1.

OBJECTIVE
To determine the organic oxidize able matters content of water samples.
2. LEARNING OUTCOME
At the end of the study, the students will be able:
I. To understand the oxidation of oxidize able matter with a known
amount of potassium chromate, the titration of excess chromate,
II.

and the calculation of oxygen used.

To identify the organic oxidize able matter pollutant content in water

III.

samples.
To evaluate the water quality status at the location of water or

IV.

wastewater sampling point.

To choose the appropriate analytical methodology for measuring
COD parameter.

3. THEORY
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 (e.g. lakes and rivers), making COD a useful
measure of water quality. It is expressed in milligrams per litre (mg/L), which indicates the
mass of oxygen consumed per litre of solution. Older references may express the units as
parts per million (ppm). The basis for the COD test is that nearly all organic compounds
can be fully oxidized to carbon dioxide with a strong oxidizing agent under acidic
conditions.
The dichromate reflux method is preferred over procedures using other oxidants because of
superior oxidizing ability, applicability to a wide variety of samples, and ease of
manipulation. Oxidation of most organic compounds is 95-100% the theoretical value.
Most types of organic matter are oxidized by a boiling mixture of chromic and sulfuric
acids. A sample is refluxed in strongly acid solutions with a known excess of potassium
dichromate (K2Cr2O7). After dilution the remaining unreduced K2Cr2O7 is titrated with
ferrous ammonium sulphate to determine the amount of K2Cr2O7 consumed and, oxidize
able organic matter is calculated in terms of oxygen equivalent. Keep ratios of reagent
weights, volumes and strengths constant when sample volumes other than 50 ml are used.
The standard 2 hours reflux time may be reduced if it has been shown that a shorter period
yields the same results. Dichromate does not oxidize ammonia into nitrate, so this

nitrification can be safely ignored in the standard chemical oxygen demand test. The
International Organization for Standardization describes a standard method for measuring
chemical oxygen demand in ISO 6060 [1].
Potassium dichromate is a strong oxidizing agent under acidic conditions. (Acidity is
usually achieved by the addition of sulfuric acid.). In the process of oxidizing the organic
substances found in the water sample, potassium dichromate is reduced (since in all redox
reactions, one reagent is oxidized and the other is reduced), forming Cr3+. The amount of
Cr3+ is determined after oxidization is complete, and is used as an indirect measure of the
organic contents of the water sample.

4. EQUIPMENT
i.

COD Reflux System consisting Erlenmeyer flask (250 mL or 500 mL) with
ground-glass 24/40 neck and 300-mm jacket Liebig West, or equivalent condenser
with 24/40 ground-glass joint, and a hot plate having sufficient power to produce at

ii.
iii.
iv.

least 1.4 W/cm2 of heating surface.

Burette.
Pipette.
COD Vial

4.1 REAGENT
a. Standard potassium dichromate 0.01667M
1000ml distilled water.
4.903g potassium dichromate (K2 CR2 O7) dry 2 hour 150C.
167ml acid sulfuric (H2 SO4).

 3g mercury sulphate (Hg SO4)

b. Acid sulfuric reagent
5.5g silver sulphate (Ag SO4)
1kg acid sulfuric (H2 SO4)
c. Standard ferrous ammonium sulphate
39.2g ammonium iron II sulphate 6-Hydrate {Fe (NH4)2(SO4)2.
6H2O}
20ml acid sulfuric (H2 SO4)
1L distilled water
d. Ferroin indicator

5. PROCDEDURE
1. The sample was taking from the lake in front of FKAAS UTHM.
2. Two COD Vial was taking out and fill the COD Vial with following:
a. COD Vial No. 1: 2.5ml distilled water
b. COD Vial No. 2: 2.5ml sample
3. COD Vial has be close the cap tightly.
4. The COD Vial has be shake up to mixture the sample.
5. Put the COD Vial into the COD reactor and digest at 150oC for 1 hour.
Figure 5.1

6. Take out the COD Vial from the COD reactor, leave to cool at room temperature

7. The solution has be transfer to the conical flask and was added with
3 drops ferroin indicator and the conical flask be stir slowly to
change it colour from yellow to blue greenness.

