The van der Waals gas (vdW.G.

The ideal gas (I.G.) equation of state (EoS) is:

nRT RT
P= =
V Vm
When considering real gasses, this equation of state needs to be modified. It is
interesting to think about how the modification should be done. The first person to
suggest how to modify it was van der Waals. He proposed two modifications of the I.G.
equation to include molecular interactions. The first modification is to realize that
molecules take up space. This means that the accessible volume is reduced by the
amount of space each molecule takes up. The first correction to the I.G. is to try an
equation of state of the form:
RT
P=
Vm b
Here, b is, as yet, an unknown adjustable constant that is different for each gas molecule.
We know that (at room temperature) air is 1 gram/liter and water is 1 gram/cc. So there
is roughly a 1000 fold volume change in going from gas to liquid. The molar volume of
a gas is 22.4 liters/mole (Avagadros principle) and, therefore, we would expect the
actual volume of the gas molecules to be about 1/1000 of that or b 0.0224 liters/mole or
dm3/mole. The correction van der Waals made was to subtract this volume, called b ,
from the molar volume of the gas. Therefore, we expect b to be related to the actual
molar-volume of the gas molecule. And b as determined experimentally should be on the
order of 0.02 and be larger for larger molecules. In terms of a potential energy of
interaction between any two molecules, this correction is consistent with the idea that
there is no repulsion or attraction between gas molecules when the distance between the
centers of two molecules is greater than the closest point of contact ( r = 2ro = d ) but that
the potential rises very (infinitely) steeply as the distance becomes less than the
molecular diameter. This repulsive potential keeps the molecules from inner-penetrating.
A more careful consideration of the molecules as simple spheres suggests that (at low
density) the excluded volume is 4 times the actual volume. A look at the values of this
parameter bear out the idea that b represents the actual volume of the molecule
expressed as a molar volume, where vm is the volume of a single molecule:
4 3 3
b = 4vm N A where vm = ro = d
3 6
Van der Waals radii are used universally in molecular structure in chemistry and arose of
considerations of just this sort.

Secondly, van der Waals reasoned that the gas molecules were attracted to each other, up
until they were repelled when they touched. There is an optimum distance then, at which
the bimolecular attraction potential has an energy (as a negative potential) of o , also
expressed on a per mole basis. Van der Waals reasoned that the attraction then should
reduce the pressure. The reduction in pressure should be proportional to the
concentration of molecules times the concentration of other attractive molecules. As
these two concentrations are one and the same, the attraction should go as the density

1
squared. The (molar) density is just the reciprocal of the molar volume, so the attraction
1
should scale as 2 . This is very much parallel to the law of gravity where the potential
Vm
energy of attraction is proportional to the product of the two masses that are attracted.
Therefore, the second correction to the equation of state is:
RT a
P= 2
Vm b Vm
The correction factor is subtracted so that an increase in this term will reduce the
observed pressure. The units of a must be energy times volume. You can see this by
multiplying the equation through by Vm , and realizing PV has units of energy. A careful
calculation, using the Lennard-Jones 6-12 potential, shows that a is proportional to the
energy of attraction times the molecular volume: a = 4 o b . So the larger the attraction
between molecules the larger a will be and the smaller will be the pressure on the walls.
The energy of a hydrogen bond (in water) is about 2 to 4kcal/mol or about 8 16
kJoules/mol. The type of attraction among gas molecules, especially between molecules
that have no initial pension for bonding (such as oxygen or argon), should be much less
than that. A perusal of the values of a shows that the attraction between hydrogen
molecules is on the order of 1 kJ/mol, and the other attractive energies vary by an order
of magnitude or so on either side of that value.

The choice of equation of state has some flexibility in it, given the several forms around
with two adjustable parameters. One might have thought that the second correction term
a
should have been . I see no reason for not doing this, then one could have
(Vm b )
2

envisioned the pressure expanded in a power series of the fundamental parameter:

1
. Moreover, it seems that the second correction term form was perhaps chosen
(Vm b )
not only from physical insight of attractive bodies (like stars) but because this would
represent the second order term in a density power series expansion. Perhaps because
1
contains an adjustable constant it is not so fundamental, so one would not want
(Vm b )
to generate a series in powers of this parameter. Finally, the justification for any
scientific guess is in the accuracy of the result. The values of the constants seem to fit
well with the intuition that went into the guesswork in the first place, somewhat justifying
the placement into the equation of state of the two adjustable parameters.

