INTRODUCTION TO INORGANIC

CHEMISTRY (SKT1013)

Chapter 2
Solid state chemistry 1
WHAT IS SOLID STATE CHEMISTRY?

• The study of synthesis, structure, bonding,

reactivity and physical properties of solids.

• Interdisciplinary overlap with condensed

matter physics, mineralogy, crystallo-
graphy, metallurgy, ceramics, and
materials science.
WHAT IS SOLID STATE CHEMISTRY?
• a sub discipline of Chemistry, primarily involves
the study of extended solids.

• Except for helium*, all substances form a solid if

sufficiently cooled at 1 atm.

• The vast majority of solids form one or more

crystalline phases – where the atoms, molecules,
or ions form a regular repeating array (unit cell).

• The properties of solids are related to its

structure and bonding.
WHAT IS SOLID STATE CHEMISTRY?
• In order to understand or modify the properties of a solid,
we need to know the structure of the material.

• Crystal structures are usually determined by the

technique of X-ray crystallography.

• Structures of many inorganic compounds may be initially

described in terms of simple packing of spheres.
Classification of matter

matter

Liquids and
Gases solids
liquid crystals
Classification of solid materials
Solid
materials

crystalline polycrystalline amorphous

Single crystal
 Crystal structure

• The periodic arrangement of atoms in the crystal

• Having a regular and continuous three-dimensional
arrangement of atoms in the solid state
• Possesses rigid and long-range order
• Its atom, molecules or ions occupy specific positions

snow ruby diamond

 Single crystal

• also called as monocrystalline solid

• is a material in which the crystal lattice of the entire
sample is continuous and unbroken to the edges of
the sample, with no grain bondaries.

Single Pyrite
Crystal

Amorphous
Solid
Single Crystals
 Polycrystalline materials
 Polycrystalline materials are made up of an aggregate of
many small single crystals (also called crystallites or grains).
 Polycrystalline materials have a high degree of order over
many atomic or molecular dimensions.
 Grains (domains) are separated by grain boundaries.

Polycrystalline
Pyrite form
(Grain)

9
 Amorphous solid
• are made up of randomly orientated atoms, ions,
or molecules that do not form defined patterns or
lattice structures.
• Amorphous materials do not have any long-range
order, but they have varying degrees of short-range
order.
• Examples to amorphous materials include
amorphous silicon, plastics, and glasses.
 TYPES OF CRYSTALS AND GENERAL PROPERTIES
TYPES OF FORCES HOLDING GENERAL PROPERTIES EXAMPLES
CRYSTAL THE UNITS
TOGETHER

IONIC Electrostatic attraction Hard, brittle, high melting NaCl, LiF, MgO,
point, poor conductor of CaCO3
heat and electricity

COVALENT Covalent bond Hard, high melting point, C(diamond),

poor conductor of heat SiO2(quartz)
and electricity

MOLECULAR Dispersion forces, Soft, low melting point, Ar, CO2, I2, H2O,
dipole-dipole forces, poor conductor of heat C12H22O11(sucrose)
hydrogen bonds and electricity

METALLIC Metallic bond Soft to hard, low to high All metallic elements:
melting point, good Na, Mg, Fe, Cu
conductor of heat and
electricity
 Ionic bonding
 Ionic bonding is the electrostatic force of attraction between
positively and negatively charged ions (between non-metals
and metals).

 All ionic compounds are crystalline solids at room

temperature.

 Example; NaCl, CuCl2 and PbO2.

Metallic elements have only up to the valence electrons in their
outer shell.

When losing their electrons they become positive ions.

Electronegative elements tend to acquire additional electrons to

become negative ions or anions.

Na Cl
• When the Na+ and Cl- ions approach each other closely
enough so that the orbits of the electron in the ions
begin to overlap with each other, then the electron
begins to repel each other by virtue of the repulsive
electrostatic coulomb force. Of course the closer
together the ions are, the greater the repulsive force.

• Pauli exclusion principle has an important role in

repulsive force. To prevent a violation of the exclusion
principle, the potential energy of the system increases
very rapidly.
 Covalent bonding

• Covalent bonding takes place between atoms with

small differences in electronegativity which are
close to each other in the periodic table (between
non-metals and non-metals).

• The covalent bonding is formed when the atoms

share the outer shell electrons (i.e., s and p
electrons) rather than by electron transfer.

• Each electron in a shared pair is attracted to both

nuclei involved in the bond.
• The approach, electron overlap, and attraction can
be visualized as shown in the following figure
representing the nuclei and electrons in a hydrogen
molecule.

e
 Covalent bonding
Diamond Graphite
• sp3-hybridized (each atom • sp2-hybridized (each atom is
carbon is covalently covalently bonded to 3 atom
bonded with 4 atom carbon)
carbon) • Each layer of graphite –
• strong covalent bonds – electrons are free to move
hardest material) around – good conductor
• The layers – held together by
weak Van der Waals forces –
the layers can slide over one
another

Graphite
Diamond
 Metallic bonding
• Metallic bonding is found in metal
elements. This is the electrostatic force
of attraction between positively
charged ions and delocalized outer
electrons.

• The metallic bond is weaker than the

ionic and the covalent bonds.

• A metal may be described as a low- + + +

density cloud of free electrons.
+ + +
• Therefore, metals have high electrical
and thermal conductivity.
+ + +
• The weakest of all the bond types.
They form fairly soft metals. Example:
copper, gold
 Van der Waals and or hydrogen
bonding

• Examples : H2O, CO2, O2, O3, CH4, P4

• The lattice points are occupied by molecule
• Attractive forces between them are Van der Waals
and or hydrogen bonding
• Intermolecular hydrogen bonding responsible for
maintaining the 3D lattice of ice
• Molecular crystal-more easily broken apart than
ionic and covalent crystals – Van der Waals and
hydrogen bonding quite weak
• Most crystals melt at temperature below 100°C

Hydrogen bonding