This procedure covers the determination of chemical oxygen demand (COD) and the calculation for the analysis of waste-water in different stages of Effluent Treatment Plant (ETP) in the lab. chemical oxygen demand is a measure of the oxygen required to oxidize all compounds, both organic and inorganic in water.
Reagents preparation for chemical oxygen demand:
- Standard potassium dichromate solution (0.25N): weigh 12.259gm of previously dried potassium dichromate at 103°C to 105°C for 2 hrs and dissolve in distilled water and makeup to 1000 ml in a volumetric flask.
- Ferro indicator solution: Weigh 1.485 gm of 1,10-Phenanthroline monohydrate and 695 mg ferrous sulphate dissolved in distilled water and dilute to 100 ml in a volumetric flask.
- 0.1N Ferrous Ammonium Sulphate (FAS): Weigh 39.212gm of FAS and dissolve in distilled water. Add 20 ml concentrated sulphuric acid, cool and dilute to 1000 ml in a volumetric flask.
- Mercuric Sulphate (powder)
- Sulphuric acid reagent:
- Prepare sulphuric acid reagent by dissolving 22 gm of silver sulphate in 2.5 litres of conc. sulphuric acid.
- Potassium Hydrogen Phthalate standard:
- Dissolve 0.425 gm of KHP, previously dried at 120°C for 2 hrs, in 1 litre distilled water. KHP has theoretical COD of 1.176 O2/mg and this solution has theoretical COD of 500 micrograms of O2/ml of 500ppm.
- 0.1N Potassium Dichromate Solution:
- Dissolve 0.5gm of Potassium dichromate in 100ml of water
Standardization of FAS:
- Take an iodine flask containing 90 ml of water.
- Take 10 ml of 0.1N Potassium dichromate solution (prepare 0.1N Potassium dichromate solution by dissolving about 0.5 gm potassium dichromate in 100 ml of water.
- Add 12 ml of conc.sulphuric acid. Cool the content in the flask to laboratory temperature.
- Add 3 to 5 drops of ferroin indicator solution.
- Titrate against 0.1N ferrous ammonium sulphate solution until the colour changes from blue to red.
- Note down the initial burette reading (I) and note down the final burette reading.
Calculate the normality of FAS as follows.
Normality of FAS = W/ (TV×0.04904×10).
Where TV= (F-I) volume of ferrous ammonium sulphate solution consumed in the titration
W= weight of potassium dichromate taken.
Determination of chemical oxygen demand, COD:
- Pipette 20 ml of sample in 250 ml of refluxing flask.
- Add approximately 400 mg (a pinch) of mercuric sulphate.
- Add 10 ml of potassium dichromate by pipette.
- 30 ml of the conc.sulphuric acid reagent by measuring cylinder. Acid should be added in a controlled manner with the mixing of the sample.
- If the sample colour changes to green, dilute the sample and repeat the procedure for the diluted sample.
- Connect the reflux flask through the condenser and reflux for a minimum period of 2hrs at 150°C.
- Add 80 ml distilled water through condenser cool it to room temp and titrated with standard sulphate using 2 to 4 drops of ferroin indicator.
- The endpoint is the sharp colour change from blue-green to brick red, even though blue-green reappear within minutes. Let the titrate value be ‘V’ ml
- Reflux in the same manner a blank with distilled water 20ml and follow the procedure from previously. Let the titrate value be ‘B’ ml.
- Calculate the COD (mg/lt) as follows
COD= ((B-V)×N(FAS)×8000)/vol of sample(ml).
Application of chemical oxygen demand for the treatment of effluent generated in vegetable oil refinery:
We have evidence that chemical oxygen demand represents the amount organic matter content in effluents. It is used as measuring variable to develop the kinetic data of biological process units. For example, estimation of reaction rate constants of Fenton type reagents is done using chemical oxygen demand as measuring variable. The order of the reaction is determined by the analyzing the kinetic data to design the process equipment that conducts advanced oxidation processes.
Most biological treatments designs cannot eliminate organic matter even the effluents undergo pre-treatment as separation of oil and alum flotation treatment. The need of oxidizing reagents like Fenton reagent (possess hydroxyl radicals) is required to recalcitrant organic compounds and chemical oxygen demand is only possible specification to know the performance of the reagents.