An Introductory Course of Quantitative Chemical Analysis Part 16

Transfer the moist precipitate to a weighed porcelain or platinum crucible and ignite, using great care to raise the temperature slowly while drying the filter in the crucible, and to insure the ready access of oxygen during the combustion of the filter paper, thus guarding against a possible reduction of the phosphate, which would result in disastrous consequences both to the crucible, if of platinum, and the a.n.a.lysis. Do not raise the temperature above moderate redness until the precipitate is white. (Keep this precaution well in mind.) Ignite finally at the highest temperature of the Tirrill burner, and repeat the heating until the weight is constant.

If the ignited precipitate is persistently discolored by particles of unburned carbon, moisten the ma.s.s with a drop or two of concentrated nitric acid and heat cautiously, finally igniting strongly. The acid will dissolve magnesium pyrophosphate from the surface of the particles of carbon, which will then burn away. Nitric acid also aids as an oxidizing agent in supplying oxygen for the combustion of the carbon.

From the weight of magnesium pyrophosphate (Mg_{2}P_{2}O_{7}) obtained, calculate the phosphoric anhydride (P_{2}O_{5}) in the sample of apat.i.te.

[Note 1: The ionic change involved in the precipitation of the magnesium compound is

PO_{4}^{---} + NH_{4}^{+} + Mg^{++} --> [MgNH_{4}PO_{4}].

The magnesium ammonium phosphate is readily dissolved by acids, even those which are no stronger than acetic acid. This is accounted for by the fact that two of the ions into which phosphoric acid may dissociate, the HPO_{4}^{--} or H_{2}PO_{4}^{-} ions, exhibit the characteristics of very weak acids, in that they show almost no tendency to dissociate further into H^{+} and PO_{4}^{--} ions.

Consequently the ionic changes which occur when the magnesium ammonium phosphate is brought into contact with an acid may be typified by the reaction:

H^{+} + Mg^{++} + NH_{4}^{+} + PO_{4}^{---} --> Mg^{++} + NH_{4}^{+} + HPO_{4}^{--};

that is, the PO_{4}^{--} ions and the H^{+} ions lose their ident.i.ty in the formation of the new ion, HPO_{4}^{--}, and this continues until the magnesium ammonium phosphate is entirely dissolved.]

[Note 2: During ignition the magnesium ammonium phosphate loses ammonia and water and is converted into magnesium pyrophosphate:

2MgNH_{4}PO_{4} --> Mg_{2}P_{2}O_{7} + 2NH_{3} + H_{2}O.

The precautions mentioned on pages 111 and 123 must be observed with great care during the ignition of this precipitate. The danger here lies in a possible reduction of the phosphate by the carbon of the filter paper, or by the ammonia evolved, which may act as a reducing agent. The phosphorus then attacks and injures a platinum crucible, and the determination is valueless.]

a.n.a.lYSIS OF LIMESTONE

Limestones vary widely in composition from a nearly pure marble through the dolomitic limestones, containing varying amounts of magnesium, to the impure varieties, which contain also ferrous and manganous carbonates and siliceous compounds in variable proportions.

Many other minerals may be inclosed in limestones in small quant.i.ties, and an exact qualitative a.n.a.lysis will often show the presence of sulphides or sulphates, phosphates, and t.i.tanates, and the alkali or even the heavy metals. No attempt is made in the following procedures to provide a complete quant.i.tative scheme which would take into account all of these const.i.tuents. Such a scheme for a complete a.n.a.lysis of a limestone may be found in Bulletin No. 700 of the United States Geological Survey. It is a.s.sumed that, for these practice determinations, a limestone is selected which contains only the more common const.i.tuents first enumerated above.

DETERMINATION OF MOISTURE

The determination of the amount of moisture in minerals or ores is often of great importance. Ores which have been exposed to the weather during shipment may have absorbed enough moisture to appreciably affect the results of a.n.a.lysis. Since it is essential that the seller and buyer should make their a.n.a.lyses upon comparable material, it is customary for each a.n.a.lyst to determine the moisture in the sample examined, and then to calculate the percentages of the various const.i.tuents with reference to a sample dried in the air, or at a temperature a little above 100C., which, unless the ore has undergone chemical change because of the wetting, should be the same before and after shipment.

