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)
Since it is necessary to take into account not only the changing
composition of the liquid phase, but also the variation of the temperature,
we shall employ the right prism for the graphic representation of the
systems, as shown in Fig. 95. A, B, and C in this figure, therefore, denote
the melting points of the pure components. If we start with the component A
at its melting point, and add B, which is capable of dissolving in liquid
A, the freezing point of A will be lowered; and, similarly, the freezing
point of B by addition of A. In this way we get the freezing point curve
A_k__{1}B for the binary system; _k__{1}; being an eutectic point. This
curve will of course lie in the plane formed by one face of the prism. In a
similar manner we obtain the freezing point curves A_k__{2}C and B_k__{3}C.
These curves give the composition of the binary liquid phases in
equilibrium {254} with one of the pure components, or at the eutectic
points, with a mixture of two solid components. If, now, to the system
represented say by the point _k__{1}, a small quantity of the third
component, C, is added, the temperature at which the two solid phases A and
B can exist in equilibrium with the liquid phase is lowered; and this
depression of the eutectic point is all the greater the larger the addition
of C. In this way we obtain the curve _k__{1}K, which slopes inwards and
downwards, and indicates the varying composition of the ternary liquid
phase with which a mixture of solid A and B are in equilibrium. Similarly,
the curves _k__{2}K and _k__{3}K are the corresponding eutectic curves for
A and C, and B and C in equilibrium with ternary solutions. At the point K,
the three solid components are in equilibrium with the liquid phase; and
this point, therefore, represents _the lowest temperature attainable with
the three components given_. Each of the ternary eutectic curves, as they
may be called, is produced by the intersection of two surfaces, while at
the ternary eutectic point, three surfaces, viz. A_k__{1}K_k__{2},
B_k__{1}K_k__{3}, and C_k__{1}K_k__{3} intersect. Any point on one of these
surfaces represents a ternary solution in equilibrium with only one
component in the solid state; the lines or curves of intersection of these
represent equilibria with two solid phases, while at the point K, the
ternary eutectic point, there are three solid phases in equilibrium with a
liquid and a vapour phase. The surfaces just mentioned represent bivariant
systems. One component in the solid state can exist in equilibrium with a
ternary liquid phase under varying conditions of temperature and
concentration of the components in the solution; and before the state of
the system is defined, these two variables, temperature and composition of
the liquid phase, must be fixed. On the other hand, the curves formed by
the intersection of these planes represent univariant systems; at a given
temperature two solid phases can exist in equilibrium with a ternary
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