Course No.

Phy- 1203(B), Heat & Thermodynamics, Physics Discipline, KU

Chapter - 6
The Second Law of Thermodynamics

Md. Shohel Parvez

Lecturer
Physics Discipline, Khulna University, Khulna
Reversible and Irreversible Process:
A reversible process is one which can be retracted in opposite direction
by changing the external conditions infinitesimally.
The condition of reversibility for any heat engine or process can be
stated as follows:
 The pressure and temperature of the working substance must not
differ appreciably from those of surrounding at any stage of the
cycle of operation.
 All process taking place in the cycle of operation must be
infinitely slow.
 The working parts of the engine must be completely free from
friction.
 There should not be any loss of energy due to conduction, convection
or radiation during the cycle of operation.

Irreversible process
The irreversible process is also called the natural process because all
the processes occurring in nature are irreversible processes.
We also say that an irreversible process is one which can not be
retracted in opposite direction by changing the external conditions
infinitesimally.
Example of some natural irreversible processes are: spontaneous
expansion of a gas into an evacuated space, spontaneous conduction of
heat along a metal bar which is hot at one end and cold at the other,
transfer of heat by radiation from a hotter to a cold body etc.
Second law of thermodynamics
The second law is a generalization of certain experiences and
observations and is concerned with the direction in which energy transfer
takes place. The law has been stated in a number of ways, which means
the same thing.
Lord Kelvin’s statement
“It is impossible to get a continuous supply of work from a body by
cooling it to a temperature lower than that of surroundings”

Planck’s statement
“It is impossible to construct an engine which, working in a complete
cycle, will produce no effect other than the raising of a weight and the
cooling of a heat reservoir”.
 Thus, it is impossible to construct an engine which working in a
complete cycle, will produce no effect other than the absorption of heat
from a reservoir and its conservation into an equivalent amount of work.

These two statements can be combined into one equivalent statement,

known as the Kelvin-Planck’s statement of the second law of
thermodynamics.

Kelvin-Planck’s statement
“It is impossible to construct an engine which operating in a cycle,
has the sole effect of extracting heat from a reservoir and performing an
equivalent amount of work.”
Clausius’s Statement
“It is impossible for a self-acting machine working in a cycle
process, unaided by external agency, to transfer heat from a body at a
lower temperature to a body at a higher temperature.”
In other words it may be stated as, Heat can not flow of itself from a
colder body to a hotter body.

Carnot’s Cycle:
In order to obtain a continuous supply of work, the working
substance is subjected to the following cycle of quasi-static operations
known as Carnot’s Cycle.
 A(𝑝1 𝑣1)
(𝑇1 𝑄1 )
B(𝑝2 𝑣2 )

D(𝑝4 𝑣4 ) C(𝑝3 𝑣3 )
(𝑇2 𝑄2 )
E F G H

Isothermal Expansion: The cylinder is first placed on the source, so

that the gas acquires the temperature 𝑇1 of the source. It is then allowed
to undergo quasi static expansion. As the gas expands, its temperature
tends to fall. Heat passes into cylinder through perfectly conducting
base which is in contact with the source. The gas therefore, undergoes
slow isothermal expansion at the constant temperature 𝑇1 .
Let the working substance during isothermal expansion goes from state
A(𝑃1 , 𝑉1 , 𝑇1 ) to state B(𝑃2 , 𝑉2 , 𝑇1 ) at constant temperature 𝑇1 along AB.
So the work done 𝑊1 is
𝑉2 𝑉2
𝑊1 = 𝑉1
𝑃𝑑𝑉 = 𝑅𝑇1 𝑙𝑜𝑔𝑒 = 𝑎𝑟𝑒𝑎 𝐴𝐵𝐺𝐸𝐴
𝑉1

Adiabatic expansion:

