Determination of Chemical Oxygen Demand (COD)

Objective:

To determine chemical oxygen demand in the given water sample

Introduction:

The chemical oxygen demand (COD) test is commonly used to indirectly measure the amount
of organic compounds in water. COD is also used to determine the amount of organic pollutants
found in surface water (e.g. lakes and rivers), making COD a useful measure of water quality.
It is expressed in milligrams per liter (mg/L), which indicates the mass of oxygen consumed
per liter of solution.

COD is the measurement of the amount of oxygen in water consumed for chemical oxidation
of pollutants. It determines the quantity of oxygen required to oxidize the organic matter in
water or waste water sample, under specific conditions of oxidizing agent, temperature, and
time. This method covers the determination of COD in ground and surface waters, domestic
and industrial wastewaters. The applicable range is 3-900 mg/L.

The organic matter present in sample gets oxidized completely by potassium dichromate
(K2Cr2O7) in the presence of sulfuric acid (H2SO4), silver sulfate (AgSO4) and mercury sulfate
(HgSO4) to produce CO2 and H2O, while dichromate is reduced to Cr3+.

𝐶𝑟2 𝑂72− + 14𝐻 + + 6𝑒 − → 2𝐶𝑟 3+ + 7𝐻2 𝑂

The sample is refluxed with a known amount of K2Cr2O7 in the sulfuric acid medium and the
excess of K2Cr2O7 is determined by titration against ferrous ammonium sulfate, using ferroin
as an indicator. This method is called a “back titration” in analytical chemistry.

6𝐹𝑒 2+ + 𝐶𝑟2 𝑂72− + 14𝐻 + → 6𝐹𝑒 3+ + 2𝐶𝑟 3+ + 7𝐻2 𝑂

The dichromate consumed by the sample is equivalent to the amount of O 2 required to oxidize
the organic matter.

Prelab Questions:

1. What are the advantages of COD over the biochemical oxygen demand (BOD) test?
2. The apparent results of the COD tests are usually higher than they supposed to be. What
compounds can interfere with the estimation of COD in water samples?

Procedure:

1. Pour 2.5 mL of water sample into a tube and 2.5 mL of distilled water in another tube.
2. Add 1.5 mL of potassium dichromate into both tubes
3. Carefully add 3.5 mL of sulfuric acid reagent into both tubes.
4. Close the tubes tightly and incubate in COD digester at 150⁰C for 2 hours.
5. After cooling to room temperature, transfer the content to a conical flask

ESC3204 Wastewater Treatment, Faculty of Environmental Studies

 6. Add 2 drops of Ferroin indicator.
7. Titrate the contents against ferrous ammonium sulfate. Continue the titration until the
color changes to reddish brown.

Results: Record the calculations and answer the question in your lab notebook or report.

Calculation:

COD as mg/L O2

(𝐴 − 𝐵) × 𝑁 × 8000
=
𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑠𝑎𝑚𝑝𝑙𝑒 𝑢𝑠𝑒𝑑 (𝑚𝐿)

where
A = mL FAS used for blank
B = mL FAS used for sample
N = normality of FAS
8000 = milliequivalent weight of oxygen x 1000 mL/L

Discussion:

1. What are the legal limits (if any) of COD in wastewater discharge?
2. The presence of chloride can interfere in this analytical determination. How could it be
overcome?
3. Compare your results with the legal limits for rivers or streams; do your values exceed
such legal limits?

ESC3204 Wastewater Treatment, Faculty of Environmental Studies