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FACULTY : ENGINEERING

EDITION:
TECHNOLOGY
LABORATORY: CIVIL 2
REVISION NO:
ENGINEERING TECHNOLOGY
FEB
EXPERIMENT: CHEMICAL EFFECTIVE DATE:
2015
OXYGEN DEMAND (COD)
AMENDMENT DATE:

FACULTY OF ENGINEERING TECHNOLOGY


DEPARTMENT OF CIVIL ENGINEERING TECHNOLOGY

ENVIRONMENTAL ENGINEERING TECHNOLOGY


LABORATORY

LABORATORY INSTRUCTION SHEETS

COURSE CODE BNP 20503


EXPERIMENT CODE EXPERIMENT 3

EXPERIMENT TITLE CHEMICAL OXYGEN DEMAND (COD)


DATE Aas 15/3/2015
GROUP NO. 2 1
LECTURER/INSTRUCTOR/TUTO 1) Miss Nadzirah Binti Zayadi
R 2) Miss Izzati Izwanni Binti Ibrahim
DATE OF REPORT SUBMISSION
ATTENDANCE/PARTICIPATION/DISIPLINE: /5%
INTRODUCTION: /5%
PROCEDURE: /5%
RESULTS & CALCULATIONS /15%
ANALYSIS /15%
DISTRIBUTION OF MARKS FOR DISCUSSIONS: /20%
LABORATORY REPORT ADDITIONAL QUESTIONS /15%
CONCLUSION /10%
SUGGESTIONS & RECOMENDATIONS /5%
REFERENCES: /5%
TOTAL: /100%

EXAMINER COMMENTS: RECEIVED DATE AND STAMP:

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FACULTY : ENGINEERING
EDITION:
TECHNOLOGY
LABORATORY: CIVIL 2
REVISION NO:
ENGINEERING TECHNOLOGY
FEB
EXPERIMENT: CHEMICAL EFFECTIVE DATE:
2015
OXYGEN DEMAND (COD)
AMENDMENT DATE:

STUDENT CODE OF ETHICS

DEPARTMENT OF CIVIL ENGINEERING TECHNOLOGY

FACULTY OF ENGINEERING TECHNOLOGY

I hereby declare that I have prepared this report with my own efforts. I also admit to

not accept or provide any assistance in preparing this report and anything that is

in it is true.

1) Group Leader __________________________________________(Signature)


Name : __________________________________
Matrix No. : __________________________________

2) Group Member 1 __________________________________________(Signature)


Name : __________________________________
Matrix No : ___________________________________

3) Group Member 2 __________________________________________(Signature)


Name : __________________________________
Matrix No. : __________________________________ 2

4) Group Member 3 __________________________________________(Signature)


Name : __________________________________
FACULTY : ENGINEERING
EDITION:
TECHNOLOGY
LABORATORY: CIVIL 2
REVISION NO:
ENGINEERING TECHNOLOGY
FEB
EXPERIMENT: CHEMICAL EFFECTIVE DATE:
2015
OXYGEN DEMAND (COD)
AMENDMENT DATE:

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1.0 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.

2.0LEARNING OUTCOMES
At the end of this course students are able to:
a) Understand the concept of chemical oxygen demand in a given

water/wastewater sample.
b) Identify the principle of dichromate reflux and reactor digestion methods to

determine COD.
c) Evaluate the water parameter quality in domestic wastewater sample and

water supply.
d) Identify problems and use their generic skill to solve problems.
e) Develop their ability to work in group.

3.0INTRODUCTION
The principle of this experiment is to completely oxidize the organic

matter present in sample by potassium dichromate (K 2Cr2O7) in the

sulphuric acid (H2SO4) medium and the excess K2Cr2O7 is determined by

titration against ferrous ammonium sulphate, using ferroin indicator. The

dichromate consumed by the sample is equivalent to the amount to the

amount of O2 required to oxidize the organic matter.


Chemical oxygen demand (COD) test is used widely to measure the

pollution strength of domestic and industrial wastewaters. It said to

measure the capacity of water to consume oxygen during the

decomposition of organic matter and the oxidation of inorganic chemicals

such as ammonia and nitrite. The dichromate reflux method is preferred

over procedures using other oxidants (e.g. potassium permanganate)

because of its superior oxidizing ability, applicability to a wide variety of

samples and ease of manipulation. Oxidation of most organic compounds

is 95 100% of the theoretical value.

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4.0INSTRUMENTS /APPARATUS / CHEMICAL / REAGENTS
4.1 Chemicals / Reagents
4.4. Closed Reflux, Titrimetric Method (Prepared by Technician)
Caution: In carrying out the following procedures, use proper safety

measures, including protective clothing, eye protection and a fume

hood. Reagents containing heavy metals (HgSO4 and Ag2SO4) should

be disposed of as toxic wastes.

