An Introductory Course of Quantitative Chemical Analysis Part 7

Repeat the standardization until the results are concordant within at least two parts in one thousand.

[Note 1: The hydrochloric acid is added to the ferrous solution to insure the presence of at least sufficient free acid for the t.i.tration, as required by the equation on page 48.

The solution of the wire in hot acid and the short boiling insure the removal of compounds of hydrogen and carbon which are formed from the small amount of carbon in the iron. These might be acted upon by the bichromate if not expelled.]

[Note 2: It is plain that all the iron must be reduced to the ferrous condition before the t.i.tration begins, as some oxidation may have occurred from the oxygen of the air during solution. It is also evident that any excess of the agent used to reduce the iron must be removed; otherwise it will react with the bichromate added later.

The reagents available for the reduction of iron are stannous chloride, sulphurous acid, sulphureted hydrogen, and zinc; of these stannous chloride acts most readily, the completion of the reaction is most easily noted, and the excess of the reagent is most readily removed. The latter object is accomplished by oxidation to stannic chloride by means of mercuric chloride added in excess, as the mercuric salts have no effect upon ferrous iron or the bichromate. The reactions involved are:

2FeCl_{3} + SnCl_{2} --> 2FeCl_{2} + SnCl_{4} SnCl_{2} + 2HgCl_{2} --> SnCl_{4} + 2HgCl

The mercurous chloride is precipitated.

It is essential that the solution should be cold and that the stannous chloride should not be present in great excess, otherwise a secondary reaction takes place, resulting in the reduction of the mercurous chloride to metallic mercury:

SnCl_{2} + 2HgCl --> SnCl_{4} + 2Hg.

The occurrence of this secondary reaction is indicated by the darkening of the precipitate; and, since pota.s.sium bichromate oxidizes this mercury slowly, solutions in which it has been precipitated are worthless as iron determinations.]

[Note 3: The solution should be allowed to stand about three minutes after the addition of mercuric chloride to permit the complete deposition of mercurous chloride. It should then be t.i.trated without delay to avoid possible reoxidation of the iron by the oxygen of the air.]

DETERMINATION OF IRON IN LIMONITE

PROCEDURE.--Grind the mineral (Note 1) to a fine powder. Weigh out accurately two portions of about 0.5 gram (Note 2) into porcelain crucibles; heat these crucibles to dull redness for ten minutes, allow them to cool, and place them, with their contents, in beakers containing 30 cc. of dilute hydrochloric acid (sp. gr. 1.12). Heat at a temperature just below boiling until the undissolved residue is white or until solvent action has ceased. If the residue is white, or known to be free from iron, it may be neglected and need not be removed by filtration. If a dark residue remains, collect it on a filter, wash free from hydrochloric acid, and ignite the filter in a platinum crucible (Note 3). Mix the ash with five times its weight of sodium carbonate and heat to fusion; cool, and disintegrate the fused ma.s.s with boiling water in the crucible. Unite this solution and precipitate (if any) with the acid solution, taking care to avoid loss by effervescence. Wash out the crucible, heat the acid solution to boiling, add stannous chloride solution until it is colorless, avoiding a large excess (Note 4); cool, and when !cold!, add 40 cc. of mercuric chloride solution, dilute to 200 cc., and proceed with the t.i.tration as already described.

From the standardization data already obtained, and the known weight of the sample, calculate the percentage of iron (Fe) in the limonite.

[Note 1: Limonite is selected as a representative of iron ores in general. It is a native, hydrated oxide of iron. It frequently occurs in or near peat beds and contains more or less organic matter which, if brought into solution, would be acted upon by the pota.s.sium bichromate. This organic matter is destroyed by roasting. Since a high temperature tends to lessen the solubility of ferric oxide, the heat should not be raised above low redness.]

[Note 2: It is sometimes advantageous to dissolve a large portion--say 5 grams--and to take one tenth of it for t.i.tration. The sample will then represent more closely the average value of the ore.]

[Note 3: A platinum crucible may be used for the roasting of the limonite and must be used for the fusion of the residue. When used, it must not be allowed to remain in the acid solution of ferric chloride for any length of time, since the platinum is attacked and dissolved, and the platinic chloride is later reduced by the stannous chloride, and in the reduced condition reacts with the bichromate, thus introducing an error. It should also be noted that copper and antimony interfere with the determination of iron by the bichromate process.]

