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7 Pauling
7 Pauling
7 Pauling
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
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
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:
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
Paulings Rules
5th Rule:
The spinel
2+ IV
3 VI
2
Paulings Rules
5th Rule:
The spinel
2+ IV
3 VI
2
Paulings Rules
5th Rule:
The spinel
2+ IV
3 VI
2
Paulings Rules
5th Rule:
The spinel
2+ IV
3 VI
2
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
10
Pressure (GPa)
Coesite
- quartz
- quartz
600
Liquid
Cristobalite
Tridymite
1000
1400
1800
2200
Temperature C
o
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
P6222
Low
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.
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
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
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
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
Exsolution
Lower T
Limits impurity
Exsolution
Oriented lamellae, or
Non-coherent masses
Exsolution
The process is exsolution and the product may be oriented
lamellae of the lesser complementary phase in the greater host
Order - Disorder
Random vs. ordered atoms
1. Random
2. Perfect Order
Order - Disorder
Triclinic monoclinic
in KAlSi3O8 requires
mirror symmetry
potential
mirror
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!
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
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)
Crystal Defects
3. Plane Defects
g) Domain structure (antiphase domains)
Also has short-range but not long-range order
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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