SOLID STATE

CHEMISTRY

contents

Introduction
Types of solids
Crystal Structures
Elements of Symmetry
Braggs equation
Allotropes of carbon: Diamond, graphite &
Fullerene

INTRODUCTION
Three phases of matter:
Gas
Liquid
Solid

Gas
molecules

Liquid
molecules

Solid
molecules

What is solid?

Definite shape.
Definite volume.
Highly incompressible.
Rigid.
Constituent particles held closely by strong
intermolecular forces.
Fixed position of constituents.

TYPES OF SOLIDS
Two types (based upon atomic arrangement,
binding energy, physical & chemical
properties):
1.Crystalline
2. Amorphous

Crystalline solids
The building constituents arrange themselves in regular
manner throughout the entire three dimensional network.
Existence of crystalline lattice.
A crystalline lattice is a solid figure which has a definite
geometrical shape, with flat faces and sharp edges.
Incompressible orderly arranged units.
Definite sharp melting point.
Anisotropy.
Definite geometry.
Give x-ray diffraction bands.
Examples: NaCl, CsCl, etc.

AMORPHOUS SOLIDS
Derived from Greek word Omorphe meaning
shapeless.
No regular but haphazard arrangement of atoms or
molecules.
Also considered as non-crystalline solids or supercooled liquids.
No sharp m.p.
Isotropic.
No definite geometrical shape.
Do not give x-ray diffraction bands.
Examples: glass, rubber, plastics.

Types of crystal structures

Ionic crystals
Covalent crystals
Molecular crystals
Metallic crystals

Ionic crystals

Lattice points are occupied by positive and negative ions.

Hard and brittle solids.
High m.p. due to very strong electrostatic forces of
attraction.
Poor conductors of electricity in solid state but good in
molten state.
Packing of spheres depends upon:
presence of charged species present.
difference in the size of anions and cations.
Two types:
AB types.
AB2 types.

Covalent crystals

Lattice points are occupied by neutral atoms.

Atoms are held together by covalent bonds
Hard solids.
High m.p.
Poor conductors of electricity.
Two common examples: diamond & graphite.

Molecular crystals
Lattice points are occupied by neutral molecules.
The molecules are held together by vander
Waals forces.
Very soft solids.
Low m.p.
Poor conductors of electricity.

Metallic crystals
Lattice points are occupied by positive metal ions
surrounded by a sea of mobile e-.
Soft to very hard.
Metals have high tensile strength.
Good conductors of electricity.
Malleable and ductile.
Bonding electrons in metals remain delocalized over
the entire crystal.
High density.

Laws of symmetry
Plane of symmetry
Centre of symmetry
Axis of symmetry.

Elements of symmetry
in cubic crystal

Rectangular planes of symmetry: 3

Diagonal planes of symmetry: 6
Axes of four-fold symmetry: 3
Axes of three-fold symmetry: 4
Axes of two-fold symmetry: 6
Centre of symmetry: 1
Total symmetry elements: 23

Planes of symmetry
Rectangular plane of symmetry: 3

Diagonal plane of symmetry: 6

Axis of symmetry
Four-fold axis of symmetry: 3

Three-fold axis of symmetry: 4

Axis & centre of symmetry

Centre of symmetry: 1
Two-fold axis of symmetry: 6

Types of cubic crystals

Four types:
1.Simple or primitive type
2. Body-centered
3. Face-centered
4. End face-centered

Simple or primitive type (sc)

Body-centered cell (bcc)

Face-centered cell (fcc)

End face-centered cell

Number of atoms per unit cell

in a cubic lattice

Simple cubic cell: 1atom/unit cell of sc

Body-centered cell: 2 atoms/unit cell of bcc
Face-centered cell: 4 atoms/unit cell of fcc
End face-centered cell: 2 atoms/unit cell

No of atoms per unit cell= 8 x 1/8

No of atoms per unit cell= 8 x 1/8 =

e.g.Polonium
52% of the space is occupied by the atoms

No of atoms present per unit cell

= (8 x 1/8 ) + (1 x

No of atoms per unit cell= (8 x 1/8) +1

=2

e.g. CsCl, CsBr

68% of the space is occupied by the atoms

No of atoms present per unit cell

= (8 x 1/8 ) + (6 x

e.g. NaCl, NaF, KBr, MgO

74% of the space is occupied by the atoms

of atoms present per unit cell

= (8 x 1/8 ) + (2 x 1/2) =

Atomic radius of a cubic lattice

Simple cubic cell:
r = a/2
Face-centered cubic cell:
r = a/8
Body-centered cubic cell:
r = 3a/4
(where a length of cube)

Radius ratio rule

Relation between the radius, co-ordination
number and the structural arrangement of the
molecule.
Radius ratio =
Greater the radius ratio, larger the size of the
cation and hence the co-ordination number.
density = (z*Ma)/Na*a^3
Ma=mass no.,
Na=avogadro, a= side length, z=no. of atoms

Structural analysis by radius

ratio rule
S.NO.

RADIUS
RATIO

CO-ORDINATION
NUMBER

SHAPE

EXAMPLE

1.

0.0 0.155

Linear

HF-

2.

0.1550.225

Triangular
planar

B2O3, BN

3.

0.225 0.414

Tetrahedral

ZnS, SiO4-4

4.

