71. Composition of Basic Slag.—The slags produced by the method above outlined may be amorphous or crystalline. When large masses are slowly cooled the interior often discloses a crystalline composition. In some samples analyzed in this laboratory the crystals were found to be of two forms; viz., acicular and tabular.[62] They had the following composition:
Calculated Per Cents as
| CaO. | Fe₂O₃. | Al₂O₃. | MgO. | V₂O₂ . | P₂O₅. | SiO₂. | |
|---|---|---|---|---|---|---|---|
| Acicular crystals | 42.69 | 20.98 | 3.71 | 0.49 | 0.18 | 27.06 | 4.96 |
| Tabular crystals | 53.61 | 9.64 | 0.91 | 0.08 | —— | 33.92 | 1.75 |
These data show that the two sets of crystals belong to two distinct mineral forms. The presence of vanadium in one of the samples is worthy of remark, and leads to the suggestion that in the slags made of phosphoriferous pigs may be found any of the rare metals which may exist in the ores from which the pigs were made. The amorphous portions may have a widely varying composition and consequent content of phosphoric acid. In all good slags, however, whether in crystalline form or as amorphous powder, the lime and phosphoric acid will be found combined as tetracalcium phosphate (Ca₄P₂O₉).
72. Molecular Structure of Tetracalcium Phosphate.—Several theories have been advanced in respect of the atomic arrangement of the elements contained in a molecule of tetracalcium phosphate. It must be confessed that so little is known concerning the reactions of this body as to make theories of its constitution largely visionary. But the existence in definite crystalline form of this salt shows that it is not merely an intimate mechanical mixture, but a true molecular form. As a type of the supposed arrangement of its particles the graphic formula proposed by Kormann may be consulted; viz.,
The crystals of this salt, as may be seen by inspection of the analytical data, contain other bodies than calcium, oxygen, and phosphorus. It would be of interest to push the investigation of their constitution further and see if crystals of pure tetracalcium phosphate could be obtained, and under what conditions they would be contaminated by other metallic oxids. Usually, by the color of the crystals, it will be easy to determine something of the nature, if not the extent of the contamination.
73. Solubility of Phosphatic Slags.—The high agricultural value of basic slags led to an early study of their solubility in ammonium citrate, citric acid, and other organic solutions. Even finely ground mineral phosphates and bones are soluble to some extent in ammonium citrate, as was pointed out as long ago as 1882.[63] The most common solvents used for basic slags are ammonium citrate and citric acid. The ammonium citrate should be the same as that used for the determination of reverted phosphoric acid and the citric acid solution commonly used contains five grams in a hundred cubic centimeters. The slags of different origin and even of different age vary greatly in respect of the quantity of soluble matter they contain. It is believed, however, that a very fair idea of the agricultural value of a slag may be obtained by determining its degree of solubility in one of the menstrua named.
74. Separation by Sifting.—The relative availability of a slag, as in the case of a mineral phosphate, is determined by the percentage of fine material it contains. Sieves of varying apertures are used to determine this percentage. A one-half millimeter or a one-quarter millimeter circular aperture is best, and the percentage of the total material passing through is determined. A method used in Germany consists in sifting the slag in a sieve twenty centimeters in diameter the meshes of which are from 0.14 to 0.17 millimeter square and which measure diagonally from 0.22 to 0.24 millimeter.
75. Solution of Phosphatic Slags.—Sulfuric acid has been found to be an excellent solvent for basic slags preparatory to the determination of phosphoric acid. There is, however, no unanimity of opinion concerning the best method or means of solution. Aqua regia and nitric acid are objected to because they may convert any phosphorus in combination with the iron into phosphoric acid and thus increase the quantity present.[64] But iron phosphid is seldom or ever found in slags and therefore this objection is not always tenable. Sulfuric acid has also been deemed objectionable because the gypsum separated is likely to carry with it some of the other substances to be determined.