Chemical bonding and shapes of molecules

Valence shell and Valency

The outermost shell of an atom is called valence shell. The electrons present in this shell are
called valence electrons. The number of electron have been shared or transferred between atoms
to complete their octet or duplet during the chemical bond formation is called valency.
Lewis symbols
G. N. Lewis introduce the symbol to denote the outer shell electrons in an atom. The outer shell
electrons are shown as dots surrounding the symbol of the atom. These symbols are known as
Lewis symbols.

Octet rule
The tendency of the atoms to acquire eight electrons in their outermost shell by gaining, losing
or sharing of electrons is known as octet rule.
Limitation of octet rule
1. It could not explain the formation electron deficient molecules such as BeCl2, BF3, AlCl3 etc.
2. It could not explain about the excess electron of P atom in PCl5, S in SF6 etc.
Chemical Bond
The force of attraction that binds the atoms of the elements together in a
molecule is called chemical bond. The tendency of such atoms to gain stability is
the reason for the chemical combination.

Types of Chemical bond

1. Electrovalent bond or ionic bond
The bond formed by the complete transfer of electrons from one combining atom
to the valence shell of another combining atom is called electrovalent bond.
The no. of electrons lost or gained during the formation of electrovalent bond is
termed as electro-valency of the element. The compound formed through ionic
bond is called ionic compound. For the formation of ionic bond, the atoms must
have low I.E. and high E.A.
Formation of ionic compound (Lewis symbols)
i) Formation of sodium chloride
NaCl is formed by complete transfer of one electron from valence shell of
sodium to valence shell of chlorine.
Na + Cl Na+ + Cl-
(2,8,1) (2,8,7) (2,8) (2,8,8)
ii) Formation of MgCl2
Mg + Cl + Cl Mg++ + Cl- + Cl-
2,8,2 2,8,7 2,8,7 2,8 2,8,8 2,8,8
Characteristics of ionic compound
Ionic compound have following characteristics.
1. Ionic compound are generally crystalline in nature.
2. They are soluble in water and other polar solvent but insoluble in non polar solvent like
benzene.
3. Ionic compound have high melting and boiling point since electrovalent bond is very strong
bond so large amount of heat is required to break the bond.
4. Ionic compounds do not conduct the electricity at solid state. However, They are able to
conduct electricity in the molten state or in aqueous solution.
5. They are hard but brittle in nature.
6. The reactions of ionic compounds are very fast.
2. Covalent Bond
The bond formed by mutual sharing of valance electrons between the combining atoms of
same or different element is called covalent bond. The number of electron shared by an atom
during the formation of covalent bond is called covalency. For the formation of covalent bond,
both the atoms must have high I.E. and E.A. and have low electronegativity difference (<1.8).
The compounds formed by formation of covalent bond are called covalent compounds. e.g.
CH4, C2H6, H2O etc.

3. Coordinate covalent bond or coordinate bond or dative bond

The covalent bond formed by sharing of electrons in which shared pair of electron belongs to
only one atom is called coordinate bond. The atom which provides the electron pair is termed
as the donor atom while the other atom which accept it is termed as acceptor. A coordinate
covalent bond is represented by an arrow (→) pointing towards the acceptor atom. It has some
polar character. For the formation of coordinate bond the donor atom must have at least one
lone pair of electron. The resulting compounds are known as coordinate covalent compound.
Characteristics of covalent compound
The covalent compound have following characteristics.
1. Covalent compound exist in solid, liquid and gaseous state.
2. They have low melting and boiling point as there is weaker force of attraction
among molecules in covalent compounds.
3. They are insoluble in water but soluble in nonpolar solvent.
4. They do not conduct the electricity.
5. The reaction of covalent compounds are slower than that of ionic compound.
Lewis structure of some covalent compounds or ions
Resonance
The phenomenon in which a molecule or ion can be represented by more than one structures to
explain its properties is called resonance. Such Lewis structures are called resonating structure.
None of these structures correctly represent the actual structure of molecule or ion. The real
structure is combination of these structures which is called resonance hybrid.
Resonating structure of some molecules
i) Ozone (O3)

ii) Sulphur trioxide (SO3)

iii) Sulphur dioxide (SO2)

iv) Carbonate ion (CO3- -)

