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UNIT 2
Second Law of Thermodynamics
 Limitations of I Law
2

 Does not specify the direction of flow of heat and

work
 i.e,whether the heat flows from hot body to cold body
or cold body to hot body.
 Q and W are mutually convertible.
W – Converted fully to Q
 This violates the foresaid statements.
 Heat Engine
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 Device which extracts heat

Hot reservoir
from a hot reservoir (source),
converts it into useful work Q1=Qin Energy intake
and a part of heat energy is
rejected to a cold reservoir
W=Qin-Qbody
Working W = Qin - Qout
(sink). out

 Heat source: (TERH) supplies Q2=Qout Energy exhaust

heat continuously to the
system operating in a cyclic Cold reservoir

process.
 Heat sink: (TERS) absorbs W Qin  Qout
heat continuously from the  
system operating in a cyclic Qin Qin
process.
 Refrigerator and Heat pump
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 Refrigerator Hot reservoir

 devicewhich extracts heat from Q2=Qout =Qin + W

a system to maintain its
temperature lower than the W=Qin-Qbody
Working W
surrounding.
out

 Heat pump Qin = Q1

 devicewhich supplies heat to a Cold reservoir

system to maintain its
temperature higher than the
surrounding.
 Performance of heat engines and
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reversed heat engines
 Heat engine

where, W = Net work transfer from the engine,

Q1= Heat transfer to engine.
 Refrigerator

where, Q2 = Heat transfer from cold reservoir, and

W = Net work transfer to the refrigerator.
 Heat Pump

where, Q1 = Heat transfer to hot reservoir, and

W = Net work transfer to the heat pump.
 Performance of heat engines and
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reversed heat engines

ηth is always less than unity and (C.O.P.) heat

pump is always greater than unity.

COP of heat pump = 1 + COP of refrigerator.

 Statements of second law of
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thermodynamics
1. Kelvin-Planck Statement
2. Clausius Statement
Kelvin-Planck Statement
 “It is impossible to construct an engine, which while
operating in a cycle produces no other effect except
to extract heat from a single reservoir and do
equivalent amount of work”.
 It means that the efficiency of a heat engine cycle is
never 100%.
 This precludes a perfect heat engine.
 Statements of second law of
thermodynamics
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Clausius Statement
 “It is impossible for a self acting machine working in a

cyclic process unaided by any external agency, to

convey heat from a body at a lower temperature to a
body at a higher temperature”.
 In other words, heat of, itself, cannot flow from a colder

to a hotter body.
 This precludes a perfect refrigerator.
 Applies to refrigerators , air conditioners and heat pumps
 Perpetual motion machine of the
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second kind (PMM- II)
 Without violating the first
law, a machine can be Thermal Reservoir
imagined which would
Q1
continuously absorb heat
from a single thermal W=Q1
PMM2
reservoir and would convert
this heat completely into
Q2=0
work.
 The efficiency of such a
machine would be 100 per
cent.
Equivalence of the statements
Violation of Kelvin-Planck Statement leads to
violation of Clausisus statement

T1
Q1 Q1 + Q2

W=Q1
HE HP

Q2=0
Q2

T1
 Equivalence of Clausius Statement to the Kelvin-
Planck Statement
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T1
Q1 Q1 = Q2
W=Q1 - Q2
HE HP

Q2
Q2

T1
 REVERSIBILITY AND IRREVERSIBILITY
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 Reversible or ideal process &

Irreversible or natural process
y A
 Reversible process
 System and surroundings restored
to their initial states, without
producing any changes in the rest
B
of the universe.
 Infinitely slow process
 Consists of succession of x
equilibrium states
 Irreversible process
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 Thermodynamic equilibrium
is not satisfied
 Dissipative effects are y A
present
 Friction, viscosity, inelasticity,
electrical resistance, magnetic
hysterisis etc B
 Conditions for reversibility
 Equilibrium is attained
 No dissipative effects
x
 Quasi-static process
 Carnot cycle
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 Efficiency of the reversible heat
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engine
 Carnot engine- Not possible
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 Isothermal process – Slow

 Adiabatic process – Fast
 Not possible to avoid friction b/w moving parts
 Heat source with const T is not possible
 Carnot theorem
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 No engine operating on a cyclic process is more

efficient than Carnot engine when working between
same temperature limits.
T1
Q1 Q1 Q1
HE andHE  R.HE
1 2
HE1 HE2 R.HE
W W’’
W’
Q2 Q’2 Q’’2

T1
 Corollaries of Carnot Theorem
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 All the reversible engines operating b/w the two

given TR with fixed temperature have the same
efficiency
 ηR.HE operating b/w two reservoirs is independent
of the nature of the working fluid and depends only
on the T of the reservoirs
 Clausius inequality
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 Whenever the closed system undergoes cyclic

process, the algebraic sum of or cyclic integral of
ratio of heat transfer to absolute temperature is
always less than or equal to zero.

Or
dQ
 T 0
It provides a criterion for the reversibility of a cycle
 Q1 T1
Clausius inequality 
Q2 T2
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We know that, Q1 Q2

irrev  rev T1 T2

 Q2   T2  Q1 Q2

1    1    0
T1 T2
 Q1 irrev  T1  rev
Q1 Q2
 0
 Q2   T2  T1 T2
      
 Q1 irrev  T1  rev dQ
When changing the sign, the equality changes  T 0
Q2 T2 dQ

Q1 T1  T 0 Rev. Cycle

dQ
 T 0 Irrev. Cycle
 Entropy
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 Index of unavailaibility or degradation of energy.

 Increases with the addition of heat and decreases
with its removal.
 Mathematically, dS  dQT
2 dS  2 dQ
1 1 T

 Property of a system, depends only on end state of

the process.
 Principle of increase of entropy
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 For infinitesimal process, ds  dQ

T
 For an isolated system, dQ = 0
 Therefore dsiso  0
 For a reversible process dsiso  0 or S = constant
 For an irreversible process dsiso  0
 Proved that entropy of an isolated system can never
decrease .
 It always increases and remains constant only when the
process is reversible.
 This is known as the principle of increase of entropy or
simply the entropy principle.
 ENTROPY AND DIRECTION: THE SECOND LAW
A DIRECTIONAL LAW OF NATURE
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 All spontaneous process or natural(irreversible

process)
 occuronly in one direction from a higher to a lower
potential
 Increase entropy of the Universe (system &
surrounding)
 II law gives the direction of an increase in the
entropy of the universe.
 I and II law of TD summarised by
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Rudolf Clausius
 The energy of the world (universe) is constant
 The entropy of the world tends towards a maximum.

III law of TD
 It is impossible by any procedure, no matter how
idealized, to reduce any system to the absolute
zero of temperature in a finite number of
operations