Dr.

Ulva Ria Irfan

Geological Engineering Study Program

Gowa, 06/04/2020
Mineral Structures
 From definition of a mineral:
 “…an ordered atomic arrangement…”
 How do Pauling’s rules control “ordered atomic
arrangement?”
 How can crystal structure make one mineral different
from another?
 Can mineral structures be used to group minerals (e.g.
classify them)?
Illustrations of mineral structures
 2-D representation of 3-D materials
 Ions represented as spheres – drawn to scale
 Stick and ball method
 Polyhedron method
 Hybrid: Stick and Ball, plus polyhedron
 Map view – unit cell dimensions
 Unit cell outline

Olivine – view down

a crystallographic
axis
Fig. 4-10
Structures
 Isostructural minerals (isomorphous substitution)
 Same structure, different composition

 Polymorphism – polymorphic minerals

 Same composition, different structures
Isostructural Minerals
Many minerals have identical
structures, different
compositions
 Example: halite (NaCl) and
Galena (PbS)
 Differ in many physical
properties - composition
 Identical symmetry,
cleavage, and habit –
elemental arrangement
Isostructural group
 Several isostructural minerals have common anion
group
 Much substitution between cations
 Example: calcite group
Calcite Isostructural
 Polymorphism_1
 The ability for compounds with identical
compositions to crystallize with more than one
structure
 Polymorphs
 Polymorphic groups
Polymorphism_2
 Caused by balance of conflicting
requirements and environmental factors:
 Attraction and repulsion of cations and anions
(charge)
 Fit of cations in coordination site (size)
 Geometry of covalent bonds
P & T primary environmental variables
 Polymorphism_3
P and T controls:
 High P favors tightly packed lattice, high density
 High T favors open lattice, low density, wide substitution

 Composition of environment unimportant

 All same elements in polymorphs

 Presence or absence of polymorphs provide

information on P and T conditions
 Polymorphism_4
 Fourtypes of mechanisms to create
polymorphs:
1. Reconstructive – break bonds
2. Order-disorder – cation placement
3. Displacive – kink bonds
4. Polytypism – stacking arrangement
1. Reconstructive polymorphism
 Requires breaking bonds –
major reorganization
 Symmetry and/or structural
elements may differ
between polymorphs
 Symmetry and/or structural
elements may be similar
because identical
composition
 Example: Carbon
C = Diamond and Graphite
 Diamond – all 100%
covalent bonds
 Graphite – covalent
bonds within sheets, van
der Waal bonds between
sheets
 What conditions cause
one mineral or the other
to form?
 C = Diamond and Graphite
 Graphite – stable at earth surface T and P

 Diamond stable only at high P and T – but

found on earth surface
 Won’t spontaneously convert to graphite
 Minerals that exists outside of their stability fields
are metastable
 What are temperatures at these depths?
Found on a Phase Diagram – e.g. for single component

Increasing
Depth
(linear) ~200 km depth

~100 km depth

Single component = C

Increasing
Depth (non-linear)

Where on (in) the earth would diamond form/be stable?

Fig. 4-11
 Diamond stability versus geothermal gradient

Kimberlite
Red line is

Diamond window
geothermal
gradient

Stability
Boundary of
Diamond Lithosphere
and
Graphite
Asthenosphere

Phase diagram Conceptual model of earth

 Metastable minerals occur because of energy
required for conversion
 Bonds must be broken to switch between
polymorphs
 Cooling removes energy required to break bonds
 Rate of cooling often important for lack of
conversion – e.g. fast cooling removes energy
before reactions occur
 Quenching – “frozen”: e.g. K-feldspars
 Example of Order-disorder polymorphism
2. Order-disorder polymorphism
 The mineral structure remains same between
polymorphs

 Differenceis in the location of cations in structure

 Good examples are the K-feldspars
 One end-member of the alkali feldspars
 Idealized feldspar structure
Si or Al

K (or Na, Ca)

Si or Al

➢ K-feldspar has 4 tetrahedral sites called T1 and T2

(two each)
Fig. 12-6
“K-spars”
 KAlSi3O8 – one Al3+ substitutes for one Si4+
 High Sanidine (high T) – Al can substitute for
any Si – completely disordered
 Low Microcline (low T) – Al restricted to one
site – completely ordered
 Orthoclase (Intermediate T) – Intermediate
number of sites with Al
Order-disorder in the K-feldspars

