1.

OBJECTIVES

a) To determine the chemical oxygen demand (COD) in water/wastewater

sample.
b) To compare the laboratory result between influent and effluent of
water/wastewater sample.
3.0

INTRODUCTION

The chemical oxygen demand (COD) determines the amount of oxygen

required for chemical oxidation of organic matter using a strong chemical
oxidant, such as, potassium dichromate under reflux conditions. This test is
widely used to determine:
a) Degree of pollution in water bodies and their self-purification capacity,
b) Efficiency of treatment plants,
c) Pollution loads, and
d) Provides rough idea of Biochemical oxygen demand (BOD) which can be
used to determine

sample volume for BOD estimation.

The limitation of the test lies in its inability to differentiate between the
biologically oxidizable and biologically inert material and to find out the
system rate constant of aerobic biological stabilization. Most of the organic
matters are-destroyed when boiled with a mixture of potassium dichromate
and sulphuric acid producing carbon dioxide and water. A sample is refluxed
with a known amount of potassium dichromate in sulphuric acid medium and
the excess of dichromate is titrated against ferrous ammonium sulphate. The
amount of dichromate consumed is proportional to the oxygen required to
oxidize the oxidizable organic matter.

4.0
i.
ii.
iii.
iv.
v.
vi.
vii.
viii.
ix.
x.
xi.
xii.
xiii.
xiv.
xv.

INSTRUMENT/ APPARATUS/ CHEMICAL/ REAGENTS

Potassium dichromate ( K2Cr2O7)
Sulphuric acid (H2SO4)
Ferrous ammonium sulphate (FAS), Fe(NH4)2(SO4)2
Ferroin indicator solution
Digestion vessel
Block heater to operate 150 + 22C with holes to accommodate digestion
vessels
Pipettes (10,25 and 50 mL)
Burette (50 mL), burette stand and clamp
Analytical balance
Spatula
Volumetric flask
Magnetic stirrer and stirring bars
Measuring cylinder
Beakers
Conical flask

5.0

PROCEDURE

5.1

Closed Reflux, Titrimetric Method

5.1.1 Standardization of FAS solution : The ferrous ammonium sulphate

(FAS) solution must be standardized by the following procedure:
i.

The clean burette was prepared. The clean burette was rinsed

ii.

with FAS three times prior to fill it in with FAS.

1.5 mL of digestion reagent was dispensed into a 100 mL conical

iii.
iv.

flask, 15 mL of distilled water was added and mix.

3.5 mL of catalyst was added very slowly to the mixture.
3 drops of ferroin indicator was added and titrated with FAS until
the solution turns red. Changes in colour will be observed as
follows :
yellow-> green -> blue -> red.

v.

The initial and final reading of FAS was recorded.

5.1.2 Digestion
i.

The digestion block was turned on after being checked that was

ii.

cleared from chemical contamination.

The digestion tubes was ensured to be used was completely

iii.

intact, with no cracks or chips.

1.5 mL of digestion solution was placed into a digestion tube by

iv.
v.

autodispenser.
2.5 mL of sample was added by using a pipette.
3.5 Ml of catalyst solution was added very slowly using
autodispenser, so that it formed a layer at the bottom of the

vi.

tube.
Steps 3 to 5 was repeated for all samples in duplicate and 1

vii.

blanks (distilled water in the place of sample).

The tube cap was checked to ensure the PTFE inserted was
present, and capped the tube very tightly. The tube was hold by
the cap from this point onwards.

viii.
ix.

Contents was mixed by shaking from side to side (do not invert).
All tubes was placed in the digestion block, covered with perspex

x.

cover. Digested for two hours.

The tubes was removed from the block and was allowed to
cooled to room temperature before being titrated.

5.1.3 Titration
i.

The contents of a digestion tube was poured into a clean 100 Ml

conical flask. The tube was rinsed into the flask twice with

ii.

distilled water to ensured all the contents was transferred.

3 drops of ferroin indicator was added and titrated with FAS until

iii.

the colour changes to red.

Titre (FAS) for blanks = A mL and the titre for the samples = B
mL. The initial and final reading for FAS was recorded.

5.2

Closed Reflux, Colorimetric Method

5.2.1 Digestion
i.
ii.

The COD reactor was turned on. Preheated to 1502C.

The caps of COD digestion reagent was removed vials for the

iii.

appropriate range.
The vial was hold at a 452 angle. 2.0 mL (for low range) and 0.2

iv.

mL (for high range) of sample was pipette into the vials.

The vials was capped tightly. The outside of COD vial was rinsed
with deionised water and the vial was wiped cleaned with paper

v.

towel.
The vial was hold by the cap and over a sink. Inverted gently
several times to mix the contents. The vial was placed in the

vi.

preheated COD reactor.

A blank was prepared by repeating steps 2 to 5, substituting 2.0
mL (for low range) and 0.2 mL (for high range) deionised water

vii.

for the sample. The vials was heated for 2 hours.

The reactor was turned off. Wait about 20 minutes for the vials to
cool to 1202C or less.

viii.

Each vials was placed into a rack and was cooled to room
temperature.

5.2.2 Calorimetric determination

i.

Based

on

Hach

method

8000,

used

on

Hach

DR6000

ii.
iii.

spectrophotometer.
Select programme: 430 COD LR or 435 COD HR. Touch start.
Clean the outside of the vial with a wipe tissue to remove fingerprints

iv.
v.
vi.

or other marks.
Place the blank into the cell holder.
Touch zero. The display will show: 0 mg/L COD.
When the timer beeps, place the sample vial into the sample cell
holder. Results will appear in mg/L COD and the results was recorded.

SUGGESTION AND RECOMMENDATION

From the experiment, there are several suggestion and recommendation that
can improved our results and data analysis. Firstly, we must collect or store
the samples carefully. The failure to store samples correctly, or to have them
analysed as soon as possible may lead to erroneous results being
determined. Samples should be stored in suitable containers. Changes can
be inhibited by refrigerating the sample at a temperature between 2 - 5 2C, or
by reducing the pH to a value between 1 - 2 with sulphuric acid. The time for
which preservation is effective should be established for each type of
sample, as this may vary from a few hours to several days.
In the other hand, poisonous gases may be evolved from samples
which are acidified with sulphuric acid. The acidification of samples
containing, for example, cyanide or sulphide should always be carried out in
a fume cupboard. In addition, dangers of spillage arise if the sample contains
carbonate. Acidification should, therefore, be conducted in a fume cupboard.
Addition of concentrated sulphuric acid to water should always be carried out
with care and with 10 gentle swirling of the contents of the flask. The
methods described involve the handling of boiling, concentrated solutions of
sulphuric acid and potassium dichromate. Protective equipment is essential.
In the event of spillage, immediate rinsing with copious amounts of clean
water is generally the most effective remedy. Adsorbents are also available
which facilitate removal of the bulk of the spillage. Inhalation and ingestion
of dichromate dust should be avoided. Care is required when preparing and
handling concentrated solutions containing silver or dichromate as these
salts are toxic.

Last but not least, in closed-tube methods, the tubes are under
pressure during and immediately after the heating stage. Care should,
therefore, be exercised when handling, sealing or unseating tubes, the
opening of which should always be directed away from staff. The closure,
heating, removal from the heating block, and subsequent opening of closed
tubes after cooling should be carried out behind a protective screen in a well
ventilated hood. Care should be taken when opening the tubes so that any
build-up of pressure is released gently and in a controlled manner