Paper IV - Thermodynamics &radiation Physics

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Unit – I
Chapter – 1: Kinetic theory of gases
 Postulates of Kinetic theory

Kinetic theory was developed mainly by Maxwell, Claussius and others in explaining
satisfactorily the behaviour of perfect gases.
The fundamental postulates of thee kinetic theory of an ideal gas are
1. All gases are made up of molecules which are considered to be rigid, perfectly elastic and identical in
all respects.
2. The molecules are in random motion with all possible speeds in all directions.
3. During their random motion, the molecules collide with one another and with the walls of the vessel.
The intermolecular forces between the molecules are neglected.
4. All collisions are perfectly elastic and there is no loss of kinetic energy during collision. Between two
successive collisions, a molecule moves in a straight line. The distance is called the free path of the
molecule. The average distance travelled by a molecule between two collisions is known as its mean
free path.
5. The time spent at a collision is negligibly small in comparison with the time taken to travel the mean
free path.
----------------
 Maxwell’s distribution law of velocities:

To derive the law of distribution of speeds among the molecules of a gas, Maxwell made the
following assumptions
1. The gas consists of molecules with all possible speeds between 0 to ∞
2. A definite number of molecules have speeds between definite ranges.
3. The probability that any selective molecule has velocity lying between a definite range is purely a
function of velocity and limits considered.
Expression:
Consider a point ' P ' in an element of volume dudvdw . Let the point corresponds to gas molecules
whose velocity lies between u , u+du , v , v + dv and w , w+dw . Let f ( u ) , f (v ) and f (w) be the probability
function.
SURENDRA JINKA, LECTURER IN PHYSICS LEPAKSHI DEGREE COLLEGE, PRODDATUR

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The probability that a molecule may have velocity in the range dudvdw is f ( u ) f ( v ) f ( w ) dudvdw .
From fig, the resultant velocity of the molecules ' C ' is given by C 2=u2 +v 2 + w2
f ( u ) f ( v ) f ( w ) dudvdw =ϕ ( C ) dudvdw
2
f ( u ) f ( v ) f ( w ) =ϕ ( u2 +v 2 +w 2 ) ………. (1)
2 2 2 2
Where C =u +v + w
To solve equation (1), we note that for a particular value of C , ϕ ( C 2) is constant
Differentiating eq. (1), we get d [ f ( u ) f ( v ) f ( w ) ] =d [ ϕ ( C 2 ) ]=0 …….. (2)
f ' ( u ) f ( v ) f ( w ) du+ f ( u ) f ' ( v ) f ( w ) dv +f ( u ) f ( v ) f ' ( w ) dw=0 …….. (3)
On dividing with f ( u ) f ( v ) f ( w )
f ' ( u) f ' (v ) f ' ( w)
du+ dv+ dw=0 ……… (4)
f (u) f (v) f (w)
But C 2=u2 +v 2 + w2
On differentiating 0=2u du+2 v dv+ 2 w dw
u du+ v dv+ w dw=0 …….. (5)
Multiplying equation (5) by λ , we get
λu du+ λv dv + λw dw=0 ……… (6) where λ=constant
( ) ( ) ( )
' ' '
f (u) f (v ) f ( w)
+ λu du+ + λv dv + + λw dw=0 ……… (7)
f (u) f ( v) f (w)
i.e.,
( )
'
f ( u)
+ λu du=0 ……… (8)
f (u)
( f '(v)
f (v ) )
+ λv dv=0 ………. (8)
( )
'
f (w )
+ λw dw=0 ………. (8)
f (w)

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'
f (u)
From first equation of equation (8), du=−λudu
f (u )
u2
On integrating , log e f (u)=−λ + log e a
2
f (u) −λ u2
log e =
a 2
2
− λu
2
f (u)=a e
2 2
−λ v −λ w
Similarly f (v )=a e 2 and f (w)=a e 2
3 ( 2 2 2
) /2
∴ f ( u ) f ( v ) f ( w )=a e−λ u + v +w ………. (9)
λ
⇒ f (u ) f ( v ) f ( w )=a3 e−b ( u +v + w ) where b=
2 2 2
2
From the definition of probability we know that total probability = 1
∞
i.e., ∭ a e−b u + v +w du dv d w=1

3 ( 2 2 2
)
0
∞ ∞ ∞
∫e du∫ e dv ∫ e
2 2 2
3 −b u −b v −b w
a dw=1
0 0 0
a
3
√√√ π
b
π
b
π
b
=1
( ) =1
3 /2
3 π
a
b
a =( )
3 /2
b 3
π
a=( )
1 /2
b
π
a=(
2 πkT )
1 /2
m m
where =b
2 kT
From equation (9),
( )
3 /2 −m 2 2 2
m 2 kT
(u +v +w )
f (u ) f ( v ) f (w)= e
2 πkT
If ‘n ’ is the total no of molecules per cubic centimeter of the gas, then the number of ‘dn’ molecules
having velocities lying between u , u+du , v , v + dv, w , w+dw is given by
( )
3/ 2 −m 2 2
m 2 kT
(u + v +w 2)
∴ dn=n e du dv dw …….. (10)
2 πkT

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Which is the Maxwell’s distributive law.

The number of molecules having speeds in a range c and c +dc is obtained by taking the volume
element as the space between two concentric spheres of radius c and c +dc drawn from the origin.
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The volume of annulus du dv dw= π [ ( c+ dc ) −c ]
3 3
3
4
¿ π [ ( c + dc +3 c dc+ 3 c dc )−c ]
3 3 2 2 3
3
4
¿ π × 3 c 2 dc (Here dc 3 , dc2 terms are neglected)
3
d u dv dw=4 π c 2 d c
2
( )
3 /2 −m c
∴ From equation (10) dn c =n m e 2 kT 2
4 π c dc
2 πkT
2
( )
−m c
dnc m
3 /2
=4 π e 2 kT
c2 dc
n 2 πkT
The above equation is called the Maxwell’s law of distribution of velocities.
-------------------
 Average speed:
The average speed c is the speed of all the particles divided by the total number of particles.
2
∞ ∞
( )
−m c
dn c m
3 /2
∴ c=∫ c =∫ 4 π e 2 kT
c 3 dc
0 n 0 2 πkT
3 /2 ∞
()
b
∫ c 3 e−b c dc
2
¿4 π
π 0
¿4 π ( )
( 2b )
3 /2
b −1
π 2
√ ( ) b1 =√ πb4 = √ π4 × 2mkT
3
2 b
¿ 4π
π 4
¿
√ 8 kT
πm
=1.59
kT
m √
c=1.59
√ kT
m
 Most probable speed:
The most probable speed is the speed possessed by maximum number of molecules in a sample for this
the following condition should be satisfied.

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d dnc
dc dc [ ]
=0
[ ]
2
3/ 2 −m c
d
dc
4 πn
m
2 πkT ( ) 2 kT
e c 2 =0
4 πn
m
2 πkT( )
3/ 2
d
dc
e [ −m c 2
2 kT
c =0
2
]
[ kT )]
2 2
−m c −m c
( ) (−2mc
3/ 2
m 2 kT 2 2 kT
4 πn e 2 c+ c e =0
2 πkT
[ ]
2
( )
3/ 2 −m c
m m
4 πn e 2 kT
2 c−c 3 =0
2 πkT kT
3 m 3 m
2 c−c =0 ⇒2 c=c
kT kT
2
2 kT =c m
c p=
√ 2 kT
m
or c p=1.414
kT
m √
Which is the most probable speed.
 R.M.S Speed:
The mean square speed is given by
2
∞
dnc c 2 1 ∞
( )
3 /2 −m c
m
c =∫2
= ∫ 4 πn e 2 kT
c 4 dc
0 n n 0 2 πkT
3/ 2 ∞
b
() ∫ e−b c c 4 dc
2
2
c =4 π
π 0
()[( ) ]
3/ 2 1 /2 3/ 2 1/ 2
2 b 3 π 12 π b π
c =4 π =
π 8 b5 8 π 3 / 2 b5 /2
2 3
∴c =
2b
The R.M.S speed is given by c rms =√ c 2=

√ √ 3
2b
3 2 kT
= ×
2 m
=
3 kT
m √
∴ c rms =
√ 3 kT
m
or c rms =1.732
kT
m √
 Relation between C , C p and C rms:
We know that c=1.59

√ kT
m
, c p=1.414
kT
m
c
and c rms =1.732
1.59
√kT
m √
∴ = =0.921
c rms 1.732

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c=0.921c rms
c p 1.414
Now = =0.817 or c p=0.817 c rms
c rms 1.732
Note that C rms >C >C p
-------------
 Experimental verification of Maxwell’s distribution of law of velocities (or)
Lammert’s toothed wheel method:
Construction:
Lammert used the toothed wheel method for sorting out the molecules having different
velocities. The experimental arrangement is shown in figure. Two equal toothed wheels W 1 and W2 (with
50 teeth each, i.e., 50 narrow slits in between them) are mounted on the same axle. The slits in W 2 are not
parallel to those in W1 but are displaced at an angle of 20 behind them. An oven O contains mercury
vapour which comes out of a slit S1. With the help of another slit a thin and parallel molecular beam is
obtained.
Working: The wheels are set in rapid rotation. Mercury is then heated in the oven. The principle of the
experiment is based on the fact that those molecules are able to pass through a slot in W 2 which have
the requisite speed to cover the distance W 1W2 in the small interval of time taken by the wheel to turn
through an angle of 20. These molecules are deposited on the plate P. Thus the molecules having a
particular speed can be separated from the rest. By rotating the wheels with various speeds, the molecules
of different speeds are collected at different places on the plate P.
-------------------
 Mean free path ( λ ):
Mean free path is defined as the average distance travelled by a molecule between two
successive collisions.
Expression for mean free path:

To calculate the mean free path, assume that
1. Only one molecule under consideration is in motion while all other molecules of the gas are at rest.
2. The molecule under consideration will collide with all those molecules whose centers lie within a
distance d from its center.
Alternatively we may describe the collision by regarding the moving molecule of diameter
‘2d’ and all other molecules as point particles. Consider a molecule of equivalent diameter 2d is moving

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with speed v in speed in time t . The moving molecule sweep out a cylinder of length vt and cross
sectional area π d 2. Moreover in time t this molecule will collide with all the molecules whose centers lie
within the cylinder.
The volume of the cylinder ¿ π d 2 vt
If n is the no of molecules per unit volume
The number of molecules in the cylinder ¿ π d 2 vtn
∴ number of collisions made by the molecules in one second ¿ π d 2 vn
∴ Average distance between 2 successive collisions (or)
Distance of ∈1 sec
mean free path ( λ )=
No of collisions ∈1 sec
v 1
λ= 2 = 2
π d vn π d n
1
λ= 2
πd n
m
In terms of density ρ the mean free path is given by λ= mn=ρ
π d2 ρ
1
λ∝
ρ
According to Maxwell’s law of distribution of speeds, Mean free path ( λ ) is given by
1 kT
λ= or λ=
√2 π d n
2
π √ 2 d2 ρ
--------------------
 Transport phenomena:
When kinetic theory of gases is applied to a gas which is not in thermal equilibrium state, we have the
following three cases:
 Transport of momentum or viscosity:
The components of velocity ( u , v , w ) may not have same value in all parts of the gas. This will
result in relative motion between the gas layers with respect to one another. Now the layers moving faster
transport momentum to the slower moving layers to bring the equilibrium state. This gives rise to the
phenomenon of viscosity.
Explanation:
In the graph shown, the molecules of the gas
above AB have greater velocity and hence possess
a greater momentum. Now due to the thermal
agitation, some of the molecules above AB will
move downwards while some molecules below AB
having smaller momentum will be moving
upwards. In this way the slower stream of gas
below AB gains momentum while the faster stream
above AB loses momentum. According

