cycle the net work clone by the system is equal to the difference
of heat gained by system at temperature T1 and the heat given out by the system at
temperature T.

2. State and prove Carnot’s theorem.

3. Define what is meant by efficiency of a heat engine. Derive an expression for the
efficiency of the heat engine for the efficiency of the, heat engine in terms of temperature
of the source and sink.

II. Solve the following problems

1. An ideal heat engine operates. in a Carnot cycle between 300 and I 50°C, It absorbs 50
X I 04J of heat at the high temperature. How much work per cycle is turned out by this
engine? (Ans: 13.1 J)

2. In a Carnot cycle the isothermal expansion of the gas takes place at 5000 K and the
isothermal compression at 300. During the expansion 2500 J of heat energy is transferred
to the gas. Determine the ehat rejected by the gas during the isothermal compression.
(Ans. 1500 J)

4.10 GLOSSARY

Heat Engine: A heat engine generally consists of a hot body called source which can
supply heat at a higher temperature.

4.11 FURTHER READING

1. Text book of Heat by Sahas Srivatsava

2. Unified Physics - Vol II, Dr. S. L Gupta and Sanjeev Gupta

58
 BLOCK - II

LAWS OF THERMODYNAMICS - 2
In this block the learners learn about second law of thermodynamics and
thermodynamics temperature scale, student are exposed to the introduction of entropy,
change in entropy in a reversible processes and they will explains the entropyu and
disorder.

In this block the following units are included.

Unit - 5: Second Law of Thermodynamics

Unit - 6: Entropy

59
UNIT - 5 SECOND LAW OF THERMODYNAMICS
Contents

5.0 Objectives

5.1 Introduction

5.2 Formulation of Second Law of Thermodynamics

5.3 Thermodynamics Temperature Scale

5.4 Summary

5.5 Check Your Progress - Answers

5.6 Model Examination Questions

5.7 Further Reading

5.0 OBJECTIVES
After going through this unit, you will be able to:

 Explain the formulation of second law of thermodynamics

 Describe the application of second law of thermodynamics in the formation of

thermodynamic temperature scale.

5.1 INTRODUCTION

The first law of thermodynamics establishes the internal convertibility of heat and
work. Experience tells us that no law achieves 100% efficiency in converting work into heat.
For example by devising a machine whose sole function is to create friction between moving
part. The convert process, that is complete conversion of heat into work, has not been found
possible. Investigations on the possibility to achieve complete conversion of heat into work led
to the formulation of second law of thermodynamics. The formulation of second law of
thermodynamics and its important application in the formulation of thermodynamic temperature
scale are discussed in this unit.

The second law of thermodynamics as stated by Kelvin and Clausius does not specify
the direction of change in a chemical or physical process.

60
5.2 FORMULATION OF SECOND LAW OF
THERMODYNAMICS

The analysis of the various thermodynamic processes in the ideal Carnot engine, which
works on the Carnot cycle, indicates that it is impossible to convert heat completely into work.
While it was the desire to design a perfect heat engine where all the heat input is converted into
work output as shown in fig 5.1 (a). Practical experience showed that a sizeable portion of the
absorbed heat by the system was still discharged at the lower temperature exhaust of the
engine. A fraction of the absorbed heat alone was converted into work. This is illustrated in
Fig 5.1 b.

Fig. 5.1

The design of heat engines working on the reverse carnot cycle, the refrigerator, to
simply transfer heat from a cold body to a hot body without the expense of outside work as
illustrated in 5.2a. work W is needed to transfer heat from a low temperature reservoir to a high
temperature reservoir.

Fig. 5.2

61
 Clausius and Kelvin generalized the discovery made by carnot and stated the second
law of thermodynamics in two different forms. Lord Kelvin along with Planck stated the law,
which is as follows:

It is impossible to construct a device which operating on a cycle will produce no other

effect than extraction of heat from a reservoir and the performance of an equivalent amount of
work.

Extensive experience with refrigerating devices led to the generalisation of’ the second
law of thermodynamics. Clausius stated the law as it is impossible to construct a device which,
operating on a cycle, will produce no other effect than the transfer of heat from a cooler to a
warmer body.

There are many statements of second law, which means the same as that of the two
statements given above. This law stated in either way cannot be proved directly since it is in the
negative form. To show that the two statements are equivalent it is enough if we simply prove
that if one statement is false the other statement also is false.

Let us suppose that the Clausius statement be false. Then we can have a refrigerator
operating without external work. By connecting this perfect refrigerator to an ordinary engine
as shown in Fig 5.3a heat would be returned to the hot body without expenditure of work and
would be returned to the hot body without expenditure of work and would become available
again for use by the heat engine. Hence the combination of an ordinary engine and the perfect
refrigerator would constitute a heat engine, which violates Kelvin - Planck statement.

Figure 5.3

If Kelvin - Planck statement were wrong we can have a heat engine which simply
takes heat and converts it completely into work. By connecting this perfect heat engine to an
ordinary refrigerator as shown in Figure 5.3 (b). We can extract heat from the hot body convert
it completely to work which can be used to run the refrigerator. The refrigerator extracts heat
from the body cold body and delivers it plus the work converted to heat by the refrigerator to
the hot body. The net result is transfer of heat from cold body to hot body without expenditure
of work. This process violates the Clausius statement.

62
 From the above argument we can conclude that if Kelvin - Planck statement is correct
Clausius statement is also correct and thereby proving the second law of thermodynamics.

The second law of thermodynamics is related to equilibrium because work can be

obtained from a system only if it is not already at equlibrium. If a system is at the equilibrium, no
process tends to occur spontaneously and there is nothing to harness to produce work. The
second law also implies that spontaneous flow of heat is from a high to a low temperature and
that the reverse is possible only when work is expanded.

The statements of Kelvin and Clausius provide fundamental definitions for temperature
and discussed in the following section. Temperature defined based on second law of
thermodynamics is identical with the temperature scale which makes the relation PV=RT which
holds good for ideal gases.

5.3 THERMODYNAMIC TEMPERATURE SCALE

The change in the physical property of a substance like expansion of a liquid or gas,
change in electrical resistance of platinum etc is generally employed in measuring the temperature
of a substance in the Centigragde scale or Fahrenheit scale or Reanmur scale. The temperature
so determined depends on the nature of the substance and hence the temperature measured is
not absolute but is relative since these scales are defined with respect to the specify property of
the substance namely the freezing and boiling point of water which are taken as reference
standards. From the work of carnot on ideal heat engines and the second law of thermodynamics,
Lord Kelvin realized the possibility to define temperature in terms of energy which is independent
of the nature of any particular substance. Lord Kelvin worked out the theory of such an absolute
scale starting from the result of the efficiency of ideal Carnot engine. This temperature scale is
called as Kelvin (or thermodynamics) temperature scale.

The efficiency  , of all reversible heat engine working between two temperatures
1 ,  2 depends only on these temperatures and is independent of the working substance.

Hence   f 1 ,  2  ... 5.1

We can also represent  as

Q1  Q2 Q
1 2 ... 5.2
Q1 Q1

Where Q1 is the amount of heat absorbed at higher temperature 1 and Q2 is the

account of heat rejected at the temperature  2 , where 1 and  2 are being measured any
arbitrary scale.

5.1 and 5.2

Q2
1  f 1 , 2  ... 5.3
Q1

63
or

Q1 1
  F 1 , 2  ... 5.4
Q2 1  f 1 , 2 

Where F denotes some other function of 1 , 2 . For a reversible engine working between
1 , 2 , where 1   2 , we have

Q2
 F  2 ,3  ... 5.5
Q3

For a reversible engine working between 1 , 2 where 1  3 , we have

Q1
 F 1 ,3  ... 5.6
Q3

Multiply Eqs 5.2 and 5.5 we get

Q1 Q2 Q1
   F 1 ,3   F 1 , 2   F  2 ,3  ... 5.7
Q2 Q3 Q3

Eq.5.7 is valid only if

 1 
F 1 , 2   ... 5.8
 2 

where  is another function of temperature. Therefore, for any reversible engine we can write

Q1  1 
 ... 5.9
Q2   2 

Since 1   2 and Q1  Q2 we have  1     2  .

This indicates that    is a linear function of  and may be used to measure the
temperature. Let    be denoted by T. Then Eq.5.9 becomes

Q1 T1
 ... 5.10
Q2 T3

Equation 5.10 can be used to define a new scale of temperature T, which is called
thermodynamic scale or Kelvin scale. This scale is independent of the properties of any particular
substance and Eq.5.10 is universally true. The ratio of any two temperatures on this scale is
equal to the ratio of heats taken in and rejected out by an engine working reversibly between
these two temperatures.

64
 The zero Kelvin’s temperature scale i.e.,   0 is that temperature at which Q2  0 .
Hence W  Q1 . Thus all the heat taken by the engine has been converted into work and the
efficiency of the engine is 100% i.e.   1 .  cannot be less than 0, that is negative since Q2
becomes negative implying that the engine would draw heat both from the source and the sink.
This is against the second law of thermodynamics. Hence  = 0 is the lowest temperature
conceivable. This is called the absolute zero of temperature.

To determine the size of each degree in Kelvin’s temperature scale let us suppose that
the reversible engine by working between the boiling point and freezing points of water normal
pressure. Let ABCD represent indicator diagram as shown in fig 5.4 for the Carnot cycle for
its operation. The work done by the engine is given by the area ABCD. Let the area ABCD be
divided into 100 equal parts by drawing isothermals parallel to AB and CD. The area of each
point will correspond to one degree on the Kelvin’s absolute scale. This degree Kelvin may be
defined as the difference in the temperatures between which the reversible engine should be
worked to get energy equal to one hundredth of the area of the indicator diagram representing.
Carnot’s cycle between the temperatures of boiling water and melting ice

Fig. 5.4

By keeping the temperature of the source constant say at the boiling point of water, the
work done by the engine will be made to increase as the temperature of the sink is reduced. If
we let the adiabatic expansion BC to continue so that the working substance cools continuously.
A stage will be reached when the substance no longer expands. The isothermal corresponding
to this stage is called the zero isothermal. The temperature of the isothermal as shown as
Fig.5.5 represents the zero degree of the absolute scale.

65
 Fig. 5.5

The above theoretically developed Kelvin’s temperature scale can be realized in practice
since it agrees completely with the perfect gas scale as proved below.

For a reversible engine - containing perfect gas as the working substance the efficiency
 can be given by

Q2 T
  1  1 2 ... 5.11
Q1 T1

Where T1 and T2 represent the temperature of the source and sink measured on the
perfect gas scale. As per Eq.5.11 we get

T1 T1
 ... 5.12
T2 T2

Eq.5.12 indicates that the ratio of any two temperatures on the perfect gas scale and
the thermodynamic gas scale are equal If   0 and hence the zero of the thermodynamic
scale coincides with the zero of the perfect gas scale. If T1 , T2 represents the temperatures of
boiling point of water and melting point of ice measured on the perfect gas scale we have

T1  T2  100 ... 5.13

On the Kelvins temperature scale we have for the two fixed points

T1  T2  100 .. 5.14

We can write

T1  T2 100
 
T1 T1

66
 Eqs. 5.15 and 5.16 indicate that the temperatures of the boiling point of water and the
melting point of ice are identical on the two scales. Hence, any temperatures has the same
value on the two scales and hence the two scales as identical. The melting point of ice given in
Clausius scale as 00 C is equal to 273.15 K in that Kelvin’s temperature scale.

It is worthwhile to note here that the fundamental feature of all cooling processes in
heat the lower temperature, the more difficulty it is to still over. This practical experience has
led to the formulation of the third law of thermodynamics. It can be states as that it is impossible
by any procedure, however idealized it may be, to reduce any system to the absolute zero of
temperature in a finite number of operations. Since we cannot have a sink at absolute zero, to
realize a heat engine with 1000 efficiency is a practical impossibility..

Check Your Progress:

Note: (a) Space is given below for writing your answer.

(b) Compare your answer with the one given at the end of this unit.

Formula for Ideal gas.

_____________________________________________________________________
_____________________________________________________________________
_____________________________________________________________________

5.4 SUMMARY
It is impossible to construct a device which operating on a cycle, will produce no other
effect than the extraction of heat from a reservoir and the performacne of an equivalent amount
of work (According to Kelvin).

It is impossible to construct a device which operating on a cycle will produce no other

effect than the extraction of heat from a cooler to a warmer body (Clausius statement). Lord
Kelvin defined temperature in terms of energy, which is independent of the nature of any
particular substance. The degree Kelvin is the difference in temperatures between which the
 1 th 
reversible engine works to get energy equal to the   of the area of the indicator diagram
 100 
representing Carnot’s cycle between the temperatures of boiling water and melting ice. The
third law of thermodynamics can be stated as it is impossible by any procedure to reduce any
system to the absolute zero of temperature in a finite number of operations.

5.5 MODEL EXAMINATON QUESTIONS

I. Answer the following questions in about 30 lines.

1. Discuss the formulation of thermodynamic temperature scale based on second law of

thermodynamics.

2. Discuss the formulation of second law of thermodynamics from the results of the
working of ideal CArnot engine. Give an account of the experimental verification of
the second law.

67
5.6 CHECK YOUR PROGRESS - ANSWERS

PV  nRT

5.7 FURTHER READING

1. Heat & Thermodynamics - Zemanski

2. Text book of Heat by Sahas Srivatsava

68
UNIT - 6: ENTROPY

Contents

6.0 Objectives

6.1 Introduction

6.2 Definition of Entropy

6.3 Change in Entropy in Reversible Process

6.4 Change in Entropy in Irreversible Process

6.4.1 Heat Conduction

6.4.2 Free Expansion

6.5 Second Law of Thermodynamics Interms of Entropy

6.6 Entropy and Disorder

6.7 Summary

6.8 Check Your Progress - Answers

6.9 Worked examples

6.10 Model Examination Questions

6.11 Further Reading

6.0 OBJECTIVES

After going through this unit, you will be able to:

 Define Entropy and discuss how it changes in Reversible and irreversible process.

 Describe the second law of thermodynamics interms of Entropy.

 Describe how entropy is a measure of disorder

69
6.1 INTRODUCTION

The second law of thermodynamics as stated by Kelvin and Clausis does not specify
the direction of change in a chemical or physical process. By defining a new state function
called entropy it is possible to express second law of thermodynamics in a mathematical form.
Let us now study what is meant by entropy, how it can be calculated for reversible and irreversible
processes and the relation between entropy and disorder. The physical quantity entropy was
introduced by Clausius.

6.2 DEFINITION OF ENTROPY

In the carnot cycle, the wrong substance undergoes a thermodynamic change in the
process. If Q1 represents the heat given to the working substance at temperature T1 and Q2
represents the heat taken away from the working substance at temperature T2 we have from
5.15 (see unit 5).

Q1 Q2
 ... 6.1
T1 T2

In the above equation Q’s are taken as positive quantities. If Q is taken as positive
when it enters the system and as negative when it leaves the system. We have

Q1 Q2
 0 ... 6.2
T1 T2

The above equation indicates that teh sum of the algebraic quantities Q/T is zero for a
Carnot cycle.

A reversible Carnot cycle can be taken equivalent to a large number of Carnot cycles
as illustrated in Fig 6.1, Fig. 6.1(a) represents an arbitrary reversible cycle super imposed or a
family of isotherms. By connecting these isotherms by suitable adiabatic as shown in fig. 6.1b.
The actual cycle can be split up into as assembly of Carnot cycles. This is because the outer
parts of the set of Carnot cycles trace out a curve that approximates with that of the original
cycle. If one performs all the Carnot cycles in the set, the net result would be almost the same
as performing the original cycle. This is because of the fact that all the Carnot cycle steps that
are inside the boundary are cancled out since each is traced in both a forward and reverse
direction. By dividing the original Carnot cycle into infinitely large. Carnot cycles we can get the
exact reproduction of the process. For the isothermal - adiabatic sequence of lines as shown in
Fig. 6.1b we get

70
 Fig. 6.1

Q
 O ... 6.3
T

In the limit of infinite small temperature difference between the isotherms we get

dQ
 T
... 6.4

The sign signified integration around a complete cycle. A zero value for a cyclic integral
implies that the function being integrated is independent of the path over which the integration is
made. Such a function is called a state function a thermodynamic property. This thermodynamic
property is called entropy and hence we have

dQ
ds  ... 6.5
T

and

 ds  0 ... 6.6

The units of entropy is JK 1 .

Entropy may be defined as that thermal property of a substance which remains constant
when the substance undergoes adiabatic changes since heat is neither communicated to the
system nor taken away from it. It is a physical quantity which cannot be felt like temperature
and pressure. It is a definite single valued function of the thermodynamic coordinates which
define the state of the substance namely temperature, pressure, volume and internal energy.

71
6.3 CHANGE IN ENTROPY IN A REVERSIBLE PROCESS

Consider any two equilibrium states A and B of a system and the paths connecting them
are reversible as shown in Fig 6.2. For this type of system where the process is a reversible
process we have

Fig 6.2

B A

 ds   ds  0
1A 2B
... 6.7

where 1 and 2 describe the paths connecting the points A and B since the cycle is reversible.

