Entropy

Chapter 6
Entropy Change
We need to define another important inequality that has
major consequences in thermodynamics is the Clausius
inequality.
This inequality is valid for all cycles, reversible or
irreversible.
The symbol (integral symbol with a circle in the middle) is
used to indicate that the integration is to be performed over
the entire cycle.
Entropy Change
Any heat transfer to or from a system can be considered to
consist of differential amounts of heat transfer.
Then the cyclic integral of dQ/T can be viewed as the sum
of all these differential amounts of heat transfer divided by
the temperature at the boundary.
Temperature of T
R
through a reversible cyclic
device. The cyclic device receives heat QR
from the reservoir and supplies heat Q
to the system whose temperature at that part of
the boundary is T. while producing work Wrev.
The system produces work Wsys as a
result of this heat transfer.
Entropy Change
Applying the energy balance to the combined system identified by
dashed lines yields
where WC is the total work of the combined system
(Wrev +Wsys) and dE
C
is the change in the total energy
of the combined system.

Considering that the cyclic device is a reversible one, we
have
Entropy Change
where the sign of Q is determined with respect to the system
(positive if to the system and negative if from the system) and
the sign of QR is determined with respect to the reversible
cyclic device.
We now let the system undergo a cycle while the cyclic device
undergoes an integral number of cycles. Then the preceding
relation becomes
Entropy Change
It looks like that the combined system is exchanging heat with a
single thermal energy reservoir while involving (producing or
consuming) work W
C
during a cycle.
On the basis of the KelvinPlanck statement of the second law,
which states that No system can produce a net amount of
work while operating in a cycle and exchanging heat with a
single thermal energy reservoir,
We reason that W
C
cannot be a work output, and thus it cannot
be a positive quantity. And Considering that T
R
is a positive
quantity
Entropy Change
Then it follows that W
C,int rev
=0 since it cannot be a
positive or negative quantity, and therefore
For internally reversible cycles. Thus, we conclude that the
equality in the Clausius inequality holds for totally or just
internally reversible cycles and the inequality for the
irreversible ones.
Entropy Change
That is, the cyclic integral of volume (or any
other property) is zero. Conversely,
a quantity whose cyclic integral is zero depends
on the state only and not the process path, and
thus it is a property. Therefore, the quantity
(Q/T )
int rev
must represent a property in the
differential form.
Clausius realized that he had discovered a new
thermodynamic
Entropy Change
This property is entropy. It is designated S and is defined as
Entropy is an extensive property of a system and sometimes is
referred to as total entropy.
Entropy per unit mass, designated s, is an intensive property
and has the unit (kJ /kg K.)
The term entropy is generally used to refer to both total entropy and
entropy per unit mass since the context usually clarifies which one
is meant.
Entropy Change
Notice:
That the entropy change of a system during an internally
reversible isothermal process can be positive or negative,
depending on the direction of heat transfer.
Heat transfer to a system increases the entropy of a system,
whereas heat transfer from a system decreases it. In fact, losing
heat is the only way the entropy of a system can be decreased.
Entropy Change
Ex: A pistoncylinder device contains a liquidvapor 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.
Entropy Balance for Closed
Systems
Change in the
amount of entropy
contained in the
system during some
time interval
Net amount of
entropy transferred
in across the
boundary during the
time interval
Amount of entropy
produced within the
system during the
time interval

=
2
1
1 2

b
T
Q
S S

=
b
T
Q
dS

+ =

j
j
j
T
Q
dT
dS
As a time rate
The only process that can occur are
those for which the entropy of the
isolated system increases
0 ] ] > = +
isol surr system
S S
Entropy Balance for Control
Volumes
cv
e
e e
i
i i
j
j
j
cv
s m s m
T
Q
dt
dS

+ + =

Rate of
entropy
change
Rates of
entropy
transfer
Rate of
entropy
production
For steady state

+ + =
j
cv
e
e e
i
i i
j
j
s m s m
T
Q

0
For 1 inlet 1 outlet
m T
Q
m
s s
s s m
T
Q
cv
j
j
j
cv
j
j
j

=
+ + =

1
) ( 0
1 2
2 1
Entropy Change

cycle
b
T
Q

2
1
1
2
cycle
C A
T
Q
T
Q

2
1
1
2
cycle
C B
T
Q
T
Q

As the cycles are
reversible,
cycle
=0

2
1
2
1 B A
T
Q
T
Q
This means that the qty (Q/T)
is the same for all internally
reversible processes
And that quantity is defined
as the change in entropy

