Combustion, according to what has been already said in the First Part of this Work, is the decomposition of oxygen gas produced by a combustible body. The oxygen which forms the base of this gas is absorbed by, and enters into, combination with the burning body, while the caloric and light are set free. Every combustion, therefore, necessarily supposes oxygenation; whereas, on the contrary, every oxygenation does not necessarily imply concomitant combustion; because combustion, properly so called, cannot take place without disengagement of caloric and light. Before combustion can take place, it is necessary that the base of oxygen gas should have greater affinity to the combustible body than it has to caloric; and this elective attraction, to use Bergman's expression, can only take place at a certain degree of temperature, which is different for each combustible substance; hence the necessity of giving a first motion or beginning to every combustion by the approach of a heated body. This necessity of heating any body we mean to burn depends upon certain considerations, which have not hitherto been attended to by any natural philosopher, for which reason I shall enlarge a little upon the subject in this place.
Nature is at present in a state of equilibrium, which cannot have been attained until all the spontaneous combustions or oxygenations possible in the ordinary degrees of temperature had taken place. Hence, no new combustions or oxygenations can happen without destroying this equilibrium, and raising the combustible substances to a superior degree of temperature. To illustrate this abstract view of the matter by example: Let us suppose the usual temperature of the earth a little changed, and that it is raised only to the degree of boiling water; it is evident, that, in this case, phosphorus, which is combustible in a considerably lower degree of temperature, would no longer exist in nature in its pure and simple state, but would always be procured in its acid or oxygenated state, and its radical would become one of the substances unknown to chemistry. By gradually increasing the temperature of the earth the same circumstance would successively happen to all the bodies capable of combustion; and, at last, every possible combustion having taken place, there would no longer exist any combustible body whatever, as every substance susceptible of that operation would be oxygenated, and consequently incombustible.
There cannot therefore exist, so far as relates to us, any combustible body, except such as are incombustible in the ordinary temperatures of the earth; or, what is the same thing, in other words, that it is essential to the nature of every combustible body not to possess the property of combustion, unless heated, or raised to the degree of temperature at which its combustion naturally takes place. When this degree is once produced, combustion commences, and the caloric which is disengaged by the decomposition of the oxygen gas keeps up the temperature necessary for continuing combustion. When this is not the case, that is, when the disengaged caloric is insufficient for keeping up the necessary temperature, the combustion ceases: This circumstance is expressed in common language by saying, that a body burns ill, or with difficulty.
Although combustion possesses some circumstances in common with distillation, especially with the compound kind of that operation, they differ in a very material point. In distillation there is a separation of one part of the elements of the substance from each other, and a combination of these, in a new order, occasioned by the affinities which take place in the increased temperature produced during distillation: This likewise happens in combustion, but with this farther circumstance, that a new element, not originally in the body, is brought into action; oxygen is added to the substance submitted to the operation, and caloric is disengaged.
The necessity of employing oxygen in the state of gas in all experiments with combustion, and the rigorous determination of the quantities employed, render this kind of operations peculiarly troublesome. As almost all the products of combustion are disengaged in the state of gas, it is still more difficult to retain them than even those furnished during compound distillation; hence this precaution was entirely neglected by the ancient chemists; and this set of experiments exclusively belong to modern chemistry.
Having thus pointed out, in a general way, the objects to be had in view in experiments upon combustion, I proceed, in the following sections of this chapter, to describe the different instruments I have used with this view. The following arrangement is formed, not upon the nature of the combustible bodies, but upon that of the instruments necessary for combustion.
In these combustions we begin by filling a jar, capable at least of holding six pints, with oxygen gas in the water apparatus, Pl. V. Fig. 1.; when it is perfectly full, so that the gas begins to flow out below, the jar, A, is carried to the mercury apparatus, Pl. IV. Fig. 3. We then dry the surface of the mercury, both within and without the jar, by means of blotting-paper, taking care to keep the paper for some time entirely immersed in the mercury before it is introduced under the jar, lest we let in any common air, which sticks very obstinately to the surface of the paper. The body to be submitted to combustion, being first very accurately weighed in nice scales, is placed in a small flat shallow dish, D, of iron or porcelain; this is covered by the larger cup P, which serves the office of a diving bell, and the whole is passed through the mercury into the jar, after which the larger cup is retired. The difficulty of passing the materials of combustion in this manner through the mercury may be avoided by raising one of the sides of the jar, A, for a moment, and slipping in the little cup, D, with the combustible body as quickly as possible. In this manner of operating, a small quantity of common air gets into the jar, but it is so very inconsiderable as not to injure either the progress or accuracy of the experiment in any sensible degree.
