Statistical Mechanics

PH 324
CH5
 CH5 Distribution Laws
5.1 Maxwell-Boltzmann Distribution
• Consider a system of 𝑵 identical distinguishable non-interacting particles confined
to move freely in a vessel of volume 𝑽. The system is in equilibrium at temperature
𝑻. The total energy of the system is 𝑬.
• A monatomic ideal gas containing N molecules in a container of volume V is an
example of our system. A macrostate of the system is specified by specifying how
the total energy E of the system is distributed among N particles.
• Let 𝜺𝟏 , 𝜺𝟐 , ….. 𝜺𝒊 , … be the allowed single-particle energy levels and
𝒈𝟏 , 𝒈𝟐 , ….. 𝒈𝒊 , … the degeneracies of these energy levels respectively.
The description of a macrostate is given by specifying the number of particles in
each energy level 𝜺𝒊 .
Let 𝒏𝟏 be the number of particles in energy level 𝜺𝟏 with degeneracy 𝒈𝟏
𝒏𝟐 be the number of particles in energy level 𝜺𝟐 with degeneracy 𝒈𝟐 … ….. …..
𝒏𝒊 be the number of particles in energy level 𝜺𝒊 with degeneracy 𝒈𝒊 and so on.
The set of numbers {𝒏𝟏 , 𝒏𝟐 , …., 𝒏𝒊 } defines a macrostate.
 Our objective is to determine 𝒏𝟏 , 𝒏𝟐 , …., 𝒏𝒊 . In classical (Maxwell-Boltzmann)
statistics all the particles are assumed to be identical and distinguishable from
one another.
 Cont. 5.1 Maxwell-Boltzmann Distribution
• We wish to find the number of different arrangements or microstates
corresponding to a macrostate. The required number of accessible microstates is
equal to the number of ways a given macrostate is realized by arranging the
particles in different states.
 The total number of distinct ways (accessible microstates) in which N particles
can be distributed among possible energy levels such that
𝒏𝟏 particles are in level 𝜺𝟏 with degeneracy 𝒈𝟏 ,
𝒏𝟐 are in level 𝜺𝟐 with degeneracy 𝒈𝟐 ..... and so on, is

….(5.1)

• According to the principle of equal a priori probabilities, all the microstates are
equally probable. The most probable macro state specified by 𝒏𝟏 , 𝒏𝟐 , …..is one
which corresponds to the maximum number of micro states.
• So to obtain most probable distribution we must maximize 𝜴𝑴𝑩 taking care of the
conditions that the total number of particles and the total energy of the system is
constant. These two restrictions are expressed as
….(5.2) ….(5.3)
 Cont. 5.1 Maxwell-Boltzmann Distribution

….(5.4)

….(5.10)
 Cont. 5.1 Maxwell-Boltzmann Distribution

• The ratio 𝒏𝒊 /𝒈𝒊 represents the average number of particles per state of the system
and is called energy distribution function 𝒇𝑴𝑩 (𝜺). The distribution function represents
the average number of particles in each of state of energy 𝜺 or the probability of
occupancy of each of state of energy 𝜺.
𝒏
• 𝒇𝑴𝑩 𝜺 = 𝒈𝒊 = 𝒆 𝜶 𝒆 𝜷 .....(5. 11)
𝒊

• In other words 𝒇𝑴𝑩 𝜺 gives the probability that a particle, selected randomly from
the system, will have its energy 𝜺. This is the classical (MB) distribution function. It is
applicable to system whose constituent particles are distinguishable and don’t obey
Pauli’s exclusion principle. It is the most probable distribution of particles among the
accessible energy levels at equilibrium for a system of constant total energy.

• For a system comprising of large number of particles the most probable distribution
describes the actual behavior of the system.

• In deriving MB distribution function no assumption regarding the nature of energy

was made so it is valid for translational, rotational, vibrational and electronic.
 Cont. 5.1 Maxwell-Boltzmann Distribution

 If the energy levels of the system are very close together, such as those of molecules
in a gas, the 𝐠(𝜺) (density of states) is replaced by 𝐠 𝜺 𝒅𝜺, which represents the
number of states with energies between 𝜺 and 𝜺 + 𝒅𝜺.
 The number of particles occupying the states in the energy range 𝒅𝜺 about 𝜺 is
n 𝜺 𝒅𝜺 = 𝒇𝑴𝑩 𝜺 𝐠 𝜺 𝒅𝜺
• For a system of free particles each of mass 𝒎,
enclosed in a vessel of volume V, the number of ...(5. 18)
states in the energy range 𝒅𝜺 about 𝜺 is

