Faculty of Applied Sciences

CMT 565

Wastewater and Technology

Tittle of the experiment: Experiment 5 – Chemical Oxygen

Demand (COD)

Name of students 1. Amy Nabila bt Rusli (2014473722)

2. Balkis bt Hazmi (2014636182)
3. Mohammad Syazwan bin Mohd Jafri
(2014838732)
Date of Experiment 15/4/2016
Name of Lecturer Dr. Shariff bin Che Ibrahim
Date of Submission 24/4/2016
Experiment 13 - Coagulant & Flocculant

Objectives

- To determine and measure of oxygen requirement of the sample waste water through
chemical oxygen demand (COD) process.

Introduction

- Chemical oxygen demand (COD) is a quick, inexpensive means to determine organics in

water. It is normally measured in both municipal and industrial wastewater treatment plants
and gives an indication of the efficiency of the treatment process. Chemical oxygen demand
test uses a strong chemical oxidant in an acid solution and heat to oxidize organic carbon to
CO2 and H2O. It can be expressed in milligrams per liter (mg/L) also referred to part per
million (ppm) which indicates the mass of oxygen consumed per liter solution. COD always
used and measure as the rapid indicator of organic pollutant in water, making COD a useful
measure of water quality. It is normally measured in both municipal and industrial
wastewater treatment plants and gives an indication of the efficiency of the treatment process.
The basic of COD test is nearly all organic compounds can be fully oxidize an organic
compound to carbon dioxide, ammonia and water. Dichromate has been used to oxidize
organic matter it is preferred over other oxidants because of its superior oxidising ability,
applicability to a wide variety of samples and ease of manipulation. The degree of oxidation
depends on the type of substances, pH value, temperature, reaction time and concentration of
oxidizing agent.

Apparatus

- Digestion reactor/ COD reactor, spectrophotometer, pipette, 0.1 – 1 mL + tips, COD vials
rack.

Reagents/ chemicals

- COD digestion reagent vials and COD standard solution.

Procedure

Firstly, the accuracy of the 20 – 1500 mg/L range was checked by used 300 mg/L of standard
solution. The 2 mL of one of these solutions was used as the sample volume. The result must
be 100 mg/L COD respectively, if not the calibration on the instrument used was adjusted.
The sample contains suspended solid was homogenise 100mL of sample for 30 seconds in a
blender. The homogenised sample was pour into a 250 mL beaker and gently stir on a
magnetic plate for the 200 – 1500 mg/L range to improve the accuracy and reproducibility of
other ranges. The COD reactor was turned on and preheater to 150 o C. The safety shield was
place in front of the reactor. The caps of a COD digestion reagent vial was remove for the
appropriate range. The vial was hold at 45o angle,2.0 mL of the sample was pipetted into the
vial. The vial was cap tightly and the exterior of the COD vial was rinse and wipe clean with
paper towel. The vial was gently invert several times to mix the content and the vial was
placed in the preheated COD reactor. The blank was prepared by repeating the steps by
substituted the blank of 2.0 mL distilled water for the sample. The vial was heated for 2
hours. The reactor was turned off and waited about 20 minutes to cool the vial to 120oC.
Each of the vial was invert several times while still warm. The vial was placed into rack and
cooled to the room temperature. The procedure was proceed to the colorimetric determination
to measure the COD.

Result

COD (mg/L)
Blank 0
Sample 1 142
Sample 2 159
Sample 3 139
Standard 498

Observation
Photo 1: The color of the solution before place in COD reactor

Photo 2: The color of the solution after 2 hours placed in COD reactor

Discussion

The measurement oxygen required to oxidize biodegradable and non-biodegradable organic

matter in water is known as Chemical Oxygen Demand (COD). In this water quality test, the
strong oxidizing agent like potassium dichromate (Cr2O72-) was used to oxidize organic
matter in the water sample.

The acid (sulphuric acid) is needed and acted as catalyst to complete the reaction. The COD
test only takes a few hours to obtain the result. After the sample (2 ml) and reagents put
inside the vial, the solution was preheated in the COD reactor for two hours to increase the
rate of the reaction. As all of the reagent mixed well with sample, the vial became hot
because the exothermic reaction was took place. Based on observation, white precipitate
formed in each vial and the solution turn light brown from colourless. Blank is required to
ensure no outside organic material be accidently added.

After 2 hours, the organic matter was oxidized and the colour of the solution was changed
from light brown colour to light green which mean, the Cr2O72- was reduced to Cr3+.

Ag2SO4

3[C] + 2 Cr2O72- + 16 H+ 4 Cr3+ + 3CO2 + 8H2O

The COD reading (mg/L) obtained for blank, standard , sample 1,2 and 3 are 0, 142, 159,139
and 498 mg/L respectively. From the above result, the parameter of water sample is
considered as level IV which is more than 100 mg/l and need to treat because the amount of
oxygen reduction is high and can lead to anaerobic conditions, which is deleterious to higher
aquatic life forms.

There are some precautions should be alert in this experiment. Firstly, samples must be mixed
well and measured quickly to avoid settling errors. The wastewater samples need to be
shaken before pipette it for the dilution. The spectrophotometer must be warmed up and zero
using the reagent blank. If the volume of deionized water added to the reagent blank is not
2.0 mL, the color of the reagent blank will be either lighter or darker than expected. Besides
using this common method, we can apply other method in determination of chemical oxygen
demand such as photoelectrocatalysis of nanoporousTiO2 electrodes for more accurate and
short time test.
Parameter Classes
I II III IV V
COD value < 10 10 – 25 25 – 50 50 – 100 > 100

Table 2: Classes in Malaysian Water Quality Index for Chemical Oxygen Demand (COD)

Conclusion

Chemical Oxygen Demand (COD) of the sample can be measured using Reactor Digestion
Method. The COD ranges (mg/L) obtained for blank, standard , sample 1,2 and 3 are 0, 142,
159,139 and 498 mg/L respectively. COD range (mg/L) obtained is between 20-1500 which
is in high range.

References

Esteves, L., Oliveira, T., Elias, C., Bomfeti, C., Gonçalves, A., Oliveira, L., et al. (2015). A fast and
environment-friendly method for determination of chemical oxygen demand byusing the
heterogeneous Fenton-like process as anoxidant. Talanta, 75–80.

Zhaoyang, Z., Xin, C., & Aicheng, C. (2016). Determination of chemical oxygen demand based on
photoelectrocatalysis of nanoporous TiO2 electrodes. Elsevier, 664–670.

Question

1. Why is it important to perform COD test in wastewater treatment?

To determine the amount of organic pollutants found in surface water or wastewater.
This makes COD a useful measure of water quality.

2. What is the function of the blank vial in the determination?

To compensate for any error that may result because of the presence of extraneous
organic matter in the reagents.

3. What will happen to the COD value if HgSO4 and Ag2SO4 are not added?
Chlorine will not be separated out of the sample effluent, making COD value higher
than it should be.
4. What is the reason that some time a green solution is formed after digestion? How do
you overcome this problem?
The organic matter present in sample gets oxidized completely by potassium
dichromate (K2Cr2O4) in the presence of sulphuric acid (H2SO4), silver sulphate
(AgSO4) and mercury sulphate (HgSO4) to produce CO2 and H2O. Dichromate ions
form orange-coloured solutions. When dichromate is reduced to chromic ion, the
solution becomes green.
To overcome this problem, it must be treated as hazardous wastes and mercury.