We have shewn, that the production of the æthereal liquor is owing to a semi-decomposition of the Spirit of Wine effected by the Vitriolic Acid during the distillation; that this Acid continuing to act, produces a total decomposition, or perfect separation of the Oil and Phlegm of the Spirit of Wine from each other; and that the Vitriolic Acid, uniting with these two principles, forms the sulphureous phlegm, the fluid oil, and the bituminous matter, all frequently mentioned above. Why then, in this experiment of Mr. Hellot's, do we obtain only a Spirit of Wine replete with Æther, while none of the other productions appear? The reason is a very natural one, and very clear: it is this; the potter's clay containing an earth of that kind which we called Absorbent, because it possesses the property of uniting with Acids, that earth joins with the Vitriolic Acid in the mixture, reduces it to a Neutral Salt, and thereby prevents its continuing to act upon the Spirit of Wine, as is necessary to the total decomposition thereof.
Mr. Hellot says on this occasion, "that part of the Vitriolic Acid turning its action on this soluble earth or bole, which it finds in the potter's clay, ceases to act on the inflammable principle of the Spirit of Wine; that, consequently, as there is not an immediate and continuous combination of these two substances, neither a resin nor a bitumen can result therefrom. This is so true, that a great part of the Oil of Vitriol may be afterwards recovered from the potter's clay as colourless as when it was first used."
Mr. Hellot makes use of the following method for procuring the Æther from the acid vinous Spirit obtained by this distillation. "You must," says he, "put all this liquor into a glass body, made of one piece with its head; pour upon it, through the hole in the upper part of the head, twice or thrice as much well-water, the hardest to the taste, and the most impregnated with gypsum, that can be got. Very pure water, he observes, produces much less Æther.
"If the vinous acid Spirit have such a sulphureous smell, as to occasion a suspicion that it contains a little too much of a Volatile Vitriolic Acid, you must add to the water two or three drams of Salt of potash to absorb that Acid; and then distil with a lamp-heat.
"While any true Æther remains in the mixture, you will see it ascend like a white pillar issuing from the midst of the liquor, and consisting of an infinite number of air bubbles inexpressibly small. Nothing seems to condense in the cavity of the head, which always remains clear, and without any visible humidity. The gutts which light on the sides of the receiver, instead of forming a net-work thereon, as Spirit of Wine doth when it is a little aqueous, spread to the breadth of two inches or more, when they consist of true Æther. As soon as you perceive this track begin to grow considerably narrower, the fire must be put out; for what rises afterwards will be mixed with water, and communicate that fault to the Æther already collected in the receiver.
"Then pour this ætherial liquor into a long bottle, and add to it an equal quantity of well-water. Shake the bottle; the liquor will become milky, and the true Æther will instantly separate, float upon the water, and mix no more with it. Separate it then by a siphon, and keep it in a glass bottle shut close with a glass stopple."
Spirit of Wine combined with Spirit of Nitre. Sweet Spirit of Nitre.
Into an English retort of crystal glass put some highly rectified Spirit of Wine; and, by means of a glass funnel with a long pipe, let fall into your Spirit of Wine a few drops of the Smoking Spirit of Nitre. There will arise in the retort an effervescence attended with heat, red vapours, and a hissing noise like that of a live coal quenched in water. Shake the vessel a little, that the liquors may mix thoroughly, and that the heat may be equally communicated to the whole. Then add more Spirit of Nitre, but in a very small quantity, and with the same precautions as before. Continue thus adding Spirit of Nitre, by little and little at a time, till you have put into the retort a quantity equal to a third part of your Spirit of Wine. Let this mixture stand quiet, in a cool place, for ten or twelve hours; then set it to digest in a very gentle warmth for eight or ten days, having first luted on a receiver to the retort.
During this time a small quantity of liquor will come over into the receiver, which must be poured into the retort. Then distil with a somewhat stronger degree of heat, but still very gently, till nothing be left in the retort but a thick matter. In the receiver you will find a spirituous liquor, of a quick grateful smell, which will excite a very smart sensation on the tongue, but without any corrosive acrimony. This is The Sweet Spirit of Nitre.
OBSERVATIONS.
By this operation Spirit of Nitre is combined with Spirit of Wine; these two liquors being united with each other, much in the same manner as the Vitriolic Acid is with Spirit of Wine in Rabel's Water.
The proportion of the liquors which form this combination is not absolutely determined, and the several authors who have written on the subject differ much about it. Some require equal parts of the ingredients; others again from two as far as ten parts of Spirit of Wine to one of Spirit of Nitre. This depends on the degree to which the Spirit of Nitre made use of is concentrated, and on the greater or less acidity which your dulcified Spirit of Nitre is intended to have.
The Dispensatory of the College of Paris orders one part of Spirit of Nitre distilled from dried clay, that is, of Spirit which doth not smoke, to be mixed with two parts of rectified Spirit of Wine, and the whole to stand in digestion for a month, without distilling the mixture at all. This is a very good method: because the long digestion supplies the place of distillation, and the Spirit of Nitre, not being highly concentrated, doth not greatly alter the Spirit of Wine; besides that many inconveniences, to be presently taken notice of, are by this means avoided.
But as our design is not to describe such Chymical preparations only as are commonly used in medicine, our plan requiring us to treat particularly of those which may give any light into the fundamental properties of bodies, the process here set down appeared the fittest for our purpose; because the action which Spirit of Nitre exerts upon Spirit of Wine is therein stronger and more perceptible.
One of the first particularities attending the mixture of those two liquors, is the great effervescence, accompanied with violent heat, abundance of fumes, and loud hissing, which arises as soon as the Spirit of Nitre and the Spirit of Wine come into contact with each other. There is great reason to think, that these phenomena are produced only by the rapidity and vigour with which the Nitrous Acid rushes into union with the inflammable part of the Spirit of Wine. We observed, in treating of the Æther, that phenomena of the same kind appear at the instant when the Vitriolic Acid unites with Spirit of Wine: but on that occasion, how highly soever the Vitriolic Acid be concentrated, all these effects are in a less degree than those produced in the present experiment; because the Nitrous Acid, though weaker than the Vitriolic, generally acts much more vigorously and violently on the bodies with which it unites, than any other sort of Acid.
Concerning these mixtures of Acids with Spirit of Wine, Mr. Pott observes, that it is not a matter of indifference whether you pour the Spirit of Wine upon the Acid, or the Acid on the Spirit of Wine; but that every thing passes much more quietly, when the Acid is poured to the Spirit of Wine, than when the contrary is done: and he gives the true reason thereof; to wit, that when the Acid is poured on the Spirit of Wine it finds in that liquor a great quantity of water, with which it immediately unites; that this weakens it, and hinders it from acting on the inflammable part with so much impetuosity as it otherwise would; and therefore he advises that such mixtures be always made in this manner. But it is evident that this advantage is gained only by mixing the Acid with the Spirit of Wine very gradually, and drop by drop, as directed in the process after Mr. Pott. For, if the two liquors were to be mixed together suddenly, and all at once, it is certain that the Acid would not meet with a single drop of phlegm more or less in that way than in the other.
