DSCC-5: Chemistry (Theory) - V (Code: 033CHE011)

UNIT-I : CHEMICAL BONDING & CHEMISTRY OF s- & p- BLOCK ELEMENTS

Metallic Bond: Explanation of physical properties of metals (conductivity, lustre,

malleability, ductility and cohesive force) based on free electron theory. Band theory of
metals to explain conductors, insulators, extrinsic and intrinsic semi conductors.
Hydrogen bond: Definition, properties and types of hydrogen bond. Consequences of
hydrogen bonding.
van der Waals forces: Definition and types of van der Waals forces. Factors affecting the
strength and magnitude of van der Waals forces.
(4 Lectures)
Chemistry of s- and p- block elements:
General characteristics, anomalous properties of lithium. Diagonal relationship of Li with
Mg, and Be with Al. Preparation, uses, structure and bonding in diborane, borazine, boron
nitride and carboranes. Silicates-Classification and structures. Preparation, properties and
structure of oxides and oxyacids of nitrogen. Preparation and bonding in oxoacids of
phosphorus, sulphur and chlorine. Inter halogen compounds (preparation and bonding in
ClF3, BrF5 and IF7), Xenon compounds- XeF2, XeF4, XeF6, XeOF4 and XeO3 (preparation
and bonding).
(10 Lectures)

Metallic Bond
The most numerous of all the elements are the metallic elements. All the elements in
the s, d and f blocks are metals: aluminium, gallium, indium, thallium, tin, lead and bismuth
of the p-block are considered to be metals. Further, germanium and polonium are also
sometimes taken to be metallic elements. Thus the metals constitute about eighty percent of
the element in the periodic Table. It appears that the element with too little electrons in the
valence shell but with too many orbitals behave as metals. No doubt, metals are marvels
among elements. The marvelous characteristics such as luster, conductivity, malleability,
ductility, etc of metals have been attributed to the metallic bond.

What is metallic Bond?

Metal possesses free electrons. In solids atoms are closely packed hence the orbitals are
overlap each other. So the valence electron do not localized. It jump from one orbital to the
another orbital of the other atom and continuously move on the surface of the metals with
certain energy. It is also called conduction electron. When metal atom loss a electron it
converted into positive ion and it holds an electron with an electrostatic force for the surface
of the metal. (below figure)
Metallic bonding is formed by the sharing of free electrons among a lattice of positively
charged metal ions. It formed a “sea” of electrons that surrounds the positively charged
atomic nuclei of the interacting metal ions. The electrons then move freely throughout the
space between the atomic nuclei.

Metallic bonding is a type of chemical bonding and is responsible for several characteristic
properties of metals such as their shiny lustre, their malleability, and their conductivities for
heat and electricity.

In other words ‘Metallic bond’ is a term used to describe the collective sharing of a sea of
valence electrons between several positively charged metal ions.

Example – Metallic Bonding in Sodium

The electron configuration of sodium is 1s2 2s2 2p6 3s1; it contains one electron in its valence
shell. In the solid-state, metallic sodium features an array of Na+ ions that are surrounded by
a sea of 3s electrons. An illustration describing the metallic bonding in sodium is provided
below.

The softness and low melting point of sodium can be explained by the relatively low number
of electrons in the electron sea and the relatively small charge on the sodium cation. For
example, metallic magnesium consists of an array of Mg 2+ ions. The electron sea here
contains twice the number of electrons than the one in sodium (since two 3s electrons are
delocalized into the sea). Due to the greater magnitude of charge and the greater electron
density in the sea, the melting point of magnesium (~650oC) is significantly higher than that
of sodium.

The factors that affect the strength of a metallic bond include:

 Total number of delocalized electrons.

 Magnitude of positive charge held by the metal cation.
 Ionic radius of the cation.

Properties Attributed by Metallic Bonding

Metallic bonds impart several important properties to metals that make them commercially
desirable. Some of these properties are briefly described in this subsection.

1. Electrical Conductivity

Electrical conductivity is a measure of the ability of a substance to allow a charge to move

through it. Since the movement of electrons is not restricted in the electron sea, any electric
current passed through the metal passes through it, as illustrated below.

When a potential difference is introduced to the metal, the delocalized electrons start moving
towards the positive charge. This is the reason why metals are generally good conductors of
electric current.

2. Thermal Conductivity

The thermal conductivity of a material is a measure of its ability to conduct/transfer heat.

When one end of a metallic substance is heated, the kinetic energy of the electrons in that
area increases. These electrons transfer their kinetic energies to other electrons in the sea via
collisions.

The greater the mobility of the electrons, the quicker the transfer of kinetic energy. Due to
metallic bonds, the delocalized electrons are highly mobile, and they transfer the heat through
the metallic substance by colliding with other electrons.
3. Ductiliy

The physical property of a metal that can be drawn into the thin wire is called ductility or
ductility is the property of metal associated with the ability to be hammered thin or stretched
into wire without breaking. The ductile materials are nickel, copper, steel etc.

