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)
These curves have been investigated at high pressures by Tammann, and the
results are represented according to scale in Fig. 6,[57] _a_ being the
curve for monoclinic sulphur and liquid; _b_, that for rhombic sulphur and
liquid; and _c_, that for rhombic and monoclinic sulphur.
Bivariant Systems.--Just as in the case of the diagram of states of water,
the areas in Fig. 5 represent the conditions for the stable existence of
the single phases: rhombic sulphur in the area to the left of AOCD;
monoclinic sulphur in the area OBC; liquid sulphur in the area EBCD;
sulphur vapour below the curves AOBE. As can be seen from the diagram, {40}
the existence of monoclinic sulphur is limited on all sides, its area being
bounded by the curves OB, OC, BC. At any point outside this area,
monoclinic sulphur can exist only in a metastable condition.
[Illustration: FIG. 6.]
Other crystalline forms of sulphur have been obtained,[58] so that the
existence of other systems of the one-component sulphur besides those
already described is possible. Reference will be made to these later
(p. 51).
{41}
C. _Tin._
Another substance capable of existing in more than one crystalline form, is
the metal tin, and although the general behaviour, so far as studied, is
analogous to that of sulphur, a short account of the two varieties of tin
may be given here, not only on account of their metallurgical interest, but
also on account of the importance which the phenomena possess for the
employment of this metal in everyday life.
After a winter of extreme severity in Russia (1867-1868), the somewhat
unpleasant discovery was made that a number of blocks of tin, which had
been stored in the Customs House at St. Petersburg, had undergone
disintegration and crumbled to a grey powder.[59] That tin undergoes change
on exposure to extreme cold was known, however, before that time, even as
far back as the time of Aristotle, who spoke of the tin as "melting."[60]
Ludicrous as that term may now appear, Aristotle nevertheless unconsciously
employed a strikingly accurate analogy, for the conditions under which
ordinary white tin passes into the grey modification are, in many ways,
quite analogous to those under which a substance passes from the solid to
the liquid state. The knowledge of this was, however, beyond the wisdom of
the Greek philosopher.
For many years there existed considerable confusion both as to the
conditions under which the transformation of white tin into its allotropic
modification occurs, and to the reason of the change. Under the guidance of
the Phase Rule, however, the confusion which obtained has been cleared
away, and the "mysterious" behaviour of tin brought into accord with other
phenomena of transformation.[61]
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