The Monist, Vol. 3, 1892-1893 : $b A quarterly magazineVarious
Philosophy
The Monist, Vol. 3, 1892-1893 : $b A quarterly magazine
Various
Philosophy -- Periodicals
The quantity _b_ is the volume of a molecule, which he supposes to
be an impenetrable body, and all the virtue of the equation lies in
this term which makes the equation a cubic in _V_, which is required
to account for the shape of certain isothermal curves.[6] But if the
idea of an impenetrable atom is illogical, that of an impenetrable
molecule is almost absurd. For the kinetical theory of matter teaches
us that a molecule is like a solar system or star-cluster in miniature.
Unless we suppose that in all heating of gases and vapors internal
work is performed upon the molecules, implying that their atoms are at
considerable distances, the whole kinetical theory of gases falls to the
ground. As for the term added to _P_, there is no more than a partial
and roughly approximative justification for it. Namely, let us imagine
two spheres described round a particle as their centre, the radius of
the larger being so great as to include all the particles whose action
upon the centre is sensible, while the radius of the smaller is so large
that a good many molecules are included within it. The possibility of
describing such a sphere as the outer one implies that the attraction
of the particles varies at some distances inversely as some higher
power of the distance than the cube, or, to speak more clearly, that
the attraction multiplied by the cube of the distance diminishes as the
distance increases; for the number of particles at a given distance
from any one particle is proportionate to the square of that distance
and each of these gives a term of the virial which is the product of
the attraction into the distance. Consequently unless the attraction
multiplied by the cube of the distance diminished so rapidly with the
distance as soon to become insensible, no such outer sphere as is
supposed could be described. However, ordinary experience shows that such
a sphere is possible; and consequently there must be distances at which
the attraction does thus rapidly diminish as the distance increases. The
two spheres, then, being so drawn, consider the virial of the central
particle due to the particles between them. Let the density of the
substance be increased, say, _N_ times. Then, for every term, _Rr_, of
the virial before the condensation, there will be _N_ terms of the same
magnitude after the condensation. Hence, the virial of each particle will
be proportional to the density, and the equation of the virial becomes
aθ = PV̅ + c⁄V̅.
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