08-Nov-13

Bonding in Ceramics

CERAMIC STRUCTURES

Dr. Mohsin Ali Raza

Department of Metallurgy and Materials Engineering
University of the Punjab

How to calculate % Ionic Character ?

Dipole moment of molecule is used to
calculate ionic character
Covalent bonds
- Equally shared electrons --- non-polar
- Unequal sharing of electrons--- polar
Ionic bonds
Complete transfer of electrons when one
becomes +ve (cation) and other becomes ve
(anion)

Ceramics Crystal structures

If the atomic bonding is mainly ionic the crystal
structures are composed of electrically charged
ions instead of atoms.
Cation (+vely charged, Na+, Fe+2, Fe+3, Mg+2,
NH4+) and Anion (-vely charged, O-2, Cl-1, F-1,
CN-1,)
Ions do not exists on their own
Ions binds with ions of opposite charge to form a
crystal lattice.

Atomic bonding ranges from purely ionic to

totally covalent
Many ceramics possess combination of
both types of bonding
Ionic character depends on
Electronegativities of atoms
We can calculate % ionic character of
ceramic materials

Dipole moment
The measure of net polarity of a bond is
called dipole moment, ()
Mathematically,
=
Q = Charge
r= distance between charges
Units: debye
1 D = 3.336 x 10-30 C.m

Formation of ions
Removal of electron gives Cation (+vely
charged ions), has more number of
protons than electrons (All metals form
cations)
Addition of electron gives anion (-vely
charged), has more electrons than protons

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Criteria that influence crystal structure of

ceramics
First Criteria
The magnitude of the electrical charge on
each of the component ions.
- The crystal must be electrically neutral
- Charge must be balanced
Bonding in MgCl2 and CaF2
Ca+2 and F-1 (Two flouride ions are required for
ionic bonding and for charge neutrality)

Second Criteria
Each Cation prefers to have as many nearest
neighbours anions as possible and likewise.
Stable ceramic structures form when anions
surrounding a cation are in contact with that cation.
Size or ionic radii of the cations and anions is
important
Cation ion radius (rc) and anion radius (rA)
Cations are smaller than anions, the relative size is
quantified by the radius ratio ()

= < 1

Requirement for stable

structure
Anions surrounding a cation are all in contact with
that cation.
Closed packing of anions and cations necessary
The condition for minimum energy implies maximum
attraction and minimum repulsion. This leads to
contact, configurations where the anions have
highest number of cations neighbours and vice
versa.

Concept of stable structure

Coordination number (CN)

The number of nearest neighbours anions or
cations (In crystallography)

UNSTABLE

For a specific CN,

there is a critical or minimum radius ratio
(rC/rA), for which the cation-anion contact develops
and this can be found by geometrical analysis

STABLE

08-Nov-13

Concept of Ionic and Atomic Radii

Measure of size of atom (distance from the nucleus to

the boundary of surrounding electrons)
Ionic radii cant be determined absolutely
Determined on the probability of encountering electron

Tetrahedron

Octahedron

Bond length: Average

distance between nuclei
of two bonded atoms

Cube

Atomic and Ionic Radii

Pure element first
Native Cu. Atomic radius = 1/2 bond length

Bonds between identical

atoms atomic radius is half the
interatomic distance

X-ray d100 a

Ionic radius =

2
4

In the bonds between different

ions, distance is controlled by
attractive and repulsive forces
between the charges

Charge and Attractive Force Control on

Effective Ionic Radii

Approach until Repulsive and Attractive Forces

the same

08-Nov-13

Interionic forces for an ion pair

Fnet = Fattractive + Frepulsive

Interatomic Energies for an ion pair

= +

1 2 2

+
40
Repulsive energy

Attractive energy

Attractive energy : Released as the ions come close together (-ve)

Repulsive energy : absorbed as the ions come close together (+ve)

Minimum energy is achieved when ions are at their

equilibrium separation distance (ao)

Ref. Principles of Materials Science Engineering by William F. Smith

Homework problems

Lattice Energy
Amount of Energy released on the formation of bonds (-ve)
Indicator of bond strength

Example Problem 2.10

Table: Lattice Energies and Melting points of

selected ionic solids

Problems 2.5.4-2.5.9 (HW)

Example 2.11

Ionic radii of selected ions

Book
Principles of Materials Science and Engineering by W. F. Smith
3rd Edition

As the size of ion increases in a group, lattice energy decreases and

melting points decreases because bonding electrons are far from
the nucleus
Multiple bonding electrons in an ionic solid increase lattice energy

