Joseph Black (1728-1799)

Experiments upon Magnesia Alba, Quick-Lime, and some other Alkaline Substances

By the following experiments, I proposed to know whether this substance could be reduced to a quick-lime.

An ounce of magnesia was exposed in a crucible for about an hour to such a heat as is sufficient to melt copper. When taken out, it weighed three drams and one scruple, or had lost 7/12 of its former weight.

I repeated, with the magnesia prepared in this manner, most of those experiments I had already made upon it before calcination, and the result was as follows.

It dissolves in all the acids, and with these composes salts exactly similar to those described in the first set of experiments: but what is particularly to be remarked, it is dissolved without any the least degree of effervescence.

It slowly precipitates the corrosive sublimate of mercury in the form of a black powder.

It separates the volatile alkali in a salt-ammoniac from the acid, when it is mixed with a warm solution of that salt. But it does not separate an acid from a calcarious earth, nor does it induce the least change upon lime-water.

Lastly, when a dram of it is digested with an ounce of water in a bottle for some hours, it does not make any the least change in the water. The magnesia, when dried, is found to have gained ten grains; but it neither effervesces with acids, nor does it sensibly affect lime-water.

Observing magnesia to lose such a remarkable proportion of its weight in the fire, my next attempts were directed to the investigation of this volatile part, and, among other experiments, the following seemed to throw some light upon it.

Three ounces of magnesia were distilled in a glass retort and receiver, the fire being gradually increased until the magnesia was obscurely red hot. When all vas cool, I found only five drams of a whitish water in the receiver which had a faint smell of the spirit of hartshorn, gave a green colour to the juice of violets, and rendered the solutions of corrosive sublimate and of silver very slightly turbid. But it did not sensibly effervesce with acids.

The magnesia, when taken out of the retort, weighed an ounce, three drams, and thirty grains, or had lost more than half of its weight. It still effervesced pretty briskly with acids, tho' not so strongly as before this operation.

The fire should have been raised here to the degree requisite for the perfect calcination of magnesia. But even from this imperfect experiment, it is evident, that of the volatile parts contained in that powder, a small proportion only is water; the rest cannot, it seems, be retained in vessels, under a visible form. Chemists have often observed, in their distillations, that part of a body has vanished from their senses, notwithstanding the utmost care to retain it; and they have always found, upon further inquiry, that subtile part to be air, which having been imprisoned in the body, under a solid form, was set free, and rendered fluid and elastic by the fire. We may therefore safely conclude, that the volatile matter, lost in the calcination of magnesia, is mostly air; and hence the calcined magnesia does not emit air, or make an effervescence when mixed with acids.

The water, from its properties, seems to contain a small portion of volatile alkali, which was probably formed from the earth, air, and water, or from some of these combined together; and perhaps also from a small quantity of inflammable matter which adhered accidentally to the magnesia. Whenever Chemists meet with this salt, they are inclined to ascribe its origin to some animal, or putrid vegetable, substance; and this they have always done, when they obtained it from the calcarious earths, all of which afford a small quantity of it. There is, however, no doubt that it can sometimes be produced independently of any such mixture, since many fresh vegetables and tartar afford a considerable quantity of it. And how can it, in the present instance, be supposed, that any animal or vegetable matter adhered to the magnesia, while it was dissolved by an acid, separated from this by an alkali, and washed with so much water?

Two drams of magnesia were calcined in a crucible, in the manner described above, and thus reduced to two scruples and twelve grains. This calcined magnesia was dissolved in a sufficient quantity of spirit of vitriol, and then again separated from the acid by the addition of an alkali, of which a large quantity is necessary for this purpose. The magnesia being very well washed and dryed, weighed one dram and fifty grains. It effervesced violently, or emitted a large quantity of air, when thrown into acids, formed a red powder when mixed with a solution of sublimate, separated the calcarious earths from an acid, and sweetened lime-water: and had thus recovered all those properties which it had but just now lost by calcination: Nor had it only recovered its original properties, but acquired besides an addition of weight nearly equal to what had been lost in the fire; and, as it is found to effervesce with acids, part of the addition must certainly be air.

