FACULTY : CIVIL & ENVIRONMENTAL ENG.

EDITION:
DEPART : WATER & ENVIRONMENTAL
REVISION NO: 02
ENG.
EFFECTIVE 28/12/2015
LAB : ENVIRONMENTAL ENGINEERING
DATE:
EXPERIMENT : CHEMICAL OXYGEN AMENDMENT
DEMAND (COD) DATE:
1.0 OBJECTIVES
To determine the organic oxidizeable matters content of water samples.
2.0 LEARNING OUTCOMES

At the end of the study, the students will be able:

a. To understand the oxidation of oxidizeable matter with a known amount of potassium chromate,
the titration of excess chromate, and the calculation of oxygen used.
b. To identify the organic oxidizeable matter pollutant content in water samples.
c. To evaluate the water quality status at the location of water or wastewater sampling point.
d. To choose the appropriate analytical methodology for measuring COD parameter.

3.0 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 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 liter (mg/L), which in indicates the mass of oxygen consumed per liter of solution.
Older references mat 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 oxidiziing 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 (K2Or2O7). After dilution the remaining
unreduced K2Or2O7 consumed and oxidizable organic matter is calculated in terms of oxygen
equivalent. Keep ratios reagent weights, volumes and strengths constant when sample volumes other
than 50ml are used. The standard 2hours 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 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+ determined after oxidization is complete, and is
used as an indirect measure of the organic contents of the water sample.

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 FACULTY : CIVIL & ENVIRONMENTAL ENG. EDITION:
DEPART : WATER & ENVIRONMENTAL
REVISION NO: 02
ENG.
EFFECTIVE 28/12/2015
LAB : ENVIRONMENTAL ENGINEERING
DATE:
EXPERIMENT : CHEMICAL OXYGEN AMENDMENT
DEMAND (COD) DATE:

4.0 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 least 1.4 W/cm2 of heating surface.
ii. Burette
iii. Pipette
iv. COD Vial

4.1 REAGENT

1. Standard potassium dichromate 0.01667M

1000ml distilled water
4.903g potassium dichromate (K2 CR2 O7) dry 2 hour 150C
167ml acid sulfuric (H2 SO4)
33.3g mercury sulfate (Hg SO4)

2. Acid sulfuric reagen

5.5g silver sulfate (Ag SO4)
1kg acid sulfuric (H2 SO4)

3. Standard ferrous ammonium sulfate

39.2g ammonium iron II sulfate 6-Hydrate {Fe(NH4)2(SO4)2. 6H2O}
20ml acid sulfuric (H2 SO4)
1L distilled water
4. Ferroin indicator

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 FACULTY : CIVIL & ENVIRONMENTAL
EDITION:
ENG.
DEPART : WATER & ENVIRONMENTAL
REVISION NO: 02
ENG.
EFFECTIVE
LAB : ENVIRONMENTAL ENGINEERING 28/12/2015
DATE:
EXPERIMENT : CHEMICAL OXYGEN AMENDMENT
DEMAND (COD) DATE:

5.0 PROCEDURES:
5.1 STANDARD METHOD 5220 C
5.2 SAMPLING PRODURE
i. Collect the samples in glass bottles, if possible. Use of plastic containers is permissible
if it is known that no organic contaminants are present in the containers.
ii. Biologically active samples should be tested as soon as possible. Samples containing
settleable material should be well mixed, preferably homogenized, to permit removal
of representative aliquots.
iii. Samples should be preserved with sulfuric acid to pH<2 and maintained at 4C until
analysis.
5.3 LABORATORY PROCEDURES:
1) The substances must be added in COD Vial following the sequences below:
a. Place in COD Vial 1 and 2 with:
i. 1.5ml Potassium Dichromate Reagent
ii. 3.5ml Acid Sulfuric Reagent
NOTE : Mixture reflux thoroughly before applying heat to prevent local heating
of flask bottom and possible blowout of flask contents
b. COD Vial No. 1 : 2.5ml sample
COD Vial No. 2 : 2.5ml distilled water
2) Entering the refluxing mixture at COD Reactor with temperature 150 for 2 hours. At a
meantime, please proceed to Procedure no. 6.
3) After 2 hours, cool wash down the condenser with distilled water. Continue cooling the
condenser to room temperature.
4) Disconnect reflux condenser. Transfer the solution to the conical flask and dilute the
mixture up 150ml with distilled water. Add with 3 drops ferroin indicator. Place the
magnetic bars and stir it with magnetic stirrer.
5) Titrate K2Cr2O7 with Ferrous Ammonium Sulfate (FAS). First and last reading should be jot
down in Table 2. Take as the end point of the titration the sharp colour to blue-green.
Stop titration, add 3 drops of Ferroin Indicator. Continue titration until the colour change
to reddish brown that persist for 1 minute or longer. Stop titration and jot down the last
reading in Table 2. Take a precaution that the end point colour changes of titration is
fast. Calculate the volume of FAS used in titration Table 2.

