The Gases of the Atmosphere: The History of Their DiscoveryRamsay, William
History
The Gases of the Atmosphere: The History of Their Discovery
Ramsay, William
Air; Argon; Chemistry -- History
It was next deemed necessary to test whether nitrogen was homogeneous
by preparing it too by several different methods. In the same paper
Lord Rayleigh (p. 146) mentions that nitrogen, prepared from ammonia,
its compound with hydrogen, is somewhat lighter than “atmospheric
nitrogen,” the deficiency in weight amounting to about 1 part in 200.
Now it is evident from inspection of the numbers quoted above, that
the accuracy of the density determination may be trusted to within
1 part in 10,000, and that the balance would detect a discrepancy
one-fiftieth of that observed in the densities of “atmospheric” and
“chemical” nitrogen. In a letter to _Nature_, Lord Rayleigh asked for
suggestions from chemists as to the reason of this curious anomaly, but
his letter went without reply. He himself was inclined to believe that
the difference was due to the decomposition of some of the ordinary
molecules of nitrogen, usually believed to consist of two atoms in
union with each other, into molecules consisting of one atom; and as it
is held that equal numbers of molecules inhabit the same volume,
temperature and pressure being equal, if the total number of molecules
in his globe were increased by the splitting of some double-atom
molecules into single-atom molecules, the effect would be that, owing
to an admixture of some lighter molecules, the density would be
somewhat reduced.
But two other suppositions were entertained as possible. The oxygen
might have been imperfectly removed from the nitrogen derived from the
atmosphere; or, on the other hand, the nitrogen from ammonia might
conceivably have retained traces of hydrogen. In the former case, the
nitrogen would have an increased weight owing to admixture of some
heavier oxygen; in the latter, a diminished weight, due to the presence
of the lighter hydrogen. The first of these suppositions is out of
the question, inasmuch as it would have required that the nitrogen
should contain one-thirtieth of its volume of oxygen, or one-sixth of
that present in air, in order that its density should be raised by one
two-hundredth; for the densities of oxygen and nitrogen are not so very
different. The second supposition was negatived by introducing hydrogen
purposely, and removing it by passing the gas over red-hot copper
oxide, which oxidises the hydrogen to water. This yielded nitrogen of
the same density as that which had not undergone that treatment.
One other possibility was considered: the atmospheric nitrogen might
contain some molecules of greater complexity than two-atom molecules,
say N_{3}-molecules. Now it is known that when oxygen is electrified
by the passage of a rain of small sparks through it, it acquires
new properties: it possesses an odour, and attacks metallic mercury
and silver. And this product, ozone, has been shown to consist of
three-atom molecules of oxygen, by various experiments of which an
account cannot be given here.
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