QUANTITATIVE

DETERMINATION
OF
DISSOLVED OXYGEN CONTENT BY WINKLER
REDOX TITRATION
J.G.K.B. CORTEZ1 and J.P.P. PAMINTUAN2
1

COLLEGE OF PUBLIC HEALTH

UNIVERSITY OF THE PHILIPPINES, ERMITA, CITY OF MANILA 1000, PHILIPPINES
2
NATIONAL INSTITUTE OF GEOLOGICAL SCIENCES, COLLEGE OF SCIENCE
UNIVERSITY OF THE PHILIPPINES, DILIMAN, QUEZON CITY 1101, PHILIPPINES
DATE SUBMITTED: JULY 13, 2015
DATE PERFORMED: JULY 6, 2015

ANSWERS TO QUESTIONS
1. Give the pertinent chemical equations and stoichiometry in the standardization of
Na2S2O4.
The weighed KIO3 is placed in the beaker and dissolved in 50mL distilled water. From
here, three 10mL aliquots are obtained and added with 1 gram KI and 10mL 0.5M H 2SO4
each. It should be noted that each of these components should be added in proper order
(will be explained in numbers 2 and 4). The solution will exhibit a dark yellow color and
will follow equation 1 (Michaels & Dow, 1989).

(1)

+ 3 H 2 O
+ 3 I 3
+ 6 H
+8 I
IO3

As we can see in equation 1, there is a presence of a trioiodide in the product side. This
will immediately decompose (2) to produce I2 (Michaels & Dow, 1989).
(2)

+ I 2
I
I 3

Right after the preparation of the solution, it was titrated with standard Na 2S2O4 until it
changes its color into a pale yellow solution. From here, starch is added which will turn
the solution into blue. It will be further titrated until the solution turns colorless as shown
in equation 3 (King, 2011).

(3)

2
+S4 O6
2 2 I
I 2 +2 S 2 O3

The significant stoichiometric ratio observed in these reactions is 1 mole IO 3- = 3 moles

of I2 = 6 moles S2O32- (Michaels & Dow, 1989).
2. Explain the purpose of the addition of H 2SO4 and excess KI during standardization and
why KI was added before the acid.
The addition of H2SO4 before KI to the solution turns the environment of the solution
acidic. If the acid is added before KI, this will favor the reaction of the IO 3- to produce
HIO3. This is a weak acid which means that dissociation will be incomplete for the
solution. If the dissociation will be incomplete, there will be less IO 3- to produce iodine
(which will eventually interact with the titrant), therefore decreasing the volume of titrant
needed to meet the end point (Michaels & Dow, 1989).

3. Give the pertinent chemical equations and stoichiometry in the sample analysis.
The water sample, which is covered and wrapped in aluminum foil, is added with MnSO 4
solution and another solution of NaOH, KI and NaN3. The bottle should be secured of air
bubbles. After the addition of these solutions, the bottle is vigorously shaken until
appearance of precipitates is observed as shown in equation 4 and 5. The oxygen
content of the sample will be fixed with respect to the precipitate (King, 2011). This
means that after the precipitation, the oxygen content of the solution will be constant,
and it will make way for measurement of O 2 thru the dissolution of the MnO(OH)2
(Michaels & Dow, 1989).
(4)

(5)

Mn ( OH )2
2+ +2OH
Mn

1
2 Mn (OH )2 + O 2+ H 2 O 2 MnO (OH )2
2

H3PO4 will now be added to dissolve the precipitate as seen in equation 6. When all the
precipitates are completely dissolved, titration of the sample shall be started (Michaels &
Dow, 1989).

(6)

2++ I 2+ 6 H 2 O
2 Mn
++2 MnO(OH )3 +2 I
6 H

The significant stoichiometric ratio observed in these reactions is 1 mole of O 2 = 4 moles

S2O32- (Michaels & Dow, 1989).
4. 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.
Basically, the mechanism seen from equations 5 and 6 are the initial part of how O 2 has
interacted with the Mn(OH)2 and water to form MnO(OH) 2. The I2 from the product side of
equation 6 will react with free I - ions to form I3-. This is exhibited by equation 7. From
here, we will now follow the mechanism of equation 8 which shows the titration of I 3- with
thiosulfate. I3- will react with 2 moles of the thiosulfate and will produce 3 moles of I (Michaels & Dow, 1989). This displays the ratio of O 2 molecules in the sample with the
thiosulfate needed for titration.
(7)