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to Newton’s 2nd law, the gain in momentum means a force in forward direction while the loss in momentum
means a force in the backward direction. Therefore, the layer above AB experiences a retarding force in the
backward direction while the layer below AB experiences an accelerating force in forward direction. This
gives rise to the phenomenon of viscosity.
Expression for Viscosity:
Let n be the no of molecules per unit volume of the gas and c be their average velocity.
Suppose that 1/3 of molecules are moving along each of three co-ordinate axes ( x , y , z ). The n /6 molecules
move upward and n /6 downward.
n
No of molecules crossing unit area of AB in one second ¿ C
6
mn
Total mass crossing unit area of AB in one sec ¿ C
6
( )
Velocity of gas in layer CD ¿ u+ λ
du
dy
Velocity of gas in layer EF ¿ ( u−λ )

du
dy
∴ Momentum carried downward in one sec ¿ mass × velocity
1
¿ mn C u+ λ
6
du
dy ( )
Similarly momentum carried upward in one sec =
1
6
mn C u−λ (
du
dy )
1
∴ momentum transferred in one sec ¿ mn C u+ λ
6 (
du 1
)
− mnC u−λ
dy 6
du
dy ( )
1
( du
¿ mn C u+ λ −u+ λ
6 dy
du
dy )
¿ mn C ( 2 λ )
1 du
6 dy
1 du
¿ mn C λ
3 dy
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1 du
In equilibrium this is equal to viscous force, Viscous force F= mnC λ
3 dy
Viscous force
∴ Co – efficient of viscosity ¿
Velocity gradient
1 du
mn C λ
3 dy 1
¿ = mnC λ
du 3
dy
1 1
∴ η= mn C λ or η= ρ C λ
3 3
1
But we know that λ=
√2 π d 2 n
1 1
η= mnC
3 √ 2 π d2 n
mC
∴ η=
3 √2 π d 2
 Transport of kinetic energy or thermal conduction:

The different parts of the gas may be at different temperatures. Now to bring the equilibrium
state the molecules of the gas will transport kinetic energy from the regions of higher temperature to a region
of lower temperature. This gives rise to the phenomenon of thermal conduction.
Explanation:
Consider a gas at rest and let it be divided into several layers. The molecules of one layer differ from the
others in respect of temperature. Thus, there exists a uniform temperature gradient ( dT /dy ) in the gas.
Consider a layer AB at a distance of y from OX which is at temperature T. There are two layers CD and EF
on either side of AB at a distance λ (mean free path of molecules) whose temperatures are T +λ ( dT
dy) and
(T −λ dTdy )respectively.
The molecules of the gas above plane AB are at higher temperature than the molecules of the gas below AB.
Hence, the molecules of the gas coming from CD and passing downwards across AB will posses more
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kinetic energy than the molecules coming from the EF and passing across AB in the upward direction. In this
way the energy of the molecules below AB is continuously increases while that of the molecules above AB
continuously decreases. This transport of energy takes place until the gas attains thermal equilibrium.
Expression for thermal conductivity:
Let n be the no of molecules per unit volume of the gas and C be their average velocity.
Suppose that 1/ 3 of the molecules are moving along each of the three co – ordinate axes ( x , y , z ). The
n /6 molecules move upward and n /6 downward.
n
No of molecules crossing unit area of AB in one second ¿ C
6
mn
Total mass crossing unit area of AB in one sec ¿ C
6
(
Temperature of the gas in layer CD ¿ T + λ
dT
dy )
Temperature of the gas in layer EF ¿ ( T −λ
dy )
dT
Heat energy carried downward in one sec is given by Q1=¿ mass × specific heat × temp
¿
mn
6 (
C cv T + λ
dT
dy ) ( )
( mn6 C ) c ( T −λ dTdy )
Similarly, heat energy carried upward in one sec Q2= v
Heat energy transferred in one sec Q=Q −Q =( C ) c (T + λ

dy )
mn dT dT
1 2 v −T + λ
6 dy
C c (2λ )
mn dT 1 dT
Q= v = mnC c λ v
6 dy 3 dy
Heat energy
∴ co – efficient of thermal conductivity K=
Temparature gradient
1 dT
mn C c v λ
3 dy 1
K= = mn C c v λ
dT 3
dy
1 1
K= mn C c v λ= ρ C c v λ
3 3
1
But we know that λ=
√2 π d 2 n
1 1 mC c v
K= mnC c v λ =
3 √2 π d 2 n 3 √ 2 π d 2
mC c v
K=
3 √ 2 π d2
 Transport of mass or diffusion of gases:

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The different parts of the gas may have different densities. Now to bring the equilibrium state
the mass of the gas transferred from high density region to low density region. This gives rise to
phenomenon of diffusion.
Explanation:
Consider that a mass of gas is moving between parallel planes AB and CD. Let the density
increases in vertical direction as we go from AB to CD through the intermediate plane XY. Thus the
density of the gas above XY is greater than that below XY. In order to bring equilibrium, the molecules
of the gas will cross the plane XY from AB to CD and vice-versa due to thermal agitation. This
phenomenon is known as diffusion. The diffusion of the gas is considered as the transport of mass.
Expression for diffusion coefficient (D):

dn
Let n be the concentration of gas molecules in plane XY. If is the concentration gradient,
dz
then
( dndz )
Concentration at plane CD ¿ n+ λ
Concentration at plane AB ¿ ( n− λ )
dn
dz
Suppose that 1/3 of total number of molecules move along any axis. Then 1/6 of molecules move upward
and 1/6 move downward.
1
( )
∴ number of molecules crossing unit area of XY upward in one sec ¿ C n−λ
6
dn
dz
number of molecules crossing unit area of XY downward in one sec ¿ C ( n+ λ )

1 dn
6 dz
The net number of molecules crossing unit area of XY in downward direction is given by
1
6 ( ) ( )
¿ C n+ λ
dn 1
dz
− C n−λ
6
dn
dz
¿ C ( n+ λ −n+ λ )
1 dn dn
6 dz dz
1 dn
¿ Cλ
3 dz

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No of molecules crossingunit area per sec

The coefficient of diffusion D is given by D=
Concentration gradient
1 dn
Cλ
3 dz 1
D= = Cλ
dn 3
dz
1
D= C λ=
3
η
ρ ( 1 η 1
∵ η= ρC λ ⇒ = C λ
3 ρ 3 )
-------------------
Unit – II
Chapter – 2: Thermodynamics
 Introduction:
Thermodynamics is a branch of physics that deals with the transformation of thermal or heat energy into
mechanical work or mechanical work into heat energy. It also deals with the transformation of heat
energy to other forms of energy such as electrical, chemical, light energy etc.
The study of thermodynamics can be broadly divided into two parts.
1st part – This part deals with the relationships between different types of energy based on first law of
thermodynamics.
2 part – This part deals with direction in which these energy changes takes place based on second law
nd
of thermodynamics.
 Terms related to thermodynamics:
1. System: A definite quantity of matter surrounded by some closed surface is known as system.
Example: A gas contained in a cylinder with a movable piston.
Types of System
(i) Open System: A system which can exchange both energy and matter with the surroundings is
called as open system.
(ii) Closed System: A system which can exchange only energy but not matter with the surroundings
are known as closed system.
(iii) Isolated System: A system which exchange neither energy nor matter with the surroundings is
known as isolated system.
2. Surroundings: All those things which are outside the system and influence its behaviour are known
as Surroundings.

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 Thermodynamic co – ordinates (or)

Thermodynamic variables:
In thermodynamics, the state of a system

can be represented by pressure (P), volume (V) and
temperature (T). These three parameters are known
as thermodynamic coordinates.
When thermodynamic variable attain a
steady value then the system is said to be in thermodynamic equilibrium.
 Zeroth law of thermodynamics :
Statement: If two systems ‘A’ and ‘B’ are separately in thermal equilibrium with a third system ‘C’ then
they themselves ‘A’ and ‘B’ are also in thermal equilibrium with each other.
Consider two systems ‘A’ and ‘B’ which are separated by adiabatic wall (non conducting
wall) and the third system ‘C’ which is separated by diathermic wall (conducting wall) after some time
‘A’ and ‘B’ will be separately in thermal equilibrium with ‘C’.
When adiabatic and diathermic walls are interchanged. It is observed that there is no change
in states ‘A’ and ‘B’. This shows that ‘A’ and ‘B’ are also in thermal equilibrium with each other.
 Concept of Temperature:
Zeroth law gives a basic thermodynamic concept called temperature, which determines
whether two systems are in thermal equilibrium or not. If the temperature of two systems is different then
they are not equal in thermal equilibrium.
The temperature is the concept which determines whether two systems are in thermal
equilibrium or not.
 External and internal works:

 External work: Consider a gas enclosed in cylinder piston arrangement, if the external force
displaces the piston then the work is said to be done on the gas. On the other hand if gas expands and
displaces the piston outwards then the work is said to be done by the gas. In both the cases the work
is called External work.
 Internal work: If one part of the system exerts force on the other part of the system, then the work Is
called Internal work.
Example – work done by the forces acting between the molecules of a gas.
 Work done by the gas is taken as positive.
 Work done on the gas is taken as negative.
 Internal energy:
Every thermodynamic system has a definite amount of energy itself. The stored energy in
a system which is not apparently shown is called as its internal energy (or) intrinsic energy.

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Example: Consider a gas enclosed in a cylinder piston arrangement. According to kinetic theory of
gases, the molecules of gas are in rapid motion and hence posses kinetic energy, due to intermolecular
force of attraction the system has potential energy, then the sum of potential and kinetic energy is equal
to internal energy of the system.
Note: The internal energy (U) is independent path followed in a cyclic process (path). The change in
internal energy is zero. To increase internal energy you have to increase speed of molecules and change
distance between them.
 Isothermal process (or) Isothermal change:
Isothermal change is that when a thermodynamic system undergoes a physical change in such
a way that the temperature remains constant then the process is known as isothermal process. In
isothermal process the head produced or lost is given out or
taken from the surroundings.
Example: When a gas is compressed is slowly, the heat
generated is conducted to the surroundings with results that
the temperature remains constant. Similarly, when gas is
allowed to expand slowly, a slight cooling is produced but
heat is taken from the surroundings such that temperature
remains constant.
Boyle’s law holds good for such a change.
PV =RT for one mole of gas
Work done in isothermal process:
Consider one mole of an ideal gas which undergoes
isothermal process. Let its initial pressure and volume be
(P1, V1) and final pressure and volume be (P 2, V2). Assume
that the pressure ‘P’ remains constant for a small change in volume ‘dV ’.
Work done for small change in volume dV is
dW =P dV
V2
Therefore, total work done W =∫ P dV -------①

V1
For isothermal process PV =RT (Boyle’s law)

RT
⇒ P=
V
V2
∴ eq (1) ⇒ W =∫
V1
( RTV ) dV
V2
¿ RT ∫
V1
( V1 ) dV
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V2
¿ RT [ log e V ] V
1
¿ RT [ log e V 2−log e V 1 ]
¿ RT log e
( )
V2
V1
∴ W =2.303 RT log 10 ( )
V2
V1
 For isothermal expansion V 2 >V 1 and hence W =+ve i.e., work done by the gas is positive.
 For isothermal compression V 2 <V 1 and hence W =−ve
i.e., work done on the gas is negative.
 Adiabatic process:
When a thermodynamic system undergoes a
physical change in such a way that no exchange of heat
takes place between system and surroundings then the
process is known as adiabatic process. Under adiabatic
change, there is change of temperature. In this change, the
heat developed or lost cannot be given out or taken up from the surroundings.
Example: when a gas is compressed suddenly or allowed to expand rapidly there is no time for the
system to exchange heat with the surroundings.
Boyle’s law doesn’t hold good for this change.
Under this change, the pressure and volume of a gas are related by
CP
P V γ =constant where γ=
CV
Work done in adiabatic process:
Consider one mole of an ideal gas which undergoes adiabatic process. Let its initial pressure,
volume and temperature be (P1 ,V1, T1) and final pressure, volume and temperature be (P2, V2, T2).
Assume that the pressure ‘P’ remains constant for a small change in volume ‘dV ’.
Work done in small change in volume dW =P dV

V2
∴ Total work done W =∫ P dV ……….. (1)

V1
For an adiabatic process P V γ =K (constant )

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K
P= γ
V
V2
∴ eq (1) ⇒ W =∫
V1
( VK ) dV
γ
V2
¿ K ∫ V −γ dV
V1
( )
V2
V −γ +1
¿K
−γ +1 V1
K
¿
1−γ
( V 2 −V 1 )
−γ +1 −γ +1
1
¿
1−γ
( P 2 V γ2 V −γ
2
+1
−P1 V γ1 V −γ
1
+1
) ( P2 V γ2=P1 V γ1=K )
1
¿ ( P V −P1 V 1)
1−γ 2 2
1
¿
1−γ
( R T 2−R T 1 )
R
∴W=
1−γ 2
( T −T 1 )
 For adiabatic expansion T 2<T 1 and hence W =+ve i.e., work done by the gas is positive.
 For adiabatic compression T 2>T 1 and hence W =−ve i.e., work done on the gas is negative.

