Derivation of the van der Waals

Equation of State for Real Gases

Part One
written by: Dr. Crystal Cooper
edited by: Lamar Stonecypher
updated: 6/7/2011
In this article, we begin deriving an
equation of state for real gases by
using van der Waals' modification of
kinetic theory.

From the ideal gas law, we know that

1) PV = nRT
where P is pressure, V is volume, T is
temperature, R is the universal gas
constant, and n is the number of
moles. If we let b equal the amount
of the unavailable or excluded
volume per mole of the gas, then the
actual volume will be the total minus
this excluded amount:
2) V (actual) = V nb

The Reduced Volume

The number and size of molecules
limit
their
motion
inside
the
container, and the space they cannot
reach
is referred
to
as
the
unavailable volume. For the kinetic
theory of gases, where we consider
ideal gases, we assume that our
molecules are point sized and can
take up the entire volume of the
container. An example is shown in
figure 1.
The size, placement, and motion of
the molecules are exaggerated, and
a large enough number is not shown,
but it is easy to picture that
extremely small molecules would fill
up the space.
For the van der Waals model, where
we
consider
real
gases,
the
molecules have an actual size and
thus are unable to fill up a container
space, even after they collide. An
exaggeration of their size and motion
is shown in figure 2. The container is
the same size as that of figure 1, but
the molecules are prevented from
inhabiting all of the volume.
In other real gas models, the
molecules are further limited in the
amount of space they can occupy by
a repulsive force that exists between
them if they are too close to each
other, but we do not consider that
here.

Substituting 2 into equation 1 gives

us:
3) P(V - nb) = nRT
Dividing both sides by n we finally
have:
4) P(V/n - b) = RT
What does this equation tell us?
Suppose we have a set volume V and
temperature T. Then the pressure P is
greater for our real gas than that of
our ideal gas in equation 1. This is
because the number of molecules
colliding with the walls will increase
since the available volume is smaller.
In part two, we will finish our
derivation of van der Waals' equation
by considering intermolecular forces.

Derivation of the van der Waals

Equation of State for Real Gases
Part Two
written by: Dr. Crystal Cooper
edited by: Lamar Stonecypher
updated: 5/14/2009
In this article, we conclude our
derivation of the van der Waals
equation of state for real gases.
Intermolecular Forces
We can use equation 4 in the
preceding article to help us derive
the final form of the van der Waals

equation of state for real gases. To

recall, we found that
4) P(V/n - b) = RT.
We
begin
by
considering
intermolecular forces. Intermolecular
forces have a behavior that is
nonexistent
at
long
distances,
attractive at intermediate distances,
and repulsive at short distances.
Here, we take into account only their
attractive forces, which are electrical
in nature.
Molecules that are close can attract
each other over certain ranges, and
if the attraction is great enough
gases condense into liquids. We saw
in our discussion on the kinetic
theory of gases that the kinetic
energy of collisions affects the
pressure that the molecules exert on
the container walls. Under certain
conditions,
short-range
intermolecular forces also contribute
to wall pressure. How so?
Because of weak electrical attraction,
molecules
that
are
near
the
container wall at the edge of the gas
have a net force that tends to pull
them back, thus lessening the
number of molecules impacting the
wall and hence the gas pressure.
This
pressure
is
reduced
in
proportion to the density of the
molecules, namely those that reside

in the surface layer as well as in the

layer directly underneath. The layer
that is directly underneath the
surface contributes by exerting an
inward force on the edge molecules,
as seen in figure 1. The weak
attraction that exists between the
molecules is akin to that of Newton's
law of gravitation, and the effect is
that the net pressure is reduced by a
factor proportional to 1/V2.
Taking all this into account, we can
replace P by an effective pressure
5) P (effective) = P + a/(V/n)2,
where a is a constant dependent on
the amount of attraction between
the molecules; it takes into account
the overlap of their electron clouds.
Substituting this into equation 4
above gives us
6) (P + a/(V/n)2)(V/n - b) = RT.
If we let V/n = the specific volume V,
then we have:
7) (P + a/V2)(V - b) = RT.
Equations 6 and 7 are known as the
van der Waals equation of state. The
constants a and b are chosen to fit
the experimental data for the gas
under consideration. When a and b
are zero, the equation reduces to
that of the ideal gas law.