Chemical Oxygen Demand (COD)

1
Introduction
Chemical oxygen demand (COD) is defined as the amount of a specified
oxidant that reacts with the sample under controlled conditions.
The quantity of oxidant consumed is expressed in terms of its oxygen
equivalence.
Because of its unique chemical properties, the dichromate ion (Cr2O72-) is
the specified oxidant; it is reduced to the chromic ion (Cr3+) in these
tests.

2
Introduction

Both organic and inorganic components of a

sample are subject to oxidation, but in most
cases the organic component predominates.
If it is desired to measure either organic or
inorganic COD alone, additional steps is not
described here must be taken to distinguish
one from the other.
COD is a defined test; the extent of sample
oxidation can be affected by
• digestion time,
• reagent strength,
• sample COD concentration.

3
Introduction

 COD often is used as a measurement of pollutants in wastewater and

natural waters.
Other related analytical values are biochemical oxygen demand (BOD),
total organic carbon (TOC), and total oxygen demand (TOD).
BOD is a measure of oxygen consumed by microorganisms under
specific conditions;
TOC is a measure of organic carbon in a sample;
TOD is a measure of the amount of oxygen consumed by all elements in
a sample when complete (total) oxidation is achieved.

In many cases it is possible to correlate two or more of these values for a

given sample.

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5
Introduction

In a COD analysis, hazardous wastes of mercury, hexavalent

chromium, sulfuric acid, silver and acids are generated. The closed reflux
method reduce these waste problems but may be less accurate and less
representative.
The major advantage of the COD test is the short time required for
evaluation. The determination can be made in about 2 hours rather than
the 5 days required for the measurement of BOD.
COD data can often be interpreted in terms of BOD values after sufficient
experience has been accumulated to establish reliable correlation factors.

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7
COD Analysis

Organic and oxidizable inorganic material present in a water sample is

oxidized by a standard potassium dichromate solution. In order for
potassium dichromate to oxidize organic matter completely, the solution
is made acidic and kept at an elevated temperature.
Reflux condensers (150 oC, 2 hours) are used to allow the sample to be
boiled without significant loss of volatile organic compounds.
Essentially complete oxidation to CO2, H2O, NH4+, etc. of many organic
compounds is obtained under the conditions of the test, especially in the
presence of Ag2SO4 catalyst. The reaction involved may be represented in
a general way as follows:

𝑎+8𝑐
CnHaOb + cCr2O72- + 8cH+ nCO2 + ( 2
)H2O + 2cCr3+

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 COD Analysis

KC8H3O4 + 10K2Cr2O7 + 41H2SO4 16CO2 + 46H2O + 10Cr2(SO4)3 + 11K2SO4

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COD Analysis
After the sample is refluxed with potassium dichromate and sulfuric
acid, excess dichromate is titrated with a reducing agent, ferrous
ammonium sulfate. The amount of oxidized organic matter is
proportional to the potassium dichromate consumed. Oxidation of Fe2+
proceeds as follows:
6Fe2+ + Cr2O72- + 14H+ 6Fe3+ + 2Cr3+ + 7H2O

Chloride ion present in wastewaters causes very high results in COD test
since it is oxidized by dichromate too.
6Cl- + Cr2O72- + 14H+ 3Cl2 + 2Cr3+ + 7H2O

This interference is eliminated by addition of mercuric sulfate to the

sample prior to the addition of other reagent.

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COD Analysis

11
Selection of Method
The open reflux method is suitable for a wide range of wastes where a
large sample size is preferred. The closed reflux methods are more
economical in the use of metallic salt reagents and generate smaller
quantities of hazardous waste, but require homogenization of samples
containing suspended solids to obtain reproducible results. Ampules and
culture tubes with premeasured reagents are available commercially.
Measurements of sample volumes as well as reagent volumes and
concentrations are critical. Consequently, obtain specifications as to limits
of error for premixed reagents from manufacturer before use.
 Determine COD values of >50 mg O2/L by using procedures open reflux
or closed reflux method.
 Use procedure open reflux method to determine, with lesser accuracy,
COD values from 5 to 50 mg O2/L.

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Open Reflux Method

Principle: Most types of organic matter are oxidized by a boiling mixture of chromic
and sulfuric acids. A sample is refluxed in strongly acid solution with a known
excess of potassium dichromate (K2Cr2O7). After digestion, the remaining
unreduced K2Cr2O7 is titrated with ferrous ammonium sulfate (FAS) to determine
the amount of K2Cr2O7 consumed and the oxidizable 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-h reflux
time may be reduced if it has been shown that a shorter period yields the same
results. Some samples with very low COD or with highly heterogeneous solids
content may need to be analyzed in replicate to yield the most reliable data.
Results are further enhanced by reacting a maximum quantity of dichromate,
provided that some residual dichromate remains.

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Open Reflux Method

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Closed Reflux, Titrimetric Method and
Colorimetric Method
Principle: Digestion is same as open reflux method
Colorimetric Method When a sample is digested, the dichromate ion
oxidizes COD material in the sample. This results in the change of chromium
from the hexavalent (VI) state to the trivalent (III) state. Both of these chromium
species are colored and absorb in the visible region of the spectrum. The
dichromate ion (Cr2O72-) absorbs strongly in the 400nm region. The chromic ion
absorbs strongly in the 600nm region, where the dichromate has nearly zero
absorption. In 9M sulfuric acid solution, the approximate molar extinction
coefficients for these chromium species are as follows:
 Cr3+ 50 L/mole cm at 604 nm;
 Cr2O72- 380 L/mole cm at 444 nm;
 Cr3+ 25 L/mole cm at 426 nm.
The Cr3+ ion has a minimum in the region of 400nm. Thus a working absorption
maximum is at 420nm.

