Laboratory 1: CHEMICAL OXYGEN DEMAND(COD) 2013

1.0 INTRODUCTION
The COD (Chemical Oxygen Demand) test is commonly used to indirectly measure
the amount of organic compound in water. Most applications of COD determine the
amount of organic pollutants found in surface water like lakes and rivers. COD also
represents the amount of chemically digestible organics (food). COD measures all
organics that were biochemically digestible as well as all the organics that can be digested
by heat and sulfuric acid. It is used in the same applications as BOD. COD has the
advantage over BOD in that the analysis can be completed within a few hours whereas
BOD requires 5 days. The major drawback of the COD test is the presence of hazardous
chemicals and toxic waste disposal.

2.0 OBJECTIVE
To measure the effectiveness of waste water sample (usually industrial waste water)
through the oxidation and reduction reaction

3.0 THEORY AND PRINCIPLES

COD or Chemical Oxygen Demand is the total measurement of all chemicals in the
water that can be oxidized. COD is used as a measurement of pollutants in natural and
wastewaters to assess the strength of discharged waste such as sewage and industrial effluent
waters. It is normally measured in both municipal and industrial wastewater 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 with wide variety of samples, and ease of manipulation. Oxidation
of most organic compounds is 95-100% the theoretical value.
Most types of organic matter are oxidized by a boiling mixture of chromic and suluric
acids. A sample is refluxed in strongly acid solutions with a known excess of potassium
dichromate (K2Cr2O7). After dilution the remaining unreduced K2Cr2O7 is titrated with
ferrous ammonium sulphate to determine the amount of K2Cr2O7 consumed and oxidizable
organic matter is calculated in terms of oxygen equivalent. Keep ratios of reagent weights,
volumes and strengths constant when sample volumes other than 50 ml are used. The
standard 2 hours reflux time may be reduced if it has been shown that a shorter period yields
the same results
 Laboratory 1: CHEMICAL OXYGEN DEMAND(COD) 2013

 The stoichiometry organic substances with dichromate is given in Eqn. 1:

CnHaOb + c Cr2O72- 8 c H+ Heat n CO2 + A + 8c/2 + H2O + 2 Cr3+

Organics Ag2O4 catalysts

where: c =2/3 n + a/6 – b/3

 Ferrous ion reacts with dichromate ion as in Eqn. 2. The oxidation process ended with
dichromate reduction:

6Fe2+ + 14H+ + Cr2O72- 6Fe3+ + 2 Cr3 + 7H2O , Eo = 1.33 volts

 Since 1 mole of Cr2O72- equals to 6 equivalent, so 6 x C is similar with the

equivalent number as required to oxidize 1 mole of organic substance.

 If oxygen is used as a oxidation agent, the calculation of equivalent numbers are as

Eqn. 3 :

O2 + 4e + 4H+ = 2H2O

 Equivalent Weigh = 32 g/mole ÷ 4 equivalent/ mole

= 8g / equivalent

Where else,6 x C x 8 = g O2 to oxidize 1 mole organic substance.

4.0 APPARATUS AND REAGENTS

a) 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.
b) Burette
c) Pipette
d) Glass beads
 Laboratory 1: CHEMICAL OXYGEN DEMAND(COD) 2013

e) Magnetic stirrer bars

i. Standard potassium dichromate (K2C2O7) solution (0.04167 M) : (Prepare by the

technician; Dissolve 12.259 g K2Cr2O7, primary standard grade, previously dried at
150°C for 2 hours in distilled water and dilute to 1000 mL).
Notes: This reagent undergoes a six-electron reduction reaction; the equivalent
concentration is 6 X 0.04167M or 0.2500N.
ii. Mercuric sulfate (Hg SO4)
iii. Sulfuric acid reagent
(Prepare by the technician : Add Ag2SO4, reagent or technical grade, crystals
or powder, to concentration H2SO4 at the rate of 5.5 g Ag2SO4 /kg H2 SO4. Mix)
iv. Ferroin indicator solution
(Prepare by the technician: Dissolve 1.485 g 1,10-phenanthroline
monohydrate and 695 mg FeSO4·7H2O in distilled water and dilute to 100 mL. This
indicator solution may be purchased already prepared)
v. Standard ferrous ammonium sulfate or FAS (Fe (NH4)2(SO4)2 solution (0.25 M)
titrant
(Prepare by the technician: Dissolve 98 g Fe(NH4)2(SO4)2·6H2O in distilled
water. Add 20 mL of concentration H2SO4, cool and dilute to 1000 mL. Standardize
this solution daily against standard K2Cr2O7 to about 100 mL. Add 30 mL
concentration H2SO4 and cool.

