Determination of chemical oxygen demand of

water

Principle of chemical oxygen demand

In dichromate method the organic matter in water oxidize with the strong oxidizing agent potassium
dichromate under acidic conditions. Normally sulfuric acid is used to achieve the acidity in this COD test
method. An additional amount of potassium dichromate are taken, to sure completely oxidation of all
organic matter. After complete the oxidation, measure the excess amount of potassium dichromate by
titrating with ferrous ammonium sulfate. During the titration the ferroin is used as indicator. At the end
point the color of the ferroin changes from blue-green to a reddish brown. The consumption of the
dichromate is proportional to the amount of organic matters that are present in the water.
3[CH2O] + 16H+ + 2Cr2O72- 4Cr3+ + 3CO2 + 11H2O

It is a fast applicable parameter for industrial wastewater, water controlling plant, sewage, rivers, lakes or
aquifers but not applicable for drinking water as the lower content of oxidizable organic matter.
Frequently, a silver compound like Silver sulfate is used as a catalyst to promote oxidation of certain
organic compounds such as linear aliphatic compounds, aromatic compounds and pyridine. Some
inorganic materials like chloride, nitrite may interfere with the result of COD. Chloride interference can
eliminate by adding Mercuric sulfate whereas nitrite interference can eliminate by adding sulfamic acid.

COD testing equipment and reagents

1. Water sample

2. Distilled water

3. Standard Potassium dichromate solution (0.25N)

4. Sulfuric acid reagent

5. Standard ferrous ammonium sulfate (0.25 N)

6. Ferroin indicator

7. Mercuric sulfate
 8. Silver sulfate

9. Water bath

10. Titration apparatus

11. 500ml conical flask (Erlenmeyer Flask)

12. Burette

13. Pipettes

14. Pipette bulb

15. Wash bottle

COD test procedure

1. Collect the sample water from a source.

2. Take 500 ml conical flask/ reflux flask and filled with 50ml of sample water.

3. Place several boiling stones in the reflux flask.

4. Determinate the chloride ion. If it contains a significant amount then, add 1 g of HgSO4
and 5.0 ml conc. H2SO4; then swirl the mixture until the mercuric sulfate dissolves.

5. After that place the reflux flask in an ice bath and slowly add 25ml of potassium
dichromate solution (K2Cr2O7) with swirling.

6. Now add 75 ml of a mixture of sulfuric acid-silver sulfate solution to the cooled reflux
flask with swirling.

7. Apply heat to the mixture under reflux in water bath at 150C temperature for two hours.

8. Then allow the flask to cool about room temperature and wash the condenser with
distilled water. Transfer the mixture into 500 ml Erlenmeyer flask.

9. Then titrate the excess dichromate with 0.25 N ferrous ammonium sulfate, Fe(NH4)2SO4
solution by using 2 to 4 drops of ferroin indicator. At the end point the color turns from
blue-green to reddish brown and take the burette reading. Let the reading is B ml.

10. Run a blank titration similarly. Let the reading is A ml.

Chemical oxygen demand calculation
COD in mg/L= 8000 (A-B) N / V

Where,
A is the volume of FAS used in the blank sample, in milliliters.
B is the volume of FAS in the original sample, in milliliters.
N is the normality of FAS solution.
V = milliliters of sample used for the test.