CHAP. 7: PHASE EQUILIBRIA [CONTENTS] 217
For integration we need to know the temperature dependence of the enthalpy of melting of a
pureithcomponent, ∆fusHi.Tfiis the melting (fusion) temperature of a pureithcomponent.
7.9.3 Two-component systems with totally immiscible components
in the solid phase
The coexistence curve of a liquid mixture with crystals of component 2 (lineTf, 2 E in Figure
7.11) is given by the equation
lnγ(l) 2 x(l) 2 =
∫T
Tf, 2
∆fusH 2
RT^2
dT. (7.63)
and the coexistence curve of a liquid mixture with crystals of component 1 (line ETf, 1 ) by the
equation
lnγ 1 (l)x(l) 1 =
∫T
Tf, 1
∆fusH 1
RT^2
dT. (7.64)
The common solution of both equations gives the temperature and composition of the
eutectic point E [see7.9.1].
Note:Most organic substances do not mix in the solid phase.
- Ideal solubility
If the liquid phase forms an ideal solution and the enthalpy of melting is independent
on temperature, we have
−lnx(l) 1 =
∆fusH 1
R
(
1
T
−
1
Tf, 1
)
(7.65)
and similarly for the second part of the liquidus curve. From this it follows that:
- The slope of the dependenceT–x 1 does not depend on substance 2.
- Solubility increases with increasing temperature.
- Of the two substances with roughly the same enthalpies of melting, the one with a
lower temperature of melting will dissolve more.