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1. To introduce titration as a useful technique in chemical analysis.

2. To analyze a sample for total alkalinity and then determine the individual amount of
carbonate and bicarbonate.


Carbonate and Bicarbonate

The carbon dioxide that is dissolved by naturally circulating waters appears in chemical analysis
principally as bicarbonate and carbonate ions.

Carbonate that follows this path represents a linkage between the carbon cycle and the
hydrologic cycle. The large supply of atmospheric carbon dioxide is partly intercepted by
photosynthesizing vegetation. They convert it to cellulose starch and related carbohydrates.
These products are later reduced via respiration to carbon dioxide and water with a release of
stored energy. The concentration of carbonates in natural waters is a function of dissolved carbon
dioxide, temperature, pH, cations and other dissolved salts.

At one atmosphere of pressure, pure C02 gas over distilled water will produce a solution that
would have a pH near 3.6. In the presence of excess calcite, however, the solution would contain
some 350 mg/L of dissolved calcium and its pH would be near 6.

A considerable part of the released carbon dioxide must return directly to the atmosphere and
obviously the efficiency of utilization of the dissolved portion will be far below the theoretical
maximum. Water quality records for streams in the United States indicate that the maximum rate
for calcium and bicarbonate removal is near 400 tons per square mile per year, but most streams
carry far less than half this much. These figures do suggest that under most favorable conditions,
limestone may be rather rapidly eroded.

It may also be of interest to note that a considerable part of the anionic load of many streams is a
contribution from carbon dioxide of the atmosphere rather than from the rocks of the drainage
Bicarbonate concentration of natural waters generally is held within a moderate range by the
effects of the carbonate equilibria.

Most surface streams contain less than 200 mg/L Carbonate and Bicarbonate, but in ground
water somewhat higher concentrations are not uncommon. Concentrations over 1,000 mg/L
sometimes occur in waters which are low in calcium and magnesium and especially where
processes releasing carbon dioxide such as sulfate reduction are occurring in the ground water

Many of the carbonates are quite insoluble in water, generally more so than the chlorides,
nitrates or sulfates. There is a tendency for certain carbonate salts to be removed by precipitation
or absorption. In more calcareous environments, the circulation of water rich in carbon dioxide
may produce solutions that are highly supersaturated when exposed to the air. Such solutions
may deposit large quantities of calcium carbonate as travertine near their points of discharge. In
hard waters, particularly in headwaters that are fed by limestone springs, deposits of calcium
carbonate are often layed down. These may form large solid structures that can dam up a stream
or produce waterfalls.

This precipitated material is travertine. Some of the deposition is probably purely chemical and
is caused by the loss of equilibrium carbon dioxide necessary to keep the calcium carbonate and
bicarbonate in solution. However, it is nearly always associated with algae and to a lesser extent
with mosses that cause deposition of calcium carbonate by photosynthesis.

As will be discussed in alkalinity, it is important to note that bicarbonates tend to reach

equilibrium with the carbonates. For this reason, most running waters are bicarbonate waters in
a limnological sense and show the complicated relationships between

pH, C02, H2CO3, H+, C03, HCO3-, calcium +2 and magnesium +2.

For this discussion, it is sufficient to stress only a few points:

(1) rainwater reaching the water courses as a runoff from bogs, dense forest litter, and similar
substrata tends to have a low pH because of the hydrogen ions produced by disassociation of
carbonic acid and the loss of cations by base exchange with the organic matter,
(2) water which has percolated through the soil is also rich in carbon dioxide and similarly tends
to be rich in hydrogen ions according to this equation:
H20 + C02 -> H2CO3 H + HCO3
(3) calcium carbonate which is a common constituent of many rocks is almost insoluble in water,
but it dissolves fairly readily as bicarbonate in carbonic acid, and it neutralizes soil water where
it occurs, according to this reaction:
CACO3 + H2CO3 -> cA(Hco3>2 CA+2 + 2HC03-2.
(4) Calcium bicarbonate in solution is a good buffer system and thus resists change in pH, but it
remains in solution only in the presence of a certain amount of free carbon dioxide. Any process
which removes carbon dioxide, as does photosynthesis, tends to cause precipitation of calcium
carbonate from solution, especially where the bicarbonate is abundant.
Therefore, springs in limestone regions are often very rich in calcium bicarbonate where they
emerge to the surface. As the water flows along, it looses carbon dioxide to the atmosphere and
by photosynthesis. After some distance this loss becomes the loss of equilibrium C02 and the
deposition of calcium carbonate occurs by a reversal of the first part of the equation under #3
above. This process is also aided by the ability of many plants to make direct use of bicarbonate
ions as shown in this equation:
CA(HCO3)2 -> CAC03 + H20 + C02 (photosynthesized).

