Entropy

In 1850 Clausius introduced a new thermodynamic

state variable Entropy (its a Greek word meaning
turning into).
Entropy is a measure of how much heat is
unavailable for conversion into work.
A thermodynamic system can described by a
temperature T, an internal energy U and an entropy
S. The entropy provides a relation between heat
and temperature.

Entropy-2
The change in entropy, dS, between two
equilibrium states is given by the heat
transferred, dQ, divided by the absolute
temperature T, of the system in this
interval ,that is
dQ
dS
T

Entropy-3
In any spontaneous process the entropy can
not decrease.

dS 0.
This is the second law of thermodynamics,
with equality holding for a reversible
process.

Entropy-4
Because of the second law , all of the internal
energy in a system is not available to do work on
another system. Integrating the last equation we
have the total heat energy of a system is Q=TS.
Therefore the free energy, A is defined to be

A U TS ,
Is the difference between the internal energy and
the heat energy in the system that is available to do
work.

Entropy-5
Microscopic origin of entropy was essentially
explained by Maxwell, Boltzmann and Gibbs
around 1870.
Let i index the possible states of a system, pi be
the probability to be in the i-th state and let there
be total states. Then the microscopic definition

of the entropy is
S k
i 0

p ln p ,
i

Where k is Boltzmanns constant

Entropy-6
If all the states are equally likely then
1

therefore , S k ln
pi

This equation was so important to

Boltzmann that it appears on his grave.

Change of Entropy in a Carnot

cycle
In a Carnot cycle

Q
Q
dS

T
T
Q
but
T
Q cold T
hot

cold

hot

h
c

Therefore , dS 0

The entropy of the universe remains constant in a

reversible process. So the entire energy is available to
do work and after a complete reversible cycle. If we
have a computer made up of reversible gates only we
can do our computation without expensing energy.

Entropy change in ideal gas

For an ideal gas (Ti ViTf Vf)
dQ dU PdV
dV
nCV dT nRT
V
f

dQ
Therefore , S
T
i
nCV

T
ln
T

f
i

V
nR ln
V

f
i

Entropy change for free

expansion
For free expansion Tf=Ti

V
S nR ln
V

f
i

Entropy change in heat

conduction
Entropy change in Heat conduction is
S

T h T c