Therefore the chief, and, in some measure, the only precaution necessary to be taken, in the making of such mixtures, to prevent the violent effervescence and other inconveniences that may attend it, such as explosion, and the bursting of the vessels, is to pour but a very small quantity of one liquor into the other at a time, and to add no more till the effervescence, and even the heat, produced by the first portion, be entirely ceased. With these precautions you may proceed either way, and be always sure that the vessels will not burst; because it is in your power to add such a small quantity of liquor at a time, as shall scarce produce a sensible effervescence. We own, however, that Mr. Pott's observation is a very just one. There is even an advantage in pouring the Acid to the Spirit of Wine, as he directs; which is, that the mixture is a little sooner made, and without any danger.
We have shewn, that the Vitriolic Acid becomes aqueous and sulphureous by mixing Spirit of Wine with it: the Nitrous Acid is changed by this mixture in a manner no less remarkable. Mr. Pott observes, that when Spirit of Nitre is dulcified, that is, when it is perfectly combined with Spirit of Wine, it loses the disagreeable odour peculiar to it, and acquires another that is quick and fragrant; it doth not afterwards emit any red fumes; it rises with a less degree of heat than when pure; it acts with less vigour on Fixed Alkalis and Absorbent earths. Lastly, we shall here relate an experiment made by that Chymist, which seems to prove that the Nitrous Acid loses its most characteristic properties, and entirely changes its nature, by being combined with Spirit of Wine.
Mr. Pott examined the thick liquor left in the retort, when the dulcified Spirit of Nitre is distilled off. By analyzing it he obtained an acid liquor, of a yellow colour, and of a somewhat empyreumatic smell. This Acid was followed by some drops of a red empyreumatic Oil; and there remained, at the bottom of the distilling vessel, a black, shining, charred matter, like that which remains after the rectification of a fetid Oil.
The Oil extracted from this residue is a portion of that which helped to constitute the Spirit of Wine; being separated therefrom by the Nitrous Acid, in the same manner as that treated of in the preceding process, and called Sweet Oil of Vitriol, is separated by the Vitriolic Acid. But as the Nitrous Acid, which is weaker than the Vitriolic, doth not so effectually decompose the Spirit of Wine, the Oil, obtained in the present experiment, is in smaller quantity than that procured in the distillation of a mixture of the Vitriolic Acid with Spirit of Wine.
As to the Acid which Mr. Pott drew off in his experiment, there is great reason to think it a part of that which was an ingredient in the mixture; namely, of the Nitrous Acid. And yet Mr. Pott having saturated with a Fixed Alkali one part of the residuum, which he had a mind to examine before the Acid was separated from it by distillation, and expecting this matter to contain a regenerated Nitre, he threw it on a live coal; but was surprised to see it burn without the least sign of detonation; and thence concluded, that the Nitrous Acid had changed its nature. This experiment, he thinks, may furnish hints for the transmutation of Acids; and he is of opinion, that the Nitrous Acid loses its virtue of detonating, in the present case, only because its inflammable part, to which it owes its distinguishing properties, hath deserted it, and joined with that of the Spirit of Wine.
Indeed if the Acid obtained by Mr. Pott, which being reduced to a Neutral Salt doth not detonate, derives its origin from the Nitrous Acid that was combined with the Spirit of Wine, there is no doubt of its being depraved in a peculiar manner, and having entirely changed its nature. But may we not suppose it to have another origin? May it not be the Acid of the Spirit of Wine itself, resulting from the decomposition of that mixt in the distillation?
Mr. Navier, whom we mentioned in our Elements of the Theory, extracted a very singular oily liquor from the mixture of Spirit of Wine and Spirit of Nitre, without distillation, and even without the help of fire. He put equal parts of the two liquors, by measure, not by weight, into a bottle, which he stopped close with a good cork, fastened down with pack-thread. Nine days afterwards he found about a sixth part of the mixture separated from, and floating on, the rest of the liquor. This was a very fine æthereal Oil, very limpid, and almost as colourless as water.
In another experiment Mr. Navier substituted a solution of Iron in the Nitrous Acid for pure Spirit of Nitre; and with this solution he mixed an equal weight of Spirit of Wine. From the mixture, after a fermentation which appeared in it, he obtained by the same method an æthereal Oil, like that of his former experiment; except that the latter, which was at first as colourless as the other, acquired a redness in the space of about three weeks. He conjectures, with probability, that this colour proceeded from some particles of Iron which were united with it, and which gradually exhaled.
If a few drops of Oil of Tartar per deliquium be poured on this Oil, as soon as it is separated, there appears at first no sensible change therein: but after some time needle-like crystals shoot in it, which are a true regenerated Nitre; and if the bottle be then unstopped, the liquor emits a most pungent nitro-sulphureous odour; which leaves no doubt of this Oil's containing a Nitrous Acid. When it is thus freed of its Acid, by means of the Oil of Tartar, it is much more volatile than before.
Neither the Vitriolic nor the Marine Acid is capable of separating such an Oil from Spirit of Wine: but the Nitrous Acid always produces it, even when it is not concentrated, and doth not smoke.
It is very certain that this Oil derives its origin from the Spirit of Wine: but there are not yet experiments enough made upon it, to enable us to speak very accurately about the manner in which this liquor is formed, or of the cause of its separation from the Spirit of Wine.
Spirit of Wine combined with the Acid of Sea-salt. Dulcified Spirit of Salt.
Mix together, little by little, in a glass retort, two parts of Spirit of Wine with one part of Spirit of Salt. Set this mixture to digest for a month in a gentle heat, and distil it, till nothing remain in the retort but a thick matter.
OBSERVATIONS.
The Acid of Sea-salt is much less disposed to unite with inflammable matters than the other two mineral Acids; and therefore, though it be ever so highly concentrated, when mixed with Spirit of Wine, it never produces an effervescence comparable to that which is produced by the Spirit of Nitre. Neither the proportion nor strength of the Spirit of Salt, requisite to prepare the Sweet Spirit of Salt, are unanimously agreed upon by Authors. Some direct equal parts of the two liquors; while others prescribe from two to four or five parts of Spirit of Wine to one part of Spirit of Salt. Some use only common Spirit of Salt; others require the Smoking Spirit, distilled by means of Spirit of Vitriol. Lastly, some order the mixture to be distilled, after some days digestion; and others content themselves with barely digesting it. The whole depends on the degree of strength which the Sweet Spirit of Salt is intended to have. This composition, as well as the Sweet Spirit of Nitre, is esteemed in medicine to be very aperitive and diuretic.
When the mixture of Spirit of Salt and Spirit of Wine is distilled, there comes over but one liquor, which appears homogeneous. This is the Sweet Spirit of Salt. The nature of the Marine Acid is not changed in this combination: the Acid is only weakened and rendered more mild; but in other respects it retains its characteristic properties.
Some authors pretend, that an Oil is obtained by distilling the mixture for the Sweet Spirit of Salt; but others expressly deny the fact. This variety may be occasioned by the quality of the Spirit of Wine employed. It would not be surprising if a Spirit of Wine, which contains much Oil that is unnecessary to its nature, and, as it were, adventitious to it, should yield an Oil when distilled with Spirit of Salt.
The thick residue, found in the retort after distillation, contains the most ponderous part of the Acid, united with part of the Spirit of Wine. If the distillation be continued to dryness, there remains in the retort a black charred matter, much like that which is left by the combinations of Spirit of Wine with the other Acids.
