CH182: CHEMISTRY FOR ENGINEERS II (PART 2)

CHEMICAL BONDING AND STRUCTURE [CONTINUED]

Possibility of resonance structures

Sometimes more than one valid Lewis structure is possible for a given molecule. Let us consider nitrate ion.
It has 24 valence electrons; in order to achieve octet of electrons around each atom, the structure has to be:
:O:

.. :
:O :O
.. :

It is clear that there are two types of bonds. But experiments reveal that only one type of bond is present in
this ion. So, there are really three valid Lewis structures:
:O: .. ..
:O: :O: :O :

N N N N
..
.. :
:O :..O : :..O :..O : :..O O:
.. :O
.. ..O :

So, the correct description of nitrate ion is not given by any one of the three Lewis structures, but is given
only by the superposition of all the three structures (fourth structure above).

Thus resonance is invoked when more than one valid Lewis structure can be written for a particular
molecule. The resulting electron structure of the molecule is given by the average of these resonance
structures.

Orbital overlap

Two electron orbitals (usually s, p and d) from each of two different atoms overlap with each other in a
specified manner to result in the sharing of electron between them, resulting in a chemical bond. Depending
on the elements present, the bonding can be different for different molecules.

Valence bond theory: hybridization of orbitals

Here, the electrons that are involved in bonding remain localized between pairs of atoms, and bonding in the
whole structure is taken to be equal to the sum of individual bonds between pairs of atoms. This approach is
conceptually simpler and is widely used in organic chemistry, but it fails to adequately explain the bonding
in certain classes of molecules including aromatic compounds.

Electronic configuration and hence the valency of an atom plays vital role in deciding the chemical
properties. The valence electronic configuration for carbon is 2s22p2. In the box notation, it is written as:
2s 2p

(Ground state)

Only two of these four electrons are unpaired and hence available for bond formation. This can be overcome
if the carbon atom is excited to an s1p3 configuration as shown below:

CH182: Chemistry for Engineers II (Prepared by Janarthanan G.) 1

 2s 2p

(Excited state)

This has four unpaired electrons available in one s- and three p- orbitals, for the formation of four C-Cl
bonds, in case of carbon tetrachloride, CCl4 for example. These four orbitals are hybridized (or mixed or
overlapped) together to form a hybrid orbital. As a result, four equivalent sp3 hybrid orbitals (i.e., s + px +
py + pz sp3 hybrid orbitals) are formed, which separately point towards the four corners of a regular
tetrahedron.

Hybridization concept is discussed here for the formation of CCl4 molecule. In the same way, the argument
can be extended to the formation of other molecules like BeCl2, BCl3, PCl5, SF6 and so on. Due to the
hybridization, electrons are localized in the bond region. The overlapping atomic orbitals can be of different
types, for example, a sigma () bond may be formed by the overlapping of s-s (Li-H), s-p (H-C) or p-p (C-
C) orbitals. The table below lists various hybridizations leading to various hybridized orbitals. Here,
coordination number is defined as the total number of atoms directly bonded to the central atom.

Coordination number Hybrid orbitals Geometry Examples

2 sp Linear BeCl2
3 sp2 Trigonal planar BCl3
4 sp3 Tetrahedral CCl4
5 dsp3 Trigonal bipyramidal PCl5
6 d2sp3 Octahedral SF6

The atom at the centre (central atom) is surrounded by other atoms (surrounding atoms). In order to satisfy
the surrounding atoms, the orbitals of the central atom are appropriately hybridized to form a set of
equivalent orbitals called hybridized orbitals.

Formation of sp3 hybrid orbitals: another example CCl4

Mixing one s and all three p atomic orbitals produces a set of four equivalent sp3 hybrid atomic orbitals. The
four sp3 hybrid orbitals points towards the vertices of a tetrahedron. When sp3 hybrid orbitals are used for
the central atom in the formation of molecule, the molecule is said to have the shape of a tetrahedron.

forms 4 sigma bonds with

4 Cl atoms
Cl

C
Cl
Cl
Cl

Multiple bonds

The sharing of a pair of electrons constitutes a single covalent bond, generally referred to as a sigma bond
(bond order 1). In many molecules, atoms attain complete octet by sharing more than one pair of electrons
CH182: Chemistry for Engineers II (Prepared by Janarthanan G.) 2
between them. When two electron pairs are shared, a double bond results (1 sigma + 1 pi, bond order 2).
When three electron pairs are shared, a triple bond results (1 sigma + 2 pi, bond order 3).

