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)
Suspended Transformation.--In many respects the transition point of two
solid phases is analogous to the melting point of a solid, or point at
which the solid passes into a liquid. In both cases the change of phase is
associated with a definite temperature and pressure in such a way that
below the point the one phase, above the point the other phase, is stable.
The transition point, however, differs in so far from a point of fusion,
that while it is possible to supercool a liquid, no definite case is known
where the solid has been heated above the triple point without passing into
the liquid state. Transformation, therefore, is suspended only on one side
of the melting point. In the case of two solid phases, however, the
transition point can be overstepped in both directions, so that each phase
can be obtained in the metastable condition. In the case of supercooled
water, further, we saw that the introduction of the stable, solid phase
caused the speedy transformation of the metastable to the stable condition
of equilibrium; but in the case of two solid phases the change from the
metastable to the stable modification may occur with great slowness, even
in presence of the stable form. This tardiness with which the stable
condition of equilibrium is reached greatly increases in many cases the
difficulty of accurately determining the transition point. The phenomena of
suspended transformation will, however, receive a fuller discussion later
(p. 68).
Transition Curve--Rhombic and Monoclinic Sulphur.--Just as we found the
melting point of ice to vary with the pressure, so also do we find that
change of pressure causes an alteration in the transition point. In the
case of the transition point of rhombic into monoclinic sulphur, increase
of pressure by 1 atm. raises the transition point by 0.04°-0.05°.[53] The
transition curve, or curve representing the change of the transition point
with pressure, will therefore slope to the right away from the pressure
axis. This is curve OC (Fig. 5).
{38}
Triple Point--Monoclinic Sulphur, Liquid, and Vapour. Melting Point of
Monoclinic Sulphur.--Above 95.5°, monoclinic sulphur is, as we have seen,
the stable form. On being heated to 120°, under atmospheric pressure, it
melts. This temperature is, therefore, the point of equilibrium between
monoclinic sulphur and liquid sulphur under atmospheric pressure. Since we
are dealing with a condensed system, this temperature may be regarded as
very nearly that at which the solid and liquid are in equilibrium with
their vapour, _i.e._ the triple point, solid (monoclinic)--liquid--vapour.
This point is represented in the diagram by B.
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