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)
The relations which are found here will be best understood with the help of
Fig. 32.[207] In this figure, OB represents the sublimation curve of ice,
and BC the vaporization curve of water; the curve for the solution must lie
below this, and must cut the sublimation curve of ice at some temperature
below the melting point. The point of intersection A is the cryohydric
point. If the solubility increases with rise of temperature, the increase
of the vapour pressure due to the latter will be partially annulled. Since
at first the effect of increase of temperature more than counteracts the
depressing action of increase of concentration, the vapour pressure will
increase on raising the temperature above the cryohydric point. If the
elevation of temperature is continued, however, to the melting point of the
salt, the effect of increasing concentration makes itself more and more
felt, so that the vapour-pressure curve of the solution falls more and more
below that of the pure liquid, and the pressure will ultimately become
equal to that of the pure salt; that is to say, practically equal to zero.
The curve will therefore be of the general form AMF shown in Fig. 32. If
the solubility should diminish with rise of temperature, the two factors,
temperature and concentration, will act in the same direction, and the
vapour-pressure curve will rise relatively more rapid than that of the pure
liquid; since, however, the pure salt is ultimately obtained, the
vapour-pressure curve must in this case also finally approach the value
zero.
[Illustration: FIG. 32.]
Other Univariant Systems.--Besides the univariant system {128}
salt--solution--vapour already considered, three others are possible, viz.
ice--solution--vapour, ice--salt--solution, and ice--salt--vapour.
The fusion point of a substance is lowered, as we have seen, by the
addition of a foreign substance, and the depression is all the greater the
larger the quantity of substance added. The vapour pressure of the water,
also, is lowered by the solution in it of other substances, so that the
vapour pressure of the system ice--solution--vapour must decrease as the
temperature falls from the fusion point of ice to the cryohydric point.
This curve is represented by BA (Fig. 32), and is coincident with the
sublimation curve of ice.
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