When the cup, D, is introduced under the jar, we suck out a part of the oxygen gas, so as to raise the mercury to EF, as formerly directed, Part I. Chap. V. otherwise, when the combustible body is set on fire, the gas becoming dilated would be in part forced out, and we should no longer be able to make any accurate calculation of the quantities before and after the experiment. A very convenient mode of drawing out the air is by means of an air-pump syringe adapted to the syphon, GHI, by which the mercury may be raised to any degree under twenty-eight inches. Very inflammable bodies, as phosphorus, are set on fire by means of the crooked iron wire, MN, Pl. IV. Fig. 16. made red hot, and passed quickly through the mercury. Such as are less easily set on fire have a small portion of tinder, upon which a minute particle of phosphorus is fixed, laid upon them before using the red hot iron.
In the first moment of combustion the air, being heated, rarifies, and the mercury descends; but when, as in combustions of phosphorus and iron, no elastic fluid is formed, absorption becomes presently very sensible, and the mercury rises high into the jar. Great attention must be used not to burn too large a quantity of any substance in a given quantity of gas, otherwise, towards the end of the experiment, the cup would approach so near the top of the jar as to endanger breaking it by the great heat produced, and the sudden refrigeration from the cold mercury. For the methods of measuring the volume of the gasses, and for correcting the measures according to the heighth of the barometer and thermometer, &c. see Chap. II. Sect. V. and VI. of this part.
The above process answers very well for burning all the concrete substances, and even for the fixed oils: These last are burnt in lamps under the jar, and are readily set on fire by means of tinder, phosphorus, and hot iron. But it is dangerous for substances susceptible of evaporating in a moderate heat, such as ether, alkohol, and the essential oils; these substances dissolve in considerable quantity in oxygen gas; and, when set on fire, a dangerous and sudden explosion takes place, which carries up the jar to a great height, and dashes it in a thousand pieces. From two such explosions some of the members of the Academy and myself escaped very narrowly. Besides, though this manner of operating is sufficient for determining pretty accurately the quantity of oxygen gas absorbed, and of carbonic acid produced, as water is likewise formed in all experiments upon vegetable and animal matters which contain an excess of hydrogen, this apparatus can neither collect it nor determine its quantity. The experiment with phosphorus is even incomplete in this way, as it is impossible to demonstrate that the weight of the phosphoric acid produced is equal to the sum of the weights of the phosphorus burnt and oxygen gas absorbed during the process. I have been therefore obliged to vary the instruments according to circumstances, and to employ several of different kinds, which I shall describe in their order, beginning with that used for burning phosphorus.
Take a large balloon, A, Pl. IV. Fig. 4. of cristal or white glass, with an opening, EF, about two inches and a half, or three inches, diameter, to which a cap of brass is accurately fitted with emery, and which has two holes for the passage of the tubes xxx, yyy. Before shutting the balloon with its cover, place within it the stand, BC, supporting the cup of porcelain, D, which contains the phosphorus. Then lute on the cap with fat lute, and allow it to dry for some days, and weigh the whole accurately; after this exhaust the balloon by means of an air-pump connected with the tube xxx, and fill it with oxygen gas by the tube yyy, from the gazometer, Pl. VIII. Fig. 1. described Chap. II. Sect II. of this part. The phosphorus is then set on fire by means of a burning-glass, and is allowed to burn till the cloud of concrete phosphoric acid stops the combustion, oxygen gas being continually supplied from the gazometer. When the apparatus has cooled, it is weighed and unluted; the tare of the instrument being allowed, the weight is that of the phosphoric acid contained. It is proper, for greater accuracy, to examine the air or gas contained in the balloon after combustion, as it may happen to be somewhat heavier or lighter than common air; and this difference of weight must be taken into account in the calculations upon the results of the experiment.
The apparatus I have employed for this process consists of a small conical furnace of hammered copper, represented in perspective, Pl. XII. Fig. 9. and internally displayed Fig. 11. It is divided into the furnace, ABC, where the charcoal is burnt, the grate, d e, and the ash-hole, F; the tube, GH, in the middle of the dome of the furnace serves to introduce the charcoal, and as a chimney for carrying off the air which has served for combustion. Through the tube, l m n, which communicates with the gazometer, the hydrogen gas, or air, intended for supporting the combustion, is conveyed into the ash-hole, F, whence it is forced, by the application of pressure to the gazometer, to pass through the grate, d e, and to blow upon the burning charcoal placed immediately above.
Oxygen gas, which forms 28/100 of atmospheric air, is changed into carbonic acid gas during combustion with charcoal, whilst the azotic gas of the air is not altered at all. Hence, after the combustion of charcoal in atmospheric air, a mixture of carbonic acid gas and azotic gas must remain; to allow this mixture to pass off, the tube, o p, is adapted to the chimney, GH, by means of a screw at G, and conveys the gas into bottles half filled with solution of caustic potash. The carbonic acid gas is absorbed by the alkali, and the azotic gas is conveyed into a second gazometer, where its quantity is ascertained.
