OBJECTIVE

 To determine and calculate the organic oxidizeable matter content of water samples
given.

INTRODUCTION

There are many ways to measure the amount of organic matter in the water samples and one
of them is by using chemical oxygen demand (COD). This organic matter is oxygen required
to completely oxidise the organic matter to carbon dioxide and water. This follows the below
reaction:-

Organic Matter + oxidised CO2 + H2O

This oxygen that used to oxidise the organic matter can be calculated by using COD by the
present of a strong oxidants such as dichromate solution.

The method that used in this experiment is closed reflux, titrimetric method which the sample
is reflux or digests with a high temperature and strong acid. After the reflux is done, this
reaction happened:-

The sample titrates with Ferrous Ammonium sulfate (FAS) solution to determine to
consumption of K2Cr2O7.
ABSTRACT

A biodegradable and non-biodegradable organic matter and be chemically oxidised to know

the entire quantity of oxygen for chemical oxygen demand (COD. The purpose of this to
determine and get the organic oxidizeable matter content (COD) of the water samples that
given and measure the strength of the wastewater. Samples of 2.5 mL wastewater, QC that is
the stock standard of COD and a blank were pipetted into the test tube then added with
0.0167M potassium dichromate. After that a concentrated sulfuric acid added to the tubes.
The colour of the starting is orange. All of the tubes that contain the sample, QC and blank
digest at 150 ̊C for two hours. After cool it down, it were transferred into the conical flask
and add 2 drops of ferroin indicator then titrate the content with 0.1M Ferrous ammonium
sulfate. The colour will change to whether reddish brown. The titration result, the amount of
0.1M Ferrous ammonium sulfate in mL can calculate the amount of COD in the sample. The
higher the concentration of COD, the higher strength f the water which indicates the water is
polluted.
MATERIALS AND METHOD

Sample collection and preservation:

a) Containers: Plastic or glass

b) Preservative: Acidify with H2SO4 to pH < 2.0 and refrigerate
c) Holding times: 7 days

Reagent preparation

1. Standard potassium dichromate solution (K2Cr2O7), 0.0167M:-

4.913 g (K2Cr2O7), primary standard grade (previously dried at 103̊C for 2 hours), 167
mL H2SO4 and 33.3 g of HgSO4 in 500 mL distilled water prepared by dissolved all
chemicals.

2. Sulfuric acid reagent:-

5.50 g Ag2SO4 added per 1.0 litre of sulfuric acid (1 to 2 days required to dissolved
Ag2SO4) was prepared.

3. Standard ferrous ammonium sulphate (FAS) titrant, 0.10 M:-

39.2 g Fe(NH4)2(SO4)2.6H2O in 500 mL distilled water was dissolved. 20 mL of

concentrated H2SO4 added, cooled and diluted to 1000mL.

Standardised FAS solution as follows:-

5.0 mL standard (K2Cr2O7) pipetted in a beaker. 10 mL distilled water added. Cooled

to room temperature. 2 drops of ferroin indicator added and titrated with FAS titrant.

4. Ferroin indicator solution:-

1.485g 1,10-phenanthroline monohydrate dissolved and 0.695 g FeSO4.7H2O in

distilled water and diluted to 100 mL.

5. Mercuric sulphate, (HgSO4)

Analytical grade crystal

 6. Potassium hydrogen phthalate (KHP) standard:

Crushed lightly then dried potassium hydrogen phthalate (HOOCC6H4COOK) to

constant weight at 120̊C. 425 mg was dissolved in distilled water and diluted to 1000
mL. This solution has theoretical COD of 500mg O2/L. It is stable for up to 3 months
when refrigerated.

Analytical procedure

1. The digestion vessel and caps washed with 20% sulfuric acid before used to prevent
contamination.
2. Then, 2.5 mL sample, 1.5 mL K2Cr2O7 solution (0.0167M) and 3.5 mL sulfuric acid
reagent added to the digestion vessel.
3. The digestion vessel was capped tightly and inverted several times to mix it
completely.
4. The vessel placed in block digester and preheated to 150̊C for 2 hours.
5. After cooling to room temperature, the content transferred to the conical flask, the
burette filled with 0.1M ferrous ammonium sulphate.
6. 2 drops of ferroin indicator added. The contents against 0.1M ferrous ammonium
sulphate.
7. The titration continued until the color changes to reddish brown. The COD
concentration calculated.
RESULTS AND CALCULATION

DATA

Sample

Volume FAS before Volume FAS after titration,

Volume of FAS used, v2-v1
titration, v1 v2
10.8 15.3 4.5
15.3 20.5 5.2
20.5 24.6 4.1
24.6 29.6 5.0
29.6 33.6 4.0

The average FAS used in sample: 4.56 mL

Standard

Volume FAS before Volume FAS after titration,

Volume of FAS used, v2-v1
titration, v1 v2
1.0 9.2 8.2
9.2 15.7 6.5
15.7 24.8 9.1
24.8 33.4 8.6
33.4 34.9 1.5

The average FAS used in standard: 6.78mL

Blank

Volume FAS before Volume FAS after titration,

Volume of FAS used, v2-v1
titration, v1 v2
5.2 20.2 15.0
20.2 34.9 14.7
21.3 41.6 14.2
4.0 20.6 16.6
20.6 31.3 10.7

The average FAS used in standard: 14.23 mL

CALCULATION:

MOLARITY OF FAS SOLUTION:

Standard ammonium sulfate titrant (FAS), approximately 0.01 M. Standardize solution daily
against standard K2Cr2O7 digestion solution as follows:

 Pipette 5.00 mL digestion solution into small beaker.

