IV.

Entropy and the Second Law

of Thermodynamics
Outcomes
• Understand the second law of thermodynamics
• Define and calculate entropy
• Applications of 2nd law: engines and
refrigerators

1
IV. Entropy and the Second Law
of Thermodynamics
Introduction
◦ We are accustomed to many irreversible process: An
egg is dropped onto a floor, a pizza is baked, a car is
driven into a lamppost, etc.
◦ For reversible processes the system is in equilibrium
with its environment, while for irreversible processes
it is not.
◦ Why these processes are irreversible??
◦ The idea of entropy provides a mathematical way to
encode the intuitive notion of which processes are
impossible.

2
IV. Entropy and the Second Law
of Thermodynamics
Introduction
◦ Entropy: A measure of the molecular “disorder”, or
randomness, of a system
◦ The term was coined in 1865 by Clausius from
Greek, meaning transformation, turning, change
◦ This concept was first developed in response to the
observation that a certain amount of functional
energy released from combustion reactions is always
lost to dissipation or friction and is thus not
transformed into useful work.
◦ 3
Entropy What is entropy?
02 ways to define entropy
of a system:
(1) Macroscopic
perspective: in terms of the
system’s temperature and
the energy the system gains
or loses
(2) Microscopic
perspective: by counting
the ways in which the
atoms or molecules that
make up the system can be
arranged 4
Entropy What is entropy?
02 ways to define entropy
of a system:
(1) Macroscopic
perspective: in terms of the
system’s temperature and
the energy the system gains
or loses

5
 Entropy The change in entropy is
Entropy: the measure of a system’s thermal energy per unit temperature that
is unavailable for doing useful work. Because work is obtained from
often more useful and
ordered molecular motion, the amount of entropy is also a measure of the practical because it helps us
molecular disorder, or randomness, of a system. understand how systems
evolve during processes,
Change in entropy:
whether a process is
An entropy change (J/K) depends not only on the energy transferred as heat but also on the spontaneous, and how
temperature at which the transfer takes place energy and disorder are
For an isothermal process:
distributed. Absolute
When the temperature change is small relative to entropy values are less
the temperature before and after the process: frequently used in practical
Entropy is a state property (or a state function): it depends only on those states and not at all on applications, except in very
the way the system went from one state to the other. specific cases like low-
To find the entropy change for an irreversible process, replace that process with any temperature physics.
reversible process that connects the same initial and final states.
6
 Entropy as a State Function
Consider a reversible process, with the ideal gas in equilibrium states.
First law in differential form:
We have assumed that S (like V,
P, Eint) is a state function: this can
be deduced only by experiment.

Applying the ideal gas law: However, we can prove it is a

state function for the special and
important case in which an ideal
gas is taken through a reversible
process.

Note that we did not have to specify a particular reversible process when we
integrated. Therefore, the integration must hold for all reversible processes that take
the gas from state i to state f.
The change in entropy between the initial and final states of an ideal gas 7

does not depend on how the gas changes between the two states.
Exercise
Two identical copper blocks of mass m = 1.5 kg:
block L at TiL = 60°C and block R at TiR = 20°C.
The blocks are in a thermally insulated box and are
separated by an insulating shutter. When we lift
the shutter, the blocks eventually come to the
equilibrium temperature Tf = 40°C. What is the
net entropy change of the two-block system
during this irreversible process? The specific heat
of copper is 386 J/kg.K

8
Exercise
TiL = 60°C, TiR = 20°C, Tf = 40°C.
cm = 386 J/kg.K. ΔS?

9
Exercise
Suppose 1.0 mol of nitrogen gas is
confined to the left side of the
container. You open the stopcock, and
the volume of the gas doubles. What is
the entropy change of the gas for this
irreversible process? Treat the gas as
ideal.

10
Exercise
nN2 = 1 mol,V2 = 2V1. ΔS?
(1) We can determine the entropy change
for the irreversible process by calculating it
for a reversible process that provides the
same change in volume
(2) The temperature of the gas does not
change in the free expansion. Thus, the
reversible process should be an isothermal
expansion

11
 2nd law of
Second law of thermodynamics
thermodynamics
The entropy postulate:
“Many past efforts to provide the
Second Law with a firm
mathematical foundation. None have
succeeded.”
But:
“Physics is science based on empirical
The second law of thermodynamics: evidence.”

