Pauling's Rules

Assignment 1 Material synthesis course.

Rule #1 - A coordinated polyhedron of anions is formed about

each cation, the cation-anion
distance equaling the sum of their characteristic packing radii
and the coordination
polyhedron being determined by the radius ratio
Rule #2 - An ionic structure will be stable to the extent that
the sum of the strengths of the
electrostatic bonds that reach an anion equal the charge on
that anion.
Rule #3 - The sharing of edges and particularly faces by two
anion polyhedra decreases the
stability of an ionic structure
Rule #4 - In a crystal containing different cations, those of
high valency and small coordination number tend not to share polyhedron elements with one
another
Rule #5 - The number of essentially different kinds of
constituents in a crystal tends to be
small.
Zinc Blende structure
Many AB compounds form Zinc Blende structure by arranging anions in hcp stacking.
ZnS is a tetrahedral stack of ABCABC.
Coordination number for both anions and cations is 4 since for ZnS radius ratio is .34
The bonding between Zn2+ and S2- has a large covalent component. So Pauling may not be
suitable since it deals with ionic.
Zn2+ ions are located in half the tetrahedral interstices to maximize their separation.
Spinel Structure
Has the form AB2O4. Magnetic ferrites are spinel. BL is FCC.
Oxygen ions are in fcc close packing.
There are 4 atoms, 4 octahedral interstices and 8 tetrahedral interstices.
Total 12 interstices to be filld by 3 cations=> 1 divalent and two trivalent.

In normal spinel the A2+ ions are on tetrahedral sites and B3+ are on the octahedral sites
In inverse spinels the A2+ ions and half the B3+ ions are on octahedral sites;the other half of the
B3+ are on tetraheral sites B(AB)O4
Corundum structure(Alumina)
In Al2O3 the preferred CN is 6 so that the valence of 3 there is a bond strenth of half. This requires
4 Al3+ adjacent to each O2Rutile Structure
TiO2 is the famous rutile structure. CN for Ti is 6 with a valence of +4 leading to a bond strength of
2/3 and requires 3fold coordination of Ti4+ around each oxygen ion.
Caesium Chloride
CsCl needs 8 fold coordination. Bond strength is 1/8. This leads to a simple cubic array with Cs/Cl
atoms in the interstices.
Flourite structure
Thorium oxide. CN of 8 Leading to bond strength of half. SC packing for oxygen.
This has a large number of vacant space which allows Uranium oxide to accomodate fission
products in nuclear reactions.