Thermal Physics

Lecture 2
KINETIC THEORY OF GASES

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Assumptions of Kinetic Theory of Gases

Matter is composed of very large number of atoms and molecules.

Kinetic theory of gases attempts to relate the macroscopic or bulk

properties such as pressure, volume and temperature of an ideal gas with its
microscopic properties such as speed and mass of its individual molecules.

The kinetic theory is based on certain assumptions. (A gas whose

molecules can be treated as point masses and there is no intermolecular force
between them is said to be ideal.) A gas at room temperature and atmospheric
pressure (low pressure) behaves like an ideal gas

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Assumptions of Kinetic Theory of Gases

Clark Maxwell in 1860 showed that the observed properties of a gas can
be explained on the basis of certain assumptions about the nature of
molecules, their motion and interaction between them. These resulted in
considerable simplification

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 Assumptions1 of Kinetic Theory of Gases

A gas consists of a very large number of identical rigid molecules, which

move with all possible velocities randomly. The intermolecular forces
between them are negligible. The number of molecules in a kilo-mole is
6.023x1026.And this is known as Avagadro’s number.

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Assumption 2 of Kinetic Theory of Gases

Gas molecules collide with each other and with the walls of the
container. These collisions are perfectly elastic or the molecules of a
gas behave as rigid ,perfectly elastic hard spheres. It means that
molecules neither lose energy nor deform in shape when they collide
amongst themselves or with the walls of the container.

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Assumption 3 of Kinetic Theory of Gases

The gas can be regarded as point masses. Experiments show that the
diameter of a gas molecule is about 2-3x10-10m which is negligible
compared to the separation between them. The distance between any two
neighboring gas molecules at STP, on an average is about 3x10-9m , which
is an order of magnitude bigger than their diameter.

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Assumption 4 of Kinetic Theory of
Gases

The gas molecules are in the state of constant random motion. Infact, the
motion of gas molecules resembles the motion of honeybees distributed
from their hive. It means that molecules of an ideal gas can move in all
possible directions and all positions are equally probable. The support for
this assumption came in the form of Brownian motion.

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Assumption 5 of Kinetic Theory of
Gases

In absence of any external force field, the molecules are

distributed uniformly in the container .It means an ideal gas
behaves as an isotropic medium. In practice, however some
randomness in the direction of the velocities may arise because
of irregularity on the walls of the container.

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Assumption 6 of Kinetic Theory of
Gases
The molecules of a gas experience force only during collisions. This
assumption implies that there are no intermolecular forces ( of mutual
attraction or repulsion) between the molecules and the walls of the
container. That is, molecule of a gas can be thought of as moving freely
unaware of the presence of other molecules. In other words, the
molecules of an ideal gas possess only kinetic energy.

Since the particles are always in motion, they have average kinetic
energy proportional to the temperature of the gas.

The average kinetic energy of the gas particles changes with

temperature. i.e., The higher the temperature, the higher the average
kinetic energy of the gas.

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Assumption 7 of Kinetic Theory of Gases
Time taken in a collision is negligible as compared to the time
taken by a molecule between two successive collisions

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Assumption 8 of Kinetic Theory of Gases

These molecules are in constant random motion which results in

colliding with each other and with the walls of the container. As the gas
molecules collide with the walls of a container, the molecules impart
some momentum to the walls. Basically, this results in the production of
a force that can be measured. So, if we divide this force by the area it is
defined to be the pressure.

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 Assumption 9 of Kinetic Theory of
Gases
All molecules do not move with the same speed. That is, there is spread of
molecular speeds ranging from zero to infinity .

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 Assumption 10 of Kinetic Theory of
Gases

The gravitational potential energy does not in any way affect the
motion of gas molecules. This assumption is quite justified since the
magnitude of gravitational force is 10-43N,which is much less than
the molecular force whose magnitude is about 10-13N for normal
separation between two molecules.

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Pressure Exerted by an Ideal gas

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 Pressure Exerted by a Gas
Every body is made up of molecules. Depending on its nature and
temperature, the molecules may possess translatory motion, vibratory
motion and rotatory motion about its axis.

Each type of motion provides some kinetic energy to the molecules.

