Exp No:

Date: xx/xx/2015

ESTIMATION OF CHEMICAL OXYGEN DEMAND

Aim:
To determine the COD in a given water sample.
Theory:
Water is a universal solvent and it dissolves almost anything that it passes by, organic
compounds being no exception. The large amount of organic compounds present in water
bodies are contributed by aquatic plants, animals, industrial effluents etc. Organic compounds
oxidize readily in presence of oxygen to give carbon dioxide, water and ammonia. Hence an
excess of organic compounds in water could deplete oxygen jeopardizing aquatic life.

Chemical Oxygen Demand is used as an indirect measure of the amount of organic

matters. It is actually the amount of oxygen needed to completely oxidize the entire organic
compounds present in water. It is measured as milligrams of oxygen needed to oxidize 1 litre
of water. Potassium dichromate is used as the oxidizing agent owing to its easy availability,
cheapness and strong oxidizing ability. Sulphuric acid provides the acidic environment for
potassium dichromate to carry out its oxidization. Inorganic interference can be a serious
concern especially by chlorine. Chlorine is dealt by using mercuric sulphate which gets
converted to mercuric chloride. Silver sulphate plays the role of catalyst. Mohr’s salt oxidizes
the excess dichromate while ferroin acts as the redox indicator.

The organic matter present in sample gets oxidized completely by potassium

dichromate in the presence of sulphuric acid, silver sulphate, and mercury sulphate to
produce carbon dioxide and water. The sample is refluxed with a known amount of potassium
dichromate in the sulphuric acid medium and the excess potassium dichromate 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 oxygen required to oxidize the
organic matter.
Observation:

Sl Volume (ml) Burette Reading Volume of 0.25N

No. FAS (ml)
Initial Final
SAMPLE
1 25 0

BLANK
1 25 0

Calculation:

Volume of 0.25N FAS used for sample titration (V1) = ml

Volume of 0.25N FAS used for blank titration (V2) = ml

Volume of sample used = 25 ml

(V ¿ ¿ 2−V 1)× M × 8
COD = ¿= = g/ml
Volume of sample

M= molarity of FAS
Milliequivalents of oxygen per ml =

Actual COD = COD x Dilution Factor = = g/ml

Apparatus:

1 Burette and Burette stand.

2 2 x 250 ml conical flask (Erlenmeyer Flask).
3 Reflux flask.
4 100 ml measuring cylinder.
5 10 ml cylinder measuring cylinder.
6 Distilled water.

Reagents:

1 Potassium Dichromate (K2Cr2O7)(0.25N).

2 Mohr’s Salt: Ferrous Ammonium Sulphate (FAS)(0.25N).
3 Mercuric Sulphate.
4 Silver Sulphate.
5 Phenanthroline Ferrous Sulphate Indicator Solution (Ferroin Indicator).
6 Concentrated Sulphuric Acid.

Procedure:
 25 ml of sample was taken into a refluxing flask and 0.25 gm of HgSO 4 is added
to the solution.
 37.5 ml of COD acid (Ag2SO4 – H2SO4) is added slowly. The solution is swirled
slowly.
 12.5 ml of K2Cr2O7 solution is then added.
 Thorough mixing of the solution is ensured by swirling the flask in a water bath to
recover any volatile substances that may have escaped from the liquid phase.
 The solution is then refluxed for 2 hours.
 A blank run (using 25 ml distilled water instead of sample) is simultaneously
conducted with the same procedure.
 After cooling, the solution is transferred to an Erlenmeyer flask. The reflux flask
is rinsed pouring the rinsing water to the Erlenmeyer flask.
  The solution is diluted to about 150ml and about 3 drops of ferroin indicator is
added.
 The solution is titrated against the Mohr’s salt and the titre value required for the
colour change from blue-green to reddish brown is noted.
 The procedure is repeated for the blank run.

Discussions:

 K2Cr2O7 acts as a strong oxidising agent and oxidizes the organic and inorganic
matter in the waste water
Cr2O72- + 14H+ + 6e- 2Cr3+ + 7H2O
 If Chlorides are present in the sample it will interfere with the oxidation of the
organic matter. To ensure non-interference of Chlorides, Mercuric Sulphate is
added which will form complex of Mercuric Chloride. An amount of 10gm of
Mercuric Sulphate is required for 1gm of Chloride to form complex.
 H2SO4is added to the mixture so that the mercury is completely dissolved. Besides
it assists in oxidizing the nitrogen compounds in the sample and the increased heat
will accelerate the reaction rate.
 Silver Sulphate catalyses the reaction and also assists in the oxidation of the
nitrogen compounds.
 Mercury Sulphate is added first in order to allow the chlorine atoms to combine
with mercury. If Silver Sulphate is added first, the Chlorine would bind with
Silver, it will take some time for the Chlorine to detach from the Silver and bind
to Mercury present in Mercury Sulphate. Thus, it is best to add Mercury Sulphate
first.
 The titre volume of the sample gives the volume of FAS required to react with the
excess K2Cr2O7in the solution. Similarly, the titre volume for the blank (distilled
water) gives the volume of FAS required to react with the excess K 2Cr2O7 in the
blank.
Cr2O72- + FeSO4(NH4)2SO4 Cr3+ + NH4++ Fe3+

Result:
Chemical oxygen demand of the given sample of water = 20.8 g/ml