CHEM3003 – Process Engineering

Thermodynamics

Chapter 7
ENTROPY

Thermodynamics: An Engineering Approach, 6th Edition

Yunus A. Cengel, Michael A. Boles
McGraw-Hill, 2008

Dr Wathiq M Taama - Chapter 7 1

 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.

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 ENTROPY

Clasius
inequality

Formal
definition
of entropy

The system considered in The equality in the Clausius inequality holds

the development of the for totally or just internally reversible cycles
Clausius inequality. and the inequality for the irreversible ones.
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 A quantity whose cyclic
integral is zero (i.e., a
property like volume)
Entropy is an extensive
property of a system.

The entropy change between two The net change

specified states is the same whether in volume (a
property) during
the process is reversible or irreversible.
a cycle is
A Special Case: Internally Reversible always zero.
Isothermal Heat Transfer Processes

This equation is particularly useful for determining

the entropy changes of thermal energy reservoirs.
4
Dr Wathiq M Taama - Chapter 7
THE INCREASE OF ENTROPY PRINCIPLE

The equality holds for an internally

reversible process and the inequality
for an irreversible process.

A cycle composed of a
reversible and 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?
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The entropy change of an isolated
system is the sum of the entropy
changes of its components, and is
never less than zero.

A system and its surroundings

form an isolated system.

The increase of
entropy
principle
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Some Remarks about Entropy
1. 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.
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,
The entropy change of a and entropy generation is a measure of the
system can be negative, magnitudes of the irreversibilities during that
but the entropy generation process. It is also used to establish criteria
cannot. for the performance of engineering devices.

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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.

Schematic of the T-s diagram for water.

The entropy of a pure substance Entropy change

is determined from the tables
(like other properties).
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ISENTROPIC PROCESSES
A process during which the entropy remains constant is called
an isentropic process.

During an internally
reversible, adiabatic
The isentropic process appears as a
(isentropic) process, the
vertical line segment on a T-s diagram.
entropy remains constant.
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PROPERTY DIAGRAMS INVOLVING ENTROPY

On a T-S
diagram, the
area under the
process curve
represents the
heat transfer for
internally
reversible
processes.
For adiabatic steady-flow
devices, the vertical distance
∆h on an h-s diagram is a
measure of work, and the
horizontal distance ∆s is a
measure of irreversibilities.

Mollier diagram: The h-s diagram

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WHAT IS ENTROPY?
Boltzmann
relation

A pure crystalline substance at absolute zero

temperature is in perfect order, and its entropy is
zero (the third law of thermodynamics).

The level of molecular

disorder (entropy) of a
substance increases as it Disorganized energy does not create much
melts or evaporates. useful effect, no matter how large it is.
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 The paddle-wheel work done on a gas increases the
level of disorder (entropy) of the gas, and thus energy
is degraded during this process.

In the absence of During a heat

friction, raising a transfer process, the
weight by a rotating net entropy
shaft does not increases. (The
create any disorder increase in the
(entropy), and thus entropy of the cold
energy is not body more than
degraded during this offsets the decrease
process. in the entropy of
Dr Wathiq M Taama - Chapter 7 the hot body.) 12
THE T ds RELATIONS

the first T ds, or Gibbs equation

The T ds relations are valid for

both reversible and irreversible the second T ds equation
processes and for both closed
and open systems.
Differential changes
in entropy in terms
of other properties

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ENTROPY CHANGE OF LIQUIDS AND SOLIDS
Liquids and solids can be
approximated as
incompressible substances
Since for liquids and solids since their specific volumes
remain nearly constant
during a process.

For and isentropic process of an incompressible substance

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

A broadcast
from channel IG.

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Constant Specific Heats (Approximate Analysis)

Entropy change of an ideal gas on a

unit–mole basis

Under the constant-specific-

heat assumption, the specific
heat is assumed to be constant
at some average value.
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Variable Specific Heats (Exact Analysis)
We choose absolute zero as the reference
temperature and define a function s° as

On a unit–mass basis The entropy of an

ideal gas depends on
both T and P. The
function s represents
only the temperature-
On a unit–mole basis
dependent part of
entropy.

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

Setting this eq. equal to

zero, we get

The isentropic relations of ideal

gases are valid for the isentropic
processes of ideal gases only.

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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
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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 Reversible work
device that involves no work interactions work produced relations for
(such as a pipe section), the work term is (or consumed) steady-flow
zero (Bernoulli equation): by a steady- and closed
flow device. systems.
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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

A reversible turbine delivers more

work than an irreversible one if
Work-producing devices such as
both operate between the same
turbines deliver more work, and work-
end states.
consuming devices such as pumps
and compressors require less work
when they operate reversibly.
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MINIMIZING THE COMPRESSOR WORK
When kinetic and
potential energies
are negligible

Isentropic (Pvk = constant):

Polytropic (Pvn = constant):

Isothermal (Pv = constant): P-v diagrams of isentropic,

polytropic, and isothermal
compression processes between
the same pressure limits.
The adiabatic compression (Pvk = constant)
requires the maximum work and the
isothermal compression (T = constant)
requires the minimum. Why?
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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.
P-v and T-s
diagrams for a two-
stage steady-flow
compression
process.

