Chemical Oxygen Demand (COD) : Pillai College of Arts, Commerce and Science (Autonomous)

Mahatma Education Society`s
Pillai College of Arts, Commerce and Science (Autonomous)

New Panvel
Chemical oxygen demand

(COD)
Ms. Bhakti Hirani
Assistant Professor
Department of Biotechnology
To determine the chemical oxygen demand
(COD) of the given effluent sample.
• Chemical oxygen demand (COD) is the amount of oxygen required for oxidation of organic and
inorganic) matter by virtue of strong chemical oxidant such as potassium dichromate.
• The COD value is however, a poor measure of strength of organic matter because oxygen is also
consumed in the oxidation of inorganic ions and also because the method is a laboratory
oxidation method.
• Not withstanding its problems, it is a very important parameter in management and design of
treatment plants because of its rapidity in determination.
• Presence of toxins or unfavourable conditions does not affect the COD values and hence
COD values are especially important when BOD values cannot be accurately determined due to
the presence of toxins and other conditions unfavourable for the growth of microorganism.
• The sewage sample is refluxed by boiling with potassium dichromate, AgSO, HgSO4 in presence
of sulphuric acid.
• Organic matter in the sewage reduces potassium dichromate and the excess is determined by
titration with ferrous ammonium sulphate (0.1N) using phenanthroline indicator. The end point is
bluish green to wine red
• Potassium dichromate, used as the oxygen source with concentrated sulphuric acid
added to yield a strong acid medium. Several reagents are added during the setup of
the analysis to drive the oxidation reaction to completion and also to remove any
possible interferences. Specifically, these reagents are mercuric sulphate, silver
sulphate and sulphuric acid.
• Mercuric sulphate is added to remove complex chloride ions present in the sample.
• Without the mercuric sulphate the chloride ions would form chlorine compounds in the
strong acid media used which would oxidize the organic matter in the sample,
resulting in a COD value lower than the actual value
• Silver sulphate is added as a catalyst for the oxidation of short straight chain
organics and alcohols. Again, without the silver sulphate the COD of the sample
would be lower than the actual value.
• Sulphuric acid is added to remove interferences caused by nitrite ions. Without
sulphuric acid the COD of the sample would measure higher than the actual
value. Even with the use of these additional reagents the oxidation of the organic
matter is not always 100% complete. Volatile organics, ammonia and aromatic
are not oxidized to any great degree during the procedure.
• The advantages of the COD test as compared to the BOD test are:
1. COD results are available much sooner since there is no incubation

period.
2. The COD test requires fewer manipulations of the sample.
3. The COD test oxidizes a wider range of chemical compounds,
4. It can be standardized more easily.

• The other advantages of the test include that the O2 is also consumed by
oxidation of inorganic matter such as nitrites, sulphites, sulphides, reduced metal
ions, thiosulfates and some other organic matter such as benzene, pyridine and
other cyclic organic compounds that are oxidised by dichromate.
• As a result COD is usually higher than BOD because some organic materials
present in water may be resistant to microbial oxidation.
• Hence, such materials will be oxidised chemically and contribute to COD.
• This is also a disadvantage since it means that the test is a poor measure of
organic matter unless the presence of these compounds is taken into
consideration,
• The other disadvantages of the COD test include that the results are not directly
applicable to the 5-day BOD results without correlation studies over a long period of
time.
• The COD test neither indicates whether the waste is biodegradable nor does it
indicate the rate at which biological oxidation would proceed and hence, the rate at
which O2 would be required or depleted.
• The samples used for the COD analysis may be grab or composite.
• Preservation of the sample can be accomplished by adding sulphuric acid to depress
the pH to 2 and the holding time with preservation is 7 days
• COD is an important parameter in management and design of a treatment plant since
for all practical purposes, the COD values are very close to the amount of chemically
oxidizable carbonaceous material, and hence used in the control of treatment process.
• COD values are taken as basis for calculation of efficiency of treatment plants and
also figure in standard for discharging the industrial or domestic wastewater in
various kinds of water bodies.
Requirements
• Raw and treated sewage samples

• reflux apparatus
• round bottom flask with condenser
• distilled water
• 0.25N K2Cr2Or (Dissolve 12.25 gm of K2Cr207 in distilled water and
make volume to 1 litre)
• AgSO. Reagent
• 0.1N Ferrous ammonium sulphate solution (Dissolve 39.2 gm of ferrous
ammonium sulphate solution in distilled water, add 30 ml of conc. H2SO4.
Cool and dilute to 1000 ml).
• orthophenanthroline indicator - available as 0.025M solution and used
directly
Procedure
1 Take 10 ml of 0.25N K2Cr2O; solution in a clean, round bottom flask.
2. Add 20 ml of appropriately diluted sewage sample (raw or treated).
3. Add 20 ml of distilled water for blank.

4. Add 0.4 gm of mercuric sulphate powder and 5 ml of acid reagent
5. Add 25 ml of acid reagent.
6. Add glass beads and heat contents on a hot plate and reflux for 2 hours.
7 Cool the flask and add about 80 ml of cold distilled water.
8. Add 4 drops of phenanthroline indicator
9. Titrate against 0.1N ferrous ammonium sulphate.
Calculation
Calculate COD as follows:
• COD mg/l= (B-S) x N x 8000 x dilution factor / ml of sample
Where,
• B = Blank reading
• S = Sample reading
• N = Normality of ferrous ammonium sulphate.
Note:
• Efficiency of an effluent treatment process can be determined as percentage reduction in the COD as
• [COD(before treatment) - COD(after treatment)x 100/ COD(before treatment)
• Maximum permissible limits for effluent COD for discharge into:
• Inland surface water - 250 mg/L.
• Public sewer - NA,
• Land for irrigation - NA and
• Marine coastal areas - 250 mg/L.

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Mahatma Education Society`s

Pillai College of Arts, Commerce and Science (Autonomous)

Chemical oxygen demand

1. COD results are available much sooner since there is no incubation

2. The COD test requires fewer manipulations of the sample.

3. The COD test oxidizes a wider range of chemical compounds,

4. It can be standardized more easily.

• Hence, such materials will be oxidised chemically and contribute to COD.

• Raw and treated sewage samples

1 Take 10 ml of 0.25N K2Cr2O; solution in a clean, round bottom flask.

2. Add 20 ml of appropriately diluted sewage sample (raw or treated).

3. Add 20 ml of distilled water for blank.

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