The weight of the furnace, ABC, is first accurately determined, then introduce the tube RS, of known weight, by the chimney, GH, till its lower end S, rests upon the grate, d e, which it occupies entirely; in the next place, fill the furnace with charcoal, and weigh the whole again, to know the exact quantity of charcoal submitted to experiment. The furnace is now put in its place, the tube, l m n, is screwed to that which communicates with the gazometer, and the tube, o p, to that which communicates with the bottles of alkaline solution. Every thing being in readiness, the stop-cock of the gazometer is opened, a small piece of burning charcoal is thrown into the tube, RS, which is instantly withdrawn, and the tube, o p, is screwed to the chimney, GH. The little piece of charcoal falls upon the grate, and in this manner gets below the whole charcoal, and is kept on fire by the stream of air from the gazometer. To be certain that the combustion is begun, and goes on properly, the tube, q r s, is fixed to the furnace, having a piece of glass cemented to its upper extremity, s, through which we can see if the charcoal be on fire.
I neglected to observe above, that the furnace, and its appendages, are plunged in water in the cistern, TVXY, Fig. 11. Pl. XII. to which ice may be added to moderate the heat, if necessary; though the heat is by no means very considerable, as there is no air but what comes from the gazometer, and no more of the charcoal burns at one time than what is immediately over the grate.
As one piece of charcoal is consumed another falls down into its place, in consequence of the declivity of the sides of the furnace; this gets into the stream of air from the grate, d e, and is burnt; and so on, successively, till the whole charcoal is consumed. The air which has served the purpose of the combustion passes through the mass of charcoal, and is forced by the pressure of the gazometer to escape through the tube, o p, and to pass through the bottles of alkaline solution.
This experiment furnishes all the necessary data for a complete analysis of atmospheric air and of charcoal. We know the weight of charcoal consumed; the gazometer gives us the measure of the air employed; the quantity and quality of gas remaining after combustion may be determined, as it is received, either in another gazometer, or in jars, in a pneumato-chemical apparatus; the weight of ashes remaining in the ash-hole is readily ascertained; and, finally, the additional weight acquired by the bottles of alkaline solution gives the exact quantity of carbonic acid formed during the process. By this experiment we may likewise determine, with sufficient accuracy, the proportions in which charcoal and oxygen enter into the composition of carbonic acid.
In a future memoir I shall give an account to the Academy of a series of experiments I have undertaken, with this instrument, upon all the vegetable and animal charcoals. By some very slight alterations, this machine may be made to answer for observing the principal phenomena of respiration.
Oils are more compound in their nature than charcoal, being formed by the combination of at least two elements, charcoal and hydrogen; of course, after their combustion in common air, water, carbonic acid gas, and azotic gas, remain. Hence the apparatus employed for their combustion requires to be adapted for collecting these three products, and is consequently more complicated than the charcoal furnace.
The apparatus I employ for this purpose is composed of a large jar or pitcher A, Pl. XII. Fig. 4. surrounded at its upper edge by a rim of iron properly cemented at DE, and receding from the jar at BC, so as to leave a furrow or gutter xx, between it and the outside of the jar, somewhat more than two inches deep. The cover or lid of the jar, Fig. 5. is likewise surrounded by an iron rim f g, which adjusts into the gutter xx, Fig. 4. which being filled with mercury, has the effect of closing the jar hermetically in an instant, without using any lute; and, as the gutter will hold about two inches of mercury, the air in the jar may be made to sustain the pressure of more than two feet of water, without danger of its escaping.
The lid has four holes, T h i k, for the passage of an equal number of tubes. The opening T is furnished with a leather box, through which passes the rod, Fig. 3. intended for raising and lowering the wick of the lamp, as will be afterwards directed. The three other holes are intended for the passage of three several tubes, one of which conveys the oil to the lamp, a second conveys air for keeping up the combustion, and the third carries off the air, after it has served for combustion. The lamp in which the oil is burnt is represented Fig. 2; a is the reservoir of oil, having a funnel by which it is filled; b c d e f g h is a syphon which conveys the oil to the lamp 11; 7, 8, 9, 10, is the tube which conveys the air for combustion from the gazometer to the same lamp. The tube b c is formed externally, at its lower end b, into a male screw, which turns in a female screw in the lid of the reservoir of oil a; so that, by turning the reservoir one way or the other, it is made to rise or fall, by which the oil is kept at the necessary level.
When the syphon is to be filled, and the communication formed between the reservoir of oil and the lamp, the stop-cock c is shut, and that at e opened, oil is poured in by the opening f at the top of the syphon, till it rises within three or four lines of the upper edge of the lamp, the stop-cock k is then shut, and that at c opened; the oil is then poured in at f, till the branch b c d of the syphon is filled, and then the stop-cock e is closed. The two branches of the syphon being now completely filled, a communication is fully established between the reservoir and the lamp.
