Abstract

The objectives of this studies are to assess the quality of surface waters. Besides, to determine
the amount of dissolved oxygen in waste water samples. The studies are to establish the
concentration of organic matter in waste water samples. Lastly, to understand the
characteristics of DO contained in water and wastewater.

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Table of Contents
Abstract ...................................................................................................................................... 1

Introduction ................................................................................................................................ 3

Chemical oxygen demand ...................................................................................................... 3

Biological oxygen demand ..................................................................................................... 3

Ways to minimize cod ............................................................................................................ 4

1. COD Reducement using Precipitation Process (Coagulation) .................................... 4

2. Microbiology Process for COD Reducement.............................................................. 5

3. Reduce COD with Oxidation ...................................................................................... 5

4. COD Reducing process by Fenton Reaction ............................................................... 5

5. Advanced Oxidation Process, The latest COD Reducing Method.............................. 6

6. Process Filtration and Adsorption with Activated Carbon.......................................... 6

Determination of COD ........................................................................................................... 6

Experimental procedure ............................................................................................................. 7

Experimental Results ................................................................................................................. 8

Discussion .................................................................................................................................. 8

Conclusion ................................................................................................................................. 9

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Introduction
There are about 40 million organic compounds known in the environment which cannot
be defined individually with considerable analytical effort and in short time. Therefore, the so-
called sum parameters are used. These parameters reflect effect and material characteristics of
one or more substances. The most popular sum parameter in waste water analysis are the BOD
(biochemical oxygen demand), COD (chemical oxygen demand), TOD (total oxygen demand)
and TOC (total organic carbon). The TOC reflects the organic pollution on the basis of a direct
carbon determination. The other parameters are based on oxygen, which is required to reduce
or to oxidise the samples' substances. (Thomas, 1998)

Chemical oxygen demand

The COD value has been developed analogically to the BOD measurement. Since there
are many organics which are rather hard or not possible to decompose biologically, a parameter
has been defined indicating the amount of oxygen which would be needed when all organic
ingredients would be oxidised completely. As, according to the name, the oxidation takes place
chemically, the chemical oxygen demand can only be defined indirectly. A chemical oxidant
is added to the sample in question, the consumption of which is then determined. The
internationally dominant method today is the so-called 'Dichromate' method which is
characterized by the acidification of the sample with sulphuric acid and the addition of silver
sulphate. To avoid false measurements in chloride-containing samples, the chloride must be
masked by mercuric sulphate first. Due to the application of hazardous chemicals and having
an analysis time of 2 hours the method is not suitable for online use. (Thomas, 1998)

Biological oxygen demand

The BOD indicates the content of oxygen needed to decompose organic compounds in
waste water by bacteria. In most cases the special factor BOD5 is perceived as the BOD, which
requires a detailed definition (5 represents the 5 days analysis time). For the determination of
BOD5 there are nitrification inhibitors added to the samples, which suppress the degradation of
nitrogen compounds. Consequently, it results in the determination of the decomposition of
carbon compounds only (carbonaceous BOD, cBOD). Due to this limitation, an essential

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process of sewage treatment is not considered: The nitrification. Obviously, a WWTP can only
be controlled and monitored reliably by total BOD measurements, instead of the determination
of the insufficient BOD5. In the real sense, BOD measurements are respiration measurements.
Due to their rapidity, respiration measurements are preferred for online analysis. Provided that
the conditions are known, respiration measurements [mg/(l*min)] can be converted into BOD
measurements [mg/l]. Due to the 5-day analysis time and the measurement of the carbonaceous
BOD instead of total BOD, the BOD5 is not suitable to assess the current capacity of the waste
waters' degradation by bacteria. The BOD5 is only a time-delayed information about the
pollution of waste water and cannot be used for optimization or control of a WWTP.
Alternatively, BOD analysers or respiration analysers can be used, which enable measurements
within 5 to 60 minutes. Thus, estimations can be made promptly for the biodegradability of the
waste water and its behaviour in the plants. The market is dominated by short-time respiration
measurements by O2 electrodes. Due to the low oxygen solubility of the waste water, the small
respirations are extrapolated to the final result by using factors. Essentially, only the easy
biodegradable substances are detected this way. Alternatively, LAR AG provides an online
respirometer that operates like a miniature waste water treatment plant: The BioMonitor. This
BOD analyser degrades nitrogen and carbon compounds in special waste water cascades, so
that the significant total BOD is determined. Due to the multi-stage cascade structure also
difficult to degrade components are reliably detected. The oxygen required for the degradation
is measured by an O2 sensor. Especially advantageous is the use of the plant's activated sludge,
whereby the conditions at the WWTP are simulated reliably. (Thomas, 1998)

