The Mineralogical Phase Rule

In any chemical system at equilibrium, the following relationship holds:

FDegrees of Freedom = Components - Phases + 2

F equals the minimum number of variables that must

be specified in order to completely define the state of
a system. F is thus the variance of the system, the
number of unknowns.

C equals the number of independent chemical

components needed to define the composition of the
system.
P equals the number of physical phases present in
the system, which include the number of solid
minerals, plus liquid and gas phases, if present.
2 represents the variables pressure and temperature.
Single Component Systems:

SiO2
When a solid consist of 2 coexisting minerals
(phases):

F = C– P+2 = 1 -2 +2 = 1

Such a system is invariant at any given

pressure, and thus a single component solid
phase will melt at 1 unique temperature at
any specified pressure. The boundary
between the 2 phases in P - T space will be a
univariant line with a slope approximated by:

dG = - SdT + VdP = 0

dP/dT = S/ V

This is also true for solid - liquid phase

boundaries because, to a first approximation,
H and So are constant for small changes in
 o

temperature (true for all reactions not

involving a relatively compressible vapour
phase).
Two Component Systems:

Mg2SiO4 – SiO2

Pure forsterite melts at 2163oC at 1 atm. If extra SiO2 is added to the

system, SiO2 will be present only in the melt phase, while
forsterite will remain a pure phase. The temperature at which
forsterite crystallizes is now an inverse function of SiO2 content:

at equilibrium:

GFoOl = GFoLiq and  GFo = 0

GoFo + R × T × Ln(aFoOl) = GoFoLiq + R × T × Ln(aFoLiq)

 GoFo = - R × T × Ln(aFoLiq/aFoOl)

or

 GoFo = - R × T × Ln(1-XSiO2),

aFoOl = 1.0, assume activity (a) = mole fraction X)

and
 GoFo = HoFo – T × SoFo =  HoFo – T × HoFo / TFo

If Ho and So are insensitive to small changes in T & P, then:

 HoFo – T × HoFo / TFo = - R × T × Ln(1-XSiO2)

or

Ln(1-XSiO2) = HoFo / R × (T - TFo) / (T×TFo)

van't Hoff equation for melting point depression
 Two Component Systems:
If a system is comprised of 2 Binary Phase Diagrams
components, then where a solid
and liquid phase coexist:

F =2-2+2=2

Such a system is univariant

at any given pressure, and
thus the melting point of a e
solid will depend on the
proportions of the two
components. In the absence
of extensive solid solution,
the presence of an additional
component will reduce the
melting temperature of No solid-solution
single component solid Between end-members
phases because the
additional component The Eutectic point “e” of a two component system is invariant (F =
typically dissolves 0, if pressure fixed) and is defined by the intersection of two
preferentially in the liquid univariant (F = 1) liquidus curves, originating from the melting
phase. temperatures of the two pure end-member phases.
 Peritectic versus Eutectic
Invariant points

e2

e1

p - oliv + liq opx e1 - liq albite + qtz

e - liq opx + qtz e2 - liq neph + albite

 THE LEVER RULE
X

T3 : Forst / liquid : b / a; Forst / whole = b /(a+b)

For bulk
Composition X T2 : Forst / liquid : c / a; Forst / whole = c /(a+c)

T1 : Forst / Enst : d / a; Forst / whole = d /(a+d)

 Cumulate Rocks versus Rocks
that represent liquids
Liquids
vs
Cumulates

Equilibrium
1557
vs
Fractional

Fractional Crystallization vs Partial Melting

Upon cooling to 1557oC, early crystallized olivine exhibits a reaction relationship with the residual
liquid of composition “p” to form orthopyroxene. Either olivine or melt must disappear before
cooling can continue. During partial melting, orthopyroxene begins to melt incongruently at 1557 oC
to form olivine plus a liquid of composition “p”. Orthopyroxene must be consumed before the
temperature can increase.
The presence of other components in
solid solution at levels that are
insufficient to stabilize a separate phase
destroys the invariant nature of melting.
The temperature and composition of the
first melt are determined by the amount
of the additional component. During
partial melting, these additional
components are typically the first to be
refined out into the melt.
Bianary Systems with extensive Solid
Solution:
Olivine exhibits complete solid solution between the
forsterite (Mg2SiO4) and fayalite (Fe2SiO4) end-members.
In Fe and Mg bearing systems, neither the olivine solid
nor the olivine liquid are pure end-member components:
We now have two van't Hoff equations:
Ln(XFoLiq / XFoOl) = HoFo / R × (T - TFo) / (T × TFo)

Ln(XFaLiq / XFaOl) = HoFa /R × (T - TFa) /(T × TFa)

Because: XFaLig = 1-XFoLiq and XFaOl = 1-XFoOl

Then:
Ln(XFoLiq / XFoOl) = HoFo / R × (T - TFo) / (T × TFo)

Ln(1-XFoLiq / (1-XFoOl)) = HoFa /R × (T - TFa) / (T × TFa)

The choice of any T between TFo and TFa will enable the
calculation of the compositions of the coexisting olivine
and liquid for that T, and thus the solidus and liquidus at
any T. Exactly analogous solid solution relationships can
be developed for the plagioclase series feldspars:
anorthite CaAl2Si2O8 -
albite NaAlSi3O8
 Ternary Systems: Forsterite – Diopside – Anorthite
Liquidus Projection

In order to portray the magmatic phase P = 1 atm

relations of systems with more than two
chemical components, we need to
develop specialized projection schemes.

