Second law

of
Thermodynamics
Reversible and Irreversible Process
A process which can be retraced in the opposite direction so
that the working substance passes through exactly the same
conditions as it does in the direct process.

It means both system and surroundings are returned to their

initial states at the end of the reverse process.

Conditions of Reversibility for any heat engine process:

 All the processes must be infinitely slow.
 The working parts of the engine must be completely free
from friction.
 No loss of energy due to conduction, convection or radiation
during the cycle of operation
Reversible and Irreversible Process….

The process which cannot be retraced in opposite order by

reversing the controlling factors is called an Irreversible
process.

In nature all changes are irreversible.

Examples of irreversible processes

(i) Heat produced by Friction

(ii) Electricity flow through a resistance
(iii)Heat transfer by Radiation
(iv)Plastic deformation
Reversible and Irreversible Process….

Reversible process is only an ideal case.

 In practice no mechanical process is frictionless

 No insulator or conductor is perfect.
 There is always loss of heat due to friction, conduction,
convection or radiation.

Some examples of nearly reversible processes are:

(i) Expansion and compression of spring.
(ii) Frictionless adiabatic expansion or compression of fluid.
(iii) Isothermal expansion or compression.
(iv)Evaporation
Cyclic process
When a process returns to its original state after completing a
series of changes, then it is called a cyclic process.

 U of a system depends only on the state of a system

 In a cyclic process, the initial state and final state are same.
 ∆U will be zero i.e., ∆U=0.

Hence from the first law of energy,

∆Q=∆U + ∆W
or ∆Q = 0 + ∆W
∆Q = ∆W

The work done by the system in a cyclic process is equal to the

heat absorbed by the system.
Heat Reservoir and Heat Engine
HEAT RESERVOIR a system having very large heat capacity i.e.
it is a body capable of absorbing or rejecting finite amount of
energy (heat) without any appreciable change in its’
temperature.

Two types depending upon nature of heat.

Heat reservoir which rejects heat from it is called source.

While the heat reservoir which absorbs heat is called sink.

HEAT ENGINE a device used for converting heat into work.

Second law of thermodynamics

 First law of thermodynamics establishes equivalence

between the quantity of heat used and the mechanical work

 but does not specify the conditions under which conversion

of heat into work is possible, neither the direction in which
heat transfer can take place.

 This gap has been bridged by the second law of

thermodynamics.

First Law- Law of conservation of energy

Second Law- Law of possibility of energy transformation and
direction.
Statement of Second law of thermodynamics

Clausius statement: it is impossible for a self acting machine

working in a cyclic process, without any external force, to transfer
heat from a body at a lower temperature to a body at a higher
temperature.

Kelvin statement: it is impossible to get a continuous supply of

work from a body by cooling it to a temperature lower than that of
its surroundings.

Planck statement: it is not possible to construct an engine which,

working in a complete cycle, will produce no other effect than the
absorption of heat from a reservoir and its conversion into an
equivalent amount of work.

Edser statement : The heat itself flows from a body of higher

temperature to a body of lower temperature.
 Carnot cycle

 A thermodynamic cycle in which the working substance starting

from a given condition of temperature, pressure and volume is
made to undergo through four successive operations(two
expansions -one isothermal and other adiabatic and two
compression- one isothermal and other adiabatic) at the end of
which the working substance back to its initial state/condition is
called a Carnot cycle.

 A theoretical cycle concept proposed by Nicolas Leonard Sadi

Carnot, a French engineer, in 1824.
 Carnot reversible engine

A theoretical engine which is free from all the defects of practical

engines. Efficiency is maximum and is an ideal engine.

Cylinder:
 Made up of non-conducting
walls and conducting bottom.
 A perfect gas as a working
substance.
 Cylinder fitted with a
perfectly non-conducting and
frictionless piston.
Source:
 a hot body which is kept at a
constant temperature T1.
 It has infinite thermal capacity.
Temperature will remain the
same even after drawing any
amount of heat from it.
 Carnot reversible engine……

Sink:
 a cold body which is kept at a
constant lower temperature
T2 .
 Thermal capacity is also
infinite. Any amount of heat
added to it will not increase
its temperature.

Stand:
 Made up of non-conducting
material so as to perform
adiabatic operations.
Working principle and work done
Step 1, Isothermal Expansion:
 Heat, Q1, is absorbed from the hot
reservoir at T1.
 Because none of the heat goes into
changing the temperature of the gas,
all of the heat goes into pushing the
=
piston up as the gas expands.
 All of Q1 is turned into work. T1 T2

V2 V2
W1   P.dV  
RT1
.dV 𝑃𝑉 = 𝑛𝑅𝑇
V
V1 V1
V2
 RT1 
dV V
 RT1 ln 2
𝑅𝑇
V V1 𝑃= [𝑛 = 1]
V1 𝑉
 areaABGE
Working principle and work done…..
Step 2, Adiabatic Expansion:
 hot reservoir heat source is
removed and the gas is allowed to
expand adiabatically.
 The gas continues to expand, and
T1 T2
the temperature drops to T2 , cold
reservoir temperature, to
compensate.

