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)
In connection with this curve, attention may be called to the interesting
fact that although the solid produced by cooling the liquid phase at the
eutectic point has a composition approximating to that of a compound of
equimolecular proportions of the phenol and toluidine, and a constant
melting point, it is nevertheless a _mixture_. Although, as a rule, the
constituents of the eutectic mixture are not present in simple molecular
proportions, there is no reason why they should not be so; and it is
therefore necessary to beware of assuming the formation of compounds in
such cases.[293]
Fig. 67, on the other hand, indicates with perfect certainty the formation
of a compound between phenol and [alpha]-naphthylamine.[294] (_Cf._ curve
I., Fig. 64.)
Phenol freezes at 40.4°, but the addition of [alpha]-naphthylamine lowers
the freezing point as represented by the curve AC. At C (16.0°) the
compound C_{6}H_{5}OH,C_{10}H_{7}NH_{2} is formed, and the system becomes
invariant. On increasing the amount of the amine, the temperature of
equilibrium rises, the solid phase now being the compound. At D, the curve
passes through a maximum (28.8°), at which the solid and liquid phases have
the same composition. This is the melting point of the compound. Further
addition of the amine lowers the temperature of equilibrium, until at E
solid [alpha]-naphthylamine separates out, and a second eutectic point
(24.0°) is obtained. BE is the {214} freezing-point curve of
[alpha]-naphthylamine in presence of phenol, the freezing point of the pure
amine being 48.3°.
On account of the great sluggishness with which the compound of phenol and
[alpha]-naphthylamine crystallizes, it was found possible to follow the
freezing point curves of phenol and the amine to temperatures considerably
below the eutectic points, as shown by the curves CF and EG.
[Illustration: FIG. 67.]
Phenol can also combine with _p_-toluidine in equimolecular proportions;
and this compound is of interest, from the fact that it exists in two
crystalline forms melting at 28.5° and 30°. Each of these forms now must
have its own equilibrium curve, and it was found that the intermediate
portion of the freezing point curve was duplicated, as shown in Fig.
68.[295]
{215}
[Illustration: FIG. 68.]
[Illustration: FIG. 69.]
{216}
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