D. Y.

Patil College of Engineering, Akurdi Waste Water Engineering Lab

Experiment No. 3 Date:

Title: Determination of Chemical Oxygen

Demand (COD) in a given wastewater sample

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D. Y. Patil College of Engineering, Akurdi Waste Water Engineering Lab

Aim:- To determine Chemical Oxygen Demand (COD) in a given wastewater sample.

Introduction:-

COD is a measure of the total quantity of oxygen required for oxidation of nearly all organic compounds in
waste water by the action of strong oxidizing agent. K2Cr2O7 is used as the chemical oxidizing agent; as it
can be oxidize a large variety of organic substance into CO2 and H2O. Aromatic hydrocarbons and pyridine
are exceptions – they remain unoxidized.

Chemically oxidized matter (estimated by COD test)

Inorganic Oxidizable matter Organic matter

(Cyanide, ferrous compounds
Nitrites chlorides, sulphates, etc

Biodegradable Non-Biodegradable
(Cellulose, lignin)

Nitrogenous Carbonaceous
(Estimated by BOD test)
BOD is a measure of the cabonacous component of biodegradable organic matter in a waste, whereas COD
measure nearly all oxidizable matter in the waste. Therefore COD for a waste is greater than BOD value.
Both BOD & COD values of any waste are important parameters as their interrelationship decides the type
of treatment to be adopted for the waste. If COD is very much greater than BOD, then the waste water is
not biodegradable. Biodegradability of waste is indicated by the treatability index (T.I).

T.I = BOD/ (COD-BOD)

T.I. less than 0.5 indicates that the waste is not amenable to biological treatment especially aerobic.
Chemical treatment may be suggested.

Chemical treatment may be precipitation of pollutants, coagulation (followed by flocculation and

sedimentation), oxidation, absorption etc.

T.I between 0.5 & 1.0 indicates that biological treatment for the waste may be considered with necessary
nutrient supplementation.

T.I more than 1.0 indicates that the waste is amenable to biological treatment.

All biodegradable waste is chemically degradable. However for any water providing biological treatment
should be first explored as it is more economical.

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Table 3.1 COD/BOD ratios & treatability indicates of some common waste

Waste COD/BOD T.I Waste COD/BOD T.I

Phenolic waste 1.3 3.0 Soft drinks 2.1 0.9
Pharmaceuticals 1.4 2.3 Synthetic textiles 2.2 0.8
Dairy waste 1.5 2.0 Paper and pulp 2.4 0.7
Domestic waste 1.8 1.2 Straw board waste 3.0 0.5
Meat processing 1.9 1.1 Metal plating 4.5 0.3
Sugar mill waste 2.0 1.0 Electroplating 0 0

Importance of COD test:-

1. COD value indicates practically the overall; pollutional strength of a raw waste, domestic or
industrial.
2. COD and BOD values of waste are used for determining its treatability index.
3. COD test is used for quickly evaluation performance efficiency of treatment units and correction
errors immediately, as the test can be completed in 3 hours as against 5 days required for BOD test.
4. By knowing the general COD/BOD ratio for a waste, BOD values can be worked out in an
emergency for COD test results.
5. COD test is used for determining the suitability of a treated waste for disposal.

Limitations of COD test:-

The test adopts an artificial procedure. It cannot differentiate between biologically degradable and
biologically resistant organic matter, whereas BOD test simulates conditions obtainable in a natural stream.

COD test does not indicate, time-wise, the rate and extent of removal of pollutional load of waste in nature
whereas BOD1, BOD2, BOD3 and BOD20 indicate the natural rate of biodegradation of a particular waste.

Table 3.2 Standards Recommended

Sr. Maximum Permissible

Description
No. COD
1 Industrial effluents discharged into inland surface water 250 mg/l, IS 2490
2 Industrial effluents falling into marine coastal area 250 mg/l, IS 7968

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Determination of COD

Principle:-

A known volume and normality of a potent oxidizing agent is used to oxidize all oxidizable matters in the
waste sample as completely as possible. Oxidation is carried out for an extended period at 100 C. the
residual oxidizing agent is estimated using a suitable reducing agent, the amount of oxidizing agent
consumed as a measure of the overall pollutional load of the waste.

Discussion:-

Oxidizing Agent:-

The oxidizing chemical used is K2Cr2O7. It is readily available in a pure analytical grade and the standards
prepared retain their normality for very long, acidified dichromate oxidizes nearly all types of organic
matters into CO2 and water.

C6H12O6 + [4 K2Cr2O7 + excess of K2Cr2O7] + 16 H2SO4 6CO2 + 22H2O + 4 Cr2 (SO4)3 +

4 K2SO4 + [excess of K2Cr2O7]

The colour of dichromate, being orange, helps in recogning the presence of residual dichromate after
heating – which is essential for the success of the test. Dichromate consumed during the test is the
difference between the dichromate concentration remaining as excess after hot digestion. The initial
concentration of dichromate is estimated by running a blank through the test, which will practically
eliminate error due to any oxidizable matter present in dilution water.

