Entropy

What is Entropy ?

 A measure of the disorder or randomness in a system

 It is an extensive property

 It is denoted by S (kJ/K)

 Specific entropy…..s (kJ/kg K)

 The greater the disorderness , the more will be the entropy.

Which one is more disordered ?

The glass of ice cubes or the glass of water ?????

The molecules in the solid are in a much more ordered state so

they have less entropy.
Entropy increases on Melting

Entropy decreases on Freezing

Entropy increases with :
Entropy Curve :
Sign Convention :

+Δs ------- entropy increases

- Δs-------- entropy decreases

Clausius Theorem :

 The cyclic integral of dQ for a reversible cycle is equal

to zero. T

dQ

R
T
0
Property of Entropy :

For any reversible path

dQ
 ds
T
Clausius Inequality :

dQ
 T
0 dQ
 ds
T
dQ
 T
 0  Re versible dQ
 ds...Re versible
T
dQ
 T
 0  Irreversible dQ
 ds...Irreversible
T
dQ dQ
 T
 0  Im possible
T
 ds...Im possible
Entropy Principle :
dQ
ds 
T
 For Isolated system, dsiso  0
dsiso  0...Re versible
dsiso  0...Irreversible
dsiso  0...Im possible

 Entropy of an isolated system can never decrease.

dsuniv  0
dssystem  dssurroundings  0
Entropy Generation (Sgen):
 The entropy generation is always a positive quantity or

zero.
 It is not a property of the system as its value depends on the

process.

Sgen  0.....Irreversible
Sgen  0.....Re versible
Sgen  0.....Im possible
Change in Entropy in different process :
 Isothermal Process :

P1
ds  mR ln( )
P2
V2
ds  mR ln( )
V1
 Isobaric Process :

T2
ds  mCP ln( )
T1
V2
ds  mCP ln( )
V1
 Isochoric Process :

T2
ds  mCV ln( )
T1
P2
ds  mCV ln( )
P1

 Isentropic process :

ds  0
 Polytropic Process :

 V2 P2 
ds  m CP ln( )  CV ln( ) 
 V1 P1 
 T2 P2 
ds  m CP ln( )  R ln( ) 
 T1 P1 
 T2 V2 
ds  m CV ln( )  R ln( ) 
 T1 V1 
Tds Relations :
 1st Tds Relation :
Q  dU  W
 dQ  dU  PdV
 Tds  dU  PdV
dU PdV
 ds  
T T
mCVdT mRTdV
 ds  
T VT
mCVdT mRdV
 ds  
T V
2 2 2
dT dV
  ds  mCV   mR 
1 1
T 1
V
 T2 V2
 s 2  s1  m CV ln  R ln
 T1 V1 

 2nd Tds Relation :

H  U  PV
 dH  dU  PdV  VdP
 dH  dQ  VdP
 dQ  dH  VdP
mRTdP
 Tds  mCPdT 
P
mCPdT mRTdP
 ds  
T PT
mCPdT mRdP
 ds  
T P
2 2 2
dT dP
  ds  mCP   mR 
1 1
T 1
P
 T2 P2 
 s 2  s1  m CP ln  R ln
 T P1 

 3rd Tds Relation :

 T2 P2 
s 2  s1  m CP ln  R ln 
 T1 P1 
 T2 P2 
 s 2  s1  m CP ln  CP  CV  ln 
 T1 P1 
 T2 P2 P2 
 s 2  s1  m CP ln  CP ln  CV ln 
 T1 P1 P1 
 T 2 P1 P2 
 s 2  s1  m CP ln  CV ln 
 T 1P 2 P1 
 V2 P2 
 s 2  s1  m CP ln  CV ln 
 V1 P1 
Entropy Applications :
 Heat Transfer through a finite temperature difference :

Q
T1 T2
T1>T2

dsuniv  ds1  ds 2
Q Q
dsuniv  
T1 T2
 T1 T 2 
dsuniv  Q 
 T 1T 2 
 Adiabatic mixing of two fluids:

1 2

m1 m2

C1 C2

t1 t2
Let tf = final(mixing) temperature

t 1  tf  t 2
Heat rejected by fluid 1 = heat gained by fluid 2

m1C 1(t1  tf )  m 2C 2(tf  t 2)

m1C 1t1  m 2C 2t 2
tf 
m1C 1  m 2C 2
Tf Tf
dQ m1C1dT Tf
ds1     m1C1 ln
T1
T T1
T T1
Tf Tf
dQ m 2C 2 dT Tf
ds 2     m 2C 2 ln
T2
T T2
T T2
dsuniv  ds1  ds 2
Tf Tf
dsuniv  m1C 1 ln  m 2C 2 ln
T1 T2
T1  T 2
m1  m 2, C 1  C 2  Tf 
2
Tf 2
dsuniv  mc ln
T 1T 2
2
 T1  T 2 
 2 
dsuniv  mc ln  
 T 1T 2 
 
 T1  T 2 
 2 
dsuniv  2mc ln  
 T 1T 2 
 
dsuniv is +ve as
T1  T 2
 T 1T 2
2 D
E
Proof :
r  radius
AO  CO  DO  r A C
O B
AC  T 1  T 2  2r
T1  T 2 T1 T2
DO  r 
2
BE 2  T 1T 2
BE  T 1T 2
DO  BE
T1  T 2
 T 1T 2
2
 Maximum work obtained from two finite bodies :

Let tf = final(mixing) temperature

T1 T2 W=0

t 1  tf  t 2
T1  T 2
Tf 
2
 In order to get maximum work a reversible heat engine is to
be placed in between the two bodies.
Q1  mCP (T 1  Tf )
T1
Q 2  mCP (Tf  T 2)
W  Q1  Q 2  mCP (T 1  T 2  2Tf ) Q1
W  W max when, Tf  min W
HE
Tf
ds1  mCP ln
T1
Q2
Tf
ds 2  mCP ln
T2 T2
Tf 2
dsuniv  ds1  ds 2  mCP ln
T 1T 2
To get Wmax Tf will be min

As per the entropy principle,

dsuniv  0
Tf 2
 mCP ln 0
T 1T 2
Tf 2
 mCP ln  0  min
T 1T 2
Tf 2
 ln  0, mCP  0
T 1T 2
Tf 2
 ln  ln1
T 1T 2
 Tf  T 1T 2
 T1  T 2
 T 1T 2
2
So for Wmax,

Tf  T 1T 2
W max  mCP (T 1  T 2  2 T 1T 2 )
 Maximum work obtained between a finite body and
TER :

Body,T
T0
dsbody  mCP ln
T Q
Q W
dsTER  W
T0
HE
T 0 Q W
dsuniv  mCP ln 
T T0
Q-W
dsuniv  0
T 0 Q W
mCP ln  0 TER,T0
T T0
 T0 W Q
mCP ln 
T T0
T0
W  Q  T 0mCP ln
T
T0
W max  Q  T 0mCP ln
T
T0
W max  mCP (T  T 0)  T 0mCP ln
T
 Process exhibiting external mechanical irreversibility:
a) Isothermal Dissipation of work :

T = temp of resistor = temp of surrounding

I = current flow through the resistor

Q = W (at const T, ΔU =0)

dssys  0(T  const )
Q W
dssurr  
T T
Q W
dsuniv  dssys  dssurr  
T T
b) Adiabatic Dissipation of Work :

Ti Tf

dssurr  0
Tf
dQ
dssys  
Ti
T
Tf
mCPdT
dssys  
Ti
T
Tf
dssys  mCP ln
Ti