Thermodynamics and Phase diagram

capo regime
G
H
S
Dominate G at low temperatures
Dominate G at High temperatures
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
Relative stability of a system is determined by Gibbs free energy (G)
TS H G =
Enthalpy
Absolute temperature
Entropy
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
Gibbs free energy (G)
PV E H + =
Internal Energy
Pressure
Volume
(K.E. + P.E. of the system)
Atomic vibrations (Liquid and Solid), or
Translational and rotational energies
of atoms or molecules within a liquid and gas
Interaction/bonds between atoms
Enthalpy
A system is said to be in equilibrium when it is in the most stable state
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
0 = dG
Gibbs free
energy G
dG = 0
Equilibrium
Necessary criterion for phase transformation
0
1 2
< = A G G G
Gibbs free
energy G
State of system
1 2
G
1

G
2

dG=0
dG=0
Metastable equilibrium Stable equilibrium
G
1
> G
2

Equilibrium cont..
dG=0
Single component systems (pure element or molecule)
Time
T
M

Liquid
Solid
Phase transformation at
constant temperature
T
e
m
p
e
r
a
t
u
r
e

Time-Temperature curve
Enthalpy and Entropy as a
function of temperature
P
p
T
H
C
|
.
|

\
|
c
c
=
}
=
T
p
dT C H
298
P
p
T
S
T
C
|
.
|

\
|
c
c
=
}
=
T
p
dT
T
C
S
0
H = 0 for pure element in its
most stable state at 25
o
C
Quantity of heat required to
raise the temp. of the
substance by 1 K
VdP SdT dG + =
@ constant pressure
S
T
G
p
=
|
.
|

\
|
c
c
Gibbs free energy as a function of temperature
System of fixed mass and composition
Varying pressure and temperature
Variation of G with
temperature for
the solid and liquid
phases of a pure
metal
Latent heat
S
L
> S
s
H
L
> H
S
@ all temps.
Effect of pressure on equilibrium phase diagram for pure iron
hcp
V T
H
dT
dP
eq eq
A
A
=
|
|
.
|

\
|
Clausius-Clapeyron Equation
0 < = A
o
m m
V V V
0 > = A
o
H H H
dP/dT is negative
Driving force for solidification
m
T
T L
G
A
~ A
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
Gibbs free energy of pure A
Gibbs free energy of binary solutions of A and B elements
Gibbs free energy of pure B
+
Step 1 Step 2
Gibbs free energy of binary solutions

Mix
B B A A
G X G X G + =
1
Step 1
mix
G G G A + =
1 2
After step 2, G
mix
??
mix mix mix
S T H G A A = A
Step 2 - Mixing
Ideal solutions
Regular solutions
Real solutions

mix
G A
will depend on definition of binary solution