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)
On account of the great frequency with which the prior formation of the
less stable form occurs, Ostwald[144] has put forward the _law of
successive reactions_, which states that when a system passes from a less
stable condition it does not pass directly into the most stable of the
possible states; but into the next more stable, and so step by step into
the most stable. This law explains the formation of the metastable forms of
monotropic substances, which would otherwise not be obtainable. Although it
is not always possible to observe the formation of the least stable form,
it should be remembered that that may quite conceivably be due to the great
velocity of transformation of the less stable into the more stable form.
From what we have learned about the velocity of transformation of
metastable phases, we can understand that rapid cooling to a low
temperature will tend to preserve the less stable form; and, on account of
the influence of temperature in increasing the velocity of change, it can
be seen that the formation of the less stable form will be more difficult
to observe in superheated than in supercooled systems. The factors,
however, which affect the readiness with which {75} the less stable
modification is produced, appear to be rather various.[145]
Although a number of at least apparent exceptions to Ostwald's law have
been found, it may nevertheless be accepted as a very useful generalization
which sums up very frequently observed phenomena.
* * * * *
{76}
CHAPTER V
SYSTEMS OF TWO COMPONENTS--PHENOMENA OF DISSOCIATION
In the preceding pages we have studied the behaviour of systems consisting
of only one component, or systems in which all the phases, whether solid,
liquid, or vapour, had the same chemical composition (p. 13). In some
cases, as, for example, in the case of phosphorus and sulphur, the
component was an elementary substance; in other cases, however, _e.g._
water, the component was a compound. The systems which we now proceed to
study are characterized by the fact that the different phases have no
longer all the same chemical composition, and cannot, therefore, according
to definition, be considered as one-component systems.
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