Revision Notes on Solid State

Classification of solids:
Crystalline and Amorphous solids:
S.No. Crystalline Solids Amorphous solids

1 Regular internal arrangement of particles irregular internal arrangement of particles

2 Sharp melting point Melt over a rage of temperature

3 Regarded as true solids Regarded as super cooled liquids or pseudo solids

4 Undergo regular cut Undergo irregular cut.

5 Anisotropic in nature Isotropic in nature

Based on binding forces:

Crystal Classification Unit Binding Forces Properties Examples
Particles
Atomic Atoms London dispersion Soft, very low melting, Noble gases
forces poor thermal and electrical
conductors
Molecular Polar or Vander Waal’s Fairly soft, low to Dry ice
non – polar forces (London moderately high melting (solid,
molecules dispersion, dipole – points, poor thermal and methane
dipole forces electrical conductors
hydrogen bonds)
Ionic Positive and Ionic bonds Hard and brittle, high NaCl, ZnS
negative ions melting points, high heats
of fusion, poor thermal and
electrical conductors
Covalent Atoms that are Covalent bonds Very hard, very high Diamond,
connected in melting points, poor quartz,
covalent bond thermal and electrical silicon
network conductors
Metallic Solids Cations in Metallic bonds Soft to very hard, low to All metallic
electron cloud very high melting points, elements, for
excellent thermal and example, Cu,
Fe, Zn
 electrical conductors,
malleable and ductile
Bragg Equation:
nλ = 2dsinθ,
Where
 d= distance between the planes
 n = order of refraction
 θ= angel of refraction
 λ = wavelength
Crystal Systems:
 Total number of crystal systems: 7
 Total number of Bravais Lattices: 14

Crystal Systems Bravais Lattices Intercepts Crystal angle Example

Cubic Primitive, Face a = b = c a = b = g = 90o Pb,Hg,Ag,Au

Centered, Body Diamond, NaCl,
Centered ZnS
Orthorhombic Primitive, Face a ≠ b ≠ c a = b = g = 90o KNO2, K2SO4
Centered, Body
Centered, End
Centered
Tetragonal Primitive, Body a = b ≠ c a = b = g = 90o TiO2,SnO2
Centered
Monoclinic Primitive, End a ≠ b ≠ c a = g = 90o, b≠ 90o CaSO4,2H2O
Centered
Triclinic Primitive a≠b≠c a≠b≠g≠900 K2Cr2O7,
CaSO45H2O
Hexagonal Primitive a=b≠c a = b = 90 , g = 120
0 o
Mg, SiO2, Zn, Cd

Rhombohedra Primitive a=b=c a = g = 90o, b≠ 90o As, Sb, Bi,

CaCO3
Number of atoms in unit cells.
Primitive cubic unit cell:
 Number of atoms at corners = 8×1/8 =1
 Number of atoms in faces = 0
 Number of atoms at body-centre: =0
 Total number of atoms = 1
Body-centred cubic unit cell:
 Number of atoms at corners = 8×1/8 =1
 Number of atoms in faces = 0
 Number of atoms at body-centre: =1
 Total number of atoms = 2
Face-centred cubic or cubic-close packed unit cell:
 Number of atoms at corners = 8×1/8 =1
 Number of atoms in faces = 6×1/2 = 3
 Number of atoms at body-centre: = 0
 Total number of atoms = 4
Packing Efficiency
Packing Efficiency = (Volume occupied by all the atoms present in unit cell / Total volume of unit cell)×100
Close structure Number of atoms per Relation between edge Packing Efficiency
unit cell ‘z’. length ‘a’ and radius of
atom ‘r’
hcp and ccp or fcc 4 r = a/(2√2) 74%

bcc 2 r = (√3/4)a 68%

Simple cubic lattice 1 r = a/2 52.4%

Density of crystal lattice:

r = (Number of atoms per unit cell × Mass number)/(Volume of unit cell × NA)

or

Octahedral and Tetrahedral Voids:

Number of octahedral voids = Number of effective atoms present in unit cell
Number of tetrahedral voids = 2×Number of effective atoms present in unit cell
So, Number of tetrahedral voids = 2× Number of octahedral voids.
Coordination numbers and radius ratio:
Coordination Geometry Radius ratio (x) Example
numbers
2 Linear x < 0.155 BeF2

3 0.155 ≤ x < 0.225 AlCl3

Planar Triangle
4 0.225 ≤ x < 0.414 ZnS
Tetrahedron
4 0.414 ≤ x < 0.732 PtCl42-
Square planar
6 0.414 ≤ x < 0.732 NaCl
Octahedron
8 Body centered cubic 0.732 ≤ x < 0.999 CsCl

Classification of Ionic Structures:

Structures Descriptions Examples

Rock Salt Anion(Cl-) forms fcc units and cation(Na+) occupy NaCl, KCl, LiCl, RbCl
Structure octahedral voids. Z=4 Coordination number =6
Zinc Blende Anion (S2-) forms fcc units and cation (Zn2+) occupy ZnS , BeO
Structure alternate tetrahedral voids Z=4 Coordination number =4
Fluorite Structures Cation (Ca2+) forms fcc units and anions (F-) occupy CaF2, UO2, and ThO2
tetrahedral voids Z= 4 Coordination number of anion = 4
Coordination number of cation = 8
Anti- Fluorite Na2O, K2O and Rb2O.
Structures Oxide ions are face centered and metal ions occupy all
the tetrahedral voids.
Cesium Halide Halide ions are primitive cubic while the metal ion All Halides of Cesium.
Structure occupies the center of the unit cell.
Z=2
Coordination number of = 8
Pervoskite One of the cation is bivalent and the other is tetravalent. CaTiO3, BaTiO3
Structure The bivalent ions are present in primitive cubic lattice
with oxide ions on the centers of all the six square faces.
The tetravalent cation is in the center of the unit cell
occupying octahedral void.
Spinel and Inverse Spinel :M2+M23+O4, where M2+ is present in one-eighth of MgAl2O4 , ZnAl2O4,
Spinel Structure tetrahedral voids in a FCC lattice of oxide ions and M 3+
Fe3O4,FeCr2O4 etc.
ions are present in half of the octahedral voids. M2+ is
 usually Mg, Fe, Co, Ni, Zn and Mn; M3+ is generally Al,
Fe, Mn, Cr and Rh.
Defects in crystal:
Stoichiometric Defects
1. Schottky Defects

 Some of the lattice points in a crystal are unoccupied.

 Appears in ionic compounds in which anions and cations are of nearly same size.
 Decreases the density of lattice
 Examples: NaCl and KCl
2. Frenkel Defects
 Ion dislocate from its position and occupies an interstitial position between the lattice points
 Appears in crystals in which the negative ions are much larger than the positive ion.
 Does not affect density of the crystal.
 Examples: AgBr, ZnS
Non-Stoichiometric Defects
1. Metal Excess defect:
Metal excess defect occurs due to
 anionic vacancies or
 presence of extra cation.
 F-Centres: hole produced due to absence of anion which is occupied by an electron.
2. Metal deficiency defect:
Metal deficiency defect occurs
 due to variable valency of metals
 when one of the positive ions is missing from its lattice site and the extra negative charge is balanced by
some nearby metal ion acquiring two charges instead of one