ARGON, A NEW CONSTITUENT OF THE ATMOSPHERE Written by PROFESSOR MENDELÉEFF IN FEBRUARY 1895 The remarks made in Chapter V., Note 16 bis respecting the newly discovered constituent of the atmosphere are here supplemented by data (taken from the publications of the Royal Society of London) given by the discoverers Lord Rayleigh and Professor Ramsay in January 1895, together with observations made by Crookes and Olszewsky upon the same subject. This gas, which was discovered by Rayleigh and Ramsay in atmospheric nitrogen, was named argon When it became known (Chapter V., Note 4 bis) that the nitrogen obtained from air (by removing the oxygen, moisture and CO2, by various reagents) has a greater density than that obtained from the various (oxygen, hydrogen and metallic) compounds of nitrogen, it was a plausible explanation that the latter contained an admixture of hydrogen, or of some other light gas lowering the density of the mixture. But such an assumption is refuted not only by the fact that the nitrogen obtained from its various compounds (after purification) has always the same density (although the supposed impurities mixed with it should vary), but also by Rayleigh and Ramsay's experiment of artificially adding hydrogen to nitrogen, and then passing the mixture over red-hot oxide of copper, when it was found that the nitrogen regained its original density, i.e. that the whole of the hydrogen was removed by this treatment. Therefore the difference in the density of the two varieties of nitrogen had to be explained by the presence of a heavier gas in admixture with the nitrogen obtained from the atmosphere. This hypothesis was confirmed by the fact that Rayleigh and Ramsay having obtained purified nitrogen (by removing the O2, CO2, and H2O), both from ordinary air and from air which had been previously subjected to atmolysis, that is which had been passed through porous tubes (of burnt clay, e.g. pipe-stem), surrounded by a rarefied space, and so deprived of its lighter constituents (chiefly nitrogen), found that the nitrogen from the air which had been subjected to atmolysis was heavier than that obtained from air which had not been so treated. This experiment showed that the nitrogen of air contains an admixture of a gas which, being heavier than nitrogen itself, Thus the first positive and very important fact respecting argon is that its specific gravity is nearly 20—that is, that it is 20 times heavier than hydrogen, while nitrogen is only 14 times and oxygen 16 times heavier than hydrogen. This explains the difference observed by Rayleigh between the densities of nitrogen obtained from its compounds and from the atmosphere (Chapter V., Note 4 bis). At 0° and 760 mm. a litre of the former gas weighs 1·2505 grm., while a litre of the latter weighs 1·2572, or taking H = 1, the density of the first = 13·916, and of the latter = 13·991. If the density of argon be taken as 20, it is contained in atmospheric nitrogen to the extent of about 1·23 per cent. by volume, whilst air contains about 0·97 per cent. by volume. When argon had been isolated the question naturally arose, was it a new homogeneous substance having definite properties or was it a mixture of gases? The former may now be positively asserted, namely, that argon is a peculiar gas previously unknown to chemistry. Such a conviction is in the first place established by the fact that argon has a greater number of negative properties, a smaller capacity for reaction, than any other simple or compound body known. The most inert gas known is nitrogen, but argon far exceeds it in this respect. Thus nitrogen is absorbed at a red heat by many metals, with the formation of nitrides, while argon, as is seen in the mode of its preparation and by direct experiment, does not possess this property. Nitrogen, under the action of electric sparks, combines with hydrogen in the presence of acids and with oxygen in the presence of alkalis, while argon is unable to do so, as is seen from the method of separation from nitrogen. Rayleigh and Ramsay also proved that argon is unable to react with chlorine (dry or moist) either directly or under the action of an electric discharge, or with phosphorus or sulphur, at a red heat. Sodium, potassium, and tellurium may be distilled in an atmosphere of argon without change. Fused caustic soda, incandescent soda-lime, molten nitre, red-hot peroxide of sodium, and the polysulphides of calcium and sodium also do not react with argon. Platinum black does not absorb it, and spongy platinum is unable to excite its reaction with oxygen or chlorine. Aqua regia, bromine water, and a mixture of hydrochloric acid and KMnO4 were also without action upon argon. Besides which it is evident from the method of its preparation that it is not acted upon by red-hot oxide of copper. All these facts exclude any possibility of argon containing any already known body, and prove it to be the most inert of all the gases known. But besides these negative points, the independency of argon is 1. The spectrum of argon observed by Crookes under a low pressure (in Geissler-PlÜcker tubes) distinguishes it from other gases. 