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f( ) =
and the energy is given by the 3-dimensional particle in a box model:
2
h 2 nx2 ny nz2
=
+ +
8m L2x L2y L2z
We define
n 2 = n 2x + n 2y + n 2z
(the square of n is taken to eliminate directionality), then
n2h2
=
8mL2
where we have let the lengths of each side of the box be equal.
page 1
As we previously saw, the energy spacing between translational energy states is very small such that
we can describe the states as forming a continuum in energy space (indexed by n). In determining
the distribution of energies. We can think of this density of translational states as a sphere in
space. The volume of the sphere determined over a given interval of n is the density of translational
states. The figure below depicts the sphere octet of interest (why only and octet?):
nz
nx
n
dn
ny
Total volume of the sphere () is:
n
4
=
8
dn
such that:
d =
n2 dn
We now need an expression for n. We can get this by equating the kinetic energy to the
translational energy derived above:
n 2h 2
n2 h 2
1 2
=
=
=
mu
8mL2 8mV 2 3 2
page 2
2mV
dn =
h
du
We can then use these expressions for n and dn with the differential expression for our sphere as
follows:
d =
n2 dn =
We now modify the relationship stated at the beginning of this lecture that gave the fraction of
molecules at a specific energy to be the fraction of molecules in a given region of energy space:
dNi d
=
e
N
q
page 3
m
1 dN
= 4 u2
2 kT
N du
mu 2
2
e 2kT
0.004
CO2
100 K
0.003
f(v)
0.002
600 K
0.001
0
0
200
400
600
v(m/s)
page 4
800
1000
1200
Characterizing Distributions
To get a general accounting of the velocity of a gas, rather than plot the entire distribution,
we use the Maxwell-Boltzmann distribution to provide information on the average and root-meansquared (rms) speeds as follows. First, the average is defined as:
f (u)
dnu
N
0
f (u) =
where f(v) represents some function of velocity (or speed in our case since we have not defined the
direction of translation) and N is the total number of molecules. For example, the rms average
speed would be the square root of the average speed squared:
2
u
dnu
N
0
Now
dN =
u2
3 mu 2
u
2 m 2 2kT
=
N
4
u
e
du
2 kT
0 N
page 5
Now
3
8 a5
4 ax
x e =
2
such that
and
urms =
u2 =
3kT
m
In addition, we could do the same development for the average speed except that now:
f (u) = u
and we would find that:
uave =
8kT
m
ump =
2kT
m
page 6