4.

CHEMICAL BONDING
Definition of Chemical bond: - The attractive force which holds various constituents (atoms, ions, etc.)
together in different Chemical species is called a chemical bond.
KOSSEL-LEWIS APPROACH TO CHEMICAL BONDING: -
Lewis postulated that atoms achieve the stable octet when they are linked by chemical bonds.
➢ This theory was also called as electronic theory of valency (or) chemical bond theory
➢ Kossel explained the formation of electrovalent bond while Lewis explained the formation of covalent
bond. Their explanation of valency is mainly based on the inertness of noble gases
➢ The electrons that are participate in the formation of chemical bonds are called valence electrons.
➢ In the case of sodium and chlorine, this can happen by the transfer of an electron from sodium to
chlorine thereby giving the Na+ and Cl– ions.
➢ In the case of other molecules like Cl 2, H2, F2, etc., the bond is formed by the sharing of a pair of
electrons between the atoms. In the process each atom attains a stable outer octet of electrons.
➢ Lewis symbols: - Lewis symbol is the symbol of an element surrounded by ‘dots’ to represent the
number of valence electrons.
➢ Lewis symbols for second period elements
Group 1 2 13 14 15 16 17 18
No
➢ Li Be B C N O F Ne
Valence
Electrons 1 2 3 4 5 6 7 8

➢ Significance of Lewis Symbols: -

➢ The number of dots around the symbol represents the number of valence electrons.
➢ This number of valence electrons helps to calculate the common or group valence of the element.
The group valence of the elements is generally either equal to the number of dots in Lewis symbols
or 8 minus the number of dots or valence electrons.

➢ Octet rule: - The tendency of an atom achieves eight electrons in their outer most shell is known as
octet rule.

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 ➢ Every atom must possess 8 electrons in its outer most energy level for its stability.
➢ Atoms combine in two ways to get octet either by transfer of electrons (or) by mutual sharing of
electrons. They can attain ns2 np6 electronic configuration.
➢ Formation of Ionic Bond: - The electrostatic force that binds the oppositely charged ions and form
ionic bond.
➢ Definition: - The completely transfer of one (or) more electrons from one atom to another atom which
is leads to formation of Ionic Bond.
➢ It is formed when the electron negativity difference between the two atoms is more than 1.70.
➢ Example
➢ Formation of NaCl in terms of orbital concept: -
➢ Na(Z=11) the electronic configuration is 1s2 2s2 2p6 3s1 this can be expressed as

➢ Cl(Z=17) the electronic configuration is 1s 2 2s2 2p6 3s2 3p5 this can be expressed as

➢ The configurations after the transfer of electrons forming ions can be expressed as

➢ In the formation of NaCl the 3s electron of Na atom is transferred to the 3pZ orbital of chlorine atom
➢ The Na+ ion and Cl– so formed are now bound by strong columbic electrostatic forces of attraction
forming NaCl.
➢ Factors favorable for the formation of Ionic compounds.
➢ a) Cation formation
➢ i) Lower Ionization energy:- Lower Ionization energy of an atom greater is the formation of cation
➢ Example: - The Ionization energy of Na is 117.9 K Cal mol -1 and that of K is 100 K Cal mol-1. So K+
ion can readily form than Na+.
➢ ii) Large size of the atom: - Large atoms can easily lose the valence electrons. If the size large the
distance between the nucleus and the valence electrons is more and so the force of attraction is less.
Therefore the electron can be removed easily from the atom forming cation.
➢ iii) Ion with lower charge: - Small magnitude of charge favours the formation of ions easily,
example: - The ease of ion formation increases in the order Na+ > Mg2+ > Al3+.
➢ iv) Cations with inert gas configuration: - Ion possessing electronic configuration similar to zero
group elements are more stable than those ions which do not have such configuration. Example Ca2+
(2, 8, 8) is more stable than Zn2+ (2, 8, 18) because the former has inert gas configuration.
➢ b) Anion formation :-
➢ i) High electron affinity: - If the electron affinity of an element is high its anion can be easily formed.
➢ Example Cl + 1e– Cl–
➢ ii) smaller size of atom: - Smaller the size of the atom lesser is the distance between the nucleus
and the valence orbit. Hence the nuclear attraction on incoming electron is more. So the anion is
readily formed.
➢ iii) Lower charge: - Ions with lower charge are more readily formed than those with higher charge.
➢ Example Cl– O–2 N–3
➢ iv) The ions with inert gas electronic configuration: - The ions with inert gas electronic
configuration are more readily formed than others with the same charge.
➢ c) If the two bonded atoms differ by more than 1.70 in their EN values, the bond between them is
ionic in nature.
➢ d) High lattice enthalpy (or) energy.
➢ General properties of ionic compounds: -
➢ Ionic compounds are hard and possess high melting and boiling points
➢ Ionic compounds are dissolved in polar solvents like water. Their solubility in non polar solvents like
benzene, carbon tetrachloride is very negligible.
➢ In aqueous solutions (or) in fused stat, ionic compounds are act as conductors.
➢ Since ionic compounds are formed by non-directional bonds, they do not isomerism.

