Pauling Rules

3.4.
The Rules of Bonding and Coordination in Ionic

Crystals
The rules of bonding and coordination in ionic crystals were deduced and formalized
by Linus Pauling in his five famous rules.
3.4.1. Pauling's First Rule
Around every cation, a coordination polyhedron of anions forms, in which the cationanion distance is determined by the radius sums and the coordination number is
determined by the radius ratio.
In this view anions are large and cations are small. To a first approximation they
behave in ionic structures as hard spheres such that cations just touch anions. Thus,
what the second part of the first rule is based on is constant inter-atomic distance.
Si-O 1.62 + .03 Mg-O 2.08 + .09
The third part of the first rule says that the CN is determined by the radius ratio. A
couple of exam ples of how this can be determined geometrically follows: Table 3.2
Radius ratios for various coordination polyhedra
CN
Polyhedron
Example Radius Ratio Range
3
4
5
6
8
8
12
Triangle
Tetrahedron
Trigonal Bipyramida
Octahedron
Square Antiprism
Cube
Dodecahedron
C in Calcite
Si in Quartz
Al in Andalusite
Mg in Forsterite
Ca in Garnet
Ca in Fluorite
Native gold
0.155-0.22
0.22-0.41
0.41-0.645
0.645-0.730
0.73-1.00
1.00
3.4.2. Pauling's Second Rule: The Electrostatic Valence Rule

An ionic structure will be stable to the extent that the sum of the strengths of the
electrostatic bonds that reach an anion equals the charge on that anion.
Work this out for the NaCl structure:
Each Na is surrounded by 6 Cl - ions, 1/6 of each Cl is in turn coordinated by 6

Na+ ions. Hence, each are balanced.
3.4.3. Pauling's Third Rule
The sharing of edges, and particularly faces by two anion polyhedra decreases the
stability of a crystal.
This is related to the second rule. Two Si tetrahedra never share faces because this
would completely saturate the oxygens of the shared face leaving no more bond
strength available for the rest of the structure.
3.4.4. Pauling's Fourth Rule - an extension of the third rule
In a crystal which contains different cations, those with high charge and low
coordination numbers tend not to share elements of their coordination polyhedra.
3.4.5. Pauling's Fifth Rule: The Rule of Parsimony
The number of essentially different kinds of constituents in a crystal tends to be small.

This rule states that structures tend to be simple and contain only two or three types of
cation sites. There is no single mineral which can encompass all the different elements
in, say, a granite or a ba salt. Hence, most rocks are poly-mineralic.
3.5. Packing of Spheres
Although there is considerable reason to doubt hard sphere models for anions,
consideration of how hard spheres pack to fill space can yield much insight into how
atoms arrange themselves into crystals.
Let us begin with the simple cubic packing (primitive cubic) because it is the easiest
to visualize. No known minerals crystallize with the simple cubic structure because
the packing is inefficient. However, some anions are packed in this way in ionic
structures. There is a more efficient way to stack a simple cubic array. This is the body
centered cubic (bcc) structure. Native Fe in meteorites has this structure and is known
as the mineral kamacite (a=2.80 ).
But there are two more efficient ways to pack spheres: Hexagonal closest
packing and Cubic Closest Packing. Hexagonal closest packed layers may be
stacked in two different ways. If we put one layer over the B interstices, then when we
put the third layer on it can be in the B or the C positions. If we put the third layer in
the B position we have a stacked se quence ABABAB..., and we preserve 6-fold
symmetry. This is called Hexagonal Close Packing (HCP). It is rare for elements to
crystallize in this form in nature. However, the mineral Iridosmine (Os-Ir-Fe) and
many synthetic alloys have this structure. It is most important as a way to stack anions
in ionic crystals.
If the third layer is place over the C interstices, then the repeat is ABCABCABC... and
you have Cubic Close Packing (CCP). Only a three-fold is preserved, but four-fold
and two-fold symmetry axes are generated. This type of packing has more symmetry
than HCP and is represented by many structures of metallic elements (e.g. Cu, Ag, Pb,
Pt, Pd, Ir). It also forms the basis for stacking oxygens in numerous minerals and
complex oxides. We can use the NaCl model to point out octahedral and tetrahedral
voids and the relationship of NaCl to face-centered cubic (FCC).

Pauling Rules

Uploaded by

Copyright:

Available Formats

Pauling Rules

Uploaded by

Document Information

Original Description:

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Pauling Rules

Uploaded by

Copyright:

Available Formats

3.4.

The Rules of Bonding and Coordination in Ionic

Example Radius Ratio Range

3.4.2. Pauling's Second Rule: The Electrostatic Valence Rule

Each Na is surrounded by 6 Cl - ions, 1/6 of each Cl is in turn coordinated by 6

The number of essentially different kinds of constituents in a crystal tends to be small.

You might also like