The particles of iron, nickel, and cobalt, it should be borne in mind, are attracted by the magnet.
The following substances are neither fused nor reduced in soda, viz.
alumina, magnesia, lime, baryta, strontia, the oxide of uranium, the oxides of cerium, zirconia, tantalic acid, thorina, glucina, and yttria. Neither are the alkalies, as they sink into the charcoal. The carbonates of the earths, strontia, and baryta fuse.
Part III
SPECIAL REACTIONS; OR, THE BEHAVIOR OF SUBSTANCES BEFORE THE BLOWPIPE.
a.n.a.lytical chemistry may be termed the art of converting the unknown const.i.tuents of substances, by means of certain operations, into new combinations which we recognize through the physical and chemical properties which they manifest.
It is, therefore, indispensably necessary, not only to be cognizant of the peculiar conditions by which these operations can be effected, but it is absolutely necessary to be acquainted with the forms and combinations of the resulting product, and with every modification which may be produced by altering the conditions of the a.n.a.lysis.
We shall first give the behavior of simple substances before the blowpipe; and the student should study this part thoroughly, by repeating each reaction, so that he can acquire a knowledge of the color, form, and physical properties in general, of the resulting combination. There is nothing, perhaps, which will contribute more readily to the progress of the pupil, than thorough practice with the reactions recommended in this part of the work, for when once the student shall have acquired a practical eye in the discernment of the peculiar appearances of substances after they have undergone the decompositions produced by the strong heat of the blowpipe flame, together with the reactions incident to these changes, then he will have greatly progressed in his study, and the rest will be comparatively simple.
A. METALLIC OXIDES.
GROUP FIRST.--THE ALKALIES: POTa.s.sA, SODA, AMMONIA, AND LITHIA.
The alkalies, in their pure, or carbonated state, render reddened litmus paper blue. This is likewise the case with the sulphides of the alkalies. The neutral salts of the alkalies, formed with the strong acids, do not change litmus paper, but the salts formed with the weak acids, render the red litmus paper blue; for instance, the alkaline salts with boracic acid. Fused with borax, soda, or microcosmic salt, they give a clear bead. The alkalies and their salts melt at a low red heat. The alkalies cannot be reduced to the metallic state before the blowpipe. They are not volatile when red hot, except the alkali ammonia, but they are volatile at a white heat.
(_a._) _Pota.s.sa._(KO).--It is not found free, but in combination with inorganic and organic acids, as well in the animal as in the vegetable organism, as in the mineral kingdom. In the pure, or anhydrous state, or as the carbonate, pota.s.sa absorbs moisture, and becomes fluid, or is deliquescent, as it is termed. By exposing pota.s.sa, or its easily fusible salts (except the phosphate or borate), upon platinum wire, to the point of the blue flame, there is communicated to the external flame a violet color, in consequence of a reduction and reoxidation.
This color, though characteristic of all the pota.s.sa compounds, is scarcely visible with the phosphate or borate salts of that alkali.
The admixture of a very little soda (1/300th) destroys the color imparted by the pota.s.sa, while the flame a.s.sumes a yellow color, characteristic of the soda. The presence of lithia changes the violet color of the potash into red. The silicates of pota.s.sa must exist in pretty large proportion before they can be detected by the violet color of the flame, and those minerals must melt easily at the edges.
The presence of a little soda in these instances conceals the reaction in the pota.s.sa entirely.
If alcohol is poured over pota.s.sa compounds which are powdered, and then set on fire, the external flame appears violet-colored, particularly when stirred with a gla.s.s rod, and when the alcohol is really consumed. The presence of soda in lithia will, in this case likewise, hide by their own characteristic color, that of the pota.s.sa.
The salts of pota.s.sa are absorbed when fused upon charcoal. The sulphur, bromine, chlorine, and iodine compounds of pota.s.sa give a white, but easily volatile sublimate upon the charcoal, around the place where the fused substance reposed. This white sublimate manifests itself only when the substance is melted and absorbed within the charcoal, and ceases to be visible as soon as it is submitted to the reducing flame, while the external flame is colored violet; sulphate of pota.s.sa, for instance, is reduced by the glowing charcoal into the sulphide. This latter is somewhat volatile, but by pa.s.sing through the oxidation flame, it is again oxidized into the sulphate.
