Standard Methods for the Examination of Water and Wastewater
BIOCHEMICAL OXYGEN DEMAND (BOD)*#(1)
CHEMICAL OXYGEN DEMAND (COD)*#(2)
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 in Methods Section 5220B, Section 5220C, and Section 5220D; it is reduced to the chromic ion (Cr3+) in these tests. Both organic and inorganic components of a sample are subject to oxidation, but in most cases the organic component predominates and is of the greater interest. If it is desired to measure either organic or inorganic COD alone, additional steps 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, and sample COD concentration. 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). In many cases it is possible to correlate two or more of these values for a given sample. 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 a COD analysis, hazardous wastes of mercury, hexavalent chromium, sulfuric acid, silver, and acids are generated. Methods Section 5220C and Section 5220D reduce these waste problems but may be less accurate and less representative. (See ¶ 2 below.) 1. Selection of Method The open reflux method (B) is suitable for a wide range of wastes where a large sample size is preferred. The closed reflux methods (C and D) 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 Section 5220B.4a, Section 5220C.4, or Section 5220D.4. Use procedure Section 5220B.4b to determine, with lesser © Copyright 1999 by American Public Health Association, American Water Works Association, Water Environment Federation
Standard Methods for the Examination of Water and Wastewater accuracy, COD values from 5 to 50 mg O2/L. 2. 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. Bromide, iodide, and any other reagent that inactivates the silver ion can interfere similarly. Such interferences are negative in that they tend to restrict the oxidizing action of the dichromate ion itself. However, 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...
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