Phase Equilibrium

Makaopuhi Lava Lake

Magma samples recovered from various
depths beneath solid crust

From Wright and Okamura, (1977) USGS Prof. Paper, 1004.

 Makaopuhi Lava Lake
Thermocouple attached to sampler to
determine temperature

From Wright and Okamura, (1977) USGS Prof. Paper, 1004.

 Makaopuhi Lava Lake
 Temperature of sample vs. Percent Glass
1250

1200
Temperature oc

1150

1100

1050

1000

950

900
0 10 20 30 40 50 60 70 80 90 100

Percent Glass From Wright and Okamura, (1977)

USGS Prof. Paper, 1004.
 Makaopuhi Lava Lake
Minerals that form during crystallization
Olivine Clinopyroxene Plagioclase Opaque
1250

Liquidus
1200

note olivine 1150

Temperature oC

decreases
below 1100
1175oC Melt
Crust
1050

1000

Solidus
950
0 10 0 10 20 30 40 50 0 10 20 30 40 50 0 10
From Wright and Okamura, (1977) USGS Prof. Paper, 1004.
 Makaopuhi Lava Lake
Mineral composition during crystallization
100

Olivine Augite Plagioclase

90
Weight % Glass

80

70

60

50
.9 .8 .7 .9 .8 .7 .6 80 70 60
Mg / (Mg + Fe) Mg / (Mg + Fe) An

From Wright and Okamura, (1977) USGS Prof. Paper, 1004.

 Crystallization Behavior of Melts
1. Cooling melts crystallize from a liquid to a solid over a range of
temperatures (and pressures)
 Crystallization Behavior of Melts
1. Cooling melts crystallize from a liquid to a solid over a range of
temperatures (and pressures)
2. Several minerals crystallize over this T range, and the number of
minerals increases as T decreases
 Crystallization Behavior of Melts
1. Cooling melts crystallize from a liquid to a solid over a range of
temperatures (and pressures)
2. Several minerals crystallize over this T range, and the number of
minerals increases as T decreases
3. The minerals that form do so sequentially, with consideral overlap
 Crystallization Behavior of Melts
1. Cooling melts crystallize from a liquid to a solid over a range of
temperatures (and pressures)
2. Several minerals crystallize over this T range, and the number of
minerals increases as T decreases
3. The minerals that form do so sequentially, with consideral overlap
4. Minerals that involve solid solution change composition as cooling
progresses
 Crystallization Behavior of Melts
1. Cooling melts crystallize from a liquid to a solid over a range of
temperatures (and pressures)
2. Several minerals crystallize over this T range, and the number of
minerals increases as T decreases
3. The minerals that form do so sequentially, with consideral overlap
4. Minerals that involve solid solution change composition as cooling
progresses
5. The melt composition also changes during crystallization
 Crystallization Behavior of Melts
1. Cooling melts crystallize from a liquid to a solid over a range of
temperatures (and pressures)
2. Several minerals crystallize over this T range, and the number of
minerals increases as T decreases
3. The minerals that form do so sequentially, with consideral overlap
4. Minerals that involve solid solution change composition as cooling
progresses
5. The melt composition also changes during crystallization
6. The minerals that crystallize (as well as the sequence) depend on T
and X of the melt
 Crystallization Behavior of Melts
1. Cooling melts crystallize from a liquid to a solid over a range of
temperatures (and pressures)
2. Several minerals crystallize over this T range, and the number of
minerals increases as T decreases
3. The minerals that form do so sequentially, with consideral overlap
4. Minerals that involve solid solution change composition as cooling
progresses
5. The melt composition also changes during crystallization
6. The minerals that crystallize (as well as the sequence) depend on T
and X of the melt
7. Pressure can affect the types of minerals that form and the
sequence
 Crystallization Behavior of Melts
1. Cooling melts crystallize from a liquid to a solid over a range of
temperatures (and pressures)
2. Several minerals crystallize over this T range, and the number of
minerals increases as T decreases
3. The minerals that form do so sequentially, with consideral overlap
4. Minerals that involve solid solution change composition as cooling
progresses
5. The melt composition also changes during crystallization
6. The minerals that crystallize (as well as the sequence) depend on T
and X of the melt
7. Pressure can affect the types of minerals that form and the
sequence
8. The nature and pressure of the volatiles can also affect the minerals
and their sequence
 The Phase Rule
F=C-+2
F = # degrees of freedom
The number of intensive parameters that must be specified in
order to completely determine the system
 The Phase Rule
F=C-+2
F = # degrees of freedom
The number of intensive parameters that must be specified in
order to completely determine the system
 = # of phases
phases are mechanically separable constituents
 The Phase Rule
F=C-+2
F = # degrees of freedom
The number of intensive parameters that must be specified in
order to completely determine the system
 = # of phases
phases are mechanically separable constituents
C = minimum # of components (chemical constituents that must
be specified in order to define all phases)
 The Phase Rule
F=C-+2
F = # degrees of freedom
The number of intensive parameters that must be specified in
order to completely determine the system
 = # of phases
phases are mechanically separable constituents
C = minimum # of components (chemical constituents
that must be specified in order to define all
phases)
2 = 2 intensive parameters
Usually = temperature and pressure for us geologists
High Pressure Experimental Furnace
Cross section: sample in red

