1 CHEMICAL BONDING AND MOLECULAR STRUCTURE

The attractive force which holds various constituents (atoms, ions, etc.) together in different chemical species is
called a chemical bond
KÖSSEL-LEWIS APPROACH TO CHEMICAL BONDING
Lewis pictured the atom in terms of a positively charged ‘Kernel’ (the nucleus plus the inner electrons) and the
outer shell that could accommodate a maximum of eight electrons.
Lewis postulated that atoms achieve the stable octet when they are linked by chemical bonds.
Lewis Symbols: In the formation of a molecule, only the outer shell electrons take part in chemical combination
and they are known as valence electrons
Lewis Structures:
The dots represent electrons. Such structures are referred to as Lewis dot structures.
 Pair of bonded electrons is by means of a ‘dash’ (-) usually called a ‘bond’.
 Lone pairs or ‘non-bonded’ electrons are represented by ‘dots’.
 Electrons present in the last shell of atoms are called valence electrons.
Kössel
1. According to it, highly electronegative atoms like halogens are at extreme right and electropositive atoms
like alkali metals are at extreme left.
The halogen, for completing orbit gains 1 electron and alkali metals loses 1 electron to attain stable
configuration.
The negative and positive ions are stabilized by electrostatic attraction
The bond formed, as a result of the electrostatic attraction between the positive and negative ions was termed
as the electrovalent bond. The electrovalence is thus equal to the number of unit charge(s) on the ion.
Octet Rule
Kössel and Lewis in 1916 developed electronic theory of chemical bonding.
Atoms can combine either by transfer of valence electrons from one atom to another (gaining or losing) or by
sharing of valence electrons in order to have an octet in their valence shells. This is known as octet rule.
Limitations of the Octet Rule
1)The incomplete octet of the central atom. In some compounds, the number of electrons surrounding the
central atom is less than eight i.e. having less than four valence electrons. Examples are LiCl, BeH 2 and BCl3 .
2) In molecules with an odd number of electrons like nitric oxide, NO and nitrogen dioxide, NO 2 , the octet rule is
not satisfied for all the atoms
3) The expanded octet In a number of compounds of these elements there are more than eight valence
electrons around the central atom. This is termed as the expanded octet. Obviously the octet rule does not apply
in such cases. are: PF5 , SF6 , H2SO4.
4) It could not explain the shapes of molecules containing covalent bonds.
(5) It could not explain the release of energy during the formation
of a covalent bond.

Formal Charge: Formal charge is the difference between the number of valence electrons in an isolated atom and
number of electrons assigned to that atoms in Lewis structure.
Formal charge = [Total number of valence electrons in the free atom ) - (Total number of lone pairs of electrons)
-1/2(Total number of shared electrons i.e. bonding electrons)]
Types of chemical bond
1) Electrovalent or ionic bond 2) Covalent bond 3) Coordinate bond
Ionic bond and factors affecting it
o It is formed by transfer of electrons.
o It is formed between metal and no metal.
o In it metal always loses electrons and non-metal always accepts electron.
Explanation of Ionic Bond
Atoms are electrically neutral. Therefore, they possess equal number of protons and electrons. On losing an
electron, an atom becomes positively charged since now the number of protons exceeds the number of electrons.
On the other hand, in case of atom, gaining the electron, the number of electrons exceeds the number of protons
and thus the atom becomes negatively charged.
The oppositely charged particles formed above attract each other by electrostatic forces of attraction. The bond thus
formed is known as electrovalent or ionic bond.
Formation of ionic compounds depend upon: 1
 • The ease of formation of the positive and negative ions from the respective neutral atoms; • The arrangement of
the positive and negative ions in the solid, that is, the lattice of the crystalline compound.
The formation of a positive ion involves ionization, i.e., removal of electron(s) from the neutral atom The ionization is
always endothermic and that of the negative ion involves the addition of electron(s) to the neutral atom The electron
gain process may be exothermic or endothermic.
Lattice Enthalpy The Lattice Enthalpy of an ionic solid is defined as the energy required to completely separate one
mole of a solid ionic compound into gaseous constituent ions.
Conditions required of formation of ionic bonds:
1) Low I.E of cation. 2) High E.A of anion. 3) High lattice energy.
In ionic solids, the sum of the electron gain enthalpy and the ionization enthalpy may be positive but still the
crystal structure gets stabilized due to the energy released in the formation of the crystal lattice.
General properties of ionic compounds:
1. Physical state: They form definite pattern that is crystal lattice. Crystal lattice is 3D arrangement of cation
and an anion.
For example, in NaCl crystal due to crystal formation they all are solids due to strong bonding between constituents.

