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)
Transition Point.--Just as in the case of sulphur, so also in the case of
tin, there is a transition point above which the {42} one form, ordinary
white tin, and below which the other form, grey tin, is the stable variety.
In the case of this metal, the transition point was found by Cohen and van
Eyk, who employed both the dilatometric and the electrical methods
(Appendix) to be 20°. Below this temperature, grey tin is the stable form.
But, as we have seen in the case of sulphur, the change of the metastable
into the stable solid phase occurs with considerable slowness, and this
behaviour is found also in the case of tin. Were it not so, we should not
be able to use this metal for the many purposes to which it is applied in
everyday life; for, with the exception of a comparatively small number of
days in the year, the temperature of our climate is below 20°, and _white
tin is, therefore, at the ordinary temperature, in a metastable condition_.
The change, however, into the stable form at the ordinary temperature,
although slow, nevertheless takes place, as is shown by the partial or
entire conversion of articles of tin which have lain buried for several
hundreds of years.
On lowering the temperature, the velocity with which the transformation of
the tin occurs is increased, and Cohen and van Eyk found that the
temperature of maximum velocity is about -50°. Contact with the stable form
will, of course, facilitate the transformation.
The change of white tin into grey takes place also with increased velocity
in presence of a solution of tin ammonium chloride (pink salt), which is
able to dissolve small quantities of tin. In presence of such a solution
also, it was found that the temperature at which the velocity of
transformation was greatest was raised to 0°. At this temperature, white
tin in contact with a solution of tin ammonium chloride, and the grey
modification, undergoes transformation to an appreciable extent in the
course of a few days.
Fig. 7 is a photograph of a piece of white tin undergoing transformation
into the grey variety.[62] The bright surface of the tin becomes covered
with a number of warty masses, formed of the less dense grey form, and the
number and size of these continue to grow until the whole of the white tin
has passed {43} into a grey powder. On account of the appearance which is
here seen, this transformation of tin has been called by Cohen the "tin
plague."
[Illustration: FIG. 7.]
{44}
Enantiotropy and Monotropy.--In the case of sulphur and tin, we have met
with two substances existing in polymorphic forms, and we have also learned
that these forms exhibit a definite transition point at which their
relative stability is reversed. Each form, therefore, possesses a definite
range of stable existence, and is capable of undergoing transformation into
the other, at temperatures above or below that of the transition point.
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