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Mean Free Path
The mean free path or average distance between collisions for a gas
molecule may be estimated from kinetic theory. Serway's approach is a good
visualization - if the molecules have diameter d, then the effective cross-
section for collision can be modeled by
using a circle of diameter 2d to represent a molecule's effective collision area
while treating the "target" molecules as point masses. In time t, the circle
would sweep out the volume shown and the number of collisions can be
estimated from the number of gas molecules that were in that volume.
The mean free path could then be taken as the length of the path divided by
the number of collisions.
The problem with this expression is that the average molecular velocity is
used, but the target molecules are also moving. The frequency of collisions
depends upon the average relative velocity of the randomly moving
molecules.
Refinement of mean free path Calculation Frequency of collision
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Refinement of Mean Free Path
The intuitive development of the mean free path expression suffers from a
significant flaw - it assumes that the "target" molecules are at rest when in
fact they have a high average velocity. What is needed is the average relative
velocity, and the calculation of that velocity from the molecular speed
distribution yields the result
Show
which revises the expression for the effective volume swept out in time t
The resulting mean free path is
The number of molecules per unit volume can be determined from
Avogadro's number and the ideal gas law, leading to
Calculation
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Mean Free Path Calculation
The mean free path equation depends upon the temperature and pressure as
well as the molecular diameter.
For pressure P
0
= mmHg = inHg = kPa
and temperature T= K = C = F,
Molecules of diameter x 10
-10
meters (angstroms)
should have a mean free
path of
= x 10^
m
which is times the molecular diameter
and times the average molecular separation of x 10^
m.
The values for pressure, temperature, and molecular diameter may be
changed above to recalculate the mean free path. A nominal molecular
diameter of 0.3nm = 3 x 10
-10
m will give you a reasonable approximation.
The pressure required for a given mean free path can be calculated by
changing the value of the mean free path above. The calculation is not
designed to allow any other changes (their values will be replaced
unchanged by the calculation.)
From the mean free path and the average velocity, the mean time between
collisions and the frequency of collision can be calculated.
Example of mean free path compared to molecular separation.
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Mean Free Path Perspective
You may be surprised by the length of the mean free path compared to the
average molecular separation in an ideal gas. An atomic size of 0.3 nm was
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assumed to calculate the other distances.
Mean Free Path Calculation Frequency of collision
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Average Relative Velocity
In order to calculate the mean free path for a molecule of a gas, it is
necessary to assess the average relative velocity of the molecules involved
rather than just the average velocity of any given molecule. The relative
velocity of any two molecules can be expressed in terms of their vector
velocities.
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The magnitude of the relative velocity can be expressed as the square root of
the scalar product of the velocity with itself.
This expression can be expanded as follows.
Taking the average of the terms leads to
Since the same average velocity would be associated with each molecule,
this becomes
Mean Free Path Calculation Frequency of collisions
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