Of the Combinations of Caloric, and the Formation of Elastic Aëriform Fluids.
That every body, whether solid or fluid, is augmented in all its dimensions by any increase of its sensible heat, was long ago fully established as a physical axiom, or universal proposition, by the celebrated Boerhaave. Such facts as have been adduced for controverting the generality of this principle offer only fallacious results, or, at least, such as are so complicated with foreign circumstances as to mislead the judgment: But, when we separately consider the effects, so as to deduce each from the cause to which they separately belong, it is easy to perceive that the separation of particles by heat is a constant and general law of nature.
When we have heated a solid body to a certain degree, and have thereby caused its particles to separate from each other, if we allow the body to cool, its particles again approach each other in the same proportion in which they were separated by the increased temperature; the body returns through the same degrees of expansion which it before extended through; and, if it be brought back to the same temperature from which we set out at the commencement of the experiment, it recovers exactly the same dimensions which it formerly occupied. But, as we are still very far from being able to arrive at the degree of absolute cold, or deprivation of all heat, being unacquainted with any degree of coldness which we cannot suppose capable of still farther augmentation, it follows, that we are still incapable of causing the ultimate particles of bodies to approach each other as near as is possible; and, consequently, that the particles of all bodies do not touch each other in any state hitherto known, which, tho' a very singular conclusion, is yet impossible to be denied.
It is supposed, that, since the particles of bodies are thus continually impelled by heat to separate from each other, they would have no connection between themselves; and, of consequence, that there could be no solidity in nature, unless they were held together by some other power which tends to unite them, and, so to speak, to chain them together; which power, whatever be its cause, or manner of operation, we name Attraction.
Thus the particles of all bodies may be considered as subjected to the action of two opposite powers, the one repulsive, the other attractive, between which they remain in equilibrio. So long as the attractive force remains stronger, the body must continue in a state of solidity; but if, on the contrary, heat has so far removed these particles from each other, as to place them beyond the sphere of attraction, they lose the adhesion they before had with each other, and the body ceases to be solid.
Water gives us a regular and constant example of these facts; whilst below Zero of the French thermometer, or 32° of Fahrenheit, it remains solid, and is called ice. Above that degree of temperature, its particles being no longer held together by reciprocal attraction, it becomes liquid; and, when we raise its temperature above 80°, (212°) its particles, giving way to the repulsion caused by the heat, assume the state of vapour or gas, and the water is changed into an aëriform fluid.
The same may be affirmed of all bodies in nature: They are either solid or liquid, or in the state of elastic aëriform vapour, according to the proportion which takes place between the attractive force inherent in their particles, and the repulsive power of the heat acting upon these; or, what amounts to the same thing, in proportion to the degree of heat to which they are exposed.
It is difficult to comprehend these phenomena, without admitting them as the effects of a real and material substance, or very subtile fluid, which, insinuating itself between the particles of bodies, separates them from each other; and, even allowing the existence of this fluid to be hypothetical, we shall see in the sequel, that it explains the phenomena of nature in a very satisfactory manner.
This substance, whatever it is, being the cause of heat, or, in other words, the sensation which we call warmth being caused by the accumulation of this substance, we cannot, in strict language, distinguish it by the term heat; because the same name would then very improperly express both cause and effect. For this reason, in the memoir which I published in 1777, I gave it the names of igneous fluid and matter of heat. And, since that time, in the work published by Mr de Morveau, Mr Berthollet, Mr de Fourcroy, and myself, upon the reformation of chemical nomenclature, we thought it necessary to banish all periphrastic expressions, which both lengthen physical language, and render it more tedious and less distinct, and which even frequently does not convey sufficiently just ideas of the subject intended. Wherefore, we have distinguished the cause of heat, or that exquisitely elastic fluid which produces it, by the term of caloric. Besides, that this expression fulfils our object in the system which we have adopted, it possesses this farther advantage, that it accords with every species of opinion, since, strictly speaking, we are not obliged to suppose this to be a real substance; it being sufficient, as will more clearly appear in the sequel of this work, that it be considered as the repulsive cause, whatever that may be, which separates the particles of matter from each other; so that we are still at liberty to investigate its effects in an abstract and mathematical manner.