=
2
1
int
1 2
rev
T
Q
S S

rev
T
Q
dS
int

=

Units
SI ->kJ /K
Eng->BTU/
0
R
Entropy Change
THE INCREASE OF ENTROPY PRINCIPLE
Consider a cycle that is made up of two processes: process 1-2,
which is arbitrary (reversible or irreversible), and process 2-1,
which is internally reversible. From the Clausius inequality,
Entropy Change
THE INCREASE OF ENTROPY PRINCIPLE
The second integral in the previous relation is recognized as the
entropy change S1 - S2. Therefore,
or
then
where the equality holds for an internally
reversible process and the inequality for an
irreversible process.
Entropy Change
THE INCREASE OF ENTROPY PRINCIPLE
The inequality sign in the preceding relations is a constant
reminder that the entropy change of a closed system during an
irreversible process is always greater than the entropy transfer.
That is, some entropy is generated or created during an
irreversible process, and this generation is due entirely to the
presence of irreversibilities.
The entropy generated during a process is called entropy
generation and is denoted by S
gen
.

Noting that the difference between the entropy change of a
closed system and the entropy transfer is equal to entropy
generation
Entropy Change
THE INCREASE OF ENTROPY PRINCIPLE
Note that the entropy generation S
gen
is always a positive quantity
or zero. Its value depends on the process, and thus it is not a
property of the system. Also, in the absence of any entropy
transfer, the entropy change of a system is equal to the entropy
generation. For an isolated system (or simply an adiabatic closed
system), the heat transfer is zero, and equation is reduced to
Entropy Change
THE INCREASE OF ENTROPY PRINCIPLE
This equation can be expressed as the entropy of an isolated
system during a process always increases or, in the limiting
case of a reversible process, remains constant. In other words,
it never decreases.

This is known as the INCREASE OF ENTROPY
PRINCIPLE.

Note that in the absence of any heat transfer, entropy change is
due to irreversibilities only, and their effect is always to
increase entropy.
Entropy Change
THE INCREASE OF ENTROPY PRINCIPLE
Entropy is an extensive property,
and thus the total entropy of a
system is equal to the sum of the
entropies of the parts of the
system. An isolated system may
consist of any number of
subsystems
Entropy Change
THE INCREASE OF ENTROPY PRINCIPLE
A system and its surroundings can be
viewed as the two subsystems of an
isolated system, and the entropy change
of this isolated system during a process
is the sum of the entropy changes of the
system and its surroundings, which is
equal to the entropy generation since an
isolated system involves no entropy
transfer. That is,
Reversible
Irreversible
Entropy Change
THE INCREASE OF ENTROPY PRINCIPLE
Processes can occur in a certain direction only, not in any direction. A process
must proceed in the direction that complies with the increase of entropy
principle, that is, S
gen
0. A process that violates this principle is impossible.

Entropy is a nonconserved property, and there is no such thing as the
conservation of entropy principle. Entropy is conserved during the idealized
reversible processes only and increases during all actual processes.

The performance of engineering systems is degraded by the presence of
irreversibilities, and entropy generation is a measure of the magnitudes
of the irreversibilities present during that process.
Entropy Change
Ex: A heat source at 800 K loses 2000 kJ of heat to a sink at
(a) 500 K and (b) 750 K. Determine which heat transfer
process is more irreversible.
Entropy from tables
Entropy is listed in the tables like all other
properties we talked about (u, h etc)
The tables give us the specific entropy
s in
the super heated tables is directly read out of
the tables ( or interpolated)
saturation zone is given as s=s
f
+ x (s
g
s
f
)
liquid zone is approximated as s
f
(T)

Entropy from tables
Entropy
ISENTROPIC PROCESSES

We mentioned earlier that the entropy of a fixed mass can be changed
by (1) heat transfer and (2) irreversibilities.
The entropy of a fixed mass does not change during a process that is
internally reversible and adiabatic
A process during which the entropy remains constant is called an
isentropic process. The term isentropic process is customarily used in
thermodynamics to imply an internally reversible, adiabatic process.