The cylinder is now removed from the source and is placed on the
insulating stand. The gas is allowed to undergo slow adiabatic expansion,
performing external work at the expense of its internal energy until its
temperature falls to 𝑇2 . This operation is represented by the adiabatic BC
starting from the state B(𝑃2 𝑉2 𝑇1 ) to the state C(𝑃3 , 𝑉3, 𝑇2 ). So the work
done is,
 𝑉3 𝑉3 𝑑𝑉
𝑊2 = 𝑉2
𝑃. 𝑑𝑉 =𝐾 𝑉2 𝑉 𝛾
(Since P𝑉 𝛾 = 𝐾)

KV31−γ −KV21−γ
=
1−γ

𝑃3 𝑉3 −𝑃2 𝑉2
=
1−𝛾

𝑅𝑇2 −𝑅𝑇1
=
1−𝛾

𝑅(𝑇1 −𝑇2 )
= = 𝐴𝑟𝑒𝑎 𝐵𝐶𝐻𝐺𝐵
𝛾−1

Isothermal Compression: The cylinder is now removed from the

insulating stand is placed on the sink which is at temperature 𝑇2 . The
piston is now very slowly moved inwards so that the work is done on
the gas . the temperature tends to increase due to heat produced
by compression.
 This operation is represented by isothermal CD, starting from the
state C(𝑃3 , 𝑉3 , 𝑇2 ) to the state D(𝑃4 , 𝑉4 , 𝑇2 ). So the work done is,

𝑉4
𝑣4
𝑊3 = 𝑃𝑑𝑉 = 𝑅𝑇2 [𝑙𝑜𝑔𝑒 𝑉]𝑣3
𝑉3

𝑉3
= −𝑅𝑇2 𝑙𝑜𝑔𝑒 = 𝑎𝑟𝑒𝑎 𝐶𝐻𝐹𝐷𝐶
𝑉4
Adiabatic compression:
The cylinder is now removed from sink and again placed on the
insulating stand. The piston is slowly moved inwards so that the gas is
adiabatically compressed and temperature rises. The adiabatic
compression is contained till the gas comes back to its original
condition; state A(𝑃1 , 𝑉1 , 𝑇1 ), thus completing one full cycle.
This operation is represented by adiabatic DA, starting from D(𝑃4 , 𝑉4 , 𝑇2 )
to the final state A(𝑃1 , 𝑉1 , 𝑇1 ).
So work done 𝑊4 is
𝑉1
𝑊4 = 𝑉4
𝑃. 𝑑𝑉

𝑅(𝑇1 − 𝑇2 )
=−
𝛾−1
Since 𝑊2 𝑎𝑛𝑑 𝑊4 are equal and opposite sign. So they cancel each other.
So net work done,
𝑊 = 𝑊1 + 𝑊3
Work done by the engine per cycle: During the above cycle, working
substance absorbs an amount of heat 𝑄1 from the source and rejects 𝑄2 to
the sink.
so the net amount of heat absorbed by the gas per cycle
= 𝑄1 − 𝑄2
The net work done by the engine per cycle
= 𝑊1 + 𝑊2 + 𝑊3 + 𝑊4
=𝑊1 + 𝑊3
According to the conservation law,
Net heat absorbed = Net work done per cycle
𝑄1 − 𝑄2 = 𝑊1 + 𝑊3
𝑉2 𝑉3
= 𝑅𝑇1 𝑙𝑜𝑔𝑒 − 𝑅𝑇2 𝑙𝑜𝑔𝑒 ………………(1)
𝑉1 𝑉4

Since the points A and D lie on the same adiabatic DA

𝑇1 V1γ−1=𝑇2 V4γ-1
 𝑇2 𝑉
= ( 1 )𝛾−1 …………………………….(2)
𝑇1 𝑉4

Similarly the points B and C lie on the same adiabatic BC

𝑇1 V2γ−1=𝑇2 V3γ−1
𝑇2 𝑉
= ( 2 )𝛾−1 …………………………(3)
𝑇1 𝑉3

From equation (2) and (3) we can write,

𝑉1 𝛾−1 𝑉2 𝛾−1
( ) =( )
𝑉4 𝑉4

𝑉1 𝑉2
=
𝑉4 𝑉3

𝑉2 𝑉3
=
𝑉1 𝑉4
Substituting in equation (1), we get
𝑉2 𝑉2
Net work done, 𝑊 = 𝑄1 − 𝑄2 = 𝑅𝑇1 𝑙𝑜𝑔𝑒 − 𝑅𝑇2 𝑙𝑜𝑔𝑒
𝑉1 𝑉1