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 ➢ Lattice enthalpy: - the lattice enthalpy of ionic crystal is defined as the energy required to completely
separate a one mole of solid ionic compound into gaseous constituent ions. e) higher lattice enthalpy,
higher stability of the ionic compounds
➢ Covalent bond: - A covalent bond is formed when the atoms of same (or) different elements combine
by mutual sharing of electrons.
➢ Example: - formation of chlorine molecule.
➢ The Cl atom with electronic configuration, [Ne] 3s 2 3p5, is one electron short of the argon
configuration.
➢ The formation of the Cl2 molecule can be understood in terms
of the sharing of a pair of electrons between the two chlorine
atoms, each chlorine atom contributing one electron to the
shared pair.
➢ In the process both chlorine atoms attain the outer shell octet
of the nearest noble gas (i.e., argon).

➢ Formal charge: - The formal charge of an atom in a polyatomic molecule or ion may be defined as
the difference between the number of valence electrons of that atom in an isolated or Free State and
the number of electrons assigned to that atom in the Lewis structure.
➢ It is expressed as:
➢ Formal charge (F.C.) on an atom in a Lewis structure = total number of valence electrons in the free
atom-total number of non-bonding (lone pair) electrons-total number of Bonds around the atom.
➢ The atoms have been numbered as 1, 2 and 3.
➢ The central O atom marked 1
FC = 6 – 2 –3 = +1
➢ The end O atom marked 2
➢ FC = 6 – 4 –2 = 0
➢ The end O atom marked 3
➢ FC = 6 – 6 –1 = –1
➢ Hence, we represent O3 along with the formal charges as follows:

➢ Formal charges help in the selection of the lowest energy structure from a
number of possible Lewis structures for a given species.
➢ Generally the lowest energy structure is the one with the smallest formal charges on the atoms.
➢ The formal charge is a factor based on a pure covalent view of bonding in which electron pairs are
shared equally by neighbouring atoms.
➢ Limitations of the Octet Rule
➢ The incomplete octet of the central atom
➢ In some compounds, the number of electrons surrounding the central atom is less than eight.
Examples are LiCl, BeH2 and BCl3. And other examples are AlCl3 and BF3.

➢ Odd-electron molecules
➢ In molecules with an odd number of
electrons like nitric oxide, NO and nitrogen
dioxide, NO2, the octet rule is not satisfied
for all the atoms
➢ The expanded octet
➢ Elements in and beyond the third period of
the periodic table have, apart from 3s and
3p orbital’s, 3d orbital’s also available for bonding.
➢ In a number of compounds of these elements there are more than eight valence electrons around the
central atom.

