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THERMODYNAMICS OF PHASE

TRANSFORMATION

Presented by:
Submitted To: MOHIT LUDHWANI(MT18MTE005)
DR. S.N PAUL D.SAICHARAN(MT18MTE006)
WHAT IS PHASE
TRASFORMATION ??
BASICE OF THERMODYNAMICS

 ENTHALPY:
Enthalpy (H) = Internal Energy + PV (work done by the system)
H=U+PV
dH =dU+PdV+VdP
 INTERNAL ENERGY:
Internal Energy (U or E) = Kinetic Energy (KE) + Potential Energy (PE)

 HELMHOLTZ FREE ENERGY:


Helmholtz Free Energy (A or F) = U − T.S
GIBBS FREE ENERGY
 In phase transformation, Concerned
with change toward equilibrium.
 For transformations that occur at
constant temperature and pressure
the relative stability of a system is
determined by its Gibbs free
energy(G)
G = H – TS
Equilibrium --no change in mass
/comp.
dG=0
Ex-Diamond and graphite
THERMODYNAMICS OF SINGLE
COMPONENT SYSTEM
 One containing a pure element
or one type of molecule that
does not dissociate over the
range of temperature of interest.
 Variation of G with temperature
dG = -SdT + VdP

At constant pressure dP = 0 and


 G 
   S
 T  P
 Enthalpy for a liquid phase is always
higher than the solid phase.

 Therefore at low temp. GL >GS

 Temperatures up to Tm the solid


phase has the lowest free energy and
is therefore the stable equilibrium
phase, whereas above Tm the liquid
phase is the equilibrium state of the
system.
 At melting point, free energy for both
the phases are the same and the
difference between the enthalpy of
these two phases is equal to the
latent heat of fusion L.
GIBBS FREE ENERGY FOR
SOLIDIFICATION
 If a liquid metal is undercooled
by ΔT below Tm before it
solidifies, solidification will be
accompanied by a decrease in
free energy ΔG given by
ΔG=ΔH-TΔS
At Tm(ΔG=0):

For small ΔT
BINARY SYSTEM
 Previously we are considered one element only. Now we consider
interaction between two elements. This is not straightforward since
elements can interact differently and thermodynamic parameters may
change accordingly.
 Let us consider a Binary system with elements A and B. For our
analysis, we consider XA mole of A and X B mole of B so that
XA + X B = 1
Before mixing
G1 = XAGA + XBGB

After Mixing
G2 = G1 + ΔGmix
Where
ΔGmix=ΔHmix - TΔSmix
IDEAL SOLUTION
 The simplest type of mixing to treat
first is when ΔHmix = 0, in which
case the resultant solution is said to
be ideal.
ΔGmix = - T Δsmix
Δ Smix = -R(XA In XA + XB In XB)
 XA and XB are less than unity,
ΔSmix is positive, i.e. there is an
increase in entropy on mixing.
Therefore,
Δ Gmix = RT(XA In XA + XB In XB)
G2 = XAGA + XBGB + RT( XA In XA + XB In XB)

 With the increase in temperature,


-TΔSmix will become even more
negative.
 The values of GA and GB also
will decrease
 Following the slope G1might
change since GA and GB will
change differently with
temperature.
REGULAR SOLUTION
 Returning to the model of a solid
solution,so far it has been
assumed that ΔHmix = 0;
usually mixing is endothermic
(heat absorbed) or exothermic
(heat evolved).
 For real solution,
ΔHmix = Ω XA XB(Ω = Na Z Ɛ)
(Depend on bond energies)
free energy change on mixing
regular solution:
ΔGmix = Ω XA XB + RT(XA In
XA + XB In XB)
EQUILLIBRIUM IN HETEROGENOUS
SYSTEM
 If the atoms are arranged as a
homogeneous phase. The free energy
will be lowest as α , i.e 𝐺0α per mole.
 However, from the above it is clear that
the system can lower its free energy if
the atoms separate into two phases with
compositions. α and ß for example The
free energy of the system will then be
reduced to Gl .
 Further reductions in free energy can be
achieved if the A and B atoms
interchange between the and ß phases
until the αe and ße are reached.
 The free energy of the system Ge is now
a minimum and there is no desire for
further change.
FREE ENERGY VS COMPOSITION DIAGRAM
FOR ISOMORPHOUS SYSTEM
 With decreasing temperature,
free energy for the solid, GS
and liquid phase GL will
change differently with
different rates of change of
GA and GB.
 At higher temperature,
GL<GS (fig a), so that the
liquid phase is stable. At
lower temperature GS < GL
(fig e) so that the solid phase
is stable.
 In between, GS and GL
intersects to find the situation
as explained in Fig. c.
 Common tangent drawn
gives the composition range
where both solid and liquid
phases can be found together.
EUTECTIC SYSTEM WITH SAME CRYSTAL
STRUCTURE
 At a high temperature T1 > T m(A) >
Tm(B) the liquid will be the stable phase
for pure A and pure B.

 At T2 the free energy curves cross and


common tangent indicates the phases
alpha and liquid are stable up to certain
compositions. These points are plotted
on the equilibrium phase diagram at T2.
 At T4=Te liquid ,alpha-1 and alpha-2 all
will coexist at eutectic point. Below
eutectic temperature the common
tangent between two minima shows that
alpha 1 and alpha 2 are stable.
EUTECTIC SYSTEM WITH DIFFERENT
CRYSTAL STRUCTURE
HOMOGENEOUS AND HETEROGENEOUS
NUCLEATION

Free energy change for the formation of solid

Which further can be written as

r is radius of sphere
Free energy change for heterogeneous
nucleation
DISCUSSION
 Thermodynamics of single component system and binary
system studied.
 Enthalpy and free energy of mixing in case of binary system
is obtained. Its variation with alloy composition is studied.
 Equilibrium condition for heterogeneous system in form of
chemical potential is obtained.
 The derivation of isomorphs (complete solubility in both solid
and liquid phase) and eutectic system(complete solubility in
liquid but partial solubility in solid phase) from free energy vs
composition diagrams has been studied.
THANK YOU