TABLE OF CONTENTS

No. Title Page

1.0 Introduction 2
2.0 Principles 3
3.0 Objectives 3
4.0 Apparatus 4
5.0 Procedures 5
6.0 Results 7
7.0 Discussion / Analysis 8
8.0 Conclusion 11
9.0 References / Appendices 12

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 CHEMICAL OXYGEN DEMAND

1.0 INTRODUCTION

The chemical oxygen demand (COD) is an indicative measure of the amount of oxygen
that can be consumed by reactions in a measured solution. It is commonly expressed in mass of
oxygen consumed over volume of solution which in SI units is milligrams per litre (mg/L). A
COD test can be used to easily quantify the amount of organics in water. The most common
application of COD is in quantifying the amount of oxidizable pollutants found in surface
water (e.g. lakes and rivers) or wastewater. COD is useful in terms of water quality by
providing a metric to determine the effect an effluent will have on the receiving body much
like biochemical oxygen demand (BOD).

A common method for Chemical Oxygen Demand analysis is Method 410.4. The
method involves using a strong oxidizing chemical, potassium dichromate Cr2O72-, to oxidize
the organic matter in solution to carbon dioxide and water under acidic conditions. Often, the
test also involves a silver compound to encourage oxidation of certain organic compounds and
mercury to reduce the interference from oxidation of chloride ions. The sample is then digested
for approximately 2 hours at 150°C. The amount of oxygen required is calculated from the
quantity of chemical oxidant consumed.

Chemical Oxygen Demand is an important water quality parameter because, similar

to BOD, it provides an index to assess the effect discharged wastewater will have on the
receiving environment. Higher COD levels mean a greater amount of oxidizable organic
material in the sample, which will reduce dissolved oxygen (DO) levels. A reduction in DO
can lead to anaerobic conditions, which is deleterious to higher aquatic life forms. The COD
test is often used as an alternate to BOD due to shorter length of testing time.

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2.0 PRINCIPLES

The mg/L COD results are defined as the mg of O² consumed per liter of sample under
conditions of this procedure. In this procedure, the sample is heated for two hours with a strong
oxidizing agent, potassium dichromate. Oxidizable organic compounds react, reducing the
dichromate ion (Cr²O7²-) to green chromic ion (Cr³+). When the 0.7- 40.0 or the 3-150 mg/L
colorimetric method is used, the amount of 𝐶𝑟 6+ remaining is determined. When the 20-1500
mg/L or the 200-15,000 mg/L colorimetric method is used, the amount of Cr³+ produced is
determined. The COD reagent also contains silver and mercury ions. Silver is a catalyst, and
mercury is used to complex chloride interference. Test results for the 0.7 to 40.0 mg/L range
are measured at 350 nm. Test result for the 3 to 150 mg/L range are measured at 420nm. Test
results for the 20 to 1500 and the 2000 to 15,000 mg/L COD range are measured at 620 nm.

3.0 OBJECTIVES

This test method is appropriate for the determination of Chemical Oxygen Demand (COD) in
all types of water and wastewater.

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4.0 APPARATUS:

1) Micropipette 2) COD sample

3) Beaker 4) COD Reactor

5) UV-VIS Spectrophotometer 6) COD’ specimen tube

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5.0 PROCEDURES
Digestion procedure

100 ml of sample was

homogenized for 30 seconds in a
blender. Sample that have large
amounts of solids, increase the
homogenization time.

The homogenized sample was

poured into the beaker and stired
gently with a magnetic stir plate.
(For 200-15000 mg/L range or to
improve accuracy and
reproducibility of the other range).

The COD reactor was turned on

and preheat to 150 ℃. For selecting
pre- programmed temperature
application,just saw the COD
reactor.

Prepared sample
1. One vial was hold at 45-degree angle. A clean volumetric pipette was used to add 2.00
mL of sample to the vial. A micro pipette was used to add 0.2 mL for the 200 – 15,000
mg/L range.

