Wastewater Treatment for

Chemical Engineer
Determination of BOD and COD

By: Omar Samir

ID :117781

Supervision: Dr. Mohamed El-Dessouky

Eng. Omar Abo EL-Azayem
 Abstract

This experiment aims to characterize the waste water included in the lab in terms of determining
the value of COD in the sample. To be able to carry out the experiment the following reagents
should be available: Sulfuric acid ,silver sulfate solution, Potassium dichromete solution, 0.25N
Ferroin indicator solution, Ferrous ammonium sulfate solution 0.25N, Mercuric sulfate (H2SO4),
analytical grade crystals. By obtaining the equivalent weight of oxygen and substituting it in the
general equation of COD, the value of COD will be obtained to be 300 mg/l . depending on the
VLAREM II Basic Environmental Quality Standards for Surface Water, the value of COD
should not exceed 30 mg/l.

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Table of content

Abstract ........................................................................................................................................... 1
Table of content .............................................................................................................................. 2
1. Introduction ............................................................................................................................. 3
1.1. Biological Oxygen Demand (BOD)..................................................................................... 4
1.2. Chemical Oxygen Demand (COD) ...................................................................................... 4
1.2.1. Case Study: Determination of COD in aqueous samples without Electrochemical
methods 4
2. Experimental methods and procedures .................................................................................... 7
2.1. COD ................................................................................................................................. 7
2.1.1. Equipment ................................................................................................................. 7
2.1.2. Materials ................................................................................................................... 7
2.1.3. Procedure .................................................................................................................. 7
3. Experimental Results ............................................................................................................... 8
4. Discussion and Conclusion ...................................................................................................... 9
5. Sources of Error ..................................................................................................................... 10
6. Bibliography .......................................................................................................................... 11

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1. Introduction

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 1.1. Biological Oxygen Demand (BOD)

The Biological Oxygen Demand could be demonstrated as the amount of oxygen applied by the
micro-organisms in a biological process, in which it breaks down the organic matter in water.
Moreover, it could be expressed as the measure of organic pollutant magnitude. The BOD is
determined by the amount of oxidizable organic matter in water (Ph.Namour, 2010). In other
words, they are directly proportional to each other. Consequently, the strength of waste water is
demonstrated in terms of (BOD). The BOD is a critical parameter in which it could represent the
quantity if organic matter existing in the waste water and the amount of oxygen needed to be able
to stabilize it. For sake of measuring the treatment plant operation and efficiency in process design,
values of BOD are necessary for this particular point.

Organic matter could take time period from 20-30 days to be fully degraded. For example, glucose
compound (simple organic compound) is oxidized completely in 5 days. However, applying the
same period on domestic sewage will only oxidize 65% of it. The period from 20-30 days is of
lowest significance in experimenting. Subsequently, the BOD experiment is adjusted to be
performed for 5 days at 20 C0 (Torrades, 2012). This test gives us the privilege to obtain a
qualitative reference for the organic matter in which they are degraded rapidly in a relatively short
period.

1.2. Chemical Oxygen Demand (COD)

1.2.1. Case Study: Determination of COD in aqueous samples without

Electrochemical methods

The contamination of water became a critical issue globally, considering the chemical oxygen
demand (COD) as a main criterion in the water treatment industry, enhancing information around
the possibility of chemical degradable fractions of the organic pollutants. Yet the classic methods
of COD test are time consuming and not preferable from the economic aspect. To be able to

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overcome these obstacles, efforts was gathered to improve the digestion and detection techniques.
As this review refer to recent methods in the determination of the COD within aqueous samples,

depending on previous establishments since year 2000. This review includes several critical
methods used and show their applicability. The review demonstrated the following: 1) the typical
standard methods, 2) several detection methods, 3) Novel digestion techniques and 4) future
methods for the measurement of COD. (Ma, 2017)

This paper highlighted and discussed the major strategies and technology designed to determine
COD in aqueous solution (Ma, 2017). It was concluded that due to the routine analysis of such an
experiment has limited the applicability of the mentioned methods. Several aspects us be
considered to choose the most suitable method for determining the COD such as: measurement
frequency, cost of both instruments and labour, samples numbers for the routine analysis,
allowable error rate and the type of applications which are considered.

To be able to reach the optimum methods for the determination of COD, the following aspects are
recommended to be included (Ma, 2017):

1. Several factors could affect the COD measurement such as: types and concentration of the
applied oxidant, time and temperature of the reaction, pH value of the reagents used and
the use of the catalyst. Which means that the conditions of measuring COD must be strictly
control as far as possible, also procedures must be defined well. In order to study and make
sure of the efficiency of the new methods applied for measuring the COD, a comparison
between the new and standard methods should be performed.
2. It is very important to analyze the riverine organic sludge input recycle into the oceans, by
the use of precise data of COD from coastal water with coordinating several salinity. Yet
the values of COD obtained from the coastal water are not consistent always when applying
the standard methods. To be able to resolve the problems on comprising the surface water
quality and marine quality ordinary data. Developments and improvements must be applied
on the coastal water quality measurements.

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3. Various model compounds has been applied for evaluating the digestion efficiency such
as: D-glucose, lactic and acetic acid, potassium hydrogen phthalate and phenol. Yet most
of the methods utilize one of the previous compounds, and focusing on the potassium
hydrogen phthalate. To evaluate the limitations and reliability of digestions techniques, the
refactory and labile compounds should be considered.

