Seventeen molecules of permanganate are equal to sixty molecules of molybdenum trioxid. The iron or steel is dissolved in nitric acid, evaporated to dryness, heated, and redissolved in hydrochloric acid, then treated again with nitric acid and evaporated until a clear and concentrated solution is obtained free from hydrochloric acid.
The solution obtained is diluted to forty cubic centimeters with water and washed into a 400 cubic centimeter flask, making the total volume about seventy-five cubic centimeters. Add strong ammonia, shaking after each addition, until the mass sets to a thick jelly from the ferric hydroxid. Add a few more cubic centimeters of ammonia and shake thoroughly, being sure the ammonia is present in excess. Add next nitric acid gradually, with shaking, until the precipitate has all dissolved; add enough more nitric acid to make the solution a clear amber color. The volume should now be about 250 cubic centimeters. Bring the solution to 85° and add, at once, forty cubic centimeters of molybdate solution of the following strength: Dissolve 100 grams of molybdic acid in 300 cubic centimeters of strong ammonia and 100 cubic centimeters of water, and pour the solution into 1,250 cubic centimeters of nitric acid (1.20); close the flask with a rubber stopper, wrap it in a thick cloth, and shake violently for five minutes. Collect the precipitate on a filter, using pump, and wash with dilute nitric acid (1 HNO₃ : 50 H₂O). If a thin film of the precipitate should adhere to the flask it can be removed by the ammonia in the next operation. Wash the molybdate precipitate into a 500 cubic centimeter flask with dilute ammonia (1 H₃N : 4 H₂O), using about thirty cubic centimeters. Add hot dilute sulfuric acid (1 H₂SO₄ : 4 H₂O) and cover the flask with a small funnel. Add ten grams of granulated zinc and heat until rapid action begins, and then heat gently for five minutes. The reduction is then complete. During the reduction the colors, pink, plum, pale green, and dark green, are seen in the molybdate solution, the latter color marking the end of the reaction.
To remove the zinc, pour through a large folded filter, wash with cold water, and fill up the filter once with cold water. But little oxidation takes place in this way. A port-wine color is seen on the filter, but this does not indicate a sufficient oxidation to make an error.
In titrating, the wine color becomes fainter and finally the solution is perfectly colorless and shows a single drop in excess of the permanganate. The permanganate solution, for convenience, is made so that one cubic centimeter is equal to 0.0001 gram of phosphorus. With iron its value is one cubic centimeter equals 0.006141 gram of iron; and one cubic centimeter equals 0.005574 gram of molybdenum trioxid.
112. Variation of Dudley and Noyes.—The method of Emmerton to determine small quantities of phosphoric acid, or of phosphorus in presence of a large excess of iron, has been modified by Dudley and Pease,[93] and by Noyes and Royse.[94] As modified, the method is not intended for fertilizer analysis, but the principle on which it rests may some time, with proper modifications, find application in fertilizer work. The reduction is accomplished in a Jones’ tube,[95] much simplified, so as to render it suitable for common use. The molybdic acid is reduced to a form, or series of forms, corresponding to molybdenum sesquioxid, as in the Emmerton method, and subsequently as in that method, titrated by a set solution of potassium permanganate.
The iron or steel filings, containing phosphorus, are brought into solution by means of nitric acid. For this purpose two grams of them are placed in a half liter flask together with fifty cubic centimeters of nitric acid of 1.18 specific gravity. The mixture is boiled for one minute, and ten cubic centimeters of permanganate solution of one and a quarter per cent added. Boil again until the pink color disappears. Ferrous sulfate solution is next to be carefully added, shaking meanwhile, until the solution clears. Cool to 50° and add eight cubic centimeters of ammonia of 0.90 specific gravity, stopper the flask, and shake until any precipitate which may form is redissolved. Cool or warm, as the case may be, until the solution is as many degrees above or below 60° as the molybdic solution is above or below 27°. Add sixty cubic centimeters of molybdic solution, stopper, and shake on a machine or by hand for five minutes. After remaining at rest for five minutes pour into a nine centimeter filter of fine texture and wash with the acid ammonium sulfate solution in quantities of from five to ten cubic centimeters each time. The filtrate and washings must be perfectly bright. Continue the washings until the filtrate gives no color with hydrogen sulfid.
Dissolve the yellow precipitate with twelve cubic centimeters of 0.96 ammonia diluted with an equal volume of water, and wash the filter with 100 cubic centimeters of water. Finally add to the filtrate and wash-water eighty cubic centimeters of water and ten of strong sulfuric acid. Pass the mixture through the Jones’ reducing tube and follow it with 200 cubic centimeters of water, taking care that no air enter the tube during the operations. The solution collected in the flask should be at once titrated with potassium permanganate.
Solutions used: (1) Nitric acid.—One part of nitric acid of 1.42 specific gravity and two parts of water by volume. The specific gravity of the mixture is about 1.18.
(2) Permanganate solution for oxidizing.—Dissolve 12.5 grams of potassium permanganate in one liter of water.
(3) Ferrous sulfate.—Fresh crystals not effervesced and free from phosphorus.