VSEPR Theory
Valence Shell Electron Pair Repulsion(VSEPR) theory is a simple theory to predict and
explain the shape and bond angles in a number of simple covalent molecules and ions.
This theory was proposed by Sedgwick and Powell in 1940 and developed by Gillespie
and Nyholm in 1957. The main postulates of this theory are as follows:
1. The shape of a covalent molecule or ion is determined by the total number of
electron pairs present in the valence shell of the central atom in the molecule. The
electron pairs remain arranged around the central atom in space so as to get
minimum repulsion and hence determines the shape.
2. If the central atom has lone pairs along with bond pairs, the ideal shape gets distorted
to give different bond angle than expected.
3. The repulsion between electron pairs decreases in the order
l.p.-l.p. > l.p.-b.p. > b.p.-b.p.
4. The electronegativity of atoms in the molecule also affects the bond angle of the
molecule.
Shape of molecules on the basis of VSEPR theory
1. BeF2
In BeF2 , the central Be-atom has two bond pairs of electrons in its valence shell.
According to VSEPR theory , these two b.p. of electrons arrange themselves at an
angle of 1800 so as to get minimum repulsion. Thus the molecule of BeF2 will
have linear shape.
F Be F
Fig: linear structure of BeF2
2. BF3(BCl3)
The central B-atom has three bond pairs of electrons in its valence shell. The
repulsion of three electron pairs is minimum in trigonal planer geometry with
bond angle of 1200. Hence BF3 has trigonal planer structure.
F
B F
F
3. CH4 (CCl4, CHCl3, CH3Cl)
In CH4 molecule, the central C-atom has four bond pairs of electrons in its valence
shell. According to VSEPR theory the repulsion of four b.p.s is minimum in
tetrahedral geometry with bond angle of 109028’.
H

C
H H
H
fig: tetrahedral structure of CH4
4.NH3(PH3, PCl3)
In NH3, the central N-atom has four electron pairs, three b.p.s and one l.p. hence
the expected geometry is tetrahedral with bond angle of 109028’.but there is one
l.p. and the repulsion of electron pair is in order l.p.-b.p. > b.p.-b.p. , so the bond
angle gets reduced from 109.50 to 107.50 and shape becomes trigonal pyramidal.
..
N
H H
H
Fig: pyramidal structure of NH3
5. H2O(H2S with bond angle 92.50)
In H2O, the central O-atom has four electron pairs two b.p. and two l.p. hence the
expected geometry is tetrahedral with bond angle of 109.50 but there is two l.p.
of electrons on O-atom and repulsion is in order l.p.-l.p. > l.p.-b.p. > b.p.-b.p.
,the bonded pair get closer and bond angle decreases from 109.50 to 104.50 and
the shape becomes bent or angular.
: O:

