Thermodynamics and Concept of Equilibrium: Prof. Dr. Ir. Bondan Tiara Sofyan, M.Si

Module 1.
Thermodynamics and Concept

of Equilibrium
Prof. Dr. Ir. Bondan Tiara Sofyan,M.Si.

Module 1: Thermodynamics and Concept
of Equilibrium
1. Concept of Equilibrium
2. Single Component System
3. Binary Component System
4. Equilibrium in Heterogeneous System
Learning Outcomes
After learning this module, students are expected to:
1. Understand the concept of equilibrium in terms of ΔG(C2) and the effects of

temperature on it (C3).
2. Be able to apply the concept of equilibrium in a single component system
(C3).
3. Be able to apply the Clapeyron equation in determining the change of
density of a single component system (C4).
4. Be able to apply the concept of equilibrium in an ideal solution of a binary
component system (C3).
5. Be able to apply the concept of equilibrium in a random solid solution (C3).
6. Understand the situation in which ordered solid solution is stable (C3).
7. Be able to understand the concept of equilibrium in an intermediate phase
(C3)
8. Be able to apply the concept of equilibrium in a high enthalpy system (C3).
9. Be able to apply the concept of equilibrium in a heterogeneous system (C3).
Dept. Metallurgy and Materials

University of Indonesia
1. Concept of Equilibrium
Definition
 Component - chemically recognizable species (Fe and C in carbon
steel, H2O and NaCl in salted water), which are mixed initially. A
binary alloy contains two components, a ternary alloy – three, etc.
 Materials consist of phases or mixtures of phases. A phase is a
portion of a system that has uniform properties and composition and
physically and chemically distinct material regions The phase may
or may not be in an equilibrium state.
 Two distinct phases in a system have distinct physical or chemical
characteristics (e.g. water and ice) and are separated from each
other by definite phase boundaries.
 A phase may contain one or more components.
 A single-phase system is called homogeneous.
 Systems with two or more phases are mixtures or heterogeneous
systems.

Phase
Aluminum-  (lighter
Copper
phase)
Alloy
(darker
phase)
Adapted from
Fig. 9.0,
Callister 3e.

Definition
• Water-ethanol solution
• How many components?
• How many phases?
• Ice water
• Air (dry and particulate free)

Concept of Equilibrium
 The phases that are not in equilibrium
can undergo a spontaneous phase
transformation to an equilibrium phase or
mixture of phases.
 Thermodynamics can be used to predict
weather the system is in equilibrium and to
analyze the phase stability and phase
transformations.

 Equilibrium is determined by the Gibbs free energies
of the system, ΔG = Δ Gfinal - ΔGinitial = Δ H - T Δ S.
 H is the enthalpy, a measure of the heat content of
the system:
H = E + PV, E = internal energy
 For condensed phase and constant pressure: H ~ E.
 S is a measure of the randomness of the system.

A pure substance is
heated at constant
pressure
H = E + PV

 A system is said to be in equilibrium when

it is in the most stable state or at the
lowest possible value of Δ G ,.i.e, shows
no desire to change ad infinitum.
 At low temp: ΔG = Δ H - T Δ S ??
 At high temp: ΔG = Δ H - T Δ S ??

The concept of equilibrium can

be illustrated by this figure.
Configuration B is said
metastable equilibrium state, A
is stable equilibrium state.
•Δ G < 0  process is allowed

•Δ G > 0  process is forbidden B A
•Δ G = 0  equilibrium

 Thermodynamics tells us what can happen - not how fast
it will happen .
 “How fast?” is the question addressed by kinetics.
 Higher hump  slower transformation rates
 Most kinetic phenomena in materials involve diffusion.
 Therefore mechanisms of diffusion in materials should
be understood before discussing kinetics of the
nucleation and growth of a new phase.

2. Single Component System
Single Component System
H and S as function of T at constant P
In a closed one-component system equilibrium, at temperature T
and pressure P, corresponds to the state with minimum Gibbs free
energy G.
Therefore, in order to predict what phases are stable under
different conditions we have to examine the dependence of G on
T and P.
Let’s use thermodynamic relations to predict the

temperature dependence of H, S, and G at constant P.

