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–90°, failed. No appearance of liquefaction could. be observed.
Professor Charles Olszewski, of Cracow, the well-known authority on the constants of liquefied gases at low temperatures, kindly offered to make experiments on the liquefaction of argon. His results are embodied in a separate communication, but it is allowable to state here that the gas has a lower critical temperature (-121°) and a lower boiling point (-1870) than oxygen, and that he has succeeded in solidifying argon to white crystals, melting at -189•6o. The density of the liquid is approximately 1.5, that of oxygen being 1.124, and of nitrogen 0.885. The sample of gas he experimented with was exceptionally pure, and had been prepared by help of magnesium. It showed no trace of nitrogen when examined in a vacuum tube.
XIV. Ratio of Specific Heats. In order to decide regarding the elementary or compound nature of argon, experiments were made on the velocity of sound in it. It will be remembered that, from the velocity of sound in a gas, the ratio of specific heat at constant pressure to that at constant volume can be deduced by means of the equation
when n is the frequency, a the wave-length of sound, v its velocity, e the isothermal elasticity, d the density, (1 + at) the temperature correction, C, the specific heat at constant pressure, and C, that at constant volume. In comparing two gases at the same temperature, each of which obeys Boyle's law with sufficient approximation, and in using the same sound, many of these terms disappear, and the ratio of specific heats of one gas may be deduced from that of the other, if known, by means of the proportion
1'd:'d' :: 1:41 : x where, for example, à and d refer to air, of which the ratio is 1:41, according to observations by Röntgen, Wüllner, Kayser, and Jamin and Richard.
Two completely different series of observations, one in a tube of about 2mm. diameter, and one in one of 8mm., made with entirely different samples of gas, gave, the first, 1.65 as the ratio, and, the second, 1.61.
Experiments made with the first tube, to test the accuracy of its working, gave for carbon dioxide the ratio 1.276, instead of 1.288, the mean of all previous determinations; and the half wave-length of sound in hydrogen was found to be 73.6, instead of 74.5, the mean of those previously found. The ratio of the specific heats of hydrogen found was 1:39, instead of 1.402.
There can be no doubt, therefore, that argon gives practically the ratio of specific heats, viz: 1.66, proper to a gas in which all the energy is translational. The only other gas which has been found to behave similarly is mercury gas, at a high temperature.*
XV. Attempts to induce Chemical Combination. Many attempts to induce argon to combine will be described in full in the complete paper. Suffice it to say here, that all such attempts have as yet proved abortive. Argon does not combine witli oxygen in presence of alkali under the influence of the electric discharge, nor with hydrogen in presence of acid or alkali also when sparked; nor with chlorine, dry or moist, when sparked; nor with phosphorus at a bright-red heat, nor with sulphur at bright redness. Tellurium may be distilled in a current of the gas; so may sodium and potassium, their metallic luster remaining unchanged. It is unabsorbed by passing it over fused red-hot caustic soda, or soda-lime heated to bright redness; it passes unaffected over fused and bright red-hot potassium nitrate; and red-hot sodium peroxide does not combine with it. Persulphides of sodium and calcium are also without action at a red heat. Platinum black does not absorb it, nor does platinum sponge, and wet oxidizing and chlorinating agents, such as nitro-hydrochloric acid, bromine water, bromine and alkali, and hydrochloric acid and potassium permanganate, are entirely without action. Experiments with fluorine are in contemplation, but the difficulty is great; and an attempt will be made to produce a carbon arc in the gas. Mixtures of sodium and silica and of sodium and boracic anhydride are also without action, hence it appears to resist attack by nascent silicon and by nascent boron.
XVI. General Conclusions. It remains, finally, to discuss the probable nature of the gas, or mixture of gases, which we have succeeded in separating from atmospheric air, and which we provisionally name argon.
The presence of argon in the atmosphere is proved by many lines of evidence. The high density of “atmospheric nitrogen,” the lower density of nitrogen from chemical sources,
* Kundt and Warburg, Pogg. Ann. vol. CXXIV, pp. 337 and 527.
and the uniformity in the density of samples of chemical nitrogen prepared from different compounds, lead to the conclusion that the cause of the anomaly is the presence of a heavy gas in air. If that gas possess the density 20 compared with hydrogen, “atmospheric ” nitrogen should contain of it approximately 1 per cent. This is, in fact, found to be the case. Moreover, as nitrogen is removed from air by means of red-hot magnesium, the density of the remaining gas rises proportionately to the concentration of the heavier constituent.
Second. This gas has been concentrated in the atmosphere by diffusion. It is true that it has not been freed from oxygen and nitrogen by diffusion, but the process of diffusion increases, relatively to nitrogen, the ainount of argon in that portion which does not pass through the porous walls. This has been proved by its increase in density.
Third. As the solubility of argon in water is relatively high, it is to be expected that the density of the mixture of argon and nitrogen, pumped out of water along with oxygen, should, after the removal of the oxygen, be higher than that of “ atmospheric” nitrogen. Experiment has shown that the density is considerably increased.