B B

 ds 
1A
 ds  O
2A
... 6.7

or

B B

 dS 
1A
 dS
2A
... 6.8

Eqn 6.8 indicated that the quantity  dS between any two equilibrium states of a system
A

such as A and B is independent between the states A and B. The change in entropy between the
states A and B is given by

B B
dQ
SB  SA   dS   ... 6.9
A A T

In a reversible Carnot cycle there are two adiabatic and two isothermal processes,
during the adiabatic processes no heat enters or leaves the system. Hence there is no change in
entropy. Out of the two isothermal process one is an expansion at temperature T1 and another

72
is a compression at T2 . In the isothermal expansion process an amount of heat Q1 is obsorbed

 Q4 
at T1 net gain of entropy is  T  . In the isothermal compression process an amount of heat
 1 
Q2
Q2 is liberated at T2 . Net loss of entropy is T . Hence the effective change in entropy S for
2

the whole cycle is given by

Q1 Q2
S   ... 6.10
T1 T2

Q1 Q2
For a reversible cycle T  T . Hence
1 2

S  O ... 6.11

Eq. 6.11 indicates that the entropy of a system remains constant in all reversible processes.
If a process is carried out reversibly between two states A and B then as per Eq. 6.10

B B

 dS   dS
A A
... 6.12

or

S B  S A  S AB  S AB ... 6.13

Eqn. 6.3 indicates that the heat which is absorbed or lost by the system during the
process A, B must be transferred reversibly from or to the surrounding. Hence in any process
carried out reversibly, the entropy gained or lost by the system must be lost or gained by the
surroundings. Hence the sum of entropy changes of the system and the surroundings must be
zero. Hence

S AB  system   S AB  surroundings  ... 6.14

Stotal  S BA sys  S AB  surroundings  ... 6.15

6.4 CHANGE IN ENTROPY IN IRREVERSIBLE PROCESS

Since the entropy of a system depends only on the state of the system we can calculate
the change in entropy for irreversible processes also. The only criteria required is that the
irreversible process states from an equilibrium state and ends in another equilibrium state. We
know that irreversible processes are spontaneous processes like transfer of heat from hot body
to cold body (heat conduction) and expansion of a gas into vacuum. Let us calculate the change
in entropy in the above processes.

73
6.4.1 Heat conduction

As shown in fig 6.4 let heat flow from the hot body at temperature T1 to cold body at
temperature T2

Fig 6.4

If Q represents the quantity of heat transferred from the hot body to cold body, then the
change in entropy of the hot body.

Q
Shot body  
T1

The change in entropy of the cold body

Q2
Scold body   ... 6.16
T2

The entropy change of the system

S  system   S hot body  S cold body ... 6.17

Q Q 1 1
S  system      Q   ... 6.18
T1 T2  T2 T1 

Since T1  T2 ... 6.19

S  system   0 ... 6.20

In the irreversible adiabatic heat conduction process the entropy of the system increase.

6.4.2 Free expansion

Consider an ideal gas of volume V1 expand into vacuum and let the final volume be V2 .
Since no work is done on the system in the expansion process and the gas is enclosed by non-
conducting walls as shown in Figure 6.5 (a)

74
 Fig. 6.5

F.Q = 0 from the first law of thermodynamics V  0 that is U i  U f where i and f

represents the initial and final states. Since the gas is an ideal U depends on the temperature and
not on volume or pressure. Hence the temperature of initial and final states is the same i.e.
Ti  T f  T .

The free expansion is a irreversible process. There occurs a change in entropy of the
system when the volume changes from V1 to V2 . We cannot analyse this process directly to find
the entropy difference between the expanded gas and the initial gas. It is necessary to think of
a process which can be carried out reversible that takes the system from the same initial state
to the same final state as in free expansion. Fig 6.5b illustrates how this can be achieved. This
is an isothermal process. The heat absorbed can be calculated based on first law of
thermodynamics. Thus

dV
dQ  dw  PdV   RT ... 6.21
V

where  represents the number of moles of the gas.

The entropy change of the system

V2 2V
dQ dV
S  system     R  ... 6.22
V1 T V1 V

V 
S  system    R lo ng  2  ... 6.23
 V1 

since V2  V1 ... 6.24

S system > 0 ... 6.25

Hence the entropy of the system increases in the irreversible process.

75
6.5 SECOND LAW OF THE THERMODYNAMICS IN TERMS
OF ENTROPY

The second law of thermodynamics can be stated in terms of entropy of the system
which is as follows.

A natural process that starts in one equilibrium state and ends in another equilibrium
state will go in the direction that causes the entropy of the system plus the environment to
increase.

All irreversible processes which are spontaneous and hence natural are consistent with
the above statement. The essence of second law is that there exists an useful thermodynamic
variable called entropy. This way of viewing at the second law is similar to the statements there
exists an useful thermodynamics quantity called temperature in the case of zeroth law and there
exists an useful thermodynamics quantity called internal energy in the case of first law.

The second law as stated above applies only for irreversible process, which have a
natural direction. An important deduction of this law can be seen in the famous view of Clausius.
‘The energy of the universe is constant the entropy of the universe tends always towards a
maximum’. Since all natural processes occurring in the, universe are spontaneous there must
occur in increase of entropy and hence the sum total of the entropy of the universe is continously
increasing. A philosophical deduction of this due to sir Arthur Eddington is that ‘entropy is time’s
arrow’.

Reversible processes can go equally well in either direction. For reversible processes
the entropy of the system plus environment remains unchanged. When the process is reversible
the environment and the system differ in temperature by only a differential amoutn dT, when the
heat transfer takes place.

In adiabatic processes, which can be reversible or irreversible, there is no transfer of

heat with the environemnt and hence entropy change occurs only in the system. As per the
statement of second law in terms of entropy we have.

S f  Si

for reversible adiabatic process and

S f  Si ... 6.26

for irreversible adiabatic process, where Si and Sf represent the initial and final entropies oldie
system.

The statement of second law in terms of entropy of the system is consistent with the
statement of Clausius that there is no such thing as perfect refrigerator. If there exists a perfect
refrigerator then the entropy of the lower temperature reservoir should decrease by Q/T2 and

76
that of the upper temperature reservoir should increase by Q/T1. The entropy of the system
th
1
should remain constant since it undergoes a complete cycle. Hence the net ange in the
4
entropy of the system plus environment is a decrease. This violates the principle of second law
and if the law is to be retained as applicable then there is no such thing as perfect refrigerator.

The statement of second law in terms of entropy of the system is also consistent with
Kelvin-Planck statement, which implies that there is no such thing as perfect heat engine. If
there is a perfect heat engine then the entropy of the reservoir at temperature T should decrease
by Q/t whereas the entropy of the system remains unchanged giving rise to a net decrease in
entropy of the system plus environment. This violates the second law stated in terms of entropy
and hence there is no such thing as a perfect heat engine.

6.6 ENTROPY AND DISORDER

Heat is a disordered energy. Energy can exist without disorder. A flying rifle bullet or
an atom of U235 carries ordered energy. The moving bullet has kinetic energy. When the bullet
hits a metallic plate it transfers its energy to the plate and gets stopped. The kinetic energy of
the bullet is transferred into random motions of the atoms of the bullet and as well as the metal
plate. This is a disordered energy which is felt in the form of heat.

The energy in U235 is potential energy arising out of the forces binding the nucleus
inside the nucleus. When the U235 atom undergoes fission results in a disordered energy, which
is felt in the form of heat.

The above two examples illustrate that energy, becomes heat as soon as it is disordered.
Disorder can exist without energy and if it is energized it becomes heat. The quantity of disorder
and energy can be expressed in terms of the physical quantities namely entropy and Joule. If
disorder and entropy are related then like entropy, disorder must also increase in natural
processes. Indeed this is true in the irreversible processes like free expansion and heat
conduction.

In free expansion the gas molecules confined to one half of a box say left half before
expansion fill the entire box. We know that in this case entropy increases. Disorder also increases.
This is because before expansion we say that the molecules are in the box. That is the system
is specified more generally than specifically.

In heat conduction two bodies at temperatures T1 and T2 come to uniform temperature

T when they are brought together. The system has become more disordered in this natural
process. Now we say that all molecules in the system correspond to the temperature T. Before
the bodies are brought into contact we can say that all molecules of body A are at temperature
T1 and all molecules of body B are at temperature T2 . Because of heat conduction we are
going from more specific to less specific state. That is disorder has increased.

The above examples indicate that there is a tendency for natural process to proceed
towards a state of greater disorder.

77
 In the universe all processes occur spontaneously. Hence entropy of the universe is
increasing. That is an ordered state of the universe we are tending towards a disordered state.

Statistical mechanics enables us to connect the entropy and disorder by the following
relation.

S  K log c W ... 6.27

Where K represents the Boltzmann’s constant and W represents the disorder parameter.
We represents the probability that the system can exist in the state in relation to all possible
states it could be in. This equation connects a thermodynamic quantity (S) with a statistical
quantity(W).

In terms of disorder we can calculate the change in entropy of an ideal gas in an

isothermal expansion. In this process the number of molecules (N) and the temperature(T)
remain constant and volume alone changes. The probability that molecule can be found in a
volume V is proportional to W. Hence the probability of finding a single molecule in V given by

W1  cV ... 6.28

Where c is constant. The probability of finding N molecules simultaneously in the

volume V is W given by

N
W  W1N   CV  ... 6.29

Substituting Eq.6.29 in Eq. 6.27, we get

S  KN log c V  KN  log C  log V  ... 6.30

The difference in entropy between a state of volume V f and a state of volume Vi

when T and N are constant can be given by

S f  S i  KN  log C  log V   KN  log C  log V  ... 6.31

or

VJ RN Vf
S f  Si  KN log  log ... 6.32
VI No Vi

Vf
S f  Si   R log ... 6.33
Vi

Where N o represents the Avagadro’s number..

Eq.6.23 is the same as the Eq.6.33.

78
 Due to irreversible expansion if the volume of the gas doubles then W goes from
(C1V) to (C2 V)N. Since W represents disorder, it increases in the natural process of free
N

expansion. The second law of thermodynamics can be stated based on statistical mechanics.
The direction in which natural process take place is determined by the laws of probability that
is towards a more probable state. The equilibrium state is the state of maximum entropy
thermodynamically and the most probable state statistically. Hence second law of
thermodynamics shows us the most probable course of events and not the only possible.

Check Your Progress:

Note: (a) Space is given below for writing your answer.

(b) Compare your answer with the one given at the end of this unit.
1. Unit of Entropy ____
_____________________________________________________________________

_____________________________________________________________________

2. The moving bullet has ____ energy.

_____________________________________________________________________

_____________________________________________________________________

6.7 SUMMARY
The entropy of a system is a function of the state. The change in entropy of a system
depends only on the initial and final states of the system and not on the nature of the process.
The entropy of the universe is increasing. Entropy is a measure of disorder. Disorder increases
with the increase in entropy.

6.8 CHECK YOUR PROGRESS - ANSWERS

1. JK 1
2. Kinetic

6.9 WORKED EXAMPLES

Example 1:

Determine the change in entropy in the conversion of 1 mole of liquid water at 1000 C
to vapour 1000 C at 1 atm pressure.

The system consists of 1 mole of water and the surroundings consists of a heat reservoir
at 1000 C as shown in figure 6.3.

79
 Fig. 6.6

The temperature gradient between heat reservoir and the water is infinitesimally small.
Hence the system absorbs the necessary heat from the reservoir reversibly and the water gets
converted into vapour.

The change in entropy of the system.

dQ
S  
T

since T is constant

1 Q
S   dQ 
T T

The amount of heat required to change 1 g of water to vapor is the latent heat of
vaporization given by 2258 J/g. Hence the heat absorbed to convert 1 mole of water to vapor Q
is given by

Q = 2258 J/g x 18 = 40644 J.

Q 40644 J
S  system     104 JK 1
T 373

The surroundings, that is the heat reservoir also experience a change in entropy due to
loss of heat equal to 4066 J at temperature 373 K. Thus the change in entropy of the surroundings.

40644
S  surroundings     109 JK 1
373

The total change in the entropy as the isolated system consisting of the actual system
and surroundings is zero.

80
Example 2:

Determine the entropy change of a system consisting of 5Kg of ice at 0°C which melts
irreversibly to water at 0° C. The latent heat of melting is 333 J/g. Since ice is made to melt
irreversibly, it must be kept in contact with a heat reservoir whose temperature is 0°C by only
a differential amount. When the temperature of the reservoir is lowered by a differential amount
the melted ice begins to freeze. Since the process is reversible the change in entropy.

T
dQ Q
S   
0 T T

now Q  5  103 g x 333 J/g = 1665 x 106 J

1.665  106 J
S system    6.1 103 J .K 1
2730 K

The change in entropy of the environment.

1.665  106
S environment  0
 6.1 103 JK 1
273 K

The net change in the entropy of the system plus reservoir is zero.

In practice melting of ice is an irreversible process. Suppose ice is made to melt in a

glass of water, the entropy of the system plus environment in this case increases.

6.9 MODEL EXAMINATION QUESTIONS

I. Answer the following questions in about 30 lines.

1. Define the term entropy, show that in all reversible processes the total entropy of the
system and its surroundings remains constant.

2. Show with suitable examples the change in entropy of the system undergoing an
irreversible process is always positive.

3. Show that when the entropy of a system increases its disorder also increases.

4. State and explain second law of thermodynamics in terms of entropy of the systems.
Show that this statement is consistent with Clausius and Kelvin Planck statement.

6.11 FURTHER READING

1. Heat & Thermodynamics - Zemanski

2. Text book of Heat by Sahas Srivatsava

81
 BLOCK - III

THERMODYNAMICS POTENTIALS
Block - III discusses about the thermodynamic potentials. Here introduction of
thermodynamics potentials and the learners study about the Maxwell’s thermodynamic
equations and also explained there applications of Maxwell’s thermodynamics equations
in details.

The following units are included in this block.

Unit - 7: Thermodynamic Potentials

Unit - 8: Maxwell’s Thermodynamic Equations & Applications

82
UNIT 7 : THERMODYNAMIC POTENTIALS
7.0 Objectives

7.1 Introduction

7.2 Thermodynamic Potentials

7.3 Summary

7.4 Check Your Progress - Answers

7.5 Model Examination Questions

7.6 Further Reading

7.0 OBJECTIVES

After going through this unit you will be able to:

 Derive relations between thermodynamic potentials by combining them.

 Explain the physical quantities T, P, V, S interms of thermodynamic potentials.

7.1 INTRODUCTION

Many useful thermodynamic relations can be obtained based on the laws of

thermodynamics and the properties of the system. From the first law of thermodynamics we
have

dE  dQ  dW ... 7.1

Where dE represents the change in energy of the system dQ represents the elemental
heat produced and dW represents the elemental work done. Eq.7.1 applies to both reversible
and irreversible process.

For a reversible process we have, based on Carnot’s theorem

dQ = Tds ... 7.2

If P represents the pressure and V represents the volume of the system then the
workdone on the system

dW = Pdv ... 7.3

Substituting Eq. 7.2 and 7.3 in Eq. 7.1. we get

dE = Tds - Pdv ... 7.4

83
 The above equation is called Clausius’ differential relation. This equation applies to the
closed system performing PV work only. It incorporates the mathematical content of the first
and second law of thermodynamics. The significance of Clausius differential equation is that it
connects the five most fundamental functions of a state.

7.2 THERMODYNAMIC POTENTIALS

Clausius differential relation can be interpreted as the total differential of E represented

as a function of S and V. Hence

E = E(S.V) ... 7.5

We have

 dE   dE 
dE    dS    dV ... 7.6
 ds V  dV s

Comparing this with the Clausius’s differential relation

dE = Tds - PdV

we get

 dE 
  T
 dS V

and

 dE 
   P
 dV  s

The enthalpy H of a system which is a function of S and P can be written as

H(S.P) = E + PV ... 7.7

since H = H(S, P)

 dH   dH 
dH    ds    dP ... 7.8
 dS  p  dP  s

Also since H = E + PV ... 7.9

dH = dE + PdV + VdP ... 7.10

using Eq. (7.4) in Eq. (7.10)

dH = TdS - PdV + PdV + VdP ... 7.11

84
or

dH = TdS + VdP ... 7.12

Comparing Eq 7.8 and 7.12 we get

 dH 
  T ... 7.13
 dP  p

and

 dH 
  V ... 7.14
 dP  s

The Helmoholtz free energy of the system A is characteristic function of T and V. It is

defined as

A(T.V) = E - TS ... 7.15

Since

A = A(T.V)

We can write

 dA   dA 
dA    dT    dV ... 7.16
 dT V  dV T

Also since

A = E - Ts ... 7.17

dA = dE - TdS - SdT ... 7.18

Using Eq. 7.4 in Eq. 7.18 we get

dA = TdS - PdV - TdS - SdT ... 7.19

or

dA = -PdV - SdT ... 7.20

Comparing Eq.7.16 and &.20 we get

 dA 
   S ... 7.21
 dT V

85
and

 A 
   P ... 7.22
 V  v

The Gibbs free energy of the system G is a characteristic function of T and P. It is

given by

G(T.P) = E + PV - TS ... 7.23

From Eq.7.7

G(T.P) = H - TS ... 7.24

Also from Eq. 7.15

G(T.P) = A + PV ... 7.25

Since

G = G (T.P) ... 7.26

 dG   dG 
dG    dT    dP ... 7.27
 dT  P  dP T

From the relation

G = A + PV

dG = dA + PdV + VdP ... 7.28

dG = -PdV - SdT + PdV + VdP ... 7.29

Using eq. 7.20

dG = -SdT + VdP ... 7.30

Comparing Eq.7.27 with Eq.7.30 we get

 dG 
   S ... 7.31
 dT  P

 dG 
  V ... 7.32
 dP T

The parameters E, H, A and G are called the thermodynamic potentials. The sequence
for transformations leading to these thermodynamic potentials was first devised by Gibbs.
From a knowledge of any one of these potentials as a function of its natural variables one can
calculate the other thermodynamic potentials. To illustrate if E(S, V) is know we can determine

86
T(S,V) and P(S, V) from Eq.7.5 and 7.6. By eliminating from the equation 7.5 and 7.6 we can
get the equation of the state F(P, V, T) = 0.