To minimize compression work during two-stage

compression, the pressure ratio across each
stage of the compressor must be the same.
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ISENTROPIC
EFFICIENCIES OF
STEADY-FLOW DEVICES
The isentropic process involves no
irreversibilities and serves as the ideal
process for adiabatic devices.

Isentropic
Efficiency
of
Turbines

The h-s diagram for

the actual and
isentropic
processes of an
adiabatic turbine.
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Isentropic Efficiencies of Compressors and Pumps

When kinetic and

potential energies
are negligible
For a
pump
The h-s diagram
Isothermal
of the actual and
efficiency
isentropic
processes of an
adiabatic
compressor.
Compressors are Can you use isentropic efficiency for a
sometimes intentionally non-adiabatic compressor?
cooled to minimize the
Can you use isothermal efficiency for
work input.
an adiabatic compressor?

Dr Wathiq M Taama - Chapter 7 25

Isentropic Efficiency
of Nozzles

If the inlet velocity of the

fluid is small relative to
the exit velocity, the
The h-s diagram
energy balance is
of the actual and
isentropic
processes of an
adiabatic nozzle.
Then,

A substance leaves
actual nozzles at a
higher temperature
(thus a lower velocity)
as a result of friction.

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ENTROPY BALANCE

Entropy Change of a
System, ∆Ssystem

When the properties of the

system are not uniform

Energy and entropy

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

Entropy transfer by work:

Heat transfer is always

accompanied by entropy transfer
in the amount of Q/T, where T is
the boundary temperature.
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.
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Mechanisms of Entropy Transfer, Sin and Sout
2 Mass Flow
Entropy transfer by mass:

When the properties of the mass

change during the process

Mass contains entropy as well as

energy, and thus mass flow into or
out of system is always
accompanied by energy and
entropy transfer.

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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.
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Closed Systems

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 Control Volumes

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

Entropy balance for

a throttling process

Dr Wathiq M Taama - Chapter 7 33

Entropy generation associated
with a heat transfer process

Graphical representation of entropy generation during a heat transfer process

through a finite temperature difference.
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Dr Wathiq M Taama - Chapter 7
EXERGY: WORK POTENTIAL OF ENERGY
The useful work potential of a given amount of energy at some
specified state is called exergy, which is also called the availability or
available energy.
A system is said to be in the dead state when it is in thermodynamic
equilibrium with the environment it is in.

At the dead state, the useful

work potential (exergy) of a
system is zero.

A system that is in equilibrium with its

environment is said to be at the dead
state.
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A system delivers the maximum possible work as it undergoes a reversible
process from the specified initial state to the state of its environment, that is,
the dead state.
This represents the useful work potential of the system at the specified state
and is called exergy.
Exergy represents the upper limit on the amount of work a device can deliver
without violating any thermodynamic laws.

The immediate surroundings of a hot The atmosphere contains a

potato are simply the temperature tremendous amount of energy, but
gradient zone of the air next to the no exergy.
potato.
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Exergy (Work Potential) Associated with Kinetic and
Potential Energy
Exergy of kinetic energy:

Exergy of potential energy:

The work
potential or
exergy of
potential energy
The exergies of is equal to the
kinetic and potential energy
potential energies itself.
are equal to
themselves, and
they are entirely
Unavailable energy is
available for work.
the portion of energy
that cannot be
converted to work by
even a reversible heat
engine.
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REVERSIBLE WORK AND IRREVERSIBILITY
Reversible work Wrev: The maximum amount of
useful work that can be produced (or the
minimum work that needs to be supplied) as a
system undergoes a process between the
specified initial and final states.
As a closed
system expands,
some work needs
to be done to push
the atmospheric
air out of the way
(Wsurr).

The difference between

reversible work and
actual useful work is the
irreversibility.

For constant-volume
systems, the total
actual and useful
works are identical
(Wu = W).
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SECOND-LAW EFFICIENCY, II

Two heat engines that have

Second-law efficiency is a the same thermal efficiency,
measure of the performance of a but different maximum
device relative to its performance thermal efficiencies.
under reversible conditions.
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 General definition of
exergy efficiency

The second-law efficiency of

naturally occurring processes is
zero if none of the work potential is
recovered.
Second-law efficiency of all
reversible devices is 100%.
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 Summary
• Entropy
• The Increase of entropy principle
• Some remarks about entropy
• 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

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