KINETIC THEORY OF GASES

Kinetic theory is one of the greatest theories in present. It deals with the
constant motion of molecule in any matter. But we study the KINETIC THEORY
OF GASES. That’s only because molecule of gases are in random motion
constantly. As we know that – molecules of solid are tightly packed so the
obtained motion is negligible, same molecules of liquid are loosely packed but
have high intermolecular force of attention compared to gases. Molecules in
gases are in motion because of free space.

That’s a fact that we can’t study the actual properties of gases so we study
average properties of gases (as we study same for centre of mass).

Properties of gases:
1) Mean free path ‘λ’– It is an average distance travelled
by a molecule between two successive collisions.
λ1+λ2+λ3+...+λn
λm =
n

where, λm is the MEAN FREE PATH of molecule(average distance),

λ1,λ2...λn are the distance between different molecule and n is the
total no. of molecules.

2) Average relaxation time ‘τ’ – It is the average time period between 2

successive collisions. It is given by
τ1+ τ2+ τ3+...+ τn
τm =
n
Kinetic theory deals with the ideal behaviour of gases:

1) It is a perfect gas which strictly flows all gas laws like Boyle’s, Charles’
etc.
2) In fact, this gas is a imaginary gas, it can’t be found in surrounding.
3) On heating sometimes real gases behaves like ideal gas.
4) It doesn’t have intermolecular attraction between molecules.
5) A molecule of ideal gas is a point mass with no geometric dimension.
Before starting kinetic theory it’s important to study the laws which were
discovered earlier.

1) Boyle’s law (in 1627) – According to this law, at constant

temperature the volume (V) of a fixed mass of a gas is inversely
proportional to the pressure (P).
1
Here, T = constant P ∝ or PV = constant or P1V1= P2V2
V

2) Charles’ law (in 1802) – According to this law, at constant pressure

the volume (V) is directly proportional to temperature (T)
Here, P = constant
𝑉
V∝T or = constant
𝑇

3) Avogadro’s hypothesis (in 1811) – At constant temperature (T) and

pressure (P), equal volume of any gases has equal number of
molecules. i.e. number of particle in 1 litre of oxygen is equal to that
in 1 litre of hydrogen or xeon etc. that is 6.022 × 1023
V∝n

Combining the laws,

1
=> V ∝ ; V ∝ T ; V ∝ n
𝑃

1
(Or) => V ∝ ∝ T ∝ n
𝑃

𝑛𝑇
(Or) => V ∝
𝑃

(Or) => PV ∝ nT

(Or) => PV = nRT

Where P is pressure exerted by gas, V is volume, n is no. of moles, T is

temperature(in Kelvin) and R is the universal as constant which is 8.314 J/mol K

This equation is widely known as ideal gas equation.

Kinetic Theory Of Gases (in 1859)
The kinetic theory was developed in 19th century by Maxwell and Boltzmann.
Kinetic theory explains the behaviour of gases based on the idea that the gas
consists of rapidly moving atoms or molecules. Kinetic theory has to satisfy all
gas laws to proof its importance. This theory is 100% valid on ideal gases. And
this theory only deals with the monatomic gases (Xe, He etc.) but then to it is
used for diatomic and polyatomic gases.

There are many assumption of kinetic theory, which is known as postulates of

kinetic theory.

Postulates of kinetic theory:

1) Molecules of same gas are identical in all respect.

2) Matter is made up of molecules.
3) Molecules are in random motion along straight line.
Let µ be the speed of the molecule
µ = µx i+ µy j+ µz k
|µ|= √µx2+ µy2+ µz2
µ2 = 3µx2 {µx = µy = µz; speed is same in all direction}
4) All the collisions of gas among themselves or with the walls of container
are perfectly elastic in nature.
It means that there is no loss of momentum and kinetic energy.
5) The pressure of a gas is due to collisions of molecules with the walls of
vessel.
P ∝ no. of collision of molecules per unit area
6) The kinetic theory depends only and only on temperature.
7) The volume occupied by gas molecules is negligible when compared to
volume of gas.
For e.g. if a gas is realized in a container of volume V, and then all
the molecules of that gas is gathered in the corner of the same
container then the volume occupied by molecules is nothing when
compared with the volume of gas.
8) There is no intermolecular force of attraction among molecules.
9) Molecules obey Newton’s law of motion.
 Equation of kinetic theory of gases:
1
PV = Mnc2
3

Where, P is the pressure, V is the volume, M is the mass of molecules, n is no.

of moles and c is the root mean square velocity of molecules.

µ12+ µ22+ µ32+…+ µn2

c=√
n

In short c is the root of mean of square of velocity of molecules of gases.

Derivation:

Consider a molecule of mass m in a cubic

container of dimension L. Let the molecule be
moving toward wall A with velocity of µx1.after a
period of time it collides with wall A and bounce
towards wall B with same velocity µx1.