In the present state of our knowledge, we are unable to determine whether light be a modification of caloric, or if caloric be, on the contrary, a modification of light. This, however, is indisputable, that, in a system where only decided facts are admissible, and where we avoid, as far as possible, to suppose any thing to be that is not really known to exist, we ought provisionally to distinguish, by distinct terms, such things as are known to produce different effects. We therefore distinguish light from caloric; though we do not therefore deny that these have certain qualities in common, and that, in certain circumstances, they combine with other bodies almost in the same manner, and produce, in part, the same effects.
What I have already said may suffice to determine the idea affixed to the word caloric; but there remains a more difficult attempt, which is, to give a just conception of the manner in which caloric acts upon other bodies. Since this subtile matter penetrates through the pores of all known substances; since there are no vessels through which it cannot escape, and, consequently, as there are none which are capable of retaining it, we can only come at the knowledge of its properties by effects which are fleeting, and difficultly ascertainable. It is in these things which we neither see nor feel, that it is especially necessary to guard against the extravagancy of our imagination, which forever inclines to step beyond the bounds of truth, and is very difficultly restrained within the narrow line of facts.
We have already seen, that the same body becomes solid, or fluid, or aëriform, according to the quantity of caloric by which it is penetrated; or, to speak more strictly, according as the repulsive force exerted by the caloric is equal to, stronger, or weaker, than the attraction of the particles of the body it acts upon.
But, if these two powers only existed, bodies would become liquid at an indivisible degree of the thermometer, and would almost instantaneously pass from the solid state of aggregation to that of aëriform elasticity. Thus water, for instance, at the very moment when it ceases to be ice, would begin to boil, and would be transformed into an aëriform fluid, having its particles scattered indefinitely through the surrounding space. That this does not happen, must depend upon the action of some third power. The pressure of the atmosphere prevents this separation, and causes the water to remain in the liquid state till it be raised to 80° of temperature (212°) above zero of the French thermometer, the quantity of caloric which it receives in the lowest temperature being insufficient to overcome the pressure of the atmosphere.
Whence it appears that, without this atmospheric pressure, we should not have any permanent liquid, and should only be able to see bodies in that state of existence in the very instant of melting, as the smallest additional caloric would instantly separate their particles, and dissipate them through the surrounding medium. Besides, without this atmospheric pressure, we should not even have any aëriform fluids, strictly speaking, because the moment the force of attraction is overcome by the repulsive power of the caloric, the particles would separate themselves indefinitely, having nothing to give limits to their expansion, unless their own gravity might collect them together, so as to form an atmosphere.
Simple reflection upon the most common experiments is sufficient to evince the truth of these positions. They are more particularly proved by the following experiment, which I published in the Memoirs of the French Academy for 1777, p. 426.
Having filled with sulphuric ether a small narrow glass vessel, A, (Plate VII. Fig. 17.), standing upon its stalk P, the vessel, which is from twelve to fifteen lines diameter, is to be covered by a wet bladder, tied round its neck with several turns of strong thread; for greater security, fix a second bladder over the first. The vessel should be filled in such a manner with the ether, as not to leave the smallest portion of air between the liquor and the bladder. It is now to be placed under the recipient BCD of an air-pump, of which the upper part B ought to be fitted with a leathern lid, through which passes a wire EF, having its point F very sharp; and in the same receiver there ought to be placed the barometer GH. The whole being thus disposed, let the recipient be exhausted, and then, by pushing down the wire EF, we make a hole in the bladder. Immediately the ether begins to boil with great violence, and is changed into an elastic aëriform fluid, which fills the receiver. If the quantity of ether be sufficient to leave a few drops in the phial after the evaporation is finished, the elastic fluid produced will sustain the mercury in the barometer attached to the air-pump, at eight or ten inches in winter, and from twenty to twenty-five in summer. To render this experiment more complete, we may introduce a small thermometer into the phial A, containing the ether, which will descend considerably during the evaporation.
