Chapter (5)

Maxwell-Boltzmann distribution statistics and

Application to molecular energies in an ideal gas

Introduction
Statistical mechanics provides a bridge between the macroscopic realm
of classical thermodynamics and the microscopic realm of atoms and
molecules. We are able to use computational methods to calculate the
thermodynamic parameters of a system by applying statistical mechanics.
We must remember that the energies of molecules, atoms, or electrons
are quantized. To describe the systems we must know the energies of the
quantum states and the distribution of particles (i.e., molecules, atoms, or
electrons) among the quantum states. The Schrodinger equation that we
discussed in the section on quantum mechanics provides a method for
calculating the allowed energies. The Boltzmann distribution law that is a
fundamental principle in statistical mechanics enables us to determine
how a large number of particles distribute themselves throughout a set
of allowed energy levels.
Consider a system composed of N molecules, and its total energy E is a
constant. These molecules are independent, i.e. no interactions exist
among the molecules. Countless collisions occur. It is hopeless to keep
track positions, moments, and internal energies of all molecules. All
possibilities for the distribution of energy are equally probable provided
the number of molecules and the total energy are kept the same. That is,
we assume that vibrational states of a certain energy, for instance, are as
likely to be populated as rotational states of the same energy. For
instance, four molecules in a three-level system: the following two
conformations have the same probability.
---------l-l-------- 2

---------l--------- 2

---------l----------

---------1-1-1----

---------l---------- 0

------------------- 0

Imagine that there are total N molecules among which n0 molecules with
energy 0, n1 with energy 1, n2 with energy 2, and so on, where 0 < 1 < 2

< .... are the energies of different states. The specific distribution of
molecules is called configuration of the system, denoted as { n0, n1,
n2, ......}
STATE

10
3

15

2
13
12

14

2
11

5
16

17

The above configuration is thus, { 4, 6, 4, 3 }

THE DISTRIBUTION OF MOLECULAR STATES
{N, 0, 0, ......} corresponds that every molecule is in the ground state,
there is only one way to achieve this configuration; {N-2, 2, 0, ......}
corresponds that two molecule is in the first excited state, and the rest
in the ground state, and can be achieved in N(N-1)/2 ways.
A configuration { n0, n1, n2, ......} can be achieved in W different ways,
where W is called the weight of the configuration. And W can be
evaluated as follows,

1. N! different ways to arrange N molecules;

2. ni! arrangements of ni molecules with energy i correspond to the
same configuration;
Example 1:
1. Calculate the number of ways of distributing 3 objects a, b and c
into two boxes with the arrangement {1, 2}.
Answer:
| a | b c |, | b | c a |, | c | a b |.
Therefore, there are three ways 3! / 1! 2! or
| a | c b |, | b | a c |, | c | b a |
Example 2:
Calculate the number of ways of distributing 20 objects into six
boxes with the arrangement {1, 0, 3, 5, 10, 1}.

Answer:
20! / 1! 0! 3! 5! 10! 1! = 931170240
It is easy to calculation the number of ways of distributing of one
molecules (A), the probability (w) is A=1. The number of ways of
distributing of two molecules, the probability (w) is AB=2 or BA=2. The
number of ways of distributing of three molecules, the probability (w) is
ABC, ACB, BAC, BCA, CAB, CBA= 3x2=6. The number of ways of
distributing of three molecules, the probability (w) is ABCD, ABDC,
ADBC, DABC,BCDA, BCAD, BACD, ACDB, CDAB, CDAB,CDBA, CBDA,
BDAC, DABC, DABC, DACB, DCAB, CABD= 4x4=16.
The Distribution of Internal Energies in Molecules
What happens if we apply thermal energy (kT energy) to a mol of
molecules confined in a jar at constant temperature? The molecule takes
up the energy and distributes it among the available energy levels. This
distribution was studied by Boltzmann who showed that:
Ni/Nj = exp (-(Ei-Ej))/kT
Ni = No. of molecules in level i (higher)
Nj =

j (lower)
Ei = energy of molecules in level I (higher)
Ej =

j (lower)
The ratio, Ni/Nj is the relative occupancy. The Boltzmann distribution, as
the equation is known, applies only when the system is in thermal
equilibrium. It gives the relative occupancy for two energy states, E i and
Ej. What are some of the properties of this equation? Suppose we look
at rotation at very low temperature i.e. when Nj = No and Ev = Eo = 0
Ni/No = exp (-(Ei-Eo))/kT
Ni = Noe -Ei/kT
ie. at constant temperature there is an exponential decrease in the
number of molecules in the higher energy states (Fig. 1)

Ni

J=0

J=1

J=2

J=3

Fig. 1
e.g. CO vibration at room temperature (RT = 25 0C; Ev = 25 kJ mol-1)

N i (1st excited state)

e 25
N o (ground state)

kJ mol1 2.5 kJ mol1

= e -10 5 10-5 or 0.005

%
i.e. only 0.005% of molecules in first excited state, N i the rest is in the
ground state, No.
Test of the Distribution at Constant, Low and High Temperatures
What happens if temperature is not kept constant?
Ni/Nj = e -(Ei-Ej)/kT
Ni/Nj = e -Eij/kT

Suppose at high temperature, kT >> Eij

Eij 0
i.e. Ni/Nj = e -0 = 1 i.e. we get a uniform distribution of molecules over all
available energy levels (Fig. 2a)
If Eij >> kT (at low temperatures)
Then Ni/Nj = e - = 0 i.e. only the lowest energy level is occupied; others
are empty (Fig. 2b)

EJ

Fig. 2a

Fig. 2b
Fig. 2

Since we have several degenerate rotational levels, the equation is

modified to account for this:
Ni/Nj = gi/gj e (Ei-Ej)/kT ..where g = degeneracy and
g = (2J + 1) = No. of degenerate levels e.g.
EJ
J=2
J=1

three degenerate energy levels in J = 1

J=0
Partition Function
If N = total No. of molecules in a sample:
Ni/N = e Ei/kT/i e Ei/kT
Define ie Ei/kT = Z = Molecular Partition Function
q = measure of availability of states.
If more than one state with energy level Ei (degenerate rotation)
NJ = gi e EJ/kT/ J gi e EJ/kT
Z = J gi e EJ/kT
or Z = J gi e EJ ..where = 1/kT
Boltzmann Distribution Law.
Microstates and Configurations
Consider a simple assembly of three localized (i.e., distinguishable)
particles that share three identical quanta of energy. These quanta can
be distributed among the particles in ten possible distributions as
illustrated in the figure below.

Each of the ten distributions is called a microstate; in our example

the ten microstates fall into three groups, or configurations,
denoted A, B, and C. When dealing with only three particles, we can
count the number of microstates and configurations, but for larger
numbers of particles, we need to calculate them. Our simple
example above can be used to understand how to calculate the
number of microstates and configurations.
For configuration B: The two-quanta parcel of energy can be
assigned to any of the three particles, the one-quantum parcel to
either of the two remaining particles, and the zero-quantum parcel
to the remaining particle. Thus, the total number of ways in which
assignments can be made is
For configuration A: We again have three choices in assigning the
first (three-quanta) parcel of energy, two choices when we assign
the second (zero-quantum), and one choice when we assign the
third (zero-quantum). But because the last two parcels are the
same, the final distribution is independent of the order in which
they are assigned. That is,
distinguishable assignments collapse into one microstate because
the two particles end up in the same quantum level. Thus, the total
number of microstates associated with configuration A is

For configuration C: We have triple occupancy of the first quantum

level and the final distribution is independent of the order in which
the particles are assigned. Thus, we have one microstate.

This approach can be generalized to a larger number (N) of

localized particles. We have N choices of the particle to which we

assign the first parcel of energy, (N-1) choices in assigning the
second, etc., to give a total of

distinguishable possibilities if no two energy parcels are the same.

