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C.6. DEGRADATION - CHEMICAL OXYGEN DEMAND



1. METHOD

1.1. INTRODUCTION
The purpose of the method is the measurement of the chemical oxygen demand (COD) of solid or
liquid organic substances in a standard, arbitrary manner, under fixed laboratory conditions.

Information on the formula of the substance will be useful to conduct this test and interpret the result
obtained (e.g. halogen salts, ferrous salts of organic compounds, organochlorine compounds).

1.2. DEFINITIONS AND UNITS

The chemical oxygen demand is a measure of the oxidizability of a substance, expressed as the
equivalent amount in oxygen of an oxidizing reagent consumed by the substance under fixed laboratory
conditions.

The result is expressed in grams of COD per gram of tested substance.

1.3. REFERENCE SUBSTANCES

Reference substances do not need to be employed in all cases when investigating a new substance.
They should serve primarily to calibrate the method from time to time and to allow comparison of
results when another method is applied.

1.4. PRINCIPLE OF THE TEST METHOD

A predetermined amount of the substance, dissolved or dispersed in water, is oxidized by potassium
dichromate in a strong sulphuric acid medium with silver sulphate as a catalyst, under reflux for t wo
hours. The residual dichromate is determined by titration with standardized ferrous ammonium
sulphate.

In case of chlorine-containing substances, mercuric sulphate (

) is added to reduce chloride

interference.

1.5. QUALITY CRITERIA

Because of the arbitrary manner of determination, COD is an 'oxidizability indicator' and as such is
used as a practical method to measure organic matter.

Chloride can interfere in this test; inorganic reducing or oxidizing agents may also interfere with the
COD determination.

Some cyclic compounds and many volatile substances (e.g. lower fatty acids) are not fully oxidized by
this test.

1.6. DESCRIPTION OF THE TEST METHOD

A preliminary solution or dispersion of the substance is prepared to obtain a COD between 250 and
600 mg per litre.

Remarks:

In the case of poorly soluble and non-dispersible substances, an amount of finely powdered substance
or liquid substance corresponding to about 5 mg of COD can be weighed and put in the experimental
apparatus with water.

The chemical oxygen demand (COD) is often and especially in case of poorly soluble substances
determined advantageously in a variant of the method, i.e., in a closed system with a pressure equaliser

After use, solutions containing mercur y salts should be treated to avoid dissemination of mercury in
the environment.


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(H. Kelkenberg, 1975). In this modification compounds which are only with difficulty determined by
the conventional method - e.g. acetic acid - may often be successfully quantified. The method also
fails, however, in the case of pyridine. If the potassium dichromate concentration, as prescribed in
ref.(1), is raised to 0,25 N (0,0416 M), the direct weighing-in of 5-10 mg of substance is facilitated
which is essential for the COD determination of poorly water soluble substances (ref. (2)).

Otherwise, the COD is then determined following any suitable national or internat ional standardized
method.


2. DATA AND EVALUATION

The COD contained in the experimental flask is calculated following the selected normalized method,
and converted to grams of COD per gram of tested substance.


3. REPORTING

The reference merhod used should be stated.

The chemical oxygen demand should be a mean of at least three measurements. All information and
remarks relevant to the interpretation of the results have to be reported, especially with regard to
impurities, physical state and inherent properties of the substance (if known) which would affect the
results.

The use of mercuric sulphate to minimize the chloride interference must be reported.


4. REFERENCES

(1) Kelkenberg, H.,Z. von Wasser und Abwasserforschung, 1975, vol. 8, 146.

(2) Gerike, P. The biodegradability testing of poorly water soluble compounds. Chemosphere, 1984,
vol. 13,169.

List of standardized methods, for example:

NBN T 91-201 Determination of t he chemical oxygen demand.

ISBN O 11 7512494 Chemical oxygen demand (dichromate value) of polluted and waste waters.

NF T 90-101 Determination of the chemical oxygen demand.

DS 217 = water analysis Determination of the chemical oxygen demand.

DIN 38409-H-41 Determination of the chemical oxygen demand (COD) within the range above 15 mg
per litre.

NEN 3235 5.3 Bepaling van het chemisch zuurstofverbruik.

ISO 6060 Water quality: chemical oxygen demand dichromate methods.