ADDIS ABABA SCIENCE AND TECHNOLOGY UNIVERSITY

COLLEGE OF ENGINEERING
MECHANICAL ENGINEERING DEPARTMENT

Engineering Thermodynamics
(EMEg3101)
CHAPTER- FIVE
ENTROPY

1
Lecture notes prepared by Bonsa R.
 Learning objectives
 By the end of this chapter you will be able to:
 Discuss the Clausius inequality
 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.

2
 Introduction
 In the preceding chapter we’ve applied the second law to cycles, this time we will
apply the second law to processes.
 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.

3
 The Clausius inequality and Entropy
 The second law of thermodynamics leads to expressions that involve inequality
(𝜂𝑟𝑒𝑣 > 𝜂𝑖𝑟𝑟𝑒𝑣 ; and 𝐶𝑂𝑃𝑟𝑒𝑣 > 𝐶𝑂𝑃𝑖𝑟𝑟𝑒𝑣 )
 Another important inequality is given by Clausius and termed as the Clausius
inequality and is given by;

𝛿𝑄
ර ≤0
𝑇
Where Q is the heat transfer between the system and the surroundings (reservoir) and T is the
temperature at the system boundary where the heat is being transferred.

4
 The Clausius inequality and Entropy
 To develop the Clausius inequality consider a combined system of
a reversible cyclic device and a piston cylinder system as shown.
Defining the combined work as;
𝛿𝑊𝑐 = 𝛿𝑊𝑟𝑒𝑣 + 𝛿𝑊𝑠𝑦𝑠

From the first law the energy balance for the combined system
𝐸𝑖𝑛 − 𝐸𝑜𝑢𝑡 = ∆𝐸𝑠𝑦𝑠
𝛿𝑄𝑅 − 𝛿𝑊𝑐 = 𝑑𝐸𝑠𝑦𝑠
Rearranging;
𝛿𝑊𝑐 = 𝛿𝑄𝑅 − 𝑑𝐸𝑠𝑦𝑠
For the reversible cyclic device;
𝛿𝑄𝑅 𝑇𝑅
=
𝛿𝑄 𝑇
Rearranging ;
𝛿𝑄
𝛿𝑄𝑅 = 𝑇𝑅
𝑇
5
 The Clausius inequality and Entropy
Sunstituting 𝛿𝑄𝑅 in the energy balance equation;
𝛿𝑄
𝛿𝑊𝑐 = 𝑇𝑅 − 𝑑𝐸𝑠𝑦𝑠
𝑇
For the system undergoing a cycle;
𝛿𝑄
𝑊𝑐 = ර 𝛿𝑊𝑐 = ර 𝑇𝑅 − 𝑑𝐸𝑠𝑦𝑠
𝑇
The cyclic integral of the change of energy of a system is zero and TR is constant then
we will have;
𝛿𝑄
𝑊𝑐 = 𝑇𝑅 ර
𝑇
The combined system is violating the Kelvin-Planck statement therefor the combined
work can not be positive.
𝑊𝑐 ≤ 0

6
 The Clausius inequality and Entropy
 To develop the Clausius inequality consider a combined system of
a reversible cyclic device and a piston cylinder system as shown.
TR is positive since its absolute temperature; therefore we remain with the
cyclic integral term to be less than or equal to zero. i.e.

𝛿𝑄
ර ≤0
𝑇
𝛿𝑄 𝛿𝑄
ර <0 ර =0
𝑇 𝑇

For irreversible process For internally reversible process

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 The Clausius inequality and Entropy
 For internally reversible process the cyclic integral is equal to zero; therefore the term
inside must be a change in a point function or a property.
𝛿𝑄
ර =0
𝑇
For example; during a cyclic process the total change in volume
would be;
ර 𝑑𝑉 = 0

