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

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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.

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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 Rudolf Clausius
from Greek en- = in + trope = a turning (point).
◦ Concept 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.  
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 What is
Entropy 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
arranged
(2) Macroscopic
perspective: in terms of
the system’s temperature
and the energy the system
gains or loses 4
 What is
Entropy 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:
(1) 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 More entropy!
measure of the number of possible microscopic
states (microstates) of a system 5
in thermodynamic equilibrium
 What is
Entropy 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: perspective: by counting
the 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

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 What is
Entropy 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, 7

or 6 x 5 x 4 x 3 x 2 x 1 = 720 or 6! = 720
 What is
Entropy 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 arranged
720 arrangements are not all different.

To get the number of different arrangements:

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(the number of microstates that correspond to a given configuration)
 What is
Entropy 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 9
halves of the box, and probability for configurations I an VII are mostly
 What is
Entropy 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 make up the system can be
W of that configuration: arranged

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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

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 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

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 What is
Entropy entropy?
Entropy: the measure of a system’s thermal energy per
unit temperature that is unavailable for doing useful work. Because work
is obtained from ordered molecular motion, the amount of entropy is also 02 ways to define entropy
a measure of the molecular disorder, or randomness, of a system.  of a system:
(2) Macroscopic
Change in entropy: perspective: in terms of
An entropy change (J/K) depends not only on the energy transferred as heat the system’s temperature
but also on the temperature at which the transfer takes place and the energy the system
When the temperature change is small relative to the temperature before and after gains or loses
the process:

Entropy is a state property (or a state function): it depends only on those states
and not at all on the way the system went from one state to the other.
To find the entropy change for an irreversible process, replace that process with any
reversible process that connects the same initial and final states.
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Entropy as a State Function
Consider a reversible process, with the ideal gas in equilibrium states.
We have assumed that S (like V,
P, Eint) is a state function: this
First law in differential form:
can be deduced only by
experiment.

However, we can prove it is a

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

The change in entropy between the initial and final states of an ideal 14

gas 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

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

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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.

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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

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 2nd law of
Second law of
thermodynamic
thermodynamics s
Consider a closed system of the thermal reservoir and the
ideal gas inside the piston that expands isothermally
If a process occurs in a closed
The entropy changes for the gas (which loses |Q|): system, the entropy of the
system increases for
irreversible processes and
remains constant for
The entropy changes for the reservoir (which gains|Q|): reversible processes. It never
decreases.

The entropy change of the closed system = 0.

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 2nd law of
Second law of
thermodynamic
thermodynamics s
The entropy postulate:
If a process occurs in a closed
system, the entropy of the
system increases for
irreversible processes and
remains constant for
reversible processes. It never
The second law of thermodynamics: decreases.

(The greater-than sign applies to irreversible

processes and the equals sign to reversible
processes) 20
Entropy in real world: Engines Heat engines
A heat engine (more simply,
In a steam engine, the working an engine): a device that
extracts energy from its
substance is water, in both its
environment in the form of
vapor and its liquid form. heat and does work.

At the heart of every engine is

a working substance.

If an engine is to do work on a
sustained basis, the working
In an automobile engine the substance must operate in a
working substance is a cycle.
gasoline–air mixture.
The working substance must
pass through a closed series of
thermodynamic processes, 21
called strokes, returning again
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 energy transfers occur due to,
if 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
|QL| is transferred as heat from work.
the working substance to the low-
temperature reservoir at TL. Carnot was able to analyze the
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!!! 22
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
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Entropy in real world: Engines Carnot engine
Assuming that heat transfers to or from Imagine the working substance
the working substance can take place to be a gas, confined to an
only during the isothermal processes ab insulating cylinder with a
and cd. weighted, movable piston.

Therefore, processes bc and da which The cylinder may be placed

connect the two isotherms must be at will on either of the two
(reversible) adiabatic processes. 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.

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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 low- 25
temperature reservoir.
Entropy in real world: Engines Carnot engine
No real engine can have
a thermal efficiency
greater than Carnot
engine!

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Entropy in real world: Engines Stirling engine

Isothermal heat transfers at temperatures TH The Stirling engine was

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

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Exercise
Imagine a Carnot engine that operates between the
temperatures TH = 850 K and TL = 300 K. The engine
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?

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 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?
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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.
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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 + 31

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

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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.
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Efficiency of real engines: Engine
Because the unit operates in cycles, the efficiency
entropy 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
Thus, the net entropy change for the entire a Carnot engine when both
system is engines work between the
same two temperatures

Because TH > TL  ΔS <0.

Violation of the second law  a perfect

refrigerator does not exist!! 34
 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.
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Summary
• Reversible and Irreversible process
• Entropy: two ways to define
• Change in Entropy
• The second law of thermodynamics
• Engines
• Refrigerators

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