Thermodynamics: An Engineering Approach, 6th Edition

Yunus A. Cengel, Michael A. Boles

McGraw-Hill, 2008

Chapter 7
ENTROPY

Ummi Kalthum Binti Ibrahim

Faculty of Chemical Engineering
UiTM Malaysia
 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
 What is ENTROPY?
• The first law of thermodynamics deals with the property energy and
the conservation of it.
• The second law leads to the definition of a new property called
entropy.
• Energy spreads out and disperses rather than staying concentrated,
i.e., localized in one place.
• Entropy  measures what happens in that kind of process of energy
dispersing.
• Formal definition of entropy:

• “Entropy change"  measuring the difference in energy distribution

"after" some happening versus the "before".)

3
 ENTROPY
Clausius Inequality

• To define the entropy, we will develop the

Clausius inequality
• Consider the system to the right
• Applying the first law to the combined system we
get
Ein  Eout  EC
QR  Wrev  Wsys  dEC
• EC is the energy of the combined system
• The combined work is
WC  Wrev  Wsys
• The energy balance is now

QR  WC  dEC Rudolf

Clausius

4
 ENTROPY
Clausius Inequality (cont.)

• If the engine is totally reversible then,

QR Q  QH  T
 from    H
TR T  QL  rev TL
• The total work becomes
Q
WC  TR  dEC
T
• Now, the total work done is found by taking the
cyclic integral of the incremental work
Q
WC  TR    dEC
T
 ENTROPY
Clausius Inequality (cont.)

• If the system, as well as the heat engine, is

allowed to undergo a cycle then,

 dE C 0
• Since energy is a property, the total work
becomes
Q
WC  TR 
T
• If WC is positive, then there exist a cyclic device
exchanging energy with a single heat reservoir
and producing an equivalent amount of work
• Such a device violates the Kelvin-Planck
statement of the second law
 ENTROPY
Clausius Inequality (cont.)

• This indicates that WC has to be zero or negative

to not violate the Kelvin-Planck statement
Q
WC  TR  0
T
• Since TR > 0 and Q is the net heat added to the
system (Qnet)
Q
T 0

• This is the Clausius inequality

• The inequality is valid for all thermodynamic
cycles, reversible or irreversible
 ENTROPY

Clausius Inequality (cont.)

• If no irreversibilities occur within the system as well as the cyclic device, then
the cycle undergone by the combined system will be internally reversible
• As a result, the cycle can be reversed, with all of the quantities having the same
magnitude, but the opposite sign
• In the reverse case, WC has to be zero or positive to avoid violation of the
Kelvin-Planck statement
• Therefore, to avoid violation of the Kelvin-Planck statement for both the forward
and reverse case, WC, int rev = 0, from which follows

 Q 
  T int rev  0
 ENTROPY
Clausius Inequality (cont.)
 Q 
• It follows that the quantity   must represent a property
 T int rev
• This property is given the name entropy

 Q 
dS   
 T int rev
• The term entropy is generally used to refer to both total entropy (S, extensive)
and entropy per unit mass (s, intensive)
• The entropy change can be obtained from integration
2  Q 
S  S2  S1    
1
 T int rev
• To use the above expression, the relationship between Q and T during a
process must be known
Q
• Example: int. rev. isothermal heat transfer process, S 
To
 ENTROPY

Clasius
inequality

Formal
definition
of entropy

The system considered in

the development of the The equality in the Clausius inequality holds
Clausius inequality. for totally or just internally reversible cycles
and the inequality for the irreversible ones.
10
 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.
11
 THE INCREASE OF ENTROPY PRINCIPLE

• Introducing the definition of entropy

2 Q
S2  S1  
1 T
• In differential form
Q
dS 
T
• Internally reversible → =
• Irreversible → >
• This suggests that some entropy is generated or created during an irreversible
process
• The entropy generated during a process is called entropy generation, Sgen
 THE INCREASE OF ENTROPY PRINCIPLE
Reversible process: A process that can be reversed without leaving any trace on the surroundings.
Irreversible process: A process that is not reversible.
Irreversibilities: The factors that cause a process to be irreversible are called.
Internally reversible process: If no irreversibilities occur within the boundaries of the system during the process.

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?
13
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
14
 Example 1: Entropy Generation during Heat
Transfer Processes
• 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.
(a) For the heat transfer process to a sink at 500 K:

(b) for a sink temperature of 750 K:

The total entropy change for the
process in part (b) is smaller, and
therefore it is less irreversible.

15
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.

16
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).
17
Example 2: Entropy Change of a Substance in
a Tank
• A rigid tank contains 5 kg of refrigerant-134a initially at 20°C 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.
The properties of the refrigerant at both states are:
P2 =100 kPa
P1 = 140 kPa (v2 = v1 )
State 1: T1 = 20°C State 2: vf = 0.0007259 m3/kg
s1 =1.0624 kJ/kg·K vg = 0.19254 m3/kg
v1 = 0.16544 m3/kg s2 = ?
The refrigerant is a saturated liquid–vapor mixture at the final state since vf < v2 < vg at 100 kPa
pressure. Therefore, we need to determine the quality first:

Then the entropy change of the refrigerant during this process is:

18
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.
19
Example 3: Isentropic Expansion of Steam in a
Turbine
• Steam enters an adiabatic turbine at 5 MPa and 450°C and leaves
at a pressure of 1.4 MPa. Determine the work output of the turbine
per unit mass of steam if the process is reversible.
The power output of the turbine is determined from the rate form of the energy
balance:

The inlet state is completely specified since two properties are given. But only one property (pressure) is
given at the final state, and we need one more property to fix it. The second property comes from the
observation that the process is reversible and adiabatic, and thus isentropic. Therefore, s 2 = s1.

