According to Kinetic molecular theory of gases,
A gas is made of molecules dispersed inspace in a container(1) but the actual volume
of the gas molecules is negligible(2).
(1) (2)
There are generally no intermolecular interactions in a gas because the molecules are
far apart and move freely, and the kinetic energy of the molecules is greater than the
attractive force between them.
Large distances
The molecules in a gas are usually far apart compared to liquids and solids.
Negligible forces
The intermolecular forces in a gas are usually very weak and are often considered negligible.
Free motion
The molecules in a gas are in continual straight-line motion and can move freely.
Thermal energy
The thermal energy of the molecules overcomes the attractive force between them.
van der Waals Equation:
van der Waals (1873) attributed the deviations of real gases from ideal behaviour to above
wrong postulates of the kinetic theory. These are :
(1) the molecules in a gas are point masses and possesses no volume.
(2) there are no intermolecular attractions in a gas.
Therefore, the ideal gas equation PV = nRT derived from kinetic theory could not hold for
real gases. van der Waals pointed out that both the pressure (P) and volume (V) factors in the
ideal gas equation needed correction in order to make it applicable to real gases.
(1) Volume Correction:
Volume V of an ideal gas is the same as the volume of the container.
The dot molecules of ideal gas have zero-volume and the entire space in the container is
available for their movement. However,van der Waals assumed that molecules of a real gas
are rigid spherical particles which possess a definite volume.
The volume of a real gas is, therefore, ideal volume minus the volume occupied by gas
molecules. If b is the effective volume of molecules per mole of the gas, the volume in the
ideal gas equation is corrected as : (V – b)
For n moles of the gas, the corrected volume is : (V – nb)
where b is termed the excluded volume which is constant and characteristic for each gas.2r
Excluded volume
Fig. Excluded volume for a pair of gas molecules.
Excluded volume is four times the actual volume of molecules.
The excluded volume is not equal to the actual volume of the gas molecules. In fact, it is four
times the actual volume of molecules and can be calculated as follows.
Let us consider two molecules of radius r colliding with each other. Obviously, they cannot
approach each other closer than a distance (2r) apart. Therefore, the space indicated by the
dotted sphere having radius (2r) will not be available to all other molecules of the gas. In
other words the dotted spherical space is excluded volume per pair of molecules. Thus,
4
Excluded volume of two molwcules = π (2 r ) 3
3
4
= π .23 r3
3
4
= 23 ( π r3)
3
4 3
=8( πr)
3
1 4
Excluded volume per molecule (Ve) = 8 ( π r3)
2 3
4
=4V Because V=( π r3)
3
= 4 Vm
where Vm is the actual volume of a single molecule.
Therefore, in general, excluded volume of the gas molecules is four times the actual volume
of molecules.
(2) Pressure Correction
A molecule in the interior of a gas is attracted by other molecules on all sides. These
attractive forces cancel out. But a molecule about to strike the wall of the vessel is attracted
by molecules on one side only. Hence it experiences an inward pull .Therefore, it strikes the
wall with reduced velocity and the actual pressure of the gas, P, will be less than the ideal
pressure. If the actual pressure P, is less than Pi (ideal) by a quantity pe, we have
P = Pi – pe
or Pi = P + pe
(a) A molecule about to strike the wall has a net inward pull;
(b) A molecule in the interior of gas has balanced attractions.
p is determined by the force of attraction between molecules (A) striking the wall of
container and the molecules (B) pulling them inward.
The net force of attraction is, therefore, proportional to the concentration of (A) type
molecules and also of (B) type of molecules. That is,
pe α CA x CB
n n
pe α x
V V
an 2
pe =
V2
where n is total number of gas molecules in volume V and a is proportionality constant
characteristic of the gas. Thus the pressure P in the ideal gas equation is corrected as :
Because
Pi = P + pe
Therefore we can put the value of pe in the above equation
an 2
Corrected pressure is Pi = P +
V2
Substituting the values of corrected pressure and volume in the ideal gas equation, PV = nRT,
we have
(P+
an 2
V2 ) ( V −nb ) = nRT
This is known as van der Waals equation for n moles of a gas. For 1 mole of a gas (n = 1),
van der Waals equation becomes
Constant a and b in van der Waals equation are called van der Waals constants. These
constants are characteristic of each gas.
Determination of a and b
From the above expression, the value of a is given by the relation
If the pressure is expressed in atmospheres and volume in litres,
Thus a is expressed in atm litre2 mol–2 units.
Since nb is excluded volume for n moles of gas
If volume is expressed in litres, b is expressed in litre mol–1 units.
SI units of a and b. If pressure and volume are taken in SI units, we have
and
The values of (a) and (b) can be determined by knowing the P, V and T of a gaseous system
under two different conditions.
Significance of Van der Waals Constant
Significance of Pressure Correction Factor
The pressure correction factor (a) originates from the intermolecular attraction and Pa =
an2/V2. Therefore, the internal pressure of the gas can be measured by the pressure
correction factor.
The higher the value of the pressure correction factor greater the intermolecular attraction and
the more easily the gas liquefied.
Van der Waals constant (a) for greenhouse gas carbon dioxide gas = 3.95 but hydrogen gas =
0.22.
Significance of Volume Correction Factor
Another constant volume correction factor (b) measures the molecular size and also repulsive
forces.
The greater, the value of b larger the size of the gas molecule. Van der Waals constant b for
carbon dioxide = 0.04 but hydrogen = 0.02.
Compressibility Factor for Real Gas
Van der Waals equation is used for the calculation of Boyle temperature, and critical
temperature. It also explains the compressibility factor and Amagat curves for n-mole real
gases.
Mathematical calculation of Boyle temperature for real gases,
TB = a/Rb
The compressibility factor is the function of temperature and pressure only.