5.0 PROCEDURES
1. The substances must be added in Erlenmeyer flask following the sequences below:
a. Erlenmeyer flask no. 1 : 10 mL of asid asetic (C2H5COOH) sample.
Erlenmeyer flask no. 2 : 10 mL distilled water as a blank.
b. Placed in beaker 1 and 2 with:
i. 3 glass boiling beads – act as a antibumping
ii. HgSO4– 0.4g
iii. 0.0417M K2Cr2O7 – 10 mL
iv. Acid sulphuric reagent H2SO4 (contain Ag2SO4)- 30 mL
 Laboratory 1: CHEMICAL OXYGEN DEMAND(COD) 2013

c. The beaker is placed at the fume hood. H2SO4 is added slowly. Mixing to
avoid possible loss of volatile materials. Continued swirling and mixing while
adding sulphuric acid reagent.
CAUTION: Mix reflux mixture thoroughly before applying heat to prevent local
heating of flask bottom and a possible blowout of flask contents.
2. Flask is attached to condenser and turn on cooling water. Open end of condenser is
covered with a small beaker to prevent foreign material from entering refluxing
mixture and reflux for 2 hours. At a meantime, please proceed to procedure no. 6.
3. After 2 hours, cool wash down the condenser with distilled water. Continue cooling
the condenser to room temperature.
4. Reflux condenser is disconnected. The solution is transferred to the cone flask and the
mixture is diluted up to 150 mL with distilled water. Added with 3 drops of ferroin
indicator. Place the magnetic bars and stir it with magnetic stirrer.
5. Titrate K2Cr2O7 with ferrous ammonium sulphate (FAS). First and last reading should
be jot down in Table 2. Take as the end point of the titration the first sharp colour
change to blue-green. Stop titration, add 3 drops of ferroin indicator. Continue
titration until the colour change to reddish brown that persists for 1 minute or longer.
Stop titration and jot down the last reading in Table 2. Take a precaution that the end
point colour changes of titration is fast. Calculate the volume of FAS used in titration
in Table 2.
6. Preparation of Standard ferrous ammonium sulfate (FAS) titrant as follows:
a. Dilute 10 mL K2Cr2O7 standard (0.0417 M) to about 100 mL with adding 90
mL distilled water in the cone flask 250 mL. Swirl and mix slowly.
b. Slowly and carefully add 30 mL conc H2SO4 and cool. Refer to Figure 1,
titrate with the FAS titrant using 3 drops of ferroin indicator. First and last
reading should be jot down in Table 1.
c. Take as the end point of the titration the first sharp colour change to blue-
green. Stop titration, add 3 drops of ferroin indicator. Continue titration until
the colour change to reddish brown that persists for 1 minute or longer.
d. Take a precaution that the end point colour changes of titration is fast. Jotted
down the volume of FAS used in titration in Table 1.
 Laboratory 1: CHEMICAL OXYGEN DEMAND(COD) 2013

After heating in 2 hours

Fill the both of the Erlenmeyer cones with distill water up to 150 mL.
 Laboratory 1: CHEMICAL OXYGEN DEMAND(COD) 2013

6.0 RESULT AND DATA ANALYSIS

TABLE 1: FAS Standard Titration Data

Reading of buret / pipet Cone flask (Standard)

First Reading 13mL
Last Reading 23.1mL
Volume of FAS standard (mL) 10.1mL

Normality for the FAS standard using formula:

= 0.248
.
Range of normality of FAS is 0.23 < (N) < 0.27

Hence, the result is 0.248 so it is included in the range, 0.23 < 0.248 < 0.27.

The result was acceptable.

 Laboratory 1: CHEMICAL OXYGEN DEMAND(COD) 2013

TABLE 2: Sample and Blank Titration Data

Reading of burette / pipette (A ) Cone flask 1 (Sample) (B) Cone flask 2 (Blank)
First Reading 18.1mL 7.5mL
Last Reading 27.9mL 17.6mL
Volume of FAS standard (mL) 9.8mL 10.1mL

COD concentration in mg/L for the samples using formula

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

Where:

A = mL FAS used for sample

B = mL FAS used for blank
NFAS = Normality of FAS, and
8000 = milliequivalent weight of oxygen X 1000 mL/L.

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

(10.1 – 9.8) X 0.248 X 8000

COD as mg O2/L = ------------
9.8

= 60.734mg/L