V3 V3

 
K
W2  P .dV  .dV
V
V2 V2
V3
dV KV3    1  KV2   1
K

V
V2

 1

P3V3 V3    1  P2V2 V2   1 P3V3  P2V2

 
1 1
RT2  RT1 R( T1  T2 )
 
1  1
 AreaBCHG
Working principle and work done…..
Step 3, Isothermal compression:
 Work is done on the gas to
compress it, but simultaneously
hold the temperature of the gas
constant at T2.
 Heat, Q2, is transferred to the T1 T2
cold reservoir.
 As the temperature is constant,
all of Q2 is turned into work.

V4 V4

 
RT2
W3  P .dV  .dV
V
V3 V3
V2


dV V V
 RT2  RT2 ln 4   RT2 ln 3
V V3 V4
V1

 AreaCHFD
Working principle and work done…..
Step 4, Adiabatic compression:
 Further work on the gas, but no longer allow
the heat to be transferred to the cold
reservoir
 The temperature of the gas rises back to T1.
T1 T2
V1
R( T1  T2 )
W4 

V4
P .dV  
 1

 AreaDFEA

W  W1  W 2  W 3  W 4
V2 R( T1  T2 ) V R( T1  T2 )
 RT1 ln   RT2 ln 3 
V1  1 V4  1
 AreaABGE  AreaBCHG  AreaCHFD  AreaDFEA
V2 V
 RT1 ln  RT2 ln 3
V1 V4
 AreaABCD
 Q1  Q2
Schematic diagram of heat engine
Efficiency
Efficiency……..

…..(1)

…..(2)
Efficiency……..
Adiabatic expansion ratio & Efficiency
Considering the two adiabatics BC and DA
1
V3 V4 T1   1
 ( )
V2 V1 T2
V3 V4
But   , adiabatic expansion ratio
V2 V1
1
T1  1
  ( )
T2
T2 1  1
or ( )
T1 

T2 1  1
  1  1( )
T1 
Entropy
A thermodynamic property of a working
substance which remains constant during an
adiabatic process.
Change in entropy
Change in entropy……..
Let ABCD and DCEF represent Carnot's
reversible cycles. During cycle ABCD, Q1 heat is
absorbed at T1 in going A to B and Q2 heat is
rejected at T2 in going C to D.
Q1  Q2 T1  T2
Hence  
Q1 T1
Q2 T
1  1 2
Q1 T1

Q2 T2

Q1 T1
Q1 Q2

T1 T2
Change in entropy……..
Considering the cycle DCEF
Q2 Q3

T2 T3

Then Q1 Q2 Q3
   consant
T1 T2 T3
If Q is heat absorbed or rejected at T going from
one to another adiabatic, then
Q
 consant
T
Change in entropy……..
If two adiabatics are very close
Q
 consant
T
This constant is the entropy.
Q
S 
T
For a finite reversible process from A to B
SB B dQ

 dS  
SA A T
B dQ
SB  S A 

A T
Entropy in terms of unavailable energy

Let TS -temperature of a source

TR- temperature of sink

Consider a cycle absorbing QS heat at TS

and rejecting QR heat at TR.

Available energy = work done

= heat absorbed at TS- heat
rejected at TR
=QS-QR=QS(1-QR/QS)
=QS(1-TR/TS)
 Entropy in terms of unavailable energy…
Unavailable energy= heat absorbed at TS Total energy -
( )

Available energy
=QS- QS(1-TR/TS)
=(QS/TS).TR
Smaller TR, smaller unavailable energy

If TO is the lowest possible temperature of sink,

then
QO=unavailable energy at TO
= QS/TS.TO
=entropy.TO
Entropy is a measure of unavailability of energy of
a system.
Entropy change for reversible process
(i) Reversible adiabatic process:
For reversible process, change in entropy
dQ
 dS   T
But for adiabatic process dQ=0
0
 dS   T   0
S  cons tan t

Entropy remains constant for reversible adiabatic

process and hence this type of process is called
isentropic.
Entropy change for reversible process
(ii) Reversible isothermal process:
For reversible process, change in entropy
dQ
 dS   T
But for isothermal process T=constant
1
 dS  T  dQ
Q
S 
T
If heat flows into a system, Q is positive, entropy
increases.
If heat flows out of a system, Q is negative, entropy
decreases.
 T-S diagram for Carnot cycle
 From A to B, fig1(a), heat Q1 is absorbed at constant
temperature T1 (isothermal). The increase in entropy ΔS
takes place, fig.1(b).
 From B to C, no entropy change (adiabatic).The
temperature decreases at constant entropy.
 From C to D, there is decrease in entropy at constant
temperature T2 (isothermal).
 From D to A, there is no change in entropy (adiabatic) but
the temperature increases.

(a) (b)
Fig1
T-S diagram………
Area under AB represents the heat absorbed in the
isothermal expansion
Area under CD is the heat expelled in the isothermal
compression. The differences of the heat is the work done.

Q1= heat absorbed

= T1 ΔS
Q2 = heat rejected
= T2 ΔS
Work done, W = Q1- Q2
= T1 ΔS - T2 ΔS
= (T1 - T2) ΔS
W (T1  T2 )S
Then the Carnot engine efficiency, η  
Q1 T1 S
(T1  T2 )

T1
 References:

Heat Thermodynamics and Statistical Physics- By Brij Lal (Reprint-2008)

A Text Book of Heat – By. Dr. Tafazzal Hossain (Reprint-1996)