SCOE/CIVIL/2018-19 REV R8

EXPERIMENT NO. 3
DETERMINATION OF CHEMICAL OXYGEN DEMAND (COD)
3. Introduction

COD is a measure of the total

quantity of oxygen required for oxidation of nearly all
compounds in wastewaters,
by the action of a strong oxidation agent. Potassium Dichromate
(K:Cr:01) is used as the chemical oxidizing agent, as it can oxidize a large variety of
organic substances into CO and H20. Aromatic hydrocarbons and Pyridine are
exceptions
they remain unoxidized.

Chemically
Oxidisable Matter
Estimated by COD)

Organic Oxidisable InorganicOxidisable

Matter Matter

Non-
cyanide, ferrous
biodegradable
Biodegradable compounds,
(Celulose, lignn) nitrates

Carbonaceous
Estinated by BOD
test

Nitrogenous

BOD is a measure of the carbonaceous component of bio-degradable organic matter in

a waste, whereas COD measures nearly all the oxidizable matter in the waste.
Therefore COD for a waste is greater than its BOD value. Both BOD and COD values of
any waste are important parameters, as their inter-relationship decides the type of treatment
to be adopted for the waste. If COD is very much greater than BOD, then the waste is not
biodegradable. Biodegradability of a waste is indicated by the treatability index (T.I.)

T.I. =BOD/(COD-BOD)

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1.1less than 0.5 indicates that the waste is not amenabie to bio!ogicai treatment-espeClany

aerobic. Chemical treatment may be suggested. (Chemical treatment may be precipitation of

pollutants, coagulation (followed by flocculation and sedimentation). oxidation, adsorption

etc.)

T.I. between 0.5 and 1.0 indicates that biological treatment for the waste may be considered

with necessary nutrient

supplementation.
TImore than 1.0 indicatesthatthe waste is amenabie to biological treatment.

All biodegradable wastes are chemically degradable. However for any waste, providing

biological treatment should be explored first, as it is more economical. Also, when

chemical treatment is adopted, whatever sludge gets formed needs careful treatment
before it can be discharged into the environment.
COD/BOD Ratios and treatability Indices of some cemmon astes:-
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
23Synthetic Textiles | 2.2 0.8

Dairy Waste 1.5 2.0 Paper &pulp 2.4 0.7

Domesiic 1.8 1.2 Straw board waste 3.0 0.5

Sewage

Meat processing 1.9 1.iMetalplating 4.5 0.3

Sugar mi!! wasie 2.0 1.0 Electroplating

0

3.2 Importance of COD Test

i) COD value indicates

practically the overall
poilution strength of a raw waste
or industrial. domestic

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i) COD and BOD
values of a waste are used for determining its
treatability index.
iii) COD test is used for
quickly evaluating performance eificiency of
treatment unit and
correcting error immediately, as, the test can be
required for BOD test.
completed in 3 hours as against 5 days

iv) If COD/ BOD ratio is

known, then BOD value can be worked out in an
COD test result. emergency from

v) COD test is used for

determining the suitability of a treated waste for disposal.
3.3 Limitation of COD test
The test adopts an artificial procedure. It cannot differentiate between biologically
degradable and biologically resistant organic matter, whereas BOD test simulates condition
obtainable in a natural stream.

COD test does not

indicate, time wise, the rate and extent of removal of
waste in
po!lution load of
nature, whereas BOD1, BOD, BOD3, to BODz0 indicate the natural rate of
biodegradation of a particular waste.
3.4 Standards Recommended:

Max. Allowable Limit

i) Domestic /Industrial effluents discharged into inland

surface water. 250 mg/i

ii) industrial effluents falling into marine coastal area. 250mg 1

3.5 Determination of COD

3.5.1 Principle

A known volume 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 extended period at

150 C. The residual oxidizing agent is estimated using a suitable reducing agent. The
amount of oxidizing agent consumed is a measure of the overall pollution load of the waste.

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3.5.2 Discussions

readily available in pure

Oxidizing agent: The oxidizing chemical used is K:Cr:07. It is
analytical grade and the standards prepared retain their normality for very long period.

Acidified dichromate oxidizes nearly all types of organic matters into CO2 and water.

CaHi206+ 14 K:Cr:07+ Excess of K:Crn0:| + 16HSO4 Heat

6 CO1 +22H20 + 4 Cra (SO4)s + 4 K2SO4 + [Excess K:Cr:07]

The colour of dichromate, being orange, helps in recognizing the presence of residual

dichromate after heating, which is essentiaB for the success of the test. Dichromate

consumed during the test is the difference between the dichromate concentration at the start
and the dichromate cóncentration 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 the dilution water.

