Weve spent quite a bit of time learning about how the

individual fundamental particles that compose the

universe behave.
Naturally, I am sure you are wondering:

Can we start with that microscopic

knowledge and learn something about bulk
properties of matter such as temperature?

Will the peculiar rules governing the

behavior of an individual particle or small
group of particles
(such as the Pauli principle) influence
the properties of the matter they
compose?
Particles have identical physical
propertiesbut can be
distinguished by following their
(well defined) classical paths.

ASSUMPTIONS
ASSUMPTIONS

In equilibrium, the energy distribution

of the particles will converge
to the most probable allowed.
In principle, there is no
limit on the number of particles
occupying each state.
 Imagine 6 particles with 9 indivisible quanta of energy divided among them.

If the particles are indistinguishable, we only care about how many particles
are in each state, and there are 26 unique ways to distribute the energy
among them26 unique combinations.
If the particles are distinguishable (we make a distinction as to which particle
is in which energy state), there are 2002 unique permutations.

Remember that for now we have assumed that these particles are distinguishable.
 If you are making choices from n objects, then on your first pick you have n
choices. On your second pick, you have n-1 choices, n-2 for your third choice
and so forth. As illustrated before for 5 objects, the number of ways to pick
from 5 objects is 5! .

Suppose you are going to pick a subset r out of the total number of objects n,
like drawing 5 cards from a deck of 52. For the first pick, you have n choices,
then n-1 and so on down to n-r+1 for the last pick. The number of ways you
can do it is:

n!
n(n 1)(n 2)...(n r 1) n Pr
(n r )!
 Here we have to choose
If we care about which more than one particle
particle is in which for each state, and we
state, there are six can distinguish between
different states where different combinations
one particle one particle of particles in each
has all of the energy. state, so the
multiplicity gets bigger.

If each of these microstates is equally likely (and we assumed that we

will converge on the most probable), it seems that nature doesnt favor the
situation where one particle has all of the energy.
We assume that each microstate (unique permutation) is equally probable.
In other words, if there are 180 permutations that will produce a particular
energy distribution, then that distribution is more probable than a distribution
that can only be produced by six permutations.

Energy Average
level number To find the average number of particles in each state
0 2.143
n j n j1 p1 n j 2 p2
1 1.484 average number of
particles in the multiply by the number
2 0.989 jth energy level count the of permutations that
number of can produce this
3 0.629 particles in distribution divided by
4 0.378 each state for the total number of
this permutation for all
5 0.210 distribution distributions
6 0.105
7 0.045 There are only 6 (out of 2002) permutations that can
produce a situation where one particle has all 9E.
8 0.015 Apparently its not very probable.
9 0.003
 y

v constant

z x
x

z
dv
 The Maxwell-Boltzmann distribution
can be shown graphically as the plot of
the number of molecules traveling at a
3k BT given speed versus the speed. As the
rms
m temperature increases, this curve
broadens and extends to higher
speeds.
 3k BT
Using: rms follows
m

1 3 A classical molecule in thermal

The equipartition theorem m 2 K k BT equilibrium has an average energy
2 2 of kT/2 per degree of freedom.

But generally, there are more than three degrees of freedom (more than just the
translational motion in each of x, y, and z):

1 2
Erot I For molecules that can rotate, you can have a rotational
2 degree of freedom.

1 1 2 A one dimensional harmonic oscillator has two

E m x kx
2
degrees of freedom, one corresponding to its
2 2 potential energy, the other to its kinetic energy.

There is an energy kT/2 associated with each of these degrees of freedom.

The first two pictures give the same outcome. Even though a and b are
identical, you can tell them apart by following them along their unique paths.

a b

a b a b a ?? b

b a

Quantum mechanically, each particle has some probability of being

somewhere at a particular time, which overlaps greatly at the collision point.
Which particle emerges where? In wave terms, they interfered.
Since we know that particles are really wavicles and Maxwell Boltzmann
statistics is only good for distinguishable particles, what good is it?
The Maxwell-Boltzmann distribution assumes that the particles they describe
are distinguishable. Two particles can be considered distinguishable if the
distance separating the particles is large compared to their DeBroglie
wavelength.
Put in mathematical terms, if their average separation is larger than the
the uncertainty in their momentum. d x

Using the uncertainty principle: px
2
the particles are moving randomly and the
At thermal equilibrium: px 0 directions will cancel each other

p x2 0 but their magnitudes arent zero

p x2 k BT
p x2 p x mk BT
2
KE for each degree of freedom p x
2m 2
1
Maxwell Boltzmann
V 3 N statistics are valid for
x using d 1 low density and high
V 8 mk BT 2
3
2 mk BT N temperature and
particle mass
Before, we had distinguishable particles.
a ( r1 ) b (r2 ) assuming they are in two different states, you get two
distinct wavefunctions, where r1 and r2 are the positions
of the toe particles
a ( r2 ) b (r1 )

the probabililty of both particles 2

* a* (r1 ) a* (r2 ) a (r1 ) a (r2 ) a (r1 ) a (r2 )
2
being in the same state is then

but indistinguishable particles require a more complicated wavefunction.