This air seems to have been furnished by the alkali from which it was separated by the acid; for Dr. Hales has clearly proved, that alkaline salts contain a large quantity of fixed air, which they emit in great abundance when joined to a pure acid. In the present case, the alkali is really joined to an acid, but without any visible emission of air; and yet the air is not retained in it: for the neutral salt, into which it is converted, is the same in quantity, and in every other respect, as if the acid employed had not been previously saturated with magnesia, but offered to the alkali in its pure state, and had driven the air out of it in their conflict. It seems therefore evident, that the air was forced from the alkali by the acid, and lodged itself in the magnesia.

These considerations led me to try a few experiments, whereby I might know what quantity of air is expelled from an alkali, or from magnesia, by acids.

Two drams of a pure fixed alkaline salt, and an ounce of water, were put into a Florentine flask, which, together with its contents, weighed two ounces and two drams. Some oil of vitriol diluted with water was dropt in, until the salt was exactly saturated; which it was found to be, when two drams, two scruples, and three grains of this acid had been added. The phial with its contents now weighed two ounces, four drams, and fifteen grains. One scruple, therefore, and eight grains were lost during the ebullition, of which a trifling portion may be water, or something of the same kind. The rest is air.

The celebrated Homberg has attempted to estimate the quantity of solid salt contained in a determined portion of the several acids. He saturated equal quantities of an alkali with each of them; and, observing the weight which the alkali had gained, after being perfectly dryed, took this for the quantity of solid salt contained in that share of the acid which performed the saturation. But we learn from the above experiment, that his estimate was not accurate, because the alkali loses weight as well as gains it.

Two drams of magnesia, treated exactly as the alkali in the last experiment, were just dissolved by four drams, one scruple, and seven grains of the same acid liquor, and lost one scruple and sixteen grains by the ebullition.

Two drams of magnesia were reduced, by the action of a violent fire, to two scruples and twelve grains, with which the same process was repeated, as in the two last experiments; four drams, one scruple, and two grains of the same acid, were required to compleat the solution, and no weight was lost the experiment.

As in the separation of the volatile from the fixed parts of bodies, by means of heat, a small quantity of the latter is generally raised with the former; so the air and water, originally contained in the magnesia, and afterwards dissipated by the fire, seem to have carried off a small part of the fixed earth of this substance. This is probably the reason, why calcined magnesia is saturated with a quantity of acid, somewhat less than what is required to dissolve it before calcination: and the same may be assigned as one cause which hinders us from restoring the whole of its original weight, by solution and precipitation.

I took care to dilute the vitriolic acid, in order to avoid the heat and ebullition which it would otherwise have excited in the water; and I chose a Florentine flask, on account of its lightness, capacity, and shape, which is peculiarly adapted to the experiment; for the vapours raised by the ebullition circulated for a short time, thro' the wide cavity of the phial, but were soon collected upon its sides, like dew, and none of them seemed to reach the neck, which continued perfectly dry to the end of the experiment.

We now perceive the reason why crude and calcined magnesia, which differ in many respects from one another, agree however in composing the same kind of salt, when dissolved in any particular acid; for the crude magnesia seems to differ from the calcined chiefly by containing a considerable quantity of air, which air is unavoidably dissipated and lost during the dissolution.

From our experiments, it seems probable, that the increase of weight which some metals acquire, by being first dissolved in acids, and then separated from them again by alkalis, proceeds from air furnished by the alkalis, and that in the aurum fulminans, which is prepared by the same means, this air adheres to the gold in such a peculiar manner, that, in a moderate degree of heat, the whole of it recovers its elasticity in the same instant of time; and thus, by the violent shock which it gives to the air around, produces the loud crack or fulmination of this powder. Those who will imagine the explosion of such a minute portion of fixed air, as can reside in the aurum fulminans, to be insufficient for the excessive loudness of the noise, will consider, that it is not a large quantity of motion communicated to the air, but rather a smart stroke which produces sound, and that the explosion of but a few particles of fixed air may be capable of causing a loud noise, provided they all recover their spring suddenly, and in the same instant.

