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Indian Institute of Technology Delhi
Department of Civil Engineering
CEL212 Environmental Engineering (Second Semester 2011-2012)
Experiment 4: Chemical Oxygen Demand (Closed Reflux Method)- Demonstration
1.0 Objective: Measure chemical oxygen demand
2.0 Background:
Chemical oxygen demand (COD) is termed as the amount of a specific oxidizing agent
that reacts with sample under controlled conditions and it is expressed as oxygen equivalence.
This parameter indicates the extent of organic matter contamination of water and is always
higher than the biochemical oxygen demand (BOD). It is used to indicate organic matter
contamination and it helps in knowing overall organic load to the receiving body.
Selection of Method
There are two methods for COD determination. The first method: open reflux method is
suitable for a wide range of wastes where large volume of sample is required (for samples with
COD= 50 mg O2/L). In the second method: closed reflux methods, small quantities of metallic
salt reagents are required and small quantities of hazardous waste is produced (for samples with
COD= 5 to 50 mg O2/L). In the closed reflux method, ampules and culture tubes with
premeasured reagents are used and then samples is placed in the tube and COD is determined. In
this experiment, closed reflux method is used and samples with COD < 50 mg O2/L are tested.
Reaction with dichromate solution of sample:
Potassium dichromate is a strong oxidizing agent and it can be used to prepare solution of exact
normality.
CnHaObNc+d Cr2O72- + (8d+c) H+ => nCO2 +[(a+8d-3c)/2]H2O+c NH4+ +2dCr3+ (1)
Here d=(2n/3)+(a/6)-(b/3)-(c/2)
During experiment, excess dichromate concentration is determined by titrating it with ferrous
ammonium sulfate (FAS). The reaction is given by:
6Fe2+ Cr2O72- + 14 H+ => 6Fe3++ 2Cr3+ +7H2O (2)
Here d=(2n/3)+(a/6)-(b/3)-(c/2)
Ferroin (ferrous 1,10-phenanthroline sulfate): It is used to indicate change in oxidation-reduction
potential of the solution and it indicates the condition when all dichromate has been reduced by
ferrous ion. It gives a very sharp brown color change which can be seen in spite of blue color
generated by the Cr3+ ions formed on reduction of the dichromate.
3.0 Lab Procedure:
Apparatus: Digestion vessels; block heater; microburet; ampule sealer. Borosilicate culture tubes
(16mm*100 mm or 20 mm*150mm) with TFE lined-screw caps are used. The block heater is
required to operate at 150±2°C with holes to accommodated digestion vessels. Do not use an
oven because of the possibility of leaking samples generating corrosive and explosive
atmosphere.
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Reagents:
a. Standard potassium dichromate digestion solution, 0.01667M: Add to about 500 mL distilled
water 4.903 g K2Cr2O7, primary standard grade, previously dried at 150°C for 2 h, 167 mL conc.
H2SO4, and 33.3 g HgSO4. Dissolve, cool to room temperature, and dilute to 1000 mL.
b. Sulfuric acid reagent:
c. Ferroin indicator solution: Dilute it by a factor of 5 as required. This indicator is used to
indicate change in oxidation-reduction potential of the solution.
d. Standard ferrous ammonium sulfate titrant (FAS), approximately 0.10M: Dissolve 39.2 g
Fe(NH4)2(SO4)2.6H2O in distilled water. Add 20 mL conc H2SO4, cool, and dilute to 1000 mL.
Standardize solution daily against standard K2Cr2O7 digestion solution as follows: Pipet 5.00
mL digestion solution into a 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.
Molarity of FAS solution = [VK2Cr2O7 ×0.1] / (VFAS) (3)
Where: VK2Cr2O7 = volume of K2Cr2O7 (mL); VFAS = volume of FAS (mL)
e. Sulfamic acid:
f. Potassium hydrogen phthalate standard:
Steps:
1. Wash culture tubes and caps with 20% H2SO4 before using to prevent contamination.
2. Place sample in culture tube or ampule and add digestion solution. Carefully run sulfuric
acid reagent down inside of vessel so an acid layer is formed under the sample-digestion
solution layer and tightly cap tubes or seal ampules, and invert each several times to mix
completely.
3. Place tubes or ampules in block digester preheated to 150°C and reflux for 2 h behind a
protective shield. CAUTION: These sealed vessels may be under pressure from gases
generated during digestion. Wear face and hand protection when handling and dangerous
pressures will be generated at 150°C.
4. Cool to room temperature and place vessels in test tube rack. Some mercuric sulfate may
precipitate out but this will not affect the analysis.
5. Remove culture tube caps and add small TFE-covered magnetic stirring bar. If ampules
are used, transfer contents to a larger container for titrating.
6. Add 0.05 to 0.10 mL (1 to 2 drops) ferroin indicator and stir rapidly on magnetic stirrer
while titrating with standardized 0.10M FAS. The end point is a sharp color change from
blue-green to reddish brown, although the bluegreen may reappear within minutes. In the
same manner reflux and titrate a blank containing the reagents and a volume of distilled
water equal to that of the sample.
7. COD is given by
COD as mg/L O2/L = [(A-B)× M ×8000) / (Vsample) (4)
Where: A = volume of FAS used for blank (mL);
B= volume of FAS used for sample (mL);
M=molarity of FAS; 8000= miliquivalent weight of oxygen ×1000 mL/L
Analyze samples in duplicates because of small sample size.
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4.0 Answer these questions also:
1. Why do the COD analysis and BOD analysis give different results for the same waste?
2. What could be inferred from the following samples concerning the relative ease of
biodegradability: Sample A (5-d BOD/COD=24/30) and Sample B (5-d
BOD/COD=10/50)?
5.0 Reference Materials:
AWWA, WEF, APHA, 1998, Standard Methods for the Examination of Water and Wastewater
(Methods: 5220 C. Closed Reflux Titrimetric Method)
Sawyer, C.N., McCarty, P.L., and Parkin, G.F. 2000. Chemistry for Environmental Engineering
4th Edition. Tata McGraw-Hill Publishing Company Limited.
