Nuclear reactions

determine element
abundance
Is the earth
homogeneous
though?
Is the solar
system??
Is the universe???

Earth = anion balls with cations

in the spaces
View of the earth as a system of anions
packed together By size and abundance,
Si and O are the most important
If we consider anions as balls, then their
arrangement is one of efficient packing, with
smaller cations in the interstices
Closest packed structures are ones in which
this idea describes atomic arrangement OK
for metals, sulfides, halides, some oxides

Closest Packing
Coordination number (C.N) - # of anions bonded
to a cation larger cation, higher C.N.
Anions are much larger than most cations
anion arrangements in 3 dimensions = packing
Hexagonal Closest Packed (HCP) - spheres lie
atop each other vertical sequence ABABAB
Cubic closest packed (CCP) spheres fill in gaps
of layer below vertical sequence ABCABC
Exceptions to closest packing Body centered
cubic (BCC), polyhedra, and others

Paulings Rules for ionic structures

1. Radius Ratio Principle

cation-anion distance can be calculated from

their effective ionic radii
cation coordination depends on relative radii
between cations and surrounding anions

Geometrical calculations reveal ideal Rc/Ra ratios

for selected coordination numbers
Larger cation/anion ratio yields higher C.N. as
C.N. increases, space between anions increases
and larger cations can fit
Stretching a polyhedra to fit a larger cation is
possible

C.N. calculations
Application of pythagorean theorem:
c2=a2+b2
End up with ranges of Rc/Ra values
corresponding to different C.N.

Rc/Ra

Expected coordination

C.N.

<0.15
0.15
0.15-0.22
0.22
0.22-0.41
0.41
0.41-0.73
0.73
0.73-1.0
1.0
>1.0

2-fold coordination
Ideal triangular
Triangular
Ideal tetrahedral
Tetrahedral
Ideal octahedral
Octahedral
Ideal cubic
Cubic
Ideal dodecahedral
dodecahedral

2
3
3
4
4
6
6
8
8
12
12

Paulings Rules for ionic structures

2. Electrostatic Valency Principle
Bond strength = cation valence / C.N.
Sum of bonds to a ion = charge on that ion
Relative bond strengths in a mineral containing
>2 different ions:

Isodesmic all bonds have same relative strength

Anisodesmic strength of one bond much stronger
than others simplify much stronger part to be an
anionic entity (SO42-, NO3-, CO32-)
Mesodesmic cation-anion bond strength =
charge, meaning identical bond strength available
for further bonding to cation or other anion

Bond strength Paulings 2nd Rule

Bond Strength of Si = the charge of O2-

Si

4+

O2- has strength (charge) to attract either another

Si or a different cation if it attaches to another Si,
the bonds between either Si will be identical

Bond Strength
= 4 (charge)/4(C.N.) = 1

O2-

Si4+

O2-

Si4+

Mesodesmic subunit SiO

Each Si-O bond has
strength of 1
This is the charge of O2 O2- then can make an
equivalent bond to cations
or to another Si4+ (two Si4+
then share an O)
Reason silicate can easily
polymerize to form a
number of different
structural configurations
(and why silicates are
hard)

44

Nesosilicates
SiO44Sorosilicates
Si2O76-

Cyclosilicates
Si6O1812-

Inosilicates
(single)
Si2O64-

Inosilicates
(double)
Si4O116-

Phyllosilicates
Si2O52-

Tectosilicates
SiO20

Paulings Rules for ionic structures

3. Sharing of edges or faces by coordinating
polyhedra is inherently unstable
This puts cations closer together and they will
repel each other

Paulings Rules for ionic structures

4. Cations of high charge do not share
anions easily with other cations due to
high degree of repulsion
5. Principle of Parsimony Atomic
structures tend to be composed of only a
few distinct components they are simple,
with only a few types of ions and bonds.