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
Heat absorbed
Q = ∆Ē + W Work done
by the system by the system
Change in the system’s
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
Change in entropy
of the system
DS ³ 0
• This gives the Preferred (natural)
Direction of Energy Transfer
• This determines whether a process can occur or not.
 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.

 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.”