Aum Sri Sai Ram

Statistical Mechanics
Course Code - PPHY 302
Lecture - 5
Recap on “ensembles”

2
Illustration of microstates (2 particles in a box)

3
Some terminology
Ensemble

For a given macrostate (N,V,E), a statistical system, at any time t, is

equally likely to be in any one of an extremely large number of distinct
microstates.

As time passes, the system continually switches from one microstate to

another.

Over a reasonable span of time, all one observes is a behavior “averaged”

over the variety of microstates through which the system passes.

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Ensemble
It may, therefore, make sense if we consider, at a single
instant of time, a rather large number of systems — all being
some sort of “mental copies” of the given system — which are
characterized by the same macrostate as the original
system but are in all sorts of possible microstates.

This collection of systems is called an ensemble.

It is a mental construct.

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6
Query on Entropy

Disorder is used as a synonym for entropy

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Few examples

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Expansion of an ideal gas
● The difference between the initial
state and the final state of the ideal
gas is an increase of volume,
which provides the gas particles
with more space for their motion.
● Disorder, in this case, is not linked
to a structural change that
provides freedom of movement, as
in the case of sublimation, but,
rather, more freedom of movement
is provided in a larger volume.
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Ferromagnet and paramagnet
Ferromagnet

Paramagnet

In the microscopic picture, the magnetic moments of the ferromagnetic

material are mostly aligned in one direction (ordered). At temperatures
above the Curie point, the magnetic moments are randomly oriented
(disordered) to produce paramagnetic behavior. From a thermodynamic
point of view, the entropy increases in the transition from ferromagnetism
to paramagnetism. 11
Problem
Two-state system

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 Internal energy as a function of T

At low temperature, the

system is in the lower level
and the internal energy is
U = - Δ/2 .

At high temperature, the

two levels are each
occupied with probability
1/2, U therefore tends to 0
(which is halfway between
-Δ/2 and Δ/2)
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Entropy as a function of T
At low temperature, the
system is in the lower level.

No. of microstates = 1

At high temperature, the two

levels are each occupied
with probability 1/2,
No. of microstates = 2
entropy tends to
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 Entropy as a function of T
The entropy rises as the
temperature increases because it
reflects the freedom of the system
to exist in different states, and at
high temperature the system has
more freedom (in that it can exist in
either of the two states).

Conversely, cooling corresponds to

a kind of “ordering” in which the
system can only exist in one state
(the lower), and this gives rise to a
reduction in the entropy.

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Heat capacity as a function of T

The heat capacity is very small both

(i) at low temperature (kBT<<Δ) and
(ii) at very high temperature
(kBT>>Δ),

because changes in temperature

have no effect on the internal energy
when (i) the temperature is so low
that only the lower level is occupied
and even a small change in
temperature won’t alter that, and

(ii) the temperature is so

high that both levels are occupied
equally and a small change in
temperature won’t alter this.
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Heat capacity as a function of T

At very low temperature, it is hard to

change the energy of the system
because there is not enough energy
to excite transitions from the ground
state and therefore the system is
“stuck”.

At very high temperature, it is hard to

change the energy of the system
because both states are equally
occupied.

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Heat capacity as a function of T
In between, roughly around a

temperature T ≈ Δ/kB, the heat

capacity rises to a maximum,

known as a Schottky anomaly.

This arises because at this temperature, it is possible to thermally excite

transitions between the two states of the system.
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Schottky anomaly

The Schottky anomaly is an effect observed in solid-state physics where

the specific heat capacity of a solid at low temperature has a peak. It is
called anomalous because the heat capacity usually increases with
temperature, or stays constant.

It occurs in systems with a limited number of energy levels

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