If in the study of the statics of a simple fluid the experimental
results are already complex, we ought to expect much greater
difficulties when we come to deal with mixtures; still the problem has
been approached, and many points are already cleared up.
Mixed fluids may first of all be regarded as composed of a large
number of invariable particles. In this particularly simple case M.
Van der Waals has established a characteristic equation of the
mixtures which is founded on mechanical considerations. Various
verifications of this formula have been effected, and it has, in
particular, been the object of very important remarks by M. Daniel
Berthelot.
It is interesting to note that thermodynamics seems powerless to
determine this equation, for it does not trouble itself about the
nature of the bodies obedient to its laws; but, on the other hand, it
intervenes to determine the properties of coexisting phases. If we
examine the conditions of equilibrium of a mixture which is not
subjected to external forces, it will be demonstrated that the
distribution must come back to a juxtaposition of homogeneous phases;
in a given volume, matter ought so to arrange itself that the total
sum of free energy has a minimum value. Thus, in order to elucidate
all questions relating to the number and qualities of the phases into
which the substance divides itself, we are led to regard the
geometrical surface which for a given temperature represents the free
energy.
I am unable to enter here into the detail of the questions connected
with the theories of Gibbs, which have been the object of numerous
theoretical studies, and also of a series, ever more and more
abundant, of experimental researches. M. Duhem, in particular, has
published, on the subject, memoirs of the highest importance, and a
great number of experimenters, mostly scholars working in the physical
laboratory of Leyden under the guidance of the Director, Mr Kamerlingh
Onnes, have endeavoured to verify the anticipations of the theory.
We are a little less advanced as regards abnormal substances; that is
to say, those composed of molecules, partly simple and partly complex,
and either dissociated or associated. These cases must naturally be
governed by very complex laws. Recent researches by MM. Van der Waals,
Alexeif, Rothmund, Künen, Lehfeld, etc., throw, however, some light on
the question.
The daily more numerous applications of the laws of corresponding
states have rendered highly important the determination of the
critical constants which permit these states to be defined. In the
case of homogeneous bodies the critical elements have a simple, clear,
and precise sense; the critical temperature is that of the single
isothermal line which presents a point of inflexion at a horizontal
tangent; the critical pressure and the critical volume are the two
co-ordinates of this point of inflexion.
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