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 First law of thermodynamics:
Statement 1: When a definite amount of work is done an equivalent amount of heat is produced and vice
versa.
i.e., W ∝H
W =JH
Where J=4.2 joule /cal
First law is nothing but the statement of law of conversion of energy. This statement is used
when the total work is converted in to heat.
Statement 2: If dQ amount of heat is supplied to a system, then

1. A part is used to increase the internal energy dU
2. The remaining part is used in doing external work dW
∴ dQ=dU +dW
which is the mathematical form of first law of thermodynamics.
Applications of first law of thermodynamics:
 Isothermal process: An isothermal process is one in which the temperature of the system remains
constant ( dT =0 ) then dU =CV dT =0. i.e., there is a change in the internal energy of the system.
From 1st law, dQ =dU +dW
∴ dQ=dW
In an isothermal process the heat supplied to a system is used only to do external work.
 Adiabatic process: In an adiabatic process, there is no heat exchange between system and
surroundings, then dQ =0
From 1st law dQ =dU +dW
0=dU + dW
∴ dU =−dW
 During adiabatic compression, work is done on the gas and hence internal energy increases.
 During adiabatic expansion, work is done by the gas and hence internal energy decreases.

18
 Cyclic process: When a system undergoes a cyclic process then dU =0

From 1st law dQ =dU +dW
dQ=0+dW
∴ dQ=dW
i.e., in cyclic process the energy supplied to the system is used to external work only.
 Isobaric process: A process that takes place at constant pressure is known as isobaric process.
Ex – 1. Boiling of water to steam at constant pressure.
2. Melting of ice into water.
In isobaric process, a gas either expands or contracts to maintain a constant pressure. The amount of
heat supplied to the system is partly used to increase temperature and remaining is used to do external
work. From 1st law dQ =dU +dW
dQ =C P dT + dW
 Isochoric process: A process that takes place at constant volume is known as isochoric process.
i.e., in an isochoric process dV =0
From 1st law, dQ =dU +dW
dQ=dU + P dV
∴ dQ=dU
i.e., the total heat energy supplied to a system is equal to the increase internal energy of the system.
 Adiabatic relations between pressure, volume and temperature of an ideal gas:

Consider one gram-mole of a perfect gas having a volume V , pressure P and
temperature T is enclosed in a perfectly insulating cylinder with a piston. Suppose the gas undergoes a
small adiabatic expansion.
dW =P dV ……….. (1)
The decrease in the internal energy of the gas is equal to the product of its specific heat at
constant volume and the fall in temperature dT , i.e.,
dU =CV dT …………. (2)
From first law of thermodynamics, dQ =dU +dW
0=dU + dW (∵ dQ=0 in adiabatic process)
Substituting the values of dW and dU from eq (1) and (2)
C V dT + P dV =0 ……….. (3)
Consider ideal gas equation PV =nRT ⇒ PV =RT (for one mole n=1)
RT dV
P= From eq (3) C V dT =−RT
V V
dT dV
CV =−R …………. (4)
T V
Integrating both sides
T2 V2
dT dV
CV∫ =−RT ∫
T1
T V1
V

19
C V log ( )T2
T1
=−R log
V2
V1 ( )
C V log
( ) (
T2
T1
=− C p−C V ) log
V2
V1 ( ) (∵ C p−CV =R)
log
( ) (
T2
T1
C V
=− P −1 log 2
CV V1 ) ( )
log
( )
T2
T1
V
=− ( γ −1 ) log 2
V1 ( )
( ) ( )
γ −1
T2 V1
log =log
T1 V2
( )
γ−1
T2 V 1
= ……………. (5)
T1 V 2
T 1 V γ1−1=T 2 V 2γ−1
TV
γ−1
=K (constant ) ……………….. (a)
Eliminating temperature T from eq (5)
( )
γ−1
P2V 2 T2 V 1
= =
P1V 1 T1 V 2
( )
γ
P2 V 1
=
P1 V 2
γ γ
P1 V 1=P2 V 2
P V γ =K (constant ) ………………. (b)
Eliminating V from eq (b), we have
P ( )
RT γ
P
=K
P1−γ T γ =K
………………. (c)
Equations (a), (b) and (c) are called adiabatic relations.
 Reversible process:
A reversible process is one which can be reversed in such a way that all changes occurring in
the direct process are exactly repeated in the opposite order and inverse sense. If heat is absorbed in the

20
direct process, the same amount of heat should be given out in the reverse process then the same amount
of work should be done by the working substance in the reverse process.
Examples:
1. All isothermal and adiabatic processes are reversible if they perform slowly.
2. If certain amount of heat is given to ice then it melts and water if formed. If the same amount of heat
is removed from water then ice if formed.
3. If a perfectly elastic ball is dropped from a certain height on the perfectly elastic surface, then the ball
reaches to the same height.
Note: A reversible process is only an ideal concept and it can be never realized in actual practice this is
because heat loss due to radiation and conduction.
 Irreversible process:
Any process which is not reversible exactly is an irreversible process. All natural process such
as conduction, radiation, radioactive decay, etc. is irreversible.
Examples:
1. Heat produced by the passage of an electric current through the wire is irreversible.
2. Heat transfer between two bodies at different temperatures is also irreversible.
3. Heat produced due to friction is also irreversible.
 Carnot’s heat engine or Carnot’s reversible engine:

A heat engine is a device that converts heat in to work. Carnot’s heat engine consists of
working substance is an ideal gas enclosed in cylinder - piston arrangement, source at very high
temperature T1 K , a sink at very low temperature T2 K and insulating stand. The thermal capacities of
source and sink do not alter their condition.

21
Now the working substance is made to undergo a cyclic process as shown in graph.
(a) Isothermal expansion (AB):

Let the initial state of gas in the cylinder is
represented by the point ‘A’ and final state is represented
by the point ‘B’ on the graph at which pressure, volume and temperature are P 1, V1 and T1 and P2, V2 and
T1.
Now the cylinder is placed on the source and the gas is allowed to expand
isothermally (temperature remains constant) in this case work done by the gas and there should be fall in
temperature of the gas, the necessary heat required is taken from the source. In this operation, pressure of
gas decreases and volume increases.
Let the amount of heat absorbed from the source be ‘Q1’
The work done by the gas W 1=Q 1=RT 1 log e ( )

V2
V1
……….. (1)
¿ Area ABB’ A’ A
(b) Adiabatic expansion (BC):
Now the system is detached from the source and is placed on the insulating stand. Now the
gas is allowed expand further adiabatically till the temperature of the gas is same as that of the sink‘T 2’
K. Hence the gas does external work at the expense of internal energy, this is represented by the curve
‘BC’ in the final state the pressure and volume of gas are P3 and V3.
R
The work done by the gas W 2=
γ−1 1
( T −T 2 ) ………… (2)
¿ Area BCC’ B’ B
After this stage, the pressure of gas is very much reduced such that the gas is not able to do any work. So
now the gas is brought back to its state by following isothermal compression and adiabatic compression.
(c) Isothermal compression(CD):
Now the cylinder is detached from the insulating stand and it is placed on the sink. Now the
gas is compressed isothermally, heat developed passes to the sink. This is represented by the curve ‘CD’
on the graph. The quantity of heat rejected to sink is equal work done on the gas.
The work done on the gas W 3 =Q2=R T 2 log e ( ) V4

V3

22
W 3 =Q2=−R T 2 log e ( )
V3
V4
…………… (3)
¿ Area CC’ D’ DC
(d) Adiabatic compression(DA):
Now the cylinder is detached from the sink and it is placed on the insulating stand. Now the
gas is compressed adiabatically until it reaches to initial state. Now the temperature raises from T2 K to T1
K This is represented by the curve ‘DA’ on the graph. The equal work done on the gas is equal to
increase in its internal energy
−R
The work done on the gas W 4= ( T −T 2 ) ………… (4)
γ −1 1
= Area DD’ A’ AD
From equations (2) and (4) W 2=W 4 and hence
The total work done W =W 1−W 3
¿ Q1−Q2
Net heat absorbed by the gas ¿ Q1−Q2=W 1−W 3
Efficiency of the engine:

The efficiency of the Carnot’s engine is defined as the ratio of work done in the cycle to the
heat taken from the source.
work done by the engine heat converted into work
η= the source ¿=
heat taken ¿ heat taken
W Q 1−Q2 Q2
η= = =1−
Q1 Q1 Q1
Q2
η=1−
Q1
η=1−
RT 2 log e ( )
V3
V4
……….. (1)
V
R T 1 log e 2
V1( )
We know that from adiabatic relations,
γ−1
TV =K
for adiabatic curve BC for adiabatic curve DA
γ −1 γ−1 γ−1 γ−1
T 1 V 2 =T 2 V 3 T 2 V 4 =T 1 V 1
T 1 V γ3−1 V 3
( ) ( )
γ −1
T 1 V γ4−1 V 4 γ−1
= = …… (2) = = ……. (3)
T 2 V γ2−1 V 2 T 2 V γ1−1 V 1
from (2) and (3), we get

23
( ) ( )
γ −1 γ −1
V3 V4
=
V2 V1
V3 V2
= …….. (4)
V4 V1
Substitute equation (4) in equation (1), we get
η=1−
RT 2 log e
V2
V1 ( )
=1− 2
T
( )
V T1
RT 1 log e 2
V1
T2
η=1−
T1
The efficiency of heat engine is independent of working substance and depends only on the temperature
of source and sink.
 Second law of thermodynamics:
Clausius statement: It is impossible for any cyclical machine to transfer

heat continuously from a cold body to hot body (or) there is no perfect
refrigerator.
This statement implies that to transfer heat
from one body to another body at a high temperature, some amount of
work should be done by an external agent.
kelvin – planck statement: It is impossible for any heat engine to convert
total heat in to work. (or) there is no perfect heat engine.
This statement implies that a heat engine
should reject a part of heat to a body at low temperature while converting
heat into work.
importance of second law: first law of thermodynamics says that heat and mechanical work are
interconvertable but if does not give any limitation and condition for this conversion. But second law of
thermodynamics specifies the direction of flow of heat energy.
 Carnot’s theorem:
Statement: Carnot’s theorem states that the efficiency of all reversible engine working between the same
two temperatures is same and no irreversible engine working between the same temperature can have a
greater efficiency than the reversible engine.

24
Proof: To prove the first part of Carnot’s theorem consider two reversible engines operating between T 1
and T2. Assume that engine ‘ H ’ runs in forward direction (heat engine) and engine ‘ H ' ’ runs in
backward direction (refrigerator).
Let engine H takes an amount of heat ‘Q1’ at ‘T1’ and rejects heat ‘Q2’ at ‘T2’. Assume
that the work done by H (W) is equal to work needed to run refrigerator H ' (W’ ). Let H ' receives a heat
' '
Q 2 at T2 and transfer Q 1 at T1.
Assume that e >e ' where e−¿ efficiency of H
e ' −¿ efficiency of H '
' '
Q1−Q2 Q1−Q2
> ' ………. (1)
Q1 Q1
But from work equality W =W '
' '
Q1−Q2=Q1−Q2 ……….. (2)
1 1
From (1) and (2) Q > '
1 Q1
'
Q1 <Q1
Similarly Q2 <Q'2 (from work equality)
This means that the hot source gains a heat Q'1−Q 1 and cold source
losses a heat of Q '2−Q2 . But the external agent did not perform any
work. This means that we have transferred heat from a cold body to hot
body without using external agent, this is a direct contradiction to the
Clausius statement of second law.
∴ e> e' ………… (3)
By reversing the arguments we can prove that e ' > e ……… (4)
'
From (3) and (4) e=e
Which is the proof of Carnot’s theorem.
 Coefficient of performance K of a refrigerator:

The coefficient of performance ( K ) of a refrigerator defined as the ratio of heat taken from the
cold body to the work needed to run the refrigerator.
Q2
K=
W
Q2
K=
Q 1−Q 2
1
K=
Q1
−1
Q2
Q1 T 1
But =
Q2 T 2

25
1
K=
T1
−1
T2
T2
K=
T 1−T 2
 relation between the efficiency of a carnot’s engine η and the coefficient of performance ( K ) of
carnot’s refrigerator:
Consider a Carnot engine and a Carnot refrigerator work between the same temperature T1
and T2. We know that
T 1−T 2
η= ………. (1)
T1
T2
K= ………. (2)
T 1−T 2
T2
From equation (2), K +1= +1
T 1−T 2
T 2+ T 1−T 2
K +1=
T 1−T 2
T1
K +1=
T 1−T 2
1 1
K +1= Or η=
η K +1
This is the relation between η and K
 ENTROPY:
Entropy is a Greek term used for transformation. The concept of entropy was developed by
Clausius. Clausius showed that something must be constant in an adiabatic process just like temperature
remains constant in isothermal process.
The thermal property of a working substance that remains constant during in adiabatic
process is called as entropy.
Q1 T 1
We know that in adiabatic process =
Q2 T 2

26
Q1 Q 2
=
T 1 T2
Q1 Q2 Q 3 Q
Similarly = = =… ⋯ ⋯= =constant
T 1 T2 T 3 T
Q
The quantity is a definite thermal property of the working substance known as entropy. Entropy is the
T
definite physical entity like pressure or volume but there is nothing physical to represent it. It’s not
possible to measure the absolute value of entropy but, we can only measure the change in entropy as the
substance moves from one state to another.
physical significance of entropy :

By definition
heat energy
change ∈entropy=
temperature
Heat energy = temperature × change in entropy
We know that gravitational potential energy = mgh
If we compare the above two relations regarding temperature is equivalent to height, entropy is
equivalent to mass or mechanical inertia i.e., entropy in thermodynamics plays the same role as mass in
linear motion.
Hence entropy is known as thermal inertia.
More entropy of a system results in less amount of heat energy is being converted in to work.
In other words increase in entropy means transformation of heat energy from available form to
unavailable form for conversion in to work.
Measurement of entropy : we cannot measure the absolute value of entropy but it is possible to measure
change in entropy in a process. If dQ amount of energy absorbed or rejected in a process at temperature
‘T1’
dQ
The change in entropy dS=
T
Now the system changes from state ‘A’ to state ‘B’, then change in entropy
B
dQ
S A −SB =∫
A T
If we take state ‘A’ as arbitrary zero state, then
B
dQ
S B= ∫
A =0 T
 Change in entropy in reversible process (or) clausius theorem:

27
Statement: In a reversible process, change in entropy is zero.
Proof: consider Carnot’s reversible engine working between temperatures T1 and T2. In Carnot’s cycle
we know that the working substance is made to undergo a cyclic process (AB, BC, CD, and DA). During
isothermal expansion it absorbs heat Q1 from source at T1, during isothermal compression it reject heat Q2
to sink at T2.
Hence in
Q1
Isothermal Expansion: Change in entropy (AB) dS 1= (+ve heat absorption)
T1
Adiabatic Expansion: Change in entropy (BC) dS 2=0 (entropy is constant in adiabatic process)
Q2
Isothermal Compression: Change in entropy (CD) dS 3= (-ve heat absorption)
T2
Adiabatic Compression: Change in entropy (BC) dS 4 =0 (entropy is constant in adiabatic process)
∴ Change in entropy in reversible process is given by dS=dS1 +dS 2+ dS3 +dS 4
Q1 Q2
dS= +0− +0
T1 T2
Q1 Q2
But in Carnot’s cycle =
T 1 T2
∴ dS=0
Hence Clausius theorem is proved.
 Change in entropy in irreversible process:

Heat conduction, heat radiation etc are the
examples of irreversible process. Heat conduction always
takes place from a body of higher temperature to a body of
lower temperature respectively. Consider two bodies A and B at temperatures T 1 and T2. Let T1 > T2 heat
flows from A to B.
Q
∴ Decrease in entropy of A=
T1
Q
Increase in entropy of B=
T2
Q Q
Net change in entropy ¿ −
T2 T1
¿Q ( 1 1
−
T2 T1 )
¿Q
( T 1 −T 2
T1 T2 )
28
i.e., entropy increases

∴ In all reversible process, entropy increases.
 Entropy of universe:
We know that all process in nature are irreversible and in all irreversible processes, entropy
increases. So in every process in nature, a part of the energy of the universe becomes unavailable for
useful work. So, in distant future energy existing in different forms in the universe will be converted in to
heat and will not be available for conversion in to useful work. Thus energy available in the universe
slowly decreases. This is known as principle of degradation of energy states which tends to universe
death. So, we can say that the entropy of the universe always tends towards maximum values.
 Change in entropy of a perfect gas:

Consider one mole of perfect gas with thermodynamic coordinates ( P, V, T). If dQ amount of
heat is given to the gas then increase in entropy is given by
[ ( ) ][ ] [ ][ ]
But from first law of thermodynamics, dQ=dU +dW
Where dU = change in internal energy = CV dT,
dW = External work = P dV
dQ=CV dT + P dV
1 dQ dQ dU+dW dU+pdV dU
dS=
CV dT + P dV
∵CV= = ¿ = ¿ = ¿ CV= ⇒dU=CVdT ¿¿
m dT dT dT dT dT
T
C dT P dV
∴ dS= V + ………. (1)
T T
(a) dS in terms of V and T
¿
We know that for one mole of perfect gas PV =RT
RT
P=
V
( )
CV dT RT dV
From equation (1) ⇒ dS= +
T V T
C V dT dV
⇒ dS= +R
T V
On integrating from Si to Sf
Sf Tf Vf
dT dV
∫ dS=CV ∫ T + R∫ V
S i T V i i
[ S ] SS =C V [ log e T ]TT + R [ log e V ] VV

f
i
f
i
f
Sf −Si=CV [ log e T f −log e T i ]+ R [ log e V f −log e V i ]
Sf −Si=CV log e
[ ( )] [ ( )]
Tf
Te
V
+ R log e f
Vi

29
Sf −Si=2.303C V log 10
[ ( )] Tf
Te [ ( )]
V
+ 2.303 R log 10 f
Vi
(b) dS in terms of P and T

We know that for one mole of perfect gas PV =RT
On differentiating we get P dV +V dP=R dT
P dV =R dT −V dP
R dT −V dP
dV = ……… (1)
P
( )( )
CV dT P R dT −V dP
From equation (1) ⇒ dS= +
T T P
( )
C dT dT dP
⇒ dS= V + R −V
T T T
dT dT dP
dS=C V +R −V
T T T
dT dT dP
dS=C V + ( C P−C V ) −V
T T T
dT dT dT dP
dS=C V +C P −C V −V
T T T T
dT dP
dS=C P −V
T T
On integrating from Si to Sf
Sf Tf Pf
dT dP V R
∫ dS=C P∫ T + R ∫ P ∵ PV =RT ⇒ =
T P
S i T Pi i
Sf Tf Pf
[ S ] S =C P [ log e T ]T + R [ log e P ] P
i i i
Sf −Si=C P [ log e T f −log e T i ] + R [ log e P f −log e Pi ]
Sf −Si=C P log e
[ ( )] [ ( )]
Tf
Te
P
+ R log e f
Pi
Sf −Si=2.303C V log 10
[ ( )] [ ( )]
Tf
Te
P
+ 2.303 R log 10 f
Pi

30
 Tephigrams (or) Temperature (t) – Entropy (s) diagrams:

A graph between temperature (T) and entropy (S) is known as Tephigrams earlier it was
denoted by ‘ϕ ’ and so Tephigram is given as the name of T – S diagrams.
“The area of tephigrams gives the available thermal energy for conversion in to work”.
Consider a Carnot’s reversible engine and plot its indicator diagram. The corresponding T – S diagram
will be in the shape of rectangle as shown in fig.

31
Amount of heat absorbed during isothermal expansion ‘AB’ Q1=T 1 ( S 2−S 1 )

= Area ABEF
= AB X AF
Amount of heat rejected during isothermal compression ‘CD’ Q2=T 2 ( S 2−S 1 )
= Area CDEF
= CD XDF
Available thermal energy for conversion in to work W =Q 1−Q2
= Area ABEF - Area CDEF
=Area ABCD (or) Area of tephigram
∴ The area of tephigrams gives the available thermal energy for conversion in to work.
Efficiency ( η ) :
W
η=
Q1
Q1−Q2
¿
Q1
Area of ABCD
¿
Area of ABEF
AB × AD
¿
AB× AF
AD
η=
AF
The ratio of AD to AF gives the efficiency of Carnot’s engine.
USES OF TEPHIGRAMS:
1. Tephigrams are used in meteorology.
2. For mechanical and automobile engineers, Tephigrams are useful to predict the defects in
performance engine.
3. To check the efficiency of heat engine.
4. To obtain the work value of the fuel used.
-------------
Unit – III
Chapter – 3: Thermodynamic potentials and Maxwell’s equations
 Thermodynamic potentials:

32
The thermodynamic state of a system is specified by means of 4 basic thermodynamic variables P ,V , T

and S.
“Thermodynamic potentials are the energy functions they are mathematically formed by
combining the basic thermodynamic variables P ,V , T and S in different ways”. There are four
thermodynamic potentials namely
1. Internal energy (U )
2. Helmholtz function (or) Helmholtz frees energy ( F )
3. Enthalpy (or) total heat energy ( H )
4. Gibb’s free energy (G )
1. Internal energy (U ): From First law of thermodynamics, we know that every system has within
itself definite amount of energy called internal energy (U ) is the characteristic property of the system
that changes when the system goes form one state to another. ‘U ’ is independent of the path followed.
from 1st law,
dQ =dU +dW
dU =dQ −dW
but dW =P dV
dQ =T dS
∴ dU =T dS−PdV ………………. (1)
This is an exact differential equation , where ‘S’ and ‘U’ are independent variables, ‘T’ and ‘P’ are
dependent variables.
2. Helmholtz function (or) Helmholtz frees energy ( F ):
F=U−TS
On differentiating dF=dU −d ( TS )
dF=dU −T dS−S dT
but from (1), dU =T dS−P dV
dF=T dS−P dV −T dS−S dT
dF=−P dV −S dT
This is an exact differential equation, where ‘V’ and ‘T’ are independent variables, ‘P’ and ‘S’ are
dependent variables
 For an isothermal process dT =0
∴ dF=−P dV
i.e., Helmholtz free energy (F) denotes the work done by the system in an isothermal process.
 For an isothermal as well as isochoric process dT =0 and dV =0
dF=0 or F=constant
i.e., Helmholtz free energy remains constant in an isothermal as well as isochoric process.
3. Enthalpy (or) total heat energy ( H ): The Enthalpy or Total heat function of a system is
mathematically defined as
H=U + PV
On differentiation dH =dU + d ( PV )
dH =dU + P dV +V dP

