ME-207 Thermodynamics-II

PROPERTY DIAGRAMS INVOLVING ENTROPY

(Lecture # 03)
TEXT BOOK: CHAPTER 7 (7.5,7.6)
Learning Objectives
• Property Diagrams Involving Entropy
• What Is Entropy?

Slide 2
Property Diagrams Involving Entropy
 Property diagrams serve as great visual aids in the
thermodynamic analysis of processes.
 The two diagrams commonly used in the second-law analysis
are the temperature-entropy and the enthalpy-entropy
diagrams.
 From the definition of entropy

(7.14)

Slide 3
Property Diagrams Involving Entropy
 δQrev,int corresponds to a differential area on a T-S diagram.
 The total heat transfer during an internally reversible process
is determined by integration to be

(7.15)

which corresponds to the area

under the process curve on a T-S
diagram.
Fig 7–16 On a T-S diagram, the area under
the process curve represents the heat
transfer for internally reversible processes.

Slide 4
Property Diagrams Involving Entropy
 The area has no meaning for irreversible processes.
 on a unit-mass basis, heat transfer can be expressed as

(7–16)
or
(7–17)

 One special case for which these integrations can be performed

easily is the internally reversible isothermal process. It yields
(7–18)
(7–19)
Slide 5
Property Diagrams Involving Entropy
 An isentropic process on a T-s diagram is easily recognized as a
vertical-line segment.
 An isentropic process involves no heat transfer, and therefore the
area under the process path must be zero

Fig 7–17 The isentropic process

on a T-s diagram.
Slide 6
Property Diagrams Involving Entropy

h-s diagram

Fig A-10 Mollier diagram (h-s) for water.

Physical meaning of Entropy?
Physical meaning of Entropy?
 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.
Thus, it is not surprising that the entropy of a substance is
lowest in the solid phase and highest in the gas phase.
 An isolated system that appears to be at a state of equilibrium
actually exhibits a high level of activity because of the
continual motion of the molecules.

Slide 9
What Is Entropy?
 From a microscopic point of view, the entropy of a system
increases whenever the thermal randomness or disorder 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.
 In the case of gases, oscillations fade as the temperature is
decreased, and the molecules supposedly become motionless
at absolute zero.
 Therefore, the entropy of a pure crystalline substance at
absolute zero temperature is zero, known as the third law of
thermodynamics.

Slide 10
What Is Entropy?
 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.
 The entropy of a substance that is not pure crystalline (such as a
solid solution) is not zero at absolute zero temperature. Because
some uncertainty about the microscopic state of the substance
exist for more than one molecular configuration.
 because the energy of gas molecules are disorganized, they
cannot produce work all the time. Just like pulling a cart equally
from opposite directions cannot move.

Slide 11
What Is Entropy?
A Rotating Shaft
What Is Entropy?
A Rotating Shaft
 In the case of a rotating shaft, the energy of the molecules are
completely organized since the molecules of the shaft are rotating
in the same direction.
 There is no entropy transfer associated with energy transfer as
work. Being an organized form of energy, work is free of disorder
or randomness and thus free of entropy.

 Therefore, in the absence of any friction, the

process of raising a weight by a rotating shaft
(or a flywheel) does not produce any entropy.

Fig 7–23 Rotating shaft

with weight

Slide 13
What Is Entropy?
Paddle Wheel In A Container Filled With Gas
What Is Entropy?
Paddle Wheel In A Container Filled With Gas
 let us operate the paddle wheel in a container filled with a gas.
The paddle-wheel work in this case is converted to the internal
energy of the gas, creating a higher level of molecular disorder
in the container.
 Paddle wheel energy is now converted to a highly disorganized
form of energy, which cannot be converted back to the paddle
wheel as the rotational kinetic energy.
 Therefore, energy is degraded during this
process, the ability to do work is reduced,
molecular disorder is produced, and
associated with all this is an increase in
entropy.
Fig 7–24 The paddle-wheel work done on a gas

Slide 15
What Is Entropy?

 The quantity of energy is always preserved during an actual

process (the first law), but the quality is bound to decrease (the
second law).
 For example, transfer of 10 kJ of energy as heat from a hot
medium to a cold one. At the end of the process, we still have the
10 kJ of energy, but at a lower temperature and thus at a lower
quality.

Slide 16
What Is Entropy?
 Boltzmann first hypothesized that the entropy of a system at
a specified macrostate is related to the total number of
possible relevant microstates of that system, W
(probability).

where k is known as the Boltzmann relation.

Gibbs generalized it as

Gibbs’ formulation is more general since it allows for non-

uniform probability, pi, of microstates.

Slide 17
What Is Entropy?

Slide 18
Conclusion
 Temperature-entropy and the enthalpy-entropy diagrams are
useful in thermodynamics.
 The area under the process curve on a T-S diagram represents
heat transfer during an internally reversible process.
 Boltzmann relation for entropy is introduced.
 Physical meaning of entropy is elaborated with the help of
examples.

Slide 19