It should be recognized that a reversible adiabatic process is
necessarily isentropic (s
2
=s
1
), but an isentropic process is not
necessarily a reversible adiabatic process.

Entropy
PROPERTY DIAGRAMS INVOLVING ENTROPY
Property diagrams serve as great visual aids in the
thermodynamic analysis of processes. We have used P-v and
T-v diagrams extensively in previous chapters in conjunction
with the first law of thermodynamics.
The T dS equations
pdV dU TdS + =
rev rev
W dU Q
int int
) ( ) ( + = From 1
st
law
TdS Q
pdV W
rev
rev
=
=
int
int
) (
) (

From
previous slide
Vdp pdV dU pV d dU dH + + = + = ) (
Vdp dH pdV dU = +
Vdp dH TdS =
vdp dh Tds =
pdv du Tds + =
T
h h
f g
f g
s s

=
For a phase change ( only between
the saturation zones)
(1/m)
(1/m)
In the saturation
zone p is const, i.e.
dp=0
Entropy Change
Incompressible substances

=
= + =
2
1
) (
) ( ) (
1 2
T
T
dT
T
T c
s s
T
dT T c
T
pdv
T
dT T c
ds
1
2
1 2
ln
T
T
c s s =
If c is constant
Ideal Gas
RT pv
dT T c dh
dT T c du
p
v
=
=
=
) (
) (
+Tds equations

p
dp
R
T
dT
T c ds
v
dv
R
T
dT
T c ds
p
v
=
+ =
) (
) (
Entropy Change
1
2
1 1 2 2
1
2
1 1 2 2
ln ) ( ) , ( ) , (
ln ) ( ) , ( ) , (
2
1
2
1
p
p
R
T
dT
T c p T s p T s
v
v
R
T
dT
T c v T s v T s
T
T
p
T
T
v
=
+ =

p
dp
R
T
dT
T c ds
v
dv
R
T
dT
T c ds
p
v
=
+ =
) (
) (
Integrating
R is const,
c is not const
Introduce
( )

=
T
T
p o
dT
T
T c
T s
'
) (
where T is any reference temp
( ) ( ) ( )

=
1 2 2
1
' '
T
T
p
T
T
p
T
T
p
dT
T
T c
dT
T
T c
dT
T
T c
( ) ( )
1 2
T s T s
o o
=
( ) ( )
( ) ( )
1
2
1 2 1 1 2 2
1
2
1 2 1 1 2 2
ln ) , ( ) , (
ln ) , ( ) , (
p
p
R T s T s p T s p T s
v
v
R T s T s v T s v T s
o o
o o
=
+ =
1
2
1
2
1 1 2 2
1
2
1
2
1 1 2 2
ln ln ) , ( ) , (
ln ln ) , ( ) , (
p
p
R
T
T
c p T s p T s
v
v
R
T
T
c v T s v T s
p
v
=
+ =
C is
const
Entropy Change
Internally Reversible Process
rev
T
Q
dS
int

=

( ) TdS Q
rev
=
int

=
2
1
int
TdS Q
rev
Carnot Cycle Application
If Q=0 then dS=0
i.e if an reversible process is
an adiabatic process it is also
an isentropic process meaning
it is a const entropy process.
Isentropic Process
Any process in which the entropy at the two
end states is the same or S
1
=S
2

( ) ( ) 0 ln
1
2
1 2
=
p
p
R T s T s
o o
( ) ( )
1
2
1 2 1 1 2 2
ln ) , ( ) , (
p
p
R T s T s p T s p T s
o o
=
( ) ( )

=
R
T s T s
p p
o o
1 2
1 2
exp
( )
( ) R T s
R T s
p
p
/ ) ( exp
/ ) ( exp
1
0
2
0
1
2
=
Isentropic for Air
ONLY, the expression
exp(s
o
(T
2
)/R)
is given in the book as in
table A-22, under the
name of Relative Pressure
P
r
(not Reduced Pressure)
( ) R T s p
r
/ ) ( exp
2
0
2
=
1
2
1
2
r
r
p
p
p
p
=
1
2
1
2
r
r
v
v
v
v
=
Using
pv=RT
v
ri
=(RT
i
/p
r
(T
i
))
Ideal Gas

