Second Law of Thermodynamics

1st and 2nd laws are fundamental unifying principles of thermodynamics

Restrictions on the energy transfer
Energy is conserved
Heat is a form of energy transfer
Kelvin statement of the second law:
There is no process whose only effect is to
accept heat from a single heat reservoir and
transform it entirely into work.
Lord Kelvin (William Thomson) (1824-1907)

Hypothetical devices violating the 2nd Law

Clausius statement of the second law:

There is no process whose only effect is to accept heat
from a colder reservoir and transform it to a hotter one.
Rudolf Clausius
(2.1.1822 -24.8.1888)

x
Note the careful wording:
Kelvin statement of the second law:

~
dV
W nRT ~
V0 V
V

nRT ln

There is no process whose only effect is to

accept heat from a single heat reservoir and
transform it entirely into work.

V0 V

T=const
Q in

Why is this no contradiction

Because: Transformation of heat

Note:

work is not the only effect (piston moved)

In a cyclic process engine remains unchanged

Alternative Kelvin statement:

only

Clausius statement of the second law:

There is no process whose only effect is to accept heat
from a colder reservoir and transform it to a hotter one.
Again: A refrigerator accepts heat from a colder reservoir and transfers heat
to the hotter reservoir

Why is this no contradiction

Because: This is not the only thing a refrigerator does.

It uses electrical or mechanical energy.

Alternative Clausius statement

Michael Flanders and Donald Swan

The First Law of Thermodynamics:
Heat is work and work is heat.
Very good!

The Second Law of Thermodynamics:

Heat cannot of itself pass from one body to a hotter body.
Heat wont pass from a cooler to a hotter.
You can try it if you like, but you far better notter,
Cause the cold in the cooler will get hotter as a ruler,
Cause the hotter bodys heat will pass to the cooler.
First law: Heat is work and work is heat.
Heat will pass by conduction,
And heat will pass by convection,
And heat will pass by radiation,
And thats a physical law.
Heat is work and works a curse,
And all the heat in the universe is gonna to cool down,
Cause it cant increase,
And then therell be no more work and therell be perfect
peace.
Really!
Yeah, thats entropy man.
And all because of the second law of thermodynamics which
lays down that:
You cant pass heat from a cooler to a hotter.
You can try it if you like, but youd far better notter,
Cause the cold in the cooler will get hotter as a ruler,
Cause the hotter bodys heat will pass to the cooler.
And thats a physical law.
Ooh, Im hot!
Hot! Thats because youve been working!
Thats the first and second law of thermodynamics.

We show with the help of the Kelvin statement that:

(*)

All 2-temperature engines accept heat at the hotter reservoir and

reject heat at the colder reservoir

Lets call it test engine

Indirect proof:

Contradiction of (*): There is at least one 2-temperature engine which accepts

heat from the colder reservoir and rejects
heat to the hotter reservoir
Q rod
h

=
e.g., by adjusting copper rod

Q htest

Th
Test engine
Copper
rod

W
Tc

Q rod
h

=
e.g., by adjusting copper rod

Q htest

Non-Kelvin
device

Th

Test engine
Copper
rod

W
Tc

Since the Kelvin statement rules out the possibility of the device
Contradiction of (*)

(* )

true

False

All 2-temperature engines accept heat at the hotter reservoir and

reject heat at the colder reservoir

Equivalence of the Clausius and Kelvin statements

Logical structure of the proof of equivalence:
I

II

Kelvin-statement

true

false

true

false

Clausius-statement

true

true

false

false

possibility

III

IV

We show:
1 Kelvin-statement false

Clausius-statement false

2 Clausius-statement false

Kelvin-statement false

The decision between possibility I and IV is made by experimental experience

1 Kelvin-statement false

There is a non-Kelvin engine

Lets combine this non-Kelvin engine with a heat pump (which we know to exist)

There is a non-Clausius engine

Clausius-statement false

2 Clausius-statement false

There is a non-Clausius engine

Lets combine this non-Clausius engine with a heat engine (which we know to exist)

Q
Q

Q Q

There is a non-Kelvin engine

Kelvin-statement false