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 ➢ This is termed as the expanded octet. Obviously the octet rule does not apply in such cases.
➢ Some of the examples of such compounds are: PF5, SF6, H2SO4 and a number.
➢ Other drawbacks of the octet theory
➢ It is clear that octet rule is based upon the chemical inertness of noble gases. However, some noble
gases (for example xenon and krypton) also combine with oxygen and fluorine to form a number of
compounds like XeF2, KrF2, XeOF2 etc.
➢ This theory does not account for the shape of molecules.
➢ It does not explain the relative stability of the molecules being totally silent about the energy of a
molecule.
➢ 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.
➢ Units of bond length A° (or) cm (or) m (or) pm.
➢ As the number of bonds between two atoms increases the bond length decreases.
➢ Example:
bond Bond length
C–C 1.54 A°
C=C 1.33 A°
C≡C 1.20 A°

➢ Covalent radius: - Covalent radius of an atom is equal to half the inter nuclear distance between
two identical atoms that are held together by a covalent bond.
𝑑
➢ Covalent radius of A = 𝐴𝐴 Where dAA is the bond length.
2
➢ For hetero nuclear diatomic molecules the relation
𝑑
rA+rB = 𝐴𝐵 is no longer valid.
2
➢ In such cases, the covalent radius of atom A in a molecule AB calculated by using Pauling’s empirical
equation.
➢ dAB = rA+rB+C(XA-XB) where, XA and XB are the electro negativities of atom A and B respectively.
➢ The value C depend upon the type of atoms for second period atoms C = 0.08. and for bonds between
Si, P and S bonded to more electronegative atoms not belonging to first period C = 0.06.
➢ Bond angle: -It is defined as the angle between the orbital’s containing bonding electron pairs around
the central atom in a molecule/complex ion.
➢ Bond angle is expressed in degree which can be experimentally determined by spectroscopic
methods.
➢ Example bond angle in water molecule is 104.5°.
➢ Bond length and bond angles comparison.
➢ Size of the atom 𝛼 bond length HF<HCl<HBr<HI.
➢ F–F<Cl–Cl<Br–Br<I–I.
➢ CH4<SiH4<GeH4<SnH4.
➢ Multiplicity of bond (nearly same period element)
➢ Single bond>double bond>triple bond
➢ C–C>C=C>C≡C.
➢ F–F>O=O>N≡N.
➢ Electronegativity difference.
➢ H–C>H–N>H–O>H–F.
➢ How to compare bond angles.
➢ Hybridisation sp> sp2> sp3> sp3d2
➢ 180° 120° 109°28’ 90°

➢ Number of lone pair: - if hybridisation of central atom is same but number of lone pair is different
then more is the number of lone pair less is the bond angle.

Example CH4 NH3 H2O

Hybridisation Sp3 Sp3 Sp3
Lone pair Lp = 0 Lp = 1 Lp = 2
Bond angle 109°28’ 107°48’ 104°.5
➢ Size or electronegativity of central atom: - when hybridization is same and number of lone pair
is same but central atom is different then see the electronegativity of central atom. More is the
electronegativity more is the bond angle.
Example NH3 PH3 AsH3 SbH3
Hybridisation Sp3 Sp3 Sp3 Sp3
Lone pair Lp = 1 Lp = 1 Lp = 1 Lp = 1
Bond angle 107°48’ 93° 92° 91°

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 ➢ Size or electronegativity of terminal atom: -hybridisation same, lone pair same, central atom
same but terminal atom is different than greater is the size of the terminal atom greater will be the
bond angle.
Example PF3 PCl3 PBr3 PI3
Hybridisation Sp3 Sp3 Sp3 Sp3
Lone pair Lp = 1 Lp = 1 Lp = 1 Lp = 1
Bond angle 98° 100° 101° 102°
➢ Other examples of bond angle Cl2O>OF2
➢ Bond angle of COF2<COCl2<COBr2<COI2
➢ 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.
➢ The unit of bond enthalpy is kJ mol–1.
➢ For example, the H – H bond enthalpy in hydrogen molecule is 435.8 kJ mol –1.
➢ H2(g) → H(g) + H(g); ΔaHɵ = 435.8 kJ mol–1
➢ Similarly the bond enthalpy for molecules containing multiple bonds, for example O2 and N2 will be
as under :
➢ O2 (O = O) (g) → O(g) + O(g); ΔaHɵ = 498 kJ mol–1
➢ N2 (N ≡ N) (g) → N(g) + N(g); ΔaHɵ = 946.0 kJ mol–1
➢ It is important that larger the bond dissociation enthalpy, stronger will be the bond in the molecule.
➢ For a heteronuclear diatomic molecules like HCl, we have
➢ HCl (g) → H(g) + Cl (g); ΔaHɵ = 431.0 kJ mol–1
➢ In case of polyatomic molecules, the measurement of bond strength is more complicated.
➢ For example in case of H2O molecule, the enthalpy needed to break the two O – H bonds is not the
same.
➢ H2O(g) → H(g) + OH(g); ΔaH1ɵ = 502 kJ mol–1
➢ OH(g) → H(g) + O(g); ΔaH2ɵ = 427 kJ mol–1
➢ The difference in the ΔaH value shows that the second O – H bond undergoes some change because
of changed chemical environment.
➢ Therefore in polyatomic molecules the term mean or average bond enthalpy is used. It is obtained
by dividing total bond dissociation enthalpy by the number of bonds broken
502+427
➢ Average bond enthalpy = = 464.5 kJ mol–1
2
➢ Bond order: - The Bond Order is given by the number of bonds between the two atoms in a
molecule.
bond Bond order Bond energy Bond length
H–H 1 435.8 kJ mol–1 74 pm
O=O 2 498.0 kJ mol–1 121 pm
N≡N 3 946.0 kJ mol–1 109 pm

