November 5, 2001

Reading: Chapter X
Homework: 10.1, 10.3, 10.5, 10.6, 10.7
Criterion on Regular solution:
The schematic (previous note) shows that at low temperatures, the GM vs. xB curve can
be convex up. Such a trace is characterized by one maximum, two minima and two
inflexion points. Let us examine this mathematically.

G M = x A x B + RT {x A ln x A + x B ln x B }
dG M
= x A x B + RT { ln x A 1 + ln x B + 1}
dx B
dG M
At extremum,
=0
dx B
x A x B + RT { ln x A + ln x B } = 0
So,

(1 2 x B ) + RT ln

xB
=0
1 xB

The above is satisfied at xB =1/2. But, this is due to symmetry and corresponds to the
maximum. The minima are also symmetrically situated about xB =1/2. Thus, the
compositions corresponding to the minima are given by xB =1/2. Substituting in the
above,
1

1
2
1 2 + RT ln
=0
1
2

m
2
1

m 2 + RT ln 2
=0
1
m
2
1 2
2 = RT ln
1 m 2
1 + 2
2 = RT ln
1 2
The solution will give = (T ) , as a function of T. It must be solved numerically, as
there is no explicit analytical solution. When =1/2, the left side is ; the right side

1+1
= T . Clearly, this can be satisfied only at T=0 K. Thus, at T=0, the
11
minima are xB =0 and xB=1.

becomes T ln

When is very small (<<1), the logarithmic terms can be expanded in Taylors
expansion, and retain only the first few terms.
So,

1 + 2
1 2
2 = RT {ln(1 + 2 ) ln(1 2 )}
2 = RT ln

1
1
1
1

= RT 2 ( s 2 ) 2 + (2 ) 3 + ... + 2 + (2 ) 2 + (2 ) 3
2
3
2
3

4 2
2 = 4 RT 1 +

4 2
= 2 RT 1 +

When T=Tc, =0, i.e., minima at xB=1/2 and GM concave up. We have
Tc=/2R.
Above Tc, i.e., for TTc, the GM vs. xB curve is concave up. So, the solution is stable.
Tc=/2R is known as the critical temperature.
For T slightly lower than Tc, <<1, retaining the 3 term we have
4 2
= 2 RT 1 +

T
4 2

1+
=
= c
3
2 RT T
3T

2 = c 1
4 T

3 Tc
1
2 T

The above shows that the behavior of near the critical point. The corresponds to
the compositions of the minima. Although we did not discuss in the class, in the case of
the van der Waals gas, the difference in densities (gm/cm3) of the coexisting phases,
liquid and gas, namely, l-g, also exhibits a similar behavior near the critical point of the
gas. That is

Tc
1 .
T
For this reason, many characteristics of liquid-gas transition are similar to a regular
solution with >0

l g ~

Returning to the dependence of GM on compositions and temperature, we note that for

T<Tc, the shape of GM vs. xB is characterized by two minima, one maximum, and thus
two inflexion points.

G M = x A x B + RT {x A ln x A + x B ln x B }
d 2 G M
The inflexion points are characterized by
dx B2
dG M
= x A x B + RT { ln x A 1 + ln x B + 1}
dx B

1
d 2 GM
1
=

+
+
RT

=0
x
x
dx B2
B
A
1
RT
RT
1
2 = RT + =
=
2
x A xB x A xB xB xB
RT
x B2 x B +
=0
2
T
x B2 = x B +
=0
4Tc

1 1
xB =

T
Tc

T
1
1 1
2
Tc

Shapes of GM vs. xB and G vs. xB for T<Tc:

GB0

GM

xB

GA0

m
p

xB

q
n

xB0
xB

xB

For a homogeneous solution of composition xB0, Gibbs free energy per mole is G (xB0)
and is given by point m. Suppose this solution split into two homogeneous solutions of
composition xB and xB the point corresponding to the common tangent on the G vs. xB
curve. The free energy corresponding to the mixture is given by
x B ' ' x B0
x B0 x B '
G=
G ( P) +
G ( P)
x B ' ' x B '
x B ' ' x B '
= G ( n)
Clearly G (n) < G (m)
Thus, the two phase mixture corresponding to xB and xB is more stable than the original
homogeneous solution of xB0. This is true for any value of xB0 between xB and xB; i.e.,
between p and q. Thus, a solution of composition xB0 will decompose into a mixture of
two solutions; one of xB and the other of xB. Relative proportions will depend on the
location of xB0 between the two limits. Between these two limits, the lowest free energy is
obtained on the line pq, which is the common tangent (tangential at xB and also at xB).
That is,
dG
dG
=
dx B x ' dx B x ''
B

Intercepts at xA=1, gives G A ( x B ' ) = G A ( x B ' ' ), i.e., A ( x B ' ) = A ( x B ' ' )
Intercepts at xB=1, gives G A ( x B ' ) = G B ( x B ' ' ), i.e., B ( x B ' ) = B ( x B ' ' )
That is, at equilibrium, the partial molar free energy (chemical energy) of A is the same is
both coexisting solution. Similarly, at equilibrium, the partial molar free energy
(chemical potential) of B is the same in both coexisting solutions.
Now, G = x A G A0 + x B G B0 + G M . So,
d G M
dG
= G A0 + G B0 +
dx B
dx B
G M = x A x B + RT {x A ln x A + x B ln x B }
Which is symmetric in xA and xB.
So, at the common tangent,

dG M
= 0 (regular solution)
dx B

dG
= G A0 + G B0
dx B
Thus, the points p and q correspond to the minima in the GM vs. xB curve. But we have
seen p and q are given by

Then,

2 = RT ln

1 + 2
1 2

T
1 + 2
ln
with p and q given by 1/2.
4Tc 1 2
These points are called bimodal points and represent the coexistence of two phases.
Essentially, the above gives the simple miscibility gap as the phase diagram.

Or

The following is a schematic of phase diagram.

Two phase
mixture
A

xB

Also shown in the figure are points corresponding to the inflexion points given by
T
1
x B = 1 1 by broken lines. These points are called Spinodal points, and the
Tc
2
locus is called the spinodal curve. At a given T, the region between binodal and the
spinodal corresponds to the metastable region- that between the spinodals is the unstable
region. This region is similar to van der waals gas. A comparison between the two is
shown below.
b1(p) to S1 and b2(q) to S2 are metastable region. S1 to S2 is the unstable region. This is
similar to van der waals gas: b1S1 and b2S2 metastable; S1S2-unstable.

S2

S1

q
b2

p
b1

xB

P
S2

S1

q
b2

b1

S2

G
q

b1, b2

S1
V