Redueing agent The reducing agemt which is used as a titrant, is Ferrous ammonium
sulphate. The ferrous ion reduces dichromate completely and excess of Fe" gives a sharp
reddish brown end point with ferroin indicator.

6Fe (NHA)2 (SO4)3 +

K2Cr207+ 7 H2S04 3Fe: (SO4)3 + 7 H2O +6(NH4)2SO4 +

Cr:(S04)3 +K:SO4

COD of waste sample, mg/l =

(a-b) * [N or tirant} Fq.wt.of oxvgen ]* 1000 * DE

Volume of San1ple in m!

a ml of titrant used for blank,

b ml of titrant used for sample (direct or diluted),

Volume of sample taken is generaliy 20 ml (direct or

diluted).

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I is conventional to use 0.25 N K2Cr207, as each ml of dichromate is equivalent to 2 mg of

OXygen and so. large range of COD is determinable.

The titrant e(NH4)2(SO4)2 is prepared to be 0.1 N, so that, in an ideal case, 25 ml will be

required to reduce 10 ml of 0.25 N KCr07 in the blank, allowing sufficient reaction time
for the complete reduction of dichromate (Cr") to chromate (Cr*)

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

Dilution Techniques

This is based the

on
expected COD of the test sample. Considering the equation:
COD, mg/i = (a-b) ml * 0.1 (mg/ml) * 8 *1000 (ml/) * Dilution Factor

20 ml

COD may be =
(25-21)*0.1 *8 * 1C00* DF (Min)

20 ml

OR

COD (25-4* 0.1 *8 *!000 * DF (Max)

20 mi

i.e.. COD= 160 *DF (Min) & 840 * DF (Max.)

The dilution factor should be so chosen, that the expected COD value of a sample lies
within the range ofminimum & maximum COD values obiainable.

Ex. If expected COD value is 2000 mg/l, D.F. may be 5 & 10.There should be two

Overlapping dilutions for each sample. The range of COD obtainable will be from 800 mg/
to 8.400 mg/1. Ito5 dilution is carried out by diluting 20 mi of the (well mixed) sample to

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-the rest of
COD test
for the
diluted sample
ml of the
extracting 20
TO0 ml , mixing well &
the diluted sample is rejected.

errors.
minimize
to
serial dilution technique is adopted
Beyond 1 to 5 dilutions,
areI& 5.
recommended
dilution factors
effluents,
& treated industrial
Fordomestic sewage waste, dairy waste, paper & pulp mi
industrial effluents such as sugar factory
For raw 200 &
100 & 200 or

5 & 20. For distillery spent wash, D.F. may be

waste, etc. D.F. may be

250.

D.F. may be 200& 500.

For sugar factory molasses,

Failure of the COD test

The COD test is considered a failure when

1. b>a

2. (a-b)<4 ml (2mi absolute minimum) -dilution is too high.

dilution is too less.
3. b<4 ml (2ml absolutely minimum)
immediately after addition of acid or
4. When the sample flasks show green colour either
the diiution is too less & the
during after heating but before titration. This happens, when
or
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 (C*) to chromate (Cr).
Lack of residual dichromate before titration makes dichromate consumption indeterminate.

5. The test is also failure, when the blank also turns green after the addiiion of H:sO

indicating that the acid used is substandard.

Importance of HgS04

HgSO4 is used during the test to prevent the interference due to chlorides in wastewater.
Chlorides reduce dichromate (Cr ") to chromate (Cr) in an acidic mediun thus resulting
in a higher COD value.

6NaCI+K2Cr207+ 7H2SO4 3 C l + 7H20 +3NazSO4+Cr: (SO4)3 +K2SO4

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If
Hgso4 is present, it
combines with chlorides to form
poorly ionized HgClh thus
preventing reduction of dichromate by chlorides.
HgSO4+ 2NaCI HgClh +NazSO
HgSO should be added to the sample hefore addition of dichromale and acid. 400 mg of
HgSO added to 20 ml of sample suppresses interference due 1o 4780 mg/l of chloride
concentration in the sample, which is generaly not exceeded in inland
wastewaters.
However if sea water
infiltration is suspected, use ofl to 2 g of HgSO4 may be necesscry to
suppress interference due to chlorides in the range of 11.000 mg/l to 23,000
mg/l in the
sample.