 The expression for partition for a gas, with continuous energy levels, is obtained
by replacing the summation sign by integral sign. 𝑍 = ∫ 𝑔( 𝜺)𝑒 𝒅𝜺 .....(5. 19)
 Cont. 5.1 Maxwell-Boltzmann Distribution
• The number of particles occupying the energy states in the interval 𝒅𝜺 at 𝜺 in a N-particle
system in equilibrium at temperature T is

...(5. 22)
• Comparison of these two expressions gives

• From kinetic theory we know that,

the total translational energy of an
ideal gas containing N molecules is
𝐸 = 𝑁𝐾𝑇 ...(5. 24)
Comparison of these two expressions
gives 𝛽 = 1/𝐾𝑇 ...(5. 25)

𝜞 𝒏 = ∫𝟎 𝒙𝒏 𝟏 𝒆 𝒙 𝒅𝒙 , 𝒏 > 𝟎
𝜞 𝒏 + 𝟏 = 𝒏!
𝜞 𝟏/𝟐 = 𝝅
...(5. 23)
 5.2 Heat Capacity of an Ideal Gas

• The total energy of one mole of an ideal gas is

, universal gas constant …(5.26)
• The molar heat capacity at constant volume is
. …(5.27)

5.3 Maxwell’s Speed Distribution Function

 Now we shall derive Maxwell speed distribution for a perfect classical
gas. To obtain the required distribution function we must convert the
energy distribution into appropriate speed distribution.

 In a perfect gas of free molecules possessing no internal degree of

freedom (such as monatomic molecule) all the energy resides in the
form of translational kinetic energy of molecules.
 Cont. 5.3 Maxwell’s Speed Distribution Function

So from eq. (5.22)

𝒅𝑵𝒗

…(5.28)

…(5.29)

The function gives the fraction of all molecules having speeds in the
interval about .
In other words, represents the probability that a molecule selected
at random from the gas will have its speed in the interval about
 Cont. 5.3 Maxwell’s Speed Distribution Function

 Now suppose that we wish to know

 How many molecules of the gas have velocities such that
the 𝒙-component of velocity is in a range 𝒅𝒗𝒙 about 𝒗𝒙 ,
the 𝒚-component is in a range 𝒅𝒗𝒚 about 𝒗𝒚 ,
and 𝒛-component is in a range 𝒅𝒗𝒛 about 𝒗𝒛 .
 This number of molecules is in a rectangular volume element
𝒅𝒗𝒙 𝒅𝒗𝒚 𝒅𝒗𝒛 in velocity space centered on the value (𝒗𝒙 , 𝒗𝒚 , 𝒗𝒛 ).

 We shall call this number 𝐧(𝒗𝒙 , 𝒗𝒚 , 𝒗𝒛 )𝒅𝒗𝒙 𝒅𝒗𝒚 𝒅𝒗𝒛 .

Fig. 5.1 Velocity space for molecules

𝐧(𝒗𝒙 , 𝒗𝒚 , 𝒗𝒛 )𝒅𝒗𝒙 𝒅𝒗𝒚 𝒅𝒗𝒛 = 𝑓 𝒗𝒙 , 𝒗𝒚 , 𝒗𝒛 g 𝒗𝒙 , 𝒗𝒚 , 𝒗𝒛 𝒅𝒗𝒙 𝒅𝒗𝒚 𝒅𝒗𝒛

( )/ …(5.33)
𝒙 𝒚 𝒛 𝒙 𝒚 𝒛 𝒙 𝒚 𝒛
 Cont. 5.3 Maxwell’s Speed Distribution Function
Expression for 𝐧(𝒗𝒙 ):
• The number of molecules whose 𝑥-component of velocity lies in a range 𝒅𝒗𝒙
about 𝒗𝒙 regardless of what values the 𝑦-component and 𝑧-component of
velocity may have, is given by 𝒗𝒚 𝒗𝒛
𝐧(𝒗𝒙 , 𝒗𝒚 , 𝒗𝒛 )𝒅𝒗𝒙 𝒅𝒗𝒚 𝒅𝒗𝒛
𝒗𝒚 𝒗𝒛
𝒎 𝟏
𝒎𝒗𝟐𝒙 /𝟐𝑲𝑻
𝒏 𝒗𝒙 𝒅𝒗𝒙 = 𝐍 ( )𝟐 𝒆 𝒅𝒗𝒙 …(5.34)
𝟐𝝅𝑲𝑻
 Table of some useful
definite integrals.

