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(C-1) to (C-7)
APPENDIX C
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)
∗ 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