08-Nov-13

Bond Length

Average distance between the nuclei of the two bonded atoms

Shorter bond length means stronger bonds
Bond length is related to bond order
Bond order is number of bonding pair of electrons between two
atoms
More electrons involved means stronger bond

Bond strength and melting

temperature
MgO

NaCl

LiF

Structure

Melting
point

2852 C

801 C

848 C

Rocksalt

Inter-ionic
equilibrium
distance

212 pm

283 pm

209 pm

Rocksalt

Factors on which Bond strength depends

Bond energies and length of selected

covalent bonds

Comparison of Potential-interatomic
distance curves

Melting points of ionic compounds

Bond strength depends on valency and ionic radii

Higher the valency stronger will be the bond
Bond strength is directly proportional to multiplication
of ionic charges and inversely proportional to
equilibrium interionic distance
MgO

NaCl

LiF

Structure

Melting
point

2852 C

801 C

848 C

Rocksalt

Inter-ionic
equilibrium
distance

212 pm

283 pm

209 pm

Rocksalt

Ionic character of the bond is > 60 %

Why MgO has higher melting point than LiF despite having larger interionic distance?

08-Nov-13

Improve the criteria (Look for other factors)

Covalent Character of a Bond depends on EN difference

Melting point of Al2O3 = 2054 C

Melting point of MgO = 2852 C
Look at the bonding :
Al2O3 has higher covalent character than MgO

How we can qualitatively judge the COVALENCY of the

Higher
bonds?
electronegativity
Look at the Electronegativity (EN) differences
difference, Higher
will be the ionic
Al2O3 EN = EN of O EN of Al = 3.44-1.61= 1.83
character and the
MgO EN = EN of O EN of Mg = 3.44-1.31= 2.13
melting point

% Ionic Character vs EN

Covalent character increases

Melting point decreases
Structure also changes

Calculate % ionic character of mixed ionic-covalent

bonding
% = (1

1
4

)(100%)

Where, XA = EN of atom A
XB = EN of atom B

Polarisation

Polarization

Cations tend to attract outer electrons of the anion and at the same time it tends to
repel the positively charged nucleus of the anions. This result in distortion of the
anion (anion is polarised). The effect is called polarising effect.

Polarising power of Cation

The tendency of metal cation to distort the electron cloud of anion. It is
directly proportional to charge on cation and inversely proportional to
size of cation.
Polarising power of Anion

Polarisation arise due to the asymmertical distribution of the charges

The tendency of anion to get distorted because of the polarising power of

cation is called polarisibilty power of anion.

Due to high polarizing power of Al ion, Al2O3 develops

some covalent bonding and hence has lower melting point
than MgO

08-Nov-13

Factors Effecting Covalency of Ionic Bonds

Polarizing power of the Cation
It is the ratio of the charge to the ionic radius
Check for (Al+3) = 60 nm-1 for Mg+2 = 31 nm-1
Polarizing power of the anion
Same for oxide anions
Electron configuration of the Cation
no of electrons in d-orbital
Both Al2O3 and MgO have no d shell electrons

Smaller the cation,

larger the anion greater
is tendency for the
covalency
AgCl is more covalent
than NaCl because the
former has 18 electrons
in outermost shell while
in the latter Na+ has 8
electrons in outermost
shell.

Factors Effecting Covalency of Ionic Bonds

If polarisation is quite small, bonding is ionic.
If polarisation is very high, bonding is covalent.
If polarisation is in between the two values (above mentioned), the
bond is partial covalent.

AlI3 (melting point 189 C and AlF3 (1291 C)

Crystal Structures
Simple Cubic structure
Packing of spheres in a simple cubic array

Interstitial site
surrounded by eight
atoms

CN = 8

Close-packed cubic structures

Close-packed cubic structures

1

Octahedral
site (Type 2)

Tetrahedral
Sites (Type 1)

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Add next layer of atoms

Add third layer of atoms

(if it sits exactly on the atoms in layer 1
resulting structure is hexagonal closed pack with a
layer ordering of A-B-A-B)