Three component systems can be

represented on a two dimensional sheet of
paper, if we project only those phase
relationships for which a magmatic liquid
is present.
 Ternary Systems: Forsterite – Diopside - Anorthite

A Liquid of bulk composition X cools to the

P = 1 atm
olivine liquidus surface at 1600°C, at which
point Forsterite begins to crystalize

The liquid composition moves directly

away from Fo, producing a dunite cumulate,
until it reaches the cotectic, at which point
Diopside begins to crystallize with
Forsterite.

X
 Forsterite – Diopside - Anorthite

P = 1 atm

Co-precipitation of Forsterite + Diopside

causes liquid composition to move down
cotectic curve, producing a wehrlite
cumulate.

X
FORSTERITE – DIOPSIDE - ANORTHITE

The liquid composition reaches

the ternary eutectic at 1270°C, at
which point Anorthite begins to
crystallizewith Diopside and
Forsterite, producing a gabbroic
cumulate.

The composition of the liquid

remains at the eutectic point until
all the liquid is consumed.
 Ternary Systems

The composition of the first melt of

an assemblage ABD is that of
invariant eutectic point eABD, while
the composition of the first melt of
assemblage DBC is that of invariant
eutectic point eDBC.

The intersection of a univariant

curve with the Alkemade line
joining the compositions of the
coexisting solid phases defines
a thermal maximum along the
univariant curve.
Ternary Systems
with
Solid Solution:
 Oliv - Cpx - Qtz Liquidus Projection:
The invariant point “p”, at which olivine,
clinopyroxene and orthopyroxene coexist with a
liquid, is a peritectic point because it lies outside
of the compositional volume of the solid phases.
It represents the first melt of any assemblage
consisting of olivine, opx, and cpx (mantle
peridotite) at 1 atm., and is analogous in
composition to a quartz-normative basalt.

Similarly, the univariant curve along which

olivine and orthopyroxene coexist with a liquid is
a reaction curve because the tangent to the curve
at any point cuts the olivine - orthopyroxene
Alkemade line with a negative olivine intercept.

The invariant point “e” is a eutectic and

represents the composition of the first melt of an
assemblage of quartz-diopside-orthopyroxene.
The composition of “e” approximates that of the
Earth’s continental crust.
 Mantle Ocean Continent
crust crust

SiO2 45.2 49.4 60.3

TiO2 0.7 1.4 1.0
Al2O3 3.5 15.4 15.6
MgO 37.5 7.6 3.9
FeO 8.5 10.1 7.2
CaO 3.1 12.5 5.8
Na2O 0.6 2.6 3.2
K2 O 0.1 0.3 2.5
Total 99.2 99.3 99.5
Cations normalized to 100 cations

Si 38.5 46.1 56.4

Ti 0.5 1.0 0.7
Al 3.6 16.9 17.2
Mg 47.6 10.6 5.4
Fe 6.0 7.9 5.6
Ca 2.8 12.5 5.8
Na 0.9 4.7 5.8
K 0.1 0.5 3.0
O 140.2 153.0 161.3

Mineralogy (oxygen units, XFe3+ = 0.10) Oceanic crust - MORB basalt p

Quartz 0.0 0.0 13.0
Feldspar 13.2 57.3 64.3 Continental crust - granite e
Clinopyroxene 6.7 25.7 5.9
Orthopyroxene 18.3 4.1 14.7
Olivine 59.9 9.9 0.0
Oxides 1.8 3.0 2.0
 Liquidus Projections for haplo-basalts
The Basalt Tetrahedron at 1 atm:

The olivine - clinopyroxene -

plagioclase plane is a thermal
divide in the haplo-basalt
system at low pressures and
separates natural magmas into
two fundamentally different
magmatic series. Sub-alkaline
basaltic magmas with
compositions to the Qtz-rich
side of the plane fractionate
towards Qtz-saturated residual
liquids, such as rhyolite.
Alkaline basaltic magmas with
compositions to the Qtz-poor
side of the plane fractionate
towards residual liquids
saturated in a feldspathoid,
such as nepheline phonolite.
Since the dominant mineral in the mantle source of basaltic magmas is olivine, we can achieve a
further simplification by projecting the liquidus of basaltic systems from the perspective of olivine:
Alkaline basalts fall to the Foid-side of the olivine-
clinopyroxene-plagioclase plane (1 atm thermal divide) and
fractionate to foid-saturated residual liquids. Sub-alkaline
basalts fall to the Quartz-side and fractionate towards
quartz-saturated residual liquids.

Alkaline basaltic lavas are volumetrically insignificant (~1%), but strongly enriched in highly
incompatible trace elements profiles compared to sub-alkaline lavas, and low in HREE, Y, & Sc.
These characteristics are generally ascribed to small degrees of partial melting at elevated
pressures, leaving garnet as a phase in the refractory residue.
 The Effect of Pressure

1 atm

Increasing pressure shifts the oliv-

cpx-opx peritectic point towards
less Si-rich compositions. At
approximately 10 kbs this invariant
point moves into the oliv - cpx- opx
compositional volume, and the first
melt of the mantle has an olivine
basalt composition. The invariant
point is still a peritectic point,
however, because of the extensive
solid solution of cpx towards opx.
At pressures exceeding 15-20 kbs,
this invariant point moves outside
the simple olivine - cpx - qtz
system, into the Neph-normative
volume of the basalt tetrahedron.
The first melt of mantle peridotite is
an alkaline olivine basalt at these
high pressures.
Since the dominant mineral in the mantle source of basaltic magmas is olivine, we can achieve a
further simplification by projecting the liquidus of basaltic systems from the perspective of olivine:

Movement of the invariant point

determining the composition of the
first melt with increasing pressure.