 Add 10 mL reagent water to substitute for sample. Cool to room temperature.
 Add 1 to 2 drops diluted ferroin indicator and titrate with FAS titrant.

Volume 0.01667M K2Cr2O7 solution titrated,mL

= × 0.1000
Volume FAS used in titration,mL

5.0 mL
= × 0.10
44.5 mL

= 0.0113 M
CALCULATION OF COD:

(A−B)×C ×8000
COD, mg/L =
S

S = volume of sample taken (mL)

A = mL Fe(NH4)2(SO4)2 used for blank
B = mL Fe(NH4)2(SO4)2 used for sample
C = molarity of Fe(NH4)2(SO4)2
8000 = miliequivalent weight of oxygen x 1000 mL/L

(14.23−6.78)mL 0.0113 M ×8000

COD of standard, mg/L =
2.5 mL
= 269.39 mg/L

(14.23−4.56)mL 0.0113 M ×8000

COD of sample, mg/L =
2.5 mL
= 349.67 mg/L
DISCUSSION

COD means the chemical oxygen demand which means the measurements of
specified oxidants react with sample under control conditions. Moreover, it also can measure
the amount of potential pollution by calculate the amount of water that need to decompose of
organic matter with the addition amount of oxygen. COD measured in the laboratory in a
closed water sample by adding strong chemical oxidant under specific conditions of
temperature and period of time as in this experiment it is 2 hours under 150̊C. Oxidants that
are usually used in COD is potassium dichromate (K2Cr2O7) and sulfuric acid (H2SO4) as
both of the chemicals do not have a specific amount to consume oxygen that are organic and
inorganic.

In this experiment, there were about 15 tubes that used 5 tubes for the samples, 5
tubes for the blank and the other 5 is for QC. For the sample, the samples, 0.0167M, K2Cr2O7
solution and sulfuric acid reagent added in the test tubes then cap the tube. Make sure the
mixture is homogenous. As for the standard and blank, the differences is QC will used stock
standard COD and blank with distilled water in exchange with the sample. All the tubes
digest with COD digestor at 150̊C for 2 hours.

Cool it down before adding it with few drops of ferroin indicator to titrate it with 0.1M
ferrous ammonium sulphate. The color for the end point of the titration is reddish brick.

There are a few calculations is done in this experiment as the first one is to calculate
the molarity of FAS solution using this formula:-

Volume 0.01667M K2Cr2O7 solution titrated,mL

= × 0.1000
Volume FAS used in titration,mL

The molarity that we get for the FAS solution is 0.0113 M. Then the COD concentration
value can be calculated by using this formula:-

(A−B)×C ×8000
COD, mg/L =
S
 S = volume of sample taken (mL)
A = mL Fe(NH4)2(SO4)2 used for blank
B = mL Fe(NH4)2(SO4)2 used for sample
C = molarity of Fe(NH4)2(SO4)2
8000 = miliequivalent weight of oxygen x 1000 mL/L

The COD value for the standard is 269.39 mg/L and for the sample is 349.67 mg/L.

Table 2: The Parameter of COD based on the revised standards

According to table 1, from the value of the COD concentrations for the standard that
is 269.39 mg/L, the concentration of the COD level is medium because it is in the range of
the medium type of concentration. The sample concentration is 39.67 mg/L is also enter the
medium range of type concentration. Based on table 2, the water samples that used is in the
range of revised standard that is into sewage treatment or into the sea. This shows, the higher
the COD concentration of the sample the higher the strength of the water.
 There are a few precautions that can be taken during the experiment as the first one
the all the tubes need to be wash with 20% sulfuric acid to avoid contamination happened
during the experiment that can vary the titration. Besides that, a special precaution needs to
be taken is to make sure that the distilled water that used need to below in organic matter as it
can increase COD level for the blank.
CONCLUSION

As a conclusion, the objective of the experiment is achieved. The chemical oxygen

demand (COD) ranges (mg/L) for the standard is 269.39 mg/L and for the sample is 349.67
mg/L. The samples are in the medium range of type of water and the revised standard for the
sample is the samples should be into the sewage treatment or into the sea which mean the
concentration of COD level is quite high to enter the inland water.

REFERENCES

 Esteves, L., Oliveira, T., Elias, C., Bomfeti, C., Gonçalves, A., Oliveira, L., et
al. (2015). A fast and environment-friendly method for determination of
chemical oxygen demand byusing the heterogeneous Fenton-like process as
anoxidant. Talanta, 75 –80. (May, 23, 2019)

 ‘Understanding Laboratory Wastewater Tests: I. ORGANICS (BOD, COD,

TOC, O&G)’ by The University of Georgia Faculty of Engineering Outreach
Service (EOS) Retrieve at:
https://extension.uga.edu/publications/detail.html?number=C992&title=Under
standing%20Laboratory%20Wastewater%20Tests:%20I.%20ORGANICS%2
0(BOD,%20COD,%20TOC,%20O&G) (May, 23, 2019)

 ‘COD Method 410: Chemical Oxygen Demand (Titrimetric, Mid-Level)’ by

Envirnmental Express retrieved at: http://www.envexp.com/technical/method-
downloads/cod-method-410(May, 23, 2019)