Type 1 are
now covered
But type 2 are
still left vacant

Hexagonal close-packed structure

Cubic Closest packing

Add next layer of atoms

Type 1 are
now covered
But type 2 are
still left vacant

Interstitial site 3

08-Nov-13

Add next layer on site 3

Ordering is A-B-C

FCC lattice

Octahedral hole

Octahedral hole is surrounded by 6 atoms

Tetrahedral hole

Tetrahedral hole is surrounded by 4 atoms

08-Nov-13

Limiting Conditions for different Coordination numbers

For CN = 8

Ratio of Rc/Ra defines the limiting situation in which all atoms

touch contact each other

+ = 1.732

Determine the limiting condition i.e., Rc/Ra for the cation to

remain in 8 CN

dA = 1
Then

dC = 0.732

1 (arbitrary)
Cation will rattle if Relative
Radius goes below 0.732

1 (arbitrary)

For CN = 6

= = 0.732

+ = 2
dA = 1
Then
dC = 0.414

Use this plane

= = 0.414

Cation will rattle if Relative

Radius goes below 0.414

Home work problem

1. Calculate the critical (minimum) radius ratio (rc/ra)

Example problem 10.1

Calculate the critical (minimum) radius ration rC/RA for the
triangular coordination (CN =3) of three anions of radii R A
surrounding a central cation of radius r in an ionic solid.

for the tetrahedral coordination (CN=4) of 4 anions

of radii R surrounding a central cation of radius r in
an ionic solid (consider FCC unit cell).
2. Prove that the tetrahedral site is bigger in BCC
unit cell than FCC unit cell.

3. Calculate the octahedral vacancy for BCC unit cell.

Cation will rattle if Relative
Radius goes below 0.155

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08-Nov-13

Example Problem 10.2

Predict the CN for the ionic solids CsCl and NaCl. Use the following ionic
radii for the prediction:
Cs+ = 0.170 nm , Na+ = 0.102 nm and Cl- = 0.181
What will be the CN if the ionic radii of Na+ ions = 0.118 nm

AX Types crystal structures

Type 1 when CN= 8
Cesium Chloride (CsCl)

Cl
Cl-1
Cs

1 1 1

( , , )
2 2 2

Position of Cs
cation in unit
cell

Cs+1
Lattice of CsCl
Hard sphere model to represent
unit cell of CsCl

Examples of AX type ionic compounds

which have CsCl like structure
CsBr
TlCl
TlBr
Intermetallic compounds

Ball and Stick model for CsCl

Example 10.3
Calculate the ionic packing factor for CsCl. Ionic radii are
Cs+ = 0.170 nm and Cl-= 0.181 nm
Ionic packing factor =

3 = 2 + 2
= 0.405

CsCl ionic packing factor =

=

AlNi

R = Cl-1 ion and r = Cs+1

AgMg
LiMg

4
3
3

4
3

1 + 3 (1 )
3

0.68

-Cu-Zn

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08-Nov-13

Positions of octahedral site in FCC unit cell

Formation of Octahedrons

Octahedron sites are

Bound by 6 ions

Eight

In FCC unit cell, there are 13 octahedral sites, and octahedrons can
be formed

Rocksalt Structure

AX type crystal structures

Type 2
When CN = 6, rc/Ra is between 0.414 and 0.732
Example NaCl (Rock salt structure), MgO, MnS, LiF,etc.
Rock salt structure can be visualised as two interpenetrating
FCC lattices, one composed of cations and the other of anion

ClNa+

Positions of Na+ and Cl- in NaCl unit cell

Charge Balance in NaCl (Halite)

In Halite, Na+ has CN 6 and valence +1

Interpretation: Each Na+ has 6 Cl- neighbors, so each Cl- contributes a charge
of -1/6 to the Na+
6 x -1/6 = -1, so a charge balance results between the Na+ cation and the six
polyhedral Cl- anions with which it bonded. NEUTRALITY IS ACHIEVED

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08-Nov-13

Positions of octahedral sites

Example Problem 13.2

The octahedral sites are located at the centre of the unit cell (1/2, 1/2, 1/2)
as well as at the edges of the unit cell (1/2, 0, 0), etc.

On the basis of ionic radii, what crystal structure would

you predict for FeO?
rFe2+ = 0.077 nm
RO-2 = 0.140 nm

r/R = 0.550 , It is between 0.414 and 0.732 (consult Table

13.2) , the CN number for Fe+2 ion is 6 ; this is also the CN of
O-2, since there are equal number of cations and anions. The
predicted structure will be Rock Salt, which is AX type
structure having CN = 6

Density calculation from the knowledge of crystal structure

Example Problem 10.5

Calculate the linear density of Ca+2 and O-2 ions in ions per nm in the
[110] direction of CaO which has the NaCl structure. (ionic radii: Ca+2=
0.106 nm and O-2 = 0.132 nm

Calculate the planar density of Ca+2 and O-2 ions in ions/nm2 on the
(111) plane of CaO.