(a) Potassium dichromate (K2Cr2O7), (COD digestion reagent):


(i) 10.216 g of oven-dried (primary standard grade, previously

dried at 103oC potassium dichromate (K2Cr2O7) is weighed

out into a 1 litre beaker.


(ii) 30g of mercuric sulphate is weighed out into a 250 ml

beaker.
(iii) A tray of ice is placed on a magnetic stirrer in the fume

cupboard.
(iv) Both beakers are transferred to the fume cupboard; the 1

litre beaker is put into the ice tray and a stirrer bar is

added.
(v) Approx. 500ml of distilled water is added to the 1 litre

beaker. Begin stirring and the mercuric sulphate is

gradually added and the 250 ml beaker is rinsed into the

other with distilled water.


(vi) A clean, dry measuring cylinder is used to measure out 167

ml of concentrated sulphuric acid (Use a 500 ml bottle and

wipe before and after use).


(vii) The acid is added to the mixture about 10 ml at a time,

stirring continuously.
(viii) The mixture is allowed to cool to room temperature, and

then remove the stirrer bar.


(ix) Using a funnel, the mixture is poured into a 1 litre

volumetric flask, rinsing the beaker into the flask until all

residues are removed.


(x) Make up to 1 litre with distilled water. Top securely and

invert to mix.

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(xi) The contents of the flask are transferred into the correct

COD reagent dispenser.

(b) Sulphuric acid (H2SO4) / silver sulphate (Ag2SO4) solution (COD

catalyst reagent):
(i) 22. 5 g of silver sulphate is weighed out into a 250 ml

beaker.
(ii) A full 2.5 L bottle of concentrated sulphuric acid is

collected from the acid cupboard.


(iii) The top is carefully removed from the acid bottle and a

powder funnel is inserted.


(iv) The silver sulphate is tipped into the funnel, the funnel is

tapped to release the powder sticking to it. DO NOT ADD

WATER. When removing the funnel ensure that it is free

from acid.
(v) Any remaining silver sulphate in the beaker or on the

funnel should be washed down the sink with plenty of cold

water.
(vi) The solution is left in a safe cupboard for 24 hours, and

mixed thoroughly before use.

(c) Ferrous ammonium sulphate (FAS), Fe(NH4)2(SO4)2,


(i) Into the 600 ml beaker, 9.8 g of Ferrous Ammonium

Sulphate (FAS) is weighed out.


(ii) Approx. 300 ml of distilled water is added and stirred with a

glass rod.
(iii) 25 ml of conc. sulphuric acid is measured out using the

measuring cylinder.
(iv) The acid is poured into the beaker very slowly, whilst

stirring.
(v) Ensure that all the FAS has dissolved.
(vi) The beaker is allowed to reach room temperature
(vii) The solution is poured into a 1 litre volumetric flask via a

funnel and the beaker is rinsed into it. Make up to 1 litre

with distilled water.

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Note: The deterioration of FAS can be decreased if it is stored in a dark
bottle.

(d) Ferroin indicator solution: 1.485 g of 1, 10-phenanthroline

monohydrate (C12H8N2.H2O) and 0.695 g of ferrous ammonium

sulphate hepahydrate are dissolved in distilled water and dilute to

approximately 100 mL.

4.1.2 Closed Reflux, Colorimetric Method

i) COD digestion reagent vials with all premixed reagents included (e.g.

Hach COD digestion vial low range and COD digestion vial high

range)

4.2. Apparatus /Instruments


4.2.1 Closed Reflux, Titrimetric Method
i) Digestion vessels: {refereably use borosilicate culture tubes (at

least 16mm x 100 mm) with TFE-lined screw caps.


ii) Block heater to operate 150 2C with holes to accommodate

digestion vessels
iii) Pipettes (10, 25 and 50 mL)
iv) Burette (50 mL), burette stand and clamp
v) Analytical balance
vi) Spatula
vii) Volumetric flask
viii) Magnetic stirrer and stirring bars
ix) Measuring cylinder
x) Beakers
xi) Conical flask

4.2.2. Digestion vessels with premixed reagents method


i) Block heater to operate 150 2C with holes to accommodate

digestion vessels.
ii) Spectrophotometer (DR 6000)
iii) COD digestion reagent vials
iv) Test tube rack
v) Wipe tissue

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5 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 is prepared. The clean burette is rinsed with
FAS three (3) times) prior to fill it in with FAS.
(ii). 5 ml of digestion reagent is dispensed into a beaker and

then 10ml of distilled water is added and mixed.


(iii). To the mixture carefully and very slowly add 3.5 ml of

catalyst.
(iv). 2 drops of ferroin indicator is added and titrated with FAS

until the solution turns red. Colour change will be observed as

follows: yellow -> green -> blue -> red.

