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)
As we have already seen (p. 122), water and succinic nitrile can form two
liquid layers between the temperatures 18.5° and 55.5°; while alcohol and
nitrile can form two liquid layers between 13° and 31°. If, then, between
these two temperature limits, alcohol is added to a heterogeneous mixture
of water and nitrile, or water is added to a mixture of alcohol and
nitrile, two heterogeneous ternary systems will be formed, {250} and two
boundary curves will be obtained in the triangular diagram, as shown in
Fig. 90.[328] On changing the temperature, the boundary curves will also
undergo alteration, in a manner similar to that just discussed. As the
temperature falls, the two curves will spread out more and more into the
centre of the triangle, and might at last meet one another; while at still
lower temperatures we may imagine the curves still further expanding so
that the two heterogeneous regions flow into one another and form a _band_
on the triangular diagram (Fig. 91). This, certainly, has not been realized
in the case of the three components mentioned, because at a temperature
higher than that at which the two heterogeneous regions could fuse
together, solid separates out.
[Illustration: FIG. 92.]
The gradual expansion of a paraboloid into a band-like area of
heterogeneous ternary systems, has, however, been observed in the case of
water, phenol, and aniline.[329] In Fig. 92 are shown three isothermals,
viz. those for 148°, 95°, and 50°. At 148°, water and aniline form two
layers having the composition--
Water, 83.5 per cent. } { water, 20 per cent.
} and {
Aniline, 16.5 " } { aniline, 80 "
{251}
and the critical point _k'_ has the composition--
Water, 65; phenol, 13.2; aniline, 21.8 per cent.
At 95°, the composition of the two binary solutions is--
Water, 93 per cent. } { water 8 per cent.
} and {
Aniline, 7 " } { aniline, 92 "
while the point _k"_ has the composition
Water, 69.9; phenol, 26.6; aniline, 3.5 per cent.
At 50°, the region of heterogeneous states now forms a band, and the two
layers formed by water and aniline have the composition--
Water, 96.5 per cent. } { water, 5.5 per cent.
} and {
Aniline, 3.5 " } { aniline, 94.5 "
while the two layers formed by water and phenol have the composition--
Water, 89 per cent.} { water, 38 per cent.
} and {
Phenol, 11 " } { phenol, 62 "
All mixtures of water, phenol, and aniline, therefore, the composition of
which is represented by any point within the band _abcd_, will form two
ternary solutions; while if the composition is represented by a point
outside the band, only one homogeneous solution will be produced.
3. _The three components form three pairs of partially miscible liquids._
[Illustration: FIG. 93.]
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