QUANTITATIVE

DETERMINATION
OF
DISSOLVED OXYGEN CONTENT BY WINKLER
REDOX TITRATION
M. BLAS and C. TAN
INSTITUTE OF BIOLOGY, COLLEGE OF SCIENCE
UNIVERSITY OF THE PHILIPPINES, DILIMAN, QUEZON CITY 1101, PHILIPPINES
DATE SUBMITTED: 14 APRIL 2016
DATE PERFORMED: 7 APRIL 2016

ABSTRACT
This experiment aims to observe the chemistry behind the Winkler redox titration method. Water samples from
various ponds around the university were collected, titrated with Na 2 S2 O 3 , and starch was used as an
indicator in the analysis. Na2S2O3 acted as the oxidizing agent and treated with an excess KI to produce I2. The
sample analysis was done in triplicate and the dissolved oxygen content was calculated to have an average of 2.2612
ppm O 2 was obtained. It can be presumed that the experiment was successful for having a 0.7007 standard
deviation. Based on the water quality guidelines, the water sample was deduced to be highly polluted.

water quality guidelines, as per American Public

Health Association, Inc.

INTRODUCTION
Water is one of the prime and vital elements
responsible for life on earth. Water has
numerous domestic, commercial, and industrial
uses, and because of this, its suitability and
sustainability for those said functions can be
greatly affected by other substances suspended
in the water. For an instance, dissolved gases
present in bodies of water.
Dissolved oxygen refers to the volume of
molecular oxygen contained in water. Just like
humans, both plants and animals in aquatic
environments also need a constant supply of
oxygen for their own survival and growth. [1]
The amount of dissolved oxygen in both natural
and wastewater is dependable on the physical,
chemical, and biochemical processes involved in
the entire water system. [2] Table 1 shows the

Table 1. Dissolved oxygen content and water

quality relationship.
DO content (ppm
O2), at 20C
8.00 9.00
6.7 7.9
4.5 6.6

4.5 and below

0.00 2.00

Water Quality
Clean, good water
Slightly polluted
Moderately polluted, can
sustain lives of warm water
fishes
Highly polluted
Cannot sustain life

There are several ways of measuring dissolved

oxygen, and the Winkler Method is one of those.
This method was developed by Hungarian
chemist L.W. Winkler in 1884. The Winkler

Page 1 of 5

method, also known as the iodometric method,

is an oxidation-reduction titrimetric procedure
based on the oxidizing property of dissolved
oxygen. The analysed oxidizing agent is made to
react with excess Iodide under suitable
conditions, yielding Iodine which will then be
titrated sodium thiosulfate. [3]
The main objectives of the experiment include
performing water sampling and pre-treatment
techniques for dissolved oxygen analysis,
determining dissolved oxygen content in a water
sample, and discussing the chemistry behind the
winkler method.

METHODOLOGY

the bottle using a syringe. The bottle was then

shaked thoroughly and vigorously. At this point,
precipitate will accumulate. 2.0 mL of
H 3 PO 4 was added with a
concentrated
measuring pipette. This dissolved the precipitate
previously formed.
After covering and shaking, it was left alone to
stand for about 10 minutes. A 50.0 mL aliquot
was taken from here. The aliquot was
transferred into a 250-mL erlenmeyer flask. It
was immediately titrated with the standard
Na2 S2 O3 until a pale yellow color was
obtained. 1.0 mL of starch was added and
titrated until the blue color disappears. This was
performed in triplicate.

For the standardization of

Na 2 S2 O3 , 0.048
grams of the primary standard KIO 3 was

RESULTS AND DISCUSSION

weighed and dissolved in about 50 mL distilled

water.
The
solution
was
transferred
quantitatively into a 100-mL volumetric flask. It
was then diluted to mark. Three 5.0 mL aliquots
of this were taken and transferred into three 250mL erlenmeyer flasks. About 20.0 mL distilled
water was added to each flask. Approximately
0.5 grams of KI and 5 mL of 0.5 H 2 SO 4 were
also added to each solution.