the sample!
sample
800 Ton Ram

Carbide
Pressure
Vessle

SAMPLE

Talc

Talc
Graphite Furnace

1 cm Furnace
Assembly

After Boyd and England (1960), J. Geophys. Res., 65, 741-748. AGU
 1 - C Systems
1. The system SiO2
Stishovite
10
After Swamy and
Saxena (1994), J.
8 Geophys. Res., 99,
Pressure (GPa)

11,787-11,794. AGU

6
Coesite

- quartz
2
- quartz Liquid
Cristobalite
Tridymite

600 1000 1400 1800 2200 2600

Temperature C o
 1 - C Systems
2. The system H2O
Ice VII
Ice VI
3 Ice V
Ice II Ice III
2 critical point
log Pressure (MPa)

1 374oC
Liquid & 21.8 MPa
0
Ice I
-1 1 atm

-2 Vapor

-3 After Bridgman
0.01oC & 0.0006 MPa
(1911, Proc. Amer.
-4 Acad. Arts and Sci.,
5, 441-513; 1936, J.
Chem. Phys., 3, 597-
-100 0 100 200 300 400 605; 1937, J. Chem.
Temperature oC Phys., 5, 964-966.
 2 - C Systems
A. Systems with Complete Solid Solution
1. Plagioclase (Ab-An, NaAlSi3O8 - CaAl2Si2O8)
1557
i qu idus
L
1500 Isobaric T-X phase diagram
Liquid at atmospheric pressure
(after Bowen 1913, Amer. J.
Sci., 35, 577-599).
1400 Plagioclase
o
T C
plus
1300
Liquid
Plagioclase
u
s

1200 ol id
S

1118
1100

Ab 20 40 60 80 An
Weight % An
Bulk composition a = An60
= 60 g An + 40 g Ab
XAn = 60/(60+40) = 0.60
a
1557

1500
Liquid

1400 Plagioclase
o
T C
plus
1300
Liquid
Plagioclase
1200

1118
1100

Ab 20 40 60 80 An

Weight % An (100 XAn)

 F=2

1. Must specify 2 independent intensive

variables in order to completely determine
the system
= a divariant situation
same as:

2. Can vary 2 intensive variables independently

without changing , the number of phases
 liq liq
Must specify T and X An or can vary these without
changing the number of phases

a
1557

1500
Liquid b

1400 Plagioclase
o
T C
plus
1300
Liquid
Plagioclase
1200

1118
1100

Ab 20 40 60 80 An

Weight % An
Get new phase joining liquid:
plag
first crystals of plagioclase: X An= 0.87 (point c)

F=?
a
1557

1500
Liquid b c

1400 Plagioclase
o
T C +
1300
Liquid
Plagioclase
1200

1118
1100

Ab 20 40 60 80 An
 F = 2 - 2 + 1 = 1 (“univariant”)
Must specify only one variable from among:
liq liq plag plag
T X An X Ab X An X Ab (P constant)
liq plag
X An and X An a
are dependent upon T 1557

