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)
We have seen, in Chapter VI., that two liquids can form two immiscible
solutions, and the same has also been found true of solid solutions, as we
shall presently learn more fully. If, now, two immiscible solutions are
formed, then the system will become univariant, and at constant temperature
the _pc_-curve will be a straight line, as in the case of the formation of
a compound (cf. p. 86). The behaviour of this system will, therefore, also
be represented diagrammatically by Fig. 47.
[Illustration: FIG. 47.]
_Palladium and Hydrogen._--The phenomenon of the absorption of hydrogen by
palladium, to which Graham gave the name "occlusion," is one that has
claimed the attention of several investigators. Although Graham was not of
opinion that a compound is formed, but rather that the gas undergoes very
great condensation, acts as a quasi-metal (to which he gave the name
hydrogenium), and forms a homogeneous alloy with the palladium, later
investigations, especially those of Troost and Hautefeuille,[259] pointed
to the formation of a definite chemical compound, having the formula
Pd_{2}H. This conclusion has, however, not been confirmed by subsequent
investigation.[260]
Roozeboom and Hoitsema[261] sought to arrive at a final decision as to the
nature of the phenomenon by an investigation of the equilibrium between
hydrogen and palladium on the basis of the Phase Rule classification given
above. If a compound is formed, diminution of volume would cause no
increase of pressure, but only an increase in the amount of the compound.
As this is the only case of gas absorption which has been {179} accurately
studied from this point of view, a brief account of the results obtained
will be given here, although these are not so clear and free from ambiguity
as one would desire.
The scientists just mentioned investigated the variation of the pressure of
hydrogen with the amount absorbed by the metal at different temperatures,
and a few of their results, typical of all, are represented graphically in
Fig. 48; the curves indicating the variation of the gas pressure with the
concentration of the hydrogen in the palladium at the temperatures 120°,
170°, and 200°. As can be seen, the curve consists of three parts, an
ascending portion which passes gradually and continuously into an almost
horizontal but slightly ascending middle part, which in turn passes without
break into a second rapidly ascending curve. This, as Fig. 48 indicates, is
the general form of the curve; but the length of the middle portion varies
with the temperature, being shorter at higher than at lower temperatures.
[Illustration: FIG. 48.]
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