33
but dQ =dU + P dV and dQ =T dS

dH =dQ +V dP
dH =T dS +V dP ………….. (2)
This is an exact differential equation , where ‘S’ and ‘P’ are independent variables, ‘T’ and ‘V’ are
 For an isobaric process dP=0
∴ dH =T dS or dH =( dQ ) p
i.e., Enthalpy is a measure of total heat content of a system at constant pressure.
4. Gibb’s free energy (G ): Gibb’s function is mathematically defined as
G=H −TS
On differentiating dG=dH−d ( TS )
dG =dH−T dS−S dT
But dH =T dS +V dP
dG =T dS +V dP−T dS−S dT
dG=V dP−S dT
This is an exact differential equation , where ‘T’ and ‘P’ are independent variables, ‘S’ and ‘V’ are
 For an isothermal and isobaric process dT =0 and dP=0
dG=0 or G=constant
Gibb’s function remains constant in an isothermal and isobaric process.
 MAXWELL’S EQUATIONS (OR) THERMODYNAMIC RELATIONS:
Maxwell’s equations are differential relations among the four basic thermodynamic
coordinates P, V, T and S. these equations are derived from the four thermodynamic potentials namely.
 Maxwell’s 1st thermodynamic relation:
from 1st law,
dQ =dU +dW
dU =dQ −dW
but dW =P dV
dQ =T dS
∴ dU =T dS−PdV ………………. (1)
This is an exact differential equation, where ‘S’ and ‘U’ are independent variables, ‘T’ and ‘P’ are
On comparing the above the equation with dZ=M dX + N dY
Z=U , M =T , X =S , N =−P ,Y =V
We know that the condition for exactness which is given by
( ) ( )
∂M
=
∂Y X ∂ X Y
∂N
( ∂T
∂V )
SURENDRA JINKA, LECTURER IN PHYSICS
=−(
S ∂S)
∂P
V
LEPAKSHI DEGREE COLLEGE, PRODDATUR
34
This is Maxwell’s 1st thermodynamic relation.

 Maxwell’s 2nd thermodynamic relation:
F=U−TS
On differentiating dF=dU −d ( TS )
dF=dU −T dS−S dT
but from (1), dU =T dS−P dV
dF=T dS−P dV −T dS−S dT
dF=−P dV −S dT
This is an exact differential equation, where ‘V’ and ‘T’ are independent variables, ‘P’ and ‘S’ are
M =−P , X =V , N =−S ,Y =T
( ) ( )
∂M
=
∂Y X ∂ X Y
∂N
−( ) =−(
∂V )
∂P ∂S
∂T V T
( ∂∂ TP ) =( ∂∂VS )
V T
This is Maxwell’s 2nd thermodynamic relation.

 Maxwell’s 3rd thermodynamic relation:
We know that Enthalpy H=U + PV
On differentiation dH =dU + d ( PV )
dH =dU + P dV +V dP
but dQ =dU + P dV and dQ=T dS
dH =dQ+V dP
dH =T dS +V dP ………….. (2)
This is an exact differential equation , where ‘S’ and ‘P’ are independent variables, ‘T’ and ‘V’ are
M =T , X=S , N=V , Y =P
( ) ( )
∂M
=
∂Y X ∂ X Y
∂N
( ∂∂ TP ) =( ∂∂VS )
S P

35
This is Maxwell’s 3rd thermodynamic relation.

 Maxwell’s 4th thermodynamic relation:
G=H −TS
On differentiating dG =dH−d ( TS )
dG=dH−T dS−S dT
But dH =T dS +V dP
dG=T dS +V dP−T dS−S dT
dG =V dP−S dT
This is an exact differential equation , where ‘T’ and ‘P’ are independent variables, ‘S’ and ‘V’ are
M =V , X =P , N =−S ,Y =T
( ) ( )
∂M
=
∂Y X ∂ X Y
∂N
( ∂∂TV ) =−( ∂∂ PS )
P T
This is Maxwell’s 4th thermodynamic relation.
 CLAUSIUS – CLAYPERON EQUATION:

The Clausius – clapeyron’s latent heat equation relates the change in melting and boiling point
with the change in pressure.
From Maxwell’s 2nd relation,
( ) ( )
∂P
=
∂T V ∂V T
∂S
Multiplying both sides by T , we have

T ( ) ( )
∂P
∂T V
=T
∂S
∂V T
T( ) =(
∂V )
∂P T ∂S
∂T V T
T( ) =(
∂V )
∂P ∂Q
………… (1)
∂T V T
Where dQ =T dS (IInd law of thermodynamics)

Now assume that unit mass of a substance undergoes a phase change (solid to liquid) or (liquid to gas at
constant temperature) then the heat absorbed at constant temperature is given by dQ=L
Also let V 1 ,V 2 be the specific volumes in I and II states respectively.
[ Specific Volume=
Volume
]
Unit mass
∂P L
∴ ( 1) ⇒ T =
∂T V 2−V 1
36
∂P L
=
∂ T T ( V 2−V 1 ) (
∵ ∂ V =V 2−V 1)
Which is Clausius – clapeyron’s latent heat equation.

Uses: It is used to study the change in melting point and boiling point with the change in pressure.
Applications:
 Effect of pressure on melting point of solids:
∂P L
=
∂ T T ( V 2−V 1 )
Where V 1 and V 2 are specific volumes in solid and liquid.
In case of wax and sulphur the volume increases when they melt.
∴ V 2−V 1=+ ve
∂P
=+ ve
∂T
i.e., if pressure increases, the melting point increases and viceversa. In case of ice, volume decreases
when it melts
∴ V 2−V 1=−ve
∂P
∴ =−ve
∂T
i.e., in case of ice melting point decreases with the increase of pressure and vice versa.
 Effect of pressure on boiling point of liquids:
∂P L
=
∂ T T ( V 2−V 1 )
Where V 1 and V 2 are specific volumes in liquid and vapour phases respectively.
In case of liquids always volume increases whey they get boiled.
∴ V 2−V 1=+ ve
∂P
=+ ve
∂T
i .e . , the boiling point of liquids increases with increase of pressure and vice versa.
 Specific heat
The amount of heat energy required to rise the temperature of a body of unit mass by 10C or 1
K is known as specific heat.
1 dQ
C=
M dT
For gases there exist two types of specific heats.
(1) Specific heat at constant pressure ( C P ) :
At constant pressure, the amount of heat required to rise the temperature of gas of
unit mass by 10C or 1 K is known as specific heat at constant pressure ( C P )

37
CP=
1 dQ
M dT ( ) P
(2) Specific heat at constant volume ( C V ):

At constant volume, the amount of heat required to rise the temperature of gas of
unit mass by 10C or 1 K is known as specific heat at constant pressure ( C V )
CV=
1 dQ
M dT ( ) V
Note:
1. Bulk modulus at constant temperature is known as isothermal elasticity.
2. Bulk modulus at constant entropy is known as adiabatic elasticity.
1
3. compressibility=
Bulk modulus
 Ratio of specific heats ( C P ES

=
CV E T
: )
Stress −∂ P
The coefficient of volume elasticity is defined by E= =
Volume Strain dV / V
∂P
E=−V
∂V
Where '−' denotes as pressure increases volume decreases.
Now, if we consider a gas at unit mass then adiabatic elasticity,
E S=−V ( )
∂P
∂V S
(∵ Entropy S is constant)
Isothermal elasticity ET =−V ( ∂∂ VP ) T
ES
∴ =
−V ( ∂∂VP ) S
−V (
∂V )
ET ∂P
T
E S
=
( ∂T ∂V )
∂P ∂T
S
E T
( ∂∂ PS ∂∂VS )T
(¿ ∂∂ PT ) ( ∂∂ VT )
S S
( ∂∂ PS ) ( ∂∂VS )
T T
Now apply Maxwell’s relations

38
ES
=
( ∂S
∂ V ) [ −(
P
∂P
∂ S ) ] =
( ∂S
∂VV
) ( ∂S )
∂P
P V
−( ) ( ) ( ) ( ∂T )
ET ∂T ∂P ∂T ∂P
∂V ∂T
P ∂VV P V
( )( )
∂S ∂P
ES
ET
=
∂V
∂T
∂S
∂P
= ( ∂∂TS ) ( ∂T∂S )
P V
∂V P ∂T V
( ) /( ∂∂TS )
ES ∂ S
=
ET ∂T P V
Multiplying both numerator and denominator with T , we get
ES
=
T
∂S
∂T P
=
∂Q
∂T ( ) ( ) P
ET
T
∂S
∂T V
∂Q
∂T ( ) ( ) V
But ( ∂∂TQ ) =C
P
P and ( ∂∂TQ ) =C
V
V
CP E
=γ = S
CV ET
Thus, the ratio of specific heats of the substance at constant pressure and at constant volume is equal to
the ratio of adiabatic and isothermal elasticities.
 Difference of two specific heats or specific heat relation for a perfect gas: [ C P−CV =R ]
Consider one mole of perfect gas we know that the specific heat ( C ) is defined as the amount
of heat required for unit mass to raise the body temperature by i.e.,
C=
dQ
dT
⇒ CP=
∂Q
∂T P
=T
∂S
∂T P ( ) ( )
Similarly C V = ( ∂Q
∂T ) =T (
V ∂T )
∂S
V
Now let entropy S=S ( T ,V )

dS= ( ∂∂TS ) dT +( ∂∂VS ) dV
V T
Dividing with dT at constant pressure
( ∂∂ TS ) =( ∂∂TS ) +( ∂∂VS ) ( ∂V
P V ∂T ) T P
C = C +( ) ( ∂T )
1 1 ∂S ∂V
P V
T T ∂V T P

39
Maxwell’s 2nd relation is ( ∂∂ TP ) =( ∂∂VS )

V T
C P −CV =T ( ∂∂TP ) ( ∂V
V ∂T ) P
For one mole of perfect gas PV =RT

RT RT
P= or V =
V P
( )
∂P
∂T V V
=
R
( )
∂V
∂T P P
=
R
C P −CV =T ( ∂∂TP ) ( ∂V
V ∂T ) C −C =T
P
RR
V P P V
2 2
R R
C P −CV =T =T =R
PV RT
C P −CV =R
Which is the specific heat relation.
 Difference of specific heats ( C P −CV ) in terms of isothermal elasticity and coefficient of volume:
We know that C P −CV =T ( ∂∂TP ) ( ∂V

∂T )
V P
………… (1)
Isothermal elasticity E =−V (

∂V )
∂P
T
T
1 ∂V
Co – efficient of volume expansion α =
V ∂T
Let us take P=P ( T ,V )
dP= ( ∂∂ TP ) dT +( ∂∂VP ) dV
V T
If the change takes place at constant pressure then dP=0