Reducing agent:- the reducing agent, which is used as titrant, is ferrous ammonium sulphate. The ferrous
ion reduces dichromate completely and excess of Fe2+ gives a sharp reddish brown end point with ferrion
indicator.

6Fe(NH4) (SO4)2 + K2Cr2O7 + 7 H2SO4 Fe2(SO4)3 + 7 H2O + 6(NH4) 2SO4 + Cr2 (SO4)3 + K2 SO4

Where, a = ml of titrant used for blank

b = ml of titrant used for sample (direct or diluted) volume of sample taken is generally 20 ml

It is conventional to use 0.25N K2Cr2O7 as each ml of dichromate is equivalent to 2 mg of oxygen and so

large range of COD is determinable.

The titrant Fe(NH4)2(SO4)2 is prepared to be 0.1 N; so that, in an ideal case, 25 ml will be required to
reduced 10 ml of 0.25 N K2Cr2O7 in the blank, allowing sufficient reaction time for the complete reduction
of dichromate (Cr3+).

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During the estimate of dichromate consumption, for most significant results, should be a minimum of 4 ml
and (a-b) should be a minimum of 4 ml.

Dilution technique:-

This is based on the expected COD of the test sample. Considering the equation

That is COD = 160 x DF (minimum) & 840 x DF (maximum)

The dilution factor should be so chosen that the expected COD value of a each sample lies within range of
minimum and maximum COD values obtainable.

Ex. If expected COD value is 2000 mg/l

DF may be 5 and 10. There should be two overlapping dilutions for each sample. The range of COD
obtainable will be from 800 mg/l to 8400 mg/l. 1 to 5 dilution is carried out by diluting 20 ml of the (well
mixed) sample to 100 ml, mixing well and extracting 20 ml of the diluted sample for the COD test- the test
of the diluted sample is rejected.

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Table 3.3 Consecutive dilutions for COD measurable from 160 mg/l to 4,20,000 mg/l

Sr. D.F Dilution Range of

No. Volume of Volume of actual overall COD
Diluted measurable
Original sample Diluted sample dilution mg/l
sample
1 1 1 1 20 ml 20 ml 160-840
2 2 1 2 50 ml 100 ml 320-1680
3 5 1 5 20 ml 100 ml 800-4200
4 10 1 10 50 ml 100 ml 1600-8400

20 ml 100 ml
5 20 1 20 50 ml 100 ml 3200-16800

10 ml 100 ml
6 50 1 50 20 ml 100 ml 8000-42000

25 ml 1000 ml
7 100 1 100 50 ml 100 ml 16000-84000

20 ml 100 ml

10 ml 100 ml
8 200 1 200 50 ml 100 ml 32000-168000

10 ml 100 ml

10 ml 100 ml
9 250 1 250 20 ml 100 ml 40000-210000

20 ml 100 ml

10 ml 100 ml
10 500 1 500 20 ml 100 ml 80000-420000

10 ml 100 ml

ml 100 ml

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Beyond 1 to 5 dilution, serial dilution technique is adopted to minimize errors for domestic sewage and
treated industrial effluents, recommended dilution factors are 1 and 5.

For raw industrial effluents such as sugar factory waste, dairy waste. Paper and pulp mill waste etc. DF
may be 5 to 20

For distillery spent wash DF may be 100 and 200 or 200 and 250

Failure of COD test:-

The COD test is considered as a failure when-

1. b >a
2. (a-b) < 4 ml (2 ml absolute minimum) – dilution is too high
3. b < 4 ml (2 ml absolute minimum) – dilution is too less
4. When the sample flasks show green colour either immediately after addition of acid or during or
after heating but before titration. This happens, when the dilution is too less and the oxidizable
matter in the sample is in excess of the oxidizing agent added. The total green colour is because of
complete reduction of all the dichromate (Cr6+) to chromate (Cr3+). Lack of residual dichromate
before titration makes dichromate consumption indeterminate.
5. The test is also a failure when the blank also turns green after the addition of H2SO4 indicating that
the acid is used substandard.

Importance of HgSO4:-

HgSO4 is used during the test to prevent the interference due to chlorides in waste water. Chlorides reduce
dichromate (Cr6+) to chromate (Cr3+) in an acidic medium thus resulting in a higher COD values.

6NaCl + K2Cr2O7 + 7H2O 3Cl2 + 7H2O + 3Na2SO4 + Cr2(SO4)3 + K2SO4

If HgSO4 is present it combine with chlorides to form poorly ionized HgCl2 thus preventing reduction of
dichromate by chlorides.

