Equilibrium and Le Chatelier’s principle.

Equilibrium is a state of a system where there is no observable change in the properties of the system
with respect to time.

The balanced see-saw is an example of static equilibrium, since the see-saw is at rest or stationary.

The saturated solution is an example of dynamic equilibrium since the salt particles are dissolving and
depositing at the same rate, i.e. there is constant motion in the system.

A volatile liquid in an air-tight container is also an example of a system that can exist in a state of
dynamic equilibrium.

In general, dynamic equilibrium can occur during a physical change or a chemical change that is
reversible. Dynamic equilibrium involving a physical change is referred to as physical equilibrium while
that involving a chemical change is known as chemical equilibrium. In a physical equilibrium, there is no
change in the composition of the substances involved.

In a chemical equilibrium, the reactants undergo a change in composition to form the products, which in
turn are reconverted to the original reactants at the same rate.

LE CHATELIER’S PRINCIPLE

Le Chatelier's Principle states that if an external constraint such as a change in temperature, pressure or
concentration, is imposed on a chemical system in equilibrium, the equilibrium will shift so as to annul or
neutralize the constraint.

This principle is of great importance in chemical industry because it can help to

i. define the optimum conditions for the chemical processes employed in industry;

ii. reduce undesirable reversibility;

iii. predict the effect of an altered factor on the equilibrium position of an untried reaction.

Teacher explains the factors affecting equilibrium of chemical reactions.

Effect of a change in temperature

In the following thermochemical equations,

A + B--C

AH = +ve

X+ YPZ

AH = -ve
• if AH is positive, the forward reaction is endothermic, and the backward reaction is exothermic;

• if AH is negative, the forward reaction is exothermic, and the backward reaction is endothermic.

If a chemical system is in equilibrium and the temperature is lowered, then according to Le Chatelier's
Principle, the equilibrium position will shift so as to annul the cooling effect by releasing more heat.

Conversely, if the temperature is raised, then the equilibrium position will shift so as to annul the heating
effect by absorbing more heat. In the following reversible reaction, the forward reaction is endothermic.

Increasing the temperature of the system will shift the equilibrium position to the right, favouring the
forward reaction, i.e. product formation.

Hence, the value of the equilibrium constant K also increases. So, for a given reversible reaction, a higher
value of K would mean a greater yield of product(s).

Lowering the temperature of the system will shift the equilibrium position to the left, favouring the
backward reaction, i.e. reactant formation.

This results in a lowering of the K value. So, for a given reversible reaction a lower value of K would mean
a greater yield of reactant(s).

Effect of a change in pressure

For a change in pressure to affect a chemical system in equilibrium,

one of the reactants or products in the reversible reaction must be gaseous;

the total number of moles of gaseous molecules on the left side of the equation must be different from
the total number of moles of gaseous molecules on the right side.

Effect of a change in concentration In an equilibrium mixture, there is a balance between the

concentrations of the reactants and the products, i.e. these concentrations are in a definite ratio which
depends on the conditions of the reaction. If more reactants are introduced into the equilibrium system,
the balance will be upset. In order to relieve this constraint (i.e. the increase in the concentration of
reactants), the equilibrium position will shift to the right, favouring the forward reaction. This results in a
proportional increase in the concentration of the products, and so the equilibrium constant remains
unchanged.