Since conditions of constant pressure are more prevalent than the conditions of constant
volume, H and G occur more naturally in experimental thermodynamics than E and A.

Since volume can be more easily defined theoretically than pressure. E and A are more
fundamental quantities in statistical thermodynamics. A and G are important in the study do
thermodynamic equilibrium. The four differential expressions

dE = TdS - PdV

dH = TdS + VdP

dA = -SdT - PdV

dG = -SdT + VdP

Provide a starting point for the derivation of many useful relationships among
thermodynamic variables. To remember the above differential relations a device can be used
as illustrated in 7.1

Fig 7.1

The four independent variables P, S, T, V (In alphabetical order) are placed at the
corners of a square. The potentials E, H, A, G are placed at the sides such that each lies
between its naturals variables. To write the differential expression for the potentials multiply
the differential of each independent variable by the quantity diagonally opposite. Add if the
diagonal move follows an arrow and subtract if it opposes an arrow. To illustrate let us write the
differential relation for E. In the diagram dE contains dV and dS. The coefficient of dV opposes
the arrow. Hence we take it as (-P). The coefficient of dS is along the arrow. So it is (+T).
Hence dE = TdS - PdV. Similarly we can write for dH, dA and dG easily.

87
Check Your Progress:

Note: (a) Space is given below for writing your answer.

(b) Compare your answer with the one given at the end of this unit.

1. Write the equations for any two thermodynamic potentials?

_____________________________________________________________________
_____________________________________________________________________
_____________________________________________________________________

7.3 SUMMARY

E, A, H & G are thermodynamic potentials. The relation between them is

dE = TdS - PdV

dH = TdS + VdP

dA = -SdT - PdV

dG = -SdT + VdP

The physical quantities T, P, V, S in terms of thermodynamic potentials can be given by

the following equations

 dE   dH 
T    
 dS V  dS  P

 dH   dG 
P     
 dP  S  dP T

 dH   dG 
V    
 dP  S  dP T

 dA   dG 
S      
 dT  A  dT  P

88
7.4 CHECK YOUR PROGRESS - ANSWERS

 dE   dH 
1. T       and
 dS  V  dS  P

 dA   dG 
S     
 dT  A  dT  P

7.5 MODEL EXAMINATION QUESTIONS

I. Answer the following questions in about 30 lines.

1. What are thermodynamic potentials?

2. Write down the differential relations for the thermodynamic potentials.

7.6 FURTHER READINGS

1. Heat & Thermodynamics by D.S. Mathur, Sultan Chand and Sons, New Delhi.

2. Text book of Heat by Sahas Srivatsava

89
UNIT - 8: MAXWELL’S THERMODYNAMIC EQUATIONS
AND APPLICATIONS
Contents

8.0 Objectives

8.1 Introduction

8.2 Maxwell’s Equations

8.3 Applications

8.3.1 Clausius Clapyton’s Latent Heat Equations

8.3.2 Joule - Kelvin’s Effect

8.4 Summary

8.5 Check Your Progress - Answers

8.6 ModelExamination Questions

8.7 Glossary

8.8 Further Reading

8.0 OBJECTIVES

After going through this unit you will be able to:

 Derive the Maxwell’s thermodynamic equations and its applications.

 Understand the Maxwell’s thermodynamic equations.

 Explain the applications of Maxwell’s thermodynamic equations.

8.1 INTRODUCTION

The man aim of this chapter is to make use of 2 laws of thermodynamics in convenient
form and to a set of fundamental relations known as thermodynamic relations, which find ready
application to particular problems. Here the main aim is to deduce these relations & indicate
their application to some thermal phenomena.

In general the condition of a substance is completely determined by any pair of the

quantities P, T, V, S. In solving therefore, any thermodynamic problem, the pair most suitable is
chosen as independent variables. Also the applications aspect especially to that of (1) Clausius
Clapyron’s latent heat equation and (2) Joule - Kelvin Effect is dealt in this chapter, though
there are many other applications. The quantities dealt above as P, V, T & S are pressure,
volume, temperature and entropy respectively.

90
8.2 MAXWELL’S EQUATIONS

Maxwell’s equation can be derived directly from thermodynamic potentials and also
using 1st law of Thermodynamics.

Maxwell’s first relation

du = Tds - Pdv

 du   du   du 
We write   , constant = T and    P    P... ... 8.1
 ds  dv
   dv 

du being a perfect differential, the condition

d 2u du
 must be satisfied ... 8.2
duds dvds

du
Partially differentiating the expression V  T w.r.t
ds

du
and = -P w.r.t S, we have
ds

d2 u  dT  d2 u  dp 
   and   
dvds  dv s dvds  di s

Substituting these values in (1) we get

 dT   dp 
    ... 8.3
 dv s  ds  v

This is Maxwell’s 1st equation.

II. Relation

Enthalpy h = U + PV

Interms of basic coordinates dH = Tds - Vdp

We have from the above equations

 dh   dh 
 ds   T &  dp   V
 P  S

91
differentiating partially

 d 2 h   dT   d 2 h   dv 
   &   
 dsdp   dv s  dpds   ds P

Since dh is a perfect differential, we have

 dT   dV 
    ... 8.4
 dp S  ds P

This is Maxwell’s 2nd equation

III. Relation:

Helmholtinz Fuctions F = U - Ts

df = -Pdv - Sdt ( du = dq - Pdv from I law & dp = T ds from II law)

 df   df 
which gives     P and     S
 dq T  dt V

Partially differentiation w.r.t t and w.r.t. v respectively

we have

d 2 f  dp  d 2 f  ds 
   and  
dVdt  dt V dtdv  dv T

 dp   ds 
Since df is a perfect differential we have      ... 8.5
 dt  V  dv T

This is Maxwell’s 3rd equation

IV. Relation

Gibb’s function G  U  Pv  Ts

In terms of basic coordinates

dG = Vdp - sdT

 dg   dg 
which gives    V &     S
dp
 T  dt  P

92
Differentiating w.r.t T and differentiating w.r.t P, respectively, the above equations, we have

d 2 G  dv  d 2 G  ds 
 &  
dpdT  dT P dTdp  dp T

d 2 G d 2G
Since dG is a perfect differential 
dpdt dTdp

Hence we write

 dv   ds 
 dT    dp  ... 8.6
 P  T

This is Maxwell’s 4th equation.

These above Maxwell’s thermodynamic equations 1, 2, 3 and 4 must hold good for any pure
substance.

8.3 APPLICATIONS

8.3.1 Clausius Clapyton’s Latent Heat Equations

The Clausius Clapyrons latent heat equation relates the change in melting point or
boiling point with change in pressure. We take the Maxwell’s third - equation, which contains

dp/dT term for the purpose and obtaining this equation

 dp   ds 
    ... 8.7
 dT V  dv T

Multiplying both the sides by T, we have

 dp   Tds   Tds 
T   T    . since T is a constant.
 dT  V  dv  T  dv T

 dq 
  Tds  dq 
 dv T

L
V f  Vi putting (dq/T) = L latent heat and dv = v from B.

 dp  L
   ... 8.8
 dT V V f  Vi

93
 This equation (8.8) is known as Clausius Clapyrons latent heat equation. This equation
pertains to first order phase transition when there is a emission or absorption of heat without
any change in temperature. As there is transfer of heat in phase transitions of the orders there
is a change in entropy a Volume. The pressure also remains constant. The suitable
thermodynamics potential to describe such a physical process is the Gibbs potential.

Gibbs function G = U + Pv - Ts ( du = dq - Pdv from 1 and = Tds - Pdv laws)

or dG = dP - Sdt

 dG   dG 
which gives   V &    S
 dP T  dP  P

The first order derivative of Gibb’s functions giving Entropy and Volume, change
discontinuously.

Thus during first order phase transition such as melting, vapourisation and sublimation.
The Gibbs function first derivative change discontinuously at the transition point.

There are changes in entropy & volume because of the transference of heat.

However it should be noted that Gibbs function in the same in both the phases at
equilibrium in an isothermal - isobaric change.

8.3.2 Joule - Kelvin’s Effect

Whenever real gas in throttled through a porous plug, there is always a change in the
temperature of the gas, a cooling in general, which is reffered to as Joule - Kelvins or Jolue -
Thomsan effect. This effect was discovered for the first time in 1852 by Joule - Thomson.

One essential condition of Joule - Kelvin’s expansion of a real gas is that the enthalpy
of the gas h = u + Pv must remain constant i.e. h = 0 although there is a pressure difference
across the throttling valve or porous plug.

Joule Kelvins coefficient is defined as the ratio of the temperature of a gas to the
change of pressure upon throttling at constant enthalpy & represented by  .

Thus  = (dT/dP)h

The expn for  can be achieved i.e. Joule - Kelvin coefficient is terms of the basic
thermodynamics coordinates from enthalpy and second T ds equations.

Enthalpy h = u + Pv ... 8.9

and dh = Tds + Vdp

Taking the second Tds equation

 dV 
Tds  C p dT  T   dp ... 8.10
 dT  P

94
and substituting the value in equation 8.9 above we get

 dv 
dh  Cp dt  T   dp  Vdp
 dT  P

  dv  
 C p dT   T    v  dp or
  dT  

  dv  
Cp dt  dh  T    v  dp or
  dT  v 

dh   dv  
dT  T    v  dp
C p   dT  v 

dh = 0 since enthalpy h is constant.

  dv  
 dT  1  T    v  dp
  dT  p 

 dT 
But dT     dt dp
 dP  h

 dT  1   dv  
so we write  dP  dt  CP  T  dT   v 
 h   P 

 dT 
   we have
 dP  h

Joule - Kelvin coefficient

1   dv  
 T   V  ... 8.11
Cp   dT  p 

 dT 
When i)     is negative a cooling effect is produced.
 dP  

 dT 
ii)     is positive, a heating effect is produced.
 dP  

 dT 
iii)    
 dP  

95
 is zero there is neither cooling nor heating and the corresponding transition temperature
known as inversion temperature which is a characteristic of the gas. Below the inversion
temperature we have J. T. cooling which is of great importance in liquidification of gases.

Check Your Progress:

Note: (a) Space is given below for writing your answer.

(b) Compare your answer with the one given at the end of this unit.

1. Write Maxwell’s 4th equation?

_____________________________________________________________________
_____________________________________________________________________

8.4 SUMMARY

Maxwell’s relations are of great importance in cooling devices. The applications are of
primary importance in liquidification of gases. In this Joule Kelvin effect is used. Most critical
thermodynamic problems can be solved by these equations. Use of these is also enunciated in
heat engines.

8.5 CHECK YOUR PROGRESS - ANSWERS

 dv   ds 
1.    
 dT  P  dP T

8.6 MODEL EXAMINATION QUESTIONS

I. Answer the following questions in about 30 lines.

1. Maxwell’s equations - derive them from primary considerations.

2. Joule - Kelvin effect - write about this also derive the Joule - Kelvin coefficient.

3. Clausius Clapyron’s equation - derive it.

II. Answer the following questions in about 10 lines.

1. Enthalpy

2. Helm Holtz function

3. Gibbs function

96
8.7 GLOSSARY

Joule - Kelvin’s effect: Whenever or real gas in throttled through a porous. Plug, there
is always a change in the temperature of the gas, a cooling in general, which is referred to as
Joule - Kelvin’s.

8.8 FURTHER READING

1. Unified Physics - Vol II, Dr. S. L Gupta and Sanjeev Gupta

2. Heat & Thermodynamics by Dr.S.Mathur, Sultan Chand and Sons, New Delhi.

97
 BLOCK - IV

QUANTUM THEORY OF RADIATION

In Block - IV the learners study about the quantum theory of radiation. They learn
about the low temperature physics, applications of low temperature physics, they also
studyblack body radiation in classical concepts and black body radiation in quantum
concepts in detail.

The following units are included in this block.

Unit - 9: Low Temperature Physics

Unit - 10: Applications of Low Temperature Physics

Unit - 11: Block Body Radiation (Classical Concepts)

Unit - 12: Block Body Radiation (Quantum Concepts)

98
UNIT - 9: LOW TEMPERATURE PHYSICS
Contents

9.0 Objectives

9.1 Introduction

9.2 Initial Experiments in Low Temperatures

9.3 Liquifaction of Gases

9.3.1 Porous Plug Experiment

9.4 Principle of Porous Plug Experiment

9.4.1 Three Types of Expansion of Gas

9.5 Results of Porous Plug Experiment

9.6 Analysis of Joule-Kelvin Experiment

9.7 Expression for Joule-Thomson Cooling

9.8 Regenerative Cooling Process

9.9 Liquifaction of Helium

9.10 Adiabatic Demagnetisation

9.11 Thermodynamic Theory of Adiabatic Demagnetisation

9.12 Summary

9.13 Check Your Progress - Answers

9.14 Worked Out Examples

9.15 Model Examination Questions

9.16 Glossary

9.17 Further Reading

9.0 OBJECTIVES
After going through this unit you will be able to explain the following:
 Phase diagram

 Critical temperature, Boyle’s temperature and inversion temperature

 Porous plug and Joule-Kelvin cooling

 Liquifaction of helium and

 Adiabatic demagnetisation

99
9.1 INTRODUCTION

The lowest temperature known to physicists was ice temperature. In Celsius centi-
grade scale it is assigned as zero degree C and steam temperatures 1000 C . This is very near to
triple point of water. At this temperature sublimation curve, fusion curve and vapourisation
curve meet. Fig 9.1 gives the three phases namely solid, liquid and gaseous regions for a sub-
stance like water. The phases of material is controlled by pressure as well as temperature. The
triple point of water temperature also depends on the pressure on it. For example this tempera-
ture varies between about 300 C to 800 C for different pressures. There are several stages
of achieving temperatures lower than zero degree C. Critical temperature of substance is that at
and above which it is in vapour form and can not be liquefied whatever may be the pressure
applied.

Fig. 9.1. Phase diagram

The work of Boyle, Charles and Gaylussac gives us the gas equation at around normal
temperature and pressure (NTP). As the technology of increasing and decreasing temperature
improved, the results deviate from gas equation. So we call the earlier one as ideal gas equation.
Hence we require a real gas equation. The first attempt to improve it is called as Van der Wall’s
equation. In this way as and when experimental results deviate from the existing theory a new
theory or an improvement over the earlier one is developed by physicists.

9.2 INITIAL EXPERIMENTS IN LOW TEMPERATURES

Fahrenheit observed a temperature lower than ice temperature when he mixed ice and
common salt. So he had to design a scale of measurement of temperature. Later it is known
after him. The ice point is 320 F and steam point at 2120 F . Other scientists mixed various salts
with ice at different proportions and formed various minimum temperatures such as

100
MgSO 4  3.90 C  ; KCl  11.10 C  ; NaCl  21.20 C  ; MgCl 2  33.60 C  ; CaCl2  550 C 

and KOH  650 C  respectively. The cooling is found to be due to large negative heat of

solutions. Faraday used a sealed inverted V-shaped stout glass tube to make chlorine liquified.
Hot end of the tube has manganese dioxide with hydrochloric acid. Cold end is in a freezing
mixture of ice to collect liquid chlorine under its own pressure. He could not liquify some gases
like O 2 , N 2 , H 2 ,... and called them as permanent gases.

An isothermal is a curve drawn on a P-V graph diagram for a fixed temperature. A

scientist Andrews has conducted experiments on air and CO 2 for different isothermals and
0 0
compared them. The isothermals of both gases at 480 C and isothermals 21 C,13 C of air
followed Boyle’s law. But isothermals of CO 2 at 350 C and lower values derivated from Boyle’ss
law. Andrews, thus, determined the critical isothermal for CO 2 at 30.90 C which is its critical
temperature  Tc  . He found that below  Tc  only it is possible to liquify a gas if pressure
increased. A gas cannot be liquified above its  Tc  whatever is the pressure on it. The pressure
Pc and volume Vc of a gas at its Tc called as critical constants of the gas. The Tc of O 2 and
N 2 are 1190 C and 147 0 C respectively. Andrews concluded that

(1) The densities of a liquid and the vapour gradually approach each other till they become
equal at critical point.

(2) At Tc the boundary line between the liquid and vapour disappears and

(3) The compressibility of vapour is very great near the critical point itself showing that it is
the first order transition between two phases of a gas.

Physicists Amagat, Holborn and others conducted extensive experiments on many gases
for various pressures and temperatures. Their results are represented by the following equation.

PV  A  BP  CP2  DP3  ... ... 9.1

Where A, B, C, D, ... are virial coefficients; different for different gases.

A  B  C  D etc. At very low pressures and high temperatures all gases follow Boyle’ss
law. At low pressures Boyle’s law is followed approximately with negligible deviations. As the
pressure increases more and more the deviation from Boyle’s law is more showing Boyle’s law
is not universal.

Now differentiating the equation 9.1 with respect to P, neglecting higher order terms
and equating it with zero we get

d  PV 
B0 ... 9.2
dP

The particular temperature at which the slope B = 0 is called as Boyle temperature.

101
Boyle temperature is approximately 3 times the critical temperature of a gas and it is different
for different gases.

Size of the molecule and inter molecular attraction were not taken into consideration
while obtaining ideal gas equation of state. With the advent of these Van der Waals provided a
better equation of state which is

 a 
 P  2   V  b   RT ... 9.3
 V 

where a and b are constants of that gas.

