Thermodynamics: An Engineering Approach

8th Edition in SI Units

Yunus A. Çengel, Michael A. Boles
McGraw-Hill, 2015

CHAPTER 7
ENTROPY

Lecture slides by
Mehmet Kanoglu

Copyright © 2015 The McGraw-Hill Education. Permission required for reproduction or display.
 Objectives
• Apply the second law of thermodynamics to processes.
• Define a new property called entropy to quantify the second-
law effects.
• Establish the increase of entropy principle.
• Calculate the entropy changes that take place during
processes for pure substances, incompressible substances,
and ideal gases.
• Examine a special class of idealized processes, called
isentropic processes, and develop the property relations for
these processes.
• Derive the reversible steady-flow work relations.
• Develop the isentropic efficiencies for various steady-flow
devices.
• Introduce and apply the entropy balance to various systems.

2
Second Law of Thermodynamics – INEQUALITIES!

Irreversible (actual) heat engine is less efficient than a reversible one operating
between the same two thermal energy reservoirs.

Irreversible refrigerator or heat pump has a lower COP than a reversible one
operating between the same temperature limits.

These proved that second law is used to understand engineering process

Clausius inequality

The cyclic integral of dQ/T is always less than or equal to zero.

Valid for all cycles; reversible and irreversible
The integral symbol is used to indicate that the integration to be performed over
the entire cycle.

Any heat transfer to or from the system consist of differential amounts of heat
transfer.

Sum of all these differential amounts of heat transfer divided by the

temperature at the boundary. 3
ENTROPY

Clasius
inequality

Formal
definition
of entropy

The equality in the Clausius inequality holds

for totally or just internally reversible cycles
and the inequality for the irreversible ones. 4
• System connected to a thermal energy reservoir at constant thermodynamic
temperature, TR
• The heat engine/cyclic device receives heat, dQR from reservoir and supplies
heat dQ to the system whose temperature at boundary is T while producing
work, dWrev
• System produces work dWsys as a result of this heat transfer
• Apply energy balance to the combined system,

• Cyclic device is reversible,

• dQ is +ve if to the system
• dQ is –ve if from the system

• Eliminate dQR from above and substitute into energy balance equation,

• System undergo cycle; cyclic device undergoes integral number of cycles,

• Wc is the cyclic integral of dWc and it represents the net work of combined
cycle. 5
• It appears that the combines system is exchanging heat with a single thermal
reservoir while producing work, Wc during a cycle
• But Kelvin-Planck statement : no system can produce a net amount of work
while operating in a cycle and exchanging heat with a single thermal energy
reservoir!
• Therefore, we reason that Wc cannot be a work output and thus it cannot be a
positive quantity.
• Clausius inequality :

• If no reversibilities occur within the system as well as the reversible cyclic

device, then the cycle undergone by the combined system is internally
reversible; it can be reversed.
• In the reverse cycle case, all the quantities have the same magnitude but the
opposite sign.
• Therefore, the work, Wc which could not be positive in a regular case, cannot be
negative in a reverse case.
• So, Wc,int rev = 0
The equality in the Clausius inequality holds
for totally or just internally reversible cycles
and the inequality for the irreversible ones.
• For internally reversible cycles. 6
• To develop a relation for the definition of
entropy.
• A volume occupied by a gas in a piston-cylinder
device undergoing a cycle.
• When the piston returns to its initial position at
the end of a cycle, the volume of the gas also
returns to its initial value.
• Thus, the net change in volume during a cycle is
zero.
• The cyclic integral of volume 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 (dQ/T)int rev must
represent a property in the differential form.
• ENTROPY !
  int rev

 Entropy is an extensive property of a system

int rev

7
 Absolute values of entropy
are determined on the
basis of third law of thermo.
A quantity whose cyclic
integral is zero (i.e., a
The entropy of a substance
property like volume)
can be assign to a zero
Entropy is an extensive value at some arbitrarily
property of a system. selected reference state
and the entropy at other
states can be determined
from equation by choosing
state 1 to be the reference
state (S=0) and state 2 to
be the state at which
entropy is to be
A Special Case: Internally Reversible determined.
Isothermal Heat Transfer Processes

This equation is particularly useful for determining

the entropy changes of thermal energy reservoirs. 8
THE INCREASE OF ENTROPY PRINCIPLE

The equality holds for an internally

reversible process and the inequality
for an irreversible process.

Some entropy is generated or created during an irreversible process,

and this generation is due entirely to the presence of irreversibilities.

The entropy generation Sgen is always a positive quantity or zero.

Can the entropy of a system during a process decrease?
9
The increase
of entropy
principle
10
Some Remarks 1. Processes can occur in a certain
about Entropy 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.
2. 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.
3. The performance of engineering
systems is degraded by the presence
of irreversibilities, and entropy
generation is a measure of the
magnitudes of the irreversibilities
during that process. It is also used to
establish criteria for the performance
of engineering devices.
11
 ENTROPY CHANGE OF PURE SUBSTANCES
Entropy is a property, and thus
the value of entropy of a
system is fixed once the state
of the system is fixed.

Entropy change
12
ISENTROPIC PROCESSES
A process during which the entropy remains constant is called
an isentropic process.

13
PROPERTY DIAGRAMS INVOLVING ENTROPY

On a T-S
diagram, the
area under the
process curve
represents the
heat transfer for
internally
reversible
processes.