Importance of Ag:SO4

Ag2SO4 is
catalyst which enables dichromate
a
to oxidize low molecular weight faty acids
& straight chain
aliphatic compomds
Ferroin (Ferrous 1, 10-phenanthroline suiphate)
This is a soluble organic indicator, which exists in two different colours. The change in
colour occurs with a change in oxidation -reduction
potential.
In the first state, when the oxidizing
agent is in excess, the colour of the indicator meryes
with the coiour of the dicl1romate. As titration
progresses, orange chrornate (Cr *) is
reduced and green chromate Cr" increases. At the end
point, when all the dichromate ions
are
completely reduced, addition of'a very little excess of titrant makes ferrous ion available
to 1, 10-phenanthroline in fernoin to from a reddish -brown complex (the coclour &
composition ofthe indicator of itself) in the second state.

3.5.3 Apparatus and equipmert

50 mi burette, 10 ml pipette. 100 ml measuring cylinder, 250 ml beaker, and Reflux

apparatus (Coiled condensers attached to 250ml COD fiasks with ground glass, mounted on
heating equipment). COD Digestion Apparutus can aso be used for coD determination.
We have used this Digestion Apparatus for the COD Test.

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3.5.4 Chemicals

0.25N Potassium dichromate (K2Cr207 (12.259) g per liter)-oxidizing agent

2) Conc. H:SO4 (36N) - provides low pH necessary for oxidation by dichromate

3)0.1 N Ferrous ammonium sulphate [Fe (NHa)2(SO1)2 6 H20 (39 G) +36 NH:SO: (20ml)
per litre]

4) Ferroin [1. 10- phenathroline monohydrate (1.735g) +FeSOs.7H20 (0.695g) per 100 ml,

acidified)

5) Mercuric Sulphate (Analytical crystals)

6) Silver Sulphate (Reagent powder)

3.5.5 Standardization of Ferrous ammonium

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

Procedure

1. Pipette out !0 ml of 0.25 N K2Cr207 accurately into a 100 ml volumeiric fiask and dilute
to 100 ml (using distilled water).

2. Add 30 ml of Conc. H2SO;: (36 N).

3. Cooi to tenmperature (This is very
room
important).
4. Add 2to 3 drops of ferroin indicator.
5. Titrate against the given ferrous ammonium sulphate.
6. Record the amount of titrant (Xml) used up to the end
point, when the contents
change
from dark-green to stable brown colour.

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Fe (NH):(SOa)»
KCr2O7
N1 VI (ml) =
N2 *
V2 ml

ie N* X ml
of titrant 0.25* 100 (ml)

Normality of titrant N= 0. 25* 100 ml

ml

3.5.6 Procedure of COD Test: {A)

1. Take three COD flasks P. Q & R. 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& R (adopt two different dilutions for each sample).
3. Add 10 ml of 0.25 N KCr:07 accurately, using a pipette, to each flask.
4. Add 30 ml Conc. H2SO4 (36N) to each flask slowly in instalments, stürring the contents

carefully.
5. Addabout 200 mg of Ag:SO4 to each flask.

6. Add 3 to 4 glass beads or rounded quartz pebbles (to minimize bumping of acid mixture

during boiling)
(B)

1. Attach all three flasks to reflux condensers or COD Digestion Unit. Heat & digest for iwo

hours.

2. Cool the flasks. Add 20 ml of distilled water down each condenser attached to B & C (to
wash down condensed organics sticking to coiled surfaces)
3. Detach the flaks and add 70 ml of distilled water to each.
4. Cool the 1lasks io rocm temperature (7This is very important. If the flask contents are at a

higher iemperature than the titrant, then very large quantities of titrant will be used up &

COD results will be erroneous).

(C)

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itrate all the three flasks against standardized ferrous ammenium sulphate using 2 to 3
drops of Ferroin indicator
Record titrant used (a) ml for blank flask P & flask Q & (¢) ml
(b) iml for sample tor sainple
flask R.
. a k e the photograph from start tili end of titration to understand the range of colour

variation during the titration.

Caiculations

Sample No-1 Diiution-1 COD =F (a-b)(ml *N (n:g/) *8*i000(mi/ *D.

(Ito....) mg/l 20ml

Dilution-2 COD (a-c)(mi) *N (mg/) *8*1000(ml/)*DF.

(lto....) mg/l 20ml

Note i) f both dilutions give satisfactory results, variation being within 10 % record the
average COD value.

i) If the variation in results is more than 10%, choose the result for which
(a-b)
or (a-c) is greater.

iii) Show calculations for

ail samples and all DFs.

Observation Table

Sample Sample Dilution ml of titrant used COD Remarks

No
descriptior mgi
For blank | For
sample
1to.....
to....
2
Tto...... b

I to.....

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