QUANTITATIVE DETERMINATION OF DISSOLVED

OXYGEN CONTENT BY WINKLER REDOX TITRATION

J. Tan​1
1`​
College of Education
University of the Philippines, Diliman, Quezon City 1101, Philippines.
Date submitted: October 18, 2019
Date Performed: October 4, 2019

ANSWERS TO QUESTIONS

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

NaS​2​O​3​.

The pertinent chemical equations, in their net ionic form, in the standardization of ​NaS​2​O​3 are,
​

𝐼𝑂​3​-​(𝑎𝑞) + 5𝐼​-​(𝑎𝑞) + 6𝐻​+​(𝑎𝑞) → 3𝐼​2​-​(𝑎𝑞) + 3𝐻​2​𝑂(𝑙) ​ (𝟏)

𝑂𝐻𝑅:5(2𝐼​-​(𝑎𝑞) → 𝐼​2​(𝑎𝑞) + 2𝑒​-​)

𝑅𝐻𝑅:10𝑒​-​ + 2𝐼𝑂​3​-​(𝑎𝑞) + 12𝐻​+​(𝑎𝑞) → 𝐼2(𝑎𝑞) + 6𝐻​2​𝑂(𝑙)

2𝐼𝑂​3​-​(𝑎𝑞) + 12𝐻​+​(𝑎𝑞) + 10𝐼​-​(𝑎𝑞) → 6𝐼​2​(𝑎𝑞) + 6𝐻​2​𝑂(𝑙) ​ (2)

𝐻​+​(𝑎𝑞) + 𝐼𝑂​3​-​(𝑎𝑞) → 𝐻𝐼𝑂​3​(𝑎𝑞) ​ (𝟑)

𝐼​2​(𝑎𝑞) + 𝐻​2​𝑂(𝑙) ↔ 𝐼​-​(𝑎𝑞) + 𝐻​+​(𝑎𝑞) + 𝐻𝐼𝑂(𝑎𝑞) ​(𝟒)

𝐼​2​(𝑎𝑞) + 𝐼(𝑎𝑞) − → 𝐼​3​_​(𝑎𝑞) ​ (𝟓)

𝐼​3​_​(𝑎𝑞) + 2𝑆​2​𝑂​3​2−​(𝑎𝑞) → 3𝐼​ −​(𝑎𝑞)​ ​+ 𝑆​4​𝑂​6​2− ​ ​(𝑎𝑞)​ ​ (𝟔)

Established stoichiometric ratio between IO​3​-​, 𝐼​2 and

​ S​2​O​3​2-​:

1 𝑚𝑜𝑙𝑒 𝑜𝑓 𝐼𝑂​3 =
​ 3 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝐼​2​ = 6 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 S​2​O​3​
2-

2. Explain the purpose of the addition of H​2​SO​4 and the excess KI during
standardization and why KI was added before the acid.

Because an acidic environment was needed for the reaction of IO3- to occur, sulfuric acid and
potassium iodide was added. Potassium iodide and sulfuric acid was added in order respectively
to avoid the formation of ionic acid, HIO3-. Iodic acid is a weak acid, hence, it will dissociate
incompletely, meaning, there is less iodine ions, which results to less triiodide ions. If procedure
was not done respectively and accordingly, it may affect the accuracy of the results.

3. Give the pertinent chemical equations and stoichiometry in the sample analysis.

​ (​ 𝑎𝑞) + 𝑆𝑂​4​ 2​ −​(𝑎𝑞)​ ​

𝑀𝑛𝑆𝑂​4(​ 𝑎𝑞) → 𝑀𝑛 2+ (𝟏)
 ​ (​ 𝑎𝑞) + 2𝑂𝐻 ​_​(𝑎𝑞) → 𝑀𝑛𝑂𝐻​2​(𝑎𝑞)
𝑀𝑛 2+ (𝟐)