Same for Ca+2 ions

2.14 g/cm3
The handbook value of for the density of NaCl is 2.16 g/cm 3

Positions of tetrahedral sites in FCC unit cell

Positions of tetrahedral sites in unit cell

8 tetrahedral positions in FCC lattice and 24 in BCC lattice

4 Sites available for FCC unit cell

FCC

( , , )

(, , )

FCC
BCC
12 Sites available for BCC unit cell

BCC

In FCC unit cell, 8 tetrahedral sites are positioned within the cell, at the general
fractional Coordinates (n/4,n/4,n/4) where n = 1 or 3, e.g., (,, , ) or (, , )

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08-Nov-13

Positions of tetrahedral sites in unit cell

AX type crystal structures

Type III
When CN = 4
Ions are tetrahedrally Coordinated

Zinc Sulphide (ZnS) Crystal Structure

(Zinc Blende or Sphalerite)

Zinc Sulphide (ZnS) Crystal Structure

(Zinc Blende or Sphalerite)

rZn/RS=0.60/1.84=0.32 (tetrahedral)
S-2

Zn+2

4 S atom per unit

cell so only 4
tetrahedral sites
can be occupied
to achieve charge
balance

4 tetrahedral
sites are
occupied per unit
cell to maintain
charge neutrality
Bonding is
typically covalent

Examples of other Zinc blende structures

Important Ceramic material which form such structure is SiC
Electronic materials are GaAS, ZnTe, etc.
Diamond also form Zinc blende structure

Diamond

Example 3.16
Calculating the Theoretical Density of GaAs
The lattice constant of gallium arsenide (GaAs) is 5.65 . Show that
the theoretical density of GaAs is 5.33 g/cm3.
For the Zinc blende GaAs unit cell, there are four Ga
and four As atoms per unit cell.
Each mole (6.023 1023 atoms) of Ga has a mass of
69.7 g. Therefore, the mass of four Ga atoms will be (4
* 69.7/6.023 1023) g.

Silicon carbide (carborundum)

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08-Nov-13

Each mole (6.023 1023 atoms) of As has a mass of 74.9

g. Therefore, the mass of four As atoms will be (4 *
74.9/6.023 1023) g. These atoms occupy a volume of
(5.65 10-8)3 cm3.

density

mass
4(69.7 74.9) / 6.023 10

8
3
volume
(5.65 10 cm)

Check the covalent character of ceramic compounds

23

Hence, the theoretical density of GaAs is 5.33 g/cm3.

Example Problem 10.7

AmXp Type Crystal Structures

Calculate the density of zinc blende (r(Zn2+) = 0.060 nm,

r(S2-) = 0.174 nm)

If the charges on the cations and anions are not same, a compound can
exist with the chemical formula AmXp ,where m and/or p 1
AX2 type compounds
Examples CaF2 (fluorite), UO2, PuO2, ThO2, BaF2, PbMg2

Fluorite Structure (AX2)

Fluorite Structure (AX2)

rca+2/RF- = 0.8
CN = 8

rca+2/RF- = 0.8
CN = 8 for

Ca+2

What is CN for F-?

Half of the centre cube positions are occupied by Ca+2 ions

Ca+2 occupy FCC lattice

8 tetrahedral
sites are
occupied by Fions to maintain
charge neutrality

Many octahedral
sites are vacant.
In UO2 this
allows to
accommodate
fission products

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08-Nov-13

Fluorite Structure (AX2)

Fluorite Structure (AX2)

Examples: some Halides (CaF2, BaCl2...); Oxides (ZrO2...)

Calculate the density of UO2 (r (U+4) = 0.105 nm and r(O-2) = 0.132 nm

Anti Fluorite Crystal Structure

The reverse of the fluorite structure
Anions (F-) goes on the FCC lattice sites
Cations will fill up the tetrahedral sites

3
+

= 4 + 2
4

A2X type structures (A is cation and X is anion)

Examples
Li2O, Na2O, K2O and Mg2Si
The handbook value of for the density of UO2 is 10.96

Structure of Li2O

g/cm3

Connections of tetrahedrons in Antifluorite

structures

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08-Nov-13

Bond strength and coordination number

Octahedral sites in HCP unit cell

Two atoms shared by 2 cells

12 atoms shared by six cells

Bond strength of ionic bond donated from a cation to anion is

defined as
Formal charge on the cation divided by its coordination
number

Octahedral
sites

Example:
Silicon with a valence of 4 has tetrahedral coordiantion (CN=4) ,
the bond strength is 4/4 = 1
Al+3 ions in octahedral coordiantion (CN=6) , the bond strength
is 3/6 = 1/2