H H
Fig: Bent structure of H2O
6. PCl5
In PCl5, the central P-atom has five electron pairs in its valence shell. Repulsion of
five electron pair is minimum in trigonal bipyramidal geometry. Hence PCl5 has
trigonal bipyramidal shape. Three bonds are in the same plane with angle 1200 to
each other called equatorial bond and the remaining two are at 900 above and
below the plane called axial bond.
Cl
Cl
P Cl
Cl
Cl
Fig: trigonal bipyramidal structure of PCl5
7. SF6
In SF6, central S-atom has six bond pairs of electron in its valence shell. Hence
according to VSEPR theory it will have octahedral geometry with bond angle of
900.
F
F F
S
F F
F
Fig : Octahedral structure of SF6
Valence bond theory
Valence bond theory was proposed by Heitler and London in 1927 and improved
by Linus Pauling to explain the nature of bonding in covalent molecules.
According to this theory, a covalent bond is formed by overlapping of atomic
orbitals having unpaired electrons. The main pustulates of this theory are:
1. Half filled atomic orbitals of one atom overlaps with half filled atomic orbitals
of another atom to form a covalent bond.
2. The two half filled atomic orbitals involved in the covalent bond formation
should contain electrons with opposite spins.
3. The completely filled orbitals do not take part in the bond formation.
4. Atomic orbitals undergoing overlapping must be close to each other with proper
alignment.
5. The strength of bond formed depends upon the extent of overlapping of atomic
orbitals. Greater the overlapping, stronger will be the bond formed.
Types of covalent bond
There are two types of covalent bond depending upon type of overlapping of
orbitals.
1. Sigma(σ) bond
The covalent bond formed by end to end or head on or axial overlapping of half
filled atomic orbitals is called sigma bond. Overlapping takes place along the
internuclear axis. The extent of overlapping is large so the bond formed is strong.
It is formed by following types of overlapping
i. s-s overlapping
ii. s-p overlapping
iii. p-p overlapping
2. Pi (Π) bond
The covalent bond formed by sideways or lateral overlapping of half filled atomic
orbitals is called pi-bond. Overlapping takes place perpendicular to the
internuclear axis. The extent of overlapping is small so the bond formed is weak.
It is formed only by p-p overlapping.
Hybridization
The process of mixing of same or different orbitals of nearly equal energy in an
atom to form new orbitals of equivalent energy and identical shape is called
hybridization and the orbitals so formed are called hybrid orbitals. The major
characteristics of hybridization are
1. Atomic orbitals undergoing hybridization must have nearly equal energy.
2. Full filled, half filled as well as empty atomic orbitals can undergo
hybridization.
3. The number of hybrid orbitals formed is equal to total number of atomic
orbitals involved.
4. Hybrid orbitals have new character and are equivalent in energy and identical
in shape and take the geometry so as to get minimize repulsion.
Types of hybridization
There are three types of hybridization depending upon the involvement of s- and p- orbitals
1. sp-hybridization( linear or diagonal hybridization)
The mixing of one s- and one p- orbital of nearly equal energy in an atom to form two new
orbitals of equivalent energy and identical shape is called sp-hybridization and the orbitals so
formed are called sp-hybrid orbitals. The characteristics of sp-hybridization are
i. sp-hybrid orbitals take linear geometry with bond angle 1800.
ii. Each sp-hybrid orbital has 50 % s-character and 50% p-character.
2. sp2-hybridization(trigonal planer hybridization)
The mixing of one s- and two p- orbital of nearly equal energy in an atom to form
three new orbitals of equivalent energy and identical shape is called sp2-
hybridization and the orbitals so formed are called sp2-hybrid orbitals. The
characteristics of sp2-hybridization are
i. sp2-hybrid orbitals take trigonal planer geometry with bond angle 1200.
ii. Each sp2-hybrid orbital has 33.33% s-character and 66.67% p-character.
3. sp3-hybridization( tetrahedral hybridization)
The mixing of one s- and three p- orbitals of nearly equal energy in an atom to
form four new orbitals of equivalent energy and identical shape is called sp3-
hybridization and the orbitals so formed are called sp3-hybrid orbitals. The four
sp3-hybrid orbitals take tetrahedral geometry with bond angle 109.50. Each sp3-
hybrid orbital has 25 % s-character and 75% p-character.
Bond length
Bond length is the average distance between the nuclei of two bonded atoms in a molecule or
chemical species. Bond length is inversely proportional to bond strength and bond enthalpy.
Ionic character
In a homonuclear diatomic molecules like H2, Cl2, F2, O2 etc., the shared pair of electrons are
equally distributed between the bonded atoms and polarity is not produced. Such bonds are
called non-polar bonds. However, when the covalent bond is formed between the atoms of
different elements, the shared pair of electrons are attracted more towards the more
electronegative atom. Due to this, polarity is developed in the bond. Such bonds are called
polar covalent bonds.
The covalent bond formed between two atoms of different elements is called polar covalent
bond and the compounds are called polar covalent compounds. E.g. HCl, HBr, H2O etc.
The covalent bond formed between two atoms of same element is called non-polar covalent
bond and compounds are called non-polar covalent compounds. Eg: H2, Cl2, F2, O2 etc.
Dipole moment (μ)
The ionic character in a covalent molecule is expressed in terms of dipole
moment. It is defined as the product of magnitude of charge on any one of atoms
and distance between them. It is denoted by ‘μ’ and given by
μ=q×d
Where, q = The magnitude of charge on either atoms
d = The distance between positive and negative charge
It is a vector quantity. It is represented as

The unit of dipole moment is Debye (D).

