Determination of Chemical Oxygen Demand

The Chemical Oxygen Demand (COD) test measures the

oxygen required to oxidize organic matter in water and
wastewater samples by the action of strong oxidizing
agents under acid conditions.

COD is often used as a quality parameter to assess the

extent of organic pollutants in municipal and industrial
wastewaters. This analysis is of interest since carbon
compounds serve as a food source for microorganisms.
Org + Micro + O2 - More Micro + CO2 + H2O + Others
If discharged untreated, organic compounds will result in
microorganism blooms, resulting in oxygen depletion and fish
kills. COD measurement provides a rapid means of monitoring
the organic pollutants within the wastewater treatment plant,
allowing for control of the treatment process to maintain
optimum plant operation.

COD Measurement COD is measured by the oxidation of

organic pollutants using a strong oxidizing agent (Potassium
dichromate) under acidic conditions. The reaction of potassium
dichromate with organic compounds is given by:
In the process of oxidation, potassium dichromate is reduce
d
 forming Cr3+. The amount of Cr3+ is determined after
oxidization is complete, and is used as an indirect measure of
the organic contents of the water sample. For all organic matter
to be completely oxidized, an excess amount of potassium
dichromate must be present.
Once oxidation is complete, the amount of excess potassium
 dichromate must be measured to ensure that the amount of
Cr3+ can be determined with accuracy. To do so, the excess
potassium dichromate is titrated with ferrous ammonium
sulfate (FAS) until all of the excess oxidizing agent has been
reduced to Cr3+.
The oxidation-reduction indicator Ferroin is added during
 this titration step. Once all the excess dichromate has been
reduced, the Ferroin indicator changes from blue-green to
reddish-brown. The amount of ferrous ammonium sulfate
added is equivalent to the amount of excess potassium
dichromate added to the original sample. A blank sample is
created by adding all reagents (e.g. acid and oxidizing agent)
to a volume of distilled water. COD is measured for both the
sample and the blank, and the two are compared. The oxygen
demand in the blank sample is subtracted from the COD for
the original sample to ensure a true measurement
Inorganic interference Some samples of water
contain high levels of oxidizable inorganic
materials which may interfere with the
determination of COD. Chloride is often the most
serious source of interference. Its reaction with
potassium dichromate follows the equation: Prior
to the addition of other reagents, mercuric sulfate
can be added to the sample to eliminate chloride
interference.
Principle: A suitable known volume of wastewater sample is refluxed
with a known excess of K2Cr2O7 solution in H2SO4 medium and in
the presence of Ag2SO4 and HgSO4. K2Cr2O7 oxidizes all
oxidisable impurities. Ag2SO4 catalyses oxidation of straight chain
organic compounds, aromatic and pyridine. HgSO4 avoids the
interference of Cl- ions. The amount of unconsumed K2Cr2O7 is
determined by titration with standard ferrous ammonium sulfate
solution. The amount of K2Cr2O7 solution consumed corresponds to
COD of the wastewater sample.
Procedure: Pipette out 25ml of the water sample into
a conical flask. Add 1gm of HgSO4, 1gm of Ag2SO4,
25 ml of K2Cr2O7 solution and 25 ml of 1:1 H2SO4.
The conical flask is fixed with a water condenser and
the solution is refluxed for two hours. The contents
are cooled and titrated with standard ferrous
ammonium sulfate solution, using ferroin as indicator,
till the color changes from blue green to reddish
brown. Perform a blank titration taking the same
amount of distilled water in place of the wastewater.
Let the volume required be B ml.
Calculations:
Volume of waste water sample taken = 25 ml
Volume of standard FAS used in sample titration = A ml
Volume of standard FAS used in blank titration = B ml
Normality of FAS solution = X N
Amount of K2Cr2O7 consumed in satisfying the COD
in terms of FAS solution = (B-A) ml
Normality of COD N1 = X x (B-A) /V
COD of the sample = X x (B-A) x 8 gm.dm-3 / V
= X x (B-A) x 8 x 1000 mg dm-3/V
PROBLEMS ON COD:
(1) In a COD experiment, 30 cm3 of an effluent sample
required 9.8 cm3 of 0.001 M K2Cr2O7
solution for oxidation. Calculate the COD of the sample.
1000 cm3 of 1M K2Cr2O7 = 48 gm of O2
9.8 cm3 of .001M K2Cr2O7 = 48 x .001x 9.8 gm of O2/

1000x1
30 cm3 of an effluent required = 0.4704 mg of O2
COD of the effluent sample = 0.4704 x 1000 /30
= 15.69 mg of O2 / dm3