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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


Goldschmidts
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


Goldschmidts
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


Goldschmidts
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


Goldschmidts
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!

lets 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