Solid State Chemistry: Basic Concepts
Na Cl
Dr. Bhaskar Devu Mukri
Assistant Professor
Department of Chemistry
Motilal Nehru National Institute of Technology Allahabad,
Prayagraj, Uttar Pradesh – 211004, India
Definition:
“It is the study of synthesis, structure and properties of solid materials”
Solid is one of the four fundamental states of matter (solid, liquid, gas and plasma)
Increasing Energy
Solid Liquid Gas Plasma
Ex:
Solid materials broadly classified into two types:
• Crystalline solid
• Amorphous solid
Crystalline solid: A solid material whose constituents like atoms or molecules or ions are arranged in a
highly regular order. Ex: NaCl, diamond, etc.
Amorphous solid: A solid material whose constituents do not arranged in regular order.
Ex: Glass, rubber, etc.
In crystalline solid, atoms or molecules are geometrically arranged or packed within the unit volume
Crystal lattice:
Lattice – It is a translationally periodic arrangement of points in 3D space.
Unit cell - It is defined as the smallest repeating unit having the geometrically arranged constituents.
Crystal systems
Tetragonal Orthorhombic Hexagonal
Cubic
b b
b a a b
a a
c
c c c
β α β α
β α β α
γ
γ γ γ
a=b=c a=b≠c a≠b≠c a =b ≠ c
and α = β = γ = 90° and α = β = γ = 90° and α = β = γ = 90° and α = β = 90°, γ = 120°
Crystal systems
Monoclinic Triclinic
Rhombohedral
b b
a a
a b
c c
α c β α
β β α
γ
γ γ
a=b=c a≠b≠c a≠b≠c
and α = β = γ ≠ 90° and α = γ = 90° ≠ β and α ≠ β ≠ γ ≠ 90°
Bravais lattices
Crystal systems Primitive (P) Body centered (I) Face centered (F) Base centered (C)
Cubic
Tetragonal
Orthorhombic
Hexagonal
Bravais lattices
Crystal systems Primitive (P) Body centered (I) Face centered (F) Base centered (C)
Rhombohedral
Monoclinic
Triclinic
Cubic crystal system
Lattice point locations
Cubic Unit cells
Simple Cubic Body-Centered Cubic (BCC) Face-Centered Cubic (FCC)
Atomic packing factor (APF)
It is defined as the volume of atoms arranged in the unit cell divided by the volume of the unit cell.
Close packing – hexagonal close packing (HCP) and cubic close packing (CCP)
AB
ABABAB – ABCABCABC –
HCP structure CCP structure
ABA ABC
Simple cubic
APF = 0.52 and the percentage of packing = 52%
Body-centered cubic (BCC)
Close-packed directions:
length = 4R
= 3a
Unit cell contains:
1 + 8 x 1/8
= 2 atoms/unit cell
atoms volume
4 3
unit cell 2 ( 3a/4)
3 atom
APF =
volume
a3
unit cell
APF = 0.68 and the percentage of packing = 68%
Face-centered cubic
Close-packed directions:
length = 4R
= 2a
Unit cell contains:
6 x 1/2 + 8 x 1/8
= 4 atoms/unit cell
atoms volume
4 3
unit cell 4 ( 2a/4)
3 atom
APF =
volume
a3
unit cell
APF = 0.74 and the percentage of packing = 74%
In simple cubic system,
2R = a
In body-centered cubic system,
In face-centered cubic system,
Number of atoms Volume of an atom
in a unit cell × (sphere)
R % of atomic packing factor (APF) =
Volume of a unit cell
× 100
R R
n ×
= × 100
a3
Density of a unit cell
The unit cell contains atleast one formula unit.
where N is Avogadro’s number. If the unit cell of volume, V contains Z formula units, then
V = Volume of one formula unit × Z
Therefore,
D=
V is usually expressed as Å3 i.e. 10-24 cm3 and Avogadro’s number is 6.023 × 1023. Then, above formula reduces to
D= in g/cm3
For cubic unit cell, V = a3, where a is the edge length of the unit cell.
Crystalline solids:
4 types of crystalline solids
• Ionic crystalline solid: It consists of positively and negatively charged ions held together by electrostatic
forces.
High melting and boiling points, hard and brittle, and electrically
insulator, but highly conductive when it melt or dissolve in water.
Ex: NaCl, CdI2, NH4NO3, etc.
Ionic bond:
An ionic bond is formed by the complete transfer of some electrons from one atom to another. The atom losing one or more
electrons becomes a cation—a positively charged ion. The atom gaining one or more electron becomes an anion—a negatively
charged ion.
Na+ Cl−
Na atom Cl atom Na+ ion Cl− ion
(a cation) (an anion)
Sodium Chloride (NaCl)
• Covalent crystalline solid: The atoms are bonded by covalent bonds in a continuous network, resulting in a big
crystal.
High melting point, very hard and little brittle, and variable electrical conductivity, but
low conductivity when it melted.
Ex: Diamond, graphite, quartz, SiC, etc.
Covalent bond:
A covalent bond consists of the mutual sharing of one or more pairs of electrons between two atoms. These electrons are
simultaneously attracted by the two atomic nuclei. A covalent bond forms when the difference between the electronegativities of
two atoms is too small for an electron transfer to occur to form ions.
Single bond Double bond Triple bond
H2O: H−O−H CO2: O═C═O N2: N≡N
Diamond structure Graphite structure
• Molecular crystalline solid: It consists of discrete molecules, which bind together by the cohesive forces.
Low melting and boiling points, soft, ductile or brittle, and electrically insulator.
Ex: Ice, naphthalene, fullerene, As4, etc.
The cohesive forces that bind the molecules together are van der Waals forces, dipole-dipole interactions,
quadrupole interactions, π−π interactions, hydrogen bonding, halogen bonding, London dispersion forces.
Hydrogen Bonding:
It is a primarily electrostatic force of attraction between an hydrogen atom which is covalently bound to a more
electronegative atom or group and another electronegative atom bearing a lone pair of electrons. This bond is weaker than an
ionic bond or covalent bond but stronger than van der Waals forces.
Salicylic acid
Intramolecular hydrogen bonding
P-hydroxy benzoic acid Hexagonal Ice crystal structure
Intermolecular hydrogen bonding
Naphthalene monoclinic crystal structure Fullerene (C60) cubic crystal structure
• Metallic crystalline solid: The metal atoms are held together by metallic bonding, which one between an electron
cloud of delocalized electrons and positively charged metal ion.
Variable melting point, ductile and malleable, high electric
and thermal conductivity, and luster.
Ex: Fe, Cu, Zn, etc.
Metallic Bonding:
It is a type of chemical bonding that arises from the electrostatic attractive force between conduction electrons and positively
charged metal ions.
Delocalized electrons Metal ions
Close packed structures
Hexagonal close packed (hcp)
Cubic close packed (ccp) or face-centered cubic (fcc)
A
Interstitial sites in close packed structures
Tetrahedral void or site Octahedral void or site Cubic close packed (ccp) or fcc
Hexagonal close packed (hcp)
Metal atom Metal atom
Octahedral void or site Tetrahedral void or site
In a close packed structure, the number of tetrahedral voids is two times the
number of spheres and number of octahedral voids is same as the number of
spheres.