𝑉2
𝑊 = 𝑄1 − 𝑄2 = 𝑅 𝑇1 − 𝑇2 𝑙𝑜𝑔𝑒
𝑉1
Efficiency: The efficiency of the heat engine is the rate of quantity of
heat converted into work (useful output) per cycle to the total amount
of heat absorbed per cycle.

𝑢𝑠𝑒𝑓𝑢𝑙 𝑜𝑢𝑡𝑝𝑢𝑡 𝑊
𝐸𝑓𝑓𝑖𝑐𝑖𝑒𝑛𝑐𝑦, η= =
𝐼𝑛𝑝𝑢𝑡 𝑄1

(𝑄1 − 𝑄2 )
=
𝑄1
 𝑉2
𝑅 𝑇1 − 𝑇2 𝑙𝑜𝑔𝑒 𝑉
1
=
𝑉2
𝑅𝑇1 𝑙𝑜𝑔𝑒
𝑉1
𝑇1 − 𝑇2
η=
𝑇1
𝑇2
η=1− ………………………….. 𝑎
𝑇1

From equation (a) we conclude that the efficiency depends only upon
the temperature of the source and sink and is always less than the
quantity. The efficiency is independence of working substance.

From equation (a) we can get η = 1, if 𝑇2 = 0𝑘 i.e. the temperature of

the sink is at absolute zero degree.
 In practice, it is never possible to reach absolute zero and hence
100% conversion of heat energy into mechanical work is not possible.
Again the efficiency is minimum or zero when 𝑇1 = 𝑇2 , the
temperature of the source is equal to the temperature of sink. Then the
engine does not work.

Heat Engine
Any practical machine which converts heat into mechanical work is
called a heat engine.
In thermodynamics, a heat engine is a system that converts heat or
thermal energy and chemical energy to mechanical energy, which can
then be used to do mechanical work.
 Heat engines in their operation absorb heat at a higher temperature,
converts part of it into mechanical work and rejects the remaining heat at
a low temperature. In this process, a working substance is used. In steam
engines, the working substance is water vapour, and in all gas engines
the working substance is a combustible mixture of gases.
In any heat engine, the working substance goes through certain
changes of pressure, volume and temperature, and then returns to the
initial state. The complete changes through which the working substance
undergoes from its initial state and back to its starting state constitute one
cycle of operation.
Diesel Engine
In the case of a diesel engine, air is admitted into the cylinder in the
beginning. This air is compressed adiabatically so that the temperature is
high enough to ignite the oil sprayed into the cylinder. The ideal
conditions are assumed while discussing the complete cycle viz. (i) the
working substance is air all the time and it behaves as a perfect gas and
(ii) there is no friction. The cycle is called the diesel cycle.
1. 𝑒 to 𝑎 (Fig.) represents the intake of air and its volume changes to
𝑉1 . This is the charging stroke.
2. a to b represents the compression stroke. Air is compressed
adiabatically. The temperature changes from 𝑇1 𝑡𝑜 𝑇2 and the
volume changes from 𝑉1 𝑡𝑜 𝑉2 .
3. b to c represents the stage when the oil is
sprayed into the cylinder. The oil burns
immediately. The pressure is maintained
constant. The temperature changes from 𝑇2
to 𝑇3 (to 2000ºC) and the volume changes
from 𝑉2 𝑡𝑜 𝑉3 .
4. c to d represents the working stroke. The
mixture of air and diesel oil vapour expand
adiabaticlly.
5. As the point d is reached, the exhaust, the
exhaust valve opens and the pressure drops
 the pressure drops to the point a the volume remains constant, but
temperature and pressure decrease.
6. a to e represents the exhaust stroke. The unburnt vapours of the oil
and the mixture of gases in the cylinder are exhausted out of the cylinder.

