Chapter 6

Entropy
A Measure of Disorder
Engineering
Thermodynamics I
(MEng 5211)
Prepare By: Mr. Hiwot Berhanu (MSc.)
E-mail: [email protected]
(comments, suggestions, questions … are welcome)
THE OBJECTIVES OF THE CHAPTER
 THE OBJECTIVES OF THE CHAPTER
Entropy
The increase of entropy principle
Entropy change of pure substance
Isentropic processes
Property diagrams involving entropy
The Tds relations
Entropy change of liquids, solids, and ideal gases
Reversible steady-flow work
Minimizing the compressor work
Reducing the cost of compressed air
Isentropic efficiencies of steady-flow device
 Introduction
Entropy can be viewed as a measure of molecular
disorder, or molecular randomness.
The entropy of a substance is lowest in the solid
phase and highest in the gas phase

The fig. shows, during a heat transfer

process, the net entropy increases. (The
increase in the entropy of the cold body Fig. shows, The level of molecular disorder
more than offsets the decrease in the (entropy) of a substance increases as it melts or
entropy of the hot body.) evaporates.
 Entropy and the Clausius Inequality:
 The second law of thermodynamics leads to the
definition of a new property called entropy, a
quantitative measure of microscopic disorder for a
system.
 To obtain the working definition of entropy and,
thus, the second law, let's derive the Clausius
inequality.
 Consider a heat reservoir giving up heat to a
reversible heat engine, which in turn gives up heat
to a piston-cylinder device as shown below.
 Entropy and the Clausius Inequality:
We apply the first law on an incremental basis
to the combined system composed of the heat
engine and the system. Ein  Eout  Ec
QR  (Wrev  Wsys )  dEc
Where, Ec is the energy of the combined system.
Let Wc be the work done by the combined system.
Then the first law becomes:
Wc  Wrev  Wsys
QR  Wc  dEc
If we assume that the engine is totally reversible,
then: QR Q

TR T
Q
QR  TR
T
The total net work done by the Q
Fig. The system considered in the combined system becomes: Wc  TR  dEc
development of the Clausius inequality. T
 Entropy and the Clausius Inequality:
 Now the total work done is found by taking the
cyclic integral of the incremental work.
If the system, as well as the heat engine, is required to
undergo a cycle, then:
and the total net work becomes:
 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.
 Considering that TR is the thermodynamic temperature and
thus a positive quantity, we must have
 Therefore, since TR > 0 (absolute temperature), we conclude
 Entropy and the Clausius Inequality:
or
Here Q is the net heat added to the system, Qnet.

 This equation is called the Clausius inequality.

 The equality holds for the reversible process and the
inequality holds for the irreversible process.
Example 1:
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 440 0 C and is rejected in the amount of 1950 kJ at 200 C.
Is the Clausius inequality satisfied and is the cycle reversible or
irreversible?
 Entropy and the Clausius Inequality:
 2. For a particular power plant, the heat added and
rejected both occur at constant temperature; no other
processes experience any heat transfer. The heat is
added in the amount of 3150 kJ at 440 0 C and is
rejected in the amount of 1294.46 kJ at 𝟐𝟎𝟎 C. Is the
Clausius inequality satisfied and is the cycle reversible
or irreversible?
 Definition of Entropy:
 Now consider the volume occupied by a gas in a piston-
cylinder device undergoing a cycle, as shown below.
 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. This is also expressed as:
 We see that the cyclic integral of a property
is zero.
 A quantity whose cyclic integral is zero
depends only on the state and not on the
process path; thus it is a property.
 Therefore the quantity (Qnet/T)int rev must
be a property. Figure: The net change in volume (a
property) during a cycle is always zero.
 Definition of Entropy:
 Consider the cycle shown below composed of two reversible
processes A and B.
 Apply the Clausius inequality for this cycle.
 What do you conclude about these two integrals?
P 2 B

A 1

V
Fig. A cycle composed of
two reversible processes.
Apply the Clausius inequality for the cycle made of two internally
reversible processes:
 Definition of Entropy:
You should find:
 Since the quantity (Qnet/T)int rev is independent of the path
and must be a property, we call this property the entropy S.
The entropy change occurring during a process is
related to the heat transfer and the temperature of
the system.
 The entropy is given the symbol S (kJ/K), and the specific
entropy is s (kJ/kg.K).
 The entropy change during a reversible process, sometimes
called an internally reversible process, is defined as:
 Definition of Entropy:
In general the entropy change during a process is
defined as: Qnet
dS 
T
Where = holds for the internally reversible process
> holds for the irreversible process