The electron-sea model explains the malleability and ductility properties of metal. The sea
of electrons surrounding the protons acts like a cushion, and so when the metal is hammered
on, for instance, the overall composition of the structure of the metal is not changed. The
protons may be rearranged but the sea of electrons will adjust to the new formation of protons
and keep the metal intact.

4. Malleability

Malleability is the physical property of a solid to bend or be hammered into another shape
without breaking. If malleable, a material may be flattened into a thin sheet by hammering or
rolling. Examples of malleable metals are gold, silver, aluminium, copper etc.

5. Metallic Luster
When light is incident on a metallic surface, the energy of the photon is absorbed by the sea
of electrons that constitute the metallic bond. The absorption of energy excites the electrons,
increasing their energy levels. These excited electrons quickly return to their ground states,
emitting light in the process. This emission of light due to the de-excitation of electrons
attributes a shiny metallic lustre to the metal.

6. Cohesive Force
Cohesive forces are attractive forces between similar molecules. The enhanced Cohesion force
is due to the exchange of energy in mobile electrons. Cohesive force is associated with bulk (or
macroscopic) properties.
Cohesion or Cohesive Force is the activity or property of like atoms remaining together,
being commonly attractive. in metals, metallic bonds take place between two metals and
these metals contain free electrons known as mobile electrons. These mobile electrons are
free to move and they exchange energy. Because of these exchanges of energy, the force of
cohesion occurs. The enhanced force of cohesion in metals is due to the exchange energy of
mobile electrons.

Band theory of metals

Conductors are generally substances which have the property to pass different types of
energy. The alternatives are aluminum and copper.

Insulators are possess no free charge carriers and thus are non-conductive. Ex: Non-metals,
glass, plastic, rubber, air, and wood.

Semiconductors are solids whose conductivity lies between the conductivity of conductors
and insulators. Due to exchange of electrons - to achieve the noble gas configuration -
semiconductors arrange as lattice structure. Unlike metals, the conductivity increases with
increasing temperature. Ex: germanium, and silicon.

The energy bands

If we consider a single atom, there are according to the Bohr model of atoms sharply distinct
energy levels, which may be occupied by electrons. If there are multiple atoms side by side
they are interdependent, the discrete energy levels are fanned out. In a silicon crystal, there
are approximately 1023 atoms per cubic centimeter, so that the individual energy levels are
no longer distinguishable from each other and thus form broad energy ranges.

The width of the energy bands depends on how strongly the electrons are bound to the atom.
The valence electrons in the highest energy level interact strongly with those of neighboring
atoms and can be solved relatively easily from an atom; with a very large number of atoms, a
single electron can no longer be assigned to one single atom. As a result, the energy bands of
the individual atoms merge to a continuous band, the valence band.

Band theory of metals to explain conductors, insulators, extrinsic and intrinsic semi
conductors.

The Band theory is an energy scheme to describe the conductivity of conductors, insulators,
and semiconductors. The scheme consists of two energy bands (valence and conduction
band) and the band gap. The valence electrons - which serve as charge carriers - are located
in the valence band, in the ground state the conduction band is occupied with no electrons.
Between the two energy bands there is the band gap, its width affects the conductivity of
materials.

The band model of conductors

In conductors, the valence band is either not fully occupied with electrons, or the filled
valence band overlaps with the empty conduction band. In general, both states occure at the
same time, the electrons can therefore move inside the partially filled valence band or inside
the two overlapping bands. In conductors there is no band gap between the valence band and
conduction band.

The band model of insulators

In insulators the valence band is fully occupied with electrons due to the covalent bonds. The
electrons can not move because they are “locked up” between the atoms. To achieve a
conductivity, electrons from the valence band have to move into the conduction band. This
prevents the band gap, which lies in-between the valence band and conduction band.

Only with considerable energy expenditure (if at all possible) the band gap can be overcome;
thus leading to a negligible conductivity.

The band model of semiconductors

Even in semiconductors, there is a band gap, but compared to insulators it is so small that
even at room temperature electrons from the valence band can be lifted into the conduction
band. The electrons can move freely and act as charge carriers. In addition, each electron also
leaves a hole in the valence band behind, which can be filled by other electrons in the valence
band. Thus one gets wandering holes in the valence band, which can be viewed as positive
charge carriers.

There are always pairs of electrons and holes, so that there are as many negative as positive
charges, the semiconductor crystal as a whole is neutral. A pure undoped semiconductor is
known as intrinsic semiconductor. Per cubic centimeter there are about 1010 free electrons
and holes (at room temperature).

