Chapter III: Part 3

=55. The Molybdic Acid Method, as Practiced by Direction of the Union of the German Experiment Stations.=—The method adopted by the German Experiment Stations is essentially that used at Halle.[41] The samples are brought into solution in the following way: For the estimation of phosphoric acid in bone-meal, fish-guano and raw phosphates, and the total phosphoric acid in superphosphates, five grams of the sample are dissolved in fifty cubic centimeters of aqua regia, made of three parts of hydrochloric acid of 1.12 specific gravity and one part of nitric acid of 1.25 specific gravity, or the solution may be made of a mixture of twenty cubic centimeters of nitric acid of 1.42 specific gravity and fifty cubic centimeters of sulfuric acid of 1.8 specific gravity. The boiling should continue for half an hour. The solution is made up to half a liter and filtered. Fifty cubic centimeters of the filtrate containing the phosphoric acid, with double superphosphates twenty-five cubic centimeters, are digested with 200 cubic centimeters of ammonium molybdate solution for three hours at 50° in a water-bath and, after cooling, filtered, so that as little as possible of the precipitate is collected upon the filter, which is made of strong paper.

The yellow precipitate is washed by decantation in the flask nine times with twenty cubic centimeters of molybdic solution diluted with one volume of water and the filter washed out once with the same quantity of liquid. The funnel, with the filter, is immediately placed upon the flask and the portion of the precipitate collected in the filter dissolved in five per cent ammonia, which is easily accomplished by throwing ammonia upon it from a wash-bottle. Afterwards the filter is washed with a sufficient quantity of hot water and finally removed. The contents of the flask are neutralized warm, with hydrochloric acid, the acid being added until the precipitate first formed, after continued shaking, is again dissolved in the liquid. The solution is then cooled and treated, drop by drop, with constant stirring, with twenty cubic centimeters of magnesia mixture. Finally twenty-five cubic centimeters of dilute ammonia solution are added, the precipitate is not shaken, and, after two hours, is filtered through a gooch.

For the filtering of the ammonium magnesium phosphate by the molybdic method, freshly prepared felts are always employed since the remarkably fine crystalline precipitates will pass through a filter which has once been used. It is necessary also that special precautions be taken in the ignition. The crucible should be heated in a platinum cap, which has the purpose of protecting the contents of the crucible from the access of reducing gases during the ignition. After redness has been reached the cap can be removed and the crucible transferred to a blast where it is strongly ignited for ten minutes before weighing. The precipitate should be pure white.

The molybdic solution is prepared as follows: 150 grams of ammonium molybdate are dissolved in a liter of water, and after the solution is completely cooled, poured into a liter of nitric acid of 1.2 specific gravity.

=56. Estimation of Soluble Phosphoric Acid.=—1. The extraction of the superphosphates is made as follows: Twenty grams of the superphosphates are placed in a liter flask with 800 cubic centimeters of water and shaken continuously for thirty minutes. The flask is then filled with water to the mark and the whole again thoroughly shaken and filtered. For shaking, a machine is recommended, driven by hand or water power. The normal rate of the machine is fixed at 150 turns per minute.

2. The solution of the total superphosphates, obtained as above, must be boiled with nitric acid before the precipitation of the phosphoric acid in order to convert any phosphoric acid present as pyrophosphoric into tribasic phosphoric acid. For each twenty-five cubic centimeters of the superphosphate solution ten cubic centimeters of concentrated nitric acid are added and the mixture boiled.

3. The precipitation of the phosphoric acid is conducted by the molybdenum method as usually practiced.

4. For the estimation of iron and alumina in each of the superphosphates the Glaser method is recommended provisionally.

=57. Methods for Phosphoric Acid used in the Norway Stations.=[42]—1. _Description of the Method for Total Phosphoric Acid._—For determining the phosphoric acid in bone-meal, fish-guano, and superphosphates, five grams of the substance, with twenty cubic centimeters of nitric acid of 1.42 specific gravity, and fifty cubic centimeters of sulfuric acid of 1.8 specific gravity, are boiled half an hour in a half liter flask, diluted with water, and after cooling, made up to the mark. Fifty cubic centimeters of the filtrate are made alkaline with ammonia, then acid with nitric acid, precipitated with fifty cubic centimeters of molybdic solution for every one-tenth gram of phosphorus pentoxid present, heated over the water-bath for one hour, and allowed to stand twelve hours more, when the supernatant liquid is separated by decantation the precipitate washed thoroughly with dilute molybdate solution (1: 4) dissolved in warm dilute ammonia, and the filter washed with hot water. The ammoniacal solution is neutralized with hydrochloric acid, cooled, mixed, drop by drop, with constant stirring, with from ten to twenty cubic centimeters of magnesia mixture, and after a quarter of an hour one-third the volume of ten per cent ammonia is added. This is allowed to stand two hours, is filtered, washed with five per cent of ammonia until the disappearance of the chlorin reaction, dried, burned in an open crucible over a bunsen, and finally for a quarter of an hour, in a covered crucible heated over the blast.

2. _Water-Soluble Phosphoric Acid._—To twenty grams of the substance in a liter flask, are added 800 cubic centimeters of water, and shaken every fifteen minutes for two hours; the volume made up to the mark and the phosphoric acid in fifty cubic centimeters of the filtrate, equaling one gram substance, is determined as under total.

3. _Reverted Citrate-Soluble Phosphoric Acid._—Two and five-tenths grams substance are rubbed up with water, then washed upon the filter with about 100 cubic centimeters of water, the residue on the filter washed into a flask with a part of the measured citrate solution, and digested one hour at 35° to 40° with 200 cubic centimeters of Petermann’s citrate solution. The water and citrate extracts are made up to a quarter of a liter each, and the phosphoric acid determined in from twenty-five to fifty cubic centimeters, according to the quantity present.

_Solutions._ 1. _Molybdate Solution._—375 grams of ammonium molybdate are dissolved in two and five-tenths liters of water, and the solution poured into two and five-tenths liters of nitric acid of 1.20 specific gravity.