T
 H  H (T )  H 298   C P dT
For H(T) we have Cp   
 T  P T 298
 S  CP CP
For S(T) we have    S (T )   dT
 T  P T T
0
H
Slope = Cp
Cp
0
298 T (K)
S Slope = Cp/T
0
0 T (K)
0
0 T (K)
For G = H – TS we have dG = -SdT +VdP and for P = const
 G    2G   S  C for the
   S for the  2       P
 T  P slope  T  P  T  P T curvature
H liquid Hm
solid
H
Slope = Cp
Tm T (K)
298
TS
Slope = -S
Hl >Hs,
solid
Sl>Ss
G
G
at all T
liquid

A typical P-T phase diagram for a pure material
 Effects of Pressure :
 Allotropic change
 At constant T, ΔG of a phase increased with
pressure:
 G 
  V
 P T

A typical P-T phase diagram for a pure material
The red lines on the phase diagram show the conditions where different phases
coexist in equilibrium: Gphase1 = Gphase2

Equilibrium between two phases: Clapeyron equation
If two phases in equilibrium have different molar volumes, their free

energies will increase by different amounts when pressure changes at a
fixed T.
The equilibrium, therefore will be disturbed by the change in pressure. The
only way to maintain equilibrium at different pressures is to change
temperature as well.
For two phases in equilibrium Gl = Gs and dGl = dGs for infinitesimal
change in T and P (so that the system remains in equilibrium)

Equilibrium between two phases: Clapeyron equation
At equilibrium
Therefore the Clapeyron equation
The Clapeyron equation gives the relationship between the

variations of pressure and temperature required for
maintaining equilibrium between the two phases.
G as function of P and T for liquid and solid phases
Schematic representation
of the equilibrium surfaces
of the solid and liquid
phases of water in G-T-P
space.
The planes show the free
energies of liquid and solid
phases, the intersections
of the planes correspond to
the (P, T) conditions
needed for maintaining
equilibrium between the
phases, Gl = Gs.

Clapeyron equation: examples
For liquid to gas transition: A typical diagram for a pure material:
ΔV =Vg - Vl >> 0
Δ H = Hg - Hl > 0 – we have to add
heat to convert liquid to gas.
Therefore:
For liquid to solid transition:

ΔV =Vs - Vl < 0
Δ H = Hs - Hl < 0 –heat is released
upon crystallization.
Therefore:

Clapeyron equation: examples
A typical diagram for a pure material:
In general, it takes heat (Δ H > 0)

to proceed from a low-temperature
to a high-temperature phase
(entropy of a high-temperature
phase is higher than the entropy of
a low-temperature phase).
Therefore, the slope of the For some materials, however, ΔV

equilibrium lines in a P-T phase =VS - Vl > 0, and
diagram of a pure material
reflects the relative densities of
the two phases. This is the case for H2O (ice
floats in liquid water), Ga, Ge,
diamond
Clapeyron equation: more
examples
Some materials may exist in more
than one crystal structure, this is
called polymorphism. If the
material is an elemental solid, it is The diagram shows the stable phases
called allotropy. for pure iron at varying temperature and
pressure.
Close-packed FCC g-Fe has a

smaller molar volume than BCC
-Fe: ΔV = Vg - V < 0
At the same time Δ H = Hg - H > 0
Therefore:
<0
Which phase has higher density? Dept. Metallurgy and Materials

Clapeyron equation: more examples
Another example of allotropy is silica (SiO2), which can exist as
quartz, trydimite, coesite and stishovite.

Another example of allotropy is carbon, which can exist as diamond,
graphite, and amorphous carbon.

From the phase diagram, what phase has higher density near
two-phase equilibrium conditions:
Diamond or graphite?
Diamond or liquid carbon?
Graphite or liquid carbon?
Why do not we see fullerenes and nanotubes on the phase
diagram?