State 1: Then the work output of the turbine per unit mass of the
steam becomes:

State 2:

20
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

21
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 Disorganized energy does not create much
it melts or evaporates. useful effect, no matter how large it is.

22
 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
the hot body.) 23
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

24
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

25
 Example 4: Entropy Change of Liquids and
Solids
• A 25-kg iron block initially at 350°C is quenched in an insulated tank that
contains 100 kg of water at 18°C. Assuming the water that vaporizes during
the process condenses back in the tank, determine the total entropy change
during this process.

Properties: The specific heat of water at 25°C is cp = 4.18 kJ/kg.°C. The specific heat of iron at room
temperature is cp = 0.45 kJ/kg.°C (Table A-3).
The energy balance for this system can be expressed as:

Substituting, Thus,

The entropy generated during this process is determined from:

26
THE ENTROPY CHANGE OF IDEAL GASES
From the first T ds relation From the second T ds relation

A broadcast
from channel IG.

27
Constant Specific Heats (Approximate Analysis)
Assuming constant specific heats for ideal gases is common approximation.
The entropy change relations for ideal gases under constant specific heat assumption are obtained by
replacing cv(T) and cp(T) by cv,avg and cp,avg.

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.
28
 Variable Specific Heats (Exact Analysis)
Exact analysis equation is used when the temperature change during a process is large
and the specific heats of ideal gas are very nonlinearly within the temperature range.

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
On a unit–mole basis function so represents
only the temperature-
dependent part of
entropy.
29
 Example 5: Entropy Change of Ideal Gases

• A mass of 7 kg of helium undergoes a process from an initial state of 0.3 m3/kg and
27°C to a final state of 0.6 m3/kg and 95°C. Determine the entropy change of helium
during this process.

Properties The gas constant of helium is R = 2.0769 kJ/kg.K (Table A-1). The constant volume
specific heat of helium is cv = 3.1156 kJ/kg.K (Table A-2).

From the ideal-gas entropy change relation,

30
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.

31
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
32
 Example 6:Isentropic Processes of Ideal Gases
• An ideal gas at 100 kPa and 27°C enters a steady-flow compressor. The gas is compressed to
400 kPa, and 10 percent of the mass that entered the compressor is removed for some other use.
The remaining 90 percent of the inlet gas is compressed to 600 kPa before leaving the
compressor. The entire compression process is assumed to be reversible and adiabatic. The
power supplied to the compressor is measured to be 32 kW. If the ideal gas has constant specific
heats such that cv = 0.8 kJ/kg K and cp = 1.1 kJ/kg K, (a) sketch the compression process on a
T-s diagram, (b) determine the temperature of the gas at the two compressor exits, in K, and (c)
determine the mass flow rate of the gas into the compressor, in kg/s.
Properties: The properties of ideal gas are given to be cp = 1.1 kJ/kg.K and cv = 0.8 kJ/kg.K.

(a) T-s Diagram: (b) The specific heat ratio of the gas is

The exit temperatures are determined from ideal gas

isentropic:

33
Example 6:Isentropic Processes of Ideal Gases
(c) A mass balance on the control volume gives:

The energy balance for this steady-flow system can be expressed in the rate form as:

Solving for the inlet mass flow rate, we obtain:

34
ENTROPY BALANCE

Entropy Change of a
System, ∆Ssystem

When the properties of the

system are not uniform

Energy and entropy

balances for a system.
35
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. 36
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.

37
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.
38
Closed Systems

39
 Control Volumes

The entropy of a
substance always
increases (or
remains constant in The entropy of a control
the case of a volume changes as a
reversible process) result of mass flow as well
as it flows through a as heat transfer.
single-stream,
adiabatic, steady-
flow device. 40
EXAMPLES
Entropy balance for heat
transfer through a wall

Entropy balance for

a throttling process

41
 Example 10
• Cold water (cp = 4.18 kJ/kg·°C) leading to a shower enters a well-insulated, thin-walled, double-
pipe, counter-flow heat exchanger at 15°C at a rate of 0.25 kg/s and is heated to 45°C by hot
water (cp = 4.19 kJ/kg·°C) that enters at 100°C at a rate of 3 kg/s. Determine (a) the rate of heat
transfer and (b) the rate of entropy generation in the heat exchanger.

(a) The energy balance for this steady-flow system can be

expressed in the rate form as:

(b) The rate of entropy generation within the heat

exchanger is determined by applying the rate form of
the entropy balance on the entire heat exchanger:

Then the rate of heat transfer to the cold water in this

heat exchanger becomes:

The outlet temperature of the hot water is determined The rate of entropy generation is determined
to be: to be:

43