[Note 3: Barium sulphate, in a larger measure than most compounds, tends to carry down other substances which are present in the solution from which it separates, even when these other substances are relatively soluble, and including the barium chloride used as the precipitant. This is also notably true in the case of nitrates and chlorates of the alkalies, and of ferric compounds; and, since in this a.n.a.lysis ammonium nitrate has resulted from the neutralization of the excess of the nitric acid added to oxidize the iron, it is essential that this should be destroyed by repeated evaporation with a relatively large quant.i.ty of hydrochloric acid. During evaporation a mutual decomposition of the two acids takes place, and the nitric acid is finally decomposed and expelled by the excess of hydrochloric acid.
Iron is usually found in the precipitate of barium sulphate when thrown down from hot solutions in the presence of ferric salts. This, according to Kuster and Thiel (!Zeit. anorg. Chem.!, 22, 424), is due to the formation of a complex ion (Fe(SO_{4})_{2}) which precipitates with the Ba^{++} ion, while Richards (!Zeit. anorg. Chem.!, 23, 383) ascribes it to hydrolytic action, which causes the formation of a basic ferric complex which is occluded in the barium precipitate.
Whatever the character of the compound may be, it has been shown that it loses sulphuric anhydride upon ignition, causing low results, even though the precipitate contains iron.
The contamination of the barium sulphate by iron is much less in the presence of ferrous than ferric salts. If, therefore, the sulphur alone were to be determined in the ferrous ammonium sulphate, the precipitation by barium might be made directly from an aqueous solution of the salt, which had been made slightly acid with hydrochloric acid.]
[Note 4: The precipitation of the barium sulphate is probably complete at the end of a half-hour, and the solution may safely be filtered at the expiration of that time if it is desired to hasten the a.n.a.lysis.
As already noted, many precipitates of the general character of this sulphate tend to grow more coa.r.s.ely granular if digested for some time with the liquid from which they have separated. It is therefore well to allow the precipitate to stand in a warm place for several hours, if practicable, to promote ease of filtration. The filtrate and washings should always be carefully examined for minute quant.i.ties of the sulphate which may pa.s.s through the pores of the filter. This is best accomplished by imparting to the filtrate a gentle rotary motion, when the sulphate, if present, will collect at the center of the bottom of the beaker.]
[Note 5: A reduction of barium sulphate to the sulphide may very readily be caused by the reducing action of the burning carbon of the filter, and much care should be taken to prevent any considerable reduction from this cause. Subsequent ignition, with ready access of air, reconverts the sulphide to sulphate unless a considerable reduction has occurred. In the latter case it is expedient to add one or two drops of sulphuric acid and to heat cautiously until the excess of acid is expelled.]
[Note 6: Barium sulphate requires about 400,000 parts of water for its solution. It is not decomposed at a red heat but suffers loss, probably of sulphur trioxide, at a temperature above 900C.]
DETERMINATION OF SULPHUR IN BARIUM SULPHATE
PROCEDURE.--Weigh out, into platinum crucibles, two portions of about 0.5 gram of the sulphate. Mix each in the crucible with five to six times its weight of anhydrous sodium carbonate. This can best be done by placing the crucible on a piece of glazed paper and stirring the mixture with a clean, dry stirring-rod, which may finally be wiped off with a small fragment of filter paper, the latter being placed in the crucible. Cover the crucible and heat until a quiet, liquid fusion ensues. Remove the burner, and tip the crucible until the fused ma.s.s flows nearly to its mouth. Hold it in that position until the ma.s.s has solidified. When cold, the material may usually be detached in a lump by tapping the crucible or gently pressing it near its upper edge. If it still adheres, a cubic centimeter or so of water may be placed in the cold crucible and cautiously brought to boiling, when the cake will become loosened and may be removed and placed in about 250 cc.
of hot, distilled water to dissolve. Clean the crucible completely, rubbing the sides with a rubber-covered stirring-rod, if need be.
