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)
chlorine being -102°.
Although complete measurements of the vapour pressure of the different
systems of pure iodine to pure chlorine have not been made, the
experimental data are nevertheless sufficient to allow of the general form
of the curves being indicated with certainty.
Bivariant Systems.--To these, only a brief reference need be made. Since
there are two components, two phases will form a bivariant system. The
fields in which these systems can exist are shown in Fig. 43 and Fig. 44,
which is a more diagrammatic representation of a portion of Fig. 43.
I. Iodine--vapour.
II. Solution--vapour.
III. Iodine trichloride--vapour.
IV. Iodine monochloride--vapour.
[Illustration: FIG. 44.]
The conditions for the existence of these systems will probably be best
understood from Fig. 44. Since the curve B'A' {168} represents the
pressures under which the system iodine--solution--vapour can exist,
increase of volume (diminution of pressure) will cause the volatilization
of the solution, and the system iodine--vapour will remain. If, therefore,
we start with a system represented by _a_, diminution of pressure at
constant temperature will lead to the condition represented by _x_. On the
other hand, increase of pressure at _a_ will lead to the condensation of a
portion of the vapour phase. Since, now, the concentration of chlorine in
the vapour is greater than in the solution, condensation of vapour would
increase the concentration of chlorine in the solution; a certain amount of
iodine must therefore pass into solution in order that the composition of
the latter shall remain unchanged.[249] If, therefore, the volume of vapour
be sufficiently great, continued diminution of volume will ultimately lead
to the disappearance of all the iodine, and there will remain only solution
and vapour (field II.). As the diminution of volume is continued, the
vapour pressure and the concentration of the chlorine in the solution will
increase, until when the pressure has reached the value _b_, iodine
monochloride can separate out. The system, therefore, again becomes
univariant, and at constant temperature the pressure and composition of the
phases must remain unchanged. Diminution of volume will therefore not
effect an increase of pressure, but a condensation of the vapour; and since
this is richer in chlorine than the {169} solution, solid iodine
monochloride must separate out in order that the concentration of the
solution remain unchanged.[250] As the result, therefore, we obtain the
bivariant system iodine monochloride--vapour.
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