Chapter 7

ENTROPY
Second Law of
Thermodynamics-Entropy

1
CONTENTS

Entropy
The Increase of Entropy Principle
Entropy Change of Pure Substances
Isentropic Processes
Property Diagrams
The T-ds relations
The Entropy Change of Ideal Gases
Isentropic Efficiencies of Steady-Flow Devices
LESSON OBJECTIVES

At the end of this lesson, you should be able to:

 Define entropy, entropy change and entropy generation

 Differentiate between reversible and irreversible process

 Describe the Increase of Entropy principle

 Evaluate whether a process is irreversible, reversible or

impossible
Entropy
 Entropy measures the spontaneous dispersal of energy:
how much energy is spread out in a process, or
how widely spread out it becomes — at a specific
temperature. (Sometimes, it’s a simple equation, Entropy
change = “energy dispersed”/T, or qreversible/T ,
 The quantitative measure of the amount of thermal energy not
available to do work." So it's a negative kind of quantity, the
opposite of available energy.

A quantitative measure of the microscopic disorder for a system.

Definition: Theoretical measure of thermal energy that cannot be

transformed into mechanical work in a thermodynamic system.
 ENTROPY
 Clausius inequality states that for any thermodynamic cycle:.

 Q 
  T b  0
where Q = heat transfer at the system boundary
T = absolute temperature at the boundary (K)
 = integration to be performed over the entire cycle Rudolf
Clausius

 This equation is valid for ALL cycles – reversible or irreversible

 Q 
 It was found that:
  T  int  0
rev
 A quantity whose cyclic integral is zero, depends ONLY on the
states, not the process path A PROPERTY
Defining Entropy Change
 Therefore:
 Q  where S is called entropy (kJ/K)
   dS
 T  int
rev

 Integrating the above equation between initial and final states:

2  Q 
 S  S 2  S1     int Entropy change of a system
1
 T  rev
 Entropy change can be positive or negative, depending on the direction of
heat transfer
Q +ve S +ve

Q -ve S -ve
 Defining Entropy Change (cont’d)
 The change in entropy is given by:
N/B:
 Q  Integral of Q/T give value of dS IF the
dS    integration is carried out along an internally
 T  int,rev reversible path between 2 states

 Q 

2
S 2  S1   
 1 T  int,rev

 Entropy is a property

 Therefore entropy change S between 2

specific states is the same whether the
process is reversible or irreversible.

 Units of Entropy is kJ/K, specific entropy

kJ/kg.K
 A Special Case: Internally Reversible Isothermal
Heat Transfer Processes

 Isothermal process ---> internally reversible process

 Q  2 Q 
 S     int     int    Q  int
2 1 2
1
 T  rev 1  To  rev To 1 rev

Q
S 7.6
To

 Eq. 7.6 is useful in determining the entropy changes of thermal energy

reservoirs that can absorb or supply heat indefinitely at constant
temperature
Example
For a particular power plant, the heat added and rejected both
occur at constant temperature and no other processes
experience any heat transfer. The heat is added in the amount
of 3150 kJ at 440oC and is rejected in the amount of 1950 kJ at
20oC. Is the Clausius inequality satisfied and is the cycle
reversible or irreversible?
Calculate the net work, cycle efficiency, and Carnot efficiency based on TH and TL for
this cycle.
Wnet  Qin  Qout  (3150  1950) kJ  1200 kJ
Wnet 1200 kJ
th    0.381 or 38.1%
Qin 3150 kJ
TL (20  273) K
th, Carnot  1   1  0.589 or 58.9%
TH (440  273) K
The Clausius inequality is satisfied. Since the inequality is less than zero, the cycle has
at least one irreversible process and the cycle is irreversible.
 The Increase of Entropy Principle
 Consider a cycle made up of 2 processes
 Q 
  T b  0
From the Clausius Inequality:

 Q   Q 
or 2 1

1  T  2  T   0

b int,rev

The second integral can be expressed as

 1 Q 
 2   S1  S 2
 T  int,rev
 Q 
2
S 2  S1     Q
7.7 OR dS  7.8

1 
T b T

Note: T is the temperature (in K) at boundary where Q is transferred between system

and boundary
The Increase of Entropy Principle (cont’d)
From Eq. 7.8 Q
dS 
T

If Q Process 1-2 is internally reversible

dS 
T
Q
dS  Process 1-2 is irreversible
T

 Entropy change for an irreversible process is greater than that for internally
reversible.
 Therefore, some entropy must have been generated during the irreversible
process - due to the presence of irreversibilities
 This is called entropy generation, Sgen
 It is a measure of the magnitudes of irreversibilities present during the process
 The greater the Sgen, the greater is the extent of irreversibilities
 Used to establish criteria for the performance of engineering devices
 The Increase of Entropy Principle (cont’d)
 Re-write Eq. 7.7, to include entropy generation

