Phase rule

• Gibbs Phase Rule

• Goldschmidt mineralogical phase rule

• implications for chemographic analysis

Sunday, September 13, 2009

 basis of phase rule

• minerals (phases) are reaction products!

therefore, they record the reactions that
occurred, as well as conditions

• why is phase rule useful?

• helps to characterize state of the system

• predict equilibrium relations of phases

• helps to construct phase diagrams

Sunday, September 13, 2009

 F=C-P+2

• F = degrees of freedom (variance)

• C = minimum # components in system

• P = # phases

• integers related to # intensive variables (scale

independent; e.g., P, T, density, Xmineral)

Sunday, September 13, 2009

 F=C-P+2

• what does Gibbs say?

• variance of the system is the minimum # of

intensive variables needed to define the
state of the system at equilibrium

• for each C we add, must specify 1 more

variable (more stuff)

• for each P we add, 1 less variable need be

specified (fewer boxes to put it in)

Sunday, September 13, 2009

 F=C-P+2

• or, if you change 1 variable, how many other

things must you change to maintain the
system?

• if F = 2, can change either P or T

independently

• if F = 1, if change one thing, must change

the other (or, if know one, you know the
other)

• if F = 0, cannot change anything and still

keep system the same

Sunday, September 13, 2009

 degrees of freedom

• F = 0 invariant (no change in system)

• F = 1 univariant (equilibrium line)

• F = 2 divariant (stable phase region)

Sunday, September 13, 2009

 F=2

F=1

F=0

Sunday, September 13, 2009

 selecting components

CaMg(CO3)2 + 2 SiO2 = CaMgSi2O6 + 2 CO2

dolomite + 2 quartz = diopside + 2 carbon dioxide

possible components CaO, MgO, SiO2, CO2

or

CaMgO2, SiO2, CO2

which is best? how do we choose?

Sunday, September 13, 2009

 selecting components

suppose we have a pelitic rock containing 5 phases

typical of lower amphibolite facies:

St + Grt + Bt + Ms + Qtz

how many components?

Sunday, September 13, 2009

 selecting components
or suppose we have a mafic rock containing 5 phases
typical of greenschist metavolcanics:

Act + Chl + Ep + Ab + Qtz

how many components?

Sunday, September 13, 2009

 “degenerate” systems

if you can reduce the # components to a limited sub-

set of the whole system that still explains the
observed mineral assemblage, this is simpler
A
e.g., use B-C,
rather than A-B-C

A33B33C33

B100C0 B0C100
B50C50
B C
Sunday, September 13, 2009
 selecting components
so for our greenschist:

Act + Chl + Ep + Ab + Qtz

how can we reduce the ACNFMS components?

• assume free substitution of Fe & Mg
• assume plagioclase is pure Ab (and no Na in others)
• assume system is Si-H2O saturated
end up with 3 components (ACF);
phase rule says F = 3 - 3 + 2 = 2 (not counting Ab & Qtz)
so the system is divariant, and might even have more freedom
(will come back to this)

Sunday, September 13, 2009

 intensive variables

• need to know how many intensive (mass-

independent) variables govern the system

• if T & P are variables, F = C - P + 2

• if either one is fixed (constant), the “modified”

phase rule becomes F = C - P + 1

Sunday, September 13, 2009

 “modified” phase rule

for a T-X A
diagram,
P = const.

so, only 1
intensive variable
B

Sunday, September 13, 2009

 assumptions

• assumptions when applying Gibbs phase rule:

• EQUILIBRIUM!!! sufficient time & energy

• minerals have uniform, simple structural

states (but allows for zoning, disorder, etc.)

• no kinetic effects

Sunday, September 13, 2009

 Goldschmidt’s
mineralogical phase rule

• consider F = C - P + 2

• normally:

• as C increases, F increases

• as P increases, F decreases ...

Sunday, September 13, 2009

 • as C increases, F increases

• as P increases, F decreases

C=1
C=2
P=1

P=2

Sunday, September 13, 2009

 Goldschmidt’s
mineralogical phase rule

• consider F = C - P + 2; normally:

• as C increases, F increases

• as P increases, F decreases

• GMPR says that for a given rock in equilibrium

at a fixed P & T, generally:

# phases ≤ # components (P ≤ C)

Sunday, September 13, 2009

 Goldschmidt’s
mineralogical phase rule

• Goldschmidt observed that “common” mineral

assemblages occur over wide areas in rocks
of varying composition

• he reasoned, then, that this simpler

assemblage (low #P) is a consequence of
variable (P, T, X) and hence high #C

• it follows, then, that the common situation is to

have C > P, and more F

Sunday, September 13, 2009

 Goldschmidt’s
mineralogical phase rule

• hence, GMPR rule says that for a rock in equilibrium

at fixed P & T, # phases ≤ # components

• in general, rock systems are divariant for P & T (i.e.,

F = 2), so P = C

• but because of natural variation in T-P-Xminerals, it is

also common that F ≥ 2

• if F ≥ 2 and F = C - P + 2, then P ≤ C!

let’s see how this works...

Sunday, September 13, 2009
 if P = C

• this is the standard divariant condition, where

F=2

• you are probably within a mineral zone

• all is good

Sunday, September 13, 2009

 if P ≤ C

• how do we get higher F?

• either higher C or
variable P-T
• if we simplify to easy-to-
understand 3-component
projection, then we can
still maximize C by
allowing for solid solution
• so, consider the system
xyz...

Sunday, September 13, 2009

 3-component projections
what do we
P, T = const. know?

Sunday, September 13, 2009

 3-component projections
the what does the
P, T = const. independent phase rule say?
variable is
composition
(not P or T) for rock (B)

for rock (f)

compositionally
degenerate
for rock (xyz)

Sunday, September 13, 2009

 3-component compatibility diagrams

P, T = limited phases:
C=3 • pure
• 2C ss
• 3C ss
P=1

P=2
P=3

Sunday, September 13, 2009

 3-component compatibility diagrams
for (D),
P, T = limited F=3-3+2=
C=3 2, but because
solid solution
allows for
small system
variation in X,
P=3 variance F
corresponds to
P&T

there is no
compositional
freedom in
phases!!
Sunday, September 13, 2009
 3-component compatibility diagrams

P, T = limited for (f):

F=3-2+2=
C=3 3

variance is in
P, T and phase
P=2 compositions
(ss)

phase
compositions
(f) determined by
system
composition

Sunday, September 13, 2009

 recap 3-component compatibility diagrams

P, T = limited
F=
C=3
F=

F=

Sunday, September 13, 2009

 more phases than components?

if C = 3,
A P = 4? NO!

???

B C

Sunday, September 13, 2009

 if P > C
• F < 2 (you are either on a univariant curve or
at an invariant point)

• as Winter points out, this has lower

probability so more common to be divariant

• disequilibrium? (check phases and textures)

• are your minerals in 1 “system”?

• are some minerals retrograde?

• is there evidence of incomplete reaction?

• did not choose components carefully!

Sunday, September 13, 2009