Entropy and Entropy Generation

Entropy calculations–closed systems

Dr. Amr Ibrahim

Thermodynamics
Dr. Amr Ibrahim

Entropy can be viewed as a measure of molecular disorder, or molecular randomness.

• Efficient people lead low-entropy (highly organized) lives. They have a place for
everything (minimum uncertainty), 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 (if not hours) 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
• some people seem to learn fast and remember well what they learn. We can call this type
of learning organized or low-entropy learning. These people make a conscientious effort to
file the new information properly by relating it to their existing knowledge base and creating
a solid information network in their minds.
• On the other hand, people who throw the information into their minds as they study, with
no effort to secure it, may think they are learning. During a test, It is not easy to retrieve
information
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Thermodynamics
Dr. Amr Ibrahim

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. To each state
of macroscopic equilibrium there correspond a large number of possible microscopic states or molecular
configurations.

The entropy of a system is related to the total number of possible microscopic States of
that system, called thermodynamic probability

Thus, it is not surprising that the entropy of a substance is lowest in the solid phase and highest in the gas
phase. In the solid phase, the molecules of a substance continually oscillate about their equilibrium
positions, but they cannot move relative to each other, and their position at any instant can be predicted
with good certainty. In the gas phase, however, the molecules move about at random, collide with each
other, and change direction, making it extremely difficult to predict accurately the microscopic state of a
system at any instant.

Thus, entropy is a measure of molecular disorder, and the molecular disorder (uncertainty (i.e., molecular
probability) of an isolated system increases anytime it undergoes a process
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Thermodynamics
Dr. Amr Ibrahim

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).

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

Notice that the entropy of a substance that is not pure crystalline (such as a solid solution) is not zero
at absolute zero temperature. This is because more than one molecular configuration exists for such
substances, which introduces some uncertainty about the microscopic state of the substance.

The entropy of a system approaches a constant value as its temperature approaches

absolute zero.
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Thermodynamics
Dr. Amr Ibrahim

Entropy generation is not related to energy transfer by work

Clausius inequality that states that for any thermodynamic cycle

Where δQ represents the heat transfer at a part of the

system boundary during a portion of the cycle,

T is the absolute temperature at that part of the

boundary.
The subscript “b” serves as a reminder that the
integration is evaluated at the boundary of the system
executing the cycle.

The symbol ∫ indicates that the integral is to be

performed over all parts of the boundary and over the
 Q 
entire cycle.
The equality hold for internally or totally reversible
  T b  0
process and the inequality hold for irreversible process 5
Thermodynamics
Dr. Amr Ibrahim

• A reversible process is defined as a process that can be

reversed without leaving any trace on the surroundings .That is,
both the system and the surroundings are returned to their initial
states at the end of the reverse process. Processes that are not
reversible are called irreversible processes.

• Reversible processes actually do not occur in nature.

• There are two reasons to study reversible processes:
• First, they are easy to analyze, since a system passes through a
series of equilibrium states during a reversible process. Second,
they serve as idealized models to which actual processes can be
compared.

Engineers are interested in reversible processes because work-producing devices such as car engines and gas or
steam turbines deliver the most work, and work-consuming devices such as compressors, fans, and pumps
consume the least work when reversible processes are used instead of irreversible ones. Reversible processes
can be viewed as theoretical limits for the corresponding irreversible ones.
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Thermodynamics
Dr. Amr Ibrahim

Irreversibilities: factors that cause a process to be irreversible (present within the system, its
surroundings, or both.)
Irreversibilities:
 Unrestrained expansion of a gas or liquid to a lower pressure
 Spontaneous chemical reaction
 Spontaneous mixing of matter at different compositions or states
 Friction—sliding friction as well as friction in the flow of fluids
 Electric current flow through a resistance

Internally Reversible Processes

is one in which there are no irreversibilities within the system. Irreversibilities may be located within the
surroundings

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Thermodynamics
Dr. Amr Ibrahim

 Q  2 𝛿𝑄 1 𝛿𝑄
  T b  0 ‫׬‬1 𝑇 + ‫׬‬2 𝑇 =0
𝐴 𝐵

Assume three 2 𝛿𝑄 1 𝛿𝑄
internally reversible ‫׬‬1 𝑇 + ‫׬‬2 𝑇 =0
processes
𝐴 𝐶
2
𝛿𝑄
𝑇ℎ𝑖𝑠 𝑚𝑒𝑎𝑛𝑠 𝑡ℎ𝑒 𝑖𝑛𝑡𝑔𝑟𝑎𝑙: න = 𝑑𝑜𝑒𝑠 𝑛𝑜𝑡 𝑑𝑒𝑝𝑒𝑛𝑑 𝑜𝑛 𝑡ℎ𝑒 𝑝𝑎𝑡ℎ
1 𝑇
the integral represents the change in some property of the system. Selecting
the symbol S to denote this property, which is called entropy