2. _Magnesia Mixture._—275 grams of crystallized magnesium chlorid and 350 grams of ammonium chlorid are dissolved in 3250 cubic centimeters of water and filled up to five liters with ammonia of 0.96 specific gravity.

3. _Petermann’s Solution._—One kilogram of citric acid is dissolved in about two liters of water and 1350 cubic centimeters of ammonia of 0.925 specific gravity and filled up with water to 5750 cubic centimeters. The solution then has a specific gravity of 1.09; 300 cubic centimeters of ammonia of 0.925 specific gravity are now added.

=58. Swedish Official Method for Determination of Phosphoric Acid.=[43]—The Swedish chemists determine phosphoric acid in fertilizers both by the molybdate and the citrate methods. These methods carefully conducted according to the directions given below, give very concordant results. In doubtful cases the former method is taken as the deciding one, it having proved by long practice to give very satisfactory results.

_Reagents for the Molybdate Method._—1. _Molybdic Solution._—Prepared by dissolving 100 grams of finely powdered molybdic acid with heat, in 400 grams of eight per cent ammonia of 0.967 specific gravity and pouring the solution into 1,500 grams of nitric acid of one and two-tenths specific gravity; or else by dissolving 150 grams ammonium molybdate in one liter of hot water, and pouring the solution into one liter of nitric acid of 1.2 specific gravity. Prepared in this way, the molybdic solution will contain, in the former case five per cent, in the latter case from five to six per cent of molybdic acid, and 100 cubic centimeters of it are required for precipitating one-tenth gram of phosphorus pentoxid.

2. _Magnesia Mixture._—Prepared from 110 grams of crystallized magnesium chlorid, 140 grams ammonium chlorid, 700 grams of eight per cent ammonia of 0.967 specific gravity and 1,300 grams of distilled water. The mixture is filtered after a few days, if necessary; ten cubic centimeters of the same are required for precipitating one-tenth gram of phosphorus pentoxid.

3. _Ten per cent ammonia_ of 0.959 specific gravity.

(a) _Water-Soluble Phosphoric Acid._—1. _Preparation of the Aqueous Solution._—Of superphosphates and in general fertilizers containing water-soluble phosphoric acid, a sample of twenty grams is taken, and water poured over it in a mortar; lumps are crushed lightly, but completely with the pestle without pulverizing it finer; the whole mass is then washed into a graduated flask holding one liter, which at once is filled up to the mark. The volume taken up by the residue insoluble in water, is left out of consideration in the calculation. The sample is left standing in the flask (which is occasionally shaken) at the ordinary temperature of the room for two hours, and the solution is then filtered.

2. _The Determination._—Take twenty-five cubic centimeters of the superphosphate solution thus prepared (when a twenty per cent sample is taken equal to one-tenth gram phosphorus pentoxid); add a quantity of molybdic solution sufficient for complete precipitation, leave standing for four hours in a beaker covered with a watch-glass; decant the solution through a small filter, wash the precipitate first by decantation, then on filter, with a mixture containing 100 parts molybdic solution, twenty parts nitric acid of 1.2 specific gravity, and eighty parts water, until a few drops put into alcohol, to which some dilute sulfuric acid has been added, does not, any longer, cause turbidity. The molybdic precipitate is now washed with but little water from the filter into a beaker, and particles adhering to the filter are dissolved by a hot mixture of one part ammonia and three parts water, which is allowed to flow into the beaker till the precipitate is, finally, completely dissolved in it. To the clear solution, add dilute hydrochloric acid while stirring, till the yellow precipitate formed by the acid is no longer immediately dissolved; then add from six to eight cubic centimeters of ammonia through the filter. The volume of the solution is not to exceed seventy-five cubic centimeters. It is now cooled completely and one cubic centimeter of magnesia mixture is added from a burette for every centigram of phosphorus pentoxid which it is expected to contain, and finally one-quarter of its volume of ammonia is added. The precipitate may be filtered after four hours. This is washed on the filter, preferably by means of suction, with a mixture of one part ammonia and three parts water till the filtrate is entirely free from chlorin. After drying, heat the precipitate, first gently, then stronger, and finally with a blast for a few minutes and then weigh it.

Treated with hydrochloric acid it must leave no insoluble residue (SiO₂), nor should hydrogen sulfid cause any precipitation in the solution thus formed (MoO₃).

(b) _Total Phosphoric Acid._—1. _In Superphosphates._—For the determination of total phosphoric acid, treat a weighed quantity of the superphosphate with nitric acid, if necessary to bring a difficultly soluble residue into solution, with addition of hydrochloric acid, or of potassium chlorate, to destroy organic matter present. Dilute the solution to a definite volume, and determine the phosphoric acid in a measured quantity of the same, as directed under (a) 2; if hydrochloric acid or potassium chlorate, be applied in the preparation of the solution, however, not till the measured quantity has been repeatedly evaporated to dryness with concentrated nitric acid.

2. _In Bone-meal._—Destroy organic matter in five grams of the sample by ignition, dissolve the residue in nitric acid, filter from the insoluble residue, dilute the filtrate to half a liter, take an aliquot part containing about one-tenth gram phosphorus pentoxid and determine the phosphoric acid as directed under (a) 2.

3. _In Fish-guano_ (and other fertilizing materials of organic origin).—The organic matter cannot here be removed by simple ignition, as in this way a loss of phosphorus may take place; It is therefore destroyed either in the wet way through nitric acid and potassium chlorate or in the dry way by fusion with a mixture of potassium nitrate and sodium carbonate, otherwise the procedure is as in (b) 1.

4. _In Mineral Phosphates._—Determine the phosphoric acid in a solution obtained by nitric acid; organic matter is destroyed preferably in the wet way.