(8)

I 3

I 2+ I

2
+ S 4 O6
2 3 I
+ 2 S2 O3
I 3

One of the most important reasons in the ordered addition of crystals and solutions to
the sample is the issue of solubility. If the researchers do not follow the prescribed order
of reagent addition, each mechanism in the process will be affected by the change.
Certain reagents if introduced in the wrong time can react unknowingly to different ions.
On the other hand, timing errors for addition may also cause non-dissolution of reagents.
The MnSO4 should be added first so that Mn 2+ will be able to dissociate in the water.
Apart from this NaOH is also added next to increase alkalinity of the environment. The
basic environment helps in the formation of the MnO(OH) 2 (King, 2011). Another example
would be the precipitation of MnO(OH)2, it will not happen as it is if the solution of NaOH
will be added first before the MnSO 4 solution. It all depends on the characteristics of the
reagent being introduced to the reaction. Apart from this, certain acids and bases (H 2SO4
for the standardization) is added accordingly to control the acidity of the solution to favor
the reaction of iodate, therefore getting a more accurate concentration of titrant
(Michaels & Dow, 1989).
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.

The usage of starch as the indicator in the experiment is due to its ability to create a triiodide complex in the presence of excess I3. This turns the solution blue during titration
and changes into colorless as it gets to the end point of the process. On the other hand,
it should be noted that starch is added only near the endpoint due to another ability to
create an I2-starch complex in the beginning of the titration wherein I 2 is present. If this
happens, titrating for an accurate end point would be difficult due to the loss of some of
the iodine in the initial part of the experiment (King, 2011).
6. How is this analysis (an iodometric process) different from an iodimetric one?
Determination of dissolved oxygen using Winkler method is a type of iodometric titration.
This means that it involves the oxidation of iodide to iodine (analyte) which can then be
titrated with standard thiosulfate solution to convert the released iodine to back to
iodide. From there, the amount of oxygen can be computed from the amount of
thiosulfate (titrant) used (Senese, 2010).
Iodimetry titration, on the other hand, is titration using an iodine solution as the titrant. It
is used for determining substances that have reducing properties (such as Na 2S2O4 as
analyte). The reaction results to the reduction of iodine to iodide. Starch can also be used
as indicator for this (Senese, 2010).
7. From the calculated ppm O2, identify the degree of water pollution and ability of the
water sample source to sustain aquatic life.
The computed average dissolved oxygen in the sample is 4.4 mg/L (ppm). This is under
the highly polluted catergory based in the dissolved oxygen-water quality table. With
respect to this value, the water sample that the researchers have obtained has a very
low capability to support organic life. As we know, dissolved oxygen (DO) in the bodies of
water is the source of aquatic lifeforms, including fishes, invertebrates, bacteria and
aquatic plants, of oxygen. These organisms use oxygen in respiration. Fishes and
invertebrates uses their gills to respire DO; plants and phytoplankton uses DO for
respiration when there is no light for photosynthesis; and, bacteria and fungi uses DO to
decompose organic material at the bottom of the water (King, 2011).
Low amount of DO in water can hamper reproduction and kill aquatic lifeforms. It can
also cause major shift in the kinds of aquatic species in the body of water. Wherein
species that can tolerate low level DO, pollution-tolerant organisms like worms and fly
larvae and algae and anaerobic organisms, will replace or dominate over other species
(King, 2011).
8. Predict the effect, if any, of each of the following on the dissolved oxygen content
obtained:
a. The water sample is made to stand overnight before the analysis
If the water sample is made to stand overnight before analysis, the dissolved oxygen
content will decrease. This is because the microbes present, bacteria and fungi, utilize
the dissolved oxygen to decompose the organic material present in the water sample,
and the heterotrophic organisms will also utilize dissolved oxygen for respiration since
they cannot photosynthesize without the presence of the sun. Moreover, since it is left to
stand overnight, there is no aeration or disturbances that can cause the diffusion of
oxygen from the atmosphere to the water sample (Oram, 2014).