=
k
k
p
p
T
T
1
1
2
1
2
( ) 1
2
1
1
2

=
k
v
v
T
T
k
v
v
p
p

=
2
1
1
2
R c c
k
c
c
v p
v
p
=
=
1 1
=

=
k
R
c
k
kR
c
v p
Isentropic Efficiencies
For a well insulated turbine, we know
that work done, W is
s s
a
h h
h h
W
W
2 1
2 1

= =
( )

+ + =
e i
e i
e i
z z g
V V
h h m W Q
2
0
2 2

e i
h h
m
W
=

2 1
h h
m
W
a
=

s
s
h h
m
W
2 1
=

The actual work done in the

process shown here is
The isentropic work done in the
process shown here is
The isentropic
efficiency is defined as
Turbines
Isentropic Efficiencies
Nozzle
( )
( )
s
nozzle
V
V
2 /
2 /
2
2
2
2
=
The nozzle isentropic efficiency is
defined as the ratio of actual exit
Kinetic Energy to the exit Kinetic
Energy for an isentropic expansion
Pump/Compressor
1 2
1 2
h h
h h
s
c

=
It is defined as the ratio of work needed
for an isentropic compression to the
work required in the actual process
Note that the ratio
is opposite to that
for a turbine
Isentropic Efficiencies
Example: 6.147
Known:
c
=80%,
t
=90%,
=5.8kg/s m
State Pressure Temperature
1 1 bar 300 K
2 10 bar -------
3 10 bar 1400 K
4 1 bar ------
Find: (a) Power required by the Compressor,
(b) Power generated by the turbine, and
(c) Net power output of the plant
Reversible Flow Processes
cv
cv
s s m
T
Q

+ + = ) ( 0
2 1
Reversible
) (
1 2
s s m
T
Q
cv
=

2
1
int
Tds
m
Q
rev
cv

( ) ( )
2 1
2
2
2
1
2 1
2
z z g
V V
h h
m
Q
m
W
j
cv
+

+ + =

( ) ( )
2 1
2
2
2
1
2 1
2
1
2
z z g
V V
h h Tds
m
W
cv
+

+ + =

=
=
2
1
1 2
2
1
) ( vdp h h Tds
vdp dh Tds

=
2
1
vdp
m
W
cv

Const v
) (
1 2
p p v
m
W
cv
=

Concludes that less work is required to pump

water (low v) than steam(higher v) between
the same pressures
Thats the reason for condensing the water in
a steam power plant
Polytropic Process (pv
n
=const)
( ) 1
1
1 1 2 2

= n v p v p
n
n
m
W
cv

( ) 1 / ln
1 2 1 1
= = n p p v p
m
W
cv

WHAT IS ENTROPY?
It is clear from the previous discussion that entropy is a
useful property and serves as a valuable tool in the second-
law analysis of engineering devices.
But this does not mean that we know and understand
entropy well.
Because we do not. In fact, we cannot even give an
adequate answer to the question.
Entropy can be viewed as a measure of molecular
disorder, or molecular randomness.
WHAT IS ENTROPY?
As a system becomes more disordered, the positions of the
molecules become less predictable and the entropy
increases.
Thus, it is not surprising that the
entropy of a substance is lowest in
the solid phase and highest in the
gas phase (Associated with this
molecular chaos is a high value of
entropy.)
WHAT IS ENTROPY?
When viewed microscopically (from a statistical thermodynamics
point of view), an isolated system that appears to be at a state of
equilibrium may exhibit a high level of activity because of the
continual motion of the molecules.

To each state of macroscopic equilibrium there corresponds a large
number of possible microscopic states or molecular
configurations.

The entropy of a system is related to the total number of possible
microscopic states of that system, called thermodynamic
probability p, by the Boltzmann Relation.
WHAT IS ENTROPY?
Boltzmann Relation.
where k = 1.3806 x10
-23
J /K is the Boltzmann
constant.
From a microscopic point of view, the entropy of a system
increases whenever the molecular randomness or uncertainty
(molecular probability) of a system increases.
Thus, entropy is a measure of molecular disorder, and the
molecular disorder of an isolated system increases anytime it
undergoes a process
End of Chapter 6