0=
∂P
∂T V ( ) ( ) ( dV )
( dT )P +
∂P
∂V T
P
( ∂∂ TP ) ( dT ) =−( ∂∂VP ) ( dV )
V
P
T
P
( ∂∂ TP ) =−( ∂∂VP ) ( ∂V
V ∂T ) T P
Substituting this in equation (1)
( )( )
( 1 ) ⇒ C P−C V =T
∂V ∂P
∂T P ∂T V
=−T
∂V
∂T ( ) ( ∂∂VP ) ( ∂∂VT )
P T P
C −C =−T [ (
∂V ) ( ∂T ) ]
2
∂ P ∂V
P V
T P

40
[ ( ) ( )]
2
1 ∂P 2 ∂ V /V
C P −CV =−T V
V ∂V /V ∂T
[( )( ) ]
2
∂P ∂ V /V
C P −CV =−T V
∂ V /V ∂T
C P −CV =−T [ −E α 2 ] V
C P −CV =T E α 2 V
From the following equation, we note the following points.
(1). At absolute zero T =0 , C P −CV =0 ⇒ C P=CV
(2). As E , α are always positive, C P −CV =+ve , i.e., C P is always greater than C V .
 Joule – Thomson effect or Joule – Kelvin effect:

When a gas under constant high pressure is passed through porous material (like cotton) to a
region of constant low pressure, there is a change in temperature. This is called as Joule – Thomson or
Joule – Kelvin effect.
Observations:
1. All the gases when passed through a porous plug suffer a change in temperature. At ordinary
temperatures all gases except hydrogen and helium suffer a fall in temperature (cooling effect)
while hydrogen and helium suffer a slight rise in temperature (heating effect).
2. The change in temperature is directly proportional to the pressure difference on the two sides of
the plug.
3. As the initial temperature of the gas rises, the cooling effect diminishes. At a certain initial
temperature, known as inversion temperature, the cooling effect is changed to heating effect.
Expression for Joule – Kelvin co – efficient:
The ratio of change in temperature ( dT ) to the change in pressure ( dP ) at constant enthalpy is
known as Joule – Kelvin co – efficient.
i.e., μ= ( )
dT
dP H
μ−¿ Joule – Kelvin co – efficient
In a cyclic process, enthalpy H=constant ⇒U + PV =constant

⇒ dU + P dV + V dP=0 ( ¿ 1 st law dQ=dU + P dV )
dQ+V dP=0
T dS+V dP=0 ………… (1)
Let us take S=S ( T , P )
dS= ( )
∂S
∂T P
dT +
∂S
∂P T ( )
dP
Substituting this in eq (1)
T
[( ) ( ) ]
∂S
∂T P
dT +
∂S
∂P T
dP +V dP=0

41
( ∂∂TS ) dT +T ( ∂∂ SP ) dP+V dP=0

T
P T
( ∂∂TQ ) dT +[T ( ∂∂ PS ) +V ] dP=0

P
……… (2)
T
But ( ) =C and ( ) =−(

∂T )
∂Q ∂S ∂V
P (Maxwell’s IV relation) th
∂T P ∂P T P
∴ (2) ⇒ C dT + [ −T ( ]
∂T )
∂V
P +V dP=0
P
∂T 1
=
[( ) ]
∂ P CP
T
∂V
∂T P
−V
μ=
1
CP
T
[( ) ]
∂V
∂T P
−V ………. (3)
μ= ( ∂∂ TP )
H
Joule – Kelvin coefficient
Joule – Kelvin effect for a perfect gas:

For one mole of perfect gas PV =RT
RT
V=
P
Differentiate with respect to T at constant pressure ( ∂∂TV ) = RP

P
∴ (3)⇒ μ=
1 R
[
T −V
CP P ]
1 RT
¿
CP P [ 1
]
−V = [ V −V ] =0
CP
i .e., for a perfect gas there is no Joule – Kelvin effect.
Joule – Kelvin effect for Vander wall gas:

For Vander wall gas
a
(
P+ 2 (V −b )=RT
V ) ………… (A)
Where a , b are Vander wall constants.

On differentiating with respect to T at constant pressure
P+ 2
V
a ∂V
∂T P (
+ (V −b )
V3 )( )
−2 a ∂V
∂T P
=R
( )( )
( ∂∂TV ) [( P+ Va )+( V −b ) ( −2V a )]=R
P
2 3

42
( ∂∂TV ) = R
( a
) RT
P
[ RT 2a
− 3 ( V −b )
( V −b ) V ] from eq (A) P+
V 2
=
( V −b )
( ∂∂TV ) = RT−R 2( Va−b( V −b

)
V
P
[ ) 3
2
]
∂V
=( ) R ( V −b )
∂T P 2a 2
RT− 3 ( V −2 Vb+ b )
V [ 2
]
As ‘b’ is very small, b and 2 Vb can be neglected.
2
∂V
( )
=
R (V −b )
=
R ( V −b )
∂T P 2a
RT− 3 V 2
V [
RT −
2a
V ][ ]
Multiply both sides with T
T
∂V
= ( )
RT ( V −b )
∂T P
RT −
2a
V [ ]
( ) RT ( V −b )
( )
−1
∂V 2a
T = =( V −b ) 1−
∂T P
RT 1−
2a
VRT [ VRT
]
T ( ∂V
∂T ) =( V −b ) (1+
P VRT )
2a
Substitute this in equation (3)
μ=
1
CP [ (
( V −b ) 1+
2a
VRT
−V ) ]
¿
1
CP
V+
[2 aV
VRT
−b−
2 ab
VRT
−V
]
μ=
1 2a
C P RT [
−b ] ( ∵
2 ab
VRT
can be neglected )
Which is Joule – Kelvin co – efficient for Vander wall gas
2a 2a
If =b or T = then μ=0
RT Rb
This temperature is known as inversion temperature.
2a
∴ T i=
Rb
 If T < T i then the gas suffers cooling
 If T > T i then the gas suffers heating

43
Unit – IV
Low Temperature Physics
 Joule – Kelvin effect (POROUS PLUG EXPERIMENT):

Consider a thermally insulated cylinder containing porous plug fitted with two non conducting
pistons A and B. Let the gas is compressed to a high pressure P1 on one side and there is a constant lower
pressure P2 on other side of the porous plug.
When a gas under a constant pressure is

passed through a porous plug to a region of lower
constant pressure, the gas suffers a change in
temperature. Such a change was actually
demonstrated by Joule and Kelvin and hence
known as Joule – Kelvin or Joule – Thomson
effect.
Results of Joule – Kelvin effect:
1. All gases suffer a change in temperature after passing through porous plug.
2. The change in temperature is directly proportional to pressure difference on two sides of the porous
plug.

44
3. At ordinary temperatures all gases except H2 and He gets cooled when they are passed through porous
plug but H2 and He show heating effect.
4. At a particular temperature known as inversion temperature cooling effect changes into heating effect.
 Liquefaction of Helium – Kammerlingh onnes method:

The critical temperature of helium is – 268 0C or 5 K. So it is necessary to cool it below –
2680C before it gets liquefied. Kammerlingh ones succeeded in liquefying helium by using Joule –
Thomson effect.
Kammerlingh ones helium liquefier is shown in fig. Pure, dry and pre cooled helium is
compressed to about 40 atm pressure by compressor P. it is then divided into two parts of B. A part flows
through spiral tube S and is cooled by liquid H2 boiling under reduced pressure. The other part flows
through the spiral tubes S2 and cooled by the vapour which has already suffered Joule – Kelvin expansion
(regenerative cooling). Both these streams reunite at C where they again divided into two parts. A similar
process takes place in spiral tube S3 and S4. Now the two streams are again cooled and meet at D. here the
gas suffers Joule – Kelvin expansion at nozzle N. the expanded gas cools down and raises up so it cools
the incoming gas. The process continuous again and again till the temperature reaches -268 0C where
helium gets liquefied at atmospheric pressure.
 Production of very low temperature adiabatic demagnetization:

Principle: A paramagnetic substance contains molecules which are lying in disorderly manner. When the
substance is magnetized, the molecules are set in the direction of magnetic field. Certain amount of work
is done in this process which is added to the internal energy of the substance. Due to this fact, the
temperature of the substance rises. When a paramagnetic substance already magnetized is suddenly
demagnetized, it shows a slight fall in temperature. If the substance is already at a sufficient low
temperature, the fall in temperature is considerable.
Construction:

45
A paramagnetic substance is suspended in vessel A. The vessel is surrounded by liquid helium

at temperature 1 K in a Dewar flask B. This is again surrounded by another Dewar flask C containing
liquid hydrogen. The whole arrangement is kept between the poles of a very powerful electromagnet. The
coil M around A are used to measure temperature by susceptibility measurements.
Theory:
When a paramagnetic substance is magnetized, work is done by the magnetic field, when the
substance is demagnetized then the work done by the substance.
dW =−B dI
P dV =−B dI
Where B=¿ magnetic field, I =¿ intensity of magnetization
From Maxwell’s 3rd relation,
( ) ( )
∂T
=
∂V
∂ P s ∂S P
To obtain a similar relation we substitute P=−B and V =I
( ) ( )
∂T
∂B s
=−
∂I
∂S B
( ∂ B ) [ ( ∂ S /∂T ) ] ………. (1)

∂T ( ∂ I /∂T )
B
=−
s B
∂ T ) T [ ∂ T ] T ( ∂T )
But (
∂S 1 ∂S 1 ∂Q mc B
= T = =
B B B T
Where m=¿ mass of paramagnetic substance
c B =¿ Specific heat at constant magnetic field
∴ (1)
∂ T −T ∂ I
=
∂ B mC B ∂ T( )
I
We know that Susceptibility χ =
B

46
C
From Curie’s law χ = where C=¿ Curie’s constant
T
I C
=
B T
CB
I=
T
∂ T −T ∂ CB
=
∂ B mC B ∂T T ( )
∂ T −T
=
∂ B mC B
CB 2
( )
−1
T
CB
∂T= ∂B
mC B T
On integrating
Tf 0
C
∫ ∂T = mC T ∫ B ∂ B
Ti
B B
T f −T i = [ ]
C /m −B 2
CB T 2
T f −T i = [ ]
K −B 2
CB T 2
where K=
C
B
Curies constant per unit mass
−K B2
T f −T i =
2C B T
The negative sign indicates the fall in temperature due to adiabatic demagnetization.
 Liquifaction of Helium – Kaptiza’s method:

47
Kaptiza’s Helium liquefier is shown in figure. Pure and dry helium is compressed to 30 atm by
compressor P. The heat generated due to compression is removed by flowing water in a jacket
surrounding a portion of the tube. The gas is then precooled by passing it through liquid N2 boiling under
reduced pressure. The precooled gas is divided into two parts at A in the heat exchanger. One part passes
to the expansion engine E. Due to adiabatic demagnetization of the gas it cools to – 263 0C. This cooled
gas rises up in the heat exchanger and cools the second part coming towards the nozzle N. The second
part is now so cooled that after the expansion at nozzle N, it is liquefied. The liquefied portion is
collected in Dewar flask and the remaining part goes back to the compressor through heat exchanger.
 Distinction between Joule’s expansion, adiabatic expansion and Joule – Kelvin expansion :
(1) Joule’s expansion: Joule’s expansion is a free expansion in which gas doesn’t do any external work
and only internal work is done to overcome the intermolecular attraction. In this expansion, heating
and cooling effect of gas takes place depending on the initial temperature of the gas.
(2) Adiabatic expansion: In this expansion, the compressed gas is suddenly released to atmosphere. The
gas performs the external work against the pressure of atmosphere. The external work is drawn from
the internal energy of the gas. Thus the gas cools.
(3) Joule – Kelvin expansion: In this expansion, the gas under high pressure is forced to pass through the
porous plug to a region of low pressure. Hence the gas does internal work as well as external work.
So in this expansion, heating or cooling of the gas takes place depending upon the initial temperature
of the gas. At ordinary temperature, all the gases expect H2 and He shows cooling effect.
 Applications of Low temperature physics:

1. Liquid NH3, SO2 used in refrigerators and air conditioners.
2. Liquid O2 is used for respiration and also in the manufacturing of explosives.
3. Liquid air, liquid O2, liquid H2 are extensively used in calorimeters that are used for research on
specific heat at low temperature.
4. The property of superconductivity exhibited by the matter at very low temperatures can be used for
advantage in electrical conduction.
5. Low temperature physics has got much importance in cryogenic rocket engineering in space research.
6. Super conducting coils are used in producing electromagnetic field in adiabatic demagnetization.

