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The Freezing Point Depression Law

in Physical Chemistry
Is It Time for a Change?
Hugo F. Franzen
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The freezing point depression law has been taught for A(in solid solution) =
A (in liquid solution) (2)
many years as part of both freshman and physical chemistry B(in solid solution) =
B(in liquid solution) (3)
courses. On the freshman level the law is usually taught
phenomenologically, whereas in physical chemistry its ori- be considered instead. Taking the Raoult’s law (pure liquid
gin in the thermodynamics of heterogeneous equilibrium is and solid) standard states for A and the Henry’s law (B in
the focus of attention. The teaching of the law at this level the hypothetical ideal Xb 1 liquid and solid solutions)
=

has a number of purposes among which are (1) to display the standard states for B and applying the Gibbs-Helmholz
thermodynamic origin of the law, (2) to provide experience equation in ideally dilute solution and, as usual in the devel-
in the determination of molecular weight or freezing point opment of the freezing point depression law, assuming
depression, (3) to provide a basic understanding of eutectic ACP° AT to be negligible relative to AH°, yields
melting and solidification, (4) to provide a basis for a deeper
understanding of both Raoult’s law behavior (colligative In
XA' _
Aif°fuaion
ri.ri (4)
[t
_
~

XT R
properties) and departures from ideality, and (5) to illus- T,J
trate the linearization of a more complex functional relation- and
ship.
The purpose of this article is to suggest a change in physi-
cal chemistry courses to a slightly more complicated but
significantly more useful generalization of the simple freez-
where XA' and XAS are the mole fractions of A in the liquid
ing point depression law, one that achieves all of the pur-
and solid phases, Tf is the melting temperature of A,
poses stated above and a number of additional purposes as
well. The time is appropriate for this move for two reasons. AH0fusion is the enthalpy of fusion of pure A, K is the distri-
The first is that the simple freezing point depression law is bution equilibrium constant, Xb’/Xbs, K° is the limiting
value of K at Tf( and AH ** is the standard enthalpy change
currently being taught in freshman chemistry courses mak-
for reaction 3.
ing the treatment common to most physical chemistry texts
somewhat redundant (not totally so, of course, because the For sufficiently dilute solutions
freshman-level treatment generally is not based upon an XA'
In XB 1
(6)
understanding of calculus or chemical potential). The sec-
» —

XBS
——

ond is that freezing point depression is no longer as impor-

tant as it once was in the determination of molecular weight. and
This is where the generalization suggested here, namely 1 1 AT
(7)
_

treatment of solid-liquid equilibria in which solid-solution T T~ T{2

is allowed, really shines, for some modern separations and
materials handling technologies (zone refining, skull melt- where AT -

Tf —

T, and thus,
ing) depend for their success upon control of the distribution fusion
of impurities between solids and melts. XB'-X (8)
What is suggested here is that the usual two-component, RT(2
two-phase liquid-solid treatment be generalized to the case Furthermore, taking K = K° + AK for sufficiently dilute
of ideally dilute solid-liquid solution equilibrium. This has solution
the advantage of removing the assumption that in both prac- K AK
tice and principle is false, namely the assumption that there ln
,
“ (9)
K° K°
is zero solid solubility; nonetheless, the usual freezing point
depression law is recovered when the solubility of solute in and therefore,
the solid is negligibly small.
The traditional freezing point depression treatment is AK A/T^AT
(10)
,
~

based upon the reaction K° RT2

A(pure solid) =
A(in liquid solution with B) (1)
and what is suggested here is that the
reactions
more realistic net K = K' Yi-^a
{
t)) RTf2
(11)

Volume 65 Number 12 December 1988 1077

 sion law. For K° < 1 (B more soluble in solid than in the
liquid) eqs 13 and 14 imply AT < 1 (freezing point elevation),
and for K° > 1 they yield depression of the melting point
with solid solution. For all cases eqs 13 and 14 are linear
equations appropriate for the analysis of solid-liquid equi-
libria in sufficiently dilute solutions. The quantity K° can be
viewed as a parameter that determines the behavior: K° » »
means zero solid solubility and the usual freezing point de-
pression law, K° > 1 means some solid solubility but greater
solubility in the liquid and freezing point depression, and K°
< 1 means greater solubility in the solid than in the liquid
and freezing point elevation.
As the solutions become more concentrated the linear laws
will no longer apply because the approximations are no long-
er valid, and because the solutions will in general no longer
be ideal (will no longer obey Raoult’s and Henry’s laws). In
=
the case of higher concentrations of solute the appropriate
XSi '"XGe laws are
Phase diagram for Ge-Si. A H° fusion
> >< "_1 _T
In II _

(14)
7a5Aas R T Ts
and
K A "1 __1_'
ln
1 ~

(15)
~K° R r T,
Eliminating Xb1 between eq 8 and eq 11 yields
AH° „AT where K = tb'-XbVyb^b5 and the activity coefficients de-
+ AA71)
(12) pend upon the nature of A and B and their liquid and solid
(1 -

K°)RTfHl solution interactions.

where A A/f^Xf/RTf^X0
=
1), which for sufficiently
—
The figure shows the Ge-Si phase diagram.1 On the Si-rich
small AT yields (to first order in AT): end, K° (the limit of Xce'/Xce1 as T goes to 1414 °C, the
fusion
melting temperature of Si) is greater than unity, and the
(13) freezing point is depressed. Furthermore, Si can be purified
(K° -
1)RT* of a Ge impurity by zone refining. On the Ge-rich end, X°
and (the limit of Xsi'/Xsi3) is less than unity, and the freezing
point is elevated. Ge cannot be purified of a Si impurity by
zone refining.
(14)

These are the generalized limiting laws for solid-liquid two-

component equilibria. For K° » 1 (solute much more solu-
ble in liquid than in solid solution) these become X2S 0 and ~ 1
Binary Alloy Phase Diagrams] Massalski, Thaddeus B., Ed.; Amer-
X21« A/irofUSionATRTf2, the linearized freezing point depres- ican Society for Metals: Metals Part, OH, 1986; Vol. 2.

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1078 Journal of Chemical Education