Chapter LIV: Section I: Operations on unfermented Vegetables (3)

To make the experiment succeed he requires, "That the Oil of Vitriol be dephlegmated as much as possible, and that the Oil of Turpentine be the last that comes over in distillation, which is thick like a syrop, and of a dark-brown colour; for that which is white, and rises at the beginning of the distillation, never takes fire." These are his own words: but no body else hath ever succeeded in making the experiment.

Tournefort had succeeded, a little before Homberg, in firing, not Oil of Turpentine indeed, in which he always failed, but the Oil of Sassafras, by mixing it with an equal quantity of well dephlegmated Spirit of Nitre. Homberg came afterwards, as appears by the Memoirs of the Academy for the year 1702, to fire with Spirit of Nitre the Essential Oils of the aromatic plants of India; and in 1706 Mr. Rouviere fired, with Spirit of Nitre, the empyreumatic Oil of Guaiacum. While this Oil of Guaiacum is burning, a porous spongy body rises from the midst of the flame, to the height of about two feet above the vessel.

Lastly, several years after all these discoveries, Messrs. Geoffroy and Hoffman, the one at Paris, and the other at Hall in Saxony, found a way to fire the Æthereal Oil of Turpentine, each by a different process; yet agreeing in this, that they both combined the Vitriolic Acid with the Nitrous, and with this compound Acid fired that Æthereal Essential Oil, which is one of the thinnest, and, probably for that very reason, the most unfit to produce a flame with Acids.

The most celebrated Chymists, as appears from this short account, have employed themselves in firing Essential Oils; but no body attempted the experiment on Fat Oils. It was not so much as suspected that they were capable of taking fire after this manner, till in 1745 I read before the Academy a Memoir on Oils, which I have already mentioned, and in which I express myself thus:

"I put two ounces and a half of Walnut Oil into the bottom part of a broken retort, having the figure of a cap, or concave hemisphere; and poured thereon two ounces of smoking Spirit of Nitre. It was scarce put in when a considerable ebullition arose, with a very thick smoke. As I found it continually increasing, and very fast too, I retired a little, that I might observe the event without danger. This caution was not unnecessary: for immediately the whole mixture blew up as high as the ceiling, with a noise like the discharge of a musket. Nothing was left in the vessel but a black matter, which still continued to boil a little and run over, and at last remained very rare, spungy, and as full of holes as a honeycomb: its consistence also was such that it did not stick to my fingers when I handled it.

"As Mr. Geoffroy, who first found the means of firing the natural Balsams, observed in them a similar explosion on that occasion, it appears that my Oil was very near taking fire in this experiment: which makes me presume that we may at last succeed in firing Fat Oils likewise, and consequently all others; seeing these have always been looked upon as the most unlikely to produce that phenomenon. I imagine that, to accomplish this, nothing more is necessary than to make use of sufficiently great quantities, and to order it so that the surfaces of the liquors, where they come into contact, may be of a large extent."

Afterwards, in 1747, Mr. Rouelle read before the Academy a Memoir on the accension of Oils by Acids. That Memoir contains a great number of curious experiments, and peculiar manual operations described very distinctly, from which there results a general method of firing without fail, not only Essential Oils, but even any Fat Oil whatever: so that my conjecture, concerning the possibility of firing these latter Oils, mentioned in my above-cited Memoir of 1745, is now changed into a certainty. I shall proceed to explain how I conceive these accensions are brought about, and endeavour to account for the phenomenon from such causes as to me seem the most probable.

A due attention to the phenomena produced by mixing Oils with Acids will enable us, I imagine, to discover the natural cause why the Oils take fire. It is certain, and demonstrated by the most decisive experiments, that the friction of several bodies rubbing against each other produces heat; and that when these bodies are combustible, and the heat produced by their friction rises to a certain degree, they take fire. This, in my opinion, is what happens to Oils when mixed with concentrated Acids. When these two sorts of substances rush into union with rapidity, as in the experiments under consideration, there must necessarily be a great friction among their parts. This friction produces the heat observed at the time of their union. The more concentrated the Acids are, with the greater violence and rapidity do they act upon the Oils, and the greater is the heat raised. If the Acids be concentrated to such a degree as to produce, by uniting with the Oils, a heat equal to that of an ignited body, the combustible substances that are exposed to it, which in this case are Oils, must needs take fire and flame.

The heat produced on this occasion is so great, that, even when the inflammation doth not take place, if you touch the surface of the Oil with your finger, as soon as the Acid hath had its effect, you will find it burn you like a live coal.

Two pieces of wood, rapidly and violently rubbed against each other, take fire. What is it that is kindled in this case? It can be nothing but their Oil: for they contain no other combustible principle. Why doth this Oil take fire? I do not think it possible to assign any reason for it, but the heat produced by the friction of the pieces of wood containing the Oil. If, when Oil is dispersed in a body, of which it is only one component principle, and consequently mixed with many saline, aqueous, and earthy parts, that are not inflammable, but, on the contrary, make the Oil less so, the Oil nevertheless takes fire, and burns when agitated by a sufficient degree of heat; why shall not this very Oil, when separated from the mixt of which it made a part, when united into one distinct mass, and entirely, or almost entirely, freed from the heterogeneous, incombustible parts with which it was combined, and consequently now more inflammable than before; why, I say, shall it not take fire, when exposed to a degree of heat equal, or rather superior, to that which is produced by rubbing two pieces of wood together?

