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The same changes in the phases occur when heat is added or withdrawn at
constant pressure, so long as the three phases are present. Continued
addition of heat, however, at constant pressure will ultimately cause the
formation of the bivariant system vapour alone; continued withdrawal of
heat will ultimately cause the formation of solid alone. This will be
readily understood from Fig. 15. The dotted line D'OD is a line of constant
pressure; on adding heat, the system passes along the line OD into the
region of vapour; on heat being withdrawn, the system passes along OD' into
the area of solid.
[Illustration: FIG. 15.]
Similar changes are produced when the volume of the system is altered.
Alteration of volume may take place either while transference of heat to or
from the system is cut off (adiabatic change), or while such transference
may occur (isothermal change). In the latter case, the temperature of the
system will remain constant; in the former case, since at the triple point
the pressure must be constant so long as the three phases are present,
increase of volume must be compensated by the evaporation of liquid. This,
however, would cause the temperature to fall (since communication of heat
from the outside is supposed to be cut off), and a portion of the liquid
must therefore freeze. In this way the latent heat of evaporation is
counterbalanced by the latent heat of fusion. As the result of increase of
volume, therefore, the process occurs L --> S + V. Diminution of volume,
without transference of heat, will bring about the opposite change, S + V
--> L. In the former case there is ultimately obtained the univariant
system S-V; in the latter case there will be {61} obtained either S-L or
L-V according as the vapour or solid phase disappears first.
This argument holds good for both types of triple point shown in Figs. 13
and 14 (p. 57). A glance at these figures will show that increase of volume
(diminution of pressure) will lead ultimately to the system S-V, for at
pressures lower than that of the triple point, the liquid phase cannot
exist. Decrease of volume (increase of pressure), on the other hand, will
lead either to the system S-L or L-V, because these systems can exist at
pressures higher than that of the triple point. If the vapour phase
disappears and we pass to the curve S-L, continued diminution of volume
will be accompanied by a fall in temperature in the case of systems of the
first type (Fig. 13), and by a rise in temperature in the case of systems
of the second type (Fig. 14).
[Illustration: FIG. 16.]
[Illustration: FIG. 17.]
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