The Liquefaction of Gases/Note-Additional Remarks Respecting the Condensation of Gases
Note.—Additional remarks respecting the Condensation of Gases.
Received February 20,—Read February 20, 1845.
Nitrous oxide.—Suspecting the presence on former occasions of nitrogen in the nitrous oxide, and mainly because of muriate in the nitrate of ammonia used, I prepared that salt in a pure state from nitric acid and carbonate of ammonia previously proved, by nitrate of silver, to be free from muriatic acid. After the nitrous oxide prepared from this salt had remained for some days in well-closed bottles in contact with a little water, I condensed it in the manner already described, and when condensed I allowed half the fluid to escape in vapour, that as much as possible of the less condensable portion might be carried off. In this way as much gas as would fill the capacity of the vessels twenty or thirty times or more was allowed to escape. Afterwards the following series of pressures was obtained:—
These numbers may all be taken as the results of experiments. Where the temperatures are not those actually observed, they are in almost all cases within a degree of it, and proportionate to the effects really observed. The departure of the real observations from the numbers given is very small. This table I consider as far more worthy of confidence than the former, and yet it is manifest that the curve is not consistent with the idea of a pure single substance, for the pressures at the lowest temperature are too high. I believe that there are still two bodies present, and that the more volatile, as before said, is condensable in the liquid of the less volatile; but I think there is a far smaller proportion of the more volatile (nitrogen, or whatever it may be) than in the former case.
Olefiant gas.—The olefiant gas condensed in the former experiment was prepared in the ordinary way, using excellent alcohol and sulphuric acid; then washed by agitation with about half its bulk of water, and finally left for three days over a thick mixture of lime and water with occasional agitation. In this way all the sulphurous and carbonic acids were removed, and I believe all the ether, except such minute portions as could not interfere with my results. In respect of the ether, I have since found that the process is satisfactory; for when I purposely added ether vapour to air, so as to increase its bulk by one-third, treatment like that above removed it, so as to leave the air of its original volume. There was yet a slight odour of ether left, but not so much as that conferred by adding one volume of the vapour of ether to 1200 or 1500 volumes of air. I find that when air is expanded 4th or 3rd more by the addition of the vapour of ether, washing first of all with about 10 of its volume of water, then again with about as much water, and lastly with its volume of water, removes the ether to such a degree, that though a little smell may remain, the air is of its original volume.
As already stated, it is the presence of other and more volatile hydrocarbons than olefiant gas, which the tensions obtained seemed to indicate, both in the gas and the liquid resulting from its condensation. In a further search after these I discovered a property of olefiant gas which I am not aware is known (since I do not find it referred to in books), namely its ready solubility in strong alcohol, ether, oil of turpentine, and such like bodies. Alcohol will take up two volumes of this gas; ether can absorb two volumes; oil of turpentine two volumes and a half; and olive oil one volume by agitation at common temperatures and pressure; consequently, when a vessel of olefiant gas is transferred to a bath of any of these liquids and agitated, absorption quickly takes place.
Examined in this way, I have found no specimen of olefiant gas that is entirely absorbed; a residue always remains, which, though I have not yet had time to examine it accurately, appears to be light carburetted hydrogen; and I have no doubt that this is the substance which has mainly interfered in my former results. This substance appears to be produced in every stage of the preparation of olefiant gas. On taking six different portions of gas at different equal intervals, from first to last, during one process of preparation, after removing the sulphurous and carbonic acid and the ether as before described, then the following was the proportion per cent, of insoluble gas in the remainder when agitated with oil of turpentine, 10.5; 10; 10.1; 13.1; 28.3; 61.8. Whether carbonic oxide was present in any of these undissolved portions I cannot at present say.
In reference to the part dissolved, I wish as yet to guard myself from being supposed to assume that it is one uniform substance; there is indeed little doubt that the contrary is true; for whilst a volume of oil of turpentine introduced into twenty times its volume of olefiant gas cleared from ether and the acids, absorbs 22 volumes of the gas, the same volume of fresh oil of turpentine brought into similar contact with abundance of the gas which remains when one-half has been removed by solution only dissolved 1.54 part, yet there was an abundant surplus of gas which would dissolve in fresh oil of turpentine at this latter rate. When two-thirds of a portion of fresh olefiant gas were removed by solution, the most soluble portion of that which remained required its bulk of fresh oil of turpentine to dissolve it. Hence at first one volume of camphine dissolved 2.50, but when the richer portion of the gas was removed, one volume dissolved 1.54 part; and when still more of the gas was taken away by solution, one volume of camphine dissolved only one volume of the gas. This can only be accounted for by the presence of various compounds in the soluble portion of the gas.
A portion of good olefiant gas was prepared, well-agitated with its bulk of water in close vessels, left over lime and water for three days, and then condensed as before. When much liquid was condensed, a considerable proportion was allowed to escape to sweep out the uncondensed atmosphere and the more condensable vapours; and then the following pressures were observed:—
On examining the form of the curve given by these pressures, it is very evident that, as on former occasions, the pressures at low temperatures are too great to allow the condensed liquid to be considered as one uniform body, and the form of the curve at the higher pressures is quite enough to prove that no ether was present either in this or the former fluids. On permitting the liquid in the tube to expand into gas, and treating 100 parts of that gas with oil of turpentine, eighty-nine parts were dissolved, and eleven parts remained insoluble. There can be no doubt that the presence of this latter substance, soluble as it is under pressure in the more condensable portions, is the cause of the irregularity of the curve, and the too high pressure at the lower temperatures.
