Paulings Rules

J.D. Price

Pauling's Rules
Rule 1. Interatomic Distance. A coordination
polyhedron of anions is formed about each cation.
The cation-anion distance being determined by the
radius sum and the coordination number of the
cation by the radius ratio.
Rule 2. Electrostaic Valency Principle. In a stable
coordination structure, the total strength of the
valency bonds that reach an anion from all neighboring cations is equal to
the charge of the anion.
Rule 3. Sharing of Polyhedral Elements I. The existence of edges and
particularly of faces, common to two coordination polyhedra decreases the
stability of ionic structures.
Rule 4. Sharing of Polyhedral Elements II. In a crystal containing different
cations, those with large valence and small coordination tend not to share
polyhedral elements with each other.
Rule 5. Principle of Parity. The number of essentially different kinds of
constituents in a crystal structure tends to be small.

Rule 1. Interatomic Distance. A coordination polyhedron of anions is

formed about each cation. The cation-anion distance being determined
by the radius sum and the coordination number of the cation by the
radius ratio.

**Old news to us**

Now is the time to talk of the
limitations:
1. Ionic radii - and an approximation
2. Ionic - you mean % ionic
3. What if we are close to a limiting
value

Rule 2. Electrostatic Valency Principle. In a stable coordination

structure, the total strength of the valency bonds that reach an anion
from all neighboring cations is equal to the charge of the anion.

V
= Strength
CN
Na
Cl
0.11 nm 0.172 nm

V=?
CN =?

Rule 3. Sharing of Polyhedral Elements I. The existence of edges and

particularly of faces, common to two coordination polyhedra decreases the
stability of ionic structures.

Why?

Rule 4. Sharing of Polyhedral Elements II. In a crystal containing

different cations, those with large valence and small coordination tend not
to share polyhedral elements with each other.

Highly charged cations (e.g. +4),

particularly small ones, repel other
highly charged cations - difficult to
allow them to share more than one
oxygen.

Rule 5. Principle of Parity. The number of essentially

different kinds of constituents in a crystal structure tends to be
small.

Simple is Good!