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
3

1. Metastable, 2. unstable, 3. stable

Mechanical push to overcome

activation barrier

unstable

Activation
barrier

P.E
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

This expression can also be expressed as: U = Uo + Cv dT

Courtsey: H. Bhadhesia

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

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

E
n

exp
N
kT
*

Maxwell-Boltzmann Distribution

E
n

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