Van der Waals equation differs from the ideal gas law in that it

makes allowance both for the volume occupied by the molecules

themselves & for the attractive forces between them .

• Real gas molecules do attract one another

(Pid = Pobs + constant)
• Real gas molecules are not point masses
(Vid = Vobs - const.)
Vid = Vobs - nb
b is a constant for different gases
Pid = Pobs + a (n / V)2
a is also different for different gases
Ideal gas Law Pid Vid = nRT

  n 
2

 P  a   V  nb   nRT
 obs V  
 
RT a
Pobs  
V m  b V m 2
 Van der Waals equation

 
2
an
P  2   V – nb   nRT
 V 
Correction for
Intermolecular Correction for
VReal > VIdeal
Attractions Molecular Volume

PReal < PIdeal n = moles of gas

a and b are constants given in the problem
3 Chapter 9
 ‘a’ is called van der Waals constant of attraction. Higher values
of ‘a’ indicate greater attraction between gas molecules.
The easily compressible gases like ammonia, HCl possess
higher ‘a’ values.
Greater the value of ‘a’ for a gas easier is the liquefaction.

* ‘b’ is called excluded volume of the gas.

Where NA = Avogadro number and r = radius of molecule

At low pressures: Since V is large and therefore
‘b’ is negligible compared to V, the van der Waals
:equation for one mole of a gas is reduced to

*Note that V = Vm = molar volume .

Therefore: PV ˂ RT at lower pressures. This is
the reason for decrease in the Z value at low
pressures .
Note: By dividing with RT on each side, the
above equation can be written as:
At very low pressures: Since V is very large and therefore both
‘b’ and ‘a/V2’ values become negligible. Hence the van der
Waals equation for one mole of gas is reduced to:
PV = RT
Therefore, at very low pressures all the gases obey the ideal
gas equation.
At high pressures: Since the volume of the gas is small, the
value of ‘b’ cannot be neglected. Although a/V2 is also large
its value may be neglected in comparison with very high
value of P. Hence the van der Waals equation is reduced to:
P(V - nb) =n RT
PV - Pb = RT
PV = RT + Pb
Therefore: at high pressures, PV > RT. This explains the
raising parts of the isotherms, at high pressures, plotted
between Z vs P .
Note: By dividing with RT on each side, the above
equation can be written as:
 van der Waals constants

a (dm6 atm mole-2) b (dm3 mole-1)

He 0.0346 0.0237
Ar 1.363 0.0322
N2 1.408 0.0391
O2 1.378 0.0318
CO2 3.640 0.0427