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 TR through a reversible cyclic
device. The cyclic device receives heat δQR from
the reservoir and supplies heat δQ
to the system whose temperature at that part of the
boundary is T. while producing work δWrev.
The system produces work δWsys as a result of
this heat transfer.
 Entropy Change
Applying the energy balance to the combined system identified by
dashed lines yields

where δWC is the total work of the combined system

(δWrev + δWsys) and dEC 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 δQ is determined with respect to the system
(positive if to the system and negative if from the system) and
the sign of δQR 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 WC during a cycle.
• On the basis of the Kelvin–Planck 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 WC cannot be a work output, and thus it cannot
be a positive quantity. And Considering that TR 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 (δQ/T )int rev must represent a

property in the differential form.

“Clausius realized that he had discovered a new

thermodynamic Property”.
 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
Notice:

The integral of dQ/T along an irreversible path is not a

property, and in general, different values will be obtained
when the integration is carried out along different irreversible
paths. Therefore, even for irreversible processes, the entropy
change should be determined by carrying out this integration
along some convenient imaginary internally reversible path
between the specified states.
 Entropy Change
Ex: 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.
 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

or

The second integral in the previous relation is recognized as

the entropy change S1 - S2. Therefore,

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 Sgen.

“Noting that the difference between the entropy change of a

closed system and the entropy transfer is equal to entropy
generation”
 Entropy Balance for Closed
Systems
Change in the Net amount of Amount of entropy
amount of entropy entropy transferred produced within the
contained in the in across the system during the
system during some boundary during the time interval
time interval time interval

 Q 
2
S 2  S1   
1
 T b
 Q  dS Q j
dS        As a time rate
 T b dT j Tj

The only process that can occur are

those for which the entropy of the
S ]system  S ]surr  isol  0
isolated system increases
 Entropy Balance for Control
Volumes
dS cv Q j
   m i si   m s e e   cv
dt j Tj i e

Rate of
Rate of Rates of entropy
entropy entropy production
change transfer

Q j
For steady state 0    m i si   m s e e   cv
j Tj i e

Q j
0   m ( s1  s2 )   cv
j Tj
For 1 inlet 1 outlet
1  Q j   cv
s2  s1   
m  j T j  m

 Entropy Change
Units
 Q 
 T  b   cycle SI -> kJ/K
2
 Q 
1
 Q  Eng-> BTU/0R

1
      cycle
T  A 2  T C
2 1
As the cycles are
 Q   Q  reversible, σcycle = 0

1

 T

 B
 
2

 T
   cycle
C

2 2
This means that the qty (δQ/T)
 Q   Q  is the same for all internally
    
1
T A 1  T B reversible processes

 Q 
2
And that quantity is defined  Q 
S 2  S1   dS  
as the change in entropy 1
T  int
rev  T  int
rev
 Entropy Change
THE INCREASE OF ENTROPY PRINCIPLE

Note that the entropy generation Sgen 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, Sgen ≥ 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=sf + x (sg – sf)
– liquid zone is approximated as sf (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

(s2 =s1), 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
(Q) int dU  (W ) int From 1st law
rev rev

(W ) int  pdV

rev
TdS dU  pdV
(Q) int TdS
From previous
rev
slide (1/m)

dH dU  d ( pV ) dU  pdV  Vdp

Tds du  pdv
dU  pdV dH  Vdp Tds dh  vdp
TdS dH  Vdp (1/m)

hg  h f For a phase change ( only between

In the saturation
zone p is const, i.e.
sg  s f  T the saturation zones)
dp=0
 Entropy Change
• Incompressible substances
c(T )dT pdv c(T )dT
ds   
T T T
T2 c (T ) T2
s2  s1  dT s 2  s1 c ln If c is constant
T1 T T1
• Ideal Gas
du cv (T )dT dT dv
ds cv (T ) R
dh c p (T )dT T v
+Tds equations 
dT dp
ds c p (T )  R
pv RT T p
 Entropy Change
dT dv Integrating T2 dT v
ds cv (T ) R s(T2 , v2 )  s(T1 , v1 )  cv (T )  R ln 2
T v R is const,
T1 T v1
dT dp T2 dT p
ds c p (T )  R s(T2 , p2 )  s(T1 , p1 )  c p (T )  R ln 2
T p c is not const T1 T p1