0.414 0.732

Octahedral

NaCl

5.

0.732 1.0

Body-centered
cubic

CsCl

BRAVAIS LATTICES
Unit cell parameters:
Lengths a, b & c.
Angles , & .
Total crystal lattices: 7
Total Bravais lattices: 14

Crystal systems with unit cell

parameters
S.No.

System

Cell
Dimensions

Crystal
Angles

Bravais
Lattices

Min. Sym.
Elements

1.

Cubic

a=b=c

===90

sc, fcc,
bcc = 3

3-fold axes: 4
4-fold axes: 3

2.

Orthorhombic

abc

===90

sc, fcc,
bcc, efcc
=4

2-fold axes: 3

3.

Tetragonal

a=bc

===90

sc, bcc= 2 4-fold axis: 1

S.No.

System

Cell
Dimensions

Crystal
Angles

Bravais
Lattices

Min. Sym.
Elements

4.

Monoclinic

abc

= = 90
90

sc, efcc = 2

2-fold axis: 1

5.

Triclinic

abc

90

sc = 1

1-fold axis: 1

6.

Hexagonal

a=bc

= = 90
= 120

sc = 1

6-fold axis: 1

7.

Rhombohedral
or Trigonal

a=b=c

== 90

sc = 1

3-fold axis: 1

Examples of different crystal

systems
S.No.

System

Example

1.

Cubic

NaCl, KCl, CaF2, Cu, ZnS, CsCl, Cu2O

2.

Orthorhombic

BaSO4, KNO3, MgSiO3, K2SO4, CdSO4,

AgBr

3.

Tetragonal

SnO2, TiO2, ZrSiO4

4.

Monoclinic

CaSO4.2H2O, monoclinic S

5.

Triclinic

CuSO4.5H2O, NaHSO4, H3PO3

6.

Hexagonal

PbI2, Mg, Cd, Zn, ZnO, BN, SiO2, HgS,

CdS

7.

Rhombohedral or Trigonal

Graphite, ICl, Al2O3, calcite (CaCO3), As,

Sb, Bi

Cubic lattice

Orthorhombic lattice

Tetragonal lattices

Monoclinic lattice

Triclinic lattice

Hexagonal lattice

Rhombohedral (Trigonal) lattice

Structures of important ionic

compounds
1. AB type: NaCl (rock salt)
CsCl
ZnS (zinc blende / sphalerite)
2.

AB2 type: CaF2 (fluorite)

TiO2 (rutile)
SiO2

3. A2B type: K2O (antifluorite)

Structure of NaCl (Rock

salt)

FCC type.
Co-ordination number 6:6.
Calculation of no. of atoms of NaCl/unit
cell:
Cl at corners: (8 1/8)
Cl at face centres (6 1/2)

=1
=3

Na at edge centres (12 1/4) = 3

Na at body centre
=1
Unit cell contents are 4(Na+Cl-)
i.e. per each unit cell, 4 NaCl
units will be present.

Structure of sodium
choride
Cubic unit cell:
smallest repeatable unit

Structure of CsCl

bcc type.
Co-ordination number 8:8.
Number of atoms/unit cell:1

Structure of ZnS
fcc type.
Co-ordination number
4:4.
Calculation of no. of
atoms/unit cell:
Total S = 8x1/8 + 6x1/2 = 4
Total Zn = 4
Hence, total ZnS = 4

Structure of CaF2
Ca+
F-

fcc type.
Co-ordination number: 8:4
(8 for cation, 4 for anion)
*Note: All the compounds of AB 2 type follow the same pattern.

Structure of K2O
O

-2

Na+

fcc type.
Co-ordination number: 4:8
4 for cation
8 for anion

Structure of important
covalent compounds
1.Diamond
2. Graphite

Diamond

Structure of diamond

fcc type.
Tetrahedral
C-C bond length = 1.34A
Refractive index = 2.4
High dispersive power of light
Non-conductor of electricity
3d network
Hardest substance ever known.
Used as abrasive.

3d- structure of diamond

Graphite

Structure of Graphite

One of the softest substances ever known.

2-d hexagonal layer structure
C-C bond length = 1.45A
Inter layer distance = 3.54A
Sliding nature
sp2 hybridisation with one electron left over.
Specific gravity 2.2
Electrical conductor
Metallic lustre
Used as good lubricant.

2d- structure of graphite

FULLURENES

Important points about Fullurenes

Discovered in 1985 as C60.
Consists of spherical, ellipsoid or cylindrical
arrangement of dozens of C-atoms.
3 types:

Spherical: Also called bucky balls. Molecule

of the year 1991 by Science magazine.
Cylindrical: C nanotubes or buckytubes.
Planar.

Structure of fullurenes
60 C-atoms arranged in pentagons and hexagons.
7 in diameter.
Soccer-ball shaped molecule with 20 six-membered & 12
five-membered rings.
Each pentagon is surrounded by five hexagons.
No two pentagons are adjecent.
Each carbon is sp2-hybridized.
Used:
as photoresistant.
in the preparation of super-conductors.
in optical devices.
in batteries as charge carriers.

X-ray
Tube

BRAGGS EQUATION
Detector

Incident radiation

Reflected radiation

1
2

Z
Y

Transmitted radiation
Beam 2 lags beam 1 by XYZ = 2d sin
so

2d sin = n

Braggs Law