Discovery of Oxygen Part 1

Discovery of Oxygen.

by Carl Wilhelm Scheele.

Part 2.

PREFACE

The portions of Scheele's "Chemical Treatise on Air and Fire" here reproduced in English are intended to form a companion volume to No. 7 of the Club Reprints, which contains Priestley's account of his discovery of oxygen. Not only have the claims of Scheele to the independent discovery of this gas never been disputed, but the valuable volume of "Letters and Memoranda" of Scheele, edited by Nordenskjold, which was published in 1892, places it beyond doubt that Scheele had obtained oxygen by more than one method at least as early as Priestley's first isolation of the gas, although his printed account of the discovery only appeared about two years after Priestley's. The evidence of this has been found in Scheele's laboratory notes, which are still preserved in the Royal Academy of Science in Stockholm.

In his "Chemical Treatise" Scheele endeavours, at considerable length, to prove by experiments his views as to the compound character of heat and of light. These portions of the work have been entirely omitted from what is reproduced here. All the places where omissions have been made are indicated.

Every care has been taken in the endeavour to make the translation a faithful reproduction of the meaning of the original, whilst literal accuracy has been aimed at rather than literary elegance.

L. D.

CHEMICAL TREATISE ON AIR AND FIRE.[A]

+1.+ It is the object and chief business of chemistry to skilfully separate substances into their const.i.tuents, to discover their properties, and to compound them in different ways.

How difficult it is, however, to carry out such operations with the greatest accuracy, can only be unknown to one who either has never undertaken this occupation, or at least has not done so with sufficient attention.

+2.+ Hitherto chemical investigators are not agreed as to how many elements or fundamental materials compose all substances. In fact this is one of the most difficult problems; some indeed hold that there remains no further hope of searching out the elements of substances.

Poor comfort for those who feel their greatest pleasure in the investigation of natural things! Far is he mistaken, who endeavours to confine chemistry, this n.o.ble science, within such narrow bounds! Others believe that earth and phlogiston are the things from which all material nature has derived its origin. The majority seem completely attached to the peripatetic elements.

+3.+ I must admit that I have bestowed no little trouble upon this matter in order to obtain a clear conception of it. One may reasonably be amazed at the numerous ideas and conjectures which authors have recorded on the subject, especially when they give a decision respecting the fiery phenomenon; and this very matter was of the greatest importance to me. I perceived the necessity of a knowledge of fire, because without this it is not possible to make any experiment; and without fire and heat it is not possible to make use of the action of any solvent. I began accordingly to put aside all explanations of fire; I undertook a mult.i.tude of experiments in order to fathom this beautiful phenomenon as fully as possible. I soon found, however, that one could not form any true judgment regarding the phenomena which fire presents, without a knowledge of the air. I saw, after carrying out a series of experiments, that air really enters into the mixture of fire, and with it forms a const.i.tuent of flame and of sparks. I learned accordingly that a treatise like this, on fire, could not be drawn up with proper completeness without taking the air also into consideration.

[Footnote A: Carl Wilhelm Scheele's Chemische Abhandlung von der Luft und dem Feuer. Upsala and Leipzig, 1777.]

+4.+ Air is that fluid invisible substance which we continually breathe, which surrounds the whole surface of the earth, is very elastic, and possesses weight. It is always filled with an astonis.h.i.+ng quant.i.ty of all kinds of exhalations, which are so finely subdivided in it that they are scarcely visible even in the sun's rays. Water vapours always have the preponderance amongst these foreign particles. The air, however, is also mixed with another elastic substance resembling air, which differs from it in numerous properties, and is, with good reason, called aerial acid by Professor Bergman. It owes its presence to organised bodies, destroyed by putrefaction or combustion.