If some number (na) of the parcels are the same, we can have only

N!/na! distinct microstates. Symbolizing by W the total number of

microstates

in

given

configuration,

we

can

write

where na represents the number of units occupying some quantum

level, nb represents the number of units occupying some other
quantum level, etc.
This

equation

can

be

written

in

the

general

form

For our simple example above, we can calculate the number of

microstates in configuration A as

For very large N, it is necessary to deal with natural logarithms.

That is,

We

can

now

apply

Stirling's

approximation

in

the

form

We can then approximate the expression for the number of

microstates as

Because

, we can simplify to

Predominant Configuration
Note that in our simple example, one of the configurations (B) had
a greater number of microstates associated with it than the
others. As N increases, a predominant configuration becomes even
more apparent.
We of course want to be able to identify this predominant
configuration. For large N, it is not practical to do this by the
approach we have illustrated above. However, it can be shown that
the distribution of microstates for large N can be described by a
smooth curve, the sharpness of which increases as the number of
particles increases.

In the graph above, the configuration index number represents the

fraction

describing

the

number

of

times

microstate

corresponding to a given configuration is observed divided by the

total number of microstates. The predominant configuration
corresponds to the very peak of the curve. That is,
where dX denotes a change from the predominant configuration to
another configuration only infinitesimally different from it. Using
this criterion, we can now develop a simple formula that describes
the predominant configuration.

The Boltzmann distribution law

Consider an isolated macroscopic assembly of N particles, identical
but distinguishable by spatial localization, which share a large number
of energy quanta, each of which suffices to promote a particle from
one quantum level to the next level above it. Because the assembly is
isolated, both N and the energy will remain constant. We now want to
determine for which of the enormous number of configurations that
can be assumed by the assembly will the number of associated
microstates realize its maximum value.
Consider any three successive quantum levels l,

m, n, with

associated energies el, em,en and numbers of particles nl, nm, nn,
respectively. For any given configuration, the number of microstates
can be calculated from

Now make a change in the initial configuration such that one particle
is shifted from each of levels l and n into level m. This change
maintains a constant number of particles and energy but creates a
new

configuration

that

differs

from

the

first

in

that

Hence,

Because we want to calculate the properties of the predominant

configuration, let us assume that the original configuration was in
fact the predominant configuration for which the number of
associated

microstates

reaches

its

maximum

value,

where

Because the change we have made in the configuration is extremely

small, we would expect essentially no change in W. Therefore,
from which we can write

Canceling terms that are common to both sides of the equation and
inverting gives

Rearranging gives

Expanding some of the factorial terms gives

Cancellation gives

But numbers such as 1 and 2 are small in comparison to the large

populations being studied. Hence,

or

This relationship also holds for other successive energy levels. Thus,
for a macroscopic assembly of particles with uniform energy spacing
between their quantum states, we can describe the predominant

configuration as the one for which the following geometric series

applies:

A similar approach can be taken when considering a system in which

the energy spacing is not uniform. Without going through the
derivation, the appropriate equation is

The values of p and q are small, positive integers selected so that the
following equation holds:

Thus,

Since

Then,

Note that l, m, and n are any three quantum levels. Thus, for any two
quantum levels, the indicated function must have exactly the same
value. That is, this function is a constant; it is denoted by beta.
For

any

two

quantum

states,

and

n,

we

can

write

If i is taken to be the ground state, with population n0 and energy e0

= 0, this equation reduces to

or

This equation is the Boltzmann distribution law. It defines the

predominant configuration for an isolated macroscopic assembly of
identical but distinguishable particles, with any kind of energy
spacing between their quantum states. When a system is said to obey
a Boltzmann distribution, it will be consistent with the above
equation. At equilibrium, the configuration of an isolated macroscopic
assembly is typically that described by the Boltzmann distribution
law.
The Meaning of Beta
The constant beta has a significant physical meaning. We will not
show the derivation, but beta is inversely related to temperature.
That is,

where T is in Kelvin, k has unit of energy/K.

Degeneracy
The Boltzmann distribution law, as derived above, considers the
population of each distinct quantum state. Some of these quantum
states may have the same energy, in which case these states are said
to be degenerate. To account for degeneracy, one simply multiplies
the energy level by the number of quantum states that have that

energy. Degeneracy will be included explicitly in the derivation that

follows.
Derivation of Boltzmann Distribution Law
Consider now how an Avogadro's number (N) of molecules will
distribute themselves throughout their allowed energy levels.

where W is the probability of a given distribution. We want to find

the distribution such that W is a maximum. It is more convenient
mathematically to seek a maximum in ln W. Taking the natural
logarithm

of

the

above

equation,

and

applying

Stirling's

approximation to the ni terms gives

In solving for a maximum in ln W, we must impose two conditions, a

constant number of molecules and a constant total energy of the
system. That is,

and
These conditions are imposed by applying Lagrange's method of
undetermined multipliers. Two parameters, a and b, are introduced.
Rather than looking for a maximum in ln W, we seek a maximum in
Thus, we can assure constant N and constant E, and the maximum we
find is still a maximum in ln W. To find the maximum with respect to

ni, we solve

Recall

our

previous

expression

for

ln

W.

That

is,

N is a constant that is independent of the individual ni's, so we can

write

Substituting, we obtain

Considering the relative populations of two energy levels, i and j, we

can write

This again is the Boltzmann distribution law, in this case with the
degeneracy (gi's) explicitly shown.
c. Partition function

The sum over states (Zustandsumme) is called the partition

function. In principle, its a sum over all the particle states of a system,
and therefore contains the statistical information about the system. All
of the thermodynamic properties of the system are derivable from the
partition function.

Z e

Ei
kT

Remember, the partition function is written as a sum over all

microstates, rather than over energy macrostates, so that the
multiplicity factor does not appear explicitly. All of the macroscopic
thermodynamic quantities are obtainable from the microscopic statistics
of the single particle energy states. For instance, internal energy:
E
E i Z
Z

i 2 e kT
Z
i kT
T V

Z
Ei N i
kT 2 i
ZU

kT 2
ln Z
U kT 2

T V

Entropy:

S k ln k N i ln N i kN
i

N E
k N i ln i kN
i
Z kT
Z U
Nk ln Nk
N T
Pressure:

TdS dU PdV
P

dU
dS
U TS
T

dV
dV
V
T
V

ln Z
P NkT

V T

Z
NkT ln NkT
N

2.

Probability

a. Ensembles
microcanonical
In an isolated system, every microstate has equal probability of
being occupied. The total energy is fixed. The collection of all the
possible microstates of the system is called the microcanonical ensemble
of states.
canonical
If the probability distribution is the Boltzmann distribution, the
collection of energy states is called the canonical ensemble. Weve seen
that such a distribution applies to a system at constant temperature and
fixed number of particles, in contact with an energy reservoir. The
internal energy is not fixed, but we expect only small fluctuations from an
equilibrium value.

grand canonical
If the number of particles is allowed to change, then we have to sum
also over all possible numbers of particles, as well as all possible energy
states, giving the grand canonical ensemble.
b. Average values
The probability that a particle will be observed to occupy a particular
energy state is given by the Boltzmann distribution.

P( E )

E
kT

The average value of the particle energy would be computed in the usual
way,

E Ei
i

Ni

Eie

Ei
kT

The internal energy of the system of N particles is U = N<E>. We are

averaging over a collection of particles whose energies are distributed
according to the Boltzmann distribution.
3.

A Couple of Applications

a. Equipartition Theorem
A particles kinetic energy is proportional to the square of its
velocity components.

In Cartesian coordinates, K vx2 v y2 vz2 .

