Introduction:

In recent times, with the increase of pollution by discharging large amount of various
chemicals, oxidizable organic substances of different matter enter in the aquatic
system. BOD values alone does not give a clear picture of organic matter content of
the water sample. In addition, the presence of various toxicants in the sample may
severely affect the validity of BOD test. Hence chemical oxygen demand (COD) test
is a better estimate of organic matter which needs no sophistication and is time
saving. However COD that is the oxygen consumed (OC) does not differentiate the
stable organic matter from the unstable form, therefore the COD value are not
directly comparable to that of BOD.
The amount of organic matter in water is estimated based on their oxidizability by
chemical oxidants, such as potassium permanganate or potassium dichromate. For
many years, the potassium permanganate was used as oxidizing agent for
measuring chemical oxygen demand. But the oxidizing capacity of potassium
permanganate varied widely. Nowadays, Potassium dichromate is used instead of
potassium permanganate because it is more effective, relatively cheap, easy to
purify and is able to oxidize almost all organic compounds.
In this method, a fixed volume of oxidant (here potassium dichromate) is added to
the water sample. The organic matter present in the water sample is first oxidized
with known volume of potassium dichromate and then excess of oxygen is allowed to
react with potassium iodide to liberate iodine in amounts equal to the excess oxygen,
which is estimated titrimetrically with sodium thiosulphate as an indicator.

Objectives:
1. To determine the concentration of chemical oxygen demand in wastewater
samples (influent and effluent) taken from Canseleri UiTM Shah Alam
Treatment Plant by using EPA Method 410.3 (Dichromate Reflux Method) and
EPA Method 410.4 (Reactor Digestion Method).
2. To measure the effectiveness of a wastewater treatment plant based on the %
removal of chemical oxygen demand (COD).

Procedures:
Name of method:
1. Dichromate Reflux Method
2. Reactor Digestion Method
No. of standard method:
1. EPA Method 410.3
2. EPA Method 410.4
Procedures based on reference 1. Page 15-23.
In-situ Data:
Influent

Effluent

Temperature (C)

28.87

24.42

DO (mg/L)

2.06

1.59

pH

1.48

1.35

Odour

Odourless

Odourless

Colour

Light brown

Light brown

Conductivity (s/cm)

5378

4652

Ex-situ Data:
1. Dichromate Reflux Method
Group

Sample

Sample

Titration of

Titration

Titration of

Normality

COD for

volume,

sample, mL

sample

standard, mL

of FAS

each

removal

group,

of COD

mL

Initial

Final

average,

Initial

Final

mL
1

mg/L

I1

50

0.0

40.0

42.5

0.0

I2

50

0.0

45.0

Blank

50

0.0

69.5

69.5

0.0

E1

50

0.0

54.5

53.0

0.0

E2

50

0.0

51.6

Blank

50

0.0

50.5

50.5

0.0

I1

*25

0.0

53.4

49.8

0.0

I2

*25

0.0

46.2

Blank

*25

0.0

55.5

55.5

0.0

E1

*25

0.0

51.0

51.6

0.0

E2

*25

0.0

52.2

Blank

*25

0.0

50.3

0.0

0.0

0.0

0.0
50.3

21.2

475.2
109.4

22.7

-44.9
0.11

22.2

200.6
122.8

24.0

-45.8

0.0

2. Reactor Digestion Method

Groups

Sample

COD digestion reagent

Spectrophotometer

COD

Average of

vial type and volume,

reading, mg/L

actual,

COD value,

mg/L

mg/L
17.87

mL
5

I1

HR 0.2

22.0

18.3

I2

HR 0.2

21.0

17.5

Blank

HR 0.2

0.0

0.0

0.0

I1

LR 2.0

284.0

236.0

236.0

I2

LR 2.0

284.0

236.0

Blank

LR 2.0

0.0

0.0

0.0

E1

HR 0.2

ND

ND

ND

E2

HR 0.2

ND

ND

E1

LR 2.0

109.0

90.6

E2

LR 2.0

102.0

84.8

Standard

LR 2.0

121.0

100.5

% COD removal

LR = 71.3

67.7

100.5

HR = ND

Discussions:
Dichromate Reflux Method
Based on the result obtained, the volume of titration for influent 50 mL are 40.0 mL
and 45.0 mL with an average of 42.5 mL, the COD concentration for this influent is
475.2 mg/L. The volume of titration for effluent 50 mL are 54.5 mL and 51.6 mL with
an average of 53.0 mL, the COD concentration for this effluent is -44.9 mg/L which
can be considered as ND. The volume of titration for influent 25 mL are 53.4 mL and
46.2 mL with an average of 49.8 mL, the COD concentration for this influent is 200.6
mg/L. The volume of titration for effluent 25 mL are 51.0 mL and 52.2 mL with an
average of 51.6 mL, the COD concentration for this influent is -45.8 mg/L which also
can be considered as ND.
Since the reading for effluent obtained is negative, the % removal of COD has
become more than 100%. The result of getting negative COD concentration is
indicates that the COD is not detectable (ND). This shows that theres a significant
reduction of COD concentration because even from influent the COD reading is not
very high which lead to very low concentration of COD in effluent. When
concentration of COD too low, it will become negative which proves the COD
concentration in the sample is ND.
Based on Malaysia Sewage and Industrial Effluent Discharge Standards, the
permissible limit for COD is 100 mg/L for standard B which is used for this effluent
because it released to Sungai Klang. The result obtained in this experiment for
effluent are -44.9 mg/L and -45.8 mg/L which is considered as ND and result is
acceptable as well as the effluent is permitted if being discharge into Sungai Klang.
Reactor Digestion Method
Based on the result obtained, the concentration of COD for influent in high range is
18.3 mg/L and 17.5 mg/L with an average of 17.87 mg/L. For the low range, the
concentration of COD for influent is 236.0 mg/L and 236.0 mg/L with having same
value for average. For effluent reading, the high range both reading is not detectable
(ND) which means the reading of COD concentration of that sample is too low for the
detectable limit for spectrophotometer. For effluent reading in low range, COD
concentration is 90.6 mg/L and 84.8 mg/L with an average reading 67.7 mg/L.