PROCEDURE.--Spread 25 grams of the powdered sample on a weighed watch-gla.s.s; weigh to the nearest 10 milligrams only and heat at 105C.; weigh at intervals of an hour, after cooling in a desiccator, until the loss of weight after an hour's heating does not exceed 10 milligrams. It should be noted that a variation in weight of 10 milligrams in a total weight of 25 grams is no greater relatively than a variation of 0.1 milligram when the sample taken weighs 0.25 gram

DETERMINATION OF THE INSOLUBLE MATTER AND SILICA

PROCEDURE.--Weigh out two portions of the original powdered sample (not the dried sample), of about 5 grams each, into 250 cc.

ca.s.seroles, and cover each with a watch-gla.s.s (Note 1). Pour over the powder 25 cc. of water, and then add 50 cc. of dilute hydrochloric acid (sp. gr. 1.12) in small portions, warming gently, until nothing further appears to dissolve (Note 2). Evaporate to dryness on the water bath. Pour over the residue a mixture of 5 cc. of water and 5 cc. of concentrated hydrochloric acid (sp. gr. 1.2) and again evaporate to dryness, and finally heat for at least an hour at a temperature of 110C. Pour over this residue 50 cc. of dilute hydrochloric acid (one volume acid (sp. gr. 1.12) to five volumes water), and boil for about five minutes; then filter and wash twice with the dilute hydrochloric acid, and then with hot water until free from chlorides. Transfer the filter and contents to a porcelain crucible, dry carefully over a low flame, and ignite to constant weight. The residue represents the insoluble matter and the silica from any soluble silicates (Note 3).

Calculate the combined percentage of these in the limestone.

[Note 1: The relatively large weight (5 grams) taken for a.n.a.lysis insures greater accuracy in the determination of the ingredients which are present in small proportions, and is also more likely to be a representative sample of the material a.n.a.lyzed.]

[Note 2: It is plain that the amount of the insoluble residue and also its character will often depend upon the strength of acid used for solution of the limestone. It cannot, therefore, be regarded as representing any well-defined const.i.tuent, and its determination is essentially empirical.]

[Note 3: It is probable that some of the silicates present are wholly or partly decomposed by the acid, and the soluble silicic acid must be converted by evaporation to dryness, and heating, into white, insoluble silica. This change is not complete after one evaporation.

The heating at a temperature somewhat higher than that of the water bath for a short time tends to leave the silica in the form of a powder, which promotes subsequent filtration. The siliceous residue is washed first with dilute acid to prevent hydrolytic changes, which would result in the formation of appreciable quant.i.ties of insoluble basic iron or aluminium salts on the filter when washing with hot water.

If it is desired to determine the percentage of silica separately, the ignited residue should be mixed in a platinum crucible with about six times its weight of anhydrous sodium carbonate, and the procedure given on page 151 should be followed. The filtrate from the silica is then added to the main filtrate from the insoluble residue.]

DETERMINATION OF FERRIC OXIDE AND ALUMINIUM OXIDE (WITH MANGANESE)

PROCEDURE.--To the filtrate from the insoluble residue add ammonium hydroxide until the solution just smells distinctly of ammonia, but do not add an excess. Then add 5 cc. of saturated bromine water (Note 1), and boil for five minutes. If the smell of ammonia has disappeared, again add ammonium hydroxide in slight excess, and 3 cc. of bromine water, and heat again for a few minutes. Finally add 10 cc. of ammonium chloride solution and keep the solution warm until it barely smells of ammonia; then filter promptly (Note 2). Wash the filter twice with hot water, then (after replacing the receiving beaker) pour through it 25 cc. of hot, dilute hydrochloric acid (one volume dilute HCl [sp. gr. 1.12] to five volumes water). A brown residue insoluble in the acid may be allowed to remain on the filter. Wash the filter five times with hot water, add to the filtrate ammonium hydroxide and bromine water as described above, and repeat the precipitation.

Collect the precipitate on the filter already used, wash it free from chlorides with hot water, and ignite and weigh as described for ferric hydroxide on page 110. The residue after ignition consists of ferric oxide, alumina, and mangano-manganic oxide (Mn_{3}O_{4}), if manganese is present. These are commonly determined together (Note 3).

Calculate the percentage of the combined oxides in the limestone.

[Note 1: The addition of bromine water to the ammoniacal solutions serves to oxidize any ferrous hydroxide to ferric hydroxide and to precipitate manganese as MnO(OH)_{2}. The solution must contain not more than a bare excess of hydroxyl ions (ammonium hydroxide) when it is filtered, on account of the tendency of the aluminium hydroxide to redissolve.

The solution should not be strongly ammoniacal when the bromine is added, as strong ammonia reacts with the bromine, with the evolution of nitrogen.]

[Note 2: The precipitate produced by ammonium hydroxide and bromine should be filtered off promptly, since the alkaline solution absorbs carbon dioxide from the air, with consequent partial precipitation of the calcium as carbonate. This is possible even under the most favorable conditions, and for this reason the iron precipitate is redissolved and again precipitated to free it from calcium. When the precipitate is small, this reprecipitation may be omitted.]

