The bulb is also a convenient little instrument for the purpose of heating those substances which phosph.o.r.esce, and likewise those salts that decrepitate.
Should the above reactions not be readily discerned, it should not be considered as an indication that the substances are not present, for they are frequently expelled in such combinations that the above reactions will not take place. This is often the case with sulphur, selenium, a.r.s.enic, and tellurium. It frequently happens, likewise, that these substances are in such combinations that heat alone will not sublime them; or else two or more of them may arise together, and thus complicate the sublimate, so that the eye cannot readily detect either substance. Sometimes sulphur and a.r.s.enic will coat the tube with a metal-like appearance, which is deceptive. This coating presents a metallic l.u.s.tre at its lower portion, but changing, as it progresses upward, to a dark brown, light brown, orange or yellow; this sublimate being due to combinations of a.r.s.enic and sulphur, which compounds are volatilized at a lower temperature than metallic a.r.s.enic.
If certain reagents are mixed with many substances, changes are effected which would not ensue with heat alone. _Formiate of soda_ possesses the property of readily reducing metallic oxides. When this salt is heated, it gives off a quant.i.ty of carbonic oxide gas. This gas, when in the presence of a metallic oxide, easily reduces the metal, by withdrawing its oxygen from it, and being changed into carbonic oxide. If a little fly-stone is mixed with some formiate of soda, and heated in the bulb, the a.r.s.enic is reduced, volatilized, and condenses in the cool portion of the tube. By this method, the smallest portion of a grain of the a.r.s.enical compound may be thus examined with the greatest readiness. If the residue is now washed, by which the soda is got rid of, the metallic a.r.s.enic may be obtained in small spangles. If the compound examined be the sulphide of antimony, the one-thousandth part can be readily detected, and hence this method is admirably adapted to the examination of medicinal antimonial compounds. The a.r.s.enites of silver and copper are reduced by the formiate of soda to their metals, mixed with metallic a.r.s.enic. The mercurial salts are all reduced with the metal plainly visible as a bright silvery ring on the cool portion of the tube. The chloride and nitrate of silver are completely reduced, and may be obtained after working out the soda, as bright metallic spangles. The salts of antimony and zinc are thus reduced; also the sulphate of cadmium. The sublimate of the latter, although in appearance not unlike that of a.r.s.enic, can easily be distinguished by its brighter color. It is, in fact, the rich yellow of this sublimate which has led artists to adopt it as one of their most valued pigments.
2. EXAMINATIONS IN THE OPEN TUBE.
The substance to be operated upon should be placed in the tube, about half an inch from the end, and the flame applied at first very cautiously, increasing gradually to the required temperature. The tube, in all these _roasting_ operations, as they are termed, should be held in an inclined position. The nearer perpendicular the tube is held, the stronger is the draught of air that pa.s.ses through it. If but little heat is required in the open tube operation, the spirit-lamp is the best method of applying the heat. But if a greater temperature is required, then recourse must be had to the blowpipe.
Upon the angle of inclination of the tube depends the amount of air that pa.s.ses through it, and therefore, the rapidity of the draught may be easily regulated at the will of the operator. The inclination of the tube may, as a general rule, be about the angle represented in Fig. 14.
[Ill.u.s.tration Fig. 14.]
The length of the tube must be about six inches, so that the portion upon which the substance rested in a previous examination may be cut off. The portion of the tube left will answer for several similar operations.
When the substance is under examination, we should devote our attention to the nature of the sublimates, and to that of the _odors_ of the gases. If sulphur be in the substance experimented upon, the characteristic odor of sulphurous acid gas will readily indicate the sulphur. If metallic sulphides, for instance, are experimented upon, the sulphurous acid gas eliminated will readily reveal their presence.
As it is a property of this gas to bleach, a piece of Brazil-wood test paper should be held in the mouth of the tube, when its loss of color will indicate the presence of the sulphurous acid. It often happens, too, that a slight deposition of sulphur will be observed upon the cool portion of the tube. This is particularly the case with those sulphides, which yield sublimates of sulphur when heated in the bulb.
_Selenium_ undergoes but slight oxidation, but it becomes readily volatilized, and may be observed on the cool portion of the tube. At the same time the nose, if applied close to the end of the tube, will detect the characteristic odor of rotten horse-radish. a.r.s.enic also gives its peculiar alliaceous odor, which is so characteristic that it can be easily detected. A few of the a.r.s.enides produce this odor. The _sublimates_ should be carefully observed, as they indicate often with great certainty the presence of certain substances; for instance, that of a.r.s.enic. The sublimate, in this case, presents itself as the a.r.s.enious acid, or the metallic a.r.s.enic itself. If it be the former, it may be discerned by aid of the magnifying gla.s.s as beautiful glittering octohedral crystals. If the latter, the metallic l.u.s.tre will reveal it.
