Acid digestion.—Place in a flask 100 cc. of the water, or, if the water is of high organic content, a smaller portion diluted to 100 cc. Add 10 cc. of sulfuric acid solution and 10 cc. of standard potassium permanganate and digest the liquid exactly 30 minutes in a bath of boiling water the level of which is kept above the level of the contents of the flask.[[70]][[71a]] If the quantity of permanganate is insufficient for complete oxidation repeat the digestion with a larger quantity; at least 5 cc. excess of the standard permanganate should be present when the ammonium oxalate solution is added. Remove the flask, add 10 cc. of the ammonium oxalate solution, and titrate with the standard permanganate until a faint but distinct color is obtained. If 100 cc. of water is used the number of cubic centimeters of potassium permanganate solution in excess of the number of cubic centimeters of ammonium oxalate solution is equal to parts per million of oxygen consumed.
If oxidizable mineral substances, such as ferrous iron, sulfide, or nitrite, are present in the sample corrections should be applied as accurately as possible by suitable procedures. Direct titration of the acidified sample in the cold, using a three-minute period of digestion, serves this purpose quite well for polluted surface waters and fairly well for purified sewage effluents. Few raw sewages containing no trade wastes need such a correction, but raw sewages containing “pickling” liquors do need it. If the sample contains both oxidizable mineral compounds and gaseous organic substances the latter should be driven off by heat and the sample allowed to cool before applying this test for the correction factor. If such corrections are made the fact should be stated with the amount of correction.
Period and temperature of digestion.—As the practice in regard to the period and temperature of digestion has varied widely it is difficult to compare the results obtained at one laboratory with those obtained at another. None of the methods gives absolute results. They are all relative[[26]][[29]][[57]] at best. Digesting 30 minutes at the boiling temperature is herein designated the recommended method. If samples are analyzed by any other method the method should be noted, and, representative results by the standard method should be placed on record for purposes of comparison.
OTHER METHODS.
Additional reagents.—1. Potassium iodide solution. Ten per cent solution, free from iodate.
2. Standard sodium thiosulfate. Dissolve 1.0 gram of the pure crystallized salt in 1 liter of distilled water. Standardize this solution against the standard potassium permanganate. As the thiosulfate solution does not keep well determine its actual strength at frequent intervals.
3. Starch indicator. Prepare as directed in the section on dissolved oxygen (pp. [65]–66).
4. Sodium hydroxide solution. Dissolve 1 part of pure sodium hydroxide in 2 parts of distilled water.
Certain widely practiced deviations from the standard procedure just described are noted in the following paragraphs.
1. Heat the acidified sample to boiling, add the permanganate solution, and digest for two minutes[[16]] at boiling temperature. This procedure is facilitated by agitating the liquid constantly with a small current of air to guard against bumping.