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)
complete and reversible transformation of one form into the other occurs.
This temperature, which refers to equilibrium in absence of the vapour
phase, is known as the _transition temperature_ or _inversion temperature_.
Were we dependent on measurements of pressure and temperature, the
determination of the transition point might be a matter of great
difficulty. When we consider, however, that the other physical properties
of the solid phases, _e.g._ the density, undergo an abrupt change on
passing through the transition point, owing to the transformation of one
form into the other, then any method by which this abrupt change in the
physical properties can be detected may be employed for determining the
transition point. A considerable number of such methods have been devised,
and a description of the most important of these is given in the Appendix.
In the case of sulphur, the transition point of rhombic into monoclinic
sulphur was found by Reicher[51] to lie at 95.5°. Below this temperature
the octahedral, above it the monoclinic, is the stable form.
Condensed Systems.--We have already seen that in the change of the melting
point of water with the pressure, a very great increase of the latter was
necessary in order to produce a comparatively small change in the
temperature of equilibrium. This is a characteristic of all systems from
which the vapour phase is absent, and which are composed only of solid and
liquid phases. Such systems are called _condensed systems_,[52] and in
determining the temperature of equilibrium of such systems, practically the
same point will be obtained whether the measurements are carried out under
atmospheric pressure or under the pressure of the vapour of the solid or
liquid phases. The transition point, therefore, as determined in open
vessels at atmospheric pressure, will differ only by a very slight amount
from the triple point, or point at which the two solid or liquid phases are
in equilibrium under the pressure of their vapour. {37} The determination
of the transition point is thereby greatly simplified.
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