➢ Iso electronic molecules and ions have identical bond orders for example F 2 and O2-2 bond order is 1.
➢ N2, CO and NO+ have bond order is 3.
➢ Increase in bond order, bond enthalpy increases and bond length decreases. Lower the bond length
and higher the stability.
➢ Resonance structures: -According to the concept of 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.
➢ The weighted average contributing canonical structures is called resonance hybrid. Resonance is
represented by double headed arrow mark (↔).
➢ Some important resonance structures
➢ N2O molecule

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 ➢ Resonance energy: - The difference in the energy of the resonance hybrid and the most stable
contributing structure (having least energy) is called resonance energy.
➢ Characteristics of Resonance: -
➢ The contributing structures (canonical forms) do not have any real existence. They are only
imaginary. Only the resonance hybrid has the real existence.
➢ As a result of resonance, the bond length in a molecule becomes equal, example. O−O bond length
in ozone or C−O bond lengths in CO3-2 ion.
➢ The resonance hybrid has lower energy and hence greater stability than any of the contributing
structures.
➢ Greater is the resonance energy, greater is the stability of the molecule.
➢ Greater is the number of canonical forms especially with nearly same energy, greater is the stability
of the molecule.
➢ Non polar covalent bond: - The covalent bond in which the atoms having same electro negativity
are equally attracted with respect to each other is called non - polar covalent bond.
➢ Example; H2, O2, Cl2, N2 and F2.
➢ Polar covalent bond: - The covalent bond in which the shared electron pair between the two different
atoms gets displaced more towards high electronegative atom induces the polarity. This bond is
called polar covalent bond.
➢ Example; H–F
➢ Dipole moment: - The product of magnitude of the charge and the distance between the two poles
(bond length) is called dipole moment.
➢ Dipole moment 𝜇 = q×d where q = charge d = bond length.
➢ Dipole moment is usually expressed in Debye units (D).
➢ The conversion factor is 1 D = 3.33564 × 10–30 C m where C is coulomb and m is meter.
➢ Applications: - it is used to calculate the percentage of ionic character in a molecule.

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 ➢ It is used to know shape of the molecule.
➢ Symmetrical or un symmetrical of the molecule known by dipole moment.
➢ Dipole moment is a vector quantity and is depicted by a small arrow with tail on the positive centre
and head pointing towards the negative centre.
➢ For example the dipole moment of HF may be represented as H F
➢ Let us study an interesting case of NH3 and NF 3 molecule.
➢ Both the molecules have pyramidal shape with a lone pair of electrons on nitrogen atom.
➢ Although fluorine is more electronegative than
nitrogen, the resultant dipole moment of NH3 (4.90 ×
10–30 C m) is greater than that of NF 3 (0.8 × 10–30 C
m).
➢ This is because, in case of NH3 the orbital dipole due
to lone pair is in the same direction as the resultant
dipole moment of the N – H bonds, whereas in NF 3
the orbital dipole is in the direction opposite to the
resultant dipole moment of the three N–F bonds.
➢ The orbital dipole because of lone pair decreases the
effect of the resultant N – F bond moments, which results in the low dipole moment of NF 3 as
represented as

