Experiment 1: CHEMICAL OXYGEN DEMAND (COD)

1.0 OBJECTIVE
To determine the organic oxidize able matters content of water samples.

2.0 LEARNING OUTCOMES

i. To identify the principle of dichromate method to determine COD.
ii. To evaluate the water parameter quality in domestic waste water sample and water
supply.
iii. To choose appropriate analytical methodologies water quality measurement.

3.0 THEORY
The chemical oxygen demand (COD) is the amount of oxygen consumed to
completely chemically oxidize the organic water constituent to inorganic end products.
COD is an important, rapidly measured variable for the approximate determination of the
organic matter content of water samples. Some water samples may contain substances
that are difficult to oxidize. In these cases, because of incomplete oxidation under the
given test methods, COD values may be a poor measure of the theoretical oxygen
demand. It should also be noted that the significance of the COD value depends on the
composition of the water studied.
COD is used as a measurement of pollutants in natural and waste water to assess
the strength of discharged waste such as sewage and industrial effluent waters. It is
normally measured in both municipal and industrial waste water treatment plants and
gives an indication of the efficiency of the treatment process. The dichromate reflux
method is preferred over procedures using other oxidants because of superior oxidizing
ability, applicability to a wide variety of samples, and ease of manipulation. Oxidation of
most organic compounds is 95-100% the theoretical value.

4.0 EQUIPMENT & REAGENTS

4.1 Equipment:
1. COD reflux system – consisting Erlenmeyer flask (250 mL or 500 mL) with
ground glass 24/40 neck and 300—mm jacket Liebig West, or equivalent
condenser with 24/40 ground glass joint, and a hot plate having sufficient
power to produce at least 1.4 W/cm2 of heating surface.
2. Burette.
3. Pipette.
4. COD vial.
 4.2 Reagents:
i. Standard potassium dichromate (K2C2O7) solution (0.04167 M)
ii. Standard ferrous ammonium sulphate, (FAS) (Fe (NH4)2(SO4)2 solution
(0.25 M)
iii. Sulfuric acid reagent : Add Ag2SO4, to concentration H2SO4
iv. Ferroin indicator solution
v. Concentrated Sulfuric acid H2SO4

5.0 PROCEDURE

Reagents preparation for chemical oxygen demand:

1. Standard potassium dichromate solution (0.25N): Weight 12.259gm of previously

dried potassium dichromate at 103°C to 105°C for 2 hours and dissolve in distilled water and
make up to 1000 ml in volumetric flask.

2. Ferro indicator solution: Weigh 1.485gm of 110-Phenanthroline monohydrate and 695

mg ferrous sulphate dissolved in distilled water and dilute to 100 ml in volumetric flask.

3. 0.1N Ferrous Ammonium Sulphate (FAS): Weight 39.212gm of FAS and dissolve in
distilled water. Add 20 ml concentrated sulphuric acid, cool and dilute to 1000 ml in
volumetric flask.

4. Mercuric Sulphate (powder)

5. Sulphuric acid reagent:

6. Prepare sulphuric acid reagent by dissolving 22gm of silver sulphate in 2.5liter of

conc. sulphuric acid.

7. Potassium Hydrogen Phthalate standard:

8. Dissolve 0.425gm of KHP, previously dried at 120°C for 2 hours, in 1liter distilled
water. KHP has theoretical COD of 1.176 O2/mg and this solution has theoretical COD of
500 microgram of O2/ml of 500ppm.

9. 0.1N Potassium Dichromate Solution:

10. Dissolve 0.5gm of Potassium dichromate in 100ml of water

Standardization of FAS:

1. Take an iodine flask containing 90 ml of water.

2. Take 10 ml of 0.1N Potassium dichromate solution (prepare 0.1N Potassium
dichromate solution by dissolving about 0.5gm potassium dichromate in 100 ml of
water.
3. Add 12 ml of conc.sulphuric acid. Cool the content in the flask to laboratory
temperature.
4. Add 3 to 5 drops of Ferroin indicator solution.
5. Titrate against 0.1N ferrous ammonium sulphate solution until the colour changes
from blue to red.
6. Note down the initial burette reading (I) and note down the final burette reading.