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a. Blank preparation

A second vial was hold at 45 degree angle. A clean

volumetric pipet was used to add 2.00 ml of deionized
water to the vial and micro pipet was used to add 0.20 ml
for the 200-15000 mg/L range.

The vials was cap tightly. It was rinse with water and wipe
it with a clean paper towel. The vials was hold by the cap
over a sink. It was invert gently several times to mix. The
vials was inserted in the preheated COD Reactor. The
sample will became very hot during mixing. The vials was
heated for 2 hours.

Each vials was inverted several times while still warm. The
vials was placed into a rack and cool to room temperature.
Colorimetric Determination was proceed.

b. Calorimetric Determination Method

The ultra-low range, low range or high range test was selected
based on the sample.

The outside of the vials was cleaned with a

damp towel followed by a dry one.

The blank was inserted into to 16-mm cell holder.

ZERO was press and the display will show : 0.0
mg/L COD.

The sample vial was inserted into the 16-mm cell holder. Result was in
mg/L. (if using High Range Plus COD Digestion Reagent Vials, the
result was multiply by 10)

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6.0 RESULTS

Type of COD Digestion Reagent Vials: Low Range (3 – 150 mg/L)

Reading (mg/L) Average

No. Vial
1 2 3 (mg/L)
1 Blank 0 0 0 0
2 Sample 38 38 37 37.67

Calculation:

38 + 38 + 37
Average = = 37.67 mg/L
3

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7.0 DISCUSSION / ANALYSIS

1. What is the purpose of using HgSO4 and Ag2SO4 in the COD test?

In COD test, Mercuric Sulfate (HgSO4) and Silver Sulfate (Ag2SO4) act as chemical
oxidizing agents. The purpose of using HgSO4 and Ag2SO4 in the COD test is to oxidize
organic matter in distilled water and wastewater samples. Mercuric sulfate (HgSO4) added
to remove interference of chlorides. Cl- ions interfere in the COD digestion by complexing
with the silver to reduce its catalytic effect and by reacting with the dichromate to form
elemental halogens thus giving falsely high readings.
HgSO4 is used as strong oxidant to complex Cl- ion or eliminate chloride interference
in order to maintain acidic condition and provides the primary digestion catalyst of the
solution. Ag2SO4 is used to oxidize the straight chain of hydrocarbon such as low
molecular weight fatty acid present if any in the sample and act as secondary catalyst.
Interference from nitrites can be prevented by the addition of 10:1 ratio of sulphuric
acid: nitrite. The addition of the Silver Sulfate (Ag2SO4) and concentrated sulphuric acid
(H2SO4) refluxing acid will aid in the oxidation of some organic nitrogen compounds, but
aromatic hydrocarbons and pyridine are not oxidized to any appreciable amount.

2. What are the applications for COD analysis?

Chemical oxygen demand (COD) test is commonly used to indirectly measure the
amount of organic compounds in water. In another word, COD is often measured as a rapid
indicator of organic pollutant in water. Most applications of COD are to determine the
amount of organic pollutants found in the surface water such as lakes and rivers or waste
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. COD is measured on both influent and effluent water.
The efficiency of the treatment process is normally expressed as COD Removal, measured
as a percentage of the organic matter purified during the cycle. COD is measured in mg/L
through a colorimetric method in which dichromate is added and the sample is digested.
The applications for COD analysis are mostly for the environmental applications

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3. Why are COD results generally higher than the BOD results?

Chemical oxygen demand (COD) test is commonly used to indirectly measure the
amount of organic compounds in water. Most applications of COD determine the amount
of organic pollutants found in surface water. However Biochemical oxygen demand
(B.O.D) is the amount of dissolved oxygen needed by aerobic biological organisms in a
body of water to break down organic material present in a given water sample at certain
temperature over a specific time period.
Besides, COD results generally higher than the BOD results because COD test is used
as primarily operational control which only takes 3 hours as compared to BOD test which
need to conduct in 5 days. Next, COD is chemical oxidation process where BOD is
biological oxidation. Chemical reaction is more complete compare to biological process
which may be affected by environmental factors. COD is preferred to use as daily analysis
since it is inherently more reproducible, accounts for changing conditions and takes a short
time to complete. A COD test measures all of the chemicals in a sample which can be
oxidized. Moreover, BOD contains only biodegradable compound inside the water sample
whereas COD includes biodegradable and non- biodegradable this make the reason why
COD is larger than BOD results.What advantages and disadvantages of the COD test
compared to the BOD test?