In a

similar vein, the rotational kinetic energy of a rigid body is also

proportional to the square of the angular velocity, thus K rotation 2 . In
the case of a harmonic oscillator, the potential energy is also
proportional

to a square,

namely the displacement

components,

U potential x 2 y 2 z 2 . Very often, we approximate the real force acting

on a particle with the linear restoring force of the harmonic oscillator.

Let us consider a generalized quadratic degree of freedom, E q cq 2 .

Each value that q takes on represents a distinct particle state. The
energy is quantized, so the q-values are discrete, with spacing q .
The partition function for this system is a sum over those q-states

Z e

E q
kT

cq 2
kT

In the classical limit q is small, and the sum goes over to an integral

Z e

cq 2
kT

dq kT e cy dy kT
2

The average energy is

3

1 1 2
1 Z
1
1
E

kT .
Z 1
2
kT 2 kT

kT
So, each quadratic degree of freedom, at equilibrium, will have the
same amount of energy. But, this equipartition of energy theorem is
valid only in the classical limit and high temperature limits. That is,
when the energy level spacing is small compared to kT. We saw
earlier that degrees of freedom can be frozen out as temperature
declines.
The Kinetic Theory of Gases
1.
Sample of gas huge number of atoms (molecules).
2.
Atoms are very small compared the space in which they travel.
3. Atoms have translational energy only (ignore rotational, vibrational or
other internal structure).
Molecular View of Pressure
Atoms have translational energy coming motion in three dimensions.
1
1
tr m v2x v2y v2z mv2
2
2
Assume gas is in a box with lengths, lx, ly, lz.
Assume gas is in thermodynamic equilibrium
- No net energy transfer between walls of box and gas atoms.
Consider the z-component of an atoms velocity as it hits the wall of the
box with lengths lx and ly.
1.
Collision reverses vz.
2.
vx and vy remain unchanged.
3.
Overall speed and energy are unchanged. (elastic collisions)
Force is the time derivative of momentum.
d mvz dm
dp
dv
dv
Fz z

vz m z m z ma z
dt
dt
dt
dt
dt

Find the change in the momentum of the collision with the wall
pz pf pi m vz mvz 2mvz
For a single atom i, the time average of the force is:
pz,i Fz,i dt Fz,i t 2 t1

Assuming a constant speed, the time change can be related to the

distance travelled by the atom.
2l
t 2 t1 z
v z,i
Consider the force on the wall using Newtons third law.
2

2m v z,i 2m v z,i
m v z,i
F Fz,i

t 2 t1 2lz v z,i
t 2 t1
lz

Find the total force on the wall by summing over all of the atoms.
pz,i

W
z,i

W
z

W
z,i

N F

W
z,i

Nm vz,i

lz

Using the average force, calculate the pressure on the wall

perpendicular to the z-direction.

FzW
Nm v z,i
F
p

A
Az
lx ly

lz

Nm v z,i
l x l ylz

Nm v z,i

Consider that choosing z-direction to calculate the pressure is arbitrary.

1.
Pressure is the same on any wall.
2.
Average molecular velocity is the same in all directions.
v x,i v y,i vz,i
vi

vx,i

v y,i

v z,i

vz,i

v
i
3

3 vz,i

Nm vi
p
3V
Pressure can be written in terms of the molecular translational energy.
1.
For a single molecule,
1
2
tr m vi
2
2.
For N molecules,
2E
1
2
2
E tr N tr Nm vi
p tr pV E tr
2
3V
3
Each type of molecule has its own translational energy and therefore its
own pressure.

pa

2E tr,a

pb

2E tr,b

pc

2E tr,c

3V
3V
3V
E tr,total E tr,a E tr,b E tr,c
2E
2E
2E
2E
pa pb pc tr,a tr,b tr,c tr p
3V
3V
3V
3V

Molecular View of Temperature

Temperature is a measure of how energy is distributed in a material
sample.
1. Higher temperature means more modes of motion are available for
a molecule to move.
- Types of motion include translational, rotational, vibrational and
electronic.
2. Lowest temperature implies one mode of motion. (3 rd Law of
Thermodynamics)
Thus temperature is a function of energy (microscopic or macroscopic).
1.
For a gas without internal structure,
T f tr or T g E tr
2. Note the temperature function is different for microscopic and
macroscopic energies.
We can define temperature macroscopically in terms of the ideal gas law.
2
3
pV nRT
E tr E tr nRT
3
2
E
3
E E tr RT
n
2
E tr
3 nRT 3 RT
EN
tr

N
2 N
2 NA
NA Avogadro 's number
The corresponding microscopic definition follows from a definition of
Boltzmanns constant, k.
R
8.314 J mol K
k

1.3811023 J K
23
N A 6.022 10 mol
1.
2.

R is used for macroscopic quantities (moles)

k is used for microscopic quantities (a molecule)
3 RT 3
tr
kT
2 NA 2

Velocity Distributions
RMS (root-mean-square) Velocity

v
v
i N
N

2
i

1
2

3
1
2
3kT 2 3RT 2
tr kT m v
v

2
2
m M
Maxwell (Maxwell-Boltzmann) Distribution Function

Introductory assumptions

A gas sample has a broad distribution of speeds.

Let the number of molecules with speed between v and v + dv = dN v
The distribution function relates the fraction of total molecules within a
range of velocities between v and v + dv. (This function is what we want
to find!).
dN v
G v dv
N
- Probability of finding molecules with velocity between v1 and v2
v2

G v dv
v1

- Probability of finding molecules with any speed is

G v dv 1

- G v is a probability density.

To find the distribution function for any speed, G v , first find the
distribution function for velocities in z-direction only, g v z .

dN vz

g v z dv z
N
One-dimensional velocity distribution function
Because our sample is in isotropic space (no preferred direction exists),
the distribution functions for the velocities in the other directions are
similar.
Let us examine the product of probability densities in all three
directions.
g vx g v y g vz v
To find g, take derivative w.r.t. vx.
v v
g v x g v y g v z
v v x

vx

vy

vz

2v dv 2v x dv x 2v y dv y 2v z dv z

v v x
v v
g v x g v y g v z
v
vx

vx g vx g v y g vz vx g vx g v y g vz v

v v x

v x
v

g v x g v y g v z

g v x
v v x v

vx g vx vx v v v v

Similar relationships can be found for the y and z directions.

g v y

vyg vy

g v z
v

vz g vz v v

v
v v

g v y
g v x
g v z

b
vx g vx v yg v y vzg vz

Since b does not depend on vx, vy or vz; it must be a constant.

g v x
bv x
g vx
1 2
bv x
g v x
1 2
2
bv
dv

dv

bv

ln
g
v

g
v

Ce
x
x
x
x x g vx x
2

v g v x g v y g vz Ce

1 2
bvx
2

Ce

1 2
bv y
2

Ce

1 2
bvz
2

1
b v2x v2y vz2
3 2

C e

1 2
bv
3 2

C e

Evaluate C by letting the total probability equal one.

bv2x

bv2x

g v x dv x Ce 2 dv x C e 2 dv x 1

A table of definite integrals would include:

e ax dx

1
2 a

1 2
b
b
dv x C 2
when a
1 C

2
2
2 b
b 12 bv2x
g vx
e
2
3
To evaluate b, recall that tr kT
2
1
1
1
tr m v2 m v2x v2y vz2 m 3v2x
2
2
2
3
3
kT
m v2x kT v 2x
2
2
m
2
Alternatively, calculate v x using the probability density.

C e

1 2
bv x
2

2
x

v g v x dv x
2
x

From a table of integrals,

x 2n e ax dx

To apply the integral, n = 1 and a

b
,
2

b 2 bv2x
v x e dv x
2

2n !
22n 1 n!

2
a

bv2x
2

b
b
2!