Iodine is made use in two kinds of reductionoxidation processes. The first one is iodimetry,
wherein iodine as I 2 is used as an oxidizing
agent and is used directly to titrate the reducing
agent. On the other hand, iodometry is an
indirect titration. In this experiment, iodometry
is projected. Iodine is mild oxidizing agent
reduced to form the iodide ion. [4]

The solution was immediately titrated with the

standard Na 2 S2 O 3 until a pale yellow color
was obtained. 1 mL of starch was added to the
solution. Titration was immediately continued
afterwards until the color blue disappears
completely. This procedure was done thrice.
For the analysis of the water sample, a surface
water sample was taken from the stagnant water
area of the UP Lagoon, covered with carbon
paper and aluminum foil. This was done to
prevent its exposure to sunlight. It was made
sure that air bubbles were not included before
covering the bottle.
0.5 mL of
KI and

Mn SO 4 and 0.5 mL of NaOH with

NaN 3 , in succession, were added to

2 I (1)
I 2+2 e
The above reaction is reversible, so the iodide
ion is a moderately reducing agent that will
react with oxidizing analytes to produce iodine.
In iodometric titrations, an oxidizing agent
reacts with an excess of iodide to produce
iodine.

X ox + I 2
X + 2 I

(2)

For the standardization of Na 2 S2 O 3 , KIO 3

was used as the primary standard as shown
below:

Page 2 of 5

+ 3 H 2 O
+ 3 I 3
(3)
+ 6 H

+8 I
IO3
+ I 2
I
I 3
2
+S4 O6
(5)
2 2 I

I 2 +2 S 2 O3
H 2 SO 4
succession, to the KIO 3
Water, KI, and

Table 2. Molarity of
TRIA
L
1
2
3

(4)

S 2 O3 .

VOLUME, mL

MOLARITY, M

11.0
10.5
10.7

0.01216
0.01274
0.01250

The average molarity of

Manganese sulfate,

were added, in

that was initially

placed in a beaker. KI was added to the solution
to produce more complex triiodide ions for a
sharper endpoint. Sulfuric acid was also added
to the solution as an acidic environment was a
necessity for the iodate reaction to take place. It
would cause the equilibrium to shift towards the
left, abling it to producing more iodine. [3] This
projected the concept of the common-ion effect.
KI was added before the sulfuric acid to prevent
the formation of iodic acid, HIO 3

KIO 3 was used as the primary standard as it

oxidizes the iodide quantitatively to triiodide in
acid solution. This solution yielded the products
in equation 3 in a dark yellow solution. The
triiodide formed in equation 3 is unstable, so it
immediately decomposes into iodine and iodide
as shown in equation 4. The standard (employed
as the X
in equation 11) used in this
iodometric process was the sodium thiosulfate.
The solution was titrated with thiosulfate until a
pale yellow color is achieved.
The endpoint of the iodometric method is based
on the liberated iodine. Starch was added to the
solution to detect them. [5] The solution turned
into a deep blue complex, and must be titrated
until the colorless endpoint is achieved, as
shown in equation 5.

S 2 O3 is 0.01247 M.

Mn SO 4 , and an NaOH

with KI and NaN 3 solution, in specific order,

was added to the water sample from a specific
pond in the university. The following reactions
proceed as a result:

Mn(OH )2
(6)
2++2 OH
Mn
4 Mn (OH )2 +O2+ 2 H 2 O 4 Mn (OH )3
(7)

2+ + I 2+6 H 2 O
+ 2 Mn
(8)
+6 H
2 Mn (OH )3 +2 I

I 3 (9)
I 2 + I
2
+ S 4 O6
2 3 I
(10)

+ 2 S2 O3
I 3

The reagents are added in this specific sequence

as each reagent contributes to a chain of specific
reactions. Changes in the succession will yield
different and unwanted products.

Mn SO 4

was added to provide Mn(II) ions.

This fixes the dissolved oxygen under basic
conditions, resulting to brown precipitate.

Page 3 of 5

Mn(II) ions will then bind with the

from

OH ions

the

addition of NaOH to form

Mn(OH )2 as shown in equation 6. [6] In
equation 7, it is projected that the produced
Mn(OH )2 will be oxidized if dissolved
oxygen is present.
The addition of KI institutes the excess

into the solution. Adding phosphoric acid

provides the

+
H ions which acidifies the

solution, dissolving the precipitate. These are

both evident in equation 8. Produced I 2 will
then react with excess iodide to form triiodide
complex, as shown in equation 9. [7] Upon
titration with thiosulfate, the complex will again
be reduced to iodide, as shown in equation 10.
Table 3. Dissolved oxygen content in ppm
O2 .
TRIAL

VOLUME, mL

1
2
3

1.5
0.8
1.1

DO, ppm
2.9928
1.5961
2.1947

The average dissolved oxygen content is 2.2612

ppm O 2 . According to table 1, we can infer
that the surface water in the stagnant area in the
UP Lagoon is highly polluted.
However, the DO content calculated may change
depending on different circumstances. If the
water sample was made to stand overnight
before the sample analysis, the calculated DO
may either increase or decrease. One occurrence
where the DO content might decrease is the
presence of microorganisms in the sample.
These microorganisms consume oxygen, leading
to the reduction of DO content. On the other
hand, photosynthetic microorganisms could also
be present in the water samples. These
microorganisms produce oxygen as a product of

photosynthesis, meaning the DO content could

also increase in their presence.

