Prepared by N.C.

Pomal
 Postulates of Kinetic Molecular Theory (K.M.T.)

 Maxwell proposed the following postulates

under the heading of kinetic theory of gases.
 Each gas is made up of a large number of small
(tiny) particles known as molecules.
 The volume of a molecule is so small that it may
be neglected in comparison to total volume of
gas.
 The molecules are never in stationary state but
they are believed to be in chaotic (random)
motion. They travel in straight line in all
possible directions with altogether different but
constant velocities. The direction of motion is
changed by the collision with container or with
other molecules.
 Continue…K.M.T.

 The molecules are perfectly elastic and bear

no change in energy during collision.
 The effect of gravity on molecular motion is
negligible.
 The temperature of gas is a measure of its
kinetic energy.
 The pressure of the gas is thus due to the
continuous collision of molecules on the
walls of container. Pressure P = Force/Area.
Maxwell’s Distribution of Velocity
 Average Velocity
 As per kinetic theory of gases, each molecule is
moving with altogether different velocity. Let ‘n’
molecules be present in a given mass of gas,
each one moving with velocity v1, v2, v3… vn.
 The average velocity or Uav = average of all such
velocity terms.
 Average velocity (uav)
 uav = u1+u2+u3+….+un/ n.

 uav = or
 Root Mean Square Velocity:-
 Maxwell proposed the term Urms as the
square root of means of square of all such
velocities also
 Most probable velocity:-
 It is the velocity which is possessed by
maximum no. of molecules.

 Furthermore
 Kinetic Energy of Gas
 As per kinetic equation

 For 1 mole m × n = Molecular Mass (M)

 Also

 Where k is the Boltzmann constant (k = R / N)

 Deviation from ideal behavior & cause of
deviation:

 A gas which obeys the gas laws and the gas

equation PV = nRT strictly at all temperatures
and pressures is said to be an ideal gas.
 The molecules of ideal gases are assumed to be
volume less points with no attractive forces
between one another.
 But no real gas strictly obeys the gas equation
at all temperatures and pressures. Deviations
from ideal behavior are observed particularly at
high pressures or low temperatures.
 The deviation from ideal behaviour is
expressed by introducing a factor Z known
as compressibility factor in the ideal gas
equation. Z may be expressed as

Z = PV / nRT

 In case of ideal gas, PV = nRT ∴ Z = 1

 In case of real gas, PV ≠ nRT ∴ Z ≠ 1
 Thus in case of real gases Z can be < 1 or > 1
 When Z < 1, it is a negative deviation. It shows
that the gas is more compressible than
expected from ideal behaviour.

 When Z > 1, it is a positive deviation. It shows

that the gas is less compressible than expected
from ideal behaviour.
Deviation Curve of Real gases
 Causes of Deviation from Ideal Behaviour:

 The causes of deviations from ideal

behaviour may be due to the following two
assumptions of kinetic theory of gases.
1. The volume occupied by gas molecules is
negligibly small as compared to the total
volume occupied by the gas.
2. The forces of attraction between gas
molecules are negligible.
 The first assumption is valid only at low pressures and
high temperature.
 It can be shown by calculations that in some common
gases, volume occupied by molecules is only 0.014% of
total volume of gas. This is indeed a negligible value.
 But at low temperature or at high pressure, the molecules
being incompressible. Hence volume of molecules will no
longer negligible in comparison with total volume of the
gas.
 The second assumption is only valid at the low
pressure and high temperature because under
These conditions the molecules lie far apart from
one another.

 But at high pressure and low temperature the

volume is small and molecules are closer to one
another. The intermolecular forces of attraction,
therefore are appreciable and cannot be ignored.

 Conclusion:
 Under high pressure and low temperature the
postulate no.1 & 2 does not hold. Therefore it is
necessary to apply suitable correction to the
ideal gas equation so as to make it applicable to
real gases.
The Vander Waals Equation of State
 In 1873, Vander Waals derived his famous
equation of state for non-ideal gas.
 He modified the ideal gas equation by
suggesting that the gas molecules are not mass
points but behave like rigid spheres having
definite diameter and there exists
intermolecular forces of attraction between
them. The two correction term were
introduced by him are:
1. Correction due to volume of gas molecules
2. Correction due to intermolecular forces of
attraction.
 Let, we understand above two points one by
one.
1. Correction due to Volume: Ideal gas equation
derived on the assumption of molecules are mass
points, i.e. they do not have finite volume. In
order to get the ideal volume which is
compressible, the correction term ‘nb’ should be
subtracted In order to understand the correction
term ‘nb’, let us assume two gaseous
molecules as impenetrable and
incompressible spheres, each of which has
diameter d.

It is evident that they cannot approach

each other more closely than the distance R.
R=2r
(because of repulsion)

For this pair of molecule, therefore a

D
spheres of radius of R has volume 4/3πR3
and this volume is known as excluded
volume.
 The volume of two molecule of radius r is
(V=4/3πR3 ) = 4/3π(2r)3
= 4/3π 8r3
= 8 x 4/3πr3
V=8xv
The actual volume of one molecule is
V = 8/2 v
V = 4 v.
 Thus, the excluded volume of molecule is 4
times greater then its original volume.
 Excluded volume per mole would be NA x 4 x v.
Where, NA is Avogadro’s number.
 The Compressible volume per mole of the gas is V-
b, for ‘n’ moles of gas volume will be V- nb. This V-
nb also known as co-volume.
2. Correction due to intermolecular forces:
 In the second postulate of KMT we have seen
that there are no intermolecular force of
attraction between molecules but for real
gases this is not so.
 Consider molecule C in the figure, it is
attracted by all the molecules surrounding it.

C W
 The forces on C neutralize one another and no
resultant attractive force on it.
 As this molecule approaches to the wall W, the
molecule now experiences force from behind it
and hence the pressure exert by molecule on
wall will be less then it would have been.
 Thus it is necessary to add certain quantity to
the pressure of the gas in order to get the ideal
pressure. The correct pressure should be P + p.
 Calculation of p: Pressure p is proportional to
the concentration of gas,
p α C2 Where C = Concentration.
p = a/ C2
But C = n/V
 Therefore, p = an2/V2
Thus, Vander Waals gas equation for one mole
of gas should be written as
( P + an2/V2 ) (V- nb) = RT.
and for ‘n’ mole of gas
( P + an2/V2 ) (V- nb) = nRT.
Where, a & b = Vander Waals Constant.
Units of Vander Waals Constant
 Unit of a:
 From ( P + an2/V2 )
a = PV2/n2 ,
P is in atmosphere and V in dm3 and n in mol2 the
unit becomes atm dm6 mol-2

 Unit of b:
From (V- nb)
b = V/n, hence unit becomes dm3 mol-1