Efficiency
From b to c, the pressure remains constant. Considering 1 gram of
the working substance, the quantity of heat absorbed,
𝑄1 = 1 × 𝐶𝑝 (𝑇3 − 𝑇2 )
From d to a the volume remains constant.
The quantity of heat rejected,
𝑄2 = 1 × 𝐶𝑣 (𝑇4 − 𝑇1 )
Dividing, we get

𝑄2 𝐶𝑣 (𝑇4 − 𝑇1 )
=
𝑄1 𝐶𝑝 (𝑇3 − 𝑇2 )

1 (𝑇4 − 𝑇1 )
=
𝛾 (𝑇3 − 𝑇2 )
We know that efficiency

𝑄2
𝜂 =1−
𝑄1

1 𝑇4 − 𝑇1
=1− ……………. 1
𝛾 𝑇3 − 𝑇2
𝑇4 −𝑇1
To evaluate , all the temperatures are to be expressed in terms
𝑇3 −𝑇2
 of 𝑇2 . Compression

𝑉1
Let ρ be the adiabatic expansion ratio. Then 𝜌 = and 𝜀 the
𝑉2

𝑉3
combustion expansion ratio or fuel cut off ratio = .
𝑉2

1. The points a and b are on same adiabatic,

𝛾−1 𝛾−1
∴ 𝑇1 𝑉1 = 𝑇2 𝑉2

𝑉2 𝛾−1
𝑇1 = 𝑇2 [ ]
𝑉1

1 𝛾−1
= 𝑇2 [ ] … … . . (2)
𝜌
2. The points b and c are at same pressure
 𝑇3 𝑇2
=
𝑉3 𝑉2

𝑉3
𝑇3 = 𝑇2 = 𝑇2 𝑒 ……….. 3
𝑉2
3. The points c and d are on the same adiabatic.
𝛾−1 𝛾−1
𝑇4 𝑉4 = 𝑇3 𝑉3
But 𝑉4 = 𝑉1

𝑉3 𝛾−1 𝑉3 𝑉2 𝛾−1
𝑇4 = 𝑇3 [ ] = 𝑇3 [ × ]
𝑉1 𝑉2 𝑉1

𝑉3 𝛾−1 𝑉2 𝛾−1
𝑇4 = 𝑇3 [ ] [ ]
𝑉2 𝑉1
 𝛾−1
1 𝛾−1
𝑇4 = 𝑇3 [𝑒] [ ]
𝜌

1 𝛾−1
𝑇4 = 𝑇2 𝑒 [𝑒]𝛾−1 [ ]
𝜌

1 𝛾−1
𝑇4 = 𝑇2 [𝑒]𝛾 [ ] … … . . (4)
𝜌

1 𝑇4 − 𝑇1
𝜂 =1−
𝛾 𝑇3 − 𝑇2

𝛾 1 𝛾−1 1 𝛾−1
𝑇
1 2 [𝑒] [ ] − 𝑇2 𝜌]
[
𝜌
=1−
𝛾 𝑇2 𝑒 − 𝑇2
 1 1 𝛾−1 𝑒 𝛾 − 1
𝜂 =1− ( ) … … … (5)
𝛾 𝜌 𝑒−1

For some compression ratio, the efficiency of an Otto engine is more

than a diesel engine. In practice the compression ratio for an Otto engine
is from 7 to 9 and for diesel engine it is from 15 to 20. due to the higher
compression ratio, an actual diesel engine has higher efficiency than the
Otto (petrol) engine. The cylinder must be strong enough to withstand
very high pressure.
Entropy:
The thermal property of a working substance which remains constant
during an adiabatic process.
Or, for describing the condition of a working substances completely;
another variable of state, in addition to pressure, volume, temperature,
internal energy etc.
Or, lack of order or predictability; gradual decline into disorder.
According to definition we can write,

