11/18/2021
Unit-III
Entropy : Clausius inequality, Concept of Entropy, Entropy change in
different thermodynamic processes, Tds equation, Principle of
entropy increase, T-S diagram, Statement of the third law of
thermodynamics.
Availability and Irreversibility: Available and unavailable energy,
Availability and Irreversibility, Second law efficiency, Helmholtz &
Gibb’s function.
Two Reversible Adiabatic Paths Cannot intersect each
other
1
11/18/2021
Clausius Theorem
Clausius Theorem
Reversible Path Substituted by
two Reversible Adiabatics and
a Reversible Isotherm
The cyclic integral of δQ/T is always less than or equal to zero. This
inequality is valid for all cycles, reversible or irreversible. The symbol
(integral symbol with a circle in the middle) is used to indicate that the
integration is to be performed over the entire cycle.
2
11/18/2021
Clausius Theorem
Definition of Entropy
The cyclic integral of volume (or any
other property) 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 (δQ/T)int rev
must represent a property in the
differential form.
Clausius realized in 1865 that he had
discovered a new thermodynamic
property, and he chose to name this
property entropy. It is designated S
and is defined as
3
11/18/2021
Definition of Entropy
• Entropy is an extensive property of a system and sometimes is referred to
as total entropy.
• Entropy per unit mass, designated s, is an intensive property and has the
unit kJ/kg · K.
• The term entropy is generally used to refer to both total entropy and
entropy per unit mass since the context usually clarifies which one is
meant.
• The entropy change of a system during a process can be determined by
integrating Eq. between the initial and the final states:
• Entropy is a property, and like all other properties, it has fixed values at
fixed states.
• Therefore, the entropy change S between two specified states is the
same no matter what path, is followed during a process.
Definition of Entropy
• Also note that the integral of dQ/T gives us the
value of entropy change only if the integration
is carried out along an internally reversible path
between the two states.
• The integral of dQ/T along an irreversible path
is not a property, and in general, different
values will be obtained when the integration is
carried out along different irreversible paths.
• Therefore, even for irreversible processes, the
entropy change should be determined by
carrying out this integration along some
convenient imaginary internally reversible path
between the specified states.
4
11/18/2021
The Property of Entropy
Temperature Entropy Plot
Inequality of Clausius
10
5
11/18/2021
Inequality of Clausius
11
Entropy Change in an Irreversible Process:
12
6
11/18/2021
Tds Equations
13
THE INCREASE OF Entropy Principle
14
7
11/18/2021
THE INCREASE OF Entropy Principle
15
THE INCREASE OF Entropy Principle
• The equality holds for an internally reversible process and the
inequality for an irreversible process.
• We may conclude from these equations that the entropy change of
a closed system during an irreversible process is greater than the
integral of dQ/T evaluated for that process.
• In the limiting case of a reversible process, these two quantities
become equal.
16
8
11/18/2021
THE INCREASE OF Entropy Principle
• The inequality sign in the preceding relations is a constant reminder
that the entropy change of a closed system during an irreversible
process is always greater than the entropy transfer.
• 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 by Sgen.
• The difference between the entropy change of a closed system and the
entropy transfer is equal to entropy generation and can be rewritten as
• The entropy generation Sgen is always a positive quantity or zero
• Its value depends on the process, and thus it is not a property of the
system.
17
THE INCREASE OF Entropy Principle
• For an isolated system (or simply an adiabatic closed system), the heat
transfer is zero, the equation reduces to
• This equation can be expressed as the
entropy of an isolated system during a
process always increases or, in the
limiting case of a reversible process,
remains constant. In other words, it
never decreases. This is known as the
increase of entropy principle.
• In the absence of any heat transfer,
entropy change is due to
irreversibilities only, and their effect is
always to increase entropy.
18
9
11/18/2021
THE INCREASE OF Entropy Principle
• No actual process is truly reversible, we can conclude that some
entropy is generated during a process, and therefore the entropy of
the universe, which can be considered to be an isolated system, is
continuously increasing.
• The more irreversible a process, the larger the entropy generated
during that process.
• No entropy is generated during reversible processes (Sgen = 0).
• The increase of entropy principle does not imply that the entropy of
a system cannot decrease. The entropy change of a system can be
negative during a process, but entropy generation cannot.
• The increase of entropy principle can be summarized as follows:
19
SOME REMARKS ABOUT ENTROPY
• 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.
• Entropy is a non-conserved 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.
• 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.
• The greater the extent of irreversibilities, the greater the entropy
generation. Therefore, entropy generation can be used as a
quantitative measure of irreversibilities associated with a process.
20
10
11/18/2021
Third Law of Thermodynamics
• The entropy of a pure crystalline substance at absolute zero
temperature is zero since there is no uncertainty about the state
of the molecules at that instant.
• This statement is known as the third law of thermodynamics.
• The third law of thermodynamics provides an absolute reference
point for the determination of entropy.
• The entropy determined relative to this point is called absolute
entropy, and it is extremely useful in the thermodynamic
analysis of chemical reactions.
21
Application of Entropy Principle
• Transfer of heat through a Finite Temperature Difference
22
11
11/18/2021
Application of Entropy Principle
• Mixing of Two Fluids
23
• Maximum work obtainable from Two Finite Bodies at Temperatures T1 and T2
24
12
11/18/2021
• Maximum work obtainable from a Finite Bodies and a TER
25
Entropy - Numerical
Q1. Two kg of water at 80°C are mixed adiabatically with 3 kg of water at 30°C in a
constant pressure process of 1 atmosphere. Find the increase in the entropy of the total
mass of water due to the mixing process (cp of water = 4.187 kJ/kg K).
[Ans. 0.0576 kJ/K]
26
13
11/18/2021
Entropy - Numerical
Q2. A heat engine receives reversibly 420 kJ/cycle of heat from a source at 327°C, and rejects heat
reversibly to a sink at 27°C. There are no other heat transfers. For each of the three hypothetical
amounts of heat rejected, in (a), (b), and (c) below, compute the cyclic integral of dQ/T. which
impossible:
(a) 210 kJ/cycle rejected
(b) 105 kJ/cycle rejected
(c) 315 kJ/cycle rejected
[Ans: (a) Reversible, (b) Impossible, (c) Irreversible]
27
Entropy - Numerical
Q3. Water is heated at a constant pressure of 0.7 MPa. The boiling point is 164.97°C. The initial
temperature of water is 0°C. The latent heat of evaporation is 2066.3 kJ/kg. Find the increase of
entropy of water, if the final state is steam
[Ans. 6.6967 kJ/kg K]
28
14
11/18/2021
Entropy - Numerical
Q5. Ten grammes of water at 20°C is converted into ice at –10°C at constant atmospheric
pressure. Assuming the specific heat of liquid water to remain constant at 4.2 J/gK and that of ice
to be half of this value, and taking the latent heat of fusion of ice at 0°C to be 335 J/g, calculate
the total entropy change of the system.
[Ans. 16.02 J/K]
29
A reversible engine, as shown in Figure during a cycle of operations draws 5 MJ from
the 400 K reservoir and does 840 kJ of work. Find the amount and direction of heat
interaction with other reservoirs.
[Ans: Q3 = +820 kJ/kg, Q2 = - 4980 kJ/kg]
30
15
11/18/2021
A heat engine receives reversibly 420 kJ/cycle of heat from a source at 327°C, and
rejects heat reversibly to a sink at 27°C. There are no other heat transfers. For each
of the three hypothetical amounts of heat rejected, in (a), (b), and (c) below, compute
the cyclic integral of dQ/T. which impossible:
(a) 210 kJ/cycle rejected
(b) 105 kJ/cycle rejected
(c) 315 kJ/cycle rejected
31
Ten grammes of water at 20°C is converted into ice at –10°C at constant
atmospheric pressure. Assuming the specific heat of liquid water to remain constant
at 4.2 J/gK and that of ice to be half of this value, and taking the latent heat of fusion
of ice at 0°C to be 335 J/g, calculate the total entropy change of the system.
(Ans. 16.02 J/K)
32
16
11/18/2021
33
34
17
11/18/2021
35
36
18
11/18/2021
37
THANK YOU
38
19