1 D = 1 × 10 -18 esu cm
For polyatomic molecule, the total dipole moment is calculated by taking the
vector sum of dipole moment of all the bonds in the molecule. If the net dipole
moment of polyatomic molecule is zero then the molecule becomes non polar and
has regular geometry and if the net dipole moment of polyatomic molecule is
non zero then molecule becomes polar and has irregular geometry.

Application of dipole moment

1. It determines the ionic character of covalent molecule.
2. It helps to determine the polarity and non-polarity of the molecule.
3. It helps to explain the geometry of some molecules.
CO2, CS2, HgX2 etc. ( zero dipole moment value) has linear where as H2O, H2S,
SO2, N2O, BF2etc.(non-zero dipole moment) has bent structure.
Hydrogen Bond
The force of attraction between hydrogen bonded to highly electronegative atom
and a highly electronegative atom of the same or different molecule is called
hydrogen bond. It is a weak force of attraction. As a result of H-bonding, one H-
atom is linked to two electronegative atoms simultaneously- one through covalent
bond and another by H-bond. It is shown by dotted line (……….).
For the formation of H-bond, H-atom should be covalently bonded to highly
electronegative atom and the size of electronegative atom should be very small.
For eg: F, O, N.
Types of Hydrogen Bond
1. Intermolecular hydrogen bond
The hydrogen bonding between the H- atom of one molecule and highly
electronegative atom of another molecule is called intermolecular hydrogen bond.
For example hydrogen bonding in water, ammonia etc.
H – O ……H – O……..H – O ….. H – O
| | | |
H H H H
2. Intramolecular hydrogen bond
The hydrogen bonding between the hydrogen atom and highly electronegative
atom of same molecule is called intramolecular hydrogen bond. For example
hydrogen bonding in o- nitrophenol, salicylic acid etc.
Application of hydrogen bond
1. Solubility: alcohols, aldehydes, amines etc. can form hydrogen bond with water molecules.
They are soluble in water.
2. Physical state: Hydrogen bonding affects the physical state of a substance. For example
H2O is liquid while H2S gas at room temperature.
3. Intramolecular H- bonding decreases boiling point whereas intermolecular H-bonding
increases boiling point of liquids.
4. It increases viscosity of the liquids.
Van der Waal’s force of attraction
Dutch chemist Vander waal proposed that there is a force of attraction between the non-polar
molecule. This force is called Van der Waal's force. Due to rapid movement of electrons, the
electron distribution of atom may be unsymmetrical with slight increase in electron density in
one side which develops the positive and negative end at a particular instant. i.e. a temporary
dipole is formed. Such dipole is called instantaneous dipole which develops the induced dipole
to another atom near to it.
The force of attraction between the instantaneous dipole and induced dipole is called
Vander Waal force or London force.
It is weaker than H-bond. It increases with increase in surface area of the molecules. And
increasing polarity in the molecule. It can be classified into following types.
1. Dipole-dipole interactions (eg: HCl, CO2 etc.)
2. Ion-dipole interaction (eg: force of attraction between NaCl and H2O)
3. Instantaneous dipole-induced dipole interaction (Ar, He, H2, O2, Cl2 etc.)
Metallic Bond
Metallic bond appears in metal. The bonding in metal was first explained by
Drude and Lorentz. According to them metal consist of positively charged
metallic ions (kernal) and valence electrons are moving between the ions like gas
molecule so this is also called electron sea model.
The simultaneous force of attraction between the mobile electron and positive
charged ion which binds the metal atoms together is known as metallic bond.

Properties of metallic solids

1. Metallic lustre
2. Electrical and thermal conductivity
3. Malleability and ductility
4. Hardness