The only effect produced in this experiment is, the taking away the weight of the atmosphere, which, in its ordinary state, presses on the surface of the ether; and the effects resulting from this removal evidently prove, that, in the ordinary temperature of the earth, ether would always exist in an aëriform state, but for the pressure of the atmosphere, and that the passing of the ether from the liquid to the aëriform state is accompanied by a considerable lessening of heat; because, during the evaporation, a part of the caloric, which was before in a free state, or at least in equilibrio in the surrounding bodies, combines with the ether, and causes it to assume the aëriform state.
The same experiment succeeds with all evaporable fluids, such as alkohol, water, and even mercury; with this difference, that the atmosphere formed in the receiver by alkohol only supports the attached barometer about one inch in winter, and about four or five inches in summer; that formed by water, in the same situation, raises the mercury only a few lines, and that by quicksilver but a few fractions of a line. There is therefore less fluid evaporated from alkohol than from ether, less from water than from alkohol, and still less from mercury than from either; consequently there is less caloric employed, and less cold produced, which quadrates exactly with the results of these experiments.
Another species of experiment proves very evidently that the aëriform state is a modification of bodies dependent on the degree of temperature, and on the pressure which these bodies undergo. In a Memoir read by Mr de la Place and me to the Academy in 1777, which has not been printed, we have shown, that, when ether is subjected to a pressure equal to twenty-eight inches of the barometer, or about the medium pressure of the atmosphere, it boils at the temperature of about 32° (104°), or 33° (106.25°), of the thermometer. Mr de Luc, who has made similar experiments with spirit of wine, finds it boils at 67° (182.75°). And all the world knows that water boils at 80° (212°). Now, boiling being only the evaporation of a liquid, or the moment of its passing from the fluid to the aëriform state, it is evident that, if we keep ether continually at the temperature of 33° (106.25°), and under the common pressure of the atmosphere, we shall have it always in an elastic aëriform state; and that the same thing will happen with alkohol when above 67° (182.75°), and with water when above 80° (212°); all which are perfectly conformable to the following experiment.
I filled a large vessel ABCD (Plate VII. Fig. 16.) with water, at 35° (110.75°), or 36° (113°); I suppose the vessel transparent, that we may see what takes place in the experiment; and we can easily hold the hands in water at that temperature without inconvenience. Into it I plunged some narrow necked bottles F, G, which were filled with the water, after which they were turned up, so as to rest on their mouths on the bottom of the vessel. Having next put some ether into a very small matrass, with its neck a b c, twice bent as in the Plate, I plunged this matrass into the water, so as to have its neck inserted into the mouth of one of the bottles F. Immediately upon feeling the effects of the heat communicated to it by the water in the vessel ABCD it began to boil; and the caloric entering into combination with it, changed it into elastic aëriform fluid, with which I filled several bottles successively, F, G, &c.
This is not the place to enter upon the examination of the nature and properties of this aëriform fluid, which is extremely inflammable; but, confining myself to the object at present in view, without anticipating circumstances, which I am not to suppose the reader to know, I shall only observe, that the ether, from this experiment, is almost only capable of existing in the aëriform state in our world; for, if the weight of our atmosphere was only equal to between 20 and 24 inches of the barometer, instead of 28 inches, we should never be able to obtain ether in the liquid state, at least in summer; and the formation of ether would consequently be impossible upon mountains of a moderate degree of elevation, as it would be converted into gas immediately upon being produced, unless we employed recipients of extraordinary strength, together with refrigeration and compression. And, lastly, the temperature of the blood being nearly that at which ether passes from the liquid to the aëriform state, it must evaporate in the primae viae, and consequently it is very probable the medical properties of this fluid depend chiefly upon its mechanical effect.
These experiments succeed better with nitrous ether, because it evaporates in a lower temperature than sulphuric ether. It is more difficult to obtain alkohol in the aëriform state; because, as it requires 67° (182.75°) to reduce it to vapour, the water of the bath must be almost boiling, and consequently it is impossible to plunge the hands into it at that temperature.
