Elements of Chemistry Part 33

In this manner of operating it is impossible to determine the quant.i.ty of carbonic acid gas disengaged, because a part of it is absorbed by the water while pa.s.sing through it; but, when the carbonic acid is absorbed, the azotic gas remains; and, if it be agitated for a few minutes in caustic alkaline solution, we obtain it pure, and can easily determine its volume and weight. We may even, in this way, acquire a tollerably exact knowledge of the quant.i.ty of carbonic acid by repeating the experiment a great many times, and varying the proportions of charcoal, till we find the exact quant.i.ty requisite to deflagrate the whole nitre employed. Hence, by means of the weight of charcoal employed, we determine the weight of oxygen necessary for saturation, and deduce the quant.i.ty of oxygen contained in a given weight of nitre.

I have used another process, by which the results of this experiment are considerably more accurate, which consists in receiving the disengaged ga.s.ses in bell-gla.s.ses filled with mercury. The mercurial apparatus I employ is large enough to contain jars of from twelve to fifteen pints in capacity, which are not very readily managed when full of mercury, and even require to be filled by a particular method. When the jar is placed in the cistern of mercury, a gla.s.s syphon is introduced, connected with a small air-pump, by means of which the air is exhausted, and the mercury rises so as to fill the jar. After this, the gas of the deflagration is made to pa.s.s into the jar in the same manner as directed when water is employed.

I must again repeat, that this species of experiment requires to be performed with the greatest possible precautions. I have sometimes seen, when the disengagement of gas proceeded with too great rapidity, jars filled with more than an hundred and fifty pounds of mercury driven off by the force of the explosion, and broken to pieces, while the mercury was scattered about in great quant.i.ties.

When the experiment has succeeded, and the gas is collected under the jar, its quant.i.ty in general, and the nature and quant.i.ties of the several species of ga.s.ses of which the mixture is composed, are accurately ascertained by the methods already pointed out in the second chapter of this part of my work. I have been prevented from putting the last hand to the experiments I had begun upon deflagration, from their connection with the objects I am at present engaged in; and I am in hopes they will throw considerable light upon the operations belonging to the manufacture of gun-powder.

CHAP. X.

_Of the Instruments necessary for Operating upon Bodies in very high Temperatures._

SECT. I.

_Of Fusion._

We have already seen, that, by aqueous solution, in which the particles of bodies are separated from each other, neither the solvent nor the body held in solution are at all decomposed; so that, whenever the cause of separation ceases, the particles reunite, and the saline substance recovers precisely the same appearance and properties it possessed before solution. Real solutions are produced by fire, or by introducing and acc.u.mulating a great quant.i.ty of caloric between the particles of bodies; and this species of solution in caloric is usually called _fusion_.

This operation is commonly performed in vessels called crucibles, which must necessarily be less fusible than the bodies they are intended to contain. Hence, in all ages, chemists have been extremely solicitous to procure crucibles of very refractory materials, or such as are capable of resisting a very high degree of heat. The best are made of very pure clay or of porcelain earth; whereas such as are made of clay mixed with calcareous or silicious earth are very fusible. All the crucibles made in the neighbourhood of Paris are of this kind, and consequently unfit for most chemical experiments. The Hessian crucibles are tolerably good; but the best are made of Limoges earth, which seems absolutely infusible. We have, in France, a great many clays very fit for making crucibles; such, for instance, is the kind used for making melting pots at the gla.s.s-manufactory of St Gobin.

Crucibles are made of various forms, according to the operations they are intended to perform. Several of the most common kinds are represented Pl. VII. Fig. 7. 8. 9. and 10. the one represented at Fig.

9. is almost shut at its mouth.

Though fusion may often take place without changing the nature of the fused body, this operation is frequently employed as a chemical means of decomposing and recompounding bodies. In this way all the metals are extracted from their ores; and, by this process, they are revivified, moulded, and alloyed with each other. By this process sand and alkali are combined to form gla.s.s, and by it likewise pastes, or coloured stones, enamels, &c. are formed.

