Engineering Thermodynamics The concept of entropy

Chapter Six
The Concept of Entropy
Engineering Thermodynamics The concept of entropy

Definition of Entropy
• Entropy is a somewhat abstract property, and it is difficult to give a physical
description of it without considering the microscopic state of the system.
• Entropy is best understood and appreciated by studying its uses in commonly
encountered engineering processes, and this is what we intend to do.
• The second law of thermodynamics leads to the definition of a new property
called entropy.
• Entropy is a quantitative measure of microscopic disorder for a system.
• Entropy is a measure of energy that is no longer available to perform useful
work within the current environment.

By: Berihu G.(PhD) 2

Engineering Thermodynamics The concept of entropy

Entropy and the Clausius Inequality

• Another important inequality that has major consequences in thermodynamics is
the Clausius inequality and it is derived to obtain the working definition of
entropy and, thus, the second law.
(6.1)

• This equation is called the Clausius inequality.

• The equality holds for the reversible process and the inequality holds for the irreversible
process.
• That is, the cyclic integral of dδ/T is always less than or equal to zero.
• This inequality is valid for all cycles, reversible or irreversible.
3
Engineering Thermodynamics The concept of entropy

Definition of Entropy
• 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.
• Any heat transfer to or from a system can be considered to consist of differential
amounts of heat transfer.
• If no irreversibilities occur within the system as well as the reversible cyclic
device, then the cycle undergone by the combined system is internally
reversible.
• Therefore, for internally reversible cycles.
(6.2)

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Engineering Thermodynamics The concept of entropy

Definition of Entropy
• 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 (Q/T)int rev must be a property and called entropy (S).
• Entropy is an extensive property 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.

By: Berihu G.(PhD) 5

Engineering Thermodynamics The concept of entropy

Definition of Entropy
• The entropy change of a system during a process can be determined by integrating
Eq. 6.1 between the initial and the final states:
(kJ/K) (6.3)

By: Berihu G.(PhD) 6

Engineering Thermodynamics The concept of entropy

The Increase of Entropy Principle

• Consider the cycle that is made up of two process, process 1-2, which is arbitrary (rev. or
irreve.) and process 2-1, which is internally reversible.

• From the Clausius inequality Eq. (6.1)

2 1 (6.4)
𝛿𝑄 𝛿𝑄
න +න ≤0
1 𝑇 2 𝑇 𝑖𝑛𝑡𝑒,𝑟𝑒𝑣

• The second integral along the internally reversible path is considered as the entropy
change, S1–S2. Therefore,

• Which can be rearranged as (6.5)

• It can also be expressed in differential form as (6.6)

By: Berihu G.(PhD) 7
Engineering Thermodynamics The concept of entropy

The Increase of Entropy Principle….

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.

(6.7)
• It is important for you to recognize that Q has a sign depending on the direction of heat
transfer.
• 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
• The reversible, adiabatic process is called an isentropic process. S2 = S1 (6.8)
By: Berihu G.(PhD) 8
Engineering Thermodynamics The concept of entropy

The Increase of Entropy Principle…..

• 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.
• The entropy change during a process is obtained by integrating the dS equation over the
process: (6.9)
• 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.

By: Berihu G.(PhD) 9

Engineering Thermodynamics The concept of entropy

The Increase of Entropy Principle…..

• 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
(6.10)
• 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.
By: Berihu G.(PhD) 10
Engineering Thermodynamics The concept of entropy

Definition of Second Law of Thermodynamics

• 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

(6.11)
• 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.
By: Berihu G.(PhD) 11
Engineering Thermodynamics The concept of entropy

Definition of Second Law of Thermodynamics…

• Now consider a general system exchanging mass as well as energy with
its surroundings. S gen = Stotal = S sys +  S surr  0 (6.12)

where = holds for the totally reversible process

> holds for the irreversible process
• 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 total entropy change for a process is the amount of entropy generated during that process
(Sgen), and it is equal to the sum of the entropy changes of the system and the surroundings.