2. According to Rayleigh and Ramsay the solubility of argon in water is approximately 4 volumes in 100 volumes of water at 13°. Thus argon is nearly 2½ times more soluble than nitrogen, and its solubility approaches that of oxygen. Direct experiment proves that nitrogen obtained from air from boiled water is heavier than that obtained straight from the atmosphere. This again is an indirect proof of the presence of argon in air. 3. The ratio k of the two specific heats (at a constant pressure and at 4. Argon was liquefied by Professor Olszewsky, who is well known for his classical researches upon liquefied gases. These researches have an especial interest since they show that argon exhibits a perfect constancy in its The discovery of argon is one of the most remarkable chemical acquisitions of recent times, and we trust that Lord Rayleigh and Professor Ramsay, who made this wonderful discovery, will further elucidate the true nature of argon, as this should widen the fundamental principles of chemistry, to which the chemists of Great Britain have from early times made such valuable contributions. It would be premature now to give any definite opinions upon so new a subject. Only one thing can be said; argon is so inert that its rÔle in nature cannot be considerable, notwithstanding its presence in the atmosphere. But as the atmosphere itself plays such a vast part in the life of the surface of the earth, every addition to our knowledge of its composition must directly or indirectly react upon the sum total of our knowledge of nature. Footnotes:
While if we place argon in a similar manner,
although from a numerical point of view there is a similar sequence to the above, still from a chemical and physical point of view the result is quite different, as there is no such resemblance between the properties of O, F and Na, Mg, as between Cr, Mn, and Cu, Zn. I repeat that only the typical character of the elements with small atomic weights can justify the atomic weight A = 20, and the placing of argon in Group VIII. amongst the typical elements; then N, O, F, A are a series of gases. It appears to me simpler to assume that argon contains N3, especially as argon is present in nitrogen and accompanies it, and, as a matter of fact, none of the observed properties of argon are contradictory to this hypothesis. These observations were written by me in the beginning of February 1895, and on the 29th of that month I received a letter, dated February 25, from Professor Ramsay informing me that ‘the periodic classification entirely corresponds to its (argon's) atomic weight, and that it even gives a fresh proof of the periodic law,’ judging from the researches of my English friends. But in what these researches consisted, and how the above agreement between the atomic weight of argon and the periodic system was arrived at, is not referred to in the letter, and we remain in expectation of a first publication of the work of Lord Rayleigh and Professor Ramsey. [For more complete information see papers read before the Royal Society, January 31, 1895, February 13, March 10, and May 21, 1896, and a paper published in the Chemical Society's Transactions, 1895, p. 684. For abstracts of these and other papers on argon and helium, and correspondence, see ‘Nature,’ 1895 and 1896.
where tc is the absolute (critical) boiling point, pc the pressure (critical) in atmospheres corresponding to it, t the boiling point (under a pressure of 760 mm.), t1 the melting point, and s the specific gravity in a liquid state at t. The above shows that argon in its properties in a liquid state stands near to oxygen (as it also does in its solubility), but that all the temperatures relating to it (tc, t, and t1) are higher than for nitrogen. This fully answers, not only to the higher density of argon, but also to the hypothesis that it contains N3. And as the boiling point of argon differs from that of nitrogen and oxygen by less than 10°, and its amount is small, it is easy to understand how Dewar (1894), who tried to separate it from liquid air and nitrogen by fractional distillation, was unable to do so. The first and last portions were identical, and nitrogen from air showed no difference in its liquefaction from that obtained from its compounds, or from that which had been passed through a tube containing incandescent magnesium. Still, it is not quite clear why both kinds of nitrogen, after being passed over the magnesium in Dewar's experiments, exhibited an almost similar alteration in their properties, independent of the appearance of a small quantity of hydrogen in them. Concluding Remarks (March 31, 1895).—The ‘Comptes rendus’ of the Paris Academy of Sciences of March 18, 1895, contains a memoir by Berthelot upon the reaction of argon with the vapour of benzene under the action of a silent discharge. In his experiments, Berthelot succeeded in treating 83 per cent. of the argon taken for the purpose, and supplied to him by Ramsay (37 c.c. in all). The composition of the product could not be determined owing to the small amount obtained, but in its outward appearance it quite resembled the product formed under similar conditions by nitrogen. This observation of the famous French chemist to some extent supports the supposition that argon is a polymerised variety of nitrogen whose molecule contains N3, while ordinary nitrogen contains N2. Should this supposition be eventually verified, the interest in argon will not only not lessen, but become greater. For this, however, we must wait for further observations and detailed experimental data from Rayleigh and Ramsay. The latest information obtained by me from London is that Professor Ramsay, by treating cleveite (containing PbO, UO3, Y2O3, &c.) with sulphuric acid, obtained argon, and, judging by the spectrum, helium also. The accumulation of similar data may, after detailed and diversified research, considerably increase the stock of chemical knowledge which, constantly widening, cannot be exhaustively treated in these ‘Principles of Chemistry,’ although very probably furnishing fresh proof of the ‘periodicity of the elements.’ |