Consider the effect of heat transfer on entropy for the internally

reversible case. Qnet
dS 
T
Which temperature T is this one? If:
Qnet  0, then dS  0
Qnet  0, then dS  0
Qnet  0, then dS  0
 Definition of Entropy:
 This last result shows why we have kept the subscript
net on the heat transfer Q.
 It is important for you to recognize that Q has a sign
depending on the direction of heat transfer.
 The net subscript is to remind us that Q is positive when
added to a system and negative when leaving a system.
 Thus, the entropy change of the system will have the
same sign as the heat transfer in a reversible process.
 From the above, we see that for a reversible, adiabatic
process dS  0
S2  S1
 The reversible, adiabatic process is called an isentropic
process.
 Causes of Entropy:

 Entropy change is caused by heat transfer and

irreversibilities.
 Heat transfer to a system increases the entropy;
 Heat transfer from a system decreases it.
 The effect of irreversibilities is always to increase the
entropy.
 In fact, a process in which the heat transfer is out of
the system may be so irreversible that the actual
entropy change is positive.
Friction is one source of irreversibilities in a system.
 Example:
1. 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 Generation :
 The entropy change during a process is obtained by
integrating the dS equation over the process:

 Here, the inequality is to remind us that the entropy change

of a system during an irreversible process is always greater
than , called 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 as Sgen.
 We can remove the inequality by noting the following:
 Entropy Generation:
 Sgen is always a positive quantity or zero.
 Its value depends upon the process and thus it is not
a property.
 Sgen is zero for an internally reversible process.
 The integral is performed by applying the
first law to the process to obtain the heat transfer as
a function of the temperature.
 The integration is not easy to perform, in general.
 THE INCREASE OF ENTROPY PRINCIPLE:

 Now consider an isolated system composed of several subsystems

exchanging energy among themselves.
 Since the isolated system has no energy transfer across its system
boundary, the heat transfer across the system boundary is zero.

Applying the definition of entropy to the isolated system:

The total entropy change for the isolated system is:

Sisolated  0
 THE INCREASE OF ENTROPY PRINCIPLE:

 This equation is the working definition of the second

law of thermodynamics.
 The second law, known as the principle of increase of
entropy, is stated as “The total entropy change of an
isolated system during a process always increases or,
in the limiting case of a reversible process, remains
constant.”
 Now consider a general system
exchanging mass as well as energy with
its surroundings.
S gen  Stotal  Ssys   Ssurr  0
where = holds for the totally reversible process
> holds for the irreversible process
 THE INCREASE OF ENTROPY PRINCIPLE:

 Thus, the entropy generated or the total entropy

change (sometimes called the entropy change of the
universe or net entropy change) due to the process of
this isolated system is positive (for actual processes) or
zero (for reversible processes).
 The entropy changes of the important system (closed
system or control volume) and its surroundings do not
both have to be positive.
 The entropy for a given system (important or
surroundings) may decrease during a process, but the
sum of the entropy changes of the system and its
surroundings for an isolated system can never
decrease.
 THE INCREASE OF ENTROPY PRINCIPLE:

 Entropy change is caused by heat transfer and

irreversibilities.
 Heat transfer to a system increases the entropy, and
heat transfer from a system decreases it.
 The effect of irreversibilities is always to increase the
entropy.
 The increase in entropy principle can be summarized
as follows:
 Some Remarks about Entropy:

1. Processes can occur in a certain direction only, not in

just any direction, such that Sgen≥0.
2. Entropy is a no conserved property, and there is no
such thing as the conservation of entropy principle.
3. The entropy of the universe is continuously increasing.
4.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.
 Example:
Entropy Generation during Heat Transfer Processes:
1. 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 CHANGE OF PURE SUBSTANCES:

Third Law of Thermodynamics

 The third law of thermodynamics states that the entropy of a
pure crystalline substance at absolute zero temperature is zero.
 This law provides an absolute reference point for the
determination of entropy.
 The entropy determined relative to this point is called absolute
entropy.

Entropy as a Property
 Entropy is a property, and it can be expressed in terms of more
familiar properties (P, v, T) through the Tds relations.
 These relations come from the analysis of a reversible closed
system that does boundary work and has heat added.
 Writing the first law for the closed system in differential form
on a per unit mass basis:
 ENTROPY CHANGE OF PURE SUBSTANCES:

The temperature-entropy and enthalpy-entropy diagrams for

water are shown below.

The entropy change of a specified mass m (a

closed system) during a process is simply
Figure Schematic of the T-s diagram for water.
 Example:
1. 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.
 ISENTROPIC PROCESSES:
 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. s  s2  s1
s2  s1
 That is, a substance will have the
same entropy value at the end of
the process as it does at the
beginning if the process is carried
out in an isentropic manner.
 Example:
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.
 ISENTROPIC PROCESSES:

 Many engineering systems or devices such as pumps,

turbines, nozzles, and diffusers are essentially
adiabatic in their operation, and they perform best
when the irreversibilities, such as the friction
associated with the process, are minimized.
 Therefore, an isentropic process can serve as an
appropriate model for actual processes.
 Also, isentropic processes enable us to define
efficiencies for processes to compare the actual
performance of these devices to the performance
under idealized conditions.
 PROPERTY DIAGRAMS INVOLVING ENTROPY:

For the reversible process, the equation for dS implies that

or the incremental heat transfer in a process is the
product of the temperature and the differential of the
entropy, the differential area under the process curve
plotted on the T-S diagram.

Qnet
dS 
T
Qnet  TdS

Figure On a T-S diagram, the area under the process curve

represents the heat transfer for internally reversible processes.
 Entropy and Entropy Generation in Daily Life:
 Entropy can be viewed as a measure of disorder or
disorganization in a system.
 Efficient people lead low-entropy (highly organized)
lives.
 They have a place for everything, and it takes minimum
energy for them to locate something.
 Inefficient people, on the other hand, are
disorganized and lead high-entropy lives.
 It takes them minutes to find something they need, and
they are likely to create a bigger disorder as they are
searching since they will probably conduct the search in
a disorganized manner.
 People leading high-entropy lifestyles are always on the run,
and never seem to catch up.
 THE Tds RELATIONS:
The change in internal energy and volume for an
incompressible substance is:

The second T ds equation is obtained by eliminating du from above

equation by using the definition of enthalpy (h = u + Pv):
 ENTROPY CHANGE OF LIQUIDS AND SOLIDS:

 Recall that liquids and solids can be approximated as

incompressible substances since their specific volumes
remain nearly constant during a process.
 ENTROPY CHANGE OF IDEAL GASES:

Constant Specific Heats (Approximate Analysis)

 Assuming constant specific heats for ideal gases is a common approximation,
and we used this assumption before on several occasions.
 It usually simplifies the analysis greatly, and the price we pay for this
convenience is some loss in accuracy.
 ENTROPY CHANGE OF IDEAL GASES:

Variable Specific Heats (Exact Analysis)

 When the temperature change during a process is large and the
specific heats of the ideal gas vary nonlinearly within the
temperature range, the assumption of constant specific heats
may lead to considerable errors in entropy-change calculations.
 For those cases, the variation of specific heats with temperature
should be properly accounted for by utilizing accurate relations
for the specific heats as a function of temperature.
 ENTROPY CHANGE OF IDEAL GASES:

Isentropic Processes of Ideal Gases

 Several relations for the isentropic processes of ideal gases can
be obtained by setting the entropy-change relations developed
previously equal to zero.
 Again, this is done first for the case of constant specific heats:

the first isentropic relation for

ideal gases

the second isentropic relation

for ideal gases
ENTROPY CHANGE OF IDEAL GASES:

Isentropic Processes of Ideal Gases

the third isentropic relation for
ideal gases
 Example:
1. Air is compressed in a piston–cylinder device from
100 kPa and 17°C to 800 kPa in a reversible,
adiabatic process. Determine the final temperature
and the work done during this process, assuming
constant specific heats.
 Example:
2. A container filled with 45 kg of liquid water at 95°C
is placed in a 90-𝒎𝟑 room that is initially at 12°C.
Thermal equilibrium is established after a while as a
result of heat transfer between the water and the air
in the room. Using constant specific heats, determine
(a) the final equilibrium temperature, (b) the amount
of heat transfer between the water and the air in the
room. Assume the room is well sealed and heavily insulated.