Thermodynamics and Phase diagram

S
H

capo regime

Dominate G at low temperatures

Dominate G at High temperatures

Gibbs free energy (G)

Relative stability of a system is determined by Gibbs free energy (G)

G H TS
Enthalpy

Entropy

Absolute temperature

Entropy is a measure of randomness of the system (or degree of

irreversibility of the process)
Enthalpy is a measure of the heat content of the system

Enthalpy

H E PV

Volume

Pressure
Internal Energy
(K.E. + P.E. of the system)

Interaction/bonds between atoms

Atomic vibrations (Liq and Solid), or
Translational and rotational energies
of atoms or molecules within a liq. and gas

Enthalpy and Entropy as a function of temperature

H
Quantity of heat required to raise
Cp

the temp. of the substance by 1 K

T
Ho Enthalpy of the system at
absolute zero
H = 0 for pure element in its
most stable state at 25oC

T T

H H o C p dT
0

Cp

S
0

Cp
T

dT

Equilibrium
A system is said to be in equilibrium when it is in the most stable state
i.e. shows no desire to change ad infinitum

At constant temperature and pressure a closed system (fixed

mass and composition) will be in stable equilibrium if dG 0
dG = 0

Gibbs free
energy G

Equilibrium cont..

Gibbs free
energy G

dG = 0
dG = 0

G1
G2
1

Metastable equilibrium

State of system

Stable equilibrium

G1 > G2
Necessary criterion for phase transformation (G<0)

G G2 G1 0

Single component systems (pure element or molecule)

Time-Temperature curve
Liquid
Phase transformation at
constant temperature

Temperature

TM
Solid

Time

Variation of G with temperature of a single component

Latent
heat

System of fixed mass and composition

Varying pressure and temperature

dG SdT VdP

@ constant pressure
G

S
p

Enthalpy of liquid is more than solid

at all temperatures
Entropy of liquid is more than that of
solid

Binary solutions

Ideal solutions
Regular solutions
Real solutions

Gibbs free energy of binary solutions

Depends on
Pressure
Temperature
Composition

Usually treated constant (1 atm.) in

solid state transformations
Two variables

G X AG A X B GB Gmix
Gmix H mix TS mix

H mix
S mix

Enthalpy of mixing, due to broken A-A and B-B bonds and

formation of new A-B bonds
Entropy of mixing

Thermal entropy
Configurational entropy

1. Ideal solution

H mix 0

Assumptions
Pure A and pure B are having same crystal structure and solution of A and B also has
same crystal structure
Enthalpy of mixing is zero
no preference for any type of bond formation or destruction
any atom can sit next to any other atom or random arrangement of atoms
Entropy of mixing
Thermal entropy will be zero (since enthalpy is zero)
Configurational entropy randomness in the solution due to number of
distinguishable ways in which A and B atoms can be arranged

S mix R ( X A ln X A X B ln X B )
Free energy of mixing for an ideal solution

Gmix RT ( X A ln X A X B ln X B )

Molar free energy for an ideal solution

+
G X AG A X B GB RT ( X A ln X A X B ln X B )

GB
GA

More curvature

Chemical Potential (or Partial molar free energy)

Equilibrium in two or more than two component systems (at constant T and P)
will be reached by the transfer of atoms between the phases.
How the free energy of a given phase will change when atoms are added or
removed??
G '

i
ni

T , P , n j , j i

Partial molar free energy is the increase/decrease

in the property of a large system when the
amount of one component is increased by one
mole while keeping the pressure, temperature and
number of moles of other components is fixed

G X AG A X B GB RT ( X A ln X A X B ln X B )
G X A (G A RT ln X A ) X B (GB RT ln X B )

A X A B X B

Graphical representation of Chemical Potential

Chemical potential of any component in a given phase can be obtained by

drawing a tangent to the free energy at particular composition and
extrapolating it such that it intersect with
XA = 1 (XB = 0) - Chemical potential of A in the given phase
or XA = 0 (XB = 1) Chemical potential of B in the given phase

2. Regular solutionsH mix 0

Usually mixing is either endothermic or exothermic but random
Quasichemical approach
Hmix is due to the bond
energies between adjacent atoms only
Vols. of pure A and B are equal and do
not change during mixing
Assumption Entropy of mixing is equal
to that obtaianed for ideal solution

Variation of Hmix with composition for a regular solution

Types of interatomic bonds
A-A bonds with an energy AA
B-B bonds with an energy BB
A-B bonds with an energy AB

Change in Internal energy on mixing

H mix PAB
1
where, AB ( AA BB )
2
For random mixing of A and B atoms

PAB N a zX A X B

If
<0 system will prefer AB bonds over AA or BB bonds, increase in PAB
>0, system will prefer to be surrounded by like atoms PAB less than random

Free energy of mixing for a regular solution

For the assumption that PAB is given by random arrangment

H mix PAB
H mix X A X B
where, N a Z

Hmix
per mol

Free energy of mixing for an ideal solution

Gmix H mix TS mix

Gmix X A X B RT ( X A ln X A X B ln X B )

Free energy change with composition in a regular solution

3. Real solutions
Assumption of random arrangement of atoms is not possible
Compromise between lowest internal energy and entropy (randomness)
< 0, A-B bonds
(increase, reduce
internal energy)

> 0, Increase no.

of A-A and B-B
bonds (reduce
internal energy

for large size

difference,
interstitial

Equilibrium in heterogeneous system

If A & B do not have same crystal structures (assumption in the ideal model)
This result in two free energy curves
Let, stable form of A is fcc
and that of B is bcc

phase solid sol. of Afcc and Bfcc

phase is solid sol. of Abcc and Bbcc
GA (Abcc)

GB (Bfcc)
GA (Afcc)

GA (Afcc)
GB (Bbcc)
A rich

G < G
( stable phase)

B rich

G > G
( stable phase)

Composition between crossover??

G0 G0

but
Instead of single phase ,
Mixture of two phase and

G1 G0

Till
Composition of two phases reach e and e
And, free energy of the system reach min. Ge
Equilibrium between two phase requires that the
tangents to each G curve lie on a common line
Or
Each component in the different phases must
have same chemical potential

A A
B B

Binary phase diagrams

Simple phase diagram

Systems with miscibility gap
Ordered alloys
Simple eutectic system
Phase diagram containing intermediate phases

A&B are completely miscible in both the solid and liquid states
(both are ideal solutions)

Example:
Cu-Ni system

Systems with Miscibility gap

Liquid phase is approx. ideal,
solid phase Hmix > 0

Example: Cu-Fe alloy

Miscibility gap

Hmix >> 0
Miscibility gap can extend in to the liquid phase
Eutectic phase diagram
T1

T2

T3

Example: lead-antimony, silver-copper

Phase diagram
A & B have different crystal structure
Eutectic phase diagram

Example:
chromium-nickel, lead-tin

Ordered alloys
If attraction between unlike
atoms is very strong
Hmix << 0

Hmix more negative

Intermediate phases
Crystal structure different from both the components
Have ideal atom ratio

Narrow stability range

Wide stability range

Extra free energy curve appears for intermediate phase

Example: Mg-Sn, Mg-Pb

Solubility of B in A
B is soluble in , but
A is virtually insoluble in

B B GB
For a regular solid solution

B GB (1 XB )2 RT ln XB
For XB=XBe

GB (1 XBe )2 RT ln XBe
For Xbe <<1

GB
X exp

RT
GB H B TSB
e
B

Solubility of B in A
SB
H B
X exp
exp

R
RT
SB
exp
A
R
H B Q
e
B

X Be

Q
A exp
RT

XBe can never be zero,

No two components are ever completely insoluble in each other

Equilibrium vacancy concentration

Creation of Vacancy
Increases internal energy due to broken bonds around it
At the same time increases randomness or configurational entropy

Equilibrium vacancy concentration

Calculation of Xve is same as calculation of Gmix when Hmix>0
Total entropy change when XV mole fraction of vacancies are added

S XV SV R(XV ln XV (1 XV )ln(1 XV ))
G GA G GA HV XV TXV SV RT(XV ln XV (1 XV )ln(1 XV ))
Equilibrium vacancy concentration

dG
dXV

0
XV XVe

Differentiating above equation and for XV <<1

e
Xv

HV TSV RT ln XVe 0

Gv
exp
RT

Diffusion

Why?

Diffusion to decrease G
G3
G4

Diffusion from high

concentration to low

Alloy with Hmix > 0

Diffusion from low
concentration to high !!!
In general:
Diffusion from region where
chemical potential of species
is high to where it is low, till
equilibrium is reached

Assignment

1. Show tangent to free energy curve extended to XA =0, or =1 will give

chemical potential of pure A or pure B
2. Show from entropy or free energy curve that it is impossible to get a pure
substance
3. Derive Gibbs Phase Rule use equilibrium condition of equal chemical
potential of different component in phases at equilibrium

Effect of pressure on equilibrium phase diagram for pure iron

hcp

Driving force for solidification

Phase: Portion of the system whose properties and composition are

homogeneous and which is physically distinct from other parts of the system
phase is a region of material that is chemically uniform, physically distinct, and
(often) mechanically separable
Components: are the different element or chemical compounds which make up
the system

Gibbs free energy of binary solutions

Step 1

Step 2

Step 1

G1 X AG A X B G B

After step 2, Gmix ??

Gmix H mix TS mix

Total

G2 X AG A X B GB Gmix