QUANTITATIVE DETERMINATION OF DISSOLVED OXYGEN

CONTENT BY WINKLER REDOX TITRATION

ANSWERS TO QUESTIONS

1. Give the pertinent chemical equations and stoichiometry in the standardization of

Na2S2O3.
Na2S2O3 produces a thiosulfate solution that is not stable and must be standardized with
potassium iodate (KIO3). Standardization is based on the comproportionation reaction of
iodide with iodate with the end product as iodine. The iodine binds with excess iodide, and the
complex is titrated with thiosulfate. Na2S2O3 was first standardized in order to know the actual
number of moles of Na2S2O3 that will react with the solution. From the number of moles of
Na2S2O3, the amount of moles of O2 in the solution can be determined stoichiometrically. One
mole of iodate produces three moles iodine, which are consumed by six moles of thiosulfate.
The reaction is as follows:
2Na2S2O3.5H2O+I2 →Na2S4O6 +2NaI+10H2O
2S2O32-+I2 →S4O6 2-+2I-
2IO3-+10I-+12H+ → 6I2+6H2O-

2. Explain the purpose of the addition of H2SO4 and excess KI during standardization
and why KI was added before the acid
KI acts as the major source of iodide ions in the reaction. Since it is an ionic compound, upon
reacting with water, it readily yields ions upon dissociation. Excess KI during the
standardization functions as a resource for acidic medium in order for KIO3 standard to react
with Na2S2O3. The acid, MnSO4 was first added so that the dissociate ion of Mn2+ could
precipitate and the formation of iodide ions could proceed.

3. Explain stepwise how I3- was produced from the dissolved O2 in the water sample.
Explain briefly why the reagents are added in a definite sequence
Dissolve oxygen, O2, found in the water sample could be determined through iodometric
titration. The triodide end product of this process was produced through a series of reactions.
First, Mn(OH)2 was oxidized to MnO(OH)2 by dissolved oxygen; thereby, forming a brown
precipitate. Then, after KI, NaOH, and NaN3 were added, I- is oxidized to I2 after reducing Mg.
But, since Iodide is in excess, I2 reacts with the iodide ion to form the triodide. NaOH along with
KI, and NaN3 were added sequentially because the OH- ions will precipitate the Mn2+. KI was
added next because Iodide ions will be needed to oxidize Manganese to a higher state.
Mn2+ + 2OH- → Mn (OH)2
Mn2+ + 2OH- +0.5O2 → MnO2 + H2O
Mn(OH)2 + ½ O2 → MnO2 +H2O
MnO2 +2I- + 4H+ → Mn2+ +I2 +2H2O
I2 +I- → I3-

4. Give the reason why starch was used as the indicator in this analysis and why it was
added towards the end of the titration
Starch functions as an indicator for the complete reaction of iodine with Na2S2O3 and the
formation of triodide. Starch forms a complex with iodine that yields a triodide anion; this
complex gives off the change in color during titration. As could be seen in the series of steps to
produce triodide, it is in the titration step where the thiosulfate is titrated with iodine to
 produce triodide; and starch only changes color on the presence of iodide. If Iodide were
oxidized, the solution would become blue again.

5. How is this analysis (an iodometric process) different from an iodimetric one?
This is an iodometric process because it determines the amount of an oxidizing agent present
in a solution through titration with Na2S2O3 while on the other hand, the iodimetric process
determines the amount of a reducing agent through titration with a standard Iodine solution.

6. From the calculated ppm O2, identify the degree of water pollution and ability of the
water sample source to sustain aquatic life.
The calculated dissolve oxygen is 4.64 ppm. According to the quality guidelines per American
Public Health Association, Inc, the water in the Institute of Biology pond falls on the category of
polluted but could sustain life of warm water bodies.

7. Predict the effect, if any, of each of the following on the DO oxygen content obtained:
a. The water sample is made to stand overnight before analysis.
If the water sample was left to stand in over a 24-hour period, the dissolved oxygen in
the water sample would be affected indeterminately (it could either decrease or
increase) depending on the microorganisms present in the sample. These
microorganism could either use up or contribute to the dissolved oxygen through their
biochemical respiration or processes. In addition, if the water sample was not freshly
prepared, the dissolved oxygen content would be reduced since dissolved oxygen’s
solubility decreases as temperature increases.

b. MnSO4 is added and the solution made to stand for an hour before the alkaline
KI solution is added.
When MnSO4 is added and the solution made to stand for an hour before the alkaline
KI solution is added, calculated DO will decrease. This is because the manganese ion
will react with O2 to produce MnO.