(v). The initial and the final reading of FAS (titre) is recorded and

used in Table 6.1.

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5.1.2. Digestion
(i) The digestion block is turned on after checking that it is clear

from chemical contamination.


(ii) The digestion tubes to be used are ensured that completely

intact, with no cracks or chips.


(iii) Using the autodispenser, 1.5 ml of digestion solution is placed

into a digestion tube.


(iv) Add 2.5 ml of sample using a pipette.
(v) Using the autodispenser, 3.5 ml of catalyst solution is added

very slowly, so that it forms a layer at the bottom of the tube.

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(AT THIS POINT THE TUBE CONTENTS WILL UNDERGO

RAPID TEMPERATURE INCREASE).


(vi) Steps 3 to 5 are repeated for all samples in duplicate and 1

blanks (distilled water in the place of sample).


(vii) The tube cap is checked to ensure the PTFE insert is present,

and the tube is capped very tightly. Hold the tube by the cap

from this point onwards.


(viii) Contents are mixed by shaking from side to side (do not invert).
(ix) All tubes are placed in the digestion block, cover with perspex

cover and digested for two hours.


(x) The tubes are removed from the block and allow them to cool to

room temperature before titrating.

5.1.3 Titration
(i) The contents of a digestion tube are poured into a clean 100 ml

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

distilled water to ensure all the contents are transferred.


(ii) Two (2) drops of ferroin indicator is added and titrate with FAS

until the colour changes to red.


(iii) Let the titre (FAS) for blanks = A ml and the titre for the

samples = B ml. The initial and the final reading of FAS are

recorded in Table 6.2 and 6.3.

5.2 Closed Reflux, Colorimetric Method

5.2.1 Digestion

(i) The COD reactor is turned on and preheated to 150oC.


(ii) The caps of COD digestion reagent vials are removed for the

appropriate range.
(iii) The vial is held at a 45o angle. Pipette 2.0 mL (for low range)

and 0.2 mL (for high range) of sample into the vials.


(iv) The vials are capped tightly. The outside of COD vial is rinsed

with deionised water and the vial is wiped clean with paper

towel.

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(v) The vial is held by the cap and over a sink and inverted gently
several times to mix the contents. The vial is placed in the

preheated COD reactor.


(vi) A blank is prepared by repeating steps (b) to (e), substituting

2.0 mL (for low range) and 0.2 mL (for high range) deionised

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


Note: One blank must run with each set of samples.
(vii) The reactor is turned off. Wait about 20 minutes for the

vials to cool to 120oC or less.


(viii) Each vial is inverted several times still warm. The vials

are placed into a rack and cool to room temperature.


(ix) Proceed to the colorimetric determination to measure the COD.
Note: For greater accuracy, analyse a minimum of three replicates and

average the results.

COD reactor

5.2.2 Colorimetric determination

(i) Procedure is based on Hach method 8000, used on Hach

DR6000 spectrophotometer.
(ii) Select programme: 430 COD LR or 435 COD HR. Touch start.
(iii) Clean the outside of the vial with a wipe tissue to remove

fingerprints or other marks.


(iv) The blank is placed into the cell holder.
(v) Touch Zero. The display will show: 0 mg/L COD.
(vi) When the timer beeps, The sample vial is placed into the

sample cell holder. Results will appear in mg/L COD and record

the result in Table 6.4.

6 RESULTS CALCULATIONS
6.1 Results

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Table 6.1: FAS standard titration (Closed Reflux, Titration method)

Volume of FAS reading, Volume of


Volume of
mL FAS
K2Cr2O7 used,
required
mL Initial Final
(T), mL
Table 6.2: 5.0 7.2 15.0 7.8 Volume of
FAS required
for blank (Closed Reflux, Titration method)

Volume of Volume of FAS reading, mL


Volume FAS
sample used,
Initial Final required (A), mL
mL
2.5 15.0 23.8 8.8

Table 6.3: Volume of FAS required for Sample (Closed Reflux, Titration
method)

Type of Sample:

Volume of Volume of FAS reading, mL


Volume FAS
sample used,
First Last required (B), mL
mL
2.5 23.8 31.5 7.7

Table 6.4: COD concentration of samples (Reactor Digestion method)

COD for low range, mg/L

Blank Sample 1
0.0 122.0

6.2 Calculations

COD, mg/L = (A-B) x D x 1,000

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Where: A = volume of FAS used for blank, mL

B = volume of FAS used for sample, mL

T = Volume of titre (FAS) to be used in FAS standardization

D = Dilution factor for sample (if the sample needed to be

diluted)

COD, mg/L = (8.8-7.7) x 1 x 1000

7.8

= 141 mg/L

7 ANALYSIS

From the result, the volume of FAS required for FAS standardization

(T) and the volume of FAS used for blank (A) and sample (B) in closed reflux,

titration method are used to calculate the COD value of the sample in mg/L.