2
𝛿𝑄
න = ∆𝑆 = 𝑆2 − 𝑆1
1 𝑇
2
𝛿𝑄
= 𝑑S, then Q = TdS === Q =  TdS
𝑇
1
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Thermodynamics
Dr. Amr Ibrahim

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Thermodynamics
Dr. Amr Ibrahim

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Thermodynamics
Dr. Amr Ibrahim

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Thermodynamics
Dr. Amr Ibrahim

Steam Gas

𝚫𝑼 = 𝒎(𝒖𝟐 − 𝒖𝟏) 𝚫𝑼 = 𝒎𝑪𝒗𝚫𝑻

𝚫𝑯 = 𝒎(𝒉𝟐 − 𝒉𝟏) 𝚫𝑯 = 𝒎𝑪𝒑𝚫𝑻

𝚫𝑺 = 𝒎(𝒔𝟐 − 𝒔𝟏)
𝚫𝑺 = 𝑫𝒆𝒑𝒆𝒏𝒅𝒔 𝒐𝒏 𝒕𝒉𝒆 𝒑𝒓𝒐𝒄𝒆𝒔𝒔

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Thermodynamics
Dr. Amr Ibrahim

𝑹𝒊𝒈𝒊𝒅 𝑪𝒐𝒏𝒕𝒂𝒊𝒏𝒆𝒓 (V1=V2)

Ein-Eout= 𝐄𝐬𝐲𝐬𝐭𝐞𝐦
??
𝑸 − 𝑾 = ∆𝑼 + ∆𝑲𝑬 + ∆𝑷𝑬 For stationary system: ∆𝑲𝑬 + ∆𝑷𝑬=0

𝑸 − [𝑾𝒃 − 𝑾𝒐𝒕𝒉] = ∆𝑼

𝟐 0
𝑾𝟏−𝟐 = න 𝑷. 𝐝𝑽 = 𝟎 If the Woth=0
𝟏

𝑸 − [𝑾𝒃 − 𝑾𝒐𝒕𝒉] = ∆𝑼

For Steam: 𝑸 = 𝒎(𝒖𝟐 − 𝒖𝟏)

For gas: 𝑸 = ∆𝑼= 𝒎𝑪𝒗∆T

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Thermodynamics
Dr. Amr Ibrahim

𝛿𝑄
𝑸 = ∆𝑼= 𝒎𝑪𝒗∆T = 𝑑S
𝑇
𝛿𝑸 = 𝒅𝑼= 𝒎𝑪𝒗𝒅T
𝛿𝑄 = 𝑇𝑑S
𝑇𝑑S= 𝒎𝑪𝒗𝒅T

𝒅𝑻
𝑑S= 𝒎𝑪𝒗
𝑻
𝟐 𝟐
𝒅𝑻
න 𝑑S = න 𝒎𝑪𝒗
𝟏 𝟏 𝑻
𝑇2
∆𝑺 = 𝑺𝟐 − 𝑺𝟏 = 𝒎𝒄𝒗 ln
𝑇1

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Thermodynamics
Dr. Amr Ibrahim

(P1=P2)
Ein-Eout= 𝐄𝐬𝐲𝐬𝐭𝐞𝐦
𝑸 − 𝑾 = ∆𝑼 + ∆𝑲𝑬 + ∆𝑷𝑬 For stationary system: ∆𝑲𝑬 + ∆𝑷𝑬=0

𝑸 − [𝑾𝒃 − 𝑾𝒐𝒕𝒉] = ∆𝑼

𝟐 𝟐
𝑾𝟏−𝟐 = න 𝑷. 𝐝𝑽 = 𝟎 = 𝑷 න 𝐝𝑽 = 𝑷 𝑽𝟐 − 𝑽𝟏 = 𝒎𝑷 𝒗𝟐 − 𝒗𝟏
𝟏 𝟏

If the Woth=0
𝑸 − 𝑷 𝑽𝟐 − 𝑽𝟏 = 𝑼𝟐 − 𝑼𝟏 For Steam 𝑸 = 𝒎(𝒉𝟐 − 𝒉𝟏)