2
2

1
2
vx
v x e dv x 2
3

b
2
2
23 1! b 2

2
Equate the two calculations of v 2x .

1
2

1 kT
m

b
b
m
kT
Thus the one-dimensional velocity distribution function for an ideal gas is:
v2x

tr ,x
x
m mv
m kT
g vx
e 2kT
e
2kT
2kT
Three-dimensional velocity distribution function
The one-dimensional distribution function yields the probability of
finding an atom with a specific component of the velocity, v z, within a
differential range, vz and vz + dvz
To find the three-dimensional distribution function yielding a velocity, v,
within a range of v and v + dv, we need to recognize that an atom with
velocity, v, can travel in any direction. The velocity of a particle moving in
an arbitrary direction can be represented in a three-dimensional
velocity space.
vy

}dv

vx

vz

An atom with velocity, v, could be anywhere on the sphere with radius, v.

The total probability density of an atom with a velocity between v and v +
dv lies between a sphere of radius, v, and a sphere of radius v + dv in
velocity space..
The volume of this shell is the difference between the volume of the two
spheres.
4
4
3
Vshell Vsphere v dv Vsphere v v dv v3
3
3
4
4
4
4
4
2
3
v3 3v 2 dv 3v dv dv v3
3
3
3
3
3
4
4
4
2
3
3v 2 dv 3v dv dv
3
3
3
4
3v 2 dv 4v 2dv
3
The three-dimensional distribution function is the product of the onedimensional distribution functions and the volume of the shell in velocity
space.
dN v
G v dv v 4v 2dv g v x g v y g v z 4v 2dv
N

x
x
x
m mv
m mv
m mv
g v x g v y g vz 4v dv
e 2kT
e 2kT
e 2kT 4v 2dv
2kT
2kT
2kT

mv
Mv
m 2 2kT
M 2 2RT
2
G v dv
e
4

v
dv

e
4v 2dv

kT
2

RT

The above equation is known as the Maxwell (Maxwell-Boltzmann)

distribution function.
Graphs of Maxwell-Boltzmann distribution function velocity

.55

298 K

0.5

398 K

0.4

f ( u 2 298)
0.3

f ( u 2 398)

2000 K

f ( u 2 2000)
0.2

0.1

0
0

10

- The average velocity of the gas molecules increases as the

temperature increases.
- At low velocities, the shape of the curve resembles a quadratic
function; whereas at moderate to high velocities, the shape of the
curve resembles a Gaussian function.

12
12

4.5
4

SF6, 298
K

f ( u 2 298 )

CO2, 298 K

f ( u 44 298 )
f ( u 146 298 )

f ( u 146 2000)

SF6, 2000
K
1

H2, 298 K

4.5

- The average velocity of the gas molecules decreases as the molar

mass increases.
Aside: The speed of sound in a gas medium is proportional to the
average velocity of the gas molecules. Thus, breathing He
makes your voice higher and breathing SF6 makes your voice
lower.
Other Gas Velocity Averages

Average speed

mv
mv
m 2 2kT
m 2 2kT 3
2
v v G v dv v
e
4

v
dv

e
v dv

kT
2

kT

0
0
0

2
n!
From a table of integrals: x 2n 1e ax dx n 1
0
2a

mv
1!
m 2 2kT 3
m 2
8kT 2 8RT 2
v 4
e
v dv 4

11
2kT 0
2kT m m M
2

2kT

Most probable speed

The most probable speed, vmp, is the speed with the highest probability;
that is, the speed where the velocity distribution is a maximum.
We can find vmp by taking the derivative of the Maxwell-Boltzmann
distribution function, setting it equal to zero and solving for v.
3

dG v d m 2 mv
2kT

4v 2dv 0
e
dv
dv 2kT
2

d mv
d mv
m 2
2kT 2
4

e
v
dv

e 2kT v 2dv 0

dv
dv
2kT
2

mv
mv

d mv
2mv mv
mv3 mv
2kT 2
2kT 2
2kT
2kT

e
v dv
e
v e
2v 0
e
2ve 2kT 0
dv
2kT
kT

mv2
2kT
2kT 2 2RT 2

2 0 v2
v mp

kT
m
m M
RMS speed (from above)
1

3kT 2 3RT 2
v rms v

m M
Comparison of all three averages
vmp v vrms
2

vmp : v : vrms

2 : 8 : 3 1.414 :1.596 :1.732 1:1.128 :1.225

We shall now work out population ratios for different kinds of

energy mode at room temperature, 25 oC (298.15 K). We calculate
population distributions for one mole. The denominator of exponent takes
the value R=NA k = 8.314 JK-1mol-1, and RT = 298.158.314 = 24789 Jmol-1
RT = 2.48 kJmol-1 (rounding).

Electronic level population

For an electronic level difference is quite high. If we take a
hydrogen atom in gas phase = 1000 kJmol -1. The population of the
2s excited state n2s relative to ground state, n1s is

n2 s
1000
403
exp
10 175 , so the number 2s He
n1s
2.48
atoms

n2 s n1s e 403
so that we can be very confident that there are no 2s hydrogen
atoms around at room temperature.
Vibrational level population
Next we consider vibrational modes. If we take CO molecules, the
vibrational quantum levels have an energy separation of around =25
kJmol-1. Vibrational energy levels (v = 1, 2, 3) are much more closely
spaced than electronic ones. Hence

n v 1
25
10
5
exp
e 5 10
nv 0
2.48

If we have a system containing 20000 molecules, than

nv1 20000 5 105 1

It means that one out of every 20000 molecules is found at the first
vibration excited state in a time average.
Rotational levels are much more closely spaced than vibrational
levels. For CO the rotational energy levels are around 0.05 kJmol -1
apart. We can write

nJ 1
0.05
0.02
3 exp
2.94
3 e
nJ 0
2.48
The factor of 3 in the equation above requires some explanation. It
arises because the first excited level J=1 is actually threefold
degenerate (i.e. there are 3 levels all with the same energy). This
degeneracy factor must be taken into account when assessing the
probability of finding a molecule in a given level.
Example 3: Temperature dependence of population. A comparison of
population density between temperatures 25 and 1000 oC.
Calculate the ratio of molecules in excited rotation, vibration and
electronic energy level to that in the lowest energy level.
Data:
T1 = 25 oC, T2 = 1000 oC
first excited energy levels are at
30 cm-1
rotation,
1000 cm-1
vibration,
40 000 cm-1
electronic,
above the lowest one.
Assume that, J = 4 for excited rotation level, and such a level is 2 J+1
fold degenerate.
Vibration and electronic states have no degeneracies.
h = 6.626 10-34J/s, c = 3 1010 cm/s, k = 1.38 10-23 J/K, T1 = 298 K, T2 =
1273 K

Rotation

c
hc~

hc~
nupper

7.8 and at T2
9 exp
nlower
kT

1
~
hc
nupper
8.7
exp
nlower
kT2
h h

In each set of ten molecules at T2 = 1000 oC only one is at the lowest

energy level.

Vibration

hc~
nupper

0.008 and at T2
exp
nlower
kT

1
hc~
nupper

0.323
exp
nlower
kT

A 40-fold increment in population inversion is caused by the increase

in temperature.

Electronic

hc~
nupper

1.24 1084 and at T2

exp
nlower
kT1
hc~
nupper

2.34 10 20
exp
nlower
kT2

Practically, all the molecules are in ground electronic state at room

temperature.
2.
Ideal Gas
a. One molecule

Z1 e

Ei
kT

Ei
kT

translational
states, i

rotational
states, j

Ej
kT

En
kT

ZtransZ rotZ int

internal
states, n

b. Two or more molecules

If the molecules are not interacting, then as before, the partition
ZN
function for N molecules is just Z N Z1N or Z N i depending on
N!
whether the molecules are distinguishable or not. In the ideal gas, the
molecules are not distinguishable one from another. If the molecules
were in a solid, then they would be distinguishable because their positions
would be distinctly different.
[Note that the rotational partition function is lumped in with the internal
partition function.]
c. Internal partition function
The internal partition function sums over the internal vibrations of the
constituent atoms. We would usually approximate the energy levels by
harmonic oscillator energy levels.

