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
0
The cyclic integral of Q/T is always less than or equal to zero :
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.

dV V

cycle

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

int. rev.

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

DEFINITION OF ENTROPY

DEFINITION OF ENTROPY
Q
dS

int.rev.

This is not the definition of entropy.

It is definition of entropy change.

Q
S S 2 S1

T
1

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

T
1
relation between Q and T.

we need a
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
S

T
1

T0
1
2

int.rev.

int.rev.

T0

Q
1

int.rev.

T0

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
2

int.rev.

Q
Q

1 T 1 T
2

0
0
int.rev.

S S 2 S1 (Definition of entropy)

Q
1 T S 2 S1 0
2

Q
S 2 S1
T
1

Q
S 2 S1
T
1

(for irrev. processes)

Q
T
1

S 2 S1

(for rev. processes)

Q
S 2 S1

T
1

CONCLUSION

Q
S 2 S1
Entropy change of a closed system

T
Entropy
change
of aansystem
1
during
irreversible process is
always greater than the entropy
Entropy change Entropy transfer
2
of system, with heat
transfer
Qwith heat.

S sys S 2 S1

Ssys

Inequality
Equality

S gen

T
That
1 means ; Some entropy is
generated (Sgen) during an
irreversible process.

Q
S 2 S1
S gen
T
1

To convert inequality into equality

ENTROPY CHANGE OF A SYSTEM :

+ - 0
2

S sys

Q
S 2 S1
S gen
T
1
+
Entropy transfer
with heat transfer

Heat transfer
to system

Heat transfer
from system

Adiabatic

+
-

Entropy generation within

the system boundary due to
internal irreversibilities

Entropy of a system can

increase (+), decrease (-)
or stay constant (0)

0
Inter.
rev.
Inter.
irrev.

ENTROPY CHANGE OF A SYSTEM :

2

S sys

S gen
T
1
0
Q

S gen
T
1
2

For an adiabatic process : S sys

Q
0
S gen
T
1
0
2
Q
0

S gen
T
1

S sys S gen
2

For an int. reversible process : S sys

S sys

For an int. reversible and

adiabatic process : S sys
(isentropic process)

S sys 0

For an int. reversible and

isothermal process : S sys

0
Q
1 T S gen

S sys

Q
T

Q Q

T
T0
1

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

S sys

Q
750

2.5 kJ/K
Tsys 300

FOR AN ISOLATED SYSTEM :

A system and its surroundings form an
isolated system. For an isolated system :
2

Q
S isolated sys S 2 S1
T
1
S isolated sys 0

D
E
T
LA

M
E
T
S
SY

O
S
Entropy of an isolated systemI during a?
process
? of a
always increases or, in the
limiting
case
N
?
Aremains??
reversible process,
constant.
S
I
O
E
SOR
S
R
E
0
2
V
Q
I
N
S isolated
U sys S tot S sys S surr 1 T S gen
S isolated sys S gen
+ 0

S isolated sys 0

INCREASE OF
ENTROPY
PRINCIPLE

INCREASE OF ENTROPY PRINCIPLE

2

S isolated sys S tot S sys S surr

+ - 0

+ - 0

S gen S gen 0
T
1

+ 0
Entropy of a system can
increase, decrease or stay
constant.
However, Stot=Sgen increases
or in the limiting case, it is
zero.

Stot= Sgen

>0
=0
<0

Irreversible process
Reversible process
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
irreversibilities

No
irreversibilities

(heat transfer)

(friction)
(non-quasisystem
equilibrium
boundary
expan. & comp.)

system
boundary

Totally Reversible Process

(internally + externally)
No
irreversibilities
system
boundary

50 oC

No
irrever.
Externally
rev.

50 oC

50 oC

60 oC

50.0001 oC

Externally
irrev.

Externally
rev.

Ext. rev.

S sys

50 oC

60 oC

Int.rev.

Tot.
rev.

50 oC

Ext. irrev.
2

0
Q
S gen
T

Stot>0

Ex
a

Stot=0

Stot>0
Int.rev.

0
0
Q
S gen 0
T

S sys

50.001 oC

Ext. rev.
2

Q
T

S sys

0
Q
S gen
T

Q
T

(IF THERE IS HEAT TRANSFER S sys

m
pl
e

2 3 : (adiabatic)
Int. rev + ext. rev.

