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)
Since in systems of two components the two phases, solution and vapour,
constitute a bivariant system, the vapour pressure is undefined, and may
have different values at the same temperature, depending on the
concentration. In order that there may be for each temperature a definite
corresponding pressure of the vapour, a third phase must be present. This
condition is satisfied by the system solid--liquid (solution)--vapour; that
is, by the saturated solution (p. 108). In the case of a saturated
solution, therefore, the pressure of the vapour at any given temperature is
constant.
Vapour Pressure of Solid--Solution--Vapour.--It has long been known that
the addition of a non-volatile solid to a liquid in which it is soluble
lowers the vapour pressure of the solvent; and the diminution of the
pressure is approximately proportional to the amount of substance dissolved
(Law of Babo). The vapour-pressure curve, therefore, of a solution of a
salt in water must lie below that for pure water. Further, in the case of a
pure liquid, the vaporization curve is a function only of the temperature
(p. 63), whereas, in the case of a solution, the pressure varies both with
the temperature and the _concentration_. These two factors, however, act in
opposite directions; for although the vapour pressure in all cases
increases as the temperature rises, increase of concentration, as we have
seen, lowers the vapour pressure. Again, since the concentration itself
varies with the temperature, two cases have to be considered, viz. where
the concentration increases with rise of {127} temperature, and where the
concentration diminishes with rise of temperature.
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