Z int e
i

nh i
kT

n 1

The index i labels the vibrational modes, while n labels the uniformly
spaced energy levels for each mode. For instance, the water molecule has

three intermolecular modes. A molecule having more atoms has more

modes. A diatomic molecule has just one mode of vibration.
d. Rotational partition function
A molecule is constrained to a particular shape (internal vibrational
motions apart), which we regard as rotating like a rigid body. The angular
momentum, and therefore the rotational kinetic energy, is quantized,
2
thusly E j j j 1 , where I is the moment of inertia of the molecule
2I
about the rotational axis. Classically, if is the angular velocity and L is
the magnitude of the angular momentum, then the kinetic energy of

I L2 . Quantum mechanically, the angular

1
rotation is KErot I 2
2
2I
2I
momentum is quantized, so that L2 j j 12 with j equaling an integer.
2

Now, this applies to each distinct axis of rotation. In three dimensions,

we start with three axes, but the symmetry of the molecule may reduce
that number. The water molecule has three axes, but a carbon monoxide
molecule has only one. Basically, we look for axes about which the
molecule has a different moment of inertia, I. But it goes beyond that.
If the symmetry of the molecule is such that we couldnt tell, so to speak,
whether the molecule was turning, then that axis does not count. Thats
why there are no states for an axis that runs through the carbon and
oxygen atoms of carbon monoxide.
Therefore, a rotational partition function will look something like this for
three axes
3

Z rot e
i 1

j j 1 i
kT

e. Translational partition function

In an ideal gas, the molecules are not interacting with each other. So the
energy associated with the molecular center of mass is just the kinetic
1
p2
energy, mv2
. The molecule is confined to a finite volume, V, so
2
2m
that kinetic energy is quantized also.
First consider a molecule confined to a finite box of length Lx on the xaxis.
The wave function is limited to standing wave patterns of
2L
wavelengths n x , where
nx

nx = 1, 2, 3, 4, . . . This means that the x-component of the momentum is

h hnx
limited to the discrete values px , n
. The allowed values of

n 2 Lx
kinetic energy follow as

En

h 2 nx2
.
8mL2x

Naturally, the same argument holds for motion along the y- and z-axes.

Z tr e
nx

ny

n2
n 2y
n2
h 2 x 2
z
8 mL x 8 mL2y 8 mL2z

kT

nz

Unless the temperature is very low, or the volume V is very small, then
the spacing between energy levels is small and we can go over to integrals.
2 2
h 2 n 2y
h 2 nx2
1

h nz

2
8 mL2y
8 mLx
8 mL2z
Z tr e
dn x e
dn y e
dn z e kT
0

0
0

2mkT
2mkT
2mkT
Lx
Ly
Lz
2
2
h
h
h2

2mkT
V

2
h

h2 2
vQ is the quantum volume of a single molecule.
The quantity

2mkT
Its a box whose side is proportional to the de Broglie wavelength of the
V
molecule. In terms of that, the Z tr
.
vQ

[Actually, in the classical form of the partition function, we are

integrating over the possible (continuous) values of particle momentum
and position.

Ztr , x

Lx

p x2
2 mkT

dpx dx Lx 2mkT

0 0

The classical partition functions differ from the classical limit of the
quantum mechanical partition functions by factors of h. Because h is
constant, this makes no difference in the derivatives of the logarithm of
Z.]
Putting the parts all together, for a collection of N indistinguishable
molecules
1
N
Z Ztr Z rotZint
N!
3.
Thermodynamic Properties of the Ideal Monatomic Gas
a. Helmholz free energy
Consider the derivative of the partition function with respect to
temperature.


1 Z
ln Z

T
Z T

Ei
kT

e
T

Ei
kT

1
Ei kTi
U
e
2

2
Z
kT
kT

On the other hand, recall the definition of the Helmholtz free energy.
F
F U TS U T

T V

F
F T
U
T V
F

2 T
T
U
T

V
F

U
T
T T 2

V
Evidently, we can identify the Helmholtz free energy in terms of the
partition function thusly,
F kT ln Z .
N

1 V
For the monatomic ideal gas, Z , whence (using the Stirling
N ! vQ
approximation)
F kT N ln V N ln vQ N ln N N NkT ln N 1 ln vQ ln V .

b. Energy & heat capacity

ln vQ
ln Z
1 vQ
NkT 2
U kT 2
NkT 2

vQ T
T V
T V

2mkT
NkT 2

2
h

2mkT
NkT

2
h

CV

2mkT

T h 2

3 2mkT

2 h 2

2mk 3
2 NkT
h 2

3
U
3

NkT Nk
T T 2
2

c. Pressure
Of course, were going to get the ideal gas law.

NkT ln N 1 ln vQ ln V
F
P

V
V T , N
d. Entropy and chemical potential
NkT ln N 1 ln vQ ln V
F
S

T
T V , N
ln vQ
S Nk ln N 1 ln vQ ln V NkT
T

ln V
NkT V

T , N

NkT

V
T , N

V , N

h2

S Nk ln N 1 ln vQ ln V NkT

2mkT

h2

S Nk ln N 1 ln vQ ln V NkT

2mkT
3
S Nk ln N 1 ln vQ ln V Nk
2
V 5

S Nk ln
NvQ 2

NkT ln N 1 ln vQ ln V
F

N
N T ,V
ln N
kT ln N 1 ln vQ ln V NkT
N
V

kT ln
NvQ

2mkT

T h 2

3 2mk
2
2 h

T ,V

Rotation and vibration of diatomic and polyatomic molecules

For a diatomic molecule as well as the three translational degrees of
freedom there are also two rotational and one vibrational degree of
freedom:
z

NOTE - the molecule could equally well have been drawn along the z axis.
there is nothing special about the y axis.

As shown in the diagram there can be rotation of the whole molecule

about the x and z axes. The atomic masses are concentrated in a tiny
nucleus and the moment of inertia about the y axis is so small that for
the present we will simply state that there is no contribution to the
rotational kinetic energy from rotation about the y axis.
There is one vibrational degree of freedom which is along the y axis.
Degree of freedom - examples are motion in the x, y and z directions.
Motion in each is independent of motion in either of the other two. A
diatomic molecule is able to vibrate and this vibrational motion is
independent of translation in the x, y or z directions. It is another degree
of freedom. Electronic motion introduces other degrees of freedom.
Consider an atom. It can move in the x, y and z directions. It's motion in
any direction is independent of it's motion in the other two. It is said to
have three degrees of freedom.
Consider two atoms moving independently of each other. Between them
they have six degrees of freedom. N independent atoms have 3N degrees
of freedom.
What about a diatomic molecule? There are two atoms but they are not
independent of each other. It turns out that there are still 6 degrees of
freedom. Three of them are the translational of the centre of mass of
the molecule and of the other three, one is the vibration of the molecule
and two are the rotation.
A triatomic molecule has 9 degrees of freedom. Three of these are the
translation of the centre of mass. A linear triatomic has a further four
vibrational and two rotational degrees of freedom. A bent triatomic has
three vibrational and three rotational:

vibration

rotation

Rotation and vibration of a diatomic molecule.

Normal modes of vibration of linear triatomic molecules.

Normal modes of vibration of bent triatomic molecules.

