Pyroxene Mineral Formula

Orthopyroxene 91145
Col 1
Col 2
Wt% Ox Mol Wt
Mol Ox
SiO2
52.09
60.09
0.8669

Col 3
Col 4
Col 5
At Ox # anions Cations
1.7337
3.919
1.96

IV
1.96

VI

TiO2

0.12

79.9

0.0015

0.0030

0.007

0.00

0.00

Al2O3

1.63

101.94

0.0160

0.0480

0.109

0.07

0.04

27.06
0.66
19.11
0.51
0.05

159.7
71.85
70.94
40.32
56.08
61.98

0.0000
0.3766
0.0093
0.4740
0.0091
0.0008

0.0000
0.3766
0.0093
0.4740
0.0091
0.0008

0.000
0.858
0.021
1.079
0.021
0.002

0.00
0.86
0.02
1.08
0.02
0.00

0.00
0.86
0.02
1.08
0.02
0.00

94.2

0.0000

0.0000

0.000

0.00

0.00

Fe2O3
FeO
MnO
MgO
CaO
Na2O
K2O

0.04

Paulings Rules
for Ionic Crystals
Deal with the energy state of the crystal structure
1st Rule
The cation-anion distance = radii
Can use RC/RA to determine the coordination number of
the cation
This is our previous discussion on coordination polyhedra

Paulings Rules
for Ionic Crystals
2nd Rule
First note that the strength of an electrostatic bond
= valence / CN
Na+ in NaCl is in VI coordination
For Na+ the strength =
+1 divided by 6 = + 1/6

Cl

Cl

Cl
Cl

Na

Paulings Rules
for Ionic Crystals
2nd Rule: the electrostatic valence principle
An ionic structure will be stable to
the extent that the sum of the
strengths of electrostatic bonds that
reach an anion from adjacent
cations = the charge of that anion
6 ( + 1/6 ) = +1 (sum from Nas)
charge of Cl = -1
These charges are equal in magnitude so
the structure is stable

Na

+ 1/6

+ 1/6
Na
+

Na

/6

Cl
Na

+ 1/6

Paulings Rules
3rd Rule:
The sharing of edges, and particularly of faces, of
adjacent polyhedra tend to decrease the
stability of an ionic structure

Fig 9-18 of Bloss, Crystallography

and Crystal Chemistry. MSA

Paulings Rules
4th Rule:
In a crystal with different cations, those of high valence
and small CN tend not to share polyhedral elements
An extension of Rule 3

Si4+ in IV coordination is very unlikely to share edges or faces

Paulings Rules
5th Rule:
The number of different kinds of constituents in a crystal
tends to be small
Using the analogy of CP oxygens this rule states that the
number of types of interstitial sites that are filled in a
regular and periodic array tends to be small
4 common types of cation sites in such an array:

XII (large cations replace O positions)

VI
IV
III (small and uncommon cations)

VIII is not CP

Paulings Rules
5th Rule:
VI and IV sites in HCP array of oxygen anions
(not all will be occupied due to charge balance)

HCP
Cant fill
both
(share face)

IV sites

VI sites

Paulings Rules
5th Rule:
VI and IV sites in CCP array of oxygen anions
(not all will be occupied due to charge balance)

CCP

IV sites

VI sites

Paulings Rules
5th Rule:
The spinel

2+ IV

3 VI
2

( A ) ( B ) O 4 structure at various angles

Note
CCP abcabc layers
of Oxygens
White VI sites
Blue IV sites

Paulings Rules
5th Rule:
The spinel

2+ IV

3 VI
2

( A ) ( B ) O 4 structure at various angles

Polyhedral model
White VI sites
Blue IV sites

Paulings Rules
5th Rule:
The spinel

2+ IV

3 VI
2

( A ) ( B ) O 4 structure at various angles

Now see lines of VI and
IV sites
Not all are occupied
1/8 of IV sites
1/2 of VI sites