It is evident that, if water were used in the foregoing experiment, it would be changed into gas, when exposed to a temperature superior to that at which it boils. Although thoroughly convinced of this, Mr de la Place and myself judged it necessary to confirm it by the following direct experiment. We filled a glass jar A, (Plate VII. Fig. 5.) with mercury, and placed it with its mouth downwards in a dish B, likewise filled with mercury, and having introduced about two gross of water into the jar, which rose to the top of the mercury at CD; we then plunged the whole apparatus into an iron boiler EFGH, full of boiling sea-water of the temperature of 85° (123.25°), placed upon the furnace GHIK. Immediately upon the water over the mercury attaining the temperature of 80° (212°), it began to boil; and, instead of only filling the small space ACD, it was converted into an aëriform fluid, which filled the whole jar; the mercury even descended below the surface of that in the dish B; and the jar must have been overturned, if it had not been very thick and heavy, and fixed to the dish by means of iron-wire. Immediately after withdrawing the apparatus from the boiler, the vapour in the jar began to condense, and the mercury rose to its former station; but it returned again to the aëriform state a few seconds after replacing the apparatus in the boiler.
We have thus a certain number of substances, which are convertible into elastic aëriform fluids by degrees of temperature, not much superior to that of our atmosphere. We shall afterwards find that there are several others which undergo the same change in similar circumstances, such as muriatic or marine acid, ammoniac or volatile alkali, the carbonic acid or fixed air, the sulphurous acid, &c. All of these are permanently elastic in or about the mean temperature of the atmosphere, and under its common pressure.
All these facts, which could be easily multiplied if necessary, give me full right to assume, as a general principle, that almost every body in nature is susceptible of three several states of existence, solid, liquid, and aëriform, and that these three states of existence depend upon the quantity of caloric combined with the body. Henceforwards I shall express these elastic aëriform fluids by the generic term gas; and in each species of gas I shall distinguish between the caloric, which in some measure serves the purpose of a solvent, and the substance, which in combination with the caloric, forms the base of the gas.
To these bases of the different gases, which are hitherto but little known, we have been obliged to assign names; these I shall point out in Chap. IV. of this work, when I have previously given an account of the phenomena attendant upon the heating and cooling of bodies, and when I have established precise ideas concerning the composition of our atmosphere.
We have already shown, that the particles of every substance in nature exist in a certain state of equilibrium, between that attraction which tends to unite and keep the particles together, and the effects of the caloric which tends to separate them. Hence the caloric not only surrounds the particles of all bodies on every side, but fills up every interval which the particles of bodies leave between each other. We may form an idea of this, by supposing a vessel filled with small spherical leaden bullets, into which a quantity of fine sand is poured, which, insinuating into the intervals between the bullets, will fill up every void. The balls, in this comparison, are to the sand which surrounds them exactly in the same situation as the particles of bodies are with respect to the caloric; with this difference only, that the balls are supposed to touch each other, whereas the particles of bodies are not in contact, being retained at a small distance from each other, by the caloric.
If, instead of spherical balls, we substitute solid bodies of a hexahedral, octohedral, or any other regular figure, the capacity of the intervals between them will be lessened, and consequently will no longer contain the same quantity of sand. The same thing takes place, with respect to natural bodies; the intervals left between their particles are not of equal capacity, but vary in consequence of the different figures and magnitude of their particles, and of the distance at which these particles are maintained, according to the existing proportion between their inherent attraction, and the repulsive force exerted upon them by the caloric.
In this manner we must understand the following expression, introduced by the English philosophers, who have given us the first precise ideas upon this subject; the capacity of bodies for containing the matter of heat. As comparisons with sensible objects are of great use in assisting us to form distinct notions of abstract ideas, we shall endeavour to illustrate this, by instancing the phenomena which take place between water and bodies which are wetted and penetrated by it, with a few reflections.
