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 passing to the ternary systems, the composition of the solutions must be
represented by points or curves situated _between_ the two planes. We shall
now turn to the consideration of these. BD and CD are ternary eutectic
curves (p. 284). They give the composition of solutions in equilibrium with
ice and magnesium chloride dodecahydrate (BD), and with ice and potassium
chloride (CD). D is a _ternary cryohydric point_. If the temperature is
raised and the ice allowed to disappear, we shall pass to the solubility
curve for MgCl_{2},12H_{2}O + KCl (curve DE). At E carnallite is formed and
the potassium chloride disappears; EFG is then the solubility curve for
MgCl_{2},12H_{2}O + carnallite (KMgCl_{3},6H_{2}O). This curve also shows a
point of maximum temperature (F) and a retroflex portion. GH and HJ
represent the solubility curves of carnallite + MgCl_{2},8H_{2}O and
carnallite + MgCl_{2},6H_{2}O, G and H being transition points. JK is the
solubility curve for carnallite + MgCl_{2},4H_{2}O. At the point K we have
the _highest temperature at which carnallite can exist with magnesium
chloride in contact with solution_. Above this temperature decomposition
takes place and potassium chloride separates out.
If at the point E, at which the two single salts and the double salt are
present, excess of potassium chloride is added, the magnesium chloride will
all disappear owing to the formation of carnallite, and there will be left
carnallite and potassium chloride. The solubility curve for a mixture of
these two salts is represented by EMK; a simple curve exhibiting, however,
a temperature maximum at M. This maximum point corresponds with the fact
that dry carnallite melts at this temperature with separation of potassium
chloride. _At all temperatures {287} above this point, the formation of
double salt is impossible_. The retroflex portion of the curve represents
solutions in equilibrium with carnallite and potassium chloride, but in
which the ratio MgCl_{2} : KCl is greater than in the double salt.
Throughout its whole course, _the curve EMK represents solutions in which
the ratio of MgCl_{2} : KCl is greater than in the double salt_. As this is
a point of some importance, it will be well, perhaps, to make it clearer by
giving one of the isothermal curves, _e.g._ the curve for 10°, which is
represented diagrammatically in Fig. 114. E and F here represent solutions
saturated for carnallite plus magnesium chloride hydrate, and for
carnallite plus potassium chloride. As is evident, the point F lies above
the line representing equimolecular proportions of the salts (OD).
[Illustration: FIG. 114.]
Summary and Numerical Data.--We may now sum up the different systems which
can be formed, and give the numerical data from which the model is
constructed.[366]
I. _Bivariant Systems._
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