The above experiments lead us also to conclude, that volatile alkalis, and the common absorbent earths, which lose their air by being joined to acids, but shew evident signs of their having recovered it, when separated from them by alkalis, received it from these alkalis which lost it in the instant of their joining with the acid.

The following are a few experiments upon three of the absorbent earths, made in order to compare them with one another, and with magnesia.

Suspecting that magnesia might possibly be no other than a common calcarious earth, which had changed its nature by having been previously combined with an acid, I saturated a small quantity of chalk with the muriatic acid, separated the acid from it again by means of a fixed alkali and carefully washed away the whole of the salt.

The chalk when dryed was not found to have suffered any alteration; for it effervesced with the vitriolic acid, but did not dissolve in it; and when exposed to a violent fire, was converted into a quick-lime, in all respects similar to that obtained from common chalk.

In another experiment of the same kind, I used the vitriolic acid with same event.

Any calcarious matter reduced to a fine powder, and thrown into a warm solution of alum, immediately raises a brisk effervescence. But the powder is not dissolved; it is rather increased in bulk: and if the addition be repeated until it is no longer accompanied with effervescence, the liquor loses all taste of the alum, and yields only a very light cloud upon the admixture of an alkali.

From this experiment we learn, that acids attract the calcarious earth more strongly then [sic] they do the earth of alum; and as the acid in this salt is exactly the same with the vitriolic, it composes with the calcarious earth a neutral substance, which is very difficultly soluble in water, and therefore falls down to the bottom of the vessel along with the earth of alum, which is deprived of its acid. The light cloud formed by the alkali proceeds from the minute portion of the calcarious compound which saturates the water.

The earth of animal bones, when reduced to a fine powder and thrown into a diluted vitriolic acid, gradually absorbs the acid in the same manner as the calcarious earths, but without any remarkable effervescence. When it is added to the nitrous or to the muriatic acid, it is slowly dissolved. The compound liquor thence produced is extremely acrid, and still changes the colour of the juice of violets to a red, even after it is fully saturated with the absorbent. Distilled vinegar has little or no effect upon this earth; for after a long digestion it still retains its sour taste, and gives only a light cloud upon the addition of an alkali.

By dropping a dissolved fixed alkali into a warm solution of alum, I obtained the earth of this salt, which after being well washed and dryed, was found to have the following properties:

It is dissolved in every acid but very slowly, unless assisted by heat. The several solutions, when thoroughly saturated, are all astringent with a slight degree of an acid taste, and they also agree with a solution of alum in this, that they give a red colour to the infusion of turnsol.

Neither this earth, nor that of animal bones, can be converted into quick-lime by the strongest fire, nor do they suffer any change worth notice. Both of them seem to attract acids but weakly, and to alter their properties less when united to them than the other absorbents.

PART II.

In reflecting afterwards upon these experiments, an explication of the nature of lime offered itself, which seemed to account, in an easy manner, for most of the properties of that substance.

It is sufficiently clear, that the calcarious earths in their native state, and that the alkalis and magnesia in their ordinary condition, contain a large quantity of fixed air, and this air certainly adheres to them with considerable force, since a strong fire is necessary to separate it from magnesia, and the strongest is not sufficient to expel it entirely from fixed alkalis, or take away their power of effervescing with acid salts.

These considerations led me to conclude, that the relation between fixed air and alkaline substances was somewhat similar to the relation between these and acids; that as the calcarious earths and alkalis attract acids strongly and can be saturated with them, so they also attract fixed acids strongly and can be saturated with them, so they also attract fixed air, and are in their ordinary state saturated with it: and when we mix an acid with an alkali or with an absorbent earth, that the air is then set at liberty, and breaks out with violence; because the alkaline body attracts it more weakly than it does the acid, and because the acid and air cannot both be joined to the same body at the same time.