𝐻𝑒𝑎𝑡 𝑎𝑑𝑑𝑒𝑑 𝑜𝑟 𝑠𝑢𝑏𝑡𝑟𝑎𝑐𝑡𝑒𝑑 𝑜𝑟 𝑕𝑒𝑎𝑡 𝑐𝑕𝑎𝑛𝑔𝑟 𝑑𝑄

𝐸𝑛𝑡𝑟𝑜𝑝𝑦 = =
𝐴𝑏𝑠𝑜𝑙𝑢𝑡𝑒 𝑡𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒 𝑇
In case of adiabatic process no heat is allowed to enter or leave the
system. Hence 𝑑𝑄 = 0
 𝑑𝑄
∴ 𝑑𝑆 = =0
𝑇
Thus, there is no change of entropy during an adiabatic process or
entropy remains constant.
Change of entropy in reversible cycle

Consider complete reversible Carnot’s cycle ABCD as shown in fig.

for an ideal gas formed by two isothermals i.e. AB at a temperature
𝑇1 and CD at a temperature 𝑇2 and two adiabatic BC and DA.

Isothermal Expansion AB
Let 𝑄1 be the quantity of heat absorbed by the working substance in
going from state A to state B during
Isothermal expansion AB at a constant temperature 𝑇1 . The increase in
entropy of the working substance is given by

𝐵
𝑄1
𝑑𝑆 = +
𝑇1
𝐴
Adiabatic Expansion BC: In going from state B to C along the
adiabatic BC there is no change in entropy of the working substance but
the temperature falls from 𝑇1 𝑡𝑜 𝑇2 due to expansion.

𝑑𝑆 = 0
𝐵
Isothermal compression CD: In going from state C to D along the
isothermal CD, the working substance rejects heat 𝑄2 to the sink at
temperature 𝑇2 . The entropy of the working substance decreases and the
change in entropy is given by

𝐷
𝑄2
𝑑𝑆 = −
𝑇2
𝐶
Adiabatic compression: In going from state D to A along the adiabatic
DA, there is no change in entropy but temperature rises from 𝑇2 to 𝑇1

𝑑𝑆 = 0
𝐷
Thus the net gain in entropy of the working substance in the whole cycle
ABCDA

𝐵 𝐶 𝐷 𝐴

= 𝑑𝑆 + 𝑑𝑆 + 𝑑𝑆 + 𝑑𝑆
𝐴 𝐵 𝐶 𝐷

𝑄1 𝑄2
𝑑𝑆 = −
𝑇1 𝑇2

But for a reversible Carnot’s Cycle

𝑄1 𝑄2 𝑄1 𝑄2
= 𝑜𝑟 − =0
𝑇1 𝑇2 𝑇1 𝑇2
Substituting, we get
𝑄1 𝑄2
𝑑𝑆 = − =0
𝑇1 𝑇2

S = Constant
Where the integral sign with a circle refers to a complete cycle.
Thus in a cycle of reversible process, the entropy of the system remains
unchanged or remains constant. In other words, the total change in
entropy is always zero
B
A 𝑇1

𝑇2
C
D
Change of entropy in Irreversible Process: The thermodynamic state
of a system can be defined with the help of the thermodynamical
coordinates of the system. The state of a system can be changed by
alternating the thermodynamical coordinates.
Changing from one state to the other by changing the thermodynamical
coordinates is called a process.
Consider a simple irreversible cycle in which the working substance
absorbs a quantity of heat 𝑄1 𝑎𝑡 𝑇1 and rejects a quantity of heat
𝑄2 𝑎𝑡 𝑇2 . Then the efficiency of the engine performing such a cycle is
given by
𝑄1 − 𝑄2
η′ =
𝑄1
Let a reversible engine work between the same two temperature limits.
Then its efficiency

𝑇1 − 𝑇2
η=
𝑇1
According to Carnot’s theorem
η′ < η
𝑄1 − 𝑄2 𝑇1 − 𝑇1
Or <
𝑄1 𝑇1

𝑄2 𝑇2
1− <1 −
𝑄1 𝑇1

𝑄2 𝑇2
𝑜𝑟, >
𝑄1 𝑇1
 𝑄2 𝑄1
𝑜𝑟, >
𝑇2 𝑇1
𝑄2 𝑄1
𝑜𝑟, − >0 …………………(1)
𝑇2 𝑇1

Which is positive. So in case of irreversible process entropy

increases.