Ways to minimize cod

1. COD Reducement using Precipitation Process (Coagulation)
The most important way to get rid of the sludge is to use coagulants and flocculants.
The principle is to bind the sludge to one another so that a larger clump of sludge and then be
deposited in a sedimentation tank. Some chemicals commonly used as a coagulant, among
others; PAC, FeCl3 (Ferric Chloride) and Alum. This deposition process will greatly affect the
value of COD. Especially in wastewater with a high enough amount of TSS. For additional
information for the 1 mg / L TSS you can get a drop of up to 10 mg / L COD. COD reduction
process in order to become more perfect, it is advisable to give more concern to the process of

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mixing and sedimentation. Due without proper mixing process, the precipitation reaction that
occurs will be less than perfect. (G. J. Schroepfer, 1964)

2. Microbiology Process for COD Reducement

COD reduction process by the method of using bacteria or microorganisms, devoted to

COD derived from organic matter with a high content of biodegradable. This process is done
in two main ways, namely aeration and anaerobic. In the aeration process, COD reduced by
making the bacteria can break down organic compounds in water. These bacteria are called
heterotrophic bacteria break down organic compounds due to the use of oxygen. This process
is usually used in waste water with a COD of less than 3000 mg / L. In the process of anaerobic
bacteria work in a room with minimal oxygen content. This process is also called fermentation,
in which bacteria break down autotroph working with organic compounds from wastewater
with three stages of one of them is by taking oxygen from organic compounds. The anaerobic
process is suitable for waste water with BOD levels over 2000 mg / L. Before deciding whether
to take this method, it is important for you to understand what types of wastewater that you
face. Because microbiological process is only suitable for wastewater with organic contents.
You can determine this by looking at the comparison between COD and BOD. (G. J.
Schroepfer, 1964)

3. Reduce COD with Oxidation

Some chemicals can help you to reduce the COD of waste water. Chlorine, Hydrogen
peroxide and Ozone will mengoksdiasikan chemicals in the water so that the automatic COD
value will go down. But of course you should limit dose usage of oxidator, because oxidator
possess sufficient berhaya especially for living organisms. COD reduction technique is suitable
for waste have COD values derived from non-biodegradable waste such as Phenol, surfactants.
(G. J. Schroepfer, 1964)

4. COD Reducing process by Fenton Reaction

Fenton reaction is a reaction that has been widely known is able to reduce the COD value.
The principle is the formation of free radicals that are created from the reaction between Fenton
reagent is FeSO4 with Hydrogen peroxide. Fenton reaction is what will be the forerunner of
the birth of AOP system. (G. J. Schroepfer, 1964)

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 5. Advanced Oxidation Process, The latest COD Reducing Method

AOP is the latest technology that is able to reduce the COD value of the wastewater. Even
of COD with a value above 100 thousand though. AOP was created from the added refinement
of Fenton reaction in the presence of ozone injection so adding reproduce free hydroxyl finally
able to oxidize chemicals in water. Excess AOP process is very fast reaction speed. If the
processing by microbiological reduction in COD can take days. Then the AOP process only
takes a matter of hours or even minutes. Another plus is also located in the area used for this
system is very small is compared with other systems. Moreover, this process does not require
a lot of chemicals to be added in the wastewater. (G. J. Schroepfer, 1964)

