TR 9

CHAPTER 9
Statistical Physics
 9.1 Historical Overview
 9.2 Maxwell Velocity Distribution
 9.3 Equipartition Theorem
 9.4 Maxwell Speed Distribution
 9.5 Classical and Quantum Statistics
 9.6 Fermi-Dirac Statistics
 9.7 Bose-Einstein Statistics
Ludwig Boltzmann, who spent much of his life studying statistical

mechanics, died in 1906 by his own hand. Paul Ehrenfest, carrying on
his work, died similarly in 1933. Now it is our turn to study statistical
mechanics. Perhaps it will be wise to approach the subject cautiously.
- David L. Goldstein (States of Matter, Mineola, New York: Dover, 1985)

1
9.1: Historical Overview
Statistics and probability

 New mathematical methods developed to understand the
Newtonian physics through the eighteenth and nineteenth
centuries.
Lagrange around 1790 and Hamilton around 1840.

 They added significantly to the computational power of
Newtonian mechanics.
Pierre-Simon de Laplace (1749-1827)

 Made major contributions to the theory of probability.
2
Historical Overview
Benjamin Thompson (Count Rumford)
 Put forward the idea of heat as merely the motion of individual
particles in a substance.
James Prescott Joule

 Demonstrated the mechanical equivalent of heat.
James Clark Maxwell

 Brought the mathematical theories of probability and statistics to
bear on the physical thermodynamics problems.

 Showed that distributions of an ideal gas can be used to derive the
observed macroscopic phenomena.

 His electromagnetic theory succeeded to the statistical view of
thermodynamics.
3
Historical Overview
Einstein
 Published a theory of Brownian motion, a theory that supported
the view that atoms are real.
Bohr
 Developed atomic and quantum theory.
4
9.2: Maxwell Velocity Distribution
 There are six parameters—the position (x, y, z) and the velocity
(vx, vy, vz)—per molecule to know the position and instantaneous
velocity of an ideal gas.
 These parameters six-dimensional phase space
 The velocity components of the molecules are more important

than positions, because the energy of a gas should depend only
on the velocities.
 Define a velocity distribution function .
= the probability of finding a particle with velocity
between .
where
5
Maxwell Velocity Distribution
 Maxwell proved that the probability distribution function is
proportional to exp(−½ mv2 / kT).
Therefore .
where C is a proportionality factor and β ≡ (kT)−1.
 Because v2 = vx2 + vy2 + vz2

then
 Rewrite this as the product of three factors.
6
 g(vx) dvx is the probability that the x component of a gas
molecule’s velocity lies between vx and vx + dvx.
if we integrate g(vx) dvx over all of vx, it equals to 1.
then
 The mean value of vx
7
 The mean value of vx2
 The velocity component distributes

around the peak at vx = 0
at
8
 The results for the x, y, and z velocity components are identical.
 The mean translational kinetic energy of a molecule:
 Purely statistical considerations is good evidence of the validity

of this statistical approach to thermodynamics.
9
9.3: Equipartition Theorem
 Think of oxygen molecule as two oxygen atoms connected by a
massless rod.
How much rotational energy is there and how is it related to
temperature?
Equipartition Theorem:
 In equilibrium a mean energy of ½ kT per molecule is associated
with each independent quadratic term in the molecule’s energy.

 Each independent phase space coordinate:
degree of freedom
10
Equipartition Theorem
 In a monatomic ideal gas, each molecule has
 There are three degrees of freedom.

 Mean kinetic energy is 3(1/2 kT) = 3/2 kT.
 In a gas of N helium molecules, the total internal energy is
 The heat capacity at constant volume is CV = 3/2 Nk.

 For the heat capacity for 1 mole,
 The ideal gas constant R = 8.31 J/K.
11
The Rigid Rotator Model
 For diatomic gases, consider the rigid rotator model.
 The molecule rotates about either the x or y axis.

