KINETIC MOLECULAR THEORY OF

GASES
KINETIC MOLECULAR THEORY
- Provides a model (microscopic approach) which can
account for the properties exhibited by gases
Postulates
1. Gases are made up of molecules which are very small compared to
the distance separating them.
2. The force of attraction between the molecules is negligible.
3. The molecules are in constant random motion, and therefore possess
kinetic energy (Brownian movement).
4. The molecules collide with each other and with the walls of the
container in an elastic manner (do not involve any loss of
momentum).
5. The kinetic energy of the molecules is directly proportional to the
absolute temperature.
The postulates of KMT can be used to explain
the properties exhibited by gases:
1. Compressibility – can be explained by the great
distance between the molecules.
2. Diffusibility – can be attained to the motion of
molecules and to the lack of intermolecular
attractions.
3. Gases exhibit pressure as a result of the collision of
the molecules with the walls of the containers.
KMT Equation for Gas Pressure
The mathematical expression for the pressure exerted by
a gas can be derived based on the KMT:
• A gas can be pictured as being made up of a great number of
molecules.
• High frequency of collisions of the molecules with the walls of
the container (due to the KE present in the individual
molecules), pressure of the gas is constant at a constant
temperature.
Derivation for the pressure of a gas
In order to derive the eq for the pressure of a gas, consider a
collection of n’ gas molecules, each with mass m, inside a
cubic box of side l. Each molecule has a velocity of v, in the x,
y and z axis
v2 = vx2 + vy2 + vx2
➢ Before collision: momentum px = m vx
After collision: momentum px = -m vx
Change in momentum: Dpx = m vx – (-m vx) = 2 m vx

➢ Within 1 s, the molecule travels through a distance equal to vx

Distance traversed by the molecule before it strikes the same wall = 2 l
Number of collisions in 1s = vx /(2 l)
Derivation for the pressure of a gas
➢ In 1 s, number of collisions = vx /(2 l)
Each collision involves a change in momentum Dpx = 2 m vx
Total change in momentum of the molecule in 1 s:
Dpx = (2 m vx) [vx / (2 l)] = m v2 / l

➢ Recall: F = m a
Substituting for the defining eq for acceleration, i.e a = dv/dt,
F = m a = m (dv/dt)
F = m a = d (mv/dt)
Momentum p = m v, therefore
F = dp/dt
The equation states that the rate of change of momentum p with respect to t is equal
to the force acting on the moving body.
Derivation for the pressure of a gas
➢ It was shown earlier that:

Dpx = m vx2 / l
therefore, F = m v2 / l
For n’ molecules contained in the vessel, F = n’ m v2 / l
On which the force of collision give rise to the pressure exhibited by the
gas system.

P = F/A = (n’ m vx2 / l) / A

P = F/A = n’ m vx2 / (l A)
P = F/A = n’ m vx2 / (V)
Derivation for the pressure of a gas
➢ Note the simplified assumption from the start: v2 = vx2 + vy2 + vx2
Since the system is made up of a huge number of molecules,
vx2 = vy2 = vx2
So that v2 = 3 vx2
or v2 = v2 / 3

➢ Therefore, the pressure of the gas is

P = n’ mv2 / 3V
Rearrangement PV = n’ mv2 / 3
This equation gives the relationship between the pressure exhibited by
the gas and the mean velocity of the moving molecules.
Derivation for the pressure of a gas
➢ PV = n’ mv2 / 3
n’ = number of molecules, can be calculated from the number
of moles n, and Avogadro’s number NA through
n’ = n NA

The mass m of each molecule can also be calculated from M and NA

through
m = M / NA

Substitution, PV = n M v2 / 3
The equation involves the number of moles n, and the molar mass M. The
product n M gives the total mass of the gas molecules.
KINETIC ENERGY OF THE GAS MOLECULES
➢ A moving gas molecules possess kinetic energy
EK = m v2 / 2
It can be shown from the KMT equation the m v2 = 3 P V/ n’, so that
EK = 3 P V / 2
This equation related the pressure of the gas with the KE of the gas molecules.