By: Berihu G.(PhD) 12

Engineering Thermodynamics The concept of entropy

Definition of Second Law of Thermodynamics…

• 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.
• 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:

(6.13)
By: Berihu G.(PhD) 13
Engineering Thermodynamics The concept of entropy

Some Remarks about Entropy

i. Processes can occur in a certain direction only, not in just any direction. A process must
proceed in the direction that complies with the increase of entropy principle, such that Sgen≥0.
ii. 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 entropy of the universe is continuously increasing.
iii. 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. It is also used to establish criteria for the performance of
engineering devices.

By: Berihu G.(PhD) 14

Engineering Thermodynamics The concept of entropy

Property Diagrams Involving Entropy

• Property diagrams serve as great visual aids in the thermodynamic analysis of processes.
• We have used P-v and T-v diagrams extensively in previous chapters in conjunction with
the first law of thermodynamics.
• In the 2nd TD law analysis, it is very helpful to plot the processes on diagrams for which
one of the coordinates is entropy.
• The two diagrams commonly used in the second-
law analysis are the temperature-entropy and the
enthalpy-entropy diagrams.

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Engineering Thermodynamics The concept of entropy

Property Diagrams Involving Entropy…

❖ Heat Transfer at the Area under a T-S Curve
• For the reversible process, the equation for dS implies that
Qnet
dS =
T
Qnet = TdS
• 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. (6.14)
• In the above figure, the heat transfer in an internally reversible process is shown as
the area under the process curve plotted on the T-S diagram.

By: Berihu G.(PhD) 16

Engineering Thermodynamics The concept of entropy

Property Diagrams Involving Entropy…

❖ Isothermal Reversible Process
• For an isothermal, reversible process, the temperature is constant and the integral
to find the entropy change is readily performed.
• If the system has a constant temperature, T0, the entropy change becomes

(6.15)

• For a process occurring over a varying temperature, the entropy change must be
found by integration over the process.

By: Berihu G.(PhD) 17

Engineering Thermodynamics The concept of entropy

Property Diagrams Involving Entropy…

❖ Adiabatic Reversible (Isentropic) Process

• For an adiabatic process, one in which there is no heat transfer, the entropy change is

(6.16)
• If the process is adiabatic and reversible, the equality holds and the entropy change is
S = S2 − S1 = 0
S2 = S1
S
• On a per unit mass basis s=
m
s2 = s1
• The adiabatic, reversible process is a constant entropy process and is called isentropic.

By: Berihu G.(PhD) 18

Engineering Thermodynamics The concept of entropy

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.

By: Berihu G.(PhD) 19

Engineering Thermodynamics The concept of entropy

Entropy Change of Pure Substances

• 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
Qint rev − Wint rev, out = dU
Qint rev Wint rev, out Qint rev = T dS
Wint rev, out = P dV
System used to find expressions for ds
TdS − P dV = dU
• On a unit mass basis we obtain the first Tds equation, or Gibbs equation, as
Tds = du + Pdv (6.17)
• Recall that the enthalpy is related to the internal energy by h = u + Pv.
• Using this relation in the above equation, the second Tds equation is
By: Berihu G.(PhD)
T ds = dh − v dP (6.18) 20
Engineering Thermodynamics The concept of entropy

Entropy Change of Pure Substances……

• These last two relations have many uses in thermodynamics and serve as the starting point in
developing entropy-change relations for processes.
• The successful use of Tds relations depends on the availability of property relations.

• Such relations do not exist in an easily used form for a general pure substance but are available
for incompressible substances (liquids, solids) and ideal gases

By: Berihu G.(PhD) 21

Engineering Thermodynamics The concept of entropy

Entropy Change of Pure Substances……

• For the general pure substance, such as water and the refrigerants, we must resort to
property tables to find values of entropy and entropy changes.
• The temperature-entropy and enthalpy-entropy diagrams for water are shown below.

• The Fig. shown below is the temperature-entropy

and enthalpy-entropy diagrams for water.
• The h-s diagram, called the Mollier diagram, is a
useful aid in solving steam power plant problems.

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Engineering Thermodynamics The concept of entropy

Entropy Change and Isentropic Processes

• The entropy-change and isentropic relations for a process can be summarized as follows:
1. Pure substances:
Any process: s = s2 − s1 (kJ/kgK)
Isentropic process: s2 = s1
du P
2. Incompressible substances (Liquids and Solids): ds = + dv
T T
• The change in internal energy and volume for an incompressible substance is
du = C dT
dv  0

• The entropy change now becomes

(6.19)
By: Berihu G.(PhD) 23
Engineering Thermodynamics The concept of entropy

Entropy Change and Isentropic Processes…..