+5.+ Nothing has given philosophers more trouble for some years than just this delicate acid or so called fixed air. Indeed it is not surprising that the conclusions which one draws from the properties of this elastic acid are not favourable to all who are prejudiced by previously conceived opinions. These defenders of the Paracelsian doctrine believe that the air is in itself unalterable; and, with Hales, that it really unites with substances thereby losing its elasticity; but that it regains its original nature as soon as it is driven out of these by fire or fermentation. But since they see that the air so produced is endowed with properties quite different from common air, they conclude, without experimental proofs, that this air has united with foreign materials, and that it must be purified from these admixed foreign particles by agitation and filtration with various liquids. I believe that there would be no hesitation in accepting this opinion, if one could only demonstrate clearly by experiments that a given quant.i.ty of air is capable of being completely converted into fixed or other kind of air by the admixture of foreign materials; but since this has not been done, I hope I do not err if I a.s.sume as many kinds of air as experiment reveals to me. For when I have collected an elastic fluid, and observe concerning it that its expansive power is increased by heat and diminished by cold, while it still uniformly retains its elastic fluidity, but also discover in it properties and behaviour different from those of common air, then I consider myself justified in believing that this is a peculiar kind of air. I say that air thus collected must retain its elasticity even in the greatest cold, because otherwise an innumerable mult.i.tude of varieties of air would have to be a.s.sumed, since it is very probable that all substances can be converted by excessive heat into a vapour resembling air.

+6.+ Substances which are subjected to putrefaction or to destruction by means of fire diminish, and at the same time consume, a part of the air; sometimes it happens that they perceptibly increase the bulk of the air, and sometimes finally that they neither increase nor diminish a given quant.i.ty of air; phenomena which are certainly remarkable. Conjectures can here determine nothing with certainty, at least they can only bring small satisfaction to a chemical philosopher, who must have his proofs in his hands. Who does not see the necessity of making experiments in this case, in order to obtain light concerning this secret of nature?

+7. General properties of ordinary air.+

(1.) Fire must burn for a certain time in a given quant.i.ty of air. (2.) If, so far as can be seen, this fire does not produce during combustion any fluid resembling air, then, after the fire has gone out of itself, the quant.i.ty of air must be diminished between a third and a fourth part. (3.) It must not unite with common water. (4.) All kinds of animals must live for a certain time in a confined quant.i.ty of air. (5.) Seeds, as for example peas, in a given quant.i.ty of similarly confined air, must strike roots and attain a certain height with the aid of some water and of a moderate heat.

Consequently, when I have a fluid resembling air in its external appearance, and find that it has not the properties mentioned, even when only one of them is wanting, I feel convinced that it is not ordinary air.

+8. Air must be composed of elastic fluids of two kinds.+

+First Experiment.+--I dissolved one ounce of alkaline liver of sulphur in eight ounces of water; I poured 4 ounces of this solution into an empty bottle capable of holding 24 ounces of water, and closed it most securely with a cork; I then inverted the bottle and placed the neck in a small vessel with water; in this position I allowed it to stand for 14 days. During this time the solution had lost a part of its red colour and had also deposited some sulphur: afterwards I took the bottle and held it in the same position in a larger vessel with water, so that the mouth was under and the bottom above the water-level, and withdrew the cork under the water; immediately water rose with violence into the bottle. I closed the bottle again, removed it from the water, and weighed the fluid which it contained. There were 10 ounces. After subtracting from this the 4 ounces of solution of sulphur there remain 6 ounces, consequently it is apparent from this experiment that of 20 parts of air 6 parts have been lost in 14 days.

+9. Second Experiment.+--(_a._) I repeated the preceding experiment with the same quant.i.ty of liver of sulphur, but with this difference that I only allowed the bottle to stand a week, tightly closed. I then found that of 20 parts of air only 4 had been lost. (_b._) On another occasion I allowed the very same bottle to stand 4 months; the solution still possessed a somewhat dark yellow colour. But no more air had been lost than in the first experiment, that is to say 6 parts.

+10. Third Experiment.+--I mixed 2 ounces of caustic ley, which was prepared from alkali of tartar and unslaked lime and did not precipitate lime water, with half an ounce of the preceding solution of sulphur which likewise did not precipitate lime water. This mixture had a yellow colour. I poured it into the same bottle, and after this had stood 14 days, well closed, I found the mixture entirely without colour and also without precipitate. I was enabled to conclude that the air in this bottle had likewise diminished, from the fact that air rushed into the bottle with a hissing sound after I had made a small hole in the cork.

