Sanitary Lab

Asst. lect. Nuralhuda A. Jasim

Eighth Experiment (12) Determination of Chemical Oxygen Demand

Figure (18) Chemical Oxygen Demand

The chemical oxygen demand (COD) is a measure of water and wastewater quality.
The COD test is often used to monitor water treatment plant efficiency. This test is
based on the fact that a strong oxidizing agent, under acidic conditions, can fully
oxidize almost any organic compound to carbon dioxide. The COD is the amount of
oxygen consumed to chemically oxidize organic water contaminants to inorganic end
products.
The COD is often measured using a strong oxidant (e.g. potassium dichromate,
potassium iodate, potassium permanganate) under acidic conditions. A known excess
amount of the oxidant is added to the sample. Once oxidation is complete, the
concentration of organics in the sample is calculated by measuring the amount of
oxidant remaining in the solution. This is usually done by titration, using an indicator
solution. COD is expressed in mg/L, which indicates the mass of oxygen consumed
per liter of solution.

The COD test only requires 2-3 hours, while the Biochemical (or Biological) Oxygen
Demand (BOD) test requires 5 days. It measures all organic contaminants, including
those that are not biodegradable. There is a relationship between BOD and COD for

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each specific sample, but it must be established empirically. COD test results can then
be used to estimate the BOD of a given sample. Unlike for the BOD test, toxic
compounds (such as heavy metals and cyanides) in the samples to be analyzed do not
have an effect on the oxidants used in the COD test. Therefore, the COD test can be
used to measure the strength of wastes that are too toxic for the BOD test. Some
organic molecules (e.g., benzene, pyridine) are relatively resistant to dichromate
oxidation and may give a falsely low COD.

COD contrasts with biochemical oxygen demand (BOD), which relies on the use of
microorganisms to break down the organic material in the sample by aerobic
respiration over the course of a set incubation period (typically five days).

BOD and COD correlate with one another in virtually all samples, but BOD is always
lower than COD as the biochemical breakdown of organics is often not as complete as
the chemical method.

Importance of Chemical Oxygen Demand

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
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.

Wastewater facilities reduce COD and BOD by using these same microbes under
controlled conditions. These facilities aerate chambers injected with specialized
bacteria that can break down the organic matter in an environment that does not harm

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natural waters. A reduction in BOD is used in these facilities as a benchmark for

treatment effectiveness.

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.

How to Measure Chemical Oxygen Demand?

As mentioned before, COD measures organic matter by using a chemical oxidant. It’s
critical that a strong enough oxidant is used to react with virtually all organic material
in the sample. Historically, potassium permanganate filled this role, but it was found
to be inconsistent in its ability to oxidize all the organic matter in a wide variety of
waste samples.

Currently, most COD tests use potassium dichromate as the oxidant. Potassium
dichromate is a hexavalent chromium salt that is bright orange in color and is a very
strong oxidant. Between 95-100% of organic material can be oxidized by dichromate.
Once dichromate oxidizes a substance it's converted to a trivalent form of chromium,
which is a dull green color.

Digestion is performed on the samples with a set amount of the oxidant, sulfuric acid,
and heat (150°C). Metal salts are usually included to suppress any interferences and to
catalyze the digestion. The digestion typically takes two hours to perform.

During the digestion, it's necessary to have excess oxidant; this ensures complete
oxidation of the sample. As a result, it’s important to determine the quantity of excess
oxidant. The two most common methods for this are titration and colorimetry.

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Titrimetric Method of COD

In the titration method for determining COD, the excess dichromate is reacted with a
reducing agent, ferrous ammonium sulfate. As the ferrous ammonium sulfate (FAS) is
added slowly, the excess dichromate is converted into its trivalent form.

As soon as all the excess dichromate reacts, an equivalence point is reached. This
point means that the amount of ferrous ammonium sulfate you added is equal to the
amount of excess dichromate. Color indicators can also signal this endpoint, but the
process may be automated with a potentiometric indicator (like an electrode).

Afterwards, you can calculate how much dichromate went towards oxidizing organic
material based on how much we initially added and how much was left over.

Colorimetric Method of COD

It is looked at the consumption of dichromate by looking at the change in the

absorbance of the sample. The samples absorb at particular wavelengths due to the
color of trivalent chromium (Cr3+) and hexavalent chromium (Cr6+).

It is quantified the amount of trivalent chromium in a sample after

digestion by measuring the absorbance of the sample at a wavelength
of 600 nm in a photometer or spectrophotometer. Alternatively, the
absorbance of hexavalent chromium at 420 nm can be used to
determine the amount of excess chromium at the end of digestion to
determine COD values.

This method is easy and requires just a few simple steps.

1. Digest your samples and a reagent blank. (The reagent blank is just a sample
of deionized water that’s treated the same as your actual samples. You can
even reuse the blank for as long as your reagent batch lasts.)

2. Let the digested samples and blank cool.

3. Zero the instrument using the blank vial.

4. Read the samples.

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The estimation of COD is of great importance for waters having unfavourable

conditions for the growth of microorganisms, such as presence of toxic chemicals. In
such water BOD cannot be determined accurately. COD is always higher than BOD,
by approximately 2 to 3 times of BOD.

Objective
To determine COD of the given sample of waste water.

