Kinetic Theory of Gases

➢ The Gas Laws

Experiments involving gases have revealed that four variables are needed to define the physical
condition or state of a gas. These 4 variables are: temperature (T), pressure (P), volume (V)
and the amount of gas present (usually expressed as no. of moles, n). The equations that express
the relationships among T, P, V and n are known as the Gas Laws.

▪ Boyle’s Law (the pressure-volume relationship)

The volume of a fixed quantity of gas maintained at a constant temperature is inversely
proportional to the pressure.
Vα1 or: V = constant x 1 or: pV = constant
P P
i.e. As volume increases, pressure decreases; as volume decreases, pressure increases.

▪ Charles’ Law (the temperature-volume relationship)

The volume of a fixed amount of gas maintained at a constant pressure is directly proportional to
its absolute temperature (i.e. its temperature in Kelvin).
VαT or: V = constant x T
i.e. As temperature increases, volume increases; as temperature decreases, volume decreases.

▪ Avogadro’s Law (the quantity-volume relationship)

The volume of a gas maintained at constant temperature and pressure is directly proportional to
the number of moles of the gas.
Vαn or: V = constant x n
i.e. If no. of mol increases, volume increases; if no. of mol decreases, volume decreases.

If: Vα1
P
VαT
Vαn
We can combine these 3 relationships/ gas laws to create a more general gas law:
V α nT
P
Or: V = constant x nT
P
If we let R be the proportionality constant:
V = R nT
P

Rearranging this relationship we obtain:

The Ideal Gas Equation:

PV = nRT where: P = pressure (atm)
V = volume (L)
n = number of moles
R = universal gas constant (0.0821 L atm mol-1 K-1)
T = absolute temperature (K)

In other words, the ideal gas equation is an amalgamation of the 3 gas laws:
Boyle’s Law
Charles’ Law
Avogadro’s Law

Note that an ideal gas is a hypothetical/ theoretical gas whose pressure, volume and
temperature behaviour are described completely by the ideal gas equation, i.e. ideal gases obey
this equation.
e.g. Calcium carbonate, CaCO3 (s) decomposes on heating to produce carbon dioxide, CO2(g).
The CO2 is collected in a 250 mL flask and has a pressure of 1.3 atm at a temperature of
31oC. How many moles of CO2 were generated?

P = 1.3 atm
V = 250 mL = 0.25 L
T = 31oC = 304 K

PV = nRT
(1.3 atm)(0.25 L) = n(0.0821 L atm mol-1 K-1)(304 K)
n = 0.013 mol

Therefore, 0.013 mol of CO2 were produced from the decomposition of the sample of CaCO3.

➢ Kinetic Theory of Gases

The ideal gas equation describes how gases behave but it does not explain why they behave as
they do. To understand the physical properties of gases, we need a theory to describe what
happens to gas particles as experimental conditions such as temperature or pressure change.
This theory is called the Kinetic Molecular Theory or Kinetic Theory of Gases.
This theory consists of some general postulates that describe and define the properties and
behaviour of ideal gases:
▪ Gases consist of a large number of molecules that are in constant random motion.
▪ The combined volume of all the individual gas molecules of a sample is negligible
compared to the volume of their container.
▪ The attractive and repulsive forces between gaseous molecules is negligible.
▪ The average kinetic energy of the gaseous molecules at a given/ fixed temperature
remains constant over time.
▪ The average kinetic energy of the gaseous molecules is directly proportional to the
absolute temperature of the system.
The Kinetic Theory explains both pressure and temperature:
The pressure of a gas is caused by collisions of the molecules with the walls of the container.
The magnitude of the pressure is determined by how often and how forcefully the molecules
strike the walls.

The absolute temperature of a gas is a measure of the average kinetic energy of its molecules.
If 2 different gases are at the same temperature, their molecules have the same average kinetic
energy. If the absolute temperature of the gas is doubled, the average kinetic energy of its
molecules doubles as well. Thus, motion of gas molecules increases with increasing temperature.

➢ Average Kinetic Energy

For a gas, the average kinetic energy may be calculated from the following expression:
E = ½ mu2 where: E = average kinetic energy (J)
m = mass of 1 gas molecule (kg)
u = root mean square speed of a gaseous molecule (m s-1)

Although the molecules in a gas have an average kinetic energy and hence an average speed, the
individual molecules are moving at varying speeds. The moving molecules collide frequently
with other molecules and hence, the molecules at any instant have a wide range of speeds.

The root mean square speed, u of the molecules at a given temperature is the speed of a
molecule possessing average kinetic energy. The root mean square speed is very similar to the
average speed of the molecules (but there is still a numerical difference between the 2 values).

u = 3RT ½ where: u = root mean square speed (m s-1)

M R = 8.314 J mol-1 K-1
T = temperature (K)
M = molecular mass of the gas (kg)

1 J = 1 kg m2 s-2

The root mean square speed is important because the average kinetic energy of the gas
molecules in the sample is related directly to u (see equation above to calculate E). Thus, as
temperature increases, root mean square speed increases and average kinetic energy also
increases.
Calculating root mean square speed
e.g. Calculate the root mean square speed of an N2 molecule at 25oC.

