CHAPTER 6

ENTROPY
 ENTROPY
It is difficult to give a physical description of entropy.
Entropy is best understood and appriciated by studying its uses in
commonly encountered engineering processes.

CLASIUS INEQUALITY
Q
The cyclic integral of Q/T is always less than or equal to zero : 0
T
Q
T int.rev. 0 (for internally reversible cycles)
Q
T 0 Q
T 0 (for irreversible cycles)

This inequality is valid for all thermodynamic cycles (rever. & irrever.)
ENTROPY
Systems are charecterezed by their properties : P, T, v, u, h
Cyclic integral of any property is always zero. The net change in a property
CONCLUSION
during a cycle is always zero.
For example : Entropy (s) is a property of systems.

P
T dV V
cycle 0

v
u
h
A quantity whose cyclic integral is zero depends on the state only and not
on the process path. Therefore thats quantity is a property.
For an internally reverible cycle : Q
T

int. rev.
0

Therefore (Q/T)int. rev must be a property. This quantitiy is called entropy.

 DEFINITION OF ENTROPY

Q
dS
T int.rev. This is not the definition of entropy.
2
Q It is definition of entropy change.
S S 2 S1
1
T int.rev.

NOTE 1 : In these equations, T is temperature of the system boundary.

NOTE 2 : Entropy is a property, and like all

other properties, it has fixed values at fixed states.
Therefore, entropy change dS (or S) between
two specified states is the same for both reversible
and irreversible paths between the states.
 DEFINITION OF ENTROPY
NOTE 3 : Integral of Q/T will give us S only if the integration is carried
out along an internally reversible path between the two states. Integral of
Q/T along an irreversible path will not give us S. Therefore, even for
irreversible processes, S should be determined by calculating integral along
some convenient imaginary internally reversible path between the specified
states.
2
Q
NOTE 4 : To be able to calculate S using the integral we need a
1
relation between Q and T. T int.rev.

This relation is often not available. It is available only few special

cases.
Therefore, for the majority of the ceses, we use tabulated data for
entropy.
SPECIAL CASE : INT. REV. ISOTHERMAL HEAT TRANSFER PROCESS

2
Q
2
Q 1
2
Q
S
1
T

int.rev.

1
T0

T0 Q
1
int.rev.
T0
int.rev.
THE INCREASE OF ENTROPY PRINCIPLE
Consider a cycle that is made up 2 processes.
If we write Clasius inequality for this cycle :
Q
T 0
2 1
Q Q Q
T 1 T 2 T 0
int.rev.
2 2
Q Q
1 T 1 T
0
int.rev.

S S 2 S1 (Definition of entropy)
2
Q
1 T S 2 S1 0 2
Q
S 2 S1 (for irrev. processes)
2 T
Q 1
S 2 S1 2
T Q
1
S 2 S1 (for rev. processes)
1
T
 2
Q
S 2 S1
1
T

2 CONCLUSION
Q
S 2 S1 Entropy change of a closed system
Entropy
1
T change of aansystem
during irreversible process is
Entropy change Entropy transfer always greater than the entropy
2
of system, with heat Qwith heat.
transfer
Ssys S sys S 2 S1 S gen
That T
1 means ; Some entropy is
Inequality generated (Sgen) during an
Equality irreversible process.
2
Q
S 2 S1 S gen
1
T
To convert inequality into equality
ENTROPY CHANGE OF A SYSTEM :
2 + - 0
Q
S sys S 2 S1 S gen
+ 1
T
Entropy transfer Entropy generation within
with heat transfer the system boundary due to
internal irreversibilities
Heat transfer
to system + - 0 + + 0

Heat transfer Inter.

from system
+ - 0 rev.

Adiabatic Entropy of a system can Inter.

irrev.
increase (+), decrease (-)
or stay constant (0)
 ENTROPY CHANGE OF A SYSTEM :
2
Q
S sys S gen
1
T
2 0
Q S sys S gen
For an adiabatic process : S sys S gen
1
T
2 2
Q 0 Q
For an int. reversible process : S sys S gen S sys
1
T 1
T
2 0
For an int. reversible and Q 0
adiabatic process : S sys S gen S sys 0
T
(isentropic process) 1

2 2
For an int. reversible and Q 0 Q Q
isothermal process : S sys 1 T S gen S sys
1
T

T0
Example 6.1 : A piston-cylinder device contains a liquid-vapor mixture
of water at 300 K. During a constant pressure process, 750 kJ of heat is
transferred to the water. As a result, part of the liquid in the cylinder
vaporizes. Determine the entropy change of the water during this process.