Therefore ;
𝛿𝑄
𝑑𝑆 = (kJ/K)
𝑇 𝑖𝑛𝑡,𝑟𝑒𝑣

8
 The Clausius inequality and Entropy
 S is called entropy which is defined from the second law of thermodynamics.
 Entropy is an extensive property and the change in entropy during a process (1-2) can be given by
2
𝛿𝑄
𝑆2 − 𝑆1 = න
1 𝑇 𝑖𝑛𝑡,𝑟𝑒𝑣
 To perform the integration, one need to know the functional relationship between Q and T. In
most of cases its not available so we relay on property data tables.
A Special Case: [Internally Reversible Isothermal Heat Transfer Processes]
2 2
𝛿𝑄 𝛿𝑄 1 2 𝑄
∆𝑆 = න =න = න 𝛿𝑄 =
1 𝑇 𝑖𝑛𝑡,𝑟𝑒𝑣 1 𝑇0 𝑖𝑛𝑡,𝑟𝑒𝑣 𝑇0 1 𝑇
particularly useful for determining the entropy changes of thermal energy
reservoirs that can absorb or supply heat indefinitely at a constant temperature.

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 The Increase of Entropy Principle
 Consider a cycle that is made up of two processes as shown;
From Clausius inequality we have;
𝛿𝑄
ර ≤0
𝑇
Applying the Clausius inequality to this given cycle;
2 1
𝛿𝑄 𝛿𝑄 𝛿𝑄
ර =න +න ≤0
𝑇 1 𝑇 2 𝑇 𝑖𝑛𝑡,𝑟𝑒𝑣
2
𝛿𝑄
න + 𝑆1 − 𝑆2 ≤ 0
1 𝑇
Rearranging ;
2
𝛿𝑄
𝑆2 − 𝑆1 ≥ න
1 𝑇
Therefore :
2
𝛿𝑄
𝑑𝑆 ≥ න
1 𝑇
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 The Increase of Entropy Principle
 where the equality holds for an internally reversible process and the inequality for an
irreversible process.
 the change in entropy of a closed system undergoing an irreversible process is greater
than the entropy transfer by heat 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

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 The Increase of Entropy Principle
2
𝛿𝑄
∆𝑆𝑠𝑦𝑠 = 𝑆2 − 𝑆1 = න + 𝑆𝑔𝑒𝑛
1 𝑇
 The entropy generation is dependent on the process path, therefore it is not a property.
 In the absence of entropy transfer, the entropy change of a system is due to the entropy
generation.
 For an isolated system (or simply an adiabatic closed system), the heat transfer is zero;
∆𝑆𝑖𝑠𝑜𝑙𝑎𝑡𝑒𝑑 ≥ 0

The entropy of an isolated system during a process always increases or, in the limiting case of a reversible
process, remains constant. Entropy never decreases. This is known as the increase of entropy
principle.

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 The Increase of Entropy Principle
 The entropy change of this isolated system during a
process is the sum of the entropy changes of the
system and its surroundings, which is equal to the
entropy generation since an isolated system
involves no entropy transfer
𝑆𝑔𝑒𝑛 = ∆𝑆𝑡𝑜𝑡 = ∆𝑆𝑠𝑦𝑠 + ∆𝑆𝑠𝑢𝑟𝑟 ≥ 0
 The entropy of the universe is continuously
increasing.

• 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.

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 The Increase of Entropy Principle
 The increase of entropy can be summarised by;

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.
2. Entropy is a non-conserved property. 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 present during that
process.

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 Entropy Change of a pure substance
 Entropy is a property, i.e. it is defined
at a given state.
 Entropy as a property can be
determined from thermodynamic
property relation or from property
data like other properties.
 The entropy change of a specified mass
m (a closed system) during a process is
simply;

∆𝑆 = 𝑚(𝑠2 − 𝑠1 )

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 Entropy Change of a pure substance
 When studying the second-law aspects
of processes, entropy is commonly
used as a coordinate on diagrams such
as the T-s and h-s diagrams

General T-s diagram of a pure substance (water)

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 Entropy Change of a pure substance
Example:
A well-insulated rigid tank contains 3 kg of a saturated liquid–vapor mixture of water at 200 kPa.
Initially, three-quarters of the mass is in the liquid phase. An electric resistance heater placed in the
tank is now turned on and kept on until all the liquid in the tank is vaporized. Determine the entropy
change of the steam during this process.

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 Entropy Change of a pure substance
Isentropic process
 A process during which the entropy remains constant is called an isentropic process. It is
characterized by
∆𝑆 = 𝑆2 − 𝑆1 = 0
 For a closed system the entropy change is due to either by heat transfer or irreversibilities.
Therefore for a process involving no irreversibilities (reversible process) and no heat transfer
(adiabatic) the change in entropy is zero (isentropic).
 Reversible and adiabatic processes are always isentropic but the reverse is not true.

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 Entropy Change of a pure substance
Example:
Steam enters an adiabatic turbine at 5 MPa and
450 ℃ 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.

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 Property diagrams involving entropy
 In the second-law analysis, it is very helpful to
plot the processes on diagrams for which one of
the coordinates is entropy.
 The two common diagrams involving entropy
are the T-s and h-s diagrams.
 On a T-S diagram, the area under the process
curve represents the heat transfer for internally
reversible processes.
 Can you represent the Carnot cycle on a T-s diagram?

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 Property diagrams involving entropy
 The h-s diagram also known as Mollier
diagram is quite valuable in the analysis of
steady-flow devices such as turbines,
compressors, and nozzles.
 In analyzing the steady flow of steam through
an adiabatic turbine, for example, the vertical
distance between the inlet and the exit states
Δh is a measure of the work output of the
turbine, and the horizontal distance Δs is a
measure of the irreversibilities associated with
the process.

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 What is entropy?
The physical meaning of entropy can be discussed by considering the microscopic nature of matter
Entropy can be viewed as a measure of molecular disorder, or molecular randomness. As a system becomes
more disordered, the positions of the molecules become less predictable and the entropy increases.

From a microscopic point of view, the entropy of a system increases whenever the thermal randomness or disorder (i.e.,
the number of possible relevant molecular microstates corresponding to a given bulk macrostate) of a system increases.
Thus, entropy can be viewed as a measure of thermal randomness or molecular disorder, which increases anytime an
isolated system undergoes a process
As mentioned earlier, the molecules of a substance in solid phase continually oscillate, creating an uncertainty about their
position. These oscillations, however, fade as the temperature is decreased, and the molecules supposedly become motionless
at absolute zero. This represents a state of ultimate molecular order (and minimum energy). Therefore, 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

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 The T ds relations
 The differential change in entropy is defined from internally reversible process as
𝛿𝑄
𝑑𝑆 =
𝑇 𝑖𝑛𝑡,𝑟𝑒𝑣
 The change in entropy during a process is obtained by integrating the differential change from
initial to the final state. To do so one need to know functional relationship between 𝛿𝑄 and 𝑇.
 Assume a closed stationary system of a simple compressible substance undergoing a reversible
process; the differential energy balance is given by;

𝛿𝑄𝑖𝑛𝑡,𝑟𝑒𝑣 − 𝛿𝑊𝑖𝑛𝑡,𝑟𝑒𝑣 = 𝑑𝑈
𝛿𝑄𝑖𝑛𝑡,𝑟𝑒𝑣 = 𝑇𝑑𝑆
𝛿𝑊𝑖𝑛𝑡,𝑟𝑒𝑣 = 𝑃𝑑𝑉

23
 The T ds relations
 Thus;
𝑇𝑑𝑆 = 𝑑𝑈 + 𝑃𝑑𝑉 𝑘𝐽
𝑇𝑑𝑠 = 𝑑𝑢 + 𝑃𝑑𝑣 (𝑘𝐽/𝑘𝑔)
This equation is known as the first T ds, or Gibbs equation.
 The second T ds equation is obtained by eliminating du by the definition of enthalpy (h = u + Pv)
ℎ = 𝑢 + 𝑃𝑣 → 𝑑ℎ = 𝑑𝑢 + 𝑃𝑑𝑣 + 𝑣𝑑𝑃
𝑇𝑑𝑠 = 𝑑ℎ − 𝑣𝑑𝑃
 The T ds relations are defined from a reversible process but since they are property relations and
properties are state functions, they can be applied to any process (reversible or irreversible)
 The T ds relations are valid for both reversible and irreversible processes and for both closed and
open systems.

