The Principles of Chemistry, Volume IMendeleyev, Dmitry Ivanovich
Science
The Principles of Chemistry, Volume I
Mendeleyev, Dmitry Ivanovich
Argon; Chemistry; Periodic law
[36] From the very commencement of the promulgation of the idea of
dissociation, it might have been imagined that reversible
reactions of combination (the formation of H_{2} and O belongs
to this number) commence at the same temperature as that at
which dissociation begins. And in many cases this is so, but
not always, as may be seen from the facts (1) that at 450-560°,
when detonating gas explodes, the density of aqueous vapour not
only does not vary (and it hardly varies at higher temperatures,
probably because the amount of the products of dissociation is
small), but there are not, as far as is yet known, any traces
of dissociation; (2) that under the influence of contact the
temperature at which combination takes place falls even to the
ordinary temperature, when water and similar compounds naturally
are not dissociated and, judging from the data communicated
by D. P. Konovaloff (Introduction, Note 39) and others, it is
impossible to escape the phenomena of contact; all vessels,
whether of metal or glass, show the same influence as spongy
platinum, although to a much less degree. The phenomena of
contact, judging from a review of the data referring to it,
must be especially sensitive in reactions which are powerfully
exothermal, and the explosion of detonating gas is of this kind.
The combination of hydrogen with oxygen is accompanied by the evolution
of a very considerable amount of heat; according to the determinations
of _Favre_ and _Silbermann_,[37] 1 part by weight of hydrogen in
forming water evolves 34,462 units of heat. Many of the most recent
determinations are very close to this figure, so that it may be taken
that in the formation of 18 parts of water (H_{2}O) there are evolved 69
major calories, or 69,000 units of heat.[38] _If the specific heat of
aqueous vapour_ (0·48) _remained constant from the ordinary temperature
to that at which the combustion of detonating gas takes place_
(but there is now no doubt that it increases), were the combustion
concentrated at one point[39] (but it occurs in the whole region of a
flame), were there no loss from radiation and heat conduction, and _did
dissociation not take place_--that is, did not a state of equilibrium
between the hydrogen, oxygen, and water come about--_then it would be
possible to calculate the temperature of the flame of detonating gas_.
It would then be 8,000°.[40] In reality it is very much lower, but it
is nevertheless higher than the temperature attained in furnaces and
flames, and is as high as 2,000°. The explosion of detonating gas is
explained by this high temperature, because the aqueous vapour formed
must occupy a volume at least 5 times greater than that occupied by
the detonating gas at the ordinary temperature. Detonating gas emits a
sound, not only as a consequence of the commotion which occurs from the
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