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Mean Free Path of Gas Molecules

The mean free path expression assumes target molecules are at rest, but they are moving. Accounting for the average relative velocity of randomly moving molecules yields a revised expression. This treats molecules as hard spheres and gives a good estimate for noble gases, but real molecules interact electrically as they approach. Further refinements consider electrical potentials and measured viscosity.

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413 views3 pages

Mean Free Path of Gas Molecules

The mean free path expression assumes target molecules are at rest, but they are moving. Accounting for the average relative velocity of randomly moving molecules yields a revised expression. This treats molecules as hard spheres and gives a good estimate for noble gases, but real molecules interact electrically as they approach. Further refinements consider electrical potentials and measured viscosity.

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AISHEE DIBA
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© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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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


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

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.

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