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the peroxide of uranium, UO,, prepared by Fairley ; 14 while OsO, is the highest oxide giving salts. The line of argument which is inspired by the periodic law, so far from being weakened by the discovery of peroxides, is thus actually strengthened, and we must hope that a further exploration of the region under consideration will confirm the applicability to chemistry generally of the principles deduced from the periodic law.
Permit me now to conclude my rapid sketch of the oxygen compounds by the observation that the periodic law is especially brought into evidence in the case of the oxides which constitute the immense majority of bodies at our disposal on the surface of the earth.'
The oxides are evidently subject to the law, both as regards their chemical and their physical properties, especially if we take into account the cases of polymerism which are so obvious when comparing CO, with Si,Ogn In order to prove this I give the densities s and the specific volumes v of the higher oxides of two short periods. To render comparison easier, the oxides are all represented as of the form R,On. In the column headed A the differences are given between the volume of the oxygen compound and that of the parent element, divided by n--that is, by the number of atoms of oxygen in the compound : 15
A Na,O ................ 2:6 24 -22 | K.,O................. 2:7 35 -- 55 Mg,O................ 3•6 22 -3 Ca, O ................ 3.15 36 -7 A1,0, ............... 4:0 26 +1:3 Sc, 0, ................ 3.86 35 0 Si, O, ............... 2:65 45 5•2 Li,O, ............... 4.2 38 +5 P,0,............... 2:39 59 6•2 V.,0, ................ 3•49 52 6:7 S,06 ............... 1.96 82 8•7 | Cr,O. ............... 2:74 73 9.5
. I have nothing to add to these figures, except that like relations appear in other periods as well. The above relations were precisely those which made it possible for me to be certain that the relative density of ekasilicon oxide would be about 4:7; germanium oxide, actually obtained by Winkler, proved, in fact, to have the relative density 4.703.
The foregoing account is far from being an exhaustive one of all that has already been discovered by means of the periodic law telescope in the bound. less realms of chemical evolution. Still less is it an exhaustive account of all that may yet be seen, but I trust that the little which I have said will account
14 The compounds of uranium prepared by Fairley seem to me especially instructive in understanding the peroxides. By the action of hydrogen peroxide on uranium oxide, U03, a peroxide of uranium, U04,4H.,0, is obtained (U=240) if the solution be acid; but if hydrogen peroxide act on uranium oxide in the presence of caustic soda, a crystalline deposit is obtained which has the composition Na U03,4H2O, and evidently is a combination of sodium peroxide, Na,O., with uranium peroxide, U04. It is possible that the former peroxide, U04,4H.,O, contains the elements of hydrogen peroxide and uranium peroxide, U,O7, or even U(OH),,H.,O2, like the peroxide of tin recently discovered by Spring, which has the constitution Sn,0;,H,O..
15 A thus represents the average increase of volume for each atom of oxygen contained in the higher salt-forming oxide. The acid oxides give, as a rule, a higher value of A, while in the case of the strongly alkaline oxides its value is usually negative.
for the philosophical interest attached in chemistry to this law. Although but a recent scientific generalisation, it has already stood the test of laboratory verification, and appears as an instrument of thought which has not yet been compelled to undergo modification ; but it needs not only new applications, but also improvements, further development, and plenty of fresh energy. All this will surely come, seeing that such an assembly of men of science as the Chemical Society of Great Britain has expressed the desire to have the his. tory of the periodic law described in a lecture dedicated to the glorious name of Faraday.
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 obser. vations made by Crookes and Olszewsky upon the same subject.
This gas, which was discovered by Rayleigh and Ramsay in atmo. spheric nitrogen, was named argon' 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 14 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. 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 Apydy-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, N3, bearing the same relationship to nitrogen, N2, that ozone, O3, 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, CO2). 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. .
When it became known (Chapter V., Note 4 bis) that the nitrogen obtained from air (by removing the oxygen, moisture and Co, 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 0.,, CO, and H.,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," diffuses more slowly than nitrogen through the porous material. It remained, therefore, to separate this im. purity 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 hy 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 accom. panying it. As an illustration we will describe how argon was obtained from the atmospheric nitrogen by means of magnesium. 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.,0;, heated magnesium 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
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.
5 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 N3, 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 HNO3, 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 Mg3N2 (Chapter XIV., Note 14) will melt the tube.