A sweet Spirit of Salt may also be prepared by digesting Spirit of Wine with, or distilling it from, metallic compositions replete with the Marine Acid adhering but slightly to them; such as Corrosive Sublimate, and Butter of Antimony. Part of this Acid, which is very highly concentrated, quits the metallic substance with which it is but superficially combined, in order to unite with the Spirit of Wine. If Butter of Antimony be used for this purpose, Mr. Pott, the author of these experiments, observes, that a Mercurius Vitæ precipitates; which is nothing else, as we observed in its place, but the reguline part of the Butter of Antimony deserted by its Acid.
Oils, or Oily Matters, that are soluble in Spirit of Wine, separated from Vegetables, and dissolved by means of that Menstruum. Tinctures; Elixirs; Varnishes. Aromatic Strong Waters.
Put into a matrass the substances from which you intend to extract a Tincture, having first pounded them, or pulverized them if they are capable of it. Pour upon them Spirit of Wine to the depth of three fingers breadth. Cover the matrass with a piece of wet bladder, and tye it on with pack-thread. Make a little hole in this bit of bladder with a pin, leaving it in the hole to keep it stopped. Set the matrass in a sand-bath very gently heated. If the Spirit of Wine dissolve any part of the body, it will accordingly acquire a deeper or lighter colour. Continue the digestion till you perceive that the Spirit of Wine gains no more colour. From time to time pull out the pin, to give vent to the vapours, or rarefied air, which might otherwise burst the matrass. Decant your Spirit of Wine, and keep it in a bottle well corked. Pour on some fresh Spirit in its stead; digest as before; and go on in this manner, pouring on and off fresh Spirit of Wine, till the last come off colourless.
OBSERVATIONS.
It is commonly said, that Spirit of Wine is the solvent of Oils and oily matters: but this proposition is too general; for there are several sorts of Oils and oily matters which this menstruum will not dissolve. Of this number are the Fat Oils, Bees-Wax, and the other Oily compounds of that kind. Properly speaking, it dissolves but two sorts of oily substances; namely, Essential Oils, and Balsams or Resins, which are matters of the same kind, differing from each other only as they are more or less thick; and Oils that are in a saponaceous state.
In our Elements of the Theory we have explained our opinion on this head, from a Memoir on the subject printed among those of the Academy for 1745. To repeat it in a few words: we take the cause of the solubility of Oils in Spirit of Wine to be an Acid, which is but superficially united with them, and so as still to retain its properties.
The principal proofs on which we found this opinion are drawn from that property of Essential Oils, Balsams, and Resins, which are naturally soluble in Spirit of Wine, that they become so much the less soluble in this menstruum, the oftener they are distilled or rectified; and from that property which Fat Oils, or other Oily matters, naturally indissoluble in Spirit of Wine, possess, of becoming more and more soluble therein the oftener they are distilled. We shewed that distillation lessens the solubility of Essential Oils, Balsams, and Resins, only by depriving these substances of part of the manifest Acid which they contain, and which is the cause of their solubility; and that Fat Oils, and other oily matters, naturally indissolvable in Spirit of Wine, are by the same operation rendered capable of dissolving therein, only because it discovers, and partly extricates, an Acid, which is naturally combined with them so intimately that it is entirely deprived of action, and all its properties perfectly masked. If these principles be well attended to, and if it be recollected withal, that Spirit of Wine unites with Water preferably to Oils; insomuch that, if it be mixed with water when it hath dissolved an Oil, it quits the Oil to unite with the Water; that for the same reason it is not capable, when very aqueous, of dissolving any Oil, seeing that, as Oil and water are not susceptible of contracting any union, it must then desert its phlegm to unite with the Oil; which it cannot do, because it hath a greater affinity with phlegm than with Oil; and, lastly, that if Oil be combined with any saline substance, which makes it soluble in water; that is, if it be in a saponaceous state, it will then remain dissolved in Spirit of Wine, without being precipitated by water; or will be dissolved by a very aqueous Spirit of Wine, and frequently much better than by a highly rectified Spirit: if these things, I say, be considered, we shall easily perceive what must be the effect of digesting Spirit of Wine with any vegetable substance whatever.
Spirit of Wine dissolves all the Essential Oil, Balsam, and Resin contained in any vegetable; and as these matters are not soluble in water, they may be separated from the Spirit in which they are dissolved, by lowering it with much water. It instantly becomes white and opaque, like milk; the oily parts gradually unite, and form considerable masses, especially if they be resinous. This is the method commonly made use of to extract the Resin of Scammony, Jalap, Guaiacum, and several other vegetable substances, which it would be difficult to procure by any other means.
If the matters digested with Spirit of Wine contain any saponaceous juices, the Spirit will take up those juices also. But as soaps are soluble in water, as well as in Spirit of Wine, they cannot be separated, by the addition of water, from the Spirit in which they are dissolved. Whatever quantity of water therefore you mix with a Spirit that is impregnated with such juices, no separation thereof will be produced; and for the same reason the saponaceous matters will be dissolved by a very aqueous Spirit of Wine.
Spirit of Wine impregnated with such parts of any vegetable substance, as it is capable of dissolving, is commonly called a Tincture. Several Tinctures mixed together, or a Tincture drawn from sundry vegetable substances at the same time, and in the same vessel, take the name of an Elixir. Tinctures or Elixirs impregnated with Resinous matters only are true Varnishes. All these preparations are made in the same manner; to wit, as directed in our process. We shall only add here, that if the substances from which a Tincture or Elixir is to be made contain too much moisture, it is proper to free them from it by a gentle desiccation; especially if you design that the Tincture should be well impregnated with the oily and resinous parts: for their excess of moisture uniting with the Spirit of Wine would weaken it, and render it unable to act on those matters, which it cannot dissolve when it is aqueous.
Vegetable substances which have been repeatedly digested with different parcels of Spirit of Wine, till the last would extract nothing, are deemed to be exhausted of all their Essential Oils, and saponaceous juices: but if they contain moreover any Fat Oil, Wax, or Gum, these principles will still remain therein after the digestion, in the same quantity as before; because Spirit of Wine is incapable of dissolving them.
With regard to the Fat Oil and Wax, this is not at all surprising: we have explained in another place why these matters are indissoluble by Ardent Spirits: but as for the Gum, it would seem, according to the general principles above-mentioned, that it should be soluble in that menstruum, even with more ease than Resins; as it consists almost entirely of water, with which Spirit of Wine is known to unite more easily than with Oils. Indeed there is also a little Oil in its composition: but this Oil seems to be in a perfectly saponaceous state; for Gum dissolves wholly and easily in water, without lessening its transparency in the least.
I own that it is extremely difficult to give a very satisfactory account of this matter. We may however venture to throw out some conjectures concerning it, deduced from what hath been already said, relating to the cause of the solubility of Oils in Spirit of Wine. We shewed that the Oils which dissolve in this menstruum derive that property from a manifest Acid, which is united with them but superficially, and in such a manner as to retain all its virtue; but that if this same Acid be too intimately united with the Oil, so as to have no manifest power, but be in a manner destroyed, and converted as it were into a Neutral Salt, it will not then produce this effect.
A modern author[13] relates two experiments which agree very well with this opinion, and indeed confirm it. He mixed together Oil of Vitriol and Oil of Turpentine, with a view to imitate by art a bituminous matter; which, we know, is not at all, or at least scarcely, soluble in water. These two matters being united together produced a red, thick compound, which by evaporation became like a natural Bitumen.
The author observes, that when this mixture is just made it dissolves in Alcohol; but that in some time it changes its nature, and communicates scarce any part of its substance to that solvent. Now whence can such a difference arise, but from this, that when the mixture is new, the Acid is as yet but superficially united with the Oil, and combines with it more and more intimately, as the mixture grows older.
