PRACTICAL REPORT

CHE 790 – PRACTIACL AND FIELDWORK

EXPERIMENT SIX

DETERMINATION F COD IN DRINKING, TAP WATER AND

WASTEWATER SAMPLES (TITRIMETRY)

ON
27 – 02 – 2013

BY
OKUNNUWA SEGUN O.
165904
GROUP 28

ENVIRONMENTAL (ACADEMIC) UNIT

DEPARTMENT OF CHEMISTRY
UNIVERSITY OF IBADAN

PRACTICAL DEMONSTRATOR
DR. OKETOLA

SUBMISSION DATE: MAR., 2013

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 DETERMINATION F COD IN DRINKING, TAP WATER AND WASTEWATER
SAMPLES (TITRIMETRY)

INTRODUCTION

The Chemical Oxygen Demand, or COD, is a measurement of the amount of material that
can be oxidized (combined with oxygen) in the presence of a strong chemical oxidizing
agent. Since the COD test can be performed rapidly, it is often used as a rough approximation
of the water's BOD, even though the COD test measures some additional organic matter
(such as cellulose) which is not normally oxidized by biological action. As with the BOD
test, the COD test is reported as mg/L of oxygen used.

Chemical oxygen demand (COD) is defined as the amount of a specified oxidant that reacts
with the sample under controlled conditions. The Chemical Oxygen Demand (COD) method
determines the quantity of oxygen required to oxidize the organic matter in a waste sample,
under specific conditions of oxidizing agent, temperature, and time. The quantity of oxidant
consumed is expressed in terms of its oxygen equivalence. Because of its unique chemical
properties, the dichromate ion (Cr2O7) is the specified oxidant, and is reduced to the chromic
ion (Cr+3). Both organic and inorganic components of a sample are subject to oxidation, but in
most cases the organic component predominates and is of the greater interest.

The chemical oxygen demand gives information on the oxygen required by a water of
oxidation of almost all water‐soluble organic substance, the exceptions being a number of
compounds containing nitrogen and only very slightly soluble hydrocarbons.

INTERFERENCES
The most common interferent is chloride ion. Under the rigorous digestion procedures for
COD analyses, chloride, bromide, or iodide can react with dichromate to produce the
elemental form of the halogen and chromic ion. Results then are in error on the high side. The
difficulties caused by the presence of the chloride can be overcome largely, though not
completely, by complexing with mercuric sulfate, which is used in this procedure. This
method is suitable for chloride levels up to 1000 mg/L.

ENVIRONMENTAL SIGNIFICANCE OF COD

COD values are particularly important in the surveys designed to determine and control the
losses of sewer systems.

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The ratio of BOD to COD 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 waste water is
highly polluted and amenable to the biological treatment.
It is useful to assess strength of wastes, which contain toxins and biologically resistance
organic substances.
COD can be related to TOC (Total Organic Compound), however does not account for
oxidation state of the organic matter
BOD value is always lower than COD value. For domestic and some industrial wastewater,
COD value is about 2.5 times BOD value.

AIM

To determine the chemical oxygen demand of various samples of water (drinking, tap water
and wastewater) in the University of Ibadan.

SAMPLE
Sample 1. ------ Zoological Garden
Sample 2. ------ Chemistry Laboratory Water
Sample 3. ------- Sachet Water

APPARATUS
Erlenmeyer flask
Small beaker
100 ml graduated cylinder
Rrubber-tipped stirring rod, or magnetic stirrer and stir bar
White porcelain evaporating dish
Reflux apparatus
300-mm jacket Liebig
Condenser with ground-glass joint
Hot plate / waterbath
Blender
Pipette
Analytical balance
Oven
Glass beads

REAGENTS

Standard potassium dichromate solution (0.250N)

Sulfuric acid reagent containing silver sulfate catalyst

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Standard ferrous ammonium sulfate

Ferroin indicator solution

Mercuric sulfate crystals

Concentrated sulfuric acid

Distilled water

THEORY

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

This expression does not include the oxygen demand caused by the oxidation of ammonia
into nitrate.

Dichromate does not oxidize ammonia into nitrate, so this nitrification can be safely ignored
in the standard chemical oxygen demand test.

Because COD measures the oxygen demand of organic compounds in a sample of water, it is
important that no outside organic material be accidentally added to the sample to be
measured. To control for this, a so-called blank sample is required in the determination of
COD (and BOD -biochemical oxygen demand - for that matter). 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 water and blank samples, 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 of organic matter.

Inorganic interference

Some samples of water contain high levels of oxidizable inorganic materials which may
interfere with the determination of COD. Because of its high concentration in most

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wastewater, 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.

The following table lists a number of other inorganic substances that may cause interference.
The table also lists chemicals that may be used to eliminate such interference, and the
compounds formed when the inorganic molecule is eliminated.

