CE 370 - Lab

Chemical Oxygen Demand

(COD)
 Basic Principles
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.

Cr2O72
Cn H aOb Nc O2 CO2 H 2O NH3
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:

Cn H aOb N c Cr2O72- H CO2 H 2O NH 4 Cr 3

In the process of oxidation, potassium dichromate
is reduced 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.