this for ten days 1,500 c.c. of gas were reduced to 200 cc., and the density increased to 16·1 (if that of H2-1 and N, -14). Further treatment of the remainder brought the density up to 19.09. After adding a small quantity of oxygen and repassing the gas through the apparatus, the density rose to 200. To obtain argon by this process Ramsay and Rayleigh (employing a mercury air pump and mercury gasometers) once treated about 150 litres of atmospheric nitrogen. On another occasion they treated 7,925 c.c. of air by the oxidation method and obtained 65 c.c. of argon, which corresponds to 0.82 per cent. The density of the argon obtained by this means was nearly 19.7, while that obtained by the magnesium method varied between 19-09 and 20.38.

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 nega tive 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 KMnO, 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

confirmed by four observed positive properties possessed by it, which

are:

1. The spectrum of argon observed by Crookes under a low pressure (in Geissler-Plücker tubes) distinguishes it from other gases. It was proved by this means that the argon obtained by means of magnesium is identical with that which remains after the conversion of the atmospheric nitrogen into nitric acid. Like nitrogen, argon presents two spectra produced at different potentials of the induced current, one being orange-red, the other steel-blue; the latter is obtained under a higher degree of rarefaction and with a battery of Leyden jars. Both the spectra of argon (in contradistinction to those of nitrogen) are distinguished by clearly defined lines. The red (ordinary) spectrum of argon has two particularly brilliant and characteristic red lines (not far from the bright red line of lithium, on the opposite side to the orange band) having wave-lengths 705-64 and 696-56 (see Vol. I., p. 565). Between these bright lines there are in addition lines with wave lengths 603-8, 565·1, 561′0, 555·7, 518·58, 516′5, 450·95, 420-10, 415.95 and 394-85. Altogether 80 lines have been observed in this spectrum and 119 in the blue spectrum, of which 26 are common to both spectra.9

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 2 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

7 The greatest brilliancy of the spectrum of argon is obtained at a tension of 3 mm., while for nitrogen it is about 75 mm. (Crookes). In Chapter V., Note 16 bis, it is said that the same blue line observed in the spectrum of argon is also observed in the spectrum of nitrogen. This is a mistake, since there is no coincidence between the blue lines of the argon and nitrogen spectra. However, we may add that for nitrogen the following moderately bright lines are known of wave-lengths 585, 574, 544, 516, 457, 442, 436, and 426, which are repeated in the spectra (red and blue) of argon, judging by Crookes' researches (1895); but it is naturally impossible to assert that there is perfect identity until some special comparative work has been done in this subject, which is very desirable, and more especially for the bluish-violet portion of the spectrum, more particularly between the lines 442-436, as these lines are distinguished by their brilliancy in both the argon and nitrogen spectra. The above-mentioned supposition of argon being polymerised nitrogen (N), formed from nitrogen (N2), with the evolution of heat, might find some support should it be found after careful comparison that even a limited number of spectral lines coincided.

8 At first the spectrum of argon exhibits the nitrogen lines, but after a certain time these lines disappear (under the influence of the platinum, and also of Al and Mg, but with the latter the spectrum of hydrogen appears) and leave a pure argon spectrum. It does not appear clear to me whether a polymerisation here takes place or a simple absorption. Perhaps the elucidation of this question would prove important in the history of argon. It would be desirable to know, for instance, whether the volume of argon changes when it is first subjected to the action of the electric discharge.

9 Crookes supposes that argon contains a mixture of two gases, but as he gives no reasons for this, beyond certain peculiarities of a spectroscopic character, we will not consider this hypothesis further.

a constant volume) of argon was determined by Rayleigh and Ramsay by the method of the velocity of sound (see Chapter XIV., Note 7 and Chapter VII., Note 26) and was found to be nearly 1.66, that is greater than for those gases whose molecules contain two atoms (for instance, CO,H,N2, air, &c., for which is nearly 14) or those whose molecules contain three atoms (for instance, CO,,N,O, &c., for which k is about 1.3), but closely approximate to the ratio of the specific heats of mercury vapour (Kundt and Warburg, k = 167). And as the molecule of mercury vapour contains one atom, so it may be said that argon is a simple gaseous body whose molecule contains one atom.10 A compound body should give a smaller ratio. The experiments upon the liquefaction of argon, which we shall presently describe, speak against the supposition that argon is a mixture of two gases. The importance of the results in question makes one wish that the determinations of the ratio of the specific heats (and other physical properties) might be confirmed with all possible accuracy. If we admit, as we are obliged to do for the present, that argon is a new element, its density shows that its atomic weight must be nearly 40, that is, near to that of K = 39 and Ca = 40, which does not correspond to the existing data respecting the periodicity of the properties

