FAJANS’ RULE

COVALENT CHARACTER
OF IONIC BOND
 FAJANS’ RULE
• Formulated by the Polish-born chemist Kasimir Fajans in 1923/4, these rules
govern the degree of nonpolar character (covalency) present in ionic
compounds.

• Theoretically, the bonding in these compounds is purely ionic – an attraction

between positive and negative ions.

• In practice, however, the electrons on the negative ion (the anion) can also be
attracted towards the positive ion (the cation), distorting the shape of the anion
and resulting in a degree of covalency (electron sharing).
 FAJANS’ RULE

Polarizability =
the ease in which the
electron cloud of a particle
can be distorted
 FAJANS’ RULE (Polarization)
Polarization will be increased by:-

1. High charge and small size of the cation

Z+/r+ (= polarizing power)

2. High charge and large size of the anion

The polarizability of an anion is related to the deformability of its electron
cloud

3. An incomplete valence shell electron configuration

Noble gas configuration of the cation better shielding less polarizing
power
i.e. charge factor in (1) should be effective nuclear charge
e.g. Hg2+ (r+ = 102 pm) is more polarizing than Ca2+ (r+ = 100 pm)
• Linus Pauling dealt with variations in polarity in terms of the degree of ionic
character in covalent bonds.

• Fajans, discussed the variation in the degree of nonpolar/covalent

character/covalency in ionic compounds in terms of polarization effects.

• Fajans’ rules:
- focus on size and charge relationships
- electronic configuration of the cation

Charge density = charge

size
FOR CATION
• Nonpolar (or covalent) character increases with decreasing cation size or
increasing cation charge

• Very small cations or cations with high charge density consequently tend to distort
or polarize the electron cloud around the anion. The greater the polarization of the
anion the more nonpolar (or covalent) the bond between the atoms.

FOR ANION
• Nonpolar (or covalent) character increases with an increase in anion size or
anion charge.

• The larger the anion or the higher its negative charge the more easily it is polarized
by cations because the electrons are held more loosely.
 FAJANS’ RULE
A COMPOUND IS MORE LIKELY TO HAVE
SOME COVALENT CHARACTER IF...

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

* it is “highly polarizing” and attracts electrons in the anion

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

* it is “highly polarizable” and electron cloud will be easily distorted
Nonpolar (covalent) character non-noble gas configuration than
for noble gas type cations.

• Cations with eight electrons structures cause less distortion, and undergo less
distortion themselves, than those with 18 electron structures (pseudo-noble gas
structures).

• If we compare cations of about the same size (Na+, Cu+), the pseudo-noble gas
cation has a much higher nuclear charge and the d electrons in the 18 electron
outer shell do not shield the nuclear charge effectively.
Cu+ : [Ar] 3d10 Na+ : [Ne] Size and charge
(Pseudo noble gas configuration) (Noble gas configuration) are
Cu+ Na+ almost
(0.96 Å) (0.95 Å) same.
No. of proton = 29 No.of proton = 11
Ø An anion near a Cu+ ion, compared with a Na+ ion, behaves as though it
were under the influence of a greater ionic charge and is distorted to a
greater extent.

Ø The spherical filled d electron cloud is also more easily polarized by anions
than is an eight electron shell.

Ø This results in some polarization of a pseudo-noble gas cation by the anion

 Covalent Characteristic

• Physical properties of ionic compounds such as melting and boiling points,

solubility and conductivity etc are affected by the covalency of the ionic bonds.
Consider the following examples:

• Fajans described as the covalency increases, solubility decreases and melting point
also decreases. So
– Covalent character increase with increase of size of the anion

MgS is less soluble than MgO

– Covalent character increase with decrease of size of the cation
Example: the melting point of BeCl2 = 405 °C and CaCl2 = 772 °C
 Covalent Characteristic

• Fajan’s described as
– Covalent character increases with increasing charge on either ion
• Fe(OH)3 is much less soluble than Fe(OH)2
• Fe3+ has higher charge, thus higher polarizing power than Fe2+, thus
higher covalent character

– Covalent character is greater for cation with non-noble gas configuration

• Transition metal are generally less soluble than those of alkali and
alkaline earth metals
• The melting point of HgCl2 = 276 °C, CaCl2 = 772 °C
 Conclusions: Fajans Rule

1. For a given cation, covalent character increases with increasing anion

size.

2. For a given anion, covalent character increases with decreasing cation

size.

3. The covalent character increases with increasing charge on either ion.

4. Covalent character is greater for cations with non-noble gas electronic

configurations.

A greater covalent character resulting from a soft-soft interaction is related with

lower solubility, color and short interionic distances, whereas hard-hard
interactions result in colorless and highly soluble compounds