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 Na 2S2O3, explain the
addition of sulfuric acid and excess KI, give the effect of adding the acid
before KI.
IO3- + 8I- + 6H+ 3I3- + 3H2O (1)
2S2O32- + 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,
HIO3 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 Mn2+ + SO4MnSO4 was added to provide Mn2+ ions in the solution. Mn2+ 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.
Mn2+ + 2OH- Mn(OH)2
The Mn 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.
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+ 2Mn2+ + I2 + 6H2O / 6H+ + 2MnO(OH)(s) + 2I- 2Mn2+ + 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.
Mn2+ and I2 will then be produced.
I2 + I- I3Produced I2 will react with excess I- to form an iodine cmplex, I3-.
2S2O32- + I3- S4O6- + 3IUpon 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 O 2 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
Mn2+ 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 HIO3 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/imagefiles/light_dark_reactions.gif&imgrefurl=http://www.the-simplehomeschool.com/teachingphotosynthesis.html&usg=___jDqSEi8wygsnJeDEVEZ7_7Wt0c=&h=586&w=70
0&sz=95&hl=en&start=0&sig2=D_mchoSc1y4yuXlNWeDvQ&zoom=1&tbnid=krA6daxt_tH7eM:&tbnh=145&tbnw=173&ei=Rc2P
TJ_-MI2WcZPU2bgM&prev=/images%3Fq%3Dphotosynthesis%2Bdark
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