T c p T 
Introduce s o (T )  dT where T’ is any reference temp
T' T
T2 c p T  T2 c p T  T1 c p T 
 dT  dT   dT s o T2  s o T1 
T1 T T' T T' T

v2
s (T2 , v2 )  s (T1 , v1 ) s o T2  s o T1  R ln
v1 T2 v
s (T2 , v2 )  s (T1 , v1 ) cv ln  R ln 2
p2 T1 v1
s (T2 , p2 )  s (T1 , p1 ) s o T2  s o T1  R ln
p1 C is T2 p
const s (T2 , p2 )  s (T1 , p1 ) c p ln  R ln 2
T1 p1
 Entropy Change
Internally Reversible Process

 Q 
dS  
 T  int
rev
2
 Q int
rev
TdS Qint TdS
1
rev

Carnot Cycle Application

If δQ=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
Ideal Gas
Any process in which the entropy at the two Isentropic for Air
end states is the same or S1=S2 ONLY, the expression
p2 exp(so(T2)/R)
s (T2 , p2 )  s (T1 , p1 ) s o T2  s o T1  R ln
p1
 s o T2  s o T1 
is given in the book as in
p
s T2  s T1  R ln 2 0
o o p2  p1 exp
R
 table A-22, under the
p1  
name of Relative Pressure

p2 exp s 0 (T2 ) / R

 Pr (not Reduced Pressure)

p1 exp s 0 (T1 ) / R 
cp
cv
k
cp 
kR
cv 
R 
pr 2 exp s 0 (T2 ) / R 
c p  cv R
k1 k1 p2 pr 2 v2 vr 2
 Using 
p1 pr1 pv=RT v1 vr1
 k1 k
k  1
T2  p2 

 k 

T2  v1  p2  v1 
      vri = (RTi/pr(Ti))
T1  p1  T1  v2  p1  v2 
 Isentropic Efficiencies
Turbines
• For a well insulated turbine, we know
that work done, W is
 Vi 2  Ve2 
 
0 Q  W  m  hi  he   g zi  ze 
 2 
W
hi  he
m
• The actual work done in the
process shown here is
W a
h1  h2
m
• The isentropic work done in the
process shown here is • The isentropic Wa h1  h2
efficiency is defined as  W  h  h
W s s 1 2s
h1  h2 s
m
 Isentropic Efficiencies
Nozzle
The nozzle isentropic efficiency is
defined as the ratio of actual exit  nozzle 
V / 2
2
2

Kinetic Energy to the exit Kinetic V / 2

2
2
s
Energy for an isentropic expansion

Pump/Compressor
It is defined as the ratio of work needed h h Note that the ratio
for an isentropic compression to the c  2 s 1 is opposite to that
work required in the actual process h2  h1
for a turbine
 Isentropic Efficiencies
Example: 6.147
Known: ηc=80%, ηt=90%,
m =5.8kg/s

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
Reversible
Q cv W cv Q j  V12  V22 
0  m ( s1  s2 )   cv   h1  h2     g z1  z 2 
T m m  2 
W cv  V12  V22 
Q cv
2
Tds  h1  h2     g z1  z 2 
m ( s2  s1 ) m 1
 2 
T Tds dh  vdp
 Q cv  2 2 2
   Tds
 m  int  1
Tds (h2  h1 ) 
1 vdp
1
  rev
W cv 2
Const v W cv
 vdp  v( p2  p1 )
m 1 m
Polytropic Process (pvn=const)
Concludes that less work is required to pump
W cv n
 p2v2  p1v1  n 1 water (low v) than steam(higher v) between
m n 1 the same pressures
W cv That’s the reason for condensing the water in
 p1v1 lnp2 / p1  n 1 a steam power plant
m
 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