CHEMICAL OXYGEN DEMAND The following procedure uses a method of “baci ‘ation’ to determine the Chemical Oxygen Demand of a water sample. The method is rich in oxidation-reduction chemistry, and is used in this laboratory to illustrate a “redox titration" to you. INTRODUCTION The amount of oxygen dissolved in water is important to aquatic life. Decaying matter in sewage, industrial discharges, agricultural and urban runoff uses up the dissolved oxygen in water. The chemical oxygen demand (COD) is a measure of the amount of chemicals (usually organics) that consume dissolved oxygen. Biochemical oxygen demand (BOD) is a measure of the amount of oxygen consumed by the bacteria that are decomposing organic matter. Water quality standards for dissolved oxygen are set by state regulations to protect aquatic life. ‘Many lakes and streams across the country do not meet these standards. Improving the quality of water means controlling or improving agricultural practices, revegetating stream-banks, and controlling storm water. For those areas affected by industrial wastewater, improvements in wastewater purification are necessary. THE REDOX TITRATION Organic matter in aqueous samples may be determined by oxidation with dichromate. The amount of O> that is chemically equivalent to the dichromate consumed is defined as the chemical ‘oxygen demand (COD) of the sample. During the oxidation in which the sample is heated with a known excess of dichromate, organic matter is converted to carbon dioxide and water while dichromate is reduced to C>*: 1,0," +14H" +60" 9 2Cr* +70 The excess dichromate is determined by means of an oxidation-reduction titration with ferrous ammonium sulfate using an Fe({)-orthophenanthroline complex as an indicator. This method is called "back titration" in analytical chemistry. The half-reaction of the iron reduction is: Feet oo Feet em The excess dichromate is reduced in the back titration. Subtracting the mmoles of excess dichromate in the sample from the original mmoles of dichromate added to the sample, you can calculate the mmoles of dichromate consumed by the organic material in the sample. Since it is difficult to express the concentration of the myriad of oxidizable organic substances in a sample, COD results are expressed as the amount of oxygen (in mg Oz /L.) necessary to carry out the oxidation of the sample to CO and HO COD measurements are extremely useful to those concerned with water quality since they represent the amount of oxygen necessary for the aerobic biological oxidation of the organics in a water sample to COz and H20 if it is assumed the organics are biodegradable. The test does not, however, distinguish between oxidizable organics that are degraded and those that are not.Any substance that reduces Cr,07?~ will interfere with COD procedure. One of the most, common interferences is CI” which is quantitatively oxidized to Cly by dichromate. If chloride is known to be present in the sample, this difficulty is overcome in the method described by adding HgSO, to the reaction mixture to tie up C]~ as a soluble Hg(II) chloride complex. The procedure described here is applicable to samples having COD values of 50 mg/L or more. Samples are usually preserved for analysis with HySO at the rate of 2 mL of concentrated HySO4 per liter of sample. PRELABORATORY EXERCISES 1. Results of this experiment are reported in ppm Op or mg Oz/L. Thus we must consider the reduction of O> in determining quantities of oxygen present in our sample. Write out the reduction reaction for HO, (with O, as a product). 2. Write out the reduction reaction for dichromate. Determine the equivalent amount of O,--in other words, derive a balanced equation that relates moles of dichromate to moles of O2. Write out this equation in your notebook. For 1 dichromate molecule, how many electrons are consumed (or gained)? 3. What is the molar ratio of the reaction between Oz and dichromate? 