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)
Suspended Transformation.--Just as in systems of one component we found
that a new phase was not necessarily formed when the conditions for its
existence were established, so also we find that even when the vapour
pressure is lowered below the dissociation pressure of a system,
dissociation does not necessarily occur. This is well known in the case of
Glauber's salt, first observed by Faraday. Undamaged crystals of
Na_{2}SO_{4},10H_{2}O could be kept unchanged in the open air, although the
vapour pressure of the system Na_{2}SO_{4},10H_{2}O--Na_{2}SO_{4}--vapour
is greater than the ordinary pressure of aqueous vapour in the air. That is
to say, the possibility of the formation of the new phase Na_{2}SO_{4} was
given; nevertheless this new phase did not appear, and the system therefore
became metastable, or unstable with respect to the anhydrous salt. When,
however, a trace of the new phase--the anhydrous salt--was brought in
contact with the hydrate, transformation occurred; the hydrate effloresced.
The possibility of suspended transformation or the non-formation of the new
phases must also be granted in the case where the vapour pressure is raised
above that corresponding to the system hydrate--anhydrous salt (or lower
hydrate)--vapour; in this case the formation of the higher hydrate becomes
a possibility, but not a certainty. Although there is no example of this
known in the case of hydrated salts, the suspension of the transformation
has been observed in the case of the compounds of ammonia with the metal
chlorides (p. 82). Horstmann,[158] for example, found that the pressure of
ammonia in contact with 2AgCl,3NH_{3} could be raised to a value higher
than the dissociation pressure of AgCl,3NH_{3} without this compound being
formed. We see, therefore, that even when the existence of the higher
compound in contact with the lower became possible, the higher compound was
not immediately formed.
Range of Existence of Hydrates.--In Fig. 19 the vapour {90} pressure curves
of the different hydrates of copper sulphate are represented as maintaining
their relative positions throughout the whole range of temperatures. But
this is not necessarily the case. It is possible that at some temperature
the vapour pressure curve of a lower hydrate may cut that of a higher
hydrate. At temperatures above the point of intersection, the lower hydrate
would have a higher vapour pressure than the higher hydrate, and would
therefore be metastable with respect to the latter. The range of stable
existence of the lower hydrate would therefore end at the point of
intersection. This appears to be the case with the two hydrates of sodium
sulphate, to which reference will be made later.[159]
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