The same author, having repeated the experiment with Spirit of Vitriol, obtained a compound which continued always very soluble in Spirit of Wine: because Spirit of Vitriol being much weaker and more aqueous than Oil of Vitriol, was incapable of combining so closely with the Oil of Turpentine, as that concentrated Acid did in the former experiment. By the by, there is great reason to believe that the very intimate union of a mineral Acid with an oily matter is the true cause why Bitumens will not dissolve in Spirit of Wine.
It seems therefore pretty probable, that the Acid which makes the Oil of Gummy matters soluble in water, and reduces it to a saponaceous state, is so intimately united with that Oil, that it loses its properties, and is in a manner converted into a Neutral Salt. Now we know that such Salts are soluble in water, but are not so, for the most part, in Spirit of Wine.
If your Tinctures or Elixirs be not so strong or so saturated as you desire, you may by distillation abstract part of the Spirit of Wine which they contain, and by that means give them such a degree of thickness as you judge proper. But the Spirit of Wine thus drawn off constantly carries along with it a good deal of the aromatic principle. It is a truly Aromatic Strong Water. This Spirit of Wine also carries up with it a portion of thin Oil, which is so much the more considerable as the degree of heat employed is greater: and this is the reason why it becomes of a milky colour when mixed with water.
If you intend to make an Aromatic Strong Water only, you need not previously extract a Tincture from the vegetable substance with which you mean to prepare your water: you need only put it in a cucurbit, pour Spirit of Wine upon it, and distil with a gentle heat. By this means you will obtain a Spirit of Wine impregnated with all the odour of the plant.
Of Tartar.
Tartar analyzed by distillation. The Spirit, Oil, and Alkaline Salt of Tartar.
Into a stone retort, or a glass one coated with lute, put some white Tartar broken into small bits, observing that one half, or at least a full third, of the vessel be left empty. Set your retort in a reverberating furnace. Fit on a large ballon, having a small hole drilled in it; lute it exactly with fat lute, and secure the joint with a linen cloth smeared with lute made of quick-lime and the white of an egg. Apply at first an exceeding gentle heat, which will raise a limpid, sourish, pungent water, having but little smell, and a bitterish taste.
When this first phlegm ceases to come off, increase your fire a little, and make the degree of heat nearly equal to that of boiling water. A thin limpid Oil will rise, accompanied with white vapours, and with a prodigious quantity of air, which will issue out with such impetuosity, that if you do not open the little hole in the receiver time enough to give it vent, it will burst the vessels with explosion. An acid liquor will rise at the same time. Continue the distillation, increasing the heat by insensible degrees, and frequently unstopping the little hole of the receiver, till the elastic vapours cease to issue, and the oil to distil.
Then raise your fire more boldly. The acid Spirit will continue to rise, and will be accompanied with a black, fetid, empyreumatic, ponderous, and very thick Oil. Urge the fire to the utmost extremity, so that the retort may be of a perfect red heat. This violent fire will raise a little Volatile Alkali, besides a portion of Oil as thick as pitch. When the distillation is finished, you will find in the retort a black, saline, charred matter, which grows hot when wetted, attracts the moisture of the air, runs per deliquium, and hath all the properties of a Fixed Alkali.
This mass, being exposed to a naked fire in the open air, burns, consumes, and is reduced to a white ash, which is a fiery, caustic, Fixed Alkali.
OBSERVATIONS.
The matters qualified to produce a spirituous liquor by fermentation, do not all contain the just and accurate proportion of Acid necessary to constitute an Ardent Spirit. Many of them, the juices of fruits for instance, and especially that of the Grape, are replete with a super-abundant quantity of Acid, more than concurs to form that product of fermentation. This super-abundant Acid, combined with some of the Oil and earth contained in the fermented liquor, produces a sort of Salt, which hangs for a while suspended in that liquor, but after some time, when the Wine stands quiet in a cool place, separates from it, and forms a stone-like incrustation on the inside of the vat in which the Wine is kept. This matter is called Tartar.
The Lees of Wine resemble Tartar, in as much as they contain, and yield when analyzed, the same principles; but they differ from it in this, that they contain, moreover, a greater quantity of earth, of phlegm, and a little Ardent Spirit, which are only mixed, but not united, with the tartarous Acid.
The residue, or sort of extract, which remains in the cucurbit after Wine hath been deprived of its Ardent Spirit by distillation, hath also a great conformity with Tartar. It even contains that portion of Tartar which remained suspended in the Wine at the time of its distillation: and accordingly this residue of Wine, being analyzed, yields the same principles with Tartar.
Hence we see, that liquors, which have undergone the spirituous fermentation, consist of an Ardent Spirit and a Tartarous Acid suspended in a certain quantity of Water.
In the analysis of Tartar there are several things worthy of notice. The first is, the vast quantity of Air that this mixt body yields when it begins to be decomposed. The chief difficulty attending its analysis arises from this air; which issues out and exerts its elastic force with such impetuosity, that all the precautions above-mentioned are no more than necessary to prevent the bursting of the vessels.
The singular nature of the thin limpid Oil, which rises with this air, after the first acid phlegm, deserves likewise our particular attention. This Oil is one of the most penetrating we know. Boerhaave, who distilled Tartar without having a vent-hole in his receiver, was obliged, in order to prevent its bursting, to apply it to his retort with a lute so weak that most of the elastic vapours might perspire through it; and he observed, that, though the neck of his retort entered above five inches into the mouth of his receiver, and was luted on as closely as possible with such a lute, yet this light Oil of Tartar constantly returned back again, as it were, and pervaded the substance of the lute, so that a good deal of it dropped in a dish placed on the outside on purpose to receive it. This Oil is probably rendered so active and subtile, only by having been exceedingly attenuated by the fermenting motion. This experiment is one of those which sufficiently prove the necessity of employing receivers having a small vent-hole, that may be opened and shut as occasion requires.
The last remark we shall make, on the productions of Tartar by distillation, relates to the caput mortuum found in the retort when the operation is finished. This residue is very different from that which other vegetable matters afford: for, when they are decomposed in close vessels, they leave nothing but a mere charred matter, in which no saline property appears, and from which no Fixed Alkali can be obtained, but by carrying their analysis to the utmost; that is, by burning them in the open air. Tartar, on the contrary, only by being distilled in close vessels, without burning it afterwards in the open air, is changed into a substance which hath all the properties of a Fixed Alkali. This is probably owing to the Tartar's containing the principles requisite to form a Fixed Alkali in a much greater quantity than they are to be found in any other substance. As Tartar thus alkalizated in close vessels still contains much inflammable matter, it might be employed with advantage as a reducing flux, in several operations of metallurgy.
Of all the vegetable matters we know, calcined Tartar yields the greatest quantity of Fixed Alkali; which is likewise very pure, and therefore much used in Chymistry.
Burnt Lees of Wine also afford a great quantity of Fixed Alkali, which is of the same nature with that of Tartar. This Salt is used in different trades, and particularly in Dying. The French Vinegar-makers collect quantities of these Lees, which they make up into cakes and dry: while it is in this state they call it Gravelle or Gravelée; and Cendre Gravelée when it is burnt.
If the extract of Wine, which remains after the Spirit is drawn off, be gently evaporated to dryness, and that dry matter burnt like Tartar or Gravelle, it will make a sort of Cendre Gravelée very rich in alkaline Salt.
