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Pyroxene Mineral Formula

Orthopyroxene 91145
Col 1 Col 2 Col 3 Col 4 Col 5
Wt% Ox Mol Wt Mol Ox At Ox # anions Cations IV VI
SiO2 52.09 60.09 0.8669 1.7337 3.919 1.96 1.96
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 0.04
Fe2O3 159.7 0.0000 0.0000 0.000 0.00 0.00
FeO 27.06 71.85 0.3766 0.3766 0.858 0.86 0.86
MnO 0.66 70.94 0.0093 0.0093 0.021 0.02 0.02
MgO 19.11 40.32 0.4740 0.4740 1.079 1.08 1.08
CaO 0.51 56.08 0.0091 0.0091 0.021 0.02 0.02
Na2O 0.05 61.98 0.0008 0.0008 0.002 0.00 0.00
K2O 94.2 0.0000 0.0000 0.000 0.00 0.00
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


Cl

For Na+ the strength =


+1 divided by 6 = + 1/6 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 + 1/6 Na
strengths of electrostatic bonds that
reach an anion from adjacent + 1/6
cations = the charge of that anion Na
- Na
Cl
+ 1/
6 ( + 1/6 ) = +1 (sum from Nas) 6

charge of Cl = -1
Na + 1/6

These charges are equal in magnitude so


the structure is stable
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 VIII is not CP
IV
III (small and uncommon cations)
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:
2+ IV 3 + VI
The spinel ( A ) ( B ) O 4 structure at various angles
2

Note
CCP abcabc layers
of Oxygens
White VI sites
Blue IV sites
Paulings Rules
5th Rule:
2+ IV 3 + VI
The spinel ( A ) ( B ) O 4 structure at various angles
2

Polyhedral model
White VI sites
Blue IV sites
Paulings Rules
5th Rule:
2+ IV 3 + VI
The spinel ( A ) ( B ) O 4 structure at various angles
2

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:
2+ IV 3 + VI
The spinel ( A ) ( B ) O 4 structure at various angles
2

Rotating to where cation


sites almost line up
Paulings Rules
5th Rule:
2+ IV 3 + VI
The spinel ( A ) ( B ) O 4 structure at various angles
2

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
Stishovite
The compound SiO2 has several
10
different structural forms, or
polymorphs
8

Pressure (GPa)
The common form is - or low-
quartz, but there are others that 6
Coesite
become stable under different
conditions, including - or 4

high-quartz, tridymite, - quartz


2
cristobalite, coesite, and - quartz
Cristobalite
Liquid

stishovite Tridymite

600 1000 1400 1800 2200 2600

The SiO2 phase diagram After Swamy and Saxena (1994) J.


Temperature oC

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


Polymorphism
1. Displacive polymorphism
quartz at 573oC at
atmospheric pressure 4 Coesite

Pressure (GPa) 2
Low-Quartz High-Quartz

0 500

Temperature
Polymorphism
High
1. Displacive polymorphism
Note: higher T higher
symmetry due to more
thermal energy (may twin as
lower T) P6222
Transition involves small
adjustments and no Low
breaking of bonds
Easily reversed and non-
quenchable (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
Such an analysis is very difficult
FeO 22.9 to interpret in terms of the
MgO 38.6 mineral that it represents
Total 100.0
Solid Solutions
Intermediate compositions can be expressed as:
1. A chemical analysis (in weight % oxides)
SiO2 38.5
Such an analysis is very difficult
FeO 22.9 to interpret in terms of the
MgO 38.6 mineral that it represents
Total 100.0
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
Such an analysis is very difficult
FeO 22.9 to interpret in terms of the
MgO 38.6 mineral that it represents
Total 100.0
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
(Fo75 implies Fa25)
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 Rock-


whispy perthite lamellae as albite is Forming Minerals vol
exsolved from orthoclase 1A. WIley

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 2. Perfect Order

Each atom is statistically identical Alternating A and B- Lower T


(chance of being A is the same for
Note larger unit cell!
each position) Higher T
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

a. Schottky defect
b) Impurity
Foreign ion replaces normal one

(solid solution)
Not considered a defect
Foreign ion is added (interstitial)

Both combined

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 (V4)

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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