[Note 6: The sodium peroxide cannot be used in porcelain, platinum, or silver crucibles. It attacks iron and nickel as well; but crucibles made from these metals may be used if care is exercised to keep the temperature as low as possible. Preference is here given to iron crucibles, because the resulting ferric hydroxide is more readily brought into solution than the nickelic oxide from a nickel crucible. The peroxide must be dry, and must be protected from any admixture of dust, paper, or of organic matter of any kind, otherwise explosions may ensue.]
[Note 7: When an iron crucible is employed it is desirable to allow the fusion to become nearly cold before it is placed in water, otherwise scales of magnetic iron oxide may separate from the crucible, which by slowly dissolving in acid form ferrous sulphate, which reduces the chromate.]
[Note 8: Upon treatment with water the chromate passes into solution, the ferric hydroxide remains undissolved, and the excess of peroxide is decomposed with the evolution of oxygen. The subsequent boiling insures the complete decomposition of the peroxide. Unless this is complete, hydrogen peroxide is formed when the solution is acidified, and this reacts with the bichromate, reducing it and introducing a serious error.]
[Note 9: The addition of the sulphuric acid converts the sodium chromate to bichromate, which behaves exactly like potassium bichromate in acid solution.]
[Note 10: If a standard solution of a ferrous salt is not at hand, a weight of iron wire somewhat in excess of the amount which would be required if the chromite were pure FeO.Cr_{2}O_{3} may be weighed out and dissolved in sulphuric acid; after reduction of all the iron by stannous chloride and the addition of mercuric chloride, this solution may be poured into the chromate solution and the excess of iron determined by titration with standard bichromate solution.]
PERMANGANATE PROCESS FOR THE DETERMINATION OF IRON
Potassium permanganate oxidizes ferrous salts in cold, acid solution promptly and completely to the ferric condition, while in hot acid solution it also enters into a definite reaction with oxalic acid, by which the latter is oxidized to carbon dioxide and water.
The reactions involved are these:
10FeSO_{4} + 2KMnO_{4} + 8H_{2}S_{4} —> 5Fe_{2}(so_{4})_{3} + K_{2}so_{4} + 2MnSO_{4} + 8H_{2}O
5C_{2}H_{2}O_{4}(2H_{2}O) + 2KMnO_{4} +3H_{2}so_{4} —> K_{2}so_{4} + 2MnSO_{4} + 10Co_{2} + 1 H_{2}O.
These are the fundamental reactions upon which the extensive use of potassium permanganate depends; but besides iron and oxalic acid the permanganate enters into reaction with antimony, tin, copper, mercury, and manganese (the latter only in neutral solution), by which these metals are changed from a lower to a higher state of oxidation; and it also reacts with sulphurous acid, sulphureted hydrogen, nitrous acid, ferrocyanides, and most soluble organic bodies. It should be noted, however, that very few of these organic compounds react quantitatively with the permanganate, as is the case with oxalic acid and the oxalates.