Explaining the shape of titration curves

1. Strong acid – strong base titrations

Imagine we are titrating a strong acid such as hydrochloric acid against a

strong base such as sodium hydroxide

HCl (aq) + NaOH (aq) ⇾ H2O (l) + NaCl (aq)

And removing the spectator ions leaves us with the ionic equation for
neutralisation

H+ (aq) + OH– (aq) ⇾ H2O (l)

When [H+(aq)] = [OH–(aq)] neutralisation is complete – this is known as

the equivalence point and in the case of a titration between a strong acid
and and a strong base, this will also mean we have a solution with a pH of
7.

A graph showing the change in pH during a titration is called a titration

curve.
2. Weak acid – strong base titrations

For example, titrating sodium hydroxide against ethanoic acid

CH3COOH (aq) + NaOH (aq) ⇾ CH3COO–Na+ (aq) + H2O (l)

Why has the first part of the curve changed?

Weak acids are not fully dissociated in solution so to begin with we have a
lower [H+], a higher starting pH and the presence of both ethanoic acid
molecule and ethanoate ions in an equilibrium system.

CH3COOH (aq) ⇌ CH3COO– (aq) + H+ (aq)

As both the acid (HA) and the conjugate base (A–) are present, the solution
acts as a buffer initially when the OH– ions are added. These OH– ions react
with the H+ ions causing the equilibrium position to shift to the right,
generating more H+. As a result, the H+ ion concentration and hence the
pH changes very slowly at the start of the titration.
Why is the equivalence point greater than pH7?

CH3COOH (aq) + NaOH (aq) ⇾ CH3COO–Na+ (aq) + H2O (l)

At neutralisation, [H+(aq)] = [OH–(aq)] and the reaction is complete, but the

ethanoate ion hydrolyses / reacts with the water

CH3COO– (aq) + H2O (l) ⇌ CH3COOH (aq) + OH– (aq)

The presence of hydroxide ions means the neutralised solution (and

equivalence point) is alkaline.

3. Strong acid – weak base titrations

In these titrations, the acid is added to the base …

HCl (aq) + NH3 (aq) ⇾ NH4Cl (aq)

Why has the first part of the curve changed?

At the beginning of the titration pH changes more slowly as the strong

acid is added (compared with a strong acid – strong base titration curve).
Once again, the initial weak base solution is actually a buffer system
containing the weak base and its conjugate acid.

NH3 (aq) + H2O (l) ⇌ NH4+ (aq) + OH- (aq)

As H+ are added they react with the OH– present, shifting the equilibrium
position to the right: pH is maintained as the H+ concentration hardly
changes.

Why is the equivalence point lower than pH7?

The equivalence point is lower than pH7 because although once the
neutralisation reaction is complete and [H+(aq)] = [OH–(aq)], the ammonium
chloride salt formed hydrolyses / reacts with water producing acidic
H3O+ ions.

NH4+ (aq) + H2O (l) ⇌ NH3 (aq) + H3O+ (aq)