The Laws of

Thermodynamics
The Zeroth Law of Thermodynamics

“If two systems are separately in thermal

equilibrium with a third system, they are
in thermal equilibrium with each other.”
This allows the design & the use of
Thermometers!
 The First Law of Thermodynamics
Q = ∆Ē + W
Heat absorbed Work done
by the system by the
Change in the system’s system
internal energy
For Infinitesimal, Quasi-Static Processes

đQ = dĒ + đW

Total Energy is Conserved

“Energy can neither be
created nor destroyed.
It can only be changed
from one form to
another.”
Rudolf Clausius, 1850
• The 1st Law of Thermodynamics is
Conservation of Total Energy!!!!
• It says nothing about
The Direction of Energy Transfer!
(courtesy F. Remer)
 The Second Law of Thermodynamics
“The entropy of an isolated system increases in any
irreversible process and is unaltered in any reversible
process.”
• This is sometimes called

The Principle of Increasing Entropy S  0

• This gives the Preferred (natural)
Change in entropy
Direction of Energy Transfer
of the system
• This determines whether a process can occur or not.

(courtesy F. Remer)
 Historical Comments
• Much early thermodynamics development was driven by practical considerations.
• For example, building heat engines & refrigerators.

• So, the original statements of the

Second Law of Thermodynamics
may seem different than that just mentioned.
 Various Statements of the Second Law
1. “No series of processes is possible whose sole
result is the absorption of heat from a thermal
reservoir and the complete conversion of this
energy to work.” That is
There are no perfect engines!
2. “It will arouse changes while the heat transfers
from a low temperature object to a high
temperature object.”
Rudolf Clausius’
statement of the Second Law.
Strange sounding?
3. “It will arouse other changes while the
heat from the single thermal source is
taken out and is totally changed into
work.”

Lord Kelvin’s (William Thompson’s)

statement of the Second Law.
4. “It is impossible to extract an amount
of heat QH from a hot reservoir and use
it all to do work W. Some amount of
heat QC must be exhausted to a cold
reservoir.”

The Kelvin-Planck
statement of the Second Law.
 Heat Engine 
A system that can convert some of the random molecular
energy of heat flow into macroscopic mechanical energy.

QH  HEAT absorbed by a Heat Engine from a

hot body
-W  WORK performed by a Heat Engine on
the surroundings
-QC  HEAT emitted by Heat Engine to a cold body
The Second Law Applied to Heat Engines

Efficiency
= (W/QH) = [(QH - QC)/QH]
A “Heat Engine” That Violates the Second Law

Heat Reservoir

Heat q

Cyclic Machine

Work Output=q
 Refrigerator 
A system that can do macroscopic work to extract heat from a
cold body and exhaust it to a hot body, thus cooling the cold
body further. A system that
operates like a Heat Engine in reverse.

QC  HEAT extracted by a Refrigerator from a cold body

W  WORK performed by a Refrigerator on
the surroundings
-QH  HEAT emitted by a Refrigerator to a hot body
 The 2nd Law of Thermodynamics
Clausius’ statement for Refrigerators
• “It is not possible for heat to flow
from a colder body to a warmer body
without any work having been done
to accomplish this flow. Energy will
not flow spontaneously from a low
temperature object to a higher
temperature object.”
There are no perfect Refrigerators!
• This statement about refrigerators also applies to air
conditioners and heat pumps which use the same principles.
The Second Law Applied to Refrigerators

Efficiency
= (QC/W) = [(QC)/(QH - QC)]
The 2nd Law of Thermodynamics
can be used to classify Thermodynamic
Processes into 3 Types:
1. Natural Processes
(or Irreversible Processes,
or Spontaneous Processes)
2. Impossible Processes
3. Reversible Processes

We’ll discuss each more thoroughly with examples soon.

(courtesy F. Remer)
 The Third Law of Thermodynamics
“It is impossible to reach a temperature of
absolute zero.”

On the Kelvin Temperature Scale,

T=0K
is often referred to as
“Absolute Zero”
 Another Statement of The Third Law of
Thermodynamics
“The entropy of a true equilibrium
state of a system at T = 0 K is zero.”
(Strictly speaking, this is true only if the quantum mechanical ground state
is non-degenerate. If it is degenerate,
the entropy at T = 0 K is a small constant, not 0!)

This is Equivalent to:

“It is impossible to reduce the temperature of a
system to T = 0 K using a finite number of
processes.”
Some Popular Versions of
The Laws of Thermodynamics
1st Law: You can’t win.

2nd Law: You can’t break even.