Mn SO 4 and
Another instance is adding
letting it stand for an hour before adding the
alkaline KI solution. This may lead to deduction
of DO content as Mn2+ will react with O2 to
produce MnO2. This compound is insoluble in
water.
CONCLUSIONS
The experiments main objective was to
determine the amount of dissolved oxygen in a
water sample from a pond in the university
using winkler redox tiration.
The average molarity of Na 2 S2 O 3 as it was
standardized is 0.01247 M. The average
dissolved oxygen content was 2.2612 ppm
O2 , which according to the American
Public Health Association, Inc. was highly
polluted.
To avoid possible sources of errors, extra caution
must be made during the entirety of not only the
experiment, but also the preparation. During the
collection of water sample, inclusion of air
bubbles will result to a higher amount of
calculated DO. Errors in solution preparation
will also yield relevant differences.
Not following the correct sequence of adding
reagents may result in chemical reactions that
are significantly different from those that are
expected. Air oxidation of iodide ion which
I 2 will
leads to the production of more
increase the DO content.
Although human errors may be minimized, it
cannot be physically absent. Even then, this
experiment can be considered as a success, as
there was no deviation from the values
gathered.

REFERENCES

Page 4 of 5

[1] Kemker, C. (2013, November, 19). "Dissolved

Oxygen." retrieved April 11 2016, from
Fundamentals of Environmental Measurements
Web Site.
[2] Analytical Chemistry Academic Group.
(2013) Analytical Chemistry Laboratory Manual
Elementary Quantitative Inorganic Analysis
Chem 26.1. Quezon City: UP Diliman.
[3] Day, R.A. & Underwood, A.L. (1991).
Quantitative Analysis. New Jersey: Prentice Hall.

[4] Harris, D.C. (2006). Quantitative Chemical

Analysis. New York: W.H. Freeman and
Company.
[5] Haenisch, E.L., Pierce, C., Sawayer, D.T.
(1958). Quantitative Analysis. London: John
Wiley and Sons, Inc.
[6] Grasshoff, K. Ehrhardt, M, and K. Kremling
(1983). Methods of Seawater Analysis.
Weinheim: Wiley-VCH.
[7] Skoog, D., West, D., Holler, F., Crouch, S.
(2014). Fundamentals of Analytical Chemistry.
Belmont, California: Brooks/Cole, Cengage
Learning.

Page 5 of 5

Page 6 of 5

APPENDIX
Molarity

S 2 O3 , M

O
3
2 mol S2
1 mol I 2

Trial 1:
0.1 AF
1 mol KIO 3
0.048 g0.994 purity
214.0 g KIO 3
M =

)(

3 mol I 2

1 mol IO3

)(

3 mol I 2

1 mol IO3

)(

3 mol I 2

1 mol IO3

O3
2 mol S2
1 mol I 2

Trial 2:
0.1 AF
1 mol KIO 3
0.048 g0.994 purity
214.0 g KIO 3
M =

O3
1 mol I 2

Trial 3:
0.1 AF
1 mol KIO 3
0.048 g0.994 purity
214.0 g KIO 3
M =
2 mol S2

Average:

0.01216+0.01274+ 0.01250
3

Dissolved Oxygen content, ppm

= 0.01247 M

O2

Trial 1:

4 mmol S 2 O 3
1 mmolO 2 32 mg O 2
(
)

1 mmol O 2

0.01247 M Na2 S 2 O 31.5 mL Na2 S 2 O 3

= 2.9928 ppm

O2

Trial 2:

4 mmol S 2 O3
1 mmolO2 32 mg O2
(
)

1 mmol O2

0.01247 M Na 2 S 2 O30.8 mLNa 2 S 2 O3

Trial 3:

4 mmol S 2 O
3
1 mmolO2 32 mgO2
(
)

1 mmolO 2
= 2.1947 ppm O 2

0.01247 M Na 2 S 2 O31.1 mL Na 2 S 2 O3

Average:

2.9928+ 1.5961+2.1947
3

= 2.2612 ppm O2

Standard deviation: 0.7007

Relative standard deviation:

RSD=

0.7007
1000 ppt=30.99
2.2612

Confidence interval:

CI =2.2612
LL: 0.5216
UL: 4.0008

(4.30)(0.7007)
= 2.2612
3

= 1.5961 ppm

1.7396

O2