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STATE FOR
REAL GASES
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
non-elastic
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
an 2
2 (
P + V − nb ) = nRT Eq. 2
V
Since
Vreal = V − nb
Substitute V in Eq(2) with V - nb
2
nRT n
P= −a Eq(2)
V − nb V
n
2
P + a (V − nb ) = nRT Eq(3)
V
❖ 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?
Solution:
(a) The ideal gas law yields
(b) The pressure and the volume correction terms in
the van der Waals equation are
and