[Note 4: The quant.i.ty of stannous chloride required for the reduction of the iron in the limonite will be much larger than that added to the solution of iron wire, in which the iron was mainly already in the ferrous condition. It should, however, be added from a dropper to avoid an unnecessary excess.]

DETERMINATION OF CHROMIUM IN CHROME IRON ORE

PROCEDURE.--Grind the chrome iron ore (Note 1) in an agate mortar until no grit is perceptible under the pestle. Weigh out two portions of 0.5 gram each into iron crucibles which have been scoured inside until bright (Note 2). Weigh out on a watch-gla.s.s (Note 3), using the rough balances, 5 grams of dry sodium peroxide for each portion, and pour about three quarters of the peroxide upon the ore. Mix ore and flux by thorough stirring with a dry gla.s.s rod. Then cover the mixture with the remainder of the peroxide. Place the crucible on a triangle and raise the temperature !slowly! to the melting point of the flux, using a low flame, and holding the lamp in the hand (Note 4). Maintain the fusion for five minutes, and stir constantly with a stout iron wire, but do not raise the temperature above moderate redness (Notes 5 and 6).

Allow the crucible to cool until it can be comfortably handled (Note 7) and then place it in a 300 cc. beaker, and cover it with distilled water (Note 8). The beaker must be carefully covered to avoid loss during the disintegration of the fused ma.s.s. When the evolution of gas ceases, rinse off and remove the crucible; then heat the solution !while still alkaline! to boiling for fifteen minutes. Allow the liquid to cool for a few minutes; then acidify with dilute sulphuric acid (1:5), adding 10 cc. in excess of the amount necessary to dissolve the ferric hydroxide (Note 9). Dilute to 200 cc., cool, add from a burette an excess of a standard ferrous solution, and t.i.trate for the excess with a standard solution of pota.s.sium bichromate, using the outside indicator (Note 10).

From the corrected volumes of the two standard solutions, and their relations to normal solutions, calculate the percentage of chromium in the ore.

[Note 1: Chrome iron ore is essentially a ferrous chromite, or combination of FeO and Cr_{2}O_{3}. It must be reduced to a state of fine subdivision to ensure a prompt reaction with the flux.]

[Note 2: The scouring of the iron crucible is rendered much easier if it is first heated to bright redness and plunged into cold water. In this process oily matter is burned off and adhering scale is caused to chip off when the hot crucible contracts rapidly in the cold water.]

[Note 3: Sodium peroxide must be kept off of balance pans and should not be weighed out on paper, as is the usual practice in the rough weighing of chemicals. If paper to which the peroxide is adhering is exposed to moist air it is likely to take fire as a result of the absorption of moisture, and consequent evolution of heat and liberation of oxygen.]

[Note 4: The lamp should never be allowed to remain under the crucible, as this will raise the temperature to a point at which the crucible itself is rapidly attacked by the flux and burned through.]

[Note 5: The sodium peroxide acts as both a flux and an oxidizing agent. The chromic oxide is dissolved by the flux and oxidized to chromic anhydride (CrO_{3}) which combines with the alkali to form sodium chromate. The iron is oxidized to ferric oxide.]

[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 pa.s.ses 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 pota.s.sium 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 t.i.tration with standard bichromate solution.]

PERMANGANATE PROCESS FOR THE DETERMINATION OF IRON

Pota.s.sium 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 pota.s.sium 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 quant.i.tatively with the permanganate, as is the case with oxalic acid and the oxalates.

Pota.s.sium permanganate is acted upon by hydrochloric acid; the action is rapid in hot or concentrated solution (particularly in the presence of iron salts, which appear to act as catalyzers, increasing the velocity of the reaction), but slow in cold, dilute solutions.

However, the greater solubility of iron compounds in hydrochloric acid makes it desirable to use this acid as a solvent, and experiments made with this end in view have shown that in cold, dilute hydrochloric acid solution, to which considerable quant.i.ties of manganous sulphate and an excess of phosphoric acid have been added, it is possible to obtain satisfactory results.

It is also possible to replace the hydrochloric acid by evaporating the solutions with an excess of sulphuric acid until the latter fumes.

This procedure is somewhat more time-consuming, but the end-point of the permanganate t.i.tration is more permanent. Both procedures are described below.

Pota.s.sium permanganate has an intense coloring power, and since the solution resulting from the oxidation of the iron and the reduction of the permanganate is colorless, the latter becomes its own indicator.

The slightest excess is indicated with great accuracy by the pink color of the solution.