So, the momentum

Pf = mµx1

Pi = -mµx1

∆P = Pf - Pi = 2mµx1
𝐷 2L
Time taken by each collision = =
𝑆 µx1

Δ𝑃 2𝑚µx1 𝑚(µx1)2
Force = = 2𝐿 =
Δ𝑡 𝐿
µx1

1𝑚
So, f = (µ1)2 {3(µx1)2 = (µ1)2}
3 𝐿

Now, force due to n no. of molecules

1𝑚 1𝑚 1𝑚 1𝑚
= (µ1)2 + (µ2)2 + (µ3)2 +…+ (µn)2
3 𝐿 3 𝐿 3 𝐿 3 𝐿
 1𝑀
= {(µ1)2 + (µ1)2 +…+ (µn)2}
3𝐿

Dividing and multiplying by n

1𝑀 {(µ1)2 + (µ1)2 +…+ (µn)2}
= n[ ]
3𝐿 𝑛

1𝑀
= nc2
3𝐿
1𝑀
𝑓 nc2
3𝐿
Pressure = =
𝐴 L2

1M
P= nc2
3 L3

1M 1
P= nc2 OR PV = Mnc2
3V 3

Kinetic energy of gases:

1
K.E. = m(µ1)2
2

1 1 1 1
K.E. for n moles = m(µ1)2 + m(µ2)2 + m(µ3)2 +…+ m(µn)2
2 2 2 2

1
= M {(µ1)2 + (µ2)2 +…+(µn)2}
2

Dividing and multiplying by n

1 (µ1)2 + (µ2)2 +…+ (µn)2
= Mn [ ]
2 𝑛

1
= Mnc2
2

Now dividing K.E. and PV

1
𝐾.𝐸.
Mnc2
2
= = 1
𝑃𝑉 Mnc2
3

3
= K.E. = PV
2

For one mole of ideal gas,

 PV=RT {where, n=1}

So,
3
= K.E. = RT
2

Kinetic energy here is of molecules. Total energy is taken internally. So, here
K.E. = ∆U (where, u is internal energy)

It show that
K.E. ∝ T

K.E. ∝ T – it is known as kinetic interpretation of temperature. According to

this average of kinetic energy is zero at T = 0.

On constant temperature 1 mole of any gas (H2, O2) all will have equal kinetic
energy.
3
K.E. of n moles = n× RT
2

3 RT 3 𝑅
K.E. of 1 molecule = = KBT {KB [Boltzmann constant]= = 1.38 × 10-23}
2 NA 2 NA

It is known as kinetic interpretation of temperature.

Degree Of Freedom
The total number of independent co-ordinate required specifying the position
of a molecule or the number of independent modes of motion possible with
any molecule is called degree of freedom.

Mono-, di- and polyatomic molecules have 3, 5 or (3 N-K) number of degree of

freedom where k is the number of constraints (restrictions associated with the
structure).

Molecules Degree Of Freedom (ϝ)

Monatomic gases 3
Diatomic gases 5
Polyatomic 6
CP = Specific Heat Capacity at constant Pressure

CV = Specific Heat Capacity at constant Volume

Mayor’s relation = CP - CV = R
ϝ
CV = R
2
ϝ
CP = [ + 1] R
2

CP 2
Heat Capacity ratio = 𝛾 = =1+
CV ϝ

For monatomic gases:

ϝ 3
CV = R = R
2 2 CP 5
𝛾= =
ϝ 5 CV 3
CP = [ + 1] R = R
2 2

For diatomic gases:

ϝ 5
CV = R = R CP 7
2 2
𝛾= =
CV 5
ϝ 7
CP = [ + 1] R = R
2 2

For polyatomic gases:

ϝ 6
CV = R = R CP 4
2 2
𝛾= =
CV 3
ϝ 8
CP = [ + 1] R = R
2 2

Nature of gas ϝ CP Cv CP – Cv 𝛾
Monatomic 3 20.8 12.5 8.31 1.67
Diatomic 5 29.1 20.8 8.31 1.40
Polyatomic 6 33.24 24.98 8.31 1.33
Law of equipartition of energy
In equilibrium, the total energy is equally distributed in all possible modes,
1
with each mode having an average speed equal to KBT. This is known as law
2
of equipartition of energy

Kinetic energy of 1 molecule

1 1 1
K.E. = mvx2 + mvy2 + mvz2
2 2 2

Average of energy ⟨K.E.⟩

1 1 1
⟨K.E.⟩ = ⟨ mvx2⟩+⟨ mvy2⟩+⟨ mvz2⟩
2 2 2

3
= KBT
2

Since no preference is given to direction

So,
1 1 1 1 1 1
⟨ mvx2⟩ = KBT ; ⟨ mvx2⟩ = KBT ; ⟨ mvx2⟩ = KBT
2 2 2 2 2 2