Bisulphate of Potassa (KO, 2S03).—At a red heat the half of the sulphuric acid of this salt becomes free, and thus separates and expels volatile substances, by which we can recognize lithium, boracic acid, nitric acid, fluoric acid, bromine, iodine, chlorine; or it decomposes and reveals some other compounds, as, for instance, the salts of the titanic, tantalic and tungstic acids. The bisulphate of potash is also used for the purpose of converting a substance into sulphate, or to free it at once from certain constituents. These sulphates are dissolved in water, by which we are enabled to effect the separation of its various constituents.
PREPARATION.—Two parts of coarsely powdered sulphate of potash are placed in a porcelain crucible, and one part of pure sulphuric acid is poured over it. Expose this to heat over the spirit-lamp, until the whole becomes a clear liquid. The cooled mass must be of a pure white color, and may be got out of the crucible by inverting it. It must be kept in a fine powder.
4. Oxalate of Potassa (KO, O).—Dissolve bioxalate of potash in water, and neutralize with carbonate of potash. Evaporate the solution at a low heat to dryness, stirring constantly towards the close of the operation. The dry residue is to be kept in the form of a powder.
The oxalate of potash, at a low red heat, eliminates a considerable quantity of carbonic oxide, which, having a strong affinity for oxygen, with which it forms carbonic acid, it is therefore a powerful agent of reduction. It is in many cases preferable to carbonate of soda.
5. Cyanide of Potassium (Cy, K).—In the dry method of analysis, this salt is one of the most efficient agents for the reduction of metallic oxides. It separates not only the metals from their oxygen compounds, but likewise from their sulphur compounds, while it is converted through the action of the oxygen into carbonate of potash, or, in the latter case, combines with the sulphur and forms the sulphureted cyanide of potassium. This separation is facilitated by its easy fusibility. But in many cases it melts too freely, and therefore it is better to mix it, for blowpipe analysis, with an equal quantity of soda. This mixture has great powers of reduction, and it is easily absorbed by the charcoal, while the globules of reduced metal are visible in the greatest purity.
PREPARATION.—Deprive the ferrocyanide of potassium (2KCy + FeCy) of its water by heating it over the spirit-lamp in a porcelain dish. Mix eight parts of this anhydrous salt with three parts of dry carbonate of potash, and fuse the mixture by a low red heat in a Hessian, or still better, in an iron crucible with a cover, until the mass flows quiet and clear, and a sample taken up with an iron spatula appears perfectly white. Pour the clear mass out into a china or porcelain dish or an iron plate, but with caution that the fine iron particles which have settled to the bottom, do not mix with it. The white fused mass must be powdered, and kept from the air. The cyanide of potassium thus prepared, contains some of the cyanate of potassa, but the admixture does not deteriorate it for blowpipe use. It must be perfectly white, free from iron, charcoal, and sulphide of potassium. The solution of it in water must give a white precipitate with a solution of lead, and when neutralized with hydrochloric acid, and evaporated to dryness, it must not give an insoluble residue by dissolving it again in water.
6. Nitrate of Potassa, Saltpetre (KO, NO5).—Saturate boiling water with commercial saltpetre, filter while hot in a beaker glass, which is to be placed in cold water, and stir while the solution is cooling. The greater part of the saltpetre will crystallize in very fine crystals. Place these crystals upon a filter, and wash them with a little cold water, until a solution of nitrate of silver ceases to exhibit any reaction upon the filtrate. These crystals must be dried and powdered.
Saltpetre, when heated with substances easy of oxidation, yields its oxygen quite readily, and is, therefore, a powerful means of oxidation. In blowpipe analysis, we use it particularly to convert sulphides (as those of arsenic, antimony, &c.) into oxides and acids. We furthermore use saltpetre for the purpose of producing a complete oxidation of small quantities of metallic oxides, which oxidize with difficulty in the oxidation flame, so that the color of the bead, in its highest state of oxidation, shall be visible, as for instance, manganese dissolved in the microcosmic salt.
7. Biborate of soda, borax—(NaO + 2BO3).—Commercial borax is seldom pure enough for a reagent. A solution of borax must not give a precipitate with carbonate of potassa; or, after the addition of dilute nitric acid, it must remain clear upon the addition of nitrate of silver, or nitrate of baryta. Or a small piece of the dry salt, fused upon a platinum wire, must give a clear and uncolored glass, as well in the oxidation flame as in the reduction flame. If these tests indicate a foreign admixture, the borax must be purified by re-crystallization. These crystals are washed upon a filter, dried, and heated, to expel the crystal water, or until the mass ceases to swell up, and it is reduced to powder.
Boracic acid is incombustible, and has a strong affinity for oxides when fused with them; therefore, it not only directly combines with oxides, but it expels, by fusion, all other volatile acids from their salts. Furthermore, boracic acid promotes the oxidation of metals and sulphur, and induces haloid compounds, in the oxidation flame, to combine with the rising oxides. Borates thus made, melt generally by themselves; but admixed with borate of soda, they fuse much more readily, give a clear bead. Borax acts either as a flux, or through the formation of double salts.
In borax, we have the action of free boracic acid, as well as borate of soda, and for that reason it is an excellent reagent for blowpipe analysis.
All experiments in which borax is employed should be effected upon platinum wire. The hook of the wire should be heated red hot, and then dipped into the powdered borax. This should be exposed to the oxidation flame, when it will be fused to a bead, which adheres to the hook. This should be then dipped into the powdered substance, which will adhere to it if it is hot; but if the bead is cool, it must be previously moistened. Expose this bead to the oxidation flame until it ceases to change, then allow it to cool, when it should be exposed to the reduction flame. Look for the following in the oxidation flame:
(1.) Whether the heated substance is fused to a clear bead or not, and whether the bead remains transparent after cooling. The beads of some substances, for instance those of the alkaline earths, are clear while hot; but upon cooling, are milk-white and enamelled. Some substances give a clear bead when heated and when cold, but appear enamelled when heated intermittingly or with a flame which changes often from oxidation to reduction, or with an unsteady flame produced by too strong a blast. The reason is an incomplete fusion, while from the basic borate compound a part of the base is separated. As the boracic acid is capable of dissolving more in the heat, a bead will be clear while hot, enamelled when cold, as a part in the latter instance will become separated.
(2.) Whether the substance dissolves easily or not, and whether it intumesces from arising gases.
(3.) Whether the bead, when exposed to the oxidation flame, exhibits any color, and whether the color remains after the bead shall have cooled, or whether the color fades.
(4.) Whether the bead exhibits any other reaction in the reduction flame.
The bead should not be overcharged with the substance under examination, or it will become colored so deeply as not to present any transparency, or the color light enough to discern its hue.
8. Microcosmic Salt—Phosphate of Soda and Ammonia—(NaO, NH4O + PO5).—Dissolve six parts of phosphate of soda (2NaO, HO, PO5), and one part of pure chloride of Ammonium (NH4Cl.), in two parts of boiling water, and allow it to cool. The greatest part of the formed double salt crystallizes, while the mother-liquid contains chloride of sodium, and some of the double salt. The crystals must be dissolved in as little boiling water as possible, and re-crystallized. These crystals must be dried and powdered.
When this double salt is heated, the water and the ammonia escape, while the incombustible residue has a composition similar to borax, viz., a free acid and an easily fusible salt. The effect of it is, therefore, similar to the borax. The free phosphoric acid expels, likewise, most other acids from their combinations, and combines with metallic oxides.
For supports, the platinum wire may be used, but the hook must be smaller than when borax is used, or the bead will not adhere. As for all the other experiments with this salt, the microscosmic salt is used the same as borax.
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