b. MnSO4 is added and the solution made to stand for an hour before the alkaline KI
solution is added.
The MnSO4 in the solution left to stand an hour will most likely lower the calculated
dissolved oxygen. This is rooted to the photosensitivity of Mn 2+ in the solution.
Manganese is easily reduced under exposure to light sources. When this happens, the
amount of Mn2+ will decrease, favoring higher oxidation states of the element. The lower
Mn2+ in the solution will decrease volume of titrant used, and eventually will also
decrease the calculated dissolved oxygen in the water sample (Hakala, Rantamaki,
Puputti, Tyystjarvi, & Tyystjarvi, 2006).
9. What are the possible sources of errors and their effect on the calculated parameters?
Rationalize.
Common problems in this experiment are partially filled sample bottles. This means that
there is air space which can result to the addition of oxygen dissolved into the water
sample thus increasing the dissolved oxygen content of the water sample (Michaels &
Dow, 1989).
Apart from this, if the bottle is not shaken well after addition of NaOH, then it is possible
that not all the oxygen of the water sample will be precipitated into MnO(OH). In this
case, not all of the dissolved oxygen content will be accounted for thus there will be a
decrease in the calculated dissolved oxygen content. On the other hand, if the bottle is
not shaken well after addition of H 3PO4, then not all of the oxygen will be dissolved thus
decreasing the calculated DO content.
Use of water that isnt boiled for the standardization of sodium thiosulfate can result to
the formation of carbonic acid. Presence of this acid can provide as a source of hydrogen
ions which can react with the thiosulfate titrant. This will result to a decrease in the
concentration of thiosulfate which leads to the increase in volume of titrant required and
the decrease in the molarity of sodium thiosulfate. Apart from these, personal errors,
instrumental errors, and measurement errors are the most plausible sources of erroneous
data (Skoog, West, Holler, & Crouch, 2004).

REFERENCES

Hakala, M., Rantamaki, S., Puputti, E.-M., Tyystjarvi, T., & Tyystjarvi, E. (2006). Photoinhibition
of manganese enzymes. Journal of Experimental Botany .
King, W. (2011, February 11). Winkler Titrations Measuring Dissolved Oxygen. Retrieved
June 6, 2015, from Colby College: http://web.colby.edu/colbyatsea/2011/02/11/winklertitrations-measuring-dissolved-oxygen/
Michaels, A., & Dow, R. (1989, October). Determination of Dissolved Oxygen by the Winkler
Procedure. Retrieved June 6, 2015, from Bermuda Atlantic Time-Series Study:
http://bats.bios.edu/methods/chapter6.pdf
Oram, B. (2014). Dissolved Oxygen in Water. Retrieved July 6, 2015, from Water Research
Center: http://www.water-research.net/index.php/dissovled-oxygen-in-water
Senese, F. (2010). REDOX Reactions. Retrieved June 6, 2015, from General Chemistry Online:
http://antoine.frostburg.edu/chem/senese/101/redox/faq/iodometry-iodimetry.shtml
Skoog, D., West, D., Holler, J., & Crouch, S. (2004). Fundamentals of Analytic Chemistry. In S.
Kiselica (Ed.). Thomson Learning Academic Resource Center.

SAMPLE COMPUTATIONS
M Na2S2O3 (Trial 1)

0.1500 g

99.4 1 mol KIO 3 6 mol Na2 S2 O 3 10

100 214 g KIO 3

1 mol KIO 3
100
=0.01088639019 M Na2 S 2 O3
1L
38.4 mL
1000 mL
Table 1. Calculated M Na2S2O3 from different trials
Trial

M Na2S2O3

0.01088639019

0.01050345184

0.01058322489

0.01026434132

0.01123007235

0.01108113240

AVERAGE

0.01075810217

ppm dissolved oxygen (DO) (Trial 1)

0.01075810217

1 mmol O2
32 mgO2
mmol
Na 2 S2 O3 1.9 mL Na2 S 2 O3

mL
4 mmol Na 2 S 2 O3 1 mmolO2
=3.27046306 ppm DO
1L
50.0 mL
1000 mL

Table 2. Calculated ppm dissolved oxygen (DO) from different trials

Trial

M Na2S2O3

3.270463060

5.163889042

4.647500137

AVERAGE

4.360617413

Standard
Deviation

0.9787705351

Relative Standard Deviation

0.9787705351
1000 ppt=224.4568698 ppt
4.360617413

Confidence Limits

4.360617413

4.30 0.9787705351
=4.360617413 2.429901757 ppm DO
3