The three critical constants may be determined, as Mr S. Young and M.
Amagat have shown, by a direct method based on the consideration of
the saturated states. Results, perhaps more precise, may also be
obtained if one keeps to two constants or even to a single one--
temperature, for example--by employing various special methods. Many
others, MM. Cailletet and Colardeau, M. Young, M.J. Chappuis, etc.,
have proceeded thus.
The case of mixtures is much more complicated. A binary mixture has a
critical space instead of a critical point. This space is comprised
between two extreme temperatures, the lower corresponding to what is
called the folding point, the higher to that which we call the point
of contact of the mixture. Between these two temperatures an
isothermal compression yields a quantity of liquid which increases,
then reaches a maximum, diminishes, and disappears. This is the
phenomenon of retrograde condensation. We may say that the properties
of the critical point of a homogeneous substance are, in a way,
divided, when it is a question of a binary mixture, between the two
points mentioned.
Calculation has enabled M. Van der Waals, by the application of his
kinetic theories, and M. Duhem, by means of thermodynamics, to foresee
most of the results which have since been verified by experiment. All
these facts have been admirably set forth and systematically
co-ordinated by M. Mathias, who, by his own researches, moreover, has
made contributions of the highest value to the study of questions
regarding the continuity of the liquid and gaseous states.
The further knowledge of critical elements has allowed the laws of
corresponding states to be more closely examined in the case of
homogeneous substances. It has shown that, as I have already said,
bodies must be arranged in groups, and this fact clearly proves that
the properties of a given fluid are not determined by its critical
constants alone, and that it is necessary to add to them some other
specific parameters; M. Mathias and M. D. Berthelot have indicated
some which seem to play a considerable part.
It results also from this that the characteristic equation of a fluid
cannot yet be considered perfectly known. Neither the equation of Van
der Waals nor the more complicated formulas which have been proposed
by various authors are in perfect conformity with reality. We may
think that researches of this kind will only be successful if
attention is concentrated, not only on the phenomena of
compressibility and dilatation, but also on the calorimetric
properties of bodies. Thermodynamics indeed establishes relations
between those properties and other constants, but does not allow
everything to be foreseen.
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