Mollier diagram: The h-s diagram

14
15
WHAT IS ENTROPY?
Boltzmann relation W the total number of
possible relevant
microstates of the system

Gibbs’ formulation

pi sum of all microstates’ uncertainties,

i.e., probabilities

Boltzmann constant

A pure crystalline
substance at absolute
zero temperature is in
perfect order, and its
entropy is zero (the third
law of thermodynamics). 16
17
18
19
THE T ds RELATIONS

the first T ds, or Gibbs equation

the second T ds equation

Differential changes
in entropy in terms
of other properties
20
ENTROPY CHANGE OF LIQUIDS AND SOLIDS
Since for liquids and solids
Liquids and solids can be
approximated as
incompressible substances
since their specific volumes
remain nearly constant
during a process.

For and isentropic process of an incompressible substance

21
THE ENTROPY CHANGE OF IDEAL GASES
From the first T ds relation From the second T ds relation

22
Constant Specific Heats (Approximate Analysis)

Entropy change of an ideal gas on a

unit–mole basis

23
 Variable Specific Heats (Exact Analysis)
We choose absolute zero as the reference
temperature and define a function s° as

On a unit–mass basis

On a unit–mole basis

24
25
Isentropic Processes of Ideal Gases
Constant Specific Heats (Approximate Analysis)

Setting this eq. equal to

zero, we get

26
Isentropic Processes of Ideal Gases
Variable Specific Heats (Exact Analysis)

Relative Pressure and Relative Specific Volume

exp(s°/R) is The use of Pr data
the relative for calculating the
pressure Pr. final temperature
during an isentropic
process.

The use of vr data for

calculating the final
T/Pr is the relative
temperature during an
specific volume vr.
isentropic process 27
REVERSIBLE STEADY-FLOW WORK

When kinetic and

potential energies
are negligible

The larger the

specific
volume, the
For the steady flow of a liquid through a
greater the
device that involves no work interactions
(such as a pipe section), the work term is work produced
zero (Bernoulli equation): (or consumed)
by a steady-
flow device.
28
EXAMPLE: Compressing a
Substance in the Liquid versus Gas
Phases

29
Proof that Steady-Flow Devices Deliver the Most and Consume
the Least Work when the Process Is Reversible
Taking heat input and work output positive:
Actual
Reversible

Work-producing devices such as

turbines deliver more work, and work-
consuming devices such as pumps
and compressors require less work
when they operate reversibly. 30
 MINIMIZING THE COMPRESSOR WORK
When kinetic and
potential energies
are negligible

Isentropic (Pvk = constant):

Polytropic (Pvn = constant):

Isothermal (Pv = constant):

The adiabatic compression (Pvk = constant)

requires the maximum work and the
isothermal compression (T = constant)
requires the minimum. Why?
31
Multistage
Compression
with
Intercooling
The gas is compressed
in stages and cooled
between each stage by
passing it through a
heat exchanger called
an intercooler.

To minimize compression work during two-stage

compression, the pressure ratio across each
stage of the compressor must be the same. 32
ISENTROPIC EFFICIENCIES
OF STEADY-FLOW DEVICES

Isentropic Efficiency
of Turbines

33
34
Isentropic Efficiencies of Compressors and Pumps

When kinetic and

potential energies
are negligible
For a
pump
Isothermal
efficiency

Compressors
are sometimes
intentionally Can you use isentropic efficiency for a
cooled to non-adiabatic compressor?
minimize the Can you use isothermal efficiency for
work input. an adiabatic compressor? 35
36
Isentropic Efficiency
of Nozzles

If the inlet velocity of the

fluid is small relative to
the exit velocity, the
energy balance is

Then,

37
38
ENTROPY BALANCE

Entropy Change of a
System, ∆Ssystem

When the properties of the

system are not uniform

Energy and entropy

balances for a system.
39
Mechanisms of Entropy Transfer, Sin and Sout
1 Heat Transfer
Entropy transfer by heat transfer:

Entropy transfer by work:

No entropy accompanies work as it crosses the

system boundary. But entropy may be
generated within the system as work is
dissipated into a less useful form of energy. 40
2 Mass Flow
Entropy transfer by mass:

When the properties of the mass

change during the process

41
Entropy Generation, Sgen Entropy generation
outside system
boundaries can be
accounted for by
writing an entropy
balance on an
extended system that
includes the system
and its immediate
surroundings.

Mechanisms of entropy transfer for a

general system.
42
Closed Systems

The entropy change of a closed system during a process is equal to the

sum of the net entropy transferred through the system boundary by heat
transfer and the entropy generated within the system boundaries.

43
 Control Volumes

The entropy of a
substance always
increases (or
remains constant in
the case of a
reversible process)
as it flows through a
single-stream,
adiabatic, steady-
flow device. 44
EXAMPLES
Entropy balance for heat
transfer through a wall

Entropy balance for

a throttling process

45
Entropy Generated when a Hot
Block Is Dropped in a Lake

or

Entropy Generation in a Heat Exchanger

46
Entropy Generation Associated
with Heat Transfer

47
Entropy generation associated with a
heat transfer process

48
 Summary
• Entropy
• The Increase of entropy principle
• Entropy change of pure substances
• Isentropic processes
• Property diagrams involving entropy
• What is entropy?
• The T ds relations
• Entropy change of liquids and solids
• The entropy change of ideal gases
• Reversible steady-flow work
• Minimizing the compressor work
• Isentropic efficiencies of steady-flow devices
• Entropy balance
49