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)
Similarly, starting with the pure [beta] modification, the freezing point
after fusion will gradually fall owing to the formation of the [alpha]
modification; and the composition of the liquid phase will pass along the
curve BC. If, now, the rate of cooling is not too great, or if the velocity
of isomeric transformation is sufficiently rapid, complete solidification
will not occur at the eutectic point; for at this temperature solid and
liquid are not in stable equilibrium with one another. On the contrary, a
further quantity of the [beta] modification will undergo isomeric change,
the liquid phase will become richer in the [alpha] form, and the freezing
point will _rise_; the solid phase in contact with the liquid being now the
[alpha] modification. The freezing point will continue to rise until the
point D is reached, at which complete solidification will take place
without further change of temperature.
The diagram also allows us to predict what will be the result of rapidly
cooling a fused mixture of the two isomerides. Suppose that either the
[alpha] or the [beta] modification has been maintained in the fused state
at the temperature _t'_ sufficiently long for equilibrium to be
established. The composition of the liquid phase will be represented by
_x'_. If the liquid is now _rapidly_ cooled, the composition will remain
unchanged as represented by the dotted line _x'_G. At the temperature of
the point G solid [alpha] modification will be deposited. If the cooling is
not carried below the point G, so as to cause complete solidification, the
freezing point will be found to rise with time, owing to the conversion of
some of the [beta] form into the [alpha] form {200} in the liquid phase;
and this will continue until the composition of the liquid has reached the
point D. From what has just been said, it can also be seen that if the
freezing point curves can be obtained by actual determination of the
freezing points of different synthetic mixtures of the two isomerides, it
will be possible to determine the condition of equilibrium in the fused
state at any given temperature without having recourse to analysis. All
that is necessary is to rapidly cool the fused mass, after equilibrium has
been established, and find the freezing point at which solid is deposited;
that is, find the point at which the line of constant temperature cuts the
freezing point curve. The composition corresponding to this temperature
gives the composition of the equilibrium mixture at the given temperature.
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