Phase Equilibrium

System
Tim Dosen Geokimia
FTG UNPAD
2016
 Ionic Substitution Review
GOLDSMITH’S RULE

1. The ions of one element can extensively replace those of

another in ionic crystals if their radii differ by less than
approximately 15%.
2. Ions whose charges differ by one unit substitute readily for one
another provided electrical neutrality of the crystal is
maintained. If the charges differ by more than one unit,
substitution is generally slight.
3. When two different ions can occupy a particular position in a
crystal lattice, the ion with the higher ionic potential forms a
stronger bond with the anions surrounding the site.
RINGWOOD’S MODIFICATION OF

GOLDSCHMIDT’S RULES

4. Substitutions may be limited, even when the size

and charge criteria are satisfied, when the
competing ions have different electronegativities
and form bonds of different ionic character.
This rule was proposed in 1955 to explain
discrepancies with respect to the first three
Goldschmidt rules.
For example, Na+ and Cu+ have the same radius
and charge, but do not substitute for one another.
 Coupled Substitution

• When the ion of a major element in a mineral is replaced

with something having a different charge, the charge
imbalance created must be neutralized by addition of a
counter ion
• Example ! addition of Al3+ in a silicate structure
(replacing Si4+) requires addition of a Na+ or K+ (Key to
understanding feldspar chemistry…). When 2 Al3+ are
added for Si4+, this then can be balanced by adding a
Ca2+ ion
 SOLID SOLUTION

• Occurs when, in a crystalline solid, one element

substitutes for another.
• For example, a garnet may have the composition:
(Mg1.7Fe0.9Mn0.2Ca0.2)Al2Si3O12.
• The garnet is a solid solution of the following end
member components:
Pyrope - Mg3Al2Si3O12; Spessartine - Mn3Al2Si3O12;
Almandine - Fe3Al2Si3O12; and Grossular - Ca3Al2Si3O12.
 CHEMICAL FRACTIONATION
& PARTITION COEFFICIENT
Chemical fractionation:
The uneven distribution of an ion between two
competing (equilibrium) phases
Exchange equilibrium
Exchange equilibriumofofaacomponent i
component i between
between two phases
two phases (solid
(solid and liquid)
and liquid)
i (liquid) = i (solid)
a isolid γi X isolid
KD = a iliquid
= γi X iliquid
K = equilibrium constant
a = concentration
For dilute solutions can substitute D for K :
 For dilute solutions can substitute D f

CS
D=
CL

Where C S = the concentration of

Where Cs is the concentration of some elements in solid
some e
phase the solid phase
• incompatible elements are concentrated in
the melt:
(K or D) « 1
• compatible elements are concentrated in the
solid:

K or D » 1

where D is the partition coefficient for any given trace element

between phases; D is a constant for dilute concentrations of
elements
 INCOMPATIBLE VS. COMPATIBLE TRACE
ELEMENTS

Incompatible elements: Elements that are too large and/or too

highly charged to fit easily into common rock-forming minerals
that crystallize from melts. These elements become
concentrated in melts.
Large-ion lithophile elements (LIL’s): Incompatible owing to
large size, e.g., Rb+, Cs+, Sr2+, Ba2+, (K+).
High-field strength elements (HFSE’s): Incompatible owing to
high charge, e.g., Zr4+, Hf 4+, Ta4+, Nb5+, Th4+, U4+, Mo6+, W6+,
etc.
Compatible elements: Elements that fit easily into rock-forming
minerals, and may in fact be preferred, e.g., Cr, V, Ni, Co, Ti,
etc.
 Melts
• Liquid composed of predominantly silica and oxygen.
Like water, other ions impart greater conductivity to
the solution
• Si and O is polymerized in the liquid to differing
degrees – how ‘rigid’ this network may be is uncertain
• Viscosity of the liquid ! increases with increased
silica content, i.e. it has less resistance to flow with
more SiO2
• if there is H2O , it is magma ! 2-6% typically – H2O
decreases the overall melting T of a magma
 BOWEN’S
REACTION
SERIES
 Phase diagram
• Need to represent how mineral reactions at equilibrium vary
with P and T
 The Phase Rule
F=C-φ+2
F = # degrees of freedom
The number of intensive parameters that must be specified in
order to completely determine the system
φ = # 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
1 - C Systems
1. The system SiO2