• If the specific heat for the incompressible substance is constant, then the entropy change is
T2
Any process: s2 − s1 = Cav ln (kJ/kgK) (6.20)
T1
Isentropic process: T2 = T1
3. Ideal gases:
For Constant specific heats (approximate treatment):
✓ Any process:
𝑑𝑇 𝑑𝑉
𝑑𝑈 𝑃𝑑𝑉 (6.21) 𝑑𝑠 = 𝐶𝑣 +𝑅
𝑑𝑠 = + 𝑇 𝑇
𝑇 𝑇
𝑇2 𝑣2
𝑠2 − 𝑠1 = 𝐶𝑣 𝑙𝑛 + 𝑅𝑙𝑛 (6.22)
𝑇1 𝑣1

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Engineering Thermodynamics The concept of entropy

Entropy Change and Isentropic Processes…..

• A second relation for the entropy change of an ideal gas is obtained in a similar manner
by substituting dh = cp dT and v = RT/P into ds = dh/T – vdP/T and integrating
T2 P .
• The result is s2 − s1 = C p , av ln − R ln 2 (6.23)
T1 P1
• Isentropic process:
k
 P2   v1 
  =   (6.24)
 P1  s = const .  v2 

• For an isentropic process this last result looks like Pvk = constant which is the polytropic
process equation Pvn = constant with n = k = Cp/Cv.

By: Berihu G.(PhD) 25

Engineering Thermodynamics The concept of entropy

Example
6.1 Find the entropy and/or temperature of steam at the following states:

P T Region s kJ/(kg K)
5 MPa 120oC
1 MPa 50oC
1.8 MPa 400oC
40 kPa Quality, x = 0.9
40 kPa 7.1794

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Engineering Thermodynamics The concept of entropy

Example …
6.2 Determine the entropy change of water contained in a closed system as it
changes phase from saturated liquid to saturated vapor when the pressure is 0.1 MPa
and constant. Why is the entropy change positive for this process?

6.3 Steam at 1 MPa, 600oC, expands in a turbine to 0.01 MPa. If the process is
isentropic, find the final temperature, the final enthalpy of the steam, and the turbine
work.

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Engineering Thermodynamics The concept of entropy

Example …
6.4 Aluminum at 100oC is placed in a large, insulated tank having 10 kg of water
at a temperature of 30oC. If the mass of the aluminum is 0.5 kg, find the final
equilibrium temperature of the aluminum and water, the entropy change of the
aluminum and the water, and the total entropy change of the universe because of
this process. Before we work the problem, what do you think the answers ought
to be? Are entropy changes going to be positive or negative? What about the
entropy generated as the process takes place?

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Engineering Thermodynamics The concept of entropy

Example …
6.5 An iron cube at a temperature of 400°C is dropped into an insulated bath
containing 10 kg water at 25°C. The water finally reaches a temperature of 50°C at
steady state. Given that the specific heat of water is equal to 4186 J/kg K. Find the
entropy changes for the iron cube and the water. Is the process reversible ? If so
why ?
6.6 Air at 20°C and 1.05 bar occupies 0.025 m3. The air is heated at constant
volume until the pressure is 4.5 bar, and then cooled at constant pressure back to
original temperature. Calculate : (i) The net heat flow from the air, ii) The net
entropy change. Sketch the process on T-s diagram
By: Berihu G.(PhD) 29
Engineering Thermodynamics The concept of entropy

Example …
6.7 Calculate the change of entropy of 1 kg of air expanding polytropically in a
cylinder behind a piston from 7 bar and 600°C to 1.05 bar. The index of expansion
is 1.25.
6.8 1 kg of air initially at 8 bar pressure and 380 K expands polytropically (pv1.2 =
constant) until the pressure is reduced to one-fifth value. Calculate :
(i) Final specific volume and temperature.
(ii) Change of internal energy, work done and heat interaction.
(iii) Change in entropy.
Take : R = 0.287 kJ/kg K and γ = 1.4.
By: Berihu G.(PhD) 30