I also imagined that, when the calcarious earths are exposed to the action of a violent fire, and are thereby converted into quick-lime, they suffer no other change in their composition than the loss of a small quantity of water and of their fixed air. The remarkable acrimony which we perceive in them after this process, was not supposed to proceed from any additional matter received in the fire, but seemed to be an essential property of the pure earth, depending on an attraction for those several substances which it then became capable of corroding or dissolving, which attraction had been insensible as long as the air adhered to the earth, but discovered itself upon the separation.

This supposition was founded upon an observation of the most frequent consequences of combining bodies in chemistry. Commonly when we join two bodies together, their acrimony or attraction for other substances becomes immediately either less perceivable or entirely insensible; stances becomes immediately either less perceivable or entirely or entirely insensible; altho' it was sufficiently strong and remarkable before their union, and is composed of an acid and alkali, does not possess the acrimony of either of its constituent parts. It can easily be separated from water, has little or no effect upon metals, is incapable of being joined to inflammable bodies, and of corroding and dissolving animals and vegetables; so that the attraction both of the acid and alkali for these several substances seems to be suspended till they are again separated from one other.

Crude lime was therefore considered as a peculiar acrid earth rendered mild by its union with fixed air: and quick-lime as the same earth, in which, by having separated the air, we discover that acrimony or attraction for water, for animal, vegetable, and for inflammable substances.

That the calcarious earths really lose a large quantity of air when they are burnt to quick-lime, seems sufficiently proved by an experiment of Mr. Margraaf, an exceedingly accurate and judicious Chemist. He subjected eight ounces of osteocolla to distillation in an earthen retort, finishing his process with the most violent fire of a reverberatory, and caught in the receiver only two drams of water, which by its smell and properties shewed itself to be slightly alkaline. He does not tell us the weight of the osteocolla remaining in the retort, and only says, that it was converted into quick-lime; but as no calcarious earth can be converted into quick-lime, or bear the heat which he applied without losing above a third of its weight, we may safely conclude, that the loss in his experiment was proportional, and proceeded chiefly from the dissipation of fixed air.

According to our theory, the relation of the calcarious earth to air and water appeared to agree with the relation of the same earth to the vitriolic and vegetable acids. As chalk for instance has a stronger attraction for the vitriolic than for the vegetable acid, and is dissolved with more difficulty when combined with the first, than when joined to the second: so it also attracts air more strongly than water, and is dissolved with more difficulty when saturated with air than when compounded with water only.

A calcarious earth deprived of its air, or in the state of quick-lime greedily absorbs a considerable quantity of water, becomes soluble in that fluid, and is then said to be slaked; but as soon as it meets with fixed air, it is supposed to quit the water and join itself to the air, for which it has a superior attraction, and is therefore restored to its first state of mildness and insolubility in water.

When slaked lime is mixed with water, the fixed air in the water is attracted by the lime, and saturates a small portion of it, which then becomes again incapable of dissolution, but part of the remaining slaked lime is dissolved and composes lime-water.

If this fluid be exposed to the open air, the particles of quick-lime which are nearest the surface gradually attract the particles of fixed air which float in the atmosphere. But at the same time that a particle of lime is thus saturated with air, it is also restored to its native state of mildness and insolubility; and as the whole of this change must happen at the surface, the whole of the lime is successively collected there under its original form of an insipid calcarious earth, called the cream or crusts of lime-water.

When quick-lime itself is exposed to the open air, it absorbs the particles of water and of fixed air which come within its sphere of attraction, as it meets with the first of these in greatest plenty, the greatest part of it assumes the form of slaked lime; the rest is restored to its original state; and if it be exposed for a sufficient length of time, the whole of it is gradually saturated with air, to which the water as gradually yields its place.

We have already shewn by experiment, that magnesia alba is a compound of a peculiar earth and fixed air. When this substance is mixed with lime-water, the lime shews a stronger attraction for fixed air than that of the earth of magnesia; the air leaves this powder to join itself to the lime. And as neither the lime when saturated with air, nor the magnesia when deprived of it, are soluble in water, the lime-water becomes perfectly pure and insipid, the lime which it contained being mixed with the magnesia. But if the magnesia be deprived of air by calcination before it is mixed with the lime-water, this fluid suffers no alteration.

