1.

THE SOLID STATE

HAIZEL G. ROY
H.S.S.T. (HG) CHEMISTRY
GOVT. H.S.S. KALAMASSERY
ERNAKULAM
 GENERAL CHARACTERISTICS OF SOLIDS

Have definite mass, volume and shape.

Intermolecular distances are short.

Intermolecular forces are strong.

Constituent particles have fixed positions.

They can only oscillate about their mean positions.

Incompressible and rigid.

 CLASSIFICATION OF SOLIDS

Solids can be classified into two types. They are

Crystalline Solids

Amorphous Solids
DIFFERENCE BETWEEN CRYSTALLINE AND AMORPHOUS SOLIDS
 ANISOTROPY

The physical properties like electrical

resistance or refractive index show

different values when measured along

different directions in the same crystal.

The arrangement of particles is different in

different directions.
 ISOTROPY

The value of any physical property

would be same along any
directions.
No long range order and the
arrangement is irregular along all
the directions.
 PSUEDO SOLIDS OR SUPER COOLED LIQUIDS

Amorphous solids have a tendency to flow very slowly.

Therefore, they are called pseudo solids or super cooled liquids.

 NOTE-1

Glass objects from ancient civilizations are milky in appearance

due to crystallization.

Glass is an amorphous solid.

On heating, glass become crystalline at some temperature.

 NOTE-2

Glass panes fixed to windows or doors of old buildings are found

to be slightly thicker at the bottom than at the top.

Glass flows down very slowly and makes the bottom portion

slightly thicker.
 CLASSIFICATION OF CRYSTALLINE SOLIDS

Classification is based on the intermolecular forces.

Crystalline solids are classified into four. They are

Molecular Solids

Ionic Solids

Metallic Solids

Covalent solids
MOLECULAR SOLIDS
 A. NON POLAR MOLECULAR SOLIDS

The atoms or molecules are held by weak dispersion forces or

London forces.

They are Soft and non-conductors of electricity.

They have low melting points.

Exist in liquid or gaseous state at room temperature and pressure.

Eg: H2, Cl2, I2 etc.

 B. POLAR MOLECULAR SOLIDS

The molecules are held together by dipole-dipole interactions.

They are soft and non-conductors of electricity.

Their melting points are higher than those of non polar molecular

solids.

Eg: Solid SO2 and Solid NH3.

 C. HYDROGEN BONDED MOLECULAR SOLIDS

The molecules are held together by strong hydrogen bonding.

They are non conductors of electricity.

They are generally volatile liquids or soft solids under room

temperature and pressure.

Eg: H2O.
 2. IONIC SOLIDS

Ions are the constituent particles.

Formed by the 3 dimensional arrangements of
cations and anions bound by strong
electrostatic forces.
These solids are hard and brittle in nature.
They have high melting and boiling points.
They are insulators in solid state.
In aqueous solutions, they conduct electricity.
 3. METALLIC SOLIDS

Consist of +ve ions in a sea of mobile

electrons.
Held together by strong electrostatic
force of attraction.
They are malleable and ductile.
Good conductors of heat and electricity.
 4. COVALENT OR NETWORK SOLIDS

The molecules are held together by

strong covalent bonds.
They are very hard and brittle.
They are insulators.
Eg: Diamond, Silicon Carbide etc.
 NOTE - 3

Graphite is soft and conductor of electricity.

The free electrons make graphite a good
conductor of electricity.
Graphite is a soft solid and a good solid
lubricant.
Because different layers can slide one over
the other.
 CRYSTAL LATTICE

A regular 3 dimensional
arrangement of points in
space is called a crystal
lattice.
 BRAVAIS LATTICES

The 14 possible 3 dimensional lattices are called Bravais lattices.

 CHARACTERISTICS OF CRYSTAL LATTICE
Each point in a lattice is called lattice point or lattice site.
Lattice site represents one constituent particle.
The constituent particle may be an atom, a molecule or an ion.
Lattice points are joined by straight lines which give the geometry of the lattice.
 UNIT CELL

Unit cell is the smallest

repeating unit of a crystal

lattice which when repeated in

different direction generates

the entire crystal.

 CHARACTERISTICS OF UNIT CELL

The dimensions are along the three edges a, b and c.

These edges may or may not be mutually perpendicular.

Angles between the edges a, b and c are α, β and γ.

A unit cell is characterized by six parameters a, b, c, α, β and γ.

PRIMITIVE AND CENTERED UNIT CELLS
 PRIMITIVE UNIT CELL OR SIMPLE CUBIC

The constituent particles are present at all the 8 corners of a cube.