The action of violent fire was much more frequently employed by the ancient chemists than it is in modern experiments. Since greater precision has been employed in philosophical researches, the _humid_ has been preferred to the _dry_ method of process, and fusion is seldom had recourse to until all the other means of a.n.a.lysis have failed.

SECT. II.

_Of Furnaces._

These are instruments of most universal use in chemistry; and, as the success of a great number of experiments depends upon their being well or ill constructed, it is of great importance that a laboratory be well provided in this respect. A furnace is a kind of hollow cylindrical tower, sometimes widened above, Pl. XIII. Fig. 1. ABCD, which must have at least two lateral openings; one in its upper part F, which is the door of the fire-place, and one below, G, leading to the ash-hole.

Between these the furnace is divided by a horizontal grate, intended for supporting the fewel, the situation of which is marked in the figure by the line HI. Though this be the least complicated of all the chemical furnaces, yet it is applicable to a great number of purposes. By it lead, tin, bis.m.u.th, and, in general, every substance which does not require a very strong fire, may be melted in crucibles; it will serve for metallic oxydations, for evaporatory vessels, and for sand-baths, as in Pl. III. Fig. 1. and 2. To render it proper for these purposes, several notches, m m m m, Pl. XIII. Fig. 1. are made in its upper edge, as otherwise any pan which might be placed over the fire would stop the pa.s.sage of the air, and prevent the fewel from burning. This furnace can only produce a moderate degree of heat, because the quant.i.ty of charcoal it is capable of consuming is limited by the quant.i.ty of air which is allowed to pa.s.s through the opening G of the ash-hole. Its power might be considerably augmented by enlarging this opening, but then the great stream of air which is convenient for some operations might be hurtful in others; wherefore we must have furnaces of different forms, constructed for different purposes, in our laboratories: There ought especially to be several of the kind now described of different sizes.

The reverberatory furnace, Pl. XIII. Fig. 2. is perhaps more necessary.

This, like the common furnace, is composed of the ash-hole HIKL, the fire-place KLMN, the laboratory MNOP, and the dome RRSS, with its funnel or chimney TTVV; and to this last several additional tubes may be adapted, according to the nature of the different experiments. The retort A is placed in the division called the laboratory, and supported by two bars of iron which run across the furnace, and its beak comes out at a round hole in the side of the furnace, one half of which is cut in the piece called the laboratory, and the other in the dome. In most of the ready made reverberatory furnaces which are sold by the potters at Paris, the openings both above and below are too small: These do not allow a sufficient volume of air to pa.s.s through; hence, as the quant.i.ty of charcoal consumed, or, what is much the same thing, the quant.i.ty of caloric disengaged, is nearly in proportion to the quant.i.ty of air which pa.s.ses through the furnace, these furnaces do not produce a sufficient effect in a great number of experiments. To remedy this defect, there ought to be two openings GG to the ash-hole; one of these is shut up when only a moderate fire is required; and both are kept open when the strongest power of the furnace is to be exerted. The opening of the dome SS ought likewise to be considerably larger than is usually made.

It is of great importance not to employ retorts of too large size in proportion to the furnace, as a sufficient s.p.a.ce ought always to be allowed for the pa.s.sage of the air between the sides of the furnace and the vessel. The retort A in the figure is too small for the size of the furnace, yet I find it more easy to point out the error than to correct it. The intention of the dome is to oblige the flame and heat to surround and strike back or reverberate upon every part of the retort, whence the furnace gets the name of reverberatory. Without this circ.u.mstance the retort would only be heated in its bottom, the vapours raised from the contained substance would condense in the upper part, and a continual cohabitation would take place without any thing pa.s.sing over into the receiver, but, by means of the dome, the retort is equally heated in every part, and the vapours being forced out, can only condense in the neck of the retort, or in the recipient.

To prevent the bottom of the retort from being either heated or coolled too suddenly, it is sometimes placed in a small sand-bath of baked clay, standing upon the cross bars of the furnace. Likewise, in many operations, the retorts are coated over with lutes, some of which are intended to preserve them from the too sudden influence of heat or of cold, while others are for sustaining the gla.s.s, or forming a kind of second retort, which supports the gla.s.s one during operations wherein the strength of the fire might soften it. The former is made of brick-clay with a little cow's hair beat up alongst with it, into a paste or mortar, and spread over the gla.s.s or stone retorts. The latter is made of pure clay and pounded stone-ware mixed together, and used in the same manner. This dries and hardens by the fire, so as to form a true supplementary retort capable of retaining the materials, if the gla.s.s retort below should crack or soften. But, in experiments which are intended for collecting ga.s.ses, this lute, being porous, is of no manner of use.

