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)
Triple Point.--We have already (p. 28) defined a triple point in a
one-component system, as being that pressure and temperature at which three
phases coexist in equilibrium; it represents, therefore, an invariant
system (p. 16). At the triple point also, three curves cut, viz. the curves
representing the conditions of equilibrium of the three univariant systems
formed by the combination of the three phases in pairs. The most common
triple point of a one-component system is, of course, the triple point,
solid, liquid, vapour (S-L-V), but other triple points[99] are also
possible when, as in the case of {56} sulphur or benzophenone, polymorphic
forms occur. Whether or not all the triple points can be experimentally
realized will, of course, depend on circumstances. We shall, in the first
place, consider only the triple point S-L-V.
As to the general arrangement of the three univariant curves around the
triple point, the following rules may be given. (1) The prolongation of
each of the curves beyond the triple point must lie between the other two
curves. (2) The middle position at one and the same temperature in the
neighbourhood of the triple point is taken by that curve (or its metastable
prolongation) which represents the two phases of most widely differing
specific volume.[100] That is to say, if a line of constant temperature is
drawn immediately above or below the triple point so as to cut the three
curves--two stable curves and the metastable prolongation of the third--the
position of the curves at that temperature will be such that the middle
position is occupied by that curve (or its metastable prolongation) which
represents the two phases of most widely differing specific volume.
Now, although these rules admit of a considerable variety of possible
arrangements of curves around the triple point,[101] only two of these have
been experimentally obtained in the case of the triple point
solid--liquid--vapour. At present, therefore, we shall consider only these
two cases (Figs. 13 and 14).
[Illustration: FIG. 13.]
[Illustration: FIG. 14.]
An examination of these two figures shows that they satisfy the rules laid
down. Each of the curves on being prolonged passes between the other two
curves. In the case of substances of the first type (Fig. 13), the specific
volume of the solid is greater than that of the liquid (the substance
contracts on fusion); the difference of specific volume will, therefore, be
greatest between liquid and vapour. The curve, therefore, for liquid and
vapour (or its prolongation) must lie between the other two curves; this is
seen from the figure to be the case. Similarly, the rule is satisfied by
the arrangement of curves in Fig. 14, where the difference of specific
volumes is {57} greatest between the solid and vapour. In this case the
curve S-V occupies the intermediate position.
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