CHM 224 Structure and Bonding Note 2

Ionic Solids

Part of one layer of a close packed

arrangement of equal-sized spheres containing hexagonal motifs

Layer A (Red) Layer A (Red) and Layer B (Grey)

Layer A (Red), B (Grey) and C (Blue) (ccp) Layer A (Red), B (Grey) and A (Red)
(hcp)
ABABAB…. Arrangement ABCABC….. Arrangement
Defects in Solids
All pure solid substances do not have ideal lattices in which every site is occupied by the correct type
of atom or ion. Perfect lattices are possible only at a temperature of 0 K. Above this temperature,
lattice defects are always present. The increase in entropy produced after a defect is created in the
structure of a solid substance is greater than the energy needed to create the defect. Hence, real
crystals are never perfect.
Types of Lattice Defects
Defects can occur in stoichiometric and non-stoichiometric compounds.
Stoichiometric Defects
1. Schottky defect: This type of defect consists of an atom or ion pair vacancy (missing) in a crystal
lattice, but the stoichiometry of the compound or electrical neutrality is retained. Vacant atom
sites may be present in a metal lattice or ionic crystal. Example of this type of defect in ionic
lattices are a vacant cation and a vacant anion site in an MX salt. Another example is a vacant
cation site and two vacant anion sites in a MX2 salt. Holes are present where ions are expected on
the basis of the ideal lattice. Schottky defect has been found to occur in sodium chloride,
potassium chloride, caesium chloride and potassium bromide.
2. Frenkel defect: in this defect, an atom or ion occupies a normally vacant site, leaving its ‘own’
site vacant. Example is found when silver bromide adopts an NaCl structure type. The central
silver ion is in an octahedral hole with respect to the face centred cubic arrangement of bromide
ions. Migration of the Ag+ ion to one of the previously unoccupied tetrahedral holes generates a
Frenkel defect in the lattice. This defect type is possible if there is a relatively large difference in
size between cation and anion. In AgBr Frenkel defect, the cation must be accommodated in a
tetrahedral hole which is significantly smaller than the octahedral site. Generally, Frenkel defects
are found in lattices which are relatively open and in which coordination number is low. Other
example of compound with Frenkel defect include zinc sulphide, silver chloride, and silver
iodide.
Schottky and Frenkel defects occur in stoichiometric crystals. They are studied simply by measuring
the density of the crystal extremely accurately. Low concentration of Schottky defects lead to the
observed density of a crystal being lower than that calculated from X-ray diffraction and data based
on the size and structure of the unit cell. On the other hand, no such differences will be observed in
the case of Frenkel defect since it does not involve a change in the number of atoms or ions present.
Crystals with Frenkel defects have only one type of hole, but crystals containing Schottky defects
have holes for both positive and negative ions. Conduction may arise by using either one type of hole
or both types.
Non-stoichiometric Defects
There are compounds having the ratio of the number of atoms of one kind to the number of the other kind
not corresponding exactly to the ideal whole number ratio implied by the formula. The law of constant
composition is not obeyed. Example of such compounds are Fe0.84O, Fe0.9S instead of FeO and FeS
respectively. This is due to the presence of excess or deficiency of metal ions. This makes the structure
irregular or to contain defects. Non-stoichiometric defects are of two types – metal excess defects and
metal deficiency defects.
3. Metal excess defects: This defect type occurs in two ways:
a. Formation of Farbe-centres (F-centres) – A negative ion may be absent from its lattice site,
leaving a ‘hole’ which is then occupied by an electron to maintain electrical neutrality.
Consider an ionic solid with A+B- ions in the following arrangement:

