Ionic Bonding

An ionic bond is a type of chemical bond formed through electrostatic attraction between two
oppositely charged ions. Ionic bonds are formed between a metal and a nonmetal ion. Pure ionic
bonding is not known to exist. All ionic compounds have a degree of covalent bonding. The larger
the difference in electronegativity between two atoms, the more ionic the bond. Bonds with partially
ionic and partially covalent character are called polar covalent bonds.

Mechanism

The metal donates one or more electrons, forming a positively charged ion or cation with a
stable electron configuration. These electrons then enter the non metal, causing it to form a
negatively charged ion or anion which also has a stable electron configuration. The
electrostatic attraction between the oppositely charged ions causes them to come together
and form a bond.

For example, common table salt is sodium chloride. When sodium (Na) and chlorine (Cl) are
combined, the sodium atoms each lose an electron, forming cations (Na+), and the chlorine
atoms each gain an electron to form anions (Cl−). These ions are then attracted to each
other in a 1:1 ratio to form sodium chloride (NaCl).

Na + Cl → Na+ + Cl− → NaCl

The removal of electrons from the atoms is endothermic and causes the ions to have a
higher energy. There may also be energy changes associated with breaking of existing bonds
or the addition of more than one electron to form anions. However, the attraction of the
ions to each other lowers their energy.

Ionic bonding will occur only if the overall energy change for the reaction is favourable –
when the bonded atoms have a lower energy than the free ones. The larger the resulting
energy change the stronger the bond. The low electronegativity of metals and high
electronegativity of non-metals means that the energy change of the reaction is most
favorable when metals lose electrons and non-metals gain electrons.

Ionic structure
Ionic compounds in the solid state form lattice structures. The two principal factors in determining
the form of the lattice are the relative charges of the ions and their relative sizes. Some structures
are adopted by a number of compounds; for example, the structure of the rock salt sodium chloride
is also adopted by many alkali halides, and binary oxides such as MgO.
Strength of an ionic bond
For a solid crystalline ionic compound, the enthalpy change in forming the solid from gaseous ions is
termed the lattice energy. The experimental value for the lattice energy can be determined using the
‘Born-Haber cycle’. It can also be calculated using the ‘Born-Landé equation’ as the sum of the
electrostatic potential energy, calculated by summing interactions between cations and anions, and
a short range repulsive potential energy term. The electrostatic potential can be expressed in terms
of the inter-ionic separation and a constant (Madelung constant) that takes account of the geometry
of crystal. The Born-Landé equation gives a reasonable fit to the lattice energy of e.g. sodium
chloride where the calculated value is -756 kJ/ml which compares to -787 kJ/mol using the Born-
Haber cycle.

Polarization effects
Ions in crystal lattices of purely ionic compounds are spherical; however, if the positive ion is small
and/or highly charged, it will distort the electron clould of the negative ion, an effect summarised in
‘Fajan’s rules’. This polarization of the negative ion leads to a build-up of extra charge density
between the two nuclei, i.e., to partial covalency. Larger negative ions are more easily polarized, but
the effect is usually only important when the positive ions with charges of 3+ (e.g., Al 3+) are involved.
However, 2+ ions (Be2+) or even 1+ (Li+) show some polarizing power because their sizes are so small
(e.g., Li is ionic but has some covalent bonding present). Note that this is not the ionic polarization
effect which refers to displacement of ions in the lattice due to the application of an electric field.

Electrical conductivity
Ionic substances in solution conduct electricity because the ions are free to move and carry the
electrical charge from the anode to the cathode. Ionic substances conduct electricity when molten
for the same reason i.e. that ions are free to move.

Some ionic compounds conduct electricity when solid. This is due to migration of ions under the
influence of an electric field. These compounds are known as ‘fast ion conductors’