The burette readings are taken as final reading of table 6.1, 6.2 and 6.3 when

the colour of the contents changed from yellow to red. The value of A, B and T

is calculated by using the final reading minus the initial reading of the

burette reading. The value of COD is calculated by using the formula given

and it is 141 mg/L. The result obtained from the closed reflux, colorimetric

method by Hach DR6000 spectrophotometer is 122 mg/L.

8 DISCUSSIONS

The COD test is used widely to estimate the amount of organic matter

in wastewater. It is a measurement of the oxygen equivalent of the materials

present in the wastewater that are subject to oxidation by a strong chemical

oxidant (in this case, dichromate). When wastewater contains only readily

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available organic bacterial food and no toxic matter, the COD test results

provide a good estimate of Biochemical Oxygen Demand (BOD) values.

The procedure of colorimetric method is greatly simplified over the

titrimetric method. Besides, the colorimetric method is using

spectrophotometer to determine the COD value and it will more accurate

than titrimetric method. For colorimetric method, the chromium (III) ion in

the specimen is measured by spectrophotometer after the mixture has been

cooled. The excess chromium (III) ion shows how much chromic was use by

organics matter. 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.

There are few results obtained from the experiment because the vials

stuck in the COD reactor that caused by unclean of vials surface. The result

of the titrimetric method and colorimetric method are different with the value

of 122 mg/L and 141mg/L. This difference may happen when titrate the

sample with FAS solution until it changes to red colour. In addition, it will be

a large difference in the result although the reading obtained from titration

has a difference about 0.1ml. The value of COD got from this experiment was

122mg/L and 141mg/L and under low range of COD (<150mg/L). Based on

Department of Environment, Ministry of Natural Resources and

Environment, the COD values above the 100mg/L are class V and useless for

any activities such as irrigation, fishery and water supply by referring

Interim National Water Quality Standard (INWQS).

9 ADVANCED QUESTIONS
1. What will happen to the COD value if HgSO4 is not added?
Chlorine will not be separated out of the sample effluent and the value of

COD will be higher than it should be.

2. What was the purpose of the blank sample?

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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.

3. Why is it important to determine COD test in wastewater treatment?


It is used to measure or determine the amount of organic pollutants found

in surface water such as lakes or wastewater, and make COD a useful

measure of water quality.

4. Summarize the method and write the chemical reactions involved and

interpret your test results (Closed Reflux, Titration Method).


Sample is refluxed with known amount of excess dichromate in presence of

sulphuric acid. Catalyst is used to bind or complex chlorides. The

remaining dichromate is titrated with FAS to determine that used for

oxidizing the organic matter.


6Fe2++ Cr2O72--> 6Fe3++ 2Cr3++ 7H2O
Ferroin indicator gives a change yellow to re colour on complete reduction

of dichromate. Result expressed as mg/LCOD.

5. A sample is collected for COD analysis and it is to be performed on the

following day. Describe two ways by which the sample can be preserved.

Why is it necessary to preserve the sample?


Two ways to preserved water sample are adding a little bit acid and

keeping samples in ice. Keeping samples in ice until they are submitted to

the laboratory will preserve them well enough for most tests. It is

necessary to preserve the sample because it can retard the chemical and

biological changes in the sample.

10 CONCLUSION

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

requirement of sample that is susceptible to oxidation by strong chemical

oxidant. The COD value for sample in this experiment under low range and it

is classified as class V based on INWQS. Hence, we can conclude that this

water sample has high organic matter. Lastly, COD is the total measurement of

all chemicals in the water that can be oxidized.

11 SUGGESTIONS AND RECOMMENDATIONS

The vial must be cleaned and removed all tags on the vials surface

before putting in to the COD reactor and the tags should be putting on the

cap of vial. This should be considered a precaution during carry out the

experiment. The parallax error should be avoided when taking the reading of

the burette.

12 REFERENCES

1) Davies, M.L et. al. Principles of Environmental Engineering and Science;


McGraw Hill; 2004.
2) http://education.seattlepi.com/titration-different-colorimetry-4356.html
3) http://science.jrank.org/pages/1388/Chemical-Oxygen-Demand.html
4) http://www.pcd.go.th/info_serv/en_reg_std_water04.html

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Prepared by/Disediakan oleh : Approved by/Disahkan oleh :

Signature/Tandatangan : Signature/Tandatangan :
Name/Nama : DR. NOR HASLINA HASHIM Name/Nama : DR. SURAYA HANI ADNAN

Date/Tarikh : FEBRUARY 2015 Date/ Date/Tarikh : FEBRUARY 2015

APPENDIX: COD PROCEDURE

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