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)
We see, further, that the different areas are the regions of stability of
the phase common to the two curves by which the area is enclosed.[37] Thus,
the phase common to the two systems {30} represented by BO (ice and
vapour), and OA (water and vapour) is the vapour phase; and the area BOA is
therefore the area of the vapour phase. Similarly, BOC is the area of the
ice phase, and COA the area of the water phase.
Supercooled Water. Metastable State.--When heated under the ordinary
atmospheric pressure, ice melts when the temperature reaches 0°, and it has
so far not been found possible to raise the temperature of ice above this
point without liquefaction taking place. On the other hand, it has long
been known that water can be cooled below zero without solidification
occurring. This was first discovered in 1724 by Fahrenheit,[38] who found
that water could be exposed to a temperature of -9.4° without solidifying;
so soon, however, as a small particle of ice was brought in contact with
the water, crystallization commenced. Superfused or supercooled
water--_i.e._ water cooled below 0°--is unstable only in respect of the
solid phase; so long as the presence of the solid phase is carefully
avoided, the water can be kept for any length of time without solidifying,
and the system supercooled water and vapour behaves in every way like a
stable system. A system, now, which in itself is stable, and which becomes
instable only in contact with a particular phase, is said to be
_metastable_, and the region throughout which this condition exists is
called the metastable region. Supercooled water, therefore, is in a
metastable condition. If the supercooling be carried below a certain
temperature, solidification takes place spontaneously without the addition
of the solid phase; the system then ceases to be metastable, and becomes
_instable_.
Not only has water been cooled to temperatures considerably below the
melting point of ice, but the vapour pressure of the supercooled water has
been measured. It is of interest and importance, now, to see what
relationship exists between the vapour pressure of ice and that of
supercooled water at the same temperature. This relationship is clearly
shown by the numbers in the following table,[39] and is represented in Fig.
3, {31} p. 27., and diagrammatically in Fig. 4, the vapour pressures of
supercooled water being represented by the curve OA', which is the unbroken
continuation of AO.
VAPOUR PRESSURE OF ICE AND OF SUPERCOOLED WATER.
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