Deposition of calcium carbonate is therefore a common feature of streams in limestone areas and
is a subject which we shall discuss further in the alkalinity section.

The carbon dioxide released within the soil by respiration and decay is capable of producing low
pH in circulating water if minerals that act as proton acceptors are scarce. Soils of humid,
temperate regions may become depleted in calcium carbonate by leaching and the pH of ground
water at shallow depths may be rather low.

In general, it may be expected that carbonates in themselves are not detrimental to fish life, but
their buffering action and effect upon pH may contribute to the toxicity of high pH values. Little
is known about the influence of carbonate or bicarbonate on higher plants in rivers.

Carbon dioxide may be a limiting factor in soft waters where no bicarbonate ions are available
because water in equilibrium with normal air containing 4.0 ml/L contains only 0.68 ml/L in
solution of carbon dioxide. This is much less than is available to land plants. This difference is
one of the chief reasons for many of the peculiarities of submerged aquatic plants.

To summarize carbonate and bicarbonate, if a spring is from limestone or some other very
calcareous rock, the water will be heavily charged with calcium bicarbonate. It will loose carbon
dioxide very rapidly and its pH will rise. After some distance, the loss of carbon dioxide to the
atmosphere and by photosynthesis will lead to the deposition of calcium carbonate. This process
will decline steadily as equilibrium is attained.

In this well buffered hard water the pH will not rise above about 8.3 even at times of very active
photosynthesis, and these changes will occur while the water flows only a very short distance
from a few hundred meters to a few kilometers, according to the situation.

Water from noncalcareous springs will similarly loose carbon dioxide, increase its pH and
acquire oxygen in quite a short distance. If the source of the spring is a big, acid swamp, swampy
woodland, or rain forest, the water may contain ferrous bicarbonate. As pH rises and oxygen is
acquired, ferric hydroxide will be deposited probably over a distance measurable only in tens or
hundreds of meters.

Unless the water remains acidic, little iron will remain in solution. This part of the stream could
be coated with rust colored masses of iron bacteria. If this water is soft, its pH will fluctuate
markedly because of photosynthesis and it may exceed 8.3 in the daytime

The component in a solution containing sodium carbonate and sodium hydrogen carbonate
provides examples of how neutralization titration can be used to analyze mixtures. Numerous
inorganic species can be determined by titration with strong acids or strong bases. Some of these
examples are the mixtures containing hydroxide (OH-), carbonate
(CO32-) and bicarbonate (HCO3-) ions. The quantitative and qualitative determination of more
than two of these components mentioned above can exist in a substantial amount in any solution,
because reaction will remove one of them.

Carbonate (CO32-) and bicarbonate (HCO3-) ions requires two titrations.

One with a base range such as phenolphthalein and the other with acid range indicator such as
The total alkalinity (defined as total base concentration in this case is measured by titrating the
mixture with standard HCl to a Bromocresol green end point:

Total alkalinity= [HCO3-] +2[CO32-]. For these samples, this is approximately the amount of
base that reacts with an added acid, hence the term total alkalinity and the original amount of
carbonate and bicarbonate present in your sample.

To determine total alkalinity, you have to titrate your sample with the standard hydrochloric acid
using a bromocresol green end point. The reactions are:
HCO3-(aq) + H+(aq) H2CO3 (aq)
CO32-(aq) + 2H+(aq) H2CO3(aq)

In this first titration, there is no way to differentiate between the second and first reactions, so the
endpoint of the reaction is for both of the reactions, together. In the second step, you will
determine the original carbonate concentration of your unknown by exploiting a number of
methods, including selective precipitation. You will treat a fresh aliquot with an excess of the
standard sodium hydroxide from Experiment 1, converting all HCO3- to CO32-:
HCO3-(aq) + OH-(aq) CO32-(aq) + H2O
The sample then consists entirely of CO32, which you will precipitate by adding excess barium
Ba2+(aq) + CO32-(aq) BaCO3(s)
The excess NaOH is then immediately titrated with standard hydrochloric acid to determine how much
bicarbonate had been originally present in the sample. From the total alkalinity, and bicarbonate the
original carbonate concentration can be calculated.


