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)
Temperature, also, has a very considerable influence on the velocity of
transformation. The higher the temperature, and the farther it is removed
from the equilibrium point (transition point), the greater is the velocity
of change. Above the transition point, these two factors act in the same
direction, and the velocity of transformation will therefore go on
increasing indefinitely the higher the temperature is raised. Below the
transition point, however, the two factors act in opposite directions, and
the more the temperature is lowered, the more is the effect of removal from
the equilibrium point counteracted. A point will therefore be reached at
which the velocity is a maximum. Reduction of the temperature {72} below
this point causes a rapid falling off in the velocity of change. The point
of maximum velocity, however, is not definite, but may be altered by
various causes. Thus, Cohen found that in the case of tin, the point of
maximum velocity was altered if the metal had already undergone
transformation; and also by the presence of different liquids.[131]
Lastly, the presence of small quantities of different substances--catalytic
agents or catalyzers--has a great influence on the velocity of
transformation. Thus, _e.g._, the conversion of white to red phosphorus is
accelerated by the presence of iodine (p. 47).
Greater attention, however, has been paid to the study of the velocity of
crystallization of a supercooled liquid, the first experiments in this
direction having been made by Gernez[132] on the velocity of
crystallization of phosphorus and sulphur. Since that time, the velocity of
crystallization of other supercooled liquids has been investigated; such as
acetic acid and phenol by Moore;[133] supercooled water by Tumlirz;[134]
and a number of organic substances by Tammann,[135] Friedländer and
Tammann,[136] and by Bogojawlenski.[137]
In measuring the velocity of crystallization, the supercooled liquids were
contained in narrow glass tubes, and the time required for the
crystallization to advance along a certain length of the tube was
determined, the velocity being expressed in millimetres per minute. The
results which have so far been obtained may be summarized as follows. For
any given degree of supercooling of a substance, the velocity of
crystallization is constant. As the degree of supercooling increases, the
velocity of crystallization also increases, until a certain point is
reached at which the velocity is a maximum, which has a definite
characteristic value for each substance. This maximum velocity remains
constant over a certain range of {73} temperature; thereafter, the velocity
diminishes fairly rapidly, and, with sufficient supercooling, may become
zero. The liquid then passes into a glassy mass, which will remain
(practically) permanent even in contact with the crystalline solid.
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