Entropy Balance

The property entropy is a measure of molecular disorder or

randomness of a system

the entropy of a pure crystalline substance at absolute zero

temperature is zero

This statement is known as the third law of thermodynamics.


the molecules of the shaft are rotating in
the same direction together. This
organized energy can readily be
used to perform useful tasks such as
raising a weight or generating electricity.
Being an organized form of energy, work is
free of disorder or randomness and thus
free of entropy. There is no entropy
transfer associated with energy transfer as
work.
In the absence of friction, raising a weight
by a rotating shaft does not create any
disorder (entropy), and thus energy is not
degraded during this process.
The Paddle-wheel work is converted to
the internal energy of the gas, raising the
gas temperature, creating a higher level
of molecular disorder in the container.
the paddle-wheel energy is now
converted to a highly disorganized form
of energy, which cannot be converted
back to the paddle wheel. Only a portion
of this energy can be converted to work
by partially reorganizing it through the
use of a heat engine.
Therefore, energy is degraded during
this process, the ability to do work is
reduced, molecular disorder is produced,
and associated with all this is an
increase in entropy.
Isentropic Efficiency
The quantity of energy is always preserved during an actual process (the first law),
but the quality is bound to decrease (the second law).
This decrease in quality is always accompanied by an increase in entropy.

S=100/(20+273)
S=100/(80+273) =0.3413 kJ/K
=0.2833 kJ/K

Q=100 kJ Q=100 kJ Q=100 kJ

Hot Body at 80 C Cold Body at 20 C

Principle of Increase in Entropy
Q
dS 
T
Q
dS   dSGenerated
T
• entropy change of a system is greater than
the entropy transfer by an amount equal to
the entropy generated during the process
within the system
• Energy can neither be created nor destroyed
(1 st Law)
• Entropy can be created but it cannot be destroyed
(2 nd Law)

System
Into sys = + ve Ein Esystem Eout

Ssystem
Sin Sgen  0 Sout
Ein - Eout = Esystem

Sin - Sout + Sgen = Ssystem

 Sin - Sout + Sgen = Ssystem

Entropy Entropy Total Entropy

Transfer Generation Change

 Total   Total   Total   Change in the 

       
 entropy    entropy    entropy    total entropy 
 entering   leaving   generated   of the system 
       
 Sin - Sout + Sgen = Ssystem

Entropy Balance
• the entropy change of a system during a
process is equal to the net entropy transfer
through the system boundary and the
entropy generated within the system.
 Change of Entropy Ssystem
Ssystem = Sfinal state - Sinitial state
• Ideal Gas
T2 P2
s  c p ln  R ln
T1 P1
• Pure Substance
s  s2  s1
• Solids & Liquids
dT T2
s   c(T )  cm ln
T T1
Mechanisms of Entropy Transfer,
Sin, and Sout
• Energy is transferred into or out of a
system by:
• Heat Work Mass flow

• Entropy is transferred into or out of a

system by:
• Heat Mass flow
• Work transfer is entropy free
• Define Heat & Work
Entropy Transfer
Mass System Mass
Sin Ssystem Sout
Heat Heat
Sgen  0

• Is recognized at the boundary only

• It represents the entropy gained or lost by a
system during a process
• For closed system;
Entropy transfers by heat only
• For adiabatic closed system:
Entropy Transfer = 0
 Entropy Transfer by Heat

system
Q=500 kJ Tb= 400 K

Sheat=Q/Tb = 1.25 kJ/K

Entropy transfer by heat transfer (Entropy Flow)

Q
S heat  (T = constant)
T
2 Q Qk
S heat   
1 T Tk
Entropy Transfer by Mass flow
Mass contains entropy as well as energy,
The entropy and energy contents of a
system are proportional to the mass


Smass  m
 .s
 Entropy Generation

• The term Sgen represents the entropy generation

within the system boundary only, and not the
entropy generation that may occur outside the
system boundary during the process as a result
of external irreversibilities.
• Therefore, a process for which Sgen = 0 is
internally reversible, but not necessarily totally
reversible.
• The total entropy
generated during a
process can be
determined by Immediate
applying the entropy surroundings Tsurr
balance to an
extended system that
includes the system Q system
itself and its
immediate
surroundings where
external irreversibility
might be occurring.

