Muhammad Javed

Department of Physics
University Of Malakand

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 Lecture 17
EQUATIONS OF STATE FOR
REAL GASES

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Van der Waals Equation

 Modified from ideal gas equation

 Accounts for:
 Non-zero volumes of gas particles (repulsive effect)
 Attractive forces between gas particles (attractive effect)

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Van der Waals Equation

 Attractive effect
 Pressure = Force per unit area of container exerted by gas
molecules
 Dependent on:
 Frequency of collision
 Force of each collision
 Both factors affected by attractive forces
 Each factor dependent on concentration (n/V)

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Van der Waals Equation

 Hence pressure changed proportional to (n/V)2

 Letting a be the constant relating p and (n/V)2…
 Pressure term, p, in ideal gas equation becomes
[p+a(n/V)2]

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Van der Waals Equation

 Repulsive effect
 Gas molecules behave like small, impenetrable spheres
 Actual volume available for gas smaller than volume of
container, V
 Reduction in volume proportional to amount of gas, n

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Van der Waals Equation

 Let another constant, b, relate amount of gas, n, to

reduction in volume
 Volume term in ideal gas equation, V, becomes (V-nb)

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 Pressure Correction
❖ Because the molecules are
attracted to each other, the
pressure on the container will be
less than ideal.
❖ Pressure depends on the number of
molecules per liter.
❖ Since two molecules interact, the
effect must be squared.
n 2
Pobserved = P−a ( )
V
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 But since real gases do have volume, we need:

Volume Correction
❖ The actual volume free to move in is less because of
particle size.
❖ More molecules will have more effect.
❖ Corrected volume V’ = V – nb
❖ “b” is a constant that differs for each gas.

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 Van der Waal’s equation
n 2
[Pobs + a ( ) ] (V − nb) = nRT
V

Corrected Pressure Corrected Volume

❖ “a” and “b” are
determined by experiment
❖ “a” and “b” are
different for each gas
❖ bigger molecules have larger “b”
❖ “a” depends on both
size and polarity
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Virial Equations

 Recall compressibility factor Z?

 Z = pVm/RT
 Z = 1 for ideal gases
 What about real gases?
 Obviously Z ≠ 1
 So how do virial equations address this problem?

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Virial Equations

 Form
 pVm/RT = 1 + B/Vm + C/Vm2 + D/Vm3 + …
 pVm/RT = 1 + B’p + C’p2 + D’p3 + …
 B,B’,C,C’,D & D’ are virial coefficients
 Temperature dependent
 Can be derived theoretically or experimentally

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Virial Equations

 Most flexible form of state equation

 Terms can be added when necessary
 Accuracy can be increase by adding infinite terms
 For same gas at same temperature
 Coefficients B and B’ are proportionate but not equal to
each other

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