Example: N2 molecule.
.. ..
: . + N.:
N : N ::: N : OR :N N:
Each N atom possesses 5 electrons in its valence shell. The sharing of 3 electron pairs is required to achieve
the octet configuration. N2 molecule possesses low reactivity because of stronger and stable triple bond.
Bond length decreases with increase in bond order (N-N, 1.47, N=N, 1.24 , NN, 1.10 ).

Another example is CO2.

... . ..
O . . C . .O .
.. . ..
.. ..
O ::C::O
..
.. ..
.. ..
OR O C O
..
Bond type No. of bond No. of bonds
Single (C-H) 1 0
Double (C=C) 1 1
Triple (CC) 1 2

Hybridization in ethane

Hybridization in ethene (ethylene)

If two p orbitals are utilized in making hybrids with the s orbital, then three new hybrid orbitals (called sp2
hybrid orbitals) form and they constitute the framework. The unused p orbital will participate in type
bonding

p orbital
H 1s orbital
C

sp2 hybrid orbitals

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Hybridization in carbon dioxide

Hybrid orbitals in CO2 Formation of sp hybrid orbitals of C

Orbitals of sp hybridized C atom (1s + 3p) Orbitals of sp2 hybridized O atom (1s + 3p)

Orbitals used to form bonds in CO2 molecule

Differences between sigma and pi bonds

No. Sigma () bond Pi () bond

1 This bond is formed by the axial overlap of atomic This bond is formed by the sidewise overlap
orbitals (head-on or end-to-end overlap) of atomic orbitals (lateral overlap)
- -
axis +
+
+ + axis

2 Formed by overlap of s-s, s-p or p-p orbitals
3 The bond is stronger because overlapping can take
place to a larger extent
4 The molecular orbital is symmetrical about the
internuclear axis and consists of single charged cloud
CH182: Chemistry for Engineers II (Prepared by Janarthanan G.)
- -
Involves the overlap of p-p, d-d, p-d orbitals
The bond is weaker because the overlapping
occurs to a smaller extent
The molecular orbital is discontinuous and
consists of two charged clouds above and
4
 - + + - below the plane of atoms
+ + +
+
+
- - -
5 There can be a free rotation of atoms around the Not possible in bond because it involves
bond breaking of the bond

only : possible + : not possible

6 The bond may be present between two atoms either The bond is always present between two
alone or along with bond atoms along with the bond (it is always
superimposed on bond)
7 The shape of molecule is determined by the sigma The bonds do not contribute to the shape,
framework around the central atom however they modify the dimensions of the
molecule

Molecular geometries: Valence Shell Electron Pair Repulsion Theory (VSEPR)

This theory is used to predict and explain the exact shapes and bond angles of molecules, anions and cations.
Covalent bonds that make up a covalent molecule are directional in nature and most of the molecules have
three-dimensional shape. This shape is determined by the number of electron pair bonds in the valence shell
configuration of the central atom about which the shape of the molecule is described. So, given an example,
identification of the central atom is the first task in working out this model.

The idea is based on the fact that, valence electron pairs, being negatively charged stay as far apart from
each other as possible so that the repulsions between them are at a minimum. Valence Shell Electron Pair
Repulsion theory (VSEPR) was developed by Gillespie and Nyholm during 1957. There is no direct
relationship between the formula of a compound and the shape of its molecules. The shapes of these
molecules can be predicted from their Lewis structures with the help of VSEPR.

Summary of VSEPR theory

1) For molecules with resonance structures, any of the structures can be used for predicting the molecular
structure.
2) The shape of the molecule is determined by repulsions between all of the electron pairs present in the
valence shell.
3) Lone pair (lp) of electrons occupy more space around the central atom than a bond pair, because the lone
pair is attached to only one nucleus, while, bond pair (bp) is shared by 2 nuclei. So, lp-lp repulsion > lp-
bp repulsion > bp-bp repulsion.