Figure 5.2
8. The initial reading of burette that be filled with Ferrous Ammonium Sulphate (FAS)
was be recorded.
9. The sample in the conical flask has be titrated with Ferrous
Ammonium Sulphate (FAS) and be stir slowly. Titration discontinued after
colour changed from blue greenness to red-brown.
Figure 5.3

Figure 5.4

10. The final reading of burette that be filled with Ferrous Ammonium Sulphate (FAS)
was be recorded after colour changed from blue greenness to red-brown as in figure
5.1 and 5.2.
11. The Step 3 to 10 has be repeated for COD Vial No.2 (sample).
12. For the FAS Standard Titration Data (molarity) the step start from step 7 to 10 and the
COD Vial doesnt need to be added with any sample or solution.

6. RESULT AND CALCULATION

Table 1: FAS Standard Titration Data:
Reading of burette/pipet
First Reading
Last Reading
Volume of FAS standard (ml)

Cone Flask (Standard)

4.7
6.6
1.9

10
0.100
LRFR

10
0.100
1.9

= 0.53
Table 2: COD test Data Collections:
Normality of FAS

Sample volume

(N)
0.53
0.53

(mL)
2.5
2.5
Total FAS used

readin
g
Initial
Final

CALCULATION:

COD as mg

O2 L =

( AB ) X M X 8000
( ml ) sample

Volume of FAS used

In the original sample, b In the blank sample, s
(mL)
6.6
8.7
2.1

(mL)
4.7
6.6
1.9

( 2.11.9 ) X 0.53 X 8000

2.5

= 339.2 mg/L

7. ANALYSIS
1. Which volume is larger, in the blank sample or in the original sample?
The original sample has more volume than blank sample that for the original
sample is 2.1 ml and for blank sample that is 1.9 ml.
2. How to obtain the normality of FAS equal 0.25N.
Potassium dichromate is usually prepared by the reaction of potassium
chloride on sodium dichromate. Alternatively, it can be obtained from
potassium chromate by roasting chrome ore with potassium hydroxide. It is
soluble in water and in the dissolution process it ionizes:
K2Cr2O7 2 K+ + Cr2O72
Cr2O72 + H2O 2 CrO42 + 2 H+
3. If the original sample has to be diluted, how can you calculate the value of COD?

COD

8000(b s)n
sample..volume

By using the formula:

COD=

8000(2.11.9)(0.1)
2.5

COD = 64 mg/L

8.0 DISCUSSION

1. What is the purpose of using blank sample in this experiment?

The main reason for using the blank sample is to control the volume of
organic material in the sample. COD was carried out to measure the oxygen

demand of organic compounds in a sample of water, and we have to ensure

there were no accidentally outside organic materials added to the sample to
be measured. A blank sample is created by adding the reagents to a volume
of distilled water. Both water and blank sample will be compared. The
oxygen demand for the blank sample is subtracted from the COD for the
original sample to ensure the true measurement of organic matter.
2. What is the objective of COD test and what is the different between COD and
BOD test
The main objective of COD test is to determine the organic oxidize able
matters content of water samples.
Differences between COD and BOD test
COD test

BOD test

COD or Chemical Oxygen Demand is the Biochemical Oxygen Demand is supposed

total measurement of all chemicals in the to measure the amount of food (or organic
water that can be oxidized.
carbons) that bacteria can oxidize.
COD is usually measured and the test is BOD usually takes 5 days.
simple and easy to perform with the right
equipment and can be done in 2 hours.
3. Why the CODs value needs to be monitor for the polluted surface water such as
in lakes and rivers as well as for wastewater.
In environmental, the 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 such as lakes and rivers, making COD a useful measure of
water quality. The amount of organic matter in the lake or river will show
the index of the water quality and we also can categorize whether the lake or
river extremely polluted or not.