In Pl. XII. Fig. 1. all the parts of the lamp 11, Fig. 2. are represented magnified, to show them distinctly. The tube i k carries the oil from the reservoir to the cavity a a a a, which contains the wick; the tube 9, 10, brings the air from the gazometer for keeping up the combustion; this air spreads through the cavity d d d d, and, by means of the passages c c c c and b b b b, is distributed on each side of the wick, after the principles of the lamps constructed by Argand, Quinquet, and Lange.
To render the whole of this complicated apparatus more easily understood, and that its description may make all others of the same kind more readily followed, it is represented, completely connected together for use, in Pl. XI. The gazometer P furnishes air for the combustion by the tube and stop-cock 1, 2; the tube 2, 3, communicates with a second gazometer, which is filled whilst the first one is emptying during the process, that there may be no interruption to the combustion; 4, 5, is a tube of glass filled with deliquescent salts, for drying the air as much as possible in its passage; and the weight of this tube and its contained salts, at the beginning of the experiment, being known, it is easy to determine the quantity of water absorbed by them from the air. From this deliquescent tube the air is conducted through the pipe 5, 6, 7, 8, 9, 10, to the lamp 11, where it spreads on both sides of the wick, as before described, and feeds the flame. One part of this air, which serves to keep up the combustion of the oil, forms carbonic acid gas and water, by oxygenating its elements. Part of this water condenses upon the sides of the pitcher A, and another part is held in solution in the air by means of caloric furnished by the combustion. This air is forced by the compression of the gazometer to pass through the tube 12, 13, 14, 15, into the bottle 16, and the worm 17, 18, where the water is fully condensed from the refrigeration of the air; and, if any water still remains in solution, it is absorbed by deliquescent salts contained in the tube 19, 20.
All these precautions are solely intended for collecting and determining the quantity of water formed during the experiment; the carbonic acid and azotic gas remains to be ascertained. The former is absorbed by caustic alkaline solution in the bottles 22 and 25. I have only represented two of these in the figure, but nine at least are requisite; and the last of the series may be half filled with lime-water, which is the most certain reagent for indicating the presence of carbonic acid; if the lime-water is not rendered turbid, we may be certain that no sensible quantity of that acid remains in the air.
The rest of the air which has served for combustion, and which chiefly consists of azotic gas, though still mixed with a considerable portion of oxygen gas, which has escaped unchanged from the combustion, is carried through a third tube 28, 29, of deliquescent salts, to deprive it of any moisture it may have acquired in the bottles of alkaline solution and lime-water, and from thence by the tube 29, 30, into a gazometer, where its quantity is ascertained. Small essays are then taken from it, which are exposed to a solution of sulphuret of potash, to ascertain the proportions of oxygen and azotic gas it contains.
In the combustion of oils the wick becomes charred at last, and obstructs the rise of the oil; besides, if we raise the wick above a certain height, more oil rises through its capillary tubes than the stream of air is capable of consuming, and smoke is produced. Hence it is necessary to be able to lengthen or shorten the wick without opening the apparatus; this is accomplished by means of the rod 31, 32, 33, 34, which passes through a leather-box, and is connected with the support of the wick; and that the motion of this rod, and consequently of the wick, may be regulated with the utmost smoothness and facility; it is moved at pleasure by a pinnion which plays in a toothed rack. The rod, with its appendages, are represented Pl. XII. Fig. 3. It appeared to me, that the combustion would be assisted by surrounding the flame of the lamp with a small glass jar open at both ends, as represented in its place in Pl. XI.
I shall not enter into a more detailed description of the construction of this apparatus, which is still capable of being altered and modified in many respects, but shall only add, that when it is to be used in experiment, the lamp and reservoir with the contained oil must be accurately weighed, after which it is placed as before directed, and lighted; having then formed the connection between the air in the gazometer and the lamp, the external jar A, Pl. XI. is fixed over all, and secured by means of the board BC and two rods of iron which connect this board with the lid, and are screwed to it. A small quantity of oil is burnt while the jar is adjusting to the lid, and the product of that combustion is lost; there is likewise a small portion of air from the gazometer lost at the same time. Both of these are of very inconsiderable consequence in extensive experiments, and they are even capable of being valued in our calculation of the results.
In a particular memoir, I shall give an account to the Academy of the difficulties inseparable from this kind of experiments: These are so insurmountable and troublesome, that I have not hitherto been able to obtain any rigorous determination of the quantities of the products. I have sufficient proof, however, that the fixed oils are entirely resolved during combustion into water and carbonic acid gas, and consequently that they are composed of hydrogen and charcoal; but I have no certain knowledge respecting the proportions of these ingredients.
