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)
If an unsaturated solution, the composition of which is represented by a
point in the field to the right of the solubility curves, is cooled down,
the result obtained will differ according as the composition of the
solution is the same as that of a cryohydric point, or of a melting point,
or has an intermediate value. Thus, if a solution represented by _x__{1} is
cooled down, the composition will remain unchanged as indicated by the
horizontal dotted line, until the point D is reached. At this point,
dodecahydrate and heptahydrate will separate out, and the liquid will
ultimately solidify completely to a mixture or "conglomerate" of these two
hydrates; the temperature of {155} the system remaining constant until
complete solidification has taken place. If, on the other hand, a solution
of the composition _x__{3} is cooled down, ferric chloride dodecahydrate
will be formed when the temperature has fallen to that represented by C,
and the solution will completely solidify, without alteration of
temperature, with formation of this hydrate. In both these cases,
therefore, a point is reached at which complete solidification occurs
without change of temperature.
Somewhat different, however, is the result when the solution has an
intermediate composition, as represented by _x__{2} or _x__{4}. In the
former case the dodecahydrate will first of all separate out, but on
further withdrawal of heat the temperature will fall, the solution will
become relatively richer in ferric chloride, owing to separation of the
hydrate, and ultimately the eutectic point D will be reached, at which
complete solidification will occur. Similarly with the second solution.
Ferric chloride dodecahydrate will first be formed, and the temperature
will gradually fall, the composition of the solution following the curve CB
until the cryohydric point B is reached, when the whole will solidify to a
conglomerate of ice and dodecahydrate.
Suspended Transformation.--Not only can the upper branch of the solubility
curve of the dodecahydrate be followed backwards to a temperature of 8°, or
about 19° below the temperature of transition to the heptahydrate; but
suspended transformation has also been observed in the case of the
heptahydrate and the pentahydrate. To such an extent is this the case that
the solubility curve of the latter hydrate has been followed downwards to
its point of intersection with the curve for the dodecahydrate. This point
of intersection, represented in Fig. 39 by M, lies at a temperature of
about 15°; and at this temperature, therefore, it is possible for the two
solid phases dodecahydrate and pentahydrate to coexist, so that M is a
eutectic point for the dodecahydrate and the pentahydrate. It is, however,
a metastable eutectic point, for it lies in the region of supersaturation
with respect to the heptahydrate; and it can be realized only because of
the fact that the latter hydrate is not readily formed.
Public-domain text, read in full here on John Shaqi.
Reviews
Reviews
No reviews yet
Be the first to share your thoughts on this work.
Elsewhere in the archive
Join the Discussion
Join the discussion
Sign in to leave a comment or review.
Sign InorCreate an account