If quick-lime be mixed with a dissolved alkali, it likeways shews an attraction for fixed air superior to that of the alkali. It robs this salt of its air, and thereby becomes mild itself, while the alkali is consequently rendered more corrosive, or discovers its natural degree of acrimony or strong attraction for water, and for bodies of the inflammable, and of the animal and vegetable kind; which attraction was less perceivable as long as it was saturated with air. And the volatile alkali when deprived of its air, besides this attraction for various bodies, discovers likeways its natural degree of volatility, which was formerly somewhat repressed by the air adhering to it, in the same manner as it is repressed by the addition of an acid.

This account of lime and alkalis recommended itself by its simplicity, and by affording an easy solution of many phaenomena, but appeared upon a nearer view to be attended with consequences that were so very new and extraordinary, as to render suspicious the principles from which they were drawn.

I resolved however to examine, in a particular manner, such of these consequences as were the most unavoidable, and found the greatest number of them might be reduced to the following propositions:

I. If we only separate a quantity of air from lime and alkalis, when we render them caustic they will be found to lose part of their weight in the operation, but will saturated the same quantity of acid as before, and the saturation will be performed without effervescence.

II. If quick-lime be no other than a calcarious earth deprived of its air, and whose attraction for fixed air is stronger than that of alkalis, it follows, that, by adding to it a sufficient quantity of alkali saturated with air, the lime will recover the whole of its air, and be entirely restored to its original weight and condition: and it also follows, that the earth separated from lime-water by an alkali, is the lime which was dissolved in the water now restored to its original mild and insoluble state.

III. If it be supposed that slaked lime does not contain any parts which are more firey, active, or subtile than others, and by which chiefly it communicates its virtues to water; but that it is an uniform compound of lime and water: it follows, that, as part of it can be dissolved in water, the whole of it is also capable of being dissolved.

IV. If the acrimony of the caustic alkali does not depend on any part of the lime adhering to it, a caustic or soap-ley will consequently be found to contain no lime, unless the quantity of lime employed in making it were greater than what is just sufficient to extract the whole air of the alkali; for then as much of the superfluous quick-lime might possibly be dissolved by the ley as would be dissolved by pure water, or the ley would contain as much lime as lime-water does.

V. We have shewn in the former experiments, that absorbent earths lose their air when they are joined to an acid; but recover it, if separated again from that acid, by means of an ordinary alkali: the air passing from the alkali to the earth, at the same time that the acid passes from the earth to the alkali.

If the caustic alkali therefore be destitute of air, it will separate magnesia from an acid under the form of a magnesia free of air, or which will not effervesce with acids; and the same caustic alkali will also separate a calcarious earth from acids under the form of a calcarious earth destitute of air, but saturated with water, or under the form of slaked lime.

These were all necessary conclusions from the above suppositions. Many of them appeared too improbable to deserve any further attention: some however, I found upon reflection, were already seconded by experience. Thus Hoffman has observed, that quick-lime does not effervesce with spirit of vitriol; and it is well known that the caustic spirit of urine, or of salt ammoniac, does not emit air, when mixed with acids. This consideration excited my curiosity, and determined me to inquire into the truth of them all by way of experiment. I therefore engaged myself in a set of trials; the history of which is here subjoined. Some new facts are likeways occasionally mentioned; and here it will be proper to inform the reader, that I have never mentioned any, without satisfying myself of their truth by experiment, tho' I have sometimes taken the liberty to neglect describing the experiments when they seemed sufficiently obvious.

Desiring to know how much of an acid a calcarious earth will absorb, and what quantity of air is expelled during the dissolution, I saturated two drams of chalk with diluted spirit of salt, and used the Florentine flask, as related in a similar experiment upon magnesia. Seven drams and one grain of the acid finished the dissolution, and the chalk lost two scruples and eight grains of air.

