J.N. Macabata / Chemistry 26.

1 (2016) Page |1

Quantitative Determination of Dissolved Oxygen Content by Winkler Redox

Titration
Jelica N. Macabata
a
National Institute of Geological Sciences. University of the Philippines- Diliman, 1101, Quezon City
Performed 30 June 2016; Submitted 4 July 2016

ABSTRACT
Dissolved oxygen
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Introduction 3. 250.0 mL 0.125 M stock Na2S2O3 solution from

Na2S2O3∙5H2O crystals – weigh g of crystals in a
In studying environmental and marine science, beaker and
it is important to have knowledge on dissolved dissolve in about 100.0 mL boiled distilled
oxygen (O2) content of a freshwater sample. water
Dissolved oxygen concentration is expressed as then transfer to a 250-mL volumetric flask.
the number of millilitres of oxygen gas (O2) per Wash
litre of freshwater sample (mL or L-1). Water the beaker with boiled distilled water and
pollution control and waste water treatment catch
process control are determined by the dissolve the washings into the flask.
oxygen test2. It may be used by marine biologist 4. 50.0 mL 0.5 M H2SO4 solution
to measure primary production or by physical 5. Starch solution – weigh 1.0 g of starch in a
oceanographers to study water masses in the beaker and
ocean. In terms of chemistry, it provides measure dissolve until a smooth paste is obtained.
of the redox potential of a water column. Pour it
Winkler method, developed in 1888, is used to in a 100.0 ml boiled distilled water and
accurately measure the dissolved oxygen keep the
concentration of a particular sample. The method solution in 90-100 degrees Celsius to avoid
was then modified by Strickland and Parsons in drying up.
1968. This experiment provides the readers the 6. 250.0 mL 0.0125 M standard Na 2S2O3 solution
knowledge to perform the water sampling and from the
pre-treatment techniques for dissolved oxygen 0.125 M stock Na2S2O3 solution – pipette
analysis. It will also determine the amount of 0.125 M
dissolved oxygen in a water sample from a pond stock solution and transfer to a 250.0 ml
in the Institute of Mathematics, College of Science volumetric flask and dilute to mark.
University of the Philippines-Diliman using Standardization of the titrant Na2S2O3 was
Winkler redox titration and discuss the chemistry done by weighing 0.15 grams of the primary
behind the Winkler method for dissolved oxygen standard KIO3 and dissolved in 50.0 mL of distilled
determination. water. Then the solution was transferred
quantitatively into a 100-mL volumetric flask and
Materials and Methods diluted to mark. Three 10-mL aliquots was taken
from the solution and transferred into three 250-
In performing the experiment, iron stands, mL Erlenmeyer flasks. 20.0 ml of water, 1.0g of KI
burette clamps and aluminium foil are needed. and 10.0 mL of 0.5 M H2SO4 was also added to
We also prepared clean glass bottle with cap, each of the solution in the flask and immediately
burettes (50 mL), beakers (50-, 100-mL), titrated with the standard Na2S2O3. When the pale
volumetric flasks (25-, 100-, 250-mL), volumetric yellow solution is obtained, we added 1 mL or 20
pipettes (10-, 50-mL), Erlenmeyer flasks (250-ml), drops of starch solution that causes it to turn to
watch glass and syringe. We also used analytical blue. Immediately titrate it again until the blue
balance, top-loading balance and hot plate for the colour disappears. Record the initial and final
experiment. solution of the titrant in each sample solution.
The following solutions should also be For the water analysis sample, we went to the
prepared: Institute of Mathematics front yard and filled the
1. 25.0 mL 4.0 M MnSO 4 from MnSO4∙2H2O empty glass bottle covered with aluminium foil to
crystals – weigh overflowing with the pond water. We covered the
18.62 grams of the crystals and dissolve in mouth of the glass bottle with its air-tight cap
about while it is still submerged in the water to avoid
10-ml distilled water then filter the the inclusion of air bubbles. After getting the
solution into a sample, we added the following reagents in
25-ml volumetric flask and dilute to mark. succession: 0.5 mL of MnSO 4 and 0.5 mL of NaOH
2. 25.0 mL 18 M NaOH with 5.0 g KI and 0.15 g with KI and NaN3 solution. Then, close the bottle
NaN3 – and shake it thoroughly. Remove the cover again
weigh the following solids and dissolve in a and slowly add 2.0 mL of concentrated H 3PO4. All
beaker the addition of reagents performed was done
with 10 mL distilled water while stirring in below the surface of the water using measuring
a hot pipettes to avoid inclusion of air bubbles.
plate then transfer to a 25-mL volumetric Cover and shake the bottle and let it stand for
flask and dilute to mark. This must be 10 minutes as instructed. Then, take a 50.0 mL
done in a water bath, under the fume aliquot of the solution and transfer into a 250-mL
hood. 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
 J.N. Macabata / Chemistry 26.1 (2016) Page |3