Inorganic molecule Eliminated by Elimination forms

Chloride Mercuric sulfate Mercuric chloride complex

Nitrite Sulfamic acid N2 gas

Ferrous iron - -

Sulfides - -

PRINCIPLE
Most types of organic matter are oxidized by a boiling mixture of chromic and sulfuric acids.
A sample is refluxed in strongly acid solution with a known excess of potassium dichromate
(K2Cr2O7). After digestion, the remaining unreduced K2Cr2O7 is titrated with ferrous
ammonium sulfate to determine the amount of K2Cr2O7 consumed and the oxidizable matter
is calculated in terms of oxygen equivalent. Silver sulfate is used as a catalyst and mercuric
sulfate is added to remove chloride interference. The excess dichromate is titrated with
standard ferrous ammonium sulfate, using orthophenanthroline ferrous complex as an
indicator. In this experiment, the sample is heated for two hours with a strong oxidizing
agent. Oxidizable organic compounds react, reducing the dichromate ion to green chromic
ion.

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SAMPLE COLLECTION AND PRESERVATION
Samples were collected in a narrow necked 200‐300 cm3 glass bottle having an accurately
fitting ground glass stopper. When sampling zoological garden water, water in the bottle
displaced several times before collecting the sample.
Samples were collected in glass bottles.
Samples were preserved with sulfuric acid to a pH < 2 and maintained at 4°C until analysis.

PROCEDURE

Preparation of Reagents

Standard Potassium Dichromate (K2Cr2O7) (0.025 moldm‐3 ) – Digestion Solution

Potassium dichromate was dried for two hours in the oven at 103 0C before weighing. 4.9130g
of dried potassium dichromate was dissolved in 500ml of distilled water. 167ml conc. H 2SO4
and 33.3g of HgSO4 were added. The solution was diluted to 1L.

Standardization: To approximately 200ml of distilled water, 25.0ml of 0.25 N K2Cr2O7

solution was added. 20ml of H2SO4 was also added and cooled. This was titrated against
ferrous ammonium sulfate using 3 drops of ferroin indicator. The colour change is sharp,
going from blue-green to reddish-brown.

Sulfuric acid reagent: Ag2SO4, reagent or technical grade, crystals or powder was added to
conc. H2SO4 at the rate of 5.5 g Ag2SO4 /kg H2 SO4. This was allowed to stand for 1 day to
dissolve.

Standard ferrous ammonium sulfate (FAS) titrant: approximately 0.1M: Dissolve 39.2g
of Fe(NH4)2(SO4)2·6H2O was dissolved in distilled water. 20ml of conc. H 2SO4 was added,
cooled, and diluted to 1000ml.

Mercuric sulphate: HgSO4, crystals or powder

Ferroin Indicator
0.0695mg of FeSO4. 7H2O and 0.0149g of 1, 10‐phenanthroline were dissolved in distilled
water and made up to 100ml.

Potassium hydrogen phthalate (KHP) standard: HOOCC6H4COOK: was lightly crushed

and then dried to constant weight at 120°C. 0.850g was dissolved in distilled water and dilute
to 1000 ml. KHP has a theoretical COD of 1.176 mg O2/mg and this solution has a theoretical
COD of 500µg O2/ ml. This solution is stable when refrigerated, but not indefinitely.

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Determination of COD
Preparation of a Blank

2.5ml of distilled water was measured into a 500ml refluxing flask.

1g of mercuric sulfate was added to the distilled water.

Several glass beads were added to the solution.

5.0ml of sulfuric acid reagent was added very slowly and swirled to help dissolve the
mercuric sulfate.

25.0ml of the 0.250 N potassium dichromate solution was added and mix.

Preparation of Sample

2.5ml of water sample was measured into a 500ml refluxing flask.

1g of mercuric sulfate was added to the distilled water.

Several glass beads were added to the solution.

5.0ml of sulfuric acid reagent was added very slowly and swirled to help dissolve the
mercuric sulfate.

25.0ml of the 0.250 N potassium dichromate solution was added and mix.

Reflux of both the Sample flask and the Blank flask

Both the sample flask and the blank flask were attached to separate condensers and the
cooling water was turned on.

70ml of sulfuric acid reagent was added to each flask through the open end of the condenser.
The flasks were swirled several times while adding the sulfuric acid reagent.

The end of the condenser was covered with a small beaker to prevent foreign material from
entering the reflux mixture.

The hot plate / waterbath was turned on and the mixtures were refluxed (boiled) for two
hours.

The flasks and condensers were cooled.

The inside of the each of the condensers was washed down with distilled water and the
condensers were removed.

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Titration of both the Sample flask and the Blank flask

The content of each flask was diluted to approximately twice its volume with distilled water.

2 drops of ferroin indicator was added to each flask.

Each flask was titrated with ferrous ammonium sulfate until the contents change colour from
blue-green to reddish-brown and the colour change remained for 1 minute or longer.

Amount of titrant used for each was recorded.

PRECAUTION
Reflux mixtures were mixed thoroughly before applying heat to prevent local heating of flask
bottom and a possible blowout of flask contents.
Special precautions were taken to insure that distilled water used in this test was low in
organic matter.

Traces of organic material either from the glassware or atmosphere were removed.