9.3 LIQUIFACTION OF GASES

The study of pure substances, like water, during the transition from one phase to an-
other is easy because ice, water and steam have a range of pressure and temperature easily
accessible without special apparatus. The gases nitrogen, hydrogen and helium have their phase
transitions at low temperatures. So it is important to learn the methods of achieving and main-
taining them. The first step is to liquify air and the most economical method to accomplish this is
with the aid of a porous plug.

9.3.1 Porous Plug Experiment

Fig. 9.2 Porous Plug

Fig. 9.2 describes a stout box wood thermally insulated cylindrical tube containing from
left in serial order an inlet piston, a prorous plug and an out let piston properly fixed. The pistons

102
are nonconducting. The porous plug is made of fibres like cotton, silk, wool. Sufficiently large
cotton fibre is taken and compressed suitably tightly between two perforated brass discs. This
forms as a porous plug unit and is surrounded by a box wood tube. This assembly is fixed in a
brass case filled with cotton wool. To such an arrangement copper tubes are fitted on either side
and kept in a water bath as shown the fig. 9.3.

Fig. 9.3 Joule-Kelvin Throttle Expansion Apparatus

The copper tubes are connected to gas inlet and outlet piston on either side of porous
plug. All this arrangement is to be made for thermal isolation. The water bath is to maintain gas
at constnat temperature before gas reaches the porous plug.

9.4 PRINCIPLE OF POROUS PLUG EXPERIMENT

The principle of this experiment is to send gas by a compressor at a constants pressure

Pi through a porous plug and note the temperatures of the gas ( Ti and Tf ) it enters and leaves
the prorous plug. The porous plug has a number of pores or fine holes and is treated as having
a number of narrow ortifices in parallel. Under a large drop in pressure difference  Pi  Pf 
the gas gets throttled or wire drawn. The word throat is referred to thin tube. Gas flowing
through porous plug is said to be throttled or forced to go through. The molecules of gas are
pulled apart from one another. Joule and Thomson conducted this experiment to verify whether

103
inter molecular attraction exists or not. If the gas does internal work utilising its own heat energy
they expected and achieved fall in temperature  Tf  Ti  . Joule and Kelvin called this process
as throttle expansion.

9.4.1 Three Types of Expansion of Gas

(a) Throttle Expansion:

When a gas under high pressure is forced to pass through thin pores of a porous plug to
a region of low pressure the gas is throttled to expand. This was experimentally discovered by
Joule and Thomson hence it is also called as Joule - Thomson or Joule - Kelvin expansion.
During this process a change in temperature difference  dt  Ti  Tf  like cooling or heating is
realised. This was found to depend on initial temperature Ti of the gas. Under normal conditions
hydrogen and helium show heating. All other gases show cooling. This method is useful to cool
gases.

(b) Adiabatic Expansion:

If gas is compressed suddenly and released to atmosphere it is said to be adiabatic

expansion. The gas performs external work against the pressure of the atmosphere. During this
process no heat is said to flow into the gas from surroundings. So the external work is drawn
from the internal energy of the gas. So that gas cools.

(c) Joule Expansion:

This is a free expansion in which the gas expands into vacuum so no external work is
done. But internal work is done against inter molecular attraction. So cooling is produced but
because of large heat capacity of the apparatus this cooling cannot be observed.

9.5 RESULTS OF POROUS PLUG EXPERIMENT

the temperatures, pressure and volumes are Ti , Pi and Vi at inlet and Tf , Pf and Vf
are at outlet of porous plug.

(1) The change in temperature dT  Ti  Tf is directly proportional to dP  Pi  Pf .

(2) All gases show a change in temperature after passing through the porous plug.

(3) If Ti  Tf then gas cools and if Ti  Tf the gas heats up. Porous plug experimental
results show that hydrogen and helium produce heating effect. All other gases show
cooling effect.

(4) The fall in dT per atmosphere pressure dP is dependent on initial temperature Ti of the
gas. As Ti is increased up to a temperature called temperature of invertion at which
final temperature is the same as initial temperature (i.e.) Ti  Tf . Above this initial

104
 temperature the gas gets heated up. In this way each gas has its own temperature of
inversion like the critical temperature  Tc  and Boyle temperature  TB  .

9.6 ANALYSIS OF JOULE-KELVIN EXPERIMENT

Ti , Pi and Vi are inlet temperature, pressure and volume; Tf , Pf and Vf are outlet ones
of the porous plug. Let Ui and Uf of the internal energies of unit mass of gas passing through
porous plug.

Then work done on the gas by piston (1) = Pi Vi and

work done by the gas on piston (2) = Pf Vf so

net work done by the gas  Pf Vf  Pi Vi  ... 9.4

Because of thermal insulation of gas the work is done at the expense of the internal
energy of the gas. So Pf Vf  Pi Vi  Ui  U f and U i  Pi Vi  Uf  Pf Vf = constants, which is
enthalpy or total energy.

Now for a PERFECT GAS according to Boyle’s law Pi Vi  Pf Vf so Ui  U f . Consid-

ering the kinetic energy and potential energy on either side of porous plug total energy before
throttling = total energy after throttling.

 K.E.i   P.E.i   K.E.f   P.E.f

There is no force of attraction between molecules of a perfect gas so

 P.E i   P.E f  0 . So  K.E.i   K.E.f and hence, Ti  Tf . The meaning of this is

that there is no change in temperature on either side of porous plug. So the Joule-Thomson
effect is zero for a perfect gas.

For REAL GASES Pi Vi  Pf Vf hence the net external workdone by the gas,
 Pf Vf Pi Vi  is not zero. So dT depends on the intial temperature Ti of the gas in the porous
plug experiment. According to equation 9.2

 d  pV  
  0 at a temperature called Boyle 's temperature 
 dP 

Let us try to understand the Porous - plug experiment with respect to Boyle tempera-
ture.

As per the experiment

above Boyle temperature PV increases as pressure increases i.e., Pi Vi  Pf Vf or U f  U i .

So Tf  Ti and heating effect is observed.

105
Below Boyle temperature Product PV decreases as pressure increases i.e. Pf Vf  Pi Vi and
U i  U f . The internal energy of the gas decreases so Tf  Ti hence cooling effect is observed.

At Boyle temperature the gas obeys Boyle’s law. That is Pi Vi  Pf Vf so U f  U i . Hence

temperature of the gas remains unchanged or Tf  Ti .

9.7 EXPRESSION FOR JOULE-THOMSON COOLING

Let us consider equations (9.3) and (9.4) as well as observer figures 9.2 and 9.3 with
the advent of definite size of the molecule and intermolecular attraction Van der Walls initiated
eqn. (9.3). The net work done by the gas during throttle expansion gives eqn. (9.4). The term
 a 
 2  of eqn (9.3) gives the internal pressure which is due to the inter molecular attraction. So
v 
the internal workdone against these forces when one gm mole of gas undergoing throttle expan-
sion to change volume from Vi to Vf is given by

Vf
 a  a a
  V2 
dv  
Vi  Vi Vf , so the total W work done is

a a
W   Pf Vf  Pi Vi    ... 9.5
Vi Vf

Van der Waal’s equation of gas is

 a 
 P  2   v  b   RT ; after re wrting we get
 V 

a ab  ab 
PV   Pb  2  RT ; as a and b are small we neglect  2  and on rewriting we
V V V 
get

a a
PV   Pb  RT; or PV  RT   Pb
V V

Applying this at inlet and outlet pistons we get

a a
Pi Vi  RT   Pi b and Pf Vf  RT   Pf b
Vi Vf

 1 1 
 Pf Vf  Pi Vi  a     b  Pi  Pf  ... 9.6
 Vi Vf 

From equations (9.5) and (9.6) we get net work done as

106
  1 1  a a
W  a     b  Pi  Pf   
 Vi Vf  Vi Vf

 a a 
W  2     b  Pi  Pf  ... 9.7
 Vi Vf 

a aPi a aPf
From PV = RT ; V  RT and V  RT
i f

using this in equation (9.7) we get

2a
W  Pi  Pf   b  Pi  Pf 
RT

 2a 
W   Pi  Pf    b ... 9.8
 RT 

Because of the thermal insulation of the system the work has to be drawn from internal
energy of the gas. The gas cools under these situations. If dT is fall in temperature and C P is
the specific heat at constant pressure, then the amount of heat that is necessary to restore the
original temperature is C P dT. Calories. So

 2a 
C P dT J   Pi  Pf    b
 RT 

 Pi  Pf   2a 
 dT   RT  b  ... 9.9
CP J  

[Here C P dT in calories = C P dT J in ergs]

2a 2a
On analysing eqn (9.9) while Pi  Pf , if  b we find dT=0 or Ti  Tf . And if b
RT RT
2a
we get dT = -ve or Ti  Tf i.e. gas becomes heated up on throttle expansion. If  b we
RT
know that dT = +ve or Ti  Tf i.e. on the throttle expansion of the gas in the porous plug
experiment the gas cools or cooling effect is observed. The temperature at which dT = 0 or
2a 2a is called as temperature of inversion. As a and b are constants associated
 b or T 
RT Rb
with the gas so the temperature of inversion of each gas is different. Hydrogen and helium can
be liquified if their temperatures of inversion are known. They were found to be 800 C and

107
2400 C for H and He respectively. So below these temperatures only these gases can be
cooled otherwise they are heated. In this way all gases are cooled. The ratio of temperature of
T  27
inverseion  Tinv  and critical temperature  Tc  is given by  inv   6.75 ; so Tinv  6.75TC .
 TC  4
Hence if TC of a gas is known we can estimate Tinversion and Boyle temperature TB  3.375TC .

9.8 REGENERATIVE COOLING PROCESS

Our air contains nearly 78% of N 2 and 21% of O2 . The temperatures of inversion are

for N 2  277 C  and O 2  770 C  . The inlet piston temperature i.e. at 300 C is comfortably
0 0

lower than the inversion temperatures of N 2 and O 2 . So it is easy to cool N 2 and O2 gases by
throttle expansion using Joule - Thomson porous plug experiment. But the fall in temperature
increases as the initial temperature of the gas is decreased. While it is easy to cool N 2 gas we
find difficulty in cooling H 2 and He. This difficulty is removed by an ingenions technique called
regenerative cooling process. In this process the gases which are already throttle expanded
made to flow back over the tube containing the incoming gas. So the gas is cooled again and
again experiencing Joule - Thomson effect to make the gas cooled more and more. In this way
by continuing the throttle expansion ultimately the gas will be liquified. Hence N 2 and O 2 gases
are liquified and the temperatures achieved are about 1700 C .

9.9 LIQUIFACTION OF HELIUM

Kamerlingh Onnes Method

A chamber with liquid N 2 at about 1700 C by a throttle expansion and regenerative

cooling will act as an outer casing like thing. Using this as inlet piston temperature and at 200
atmosphere pressure again by regenerative process H 2 gas is cooled and liquified. Because of
the inversion temperature of H 2 is 800 C which is about 1000 above liquid N 2 bath. Now we
have H 2 liquid at about 2500 C . Helium has its temperature of inversion 2400 C . H 2 liquid
acts as a inner casing to a tube containing helium. And at that temperature Joule - Kelvin porous
plug throttle expansion regenerative process is performed. As 2500 C is lower than 2400 C ,
the regenerative process realises helium be cooled and liquified at about 2680 C . This was the
method adopted by Kamerlingh Onnes.

Kapitza method:

The modification made by Kapitza is in the invention of expansion engine associated

with reverse current heat exchanger. While all lubricants used in compressors and pistons be-
come solidified at such very low temperatures they were dispensed with. Hence Kapitza used
a compressor where the piston is just sufficiently loosely fitted with its cylinder which was a
very small clearance and has no lubricant. But there is a difficulty of escaping of gas through
this small clearance while the gas is expanding. As the expansion is very rapid the escaped gas

108
is very little. Another advantage of this method is we can completely avoid liquid hydrogen as
an intermediary pre-cooler. This helps reduce machinery complications. The equipment used
by Kapitza is shown in figure 9.4.

Fig. 9.4 Liquification of Helium

Helium, in its pure and dry form, is compressed to 30 atmospheres by compressor P. A

jacket with flowing water is used around a part of He gas tube to remove heat of compression.
A liquid N 2 bath at 2080 C boiling under redused pressure is used to pre-cool He gas. Now
this pre-cooled He gas is divided into two parts in the reverse current heat exchanger. One part
passes to the expansion engines. Here adiabatic expansion makes He gas to cool to 2630 C .
Helium, thus cooled, is made ro rise in heat exchanger and cools another part which expands
again at the nozzle N and finally liquified. Liquified part is sent to Dewar flask remaining part
goes back to compressor through reverse current heat exchanger.

9.10 ADIABATIC DEMAGNETISATION

If  is magnetic susceptibility of a salt and T is its Kelvin temperature according to

C
Curie’s law   , where C is constant. To reduce temperature by adiabatic demagnetisation
T
we need a high susceptibility paramagnetic a mixture of salt like gadalinium sulphate or chro-
mium potassium alum and aluminium potassium alum. Because these salts have high suscepti-
bility and low retentivity. Molecules in a para magnetic specimen behave like tiny magnetic
dipoles. If a very strong magnetic field is applied to the salt isothermally many dipoles are
aligned in the applied magnetic field direction work is done on the molecules and the sample is
heated so temperature is raised. If magnetic field is more the rise in temperature is also more. If
applied magnetic field is switched off all the molecular dipoles rotate back to their original

109
direction. In this process work is done by the substance. The energy to do this work is drawn
from the substance itself. Temperature of the salt is reduced if it undergoes adiabatic
demagnetisation.

So this is like isothermal magnetisation and adiabatic demangetisation of a suitable para

magnetic salt to realize a large drop in temperature. Physicists like Debye, Giauque, de Hass
have developed experimental methods to achieve upto a milli degree Kelvin (A very low tem-
perature indeed!!).

Fig. 9.5 Adiabatic Demagnatisation

As shown in the figure 9.5 there are three containers one surrounding the other. Inner
most one specimen container, has the high susceptibility para magnetic salt (already mentioned)
of a single crystal or a powder in a spherical form. This also has helium gas facility to take heat
of the salt away when isothermal magnetisation is done. Surrounding this container is filled with
liquid He. The outer most container is liquid N 2 Dewar flask. The middle and outer containers
are essential to keep as low a temperature of the salt as possible. (preferably less than 1.5
degree K). The temperature of the salt is known from self inductance of a solenoid coil cc as
shown in figure 9.5. The temperatures are measured before and after the experiment with an
a.c. bridge, this depends on the susceptibility of the specimen.

9.11 THERMODYNAMIC THEORY OF ADIABATIC DELUAG

The workdone on the salt is BdI. Here dI is the decrease in intensity of magnetisation of
the paramagnetic specimen salt and B is the magnetic flux density.

Now dQ = dU + PdV becomes

dQ = dU + PdV - BdI

110
 workdone on the system is negative i.e. the temperature rises. The demangetisation is
at constnat pressure dV = 0

 dQ = dU - BdI = TdS.

If -B = P, I = V and use Maxwell’s 3rd relation will be

 T   I 
    
 B s  S  B

 T   I   T 
or,        
B
 s  T B  S B

 T   I / T 
or,      
 B B  S/ T  B

 S  1  Q  mCB
but      
 T B T  T B T

Here CB is the specific heat of m mole of gas at constant magnetic field. Now we get

 T    I / T B T  I 
     
 B s mCB / T mCB  T B

T  I 
dT    dB ... 9.10
mCB  T  B

The above equation gives fall in temperature because of the adiabatic demagnetisation.
We also know that

I C
X 
B T

CB
I  ... 9.11
T

putting eq. (9.10) in eq. (9.11) we get

T d  CB 
dT     dB
mCB dT  T 

Tf Bf
T d  CB 
or,  dT  
Ti
mC B  dT 
Bi
 dB
T 

111
 Bf
T  CB 
    dB
mC B Bi T2 

B
 C  f
  Tf  Ti       BdB
 mC B T  Bi

C
  Tf  Ti  
2mC B T
 Bf2  Bi2 

K
or,  Tf  Ti  
2C B T
 B f2  B i2  ... 9.12

C
where K  is Curie constant per unit mass and Ti , Tf , Bi and Bf are the initial and
m
final values of temperatures and magnetic flux densities of the paramagnetic salt. When the
magnetic field is switched off

Bf  0 ,

KBi2
  Tf  Ti    ... 9.13
2CBT

The meaning of the negative sign is that there is a fall in temperature due to adiabatic
demangetisation.

9.12 SUMMARY

Achieving below zero degrees centigrade started with the work of Farenheit and oth-
ers. Ice and salt mixtures made us to get upto 650 C . Faraday liquified chlorine gas. Work of
Andrew and Amagat was important in the low temperature physics. Critical temperature Boyle
temperature became useful discoveries. Joule-Kelving porus plug experiment is an important
turning point in liquidifying O2 and N 2 gases. Inversion temperature of a gas is a prerequisite in
making gas to liquify. Throttle expansion, adiabatic expansion and Joule free expansion are
compared. Expression for Joule-Thomson cooling is obtained. Regenerative cooling process
with Joule - Kelvin experiment helped Kamerhingh Onnes to achieve helium liquified. Kapitza
improved the processes. A new concept called adiabatic demangetisation is used to reduce
temperature to as low as milli degree Kelvin. The associated thermodynamic theory is ex-
plained.

112
9.13 CHECK YOUR PROGRESS - ANSWERS
1. What is ciritical temperature of a gas?

_____________________________________________________________________
_____________________________________________________________________
_____________________________________________________________________
A. It is the temperature at and above which the gas cannot be liquified, whatever be the
pressure applied.

2. How Boyle temperature is found?

_____________________________________________________________________
_____________________________________________________________________
_____________________________________________________________________
A. In a graph of PV vs. P if slope is zero for an isothermal then that temperature is Boyle
temperature.

