A measure of disorder

Entropy and 2nd law of Thermodynamics

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• Basic concepts
• Entropy and change in entropy
• Second law of thermodynamics
• Heat engines : Carnot and Sterling
• Efficiencies of real engines
• Statistical view of entropy
Prelude

Why does
energy flow from a hot object to a
cold one but never the other way
around ?
friction always warm objects -
never cools them ?
enough internal energy never
gather in one baseball to send it
flying through the air ?
Irreversible processes
Some things happen in a certain sequence and
could never happen on their own in a reverse
sequence

Irreversible processes are one-way processes such that they

cannot be reversed (taken backward in time)
What is Entropy ?

The change in entropy, ∆S, sets direction of irreversible

processes

An ordered system.
Entropy is low. There is a
concentration of some
substance in one area.

Entropy, S, is a measure of the availability of a system’s

energy to do work
What is Entropy ?

The change in entropy, ∆S, sets direction of irreversible

processes

A disordered system.
Entropy is high. There isn’t
a concentration of a
substance.

Entropy, S, is a measure of the availability of a system’s

energy to do work
Change in entropy

To define ∆S, We can look for

• heat lost or gained during the process (macroscopic)
• ways in which atoms/molecules can be arranged (microscopic)

Clausius 1822-1888 Boltzmann 1844-1906

Irreversible processes

Consider an irreversible process -

the free expansion of an ideal gas
going from state i to f
Once the gas fills the entire
container, it cannot spontaneously
collect itself to go back to the left
half.
Irreversible processes

The change in entropy of the

process is given by

f
dQ
∆S = S f − S i =
∫i
T

Where Q is the energy transferred

as heat to or from the system
during the process
Irreversible processes

The intermediate state of the gas

between i and f can not be shown as
fluctuate unpredictably and are not
equilibrium states
Irreversible processes

Entropy is a state property and

therefore it depends on the states and
NOT on the way the system goes
from i to f . We should therefore be
able to relate it with a reversible
isothermal expansion that has the
same i and f .
Irreversible processes
Irreversible processes

To find the entropy for an irreversible

process occurring in a closed system,
replace that process with any
reversible process that connects the
same initial and final states, then
calculate the entropy change for this
reversible process.
Irreversible processes

In isothermal processes we find

∆S = S f − S i
f
1
=
T ∫
i
dQ

Q
=
T
Where Q is the total energy
transferred as heat during the process
Example
Figure below shows two identical copper blocks of mass
m=1.5kg: block L at temperature TiL= 60oC and block R at
temperature TiR= 20oC. The blocks are in thermally insulated box
and are separated by an insulating shutter. When we lift the
shutter, the blocks eventually come to the equilibrium
temperature Tf=40oC. 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.
Example
2nd law of thermodynamics

Clausius showed that the total

entropy of a system increases when
the heat flows from a HOT (higher Clausius 1822-1888
temperature) body to a COLD (lower
temperature) one.
But since heat has always been
known to flow from hot to cold, he
could then state:

The entropy of an isolated (closed)

system always increases (irreversible)
or remains constant (reversible). It
never decreases.
2nd law of thermodynamics
It means that …
An order system will naturally tend to disorder

and it requires energy to create order out of disorder .

Heat engine

A heat engine is a machine that

converts thermal (heat) energy
into other forms of energy, usually
mechanical or electric energy.
It goes through cyclical changes
in which a source of heat is
transferred.
Carnot engine

In an ideal engine, all processes are

reversible and no wasteful energy
transfer occurs due to, say, friction
and turbulence
• heat has been created or absorbed in a
high-temperature area
• this heat has a tendency to disperse
(flowing to a cooler area)
• the heat passes through an engine
Engines use energy • the heat is used to do work by the engine
as heat to do useful
work • the heat left over flows to the cold reservo
where it is expelled as waste
Carnot engine

The cyclical process is comprised of

several steps:

• 1st: isothermal expansion in a heat

reservoir
• 2nd: adiabatic expansions when Q = 0
• 3rd: isothermal compression in the
heat reservoir

Engines use energy

• 4th: adiabatic compression when Q = 0
as heat to do useful
work
Carnot engine

Engines use energy 2 isothermal processes (ab and cd )

as heat to do useful 2 adiabatic processes (bc and da )
work
Carnot engine

Engines use energy During ab and cd temperature is constant

as heat to do useful
work During bc and da entropy is constant
Carnot engine
To calculate the net work done we apply 1st law
to the working substance,
For a complete cycle ∆Eint=0

W =QH −QL
And the change in entropy
∆S = ∆S H + ∆S H
QH QL
= −
TH TL
For a complete cycle ∆S =0
QH QL
=
TH TL
Efficiency

Thermal efficiency ε is given by

energy we get
ε=
energy we pay for
W
=
QH

And for a carnot engine,

we can derive perfect engine
(doesn’t exist)
TL
ε =1−
TH
Sterling engine

Carnot Sterling

2 isotherm processes
2 adiabatic
processes 2 isotherm processes
2 constant-volume processes
Refrigerators
Refrigerators, air-conditioners, heat pumps use
work to transfer energy from low temperature
reservoir to high temperature reservoir
The coefficient of
performance KC (efficiency)
is given by

what we want
K C =
what we pay for
QL
=
W
‘ideal’ refrigerator ‘perfect’ refrigerator
(carnot refrigerator)
Refrigerators
Refrigerators, air-conditioners, heat pumps use
work to transfer energy from low temperature
reservoir to high temperature reservoir

Applying 1st law of

thermodynamics

TL
K C =
T H −T L
And for the entropy change
Q Q
∆S = − +
TL TH
‘ideal’ refrigerator ‘perfect’ refrigerator
(carnot refrigerator) doesn’t exist...
A statistical view

When energy in a system is

degraded (as Clausius said), the
atoms in the system become more
and more disordered and the
entropy increases. But a measure of
the disorder can be made. It is the
probability of the particular system -
defined as the number of ways it can
be assembled from its collection of
atoms.
Boltzmann’s equation of entropy:

S = k ln W
A statistical view

• Six gas molecules are in an

insulated box
• Each of them has the same
probability of being in the left half
as being in the right half
• We call different arrangements
of molecules ‘microstates’
• We call the number of
microstates that correspond to a
given configuration ‘multiplicity of
configuration’ W
N!
W =
n 1!n 2 !
A statistical view

For a large number of molecules, nearly all the

microstates correspond to an approximately
equal sharing of the molecules between two
halves of the box.
A statistical view

How can we understand this idea

of microstates ? Consider rolling a
pair of dice. What is the most
likely result for the sum ?
(a) 2 through 12 equally likely
(b) 7
(c) 5
Things should be made as simpler as possible
but not any simpler.

- Albert Einstein