FACULTY OF CIVIL AND ENVIRONMENTAL ENGINEERING

DEPARTMENT OF WATER RESOURCES AND

ENVIRONMENTAL ENGINEERING

ENVIRONMENTAL ENGINEERING LABORATORY

LABORATORY INSTRUCTION SHEETS

SUBJECT CODE BFC3121

EXPERIMENT CODE MA5

CHEMICAL OXYGEN
EXPERIMENT TITTLE
DEMAND
COURSE CODE
 FACULTY OF CIVIL AND ENVIRONMENTAL ENGINEERING

WATER RESOURCE AND ENVIRONMENTAL ENGINEERING

DEPARTMENT

ENVIRONMENTAL ENGINEERING LAB

SHORT REPORT

SUBJECT CODE
CODE & EXPERIMENT
TITLE
COURSE CODE
EXPERIMENT DATE
NAME OF STUDENT
NO. OF GROUP
NAME OF GROUP 1.
2.
MEMBERS
3.
4.
5.
NAME OF LECTURER/
TUTOR/TRAINER
DATE OF SUBMISSION
MARK ATTENDANCE / DISCIPLINE /10%
PARTICIPANT /15%
DATA ANALYSIS /30%
RESULT /25%
DISCUSSION /20%
TOTAL /100%
EXAMINER’S COMMENT APPROVAL RECEIVE

FACULTY: CIVIL AND ENVIRONMENTAL

NO. OF PAGES: 1/7
ENGINEERING
DEPARTMENT: WATER RESOURCE AND
EDITION: MA5
ENVIRONMENTAL ENGINEERING
LAB : ENVIRONMENTAL ENGINEERING REVISION NO: 01
EFFECTIVE DATE: 26.12.2005
TEST: CHEMICAL OXYGEN DEMAND
(COD) AMENDMENT DATE: 20.12.2005
1.0 OBJECTIVES
To measure the effectiveness of waste water sample (usually industrial waste water) through the oxidation
and reduction reaction.

2.0 LEARNING OUTCOMES

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

a. To identify the principle of dichromate method to determine COD.
b. To evaluate the water parameter quality in domestic waste water sample and water supply.
c. To choose the appropriate analytical methodologies water quality measurement.

3.0 THEORY

COD or Chemical Oxygen Demand is the total measurement of all chemicals in the water that can be
oxidized. COD is used as a measurement of pollutants in natural and waste waters to assess the strength of
discharged waste such as sewage and industrial effluent waters. It is normally measured in both municipal
and industrial wastewater treatment plants and gives an indication of the efficiency of the treatment process.
The dichromate reflux method is preferred over procedures using other oxidants because of superior
oxidizing ability, applicability to a with 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 (K 2Cr2O7).  After dilution
the remaining unreduced  K2Cr2O7 is titrated with ferrous ammonium sulphate to determine the amount of 
K2Cr2O7 consumed and oxidizable  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.

PREPARED BY: RADIN MAYA SAPHIRA

SIGNATURE:

DATE: 20.12.2005
FACULTY: CIVIL AND ENVIRONMENTAL
NO. OF PAGES: 2/7
ENGINEERING
DEPARTMENT: WATER RESOURCE AND
EDITION: MA5
ENVIRONMENTAL ENGINEERING
LAB : ENVIRONMENTAL ENGINEERING REVISION NO 01
TEST: CHEMICAL OXYGEN DEMAND EFFECTIVE DATE: 26.12.2005
§ AMENDMENT DATE: 20.12.2005
(COD)
3.1 PRINCIPLE

The stoichiometry organic substances with dichromate is given in Eqn. 1:

CnHaOb + c Cr2O72- 8 c H+ Heat n CO2 + A + 8c + H2O + 2 Cr3+ (Eqn. 1)

Organics Ag2O4 catalysts 2

where: c =2/3 n + a/6 – b/3

Ferrous ion reacts with dichromate ion as in Eqn. 2. The oxidation process ended with dichromate reduction :

6Fe2+ + 14H+ + Cr2O72- 6Fe3+ + 2 Cr3 + 7H2O , Eo = 1.33 volts (Eqn. 2)

Since 1 mole of Cr2O72- equals to 6 equivalent, so 6 x C is similar with the equivalent number as required to
oxidize 1 mole of organic substance.

If oxygen is used as a oxidation agent, the calculation of equivalent numbers are as Eqn. 3 :

O2 + 4e- + 4H+ = 2H2O (Eqn. 3)

Equivalent Weight = 32 g/mole = 8g / equivalent

4 equivalent/ mole

Where else, 6 x C x 8 = g O2 to oxidize 1 mole organic substance.