Ssys=0

Stot=0

Ssys = 0 kJ/K
Ssurr= 0 kJ/K
Stot = 0-0 = 0 kJ/K

1 2 : (isothermal)
ple Int. rev +2 ext. rev.
m
a
Q
Ex
S sys
T
1

Stot=0
2

Ext. rev.

Carnot Cycle

Int.rev.

S sys

Tot.
rev.

Int.irrev.

0
Q
S gen S gen
T

Q
AND Ssys0)
T

Stot=0

Ssys = 2 kJ/K
Ssurr= -2 kJ/K
Stot = 2-2 = 0 kJ/K

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

2
0
0
Q
Q
Ssource
S gen , source Ssink
S gen, sink
T
T

1
1

Tsource=Constant
Ssource

a)

Qsource

Tsource

2000
2,5 kJ/K
800

b)

2000
2,5 kJ/K
800

Tsink=Constant
Ssink

Qsink
Tsink

Stot Ssource Ssink

2000
4,0 kJ/K
500

2,5 4,0 1,5 kJ/K

2000
2,7 kJ/K
750

2,5 2,7 0,2 kJ/K

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

ENTROPY CHANGE OF PURE SUBSTANCES

2

It is not practical to use equations S du Pdv S dh vdP

T 1 T
T 1 T
1
1
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

P1=140 kPa s =1.0532 kJ/(kg.K)

1
0
T1=20 C
v1=0.1652 m3/kg

P2=100 kPa
vf=0.0007258 m3/kg
v2=v1=0.1652 m3/kg vg=0.1917 m3/kg
vf<v2<vg Sat. mixture

x2

v2 v f
v fg

0.1652 0.0007258
0.861
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
+
adiabatic
(isentropic)

Ssys=0 int. rev.

+
(isentropic)
adiabatic

2
-A +A
0

Q
Q
0
S gen S sys 0

S gen S sys 0 S sys

T
T
1
1
2

S sys

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
2
1
st

1
P1=5 MPa
T1=450 C

wout = h1-h2
2

h1=3316.2 kJ/kg
s1=6.8186 kJ/kg.K

P2=1.4 MPa
s2=s1

wout=h1-h2=3316.2-2966.6
wout=349.6 kJ/kg

h2=2966.6 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.
But the weight can be lifted up. Why ?

EXAMPLE 2

EXAMPLE 1

QUANTITY & QUALITY OF ENERGY

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)

WshUgas Tgas Disorder Quality
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. Why ?

Qhb=Qcb
(1st Law)
Q(-) Uhb Thb Disorderhb
Q(+) Ucb Tcb Disordercb

Quality

ENTROPY BALANCE
Energy Balance :
Total
energy
entering

Total
energy
leaving

Change in the
total energy of
the system

Ein-Eout= Esys
Net energy transfer

Entropy Balance :
Total
entropy
entering

Total
entropy
leaving

Total
entropy
generated

Energy Transfer (Ein & Eout) :

Heat transfer
Work transfer
Mass transfer

Change in the
total entropy of
the system

Sin-Sout+Sgen= Ssys
Net entropy transfer

Entropy Transfer (Sin & Sout) :

Heat transfer
2
Q
Q
Work transfer
S heat
k
T
Tk
1
Mass transfer

Swork=0
Smass=ms

Closed
Systems

Sin-Sout+Sgen= Ssys
2

Q
1 T S gen S sys
Qk
T S gen S sys
k

For system and Surroundings :

S tot S sys S surr

Qk
T S sys
gen
k

Qsurr
T
surr

For closed systems

previously we obtained :
2

Q
S gen
T
1

S sys

Open
Systems

Sin-Sout + Sgen= Ssys

2

Q
1 T mi si me se S gen S sys ( S 2 S1 ) cv
Entropy transfer
by heat

Entropy transfer
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 contains

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 condenses. 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.

a) Swater = Ssys = m(s2-s1)

Not given,
can not be calculated
with the data given

Can not be read from tables.

Because, x can not be
calculated.

1
Sat. mixt.
T1=100 C

2
Sat. mixt.
T2=100 C
P2 = P 1

0 (Frictionless cylinder = Int. Rev.)

Q
Swater
S gen , sys
T

Qsys 600

S
sys

1 ,61 kJ/K
Proses is isotermal (T1=T2)
Tsys
373
Qsur 600

S
sur

2 ,01 kJ/K
b) Surrounding is at constant temperature of 25 C
Tsur 298

c) Stot = Ssys + Ssur = -1.61 + 2.01 = 0.4 kJ/K

Stot > 0 Process is irreversible