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)
The same reluctance to form a new phase is observed also in the phenomena
of superheating of liquids, and in the "hanging" of mercury in barometers,
in which case the vapour phase is not formed. In general, then, we may say
that _a new phase will not necessarily be formed immediately the system
passes into such a condition that the existence of that phase is possible_;
but rather, instead of the system undergoing transformation so as to pass
into the most stable condition under the existing pressure and temperature,
this transformation will be "suspended" or delayed, and the system will
become metastable. Only in the case of the formation of the liquid from the
solid phase, in a one-component system, has this reluctance to form a new
phase not been observed.
_To ensure the formation of the new phase, it is necessary to have that
phase present._ The presence of the solid phase will prevent the
supercooling of the liquid; and the presence of the vapour phase will
prevent the superheating of the liquid. However, even in the presence of
the more stable phase, transformation of the metastable phase occurs with
very varying velocity; in some cases so quickly as to appear almost
instantaneous; while in other cases, the change takes place so slowly as to
require hundreds of years for its achievement. It is this slow rate of
transformation that renders the existence of metastable forms possible,
when in contact with the more stable phase. Thus, for example, although
calcite is the most stable form of calcium carbonate at the ordinary
temperature,[125] the less stable {70} modification, aragonite,
nevertheless exists under the ordinary conditions in an apparently very
stable state.
As to the amount of the new phase required to bring about the
transformation of the metastable phase, quantitative measurements have been
carried out only in the case of the initiation of crystallization in a
supercooled liquid.[126] As the result of these investigations, it was
found that, in the case of superfused salol, the very small amount of 1 ×
10^{-7} gm. of the solid phase was sufficient to induce crystallization.
Crystallization of a supercooled liquid, however, can be initiated only by
a "nucleus" of the same substance in the solid state, or, as has also been
found, by a nucleus of an isomorphous solid phase; it is not brought about
by the presence of any chance solid.
Velocity of Transformation.--Attention has already been drawn to the
sluggishness with which reciprocal transformation of the polymorphic forms
of a substance may occur. In the case of tin, for example, it was found
that the white modification, although apparently possessing permanence, is
in reality in a metastable state, under the ordinary conditions of
temperature and pressure. This great degree of stability is due to the
tardiness with which transformation into the grey form occurs.
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