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)
Efflorescence.--From Fig. 19 we are enabled to predict the conditions under
which a given hydrated salt will effloresce when exposed to the air. We
have just learned that copper {87} sulphate pentahydrate, for example, will
not be formed unless the pressure of the aqueous vapour reaches a certain
value; and that conversely, if the vapour pressure falls below the
dissociation pressure of the pentahydrate, this salt will undergo
dehydration. From this, then, it is evident that a crystalline salt hydrate
will effloresce when exposed to the air, if the partial pressure of the
water vapour in the air is lower than the dissociation pressure of the
hydrate. At the ordinary temperature the dissociation pressure of copper
sulphate is less than the pressure of water vapour in the air, and
therefore copper sulphate does not effloresce. In the case of sodium
sulphate decahydrate, however, the dissociation pressure is greater than
the normal vapour pressure in a room, and this salt therefore effloresces.
[Illustration: FIG. 20.]
Indefiniteness of the Vapour Pressure of a Hydrate.--Reference has already
been made (p. 84), in the case of the ammonia compounds of the metal
chlorides, to the importance of the solid product of dissociation for the
definition of the dissociation pressure. Similarly also in the case of a
hydrated salt. A salt hydrate in contact with vapour constitutes only a
bivariant system, and can exist therefore at different values of
temperature and pressure of vapour, as is seen from the diagram, Fig. 19.
Anhydrous copper sulphate can exist in contact with water vapour at all
values of temperature and pressure lying in the field below the curve OC;
and the hydrate CuSO_{4},H_{2}O can exist in contact with vapour at all
values of temperature and pressure in the field BOC. Similarly, each of the
other hydrates can exist in contact with vapour at different values of
temperature and pressure.
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