3rd Law: There’s no point in trying.

Other Popular Versions of
The Laws of Thermodynamics
Version 1
Zeroth Law: You must play the game.
First Law: You can't win the game.
Second Law: You can't break even in the game.
Third Law: You can't quit the game.

Version 2
Zeroth Law: You must play the game.
First Law: You can't win the game, you can only break even.
Second Law: You can only break even at absolute zero.
Third Law: You can't reach absolute zero.
 Version 3
Zeroth Law: You must play the game.
First Law: You can't win the game.
Second Law: You can't break even except on a very cold day.
Third Law: It never gets that cold!

Version 4
Zeroth Law: There is a game.
First Law: You can't win the game.
Second Law: You must lose the game.
Third Law: You can't quit the game.
“Murphy's Law of Thermodynamics”

Things get worse under pressure!!

 From Statistical Arguments
we’ve seen that a Quantitative Definition of
Entropy is
S  kBln()
kB  Boltzmann’s constant
 = (E)  Number of
microstates at a given energy
 Spontaneous Processes & Entropy
Spontaneous Processes  Processes
that can proceed with no outside intervention
Entropy
• In qualitative terms, Entropy can be viewed
as a measure of the randomness or disorder
of the atoms & molecules in a system.
2nd Law of Thermodynamics
Total Entropy always increases in a
spontaneous process!
So, Microscopic Disorder also
increases in a spontaneous
process!
 Spontaneous Processes
Spontaneous Processes 
Processes that can proceed with no outside
intervention.

• Example in the figure: Due to the

2nd Law of Thermodynamics
the gas in container B will spontaneously
effuse into container A. But, once the gas is in
both containers,
it will not
spontaneously effuse back into container B.
The 2nd Law of Thermodynamics
Processes that are spontaneous in one
direction are not
spontaneous in the reverse
direction.
Example in the figure: Due to the
2nd Law of Thermodynamics
the shiny nail in the top figure will, over a long time, rust &
eventually look as in the bottom figure. But, if the nail is
rusty,
it will not
spontaneously become shiny again!!
• Processes that are spontaneous at one temperature
may be non-spontaneous at other temperatures.
• Example in the figure:
For T > 0C ice will melt spontaneously.
For T < 0C, the reverse process is spontaneous.
 Irreversible Processes

Irreversible Processes 
Processes that cannot be undone by exactly reversing the process.
All Spontaneous Processes are Irreversible.
All Real processes are Irreversible.
Examples of Spontaneous, Irreversible Processes
1. Due to frictional effects, mechanical work changes into heat automatically.
2. Gas inflates toward vacuum.
3. Heat transfers from a high temperature object to a low temperature object.
4. Two solutions of different concentrations are put together and mixed uniformly.
Note!!
The 2 Law of Thermodynamics says that the opposite processes of these cannot proceed automatically. In order to take a system
nd

back to it’s initial state, external work must be done on it.

 Spontaneous Processes (changes):
Once the process begins, it proceeds automatically without the need to do work on the system.

• The opposite of every Spontaneous Process is a

Non-Spontaneous Process
that can only proceed if external work is done on the system.
Reversible Processes
• In a
Reversible Process,
the system undergoes changes such that the
system plus it’s surroundings can be put
back in their original states by exactly
reversing the process.
• In a
Reversible Process,
changes proceed in infinitesimally
small steps, so that the system is
infinitesimally close to equilibrium at every
step. This is obviously an idealization &
can never happen in a real system!
Another Statement of the 2nd Law of Thermodynamics
“The entropy of the universe does not change
for Reversible Processes” and also:
“The entropy of the universe increases for
Spontaneous Processes” “You can’t break even”.

For Reversible (ideal) Processes:

For Irreversible (real, spontaneous) Processes:

 Still Another Statement of the
2nd Law of Thermodynamics

“In any spontaneous process, there is

always an increase in the entropy of the
universe.”
The Total Entropy S of the Universe
has the property that, for any process,
∆S ≥ 0.
 More Examples of Spontaneous Processes
Free Expansion of a Gas
• The container on the right is filled with gas. The
container on the left is vacuum. The valve between them
is closed. Now, imagine that the valve is opened.

Valve
Vacuum Closed Gas

(courtesy F. Remer)
 Free Expansion of a Gas
• After the valve is opened, for some time, it is no longer an
equilibrium situation. The 2nd Law says the molecules on the right
will flow to the left. After a sufficient time, a new equilibrium is
reached & the molecules are uniformly distributed between the 2
containers.
The Entropy Increases!!!!

