Entropy and the second law of

thermodynamics
Introduce heat engines, which are cycle processes that
convert heat into work.
Show various forms of the second law of thermodynamics
and prove their equivalence, in particular showing that
no engine can be more efficient than a Carnot engine.
Prove Clausius theorem.
Show the concept of entropy.
Derive the important equation dU = TdS-pdV, which
combines the first and second laws of thermodynamics.
Introduce the Joule expansion.

The second law of thermodynamics was develop by three

different statements from Carnot, Clausius and Kelvin.
Clausiuss statement of the second law of thermodynamics
No process is possible whose sole result is the transfer of
heat from a colder to a hotter body
Example 1:
Pick up a brick of mass, m, and carry it up
to the top of building of height, h, and then
let it fall back to ground level by dropping it
off the top.
All the work done that carrying the brick to
the top of the building will be dissipated in
heat as the brick hits the ground (plus a
small amount of sound).

Work done = mgh

Kelvins statement of the second law of thermodynamics

No process is possible whose sole result is the complete
conversion heat into work

These two statements of the second law of

thermodynamics do not seem to be obviously connected.
The equivalence of these two statements will be discuss
later.

The Carnot engine

Kelvins statement of the second law of thermodynamics says

that you cant completely convert heat into work.
The Carnot engine will show a conversion from heat to work is
possible.

A Carnot cycle consists of two reversible

adiabats (BC and DA) and two reversible
isotherms (AB and CD).
As shown in the figure, it is operated in
the direction of ABCDA, i.e.,
clockwise around the solid curve.
Heat Q2 enters in the isotherm AB and
heat Q1 leaves in the isotherm CD.

Process: a b c d a

Example 2: Carnot engine

The Carnot cycle consists of two reversible adiabats and two reversible isotherms
for an ideal gas. The engine operates between two heat reservoirs, one at a
higher temperature, Th and one at a lower temperature, Tc. Heat enters and
leaves only during the reversible isotherms (because no heat can enter and leave
during an adiabat). Heat Q2 enters during the expansion AB and heat Q1 leaves
during the compression CD.

Because the Carnot process is cyclic, the change of internal

energy (as state function) in going round the cycle is zero.
Thus, the work done (output) by the engine, W is given by:

W Q2 Q1

The Carnot engine is drawn as a machine with

heat input Q1 from a reservoir at temperature T1,
and two outputs, one of work, W and the other
of heat, Q, which passes into the reservoir at
temperature T2.
The efficiency of an engine is important to
characterize engines.
The efficiency, of an engine is defined as the
ratio of the work out to the heat in,

HOT

Carnot

W
Q1

Note that since the work out cannot be greater than the heat in (i.e. W Q1)
we must have that 1. The efficiency must be below 100 %.

COLD

T1 T2

Example 4:
For the Carnot engine, determine the efficiency in terms of the temperatures
T2 and T1.
Carnot

Q Q1
Q
T
W
2
1 1 1 1
Q1
Q2
Q2
T2

How does this efficiency compare to that of a real engine? It turns

out that real engines are much less efficient than Carnot engines.

Example 5:
A power station steam turbine operates between T1 ~ 800 K and T2 ~ 300 K. If
it were a Carnot engine, it could achieve an efficiency of Carnot,
Carnot 1

300 K
60 %
800 K

but in fact real power stations do not achieve the maximum efficiency and
figures closer to 40 % are typical.

Carnots theorem
Of all the heat engines working between two given temperature,
none is more efficient than a Carnot engine.
Reversible engines
Q2

Q2
E

Q1

T2

Carnot

Carnot

Q1

Q1

T2

Q2

Q2

R
Q1
T1

T1

E Carnot

R Carnot

All reversible engines working between two temperatures have

the same efficiency, Carnot .
T2 T1
Carnot

T2

Equivalence of Clausius and Kelvins statements

If a system violates Kelvins
statement of the second law of
thermodynamics, one could connect
it to a Carnot engine as shown in (a).
Q2

(a)

Q2

Kelvin
violator

If a system violates Clausius

statement of the second law of
thermodynamics, one could connect
it to a Carnot engine as shown in (b).

T2

Carnot

Q1

(b)

Clausius

violator

Q1

Q1

T2

Q2

Q1

T1

The first law implies:

Q2' W

Q2 W Q1

The heat dumped in the reservoir at

temperature, T2:
Q2 Q2' W
Kelvin violator does not exist

T1

The first law implies:

Q2 Q1 W
Clausius violator does not exist

Clausius theorem

In a one Carnot cycle, heat Q2 enters and heat

Q1 leaves. Heat is therefore not a conserved
quantity of the cycle.
Q2 T2

Q1
T1

For heat entering the system at each point,

Qrev
Q1 0,
Q
2
T
T2
T1
cycle

dQrev
0
For Carnot cycle,
T
For general cycle, heat dQi enters at a particular
part of the cycle. At this point the system is
connected to a reservoir, which is at
temperature Ti. The total work extracted from
the cycle is W, given by:

dQ ,
i

cycle

from the first law of thermodynamics.

(a) A general cycle in which heat dQi

enters in part of the cycle from a
reservoir at temperature Ti. (b) The heat
entering the reservoir at Ti from a
reservoir at temperature T via a Carnot
engine.

For the heat at each point is supplied via a

Carnot engine, each Carnot engine produces
work, dWi, and,
heat to reservoir at Ti
heat to reservoir at T

Ti
T

Thus,
T

dWi dQi 1
Ti

dQi
dQi dWi

Ti
T

Total work produced per cycle =

W+

dW

cycle

dQi +

cycle

dQi 1 0
Ti

cycle

dQi
0
T
i
cycle

Clausiustheorem:
For any closed system,

dQi
0,
Ti

Where equality necessarily holds for a reversible cycle (T0).