In a great many experiments wherein very violent fire is not required, the reverberatory furnace may be used as a melting one, by leaving out the piece called the laboratory, and placing the dome immediately upon the fire-place, as represented Pl. XIII. Fig. 3. The furnace represented in Fig. 4. is very convenient for fusions; it is composed of the fire-place and ash-hole ABD, without a door, and having a hole E, which receives the muzzle of a pair of bellows strongly luted on, and the dome ABGH, which ought to be rather lower than is represented in the figure.

This furnace is not capable of producing a very strong heat, but is sufficient for ordinary operations, and may be readily moved to any part of the laboratory where it is wanted. Though these particular furnaces are very convenient, every laboratory must be provided with a forge furnace, having a good pair of bellows, or, what is more necessary, a powerful melting furnace. I shall describe the one I use, with the principles upon which it is constructed.

The air circulates in a furnace in consequence of being heated in its pa.s.sage through the burning coals; it dilates, and, becoming lighter than the surrounding air, is forced to rise upwards by the pressure of the lateral columns of air, and is replaced by fresh air from all sides, especially from below. This circulation of air even takes place when coals are burnt in a common chaffing dish; but we can readily conceive, that, in a furnace open on all sides, the ma.s.s of air which pa.s.ses, all other circ.u.mstances being equal, cannot be so great as when it is obliged to pa.s.s through a furnace in the shape of a hollow tower, like most of the chemical furnaces, and consequently, that the combustion must be more rapid in a furnace of this latter construction. Suppose, for instance, the furnace ABCDEF open above, and filled with burning coals, the force with which the air pa.s.ses through the coals will be in proportion to the difference between the specific gravity of two columns equal to AC, the one of cold air without, and the other of heated air within the furnace. There must be some heated air above the opening AB, and the superior levity of this ought likewise to be taken into consideration; but, as this portion is continually coolled and carried off by the external air, it cannot produce any great effect.

But, if we add to this furnace a large hollow tube GHAB of the same diameter, which preserves the air which has been heated by the burning coals from being coolled and dispersed by the surrounding air, the difference of specific gravity which causes the circulation will then be between two columns equal to GC. Hence, if GC be three times the length of AC, the circulation will have treble force. This is upon the supposition that the air in GHCD is as much heated as what is contained in ABCD, which is not strictly the case, because the heat must decrease between AB and GH; but, as the air in GHAB is much warmer than the external air, it follows, that the addition of the tube must increase the rapidity of the stream of air, that a larger quant.i.ty must pa.s.s through the coals, and consequently that a greater degree of combustion must take place.

We must not, however, conclude from these principles, that the length of this tube ought to be indefinitely prolonged; for, since the heat of the air gradually diminishes in pa.s.sing from AB to GH, even from the contact of the sides of the tube, if the tube were prolonged to a certain degree, we would at last come to a point where the specific gravity of the included air would be equal to the air without; and, in this case, as the cool air would no longer tend to rise upwards, it would become a gravitating ma.s.s, resisting the ascension of the air below. Besides, as this air, which has served for combustion, is necessarily mixed with carbonic acid gas, which is considerably heavier than common air, if the tube were made long enough, the air might at last approach so near to the temperature of the external air as even to gravitate downwards; hence we must conclude, that the length of the tube added to a furnace must have some limit beyond which it weakens, instead of strengthening the force of the fire.

From these reflections it follows, that the first foot of tube added to a furnace produces more effect than the sixth, and the sixth more than the tenth; but we have no data to ascertain at what height we ought to stop. This limit of useful addition is so much the farther in proportion as the materials of the tube are weaker conductors of heat, because the air will thereby be so much less coolled; hence baked earth is much to be preferred to plate iron. It would be even of consequence to make the tube double, and to fill the interval with rammed charcoal, which is one of the worst conductors of heat known; by this the refrigeration of the air will be r.e.t.a.r.ded, and the rapidity of the stream of air consequently increased; and, by this means, the tube may be made so much the longer.