Thus presence of lp on central atom causes slight distortion of bond angles from the ideal shape. If the
angle between lp, central atom and bp is increased, then, the actual bond angles between the atoms must
be decreased. If a is greater, then, b becomes smaller. That is, distortion in geometry.
4) Repulsions between the bonding pairs in a molecule depend on the difference between the
electronegativities of the central atom and the surrounding atoms. In the molecule MXn, the more the M-
X bonding electron density is drawn away from the central atom M, the less the bp-bp repulsions.
5) Double bonds cause more repulsion than single bonds and triple bonds cause more repulsion than a
double bond. Thus, triple bond-single bond > double bond-single bond > single bond-single bond.

CH182: Chemistry for Engineers II (Prepared by Janarthanan G.) 5

VSEPR treatment to simple molecules

1) BeCl2 molecule (valence e- of Be = 2, Cl = 7)

.. ..
: Cl : Be : Cl
.. :
The Lewis structure is,
..
There are two possibilities of arrangement. They are:

Be
Cl Be Cl (linear) Cl Cl (non-linear or bent or angular)

The central atom has 2 bp of electron. According to VSEPR, the repulsion between them will be minimized
only when they adopt a linear structure (the two Cl groups are away from each other by 180).
Experimentally, BeCl2 is found to have a linear structure.

2) BCl3 molecule (valence e- of B = 3, Cl = 7)

..
.. : Cl
.. : ..
The Lewis structure is, : Cl :
.. B : Cl .. :
The central atom B has 3 bp. In order to have a minimum repulsion between these 3 bp, it should adopt a
triangular structure with 3 Cl atoms located at corners of an equilateral triangle. B has no lp. So, no
repulsions due to lp-bp. Therefore, the molecule is trigonal planar. That is,

Cl

B
Cl Cl

3) CCl4 molecule (valence e- of C = 4, Cl = 7)

..
:Cl :

The Lewis structure is: .. C ..

:Cl
.. .. :
Cl
: Cl
.. :

BeCl2 and BCl3 are both two-dimensional molecules, in which the atoms lie in the same plane. If the same
restriction is placed on CCl4, a square-planar geometry is obtained in which the Cl-C-Cl bond angle is 90o
(Fig. a). However, if the system is allowed to expand into three dimensions (3D), a tetrahedral molecule is
obtained, in which the H-C-H bond angle is 109o28'. Therefore, the structure of CCl4 molecule is tetrahedral
(Fig. b).
Cl 90 Cl Cl
C 19028'
C
Cl Cl Cl
Cl
Cl
(a) Square planar (b) Tetrahedral

4) PCl5 molecule (valence e- of P = 5, Cl = 7)

..
.. .. ..

Cl
.. . .. ..
.. .. ..

..Cl
..
.

The Lewis structure is: P ..

Cl .. ..Cl
..

: Cl
.. :

CH182: Chemistry for Engineers II (Prepared by Janarthanan G.) 6

Repulsion between the five pairs of valence electrons on the phosphorus atom in PCl5 can be minimized by
distributing these electrons toward the corners of a trigonal bipyramid. Three of the positions in a trigonal
bipyramid are labeled equatorial because they lie along the equator of the molecule. The other two are axial
because they lie along an axis perpendicular to the equatorial plane. Therefore, the structure is,
Cla
Cl e
Cle P e = equatorial position
a = axial position
Cle
Cla

5) SF6 molecule (valence e- of S = 6, F = 7)

..
: F: ..
..
The Lewis structure is:
: ..F
S
..F :
.. ..
: ..F F:
..
: F.. :

All the six valence electrons of sulphur are utilized in the bond formation with six fluorine atoms. The
repulsion between the valence electrons can be minimized by distributing them toward the corners of an
octahedron. Thus the structure of SF6 molecule is octahedral:
F
F F
S
F F
F
The following table shows various shapes possible for differing coordination number (the total number of
groups / atoms attached to the central atom). The bond angles are also specified. Here, all the valence
electrons of the central atom are completely utilized for the bond formation and hence no lone pairs of
electrons are present. The following figure shows the possible shapes for various coordination numbers.

Coordination No. (C.N.) Possible shapes Bond angle

2 Linear 180
3 Trigonal planar 120
4 Tetrahedral 10928 (109.5)
5 Trigonal bipyramidal 90, 120, 180
6 Octahedral 90, 180
7 Pentagonal bipyramidal 72, 90, 180

Examples with lone pairs of electrons

In all the above cases discussed, bond pairs of electrons are only present on the central atom; no lone pairs
are present. In case of NH3, one lp is present. In case of H2O, 2 lp are present (discussed below).

