PHASE EQUILIBRIUM

INTRO
 Matter
Solid ↔ Liquid↔ Gas

 PHASE CHANGES
Melting of ice

 Principles that govern phase changes

Make alloys, synthesize diamond from graphite

Objective: We would learn about principles and effective

application.
Phase Equilibrium: Different phases come into the contact
with each other at any given instant of
time.
In order to understand this equilibrium PHASE, COMPONENT,
DEGREES OF FREEDOM need to be understood.
Let us start with some basic definitions:

PHASE EQUILIBRIUM

PHASE This is the typical textbook definition which one would see!!

Physically distinct, chemically homogenous and mechanically

separable region of a system (e.g. gas, crystal, amorphous...).

 Gases
Gaseous state always a single phase
→ mixed at atomic or molecular level
 Liquids
Liquid solution is a single phase
→ e.g. NaCl in H2O
Liquid mixture consists of two or more phases
→ e.g. Oil in water (no mixing at the atomic/molecular level)
 Solids
In general due to several compositions and crystals structures many phases are
possible
For the same composition different crystal structures represent different phases.
E.g. Fe (BCC) and Fe (FCC) are different phases
For the same crystal structure different compositions represent different phases.
E.g. in Au-Cu alloy 70%Au-30%Cu & 30%Au-70%Cu are different phases
 PHASE EQUILIBRIUM

Components

The difference between (a) constituent and (b) component

Constituent: a chemical species (an ion or a molecule) that is present in

a system

Component: a chemically independent constituent of a system

Number of components (c): the minimum number of independent

species necessary to define the composition of all the phase(s) present
in the system

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 PHASE EQUILIBRIUM

Components

Independent chemical species which comprise the system:

These could be: Elements, Ions, Compounds
E.g. Au-Cu system : Components → Au, Cu
Ice-water system : Component → H2O
H2O – C2H5OH : Components → 2
NaCl- H2O : Components → 2
N2 – O2 : Components → 2
Al2O3 – Cr2O3 system : Components → Al2O3, Cr2O3
Note that
components need not
be only elements

It is the smallest (least) number of independent chemical constituents

by means of which the composition of each phase present in the
particular system can be expressed, either directly by formula or in the
form of a chemical equation

This is important to note that components need not be just elements!!

 PHASE EQUILIBRIUM

Components

When no reaction takes place,

The number of constituents = the number of components

Pure water: a one-component system

water

Mixture of
ethanol and a two-component system
water:

ethanol water
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 PHASE EQUILIBRIUM

Components

When a reaction takes place,

CaCO3(s) CaO(s) + CO2(g)

Phase 1 Phase 2 Phase 3

a two-component system

CaO CO2

CaO + CO2 CaCO3

The number of constituents the number of components
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 PHASE EQUILIBRIUM

Components

COMPONENTS CHOSEN ARE CaCO3(s) and CaO(s)

CaCO3(s) = CaCO3(s) + 0 CaO(s)

CaO(s) = 0 CaCO3(s) + CaO(s)

CO2(g) = CaCO3(s) - CaO(s)

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 PHASE EQUILIBRIUM

Components

COMPONENTS CHOSEN ARE CaO(s) and CO2(g)

CaCO3(s) = CaO(s) + CO2(g)

CaO(s) = CaO(s) + 0 CO2(g)

CO2(g) = 0 CaO(s) + CO2(g)

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 PHASE EQUILIBRIUM

Components

COMPONENTS CHOSEN ARE CaCO3(s) and CO2(g)

CaCO3(s) = CaCO3(s) + 0 CO2(g)

CaO(s) = CaCO3(s) - CO2(g)

CO2(g) = CO2(g) + 0 CaCO3(s)

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 PHASE EQUILIBRIUM

Components
Counting components
How many components are present in a system in which ammonium
chloride undergoes thermal decomposition?

NH4Cl(s) NH3(g) + HCl(g)

Phase 1 Phase 2

three constituents two-component

a one-component system

additional NH3
NH4Cl or HCl

NH4Cl NH3 + HCl 10

 PHASE EQUILIBRIUM

Degrees of Freedom
P V=R T

CONSTANT
Any two variables are sufficient to define the system completely and
the third variable gets defined automatically.

P and V P and T V and T

System is said to possess two degree of freedom

A mixture of two gases, e.g. CO2 and O2 ? DOF

Degree of freedom or Variance (f): the number of intensive variables that can
be changed independently without disturbing the number of phases in
equilibrium.
 PHASE EQUILIBRIUM

The GIBB’S PHASE RULE

 The phase rule connects the Degrees of Freedom, the number of
Components in a system and the number of Phases present in a
system via a simple equation.
 To understand the phase rule one must understand the variables in
the system along with the degrees of freedom.
For a system in equilibrium

F=C P+2 F – Degrees of Freedom

C – Number of Components
The phase rule or P – Number of Phases
F C+P=2
The Phase rule is best understood by considering examples from actual
phase diagrams as shown in some of the coming slides
 PHASE EQUILIBRIUM
Phase diagram

Map demarcating regions of stability of various phases.

or
Map that gives relationship between phases in equilibrium in a
system as a function of T, P and composition (the restricted form of the
definition sometime considered in materials textbooks)

Phase transformation

Phase Transformation is the change of one phase into another.

E.g.:
Water → Ice
- Fe (BCC) → - Fe (FCC)
Ferromagnetic phase → Paramagnetic phase (based on a property)
 PHASE EQUILIBRIUM
Understanding

A way of understanding the Gibbs Phase Rule:

The degrees of freedom can be thought of as the difference between
what you (can) control and what the system controls

P
F = C+2

Degrees of Freedom = What you can control What the system

controls

Can control the no. System decided how

of components added many phases to
and P & T produce given the
conditions
 Variation of the number of degrees of freedom with number of
components and number of phases.

Total variables Degrees of Freedom

No. of phases
P(C – 1) +2 C – P +2
1 3 3
C=2
2 4 2
2 components
3 5 1
4 6 0

Total variables Degrees of Freedom

No. of phases
P(C – 1) +2 C – P +2

C=3 1 4 4
2 6 3
3 components
3 8 2
4 10 1
 Phase Diagram of Water
How many components
do you have?
We have only one
component which is H2O.

In the one-phase regions,

one can vary either the
temperature, or the
pressure, or both (within
limits) without crossing a
phase line.
We say that in these
regions:
f=c–p+2
=1–1+2
= 2 degrees of freedom.
Phase Diagram of Water

Along a phase line we

have two phases in
equilibrium with each
other, so on a phase line
the number of phases is 2.
If we want to stay on a
phase line, we can't
change the temperature
and pressure
independently.

We say that along a phase

line:
f=c–p+2
=1–2+2
= 1 degree of freedom.
 Phase Diagram of Water

At the triple point there

are three phases in
equilibrium, but there is
only one point on the
diagram where we can
have three phases in
equilibrium with each
other.

We say that at the triple

point:
f=c–p+2
=1–3+2
= 0 degrees of freedom.
Phase Rule

 Summary:
1component 1 phase 2 degrees of freedom
1component 2 phases 1 degree of freedom
1component 3 phases 0 degrees of freedom

Component C Phases P Degrees of

Freedom F
1 1 2
1 2 1
1 3 0
Phase Rule
Component C Phases P Degrees of
Freedom F
1 1 2
1 2 1
1 3 0
Reminder: Gibbs Phase Rule F=C–P+2
 degrees of Freedom = Components – Phases +
2

Gibbs Phase Rule