Ionic Bonding

Ionic Bonding, an Introduction

All conventional ionic compounds are solids and have the
following properties:
1. Crystals of ionic compounds are hard and brittle.
2. Ionic compounds have high melting points.
3. When heated to the molten state (if they do not
decompose), ionic compounds conduct electricity.
4. Many ionic compounds dissolve in high-polarity solvents
(such as water), and, when they do, the solutions are
electrically conducting.
Ionic Bonding
• According to the “pure” ionic model, some of the
outermost electrons have been completely transferred
from the element of lower electronegativity to the element
of higher electronegativity.
• This model is surprisingly useful although there is
evidence for some small degree of covalency even when
the electronegativity difference is very large.
• As we study the chemistry of the different groups, we will
see many examples of covalent character in supposedly
ionic compounds.
Ion Size
• The size of atoms decreases from left to right in a period
as a result of an increase in Zeff.
• The conversion of many atoms to ions results in a
significant change in size.
• For example, the metallic radius of sodium is 186 pm,
whereas its ionic radius is only 116 pm. Calculate the
volume of atom or ion!
Trends in Ionic Radii
• The cation radii become even smaller if the ions have a
multiple charge
• the negative ion is larger than the corresponding atom
Trends in Melting Points
• The ionic bond is a result of the attraction of one ion to the ions of
opposite charge that surround it in the crystal lattice.
• The melting process involves partially overcoming the strong ionic
attractions and allowing the free movement of the ions in the liquid
phase.
• The smaller the ion, the shorter the interionic distance; hence the
stronger the electrostatic attraction and the higher the melting point.
Hydrated Salts
• When an ionic compound crystallizes from an aqueous
solution, water molecules often become incorporated in
the solid crystal.
• These water-containing ionic compounds are known as
hydrates.
• In some hydrates, the water molecules are simply sitting
in holes in the crystal lattice, but in the majority of
hydrates, the water molecules are associated closely with
either the anion or the cation, usually the cation.
• Example : AlCl3•6H2O
Polarization and Covalency
• Even though most combinations of metals and nonmetals
have the characteristics of ionic compounds, there are a
variety of exceptions.
• These exceptions arise when the outermost electrons of
the anion are so strongly attracted to the cation that a
significant degree of covalency is generated in the bond;
that is, the electron density of the anion is distorted
toward the cation.
• This distortion from the spherical shape of the ideal anion
is referred to as polarization.
Fajan’s Rule
1. A cation will be more polarizing if it is small and highly
positively charged.
2. An anion will be more easily polarized if it is large and
highly negatively charged.
3. Polarization is favored by cations that do not have a
noble gas configuration
Fajans’ First Rule
One of the most obvious ways of distinguishing ionic
behavior from covalent behavior is by observing melting
points: those of ionic compounds (and network covalent
compounds) tend to be high; those of small molecule
covalent compounds, low.
Fajans’ Second Rule
• To illustrate the effects of anion size, we can compare
aluminum fluoride (m.p. 1290 C) and aluminum iodide
(m.p. 190 °C).
• The fluoride ion, with an ionic radius of 117 pm, is much
smaller than the iodide ion, of radius 206 pm.
• In fact, the iodide ion has a volume more than five times
greater than that of the fluoride ion
Fajans’ Third Rule
• The silver ion (Ag+), with an electron configuration of
[Kr]4d10, is a good example (among the others are Cu+,
Sn2+, and Pb2+).
• Since the ionic radius (and hence charge density) of the
silver ion is close to that of the potassium ion, for the
purely ionic model we might expect the melting points of
silver salts to be close to those of the corresponding
potassium salt.
The Ionic-Covalent Boundary
Unfortunately, there is no firm predictable boundary
between ionic and covalent behavior for solid compounds
of metals and nonmetals
Ionic Crystal Structures
The anions are much larger than the cations; thus, it is the
anions that form the array and the smaller cations fit in
holes (called interstices) between the anions. Before
discussing the particular types of packing, however, we
should consider general principles that apply to ionic
lattices:
• Ions are assumed to be charged, incompressible,
nonpolarizable spheres.
• Ions try to surround themselves with as many ions of the
opposite charge as possible and as closely as possible.
• The cation-to-anion ratio must reflect the chemical
composition of the compound.
• the packing arrangement adopted by an ionic compound
is usually determined by the comparative sizes of the ions
• The numerical value, r+/r-, is called the radius ratio.
The Cubic Case
The best way to picture the ionic lattice is to consider the anion
arrangement first and then look at the coordination number of
the interstices in the anion arrays. The packing arrangement that
can accept the largest cation is the simple cubic. In this
arrangement, there are eight anions surrounding each cation.
The Octahedral Case
When the radius ratio falls below 0.732, the anions in the cesium chloride
structure are no longer held apart by the cations. The potential repulsions
between the anions cause the octahedral geometry to become the
preferred arrangement. For this smaller radius ratio, six anions can fit
around a cation without touching one another. The actual anion
arrangement is based on the cubic close-packed array in which there are
octahedral holes and tetrahedral holes. Figure 5.5 shows the array with an
O marking the location of the octahedral holes in which the cations can fit.
In the octahedral packing, all the octahedral holes are filled with cations
and all of the tetrahedral holes are empty.
The Tetrahedral Case
• Ionic compounds in which the cations are very much smaller than the
anions can be visualized as close-packed arrays of anions, with the
cations fitting into the tetrahedral holes (the octahedral holes are
always empty). Both hexagonal close-packed (hcp) and cubic close-
packed (ccp) arrangements are possible, and usually a compound will
adopt one or the other, although the reasons for particular
preferences are not well understood. Figure 5.9 shows the cubic
close-packed array; a T marks the location of the tetrahedral holes.
The Bonding Continuum
• The bonding between atoms is depicted as one of
the three options: covalent, ionic, or metallic.
• In reality, bonding is often a mixture of two or even
all three components.
• Polarization of ions can result in covalent character
of ionic bonds
• Compounds of two nonmetals can have an ionic
component to their bonding (polar covalency).
• Electron density profiles for four points on this
continuum: the pure covalent, a polar covalent
bond, a polarized ionic bond, and a pure ionic
bond.
• The ratio of ionic to covalent character can be
defined as the difference in electronegativities,
EN, between the pairs of atoms.
• pairs of atoms with EN close to zero will possess
essentially pure covalent bonds with equally
shared electrons, whereas those with EN > 3.0
are regarded as purely ionic
The Allred-Rochow Electronegativity
Scale
 The Bond Triangle
• This bond triangle (or more correctly,
the Van Arkel–Ketelaar triangle) has
a horizontal axis of electronegativity.
• The metallic-covalent limits of this
axis correspond to the change in
bonding from the delocalized bonding
in the metallic structure to the overlap
of orbitals in particular directions
(covalent).
• Elements lie along this axis, from
purely metallic (such as cesium) to
purely covalent (such as fluorine).
• The EN becomes the vertical axis in
this plot, the left side of the triangle
representing the metallic to ionic
transition and the right, the covalent
to ionic transition.