Immediate Surroundings = Buffer Zone

@ ambient temperature Tsurr
Total Sgenerated:

Stot  S sys  Sbuffer zone

0

Stot  S sys
 For Closed Systems
entropy balance

Qk
 T  S gen  S system  S 2  S1
k
Adiabatic closed system

S gen  S system
System Surroundings:
any closed system and its surroundings can be treated as an adiabatic system and the
total entropy change of a system is equal to the sum of the entropy changes of its parts

S gen   S  S system  S surroundings

 For a Control Volume
Qk
 T   mi si   me se S gen  S system  (S 2  S1 ) cv
k

Q k dSCV
 T   mi si   me se S gen  d
  
k

For steady-flow process

Q k
S gen   m e se  m i si 
Tk
For steady-flow single stream

Q k
S gen  m ( se  si )  
Tk
For steady-flow single stream and adiabatic S gen  m ( se  si )
 Example
Entropy Generation in a Wall
• Brick wall
• Area 5*8 m 27 C 0 C

• Thickness = 0.3 m
Q
• Q = 1035 W
• Steady state
• Find: 20 C 5 C

• SGen, SGen, tot

 Qk
 T  S gen  S system  S 2  S1
k
• Wall at Steady conditions
• Ssys = 0
W
Sin - Sout + Sgen =0
A
 Q   Q 
      SGen  0 L
 T in  T out
L
 1035   1035 
     SGen  0
 293 in  278 out

SGen = 0.191 W/K

 Qk E
 T  S gen  S system  S 2  S1
k
X
• Wall at Steady conditions
• Ssys,tot = 0 T

Sin - Sout + Sgen,tot =0 E

 Q   Q  N
      SGen  0
 T in  T out D
 1035   1035   E
    SGen,tot  0
 300   273 
D
SGen,tot = 0.341 W/K System
 Example: Throttling Process
• Steam at 7 MPa and 450 C is throttled in
a valve to a pressure of 3 Mpa during a
steady-flow process.
• Determine the entropy generated during
this process and check if the increase of
entropy principle is satisfied
steady-flow process No Heat transfer

kinetic and potential energy changes are negligible

 State 1: P1 = 7 MPa T1 = 450°C
h1 = 3288.3 kJ/kg s1 = 6.6353 kJ/kg.K

State 2: P1 = 3 MPa h1 = h2
h2 = 3288.3 kJ/kg s2 = 7.0046 kJ/kg.K

Q k dSCV
 T   mi si   me se S gen  d
  
k

S gen  m ( se  si )
sgen = s2 - s1 = 7.0046 - 6.6353 = 0.3693 kJ/kgK

The increase of entropy principle is obviously

satisfied during this process since the entropy
generation is positive.
 Example 2
• A 50 kg block of iron is at 500 K is dropped into
a large lake at 285 K.
• The block finally reaches thermal equilibrium
with the lake water.
• The average specific heat of iron is 0.45 kJ/kgK
• Determine
• The entropy change of the iron block
• The entropy change of the lake water
• The entropy generated during the process
  T2 
Siron  m( s2  s1 )  mCav ln  
 T1 

 285 
Siron  (50) * (0.45) * ln    12.65kJ / K
 500 

Qout,iron  Qin,lake  mCav (T1  T2 )

Qin,lake  (50) * (0.45)(500  285)  4838kJ

Qlake  4838
Slake    16.97 kJ / K
Tlake 285
Assuming the lake and the block is a closed isolated
system

SGen  Stot  Ssystem  Slake

SGen  12.65  16.97  4.32kJ / K

OR applying the entropy balance to the extended
system

Sin - Sout + Sgen = Ssystem

Qk
 T  S gen  S system  S 2  S1
k
Qout 4838
SGen   S system   12.65  4.32 kJ / K
Tb 285
 Entropy Generation in Mixing
Neglecting the changes in kinetic and Air at 70 F
potential energies, determine the rate of
entropy generation during this process

steady-flow process
no work interactions
kinetic and potential energies are negligible

Apply the mass balance

Apply the heat balance

Find m2=22.7 lbm/min

Apply the entropy balance

Notice: there are 2 irreversible processes (mixing & heat transfer)

 Example: entropy generation
during heat transfer
• A frictionless piston–cylinder device contains a
saturated liquid–vapor mixture of water at 100C.
• During a constant-pressure process, 600 kJ of
heat is transferred to the surrounding air at 25C.
• As a result, part of the water vapor contained in
the cylinder condenses.
• Determine (a) the entropy change of the water
and (b) the total entropy generation during
this heat transfer process.
 No friction: process is internally reversible

Partial condensation: wet vapor at initial & final states

Both P & T remain constant at the saturation values

For the internally reversible system

For the extended system