Atq Experiment 8 Chem 26.1

J.N. Macabata / Chemistry 26.
1 (2016)
Page |1
Quantitative Determination of Dissolved Oxygen Content by Winkler Redox

Titration
Jelica N. Macabata
National Institute of Geological Sciences. University of the Philippines- Diliman, 1101, Quezon City
Performed 30 June 2016; Submitted 4 July 2016
a
ABSTRACT
Dissolved oxygen
J.N. Macabata / Chemistry 26.1 (2016)
Introduction
In studying environmental and marine science,
it is important to have knowledge on dissolved
oxygen (O2) content of a freshwater sample.
Dissolved oxygen concentration is expressed as
the number of millilitres of oxygen gas (O2) per
litre of freshwater sample (mL or L-1). Water
pollution control and waste water treatment
process control are determined by the dissolve
oxygen test2. It may be used by marine biologist
to measure primary production or by physical
oceanographers to study water masses in the
ocean. In terms of chemistry, it provides measure
of the redox potential of a water column.
Winkler method, developed in 1888, is used to
accurately measure the dissolved oxygen
concentration of a particular sample. The method
was then modified by Strickland and Parsons in
1968. This experiment provides the readers the
knowledge to perform the water sampling and
pre-treatment techniques for dissolved oxygen
analysis. It will also determine the amount of
dissolved oxygen in a water sample from a pond
in the Institute of Mathematics, College of Science
University of the Philippines-Diliman using
Winkler redox titration and discuss the chemistry
behind the Winkler method for dissolved oxygen
determination.
Materials and Methods
In performing the experiment, iron stands,
burette clamps and aluminium foil are needed.
We also prepared clean glass bottle with cap,
burettes (50 mL), beakers (50-, 100-mL),
volumetric flasks (25-, 100-, 250-mL), volumetric
pipettes (10-, 50-mL), Erlenmeyer flasks (250-ml),
watch glass and syringe. We also used analytical
balance, top-loading balance and hot plate for the
experiment.
The following solutions should also be
prepared:
1. 25.0 mL 4.0 M MnSO 4 from MnSO42H2O
crystals weigh
18.62 grams of the crystals and dissolve in
about
10-ml distilled water then filter the
solution into a
25-ml volumetric flask and dilute to mark.
2. 25.0 mL 18 M NaOH with 5.0 g KI and 0.15 g
NaN3
weigh the following solids and dissolve in a
beaker
with 10 mL distilled water while stirring in
a hot
plate then transfer to a 25-mL volumetric
flask and dilute to mark. This must be
done in a water bath, under the fume
hood.
Page |2
3. 250.0 mL 0.125 M stock Na2S2O3 solution from

Na2S2O35H2O crystals weigh g of crystals in a
beaker and
dissolve in about 100.0 mL boiled distilled
water
then transfer to a 250-mL volumetric flask.
Wash
the beaker with boiled distilled water and
catch
the washings into the flask.
4. 50.0 mL 0.5 M H2SO4 solution
5. Starch solution weigh 1.0 g of starch in a
beaker and
dissolve until a smooth paste is obtained.
Pour it
in a 100.0 ml boiled distilled water and
keep the
solution in 90-100 degrees Celsius to avoid
drying up.
6. 250.0 mL 0.0125 M standard Na 2S2O3 solution
from the
0.125 M stock Na2S2O3 solution pipette
0.125 M
stock solution and transfer to a 250.0 ml
volumetric flask and dilute to mark.
Standardization of the titrant Na2S2O3 was
done by weighing 0.15 grams of the primary
standard KIO3 and dissolved in 50.0 mL of distilled
water. Then the solution was transferred
quantitatively into a 100-mL volumetric flask and
diluted to mark. Three 10-mL aliquots was taken
from the solution and transferred into three 250mL Erlenmeyer flasks. 20.0 ml of water, 1.0g of KI
and 10.0 mL of 0.5 M H2SO4 was also added to
each of the solution in the flask and immediately
titrated with the standard Na2S2O3. When the pale
yellow solution is obtained, we added 1 mL or 20
drops of starch solution that causes it to turn to
blue. Immediately titrate it again until the blue
colour disappears. Record the initial and final
solution of the titrant in each sample solution.
For the water analysis sample, we went to the
Institute of Mathematics front yard and filled the
empty glass bottle covered with aluminium foil to
overflowing with the pond water. We covered the
mouth of the glass bottle with its air-tight cap
while it is still submerged in the water to avoid
the inclusion of air bubbles. After getting the
sample, we added the following reagents in
succession: 0.5 mL of MnSO 4 and 0.5 mL of NaOH
with KI and NaN3 solution. Then, close the bottle
and shake it thoroughly. Remove the cover again
and slowly add 2.0 mL of concentrated H 3PO4. All
the addition of reagents performed was done
below the surface of the water using measuring
pipettes to avoid inclusion of air bubbles.
Cover and shake the bottle and let it stand for
10 minutes as instructed. Then, take a 50.0 mL
aliquot of the solution and transfer into a 250-mL
Erlenmeyer flask. Titrate it with the standard
Na2S2O3 solution until a pale yellow colour is
obtained then add 1.0 ml or 20 drops of starch
solution. The pale yellow solution will turn into