This is similar to a Schottky defect since there are ‘holes’ and not interstitial ions but only one
‘hole’ is formed rather than a pair of hole in Schottky defect. This type of defect is formed by
crystals which would be expected to form Schottky defects. This is exemplified when
compounds such as NaCl, KCl, LiH or δ-TiO are heated with excess of their constituent metal
vapours or treated with high radiation, and they become deficient in the negative ions. Their
formula may be represented by AX1-δ where δ is a small fraction. Non-stoichiometric forms
of NaCl and KCl are yellow and bluish lilac in colour respectively (similar to cationic flame
colouration). The more F-centres present the greater the intensity of the colouration. Solids
with F-centres are paramagnetic since the vacant sites contain unpaired electrons. When
irradiated with light they become photoconductors (negative or n-type semiconduction)
b. Formation of interstitial ion and electrons – Metal excess defects also occur when an extra
positive ion occupies an interstitial position in the lattice, and electrical neutrality is preserved
by the inclusion of an interstitial electron. Their composition may be represented by the
general formula A1+δX. This type of defect is similar to a Frenkel defect since the ions occupy
interstitial positions, but there are no ‘holes’ and interstitial electrons are present.
 This type of defect is the more common metal excess defect and is formed in crystals which
would be expected to form Frenkel defects, that is, the ions are appreciably different in size,
have a low coordination number, and have some covalent character. Examples include ZnO,
CdO, Fe2O3, and Cr2O3. If the oxide is heated in oxygen and then cooled to room
temperature, its conductivity decreases because the dioxygen oxidizes some of the interstitial
ions which subsequently remove interstitial electrons and conductivity is reduced. The
crystals having this type of defect also contain free electrons and if these migrate, they
conduct electricity but to a less extent compared to fused metal salts or aqueous solution of
the salts. Hence, they are semiconductors with n-type semi-conductivity mechanism.
Compounds with this type of defect are usually coloured when heated (e.g., ZnO is white
when cold but yellow when hot).
4. Metal deficiency defects: Metal deficient compounds may be represented by the general formula
A1-δX. The defect type occurs in two ways, and both require variable valency of the (transition)
metal.
a. Missing positive ion defect – This occurs if a positive metal ion is absent from its lattice site
and the charges are balanced by an adjacent metal ion having an extra positive charge.

Examples include FeO, NiO, δ-TiO, FeS and CuI. If an Fe2+ ion is missing from its lattice site
in FeO, then there must be two Fe3+ ions somewhere in the lattice to balance charges. Crystals
with metal deficiency defects are semiconductors. As electron ‘hops’ from one metal ion to
another (from A+ to the positive centre A2+) electrons are transferred across the structure and
at the same time the positive hole migrates in the opposite direction across the structure. This
is called positive hole or p-type semiconduction.
 If a defect oxide of this type is heated in dioxygen, its room temperature conductivity
increases, because the dioxygen oxidizes some of the metal ions, and this increases the
number of positive centres.
b. Formation of extra interstitial negative ions – it may be possible in principle to have an extra
negative ion in an interstitial position and to balance the charges by means of an extra charge
on an adjacent metal ion. However, since anions are usually larger, it would be difficult to fit
them into interstitial positions. Hence, no example of crystals with such negative interstitial
ions are known presently.