Paulings Rules
5th Rule:
The spinel

2+ IV

3 VI
2

( A ) ( B ) O 4 structure at various angles

Rotating to where cation
sites almost line up

Paulings Rules
5th Rule:
The spinel

2+ IV

3 VI
2

( A ) ( B ) O 4 structure at various angles

This orientation is
looking down (010)
It makes an excellent
projection, since
atoms all stack up on
top of one another
toward you
The order becomes
apparent
But you lose the third
dimension

Two miscellaneous structural concepts

Isostructuralism
Minerals with the same structure, but different compositions
CaF2 - BaCl2

Antistructuralism
Minerals with the same struture, but one has cations where the
other has anions and vice-versa
CaF2 - Na2O

Polymorphism
Different structural forms for compounds of the same
composition different minerals

The common form is - or lowquartz, but there are others

that become stable under
different conditions, including
- or high-quartz, tridymite,
cristobalite, coesite, and
stishovite

Stishovite
10

Pressure (GPa)

The compound SiO2 has several

different structural forms, or
polymorphs

Coesite

- quartz
- quartz

600

The SiO2 phase diagram

Liquid

Cristobalite
Tridymite
1000

1400

1800

2200

Temperature C
o

After Swamy and Saxena (1994) J.

Geophys. Res., 99, 11,787-11,794.

2600

Polymorphism
1. Displacive polymorphism
quartz at 573oC at
atmospheric pressure
Pressure (GPa)

Coesite

High-Quartz

Low-Quartz

500

1000

Temperature

Polymorphism
1. Displacive polymorphism

High

Note: higher T higher

symmetry due to more
thermal energy (may twin
as lower T)
Transition involves small
adjustments and no
breaking of bonds

P6222
Low

Easily reversed and nonquenchable (low E barrier)

P3221

Polymorphism
2. Reconstructive polymorphs
More common: other quartz polymorphs, graphite-diamond,
calcite-aragonite, sillimanite-kyanite-andalusite
Transition involves extensive adjustments, including
breaking and reformation of bonds
High E barrier, so quenchable and not easily reversed (still
find Precambrian tridymite)
Stable
Unstable
Metastable

Pseudorphism
May be confused with polymorphs
A completely different thing
Complete replacement of one mineral by one or more other
minerals such that the new minerals retain the external
shape of the original one
Limonite after pyrite
Chlorite after garnet
etc.

Can use the shape to infer the original mineral

Very useful in petrogenetic interpretations

Solid Solutions
Substitution (mixing, solution) of ions on specific sites
Forsterite: Mg2SiO4
Mg occupies the VI sites in the olivine structure
Can substitute Fe for Mg and create Fayalite: Fe2SiO4
In olivine the substitution is very readily accomplished and
any intermediate composition is possible
Olivine: (Mg, Fe)2SiO4
This means that olivine is a solid-solution series in which any
ratio of Mg/Fe is possible as long as they sum to two ions
per formula unit (required for electric neutrality)

Solid Solutions
Intermediate compositions can be expressed as:
1. A chemical analysis (in weight % oxides)
SiO2

38.5

FeO
MgO

22.9
38.6

Total

100.0

Such an analysis is very difficult

to interpret in terms of the
mineral that it represents

Solid Solutions
Intermediate compositions can be expressed as:
1. A chemical analysis (in weight % oxides)
SiO2

38.5

FeO
MgO

22.9
38.6

Total

100.0

Such an analysis is very difficult

to interpret in terms of the
mineral that it represents

2. This can be converted to a mineral formula

Mg1.5 Fe0.5 SiO4

Solid Solutions
Intermediate compositions can be expressed as:
1. A chemical analysis (in weight % oxides)
SiO2