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2. Experimental methods and procedures

2.1. COD

2.1.1. Equipment

1. A reflux apparatus consisting of a 300 ml flask with ground glass neck and a condenser
2. A hot plate
3. Erlenmeyer flask, 500 ml

2.1.2. Materials

1. A wastewater sample
2. Reagents
a. Sulfuric acid - silver sulfate solution
b. Potassium dichromete solution, 0.25N
c. Ferroin indicator solution
d. Ferrous ammonium sulfate solution 0.25N
e. Mercuric sulfate (H2SO4), analytical grade crystals

2.1.3. Procedure

1. Add a few clean glass beads to a dry COD flask. Place 20 ml sample in the flask, add 0.4g
mercuric sulfate and add 10 ml potassium dichromate solution.
2. Carefully add 30 ml sulfuric acid-silver sulfate solution to the sample mixture, a little at a
time, mixing after each addition.
3. Make sure that the reflux mixture is mixed thoroughly before heat is applied.
4. Attach flask to the condenser and reflux the mixture for 2 hours.
5. Cool then wash down the condenser with about 25 ml distilled water.
6. Dilute the mixture to about 140 ml, cool, and titrate the excess dichromate with ferrous
ammonium sulfate solution using ferroin indicator, two or three drops of the indicator are
added to the sample just before titration.
7. Take as the end point the sharp color change from blue-green to reddish-brown, even
though the blue green may reappear within minutes.
8. Repeat steps 1 to 7 using a blank (20 ml distilled water) instead of the sample.

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 3. Experimental Results

(𝑉1−𝑉2)(𝑁1 ∗𝐸𝑞 𝑤𝑡 𝑜𝑓 𝑜𝑥𝑦𝑔𝑒𝑛)

COD =
𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑤𝑎𝑠𝑡𝑒 𝑤𝑎𝑡𝑒𝑟 𝑠𝑎𝑚𝑝𝑙𝑒

Where:

 V1: Thiosulphate Volume

 V2: Thiosulphate Volume for blank sample
 N1: Thiosulphate normality

- T be able to deduce the Equivalent weight of oxygen to calculate the COD, the following
equation should be used:

𝑀𝑤𝑡 𝑜𝑓 𝑜𝑥𝑦𝑔𝑒𝑛∗1000
𝑉𝑎𝑙𝑒𝑛𝑐𝑦

𝑀𝑤𝑡 𝑜𝑓 𝑜𝑥𝑦𝑔𝑒𝑛∗1000 16∗1000

 Equivalent weight of oxygen = = = 8000 mg
𝑉𝑎𝑙𝑒𝑛𝑐𝑦 2
(𝑉1−𝑉2)(𝑁 𝑜𝑓 𝑡ℎ𝑖𝑜𝑠𝑢𝑙𝑝ℎ𝑎𝑡𝑒∗𝐸𝑞 𝑤𝑡 𝑜𝑓 𝑜𝑥𝑦𝑔𝑒𝑛) (7.5)(0.1∗8000) 𝑚𝑔
 COD = = = 300
𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑤𝑎𝑠𝑡𝑒 𝑤𝑎𝑡𝑒𝑟 𝑠𝑎𝑚𝑝𝑙𝑒 20 𝑙

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 4. Discussion and Conclusion

The COD test is widely used in the industry to measure the quantity of organic matter in water
indirectly. COD applications are used to obtain the amount of organic pollutants sourced from the
water’s surface, which indicates that the COD technique is an efficient technique to measure the
quality of water. The value of COD is represented in mg/l, which means the mass of O2 consumed
for every liter of the solution. Under acidic conditions, Potassium dichromate is considered a
powerful oxidizing agent. In this experiment, 0.25N of potassium dichromate solution is used. As
the organic substance existing in water is oxidized, a reduction of potassium dichromate takes
place, resulting of Cr3+. After the oxidization takes place the amount of Cr3+ could be determined,
in which it could be helpful to indirectly measure the amount of organic content in the sample.

Potassium dichromate performs as a powerful oxidizing agent in which it oxidizes the

organic/inorganic substance in waste water. The reaction is illustrated as follows:

Cr2O72- + 14 H+ + 5 e- = 2 Cr+ + 7 H2O

To make sure of the non-interference of chlorides, Mercury Sulphate reagent is added, as it will
result a complex of mercuric chloride. An amount of 0.4g of Mercury Sulphate is added as
mentioned in the Experimental Procedure. After performing the results, the value of COD was
found to be 300 mg/l. Referring to VLAREM II Basic Environmental Quality Standards for
Surface Water, the value of COD should not exceed 30 mg/l. which means that the obtained result
is not acceptable according to the COD standard value.

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5. Sources of Error

1. The hugest error is due to the use of nonhomogeneous sample.

2. Always use the largest sample practical and use the largest glassware that is in keeping
with good laboratory practice.

3. Volumetric flasks/pipettes used should have large bore.

4. The oxidizing agent (K2Cr2O7 ) should be accurately measured. Using the volumetric
pipette and its preferred to use it each time if possible.

5. The clearness of the burette should be checked when titrating, and checking if its free of
air bubbles.

6. the bottom angle of the meniscus should be read carefully and make sure that the
meniscus at eyelevel to avoid parallax error

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 6. Bibliography

Ma, J. (2017). Determination of chemical oxygen demand in aqueous samples with

nonelectrochemical. Trends in Environmental Analytical Chemistry, 1-7.
Ph.Namour. (2010). Sensors for measuring biodegradable and total organic matter in water.
TrAC Trends in Analytical Chemistry, 848-857.
Simms, T. (2010). General Biology 1. Laboratory Manual. Toronto .
Torrades, F. (2012). Bias-free results in the spectrophotometric determination of chemical
oxygen demand in bleached textile mill effluents. Chemical technology and Biological
technology , 4-9.

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