solution. The pale yellow solution will turn into and dissolves the precipitates formed earlier. It
blue then continue titrating until the blue colour also inactivates Fe3+ ions that may interfere and
disappears. Record the initial and final volume of consume the oxygen in the sample. The solution
the titrant in each sample solution. now has a pH value ranging from 1 to 2.5 after
the addition of the acid. The addition of every
Results and Discussion reagent is in a definite sequence because every
added chemical reacts for the completion of the
The standardization of Na 2S2O3 includes the reaction or elimination of interfering substances.
following equations: Random addition of the reagents may cause
I2 + I- → I3- [1] errors in results or the reaction may not proceed.
2S2O3 + I3- → S4O62- + 3I- [2]
2-
The amount of I 3- formed is determined by
The stoichiometric ratio is 1mmol IO3-: 6 titrating with S2O32- using starch as an indicator. If
mmols S2O32-. H2SO4 is added to increase the we can determine the amount of I3- by titrating it
acidity of the solution and will let the reaction with S2O32-, we can also determine the amount of
with iodate [IO3-] to take place. Iodine is a dissolved oxygen present in the sample. The
common oxidizing titrant. Compared with other starch is added towards the end of the titration to
redox titrants like MnO4-, Ce 4+ and Cr2O7, iodine is prevent the stabilization of the I2- starch complex.
a weak oxidizing agent and is only useful in The starch has a helical structure and once the I 2
analysis of analytes that are strong reducing is added, it will be “encaged” within the helix and
agents1. Because of iodine’s poor solubility, achieving the endpoint will be difficult.
solutions are prepared by adding an excess In this experiment, we used an iodometric
of I-. Acidic H2SO4 was added first to adjust the titration. The difference between iodometric and
environment of the solution and increase the iodimetric titration is the choice of analyte and
acidity then KI was added to provide the I- needed titrant. In iodometric titration, sodium thiosulfate
to increase the solubility of I2 and form a more is used as the titrant and the analyte is iodine
soluble triiodide ion, I3-. while in iodimetric titration, iodine is the titrant
Since direct titration couldn’t be performed to and the analyte is sodium thiosulfate.
I- solutions because it is subjected to air oxidation With all the data gathered, we are able to
when forming I3- from I-, excess KI is added to calculate the molarity of the standard Na 2S2O3
reduce the analyte and liberate a stoichiometric solution. Using the stoichiometric ratio, we
amount of I3-. converted the moles of the primary standard to
In water sample analysis, the following the moles of the titrant divided by the total
equations are involved: volume consumed for the titration and multiplied
MnSO4∙2H2O → Mn2+ + SO42- [3] by the aliquot factor. Average molarity of Na 2S2O3
Mn2+ + 2OH- → Mn(OH)2 [4]
was 0.0111849157∨approximately 0.0112 . The
O2 + 4Mn(OH)2 + 2H2O ↔ 4Mn(OH)3(s) [5] OR
O2 + 4Mn(OH)2 ↔ 4MnO(OH)(S) + 2H2O [6] molarity of Na2S2O3 was then used to calculate the
The stoichiometric ratio is 1 mmol O 2: 4 mmols ppm of the water sample. We obtained a value of
S2O32-. The sample solution to be analysed is 1.550878041 ppmO2 and from the table below,
treated with a solution of MnSO4 and then with a
solution of NaOH and KI as shown in reactions 3 DO Content (ppm
and 4. Under these alkaline conditions, dissolved O2), 20∘ C Water Quality
oxygen (O2) oxidizes the Mn2+ to MnO2. Then, 8-9 Clean, good water
concentrated phosphoric acid (H3PO4) was added
6.7 - 7.9 Slightly polluted
to the sample. Under the new conditions, I- is
oxidized to I3- by MnO2. 4.5 – 6.6 Moderately polluted, can
MnSO4 was added first to the solution in order sustain life of warm water
to have a steady source of Mn 2+ ions needed for Below 4.5 fishes
the reaction to occur. Then, 0.5 ml of NaOH with 0-2 Highly polluted
KI and NaN3 solution was added and together Cannot sustain life
they form ammonium hydrogen carbonate we can see that the water sample cannot sustain
(NH4HCO3) and sodium azide (NaN3). NH4HCO3 is life and is highly polluted.
added to prevent the interference of organic Some factors may affect the results obtained
compounds in the solution while NaN3 was from the experiment like instead of ten minutes,
introduced to eliminate the interference of nitrite the sample solution is made to stand overnight
(NO2-) in the solution. Other than thiosulfate, before analysis. The effect of this on the dissolved
nitrite is also oxidized by iodine that results to the oxygen content would be indeterminate because
reduction of the volume of the titrant used. At this the sample might have heterotrophic and
point, precipitates were formed as stated in photosynthetic organisms that may perform
reactions 5 and 6. cellular respiration and photosynthesis. In other
Phosphoric acid was also added to the solution cases wherein the MnSO4 is added and the
to have an acidic environment for the reaction solution made to stand for an hour before the
 J.N. Macabata / Chemistry 26.1 (2016) Page |4