Process : internally reversible + isothermal

Q 750
S sys 2.5 kJ/K
Tsys 300
FOR AN ISOLATED SYSTEM :
A system and its surroundings form an
isolated system. For an isolated system :
E M
2
Q
0
ST
S isolated sys S 2 S1 SY
S isolated sys 0
1
T
E D
T
O LA
Entropy of an isolated systemI during a?
S
N ? ? of a
process INCREASE OF
always increases or, in the
Aremains??
limiting case ENTROPY
S
reversible process,
I
constant. PRINCIPLE

E
SOR S O
E R
I V 2
Q
0
N
U sys S tot S sys S surr 1 T S gen
S isolated

S isolated sys S gen S isolated sys 0

+ 0
INCREASE OF ENTROPY PRINCIPLE
2 0
Q
S isolated sys S tot S sys S surr S gen S gen 0
1
T
+ - 0 + - 0
+ 0
Entropy of a system can
increase, decrease or stay
constant.
However, Stot=Sgen increases
or in the limiting case, it is
zero.

>0 Irreversible process

Stot= Sgen =0 Reversible process
<0 Impossible process
 CHARECTERISTICS OF ENTROPY
1. Processes can occur if it obeys the increase of entropy principle,
that is Stot=Sgen 0
2. Entropy is a nonconserved property, and there is no principle as
conservation of entropy. Entropy is conserved during reversible
processes (impossible in real life) only and increases during all
actual processes.
3. Performance of engineering systems is degarded by the presence of
irreversibilities.
Entropy generation is a measure of the magnitudes of the
irreversibilities present during that process.
 INTERNALLY & EXTERNALLY REVERSIBLE PROCESSES

Internally Reversible Process Externally Reversible Process

No
No irreversibilities
irreversibilities
(heat transfer)
(friction)
system
(non-quasi- system
boundary equilibrium boundary
expan. & comp.)

Totally Reversible Process

(internally + externally) 50 oC 50 oC 50 oC

Q Q
No No
60 oC 50.0001 oC
irreversibilities irrever.
system
boundary Externally Externally Externally
rev. irrev. rev.
 T Carnot Cycle
Int.irrev. Int.rev. Tot. 2
1
rev.

Q
Ext. rev. Ext. rev.

Q
2
0 0
Q 2
Q 0 4 3
S sys T
S gen S gen S sys T
S gen 0 Ex
1 1 a m S
pl
e
Stot>0 Stot=0 2 3 : (adiabatic)
Int. rev + ext. rev.

Int.rev. Int.rev. Ssys=0 Stot=0

Tot.
Q

Q
50 C
o 60 oC rev. 50 oC 50.001 oC
1 2 : (isothermal)
Ext. irrev. Ext. rev.
mple Int. rev +2 ext. rev.
a Q
Ex
S sys
2
Q 0 2
Q
2
Q 0 2
Q T
S sys
1
T
S gen T
S sys T
S gen
T
1
Stot=0
1 1 1

Stot>0 Stot=0 Ssys = 2 kJ/K

2 Ssurr= -2 kJ/K
Q
(IF THERE IS HEAT TRANSFER S sys AND Ssys 0) Stot = 2-2 = 0 kJ/K
1
T
 Example 6-2 : A thermal energy source at 800 K
loses 2000 kJ of heat to a sink at;
a)500 K
b)750 K
Determine which heat transfer process is more
irrevesible.
2 0 0
Q
2
Q
Ssource S gen , source Ssink S gen, sink
1
T 1
T
Tsource=Constant Tsink=Constant
Qsource Qsink
Ssource Ssink Stot Ssource Ssink
Tsource Tsink
a)
2000 2000
2,5 kJ/K 4,0 kJ/K 2,5 4,0 1,5 kJ/K
800 500

b)
2000 2000
2,5 kJ/K 2,7 kJ/K 2,5 2,7 0,2 kJ/K
800 750

Stotal,b < Stotal,a Process b is less irreversible

ENTROPY CHANGE OF PURE SUBSTANCES
2 2 2 2
It is not practical to use equations S du Pdv S dh vdP
1
T 1 T 1
T 1 T

Therefore, we use : S=m(s2-s1 )

s1 and s2 can be read from property

tables.

Special Case
Isentropic processes of pure substances

Isentropc process=Adiabatic+Int. Rev.

S=m(s2-s1 )=0 and s1=s2

Example 6-3 : A rigid tank contains 5 kg of
refrigerant-134a initially at 20 0C and 140 kPa. The
refrigerant is now cooled while being stirrred until its
pressure drops to 100 kPa. Determine the entropy
change of the refrigerant during this process.

S=m(s2-s1)
1 2
P1=140 kPa s =1.0532 kJ/(kg.K) P2=100 kPa vf=0.0007258 m3/kg
1
T1=20 C
0
v1=0.1652 m3/kg v2=v1=0.1652 m3/kg vg=0.1917 m3/kg
vf<v2<vg Sat. mixture
v2 v f 0.1652 0.0007258
x2 0.861
v fg 0.1917 0.0007258
s2 = sf+x2sfg = 0.0678+0.861(0.9395-0.0678)
= 0.8183 kJ/(kg.K)
S=m(s2-s1) = 5(0.8183-1.0532) = -1.174 kJ/K
 ISENTROPIC PROCESSES

Isentropic Process : Ssys=0 or S2=S1

Note
An int. rev. and adiabatic process is necessarily isentropic.
But, an isentropic process is not necessarily int. rev. and adiabatic.