(The greater-than sign applies to irreversible

processes and the equals sign to reversible
processes) 12
 Why is entropy important to study?
There are many reasons, some of them can be:
1. Entropy is central to the Second Law of Thermodynamics that governs the direction of all natural processes
and introduces the concept of irreversibility.
It explains why certain processes occur spontaneously (like heat flowing from a hot body to a cold body) while
others do not, or why processes like mixing gases or frictional heating cannot be undone without external
intervention.
2. Thermal Energy Unavailable for Work
Entropy measures the portion of a system's thermal energy that is not available for doing useful work. The
greater the entropy, the less energy is available to do work.
3. Predicting Process Feasibility
Entropy helps determine whether a process is thermodynamically feasible. A process will only occur if the total
entropy (system + surroundings) does not decrease.
13
Entropy in real world: Engines Heat engines
A heat engine (more simply, an
In a steam engine, the working engine): a device that extracts
energy from its environment in
substance is water, in both its
the form of heat and does work.
vapor and its liquid form.
At the heart of every engine is a
working substance.

If an engine is to do work on a
sustained basis, the working
substance must operate in a cycle.
In an automobile engine the
working substance is a gasoline– The working substance must
air mixture. pass through a closed series of
thermodynamic processes, called
strokes, returning again and again
to each state in its cycle. 14
Entropy in real world: Engines Carnot engine
The two black arrowheads on the In an ideal engine, all processes
central loop suggest the working are reversible and no wasteful
substance operating in a cycle, as if energy transfers occur due to,
on a p-V plot. say, friction and turbulence.

|QH|+ is transferred as heat from Let’s focus on a particular ideal

the high-temperature reservoir at engine called a Carnot engine:
TH to the working substance. the best (in principle) at using
energy as heat to do useful work.
|QL| is transferred as heat from
the working substance to the low- Carnot was able to analyze the
temperature reservoir at TL. performance of this engine
before the first law of
W is done by the engine (actually thermodynamics and the
by the working substance) on concept of entropy had been
something in the environment. discovered!!!
15
Entropy in real world: Engines Carnot engine
If we place the cylinder in contact with Imagine the working substance
the high temperature reservoir at TH, to be a gas, confined to an
|QH| is transferred to the working insulating cylinder with a
substance from this reservoir as the gas weighted, movable piston.
undergoes an isothermal expansion from
Va to Vb. The cylinder may be placed
at will on either of the two
thermal reservoir.

With the working substance in contact

with the low-temperature reservoir at TL,
|QL| is transferred from the working
substance to the low-temperature
reservoir as the gas undergoes an
isothermal compression from Vc to Vd
16
Entropy in real world: Engines Carnot engine
Assuming that heat transfers to or from Imagine the working substance
the working substance can take place only to be a gas, confined to an
during the isothermal processes ab and cd. insulating cylinder with a
weighted, movable piston.
Therefore, processes bc and da which
connect the two isotherms must be The cylinder may be placed
(reversible) adiabatic processes. at will on either of the two
thermal reservoir.
To ensure this, during processes bc and da
the cylinder is placed on an insulating slab
as the volume of the working substance is
changed.

17
Entropy in real world: Engines Carnot engine
Work done by a Carnot engine:
Work done by a Carnot engine:
for a closed cycle: Wnet = Qnet
(first law of thermodynamics)
Entropy changes:
Entropy changes: only two
reversible energy transfers as
heat, and thus two changes in
Because entropy is a state function, the entropy of the working
ΔS = 0 for a complete cycle: substance, one at temperature
TH and one at TL.

Because TH > TL, |QH| > |QL|: more

energy is extracted as heat from the high-
temperature reservoir than is delivered to the
18
low-temperature reservoir.
Entropy in real world: Engines Carnot engine
No real engine can have a
thermal efficiency greater
than Carnot engine!