If we immerge equal pieces of different kinds of wood, suppose cubes of one foot each, into water, the fluid gradually insinuates itself into their pores, and the pieces of wood are augmented both in weight and magnitude: But each species of wood will imbibe a different quantity of water; the lighter and more porous woods will admit a larger, the compact and closer grained will admit of a lesser quantity; for the proportional quantities of water imbibed by the pieces will depend upon the nature of the constituent particles of the wood, and upon the greater or lesser affinity subsisting between them and water. Very resinous wood, for instance, though it may be at the same time very porous, will admit but little water. We may therefore say, that the different kinds of wood possess different capacities for receiving water; we may even determine, by means of the augmentation of their weights, what quantity of water they have actually absorbed; but, as we are ignorant how much water they contained, previous to immersion, we cannot determine the absolute quantity they contain, after being taken out of the water.
The same circumstances undoubtedly take place, with bodies that are immersed in caloric; taking into consideration, however, that water is an incompressible fluid, whereas caloric is, on the contrary, endowed with very great elasticity; or, in other words, the particles of caloric have a great tendency to separate from each other, when forced by any other power to approach; this difference must of necessity occasion very considerable diversities in the results of experiments made upon these two substances.
Having established these clear and simple propositions, it will be very easy to explain the ideas which ought to be affixed to the following expressions, which are by no means synonimous, but possess each a strict and determinate meaning, as in the following definitions:
Free caloric, is that which is not combined in any manner with any other body. But, as we live in a system to which caloric has a very strong adhesion, it follows that we are never able to obtain it in the state of absolute freedom.
Combined caloric, is that which is fixed in bodies by affinity or elective attraction, so as to form part of the substance of the body, even part of its solidity.
By the expression specific caloric of bodies, we understand the respective quantities of caloric requisite for raising a number of bodies of the same weight to an equal degree of temperature. This proportional quantity of caloric depends upon the distance between the constituent particles of bodies, and their greater or lesser degrees of cohesion; and this distance, or rather the space or void resulting from it, is, as I have already observed, called the capacity of bodies for containing caloric.
Heat, considered as a sensation, or, in other words, sensible heat, is only the effect produced upon our sentient organs, by the motion or passage of caloric, disengaged from the surrounding bodies. In general, we receive impressions only in consequence of motion, and we might establish it as an axiom, That, WITHOUT MOTION, THERE IS NO SENSATION. This general principle applies very accurately to the sensations of heat and cold: When we touch a cold body, the caloric which always tends to become in equilibrio in all bodies, passes from our hand into the body we touch, which gives us the feeling or sensation of cold. The direct contrary happens, when we touch a warm body, the caloric then passing from the body into our hand, produces the sensation of heat. If the hand and the body touched be of the same temperature, or very nearly so, we receive no impression, either of heat or cold, because there is no motion or passage of caloric; and thus no sensation can take place, without some correspondent motion to occasion it.
When the thermometer rises, it shows, that free caloric is entering into the surrounding bodies: The thermometer, which is one of these, receives its share in proportion to its mass, and to the capacity which it possesses for containing caloric. The change therefore which takes place upon the thermometer, only announces a change of place of the caloric in those bodies, of which the thermometer forms one part; it only indicates the portion of caloric received, without being a measure of the whole quantity disengaged, displaced, or absorbed.
The most simple and most exact method for determining this latter point, is that described by Mr de la Place, in the Memoirs of the Academy, No. 1780, p. 364; a summary explanation of which will be found towards the conclusion of this work. This method consists in placing a body, or a combination of bodies, from which caloric is disengaging, in the midst of a hollow sphere of ice; and the quantity of ice melted becomes an exact measure of the quantity of caloric disengaged. It is possible, by means of the apparatus which we have caused to be constructed upon this plan, to determine, not as has been pretended, the capacity of bodies for containing heat, but the ratio of the increase or diminution of capacity produced by determinate degrees of temperature. It is easy with the same apparatus, by means of divers combinations of experiments, to determine the quantity of caloric requisite for converting solid substances into liquids, and liquids into elastic aëriform fluids; and, vice versa, what quantity of caloric escapes from elastic vapours in changing to liquids, and what quantity escapes from liquids during their conversion into solids. Perhaps, when experiments have been made with sufficient accuracy, we may one day be able to determine the proportional quantity of caloric, necessary for producing the several species of gasses. I shall hereafter, in a separate chapter, give an account of the principal results of such experiments as have been made upon this head.
