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.
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
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.

Intermolecular Forces

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 weakelectrical 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 proportionto the density of the molecules, namely those that reside in the surface layer as well
as in the layerdirectly underneath. The layer that is directly underneath the surface contributes by
exerting aninward 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/V .
Taking all this into account, we can replace P by an effective pressure
2

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.

Critical Constants of the van der Waals Gas

We saw in our discussion of critical phenomena that the mathematical definition of the
critical point is,

(1)

and

(2)

In other words, the critical isotherm on a p-V diagram has a point of inflection.
Equations (1) and (2) constitute a set of two equation in two unknowns, V, and T. One
can test to see if an approximate equation of state gives a critical point by calculating
these two derivatives for the equation of state and trying to solve the pair of equations.
If a solution exists (and T and V are neither zero or infinity) then we say that the
equation of state has a critical point.
Let's use this test to see if a van der Waals gas has a critical point. First we have to
solve the van der Waals equation of state for pressure, p,

(3)

Now we can take the derivatives in Equations 1 and 2 and set them (independently)
equal to zero.

(4)

(5)

In order to stress that from here on the problem is pure algebra, let's rewrite the
simultaneous equations that must be solved for the two unknowns V and T (which
solutions we will call VC and TC),
(6)

(7)
There are several ways to solve simultaneous equations. One way is to multiply
Equation (6) by,

to get
(8)
Now add equations (7) and (8). Note that in this addition the terms containing T will
cancel out leaving,
(9)
Divide Equation (9) by 2an and multiply it by V 3 (and bring the negative term to the
other side of the equal sign) to get,
2

(10)
which is easily solved to get
(11)
To find the critical temperature, substitute the critical volume from Equation (11) into
one of the derivatives (which equals zero) say Equation (6). This gives,
(12)
which "cleans up" to give,
(13)
or
(14)
The critical pressure is obtained by substituting VC and TC into the van der Waals
equations of state as solved for p in Equation (3).

(15 a,b)
This simplifies to,
(16)
Our conclusion is that the van der Waals equation of state does give a critical point
since the set of simultaneous equations (Equations (1) and (2)) has a unique solution.
The van der Waals equation of state is still an approximate equation of state and does
not represent any real gas exactly. However, it has some of the features of a real gas
and is therefore useful as the next best approximation to a real gas. We will be
deriving thermodynamic relationships (equations) using the ideal gas approximation.
We can rederive some of these equations using the van der Walls equation of state in
order to see how these relationships are affected by gas nonideality. .

The Relationship between the van der Waals

Parameters and the Critical Constants
If

then

At the critical point,

and
So, differentiating our expression for pressure with respect to volume at constant temperature

so that

Differentiating again gives

so that

Dividing these two expressions gives

and so

Substitution of this result into the expression that we obtained by differentiating once

gives

which, when rearranged, gives

Substitution of the expressions for the critical volume Vc and critical temperature Tc into the van
der Waals equation gives

and so

Given these expressions for the values of the critical constants

so that

Similarly

Hence