Equipartition of energy

"When a substance is in equilibrium there is an average energy of kT/2

per molecule of RT/2 per mole associated with each degree of freedom."
According to the equipartition principle the average energy in each
degree of freedom of a gas should be the same, namely RT/2 J.mol -1 .
This implies that for each degree of freedom the contribution to Cv d ( RT / 2) - is constant at R/2 or R for vibration.
dT

This is a good approximation at room temperature for translational and

rotational degrees of freedom but not for vibration. We will see why
later.
Experimental results show that the heat capacity varies with
temperature as follows.
Molar heat capacities of ideal gases in J.K -1 - hard spheres
3N - 3
Trans
Rot
Vib
Atom
0
Diatomic
3
Linear
6
triatomic
Bent triatomic 6
Examples of observed heat
table.

3R/2
3R/2
3R/2

0
2R/2
2R/2

0
2R/2
8R/2

Cv (J.K-1)
1.5R
3.5R
6.5R

3R/2
3R/2
6R/2
6.0R
capacities for gases are given in the following

Molar heat capacities of real gases in J.K-1

-100

Temp
(C)
100

400

600

Gas
He, Ne, Ar,
Hg
H2

12.5

12.5

12.5

12.5

12.5

Ideal
gas
12.5

17.5

20.5

20.8

20.8

20.9

29.1

N2

20.7

20.7

20.8

22.2

22.7

29.1

O2

20.8

20.9

21.0

24.5

25.9

29.1

Cl2

---

24.5

24.6

26.1

26.7

29.1

H2O (bent)
CO2 (linear)

---

---

26.6

28.5

31.8

49.8

---

28.2

32.1

41.2

45.6

54.0

Why do we have this variation? To understand this we have to see why at

low temperature some gases do not seem to take up as much energy as
would be expected. Qualitatively it is easy to see that if energy levels are
quantised the equpartition theory is on dangerous grounds.
Energy level spacings
How can the deviations of the heat capacities of gases from those
predicted by the equipartition theory be explained?

room
temperature
thermal
energy

translational rotational
energy
energy

vibrational electronic
energy
energy

The translational energy levels are so close together that they can be
regarded as being continuous.
The above diagram shows energy levels in a hypothetical molecule. The
example does not correspond to any particular molecule and is purely for
the purpose of showing the participation of different degrees of freedom
in determining the heat capacity of a gas.

The average energy at room temperature is marked. The following should

be noted :
translational energy levels are extremely close together and many are
populated.
rotational spacing is quite small and a few levels will be populated.
vibrational spacing is larger and in this example only the ground and
first excited level will be significantly populated.
the first excited electronic state is very high and will not participate.
Perhaps you can see that as the temperature is increased energy can go
into translational levels without restriction ie. as T is increased the
translational energy will increase as given by 3/2RT.
However energy cannot go freely into electronic energy. In fact
essentially no collisions will be energetic enough to give electronic
excitation and this degree of freedom will contribute nothing to the heat
capacity.
For the inert gases there are no vibrational or rotational degrees of
freedom and the first electronic level is much higher than thermal
energy. The heat capacity is exactly what one would expect for a particle
with only translational degrees of freedom
For many diatomic and polyatomic gases at room temperature energy does
not freely go into vibration. For example all collisions in the range below
the first vibrational level will not give any vibrational excitation and only a
fraction of the rest will. Hence the heat capacity is lower than predicted.

Population of energy levels

The following equation from statistical mechanics :

ni
e kT

i kT
N
e

ni = no. of particles in energy level i ; N = total

no. of particles;
tells us that if the temperature is low only the lowest energy levels are
significantly populated. At room temperature k.T is about 0.6 x 10 -20 J
which is insufficient to give much vibrational excitation of common
diatomic molecules.
The denominator in this equation is a very important quantity called the
partition function (q) which you will learn more about in Statistical
Mechanics.
Example 4:

A hypothetical molecule has energy levels equally spaced by 4.14 x 10 -21 J.

What is the population of the energy levels at temperature 100K, 300K,
428.6K, 1,000K?

-21
E x 10
12.4
8.28
4.14

T (K)
q
1/kT

100
1.05
7.25
1020

300
1.58
x 2.42
1020

428.6
1,000
1.99
3.86
20
x 1.69 x 10
0.725
1020

The length of the horizontal bar represents the population of the state.
It can be seen that as the temperature is increased higher energy levels
are populated as might be expected. Note that the lowest level is always
the most populated.
Note that the equation given above for the population of energy states is
the Boltzmann distribution for distinguishable particles. The following
assumptions were made :
particles are distinguishable
any number of particles can be in the same energy level.
The distribution is different where these two assumptions are not
applicable, eg. for Fermi particles (such as an electron) and Bose particles
(such as a photon).
Example 5:
A hypothetical gas has molecules with only one excited energy level at
0.2ev. Calculate the molar heat capacity of the gas at 0K, 1,000K and
5,000K. Make a qualitative sketch of CV as a function of T and explain it's
form.
1eV = 1.6 x 10-19 J
R = 8.314 J.K-1.mol-1
k = 1.38 x 10-23 J.K-1
NA = 6x1023 molecules per mol

ANSWER
Molecule with only one excited level

The fraction F of molecules in the excited level is given by :

0.2 x1.6 x10

1 e

19

kT

0.2 x1.6 x10

19

kT

Now 0.2x1.6x10-19/k = 2319

2319 T

1 e

2319

Y
1 Y

The energy of 1 mole of the gas = E = F x 0.2 x 1.6 x 10 -19 x 6 x 1023

J.mol-1 = F x 1.92 x 104 J.mol-1
Therefore CV can be found from :

CV (E / T) V

by differentiation or computation E at appropriate intervals.

Differentiation
Using :

d u 1 du u dv
d w
dw
2
and
e ew

dT v v dT v dT
dT
dT
dF d Y
1 dY
Y d(1 Y )

dT dT 1 Y 1 Y dT 1 Y 2 dT

dY 1
Y dY 1

dT 1 Y 1 Y 2 dT 1 Y 2

Y e 2319 T
dY 2319 2319 T

2 .e
dT
T
dF 2319 e 2319 T

2
.
dT
T 1 e 2319 T 2
dF
CV
x1.92x10 4 J. K 1 . mol 1
dT

When T is very small CV 0

When T = 1,000K
0.09837
dF
2.319x10 3
0.1891x10 3
2
dT
1 0.09837

C V

dF
x1.92x10 4 3.631JK 1 0.437 R
dT

When T = 5,000K

0.6289
dF
92.76x10 6
21.98x10 6
2
dT
1 0.6289
CV

dF
x1.92x10 4 0.4221J.K 1 0.051R
dT

Example 6:
A system of five particles each having one degree of freedom and energy
levels equally spaced at 10 -20 J has a total energy of 4 x 10 -20 J. Calculate
the statistical population of the energy levels.

5 ways

N( )
1

5
N( )

1
0 1 2 3 4 5

30 ways

0 1 2 3 4 5

5 ways

N( )

10 ways

N( )

1
0 1 2 3 4 5

0 1 2 3 4 5

20 ways

N( )

0 1 2 3 4 5

Divide

by 5

0.0

0.2

0.71 1.43 2.5

70
0

20

50

100 175

N(e) average

3
2
1
0
0

From the Boltzmann equation we have:

n i Ce
i

U sin g n i 175e i
When i 1x10 20

20

100 175e .10

ln

100
.10 20
175

0.56
1

20
kT
10
T 1,294 K

Using the relation Eav = kT:

E av 0.8x10 20 J kT
T 1,159 K
How much energy? How fast do the molecules/atoms move?
Translation
Thermodynamics, Maxwell-Boltzmann, equipartition theorem, translational
kinetic energy of gas = (3/2) k T per molecule.
At room temperature, T = 300 K, Etrans = 6.21 x10-21 J molecule-1 = m v2 / 2

v = 1.36 x103 ms-1 (~3000 mph!!!) m = 4 amu,

v = 3.05 x102 ms-1 m = 78 amu

For He atom,

For C6H6

This is the velocity on average, not of any particular molecule.