Type of Example Dipole Geometry

Molecule moment,𝜇(D)
Molecule (AB) HF 1.78 Linear
HCl 1.07 Linear
HBr 0.79 Linear
HI 0.38 Linear
H2 0.00 Linear
Molecule (AB2) H2O 1.85 Bent
H2S 0.95 Bent
CO2 0.00 Linear
Molecule (AB3) NH3 1.47 Trigonal pyramidal
NF3 0.23 Trigonal pyramidal
BF3 0.00 Trigonal pyramidal
Molecule (AB4) CH4 0.00 Tetrahedral
CH3Cl 1.94 Tetrahedral
CH2Cl2 1.60 Tetrahedral
CHCl3 1.04 Tetrahedral
CCl4 0.00 Tetrahedral

➢ Note: - Regular shapes or symmetrical geometry like linear, trigonal planar, tetrahedral,
trigonalbipyramidal, octahedral, square planar containing (without lone pair) molecule has zero
dipole moment.
➢ Following molecule has zero dipole moment BF 3, CO2, SO3, CF4, PF5(g), SF6, XeF2, CS2, CCl4, PCl5(g),
IF7, XeF4.
➢ Some important dipole moment orders HF>HCl>HBr>HI
➢ CH3Cl>CH2Cl2>CHCl3>CCl4
➢ CH3Cl>CH3F>CH3Br>CH3I
➢ o-dichloro benzene> m-dichloro benzene>p-dichloro benzene
➢ For geometrical isomers usually the dipole moment of cis is more than trans but except cis and trans
form of 1– chloro propene.
➢ The valence shell electron pair repulsion(VSEPR) theory.
➢ VSEPR theory was proposed by Sidgwick and Powell and later extended by Gillespie and Nyholm. It
was developed by Ronald and Nyholm.
➢ This theory explains the shapes of simple molecules having electron pairs bonded or non-bonded.

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 ➢ The repulsions among the electron pairs present in the valence shell of the central atom decides the
shape of the molecules.
➢ According to this theory :
➢ 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 non
bonded) 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 minimize 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 singlem electron pair and the two or three electron pairs of a
multiple bond are treated as a single super pair.

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 ➢ Where two or more resonance structures can represent a molecule, the VSEPR model is applicable
to any such structure.
➢ d) The order of repulsions between various electron pairs is lone pair - lone pair > lone pair - bond
pair > bond pair - bond pair.
➢ e) The repulsive forces between different bonds is of the order triple bond > double bond > single
bond.
➢ Postulates of valence bond theory(VBT): -
➢ A covalent bond is formed by the overlapping of two half-
filled valence atomic orbitals of two same or 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.
➢ Attraction increases as the distance between the atoms
gets closer but nuclear-nuclear repulsion becomes
important if the atoms approach too close.
➢ 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.
➢ VBT explains the shape, the formation and directional properties of bonds in poly atomic molecules
in terms of overlapping and hybridization of atomic orbitals.
➢ Overlapping of atomic orbital’s: -
➢ When orbital’s of two atoms come close to form bond, their overlapping may be positive, negative (or)
zero depending on the sign(phase) and direction of orientation of amplitude of orbital wave function
in space.
➢ A) Positive overlap: - Orbital’s forming bond should have same sign (phase) and orientation in space.
This is called positive overlap.

B) Negative overlap: -
➢ Orbital’s forming bond should have opposite sign (out of phase) and orientation in space. This is
called negative overlap.

➢ C) Zero overlap: - this arises out of phase due to direction of approach.

➢ Types of Overlapping and Nature of Covalent Bonds: -

➢ The covalent bond may be classified into two types depending upon the types of overlapping:

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 ➢ (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 (hand-on) overlap of
bonding orbitals along the internuclear axis.
➢ This is called as head on overlap or axial overlap or end on end overlp . This can be formed by any
one of the following types of combinations of atomic orbital’s.
➢ s-s overlapping : In this case, there is overlap of two half filled s-orbital’s along the internuclear
axis.