3. Define temperature of inversion.

_____________________________________________________________________
_____________________________________________________________________
_____________________________________________________________________

A. After throttle expansion if a gas does not show any change in temperature i.e. Ti  Tf ;
then that Ti is called as temperature of inversion.

4. What is the technique used in making very low temperatures less than liquid helium
temperature?

_____________________________________________________________________
_____________________________________________________________________
_____________________________________________________________________
A. It is adiabatic demagnetisation.

9.14 WORKED OUT EXAMPLES

Numerical Example 1:

With the help of the following data calculate the temperature of inversion of He gas.
3 4 2
R = 8.31 joule/(mole-K), a = 3.44 10 nt  m / mol and b  0.0237  103 m3 / mol .

The formula for temperature of inversion is

113
 2a 2  3.44  103
Ti    34.93K .
Rb 8.31 0.0237  10 3

Numerical Example 2:

Using the given data calculate Boyle temperature of CO 2 . Van der Waal’s constants
a = 0.0072; b = 0.002. The unit of pressure is 1 atmosphere and that of volume is 1 gm mole of
gas at NTP.

 a 
Van der Waal’s equation is  P  2   V  b   RT
 V 

 0.0072 
1  1  1  0.002  273R

1.0072  0.998
R   3.682  103
273

8a 8  0.0072
Tc    289.6K
27Rb 27   3.682  103   0.002

TB  3.375  Tc  3.375  289.6  977.4K

9.15 MODEL EXAMINATION QUESTIONS

I. Answer the following questions in about 30 lines.

1. With suitable diagrams describe porous plug experiment. Explain the principle the re-
sults and analysis of the experiment.

2. Distinguish between throttle, free and adiabatic expansions of a gas. Obtain an expres-
sion for the Joule-Kelvin cooling.

3. Explain regenerative cooling process in which gas becomes liquid. With a good diagram
describe how helium is liquified.

4. What is adiabatic demagnetisation? discuss its thermodynamic theory.

II. Answer the following questions in about 10 lines.

1. Describe initial experiments in achieving low temperatures.

2. Explain porous plug experiment.

114
3. Explain throttle adiabatic and Joule expansions of a gas.

4. Write about the analysis of Joule - Kelvin effect.

5. Discuss the regenerative cooling in the process of liquifaction of gases.

6. Describe Kapitza method of liquifaction of helium.

7. Explain adiabatic demagnetisation in the production of very low temperatures.

9.16 GLOSSARY

1. Throttle expansion is a method of making a gas to expand when it is forced to pass

through a porous plug specially designed for it.

2. Inversion temperature is that temperature of a gas below which only after throttle
expansion, the gas cools and finally liquified.

3. Adiabatic demagnetisation: A paramagnetic salt isothermally magnetised to align

molecular magnetic dipoles, below 4 degrees Kelvin temperature and adiabatically
demagnetised to achieve still lower temperatures like milli degree Kelvin.

9.17 FURTHER READING

1. Heat and Thermodynamics by M.W. Zemansky; Mc Graw Hill Kogakusha.

2. A Text book of Heat by J B Rajam, S Chand & Co.

3. Heat and Thermodynamics by D S Mathur, Sultan Chand & Sons

4. Unified Physics: Thermodynamics by S L Gupta Sanjeev Gupta Jai Prakash Nath &
Co, Meerut.

5. Common Core Physics: Thermodynamics by D V Brahmaji et. al Vikas.

115
UNIT - 10: APPLICATIONS OF LOW TEMPERATURE
PHYSICS
Contents

10.0 Objectives

10.1 Introduction

10.1.1 Broad Applications

10.2 Refrigeration

10.2.1 Basics of Refrigeration

10.2.2 Ideal Refrigeration Cycle

10.2.3 Commercial Refrigeration Cycle

10.3 Vapour Compression Type Refrigerator

10.3.1 Characteristics of Refrigerants

10.4 CFC effect on Stratosphere Ozone

10.4.1 Earth’s Atmosphere

10.4.2 Ozone Layer

10.4.3 Harmful Effects of High Energy Radiation

10.4.4 Effect of CFC on Ozone Layer

10.5 Bobe Einstein Condensate

10.5.1 Basics of BEC

10.5.2 BEC - Ultra Cold Atoms

10.6 Summary

10.7 Check Your Progress

10.8 Model Examination Questions

10.9 Glossary

10.10 Further Reading

116
10.0 OBJECTIVES
After going through this unit you will be able to:

 Explain the thermodynamics of a refrigerator and its cycle of operation

 Define a refrigerant

 Describe Earth’s stratosphere

 Pinpoint CFC effect on Ozone layer

 Explain Bose - Einstein condensate

10.1 INTRODUCTION
10.1.1 Broad Applications

The applications to low temperature physics started from the days of discovery of liquid
helium. Kamerlingh Onnes tried to measure electrical resistance of mercury at low tempera-
tures and found that it is zero. He called it has acquired a new phase called super conducting.
That is mercury and some more substances behave as if until certain low temperature they have
normal conducting property and suddenly turn into super conducting phase. The electrical resis-
tance of such a substance will be about 10-25 ohm/cm. Immediately at several places low and
very low temperature laboratories were set up. They are called as cryogenic labs. Biological
and medical research started producing new results. Liquid O2 is stored in cylinders and trans-
ported for medical and health applications in hospitals and for industrial needs also. Helium at
around one degree K showed super fluidity a new branch of study where friction to flow
(visosity) is zero.

Air has different constituents in it. All of them have different liquefaction temperatures.
So they are separated accordingly and the proportion is fixed accurately. Low temperature
measuring activity made physicists to invent new things in cryogenic calorimetric work. The
associated new development is production of vacuum of high standard called sorption process
about 107 mm of mercury is also measured accurately. The most used application is refrigera-
tion and air conditioning. The effect of these we are enjoying day in and day out. Liquid
He& O 2 are essential in rockets to lift satellites in space. Satellites are most used in communica-
tion. Liquid He and O2 are used in military for ballistic missiles.

Our atmosphere depending on its altitude upto about 100 km has a wide temperature
range from 150 C to 1000 C . This is dependent on various gases it has. So if ozone  O3  is
created in a lab zone we can have detailed simulation study. Particularly the CFC effect on
ozone can be studied to protect our ozone layer which is shielding life on Earth. At very low
temperatures because of super fluidity a quantum condition associated with a quantised mass
particle called phonon is studied based on spin one particle phenomenon. This branch of physics
is called Bose-Einstein condensation which has many modern applications.

117
10.2 REFRIGERATION

10.2.1 Basics of Refrigeration

Let us start from the concept of Carnot cycle. If the cycle is performed in forward
stroke direction we realise a heat engine. On the other hand when the cycle is working in a
reverse direction we achieve a cold engine. If we imagine a cycle performed in a direction
opposite to that of an engine, the net result would be the absorption of some heat at a low
temperature the rejection of a larger amount of heat is at a higher temperature. The net amount
of work done is on the system. This can also be called as refrigerator. The system undergoing
the cycle is called refrigerant. Along with Carnot cycle several other cycles including internal
combustion one are developed for various purposes. We are enjoying the benefits of such
technologies. One such engine is sterling engine. The sterling cycle is capable of being reversed
with greater ease. It gives rise to one of the most useful types of refrigerator.

10.2.2 Ideal Refrigeration Cycle

The operation of an ideal refrigerator is understood using Figs 10.1 and 10.2. There are
four processes in four parts of the figure 10.1 and it is reflected in the P-V diagram in fig 10.2.
Let us see them in the following way.

Fig. 10.1 Ideal Refrigerator

118
 Fig. 10.2 PV diagram - Ideal Cycle

From (a) to (b) left piston moves up but the right piston remains at the same level. This
compresses the gas isothermally at higher temperature TH and heat Q H is rejected to the hot
reservoir. Form (b) to (c) both pistons move simultaneously to the same extent. This forces gas
through the junction and heat QJ is given to the junction. So right hand space experiences cold
all this is done with constant volume. From (c) to (d) as right piston moves down left piston
remains stationary. This makes an isothermal expansion at low temperature TL and QL is
absorbed by the gas from the cold reservoir. From (d) to (a) left piston moves down and right
one moves up the same amount. This forces the gas at constant volume from cold to hot end
through junction. Here also it takes the same heat Q J as earlier..

10.2.3 Commercial Refrigeration Cycle

Ideal cycle neglects turbulence, friction heat losses and such difficulties. Where as the
commercial one uses a needle valve making the refrigerant to undergo throttling process to get
Joule-Kelvin cooling.

Referring to Fig 10.3 helps us to understand the operational cycle of a commercial

refrigerator. Two isotherms of a refrigerant like FREON are shown in a PV diagram where the
temperature of a condenser is TH and that of the evaporator is TL .

Fig. 10.3 PV diagram of commercial refrigerator cycle

119
 Starting at the point (a) on the graph the state of one kg mass of saturated FREON at
the temperature and pressure of the condenser, the process (a) to (b) is due to throttling hence
involving a drop of pressure and temperature. The states in between (a) and (b) cannot be
described hence a dashed line. From (b) to (c) is isothermal, isobaric vaporisation in which heat
QL is absorbed by the refrigerant at the low temperature TL . Hence the refrigerant at the low
temperature TL . Hence the materials of the cold reservoir is cooled. From (c) to (d) is adiabatic
compression of the vapour to a temperature higher than that of the condenser TH . From (d) to
(a) isobaric cooling and condensation at TH . Any refrigerator has to extract as much heat as
possible from a cold reservoir with the expenditure of as little work as possible. The perfor-
mance of a refrigerator is called as a coefficient of performance also known as cooling energy
ratio is given by

heat extracted from cold reservoir


work done on refrigerant

QL QL
 
W  QH  QL  .

10.3 VAPOUR COMPRESSION TYPE REFRIGERATOR

This is a compression machine where a compression pump is driven by an electric

motor is used to compress the low pressure vapour. Freon is commonly used as the refrigerant
in this type machine. With the help of fig 10.4 the action of compression type refrigerator can be
explained. The refrigerant is compressed by the pump P. P is driven by an electric motor. The
cylinder of P has two values V1 and V2 . V1 is for the suction of the low pressure vapour from
the evaporator E. Valve V2 is for the discharge of the compressed vapour to the condenser C.
If the piston of the pump P moves upwards the pressure in the cylinder falls below the pressure
in the cylinder falls below the pressure in the evaporator and as a result the valve V1 opens and
the low pressure vapour is sucked into the pump through suction pipe. During the down ward
stroke of the piston, the vapour is compressed, this closes the valve V1 and opens the valve V2 .
This makes the compressed vapour delivered to the condenser through the discharge pipe.

120
 Fig. 10.4 vapour compression type refrigerator

The condenser is cooled by circulating cold water and the vapour liquefies due to high
pressure and lowering the temperature. The liquid refrigerant passes through the throttle expan-
sion needle valve or regulator valve N. This reduces the pressure of the liquid from high value in
the condenser to the low value in the evaporator. Due to low pressure, the liquid evaporates inE,
extracting its latent heat from the cold storage space surrounding E. The space is consequently
cooled. The low pressure vapour is sucked in again by the compressor to continue the operation
again and again.

10.3.1 Characteristics of Refrigerants

The liquids used in refrigerators are called as refrigerants. The most used are NH 3 , SO 2
and freon. Ammonia is generally used in large refrigerating plants like ice factories. Sulphur
dioxide and freon are employed in small machines and domestic uses. The properties of refrig-
erants are

(1) Its latent heat of vaporisation should be large so that a small quantity of it produces
desired effect.

(2) The refrigerant should be a vapour at N.T.P., but should be easily liquefied when com-
pressed and cooled.

(3) The pressure of the vapour of refrigerant liquid in the evaporator section maintained at
about 150 C . It must be greater than atmospheric pressure so that impurities in air
should not block the passage in the apparatus.

121
(4) The pressure of the refrigerant in the condenser section should be moderate so that
leakage will not be there, otherwise compressor should be heavy.

(5) The specific volume of the vapour of refrigerant should be suitably small otherwise
very large compressor is needed.

10.4 CFC EFFECT ON STRATOSPHERE OZONE

10.4.1 Earth’s Atmosphere

Our Earth is probably, the only life supporting and biocompatible planet. Water, plants,
photosynthesis and oxygen are most valuable ingradients of earth for us. Earth is exposed to
dilation of all frequencies either from the sun or the stars. Of all ultraviolet, x-ray and gamma
frequencies of radiation are harmful for life in general. Around the Earth the atmosphere, ac-
cording to its altitude ranges, is divided into four regions.

1. Troposphere upto about 12 km with temperature 150 to - 500 C has gases like
N 2 , O2 , H 2 , CO 2 ,O3

2. Stratosphere in the range of 13 to 50 km with 00 C to  600 C temperature range has

ozone  O3  as chief ingredient.

3. Mesosphere exists in altitude 50 to 85 km and temperature range 00 C to  850 C with

O 2 and NO gases present in it.

4. Thermosphere is in 85 km to 800 km range temperatures are unpredictable sometimes

go to very high values also. The gases present are O2 , O and NO.

10.4.2 Ozone Layer

Ozone or O3 is the major constituent in this layer. It is part of stratosphere with the
altitude range of 15 - 35 km. 90% of this layer is filled with ozone. The absorption spectrum of
ozone shows O 2 and O3 absorb almost all wavelengths less than 3000 A essentially coming
from the sun.

That is harmful ultra violet, x-ray and gamma rays fall under this region. because of
absorption the temperature of this layer increases. Thus ozone layer helps biological life to
sustain. So whatever thing that damages ozone layer should not be manufactured and used for
domestic and industrial needs.

10.4.3 Harmful Effects of High Energy Radiation

Of all the high energy radiation ultra violet happens to be more prevalent from the Sun
to our Earth. Ultra violet rays damage the deoxyribo Nucleic acid (DNA) associated with the
basic life form. Ultraviolet harms the reproductive molecules in all living beings. It has been
found that they increase the occurrence of human skin cancer. UV exposure reduces the rate

122
and efficiency of photosynthesis. Ultraviolet rays affect the climate of our earth. hence causes
global warming consequently uv rays increase the damage to all living beings in the form of
human, live stock, animal and plant life.

Global warming is associated with holes in ozone layer of our atmosphere. The holes
are mainly due to industrialisation of developed countries and leakage of CFC and various
derivatives. The holes make earth exposure to uv radiation. Holes are near north pole of earth
or at antarctic. The ice at that place melts unnaturally. So the water level in seas around the
world rise. Hence coastal regions of earth is in danger of inundation.

10.4.4 Effect of CFC on Ozone Layer

Scientists were trying to make a safer substitute for ammonia and sulphur dioxide as
refrigerant in the early parts of twentieth century. In 1928 Thomas Midgley and C.F. Kettering
made a material called CCl2 F2 , the trade name of it is ‘Freon’>. Freon is a colorless odorless,
nonflammable, non carcinogenic and moncorrosive gas. Freon and similar detrivatives haloalkane
gases have their evaporation temperature about 230 C , condensing temperature about 540 C
for an ambient temperature of 320 C . Some high cost condensers produced upto 60% of the
theoratical efficiency with CFC & HCFC. But they are double the cost of ordinary ones which
have only 45% efficiency. Hence the gases leak into atmosphere. CFC and HCFC have good
conversion from liquid to gas and back so only, their preference in the industry in the earlier
days. These substances are also used as solvents in electronics industry. CFC are used as foam
blowing agents in fire extinguishers. They are propellants in aerosol industry for asthma pa-
tients. Along with Freon, halon, carbon tetrachloride and HCFC are some other gases that leak
into atmosphere and damage ozone layer. Such materials are called as ozone depleting sub-
stances (ODS). 26% of total ODS used as refrigerants, 25% of ODS used as foam blowing
agents in fire extinguishing work, 26% are used in aerosols as solvents (mainly cleaning printed
circuit boards of electronics industry) and remaining 7% in various other applications.

The ultra violet radiation falling on CCl2 F2 releases chlorine. This chlorine atom reacts
with ozone produces ClO and oxygen molecule. The reaction is given as:

CCl 2 F2  uv  Cl and Cl  O3  ClO  O2

A chlorine atom once left in atmosphere survives and has a life time of 20-100 years.
Hence it can break large number of ozone ( O3 ) molecules. So the damage is all the more
dangerous. From 1930 until 1970 scientists were not much aware of ozone depletion damage.
From 1970 to 1990 more research helped us the seriousness of the situation.

In 1990, one thousand tonnes of ozone depleting products were identified on earth. A
big hole like thing was observed at Antarctic region in the atmosphere O3 layers. Its effects are
alarming on the health of humans and others. Because uv passes through this hole and falls on
earth. This made governments of all the countries in the world to be alert in this matter and take
decisions to stop reducing ODS materials. By 2010 the ODS materials are found to be 50
tonnes. A notable reduction indeed.

123
10.5 BOSE EINSTEIN CONDENSATE
10.5.1 Basics of BEC

Bose-Einstein condensate (BEC) is a new state of matter essentially associated with

very low temperatures of about a milli or micro degree kelvin. The other states of matter are
gas, liquid, solid and plasma. To know more about BEC we turn our attention to a quantum
phenomenon called spin of a particle. There are various fundamental particles and their deriva-
tives as atoms and molecules. Of these particles those associated with electromagnetic radia-
tion are quantum of energy as proposed by Max Planck. Planck derived his equation using some
conditions called quantum conditions. The same formula was derived by Indian scientist S.N.
Bose without any reference to classical physics. He sent the research paper to Einstein who in
turn translated into German and got it published in 1924. Einstein used the ideas of Bose and
developed a branch of quantum statistics called as Bose- Einstein statistics (BES). Similar
branches are Maxwell - Boltzmann statistics (MBS) associated with velocities of gas mol-
ecules, Fermi-Dirac Statistics (FDS) related to electron like particles.

