Kinetic Theory of Gases

Gases can be studied by considering the small scale action of
individual molecules or by considering the large scale action of

the gas as a whole. We can directly measure, or sense, the large
scale action of the gas. But to study the action of the molecules,
we must use a theoretical model. The model, called the kinetic
theory of gases, assumes that the molecules are very small
relative to the distance between molecules. The molecules are in
constant, random motion and frequently collide with each other
and with the walls of any container.
The individual molecules possess the standard physical

properties of mass, momentum, and energy. The density of a gas
is simply the sum of the mass of the molecules divided by the
volume which the gas occupies. The pressure of a gas is a
measure of the linear momentum of the molecules. As the gas
molecules collide with the walls of a container, the molecules
impart momentum to the walls, producing a force that can be
measured. The force divided by the area is defined to be the
pressure. The temperature of a gas is a measure of the mean
kinetic energy of the gas. The molecules are in constant random
motion, and there is an energy (mass x square of the velocity)
associated with that motion. The higher the temperature, the
greater the motion.
In a solid, the location of the molecules relative to each other

remains almost constant. But in a gas, the molecules can move
around and interact with each other and with their surroundings
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in different ways. As mentioned above, there is always a random
component of molecular motion. The entire fluid can be made to
move as well in an ordered motion (flow). The ordered motion is
superimposed, or added to, the normal random motion of the
molecules. At the molecular level, there is no distinction
between the random component and the ordered component. We
measure the pressure produced by the random component as the
static pressure. The pressure produced by the ordered motion is
called dynamic pressure. And Bernoulli's equation tells us that
the sum of the static and dynamic pressure is the total pressure
which we can also measure.
The Model
The five basic tenets of the kinetic-molecular theory are as

follows:
A gas is composed of molecules that are separated by average

distances that are much greater than the sizes of the molecules
themselves. The volume occupied by the molecules of the gas is
negligible compared to the volume of the gas itself.
The molecules of an ideal gas exert no attractive forces on each
other, or on the walls of the container.
2
The molecules are in constant random motion, and as material
bodies, they obey Newton's laws of motion. This means that the
molecules move in straight lines (see demo illustration at the
left) until they collide with each other or with the walls of the
container.
Collisions are perfectly elastic; when two molecules collide,
they change their directions and kinetic energies, but the total
kinetic energy is conserved. Collisions are not “sticky".
The average kinetic energy of the gas molecules is directly
proportional to the absolute temperature. Notice that the term
“average” is very important here; the velocities and kinetic
energies of individual molecules will span a wide range of
values, and some will even have zero velocity at a given instant.
This implies that all molecular motion would cease if the
temperature were reduced to absolute zero.
According to this model, most of the volume occupied by a gas
is empty space; this is the main feature that distinguishes gases
from condensed states of matter (liquids and solids) in which
neighboring molecules are constantly in contact. Gas molecules
are in rapid and continuous motion; at ordinary temperatures and
pressures their velocities are of the order of 0.1-1 km/sec and
each molecule experiences approximately 1010collisions with
other molecules every second.
If gases do in fact consist of widely-separated particles, then the

observable properties of gases must be explainable in terms of
the simple mechanics that govern the motions of the individual
3
molecules. The kinetic molecular theory makes it easy to see
why a gas should exert a pressure on the walls of a container.
Any surface in contact with the gas is constantly bombarded by
the molecules.
The kinetic theory of gases is a simple, historically significant

model of the thermodynamic behaviour of gases, with which
many principal concepts of thermodynamics were established.
The model describes a gas as a large number of identical sub
microscopic particles (atoms or molecules), all of which are in
constant, rapid, random motion. Their size is assumed to be
much smaller than the average distance between the particles.
The particles undergo random elastic collisions between
themselves and with the enclosing walls of the container. The
basic version of the model describes the ideal gas, and considers
no other interactions between the particles.
The kinetic theory of gases explains the macroscopic properties

of gases, such as volume, pressure, and temperature, as well as
transport properties such as viscosity, thermal conductivity and
mass diffusivity. The model also accounts for related
phenomena, such as Brownian motion.
Assumptions
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The application of kinetic theory to ideal gases makes the
following assumptions:
The gas consists of very small particles. This smallness of their