2. Melting and boiling point: They have high melting and boiling points because of strong attraction between
constituents.
3. Solubility: We know like dissolves like. So, polar compounds are soluble in polar solvents. Now, ionic
compounds have a charge that is they are polar. Therefore, they will dissolve in polar solvents like water. So, all ionic
compounds are soluble in polar solvents and insoluble in organic solvents.
4. Electrical conductivity: It is due to free movement of free ions when ionic compound is dissolved in water.
When dissolved they break into ions and conduct electricity.
5. Non directional in nature: When we are talking of directions in 3D structure, we are talking about 3
coordinate .So, in NaCl or any other ionic compounds the ion can take place in any direction .There direction is not
fixed. Therefore, they are non-directional in nature.
COVALENT BOND
The bond formed between the two atoms by mutual sharing of electrons between them so as to complete their
octets or duplets in case of elements having only one shell is called covalent bond or covalent linkage and the
number of electrons contributed by each atom is known as covalency.
Covalent bond is formed between two non-metals by sharing of electrons.
Electron pairs which participate in bonding are called bond pairs.
Electron pairs which do not participate in bonding are called lone pairs.
There could be single, double or triple covalent bonds between two elements depending on the number of electrons being
shared.
Lattice Enthalpy The Lattice Enthalpy of an ionic solid is defined as the energy required to completely separate one mole of a
solid ionic compound into gaseous constituent ions.
Bond Length Bond length is defined as the equilibrium distance between the nuclei of two bonded atoms in a molecule.
Bond lengths are measured by spectroscopic, X-ray diffraction and electron-diffraction techniques
Covalent radius half of the distance between two similar atoms joined by a covalent bond in the same molecule
R = rA + rB (R is the bond length and rA and rB are the covalent radii of atoms A and B respectively)
Van der Waals radius The overall size of the atom which includes its valence shell in a nonbonded situation.
Bond Angle It is defined as the angle between the orbitals containing bonding electron pairs around the central atom
in a molecule/complex ion.
Bond Enthalpy It is defined as the amount of energy required to break one mole of bonds of a particular type
between two atoms in a gaseous state.
Mean or average bond enthalpy It is obtained by dividing total bond dissociation enthalpy by the number of bonds
broken.
Bond Order is given by the number of bonds between the two atoms in a molecule. Increase in bond order, bond
enthalpy increases and bond length decreases.
Resonance, Whenever a single Lewis structure cannot describe a molecule accurately, a number of structures with
similar energy, positions of nuclei, bonding and non-bonding pairs of electrons are taken as the canonical structures
of the hybrid which describes the molecule accurately.
Resonance stabilizes the molecule as the energy of the resonance hybrid is less than the energy of any single
cannonical structure; and, • Resonance averages the bond characteristics as a whole.
Polarity of Bonds
o The hetro-atomic molecules (having different types of atoms in them) when sharing of electrons occur the
shared pair do not lie in middle, it gets displaced towards more electronegative atom.
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o So, it will acquire partial negative charge and other atom will acquire partial positive charge. Due to this the
poles are developed and the bond formed is polar covalent bond.
A molecule with positive and negative charge centres in equilibrium is called as dipole and is characterised by
possessing a quantity dipole moment (u) defined as the product of the magnitude of charge (q) and the distance(d)
separating the centres of +ve and –ve charges. Its direction is from +ve end to – ve end.
u= q × d
The charge q on an electron is 4.8 × 10–10 esu. The distance is measured in cm and is of order of 1 Å, i.e., 10–8 cm. Its
unit in CGS system is debye (D).
A molcule will have a dipole moment of 1 Debye (D) if charges of 1 × 10 –8 esu are separated by a distance of 1Å.
Thus, 1D = 1 × 10–18 esu. cm.
Dipole moment is a vector quantity and by convention it is depicted by a small arrow with tail on the negative centre
and head pointing towards the positive centre.
In case of a heteronuclear molecule like HF, the shared electron pair between the two atoms gets displaced more
towards fluorine since the electronegativity of fluorine is far greater than that of hydrogen. The resultant covalent
bond is a polar covalent bond.
In case of polyatomic molecules the dipole moment not only depend upon the individual dipole moments of bonds
known as bond dipoles but also on the spatial arrangement of various bonds in the molecule. In such case, the dipole
moment of a molecule is the vector sum of the dipole moments of various bonds.