Let us now examine the phenomena produced when Oils are fired by Acids, all the circumstances that favour or hinder their accension, and see if they agree with the explanation here offered.

First, no sort of Oil will take fire with any Acid whatever that is not highly concentrated; for weak Acids act but feebly on Oils, and dissolve them slowly; so that the friction is neither quick nor violent, and consequently produces too faint a heat, far below the degree of ignition.

Secondly, no inflammation is produced when Acids and Oils are mixed in too small quantities; but the more Acid and Oil you mix together, the greater is the certainty of succeeding: for the heat is exactly in proportion to the friction that produces it; and the total quantity, or amount, of this friction is so much the greater, as there are more particles rubbing against each other at the same time. So that if a very small quantity of Acid and Oil be mixed together, there will be but a very small quantity of friction, and consequently a very small quantity of heat; and in that case no inflammation. It was with a view to avoid these inconveniencies, and to procure the opposite advantages in as great a degree as possible, that, in the passage above quoted from my Memoir of Oils, I proposed mixing together large doses of Acid and of Oil, as one of the means by which we might succeed in the accension of Fat Oils.

Thirdly, the figure of the vessel, in which the two liquors are mixed together, is not a matter of indifference. A wide-spreading vessel, of a large diameter with respect to the quantity of liquor it is to contain, favours the inflammation much more than one of a small diameter. Nay, it may not succeed at all in too narrow a vessel, though all other circumstances be properly attended to.

The reason of this is, that the activity of heat produced by friction is not in proportion to the successive, but to the simultaneous frictions: for the heat actually produced by the frictions of an hundred particles, rubbing successively against each other, with intervals sufficient to let the heat go off, almost as fast as it is generated, would be equal to the friction of a single particle only; whereas the heat actually produced by the friction of the same number of particles, all rubbing against each other at the same instant, would be equal to the frictions of all the particles taken together, and consequently an hundred times more active than the other[11]. This being laid down, it is easy to conceive how a large vessel favours the accension more than a small one. It is certain that two liquors which mutually present large surfaces to each other, at the instant of their being mixed together, touch each other at one and the same time in a much greater number of points, than if each had but a small surface; and consequently that they must unite much sooner, and with greater rapidity, in the former case than in the latter.

[11] I believe this proposition is not strictly true: for it appears
to me, that, in order to make the heat, produced by the simultaneous
frictions of an hundred particles, an hundred times more active than
that produced by the successive frictions of the same number of
particles, it is necessary that the simultaneous frictions should act
all together in one point or center; which is impossible. But, as the
particles that rub against each other, in the present case, are very
near and contiguous, it is still true that the heat, resulting from
their simultaneous frictions, is much more active than that produced
by successive frictions only: which is sufficient for our present
purpose.

With these views, and in order to give the liquors this advantageous disposition, I recommended it as what would greatly promote the inflammation of Fat Oils, to order the liquors so, that, at the moment of their mixture, a large surface of each might come into contact with the other.

Fourthly, if we reflect on the experiments hitherto made for kindling Oils by Acids, we shall easily be convinced that all Oils are not equally apt to be fired; and that light, æthereal, very thin, Essential Oils do not produce this phenomenon so readily and so surely, as those of the same kind that are heavy and thick, or at least soon grow thick upon being mixed with Acids.

Mr. Homberg says positively in the above-cited passage of his Memoir, that he never could succeed in setting fire with the Acid of Vitriol to the white, æthereal Oil of Turpentine; that is, to the lightest which comes over first in distillation; but that the very same Acid set fire to "that which comes over last in distillation, which is thick like a syrop, and of a dark-brown colour."

All the experiments by which Oils have been fired, from those of Beccher and Borrichius down to those of Geoffroy and Hoffman, were made on the Essential Oils of the aromatic plants of India, which are the heaviest we know, and on the empyreumatic Oil of Guaiacum, which, besides being very ponderous, is also very thick.

Now these singular effects likewise agree perfectly well with our explanation. It is certain that the parts of a heavy fluid do not yield to any impulse or shock, so easily as those of a lighter fluid; just as the parts of a thick, viscous fluid undoubtedly resist any attempt to separate them, so much the more the nearer the consistence of that fluid is to solidity, or the further it is removed from the state of fluidity. Now, the more resistance the Acid meets with in separating and dividing the parts of the Oil, as it must do to dissolve them, the more considerable will be the force and motion with which it must necessarily act to surmount those obstacles; besides, as experience teaches us that the density and viscidity of the Oils do not, at least to sense, diminish the quickness and activity which the Acid exerts in uniting with them; the greater therefore must be the collisions, frictions, and heat produced: and this plainly shews why heavy, thick Oils take fire, in this case, more readily than those which are fluid and light.

It may here be objected, that Fat Oils, which are thicker and heavier than the light Essential Oils, take fire nevertheless with greater difficulty. This objection is easily answered, by observing, that when we say Acids fire heavy thick Oils with more ease than thin light Oils, this position must be restricted to Oils of the same kind, on which Acids have an equal, or nearly equal, action; that is, to such Oils as differ from each other in no other respect but their thickness and weight.

For example, Mr. Homberg, who could by no means set fire, with Oil of Vitriol, to the Oil that rises first in the distillation of Turpentine, found that the same Acid would fire the Oil that comes last over: and therefore it is reasonable to attribute his success, in firing this last Oil, to its being thicker and heavier than the former; seeing these two Oils are in other respects of the same nature; that Acids have an equal action on both; and that they differ from each other only in the qualities specified above.

But it is evident, that, if the Oils compared together be of different kinds, and differ from each other, not only in weight and thickness, but also by containing different principles, or, at least, the same principles combined differently, and in different proportions, the action of any Acid on those Oils must also be different; and that regard must be had thereto in determining their degrees of inflammability.

Now all this is applicable to Fat Oils, when compared with light Essential Oils, in point of inflammability. If all these Oils were of the same nature, and differed from each other in weight and thickness only, the objection drawn from Fat Oils, which though thicker than Essential Oils do not take fire so easily, would be a very good one, and fact would be against our reasoning. But this is far from being the case: the properties, as well as the analysis, of Fat Oils shew their nature to be very different from that of Essential Oils; that there is more water in their composition; and that they are full of a mucilaginous or gummy principle, which must greatly obstruct their inflammability, and the action of Acids upon them.

None of the effects, therefore, that attend the firing of Oils with Acids, is repugnant to our way of accounting for the phenomenon, which is one of the most beautiful in all Natural Philosophy. To conclude this important subject, nothing now remains but to consider the effects produced by the Vitriolic Acid in these accensions.

This Acid, though of a stronger nature, and capable of being more highly concentrated than the Nitrous Acid, seems however less qualified to produce a flame with Oils. Indeed Mr. Homberg fired Oil of Turpentine by mixing it with Oil of Vitriol: but I do not know that the experiment hath succeeded with any other Chymist; on the contrary, most of those who have tried it affirm, that they never could fire any Oil with that Acid alone.

Oils are probably in the same case as metallic substances, with regard to these two Acids. We know that the Nitrous Acid dissolves those substances with vastly more activity and violence than the Vitriolic Acid exerts upon them; which may depend, either on the disposition and configuration of their parts, or on the portion of phlogiston which, according to the opinion of most Chymists, is united with the Nitrous Acid, is its peculiar characteristic, and the cause of the great vivacity with which it dissolves almost all matters that contain the phlogiston.

I say _almost_ all matters that contain the phlogiston; because there are some substances that contain a great deal thereof, and yet are not at all acted on by the pure Nitrous Acid. These substances are matters perfectly charred: that is, such as are capable of enduring the greatest violence of fire in close vessels, without yielding a single atom of Oil; that burn almost quite away, yet only grow red hot without flaming; or at least produce but a very small, slight flame, from which it is impossible to obtain the least particle of soot or fuliginosity; in a word, that contain an inflammable matter, but such as is fit to be an ingredient in the composition of metallic substances, to which the peculiar title of the Phlogiston is appropriated.

I say, then, that if the Nitrous Acid be poured on a mere coal, perfectly charred, it is impossible for the Acid, be it ever so highly concentrated, to set the coal on fire, though heated before to the greatest degree that it can possibly admit of without kindling; and, which is still more remarkable, if a live coal be plunged into the most highly smoking Spirit of Nitre, it will be extinguished as if dipt in pure water.

But to return to the Vitriolic Acid: it is singular enough that this Acid, which attacks Oils with less activity, and for that reason seems less fit to set them on fire, than the Nitrous Acid, yet greatly promotes their accension, when mixed with that very Acid. This may be owing to its rendering the Oils with which it mixes heavier and thicker; or else, as Mr. Rouelle conjectures with great probability, being more concentrated than the Nitrous Acid, and having a greater affinity with water, it dephlegmates the other, and thereby increases its activity; or, lastly, this may arise from some other cause yet unknown to us, and perhaps from that by which the Acids of Nitre and of Sea-salt, which, when separate and perfectly pure, can neither of them dissolve Gold, are enabled, when combined together, to make a perfect solution of that metal.

PROCESS III.

_To combine Essential Oils with Mineral Sulphur. Balsam of Sulphur. This Composition decompounded._

Put into a matrass one part of Flowers of Sulphur; pour on them six parts of the Essential Oil of Turpentine, for instance; set the matrass in a sand-bath, and heat it gradually till the Oil boil. The Sulphur, which at first lay at the bottom of the matrass, will begin to melt, and appear to dissolve in the Oil. When it hath boiled in this manner for about an hour, take the matrass from the fire, and let the liquor cool. A great deal of the Sulphur that was dissolved therein will separate from it as it cools, and fall to the bottom of the vessel in the form of needles, much like a Salt shooting in water.

When the liquor is perfectly cold, decant it from the Sulphur that lies at the bottom of the vessel: to that Sulphur put fresh Oil of Turpentine, and proceed as before: the Sulphur will again disappear, and be dissolved in the Oil: but when the mixture is cold, you will find new crystals of Sulphur deposited at the bottom. Decant once more this Oil from the crystals, and pour on fresh Oil to dissolve them: continue the same method, and you will find that about sixteen parts of Essential Oil are required to keep one part of Sulphur dissolved when cold. This combination is called _Balsamum Sulphuris Terebinthinatum_, if made with Oil of Turpentine; _Anisatum_, if with Oil of Anise-seeds; and so of others.

_OBSERVATIONS._

Essential Oils do not dissolve Sulphur, in such quantities, and with so much ease, as Fat Oils do. It was shewn above, that a Fat Oil is capable of keeping a considerable quantity of Sulphur in solution; whereas no less than sixteen parts of Essential Oil are required to dissolve one part only of Sulphur, as in this process.

The property which Sulphur hath of separating, in part, from the Essential Oil in which it is dissolved, and falling to the bottom of the vessel in the form of crystals, as the Oil cools, proves that it is a kind of Neutral Salt, which, being insoluble in water, because of the great quantity of inflammable matter that serves it for a basis, is not to be dissolved but by substances that actually contain themselves a great deal of inflammable matter; such as Oils and Metallic substances.

Though the latter are almost always solid, it nevertheless unites with several of them into regular forms, resembling saline crystals in every thing but pellucidity; as appears, for example, in several Pyrites, Antimony, and some other sulphureous minerals. But when it is dissolved in Oils, especially in such as are capable of keeping but a small quantity thereof in solution, and consequently drop a good deal of it as they cool, it is precisely in the case of one of those Salts whereof hot water dissolves more than cold; that is, the Oil, that is saturated with as much Sulphur as it can possibly take up when boiling hot, lets some part thereof precipitate as it cools; while the Sulphur thus separated from the Oil unites into little glebes of a regular figure, and actually crystallizes; in the same manner as Nitre, when boiling water hath dissolved as much thereof as it can possibly take up, partly separates from it when it cools, and falls to the bottom of the vessel in small crystalline _moleculæ_, of the form peculiar to that Salt.

Mr. Homberg made some very curious experiments on this combination of Sulphur with an Essential Oil. In the Memoirs of the Academy he gives the following analysis thereof.

"Put your Sulphur dissolved by Oil of Turpentine into a pretty large retort, because the matter puffs up towards the end, and distil with a very gentle heat for twelve or fifteen days and nights. There will come over about two thirds of the quantity of a colourless Oil of Turpentine, and at the same time _a pretty considerable quantity_ of a whitish ponderous water, as acid as good Spirit of Vitriol. After this, the drops of Oil that come off will begin to be red. Then change your receiver, and increase the fire gradually; and in seven or eight hours time, with a very great heat, force off all that will rise, using a glass retort for your recipient. At last, most of the Oil will come over into the receiver very thick and high-coloured, still accompanied with a whitish and very acid water. In the retort will be left a black _caput mortuum_, spongy, or foliated, shining, and insipid.... This _caput mortuum_ neither grows white, nor flames, nor wastes considerably in a strong fire.

"The matter that comes over into the receiver must be distilled again, with a very gentle heat continued for several days and nights, in order to separate once more the colourless Oil and the remaining acid water, till the Oil begin to come off red. Then take the retort from the fire, and on the black gummy matter left in it pour good Spirit of Wine; mix the whole well together, and distil with a very gentle heat. When this Spirit of Wine is come off, pour some fresh on the black gum left in the retort, and distil as before. Repeat this till the Spirit of Wine cease to have a bad smell."

There is great reason to believe, that, by the union which the Sulphur contracts with the Oil, the cohesion of the Acid and the Phlogiston, which constitute that mineral, is considerably weakened; and that this is what occasions the decomposition of the Sulphur so manifest in Mr. Homberg's analysis. The inflammable matter of the Sulphur is so incorporated with that of the Oil in the solution, that they form together one homogeneous whole; by which means the Acid of the Sulphur, which is of course dispersed through the whole liquor, is not now combined with the Phlogiston, as it was in the Sulphur before it was blended with the Oil; that is, with the pure Phlogiston; but with that Phlogiston which constitutes the oily mixture, or, which is the same thing, with actual Oil. And this is the reason that a composition of Oil and Sulphur yields, in distillation, nearly the same principles that a combination of the same Oil with the Vitriolic Acid would yield.

We have already seen, under the head of Fat Oils, that when Oils are combined with Acids, if this combination be again decompounded by distillation, those two substances cannot be obtained in their original state; but that they are changed and partly decomposed. The case is the same in the experiment before us. We first get, by distillation, a pretty considerable quantity of Oil of Turpentine, that seems to have suffered no change at all. This first Oil is that which the action of fire separates from the Acid; and this it effects with so much the more ease, that, a great quantity thereof having been necessarily used to dissolve a little Sulphur, it greatly exceeds the quantity of Acid in the mixture, and that the distillation is ordered to be made with a very weak degree of heat: for M. Homberg says, it ought to be continued twelve or fifteen days and nights. Now this manner of distilling, with a very gentle heat, is the most effectual means of separating Oils, especially light Essential Oils, from Acids; because these Oils rise in distillation with very little heat; whereas the Acids, being much more ponderous, require a great deal more.

The Oil that rises first in distillation, appears indeed to be the same with that which was originally used in the mixture; but the quantity is much smaller: first, because some part of it, being combined with the Acid of the Sulphur, is thereby rendered thick and heavy, which hinders it from rising in this first distillation with a very gentle heat, and is the reason that it cannot be elevated without a much stronger degree of fire. It is this part that afterward comes over in the form of a red liquor upon increasing the fire.

The second cause why the quantity of Oil is lessened, is, that part of it is decomposed in the operation. This decomposed part of the Oil furnishes that considerable quantity of water which ascends at the same time with the Oil, or a little after it, and serves for a vehicle to the Acid that rises with it in this first distillation; which Acid, though pretty strong, is now much more loaded with water than when it was an ingredient in the combination of Sulphur. This acid water is of a milky white colour, because many oily particles are suspended and diffused in it, but not perfectly dissolved.

The _caput mortuum_ that is left in the retort, after all the red thick Oil is driven up by a very strong degree of fire, is a sort of charred matter, consisting of some of the earth of the Sulphur, and of the decomposed Oil, united with a phlogiston, which is probably furnished by both these substances. This matter contains also a little Acid fixed with it. This Acid reproduces Sulphur, or at least becomes sulphureous, and flies off in vapours, when the coal is urged by a violent forge-heat: for Mr. Homberg observed, that by this means it exhaled an odour of Sulphur, and lost in weight.

This charred matter is of a singular nature: for, by being exposed to a forge-heat, and even to the heat in the focus of a burning glass, it seemed to suffer no other change than some loss of weight, occasioned by the evaporation of the acid effluvia carried off by the heat; for it still retained its black colour, and was neither consumed nor vitrified. In order to melt it, Mr. Homberg was forced to mix it with Borax. This Salt converted it into a glass of a dark-grey colour: and, as there appeared a little verdegris on the surface of this glass after keeping it in a moist place, he thereby found that the Sulphur he had used contained a little Copper.

We know that the earth of Copper is refractory, and that it communicates a dark colour to matters vitrified along with it: and perhaps it was the cause why the fixed matter in question retained its blackish colour so obstinately, notwithstanding the phlogiston that must have been in it at first was, in all probability, consumed by the violent ignitions it underwent.

As to the thick oily matter, called _gummy_ by Mr. Homberg, from which he directs Spirit of Wine to be repeatedly distilled, till it cease to have a disagreeable smell, there is great reason for thinking it to be, as we said before, a portion of the Oil which the Acid hath rendered thick and heavy. The Spirit of Wine dissolves and carries up the most acid part, which always hath a disagreeable smell.

Mr. Homberg says, that "the part remaining after this, which he calls the _Gum of common Sulphur_, hath a pleasant balsamic odour; that it partly dissolves in Spirit of Wine, a hard resinous matter being left, which will not dissolve, either in Spirit of Wine, or in the strongest lixivium." Of consequence, therefore, it is neither a resinous matter nor a sulphur; "yet it dissolves perfectly in distilled Oils." What then is this singular body? It is certainly a subject for very curious inquiries. In general, Mr. Homberg's whole process is full of interesting facts, and well deserves to be repeated, carried further, and carefully attended to.

PROCESS IV.

_To combine Essential Oils with Fixed Alkalis. Starkey's Soap._

Take Salt of Tartar, or any other Alkali, thoroughly calcined. Heat it in a crucible till it be red, and in that condition throw it into a hot iron mortar: rub it quickly with a very hot iron pestle; and as soon as it is powdered pour on it, little by little, nearly an equal quantity of Oil of Turpentine. The Oil will enter into the Salt, and unite intimately with it, so as to form a hard paste. Continue rubbing this composition with the pestle, in order to complete the union of the two substances; and, as your Oil of Turpentine disappears, add more, which will unite in the same manner, and give a softer consistence to the soapy mass. You may add still more Oil, according to the consistence you intend to give your Soap.

_OBSERVATIONS._

Essential Oils do not unite near so easily as Fat Oils with Alkalis. For this reason, to make a Soap with an Essential Oil, we must take a method different from that used in common soaperies. For if an Essential Oil be substituted for the Fat Oil, in the ordinary way of making Soap, far from combining with the alkaline lixivium, though ever so strong, it will be wholly dissipated and vanish: so that, after boiling some time, you will find nothing but the lye, just as when first put in, only a little more concentrated.

The water, in which the Alkali is dissolved when in the form of a lye, is the principal thing that hinders the Salt from uniting with the Essential Oil. Water is such an enemy to this union, that, if the Alkali be ever so little moist, the operation will not succeed; even though all the other precautions mentioned in the process should be exactly observed.

In order, therefore, to free the Alkali from all humidity, it is necessary to begin with making it red-hot; and then, that this Salt, which is very greedy of moisture, may not imbibe any from the air, before it be mixed with the Essential Oil, it must not be suffered to cool; but the mixture must be made in a hot vessel, as soon as the Salt is reduced to powder. When every particle of the Salt is once covered with Oil, you need not fear its attracting any moisture, at least very quickly, because the Oil opposes its admission.

Starkey, the first Chymist who found the means of making Soap with an Essential Oil, and by whose name this kind of Soap is therefore called, made use of a much more tedious method than that proposed in our process. He began with mixing a very small quantity of Oil with this Salt, and waited till all the Oil united therewith of its own accord, so as to disappear entirely, before he added any more; and thus protracted his operation exceedingly, though in the main it was the same with ours. The method here proposed is more expeditious, and was invented by Dr. Geoffroy.

Starkey's Soap dissolves in water much as common Soap does, without any separation of the Oil: and by this mark it is known to be well made. It may also be decompounded, either by distillation, or by mixing it with an Acid: and its decomposition, in either of these ways, is attended with nearly the same phenomena as the decomposition of common Soap.

CHAP. VI.

_Of the_ SUBSTANCES _obtained from_ VEGETABLES _by Means of a_ GRADUATED HEAT, _from that of boiling Water, to the strongest that can be applied to them in close Vessels_.

PROCESS I.

_To analyze Vegetable Substances that yield neither a Fat nor an Essential Oil. Instanced in Guaiacum-Wood._

Take thin shavings of Guaiacum-wood, and put them into a glass or stone retort, leaving one half thereof empty. Set your retort in a reverberating furnace, and lute on a large glass receiver having a small hole drilled in it; such as is used for distilling the Mineral Acids. Put a live coal or two in the furnace, to warm the vessels gently and slowly.

With a degree of heat below that of boiling water, you will see drops of a clear insipid phlegm fall into the receiver. If you raise the fire a little, this water will come slightly acid, and begin to have a pungent smell. With a degree of fire somewhat stronger, a water will continue to rise which will be still more acid, smell stronger, and become yellowish. When the heat comes to exceed that of boiling water, the phlegm that rises will be very acid, high coloured, have a strong pungent smell, like that of matters long smoked with wood in a chimney, and will be accompanied with a red, light Oil, that will float on the liquor in the receiver.

And now it is necessary that the operation be carried on very cautiously, and vent frequently given to the rarefied air by opening the small hole in the receiver: such an incredible quantity thereof rushing out of the Wood, with this degree of heat, as may burst the vessels to pieces, if not discharged from time to time.

When this red, light Oil is come over, and the air ceases to rush out with impetuosity, raise your fire gradually, till the retort begin to redden. The receiver will be filled with dense vapours; and, together with the watery liquor, which will then be extremely acid, there will rise a black, thick, ponderous Oil, which will fall to the bottom of the receiver, and lye under the liquor.

Then give the utmost degree of heat; that is, the greatest your furnace will allow, and your vessels bear. With this excessive heat a little more Oil will rise, which will be very ponderous, as thick and black as pitch; and the vessels will continue full of vapours that will not condense.

At last, when you have kept the retort exceeding red for a long time in this extremity of heat, so that it begins to melt, if it be of glass, and you perceive nothing more come over, let the fire go out and the vessel cool. Then take off your receiver: from the black oil at bottom decant the acid liquor with the red Oil floating on it, and pour them both into a glass funnel, lined with brown filtering paper, and placed over a bottle. The acid liquor will pass through the filter into the bottle, and the Oil will be left behind, which must be kept by itself in a separate bottle. Lastly, into another funnel, prepared as the former, pour the thick Oil remaining with a little of the acid liquor at the bottom of the receiver. This liquor will filter off in the same manner, and thus be separated from the heavy Oil.

In the retort you will find your Guaiacum-shavings, not in the least altered as to their figure, but light, friable, very black, scentless, and tasteless, easily taking fire, and consuming without flame or smoke; in short, you will find them charred to a perfect coal.

_OBSERVATIONS._

Hitherto we have examined the substances that may be obtained from vegetables, either without the help of fire, or with a degree of heat not exceeding that of boiling water. The analysis of plants can be carried no further without a greater degree of heat: for, when the principle of odour, and the essential oil of an aromatic plant, are wholly extracted by the preceding processes, if the distillation be afterward continued without increasing the heat, nothing more will be obtained but a little Acid; which will soon cease, as a small part only of the quantity contained in the plant will be elevated; the rest being either too ponderous, or too much entangled with the other principles of the body, to rise with so small a degree of heat.

In order, therefore, to carry on the decomposition of a plant, from which you have, by the methods before proposed, extracted all the principles it is capable of yielding when so treated; or, which comes to the same thing, in order to analyze a vegetable matter, which affords neither an expressed nor an essential oil, it must be distilled in a retort with a naked fire, as directed in the process, and be made to undergo all the degrees of heat successively, from that of boiling water, to the highest that can be raised in a reverberating furnace.

A heat inferior to that of boiling water, with which we must begin in order to warm the vessel gradually, brings nothing over, as hath been said, but an insipid water, destitute of all acidity. By increasing it nearly to the degree of boiling water, the distilled water comes to be slightly acid.

When the heat is made a little stronger than that which is necessary for the elevation of an Essential Oil, the acidity of the water that comes off is much more considerable. It hath now both colour and smell, and there rises with it a red, light Oil, that floats on the liquor in the receiver. This is not an Essential Oil; it hath none of the odour of the plant. Though so light as to float on water, yet it will not rise with the degree of heat that raises Essential Oils; even those that much surpass it in gravity, and will not swim on water as this does. This proves that the ease or difficulty, with which a particular degree of heat raises any substance in distillation, doth not depend altogether on its gravity: its dilatability, or the volatile nature of the matters, with which it is so closely united as not to be separated from them by distillation, may probably contribute greatly to produce this effect.