Diffraction Methods
Diffraction techniques are the most important approach to the analysis of crystalline solids. The solid state
Nuclear Magnetic Resonance (NMR) spectroscopy is a powerful technique but does not provide a
detailed and complete picture of a crystalline solid. More important techniques by which ionic solids can
be structurally determined include X-ray diffraction, neutron diffraction and electron diffraction methods.
X-ray Diffraction Method
X-rays are produced in the laboratory by bombarding a metal target with high energy electrons. These
electrons knock out inner shell electrons of the core orbitals in the metal. The empty core orbitals are then
refilled by electronic transitions that lie in the X-ray region of the electromagnetic spectrum. The excess
energy is released as X-rays, the wavelength of which depends on the element the target is made up of.
Different ions scatter X-rays to differing extents depending on the total number of electrons in the ion,
and consequently different types of ions can generally be distinguished from one another.
X-ray diffraction technique is widely used for the determination of the structures of molecular solids and
of non-molecular or ionic solids. Its application has been expanded to determine polymers, proteins, and
other macromolecules. There are two X-ray diffraction techniques – X-ray Powder Diffraction or Powder
X-ray Diffraction (PXRD) and Single Crystal X-ray Diffraction (SC-XRD) and their instruments are
called Diffractometers.
X-ray powder diffraction technique is used for investigating solids with infinite lattice structures and to
assess the purity and crystallinity of materials. Each crystalline phase has a unique diffraction pattern
which is compared to a database for identification. Powder XRD gives information about the phase purity
(qualitative and quantitative), crystallinity (amorphous content, particle size and strain), unit cell size and
shape (from peak positions) and the crystal structures in simple cases. It can detect isomorphism in solid
substances.
The reference pattern has sharp well-defined peaks, and the positions of the peaks are determined by the
lattice. A plot of the intensity of the peaks (in atomic units, a.u.) against the angle 2θ (in degrees)
represents the diffraction pattern of the amorphous or crystalline solid. For example, the powder XRD
pattern for pyridine-3-carboxamide or nicotinamide is shown below (Source = Royal Society of
Chemistry, RSC):

Single crystal X-ray diffractometer typically consist of four parts:

i) An X-ray source
ii) A mounting for the single crystal
iii) Turn tables (to allow variation in the angle of incident of X-ray beam)
iv) An X-ray detector
The X-ray source provides monochromatic (single wavelength) radiation. The detector directs X-rays that
are scattered or reflected from the crystal. For two waves travelling in-phase with the lattice spacing (d)
between them, the additional distance travelled by the second wave is given as 2dsinθ, where θ is the
angle of incidence or the angle of reflection or scattering. X-rays scattered by atoms in the crystalline
sample and scattering from different atoms interfere with one another either constructively or
destructively.
Limitations of X-ray Diffraction Methods
1. The location of light atoms such as hydrogen in the presence of much heavier atoms is difficult
and, sometimes impossible to know accurately
 2. X-ray diffraction is seldom able to identify the state of ionization of the species present. It is only
for a few substances (e.g., NaCl) that the electron density distribution have been determined with
sufficient accuracy.
Neutron Diffraction Method
This diffraction technique is a useful source of structural information on crystalline materials. It is
also useful for spectroscopy and structure of liquids and glasses. Neutrons are produced by using a
nuclear reactor or a spallation source. Spallation neutrons are produced by bombarding a metal target
with pulses of protons. In neutron diffraction, the neutrons are diffracted by nuclei of the atoms. The
technique is uniquely suitable for studying magnetic materials. It is good for looking at weak X-ray
scatters such as hydrogen and oxygen in the presence of heavy metals and for crystal structure
refinement from powder diffraction data. Neutron diffraction is however an expensive technique.
Differences Between X-ray and Neutron Diffraction Techniques

S/No. X-ray Diffraction Neutron Diffraction

1. Atomic scattering power varies smoothly Power scattering varies erratically with
with atomic number or number of electron atomic number

2. Scattering power decreases as the scattering Scattering power is constant as the scattering
angle increases angle changes.

3. Rays are scattered by electrons in atom Neutrons are scattered by nuclei which are
which are approximately equal to the much smaller in wavelength than that of
wavelength of X-rays neutron.

4. X-rays diffraction is insensitive to magnetic Neutrons are scattered by magnetic moments

moments as the electron spin of magnetic material
interact with neutron spin resulting in
scattering.