Rotation
Similarly the equipartition theorem states that the average rotation
energy of a diatomic molecule is (1/2) k T per molecule per rotational
direction.

Erot,x = Re2 x2 /2 = (1/2) k T = 2.07 x10-21 J

molecule

At T = 300 K,

-1

Re = 1.2746x10-10 m (spectroscopic data)

for H 35Cl:

= mH mCl / (mH + mCl) ~ (1 x 35)/(1+35) amu ~

1.614x10-27 kg

x ~ 6.288x1012 radians s-1 = 1.000x1012 rev s-1

a revolution every 1.0 ps on average.
Vibration
If we assume a vibrational energy of 10 -19 J molecule-1 for NO which has a
force constant k = 1.54x103 Nm-1 and Re = 1.1508x10-10 m, can estimate
(classically) the extent to which the bond stretches. At maximum (or
minimum) R all the energy is Potential Energy (the atoms come to rest at
the limits of the vibration, no Kinetic Energy) therefore (k/2)(R Re)2 =
10-19 J, from which (R Re) = 1.14x10-11 m about 10% of Re When R = Re all
the energy is kinetic energy, therefore vR2/2 = 10-19 J , from which vR =
4016 ms-1 and from the classical equations of motion, estimate that a
vibration period is 2.26x10-13 s or the vibrational frequency is 4.40x10 14 s1

.Quantum Mechanical Molecular Energy of the Nuclei. The motion of

nuclei in molecules does not obey classical mechanics. The energies of

translational, rotational and vibrations motion of nuclei obey Quantum
Mechanics. In all three cases quantum mechanics finds the energy to be
quantized. Only certain values of energy are allowed. The equations for
the energy involve quantum numbers (1 quantum number for every
independent coordinate).
Translation. The Particle in the box problem. The energy of motion of a
particle of mass m in 1 D (say along x) and restricted to a path length of L
(e.g. a molecule contained in a box; an electron traveling along a copper

wire) is found to be: En = n2 h 2 / (8mL2) Joules

positive integer values >0, h = 6.626x10

-34

n = 1, 2, 3,

all

Js (Plancks constant), m (mass)

2

, kg L length of box, m, Units (Js) /(kg m ) J

In 3 D, a box of lengths A, B, C in the x, y, z directions, the energy is
specified by three quantum numbers.

En,p,q = n2 h 2 /(8m A2) + p2 h 2 /(8m B2) + q2 h 2 /(8m C2)

Joules

n = 1, 2, 3, ; p = 1, 2, 3, ; q = 1, 2, 3,
The sum of the three 1 D energies.
The 3D case demonstrates degeneracy if the box is a cube, A = B = C:

En,p,q = (n2+ p2 + q2 )h 2 /(8m A2) J

n = 1, 2, 3, ; p = 1, 2, 3, ; q = 1, 2, 3,
n = 1, p = 2, q = 3 has energy E1,2,3 = (1+ 4 + 9 )h 2 /(8m A2) = 14 h 2 /(8m A2)
J as do: E1,3,2 E2,1,3 E2,3,1 E3,1,2 E3,2,1
6 different energy levels with the same energy 6 degenerate levels.
Consider a molecule in a (1D) room: O2 (g) , m = 32 amu = 5.314x 10-26 kg, L
= 10 m

En = 1.03283x10-44 n2 Joules
Points to note about the Particle in the Box problem:
1) n 0. The particle cannot have zero translational energy. This has
to do with the Heisenberg uncertainty principle.
2) Energy levels ~ n2, get further apart with increasing n.
3) 1D box is non-degenerate (no 2 energy levels have the same
energy), 3D box has degenerate levels under special circumstances.
Quantized Rotational Energy for a diatomic molecule
Rotation. The Rigid Rotator problem. The energy of two masses, mA and

mB at a fixed distance Re rotating about their centre of mass, is found to

be: Erot = ( 2 / 2 I) J (J + 1) Joules

J = 0, 1, 2, 3 , I = Re2

Js momentum of inertia, kg m2 = h / 2

= mA mB / (mA + mB)

reduced mass, kg

Each energy level is degenerate. There are (2 J + 1) levels with the same
energy. There is a second quantum number mJ which has integer values
between J and + J , that is

(2 J + 1) values all with the same energy

determined by J. 2 quantum numbers as there are 2 separate rotational

axes/motions.
For H 35Cl (data given previously)

Erot = ( 2 / 2 I) J (J + 1) = 2.12x10-22 J (J + 1) Joules

In spectroscopy of diatomic molecules, it is usual to write

Erot = B J (J + 1)
B = ( 2 / 2 I) = ( 2 / 2 Re2)

Joules

is called the rotational

constant and in spectroscopy it is usual to give the value in wavenumbers,

cm-1, E (J) = h c E(cm-1) , c velocity of light, cm s-1 !!

For B = 2.12x10-22

10.7 cm-1
Er

qu. number energy

degeneracy

Points to note:
J = 4, E4 = 20B, (2J+1) = 9 levels

1) Energy levels ~(J2 + J),

get further apart with

J = 3, E3 = 12B, (2J+1) = 7 levels

increasing J

J = 2, E2 = 6B, (2J+1) = 5 levels

2) J = 0 is allowed.

J = 1, E1 = 2B, (2J+1) = 3 levels

3) Degeneracy (2 J + 1)

J = 0, E0 = 0B, (2J+1) = 1 level

4) Excellent agreement

with spectroscopy in the microwave region.

Specific heat of ideal gases and the equipartition theorem

Specific heats revisited

The specific heat of a material will be different depending on whether
the measurement is made at constant volume or constant pressure.

 Molar specific heat at constant volume

cV (1/n) dQ/dT|V
But if dV = 0 then dW = 0 and by the first law of thermodynamics,
dEint = dQ ,

cV = (1/n) Eint/T |V true for all materials.

Specializing to ideal gases, we know Eint(T)
cV = (1/n) dEint/dT
or

dEint = ncVdT
true for all ideal gases.
Molar specific heat at constant pressure
cP (1/n) dQ/dT|P
and using the first law,
cP = (1/n) [dEint+dW]/dT|P = (1/n)dEint/dT|P + (1/n)dW/dT|P
For an ideal gas, Eint(T) and
dW|P = d(PV)|P = P dV|P = P d(nRT/P)|P = nRdT

cP = c V + R
true for all ideal gases.
Equipartition Theorem
Each degree of freedom of a system has an energy kBT.
A degree of freedom is an independent mode of motion: translation,
rotation, and vibration. Let the number of degrees of freedom be
denoted f. Neglecting vibration,
for ideal gases:
N=nNA and R=NAkB

System
m.i.g.

f
3N
(trans.)

Eint(T)
3N kBT
3/2 nRT

1/ndE/dT
cV
3/2 R

cV+R
cP
5/2 R

d.i.g.
5N
5N kBT
dumbbell(trans.+rot.) 5/2 nRT

5/2 R

7/2 R

p.i.g.

6/2 R

4R

6N
6N kBT
(trans.+rot.) 6/2 nRT

Ideal Gas
Ideal gas law

PV = nRT

First Law of Thermo.

dEint = dQin - dWout

Processes

isothermal, adiabatic, etc.

Work by gas

Wout = p dV

Internal energy of gas

Eint(T) = f kBT

An application of the Internal Energy expression.

The Equipartition Theorem and Heat Capacities.
The Equipartition Theorem states: That when quantum effects can be
ignored, the average energy of each squared term of molecular energy is
kT .
translational energy:
mvx2 + mvy2 + mvz2 3/2 kT
rotational energy:
IA A2 + IB B2 + IC C2 3/2 kT
(kT for a linear as only 2 rotational axes)
vibrational energy:
v2 + kx2 kT per vibrational mode
This means that at a temperature T there is (on average) as much energy
in translation as there is in rotation (can seldom ignore the quantum
effects in vibrational motion).