 The corresponding rotational energies are ½ Ixωx2 and ½ Iyωy2.
 There are five degrees of freedom (three translational and two
rotational).
12
Equipartition Theorem
 In the quantum theory of the rigid rotator the allowed energy
levels are
 From previous chapter, the mass of an atom is confined to a

nucleus that magnitude is smaller than the whole atom.
Iz is smaller than Ix and Iy.
Only rotations about x and y are allowed.
 In some circumstances it is better to think of atoms connected to

each other by a massless spring.
 The vibrational kinetic energy is ½ m(dr/dt)2.
 There are seven degrees of freedom (three translational, two
rotational, and two vibrational).
13
Molar Heat Capacity
 The heat capacities of diatomic gases are temperature dependent,
indicating that the different degrees of freedom are “turned on” at
different temperatures.
Example of H2
14
9.4: Maxwell Speed Distribution
 Maxwell velocity distribution:
Where
 It is useful to turn this into a speed distribution.

 F(v) dv = the probability of finding a particle with speed
between v and v + dv.
15
Maxwell Speed Distribution
 Suppose some distribution of particles f(x, y, z) exists in normal
three-dimensional (x, y, z) space.
 The distance of the particles at the point (x, y, z) to the origin is
 the probability of finding a particle between

.
16
 Radial distribution F(r).
 F(r) dr = the probability of finding a particle between r + dr.
 The volume of the spherical shell is 4πr2 dr.
replace the coordinates x, y, and z with the velocity space

coordinates vx, vy, and vz.
 Maxwell speed distribution:
It is only valid in the classical limit.
17
 The most probable speed v*, the mean speed , and the root-
mean-square speed vrms are all different.
18
 Most probable speed (at the peak of the speed distribution):
 Mean speed (average of all speeds):
 Root-mean-square speed (associated with the mean kinetic energy):
 Standard deviation of the molecular speeds:
σv in proportion to .
19
9.5: Classical and Quantum Statistics
 If molecules, atoms, or subatomic particles are in the liquid or
solid state, the Pauli exclusion principle prevents two particles
with identical wave functions from sharing the same space.
 There is no restriction on particle energies in classical physics.

 There are only certain energy values allowed in quantum
systems.
20
Classical Distributions
 Rewrite Maxwell speed distribution in terms of energy.
 For a monatomic gas the energy is all translational kinetic

energy.
where
21
Classical Distributions
 Boltzmann showed that the statistical factor exp(−βE) is a
characteristic of any classical system.
quantities other than molecular speeds may affect the energy
of a given state.
 Maxwell-Boltzmann factor for classical system:
 The energy distribution for classical system:
 n(E) dE = the number of particles with energies between E + dE.

 g(E) = the density of states, is the number of states available per
unit energy range.
 FMB tells the relative probability that an energy state is occupied at
a given temperature.
22
Quantum Distributions
 Characteristic of indistinguishability that makes quantum statistics
different from classical statistics.
 The possible configurations for distinguishable particles in either

of two energy states:
State 1 State 2
AB
A B
B A
AB
 The probability of each is one-fourth (0.25).
23
 If the two particles are indistinguishable:
State 1 State 2
XX
X X
XX
 The probability of each is one-third (~0.33).
 Because some particles do not obey the Pauli exclusion principle, two
kinds of quantum distributions are needed.
 Fermions:
 Particles with half-spins obey the Pauli principle.
 Bosons:
 Particles with zero or integer spins do not obey the Pauli principle.
24
 Fermi-Dirac distribution:
where
 Bose-Einstein distribution:
Where
 In each case Bi (i = 1 or 2) is a normalized factor.

 Both distributions reduce to the classical Maxwell-Boltzmann
distribution when Bi exp(βE) is much greater than 1.
the Maxwell-Boltzmann factor A exp(−βE) is much less than 1.
25
 The normalization constants for the distributions depend on the

physical system being considered.
 Because bosons do not obey the Pauli exclusion principle, more
bosons can fill lower energy states.
 Three graphs coincide at high energies – the classical limit.
Maxwell-Boltzmann statistics may be used in the classical
limit.
26
Classical and Quantum Distributions
27
9.6: Fermi-Dirac Statistics
 EF is called the Fermi energy.

 When E = EF, the exponential term is 1.
FFD = ½
 In the limit as T → 0,
 At T = 0, fermions occupy the lowest energy levels.