1) NH3 and H2O molecules

Nitrogen is the central atom (in most cases, atom with least number is the central atom).
N has 5 valence electrons.

CH182: Chemistry for Engineers II (Prepared by Janarthanan G.) 7

N =5
3 (H) =3
Difference = 2 these two electrons are present as 1 lp

Therefore, the coordination number of N in NH3 = 3 bp + 1lp = 4 Tetrahedral geometry. A similar

treatment for water ends up in bent or angular or non-linear. The bond angle values are listed in the
following table.
.. ..

N O
H H
H H
H

..
VSEPR theory predicts that the valence electrons on the central atoms in ammonia will point toward the
corners of a tetrahedron (as above). The non-bonding electrons cant be located with any precision and
hence for predicting the exact geometry, the lone pairs can be omitted. Thus, the positions of the nuclei
alone in ammonia are focussed and hence the molecular geometry is trigonal pyramidal, with the nitrogen
at the top of the pyramid. The electronic geometries of ammonia and water are tetrahedral.
.. ..

N N O
H H O
H H H H H
H H H
Trigonal pyramidal .. Bent or angular or
non-linear

Compound bp lp C.N. Base structure (electronic geometry) H-X-H bond angle

CH4 4 0 4 Regular tetrahedron (tetrahedron) 10928
NH3 3 1 4 Distorted tetrahedron (trigonal pyramidal) 10748
H2O 2 2 4 Highly distorted tetrahedron (bent) 10427

Thus, in ammonia, a lp-bp repulsion is present which distorts the regular tetrahedral geometry. Similarly, in
water, there are two lonepairs available which cause a lp-lp repulsion and much more distortion is seen as
indicated by the bond angle reduction.

2) SnCl2 molecule [tin(II) chloride or stannous chloride]

This molecule has one lp of electrons. The number of valence electrons of tin is 4 and that of chlorine is 7.
..
.. .. ..
Sn
The Lewis structure is, : Cl
.. : Sn : Cl
.. :
Cl Cl

3 pairs of electrons are there around Sn: 2 bp and 1 lp. To minimize repulsion, they are placed in corners of
triangle. So, the actual shape of SnCl2 is non-linear or bent or angular.

4) SF4 molecule

There are four bp of electrons and one lp of electrons. The basic shape is therefore trigonal bipyramid. The
lp can be placed either in the axial position (Fig. left-hand side) or equatorial position (Fig. right-hand side).

CH182: Chemistry for Engineers II (Prepared by Janarthanan G.) 8

If the lonepair of electrons in SF4 are placed in an axial position, they will be relatively close (90o) to three
pairs of bonding electrons. But if the same are placed in an equatorial position, they will be 90o away from
only two pairs of bonding electrons. As a result, the repulsion between lonepair and bonding electrons is
minimized if the lonepair electrons are placed in an equatorial position in SF4. Hence, the correct shape of
the molecule is unsymmetrical tetrahedron or disphenoidal or see-saw (see below).

F
: S
F
F

Incorporating localized double and triple bonds into the structures

The geometry around an atom is determined by the number of places in the valence shell of an atom where
electrons can be found, and not the number of pairs of valence electrons. Consider the Lewis structures of
carbon dioxide (CO2) and the carbonate (CO32-) ion, for example.
: O: 2-
.. ..
CO2 : :O C O: CO32- : C
:..O: .. :
:O
There are four pairs of bonding electrons on the carbon atom in CO2, but only two places where these
electrons can be found. However, there are electrons in the C=O double bond on the left and electrons in the
double bond on the right. The force of repulsion between these electrons is minimized when the two C=O
double bonds are placed on opposite sides of the carbon atom. The VSEPR theory therefore predicts that
CO2 will be a linear molecule, with a bond angle of 180o which is found to be experimentally true.

The Lewis structure of the carbonate ion also suggests a total of four pairs of valence electrons on the central
atom. But these electrons are concentrated in three places: The two C-O single bonds and the C=O double
bond. Repulsions between these electrons are minimized when the three oxygen atoms are arranged toward
the corners of an equilateral triangle. The CO32- ion should therefore have a trigonal planar geometry, with a
120 bond angle.

