September 11, 2001

Reading: Chapter Four

Homework: None

Entropy and The Degree of Disorder:

Consider a solid crystalline material:
At zero K: All atoms frozen at fixed positions on a periodic lattice.
Add heat to a finite temperature, S increases: all atoms vibrate about their lattice
positions; so instantaneously atoms are randomly displaced from their lattice
positions --- disorder.
Add more heat to the melting temperature, S increases further: atoms moving
away completely from their lattice positions; so instantaneously atoms are
randomly distributed in the space --- more disorder. In the liquid phase, a periodic
lattice is destroyed, however, there still remains certain degree of local order. On
average, the number of nearest neighbors and the nearest-neighbor distances of
any given atom are about the same.
Add more heat to the evaporating temperature, S increases even further: atoms
moving completely randomly in the space --- even more disorder. In the gas
phase, even the local order doesnt exist; the motion of individual atoms is
completely uncorrelated.
Therefore, there must be a correlation (relationship) between the entropy and the
degree of disorder. The disorder is related to the various ways atoms can share the
total amount of energy. For example, consider we add a fixed amount of heat
(thermal energy) to a lattice to increase its lattice vibrations (kinetic energy). This
amount of heat can be distributed into the lattice in many different ways, i.e,
instantaneously each individual atom may increase its velocity of a different
amount and moving in different directions, as long as the sum of total increase of
kinetic energy from all atoms corresponds to the heat input.
Disorder is also related to various ways atoms (particles) can be distributed in the
space. For example, consider the mixing of two gases, or liquids, or solids. As an
irreversible process, the entropy is increased. However, this may happen without
any energy transfer (heat input or work done) but only disorder is increased, i.e.,
the spatial arrangement of particles become more messy.

Gas A

Gas B

adiabatic

diaphragm

Gas (A+B)

Example of liquid:
Examples of solid:

alcohol + water:
random solution
silicon + germanium: random solution
Gold + silver:
random solution

Disorder --- A measure of the number of ways a system can be realized under a
give set of state variables.
The concept of Microstates:
Consider three particles localized in space, each of them may occupy one of the
many energy levels that are equally spaced (0, u, 2u, 3u, ). [It may be easier to
visualize an equivalent case: three men of the same weight climbing an equally
spaced staircase, each one of them may stand on (occupy) one step level with
potential energies of 0, (gh), 2(gh), or 3(gh), , where h is the step height; u=gh]
If the total energy is zero U = 0,
= 3u
= 2u
=u
=0
All three men (particles) must be distributed on the ground level of zero energy.
Since interchange of them is indistinguishable as they have the same weight
(identical particle), there is only one way to realize this distribution.
If the total energy is U = u,
= 3u
= 2u
=u
=0
One of the particles must be distributed onto the first level, the other two remains
at the ground level. Since any one of them can be placed onto the first level, there
are three possible arrangements to realize this distribution.
If the total energy is U = 2u.
We can distribute particles in two different ways: in the first distribution, one
particle is put into the second level, the other two remains at the ground level.
Similar to the case of U=u, there are three possible arrangements to realize this
distribution:

 = 3u
= 2u
=u
=0
In the second distribution, two particles are put into the first level and the third
one remains on the ground level. Since any one of them can be left on the first
level, three are also three possible arrangements to realize this distribution.
= 3u
= 2u
=u
=0
The total number of arrangements for U=2u is 3+3 = 6.
If the total energy is U = 3u.
We can distribute particles in three different ways: in the first distribution, all
three particles are put on the first level. Similar to the case of U=0, there is only
one possible arrangement to realize this distribution:
= 3u
= 2u
=u
=0
In the second distribution, one particle is put into the third level, the other two
remains at the ground level. Similar to the case of U=u, there are three possible
arrangements to realize this distribution:
= 3u
= 2u
=u
=0

In the third distribution, one particle each is put into the ground, first, and second
level, respectively. Since any one of three can be put first on the second level and
then any one of the remaining two can be put on the first level, the total number of
ways to arrange them is 3x2x1=6.
= 3u
= 2u
=u
=0
and
= 3u
= 2u
=u
=0
The total number of arrangements of all distributions for U=3u is 1+3+6 = 10.
So, given a total energy, there are number of distinguishable ways to arrange
particles into different levels, amounting to the same total energy. These
individual arrangements are called microstates. So, there can be many microstates
corresponds to a given distribution and all the microstates correspond to a single
macrostate of energy U.
Calculating number of microstates for a given distribution:
Consider a system containing number of N particles of total energy U. They are
distributed into an infinite number of different energy levels such that n0j in 0, n1j
in 1, n2j in 2,, subject to nij = N and nij i = U , for a given distribution
i

j. The possible distinguishable arrangements, i.e., the number of microstates for

this distribution can be calculated as following:
The identical particle only become distinguishable when they are on different
levels. The total number of ways to distribute N identical particles into all
different levels so that all the resulting arrangements are distinguishable is N!.
This is because there is N ways to pick the first particle, N-1 ways to pick the
second particle, , one way to pick the last particle; so the total number of ways
is Nx(N-1)x(N-2)x x1 = N!.

When identical particles are distributed on the same energy level, they are
indistinguishable. So, when there are nij! ways to put number of nij particles into
the same energy level i, they resulted into nij! indistinguishable arrangements; i.e.
only one distinguishable arrangement.
j = distinguishable arrangemetns
total number of possible arrangements
number of indistinguishable arrangements
N!
j = j j j j
n0 !n1 !n2 !n3 !
j = No. of distinguishable ways that system is realized in this distribution, i.e.,
ways to arrange particles into this distribution of particles in different levels.
N! = No. of ways to to put N particles into individual levels;
nij! = No. of ways to put ni particles into level i.
j =

Consider the example of three particles we discussed before,

3!
= 1;
3!0!0!0!
3!
=
= 3;
2!1!0!0!
=

For U=0,
For U=u,

1 =

For U=2u,

3!
= 3;
2!0!1!0!

2 =

3!
= 3;
1!2!0!0!

For U=3u,
1 =

3!
= 1;
0!3!0!0!

2 =

3!
= 3;
2!0!0!1!

3 =

3!
=6
1!1!1!0!

So, j is the total number of microstates of a given distribution, then

total = j
j

denotes the total number of microstates corresponds to a macrostate.