𝑂​2(​ 𝑎𝑞) + 4𝑀𝑛(𝑂𝐻)​2​(𝑎𝑞) + 2𝐻​2𝑂 ​ (𝑙) → 4𝑀𝑛(𝑂𝐻)​3​(𝑠) or

𝑂​2(​ 𝑎𝑞) + 4𝑀𝑛(𝑂𝐻)​2​(𝑎𝑞) → 4𝑀𝑛𝑂(𝑂𝐻)(𝑠) + 2𝐻​2𝑂 ​ (𝑙) ​ (3)
𝐼​2​(𝑎𝑞) + 𝐼​ -​(𝑎𝑞) → 𝐼​3​ ​−​(𝑎𝑞)​ (​ 𝟓)
𝐼​3​ ​−​(𝑎𝑞)​ ​ + 2𝑆​2𝑂​
​ 3​
2−​
(𝑎𝑞)→ 3𝐼​ - ​(𝑎𝑞) + 𝑆​4​𝑂​62​ −​ (𝑎𝑞) (𝟔)

Established stoichiometric ratio between 𝑂​2​and S​2​O​3​2-​: 1 𝑚𝑜𝑙𝑒 𝑜𝑓 𝑂​2=

​ 4 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 S​2O
​ ​3​
2

4. Explain stepwise how I​3​-​ was produced from dissolved O​2​ in the water sample. Explain
briefly why the reagents are added in a definite sequence.

It is necessary and vital to use boiled distilled water in the preparation of standard and sample
solutions as this guarantees that there are no dissolved gases, in the form of carbon dioxide,
present in the water. If carbon dioxide is not removed and it reactions with H+ ions present in the
water, an increased concentration of carbonic acid is to be expected, which will lead to an
inaccuracy and difference in the resulting pH value.

5. 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 was used to indicate that I3- was produced from the reaction (formation of blue complex).
Starch was added towards the end of titration so that bonding of I2 with starch and stabilization
of I2starch complex will be avoided. Starch can make the complex to have less dissociation
leading to difficulty in attaining the endpoint.

6. How is this analysis (an iodometric process) different from an iodimetric one?

In an iodimetric process, the analyte is the reducing agent. The analysis done is an
iodometric process wherein the analyte, which is an oxidizing agent, is iodine and the titrant is
sodium thiosulfate.

7. From the calculated ppm O​2​, identify the degree of water pollution and ability of the
water sample source to sustain aquatic life.

The sample water from the pond near the Math Department Building, with a dissolved oxygen of
4.53 ppm is slightly polluted based on the dissolved oxygen content and water quality
relationship table. Hence, the water sample source can sustain (aquatic) life enough but only have
a 12-24 hour range of tolerance yet this calculated result might be caused by having the sample
taken hours before the experiment and reactions might have had occured in the span of time
prior the experiment.

8. 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 without analysis.

When water sample is made to stand overnight before analysis, the calculated dissolved
oxygen content may increase or decrease. Photosynthetic and heterotrophic organisms
are agents for this increase or decrease, such that they can increase the dissolved oxygen
content since they are able to give off oxygen. On the other hand, presence of
heterotrophic organisms can decrease dissolved oxygen content since they are oxygen
consumers.
 b. MnSO is added and the solution made to stand for an hour before the alkaline
KI solution is added.

Calculated dissolved oxygen value will decrease because the manganese ions will be
reduced from Mn3+ to Mn2+. Thus, there would be lesser Mn3+ that will react with the
iodide ions in the solution from potassium iodide.

9. What are the possible sources of errors and their effect on the calculated parameters?
Rationalize.

A possible source of error can come from the collection and treatment of the water
sample. Presence of air bubbles in the water bottle sample can increase the dissolved oxygen
content. Another source of error is overtitration – which can affect the accuracy of the results.
Time interval in adding the KI and MnSO​4 ​is also a possible cause of error. Prolonged interval of
the addition of KI andMnSO​4 can decrease the dissolved oxygen content since there will be a
formation of insoluble MnO which is an oxygen consumer. Errors in the reading of the volume are
also causes of error and can affect the calculation of dissolved oxygen content.

REFERENCES

[1] Bissonnette, C., Herring, F.G., Madura, J.D. and Petrucci, R.H., 2011. General Chemistry: Principles
and Modern Applications. 10th Edition. Toronto: Pearson Canada, Inc.

[2]Skoog, West, Holler, Crouch. Fundamentals of Analytical Chemistry 8th Edition. 2004. Belmont:
Thomson Learning Inc.

[3] Whitney K. (2011). Winkler titrations – measuring dissolved oxygen. Colby at Sea.