Recap

Broad classification of Materials

Key characteristics of each material class

Materials tetrahedron:
 Lecture 2:
Equilibrium and Kinetics:
Thermodynamics Review
 Concept of stability and metastability

2
1
3

1. Metastable, 2. unstable, 3. stable

 unstable
Mechanical push to overcome
activation barrier Activation
P.E barrier

metastable System automatically

attains the stable state

stable

Configuration
Otherwise Unstable

Minimum Energy STABLE EQUILIBRIUM

Maximum Energy UNSTABLE EQUILIBRIUM

Global Minimum - Most STABLE

Local Minimum - METASTABLE

 State of Materials
The materials which we are using in
metastable state: Al, Fe

What is the stable state (global minimum)

of Fe??

May be the most stable state may not be

of great use for engineers
 Thermodynamic properties
Intensive properties: independent of mass

Pressure
Temperature

Extensive properties: dependent on mass

Internal energy
Enthalpy
 U = internal
energy

At constant pressure
Courtsey: H. Bhadhesia
 T

This expression can also be expressed as: U = Uo + Cv dT
Courtsey: H. Bhadhesia
o
 Sum of internal energy and external energy

For solids the PV term is negligible

The above expression can also be expressed as: H = Ho + C p dT

o
Courtsey: H. Bhadhesia
Demonstration of PV term in solid

1 mol. of Cu at 1 atm.

PV = 0.1 x 106 N/m2 x 7.09 x 10-6 m3

= 0.716 J

U = 6 x 56.4 KJ/mole
= 338.4 KJ

Hence H and U terms can be used

interchangeably in case of solids
Can we use H or U to determine the
stability of the system??

So now we have to look at some other

stability criterion

Lets just first define entropy

 Entropy
The entropy of a system can be defined
by two components:

1. Thermal entropy: Temperature dependent

2. Configurational entropy: Temperature

independent

No. 2 is only possible in case of crystalline

solids
 Thermal Entropy

Thermal:
 Thermal Energy
Atoms in solid oscillate about mean position
with varying amplitude and directions

T , frequency

= 1013 s-1 around 200 K

This oscillatory energy available can be
defined asAverage energy per atom
per mode of oscillation = KT
 Thermal energy
K = Boltzmann constant
1.38 x 10-23 J/K

Average thermal energy per mole of atoms

per mode of oscillation is NKT=RT
In crystalline solids, large ensemble of
atoms, some may loose energy while others
may gain

One can invoke statistics and talk about

average energy

The probability that in an ensemble a specie

has energy E* at a given T
n E *
exp
N kT
 Maxwell-Boltzmann Distribution

n E *
exp
N kT

Fraction of atoms having an energy E*

at temperature T
Configurational Entropy
Boltzmanns
Epitaph

S k lnW
W is the number of
microstates
corresponding to a given
macrostate
 N!
W Cn
N

n!( N n)!

N=16, n=8, W=12,870

Two ordered arrangements possible, rest

all random
If n>>>1

Stirlings Approximation
ln n! n ln n n
S k ln W
N!
k ln
n!( N n)!
k[ N ln N n ln n ( N n) ln( N n)]
 Gibbs Free Energy
G H TS

Helmholtz Free Energy

F U TS

In solids since H U, G and F are used

interchangeably
The variation of G with temperature
 Gibbs Free Energy
G H TS

Condition for equilibrium

minimization of G

Local minimum metastable equilibrium

Global minimum stable equilibrium
 G = GfinalGinitial

G = 0 reversible change

G < 0 irreversible or
spontaneous change

G > 0 impossible