The Depuration of Tartar. Cream and Crystals of Tartar.
Reduce to a fine powder the Tartar you intend to purify, and boil it in twenty-five or thirty times as much water. Filter the boiling liquor through a flannel-bag, and then gently evaporate some part of it: there will soon form on its surface a saline crust, which is the Cream of Tartar. Let your liquor cool, and there will adhere to the sides of the vessel a great quantity of a crystallized saline matter, which is Crystal of Tartar.
OBSERVATIONS.
Tartar, when taken out of the vats in which it forms, is mixed with a considerable quantity of earthy parts, which are not intimately united therewith, but adulterate it. This extraneous earth makes about two fifths of the whole weight of common Tartar; but white Tartar, which is the best, contains but about a third part of earth.
The method of refining Tartar, and freeing it from this adventitious earth, is very simple, as appears from the process. Earthy matters, which are not intimately combined with an Acid in the form of a Neutral Salt, are not dissoluble in water: for which reason the water, in which crude Tartar is boiled, dissolves the saline part only, which passes with it through the filter; but doth not dissolve the earth of the Tartar, because that earth is not combined with the saline part, and so being only suspended in the liquor remains on the filter.
The saline parts of the Tartar, though they are now separated from the gross earth with which they were mixed, are not yet perfectly pure. These first Crystals of Tartar have a disagreeable russet colour, and are not transparent: this is owing to their being coated over, as it were, with a fatty matter, which also is foreign to their nature, and may be separated from them without decomposing them in the least.
The crystals of Tartar are but seldom perfectly depurated in Chymical Laboratories; because the operation doth not usually succeed well on small quantities: but there are manufactories which do it by the great, and supply the Chymists, as well as the several tradesmen, with very fine and very pure Crystals of Tartar. These manufactories are chiefly set up in the neighbourhood of Montpelier. Mr. Fifes, a celebrated Professor of Medicine, hath in the Memoirs of the Academy for 1725 described the operation as performed in one of these works. He tells us, that having separated the earthy part from the Crystals of Tartar, by boiling and filtering, they dissolve them again, and boil them in large caldrons, mixed with a white saponaceous earth, which cleanses and whitens them to perfection.
The saponaceous earth is found near the works; but it is not the only one that may be employed for this purpose; since, as Mr. Fifes observed, they have successively made use of several different earths in that very work, and that the earth they now use hath not been long employed. There is reason to think that most saponaceous earths might answer the purpose of refining Crystal of Tartar: but one necessary condition is, that they be altogether indissoluble by Crystal of Tartar, which being acid dissolves many sorts of earth; for, if they have not this quality, they will form a Neutral Salt with the saline part of the Tartar, the nature of which they will entirely change, and convert it into soluble Tartar, as will appear by the experiments that follow.
Crystal of Tartar combined with several Substances.
Crystal of Tartar combined with Absorbent Earths. Soluble Tartars.
Boil an Absorbent Earth, such as Chalk, in a pan with water; and, when you perceive the Earth thoroughly divided, and equally distributed through the water, throw into a pan, from time to time, some pulverized Crystal of Tartar, which will excite a considerable effervescence. Continue those projections, till you observe no effervescence excited thereby. All the Absorbent Earth, which obscured the transparency of the water, and gave it an opaque white colour, will gradually disappear as the Crystal of Tartar combines with it; and when the combination is perfected, the liquor will be clear and limpid. Then filter it, and there will be left on the filter but a very small quantity of earth. Evaporate all the filtered liquor with a gentle heat; and then set it in a cool place to shoot. Crystals will form therein, having the figure of flat quadrangular prisms, with almost always one, sometimes two, of the angles of the prism shaved down, as it were; and then the surfaces at each end are oblique, answering to those depressed angles. These crystals are a Neutral Salt, which readily dissolves in water; a true Soluble Tartar.
OBSERVATIONS.
Crystal of Tartar is a saline substance of a singular nature. Though it crystallizes like a Neutral Salt, yet it is not one: it hath only the form of one; its principal properties being those of an Acid. Nevertheless it is not a pure Acid; for it is united with a certain quantity of Oil and of earth, which give it the property of crystallizing, and it is scarce dissolvable in water. It is a middle substance between an Acid and a Neutral Salt. It is an Acid half-neutralized; on which account it is capable of acting like an Acid on all substances soluble by Acids, and so of being converted into a perfectly Neutral Salt by combining with them to the point of saturation.
In the experiments made to neutralize Crystal of Tartar, Fixed Alkaline Salts alone were formerly used. Messrs. Duhamel and Grosse were the first who discovered that Absorbent Earths might be substituted for Alkalis, and would produce nearly the same effects on Crystal of Tartar. The experiments made by these two Academicians in conjunction are circumstantially related in two curious Memoirs on this subject, given in by them jointly, and printed with those of the Academy for 1732 and 1733. From these Memoirs we took the process here given, and shall also borrow from thence most of the remarks we are now going to make.
Stone-lime holds, as it were, the middle place between mere Absorbent Earths and Fixed Alkalis. Now, seeing Crystal of Tartar may be converted into a Neutral Salt by either of these two substances, it follows, that lime ought to produce the same effect upon it. Accordingly Messrs. Duhamel and Grosse found it to be so upon trial: having formed, with Lac calcis and Crystal of Tartar, a Neutral Salt perfectly like that which results from the union of that saline matter with Chalk. Cremor calcis, or that salino-terrene pellicle which forms on lime-water, produced the same effect: but, what is most singular is, that lime-water itself, though it be clear and limpid, and consequently doth not seem to contain any earthy particles, produced nevertheless a great effervescence with Crystal of Tartar, and neutralized it as perfectly as Cremor calcis, or water ever so much impregnated with Chalk. This arises from hence, that a great quantity of the salino-terrene matter, which forms the Cremor calcis is dissolved in the lime-water.
Though lime-water neutralizes Crystal of Tartar as perfectly as Chalk does, and though the Crystals of soluble Tartar, or neutralized Tartar, thereby produced, be like those which have Chalk for their basis, yet Messrs. Duhamel and Grosse observed some differences, worthy of notice, between the phenomena accompanying the production of these two Neutral Salts, which resemble each other so much that they seem but one and the same species of Salt. The principal difference consists in this, that the water containing the Tartar neutralized by Chalk is very limpid, and leaves but a very small quantity of earth on the filter; whereas the lime-water, with which Tartar hath been neutralized, leaves on the filter a considerable quantity of earth.
This must appear the more surprising, that the water replete with Chalk was, before its union with the Crystal of Tartar, turbid and opaque; whereas the Lime water was at first clear and limpid. Messrs. Duhamel and Grosse suspect this to arise from hence, that the effervescence excited, while the Crystal of Tartar dissolves the matter contained in lime-water, is greater than that which is produced by its union with Chalk suspended in water.
"If we consider," say they, "that in a great effervescence a considerable quantity of the acid Spirit is evaporated, we shall easily perceive, that, the more of that Spirit escapes, the more of the earth of the Tartar will be precipitated. Now, as the effervescence with lime-water is more considerable, and as there is less alkaline earth to check, as it were, and restrain the Acid, than in the experiment with Chalk, a greater quantity of the acid Spirit may escape; which being entirely lost will cause more earth to precipitate in this case than in the other, where the Acid is all at once attracted by a great deal of alkaline earth: and accordingly this was the reason that our Tartar dissolved by Chalk deposited, in crystallizing, a grey earth, which was scarce perceivable in the experiment made with Lime-water.