The combustion of alkohol may be very readily performed in the apparatus already described for the combustion of charcoal and phosphorus. A lamp filled with alkohol is placed under the jar A, Pl. IV. Fig. 3. a small morsel of phosphorus is placed upon the wick of the lamp, which is set on fire by means of the hot iron, as before directed. This process is, however, liable to considerable inconveniency; it is dangerous to make use of oxygen gas at the beginning of the experiment for fear of deflagration, which is even liable to happen when common air is employed. An instance of this had very near proved fatal to myself, in presence of some members of the Academy. Instead of preparing the experiment, as usual, at the time it was to be performed, I had disposed every thing in order the evening before; the atmospheric air of the jar had thereby sufficient time to dissolve a good deal of the alkohol; and this evaporation had even been considerably promoted by the height of the column of mercury, which I had raised to EF, Pl. IV. Fig. 3. The moment I attempted to set the little morsel of phosphorus on fire by means of the red hot iron, a violent explosion took place, which threw the jar with great violence against the floor of the laboratory, and dashed it in a thousand pieces.
Hence we can only operate upon very small quantities, such as ten or twelve grains of alkohol, in this manner; and the errors which may be committed in experiments upon such small quantities prevents our placing any confidence in their results. I endeavoured to prolong the combustion, in the experiments contained in the Memoirs of the Academy for 1784, p. 593. by lighting the alkohol first in common air, and furnishing oxygen gas afterwards to the jar, in proportion as it consumed; but the carbonic acid gas produced by the process became a great hinderance to the combustion, the more so that alkohol is but difficultly combustible, especially in worse than common air; so that even in this way very small quantities only could be burnt.
Perhaps this combustion might succeed better in the oil apparatus, Pl. XI.; but I have not hitherto ventured to try it. The jar A in which the combustion is performed is near 1400 cubical inches in dimension; and, were an explosion to take place in such a vessel, its consequences would be very terrible, and very difficult to guard against. I have not, however, despaired of making the attempt.
From all these difficulties, I have been hitherto obliged to confine myself to experiments upon very small quantities of alkohol, or at least to combustions made in open vessels, such as that represented in Pl. IX. Fig. 5. which will be described in Section VII. of this chapter. If I am ever able to remove these difficulties, I shall resume this investigation.
Tho' the combustion of ether in close vessels does not present the same difficulties as that of alkohol, yet it involves some of a different kind, not more easily overcome, and which still prevent the progress of my experiments. I endeavoured to profit by the property which ether possesses of dissolving in atmospheric air, and rendering it inflammable without explosion. For this purpose, I constructed the reservoir of ether a b c d, Plate XII. Fig. 8. to which air is brought from the gazometer by the tube 1, 2, 3, 4. This air spreads, in the first place, in the double lid ac of the reservoir, from which it passes through seven tubes ef, gh, ik, &c. which descend to the bottom of the ether, and it is forced by the pressure of the gazometer to boil up through the ether in the reservoir. We may replace the ether in this first reservoir, in proportion as it is dissolved and carried off by the air, by means of the supplementary reservoir E, connected by a brass tube fifteen or eighteen inches long, and shut by a stop-cock. This length of the connecting tube is to enable the descending ether to overcome the resistance occasioned by the pressure of the air from the gazometer.
The air, thus loaded with vapours of ether, is conducted by the tube 5, 6, 7, 8, 9, to the jar A, into which it is allowed to escape through a capillary opening, at the extremity of which it is set on fire. The air, when it has served the purpose of combustion, passes through the bottle 16, Pl. XI. the worm 17, 18, and the deliquescent tube 19, 20, after which it passes through the alkaline bottles; in these its carbonic acid gas is absorbed, the water formed during the experiment having been previously deposited in the former parts of the apparatus.
When I caused construct this apparatus, I supposed that the combination of atmospheric air and ether formed in the reservoir a b c d, Pl. XII. Fig. 8. was in proper proportion for supporting combustion; but in this I was mistaken; for there is a very considerable quantity of excess of ether; so that an additional quantity of atmospheric air is necessary to enable it to burn fully. Hence a lamp constructed upon these principles will burn in common air, which furnishes the quantity of oxygen necessary for combustion, but will not burn in close vessels in which the air is not renewed. From this circumstance, my ether lamp went out soon after being lighted and shut up in the jar A, Pl. XII. Fig. 8. To remedy this defect, I endeavoured to bring atmospheric air to the lamp by the lateral tube 10, 11, 12, 13, 14, 15, which I distributed circularly round the flame; but the flame is so exceedingly rare, that it is blown out by the gentlest possible stream of air, so that I have not hitherto succeeded in burning ether. I do not, however, despair of being able to accomplish it by means of some changes I am about to have made upon this apparatus.
