REDOX TITRATION: WINKLER METHOD FOR DISSOLVED

OXYGEN DETERMINATION
CLEMENTE, JAMELA JIRAH L.
NATIONAL INSTITUTE OF GEOLOGICAL SCIENCES, COLLEGE OF SCIENCE
UNIVERSITY OF THE PHILIPPINES, DILIMAN, QUEZON CITY, PHILIPPINES
DATE SUBMITTED: MAY 10, 2013

ABSTRACT

Dissolved oxygen content in water was determined by winkler method a type of redox titration. Specifically, iodometry was used in
the experiment, where the analyte use was iodine and the titrant was thiosulfate .The experiment was done by collecting water
sample from Vinzon’s pond adding the reagents that made it acid, then it was titrated with thiosulfate solution and starch was
used as an indicator. Data showed that the dissolved oxygen of the sample is 0.00921, with a standard deviation of 0.00103
and the confidence limit has a range of 0.00665-0.0118. Supported by the computed statistical parameters, it was therefore
concluded the the water in Vinzon’s pond is highly polluted and cannot sustain life.

In the experiment the water sample used, was from

Vinzon’s pond. It was placed in a glass container and
RESULTS AND DISCUSSION was covered with foil and was sealed tightly so that no
air can enter, since addition of air and exposure to
The amount of dissolved oxygen in water samples that sunlight would increase the amount of dissolved
is exposed to air was determined by using the winkler oxygen due to free radical reaction. In addition, the
method. The concept behind Winkler method is Redox water sample was also made sure to be freshly taken
titration, it is a type of titration that deals with from the source since using water sample that was
chemicals that undergo a reaction that alter their already stored overnight would alter the amount of
oxidation state of the reagents involved, which are also dissolved oxygen due to reactions that is caused by the
known as redox reactions, to be able to determine the microorganisms in the water, furthermore leaving the
concentration of the titrant that was used. From the water overnight with added analyte which is KI
values of dissolved oxygen, the quality of water was solution would increase the amount of dissolved
assessed, table 1 shows how the water is assessed oxygen since there will be more iodide in the solution
depending on the concentration of dissolved oxygen (in therefore greater amount of thiosulfate to be used. It
ppm) While adding MnSO4 before KI solution would only
add Mn2+ ions and therefore microorganisms can still
Table 1 Water quality based on DO content
perform biological activities. It was mentioned that the
Dissolved Oxygen Implication analyte used was I2 therefore the type of redox reaction
8-9 Clean, good water that was employed in the experiment was iodometry
7-11 Ideal for stream fishes where I2 is the analyte and Na2SO3 was used as titrant
6.7-7.9 Slightly dirty where the disappearance of iodine, indicated by
4.5-6.6 Moderately dirty transparent color, determines the endpoint.
Below 4.5 Highly dirty
0-2 Cannot sustain life Since the experiment includes titration therefore
standard solutions should be made, how ther are
prepared and how their concentrations are expressed
(Skoog, West and Holler, 1996). In the standardization
of thiosulfate solution, 0.15 g of KIO 3 was dissolved in
water and diluted up to 100 mL, then an aliquot of 10
mL was transferred to three Erlenmeyer flasks, 1g of
KI crystals and 0.5 M sulfuric acid was immediately
added to the solution, then it was titrated. Addition of
sulfuric acid was needed in order to provide acidic
medium for the redox reaction so that the reaction will
will be spontaneous, while addition of excess KI
crystals was made in order to provide I- which forms I3-
with I2 . Adding sulfuric acid only after KI crystals were
added is essential, since doing the reverse would
increase the dissolved oxygen since IO 3- will form I2,
very soluble in water in effect less thiosulfate needed to
reach endpoint. Equation 1 shows the reaction upon
adding KI crystals and sulfuric acid while equation 2
shows the formation of I3-.
IO3- + 5I- + 6H+ 3I2 + 2H2O (1)
I2 + I- I3- (2)
Then the solution was titrated with thiosulfate solution,
in which the reaction is
3S2O32- + I3- 3I- + S4O62- (3)
When the color changed from wine red to yellow,
starch was added as an indicator forming a blue
complex since there is an excess oxidizing agent or the
amount of I2 is greater than I-. Titration was continued
until the blue color disappears which indicates that I2
now has lower amount compared to I-. Starch was not
added before titration starts because starch solution
undergo decomposition when mixed with high I2
concentrations, which produces higher endpoint. Table
2 shows the computed values for molarity based on the
data gathered from standardization
Table 2.Standardization
Trial Total Volume of Molarity of
titrant used titrant
1st 42.2 mL 9.90x10-3M
2nd 38.3 mL 0.0109M
3rd 34.6 mL 0.0121M
Average 0.0110 M
After standardization, titration of the water sample was
performed. 0.5 mL of MnSO4, 0.5 mL NH4HCO3 and
0.5 mL NaOH was added to the sample carefully by
dipping the tip of pipette just below the surface water
so that no air bubble can enter because presence of air
bubble would increase the dissolved oxygen in the
sample. MnSO4 was added since it contains the Mn2+
that reduces O2 and since all of the DO would react to
oxidize Mn2+ and then, the oxidized Mn would next
react with OH- from NaOH to form, Mn(OH)2 a
brownish precipitate that when reduced by an acid in
the presence of iodide ions, is equivalent to the
dissolved oxygen content of the water sample.
However since there are other organic substances in
the water NH4CO3 was added to exclude their effect by
conversion of manganese into oxygen-sensitive
carbonates. The reaction is
O2 + 4Mn(OH)2 +2H2O 4Mn(OH)3 (4)
The presence of the precipitates indicates that there are
no free dissolve oxygen in the sample anymore. Then
phosphoric acid was added first which dissolves the
precipitate producing Mn3+ which in turn oxidizes
previously added iodide ions (in NaOH) to iodine. Also
in the preparation of NaOH, KI and sodium azide was
added, this is so, so that upon addition of NaOh in the
solution, sodium azide prevents the conversion of I- to
I2 which is caused by nitrates. The overall reaction is
6H+ + 2MnO(OH)2 + 2I- 2Mn2+ +I2 + 4H2O (5)
Then the solution was covered and shaked so that there
will be no air oxidation which may cause the molarity
of iodide ions to increase. Then titration with
thiosulfate was done then the volume at the time when
the endpoint is reached was used to compute for parts
per million of dissolved oxygen as shown in table 3.
Table 3. Sample Analysis
Trials Total Volume DO of water
Titrant used sample
1st 4.9 8.62x10-3
2nd 4.9 8.62x10-3
3rd 5.9 0.0104
average 9.21x10-3
Ideally, the volume of titrant used for the three
samples, but since in the 3rd sample there was an
alteration of the procedure, specifically, it was titrated
first then the starch was added, thus it consumed
greater amount of titrant in result has different value of
DO. The formula for calculating ppm DO is given by
 1 𝑚𝑜𝑙 𝑂2 [3] http://www.emperoraquatics-
(𝑀𝑡ℎ𝑖𝑜𝑠𝑢𝑙𝑓𝑎𝑡𝑒 𝑉𝑡ℎ𝑖𝑜𝑠𝑢𝑙𝑓𝑎𝑡𝑒 ) ( ) (𝑀𝑊 𝑂2 )
4 𝑚𝑜𝑙 𝑆2 𝑂3 2− pond.com/pond_water_quality.php. retrieved:
𝑉𝑠𝑎𝑚𝑝𝑙𝑒 May 8, 2013
Since in every 4 moles of thiosulfate there is one
oxygen gas. Results showed that the water sample has
DO content of 0.00921, which falls under 0-2 range in
table 1. The statistical parameters for the DO are were
also computed and tabulated in table 4.