After some time,

there is a new
Valve
Equilibrium
Gas Open Gas

(courtesy F. Remer)
 Thermal Conduction
• A hot object (red) is brought into thermal contact with a
colder object (blue). The 2nd Law says that heat đQ will
flow from the hot object to the colder object.

Hot Cold
đQ

(courtesy F. Remer)
• After the 2 objects are brought into thermal contact, for some
time, by the 2nd Law, heat đQ flows from the hot object to the
colder object. During that time, it is no longer an equilibrium
situation. After a sufficient time, a new equilibrium is reached &
the 2 objects are at the same temperature.
The Entropy Increases!!!!

Warm
After some time,
there is a new
Equilibrium

(courtesy F. Remer)
 Mechanical Energy to Internal Energy Conversion
• Consider a ball of mass m. It’s Mechanical Energy is defined as
E = KE + PE. KE = Kinetic Energy, PE = Potential Energy.
• For conservative forces, E is conserved (a constant).
• Drop the ball from rest at a height h above the ground.

Initially,
E = PE = Conservation of
Mechanical Energy
mgh
Just before hitting
h tells us that
mgh =
the ground,
(½)mv2
E = KE = (½)mv2
Mechanical Energy E
is conserved!

(courtesy F. Remer)
• At the bottom of it’s fall, the ball collides with the ground & bounces upward. If it has an Elastic Collision with the ground, by
definition, right after it has started up, its mechanical & kinetic energies would be the same as just before it hit:
E = (½)mv2 = mgh
• In reality, the Collision will be Inelastic. So, the initial upward kinetic energy, KE', will be less than KE just
before it hit.

Just before hitting The collision is Inelastic,

the ground, so right after it bounces,
KE = (½)mv2. its kinetic energy is
KE' < KE.

Where did the lost KE go? It is converted to heat, which changes the
internal energy Ē of the ball. As a result, the ball heats up!!
(courtesy F. Remer)
The ball’s collision with the ground is inelastic, so it loses some
kinetic energy: KE' < KE. The lost kinetic energy is
converted to heat, which changes the ball’s internal energy Ē.
So, the ball gets warmer!!
In Ch. 4, we’ll show that, for an infinitesimal, quasi-static process
in which an object heats up, changing its temperature by an amount
dT, it’s internal energy change is dĒ = mcVdT
m ≡ ball’s mass & cV ≡ specific heat at constant volume

KE = (½)mv2
KE' < KE

The change in the ball’s internal energy is

dĒ = mcVdT
(courtesy F. Remer)
 Multiple Bounces of the ball
 Multiple Inelastic Collisions with the ground.
When it finally comes to rest after several bounces,
it may be MUCH warmer than when it was dropped!

The ball loses more KE on

each bounce & it eventually
stops on the ground. Thus,
after sufficient time, it tends
towards Equilibrium

The more bounces the ball

has, the warmer it gets!

The Ball’s Entropy Increases!!!!

(courtesy F. Remer)
 Brief Discussion of
“Impossible Processes” 
• Processes which are
allowed by the 1st Law of Thermodynamics
but which Cannot Occur Naturally
because they would violate the 2nd Law of Thermodynamics.
• Any process which would take a system from an equilibrium state to a non-
equilibrium state without work being done on the system would violate the
2nd Law of Thermodynamics & thus would be an Impossible Process!

(courtesy F. Remer)
 Examples of Impossible Processes
• Example 1: “Free Compression” of a Gas!
Initially, the valve is open
& gas molecules are
uniformly distributed
in the 2 containers.
Valve
Gas Open Gas

After some time, all gas

molecules are gathered in
the right container &
the left container is empty.

The Entropy Vacuum Valve Gas

Open
Decreases!!
(courtesy F. Remer)
 Thermal Conduction
Initially, an
object is warm.
Warm

After some time,

the left side is hot Hot Cold
& the right
side is
cold .
The Entropy
Decreases!!
(courtesy F. Remer)
 Conversion of Internal Energy to
Mechanical Energy
Initially, a ball is Hot
on the ground
& is hot.

After some time, the ball Warm

begins to move
upward with kinetic energy
KE = (½) mv2 The Entropy
& it cools down!
Decreases!!

(courtesy F. Remer)
 Impossible Processes
Cannot occur without the input of work

đW

(courtesy F. Remer)
• In such a process, the System’s Entropy Decreases, but the
Total Entropy of the System + Environment Increases

Decrease
Environment
in Entropy

đW

Increase
in Entropy
(courtesy F. Remer)