5. _In Basic Slag._—Dissolve ten grams of powdered slag by treating it with 100 cubic centimeters of fuming hydrochloric acid with heat; wash the solution into a graduated half liter flask, fill to the mark, shake well, and filter. Determine the phosphoric acid in twenty-five cubic centimeters of the clear filtrate, according to (a) 2, after having first, however, evaporated the solution to dryness and then at least three times evaporated the residue to dryness with concentrated nitric acid.

=59. Method Employed by the Royal Experiment Station of Holland.=—_A. Soluble Phosphoric Acid._[44]—The necessary reagents are:

(1) Molybdate solution, made by dissolving 150 grams of ammonium molybdate in a liter of water and pouring the solution into a liter of nitric acid of 1.20 specific gravity.

(2) A ten per cent solution of ammonium nitrate.

(3) Strong and dilute ammonia, the latter being between two and five-tenths and three per cent of 0.988 specific gravity.

(4) Magnesia mixture made by dissolving 110 grams of crystallized magnesium chlorid, 140 grams of ammonium chlorid, and 700 cubic centimeters of ammonia of 0.96 specific gravity in water and bringing the solution to two liters.

(5) Ammoniacal citrate solution, made by dissolving 500 grams of citric acid in a liter of water, and mixing with four liters of ten per cent ammonia of 0.96 specific gravity.

_Manipulation._—Place twenty grams of substance in a mortar together with some cold distilled water or pure rain water, stir, and decant the water and suspended matters into a liter flask. After this has been repeated several times, rub up the residual mass and wash it all into the flask. Fill up to about 900 cubic centimeters and allow to stand two hours (twenty-four hours in the case of double phosphates with more than twenty-two per cent of soluble phosphoric acid), shaking repeatedly; or shaking continuously, for half an hour. Fill up to the liter mark and filter through a dry filter. Take portions of twenty-five or fifty cubic centimeters for each determination, add 100 cubic centimeters of molybdate solution for each 100 milligrams of phosphorus pentoxid present, warm to about 80° for an hour, filter, and wash the precipitate with the ammonium nitrate solution. Add a little molybdate solution to the filtrate, warm, and, if a fresh precipitate be observed, it is to be added to the first. The precipitate is to be dissolved in ammonia, and hydrochloric acid carefully added until the precipitate caused by it only slowly redissolves on stirring. The phosphoric acid is precipitated from the clear liquid which is still ammoniacal with magnesia mixture, using ten cubic centimeters for each 100 milligrams of phosphorus pentoxid present. This is added, drop by drop, and the liquid kept stirred during the addition. Allow it to stand at least two hours, filter, wash with dilute ammonia, dry, and ignite. This last is done at first with a very small flame but is finished with the blast-lamp or in a Rössler furnace. To insure burning to whiteness, nitric acid may be used, but not more than one or two drops.

_B. Total Phosphoric Acid._—(1) For bone and flesh-meal, fish-guano, and similar fertilizers the reagents necessary are the same as before.

Carefully burn five grams to ash, boil the ash for half an hour with nitric acid of 1.32 specific gravity, dilute with water, and, after cooling, dilute to 500 cubic centimeters. Filter through a dry filter and take fifty cubic centimeters of the filtrate. Add 100 cubic centimeters of the molybdate solution for each 100 milligrams of phosphorus pentoxid present. Treat further as before described.

(2) Phosphates, guanos, bone-black, etc.

One gram of substance, after powdering, and, if necessary, igniting, is covered with four cubic centimeters of hydrochloric acid of 1.13 specific gravity and a little water and heated for an hour and a half. Evaporate to dryness without filtration, making repeated additions of nitric acid until no more vapors of hydrochloric acid are evolved. Boil the residue with nitric acid, cool, make up to 100 cubic centimeters with water, and shake. Filter and treat fifty cubic centimeters of the resulting solution by the molybdate method and proceed further as before described.

=60. Sources of Error in the Molybdate Method.=—When conducted with proper care, the gravimetric molybdate method is one of the most exact processes known to analytical chemistry.

There are, however, some sources of error in the process which should be avoided as carefully as possible or taken into account.

1. _Error Due to Occluded Silica._—When silica passes into solution in the original sample, and this may be the case especially with mineral phosphates, it may appear both in the yellow precipitate and in the final magnesium pyrophosphate. In all such cases the residue, after ignition, should be dissolved in hydrochloric acid, and any insoluble residue weighed as silica and deducted from the first weight. If the silica be removed by evaporating the solution of the original material to dryness, and igniting to destroy organic matter, care must be taken to reconvert all phosphoric acid into the ortho form by long boiling with nitric acid before precipitation.

Another method of avoiding any trouble from silica consists in using sulfuric and a little nitric acid as the solvent for the original substance. Silica is not soluble in hot concentrated sulfuric acid. The volume of the sulfuric should be about ten times that of the nitric acid used, and the boiling be continued until sulfuric vapors are evolved.

2. _Error Due to Arsenic._—Only in rare cases will arsenic be found in phosphatic fertilizing materials. In case of pyritic phosphates, the iron disulfid may carry arsenic. The solution in such a case is best accomplished in hydrochloric acid. If aqua regia be used, all nitric acid should be removed by repeated evaporation with hydrochloric. The arsenic can then be precipitated in the hot dilute hydrochloric acid solution by hydrogen sulfid.

3. _Error Due to Occluded Magnesia._—The danger of contamination of the yellow precipitate with magnesium oxid has been pointed out by some authors. The re-solution of the precipitate followed by a second precipitation is the usual remedy proposed. Lorenz states that this source of error may be entirely avoided by the addition of two per cent of citric acid to the phosphomolybdate solution.[45]

4. _Error Due to Volatility of Phosphoric Acid._—This source of error has been made the subject of a special study by Neubauer.[46]

From the results, a table has been constructed, the use of which is recommended for phosphoric acid determinations. The source of error in this method lies exclusively in the loss of phosphoric acid by volatilization. The magnesia-covered crucible lid offers a very good control of this error, and its use is recommended to the analyst. Of course, the presence of sulfur in the gas used for ignition is liable to disturb this check.