The standard reading based on spectrophotometer is 121.0 mg/L, considered as

different and too far from the actual concentration of standard. Therefore, standard
adjustment factor is done and all samples were re-calculated with SAF in order to get
the real COD concentration of each sample.
The % of COD removal for low range is 71.3% and for high range is ND since the
effluent is ND. Based on the % COD removal (low range) is 71.3% that means the
efficiency of treatment plant in removing COD is more than 50% and considered as
effective in removing COD. Based on Malaysia Sewage and Industrial Effluent
Discharge Standards, the permissible limit for COD is 100 mg/L for standard B which
is used for this effluent because it released to Sungai Klang. The result obtained in
this experiment for effluent is 67.7 mg/L which below than the limit and result is
acceptable as well as the effluent is permitted if being discharge into Sungai Klang.
Sources of error:
The LR and HR mercury containing reagents are formulated to withstand
interferences from up to 2000 ppm chloride. The HR+ mercury containing COD
reagent can be used on samples containing up to 20,000 ppm chloride without
interference. Samples with higher chloride concentrations require dilution. Also,
samples that contain high levels of chloride (>1000 ppm) and low levels of COD
(<30% of the product range) will give false positive test results. In this case, sample
dilution is recommended. Mercury free reagents (LR and HR) are also available for
samples containing less than 100 ppm chloride (less than 1000 ppm for the mercury
HR+ kit).
Good technique and elimination of contamination are necessary for accurate results.
Wash all glassware with 20% sulphuric acid.
The COD reagent is light sensitive. Vials needed to be stare in the dark when not in
use.

Conclusion:
The concentration of COD for influent were 475.2 mg/L and 200.6 mg/L, for effluent
were -44.9 mg/L and -45.8 mg/L by using dichromate reflux method. Concentration
of COD of influent obtained from reactor digestion method were 17.87 mg/L (high
range) and 236.0 mg/L (low range). For effluent were ND (high range) and 67.7 mg/L
(low range). % removal of COD were 109.4% and 122.8% which using dichromate
reflux method. % removal of COD when using reactor digestion method is 71.3% for
low range.
References:
1. Kasmawati Mohamed, Lee Kok Kheng. 2012. Methods of Analysis for Water
and Wastewater. Shah Alam, UiTM Press.
2. http://water.me.vccs.edu/courses/ENV149/cod.htm
Retrieved on 3rd November 2014.
3. http://nitttrc.ac.in/Four%20quadrant/eel/Quadrant%20-%201/exp12_pdf.pdf
Retrieved on 3rd November 2014.
4. http://www.cwc.gov.in/main/HP/download/18%20Understanding%20COD%20
test.pdf
Retrieved on 3rd November 2014.

Questions:
Reactor Digestion Method
1. Why is it important to perform COD test in wastewater treatment?
-

This is because COD measures the pollution potential of organic matter in

wastewater.
OM + oxidant CO2 + H2O

Decomposable organic matter results in consumption of DO in wastewater

samples. When theres too high of COD value, DO values will drop and
become undesirable for aerobic treatment.

2. What is the function of the blank vial in the determination?

-

To act as constant which is to check if the vial containing any

contaminants and identical in all aspect to the test solution except for the
absence of test solute.

3. What will happen to the COD value if HgSO4 and AgSO4 are not added?
-

Chlorine will not be separated out of the sample effluent. COD will be
higher than it should be.

4. What is the reason that some time a green solution is formed after digestion?
How do you overcome this problem?
-

Dichromate

ions

(Cr2O7-2)

form

orange-coloured

solutions.

When

dichromate is reduced to chromic ion (Cr+3), the solution becomes green.

By ensure that the pH of the sample when preservation is kept at 2 and
before start the reflux, pH must be around 2.

Dichromate Reflux Method

5. What was the purpose of the blank sample of distilled water?
-

To compensate for any error that may result because of the presence of
extraneous organic matter in the reagents.

6. Summarise the method and write the chemical reactions involved and
interpret your test results.
-

Sample is refluxed with known amount of excess dichromate in presence

of acid. HgSO4 is a catalyst that is used to bind or complex chlorides.
Remaining dichromate is titrated with FAS to determine that used for
oxidizing the organic matter.
6Fe2+ + Cr2O72-

->

6Fe3+ + 2Cr3+ + 7H2O

Ferroin indicator gives a sharp change to brown colour on complete

reduction of dichromate. FAS is a secondary standard, must be
standardized frequently. Result expressed as mg/L COD.

Sample Calculation:
Dichromate Reflux Method

Where;
a = mL Fe(NH4)2(SO4)2 used for blank
b = mL Fe(NH4)2(SO4)2 used for sample
N = normality of FAS titrant [Fe(NH4)2(SO4)2]
mL sample = the actual volume of sample used before dilution

Reactor Digestion Method

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