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)
The Solubility Curve.--In studying the equilibria in those systems of two
components in which the liquid phase is a solution or phase of varying
composition, we shall in the present chapter limit the discussion to those
cases where no compounds are formed, but where the components crystallise
out in the pure state. Since some of the best-known examples of such
systems are yielded by the solutions of anhydrous salts in water, we shall
first of all briefly consider some of the results which have been obtained
with them.
For the most part the solubility curves have been studied only at
temperatures lying between 0° and 100°, the solid phase in contact with the
solution being the anhydrous salt. For the representation of these
equilibria, the concentration-temperature {112} diagram is employed, the
concentration being expressed as the number of grams of the salt dissolved
in 100 grams of water, or as the number of gram-molecules of salt in 100
gram-molecules of water. The curves thus obtained exhibit the different
forms to which reference has already been made. So long as the salt remains
unchanged the curve will be continuous, but if the salt alters its form,
then the solubility curve will show a break.
[Illustration: FIG. 27.]
Now, we have already seen in Chapter III. that certain substances are
capable of existing in various crystalline forms, and these forms are so
related to one another that at a given temperature the relative stability
of each pair of polymorphic forms undergoes change. Since each crystalline
variety of a substance must have its own solubility, there must be a break
in the solubility curve at the temperature of transition of the two
enantiotropic forms. At this point the two solubility curves must cut, for
since the two forms are in equilibrium with respect to their vapour, they
must also be in equilibrium with respect to their solutions. From the table
on p. 63 it is seen that potassium nitrate, ammonium nitrate, silver
nitrate, thallium nitrate, thallium picrate, are capable of existing in two
or more different enantiotropic crystalline forms, the range of stability
of these forms being limited by definite temperatures (transition
temperature). Since the transition point is not altered by a solvent
(provided the latter is not absorbed by the solid phase), we should find on
studying the solubility of these substances in water that the solubility
curve would exhibit a change in direction at the temperature of transition.
As a matter of fact this has been verified, more especially in the case of
ammonium nitrate[187] {113} and thallium picrate.[188] The following table
contains the values of the solubility of ammonium nitrate obtained by
Müller and Kaufmann, the solubility being expressed in gram-molecules
NH_{4}NO_{3} in 100 gram-molecules of water. In Fig. 27 these results are
represented graphically. The equilibrium point was approached both from the
side of unsaturation and of supersaturation, and the condition of
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