The following course of procedure in the determination of phosphoric acid can be recommended to avoid or correct this error:

Separate the phosphoric acid in the form of the yellow precipitate and wash this latter in the usual way. Too high a heat should not be employed, nor should the solutions be allowed to stand too long lest excess of molybdic acid separate. Dissolve the phosphomolybdate in 100 cubic centimeters of cold two and five-tenths per cent ammonia and add as many cubic centimeters of the usual magnesia mixture (fifty-five grams magnesium chlorid and seventy grams ammonium chlorid dissolved in a liter of two and five-tenths per cent ammonia) as there are centigrams of phosphorus pentoxid present. Addition should not be made faster than ten cubic centimeters per minute. Stir during the addition. After the precipitation, stir briskly once more and then allow to stand at least three hours. Wash with two and five-tenths per cent ammonia till the chlorin reaction disappears, dry the filter, and introduce into a well-cleaned crucible which has been thoroughly ignited. Place the lid at an angle, carbonize the filter, and gradually raise the heat, though not higher than a medium red heat, till the pyrophosphate becomes completely white. When this happens bring the blast into action and ignite to constant weight. The weight finally accepted must not change even after half an hour’s ignition. Upon this requirement especial stress must be laid. Pure magnesium pyrophosphate does not suffer any loss even after several hours’ ignition nor does a good platinum crucible. To the weighed amount of pyrophosphate, add the correction given in the table. For example, if the weight be 250 milligrams, the correction to be added is four and two-tenths milligrams, and the correct weight is then 254.2 milligrams. Multiplication of the sum by sixty-four gives the amount of phosphorus pentoxid in the weight taken for analysis.

CORRECTION FOR PHOSPHORIC ACID DETERMINATION.

Found, Lost, Found, Lost,
Mg₂P₂O₇ milligrams Mg₂P₂O₇ milligrams
in grams. Mg₂P₂O₇. in grams. Mg₂P₂O₇.
0.10 0.6 0.24 4.0
0.12 0.8 0.25 4.2
0.14 1.2 0.26 4.6
0.15 1.4 0.27 5.0
0.16 1.6 0.28 5.5
0.17 2.4 0.29 6.1
0.18 2.6 0.30 6.8
0.19 3.2 0.31 7.6
0.20 3.5 0.32 8.6
0.21 3.6 0.33 9.6
0.22 3.8 0.34 10.6

When phosphoric acid is to be estimated as pyrophosphate it must always be first separated as molybdate, even when the original solution contains no bases capable of forming insoluble phosphates, as otherwise these corrections will not be applicable.

Using these corrections the estimation of phosphoric acid becomes one of the most accurate of known analytical methods.

=61. The Color of the Magnesium Pyrophosphate.=—After the final ignition of the magnesium pyrophosphate, whether secured by the citrate or the molybdic method, a black or grayish tint is often noticed. This may be due to traces of organic matter brought down by the precipitate and especially to a lack of care in the initial ignition. Many devices have been proposed for the purpose of avoiding this coloration, although general experiments have shown that there is no appreciable increase in the weight of the precipitate when colored in this way.

When the precipitation is carried on according to the citrate method, Neubauer[47] proposes to eliminate this coloration by the use of ammonium sulfate. About seven cubic centimeters of a saturated solution of ammonium sulfate should be added to the solution before the precipitation by the magnesium mixture. With this precaution it is possible to obtain a perfectly white precipitate after five minutes of ignition. The lively glowing of the precipitate throughout the whole mass at the time of changing into pyrophosphate, is much more easily observed by this treatment than when the mass is gray or black. Even should the addition of the ammonium sulfate solution to one containing a large amount of lime produce a precipitate of crystalline calcium sulfate, it is of no importance inasmuch as the ammonium citrate immediately dissolves large quantities of the calcium salt.

In this laboratory a white pyrophosphate is easily obtained by treating the precipitate on the gooch after washing free of chlorids with a drop or two of ammonium nitrate. The ignition is commenced very gently at first and afterwards when the mass is white the blast is used.

If the ignited residue be gray it may sometimes be whitened by moistening with a drop or two of nitric acid, burning at a very low temperature, followed by the blast. There is no appreciable difference in weight between a gray and white pyrophosphate.

=62. Determination of Phosphoric Acid and Nitrogen in the Same Solution by Treatment with Sulfuric Acid and Mercury.=—Fertilizing materials which contain organic nitrogen and phosphoric acid, such as bones, are of such a nature that it is often difficult to obtain a fair sample of them in quantities suited to the direct determination; _viz._, about one gram. Thus it often becomes important to take a much larger quantity of the material, to bring it into solution and to take an aliquot part thereof. It may also often happen that it is important to determine the phosphoric acid in the same sample which has been used for the determination of the nitrogen by moist combustion with sulfuric acid and mercury. In this connection, however, it is somewhat difficult to avoid the precipitation of some of the mercury with the phosphoric acid.

The mercuric sulfate which is produced by the Kjeldahl method is not precipitated in the presence of ammoniacal solution of ammonium citrate, but there may be small quantities of mercurous salts present or some finely divided metallic mercury which may contaminate mechanically the phosphate precipitate. These disturbing influences may be removed by previous treatment with sodium chlorid. If from fifty to sixty cubic centimeters of sulfuric acid have been used for the solution and oxidation and this be made up to half a liter, it will be sufficiently dilute to permit an almost quantitative separation of the mercurous chlorid produced by treatment with sodium chlorid.

Neubauer, who has proposed this method, finds that when sodium chlorid is used previous to the precipitation of the phosphoric acid, a precipitate of ordinary size contains, at most, only one milligram of mercury, while without the use of sodium chlorid as much as four milligrams may be found. The details of the method employed by Neubauer are as follows:

Ten grams of the fertilizing material are placed in a half liter flask with from fifty to sixty cubic centimeters of strong sulfuric acid, two grams of mercury, and a little paraffin to prevent foaming. The oxidation is carried on as usual in the Kjeldahl method. The liquid, after cooling, is diluted with water and one cubic centimeter of a citrate solution of sodium chlorid added, cooled, filled to the mark, filtered, and fifty cubic centimeters taken for the determination of the phosphoric acid, according to the citrate method and the same quantity for the determination of the ammonia by distillation.