Fig. 6.6. After Swamy and

Saxena (1994), J. Geophys.
Res., 99, 11,787-11,794. AGU
1 - C Systems
2. The system H2O

Fig. 6.7. After Bridgman

(1911) Proc. Amer. Acad. Arts
and Sci., 5, 441-513; (1936) J.
Chem. Phys., 3, 597-605;
(1937) J. Chem. Phys., 5, 964-
966.
 2 - C Systems
A. Systems with Complete Solid Solution
1. Plagioclase (Ab-An, NaAlSi3O8 - CaAl2Si2O8)

Fig. 6.8. Isobaric T-X phase

diagram at atmospheric
pressure. After Bowen (1913)
Amer. J. Sci., 35, 577-599.
 phase diagram
The following relates to the behaviour of
plagioclase under complete equilibrium
conditions during crystallization.


The conventions for the phase diagram
include the following:

1. Two components: high temperature

CaAl2Si2O8 (anorthite) and low
temperature NaAl2Si2O8 (albite) plotted
along the horizontal axis.

Low temperature, sodic plagioclase (Albite)

is on the left; high temperature calcic
plagioclase (anorthite) is on the right.



Composition is in % anorthite. A 30%
anorthite melt has 30% calcium and 70%
sodium.

 phase diagram
As we expect from Bowen's reaction series,
Ca-rich anorthite crystallizes at a much
higher temperature than Na-rich albite.

2. One variable - Temperature is plotted along

the vertical axis.

3. Pressure is held constant at 1 atmosphere.

4. Two phases: crystal and liquid melt. The

diagram is divided into three fields, ‘all
liquid’, ‘liquid + crystal’, ‘all crystal’.

The liquidus line separates the ‘all liquid’

phase from the ‘liquid + crystal’ phase. The
solidus line separates the ‘liquid + crystal’
phase from the ‘all crystal’ phase. 

 phase diagram


The solidus and liquidus lines are
experimental; they have been
determined by melting and cooling many
melts at different anothite percentages.
5. Complete miscibility (mixing) occurs in
both liquid (magma) and crystal phases.

The assumptions are:

The system remains in equilibrium
throughout its history so that all
reactions can take place and everything
can come to stability.

Early formed crystals completely react

back with the melt as temperature falls
to produce the feldspar most stable at
that temperature.

phase diagram 1

USING THE GRAPH

(numbers on phase diagram
correspond with numbers below)
2 3
1. As an example, take a hot melt
(over 1500 degrees) of 30% anorthite
(70% Albite).
2. Cool melt to liquidus line. First
crystal begins to form at about 1380o.
3. To determine the composition of
the first crystal move horizontally
across to the solidus line. The solidus
always indicates crystal composition.
4. Then drop from the solidus
straight down to the bottom scale.
The first crystal is 72% anorthite
(28% Albite). The diagram is always 4
read in this manner, ‘down-across-
down’ regardless of starting
composition.
phase diagram 1

As the temperature drops and

2 3
crystallization continues, Ca is
removed from the melt faster than
Na. (a 30% anorthite melt yields a
first crystal with a composition
ratio of 72% Ca:28% Na)
Thus as crystallization proceeds the
Na concentration of the melt
increases and Ca gets lower.
 4
phase diagram 1

5. Thus as the temperature lowers the

composition of the melt migrates down
the liquidus line. But at the same time the
composition of the crystals forming are 2 3
moving down the solidus line (that is,
decreasing in Ca.)

This is because the system cools slowly

enough to stay in equilibrium at all times. 5 5

The earlier formed crystals react with

the melt, exchanging Ca for Na, to come
to a composition in equilibrium with the
temperature at the moment.