FACULTY: CIVIL AND ENVIRONMENTAL

NO. OF PAGES: 3/7
INCLUDEPICTU ENGINEERING
DEPARTMENT: WATER RESOURCE AND
RE EDITION: MA5
ENVIRONMENTAL ENGINEERING
"http://www.kuitth LAB : ENVIRONMENTAL ENGINEERING REVISION NO: 01
TEST: CHEMICAL OXYGEN DEMAND EFFECTIVE DATE: 26.12.06
o.edu.my/pbdahari/
logo.jpg" \*
MERGEFORMAT
INET

(COD) AMENDMENT DATE: 20.12.05

4.0 APPARATUS

a. 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/cm 2 of heating surface.
b. Burette
c. Pipette
d. Glass beads
e. Magnetic stirrer bars

4.1 REAGENT

a. Standard potassium dichromate (K2C2O7) solution (0.04167 M) : (Prepare by the technician; Dissolve
12.259 g K2Cr2O7, primary standard grade, previously dried at 150°C for 2 hours in distilled water and
dilute to 1000 mL). Notes: This reagent undergoes a six-electron reduction reaction; the equivalent
concentration is 6 X 0.04167M or 0.2500N.
b. Mercuric sulfate (Hg SO4)
c. Sulfuric acid reagent : (Prepare by the technician : Add Ag2SO4, reagent or technical grade, crystals or
powder, to concentration H2SO4 at the rate of 5.5 g Ag2SO4 /kg H2 SO4. Mix)
     c. Ferroin indicator solution: (Prepare by the technician: Dissolve 1.485 g 1,10-phenanthroline
monohydrate and 695 mg FeSO4·7H2O in distilled water and dilute to 100 mL. This indicator solution
may be purchased already prepared)
d. Standard ferrous ammonium sulfate or FAS (Fe (NH 4)2(SO4)2 solution (0.25 M) titrant : (Prepare by
the technician: Dissolve 98 g Fe(NH4)2(SO4)2·6H2O in distilled water. Add 20 mL of conc H2SO4, cool
and dilute to 1000 mL. Standardize this solution daily against standard K 2Cr2O7 to about 100 mL. Add
30 mL conc H2SO4 and cool). 

INCLUDEPICTU FACULTY: CIVIL AND ENVIRONMENTAL

NO. OF PAGES: 4/7
ENGINEERING
RE
DEPARTMENT: WATER RESOURCE AND
EDITION: MA5
"http://www.kuitth ENVIRONMENTAL ENGINEERING
LAB : ENVIRONMENTAL ENGINEERING REVISION NO: 01
o.edu.my/pbdahari/
TEST: CHEMICAL OXYGEN DEMAND EFFECTIVE DATE: 26.12.2005
 logo.jpg" \*
MERGEFORMAT
INET

(COD) AMENDMENT DATE: 20.12.2005

§
5.0 PROCEDURES:

1. The substances must be added in Erlenmeyer flask following the sequences below:
a. Erlenmeyer flask no. 1 : 10 mL of asid asetic (C2H5COOH) sample
Erlenmeyer flask no. 2 : 10 mL distilled water as a blank
b. Place in beaker 1 and 2 with:
i. 3 glass boiling beads – act as a antibumping
ii. HgSO4– 0.4g
iii. 0.0417M K2Cr2O7 – 10 mL
iv. Acid sulfuric reagent H2SO4 (contain Ag2SO4)- 30 mL
c. Place the beaker at the fume hood. Add H2SO4 slowly. Mixing to avoid possible loss of
volatile materials. Continue swirling and mixing while adding sulfuric acid reagent.
CAUTION : Mix reflux mixture thoroughly before applying heat to prevent local heating of
flask bottom and a possible blowout of flask contents.
2. Attach flask to condenser and turn on cooling water. Cover open end of condenser with a small
beaker to prevent foreign material from entering refluxing mixture and reflux 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 cone flask and dilute the mixture up to 150
mL with distilled water. Add with 3 drops of 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 first sharp colour change to blue-green. Stop
titration, add 3 drops of ferroin indicator. Continue titration until the colour change to reddish brown
that persists 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 in Table 2.
6. Preparation of Standard ferrous ammonium sulfate (FAS) titrant as follows:
a. Dilute 10 mL K2Cr2O7 standard (0.0417 M) to about 100 mL with adding 90 mL distilled water
in the cone flask 250 mL. Swirl and mix slowly.
b. Slowly and carefully add 30 mL 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 the colour change to reddish
brown that persists for 1 minute or longer.
d. Take a precaution that the end point colour changes of titration is fast. Jotted down the
volume of FAS used in titration in Table 1.

