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

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Kinetic
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Reference:
Rohlf
Ch. 2

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
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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

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It should be noted that this expression for the mean free path of molecules treats them as
hard spheres, whereas real molecules are not. For noble gases, the collisions are probably
close to being perfectly elastic, so the hard sphere approximation is probably a good one.
But real molecules may have a dipole moment and have significant electrical interaction as
they approach each other. This has been approached by using an electrical potential for the
molecules to refine the calculation, and also by using the measured viscosity of the gas as a
parameter to refine the estimate of the mean free path of molecules in real gases.
Reference:

Wiki: mean free path

Wiki: viscosity
Gas viscosity

Calculation

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Mean Free Path Calculation

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The mean free path equation depends upon the temperature and pressure as well as the
molecular diameter.
For pressure P0 =

and temperature T=
Molecules of diameter

mmHg =
K=

inHg =

kPa

C=

F,

x 10-10 meters (angstroms)

should have a mean free path of

x 10^

Kinetic
theory
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which is
and

times the molecular diameter

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 collisions can be calculated.
Example of mean free path compared to molecular separation.
Relation of mean free path to viscosity

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Mean Free Path Perspective

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Gas law
You may be surprised by the length of the mean free path compared to the average molecular concepts
separation in an ideal gas. An atomic size of 0.3 nm was assumed to calculate the other
Kinetic
distances.
theory
concepts

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

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any given molecule. The relative velocity of any two molecules can be expressed in terms of
their vector velocities.

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

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Mean Free Path Calculation Frequency of collisions

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