Extreme care was exercised to avoid inclusion of organic materials in the distilled water used
for reagent preparation or sample dilution.

Glassware used in the test was conditioned by running blank procedures to eliminate traces of
organic material.

To minimize loss of volatile materials the flask was cooled during addition of the sulfuric
acid solution.

CALCULATION
Table

S/No Sample Volume of Burette Reading (ml) Volume of FAS (ml)

Sample
(ml) Initial Final

1. BLANK 2.5 0.00 1.60 1.60 (A)

2. SAMPLE 1. 2.5 2.70 2.90 0.20 (B1)

3. SAMPLE 2. 2.5 2.90 4.10 1.20 (B2)

4. SAMPLE 3. 2.5 4.10 5.50 1.40 (B3)

Molarity of the ferrous ammonium sulfate used was 0.1M

Calculate the COD of the sample using the following formula:

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 ( A−B ) x M x 8000
COD (mgL) =
volume of sample (ml)
Where:
A = ml of titrant used for blank

B = ml of titrant used for Sample

M = Molarity of ferrous ammonium sulphate

( A−B 1 ) x M x 8000 ( 1.60−0.20 ) x 0.1 x 8000

COD for sample 1 (mgL) = = = 448.0mg/L
volume of sample ( ml ) 2.5

( A−B 2 ) x M x 8000 ( 1.60−1.20 ) x 0.1 x 8000

COD for sample 2 (mgL) = = = 128.0mg/L
volume of sample (ml) 2.5

( A−B 3 ) x M x 8000 ( 1.60−1.40 ) x 0.1 x 8000

COD for sample 3 (mgL) = = = 64.0mg/L
volume of sample (ml) 2.5

RESULTS
The COD values for zoological garden (sample 1.), Chemistry Laboratory water (sample 2.)
and Sachet Water were found to be 448.0mg/L, 128.0mg/L and 64.0mg/L respectively.

DISCUSSION
Potassium hydrogen phthalate (KHP) standard, HOOCC6H4COOK, has a theoretical COD of
1.176mgO2/mg and this solution has a theoretical COD of 500µgO 2/ml. This solution is stable
when refrigerated, but not indefinitely. The COD values for zoological garden (sample 1.),
Chemistry Laboratory water (sample 2.) and Sachet Water were found to be 448.0mg/L,
128.0mg/L and 64.0mg/L respectively which are all far above the 1.176mg/L of standard
KHP.

Many governments impose strict regulations regarding the maximum chemical oxygen
demand allowed in wastewater before they can be returned to the environment. For example,
in Switzerland, a maximum oxygen demand between 200 and 1000 mg/L must be reached
before wastewater or industrial water can be returned to the environment. The COD values
for zoological garden (sample 1.), Chemistry Laboratory water (sample 2.) and Sachet Water
were found to be 448.0mg/L, 128.0mg/L and 64.0mg/L respectively all fall within the range
given above.
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The table below shows the normal range of COD found in various kinds of domestic
wastewater. The addition of industrial waste can cause these values to vary widely.

Source Normal COD range, mg/L

Plant influent 300 – 700

Primary effluent 200 – 400

Trickling filter effluent 45 – 130

Activated sludge effluent 30 – 70

Advanced waste treatment effluent 5 – 15

The COD values for zoological garden (sample 1.) - 448.0mg/L falls within plant inflent
while Chemistry Laboratory water (sample 2.) and Sachet Water with COD values of
128.0mg/L and 64.0mg/L respectively fall within trickling filter effluent.

CONCLUSION

The zoological garden water sample has the highest COD value (488.0mg/L), followed by
Chemistry Laboratory water sample with COD value of 128.0mg/L and lastly the sachet
water with COD value of 64.0mg/L.

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REFERENCES

American Public Health Association, American Water Works Association, and Water
Environment Federation. 1998. Standard Methods for the Examination of Water and
Wastewater. American Public Health Association, Washington, D.C.

DOBBS, R.A. & R.T. WILLIAMS. 1963. Elimination of chloride interference in the
chemical oxygen demand test. Anal. Chem. 35:1064.

Environmental Engineering and Science (5th ed.). New York: McGraw-Hill. ISBN 0-07-
248066-1.

Lenore S. Clescerl, Arnold E. Greenberg, Andrew D. Eaton. Standard Methods for

Examination of Water & Wastewater (20th ed.). Washington, DC: American Public
Health Association. ISBN 0-87553-235-7.

MEDALIA, A.I. 1951. Test for traces of organic matter in water. Anal. Chem. 23:1318.

MOORE, W.A., R.C. KRONER & C.C. RUCHHOFT. 1949. Dichromate reflux method for
determination of oxygen consumed. Anal. Chem. 21:953.
MOORE, W.A., F.J. LUDZACK & C.C. RUCHHOFT. 1951. Determination of oxygen-
consumed values of organic wastes. Anal. Chem. 23:1297.PITWELL, L.R. 1983.
STANDARD COD. Chem. Brit. 19:907.
Standard Methods for the Examination of Water and Wastewater, 14th Edition, p 550,
Method 508 (1975).

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