Experiment 4: COD

Objective:
1. To determine chemical oxygen demand (COD) in waste water sample.

Results:
Sample.
Blank.
Sample (trial 1)
Sample (trial 2)
Mean reading of sample

COD value (mg/L)

0
Under range
Under range
-

Discussion:
The Chemical Oxygen Demand (COD) test is used widely to estimate the
amount of organic matter in wastewater. It is a measurement of the oxygen
equivalent of the materials present in the wastewater that are subject to oxidation
by a strong chemical oxidant, in this case, dichromate. When wastewater contains
only readily available organic bacterial food and no toxic matter, the COD test
results provide a good estimate of BOD (Biochemical Oxygen Demand) values.
In the reactor digestion method test, the COD procedure is greatly simplified
over the Dichromate Reflux Method. Small volume of the water sample is pipette
into vials containing the pre-measured reagents, including catalysts and chloride
compensator. The vials are incubated until digestion is complete and then cooled.
The COD determination is made with the spectrophotometer.
The test measures the amount of oxygen required for chemical oxidation of
organic matter in the sample to carbon dioxide and water. The test procedure is to
add a known quantity of standard potassium dichromate solution, sulfuric acid
reagent containing silver sulfate. The mixture is refluxed for 2 hours by COD reactor.
Most types of organic matter are destroyed in this boiling mixture of chromic and
sulfuric acid,
Organics + Cr2O72- + H+ CO2 + H2O + 2Cr3+
After the mixture has been cooled, the chromium (III) ion in the specimen is
measured by spectrophotometer. The excess chromium (III) ion show how much
chromic was use by organics matter. The purpose of running a blank is to
compensate for any error that may result because of the presence of extraneous
organic matter in the reagents.

The value of COD got from this experiment was under range. This is may be
due to the COD digestion reagent vials type use was high range. Sample
concentration range (mg/L) is between 20 1500. Hence, COD value lower than 20
mg/L cannot be detected.
Question:
Dichromate reflux method.
1. What was the purpose of that blank sample of distilled water?
To compensate for any error that may result because of the presence of
extraneous organic matter in the reagents.
2. What will happen to COD value if HgSO 4 is not added?
- Chlorine will not be separated out of the sample effluent. COD will be
higher than it should be.
3. Summarize the dichromate reflux method and write the chemical reaction
involved.
- Sample is refluxed with known amount of excess dichromate in presence
of acid. HgSO4 catalyst is used to bind or complex chlorides. Remaining
dichromate is titrated with FAS to determine that used for oxidizing the
organic matter.
6Fe2+ + Cr2O72-

->

6Fe3+ + 2Cr3+ + 7H2O

Ferroin indicator gives a sharp change to brown color on complete

reduction of dichromate. FAS is a secondary standard, must be
standardized frequently. Result expressed as mg/L COD.
Reactor digestion method.
1. Why is it important to determine COD test in wastewater treatment?
- Determine the amount of organic pollutants found in surface water (e.g.
lakes and rivers) or wastewater, making COD a useful measure of water
quality.
2. Summarize the method and write the chemical reaction involved.
- Turn on the Reactor. Preheat to 150 C. Carefully pipette 0.20 mL of
sample into the vial. Cap and clean the outside of the vial. Hold the vial by
the cap over a sink. Invert gently several times to mix. Place the vial in
the preheated Reactor. Heat for 2 hours. Turn the reactor off. Cool down
the vial. Invert the vial several times while still hot. Insert the vial into the
cell holder. Close the lid.
3. A sample is collected for COD analysis and it is to be performed on the
following day. Describe two ways by which the sample can be preserved. Why
is it necessary to preserve the sample?
- Two ways to preserved water sample are adding a little bit acid and
refrigeration. Putting samples in ice and keeping them there until they are
submitted to the laboratory will preserve them well enough for most tests.
It is necessary to preserve the sample to retard the chemical and
biological changes in the sample.

Conclusion:
Chemical oxygen demand (COD) is used as a measure of oxygen requirement of
sample that is susceptible to oxidation by strong chemical oxidant. The COD value
for sample in this experiment was under range. Hence, we can conclude that this
water sample has low organic matter. Chemical Oxygen Demand is the total
measurement of all chemicals in the water that can be oxidized.

Appendix: