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Chapter LII: Section I: Operations on unfermented Vegetables (1)

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CHAP. I.

_Of the_ SUBSTANCES _obtained from_ VEGETABLES _by_ EXPRESSION _only_.

PROCESS I.

_To express and depurate the Juice of a Plant, containing its Essential Salt. The Crystallization of that Salt._

Before sun-rise gather a good quantity of the plant from which you design to express the juice, in order to obtain its Salt. Wash it well in running water, to clear it of earth, insects, and other adventitious matters. Bruise it in a marble mortar; put it into a bag of new, strong, thick linen cloth; tye the bag tight, and commit it to a press. By pressing it strongly you will squeeze out a great quantity of green, thick juice, which will have the same taste as the plant. Dilute this juice with six times as much pure rain-water, and filter it repeatedly through a woollen bag, till it pass clear and limpid. Evaporate the filtered juice with a gentle heat, till it be almost as thick as before it was mixed with water. Put this inspissated juice into a jar, or other vessel of earth or glass; on its surface pour olive oil to the depth of a line, and set it in a cellar. Seven or eight months after this, pour off gently the liquor contained in the vessel, the inside of which you will find covered with a crystallized Salt. Separate the crystals gently; wash them quickly with a little fair cold water, and dry them: this is the Essential Salt of the plant.

_OBSERVATIONS._

Every plant is not equally disposed to yield its Essential Salt, by the method here proposed. Succulent vegetables only, whose juices are aqueous and not too viscous, are fit for this purpose. Such, for example, as sorrel, brook-lime, succory, fumitory, water-cresses, plantain, &c. An Essential Salt cannot be procured from those that yield thick, viscid, mucilaginous juices, such as the seeds of flea-wort; unless their juices be previously attenuated by fermentation, and that viscosity destroyed which obstructs the Crystallization of this Salt.

Nor can the Essential Salt be obtained in any quantity from vegetable matters abounding in Oil. Most kernels and seeds are of this sort: they all contain a great quantity of fat oil, which so entangles and clogs this Salt, that the particles thereof cannot shoot away from the tenacious juices into crystals.

The same is to be said of dry aromatic plants; because they contain much essential oil, or resinous matters that produce the same effect. It is true the Essential Salt itself contains a certain portion of oil; for it is no other than the Acid of the plant incorporated and crystallized with part of its oil and of its earth: but then the oil must not be in too great a quantity: because it sheaths the Acid, renders it clammy, as it were, and hinders it from extricating itself, so as to be able to exert its qualities, and appear in the form of Salt.

The plants, from which you intend to extract this Salt, should be gathered in the morning before sun-rise; because they are then most succulent, not being yet dried up or withered by the heat of the sun.

The juice of plants obtained by expression is very thick; because it contains many particles of the bruised plant, that are unavoidably squeezed out along with it. In order to clear it of these superfluous parts, it is proper to filter it; but as that would be difficult, on account of the thickness of the juice, it must be thinned, by diluting it with a quantity of water, sufficient to give it the requisite degree of fluidity.

Instead of thus diluting the expressed juice, the plant may be ground with water, before it is put into the press: it will by this means furnish a more fluid juice, that will easily pass through the filter. This method may be employed with success on dry plants, or such as are not very succulent. For this operation rain-water is to be preferred to any other; because it is the purest: for all waters that have run some time through the earth, or on its surface, are to be suspected of containing some saline or selenetic matter, which would mix with and deprave the Essential Salt.

The juice of the plant, when diluted with the quantity of water sufficient to facilitate its filtration, is too aqueous to let the Salt it contains unite into crystals: it must therefore be evaporated, till it hath recovered a somewhat thicker consistence. The heat applied for that purpose must be gentle; lest the acid and oily parts, that are to form the Salt, be spoiled or dissipated, as they are not very fixed. In summer, the heat of the sun is sufficient to effect this evaporation: but if you make use of this method, the juice to be evaporated must be put into several broad flat pans; that, a larger surface being exposed to the action of the air and sun, the evaporation may be the sooner completed: for if the juice should continue too long in the degree of heat requisite for its evaporation, it might begin to ferment; which would be very detrimental.

The oil poured on the liquor prevents its fermenting, putrefying, or growing mouldy, during the long space of time required for the crystallization of the Essential Salt.

These Salts are excellent medicines, being endued with the same virtues as the plants from which they were obtained.

They cannot be procured from plants by distillation, though they consist in a great measure of volatile principles: nor are they obtainable by any other process that requires much heat; because they are easily decomposed, and the fire changes their natures entirely. The oily Acids extracted from plants by distillation do not crystallize, and always have an empyreumatic acrimony, that makes them very different from the Essential Salts, which are very mild and saponaceous.

PROCESS II.

_To draw the Oils out of Kernels, Seeds, and Fruits, by Expression._

Pound in a marble mortar, or grind in a mill, the kernels, seeds, or fruits, out of which you intend to express the Oil. If your matters be meagre, and grind to meal, suspend that meal in the steam of boiling water, in order to moisten it a little, and then dry it.

Tye up your matter thus prepared in a new, strong, thick, canvass bag, and put it into a press, between two iron plates previously heated in boiling water: squeeze it strongly, and you will see the Oil run in streams into the receiving vessel.

_OBSERVATIONS._

The Fat Oil of Plants is particularly found in kernels, seeds, and some fruits; some kernels contain such a vast quantity thereof, that, on being very slightly bruised in a mortar, they discharge it in great abundance. Sweet and bitter Almonds, Walnuts, and Lint-seed, are all of this kind; and require no other management but to be pounded and pressed, to make them yield a great deal of Oil. But there are others more meagre, that being ground produce an almost dry flower. In order to facilitate the expression of the Oil out of such, they must be expressed, when ground, to the steam of boiling water. For this purpose the meal may be put into a fine sieve, and that suspended over a pan half-full of water kept boiling on the fire. The ascending vapours will moisten the flower, render it more unctuous, and facilitate the expression of the Oil.

It is proper to dry it a little before it be put into the press, that it may yield as little water as possible along with the Oil. Nevertheless, so much water happens now and then to be left in it, that some is expressed together with the Oil: but as oil and water do not incorporate, they are easily separated after the operation is finished.

The extraction of the Oil is also greatly facilitated by heating the plates, between which the oleaginous matters are squeezed: but they must not be made too hot, if you mean to have a very mild Oil, designed either for aliment or for medicine; such as the Oil of Olives, and that of sweet almonds. For this reason the plates must be warmed in boiling water only: if you heat them to a greater degree, you run the risk of giving an acrimony to the Oils you express. But, when these Oils are intended for other uses, the plates may be made hotter, because their heat increases the yield of Oil.

It is remarkable, that all the Oils obtained by expression, with the precautions above recommended, are constantly very mild; even though the matters from which they are extracted be in themselves very acrid. Mustard-seed, which is so acrid that it is even caustic, yields, by expression, an Oil as mild as that of sweet almonds. But then the kernels, seeds, and fruits, from which the Oils are extracted, must not be old; because these Oils, which are perfectly mild when fresh and new, become intolerably acrid when they grow old, and acquire this acrimony even in the fruit itself; for it is observed that these fruits turn rancid as they grow old.

The Fat Oils obtained by expression are used in medicine, both internally and externally, as Lenitives and Emollients. Every body knows the great use of Oil of sweet Almonds, in inflammatory distempers of the breast and intestines. But it must be carefully noted, that these Oils can produce no good effects, unless they be fresh expressed, and from fruits, kernels, or seeds, that have not been long kept: for they not only lose their lenient virtue by growing old, but they even acquire an opposite quality, and contract such a sharp acrimony, that far from procuring any salutary relief or mitigation to the inflamed parts, they are capable of irritating and inflaming the sound.

It is therefore of the last importance to administer them only when they are quite fresh: they ought never to be above two or three days old. Those that are old are generally more limpid and transparent than the fresh, which look a little more cloudy. The best way to distinguish them is to taste them, and to try whether or no they leave any sensation of rancidity on the palate and in the throat.

PROCESS III.

_To draw the Essential Oils of certain Fruits by Expression._

Take the rind of a Citron, Lemon, Orange, Bergamot-pear, or other fruit of that kind; cut it in slices, and, doubling the slices, squeeze them between your fingers, over against a polished glass set upright, with its lower end in a vessel of earth or porcelain. Every time you squeeze the peel in a new ply, there will squirt out of it several fine jets of liquor, which, meeting with the surface of the glass, will be condensed into drops, and trickle down in small streams into the recipient. This liquor is the Essential Oil of the fruit.

_OBSERVATIONS._

No fruits but those of the kind above-mentioned will yield an essential Oil by expression. The rind of the fruit is the reservoir of this Oil: it is contained in little vesicles, which may be seen by the naked eye, spread all over the surface of the peel, and which, bursting when the peel is squeezed, discharge the Oil in the form of very fine slender spouts. Every body knows, that these little oily streams instantly take fire, when spirted through the flame of a candle: the Oil in this case is entirely consumed.

The Essential Oil, thus obtained by expression, hath a very sweet and most agreeable scent. It is in every respect the same as when it made a part of the fruit that yielded it, seeing it hath not undergone the action of fire. Yet this method, however good it may be, can hardly be practised but in the countries where those fruits are in great plenty; because we cannot by this means obtain any thing near the quantity of Oil they contain.

This inconvenience may be remedied by rubbing the rind, which contains the Essential Oil, on the surface of a sugar-loaf. The inequalities of that surface produce the effects of a rasp, by tearing all the oily vesicles. The Oil, which issues in abundance, is imbibed by the sugar and moistens it. When the sugar is sufficiently impregnated therewith, it may be scraped off with a knife, and put into a well-stopped bottle. The sugar does not alter the nature of the Oil; which may be kept in this manner for years, and used, though combined with the sugar, for almost all the same purposes as when in a fluid state; that is, to aromatize the several matters with which you incline to mix it. We owe these observations to Mr. Geoffroy.

This experiment, in which the Essential Oil of a vegetable is obtained by expression alone, and without the aid of fire, proves that the Oils of this kind exist naturally in vegetables; and that the Oils of the same kind obtained by distillation, as shall be shewn in its place, are not the product of the fire. Essential Oils drawn by expression do not very sensibly differ from those procured by distillation.

CHAP. II.

_Of the_ SUBSTANCES _obtained from_ VEGETABLES _by_ TRITURATION.

PROCESS I.

_To make the Extract of a Plant by Trituration._

Bruise the vegetable substance of which you intend to make the Extract; or, if it be hard and dry, grind it to a powder: put the matter thus prepared, together with seven or eight times as much rain-water, into an earthen vessel; and into this vessel fit a churning staff, so that it may be continually whirled round with a rotatory motion, by means of a cord, a wheel, and a winch. Ply this machine for ten or twelve hours; and then filter the liquor through two linen cloths spread on a hair-sieve. Let your filtered liquor stand quiet for twelve hours more: then pour it off by inclination from the sediment you will find at bottom; and filter it a second time through a flannel bag.

Pour fresh water, but in a smaller quantity, on the mass left after trituration with the machine. Triturate it again for four or five hours. Treat the liquor of this second triture just as you did that of the first, and mix them both together. Distribute all the liquor you now have among a sufficient number of shallow earthen plates, and evaporate it by a gentle warmth, such as that of the sun, or of a vapour-bath, to the consistence of an Extract, or even to dryness, as you think proper.

_OBSERVATIONS._

In trituration the water takes up, not only the Salts of plants, but also a pretty considerable quantity of their oily and earthy parts, which those Salts have rendered soluble therein, by communicating to them a saponaceous and mucilaginous quality. After trituration, therefore, nothing remains but the grossest particles of oil and earth. Hence it is evident, that the water, in which plants have been triturated, contains nearly the same principles as the juices of those plants drawn by expression; and that it is also impregnated with their Essential Salts: so that, by evaporating it to a due consistence, we have a well made Extract of the triturated plant.

The Count de la Garaye, who hath long cultivated with great assiduity those parts of Chymistry by which Medicine may be improved, hath made a great number of experiments for obtaining from plants, by triture with water, the matters in which their virtues chiefly reside, and hath also published a work, entitled Hydraulic Chymistry, in which he gives a particular account of all the processes for making such Extracts of the chief mineral, vegetable, and animal substances, as are most frequently used in the Practice of Physic. His way of evaporating, by a gentle heat, the liquor containing the Extract of a triturated substance is a very good one: for we know that heat, if but a very little too strong, is capable of changing the natures of compound bodies, by disuniting their principles, and exhaling some of them.

If all vegetable matters were fat and succulent, as most pot-herbs are, triture would not be necessary for the making an Extract of them, even without the help of fire. We should have nothing to do, for that purpose, but to express their juices, as before, clarify them, and evaporate with a gentle heat to the consistence of an Extract. But many vegetable substances, such as woods, barks, roots, &c. are dry, hard, and compact. These matters will not give out their Extract, without such an application of water as shall dissolve their saline, saponaceous, and mucilaginous parts. Now this must be effected either by triture or by fire. Trituration has the advantage of procuring Extracts, in which the principles are perfectly unaltered, and retain the same proportions, with respect to each other, as in the plant: but then it is attended with the inconveniencies of being very tedious, troublesome, and chargeable. When we come to deliver the methods of making extracts by decoction and by infusion, we shall see what are the advantages and disadvantages of preparing Extracts by heat.

The matters, from which an extract is to be made by triture, must be previously bruised and reduced into small parts, in order to facilitate the action of water upon them. The several filtrations and decantations here directed are intended to separate the grosser parts of the plant, that were only suspended in the liquor, but not truly dissolved, by means of the agitation and motion: for this reason also, the longer the liquor is left to settle, the purer will the Extract be.

Though the plant be triturated the first time with a great deal of water, and for a good while too, yet it is not by that means wholly exhausted: M. de la Garaye therefore directs the remainder to be triturated again with fresh water: but this second operation requires only half the water used in the former, and need be continued only half the time; the plant having been already opened by the former triture, and having fewer parts to give out. It is better to add fresh water, and triturate a second time, than to triturate but once, and for a greater length of time: for when the water is impregnated with the principles of the plant to a certain degree, it is less capable of acting, and of dissolving more, than when it is pure.

As the water impregnated with the principles of the plant by triture must be almost wholly evaporated, in order to bring those principles nearer together, and that the whole may lie in the smallest compass possible; and, moreover, as this evaporation must be effected by the gentlest heat, it is necessary to spread the liquor so, by distributing it among a great number of plates, that it shall be reduced in a manner entirely to surface. By this means the Extract may be evaporated even to dryness; and this is M. de la Garaye's practice. As the Extracts, thus evaporated to dryness, cannot be taken up otherwise than in little scales, the lower surfaces whereof, by adhering to the glazing of the plate, are smooth and shining, they in some measure resemble a crystallized Salt; which led M. de la Garaye into an error, and induced him to give the title of Essential Salts to the Extracts prepared in this manner. The Essential Salt is indeed contained in them; but still they are only Extracts, as Mr. Geoffroy hath shewn, in a memoir on this subject given in by him to the Academy; since, besides the Essential Salt, they contain moreover, as was said before, a great deal of the oil and earth of the matters from which they were extracted. This, in the main, is no objection, but rather an advantage to them; considering that such saline Extracts are, on that account, so much the more like the substances from which they were obtained; especially with regard to their medicinal properties.

PROCESS II.

_To extract from Seeds and Kernels, by Trituration, the Matter of Emulsions._

Blanch the kernels of which you desire to make an Emulsion; put them into a marble mortar; add a very little water; and pound them with a wooden pestle. Continue pounding and triturating till the matter become like a white paste. From time to time pour on it, by little and little, more fair water warmed, still continuing the trituration; by which means the paste will grow thinner. Go on thus till every particle of your kernels be crushed to pap. Then add, still rubbing the mixture, enough of water to make the whole an actual fluid; and you will have a liquor of a dead-white colour, resembling milk. Strain it through a clean linen cloth; it will leave on the filter some coarse parts, which must be returned to those left in the mortar. Again triturate and rub the remainder of the kernels, with the addition of water as before. This second liquor will not be so white nor so rich as the former: filter it in the same manner, and again grind with water the solid parts remaining. In this manner proceed, repeatedly rubbing and adding fresh water, till it appear no longer milky, but come off clear. The white milky waters thus obtained go by the name of an _Emulsion_.

_OBSERVATIONS._

All the matters, from which a Fat Oil is obtainable by expression, produce Emulsions when triturated with water.

An Emulsion consists chiefly of two substances. One of these is mucilaginous, and soluble in water. This substance by itself would not give a milky appearance to the Emulsion, which, with it alone, would be limpid. The other is a Fat Oil, which of itself is not soluble in water; but being divided by the means of trituration into very small globules, it is dispersed through the whole liquor, and suspended therein by the aid of the mucilaginous part. It is this oily part that gives the Emulsion its dead-white, milky colour; because it is not actually dissolved in the water, but only diffused through it.

If Oil be mixed with water in a phial, and the mixture strongly shaken for some time, with a rapid and continued motion, the Oil will be divided into a vast number of little globules, which intervening between the parts of the water will destroy its transparency, and give it a dead-white colour, like that of our Emulsion. But, as the Oil is not so minutely divided by this means, as by triturating the matters containing it; and again, there being no mucilage in this liquor, as there is in Emulsions, the Oil soon separates from the water when it is left at rest, re-unites into round globules, and these joining together rise to the surface of the liquor, which then recovers its transparency.

The case is not exactly the same with Emulsions; but something like it happens to them also. If they be left to stand quiet in a long bottle, the liquor, which at first appeared homogeneous, separates into two manifestly different parts. The upper part retains its dead-white colour, but is thicker and more opaque; while the lower part becomes perfectly transparent. This is the beginning of an entire separation of the oily from the aqueous parts. The former, being the lighter, ascend and gain the upper part of the liquor; while the lower, being freed from that which obstructed its translucence, recovers its proper limpidity: but the oily parts do not re-unite into masses large enough to form one homogeneous whole, with the appearance and limpidness of Oil; their being minutely divided and entangled in the mucilage impeding their natural tendency.

Emulsions first begin to spoil, as they grow old, not by turning rancid and acrimonious like the Fat Oils drawn by expression, but by turning sour; which is owing to the great quantity of mucilage they contain. As there is a Fat Oil in their composition, they have the same virtues with that sort of Oil; but they are, moreover, incrassating, cooling, and emollient; qualities which render them extremely useful in acute and inflammatory disorders. They grow sour in a very short time, especially in the heat of summer; nay, they sometimes do so in two hours: and therefore they ought to be prepared from time to time as they are to be used.

The matter that is left when all the substance of the Emulsion is extracted, and from which the water comes off clear and limpid, is scarce any thing but the earthy part of the seed or kernel that was triturated; which, however, still retains a portion of tenacious and gross Oil, adhering to it so firmly as not to be separable by water.

The chyle and milk of animals resemble an Emulsion in several respects, and particularly in their dead-white colour; which arises, in the same manner, from the very minute particles of Oil contained in them, and distributed through an aqueous gelatinous fluid, but not dissolved therein. In general, whenever any Oil of any kind happens to be lodged in this manner between the parts of an aqueous liquor, it always makes the whole of an opaque white: for Oil will not mix with water, so as to produce a liquor that shall appear homogeneous and transparent, unless it be intimately dissolved in the water; which cannot be effected but by means of an union previously contracted between it and some saline matter: as is the case of mucilages, certain saponaceous matters, and some other combinations of which we shall have occasion to treat in the sequel.

The methods we have hitherto proposed, for extracting from vegetable substances all that they will yield without the assistance of fire, are not capable of analyzing those substances accurately, as you may have observed; since by expression and trituration we obtain only the liquid parts, impregnated indeed with almost all the principles of plants, which, however are still combined with each other, and barely separated from the grossest earthy and oily parts. We must therefore necessarily have recourse to a more effectual expedient for carrying our analysis further. This expedient consists in making them undergo the action of fire, successively graduated, from the gentlest to the most violent heat.

But, before we enter on this Analysis of Vegetables, it is proper to describe the different operations that may be performed on Oils, the only pure principle we have been able to obtain without the help of fire. As we shall have occasion, when we come to treat of the analysis of plants by fire, to say a great deal more concerning Essential Oils, we reserve till then what relates to the operations that may be performed on them; and confine ourselves here to the operations on Fat Oils.

CHAP. III.

_Of_ OPERATIONS _on_ FAT OILS.

PROCESS I.

_To attenuate Fat Oils, and change their Nature, by exposing them to the Action of Fire, and distilling them._

Mix thoroughly three or four pounds of any Fat Oil whatever, with twice its weight of lime flaked in the air. Put this mixture into a large earthen retort, leaving a third part of it empty. Set it in a reverberating furnace, and lute on a receiver. Heat the vessel with a very gentle fire. A little phlegm will rise first, and will soon be followed by an Oil that will fall in drops from the nose of the retort. Continue the distillation very slowly, till you perceive the Oil that comes over begin to be not quite so fluid as before, but rather a little thicker.

Then unlute your receiver, and put another in its place. Continue the distillation, increasing your fire by degrees. The Oil that comes over will grow thicker and thicker, its fluidity will decrease, and it will acquire a dark-brown colour, which at last will become blackish. The Oil will then be very thick. Push the operation till nothing more will come off, though the retort be red-hot. During the whole time this distillation lasts, there rises a good deal of water, in company with the Oil. Keep the second thick Oil by itself.

Mix the Oil that came over first, in this operation, with an equal part of fresh lime flaked in the air. Put the mixture into an earthen or glass retort, of a size so proportioned to the quantity, that a third part thereof may remain empty. Distil as before. The same phenomena will appear: a clear Oil will first come over, and be succeeded by one a little thicker. Then shift your receiver, and distil off all the rest of the Oil with an increased fire. The first Oil obtained by this second distillation will be clearer and thinner than that of the first distillation; and the second Oil will not be so thick, nor of so deep a colour as before.

Distil over again, in the same manner, the thin Oil of this second distillation, and go on thus repeatedly distilling, till the first clear oil come over with a degree of heat not exceeding that of boiling water. Then, instead of mixing your Oil with lime, put it with some water into a glass retort, or into a body with its head fitted on, and distil it, keeping the water just in a simmer. Your Oil will be more and more attenuated, and, after being thus distilled twice or thrice with water, will be so limpid, so thin, and so clear, that you will scarce be able to distinguish it from water itself.

_OBSERVATIONS._

Fat Oils, which are naturally mild, unctuous, inodorous, or have at most a scarce perceptible smell, resembling that of the fruit or kernel from which they were extracted, change their natures totally when exposed to the action of fire. If they be but heated so as to boil, they become acrid, lose much of their unctuosity, and acquire a very pungent odour. From several analogies, and by several experiments, recited in a Memoir on Oils which I read to the Academy, I shewed that these alterations of Fat Oils are produced by the fire's extricating an Acid in them, which before lay concealed and inactive. What I advanced on this subject may be seen in the Memoirs of the Academy for 1745, and in my Elements of the Theory of Chymistry. I shall take occasion to add something more, in my Observations on the following process, by which these Oils are combined with Acids. In this place I shall only examine what passes in the repeated distillations they are here made to undergo.

Fat Oils do not rise in distillation without a degree of heat greater than that of boiling water; and therefore they must be distilled in a sand-bath, or with a naked fire. We prefer the latter method, for reasons elsewhere assigned, and chiefly because the operator is more master of his fire; it being absolutely necessary, in this operation, that he have it in his power to suppress it in an instant, when he finds it too strong: for, in such a case, it will impetuously raise the thin Oil mixed with the thick; nay, the whole will be burnt, as it were, to a coal, if a degree of fire ever so little too strong be kept up but for a few moments. When this accident happens, it is always predicted by a great quantity of white vapours ascending with impetuosity out of the retort, and by drops of Oil following each other very fast, that are scarce limpid at first, and soon become of a dark colour. All this may be prevented by distilling very slowly, and with great patience.

Fat Oils may be distilled and attenuated without any additament: but then the operation, which is tedious and troublesome enough, even when lime is used, as appears from our description of the process, would be much more so if the Oil were distilled alone, without the addition of any thing to divide it, spread it, and enlarge its surface.

Lime is one of the best additaments that can be employed on this occasion; not only because it procures the advantages just mentioned, but also by reason that, being an absorbent of fat matters, it unites with the grosser parts of the Oil, retains them, and so allows the thinnest and lightest parts to be readily separated from the rest. By this means it greatly expedites the operation: and, the more of it is added, with respect to the oil, the sooner is a considerable quantity of thin limpid Oil obtained: and this is the reason of our directing a double quantity of lime to be mixed with the Oil in the first distillation.

Lime slaked in the air is employed preferably to quick-lime; because it is naturally divided into a very fine powder, and capable of mixing perfectly with all sorts of matters.

The water that first appears in the distillation comes from the lime: it is part of the humidity which the lime had imbibed from the air. This water continues to rise with the Oil during the whole distillation, according as the degree of heat is increased: and, if the distillation be finished by keeping the retort red-hot for some time after all is come over, the lime in it will have a greyish cast, and, when water is poured on it, grow almost as hot as quick-lime.

If you resolve to carry on these distillations of a Fat Oil, till it becomes as light as an Essential Oil, it is necessary to begin with a pretty large quantity thereof, as three or four pounds: for the quantity of the Oil is considerably lessened by every distillation; not only because the thickest and grossest part is separated from it every time; but also because a portion of the Oil remains so strongly united with the lime, that the force of fire is not able to separate them. Moreover, there is reason to believe that some of it is decomposed every time it is distilled.

If Oil be distilled by itself, the thickest and heaviest part remains charred, as it were, in the retort, the inside of which is lined with a crust of coal, that is to the last degree fixed: this therefore always occasions a diminution of the Oil.

A Fat Oil must be distilled eight or nine times, even with lime, before it become as light as an Essential Oil, and capable of rising wholly with the heat of boiling water: by that time therefore it must be considerably diminished; and if, at least, the quantity prescribed be not taken at first, there will scarce remain a few ounces capable of being distilled with water.

The portion of thick heavy Oil, obtained in the several distillations, may, if you will, be rectified again. For this purpose you must mix it with fresh lime, and distil it as you did the clear Oil. A portion of this also will be attenuated, and come over first. Thus all the Fat Oil may be subtilized by the action of fire; an absolutely charred black part excepted, that remains fixed, and appears susceptible of no change, but by burning it in the open air, and thereby reducing it to ashes, from which a little Fixed Alkali may be obtained. In this fixed part of the Oil the acid and earthy parts are combined therewith, in a greater proportion than they ought to be in pure Oil.

The portion of Oil that hath become light and thin is nothing but the purest oily part, separated from the gross acids, and from a certain quantity of earth, which made it thick and heavy. This Oil resembles the Essential Oils in lightness, fluidity, and a penetrating agreeable odour: it dissolves in Spirit of Wine. We shall have occasion in the sequel to enlarge further on the qualities of the several sorts of Oils, and their solubility in Spirit of Wine, when we come to treat of Ardent Spirits and of Æther.

PROCESS II.

_To combine Fat Oils with Acids. The Decomposition of this Combination._

Put any Fat Oil whatever into a glass bason, and set it in a sand-bath very moderately heated. Pour on this Oil an equal quantity of concentrated Oil of Vitriol, which will immediately dissolve it with violence; a considerable ebullition and effervescence will arise, attended with great heat, and a prodigious quantity of black, thick vapours, in which may be easily perceived the smell of burnt Oil, together with that of a Sulphureous Acid. The mixture will become of a deep-red, black, and thick. Stir it with a small stick, till you observe that all is quiet.

_OBSERVATIONS._

The Vitriolic and Nitrous Acids unite with Fat Oils, and dissolve them with violence; but these Acids must be sufficiently strong and concentrated, otherwise they will not act upon the Oils. The Vitriolic Acid, in particular, dissolves them pretty thoroughly. If hot water be poured on the mixture described in our process, this water will become cloudy and milky, by dissolving some of it: so that Oils may be rendered soluble in water by the means of Acids. Spirit of Wine, which doth not attack Fat Oils in their natural state, unites perfectly with them, and makes a clear limpid solution of them, when they are thus combined with Acids.

The Acids also suffer a considerable alteration by contracting an union with Oils. They become much milder, and lose almost all their strength. If the mixture described in the process be distilled, there will come over a great quantity of an empyreumatic acidulated phlegm, that smells strong of Sulphureous Spirit; an Oil thinner than the original saponaceous mixture; a weak Oily Acid, and a very thick, black Oil. If the fire be made very strong, when the Oil ceases to rise, it sometimes happens that a little Sulphur sublimes into the neck of the retort.

By this analysis it appears, that the strong concentrated Acid, which was an ingredient in the combination, is not now to be found. The Vitriolic Acid hath changed its nature, and is considerably weakened by the union it hath contracted with the principles of the Oil. The aqueous part of this latter substance weakens the other, and loads it with phlegm; the inflammable part thereof renders it sulphureous, and even converts it into Sulphur.

Hence it follows, that same part of the Oil is decomposed, by the union it contracts with the Vitriolic Acid; for its phlogiston and its aqueous principle cannot be disunited, so as to form a Sulphureous Spirit, or an actual Sulphur, and an aqueous Acid, without the decomposition of a certain quantity of the Oil, in proportion to the two disjoined principles. Another portion of the Oil remains united with the Vitriolic Acid, without suffering any decomposition, and communicates to that portion of the Acid, with which it is combined, a somewhat saponaceous quality, which makes it resemble the Vegetable Acids.

Thus we see, that when the Vitriolic Acid and a Fat Oil are combined together, they both suffer considerable changes; the Acid by the new alliances into which it enters, and the Oil by the decomposition it undergoes. In consequence hereof a much smaller quantity of Oil is obtained, by decompounding this combination, than was at first put in.

If the Oil abstracted by distillation be combined again with a fresh quantity of the concentrated Acid, the same effects will again follow; and by this means any quantity of Oil at pleasure may be entirely decomposed. This single experiment affords an evident proof of many important truths advanced in our Elements of the Theory.

Spirit of Nitre likewise dissolves expressed Oils. With Oil of Olives it forms a white paste, resembling a fine pomatum. This compound is perfectly soluble in Spirit of Wine. The Acid must be very strong and smoking to unite with this, or with any other Fat Oil: but it dissolves some of them with more rapidity than others; in which number is the Oil of Walnuts. It acts on these Oils with so much vehemence that it burns them, in some measure, making them black and thick.

PROCESS III.

_To combine Fat Oils with Fixed Alkalis. Hard and soft Soap. The Decomposition of Soap._

Take a lixivium of Alicant kelp made more caustic by lime, as we shall shew when we come to speak of Alkalis. Evaporate this lye till it be capable of bearing a new-laid egg. Divide it into two parts; and to one of these put just water enough to weaken it so, that a new-laid egg will not swim in it, but fall to the bottom. With the lye thus weakened mix an equal quantity of fresh-drawn Olive Oil. Stir and agitate the mixture well, till it become very white. Set it over a gentle fire, and continue stirring it incessantly, that the two ingredients of which it is compounded may gradually combine together, as part of the water evaporates. When you perceive they begin to unite, pour into the mixture thrice as much of the first strong lye as you took of Olive Oil. Continue the coction with a gentle fire, always stirring the matter, till it becomes so thick that a drop of it fixes, as it cools, into the consistence that Soap ought to have. By dissolving a little of this Soap in water, you will discover whether or no it contains more Oil than ought to be in the composition. If it dissolves therein wholly and perfectly, without the appearance of the least little drop of Oil floating on the water, it is a sign that it doth not contain too much Oil. If, on the contrary, you perceive any of these little globules, you must pour into the vessel, containing your matter, a little more of the strong lye, to absorb the redundant Oil. If there be too much of the Alkali it may be discovered by the taste. If the Soap leave on your tongue the sensation of an Alkaline Salt, and produce an urinous savour, it is a sign that there is too much Salt in proportion to the Oil. In this case a little Oil must be added to the mixture, to saturate the super-abundant Alkali. An excess in the quantity of Alkali discovers itself likewise by the Soap's growing moist in the air, on being exposed to it for some time.

_OBSERVATIONS._

Fixed Alkalis, even when resolved into a liquor, that is, when loaded with much water, unite easily with Fat Oils, as appears from the experiment just recited, and require but a moderate heat to perfect that union. This combination may even be completely effected without the aid of fire, and by the heat of the sun only, provided sufficient time be allowed for that purpose; as Mr. Geoffroy found upon trial. It only requires the mixture of the Oil and Alkali to be kept five or six days in digestion, and stirred from time to time. A lixivium of pure Alkali, not acuated by lime, may also be used to make Soap: but it is observed, that the combination succeeds better, and that the Alkali unites sooner and more perfectly with the Oil, when it is sharpened by lime.

The Oil is first mixed with a weaker and more aqueous lye, to the end that the combination may not take place too hastily, but that all the particles of the two substances to be compounded together may unite equally. But as soon as the Alkali begins to dissolve the Oil gradually and quietly, the dissolution may then be accelerated; and that is done by adding the remaining lye, which is stronger and less diluted than the other.

Soap made with Olive Oil is white, hard, and hath not a very disagreeable smell: but as that Oil is dear, others, even the fat and oils of animals, are sometimes substituted for it. The Soaps made with most of these other matters are neither so hard, nor so white, as that made of Olive Oil: they are called _Soft Soaps_.

Oils thus associated with Fixed Alkalis are by that means rendered soluble in water; because the Alkaline Salts, having a great affinity with water, communicate part thereof to the Oils with which they are now incorporated. Yet the Oil is not for all that rendered thoroughly miscible with water, or perfectly soluble therein; for the water in which Soap is dissolved hath always a milky cast: now there is no other criterion of a perfect solution but transparency.

Alkalis also lose part of their affinity with water, by the union they thus contract with Oils: for, when the combination is properly made, they no longer attract the moisture of the air, nor doth water dissolve them in such quantities as before. The composition of Soap is plainly a saturation of an Alkali with an Oil; and, in order to make perfect Soap, we are forced, as was said in the process, to grope, in a manner, by repeated trials, for this point of saturation; just as when we prepare a Neutral Salt by saturating an Alkali with an Acid. The union which the Oil contracts with the Alkali makes it lose, in part, the readiness with which it naturally takes fire; because the Salt is not inflammable: the water also, which enters in pretty considerable quantities into the composition of Soap, as we shall presently see, contributes a good deal to hinder the accension of the Oil.

Soap may be decompounded either by distilling it, or by mixing it with some substance that hath a greater affinity than Oil with Alkalis.

If we decompound it by distillation, a phlegm, or transparent spirit, of a somewhat yellowish colour, first comes over. This liquor is the aqueous part of the Soap, quickened by a little of its Alkali, which gives it an acrid taste. It is followed by a red Oil, which at first is pretty thin and limpid, but thickens as the distillation advances, grows black, and has a very disagreeable empyreumatic smell. This Oil is soluble in Spirit of Wine.

When the distillation is finished, that is, when the retort being kept red-hot for some time will discharge no more, there is left in it a saline mass; which is the Alkali of the Soap, crusted over with some of the most fixed parts of the Oil, that are charred to a coal. This Salt may be restored to the same degree of purity it had before its combination with the Oil, by calcining it in a crucible with a naked fire, that may consume this burnt part of the Oil, and reduce it to ashes.

It is plain that the Oil contained in Soap is affected by distillation, much in the same manner as that which we mixed with lime and distilled.

Mr. Geoffroy, by analysing Soap with care, discovered that two ounces thereof contain ninety-six grains of Salt of kelp, freed from all Oil and moisture; or two drams and forty-eight grains of that Salt, as it is used in manufacturing Soap; that is, containing water enough to make it crystallize; one ounce three drams twenty grains of Olive Oil; and about two drams four grains of water.

As Acids have a greater affinity than any other substance with Alkalis, they may be very effectually employed to decompound Soap.

If you propose to decompound Soap by means thereof, you must first dissolve it in a sufficient quantity of water. Mr. Geoffroy, who made this experiment likewise, dissolved two ounces thereof in about three gallons of warm water, and to the solution added Oil of Vitriol, which he let fall into it drop by drop. Every time a drop of Acid falls into it, a _coagulum_ is formed in the liquor. The vessel in which the solution is contained must then be shaken, that the Acid may equally attack all the Alkali diffused in it. When no new coagulation is produced by a drop of the Acid, it is a sign you have added enough. The liquor then begins to grow clear: and if another quart of water be added, in order to facilitate the separation of the oily particles, you will see them rise and unite together on the surface of the liquor.

This is a pure, clear, true Olive Oil, hath its taste, its smell, and, like it, is fluid in warm weather, and becomes fixed by cold. Yet it differs in some respects from that which never hath been united with an Alkali in order to form a Soap; for it burns more vividly and more rapidly, and is soluble in Spirit of Wine. We shall account for these differences when we come to treat of Ardent Spirits.

Not only the Vitriolic Acid, but all others, even those obtained from vegetables, are capable of decompounding Soap, and separating the Oil from the Alkali. In the liquor wherein Soap is thus decompounded is found a Neutral Salt, consisting of the Acid made use of, united with the Alkali of the Soap. If the Vitriolic Acid be used, you will have a Glauber's Salt; a quadrangular Nitre, if the Nitrous Acid be used; and so of the rest.

The facility with which Acids decompound Soap is the reason that no water, but what is very pure, will dissolve it, or is fit to be used in washing with it.

Water that doth not dissolve Soap well is usually called _Hard Water_. Such waters contain a certain quantity of saline matters, washed out of the earths through which they pass. The hardness of water is generally occasioned by selenitic particles.

The hardness of all the well-water in and about Paris is owing to a considerable quantity of Selenetic Gypsum with which the Soil abounds. The Selenites, we know, are Neutral Salts, consisting of the Vitriolic Acid united with an earthy basis. If therefore Soap be put into water in which a Salt of this kind is dissolved, it is evident that the Vitriolic Acid in the Selenites, having a greater affinity with the fixed Alkali of the Soap than with its own earthy basis, will quit the latter to unite with the former; and thus the Soap will be decompounded instead of being dissolved. Accordingly we see, that, when we attempt to dissolve Soap in our well-water, the surface of the liquor is in a short time covered with a fat oily pellicle. However, this decomposition of Soap is not complete; at least, but a small part of it is perfectly decompounded; because the great quantity of Selenites, with which the water is impregnated, hinders the Soap from mixing so thoroughly with it, as is requisite to produce a total decomposition thereof.

All mineral waters are likewise hard, with regard to Soap; for as most of them owe their virtues to the efflorescences they have washed off from pyrites, that have grown hot and begun to be decomposed, they are impregnated with the saline matters produced by pyrites in that state: that is, with aluminous, vitriolic, and sulphureous substances, which have the same effect on Soap as the Selenites have.

Mineral waters containing Neutral Salts only, such as Sea-salt, Epsom Salt, Glauber's Salt, are nevertheless hard with regard to Soap, though the Acids of those Salts, being united with Fixed Alkalis, are incapable of decompounding it. The reason is, that those Neutral Salts are more soluble in water than Soap is; so much indeed as even to exclude it: because each of the two principles that composed them hath a very great affinity with water; whereas only one of the principles of Soap, namely, its Alkali, hath that affinity; the other, to wit, the oily principle, having none at all. Thus water impregnated with an Acid, or with any Neutral Salt, is hard with regard to Soap, and incapable of dissolving it; and hence it follows, that Soap is a sort of touchstone for trying the purity of water.

Wine dissolves Soap; but imperfectly, because it contains an acid or tartarous part. Spirit of Wine also dissolves it: but neither is this dissolution perfect; because it contains too little water: for its spirituous part can dissolve nothing but the Oil of the Soap; and the Alkali is not at all, or at least in a very small quantity, soluble in this menstruum. The true solvent of Soap is therefore a liquor that is partly spirituous, partly aqueous, and not acid.

Brandy has these qualities: and accordingly it is the solvent that unites best with Soap, dissolves the greatest quantity, and makes the most limpid solution thereof. Yet even this solution hath something of a milky cast, occasioned by its not being entirely free from an Acid, or the tartarous principle. This fault may be easily corrected, by mixing with it a little Alkali to absorb the Acid. A dram of crystallized salt of kelp mixed with three ounces and a half of good brandy, renders it capable of dissolving an ounce and two drams of good hard Soap, into a perfectly limpid liquor. This experiment also we owe to Mr. Geoffroy.

Some years ago it was discovered that Soap might be used with great success in Medicine, and that it possesses the property of dissolving the stony concretions that form in several parts of the body, particularly in the kidneys and bladder. Soap is the basis of the composition known by the name of _Mrs. Stephen's Remedy_, and in this one ingredient its whole virtue resides.

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Elements of the Theory and Practice of Chymistry, 5th ed.Chapter LII: Section I: Operations on unfermented Vegetables (1)

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