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The ideal gas equation is based upon the model that:
▪ Gases are composed of particles so small
compared to the volume of the gas that they can
be considered to be zero-volume points in space.
▪ There are no interactions, attractive or repulsive,
between the individual gas particles.
Living in the real world
▪ For many gases under most conditions, the ideal gas
equation works well
▪ Two differences between the ideal and the real gases are
▪ Real gases occupy nonzero volume
▪ Molecules do interact with each other – collisions are
At higher densities, the equation PV = nRT does not work
well for a gas.
There is much interest in finding an equation of state that
describes real gases over a range of densities.
Many empirical equations have been put forward. We discuss
two of the many approaches.
The Virial expansion:
Our first approach to an equation of state for a real gas is
to write

Eq. 1

in which B1, B2, . . . , called virial coefficients, are

functions of temperature and grow successively smaller
as the series progresses.
It is clear from Eq.1 that at small molar densities (n/V → 0),
this equation of state reduces to the ideal gas law.

• Virial coefficients vary with gas type so does the virial

equation of state.
• The virial coefficients must be found empirically, by
fitting Eq.1 to experimental data.
The van der Waals Equation of State:
• In 1873, Johannes H. van der Waals (1837-1923), a
Dutch physicist, developed an approximate equation
of state for real gases.
• Awarded 1910 Nobel Prize in Physics for his work.

 an 2 
2 (
P + V − nb ) = nRT Eq. 2
 V 

• a and b are constants whose values must be obtained

by experiment.
• a and b are different for different gases.
Comparison of Eq.2 with the ideal gas law (pV = nRT)
suggests that van der Waals arrived at his equation by
correcting perceived points of failure in the ideal gas
▪ The Pressure Correction
▪ The Volume Correction
The Volume Correction:
In ideal gas equation, it is assumed that volume occupied
by the molecules of an ideal gas is negligible. This is not
quite true for real gases.
• Assuming that the particles behave as small,
impenetrable hard spheres.
• If b is the volume of one mole of gas molecules
• n is the number of moles
• nb is the volume of the molecules
• The actual volume is given by:
Vactual = V − nb
Real gas volume is less than ideal gas
• Correcting for the volume of the particles into the
ideal gas equation:


• Taking into account the actual volume of the gas

particle results in an increase in pressure relative to
that predicted by the ideal gas law.
The Pressure Correction:
For ideal gas, we assumed that the molecules of an
ideal gas exert forces on each other only during
• This is not quite true for real gases.
a) If the molecule is not near the wall of the vessel,
it would experience no net force due to the forces
exerted on it by the surrounding molecules.
▪ i.e., these forces would balance out to zero.
b) However, if the molecule is
located near the wall of the vessel,
e.g. the molecule C in fig., such a
molecule would experience a net
force of attraction away from the
wall due to the attraction of the
surrounding molecules within the
range R of the force between
The net pressure on the walls of
the container is reduced by all
such molecules within a distance R
of the walls
• The reduction in pressure owing to the
collisions of molecule C with the wall
is proportional to the number of
molecules in the hemisphere within
the range R of its attractive force and
thus to the number of molecules per
unit volume i.e., to n/V.
• The net effect due to all the molecules
that strike the wall (C is a typical
member of this group) is also
proportional to the number of
molecules per unit volume i.e., to n/V.
The total reduction in pressure is proportional to the
product of these two quantities, i.e.,
P  (n/V)2.
For example
• If we triple the number of molecules in a given
container, molecule C will experience three times
the unbalanced force.
• In the entire gas, there will be three times as many
molecules like C.
• The overall pressure reduction thus increases
Reduction in pressure (due to long-range attractive
forces between the molecules) is = a 
V 
From ideal gas equation
P= Eq(1)
nRT n
P= − a  Eq(2)
V V 
Real gas volume is less than ideal gas

Vreal = V − nb
Substitute V in Eq(2) with V - nb
nRT n
P= −a  Eq(2)
V − nb V 

 n 

 P + a    (V − nb ) = nRT Eq(3)
 V  

which is known as the van der Waals equation.

a, b = van der Waals constants (obtained from experiment)

 an 2 
 P + 2 (V − nb ) = nRT
 V 
Correction for
intermolecular Correction for
interactions molecular
• The van der Waals constants: volume

❖ a
• Pressure correction
• Represents the magnitude of attractive forces between
gas particles
• Does not specify any physical origin to these forces
❖ b
• Volume correction
• Related to the size of the particles
• These constants:
• Are unique to each type of gas.
• Are not related to any specific molecular properties.
Since Van der Waals equation comes from modification
of kinetic molecular model (theory) while a, b comes
from experiment
• Van der waals equation is “semi-empirical”.
• Virial equation is “empirical”.
Sample Problem: For oxygen the van der Waals
coefficients have been measured to be a = 0.138
J.m3/mol2 and b = 3.18  10-5 m3/mol. Assume that 1.00
mol of oxygen at T = 50 K is confined to a box of volume
0.0224 m3. What pressure does the gas exert according to
(a) the ideal gas law and (b) the van der Waals equation?
(a) The ideal gas law yields
(b) The pressure and the volume correction terms in
the van der Waals equation are


Substituting these quantities into the van der Waals

equation and solving that equation for p yields