As the fire-place is the hottest part of a furnace, and the part where the air is most dilated in its pa.s.sage, this part ought to be made with a considerable widening or belly. This is the more necessary, as it is intended to contain the charcoal and crucible, as well as for the pa.s.sage of the air which supports, or rather produces the combustion; hence we only allow the interstices between the coals for the pa.s.sage of the air.

From these principles my melting furnace is constructed, which I believe is at least equal in power to any hitherto made, though I by no means pretend that it possesses the greatest possible intensity that can be produced in chemical furnaces. The augmentation of the volume of air produced during its pa.s.sage through a melting furnace not being hitherto ascertained from experiment, we are still unacquainted with the proportions which should exist between the inferior and superior apertures, and the absolute size of which these openings should be made is still less understood; hence data are wanting by which to proceed upon principle, and we can only accomplish the end in view by repeated trials.

This furnace, which, according to the above stated rules, is in form of an eliptical spheroid, is represented Pl. XIII. Fig. 6. ABCD; it is cut off at the two ends by two plains, which pa.s.s, perpendicular to the axis, through the foci of the elipse. From this shape it is capable of containing a considerable quant.i.ty of charcoal, while it leaves sufficient s.p.a.ce in the intervals for the pa.s.sage of the air. That no obstacle may oppose the free access of external air, it is perfectly open below, after the model of Mr Macquer's melting furnace, and stands upon an iron tripod. The grate is made of flat bars set on edge, and with considerable interstices. To the upper part is added a chimney, or tube, of baked earth, ABFG, about eighteen feet long, and almost half the diameter of the furnace. Though this furnace produces a greater heat than any hitherto employed by chemists, it is still susceptible of being considerably increased in power by the means already mentioned, the princ.i.p.al of which is to render the tube as bad a conductor of heat as possible, by making it double, and filling the interval with rammed charcoal.

When it is required to know if lead contains any mixture of gold or silver, it is heated in a strong fire in capsules of calcined bones, which are called cuppels. The lead is oxydated, becomes vitrified, and sinks into the substance of the cuppel, while the gold or silver, being incapable of oxydation, remain pure. As lead will not oxydate without free access of air, this operation cannot be performed in a crucible placed in the middle of the burning coals of a furnace, because the internal air, being mostly already reduced by the combustion into azotic and carbonic acid gas, is no longer fit for the oxydation of metals. It was therefore necessary to contrive a particular apparatus, in which the metal should be at the same time exposed to the influence of violent heat, and defended from contact with air rendered incombustible by its pa.s.sage through burning coals. The furnace intended for answering this double purpose is called the cuppelling or essay furnace. It is usually made of a square form, as represented Pl. XIII. Fig. 8. and 10. having an ash-hole AABB, a fire-place BBCC, a laboratory CCDD, and a dome DDEE.

The m.u.f.fle or small oven of baked earth GH, Fig. 9. being placed in the laboratory of the furnace upon cross bars of iron, is adjusted to the opening GG, and luted with clay softened in water. The cuppels are placed in this oven or m.u.f.fle, and charcoal is conveyed into the furnace through the openings of the dome and fire-place. The external air enters through the openings of the ash-hole for supporting the combustion, and escapes by the superior opening or chimney at EE; and air is admitted through the door of the m.u.f.fle GG for oxydating the contained metal.

Very little reflection is sufficient to discover the erroneous principles upon which this furnace is constructed. When the opening GG is shut, the oxydation is produced slowly, and with difficulty, for want of air to carry it on; and, when this hole is open, the stream of cold air which is then admitted fixes the metal, and obstructs the process.

These inconveniencies may be easily remedied, by constructing the m.u.f.fle and furnace in such a manner that a stream of fresh external air should always play upon the surface of the metal, and this air should be made to pa.s.s through a pipe of clay kept continually red hot by the fire of the furnace. By this means the inside of the m.u.f.fle will never be coolled, and processes will be finished in a few minutes, which at present require a considerable s.p.a.ce of time.

