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November 12, 2001

Homework: 10.1, 10.3, 10.5, 10.6, 10.7
Liquid solution- ideal; solid solution- Regular with >0
The activity coefficient for a regular are given by
x B2
x A2
, and ln B =
ln A =
RT
RT
Thus, partial molar free energies (chemical potentials) in the A-B solution are given by
G A ( s ) = G A0 s + RT ln a A = G A0 s + RT ln A + RT ln x A ( s )
= G A0 s + x B2 ( s ) + RT ln x A ( s )
And G B ( s ) = G B0 s + x A2 ( s ) + RT ln x B ( s )
The above assumes the standard states for A and B are solid. If not, GA0s and GB0s will be
replaced by GAs and GBs, respectively.
For the liquid solution,
G A (l ) = G A0l + RT ln x A (l )

G B (l ) = G B0l + RT ln x B (l )
Again, the above assumes that the standard states for A and B are liquid. If not, GA0l and
GB0l will be replaced by GAl and GBl, respectively.
GA

GB

s
l

s
l
TAf

T
G Al G Al = H A0 f 1 f
TA

T
G Bl G Bs = H B0 f 1 f
TB

TB f

Molar Gibbs free energies of the solutions are

Solid: G ( s ) = x A G A ( s ) + x B G B ( s )
= x A G A0 s + x B G B0 s + x A x B + RT {x A ln x A + x B ln x B }
The above assumes A and B are solids (standard states). If not,
G ( s ) = x A G As + x B G Bs + x A x B + RT {x A ln x A + x B ln x B }
Liquid: G (l ) = x A G A (l ) + x B G B (l )
= x A G A0l + x B G B0l + RT {x A ln x A + x B ln x B }
The above assumes A and B are liquids (standard state). If not,
G (l ) = x A G Al + x B G Bl + RT {x A ln x A + x B ln x B }
Let TBf >T>TAf:

T
Then, G A0l G A0 s = H A0 f 1 f
TA

T
G Bl G B0 s = H B0 f 1 f
TB

So, G (l ) = x A G A0l + x B G Bl + RT {x A ln x A + x B ln x B }
T
= x A G A0l + x B G B0 s + x B H B0 f (1 f ) + RT {x A ln x A + x B ln x B }
TB

And G ( s ) = x A G As + x B G B0 s + x A x B + RT {x A ln x A + x B ln x B }
T
= x A G A0l + x B G B0 s + x A H A0 f (1 f ) + x A x B + RT {x A ln x A + x B ln x B }
TA
Now,
dG (l )
dG (l )
G A (l ) = G (l ) x B
, G B (l ) = G (l ) + x A
dx A
dx B

G A ( s) = G( s) x B

dG ( s )
dG ( s )
, G B (s) = G( s) + x A
dx B
dx B

dG (l )
T
= G A0l + G B0 s + H B0 f 1 f
dx B
TB

x
+ RT ln B
xA

And,
T

x
dG ( s )
= G A0l + G B0 s H A0 f f 1 + ( x A x B ) + RT ln B
dx B
xA
TA

Substituting the above into the equations for partial molar free energies,

G A (l ) = G A0l + RT ln x A (l ) = G A0l + RT ln[1 x B (l )]

T
G A ( s ) = H A0 f ( f 1) + G A0l + x B2 ( s ) + RT ln x A ( s )
TA
= G A0l + H A0 f (

T
1) + x B2 ( s ) + RT ln[1 x B ( s )]
T Af

And,
G B (l ) = H B0 f (1

T
) + G A0 s + RT ln x B (l )
TBf

G B ( s ) = G B0 s + RT ln x B ( s ) + x A2 ( s ) = G B0 s + RT ln x B ( s ) + [1 x B ( s )] 2
For the coexisting of liquid and solid solutions, we must have
G A ( s ) = G A (l ), G B ( s ) = G B (l )
This gives
T
H A0 f ( f 1) + x B2 ( s ) + RT ln[1 x B ( s )] = RT ln[1 x B (l )] ----------(1)
TA
H B0 f (1