When the fused ma.s.s has completely disintegrated and nothing further will dissolve, decant the solution from the residue of barium carbonate (Note 1). Pour over the residue 20 cc. of a solution of sodium carbonate and 10 cc. of water and heat to gentle boiling for about three minutes (Note 2). Filter off the carbonate and wash it with hot water, testing the slightly acidified washings for sulphate and preserving any precipitates which appear in these tests. Acidify the filtrate with hydrochloric acid until just acid, bring to boiling, and slowly add hot barium chloride solution, as in the preceding determination. Add also any tests from the washings in which precipitates have appeared. Filter, wash, ignite, and weigh.
From the weight of barium sulphate, calculate the percentage of sulphur (S) in the sample.
[Note 1: This alkaline fusion is much employed to disintegrate substances ordinarily insoluble in acids into two components, one of which is water soluble and the other acid soluble. The reaction involved is:
BaSO_{4} + Na_{2}CO_{3}, --> BaCO_{3}, + Na_{2}SO_{4}.
As the sodium sulphate is soluble in water, and the barium carbonate insoluble, a separation between them is possible and the sulphur can be determined in the water-soluble portion.
It should be noted that this method can be applied to the purification of a precipitate of barium sulphate if contaminated by most of the substances mentioned in Note 3 on page 114. The impurities pa.s.s into the water solution together with the sodium sulphate, but, being present in such minute amounts, do not again precipitate with the barium sulphate.]
[Note 2: The barium carbonate is boiled with sodium carbonate solution before filtration because the reaction above is reversible; and it is only by keeping the sodium carbonate present in excess until nearly all of the sodium sulphate solution has been removed by filtration that the reversion of some of the barium carbonate to barium sulphate is prevented. This is an application of the principle of ma.s.s action, in which the concentration of the reagent (the carbonate ion) is kept as high as practicable and that of the sulphate ion as low as possible, in order to force the reaction in the desired direction (see Appendix).]
DETERMINATION OF PHOSPHORIC ANHYDRIDE IN APAt.i.tE
The mineral apat.i.te is composed of calcium phosphate, a.s.sociated with calcium chloride, or fluoride. Specimens are easily obtainable which are nearly pure and leave on treatment with acid only a slight siliceous residue.
For the purpose of gravimetric determination, phosphoric acid is usually precipitated from ammoniacal solutions in the form of magnesium ammonium phosphate which, on ignition, is converted into magnesium pyrophosphate. Since the calcium phosphate of the apat.i.te is also insoluble in ammoniacal solutions, this procedure cannot be applied directly. The separation of the phosphoric acid from the calcium must first be accomplished by precipitation in the form of ammonium phosph.o.m.olybdate in nitric acid solution, using ammonium molybdate as the precipitant. The "yellow precipitate," as it is often called, is not always of a definite composition, and therefore not suitable for direct weighing, but may be dissolved in ammonia, and the phosphoric acid thrown out as magnesium ammonium phosphate from the solution.
Of the substances likely to occur in apat.i.te, silicic acid alone interferes with the precipitation of the phosphoric acid in nitric acid solution.
PRECIPITATION OF AMMONIUM PHOSPh.o.m.oLYBDATE
PROCEDURE.--Grind the mineral in an agate mortar until no grit is perceptible. Transfer the substance to a weighing-tube, and weigh out two portions, not exceeding 0.20 gram each (Note 1) into two beakers of about 200 cc. capacity. Pour over them 20 cc. of dilute nitric acid (sp. gr. 1.2) and warm gently until solvent action has apparently ceased. Evaporate the solution cautiously to dryness, heat the residue for about an hour at 100-110C., and treat it again with nitric acid as described above; separate the residue of silica by filtration on a small filter (7 cm.) and wash with warm water, using as little as possible (Note 2). Receive the filtrate in a beaker (200-500 cc.).
Test the washings with ammonia for calcium phosphate, but add all such tests in which a precipitate appears to the original nitrate (Note 3).
