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)
Concentration-Temperature Diagram.--In this diagram the temperatures are
taken as the abscissæ, and the composition of the solution, expressed in
atoms of chlorine to one atom of iodine,[242] is represented by the
ordinates. In the diagram, A represents the melting point of pure iodine,
114°. If chlorine is added to the system, a solution of chlorine in liquid
iodine is obtained, and the temperature at which solid iodine is in
equilibrium with the liquid solution will be all the lower the greater the
concentration of the chlorine. We therefore obtain the curve ABF, which
represents the composition of the solution {163} with which solid iodine is
in equilibrium at different temperatures. This curve can be followed down
to 0°, but at temperatures below 7.9° (B) it represents metastable
equilibria. At B iodine monochloride can be formed, and if present the
system becomes invariant; B is therefore a quadruple point at which the
four phases, iodine, iodine monochloride, solution, and vapour, can
coexist. Continued withdrawal of heat at this point will therefore lead to
the complete solidification of the solution to a mixture or conglomerate of
iodine and iodine monochloride, while the temperature remains constant
during the process. B is the eutectic point for iodine and iodine
monochloride.
Just as we found in the case of aqueous salt solutions that at temperatures
above the cryohydric or eutectic point, two different solutions could
exist, one in equilibrium with ice, the other in equilibrium with the salt
(or salt hydrate), so in the case of iodine and chlorine there can be two
solutions above the eutectic point B, one containing a lower proportion of
chlorine in equilibrium with iodine, the other containing a higher
proportion of chlorine in equilibrium with iodine monochloride. The
composition of the latter solution is represented by the curve BCD. As the
concentration of chlorine is increased, the temperature at which there is
equilibrium between iodine monochloride and solution rises until a point is
reached at which the composition of the solution is the same as that of the
solid. At this point (C), iodine monochloride melts. Addition of one of the
components will lower the temperature of fusion, and a continuous
curve,[243] exhibiting a retroflex portion as in the case of
CaCl_{2},6H_{2}O, will be obtained. At temperatures below its melting
point, therefore, iodine monochloride can be in equilibrium with two
different solutions.
The upper portion of this curve, CD, can be followed downwards to a
temperature of 22.7°. At this temperature iodine trichloride can separate
out, and a second quadruple {164} point (D) is obtained. This is the
eutectic point for iodine monochloride and iodine trichloride.
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