6. Process Filtration and Adsorption with Activated Carbon

The latter method is widely used in the finishing process or post treatment after primary
treatment process. Usually used as an activated carbon filter. Activated carbon will absorb
organic substances, ozone or chlorine substances remaining on the processing results. So safe
effluent to be discharged into the environment. Filtration using activated carbon is also
commonly used in water treatment processes to remove odors and reduce the chemicals in the
water. (G. J. Schroepfer, 1964)

Determination of COD
To determine the COD, 10cm3 of 0.25N standard potassium dichromate solution was
added to 20cm3 of wastewater sample in a 250ml round-bottom flask. 1g of silver sulphate and
40cm3 of concentrated sulphuric acid were added in small portions with thorough swirling,
until the silver sulphate was completely dissolved. A few glass beads were added to serve as
anti-bumping aid, and the flask was connected to reflux condenser. The mixture was heated
gently for 10 minutes, after which the content of the flask was now cooled. 50cm3 of distilled
water was flushed through the condenser, and the cooling was completed under running tap
water. 2 drops of indicator solution were added and the resulting mixture titrated with
standardized ferrous ammonium sulphate solution until there was a change of colour from
yellow-green via blue-green to reddish brown. A blank value was determined in the same way
with 20cm3 of distilled water. The COD values of the respective samples were calculated using
equation (1).

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Equation 1

1000(𝑎 − 𝑏)𝐶
𝐶𝑂𝐷 =
𝑉

In equation (1), a and b are the respective volumes of ferrous ammonium sulphate used for the
blank and sample (cm3 ), V is the volume of sample (cm3 ), and c the normality of ferrous
ammonium sulphate. (G. J. Schroepfer, 1964)

Experimental procedure

1- put a few clean glass beads to COD flask. Then put 20 ml of sample in flask,
add 0.4g mercuric sulfate and add 10 ml of potassium dichromate solution

2- add 30 ml of sulfuric acid silver sulfate solution to the previous mixture

,mixing after each addition

3- before heat is applied , the reflux should be mixed well

4- attach reflux to the mixture and flask to condenser for 2 hours

5- cool it and then wash it down with 25 ml distilled water

6- dilute the mixture 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.

8- Repeat steps 1 to 7 using 20 ml distilled water instead of the sample.

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Experimental Results
After performing the procedures and obtain the needed measurements which will be used
now in the calculations. The measurements showed that:

-The volume of waste water is 20 (ml)

-The concentration of sodium thio sulphate is 0.1 (N)

-The volume titrated is 7.5 (ml)

-Then by substitute in this equation:

Equation 2 COD

COD=
𝑁 𝑠𝑜𝑑𝑖𝑢𝑚 𝑡ℎ𝑖𝑜𝑠𝑢𝑙𝑝ℎ𝑎𝑡𝑒 ×𝑑𝑉 ×𝑤𝑡.𝑜𝑓 𝑜𝑥𝑦𝑔𝑒𝑛
𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑠𝑎𝑚𝑝𝑙𝑒

0.1 ×(20−7.5)×8
COD= = 500 𝑚𝑔/𝑙
20

Discussion
After we make the calculations and the chemical oxygen demand (COD) had been

calculated it must be compared to the allowable standard limit of the COD in the water. As

its mentioned in the water standard quality that the allowable limit for COD in the water is

250 mg/L. As the allowable limit is 250 mg/L so the COD obtained isn’t acceptable

according to the water standards quality, so it’s obtained that after obtaining the

measurements and perform the needed calculations it obtained that the COD is 500 mg/L.

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Conclusion
(BOD) and (COD) are the foremost normally used parameters for the characterization

of wastewaters. each of those parameters have blessings and downsides, and therefore

the alternative typically depends on several factors like the fundamental quantity needed to

see each of them. it's essential to get a correlation between BOD and COD

for numerous effluent treatment plants, to assist within the style and operation of

those plants. Wherever the allowable limit is 250 mg/l however it had been complete to be five

hundred mg/l.

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References

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