Reversible reactions and equilibrium

Recap of previous knowledge

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What do you understand by the term brine?

Write down an equation for the cathodic and anodic reaction when brine is electrolysed.
State two possible observations made when crude (impure) copper is purified by
electrolysis

Reversible reactions and quilibrium

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Some reactions can occur from either direction. Such reactions are said to be reversible.
For reversible reactions, products can either be converted to reactants or reactants converted
product.
Such a reaction in a closed system will gradually show a decrease in rate of forward reaction
and a gradual increase rate of backward reaction until a state of dynamic equilibrium is
attained.
A reversible reaction is not necessary a reaction in dynamic equilibrium unless it takes place in
a closed system with both the forward and backward reactions occur at the same rate.

The sign in a chemical reaction indicates that the reaction is reversible or in equilibrium.
Chemical reactions such as N2(g) + 3H2(g) 2NH3(g) with the sign between the reactants and
the products are called reversible reactions or equilibrium reactions.
In the above reaction,
N2(g) + 3H2(g) 2NH3(g) is called the forward reaction and
2NH3(g) N2(g) + 3H2(g) is called the backward reaction.
Definitions:
- A Reversible reaction is defined as a reaction in which the products can react together to
reform the original reactants.
- Dynamic equilibrium is defined as a state in a reversible reaction in a closed system where
the concentrations of the reactants and the products are constant as a result of equal rate of
forward and the reverse reactions.

Characteristics of dynamic equilibrium

Thus characteristics of dynamic equilibrium are:
- It is dynamic at molecular and ionic levels:
This means that both forward and the reverse reacts continue to occur without stopping.
- Both forward and backward reactions occur at the same rate
This means that reactants change to products and products change back to reactants at the
same rate.
- A closed system is required
This is to prevent the exchange of matter between system and surroundings.
- Macroscopic properties remain constant
This is because both forward and reverse reactions occur at the same rate.
Macroscopic properties refer to observable properties such as colour, mass or concentration of a
substance that can easily be measured.

The following conditions are necessary for a system to attain chemical equilibrium:
- The system must be closed
- The chemical reaction must be reversible.
Examples of reversible reactions that attain equilibrium in a closed system

CaCO3(s) CaO(s) + CO2(g),

2SO2(g) + O2(g) 2SO3(g),

The concentrations or partial pressures of reactants and products remain constant do not
change with time in a state of dynamic equilibrium because the rate of the forward reaction is
equal to the rate of the backward reaction. For a chemical reaction such as R(g) P(g) or R(aq)
P(aq), at equilibrium, the amounts of reactant (R) and product (P) may be the same as illustrated
in Fig 9.1a or different as illustrated in Fig 9.1b and Fig 9.1c below.

In each of the graphs above, equilibrium is attained at time t. When is used between
reactants and products, it implies that the reverse reaction is rarely achieved or its occurrence
is negligible e.g. H+(aq) + OH (aq) H2O(l).
Changing the position of equilibrium
Every reversible reaction has a position of equilibrium once it has reached a state of dynamic
equilibrium.
Definition: An Equilibrium position is defined as the relative proportion of products to reactants for
an equilibrium reaction in a closed system.
Important notes about equilibrium position:
- Equilibrium position is said to lie to the right when there is a large amount of products in the
system compared to the amount of reactants and a large equilibrium constant.
- Equilibrium position is said to lie to the left when there is a large amount of reactants in the
system compared to the amount of products and a small equilibrium constant.
- Equilibrium position is said to shift to the right when the forward reaction is taking place faster
than the reverse reaction.
- Equilibrium position is said to shift to the left when the reverse reaction is taking place faster than
the forward reaction.