Since the electrons always assume the energetically lowest state, they fall back into the
valence band and recombine with the holes if there is no energy supply. At a certain
temperature an equilibrium is arranged between the electrons elevated to the conduction band
and the electrons falling back. With increasing temperature the number of electrons that can
leap the band gap is increased, and thus increasing the conductivity of semiconductors.

Types of Semiconductors
Semiconductors can be classified as:

 Intrinsic Semiconductor
 Extrinsic Semiconductor
Intrinsic Semiconductor
An intrinsic type of semiconductor material is made to be very pure chemically. It is made
up of only a single type of element.

Conduction Mechanism in Case of Intrinsic Semiconductors (a) In absence of electric field (b) In
presence of electric Field

Germanium (Ge) and Silicon (Si) are the most common type of intrinsic semiconductor
elements. They have four valence electrons (tetravalent). They are bound to the atom by
covalent bond at absolute zero temperature. When the temperature rises, due to collisions,
few electrons are unbounded and become free to move through the lattice, thus creating an
absence in its original position (hole). These free electrons and holes contribute to the
conduction of electricity in the semiconductor. The negative and positive charge carriers are
equal in number. The thermal energy is capable of ionizing a few atoms in the lattice, and
hence their conductivity is less.

Extrinsic Semiconductor
The conductivity of semiconductors can be greatly improved by introducing a small number
of suitable replacement atoms called IMPURITIES. The process of adding impurity atoms to
the pure semiconductor is called DOPING. Usually, only 1 atom in 10 7 is replaced by a
dopant atom in the doped semiconductor. An extrinsic semiconductor can be further
classified into:

 N-type Semiconductor

 P-type Semiconductor

N-Type Semiconductor

 Mainly due to electrons

 Entirely neutral
 nh >> ne
 Majority – Electrons and Minority – Holes
When a pure semiconductor (Silicon or Germanium) is doped by pentavalent impurity (P, As,
Sb, Bi) then, four electrons out of five valence electrons bonds with the four electrons of Ge
or Si.
The fifth electron of the dopant is set free. Thus, the impurity atom donates a free electron for
conduction in the lattice and is called “Donar“.
Since the number of free electron increases by the addition of an impurity, the negative
charge carriers increase. Hence, it is called n-type semiconductor.
Crystal as a whole is neutral, but the donor atom becomes an immobile positive ion. As
conduction is due to a large number of free electrons, the electrons in the n-type
semiconductor are the MAJORITY CARRIERS and holes are the MINORITY CARRIERS.

P-Type Semiconductor

 Mainly due to holes

 Entirely neutral
 nh >> ne
 Majority – Holes and Minority – Electrons
When a pure semiconductor is doped with a trivalent impurity (B, Al, In, Ga ) then, the three
valence electrons of the impurity bonds with three of the four valence electrons of the
semiconductor.
This leaves an absence of electron (hole) in the impurity. These impurity atoms which are
ready to accept bonded electrons are called “Acceptors“.
With the increase in the number of impurities, holes (the positive charge carriers) are
increased. Hence, it is called p-type semiconductor.
Crystal as a whole is neutral, but the acceptors become an immobile negative ion. As
conduction is due to a large number of holes, the holes in the p-type semiconductor are
MAJORITY CARRIERS and electrons are MINORITY CARRIERS.

Difference Between Intrinsic and Extrinsic Semiconductors

Intrinsic Semiconductor Extrinsic Semiconductor

Pure semiconductor Impure semiconductor

Density of electrons is equal to the Density of electrons is not equal to the density
density of holes of holes

Electrical conductivity is low Electrical conductivity is high

Dependence on temperature only Dependence on temperature as well as on the

amount of impurity

No impurities Trivalent impurity, pentavalent impurity

Applications of Semiconductors
Let us now understand the uses of semiconductors in daily life. Semiconductors are used in
almost all electronic devices. Without them, our life would be much different.

Their reliability, compactness, low cost and controlled conduction of electricity make them
ideal to be used for various purposes in a wide range of components and devices.
transistors, diodes, photosensors, microcontrollers, integrated chips and much more are made
up of semiconductors.

Uses of Semiconductors in Everyday life

 Temperature sensors are made with semiconductor devices.

 They are used in 3D printing machines

  Used in microchips and self-driving cars

 Used in calculators, solar plates, computers and other electronic devices.

 Transistor and MOSFET used as a switch in Electrical Circuits are manufactured

using the semiconductors.

Industrial Uses of Semiconductors

The physical and chemical properties of semiconductors make them capable of designing
technological wonders like microchips, transistors, LEDs, solar cells, etc.

The microprocessor used for controlling the operation of space vehicles, trains, robots, etc is
made up of transistors and other controlling devices which are manufactured by
semiconductor materials.

Importance of Semiconductors

Here we have discussed some advantages of semiconductors which makes them highly useful
everywhere.

 They are highly portable due to the smaller size

 They require less input power
 Semiconductor devices are shockproof
 They have a longer lifespan
 They are noise-free while operating