Mr Sage remedies these inconveniencies in a different manner; he places the cuppel containing lead, alloyed with gold or silver, amongst the charcoal of an ordinary furnace, and covered by a small porcelain m.u.f.fle; when the whole is sufficiently heated, he directs the blast of a common pair of hand-bellows upon the surface of the metal, and completes the cuppellation in this way with great ease and exactness.

SECT. III.

_Of increasing the Action of Fire, by using Oxygen Gas instead of Atmospheric Air._

By means of large burning gla.s.ses, such as those of Tchirnausen and Mr de Trudaine, a degree of heat is obtained somewhat greater than has. .h.i.therto been produced in chemical furnaces, or even in the ovens of furnaces used for baking hard porcelain. But these instruments are extremely expensive, and do not even produce heat sufficient to melt crude platina; so that their advantages are by no means sufficient to compensate for the difficulty of procuring, and even of using them.

Concave mirrors produce somewhat more effect than burning gla.s.ses of the same diameter, as is proved by the experiments of Messrs Macquer and Beaume with the speculum of the Abbe Bouriot; but, as the direction of the reflected rays is necessarily from below upwards, the substance to be operated upon must be placed in the air without any support, which renders most chemical experiments impossible to be performed with this instrument.

For these reasons, I first endeavoured to employ oxygen gas for combustion, by filling large bladders with it, and making it pa.s.s through a tube capable of being shut by a stop-c.o.c.k; and in this way I succeeded in causing it to support the combustion of lighted charcoal.

The intensity of the heat produced, even in my first attempt, was so great as readily to melt a small quant.i.ty of crude platina. To the success of this attempt is owing the idea of the gazometer, described p.

308. _et seq._ which I subst.i.tuted instead of the bladders; and, as we can give the oxygen gas any necessary degree of pressure, we can with this instrument keep up a continued stream, and give it even a very considerable force.

The only apparatus necessary for experiments of this kind consists of a small table ABCD, Pl. XII. Fig. 15, with a hole F, through which pa.s.ses a tube of copper or silver, ending in a very small opening at G, and capable of being opened or shut by the stop-c.o.c.k H. This tube is continued below the table at l m n o, and is connected with the interior cavity of the gazometer. When we mean to operate, a hole of a few lines deep must be made with a chizel in a piece of charcoal, into which the substance to be treated is laid; the charcoal is set on fire by means of a candle and blow-pipe, after which it is exposed to a rapid stream of oxygen gas from the extremity G of the tube FG.

This manner of operating can only be used with such bodies as can be placed, without inconvenience, in contact with charcoal, such as metals, simple earths, &c. But, for bodies whose elements have affinity to charcoal, and which are consequently decomposed by that substance, such as sulphats, phosphats, and most of the neutral salts, metallic gla.s.ses, enamels, &c. we must use a lamp, and make the stream of oxygen gas pa.s.s through its flame. For this purpose, we use the elbowed blow-pipe ST, instead of the bent one FG, employed with charcoal. The heat produced in this second manner is by no means so intense as in the former way, and is very difficultly made to melt platina. In this manner of operating with the lamp, the substances are placed in cuppels of calcined bones, or little cups of porcelain, or even in metallic dishes. If these last are sufficiently large, they do not melt, because, metals being good conductors of heat, the caloric spreads rapidly through the whole ma.s.s, so that none of its parts are very much heated.

In the Memoirs of the Academy for 1782, p. 476. and for 1783, p. 573.

the series of experiments I have made with this apparatus may be seen at large. The following are some of the princ.i.p.al results.

1. Rock cristal, or pure silicious earth, is infusible, but becomes capable of being softened or fused when mixed with other substances.

2. Lime, magnesia, and barytes, are infusible, either when alone, or when combined together; but, especially lime, they a.s.sist the fusion of every other body.

3. Argill, or pure base of alum, is completely fusible _per se_ into a very hard opake vitreous substance, which scratches gla.s.s like the precious stones.

4. All the compound earths and stones are readily fused into a brownish gla.s.s.

5. All the saline substances, even fixed alkali, are volatilized in a few seconds.