Practical investigation 5.

2
Measuring DO

NAME: CLASS:

AIM
To determine the amount of dissolved oxygen in a sample of water using the Winkler technique.

THEORY
The amount of dissolved oxygen (DO) in a sample of water gives an indication of the quality of the
water. This test is based on the Winkler technique. Dissolved oxygen is colourless and therefore
undetectable with the naked eye, so a chemical change must take place before it can be detected. In
this case, a chemical reaction replaces the oxygen with iodine. The depth of the red-brown colour of
iodine in the water is directly proportional to the amount of dissolved oxygen present.
Manganese sulfate and alkaline sodium iodide (NaOH–NaI) are added to the sample of water,
forming a white flocculant of manganous hydroxide. The manganous hydroxide flocculant reacts
quantitatively with the dissolved oxygen in the sample to form a hydrated tetravalent manganese
oxide (MnO(OH)2) that settles to the bottom of the sample. The sample is thus preserved or
‘pickled’ and can be stored in this form until analysis, ideally within 4–8 hours of sampling.
Water samples should be collected in rinsed 300 cm3 DO bottles. The bottles should be filled with a
minimum of agitation and exposure of the water sample to air, and be allowed to overflow. Ideally
1 cm3 of manganese(II) sulfate and 1 cm3 of alkaline iodide (NaOH–NaI solution) should be added
at once to the bottles when full. The bottles may then be stoppered, mixed and analysed at leisure,
but they must be shielded from strong light.
Immediately prior to analysis, the sample is acidified with sulfuric acid, which dissolves the
manganese hydroxide. Under acid conditions the tetravalent manganese acts as an oxidizing agent
and liberates free iodine from the iodide added originally as alkaline sodium iodide. The amount of
free iodine formed is equivalent to the amount of oxygen originally present in the solution and is
determined by redox titration with sodium thiosulfate.
2S2O32–(aq)  S4O62–(aq) + 2e–
I2(aq) + 2e–  2I–(aq)
The endpoint of this titration can be determined visually by the use of starch as an indicator
solution. Starch forms a blue-coloured complex with iodine, and the solution gradually turns
colourless as the thiosulfate is added. The endpoint of the titration is determined as the point at
which the solution becomes completely clear.

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© Pearson Australia 2009 (a division of Pearson Australia Group Pty Ltd) ISBN 9780733993794
This page from the Chemistry: For use with the IB Diploma Programme Options SL and HL Teacher’s Resource
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Practical investigation 5.2
Measuring DO
MATERIALS
300 cm3 DO bottle in which a sample of water Starch indicator
from a natural waterway has been obtained 0.00167 mol dm–3 potassium iodate (KIO3)
2 mol dm–3 manganese(II) sulfate (MnSO4) solution
solution 4  250 cm3 conical flasks
Alkaline iodide (NaOH–NaI) solution 50 cm3 pipette
Concentrated sulfuric acid Burette
Distilled water Pipette filler
0.018 mol dm–3 sodium thiosulfate (Na2S2O3) stand and clamp
solution

SAFETY
Safety glasses must be worn for this practical investigation.
See Risk Assessment for Practical investigation 5.2.

METHOD
1 Fill the DO bottle according to the proper sampling technique (see theory above). No air
bubbles should be present.
2 Add 1 cm3 of manganese(II) sulfate solution and 1 cm3 of alkaline iodide solution (in that
order) to the DO bottle. Cap the bottle immediately and shake until the precipitate is evenly
dispersed. If air bubbles are present, add distilled water from a wash bottle.
3 Allow the precipitate to settle for 3 minutes and shake again. Allow to stand until the
precipitate has settled about one-third of the way down the bottle.
4 Add 1 cm3 of sulfuric acid. Recap the bottle and shake until the precipitate dissolves. If there
are air bubbles trapped, add a little distilled water from the wash bottle.
5 Pipette a 50 cm3 aliquot of the liquid from the DO bottle into a conical flask.
6 Rinse and fill the burette with sodium thiosulfate. Record the initial volume of sodium
thiosulfate and begin titrating the sample, adding sodium thiosulfate very slowly until the
sample turns a pale straw colour.
7 Add 2 cm3 of the starch indicator solution to the sample.
8 Begin adding sodium thiosulfate dropwise until the blue colour just disappears. Be sure to
shake after each drop has been added.
9 Record the final volume, and hence the volume of sodium thiosulfate used, in the table below.
10 Perform the following titrations (steps 10.1–10.5) to calibrate the technique:
10.1 Blank: Fill a DO bottle with distilled water, add 1 cm3 conc. sulfuric acid and 1 cm3 of
alkaline iodide and mix.
10.2 Add 1 cm3 of manganese(II) sulfate and mix again.
10.3 Titrate 50.0 cm3 aliquots. If addition of starch indicator gives any blue color, titrate to
endpoint with sodium thiosulfate. Record the volume of sodium thiosulfate used.
10.4 Determination of f: Repeat steps 10.1 and 10.2. Add 5.00 cm3 of 0.01 mol dm–3
potassium iodate to the 50 cm3 aliquots and allow iodine to be liberated for 2–5 minutes.
10.5 Titrate this iodine with sodium thiosulfate and record the volume of titre.

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© Pearson Australia 2009 (a division of Pearson Australia Group Pty Ltd) ISBN 9780733993794
This page from the Chemistry: For use with the IB Diploma Programme Options SL and HL Teacher’s Resource
may be reproduced for classroom use.
Practical investigation 5.2
Measuring DO
RESULTS
Volume of water sample: 50.00 cm3
Concentration of the sodium thiosulfate solution: __________ mol dm–3

Titration number 1 2 3 4 5

Initial reading (cm3)

Final reading (cm3)

Volume of titre (cm3)

Average titre of sodium thiosulfate: ____________ cm3

Volume of sodium thiosulfate used in blank titration (steps 10.1–10.3): ____________ cm3
Volume of sodium thiosulfate used in titration to determine f (steps 10.4, 10.5): V1 =__________ cm3

QUESTIONS

No. Question Answer

1 Subtract the blank titration volume of

sodium thiosulfate from the average
titre. This is V2.

2 Determine the value of f by

substituting the volume used in the
titration (V1) into the following
equation: f = 5.00/V1

3 Calculate the concentration of

dissolved oxygen in mmol dm–3 by
substituting the values for f and V2
into the following equation:
O2 mmol dm–3 = 0.1006  f  V2

4 Calculate the concentration of

dissolved oxygen in cm3 dm–3 by
substituting the answer to question 3
into the following equation:
O2 cm3 dm–3
= 11.20  O2 mmol dm–3

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© Pearson Australia 2009 (a division of Pearson Australia Group Pty Ltd) ISBN 9780733993794
This page from the Chemistry: For use with the IB Diploma Programme Options SL and HL Teacher’s Resource
may be reproduced for classroom use.
Practical investigation 5.2
Measuring DO

No. Question Answer

5 Calculate the concentration of

dissolved oxygen in mg dm–3 (ppm)
by substituting the answer to
question 3 into the following
equation:
O2 mg dm–3 (ppm)
= 32.00  O2 mmol dm–3
6 List other factors that contribute to
the health of a waterway.

CONCLUSION

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© Pearson Australia 2009 (a division of Pearson Australia Group Pty Ltd) ISBN 9780733993794
This page from the Chemistry: For use with the IB Diploma Programme Options SL and HL Teacher’s Resource
may be reproduced for classroom use.