4. Determine a balanced chemical equation for the back titration of dichromate. Write the reaction in your notebook. What is the ratio of Fe”* to dichromate for this system? EXPERIMENTAL Begin digesting (the oxidation process) your sample as soon as you start your experiment. Tl portion of the lab can take up to one hour and must be done in one period. Samples must be analyzed immediately after the digestion is complete, and must be done while the Fe solution is still very fresh. Further preparation for the experiment can be performed while your sample is digesting. The concentrated sulfuric acid used in this experiment will burn you badly. Be attentive to adhering drops on the glassware. Remove sulfuric acid with a lot of tap water. Don't drink it. In case of eye contact wash the eyes with flowing tap water for 15 minutes, then go to the doctor. Ferrous ammonium sulfate should not be ingested or inhaled. Dichromate is extremely toxic, and very hazardous to the environment. Unused dichromate should be returned to an appropriate waste container. DO NOT POUR IT DOWN THE SINK! 1. Potassium Dichromate Solution. Obtain 500 mL the stock potassium dichromate solution This solution is approximately 0.02 M.2, Unknown sample. Your instructor will give you a 10 oz. plastic bottle filled with a solution containing an organic compound. Quantitatively transfer your organic containing sample to a 250 mL volumetric flask and dilute to the mark with deionized water. Mix well. Your sample has been preserved by adding 2 mL of cone. HySO4 per liter. 3. Oxidation of sample, Prepare at least three portions of your sample using the following steps. Pipet 50.00 mL of standardized K7Cr707 into a 500 mL Erlenmeyer flask, place at least six boiling chips into the flask. Slowly add with stirring 50 mL of 9 M S04, cool the mixture to room temperature under a stream of tap water. Cautiously pipet 25.00 mL of your diluted sample into the cooled flask. Mix well, Using a hot piate, bring the solution to a gentle boil. Cover your sample with a small watch glass to minimize the loss of water vapor. Digest the sample until completely oxidized. ‘The endpoint is not detectable visually, since dichromate is still present in significant excess. This part of the experiment will take no more than an hour. Replace volume lost to evaporation with deionized water. Keep the liquid volume about constant, This is important. 4, Preparation of standard 0.15 M ferrous ammonium sulfate solution, Place approximately 200 mL of deionized water in a clean 400 ml. beaker. Slowly add 20 mL of 9 M HySO, and mix ‘Weigh accurately the appropriate amount of Fe(NH,),(SO,), -6H,0 to prepare 500 mL of 0.15 M solution. Dissolve it in the acid in the beaker, quantitatively transfer to a 500 mL. volumetric flask and dilute to the mark with deionized water. Mix well. 5. Standardization of potassium dichromate solution. Pipet 25.00 mL of the K2Cr907 into a 250 mL Erlenmeyer flask. Slowly add 50 mL of 9 M HSOq and mix. Allow the solution to cool and add 5 drops of ferroin indicator. Titrate with standard Fe(NH4)(SO4)2. The endpoint color change is quite distinct, going from blue-green to red-brown. Titrate at least two more 25 mL aliquots. 6. Titration of excess dichromate in your sample. Dilute the contents of the flask to about 250 mL with deionized water. Cool the solution to room temperature and add 5 drops of ferroin indicator. Titrate the sample with 0.15 M ferrous ammonium sulfate. RETURN_ANY UNUSED POTASSIUM DICHROMATE SOLUTION TO THE STOCK CONTAINER. CALCULATIONS 1. Report the volume of K3Crj07 titrated, the volume of. Fe(NH4)(SO4) used for each titration and the final molarity calculated for the dichromate solution. Your answer should be reported in terms of an average and a standard deviation,2, Compute the number of moles of K7Cr,07 consumed in oxidizing the organic material in each sample. Determine the number of moles of oxygen necessary to carry out the same oxidation, 3. Calculate the chemical oxygen demand (COD) of your diluted sample in mg O per liter 4, Report the average COD value for your diluted sample as mg Q» per liter. REFERENCES 1. Methods for the Chemical Analysis of Water and Wastes, Environmental Protection Agency, Analytical Quality Control Laboratory, Cincinnati, Ohio, 1971 2. Mancy, K. H., Instrumental Analysis for Water Pollution Control, Ann Arbor Science Publishers, Inc., Ann Arbor, Michigan, 1971. Standard Methods for the Examination of Water and Waste Water, 12th ed., American Public Health Association, Inc., New York, N.Y., 1965, p. 510.Chemical Oxygen Demand Answer Sheet Name. Course. Section, Date Mass of ferrous ammonium sulfate Volume of standard Fe(NH,):(S0,)2 ee Molarity of standard Fe(NH,)x(S0,)2 Standardization of KCr,07 Solution Aliquot 1 Aliquot 3 Volume of KxC1207 titrated Volume of Fe(NH.),S0.): used to reach the end-point Molarity of KxCr0; solution Average molarity of K2Cr.07 Analysis of Unknown Sample Aliquot 1 Aliquot 2 Aliquot 3 Moles of standard K3Cr07 added _. Volume of Fe(NH,)(S0.), used to reach the end-point —___ Molarity of K2Cr20; consumed Moles of O; consumed ~ Chemical Oxygen Demand Of the sample ——— Average COD (reported with Std. Dev.)