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 farther end of the model (Fig. 116) corresponds, as already mentioned,
to the temperature -30°, so that the outline evidently represents the
isothermal curve for that temperature. Fig. 117 does not show this. We can,
however, follow the isothermal for -20°, which is the extreme curve on the
right in Fig. 117. Point A represents the solubility of 2FeCl_{3},12H_{2}O
in water. If hydrogen chloride is added, the concentration of ferric
chloride in the solution first decreases and then increases, until at point
34 the ternary double salt 2FeCl_{3},2HCl,12H_{2}O is formed. If the
addition of hydrogen chloride is continued, the ferric chloride disappears
ultimately, and only the ternary double salt remains. This salt can coexist
with solutions of the composition represented by the curve which passes
through the points 173, 174, 175. At the last-mentioned point, the ternary
salt with 8H_{2}O is formed. The composition of the solutions with which
this salt is in equilibrium at -20° is represented by the curve which
passes through a point of maximal concentration with respect to HCl, and
cuts the curve SN at the point 112, at which the solution is in equilibrium
with the two solid phases 2FeCl_{3},4H_{2}O and 2FeCl_{3},2HCl,8H_{2}O. The
succeeding portion of the isotherm represents the solubility curve at -20°
of 2FeCl_{3},4H_{2}O, which cuts the dark line OS at point 113, at which
the solution is in equilibrium with the two solid phases 2FeCl_{3},4H_{2}O
and 2FeCl_{3},2HCl,4H_{2}O. Thereafter comes the solubility curve of the
latter compound.
The other isothermal curves can be followed in a similar manner. If the
temperature is raised, the region of existence of the ternary double salts
becomes smaller and smaller, and at temperatures above 30° the ternary
salts with 12H_{2}O and 8H_{2}O are no longer capable of existing. If the
temperature is raised above 46°, only the binary compounds of ferric
chloride and water and the anhydrous salt can exist as solid phases.
The isothermal curve for 0° represents the solubility curve for
2FeCl_{3},12H_{2}O; 2FeCl_{3},7H_{2}O; 2FeCl_{3},5H_{2}O; and
2FeCl_{3},4H_{2}O. {296}
Finally, in the case of the system FeCl_{3}--HCl--H_{2}O, we find
_closed_ isothermal curves. Since, as already stated, the salt
2FeCl_{3},2HCl,8H_{2}O has a definite melting point, the temperature of
which is therefore higher than that at which this compound is in
equilibrium with solutions of other composition, it follows that the line
of intersection of an isothermal plane corresponding with a temperature
immediately below the melting point of the salt with the cone-shaped
surface of its region of existence, will form a closed curve. This is shown
by the isotherm for -4.5°, which surrounds the point Q, the melting point
of the ternary salt.
The following table gives some of the numerical data from which the curves
and the model have been constructed:--
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