But it will be observed that while some of the a.r.s.enides are sublimed at a comparatively low temperature, others require a very high one.
_Antimony_ gives a white sublimate when its salts are roasted, as the sulphide, or the antimonides themselves, or the oxide of this metal.
This white sublimate is not antimonious acid, but there is mixed with it the oxide of antimony with which the acid is sublimed. As is the case with a.r.s.enious acid, the antimonious acid may, by dexterous heating, be driven from one portion of the tube to another.
_Tellurium_, or its acid and oxide, may be got as a sublimate in the tube. The tellurious acid, unlike the a.r.s.enious and antimonious acids, cannot be driven from one portion of the tube to another, but, on the contrary, it fuses into small clear globules, visible to the naked eye sometimes, but quite so with the aid of the magnifying gla.s.s.
_Lead_, or its chloride, sublimes like tellurium, and, like that substance, fuses into globules or drops.
_Bis.m.u.th_, or its sulphide, sublimes into an orange or brownish globules, when it is melted, as directed above, for tellurium. The color of the bis.m.u.th and lead oxides are somewhat similar, although that of the latter is paler.
If any mineral containing _fluorine_, is fused, first with the microcosmic salt bead, then put into the tube, and the flame of the blowpipe be directed _into_ the tube upon the bead, hydrofluoric acid is disengaged and attacks the inside of the tube. The fluoride of calcium, or fluorspar, may be used for this experiment.
During the roasting, a brisk current of air should be allowed to pa.s.s through the tube, whereby unoxidized matter may be prevented from volatilization, and the clogging up of the substance under examination be prevented.
3. EXAMINATIONS UPON CHARCOAL.
In making examinations upon charcoal, it is quite necessary that the student should make himself familiar with the different and characteristic appearances of the deposits upon the charcoal. In this case I have found the advice given by Dr. Sherer to be the best; that is, to begin with the examination of the pure materials first, until the eye becomes familiarized with the appearances of their incrustations upon charcoal.
The greater part of the metals fuse when submitted to the heat of the blowpipe, and if exposed to the outer flame, they oxidize. These metals, termed the n.o.ble metals, do not oxidize, but they fuse. The metals platinum, iridium, rhodium, osmium and palladium do not fuse.
The metal osmium, if exposed to the flame of oxidation, fuses and is finally dissipated as osmic acid. In the latter flame, the salts of the n.o.ble metals are reduced to the metallic state, and the charcoal is covered with the bright metal.
We shall give a brief description of the appearance of the princ.i.p.al elementary bodies upon being fused with charcoal. This plan is that deemed the most conducive to the progress of the student, by Berzelius, Plattner, and Sherer. Experience has taught us that this method is the most efficient that could have been devised as an initiatory exercise for the student, ere he commences a more concise and methodical method of a.n.a.lysis. In these reactions upon charcoal, we shall follow nearly the language of Plattner and Sherer.
SELENIUM is not difficult of fusion, and gives off brown fumes in either the oxidation or reduction flame. The deposit upon the charcoal is of a steel-grey color, with a slightly metallic l.u.s.tre. The deposit however that fuses outside of this steel-grey one is of a dull violet color, shading off to a light brown. Under the flame of oxidation this deposit is easily driven from one portion of the charcoal to another, while the application of the reducing flame volatilizes it with the evolution of a beautiful blue light. The characteristic odor of decayed horse-radish distinguishes the volatilization of this metal.
TELLURIUM.--This metal fuses with the greatest readiness, and is reduced to vapor under both flames with fumes, and coats the charcoal with a deposit of tellurous acid. This deposit is white near the centre, and is of a dark yellow near the edges. It may be driven from place to place by the flame of oxidation, while that of reduction volatilizes it with a green flame. If there be a mixture of selenium present, then the color of the flame is bluish-green.
a.r.s.eNIC.--This metal is volatilized without fusing, and covers the charcoal both in the oxidizing and reducing flames with a deposit of a.r.s.enious acid. This coating is white in the centre, and grey towards the edges, and is found some distance from the a.s.say. By the most gentle application of the flame, it is immediately volatilized, and if touched for a moment with the reducing flame, it disappears, tinging the flame pale blue. During volatilization a strong garlic odor is distinctly perceptible, very characteristic of a.r.s.enic, and by which its presence in any compound may be immediately recognized.