48
Unit - V
Quantum theory of radiation
 Thermal radiation: The property of heat transfer by a body without the involvement of medium is
known as thermal radiation.
Ex: Earth receives heat from sun.
Properties:
1. Thermal radiation travels with velocity of light.
2. Thermal radiation travels in the form of electromagnetic radiation.
3. Thermal radiation shows the phenomenon like reflection, refraction, interference and diffraction etc.
4. Thermal radiation is a full radiation i.e., it contains all wavelengths.
 Emissive power: The emissive power of a body is defined as “the radiant energy emitted by a body per
sec or per unit area or per unit wavelength range.
 Absorptive power: The absorptive power of a body is defined as the ratio of radiant energy absorbed per
sec or per unit area wavelength range to the total energy incident on the same area.
 Black body:

49
A black body is one that absorbs all radiations incident on it. There is no perfect black body in nature.
But lampblack or platinum black is taken as a nearest approach to a perfect black body.
Ferry’s Black body:
Ferry’s black body is in the form of double walled conducting sphere. The inter space
between the walls is evacuated to prevent loss of heat by conduction and convection. It has a small hole
O and a conical projection P.
It is lamp blacked inside and nickel polished outside. When the radiation enters the enclosure through pin
hole, it suffers multiple reflections and finally gets absorbed. When the Ferry’s black body is cooled, then
it starts emitting radiations known as black body radiations through a pin hole. So the pin hole is treated
as perfect black body.
 Distribution of energy in the spectrum of black body:

The distribution of energy in the spectrum of black body was experimentally studied by
Lummer and Pringsheim. The experimental arrangement is shown in fig.
Construction and working: The radiation emitted by a black body is first focused onto a slit S by a
concave mirror M1. Then it is made to focus on another concave mirror M2. After reflection from mirror
M2, the radiation is allowed to incident on a fluorspar prism ABC. The prism produces the spectrum of
radiations and is incident on concave mirror M3. The radiations are detected by means of bolometer. The
deflections produced in the galvanometer gives the intensity of radiation E λ for a particular wavelength λ .

50
The experiment is repeated for different temperatures of a black body and a graph is plotted between λ
and E λ.
Experimental results:
1. The emission of a black body radiation contains all wavelengths at any temperature.
2. As temperature increases, the energy increases first and then decreases.
3. At a particular wavelength the energy E λ is maximum.
4. The wavelength λ m corresponding to maximum energy shifted towards shorter wavelength as the
temperature of the black body increases.
1
i.e., λ m ∝
T
λ m T =constant
Which is known as Wien’s law.
5. The area under the curve gives the total energy emitted by a black body at a particular temperature. It
was found that
4 4
E ∝T or E=σ T
Which is known as Stefan’s Boltzmann law.
 Wien’s displacement law:

Statement: According to Wien’s displacement law, the wavelength corresponding to maximum energy
emission is inversely proportional to the absolute temperature of the black body.
i.e., λ m ∝ T or λ m T =constant
here this constant is called as Wien’s constant and has value 0.2896 ×10−2 mK.
Derivation: consider a spherical enclosure with perfectly reflecting walls and capable of expansion
radially outwards like a foot ball bladder. Let this enclosure be filled with black body radiation of energy
density u at a temperature T . If V be the volume of the enclosure, then
Total internal energy of radiation U =uV ……….. (1)
Now assume that the walls of the enclosure move outwards such that radiation inside it expands
adiabatically.
From 1st law of thermodynamics dQ=dU + p dV
dV – change in volume of the enclosure
u
p= – pressure of radiation on the walls of enclosure.
3
dU – decrease in internal energy of radiation.
dQ=0 (for adiabatic process)
u
∴ 0=d ( uV ) + dV
3
u
0=u dV +V du+ dV
3
4u
dV +V du=0
3

51
4 dV du
On dividing with uV ⇒ + =0
3 V u
Integrating the above expression, we have
4
log e V + log e u=log c
3
log e V 4 /3 + log e u=log c
4/3
V u=c
4
According to Stefan’s law, u=σ T where σ is Stefan’s constant
V
4/3
( σ T 4 )=c
1 /3
V T =constant ……….. (A)
The radiation filled in the enclosure undergo continuous reflections from the moving walls of the
enclosure. Due to Doppler’s effect, there is a change in the wavelength, which is calculated as follows
Let OA be a ray of wavelength λ which incident at an angle θ on the wall in position S1.
Let it gets reflected along AC. Let AC ¿ λ . Now the next crest gets reflected after time T from B because
of expansion of wall from S1 to S2. Let it gets reflected along BD.
Let AB+ BD= λ1
Change in wavelength dλ=λ 1−λ=AB+ BD− AC
dλ=( AB+ BN + ND )− AC
¿ AB+ BN ( ∵ ND =AC )
'
¿ A B+ BN ( ∵ AB+ A ' B )
' '
¿ A N = A A cos θ
¿ 2 AM cos θ=2 vT cos θ
vλ
¿ 2 cos θ
c (
∵T=
λ
c ) ……….. (B)
Every ray inside the enclosure undergoes repeated reflections. The path of a single ray is shown in fig.
Distance travelled by the wave between two successive collisions ¿ 2 r cos θ
2r cos θ
Time between two successive collisions ¿
c
c
No of reflections in one second ¿
2r cos θ
c
No of reflections in time dt ¿ dt
2r cos θ

52
The change in wavelength in time dt is given by dλ=¿ change in wavelength in one reflection × number
of reflections in time dt
vλ c dt vλ
dλ=2 cos θ × = dt
c 2r cos θ r
dλ v dt dr
λ
=
r
=
r (∵v=
dr
dt)
Integrating this expression, log e λ=log e r+ log c
λ
λ=rc or =c ………….. (C)
r
From eq. (A) V 1 /3 T =constant
(3
πr )
4 3 1 /3
T =constant
rT =constant ………… (D)

λ
From eqs. (C) and (D), we get × rT =constant
r
λT =constant
This is called Wien’s displacement law.
 Rayleigh – jeans formula:

Consider a hallow cubic enclosure of side l with perfectly reflecting walls. Let it be filled with black
body radiation. According to electromagnetic theory, the radiation waves in the enclosure travel in all
possible directions and undergo multiple reflections from the walls of the enclosure. The reflected and
incident waves interfere to form stationary waves.
nλ
The allowed wavelengths are given by =l , where n=1 ,2 , 3 … ∞
2
2l
λ= ……… (1)
n
c nc
∴ allowed frequencies are given by ϑ = = ……….. (2)
λ 2l
Every allowed frequency is called as mode of vibration. If the three edges of the cube taken as three
coordinate axes, then the no of loops in each direction is given by
2l 2l 2l
n x = , n y = , n z=
λ λ λ
n x λ n y λ nz λ
l= = =
2 2 2
The radiation waves can be inclined at any angle to the coordinate axes. For waves making an angle α , β
and γ with three axes, we have
nx λ ny λ nz λ
l cos α = ,l cos β= , lcos γ =
2 2 2
n λ n λ n λ
cos α= x , cos β= y , cos γ = z
2l 2l 2l

53
We know that cos 2 α +cos 2 β +cos 2 γ =1
( )( )( )
nx λ 2 ny λ 2 nz λ 2
2l
+
2l
+
2l
=1
2 2 2
n x + n y +n z =
λ( )
2l 2
………. (3)
The above equation represents an ellipsoid with n x , n y and n z directions as coordinate axes. So the total
no of modes of vibrations are the total number of possible sets of n x , n y, n z.
To calculate the no of modes of vibration, consider a two dimensional plane. For two dimensional plane
2 2
( )
eq. (3) has form n x + n y =
2l 2
λ
Let the area of each square in the figure is unity.
∴ total no of modes of vibration = total no of squares
[ ( )]
2
1 2l
¿ π
4 λ
By extending this idea for 3D case of eq. (3)
[ ( )]
3
1 4 2l
Total no of modes of vibration f = π
8 3 λ
( )
3
4 π l −3
∴ total no of modes of vibration between λ and λ+ dλ is df = 4
dλ
3 λ
4 πV
Neglect the negative sign as dλ is positive, df = 4 dλ V – Volume of enclosure
λ
The above number should be multiplied by 2 as transverse electromagnetic waves have two polarizations
for each mode. Thus the total number of modes of vibration is given by
8 πV
df = 4 dλ
λ
8π
∴ No of modes per unit volume ¿ 4 dλ
λ
According to law of equi partition of energy, the average energy per mode of vibration is kT .
8 πdλ 8 πkT
∴ Energy density in wavelength λ and λ+ dλ is E λ dλ= 4 ×kT = 4 dλ
λ λ
8 πkT
E λ dλ= dλ
λ4
This is Rayleigh – Jeans formula for energy distribution.

 Validity of Rayleigh – Jeans formula: The graph shows that Rayleigh – Jeans formula agrees well
with experiment at longer wavelength. Hence Rayleigh – Jeans formula is valid only at longer
wavelengths.
 PLANCK’S RADIATION LAW: In 1900, Max Planck introduced the revolutionary /concept of
radiation known as quantum theory of radiation.
54
Assumptions:
1. A black body radiator (Source) contains simple harmonic oscillators of all possible
frequencies.
2. The oscillators cannot emit or absorb energy continuously. This is a contradiction to
electromagnetic theory which allows a continuous emission or absorption of energy.
3. Emission or absorption of energy takes place in discrete amounts, i.e., energy of
oscillator is quantized.
The possible values of energy E=nhϑ
Where n – positive integer
h – Planck’s constant
ϑ – frequency of oscillator
Average energy of an oscillator:
Let N be the total number of Planck’s oscillators and E be their total energy. Then the average energy
E
per oscillator ε = ………… (1)
N
Let there be N 0 , N 1, N 2, N 3,….., N r ,…..etc. oscillators having energy 0 , ε , 2 ε , 3 ε , …… rε , ….etc.
Now we have N=N 0+ N 1+ N 2+ N 3+ …+ N r +… ……….. (2)
And E=0+ε N 1 +2 ε N 2 +3 ε N 3 +…+rε N r + … ……….. (3)
From Maxwell’s distribution formula, number of oscillators having energy rε is given by
N r =N 0 e
−rε/ kT
=N 0 exp ( )
−rε
kT
……… (4)
Where k is a Boltzmann constant.
(2) ⇒ N=N 0+ N 0 exp

−ε
kT( ) ( )
+ N 0 exp
−2 ε
kT ( )
+…+ N 0 exp
−rε
kT
+…
[ −εkT )+exp( −2kTε )+ …+exp( −rεkT )+…]

¿ N 1+exp (
0
N0
N=
[ 1−exp
−ε
kT ( )] (∵ 1+ x+ x +…= 1−x
2 1
) …….. (5)
Substituting these values of N 1, N 2, N 3, …..from equation (4) in equation (3)
E=( N 0 ×0 ) + ε N 0 exp
−ε
kT ( ) ( )
+2 ε N 0 exp
−2 ε
kT ( )
+ 3 ε N 0 exp
−3 ε
kT ( )
…+rε N 0 exp
−rε
kT
+…
kT [ )+…]
¿ ε N exp ( ) 1+2 exp ( )+3 exp ( ) …+r exp (
−ε −ε −2 ε −( r −1 ) ε
0
kT kT kT
¿ N ε exp (
kT )
[ ]
−ε 1
{1−exp( −εkT )}
0 2
……….. (6)
Now the average energy of the oscillator is given by

