6.6.2

Winkler Method

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The Winkler Method

The Winkler method is a redox titration process used to determine the concentration of dissolved oxygen in water samples.

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The Winkler method

  • The Winkler method can be used to determine the biological oxygen demand (BOD) of a water sample.
  • The titration relies on a multi-step process, shown below:
    • Step 1: 2Mn2+(aq) + 4OH-(aq) + O2(g) → 2MnO(2)(s) + 2H2O(l)
    • Step 2: MnO2(s) + 2I-(aq) + 4H+(aq) → Mn2+(aq) + I2(aq) +2H2O(l)
    • Step 3: 2S2O32-(aq) + I2(aq) → S4O62-(aq) + 2I-(aq)
  • The endpoint of the titration is observed by the disappearance of the orange-brown iodine colour, which produces the colourless iodide ions.
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Stoichiometry

  • Considering the stoichiometry of the overall process, we can calculate the moles of oxygen in the initial water sample:
    • O2 : MnO2 : I2 : S2O32- = 1 : 2 : 2 : 4
  • The important ratio to consider is O2 : S2O32- = 1 : 4
  • The concentration of oxygen in the analysed water sample is typically calculated in mg dm-3, which is the same as ppm (parts per million).
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Sample question

  • A 500.0 cm3 sample of river water was analysed to determine the dissolved oxygen concentration by adding Mn2+ in basic solution, followed by acidified KI. This solution required 13.50 cm3 of 0.0420 mol dm-3 of Na2S2O3(aq) to completely react with the iodine produced.
  • Use the information and the equations for the Winkler process to determine the dissolved oxygen content of the water sample in mg dm-3 (ppm).
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Answer

  • No. of moles of S2O32-:
    • n(S2O32-) = CV = 0.0420 mol dm-3 × 0.01350 dm3 = 5.67 ×10-4 mol
  • No. of moles of O2 (1:4 stoichiometric ratio):
    • n(O2) = 5.67 × 10-4 mol ÷ 4 = 1.4175 × 10-4 mol
  • Mass of O2:
    • m(O2) = 1.4175 × 10-4 mol × 31.998 g mol-1 = 4.536 ×10-3 g
  • Convert to mg dm-3:
    • mg dm-3 = 4.536 mg ÷ 0.5000 dm3 = 9.07 mg dm-3

Jump to other topics

1Structure - Models of the Particulate of Matter

2Structure - Models of Bonding & Structure

3Structure - Classification of Matter

3.1The Periodic Table: Classification of Elements

3.2Periodic Trends

3.3Group 1 Alkali Metals

3.4Halogens

3.5Noble gases, group 18

3.6Functional Groups: Classification of Organic

3.7Functional Group Chemistry

3.8Alkanes

3.9Alcohols

3.10Halogenoalkanes

4Reactivity - What Drives Chemical Reaction?

5Reactivity - How Much, How Fast & How Far?

6Reactivity - The Mechanisms of Chemical Change

7Measurement, Data Processing & Analysis

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