CENTERED UNIT CELLS
 BODY CENTERED CUBIC
The constituent particles are present at all the corners as well as at
the centre of the unit cell.
 BODY CENTERED CUBIC
The constituent particles are present at all the corners as well as at
the centre of each of the six faces.
 END CENTERED CUBIC
The constituent particles are present at all the corners as well as at
the centre of any two opposite faces.
SEVEN PRIMITIVE UNIT CELLS
NUMBER OF ATOMS IN A UNIT CELL
 NUMBER OF ATOMS IN A UNIT CELL

Simple cubic has one atom per unit cell.

Body Centered Cubic has 2 atoms per unit cell.
Face Centered Cubic unit cell has 4 atoms per unit cell.
 CO-ORDINATION NUMBER

The number of nearest neighbour’s with which a given sphere is in

contact.
 CLOSE PACKED STRUCTURES

A close packing is a way of arranging equidimensional object in

space.
The available space is filled very effectively.
 CLOSE PACKING IN ONE DIMENSION

Each sphere is in contact with two of its neighbour’s.

The co-ordination number is 2.
 CLOSE PACKING
IN TWO DIMENSIONS
 A. SQUARE CLOSE PACKING

The particles of second, third, fourth etc

are arranged vertically with the particles
of the first row.
Each particle is in contact with four other
neighbouring particles.
So it is called square close packing.
Its co-ordination number (CN) is 4.
 B. HEXAGONAL CLOSE PACKING
The particles of the second row are
arranged in the depressions produced
by the particles of the first row.
The particles in the third row will be
vertically aligned with those in the
first row.
Each sphere is in contact with six other
spheres to form a hexagonal pattern.
So it is called hexagonal close packing.
Its coordination number is 6.
 CLOSE PACKING
IN THREE DIMENSIONS
 A. HEXAGONAL CLOSE PACKING

The particles of every third layer are in vertical

alignment with those of the first layer.
The third layer is a repetition of the first layer.
This will form the sequence AB AB AB AB …….
This type of packing is called AB AB packing or
hexagonal close packing (hcp).
Eg: Mg, Zn, Cd etc.
 B. CUBIC CLOSE PACKING

The particles of every fourth layer are in

vertical alignment with those in the first layer.
The fourth layer is the repetition of the first
layer.
This will give rise to ABC ABC ABC …………..
sequence.
This type of packing is called ABC ABC packing
or cubic close packing (ccp).
Eg: Cu, Ni, Au etc.
 INTERSTITIAL SITES OR VOIDS

The vacant space between the constituent particles in a closed

packed structure is called a void.
 TYPES OF VOIDS

Voids are classified into three types. They are

Triangular Voids

Tetrahedral Voids

Octahedral Voids
 TRIANGULAR VOID

The empty space produced in between three spheres in a close

packed structure is called a triangular void.

 TETRAHEDRAL VOID

The void formed by the close packing of four spheres which touch

each other at only one point is called a tetrahedral void.

 OCTAHEDRAL VOID

A void surrounded by six spheres in octahedral position is called

octahedral void.
 PACKING EFFICIENCY

It is the percentage of total space filled by the particles.

PACKING EFFICIENCY IN A SIMPLE CUBIC CELL
PACKING EFFICIENCY IN A BODY CENTERED CUBIC CELL
 PACKING EFFICIENCY IN
FACE CENTERED CUBIC STRUCTURES (hcp & ccp)
RELATIONSHIP BETWEEN EDGE LENGTH (a)
AND RADIUS (r) OF A SPHERE
CALCULATION OF DENSITY OF A CRYSTAL
FORMULA OF A COMPOUND
IMPERFECTIONS
IN SOLIDS
 IDEAL CRYSTAL

In an ideal crystal the constituent particles are regularly arranged

throughout the crystal.

IMPERFECTION

Any deviation from the completely ordered arrangement in a crystal

is called a defect or imperfection.
 POINT DEFECTS

The irregularities or deviations from ideal arrangement around a

point or an atom in a crystalline substance.

LINE DEFECTS

The irregularities or deviations from ideal arrangement in entire

rows of lattice points.
 TYPES OF POINT DEFECTS

Point defects can be classified into three types.

1. Stoichiometric Defects
The number of +ve and ―ve ions are exactly in the ratio indicated by the
chemical formulae.
2. Non Stoichiometric Defects
The number of +ve and ―ve ions are not exactly in the ratio indicated by the
chemical formulae.
3. Impurity Defects
This type of defect arises due to the presence of some impurities in the crystal
lattice.
 TYPES OF
STOICHIOMETRIC DEFECTS
 SCHOTTKY DEFECT

Equal number of +ve and ―ve ions are missing from the lattice
site.
Found in crystals of high co-ordination number.
It decreases the density of the crystal.
Shown by ionic substances in which the cation and anion are
almost similar sizes.
The crystals are electrically neutral.
Eg: NaCl, KCl, AgBr etc.
 FRENKEL DEFECT

A cation is dislocated from its normal site to an interstitial

site.
Found in crystals having low coordination number. It does not
change the density of the solid.
Shown by ionic substances in which there is a large difference
in the size of ions.
Eg: ZnS, AgCl, AgBr and AgI
 TYPES OF
NON STOICHIOMETRIC DEFECTS
1. METAL EXCESS DEFECT
 A. DUE TO ANION VACANCY

A ―ve ion may be absent from its lattice site leaving a hole.
This hole is occupied by an electron and the electrical
neutrality is maintained.
The electrons entrapped in this anion vacancy are called ‘F’
centres.
They impart colour to the crystals.
The colour is due to the excitation of electrons which absorb
energy from the visible light falling on the crystals.
 B. DUE TO EXTRA CATION

An extra +ve ion occupies an

interstitial position.

