AN INTRODUCTION TO

FAJAN’S RULES

D. JIM LIVINGSTON
FACULTY OF CHEMISTRY
St. JOHN’S COLLEGE
 INTRODUCTION

Observations Not all ionic compounds have high melting points.

Some covalently bonded compounds have higher than

expected boiling points due to dipoles in their structure

Reason in many substances bonding is not 100% ionic or covalent

 INTRODUCTION

Observations Not all ionic compounds have high melting points.

Some covalently bonded compounds have higher than

expected boiling points due to dipoles in their structure

Reason in many substances bonding is not 100% ionic or covalent

Ideal ionic
compound completely separate, spherical ions
electron densities are apart from each other

However, if the positive ion has a high charge density it can distort the
negative ion by attracting the outer shell electrons to give an area of electron
density between the two species ... a bit like a covalent bond
 Polarising power
the capability of cation to distort the electron charge cloud of an
anion
It is proportional to charge density.

Charge density is the ratio of charge to

volume.

Polarising power α Charge density.

More the charge density, greater is the

polarising power for that cation.
 Polarizability
property of an anion to become polarized through the deformation
of electron charge cloud by cation.

Polarizability of an anion increase

with increase in anionic size or
anionic charge.

If the polarizability of an anion

increase, then covalent character
of the resulting compound
increases
 Fajans' Rules
Rules formulated by Kazimierz Fajans in 1923,

used to predict whether a chemical bond is expected to be

predominantly ionic or covalent
The rule can be stated on the basis of 4 factors, which are:
The cation with smaller size have higher polarising power
The anions with large size have high polarisability
high charge on the cation or the anion
Cations with pseudo inert gas configuration, ns2p6d10 or with
inert pair configuration,d10(n+1)s2 have high polarizing power

FAVOURS COVALENCY
 FAJAN’S RULES

A COMPOUND IS MORE LIKELY TO HAVE

SOME COVALENT CHARACTER IF...

• THE CATION IS SMALL AND/OR HAS A HIGH CHARGE - HIGHLY POLARISING

• THE ANION IS LARGE AND/OR HAS A HIGH CHARGE - HIGHLY POLARISABLE

 FAJAN’S RULES

A COMPOUND IS MORE LIKELY TO HAVE

SOME COVALENT CHARACTER IF...

• THE CATION IS SMALL AND/OR HAS A HIGH CHARGE - HIGHLY POLARISING

• THE ANION IS LARGE AND/OR HAS A HIGH CHARGE - HIGHLY POLARISABLE

MORE COVALENT
CHARACTER
 FAJAN’S RULES

A COMPOUND IS MORE LIKELY TO HAVE

SOME COVALENT CHARACTER IF...

• THE CATION IS SMALL AND/OR HAS A HIGH CHARGE - HIGHLY POLARISING

• THE ANION IS LARGE AND/OR HAS A HIGH CHARGE - HIGHLY POLARISABLE

MORE COVALENT

MORE COVALENT
CHARACTER

CHARACTER
 FAJAN’S RULES

PROOF
Chlorides can be used to demonstrate changes in bond type as the positive charge
density increases due to higher charge (across Period 3) or larger size (down Group 1)

‘charge’ ionic rad. m.pt./°C solubility bonding

GREATER POSITIVE
CHARGE DENSITY
Period 3 NaCl 1+ 0.095nm 808 soluble ionic
MgCl2 2+ 0.065nm 714 soluble ionic
AlCl3 3+ 0.050nm 180 hydrolysed covalent
SiCl4 4+ 0.041nm -70 hydrolysed covalent

GREATER POSITIVE
CHARGE DENSITY

Group 1 LiCl 1+ 0.060nm soluble cov. character

NaCl 1+ 0.095nm soluble ionic
KCl 1+ 0.133nm soluble ionic
RbCl 1+ 0.148nm soluble ionic
 Application of Fajan’s rule with
examples

LiBr is more covalent than KBr

Reason: Size of Li+ 90 pm is less than K+ 152 pm

covalent character of lithium halides is in the order

LiI > LiBr > LiCl > LiF

covalent character of NaCl, MgCl2, AlCl3 follows the order

Na+Cl- < Mg2+Cl2 < Al3+Cl3
Reason: Charge of cation increases

Cu+Cl- is more covalent than Na+Cl-

Reason: Cu+ has pseudo inert gas configuration

 QUESTIONS

Zinc (II) chloride is more covalent than magnesium chloride –

Why?

The melting point of KCl is higher than that of AgCl though the
crystal radii of Ag+ and K+ ions are almost the same

Arrange the following according to the increasing order of

covalency: LiF, NaF KF, RbF, CsF

Arrange the following compounds in the increasing order of its

solubility in water (polar solvent) AgF AgCl ABr AgI .
Why the thermal stability of metal(II) carbonates increases down
the group?