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Determination of dissolved oxygen by Winkler‘s method

Saturday 21 December 2013



Principle: The experiment is based on the principle of iodometric titration. When a strong alkaline solution of MnSO4 (divalent) is added to a water sample containing dissolved oxygen, it picks up oxygen to form basic MnO(OH)2 (tetravalent) which is needed to oxidize KI to I2 in presence of H2SO4. The liberated I2 is titrated against standard sodium thiosulphate using starch as indicator. By knowing the volume of sodium thiosulphate consumed DO content can be determined. The reactions are shown below:
                  MnSO4 + 2KOH -------àMn(OH)2  + K2SO4
                  2 Mn(OH)2 +O2 ----à 2 MnO(OH)2 (Basic manganic oxide)
                              MnO(OH)2 + H2SO4 ----àMnSO4 + 2H2O + [O]
                  2KI + H2SO4 + [O] -----à K2SO4 + H2O + I2
                  I2 + 2Na2S2O3 ------à 2NaI + Na2S4O6


Procedure:
·         Pipette out 300ml of water sample into a clean glass stoppered bottle. Add 3ml of manganous sulphate solution and 3ml of alkaline potassium iodide solution.
·         The bottle is stoppered and shaken well for 10- 15min. The precipitate is allowed to settle down.
·         Then add 1ml of conc. H2SO4 and bottle is stoppered and mix well until the precipitate dissoveles completely. The iodine is liberated.
·         100 ml of this solution is pipette out into a clean conical flask. Add 2ml of freshly prepared starch indicator.
·         The solution is titrated against standard solution of sodium thiosulphate till the blue color disappears. Record the volume of sodium thiosulphate consumed.
Calculation:
Volume of water sample taken= 100ml
Volume of sodium thiosulphate consumed = V1 ml
Normality of sodium thiosulphate used = N1
Normality of oxygen content in water =    V1 x N1
                                                           100
                                                   = N2
Hence oxygen content in water = N2 x Equivalent weight of oxygen
                                           = N2 x 8 x 1000 mg/dm3

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