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).
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 .
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.
a lower concentration of potassium dichromate is preferred.
Using potassium dichromate
Potassium dichromate is a strong oxidizing agent under acidic conditions. In the process of oxidizing the organic substances found in the water sample. potassium dichromate is reduced (since in all redox reactions. and the two are compared. potassium dichromate (K2Cr2O7) has been shown to be the most effective: it is relatively cheap.b/3 . other oxidizing agents such as ceric sulfate. Once oxidation is complete.25 N solution of potassium dichromate is used for COD determination. The amount of Cr3+ is determined after oxidization is complete. and is able to nearly completely oxidize almost all organic compounds. COD is measured for both the water and blank samples. although for samples with COD below 50 mg/L.c/2. In these methods. an excess amount of potassium dichromate (or any oxidizing agent) must be present.for that matter). potassium iodate. To do so. acid and oxidizing agent) to a volume of distilled water. The oxygen demand in the blank sample is subtracted from the COD for the original sample to ensure a true measurement of organic matter. forming Cr3+. it is important that no outside organic material be accidentally added to the sample to be measured. and potassium dichromate have been used to determine COD.
Measurement of excess
For all organic matter to be completely oxidized. easy to purify. Most commonly. one reagent is oxidized and the other is reduced). a fixed volume with a known excess amount of the oxidant is added to a sample of the solution being analyzed. 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. Of these. the excess potassium dichromate is
Because COD measures the oxygen demand of organic compounds in a sample of water. the amount of excess potassium dichromate must be measured to ensure that the amount of Cr3+ can be determined with accuracy. To control for this. a so-called blank sample is required in the determination of COD (and BOD -biochemical oxygen demand . After a refluxing digestion step.) The reaction of potassium dichromate with organic compounds is given by:
where d = 2n/3 + a/6 . A blank sample is created by adding all reagents (e. (Acidity is usually achieved by the addition of sulfuric acid. a 0.Since then.g. and is used as an indirect measure of the organic contents of the water sample.
and n is the normality of FAS. Typically. Because of its high concentration in most wastewater. and NH3 (assume all N goes to NH3). FW = Formula weight of the oxidizable compound in the 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. the oxidation-reduction indicator Ferroin is added during this titration step as well. RMO = Ratio of the # of moles of oxygen to # of moles of oxidizable compound in their reaction to CO2. The amount of ferrous ammonium sulfate added is equivalent to the amount of excess potassium dichromate added to the original sample. H2O (assume all H goes to H2O). If milliliters are used consistently for volume measurements. Once all the excess dichromate has been reduced. s is the volume of FAS in the original sample. if a sample has 500 wppm of phenol: C6H5OH + 7O2 → 6CO2 + 3H2O COD = (500/94)(7)(32) = 1191 wppm
Some samples of water contain high levels of oxidizable inorganic materials which may interfere with the determination of COD.485 g 1. water. the result of the COD calculation is given in mg/L. the Ferroin indicator changes from blue-green to reddish-brown. using the following formula: COD = (C/FW)(RMO)(32) Where C = Concentration of oxidizable compound in the sample. and the resulting red solution is diluted to 100 mL. and ammonia For example. The COD can also be estimated from the concentration of oxidizable compound in the sample. Its reaction with potassium dichromate follows the equation:
.titrated with ferrous ammonium sulfate (FAS) until all of the excess oxidizing agent has been reduced to Cr3+.
The following formula is used to calculate COD:
where b is the volume of FAS used in the blank sample. based on its stoichiometric reaction with oxygen to yield CO2 (assume all C goes to CO2). chloride is often the most serious source of interference.10-phenanthroline monohydrate is added to a solution of 695 mg FeSO4·7H2O in water.
Prior to the addition of other reagents. mercuric sulfate can be added to the sample to eliminate chloride interference. The table also lists chemicals that may be used to eliminate such interference. and the compounds formed when the inorganic molecule is eliminated. The following table lists a number of other inorganic substances that may cause interference. Inorganic molecule Eliminated by Chloride Nitrite Ferrous iron Sulfides Sulfamic acid Elimination forms N2 gas -
Mercuric sulfate Mercuric chloride complex