The following table summarizes some simple known examples containing only double bonds (denoted as D)
and not the lp of electrons. The structures of these examples are shown in the figure.

No. of electron pairs No. of double bonds Formula Shape Examples

3 1 AB3D Trigonal planar CO32-
4 1 AB4D Tetrahedral PO43-
4 2 AB4D2 Tetrahedral SO42-
4 3 AB4D3 Tetrahedral ClO4-

3- 2- -
2-
: O: :O: :O:
: O:
.. P .. S Cl
C :..O ..O: ..
:..O :O..: : O.. ..O:
:..O: .. :
:O :O
.. : :O: :O
.. :
carbonate ion phosphate ion sulphate ion perchlorate ion

However, there are many cases where the molecule / ion contain both lone pair(s) and double bond(s). These
are quite complicated and beyond the scope of this subject.

CH182: Chemistry for Engineers II (Prepared by Janarthanan G.) 9

For the VSEPR model, multiple bonds count as one effective electron pair. When a molecule exhibits
resonance, any one of the resonance structures can be used to predict the molecular structure using the
VSEPR model.

Advantages of VSEPR

This model is very simple and requires only the electron configuration of the elements present. It works best
for simple halides of the p-block elements and species containing other substituents. Molecules of any size
can be treated by applying this model to each appropriate atom in the molecule. It emphasizes the
importance of lone pairs of electrons in determining the extent of distortion from the regular
stereochemistry.

Limitations of VSEPR

It does not work well for the d-block elements where incomplete d-shells are involved and form numerous
coordination compounds. Also, the model does not consider the steric effects of the substituents, that is, the
relative size of the substituents. Working out the details of the geometry of heavier elements of the Main
Group which involves angular trends, are difficult to rationalize (for example, the angle H-X-H in H2O is
104.5, while it is 92.5 and 90 for H2S and H2Se).

Bonding in solids: metals, insulators and semiconductors - Band theory of solids

Band theory of solids can be considered as molecular orbital theory of covalent bonds extended to solids. To
understand the band theory, imagine the construction of a crystal of lithium metal by adding Li atoms one at
a time, first forming Li2, then Li3, Li4, ....Li9, ..... LiN, where N is a very large number. In the diatomic Li2
molecule, each Li atom has electronic configuration 1s2 2s1 with a single 2s valence electron.

The two 2s atomic orbitals (AO), one from each Li atom, overlap to form the two molecular orbitals (MO):
lower energy MO (2s) called as Bonding Molecular Orbital (BMO) and higher energy MO *(2s) called as
Anti-Bonding Molecular Orbital (ABMO). BMOs correspond to positive overlap between all the atomic
orbitals to give a totally bonding combination, whereas the ABMOs contain a node between each pair of
atoms and is thus totally antibonding (see below). T The continuous set of allowed energy levels generated
in band theory when the valence orbitals of the atoms in a solid interact with one another, thus creating a set
of molecular orbitals that extend throughout the solid is called the energy band. The Molecular Orbital
Energy-Level Diagram for a linear arrangement of n atoms, each of which contains a singly occupied s
orbital is given below:

The *(2s) orbital is vacant. In general, n AO combine to form n MO. In Li3, the three 2s AO overlap to
form three MO. Electrons in the MO are spread over the three Li nuclei and they belong to the entire Li3
molecules, and not to any one Li atom (the electrons are said to be delocalized throughout the molecule).

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For N Li atoms, there are N MO that arise from the overlap of the 2s valence AO of all the N Li atoms. The
separation between the MO decreases as the number of atoms (N) increases (see figure below), so that there
is a band of N closely spaced MO. The band is only half-full, since each MO can hold 2 electrons, and there
are only N valence electrons. The band containing the outer or valence electrons is called the valence band.
A band is a group of molecular orbitals and the energy differences between these MO are so small that the
system behaves as if a continuous, non-quantized variation of energy within the band is possible. The empty
2p AO of the Li atoms also overlap to form a wide band of MO. Since the 2s and 2p orbitals do not differ
much in energy, the band of MO formed from the 2s AO and the band of MO formed from the 2p AO join
continuously, and are called the conduction band. A band that is either partly or completely vacant is called
conduction band. Electrons in the lower filled levels of the conduction band can easily be unpaired and
excited to vacant levels of the band. In these delocalized orbitals, they can circulate throughout the crystal.
When an electric field is applied across a lithium crystal, the electrons start moving in one direction and
hence Li is a good conductor of electricity. Likewise, in the next alkali metal sodium, the 3s band is half
filled and it is called the valence band. The 3p band is empty. The 3s and 3p bands overlap to form the
conduction band. For Group 2 alkaline earth metals, the valence band is filled by two valence electrons per
atom. For example, Mg has completely filled 3s band. However, the overlap of 3s and 3p bands creates a
conduction band and that is only partially filled. Hence solid Mg can conduct electricity.