T
) + RT ln x B (l ) = RT ln x B ( s ) + RT ln[1 x B ( s )] 2 ---------(2)
TBf

Solving for xB(s) and xB(l),

H A0 f
x 2 ( s )
T
(1 f ) -------------(3)
x B (l ) = 1 [1 x B ( s )] exp B exp
TA
RT
RT
2
0f
H B
[1 x B ( s )]
T
exp
(1 f ) ---------------(4)
x B (l ) = x B ( s ) exp
RT
TB
RT

From (3) and (4),

x B2 ( s )
H A0 f
T

1 [1 x B ( s )] exp
exp
(
1
)

RT
RT
T Af

------------(I)
x B ( s) =
[1 x B ( s )] 2
H B0 f
T
exp
exp
(1 f )
RT
TB

RT
The above equation is an implicit equation in xB(s). Thus, one must solve it numerically,
once xB(s) is determined, xB(l) can be readily determined from (4).
Consider T<TAf <TBf:
The standard states for both A and B are solid,

Thus,

T
G Al = G A0 s + H A0 f 1 f
TA

T
G Bl = G B0 s + H B0 f 1 f
TB

The free energies (molar) of the solid and liquid solutions are
G ( s ) = x A G A0 s + x B G B0 s + x A x B + RT {x A ln x A + x B ln x B }
G (l ) = x A G Al + x B G Bl + RT {x A ln x A + x B ln x B }
T
T
= x A G A0 s + x B G B0 s + x A H A0 f (1 f ) + x B H Bof (1 f ) + RT {x A ln x A + x B ln x B }
TA
TB
Once again, for the coexisting of liquid and solid phase, we must have
G A ( s ) = G A (l ), G B ( s ) = G B (l )
After considerable algebra, we have

H B0 f
[1 x B ( s )] 2
T
exp
(1 f
x B (l ) = x B ( s ) exp
RT
TB
RT

) ---------------(5)

And
x 2 ( s )
H A0 f
T
1 [1 x B ( s )] exp B exp
(1 f
TA
RT
RT
x B ( s) =
2
0f
[1 x B ( s )]
H B
T
exp
exp
(1 f )
RT
TB

RT

)
------------(II)

Note that equation (5) is the same as equation (4), and equation (II) is the same as (I).
Thus, for both T<TAf <TBf and for TAf <T<TBf, the equations for xB(s) and xB(l) are
identical. However, for T<TAf <TBf, there will be two values of xB(s) and two values of
xB(l). We will assume that Tc for the miscibility gap is much lower than TAf or TBf. We
will now examine the G vs. xB plots for both the solid and the liquid at various
temperatures. Also, we will examine the corresponding phase diagrams.

T>TBf >TAf>Tc
GA s

GB s

GB0l
GA0l

TBf >T>TAf>Tc
GA s
GA s
GB0s
GA0l

l+s

xB(s)

xB(l)

T<TAf <TBf
GA l

GB l

GB0s
GA0s

l+s

s
l

l+s
B

TBf >TAf>T=Tml>Tc
Where Tml is the lowest temperature at which a liquid is present.
GA l

GB l

GB0s
GA0s

The corresponding phase diagram is

TA

T Bf

l+s

l+s
T

s
Tc
Two solid phases
xB

For the case where Tc<Tml , then for TBf >TAf >Tc>T>Tml,
GA l

GB l

GB0s
GA0s

l+s
1

l
1

A xB (s)

xB2(l)

xB (l)

l+s

xB2(s)

GA l

GB l

GB0s
GA0s

l+s2

l+s1

1
A xB (s)

xB(l) xB2(s)

TB f

TAf

s2+l

s1

s1+l
1

xB (s)

xB2(s)
E

xB (l)

s2

Tm =TE

s1+s2

xB