5. Rays are available as intense beams Neutrons have low intensity beams.

6. Rays are strongly absorbed by all elements Neutrons are weakly absorbed by most
except those with low atomic numbers materials but good for investigating light
atoms

Electron Diffraction Technique

Molecules do diffract electrons and electron diffraction apparatus maintained under high vacuum is
arranged so that the electron beam interacts with a gas stream emerging from a nozzle. The electric field
of the atomic nuclei in the sample are responsible for most of the electron scattering observed.
The diffraction data mainly provide information about intermolecular bond parameters. The initial data
relate the scattering angle of the electron beam to intensity. Electron diffraction is not limited to the study
of gases, low energy electrons (10-200 eV) are also diffracted from the surface of a solid. The diffraction
pattern so obtained provides information about the arrangement of atoms on the surface of the solid
sample. This is known as Low Energy Electron Diffraction (LEED).
Electron diffraction is primarily used for phase identification, and unit cell determination on small
crystallites in the electron microscope. It can also give the space group and symmetry. This technique can
be used to obtain single crystal photographs from a microcrystalline substance and to get single phase
information from a multiphase sample.
Differences Between X-ray and Electron Diffraction Methods
S/No. X-ray Diffraction Electron Diffraction
1. X-rays are strongly attenuated by matter with Electrons are highly attenuated by matter
penetration depth of microns to millimetres. with penetration depth of nanometres

2. X-ray beams are difficult to focus Electron beams can be highly focused.

3. Intensities and peak positions can be Diffracted electrons can interact strongly
determined with a great deal of accuracy with the lattice making it difficult to get
from the pattern obtained reliable intensities.

4. The scattering power drops off smoothly as a Scattering power drops off strongly as a
function of 2θ function of 2θ

Polarization of Ions
The bond in a compound X+Y- is usually considered to be 100% ionic. However, it will always have some
degree of covalency or covalent character. When two oppositely charged ions approach each other, the
cation attracts electrons in the outermost shell of the anion but repels the positively charged nucleus. This
results in distortion, deformation, or polarization of the anion. If the degree of polarization is quite small,
an ionic bond is formed. If the degree of polarization is large, a covalent bond is obtained.
Polarization power of a cation is its ability to distort (polarize) an anion. Polarizability of an anion is its
tendency to become distorted (polarized) by a cation.
Fajans’ Rule
Fajans Kazimierz in 1923 formulated a rule that can be used to predict whether a chemical bond is
expected to be predominantly ionic or covalent. This was said to depend on the relative charges and sizes
of the cation and anion. Fajans’ rule states that if two oppositely charged ions are brought together the
nature of the bond between them depends upon the effect of one ion on the other.
The polarizing power and polarizability that enhance the formation of covalent bonds is favoured by the
following:
1. Small cation: Covalent character increases with decreasing cation size or increasing cation
charge. High charge density is able to exert a powerful polarizing effect which distort the electron
cloud around the anion. The charge effect can be observed in the heat energy needed to melt
sodium chloride (melting point, 801℃) compared to that of calcium chloride (melting point,
772℃). The ionic size effect is obvious in the melting point differences in the iodides of
potassium and lithium (LiI = 449℃; KI = 686℃; 𝑟𝐿𝑖 + = 90 pm, 𝑟𝐾+ = 152 pm). It is also
expected that KBr will be less covalent or more ionic than LiBr for the same reason.
2. Large anion: Covalent character increases with an increase in anion charge or anion size. The
electrons of larger, more negatively charged anions are more loosely held because they are more
 shielded from the nuclear charge. Thus, these anions are more easily polarized by cations.
Compare the charge effect in LiBr with Li3P and the size effect in LiF (melting point, 845℃) with
LiI (melting point, 449℃). Iodides are the most covalent in nature among the halides (ionic
radius of I-, 𝑟𝐼− = 206 pm).
3. Large charges: As the charges on an ion increases, the electrostatic attractions of the cations for
the outer electrons of the anion increases, resulting in the increase in the degree of covalency and
polarization. Therefore, since Na+ and K+ ions have smaller charges and charge densities they
tend to form ionic bond than Al3+ and Ti4+ with larger charges and charge densities which favour
covalent bonding.
4. Electronic configuration: Covalent character is greater for cations with a non-noble gas electron
configuration (that is 18-electron, pseudo-noble gas cations) than for cations with a true noble gas
configuration (8-electron cations). This effects mostly shows up in transition metal and post-
transition metal cations in which one or more d-electrons ineffectively shielded the outer
electrons, or the electrons of an adjacent ion, from the nuclear charge. Thus, for two ions of
similar size and charge, a transition metal ion with a (n-1)dxns0 configuration will be more
polarizing and more polarizable than an alkali or alkaline earth metal with a noble gas
configuration, (n-1)s2(n-1)p6ns0. Compare CuCl (melting point, 430℃, Cu+ = 3d104s0, r = 91 pm)
with NaCl (melting point, 801℃, Na+ = 2s22p6, r = 116 pm).
Note that the higher the polarization the lower the melting point, boiling point, electrical conductivity of
the molten form or in aqueous solution, solubility in polar solvents and indeed the ionic character of the
compound.
From the table:
Chloride NaCl CaCl2 MgCl2 AlCl3 SrCl2 SiCl4
Melting point/℃ 801 774 715 Sublime 870 -70
Conductance in
molten state/μS 133 52 29 1.5 x 10-5 56 -

