[Note 2: The reaction between oxalates and permanganates takes place quantitatively only in hot acid solutions. The temperatures must not fall below 70 deg.C.]
DETERMINATION OF IRON IN LIMONITE
The procedures, as here prescribed, are applicable to iron ores in general, provided these ores contain no constituents which are reduced by zinc or stannous chloride and reoxidized by permanganates. Many iron ores contain titanium, and this element among others does interfere with the determination of iron by the process described. If, however, the solutions of such ores are treated with sulphureted hydrogen or sulphurous acid, instead of zinc or stannous chloride to reduce the iron, and the excess reducing agent removed by boiling, an accurate determination of the iron can be made.
Procedure.—Grind the mineral to a fine powder. Weigh out two portions of about 0.5 gram each into small porcelain crucibles. Roast the ore at dull redness for ten minutes (Note 1), allow the crucibles to cool, and place them and their contents in casseroles containing 30 cc. of dilute hydrochloric acid (sp. gr. 1.12).
Proceed with the solution of the ore, and the treatment of the residue, if necessary, exactly as described for the bichromate process on page 56. When solution is complete, add 6 cc. of concentrated sulphuric acid to each casserole, and evaporate on the steam bath until the solution is nearly colorless (Note 2). Cover the casseroles and heat over the flame of the burner, holding the casserole in the hand and rotating it slowly to hasten evaporation and prevent spattering, until the heavy white fumes of sulphuric anhydride are freely evolved (Note 3). Cool the casseroles, add 100 cc. of water (measured), and boil gently until the ferric sulphate is dissolved; pour the warm solution through the reductor which has been previously washed; proceed as described under standardization, taking pains to use the same volume and strength of acid and the same volume of wash-water as there prescribed, and titrate with the permanganate solution in the reductor flask, using the ferrous sulphate solution if the end-point should be overstepped.
From the corrected volume of permanganate solution used, calculate the percentage of iron (Fe) in the limonite.
[Note 1: The preliminary roasting is usually necessary because, even though the sulphuric acid would subsequently char the carbonaceous matter, certain nitrogenous bodies are not thereby rendered insoluble in the acid, and would be oxidized by the permanganate.]
[Note 2: The temperature of the steam bath is not sufficient to volatilize sulphuric acid. Solutions may, therefore, be left to evaporate overnight without danger of evaporation to dryness.]
[Note 3: The hydrochloric acid, both free and combined, is displaced by the less volatile sulphuric acid at its boiling point. Ferric sulphate separates at this point, since there is no water to hold it in solution and care is required to prevent bumping. The ferric sulphate usually has a silky appearance and is easily distinguished from the flocculent silica which often remains undissolved.]