Chapter XLI: Appendix: III

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_[1] by them, and upon the supposition of its being an element, they gave it the symbol A. But its true chemical nature is not yet fully known, for not only has no compound of it been yet obtained, but it has not even been brought into any reaction. From all that is known about it at the present time, we may conclude with the discoverers that argon belongs to those gases which are permanent constituents of the atmosphere, and that it is a new element. The latter statement, however, requires confirmation. We shall presently see, however, that the negative chemical character of argon (its incapacity to react with any substance), and the small amount of it present in the atmosphere (about 1-1/4 per cent. by volume in the nitrogen of air, and consequently about 1 per cent. by volume in air), as well as the recent date of its discovery (1894) and the difficulty of its preparation, are quite sufficient reasons for the incompleteness of the existing knowledge respecting this element. But since, so far as is yet known, we are dealing with a normal constituent of the atmosphere[1 bis], the existing data, notwithstanding their insufficiently definite nature, should find a place even in such an elementary work as the present, all the more as the names of Rayleigh, Ramsay, Crookes and Olszewsky, who have worked upon argon, are among the highest in our science, and their researches among the most difficult.[2] These researches, moreover, were directed straight to the goal, which was only partly reached owing to the unusual properties of argon itself.

[1] From the Greek [Greek: Argon]--inert.

[1 bis] In Note 16 bis, Chapter V., I mentioned that, judging from the
specific gravity of argon, it might possibly be polymerised
nitrogen, N_{3}, bearing the same relationship to nitrogen, N_{2},
that ozone, O_{3}, bears to ordinary oxygen. If this idea were
confirmed, still one would not imagine that argon was formed from
the atmospheric nitrogen by those reactions by which it was
obtained by Rayleigh and Ramsay, but rather that it arises from the
nitrogen of the atmosphere under natural conditions. Although this
proposition is not quite destroyed by the more recent results,
still it is contradicted by the fact that the ratio of the specific
heats of argon was found to be 1·66, which, as far as is now known,
could not be the case for a gas containing 3 atoms in its molecule,
since such gases (_see_ Chapter XIV., Note 7) give the ratio
approximately 1·3 (for example, CO_{2}). In abstaining from further
conclusions, for they must inevitably be purely conjectural, I
consider it advisable to suggest that in conducting further
researches upon argon it might be well to subject it to as high a
temperature as possible. And the possibility of nitrogen
polymerising is all the more admissible from the fact that the
aggregation of its atoms in the molecule is not at all unlikely,
and that polymerised nitrogen, judging from many examples, might be
inert if the polymerisation were accompanied by the evolution of
heat. In the following footnotes I frequently return to this
hypothesis, not only because I have not yet met any facts
definitely contradictory to it, but also because the chief
properties of argon agree with it to a certain extent.

[2] The chief difficulty in investigating argon lies in the fact that
its preparation requires the employment of a large quantity of air,
which has to be treated with a number of different reagents, whose
perfect purity (especially that of magnesium) will always be
doubtful, and argon has not yet been transferred to a substance in
which it could be easily purified. Perhaps the considerable
solubility of argon in water (or in other suitable liquids, which
have not apparently yet been tried) may give the means of doing so,
and it may be possible, by collecting the air expelled from boiling
water, to obtain a richer source of argon than ordinary air.

When it became known (Chapter V., Note 4 bis) that the nitrogen obtained from air (by removing the oxygen, moisture and CO_{2}, 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 O_{2}, CO_{2}, and H_{2}O), 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,[3] diffuses more slowly than nitrogen through the porous material. It remained, therefore, to separate this impurity from the nitrogen. To do this Rayleigh and Ramsay adopted two methods, converting the nitrogen into solid and liquid substances, either by absorbing the nitrogen by heated magnesium (Chapter V., Note 6, and Chapter XIV., Note 14), with the formation of nitride of magnesium, or else by converting it into nitric acid by the action of electric sparks or the presence of an excess of air and alkali, as in Cavendish's method.[3 bis] In both cases the nitrogen entered into reaction, while the heavier gas mixed with it remained inert, and was thus able to be isolated. That is, the argon could be separated by these means from the excess of atmospheric nitrogen accompanying it.[4] As an illustration we will describe how argon was obtained from the atmospheric nitrogen by means of magnesium.[5] To begin with, it was discovered that when atmospheric nitrogen was passed through a tube containing metallic magnesium heated to redness, its specific gravity rose to 14·88. As this showed that part of the gas was absorbed by the magnesium, a mercury gasometer filled with atmospheric nitrogen was taken, and the gas drawn over soda-lime, P_{2}O_{5}, heated magnesium[6] and then through tubes containing red-hot copper oxide, soda-lime and phosphoric anhydride to a second mercury gasometer. Every time the gas was repassed through the tubes, it decreased in volume and increased in density. After repeating 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 H_{2} = 1 and N_{2} = 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 20·0. 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.

[3] It might also be supposed that this heavy gas is separated by the
copper when the latter absorbs the oxygen of the air; but such a
supposition is not only improbable in itself, but does not agree
with the fact that nitrogen may be obtained from air by absorbing
the oxygen by various other substances in solution (for instance,
by the lower oxides of the metals, like FeO) besides red-hot
copper, and that the nitrogen obtained is always just as heavy.
Besides which, nitrogen is also set free from its oxides by copper,
and the nitrogen thus obtained is lighter. Therefore it is not the
copper which produces the heavy gas--_i.e._ argon.

[3 bis] It is worthy of note that Cavendish obtained a small residue of
gas in converting nitrogen into nitric acid; but he paid no
attention to it, although probably he had in his hands the very
argon recently discovered.

[4] When in these experiments, instead of atmospheric nitrogen the gas
obtained from its compound was taken, an inert residue of a heavy
gas, having the properties of argon, was also remarked, but its
amount was very small. Rayleigh and Ramsay ascribe the formation of
this residue to the fact that the gas in these experiments was
collected over water, and a portion of the dissolved argon in it
might have passed into the nitrogen. As the authors of this
supposition did not prove it by any special experiments, it forms a
weak point in their classical research. If it be admitted that
argon is N_{3}, the fact of its being obtained from the nitrogen of
compounds might be explained by the polymerisation of a portion of
the nitrogen in the act of reaction, although it is impossible to
refute Rayleigh and Ramsay's hypothesis of its being evolved from
the water employed in the manipulation of the gases. Three thousand
volumes of nitrogen extracted from its compounds gave about three
volumes of argon, while thirty volumes were yielded by the same
amount of atmospheric nitrogen.

[5] The preparation of argon by the conversion of nitrogen into nitric
acid is complicated by the necessity of adding a large proportion
of oxygen and alkali, of passing an electric discharge through the
mixture for a long period, and then removing the remaining oxygen.
All this was repeatedly done by the authors, but this method is far
more complex, both in practice and theory, than the preparation of
argon by means of magnesium. From 100 volumes of air subjected to
conversion into HNO_{3}, 0·76 volume of argon were obtained after
absorbing the excess of oxygen.

[6] In these and the following experiments the magnesium was placed in
an ordinary hard glass tube, and heated in a gas furnace to a
temperature almost sufficient to soften the glass. The current of
gas must be very slow (a tube containing a small quantity of
sulphuric acid served as a meter), as otherwise the heat evolved in
the formation of the Mg_{3}N_{2} (Chapter XIV., Note 14) will melt
the tube.

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 KMnO_{4} 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.[7] 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.[8] 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]

[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_{3}), formed from nitrogen (N_{2}),
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.

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 2-1/2 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 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