Equilibrium phase diagram in ideal system:-

For a system in which ideal solutions are formed in both the liquid and
solid states, the free energy curves for both states will be the form in
fig.(1).

Fig.(1):free energy curves for ideal solutions at several

temperatures.
 At a very high temperature such as T6 in fig.(2),the liquid
free energy curve lies below that of the solid at all compositions .with
decreasing temperature the free energies of both liquid and solid state

increasing in accordance with ( ) . Since ,however the entropy

of substance at a given temperature is generally higher in liquid than in

the solid state, the rate of increase of the liquid free energy7 is greater
than that of solid. Thus the free energy curve of liquid in fig.(2)moves up
relative to that of the solid as the temperature decreases and ultimately the
two intersect. It is assumed in fig.(2)that this happens first at pure A at
temperature T5.The free energies of pure solid A and pure liquid A are
equal. This is the melting temperature of A. the temperature at which pure
liquid A and pure solid A may coexist in equilibrium .this is indicated by
the point marked a at the temperature T5 and the composition pure A in
the temperature –composition phase diagram of fig.(3).At all other
composition at T5 the stable condition is a single liquid solution.

At T4 the liquid and solid free energy curves intersect at some

intermediate composition. Under these circumstances it may be
demonstrated that within a certain composition range a mixture of two
solutions, one liquid and one solid, is more stable than either a liquid
solution or a solid solution alone.
 fig.(3):ideal –system equilibrium phase diagram
resulting from the free –energy curves in fig.(2).

Consider , for example, the alloy of composition X1in the free energy
diagram of fig.(4).if this alloy exist as a single solid solution, it has the
free energy given by the point a in the diagram. It has the lower free
energy corresponding to point b if it exist as a single liquid solution, but
the lowest free energy it may have is given at point M, representing the
free energy of the alloy when it exists as a mixture of solid and liquid
solutions with compositions given at point d and, the two points of
common tangency to the free energy curves. That this latter condition
does the fact correspond to equilibrium may be seen in the following
way. Suppose the alloy X1 exists as a mixture of liquid and solid solutions
of the general compositions XL,XSas shown in fig(4),we write for the
liquid phase:-

(1)

Since the partial molal free energy is by definition the free energy per
mole of a component in solution , the free energy of the liquid solution
is

Upon substituting XA=1-XB and dXA=-dXB, combining eq.(1)&(2),and

suitably rearranging ,we obtain:- (3)

(4)

Now comparing eq.(4) with the diagram in fig .(4),it is seen that
̅̅̅̅
̅̅̅̅ and ( )

̅̅̅̅
So that =̅̅̅̅ ̅̅̅̅ ̅̅̅̅ ̅̅̅̅

In a similar way it may be shown that ̅̅̅ ,but at equilibrium the

two chemical potentials are equal and then ̅̅̅̅= ̅

Which means that for equilibrium C and J represent the same point .This
condition of equilibrium and that expressed in:

( ) ( )
Theoretical Calculation of Binary Phase Diagram for
Ideal Solution:- Real systems which behave almost ideally in both

the solid and liquid states present the possibility of the relatively simple
quantitative calculation of phase diagram. The equations for the liquidus
and solidus curves in the systems of two metals soluble completely in
liquid and solid states will be developed from the relations,by using

G L  G M,L  RT( XLA ln XLA  XLB ln XLB ) (5)

 eq.10 for ideal solution which represent in this diagram liquid phase and
solid solution :-

GM,L in turn may be written as:

G M,L  ( XLAG LA  XLBG LB )

the chemical potential as:

dG L (4)
 LA  G L  XLB
dX LB

LB  G LB  RT ln XLB (3)

differentiating eq.(5) get that:-

Thus the chemical potential of metal B in the liquid phase is:

(3)
LB  G LB  RT ln XLB

In an analogous manner in the solid solution:

(6)

If the liquid and solid solution using are to be in equilibrium, the

chemical potentials of B in each must be identical; equating (3) and (6):-

XSB
RT ln  G LB  G SB  G B (7)
XLB
At a given temperature the difference in Gibbs free energy for metal B is:
GB  HB  TSB (8)
When B melts under equilibrium conditions at constant temperature
and pressure, at melting temperature the change in Gibbsmfree energy is
H B
zero: Eq. (9) G B  0  HB  TB SB
m m m m
or  S m
B

TBm
Assuming that neither ΔSB nor ΔHB varies with temperature, this is
equivalent to assuming that the difference between the heat capacity of
the liquid and that of the solid,ΔCp, does not change with temperature,
a good approximation for the relatively narrow range of temperature of
interest here.
SB  Sm B
and HB  Hm
B

then substitution of eq.(8)into (9) gives:-

H m T (10)
G B  H B  T mB  Hm
m
B
(1  m )
TB TB
By combining eqs.(1) and (2) it can be FPUND found :The same analysis
obviously holds for the component A in the two solutions, so that:

XSB H m  
ln L  B 1  1 
(11)
XB R  T TBm 

1  XSB H m  
ln  A 1  1 
(12)
1  XLB R  T TAm 
In this work , by assuming that metals melt and solidify at their melting
temperature under equilibrium conditions, that is ΔG=0, and using eqs.
(11) and (12) to draw the solidus and liquidus curves for ideal solutions
(isomorphous systems). The equilibrium melting temperature and the
enthalpy of fusion at constant pressure of the pure components at their
melting points are needed to determine this type of phase diagrams. In
this work these equations can be used for some phase diagrams which
dealt as ideal solution, such as Cu-Ni, Ge-Si .