8. What are the possible sources of errors and their effect on the calculated parameters?
Rationalize.
Possible errors may include overtitration error, wrong sequence of addition of reagents and
other human errors which can be reduced through repeated trials. The sequencing of the
reagents is important because of the corresponding reactions of each product and reagent.

REFERENCES

[1] Kenna, T. C. (2006, March 14). DETERMINATION OF DISSOLVED OXYGEN BY WINKLER

TITRATION.

[2] Kumar, A. (2012, February 21). CEL 212 Lab 6 Dissolved Oxygen.

[3] Lewis, M. E. (2011, August 26). DISSOLVED OXYGEN. In National Field Manual.

[4] Harris, D. Quantitative Chemical Analysis, 7th ed., W. H. Freeman and Company (2007).
Calculations
Molarity of the standard Na2S2O3 solution
𝑚𝑜𝑙 6 𝑚𝑜𝑙 𝑁𝑎2 𝑆2 𝑂3
0.1508 g KIO3 ( KIO3 )(.9994)( ) 10
213.995g 1 𝑚𝑜𝑙 KIO3
𝑀1 𝑁𝑎2 𝑆2 𝑂3 = ( ) = 0.01296 𝑀
.0326 𝐿 𝑁𝑎2 𝑆2 𝑂3 100
𝑚𝑜𝑙 6 𝑚𝑜𝑙 𝑁𝑎2 𝑆2 𝑂3
0.1508 g KIO3 ( KIO3 )(.9994)( ) 10
213.995g 1 𝑚𝑜𝑙 KIO3
𝑀2 𝑁𝑎2 𝑆2 𝑂3 = .0276 𝐿 𝑁𝑎2 𝑆2 𝑂3
(100) = 0.01531M

𝑚𝑜𝑙 6 𝑚𝑜𝑙 𝑁𝑎2 𝑆2 𝑂3

0.1508 g KIO3 ( KIO3 )(.9994)( ) 10
213.995g 1 𝑚𝑜𝑙 KIO3
𝑀3 𝑁𝑎2 𝑆2 𝑂3 = .0322 𝐿 𝑁𝑎2 𝑆2 𝑂3
(100) = 0.01312 M
0.01296+0.01531+0.01312
̅=
𝑀 = 0.0137966 = 0.01380 𝑀
3

Grubb’s Test

Suspected Value G Crit95% Gtest Outcome Conclusion

1.7 1.543 1.547 1.547>1.543 Outlier: 1.7

ppm O2 of the water samples (mg/L)

1 𝑚𝑜𝑙 𝑂2 32 g O2 1000𝑚𝑔
(0.0022 𝐿)(0.0137966 𝑁𝑎2 𝑆2 𝑂3 )( )( )( )
4 𝑚𝑜𝑙 𝑆2 𝑂3 2− 1 mol O2 1𝑔
𝑝𝑝𝑚 𝑂2 = = 4.63936 𝑝𝑝𝑚
0.05 𝐿

1 𝑚𝑜𝑙 𝑂2 32 g O2 1000𝑚𝑔
(0.0022 𝐿)(0.0137966 𝑁𝑎2 𝑆2 𝑂3 )( )( )( )
4 𝑚𝑜𝑙 𝑆2 𝑂3 2− 1 mol O2 1𝑔
𝑝𝑝𝑚 𝑂2 = = 4.63936 𝑝𝑝𝑚
0.05 𝐿

4.63936 +4.63936
*𝑝𝑝𝑚
̅̅̅̅̅̅̅̅̅̅
𝑂2 =
2
= 4.64

Statistical parameters
Groups DO
1 4.48
2 6.16 Relative Standard Deviation
1.113
3 3.46 𝑅𝑆𝐷 = (1000 𝑝𝑝𝑡) = 237.0 𝑝𝑝𝑡
4.7
4 4.70 Confidence Interval (95% level)
Average 4.7 2.36(1.113)
𝐶𝐼 = 4.7 ± ( ) = 4.58 ± 1.770
Std 1.113 √ 4