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 reactwith 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 beovercome largely, though not completely, by complexing with mercuric sulfate (HgSO4) beforethe 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