In the formation of water, two substances, hydrogen and oxygen, which are both in the aëriform state before combustion, are transformed into liquid or water by the operation. This experiment would be very easy, and would require very simple instruments, if it were possible to procure the two gasses perfectly pure, so that they might burn without any residuum. We might, in that case, operate in very small vessels, and, by continually furnishing the two gasses in proper proportions, might continue the combustion indefinitely. But, hitherto, chemists have only employed oxygen gas, mixed with azotic gas; from which circumstance, they have only been able to keep up the combustion of hydrogen gas for a very limited time in close vessels, because, as the residuum of azotic gas is continually increasing, the air becomes at last so much contaminated, that the flame weakens and goes out. This inconvenience is so much the greater in proportion as the oxygen gas employed is less pure. From this circumstance, we must either be satisfied with operating upon small quantities, or must exhaust the vessels at intervals, to get rid of the residuum of azotic gas; but, in this case, a portion of the water formed during the experiment is evaporated by the exhaustion; and the resulting error is the more dangerous to the accuracy of the process, that we have no certain means of valuing it.
These considerations make me desirous to repeat the principal experiments of pneumatic chemistry with oxygen gas entirely free from any admixture of azotic gas; and this may be procured from oxygenated muriat of potash. The oxygen gas extracted from this salt does not appear to contain azote, unless accidentally, so that, by proper precautions, it may be obtained perfectly pure. In the mean time, the apparatus employed by Mr Meusnier and me for the combustion of hydrogen gas, which is described in the experiment for recomposition of water, Part I. Chap. VIII. and need not be here repeated, will answer the purpose; when pure gasses are procured, this apparatus will require no alterations, except that the capacity of the vessels may then be diminished. See Pl. IV. Fig. 5.
The combustion, when once begun, continues for a considerable time, but weakens gradually, in proportion as the quantity of azotic gas remaining from the combustion increases, till at last the azotic gas is in such over proportion that the combustion can no longer be supported, and the flame goes out. This spontaneous extinction must be prevented, because, as the hydrogen gas is pressed upon in its reservoir, by an inch and a half of water, whilst the oxygen gas suffers a pressure only of three lines, a mixture of the two would take place in the balloon, which would at last be forced by the superior pressure into the reservoir of oxygen gas. Wherefore the combustion must be stopped, by shutting the stop-cock of the tube dDd whenever the flame grows very feeble; for which purpose it must be attentively watched.
There is another apparatus for combustion, which, though we cannot with it perform experiments with the same scrupulous exactness as with the preceding instruments, gives very striking results that are extremely proper to be shewn in courses of philosophical chemistry. It consists of a worm EF, Pl. IX. Fig. 5. contained in a metallic cooller ABCD. To the upper part of this worm E, the chimney GH is fixed, which is composed of two tubes, the inner of which is a continuation of the worm, and the outer one is a case of tin-plate, which surrounds it at about an inch distance, and the interval is filled up with sand. At the inferior extremity K of the inner tube, a glass tube is fixed, to which we adopt the Argand lamp LM for burning alkohol, &c.
Things being thus disposed, and the lamp being filled with a determinate quantity of alkohol, it is set on fire; the water which is formed during the combustion rises in the chimney KE, and being condensed in the worm, runs out at its extremity F into the bottle P. The double tube of the chimney, filled with sand in the interstice, is to prevent the tube from cooling in its upper part, and condensing the water; otherwise, it would fall back in the tube, and we should not be able to ascertain its quantity, and besides it might fall in drops upon the wick, and extinguish the flame. The intention of this construction, is to keep the chimney always hot, and the worm always cool, that the water may be preserved in the state of vapour whilst rising, and may be condensed immediately upon getting into the descending part of the apparatus. By this instrument, which was contrived by Mr Meusnier, and which is described by me in the Memoirs of the Academy for 1784, p. 593. we may, with attention to keep the worm always cold, collect nearly seventeen ounces of water from the combustion of sixteen ounces of alkohol.
The term oxydation or calcination is chiefly used to signify the process by which metals exposed to a certain degree of heat are converted into oxyds, by absorbing oxygen from the air. This combination takes place in consequence of oxygen possessing a greater affinity to metals, at a certain temperature, than to caloric, which becomes disengaged in its free state; but, as this disengagement, when made in common air, is slow and progressive, it is scarcely evident to the senses. It is quite otherwise, however, when oxydation takes place in oxygen gas; for, being produced with much greater rapidity, it is generally accompanied with heat and light, so as evidently to show that metallic substances are real combustible bodies.
All the metals have not the same degree of affinity to oxygen. Gold, silver, and platina, for instance, are incapable of taking it away from its combination with caloric, even in the greatest known heat; whereas the other metals absorb it in a larger or smaller quantity, until the affinities of the metal to oxygen, and of the latter to caloric, are in exact equilibrium. Indeed, this state of equilibrium of affinities may be assumed as a general law of nature in all combinations.