+11. Fourth Experiment.+--(_a._) I took 4 ounces of a solution of sulphur in lime water; I poured this solution into a bottle and closed it tightly. After 14 days the yellow colour had disappeared, and of 20 parts of air 4 parts had been lost. The solution contained no sulphur, but had allowed a precipitate to fall which was chiefly gypsum. (_b._) Volatile liver of sulphur likewise diminishes the bulk of air. (_c._) Sulphur, however, and volatile spirit of sulphur, undergo no alteration in it.

+12. Fifth Experiment.+--I hung up over burning sulphur, linen rags which were dipped in a solution of alkali of tartar. After the alkali was saturated with the volatile acid, I placed the rags in a flask, and closed the mouth most carefully with a wet bladder. After 3 weeks had elapsed I found the bladder strongly pressed down; I inverted the flask, held its mouth in water, and made a hole in the bladder; thereupon water rose with violence into the flask and filled the fourth part.

+13. Sixth Experiment.+--I collected in a bladder the nitrous air which arises on the dissolution of the metals in nitrous acid, and after I had tied the bladder tightly I laid it in a flask and secured the mouth very carefully with a wet bladder. The nitrous air gradually lost its elasticity, the bladder collapsed, and became yellow as if corroded by _aqua fortis_. After 14 days I made a hole in the bladder tied over the flask, having previously held it, inverted, under water; the water rose rapidly into the flask, and it remained only 2/3 empty.

+14. Seventh Experiment.+--(_a._) I immersed the mouth of a flask in a vessel with oil of turpentine. The oil rose in the flask a few lines every day. After the lapse of 14 days the fourth part of the flask was filled with it; I allowed it to stand for 3 weeks longer, but the oil did not rise higher. All those oils which dry in the air, and become converted into resinous substances, possess this property. Oil of turpentine, however, and linseed oil rise up sooner if the flask is previously rinsed out with a concentrated sharp ley. (_b._) I poured 2 ounces of colourless and transparent animal oil of Dippel into a bottle and closed it very lightly; after the expiry of two months the oil was thick and black. I then held the bottle, inverted, under water and drew out the cork; the bottle immediately became 1/4 filed with water.

+15. Eighth Experiment.+--(_a._) I dissolved 2 ounces of vitriol of iron in 32 ounces of water, and precipitated this solution with a caustic ley. After the precipitate had settled, I poured away the clear fluid and put the dark green precipitate of iron so obtained, together with the remaining water, into the before-mentioned bottle (- 8), and closed it tightly. After 14 days (during which time I shook the bottle frequently), this green calx of iron had acquired the colour of crocus of iron, and of 40 parts of air 12 had been lost. (_b._) When iron filings are moistened with some water and preserved for a few weeks in a well closed bottle, a portion of the air is likewise lost. (_c._) The solution of iron in vinegar has the same effect upon air. In this case the vinegar permits the dissolved iron to fall out in the form of a yellow crocus, and becomes completely deprived of this metal. (_d._) The solution of copper prepared in closed vessels with spirit of salt likewise diminishes air. In none of the foregoing kinds of air can either a candle burn or the smallest spark glow.

+16.+ It is seen from these experiments that phlogiston, the simple inflammable principle, is present in each of them. It is known that the air strongly attracts to itself the inflammable part of substances and deprives them of it: not only this may be seen from the experiments cited, but it is at the same time evident that on the transference of the inflammable substance to the air a considerable part of the air is lost. But that the inflammable substance[B] alone is the cause of this action, is plain from this, that, according to the 10th paragraph, not the least trace of sulphur remains over, since, according to my experiments this colourless ley contains only some vitriolated tartar.

The 11th paragraph likewise shews this. But since sulphur alone, and also the volatile spirit of sulphur, have no effect upon the air (- 11.

_c._), it is clear that the decomposition of liver of sulphur takes place according to the laws of double affinity,--that is to say, that the alkalies and lime attract the vitriolic acid, and the air attracts the phlogiston.

[Footnote B: "Das Brennbare."]