[Note 3: In the absence of significant amounts of manganese the iron and aluminium may be separately determined by fusion of the mixed ignited precipitate, after weighing, with about ten times its weight of acid pota.s.sium sulphate, solution of the cold fused ma.s.s in water, and volumetric determination of the iron, as described on page 66.

The aluminium is then determined by difference, after subtracting the weight of ferric oxide corresponding to the amount of iron found.

If a separate determination of the iron, aluminium, and manganese is desired, the mixed precipitate may be dissolved in acid before ignition, and the separation effected by special methods (see, for example, Fay, !Quant.i.tative a.n.a.lyses!, First Edition, pp. 15-19 and 23-27).]

DETERMINATION OF CALCIUM

PROCEDURE.--To the combined filtrates from the double precipitation of the hydroxides just described, add 5 cc. of dilute ammonium hydroxide (sp. gr. 0.96), and transfer the liquid to a 500 cc. graduated flask, washing out the beaker carefully. Cool to laboratory temperature, and fill the flask with distilled water until the lowest point of the meniscus is exactly level with the mark on the neck of the flask.

Carefully remove any drops of water which are on the inside of the neck of the flask above the graduation by means of a strip of filter paper, make the solution uniform by pouring it out into a dry beaker and back into the flask several times. Measure off one fifth of this solution as follows (Note 1): Pour into a 100 cc. graduated flask about 10 cc. of the solution, shake the liquid thoroughly over the inner surface of the small flask, and pour it out. Repeat the same operation. Fill the 100 cc. flask until the lowest point of the meniscus is exactly level with the mark on its neck, remove any drops of solution from the upper part of the neck with filter paper, and pour the solution into a beaker (400-500 cc.). Wash out the flask with small quant.i.ties of water until it is clean, adding these to the 100 cc. of solution. When the duplicate portion of 100 cc. is measured out from the solution, remember that the flask must be rinsed out twice with that solution, as prescribed above, before the measurement is made. (A 100 cc. pipette may be used to measure out the aliquot portions, if preferred.)

Dilute each of the measured portions to 250 cc. with distilled water, heat the whole to boiling, and add ammonium oxalate solution slowly in moderate excess, stirring well. Boil for two minutes; allow the precipitated calcium oxalate to settle for a half-hour, and decant through a filter. Test the filtrate for complete precipitation by adding a few cubic centimeters of the precipitant, allowing it to stand for fifteen minutes. If no precipitate forms, make the solution slightly acid with hydrochloric acid (Note 2); see that it is properly labeled and reserve it to be combined with the filtrate from the second calcium oxalate precipitation (Notes 3 and 4).

Redissolve the calcium oxalate in the beaker with warm hydrochloric acid, pouring the acid through the filter. Wash the filter five times with water, and finally pour through it aqueous ammonia. Dilute the solution to 250 cc., bring to boiling, and add 1 cc. ammonium oxalate solution (Note 5) and ammonia in slight excess; boil for two minutes, and set aside for a half-hour. Filter off the calcium oxalate upon the filter first used, and wash free from chlorides. The filtrate should be made barely acid with hydrochloric acid and combined with the filtrate from the first precipitation. Begin at once the evaporation of the solutions for the determination of magnesium as described below.

The precipitate of calcium oxalate may be converted into calcium oxide by ignition without previous drying. After burning the filter, it may be ignited for three quarters of an hour in a platinum crucible at the highest heat of the Bunsen or Tirrill burner, and finally for ten minutes at the blast lamp (Note 6). Repeat the heating over the blast lamp until the weight is constant. As the calcium oxide absorbs moisture from the air, it must (after cooling) be weighed as rapidly as possible.

The precipitate may, if preferred, be placed in a weighted porcelain crucible. After burning off the filter and heating for ten minutes the calcium precipitate may be converted into calcium sulphate by placing 2 cc. of dilute sulphuric acid in the crucible (cold), heating the covered crucible very cautiously over a low flame to drive off the excess of acid, and finally at redness to constant weight (Note 7).

From the weight of the oxide or sulphate, calculate the percentage of the calcium (Ca) in the limestone, remembering that only one fifth of the total solution is used for this determination.

[Note 1: If the calcium were precipitated from the entire solution, the quant.i.ty of the precipitate would be greater than could be properly treated. The solution is, therefore, diluted to a definite volume (500 cc.), and exactly one fifth (100 cc.) is measured off in a graduated flask or by means of a pipette.]

[Note 2: The filtrate from the calcium oxalate should be made slightly acid immediately after filtration, in order to avoid the solvent action of the alkaline liquid upon the gla.s.s.]