QUANTITATIVE

DETERMINATION
OF
DISSOLVED OXYGEN CONTENT BY WINKLER
REDOX TITRATION
R.Y.A. RIVERA
DEPARTMENT OF FOOD SCIENCE AND NUTRITION, COLLEGE OF HOME ECONOMICS
UNIVERSITY OF THE PHILIPPINES, DILIMAN, QUEZON CITY 1101, PHILIPPINES
DATE SUBMITTED: 21 APRIL 2015
DATE PERFORMED: 7 APRIL 2015

ANSWERS TO QUESTIONS
1. Give the pertinent chemical equations and stoichiometry in the
standardization of NaSO.
IO + 8I + 6H 3I + 3HO (1)
2SO + I SO + 3I (2)
2. Explain the purpose of the addition of HSO and excess KI during
standardization and why the acid was added before KI.
The production of I needed excess KI and sulfuric acid to be added in the
solution. Yhe sulfuric acid provided H ions while KI provided I ions. If the acid was
added first instead of KI crystals, HIO will be formed instead of I.
3. Give the pertinent chemical equations and stoichiometry in the sample
analysis.
MnSO Mn + SO
Mn + 2OH Mn(OH)
O + 4Mn(OH) + 2HO + 2HO 4Mn(OH) / O + 4Mn(OH) 4MnO(OH) + 2HO
2Mn(OH) + 2I + 6H 2Mn + I + 6HO / 6H +2MnO(OH) + 2I 2Mn + I
+4HO
I + I I
2SO + I SO + 3I
4. Explain stepwise how I was produced from the dissolved O in the
water sample. Explain briefly why the reagents are added in a 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 Mn2+ ions will then bind to the free OH- ions in the solution or to the OHfrom 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+ 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.
5. Give the reason why starch is was used as the indicator in this analysis
and why it was added towards the end of the titration.
6. How is the analysis (an iodometric process) different form an iodimetric
one?
The analysis involved an iodometric process because the analyte which was
an oxidizing agent was added to excess iodide to produce iodine. The iodine
produced was determined by titration with sodium thiosulfate. An iodimetric
process, unlike the previous one, the analyte is a reducing agent and is titrated
directly with a standard iodine solution.
7. Form the calculated ppm O, identify the degree of water pollution and
ability of the water sample source to sustain aquatic life.
The calculated dissolved oxygen in water sample obtained from the pond
near the Math building was
. This value lies between the
range which means that the water quality is

8. Predict the effect, if any, of each on the following on the DO oxygen

content obtained:
a. The water sample is made to stand overnight before 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 of
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. MnSO is added and the solution made to stand for an hour before
the alkaline KI was added.
Mn will react with O to produce MnO, compound insoluble in water.
Because of this, calculated DO will decrease in value.
9. What are the possible sources of errors and their effect on the
calculated parameters? Rationalize.
A possible source of error can be committed during the collection and
treatment of the water sample. Presence of air bubbles during collection will give a
higher amount of calculated DO. Incorrect sequence of adding the reagents in the
treatment of the water sample would result to a gross error. Diferent unwanted
products whose efect on the calculated DO is indeterminate might be formed.
Prolonged interval in the adding of reagents could also be a source of errors. For
example, prolonged interval in the addition of MnSO and KI would lead to the
production of insoluble MnO which will consume dissolved oxygen in the sample and
thus decrease the calculated DO. Another possible source of error is during titration
if the sulfuric acid is added first before the KI crystals. This will cause the formation
of HIO and less formation of I. Consequently, the amount of I will decrease and
the amount of the calculated DO will also decrease.