The composition of the melt and crystals 4

move down in tandem, exactly opposite
each other along a horizontal line.

 phase diagram 1

Thus at any temperature the

combined composition of both the
crystals and melt must equal the
original composition of the melt. 2 3
QUESTIONS:
(i) What will be the composition of
the last drop of melt?
(ii) At what temperature will it 5
crystallise? 5
(iii) What will be the composition of
the last crystal from the melt?
ANSWERS
(i) The last drop will be about 3%
anorthite (97% albite)
(ii) At a temperature of about 1185o. 4
(iii) The last crystal will be about 30%
anorthite.
phase diagram 1

EXPLANATION

If the system stays in equilibrium

at all times the final composition
must end up where we started, 2 3
30% anorthite:70% albite.

So, find the composition of the

melt on the liquidus line which is 5 5
opposite where the 30% line
crosses the solidus line.

This is the composition of the last

drop of melt.
4
The temperature is read where
this line intersects the
temperature scale.
 Zoned crystals
But what if crystallisation of the melt
takes place too rapidly and the early
Ca-rich
formed crystals do not have time to
plagioclase
react back fully with the melt?
The early Ca-rich crystal will only partly
react back with the melt and leave a
crystal remnant behind. It is around this
that a later crystal will grow which in
turn will become surrounded by later
forming crystals as temperature falls.
In this way a ZONED CRYSTAL is
formed with a central core of Ca–rich
anorthite surrounded by layers (zones)
Na-rich of increasingly Na-rich plagioclase.
5cm plagioclase

The feldspar crystal illustrated is a phenocryst as it is surrounded by a finer grained groundmass of un-zoned plagioclase
crystals that have cooled too quickly to form larger crystals - PORPHYRYTIC texture
 2-C Eutectic Systems

Fig. 6.11. Isobaric T-X phase diagram at atmospheric pressure. After Bowen (1915), Amer. J. Sci. 40, 161-185.
 More than 1 crystal can precipitate from a melt –
different crystals, different stabilities…
2+ minerals that do not share equilibrium in a melt are
immiscible (opposite of a solid solution)
Liquidus ! Line describing equilibrium between melt and
one mineral at equilibrium
Solidus ! Line describing equilibrium with melt and solid
Eutectic ! point of composition where melt and solid can
coexist at equilibrium
Solidus
Eutectic
Diopside is a pyroxene
Anorthite is a feldspar
Liquidus
 Melt at composition X cools to point Y where anorthite
(NOT diopside at all) crystallizes, the melt becomes
more diopside rich to point C, precipitating more
anorthite with the melt becoming more diopside-rich
This continues and the melt continues to cool and shift
composition until it reaches the eutectic when diopside
A
can start forming
B
At eutectic, diopside S1
C
AND anorhtite crystals S2

precipitate
Lever Rule !
diopside/anorthite
Z
(42%/58%) crystallize
until last of melt
precipitates and the
rock composition is Z
Melting ! when heated to eutectic, the rock would
melt such that all the heat goes towards heat of
fusion of diopside and anorthite, melts so that 42%
diopside / 58% anorthite…

When diopside gone, temperature can increase and

rest of anorthite can melt (along liquidus)
Note the following:
o
1. The melt crystallizes over a T range up to ~280 C
2. A sequence of minerals forms over this interval
- And the number of minerals increases as T drops
6. The minerals that crystallize depend upon T
- The sequence changes with the bulk composition
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
 TUGAS-DISKUSI
buat masing-masing 2 kelompok dalam 1 kelas

diskusikan tentang mineral yang terlibat dalam “deret bowen”. lihat perubahan unsur-unsur dalam mineral
tersebut

kenapa unsur Ca pada deret “continuos” series bisa digantikan oleh Na seiring dengan turunnya suhu
magma?

bandingkan juga untuk mineral-mineral pada deret “discontinous”

kenapa pada akhirnya mineral-mineral ini pada suhu yang lebih rendah lagi bisa menghasilkan mineral
yang sama?

lihat sifat-sifat kimia dan fisika unsur (lihat potensial ionisasi, elektronegativitas, valensi, dll)

hubungkan dengan klasifikasi unsur dalam “Goldsmiths’s geochemical periodic table”

apakah ada hubungannya dengan aturan goldsmith untuk substitusi ionik dalam pembentukan mineral?

bagaimana ikatan yang terbentuk antara unsur-unsur dalam mineral ini? apakah ada pengaruhnya
terhadap mineral yang terbentuk?
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