 Near T = 0, there is little chance that thermal agitation will kick a
fermion to an energy greater than EF.
28
Fermi-Dirac Statistics
T=0 T>0
 As the temperature increases from T = 0, the Fermi-Dirac factor “smears out”.

 Fermi temperature, defined as TF ≡ EF / k. .
T = TF T >> TF
 When T >> TF, FFD approaches a decaying exponential.
29
Classical Theory of Electrical Conduction
 Paul Drude (1900) showed that the current in a conductor should
be linearly proportional to the applied electric field that is
consistent with Ohm’s law.
 Prediction of the electrical conductivity:
 Mean free path is .
 True electrical conductivity:
30
Classical Theory of Electrical Conduction
 According to the Drude model, the conductivity should be
proportional to T−1/2.
 But for most conductors is very nearly proportional to T−1.
 The heat capacity of the electron gas is (9/2)R.
 This is not consistent with experimental results.
31
Quantum Theory of Electrical Conduction
 The allowed energies for electrons are
 Rewrite this as E = r2E1
 The parameter r is the “radius” of

a sphere in phase space.
 The volume is (4/3)πr 3.
 The exact number of states up
to radius r is .
32
 Rewrite as a function of E:
 At T = 0, the Fermi energy is the energy of the highest occupied

level.
 Total of electrons
 Solve for EF:
 The density of states with respect to energy in terms of EF:
33
 At T = 0,
 The mean electronic energy:
 Internal energy of the system:
 Only those electrons within about kT of EF will be able to absorb thermal

energy and jump to a higher state. Therefore the fraction of electrons
capable of participating in this thermal process is on the order of kT / EF.
34
 In general,
Where α is a constant > 1.
 The exact number of electrons depends on temperature.

 Heat capacity is
 Molar heat capacity is
35
 Arnold Sommerfield used correct distribution n(E) at room
temperature and found a value for α of π2 / 4.
 With the value TF = 80,000 K for copper, we obtain cV ≈ 0.02R,
which is consistent with the experimental value! Quantum theory
has proved to be a success.
 Replace mean speed in Eq (9,37) by Fermi speed uF defined

from EF = ½ uF2.
 Conducting electrons are loosely bound to their atoms.
these electrons must be at the high energy level.
at room temperature the highest energy level is close to the
Fermi energy.
 We should use
36
 Drude thought that the mean free path could be no more than
several tenths of a nanometer, but it was longer than his
estimation.
 Einstein calculated the value of ℓ to be on the order of 40 nm in

copper at room temperature.
 The conductivity is
 Sequence of proportions.
37
9.7: Bose-Einstein Statistics
Blackbody Radiation
 Intensity of the emitted radiation is
 Use the Bose-Einstein distribution because photons are bosons

with spin 1.
 For a free particle in terms of momentum:
 The energy of a photon is pc, so
38
Bose-Einstein Statistics
 The number of allowed energy states within “radius” r is
Where 1/8 comes from the restriction to positive values of ni and 2 comes
from the fact that there are two possible photon polarizations.
 Energy is proportional to r,
 The density of states g(E) is
 The Bose-Einstein factor:
39
Bose-Einstein Statistics
 Convert from a number distribution to an energy density
distribution u(E).
 For all photons in the range E to E + dE
 Using E = hc and |dE| = (hc/λ2) dλ
 In the SI system, multiplying by c/4 is required.
40
Liquid Helium
 Has the lowest boiling point of any element (4.2 K at 1 atmosphere
pressure) and has no solid phase at normal pressure.
 The density of liquid helium s a function of temperature.
41
Liquid Helium
 The specific heat of liquid helium as a function of temperature
 The temperature at about 2.17 K is referred to as the critical

temperature (Tc), transition temperature, or lambda point.
 As the temperature is reduced from 4.2 K toward the lambda point,
the liquid boils vigorously. At 2.17 K the boiling suddenly stops.
 What happens at 2.17 K is a transition from the normal phase to
the superfluid phase.
42
Liquid Helium
 The rate of flow increases dramatically as the temperature is

reduced because the superfluid has a low viscosity.
 Creeping film – formed when the viscosity is very low.
43
Liquid Helium
 Liquid helium below the lambda point is part superfluid and part
normal.
 As the temperature approaches absolute zero, the superfluid
approaches 100% superfluid.
 The fraction of helium atoms in the superfluid state:
 Superfluid liquid helium is referred to as a Bose-Einstein

