A Level Physics Notes: Thermal Physics and Gases – The van der Waals Equation
The ideal gas equation
is
derived using a simple model of a gas that ignores the attractive
forces between the gas molecules and their volume. The model becomes
less satisfactory as the pressure increases and the molecules are
forced closer together, and the temperature decreases, so the gas
gets closer to condensing.
We can make approximate corrections for these two factors by:
Taking the volume of the gas as the volume of the container
minus the volume of the gas molecules, or a least minus a term that
depends on the volume of the gas molecules. The volume
becomes
where
is
the number of mols of gas and
is
a constant which depends on the gas in question.
Including a term added to the pressure to take account of the
attractive force between the molecules. The attractive force between
the molecules is proportion to the number of molecules per unit
volume near the wall, and also in the interior of the gas so
proportional to
This
means the effective pressure becomes![]()
With these modifications the ideal gas equation becomes![]()
When
is
small, so the gas is dilute, the average distance between gas
molecules is large, so that
is small,
and
the extra terms in the van der Waals equation become insignificant.
As an example, for
and
One
mol of an ideal gas at a temperature of 0 degrees celsius and a
pressure of 1 atmosphere or
occupies
a volume of
According
to the van der Waals equation the same amount of gas at the same
volume and temperature would exert a pressure only 532 Pa less, a
difference of about 0.5%.