The ethereal solution of olefiant gas being mixed with eight or nine times its volume of water, dissolved and gradually minute bubbles of gas appeared, the separation of which was hastened by a little heat. In this way about half the gas dissolved was re-obtained, and burnt like very rich olefiant gas. One volume of the alcoholic solution, with two volumes of water, gave very little appearance of separating gas. Even the application of heat did not at first cause the separation, but gradually about half the dissolved olefiant gas was liberated.
The separation of the dissolved gas by water, heat, or change of pressure from its solutions, will evidently supply means of procuring olefiant gas in a greater state of purity than heretofore; the power of forming these solutions will also very much assist in the correct analysis of mixtures of hydrocarbons. I find that light carburetted hydrogen is hardly sensibly soluble in alcohol or ether, and in oil of turpentine the proportion dissolved is not probably 15th the volume of the fluid employed; but the further development of these points I must leave for the present.
Carbonic acid.—This liquid may be retained in glass tubes furnished with cemented caps, and closed by plugs or stop-cocks, as described, but it is important to remember the softening action on the cement which, being continued, at last reduces its strength below the necessary point. A tube of this kind was arranged on the 10th of January and left; on the 15th of February it exploded, not by any fracture of the tube, for that remained unbroken, but simply by throwing off the cap through a failure of the cement. Hence the cement joints should not be used for long experiments, but only for those enduring for a few days.
Oxygen.—Chlorate of potassa was melted and pulverized. Oxide of manganese was pulverized, heated red-hot for half an hour, mixed whilst hot with the chlorate, and the mixture put into a long strong glass generating tube with a cap cemented on, and this tube then attached to another with a gauge for condensation. The heat of a spirit lamp carefully applied produced the evolution of oxygen without any appearance of water, and the tubes, both hot and cold, sustained the force generated. In this manner the pressure of oxygen within the apparatus was raised as high as 58.5 atmospheres, whilst the temperature at the condensing place was reduced as low as -140° Fahr., but no condensation appeared. A little above this pressure the cement of two of the caps began to leak, and I could carry the observation no further with this apparatus.
From the former scanty and imperfect expressions of the elasticity of the vapour of the condensed gases. Dove. was led to put forth a suggestion, whether it might not ultimately appear that the same addition of heat (expressed in degrees of the thermometer) caused the same additional increase of expansive force for all gases or vapours in contact with their liquids, provided the observation began with the same pressure in all. Thus to obtain the difference between forty-four and fifty atmospheres of pressure, either with steam or nitrous oxide, nearly the same number of degrees of heat were required; to obtain the difference between twenty and twenty-five atmospheres, either with steam or muriatic acid, the same number were required. Such a law would of course make the rate of increasing expansive force the same for all bodies, and the curve laid down for steam would apply to every other vapour. This, however, does not appear to be the case. That the force of the vapour increases in a geometrical ratio for equal increments of heat is true for all bodies, but the ratio is not the same for all. As far as observations upon the following substances, namely, water, sulphurous acid, cyanogen, ammonia, arseniuretted hydrogen, sulphuretted hydrogen, muriatic acid, carbonic acid, defiant gas, &c., justify any conclusion respecting a general law, it would appear that the more volatile a body is, the more rapidly does the force of its vapour increase by further addition of heat, commencing at a given point of pressure for all; thus for an increase of pressure from two to six atmospheres, the following number of degrees require to be added for the different bodies named: water 69°, sulphurous acid 63°, cyanogen 64°.5, ammonia 60°, arseniuretted hydrogen 54°, sulphuretted hydrogen 56°.5, muriatic acid 43°, carbonic acid 32°.5, nitrous oxide 30°; and though some of these numbers are not in the exact order, and in other cases, as of olefiant gas and nitrous oxide, the curves sometimes even cross each other, these circumstances are easily accounted for by the facts already stated of irregular composition and the inevitable errors of first results. There seems every reason therefore to expect that the increasing elasticity is directly as the volatility of the substance, and that by further and more correct observation of the forces, a general law may be deduced, by the aid of which, and only a single observation of the force of any vapour in contact with its fluid, its elasticity at any other temperature may be obtained.
Whether the same law may be expected to continue when the bodies approach near to the Cagniard de la Tour state is doubtful. That state comes on sooner in reference to the pressure required, according as the liquid is lighter and more expansible by heat and its vapour heavier, hence indeed the great reason for its facile assumption by ether. But though with ether, alcohol and water, that substance which is most volatile takes up this state with the lowest pressure, it does not follow that it should always be so; and in fact we know that ether takes up this state at a pressure between thirty-seven and thirty-eight atmospheres, whereas muriatic acid, nitrous oxide, carbonic acid and olefiant gas, which are far more volatile, sustain a higher pressure than this without assuming that peculiar state, and whilst their vapours and liquids are still considerably different from each other. Now whether the curve which expresses the elastic force of the vapour of a given fluid for increasing temperatures continues undisturbed after that fluid has passed the Cagniard de la Tour point or not is not known, and therefore it cannot well be anticipated whether the coming on of that state sooner or later with particular bodies will influence them in relation to the more general law referred to above.
The law already suggested gives great encouragement to the continuance of those efforts which are directed to the condensation of oxygen, hydrogen and nitrogen, by the attainment and application of lower temperatures than those yet applied. If to reduce carbonic acid from the pressure of two atmospheres to that of one, we require to abstract only about half the number of degrees that is necessary to produce the same effect with sulphurous acid, it is to be expected that a far less abstraction will suffice to produce the same effect with nitrogen or hydrogen, so that further diminution of temperature and improved apparatus for pressure, may very well be expected to give us these bodies in the liquid or solid state.
- Water, as Berzelius and others have pointed out, dissolves about 8th its volume of olefiant gas, but I find that it also leaves an insoluble residue, which burns like light carburetted hydrogen.
- Poggendorff's Annalen, xxiii. 290; or Thomson on Heat and Electricity, p. 9.