"Yet perhaps," say they, "an Acid, which we suspect to be contained in lime, may have partly occasioned the precipitation of this earth." The existence of this Acid, which these gentlemen at that time only suspected, hath been since demonstrated by several experiments, and particularly by those which Mr. Malouin hath published. This Acid is the Vitriolic, which, in combination with some of the earth of the lime, forms a sort of Selenitic Salt; which adds greatly to the probability of Messrs. Duhamel and Grosse's last conjecture. I shall now explain how I conceive the Vitriolic Acid in lime may occasion the copious precipitate which falls in lime-water, when Crystal of Tartar is neutralized by it.
The quantity of Vitriolic Acid contained in lime is very inconsiderable; so that to convert it into a Neutral Salt requires its intimate union with a very small quantity of the earthy and absorbent parts. Hence it comes to pass, that, when water is poured upon quick-lime, in order to make the Lime-water, it in some sort divides the lime into two parts. All the particles of Absorbent Earth, which had not contracted an union with the Acid, are at first barely suspended in the liquor, the transparency of which they destroy, giving it an opaque white colour; and this is what makes the Lac calcis: but they soon separate from it, and fall to the bottom, in the form of a precipitate; because they are not soluble in water. By this precipitation the liquor becomes limpid, and remains impregnated only with such of the earthy parts as are united with the Vitriolic Acid, in the form of a kind of Neutral Salt, and have by that union acquired solubility. But the Vitriolic Acid finding many more Absorbent parts in the lime than were necessary to neutralize it, in a manner over-dosed itself with earthy parts, and thereby exceeded the bounds of a perfect Neutrality.
On the other hand, it hath been shewn, that Crystal of Tartar is an imperfect Neutral Salt. Now these two Salts, which are neither of them perfectly Neutral, differ from a perfectly Neutral Salt by properties directly opposite to each other; seeing the Selenitic matter in Lime exceeds in its absorbent or alkaline quality, and Crystal of Tartar exceeds, on the contrary, in acidity.
What must be the consequence, therefore, of mixing these two saline matters together? The same as when an Acid is mixed with a Fixed Alkali; that is, the Salt which exceeds in acidity will combine with the super-abundant alkaline earth of the Selenitic Salt; so that these two saline matters will both become perfectly Neutral Salts. Yet these two Neutral Salts have not the same degree of solubility in water. The neutralized Crystal of Tartar dissolves very readily in water, and is for that reason called Soluble Tartar: the Selenitic Salt, on the contrary, is hardly dissolvable in it at all. Now it is a rule that, when two Salts of this nature meet together, the most soluble always remains united with the water, exclusive of the other, which is forced to precipitate. This I imagine to be what happens in the present case; and the precipitate which we see fall, in the lime-water employed to neutralize Crystal of Tartar, seems to me to be no other than the Selenitic Salt of the Lime; which, being less soluble than the neutralized Tartar, gives place to it, and separates from the liquor.
Indeed we cannot, in my opinion, account for the precipitate under consideration, any other way, than by supposing it to be a portion either of the earth of the Crystal of Tartar, or a portion of the Lime. Now, either of these earths is dissolvable by Acids; whereas the precipitate in question, according to the observations of Messrs. Duhamel and Grosse, is not so: and this ought to be the case, if the precipitate be nothing but the selenitic Salt of the Lime, which being a Neutralized Salt, partly constituted by the most powerful of all the Acids, must be unalterable by any Acid whatever.
Messrs. Duhamel and Grosse made a great many experiments on the combinations of Crystal of Tartar with different sorts of earths. The result of the whole is, that there are some earths which this Acid dissolves, and which contract such an union with Crystal of Tartar, that they not only change its external character, that is, its tendency to crystallize, and its indissolubleness in cold water, but also entirely alter its taste and other qualities. In a word, those earths produce on this Salt all the effects of alkaline Salts. These earths are such as are called Absorbent Earths; stone-lime, animal-lime, cretaceous earths, a portion of calcined gypsum, and of potash; in short, all such as distilled vinegar is capable of dissolving: this is the mark by which those earths, which are qualified to neutralize Crystal of Tartar, and to render it soluble, may be distinguished.
Messrs. Duhamel and Grosse found also upon trial, that there are other earths, on the contrary, which are, in a manner, inaccessible to the Acid of Crystal of Tartar; that they take up, indeed, the grossest and redundant Oil of the Tartar, but without affecting its saline part at all: and if these earths are ever observed to form any union with the Crystals of Tartar, as happens in the refineries near Montpelier, that union is only superficial, not intimate; and therefore it alters none of the characters of the Salt. Among these earths are the clayey, bolar, sandy earths, and others of that kind. Hence Messrs. Duhamel and Grosse conclude, that these are the earths which ought to be employed in the purification and whitening of Crystal of Tartar. Vinegar is here also the test by which it may be known whether an earth intended for this purpose be fit for it: for you may be sure that it will form no union with Crystal of Tartar, if the Acid of Vinegar be incapable of dissolving it.
Crystal of Tartar combined with Fixed Alkalis. The Vegetable Salt. Saignette's Salt. The Decomposition of Soluble Tartars.
In eight parts of water dissolve one part of a very pure alkaline Salt, perfectly freed from the phlogiston by calcination. Heat this lixivium in a stone pan set on a sand-bath, and from time to time throw into it a little powdered Cream or Crystal of Tartar. Each projection will excite a great effervescence, attended with many bubbles, which will rise to a considerable height one over the other. Stir the liquor when the effervescence ceases, and you will see it begin again.
When no effervescence appears upon stirring the liquor, add a little more Cream of Tartar, and the same phenomena will be renewed. Go on thus till you have obtained the point of perfect saturation.
Then filter your liquor. If the Alkali you made use of was the Salt of Soda, evaporate your liquor quickly to a pellicle, and there will shoot in it crystals of nine sides, resembling a coffin; the bottom part thereof being concave, and streaked with a great many parallel lines; and this is Saignette's Salt. If you have employed any other Alkali but Soda, or the basis of Sea-salt, evaporate your liquor slowly to the consistence of a syrup: let it stand quiet, and there will form in it crystals having the figure of slatted parallellopipeds; and this is the Vegetable Salt, or Tartarized Tartar.
OBSERVATIONS.
Seeing pure Absorbent Earths are capable of neutralizing Crystal of Tartar, and converting it into Soluble Tartar, there is still more reason to expect that Fixed Alkalis should possess the same property, as they have a much greater affinity with Acids: and accordingly Crystal of Tartar always forms, with every species of these salts, a Neutral Salt which is a Soluble Tartar.
A Soluble Tartar, formed by the union of Crystal of Tartar with Tartar converted into an Alkali by fire, hath been long used in medicine as a gentle saponaceous purgative, known by the names of Tartarized Tartar, or the Vegetable Salt. But the Soluble Tartar, prepared by combining Crystal of Tartar with the Alkali of Soda, which, as we remarked before, is analogous to the basis of Sea-salt, and different from all other Alkalis, was not well known to Chymists till the year 1731, when M. Boulduc published the preparation in a Memoir printed in the Academy's collection for that year[14].