size is such that the sum of the volume of the individual gas
molecules is negligible compared to the volume of the container
of the gas. This is equivalent to stating that the average distance
separating the gas particles is large compared to their size, and
that the elapsed time of a collision between particles and the
container’s wall is negligible when compared to the time
between successive collisions.
The particles have the same mass.
The number of particles is so large that a statistical treatment of
the problem is well justified. This assumption is sometimes
referred to as the thermodynamic limit.
The rapidly moving particles constantly collide among
themselves and with the walls of the container. All these
collisions are perfectly elastic, which means the molecules are
perfect hard spheres.
Except during collisions, the interactions among molecules are
negligible. They exert no other forces on one another.
Thus, the dynamics of particle motion can be treated classically,
and the equations of motion are time-reversible.
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More modern developments relax these assumptions and are
based on the Boltzmann equation. These can accurately describe
the properties of dense gases, because they include the volume
of the particles. The necessary assumptions are the absence of
quantum effects, molecular chaos and small gradients in bulk
properties. Expansions to higher orders in the density are known
as varial expansions.
Transport properties
The kinetic theory of gases deals not only with gases in

thermodynamic equilibrium, but also very importantly with
gases not in thermodynamic equilibrium. This means using
Kinetic Theory to consider what are known as “transport
properties”, such as viscosity, thermal conductivity and mass
diffusivity.
At each collision, a molecule moving with momentum mv

strikes the surface. Since the collisions are elastic, the molecule
bounces back with the same velocity in the opposite direction.
This change in velocity ΔV is equivalent to an acceleration a;
according to Newton’s second law, a force f = ma is thus exerted
on the surface of area A exerting a pressure P = f/A.
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Kinetic Interpretation of Temperature
According to the kinetic molecular theory, the average kinetic
energy of an ideal gas is directly proportional to the absolute
temperature. Kinetic energy is the energy a body has by virtue of
its motion:
KE=mv^2/2
As the temperature of a gas rises, the average velocity of the
molecules will increase; a doubling of the temperature will
increase this velocity by a factor of four. Collisions with the
walls of the container will transfer more momentum, and thus
more kinetic energy, to the walls. If the walls are cooler than the
gas, they will get warmer, returning less kinetic energy to the
gas, and causing it to cool until thermal equilibrium is reached.
Because temperature depends on the average kinetic energy, the
concept of temperature only applies to a statistically meaningful
sample of molecules. We will have more to say about molecular
velocities and kinetic energies farther on.
Kinetic explanation of Boyle’s law: Boyle’s law is easily

explained by the kinetic molecular theory. The pressure of a gas
depends on the number of times per second that the molecules
strike the surface of the container. If we compress the gas to a
smaller volume, the same number of molecules are now acting
against a smaller surface area, so the number striking per unit of
area, and thus the pressure, is now greater.
7
Kinetic explanation of Charles’ law: Kinetic molecular
theory states that an increase in temperature raises the average
kinetic energy of the molecules. If the molecules are moving
more rapidly but the pressure remains the same, then the
molecules must stay farther apart, so that the increase in the rate
at which molecules collide with the surface of the container is
compensated for by a corresponding increase in the area of this
surface as the gas expands.
Kinetic explanation of Avogadro’s law: If we increase the

number of gas molecules in a closed container, more of them
will collide with the walls per unit time. If the pressure is to
remain constant, the volume must increase in proportion, so that
the molecules strike the walls less frequently, and over a larger
surface area.
Kinetic explanation of Dalton’s law: “Every gas is a

vacuum to every other gas”. This is the way Dalton stated what
we now know as his law of partial pressures. It simply means
that each gas present in a mixture of gases acts independently of
the others. This makes sense because of one of the fundamental
tenets of KMT theory that gas molecules have negligible
volumes. So Gas A in mixture of A and B acts as if Gas B were
not there at all. Each contributes its own pressure to the total
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pressure within the container, in proportion to the fraction of the
molecules it represents.
Derivation of the Ideal Gas Law
One of the triumphs of the kinetic molecular theory was the

derivation of the ideal gas law from simple mechanics in the late
nineteenth century. This is a beautiful example of how the
principles of elementary mechanics can be applied to a simple
model to develop a useful description of the behaviour of
macroscopic matter. We begin by recalling that the pressure of a
gas arises from the force exerted when molecules collide with
the walls of the container. This force can be found from
Newton’s law
F=ma=mdv/dt
In which v is the velocity component of the molecule in the
direction perpendicular to the wall and m is its mass.

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Gases can be studied by considering the small scale action of

individual molecules or by considering the large scale action of

The individual molecules possess the standard physical

In a solid, the location of the molecules relative to each other

The five basic tenets of the kinetic-molecular theory are as

A gas is composed of molecules that are separated by average

If gases do in fact consist of widely-separated particles, then the

The kinetic theory of gases is a simple, historically significant

The kinetic theory of gases explains the macroscopic properties

The gas consists of very small particles. This smallness of their

The kinetic theory of gases deals not only with gases in

At each collision, a molecule moving with momentum mv

Kinetic explanation of Boyle’s law: Boyle’s law is easily

Kinetic explanation of Avogadro’s law: If we increase the

Kinetic explanation of Dalton’s law: “Every gas is a

Derivation of the Ideal Gas Law

One of the triumphs of the kinetic molecular theory was the

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