ANTIMONY.--This metal fuses readily, and coats the charcoal under both flames with antimonious acid. This incrustation is of a white color where thick, but of a bluish tint where it is thin, and is found nearer to the a.s.say than that of a.r.s.enic. When greatly heated by the flame of oxidation, it is driven from place to place without coloring the flame, but when volatilized by the flame of reduction, it tinges the flame blue. As antimonious acid is not so volatile as a.r.s.enious acid, they may thus be easily distinguished from one another.
When metallic antimony is fused upon charcoal, and the metallic bead raised to a red heat, if the blast be suspended, the fluid bead remains for some time at this temperature, giving off opaque white fumes, which are at first deposited on the surrounding charcoal, and then upon the bead itself, covering it with white, pearly crystals.
The phenomenon is dependent upon the fact, that the heated b.u.t.ton of antimony, in absorbing oxygen from the air, developes sufficient heat to maintain the metal in a fluid state, until it becomes entirely covered with crystals of antimonious acid so formed.
BIs.m.u.tH.--This metal fuses with ease, and under both flames covers the charcoal with a coating of oxide, which, while hot, is of an orange-yellow color, and after cooling, of a lemon-yellow color, pa.s.sing, at the edges, into a bluish white. This white coating consists of the carbonate of bis.m.u.th. The sublimate from bis.m.u.th is formed at a less distance from the a.s.say than is the case with antimony. It may be driven from place to place by the application of either flame; but in so doing, the oxide is first reduced by the heated charcoal, and the metallic bis.m.u.th so formed is volatilized and reoxidized. The flame is uncolored.
LEAD.--This metal readily fuses under either flame, and incrusts the charcoal with oxide at about the same distance from the a.s.say as is the case with bis.m.u.th. The oxide is, while hot, of a dark lemon-yellow color, but upon cooling, becomes of a sulphur yellow. The carbonate which is formed upon the charcoal, beyond the oxide, is of a bluish-white color. If the yellow incrustation of the oxide be heated with the flame of oxidation, it disappears, undergoing changes similar to those of bis.m.u.th above mentioned. Under the flame of reduction, it, however, disappears, tinging the flame blue.
CADMIUM.--This metal fuses with ease, and, in the flame of oxidation, takes fire, and burns with a deep yellow color, giving off brown fumes, which coat the charcoal, to within a small distance of the a.s.say, with oxide of cadmium. This coating exhibits its characteristic reddish-brown color most clearly when cold. Where the coating is very thin, it pa.s.ses to an orange color. As oxide of cadmium is easily reduced, and the metal very volatile, the coating of oxide may be driven from place to place by the application of either flame, to neither of which does it impart any color. Around the deposit of oxide, the charcoal has occasionally a variegated tarnish.
ZINC.--This metal fuses with ease, and takes fire in the flame of oxidation, burning with a brilliant greenish-white light, and forming thick white fumes of oxide of zinc, which coat the charcoal round the a.s.say. This coating is yellow while hot, but when perfectly cooled, becomes white. If heated with the flame of oxidation, it shines brilliantly, but is not volatilized, since the heated charcoal is, under these circ.u.mstances, insufficient to effect its reduction. Even under the reducing flame, it disappears very slowly.
TIN.--This metal fuses readily, and, in the flame of oxidation, becomes covered with oxide, which, by a strong blast, may be easily blown off. In the reducing flame, the fused metal a.s.sumes a white surface, and the charcoal becomes covered with oxide. This oxide is of a pale yellow color while hot, and is quite brilliant when the flame of oxidation is directed upon it. After cooling, it becomes white. It is found immediately around the a.s.say, and cannot be volatilized by the application of either flame.
MOLYBDENUM.--This metal, in powder, is infusible before the blowpipe.
If heated in the outer flame, it becomes gradually oxidized, and incrusts the charcoal, at a small distance from the a.s.say, with molybdic acid, which, near the a.s.say, forms transparent crystalline scales, and is elsewhere deposited as a fine powder. The incrustation, while hot, is of a yellow color, but becomes white after cooling. It may be volatilized by heating with either flame, and leaves the surface of the charcoal, when perfectly cooled, of a dark-red copper color, with a metallic l.u.s.tre, due to the oxide of molybdenum, which has been formed by the reducing action of the charcoal upon the molybdic acid. In the reducing flame, metallic molybdenum remains unchanged.