1. Unknown sample
2. Distilled water
3. 0.1M Hydrochloric acid
4. 10%(wt/wt) BaCl2
5. Bromocresol green indicator
6. 0.1M NaOH
7. Phenolphthalein indicator
8. Two 250ml volumetric flasks
9. 25ml Pipette
10. three 250ml conical flasks
11. Funnel
12. Electronic balance,
13. Burette
14. 10ml measuring cylinder


2.01g of the unknown sample was measured
into a beaker.
The unknown was dissolved in distilled water A colorless solution of the mixture was
in the beaker and then transferred into a 250ml formed.
volumetric flask and topped up to the mark.
An indicator blank was prepared by adding There was a color change from purple to white
some of the indicator to an amount of BaCl2 solution. This indicated the end point color.
and NaOH.
The unknown sample solution was then titrated There was a color change from light blue to
with standard 0.1M HCl. light yellow.
The experiment was repeated for two more There was a color change from light blue to
values. light yellow.
25ml of the unknown sample was measured A purple solution was formed with some
into a 250ml conical flask and then 50.0ml of precipitates at the bottom.
standard NaOH and 10ml of 10% (wt/wt)
BaCl2 were added. Two drops of
phenolphthalein indicator was then added.
The solution was then titrated with standard There was a color change from purple to white
0.1M HCl. solution with some precipitate at the bottom.
The step was repeated for two more values. There was a color change from purple to white
solution with some precipitate at the bottom.



Indicator used: Bromocresol green
Number of drops: 2 drops
Colour change: Blue to pale yellow
CO32 2 H H 2CO3

Burette reading/mL Final reading/mL Initial reading/Ml Titre value/mL

1 47.20 20.00 27.20
2 27.20 0.10 27.10
3 46.90 19.9 27.00

Average titre = (27.20 +27.10 +27.00) ml = 27.10mL

Hence volume of HCl that reacted with the mixture = 27.10mL


Indicator used: phenolphthalein
Number of drops used: 2
Colour change: pink to white

Burette reading/mL Final reading/mL Initial reading/mL Titre value/mL

1 29.30 0.00 29.30
2 29.70 0.00 29.70
3 29.50 0.00 29.50

Average titre value = (29.30 + 29.70+29.50)ml = 29.50ml

volume of HCl that reacted with excess NaOH =29.50ml

Equation of reaction between NaOH and the carbonate

HCO-3 + OH- CO2-3 + H2O ------ 3
the equation of reaction between BaCl2 and the bicarbonate
Ba2+ + CO2-3 BaCO3 ------ 4
the equation of reaction between the excess NaOH and HCl is
NaOH + HClNaCl + H2O ------ 5

From the equation of reaction between HCl and the mixture

total alkalinity = [HCO-3] + 2[CO2-3]

1. 27.20ml of HCl was required to react with the first 25ml of the mixture
let x= mol of CO2-3 and let y= mol of HCO-3 in the 25ml aliquot
total alkalinity= mol of H+ needed to reach the Bromocresol green end point
hence total alkalinity= 2x + y = 0.1 27.20
2x + y= 2.72ml
50ml of 0.1M NaOH was added, hence mol of NaOH= 50 0.1= 5.0mol
when 29.30ml of the HCl reacted with the excess NaOH
mol of HCl= 0.1 29.30= 2.93mol
mol of NaOH that reacted with HCO-3= 5.002.93= 2.07mol
hence 2x= 2.72 2.07= 0.65mol
x= 0.65/2=0.33mol
total alkalinity= 0.65 + 2.07= 0.1088M

2. 27.10ml of HCl was required to react with the second 25ml of the mixture
2x + y= 2.71mol
when 29.70ml of HCl reacted with excess NaOH
mol of HCl= 0.1 29.70= 2.97mol
mol of NaOH that reacted with HCO-3= 5.00 2.97= 2.03mol
hence 2x= 2.71 2.03= 0.68mol
x= 0.68/2=0.34mol
total alkalinity= 0.68+ 2.03= 0.1084M

3. 27.00ml of HCl was required to react with the third 25ml of the mixture,
2x +y=2.70
When 29.50ml 0f HCl reacted with excess NaOH
mol ofHCl=0.1x29.50=2.95
mol of NaOH that rected with HCO-.3 =5.00-2.95=2.05
Hence 2x+y=2.70-2.05=0.65mol
. .
Total alkalinity= = 0.1080M
. . .
Average total alkalinity (x)= = 0.1084M
Let x be the values of total alkalinity

