The Monist, Vol. 3, 1892-1893 : $b A quarterly magazineVarious
Philosophy
The Monist, Vol. 3, 1892-1893 : $b A quarterly magazine
Various
Philosophy -- Periodicals
Now, the virial must be nearly independent of the temperature, and
therefore the last term almost disappears. The virial would not be
quite independent of the temperature, because if the temperature (i.
e. the square of the velocity of the molecules) is lowered, and the
pressure correspondingly lowered, so as to make the volume the same,
the attractions of the molecules will have more time to produce their
effects, and consequently, the pairs of molecules the closest together
will be held together longer and closer; so that the virial will
generally be increased by a decrease of temperature. Now, Amagat’s
experiments do show an excessively minute effect of this sort, at least,
when the volumes are not too small. However, the observations are well
enough satisfied by assuming the “coefficient of expansion at constant
volume” to consist wholly of the first term, _a_/(_V_). Thus, Amagat’s
experiments enable us to determine the values of _a_ and thence to
calculate the virial; and this we find varies for carbonic acid gas
nearly inversely to (_V_)⁰˙⁹. There is, thus, a rough approximation to
satisfying Van der Waals’s equation. But the most interesting result of
Amagat’s experiments, for our purpose at any rate, is that the quantity
_a_, though nearly constant for any one volume, differs considerably with
the volume, nearly doubling when the volume is reduced fivefold. This
can only indicate that the mean kinetic energy of a given mass of the
gas for a given temperature is greater the more the gas is compressed.
But the laws of mechanics appear to enjoin that the mean kinetic energy
of a moving particle shall be constant at any given temperature. The
only escape from contradiction, then, is to suppose that the mean mass
of a moving particle diminishes upon the condensation of the gas. In
other words, many of the molecules are dissociated, or broken up into
atoms or sub-molecules. The idea that dissociation should be favored
by diminishing the volume will be pronounced by physicists, at first
blush, as contrary to all our experience. But it must be remembered
that the circumstances we are speaking of, that of a gas under fifty
or more atmospheres pressure, are also unusual. That the “coefficient
of expansion under constant volume” when multiplied by the volumes
should increase with a decrement of the volume is also quite contrary
to ordinary experience; yet it undoubtedly takes place in all gases
under great pressure. Again, the doctrine of Arrhenius[7] is now
generally accepted, that the molecular conductivity of an electrolyte is
proportional to the dissociation of ions. Now the molecular conductivity
of a fused electrolyte is usually superior to that of a solution. Here is
a case, then, in which diminution of volume is accompanied by increased
dissociation.
Public-domain text, read in full here on John Shaqi.
Reviews
Reviews
No reviews yet
Be the first to share your thoughts on this work.
Join the Discussion
Join the discussion
Sign in to leave a comment or review.
Sign InorCreate an account