Distortion of electron cloud of the negatively charged ion by the positively charged ion is called Polarization.
Fajan's Rule: All the covalent bonds have some partial ionic character, the ionic bonds also have partial covalent
character. The partial covalent character of ionic bonds was discussed by Fajans.
rules: • The smaller the size of the cation and the larger the size of the anion, the greater the covalent character of an
ionic bond. • The greater the charge on the cation, the greater the covalent character of the ionic bond.
• For cations of the same size and charge, the one, with electronic configuration (n-1)d 10nso , typical of transition
metals, is more polarising than the one with a noble gas configuration, ns 2 np6 , typical of alkali and alkaline earth
metal cations.
The cation polarises the anion, pulling the electronic charge toward itself and thereby increasing the electronic
charge between the two.
The polarising power of the cation, the polarisability of the anion and the extent of distortion (polarisation) of anion
are the factors, which determine the per cent covalent character of the ionic bond.
THE VALENCE SHELL ELECTRON PAIR REPULSION (VSEPR) THEORY
The electron pairs surrounding the central atom repel one another and move so far apart from one another that there
are no further repulsions between them. As a result, the molecule has minimum energy and maximum stability.
o This theory was given by Sid wick and Favell.
o In this only the valence electrons participate in bond formation.
o The bonded atoms around central metal atom will have repulsions between them
o Therefore, they will arrange themselves in such way that the repulsion is minimum.
The main postulates of VSEPR theory are as follows:
• The shape of a molecule depends upon the number of valence shell electron pairs (bonded or nonbonded) around the
central atom.
• Pairs of electrons in the valence shell repel one another since their electron clouds are negatively charged.
• These pairs of electrons tend to occupy such positions in space that minimise repulsion and thus maximise distance between
them.
• The valence shell is taken as a sphere with the electron pairs localising on the spherical surface at maximum distance from
one another.
• A multiple bond is treated as if it is a single electron pair and the two or three electron pairs of a multiple bond are treated as
a single super pair.
• Where two or more resonance structures can represent a molecule, the VSEPR model is applicable to any such structure.
The repulsive interaction of electron pairs decrease in the order: Lone pair (lp) – Lone pair (lp) > Lone pair (lp) – Bond pair (bp) >
Bond pair (bp) – Bond pair (bp)
Prediction of geometrical shapes of molecules with the help of VSEPR theory, it is convenient to divide molecules into two
categories as
(i) molecules in which the central atom has no lone pair and (ii) molecules in which the central atom has one or more lone
pairs
The theoretical basis of the VSEPR theory regarding the effects of electron pair repulsions on molecular shapes is not clear and
continues to be a subject of doubt and discussion.
 Valence bond theory (VBT):
Valence bond theory was introduced by Heitler and London (1927) and developed further by Pauling and others.
According to this theory a covalent bond is formed between two atoms by the overlap of half filled valence atomic orbitals
of each atom containing one unpaired electron.Valence bond theory considers that the overlapping atomic orbitals of the
participating atoms form a chemical bond. 3