The anion Cl- is common to all the compounds while the cations vary in the ionic charges and sizes. The
nature of bond in AlCl3 and SiCl4 is expectedly covalent. The cations in NaCl, MgCl2 and AlCl3 are in the
same period, but the charge density increases as the ionic size decreases and charge size increases
resulting in increase of the polarizing power of the cation. Hence NaCl is ionic while MgCl 2 is less ionic,
but AlCl3 is more covalent. This is confirmed by the decrease in melting points and conductance of the
salts in the molten state. SrCl2 with larger ionic size is less polarizing than CaCl2 and NaCl, and as such is
obviously the most ionic among the six compounds.
Polymorphism and Isomorphism
Polymorphism is the ability of a solid material to exist in more than one crystalline form or crystal
structure and the substance is said to be polymorphic. When found in elemental solids the phenomenon is
also called allotropy. Polymorphism in molecular crystals is due to energy differences in crystal
structures. Polymorphs of carbon include diamond, graphite, and buck fullerene. Austenite, α-ferrite, and
δ-ferrite are polymorphs of iron. Tin also exhibits polymorphism because under different conditions it can
exist as β-tin or white tin (at 298 K and 1 bar), and α-tin or grey tin at 286 K or lower temperatures.
Changing of the white tin to the grey tin is accompanied by a decrease of density from 7.31 to 5.75 gcm-3
and the coordination number reduction from six to four as the α-tin adopts diamond-type lattice. Zinc
sulphide, ZnS exists as polymorphs in zinc blende and wurtzite. Other compounds that exist in
polymorphic forms also include silicon dioxide, calcium carbonate (as calcite and aragonite), and titanium
dioxide.
When chemically similar compounds crystallise with nearly identical crystal structure, the phenomenon is
isomorphism. Isomorphism in molecular crystals is due to energy similarities in crystal structures.

• Double sulfates with generic formula M2IMII(SO4)2.6H2O where MI is an alkali metal and MII
is Mg, Mn, Fe, Co, Ni, Cu or Zn form a series of isomorphous compounds.
Other examples of isomorphic substances are

• MI[AlSi3O8] and MII[Al2Si2O8] where MI = K or Na and MII = Ca or Ba; K[AlSi3O8] and

Na[AlSi3O8];
• Ba[Al2Si2O8] and Ca[Al2Si2O8].
• Alums and spinels also form such compounds.
To form isomorphous crystals two substances must have the same chemical formulation, contain atoms
which have corresponding chemical properties and the sizes of corresponding atoms should be similar.
Even though the space group of isomorphous compounds is the same, the unit cell dimensions will be
slightly different since different sizes of atoms are involved.