THE CITRATE METHOD.

=63. General Principles.=—It has been seen that in the molybdic method there is introduced a process at considerable cost, both of reagents and time, having for its object the separation of the phosphoric acid from all the other acids and bases which may have been present in the original sample. The phosphorus is thus obtained in composition with molybdenum and ammonium in a form easily soluble in ammonia, from which it can be accurately separated by means of a soluble salt of magnesia.

The citrate method has for its object the suppression of this intermediate step and the determination of the phosphoric acid by direct precipitation in presence of iron, lime, and alumina. The principle on which it is based rests on the well-known power of an alkaline ammonium citrate to hold in solution the salts of iron, alumina, and lime, while at the same time it permits of the separation of phosphoric acid, as ammonium magnesium phosphate. In no case can the citrate method be regarded as an exact analytical process, but large experience has shown that the errors of the method are compensatory and that it affords a good and ready method for fertilizer control.

When phosphoric acid solutions which contain no iron, lime, alumina, or manganese, are precipitated in presence of ammonium citrate the results obtained vary markedly with the quantity of magnesia mixture employed. Grupe and Tollens[48] were the first to point out that a portion of the phosphoric acid might remain in solution, but that the precipitate might contain a sufficient excess of magnesia to compensate for the loss. It has been further shown by Glaser[49] that a portion of the phosphoric acid may be lost by volatilization in the citrate method. When the ignition is carried on in a crucible where the cover is coated with magnesia to intercept the volatilized acid, a considerable quantity of it can be recovered by the molybdic method.

Where too little magnesia mixture is employed, therefore, two sources of loss are to be guarded against; _viz._, a part of the phosphoric acid may remain in solution and another part be volatilized on ignition. The explanation of the volatilization is as follows: In the presence of ammonium citrate, magnesium chlorid may be partly converted into magnesium citrate and ammonium chlorid. There may be a time, therefore, in the precipitation with not too great excess of magnesia mixture, when proportionally there is little magnesium chlorid and much ammonium chlorid present. The formation of a salt represented by the formula Mg(NH₄)₄(PO₄)₂ may take place which, upon ignition, breaks up into Mg(PO₃)₂ and finally passes into Mg₂P₂O₇ with loss of P₂O₅. This theoretical condition has but little weight, however, practically in the analysis of fertilizers, since in these cases a large quantity of lime is always present. But even in these cases traces of volatile P₂O₅ may be discovered.

Wells[50] has shown that the citrate method gives good results in certain conditions but that this accuracy is reached by a fortunate compensation of errors. The ammonium magnesium salt does not precipitate all the phosphoric acid in this process, but contains enough impurities to make up for this loss.

Johnson[51] in conjunction with Osborne has shown that the results by the citrate method practiced in accordance with the details laid down by Vögel, are too low, but that this difficulty could be overcome by using more and stronger magnesia mixture and a larger quantity of strong ammonia solution. The citrate method was found to give unsatisfactory results when iron and alumina were present in any considerable quantity. In the examination of the final ignited precipitate, which should be pure magnesium pyrophosphate, it was found to consist of only 94.98 to 97.83 per cent of that salt. The chief impurity found was calcium oxid, the percentage of which varied from 2.05 to 3.95 in six cases. There was also a considerable percentage of loss due, probably, to magnesia and pyrophosphoric acid.

The presence of large quantities of iron and alumina also impairs the accuracy of the molybdate method when the precipitation of the yellow salt takes place at too high a temperature. When the temperature of precipitation in the method is above 50° the results are likely to be too high while a great excess of nitric acid in the reagent may produce a contrary effect. In the latter case the filtrate from the yellow salt should be mixed with additional quantities of molybdate solution until no further precipitate takes place.

Many methods of conducting the citrate method have been proposed but the best of them are based on the one elaborated at the experiment station of Halle by Bühring, and which will be given in the next paragraph, followed by some other methods in use in other localities.

=64. Method of the Halle Agricultural Experiment Station.=[52]—The citrate method, as described by Morgen, is the one employed.[53] The principle depends upon the direct precipitation of the phosphoric acid by magnesia mixture. By the addition of a solution of ammonium-citrate the precipitation of lime, iron, alumina, and other bases, is prevented. The precipitate of ammonium magnesium phosphate is converted by ignition into magnesium pyrophosphate and weighed as such. By the use of this method a part of the phosphoric acid sometimes escapes precipitation and a portion of the other bases is sometimes thrown down with the precipitate. Experience has shown that by adhering to certain precautions the weight of impurities in the precipitate may be made to correspond exactly to the weight of the phosphoric acid which escapes precipitation.

SHAKING APPARATUS FOR SUPERPHOSPHATES.]

(1) _Soluble Acid._—The soluble phosphates are first brought into solution in such a way that one liter of water contains the soluble phosphoric acid from twenty grams of the substance. Twenty grams are rubbed in a porcelain mortar with water and through a wide-necked funnel washed into a bottle-shaped flask in which a little water has been previously placed. The flasks employed are made of thick glass in order to withstand shaking. After the substance is washed, the flasks are filled to the mark and closed with rubber stoppers. They are then placed upon a shaking rack as indicated in Fig. 3, which is also furnished with an apparatus for separating the fine meal from basic slag.

On a table, as shown in the figure, is fastened a movable horizontal board by means of hinges. At the left hand of this movable board is placed an open wooden box in which is a perforated shelf for the purpose of holding the flasks, so as to prevent their striking together during the shaking.

For the best results the substance to be examined should be placed in the flask in a dry state and then 800 cubic centimeters of water added and shaken by means of the machine indicated for half an hour. Afterwards the flasks are filled up to the mark, well shaken, and filtered through double folded filters into ordinary flasks of about 400 cubic centimeters capacity. Before any of the filtrate is collected, the first that runs through should be well shaken in the receiving flasks and rejected. Fifty cubic centimeters of the filtrate thus collected, corresponding to one gram of the substance, should be used for the determination.

(2) _Total Acid._—For total phosphoric acid, including the insoluble portions, the material is treated as follows: Five grams of the substance are placed in a 500 cubic centimeter flask with twenty cubic centimeters of nitric acid of 1.42 specific gravity, and fifty cubic centimeters of pure concentrated sulfuric acid, and boiled briskly for half an hour. With substances which contain much organic material, a little paraffin is added to avoid frothing. Such substances also require a larger quantity of nitric acid than that above specified. The flasks are allowed to cool, water added, again allowed to cool, and filled up to the mark at 17°.5. If hydrochloric instead of sulfuric acid be used in making the above solution, when the citrate method is employed, the results are always too high because the precipitate contains lime and alumina in such quantities as to render any compensation for them inaccurate. In addition to this the sulfuric has this great advantage over the hydrochloric acid; _viz._, in not separating silicic acid, inasmuch as the silicic acid is insoluble in boiling sulfuric acid.

(3) _Citrate-Soluble Acid._—Two grams of the sample are digested with 100 cubic centimeters of citrate solution, 1.09 specific gravity, for half an hour at 50° in a beaker. Afterwards the soluble matter is separated by filtration with the aid of a filter-pump and the residue washed with a solution of one part water and one part citrate solution until all the dissolved phosphoric acid is removed from the filter. Generally three or four washings are sufficient. The residue on the filter is dried, ignited, and dissolved in a mixture of two cubic centimeters of nitric and twenty cubic centimeters of sulfuric acid, the solution made up to a volume of 200 cubic centimeters, filtered, and 100 cubic centimeters of the filtrate taken for the determination. The acid in the filtrate is nearly neutralized and fifty cubic centimeters of citrate solution are added, and afterwards twenty-five cubic centimeters of magnesia mixture and twenty cubic centimeters of twenty-four per cent ammonia. After standing for forty-eight hours, the precipitate is separated by filtration, ignited, and weighed in the usual way. The difference between the total phosphoric acid and that in the insoluble residue, after treatment with ammonium citrate, as above, gives the quantity of phosphoric acid soluble in the citrate solution. The difference between the total citrate-soluble and the water-soluble gives the quantity of the reverted phosphoric acid.

The ammonium citrate solution used for the digestion is made as follows: Two hundred and fifty grams of crystallized citric acid are dissolved in half a liter of hot water, diluted with 550 cubic centimeters of water, 276 cubic centimeters of twenty-four per cent ammonia added, and finally, exactly neutralized by adding, little by little, fifty per cent citric acid solution.

The Halle methods of separating the water and citrate-soluble acids appear to be less complete and reliable than those in use by the Official Agricultural Chemists of this country. The precipitation of basic phosphates, when large quantities of water are used at once in separating soluble acid, must tend to diminish the quantity obtained, while the lack of care in assuring the neutrality of the citrate solution might lead to varying results.

(4) _Double Superphosphates._—In the case of double superphosphates, which sometimes contain large quantities of pyrophosphate, the solution is made in the usual way so that in 100 cubic centimeters there will be contained two grams of the substance. Usually ten grains are taken and the volume made up to half a liter. Twenty-five cubic centimeters of the filtrate are diluted with seventy-five cubic centimeters of water and the pyro converted to orthophosphoric acid by heating with ten cubic centimeters of strong nitric acid on a sand-bath. The heating should be continued until the volume be reduced to twenty-five cubic centimeters. The strongly acid liquid is made alkaline with ammonia, and afterwards slightly acid with nitric, and the rest of the process is carried on in the usual way.

(5) _Phosphoric Acid in the Residue of Superphosphate Manufacture._—In the mixture of superphosphates and gypsum, the residue of the manufacture of double superphosphates, the phosphoric acid is estimated in the following manner: Five grams of the substance are placed in a dish, rubbed up with absolute alcohol, and washed into a 250 cubic centimeter flask. The flask is filled with absolute alcohol to the mark, closed with a stopper, and with frequent shaking, allowed to stand for two hours; it is thereupon filtered as quickly as possible; fifty cubic centimeters of the filtrate corresponding to one gram of the substance, are taken for the estimation. This fifty cubic centimeters is evaporated on a sand-bath to a sirupy consistence, diluted with water, and treated, as in the case of the soluble phosphates above mentioned. In all cases as described above, after the solutions are obtained they are treated with the ammonium citrate solution and the phosphoric acid estimated as in the first instance given.

(6) _Solutions Employed._—

(a) The citrate solution is made as follows: 1,500 grams of
citric acid are dissolved in water, treated with five liters
of twenty-four per cent ammonia, and made up to fifteen liters.

(b) The magnesia mixture is made as follows: 500 grams of
magnesium chlorid, 1,050 grams of ammonium chlorid, three
and five-tenths liters of twenty-four per cent ammonia, and
six and five-tenths liters of distilled water are used.

In the case of the superphosphates fifty cubic centimeters of the citrate solution are employed and with the basic slags 100 cubic centimeters; and in both cases twenty-five cubic centimeters of the magnesia mixture.

(7) _Details of the Manipulation._—On the addition of the citrate solution there should be no permanent troubling of the liquid but there should be a total clearing up thereof. In order to facilitate this, after the addition of the citrate solution, the flasks should be gently shaken in order to distribute the solution throughout the mass. Solutions from bone-black superphosphates show sometimes, after the addition of the citrate solution, a more or less strong opalescence, but this opalescence does not influence the results. Should it happen that with superphosphates which are made from raw material containing large excesses of iron or clay, fifty cubic centimeters of the citrate solution are not sufficient to prevent the other bases from being precipitated, an additional quantity up to twenty-five cubic centimeters may be added. The addition of the magnesia mixture must follow as quickly as possible after the addition of the citrate solution to avoid a separation of crystalline calcium phosphate. On the addition of the citrate solution there is always a rise in temperature. Inasmuch as the precipitation of the phosphoric acid with magnesia must take place in the cold, the liquid must be cooled after the addition of the citrate,[54] and the cooling should take place as quickly as possible.