 A plot of the
distribution functions
𝐧 𝒗 and 𝐧 𝒗𝒙 as
functions of velocity
coordinates is shown
in the Fig. (5.2).
 Cont. 5.3 Maxwell’s Speed Distribution Function

𝑛(𝑣 )

The Maxwell velocity distribution for

gas molecules. The distribution is
centered on 𝑣 = 0. The shaded
strip represents the number of
molecules with velocity components
between 𝑣 and 𝑣 + 𝑑𝑣 .
Fig. 5.2 Velocity distribution functions at different temperatures
 Cont. 5.3 Maxwell’s Speed Distribution Function

 Three kinds of velocities associated with Maxwell distribution

Average velocity < 𝒗 >

Root mean square speed 𝒗𝒓𝒎𝒔
Most probable speed 𝒗𝒎𝒑

𝟐𝑲𝑻 𝟖𝑲𝑻 𝟑𝑲𝑻

𝒗𝒎𝒑 ∶ < 𝒗 > ∶ 𝒗𝒓𝒎𝒔 = ∶ ∶
𝒎 𝒎𝝅 𝒎

𝟖
= 𝟐 ∶ ∶ 𝟑
𝝅

= 𝟏 ∶ 𝟏. 𝟏𝟑 ∶ 𝟏. 𝟐𝟐

Fig. 5.3 Three kinds of velocities associated with

Maxwell distribution
 Cont. 5.3 Maxwell’s Speed Distribution Function

Average velocity < 𝒗 >

 The average velocity < 𝒗 > of a particle in M-B distribution is given by

…(5.35)
 Cont. 5.3 Maxwell’s Speed Distribution Function

Root mean square speed 𝒓𝒎𝒔

 The root mean square speed is defined by

…(5.36)
 Cont. 5.3 Maxwell’s Speed Distribution Function

Most probable speed 𝒎𝒑

 The most probable speed corresponds to the maximum value of 𝒏(𝒗). Now

…(5.37)
 Example 1 : A system of 𝑁 non-interacting classical point particles is constrained to move
on the two-dimensional surface of a sphere. The internal energy of the system is:

(a) 𝑁𝐾 𝑇 (b) 𝑁𝐾 𝑇 (c) 𝑁𝐾 𝑇 (d) 𝑁𝐾 𝑇

Solution : There are 2𝑁 degree of freedom.

The internal energy of the system is 𝑁𝐾 𝑇 + 𝑁𝐾 𝑇 = 𝑁𝐾 𝑇

Example2 : Consider a system whose three energy levels are given by 0, 𝜀 𝑎𝑛𝑑 2𝜀.
The energy level 𝜀 is two-fold degenerate and the other two are non-degenerate.
The partition function of the system with 𝛽 = 1/𝐾 𝑇 is given by
(a) 1 + 2𝑒 (b) 2𝑒 +𝑒 (c) (1 + 𝑒 ) (d) 1 + 𝑒 +𝑒

Solution: 𝜀 = 0, 𝜀 = 𝜀, 𝜀 = 2𝜀 ;
𝑔 = 1, 𝑔 = 2, 𝑔 = 1 where 𝑔 , 𝑔 and 𝑔 are degeneracy.
From eq.(5-15), the partition function 𝑍 = ∑ 𝑔 𝑒
𝑍 =𝑔 𝑒 +𝑔 𝑒 +𝑔 𝑒 = 1 + 2𝑒 +𝑒 = (1 + 𝑒 )
Example 3 : A classical gas of molecules, each of mass , is in thermal
equilibrium at the absolute temperature . The velocity components
of the molecules along the
Cartesian axes are , and . The mean value of is

(a) (b) (c) (d)

Solution:

and
Example 4 : Find the total translational kinetic energy and root mean square velocity of molecules
of 20 𝑙𝑖𝑡𝑒𝑟 of helium gas at an equilibrium pressure of 1 × 10 𝑁/𝑚 .
Example 5 : Find the number of oxygen molecules whose speeds lie between
195 and 205 𝑚/𝑠 at 0 °𝐶. The mass of oxygen gas is 0.1 𝑘𝑔 .
Example 6 : The speed distribution function of a group of 𝑁 particles is given by
𝑓(𝑣)𝑑𝑣 = 𝑑𝑁 = 𝐾𝑣 𝑑𝑣 . for 𝑣 > 𝑣 > 0 where 𝑣 is such that
𝑑𝑁 = 0. for 𝑣 > 𝑣
Sketch the distribution function.
Find (i) the value of constant
(ii) the average speed of particles
(iii) the rms speed of particles

Solution. (i) The graph of the function is parabolic in shape.

The total number of particles is given by
𝑁 = ∫ 𝑑𝑁 = 𝐾 ∫ 𝑣 𝑑𝑣 = 𝐾𝑣 → 𝐾=
∫
(ii) Average speed < 𝒗 > = 𝑣̅ = = ∫ 𝑣 𝑑𝑣 =

∫ 𝒗𝟐
(iii) 𝒗𝒓𝒎𝒔 = < 𝒗𝟐 >; 𝟐
< 𝒗 >= = ∫ 𝑣 𝑑𝑣 =

∴ 𝒗𝒓𝒎𝒔 = = 𝑣
 𝟏 𝟏
Example 7 : Show that < 𝒗 > and 𝒗
are not the same. Find their ratio.