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 The T ds relations
 Explicit relations for differential changes in entropy are obtained by solving for ds
𝑑𝑢 𝑃𝑑𝑣
𝑑𝑠 = +
𝑇 𝑇

𝑑ℎ 𝑣𝑑𝑃
𝑑𝑠 = −
𝑇 𝑇
 The entropy change during a process can be determined by integrating either of these equations
between the initial and the final states.
 To perform these integrations, however, we must know the relationship between du or dh and the
temperature.
 For substance where these relationships are available the integration is straightforward but, for
other substances, we have to rely on tabulated data.

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 Entropy change of liquids and solids
 Solids and liquids are incompressible substances since their specific volumes remain nearly constant
during a process. i.e. 𝑑𝑣 ≅ 0
𝑑𝑢
 Therefore 𝑑𝑠 =
𝑇
 And for incompressible substance; 𝑐𝑃 = 𝑐𝑣 = 𝑐 and the specific heat is also as a function of
temperature;
For solids and liquids
2
𝑑𝑇 𝑇2
𝑠2 − 𝑠1 = න 𝑐(𝑇) ≅ 𝑐𝑎𝑣 ln
1 𝑇 𝑇1
For isentropic process;
𝑇2
𝑠2 − 𝑠1 = 𝑐𝑎𝑣 ln = 0 → 𝑇1 = 𝑇2
𝑇1

26
 Entropy change of Ideal Gases
 The entropy change for ideal gases can be obtained by applying the ideal gas equation and the
changes in internal energy and enthalpy expressions.
𝑑𝑢 𝑃𝑑𝑣
We have; first T ds Relation 𝑑𝑠 = +
𝑇 𝑇
𝑑ℎ 𝑣𝑑𝑃
and second T ds relation 𝑑𝑠 = −
𝑇 𝑇
For ideal gases : 𝑃𝑣 = 𝑅𝑇 and 𝑑𝑢 = 𝑐𝑣 𝑑𝑇 ; 𝑑ℎ = 𝑐𝑃 𝑑𝑇

𝑅𝑇
𝑃=
𝑣
𝑑𝑇 𝑑𝑣
Applying on the first Tds relation; 𝑑𝑠 = 𝑐𝑣 +𝑅
𝑇 𝑣

2
𝑑𝑇 𝑣2
The change in entropy during a process would 𝑠2 − 𝑠1 = න 𝑐𝑣 𝑇 + 𝑅 ln
be obtained by integrating as; 1 𝑇 𝑣1
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 Entropy change of Ideal Gases
 Similarly taking the second Tds relation;
𝑑ℎ 𝑣𝑑𝑃
𝑑𝑠 = −
𝑇 𝑇
For ideal gases : 𝑃𝑣 = 𝑅𝑇 and 𝑑𝑢 = 𝑐𝑣 𝑑𝑇 ; 𝑑ℎ = 𝑐𝑃 𝑑𝑇

𝑅𝑇
𝑣=
𝑃
𝑑𝑇 𝑑𝑃
𝑑𝑠 = 𝑐𝑃 −𝑅
𝑇 𝑃

2
The change in entropy during a process would 𝑑𝑇 𝑃2
be obtained by integrating as; 𝑠2 − 𝑠1 = න 𝑐𝑃 𝑇 − 𝑅 ln
1 𝑇 𝑃1

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 Entropy change of Ideal Gases
 To perform the integration, one need to know the functional relationship between the specific
heats and temperature. Even the functions are available, performing long integrations every
time entropy change is calculated is not practical.
 There are two options to determine the change in entropy;
I. perform these integrations by simply assuming constant specific heats
II. evaluate those integrals once and tabulate the results.

29
 Constant Specific Heats (Approximate Analysis)
 Under the constant-specific-heat assumption,
the specific heat is assumed to be constant at
some average value.
 We can replace 𝑐𝑣 (𝑇) and 𝑐𝑃 (𝑇) by 𝑐𝑣,𝑎𝑣𝑔
and 𝑐𝑃,𝑎𝑣𝑔 respectively

30 Unit-mole basis
 Variable Specific Heats (Exact Analysis)
 Constant specific heat assumptions are valid over small temperature changes and if the temperature
change is large we need to perform the integration, since the specific heat to temperature relations
are not linear.
 But instead of performing the integration for every process we encounter we relay on a tabulated
data of the results of integrations for different temperatures.
 For this purpose, we choose absolute zero as the reference temperature and define a function 𝑠° as
𝑇
𝑑𝑇
𝑠° = න 𝑐𝑃 𝑇
0 𝑇
 𝑠° is a function of temperature alone
 its value is zero at absolute zero temperature.
 The values of 𝑠° are calculated at various temperatures, and the results are tabulated in the appendix
as a function of temperature for air.

