Lecture 7 (9/27/2006)

Crystal Chemistry
Part 6:
Phase Diagrams

Gibbs Free Energy

G the energy of a system in excess of its

internal energy. (This is the energy necessary for
a reaction to proceed)
G = E + PV - TS
dG = VdP SdT
at constant T (G/P)T = V
at constant P (G/T)P = -S

Stable phases strive to have the lowest G

Therefore, the phase with the highest density at a
given pressure and the highest entropy at a given
temperature will be preferred

Relationship of Gibbs Free Energy to

Phase Equilibrium

Clapeyron Equation

Defines the state of equilibrium between

reactants and product in terms of S and V
dGr = VrdP SrdT
dGp = VpdP SpdT
at equilibrium: VrdP SrdT = VpdP SpdT
or: (Vp Vr) dP = (Sp Sr) dT
or: dP/dT = S / V
The slope of the equilibrium curve will be
positive if S and V both decrease or
increase with increased T and P

Reactants -Products

Vice > Vlw -V

Sice < Slw +S

Slope of Phase
Reaction Boundaries
dP/dT = S / V

Reactants -Products

Vlw < Vwv +V

Slw < Swv +S

Variables

Extensive Variables dependent on the

amount of material present

mass
volume
moles of atoms

Intensive Variables independent on the

amount of material present

pressure
temperature
density
compositional proportions

Gibbs Phase Rule

F=C+2
F number of degrees of
freedom of intensive
variables (p, t, x) that will still
preserve chemical equilibrium
C number of components
number of phases

One Component Phase

Diagrams
C

Al2SiO
5

Illustrate
Polymorphism
Isochemical
P & T are
intensive
variables

SiO2

CaCO
3

Phase Rules:

divariant fields F=2

univariant lines
F=1
invariant points
F=0

Two Component Phase

Diagrams
Solid Solution
Crystallization

Eutectic Crystallization

Usually portrayed as isobaric T-X diagrams

For igneous systems, magma/melt is a phase of a simplified
composition defined by the mineral phases of interest
Liquidus denotes the temperature at which the liquid of a
particular compositions will begin to crystallize
Solidus denotes the temperature at which the liquid of a
particular composition will be completely crystallized

Eutectic Crystallization of
Anorthite (plagioclase) and Diopside (pyroxene)

Eutectic
Point

Lever Rule
Proportions

Anorthite

Diopside

Solid Solution Crystallization

Limited Solid
Solution and
Subsolidus
Exsolution:
e.g. Alkali Feldspar
Increasing Pressure

Exsolution Textures
Subsolidus Unmixing

Pyroxene
Hypersthene (Opx) exsolution
lamellae
in Augite (Cpx) host

Alkali Feldspar
Albite exsolution
(perthite)
in Microcline host

Multi-component Phase
Diagrams

Igneous Systems Liquidus Diagrams

Liquidus
Surface

Eutectic
Point

Cotectic
Lines

quilibrium assemblages in metabasalts

Multi-component
Phase Diagrams

Metamorphic Systems
Chemographic
Diagrams
e.g. ACF
A = Al O +Fe O -Na O-K O
2

C = CaO 3.3P2O5
F = FeO + MgO + MnO
Shows equilibrium assemblages
at specified P & T