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Chapter 12
Kinetic Theory
Introduction
Kinetic theory explains the behaviour of gases based on the idea that the
gas consists of rapidly moving atoms or molecules. The kinetic theory was
developed in the nineteenth century by Maxwell, Boltzmann and others.

Behaviour of Gases
Ideal gas equation
Gases at low pressures and high temperatures much above that at which
they liquefy (or solidify) approximately satisfy a simple relation
PV = μ RT------------(1)
where μ is the number of moles
R is universal gas constant.
R = 8.314 J mol−1 K −1
T is absolute temperature.
A gas that satisfies this eqn exactly at all pressures and temperatures is
defined to be an ideal gas.
But R = 𝐍𝐀 𝐤 𝐁
NA is Avogadro number
k B is Boltzmann constant
k B = 1.38 × 10−23 J K −1

PV = μ𝐍𝐀 𝐤 𝐁 T
μNA = N
N is the number of molecules of
gas
The perfect gas equation canalso be written as
PV = N𝐤 𝐁 T -------------(2)

PV
From above eq , = constant
T
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From graph it is clear that real gases approach ideal gas behaviour at low
pressures and high temperatures.
At low pressures or high temperatures the molecules are far apart and
molecular interactions are negligible. Without interactions the gas behaves
like an ideal one.
Boyle’s Law
PV = μ RT
If we fix μ and T,
PV = Constant
𝟏
P∝
𝐕
i.e., for a fixed temperature , pressure of a given mass of gas varies
inversely with volume. This is the famous Boyle’s law.
Charles’Law
PV = μ RT
If we fix P
𝐕
= 𝐜𝐨𝐧𝐬𝐭𝐚𝐧𝐭
𝐓
V∝T
i.e., for a fixed pressure, the volume of a gas is proportional to its absolute
temperature T (Charles’ law).
Dalton’s law of partial pressures.
Consider a mixture of non-interacting ideal gases μ1 moles of gas 1, μ2
moles of gas 2, etc
PV =(μ1 + μ2 +… ) RT
RT RT
P= μ1 V +μ2 V + …………..
P =𝐏𝟏 +𝐏𝟐 + …………….
Thus, the total pressure of a mixture of ideal gases is the sum of partial
pressures. This is Dalton’s law of partial pressures.
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Kinetic Theory of an Ideal Gas

▪ A given amount of gas is a collection of a large number of molecules
that are in random motion.
▪ At ordinary pressure and temperature, the average distance between
molecules is very large compared to the size of a molecule (2 Å).
▪ The interaction between the molecules is negligible.
▪ The molecules make elastic collisions with each other and also with
the walls of the container .
▪ As the collisions are elastic , total kinetic energy and total momentum
are conserved .
Pressure of an Ideal Gas

A gas is enclosed in a cube of side 𝑙

Consider a molecule moving in positive x direction makes an elastic
collision with the wall of thecontainer.
Momentum before collision = mvx
Momentum after collision = −mvx
The change in momentum of the molecule = −mvx −mvx
= −2 mvx
By the principle of conservation of momentum
Momentum imparted to wall in the collision = 2mvx
Distnace travelled by the molecule in time Δt = vx Δt
Volume covered by the molecule = Avx Δt
No of molecules in this volume = n Avx Δt
(n is number density of molecules)
Only half of these molecules move in +x direction
1
No of molecules = 2 nA vx Δt

The number of molecules with velocity vx hitting the wall in time Δt

1
= nA vx Δt
2
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The total momentum transferred to the wall
1
Q = (2mvx ) ( nA vx Δt )
2
2
Q = nmAvx Δt
Q
The force on the wall, F =
Δt
F = nmAvx 2
F
Pressure, P =
A
P = nmvx 2
All molecules in a gas do not have the same velocity; so average velocity is
to be taken
P= nmv̅̅̅2
x
v̅̅̅2 = v̅̅̅
2 ̅̅̅2 ̅̅̅2
x + vy + vz
̅̅̅
vx2 = v̅̅̅y2 = v̅̅̅
2
z
̅̅̅
v 2 = 3 ̅̅̅ vx2
̅̅̅ 1 2
vx2 =3 ̅̅̅
v
2 1 ̅̅̅
but v̅̅̅ 2
x = v
3
𝟏
̅̅̅𝟐
P= nm𝐯
𝟑
Kinetic Interpretation of Temperature
1
P= nmv̅̅̅2
3
1
PV= nVmv̅̅̅2
3
N
n= , N=nV
V
1
PV= Nmv̅̅̅2
3
where N is the number of molecules in the sample.
2 1
PV= (N mv̅̅̅2 )
3 2
The quantity in bracket is the average translational kinetic energy of the
molecules in the gas.
1
N mv̅̅̅2 =E
2
2
PV= E---------------------(1)
3
Ideal gas equation, PV =Nk B T -------------------(2)
2
From eq(1)and (2) E = Nk B T
3
3
E = Nk B T
2
𝟑
E/N = 𝟐 𝐤 𝐁 T
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The average kinetic energy of a molecule is proportional to the absolute
temperature of the gas; it is independent of pressure, volume or the nature
of the ideal gas.
Note:
This is a fundamental result relating temperature( a macroscopic
measurable parameter) to the average kinetic energy(microscopic
quantity) of a gas molecule. The two domains are connected by the
Boltzmann constant.

Root Mean Square (rms) Speed

3
E/N = k B T
2
1 3
mv̅̅̅2 = k B T
2 2
3kB T
v̅̅̅2 =
m
The square root of v̅̅̅2 is known as root mean square (rms) speed and is
denoted by vrms
𝟑𝐤 𝐁 𝐓
𝐯𝐫𝐦𝐬 = √
𝐦
Degrees f Freedom
The total number of independent ways in which a system can possess
energy is called degree of freedom.
A molecule has one degree of freedom for motion in a line.
Two degrees of freedom for motion in a plane.
Three degrees of freedom for motion in space.
Law of Equipartition of Energy
Law of Equipartition of Energy states that, in equilibrium, the total energy
is equally distributed in all possible energy modes, with each mode having
𝟏
an average energy equal to 𝐤 𝐁 T
𝟐
1
▪ Each translational degree of freedom contributes k B T
2
1
▪ Each rotational degree of freedom contributes k B T
2
1
▪ Each vibrational degree of freedom contributes , 2 𝑥 kBT = kBT
2
as a vibrational mode has both kinetic and potential energy modes.
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Specific Heat capacity

Specific Heat capacities of Monoatomic Gases
The molecule of a monatomic gas has only 3 translational degrees of
freedom.
1 3
Average energy of a molecule =3 𝑥 kBT = kB T
2 2

The total internal energy of a mole of such a gas is,

3
U= k B T x NA
2

k B NA =R
3
U = RT
2

Specific heat capacity at constant volume

dU
Cv =
dt
d 3
= (2 RT)
dT

𝟑
𝐂𝐕 = R
𝟐

For an ideal gas, CP – CV = R (Mayer’s relation)

Specific heat capacity at constant pressure,

CP = C V + R
3
= R +R
2

𝟓
𝐂𝐏 = 𝟐 R
The ratio of specific heats
5
CP R
2
= γ = 3
CP R
2

𝟓
Adiabatic constant , 𝛄=
𝟑
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Specific heat capacities of Diatomic Gases

Rigid diatomic molecule
A diatomic rigid rotator has , 3 translational and 2 rotational degrees of
freedom.i.e.,
1
Average energy of a molecule = 5 x k B T
2
5
= kB T
2

The total internal energy of a mole of such a gas is,

5
U= k B T x NA
2

k B NA =R
5
U = RT
2

Specific heat capacity at constant volume

dU
Cv =
dt
d 5
= (2 RT)
dT

𝟓
𝐂𝐕 = R
𝟐
For an ideal gas, CP – CV = R (Mayer’s relation)
Specific heat capacity at constant pressure,
CP = C V + R
5
= 2 R +R
𝟕
𝐂𝐏 = R
𝟐
The ratio of specific heats
7
CP R
2
=γ= 5
CP R
2

𝟕
Adiabatic constant , 𝛄=
𝟓

Non Rigid Diatomic Molecule

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A non rigid diatomic molecule has , 3 translational , 2 rotational and
1 vibrational degrees of freedom.
1
(Each vibrational degree of freedom contributes ,2x k B T =k B T)
2
5
Average energy of a molecule = k B T + k B T
2
7
= kBT
2

The total internal energy of a mole of such a gas is,

7
U= k B T x NA
2

k B NA =R
𝟕
U = 𝟐 RT
Specific heat capacity at constant volume
dU
Cv =
dt
d 7
= (2 RT)
dT
𝟕
𝐂𝐕 = R
𝟐
For an ideal gas, CP – CV = R (Mayer’s relation)
Specific heat capacity at constant pressure,
CP = C V + R
7
= R +R
2
𝟗
𝐂𝐏 = 𝟐 R
The ratio of specific heats
9
CP R
2
= γ = 7
CP R
2
𝟗
Adiabatic constant , 𝛄=
𝟕
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Polyatomic Gases
A polyatomic molecule has 3 translational, 3 rotational degrees of freedom
and a certain number ( f ) of vibrational modes.
3 3
Average energy of a molecule = k B T + k B T +f k B T
2 2

The total internal energy of a mole of such a gas is,

3 3
U=( k B T + k B T + f k B T ) NA
2 2
( )
U= 3 + f k B TNA
k B NA =R
U=( 3 + f )RT
Specific heat capacity at constant volume
dU
Cv =
dt
𝐂𝐕 =( 𝟑 + 𝐟 )𝐑
Specific heat capacity at constant pressure,
CP = CV + R
=( 3 + f )R +R
𝐂𝐏 =( 𝟒 + 𝐟 )𝐑
The ratio of specific heats
CP ( 4+f )R
γ= =(
CP 3 +f )R
( 𝟒+𝐟 )
Adiabatic constant , 𝛄=(
𝟑 +𝐟 )
Specific Heat Capacity of Solids
Consider a solid of N atoms, each vibrating about its mean position.
1
A vibration in one dimension has average energy = 2x k B T
2
= kBT
In three dimensions, the average energy = 3k B T
The total internal energy of a mole of solid is,
U =3k B T x NA
k B NA =R
U =3RT
dU
Specific heat capacity C= dt
d
= (3 RT)
dT

𝐂 =𝟑𝐑
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Mean Free Path

The mean free path 𝑙 is the average distance covered by a molecule
between two successive collisions.
𝟏
𝒍=
√𝟐𝐧𝛑𝐝𝟐

Consider the molecule of a gas as spheres of diameter d. Focus a single

molecule.
The volume swept by a molecule in time Δt in which any molecule
will collide with it = Area x distancd covered
= πd2 × 〈v〉Δt
The number of collisions suffered by the molecule in time Δt.
= nπ〈v〉d2 Δt
where n is the number of molecules per unit volume,

Rate of collision = nπ〈v〉d2

Time between two successive collisions is on the average,
1
τ=
nπ〈v〉d2
The average distance between two successive collisions, called the mean
free path 𝑙 , is
𝑙 = 〈v〉 τ
1
𝑙 = 〈v〉
nπ〈v〉d2
1
𝑙=
nπd2
As all molecules are moving , average relative velocity of the moleculesis to
be considered. So the exact equation is
𝟏
𝒍=
√𝟐𝐧𝛑𝐝𝟐
Seema Elizabeth
HSST Physics
MARM Govt HSS Santhipuram
Thrissur