blue then continue titrating until the blue colour
disappears. Record the initial and final volume of
the titrant in each sample solution.
Results and Discussion
The standardization of Na 2S2O3 includes the
following equations:
I2 + I- I3[1]
22S2O3 + I3- S4O62- + 3I- [2]
The stoichiometric ratio is 1mmol IO3-: 6
mmols S2O32-. H2SO4 is added to increase the
acidity of the solution and will let the reaction
with iodate [IO3-] to take place. Iodine is a
common oxidizing titrant. Compared with other
redox titrants like MnO4-, Ce 4+ and Cr2O7, iodine is
a weak oxidizing agent and is only useful in
analysis of analytes that are strong reducing
agents1. Because of iodines poor solubility,
solutions are prepared by adding an excess
of I-. Acidic H2SO4 was added first to adjust the
environment of the solution and increase the
acidity then KI was added to provide the I- needed
to increase the solubility of I2 and form a more
soluble triiodide ion, I3-.
Since direct titration couldnt be performed to
I- solutions because it is subjected to air oxidation
when forming I3- from I-, excess KI is added to
reduce the analyte and liberate a stoichiometric
amount of I3-.
In water sample analysis, the following
equations are involved:
MnSO42H2O Mn2+ + SO42- [3]
Mn2+ + 2OH- Mn(OH)2
[4]
O2 + 4Mn(OH)2 + 2H2O 4Mn(OH)3(s)
[5] OR
O2 + 4Mn(OH)2 4MnO(OH)(S) + 2H2O
[6]
The stoichiometric ratio is 1 mmol O 2: 4 mmols
S2O32-. The sample solution to be analysed is
treated with a solution of MnSO4 and then with a
solution of NaOH and KI as shown in reactions 3
and 4. Under these alkaline conditions, dissolved
oxygen (O2) oxidizes the Mn2+ to MnO2. Then,
concentrated phosphoric acid (H3PO4) was added
to the sample. Under the new conditions, I- is
oxidized to I3- by MnO2.
MnSO4 was added first to the solution in order
to have a steady source of Mn 2+ ions needed for
the reaction to occur. Then, 0.5 ml of NaOH with
KI and NaN3 solution was added and together
they form ammonium hydrogen carbonate
(NH4HCO3) and sodium azide (NaN3). NH4HCO3 is
added to prevent the interference of organic
compounds in the solution while NaN3 was
introduced to eliminate the interference of nitrite
(NO2-) in the solution. Other than thiosulfate,
nitrite is also oxidized by iodine that results to the
reduction of the volume of the titrant used. At this
point, precipitates were formed as stated in
reactions 5 and 6.
Phosphoric acid was also added to the solution
to have an acidic environment for the reaction
Page |3
and dissolves the precipitates formed earlier. It

also inactivates Fe3+ ions that may interfere and
consume the oxygen in the sample. The solution
now has a pH value ranging from 1 to 2.5 after
the addition of the acid. The addition of every
reagent is in a definite sequence because every
added chemical reacts for the completion of the
reaction or elimination of interfering substances.
Random addition of the reagents may cause
errors in results or the reaction may not proceed.
The amount of I 3- formed is determined by
titrating with S2O32- using starch as an indicator. If
we can determine the amount of I3- by titrating it
with S2O32-, we can also determine the amount of
dissolved oxygen present in the sample. The
starch is added towards the end of the titration to
prevent the stabilization of the I2- starch complex.
The starch has a helical structure and once the I 2
is added, it will be encaged within the helix and
achieving the endpoint will be difficult.
In this experiment, we used an iodometric
titration. The difference between iodometric and
iodimetric titration is the choice of analyte and
titrant. In iodometric titration, sodium thiosulfate
is used as the titrant and the analyte is iodine
while in iodimetric titration, iodine is the titrant
and the analyte is sodium thiosulfate.
With all the data gathered, we are able to
calculate the molarity of the standard Na 2S2O3
solution. Using the stoichiometric ratio, we
converted the moles of the primary standard to
the moles of the titrant divided by the total
volume consumed for the titration and multiplied
by the aliquot factor. Average molarity of Na 2S2O3
was
0.0111849157approximately 0.0112 . The
molarity of Na2S2O3 was then used to calculate the

ppm of the water sample. We obtained a value of
1.550878041 ppmO2 and from the table below,
DO Content (ppm
O2), 20 C
8-9
6.7 - 7.9
4.5 6.6
Water Quality
Clean, good water
Slightly polluted
Moderately polluted, can
sustain life of warm water
Below 4.5
fishes
0-2
Highly polluted
Cannot sustain life
we can see that the water sample cannot sustain
life and is highly polluted.
Some factors may affect the results obtained
from the experiment like instead of ten minutes,
the sample solution is made to stand overnight
before analysis. The effect of this on the dissolved
oxygen content would be indeterminate because
the sample might have heterotrophic and
photosynthetic organisms that may perform
cellular respiration and photosynthesis. In other
cases wherein the MnSO4 is added and the
solution made to stand for an hour before the
alkaline KI solution is added may result to a