int. rev.
+ Ssys=0 Ssys=0 int. rev.
adiabatic (isentropic) (isentropic) +
adiabatic
2 0 2
Q -A +A
Q 0
S sys S gen S sys 0 S sys S gen S sys 0
T 1
T
1

The term isentropic process is used in thermodynamics for

internally reversible + adiabatic processes.
Example 6-5 : Steam
enters an adiabatic turbine at
5 MPa and 450 oC and leaves
at a pressure of 1.4 MPa.
Determine the work output
of the turbine per unit mass
off steam flowing through the
turbine if the process is
reversible and the changes in
kinetic and potential energies
are negligible.
0
1 Law : q w = h -h
st
wout = h1-h2
2 1

1 2
P1=5 MPa h1=3316.2 kJ/kg P2=1.4 MPa h2=2966.6 kJ/kg
T1=450 C s1=6.8186 kJ/kg.K s2=s1

wout=h1-h2=3316.2-2966.6
wout=349.6 kJ/kg
 WHAT IS ENTROPY ?
Entropy is a measure of molecular disorder,
or molecular randomness. As a system
becomes more disordered, the positions of the
molecules become less predictable and the
entropy increases.

Even in the solid phase, the molecules of a substance continually

oscillate, creating an uncertainty about their position. These oscillations
fade as T . Molecules become completely motionless at T=0 K. This
represent a molecular order (no molecular disorder).

Third Law of Thermodynamics

Entropy of a pure substance at T=0 K is zero.
WHAT IS ENTROPY ?

LOW ENTROPY

HIGH ENTROPY
 Disorder
Molecules in the gas phase possess a
considerable amount of kinetic energy.
But they cannot rotate a paddle wheel ?
inserted into container (no work
production). Why ?

These men apply a force on the load.

But they cannot move the load. Why ?

Order
Shaft is rotating.
The weight can be lifted up. Why ?
 QUANTITY & QUALITY OF ENERGY
Example 1 : Molecules in the gas
phase possess a considerable amount
of kinetic energy.
But they cannot rotate a paddle wheel
inserted into container (no work
production). Why ?
Wsh= Ugas (1st Law)
Wsh Ugas Tgas Disorder Quality
Example 2 : Heat flows from a high
temp. body to a low temp. body.
But the same energy cannot be
transferred completely back to high
temp. body.
Qhb=Qcb (1st Law)
Q(-) Uhb Thb Disorderhb
Quality
Q(+) Ucb Tcb Disordercb
ENTROPY BALANCE
Energy Balance :
Total Total Change in the
energy - energy = total energy of Ein-Eout= Esys
entering leaving the system
Net energy transfer
Entropy Balance :
Total Total Total Change in the
entropy - entropy
+ entropy
= total entropy of Sin-Sout+Sgen= Ssys
entering leaving generated the system
Net entropy transfer

Energy Transfer (Ein & Eout) : Entropy Transfer (Sin & Sout) :
Heat transfer Heat transfer 2
Q Q
Work transfer Work transfer S heat k
T Tk
Mass transfer Mass transfer 1

Swork=0

Smass=ms
Closed Sin-Sout+Sgen= Ssys
Systems
2
Q For closed systems
1 T S gen S sys previously we obtained :
2
Qk Q
T S gen S sys S sys
1
T
S gen
k

For system and Surroundings :

S tot S sys S surr

Qk Qsurr
T S sys
gen T
k surr
Open Sin-Sout + Sgen= Ssys
Systems
2
Q
1 T mi si me se S gen S sys ( S 2 S1 ) cv
Entropy transfer Entropy transfer
by heat by mass
Qk
T mi si me se S gen S sys ( S 2 S1 ) cv
k
.
Qk . . . .
T mi si me se S gen S sys
k

For steady-flow systems :

.
Qk . . .
T mi si me se S gen 0
k
For steady-flow & single-stream systems :
.
Qk . .
T m si se S gen 0
k
Example 6-23 : A frictionless piston-cylinder device, shown in
figure 6-15, contain a saturated mixture of water at 100 C. During a
constant-pressure process, 600 kJ of heat is transfered to the
surrounding air which is at 25 C.
As a result, part of the water vapor contained in the piston-cylinder
device condences.
Determine,
a) The entropy change of water
b) The entropy change of surrounding air
during this proses
c) Whether this proses is reversible,
irreversible, or impossible.
 1 2
Sat. mixt. Sat. mixt.
T1=100 C T2=100 C
P2= P1

a) Swater Ssys m( s2 s1 )
Can not be read from tables.
Not given,
Because, x can not be
can not be calculated with
calculated.
the data given

Q
Swater S gen, sys
T
= 0 (Frictionless piston= Int. Rev.)
Proses is isotermal (T1=T2) :
Qsys 600
Ssys 1,61 kJ / K
Tsys 373
b) Surrounding is at constant temperature of 25 C
Qsur 600
Ssur 2,01 kJ / K
Tsur 298
c)
Stot Ssys Ssur
Stot 1,61 2,01 0,4 kJ / K
Stot 0 Processs is irreversible