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.
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 analysis. 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 mass 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 apatite.
[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 identity 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.]