REDOX TITRATION: WINKLER METHOD FOR DISSOLVED OXYGEN

DETERMINATION
M. J. A. DAYAO

INSTITUTE OF BIOLOGY, COLLEGE OF SCIENCE
UNIVERSITY OF THE PHILIPPINES, DILIMAN, QUEZON CITY, PHILIPPINES

ANSWERS TO QUESTIONS:
1. Pertinent chemical equations in the standardization of Na2S2O3, explain the addition of sulfuric acid
and excess KI, give the effect of adding the acid before KI.

IO
3
-
+ 8I
-
+ 6H
+
3I3
-
+ 3H2O (1)
2S2O3
2-
+ I3
-
S4O6
-
+ 3I
-
(2)
Excess KI and sulfuric acid was added to the solution because they are necessary in the production of I3
-
. The
sulfuric acid was added to provide H
+
ions while KI to provide I
-
as shown in equation 1.The KI crystals were added
first because if the acid was added first, HIO
3 will be formed instead of
I3
-
.

2. Pertinent chemical equations involved in the sample analysis and explain stepwise how I3 was
produced from the dissolved O2 in the water sample. Explain briefly why the reagents are added in
definite sequence.

MnSO4 Mn
2+
+ SO4
-
MnSO4 was added to provide Mn
2+
ions in the solution. Mn
2+
ions are necessary since Winkler Method is
based in the ability of dissolved O2 to oxidize divalent manganese added to the solution. NH4HCO3 was added to
convert Mn into oxygen-sensitive carbonates and eliminate the influence/interference of other dissolved organic
compounds.

Mn
2+
+ 2OH
-
Mn(OH)2
The Mn
2+
ions will then bind to the free OH
-
ions in the solution or to the OH
-
from the added NaOH to
form Mn(OH)2.

O2 + 4Mn(OH)2 + 2H2O 4Mn(OH)3 / O2 + 4Mn(OH)2 4MnO(OH)(s) + 2H2O
The produced Mn(OH)2 will then be oxidized if dissolved oxygen is present to form either Mn(OH)3 or
MnO(OH) precipitate
.
2Mn(OH)3 + 2I
-
+ 6H
+
2Mn
2+
+ I2 + 6H2O / 6H
+
+ 2MnO(OH)(s) + 2I
-
2Mn
2+
+ I2 + 4H2O
Addition of KI introduces excess I
-
into the solution and the phosphoric acid provides H
+
ions that
acidifies the precipitate and oxidizes the excess iodide in the solution. Mn
2+
and I2 will then be produced.
I2 + I
-
I3
-
Produced I2 will react with excess I
-
to form an iodine cmplex, I3
-
.

2S2O3
2-
+ I3
-
S4O6
-
+ 3I
-
Upon titration with thiosulfate, the iodine complex will be reduced to I
-.

The reagents are added accordingly to ensure the formation of I3
-
. Changes in the sequence will yield unwanted
products not needed in the titration.

3. The calculated ppm O2 of your sample, identify its degree of pollution and relative ability to sustain
aquatic life.

The calculated dissolved oxygen in the water sample obtained from the AS pond is 5.17 ppm O2. This value is
found in the 4.5 6.6 ppm O2 range. The quality of the water in this range is moderately polluted but can sustain life of
warm water fishes.


4. Effect, if any, of each of the following on the DO content obtained
a. the water sample is made to stand overnight before sample analysis

Calculated DO can either increase or decrease. Since the water sample was obtained from a pond, oxygen
consuming microorganisms could be present in the sample. These microorganisms undergo cellular respiration that
require oxygen, thus the calculated DO will decrease. Moreover, photosynthetic phytoplanktons could also be present in
the samples. These organisms on the other hand give off oxygen as a product of the light reaction phase of
photosynthesis thus calculated DO could increase. However, if the sample was left to stand overnight, the planktons will
concentrate on the dark reactions phase of photosynthesis, and the light reaction phase will not proceed since sunlight is
needed in this phase. Dissolved oxygen will then stop increasing once the light supply is no longer available but will still
decrease because of the presence of oxygen consuming microbes.

b. MnSO4 is added and the solution made to stand an hour before the alkaline solution KI is
added
Mn
2+
will react with O2 to produce MnO, compound insoluble in water. As a consequence, calculated DO will
decrease.

5. Possible sources of error and their effect on calculated parameters.

One possible source of error in this experiment is when the sulfuric acid is added before the KI in the
standardization part. This will result to the formation of HIO
3 and thus less I3
-
will be formed. This will lead to a
decrease in the liberated I2 and decrease in the calculated DO.


In the collection and treatment of the sample, presence of air bubble will result to an increase in the calculated
DO. Incorrect sequence of adding the reagents in the treatment of the water sample would result to a gross error.
Different unwanted products whose effect on the calculated DO is indeterminate might be formed. Prolonged interval
in the adding of reagents could also be a source of errors. Example is in the addition of MnSO4 and KI. Prolonged
interval can lead to the production of insoluble MnO which will consume dissolved oxygen in the sample and thus
decrease the calculated DO.

REFERENCES:

Crouch, S. R., Holler, F. J., Skoog, D. A., & West, D. M. (2004). Fundamentals of Analytical
Chemistry (8th ed.). United States of America: Thomson Learning Inc.

Determination of Dissolved Oxygen. 14 September 2010.
<http://www.colby.edu/chemistry/CH331/CH331%20Dis.Oxygen.pdf>

Photosynthesis. 14 September 2010. < http://www.google.com/imgres?imgurl=http://www.the-simple-
homeschool.com/image-files/light_dark_reactions.gif&imgrefurl=http://www.the-simple-
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rt=0&sig2=D_mchoSc1y4yuXl-
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MI2WcZPU2bgM&prev=/images%3Fq%3Dphotosynthesis%2Bdark%2Breaction%26um%3D1%26hl
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