Not but that it was very much used before that time: for it had been for several years in high reputation, and prescribed instead of Tartarized Tartar, which became almost quite neglected. But M. Saignette, a physician of Rochelle, who was the first inventor and vender of this Salt, did not publish the preparation of it, which he kept as a secret: and this probably contributed not a little to the great esteem which this medicine had acquired; for men are naturally inclined to put a much greater value on secrets, than on what is universally known. He gave it the name of Sal Polychrestum; and the public called it also Saignette's Salt, and Rochelle Salt. Since the discoveries of M. Geoffroy and M. Boulduc were published, the method of preparing this Salt hath been no secret; it was described in Dispensatories, and every apothecary hath made it ever since.
Saignette's Salt, as well as every other Soluble Tartar, melts when laid on live coals, boils up, emits smoke, and leaves a black charred matter behind. This resemblance of Saignette's Salt to Tartarized Tartar, joined to the smell of the vapour which exhaled in burning it, and is the same with that of Tartar, were the first notices that led M. Boulduc to suppose this Salt to be a soluble Tartar. On examining the alkaline coal produced by the calcination, and comparing it with that left by Tartarized Tartar, he perceived there was some difference between them. At last his friend, M. Grosse, having advised him, as he tells us in his Memoir, to combine Crystal of Tartar with the Salt of Soda, and to examine the new Salt that would result from their union, M. Boulduc immediately suspected that it must produce a species of Soluble Tartar, which might possibly prove to be the Salt in question. Nor was he mistaken in his conjecture: for with these two saline substances he actually composed a Salt perfectly like Saignette's.
Under the head of Borax we remarked that it contains an Alkali like the basis of Sea-salt. This Alkali is not perfectly neutralized by the sedative Salt, which is also contained in Borax: for its alkaline properties are so perceptible as to have led some Chymists to think that Borax was only an Alkali of a particular kind. This induced M. le Fevre, a Physician at Uzes, and one of the Academy's correspondents, to combine Crystal of Tartar with Borax, and to examine the result. He communicated to the Academy his experiments on this subject; by which he found that the combination of these two saline matters forms a Soluble Tartar, but greatly different from Saignette's Salt; especially in that it doth not crystallize, but remains in the form of a gummy matter, and retains all the acidity natural to pure Cream or Crystal of Tartar: a circumstance which is very remarkable.
Mr. Lemery had the curiosity to repeat M. le Fevre's experiment, and found that this singular Soluble Tartar had the properties ascribed to it by the inventor. The process he recommends for making the experiment with success is as follows:
"Take four ounces of Crystal of Tartar finely pulverized, and two ounces of Borax carefully powdered, and put these two Salts into a flint-glass body. Pour on them two ounces of water, and set the cucurbit into a sand-bath. Warm it with a gentle fire, and then increase the heat so as to make the liquor boil for a quarter of an hour; which will produce a perfect dissolution of the Cream of Tartar and Borax. After the dissolution of these two Salts united together, the liquor will remain clear and limpid, though the boiling hath dissipated a good deal of it. If the liquor be still further evaporated, the remainder will have the consistence of Honey, or Turpentine: and, if the evaporation be carried still farther, with a gentle heat, the matter remaining will in colour resemble the gum of a plumb-tree, and yield to pressure as that does; and, if it be exposed to the air in a damp place, it will grow moist and run, almost like Salt of Tartar:" a new and singular property, which belongs neither to Borax nor to Crystal of Tartar, when they are not combined together.
All Soluble Tartars are easily decompounded, by means of a certain degree of heat. They yield in the distillation the same principles as Tartar; and the Alkali that remains, when they are perfectly calcined, consists of that which the Tartar naturally affords, and of the alkaline matter with which it was converted into a Neutral Salt.
These Neutral Salts, resulting from the union of Crystal of Tartar with any alkaline matter, are also decompounded by all the Acids, even by vinegar, which nevertheless is an Oily Vegetable Acid, and consequently of the same kind with Crystal of Tartar. The reason of this is that the Acid of Vinegar, though blunted by much phlegm and oil, must be considered as a free and pure Acid, when compared with Crystal of Tartar; which is still more embarrassed with heterogeneous matters, so as to be a semi-neutral Salt.
When Soluble Tartar is decompounded by an Acid, the Crystal of Tartar, which helped to constitute the Neutral Salt, is then wholly recovered. This saline matter, being separated from that which rendered it soluble in water, ceases now to be so, and for that reason precipitates to the bottom of the liquor.
The Neutral Salts, resulting from the decomposition of Soluble Tartar by an Acid, differ according to the Acid made use of. From Saignette's Salt decompounded by the Vitriolic Acid M. Boulduc obtained a true Glauber's Salt, and a precipitate of Crystal of Tartar: and this he justly adduces as a demonstrative proof, that Saignette's Salt is no other than Crystal of Tartar neutralized by a Fixed Alkali analogous to the basis of Sea-salt.
Though all Soluble Tartars may be decompounded by Acids, as hath just been said, yet they do not all forsake their bases with equal facility. Messrs. Duhamel and Grosse found that, in this respect, they observe the following order, beginning with those which afford the readiest and most copious precipitate: viz. Soluble Tartar made 1. with Potash; 2. with Chalk; 3. with uncalcined Oyster-shells; 4. with Stone-Lime; 5. with calcined Oyster-shells; 6. with Salt of Tartar; 7. with Salt of Soda; 8. and lastly, Tartar made soluble with Borax is not precipitated by distilled vinegar.
It is not easy to account for this difference between Soluble Tartars. If the Salt of Soda were more alkaline than Salt of Tartar, and Borax more alkaline than the Salt of Soda, it might be conjectured that the more alkaline the matters are with which Crystal of Tartar is neutralized, the closer is the union it contracts with them; since it is plain, from what hath been said on this subject, that though Soluble Tartars, which have for their basis Absorbent Earths only, not converted into Lime, are more easily decompounded than those which are rendered soluble by Limes; and these again more easily than those which have a Fixed Alkali for their basis. But, on the contrary, the Salt of Soda is less alkaline than Salt of Tartar, and Borax still less than the Salt of Soda.
Crystal of Tartar combined with Iron. Chalybeated Tartar. Tincture of Steel with Tartar. Soluble Chalybeated Tartar.
Mix four ounces of Iron, in filings, with one pound of white Tartar, finely pulverized. Boil the mixture in about twelve times as much water as you took of Tartar. When the saline part of the Tartar is dissolved, filter the liquor boiling-hot through a flannel bag, and then set it in a cool place. In a very little time crystals of a russet colour will shoot therein. Decant the liquor from these crystals; evaporate it to a pellicle, and set it again to crystallize. Go on in this manner till it will shoot no more. Collect all the Salt you have thus obtained, and keep it under the name of Chalybeated Tartar.
To make the Tincture of Steel with Tartar, mix together six ounces of clean Iron filings, and one pound of white Tartar in powder. Put this mixture into a large iron kettle, and pour thereon as much rain-water as will moisten it.
Make a paste of this matter, and leave it thus in a mass for twenty-four hours. Then pour on it twelve pounds of rain-water, and boil the whole for twelve hours at least, stirring the mixture frequently, and adding from time to time some hot water, to supply the place of what evaporates. When you have thus boiled the liquor, let it stand quiet for some time, and then pour it off from the sediment at bottom. Filter, and evaporate to the consistence of a syrup; and you have the Tincture of Mars with Tartar. The Dispensatories generally order an ounce of rectified Spirit of Wine to be poured on this Tincture, in order to preserve it, and to keep it from growing mouldy, as it is very apt to do.