decrease to the dissolved oxygen content of the
water sample. The manganese will undergo
reduction since it is light sensitive and will cause
a decrease to both the volume of the titrant and
the concentration of dissolved oxygen.
Errors in every experiment is inevitable and
predictions of their possible effects on the results
may help determine what to do to correct them
and if possible, to avoid them. Possible sources of
errors in the conducted experiment may be the
incorrect order of adding reagents in the water
sample. The addition of phosphoric acid before
potassium iodide will lead to the formation of
iodic acid.
IO3- + H+ HIO3
[7]
Page |4
Conclusion and Recommendations
References
Analytical Chemistry Academic Group, Analytical
Chemistry
Laboratory
Manual
(Elementary
Quantitative Inorganic Analysis Chem 26.1),
2013, 30
Winkler, L.W. Die Bestimmung des in Wasser
gelsten Sauerstoffen. Berichte der Deutschen
Chemischen Gesellschaft, 1888, 21: 28432855.
Page |5
Appendix (single column format

A. Answers to Questions (if necessary)
B. Figures (if necessary)
C. Raw Data Table (if necessary)
D. Working Equations
E. Sample Calculations
Standardization of Na2S2O3 Solution
Primary standard used: KIO3
Formula Mass of 1 standard: 214.0
% Purity of 1 standard: 99.4 %
Weigh of standard, g: 0.1584
Volume of standard solution: 100 mL
Trial
Volume of KIO3 standard, mL
10
10
10
Final volume of Na2S2O3, mL
38.8
42
40.7
Initial volume of Na2S2O3, mL
Net volume of Na2S2O3, mL
38.8
37.0
40.7
M Na2S2O3
Trial 1:
0.1584 g x
=
Trial 2:
0.1584 g x
1mol 6 mol Na2 S 2 O3

x
x 0.994
214.0 g
1 mol KI O3
10
x
0.0388
100
0.01137751228
0.0114

x
x 0.994
214.0 g
1 mol KI O3
10
x
0.0370
100
= 0.01133086133 0.0113
Trial 3:
0.1584 g x

x
x 0.994
214.0 g
1 mol KI O3
10
x
0.0407
100
= 0.0108463735 0.0108
Average M Na2S2O3
0.01137751228+0.01133086133+ 0.0108463735
=0.01118
3
Page |6
Sample Analysis
Location of Sampling: Institute of Mathematics frontyard
Total Volume of Sample: 500 mL
Trial
Final volume of Na2S2O3, mL
1.50
6.20
Initial volume of Na2S2O3, mL
1.50
Net volume of Na2S2O3, mL
1.50
1.20
1.50
DO content, ppm O2
Trial 1:
0.0015 L x
0.0111849157 mol 4 mol O2 31.998 g

x
x
L
1 mol S2 O3 1mol O2
0.00150
1.43157973 1. 43
Trial 2:
0.0015 L x
Trial 3:
0.0015 L x
0.0111849157 mol 4 mol O2 31.998 g

x
x
L
1 mol S2 O3 1mol O2
=1.7894
0.00120
0.0111849157 mol 4 mol O2 31.998 g

x
x
L
1 mol S2 O3 1mol O2
0.00150
1.43157973 1. 43
Average DO content, ppm O2

RSD
Confidence Interval
Other remarks:
1.43157973+1.789474663+1.4317973
=1.550878041 ppm O 2
3
RSD=
0.2065679575
x 1000 ppt=133.1879702 ppt
1.550950564
1.550878041 0.2
Page |7

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J.N. Macabata / Chemistry 26.

Quantitative Determination of Dissolved Oxygen Content by Winkler Redox

J.N. Macabata / Chemistry 26.1 (2016)

3. 250.0 mL 0.125 M stock Na2S2O3 solution from

J.N. Macabata / Chemistry 26.1 (2016)

solution. The pale yellow solution will turn into

and dissolves the precipitates formed earlier. It

0.0111849157approximately 0.0112 . The

molarity of Na2S2O3 was then used to calculate the

1.550878041 ppmO2 and from the table below,

J.N. Macabata / Chemistry 26.1 (2016)

alkaline KI solution is added may result to a

Conclusion and Recommendations

J.N. Macabata / Chemistry 26.1 (2016)

Appendix (single column format

Volume of KIO3 standard, mL

Final volume of Na2S2O3, mL

Initial volume of Na2S2O3, mL

Net volume of Na2S2O3, mL

1mol 6 mol Na2 S 2 O3

1mol 6 mol Na2 S 2 O3

1mol 6 mol Na2 S 2 O3

J.N. Macabata / Chemistry 26.1 (2016)

Final volume of Na2S2O3, mL

Initial volume of Na2S2O3, mL

Net volume of Na2S2O3, mL

0.0111849157 mol 4 mol O2 31.998 g

0.0111849157 mol 4 mol O2 31.998 g

0.0111849157 mol 4 mol O2 31.998 g

Average DO content, ppm O2

J.N. Macabata / Chemistry 26.1 (2016)

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