1.

0 INTRODUCTION

1.1 OBJECTIVE

To measure the COD of solid and liquid organic substances in the sample using
reactor digestion method.

1.2 BACKGROUND MATERIAL

The Chemical oxygen demand (COD) is used as a chemical measure of oxygen

equivalent of the organic matter content of a sample water. Usually, this
measurement is widely used in municipal and industrial facilities to measure the
overall level of organic contaminant in wastewater. This is important because when
organic polluting matter is discharged to the aquatic environment it will normally
take up dissolved oxygen during its subsequent degradation thus reducing the
amount of oxygen available for the respiration of fish and other aquatic life.

A strong oxidizing agent together with acid and heat are used to oxidize all
carbon compounds in a sample. Non-biodegradable and recalcitrant (slowly
degrading) compounds, which are not detected by the test of BOD, are included in
the analysis. The actual measurement involves a determination of the amount of
oxidizing agent (typically, potassium dichromate) that is reduced during the reaction.

COD test is useful for performing rapid, frequent monitoring in determining the
aggregate organic matter, and results allow quick response to changing conditions in
the waste stream. It does not differentiate between biodegradable and non-
biodegradable organic matter. Besides, COD test is also used to measure the
strength of wastes that are too toxic for the BOD test.

1
1.3 THEORIES AND EXPLAINANTION

In a COD test, it is critical that a strong chemical oxidant is used to react with
virtually all organic material in the sample. Historically, potassium permanganate is
used, but it was found to be inconsistent in its ability to oxidize all the organic matter
in a wide variety of waste samples. Currently, potassium dichromate is used as the
oxidant in most COD tests. It is a hexavalent chromium salt that is bright orange in
colour and is a very strong oxidant. Once dichromate oxidizes a substance, it is
converted to a trivalent form of chromium, which is a dull green colour.

Digestion is performed on the sample with a set amount of the oxidant, sulfuric
acid and heat (150oC). Metal salts are usually included to suppress any interferences
and to catalyse the digestion. The digestion process takes about 2 hours. During
digestion, it is necessary to have excess oxidant to ensure complete oxidation of the
sample. To get the COD value, we have to determine the quantity of excess oxidant
by using titration method or colorimetric method.

In this experiment, colorimetric method was used. Colorimetric method is a

method to quantify the amount of trivalent chromium in a sample after digestion by
measuring the absorbance of the sample at a wavelength of 600 nm in a
spectrophotometer. Alternatively, the absorbance of hexavalent chromium at 420 nm
can be used to determine the amount of excess chromium at the end of digestion to
determine the COD values.

The colorimetric method is easy and only requiring some simple steps. First,
digest the sample water and a reagent blank. The reagent blank or known as the
control solution is prepared by treating the distilled water same as the actual sample.
Next, let the digested samples and blank cool to around 120oC before taking it out
from the COD reactor. Then, zero the spectrophotometer using the control solution.
Lastly, insert the sample into the spectrophotometer and read the COD value shown
on the screen.

2
1.4 DESCRIPTION OF SPECIALIZED EQUIPMENT

In this experiment, there are two main instruments that we used, which are
HACH COD Reactor and HACH Spectrophotometer DR 6000. The HACH COD Reactor
is a 25-well, dry-bath incubator that provides the 150oC temperature environment
required for chemical oxygen demand (COD) determination. This instrument also
provides features for timed operation as well as temperature adjustment. In the COD
digestion mode, the temperature is set at 150oC. By placing the thermometer in the
block heater block temperature can be verified. In the adjustable temperature mode,
this instrument can be used for digestion of other samples that require different
digestion temperatures. A 2-hour timer is incorporated for applications where timed
digestion is desired. When this feature is used, the bell will sound and the unit will
shut off at the end of the selected time period. The timer can also be used without
the shut-off feature when operating in the infinity mode.

Figure 1: The timer and the panel of HACH COD Reactor

3
 For HACH Spectrophotometer DR 6000, it is a laboratory spectrophotometer
used for water testing. It offers high-speed wavelength scanning across the UV and
Visible Spectrum, and comes with over 250 pre-programmed methods including the
most common water and environmental testing methods used today. This instrument
can handle wide-ranging water testing needs because it allows high-volume testing
and increased accuracy with a sample delivery system that eliminates optical
difference errors.

This DR 6000 Spectrophotometer has a wavelength range of 190 – 1100 nm.

