Introduction

Matter is anything that has mass and volume. That is, matter is anything that requires energy to
accelerate or change its motion and which also takes up space. Matter can come in many forms,
but there are four main phases or states of matter: solid, liquid, gas, and plasma. Since matter is
also composed of atoms, these phases differ in the behavior and organization of their atoms. All
elements can come in the form of any state of matter and transform between them. For example,
pure hydrogen on earth is typically in the form of a gas (unless it's bound to oxygen within
molecules of water); but if hydrogen is cold enough it can phase change into a liquid and even a
solid. However, the most common state of hydrogen and even all matter in the entire universe is
plasma. Plasma is what composes the Sun and stars. And some other examples of plasma include
lightning and fire which are less commonly found on Earth compared to solids, liquids, and
gases. Also, neon and fluorescent lights possess plasma states within their bulbs. The kinetic
theory of matter relates the macroscopic property of the gas, like – Temperature, Pressure, and
Volume to the microscopic property of the gas, like – speed, momentum, and position. In this
model, the atoms and molecules are continually in random motion, constantly colliding with one
another and the walls of the container within which the gas is enclosed. It is this motion that
results in physical properties such as heat and pressure. In this article, let us delve deeper into the
kinetic theory of gases.
What is the Kinetic Theory of Gases?
The gases are made up of a large number of molecules and they are flying in a random direction
at a certain speed. By knowing their speed or position, one can figure out the macroscopic
properties. In other words, by knowing the value of velocity or the internal energy of gas
molecules, one should be able to figure out the temperature or pressure.
Assumptions of Kinetic theory
The Kinetic theory of gases makes some basic assumptions. They are as follows:

Kinetic Theory Assumptions

 The molecules do not interact with each other.

 The collision of molecules with themselves or walls will be an elastic collision.
 The momentum is conserved.
 Kinetic energy will be conserved.

Kinetic Gas Equation Derivation

The kinetic theory of gases describes a gas as a large number of submicroscopic particles such as
atoms and molecules, all of which are in random and constant motion. The randomness arises
from the particles’ collisions with each other and with the walls of the container.
Derivation of Kinetic Gas Equation

Consider a cubical container of length ‘l ’ filled with gas molecules each having mass ‘m’ and
let N be the total number of gas molecules in the container. Due to the influence of temperature,
the gas molecules move in random directions with a velocity ‘v.’
The pressure of the gas molecules is the force exerted by the gas molecule per unit area of the
wall of the container and is given by the equation
Derivation of the Kinetic Gas Equation
The Kinetic Gas Equation relates the macroscopic properties of a gas—such as pressure, volume,
and temperature—to the microscopic properties, such as the velocities and masses of the gas
molecules. Below is the derivation of this equation.
Derivation of the Kinetic Gas Equation
1. Assumptions of Kinetic Theory of Gases:
 The gas consists of a large number of molecules moving in random directions with
different speeds.
 The molecules are small compared to the distances between them, so the volume of the
molecules is negligible compared to the volume of the container.
 Collisions between molecules and with the walls of the container are perfectly elastic (no
kinetic energy is lost).
 There are no intermolecular forces acting except during collisions.
2. Consider a Cubic Container:

 Let the side of the cube be LLL, so the volume V =L 3 V =L3 V =L3.

 Consider a single molecule of mass mmm moving with velocity

⃗v =( vx , vy , vz ) ¿ { v }=( v x , v y , v z ) v=( vx ​, vy ​, vz ) .

3. Pressure on the Walls:

 The molecule exerts a force when it collides with the wall of the container.
 Consider the collision with the wall perpendicular to the x-axis. Before the collision, the
x-component of the velocity is vxv xvx ​. After an elastic collision with the wall, this
component becomes −vx−v x −vx ​.

 The change in momentum in the x-direction is Δpx=2mvx ¿ p x =2 m v xΔpx =2 mvx ​.

 The time between successive collisions with the same wall is

Δt =2 Lvx ¿ t=¿ { 2 L } { v x } Δt=vx ​2 L ​.

 The force exerted by this molecule on the wall is:

Fx=ΔpxΔt =2 mvx 2 Lvx=mvx 2 L F x =¿ { ¿ p x } { ¿ t } =¿ { 2 mv x } {¿ { 2 L } { v x } }=¿ {m v } { L } Fx ​= ΔtΔpx ​​= vx ​2 L
2
x

4. Total Pressure:
 The total force on the wall is the sum of the forces due to all the molecules. If there are
NNN molecules in the container, and assuming each molecule has an average velocity
vˉ ¿ { v } vˉ , the total force is: F=∑ i=1 Nmvx ,i 2 LF=¿ m{iN=1¿ {} m v } L F=i=1 ∑ N ​Lmvx , i2
{ } { } 2
{x ,i }
  Pressure is defined as force per unit area. The area of the wall is L 2 L2 L 2 , so the pressure
is:
2 3 { 2 2
P=FL 2=1 L3 ∑ i=1 Nmvx ,i 2=Nm ⟨ vx 2 ⟩ VP=¿ {F }{L }=¿ {1}{L }¿{ i=1 } N }mv { x ,i } =¿ {Nm ⟨ v x ⟩ }{
over all molecules.
5. Relation Between Velocity Components:
 By the assumptions of isotropy (i.e., the gas has no preferred direction), the average
kinetic energy is the same in all directions:
⟨ vx 2 ⟩= ⟨ vy 2 ⟩= ⟨ vz 2 ⟩ ⟨ v x ⟩=⟨ v y ⟩=⟨ v z ⟩ ⟨ vx 2 ⟩ =⟨ vy 2 ⟩= ⟨ vz 2 ⟩
2 2 2

 Therefore,
⟨ v 2 ⟩= ⟨ vx 2 ⟩+ ⟨ vy 2 ⟩ + ⟨ vz 2 ⟩=3 ⟨ vx 2 ⟩ ⟨ v 2 ⟩=⟨ v2x ⟩+⟨ v 2y ⟩+ ⟨ v 2z ⟩=3 ⟨ v 2x ⟩ ⟨ v 2 ⟩= ⟨ vx 2 ⟩+ ⟨ vy 2 ⟩ + ⟨ vz 2 ⟩=3 ⟨ vx 2 ⟩

 So, ⟨ vx 2 ⟩= ⟨ v 2 ⟩ 3 ⟨ v 2x ⟩=¿ {⟨ v 2 ⟩ } {3 } ⟨ vx 2 ⟩ =3 ⟨ v 2 ⟩

6. Final Form of Kinetic Gas Equation:

 Substituting into the expression for pressure:
P=Nm ⟨ v 2 ⟩ 3 VP=¿ {Nm ⟨ v ⟩ } {3 V } P=3 VNm ⟨ v 2 ⟩
2

 The total kinetic energy of the gas molecules is:

Ekin=12 Nm ⟨ v 2 ⟩ E {¿ { kin}}=¿ {1 } {2 } N m⟨ v ¿ ​=21 ​Nm ⟨ v 2 ⟩
2

 Therefore, the pressure can also be written as:

P=23 EkinVP=¿ {2 }{3 }¿ {E {¿ {kin}}}{V } P=32 ​VEkinpartition Of Energy
Law of equipartition of energy: Statement

equipartition of energy, law of statistical mechanics stating that in a system in thermal

equilibrium, on the average, an equal amount of energy will be associated with each degree of
freedom. (A particle moving through space has three degrees of freedom because three
coordinates are needed to describe its position.) Based on the work of physicists James Clerk
Maxwell of Scotland and Ludwig Boltzmann of Germany, this law states specifically that a
system of particles in equilibrium at absolute temperature T will have an average energy
of 1/2kT associated with each degree of freedom, in which k is the Boltzmann constant. In
addition, any degree of freedom contributing potential energy will have another 1/2kT associated
with it. For a system of s degrees of freedom, of which t have associated potential energies, the
total average energy of the system is 1/2(s + t)kT.

For example, an atom of a gas has three degrees of freedom (the three spatial, or position,
coordinates of the atom) and will, therefore, have an average total energy of 3/2kT. For an atom
in a solid, vibratory motion involves potential energy as well as kinetic energy, and both modes
will contribute a term 1/2kT, resulting in an average total energy of 3kT.

According to the law of equipartition of energy, for any dynamic system in thermal equilibrium,
the total energy for the system is equally divided among the degree of freedom.

The kinetic energy of a single molecule along the x-axis, the y-axis, and the z-axis is given as

, along the x-axis

, along the y-axis

, along the z-axis

When the gas is at thermal equilibrium, the average kinetic energy is denoted as

,along the x-axis

, along the y-axis

, along the z-axis

According to the kinetic theory of gases, the average kinetic energy of a molecule is given by,
where Vrms is the root-mean-square velocity of the molecules, Kb is the Boltzmann constant and T
is the temperature of the gas.

The mono-atomic gas has three degrees of freedom, so the average kinetic energy per degree of

freedom is given by

If a molecule is free to move in space, it needs three coordinates to specify its location, thus, it
possesses three translational degrees of freedom. Similarly, if it is constrained to move in a
plane, it possesses two translational degrees of freedom and if it is a straight line, it possesses
one translational degree of freedom. In the case of a triatomic molecule, the degree of freedom is
6. And the kinetic energy of the per molecule of the gas is given as,

Molecules of a mono-atomic gas like argon and helium have only one translational degree of
freedom. The kinetic energy per molecule of the gas is given by

The diatomic gases such as O2 and N2 which have

three translational degrees of freedom can rotate only about their center of mass. Since, they
have only two independent axes of rotation, as the third rotation is negligible, due to its 2-D
structure. Thus, only two rotational degrees of freedom are considered. The molecule thus has
two rotational degrees of freedom, each of which contributes a term to the total energy consisting
of transnational energy t and rotational energy.

Degrees of Freedom

Imagine a single atom. In a three dimensional space, it can move freely along the X, Y and Z
axis. Motion from one point to another is also known as translation. Hence, this movement along
the three axes is called translational movement. If you have to specify the location of this atom,
then you need three coordinates (x, y, and z).

We can also say that a single atom has 3 Degrees of Freedom. Most monoatomic molecules (i.e.
molecules having a single atom like Argon) have 3 translational degrees of freedom, provided
their movement is unrestricted.

Let’s now imagine a diatomic molecule (a molecule having two atoms like O 2 or N2). Apart from
the three translational degrees of freedom, these molecules can also rotate around the centre of
mass. Two such rotations are possible along the axis normal to the axis that joins the two atoms.

It is important to note here that these diatomic molecules are not rigid rotators (where molecules
do not vibrate) at all temperatures. Along with the translational and rotational movements,
diatomic molecules also oscillate along the interatomic axis like a single dimensional oscillator.
This adds a vibrational degree of freedom to such molecules.

Hence, to specify the location of a diatomic molecule, you would finally need the X, Y and Z
coordinates along with the rotational and vibrational coordinates. So, in a nutshell, Degrees of
Freedom is nothing but the number of ways in which a molecule can move. This forms the basis
of the Law of Equipartition of Energy.

Law of Equipartition of Energy

The law states that: “In thermal equilibrium, the total energy of the molecule is divided equally
among all Degrees of Freedom of motion”. Before delving into the calculations, let’s understand
the law better. If a molecule has 1000 units of energy and 5 degrees of freedom (which includes
translational, rotational and vibrational movements), then the molecule allocates 200 units of
energy to each motion.

Kinetic Energy of a single molecule: KE = 1/2 mv2. A gas in thermal equilibrium at temperature
T, the average Energy is:

Eavg = 1/2 mvx2 + 1/2 mvy2 + 1/2 mvz2 = 1/2KT + 1/2 KT + 1/2 KT = 3/2 KT
where K = Boltzmann’s constant. In case of a monoatomic molecule, since there is only
translational motion, the energy allotted to each motion is 1/2KT. This is calculated by dividing
total energy by the degrees of freedom:

3/2 KT ÷ 3 = 1/2 KT

In case of a diatomic molecule, translational, rotational and vibrational movements are involved.
Hence the Energy component of translational motion= 1/2 mv x2 + 1/2 mvy2 + 1/2 mvz2. Energy
component of rotational motion= 1/2 I 1w12 + 1/2 I2w22 {I1 & I2 moments of inertia. w1 & w2 are
angular speeds}

And, the energy component of vibrational motion= 1/2 m (dy/dt) 2+ 1/2 ky2. Where k is the force
constant of the oscillator and y is the vibrational coordinate. It is important to note here that this
has both kinetic and potential modes.

According to the Law of Equipartition of Energy, in thermal equilibrium, the total energy is
distributed equally among all energy modes. While the translational and rotational motion
contributes ½ KT to the total energy, vibrational motion contributes 2 x 1/2KT = KT since it has
both kinetic and potential energy modes.