Using the vdW.G. equation of state, we can contemplate how the gas thermometer works.
Let's assume we have a vdW gas in a box and we want to measure the temperature
accurately. The setup is the gas is in a cylinder with a movable lid (piston) that will not
let the gas molecules out of the cylinder. The cylinder top has area A, and the position of
the lid is L from the bottom. So the volume is V=AL. As the lid moves up or down L
will change. We can place a weight of mass, m, on top of the lid to change the external

2
 mg
pressure. Pex = We let the gas come to equilibrium then we know the external
A
pressure is the same as the internal pressure of the gas. Measure L, and determine V,
mg A L g
then compute PV: PVm = = m L . The quantity g/n is a constant that we
A n n
know in advance. We can double-check the pressure by attaching a manometer if we
wish. Now we can use the vdW.G. equation (EoS) to model how we will measure the
correct temperature. So we assume that the real gas behaves as a vdW.G. and we know:
Vm a
PVm = RT . We can expand the right hand side (r.h.s.) of this equation using
Vm b Vm
the Taylor series expansion in powers of Vm1 . The Taylor series expansion is
1 b
= 1 + x + x 2 + x3 + x 4 where x = . Using this expansion:
1 x Vm

bRT a b 2 b3
PVm = RT + + RT 2 + 3 + . From this form, we can take the r.h.s to the
Vm Vm Vm
limit where the molar volume goes to infinity, and what is left is only RT. Therefore:
lim ( PVm ) = RT .
V

If we keep the first two terms on the r.h.s., we see that a plot of PVm vs. 1 should be
Vm
a straight line with a slope of bRT a . If we plot PV vs. P this should also be nearly a
a
straight line with a slope of b . In both cases the intercept is RT , which is the
RT
desired quantity. Because the first term dominates when the pressure is below one
atmosphere for most simple gasses, the extrapolation to zero pressure is very simple
(requiring only two data points and a straight edge).
PVm
As an example we use the parameters of oxygen (for a, b) and plot as a function of
R
the experimental pressure, which we take to be that determined from the vdW.G. No
approximations were made in the computation of the pressure, a=0.136, b=32e-6 SI. (See
table 7.4 of your text).

3
This is figure 1.3 of your text. The slope of the line is a measure of the non-ideality of
the gas. There is a temperature at which the first term will vanish, that is called the Boyle
Temperature (named after Sir Robert Boyle, the great 17th century scientist). At this
temperature the gas will behave very much as an ideal gas, and the slope will be zero.
bRTB = a = 4 ob
1
o = RTB
4
One way to visualize why the line is nearly a straight line even though we plotted PVm as
a function of pressure, is to go back to the above equations and keep only the leading
term.
bRT a
PVm RT +
Vm
Now rewrite PVm as a function of P:

PVm = RT +
( bRT a ) P
PVm
Rearrange and solve for PVm as a function of P:
( PVm ) = RT ( PVm ) + ( bRT a ) P
2

This is a quadratic equation but we can solve that and then expand that result. We will
take the positive square root so that in the limit of the ideal gas form we get no slope or
PVm is a constant, independent of P:
( PVm ) RT ( PVm ) ( bRT a ) P = 0
2

1 a P
PVm = RT 1 + 1 + 4 b
2 RT RT

4
We now expand the quadratic form and, thereby, linearize the relation:
a
PVm RT + b P
RT
This shows why, even though I plotted the data from the full vdW equation (EoS),
making no approximations, the data are very linear in pressure. At low pressure the gas
acts as a nearly ideal gas with a slope that is related to the two parameters of the vdW
gas. So from the slope we can get the relation between these parameters. Notice the two
parameters have opposite sign, so if the volume parameter (b) dominates at this particular
temperature the slope will be positive. Also notice that in the figure 1.3 in the text some
gasses have positive and some gasses have negative slopes. This demonstrates that the
parameters are different for different gasses. As noted, there is a temperature at which
the slope is zero. This is called the Boyle temperature:
a
TB =
Rb
Because the slope is negative in this case, we must be below the Boyle temperature for
oxygen. So from the slope, at two different temperatures, one can estimate a and b, and
hence the Boyle temperature.