FREE ENERGYCOMPOSITION CURVES

Equilibrium in Heterogeneous
Systems

For many systems A and B components do not

have the same crystal structure in their pure
states at a given temperature.

TWO free energy curves

must be drawn, one for each
structure.

The stable form of pure A and

B at a given T (and P) can be
denoted as and respectively.

Suppose that is fcc and is bcc,

Molar free energies of fcc A
bcc B are shown as points a
b.

and
and

Equilibrium in Heterogeneous
Systems
is fcc and is bcc

Molar free energy curve for

the phase

Molar free energy curve for

the and phases

The FIRST STEP in drawing the free-energy curve of the fcc phase is:
Convert the stable bcc arrangement of B atoms
into an unstable fcc arrangement.
This will raise the free energy from point b to c.
The free energy curve for phase can now be constructed
as before by mixing fcc A and
fcc B.
A similar procedure will
produce the molar free
energy curve for the phase.
phase
Points a and f
shows the difference in
free energy when fcc A
is converted to bcc A.
is fcc and is bcc

It is evident from this exercise that A-rich alloys will have the
lowest free energy as a homogeneous -phase,
-phase and, B-rich
alloys as -phase.
-phase

For alloys with compositions near the cross

over in the G curves, the situation is not so
straight forward.
In this case, it can be shown
that the total free energy can
be minimized by the atoms
separating into two phases.
phases

A general property of molar free

energy diagrams for phase
mixtures

Suppose an alloy consists of and phase,

each with a molar free energy of G and G
Overall composition of
the phase mixture is given
by
The lever rule gives the
relative number of moles
of and that must be
present.
The molar free energy of
the phase mixture G is
given by the point on the
straight line between

X B

The lengths ad and cf represent the

molar free energies of and phases
present in the alloy.

Point g is obtained by
the intersection of be
and dc

bcg and acd, as well as deg and dfc, form similar

triangles.
Therefore, bg/ad =
bc/ac
And

ge/cf = ab/ac.
ab/ac

According to the lever rule 1

mol of the alloy will contain
bc/ac mol of and ab/ac mol
of .
It follows that bg and ge represent the separate contributions
from the and phases to the total free energy of 1 mol of alloy.

Therefore, the length be represents

the molar free energy of the phase
mixture.

CONSIDER ALLOY X

If the atoms are arranged as a single

homogeneous phase,
phase the free energy will be
lowest as -phase
However, the system can
lower its free energy, if the
atoms separate into two
phases with compositions 1
and 1 for example.

The free energy of the

system will then be
reduced to G1

Go Go

Further reductions in free

energy can be achieved if
the phase compositions are
adjusted to e and e

The free energy of the

system, Ge, is now a
minimum
and
there
would be no desire for
further change.
Thus the system is now
in equilibrium and e and
e are the equilibrium
compositions of the
and phases.

Figure 1.27

 The result is quite general and

can be applied to any alloy with
an overall composition between e
and e
only the relative amounts of
the two phases change
according to the lever rule.
When the alloy composition lies
outside this range,
range
the minimum free energy
lies on the G and G curves
and the Equilibrium State of
the alloy is a homogeneous
single phase.

It could also be seen that the

equilibrium between two phases
requires that the tangents to
each G-curve at the equilibrium
compositions lie on a common
line.

So each component must have the

same chemical potential in the two
phases, i.e. for heterogeneous
equilibrium:

A A

and

B B

Similarly, the activities of the

components must also be equal, i.e.

aA a A

and

aB aB

VARIATION OF ACTIVITY WITH ALLOY

COMPOSITION
Between A and e, and e and
B, where single phases are
stable, the activities (or
chemical potential) vary.
vary
Note that ideal
solutions have been
assumed so we see
straight-line relationship
between a and X.
Between e and e the phase
compositions in
equilibrium do not change
and the activities are also
equal and are given by the
points q and r.
Figure 1.28