Chemical Bonding and Molecular Structure
Chemical bond is defined as the attractive force acting between two or more atoms in a
molecule involving redistribution of electrons among them to hold them together in a
stable configuration. This process accompanied by decrease in energy.
Therefore, decrease in energy ∝ strength of the bond.
Reasons for the formation of a Chemical Bond:
• Minimum Energy concept: When two atoms approach each other, both attraction and
repulsion take place between the nucleus and electrons of atoms. When the attractive
forces overweigh the repulsive forces, the potential energy of the system becomes
minimum and the bond forms.
• Octet rule (Lewis and Kossel theory): Atoms tend to complete their outermost orbit to
acquire the stable noble gas electronic configuration by transfer or sharing of electrons
in their outermost orbit.
Lewis symbol:
Lewis symbol represents valence electrons of an element as a dot. The number of dots help to
calculate the group valence of the element concerned. E.g., Li., H., He:
Exceptions of Octet Rule:
• Electron Deficient Species: The central atom of these molecules has less than 8
electrons in outermost shell. E.g.: BeCl2, BF3, AlCl3
• Odd Electron Species: Molecules like NO2, NO, O2-, ClO2, etc. violate this rule as they
have a non-bonding unpaired electron.
• Noble gases like Xe and Kr form a number of compounds with oxygen and fluorine such
as XeF2, XeOF2, KrF2 etc. Octet Rule does not account for the shape of these molecules.
• Transition metal ions: These have 9 to 18 electrons in outermost shell. Eg: Cr3+, Mn2+,
Cu+.
• Electron Efficient Species: Molecules like PCl5, SF6, IF7, SF4, XeF4 have more than eight
electrons around the central atom. These compounds also known as hypervalent
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Chemical Bonding and Molecular Structure
compounds.
Formal Charge: The charge assigned to an atom in a molecule, assuming that electrons in all
chemical bonds are shared equally between atoms, regardless of relative electronegativity.
It is given as: FC=VE-[LPE-1/2(BE)], where FC= formal charge, VE= number of valence
electrons on the free atom, LPE= number of lone pair electrons on the atom in the
molecule, and BE= number of bonding (bond pair) electrons.
Types of Chemical Bond
Ionic Bond or Electrovalent Bond:
• Involves complete transfer of e–s from electropositive to electronegative element. Eg:
NaCl, MgCl2 etc.
• The number of electrons lost or gained during the formation of bond is termed as
electro valency of the element.
• Metal is generally s-block having low ionization energy (IE) and non-metal is p-block
having high electron affinity (EA).
• High lattice energy.
• Difference in electronegativity (EN) is >1.7 for the formation of ionic bond.
• Strongest bond is formed between elements of IA & VII A due to large EN difference.
• From IA → Cs & from VIIA → F form strongest ionic bond.
Covalent Bond:
• Involves mutual sharing of one (single bond), two (double bond) or three (triple bond)
electrons between the combining atoms. E.g.: CH4, N2, CO2 etc.
• Number of electrons pairs an atom share in combination with other atoms in a
molecule is called covalency. E.g.: covalency of H in H2O=1, O in CO2=2 etc.
• Combining atoms have high IE, high EA and zero or almost equal EN difference.
• Two types: polar covalent and non-polar covalent compounds.
Coordinate Covalent Bond or Dative Bond:
• Both electrons for sharing between two atoms are contributed by one atom only. In
terms of orbital theory, it involves overlapping between empty and completely filled
atomic orbitals.
• The donor atom donates electron pair whereas the acceptor accepts the electron pair.
• The bond is represented by an arrow ( ) pointing head towards the acceptor.
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Chemical Bonding and Molecular Structure
E.g.: SO2, H3O+, NH3 and BF3 form addition product
Metallic bond:
• The constituent particles are metals floating in a sea of electrons. Bond is formed by
electrostatic force of attraction between conduction electrons and positively charged
metal ions (Kernels). E.g.: Na(s), Cu(s) etc.
Hydrogen Bond:
• Formed due to electrostatic attraction between hydrogen atom of one molecule and
highly electronegative atom (F, O and N) of another molecule of the same or different
species. It is represented as zig-zag chains with hydrogen bond shown by dotted lines.
e.g.
• Depending on electronegativity of atom involved in H-bonding, the order of bond
strength is H……. F > H…….O > H……N
Vander Waal's Forces:
Attractive forces between uncharged molecules are known as van der Waals forces.
VSEPR Theory (Valence Shell Electron Pair Repulsion Theory):
• Predict geometry of molecules based on the following repulsions between electrons
pairs: lone pair - lone pair repulsion (lp - lp) > lone pair - bond pair (lp - bp) > bond pair -
bond pair (bp - bp).
Valence Bond Theory:
• Overlapping of two half filled atomic orbitals having electrons with opposite spin results
in covalent bond formation.
• Overlapping occurs either coaxially forming stronger sigma bond (σ-bond) or collaterally
forming weaker pi - bond (π-bond).
• σ-bond involves overlap of atomic orbitals in 3 ways: s-s, s-p, p-p (axial).
• π-bond involves overlap of unhybridized p-p orbitals laterally (sideways).
• The strength of σ-bond depends upon the extent of overlapping between atomic
orbitals. It follows the following order: p – p > s – p > s – s.
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Chemical Bonding and Molecular Structure
Molecular Orbital Theory or Hund- Mulliken Theory:
• Atomic orbitals (A.O) combine to form the molecular orbitals (M.O).
• Number of M.O is equal to number of A.O involved.
• Formation of M.O is by LCAO method (linear combination of atomic orbitals) i.e. by
addition or subtraction of wave functions of individual orbitals.
• M.O of lower energy is known as bonding M.O (BMO) and of higher energy is known as
antibonding M.O (ABMO).
• Electron filling takes place according to Aufbau rule, Pauli's exclusion principle and
Hund's rule.
Hybridisation: Process in which redistribution of energy takes place by intermixing of atomic
orbitals of slightly different energies resulting in the formation of same number of new atomic
orbitals of equivalent energy and shape. The new atomic orbitals are termed hybrid atomic
orbitals.
Types of hybridization with atomic orbitals involved, shape and examples
Hybridization Atomic Orbitals Shape Example
sp s+p Linear BeCl2
sp 2 s+p (2) Trigonal planar BCl3
sp3 s+p (3) Tetrahedral H2O
dsp 2 d+s+p (2) Square planar [Ni(CN)4]2–,[Pt(Cl)4]2–
sp3d s+p (3) +d Trigonal bipyramidal PF5, PCl5
sp d3 2 s+p (3) +d (2) Square pyramidal BrF5
sp d3 2 s+p (3) +d (2) Octahedral SF6, [CrF6]3–
2
d sp 3 d (2) +s+p (3) [Co (NH3)6]3+
Resonance: Two or more alternative forms of a molecule represented by double headed arrow
and showing the movement of valence electrons from one position to another. The actual
structure is the resonance hybrid and its alternative forms are called resonating or canonical
structures. E.g.:
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Chemical Bonding and Molecular Structure
Bond parameters:
Bond length: Equilibrium distance between the nuclei of two bonded atoms in a molecule.
Bond angle: The angle between two adjacent bonds around the central atom in a molecule or
complex ion.
Bond order: Number of shared electron pairs between two atoms in a molecule.
Bond enthalpy: Amount of energy required to break one mole of bonds of a particular type
between two atoms in gaseous state.
Bond order α Bond enthalpy α 1/bond length
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