➢ If we assume an ideal gas, then PV = nRT, and the KE is

EK = 3 n R T / 2
For 1 mole of a gas, EK = (3/2) R T
For 1 molecule of a gas, EK = [(3/2) R T] / NA
EK = (3/2) kT
where k is the Boltzmann constant which is equal to R/NA.
KINETIC ENERGY OF THE GAS MOLECULES
for 1 mole of gas,
EK = (3/2) RT

This equation show that the KE of the gas molecules is

dependent only on temperature.
• Temp is related to the random motion of the molecules
• Can be used as a measure of the average KE of chaotic motion
• At absolute 0, KE = 0, no chaotic motion
PROBLEM
Calculate the average KE of one mole of
oxygen molecules at 27 C.
o

[3.74 kJ]
MOLECULAR VELOCITY
➢ From the KMT eq: PV = n M v2 / 3,
1 mole of a gas: v2 = 3 P V / M
If the gas follows the ideal gas law, v2 = 3 R T / M

➢ The equation express the mean of the square of the

velocity of the gas molecules.
𝒗rms = (𝒗2)1/2 = (3 R T / M)1/2
PROBLEM
Find the root-mean-square velocity of oxygen
molecules at 25OC.
[482 m/s]

What is the ratio of the 𝒗rms of oxygen molecules at

100OC and at 200OC, i.e., v100 / v200?
[0.89]
Maxwell distribution law
➢ Velocity of the different molecules in a gas have a wide range of values
➢ Distribution of the molecular velocities in a gas is expressed by the
Maxwell distribution law

𝟏/𝟐 −𝒎𝒗𝟐
𝒅𝑵 𝒎
= 𝑮 𝒗 𝒅𝒗 = 4𝝅 𝒆 𝟐𝒌𝑻 𝟐
𝒗 𝒅𝒗
𝑵 𝟐𝝅𝒌𝑻

where dN/N is the fraction of N molecules that have the velocities between v and v + dv.
G(v) is the distribution function
m is the mass of the molecules
T is the absolute temperature
k is the Boltzmann constant
Distribution function
➢ Dependent on the temperature
• inc T, peak shifts to a higher value, curve broadens, peak
of the G (v) value decreases.
Distribution function
➢ Dependent on the mass of the gas molecules
• inc m, peak shifts to lower values, curve becomes
narrow, and the maximum value of the function
increases.
Most probable velocity 𝒗𝒎𝒑
➢ Corresponds the peak in the distribution curve
➢ Evaluated by differentiating the distribution
function with respect to velocity and equating the
derivative to 0
𝟏
𝟐𝑹𝑻 𝟐
𝒗𝒎𝒑 =
𝑴
Mean velocity 𝒗
➢ Can be obtained from the distribution function by
applying the law of averages, then performing the
integration between the limits 0 to ∞

𝟏
𝟖𝑹𝑻 𝟐
𝒗 =
𝝅𝑴
PROBLEM

Calculate the root-mean-square velocity, the most

probable velocity, and the mean velocity of CO2
molecules at 25OC.
[411; 335; 379]
Determine the ratio of (a) the mean velocity and
(b) the KE of gaseous H2 molecules and Hg atoms
at 25OC
[9/975; 1]
COMPARISON OF THE FORMULAS AND
VALUES
MOLECULAR COLLISIONS
➢ From the KMT, it is possible to calculate the
number of intermolecular collisions per unit time,
the total number of collisions per unit volume per
unit time, and the distance travelled by a molecule
in between collisions.
COLLISION FREQUENCY
➢ Number of collisions experienced by a molecule
per second

𝒛 = (𝝅𝒅 𝒗 ) (N/V)
𝟐
COLLISION DENSITY/COLLISION NUMBER
➢ total number of collisions taking place per
second.

𝑵 𝟐
𝟐 𝟐
𝒁 = (𝝅𝒅 𝒗)
𝟐 𝑽

Unit: s-1 m-3

➢ The number of molecules present in a unit
volume (N/V) can be obtained from the ideal gas
law.

NA: N = n NA

𝑵 𝑷
=
𝑽 𝒌𝑻
PROBLEM

Estimate the collision frequency and the collision number

of O2 molecules at 25OC and 101.3 kPa. The collision
diameter of the molecules is 2.4 x 10-10 m.
[1.98 x 109 ; 3.4 x 1034]
MEAN FREE PATH
➢ Defined as the average distance that a molecule
travels between collisions.

λ= 𝟐𝝅𝒅
𝒌𝑻
𝟐
𝑷
Unit: m
PROBLEM
Estimate the mean free path of O2 molecules at
25OC and 101.3 kPa. The collision diameter of the
molecules is 2.4 x 10-10 m.
[1.6 x 107]

At an altitude of 20 km, the temperature is 217 K

and the pressure is 0.050 bar. What is the mean
free path of the N2 molecules? (σ = 0.43 nm2)
[9.7 x 10-7]