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)
So long as the four phases hydrate, two liquid phases, and vapour are
present, the condition of the system is perfectly defined. By altering the
conditions, however, one of the phases can be made to disappear, and a
univariant system will then be obtained. Thus, if the vapour phase is made
to disappear, the univariant system solution I.--solution II.--hydrate,
will be left, and the temperature at which this system is in equilibrium
will vary with the pressure. This is represented by the curve FI; under a
pressure of 225 atm. the temperature of equilibrium is 17.1°. Increase of
pressure, therefore, raises the temperature at which the three phases can
coexist.
Again, addition of heat to the invariant system at F will cause the
disappearance of the solid phase, and there will be formed the univariant
system solution I.--solution II.--vapour. In the case of this system the
vapour pressure increases as the temperature rises, as represented by the
curve FG. Such a system is analogous to the case of ether and water, or
other two partially miscible liquids (p. 103). As the temperature changes,
the composition of the two liquid phases will undergo change; but this
system has not been studied fully.
The fourth curve, which ends at the quadruple point F, is {173} that
representing the vapour pressure of the system hydrate--solution I.--vapour
(FH). This curve has been followed to a temperature of 0°, the pressure at
this point being 113 cm. The metastable prolongation of GF has also been
determined. Although, theoretically, this curve must lie below FH, it was
found that the difference in the pressure for the two curves was within the
error of experiment.
Bivariant Systems.--The different bivariant systems, consisting of two
phases, which can exist within the range of temperature and pressure
included in Fig. 45, were given on p. 170. The conditions under which these
systems can exist are represented by the areas in the diagram, and the
fields of the different bivariant systems are indicated by letters,
corresponding to the letters on p. 170. Just as in the case of
one-component systems (p. 29), we found that the field lying between any
two curves gave the conditions of existence of that phase which was common
to the two curves, so also in the case of two-component systems, a
bivariant two-phase system occurs in the field enclosed[252] by the two
curves to which the two phases are common. As can be seen, the same
bivariant system can occur in more than one field.
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