Table 4Statistical Parameters of DO

Parameters Values
Mean 9.21x10-3
SD 1.03x10-3
RSD 111.83
CL (95%) 0.00665-0.0118

SUMMARY AND CONLUSION

Since the the computed value for DO content is within

the range of 0-2, therefore the water sample can be
determined as higly polluted and could not support life,
however there were 2-3 small fishes seen in the pond,
but they are very small and pale in color which means
that the water has a very poor quality
(EmperorAquatics-POND.com). Based from the
statistical parameters there is a very little, 0.00103
deviation in the test made and since the computed
value for DO content is within the range of the
confidence limit at 95%, therefore it can be said that
the computed value has only 5% of chance that it can
be wrong. All in all, there may be some errors in the
experiment, similar to the presence of bubbles or air in
the water sample because it was not tightly sealed and
also the exposure to sunlight might increase the DO
content, and also the subjectivity of an individual for
the yellow color, which may lead to increase amount of
thiosulfate and thus increased DO. For further
experiments, it is recommended to increase the number
of trials in order to have more accurate value.

REFERENCES

[1]Skoog, et. al, 2004.Fundamentals of Analytical

Chemistry, 8th edition. Brooks|Cole.

[2]Day, RA and Underwood,L. 1991. Quantitative

Analysis.6th ed. Prentice-Hall, Inc.