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 lowest portion of the curve, AB, represents the equilibria between ice
and solutions containing ferric chloride. It represents, in other words,
the lowering of the fusion point of ice by addition of ferric chloride. At
the point B (-55°), the cryohydric point (p. 117) is reached, at which the
solution is in equilibrium with ice and ferric chloride dodecahydrate. As
{154} has already been shown, such a point represents an invariant system;
and the liquid phase will, therefore, solidify to a mixture of ice and
hydrate without change of temperature. If heat is added, ice will melt and
the system will pass to the curve BCDN, which is the solubility curve of
the dodecahydrate. At C (37°), the point of maximum temperature, the
hydrate melts completely. The retroflex portion of this curve can be
followed backwards to a temperature of 8°, but below 27.4° (D), the
solutions are supersaturated with respect to the heptahydrate; point D is
the eutectic point for dodecahydrate and heptahydrate. The curve DEF is the
solubility curve of the heptahydrate, E being the melting point, 32.5°. On
further increasing the quantity of ferric chloride, the temperature of
equilibrium is lowered until at F (30°) another eutectic point is reached,
at which the heptahydrate and pentahydrate can co-exist with solution. Then
follow the solubility curves for the pentahydrate, the tetrahydrate, and
the anhydrous salt; G (56°) is the melting point of the former hydrate, J
(73.5°) the melting point of the latter. H and K, the points at which the
curves intersect, represent eutectic points; the temperature of the former
is 55°, that of the latter 66°. The dotted portions of the curves represent
metastable equilibria.
As is seen from the diagram, a remarkable series of solubility curves is
obtained, each passing through a point of maximum temperature, the whole
series of curves forming an undulating "festoon." To the right of the
series of curves the diagram represents unsaturated solutions; to the left,
supersaturated.
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