EXERCISE 6: ANALYSIS OF CARBONATE MIXTURES BY DOUBLE

INDICATOR TITRATIONS
I.

OBJECTIVES
At the end of this exercise, the student should be able to:
1. Determine qualitatively and quantitatively the composition of a carbonate
mixture; and
2. Apply the techniques involved in double indicator titrations.

II.

PRINCIPLES

Neutralization titrations are used to identify whether a certain species is acidic or basic.
Moreover, there are different applications of neutralization titrations in which the analyte is
converted to an acid or base by subjecting it to suitable chemical treatment then titrated
against a standard strong acid or base. Some applications include elemental analysis: nitrogen
and determination of inorganic substances: ammonium salts, nitrates and nitrites, carbonates
and carbonate mixtures (Skoog, West, Holler & Crouch, 2014).
Carbonates and carbonate mixtures are examples of polyprotic bases which can be
analyzed by double indicator titration. Double indicator titration is an acid-base titration used
for polyprotic acids or bases. It contains more than one equivalence point that is why more
than one indicator should be used to determine different endpoints at different pH.
The property of certain indicators to change color at different stages of neutralization is
sometimes used to determine the proportions of the components of certain mixtures (e.g.
carbonate mixtures). This is done either by (1) Single flask method: observing two endpoints
in a single titration using two different indicators, or (2) Double flask method: performing
two separate titrations on identical samples, each employing a different indicator.
In titration of a solution containing only Na 2CO3 with a standard acid, the reaction takes
place in two stages. When dissociated, it is in the form of carbonate ion which can protonate
twice, resulting to bicarbonate, HCO3-. When it reacted with the hydronium ions present in
the solution, it can form carbonate dioxide and water.
(1) 2-++ +
(2) + + +

The principle of double indicator titration may be applied in the analysis of solutions
containing various amounts of any or all of the following substances: NaOH, NaHCO 3, or
Na2CO3. The composition of all of the possible solutions that could result are:
(a)
(b)
(c)
(d)
(e)

NaOH
Na2CO3
NaHCO3
NaOH-Na2CO3
Na2CO3-NaHCO3
The important reactions that will take place in the possible solutions that could result
are:
- + 3+
2-++ +
+ + +

The mixture of NaOH and NaHCO3 is not plausible because it is unstable. The
components reacting as follows:
OH- +
HCO3CO32- +
H2O
The composition of a carbonate sample is established by titrating two identical
samples with a standard acid, employing phenolphthalein as indicator in one and
bromcresol green in the other. At the phenolphthalein endpoint, all of hydroxide and
carbonate ions have already been neutralized. At the bromcresol green endpoint, all of
the bicarbonate ions have been neutralized. The qualitative composition of the sample
may be deduced from the relative volumes of acid required for the two titrations (V pH
for the volume of acid delivered with the phenolphthalein indicator and V bcg for the
volume of acid delivered with the bromcresol green indicator.
The table shows the relations of the volume of the standard acid delivered used to
reach the end points.
Table 1. Qualitative analysis of carbonate mixtures using volumes at endpoints
Component Present
NaOH
Na2CO3
NaHCO3
NaOH-Na2CO3
Na2CO3-NaHCO3

Volume relationship of acid used to

endpoints*
VpH = Vbcg
VpH = Vbcg
VpH = 0
VpH > Vbcg
VpH < Vbcg

*VpH = volume of standard acid used to reach end point using phenolphthalein
Vbcg = volume of standard acid used to reach end point using bromcresol green

When a solution containing both NaOH and Na2CO3 is titrated with HCI to a
phenolphthalein endpoint, the amount of acid used is that required to react with all the
OH- ions plus that required to convert CO32- to HCO3-. The volume of acid required
for this endpoint is noted, then bromcresol green or another indicator that changes
color (from blue to green to yellow) at pH 4-5 is added, and the titration is continued
to the endpoint of the second indicator. The additional volume of acid is added to
reach the bromcresol green endpoint is the amount required to convert HCO 3- to CO2..
For the second indicator, phenolphthalein, at pH 9-10 its color changes from colorless
to light pink to fuchsia.
However the two-indicator method applied in a single titration described above is
not precise in actual titrations. The buffer system produced may interfere with the
phenolphthalein endpoint. More accurate results can be obtained by a modification of
the procedure.
Separate aliquots of equal volume of the sample are taken for analysis. The total
basic strength of one portion is determined by titration with HCI solution to the
bromcresol green endpoint. The other portion is treated with BaCI 2 solution to
precipitate the CO32- as BaCO3 leaving the NaOH component in solution. This is then
titrated with HCI to the phenolphthalein endpoint. It is not necessary to filter the
BaCO3 before titration since the phenolphthalein is not high enough to give any
reaction with the precipitate.

III.

PRE LAB CALCULATIONS AND FORMULAS

Dilution factor = Vdilution/Vsample

IV.
V.

DATA AND RESULTS

PRE LAB QUESTIONS

1. Why is it necessary to use boiled and cooled distilled water in the dilution of the
carbonate sample?
Hot water less readily dissolves gases than cold water. By boiled distilled water,
dissolved gases like carbon dioxide will evaporate out of the solution faster than they
otherwise would. If the water is then allowed to cool quietly, the water will have little
opportunity to pick up more gas. Since carbon dioxide reacts with water to produce
appreciable amounts of carbonic acid, it can dissociate to bicarbonate and further to
carbonate, thus leading to a positive error. Since we dont want a positive error it is
necessary to boil the solution.

2. Why is it necessary to boil the solution?

During the determination of the total basic strength, carbonic acid is produced,
which can further dissociate to H2O and CO2 . Boiling removes CO2 and drives the
reaction forward.
3. Give a simple method to test the completeness of the precipitation with BaCl2.
Let the precipitate settle, then a drop of BaCl 2 solution. If a precipitate forms due
to the additional drop, then precipitation is incomplete; if no precipitate forms,
precipitation is complete.