MBS is called as classical statistical distribution. Whereas BES and FDS are called
quantum statistical distribution. Here BES is associated with particles of positive integral spin
like 0, 1, 2, ... and are called as Bosons. FDS is related to particles of half integral spin like
1 3 5
, , ,... and are given a name as Fermion. Example of boson is a photon (from photo electric
2 2 2
effect). Example of fermion is electron, proton, neutron. At this stage we must understand the
net spin of two electrons can be 0 or 1. Hence this situation leads us that it behaves as a boson.
According to Pauli exclusion principle no two electrons (fermions) will have same set of quan-
tum numbers or same amount of energy, but in the case of bosons i.e. photons there is no limit
to their number with same amount of energy. So with a particular wavelength e.g., in red a large
number of photons (bosons) can exist. This discussion is nearly pertaining to atomic structure
atomic spectroscopy and quantum mechanics.

10.5.2 BEC - Ultra Cold Atoms

With the help of Joule-Kelvin throttle expansion cooling and adiabatic demagnetisation
effect, ultra-low temperatures like milli degree and micro degree kelvin are achieved. Various
physical phenomena are studied under these conditions. First advancement in this direction is
super conductivity of materials. Since the days of Kamerlingh Omnes many super conducting
materials have been discovered. Scientists are finding a number of applications of super con-
ductors in magnetic resonance imaging, particle accelerators, magnetic fusion devices, electric
power transmission, very fast electronic switches, squids etc. The second phenomenon studied
is super fluidity. Fluid has a property called viscosity. Viscous flow means friction to the flow.
Now super fluidity is providing no friction to flow such was experience encountered in the case
of He-4 which is the superfluid form of an isotope of helium. Super fluidity was discovered by P.

124
Kapitsa and others in 1937. Superfluid is a substance which looks like a normal liquid but flows
without friction on any surface. Except its own inertia super fluids allow to continue to circulate
over obstructions and through pores in containers which hold it. Helium-4 atoms are Bosons.

Later a number alkali metals, alkaline earth metals and lanthanides have been found to
be superfluid BECs. These are mainly diluted vapours. Such atoms are mainly diluted vapours.
Such atoms are called ultra cold atoms. One group of physicists are able to use evaporative
laser cooling technique to produce 2000 atoms of 87 Rb trapped in an enclosure. Another group
did experiment on 1000 atoms of lithium. These are bosons and all are at almost same energy.
Such ultra cold atom groups together are called as if they are one single super atom. This
dispalys distinct quantum properties. De Broglie assigned wavelength to electron and Schrodinger
gave wave equation to it. They associated a wave function to electron in around 1925. From
1995 onwards, with the help of magnetic optical trap physicists are able to provide us images of
wave functions of ultra cold atoms (super atoms). Several Nobel prizes were awarded for such
studies.
8
The speed of light in one such experiment has been reduced from 3  10 m / s to
17 m/s. The aim is reduce the speed to zero, store the electromagnetic signal and send it later.
This leads ultra cold atoms are to be used for quantum computation and quantum simulation.
Super fluids will improve performance of atomic clocks, integrated circuits and high precision
gyroscopes.

10.6 SUMMARY

A thin hole in tanks of liquid oxygen and liquid helium produces a thrust on a rocket. This
provides a dynamic lift on the rocket. So it is made to go into its orbit around the earth. At low
temperatures biological organisms are made to live longer. There are many cases in which
human body parts are transported along with patient for proper surgical operation. This is pos-
sible with suitable refrigeration. We need refrigeration for industrial, medical research and for
domestic purposes. Air conditioning also emerges an application of low temperature.

One of the important layer in atmosphere is ozone layer. This is protecting life on earth.
Very unfortunately CFCs leaked into atmosphere convert O3 into O 2 .So ozone layer is de-
pleted. This makes uv to fall on us and cause skin cancer and global warming.

There is another development of ultra-low temperature i.e. producing ultral cold atoms
called super atoms. This branch of study is known as Bose Einstein condensate. Recently
Nobel prizes are also awarded in this field of research. Some applications are also identified.

125
10.7 CHECK YOUR PROGRESS
1. Name some refrigerants.

_____________________________________________________________________
_____________________________________________________________________
_____________________________________________________________________

Ans. NH3 ,SO2 and CCl 2 F2 are some refrigerants.

2. Define the coefficient of performance of a refrigerator.

_____________________________________________________________________
_____________________________________________________________________
_____________________________________________________________________
Ans. It is given by the following ratio.

heat extracted from cold reservoir


work done on refrigerant

3. How chlorine disturbs ozone?

_____________________________________________________________________
_____________________________________________________________________
_____________________________________________________________________
Ans. uv + Freon  Cl

Cl  O3  ClO  O2

10.8 MODEL EXAMINATION QUESTIONS

I. Answer the following questions in about 10 lines.

1. Mention applications of low temperature physics on a broad basis.

2. What are the basics of refrigeration?

3. Explain the ideal refrigeration cycle.

4. Write a note on commercial refrigeration cycle.

5. Enumerate characteristics of refrigerants.

6. Briefly write about Earth’s atmosphere.

7. What is ozone layer?

126
8. Explain harmful effects of high energy radiation.

9. What are basic concepts of Bose-Einstein condensate?

10. Explain the concepts of ultra cold atoms associated with Bose-Einstein condensate.

II. Answer the following questions in about 30 lines.

1. Describe a varpour compression refrigerator. Mention the characteristics of refriger-

ants.

2. Distinguish between ideal and commercial refrigeration cycles.

3. What is ozone layer of our atmosphere? How CFC is disturbing ozone layer?

4. Write a detailed account of Bose-Einstein condensate. Explain the developments lead-

ing to ultra cold atoms.

10.9 GLOSSARY
1. Super Conductor:

Some substances show almost zero resistivity below a low transition temperature. Such
substance is called a super conductor its resistivity is of the order of 1025 ohms m.

2. Super Fluid:

A substance like He-4 flow is such that its visosity is zero. Such substances are called
super fluids.

3. Freon:

This is brand name of a refrigerant C Cl2 F2 .

4. Super Atom:

A group of boson atoms having the same ultra cold temperature displaying distinct
quantum properties are located at a cavity called magneto optical trap.

10.10 FURTHER READING

1. Heat and Thermodynamics by M.W. Zemansky, Mc Graw Hills Publications

2. A Text Book of Heat by J B Rajam; S chand & Co

3. Heat and Thermodynamics by D.S.Mathur; Sultan Chand & Sons

4. Unified Physics: Thermodynamics by S.L Gupta & Sanjeev Gupta. Jai Prakash Nath &
Co. Meerut.

5. Wikipedia & Encyclopedia Brittanica.

6. Common Core Physics: Thermodynamics by D V Brahmajiet al, Vikas.

127
UNIT-11 : BLACK BODY RADIATION (CLASSICAL
CONCEPT)
Contents

11.0 Objectives

11.1 Introduction

11.2 The Black Body

11.3 Total Radiation From Black Body - Stefan - Boltzmann Law

11.4 Distribution of Energy in the Black Body Spectrum - Wein’s Law

11.5 Distribution of Energy in the Black Body Spectrum - Rayleigh - Jean’s Law

11.6 Summary

11.7 Check Your Progress - Answers

11.8 Worked Examples

11.9 Model Examination Question

11.10 Further Reading

11.0 OBJECTIVES

After going through this unit, you will be able to:

 Describe a perfectly black body.

 Explain the distribution of energy among the wave lengths of radiation emitted by a
black body.

11.1 INTRODUCTION

Heat energy can be transmitted from one place to the other not only by conduction and
convection but also by radiation. Heat, like light, is transmitted through vacuum. The radiation
coming from a hot body has all the properties similar to that of light like rectilinear propagation,
transmission through vacuum, same velocity of propagation, inverse square law of variation of
intensity with distance, reflection, refraction and transmission, polarization interference and
diffraction. More generally we can say that radiation or radiant energy is a more expressive
term, light being only a kind of radiant energy which has the distinctive power of affecting the
retina of the human eye. Radiation can be of any wavelength from 0 to  and the spectrum is
known as electromagnetic spectrum.

128
 When radiation falls on matter, depending on the nature of the surface, any or all of the
processes namely reflection and transmission may take place. the reflecting power of a surface
is defined as the ratio of the amount of radiation reflected by the surface to the total amount of
radiation normally incident on the surface. The absorptive power of a surface is defined as the
ratio of the amount of radiant energy absorbed by the surface in a given time to the total
radiation incident on the surface in that same time. The transmitting power of a surface is the
ratio of the amount of radiation passing through it to the total radiation incident on it. Thus if r, a
and t represent the reflecting power, absorptive power and transmitting power respectively of a
surface of the matter, then when ration falls on it, we have

r+a+t=1

The values of r, a and t of a given surface of matter for incident radiation depend on the
wavelength of the radiation. Depending on the values of r, a and t we can classify the substances.

A perfect black body is one for which r = 0, t = 0 and a = 1. That is, all the radiation
incident on the surface will be completely absorbed and no radiation is reflected or transmitted.
The body appears black. Perfect black body is an ideal realisation. Lamp black and platinum
black are the nearest approaches to the ideal black body.

A perfect white body is one for which r = 1, t = 0 and a = 0. As far as the visible
radiation is concerned, a piece of white chalk may be considered to a best approximation as
perfect white body.

Before Prevost put forward his theory of exchanges in 1792 it was thought a hot body
emits hot radiation and a cold body emits, cold radiation. According to Prevost substances at all
finite temperatures emit radiant energy which increases with increase in temperature and is not
affected by the presence of surroundings. The rise or fall in temperature of the body is due to its
exchange of radiant energy with surrounding bodies, when the radiant energy received by a
body equals the radiant energy emitted by the body then the temperature of the body remains
constant. The body ceases radiating when it is at 00K.

At any given temperature a body radiates heat in all directions and the radiation contains
waves of several wavelengths. The emissivity of a surface is the amount of heat radiated in unit
time by unit area of the surface per unit difference of temperature between the surface and the
surroundings. The emissive power of a surface is defined as the ratio of quantity of heat emitted
by a given surface in a certain time to the heat emitted in the same time by a perfectly black
body of the same area at the same temperature. Kirchhoff proposed a law which states that at
any temperature for any wavelength    , the ratio of the emissive power of a body  e  to its
absorptive power at that temperature for that wavelength  a  is constant and is equal to the
emissive power of a perfect black body  E  . Thus

129
 e
 E ... 11.2
a

In this unit we shall study in detail how we can realize a black body and the various
theories to explain the experimental observations regarding the radiation emitted by a black
body.

11.2 THE BLACK BODY

When an enclosure is maintained at constant temperature it becomes filled with radiation

characteristic of a perfectly black body. When a small hole is made on the wall of the enclosure,
the radiation coming out of it will be nearly identical with the radiation coming from a perfect
black emissive surface. The smaller the hole the more completely the radiation resembles black
body radiation. The black body devised by Fery is shown in figure 11.1. Here the radiation

11.1 Fery Black Body

comes out from hole H. The conical projection P opposite to the hole is intended to avoid direct
radiation from the surface opposite the hole which would otherwise make the body not perfectly
black. The inner side of the enclosure is painted black. The enclosure behaves as a perfect
black body towards incident radiation also. Any radiation passing through the hole into the
enclosure will be reflected internally and gets absorbed.

The black body formulated by Wein can be see in Fig 11.2. Generally, this model is in
use now a days. This consists of hollow cylinder C made of bronze or platinum. The inner walls
of the cylinder are coated black. Porcelain concentric tubes are wound round this cylinder. This
tube is heated by passing current through the platinum foil wound round the cylinder. The radiation
emitted from the inside of the cylindrical metallic cylinder passes through number of limited
diaphragm and emitted through H. The temperature of this black body is measured using a
thermocouple T.

130
 Fig. 11.2 Wiens Black Body

11.3 TOTAL RADIATION FROM BLACK BODY - STEFAN -

BOLTZMANN LAW

By annalysing the experimental data of Tyndall and Dulong and Petit, Stefan in the year
1879 deduced empirically that the total radiation from any heated body is proportional to the
fourth power of its absolute temperature. In 1884, Boltzmann gave a theoretical proof of the law
based on thermodynamic considerations. The law which goes by the names of the two scientists
is known as Stefan - Boltzmann law and is applicable to emission from black bodies only. The
law may be states as follows.

When a black body at absolute temperature T is surrounded by another black body at

absolute temperature T0 , then the amount of energy E lost per second per square centimeter of
the former is given by

E   T 4  T04 

Where  is known as Stefan’s constant. Its value is given by

5.67  105 erges s 1cm2 K 4 or 5.67  108 W / m 2 K 4

Lummer and Pringsheim investigated the emission from a black body over the
temperature range 100 0 C to 1260 0 C and found the law to hold good within the experimental
error. Assuming the Sun as a black body Stefan’s Boltzman law can be used to find the surface
temperature of the Sun.

131
11.4 DISTRIBUTION OF ENERGY IN THE BLACK BODY
SPECTRUM - WIEN’S LAW

A black body at a temperature T emits radiation of different wavelengths. The energy

distributed in different wavelengths is different. Based on thermodynamic principles Wien
attempted to explain how energy is distributed over different wavelengths.

To find the distribution of energy in the thermal spectrum Wien considered an enclosure
full of black body radiation expanding adiabatically with a velocity small compared with the
velocity of light. He proved by thermodynamic reasoning that after adiabatic expansion the
enclosure was found still full of radiation but was characteristic of a new temperature.

During the adiabatic expansion, as the perfectly reflecting walls of the enclosure move
outwards the wavelengths of all the waves incident upon the walls change due to Doppler
effect. If the radius of the enclosure changes from r to r1 then wavelength  of the radiation
changes to 1 satisfying the following relation

 r
 ... 11.4
1 r1

Thus the wavelength increases in the same ratio as the radius of the adiabatically
expanding spherical enclosure. By evaluating the work done by the radiation pressure during the
adiabatic expansion and applying Stefan - Boltzmann law and using the relation (11.4) Wien
deduced the following relation.

T 1
 ... 11. 5
T1 

or 1T1  T

So T  constant. ... 11.6

equation 11.6 is known as Wien’s first displacement law. Accordingly when the radiation
of a particular wavelength corresponding to a definite temperature is adiabatically altered to
another wavelength, the temperature changes in the inverse ratio. On raising the temperature of
a black body the ordinates of the energy curve move towards shorter wavelengths by an amount
such that the product  T is a constant.

Wien derived a relation connecting the emissive power  E  of a black body and its
temperature T and is given by

E T 5 = constant. ... 11.7

132
 The above equation is known as Wein’s second displacement law, which states that the
monochromatic emissive power of a black body varies directly as the fifth power of the absolute
temperature.

Combining Equations 11.6 and 11.7 we get

E  5 = Constant ... 11.8

Wien supposed that E  5 should be some function of  T  .

Thus

E  5  Af  T  ... 11.9

Where A is an absolute constant. The distribution of energy in the spectrum of a black body
radiation can be expressed as

E  A 5 f  T  ... 11.10

Equation 11.10 does not represent the actual distribution of energy in the spectrum of a
black body since it contains the unknown function f  T  . To obtain the form of the function
f  T  , Wien made the following assumptions regarding the emission of radiation from a black
body.

1. The radiator considered as a hollow vessel filled with a gas mixture capable of absorbing
and emitting radiations of all wavelength.

2. Each molecule of the gas emits only a single wavelength which depends on its velocity.

3. The energy of radiation wavelength lying between  and  +d  is proportional to

a) Number of molecules vibrating within the periods corresponding to the wavelength

within the limits  and  +d  . and

b) A function of molecular velocity.

By applying Maxwell’s law for the distribution of velocities and the principles of
equipartition of kinetic energy Wien obtained a form of f  T  and deduced the radiation
formula.

 C 
E  C1 5 exp  2  ... 11.11
 T 

Where C1 and C2 are constants.

133
 The distribution of energy among the wavelength of radiation emitted by a black body
was investigated experimentally by Lummer and Pringsheim in 1899 and Wein’s law was subjected
to experimental verification. A carbon plug situated in an electrically heated carbon tube was
used as the source of radiation. The tube was thermally insulated by surrounding it with coaxial
tubes of fireclay and asbestos. A current of nitrogen was passed over the carbon tube to

Fig 11.3 The Energy distribution curves

E = Emissive power

 = wavelength

Prevent it from oxidation at high temperatures. A thermocouple was used to measure

the temperature. The radiation spectrum from the carbon tube was produced by refraction
through a prism of Fluorspar. Fluorspar is transparent to infrared radiation (heat radiation) and
its two strong absorption bands are out side the region of investigation. Corrections were applied
to convert the prismatic spectrum into a normal one. The radiation after dispersion was focused
using silvered concave mirrors and the energy in the various parts of the spectrum was measured
by means of linear bolometer. The energy of distribution in the spectrum for temperatures
between 621 and 16460K was obtained. The energy distribution curves obtained are shown in
Fig 11.3.