The above method was adopted by the chemical section of the International Agricultural Congress held at Vienna, September, 1890.[55]

SHAKING MACHINE FOR AMMONIUM MAGNESIUM PHOSPHATE.]

In order to hasten the precipitation of the ammonium magnesium phosphate and to prevent the fixation of the precipitate on the walls of the erlenmeyer, the flask should be shaken for half an hour. For this purpose the flasks should be closed with smooth well-fitting rubber stoppers and placed in a shaking machine. The shaking machine of the form given in Fig. 4, recommended by the Halle station, is very conveniently used for this purpose.

On a vertical axis are carried two stages for holding the flasks. The flasks are prevented from striking each other by means of the partitions shown. The apparatus is conveniently driven by a small water-motor, as indicated, which imparts to the stages a partial back and forth revolution.

After shaking for half an hour, any precipitate adhering to the rubber stoppers is carefully washed off with ammonia water into the flask. The filtration can be made immediately after the shaking or after two or three days; the results are the same.

RÖSSLER IGNITION FURNACE.]

The filtration of the ammonium magnesium phosphate is made through perforated crucibles. The asbestos felt is prepared in the following way: The coarse fibers of asbestos are chopped up with a sharp knife on a glass plate and boiled for two hours with strong hydrochloric acid; afterwards, by repeated washing with distilled water they are freed from acid and the too fine particles of asbestos which would tend to make the filter too impervious. After the last wash-water is poured off, the asbestos is suspended in water and used for making the felt on the filter. The preparation of the crucible and the filtration under pressure are accomplished in the usual way.

The ignition of the precipitate is accomplished in a Rössler ignition oven, Fig. 5. When the muffle of the furnace shows a white heat or a white-red heat it is at the proper temperature for the estimation. At higher temperatures, the asbestos felt is easily injured. Generally, an ignition of five minutes is sufficient, but with double superphosphates, ten minutes are required.

=65. The Swedish Citrate Method.=[56]—This method of determining phosphoric acid is founded on the fact that phosphoric acid in the presence of calcium salts, without it being necessary, previously, to convert it into phosphomolybdate, is precipitated directly by magnesia mixture from a solution, to which ammonium citrate has been added, provided first, that the solution contain a sufficient quantity of sulfuric acid, and second, that only as much citrate be added as is required to keep the calcium salts in alkaline solution.[57]

_Reagents._ (1) _Citric Acid Solution._—Prepared by dissolving 500 grams of citric acid in water, and completing to a volume of one liter.

(2) _Ten Per Cent Ammonia_ of 0.959 specific gravity.

(3) _Magnesia Mixture_, of the usual composition.

The various processes are conducted as follows:

(_a_) _Water-Soluble Phosphoric Acid._—Add twenty cubic centimeters of citric acid solution to fifty cubic centimeters of the water-soluble solution obtained according to the Swedish molybdenum method, and then add thirty-three cubic centimeters of ammonia. When the mixture has cooled, add slowly twenty-five cubic centimeters of the magnesia mixture, and then forty-two cubic centimeters of the ammonia. Keep the solution stirred by means of a closely clipped feather which is pressed tightly against the sides of the beaker; by this process the phosphate is precipitated after half an hour in pure condition and completely, without, in the least, sticking to the wall of the beaker; filter, wash, and ignite, as usually directed.

(_b_) _Insoluble Phosphoric Add._—Moisten, in a porcelain dish, ten grams of the powdered sample with water; add fifty cubic centimeters of concentrated sulfuric acid, and heat for fifteen minutes so high that fumes of sulfuric acid will escape. When the mass has cooled, wash it into a half liter graduated flask, fill to the mark, and shake well. After filtration, the clear filtrate may, after some time, turn turbid by separation of calcium sulfate, but as the ammonium citrate, which is afterwards added, again brings the precipitate into solution, it is of no importance. Take fifty cubic centimeters of the solution, corresponding to one gram of the powdered sample, add twenty cubic centimeters of the citric acid solution, neutralize the mixture approximately, but not exactly, by ammonia; after cooling, add twenty-five cubic centimeters of magnesia mixture; stir the fluid by means of a feather, as described above, till no more precipitate is formed, and finally add thirty-three cubic centimeters of ammonia while stirring for a couple of minutes more; after half an hour the precipitate may be separated by filtration, washed, and ignited, as usually directed.

The above process is essentially the one used with basic slags. When much organic matter is present, by continuing the heating with sulfuric acid for some time, it may be destroyed.

=66. Methods Adopted by the Brussels Congress, 1894.=—The report of the committee on methods of analysis of phosphoric acid requires the molybdate method to be used in all cases where the quantity to be determined is very small. In other cases the citrate method may be employed.[58]

(1) _Soluble Phosphoric Acid._—The soluble phosphoric acid is determined by the method adopted at Brussels in the following manner: Five grams of the sample are rubbed to a powder in a mortar, and then from fifty to sixty cubic centimeters of water added. After allowing to settle for a few minutes the liquid portion is decanted upon a filter. This operation is repeated three or four times. Finally the solid portions are washed upon the filter, and the washing with water is continued until the filtrate amounts to about three-quarters of a liter. A few drops of hydrochloric acid are added until the filtrate is perfectly clear, and the volume is then made up to one liter. Fifty cubic centimeters of the solution are then treated with thirty cubic centimeters of ammonium citrate solution and one-third as much ammonia. Afterwards thirty cubic centimeters of magnesia mixture are added, drop by drop, with constant stirring.

For superphosphates containing more than eighteen per cent of phosphoric acid only one gram is taken, for ordinary superphosphates two grams, and for compound fertilizers four grams. The sample is first treated as above for soluble acid until the filtrate amounts to 200 cubic centimeters, then clarified with a drop of nitric acid, and made up to a quarter of a liter.

