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)
Fig. 113 is a diagrammatic sketch of the model for carnallite looked at
sideways from above. Along the X-axis is measured the concentration of
magnesium chloride in the {285} solution; along the Y-axis, the
concentration of potassium chloride; while along the T-axis is measured the
temperature. The three axes are at right angles to one another. The
XT-plane, therefore, contains the solubility curve of magnesium chloride;
the YT-plane, the solubility curve of potassium chloride, and in the space
between the two planes, there are represented the composition of solutions
containing both magnesium and potassium chlorides. Any _surface_ between
the two planes will represent the various solutions in equilibrium with
only one solid phase, and will therefore indicate the area or field of
existence of bivariant ternary systems. A _line_ or _curve_ formed by the
intersection of two surfaces will represent solutions in equilibrium with
two solid phases (viz. those belonging to the intersecting surfaces), and
will show the conditions for the existence of univariant systems. Lastly,
_points_ formed by the intersection of three surfaces will represent
invariant systems, in which a solution can exist in equilibrium with three
solid phases (viz. those belonging to the three surfaces).
We shall first consider the solubility relations of the single salts. The
complete equilibrium curve for magnesium chloride and water is represented
in Fig. 113 by the series of curves ABF_{1} G_{1} H_{1} J_{1} L_{1} N_{1}.
AB is the freezing-point curve of ice in contact with solutions containing
magnesium chloride, and B is the cryohydric point at which the solid phases
ice and MgCl_{2},12H_{2}O can co-exist with solution. BFG is the solubility
curve of magnesium chloride dodecahydrate. This curve shows a point of
maximum temperature at F_{1}, and a retroflex portion F_{1}G_{1}. The curve
is therefore of the form exhibited by calcium chloride hexahydrate, or the
hydrates of ferric chloride (Chapter VIII.). G_{1} is a transition point at
which the solid phase changes from dodecahydrate to octahydrate, the
solubility of which is represented by the curve G_{1}H_{1}. At H_{1} the
octahydrate gives place to the hexahydrate, which is the solid phase in
equilibrium with the solutions represented by the curve H_{1}J_{1}. J_{1}
and L_{1} are also transition points at which the solid phase undergoes
change, in the former case from hexahydrate to tetrahydrate; and in the
latter case, {286} from tetrahydrate to dihydrate. The complete curve of
equilibrium for magnesium chloride and water is, therefore, somewhat
complicated, and is a good example of the solubility curves obtained with
salts capable of forming several hydrates.
The solubility curve of potassium chloride is of the simplest form,
consisting only of the two branches AC, the freezing-point curve of ice,
and CO, the solubility curve of the salt. C is the cryohydric point. This
point and the two curves lie in the YT-plane.
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