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)
It has long been known that if water is placed in a closed, exhausted
space, vapour is given off and a certain pressure is created in the
enclosing vessel. Thus, when water is placed in the Torricellian vacuum of
the barometer, the mercury is depressed, and the amount of depression
increases as the temperature is raised. But, although the pressure of the
vapour increases as the temperature rises, its value at any given
temperature is constant, no matter whether the amount of water present or
the volume of the vapour is great or small; if the pressure on the vapour
is altered while the temperature is maintained constant, either the water
or the vapour will ultimately disappear; the former by evaporation, the
latter by condensation. At any given temperature within certain limits,
therefore, water and vapour can exist permanently in contact with one
another--or, as it is said, be in equilibrium with one another--only when
the pressure has a certain definite value. The same law of constancy of
vapour pressure at a given {2} temperature, quite irrespective of the
volumes of liquid and vapour,[1] holds good also in the case of alcohol,
ether, benzene, and other pure liquids. It is, therefore, not unnatural to
ask the question, Does it hold good for all liquids? Is it valid, for
example, in the case of solutions?
We can find the answer to these questions by studying the behaviour of a
solution--say, a solution of common salt in water--when placed in the
Torricellian vacuum. In this case, also, it is observed that the pressure
of the vapour increases as the temperature is raised, but the pressure is
no longer independent of the volume; as the volume increases, the pressure
slowly diminishes. If, however, solid salt is present in contact with the
solution, then the pressure again becomes constant at constant temperature,
even when the volume of the vapour is altered. As we see, therefore,
solutions do not behave in the same way as pure liquids.
Moreover, on lowering the temperature of water, a point is reached at which
ice begins to separate out; and if heat be now added to the system or
withdrawn from it, no change will take place in the temperature or vapour
pressure of the latter until either the ice or the water has
disappeared.[2] Ice, water, and vapour, therefore, can be in equilibrium
with one another only at one definite temperature and one definite
pressure.
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