November 1, 2001

Reading: Chapter X
Homework: 10.1, 10.3, 10.5, 10.6, 10.7
Free energy composition diagram for a homogeneous solid solution:
We will discuss a binary solution of A and B. Although we will discuss a solid solution,
the analysis is equally applicable to a liquid solution. Let us assume that the binary
solution of A and B is stable over the entire range of compositions at a given T. If we
assume the presence of a gas phase, the phase rule gives
F=C-P+2=2-2+2=2
Where C=A and B, P=solid and gas
Thus, the degrees of freedom are two. One can thus choose T and composition as the two
degrees of freedom. If, on the other hand, there is no gas phase, one will have one phase
(the solution), then there will be three degrees of freedom: T, composition, and P. In this
case, the entire solution occupies the entire volume of the box. These two cases are
shown schematically in the following figures.
Gas phase
A, B solution
A, B solution

At ordinary pressures (a few atmospheres), there is generally very little difference

between the two phases. Thus, in what follows, we will not make a distinction between
the two.
Molar Gibbs free energy of the solution at the temperature T is given by
G xA GA
G = x A G A + x B GB , GB =

xB
xB
The above, in combination with Gibbs-Duhem equation, namely, x A d G A + x B d G B = 0 ,
gives
dG
GB = G + x A
dx B

GA = G + xB

dG
dG
= G xB
dx B
dx A

Lets assume that the G vs. xB curve is concave up over the entire range of composition.

GB0

GA0
G(xB)
M
G(xB0)

G(xB)
P

xB

xB0

xB

Consider one mole of solid solution of composition xB0. The corresponding free energy of
the homogeneous solid solution (point P) is given by G(xB0). Suppose that we break
(decompose) the original homogeneous solid solution into two (a mixture) homogeneous
solid solutions of compositions xB and xB. And the corresponding molar free energies
of the two solutions are G(xB) and G(xB), respectively. Suppose that we have a moles
of solution of composition xB and b moles of composition xB. Clearly,
a +b =1

ax B '+bx B ' ' = x B0

ax B '+ (1 a ) x B ' ' = x B0
i.e., a =
and

x B0 x B ' ' x B ' ' x B0

=
x B ' x B ' ' x B ' ' x B '

b = 1 a =

x B0 x B '
x B ' ' x B '

The total Gibbs free energy of the mixture is

G = aG ( x B ' ) + bG ( x B ' ' )

= (1 b)G ( x B ' ) + bG ( x B ' ' )

= G( xB ' ) +

x B ' x B0
x 0 xB '
G( x B ' ) + B
G( xB ' ' )
x B ' x B ' '
x B ' ' x B '

= G( xB ' ) +

G( xB ' ' ) G( xB ' ) 0

( xB xB ' )
x B ' ' x B '

slope of the line joining G ( x B ' ) and G ( x B ' ' )

= Gibbs free energy (molar ) corresponding to the po int M
Clearly, G (mixture, at point M) > G (homogeneous solution, at point P)

Thus, as long as G vs. xB is concave up, a homogeneous solid solution is stable with
respect to the mixture.
Now, G = x A G A + x B G B = x A G A0 + x B G B0 + G M

x A G A0 + x B G B0 is a straight line. Thus, GM vs. xB determines the shape of G vs. xB curve.

If the solid solution is stable over the entire range of composition, it means, GM<0, and
d 2G
> 0 (concave up).
dx B2
If the solution is ideal,
G = x A G A0 + x B G B0 + G M

= x A G A0 + x B G B0 + RT {x A ln x A + x B ln x B }
Then,
G M = RT {x A ln x A + x B ln x B } < 0 over the entire range of compositions. Differentiating
G with respect to xB.
dG
= G A0 + G B0 + RT { ln x A 1 + ln x B + 1}
dx B

1
d 2G
RT
1
= RT + =
>0
2
dx B
x A xB x A xB
over the entire range of composition. Therefore, the ideal solution is stable over the entire
range of composition.

Regular solution:
In a regular solution, H M = x A x B 0 , where the interaction parameter is given by
1
= N 0 Z {h AB (h AA + hBB )}
2
Where, N0 = Avogadros number
Z=coordination number
h AB , h AA , hBB : bond enthalpies

Before mixing:

G0 = x A G A0 + x B G B0

After mixing:

G = x A G A + x B GB

G = x A G A0 + x A RT ln a A + x B G B0 + x B RT ln a B
= x A G A0 + x A RT ln A + x A RT ln x A + x B G B0 + x B RT ln B + x B RT ln x B
= x A G B0 + x B G B0 + RT {x A ln A + x B ln B } + RT {x A ln x A + x B ln x B }

Now, ln A

x B2
x A2
, ln B =
. So,
=
RT
RT

x B2
x A2
+ xB
G = x A G B0 + x B G B0 + RT {x A ln x A + x B ln x B } + RT x A

RT
RT

= x A G A0 + x B G B0 + x A x B + RT {x A ln x A + x B ln x B }
= x A G A0 + x B G B0 + G M

G = G 0 + H M TS M

Or,

G M = H M T S M
= x A x B + RT {x A ln x A + x B ln x B }
Again, G 0 = x A G B0 + x B G B0 = G A0 + (G B0 G A0 ) x B is a straight line as a function of
composition, the shape of the G vs, xB curve is determined by the shape of the GM vs. xB
curve. Note that TS M = RT {x A ln x A + x B ln x B } < 0 , always; while the term
H M = x A x B is positive if >0, and negative if <0.
Let us consider the case >0. (positive deviation from ideality, since this gives A>1,
B>1). Note that H M = x A x B is independent of temperature. But, TS M is linearly
dependent of the temperature. The following plots are H M , TS M , and G M at high
and low temperatures:

HM

HM

xB

GM
GM
-TSM
-TSM
High temperature

Low temperature