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Determination of Chemical Oxygen Demand (COD) Using Closed Reflux

Titrimetric Method

Objectives

Objectives of this lab includes:

 To get knowledge about COD in water

 To understand the concept and phenomenon about COD
 To learn about the role of COD in marine water quality
 To understand the precautions and procedures involved in the determination of COD in
water

THEORETICAL BACKGROUND

Definition

Chemical oxygen demand (COD) is a measure of the capacity of water to consume oxygen

during the decomposition of organic matter and the oxidation of inorganic chemicals such as
Ammonia and nitrite.

COD measurements are commonly made on samples of waste watersor of natural waters
contaminated by domestic or industrial wastes. Chemical oxygen demand is measured as a
standardized laboratory assay in which a closed water sample is incubated with a strong
chemical oxidant under specific conditions of temperature and for a particular period of time. A
commonly used oxidant in COD assays is potassium dichromate (K2Cr2O7) which is used in
combination with boiling sulfuric acid (H2SO4).

Significance of COD

 Eutrophication

As gauges of organic matter in a sample, BOD and COD are critical in wastewater for
determining the amount of waste in the water. Waste that's high in organic matter
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requires treatment to reduce the amount of organic waste before discharging into
receiving waters. If water treatment facilities do not reduce organic content of wastewater
before it reaches natural waters, microbes in the receiving water will consume the organic
matter. As a result, these microbes will also consume the oxygen in the receiving water as
part of the breakdown of organic waste. This oxygen depletion along with nutrient rich
conditions is called eutrophication, a condition of natural water that can lead to the death
of animal life.

 Better parameter than BOD in Testing

Since a BOD test takes five days to complete, COD is used to monitor the treatment
process in day-to-day operations. The COD test takes only a few hours to complete. If
BOD were always used, treated wastewater would need to be held, and a problem with
the treatment process wouldn’t be detected until five days later! This would mean that
wastewater would need to be held until results could be verified.

 Indicator to Type of Organic Matter in water

The COD/TOC ratio can be an important tool in the evaluation of wastewater treatment.
While the Total organic carbon(TOC) test directly assesses the carbon atoms present in
organic compounds, operators of processes dependent upon on biochemical oxidation
(e.g. wastewater treatment) find COD provides a measure of the oxygen-demanding
substances. The ratio of COD value to TOC value at a given point in the process may
provide information on the type of organic wastewater constituents present in the water.

NEQS Guidelines

According to NEQS provisions, the value of COD in waste water should be 150 mg/L. this value
is further revised for different water bodies:

 Into Inland Water = 150mg/L

 Into Sewage Treatment = 400mg/L
 Into Sea = 400mg/L
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COD MEASUREMENT

Working Principle

In this lab session we are using closed reflux titrimetric method. In this method, the water sample
is heated for 2 hours with a strong oxidizing agent such as Potassium dichromate, K2Cr2O7 that
is a hexavalent chromium salt which is present in bright orange colour and is a strong oxidant. It
can oxidize the organic matter up to 95-100% in water sample.

Oxidizable organic compounds react with K2Cr2O7, reducing the dichromate ion from hexavalent
to trivalent green chromium ion. The COD range also contains traces of silver and mercury.
Silver is act as catalyst and used to oxidize compound such as

 Alcohols
 Low molecular weight acids

Where mercury is used to complex the chlorine interference. Then this digested material in the
COD digester is taken out and residual dichromate are titrated with standard ferrous ammonium
sulphates (SAF).

Collection, and Sampling

 Container: For collection of sample use clean glass bottles. Use plastic container only if
container contains no organic matter in it. Sample container containing settelable material
should be well mixed and preferably contain homogeneous sample.
 Storage: Biological active sample should be analyzed as soon possible after collection
but it can be stored at 4 degrees Celsius in refrigerator by adding sulfuric acid into it to
make its pH less than 2.
 Holding Time: Sample can be stored for 28 days after collection.

Interferences
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 Traces of organic materials either from container or atmosphere cause gross positive
interference. Container should be cleaned/washed.
 Volatile material may be lost when the sample temperature rises during the sulfuric acid
addition step. To minimize this loss the flask should be cooled during this step.
 Chloride ions are quantitatively oxidized by dichromate. To stop it add mercuric sulfate
to complex the chlorides
 Nitrites are countered by sulphemic acid. But mostly they are negligible.

Materials Required

 Reagents
 Digestion Solution (0.01667 M)
Add about 500ml distilled water in a volumetric flask and add 4.903g of potassium
dichromate (primary catalyst) previously dried at 150 degrees Celsius for 2 hours.
Then add 167ml of conc. sulphuric acid and 33.3g of mercuric sulphates
(secondary digestion catalyst). Dissolve and cool to the room temperature and dilute
the solution to make it 1000ml.
 Sulphuric Acid Reagent
Add silver sulphates to conc. Sulphuric acid at the rate of 5.5g Ag2SO4/kg H2SO4.
 Sulphemic Acid
 Standard Ferrous Ammonium Sulphate (.25N)
Dissolve 98g of FAS in distilled water and add 20ml conc. H 2SO4 and cool it and
dilute it to 1000ml.
 Apparatus
 COD digester
 Glass vials (10ml) standard
 Titration apparatus
 Burette
 Pipette
 Funnel
 Titration flask
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 Burette stand
 Measuring cylinder

Procedures

 Part A
 Take vials of 10ml.
 Put 100ml sample in blender for 30sec to make the sample homogeneous.
 Set the digester ON and preheat to 150 degrees Celsius.
 Take the viols and old it to angle of 45 degrees and remove its cap. Use a clean
pipette to add 2.5ml sample, 1.5ml of digestion solution and 3.5ml of sulphuric acid
reagent. This will be total of 7.5ml.
 Replace the viol cap and rinse it from outside with distilled water and dry it with
tissue paper.
 Invert the viols several times to mix the solution in the viol.
 Also prepare a blank solution by repeating all above steps.
 Place the both viols in the pre-heated COD digester and weight for 2hours.
 After the 2 hours turn OFF the digester and weight for further 20 minutes to let the
viols to cool.
 After it take the viols out and invert it several times and place the viols into the
rack.
 Wait until the viols are cooled to room temperature.
 Part B
 After the above steps, transfer the content in a viol to 250ml titration flask. Add 1-2
drops of purine indicator.
 Fill the burette with standard FAS.
 Now titrate the sample solution I flask against standard FAS until the colour
changes from blue green to reddish brown.
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 Calculate COD using formula:

( A−B )∗8000∗Molarity of FAS
COD as mg/L of O2 =
mL of sample
Where,
A= Volume of FAS used for water sample
B= Volume of FAS used for blank sample

Observations and Calculations

 A = Volume of FAS used for water sample = 1.3 ml

 B = Volume of FAS used for blank sample = .5 ml
 ml of sample = 7.5
 Molarity of FAS = .25
( A−B )∗8000∗Molarityof FAS
COD as mg/L of O2 =
mLof sample
( 1.3−.5 )∗8000∗0.01
=
7.5
= 8.5333 mg/L

Results

The COD of the given water sample is 8.5333 mg/L.

Comments

We have performed this experiment in the lab and have learn many interesting and informative
facts about COD in water quality analysis of marine. We also have studied the methods to find
the COD of water and its importance in the waste water dumping in the natural water sources to
maintain the water quality in that water source. It was quite interesting and informative activity
indeed.