CHEM3115

INORGANIC MATERIALS
CHEMISTRY
Lecture-VI and VII
Introduction to Inorganic Materials
By TEHREEM NAZ
Contents
Bonding In solids

Types of Solids on the basis of Bonding

Defects in Crystals

Non –Stoichiometric Compounds

Bonding in Solids
• Solids can be classified according to the nature of the bonding
between their atomic or molecular components.
• The traditional classification distinguishes four kinds of bonding
1. Weak inter molecular bonding, which forms molecular solids
2. Ionic bonding, which forms ionic solids
3. Metallic bonding, which forms metallic solids
4. Covalent bonding, which forms network covalent
solids (sometimes called simply "covalent solids")
Molecular solids
Characteristics of Molecular solids
Classification of molecular solids

1. Non-Polar Molecular solids

2. Polar molecular solids
3. Hydrogen-Bonded molecular solids
Non-Polar Molecular solids
Polar Molecular solids
Hydrogen-Bonded molecular solids
• The hydrogen bonds are directional
• Relatively strong bonding
• These solids have low melting point
• No valence electrons hence good insulators
• Soluble in both polar and non-polar solvents
• They are transparent to light e.g. – water molecule, ammonic
molecules
Ionic Solids
Assignment

What is the
crystal structure
of NaCl?
Characteristics of Ionic Solids
Metallic Solids
The concept of Metallic Bond
Characteristics of Metallic Solids
Covalent Solids

• A network solid or covalent network solid

(also called atomic crystalline solids) is a
chemical compound (or element) in which
the atoms are bonded by covalent bonds in
a continuous network extending
throughout the material.
• In a network solid there are no individual
molecules, and the entire crystal or
amorphous solid may be considered a
macromolecule.
Characteristics of Covalent solids
• Hardness: Very hard, due to the strong covalent bonds throughout
the lattice (deformation can be easier, however, in directions that
do not require the breaking of any covalent bonds, as with flexing
or sliding of sheets in graphite or mica).
• Melting point: High, since melting means breaking covalent bonds
(rather than merely overcoming weaker intermolecular forces).
• Solid-phase electrical conductivity: Variable, depending on the
nature of the bonding: network solids in which all electrons are
used for sigma bonds (e.g. diamond, quartz) are poor conductors, as
there are no delocalized electrons.
• However, network solids with delocalized pi bonds (e.g. graphite)
or dopants can exhibit metal-like conductivity.
Characteristics of Covalent solids
• Liquid-phase electrical conductivity: Low, as the
macromolecule consists of neutral atoms, meaning that
melting does not free up any new charge carriers (as it would
for an ionic compound).
• Solubility: Generally insoluble in any solvent due to the
difficulty of solvating such a very large molecule.
Graphite
Diamond
Crystal Defects
• Solids are formed from many small crystals. However, during the
process of crystallization, the defect in solids occurs due to the fast or
moderate rate of formation of crystals.

• Defects, in general, are defined as those in which there will be

irregularities in the arrangements of constituent particles.

• On the basis of irregular arrangement, the defect may be a point or

line defect.
 Sources of defects in solids
• Temperature variation:
 Sources of defects in solids
• Atomic imperfection:
 Sources of defects in solids
• Lattice Imperfection:
 Sources of defects in solids
• Rate of Crystallization:
Types of Defects In Crystals
• As we know, according to the third law of thermodynamics, at
absolute 0k temperature any substance will be perfectly crystalline
but on increasing temperature defects in solids are created which are
classified into the following three types:-
• Stoichiometric defects
• Non-Stoichiometric defects
• Impurity Defects
Stoichiometric defects

These are further classified into two types;

1. Vacancy Defect: (Vacant sites in the lattice)
2. Interstitial Defect: (Constituents particles move to the interstitial site
of the lattice).
Vacancy Defect or Schottky Defects
Vacancy Defect or Schottky Defects
Interstitial Defect or Frenkel Defect
• In this type of defect, some cations are missing from their lattice site
and occupy the interstitial site of the lattice.
• This type of defect is shown by those substances which have low co-
ordination number.
• The closeness of like charges tends to increase the dielectric constant
of crystal.
Interstitial Defect or Frenkel Defect
• Frenkel defect is a kind of dislocation defect or interstitial defect in which
the smaller ion generally cation dislocate from their position to occupy
the interstitial site of the lattice or crystal.

• The density of these types of crystals remains the same because there is
no movement of ion outside the crystal.

• This defect is exhibited in those ionic compound in which the radius

ratio[r+/r–] is low. Example: ZnS , AgBr , AgI , AgCl
• Note: AgBr shows both Frenkel and Schottky defect.
Non- stoichiometric Defects
Types of Non- stoichiometric Defects
• This defect is shown by compound of d block elements of the periodic
table. These defects are classified as:
• Metal excess defect
i. Metal excess defect due to anionic vacancy

ii. Metal excess defect due to the presence of interstitial cation

• Metal Deficiency Defect

Metal excess defect
i. Metal excess defect due to anionic vacancy
i. Metal excess defect due to anionic vacancy
ii. Metal excess defect due to the presence of
interstitial cation
 ii. Metal excess defect due to the presence of
interstitial cation
• This type of defect is shown by ZnO. When ZnO is heated it loses
oxygen reversibly. The excess Zn2+ ions are occupied in the
interstitial sites for maintaining the neutrality, electrons are
enclosed in the neighboring interstitial sites. On heating, ZnO turns
yellow color by losing oxygen.
Metal Deficiency Defect
• Metal deficiency defect due to cation vacancies
Note:
Impurity Defects
Nonstoichiometric compound
• Any solid chemical compound in which the numbers of atoms of the
elements present cannot be expressed as a ratio of small whole
numbers; sometimes called berthollide compounds in distinction from
daltonides (in which the atomic ratios are those of small integers),
nonstoichiometric compounds are best known among the transition
elements.
• Several of them are important as components of solid-state electronic
devices, such as rectifiers, thermoelectric generators, photodetectors,
thermistors, and magnets useful in high-frequency circuits.
Nonstoichiometric compound
• Most nonstoichiometric compounds have compositions that are close
to those of stoichiometric compounds and can be expressed by such
formulas as WO3-x, Co1-xO, or Zn1+xO, in which x is a positive quantity
much smaller than 1.
• In certain cases apparent nonstoichiometry has been shown to result
from the existence of homologous series of stoichiometric compounds,
such as the series of molybdenum oxides having the formulas
MonO3n-1, in which the compounds corresponding to n = 8, 9, 10, 11,
12, and 14 are known; a true nonstoichiometric compound MoO3-
x would show a continuous variation of x within some range of values,
and no discrete species would be detectable.
•
Video links
• https://www.youtube.com/watch?v=Stn8L_9n5c0
• https://www.youtube.com/watch?v=Z0Ks3wjFnrk
• https://www.youtube.com/watch?v=WUqgFFmdMDI