Universiti Tunku Abdul Rahman

Faculty Lee Kong Chian Faculty of Engineering and

Science
Department: Department of Civil Engineering
Unit Code and Name UEMX 3613 Environmental Science &
Engineering
Experiment No.: 1/4
Title of Experiment: Titrimetric analysis: Winkler’s Method for
Dissolved Oxygen
Laboratory Room No. and Name: KB510
Experiment Duration (hour): 3 hours
Number of Student per Group 5 students x 4 groups
Number of Student per Session 20
Remarks 4 choose 2

Equipment and Materials

Quantity estimation
Item Description *Item category (e.g. per set/group of
student)
Water Sample SP 1L
Sample bottle (250 mL) W 6
Measuring pipette (2 mL) W 1
Pipette pump (10 mL) W 1
Conical flask (250 mL) W 6
Burette (50 mL) W 1
Beaker (100 mL) W 1
Filter Funnel (50mm) W 1
Schott Bottle (100 mL) – for solution
W 4
storage
Schott Bottle (250 mL) – for solution
W 1
storage
Volumetric Flask (250mL) – for solution
W 1
preparation
Retort Stand and Clamp W 1 set
50% Manganese sulphate solution CH 10 mL
Alkaline iodine solution CH 10 mL
85% Phosphoric acid CH 20 mL
Starch solution CH 20 mL
M/100 Sodium thiosulphate CH 200 mL

*Item category
SP Sample or specimen
C Consumable
CH Chemical

1 Latest updated: 15th Dec 2016 (DLMSA)

 W Labware, glassware, tool, and
components
E Equipment
S Software

EXPERIMENT 1: Titrimetric analysis: Winkler’s method for dissolved oxygen (DO).

*Important note: You are provided with a sample of water (polluted) which you will in this
experiment.

Objective: To measure the concentration of dissolved oxygen in water by Winkler’s titrometric

method. Winkler’s method is the standard non-instrumental method of measuring dissolved
oxygen in waters. It is still widely used in water analysis.

1. Duration 3 hours

2. Theory: The oxygen is reacted with freshly precipitated manganese hydroxide in alkaline
solution. Hydrated manganese dioxide is produced. When the solution is acidified in the
presence of iodide the manganese dioxide liberates iodine proportional to the oxygen
concentration, this is titrated with standard thiosulphate using starch as an indicator.

The reactions are:

O2 + 2 Mn(OH)2 + 2H2O = 2 Mn(OH)4

Mn(OH)4 = 2I- + 4 H+ = I2 + 4 H2O + Mn2+

I2 + 2S2O3-2 = S4O62- + 2 I-

The sum of the above reactions amounts to the reduction of dissolved oxygen by thiosulphate. This
gives a titration reaction as:

O2 + 4S2O32- + 2H2O = 2S4O62- + 4OH-

3. Experimental

4a. Reagents:
The reagents required are:
(i) 50% Manganese sulphate solution
(ii) Alkaline iodine solution
(iii) Concentrated, 85% phosphoric acid
(iv) Starch solution
(v) M/100 sodium thiosulphate

4b. Sampling the water

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When sampling a natural water for dissolved oxygen the greatest source of error is contamination
from the atmospheric air. To avoid this the sample bottle is filled under water and the stopper
placed in the bottle whilst it is still under water.
Fill a basin with tap water. Immerse the 250 ml sample bottle under the tap water. Remove the
stopper and allow the bottle to fill. Replace the stopper. Ensure that the bottle is completely full
of water and no air bubbles remain. In normal circumstances the bottle could now safely be
transported back to the laboratory for analysis. As the experiment is being conducted in the
laboratory you should now proceed with the titration.
Repeat this with a second bottle.

4c. Titrating the oxygen.

a. To the sample bottle, add 1 ml of 50% manganese sulphate solution from a pipette, placing the
tip of the pipette below the surface of the water sample.
b. In a similar manner add 1 ml of alkaline iodine solution.
c. Re-stopper the bottle, shake the content, and allow the precipitate to settle fort 15 min. During
this period
occasionally turn the bottle upside down to mix the content. The brown precipitate is the
manganese dioxide mixed with Manganouse hydroxide.
d. Next add 2 ml of 85% phosphoric acid.
e. Replace the stopper and again turn the bottle upside down two or three times to mix the acid
with the sample. The brown precipitate will redissolve and liberate iodine.
f. Pipette out 50 ml of this solution into a 250 ml conical flask.
g. Add 2 ml of starch solution and
h. Titrate with M/100 thiosulphate solution until the blue colour is discharged (the solution
becomes colourless).
i. Repeat the titration with the liquid from the second bottle.

3. Calculation
Let VA be the volume of sample solution titrated, VB be the volume of thiosulphate consumed, MB
is the molarity of the thiosulphate and MA is the molarity of the oxygen in the water. Then from
titration equation given above 4 moles of thiosulphate titrate 1 mole of oxygen. Hence:

VA x MA = VB x MB/4 Thus: MA = (VB x MB) / (4 x VA)

The concentration of oxygen can now be calculated in μg/l from the molarity.

C (μg/l) = MA x MW(O2) x 106

Calculate an oxygen concentration for the results from both bottles.

DISCUSSION:
Compare the results for different water samples, establish the trends and provide their
interpretation and explanation with identification of the factors that affect the results.

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