It remains, before finishing this article, to say a few words relative to the cause of the elasticity of gasses, and of fluids in the state of vapour. It is by no means difficult to perceive that this elasticity depends upon that of caloric, which seems to be the most eminently elastic body in nature. Nothing is more readily conceived, than that one body should become elastic by entering into combination with another body possessed of that quality. We must allow that this is only an explanation of elasticity, by an assumption of elasticity, and that we thus only remove the difficulty one step farther, and that the nature of elasticity, and the reason for caloric being elastic, remains still unexplained. Elasticity in the abstract is nothing more than that quality of the particles of bodies by which they recede from each other when forced together. This tendency in the particles of caloric to separate, takes place even at considerable distances. We shall be satisfied of this, when we consider that air is susceptible of undergoing great compression, which supposes that its particles were previously very distant from each other; for the power of approaching together certainly supposes a previous distance, at least equal to the degree of approach. Consequently, those particles of the air, which are already considerably distant from each other, tend to separate still farther. In fact, if we produce Boyle's vacuum in a large receiver, the very last portion of air which remains spreads itself uniformly through the whole capacity of the vessel, however large, fills it completely throughout, and presses every where against its sides: We cannot, however, explain this effect, without supposing that the particles make an effort to separate themselves on every side, and we are quite ignorant at what distance, or what degree of rarefaction, this effort ceases to act.
Here, therefore, exists a true repulsion between the particles of elastic fluids; at least, circumstances take place exactly as if such a repulsion actually existed; and we have very good right to conclude, that the particles of caloric mutually repel each other. When we are once permitted to suppose this repelling force, the rationale of the formation of gasses, or aëriform fluids, becomes perfectly simple; tho' we must, at the same time, allow, that it is extremely difficult to form an accurate conception of this repulsive force acting upon very minute particles placed at great distances from each other.
It is, perhaps, more natural to suppose, that the particles of caloric have a stronger mutual attraction than those of any other substance, and that these latter particles are forced asunder in consequence of this superior attraction between the particles of the caloric, which forces them between the particles of other bodies, that they may be able to reunite with each other. We have somewhat analogous to this idea in the phenomena which occur when a dry sponge is dipt into water: The sponge swells; its particles separate from each other; and all its intervals are filled up by the water. It is evident, that the sponge, in the act of swelling, has acquired a greater capacity for containing water than it had when dry. But we cannot certainly maintain, that the introduction of water between the particles of the sponge has endowed them with a repulsive power, which tends to separate them from each other; on the contrary, the whole phenomena are produced by means of attractive powers; and these are, first, The gravity of the water, and the power which it exerts on every side, in common with all other fluids; 2dly, The force of attraction which takes place between the particles of the water, causing them to unite together; 3dly, The mutual attraction of the particles of the sponge with each other; and, lastly, The reciprocal attraction which exists between the particles of the sponge and those of the water. It is easy to understand, that the explanation of this fact depends upon properly appreciating the intensity of, and connection between, these several powers. It is probable, that the separation of the particles of bodies, occasioned by caloric, depends in a similar manner upon a certain combination of different attractive powers, which, in conformity with the imperfection of our knowledge, we endeavour to express by saying, that caloric communicates a power of repulsion to the particles of bodies.
FOOTNOTES:
Whenever the degree of heat occurs in this work, it is stated by the author according to Reaumur's scale. The degrees within brackets are the correspondent degrees of Fahrenheit's scale, added by the translator. E.
Collections of the French Academy of Sciences for that year, p. 420.
Chemical Nomenclature.
As I shall afterwards give a definition, and explain the properties of the liquor called ether, I shall only premise here, that it is a very volatile inflammable liquor, having a considerably smaller specific gravity than water, or even spirit of wine.--A.
It would have been more satisfactory if the Author had specified the degrees of the thermometer at which these heights of the mercury in the barometer are produced.
Vide Memoirs of the French Academy, anno 1780, p. 335.--A.