1500
Liquid b c
The slope of the solidus
and liquidus are the 1400 Plagioclase
expressions of this o
relationship T C +
1300
Liquid
Plagioclase
1200

1118
1100

Ab 20 40 60 80 An
 At 1450oC, liquid d and plagioclase f coexist at equilibrium

a
1557
A continuous reaction 1500
b c
of the type: Liquid d f

1400 Plagioclase
liquidA + solidB = o
T C +
liquidC + solidD 1300
Liquid
Plagioclase
1200

1118
1100

Ab 20 40 60 80 An
 The lever principle:

Amount of liquid ef
=
Amount of solid de

where d = the liquid composition, f = the solid composition

and e = the bulk composition

d e f

liquidus
de ef

solidus
When Xplag  h, then Xplag = Xbulk and, according to the
lever principle, the amount of liquid  0

Thus g is the composition of the last liquid to crystallize at

1340oC for bulk X = 0.60

a
1557

1500
b
Liquid c
d
f
1400 Plagioclase
o g
T C h
plus
1300
Liquid
Plagioclase
1200
i

1118
1100

Ab 20 40 60 80 An

Weight % An
 plag
Final plagioclase to form is j when X An = 0.60

Now = 1 so F = 2 - 1 + 1 = 2

a
1557

1500
b
Liquid c
d
f
1400 Plagioclase
o g
T C h
plus
1300
Liquid
Plagioclase
j
1200
i

1118
1100

Ab 20 40 60 80 An

Weight % An
 Note the following:
1. The melt crystallized over a T range of 135oC *
4. The composition of the liquid changed from b to g
5. The composition of the solid changed from c to h

a
1557

1500
b
Liquid c Numbers refer
d
f to the “behavior
1400 Plagioclase of melts” observations
o g
T C
plus h
1300
Liquid
Plagioclase * The actual temperatures
and the range depend on the
1200
i bulk composition

1118
1100

Ab 20 40 60 80 An

Weight % An
 Equilibrium melting is exactly the opposite

Heat An60 and the first melt is g at An20 and 1340oC

Continue heating: both melt and plagioclase change X

Last plagioclase to melt is c (An87) at 1475oC

a
1557

1500
b
Liquid c
d
f
1400 Plagioclase
o g
T C
plus h
1300
Liquid
Plagioclase
1200
i

1118
1100

Ab 20 40 60 80 An

Weight % An
Fractional crystallization:
Remove crystals as they form so they can’t
undergo a continuous reaction with the melt

At any T Xbulk = Xliq due to the removal of the crystals

a
1557

1500
b
Liquid c
d
f
1400 Plagioclase
o g
T C h
plus
1300
Liquid
Plagioclase
1200
i

1118
1100

Ab 20 40 60 80 An
Weight % An
Partial Melting:
Remove first melt as forms
Melt Xbulk = 0.60 first liquid = g
remove and cool bulk = g  final plagioclase = i

a
1557

1500
b
Liquid c
d
f
1400 Plagioclase
o g
T C h
plus
1300
Liquid
Plagioclase
1200
i
i
1118
1100

Ab 20 40 60 80 An
Weight % An
Note the difference between the two types of fields

The blue fields are one phase fields

Any point in these fields represents a true Liquid

phase composition
Plagioclase

plus

The blank field is a two phase field Liquid

Any point in this field represents a bulk Plagioclase

composition composed of two phases at the
edge of the blue fields and connected by a
horizontal tie-line
2. The Olivine System
Fo - Fa (Mg2SiO4 - Fe2SiO4)
also a solid-solution series

Isobaric T-X phase

1900 1890 diagram at atmospheric
Liquid a pressure (After Bowen
and Shairer (1932),
1700 Amer. J. Sci. 5th Ser.,
b
c 24, 177-213.
Olivine
T oC plus

d Liquid
1500

1300
Olivine
1205

Fa 20 40 60 80 Fo

Wt.% Forsterite
 2-C Eutectic Systems
Example: Diopside - Anorthite
No solid solution

