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)
In the case of a binary system, in which 2FeCl_{3},12H_{2}O is in
equilibrium with a solution of the same composition, addition of hydrogen
chloride must evidently lower the temperature at which equilibrium can
exist; and the same holds, of course, {293} for all other binary solutions
in equilibrium with this solid phase. In this way we obtain the surface I.,
which represents the temperatures and concentrations of solutions in which
2FeCl_{3},12H_{2}O can be in equilibrium with a ternary solution containing
ferric chloride, hydrogen chloride, and water. This surface is analogous to
the curved surface K_{1}K_{2}_k__{4}_k__{3} in Fig. 97 (p. 256). Similarly,
the surfaces II., III., IV., and V. represent the conditions for
equilibrium between the solid phases 2FeCl_{3},7H_{2}O; 2FeCl_{3},5H_{2}O;
2FeCl_{3},4H_{2}O; FeCl_{3} and ternary solutions respectively. The lines
CL, EM, GN, and IO on the model represent univariant systems in which a
ternary solution is in equilibrium with two solid phases, viz. with those
represented by the adjoining fields. These lines correspond with the
ternary eutectic curves _k__{3}K_{1} and _k__{4}K_{2} in Fig. 97. Besides
the surfaces already mentioned, there are still three others, VI., VII.,
and VIII., which also represent the conditions for equilibrium between one
solid phase and a ternary solution; but in these cases, the solid phase is
not a binary compound or an anhydrous salt, but a ternary compound
containing all three components. The solid phases which are in equilibrium
with the ternary solutions represented by the surfaces VI., VII., and
VIII., are 2FeCl_{3},2HCl,4H_{2}O; 2FeCl_{3},2HCl,8H_{2}O; and
2FeCl_{3},2HCl,12H_{2}O respectively.
The model for FeCl_{3}--HCl--H_{2}O exhibits certain other peculiarities
not found in the case of MgCl_{2}--KCl--H_{2}O. On examining the model more
closely, it is found that the field of the ternary compound
2FeCl_{3},2HCl,8H_{2}O (VII.) resembles the surface of a sugar cone, and
has a projecting point, the end of which corresponds with a higher
temperature than does any other point of the surface. At the point of
maximum temperature the composition of the liquid phase is the same as that
of the solid. This point, therefore, represents the melting point of the
double salt of the above composition.
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