The filtrate and washings must be kept as small as possible and should not exceed 100 cc. in volume. Add aqueous ammonia (sp. gr. 0.96) until the precipitate of calcium phosphate first produced just fails to redissolve, and then add a few drops of nitric acid until this is again brought into solution (Note 4). Warm the solution until it cannot be comfortably held in the hand (about 60C.) and, after removal of the burner, add 75 cc. of ammonium molybdate solution which has been !gently! warmed, but which must be perfectly clear. Allow the mixture to stand at a temperature of about 50 or 60C. for twelve hours (Notes 5 and 6). Filter off the yellow precipitate on a 9 cm.
filter, and wash by decantation with a solution of ammonium nitrate made acid with nitric acid.[1] Allow the precipitate to remain in the beaker as far as possible. Test the washings for calcium with ammonia and ammonium oxalate (Note 3).
[Footnote 1: This solution is prepared as follows: Mix 100 cc. of ammonia solution (sp. gr. 0.96) with 325 cc. of nitric acid (sp. gr.
1.2) and dilute with 100 cc. of water.]
Add 10 cc. of molybdate solution to the nitrate, and leave it for a few hours. It should then be carefully examined for a !yellow!
precipitate; a white precipitate may be neglected.
[Note 1: Magnesium ammonium phosphate, as noted below, is slightly soluble under the conditions of operation. Consequently the unavoidable errors of a.n.a.lysis are greater in this determination than in those which have preceded it, and some divergence may be expected in duplicate a.n.a.lyses. It is obvious that the larger the amount of substance taken for a.n.a.lysis the less will be the relative loss or gain due to unavoidable experimental errors; but, in this instance, a check is placed upon the amount of material which may be taken both by the bulk of the resulting precipitate of ammonium phosph.o.m.olybdate and by the excessive amount of ammonium molybdate required to effect complete separation of the phosphoric acid, since a liberal excess above the theoretical quant.i.ty is demanded. Molybdic acid is one of the more expensive reagents.]
[Note 2: Soluble silicic acid would, if present, partially separate with the phosph.o.m.olybdate, although not in combination with molybdenum. Its previous removal by dehydration is therefore necessary.]
[Note 3: When washing the siliceous residue the filtrate may be tested for calcium by adding ammonia, since that reagent neutralizes the acid which holds the calcium phosphate in solution and causes precipitation; but after the removal of the phosphoric acid in combination with the molybdenum, the addition of an oxalate is required to show the presence of calcium.]
[Note 4: An excess of nitric acid exerts a slight solvent action, while ammonium nitrate lessens the solubility; hence the neutralization of the former by ammonia.]
[Note 5: The precipitation of the phosph.o.m.olybdate takes place more promptly in warm than in cold solutions, but the temperature should not exceed 60C. during precipitation; a higher temperature tends to separate molybdic acid from the solution. This acid is nearly white, and its deposition in the filtrate on long standing should not be mistaken for a second precipitation of the yellow precipitate. The addition of 75 cc. of ammonium molybdate solution insures the presence of a liberal excess of the reagent, but the filtrate should be tested as in all quant.i.tative procedures.
The precipitation is probably complete in many cases in less than twelve hours; but it is better, when practicable, to allow the solution to stand for this length of time. Vigorous shaking or stirring promotes the separation of the precipitate.]
[Note 6: The composition of the "yellow precipitate" undoubtedly varies slightly with varying conditions at the time of its formation.
Its composition may probably fairly be represented by the formula, (NH_{4})_{3}PO_{4}.12MoO_{3}.H_{2}O, when precipitated under the conditions prescribed in the procedure. Whatever other variations may occur in its composition, the ratio of 12 MoO_{3}:1 P seems to hold, and this fact is utilized in volumetric processes for the determination of phosphorus, in which the molybdenum is reduced to a lower oxide and reoxidized by a standard solution of pota.s.sium permanganate. In principle, the procedure is comparable with that described for the determination of iron by permanganate.]
