Chemical Oxygen

Demand
Prepared by :
Lamiaa Farghally
Ahmed

Chemical Oxygen Demand

Definition

Chemical Oxygen Demand (COD) is test used

to measure the amount of oxygen in water
consumed to chemical oxidation of
pollutants and oxidize the organic matter in
waste water sample, under specific
conditions of oxidizing agent , temperature,
and time

It is expressed in milligrams per liter

(mg/L), which indicates the mass of oxygen
consumed per liter of solution .

The ratio between COD and BOD

is useful to assess the amenability of waste
for biological treatment. Ratio of BOD to
COD greater than or equal to 0.8 indicates
that wastewater highly polluted and
amenable to the biological treatment.
it is useful to assess strength of wastes,
which contain toxins and biologically
resistant organic substances
BOD value is always lower than COD value.
For domestic and some industrial
wastewater, COD value is about 2.5 times
BOD value

 Uses
(COD) is used to measure organic matter in
1-wastewater .
2-treated effluent.
3-receiving waters.
4-organic constituents .
organic pollutants found in surface water
(e.g. lakes and rivers), making COD a useful
measure of water quality .

Sources
Sources of COD in water are varied
1-soluble organic compounds
2-Residual food waste from bottles and cans.
3- antifreeze, emulsified oils .
4-industrial stormwater
5-All aquatic plants and animals through their
metabolism and excretion of waste products.
6-Dissolution of dead organisms contributes to
the organic carbon, as well as surrounding
humus and peat

Hazards
1) Adverse human impacts:
High levels of COD in water with
threats to human health including toxic
algae blooms bacteria from organic
wastes and seafood contamination.

Adverse impacts on the-2

environment

COD levels decrease the amount of dissolved

oxygen available for aquatic organisms. Low
(generally under 3 mg/L) dissolved oxygen, or
hypoxia, causes
1- reduced cell functioning,
2- disrupts circulatory fluid balance in aquatic species
and can result in death of individual organismsas
well as large dead zones.
3- Hypoxic water can also release pollutants stored in
sediment.
A high COD-Cr load in water may signify
oxygen deficiency, and fish and other aquatic
species are consequently repelled.

Method of Measurement of COD

1.Potassium dicromatlc method (titrimetric method)
2.Spectrophotometery(NIR)

Frist (titrimetric method)

The basis for the COD test is that nearly all
organic compounds can be fully oxidized to
carbon dioxidewith a strong oxidizing agent
underacidicconditions. The amount of
oxygenrequired to oxidize an organic
compound to carbon dioxide, ammonia, and
water is given by:

 This expression includes the oxygen

demand caused by the oxidation of
ammonia into nitrate. The process of
ammonia being converted into nitrate is
referred to asnitrification.The following is
the correct equation for the oxidation of
ammonia into nitrate.

 PRINCIPLE
The organic matter present in sample gets oxidized completely
by potassium dichromate (K2Cr2O7) inthe presence of
sulphuric acid (H2SO4), silver sulphate (AgSO4)and mercury
sulphate (HgSO4)to produce CO2and H2O. The sample is
refluxed with a known amount of potassium dichromate
(K2Cr2O7)in the Sulphuric acid medium and the excess
Potassium dichromate(K2Cr2O7)is determined by titration
against ferrous ammonium sulphate, using ferroin as an
indicator. The dichromate consumed by the sample is
equivalent to the amount of O2 required to oxidize the organic
matter

 TESTING OF SAMPLE
Take three COD vials with stopper (two for the
sample and one for the blank).
Add 2.5 mL of the sample to each of the two
COD vials and the remaining COD vial is for
blank; to this COD vial add distilled water.
Add 1.5 mL of potassium dichromate
reagent
digestion solution to eachofthe three COD
vials.
Add 3.5 mL of sulphuric acid reagent catalyst
solution in the same manner
Cap tubes tightly. Switch on the COD
Digester and fix the temperature at 150 C

 Place the COD vials into a block digester at 150C and

heat for two hours.
The digester automatically switches off. Then remove the
vials and allow it to cool to the room temperature.
Meanwhile, get ready with the burette for the titration.
Fill the burette with the ferrous ammonium sulphate
solution, adjust to zero and fix the burette to the stand.
Transfer the contents of the blank vial to conical flask. Add
few drops of ferroin indicator The solution becomes bluish
green in colour.
Titrate it with the ferrous ammonium sulphate taken in the
burette
End point of the titration is the appearance of the reddish
brown colour.
Note down the volume of ferrous ammonium sulphate
solution added for the blank (A)is 14.1 mL

Transfer the contents of the sample vial to

conical flask.
Add few drops of ferroin indicator. The
solution becomes green in colour.
Titrate it with the ferrous ammonium
sulphate taken in the burette.

End point of the titration is the

appearance of the reddish brown colour.
Note down the volume of ferrous ammonium
sulphate solution added forthe sample (B)is
13.2 mL.

Calculations
The following formula is used to calculate
COD:
whereb =Volume of Ferrous Ammonium sulphatefor
blank(A)
s=Volume of Ferrous Ammonium sulphatefor
Sample (B)
n =Normality of Ferrous Ammonium sulphateN
=Volume of Sample V

, the result of the COD calculation is given in

mg/L

Measurement of COD by
stoichiometric
reaction
The COD can
also be estimated from the concentration

of oxidizable compound in the sample, based on its

stoichiometric reaction with oxygen to yield
CO2(assume all C goes to CO2), H2O (assume all H
goes to H2O), and NH3(assume all N goes to NH3),
using the following formula:
COD = (C/FW)(RMO)(32)
Where C = Concentration of oxidizable compound in the
sample,
FW = Formula weight of the oxidizable compound in the
sample,
RMO = Ratio of the # of moles of oxygen to # of moles
of oxidizable compound in their reaction to CO2, water,
and ammonia
For example, if a sample has 500 wppm of phenol:
C6H5OH + 7O2 6CO2+ 3H2O
COD = (500/94)(7)(32) = 1191 wppm

PRECAUTIONS

The following precautions should be observed while

performing the experiment:
Chlorides are quantitatively oxidized by dichromate
and represent a positive interference. Mercuric sulfate is
added to the digestion tubes to complex the chlorides
so that it does not interfere in the determination.

Nitrites also interfere in the determination of COD and

hence during the determination of samples with high
concentration of nitrites, 120mg of sulphuric acid is
added to the potassium dichromate solution.

Ferroin
preparation
Ferroin sulfate may be prepared by combining
phenanthroline to ferrous sulfate in water.
3 phen + Fe2+ [Fe(phen)3]2+
Notes
A silver compound is added as a catalyst to promote
the oxidation of certain classes of organics, and a
mercuric compound may be added to reduce
interference from
the oxidation of chloride ions by the dichromate. End
products are carbon dioxide, water, and various
states of the chromium ion

Experiment Part

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