Back titrations can be used for many reasons, including: when the sample is not soluble in water, when

the
sample contains impurities that interfere with forward titration, or when the end-point is more easily identified than
in forward titration.

Example
Consider using titration to measure the amount of aspirin in a solution. Using titration it would be difficult to
identify the end point because aspirin is a weak acid and reactions may proceed slowly.

Using back titration the end-point is more easily recognised in this reaction, as it is a reaction between a strong
base and a strong acid. This type of reaction occurs at a high rate and thus produces an end-point which is
abrupt and easily seen.

The titration curve for a strong acid with a strong alkali shows that the equivalence point occurs at pH 7. This
means that the indicator phenolphthalein can be used. The end-point will be seen when the pink solution
produced by the adding of phenolphthalein fades to colourless.

The first stage of this reaction is that of alkaline hydrolysis. This involves reacting the aspirin solution with a
measured amount of sodium hydroxide; an amount that will exceed the amount of aspirin present. Because the
hydrolysis reaction occurs at a very low rate at room temperature it will be heated to increase the reaction rate.
CH3COOC6H4COOH + 2NaOH ---> CH3COO.Na + HOC6H4COO.Na + H2O
Sodium Ethanoate + Sodium-
2-hydroxybenzoate + Water

The second stage then involves back titration of the hydrolysed sodium hydroxide solution with hydrochloric
acid. This process reacts the excess sodium hydroxide with hydrochloric acid.
NaOH + HCl ----> NaCl + H2O

Sodium Hydrochloric ---> Sodium Water

Hydroxide acid Chloride

By the method of back titration the amount of hydrochloric acid needed to neutralise the unreacted sodium
hydroxide in the solution can be determined. Knowing this and the amount of sodium hydroxide that was added
the amount of aspirin that reacted with the sodium hydroxide can be determined.

The active ingredient in Aspirin you’re looking for is an acid

so it should be possible to titrate it with NaOH to define its concentration,

C6H4(OCOCH3)COOH + NaOH ↓ C6H4(OCOCH3)COO-Na+ + H2O

But in the case of aspirin this reaction is slow and there is also some hydrolysis going
on. So it is impractical to titrate it directly with a base versus phenolphthalein indicator.
Therefore the aspirin solution is first reacted with an overdose of an NaOH solution with
a known concentration and of a measured quantity.

Then one can let it react totally , then titrate that solution back with a known
concentration of an acid, like H2SO4. this second titration(/reaction) will determine not
the aspirin concentration but the amount of NaOH left over after the first reaction.

The rest is just math you know how much ( & at which concentration) H2SO4 was used
→ so you know how much NaOH that not reacted with the aspirin-acid you have
neutralized, and you know how much of total NaOH was used, so the total amount of
NaOH minus the back titrated amount is the amount that was needed to compensate
the acid from the aspirin . So now you know how much acid came from the Aspirin. Since
you also determined / know the mass of the aspirin, you’ll know now how much the
concentration of the acid in the pill was, or mg active ingredient per pill.