Example: squeezing diamond from graphite
Superman has the power to transform
graphite into diamond by squeezing it
strongly with his hand. Assuming that the
transformation takes place isothermally at
room temperature (298 K), what is the
minimum pressure (in MPa) that Superman
must apply with his superfist?
In a reference book we can find that at 298 K:
Hgraphite– Hdiamond = -1900 J
Sgraphite = 5.73 J/K Assume: 1 mol of graphite
Sdiamond = 2.43 J/K Ar C = 12
rgraphite = 2.22 g/cm3
 G 
rdiamond = 3.515 g/cm3
  V G  H  TS
 P T
Summary
G  H  TS
For a single component system:
 G 
at constant P:    S
 T  P
 G 
at constant T:   V
 P T
Clapeyron equation: relationship between
the variations of pressure and temperature
required for maintaining equilibrium between
the two phases.

3. Binary Component System
a) Terminology
b) Temperature as thermodynamic variable
c) Gibbs free energy of a binary solution
d) Real Solutions
Reading: Chapter 1.3 – 1.4, Porter and Easterling
Terminology
Solid solutions are made of a host (the solvent or matrix) which dissolves the
minor component (solute). The ability to dissolve is called solubility.
 Solvent: in an alloy, the element or compound present in greater amount
 Solute: in an alloy, the element or compound present in lesser amount.
 Solid Solution:
 homogeneous
 maintains crystal structure
 contains randomly dispersed impurities (substitutional or interstitial)
 Second Phase: as solute atoms are added, new compounds / structures
are formed, or solute forms local precipitates
 Solubility Limit of a component in a phase is the maximum amount of the
component that can be dissolved in it (e.g. alcohol has unlimited solubility in
water, sugar has a limited solubility, oil is virtually insoluble). The same
concepts apply to solid phases: Cu and Ni are mutually soluble in any
amount (unlimited solid solubility), while C has a limited solubility in Fe.
Whether the addition of impurities results in formation of solid solution or second

phase depends the nature of the impurities, their concentration and
temperature, pressure…

Composition as a thermodynamic
variable
 Real materials are almost
always mixtures of different
elements rather than pure
substances: in addition to T
and P, composition is also a
variable.
 To understand conditions for
equilibrium and phase
diagrams we have to
understand how the Gibbs
free energy of a given phase
depends on composition,
temperature and pressure.
Since many real experiments
are performed at fixed pressure
of 1 atm, we will focus on G(T,
composition).

Mind Map ΔGmix
G  H  TS
For binary component system: Ideal solution Real solution
Δ Hmix = 0 ΔHmix ≠ 0
Gstep 2 = Gstep 1 + ΔGmix
ΔHmix < 0 ΔHmix > 0
Low T High T
(Random) solid solution:

• Substitutional
• Interstitial Intermediate phase Clustering
EAB ↓ PAB ↑
Ω semakin -
Ordered SS  phase:
• Short range, s~0.5 Dept. Metallurgy and Materials
• Long range, s=1 Intermetallic University of Indonesia
Gibbs free energy of a binary solution
 Let’s consider a binary solution of A and B atoms that have the

same crystal structures in their pure states and can be mixed in
any proportions - form a solid solution with the same crystal
structure (unlimited solid solubility). Example: Cu and Ni.
 1 mol of homogeneous solid solution contains XA mol of A and XB
mol of B. XA and XB are the mole fractions of A and B in the alloy.
XA + XB = 1
 Let’s consider two steps of mixing:
1. Bring together XA mol of pure A and XB mol of pure B
2. Mix A and B to make a homogeneous solution

Step 1 Step 2

Gstep 1 = XA GA + XB GB
ΔGmix
Gibbs free energy per

mole before mixing

where Δ Gmix is the change of the Gibbs free energy caused by the
mixing.
heat of mixing of the components (heat of

formation of a solution)
difference in entropy between mixed and

unmixed states (entropy of formation of a
solution)

 Let’s first consider an ideal solution: interactions between atoms
A-A, B-B and A-B are identical, and Δ Hmix = 0.
 The free energy change upon mixing only due to the change in
configurational entropy:
there is only one way the atoms can be

arranged before mixing


G id  Gstep 2  X AG A  X BGB  RT [ X A ln X A  X B ln X B ]
T ↑G ↓ and curvature ↑, due to greater entropy

For a non-ideal solution we have to take into account heat of formation
ΔHmix ≠ 0:
ΔHmix > 0 mixing is endothermic (heat absorbed)
ΔHmix < 0 mixing is exothermic (heat released)
Let’s account for the heat of formation ΔHmix ≠ 0 using a simple model called
statistical or quasi-chemical model. In this model the heat of mixing is only
related to the bond energies between adjacent atoms. The assumption is that
the interatomic distances and bond energies are independent of composition.
3 types of bonds:
A – A bond (energy EAA)
A – B bond (energy EAB)
B – B bond (energy EBB)
If there are PAA, PBB, PAB bonds of each type, the
internal energy of the solution is

the solution is ideal: ΔHmix = 0
ΔHmix > 0  atoms will tend to be surrounded by atoms of

the same type
ΔHmix < 0  atoms will tend to be surrounded by atoms
of the different type
But for small differences between EAB and (EAA+EBB)/2 (and for high T) we
can still consider a random arrangement of atoms in a solution (such
solutions are called regular solutions). Then
Ω is tangent at
XA=0 and 1
z= number of bonds (PAA, PBB, PAB)

N = Avogadro’s number
So,
non-ideal solution
ideal solution
For Ω < 0, ΔHmix < 0

 exothermic For Ω > 0, ΔHmix > 0  mixing (formation of A-B
solution  mixing is pairs) is avoided at low T. At low T clustering may
favorable at all T occur – solution is not regular. At high T entropy
helps to mix.

Real solutions
 For regular solutions we assumed a random arrangement of
atoms in a solution. For many real materials this is not a valid
assumption.
 If Ω < 0 the internal energy is minimized by increasing the number
of A-B bonds  can lead to ordered solution at low T
 If Ω > 0 the internal energy is minimized by increasing the number
of A-A and B-B bonds  can lead to clustering at low T
 The arrangement of atoms is a result of compromise between the
lowest internal energy and highest entropy. Degree of clustering
or ordering decreases with increasing T since the entropy
contribution (-TS) to Gibbs free energy becomes more important.
random ordered clustering

Real solutions
~ 8 nm
Cd-Mg
cluster
~ 14 nm
~ 7.4 nm
(001)
Al
Cu
Mg
~ 6 nm Cd
Cu Mg Cd
Atomic clusters in aluminium alloys
B.T. Sofyan, I.J. Polmear and S.P. Ringer, 2002, Precipitation processes in Al-4Cu-(Mg,
Cd) (wt. %) alloys, Mat. Sci. Forum, Vol. 396 – 402, pp. 613 – 618.

Real solutions
 If atoms A and B have different sizes, the statistical or quasichemical
model will underestimate ΔHmix . The energy of the elastic strain fields
due to the mismatch in atomic sizes should be taken into account. If
the size difference is large, the contribution of the strain energy term
could as important as the chemical (bonding) term.
 If the size difference between the atoms is very large, then interstitial
solid solutions are energetically favorable.
 In systems with strong chemical bonding between the atoms there is a
tendency for formation of intermediate phases. The intermediate
phases can have a different crystal structure and may be highly
ordered.

Real solutions
Substitutional Solid Solutions
 Max solute concentration = 50 at %
 e.g. Cu-Ni (unlimited solid solubility)
 Factors for high solubility:
 Atomic size factor - atoms need to “fit”
 solute and solvent atomic radii
should be within ~ 15%
 Crystal structures of solute and solvent
should be the same
 Electronegativities of solute and
solvent should be comparable
(otherwise new intermediate phases
are encouraged).
 Generally more solute goes into
solution when it has higher valency
than solvent

Real solutions
Interstitial Solid Solutions
 Factors for high solubility:
For fcc, bcc, hcp structures the voids
(or interstices) between the host atoms
are relatively small  stomic radius of
solute should be significantly less than
solvent.
 Normally, max. solute concentration
≤10%
e.g. ≤ 0.1 at% of C in α-Fe (BCC).

Ordered Phase
 Substitutional solution can be completely random 
probability that any given site in the lattice will contain
an A atom will be equal to the fraction of A 
PAB=NzXAXB, PAB=number of AB bonds, N=Avogadro
No, z=number of bonds per atom.
 If Ω<0 and PAB is greater  the solution contains short
range order (SRO) may be present. Degree of
ordering, s: PAB  PAB ( random)
s
PAB (max)  PAB ( random)
Same alloy, long-range order

PAB=200, PAB(max)~200, S=(200-
Random solution, total 100 Same alloy, short-range order 100)/(200-100)=1  all atoms
atoms, XA=XB=0.5, PAB~100, PAB=132, PAB(max)~200, S=(132- occupy their
Dept. Metallurgy andcorrect sites 
Materials
S=0 100)/(200-100)=0.32 separate
Universityphase
of Indonesia
Ordered Phase
 Examples of long-ordered phase: AuCu, Cu3Au, CdMg, CuPd

Ordered Phase
High Temperature, Low Temperature,
disordered phase ordered phase
(FCC, cF4) (L10, tP4)

Ordered Phase
Examples of common ordered structures (superlattices)
L20: CuZn L10: CuAu (I) L12: Cu3Au D03: Fe3Al
Structure Examples
L20 CuZn, FeCo, NiAl, FeAl, AgMg
L12 Cu3Au, Au3Cu, Ni3Mn, Ni3Fe, Ni3Al, Pt3Fe
L10 CuAu, CoPt, FePt
D03 Fe3Al, Fe3Si, Fe3Be, Cu3Al
D019 Mg3Cd, Cd3Mg, Ti3Al, Ni3Sn
CuPd disordered phase
CuPd ordered phase
Fig. 2 Evolution of the

microstructure during heating:
(a) initial state + 250ºC, 5 min +
360ºC, 15 min + 400°C, 5 min;
(b) state (a) + 400°C, 15 min +
440°C, 5 min + 550°C,15 min;
(c) state (a) + heating to 600°C
and cooling in the microscope
column
Fig. 1 Initial state of the

Pd-Cu-20Ag alloy after
annealing at 950ºC, 1 h,
quenching:
(a) microstructure;
(b) diffraction pattern of
the upper grain
Cu-50Pd-Ag (wt. %) Dept. Metallurgy and Materials

Ref: Volkov, A.Y., Platinum Metals Rev., 2004, 48, (1), p.3 University of Indonesia
Temperature dependence of the electrical
resistivity of the Pd-Cu-10Ag alloy disordered by
(heating rate of 600ºC/ h) annealing at 850°C, 1 h,
quenching

Cu-28Zn-2.5Al
as-cast as-homogenized

Intermediate Phase
 If an intermediate phase have a specific composition
and small deviations from the ideal composition
cause a rapid rise in G, the phase is called
compound.
 Compounds typically have a stoichiometric
composition (AnBm where n and m are integers).
 The structure of intermediate phases is determined
by
 Relative atomic size:
 RA/RB ~ 1.1-1.6 – Laves phases (e.g.MgZn2,
MgNi2)
 RA >> RB – interstitial compounds, e.g. Fe3C
 Valency: stability of phases depends on the # of
valence electrons per unit cell
 Electronegativity: different electronegativity of
components leads charge transfer and formation
of strong ionic bonding, e.g.Mg2+ + Sn4- =
Mg2Sn
 The intermediate phases can have a crystal structure
that is different from the one of the pure components,
and an additional Gibbs free energy curve for the
intermediate phase should be considered.

Intermediate Phase
Mg2Si
Matrix
Al2Cu
Si
Al5(Fe,Mn)Si

Summary ΔGmix
G  H  TS
For binary component system: Ideal solution Real solution
Δ Hmix = 0 ΔHmix ≠ 0
ΔHmix < 0 ΔHmix > 0
Low T High T
(Random) solid solution:

• Substitutional
• Interstitial Intermediate phase Clustering
EAB ↓ PAB ↑
Ω semakin -
Ordered SS  phase:
• Short range, s~0.5 Dept. Metallurgy and Materials
• Long range, s=1 Intermetallic University of Indonesia
4. Equilibrium in Heterogeneous
System
Reading: Chapter 1.4 Porter and Easterling

Systems with two or more phases are heterogeneous systems. If
pure components A and B have different equilibrium crystal
structures, phase α and phase β, we have to consider two Gibbs
free energy curves, one for each phase:
For compositions near cross-over of Gα and Gβ, the total Gibbs

free energy can be minimized by separation into two phases.

Let’s consider a systems with two phases α and β, that have compositions
XBα and XBβ and Gibbs free energies Gα and Gβ. If the average
composition of the system is XB0, the molar free energy Gα+β is given by
the point on a straight line that connects Gα and Gβ, and the relative
number of moles of phases α and β can be found by the lever rule:
Molar free energy of the

phase mixture with molar
fractions of phases α and β,
Mα and Mβ

For composition XB0 the lowest Gibbs free energy is G0α for a
homogeneous system. The total Gibbs free energy can be
additionally decreased by separation into two phases, for example
with compositions XB1 and XB1.

The total Gibbs free energy is at minimum if phases α and β have
compositions XBeq and XBeq. These are the equilibrium compositions
of the phases. In equilibrium tangents to Gα and Gβ curves are the
same (lie on a common line).
So, in a heterogeneous system  the lowest free energy may be achieved
by separation into two phases. Dept. Metallurgy and Materials
Self Study
Please do Exercise 1.1 -1.8 in Chapter 1 Porter
Easterling. Make sure you understand the
concept of ∆G, ∆H, and entropy related to
system equilibrium.


Thermodynamics and Concept of Equilibrium: Prof. Dr. Ir. Bondan Tiara Sofyan, M.Si

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Module 1.

Thermodynamics and Concept

Prof. Dr. Ir. Bondan Tiara Sofyan,M.Si.

1. Understand the concept of equilibrium in terms of ΔG(C2) and the effects of

Dept. Metallurgy and Materials

Dept. Metallurgy and Materials

Dept. Metallurgy and Materials

Dept. Metallurgy and Materials

Dept. Metallurgy and Materials

Dept. Metallurgy and Materials

Dept. Metallurgy and Materials

 A system is said to be in equilibrium when

Dept. Metallurgy and Materials

The concept of equilibrium can

•Δ G < 0  process is allowed

Dept. Metallurgy and Materials

Dept. Metallurgy and Materials

Let’s use thermodynamic relations to predict the

Dept. Metallurgy and Materials

Dept. Metallurgy and Materials

Dept. Metallurgy and Materials

Dept. Metallurgy and Materials

If two phases in equilibrium have different molar volumes, their free

Dept. Metallurgy and Materials

Therefore the Clapeyron equation

The Clapeyron equation gives the relationship between the

Dept. Metallurgy and Materials

For liquid to solid transition:

Dept. Metallurgy and Materials

In general, it takes heat (Δ H > 0)

Therefore, the slope of the For some materials, however, ΔV

Close-packed FCC g-Fe has a

Which phase has higher density? Dept. Metallurgy and Materials

Dept. Metallurgy and Materials

Dept. Metallurgy and Materials

Dept. Metallurgy and Materials

Dept. Metallurgy and Materials

Whether the addition of impurities results in formation of solid solution or second

Dept. Metallurgy and Materials

Dept. Metallurgy and Materials

ΔHmix < 0 ΔHmix > 0

(Random) solid solution:

 Let’s consider a binary solution of A and B atoms that have the

Dept. Metallurgy and Materials

Gstep 2 = Gstep 1 + ΔGmix

Gibbs free energy per

Dept. Metallurgy and Materials

heat of mixing of the components (heat of

difference in entropy between mixed and

Dept. Metallurgy and Materials

there is only one way the atoms can be

Dept. Metallurgy and Materials

Dept. Metallurgy and Materials

Dept. Metallurgy and Materials

ΔHmix > 0 mixing is endothermic (heat absorbed)

ΔHmix < 0 mixing is exothermic (heat released)

Dept. Metallurgy and Materials

the solution is ideal: ΔHmix = 0

ΔHmix > 0  atoms will tend to be surrounded by atoms of

z= number of bonds (PAA, PBB, PAB)

For Ω < 0, ΔHmix < 0

Dept. Metallurgy and Materials

random ordered clustering