It is very surprising that a substance so hard, so compact, so dry, in appearance, as Guaiacum-wood, should yield such a large quantity of water by distillation; and it is equally so, that it should discharge so much air, and with so much impetuosity, as nothing but experience could render credible. We have, in the process, directed the precautions to be taken when this air, from being prodigiously condensed in the body of which it made a part, is set at large, rushes out of confinement, and expands with all its natural elasticity. From this air arises the greatest danger attending the operation.

It hath been remarked, that the heaviest and most compact woods yield the most air in distillation: and accordingly Guaiacum-wood, which we have chosen for an instance, as exceeding almost all others in hardness and weight, discharges a vast quantity of air when analyzed.

The thick, burnt, empyreumatic Oil, that comes over last in this distillation, is heavier than water; on account, probably, of the great quantity of Acid with which it is replete. The two kinds of Oil obtained in this analysis may be rectified, by distilling them a second time, or rather several times; by which means they will become lighter and more fluid, as we have seen happen to Fat and Essential Oils. In general, all thick, heavy Oils constantly owe these qualities to an Acid united with them; and it is by being freed from some of that Acid in distillation, that they always acquire a greater degree of lightness and fluidity from that operation. To these laws all vegetable Oils are subject, of what nature soever they be.

The analysis of a vegetable substance, exhibited above, shews what may be obtained from them, when distilled in close vessels, with a graduated heat, from that of boiling water, to that which converts the mixt to a perfect coal; viz. Phlegm, an Acid, a light Oil, much Air, and a thick Oil. But this analysis is far from being a complete one: it may be carried much farther, and made more perfect.

None of the principles obtained by this analysis are pure, simple, and thoroughly separated from the rest. They are still in some measure blended all together: their separation is but begun; and each requires a second and more accurate analysis, to reduce it to the greatest degree of purity of which it is capable. The Oil and the Acid chiefly merit so much pains.

A great deal of the Acid of the plant remains, as was said, combined with the two sorts of Oil here obtained; which we have reason to think differ no otherwise from one another, than as there is more or less Acid united with each. The best way of freeing these Oils from their redundant Acid is to distil them frequently from Alkalis and Absorbents. Some of our best Chymists have taken this pains with several sorts of Oils; but the method might be still extended, and the operation carried further than hath yet been done.

The Acid is in the same circumstances nearly as the Oil. The first that rises is mortified with much water, to which it owes a good deal of its volatility. That which comes over last is much more concentrated, and consequently heavier; yet it is still very aqueous. It might be freed in a great measure from this adventitious water, and so rendered much stronger; which would give us a better opportunity to discover its nature and properties, of which we know but very little.

Water is not the only heterogeneous substance that disguises the vegetable Acid: a pretty considerable quantity of the Oil of the plant is also combined with it, and contaminates its purity. The proof of this is, that, when these Acids are kept, in the same condition in which they first come over, for any length of time, in a glass vessel, they gradually deposite, on the bottom and sides of the vessel, an oily incrustation, which grows thicker and thicker the longer it stands; and, as this oily matter separates from it, the Acid liquor appears less unctuous and saponaceous.

A very good way to separate this Oil more effectually from the Acid is to combine the whole with absorbents, and abstract the Oil again by distillation. By this means a very sensible quantity of Oil may be separated that was not perceived before. On this occasion it is proper to remark, that the Oil thus united with the vegetable Acid is perfectly dissolved by it; seeing it is thereby rendered miscible with water, so that it doth not, like Alkaline soaps, in the least obscure its limpidity, or give it a milky cast: for these aqueous, oily Acids are very transparent, especially after they have stood for some time.

The air that is discharged with impetuosity in the operation, and must be let out, is loaded with many particles of Acid and Oil reduced to vapours, which it carries off; and by this means the quantity of the principles extracted from the mixt cannot be accurately determined: nor are the vapours, of which the vessels remain full after the operation, any other than particles of Acid and Oil, which the violence of the fire hath rarefied exceedingly, and which do not easily condense.

If we distil in this manner a vegetable aromatic substance, which of course contains an Essential Oil, provided it hath not been previously extracted by the appropriated process, this Essential Oil will rise first, as soon as the distilling vessel acquires the heat of boiling water: but its scent will not be near so sweet or grateful, as if it were distilled in the manner before directed as properest for it. On the contrary, it will have an empyreumatic smell: because in this way it is impossible to avoid scorching and half-burning some of the matter distilled; especially that part of it which touches the sides of the retort. Moreover, the very same equable degree of heat can hardly be kept up with a naked fire. The Essential Oil, therefore, though it rises first, will not be pure, but contaminated with a mixture of the empyreumatic Oil that first comes over, and will be confounded therewith.

