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)
In ordinary glass we have a familiar example of a liquid which has been
cooled to a temperature at which crystallization takes place with very
great slowness. If, however, glass is heated, a temperature is reached,
much below the melting point of the glass, at which crystallization occurs
with appreciable velocity, and we observe the phenomenon of
devitrification.[138]
When the velocity of crystallization is studied at temperatures above the
maximum point, it is found that the velocity is diminished by the addition
of foreign substances; and in many cases, indeed, it has been found that
the diminution is the same for equimolecular quantities of different
substances. It would hence appear possible to utilize this behaviour as a
method for determining molecular weights.[139] The rule is, however, by no
means a universal one. Thus it has been found by F. Dreyer,[140] in
studying the velocity of crystallization of formanilide, that the
diminution in the velocity produced by equivalent amounts of different
substances is not the same, but that the foreign substances exercise a
specific influence. Further, von Pickardt's rule does not hold when the
foreign substance forms mixed crystals (Chap. X.) with the crystallizing
substance.[141]
Law of Successive Reactions.--When sulphur vapour is cooled at the ordinary
temperature, it first of all condenses to drops of liquid, which solidify
in an amorphous form, and only after some time undergo crystallization; or,
when phosphorus vapour is condensed, white phosphorus is first formed, and
not the more stable form--red phosphorus. It has also been observed that
even at the ordinary temperature (therefore much below the transition
point) sulphur may crystallize out from solution in benzene, alcohol,
carbon disulphide, and other {74} solvents, in the prismatic form, the less
stable prismatic crystals then undergoing transformation into the rhombic
form;[142] a similar behaviour has also been observed in the transformation
of the monotropic crystalline forms of sulphur.[143]
Many other examples might be given. In organic chemistry, for instance, it
is often found that when a substance is thrown out of solution, it is first
deposited as a liquid, which passes later into the more stable crystalline
form. In analysis, also, rapid precipitation from concentrated solution
often causes the separation of a less stable and more soluble amorphous
form.
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