Solution:
Example 8 : From Maxwell's energy distribution formula,
calculate the most probable energy of molecules at temperature 𝑇.

Solution: The energy distribution formula is (from eq. 5.22)

𝑑𝑁 =

Most probable energy is given by the equation

Example 9 : Assuming Maxwellian energy distribution law calculate the
average energy of molecule at temperature 𝑇.

Solution: Average energy is defined by (from 5.22)

𝜺
In order to evaluate the integral we make the substitution 𝑲𝑻 = 𝒙.
After substitution the integral transforms into Gamma function.
Example 10 : In an assembly of particles 𝑁 represents the number of particles with
speed 𝑣 , 𝑁 𝑣 (𝑚𝑠 )
2 1.0
4 2.0
8 3.0
6 4.0
3 5.0
Compute (i) average speed (ii) RMS speed (iii) most probable speed.

< 𝑣 >=
 5.4 Fermi-Dirac Statistics
 Many properties of solid materials such as thermal and electrical
conductivity, magnetic properties, specific heats etc. are related to the
electron energy states.
The understanding of these properties requires the distribution of
electrons, which are fermions, in various states.
 The distribution function for electrons must satisfy two requirements:
(1) electrons are indistinguishable particles i.e., it is not possible to
label them as electron number 1, number 2 and so on
(2) electrons obey Pauli’s exclusion principle, which states that no
quantum state may be occupied by more than one electron.
 The distribution function that results from these two considerations was
first developed by Fermi and Dirac in 1927. In fact all the particles,
which have half odd integral spin (1/2, 3/2, 5/2, …), obey exclusion
principle, are described by F-D statistics. These particles are called
fermions.
 Cont. 5.4 Fermi-Dirac Statistics
 Consider a system composed of N fermions with total energy E.
An assembly of non-interacting fermions is called fermi gas or
electron gas if the fermions are electrons.
 The assembly of free electrons in a metal is a well-known example
of fermi gas.
…(5.47)

• 𝒊 represents the number of electrons in the energy level 𝒊

𝒏
• The ration 𝒊 is called F-D distribution function and is denoted by 𝑭𝑫 .
𝒈𝒊

…(5.48)

 The function 𝒇𝑭𝑫 (𝜺) is the average number of electrons per quantum state of energy 𝜺.
It also represents the probability that a state of energy 𝜺 is occupied.
 The quantity 𝜷 is 𝟏/𝒌𝑻, where 𝑻 is temperature of the system.
 The value of ∝ is determined by the normalization condition
 Cont. 5.4 Fermi-Dirac Statistics
 It is customary to express ∝ in terms of another constant 𝝁, called chemical
potential. (In solid state physics 𝝁 is called Fermi level 𝜺𝑭 ).
…(5.49)

 In terms of chemical potential 𝝁 and Fermi energy 𝜺𝑭 the FD distribution

becomes:
…(5.50)

 For systems with continuous energy levels, the number of fermions occupying the
states in the energy range d𝜺 at 𝜺 is given by: …(5.51)

 The total number of fermion in the system is given by

…(5.52)

 For electron gas, the density of states is given by

s = 1/ 2 for electron. …(5.53)

 5.5 Bose-Einstein Statistics
 There are many systems, which are composed of weakly interacting
identical and indistinguishable particles with integral spin.
 These particles don’t obey Pauli’s exclusion principle. Thus any
number of particles can occupy the same quantum state.
 The statistical behavior of such particles is governed by a different
kind of statistics, called Bose-Einstein statistics, named in honor of
S.N. Bose and A. Einstein who independently derived it.
 Particles obeying Bose-Einstein statistics are called bosons.
Examples of bosons are photons (spin 1), molecule, helium ,
meson etc.
 Consider a system composed of bosons.
…(5.63)

…(5.64)
 Cont. 5.5 Bose-Einstein Statistics

 Eqn. (5.63) represents the BE distribution function.

 Eqn. (5.64) represents number of bosons per quantum state at energy 𝒊
or the occupation probability of state with energy of a system in
thermal equilibrium at temperature .
 In a system in which the number of bosons is not conserved, the
condition 𝒊 constant does not apply.
For example, the number of photons in a cavity increases with increasing
temperature. This in contrast to an ideal gas contained in a vessel.
Removal of this condition is equivalent to setting .
 For such system the B-E distribution becomes:

…(5.65)