31
 Variable Specific Heats (Exact Analysis)
 The integral of 𝑐𝑝 𝑇 for process 1-2 is then
2
𝑑𝑇
න 𝑐𝑃 𝑇 = 𝑠°2 − 𝑠°1
1 𝑇
 Thus the change in entropy during a process 1-2 would be
𝑃2
𝑠2 − 𝑠1 = 𝑠°2 − 𝑠°1 − 𝑅 ln (𝑘𝐽/𝑘𝑔𝐾)
𝑃1
 Or per unit mole bases;

Note that The entropy of an ideal gas depends on both T and P

32
 Variable Specific Heats (Exact Analysis)
Example:
Air is compressed from an initial state of 100 kPa and 17℃ to a final
state of 600 kPa and 57℃. Determine the entropy change of air
during this compression process by using (a) property values from the
air table and (b) average specific heats.
(a) The properties of air are given in the air table (Table A–17)

At 𝑇1 = 17℃ = 345𝐾 → 𝑠°1 = 1.66802kJ/kg.K

𝑇2 = 57℃ = 330𝐾 → 𝑠°2 = 1.79783kJ/kg.K
𝑅 = 0.2870kJ/kg.K
𝑃2
𝑠2 − 𝑠1 = 𝑠°2 − 𝑠°1 − 𝑅 ln = −0.3844 kJ/kg·K
𝑃1
33
 Variable Specific Heats (Exact Analysis)
(b) By approximation method (using average specific heats)
𝑇1 + 𝑇2
𝑇𝑎𝑣𝑔 = = 37℃ = 310𝐾
2
𝑐𝑃,𝑎𝑣𝑔 = 𝑐𝑃@𝑇𝑎𝑣𝑔 ≅ 1.006kJ/kgK
𝑇2 𝑃2
𝑠2 − 𝑠1 = 𝑐𝑃,𝑎𝑣𝑔 ln − 𝑅 ln = −0.3842 kJ/kg·K
𝑇1 𝑃1

34
 Isentropic Processes of Ideal Gases
Constant Specific Heats (Approximate Analysis)
 By setting the first and second entropy relation equal to zero;
first isentropic relation
From first entropy relation

Which can be reduced to; 𝑇𝑣 1−𝑘 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡

From second entropy relation

second isentropic relation

35 Which can be reduced to; 𝑇𝑃(1−𝑘)/𝑘 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡

 Isentropic Processes of Ideal Gases
Constant Specific Heats (Approximate Analysis)
 The third isentropic relation is obtained by equating the first and second relations
The third entropy relation

Which can be reduced to; P𝑣 𝑘 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡

third isentropic relation

36
 Isentropic Processes of Ideal Gases
Variable Specific Heats (Exact Analysis)
 Obtained by setting the entropy relation equal to zero;
𝑃2 𝑃2
0 = 𝑠°2 − 𝑠°1 − 𝑅 ln → 𝑠°2 − 𝑠°1 = 𝑅 ln
𝑃1 𝑃1
Relative Pressure and Relative Specific Volume
Rearranging the isentropic relation;
𝑠°2
𝑃2 𝑠°2 − 𝑠°1 𝑃2 𝑒𝑅 𝑃𝑟2
ln = → = 𝑠°1
=
𝑃1 𝑅 𝑃1 𝑃𝑟1
𝑒𝑅
𝑃𝑟 is called the relative pressure
 Pr is a dimensionless quantity that is a function of temperature only since s° depends on
temperature alone.
 Therefore, values of Pr can be tabulated against temperature.
37
 Isentropic Processes of Ideal Gases
Variable Specific Heats (Exact Analysis)
 Sometimes specific volume ratios are given instead of pressure ratios.
 In such cases, one needs to work with volume ratios. This can be done by applying the ideal
gas equation

38