Khulna University of Engineering & Technology (KUET), Khulna

CE 3242
Sessional on Environmental Engineering II
Exp. Name: Determination of Chemical Oxygen Demand (COD)

Submitted by
Md. Shahariar Kabir
Roll:1701018
Sec: A
Date of Performance: 10 June, 2021 Department of Civil Engineering
Date of Submission: 17 June, 2021 KUET, Bangladesh.
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1. General Discussion

Principle: Chemical oxygen demand (COD) is defined as the amount of a specified oxidant
that reacts with the sample under controlled conditions. The quantity of oxidant consumed is
expressed in terms of its oxygen equivalence. Because of its unique chemical properties, the
dichromate ion (𝐶𝑟2 𝑂72− ) is the specified oxidant in Methods 5220B, C, and D; it is reduced
to the chromic ion (Cr3+) in these tests. Both organic and inorganic components of a sample
are subject to oxidation, but in most cases the organic component predominates and is of the
greater interest. If it is desired to measure either organic or inorganic COD alone, additional
steps not described here must be taken to distinguish one from the other. COD is a defined
test; the extent of sample oxidation can be affected by digestion time, reagent strength, and
sample COD concentration. COD often is used as a measurement of pollutants in wastewater
and natural waters. Other related analytical values are biochemical oxygen demand (BOD),
total organic carbon (TOC), and total oxygen demand (TOD). In many cases it is possible to
correlate two or more of these values for a given sample. BOD is a measure of oxygen
consumed by microorganisms under specific conditions; TOC is a measure of organic carbon
in a sample; TOD is a measure of the amount of oxygen consumed by all elements in a
sample when complete (total) oxidation is achieved. In a COD analysis, hazardous wastes of
mercury, hexavalent chromium, sulfuric acid, silver, and acids are generated. Methods
5220C and D reduce these waste problems but may be less accurate and less representative.
Here we use 5220D.

When a sample is digested, the dichromate ion oxidizes COD material in the sample. This
results in the change of chromium from the hexavalent (VI) state to the trivalent (III) state.
Both of these chromium species are colored and absorb in the visible region of the spectrum.
The dichromate ion (𝐶𝑟2 𝑂72− ) absorbs strongly in the 400-nm region, where the chromic ion
𝐶𝑟 3+ absorption is much less. The chromic ion absorbs strongly in the 600-nm region, where
the dichromate has nearly zero absorption. In 9M sulfuric acid solution, the approximate
molar extinction coefficients for these chromium species are as follows: 𝐶𝑟 3+ − 50 L/mole
cm at 604 nm; (𝐶𝑟2 𝑂72− ) − 380 L/mole cm at 444 nm; 𝐶𝑟 3+ − 25 L/mole cm at 426 nm. The
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𝐶𝑟 3+ ion has a minimum in the region of 400 nm. Thus a working absorption maximum is at
420 nm.

For COD values between 100 and 900 mg/L, increase in 𝐶𝑟 3+ in the 600-nm region is
determined. Higher values can be obtained by sample dilution. COD values of 90 mg/L or
less can be determined by following the decrease in (𝐶𝑟2 𝑂72− ) at 420 nm. The corresponding
generation of 𝐶𝑟 3+ gives a small absorption increase at 420 nm, but this is compensated for
in the calibration procedure.

COD Reaction

2𝐾𝐶8 𝐻3 𝑂4 + 10𝐾2 𝐶𝑟2 𝑂7 + 41𝐻2 𝑆𝑂4 → 10𝐶𝑂2 + 46𝐻2 𝑂 + 10𝐶𝑟2 (𝑆𝑂4 )3 + 11𝐾2 𝑆𝑂4

Chemical oxygen demand (COD) is a common way to measure organics in wastewater

for environmental engineers and others in the environmental field. Like the biochemical
oxygen demand (BOD), COD measures the amount of oxygen used to oxidize organics in
wastewater to carbon dioxide. This lab will show the principle of finding the amount of
oxygen required to oxidize organic matter and how the COD can be used to measure the
strength of wastewater.