Advantages:
COD
i. Fast to complete and the results
are reproducible.
ii. Need lesser quantities of macro
nutrients, nitrogen, phosphorus
and sulfur in addition to trace
amount of micronutrients.
iii. Oxidizes wider range of
chemical compounds.
iv. Easy standardization.
v. Simple and inexpensive
apparatus required.
vi. Provides direct estimate of the
oxygen or energy potential of the
volatile solids.
BOD
i. Most widely used to test
establish concentration of
organic matter in wastewater
samples.
ii. Acid hydrolysis of the tested
water converts all the water flora
into biodegradable nutrients.
iii. Degree of waste stream which
cause pollution can be
determine.
iv. Overall health of receiving
waters can be determine.

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Disadvantages:

i. Inability to differentiate between i. Long period of incubation.

biological oxidizable and ii. Poor reproducibility.
biological inert organic matter. iii. Susceptible to inhibitions by
ii. Does not oxidize ammonia. many industrial wastes.
iii. Interference from high iv. Required high energy
concentration of chloride ions. consumptions for aeration
iv. Many in-biodegradable organic purposes.
compounds exert an oxygen v. The results are not consistent by
demand. keeping on varying depending on
the presence of microorganisms.

Cause and Error

i. The vial is not rinse cleanly with distilled water and it may contain others impurity

Safety Measure & Precautions

i. Rinse the vial with distilled water.

ii. Wear personal protective equipment (PPE) when carry out this
experiment in laboratory.
iii. Make sure the outside of the vials is cleaned before insert into the cell holder.

iv. Make sure the display is shown 0.0mg/L COD for the blank vial.

v. Do not dispose the hazard waste into the sink.

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8.0 CONCLUSION

The objectives of the experiment have been achieved. We able to determine the given
water waste samples with an average reading of 37.67 mg/L by using Chemical Oxygen
Demand (COD) test method. Apart from that, we able to understand the purpose of using
HgSO4 and Ag2SO4 in the COD test which HgSO4 is used to maintain acidic condition and
provides the primary digestion catalyst of the solution and AgSO4 is used to oxidize the straight
chain of hydrocarbon such as low molecular weight fatty acid present if any in the sample.
During digestion the sample’s organic carbon (C) material is oxidized with the hexavalent
dichromate ion (Cr2O72-) found in potassium dichromate (K2Cr2O7). The dichromate readily
gives up oxygen (O2) to bond with carbon atoms to create carbon dioxide (CO2). The oxygen
transaction from Cr2O72- to CO2 reduces the hexavalent Cr2O72- ion to the trivalent Cr3+ ion. In
essence a COD test determines the amount of carbon-based materials by measuring the amount
of oxygen the sample will react with.

The precaution and improve method for this experiment is we must rinse the vial
cleanly with distilled water to remove others impurity inside the vial. Besides that, make sure
outside of the vial is clean with dry tissue paper before determining the reading by using
Calorimetric Determination method. After the experiment, do not dispose the hazard left over
during the experiment into the sink.

The purpose of testing COD test on industries is for government to determine the
amount of pollution in a water stream to try to control and limit the amount of chemicals that
can pollute the lakes and rivers in a final effluent or discharge stream for water treatment
process.

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9.0 REFERENCES / APPENDICES
1. University Malaysia Pahang - Civil Engineering Laboratory Manual (Third Edition)
2. https://realtechwater.com/chemical-oxygen-demand/
3. https://www.merckmillipore.com/MY/en/water-purification
4. https://realtechwater.com/parameters/chemical-oxygen-demand/

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