Fajans' Rules

Fajans' rules
In inorganic chemistry, Fajans' rules,

formulated by Kazimierz Fajans in
1923,[1][2][3] are used to predict whether a
chemical bond will be covalent or ionic,
and depend on the charge on the cation
and the relative sizes of the cation and
anion. They can be summarized in the
following table:
Chart illustrating the relationship between atomic and ionic radius
Ionic Character Covalent Character
Low positive charge High positive charge
Large cation Small cation
Small anion Large anion
Non-polar covalent bond (left), polar

covalent bond (center), ionic
bond(right)
Thus sodium chloride (with a low positive

charge (+1), a fairly large cation (~1 Å) and
relatively small anion (0.2 Å) is ionic; but
aluminium iodide (AlI3) (with a high
positive charge (+3) and a large anion) is
covalent.
Polarization will be increased by:
high charge and small size of the cation

Ionic potential Å Z+/r+ (= polarizing
power)
High charge and large size of the anion
The polarizability of an anion is
related to the deformability of its
electron cloud (i.e. its "softness")
An incomplete valence shell electron
configuration
Noble gas configuration of the
cation produces better shielding
and less polarizing power
e.g. Hg2+ (r+ = 102 pm) is more
polarizing than Ca2+ (r+ = 100
pm)
The "size" of the charge in an ionic bond

depends on the number of electrons
transferred. An aluminum atom, for
example, with a +3 charge has a relatively
large positive charge. That positive charge
then exerts an attractive force on the
electron cloud of the other ion, which has
accepted the electrons from the aluminum
(or other) positive ion.
Two contrasting examples can illustrate

the variation in effects. In the case of
aluminum iodide an ionic bond with much
covalent character is present. In the AlI3
bonding, the aluminum gains a +3 charge.
The large charge pulls on the electron
cloud of the iodine. Now, if we consider
the iodine atom, we see that it is relatively
large and thus the outer shell electrons are
relatively well shielded from the nuclear
charge. In this case, the aluminum ion's
charge will "tug" on the electron cloud of
iodine, drawing it closer to itself. As the
electron cloud of the iodine nears the
aluminum atom, the negative charge of the
electron cloud "cancels" out the positive
charge of the aluminum cation. This
produces an ionic bond with covalent
character. A cation having inert gas like
configuration has less polarizing power in
comparison to cation having pseudo-inert
gas like configuration.
Graph of percentage ionic character
The situation is different in the case of

aluminum fluoride, AlF3. In this case,
iodine is replaced by fluorine, a relatively
small highly electronegative atom. The
fluorine's electron cloud is less shielded
from the nuclear charge and will thus be
less polarizable. Thus, we get an ionic
compound (metal bonded to a nonmetal)
with a slight covalent character.
References
1. Fajans, K. (1923). "Struktur und
Deformation der Elektronenhüllen in
ihrer Bedeutung für die chemischen
und optischen Eigenschaften
anorganischer Verbindungen". Die
Naturwissenschaften. 11 (10): 165–
72. Bibcode:1923NW.....11..165F (http
s://ui.adsabs.harvard.edu/abs/1923N
W.....11..165F) .
doi:10.1007/BF01552365 (https://doi.
org/10.1007%2FBF01552365) .
2. Fajans, K.; Joos, G (1924).
"Molrefraktion von Ionen und
Molekülen im Lichte der
Atomstruktur". Zeitschrift für Physik.
23: 1–46. Bibcode:1924ZPhy...23....1F
(https://ui.adsabs.harvard.edu/abs/19
24ZPhy...23....1F) .
doi:10.1007/BF01327574 (https://doi.
org/10.1007%2FBF01327574) .
3. Fajans, K. (1924). "II. Die

Eigenschaften salzartiger
Verbindungen und Atombau" (http://w
ww.degruyter.com/view/j/zkri.1924.6
1.issue-1/zkri.1924.61.1.18/zkri.1924.
61.1.18.xml) . Zeitschrift für
Kristallographie - Crystalline Materials.
61 (1): 18–48.
doi:10.1524/zkri.1924.61.1.18 (https://
doi.org/10.1524%2Fzkri.1924.61.1.1
8) .
External links
Adrian Faiers. "Chapter 4: Chemical
Bonding" (http://www.chembook.co.uk/
chap4.htm) . Chemistry in Perspective.
chembook.co.uk.
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Fajans' rules

In inorganic chemistry, Fajans' rules,

Ionic Character Covalent Character

Low positive charge High positive charge

Large cation Small cation

Small anion Large anion

Non-polar covalent bond (left), polar

Thus sodium chloride (with a low positive

Polarization will be increased by:

high charge and small size of the cation

The "size" of the charge in an ionic bond

Two contrasting examples can illustrate

Graph of percentage ionic character

The situation is different in the case of

3. Fajans, K. (1924). "II. Die

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