Interference and limitations: Here, we used 5220 D. Closed Reflux, Colorimetric Method.

All visible light-absorbing interferents must be absent or be compensated for. This includes
insoluble suspended matter as well as colored components. If either type of interference
occurs, the test is not necessarily lost because COD can be determined titrimetrically.

2. Apparatus

 COD vial 16 X 100 mm culture tube

 DR 2700
 HACH DR 200 COD digestion reactor
 DR 3900
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3. Reagents

 Digestion solution, high range: Add to about 500 mL distilled water 10.216 g
𝐾2 𝐶𝑟2 𝑂7 primary standard grade, previously dried at 150°C for 2 h, 167 mL conc.
𝐻2 𝑆𝑂4 and 33.3 g 𝐻𝑔𝑆𝑂4 .
 Alternative digestion solution (low range): Dissolve, cool to room temperature, and
dilute to 1000 mL. b. Digestion solution, low range: Prepare as in 3a, but use only
1.022 g potassium dichromate.
 Sulfuric acid reagent: Add Ag2SO4, reagent or technical grade, crystals or powder, to
conc. H2SO4 at the rate of 5.5 g Ag2SO4/kg H2SO4.

4. Procedure

I. At first 2.5 mL sample was taken in a COD vial.

II. Then 1.5 mL COD digestion solution was added into the mixture.
III. 3.5 mL 𝐻2 𝑆𝑂4 regent solution was added.
IV. The solution was mixed by using vortex mixture.
V. The solution of COD vial was digested by using COD reactor for 2.0 hour.
VI. The absorbance reading was read by using HACH spectrometer (at wavelength 600
nm High rang COD) then COD value was calculated by using equation derived from
COD calibration curve.

5. Calculation

Roll no: 1701018

𝑙𝑎𝑠𝑡 3 𝑑𝑖𝑔𝑖𝑡 𝑜𝑓 𝑟𝑜𝑙𝑙 𝑛𝑜×2 018×2

X= Absorbance = [ ]= = 0.036
1000 1000

From the calibration curve we get,

Y= COD

Y= 2440.5X + 2.1387

Y= (2440.5*0.036) + 2.1387 = 89.99 mg/L

Result: The total COD of the sample is 89.99 mg/L

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6. Precision and Bias

We had got the COD 89.99 mg/L. In this experiment, here are a few errors that could have
caused flaws in the results of this experiment. First, there could be an error if the vials heat
was not consistent between all the vials, this would cause the reaction to go at a different rate
for each vial. Another error that could occur is that while pouring the contents of the vial into
the Erlenmeyer flask before titration, used more than 1 mL of deionized water to rinse the
vial. This would dilute the solution causing the COD levels to be lower?. Finally, an error
could be that you stopped the titration too early, before it reached a dark red color. This
would result in the different measurement of FAS used for the sample which will result in a
higher COD than it actually is.

In environmental engineering, the COD test is commonly used to indirectly measure of the
amount of organic compounds in water. Most applications in COD determine the amount of
organic pollutants found is surface water (e.g. lakes and river), making COD is a useful
measure of water quality. It is expressed in milligrams per liter (mg/L), which indicates the
mass of oxygen consumed per liter solution.

7. Reference

1. AMERICAN SOCIETY FOR TESTING AND MATERIALS. 1995. Standard test methods for chemical
oxygen demand (dichromate oxygen demand) of water. D1252-95, ASTM Annual Book of Standards.
American Soc. Testing & Materials, Philadelphia, Pa.

2.https://www.studocu.com/en-us/document/university-of-nebraska-lincoln/environmental-engineering-
laboratory/coursework/laboratory-4-chemical-oxygen-demand-report/1779550/view

3.https://www.scribd.com/doc/83893641/Conclusion-Cod

8. Bibliography

1.JIRKA, A.M. & M.J. CARTER. 1975. Micro semi-automated analysis of surface and wastewaters for
chemical oxygen demand. Anal. Chem. 47:1397. HIMEBAUGH, R.R. & M.J. SMITH. 1979. Semi-micro
tube method for chemical oxygen demand. Anal. Chem. 51:108