R = 8.314 J mol-1 K-1 = 8.314 kg m2 s-2 mol-1 K-1

T = 25oC = 298 K
M = 28 g mol-1 = 0.028 kg mol-1 (Molar Mass of N2: 28 g mol-1)

u = 3RT ½

u = 3(8.314 kg m2 s-2 mol-1 K-1)(298 K) ½

= 515 m s-1
0.028 kg mol-1

Real gases and their deviation from ideal behaviour

Although the ideal gas equation is a very useful description of gases, all real gases fail to obey
the relationship to some degree.
At high pressures, the deviation from ideal behaviour is large. Real gases therefore, do not
behave ideally at high (external) pressures. At lower pressures, deviation from ideal behaviour is
small so the ideal gas equation can be used.
The deviation from ideal behaviour also depends on temperature. At low temperatures, the
deviation from ideal behaviour is large. Real gases therefore, do not behave ideally at low
temperatures. As temperature increases, the behaviour of a real gas more nearly approaches that
of an ideal gas.

No real gas exhibits ideal behaviour throughout its entire range of temperature and pressure.
Gases deviate significantly from ideal behaviour under conditions of high pressure and low
temperature, i.e. conditions under which the gas is about to liquefy.

Real gases differ from ideal gases in 2 significant ways:

Real gases have a finite and significant volume.
Real gases have attractive forces between gaseous molecules.

Consider also the effect if the volume of the container holding a sample of gas is decreased (i.e.
the container is made smaller; this means we are increasing external pressure):
The combined volume of the gas molecules now becomes significant relative to the volume
of their container.
The distance between gaseous molecules decreases and hence attractive forces become
relatively significant.
As a result of the gaseous molecules occupying less space or having less space to occupy, the
number of collisions between the gaseous molecules with each other will increase i.e. it is more
likely that the molecules will collide with each other before colliding with the walls of the
container i.e. the frequency of collision with the container walls will decrease. By definition this
will results in a drop in the pressure exerted by the gas. (Recall that the pressure of a gas is how
frequently its particles hit the walls of the container.)
In addition, lowering temperature will also result in attractive forces among gas molecules
beginning to take hold, since their kinetic energy will be reduced.
Consider then how this affects the pressure (P) and volume (V) of a real gas relative to an ideal
one:-
The pressure of a real gas is less than that of an ideal gas:
Preal < Pideal
The volume of a real gas is greater than that of an ideal gas:
Vreal > Videal

How then would one apply the ideal gas equation (PV = nRT) to a real gas?

Correction factors to increase the pressure and reduce the volume (i.e. to idealize the real gas)
must be applied.
The ideal gas equation is corrected to account for the effects of attractive forces between
gas molecules and for molecular volumes. Two constants, a and b are used to do this.

Constant a is a measure of how strongly the gas molecules attract each other.
Constant b is a measure of the volume occupied by the gas molecules themselves.
a and b are called van de Waals constants.

The ideal gas equation then becomes modified to the van de Waals gas equation:
P + n2a (V – nb) = nRT
V2

‘a’ is the measure of the attractive forces between real gas molecules.
‘b’ is a measure of the small but finite volume occupied by real gas molecules.
P and V represent the pressure and volume of the real gas i.e. they are really: Preal and Vreal.

Therefore:
Pideal = Preal + n2a
V2

Videal = (Vreal – nb)

e.g. Using the van de Waals gas equation

If 1.00 mol of Cl2 gas was confined to 22.41 L at 0.0oC, use the van de Waals equation and the
constants: a = 6.49 L2 atm mol-2 and b = 0.0562 L mol-1 to calculate the pressure that the gas
would exert at this temperature.

P + n2a (V – nb) = nRT

V2

P + (1.00 mol)2(6.49 L2 atm mol-2) 22.41 L – (1.00 mol)(0.0562 L mol-1) =

(22.41 L)2
(1.00 mol)(0.0821 L atm mol-1 K-1)(273 K)

(P + 0.0129 atm)(22.3538 L) = 22.4133 L atm

P + 0.0129 atm = 1 atm
P = 0.990 atm
Compare this with:
PV = nRT i.e. This is the
pressure of Cl2 if we
P(22.41 L) = 1.00 mol(0.0821 L atm mol-1 K-1)(273 K) assumed it was an
P = 1 atm ideal gas instead of a
real gas.

0.990 atm < 1 atm

Preal < Pideal

Summary:
Ideal gas – a hypothetical/ theoretical gas having certain characteristics; its pressure and volume
can be calculated using the ideal gas equation
Ideal gases deviate from ideal behaviour and act more like real gases under the conditions of:
high pressure and low temperature. Also if the volume of the container changes e.g. decreases,
ideal gases can act like real gases.
Real gases have characteristics opposite to ideal gases; its pressure and volume can be calculated
using the Van de Waals’ gas equation
Ideal gas Real gas
Negligible volume Significant volume
Negligible forces of attraction bet. particles Significant forces of attraction bet. particles
Pressure of gas inside container is higher (due Pressure of gas inside container is lower (due
to more collisions with the walls) as particles to less collisions with the walls) as particles are
are less attracted to each other more attracted to each other

To modify the ideal gas equation to fit real gases, correction factors: + n2a & (-nb)
V2
were inserted into the ideal gas equation since:
Preal < Pideal (Preal is lower so a value/ factor must be added to get to the ideal value)
Vreal > Videal (Vreal is higher so a value/factor must be deducted to get to the ideal value)

i.e. Pideal Videal = n R T Ideal Gas Equation

Preal + n2a (Vreal – nb) = n R T Van de Waals’ Gas

V2 Equation