The Phase Rule and Its ApplicationsFindlay, Alexander
Science
The Phase Rule and Its Applications
Findlay, Alexander
Chemistry, Physical and theoretical; Phase rule and equilibrium; Solution (Chemistry)
General.--With the conception of gaseous and liquid solutions, every one is
familiar. Gases can mix in all proportions to form homogeneous solutions.
Gases can dissolve in or be "absorbed" by liquids; and solids, also, when
brought in contact with liquids, "pass into solution" and yield a
homogeneous liquid phase. On the other hand, the conception of a _solid
solution_ is one which in many cases is found more difficult to appreciate;
and the existence and behaviour of solid solutions, in spite of their not
uncommon occurrence and importance, are in general comparatively little
known.
The reason of this is to be found, to some extent, no doubt, in the fact
that the term "solid solution" was introduced at a comparatively recent
date,[254] but it is probably also due in some measure to a somewhat hazy
comprehension of the definition of the term "solution" itself. As has
already been said (p. 92), a solution is a homogeneous phase, the
composition of which can vary continuously within certain limits; the
definition involves, therefore, no condition as to the physical state of
the substances. Accordingly, solid solutions are homogeneous solid phases,
the composition of which can undergo continuous variation within certain
limits. Just as we saw that the range of variation of composition is more
limited in the case of liquids than in the case of gases, so also we find
that the limits of miscibility are in general still more restricted in the
case of solids. Examples of complete miscibility are, however, not unknown
even in the case of solid substances.
Solid solutions have long been known, although, of course, {176} they were
not defined as such. Thus, the phenomena of "occlusion" of gases by metals
and other substances (occlusion of hydrogen by palladium; occlusion of
hydrogen by iron) are due to the formation of solid solutions. The same is
probably also true of the phenomena of "adsorption," as in the removal of
organic colouring matter by charcoal, although, in this case, surface
tension no doubt plays a considerable part.[255]
As examples of the solution of gases in solids there may be cited (in
addition to the phenomena of occlusion already mentioned), the hydrated
silicates and the zeolites. During dehydration these crystalline substances
remain clear and transparent, and the pressure of the water vapour which
they emit varies with the degree of hydration or the concentration of water
in the mineral.[256] As examples of the solution of solids in solids we
have the cementation of iron by charcoal, the formation of glass, and the
crystallization together of isomorphous substances.
Although we have here spoken of the glasses as "solid solutions," it should
be mentioned that the term "solid" is used in its popular sense. Strictly
speaking, the glasses are to be regarded as supercooled liquids (see also
p. 53, footnote).
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