X (X-X) (X-X)2
0.1088 4.0 10-4 1.6 10-7
0.1084 0.00 0.000
0.1080 -4.0 10-7 1.6 10-7
(X-X)2=3.2 10-7

[ ]
Standard deviation=
standard deviation= =4.0 10

The bicarbonate concentrations [HCO2-3] for the three values

= 0.0828

= 0.0812


. . .
Mean [HCO-3] (y) = = 0.0820

Let y be the values of concentration of bicarbonate

Y (y-y) (y-y)2
0.0828 8.010-4 6.4 10-7
0.0812 -8.010-4 6.4 10-7
0.0820 0.00 0.00
(y-y)2=1.28 10-6

[ ] .
the standard deviation of [HCO-3]= = = 8.0 10

The three values for the carbonate concentration[CO2-3] are as follows




Mean [CO2-3]=0.0132 + 0.0136 + 0.0130= 0.0133M


X x-x (x-x)2
0.0132 -1.0 10-4 1.0 10-8
0.0136 3.0 10-4 9.0 10-8
0.0130 -3.0 10-4 9.0 10-8
(x-x)2=1.90 10-7

[ ] .
The standard deviation of [CO2-3= = =3.08 10

( . ) .
The carbonate concentration [CO2-3] = =0.0792M

Molar mass of K2CO3= 2(39) + 12 + 3(16)= 138g/mol

mass of K2CO3 = (0.0792 138 25)/1000= 0.273g
mass of sample= 2.50g
% by mass of CO2-3= 0.273 100= 10.92%
. . .
The bicarbonate concentrations [HCO2-3] = =0.0100M
molar mass of NaHCO3= 23 + 1 + 12 + 16 + 3(16)= 100g/mol
mass of NaHCO3= (0.0100 100 25)/1000= 0.025g
% by mass of HCO2-3= 0.025/2.50 100= 1.00%

Hence % of K2CO3= 10.92(0.00080) wt%

% of NaHCO3= 1.00(0.00308) wt%

The titration in the first reaction was to establish a stoichiometric ratio between the HCl,
the carbonate and the bicarbonate content of the mixture. However, the second titration
was a back titration to be used to calculate the amount of each constituent present in the
sample. The barium chloride (BaCl2) was used to mask the carbonate thus, preventing it
from interfering the reaction between the NaOH and the bicarbonate (HCO -3), it was
BaCl2that formed the precipitate with CO2-3 at the bottom of the container. The excess
NaOH that reacted with the HCl was subtracted from the initial amount of NaOH to find the
amount of NaOH that actually reacted with the bicarbonate.

Consequently, showing the amount of bicarbonate present in the sample. From eq.3, the
bicarbonate reacted with NaOH to produce the carbonate. This implies that in alkaline
solution, the bicarbonate behave as a Bronsted-Lowry acid and donates a proton.
Contrarily in eq. 1, it behaved as a Bronsted-Lowry base by accepting a proton from HCl. It
can therefore be observed that the bicarbonate is an amphoteric substance. The percentage
of the carbonate 10.92(0.00080) wt% was found to be greater than that of the bicarbonate
1.00(0.00308) wt% in the mixture because the bicarbonate donates a proton to the water
which acts as a weak Bronsted-Lowry base thereby producing more of the carbonate.


1. Parallax error should be avoided when taking readings from the glass wares.
2. The solution of mixture should be swirled to enable complete formation of mixture.
3. As soon as the two drops of phenolphthalein was added the solution was titrated
against 0.1M HCl.
4. Blank solution should be used to give a clear indication about the end point of


The concentrations of carbonate and bicarbonate were determined. It is known at the end of the
experiment that The percentage of the carbonate 10.92(0.00080) wt% was found to be
greater than that of the bicarbonate1.00(0.00308) wt% in the mixture because the
bicarbonate donates a proton to the water which acts as a weak Bronsted-Lowry base
thereby producing more of the carbonate.

1. Gary D. Christian Analytical chemistry sixth edition ( page 75-85)

2. Statistics for Analytical Chemistry, J.C. Miller and J.N. Miller, 3rd edition, page 16-20
3. Vogels hand text book of Quantitative chemical analysis ,fifth edition, G.H. Jeffery,
J.Bassett, 55-60
4. Zeebee, Richard. 2006. Marine Carbonate Chemistry. The Encyclopedia of the