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Closed Reflux, Titrimetric Method and
Colorimetric Method
Principle: Digestion is same as open reflux method
Titrimetric Method Prepare your sample for the COD test. Sample can be
diluted with distilled water.

Firstly, add potassium dichromate solution, sulfuric acid containing Ag 2SO4 and
tightly close the tubes and thoroughly mixed. Then add your sample to the tubes.
The tubes are then placed in Thermoreactor at 150oC for 2 hours. After two hours,
the samples are cooled to room temperature. HgSO4 may collapse but will not affect
this analysis. The tubes are emptied into glass beakers for easy titration. 2-3 drops
of ferroin indicator is added. It is mixed while titrated with FAS. The last point is
when it turns from blue-green to reddish brown. Record the volume of titrant used.

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COD is calculated from the following equation:

COD as mg O2/L =

where:
A = mL FAS used for blank,
B = mL FAS used for sample,
M = molarity of FAS, and

8000 = milliequivalent weight of oxygen X 1000 mL/L.

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Interferences and Limitations

Oxidation of most organic compounds is 95 to 100% of the theoretical value.

Pyridine and related compounds resist oxidation and volatile organic compounds will react
in proportion to their contact with the oxidant.
Straight-chain aliphatic compounds are oxidized more effectively in the presence of a silver
sulfate catalyst.
The most common interferent is the chloride ion. Chloride reacts with silver ion to
precipitate silver chloride, and thus inhibits the catalytic activity of silver.
Under the rigorous digestion procedures for COD analyses, chloride, bromide, or iodide can
react with dichromate to produce the elemental form of the halogen and the chromic ion.
!!!!Results then are in error on the high side.
The difficulties caused by the presence of the chloride can be overcome largely, though not
completely, by complexing with mercuric sulfate (HgSO4) before the refluxing procedure.
Although 1 g HgSO4 is specified for 50 mL sample, a lesser amount may be used where
sample chloride concentration is known to be less than 2000 mg/L, as long as a 10:1 weight
ratio of HgSO4:Cl- is maintained. Do not use the test for samples containing more than 2000
mg Cl-/L. Techniques designed to measure COD in saline waters are available.

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Interferences and Limitations

Ammonia and its derivatives, in the waste or generated from nitrogen-containing

organic matter, are not oxidized. However, elemental chlorine reacts with these
compounds. Hence, corrections for chloride interferences are difficult.
Nitrite (NO2-) exerts a COD of 1.1 mg O2/mg NO2--N. Because concentrations of NO2-
in waters rarely exceed 1 or 2 mg NO2--N /L, the interference is considered
insignificant and usually is ignored. To eliminate a significant interference due to
NO2-, add 10 mg sulfamic acid for each mg NO2--N present in the sample volume
used; add the same amount of sulfamic acid to the reflux vessel containing the
distilled water blank.
Reduced inorganic species such as ferrous iron, sulfide, etc., are oxidized
quantitatively under the test conditions. For samples containing significant levels
of these species, stoichiometric oxidation can be assumed from known initial
concentration of the interfering species and corrections can be made to the COD
value obtained.

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COD Calculation

Example 1: COD levels of 60 mg/L were measured in groundwater. It is

suspected that formaldehyde contamination is the main cause. What
concentration of hydrocarbons from formaldehyde is necessary to
account for all of the COD observed?
Answer: For simplicity, assume formaldehyde to have an average unit
formula of CH2O. The oxidation reaction is
CH2O + O2® CO2 + H2O
For each carbon atom in the fuel, 1 oxygen molecules are consumed.
Weight of 1 mole of unit formaldehyde = 12 + 2 + 16 = 30 g
Weight of 1 mole of O2 = 1 * 32 = 32 g
Weight ratio of oxygen to formaldehyde is: 32/30 = 1.07
A COD of 60 mg/L requires: 60/1.07 = 56.25 mg/L formaldehyde
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COD Calculation

Example 2: The results of a COD test for raw wastewater (50 mL used) are given.
Volumes of FAS used for blank and the sample are 24.53 mL and 12.88 mL,
respectively. The molarity of FAS is 0.242. Calculate the COD concentration for the
sample.
Answer:

COD as mg O2/L = =

COD as mg O2/L = 451.088 mg O2/L

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COD Calculation

Example 3: Determine the chemical oxygen demand of 50 mg/L glucose

(C6H12O6) solution? (C:12 g/mol, H:1 g/mol, O:16 g/mol)
Answer:
C6H12O6 + 6O2 6CO2 + 6H2O
For each mole of glucose in the solution, 6 moles of oxygen are consumed.
Weight of 1 mole of glucose = 6*12 + 12*1 + 6*16 = 180 g
? M of glucose = 50 mg/L*1g/1000mg*1mol/180g = 2.78*10-4 M
? M of O2 = 6*2.78*10-4 = 1.67*10-3 M
Weight of 1 mole of O2 = 32 g
? COD = 1.67*10-3 * 32 = 0.053 g O2/L

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COD Calculation

C6H12O6 + Cr2O72- CO2 + H2O + Cr3+

C6H12O6 + 6H2O 6CO2 + 24H+ + 24e-

Cr2O72- + 14H+ + 6e- 2Cr3+ + 7H2O 4
4Cr2O72- + 56H+ + 24e- 8Cr3+ + 28H2O
Total reaction:
C6H12O6 + 4Cr2O72- + 32H+ 6CO2 + 22H2O + 8Cr3+

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