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1C.2 The van der Waals gas

An approximate equation of state suggested by van der Waals in 1873. This equation is an
excellent example of scientific modelling. It is based both on experimental evidence and on
physical arguments,
n RT n2
p= −a 2
V − nb V
RT a
or in terms of molar volume, p= − 2
Vm − b V m
where a and b are called the van der Waals coefficients. Justification of the equation:
1. First feature of real gases
• Gas molecules have indeed a volume
• This volume restricts the accessible volume to something less than V
• This volume is V−nb where nb is the total volume occupied by the molecules
themselves (the excluded volume).
• This term is important when repulsions are important (at higher pressures)


2. Second feature of real gases (interactions)
• Molecular interactions are important in determining pressure
• Pressure depends on the frequency of collisions with the wall of the container and on
the force of each collision
• Both the frequency of collisions with the walls of the container and their force are
reduced by attractive forces
• Attractive forces are proportional to the molar concentration n/V
• Therefore, the reduction in pressure is proportional to the square of the concentration 



Note that the a and b parameters are determined empirically and one has to be careful in
ascribing them a precise physical meaning. In the limit V >> nb and a(n/V )2 << nRT /V , the van
der Waals equation reduces to the ideal gas law. 


Example: Consider one mole of each of the following gases at 298 K: ideal gas, He, CO, Kr, and
CH4. The last four are treated as van der Waals gases. What pressure (in Pa) will each gas exert
if it is contained in a volume of (a) 240.0 dm3, (b) 24.0 dm3, (c) 2.40 dm3, and (d) 0.240 dm3?
(see Handout van der Waals Examples)
Gas Ideal He CO Kr CH4

a (atm dm6 mol-2) 0.0 0.0341 1.453 5.125 14.61

b (10-2 dm3 mol-1) 0.0 2.38 3.95 1.06 4.31

p for V = 240.0 dm3 (kPa) 10.3 10.3 10.3 10.3 10.3

p for V = 24.0 dm3 (kPa) 103 103 103 102 101

p for V = 2.40 dm3 (MPa) 1.03 1.04 1.02 0.947 0.794

p for V = 0.240 dm3 (MPa) 10.3 11.4 9.80 1.79 -13.1

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One of the calculations is performed below for Helium: a = 0.0341 atm dm6 mol−2; b = 2.38 ×
10−2 dm3 mol−1; R = 8.20574 L atm K−1 mol−1 [NOTE: the choice of R must be compatible with
the units given for the van der Waals coefficient a]. Also, the final pressure we obtain from using
the van der Waals equation (with the parameters as given) will be in atm. We must convert to Pa,
where 1 atm = 101.325 kPa

Calculate p at V = 240.0 dm3 for 1 mole at 298 K. Note 1 L = 1 dm3.

n RT n2
p= −a 2
V − nb V
1m ol × 8.20574 × 10−2 d m 3at m K −1m ol −1 × 298K 6 −2 (1m ol )2
p= − 0.0341at m d m m ol
240.0d m 3 − 1m ol × 2.38 × 10−2 (240.0d m 3)2
−
p = 0.101898 − 5.92 × 10 7)at m
p = 0.101898at m × 101.325k Pa /at m
p = 10.3 kPa

1) Clearly the van der Waals equation of state breaks down for CH4 at the smallest volume
(highest pressure) considered here as we cannot have negative pressure
2) P(He) >≈ P(ideal) at all volumes. This is because the measure of intermolecular interactions,
a, is very small. Physically reasonable, because He is a noble gas, very non-interacting, boils
at very low temperatures (4.22 K).
3) P(Kr) and P(CH4) < P(others) primarily because a is larger (more attractions = less pressure).
Is this physically reasonable? Kr is a large atom (CH4 modest sized molecule), which are
more polarizable, and, therefore, give strong induced dipole-induced dipole interactions. For
comparison, polarizabilities of the species considered are (in Å3): He = 0.208, CO = 1.953,
Kr = 2.498, and CH4 = 2.448.
4) b(He) > b(Kr). Is He larger than Kr? NO! Recall that a and b parameters are determined
empirically and one has to be careful in ascribing them a precise physical meaning.
5) For pressures up to 100kPa - 1 MPa, deviations from ideal gas law are fairly small 1-5%
(except for CH4). At very high pressures, very large deviations may occur o