(2) _Reverted Phosphoric Acid._—The filter containing the residue is then introduced into a quarter liter flask and treated with 100 cubic centimeters of Petermann’s alkaline ammonium citrate solution, vigorously shaken, and left at room temperature for fifteen hours. It is then digested for an hour at 40° and filtered. Fifty cubic centimeters of the filtrate are placed in a flask and, with constant shaking, thirty-five cubic centimeters of magnesia mixture added. The aqueous solution is treated in the same way. The precipitate is collected, ignited and weighed, and multiplied by 0.64 for phosphoric acid. The total acid is determined in the usual way.

=67. Dutch Method for Citrate-Soluble Phosphoric Acid.=[59]—The reagents necessary are:

(1) Citrate solution, prepared according to Petermann. Dissolve 165 grams of citric acid in 700 cubic centimeters of water, mix with 250 cubic centimeters of ammonia of 0.92 specific gravity, and, after cooling, bring to the volume of one liter.

(2) Magnesia mixture prepared according to Petermann. Dissolve 400 grams of crystallized magnesium chlorid, 800 grams of ammonium chlorid, and 1,600 cubic centimeters of ammonia of 0.96 specific gravity in water, and dilute to five liters.

The quantity to be taken for the analysis is five grams where the fertilizer contains less than six per cent of phosphoric acid (mixed fertilizers); two grams where it contains more than six and less than fifteen per cent (common superphosphates); and one gram where it contains more than fifteen per cent (double superphosphates). Place the weighed substance in a mortar and cover with 100 cubic centimeters of citrate solution. Gently rub up, wash into a half liter flask, and heat in a water-bath for an hour to a temperature between 35° and 38°. Allow to cool, fill up to 500 cubic centimeters, and filter through a dry double filter. If it is not clear at the first filtration, pour through the filter again, repeating this till clearness is attained. Measure 100 cubic centimeters and add seventy-five cubic centimeters of magnesia mixture, allowing the latter to flow into the former very slowly, and constantly stirring during the influx. Allow to stand fifteen hours, filter, wash with ammonia of 0.96 specific gravity, dry, ignite, and weigh.

The per cent of phosphoric acid, except where otherwise indicated, is always to be given as per cent of anhydrous acid (P₂O₅).

=68. Comparative Accuracy of the Citrate and Molybdate Methods.=—The general use of the citrate method of determining phosphoric acid by the German chemists has led Johnson[60] to review some trials of that method in the Yale laboratory made as early as 1880. These determinations have lately been repeated in comparison with the ordinary molybdate methods with the result that in sixty-seven determinations on bone-dust, superphosphate, cotton-hull ashes, cottonseed-meal, tankage, bone-char, phosphatic guano, and phosphate rock, only three citrate results differed from those obtained by the molybdate method by more than three-tenths of one per cent. The greatest discrepancy between the two methods was 0.41 per cent, and the average difference was 0.09 per cent.

The citrate method was found to give poor results when iron and alumina were present in considerable quantity. Ignited precipitates by the citrate method were found to contain as high as four per cent of lime, and iron and alumina in small quantities when these bodies were abundant in the original substance.

In the molybdate method the rapid precipitation from solutions at 65° was found to give unsatisfactory results and it was found necessary to conduct the process at temperatures between 40° and 50°. With a relative excess of nitric or a relative deficiency of molybdic acid some phosphoric acid may easily escape precipitation. The chief objection to precipitating at 65° is found in the fact that in presence of considerable iron and alumina some of these bodies may be found in the yellow precipitate, whence they pass to the final ammonium magnesium phosphate.

The citrate method, therefore, only gives safe results by compensating errors which in every class of phosphates must be empirically determined.

The molybdate method gives results too high when iron and alumina are present in considerable quantity and the yellow precipitate is obtained at temperatures above 50°. On the other hand, if there, be a great relative excess of nitric acid the results may be too low unless the filtrates from the yellow precipitate be mixed with additional molybdic solution and digested until no further precipitate is formed.

Comparative determinations made, by both methods, by the Association of German Experiment Stations have led to the conclusion that both give practically the same results when each one is conducted with the proper precautions peculiar to it.[61] In the latter part of 1892, at the general meeting of the Association, it was declared that the citrate method, after having been subjected to repeated tests, was found to be satisfactory, changing the composition of the solution so that it might have 1,100 instead of 1,000 grams of citric acid and four liters of twenty-four per cent ammonia to each ten liters. The data afforded by the citrate method, when applied to an artificial mixture of known composition, were more satisfactory than those obtained by the molybdic process.

In this laboratory the citrate method has been found to give nearly agreeing results with the old process. It is much shorter and less expensive; and is recommended most favorably for practical use, suggesting, however, that with every new kind of phosphate or phosphatic fertilizer varying notably in composition from the standard, the work should be checked at first by comparison with the molybdenum method.

BASIC PHOSPHATIC SLAGS.

=69. History and Manufacture.=—The basic process for the manufacture of Bessemer steel is known in Europe as the Thomas or Thomas and Gilchrist process, and the slags rich in phosphate, one of the waste products of the process, are known by the same name. In this country all the phosphatic slags which have been made in the manufacture of steel have been obtained working under the patents of Reese, and, when prepared for the market, are known as odorless phosphate. The only place where these slags have been made in this country is Pottstown, Pennsylvania. In Europe they are extensively manufactured, in England, France, and Germany, and their use for agricultural purposes has increased until it is quite equal to that of superphosphates.

The quantity of basic slag manufactured in Germany in 1893 was 750,000 tons; in England 160,000; in France 115,000, making the total production of central Europe about 1,000,000, a quantity sufficient to fertilize nearly 5,000,000 acres.

=70. Process of Manufacture.=—The principle of the process depends upon the arrangement of the furnaces, by means of which the phosphoric acid in the pig iron is caused to combine with the lime which is used as a flux in the converters. A general outline of the process is as follows: