MSE 2001 C

Fall 2015
Chapter 7

Phase Equilibria and

Phase Diagrams

Chapter 7
Objectives of the class

Gibbs phase rule

Introduction to phase diagram
Practice phase diagram
Lever rule

Phase
A chemically and structurally homogeneous region of a
material.
A part of a system, physically distinct, macroscopically
homogeneous, and of fixed or variable composition.
It is mechanically separable from the rest of the system.
That is, a phase is a region within which all the intensive
variables vary continuously, whereas at least some of them
have discontinuities at the borders between phases.
Ex: ice water = ice + water
2 phases: solid phase + liquid phase
I want to drink 2-phase system consisting
of solid water and liquid water.
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Phase diagram
Graphical representation of the combination of temperature,
pressure, composition, or other variables for which specific
phases exist at equilibrium.
State point: a position on the phase diagram
Phase diagram of Water (H2O)

Image from http://www.che.tohoku.ac.jp/~scf/

about/about%20sc%20fluid-E.htm

Phase diagram of
Carbon dioxide (CO2)

Gibbs Phase Rule

F=C-P+2
where F = number of independent state variables or
degrees of freedom
C = number of components
P = number of phases that coexist in
equilibrium
If pressure is kept constant (say at 1 atm.)

F=C-P+1
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One-Component Phase Diagrams: Water

Gibbs phase rule for systems in equilibrium: F = C P + 2
F: Degrees of freedom
C: # of Components
P: # of phases

F=2

Solid

* Triple point: F=0

F=2

(= invariant point)

F=1
F=2
F=0

0.00603 atm
0.0098oC

* Critical point: F=0

373.946 C
217.7 atm

Figure 7.2-1
* Component
mponent: a chemical
h
species whose concentration in a phase
can be varied independently of the other species concentration
* Number of degrees of freedom in equilibrium: the number of
variables (P, T, or composition) that can be independently
adjusted without disturbing equilibrium.

A Broader Perspective:
Consider the Earth

One-Component Phase Diagrams

BCC

iron

SiO2

Allotropic: when an element has

several phases
D=BCC, E=FCC, G=BCC, JJ=austenite
Figure 7.2-2 & 7.7-3

One-Component Phase Diagrams

Carbon
104 atm ~ Gpa
At RT, ~2 GPa,
graphite diamond
Industrial diamond:
at high T, high P
polycrystalline

Solubility
Unlimited solubility

Limited solubility

No solubility

Alcohol + Water

Salt + Water

Oil + Water

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Issues to address
When we combine two elements...
what equilibrium state would we expect to get?

In particular, if we specify...
-- a composition (e.g., wt% Cu - wt% Ni), and
-- a temperature (T ) and/or a Pressure (P)

then...
How many phases do we get?
What is the composition of each phase?
How much of each phase do we get?

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Similar concepts apply to solid solutions

Copper (Cu) and Nickel (Ni) are mutually
soluble in any amount
* unlimited solid solubility
* Satisfies Hume-Rothery rule

Carbon (C) has a limited solubility in Iron (Fe).

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Binary Isomorphous Alloy Systems

A mixture of two metals is called a binary alloy
and constitutes a two-component system.
Each metallic element in an alloy is called a
separate component.
Isomorphous systems contain metals which are
completely soluble in each other and have a
single type of crystal structure.

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Cu-Ni: Binary Isomorphous Alloy Example

Cu-Ni: Binary Isomorphous Alloy Example

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