55
( ){ ( )}
2
−ε −ε
N 0 ε exp / 1−exp
E kT kT
ε= =
N / {1−exp ( ) }
N −ε
0
kT
ε exp ( )
−ε
kT ε
¿ =
{1−exp( −εkT )} {exp( kTε )−1}
hϑ
¿
{ ( ) }
exp
hϑ
kT
−1
Therefore,
hϑ
ε=
{ ( ) }
exp
hϑ
kT
−1
………. (7)
 Planck’s formula:
Number of oscillators per unit volume in the frequency range ϑ and ϑ + dϑ is given by
8π ϑ2
f = 3 dϑ ………. (8)
c
hϑ
ε=
Average energy of each oscillator
exp
hϑ
kT { ( ) }
−1
hϑ 8 π ϑ2
∴ total energy of the oscillator within the frequency range dϑ is Eϑ dϑ = × 3 dϑ
{e }
hϑ
kT
c
−1
8 πh ϑ 3 1
Eϑ dϑ = dϑ
c3
{e }
hϑ
kT
−1
This is the Planck’s radiation law.
8 πhc 1
In terms of wavelength
E λ dλ= 5
λ
{
hc
e λkT −1
dλ
}
¿ dϑ ∨¿
( λc dλ )
2
 Different laws from Planck’s law:

 Wien’s formula:
hc
For shorter wavelengths, i.e., when λ is very small e λkT ≫1, one can be neglected in comparison of
hc
e λkT .
8 πhc 1
E λ dλ= dλ
According to Planck’s formula, λ5
{e } ……… (1)
hc
λkT
−1
For shorter wavelengths, formula (1) can be written as
56
8 πhc 1
E λ dλ= 5 hc
dλ
λ
e λkT
−hc
8 πhc λkT
E λ dλ= 5
e dλ
λ
hc
Putting 8 πhc=A and =B
k
−B
A
E λ dλ= 5 e kT dλ
λ
This is Wien’s formula which agrees with experimental results for shorter wavelengths.
 Rayleigh – Jeans formula:
hc
For longer wavelengths, i.e., when λ is very large hc / λkT is small and e λkT can be expanded as
hc 2 2
λkT hc h c hc
e =1+ + 2 2 2 +…=1+ , neglecting higher powers
λkT λ k T λkT
8 πhc 1
E λ dλ= 5 dλ
Now from Planck’s law, λ
{ 1+
hc
λkT
−1 }
8 πhc λkT 8 πkT
E λ dλ= 5 × dλ= 4 dλ
λ hc λ
8 πkT
E λ dλ= 4 dλ
λ
This is Rayleigh – Jeans formula which agrees with experimental results for longer wavelengths.
 Pyrometers:
Pyrometers are instruments used for measurement of high temperatures. The pyrometers based on the
principles of radiation are termed as radiation pyrometers. There two types of radiation pyrometers.
(1) Total radiation pyrometers.
(2) Optical pyrometers
(1) Total radiation pyrometers: The instruments that measure total radiation emitted by the body under
test are called as total radiation pyrometers.
(2) Optical pyrometers: The optical pyrometers compare the intensity of radiation of a certain
wavelength emitted by the body with that of the radiation of same wavelength emitted by a standard
body at a known temperature.
 Ferry’s total radiation pyrometer:

Ferry’s total radiation pyrometer consists of a large concave mirror C coated with nickel on
the front surface. The mirror has a small opening at the centre through which an eye – piece is fitted.

57
A small diaphragm is arranged before the concave mirror. Behind the diaphragm there is a blackened
strip S which is connected to one junction of a thermocouple (hot junction). The thermocouple junction
connected to a milli voltmeter (mV) which measures the thermo e.m.f developed. The concave mirror C
can be moved by using a rack and pinion screw to focus the radiation on S. To obtain accurate focusing
the diaphragm is made of two semi – circular mirrors M, M inclined at an angle of 50 with a central hole
of diameter about 1.5 mm. The focusing is perfect when the images in the two mirrors overlap exactly to
form a complete circle.
 Calculation of temperatures:
We know that according to Stefan’s law, the milli voltmeter deflection θ is proportional to T 4,
where T is the temperature of hot body
4
θ ∝T −T 0
4
where T 0 – Temperature of the surroundings
But T 0 ≪ T , therefore θ ∝T 4
 In practice it was found that the power of T lies between 3.8 to 4.2. Hence we take
K
θ ∝T
Taking logarithm, log θ=K log T ( y = mx form)
 Using bodies whose temperatures are accurately known the deflection θ are noted. Now a graph
between log θ and log T is plotted. It comes out to be a straight line.
 Any unknown temperature can be obtained with the help of this graph, if θ is known.
 Temperature of Sun:
The sun consists of a central hot core having a temperature of 20 million degrees. This central hot core is
surrounded by thick shell called photosphere. The temperature of photosphere gives the effective
temperature of sun (around 6000 K). The thick layer above photosphere is about 300 to 400 km called
reversing layer. The matter in reverse layer is in gaseous state. The extension of reversing layer is
chromosphere.
The temperature of sun can be calculated by assuming the sun as a perfect black body. Let R
be the radius of the photosphere of sun. Then
Surface area of sun ¿ 4 π R2
The total amount of energy emitted by sun per second ¿ 4 π R2 σ T 4
This energy is spread out in all directions. Let r be the mean distance of earth and sun.
∴ Energy received by the surface of earth per second ¿ 4 π r 2 S
Where S – solar constant
4 π r 2 S=4 π R 2 σ T 4
2
4 r S
T = 2
R σ
( )
1/ 4
r2 S
T= 2
R σ
Which is the temperature of the sun.

58
 Disappearing filament optical pyrometer:

Construction: The disappearing filament optical pyrometer consists of telescope fitted with an objective
O at one end and an eyepiece E at the other end. The distance between objective and eyepiece can be
adjusted by a rack and pinion arrangement. The filament F of the lamp is connected to a battery B,
rheostat Rh and ammeter A in series. The filament is heated by the electric current flowing through it and
its temperature can be changed by adjusting the current in the circuit. The current is recorded by the
ammeter. D1 and D2 are diaphragms which limit the cone of radiation entering the telescope.
Working: The objective of the pyrometer is directed towards the hot body whose temperature is to be
measured. The objective is moved until the image of the hot body is focused on the filament F. This
image is viewed with the help of eyepiece E fitted with red glass filter G. Initially, the dark lamp filament
is viewed against the bright back ground of the image of hot body. Now the filament is heated by
switching on the electric current. The current is adjusted until the brightness of the filament just matches
the brightness of the background. Then the filament disappears because there is no contrast between the
background and filament. The current in the filament is recorded with the help of ammeter.
Calculation of temperature:
The temperature of the hot body T can be calculated from the following formula.
2
I =a+ bT + c T where I =¿ current
a , b , c are constants
Using three bodies whose temperatures are known accurately the corresponding ammeter readings are
noted. When the filament gets disappeared. By solving the three equations the value of the constants a, b,
c are calculated.
After calculating a, b, c values, unknown temperatures can be measured by knowing the corresponding
current ( I value).

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1

 Postulates of Kinetic theory

 Maxwell’s distribution law of velocities:

SURENDRA JINKA, LECTURER IN PHYSICS LEPAKSHI DEGREE COLLEGE, PRODDATUR

SURENDRA JINKA, LECTURER IN PHYSICS LEPAKSHI DEGREE COLLEGE, PRODDATUR

i.e., ∭ a e−b u + v +w du dv d w=1

SURENDRA JINKA, LECTURER IN PHYSICS LEPAKSHI DEGREE COLLEGE, PRODDATUR

Which is the Maxwell’s distributive law.

SURENDRA JINKA, LECTURER IN PHYSICS LEPAKSHI DEGREE COLLEGE, PRODDATUR

The R.M.S speed is given by c rms =√ c 2=

We know that c=1.59

SURENDRA JINKA, LECTURER IN PHYSICS LEPAKSHI DEGREE COLLEGE, PRODDATUR

Expression for mean free path:

SURENDRA JINKA, LECTURER IN PHYSICS LEPAKSHI DEGREE COLLEGE, PRODDATUR

SURENDRA JINKA, LECTURER IN PHYSICS LEPAKSHI DEGREE COLLEGE, PRODDATUR

Velocity of gas in layer EF ¿ ( u−λ )

 Transport of kinetic energy or thermal conduction:

Heat energy transferred in one sec Q=Q −Q =( C ) c (T + λ

 Transport of mass or diffusion of gases:

SURENDRA JINKA, LECTURER IN PHYSICS LEPAKSHI DEGREE COLLEGE, PRODDATUR

Expression for diffusion coefficient (D):

number of molecules crossing unit area of XY downward in one sec ¿ C ( n+ λ )

SURENDRA JINKA, LECTURER IN PHYSICS LEPAKSHI DEGREE COLLEGE, PRODDATUR

No of molecules crossingunit area per sec

 Terms related to thermodynamics:

SURENDRA JINKA, LECTURER IN PHYSICS LEPAKSHI DEGREE COLLEGE, PRODDATUR

 Thermodynamic co – ordinates (or)

In thermodynamics, the state of a system

 Zeroth law of thermodynamics :

 External and internal works:

SURENDRA JINKA, LECTURER IN PHYSICS LEPAKSHI DEGREE COLLEGE, PRODDATUR

 Isothermal process (or) Isothermal change:

Therefore, total work done W =∫ P dV -------①

For isothermal process PV =RT (Boyle’s law)

Work done in small change in volume dW =P dV

∴ Total work done W =∫ P dV ……….. (1)

For an adiabatic process P V γ =K (constant )

SURENDRA JINKA, LECTURER IN PHYSICS LEPAKSHI DEGREE COLLEGE, PRODDATUR

SURENDRA JINKA, LECTURER IN PHYSICS LEPAKSHI DEGREE COLLEGE, PRODDATUR

 First law of thermodynamics:

Statement 2: If dQ amount of heat is supplied to a system, then

Applications of first law of thermodynamics:

SURENDRA JINKA, LECTURER IN PHYSICS LEPAKSHI DEGREE COLLEGE, PRODDATUR

 Cyclic process: When a system undergoes a cyclic process then dU =0

 Adiabatic relations between pressure, volume and temperature of an ideal gas:

SURENDRA JINKA, LECTURER IN PHYSICS LEPAKSHI DEGREE COLLEGE, PRODDATUR

P V γ =K (constant ) ………………. (b)

Eliminating V from eq (b), we have

SURENDRA JINKA, LECTURER IN PHYSICS LEPAKSHI DEGREE COLLEGE, PRODDATUR

 Carnot’s heat engine or Carnot’s reversible engine:

SURENDRA JINKA, LECTURER IN PHYSICS LEPAKSHI DEGREE COLLEGE, PRODDATUR

(a) Isothermal expansion (AB):

The work done by the gas W 1=Q 1=RT 1 log e ( )

The work done on the gas W 3 =Q2=R T 2 log e ( ) V4

SURENDRA JINKA, LECTURER IN PHYSICS LEPAKSHI DEGREE COLLEGE, PRODDATUR

Efficiency of the engine:

from (2) and (3), we get

SURENDRA JINKA, LECTURER IN PHYSICS LEPAKSHI DEGREE COLLEGE, PRODDATUR

Clausius statement: It is impossible for any cyclical machine to transfer

SURENDRA JINKA, LECTURER IN PHYSICS LEPAKSHI DEGREE COLLEGE, PRODDATUR

 Coefficient of performance K of a refrigerator:

SURENDRA JINKA, LECTURER IN PHYSICS LEPAKSHI DEGREE COLLEGE, PRODDATUR