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Thermodynamics

Y Y Shan
Chapter 4

Thermodynamic Entropy

Introduction:
In science, the term "entropy", which means transformation in Greek, has two
distinct interpretations: one is the thermodynamic entropy in the field of physics, the
other is information entropy in information theory. Thermodynamic entropy, being the
subject to be discussed in the following, is a fundamentally different concept from
information entropy in information theory
There are two viewpoints explaining the thermodynamic entropy.

Classical

thermodynamics gives a macroscopic viewpoint, while statistical thermodynamics


gives a microscopic viewpoint. From the two different viewpoints, two equivalent
definitions of entropy had been developed in classical thermodynamics and statistical
thermodynamics, respectively.
The definition of entropy in classical thermodynamics was developed in the early
1850s by thermodynamicist Rudolf Clausius. It makes no reference to the microscopic
nature of matter.

The entropy is interpreted simply as a state function of a

thermodynamic system: that is, a property depending only on the current state of the
system, independent of how that state came to be achieved.
The definition of entropy in statistical thermodynamics was developed by Ludwig
Boltzmann in the 1870s. This definition describes the entropy as a measure of the
number of possible microscopic configurations of the individual atoms and molecules
of the system (microstates)

1.

Macroscopic perspective of entropy in classical thermodynamics: a State

Function
In thermodynamics, if the balance of function Z remains unchanged during a
cyclic process, i.e.,

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dZ = 0 ,
or the difference between the initial state and final state is independent of paths, i.e.,

Z fi = Z f Z i
Then function Z is called a state function, such as the internal energy U,

U = 0 .

1.1 An example to calculate Q/T:


In the following thermodynamic cycle, if a function is defined as: S =
its infinitesimal change: dS =

Q
, so that
T

dQ
.
T

What is the change of the function after a cycle ABCDA:

S ABCDA = dS =

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dQ
=?
T

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S ABCDA = S AB + S BC + S CD + S DA
B

dQAB
T
A
C
dQ
= BC
T
B
D
dQ
= CD
T
C
A
dQ
= DA
T
D

S AB =

S BC

S CD
S DA

=
=

Therefore, the function S as defined is a state function


1.2. Clausius theorem: Entropy a state function proved mathematically

It has been obtained in chapter 2, that for a Carnot engine cycle, the efficiency is :

Carnot =

Q
T
W
=1 C =1 C ,
QC
QH
TH

so that
QC TC
Q
Q
=
H = C
QH TH
TH TC
From above, we get the even more useful relation:

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QH QC

=0
TH TC

eqn4-3

If we take Q to be positive value, representing heat energy added to the system,


and take Q to be negative value, representing heat taken from the system, 4-3 can be
written as:

QH QC
+
= 0, or
TH TC
Q1 Q2
+
=0 ,
T1 T2

where T1 = TH , T2 = TC

In principle, any loop(cycle) can be broken up into a grid of infinitesimal Carnot


cycles, as shown in the following:.

The smooth closed curve(black) is a reversible cycle and the zigzag closed path is made
up of alternating isothermal(red) and adiabatic(blue) processes from neighboring
Carnot cycles.

For the far left Carnot cycle abcd, we have

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Q1 Q2
+
=0
T1 T2
Then for the next Carnot cycle efgh,

Q3 Q4
+
=0
T3 T4
Similar equations can be written for each Carnot cycle and if all the equations are added,
then the result obtained is that

Q1 Q2 Q3 Q4 Q5
+
+
+
+
+ .... = 0
T1 T2 T3 T4 T5
Since no heat is transferred during the adiabatic portions of the zigzag cycle, we may
write

Qj

T
j

=0

where the summation is taken over the entire zigzag cycle consisting of Carnot cycles, j
in number. Now, imagine the cycle divided into a very large number of strips of very
narrow Carnot cycles. When the isothermal processes (ab, ef) become shorter, then a
zigzag path can be made to approximate the original cycle as closely as we please.
When these isothermal processes become infinitesimal, in limit we obtain:

Qj

T
j

=0

dQ
=0
T

4.5

It is called the Clausius theorem. This result proves that the function defined as

is a state function.

This function S, namely Entropy (in Greek, meaning

"transformation"), is developed in the 1850s by German physicist Rudolf Clausius.


This is often a sufficient definition of entropy if you don't need to know about the
microscopic details. It can be integrated to calculate the change in entropy S during
any part of a thermodynamic cycle.

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B

dQ
A T

S BA = S B S A =

For the case of an isothermal process(constant temperature) it can be evaluated simply


by S = Q/T. The unit for entropy is Joules/Kelvin (J/K) or eV/K.

1.3

An entropy generator: Joule paddle wheel apparatus


It is instructive to calculate a unit of entropy, J/K, in order to gain a feeling for this new

thermodynamic variable. Consider the Joule paddle wheel apparatus shown in the following.
The system is 1kg water at T=300K T.
The surroundings are the adiabatic cylindrical wall, the diathermic bottom in contact
with a heat reservoir, also at T=300K, and the paddle wheels.
A slowly falling mass m causes the paddle wheels to turn. The falling mass does work
on the system, which causes an increase in the temperature of the water. However, the
diathermic bottom prevents the temperature from rising by removing heat energy Q from the
system into the reservoir.

Entropy generator
The change of entropy of the reservoir is given by:

S reservoir =

dQ Q
=
T
T

Since the state of the water (temperature and volume) is unchanged at the end of the process,
the internal energy is unchanged.
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S water = 0
U water = W Q = 0
Thus, the work W, done by the falling mass, equals the heat Q that enters the reservoir. If the
paddle wheel is driven by a mass of 29.9 kg that falls 1 meter,

Q = W = mgh
The entropy of the mass turning the paddle wheels is not changed during the process, because
no heat enters or leaves the mass.

S mass = 0
Then the change of entropy is given by:

S = S reservoir + S water + S mass =

Q 29.9kg 9.8 N / kg 1m
=
= 1.0( J / K )
T
300 K

The entropy is generated by the conversion of work (done by the mass) into heat
(entering the reservoir). Thus, the paddle wheel apparatus serves as an entropy generator.

1.4 The entropy version of the second law : principle of entropy increasing:
There are different versions, but all equivalant to each other, of the second law of
thermodynamics. In chapter 3, the second law in its heat engine formulation, by Lord Kelvin,
is:
It is impossible to convert heat completely into work.
And in its heat formulation by Clausius is:
Heat cannot spontaneously flow from a material at lower temperature to
a material at higher temperature.
The version of the second law that refers to entropy directly is due to Rudolf Clausius
In an isolated thermodynamic system, a process can occur only if it
increases the total entropy of the system
Thus, the thermodynamics system can either stay the same, or undergo some physical
process that increases its entropy.
Therefore, we can say: the entropy of the universe tends to increase, this the principle
of entropy increasing. Here the universe is defined as:
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universe(isolated thermodynamic system) = a system + its surroundings

S (universe) 0
Ice melting - a classic example of entropy increasing described in 1862 by Rudolf Clausius

A small 'universe', consists of the 'surroundings' (the hot room) and 'system' (glass,
ice, cold water). In this universe, some heat energy dQ from the warmer surroundings(at
300K) will spread out to the cooler system of ice and water at its T of 273 K , the melting
temperature of ice. The heat dQ for this process is the energy required to change water
from the solid state to the liquid state.
The entropy of the system will change by the amount:

dS system =

dQ
dQ
=
Tice 273K

The entropy of the surroundings will change by an amount:

dS surrounding =

dQ dQ
=
Troom 300 K

So in this example, the entropy of the system increases, whereas the entropy of the
surroundings decreases.

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