EXP.

NO: ------------ DATE: -------------------

DETERMINATION OF DISSOLVED OXYGEN IN WATER BY WINKLER’S METHOD

Aim:
To determine the amount of Dissolved Oxygen in the given water sample by Winkler’s
method. You are provided with a standard solution of potassium dichromate of strength 0.01N.

Principle:
Pure water always has dissolved air(oxygen), usually to an extent of 8 mg /L at 25ºC. If
the water is impure the dissolved oxygen content may decrease. Hence the amount of
dissolved oxygen will indirectly indicate the purity of water sample with reference to organic
impurities.Dissolved oxygen can be determined by Winkler’s method, where the reagent
ManganousSulphate and alkali Iodide mixture are added the following reactions take place.

MnSO4+ 2 KOH K2SO4 + Mn(OH)2

2 Mn(OH)2 + O2 MnO(OH)2

Thus the Manganese hydroxide is oxidized to Manganic oxyhydroxide by the presence of

O2 dissolved in water. When Sulphuric acid is added to the mixture, the following reactions take
place.
MnO(OH)2 + H2SO4 Mn(SO4)2 + 3 H2O
Mn(SO4)2 + 2 KI MnSO4 + K2SO4 + I2

This Iodine liberated is equivalent to the amount of oxygen present in water. The
liberated Iodine can be immediately titrated with sodium thiosulphate taken in the burette.
2Na2S2O3 + I2 Na2S4O6 + 2 NaI

Equivalent weight of oxygen is 8.

Procedure:
Titration -I
Standardization of Sodium thiosulphate:
Burette is filled with sodium thiosulphate solution. 20 ml of potassium dichromate is
pipetted out into a clean 250ml conical flask and 20 ml of dil. H2SO4 is added. Then 20 ml of 10%
KI solution is added and immediately the liberated Iodine is titrated against Sodium
thiosulphate taken in the burette. When the solutions attains straw yellow colour, few drops of
starch indicator is added and the titration is continued. The end point is the disappearance of
blue colour and appearance of light green colour. The titration is repeated for concordant
values.

Titration:I
Standardisation of Sodium thiosulphate
Potassium dichromate Vs Sodium thiosulphate Indicator: Starch
Sl. Volume of Potassium Burette reading Volume of Sodium Concordant
no dichromate (V1) ml Initial Final thiosulphate (V2) ml Value

Volume of potassium dichromate (V1) = 20 ml

Strength of potassium dichromate (N1) = 0.01N
Volume of sodium thiosulphate (V2) =---------ml
Strength of Sodium thiosulphate (N2) = (V1N1/V2) = (20 x 0.01)/ V2= ------------N

Titration-II:
Estimation of dissolved oxygen:
A water sample is collected in the BOD bottle up to the neck. 2ml of Manganous
sulphate solution and subsequently 2ml of alkali-iodide reagent are added, keeping the tip of
the pipette below the surface of the liquid. The bottle is closed with stopper without
entrainment of air and mixed by inverting the bottle atleast for about 10 times. Now a brown
 precipitate of basic Manganic oxide appears. Instead of brown if a white precipitate is formed
the sample may be considered devoid of oxygen. The precipitate is allowed to settle
completely leaving a clear supernatant liquid. The stopper is carefully removed and add 2ml of
concentrated Sulphuric acid by the sides of the bottle. The bottle is closed with a stopper and
thoroughly mixed until dissolution is complete. 100ml of this solution is measured out into a
conical flask and titrated with standardized (approximately 0.01N) Sodium thiosulphate solution
using starch as indicator. The end point is disappearance of blue colour and appearance of light
green colour. The titration is repeated for concordant values.
Titration-II:
Estimation of dissolved oxygen:

Water sample Vs Standardised Sodium thiosulphate (Starch indicator)

Sl. Volume of Water Burette reading Volume of Sodium Concordant
no sample (V2) ml Initial Final thiosulphate (V1) ml Value

Calculation:

Volume of Sodium thiosulphate (V1) = --------------ml

Strength of Sodium thiosulphate (N1) = --------------N
Volume of water sample (V2) = 100 ml
Strength of water sample (N2) = Strength of DO in water (N2) = (V1N1) / V2 = V1N1 / 100

Amount of dissolved oxygen in a given water sample = N2 x 8 x 1000 mg/L

Result:

Amount of dissolved oxygen in a given water sample = -----------------mg / L