 1 Z
N z
U

Z
z
z zt z r zvt ze
U

N
( zt z r zvt ze )
zt z r z v z e

N ( zt ) N ( z r )

zt
z r

N ( zv ) N ( ze )

zv
ze

t r v e

average translational energy per molecule, etc.

Now consider each bit of the molecular energy.
Average translational energy:
Average rotational energy, linear molecules:

z r kT / B

1 qr

zr

1 kT
For a non-linear molecule:

3
kT
2

Average vibrational energy:

zv

h
1

1 zv

zv

1 e

1 e h
h e h

1 e h

1 e

1 e h

1h e

1 e

now let T , so that quantum effects can be ignored:

h 0

h e h
h (1 h )
v

1 (1 h )
1 e h
h (1 h )

1 h 1 kT
h

kT per vibration, but only in extreme conditions (very high temperature).

At reasonable temperatures:
< t > = 3/2 kT
< r > = kT (linear), 3/2 kT (non-linear)
< v > 3/2 kT per vibration
if T large (or small)
Can use these results to discuss the dependence of Heat Capacities on
Temperature.
As:

CV

T V

can separate components of CV

Ct C r Cv Ce
V

N
V
T
3 / 2N k

Ct

3 / 2kT
N

Electronic Partition Function

ze

g je

j ,e

j ,electro n ic en erg ies

g 0 g1e

1,e

g 2e

2 ,e

In nearly all cases electronic energies are very large and all terms except
the first are ~ 0

ze g 0
Justifying the value of
Consider a very simple system and calculate its Internal Energy.
System with equally spaced energy levels:

En nE ,

(n 0,1,2,)

Z n e En n e
1 e

(1 e
but e

2 E

nE

3 E

) 1

1 E

Z ~ ( E ) 1

which is a very simple result for a very simple system.

Now calculate the Internal Energy:

1 Z
1
( E ) 1
U

Z
( E ) 1

( E 2 ) 1
1
( E )
another simple result.

U is a state function of the system; (N, T, V ) fixed, U fixed.

To change U have to change (N, T, V ) to new, fixed values.
But: d U = T dS + p dV and dV = 0 as V is fixed (not variable).
Change U of the system by changing T .

U~T,

Therefore:

-1 ~ T ; ~ T

-1

= ( kT ) -1
Problems of Ch. (5)
1. Consider a mixture of Hydrogen and Helium at T=300 K. Find the
speed at which the Maxwell distributions for these gases have the
same value.

Pv, T , m
2 k BT

m1

k
T
B

3/ 2

3/ 2

mv2

4v 2 exp
2k BT

m1v 2 m2

4v exp
2
k
T
2

k
T
B
B

3/ 2

m2v 2

4v exp
2
k
T
B

3
m v2 3
m v2
ln m1 1 ln m2 2
2
2k BT 2
2k BT

3 m1
v
m1 m2
ln

2 m2 2k BT

m1
3 1.38 1023 300 ln 2
m2

1.6 km/s
m1 m2
2 1.7 1027

3k BT ln
v

2. Consider an ideal gas of atoms with mass m at temperature T.

(a) Using the Maxwell-Boltzmann distribution for the speed v, find the
corresponding distribution for the kinetic energy (dont forget to
transform dv into d).
(b) Find the most probable value of the kinetic energy.
(c) Does this value of energy correspond to the most probable value of
speed? Explain.

dN v NPv dv N
2

k
T
B

dv
2
dN NP d v
d
m

mv2
dv
4v exp
2
k
T
B

m
1 2

dv
d N
2 m
2 k BT

P
2 k BT

P
0

3/ 2

3/ 2

3/ 2

8 1 2

exp
d
m
k BT 2 m

4 2 1/ 2

exp
3/ 2
m
k BT

1/ 2
1
1 1/ 2
exp

0
exp
2
k BT
k BT k BT

2k BT
dPv
0 vmax
dv
m

v vmax
3. Using the Maxwell-Boltzman function, calculate the fraction of Argon gas
molecules with a speed of 305 m/s at 500 K.[ 0.00141].
4. If the system in problem 1 has 0.46 moles of Argon gas, how many molecules have
the spped of 305 m/s?
5. Calculate the values of vmp, vavg, and vrms for Xenon gas at 298 K. .[ vmp = 194.27
m/s, vavg =219.21 m/s, vrms= 237.93 m/s].

6. From the values calculated above, label the Boltzmann distribution Plot with the
approximate locations of vmp, vavg, and vrms.
7. What will have a larger speed distribution, Helium at 500 K or Argon at 300 K?
Helium at 300 K or Argon at 500 K? Argon at 400 K or Argon at 1000 K?.
8. Consider an assembly of N = 105 particles distributed over the five available
energy levels, j = 0, 1, 2, 3, and 4 shown in the diagram. The energy of each level (in
units of Joules) is given by j = j (100 K) kB, and the degeneracy of each level is gj
= 108. What is the population distribution, the total assembly energy E (J), and the
assembly entropy S (J/K) at a temperature of 100 K? .

9. For an ideal gas of classical non-interacting atoms in thermal equilibrium, the Cartesian
components of the velocity of are statistically independent. In three dimensions, the
probability density distribution for the velocity is

P vx ,v y ,vz 2 2
Where 2

3/2

v 2 v y2 vz2
exp x

2 2

kT
1
. The energy of a given atom is E m v 2 .
m
2

Find and sketch the probability density distribution for the energy of an atom in (i) three
dimension, (ii) two dimension and (iii) one dimension.
10. Given a gas of particles with a Maxwellian distribution for velocity:
(a) What is the most probable velocity?
(b) What is the average velocity?
(c ) What is the root-mean-square speed?
(d) What is the most probable speed?
(e) What is the average speed?
(f) What is the average energy of a particle?.
11. Compute the mean energy of the canonical distribution of mean energy
The system in the representatives statistical ensemble are distributed over their accessible
states in according with the canonical distribution

Pr

e Er
e Er
r

the mean energy given by

e E
E
e
Er

Er

where

where Z=

Er

Er

Er

the quantity Z defined the sum over state or partition function

1 Z
ln Z
=
Z

12. Using the canonical distribution compute the dispersion of the energy

The canonical distribution implies a distribution of systems over possible energies; the
resulting dispersion of the energy is also readily computed

E 2 E E 2 E 2 E

e E

e
Er

E2

here

2
r

Er

but

Er

e Er
Er =
e Er E r
r
r

then

E2

1 2Z
Z 2

using the following

1 Z
1

2
Z
Z

Z 1 2 Z

+
2
Z

E E 2 - E

E 2 E =

ln Z

10. The internal energy of the ideal gas is given by E=E(T) show that for the ideal gas its
internal energy does not depend on its volume
Answer
Let E=E(T,V)
Then we can write mathematically

E
E
dE
dT
dV
T v
V T
from the first law

TdS dQ dE dW
dS

1
vR
dE
dV using the above equation for dE
T
V

dS

1 E
1 E
vR

dT
dV
T T V
T V T V

the entropy as a function of T and V

S=S(T,V)

S
S
dS
dT
dV Comparing the equation
T V
V T
1 E
S

T V T T V

1 E
vR
S
with the second order differential equation

V T T V T V

2S
2S

VT TV
S
1 E

V T T V V T T T V

1 2E

T VT

vR
S
1 E

T V V T T V T V T V

1
2
T

2
E 1 E

V T TV

comparing the two equation

1 E 1 2 E

2

V
T

T TV

1
T 2

1 2 E
=
the right and the left equations are equal when
T VT

0 which implies E is independent of V

V