𝐐 = (𝐔2+PV2)-(U1- PV2)
For gas: 𝑸 = 𝒎 𝑪𝒑∆T
𝐐 = 𝐇𝟐 − 𝐇𝟏
𝐐 = 𝚫𝐇
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Thermodynamics
Dr. Amr Ibrahim

𝛿𝑄
𝑸 = ∆𝑼= 𝒎𝑪𝒑∆T = 𝑑S
𝑇
𝛿𝑸 = 𝒅𝑼= 𝒎𝑪𝒑𝒅T 𝛿𝑄 = 𝑇𝑑S,
𝑄 = 𝑇𝑑S
𝑇𝑑S= 𝒎𝑪𝒑𝒅T
𝒅𝑻
𝑑S= 𝒎𝑪𝒑
𝑻
𝟐 𝟐
𝒅𝑻
න 𝑑S = න 𝒎𝑪𝒑
𝟏 𝟏 𝑻

𝑇2
∆𝑺 = 𝑺𝟐 − 𝑺𝟏 = 𝒎𝒄𝒑 ln
𝑇1

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Thermodynamics
Dr. Amr Ibrahim

𝑄 − 𝑊 = ∆𝑈 >> 𝑄 − (𝑊𝑏 + 𝑊𝑜𝑡ℎ) = ∆𝑈 If the Woth=0

2

For Steam Q−𝑊𝑏 = ∆𝑈 𝛿Q−𝛿𝑊𝑏 =dU 𝛿𝑄 = 𝑇𝑑S >> 𝑄 = න 𝑇𝑑S >> 𝑄 = 𝑇∆S
1

TdS − 𝑊𝑏 =m(u2-u1)

For gas: 𝑄 − 𝑊𝑏 =mCv(T2-T1)

𝑄 = 𝑊𝑏

P1V1=mRT1 T1=T1=To, and therefore,

P2V2=mRT2 P1V1=P2V2=mRTC , PV=C

𝑉2 𝑉2 𝑉2 𝑉2
>> Q=𝑚𝑅𝑇 ln >> T ∆S=𝑚𝑅𝑇 ln >> ∆S=𝑚𝑅 ln
𝑄 = 𝑊𝑏 = 𝑐 ln 𝑉1 𝑉1 𝑉1
𝑉1
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Thermodynamics
Dr. Amr Ibrahim

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Thermodynamics
Dr. Amr Ibrahim

The process in which pressure and volume are related by 𝑃𝑉 𝑛 = C, where n and C are constants.

𝑃𝑉 𝑛 = C 𝑄 − (𝑊𝑏 + 𝑊𝑜𝑡ℎ) = ∆𝑈 if Woth=0

𝑃2𝑉2 − 𝑃1𝑉1
Steam: Q−(𝑊𝑏) = 𝑚(𝑢2 − 𝑢1) 𝑊𝑏 =
1−𝑛

gas: 𝑄𝑛𝑒𝑡 − (𝑊𝑏) = 𝑚𝐶𝑣(𝑇2 − 𝑇1) 𝑃2𝑉2 − 𝑃1𝑉1

𝑊𝑏 =
1−𝑛

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Thermodynamics
Dr. Amr Ibrahim

∆𝑺 𝟐 − 𝟏 = 𝑺𝑨 − 𝑺𝟏 + (𝑺𝟐 − 𝑺𝑨)

𝑉2 𝑇2
𝑺𝟐 − 𝑺𝟏 = 𝑚𝑅𝑇 ln + 𝒎𝒄𝒗 ln
𝑉1 𝑇1 20
Thermodynamics
Dr. Amr Ibrahim

∆𝑺 𝟐 − 𝟏 = 𝑺𝑨 − 𝑺𝟏 + (𝑺𝟐 − 𝑺𝑨)

𝑃1 𝑇2
𝑺𝟐 − 𝑺𝟏 = 𝑚𝑅𝑇 ln + 𝒎𝒄𝒑 ln
𝑃2 𝑇1 21
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Dr. Amr Ibrahim

𝑃1 𝑇2
𝑺𝟐 − 𝑺𝟏 = 𝑚𝑅𝑇 ln + 𝒎𝒄𝒑 ln
General Laws 𝑃2 𝑇1
for Entropy:
𝑉2 𝑇2
𝑺𝟐 − 𝑺𝟏 = 𝑚𝑅𝑇 ln + 𝒎𝒄𝒗 ln
𝑉1 𝑇1

