Eq.

(C-1) to (C-7)

APPENDIX C

Freezing Point Depression

Consider a dilute solution of B in solvent W at equilibrium with the pure

solid W. Imagine the situation in which a minute amount of pure W pre-
cipitates on cooling the solution. This occurs at T. The pure solid W is
in equilibrium with the solution. Hence,
ðL Þ ðSÞ
μW ¼ μ W , (C-1)

W and μW are the chemical potentials of W in the liquid solution

where μ(L) (S)

and the solid phases, respectively (see Eq. II-31). Following Eq. (II-12), μ(L)
W
is written as
ðL Þ ðL Þ
μW ¼ μ∗W + RT ln xW + μEW , (C-2)
ðL Þ
where xW is the mole fraction of W in the liquid phase, and μ∗W is the
chemical potential of pure liquid W. μEW is the excess chemical potential
of W due to the nonideality of the system and depends on the nature of inter-
molecular interactions in solution B-W. Since we take the symmetric refer-
ence system (see Section [II-1]), μEW ¼ 0 at xW ¼ 1. For the solid phase, the
pure solid W precipitates separately from the mother liquor. Hence
ðSÞ ðSÞ
μW ¼ μ∗W , (C-3)
ðSÞ
where μ∗W is the chemical potential of the pure solid W. Eqs. (C-1)–(C-3)
yield
h i.
ðL Þ ðSÞ
 ln xW  μEW =RT ¼ μ∗W  μ∗W ∗  TΔ S ∗ =RT ,
RT ¼ ½Δf us HW f us W

(C-4)
with
ðL Þ ðL Þ ðL Þ
μ∗W ¼ HW
∗ ∗ ,
 TSW (C-5)

ðSÞ ðSÞ ðSÞ

μ∗W ¼ HW
∗ ∗ ,
 TSW (C-6)

∗ ¼ H∗ ∗ ðL Þ ðSÞ
Δf us HW W  HW , (C-7)

399
400

∗ ¼ S∗ ðL Þ
∗ ðSÞ
Δf us SW W  SW : (C-8)
Generally, both heat and entropy of fusion of pure W are positive, i.e.,
∗ > 0 and Δ S ∗ > 0.
Δf us HW f us W
Consider now the equilibrium between the pure liquid W and the pure
solid W. This occurs at the freezing (or melting) point of pure W, T∗. Since
μEW ¼ 0 at xW ¼ 1, Eq. (C-4) yields
∗  T ∗Δ S∗ =RT ∗,
0 ¼ ½Δf us HW (C-9)
f us W
∗ and Δ S ∗ do not change
We assumed here that the values of Δf us HW f us W
from T to T∗, which is an acceptable assumption since T  T∗. Due to
Eqs. (C-9), (C-4) is rewritten as
 ln xW  μEW =RT ¼ ½Δf us HW
∗  T Δ H ∗ =T ∗=RT ,
f us W

or
  
∗
ðT ∗  T Þ ¼  RðT∗Þ2 =Δf us HW ln xW + μEW =RT , (C-10)
where we used a numerical approximation TT∗  (T∗)2.
We now take an arithmetic approximation that lnxW ¼ ln ð1  xB Þ  xB .
For example, if xW ¼ 0:99 and xB ¼ 0:01, then ln(0.99) ¼  0.01005. If
xW ¼ 0:999, ln(0.999) ¼ 0.0010005. We make another more serious
assumption that the solution in question is dilute enough that the solvent
obeys Raoult’s law (Section [II-4]), i.e., μEW ¼ 0. Thus, Eq. (C-10) is
rewritten as
 
∗ x :
ðT ∗  T Þ ¼ RðT ∗Þ2 =Δf us HW B (C-11)
Since Δf us HW ∗ > 0, ðT ∗  T Þ > 0, i.e., the freezing point depression

by addition of a minute amount of B. Since, the proportionality factor,

 
∗ , concerns only with solvent W, Eq. (C-11) indicates
RðT ∗Þ2 =Δf us HW
that it is only the quantity of solute, xB, but not the quality of B, that deter-
mines the freezing point depression as long as the solvent is fixed. Thus, the
freezing point depression is called one of the “colligative properties,”
together with the boiling point elevation, the vapor pressure suppression,
the osmotic pressure, etc. This is true only when the Raoult’s law assump-
tion is correct, while this assumption is approximately acceptable in dilute
enough solutions. As discussed in Sections [III-6] and [V-1], this does not
occur even at xB  105 . Thus, strictly speaking, the “colligative property”
Eq. (C-8) to (C-14) 401

is not realistic. If the solute-dependent μEW is nonzero in Eq. (C-10), it should

 
be rewritten with the activity coefficient of W, γ W μEW =RT ¼ ln γ W as,
 ∗

ðT ∗  T Þ ¼  RðT∗Þ2 =Δf us HW ln xW γ W : (C-12)
With the osmotic coefficient, ϕ defined as
ϕ ¼ 1 + ln γ W = ln xW , (C-13)
Eq. (C-12) is written as, together with the arithmetic approximation for
ln xW,
 
∗ ϕx :
ðT ∗  T Þ ¼  RðT∗Þ2 =Δf us HW B (C-14)

ϕ and γ W are now dependent, though weakly, on the identity of solute B.