Calculate the normality of FAS as follows.

Normality of FAS = W/ (TV×0.04904×10).

Where TV= (F-I) volume of ferrous ammonium sulphate solution consumed in titration

W= weight of potassium dichromate taken.

Determination of chemical oxygen demand, COD:

a. Pipette 20 ml of sample in 250 ml of refluxing flask.

b. Add approximately 400 mg (a pinch) of mercuric sulphate.
c. Add 10 ml of potassium dichromate by pipette.
d. 30 ml of conc.sulphuric acid reagent by measuring cylinder. Acid should be added in
controlled manner with mixing of the sample.
e. If the sample colour changes to green, dilute the sample and repeat the procedure for
diluted sample.
f. Connect the reflux flask through the condenser and reflux for a minimum period of
2hrs at 150°C.
g. Add 80 ml distilled water through condenser cool it to room temp and titrated with
standard sulphate using 2 to 4 drops of Ferroin indicator.
h. End point is the sharp colour change from blue green to brick red, even though blue
green reappear within minutes. Let the titrate value be ‘V’ ml
i. Reflux in same manner a blank with distilled water 20ml and follow the procedure
from previously. Let the titration value be ‘B’ ml.
j. Calculate the COD (mg/lt) as follows
COD= ((B-V) × N (FAS) × 8000)/vol of sample (ml).
6.0 RESULTS & CALCULATIONS

Table 1: FAS Standard Titration Data

Reading of burette / pipet Cone flask (Standard)

First Reading
Last Reading
Volume of FAS standard (mL)

Table 2: Sample and Blank Titration Data

Reading of burette / pipet (B ) Cone flask 1 (Sample) (A) Cone flask 2 (Blank)
First Reading
Last Reading
Volume of FAS standard (mL)

7.0 DATA ANALYSIS

7.1 Compute the molarity for the FAS standard using formula given (Table 1):

Volume 0.04167M K2Cr2O7

Solution titrated, mL
Normality of FAS solution = X 0.25
Volume FAS used in titration, Ml

Notes: The 0.25 is the Standard potassium dichromate solution, 0.04167M K2Cr2O7
undergoes a six-electron reduction reaction; the equivalent concentration is 6 X 0.04167M or
0.2500N.

7.2 Compute the COD concentration in mg/L for the samples using formula given (Table 2):

(B – A) X NFAS X 8000
COD as mg O2/L =
mL sample

Where:

A = mL FAS used for blank,

B = mL FAS used for sample,
NFAS = Normality of FAS, and
8000 = mill equivalent weight of oxygen X 1000 mL/L.

Notes: The 8000 multiplier is to express the results in units of milligrams per liter of oxsince
1 liter contains 1000 mL and the equivalent weight of oxygen is 6.
8.0 DISCUSSION

Q1. What is the purpose of using blank in this experiment?

Q2. Name the oxidation and reduction agent used in COD test.
Q3. Give the chemical formula of the following:
a. Sulfuric acid
b. Ferrous Ammonium Sulfate
c. Potassium dichromate
d. Argentum sulfate
e. Mercuric sulfate
Q4. Calculate the molecular mass of the following:
f. Sulfuric acid
g. Ferrous Ammonium Sulfate
h. Potassium dichromate
i. Argentum sulfate
j. Mercuric sulfate
Q5. Explain the precaution that must be taken during COD test?

9.0 REFERENCES

i. https://en.wikipedia.org/wiki/Chemical_oxygen_demand
ii. http://blog.hannainst.com/cod-testing
iii. http://vlab.amrita.edu/?sub=3&brch=272&sim=1413&cnt=2
iv. http://www.inclusive-science-engineering.com/determination-chemical-oxygen-
demand-cod-water-wastewater/