This, being less volatile, sublimes upon the charcoal, but by exposing it again to the flame of reduction, it is reduced and carried off to be again oxidized by its pa.s.sage through the oxidation flame.
Pota.s.sa and its compounds give, with soda, borax or microcosmic salt, as well when hot as cold, colorless beads, unless the acid a.s.sociated with the alkali should itself produce a color. When borax is fused with some pure boracic acid, and sufficient of the oxide of nickel is added, so that the beads appear of a brown color after being cooled, and then the bead thus produced fused with the substance suspected to contain pota.s.sa, in the oxidation flame, the brown color is changed to blue. The presence of the other alkalies does not prevent this reaction. As it is not possible to detect pota.s.sa compounds with unerring certainty by the blowpipe flame, the the wet method should be resorted to for the purpose of confirming it.
The _silicates of pota.s.sa_ must be prepared as follows, for a.n.a.lytical purposes by the wet way. Mix one part of the finely powdered substance with two parts of soda (free from pota.s.sa), and one part of borax.
Fuse the mixture upon charcoal in the oxidation flame to a clear, transparent bead. This is to be exposed again with the pincers to the oxidation flame, to burn off the adhering coal particles. Then pulverize and dissolve in hydrochloric acid to separate the silica; evaporate to dryness, dissolve the residue in water, with the admixture of a little alcohol, and test the filtrate with chloride of platinum for pota.s.sa.
(_b._) _Soda_ (NaO).--This is one of the most abundant substances, although seldom found free, but combined with chlorine or some other less abundant compound. Soda, its hydrate and salts manifest in general the same properties as their respective potash compounds; but the salts of soda mostly contain crystal water, which leaves the salts if they are exposed to the air, and the salts effervesce.
By exposing soda or its compounds upon a platinum wire to the blue flame, a reddish-yellow color is communicated to the external flame, which appears as a long brilliant stream and considerably increased in volume. The presence of potash does not prevent this reaction of soda.
If there is too large a quant.i.ty of potash, the flame near to the substance is violet-colored, but the edge of the flame exhibits the characteristic tint of the soda. The presence of lithia changes the yellow color to a shade of red.
When alcohol is poured over powdered soda compounds and lighted, the flame exhibits a reddish-yellow color, particularly if the alcohol is stirred up with a gla.s.s rod, or if the alcohol is nearly consumed.
Fused upon charcoal, soda compounds are absorbed by the coal. The sulphide, chloride, iodide, and bromide of soda yield a white sublimate around the spot where the substance is laid, but this sublimate is not so copious as that of the potash compounds, and disappears when touched with the reduction flame, communicating a yellow color to the external flame. The presence of soda in compounds must likewise be confined by reactions in the wet way.
(_c._) _Ammonia_ (NH^{4}O).--In the fused state, and at the usual temperature, ammonia is a pungent gas, and exerts a reaction upon litmus paper similar to potash and soda. Ammonium is considered by chemists as a metal, from the nature of its behavior with other substances. It has not been isolated, but its existence is now generally conceded by all chemists. The ammonia salts are volatile, and many of them sublimate without being decomposed.
The salts of ammonia, on being heated in the point of the blue flame, produce a feeble green color in the external flame, just previous to their being converted into vapor. But this color is scarcely visible, and presents nothing characteristic. When the ammonia salts are mixed with the carbonate of soda, and heated in a gla.s.s tube closed at one end, carbonate of ammonia is sublimed, which can be readily recognized by its penetrating smell of spirits of hartshorn.
This sublimate will render blue a slip of red litmus paper. This can be easily done by moistening the litmus paper, and then inserting the end of it in the tube. By holding a gla.s.s rod, moistened with dilute hydrochloric acid, over the mouth of the tube, a white vapor is instantly rendered visible (sal ammoniac).
(_d._) _Lithia_ (LiO).--In the pure state, lithia is white and crystalline, not easily soluble in water, and does not absorb moisture. It changes red litmus to blue, and at a low red heat it melts. Lithia or its salts, exposed to the point of the blue flame, communicates a red color to the external or oxidation flame, in consequence of a reduction, sublimation, and re-oxidation of the lithia. An admixture of potash communicates to this flame a reddish-violet color, and the presence of soda that of a yellowish-red or orange. If the soda, however, is in too great proportion, then its intense yellow hides the red of the lithia. In the latter case the substance under test must be only imperfectly fused in the oxidation flame, and then dipped in wax or tallow. By exposing it now to the reduction flame, the red color imparted to the external flame by the lithia becomes visible, even if a considerable quant.i.ty of soda be present. A particular phenomenon appears with the phosphate of lithia, viz., the phosphoric acid itself possesses the property of communicating to the flame a bluish-green color. By its combination with lithia it still exhibits its characteristic color, while the latter presents likewise its peculiar tint. Then we perceive a green flame in the centre of the flame, while the red color of lithia surrounds it.