The electrical neutrality is

maintained by an electron

present in another interstitial

position.
2. METAL DEFICIENCY DEFECT
 A. DUE TO CATION VACANCY

A cation is absent from its

lattice site.

The electrical neutrality is

maintained by an extra

charge on the adjacent

metal.
 B. DUE TO EXTRA ANION

An extra anion occupies an

interstitial position.

The electrical neutrality is

maintained by an extra charge

on the adjacent cation.

PROPERTIES OF SOLIDS
ELECTRICAL PROPERTIES
OF SOLIDS
 CONDUCTORS

Conductors are substances which allow electric current to flow through it.

Metals are good conductors of electricity.

In metals, the conduction is due to the movement of electrons under the

influence of an applied electric potential.

 SEMI CONDUCTORS

Substances which allow electric current to flow through it partially.

They have conductivity in between metals and Insulators.

INSULATORS

These are substances which do not allow electric current to flow through

it.
 BAND THEORY OF SOLIDS

Valence band is occupied by valence electrons.

Conduction band is the empty band above the valence band.

 CONDUCTORS

In a conductor, valence band overlaps the conduction band.

Therefore, no energy is required to move an electron from the valence

band to the conduction band.

 SEMI CONDUCTORS

In In semiconductors, the gap between the valence band and

conduction band is small.
Therefore, some electrons may jump from valence band to conduction
band
It shows some conductivity.
 INSULATORS

In an insulator, the valence band and conduction bands are not

overlapped.

There is a large gap in between the valence and conduction

bands.

The electrons cannot jump from the valence band to

conduction band.
 CLASSIFICATION OF SEMICONDUCTORS

INTRINSIC SEMICONDUCTOR
Semiconductors in their extremely pure state are very poor conductors of
electricity.
They are called intrinsic semiconductors.
Eg: Ge, Si.

EXTRINSIC SEMICONDUCTOR
With the addition of certain other elements in the crystal structure of
semiconductors, their conductivity can be improved.
They are called extrinsic semiconductors.
 DOPING
The process of adding certain impurities in the crystal structure

of a semiconductor to improve its conductivity is called doping.

 N-TYPE SEMI CONDUCTOR

A semiconductor crystal having an

excess of electrons by doping.

The donor atoms are 15th group

elements like N, P, As, Sb, Bi.

Electrons are the charge carriers.

 P-TYPE SEMI CONDUCTOR

A semiconductor material having an

excess of holes by doping.

Holes are the charge carriers.

The donor atoms are 13th group

elements like B, Al, Ga, In and Tl.

MAGNETIC PROPERTIES
OF SOLIDS
 PARAMAGNETISM

Substances which are weakly attracted by the magnetic field.

Paramagnetism is due to the presence of one or more unpaired

electrons which are attracted by the magnetic field.

Eg: Al, O2, TiO, CuO, Cu2+, Fe3+, Cr3+ etc.

 DIAMAGNETISM

Substances which are weakly repelled by the magnetic field

are called diamagnetic substances.

Shown by those substances in which all the electrons are

paired and there are no unpaired electrons.

Eg: H2O, Alcohol, C6H6, NaCl etc.

 FERROMAGNETISM
The substances which are strongly attracted by the magnetic

field are known as ferromagnetic substances.

They show permanent magnetism even when the magnetic

field is removed.

The magnetic moments are in the same direction.

Eg: Fe, Co, Ni, Gd, CrO2 etc.

 ANTIFERROMAGNETISM
Alignment of magnetic moments in the opposite direction in

equal numbers.

It results in zero magnetic moment and gives rise to

antiferromagnetism.

Eg: MnO, FeO, CoO etc.

 FERRIMAGNETISM
The magnetic moments are aligned in parallel and antiparallel

directions in unequal numbers.

It results in a net magnetic moment.

Eg: Fe3O4, MgFe2O4, CuFe2O4, ZnFe2O4 etc.

 CURIE TEMPERATURE

Curie point or Curie Temperature is the temperature at which certain magnetic

materials undergo a sharp change in their magnetic properties.

Curie temperature is the temperature above which the magnetic materials lose

their ferromagnetic properties. At lower temperatures, the magnetic dipoles

are aligned. Above the curie temperature, random thermal motions cause

misalignment of the dipoles.