The main postulates of this theory are as follows: 

* A covalent bond is formed by the overlapping of two half filled valence atomic orbitals of two different
atoms.
* The electrons in the overlapping orbitals get paired and confined between the nuclei of two atoms.
* The electron density between two bonded atoms increases due to overlapping. This confirms stability to
the molecule. 
* Greater the extent of overlapping, stronger is the bond formed. 
* The direction of the covalent bond is along the region of overlapping of the atomic orbitals i.e., covalent
bond is directional.
The partial merging of atomic orbitals is called overlapping of atomic orbitals which results in the pairing of electrons.

Types of Overlapping and Nature of Covalent Bonds The covalent bond may be classified into two types depending upon the
types of overlapping:
(i) Sigma(σ) bond, and (ii) pi(π) bond
(i) Sigma(σ) bond : This type of covalent bond is formed by the end to end (head-on) overlap of bonding orbitals along the
internuclear axis. This is called as head on overlap or axial overlap.
formed by any one of the following types of combinations of atomic orbitals.

• s-s overlapping : In this case, there is overlap of two half filled s-orbitals along the internuclear axis as shown below

s-p overlapping: This type of overlap occurs between half filled s-orbitals of one atom and half filled p-orbitals of another atom.
p–p overlapping : This type of overlap takes place between half filled p-orbitals of the two approaching atoms.

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(ii) pi(π ) bond : In the formation of π bond the atomic orbitals overlap in such a way that their axes remain parallel to each
other and perpendicular to the internuclear axis. The orbitals formed due to sidewise overlapping consists of two saucer type
charged clouds above and below the plane of the participating atoms.

HYBRIDISATION
To explain the characteristic
geometrical shapes of polyatomic molecules like CH 4 , NH3 and H2O etc., Pauling introduced the concept of hybridization.
Hybridization is the intermixing of orbitals of slightly different energies, so as to redistribute their energy and give
rise to new set of orbitals that are similar in shapes and energy.
The atomic orbitals combine to form new set of equivalent orbitals known as hybrid orbitals.
Salient features of hybridisation:
1. The number of hybrid orbitals is equal to the number of the atomic orbitals that get hybridised.
2. The hybridised orbitals are always equivalent in energy and shape.
3. The hybrid orbitals are more effective in forming stable bonds than the pure atomic orbitals.
4. These hybrid orbitals are directed in space in some preferred direction to have minimum repulsion between electron pairs
and thus a stable arrangement. Therefore, the type of hybridisation indicates the geometry of the molecules.
Important conditions for hybridization
(i) The orbitals present in the valence shell of the atom are hybridised.
(ii) The orbitals undergoing hybridisation should have almost equal energy.
(iii) Promotion of electron is not essential condition prior to hybridisation.
(iv) It is not necessary that only half filled orbitals participate in hybridisation. In some cases, even filled orbitals of valence shell
take part in hybridisation.
Types of Hybridisation
(I) sp hybridisation: This type of hybridisation involves the mixing of one s and one p orbital resulting in the formation of two
equivalent sp hybrid orbitals.
The suitable orbitals for sp hybridisation are s and pz , if the hybrid orbitals are to lie along the z-axis. possesses linear
geometry. Each sp hybrid orbitals has 50% s-character and 50% p-character.
This type of hybridisation is also known as diagonal hybridization
(II) sp2 hybridisation : In this hybridisation there is involvement of one s and two p-orbitals in order to form three equivalent sp 2
hybridised orbitals.
a trigonal planar arrangement with angle of 120°.
(III) sp3 hybridisation This type of hybridization formed mixing of one s-orbital and three p-orbitals of the valence shell to form
four sp3 hybrid orbital of equivalent energies and shape. There is 25% s-character and 75% p-character in each sp 3 hybrid
orbital.
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