Physical Significance of Entropy

Although it is very difficult to conceive the idea of entropy as there is
no physical method to demonstrate it, i.e., it can not be felt like
temperature, pressure, volume and does not produce any effect which can
be demonstrate; it has significance in thermodynamics. Entropy is a real
physical quantity defined by equation
 𝐵
𝛿𝑄 𝑑𝑄
𝑑𝑆 = 𝑜𝑟 𝑆𝐵 − 𝑆𝐴 =
𝑇 𝑇
𝐴
And possesses the following important properties:
1. Just like temperature remains constant in isothermal process, the
entropy remains constant in an adiabatic process.
2. It is a definite single valued function of the thermodynamic variables
describing the state of a working substance.
3. In every natural process (i.e., irreversible change) there is always an
increase in entropy.
4. The second law of thermodynamics can be stated in terms of entropy
of a system.
5. Due to increase in entropy, unavailable energy increases.
6. According to Freeman Dyson, the entropy is a measure of
disorderness. This disorderness can be evaluated by using the
relation.
𝑆 = 𝑘 log 𝑊

Where k is the Boltzmann’s constant and W is the disorder parameter.

Entropy of a Perfect Gas
Consider 1 gm of a perfect gas, occupying a volume V at pressure P
and temperature 𝑇. Let 𝑑𝑄 be the heat supplied to the gas, then according
to first law of thermodynamics we have
𝑑𝑄 = 𝑑𝑈 + 𝑑𝑊 ……… 𝑖
Let 𝐶𝑉 be the specific heat at constant volume, 𝑑𝑇 be the rise of
 temperature and 𝑑𝑉 be the change in volume then
𝑑𝑈 = 𝐶𝑉 𝑑𝑇 and 𝑑𝑊 = 𝑃. 𝑑𝑉
Substituting in eqn. (i), we get
𝑑𝑄 = 𝐶𝑉 𝑑𝑇 + 𝑃𝑑𝑉 … … … (𝑖𝑖)
If S is the entropy per unit mass of the gas, then

𝑑𝑄 1
𝑆= = 𝐶𝑉 𝑑𝑇 + 𝑃𝑑𝑉
𝑇 𝑇

𝑑𝑇 𝑃
= 𝐶𝑉 + 𝑑𝑉 … … … . (𝑖𝑖𝑖)
𝑇 𝑇

We can calculate S in terms of different thermodynamic variables.

These are:
(i) S in terms of temperature and volume
for a perfect gas 𝑃𝑉 = 𝑅𝑇

𝑃 𝑅
=
𝑇 𝑉
Substituting in equation (iii), we get

𝑑𝑇 𝑑𝑉
𝑆= 𝐶𝑉 + 𝑅
𝑇 𝑉

= 𝐶𝑉 log 𝑒 𝑇 + 𝑅 log 𝑒 𝑉 + 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡

But 𝑅 = 𝐶𝑃 − 𝐶𝑉
∴ 𝑆 = 𝐶𝑉 log 𝑒 𝑇 + 𝐶𝑃 − 𝐶𝑉 log 𝑒 𝑉 + 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 … . . 𝑖𝑣
Where 𝐶𝑃 is specific heat at constant pressure.
(ii) S in terms of temperature and pressure
For a perfect gas, 𝑃𝑉 = 𝑅𝑇

𝑅𝑇
∴ 𝑉=
𝑃
And 𝑃𝑑𝑉 + 𝑉𝑑𝑃 = 𝑅𝑑𝑇
Or, 𝑃𝑑𝑉 = 𝑅𝑑𝑇 − 𝑉𝑑𝑃
Substituting in eqn. (iii), we get

