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TECHNOLOGY
DEPARTMENT OF CHEMISTRY
YEAR TWO (CHEM 269)
EMAIL: ernopoku@gmail.com
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
basin.
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
reservoir.
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.
pH, C02, H2CO3, H+, C03, HCO3-, calcium +2 and magnesium +2.
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.
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
chloride:
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
PROCEDURE
PROCEDURE OBSERVATION
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.
TABULATION OF RESULTS
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
25ml
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
25ml
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
X=0.325mol
. .
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
.
= 0.0812
.
=0.0820
. . .
Mean [HCO-3] (y) = = 0.0820
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
3
[ ] .
the standard deviation of [HCO-3]= = = 8.0 10
.
=0.0136
.
=0.0130
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
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.
PRECAUTIONS
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
titration.
CONCLUSION
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.
REFERENCES