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Discussion. Two methods may be used for this analysis. In the first method the total
alkali (carbonate + hydroxide) is determined by titration with standard acid, using
methyl orange, methyl orange-indigo carmine. or bromophenol blue as indicator. In
a second portion of solution the carbonate is precipitated with a slight excess of
barium chloride solution, and. without filtering, the solution is titrated with standard
acid using thymol blue or phenolphthalein as indicator. The latter titration gives the
hydroxide content, and by subtracting this from the first titration, the volume of acid
required for the carbonate is obtained.
Na2C03 + BaCl 2 = BaC03 (insoluble) + 2NaCI
The second method utilises two indicators. It has been stated in Section 10.17 that
the pH of half-neutralised sodium carbonate. i.e. at the sodium hydrogencarbonate
stage, is about 8.3, but the pH changes comparatively slowly in the neighbourhood
of the equivalence point; consequently the indicator colourchange with
phenolphthalein (pH range 8.3-10.0) or thymol blue [pH range (base) 8.0-9.6J is not
too sharp. This difficulty may be overcome by using a comparison solution
containing sodium hydrogencarbonate of approximately the same concentration as
the unknown and the same volume of indicator. A simpler method is to employ a
mixed indicator (Section 10.9) composed of 6 parts of thymol blue and 1 part of
cresol red; this mixture is violet at pH 8.4, blue at pH 8.3 and rose at pH 8.2. With this
mixed indicator the mixture has a violet colour in alkaline solution and changes to blue
in the vicinity of the equivalence point; in making the titration the acid is added slowly
until the solution assumes a rose colour. At this stage all the hydroxide has been
neutralised and the carbonate converted into hydrogencarbonate. Let the volume of
standard acid consumed be v mL.
OH-+H+ =H20
CO~- + H+ = HC03
Another titration is performed with methyl orange, methyl orange-indigo carmine or
bromophenol blue as indicator. Let the volume of acid be V mL.
OH-+H+=H20
CO~- + 2H+ = H2C03
H2C03 ~ H 20 + CO2
Then V - 2( V - v) corresponds to the hydroxide, 2( V - v) to the carbonate, and V to the
total alkali. To obtain satisfactory results by this method the solution titrated must be
cold (as near 0 C as is practicable), and loss of carbon dioxide must be prevented as far
as possible by keeping the tip of the burette immersed in the liquid.

Procedure A. Weigh out accurately in a glass-stoppered weighing bottle about 2.5 g of

commercial sodium hydroxide (e.g. in flake form). Transfer quantitatively to a 500 mL
graduated flask and make up to the mark. Shake the flask well. Titrate 25 or 50 mL of
this solution with standard 0.1M hydrochloric acid, using methyl orange or methyl
orange-indigo carmine as indicator. Carry out two or three titrations: these should not
differ by more than 0.1mL. This gives the total alkalinity (hydroxide + carbonate).
Warm another 25 or 50 mL portion of the solution to 70 C and add 1 per cent barium
chloride solution slowly from a burette or pipette in slight excess, i.e, until no further
precipitate is produced. Cool to room temperature, add a few drops of phenolphthalein
to the solution, and titrate very slowly and with constant stirring with standard 0.1M
hydrochloric acid; the end point is reached when the colour just changes from pink to
colourless. If thymol blue is used as indicator, the colour change is from blue to yellow.
The amount of acid used corresponds to the hydroxide present. This method yields only
approximate results because of the precipitation of basic barium carbonate in the
presence of hydroxide. More accurate results are obtained by considering the above
titration as a preliminary one in order to ascertain the approximate hydroxide content,
and then carrying out another titration as follows. Treat 25-50 mL of the solution with
sufficient standard hydrochloric acid to neutralise most of the hydroxide, then heat and
precipitate as before. Under these conditions, practically pure barium carbonate is
precipitated.

1mL 1M HCI = 0.0401 g NaOH

1mL 1M HCI = 0.05300 g Na2C03
Procedure B. The experimental details for the preparation of the initial solution are
similar to those given under Procedure A. Titrate 25 or 50mL of the cold solution
with standard 0.1M hydrochloric acid and methyl orange, methyl orange-indigo
carmine, or bromophenol blue as indicator. Titrate another 25 or 50mL of the cold
solution, diluted with an equal volume of water, slowly with the standard acid using
phenolphthalein or, better, the thymol- blue cresol red mixed indicator; in the latter
case, the colour at the end point is rose. Calculate the result as described in the
Discussion above.

10.33 DETERMINATION OF AMIXTURE OF CARBONATE AND

HYDROGENCARBONATE
The two methods available for this determination are modifications of those
described in Section 10.32 for hydroxide/carbonate mixtures. In the first procedure,
which is particularly valuable when the sample contains relatively large amounts of
carbonate and small amounts of hydrogencarbonate, the total alkali is first
determined in one portion of the solution by titration with standard 0.1M

hydrochloric acid using methyl orange, methyl orange-indigo carmine, or

bromophenol blue as indicator:
COj- + 2H + = H2C03
HC03 + H + = H2C03
H2C03 ~ H20 + CO2
Let this volume correspond to V mL 1M HCl. To another sample, a measured excess
of standard 0.1 M sodium hydroxide (free from carbonate) over that required to
transform the hydrogencarbonate to carbonate is added:
HC03 + OH- = COj- + H20
A slight excess of 10 per cent barium chloride solution is added to the hot solution to
precipitate the carbonate as barium carbonate, and the excess of sodium hydroxide
solution immediately determined, without filtering off the precipitate, by titration
with the same standard acid; phenolphthalein or thymol blue is used as indicator. If
the volume of excess of sodium hydroxide solution added corresponds to v mL of
1M sodium hydroxide and v'mL 1M acid corresponds to the excess of the latter, then
v - Vi = hydrogencarbonate, and V - (v - v') = carbonate. In the second procedure a
portion of the cold solution is slowly titrated with standard 0.1 M hydrochloric acid,
using phenolphthalein, or better, the thymol blue-cresol red mixed indicator. This
(say, Y mL) corresponds to half the carbonate (compare Section 10.32):
CO~-

+ H+ ~ HC03

Another sample of equal volume is then titrated with the same standard acid using
methyl orange, methyl orange-indigo carmine or bromophenol blue as indicator. The
volume of acid used (say, y mL) corresponds to carbonate + hydrogencarbonate.
Hence 2Y = carbonate, and y - 2Y = hydrogencarbonate.