Chemical Oxygen Demand

CHEMICAL OXYGEN
DEMAND
Chemical Oxygen Demand

It is a measurement of the oxygen
equivalent of the materials present
in the wastewater that are subject
for oxidation by a strong chemical
oxidant, in this case, dichromate.
Representation of pollution level of
domestic and industrial wastewater,
or contamination level of surface,
ground, and potable water.
Engr. Yvonne Ligaya F. Musico

It is determined in terms of total
oxygen required to oxidize the
organic matter to CO2 and water
It defines the strength of wastewater
containing non-biodegradable
organic substances or compounds
that inhibit biological activity.
Compared to BOD, COD
determination requires short
digestion period.

Principle
A measure of the oxygen equivalent
of the organic matter susceptible to
oxidation of strong oxidizing
chemicals a mixture of chromic
acid and sulfuric acid.
K2Cr2O7 + 4H2SO4 K2SO4 + Cr2(SO4)3 + 4H2O + 3O

Organic matter + O CO2 + H2O
The dichromate reduces to Cr+3, which imparts

green color to the reacting solution
Organic matter + Cr2O72- + H+ CO2 + H2O + 2Cr3+
COD Determination Methods

Open Reflux Method
Closed Reflux, Titrimetric Method
Closed Reflux, Colorimetric Method
Selection of Method
Open Reflux Method is suitable for a wide
range of wastes where a large sample size
is preferred.
The Closed Reflux (Titrimetric and
Colorimetric) are more economical in the
use of metallic salt reagents and generate
smaller quantities of hazardous waste, but
homogenization of samples containing
suspended solids to obtain reproducible
results.
CLOSE REFLUX
(COLORIMETRIC METHOD)
Apparatus
Spectrophotometer suitable for
measurements of 600nm and
420nm
Hach COD Block Reactor or Heating
Oven capable of maintaining a
temperature of 1502oC
Culture tubes or Cuvettes
Reagents
Potassium Dichromate Digestion Solution,
High Range
Add to about 500 mL distilled water 10.216 g
K2Cr2O7 primary grade, previously dried at
150oC for 2 hours.
Add 167 mL concentrated H2SO4, and 33.3 g
HgSO4.
Dissolve, cool to room temperature, and dilute
to 1000 mL.
NOTE: Dissolution must be done in water bath under
the fume hood
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Reagents
Potassium Dichromate Digestion Solution,
Low Range
Add to about 500 mL distilled water 1.022 g
K2Cr2O7 primary grade, previously dried at
150oC for 2 hours.
Add 167 mL concentrated H2SO4, and 33.3 g
HgSO4.
Dissolve, cool to room temperature, and dilute
to 1000 mL.
NOTE: Dissolution must be done in water bath under
the fume hood.
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Reagents
Sulfuric Acid Reagent
Add Ag2SO4, reagent or technical grade,
crystal or powder, to concentrated H2SO4 at
the rate of 5.5 g Ag2SO4/kg H2SO4. Let stand
1 to 2 days to dissolve. Mix
NOTE: Prepare the reagents under the
fume hood.
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Reagents
Potassium Hydrogen Phthalate (KHP)
Standard Solution
Lightly crush and then dry KHP to constant
weight at 110oC
Dissolve 0.851g in distilled water and dilute
to 1000 mL
KHP has a theoretical COD of 1.176 mg
O2/mg.
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Precautionary Measures
Prepare the reagents (Potassium
Dichromate and Silver Catalyst and
Sulfuric Acid Solution) under the
fume hood.
Use nitrile gloves at all times.
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Calibration
High Range
Dilute the following COD standard
solution to 50 mL with water
Std. Solution, mL
COD, mg/L
2.5
50
5.0
100
10.0
200
20.0
400
30.0
600
40.0
800
15
Calibration
Low Range
Dilute the following COD standard
solution to 200 mL with water
Std. Solution, mL
COD, mg/L
10
20
40
60
10
50
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The Calibration Curve
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PROCEDURE
1.5 mL K2Cr2O7
Digestion Solution
3.5 mL Ag2SO4
Catalyst
Mix
vigorously
and cool
+2.5 mL Std. Solution

(d. H2O for the blank)
Mix vigorously
Cool, after 5 min mix contents.

Cool further at room temp.
Digest in Hach COD Reactor or

in Oven at 1502oC for 2 hrs
Measure absorbance at
420 nm (low range)
600 nm (high range)
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Operating Instructions of UV-VIS

Spectrophotometer (UV-200 RS)
1. Plug the instrument into a grounded
outlet.
2. Turn the instrument on. Allow the
instrument to warm up for at least 20
minutes.
3. Select the desired wavelength with
wavelength Up and Down arrows.
4. Select the desired operating mode as
Transmittance, Absorbance, or
Concentration by pressing the MODE
key.
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5. Choose matched cuvettes of appropriate
pathlength for analytical method you are
using. You have to use the same
pathlength cuvette for all blanks, standard
and samples.
6. Fill one of the matched cuvettes with water
or other blank solution and place in
position of once of cuvette holder. Fill the
other positions with samples solutions to
be measured.
NOTE: The solution must be at least 20 mm
high in a standard square cuvette.
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7. Close the sample compartment, put the
blank solution into the light path, set
100%T or 0Abs by pressing the
0Abs/100%T key until display reads
100.0%T or 0.000A.
8. You may then measure other samples by
pulling the cuvette selector arm into the
next position and reading the %T or Abs
value of the samples.
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Thanks for Listening
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CHEMICAL OXYGEN