𝑑𝑇 𝑅𝑑𝑇 − 𝑉𝑑𝑃
𝑆= 𝐶𝑉 +
𝑇 𝑇

𝑑𝑇 𝑅𝑑𝑇 𝑅𝑑𝑃
= 𝐶𝑉 + −
𝑇 𝑇 𝑃
 𝑑𝑇 𝑑𝑇 𝑑𝑃
= 𝐶𝑉 +𝑅 −
𝑇 𝑇 𝑃

𝑑𝑇 𝑑𝑇 𝑑𝑃
= 𝐶𝑉 + (𝐶𝑃 − 𝐶𝑉 ) −
𝑇 𝑇 𝑃

𝑑𝑇 𝑑𝑇 𝑑𝑇 𝑑𝑃
= 𝐶𝑉 + 𝐶𝑃 − 𝐶𝑉 − (𝐶𝑃 − 𝐶𝑉 )
𝑇 𝑇 𝑇 𝑃

𝑑𝑇 𝑑𝑃
= [𝐶𝑃 − (𝐶𝑃 − 𝐶𝑉 ) ]
𝑇 𝑃

= 𝐶𝑃 log 𝑒 𝑇 − 𝐶𝑃 − 𝐶𝑉 log 𝑒 𝑃 + 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 … . (𝑣)

(iii) S in terms of pressure and volume
For ideal gas, 𝑃𝑉 = 𝑅𝑇

𝑃𝑉 𝑃𝑑𝑉 + 𝑉𝑑𝑃
∴ 𝑇= 𝑎𝑛𝑑 𝑑𝑇 =
𝑅 𝑅
Substituting in equation (iii), we get

𝑃𝑑𝑉 + 𝑉𝑑𝑃 𝑃𝑑𝑉. 𝑅

𝑆= [𝐶𝑉 + ]
𝑅𝑇 𝑃𝑉

𝑃𝑑𝑉 + 𝑉𝑑𝑃 𝑃𝑑𝑉. 𝑅

= [𝐶𝑉 + ]
𝑃𝑉 𝑃𝑉

𝑑𝑉 𝑑𝑃 𝑑𝑉
= 𝐶𝑉 + + 𝐶𝑃 − 𝐶𝑉
𝑉 𝑃 𝑉
 𝑑𝑃 𝑑𝑉
= (𝐶𝑉 + 𝐶𝑃 )
𝑃 𝑉

= 𝐶𝑉 log 𝑒 𝑃 + 𝐶𝑃 log 𝑒 𝑉 + 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡

While deriving the relations for S given by eqns. (iii), (iv), (v), and
(vi), we have assumed the entropy of the gas to be zero at absolute zero
of temperature.
However, in actual practice, we are interested in change in entropy of
a gas when it goes from its state of pressure 𝑃1 , volume 𝑉1 , and
temperature 𝑇1 to another state having the values 𝑃2 , 𝑉2 𝑎𝑛𝑑 𝑇2
respectively. This is obtained by integrating eqn. (iii) between limits 𝑇1
and 𝑇2 . The change of entropy ∆𝑆 = 𝑆2 − 𝑆1 for each of the above three
cases and can be calculated as under.
 In terms of temperature and volume, the change of entropy

𝑇2 𝑉2
∆𝑆 = 𝑆2 − 𝑆1 = 𝐶𝑉 log 𝑒 + 𝐶𝑃 − 𝐶𝑉 log 𝑒 … … (𝑣𝑖𝑖)
𝑇1 𝑉1
In terms of temperature and pressure, ∆𝑆 will be

𝑇2 𝑃2
∆𝑆 = 𝑆2 − 𝑆1 = 𝐶𝑃 log 𝑒 − 𝐶𝑃 − 𝐶𝑉 log 𝑒 … . 𝑣𝑖𝑖𝑖
𝑇1 𝑃1
And in terms of pressure and volume, ∆𝑆 will be

𝑃2 𝑉2
∆𝑆 = 𝑆2 − 𝑆1 = 𝐶𝑉 log 𝑒 + 𝐶𝑃 log 𝑒 … . . (𝑖𝑥)
𝑃1 𝑉1
The above equations are evaluated for a gas of unit mass. For a gas of
m gm., the change of entropy can be obtained by multiplying these
relations by mass m of the gas.