The Liquefaction of Gases/On the Condensation of Several Gases into Liquids
II. ON THE CONDENSATION of SEVERAL
GASES INTO LIQUIDS.
Read April 10, 1823.
I HAD the honour, a few weeks since, of submitting to the Royal Society a paper on the reduction of chlorine to the liquid state. An important note was added to the paper by the President, on the general application of the means used in this case to the reduction of other gaseous bodies to the liquid state; and in illustration of the process, the production of liquid muriatic acid was described. Sir Humphry Davy did me the honour to request I would continue the experiments, which I have done under his general direction, and the following are some of the results already obtained:
Mercury and concentrated sulphuric acid were sealed up in a bent tube, and, being brought to one end, heat was carefully applied, whilst the other end was preserved cool by wet bibulous paper. Sulphurous acid gas was produced where the heat acted, and was condensed by the sulphuric acid above; but, when the latter had become saturated, the sulphurous acid passed to the cold end of the tube, and was condensed into a liquid. When the whole tube was cold, if the sulphurous acid were returned on to the mixture of sulphuric acid and sulphate of mercury, a portion was re-absorbed, but the rest remained on it without mixing.
Liquid sulphurous acid is very limpid and colourless, and highly fluid. Its refractive power, obtained by comparing it in water and other media, with water contained in a similar tube, appeared to be nearly equal to that of water. It does not solidify or become adhesive at a temperature of 0° F. When a tube containing it was opened, the contents did not rush out as with explosion, but a portion of the liquid evaporated rapidly, cooling another portion so much as to leave it in the fluid state at common barometric pressure. It was however rapidly dissipated, not producing visible fumes, but producing the odour of pure sulphurous acid, and leaving the tube quite dry. A portion of the vapour of the fluid received over a mercurial bath, and examined, proved to be sulphurous acid gas. A piece of ice dropped into the fluid instantly made it boil, from the heat communicated by it.
To prove in an unexceptionable manner that the fluid was pure sulphurous acid, some sulphurous acid gas was carefully prepared over mercury, and a long tube perfectly dry, and closed at one end, being exhausted, was filled with it; more sulphurous acid was then thrown in by a condensing syringe, till there were three or four atmospheres; the tube remained perfectly clear and dry, but on cooling one end to 0°, the fluid sulphurous acid condensed, and in all its characters was like that prepared by the former process.
A small gage was attached to a tube in which sulphurous acid was afterwards formed, and at a temperature of 45° F. the pressure within the tube was equal to three atmospheres, there being a portion of liquid sulphurous acid present: but as the common air had not been excluded when the tube was sealed, nearly one atmosphere must be due to its presence, so that sulphurous acid vapour exerts a pressure of about two atmospheres at 45° F. Its specific gravity was nearly 1.42.
A tube being bent, and sealed at the shorter end, strong muriatic acid was poured in through a small funnel, so as nearly to fill the short leg without soiling the long one. A piece of platinum foil was then crumpled up and pushed in, and upon that were put fragments of sulphuret of iron, until the tube was nearly full. In this way action was prevented until the tube was sealed. If it once commences, it is almost impossible to close the tube in a manner sufficiently strong, because of the pressing out of the gas. When closed, the muriatic acid was made to run on to the sulphuret of iron, and then left for a day or two. At the end of that time, much proto-muriate of iron had formed, and on placing the clean end of the tube in a mixture of ice and salt, warming the other end if necessary by a little water, sulphuretted hydrogen in the liquid state distilled over.
The liquid sulphuretted hydrogen was colourless, limpid, and excessively fluid. Ether, when compared with it in similar tubes, appeared tenacious and oily. It did not mix with the rest of the fluid in the tube, which was no doubt saturated, but remained standing on it. When a tube containing it was opened, the liquid immediately rushed into vapour; and this being done under water, and the vapour collected and examined, it proved to be sulphuretted hydrogen gas. As the temperature of a tube containing some of it rose from 0° to 45°, part of the fluid rose in vapour, and its bulk diminished; but there was no other change: it did not seem more adhesive at 0° than at 45°. Its refractive power appeared to be rather greater than that of water; it decidedly surpassed that of sulphurous acid. A small gage being introduced into a tube in which liquid sulphuretted hydrogen was afterwards produced, it was found that the pressure of its vapour was nearly equal to 17 atmospheres at the temperature of 50°.