If a substance abounding with Fat Oil, that hath not been expressed from it, be distilled according to the present process, it will yield no Fat Oil by distillation; but only much more of the first clear Oil, and of the second thick Oil, than if all the Fat Oil it would have afforded had been first drawn off by expression: for as the Fat Oil will not rise in distillation, without a degree of heat greater than that of boiling water, neither can it endure such a degree of heat without changing its nature, without losing that mildness, and, in a great measure, that unctuosity which is natural to it. It will therefore be confounded with the other empyreumatic Oil, which, in all probability, would itself be no other than a Fat Oil, if it could be wholly extracted, without the aid of fire, from the vegetable substances containing it.

Most vegetable substances, when distilled with a strong fire, yield the same principles with that which we have chosen for an instance. Entire plants of this kind, those from which the odorous principle, the Essential Oil, or the Fat Oil, hath been drawn, those of which extracts have been made by infusion or decoction, or the extracts themselves; all such matters being distilled yield a Phlegm, an Acid, a thin Oil, Air, and a thick Oil, and the products of their several analyses differ from each other, only on account of the different quantity or proportion that each contains of the principles here enumerated.

But there are many other plants, which, besides these substances, yield also a considerable quantity of a Volatile Alkaline Salt. This property is possessed chiefly by that tribe of plants which is distinguished by having cruciform flowers; among which there are some that being analyzed greatly resemble animal matters. We shall now analyze one of these; Mustard-seed, for instance.

PROCESS II.

_To analyze a vegetable Substance which yields the same Principles as are obtained from Animal Matters; instanced in Mustard-seed._

With an apparatus like that of the preceding process, and with the same fire, distil Mustard-seed. With a degree of heat inferior to that of boiling water, there will come over a phlegm somewhat coloured, and impregnated with a Volatile Alkaline Salt. With a degree of heat greater than that of boiling water, the same kind of phlegm, impregnated with the same Salt, will continue to come over; but it will be much higher coloured, and will be accompanied with a light Oil. At this time a considerable quantity of air is discharged; with regard to which the same precautions must be taken as in distilling Guaiacum.

If the fire be gradually raised, there will come over a black thick Oil, lighter however than water; and at the same time vapours will rise, and, condensing on the sides of the receiver, form into sprigs or ramifications. This is a Volatile Alkaline Salt, in a concrete form, like that of animals, as we shall hereafter see. These vapours are much whiter than those of Guaiacum.

When you have thus drawn off, with a very strong fire, all the Volatile Alkali and thick Oil contained in the subject, there will be nothing left in the retort but a sort of coal, from which a small quantity of phosphorus may be obtained, provided the retort you employ for that purpose be good enough to stand a very violent heat.

_OBSERVATIONS._

Mustard-seed furnishes us with an instance of a vegetable, from which we obtain, by analyzing it, the very same principles that animal matters yield. Instead of getting an Acid from it, we obtain only a Volatile Alkali; probably because the Acid, which originally enters into the composition of this kind of vegetables, as well as of all others, undergoes in passing through their strainers, and mixing with their juices, such alterations as it suffers when it enters into the composition of animals: that is, it combines with some of their Earth and of their Oil, in such a manner as to be changed into a Volatile Alkali, or at least disposed to be converted into one with the aid of fire.

We shall not here speak of the manner of separating and depurating the principles obtained by this process; but reserve it for the analysis of animals, which is absolutely the same. We shall content ourselves with observing, that the first Volatile Alkali which rises at the beginning of the operation together with the phlegm, in a degree of heat below that of boiling water, differs from that which doth not come over till towards the end of the distillation, when the last thick Oil ascends. The different times, and different degrees of heat, in which these two Alkalis rise, shew that the former exists actually and perfectly in the plant; but that the latter is generated during the distillation, and is the product of the fire, which combines together the materials whereof it is composed.

Vegetables that thus yield a Volatile Alkali with a heat less than that of boiling water, irritate the organ of smelling, affecting it with a sensation of acrimony; and the effluvia, which rise from them when bruised, make the eyes smart so as to draw tears from them in abundance. Several of these matters, being only bruised, effervesce with Acids: effects producible only by a very Volatile Alkaline principle.

This is that Alkali, the lightest of all the principles that can be extracted from bodies, which rises first in our distillation along with the phlegm, and with a degree of heat much inferior to that of boiling water. As the phlegm with which it rises is very copious, it is dissolved thereby; which is the reason it doth not appear in a concrete form. To this water it gives a slight yellowish tinge, because it is impure and oily. The saline Alkaline properties of this liquor have procured it the title of a Volatile Spirit. This Volatile Alkali, which exists naturally and perfectly formed in Mustard-seed, Onions, Garlic, Cresses, and other such vegetables, constitutes a difference between them and animal substances, which contain only the materials requisite to form a Volatile Alkali, but none ready formed, unless they have undergone the putrid fermentation.

The second Volatile Alkali which rises in our distillation, but not without a very strong degree of fire, and at the same time with the last thick Oil, seems to be a production of the fire; for if it were already formed in the mixt, as the other is, it would rise with the same heat, and at the same time, being equally volatile. It is not impossible, however, that it may exist perfectly formed in the plant; but, having contracted an union with some Acid, and therewith composing an Ammoniacal Salt, it may by that means be hindered from rising so readily as is agreeable to its natural volatility.