4. Give your opinion, if you need to compare the results of COD test to BOD and
permanganate value (test COD by using potassium permanganate, KMnO4) tests.
In my opinion, PV and COD are a measure of the amount of reduced
compounds in a sample, which have been oxidized by a strong oxidizing
agent. Although inorganic substances such as Fe2+, S2- may also be subject
to oxidation, for most natural and industrial waters, the matter to be
oxidized is organic in nature. Therefore these values can be used to
characterize the organic load of a water. For COD determinations, the
organic matter is almost completely oxidized (conversion >90%) due to the
stringent oxidizing conditions (K2Cr2O7 in excess, 2 hours, 150oC, catalyst
Ag). Moreover, the permanganate test is a much milder (KMnO4, 10 min.,
120oC) and only the readily-oxidizable compounds will be converted.
Conversion is only around 30-50% for natural waters with industrial waters
conversions vary even more (10% - 80%).The BOD characterizes the
biological biodegradability and is closely related to the PV, as it describes this
part of the COD that is more readily oxidized. Depending on the type of
water, the BOD5 (biodegradability in 5 days, expressed as ppm O2) from 0.5
up to 3 times the PV (as ppm O2), and for most waters a value of 1.5 can be
applied
5. Why the value of COD increase when the amount of pollutant increased in
surface water.
Because there is contain ammonia in surface water that can be organic
origin, the product of decomposition plant and animal matter, or of
inorganic origin, formed due to chemical or biochemical reduction of nitrate
and nitrite. Ammonia is a very unstable compound and easily undergoes
nitrification. Ammonia is an indicator of pollution originating from soil (the
excessive use of ammonarichnfertelizers) atmosphere and sewage.

6. Explain briefly the steps of COD measurement that you should follow during this
experiment.
2.5mL of sample poured into test tube which contain 1.5mL of potassium
dichromate reagent and labelled as test tube 1.
2.5mL of distilled water poured into test tube which contain 3.5mL acid
sulfuric reagent and labelled as test tube 2.
Both of the test tube mixed up properly and placed in COD Reactor with
temperature 150oC for 1 hour.
After 1 hour, cooling down both of the test tube before pouring into
conical flask. Put the sample into conical flask and conical flask 1 and
conical flask 2 labelled.
Test tube 1 and test tube 2 added with distilled water and shaked two
times and poured into conical flask prepared.
3 drops of ferroin indicator added into each of the conical flask.
Then, both of the solution titrated with K2Cr2O7 with Ferrous
Ammonium Sulfate (FAS) until the colour changed into red brick.
Initial and final reading recorded.
7. Briefly explain whether the value of COD obtain in this experiment are suitable
to be discharged to the stream.
Discharge COD limits can be different with different waste streams (from
specific industries) and COD limit values can be between 100 to 350mg/L
depending on the waste stream. Based on the result obtained, 224mg/L is
suitable to be discharged to the stream.
9.0

CONCLUSION
In conclusion, the objective of the experiment is achieved. The experiment was carried

out to measure and determine the organic oxidizeable matters content of water samples. Based
on the experiment result obtained, the blank sample has the larger volume which is 2.1 mL
compared with original sample which has 1.9 mL of volume. The COD value obtained is
339.2 mg/L. Discharge COD limits are different with different waste streams and COD limit
values can be between 100 to 350mg/L depending on the waste stream. Based on the COD
limits value, 224mg/L is suitable to be discharged to the stream.

10.0 APPENDIX

11.0

Figure 10.1

Figure 10.2

Figure 10.3

Figure 10.4

REFERENCES
Website:

i.

http://www.environmentalleverage.com/BOD%20vs%20COD.htm
Environmental Leverage, 2003.COD and BOD

ii.

http://vlab.amrita.edu/?sub=3&brch=272&sim=1413&cnt=2
vlab.amrita.edu,(2012). Chemical Oxygen Demand of Waste water.

iii.

https://en.wikipedia.org/wiki/Chemical_oxygen_demand