The _silicates_, which contain only a little lithia, produce only a slight hue in the flame, and often none at all. We have to mix one part of the silicate with two parts of a mixture composed of one part of fluorspar and one and a half parts of bisulphate of pota.s.sa.
Moisten the ma.s.s with water so that the ma.s.s will adhere, and then melt it upon a platinum wire in the reduction flame, when that of oxidation will present the red color of lithia.
The _Borates of lithia_ produce at first a green color, but it soon yields to the red of lithia. When alcohol is poured over lithia or its compounds, and inflamed, it burns with a deep red color, particularly if the fluid is stirred up with a gla.s.s rod, or when the alcohol is nearly consumed. This color presents the same modifications as the corresponding ones communicated to the blowpipe as mentioned above.
The salts of lithia are absorbed by charcoal when fused upon it. The sulphide, bromide, iodide, and chloride of lithia produce upon the charcoal a greyish-white sublimate, although not so copiously as the corresponding compounds of potash and soda. This sublimate disappears when touched by the reduction flame, while the oxidation flame gives the characteristic color of lithia.
SECOND GROUP.--THE ALKALINE EARTHS, BARYTA, STRONTIA, LIME, AND MAGNESIA.
In the pure state, the alkaline earths are caustic, cause red litmus paper to become blue, and are more or less soluble in water. Their sulphides are also soluble. The carbonates and phosphates of the alkaline earths are insoluble in water. By igniting the carbonates, their carbonic acid is expelled, and the alkaline earths are left in the caustic state. The alkaline earths are not volatile, and their organic salts are converted, by ignition, into carbonates.
(_a._) _Baryta._ (BaO).--This alkaline earth does not occur free in nature, but combined with acids, particularly with carbonic and sulphuric acids. In the pure state, baryta is of a greyish-white color, presents an earthy appearance, and is easily powdered. When sparingly moistened with water, it slakes, becomes heated, and forms a dry, white powder. With still more water it forms a crystalline ma.s.s, the hydrate of baryta, which is completely soluble in hot water. Pure baryta is infusible; the hydrate fuses at a red heat, without the loss of its hydratic water; if caustic baryta is exposed for too great a length of time to the flame, it absorbs water, originated by the combustion, and becomes a hydrate, when it will melt. Salts of baryta, formed with most acids, are insoluble in water; for instance, the salts with sulphuric, carbonic, a.r.s.enic, phosphoric, and boracic acids. The salts of baryta, soluble in water, are decomposed by ignition, except the chloride.
Carbonate of baryta loses its carbonic acid at a red heat, becomes caustic, and colors red litmus paper blue.
By exposing baryta or its compounds upon a platinum wire, or a splinter of the substance held with the platinum tongs, to the point of the blue flame, a pale apple-green color is communicated to the external flame. This color appears at first very pale, but soon becomes more intense. This color is most visible if the substance is operated with in small quant.i.ties. The chloride of barium produces the deepest color. This color is less intense if the carbonate or sulphate is used. The presence of strontia, lime, or magnesia, does not suppress the reaction of the baryta, unless they greatly predominate.
When alcohol is poured over baryta or its salts, and inflamed, a feeble green color is communicated to the flame, but this color should not be considered a characteristic of the salt.
Baryta and its compounds give, when fused with carbonate of soda upon platinum foil, a clear bead. Fused with soda upon charcoal, it is absorbed. The sulphate fuses at first to a clear bead, which soon spreads, and is absorbed and converted while boiling into a hepatic ma.s.s. If this ma.s.s is taken out, placed upon a piece of polished silver and moistened with a little water, a black spot of sulphide of silver is left after washing off the ma.s.s with water.
Borax dissolves baryta and its compounds with a hissing noise, as well in the flame of oxidation as in that of reduction. There is formed a clear bead which, with a certain degree of saturation, is clear when cold, but appears milk-white when overcharged, and of an opal, enamel appearance, when heated intermittingly, or with a vacillating flame, that changes frequently from the oxidating to the reducing flame.