19
Entropy in real world: Engines Stirling engine

Isothermal heat transfers at temperatures TH The Stirling engine was

and TL developed in 1816 by
Transfers of energy as heat Q is required to Robert Stirling.
increase/decrease the temperature between,
TL and TH Applications:
- automobiles
𝑊 𝑄𝐻 +𝑄 − 𝑄𝐿 +𝑄 - spacecraft
S = =
𝑄′𝐻 𝑄𝐻 +𝑄
𝑄 −𝑄
- military submarines
=
𝑄𝐻 −𝑄𝐿
< 𝐻 𝐿 = C (because these engines are
𝑄𝐻 +𝑄 𝑄𝐻
A p-V plot for the working
substance of an ideal Stirling more quiet than others)
engine

20
Exercise
Imagine a Carnot engine that operates between the
temperatures T = 850 K and T = 300 K. The engine
H L

performs 1200 J of work each cycle, which takes 0.25 s.

(a) What is the efficiency of this engine?
(b) What is the average power of this engine?
(c) How much energy |QH| is extracted as heat from the
high-temperature reservoir every cycle?
(d) How much energy |QL| is delivered as heat to the low
temperature reservoir every cycle?
(e) By how much does the entropy of the working substance
change as a result of the energy transferred to it from the
high-temperature reservoir? From it to the low-temperature
reservoir?

21
 Exercise
TH = 850 K and TL = 300 K. W = 1200 J each cycle of 0.25
s.
(a) What is the efficiency of this engine?

(b) What is the average power of this engine?

(c) How much energy |QH| is extracted as heat from the

high-temperature reservoir every cycle?

(d) How much energy |QL| is delivered as heat to the low

temperature reservoir every cycle?

(e) By how much does the entropy of the working

substance change as a result of the energy transferred to it
from the high-temperature reservoir? From it to the low-
temperature reservoir?

22
Entropy in real world:
Refrigerators Refrigerator
Coefficient of performance A refrigerator: device that
uses work to transfer energy
from a low temperature
reservoir to a high-temperature
reservoir
In an ideal refrigerator, all
processes are reversible and no
wasteful energy transfers occur
as a result of, say, friction and
turbulence.

Its operation is the reverse of

how the Carnot engine
operates.
23
Efficiency of real engines: Engine
Assume an engine X having (a claim)
efficiency
Here we prove that no real
Let’s couple engine X to a engine can have an efficiency
Carnot refrigerator. greater than that of a Carnot
engine.

If it could, the engine would

violate the second law of
thermodynamics

Carnot refrigerator’s stroke is adjusted so that the work it requires per cycle is
just equal to that provided by engine X (WC = WX).

Thus, no (external) work is performed on or by the system engine + refrigerator 24

Efficiency of real engines: Engine
efficiency
If is true:
Here we prove that no real
engine operating between can
have an efficiency greater than
Then: that of a Carnot engine.

If it could, the engine would

violate the second law of
thermodynamics
Because the WX = WC, from the first law of thermodynamics:
or
>0

25
Efficiency of real engines: Engine
efficiency
Here we prove that no real
engine operating between can
have an efficiency greater than
that of a Carnot engine.

If it could, the engine would

violate the second law of
thermodynamics

The transfer energy Q as heat from a low to a high-temperature reservoir

without the requirement of work  perfect refrigerator!!!

A perfect refrigerator transfers energy as heat Q from a cold reservoir to

a warm reservoir without the need for work.
26
Efficiency of real engines: Engine
Because the unit operates in cycles, the entropy efficiency
of the working substance does not change
during a complete cycle.

The entropies of the two reservoirs, however,

do change: ΔSL = -|Q|/T and ΔSH = +|Q|/T No real engine can have an efficiency
greater than that of a Carnot engine
Thus, the net entropy change for the entire when both engines work between the
system is same two temperatures

Because TH > TL  ΔS <0.

Violation of the second law  a perfect

refrigerator does not exist!!
27
 Exercise
1. Which of the following is true?
a) for an isolated system, dS>=0
b) for a reversible process, dS=0
c) for an irreversible process, dS>0
d) all of the mentioned
Answer: d). For an isolated system which does not undergo any energy interaction with the surroundings,
dQ=0 and also dS>=dQ/T.
2. Entropy may decrease locally at some region within the isolated system. How can this statement be justified?
a) this cannot be possible
b) this is possible because entropy of an isolated system can decrease.
c) it must be compensated by a greater increase of entropy somewhere within the system.
d) none of the mentioned
Answer: c). The net effect of an irreversible process is an entropy increase of the whole system.
28
 Entropy What is entropy?
The « disorder of » entropy is of the number of states that a system can
take on
02 ways to define entropy
of a system:
(2) microscopic
perspective: by counting
the ways in which the
Consider 2 systems: one with 4 atoms, one with eight
atoms
atoms or molecules that
make up the system can be
arranged

Fewer possible states

More possible states
Ludwig Boltzmann defined entropy as a measure More entropy!
of the number of possible microscopic states
(microstates) of a system in thermodynamic 29
equilibrium
Entropy What is entropy?
Consider a box that contains six identical (and thus
indistinguishable) molecules of a gas 02 ways to define entropy
of a system:
At any instant, a given molecule will be in either the left (1) microscopic
or the right half (having the same volume) of the box: the perspective: by counting
molecule has the same probability of being in either half.
the ways in which the
atoms or molecules that
Possible configurations of the six molecules: make up the system can be
arranged

30
 Entropy What is entropy?
02 ways to define entropy
of a system:
(1) microscopic
perspective: by counting
the ways in which the
atoms or molecules that
A given configuration can be achieved in a number of different ways.
make up the system can be
We call these different arrangements of the molecules microstates. arranged

Suppose N molecules are distributed with n1 molecules in one half of the

box and n2 in the other (n1 + n2 = N)

The total number of ways in which we can select all six molecules is the
product of these independent ways, 31

or 6 x 5 x 4 x 3 x 2 x 1 = 720 or 6! = 720
Entropy What is entropy?
02 ways to define entropy
of a system:
(1) microscopic
perspective: by counting
the ways in which the
atoms or molecules that
make up the system can be
However, because the molecules are indistinguishable, these 720 arranged
arrangements are not all different.

To get the number of different arrangements:

32
(the number of microstates that correspond to a given configuration)
 Entropy What is entropy?
02 ways to define entropy
of a system:
(1) microscopic
perspective: by counting
the ways in which the
Configuration IV: most probable configuration, with probability 20/64 = 0.313
(system is in configuration IV 31.3% of the time)
atoms or molecules that
 The molecules are evenly divided between the two halves of the box, make up the system can be
because that is what we expect at thermal equilibrium. arranged
Configurations I and VII, (all the molecules are in one half of the box) are
the least probable (probability 1/64 = 0.016 or 1.6%)
 There is any probability, however small, of finding all six molecules
clustered in half of the box, with the other half empty
For large values of N: nearly all the microstates belong to the configuration
in which the molecules are divided equally between the two halves of the 33
box, and probability for configurations I an VII are mostly 0!!
Entropy What is entropy?
02 ways to define entropy
of a system:
(1) microscopic
perspective: by counting
the ways in which the
In 1877, Boltzmann derived a relationship between the
atoms or molecules that
entropy S of a configuration of a gas and the multiplicity W make up the system can be
of that configuration: arranged

34
Exercise
Suppose that there are 100 indistinguishable
molecules in the previous box. How many
microstates are associated with the
configuration n1 = 50 and n2 = 50, and with
the configuration n1 = 100 and n2 = 0?
Interpret the results in terms of the relative
probabilities of the two configurations

35
 Exercise
How many microstates are associated with the
configuration n1 = 50 and n2 = 50, and with
the configuration n1 = 100 and n2 = 0?

Configuration
(50, 50):

Configuration
(100, 0):

A 50 – 50 distribution is more likely than a

100 – 0 distribution by the factor of about 1029

36
Summary
• Reversible and Irreversible process
• Entropy: two ways to define
• Change in Entropy
• The second law of thermodynamics
• Engines
• Refrigerators

37