𝑇2
For solid or liquid 𝑺𝟐 − 𝑺𝟏 = 𝒎𝒄 ln
𝑇1
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Thermodynamics
Dr. Amr Ibrahim

𝑸 − 𝑾𝒃 = ∆𝑼 𝟐 𝟐
𝒅𝒗 𝒅𝒑
𝒑𝒅𝒗 + 𝒄𝒗𝒅𝑻 = 𝟎 න 𝜸 −න
𝛿𝑸 − 𝛿𝑾𝒃 = 𝒅𝑼 𝟏 𝒗 𝟏 𝒑
𝒄𝒗
𝒑𝒅𝒗 + (𝒑𝒅𝒗 + 𝒗𝒅𝒑) = 𝟎 𝑣2 𝑝1
𝛿𝒒 − 𝛿𝒘𝒃 = 𝒅𝒖 𝑹 𝜸 ln = ln
𝑣1 𝑝2
𝒄𝒗 𝒄𝒗
𝛿𝑾𝒃 + 𝒅𝑼=0 𝒑𝒅𝒗(𝟏 + ) + 𝒗𝒅𝒑 = 𝟎 𝑣2 𝜸 𝑝1
𝑹 𝑹 ln = ln
𝑣1 𝑝2
𝒄𝒗 + 𝑹 𝒄𝒗
𝒑𝒅𝒗 + 𝒄𝒗𝒅𝑻 = 𝟎 𝒑𝒅𝒗( ) + 𝒗𝒅𝒑 = 𝟎
𝑹 𝑹 𝜸
𝑣2 𝑝1
𝑝𝑣 = 𝑅𝑇 𝒄𝒑 𝒄𝒗 =
𝒑𝒅𝒗( ) + 𝒗𝒅𝒑 = 𝟎 𝑣1 𝑝2
𝑹 𝑹
𝑝𝑑𝑣 + 𝑣𝑑𝑝 = 𝑅𝑑𝑇 + 𝑇𝑑𝑅
𝑪𝒑 ∗ 𝒑𝒅𝒗 + 𝑪𝒗 ∗ 𝒗𝒅𝒑 = 𝟎 𝑝1𝑣1𝛾 = 𝑝2𝑣2𝛾
1 𝜸 ∗ 𝒑𝒅𝒗 + 𝒗𝒅𝒑 = 𝟎
𝑑𝑇 =
𝑅
(𝑝𝑑𝑣 + 𝑣𝑑𝑝) 𝑝𝑣 𝛾 = C
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Thermodynamics
Dr. Amr Ibrahim

Entropy change is caused by heat transfer and irreversibilities. Heat

transfer to a system increases the entropy and heat transfer from the
system decreases it. The effect of irreversibilities is always to increase
the entropy.

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Thermodynamics
Dr. Amr Ibrahim

The Increase in entropy principle: (The entropy of a closed system can never Decrease)
2
Q
S system = S 2 − S1 =  + S gen. .
1
T
entropy change = entropy transfer + entropy generation

Entropy transfer: is the entropy transfer accompanying heat transfer.

When there is no heat transfer, there is no entropy transfer. (adiabatic process- isolated system) thus:
S2 − S1 = S gen..
S system  0
Its value depends on the process, thus it is not a property of a system. Depending on the presence of
irreversibilities within the system

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Thermodynamics
Dr. Amr Ibrahim

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.

Entropy is a non‐conserved property, and there is no such thing as the conservation of

entropy. Entropy can be created but it cannot be destroyed. Therefore, the entropy of
universe is continuously increasing.

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.
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Thermodynamics
Dr. Amr Ibrahim

2
Q
S system = S 2 − S1 =  + S gen. .
1
T

entropy change = entropy transfer + entropy generation

When there is heat transfer, internally reversible process

 2 Q   Q 
S = S 2 − S 1 =   
 == dS =  
1 T  int . rev .  T  int . rev .

The entropy change of a closed system during an irreversible process is always greater than
the entropy transfer.

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Thermodynamics
Dr. Amr Ibrahim

The total entropy change during a process is the amount of entropy generated during
the process and it is equal to the sum of the entropy of a system and of surrounding.
2
Q
S system = S 2 − S1 =  + S gen. .
1
T

S gen = Stotal = Ssystem + Ssurrounding  0

The total entropy change during a process is positive for actual process or zero for reversible ones

The entropy of a system or its surroundings may decrease during a process but the sum of
these two never decreases.

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