The visible spectrum (320 – 1100 nm) is covered by a halogen lamp and a deuterium
lamp produces the light in the UV spectrum (190 – 360 nm). This instrument has a
complete range of application programs and supports several languages. It also
provides digital readouts of concentration, absorbance and percent transmittance.
When selecting a user-generated or programmed method, the menus and prompts
serve to direct the user through the test. This menu system can also produce
reports, statistical evaluations of generated calibration curves and reports on
instrument diagnostic checks. The DR 6000 Spectrophotometer contains the
following programs and operating modes:

i. Stored programs (pre-installed tests)

ii. Barcode Programs

iii. User Programs

iv. Favorites

v. Single Wavelength

vi. Multi Wavelength

vii. Wavelength Scan

viii. Time course

4
 Figure 2: HACH Spectrophotometer DR 6000

1.5 JUSTIFICATION OF EXPERIMENT’S IMPORTANCE

The objective of this experiment is to measure the COD of solid and liquid
organic substances in the sample using reactor digestion method. Therefore, by
doing this experiment, the students know how to use the instruments which are COD
Reactor and Spectrophotometer DR 6000. In this method, students can also observe
the colour changing of the digestion solution from before it is mixed with the sample
to after mixed solution is heated for two hours which is known as colorimetric
determination. The DR spectrometer were used to measure the COD of water sample
by comparing it with water control.

5
2.0 METHODOLOGY

2.1 MATERIALS AND APPARATUS

1. Digestion solution for COD (Range 20 - 1000mg/L)

2. Control solution (distilled water and digestion solution for COD)
3. HACH COD reactor
4. HACH Spectrophotometer DR 6000
5. Water sample (Tasik FSSA)

2.2 PROCEDURE

1. The COD Reactor is preheated to 150 ⁰C.

2. The cap of the vial is removed. 2 mL of sample is pipetted into the vial.

3. The vial is closed. The cap of the vial is held, and the vial is inverted gently
several times so the sample mixes with the digestion solution.

4. The vial is then put into the COD Reactor for two hours.

5. After two hours, the vial is cooled down to 120 ⁰C before it is removed from
the reactor and put into a tube rack.

6. The control solution and sample solution vials are wiped with a clean cloth
before they are inserted into the reactor.

7. The control solution is inserted first into the spectrophotometer to get the
blank reading, and then the sample solution is inserted into the
spectrophotometer.

8. The COD reading of the sample solution is recorded.

6
3.0 RESULTS AND ANALYSIS

3.1 EXPERIMENTAL RESULTS

Type COD value (mg O2/L)

Distilled Water 0

Sample (Tasik FSSA) 125

Table 1: Data obtained from HACH Spectrophotometer DR6000

3.2 OBSERVATIONS

1. The sample solution is a cloudy transparent liquid with suspensions while the
digestion solution is orangish in color.

2. When the sample is added to the solution, it formed gas bubbles.

3. A light-yellow solution is formed when the mixture of sample and the digestion
solution is shaken.

4. The reaction between the sample and digestion solution released heat as the vial
felt warm, indicating that it was an exothermic reaction.

5. After two hours in the reactor, the mixture turned into a light-yellowish color.

4.0 QUESTIONS

1. Why do BOD and COD values for the same water sample are always
different? Give two reasons.

The BOD (biological oxygen demand) value is the amount of oxygen required, with
the assistance of bacteria, to oxidize the oxidizable organic materials present in 1litre
of water to carbon dioxide and water. This is therefore a measure of the degree of
pollution of the water and is expressed in mg of oxygen /Liters. The BOD value is 4.0
mg/l.

7
The COD value (chemical oxygen demand) indicates how much oxygen, measured in
mg/L is required to oxidize most of the organic material including cellulose in 1litre of
dirty water. The COD value is 125 mg/L.

The value of Chemical Oxygen Demand (COD) is usually higher than the value of
Biochemical Oxygen Demand (BOD) for the same water sample. This is because COD
is the total amount of oxygen consumed by organic and in-organics chemicals in the
water. While, BOD is a measure of the amount of oxygen that require for the
bacteria to degrade the organic components present in water.

The reason that the value of both COD and BOD is always different because more
organic compounds can be chemically oxidized than biologically oxidized. The value
of BOD in polluted water is normally higher than its value in fresh water. Lastly, COD
includes both biodegradable and non- biodegradable substances whereas BOD
contains only bio-degradable. Despite this, measurement of the COD value is often
preferred because the results can be obtained more quickly.

2. What are steps that can be taken to reduce oxygen loss while
conducting the experiment?

There are a few methods can be applied to reduce oxygen loss while conducting the
experiment. Firstly, the samples should be collected in glass bottles. The used of
plastics containers is permissible only if the container known that it does not contain
organic contaminants. Secondly, the samples should be tested as soon as possible so
the actual amount of oxygen in the sample can be tested.

8
5.0 DISCUSSION

In this experiment, we are required to measure the COD of solid and liquid
organic substances in the water sample using the reactor digestion method. Our
water sample is obtained from Tasik FSSA, Universiti Malaysia Sabah which is the
same water sample that we used for BOD and TSS experiment. The COD
experimental value that we obtained from the experiment is 125 mg O2/L. Even
though our value of COD is not that high, it is still higher than the standard A (50mg
O2/L) and standard B (100 mg O2/L) from the Environment Quality Regulation 1979.
This indicates that the water is polluted with organic contaminant like dead leaves,
twig, moss or sand and obviously is not safe to be consumed.