A2X3 structures
Hexagonal closed pack structures
Coordination number of cation is 6 and anion is 4
2/3 octahedral sites are filled
Structure name is Corundum
Examples
Al2O3, Fe2O3, Cr2O3, Ti2O3, V2O3, Ga2O, Rh2O3

Corundum (Structure of Al2O3)

CN= 6
Bond strength is
4 Al+3 ions are near to O-2
There are 6 O-2 ions available per unit cell so for
charge neutrality we need 4Al+3 ions)
6 octahedral sites are available in HCP
Only 4 (2/3 sites will be occupied in HCP unit cell)
Such charge balance can only be possible in HCP
structure.

O-2

Al+3

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08-Nov-13

Formation of Octahedrons in Corundum structure

Perovskite structures
ABO3 type structures (have two types of cations)
A is a divalent cation (La, Ba, Sr, Ca, etc)
B is tetravalent cation (Fe, Co, Ni, Mn, Ti, etc)
O is oxide anion
Examples BaTiO3, CaTiO3, LaMnO3, etc.

Perovskite structures

Formation of octahedrons in pervoskite structures

How many O-2 ions for Ti+4?

Grey sphere = B cation (Ti) (0,0,0)

(corners of cube)

Ti+4 is surrounded by 6 O-2 ions

Green, blue, cyan sphere = O anion

(occupy octahedral sites at the edges)

How many O-2 ions for Ca+2?

Ca+2 is surrounded by 12 O-2 ions

Purple sphere= A, Ca (Cation)

(occupy octahedral site at the centre of
Cube, (, , )

How many O-2 ions are near to

each O-2?
Each O-2 ions are near to 8 O-2 ions

Calculate bond strength in CaTiO3 pervoskite

Bond strength of Ti-O bond =?

Effect of size of A and B cations on the Perovskite

structures
SrTiO3 an ideal
Perovskite structure

CN for Ti is 6 , the bond strength is = 4/6= 2/3

Bond strength of Ca-O bond =?

CN for Ca is 12 , the bond strength is = 2/12= 1/6
Also, How many O-2 ions are coordinated with Ti+4
and Ca+2 ?

2 Ti+4 , 4 Ca+2
Total bond strength of Ti-O bond = 2(2/3) = 4/3
And Total bond strength of Ca-O bond = 4(1/6)

What is a in terms of cation A and O-2 ion radius?

a = (rO+rA)

Total bond strength in structure = 4/3+4/6= 2

It is equal to the oxygen valency.

What is a in terms of cation B and O-2 ion radius?

a = 2(rO+rB)

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08-Nov-13

GoldSchmidts Tolerance factor

() =

What happens when tolerance factor deviates from ideal

value?

Cubic structure exists if 0.89 < t 1

If A ion is smaller than ideal then t will be smaller than ideal value.

Problem

[BO6] octahedra will tilt in order to fill space.

Calculate GoldShmidts tolerance factor for SrTiO3? Ionic radii for Sr+2 =
0.144 nm ,Ti+4 = 0.0605 nm ,O-2 = 0.140 nm
For ideal cubic pervoskite t= 1, such as SrTiO3
Higher or lower values than ideal value (1) changes the
structure symmetry

Doubled perovskite structure

Changing the composition from ideal ABO3

Non-stoichometry in perovskite structures exist

SrFeOx (where 2.5x3)
By oxidizing or reducing , oxygen content can be varied

By doubling all the edges of cubic unit cell it is possible to occupy

equivalent positions with atoms of different elements.

Such structures are called perovskite superstructues and also called as

doubled perovskite.

In SrFeO2.875 , there will be some Fe+3 and the other Fe+4 ions. Oxygen
vacancies ordered so that FeO5 square pyramids formed.
Oxygen vacancies
provide oxide ion
conductivity to the
pervoskites, hence
used in Solid oxide
fuel cells

Barium titanate

Perovskite Superconductor
High temperature superconductor (YBa2Cu3O6.96) is superstructure
of pervoskite.

