Lecture – III

Thermodynamics

Students are advised to go through the presentation

thoroughly and derive the equations as discussed in the class.
 ENTROPY AND STATISTICAL PROBABILITY

Macroscopic approach of thermodynamics: equilibrium state of an isolated system

is that state in which the entropy has its maximum value.

Microscopic approach to thermodynamics: the equilibrium state of an isolated system

would be the state with the maximum statistical probability.

Assuming 1 mole of gas

≡ 𝑁𝐴 molecules.
Impossible
process Boltzmann postulated
𝑅/𝑁𝐴

Equilibrium gaseous Highly improbable state of

number of equally probable
system after a hole is the gaseous system after
microscopic arrangements
punched in the the hole has been for the system
diaphragm. punched.

Probability=1𝑁𝐴 =1 Probability=(1/2)𝑁𝐴 =
It is often difficult to count the number of equally probable arrangements in the
final state and in the initial state, but the ratio Ω2 /Ω1 in this case is equal to the
ratio of the probability that all the molecules are in one chamber to the probability
that they are all in one chamber or the other.

= −𝑅 ln 2
 Third law of thermodynamics

The entropy of each pure element or substance in a perfect crystalline form is

zero at absolute zero.

Ω = 1 for perfectly ordered crystal. Hence 𝑆 = 𝑘𝐵 ln Ω = 0

Exceptions to the third law

Imagine the mixed crystal to be formed from a pure crystal of A and a pure crystal of
B, then for the mixing process

• Impure crystal has at least the entropy of mixing at the absolute zero, its entropy
cannot be zero; such a substance does not follow the third law of thermodynamics
• Substances that are chemically pure do not fulfill the requirement that the crystal
be perfectly ordered at the absolute zero of temperature. E.g. CO and NO. In the
crystals of CO and NO, some molecules are oriented differently than others.

In the actual crystal of CO, the two ends of the molecule are oriented
randomly; it is as if two kinds of carbon monoxide were mixed, half
and half. The molar entropy of mixing would be

• Crystalline hydrogen has a residual entropy of 0.750 R = 6.23 J/K/mol at the

absolute zero of temperature. This entropy is not the result of disorder in the
crystal, but of a distribution over several quantum states.
 Internal energy U

Fundamental equation:
Combined 1st and 2nd law
of thermodynamics

Chemical work which involves

change in number of moles.

Chemical potential is a measure of potential a species has to move from one phase to
another or undergo a chemical reaction.

U is a function of S, V, {ni}, where {ni} is the set of amount of species i; and represented
by U(S, V, {ni}). The total differential of U is written as:

Ns is the number of different species in the system.

Equations of state

Maxwell Relations, obtained

by equating second cross-
partial derivatives as dU is an
exact differential.
 Thermodynamic potentials

Definitions:
Enthalpy: H = U + PV
Helmholtz Free Energy: A = U – TS
Gibbs Free Energy: G = H – TS
dH = dU + d(PV) = dU + PdV + VdP

What are the equations of state in terms of H, A and G?

What are the corresponding Maxwell relations?
Spontaneity criterions

Internal energy provides a criterion for whether a process can occur

spontaneously at constant S, V, and {ni}.

Substitute 2nd law 𝑑𝑆 ≥ đ𝑞/𝑇, in the 1st law with

This is one of the criterions for spontaneous change and equilibrium in the
system involving PV work and specified amounts of species. At equilibrium, U
at constant S, V, and {ni} must be at a minimum.
Similarly derive:
 Few relations in Helmholtz energy A and Gibbs energy G

Substituting 2nd law of thermodynamics (𝑑𝑆 ≥ đ𝑞/𝑇 in 1st law ( ) we

have

At constant temperature T

−𝑑 𝑈 − 𝑇𝑆 ≥ −đ𝑤 or 𝑑𝐴 𝑇 ≤ đ𝑤 or − 𝑑𝐴 𝑇 ≥ −đ𝑤

In a reversible process at constant T, the work done on the

system is equal to the increase in the Helmholtz energy

The decrease in A is an upper bound on the total work done in the surroundings
 Similarily if the 1st law is written as: 𝑑𝑈 = đ𝑞 − 𝑃𝑑𝑉 + đ𝑤nonpv

Using 2nd law: −𝑑𝑈 − 𝑃𝑑𝑉 + 𝑇𝑑𝑆 ≥ −đ𝑤nonpv

At constant T and P :

For a reversible process at constant T and P the change in Gibbs energy is equal to the
non-PV work done on the system by the surroundings. Thus, when work is done on the
system, the Gibbs energy increases, and when the system does work on the
surroundings, the Gibbs energy decreases.

The decrease in G is an upper bound on the non-PV work done on the surroundings.
 Gibbs–Helmholtz equation

𝜕𝐺
Gibbs free energy is defined as: 𝐺 = 𝐻 − 𝑇𝑆. Using 𝑆 = − we have
𝜕𝑇 𝑃,{𝑛𝑖 }

Eliminating G from above we have: Gibbs–Helmholtz

equation

For a change between state 1 and state 2:

Since

At constant T, for a single component system with no chemical reaction

we can write

Effect of pressure P
on Gibbs energy G
For ideal gas: substituting 𝑉 = 𝑛𝑅𝑇/𝑃, then:

where 𝑃∘ is the standard state pressure.

 Chemical potential

Chemical potential of species i, 𝜇𝑖 is defined as:

It is also referred to as partial molar Gibbs energy, 𝜇𝑖 = 𝐺𝑖

Suppose an infinitesimal amount dni of species i is Matter

transferred from phase 𝛼 to phase 𝛽 at constant T flow
and P.

For the transfer to be spontaneous 𝑑𝐺 < 0 and hence

𝜇𝑖 𝛼 > 𝜇𝑖 𝛽 . Hence a species diffuses spontaneously
from the phase where its chemical potential is higher to the
phase where its chemical potential is lower.

Also 𝑑𝐺 = 0 if 𝜇𝑖 𝛼 = 𝜇𝑖 𝛽 .

Thus, at equilibrium, the chemical potential of a species is the same in all of the
phases of a system.
Class test (5 marks) 5minutes

heat absorbed in a process

at constant pressure