Chemical oxygen demand

In environmental chemistry, the chemical oxygen demand (COD) test is commonly

used to indirectly measure the amount of organic compounds in water. Most applications
of COD determine the amount of organic pollutants found in surface water (e.g. lakes and
rivers), making COD a useful measure of water quality. It is expressed in milligrams per
liter (mg/L), which indicates the mass of oxygen consumed per liter of solution. Older
references may express the units as parts per million (ppm).

Overview

The basis for the COD test is that nearly all organic compounds can be fully oxidized to
carbon dioxide with a strong oxidizing agent under acidic conditions. The amount of
oxygen required to oxidize an organic compound to carbon dioxide, ammonia, and water
is given by:

This expression does not include the oxygen demand caused by the oxidation of ammonia
into nitrate. The process of ammonia being converted into nitrate is referred to as
nitrification. The following is the correct equation for the oxidation of ammonia into
nitrate.

The second equation should be applied after the first one to include oxidation due to
nitrification if the oxygen demand from nitrification must be known. Dichromate does
not oxidize ammonia into nitrate, so this nitrification can be safely ignored in the
standard chemical oxygen demand test.

The International Organization for Standardization describes a standard method for

measuring chemical oxygen demand in ISO 6060 [1].

History

For many years, the strong oxidizing agent potassium permanganate (KMnO4) was used
for measuring chemical oxygen demand. Measurements were called oxygen consumed
from permanganate, rather than the oxygen demand of organic substances. Potassium
permanganate's effectiveness at oxidizing organic compounds varied widely, and in many
cases biochemical oxygen demand (BOD) measurements were often much greater than
results from COD measurements. This indicated that potassium permanganate was not
able to effectively oxidize all organic compounds in water, rendering it a relatively poor
oxidizing agent for determining COD.
Since then, other oxidizing agents such as ceric sulfate, potassium iodate, and potassium
dichromate have been used to determine COD. Of these, potassium dichromate (K2Cr2O7)
has been shown to be the most effective: it is relatively cheap, easy to purify, and is able
to nearly completely oxidize almost all organic compounds.

In these methods, a fixed volume with a known excess amount of the oxidant is added to
a sample of the solution being analyzed. After a refluxing digestion step, the initial
concentration of organic substances in the sample is calculated from a titrimetric or
spectrophotometric determination of the oxidant still remaining in the sample.

Using potassium dichromate

Potassium dichromate is a strong oxidizing agent under acidic conditions. (Acidity is

usually achieved by the addition of sulfuric acid.) The reaction of potassium dichromate
with organic compounds is given by:

where d = 2n/3 + a/6 - b/3 - c/2. Most commonly, a 0.25 N solution of potassium
dichromate is used for COD determination, although for samples with COD below
50 mg/L, a lower concentration of potassium dichromate is preferred.

In the process of oxidizing the organic substances found in the water sample, potassium
dichromate is reduced (since in all redox reactions, one reagent is oxidized and the other
is reduced), forming Cr3+. The amount of Cr3+ is determined after oxidization is complete,
and is used as an indirect measure of the organic contents of the water sample.

Blanks

Because COD measures the oxygen demand of organic compounds in a sample of water,
it is important that no outside organic material be accidentally added to the sample to be
measured. To control for this, a so-called blank sample is required in the determination of
COD (and BOD -biochemical oxygen demand - for that matter). A blank sample is
created by adding all reagents (e.g. acid and oxidizing agent) to a volume of distilled
water. COD is measured for both the water and blank samples, and the two are compared.
The oxygen demand in the blank sample is subtracted from the COD for the original
sample to ensure a true measurement of organic matter.

Measurement of excess

For all organic matter to be completely oxidized, an excess amount of potassium

dichromate (or any oxidizing agent) must be present. Once oxidation is complete, the
amount of excess potassium dichromate must be measured to ensure that the amount of
Cr3+ can be determined with accuracy. To do so, the excess potassium dichromate is
titrated with ferrous ammonium sulfate (FAS) until all of the excess oxidizing agent has
been reduced to Cr3+. Typically, the oxidation-reduction indicator Ferroin is added during
this titration step as well. Once all the excess dichromate has been reduced, the Ferroin
indicator changes from blue-green to reddish-brown. The amount of ferrous ammonium
sulfate added is equivalent to the amount of excess potassium dichromate added to the
original sample. and also we can determine COD by boiling the water sample and we can
determine CO2 ratio by the infra-red analyzer

Preparation Ferroin Indicator reagent

A solution of 1.485 g 1,10-phenanthroline monohydrate is added to a solution of 695 mg

FeSO4·7H2O in water, and the resulting red solution is diluted to 100 mL.

Calculations

The following formula is used to calculate COD:

where b is the volume of FAS used in the blank sample, s is the volume of FAS in the
original sample, and n is the normality of FAS. If milliliters are used consistently for
volume measurements, the result of the COD calculation is given in mg/L.

The COD can also be estimated from the concentration of oxidizable compound in the
sample, based on its stoichiometric reaction with oxygen to yield CO2 (assume all C goes
to CO2), H2O (assume all H goes to H2O), and NH3 (assume all N goes to NH3), using the
following formula:

COD = (C/FW)(RMO)(32)
Where C = Concentration of oxidizable compound in the sample,
FW = Formula weight of the oxidizable compound in the sample,
RMO = Ratio of the # of moles of oxygen to # of moles of oxidizable compound
in their reaction to CO2, water, and ammonia

For example, if a sample has 500 wppm of phenol:

C6H5OH + 7O2 → 6CO2 + 3H2O

COD = (500/94)(7)(32) = 1191 wppm

Inorganic interference

Some samples of water contain high levels of oxidizable inorganic materials which may
interfere with the determination of COD. Because of its high concentration in most
wastewater, chloride is often the most serious source of interference. Its reaction with
potassium dichromate follows the equation:
Prior to the addition of other reagents, mercuric sulfate can be added to the sample to
eliminate chloride interference.

The following table lists a number of other inorganic substances that may cause
interference. The table also lists chemicals that may be used to eliminate such
interference, and the compounds formed when the inorganic molecule is eliminated.

Inorganic molecule Eliminated by Elimination forms

Chloride Mercuric sulfate Mercuric chloride complex
Nitrite Sulfamic acid N2 gas
Ferrous iron - -
Sulfides - -