A similar MO energy-level diagram for the formation of LiN is also given below:

Li Li2 Li3 Li4 Li9 LiN

The difference in energy between the highest and lowest energy levels is called the bandwidth and is
proportional to the strength of the interaction between orbitals on adjacent atoms: the stronger the
interaction, the larger the bandwidth.

Properties of metals

Band theory can explain all the properties of metals.

1. Metals conduct electricity because only a very small amount of energy is required to excite an electron
from a filled level to an empty one, where it is free to migrate rapidly throughout the crystal in response
to an applied electric field.
2. Metals have high heat capacities because the electrons in the valence band can absorb thermal energy by
being excited to the low-lying empty energy levels.
3. Metals are lustrous because light of various wavelengths can be absorbed, causing the valence electrons
to be excited into any of the empty energy levels above the highest occupied level. When the electrons
lose energy and get back to the low-lying empty levels, they emit light of different wavelengths which
results in the shiny appearance of the metals.

Salient features of band theory

1. Solids are made up of giant molecules, in which a very large number of spherical atoms are arranged
in a regular close packed pattern in the form of crystals.
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 2. When the atoms are brought together in solids, the AO of the valence shells interact forming MO.
3. There are approximately 1023 atoms in 1 cm3 of a solid; and during interaction between different
atoms, they influence each other to such an extent that their outer shells (empty as well as partially
filled) constitute one single system of electrons, common to entire array of atoms in crystal; while
inner shells (core shells and hence core electrons) remain intact and are not affected.
4. When n energy levels of identical atoms interact, each energy level gets split into a number of
infinitesimal energy levels. As a result of this, each original energy level becomes a band of very
closely spaced levels of extremely small energy differences. The individual energies within an
energy band are so close together that for all purposes, the energy band may be considered to be
continuous. Consequently, an electron in a solid crystal can thus occupy any of these large numbers
of energy levels, within the band. Thus, a band is a group of infinitesimal energy levels in a solid /
crystal.
5. Depending upon the composition of a solid / crystal, the bands are of two types:
(a) Overlapping band - The higher band overlaps lower band to some extent.
(b) Non-overlapping or separate bands The higher and the lower bands are separated by
forbidden gap.

Energy Overlappin band

Higher
band
Lower Forbidden gap
band Lower
band

6. The band of energy levels occupied by the valence electrons (or highest occupied energy band) is
called valence band. It may be: (i) partially filled with electrons, e.g., Na (3s1), Al (3p1) and Cu
(4s1); or (ii) completely filled with electrons, e.g., Be (2s2) and Mg (3s2)
7. The next higher permitted band, above the valence band, is called the conduction band, and the
electrons occupying this band are called conduction electrons. These electrons are "free electrons"
and once an electron enters the conduction band, it moves freely. The conduction band may be empty
or partially filled with electrons.

Conduction band (empty or partially filled)

Forbidden gap
Valence band (fully or partially filled)
Energy
3p
3s
2p Completely filled or
2s intact inner shells
1s

8. The gap between the valence band and the conduction band is called forbidden gap. No electron can
exist in this gap. The width of the forbidden gap is called energy gap, Eg.
9. A solid is said to be a conductor, if it has either a partially filled valence band (e.g. Li, Na, Al or Cu)
or a filled valence band overlapping with the next higher empty band (e.g. Be or Mg).
(a) Conduction in conductors with partially-filled valence band: Electrons in half-filled
valence bands are "delocalized" and can move throughout the solid like "free electrons".
When a potential is applied across the solid, some of these free electrons are raised to the
conduction band. Here, these electrons gain momentum and begin to conduct. For example,
in metals like Li, Na, Al, Cu, etc. there exist half-filled conduction bands. The transfer of

