BASIC THERMODYNAMICS

MODULE 3
REVERSIBILITY
&
ENTROPY

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 Reversibility:
Definitions of a reversible process, reversible
heat engine, importance and superiority of a
reversible heat engine and irreversible
processes; factors that make a process
irreversible, reversible heat engines.
Unresisted expansion, remarks on Carnot’s
engine, internal and external reversibility,
Definition of the thermodynamic temperature
scale. Problems
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 Entropy
Clasius inequality; Statement, proof, application to a
reversible cycle. Entropy; definition, a property,
change of entropy, principle of increase in entropy,
entropy as a quantitative test for irreversibility,
calculation of entropy using Tds relations, entropy as
a coordinate, numerical problems.
 Introduction:
• First law of thermodynamics- concept of the
internal energy U
• Second law of thermodynamics- concept of the
entropy S
• Like internal energy, entropy is also a
thermodynamic property and is defined only in
terms of mathematical operations.
• Entropy content of an isolated system is not
conserved

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General Discussion:
For a system undergoing a quasi-static process, work done
at the boundary is given by,
W  P dV          (1)

This relation gives the work done at the boundary of a

system during a reversible process, since a reversible
process is a quasi-static process
Now Consider a reversible cycle in which only work involved
is done at the boundary of the system , we have

 Q   W   P dV      (2)
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 Form the equation (2) ,
• Work is given by the cyclic integral of product of two
properties viz. P is an intensive property & dV is change in an
extensive property.
• For a reversible cycle when work (which is a path function) is
defined by the product of two properties one is intensive
and the other is change in an extensive property, why can’t
Heat (which is also a path function) is defined by the cyclic
integral of product of two properties one intensive and the
other change in an extensive property.
• Yes, the intensive property most closely associated with heat
is temperature and the other extensive property for this
answer is ENTROPY

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Then what exactly is entropy?
Entropy is:
• An extensive property
• A measure of the disorder of a system, the greater
the disorder, the greater the entropy.
• The state of disorder in a thermodynamic system:
the more energy the higher the entropy
• A measure of the dispersal or degradation of energy.
• A measure of the disorder or randomness in a closed
system. For example, the entropy of an unburned
piece of wood and its surroundings is lower than the
entropy of the ashes, burnt remains, and warmed
surroundings due to burning that piece of wood
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• Defined as a measure of unusable energy within a
closed isolated system (the universe for example). As
usable energy decreases and unusable energy
increases, "entropy" increases.
• Entropy is also a gauge of randomness or chaos
within a closed system. As usable energy is
irretrievably lost, disorganization, randomness and
chaos increase.

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Understanding entropy:
Example 1

One of the ideas involved in

the concept of entropy is that
nature tends from order to
disorder in isolated systems

This tells us that the right

hand box of molecules
happened before the left
If the particles represents gas
molecules at normal
temperatures inside a closed
container, which of the
illustration came first ?
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Example 2
If you tossed bricks off a truck, which kind of pile of
bricks would you more likely produce ?

Disorder is more probable than order

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Example 3

The jumble of ice chips

may look more disordered
in comparison to the glass
of water which looks
uniform and homogeneous

For a glass of water the Ice chips place limits on the number of
number of molecules is ways the molecules can be arranged
astronomical but not the water

The water molecules in the glass can be arranged in many more

ways They have greater "multiplicity" and therefore greater
entropy
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Solids have lesser entropy than liquids. Statistically, in
solids the atoms or molecules are in their fixed places,
whereas in liquids and even more in gases you never
know exactly where to find them. The fixed sequence of
atoms in solids reflects a higher ordered state.
•Consider a body which is heated and another one is
cooled. What happens to the entropy of the two bodies?
Entropy increases on heating. Does disorder increase,
too?
Yes, it does. We know that heat is stored in a piece of
matter as the random motion of particles. The hotter a
body, the more its atoms and molecules jiggle around. It
is not difficult to identify disorder by faster jiggling
motion.
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Clausius Theorem:
Proof: The thermal efficiency of reversible Carnot cycle is
QL TL QH QL
Carnot  1   1 or         (1)
QH TH TH TL
Considering the usual sign convention, +ve for the heat
absorbed and –ve for the heat rejected, we may write,
QH QL QH QL
 or   0          (2)
TH TL TH TL
QH Q
Equation (2) shows that the sum of the quantities, and L
TH TL

associated with absorption and rejection of heat by the fluid

of a reversible heat engine is zero for the entire cycle

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Since the working fluid returns to its initial state at the end
of the cycle, it undergoes no net change in properties,
Q Q
suggesting that the quantities T H
and
T
L
represents
H L

property changes of the working fluid because their sum is

zero for the cycle
This is the characteristic of a property or state function.
• QH and QL are path functions. However if they are
divided by the temperatures at which the transfer takes
place, the result is independent on the path. This
conclusion is for Carnot cycle.
• The above conclusion is also valid for any reversible
cycle.
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 j b Consider any arbitrary
m reversible cycle a-b-c-d-a as
f
shown. In this absorption
Pressure e and rejection of heat do not
c
a
occur at two constant
n
k temperatures but take place
g at continuously changing
d h
temperatures.
Volume

The cycle can be now broken into an infinite number

elementary Carnot cycle
Draw a series of infinitely close adiabatic lines, eh, fg, mn, etc.
efgh, fmng etc represents elementary Carnot cycle in which
sections ef, gh etc can be considered as isothermal lines.
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For any differential Carnot cycle, efgh, we may write
QH 1 QL1

TH 1 TL1
Using proper sign convention
QH 1 QL1
  0          (1)
TH 1 TL1
Similarly,
QH 2 QL 2
  0          (2) for the cycle fmng
TH 2 TL 2
From these relations we see that the algebraic sum of the
ratios of the amounts of heat transferred to the absolute
temperature for the Carnot cycles taken together is equal to
zero, thus,  QH 1  QL1    QH 2  QL 2            0
T TL1   TH 2 TL 2 
 H1
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i.e.,  QH QL 
  T  T   0          (3)
 H L 

As the number of Carnot cycles is very large, the sum of

Q
the terms T over the complete cycle becomes equal to the
cyclic integral of TQ
We may , therefore write Q

 0        (4)
R
T
Where R represents reversible cycle
Therefore the cyclic integral of Q for a reversible cycle is
T
zero.
This result is known as CLAUSIUS THEOREM
Q
T is known as ENTROPY
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 This is called the principal of increase of entropy. This equation states the
entropy of universe is continuously increasing.

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 Dr. Ezhil Vannan S, Professor, Dept. of
12/6/2020
Mech. Engg., MCE, Hassan
 Dr. Ezhil Vannan S, Professor, Dept. of
12/6/2020
Mech. Engg., MCE, Hassan
 Dr. Ezhil Vannan S, Professor, Dept. of
12/6/2020
Mech. Engg., MCE, Hassan
 Dr. Ezhil Vannan S, Professor, Dept. of
12/6/2020
Mech. Engg., MCE, Hassan
 Dr. Ezhil Vannan S, Professor, Dept. of
12/6/2020
Mech. Engg., MCE, Hassan
 Dr. Ezhil Vannan S, Professor, Dept. of
12/6/2020
Mech. Engg., MCE, Hassan
 Dr. Ezhil Vannan S, Professor, Dept. of
12/6/2020
Mech. Engg., MCE, Hassan
 Dr. Ezhil Vannan S, Professor, Dept. of
12/6/2020
Mech. Engg., MCE, Hassan
 Dr. Ezhil Vannan S, Professor, Dept. of
12/6/2020
Mech. Engg., MCE, Hassan