1 1
[ a (r1 ) b (r2 ) a (r2 ) b (r1 )] or [ a (r1 ) b (r2 ) a (r2 ) b (r1 )]
2 2
If both particles are in the same state these become
1 bosons as they are called, are
[ a (r1 ) a (r2 ) a (r2 ) a (r1 )] 2 a (r1 ) a (r2 ) more likely to be found in the
2 same energy state than apart
2 2
* 2 a (r1 ) a (r2 ) 2 *

1 fermions, however, can never be found

[ a (r1 ) a (r2 ) a (r2 ) a ( r1 )] 0 in the same state! The uncertainty
2 principleagain.
We are now considering indistinguishable particles we are now only counting
how many particles are in each energy state, rather than which particles are
in each energy state.

However, our assumption that there is no theoretical limit on the number of

particles occupying each state still holds.

Now each of the 26 energy combinations show occur with equal probability.
 Average Average n j n j1 p1 n j 2 p2
Energy number number
level Maxwell- Bose-
Boltzmann Einstein
This probability is now
0 2.143 2.269 the same for each
energy distribution,
1 1.484 1.538 just 1 divided by the
total number of
2 0.989 0.885 distributions.
3 0.629 0.538
Not surprisingly, the distribution for
4 0.378 0.269
bosons show a higher probability at
5 0.210 0.192 the extremes, where there were fewer
6 0.105 0.115 permutations producing the observed
energy spectrum.
7 0.045 0.077
8 0.015 0.038
9 0.003 0.038
 The specific heat is the amount of heat per unit mass
required to raise the temperature by one degree
Celsius.
dU here, U is the thermal energy
C
dT
Thermal energy per atom:
number of degrees of freedom per
dimension (kinetic and potential)
in real life, there are
three dimensions
k BT / 2 2 3 3k BT

energy per degree of freedom

To get the energy per mole, multiply by
(from the equipartition theorem) Avagadros number:

U 3N A k BT 3RT
 dU d Note that the specific heat predicted by
3RT 3R 5.97 cal mol K the classical equipartition theorem is
dT dT constant with temperature!

This prediction Einsteins solution:

disagrees with the
data at low Treat each atom as
temperature. an independent
quantum simple
harmonic oscillator,
and quantize its
energy.

The energy is then: The specific heat is then:

this approaches the classical
E result, kT, at high temperatures dU
2
e k BT
as we know it should (the C 3R
1
e
k BT
e dT 2
k BT
/ k B T
correspondence principle) 1
Einsteins approach worked (mostly). Some fine tuning was required, however.
Debye pointed out that the atoms in a solid do not move independently but interacts
with its neighbors. The result - continuous vibrational waves-sound.
Once again we assume that the particles are distinguishable.
Thanks to the Pauli exclusion principle, we must, however, remove
assumption that there is no theoretical limit on the number of particles in
each state!

As in the case for bosons, each

allowed energy distribution has an
equal probability.

Unlike the boson case, only five

energy distributions are allowed!
All others have more than the
permitted two particles in each
state in violation of the exclusion
principle.
 Average Average Average
number number number
E
Maxwell- Bose- Fermi- n j n j1 p1 n j 2 p2
Boltzmann Einstein Dirac
0 2.143 2.269 1.8
1 1.484 1.538 1.6 Now there are few allowed
states. Since the particles are
2 0.989 0.885 1.2 indistinguishable, each state is
again equally likely.
3 0.629 0.538 0.8
4 0.378 0.269 0.4
Note that the energy distribution
5 0.210 0.192 0.2
will flatten out at higher energies.
6 0.105 0.115 0 If one particle has all of the
7 0.045 0.077 0 energy state, that would require
all of the other particle to be in the
8 0.015 0.038 0
same energy state zero - in
9 0.003 0.038 0 violation of the Pauli principle.