Chemical Oxygen Demand or COD test is a measurement of the oxygen required

to oxidize the soluble and particulate organic matter in water and is widely used to
estimate the amount of organic matters in wastewater. The water sample is
subjected to oxidation by a strong chemical oxidant, in this case, we used potassium
dichromate. This experiment is the standard method for indirect measurement of the
amount of pollution that cannot be oxidized biologically in a sample of water.

In the reactor digestion method test, 2ml volume of the water sample is pipette
into vials along with the digestion solution for COD. Then, the vials are incubated in
the COD reactor and is refluxed for 2 hours and then cooled. Most types of organic
matter are destroyed in this boiling mixture of chromic and sulfuric acid.

Organics + Cr2O72- + H+ CO2 + H2O + 2 Cr2+

After the mixture is cooled, the excess chromium ion will show how much
chromic was used by the organic matters. The COD value of the water sample is
determined using the COD spectrophotometer. The result of COD test will indicate
the amount of water-dissolved oxygen (mg/L) consumed by the contaminants after
two hours of decomposition from the digestion solution. If the amount of pollution in
the test sample is high then the chemical oxygen demand in the water sample is
high.

Chemical Oxygen Demand is an important water quality parameter because it

provides an index to assess the effect of the water to the environment just the same
as BOD. Higher COD level means a greater amount of oxidizable organic material in
the sample which at the same time will reduce the amount of dissolved oxygen in

9
the water. Lack of dissolve oxygen (DO) will lead to anaerobic condition and will
cause harm to the aquatic life.

There are several precaution steps that should be taken when conducting this
experiment. First of all, when mixing the water sample with the digestion reagent,
the vials should be away from face and body as a chemical reaction may occur and
heat will produced from the mixing. The exothermic reaction from the mixing might
also crack the borosilicate glass and cause injury. Besides, a safety shield should be
placed around the COD reactor while heating the sample in order to prevent any
potential hazard from any unlikely event like the vial breakage. Also, the sample
should be disposed as toxic waste after the experiment is carried out because it
might contain something that would clog the drains.

Next, all chemicals must be accurately measured using the measuring cylinder in
order to obtain an accurate results. The meniscus level must be obeyed in order to
prevent any parallax error when taking the readings. Other than that, COD test
should be carried out as soon as the water sample is taken. This is to ensure that the
amount of dissolved oxygen can be measured more accurately. And lastly, COD test
reference of distilled water or known as blank is also carried out together with the
sample. 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.

6.0 CONCLUSION

After conducting this experiment, the COD value for the water sample taken from the
Tasik FSSA in UMS is 125 mg O2/L. This value is much higher than standard A (50 mg O2/L)
and standard B (100 mg O2/L) as described in the Environmental Quality Act 1974
(Environmental Quality – Sewage and Industrial Effluents) using the parameter limits of
effluent of Standard A and B. Thus, it can be concluded that the sample water is polluted
with contaminants due to high COD value. In a nutshell, chemical oxygen demand (COD) in
the sample was able to be determined. Hence, the objective of the experiment is achieved.

10
7.0 REFERENCES

Boyles. W. (1997). The Science of Chemical Oxygen Demand. United State, America:
Technical Information Series.

DR6000™ UV VIS Spectrophotometer with RFID Technology. (n.d.). Retrieved from

[Link]
technology/product?id=10239244800. 28th October 2018.

HACH Company. DR 6000 User Manual. 2nd Edition. (June 2013). Retrieved from
[Link] 27th October
2018.

HACH Company. (2000). COD Reactor Model 45600 & THM Reactor Model 49100
Instrument Manual. Retrieved on 27th October 2018 from,

[Link]

Lab Manual KC31101 Makmal 5 Semester 1 2017/2018. Universiti Malaysia Sabah:

Faculty of Engineering, Chemical Engineering Programme (HK03).

Masulli, D. (10 May 2017). Guide to Chemical Oxygen Demand (COD) Testing.
Retrieved from [Link] 8th October 2018.

Ong, K. H. (1979). Environmental Quality (Sewage and Industrial Effluents)

Regulations, 1979. Retrieved from [Link]
[Link]/resources/discharge- standards/malaysia_sewage-industrial-
[Link]. 30th October 2018.

11
8.0 APPENDICES

Figure 3: Collected water sample from Tasik FSSA stored in a 1.5L bottle.

Figure 4: Pipetting 1mL of water sample.

12
Figure 5: Adding 1ml of sample water in a test tube filled with COD digestion
solution

Figure 6: COD Digestion Solution Extra Information.

13
Figure 7: The sample is put inside the HACH COD Reactor for two hours and
maintained at 150°C.

Figure 8: Results of COD value from HACH Spectrophotometer DR6000.

14