 Q   Q 
2 2

S 2  S1     S 2  S1      S gen 7.9
1 
1
T  T b
Always positive
or zero
Entropy transfer
with heat
Sgen depends on process:
• Positive for Irreversible
• Zero for Reversible
Q
For isolated system (or simply adiabatic closed system) Q0  0
T
Sisol  S 2  S1  0
 ISOLATED SYSTEM
 May consists of any no. of subsystems
 A system and its surroundings can be viewed as 2 subsystems of
an isolated system

Sisol  Ssyst  Ssurr  0

 As there are no Q or W by an isolated system

 it is simply adiabatic closed system
Q
Q0  0
T
S gen  Sisol  S2  S1  0 Eq. 6.34

Since Sgen can never be negative, entropy of an isolated system will

increases until it reaches a maximum value (equilibrium state).
(no actual process is reversible, therefore entropy will not be constant)
 The Increase of Entropy Principle (cont’d)

S gen  Sisol  S2  S1  0

The Increase of Entropy Principle

 The entropy of an isolated system during a process always increases
or, in the limiting case of a reversible process, remains constant –
never decreases
Implication of the principle:
• Entropy of a system can decrease
• Entropy change of a system can be negative
• Entropy generation, Sgen can not be negative

0 Irreversible Process (possible)

S gen 0 Reversible Process (Ideal)

0 Impossible Process
LESSON OBJECTIVES
At the end of this lesson, you should be able to:

 Find entropy data for water and R-134a using tables

 Describe isentropic processes

Retrieving Entropy Data
 Entropy Data for Water & Refrigerant (Table)
 Tabulated in the same way in the Tables of Thermodynamics
 Superheated, Compressed, Saturation states (quality)

 Using Graphical Entropy Data

 Locate states and plot processes on diagrams having entropy as
one of the coordinates

 Using T-ds equations (liquids, ideal gases)

Entropy Change for Pure Substances
Tabulated in the same way in the Tables of Thermodynamics

Entropy change of a specified mass,

m (of a closed system) is:

 S  m  s  m  s 2  s1 
 Example 2

 A rigid tank contains 5 kg of R-134a initially at 20oC and 140 kPa.

The refrigerant is now cooled while being stirred until its pressure
drops to 100 kPa. Determine the entropy change of the
refrigerant during this process.
(x2 = 0.8587, s2 = 0.8275 kJ/kgK, ∆S = -1.1744 kJ/K)
ISENTROPIC PROCESSES
 Entropy of a fixed mass can be changed by
 Heat transfer
 Irreversibilities
 Thus, for internally reversible and adiabatic process:
entropy is constant ISENTROPIC process

s  0
or

s 2  s1
ISENTROPIC PROCESSES (cont’d)
 Many engineering systems are adiabatic and performs best when
irreversibilities are minimized.
 Isentropic process can serve as an appropriate model for actual
processes – define efficiencies to compare actual with idealized
conditions

NOTE
Internally reversible and adiabatic process means isentropic
process.
 T-ds Equations
 Previously, we find entropy change for any substance using:
 Q 

2
S 2  S1    Or from tables for water & refrigerant
 1 T  int,rev

 Need to find relationship between T and Q.

 Consider a closed system containing a simple compressible
substance:
Energy balance:  Q i n t ,r ev  d U   W i n t ,r ev
For simple compressible fluid:  Q i n t ,r ev  T d S and
 W i n t ,r ev  p d V
Substituting into the energy balance equation:

T dS  dU  pdV (k J ) 1st T-ds equation

T-ds Equations (cont’d)
Second T-dS equation is derived from d H  d U  d  p V 
dH  dU  pdV  V dp
From 1st T-ds equation:
dH  V dp  dU  pdV T dS  dU  pdV (k J )

TdS  dH  V dp 2nd T-ds equation

Writing both T-dS equations on a unit mass basis:

Tds  du  pdv the equations are also valid for irreversible

processes because they involve only properties and
so are path-independent.
Tds  dh  vdp
 Entropy Change of Ideal Gases
From Gibbs’ equations, the change of entropy of an ideal gas
can be expressed as:
du P dh v
ds   dv   dP
T T T T
For an ideal gas, u=u(T) and h=h(T), du=cv(T)dT and dh=cp(T)dT and
Pv = RT
dT dv dT dP
ds  cv (T )  R , and ds  cP (T ) R
T v T P
By integration, the change of the entropy is
2 2
dT v2 dT P2
s2  s1   cv (T )  R ln( ) or s2  s1   cP (T )  R ln( )
1
T v1 1
T P1
we need to know the function c p (T) and c v (T) in order to complete
the integration,
Entropy Change of Ideal Gases – Special Cases
The dependence of specific heats on temperature makes the
integration more complex. However, for certain cases, one can make
simplifying assumptions.
Case 1: If specific heats are assumed constant, integration is
simplified:
T2 v
s2  s1  cv ln( )  R ln( 2 ) or
T1 v1
T2 P2
s2  s1  cP ln( )  R ln( )
T1 P1

Case 2: Calculate the specific heat at an average temperature, Tavg,

and assume it to be constant. This also allows the specific heat to be
taken out of the integral

Note:
This approximation is generally fairly accurate if the temperature
difference is not too large, usually good if T < few hundred degrees.
Strictly speaking, one should look at the temp. dependence of specific
heats for the particular substance to evaluate the validity of this
approximation.
 Isentropic Processes for Ideal Gases

If a process is isentropic (that is adiabatic and reversible), ds = 0, s1=s2,

then it can be shown that:

T2 v1 k 1 T2 P2  k 1 / k
 ( ) , and ( )
T1 v2 T1 P1
P2 v1 k cp
and  ( ) , where k 
P1 v2 cv
The above are referred to as the: first, second and third, respectively,
isentropic relations for Ideal Gases (assuming constant specific heats).
They can also be written as:

Tvk-1 = constant First isentropic relation

TP(k-1)/k = constant Second isentropic relation
Pvk = constant Third isentropic relation
Example
 Air is compressed from an initial state of 100 kPa and
300 K to 500 kPa and 360 K. Determine the entropy
change using constant cp=1.003 (kJ/kg K)

T2 P2
s2  s1  cP ln( )  R ln( ) if cPis constant
T1 P1
360 500
s2  s1  1.003ln  (0.287) ln  0.279(kJ / kg K )
300 100

• Negative entropy due to heat loss to the surroundings

ISENTROPIC EFFICIENCIES –
Adiabatic Turbine
Isentropic efficiency of a turbine is:
 the ratio of the actual work output of the turbine to the
work output that would be achieved if the process
were isentropic

actual turbine work

T 
isentropic turbine work
wa h1  h2 a
 
ws h1  h2 s

Eq. 7.61
ISENTROPIC EFFICIENCIES –
Pumps / Compressors
Isentropic efficiency of a compressor is:
 the ratio of the work input required in an isentropic
manner to the actual work input

isentropic compressor work

C 
actual compressor work
ws h2 s  h1
 
wa h2 a  h1
Eq. 7.63

ws  P2  P1 
P  
wa h2 a  h1 Eq. 7.64
Example

Air enters a compressor and is compressed adiabatically from 0.1 MPa, 27oC, to a
final state of 0.5 MPa. Find the work done on the air for a compressor isentropic
efficiency of 80 percent. Assume ideal gas and constant specific heat Cp=1.005
kJ/kg.K
System: The compressor control volume

Property Relation: Ideal gas equations, assume constant properties.

2a
T 2s P2

P1
1

s
Using the ideal gas assumption with constant specific heats, the isentropic work per
unit mass flow is
wcs  h2 s  h1  C p (T2 s  T1 )

The isentropic temperature at state 2 is found from the isentropic relation

The compressor isentropic

efficiency is defined as

The conservation of energy becomes ws

C 
wa
wCs  C p (T2 s  T1 ) wcs
wCa 
 1005
.
kJ
(475.4  300) K C
kg  K kJ
kJ 176
 176.0 kg kJ
kg
  220
0.8 kg
Example
Steam enters an adiabatic turbine steadily at 3 MPa and 400oC
and leaves at 50 kPa and 100oC. If the power output of the
turbine is 2 MW, determine

a. Isentropic efficiency of the turbine

b. The mass flow rate of the steam flowing through the turbine
Example
Air is compressed by an adiabatic compressor from 100 kPa and
12oC to a pressure of 800 kPa at a steady rate of 0.2 kg/s. If
the isentropic efficiency of the compressor is 80 percent,
determine the exit temperature of air.
Summary
Entropy
The Increase of Entropy Principle
Entropy Change of Pure Substances
Isentropic Processes
Property Diagrams
The T-ds relations
The Entropy Change of Ideal Gases
Isentropic Efficiencies of Steady-Flow Devices