alkaline KI solution is added may result to a Conclusion and Recommendations

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 References
the concentration of dissolved oxygen.
Errors in every experiment is inevitable and Analytical Chemistry Academic Group, Analytical
predictions of their possible effects on the results Chemistry Laboratory Manual (Elementary
may help determine what to do to correct them Quantitative Inorganic Analysis Chem 26.1),
and if possible, to avoid them. Possible sources of 2013, 30
errors in the conducted experiment may be the
incorrect order of adding reagents in the water Winkler, L.W. Die Bestimmung des in Wasser
sample. The addition of phosphoric acid before gelösten Sauerstoffen. Berichte der Deutschen
potassium iodide will lead to the formation of Chemischen Gesellschaft, 1888, 21: 2843–2855.
iodic acid.
IO3- + H+ → HIO3 [7]
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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 1 2 3

Volume of KIO3 standard, mL 10 10 10

Final volume of Na2S2O3, mL 38.8 42 40.7

Initial volume of Na2S2O3, mL 0 5 0

Net volume of Na2S2O3, mL 38.8 37.0 40.7

M Na2S2O3 Trial 1:
1mol 6 mol Na2 S 2 O3
0.1584 g x x x 0.994
214.0 g 1 mol KI O3 10
x
0.0388 100

= 0.01137751228 ≈ 0.0114

Trial 2:
1mol 6 mol Na2 S 2 O3
0.1584 g x x x 0.994
214.0 g 1 mol KI O3 10
x
0.0370 100
= 0.01133086133 ≈ 0.0113

Trial 3:
1mol 6 mol Na2 S 2 O3
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
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Sample Analysis
Location of Sampling: Institute of Mathematics frontyard
Total Volume of Sample: 500 mL

Trial 1 2 3
Final volume of Na2S2O3, mL 1.50 6.20 3
Initial volume of Na2S2O3, mL 0 5 1.50
Net volume of Na2S2O3, mL 1.50 1.20 1.50
DO content, ppm O2 Trial 1:
0.0111849157 mol 4 mol O2 31.998 g
0.0015 L x x x
L 1 mol S2 O3 1mol O2
0.00150
¿ 1.43157973≈ 1. 43

Trial 2:
0.0111849157 mol 4 mol O2 31.998 g
0.0015 L x x x
L 1 mol S2 O3 1mol O2
=1.7894
0.00120

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

Average DO content, ppm O2 1.43157973+1.789474663+1.4317973

=1.550878041 ppm O 2
3
RSD 0.2065679575
RSD= x 1000 ppt=133.1879702 ppt
1.550950564
Confidence Interval 1.550878041 ± 0.2

Other remarks:
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