HgSO4 + 2NaCl HgCl2 + Na2SO4

HgSO4 should be added to sample before addition of dichromate and acid. 400 mg of HgSO4 added to 20
ml of sample suppress interference due to 4780 mg/l of chloride concentration in the sample, which is
generally not exceeded in inland waste water. However if sea water infiltrates is suspected, use of 1 to 2
gm of HgSO4 may be necessary to suppress interference due to chloride in the range of 11000 mg/l to
23000 mg/lit in the sample.

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Importance of Ag2SO4-

Ag2SO4 is a catalyst which enables dichromate to oxidize low molecular weight fatty acids & straight chain
aliphatic compounds.

Ferroin (Ferrous 1, 10 – phenanthroline sulphate):-

This is a soluble organic indicator, which exists two different colours. The change in colour with a change
in oxidation reduction potential.

In the first state, when the oxidizing agent is in excess, the colour of the indicator merges with the colour of
dichromate. As titration progress, orange dichromate is reduced and green chromate increases. At the end
point when all the dichromate ions are completely reduced, addition of a very little excess of the titrant
makes ferrous ions available 1-10 phenanthroline in ferroin to form a reddish – brown complex (the colour
and composition of the indicator itself) in second state.

Apparatus & Chemicals:-

50 ml burette, 10 ml pipette, 100 ml measuring cylinder, 250 ml beaker. Reflux apparatus (coiled
condensers attached to 250 ml COD flask with ground glass necks, mounted on heating equipment).

Chemicals:-

1. 0.25 N Potassium dichromate (K2Cr2O7 (12.259) gm per liter) – oxidizing agent

2. Conc. H2SO4(36 N) – provides low pH necessary for oidation by dichromate.
3. 0.1 N ferrous ammonium sulphate [(Fe(NH4)2 (SO4) 6H2O (36gm + 36 N H2SO4 (20 ml) per liter]
4. Ferrion [ 1,10 – phenathrolane monohydrate (1.735 gm) + FeSO4 7 H2O (0.695 gm) per 100 ml
acidified]
5. Mercuric sulphate (analytical crystals)
6. Silver sulphate (reagent powder)

Standardization of Ferrous ammonium sulphate

Necessity:-

Ferrous ammonium sulphate being a reducing agent is slowly oxidized by the oxygen dissolved from the
air – from the moment the titrant is prepared. The strength of the titrant gradually drops on standing and
exposure. Therefore standardization is required every time the titrant is used.

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Procedure:-

1. Pipette out 10 ml 0.25 N K2Cr2O7 accurately in to a 100 ml volumetric flask and dilute to 100 ml
(using distilled water)
2. Add 30 ml of conc. H2SO4 (36 N)
3. Cool to room temperature (this is very important)
4. Add 2 or 3 drops of ferrion indicator.
5. Titrate against the given ferrous ammonium sulphate.
6. Record the amount of titrant (X ml) used upto the end point, when the contents change from dark –
green to stable reddish brown colour.

Fe(NH4)2(SO4) = K2Cr2O7
N x (X ml) = 0.25 x 10

Normality of titrant N = 0.25 x 10 ml / X ml

Procedure of COD test:-

(A) 1. Take three COD flask P, Q and R and place about 400 mg of HgSO4 in each flask.
2. Add 20 ml of distilled water to flask P (blank flask) & 20 ml of sample direct or diluted to flasks
Q and R. (adopt two different solutions for each sample).
3. Add 10ml of 0.25 N K2Cr2O7 accurately using a pipette, to each flask.
4. Add 30 ml conc. H2SO4 to each flask using a pipette, to each flask stirring the contents carefully
5. Add about 200 mg of Ag2SO4 to each flask.
6. Add 3 to 4 glass beads or rounded quartz pebbles (to minimum bumping of acid mixture during
boiling).

(B) 1. Attach all the three flasks to reflux condensers. Heat and digest for two hours.
2. Cool the flasks. Add 20 ml of distilled water down each condenser attached to P, Q & R (to wash
down condensed organics sticking to coiled surface)
3. Detach the flasks and add 70 ml of distilled water to each.
4. Cool the flasks to room temperature (This is very important. If the flasks contents are at higher
temperature than the titrant then very large quantities of titrant will be used up & COD results will
be erroneous).

(C) 1. Titrate all three flasks against standardized ferrous ammonium sulphate using 2 to 3 drops of
ferrion indicator.
2. Record titrant used (a) ml for blank P & (b) ml for smaple flask Q (c) ml for sample flask R.

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Observation Table:-

Sample ml of sample used

Sample No. Dilutions COD mg/l Remarks
Description For blank For sample
1 to
1 to
1 to
1 to

Calculation:-

Note:-

1. If both dilutions give satisfactory results variations being within 10% record the average COD
value.
2. If variation in results are more than 10% choos the result for which (a-b) or (a-c) is greater.

Result & Conclusion:-

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