In all operations of this nature, the oxydation of metals is accelerated by giving free access to the air; it is sometimes much assisted by joining the action of a bellows, which directs a stream of air over the surface of the metal. This process becomes greatly more rapid if a stream of oxygen gas be used, which is readily done by means of the gazometer formerly described. The metal, in this case, throws out a brilliant flame, and the oxydation is very quickly accomplished; but this method can only be used in very confined experiments, on account of the expence of procuring oxygen gas. In the essay of ores, and in all the common operations of the laboratory, the calcination or oxydation of metals is usually performed in a dish of baked clay, Pl. IV. Fig. 6. commonly called a roasting test, placed in a strong furnace. The substances to be oxydated are frequently stirred, on purpose to present fresh surfaces to the air.
Whenever this operation is performed upon a metal which is not volatile, and from which nothing flies off into the surrounding air during the process, the metal acquires additional weight; but the cause of this increased weight during oxydation could never have been discovered by means of experiments performed in free air; and it is only since these operations have been performed in close vessels, and in determinate quantities of air, that any just conjectures have been formed concerning the cause of this phenomenon. The first method for this purpose is due to Dr Priestley, who exposes the metal to be calcined in a porcelain cup N, Pl. IV. Fig. 11. placed upon the stand IK, under a jar A, in the bason BCDE, full of water; the water is made to rise up to GH, by sucking out the air with a syphon, and the focus of a burning glass is made to fall upon the metal. In a few minutes the oxydation takes place, a part of the oxygen contained in the air combines with the metal, and a proportional diminution of the volume of air is produced; what remains is nothing more than azotic gas, still however mixed with a small quantity of oxygen gas. I have given an account of a series of experiments made with this apparatus in my Physical and Chemical Essays, first published in 1773. Mercury may be used instead of water in this experiment, whereby the results are rendered still more conclusive.
Another process for this purpose was invented by Mr Boyle, and of which I gave an account in the Memoirs of the Academy for 1774, p. 351. The metal is introduced into a retort, Pl. III. Fig. 20. the beak of which is hermetically sealed; the metal is then oxydated by means of heat applied with great precaution. The weight of the vessel, and its contained substances, is not at all changed by this process, until the extremity of the neck of the retort is broken; but, when that is done, the external air rushes in with a hissing noise. This operation is attended with danger, unless a part of the air is driven out of the retort, by means of heat, before it is hermetically sealed, as otherwise the retort would be apt to burst by the dilation of the air when placed in the furnace. The quantity of air driven out may be received under a jar in the pneumato-chemical apparatus, by which its quantity, and that of the air remaining in the retort, is ascertained. I have not multiplied my experiments upon oxydation of metals so much as I could have wished; neither have I obtained satisfactory results with any metal except tin. It is much to be wished that some person would undertake a series of experiments upon oxydation of metals in the several gasses; the subject is important, and would fully repay any trouble which this kind of experiment might occasion.
As all the oxyds of mercury are capable of revivifying without addition, and restore the oxygen gas they had before absorbed, this seemed to be the most proper metal for becoming the subject of conclusive experiments upon oxydation. I formerly endeavoured to accomplish the oxydation of mercury in close vessels, by filling a retort, containing a small quantity of mercury, with oxygen gas, and adapting a bladder half full of the same gas to its beak; See Pl. IV. Fig. 12. Afterwards, by heating the mercury in the retort for a very long time, I succeeded in oxydating a very small portion, so as to form a little red oxyd floating upon the surface of the running mercury; but the quantity was so small, that the smallest error committed in the determination of the quantities of oxygen gas before and after the operation must have thrown very great uncertainty upon the results of the experiment. I was, besides, dissatisfied with this process, and not without cause, lest any air might have escaped through the pores of the bladder, more especially as it becomes shrivelled by the heat of the furnace, unless covered over with cloths kept constantly wet.
This experiment is performed with more certainty in the apparatus described in the Memoirs of the Academy for 1775, p. 580. This consists of a retort, A, Pl. IV. Fig. 2. having a crooked glass tube BCDE of ten or twelve lines internal diameter, melted on to its beak, and which is engaged under the bell glass FG, standing with its mouth downwards, in a bason filled with water or mercury. The retort is placed upon the bars of the furnace MMNN, Pl. IV. Fig. 2. or in a sand bath, and by means of this apparatus we may, in the course of several days, oxydate a small quantity of mercury in common air; the red oxyd floats upon the surface, from which it may be collected and revivified, so as to compare the quantity of oxygen gas obtained in revivification with the absorption which took place during oxydation. This kind of experiment can only be performed upon a small scale, so that no very certain conclusions can be drawn from them61.