The emission is maximum at a particular wavelength  m  at any given temperature

and m shifts to lower wavelengths as the temperature is increased. m T is found to be constant
(0.2898 cm 0K) in accordance with Wien’s displacement law. The total radiation emitted per
second at any temperature is given by the area enclosed between the curve and the X-axis and
is found to be proportional to T 4 in accordance with Stefan - Boltzmann law. Within the limits of

134
experimental error EmT 5 , where Em corresponds to the maximum energy radiated at given
temperature at m , was found to be constant obeying Wien’s displacement law. However the
formula given by Eq. (11.11) does not represent the variation of radiation energy at higher
wavelengths accurately while the law accounts well at shorter wavelengths. As per Eq.(11.11)
when   0 or , E  0 . Thus no energy is emitted by a wave of infinite wavelength or zero
wavelength. The experimental curve as shown in Fig 11.3 does not pass through the origin
contradicting the Wien distribution law. Also when T  , E  A 5 which is a finite quantity..
This is wrong in view of Stefan - Boltzmann law E    T 4 , as T  ,E    . These results
indicate that the assumptions based on which the distribution law was derived may be defective
somewhere and must be rectified. This problem was tackled by Rayleigh and Jeans in 1900
which is discussed below.

11.5 DISTRIBUTION OF ENERGY IN THE BLACK BODY

RAYLEIGH - JEAN’S LAW

By the time Rayleigh and Jeans took up the problem of black body radiation, Maxwell
established the fact that light is an electromagnetic radiation with electric and magnetic vectors
vibrating in mutually perpendicular directions and perpendicular to the direction of propagation.
This concept of radiation was applied to black body radiation by Rayleigh and Jeans. According
to the electromagnetic theory a black body emits radiation of continuously variable wavelengths
from zero to infinity. The radiation suffers multiple reflection inside the cavity giving rise to
standing wave patterns. Each mode of vibration represents a standing waves. As per the laws
of probability the number of modes of vibration lying between  and  +d  is given by 8 4 d .
According to the principle of equipartition of energy the total energy per mode of vibration is
given by kT where k is called the Boltzmanns constant and T represents the absolute temperature
of the system. Hence the total energy of the system consisting of 8 4 d modes of vibration
lying within the range  and  +d  is given by

E d  8 4 d  kT ... 11.12

or E  8 4 kT ... 11.13

Since C  v ... 11.14

Where C represents the velocity of light and v represents the frequency of the mode,
we can express Eq.11.13 as

8 v 4 kT
Ev 
e4

Eq. 11.13 and 11.15 represent Rayleigh - Jeans’ law.

Rayleigh - Jeans law was found to hold good with experimental results for long wavelength
and high temperatures, When T   , E   , whereas in Wien’s relation E is finite when

135
T   . Rayleigh Jeans law does not fit in with experimental data at low temperatures and
short wavelengths. As per Eq. 11.13 at any given temperature when   0, E   which is
against the experimental observation. This is known as ultraviolet catastrophy.

The total energy E can be given by


E   E d   8 kT   4 d  ... 11.16
0


 1 
E  8 kT  3  ... 11.17
 3  0

1 1 
E  8 kT  3  3   8 kT   ... 11.18
0  

As per Rayleigh - Jeans’ law the total energy at any given temperature comes out to be
infinity whereas it should be finite except as absolute zero it becomes zero.

Thus we find Rayleigh - Jeans’ law to be successful in explaining the energy distribution
in black body spectrum only at high temperatures and higher wavelengths.

Check Your Progress:

Note: (a) Space is given below for writing your answer.

(b) Compare your answer with the one given at the end of this unit.

Rayleigh Jeans law does not hold good at _______ temperatures and ______ wavelengths.

_____________________________________________________________________
_____________________________________________________________________

11.6 SUMMARY

A perfect black body is one which absorbs completely all the radiation falling on it and
reflects or transmits no radiation from it. Lampblack and platinum black are the nearest approaches
to the ideal black body.

Prevost theory of exchanges states that substances at all finite temperatures emit radiant
energy which increases with increase in temperature and is not affected by the presence of
surroundings. The rise or fall in temperature of body is due to its exchange of radiant energy
with surrounding bodies. Stefan - Boltzmann law states that the energy radiated by a black body
per sec per square centimeter is proportional to the fourth power of its temperature in absolute
scale. According to Wien’s displacement laws, (i) the wavelength at which the emissive power
of a black body is maximum is inversely proportional to its temperature and (ii) the monochromatic

136
emissive power of black body varies directly as the fifth power of the absolute temperature.
 C 
Wien’s radiation law is given by E  C1 5 exp   2 
 Tk 

when E represents the emissive power of the black body at the wavelength  and
temperature T 0 K , C1 and C 2 are constants. Rayleigh - Jeans radiation law is given by

E  8 4 kT

Where k is the Boltzmann constant.

Wien’s law holds good with the experimental results only at shorter wavelengths whereas
Rayliegh - Jean’s law explains the experimental results, that is the energy distribution in the
spectrum of black body radiation, only at higher wavelengths.

Planck’s law explains satisfactorily the experimentally observed black body spectrum.
As limiting cases the Wein’s law, Rayleigh - Jean’s law and Stefan - Boltzmann law can be
deduced from Planck’s law.

11.7 CHECK YOUR PROGRESS - ANSWERS

1. Rayleigh Jeans’ law does not hold good at low temperature and short wavelength.

11.8 WORKED EXAMPLES

Example 1:

The average amount of solar radiation the Earth receives is 2.03  104 j / m 2 /  min . If
the Earth re-emits this radiation in the form of black body radiation, determine the temperature
of the earth.

According to Stefan - Boltzmann relation

E  T 4

where  is the Stefan - Boltzmann constant.

1/ 4
E
T   
 

E represents the energy emitted by the black body from its surface of unit area per
second.

2.03  104 Jm2 sec 1

E  2.03  104 Jm 2 min 1 
60

E  338.3 Jm2 s1

137
The Stefan - Boltzmann constant

  5.67  108 Wm2 K 4

or

  5.67  108 Js 1m2 K 4

1
4
E  338.3 Jm2 s 1 4
T      8 1 2 4 
    5.67  10 Js m K 

1/ 4
T   59.66  102 K

T  2780 K .

11.8 MODEL EXAMINATION QUESTIONS

I. Answer the following Questions in about 30 lines.

1. Discuss Wien’s law for the distribution of energy in the radiation spectrum of a black
body. Give an account of its experimental validity.

2. Derive Rayleigh - Jeans’ law. Discuss its experimental validity.

II. Answer the following Questions in about 10 lines.

1. Define and explain Prevost’s theory.

2. Define and explain Stefan-Botlzmann theory.

3. How to formulate a black body for experimental observations - Explain.

III. Solve the following problems.

1. The maximum in the energy distribution curve of radiation emitted by a black body
occurs at   3500A0 . Determine the surface temperature of the black body..

0
(Ans. 8285 K )

2. The maximum temperature in the fire ball resulting from nuclear bomb explosion is
found to be 1080 K . Determine the wavelength at which radiation emission is maximum.
Determine the corresponding quantum energy.

(Ans. 0.290 A0 ,   42.8 KeV )

138
3. The intensity of radiation emitted by a black body is found to be maximum at
  6000A0 .The temperature of the body is raised until its radiation energy emission is
doubled. Determine the wavelength at which the intensity of radiation is a maximum.

 Ans : 
max  5000 eA0 

11.9 FURTHER READING

1. Heat & Thermodynamics - Zemanski

2. Text book of Heat by Sahas Srivatsava

139
UNIT - 12 : BLACK BODY RADIATION QUANTUM
CONCEPTS
Contents

12.0 Objectives

12.1 Introduction

12.2 Black Body Radiation - Planck’s Law

12.3 Applications of Planck’s Quantum Concepts

12.3.1 Photoelectric Effect

12.3.2 Specific Heats of Solids

12.3.3 Compton Effect

12.3.4 Other Applications

12.3.5 Conclusions

12.4 Summary

12.5 Check Your Progress - Answers

12.6 Worked Out Examples

12.7 Model Examination Questions

12.8 Glossary

12.9 Further Reading

12.0 OBJECTIVES

This unit is divided into two parts.

1. Planck’s law of black body radiation

2. Applications of Planck’s law

After going through this unit you will be able to

 Understand quantisation of energy according to Max Planck.

 Apply Planck’s law to photoelectric effect as Einstein did.

 Use quantisation of energy to understand specific heats of solids at low temperature.

 Explain Compton effect and dual nature of matter.

140
12.1 INTRODUCTION

We have seen in the previous sections that Wien’s law can account satisfactorily the
energy distribution in the black body spectrum only at short wavelengths. Rayleigh-Jean’s law,
accounts well the black body spectrum only at higher wavelengths. Neither of these two laws
could account satisfactorily the distribution of energy in the complete spectrum of the black
body. These observations indicate that the assumptions made regarding the radiation emitted by
a black body based on which the Wien’s and Rayleigh-Jeans law have been derived must be
defective. In the year 1901 Max Planck put forward a new concept namely quantum concept
regarding the radiation emitted by a black body and derived an expression for the radiation law
that satisfactorily accounts for the experimentally observed spectrum throughout the range.

Black body radiation is originally associated with heat radiation. Later light, ultra violet,
X-rays and infrared, microwave, radio waves are also included in electromagnetic spectrum.
Max Planck introduced quantum or packet of energy emission where as before that energy
emission was continuous. Planck obtained Wien’s law and Rayleigh - Jeans law from his equa-
tion showing its supremacy.

The real greatness of Planck’s theory came later when Einstein used it in explaining
photoelectric effect. Again Einstein applied quantum of energy concept to the specific heats of
solids at low temperatures. Debyes used it in greater details successfully even at very low
temperatures. Neils Bohr’s atomic structure is again based on quantum concept but this time
angular momentum is quantised. Finally Compton completed the photon particle picture in ap-
plying both quantisation of energy and momentum to solve the problem of X-ray scattering. The
quantum physics continuous to grow further.

12.2 BLACK BODY RADIATION- PLANCKS LAW

Planck argued that the classical concept of continuous energy changes might be wrong
and proposed that energy changes could take place discontinuously and discretely as integral
multiples of a small unit of energy which is called quantum. It is assumed that the enclosure of
an experimental black body is filled with linear electromagnetic oscillators. Radiation emitted
by these oscillators will eventually fill the enclosure and a statistical equilibrium will be obtained
at some definite temperature. Under these conditions radiation will be both emitted and absorbed
by each oscillator. There exists a definite ratio between the density of radiation of any given
frequency and average energy of the oscillators of that frequency.

It is assumed that the linear oscillators can vibrate with integral energy values
0,  , 2 , 3 , ...,n where  represents the energy of elementary quantum. Thus if v represents
the frequency of the oscillator its energy E can be given by

E = nhv ... 12.1

here n = 0, 1, 2, ..., n

141
 Where h is called the Planck’s constant. Its value is 0.920 x 10.34 JS. The energy of
the elementary quantum E = hv.

The number of vibration of the oscillators within the range of wavelengths  and
 +d  according to classical statistics is given by 8 4 d  . The total energy emitted by the
oscillators lying in the wavelength range  and  +d  given by

E d   8 4 d  E ... 12.2

Where E represents the average energy per oscillator. E has been evaluated by
Planck applying the laws of probability. We can write


 n0
Ee  E / kT
E  ... 12.3
 n0
e  E / kT

 
where  n0
Ee  E / kT represents the total energy of all the oscillators and  n 0
e  E / kT
represents the total number of all oscillators. Substituting the value of E from Eq.12.1 in Eq.12.3
we get

  nhv / kT

E
 nhve n 0
  nhv / kT ... 12.4
 e n 0

1
Put   in Eq. 12.4, we get
kT

  nhv

E
 nhve n 0
  nhv ... 12.5
 e n0

Eq. 12.5 can be rewritten as

d  
E  log  n 0 e  nhv 
d  


Let us try to evaluate the sum  n0
e nhv


 n0
e  nhv  1  e  hv  e 2 hv  e 3 hv  ...

Let x  e  ahv then

142
 
 nx
e  1  x  x 2  x 3  ...  x n
n0

1
Since 1  x   1  x  x 2  x 3  ...  x n

We get

 1
 n0
e  n hv  1  e  hv 

d   hv 1 
Now E  
d 
log  q  e  

1  2 
E
 hv 1
 1 1  e  hv    1 e  hv   hv  
1  e 
Simplifying

hv
E 
 e  1
hv

1
Substituting for   we get
kT

hv
E ... 12.6
e hv / kT
 1

Using 12.6 in Eq.12.2 we get

hv
E d   8 4 Ed   8 4 d 
e hv / kT
 1

or

hv
E  8 4
e hv / kT
 1

Using c = v  we get

8 4 hc /  8 5 ch
E   ... 12.7
e hc /  kT
 1 e hc /  kT  1

143
Also we can write

4
c
8   hv
v 8 hv 3 1
E  kv / kT  ... 12.8
 e  1 c 3
 e  1
hv / kT

Eqs 12.7 and 12.8 represent the Planck’s radiation formulae. Which fit experimental
results very well. Both Wein’s and Rayleigh - Jeans’ formulae can be obtained from Planck’s
law.

(i) Deduction of Wien’s law from Planck’s Law

hc /  kT
For shorter wavelengths e  1 and hence 1 in the denominator of Eq. 12.7 can
be neglected. Hence

8 5 hc
E   8 5 hce  hc /  kT
e hc /  kT

This relation is similar to the Wein’s law

E  c1 5 eC2 / kT

Where C1  8 hC and C2  hc / K

(ii) Deducting of Rayleigh - Jeans law from Planck’s Law

when  is large, we can write

hc
e hc /  kT  1  ... 12.9
 kT

Using Eq. 12.8 in Eq. 12.6, we get

8 5 hc 8 5 hc kT

E 
hc hc
1 1
 kT

E  8 4 kT

This is the same as Rayleigh - Jeans’ law.

144
12.3 APPLICATIONS OF PLANCK’S QUANTUM CONCEPTS

Black body is emitting radiation at different frequencies. A black body can also be
heated to different temperatures. Such hot bodies also emit radiation of many frequencies. The
black body radiation emission experimental curve has to be fitted with a suitable theory. Max
Planck offered the quantum theory of radiation successfully. But he deviated from conventional
ideas of continuous energy emission. He had imagined the emission of energy at the cavity of
radiation only. This happened in 1901. Many physicists did not accept this proposal.

Around this time there was an unsolved problem. It is called as photoelectric effect.

12.3.1 Photoelectric Effect

The photoelectric effect was discovered by H.Hertz in 1887. If light of suitable fre-
quency falls on a photo metal it releases electrons. This phenomenon is called photoelectric
effect. Such current observed is called as photoelectric current. For a given material now called
photo metal, there is a minimum photon energy hf 0 above which only photon is released from
this photo metal. No photo electrons would be released by radiation of frequency less than f 0
called the threshold frequency. Until 1905 many physicists tried but nobody could explain this
threshold minimum frequency. To explain this further, let us have a photo metal the threshold
frequency of which is in green colour region. If we use red colour light of even very high
intensity not even one photoelectron is released. On the other hand if we use blue colour light of
even very low intensity streams of electrons are released. Photocurrent is observed. In 1905
Einstein successfully applied Planck’s quantum concept and explained the threshold frequency.
The electron to be emitted by a photo metal is bound to atom with certain energy. Einstein
identified that this energy is quantised so this minimum amount of energy is essential for a
photoelectron to get emitted.

The necessary condition for photoelectric emission to take place is E  E F  W ; where

E F represents the Fermi - energy of the electrons that are at the surface. W represents the
work function of the metal and defined as the amount of energy that must exceed E F so that the
electron barely escapes from the metal surface. When an electron having an energy Ei inside
the metal that absorbs a photon and escapes. The kinetic energy of that photoelectron outside
the metal surface is given by K   E i  hf    E F  W  . For photons of given frequency the
kinetic energy of the electron is largest when its internal energy is largest. The maximum value
of Ei is E F . Hence the maximum kinetic energy of the electron emitted is given by
1
K max  eV0   hf  W   mv 2 . W is called the work function of the metal and is the amount
2
of energy that must exceed E F so that electron just escapes from the metal surface. V0 is
stopping potential that is required to make the photoelectric current to be zero. This is called as
Einsteins photoelectric equation. The following features of photoelectric emission are explained
by Einstein equation as.

145
(1) The velocity of photoelectron is directly proportional to the frequency of radiation.

(2) The velocity of photoelectron is independent of the intensity of radiation.

(3) There exists a threshold frequency which varies with the nature of the emitter or photo
material.

(4) There is no time delay in the process of electron emission.

The energy quantisation proposed by Max Planck is supported by Einstein in solving

photoelectric emission. The particle concept of vibrating quantum of radiation is photon.

12.3.2 Specific Heats of Solids

Classical Concepts

The results of kinetic theory of gases were mainly due to the work of Clausius, Max-
well and Boltzman. They included the ideas of atomic and molecular vibrations. Mean free path
of molecules and equipartition of energy associated with the possible degrees of freedom are
also considered. This happens to be the basis of classical mechanics. Analysing many experi-
mental results Dulong and Patit found that ‘The product of atomic weight and the specific heat
is the same for all elementary solid substances”. This product is known as atomic heat; it is
numerically equal to the heat capacity per kilomole. At ordinary temperatures this Dulong and
Petit law holds roughly for many substances. The values for about 60 elements ranges from
2.7 R to 3.5 R. But for boron heat capacity is 1.7 R, beryllium 1.9 R and diamond (carbon)
0.73 R. These are light elements having high melting points. As the technology is advancing the
experimental values of heat capacity is deviating more and more from Dulong and Petit law.