11

10 This portion of Rayleigh and Ramsay's researches deserves particular attention as, so far, no gaseous substance is known whose molecule contains but one atom. Were it not for the above determinations, it might be thought that argon, having a density 20, has a complex molecule, and may be a compound or polymerised body, for instance, Nz or NX, or in general Xn; but as the matter stands, it can only be said that either (1) argon is a new, peculiar, and quite unusual elementary substance, since there is no reason for assuming it to contain two simple gases, or (2) the magnitude, k (the ratio of the specific heats) does not only depend upon the number of atoms contained in the molecules, but also upon the store of internal energy (internal motion of the atoms in the molecule). Should the latter be admitted, it would follow that the molecules of very active gaseous elements would correspond to a smaller & than those of other gases having an equal number of atoms in their molecule. Such a gas is chlorine, for which k=1.33 (Chapter XIV., Note 7). For gases having a small chemical energy, on the contrary, a larger magnitude would be expected for k. I think these questions might be partially settled by determining k for ozone (03) and sulphur (S) (at about 500°). In other words, I would suggest, though only provisionally, that the magnitude, k=16, obtained for argon might prove to agree with the hypothesis that argon is N3, formed from N2 with the evolution of heat or loss of energy. Here argon gives rise to questions of primary importance, and it is to be hoped that further research will throw some light upon them. In making these remarks, I only wish to clear the road for further progress in the study of argon, and of the questions depending on it. I may also remark that if argon is N3 formed with the evolution of heat, its conversion into nitrogen, N2, and into nitride compounds (for instance, boron nitride or nitride of titanium) might only take place at a very high temperature.

11 Without having the slightest reason for doubting the accuracy of Rayleigh and Ramsay's determinations, I think it necessary to say that as yet (February 1895) I am only acquainted with the short memoir of the above chemists in the 'Proceedings of the Royal Society,' which does not give any description of the methods employed and results obtained, while at the end (in the general conclusions) the authors themselves express some doubt as to the simple nature of argon. Moreover, it seems to me that (Note 10) there must be a dependence of k upon the chemical energy. Besides which, it is not clear what density of the gas Rayleigh and Ramsay took in determining k. (If argon be N3, its density would be near to 21.) Hence I permit myself to express some doubt as to whether the molecule of argon contains but one atom.

of the elements in dependence upon their atomic weights, for there is no reason on the basis of existing data for admitting any intermediate elements between Cl = 35·5 and K = 39, and all the positions above potassium in the periodic system are occupied. This renders it very desirable that the velocity of sound in argon should be re-determined.12

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

12 If it should be found that k for argon is less than 14, or that k is dependent upon the chemical energy, it would be possible to admit that the molecule of argon contains not one, but several atoms-for instance, either N3 (then the density would be 21, which is near to the observed density) or X, if X stand for an element with an atomic weight near to 67. No elements are known between H=1 and Li=7, but perhaps they may exist. The hypothesis A =40 does not admit argon into the periodic system. If the molecule of argon be taken as A2-i.e. the atomic weight as A=20-argon apparently finds a place in Group VIII., between F=19 and Na=23; but such a position could only be justified by the consideration that elements of small atomic weight belong to the category of typical elements which offer many peculiarities in their properties, as is seen on comparing N with the other elements of Group V., or O with those of Group VI. Apart from this there appears to me to be little probability, in the light of the periodic law, in the position of an inert substance like argon in Group VIII., between such active elements as fluorine and sodium, as the representatives of this group by their atomic weights and also by their properties show distinct transitions from the elements of the last groups of the uneven series to the elements of the first groups of the even series--for instance,

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.]

VOL. II.

K K

properties in the liquid and critical states, which almost 13 disposes of the supposition that it contains a mixture of two or more unknown gases. As the first experiments showed, argon remains a gas under a pressure of 100 atmospheres and at a temperature of - 90°; this indicated that its critical temperature was probably below this temperature, as was indeed found to be the case when the temperature was lowered to 128°.6 14 by means of liquid ethylene. At this temperature argon easily liquefies to a colourless liquid under 38 atmospheres. The meniscus begins to disappear at between 13 There only remains the very remote possibility that argon consists of a mixture of two gases having very nearly the same properties.

14 The following data, given by Olszewsky, supplement the data given in Chapter II., Note 29, upon liquefied gases.

where te 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 N. 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 81, 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 a polymerised variety of nitrogen whose molecule contains N3, while ordinary nitrogen contains N. 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, UOz, Y2O5, &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.'