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 FACULTY : CIVIL & ENVIRONMENTAL
EDITION:
ENG.
DEPART : WATER & ENVIRONMENTAL
REVISION NO: 02
ENG.
EFFECTIVE
LAB : ENVIRONMENTAL ENGINEERING 28/12/2015
DATE:
EXPERIMENT : CHEMICAL OXYGEN AMENDMENT
DEMAND (COD) DATE:

6) Preparation of Standard Ferrous Ammonium Sulfate (FAS) titrant as below:

a. Dilute 5ml Potassium Dichromate K2Cr2O7 standard (0.01667M) with 10ml distilled
water in the conical flask 250ml. swirl and mix slowly.
b. Slowly and carefully add 30ml conc H2SO4 and cool. Refer to Figure 1, titrate with
the FAS titrant using 3 drops of ferroin indicator. First and last Reading should be jot
down in Table 1.
c. Take as the end point of the titration the first sharp colour change to blue-green.
Stop titration, add 3 drops of ferroin indicator. Continue titration until color change
to reddish brown that persists for 1 minut or longer.
d. Take precaution that the end point colour changes of titration is fast. Jotted down
the colume of FAS used in titration Table 1.

6.0 DATA AND CALCULATION RESULTS

Table 1 : FAS Standard Titration Data:

Reading of buret/pipet Cone Flask (Standard)
First Reading
Last Reading
Volume of FAS standard (ml)

6.1 Compute the molarity for the FAS standards using formula given:

0.01667 2 2 7 ,
= 0.100
,

Note : The 0.1 is the Standard Potassium Dichromate solution, 0.01667M K2Cr2O7 undergoes a six-
electron reduction; the equivalent concentration is 6 X 0.01667M or 0.100N

Table 2 : COD test Data Collections:

Normality of FAS Sample volume Volume of FAS used
(N) (mL) in the original sample, b in the blank sample, s
(mL) (mL)

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 FACULTY : CIVIL & ENVIRONMENTAL ENG. EDITION:
DEPART : WATER & ENVIRONMENTAL
REVISION NO: 02
ENG.
EFFECTIVE
LAB : ENVIRONMENTAL ENGINEERING 28/12/2015
DATE:
EXPERIMENT : CHEMICAL OXYGEN AMENDMENT
DEMAND (COD) DATE:

6.2 Compute the COD concentration in mg/L for the samples using formula given:

2 ( ) 8000
= ()
Where:
A = mL FAS used for blank
B = mL FAS used for sample
M = Molarity of FAS
8000 = miliequivalent weight of oxygen X 1000ml/L

Note: The 8000 multiplier is to express the results in units of miligrams per liter of oxygen since 1 liter
contains 1000ml and the equivalent weight of oxygen is 6.

8.0 DATA ANALYSIS

(1) Which volume is larger, in the blank sample or in the original sample.
(2) How to obtain the normality of FAS equal 0.25N.
(3) If the original sample has to be diluted, how can you calculate the value of COD.

9.0 DISCUSSION

(1) What is the purpose of using blank sample in this experiment

(2) What is the objective of COD test and what is the different between COD and BOD test
(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.
(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.
(5) Why the value of COD increase when the amount of pollutant increased in surface water.
(6) Explain briefly the steps of COD measurement that you should follow during this experiment.
(7) Briefly explain whether the value of COD obtain in this experiment are suitable to be
discharged to the stream.

PREPARED BY : SIGNATURE :

POSITION :
DATE :

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