condensation.
not subject to the Pauli exclusion principle
all particles are in the same quantum state
44
Liquid Helium
 Such a condensation process is not possible with fermions
because fermions must “stack up” into their energy states, no
more than two per energy state.
 4He isotope is a fermion and superfluid mechanism is radically
different than the Bose-Einstein condensation.
 Use the fermions’ density of states function and substituting for

the constant EF yields
 Bosons do not obey the Pauli principle, therefore the density of

states should be less by a factor of 2.
45
Liquid Helium
 m is the mass of a helium atom.
 The number distribution n(E) is now
 In a collection of N helium atoms the normalization condition is
 Substituting u = E / kT,
46
Liquid Helium
 Use minimum value of B2 = 1; this result corresponds to the
maximum value of N.
 Rearrange this,
The result is T ≥ 3.06 K.

 The value 3.06 K is an estimate of Tc.
47
Bose-Einstein Condensation in Gases
 By the strong Coulomb interaction among gas particles it was
difficult to obtain the low temperatures and high densities needed
to produce the condensate. Finally success was achieved in 1995.
 First, they used laser cooling to cool their gas of 87Rb atoms to
about 1 mK. Then they used a magnetic trap to cool the gas to
about 20 nK. In their magnetic trap they drove away atoms with
higher speeds and further from the center. What remained was an
extremely cold, dense cloud at about 170 nK.
48

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CHAPTER 9

Ludwig Boltzmann, who spent much of his life studying statistical

- David L. Goldstein (States of Matter, Mineola, New York: Dover, 1985)

Statistics and probability

Lagrange around 1790 and Hamilton around 1840.

Pierre-Simon de Laplace (1749-1827)

James Prescott Joule

James Clark Maxwell

bear on the physical thermodynamics problems.

observed macroscopic phenomena.

the view that atoms are real.

 The velocity components of the molecules are more important

 Because v2 = vx2 + vy2 + vz2

 Rewrite this as the product of three factors.

 The mean value of vx

 The velocity component distributes

 The mean translational kinetic energy of a molecule:

 Purely statistical considerations is good evidence of the validity

with each independent quadratic term in the molecule’s energy.

 There are three degrees of freedom.

 In a gas of N helium molecules, the total internal energy is

 The heat capacity at constant volume is CV = 3/2 Nk.

 The ideal gas constant R = 8.31 J/K.

 The molecule rotates about either the x or y axis.

 From previous chapter, the mass of an atom is confined to a

 In some circumstances it is better to think of atoms connected to

 It is useful to turn this into a speed distribution.

 The distance of the particles at the point (x, y, z) to the origin is

 the probability of finding a particle between

replace the coordinates x, y, and z with the velocity space

 Maxwell speed distribution:

It is only valid in the classical limit.

 Mean speed (average of all speeds):

 Root-mean-square speed (associated with the mean kinetic energy):

 Standard deviation of the molecular speeds:

 There is no restriction on particle energies in classical physics.

 For a monatomic gas the energy is all translational kinetic

 Maxwell-Boltzmann factor for classical system:

 The energy distribution for classical system:

 n(E) dE = the number of particles with energies between E + dE.

 The possible configurations for distinguishable particles in either

 The probability of each is one-fourth (0.25).

 In each case Bi (i = 1 or 2) is a normalized factor.

 The normalization constants for the distributions depend on the

 EF is called the Fermi energy.

 At T = 0, fermions occupy the lowest energy levels.

 As the temperature increases from T = 0, the Fermi-Dirac factor “smears out”.

 When T >> TF, FFD approaches a decaying exponential.

 Mean free path is .

 True electrical conductivity:

 But for most conductors is very nearly proportional to T−1.

 The heat capacity of the electron gas is (9/2)R.

 This is not consistent with experimental results.

 The allowed energies for electrons are

 Rewrite this as E = r2E1

 The parameter r is the “radius” of

 At T = 0, the Fermi energy is the energy of the highest occupied

 Solve for EF:

 The density of states with respect to energy in terms of EF: