Department of Aeronautical Engineering (AE), MIST

Course Code: PHY 119, Course Title: Thermal Physics (1 credit)

Level- 1, Term- II, Fall 2024. Credit Hour: 3, Contact Hour: 3

Lecture # 6: Kinetic Theory of Gases

Introduction
At very low pressures or densities, gases obey some simple laws regarding their physical properties in
addition to their chemical properties. It was thought that since gases, in general, obey such simple laws as
Boyle's law, Charles' law, Avogadro's law, Dalton's law of partial pressures, etc., they should have a
common and simple structure. The many accurate experiments on the conversion of work into heat
established that heat is a form of energy which relates to the motion of molecules of which matter is made.
Attempts were then made to explain the behavior of gases from a simple mechanical structure. The scientists
who contributed to this structure are, among others, J.C. Maxwell Boltzmann and R. Clausius. The outcome
of their labor is known as the kinetic theory of gases.

Kinetic Theory of Gases

The kinetic theory of gases is a theoretical framework that describes the behavior of gases in terms of the
motion of their individual molecules. It provides a microscopic explanation for macroscopic properties such
as pressure, temperature and volume.

Fundamental Assumptions of the Kinetic Theory of Gases

The kinetic theory of gases is based upon the following simplifying assumptions or postulates:
(i) The kinetic theory assumes that a gas consists of an exceedingly large number of particles. These
particles are referred to as molecules in the atomic theory. For any one chemical species, all molecules are
identical.
(ii) The molecules are supposed to resemble perfectly rigid spheres like a steel ball-bearing. They obey
Newton’s laws of motion (conservation of momentum and energy).
(iii) The molecules are continuously moving at random with all Possible velocities in all possible directions,
colliding with each other and against the wall of the containing vessel. The collision between molecules and
the walls as well as molecules themselves are assumed to be perfectly elastic in words, there is no loss in
kinetic energy when collisions occur. As the chance of collisions in all directions is the same, the collisions
do not affect the molecular density.
(iv) The pressure exerted by a gas is due to the continuous bombardment on the walls of the containing
vessel by the gas molecules because of their unordered motion. Obviously, the collisions among molecules
themselves and against the walls will be greater in number when the volume is decreased because there is
now less room for motion. This explains why pressure gets increased when the volume is decreased.
(v) The molecules are themselves of very small dimensions, their actual volume being negligible in
comparison with the space at their disposal, i.e., the volume of the vessel.
(vi) The molecules of the gas are sufficiently far apart most of the time so that they do not exert any force of
attraction or repulsion on one another except when they collide with each other and with a wall. Between
two collisions, the molecules, therefore, move in a straight line with uniform velocity i.e., they obey
Newton’s law.
(vii) Because the molecules do not exert any force of attraction or repulsion on one another, they cannot
have any potential energy (other than gravitational) but have only kinetic energy.
(viii) When there is no external field or force, the molecules are distributed uniformly throughout a
container; on average the number of molecules present in a small element of volume remains constant.
(ix) The size of the molecules is infinitesimally small as compared to the distance traversed by a molecule
between any two consecutive collisions, called its free path.
(x) The time during which a collision lasts is negligible in comparison to the time taken to traverse the mean
free path.

Expression for Pressure Exerted by a Gas

Let us imagine a certain quantity of a perfect gas to be confined in a cube, the
length of whose side is L. Let the total number of molecules be n and let each
of them have a mass equal to m . The molecules are moving at random with
different speeds the average of which is c [c is not the usual average speed but
the root mean square speed].
Since the average speed of the molecules is c, we may regard that all
molecules are moving with the same velocity c in all possible directions. Let
us calculate the effect produced on each wall because of the collisions of the
molecules with the wall. Concentrating our attention upon a particular molecule, we can resolve c into three
components, u, v , and w at right angles to one another and parallel to the sides AB, AC and AD of the
containing vessel (see in the figure).
The component u parallel to AB, has effect only on the wall ACED and the wall opposite to it; it has no
effect on the other walls. The molecule strikes with the velocity u and rebounds with the same velocity,
since the walls and the molecules behave like perfectly elastic bodies. So, the momentum before collision in
the direction AB is m ⋅u and after collision in the same direction is −m .u .
Hence, the change of momentum per collision is,
ΔP=originalmomentum — final momentum
¿+ mu — mu=2 mu
If the distance between the two opposite walls be l cm, the particle suffers one collision after each l cm;
therefore, the total number of collisions per second is u/l . So, the total change of momentum per second due
to component u is,
¿ change ∈momentum per collision× total number of collisions per second
2
u 2 mu
¿ 2 mu× =
l l
Similarly, the change in momentum per second for the other components v and w are 2 m v 2 /l and 2 m w2 /l
respectively. Therefore, the total change of momentum per molecule per second is,
 2 2 2
2m u 2 m v 2 mw
¿ + +
l l l
2m 2 2 2 2m 2
¿ ( u + v +w )= c
l l
since by dynamics, c 2=u 2+ v 2+ w2.
If there are n molecules present, the total effect on the walls will be multiplied n times. Therefore, the total
change in momentum for all the molecules per second is,
2 2
2m c 2mn c
×n=
l l
According to the second law of motion, the impressed force is numerically equal to the rate of change of
momentum or momentum generated per second. Now the impressed force i.e., the total pressure on the six
walls of the cube is 6 l 2 × P where P is the force per unit area of the wall, l 2 is the area of each wall (face of
the cube) and there are six faces in a cube. Therefore,
2
2mn c 2
=P × 6 l
l
2 2
mn c 1 mn c
P= 3
=
3l 3 V
since l 3 = volume of the cube.
Above equation gives the expression for the pressure exerted by gas molecules on the walls of the
containing vessel. The deduction though made for a cube is valid for a vessel of any shape. Any vessel may
be imagined to be partitioned into many infinitesimally small cubes, the total volume of which is equal in
the limit to the volume of the particular vessel. The relation PV =(1/ 3) mn c 2 is then valid for each cube; but
the pressure on opposite sides of the common wall neutralizes each other. Then the only surface left on
which the gas pressure acts is the outward surface of the exterior cubes, which in the limit is equal to the
surface of the containing vessel.
The equation can be rearranged as:
1 2
2n. mc
2
1 mn c 2
P= =
3 V 3V
The numerator in the equation is twice the total kinetic energy of all the molecules in the gas, while the
denominator is three times the volume of the gas. Thus, we have,
2 total kinetic energy of translation
pressure=
3 volume
The pressure is therefore, two-thirds of the total kinetic energy of translation of the molecules in unit
volume.

Kinetic Interpretation of Temperature

Let us consider 1 gm-molecule of a gas occupying a volume V. Thus,
1 2 1 2
PV = mn c = M c
3 3
where M =mn is the total mass of all the molecules present in 1 gm-molecule or molecular weight. From
molar gas equation, we have,
PV =RT
where R is the molar gas constant. Combining the above two equations, we get,
 1 2
M c =RT
3
1 2 3
M c = RT
2 2
3
Thus, the total kinetic energy of a gm-molecule of a gas is equal to RT .
2
Special Case: When T =1 K ,

R= (
2 1
3 2
M c2 )
 Above equation gives a physical meaning to the gas constant R and shows that it is equal to two-
third of the total translational energy of the molecules in one gm-molecule of a gas at a tempeiature
of one degree absolute.
 The root mean square speed of the molecules of a gas at a given temperature can also be calculated
merely from a knowledge of the value of the gas constant and of the absolute temperature.
 It can further be seen that at a given temperature T K , the mean kinetic energy of translation of one
gm-molecule of any gas has the same value which is (3 /2)RT .
Now n , the total number of molecules in one gm-molecule of a gas is the Avogardo's number and is denoted
by N . Dividing both sides of the above equation by N , we have,
1M 2 3 R
c= T
2 N 2N
But M / N=m, the mass of a single molecule.
1 2 3
m c = kT
2 2
where k =R/ N , is the gas constant per molecule and is called the Boltzmann’s constant.
Thus, we see that the mean kinetic energy of translation of one molecule of any gas at a temperature T K is
(3 /2)KT . It can be seen from the above equations that whether it is one gm-molecule or one molecule of a
gas, the mean kinetic energy of translation is a function of temperature only.
In other words, temperature is a measure of kinetic energy of translation of the gas molecules. This is
referred to as the kinetic interpretation of temperature. From the above discussion it becomes obvious that
the absolute temperature is proportional to the mean kinetic energy of translation of the molecules.

The Root Mean Squared Speed

In the deduction of the pressure exerted by a gas, the speed of the gas molecules has been for simplicity
called the average speed, but it is not the average speed c av but a speed called the root mean square speed c .
The root mean square (RMS) speed may be defined as the hypothetical velocity which all the molecules of a
gas would possess if the total kinetic energy was equally divided among them. It is given by the root of the
mean value of the squares of the velocities of all molecules.
The reason that the rms speed c is to be used rather than the average speed c av , is because the total kinetic
1 2
energy is an invariable quantity at constant temperature and this total kinetic energy is M c and not
2
1 2
M c av.
2
1 2
The total kinetic energy=Number of molecules × mass × ( rms speed )
2
If n molecules have speed c 1, c 2, … c n respectively, the average speed, c av and the rms speed, c are given by,
 c 1+ c 2+ …+c n
c av =
n

c=
√
c 21+ c 22+ …+c 2n
n

Calculation of the RMS Speed

The expression for pressure exerted by a gas is,
1 2
mn c
3 1M 2 1 2
P= = c = ρc
V 3 V 3
where ρ=M /V is the density of the gas.
2 3P
c=
ρ

c=
√ 3P
ρ
This equation enables is to determine the value of c for any particular gas at a given temperature, if P and ρ
for it be known.

Derivation of the Gas Equation

For 1 gm-molecule of a gas, we have,
1 2
PV = mn c
3
where m is the mass of a molecule and n is the number of molecules. But the total number of molecules in 1
gm-molecule of the gas is the Avogadro’s number, N . Therefore,
1 2
PV = mN c
3
2 1 2 1 2
The above equation can be regarded as PV = N ×( mc ). But m c , the kinetic energy of one molecule
3 2 2
3
of a gas is equal to kT , where k is the Boltzmann’s constant. Hence,
2
2 3 2 3 R
PV = N kT = N × T
3 2 3 2N
PV =RT
where, R is the molar gas constant. This is the gas equation.

References:

1. Physics For Engineers -Part-1: Prof. Dr. Gias Uddin Ahmed

2. Fundamentals of Physics: Halliday, Resnick and Walker
3. Heat & Thermodynamics: Brijlal and N. Subrahmanyam