This experiment was necessary before the following, by which I proposed to inquire into the truth of the first proposition so far as it relates to quick-lime.

Two drams of chalk were converted into a perfect quick-lime, and lost two scruples and twelve grains in the fire. This quick-lime was slaked or reduced to a milky liquor with an ounce of water, and then dissolved in the same manner, and with the same acid, as the two drams of chalk in the preceding experiment. Six drams, two scruples and fourteen grains of the acid finished the saturation without any sensible effervescence or loss of weight.

It therefore appears from these experiments, that no air is separated from quick-lime by an acid, and that chalk saturates nearly the same quantity of acid after it is converted into quick-lime as before.

With respect to the second proposition, I tried the following experiments.

A piece of perfect quick-lime made from two drams of chalk, and which weighed one dram and eight grains, was reduced to a very fine powder, and thrown into a filtrated mixture of an ounce of a fixed alkaline salt and two ounces of water. After a slight digestion, the powder being well washed and dried, weighed one dram and fifty eight grains. It was similar in every trial to a fine powder of ordinary chalk, and was therefore saturated with air which must have been furnished by the alkali.

A dram of pure salt of tartar was dissolved in fourteen pounds of lime-water, and the powder thereby precipitated, being carefully collected and dried, weighed one and fifty grains. When exposed to a violent fire, it was converted into a true quick-lime, and had every other quality of a calcarious earth.

This experiment was repeated with the volatile alkali, and also with the fossil or alkali of sea-salt, and exactly with the same event.

The third proposition had less appearance of probability than the foregoing; but, as an accurate experiment was the only test of its truth, I reduced eight grains of perfect quick-lime made of chalk, to an exceedingly subtile powder, by slaking it in two drams of distilled water boiling hot, and immediately threw the mixture into eighteen ounces of distilled water in a flask. After shaking it, a light sediment, which floated thro' the liquor, was allowed to subside; and this, when collected with the greatest care, and dryed, weighed, as near as I could guess, one third of a grain. The water tasted strongly of the lime, had all the qualities of lime-water, and yielded twelve grains of precipitate, upon the addition of salt of tartar. In repeating this experiment, the quantity of sediment was sometimes less than the above, and sometimes amounted to half a grain. It consisted partly of an earth which effervesced violently with aqua fortis, and partly of an ochry powder, which would not dissolve in that acid. The ochry powder, as it usually appears in chalk to the eye, in the form of veins running thro' its substance, must be considered only as an accidental or foreign admixture; and, with respect to the minute portion of alkaline earth which composed the remainder of the sediment, it cannot be supposed to have been originally different from the rest, and incapable, from its nature, of being converted into quick-lime, or of being dissolved in water; it seems rather to have consisted of a small part of the chalk in its mild state, or saturated with air, which had either remained, for want of a sufficient fire to drive it out entirely, or had been furnished by the distilled water.

I indeed expected to see a much larger quantity of sediment produced from the lime, on account of the air which water constantly contains, and with a view to know whether water retains its air when fully saturated with lime, a lime-water was made as strong as possible; four ounces of which were placed under the receiver of an air-pump, together with four ounces of common water in a phial of the same size; and, upon exhausting the receiver, without heating the phials, the air arose from each, in nearly the same quantity: from whence it is evident, that the air, which quick-lime attracts, is of a different kind from that which is mixed with water. And that it is also different from common elastic air, is sufficiently proved by daily experience; for lime-water, which soon attracts air, and forms a crust when exposed in open and shallow vessels, may be preserved, for any time, in bottles which are but slightly corked, or closed in such a manner as would allow free access to elastic air, were a vacuum formed in the bottle. Quick-lime therefore does not attract air when in its most ordinary form, but is capable of being joined to one particular species only, which is dispersed thro' the atmosphere, either in the shape of an exceedingly subtle powder, or more probably in that of an elastic fluid. To this I have given the name of fixed air, and perhaps very improperly; but I thought it better to use a word already familiar in philosophy, than to invent a new name, before we be more fully acquainted with the nature and properties of this substance, which will probably be the subject of my further inquiry.