APPARATUS
(1) COD Flask
(2) Condensor
(3) Heating Mantle
(4) Measuring Cylinder

There are two methods available for COD determination namely open reflux and
closed reflux.
Open Reflux Principle:
1. Suitable for a wide range of wastes with a large sample size.
2. Due to it higher oxidizing ability dichromate reflux method is preferred over
other procedures using other oxidants (e.g. potassium permanganate).
3. Oxidation of most organic compounds is up to 95-100% of the theoretical
value.
Closed Reflux Principle:
1. This method is conducted with ampules and culture tubes with pre-measured
reagents.
2. Measurement of sample volume and reagent volume are critical.
3. This method is economical in the use of metallic salt reagents and generates
smaller quantity of hazardous wastes.
4. Volatile organic compounds (VOC) get completely oxidized in a closed
system than the open because of longer contact time with oxidants.

REAGENTS:
1. Standard Potassium dichromate (K2Cr2O7) digestion solution,
0.01667M:

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Add to about 500 mL distilled water 4.903 g K2Cr2O7, primary standard grade,
previously dried at 150°C for 2 h, 167 mL conc. H2SO4, and 33.3 g HgSO4.
Dissolve, cool to room temperature, and dilute to 1000 mL.
2. Sulfuric acid reagent:
Add H2SO4 at the rate of 5.5 g Ag2SO4/kg H2SO4 or 10.12 g silver sulphate/L
H2SO4. Let stand 1 to 2 d to dissolve and mix. This accelerates the oxidation of
straight chain aliphatic and aromatic compounds.
(1 Kg = 543.47826 mL of H2 SO4 and take 20.24 g of Ag2SO4 to 2 L of H2
SO4 or 22.264 g of Ag2SO4 to 2.2 L of H2 SO4)
3. Ferroin Indicator solution:
This indicator is used to indicate change in oxidation-reduction potential of the
solution and indicates the condition when all dichromate has been reduced by ferrous
ion. It gives a very sharp brown color change which can be seen in spite of blue color
generated by the Cr3+ ions formed on reduction of the dichromate.
4. Standard ferrous ammonium sulfate titrant (FAS), approximately 0.10M:
Dissolve 39.2 g Fe (NH4)2(SO4)2.6H2O in distilled water. Add 20 mL conc.
H2SO4, cool, and dilute to 1000 mL. Standardize solution daily against standard
K2Cr2O7 digestion solution as follows: Pipet 5.00 mL digestion solution into a small
beaker. Add 10 mL reagent water to substitute for sample. Cool to room temperature.
Add 1 to 2 drops diluted Ferroin indicator and titrate with FAS titrant.
Molarity of FAS solution = [VK2Cr2O7 ×0.1] / (VFAS)

Where: VK2Cr2O7 = volume of K2Cr2O7 (mL); VFAS = volume of FAS (mL)

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Figure (19) The chart Procedure of open reflux method

Procedure of Open Reflux Method:

1. Wash culture tubes and caps with 20% H2SO4 before using to prevent
contamination.
2. Place sample (2.5 mL) in culture tube and Add K2Cr2O7 digestion solution (1.5
mL).
3. Carefully run sulphuric acid reagent (3.5 mL) down inside of vessel so an acid
layer is formed under the sample-digestion solution layer and tightly cap tubes or seal
ampules, and invert each several times to mix completely.
4. Place tubes in block digester preheated to 150°C and reflux for 2 h behind a
protective shield.

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5. Cool to room temperature and place vessels in test tube rack. Some mercuric sulfate
may precipitate out but this will not affect the analysis.
6. Add 1 to 2 drops of Ferroin indicator and stir rapidly on magnetic stirrer while
titrating with standardized 0.10 M FAS.
7. The end point is a sharp color change from blue-green to reddish brown, although
the blue green may reappear within minutes.
8. In the same manner reflux and titrate a blank containing the reagents and a volume
of distilled water equal to that of the sample.
9. COD is given by

OR: using FAS as titrant then the COD can be calculated by this equation:
COD (mg O2 /L) = [(A-B) × M ×8000) / (V sample)
Where: A = volume of FAS used for blank (mL)
B = volume of FAS used for sample (mL)
M = molarity of FAS
8000 = milli equivalent weight of oxygen (8) ×1000 mL/L.

The other method, Closed Reflux, Titrimetric Method

Volatile organic compounds are more completely oxidized in the closed system
because of longer contact with the oxidant. Before each use inspect culture-tube caps
for breaks in the TFE liner. Select culture-tube size according to block heater capacity
and degree of sensitivity desired. Use the 25- 150-mm tube for samples with low
COD content because a larger volume sample can be treated. This procedure is
applicable to COD values between 40 and 400 mg/L. Obtain higher values by
dilution. Alternatively, use higher concentrations of dichromate digestion solution to
determine greater COD values. COD values of 100 mg/L or less can be obtained by
using a more dilute dichromate digestion solution or a more dilute FAS titrant.

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Overall accuracy can be improved by using an FAS titrant which is less than the
0.10M solution specified below. Higher dichromate concentrations or reduced FAS
concentrations probably require titrations to be done in a separate vessel, rather than
in the digestion vessel, because of the volumes of titrant required.

ANSWER THESE QUESTIONS:

1. Why do the COD analysis and BOD analysis give different results for the
same waste?
2. What are the differences between BOD and COD tests?
3. What could be inferred from the following samples concerning the relative
ease of biodegradability: Sample A (5-d BOD/COD=24/30) and Sample B (5-
d
BOD/COD=10/50)?