Derivation of the Van-Der-Waals Equation

1) The Ideal Gas Equation states that:

pV = nRT with p = pressure

V = volume
n = number of moles
R = Gas Constant
T = absolute temperature

Gas characteristics such as pressure and volume are thought to be entirely due to
molecular motion, i.e., to the gas molecules’ kinetic energy.

2) For 1 mol of gas this simplifies to:

RT
pV = RT  p = ----
V

Since gas molecules have

 actual volume and
 attractive interactions,

they do not behave like volumeless points of mass that undergo purely elastic collisions.

3) The total volume V is composed partially of the molecular volume.

The volume that is due to molecular motion is V – b.
“b” is the correction factor for the molecular volume.

RT
p = -------
V–b

4) The pressure due to molecular motion and the involved collisions is reduced due
to attractive interactions between molecules; the degree to which the pressure is
reduced is indirectly proportional to the square of the volume. Therefore a corrective term
has to be added to represent the pressure related to molecular motion. “a” is the
correction factor for the molecular interactions (attractions).

a RT
( p + --- ) = --------
V2 V–b

Overall the Ideal Gas Equation pV = nRT is now changed to

a
( p + --- ) ( V – b ) = RT
V2

In the above equation

p actually observed pressure

p + (a/V2) pressure due to molecular motion/collisions

V actually observed volume

V–b volume due to molecular motion