Lecture 16:

Introduction to Phase Diagrams

Read Chpt 4

Phase Diagrams: express behavior of solids, liquids and gases under

variable external conditions (P,T, composition) according to equilibrium
thermodynamics

P-T Phase Diagrams

Example 1: H2O (One Component)
Curve: 2 phases coexist stably
Field: 1 phase exists
t: triple point, 3 phases coexist
c=critical point; 2 phases become
indistinguishable (supercritical
fluid)

Where does the 1D

phase diagram come
from?

Gibbs free energy

relationships

Gibbs Phase Rule:

Cant have unlimited number of coexisting phases!!!
p=c+2-f
p=# of phases in coexistence
c=# of components
f=# of degrees of freedom

Degrees of Freedom: the maximum number of variables that can be

changed independently and still have the same state

Application of Gibbs Phase Rule to 1 Component P-T Diagram for H2O:

Triple point (t): must specify T, P => 0 degrees of freedom

f=c+2-p=1+2-3=0

INVARIANT POINT

Curve: you can change one variable => 1 degree of freedom

f=c+2-p=1+2-2=1

UNIVARIANT

Field: you can change two variables independently => 2 degrees of freedom
f=c+2-p=1+2-1=2

DIVARIANT

Note: You can never have greater than c+2 phases coexisting in equilibrium!!

Other examples of 1 Component P-T Diagrams:

(very important in mineralogy)

1. C (Graphite, Diamond)
Graphite is stable at earths surface (low P,T)
Diamond-metastable at earths surface (stable at higher P,T); much denser
structure (36% less volume than graphite)

Other examples of 1 Component P-T Diagrams:

(very important in mineralogy)

2. Al2SiO5 (Kyanite, Sillimanite, Andalusite)

Common minerals in metamorphic rocks, rimming shows changes in

P,T conditions
Difficult to work out the exact boundaries experimentally
Kyanite is densest: AlVIAlVISiO5

Other examples of 1 Component P-T Diagrams:

(very important in mineralogy)

3. SiO2 (Stishovite, Coesite, Quartz, Tridymite,

Cristobalite)

Coesite, Stishovite => found in meteorite impact craters

Coestite => found in diamond as inclusions

Other examples of 1 Component P-T Diagrams:

(very important in mineralogy)

4. CaCO3 (Calcite, Aragonite)

Aragonite frequently precipitates as organism shells, but its metastable!!

Remember equilibrium! kinetics!!

BINARY (TWO-COMPONENT) PHASE DIAGRAMS (P-T-X)

If phases can have more than one composition (i.e., different proportions of
two components), then we must specify P, T AND X (X=composition of
phase)
Diagram will be 3D, but this is hard to draw and hard to read, so we usually
look at slices, typically T-X slices at fixed P (but we could look at P,T,
fixed X or P,X fixed T)

BINARY (TWO-COMPONENT) PHASE DIAGRAMS (P-T-X)

What is the melting behavior of two components?

Tm,A
Tm,B

BINARY (TWO-COMPONENT) PHASE DIAGRAMS (P-T-X)

What is the melting behavior of two components?

Tm,A

Liquid
Tm,B

Solid

A+B
A

BINARY (TWO-COMPONENT) PHASE DIAGRAMS (P-T-X)

So what actually happens?
1.

ANY mixture (and proportion of A+B) will start to melt at the SAME TEMP
Furthermore, this melting T (EUTECTIC TEMP) will ALWAYS
BE LESS than the melting T of the pure endmembers

2.

The first liquid to form in ANY mixture will always have the SAME
COMPOSITION (EUTECTIC COMP)

3.

If you start with a higher proportion of B than in the eutectic composition,

you will first get only EUTECTIC LIQUID + B; if you start with a higher
proportion of A than in the eutectic composition, you will get only
EUTECTIC LIQUID +A

EXAMPLE: Diopside-Anorthite: NO SOLID SOLUTION

Tm,Do

To understand whats going

on, go back to the phase
rule:

Liquid
Di +Liq

An +Liq

Tm,An
TE

Di +An

Di
(CaMgSi2O6)

f=c-p+2

An
(CaAl2Si2O8)

But, remember, P is already

fixed, so weve used one
degree of freedom and were
left with:
f=c-p+2-1 ; c=2, so f=3-p

When we melt Di+An mixture, we have how many phases? two

When the liquid starts to form, there are three phases, thus f=3-3 =0
There are no degrees of freedom left!! Thus, T must be fixed and X must be fixed at
the melting point!!