38.5

FeO
MgO

22.9
38.6

Total

100.0

Such an analysis is very difficult

to interpret in terms of the
mineral that it represents

2. This can be converted to a mineral formula

Mg1.5 Fe0.5 SiO4
3. This can then be expressed in terms of end-members

XMg = Mg / (Mg + Fe) on an atomic basis = 1.5 / 2 = 0.75

or

Fo75 where the sum of the end-members = 1

Solid Solutions
Solid solutions are most extensive if the valence and
radius of the substituting ions are similar
Good if radii differ by < 15%
Fe 2+ = 0.80 A Mg 2+ = 0.74 A (7.5%)
Mn 2+ = 0.91 A (14% - Fe and 21% - Mg)
Limited or rare if differ by 15-30 %
Never if > 30 %

Solid Solutions
Solid solutions are most extensive if the valence and
radius of the substituting ions are similar
If valence differs will not substitute or requires coupled
substitution
NaAlSi3O8 - CaAl2Si2O8 in plagioclase
Na+ + Si4+ exchange for Ca2+ + Al3+ to maintain 5+ total

Jadeite NaAlSi2O6 - diopside CaMgSi2O6

Exsolution

Lower T

Limits impurity

Structure may reject excess

Exsolution

Oriented lamellae, or

Entirely rejected from the crystal

Non-coherent masses

Exsolution
The process is exsolution and the product may be oriented
lamellae of the lesser complementary phase in the greater host

Blebby cpx exsolved from opx

Opx with 2 lamellae of exsolved

host, Skaergaard Intrusion

cpx, Bushveld Intrusion

From Deer et al RockForming Minerals vol

1A. WIley

whispy perthite lamellae as albite is

exsolved from orthoclase
Opx with lamellae of exsolved
plagioclase, Nain anorthosite

Alternatively the exsolved material may be entirely rejected from

the crystal, or form as non-coherent masses

Order - Disorder
Random vs. ordered atoms
1. Random

Each atom is statistically identical

(chance of being A is the same for
each position) Higher T

2. Perfect Order

Alternating A and B- Lower T

Note larger unit cell!

Order - Disorder

Triclinic monoclinic
in KAlSi3O8 requires
mirror symmetry

potential

mirror

Must disorder at high

temperature before
monoclinic

Crystal Defects
Defects can affect
Strength
Conductivity
Deformation style
Color

Crystal Defects
Steel spheres:
a) Regular packed array with
3 point defects
b) Point and line defects
c) Mosaic (or domains)
separated by defect
boundaries
These are not twins!

Fig 3.50 of Klein

and Hurlbut, Manual
of Mineralogy,
John Wiley and Sons

Crystal Defects
1. Point Defects
a) Schottky (vacancy) - seen with steel
balls in last frame

b) Impurity
Foreign ion replaces normal one
(solid solution)
Not considered a defect
Foreign ion is added (interstitial)
Both combined

a. Schottky defect

b. Interstitial (impurity) defect

Crystal Defects
1. Point Defects
c) Frenkel (cation hops from lattice
site to interstitial)
= a + b combination

b. Frenkel defect

Crystal Defects
2. Line Defects
d) Edge dislocation
Migration aids ductile deformation

Fig 10-4 of
Bloss,
Crystallography
and Crystal
Chemistry.
MSA

Crystal Defects
2. Line Defects
e) Screw dislocation (aids mineral growth)

Fig 10-5 of
Bloss,
Crystallography
and Crystal
Chemistry.
MSA

Crystal Defects
3. Plane Defects
f) Lineage structure or mosaic crystal
Boundary of slightly mis-oriented volumes within a single crystal
Lattices are close enough to provide continuity (so not separate
crystals)
Has short-range order, but not long-range (V 4)

Fig 10-1 of Bloss, Crystallography and Crystal Chemistry. MSA

Crystal Defects
3. Plane Defects
g) Domain structure (antiphase domains)
Also has short-range but not long-range order

Fig 10-2 of Bloss, Crystallography and Crystal Chemistry. MSA

Crystal Defects
3. Plane Defects
h) Stacking faults
Common in clays and low-T disequilibrium
A - B - C layers may be various clay types (illite, smectite, etc.)
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