SILVER.--This metal, when fused alone, and kept in this state for some time, under a strong oxidizing flame, covers the charcoal with a thin film of dark reddish-brown oxide. If the silver be alloyed with lead, a yellow incrustation of the oxide of that metal is first formed, and afterwards, as the silver becomes more pure, a dark red deposit is formed on the charcoal beyond. If the silver contains a small quant.i.ty of antimony, a white incrustation of antimonious acid is formed, which becomes red on the surface if the blast be continued. And if lead and antimony are both present in the silver, after the greater part of these metals have been volatilized, a beautiful crimson incrustation is produced upon the charcoal. This result is sometimes obtained in fusing rich silver ores on charcoal.
SULPHIDES, CHLORIDES, IODIDES, AND BROMIDES.
In blowpipe experiments, it rarely occurs that we have to deal with pure metals, which, if not absolutely non-volatile, are recognized by the incrustation they form upon charcoal. Some compound substances, when heated upon charcoal, form white incrustations, resembling that formed by antimony, and which, when heated, may, in like manner, be driven from place to place. Among these are certain sulphides, as sulphide of pota.s.sium, and sulphide of sodium, which are formed by the action of the reducing flame upon the sulphates of pota.s.sa and soda, and are, when volatilized, reconverted into those sulphates, and as such deposited on the charcoal. No incrustation is, however, formed, until the whole of the alkaline sulphate has been absorbed into the charcoal, and has parted with its oxygen. As sulphide of pota.s.sium is more volatile than sulphide of sodium, an incrustation is formed from the former sooner than from the latter of these salts, and is considerably thicker in the former case. If the potash incrustation be touched with the reducing flame, it disappears with a violet-colored flame; and if a soda incrustation be treated in like manner, an orange-yellow flame is produced.
Sulphide of lithium, formed by heating the sulphate in the reducing flame, is volatilized in similar manner by a strong blast, although less readily than the sulphide of sodium. It affords a greyish white film, which disappears with a crimson flame when submitted to the reducing flame.
Besides the above, the sulphides of bis.m.u.th and lead give, when heated in either flame, two different incrustations, of which the more volatile is of a white color, and consists in the one case of sulphate of lead, and in the other of sulphate of bis.m.u.th. If either of these be heated under the reducing flame, it disappears in the former case with a bluish flame, in the latter unaccompanied by any visible flame.
The incrustation formed nearest to the a.s.say consists of the oxide of lead or bis.m.u.th, and is easily recognized by its color when hot and after cooling. There are many other metallic sulphides, which, when heated by the blowpipe flame, cover the charcoal with a white incrustation, as sulphide of antimony, sulphide of zinc, and sulphide of tin. In all these cases, however, the incrustation consists of the metallic oxide alone, and either volatilizes or remains unchanged, when submitted to the oxidizing flame.
Of the metallic chlorides there are many which, when heated on charcoal with the blowpipe flame, are volatilized and redeposited as a white incrustation. Among these are the chlorides of pota.s.sium, sodium, and lithium, which volatilize and cover the charcoal immediately around the a.s.say with a thin white film, after they have been fused and absorbed into the charcoal, chloride of pota.s.sium forms the thickest deposit, and chloride of lithium the thinnest, the latter being moreover of a greyish-white color. The chlorides of ammonium, mercury, and antimony volatilize without fusing.
The chlorides of zinc, cadmium, lead, bis.m.u.th, and tin first fuse and then cover the charcoal with two different incrustations, one of which is a white volatile chloride, and the other a less volatile oxide of the metal.
Some of the incrustations formed by metallic chlorides disappear with a colored flame when heated with the reducing flame; thus chloride of pota.s.sium affords a violet flame, chloride of sodium an orange one, chloride of lithium a crimson flame, and chloride of lead a blue one.
The other metals mentioned above volatilize without coloring the flame.
The chloride of copper fuses and colors the flame of a beautiful blue.
Moreover, if a continuous blast be directed upon the salt, a part of it is driven off in the form of white fumes which smell strongly of chlorine, and the charcoal is covered with incrustations of three different colors. That which is formed nearest to the a.s.say is of a dark grey color, the next, a dark yellow pa.s.sing into brown, and the most distant of a bluish white color. If this incrustation be heated under the reducing flame, it disappears with a blue flame.
Metallic iodides and bromides behave upon charcoal in a similar manner to the chlorides. Those princ.i.p.ally deserving of mention are the bromides and iodides of pota.s.sium and sodium. These fuse upon charcoal, are absorbed into its pores, and volatilize in the form of white fumes, which are deposited upon the charcoal at some distance from the a.s.say. When the saline films so formed are submitted to the reducing flame, they disappear, coloring the flame in the same manner as the corresponding chlorides.
4. EXAMINATIONS IN THE PLATINUM FORCEPS.