Titration of a Carbonate

The figure below shows the pH changes during the titration of sodium carbonate with hydrochloric
acid.
A few drops of thymol blue indicator are added to 25 cm3 of 0.10 mol dm 3 sodium carbonate
solution and the mixture is titrated with 0.20 mol dm 3 hydrochloric acid until it becomes
colourless. Some methyl orange is now added and the titration is continued until the solution again
changes colour. The diagram shows how the pH changes during the titration and also shows the pH
range of some indicators.

thymol blue

bromothymol blue
bromophenol blue
methyl orange

The reaction of Na2CO3(aq) and HCl (aq) can be represented in two stages: (a) and (b)

(a) Na2CO3(aq) + HCl(aq)

NaHCO3(aq) + NaCl(aq)

(b) NaHCO3(aq) + HCl(aq)

NaCl (aq) + CO2(g) + H2O(l)

Na2CO3(aq) + 2HCl(aq)

Indicator to exhibit
completion of reaction
thymol blue
methyl orange

2NaCl(aq) + CO2(g) + H2O(l)

If thymol blue is used as the indicator, it changes colour from blue (basic) to pale green/greenyellow (end point) (yellow at acidic) when reaction (a) is completed, i.e. when sodium carbonate
is only half-neutralised.
If methyl orange is used as the indicator, it changes colour from yellow (basic) to orange(end
point) (red is acidic) when reaction (b) is completed, i.e. when sodium carbonate is completely
neutralized to give CO2 and H2O.
From the stoichiometries of the two reactions, it can be seen that
if volume of HCl required for reaction (a) = x cm3,
then volume of HCl required for reaction (b) = x cm3,
and
volume of HCl required when using phenolphthalein as indicator = x cm3
volume of HCl required when using methyl orange as indicator = 2x cm3
Use can be made of this two stage titration to estimate the sodium carbonate and sodium hydrogen
carbonate.

The Double Indicator Method

A mixture of sodium hydroxide and sodium carbonate can be analysed by the double indicator
method.
The reaction of sodium hydroxide and sodium carbonate with hydrochloric acid are represented by
the following equations:
Reaction
1
2(a)
2(b)

NaOH + HCl
(x ymol)
Na2CO3 + HCl
(y mol)
NaHCO3 + HCl
(y mol)

NaCl + H2O

Indicator to show the

completion of reaction
any indicator

NaHCO3 + NaCl
NaCl + CO2 + H2O

thymol blue
methyl orange

If hydrochloric acid is added to a mixture of sodium hydroxide and sodium carbonate and using
thymol blue as the indicator is discharged when reactions 1 and 2(a) are completed.
If methyl orange is then added and the titration continued, a further amount of hydrochloric acid is
required to bring about a colour change. This amount of acid is required for reaction 2(b).
Amount of HCl used with thymol blue as indicator = x mol
Further amount of HCl used when methyl orange as indicator = y mol
Amount of HCl used for the complete titration neutralisation of Na2CO3 = 2y mol
Amount of Na2CO3 reacted = ()(amount of HCl which reacted with Na2CO3) = ()(2y) = y mol
Amount of HCl which reacted with NaOH = amount of NaOH present
= x y mol
The concentrations of sodium hydroxide and sodium carbonate in the solution can then be
calculated from the data obtained.

Example 1
25.0 cm3 of a solution containing sodium hydroxide and sodium carbonate was titrated against
0.100 mol dm-3 hydrochloric acid, using thymol blue as indicator. After 30.00 cm3 of acid has
been used, the indicator was pale green. Methyl orange was added and a further 12.50 cm3 of
hydrochloric acid were needed to turn the indicator orange. Calculate the concentrations of sodium
hydroxide and sodium carbonate in the solution.
Solution
With methyl orange as indicator ,
NaHCO3(aq) + HCl(aq)

NaCl (aq) + CO2(g) + H2O(l)

Amount of HCl which reacted with NaHCO3 =

=
Hence amount of NaHCO3 reacted = Amount of HCl reacted =
Since one mole of NaHCO3 comes from one mole of Na2CO3,
amount of Na2CO3 reacted = amount of NaHCO3 reacted =
Hence concentration of Na2CO3 in the solution =
=
With thymol blue as indicator,
NaOH (aq) + HCl (aq)
Na2CO3 (aq) + HCl (aq)

NaCl (aq) + H2O (l)

NaHCO3 (aq) + NaCl (aq)

Amount of HCl which reacted with both Na2CO3 and NaOH =

=
Amount of HCl reacted with Na2CO3 to give = Amount of HCl which reacted with
NaHCO3
NaHCO3
=
Amount of HCl which reacted with NaOH =
=
Concentration of NaOH in the solution =

Example 2:
A 25.0 cm3 portion of a solution containing sodium carbonate and sodium hydrogen carbonate
needed 22.50 cm3 of a solution of hydrochloric acid of concentration 0.100 mol dm-3 to pale green
of thymol blue. On addition of methyl orange, a further 28.50 cm3 of the acid was needed to turn
this indicator to its neutral colour. Calculate the concentrations of sodium carbonate and sodium
hydrogen carbonate in the solution.
Solution
With thymol blue as indicator,
Na2CO3(aq) + HCl(aq)

NaHCO3(aq) + NaCl(aq)

Amount of HCl which reacted with Na2CO3 to form NaHCO3 =

Hence amount of Na2CO3 reacted = amount of HCl reacted =
concentration of Na2CO3 in the solution =
With methyl orange as indicator,

NaHCO3(aq) + HCl(aq)

NaCl (aq) + CO2(g) + H2O(l)

Amount of HCl which reacted with all the NaHCO3 =

=
Amount of HCl which reacted with NaHCO3 from Na2CO3 =
Hence amount of HCl used to react with NaHCO3 initially present =
=
concentration of NaHCO3 in the given solution =
=