Einstein Quantum Concepts

Classical equipartition of energy gives the prediction that for solid elements, the specific
heat per kilo mole should be 3R as per Dulong and Petit law at high temperatures. But the
prediction failed completely in the low-temperature domain. At this stage Einstein in 1907 of-
fered an explanation of the temperature variation of the specific heat of solids. He treated each
atom as a 3D harmonic oscillator. But all are vibrating with single frequency f, having indepen-
dent vibration of its neighbours. For this purpose Einstein replaced the classical value KT for the
mean energy of an oscillator by the value derived by Max Planck. Multiplying this mean energy
hf
E by Avagadro’s number N and 3 for three degrees of 3 freedom. Now we have
e hf / KT
 1

 3Nhf 
for the vibrational energy of 1 kilo mole E  and for the specific heat per kilo mole
e hf / KT
 1
is

2
dE  e hf / KT   hf 
CV   3R  hf / KT   
dt e  1  KT 

146
 At high temperatures this expression reduces to the classical value of 3R. At low tem-
peratures the exponential becomes large and CV decreases rapidly. Einstein’s attempt was
reasonably good but at very low temperatures the theory does not match with experimental
values of CV which varies as T 3 near 00 K .

Debye Quantum Concepts:

At this stage Debye in 1912 modified Einstein’s theory with new concepts of atoms.
Debye introduced the idea of coupling of vibrations of atoms with each other in a solid. Each
atom exchanges energy with its neighbours by means of elastic waves propagated through the
crystal. These travelling waves can be treated as particles known as phonons. Phonon energies
are quatised in units of hf just as photons. So the vibrational energy of the crystal can be
associated with phonons travelling through the places of atoms of the solid. Hence the solid is
capable of vibrating elastically in many modes of different frequencies. Debye calculated the
number of independent modes of vibration in almost the same manner in which standing waves
of an electromagnetic field within a cavity of radiation as proposed by Max Planck. The chief
differences being
(1) The number of modes of vibration in a solid are limited and
(2) There are two kinds of elastic vibrations there are longitudinal (or compressional) waves
of a single type travelling with speed v l their number per unit volume of solid are

 4f 2
df 
3 . Whereas the number per unit volume of transverse vibrations with two
vl

8f 2
df 
independent polarisations (similar to light) are given by . Let the lowest fre-
v3t
quency be zero and the highest one be f m . Now on par with average quantum value,
the energy associated with each of these modes give the thermal energy of v0 volume
of one kilo mole of solid is given by

f
 1 2  m  hf  2
E 0  4v0  3  3    hf / KT f df
v
 l v t  0  e  1 

It is difficult to find the actual value of f m . Debye used an approximate value derived
from the condition that the total number of modes of vibration of a kg atom must be equal to the
number of degrees of freedom of all atoms, or it is 3N. So now

f
 1 2 4 1 2
3N  4v 0  3  3   f 2 df  v0  3  3  f m3
 vl vt  0 3  vl v t 

and thermal energy equation becomes

f
9N  hf  2
E0  f df .
f m3 0  e hf / KT  1 


147
 hf m
Using a characteristic temperature known as Debye temperature   , and putting
K
hf
x we get equation of E 0 as
KT

/T
T4 x3
E 0  9R 3  dx
 0
ex  1

and the specific heat is

dE 0   T 3  / T x 3 dx  1 
CV   9R  4    x  /T 
dT     0 e  1 T e  1 

This equation at high temperatures reduces to the classical value of 3R. Debye theory
of specific heats of solids is in good agreement with experiment. The quantum concept of
vibrating atom is known as phonon.

12.3.3 Compton Effect

In the analysis of the photoelectric effect a photon is considered as a wave packet or

quantum of energy. There was no mention of quantisation of momentum. A large amount of
momentum was carried away by the metal itself. Hence conservation of momentum could not
be usefully applied to the photon - electron system. If photon is a particle then it must satisfy
both quantisation of energy and quatisation of momentum. This is established in Compton ef-
fect. Compton in 1922 conducted an X-ray scattering experiment. He used X-rays from mole b
denum target and made them to fall on a graphite (carbon) block to get scattered. He measured
the wavelength of scattered X-ray photons with a machine known as Bragg spectrograph. At
each finite scattering angle he observed two peaks in the scattered beam. One at the incident
0
wavelength 0.707 A and the second at a wavelength longer by an amount  dependent on
the scattering angle  .

On the basis of the quantum theory of radiation, Compton derived the following rela-
h
tions,   1  cos    0.024 1  cos   A0 , which quantitatively predicted scattering at
m0 C
the observed higher wavelength, h is Planck’s constant, C is velocity of light and m 0 is rest
mass of electron. He assumed the scattering process to be treated as an elastic collision be-
tween a photon and an electron. This process is governed by the two basic laws of mechanics,
the conservation of energy and the conservation of momentum. Max Planck’s quantum theory
hc ; because c
gives the energy relation as, E  hf  c  f and f  . c being velocity of X-ray
 
E hc h

photon. On dividing E by c we get a relation for momentum P, of x-ray photon as  p.
c c 
So Compton used quantisation of energy concept as proposed by Planck and seconded by
Einstein. Hence he also proposed quantisation of momentum by his theory which was accu-

148
rately supported by his own experiment. This gave the most conclusive evidence of the particle
characteristic of electromagnetic radiation (x-rays).

12.3.4 Other Applications

Neils Bohr in 1913 proposed a model of atom, which supported spectra of H-atom. His
important contribution is the postulate on quantisation of angular momentum. The circular orbits
of electrons around the nucleus is modified by Sommerfeld with elliptical orbits. The vector
atom model made quatisation concept more clear.

De Broglie in 1923 proposed particles like electrons, protons, neutrons to have wave
h h
nature. The de Broglie wave length of such particle is    , here h is Planck’s constant,
p mv
m is mass of the particle and v is its velocity. This de Broglie theory is experimentally verified
independently by Davisson, Germer and GP Thomson in 1927.

12.3.5 Conclusions

Newton proposed corpuscular theory of light. Haygen’s enunciated wave theory of

light. Properties of light like, reflection, refraction and total internal reflection were explained by
Newton’s theory. But interference, diffraction and polarisation were explained by only Huygens’
wave theory.

Black body radiation spectrum is also included in electromagnetic spectrum. Planck’s

quantum theory is supported by Einstein’s photo electricity and Compton’s x-ray scattering.
This makes light to be a particle (or quantum or packet of energy or a photon) again. That
means light or electromagnetic radiation has both wave nature and particle nature.

An electron (or a particle of matter) also behaves as a wave. This is called dual nature
of matter. This wave nature is proposed by de Broglie. Hence the motion of particle like elec-
tron or atom with this wave nature is explained by Schrodinger wave mechanics. And the
associated development is vast in Physics.

Nature consists of energy and matter. Both these have particle nature as well as wave
nature. Pnysics deals with both these things in all its aspects.

Check Your Progress:

Note: (a) Space is given below for writing your answer.

(b) Compare your answer with the one given at the end of this unit.

1. Write the applications of Planck’s laws.

_____________________________________________________________________
_____________________________________________________________________

149
2. What is common in the phenomena developed by Planck, Einstein and Comption in this
unit?
_____________________________________________________________________
_____________________________________________________________________

12.4 SUMMARY

Planck introduced the quantum concept regarding the energy possessed by a cavity
oscillator. He proposed that the cavity oscillator cannot accommodate all possible energies but
can have energy n  where in n is an integer and   hv . h represents the Planck constant
and v the frequency of the oscillator.

According to Planck’s theory the average energy possessed by a cavity oscillator is

given by

hv
E
e hv / T
 1

Planck’s radiation formula is given by

8 5
E 
  hc  
exp     1
   kT  

Where c represents the velocity of light.

Planck’s law explains satisfactorily the experimentally observed black body spectrum.
As limiting cases the Wien’s law, Rayleigh - Jean’s law and Stefan - Boltzmann law can be
deduced from Planck’s law.

The emission of electrons by metals when bombarded by electromagnetic radiation is

called photoelectric effect. This was discovered by H.Herz. Einstein in 1905 offered a success-
ful explanation for this phenomenon based no Planck’s quantum theory.

Specific heats of solids at low and very low temperatures was not explained for a
longtime by classical physics. Again Einstein in 1907 offered an explanation based on Planck’s
quantum theory. Which is good but could not explain in the very low temperature regions.
Debye modified Einstein’s theory of specific heats of solids suitably and achieved success.

All along quantisation of energy is the only aspect we are observing. Quantum is a
packet of energy also called as photon, which is a particle. Hence a particle needs quantisation
of momentum. This is observed in the problem of x-ray scattering by materials. Compton did the
experiment and offered a theory very accurately to solve the problem.

Neils Bohr atomic model introduces quantisation of angular momentum, which is yet
another advancement in physics. Finally de Broglie’s wave nature of matter makes the comple-
tion of dual nature of matter and energy.

150
12.5 CHECK YOUR PROGRESS - ANSWERS
1. Deduction of Wein’s law & Deduction of Rayleigh - Jeans law

2. Particle nature of radiation.

12.6 WORKED EXAMPLES

Example 1:

Starting from Planck’s law obtain the Wien’s displacement law.

When   m E becomes maximum. Hence

d
 E   0 for a given temperature T..
d

Hence

1
E  8 5 hc
e hc /  kT
 1

d d   5 
 E   8 hc  hc / kT 
d d   3  1 


d  5 hc / kT 1

 8 hc
d  
  e  1 

1
 8 hc  e hc / kT  1  5  6   5  1 
 

 1 2 hc 
 8 hc  e hc /  kT  1  5  6   5  1  e hc /  kT  1 e hc / kT   
 kT  2 

d
When    m;  E   0 . Hence
d

 1 hc hc /  kT hc /  kT 2 
8 hc  5 6  e hc /  kT  1  7
e  e  1   0
 kT  

or

e hc /  kT / hc
5  6 
e hc /  kT
 1  7 kT

151
or

hce hc /  kT
e hc /  kT
 1 
5k T

or

 hc 
e hc / kT 1   1
 5k T 

x x hc
The above equation is of the form e 1    1 , where x 
 5  kT

the roots are x = 0 or

x 1
1 
5 ex

or

5
x 5 or x = 4.965
ex

x = 0 is absured since    . Since   max  m we take x = 4.965

Hence

hc
 4.965
m kT

hc
mT 
k  4.9650  = constant.

This is Wien’s displacement law.

Example 2:

Obtain Stefan - Boltzmann law based on Planck’s law.

The total energy emitted per unit area per second by a black body at temperature T is
given by

 
8 hv3  1 
ET   E v dv   3  hv / kT 
0 0 e e 1 


8 h 3 v3 dv
ET 
C3 0 ehv / kT  1

152
Put hv/kT = x

kT kT
dv  dx and v  x in the above equation.
h h

Then


8 h k 3T 3 x3 kT  1 
ET  3  dx  x 
C 0 h3 h  e 1

 
8 k 4T 4 x3 1 4 4
0  e x  1 dx  A0 x dx  e  1 where A  8 k3 T3
3 x
ET 
h 3c 3 hc


ET  A x3 dx  e  x  e 2 x  e3 x  ...
0


3 4 x 6
Since x e
0
dx 
r4
.


1 4 
E
 T  A6n0 r
4
 A6  
 90 

8 k 4T 4 6 4  48 5 k 4  4
ET   T
h3c 3 90  90h3 c3 

 ET  CT 4

where C is a constant.

This is Stefan - Boltzmann law.

Example 3:

The maximum in the energy distribution curve of solar radiation occurs at   4700 A0 .
Considering sun to radiate like black body determine the surface temperature of the Sun.

The Wein’s displacement law derived from Plank’s law as per worked example 1 is given

hc
max T 
k  4.965

hc
T
k  4.965  max

153
 6.626  1034 Js  3  108 m
T
4.700  1010 m  1.3805  1023 jK 1  4.965

T  61700 K .

Example 4:

Evaluate Compton shift  , for   300 ,600 and 900 of scattering angle.

  0.24 1  cos   ;

  300  cos   0.8660   0.032A0

  600  cos  0.50   0.12A 0

  900  cos  0.0   0.24A 0

12.7 MODEL EXAMINATION QUESTIONS

I. Answer the following questions in detail.

1. Derive Planck’s radiation law. Discuss how the Wein’s law and Rayleigh - Jean’s law
can be obtained from Planck’s law as limiting cases.

2. Derive Planck’s radiation law.

3. Obtain Wien’s law and Rayleigh - Jean’s law from Planck’s law.
4. Discuss Einstein’s and Debye’s quantum concepts of specific heats of solids.
II. Answer the following questions in brief.
1. What is photoelectric effect? What is Einstein’s explanation for it?
2. What is Compton effect? Explain.

12.8 GLOSSARY
1. Photoelectron:
A photoelectron is released when radiation of suitable frequency falls on a photo metal.

2. Threshold frequency:

For photoelectric effect to be observed in a photo metal a minimum amount of fre-

quency of radiation is required. This is called threshold frequency.

154
12.9 FURTHER READING
1. Introduction to Modern Physics by H S Mani and G K Mehta, affiliated East-West
Press Pvt. Ltd.
2. Elements of Modern Physics by S H Patil, Tata Mc Graw Hills
3. Introduction to Modern Physics by Richtmyer, et.al, Tata Mc Graw Hills
4. Heat & Thermodynamics - Zemanski

5. Text book of Heat by Sahas Srivatsava

6. Unified Physics - Vol II, Dr. S. L Gupta and Sanjeev Gupta

155
 Dr. B. R. Ambedkar Open University
Faculty of Science
III Semester (3 Year Degree Course)
MODEL QUESTION PAPER
PHYSICS DSC-III
COURSE - 3: THERMODYNAMICS
[Time: 3 hours] [Max. Marks: 80]
[Min. Marks : 32]
Section - A
(Short Answer Questions)
[Marks: 4 x 5 = 20]

Note: (a) Answer any FOUR of the following in about 10 lines.

(b) Each question carries 5 marks.

1. [Block - I] Explain transport phenomena in gases.

2. [Block - I] Explain with suitable examples the reversible and irreversible process in
brief.

3. [Block - II] A steam engine takes steam from the boiler at 2000C at 10 atmospheric
pressure and exhausts directly into air at 1 atmospheric pressure at 1000C. Calculate
the maximum efficiency of the steam engine.

4. [Block - II] Discuss the formulation of thermodynamic temperature.

5. [Block - III] What are thermodynamic potentials.

6. [Block - III] Clasius Clapyron’s equation - derive it.

7. [Block - IV] Define and explain Prevost’s theory.

8. [Block - IV] Define and explain Stefan - Boltzman theory.

Section - B
[Long Answer Questions]
[Marks: 4 x 10 = 40]
Note: (a) Answer the following questions in about 30 lines.
(b) Each question carries 10 marks.

156
9. [Block - I] State and prove Carnot’s theorem.
(or)
10. [Block - I] Derive the expression for the Maxwell’s distribution of molecular speed of
a gas.
11. [Block - II] Discuss the formulation of thermodynamic temperature scale based on
second law of thermodynamics.
(or)
12. [Block - II] Define entropy. Show that in all reversible processess the total entropy
of the system and its surroundings remain constant.
13. [Block - III] Write down the differential relations for the thermodynamic potentials.
(or)
14. [Block - III] Joul-Kelvin’s effect write about this also derive the Joul - Kelvin
coefficient.
15. [Block - III] Dervie Planck’s radiation law and applications of Planck’s law.
(or)
16. [Block - IV] Derive Rayleigh - Jean’s law, discuss its experimental validity.

Section - C
(Objective Type Questions)
(Marks : 20)
Note: (a) Answer the following questions.
(b) Each question carries 1 mark.
I. Multiple Choice questions. Choose the correct answer. (10 marks)
1. The number of temperature scales in use now [ ]
(a) 3 (b) 1 (c) 2 (d) none
2. Formualte convert Centigrade into Fahrenheat is [ ]

C F  32 5 9 9
(a)  (b)  F  32 (c) F (d) none
100 180 9 5 5

3. Efficiency of heat [ ]

T1  T2 T1  T2 T1 T1
(a) (b) (c) (d)
T1 T1 T1  T2 T1  T2

4. Reversible Carnot’s cycle there is [ ]

(a) change in entropy (b) no change (c) both a & b (d) none

157
5. The unit of entropy [ ]

(a) JK 1 (b) JK 2 (c) JK (d) JK 2

6. Entropy of the system in the irreversible process [ ]
(a) increases (b) does not increases
(c) decreases (d) none
7. First law of thermodynamics is [ ]
(a) dQ = dU + dW (b) dQ = dU - dW (c) dU/dW (d) none
8. Net amount of heat energy gained by the system in teh cycel is given by [ ]

Q1  Q 2
(a) Q1  Q 2 (b) Q1  Q2 (c) (d) none
2

9. ___ year Prvost put forward his theory of excahnges. [ ]

(a) 1792 (b) 1829 (c) 1762 (d) 1972

10. E    T 4  T0 4  where  is ______ [ ]

(a) Wien’s constnat (b) Stefan’s constnat

(c) Rayleigh - jean’s constant (d) none

II. Match the following. (5 marks)

1. One of the thermodynamic equation [ ] (a) dH = Tds + Vdp
2. The unit of heat [ ] (b) Calorie

Vf

3. Equation for work done by a gas as it expands[ ] (c) W   PdV

Vi

Q1  Q 2
4. Efficiency of heat engine is given by [ ] (d)
Q

(e) E    T  T0 
4 4
5. Stefan’s - Boltzman equation [ ]

Q1  Q 2
(f)
2

158
III. Fill in the blanks (5 marks)

V 
1. Q1  W1   RT1 log  2  , where  is ___________
 V1 

2. Maxwell’s 4th equation is ___________

3. Rayleigh - Jean’s equation is ___________
4. Rayleigh - Jeans law does not hold good at ___________ temperatures and _____
wavelength.
5. E = nhv, wehre h is ___________constant.
***

159