It may also be seen from the above experiments, that a given quant.i.ty of air can only unite with, and at the same time saturate, a certain quant.i.ty of the inflammable substance: this is evident from the 9th paragraph, _letter b_. But whether the phlogiston which was lost by the substances was still present in the air left behind in the bottle, or whether the air which was lost had united and fixed itself with the materials such as liver of sulphur, oils, &c., are questions of importance.

From the first view, it would necessarily follow that the inflammable substance possessed the property of depriving the air of part of its elasticity, and that in consequence of this it becomes more closely compressed by the external air. In order now to help myself out of these uncertainties, I formed the opinion that any such air must be specifically heavier than ordinary air, both on account of its containing phlogiston and also of its greater condensation. But how perplexed was I when I saw that a very thin flask which was filled with this air, and most accurately weighed, not only did not counterpoise an equal quant.i.ty of ordinary air, but was even somewhat lighter. I then thought that the latter view might be admissible; but in that case it would necessarily follow also that the lost air could be separated again from the materials employed. None of the experiments cited seemed to me capable of shewing this more clearly than that according to the 10th paragraph, because this residuum, as already mentioned, consists of vitriolated tartar and alkali. In order therefore to see whether the lost air had been converted into fixed air, I tried whether the latter shewed itself when some of the caustic ley was poured into lime water; but in vain--no precipitation took place. Indeed, I tried in several ways to obtain the lost air from this alkaline mixture, but as the results were similar to the foregoing, in order to avoid prolixity I shall not cite these experiments. Thus much I see from the experiments mentioned, that the air consists of two fluids, differing from each other, the one of which does not manifest in the least the property of attracting phlogiston, while the other, which composes between the third and the fourth part of the whole ma.s.s of the air, is peculiarly disposed to such attraction. But where this latter kind of air has gone to after it has united with the inflammable substance, is a question which must be decided by further experiments, and not by conjectures.

We shall now see how the air behaves towards inflammable substances when they get into fiery motion. We shall first consider that kind of fire which does not give out during the combustion any fluid resembling air.

+17. First Experiment.+--I placed 9 grains of phosphorus from urine in a thin flask, which was capable of holding 30 ounces of water, and closed its mouth very tightly. I then heated, with a burning candle, the part of the flask where the phosphorus lay; the phosphorus began to melt, and immediately afterwards took fire; the flask became filled with a white cloud, which attached itself to the sides like white flowers; this was the dry acid of phosphorus. After the flask had become cold again, I held it, inverted, under water and opened it; scarcely had this been done when the external air pressed water into the flask; this water amounted to 9 ounces.

+18. Second Experiment.+--When I placed pieces of phosphorus in the same flask and allowed it to stand, closed, for 6 weeks, or until it no longer glowed, I found that 1/3 of the air had been lost.

+19. Third Experiment.+--I placed 3 teaspoonfuls of iron filings in a bottle capable of holding 2 ounces of water; to this I added an ounce of water, and gradually mixed with them half an ounce of oil of vitriol. A violent heating and fermentation took place. When the froth had somewhat subsided, I fixed into the bottle an accurately fitting cork, through which I had previously fixed a gla.s.s tube A (Fig. 1). I placed this bottle in a vessel filled with hot water, B B (cold water would greatly r.e.t.a.r.d the solution). I then approached a burning candle to the orifice of the tube, whereupon the inflammable air took fire and burned with a small yellowish-green flame. As soon as this had taken place, I took a small flask C, which was capable of holding 20 ounces of water, and held it so deep in the water that the little flame stood in the middle of the flask. The water at once began to rise gradually into the flask, and when the level had reached the point D the flame went out. Immediately afterwards the water began to sink again, and was entirely driven out of the flask. The s.p.a.ce in the flask up to D contained 4 ounces, therefore the fifth part of the air had been lost. I poured a few ounces of lime water into the flask in order to see whether any aerial acid had also been produced during the combustion, but I did not find any. I made the same experiment with zinc filings, and it proceeded in every way similarly to that just mentioned. I shall demonstrate the const.i.tuents of this inflammable air further on; for, although it seems to follow from these experiments that it is only phlogiston, still other experiments are contrary to this.