Heat possessed by a body is the total thermal energy of the body, which is
the sum of kinetic energies of all the individual molecules of the body.

Temperature of a body is the degree of hotness or coldness of the body.

Heat flows from a body at high temperature to a body at low temperature
when they are in contact with each other. Temperature is the thermal state
of the body, that decides the direction of flow of heat.

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Pressure Exerted by a Gas
The molecules of a gas are in a state of random
motion. They continuously collide against the
walls of the container.

During each collision, momentum is transferred

to the walls of the container. The pressure
exerted by the gas is due to
the continuous collision of the molecules agai
nst the walls of the container.

Dueto this continuous collision, the walls exp

erience a continuous force which is equal to the
total momentum imparted to the walls per
second. The force experienced per unit area of
the walls of the container determines the
pressure exerted by the gas.
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 Pressure Exerted by a Gas
Consider a cubic container of side containing n molecules of perfect
gas moving with velocities C1, C2, C3 ... Cn as shown in figure.

A molecule moving with a velocity C1, will have velocities u1, v1 and w1 as
components along the x, y and z axes respectively. Similarly u2, v2 and
w2 are the velocity components of the second molecule and so on.

Let a molecule P as shown in figure having

velocity C collide against the wall marked I
(BCFG) perpendicular to the x-axis.

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Only the x-component of the velocity of the molecule is relevant for the wall I.
Hence momentum of the molecule before collision is mu1 where m is the mass
of the molecule. Since the collision is elastic, the molecule will rebound with
the velocity u1 in the opposite direction. Hence momentum of the molecule
after collision is –mu1.

Change in the momentum of the molecule

= Final momentum - Initial momentum
= –mu1 – mu1 = –2mu1

During each successive collision on face I the molecule must travel a

distance 2l from face I to face II and back to face I.
Time taken between two successive collisions is = 2l / u1
∴ Rate of change of momentum = Change in the momentum/Time taken
= – 2mu1/(2l/u1) = -2mu12/2l = – mu12/l
(i.e) Force exerted on the molecule = – mu12/l

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According to Newton’s third law of motion, the force exerted
by the molecule,
= – (– mu12)/l = mu12/l
Force exerted by all the n molecules is
Fx = mu12/l + mu22/l + …...+mun2/l
Pressure exerted by the molecules,
Px = Fx/A
= 1/l2 (mu12/l + mu22/l + …...+mun2/l)
= m/l3 (u12+ u22 + …...+un2)

Similarly, pressure exerted by the molecules along Y

and Z axes are,
Py = m/l3 (v12+ v22 + …...+vn2)
Pz = m/l3 (ω12+ ω22 + …...+ωn2)

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 Similarly, pressure exerted by the
molecules along Y and Z axes are,
Py = m/l3 (v12+ v22 + …...+vn2)
Pz = m/l3 (ω12+ ω22 + …...+ωn2)

Since the gas exerts the same pressure on all the walls of the
container
Px = Py = Pz = P
P = [Px+Py+Pz]/3

P = [(1/3) (m/l3)] [(u12+ u22 + …...+un2) + (v12+ v22 + …...+vn2) + (ω12+ ω22 + …...+ωn2)]

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P = [(1/3) (m/l3)] [(u12 + v12 +ω12) + (u22 + v22 +ω22) +.............+ (un2 + v
P = [(1/3) (m/l3)] [C12+C23+ …...+Cn2]
Here, C12 = (u12 + v12 +ω12)
P = [(1/3) (mn/l3)] [C12+C23+ …...+Cn2/n]
P = (1/3) (mn/V) C2
where C is called the root mean square
(RMS) velocity, which is defined as the
square root of the mean value of the squares
of velocities of individual molecules.
That is, C = √[C12+C23+ …...+Cn2/n]

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The pressure exerted by an ideal gas is numerically equal
to two-third of the mean kinetic energy of translation per
unit volume of the gas.

The kinetic energy of the gas is expressed as

K.E=1/2Mν2
Divide Pressure equation by Kinetic energy, we get

P 2
=
KE 3V

Pressure P = 2/3 X Kinetic Energy per unit volume

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