Soluble Chalybeated Tartar is prepared by mixing four ounces of Tartarized Tartar, with one pound of the Tincture of Mars with Tartar, and evaporating them together in an iron vessel to dryness; after which it is kept in a well stopped phial, to prevent its growing moist in the air.
OBSERVATIONS.
The three preparations of this process are medicines very well known and much used. There is even reason to think that those, who first thought of combining Tartar in this manner with Iron, had it in their view to prepare compositions useful in medicine, rather than merely to produce new combinations for the improvement of Chymistry. Indeed, were we to consider only the account here given of the manner in which these three compositions are made, we should be inclined to think Crystal of Tartar incapable of dissolving Iron so thoroughly and radically, that, from the union of these two substances, a Neutral Metallic Salt should arise, a Tartar neutralized and made soluble by Iron. For it is very certain that the first of these preparations, which is called Chalybeated Tartar, is nothing but the saline part of Tartar dissolved by boiling water, and then precipitated and crystallized along with particles of iron, that are reduced, at most, into a rust, or a crocus only, but have contracted no union with the crystal of Tartar, which remains as Acid and as indissoluble after this preparation as before. Accordingly it is called only Chalybeated Tartar, and not Soluble Chalybeated Tartar: and, as this latter name hath been given only to the Tartarized Tincture of Mars compounded with Tartarized Tartar; that is, with Tartar rendered soluble by a Fixed Alkali, and not by Iron; there is reason to presume, that the Tincture of Mars alone was not thought worthy of being called a Soluble Chalybeated Tartar; but that the name, importing Tartar rendered soluble by Mars, belongs to that Tincture only when compounded with a true Soluble Tartar.
It is nevertheless very certain, that the Tincture of Mars made with Tartar contains a true Soluble Chalybeated Tartar; that is, a Neutral Salt consisting of Crystal of Tartar united with Iron, and rendered soluble by that union. The long boiling, necessary to prepare this Tincture, gives the Acid of Tartar time to dissolve the Iron radically, and to unite very closely therewith: but this is not the case in the preparation of Chalybeated Tartar; to make which the Tartar is boiled in water only as long as is necessary for the dissolution of its saline parts; that is, about a quarter or half an hour; in which space the Acid of the Tartar can scarce begin to act on the surface of the Iron: for Acids have not so quick an effect on metals, as on Alkalis and Absorbent Earths. Metallic substances, being vastly more compact, are not near so soon dissolved by Acids, and especially by vegetable Acids, weakened with heterogeneous matters, as the Acid of Tartar is.
I thought the dissolution of Iron by Tartar a point of sufficient importance to deserve a little more attention than hath commonly been given to it; and for that reason resolved to examine, and trace with care, the phenomena observable in this operation.
As the crude Tartar, employed in making the Tartarized Tincture of Mars, is replete with many oily and earthy parts, which cannot but obstruct the dissolution of the Iron, and prevent our seeing clearly how that dissolution is carried on, I thought it better to make use of Cream, or Crystals, of Tartar, which, being pure and freed from all those heterogeneous parts, dissolve in boiling water without prejudicing its transparency.
I therefore pulverized Cream of Tartar, and dissolved as much thereof in boiling water as it would take up. This solution I poured boiling hot into a matrass, at the bottom of which I laid some fine iron wire cut into small pieces. I set the matrass in a sand-bath; and having heated it so as to make the liquor boil, I observed that, the instant before it boiled, the liquor began to act very perceptibly upon the Iron, in the same manner as other Acids act upon metallic substances; that is, there appeared on the surfaces of the little bits of Iron small bubbles, which immediately rose to the surface of the liquor, and succeeded each other so fast, that they formed lines, or jets, seemingly continued from the surface of the Iron to the surface of the liquor, which, little by little, acquired a faint tinge of yellow.
When the liquor was heated so as to boil, the dissolution still went on, but much more briskly, and the liquor acquired a deeper colour. After boiling about an hour, the liquor, which at first was very clear, became turbid, and of an opaque white; which made me think, that some of the Cream of Tartar, dissolved therein, began to precipitate.
I let the whole boil some time longer, and the white precipitate becoming more considerable, I resolved to filter the liquor, which passed through clear, and tinged with a greenish yellow. There remained on the filter a whitish sediment, which I found to be true Cream of Tartar. The filtered liquor tasted much like a solution of Copperas. I evaporated it in a glass bason, set in a sand-heat, but no pellicle appeared; which made me conclude that it would produce no crystals: accordingly, having taken some of it out of the bason, when it was considerably reduced by evaporation, and set it in a cool place, no crystal shot in it.
The rest of the liquor I evaporated to dryness: it left a blackish brown residuum, which had the same taste with the liquor before evaporation, but much stronger. This residuum melts very readily in the mouth, without leaving on the tongue the least gritty particle. Being exposed very dry to the air, it grows moist, and runs into a liquor in a very little time. It dissolves easily and readily in a very small quantity of cold water. This solution being mixed with Fixed Alkalis, in various proportions, doth not grow turbid, nor drops any precipitate; but with a decoction of galls it makes ink. Acids give it a much clearer colour, and at first produce no precipitation; but, in a quarter of an hour, there appears a precipitate much of the same colour with the solution. This precipitate is no other than Cream of Tartar, tinged of a russet colour by the liquor, which grows turbid, and a little whitish, when the precipitate begins to form.
These experiments, and the circumstances attending them, will not allow us to doubt the truth of what I advanced concerning the Tincture of Mars made with Tartar, viz. that it is nothing but Crystal of Tartar by which Iron is dissolved, and which is rendered soluble by that metal. We see at the very first that Crystal of Tartar acts upon Iron, just as other Acids do. Indeed this metallic solution is not precipitated by Alkalis: but we know that Alkalis possess the property of dissolving Iron, especially when the metal is previously divided by an Acid; so that there is reason to think this may be the case, when an Alkali is mixed with our Soluble Chalybeated Tartar.
As this Soluble Tartar is a saponaceous and oily Salt, it is also possible that it may be dissolved entirely by the Alkali, without suffering any decomposition; especially as Alkalis decompound Neutral Metallic Salts, by means only of the stronger affinity which they have with the Acids, than with the Metals, of which those Salts are compounded. Now, as our Soluble Chalybeated Tartar is compounded of that Metal which the Alkali dissolves with the greatest ease, and of that Acid with which it hath the least affinity of any, it is very possible that it may not have a greater affinity with the Acid than with the metallic basis of this Salt, and so be uncapable of decompounding it. However, as this Soluble Chalybeated Tartar makes a black liquor with a decoction of Galls, and as nothing but Iron dissolved by an Acid hath that property, it may be safely concluded, that this Salt really consists of Iron dissolved by the Acid of Tartar.
The precipitate which a solution of this Salt lets fall, on the addition of an Acid, is another proof that it consists of these two principles: for this precipitate can be no other than the Tartarous Acid, which, being the weakest of all Acids, is separated from the Iron by the Acid added to the solution; which Acid unites with the Martial basis, and forms another Neutral Metallic Salt, according to the Acid employed. Lastly, the great solubility of the desiccated residuum of the Tincture of Mars, made with Tartar, is a very strong and decisive proof, that this residuum is no other than Iron dissolved by the Acid of Tartar: for what else can it be? Nothing but Iron and Crystal of Tartar is made use of in the operation; and neither of these two substances singly is so soluble as this new body.