FACULTY: CIVIL AND ENVIRONMENTAL

NO. OF PAGES: 5/7
INCLUDEPICTU ENGINEERING
DEPARTMENT: WATER RESOURCE AND
RE EDITION: MA5
ENVIRONMENTAL ENGINEERING
"http://www.kuitth LAB : ENVIRONMENTAL ENGINEERING REVISION NO: 01
EFFECTIVE DATE: 26.12.2005
o.edu.my/pbdahari/
logo.jpg" \*
MERGEFORMAT
INET

TEST: CHEMICAL OXYGEN DEMAND

AMENDMENT DATE: 20.12.2005
(COD)
5.1 FIGURES:
After heating in 2 hours

COOL DOWN

DISTILLED WATER SYNTHETIC SAMPLE

(ACETIC ACID 0.0006M )

Fill the both of the Erlenmeyer cones with distill water up to 150 mL.

Titration Methods :

Jot down the first reading of the burret

in the appropriate table.
Add 3 drops of ferroin indicator
AMMONIA Titrate FAS until the first colour appear.
FERUM Stop titration, add 3 drops of ferroin
SULFAT indicator again
Continue titration until the colour
change to reddish brown. Stop titration
and jot down the last reading in the
table.
SAMPLE

FACULTY: CIVIL AND ENVIRONMENTAL

NO. OF PAGES: 6/7
INCLUDEPICTU ENGINEERING
DEPARTMENT: WATER RESOURCE AND
RE EDITION: MA5
ENVIRONMENTAL ENGINEERING
"http://www.kuitth LAB : ENVIRONMENTAL ENGINEERING REVISION NO: 01
TEST: CHEMICAL OXYGEN DEMAND EFFECTIVE DATE: 26.12.2005
o.edu.my/pbdahari/
logo.jpg" \*
MERGEFORMAT
INET

(COD) AMENDMENT DATE: 20.12.2005

6.0 DATA AND CALCULATION

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 standard using formula given :

Volume 0.04167M K2Cr2O7

                                                            solution titrated, mL          
Normality of FAS solution     =                                                            X 0.25
                                                      Volume FAS used in titration, mL

Notes : The 0.25 is the Standard potassium dichromate solution, 0.04167M K2Cr2O7 undergoes a six-electron
reduction reaction; the equivalent concentration is 6 X 0.04167M or 0.2500N.

Table 2 : Sample and Blank Titration Data :

Reading of buret / pipet (B ) Cone flask 1 (Sample) (A) Cone flask 2 (Blank)
First Reading
Last Reading
Volume of FAS standard (mL)

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

 
                                                   ( B – A) X NFAS X 8000
                     COD as mg O2/L =                                
                                                            mL sample
 
where:
 
      A = mL FAS used for blank,
      B = mL FAS used for sample,
     NFAS = Normality of FAS, and
8000 = milliequivalent weight of oxygen X 1000 mL/L.

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

FACULTY: CIVIL AND ENVIRONMENTAL

NO. OF PAGES: 7/7
INCLUDEPICT ENGINEERING
DEPARTMENT: WATER RESOURCE AND
URE EDITION: MA5
ENVIRONMENTAL ENGINEERING
"http://www.kuitt LAB : ENVIRONMENTAL ENGINEERING REVISION NO: 01
TEST: CHEMICAL OXYGEN DEMAND EFFECTIVE DATE: 26.12.2005
ho.edu.my/pbdah
ari/logo.jpg" \*
MERGEFORMA
TINET

(COD) AMENDMENT DATE: 20.12.2005

7.0 QUESTIONS

7.1 What is the purpose of using blank in this experiment.

7.2 Name the oxidation and reduction agent used in COD test.

7.3 Give the chemical formula of the following :

a. Sulfuric acid
b. Ferrous Ammonium Sulfate
c. Pottasium dichromate
d. Argentum sulfate
e. Mercuric sulfate

7.4 Calculate the molecular mass of the following:

f. Sulfuric acid
g. Ferrous Ammonium Sulfate
h. Pottasium dichromate
i. Argentum sulfate
j. Mercuric sulfate

7.5 Explain the precaution that must be taken during COD test?