1600
s 1553
Liquid Liqu
idu
1500

T oC
1400
1392 Anorthite + Liquid
1300 Diopside + Liquid
1274

1200 Diopside + Anorthite

Di 20 40 60 80 An
Wt.% Anorthite

Isobaric T-X phase diagram at atmospheric pressure (After Bowen (1915), Amer. J. Sci. 40, 161-185.
 Cool composition a:
bulk composition = An70

1600
a idus
1553
Liquid Liqu
1500

T oC
1400
1392 Anorthite + Liquid
1300 Diopside + Liquid
1274

1200 Diopside + Anorthite

Di 20 40 60 80 An
Wt.% Anorthite
 Cool to 1455oC (point b)

1600
a idus
1553
Liquid Liqu
1500
b c
T oC
1400
1392 Anorthite + Liquid
1300 Diopside + Liquid
1274

1200 Diopside + Anorthite

Di 20 40 60 80 An
Wt.% Anorthite
 Continue cooling as Xliq varies along the liquidus
 Continuous reaction: liqA  anorthite + liqB

1600
a s 1553
Liquid Liqu
idu
1500
b c
T oC
1400
1392 Anorthite + Liquid
1300 Diopside + Liquid
1274

1200 Diopside + Anorthite

Di 20 40 60 80 An
Wt.% Anorthite
at 1274oC  = 3 so F = 2 - 3 + 1 = 0 invariant
 (P) T and the composition of all phases is fixed

 Must remain at 1274oC as a discontinuous

reaction proceeds until a phase is lost

1600
a idus
1553
Liquid Liqu
1500
b c
T oC
1400
1392 Anorthite + Liquid
1300 Diopside + Liquid d
g h 1274

1200 Diopside + Anorthite

Di 20 40 60 80 An
Wt.% Anorthite
 Discontinuous Reaction: all at a single T
 Use geometry to determine

1600
a idus
1553
Liquid Liqu
1500

T oC
1400
1392 Anorthite + Liquid
1300 Diopside + Liquid d
g h 1274

1200 Diopside + Anorthite

Di 20 40 60 80 An
 Left of the eutectic get a similar situation

1600
1553
Liquid idus
Liqu
1500

T oC
1400
1392
f e Anorthite + Liquid
1300 Diopside + Liquid d
g 1274
h
1200 Diopside + Anorthite

Di 20 40 60 80 An
Wt.% Anorthite
 Note the following:
1. The melt crystallizes over a T range up to ~280oC
2. A sequence of minerals forms over this interval
#s are listed
points in text - And the number of minerals increases as T drops
6. The minerals that crystallize depend upon T
- The sequence changes with the bulk composition

1600
a idus
1553
Liquid Liqu
1500
b c
T oC
1400
1392
f e Anorthite + Liquid
1300 Diopside + Liquid d
g 1274
h
1200 Diopside + Anorthite

Di 20 40 60 80 An
Wt.% Anorthite
 Augite forms before plagioclase

Gabbro of
the
Stillwater
Complex,
Montana

This forms on the left side of the eutectic

 Plagioclase forms before augite
Ophitic texture

Diabase dike

This forms on the right side of the eutectic

 Also note:
• The last melt to crystallize in any binary eutectic
mixture is the eutectic composition
• Equilibrium melting is the opposite of equilibrium
crystallization
• Thus the first melt of any mixture of Di and An
must be the eutectic composition as well

1600
a idus
1553
Liquid Liqu
1500
b c
T oC
1400
1392
f e Anorthite + Liquid
1300 Diopside + Liquid d
g 1274
h
1200 Diopside + Anorthite

Di 20 40 60 80 An
Wt.% Anorthite
Fractional crystallization:

1600
1553
Liquid idus
Liqu
1500

T oC
1400
1392 Anorthite + Liquid
1300 Diopside + Liquid
1274

1200 Diopside + Anorthite

Di 20 40 60 80 An
Wt.% Anorthite
 Partial Melting:

1600
1553
Liquid idus
Liqu
1500

T oC
1400
1392 Anorthite + Liquid
1300 Diopside + Liquid d
1274

1200 Diopside + Anorthite

Di 20 40 60 80 An
Wt.% Anorthite
 C. Binary Peritectic Systems
Three phases enstatite = forsterite + SiO2
2000 Liquid

a
1800 Two Liquids Figure 6-12. Isobaric
T-X phase diagram of
1713 the system Fo-Silica
T oC 1695
Liquid + at 0.1 MPa. After
Forsterite b Bowen and Anderson
1600 Cristobalite + Liquid (1914) and Grieg
1557 (1927). Amer. J. Sci.
1543
e
Enstatite + Cristobalite
Forsterite 1470
+ Enstatite Enstatite + Tridymite
1400
20 40 60 80 SiO2
Mg2SiO4 MgSiO2
Forsterite Enstatite Wt.% X2
 C. Binary Peritectic Systems
2000 Liquid

a
1800 Two Liquids

1713
T oC 1695
Liquid +
Forsterite b
1600 Cristobalite + Liquid
1557
d c
1543
e
Enstatite + Cristobalite
Forsterite 1470
+ Enstatite Enstatite + Tridymite
1400
20 40 60 80 SiO2
Mg2SiO4 MgSiO2
Forsterite Enstatite Wt.% X2
 2000 Liquid

1800 Two Liquids

h 1713
T oC 1695
Liquid +
Forsterite
1600 Cristobalite + Liquid
1557 i 1543
d c Enstatite + Cristobalite
Forsterite 1470
+ Enstatite Enstatite + Tridymite
1400
20 40 60 80 SiO2
Mg2SiO4 MgSiO2
Forsterite Enstatite
Wt.% X2
 i = “peritectic” point
1557oC have colinear Fo-En-liq
 geometry indicates a reaction: Fo + liq = En

 consumes olivine (and liquid)  resorbed textures

When is the reaction finished?

im
1557
k
d
c

Fo En
Bulk X
 x
k i
y m
1557 1543
d Cr
c
bulk X
Fo En
Incongruent Melting of Enstatite
 Melt of En does not  melt of same composition
 Rather En  Fo + Liq i at the peritectic

Partial Melting of Fo + En (harzburgite) mantle

 En + Fo also  firsl liq = i
 Remove i and cool i
 Result = ?
1557 1543
d c
Cr

bulk X
Fo En
Cool X = n Immiscible Liquids
 At 1960oC hit solvus

exsolution
 2 liquids o and p n
Liquid
=2 F=1 2000
o p
both liquids follow solvus
1800 Two Liquids
At 1695 C get Crst also
o
1713
T oC 1695
Liquid +
Reaction? Forsterite
1600 Cristobalite + Liquid
1557 1543
c Enstatite + Cristobalite
1695 Crst
Forsterite 1470
+ Enstatite Enstatite + Tridymite
Silica-rich 1400
Mafic-rich 20 40 60 80 SiO2
liquid liquid Mg2SiO4 MgSiO2
Wt.% X2
 Pressure Effects
Different phases have different compressibilities
Thus P will change Gibbs Free Energy differentially
 Raises melting point

 Shift eutectic position (and thus X of first melt, etc.)

Liquid High Quartz + Liquid 1.2 GPa

Forsterite
1700 + Liquid
Enstatite + High Quartz
Figure 6-15. The
T oC Forsterite Enstatite + Liquid
system Fo-SiO2 at
+ Enstatite
atmospheric pressure
and 1.2 GPa. After
1600
Forsterite Liquid 0.0001 GPa Bowen and Schairer
+ Liquid Cristobalite + Liquid
(1935), Am. J. Sci.,
Chen and Presnall
Forsterite Enstatite + LiquidEnstatite + Cristobalite (1975) Am. Min.
1500 + Enstatite

Mg2SiO4 MgSiO3 X (wt.%) SiO2

 D. Solid Solution with Eutectic:
Ab-Or (the alkali feldspars)
Eutectic
liquidus
minimum

Figure 6-16. T-X

phase diagram of the
system albite-
orthoclase at 0.2 GPa
H2O pressure. After
Bowen and Tuttle
(1950). J. Geology.
 Effect of PH O on Ab-Or
2

Figure 6-17. The Albite-K-feldspar system at various H2O pressures. (a) and (b) after
Bowen and Tuttle (1950), J. Geol, (c) after Morse (1970) J. Petrol.