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2 2
Equipartition Theorem Examples
LC Circuit:
1 d Harmonic Oscillator:
Equipartition Theorem Examples
2 2
1
PE kT
2
E E KE PE kT
Classical Ideal Monatomic Gas
For this system, it’s easy to show
that The Temperature is related to
the average kinetic energy. For one
molecule moving with velocity v in
3 dimensions this takes the form:
1 3
KE m v kT
2
2 2
Also, for each degree of freedom, it can be shown that
1 1 1 1
m v x m v y m v z kT
2 2 2
2 2 2 2
Classical Statistical Mechanics:
Canonical Ensemble Averages
Probability Function: e E kT
P(E )
kT
Z
• P(E) dE probability to find a
particular molecule between E & E + dE
Normalization: P(E )dE P(v)dv 1
0 0
E kT
e
P(E )
kT
Z
EP(E )dE
E E 0
Average Energy:
P(E )dE
0
P(v)dv
0
Classical Kinetic Theory Results
• We just saw that, from the Equipartition
Theorem, the kinetic energy of each particle in an
ideal gas is related to the gas temperature as:
<E> = (½)mv2 = (3/2)kBT (1)
v is the thermal average velocity.
• Canonical Ensemble Probability Function:
e E kT
P(E )
kT
Z
• In this form, P(E) is known as the
Maxwell-Boltzmann Energy
Distribution
e E kT
P(E )
kT
Z
• Using <E> = (½)mv2 = (3/2)kBT along with
P(E), the Probability Distribution of
Energy E can be converted into a
Probability Distribution of Velocity P(v)
This has the form:
P(v) = C exp[- (½)m(v)2/(kT)]
• In this form, P(v) is known as the
Maxwell-Boltzmann Velocity
Distribution
Kinetic Molecular Model for Ideal Gases
Assumptions
1. The gas consists of large number of individual
point particles (zero size).
2. Particles are in constant random motion &
collisions.
3. No forces are exerted between molecules.
Equipartition Theorem:
Gas Kinetic Energy is Proportional to the
Temperature in Kelvin.
3
KE R T
2
Maxwell-Boltzmann Velocity Distribution
• The Canonical Ensemble gives a distribution
of molecules in terms of Speed/Velocity or
Energy.
• The 1-Dimensional Velocity Distribution
in the x-direction (ux) has the form:
1
dN mu x / k T
2
A e 2 du x
N
Maxwell-Boltzmann dN 1
mu x 2 / k T
Velocity Distribution N A e 2 du x
Low T High T
3D Maxwell-Boltzmann Velocity
Distribution a (½)[m/(kBT)]
dN a au x 2 dN a au z 2
e du x e du z
N 1D u x N 1D u z
dN a au y 2
e du y
N 1D u y
In Cartesian Coordinates:
3/ 2
dN a a[u x 2 u y 2 u z 2 ]
e du x du y du z
N 3D
Maxwell-Boltzmann Speed
Distribution
• Change to spherical coordinates in Velocity
Space. Reshape the box into a sphere in
velocity space of the same volume with radius u .
V = (4/3) u3 with u2 = ux2 + uy2 + uz2
dV = dux duy duz = 4 u2 du
dN / N 4 au 2
a u e
3/ 2 2
du 3D
3D Maxwell-Boltzmann Speed Distribution
Low T
High T
Maxwell-Boltzmann Speed
Distribution
dN / N 4 au 2
a u e
3/ 2 2
du 3 D u
Convert the speed-distribution into an energy-
distribution: = (½)mu2, d = mu du
3/ 2
dN / N 2 1
1/ 2
e kT
d 3D kT
Some Velocity Values from
the M-B Distribution
• urms = root mean square (rms) velocity
• uavg = average speed
• ump = most probable velocity
dN
( x ) average x
n n
N x
Comparison of Velocity Values
Ratios in Terms of
urms uavg ump
kT 8 kT kT
3 2
m m m
1/ 2 1/ 2 1/ 2
2kT 8kT 3kT
vm v vrms ;
m m m
The Probability Density Function
•Random motions of the molecules
can be characterized by a probability
distribution function.
•Since the velocity directions are
uniformly distributed, we can reduce
the problem to a speed distribution
Function f(v)dv which is isotropic.
The Probability Density Function
•Let f(v)dv fractional number of
molecules in the speed rangefrom
v to v + dv.
•A probability distribution
function has to satisfy the
Condition:
f v dv 1
0
The Probability Density Function
• We can use the distribution function to
compute the average behavior of the
molecules:
f v dv 1
0
v vf v dv v v f v dv
2 2
0 0
vrms v 2