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)
What was found in the case of tin, is met with also in the case of all
transformations in the solid state, but the velocity of the change is less
in some cases than in others, and appears to decrease with increase of the
valency of the element.[127] To this fact van't Hoff attributes the great
permanence of many really unstable (or metastable) carbon compounds.
Reference has been made to the fact that the velocity of transformation can
be accelerated by various means. One of the most important of these is the
employment of a liquid which has a solvent action on the solid phases. Just
as we have seen that at any given temperature the less stable form has the
higher vapour pressure, but that at the transition point the vapour
pressure of both forms becomes identical, so also it can be proved
theoretically, and be shown experimentally, that {71} at a given
temperature the solubility of the less stable form is greater than that of
the more stable, but that at the transition point the solubility of the two
forms becomes identical.[128]
If, then, the two solid phases are brought into contact with a solvent, the
less stable phase will dissolve more abundantly than the more stable; the
solution will therefore become supersaturated with respect to the latter,
which will be deposited. A gradual change of the less stable form,
therefore, takes place through the medium of the solvent. In this way the
more rapid conversion of white tin into grey in presence of a solution of
tin ammonium chloride (p. 42) is to be explained. Although, as a rule,
solvents accelerate the transformation of one solid phase into the other,
they may also have a retarding influence on the velocity of transformation,
as was found by Reinders in the case of mercuric iodide.[129]
The velocity of inversion, also, is variously affected by different
solvents, and in some cases, at least, it appears to be slower the more
viscous the solvent;[130] indeed, Kastle and Reed state that yellow
crystals of mercuric iodide, which, ordinarily, change with considerable
velocity into the red modification, have been preserved for more than a
year under vaseline.
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