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 (Avagadro’s 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:
4π 3 π 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 ε 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

The choice of equation of state has some flexibility in it. The units of a must be energy times volume. One might have thought that the second correction term a should have been . shows that a is proportional to the energy of attraction times the molecular volume: a = 4ε o b . The (molar) density is just the reciprocal of the molar volume. we can contemplate how the gas thermometer works.G. As the lid moves up or down L will change. and the other attractive energies vary by an order of magnitude or so on either side of that value. You can see this by multiplying the equation through by Vm . 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. Let's assume we have a vdW gas in a box and we want to measure the temperature accurately. especially between molecules that have no initial pension for bonding (such as oxygen or argon). Finally. So the volume is V=AL. the justification for any “scientific guess” is in the accuracy of the result. 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. So the larger the attraction between molecules the larger a will be and the smaller will be the pressure on the walls. A careful calculation. Moreover. I see no reason for not doing this. equation of state. Perhaps because 1 contains an adjustable constant it is not so fundamental. given the several forms around with two adjustable parameters. on top of the lid to change the external 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. The values of the constants seem to fit well with the intuition that went into the guesswork in the first place.squared. so the attraction 1 should scale as 2 . Using the vdW. m. should be much less than that. The cylinder top has area A. so one would not want (Vm − b ) to generate a series in powers of this parameter. and realizing PV has units of energy. 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. The type of attraction among gas molecules. Therefore. A perusal of the values of a shows that the attraction between hydrogen molecules is on the order of 1 kJ/mol. using the Lennard-Jones 6-12 potential. We can place a weight of mass. then one could have (Vm − b ) 2 envisioned the pressure expanded in a power series of the fundamental parameter: 1 . somewhat justifying the placement into the equation of state of the two adjustable parameters. The energy of a hydrogen bond (in water) is about 2 to 4kcal/mol or about 8 – 16 kJoules/mol. and the position of the lid is L from the bottom.

mg A ⋅ L ⎛ g ⎞ then compute PV: PVm = ⋅ = ⎜ ⎟ m ⋅ L . P this should also be nearly a a straight line with a slope of b − .G. PVm As an example we use the parameters of oxygen (for a. Therefore: lim ( PVm ) = RT .h. b) and plot as a function of R the experimental pressure. So we assume that the real gas behaves as a vdW.136.) of this equation using Vm − b Vm the Taylor series expansion in powers of Vm−1 . In both cases the intercept is RT . b=32e-6 SI. and we know: Vm a PVm = RT − . we see that a plot of PVm vs. 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.. which is the RT desired quantity.G. Measure L. V →∞ If we keep the first two terms on the r. and determine V. equation (EoS) to model how we will measure the correct temperature. The Taylor series expansion is 1 b = 1 + x + x 2 + x3 + x 4 where x = . 1 should be Vm a straight line with a slope of bRT − a .h. (See table 7. From this form. We can expand the right hand side (r. Using this expansion: 1− x Vm bRT − a ⎧ b 2 b3 ⎫ PVm = RT + + RT ⎨ 2 + 3 + ⎬ . No approximations were made in the computation of the pressure. the extrapolation to zero pressure is very simple (requiring only two data points and a straight edge). We can double-check the pressure by attaching a manometer if we wish. The quantity g/n is a constant that we A n ⎝n⎠ know in advance.s to the Vm ⎩Vm Vm ⎭ limit where the molar volume goes to infinity.s. and what is left is only RT.G.s. 3 .h. which we take to be that determined from the vdW.4 of your text). Because the first term dominates when the pressure is below one atmosphere for most simple gasses. mg pressure. we can take the r. Now we can use the vdW. a=0. If we plot PV vs.

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. At this temperature the gas will behave very much as an ideal gas. There is a temperature at which the first term will vanish. 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. is to go back to the above equations and keep only the leading term. the great 17th century scientist). that is called the Boyle Temperature (named after Sir Robert Boyle. independent of P: ( PVm ) − RT ( PVm ) − ( bRT − a ) P = 0 2 1⎛ ⎛ a ⎞ P ⎞ PVm = RT ⎜1 + 1 + 4 ⎜ b − ⎟ ⎟ 2 ⎜⎝ ⎝ RT ⎠ RT ⎟⎠ 4 . and the slope will be zero. bRTB = a = 4ε ob 1 ε 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.This is figure 1. The slope of the line is a measure of the non-ideality of the gas.3 of your text.

the data are very linear in pressure. one can estimate a and b. Also notice that in the figure 1.We now expand the quadratic form and. 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. making no approximations. This is called the Boyle temperature: a TB = Rb Because the slope is negative in this case. so if the volume parameter (b) dominates at this particular temperature the slope will be positive. and hence the Boyle temperature. Notice the two parameters have opposite sign. there is a temperature at which the slope is zero. at two different temperatures. thereby. 5 . linearize the relation: ⎛ a ⎞ PVm ≈ RT + ⎜ b − ⎟P ⎝ RT ⎠ This shows why.3 in the text some gasses have positive and some gasses have negative slopes. even though I plotted the data from the full vdW equation (EoS). So from the slope we can get the relation between these parameters. As noted. So from the slope. we must be below the Boyle temperature for oxygen. This demonstrates that the parameters are different for different gasses.