1 Phase Rule PDF

Phase rule
• Gibbs Phase Rule
• Goldschmidt mineralogical phase rule
• implications for chemographic analysis

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

Sunday, September 13, 2009
system
• predict equilibrium relations of phases
• helps to construct phase diagrams

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)

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)
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
degrees of freedom
• F=0 invariant (no change in

system)
• F=1 univariant (equilibrium line)
• F=2
Sunday, September 13, 2009 divariant (stable phase
region)
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?

suppose we have a pelitic rock containing 5 phases

typical of lower amphibolite facies:
St + Grt + Bt + Ms + Qtz
how many components?

or suppose we have a mafic rock containing 5 phases

typical of greenschist metavolcanics:
Act + Chl + Ep + Ab + Qtz
how many components?

“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 Sunday, September 13, 2009
A33B 3C33
B100C0 B0C100
B B50C50 C
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)
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

“modified” phase rule
for a T-X A
diagram,
P = const.
so, only 1
intensive variable
B
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
Goldschmidt’s mineralogical phase rule
• consider F = C - P + 2
• normally:
• as C increases, F increases
• as P increases, F decreases ...

• as P increases, F decreases
C=1
C=2
P=1

P=2
• consider F = C - P + 2; normally:
• as P increases, F decreases
• GMPR says that for a given rock in equilibrium

at a fixed P & T, generally:
# phases ≤ # components (P ≤ C)
• 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
• 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...
if P = C
• this is the standard divariant condition, where

F=2
• you are probably within a mineral zone
•
all is good
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...
3-component projections
what do we
P, T = const. know?

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)
3-component compatibility diagrams
P, T = limited phases:
C=3 • pure
• 2C ss
• 3C ss
P=1
P=2
P=3
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!!
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
recap 3-component compatibility diagrams
P, T = limited
F=
C=3
F=
F=

more phases than components?
if C = 3,
A P = 4? NO!
???
B C
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!

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Phase rule

• Gibbs Phase Rule

• Goldschmidt mineralogical phase rule

• implications for chemographic analysis

• minerals (phases) are reaction products!

• helps to characterize state of the

• predict equilibrium relations of phases

• helps to construct phase diagrams

• F = degrees of freedom (variance)

• C = minimum # components in system

• integers related to # intensive variables (scale

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

• what does Gibbs say?

• variance of the system is the minimum # of

• for each C we add, must specify 1 more

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

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

• if F = 2, can change either P or T

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

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

• if F = 0, cannot change anything and still

• F=0 invariant (no change in

• F=1 univariant (equilibrium line)

F=0 Sunday, September 13, 2009

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

possible components CaO, MgO, SiO2, CO2

CaMgO2, SiO2, CO2

which is best? how do we choose?

suppose we have a pelitic rock containing 5 phases

how many components?

or suppose we have a mafic rock containing 5 phases

Act + Chl + Ep + Ab + Qtz

how many components?

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

so for our greenschist:

Act + Chl + Ep + Ab + Qtz

how can we reduce the ACNFMS components?

end up with 3 components (ACF);

• need to know how many intensive (mass-

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

phase rule becomes F = C - P + 1

• assumptions when applying Gibbs phase rule:

• EQUILIBRIUM!!! sufficient time & energy

• minerals have uniform, simple structural

• as P increases, F decreases ...

Sunday, September 13, 2009

• GMPR says that for a given rock in equilibrium

at a fixed P & T, generally:

• Goldschmidt observed that “common” mineral

• he reasoned, then, that this simpler

variable (P, T, X) and hence high #C

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

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

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

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

also common that F ≥ 2

let’s see how this

• this is the standard divariant condition, where

• how do we get higher F?

allowing for solid solution

Sunday, September 13, 2009

the what does the