PRECIPITATION OF MAGNESIUM AMMONIUM PHOSPHATE
PROCEDURE.--Dissolve the precipitate of phosph.o.m.olybdate upon the filter by pouring through it dilute aqueous ammonia (one volume of dilute ammonia (sp. gr. 0.96) and three volumes of water, which should be carefully measured), and receive the solution in the beaker containing the bulk of the precipitate. The total volume of nitrate and washings should not much exceed 100 cc. Acidify the solution with dilute hydrochloric acid, and heat it nearly to boiling. Calculate the volume of magnesium ammonium chloride solution ("magnesia mixture") required to precipitate the phosphoric acid, a.s.suming 40 per cent P_{2}O_{5} in the apat.i.te. Measure out about 5 cc. in excess of this amount, and pour it into the acid solution. Then add slowly dilute ammonium hydroxide (1 volume of strong ammonia (sp. gr. 0.90) and 9 volumes of water), stirring constantly until a precipitate forms. Then add a volume of filtered, concentrated ammonia (sp. gr. 0.90) equal to one third of the volume of liquid in the beaker (Note 1). Allow the whole to cool. The precipitated magnesium ammonium phosphate should then be definitely crystalline in appearance (Note 2). (If it is desired to hasten the precipitation, the solution may be cooled, first in cold and then in ice-water, and stirred !constantly! for half an hour, when precipitation will usually be complete.)
Decant the clear liquid through a filter, and transfer the precipitate to the filter, using as wash-water a mixture of one volume of concentrated ammonia and three volumes of water. It is not necessary to clean the beaker completely or to wash the precipitate thoroughly at this point, as it is necessary to purify it by reprecipitation.
[Note 1: Magnesium ammonium phosphate is not a wholly insoluble substance, even under the most favorable a.n.a.lytical conditions. It is least soluble in a liquid containing one fourth of its volume of concentrated aqueous ammonia (sp. gr. 0.90) and this proportion should be carefully maintained as prescribed in the procedure. On account of this slight solubility the volume of solutions should be kept as small as possible and the amount of wash-water limited to that absolutely required.
A large excess of the magnesium solution tends both to throw out magnesium hydroxide (shown by a persistently flocculent precipitate) and to cause the phosphate to carry down molybdic acid. The tendency of the magnesium precipitate to carry down molybdic acid is also increased if the solution is too concentrated. The volume should not be less than 90 cc., nor more than 125 cc., at the time of the first precipitation with the magnesia mixture.]
[Note 2: The magnesium ammonium phosphate should be perfectly crystalline, and will be so if the directions are followed. The slow addition of the reagent is essential, and the stirring not less so.
Stirring promotes the separation of the precipitate and the formation of larger crystals, and may therefore be subst.i.tuted for digestion in the cold. The stirring-rod must not be allowed to scratch the gla.s.s, as the crystals adhere to such scratches and are removed with difficulty.]
REPRECIPITATION AND IGNITION OF MAGNESIUM AMMONIUM PHOSPHATE
A single precipitation of the magnesium compound in the presence of molybdenum compounds rarely yields a pure product. The molybdenum can be removed by solution of the precipitate in acid and precipitation of the molybdenum by sulphureted hydrogen, after which the magnesium precipitate may be again thrown down. It is usually more satisfactory to dissolve the magnesium precipitate and reprecipitate the phosphate as magnesium ammonium phosphate as described below.
PROCEDURE.--Dissolve the precipitate from the filter in a little dilute hydrochloric acid (sp. gr. 1.12), allowing the acid solution to run into the beaker in which the original precipitation was made (Note 1). Wash the filter with water until the wash-water shows no test for chlorides, but avoid an unnecessary amount of wash-water. Add to the solution 2 cc. (not more) of magnesia mixture, and then dilute ammonium hydroxide solution (sp. gr. 0.96), drop by drop, with constant stirring, until the liquid smells distinctly of ammonia. Stir for a few moments and then add a volume of strong ammonia (sp. gr.
0.90), equal to one third of the volume of the solution. Allow the solution to stand for some hours, and then filter off the magnesium ammonium phosphate, which should be distinctly crystalline in character. Wash the precipitate with dilute ammonia water, as prescribed above, until, finally, 3 cc. of the washings, after acidifying with nitric acid, show no evidence of chlorides. Test both filtrates for complete precipitation by adding a few cubic centimeters of magnesia mixture and allowing them to stand for some time.