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)
From the foregoing it will be evident that the amount of acetic acid
required to produce a homogenous solution, will depend on the relative
amounts of chloroform and water from which we start, and can be ascertained
by joining the corner C with the point on the line AB representing the
total composition of the initial binary system. The point where this line
intersects the boundary curve _a_K_b_ will indicate the minimum amount of
acetic acid which, under these particular conditions, is necessary to give
one homogeneous solution.
Retrograde Solubility.--As a consequence of the fact that acetic acid
distributes itself unequally between chloroform and water, and the critical
point K, therefore, does not lie at the summit of the curve, it is possible
to start with a homogeneous solution in which the percentage amount of
acetic acid is greater than at the critical point, and to pass from this
first to a heterogenous and then again to a homogenous system merely by
altering the relative amounts of chloroform and water. This phenomenon, to
which the term _retrograde solubility_ is applied, will be observed not
only in the case of chloroform, water, and acetic acid, but in all other
systems in which the critical point lies below the highest point of the
boundary curve for heterogeneous systems. This will be seen from the
diagram, Fig. 85. Starting with the homogeneous system represented by _x_,
in which, therefore, the concentration of C is greater than in the critical
mixture (K), if the relative amounts of A and B are altered in the
direction _xx'_, while the amount of C is maintained constant, the system
will become heterogeneous when the composition reaches the point _y_, and
will remain {246} heterogeneous with changing composition until the point
_y'_ is passed, when it will again become homogeneous. If the relative
concentration of C is increased above that represented by the line SS, this
phenomenon will, of course, no longer be observed.
[Illustration: FIG. 85.]
Relationships similar to those described for chloroform, water, and acetic
acid are also found in the case of a number of other trios, _e.g._ ether,
water, and alcohol; chloroform, water, and alcohol.[322] They have also
been observed in the case of a considerable number of molten metals.[323]
Thus, molten lead and silver, as well as molten zinc and silver, mix in all
proportions; but molten lead and zinc are only partially miscible with one
another. When melted together, therefore, the last two metals will separate
into two liquid layers, one rich in lead, the other rich in zinc. If silver
is now added, and the temperature maintained above the freezing point of
the mixture, the silver passes for the most part, in accordance with the
law of distribution, into the upper layer, which is rich in zinc; silver
being more soluble in molten zinc than in molten lead. This is clearly
shown by the following figures:--[324]
{247}
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