EXPERIMENT 11B: Chemical Oxygen Demand (COD) of Wastewater

Pre-Lab Reading: Standard Methods for Examination of Water and Wastewater, 5-12 –
5-16

Introduction

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 Reflex Method. Small volume of the water sample is pipetted 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 either with the spectrophotometer or by titration. This method is accepted for
reporting by US Environmental Protection Agency (EPA).

Theory

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, Eq 1.

Organics + Cr2O72- + H+ → CO2 + H2O + 2Cr3+ (1)

After the mixture has been cooled, the chromium (III) ion in the specimen is measured
by spectrophotometer.

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.

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Procedures

A. Preparation of Reagents

Digestion solution:

Dissolve 10.216 g K2Cr2O7 in about 500 ml DI water. Add 167 ml conc. H2SO4 and 33.3
g HgSO4 to the solution, mix well and dilute to 1000 ml. (Provided)

(CAUTION: HgSO4 is highly toxic. Wear protective gloves to prevent skin contact.)

Sulfuric acid reagent:

Dissolve 10.1 g of AgSO4 into 1000 ml of conc. H2SO4. (Provided)

(CAUTION: Conc. H2SO4 is highly corrosive. Wear protective gloves.)

Potassium hydrogen phthalate stock solution:

Dissolve 0.425 g of KHP into 50 ml DI water using a volumetric flask. And this solution
will have theoretical COD of 10000 ppm of O2.

KHP standard solutions:

Prepare KHP standard solutions of 200, 400, 600, 800, and 1000 ppm of O2 according to
the following table:

Standard No. COD/conc. (ppm) Vol. of KHP stock Total volume (ml)
added (ml)
Standard # 1 200 1.00 50.00
Standard # 2 400 2.00 50.00
Standard # 3 600 3.00 50.00
Standard # 4 800 4.00 50.00
Standard # 5 1000 5.00 50.00

B. Preparation of Sample

Obtain sample wastewater from TA and record the sample number. Pipette 10 ml of the
sample into a 100 ml volumetric flask and fill to the mark with DI water. Then, further
dilute the sample according to the following table:

Dilution No. Volume of diluted sample Total volume (ml)

(ml)
Dilution #1 25.00 50.00
Dilution #2 10.00 100.00
Dilution #3 1.00 100.00

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C. Standardization/Digestion

Pipette 2.0 ml 200 ppm standard solutions into a 16 x 100 mm culture tube. Add 2.0 ml
digestion solution into the tube. Then, carefully transfer 3.0 ml of sulfuric acid reagent
along the inner wall of the tube so that an acid layer is formed under the sample
digestion solution. Tightly cap the tube and shake gently to mix the layer.

(CAUTION: Wear protective gloves to protect hands from heat produced when
contents of vessels are mixed.)

Repeat the above procedures with the other standard solutions sample and blank (using
equal volume of DI water).

Put all the tubes into the block heater and heat the tubes at 150 oC for two hours in the
fumehood. After cooling the tubes to room temperature, invert the cooled sample, blank
and standards several times and allow solids to settle before measuring absorbance.

D. UV-VIS Measurement

Carefully transfer the solution from blank into a 1 cm cell and collect the spectrum from
550-650 nm. Then, transfer standard #1 into the cell and measure the absorbance of the
solution at 600 nm. Repeat the measurement with another standards, and sample.

E. Waste Disposal

After the experiment, discard all the solution into appropriate waste bottles as instructed
by TA.

Data Treatment and Questions

1. Calculate the COD of the sample.

2. What is the main reason using 600 nm for absorbance measurement?

3. What is BOD? What is the relationship between BOD and COD? Give a brief
account.

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