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
We have seen that to convert specific heat at constant volume into
specific heat at constant pressure 0·0692 must be added. Hence at
constant pressure the specific heat of such an ideal gas should be
0·1732. And the relation between specific heat at constant volume and
that at constant pressure should be 0·1040 to 0·1732, or 1 to 1⅔.
The conclusion to be drawn from these numbers for air, 0·1683 and
0·2375, which bear to each other the ratio of 1: 1·41, is that air
cannot be such an ideal gas; that in communicating heat to it some of
that heat must be employed in performing some kind of work other than
that of raising its temperature. What this work may possibly be we
shall consider later.
But Kundt and Warburg found, from their experiments on the ratio
between the specific heats of mercury gas, this ideal ratio, 1 to
1⅔; and Professor Ramsay obtained the same ideal ratio, or one very
close to it indeed, 1 to 1·659, for argon. He subsequently found this
ideal ratio also to hold for helium (1 to 1·652), and it must therefore
be concluded that such gases possess only three degrees of freedom; or,
in other words, their molecules, when heated, expend all the energy
imparted to them in translational motion through space.
This is the consequence which we should infer from the supposition
that such molecules are hard, smooth, elastic spheres. Were they each
composed of two atoms, we should have to picture them as dumbbell-like
structures; and here we enter on a theoretical conception put forward
by Professor Boltzmann, but which has not been accepted universally by
physicists.
[Illustration: FIG. 5.]
[Illustration: FIG. 6.]
Boltzmann imagines that to the three “degrees of freedom” of a single
atom molecule there may be added, provided the molecule consists of two
atoms, two other degrees of freedom, namely, freedom to rotate about
two planes at right angles to each other. The knobs at the end of each
imaginary dumb-bell may revolve round a central point in the handle
joining them, and it is clear that they may revolve in one horizontal
and in one vertical plane, as shown in Fig. 5. Such diatomic molecules
are said to possess five “degrees of freedom.” They will not, it is
supposed, rotate round the line joining the centres of the spheres,
because, as before said, the atoms are pictured as perfectly smooth.
But if the molecules are triatomic, as, for example, CO_{2} or N_{2}O,
they will have six degrees of freedom, for with the addition of an
additional atom they have an additional plane of rotation (see Fig.
6). Boltzmann has attempted to show that the ratio of the specific
heats of diatomic molecules should be as 1 to 1·4. In actual fact it
approximates to that number. For the commoner gases it is--
Oxygen 1·402
Nitrogen 1·411
Hydrogen 1·412
Carbon monoxide 1·418
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