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)
Transition Interval.--From what has been said, and from an examination of
the isothermal diagrams, Figs. 104-107, it will be seen that by a variation
of the temperature we can pass from a condition where the double salt is
quite incapable of existing in contact with solution (supersaturation being
excluded), to a condition where the existence of the double salt in
presence of solution becomes possible; only in the presence, however, of
one of the single salts (_transition point_, Fig. 105). A further change of
temperature leads to a condition where the stable existence of the pure
double salt in contact with solution just becomes possible (Fig. 106); and
from this point onwards, pure saturated solutions of the double salt can be
obtained (Fig. 107). _At any temperature, therefore, between that
represented by Fig. 105, and that represented by Fig. 106, the double salt
undergoes partial decomposition, with deposition of one of the constituent
salts._ The temperature range between the transition point and the
temperature at which a stable saturated solution of the pure double salt
just begins to be possible, is known as the _transition interval_ (p. 270).
As the figures show, the transition interval is limited on the one side by
the transition temperature, and on the other by the temperature at which
the solution saturated for double salt and the less soluble of the single
salts, contains the component salts in the same ratio as they are present
in the double salt. The greater the difference in the solubility of the
single salts, the larger will be the transition interval. {278}
Isothermal Evaporation.--The isothermal solubility curves are of great
importance for obtaining an insight into the behaviour of a solution when
subjected to isothermal evaporation. To simplify the discussion of the
relationships found here, we shall still suppose that the double salt
contains the single salts in equimolecular proportions; and we shall, in
the first instance, suppose that the unsaturated solution with which we
commence, also contains the single salts in the same ratio. The composition
of the solution must, therefore, be represented by some point lying on the
line OD, the bisectrix of the right angle.
From what has been said, it is evident that when the formation of a double
salt can occur, three temperature intervals can be distinguished, viz. the
single-salt interval, the transition interval, and the double-salt
interval.[359] When the temperature lies in the first interval, evaporation
leads first of all to the crystallization of one of the single salts, and
then to the separation of both the single salts together. In the second
temperature interval, evaporation again leads, in the first place, to the
deposition of one of the single salts, and afterwards to the
crystallization of the double salt. In the third temperature interval, only
the double salt crystallizes out. This will become clearer from what
follows.
[Illustration: FIG. 108.]
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