Kinetic Theory of Gases

The kinetic theory is a model proposed to help in our understanding of the behaviour of gases.
This is important as gases are one of the most pervasive aspects of our environment and we
continually exist with constant exposure to gases of all forms.
Some of the distinct and important characteristics of gases include:

• They are high compressible

• They are thermally expandable
• They have high viscosity; gases flow much easier than liquids.
• Most have low densities
• They are infinitely miscible.

The Kinetic theory is based on the following assumptions of an Ideal Gas:

1. A gas consists of very small particles (atoms/molecules) in continuous random motion.

2. The size of the particles are negligible compared with the space they occupy.
3. There are no intermolecular forces (attractive or repulsive forces) between particles,
except during collisions - gas particles act independently of each other.
4. Collisions of gas particles with themselves or the walls of the container are perfectly
elastic
5. The average kinetic energy of the gas particles is proportional to the absolute
temperature of the sample.

Real and Ideal gases

A real gas molecule has a shape and a finite size. It can interact with other real gas molecules
(intermolecular forces). An ideal gas molecule is imaginary and is a point without shape and it
occupies very small amounts of space. There are no ideal gas molecules, only real gas molecules.
However, under the conditions of very high Temperature and very low Pressure, real gas
molecules come very close to acting like ideal gas molecules.
The kinetic theory of gases is a single set of descriptive characteristics of an ideal gas. As
mentioned, the conditions required for a gas to approach ideal behaviour are high temperature
and low pressure. Under these conditions, intermolecular forces are minimised to be almost
negligible. The volume of space occupied by an ideal gas is also considered to be negligible since
it is assumed that the gas molecules have no volume of their own.
Real gases deviate from this behaviour because the gas molecules do have a volume of their own
and intermolecular forces of attraction to exist. These deviations are large for large gas molecules

1
and small for small gas molecules. The deviations also increase as the Temperature of the gas
decreases and the pressure of the gas increases.

Deviations from ideal Behaviour

A real gas deviates from an ‘ideal gas’ in two important ways as describe above:
1. Intermolecular forces exist
2. Volume of their particles is not negligible compared to the space they occupy.

For an ideal gas there is no force of attraction between gas particles or between the particles and
the walls of the container. This is valid at low pressures because the particles are so far apart. At
high pressures particles are pushed closer to each other and attractive forces become significant;
as a result, the assumption becomes invalid. Attractions reduce the frequency of collisions with
the walls of the container and therefore a real gas will exert a lower pressure.
This can be shown graphically by finding the values of PV for a real gas at various temperatures
and pressures. The gas law PV = nRT implies that the product PV will always be the same.

For an ideal gas, pV = nRT. If pV and nRT are the same, and you divide one by the other, then the
answer will, of course, be 1. For real gases, pV doesn't equal nRT, and so the value will be
something different.

The term pV / nRT is called the compression factor. The graphs below show how this varies for
nitrogen as you change the temperature and the pressure.

2
If nitrogen was an ideal gas under all conditions of temperature and pressure, every one of these
curves would be a horizontal straight line showing a compression factor of 1. That's obviously not
true!

Points to note

• At low pressures of about 100 kPa (just a bit less than 1 atmosphere), the compression
factor is close to 1. Nitrogen approximates to ideal behaviour at ordinary pressures.
• The non-ideal behaviour gets worse at lower temperatures. For temperatures of 300 or
400 K, the compression factor is close to 1 over quite a large pressure range. The nitrogen
becomes more ideal over a greater pressure range as the temperature rises.
• The non-ideal behaviour gets worse at higher pressures.
• There must be at least two different effects causing these deviations. There must be at
least one effect causing the pV / nRT ratio to be too low, especially at low temperatures.
And there must be at least one effect causing it to get too high as pressure increases. We
will explore those effects in a while.

At high pressure, deviation from ideal behaviour is large and is different for each gas. At low
pressures, the deviation from ideal behaviour is small. At high pressures, PV is always above the
ideal value. This is because the molecules are crammed together, and the total molecular volume
is a significant fraction of the total volume. PV exhibits a positive deviation from the ideal. As the
temperature falls, the molecules approaching the walls and about to exert pressure on them are
held back by the attraction of molecules in the bulk. The lower the temperature the more
noticeable this effect becomes. PV exhibits a negative deviation from the ideal.
I

3
It is easy to say that gases become less ideal at low temperatures, but what counts as a low
temperature varies from gas to gas. The closer you get to to the temperature at which the gas
would turn into a liquid (or, in the case of carbon dioxide, a solid), the more non-ideal the gas
becomes. In general, gases deviate significantly from ideal behavior at temperatures near their
liquefaction point.