The combustion of iron in oxygen gas being a true oxydation of that metal, ought to be mentioned in this place. The apparatus employed by Mr Ingenhousz for this operation is represented in Pl. IV. Fig. 17.; but, having already described it sufficiently in Chap. III. I shall refer the reader to what is said of it in that place. Iron may likewise be oxydated by combustion in vessels filled with oxygen gas, in the way already directed for phosphorus and charcoal. This apparatus is represented Pl. IV. Fig. 3. and described in the fifth chapter of the first part of this work. We learn from Mr Ingenhousz, that all the metals, except gold, silver, and mercury, may be burnt or oxydated in the same manner, by reducing them into very fine wire, or very thin plates cut into narrow slips; these are twisted round with iron-wire, which communicates the property of burning to the other metals.
Mercury is even difficultly oxydated in free air. In chemical laboratories, this process is usually carried on in a matrass A, Pl. IV. Fig. having a very flat body, and a very long neck BC, which vessel is commonly called Boyle's bell. A quantity of mercury is introduced sufficient to cover the bottom, and it is placed in a sand-bath, which keeps up a constant heat approaching to that of boiling mercury. By continuing this operation with five or six similar matrasses during several months, and renewing the mercury from time to time, a few ounces of red oxyd are at last obtained. The great slowness and inconvenience of this apparatus arises from the air not being sufficiently renewed; but if, on the other hand, too free a circulation were given to the external air, it would carry off the mercury in solution in the state of vapour, so that in a few days none would remain in the vessel.
As, of all the experiments upon the oxydation of metals, those with mercury are the most conclusive, it were much to be wished that a simple apparatus could be contrived by which this oxydation and its results might be demonstrated in public courses of chemistry. This might, in my opinion, be accomplished by methods similar to those I have already described for the combustion of charcoal and the oils; but, from other pursuits, I have not been able hitherto to resume this kind of experiment.
The oxyd of mercury revives without addition, by being heated to a slightly red heat. In this degree of temperature, oxygen has greater affinity to caloric than to mercury, and forms oxygen gas. This is always mixed with a small portion of azotic gas, which indicates that the mercury absorbs a small portion of this latter gas during oxydation. It almost always contains a little carbonic acid gas, which must undoubtedly be attributed to the foulnesses of the oxyd; these are charred by the heat, and convert a part of the oxygen gas into carbonic acid.
If chemists were reduced to the necessity of procuring all the oxygen gas employed in their experiments from mercury oxydated by heat without addition, or, as it is called, calcined or precipitated per se, the excessive dearness of that preparation would render experiments, even upon a moderate scale, quite impracticable. But mercury may likewise be oxydated by means of nitric acid; and in this way we procure a red oxyd, even more pure than that produced by calcination. I have sometimes prepared this oxyd by dissolving mercury in nitric acid, evaporating to dryness, and calcining the salt, either in a retort, or in capsules formed of pieces of broken matrasses and retorts, in the manner formerly described; but I have never succeeded in making it equally beautiful with what is sold by the druggists, and which is, I believe, brought from Holland. In choosing this, we ought to prefer what is in solid lumps composed of soft adhering scales, as when in powder it is sometimes adulterated with red oxyd of lead.
To obtain oxygen gas from the red oxyd of mercury, I usually employ a porcelain retort, having a long glass tube adapted to its beak, which is engaged under jars in the water pneumato-chemical apparatus, and I place a bottle in the water, at the end of the tube, for receiving the mercury, in proportion as it revives and distils over. As the oxygen gas never appears till the retort becomes red, it seems to prove the principle established by Mr Berthollet, that an obscure heat can never form oxygen gas, and that light is one of its constituent elements. We must reject the first portion of gas which comes over, as being mixed with common air, from what was contained in the retort at the beginning of the experiment; but, even with this precaution, the oxygen gas procured is usually contaminated with a tenth part of azotic gas, and with a very small portion of carbonic acid gas. This latter is readily got rid of, by making the gas pass through a solution of caustic alkali; but we know of no method for separating the azotic gas; its proportions may however be ascertained, by leaving a known quantity of the oxygen gas contaminated with it for a fortnight, in contact with sulphuret of soda or potash, which absorbs the oxygen gas so as to convert the sulphur into sulphuric acid, and leaves the azotic gas remaining pure.
We may likewise procure oxygen gas from black oxyd of manganese or nitrat of potash, by exposing them to a red heat in the apparatus already described for operating upon red oxyd of mercury; only, as it requires such a heat as is at least capable of softening glass, we must employ retorts of stone or of porcelain. But the purest and best oxygen gas is what is disengaged from oxygenated muriat of potash by simple heat. This operation is performed in a glass retort, and the gas obtained is perfectly pure, provided that the first portions, which are mixed with the common air of the vessels, be rejected.
61 See an account of this experiment, Part. I. Chap. iii. — A.
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