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)
For the purpose of representing the relationships found here we shall
employ a temperature-concentration diagram,[267] in which the ordinates
represent the temperature and the abscissæ the concentration of the
components. Since there are two solutions, the liquid and the solid, and
since the concentration of the components in these two phases is not, in
general, the same, two curves will be required for each system, one
relating to the liquid phase, the other relating to the solid. The
temperature at which solid begins to be deposited from the liquid solution
will be called the _freezing point_ of the mixture, and the temperature at
which the solid solution just begins to liquefy will be called the _melting
point_ of the solid solution. The temperature-concentration curve for the
liquid phase will therefore be the freezing-point curve; that for the solid
solution, the melting-point curve. The latter will be represented by a
dotted line.[268]
{183}
I.--THE TWO COMPONENTS CAN FORM AN UNBROKEN SERIES OF MIXED CRYSTALS.
Since, as has already been pointed out (p. 176), a mixed crystal (solid
solution) constitutes only one phase, it is evident that if the two
components are miscible with one another in all proportions in the solid
state, there can never be more than one solid phase present, viz. the solid
solution or mixed crystal. If the components are completely miscible in the
solid state, they will also be completely miscible in the liquid state, and
there can therefore be only one liquid phase. The system can at no point
become invariant, because there can never be more than three phases
present. When, therefore, the two components form a continuous series of
mixed crystals, the equilibrium curve must also be continuous. Of these
systems three types are found.
[Illustration: FIG. 49.]
(_a_) _The freezing points of all mixtures lie between the freezing points
of the pure components_ (Curve I., Fig. 49).
Examples.--This type of curve is represented by the mixed crystals of
naphthalene and [beta]-naphthol.[269] The addition of [beta]-naphthol to
naphthalene raises the freezing point of the latter, and the rise is
directly proportional to the amount of naphthol added. The freezing point
curve is therefore a straight line joining the melting points of the two
components. This behaviour, however, is rather exceptional, the
freezing-point curve lying generally above, sometimes also below, the
straight line joining the melting points of the pure components. Thus the
freezing-point curve of mixtures of [alpha]-monochlorocinnamic aldehyde and
[alpha]-monobromocinnamic aldehyde[270] lies above the {184} straight line
joining the melting points of the pure components (31.22° and 69.56°), as
is evident from the following table:--
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