Lecture 4 (9/18/2006)

Crystal Chemistry

Part 3:
Coordination of Ions
Paulings Rules
Crystal Structures
Coordination of Ions
For minerals formed largely by ionic bonding,
the ion geometry can be simply considered to be
spherical
Spherical ions will geometrically pack
(coordinate) oppositely charged ions around
them as tightly as possible while maintaining
charge neutrality
For a particular ion, the surrounding
coordination ions define the apices of a
polyhedron
The number of surrounding ions is the
Coordination Number

Coordination
Number and
Radius Ratio
See Mineralogy CD: Crystal
and Mineral Chemistry -
Coordination of Ions
Coordination
with O
-2

Anions
When
Ra(cation)/Rx(anion)
~1
Closest
Packed
Array
See Mineralogy
CD: Crystal and
Mineral Chemistry
Closest Packing
Paulings Rules of Mineral Structure
Rule 1: A coordination polyhedron
of anions is formed around each
cation, wherein:
- the cation-anion distance is
determined by the sum of the
ionic radii, and
- the coordination number of the
polyhedron is determined by the
cation/anion radius ratio (Ra:Rx)
Linus Pauling
Rule 2: The electrostatic valency principle
The strength of an ionic (electrostatic)
bond (e.v.) between a cation and an anion
is equal to the charge of the anion (z)
divided by its coordination number (n):
e.v. = z/n
In a stable (neutral) structure, a charge
balance results between the cation and its
polyhedral anions with which it is bonded.
Paulings Rules of Mineral Structure
Charge Balance
of Ionic Bonds
Formation of Anionic Groups
Results from high valence cations with electrostatic
valencies greater than half the valency of the
polyhedral anions; other bonds with those anions will
be relatively weaker.

Carbonate
Sulfate
Rule 3: Anion polyhedra that share edges or
faces decrease their stability due to bringing
cations closer together; especially significant for
high valency cations

Rule 4: In structures with different types of
cations, those cations with high valency and
small CN tend not to share polyhedra with each
other; when they do, polyhedra are deformed to
accommodate cation repulsion
Paulings Rules of Mineral Structure
Rule 5: The principle of parsimony

Because the number and types of different structural
sites tends to be limited, even in complex minerals,
different ionic elements are forced to occupy the same
structural positions leads to solid solution.

See amphibole structure for example (See Mineralogy CD:
Crystal and Mineral Chemistry Paulings Rules - #5)

Paulings Rules of Mineral Structure
Visualizing Crystal Structure
Ball and Stick Model Polyhedra Model
Beryl - Be
3
Al
2
(Si
6
O
18
)
Portraying Crystal Structure in Two
Dimensions
Isostructural Types
AX Compounds Halite (NaCl) structure
Anions in CCP packing
Cations in octahedral sites
Ra/Rx=.73-.41
Examples:
Halides: +1 cations (Li, Na, K, Rb) w/ -1
anions (F, Cl, Br, I)
Oxides: +2 cations (Mg, Ca, Sr, Ba, Ni) w/ O
-2

Sulfides: +2 cations w/ S
-2

(See Mineralogy CD: Crystal and Mineral Chemistry
Illustrations of Crystal Structures Halite)

Isostructural Types
AX Compounds Sphalerite (ZnS) structure
RZn/RS=0.60/1.84=0.32 (tetrahedral)


AX
2
Compounds Flourite (CaF
2
) structure
RCa/RF=1.12/1.31=0.75 (cubic)
Examples: Halides (CaF
2
, BaCl
2
...); Oxides (ZrO
2
...)
Isostructural Types
ABO
4
Compounds Spinel (MgAl
2
O
4
)structure
- Oxygen anions in CCP array
- Two different cations (or same cation with two different valences) in
tetrahedral (A) sites (e.g. Mg
2+
, Fe
2+
, Mn
2+
, Zn
2+
) or octahedral (B) sites
(e.g. Al
3+
, Cr
3+
, Fe
3+
)

Isostructural Types
Nesosilicates
Sorosilicates
Cyclosilicates
Inosilicates
(single chain)
Inosilicates
(double chain)
Phyllosilicates
Tectosilicates

Next Lecture
Crystal Chemistry IV
Compositional Variation of Minerals
Solid Solution
Mineral Formula Calculations
Graphical Representation of Mineral
Compositions

Read p. 90 - 103