Chapter 1.

Thermodynamics and Phase

Diagrams
Equilibrium
Phase: properties and chemical composition are
homogeneous
Components: different elements or chemical compounds
System vs surrounding

Equilibrium
Gibbs free energy
G = H TS
Stable equilibrium is defined as the system
at minimum G

dG = 0

Criterion of phase transformation

G = G2 G1 < 0
Thermodynamics: Possibility of transformation
Kinetics: Speed of transformation
Intensive Properties: T, P
Extensive Properties: V, E, H, S, G

Fig. 1.1 A schematic variation of Gibbs free energy with

the arrangement of atoms.
Configuration A has the lowest free energy and is
therefore the arrangement when the system is at stable
equilibrium. Configuration B is a metastable equilibrium.

Single Component System

Heat Capacity

H
CP =

T P

H = 0 at 298K for a pure element in its most stable state.

T

298

H = C P dT , S =

CP
dT
T

Fundamental equations of thermodynamics

dG = SdT + VdP

= S ,
T P

=V
P T

Single Component System

Eg. Solid = Liquid transformation

G L = G S defines the melting point, Tm

L = Hl Hs
L: Latent heat of melting at Tm

Fig. 1.4 Variation of enthalpy (H) and free energy

(G) with temperature for the solid and liquid phases
of a pure metal. L is the latent heat of melting, Tm the
equilibrium melting temperature.

Single Component System

Equilibrium (T-P) phase diagram of Fe

S
dP
=

dT
eq V

H
Teq V

Eg. = transformation:
: fcc, dense
: bcc

V = V V > 0
H = H H < 0
( is high-temperature phase)

dP
<0
dT

Fig. 1.5 Effect of pressure on the equilibrium

phase diagram for pure iron.

Single Component System

The Driving Force for
liguid=solid transformation:

G = H TS

L T
Tm

T = Tm T > 0
Fig. 1.6 Difference in free energy between
liquid and solid close to the melting point. The
curvature of the GS and GL lines has been
ignored.

Binary Solutions
Suppose that A and B, solvent and solute, respectively, form a system, either
single phase or two phase. Then

XA + XB = 1
G = X AG A + X B GB + Gmix
Gmix = H mix TS mix

Binary Solutions

Fig. 1.7 Free energy of mixing.

Binary Solutions

Fig. 1.8 Variation of G1 (the free energy before mixing) with alloy
composition (XA of XB).

Binary Solutions
For ideal solutions,

H mix = 0
S mix = R ( X A ln X A + X B ln X B )
The entropy of mixing in ideal solutions is essentially the configurational entropy
which can be computed from the number of ways of arranging atoms at the atom
sites, i.e.,

S = k ln w
( N + N B )!
= k ln A
N A! N B !
Since H = 0 for ideal solution,

G = X A G A + X B G B + RT ( X A ln X A + X B ln X B )

Binary Solutions

Fig. 1.9 Free energy of mixing for an ideal solution.

Binary Solutions

Fig. 1.10 The molar free energy (free energy per mole of solution)
for an ideal solid solution. A combination of Figs. 1.8 and 1.9.

Binary Solutions
Chemical potential:
G '

A =
n A T , P, nB

G : Gibbs energy of the whole system, Extensive

G = A X A + B X B
G = Molar Gibbs energy, Intensive

For ideal solution,

A = GA + RT ln X A
B = GB + RT ln X B

Binary Solutions

Fig. 1.11 The relationship between the free energy curve for a
solution and the chemical potentials of the components.

Binary Solutions

Fig. 1.12 The relationship between the free energy curve and
chemical potentials for an ideal solution.

Binary Solutions
Regular solution
H mix = PAB
1
= PAB ( AB ( AA + BB ))
2
PAB : Number of A - B bonds

AB : A - B bond energy

AA , BB , CC : are considered as negative quantities.

PAB = N a ZX A X B (per mole)

H mix = X A X B , ( = N a Z )
The free energy curves of regular solutions vary with temperature and the sign of :

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

Binary Solutions

Fig. 1.13 The different types of interatomic bond in a solid solution.

Binary Solutions

Fig. 1.14 The variation of Hmix with composition for a regular solution.

Fig. 1.15 The effect of Hmix and T on Gmix.

Binary Solutions
Activity
A = G A + RT ln a A
a A : Activity

For regular solution,

aA

=
ln
(1 X A ) 2
X A RT
aA
= A = activity coefficient
XA

Fig. 1.16 The relationship between molar free

energy and activity.

Raoult's law: A 1
Henry's law: A constant

Fig. 1.17 The variation of activity with composition (a) aB (b) aA. Line 1: ideal
solution (Raoults law). Line 2: Hmix<0. Line 3: Hmix>0.

Binary Solutions
Real solutions
Random solution is not attained for 0
Ordered substitutional
Clustering
Random interstitial

Fig. 1.18 Schematic representation of solid solutions: (a) ordered substitutional,

(b) clustering, (c) random interstitial.

Binary Solutions
Ordered Phases
SRO vs LRO
CuAu, Cu3Au and many other intermetallics show LRO.
A superlattice forms in materials with LRO.

Fig. 1.19 (a) Random A-B solution with a total of 100 atoms and XA=XB=0.5, PAB~100,
S=0. (b) Same alloy with short-range order PAB=132, PAB(max)~200, S=(132-100)/(200100)=0.32

Binary Solutions

Fig. 1.20 Ordered substitutional structures in the Cu-Au system: (a) hightemperature disordered structure, (b) CuAu superlattice, (c) Cu3Au superlattice.

Binary Solutions

Fig. 1.21. Part of the Cu-Au phase diagram showing the regions where the
Cu3Au and CuAu superlattices are stable.

Binary Solutions

Fig. 1.22 The five common ordered lattices, examples of which are: (a) L20: CuZn,
FeCo, NiAl, FeAl, AgMg; (b) L12: Cu3Au, Au3Cu, Ni3Mn, Ni3Fe, Ni3Al, Pt3Al, Pt3Fe;
(c) L10: CuAu, CoPt, FePt; (d) D03: Fe3Al, Fe3Si, Fe3Be, Cu3Al; (e) D019: Mg3Cd,
Cd3Mg, Ti3Al, Ni3Sn. (After R.E. Smallman, Modern Physical Metallurgy, 3rd edition,
Butterworths, London, 1970.)

Binary Solutions
Intermetallic Phase and Intermediate Phase:

Fig. 1.23 Free energy curves for intermediate phases: (a) for an intermetallic compound
with a very narrow stability range, (b) for an intermediate phase with a wide stability
range.

Equilibrium in Heterogeneous Systems

Fig. 1.26 The molar free energy of a two-phase mixture (+)

Equilibrium in Heterogeneous Systems

The equilibrium Gibbs energy of a phase
mixture is defined as the common tangent
to the free energy curves of and .
For heterogeneous equilibrium,

A = A
B = B
Also,

aA = aA
aB = aB

Fig. 1.27 (a) Alloy X0 has a free energy G1 as a mixture of 1+1.

(b) At equilibrium, alloy X0 has a minimum free energy Ge when it is
a mixture of e+e.

Fig. 1.28 The variation of aA and aB with composition for a binary

system containing two ideal solutions, and

Binary Phase Diagrams

Equilibrium phase diagram can be derived from the free energy curves.

Fig. 1.29 The derivation of a simple phase diagram from the free energy curves
for the liquid (L) and solid (S).

Binary Phase Diagrams

Fig. 1.30 The derivation of a phase diagram where Hsmix > HLmix = 0. Free
energy v. composition curves for (a) T1, (b) T2, and (c) T3.

Binary Phase Diagrams

At Tm , GS = GL
At T > Tm , GS < GL
Two-phase region (S + L) corresponds to the common tangent region of
the free energy curves of S and L.
Note that the compositions of S and L differ in the two-phase region.
When A and B atoms dislike each other,

H mix > 0
In this case, the free energy curve at low temperature has a region of
negative curvature,
i.e.,
2

d G
< 0
2
dX B

This results in a miscibility gap of and in the phase diagram

Binary Phase Diagrams

Ordered Alloys:
H mix < 0
A atoms and B atoms like each other.
When Hm<<0 then the ordered state can extend to the melting temperature.

Fig. 1.31 (a) Phase diagram when HSmix < 0; (b) as (a) but even more
negative HSmix. (After R.A. Swalin, Thermodynamics of Solids, John
Wiley, New York, 1972)

Binary Phase Diagrams

Simple Eutectic Systems
Hm>>0 and the miscibility gap extends to the melting temperature.

Fig 1.32 The derivation of a eutectic phase diagram where both solid phases have the
same crystal structure. (After A.H. Cottrell, Theoretical Structural Metallurgy,
Edward Arnold, London, 1955,Sir Alan Cottrell.)

Binary Phase Diagrams

Fig. 1.33 The derivation of a eutectic phase diagram where each solid phase has a
different crystal structure. (After A. Prince, Alloy Phase Equilibria, Elsevier,
Amsterdam, 1966.)

Binary Phase Diagrams

Phase diagrams containing intermediate phases

Fig. 1.35 Free energy diagram to illustrate that the range of compositions over which a phase is
stable depends on the free energies of the other phases in equilibrium.

Binary Phase Diagrams

The Gibbs Phase Rule
F=CP+2
F : Degree of freedom
P : Number of phases
C : Number of components
If the temperature or pressure or both are maintained constant at equilibrium
then the number 2 is reduced to 1 or 0 accordingly.
The condition of equilibrium requires that the chemical potentials of an
element (component) must be same for all the phases that contains the
element.

 Effect of Temperature on Solubility

B = B GB
= GB + (1 X B ) 2 + RT ln X B

B = GB GB ;

( GB = GB GB )

X B = exp((GB + ) / RT )
= A exp(Q / RT )
Where Q=HB+ and XB<<1.
GB means the difference in free
energy between form of B and
form of B.

Fig. 1.36. Solubility of B in A.

Binary Phase Diagrams

Equilibrium Vacancy Concentration
Vacancies increase the internal energy of crystalline metal due to broken
bonds formation.

H = H V X V
Vacancies increase entropy because they change the thermal vibration
frequency and also the configurational entropy. Therefore,

S = X V SV R ( X V ln X V + (1 X V ) ln(1 X V ))
At equilibrium, dG / dX v = 0

X ve = exp( Gv / RT ) = exp(S v / R ) exp( H v / RT )

Gv = H v TS v

The value of exp(Sv/R) is about 3 and Hv is about 1eV for metals.

Binary Phase Diagrams

Fig. 1.37 Equilibrium vacancy concentration.

The Influence of Interface on

Equilibrium
Interfaces are important especially in the early stage of transformation. The pressure
difference, as stated below, exists across a curved interface of radius r. Therefore the
pressure difference increases with decrease in size of a particle.

P =

2
r

The pressure difference results in a free energy difference:

G = P V
2Vm
G =
r

(Gibbs-Thomson Eq.)

The G-T equation states that small particles shrink while large particles grow.

The Influence of Interface on

Equilibrium
Suppose a system containing two particles embedded in , one spherical and
another one with a planar (r = ) interfaces. It can be shown that a transfer of a
small amount of , dn, from the large to small particle will increase the system free
energy by
dG = Gdn
The surface area of the small particle will then

dA 2Vm
=
dn
r

Fig. 1.38 The effect of interfacial energy on the solubility of small particles.

The Influence of Interface on

Equilibrium
The solubility of in is sensitive to the size of the particles. In Fig. 1.38 b,
the equilibrium solubility of with a curved interface, Xr, is greater than X, the
equilibrium concentration for a planar interface. Assumming that the phase is a
regular solution and that the phase is almost pure ,

X = exp( (GB + ) / RT )
X r = exp( (GB + 2Vm / r ) / RT )
= X exp(2Vm / RTr )
X (1 + 2Vm / RTr )

Ternary Equilibrium

Fig. 1.40 The Gibbs triangle.

Ternary Equilibrium
Gibbs triangle is used to express the
chemical compositions of ternary alloys
that satisfies
XA+XB+XC = 1
Equilibrium of two phases is represented
by a common tangent plane. In isothermal
section of equilibrium phase diagram, the
lines joining the compositions in
equilibrium are tie-lines. Three-phase
regions are tie-triangles.
Fig. 1.41 (a) Free energies of a liquid and three
solid phases of a ternary system.

Ternary Equilibrium

Fig. 1. 41 (Cont.) (b) A tangential plane construction to the free energy surfaces defines
equilibrium between s and l in the ternary system. (c) Isothermal section through a ternary
phase diagram obtained in this way with a two-phase region (L+S) and various tie-lines.
The amounts of l and s at point x are determined by the lever rule. (After P. Haasen,
Physical Metallurgy, Cambridge University Press, Cambridge, 1978.)

Fig. 1.42 Isothermal sections through Fig. 1.44. (After A. Prince, Alloy
Phase Equilibria, Elsevier, Amsterdam, 1966.)

Fig. 1.43 A projection of the liquidus surfaces of Fig. 1.44 onto the Gibbs triangle.

Fig. 1.44 The equilibrium solification of alloy X. (After A. Prince, Alloy Phase
Equilibria, Elsevier, Amsterdam, 1966.)

Fig. 1.45 A vertical section between points 1, 2 and X in Fig. 1.44.

(After A. Prince, Alloy Phase Equilibria, Elsevier, Amsterdam, 1966.)

Additional Thermodynamic
Relationships for Binary Solutions

Fig. 1. 46 Evaluation of the change in chemical potential due to a change in composition. (After
M. Hillert, in Lectures on the Theory of Phase Transformations, H.I. Aaronson (Ed.), The
Americal Society for Metals and The Metallurgical Society of AIME, New York, 1969.)

Additional Thermodynamic
Relationships for Binary Solutions
dG d 2G
d A d B d ( B A )
=

=
=
= d
dX B
2
1
XB
XA
dX B dX B
d 2G
X A d A = X B d B = X A X B
dX B
dX 2
For a regular solution,

G = X AG A + X B GB + X A X B + RT ( X A ln X A + X B ln X B )
d 2G
RT
=
2
2
dX
X AXB
For an ideal solution,

d 2G
RT
=
dX 2 X A X B

Additional Thermodynamic
Relationships for Binary Solutions
From the definition of the chemical potential,

B = GB + RT ln B X B
Therefore, for an ideal solution,

d B RT
d ln B
1 +
=
dX B X B d ln X B

RT
=
I
XB

and

d 2G
X AXB
= RT I
2
dX

The Kinetics of Phase Transformations

Overcoming the activation barrier,
Ga, by thermal activation is possible
with a probability of

exp G a / RT

Therefore, the rate of transition of

states is proportional to the rate defined
as

rate exp G a / RT exp H a / RT

The above equation was first derived

empirically and is known as Arrhenius
rate equation.

)
Fig. 1.47 Transformations from initial to
final state through an activated state of
higher free energy.