The gages used were made by drawing out some tubes at the blow-pipe table until they were capillary, and of a trumpet form; they were graduated by bringing a small portion of mercury successively into their different parts; they were then sealed at the fine end, and a portion of mercury placed in the broad end; and in this state they were placed in the tubes, so that none of the substances used, or produced, could get to the mercury, or pass by it to the inside of the gage. In estimating the number of atmospheres, one has always been subtracted for the air left in the tube.
The specific gravity of sulphuretted hydrogen appeared to be 0.9.
The materials used in the production of carbonic acid, were carbonate of ammonia and concentrated sulphuric acid; the manipulation was like that described for sulphuretted hydrogen. Much stronger tubes are however required for carbonic acid than for any of the former substances, and there is none which has produced so many or more powerful explosions. Tubes which have held fluid carbonic acid well for two or three weeks together, have, upon some increase in the warmth of the weather, spontaneously exploded with great violence; and the precautions of glass masks, goggles, &c. which are at all times necessary in pursuing these experiments, are particularly so with carbonic acid.
Carbonic acid is a limpid colourless body, extremely fluid, and floating upon the other contents of the tube. It distils readily and rapidly at the difference of temperature between 32° and 0°. Its refractive power is much less than that of water. No diminution of temperature to which I have been able to submit it, has altered its appearance. In endeavouring to open the tubes at one end, they have uniformly burst into fragments, with powerful explosions. By inclosing a gage in a tube in which fluid carbonic acid was afterwards produced, it was found that its vapour exerted a pressure of 36 atmospheres at a temperature of 32°.
It may be questioned, perhaps, whether this and other similar fluids obtained from materials containing water, do not contain a portion of that fluid; in as much as its absence has not been proved, as it may be with chlorine, sulphurous acid, cyanogen, and ammonia. But besides the analogy which exists between the latter and the former, it may also be observed in favour of their dryness, that any diminution of temperature causes the deposition of a fluid from the atmosphere, precisely like that previously obtained; and there is no reason for supposing that these various atmospheres, remaining as they do in contact with concentrated sulphuric acid, are not as dry as atmospheres of the same kind would be over sulphuric acid at common pressure.
Fluid euchlorine was obtained by inclosing chlorate of potash and sulphuric acid in a tube, and leaving them to act on each other for 24 hours. In that time there had been much action, the mixture was of a dark reddish brown, and the atmosphere of a bright yellow colour. The mixture was then heated up to 100°, and the unoccupied end of the tube cooled to 0°; by degrees the mixture lost its dark colour, and a very fluid ethereal looking substance condensed. It was not miscible with a small portion of the sulphuric acid which lay beneath it; but when returned on to the mass of salt and acid, it was gradually absorbed, rendering the mixture of a much deeper colour even than itself.
Euchlorine thus obtained is a very fluid transparent substance, of a deep yellow colour. A tube containing a portion of it in the clean end, was opened at the opposite extremity; there was a rush of euchlorine vapour, but the salt plugged up the aperture: whilst clearing this away, the whole tube burst with a violent explosion, except the small end in a cloth in my hand, where the euchlorine previously lay, but the fluid had all disappeared.
Some nitrate of ammonia, previously made as dry as could be by partial decomposition, by heat in the air, was sealed up in a bent tube, and then heated in one end, the other being preserved cool. By repeating the distillation once or twice in this way, it was found, on after-examination, that very little of the salt remained undecomposed. The process requires care. I have had many explosions occur with very strong tubes, and at considerable risk.
When the tube is cooled, it is found to contain two fluids, and a very compressed atmosphere. The heavier fluid on examination proved to be water, with a little acid and nitrous oxide in solution; the other was nitrous oxide. It appears in a very liquid, limpid, colourless state; and so volatile that the warmth of the hand generally makes it disappear in vapour. The application of ice and salt condenses abundance of it into the liquid state again. It boils readily by the difference of temperature between 50° and 0°. It does not appear to have any tendency to solidify at -10°. Its refractive power is very much less than that of water, and less than any fluid that has yet been obtained in these experiments, or than any known fluid. A tube being opened in the air, the nitrous oxide immediately burst into vapour. Another tube opened under water, and the vapour collected and examined, it proved to be nitrous oxide gas. A gage being introduced into a tube, in which liquid nitrous oxide was afterwards produced, gave the pressure of its vapour as equal to above 50 atmospheres at 45°.
Some pure cyanuret of mercury was heated until perfectly dry. A portion was then inclosed in a green glass tube, in the same manner as in former instances, and being collected to one end, was decomposed by heat, whilst the other end was cooled. The cyanogen soon appeared as a liquid: it was limpid, colourless, and very fluid; not altering its state at the temperature of 0°. Its refractive power is rather less, perhaps, than that of water. A tube containing it being opened in the air, the expansion within did not appear to be very great; and the liquid passed with comparative slowness into the state of vapour, producing great cold. The vapour, being collected over mercury, proved to be pure cyanogen.
A tube was sealed up with cyanuret of mercury at one end, and a drop of water at the other; the fluid cyanogen was then produced in contact with the water. It did not mix, at least in any considerable quantity, with that fluid, but floated on it, being lighter, though apparently not so much so as ether would be. In the course of some days, action had taken place, the water had become black, and changes, probably such as are known to take place in an aqueous solution of cyanogen, occurred. The pressure of the vapour of cyanogen appeared by the gage to be 3.6 or 3.7 atmospheres at 45° F. Its specific gravity was nearly 0.9.
In searching after liquid ammonia, it became necessary, though difficult, to find some dry source of that substance; and I at last resorted to a compound of it, which I had occasion to notice some years since with chloride of silver. When dry chloride of silver is put into ammoniacal gas, as dry as it can be made, it absorbs a large quantity of it; 100 grains condensing above 130 cubical inches of the gas: but the compound thus formed is decomposed by a temperature of 100° F. or upwards. A portion of this compound was sealed up in a bent tube and heated in one leg, whilst the other was cooled by ice or water. The compound thus heated under pressure fused at a comparatively low temperature, and boiled up, giving off ammoniacal gas, which condensed at the opposite end into a liquid.
Liquid ammonia thus obtained was colourless, transparent, and very fluid. Its refractive power surpassed that of any other of the fluids described, and that also of water itself. From the way in which it was obtained, it was evidently as free from water as ammonia in any state could be. When the chloride of silver is allowed to cool, the ammonia immediately returns to it, combining with it, and producing the original compound. During this action a curious combination of effects takes place: as the chloride absorbs the ammonia, heat is produced, the temperature rising up nearly to 100°; whilst a few inches off, at the opposite end of the tube, considerable cold is produced by the evaporation of the fluid. When the whole is retained at the temperature of 60°, the ammonia boils till it is dissipated and re-combined. The pressure of the vapour of ammonia is equal to about 6.5 atmospheres at 50°. Its specific gravity was 0.76.
When made from pure muriate of ammonia and sulphuric acid, liquid muriatic acid is obtained colourless, as Sir Humphry Davy had anticipated. Its refractive power is greater than that of nitrous oxide, but less than that of water; it is nearly equal to that of carbonic acid. The pressure of its vapour at the temperature of 50°, is equal to about 40 atmospheres.
The refractive power of fluid chlorine is rather less than that of water. The pressure of its vapour at 60° is nearly equal to 4 atmospheres.
Attempts have been made to obtain hydrogen, oxygen, fluoboracic, fluosilicic, and phosphuretted hydrogen gases in the liquid state; but though all of them have been subjected to great pressure, they have as yet resisted condensation. The difficulty with regard to fluoboric gas consists, probably, in its affinity for sulphuric acid, which, as Dr. Davy has shown, is so great as to raise the sulphuric acid with it in vapour. The experiments will however be continued on these and other gases, in the hopes that some of them, at least, will ultimately condense.
- [From Philosophical Transactions for 1823, Vol. 113, pp. 189-198.]
- I am indebted to Mr. Davies Gilbert, who examined with much attention the results of these experiments, for the suggestion of the means adopted to obtain the specific gravity of some of these fluids. A number of small glass bulbs were blown and hermetically sealed; they were then thrown into alcohol, water, sulphuric acid, or mixtures of these, and when any one was found of the same specific gravity as the fluid in which it was immersed, the specific gravity of the fluid was taken: thus a number of hydrometrical bulbs were obtained; these were introduced into the tubes in which the substances were to be liberated; and ultimately, the dry liquids obtained, in contact with them. It was then observed whether they floated or not, and a second set of experiments were made with bulbs lighter or heavier as required, until a near approximation was obtained. Many of the tubes burst in the experiments, and in others difficulties occurred from the accidental fouling of the bulb by the contents of the tube. One source of error may be mentioned in addition to those which are obvious, namely, the alteration of the bulk of the bulb by its submission to the pressure required to keep the substance in the fluid state.
- Quarterly Journal of Science, Vol. V. p. 74.