Conclusion 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). Using potassium dichromate Potassium dichromate is a strong oxidizing agent under acidic conditions. (Acidity is usually achieved by the addition of sulfuric acid.) 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, 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 istitrated 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 reddishbrown. The amount of ferrous ammonium sulfate added is equivalent to the amount of excess potassium dichromate added to the original sample. 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