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)
I. The Dilatometric Method.--Since, in the majority of cases,
transformation at the transition point is accompanied by an appreciable
change of volume, it is only necessary to ascertain the temperature at
which this change of volume occurs, in order to determine the transition
point. For this purpose the _dilatometer_ is employed, an apparatus which
consists of a bulb with capillary tube attached, and which constitutes a
sort of large thermometer (Fig. 129). Some of the substance to be examined
is passed into the bulb A through the tube B, which is then sealed off. The
rest of the bulb and a small portion of the capillary tube is then filled
with some liquid, which, of course, must be without chemical action on the
substance under investigation. A liquid, however, may be employed which
dissolves the substance, for, as we have seen (p. 70), the transformation
at the transition point is, as a rule, accelerated by the presence of a
solvent. On the other hand, the liquid must not dissolve in the substance
under examination, for the temperature of transformation would be thereby
altered.
{331}
In using the dilatometer, two methods of procedure may be followed.
According to the first method, the dilatometer containing the form stable
at lower temperatures is placed in a thermostat, maintained at a constant
temperature, until it has taken the temperature of the bath. The height of
the meniscus is then read on a millimetre scale attached to the capillary.
The temperature of the thermostat is then raised degree by degree, and the
height of the meniscus at each point ascertained. If, now, no change takes
place in the solid, the expansion will be practically uniform, or the rise
in the level of the meniscus per degree of temperature will be practically
the same at the different temperatures, as represented diagrammatically by
the line AB in Fig. 130. On passing through the transition point, however,
there will be a more or less sudden increase in the rise of the meniscus
per degree (line BC) if the specific volume of the form stable at higher
temperatures is greater than that of the original modification; thereafter,
the expansion will again be uniform (line CD). Similarly, on cooling,
contraction will at first be uniform and then at the transition point there
will be a relatively large diminution of volume.
[Illustration: FIG. 129.]
[Illustration: FIG. 130.]
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