High Sanidine – Al3+ equally

likely to be in any one of
the four T sites

Microcline – Al3+ is restricted

to one T1 site. Si4+ fills other
three sites

Fig. 4-13
 Order-disorder in the K-feldspars

 Degree of order depends on T

 High T favors disorder
 Low T favors order
 Sanidine formed in magmas found in volcanic rocks
– quenched at disordered state: metastable
 Microcline found in plutonic rocks – slow cooling
allows for ordering to take place
 Over time, sanidine will convert to microcline
3. Displacive Polymorphism
 No bonds broken
 a and b quartz are good examples
 b quartz (AKA high quartz)
 1 atm P and > 573º C, SiO2 has 6-fold rotation
axis.
 a quartz (AKA low quartz)
 1 atm P and < 573º C, SiO2 distorted to 3-fold axis
View down b quartz a quartz
c-axis

6-fold 3-fold rotation

rotation axis
axis

• Conversion can not be quenched, always happens

• Never find metastable b quartz
Fig. 4-12
 External crystal shape may be retained from
conversion to low form
 Causes strain on internal lattice
 Strain may cause twinning or undulatory extinction
 Must have sufficient space for mineral to form

Undulatory extinction
 4. Polytypism

 Stacking diffrences
 Common examples are micas and clays
Common Sheet silicates – like clay minerals

Orthorhombic, Orthorhombic, Monoclinic,

single stacking two stacking single stacking
vector, 90º vectors, not 90º vector, not 90º

Fig. 4-14
 Common Sheet silicates – like clay minerals

 Eventually will get to controls on compositional

variations
 First some necessary skills:
 Scheme for mineral classification
 Rules for chemical formulas
 A graphing technique – ternary diagrams
 Mineral Classification
 Based on major anion or anionic group
 Consistent with chemical organization of
inorganic compounds
 Families of minerals with common anions
have similar structure and properties
 Cation contents commonly quite variable
Mineral group Anion or anion gp
Native elements N/A
Oxides O2-
Hydroxides OH-
Halides Cl-, Br-, F-
Sulfides S2-
Sulfates SO42-
Carbonates CO32-
Phosphates PO43-
Silicates SiO44-
 Mineral Classification
 Follows from Pauling’s rules
 1, 3, and 4 (coordination polyhedron & sharing of
polyhedral elements) - anions define basic
structure
 2: (electrostatic valency principle) anionic group
separate minerals
Mineral Formulas
 Rules
 Cations first, then anions or anionic group
 Charges must balance
 Cations of same sites grouped into parentheses
 Cations listed in decreasing coordination number
○ Thus also decreasing ionic radius
○ Also increasing valence state
 Examples

 Diopside – a pyroxene: CaMgSi2O6

 Charges balance
 Ca - 8 fold coordination: +2 valence
 Mg - 6 fold coordination: +2 valence
 Si – 4 fold coordination: +4 valence
 Anionic group is Si2O6
 Examples
 Substitution within sites indicated by parentheses:
 Ca(Fe,Mg)Si2O6
 Intermediate of two end-members: Diopside
CaMgSi2O6 – Hedenbergite CaFeSi2O6 complete
solid solution series
(more on “solid solution” in a moment)
 Examples
 Can explicitly describe substitution
 E.g. Olivine: (Mg2-x,Fex)SiO4 0≤x≤2
 Alternatively: Can describe composition by relative
amounts of end members:
 Forsterite = Fo
 Fayalite = Fa
Olivine
 General composition of olivine is (Mg,Fe)2SiO4
 All of the following are the same exact
composition:
 (Mg0.78Fe0.22)2SiO4
 Mg1.56Fe0.44SiO4
 Fo78Fa22 (here numbers are percentages of
amount of each mineral)
 Fo78 (here implied that the remainder is Fa22)
 Fa22
Latihan Soal
1. Jelaskan struktur mineral berdasarkan konsep Pauling
2. Berikan contoh dan jelaskan mineral yang membentuk isostructural
3. Jelaskan 4 mekanisme pembentukan struktur mineral
polymorphism
4. Jelaskan klasifikasi mineral berdasarkan ikatan dengan anion atau
grup anion, berikan contoh masing-masing 3 mineral.

Tugas dikumpulkan ke Ketua kls A, hari Rabu, 8/4/20 jam 17.00

Selamat belajar, tetap di rumah dan sehat selalu
Salam: Ibu Ulva