CHAPTER

Chemical Bonding and

8 Molecular Structure

Chemical Bond Valence Shell Electron Pair Repulsion Theory

The force of attraction which hold atom, molecule or ions together ™ Order of repulsion:
within chemical species.
lp-lp > lp-bp > bp-bp
Exception of Octet Rule mb-mb > mb-sb > sb-sb (mb = multiple bond; sb = single bond)

(a) electron deficient (b) electron rich (c) odd electron Valence Bond Theory
Central atom: Central atom: species central
Proposed by Heitler & London as per VBT bonding takes place
No. of electron < 8 No. of atom: has odd
for attaining stability.
BeH2 electron > 8 electron NO,
1
BF3, BCl3, BBr3, NO2, ClO2, ClO3 Stability ∝
PCl5, IF7 Potential energy
BI3 SF6, XeF2 ™ During this process some extent of electron cloud merge
AlCl3, AlBr3, AlI3
into each other; this part is known as overlapped region &
this process is known as overlapping.
Electrovalent or Ionic bond
The chemical bond formed between two or more atoms as a result Hybridisation
of the complete transfer of one or more electrons from one atom
Type of No. of hybrid 3D
to another is called as Ionic or electrovalent bond. S.No. Example
orbital orbital orientation
Fajan’s Rule 1. one s + one p 2; sp Linear BeH2,
BeCl2
charge of cation 2. one s + two p 3; sp2 Triangular BCl3, BF3
Ionic potential of cation (φ) ∝
size of cation
3. one s + three p 4; sp 3
Tetrahedral CH4, CCl4
Polarisibility of anion ∝ size of anion ∝ charge of anion 4. one s + three p + 5; sp d
3
Triangular PCl5
one d bipyramidal
Smaller cation
5. one s + three p + 6; sp3d2 Octahedral SF6
Condition of polarisation Large anion two d
Higher charge 6. one s + three p + 7; sp3d3 Pentagonal IF7
three d bipyramidal
Covalent Bond
A covalent bond is formed by the mutual sharing of electrons
Molecular Orbital Theory (MOT)
between two atoms to complete their octet. (Except H which
completes its duplet) The molecular orbital theory was developed by F. Hund and R.S.
Mulliken in 1932. The salient features are:
1. The combining atomic orbitals must have the same or nearly
××

H : H H–H O=O N=N

×××
××

××

××
the same energy and same symmetry about the molecular
H2 molecule O O N N
axis.
Coordinate Bond (Dative Bond) Energy level diagram from MOs:
The bond formed between two atom in which contribution of an Molecular orbital energy diagram for up to N2 (molecule
electron pair is made by one of them while the sharing is done by both. having ≤ 14 electrons)
F3B + :NH3 → (F3B ← NH3) s1s < s*1s < s2s < s*2s < p2p = p2p < s2p < p*2p = p*2p < s*2p
x y z x y z
Molecular orbital energy diagram for O2 and F2 (molecule
d A–B= rA + rB – 0.09 × ∆EN Å
having > 14 electrons)
1
s1s < s*1s ; < s2s < s*2s < s2p < p2p = p2p < p*2p = p*2p < s*2p (iii) Bond order: Bond length ∝
z x y x y z B.O.
1
s*, p* = antibonding molecular orbital (iv) Hybridisation: Bond length ∝
% ageof s − character
s, p = bonding molecular orbital
Bond Angle
1 (i) Bond angle ∝ % age of s-character
Bond order (B.O.) = (N b – N a )
2 1 .. ..
(ii) Bond angle ∝ Eg.: CH4 > NH3 > H2O:
Dipole Moment lp
Measurement of Polarity in a molecule [when hybridisation is same]
debye = esu-cm
µ=q×d Back Bonding
1D = 10–18 esu.cm
Condition:
Diatomic Molecule (i) One atoms must have lone pair.
(a) Homoatomic DEN = 0 → µ = 0 → Non-polar. (ii) And another atoms must have vacant orbital.
H2, F2, Cl2, N2 etc. Type of Back Bond:
(b) Heteroatomic DEN ≠ 0 → µnet ≠ 0 → polar (i) (pp - pp) type of back bond eg., BF3, BCl3, CF2, CCl2
HF > HCl > HBr > HI (ii) (pp - dp) type of back bond
Polyatomic Molecule eg., CCl3–, O(SiH3), N(SiH3)2 etc.
µR → vector sum of bond moment
Hydrogen bonding
µR → µ12 + µ22 + 2µ1µ2 cos θ
™ It is dipole-dipole type of interaction.
Important Order ™ Electrostatic force of attraction between hydrogen (covalently
NH3 > NI3 > NBr3 > NCl3 > NF3 bond with F/N/O) & highly electronegative atom.
Intermolecular hydrogen bond → between the molecules
NH3 > SbH3 > AsH3 > PH3
™ Hydrogen bond
H2O > H2S Intramolecular hydrogen bond → in the molecules
CH3Cl > CH3F > CH3Br > CH3I Strength
CH3Cl > CH2Cl2 > CHCl3 > CCl4 Intermolecular H-bond > Intramolecular H-bond
Intramolecular H-bonding takes place in ortho derivatives only.
Bonding Parameter
1. Bond length: Internuclear distance
Factor affecting Bond length
(i) Atomic size: bond length ∝ size```` [No. of shell]
(ii) DEN, Bond length ∝
∆EN

22 JEE (XI) Module-3 PW