CH182: Chemistry for Engineers II (Prepared by Janarthanan G.) 12

 electrons to the conduction band can also be accompanied by "light photons". This
phenomenon called "photo conduction" is observed in metals like selenium.
(b) Conduction in conductors with filled valence band overlapping with the next higher empty
band: Mg [1s2 2s2 2p6 3s2 3p0] has all the available bands completely filled with electrons.
The 3s valence band overlaps with the empty 3p band, thereby resulting in a partially-filled
band. Hence Mg is a conductor like Na, Al, Cu, etc.
(c) Variation of conductivity of metals with temperature: The electrical conductivity of a
metal decreases with rise in temperature, because increased thermal vibrations of the metal
atoms causes scattering of electrons, thereby obstructing their free flow.
10. Insulators: Solids in which valence band electrons are tightly bound to their parent nuclei and
require very large electric fields to remove electrons to conduction band, are insulators. These solid
materials possess:
(a) full-valence band
(b) completely empty conduction band
(c) large energy gap Eg of the order of 5-10 eV (1 eV ~ 96 kJmol-1). For example, Eg for
diamond and glass are 5.47 and 10 eV respectively. Higher the Eg value, better is the
insulating property of the material. Examples of insulators are diamond, glass, solid NaCl,
plastics, porcelain and ceramics.
11. Conduction in insulators: Thermal energy of an insulating material at room temperature is ~0.025
eV, and this is far less than Eg. Consequently, at room temperature, there is no chance for electrons in
valence band to jump into conduction band. Hence, these substances show best insulating properties
at room temperature. However, at high temperatures, some of the valence band electrons acquire
sufficient (thermal) energy to overcome the forbidden gap and enter the conduction band. These
electrons in the conduction band are now free to move and hence, the insulators start exhibiting
conductivity with increased temperature. Higher is the temperature of an insulator, higher is its
conductivity. In other words, conductivity of an insulator increased with increase in temperature.
12. Semiconductors: A solid is said to be a semiconductor if it has: (i) almost filled valence band; (ii)
almost empty conduction band, and (iii) a very narrow Eg (that is, in the order of 1 eV). The
following figure compares the energy bands of: (a) an insulator; (b) a metal in which the lower band
is only partially occupied; (c) a metal in which the occupied and empty bands overlap; and (d) a
semiconductor. Eg of Si and Ge are 1.11 and 0.66 eV respectively, and so they are semiconductors.

In this figure, in (a) the valence electrons are tightly bound in the valence band; conduction band is
empty; it has large Eg. In (d), the valence band is almost filled while the conduction band is empty; it
has small Eg.
13. Effect of temperature on conductivity of semiconductors: At 0 K, all semiconductors are
insulators. At finite temperature, conduction in semiconductors starts, due to thermal energy. Some
valence electrons gain enough thermal energy to jump over the energy gap Eg into the conduction
band. The probability of the promotion of electrons from valence band to conduction band: (i)
decreases exponentially with Eg; and (ii) increases exponentially with Kelvin temperature.
Consequently, the conductivity of a semiconductor increases with increase in temperature.
CH182: Chemistry for Engineers II (Prepared by Janarthanan G.) 13
 14. Metals are, in general, good conductors; insulators are bad conductors; and semiconductors lie
inbetween. The conductivity of semiconductors can be increased by: (a) increasing the temperature;
and (b) doping with Group 13 (Eg. Ga) or Group 15 (Eg. Sb) elements into the Si or Ge matrix.
15. List of materials along with their electrical conductivities are given below:

Doping

Doping is the process of deliberately introducing small amounts of impurities into commercial
semiconductors to tune their electrical properties for specific applications.

Types of semiconductors

n-Type semiconductor: A semiconductor that has been doped with an impurity that has more valence
electrons than the atoms of the host lattice. These extra electrons act as charge carriers. Example: doping of
antimony (5e) into silicon (4e).

p-Type semiconductor: A semiconductor that has been doped with an impurity that has fewer valence
electrons than the atoms of the host lattice. These create positive holes which act as charge carriers.
Example: doping of gallium (3e) into silicon (4e).

CH182: Chemistry for Engineers II (Prepared by Janarthanan G.) 14