Perovskite structure
Piezoelectricity
High dielectric strength
Ferroelectricity (exhibition of spontaneous
polarisation and re-orientation of polarisation)
Curie temperature (120 C). It is tetragonal below 120
C (ferroelectric) but above 120 C it is cubic a perfect
pervoskite (paraelectric)
Uses:
Ultrasonic equipment, capacitors, piezoelectric devices,
doped titanate have applications in semiconductors.

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08-Nov-13

Ferroelectricity in BaTiO3

Ferroelectricity in BaTiO3

Ferroelectricity in BaTiO3

Ferroelectricity in BaTiO3

Ferroelectricity in BaTiO3

Ferroelectricity in BaTiO3

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08-Nov-13

Spinel structures (AB2X4)

Home work problems

The spinels have general formula AB2O4

10.2.5-10.2.24

AII is divalent cation e.g, Fe, Cr, Mn, Mg, Co, Ni, Cu, Zn, Cd, Sn

Principles of Materials Science and Engg.

3rd Edition
By W. F. Smith

BIII is trivalent cation e.g, Al, Ga, In, Ti, V, Cr, Mn, Fe, Co, Ni

X is O, S, Se
Named after the mineral spinel (MgAl2O4)

Spinel structure
Spinel structure is a cubic structure which is considered as
combination of the rock salt and zinc blende structures.

Spinel structure

O-2 ions are at face centred cubic position

For a subshell of this structure there are 4
atoms, 4 octahedral sites and 8 tetrahedral
sites.
12 total interstices to be filled up by three
cations, one divalent and 2 trivalent.
In each elementary cell 2 octahedral sites
are filled and one tetrahedral site
Each of these elementary cell are arranged
so as to form a unit cell containing 32
oxygen ions, 16 octahedral cations and 8
tetrahedral cations

Example :
MO.Fe2O3 (M is a divalent
metal ion)

Examples of Spinel structures

In normal spinel structures the A+2 (8M+2) ions occupy
8 tetrahedral sites and B+3 (16 Fe+3) ions are on 16
octahedral sites.
Examples
ZnFe2O4, CdFe2O4, MgAl2O4, FeAl2O4, CoAl2O4, NiAl2O4,
etc.

Inverse Spinel
Most common structure
The A+2 ions and half B+3 ions
are on octahedral sites, the
other half of B+3 are on
tetrahedral sites.
Examples
Ferrites (these have magnetic
properties) e.g.,
Fe3O4, FeMgFeO4, FeTiFeO4,
ZnSnZnO4, etc.

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08-Nov-13

Pauling rules

Pauling rules

First Rule

Second Rule

A Coordination polyhedron of anions is formed about

each cation in the structure.

Stable structures only form in ionic compounds by achieving local

electrical neutrality.

The cation-anion distance is determined by the sum of

radii.

In a stable structure the total strength of the bonds reaching an anion from all
surrounding cations should be equal to the charge of the anion.

The coordination number (i.e, the number of anions

surrounding the cation ), is determined by the ratio of
radius of the two ions. (cation should be in contact with
anion to achieve stability)

Linus Pauling

Pauling rules

Formation of Anionic groups

Second Rule
The electrostatic valency (E.V) principle
E.V = charge on cation/C.N

Charge is exactly balanced on anion and cation , this is called isodesmic bond
and the bond strength are equal from all directions.

In this case, E.V > the charge on anion

i.e., 4/3>1/2*2, the oxygen are more strongly bonded to the central
coordination ion (Anisodesmic bond)

Formation of Anionic groups

Pauling rules
Third Rule

E.N difference is also less

than 2 bond is covalent
(Si = 1.9 and C = 2.55)

Cation coordination polyhedra form links at corner, faces and edges.

In the case, E.V = the charge on

anion,
the oxygen can bound tightly to the
central coordination ion and to the
ions outside the group (mesodesmic
bond)

Sharing corners will put the cations at the greatest distance from each other.

In the stable structures, corners and faces of the coordination polyhedra tend
to be shared.

What is isodesmic bond?

E.V = 4/4= 1
SiO4-4 a building block of silicate minerals

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08-Nov-13

Pauling rules

Pauling rules
Fourth Rule

Third Rule

Cations with high valency and low coordination numbers tend to not
share their coordinating polyhedra.
Paulings fourth rule says that highly charged cations will tend to be as far
apart as possible to minimize electrostatic repulsion.

Fifth Rule
The number of different kinds of constituents in a structure tends to be
small.
Stability decreases

There are only few different kinds of anions and cations sites in a crystal.
There are only octahedral, tetrahedral and cubic sites, most crystal will be
formed by occupying these small number of sites.

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