Baryta and its compounds produce the same reactions with microcosmic salt.
Baryta and its compounds fuse when exposed to ignition in the oxidizing flame. Moistened with the solution of nitrate of cobalt, and heated in the oxidation flame, it presents a bead, colored from brick-red to brown, according to the quant.i.ty used. This color disappears when cold, and the bead falls to a pale grey powder after being exposed awhile to the air. When heated again, the color does not appear until fusion is effected. If carbonate of soda is fused upon platinum wire with so much of the sesquioxide of manganese that a green bead is produced, this bead, when fused with a sufficient quant.i.ty of baryta, or its compounds, after cooling, will appear of a bluish-green, or light blue color.
(_b._) _Strontia_ (SrO).--Strontia and its compounds are a.n.a.logous to the respective ones of baryta. The hydrate of strontia has the same properties as the hydrate of baryta, except that it is less soluble in water. The carbonate of strontia fuses a little at a red heat, swells, and bubbles up like cauliflower. This produces, in the blowpipe flame, an intense and splendid light, and now produces an alkaline reaction upon red litmus paper. The sulphate of strontia melts in the oxidation flame upon platinum foil, or upon charcoal, to a milk-white globule.
This fuses upon charcoal, spreads and is reduced to the sulphide, which is absorbed by the charcoal. It now produces the same reactions upon polished silver as the sulphate of baryta under the same conditions. By exposing strontia and its compounds upon platinum wire, or as a splinter with the platinum tongs, to the point of the blue flame, the external flame appears of an intense crimson color. The deepest red color is produced by the chloride of strontium, particularly at the first moment of applying the heat. After the salt is fused, the red color ceases to be visible in the flame, by which it is distinguished from the chloride of lithium. The carbonate of strontia swells up and produces a splendid white light, while the external flame is colored of a fine purple-red. The color produced by the sulphate of strontia is less intense. The presence of baryta destroys the reaction of the strontia, the flame presenting the light green color of the baryta.
If alcohol is poured over powdered strontia and inflamed, the flame appears purple or deep crimson, particularly if the fluid is stirred with a gla.s.s rod, and when the alcohol is nearly consumed.
The insoluble salts of strontia do not produce a very intense color.
Baryta does not prevent the reaction of the soluble salts of strontia, unless it exists greatly in excess. In the presence of baryta, strontia can be detected by the following process: mix some of the substance under examination with some pure graphite and water, by grinding in an agate mortar. Place the mixture upon charcoal, and expose it for a while to the reduction flame. The substance becomes reduced to sulphide of barium and sulphide of strontium, when it should be dissolved in hydrochloric acid. The solution should be evaporated to dryness, redissolved in a little water, and enough alcohol added that a spirit of 80 per cent. is produced. Inflame the spirit, and if strontia is present, the flame is tinged of a red color. This color can be discerned more distinctly by moistening some cotton with this spirit and inflaming it.
If strontia or its compounds are fused with a green bead of carbonate of soda and sesquioxide of manganese, as described under the head of baryta, a bead of a brown, brownish-green, or dark grey color is produced. Carbonate of soda does not dissolve pure strontia. The carbonate and sulphate of strontia melt with soda upon platinum foil to a bead, which is milk-white when cold, but fused upon charcoal they are absorbed. Strontia or its compounds produce with borax, or microcosmic salt, the same reactions as baryta. When they are moistened with nitrate of cobalt, and ignited in the oxidizing flame, a black, or grey infusible ma.s.s is produced.
(_c._) _Lime, Oxide of Calcium _(CaO).--Lime does not occur free in nature, but in combination with acids, chiefly the carbonic and sulphuric. The phosphate occurs princ.i.p.ally in bones. The hydrate and the salts of lime are in their properties similar to those of the two preceding alkaline earths. In the pure state, the oxide of calcium is white; it slakes, produces a high temperature, and falls into a white powder when sprinkled with a little water. It is now a hydrate, and has greatly increased in volume. The hydrate of lime is far less soluble in water than either those of baryta or strontia, and is less soluble in hot water than in cold. Lime, its hydrate and sulphide of calcium, have a strong alkaline reaction upon red litmus paper. Lime and its hydrate are infusible, but produce at a strong red heat a very intense and splendid white light, while the hydrate loses its water.