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basic theory about thermodynamics and phase transformation

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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 (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

G

S

T P

Enthalpy for a liquid phase is always

higher than the solid phase.

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)

-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.

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

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

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