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Le Chateliers principle and factors affecting equilibrium

Stoichiometric equation is used to predict the effect of changing concentration and
pressure while enthalpy change is used predict the effect of change in temperature.

Principle: Le Chateliers principle states that if one or more factors that affect an
equilibrium is changed, the position of equilibrium shifts in the direction which reduces
(opposes) the change.
Factors affecting the position of equilibrium
Le Chateliers principle is applied in order to explain the effect of change in pressure,
concentration or temperature on a system at equilibrium.
(a) Change in concentration:
If the concentration of one or more of the reactants or products is increased,
- The position of equilibrium shifts to the direction that consumes the added reactant(s)
or product(s) in order to oppose the change until equilibrium is restored.
If the concentration of one or more of the reactants or products is reduced,
- The position of equilibrium shifts to the direction that adds up the reduced reactant(s)
or product(s) in order to oppose the change until equilibrium is restored.
(b) Change in pressure:
Consider the equilibrium reaction: N2(g) + 3H2(g) 2NH3(g); H = -92KJmol-1.
In the above reaction there are more moles of gaseous reactants (1mol + 3mol = 4mol) than moles
of gaseous products (2mol).
If pressure is increased at constant temperature,
- molecules get closer and the position of equilibrium shifts to the direction of fewer gaseous
molecules in order to oppose the change until equilibrium is restored
If the pressure is decreased at constant temperature,
- molecules get further apart and the position of equilibrium shifts to the direction of more
gaseous molecules in order to oppose the change until equilibrium is restored

If reactant and products have equal number of moles e.g. H2(g) + I2(g) 2HI(g); then
change in pressure has no effect on equilibrium position.
In a system containing a mixture of solid and gases e.g. CaCO3(g) CaO(s) + CO2(g); or a mixture
liquids and gases, only the gases determine how pressure affect the position of equilibrium.

(c) Change in temperature:

If the temperature of an endothermic reaction e.g. 2HI (g) H2(g) + I2(g), H = +9.6KJmol-1 is

increased,
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The energy of the surroundings increases and the position of equilibrium shifts to the direction
which absorbs the added energy i.e. the endothermic reaction in order to oppose the change.
If the temperature of an exothermic reaction e.g. N2(g) + 3H2(g) 2NH3(g); H = -92KJmol-1, is

decreased,
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The energy of the surroundings decreases and the position of equilibrium shifts to the
direction which releases energy i.e. the exothermic reaction in order to oppose the change.

(d) Adding a catalyst:

Adding a catalyst to a reaction in a state of dynamic equilibrium has no effect on the position of
equilibrium. This is because a catalyst increases the rates of the forward and backward reactions
equally. A catalyst can only reduce the time taken for a reaction to reach equilibrium but has no
effect on a reaction already at equilibrium.

Equilibrium and ammonia production (Haber Process)

The equilibrium equation for the industrial manufacture of ammonia (the Haber process) is:
N2(g) + 3H2(g) 2NH3(g); H = - 92kJmol-1.
- Due to the unreactive nature of nitrogen, a high amount of energy is needed. Increasing the
temperature shifts the equilibrium position to the left as the forward reaction is exothermic. Thus
high temperatures decrease the yield of ammonia. Too low temperature makes the rate to be slow.
- The yield of ammonia is increased by using high pressures. High pressures shift the equilibrium
position to the right. Very high pressures increase the cost of the plant, and low pressures make the
reaction very slow.
- A catalyst can be used to overcome the problem of the low rate of reaction. An iron catalyst is
used, with small amounts of K, Mg, Al, and Si oxides that improve the efficiency of the catalyst.
- Removing ammonia, shifts the equilibrium position to the right in order to replace the removed
ammonia. This increases the yield of ammonia.
- Rapid expansion is used to cool the mixture. Ammonia liquefies, while unreacted nitrogen and
hydrogen are recycled into the reaction vessel.
Conditions are:
Pressure of 1.50 x 107Pa, temperature of 450C, Finely divided or porous iron catalyst.
The contact process
- In this process, sulphuric acid is manufactured from sulphur. Sulphur is burned in air at 1000C to
make SO2.
S(s) + O2(g) SO2(g)
- Sulphur dioxide is converted into Sulphur trioxide by using vanadium (v) oxide catalyst.
2SO2(g) + O2(g) 2SO3(g);
H = -197 kJ/mol
This is the main equilibrium reaction in the contact process.
- High temperatures shift position of equilibrium to the left thereby decreasing the yield of sulphur
trioxide. Too low temperature makes the rate to be slow.
- The yield of sulphur trioxide is increased at high pressures. High pressures shift the equilibrium
position to the right. Very high pressures increase the cost of the plant, and low pressures make the
reaction very slow.
- A catalyst can be used to overcome the problem of the low rate of reaction. Vanadium (V) oxide
catalyst is used.
- Removing sulphur trioxide by absorbing it in 98% sulphuric acid, shifts the equilibrium position to
the right in order to replace the removed sulphur trioxide. This increases the yield of sulphur
trioxide.
- Sulphur trioxide is dissolved in sulphuric acid to make oleum (H2S2O7) which is then diluted into
sulphuric acid.
SO3(g) + H2SO4(l) H2S2O7(l)
H2S2O7(l) + H2O 2H2SO4(l)
Conditions are:
- V2O5 catalyst
- temperature of 450C,
- pressure just above atmospheric pressure.
These conditions used to convert sulphur dioxide into sulphur trioxide are a compromise. Higher
yields of SO3 are produced when using air in excess, forcing equilibrium to the right.
Uses of sulphuric acid include:
- The manufacture of paints
- the manufacture of detergents and soaps
- the manufacture of phosphate fertilizers
- The manufacture of dyestuff