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)
Changes in Mixed Crystals with the Temperature.--In the case of the
different types of systems represented in Fig. 49, a homogeneous liquid
solution of the two components will exist at temperatures above the
freezing-point curve, a homogeneous mixed crystal at temperatures below the
melting-point curve, while at any point between the freezing-point and
melting-point {193} curves the mixture will separate into a solid phase and
a liquid phase. In the case, however, of the two types shown in Fig. 54 the
relationships are somewhat more complicated. As before, the area above the
freezing-point curve gives the conditions under which homogeneous liquid
solutions can exist; but below the melting-point curve two different mixed
crystals can coexist. This will be best understood from Figs. 57 and 58. D
and E represent, as we have seen, the composition of two mixed crystals
which are in equilibrium with the liquid solution at the temperature of the
point C. These two mixed crystals represent, in the one case, a saturated
solution of B in A (point D), and the other a saturated solution of A in B
(point E). Just as we saw that the mutual solubility of two liquids varied
with the temperature, so also in the case of two solids; as the temperature
alters, the solubility of the two solid components in one another will
change. This alteration is indicated diagrammatically in Figs. 57 and 58 by
the dotted curve similar to the solubility curves for two mutually soluble
liquids (p. 101).
Suppose, now, that a mixed crystal of the composition _x_ is cooled down,
it will remain unchanged until, when the temperature has fallen to _t'_,
the homogeneous mixed crystal breaks up into a conglomerate of two mixed
crystals the composition of {194} which is represented by _x'_ and _x"_
respectively. From this, then, it can be seen that in the case of
substances which form two solid solutions, the mixed crystals which are
desposited from the liquid fused mass need not remain unchanged in the
solid state, but may at some lower temperature lose their homogeneity. This
fact is of considerable importance for the formation of alloys.[277]
A good example of this will soon be met with in the case of the iron and
carbon alloys. The alloys of copper and tin also furnish examples of the
great changes which may take place in the alloy between the temperature at
which it separates out from the fused mass and the ordinary temperature.
Thus, for example, one of the alloys of copper and tin which separates out
from the liquid as a solid solution breaks up, on cooling, into the
compound Cu_{3}Sn and liquid:[278] a striking example of a solid substance
partially liquefying on being cooled.
* * * * *
{195}
CHAPTER XI
EQUILIBRIUM BETWEEN DYNAMIC ISOMERIDES
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