Fourth. It is in the highest degree improbable that two processes, so different from each other, should manufacture the same product. The explanation is simple if it be granted that these processes merely eliminate nitrogen from an “atmospheric” mixture. Moreover, as argon is an element, or a mixture of elements, its manufacture would mean its separation from one of the substances employed. The gas which can be removed from red-hot magnesium in a vacuum has been found to be wholly hydrogen. Nitrogen from chemical sources has been practically all absorbed by magnesium, and also when sparked in presence of oxygen; hence argon cannot have resulted from the decomposition of nitrogen. That it is not produced from oxygen is sufficiently borne out by its preparation by means of magnesium.
Other arguments could be adduced, but the above are suffi. cient to justify the conclusion that argon is present in the atmosphere.
The identity of the leading lines in the spectrum, the similar solubility and the similar density, appear to prove the identity of the argon prepared by both processes.
Argon is an element, or a mixture of elements, for Clausius has shown that if K be the energy of translatory motion of the molecules of a gas, and H their whole kinetic energy, then
C, and C, denoting as usual the specific heat at constant pressure and at constant volume respectively.
Hence if, as for mercury vapor and for argon (SXIV), the ratio of specific heats C, :C, be 18, it follows that K = H, or that the whole kinetic energy of the gas is accounted for by the translatory motion of its molecules. In the case of mercury the absence of interatomic energy is regarded as proof of the monatomic character of the vapor, and the conclusion holds equally good for argon.
The only alternative is to suppose that if argon molecules are di. or polyatomic, the atoms acquire no relative motion, even of rotation, a conclusion exceedingly improbable in itself and one postulating the sphericity of such complex groups of atoms.
Now a monatomic gas can be only an element, or a mixture of elements; and hence it follows that argon is not of a com: pound nature.
From Avogadro's law, the density of a gas is half its molecular weight; and as the density of argon is approximately 20, hence its molecular weight must be 40. But its molecule is identical with its atom; hence its atomic weight, or, if it be a mixture, the mean of the atomic weights of that mixture, taken for the proportion in which they are present, must be 40.
There is evidence both for and against the hypothesis that argon is a mixture : for, owing to Mr. Crookes's observations of the dual character of its spectrum; against, because of Professor Olszewski's statement that it has a definite melting point, a definite boiling point, and a definite critical temperature and pressure, and because on compressing the gas in presence of its liquid, pressure remains sensibly constant until all gas has condensed to liquid. The latter experiments are the wellknown criteria of a pure substance; the former is not known with certainty to be characteristic of a mixture. The conclusions which follow are, however, so startling, that in our future experimental work we shall endeavor to decide the question by other means.
For the present, however, the balance of evidence seeins to point to simplicity. We have therefore to discuss the relations to other elements of an element of atomic weight 40. We inclined for long to the view that argon was possibly one or more than one of the elements which might be expected to follow fluorine in the periodic classification of the elementselements which should have an atomic weight between 19, that of fluorine, and 23, that of sodium. But this view is completely put out of court by the discovery of the monatomic nature of its molecules.
The series of elements possessing atomic weights near 40 are :Chlorine ...
44.0 There can be no doubt that potassium, calcium, and scan. dium follow legitimately their predecessors in the vertical columns, lithium, beryllium, and boron, and that they are in almost certain relation with rubidium, strontium, and (but not so certainly) yttrium. If argon be a single element, then there is reason to doubt whether the periodic classification of the elements is complete; whether, in fact, elements may not exist which cannot be fitted among those of which it is composed. On the other hand, if argon be a inixture of two elements, they might find place in the eighth group, one after chlorine and one after bromine. Assuming 37 (the approximate mean between the atomic weights of chlorine and potassium) to be the atomic weight of the lighter element, and 40 the mean atomic weight found, and supposing that the second element has an atomic weight between those of bromine, 80, and rubidium, 85.5, viz: 82, the mixture should consist of 93:3 per cent. of the lighter, and 6:7 per cent. of the heavier element. But it appears improbable that such a high percentage as 6.7 of a heavier element should have escaped detection during liquefaction.
If it be supposed that argon belongs to the eighth group, then its properties would fit fairly well with what might be anticipated. For the series, which contains
Si,", P. 11 and V, Sito.", and C1,1 to VII, might be expected to end with an element of monatomic molecules, of no valency, i.e. incapable of forming a compound, or if forming one, being an octad; and it would forin a possible transition to potassium, with its monovalence, on the other hand. Such conceptions are, however, of a speculative nature; yet they may be perhaps excused, if they in any way lead to experiments which tend to throw more light on the anomalies of this curious element.
In conclusion, it need excite no astonishment that argon is so indifferent to reagents. For mercury, although a monatomic element, forms compounds which are by no means stable at a high temperature in the gaseous state; and attempts to produce compounds of argon may be likened to attempts to cause combination between mercury gas at 800° and other elements. As for the physical condition of argon, that of a gas,