➢ s-p overlapping: This type of overlap occurs between half filled s-orbital’s of one atom and half filled
p-orbitals of another atom.

➢ p–p overlapping : This type of overlap takes place between half filled p-orbital’s of the two
approaching atoms.

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

➢ Difference between sigma and pi bond.

S.NO Sigma bond 𝜎 Pi bond 𝜋
1. A 𝜎- Bond is formed by the axial A- 𝜋 bond is formed by the lateral
overlap of two half filled orbital’s overlap of orbital’s
belonging to the valence shells of
the two combining atoms.
2. The 𝜎- Bonding electron cloud is The 𝜋-bonding electron cloud lies above
symmetric about the internuclear and below the plane of the internuclear
axis. axis.
3. It is strong bond since the extent of It is weaker than 𝜎- Bond, since the
overlap is much. extent of overlap is less.
4. It allows free rotation of atoms or 𝜋-bond restricts such free rotation.
groups about the bond.
5. It can exist independently It is formed only after a ‘𝜎’ bond is
formed.
6. It determine the shape of the It does not determine the shape of the
molecule. molecule.

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 7. There can be only one ‘𝜎’ bond There can be one or two 𝜋- bonds
between two atoms. between the atoms.
8. Hybrid orbital’s form only ‘𝜎s’ Hybrid orbital’s cannot form 𝜋- bonds.
bonds.

Factors favouring the formation of covalent bonds

➢ 1. High ionisation enthalpy :
➢ Atoms having high ionization enthalpies do not have a tendency to lose electrons to form cations.
Such elements prefer to form covalent bonds, eg. Cl-Cl
➢ 2. Comparable electro negativity :
➢ Atoms with equal or nearly equal electro negativities tend to share equally a pair of electrons with
opposite spins. This leads to a better overlap of their atomic orbitals thus resulting in the formation
of a covalent bond.
➢ General properties of covalent substances
➢ Unlike ionic solids, covalent substances are made up of discrete molecules held together by van der
Waals forces due to which some of them exist in all three states of matter-solids, liquids and gases,
eg. I2, Br2 and Cl2.
➢ Covalent substances have low melting and boiling points with the exception of those forming three
dimensional net works like diamond.
➢ In general, covalent substances are poor conductors (with the exception of graphite).
➢ Covalent substances in general are not soluble in polar solvents, but they are soluble in non-polar
solvents.
➢ Since covalent bonds are directional, covalent compounds have definite shape.
➢ HYBRIDIZATION: - hybridization is defined as the process of mixing of atomic orbitals of nearly
equal energy of an atom to give the same number of new set of orbitals of equal energy and shapes.
➢ Salient features of hybridisation:-
➢ 1. In hybridisation, we mix a certain number orbitals, not a number of electrons.
➢ 2. The number of hybrid orbital’s forms equals the number of atomic orbitals that get hybridised.
➢ 3. Only orbital’s of similarly energy can be mixed to from hybrid orbital’s.
➢ 4. The hybrid orbitals formed are equivalent in energy and shape.
➢ 5. The hybrid orbitals are more effective in forming stronger bonds that lead to the formation of more
stable molecules.
➢ 6. The hybrid orbitals are directed in space so as to have minimum repulsions between electron
pairs.
➢ Important conditions for hybridisation
➢ i) The orbitals present in the valence shell of the atom are hybridised.
➢ ii) The orbitals undergoing hybridisation should have comparable energy.
➢ (iii) Promotion of electron is not an 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
➢ There are various types of hybridisation involving s, p and
d orbitals.
➢ sp hybridisation : In this hybridisation one 's' and one 'p'
atomic orbitals of the excited atom combine to form two
equivalent sp hybridised orbitals.
➢ This hybridisation is also known as diagonal hybridisation.
➢ In sp hybridisation each sp hybrid, orbital has 50% 's'
character and 50% 'p' character. The shape of the molecule
is linear or diagonal with a bond angle 180°.
➢ Ex. : Beryllium chloride molecule formation :
➢ 1) Be atom has 1s2 2s2 2px° 2py° 2pz° electronic configuration.

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 ➢ 2) In ground state it has no half filled orbitals. On excitation the configuration becomes 1s 2 2s1 2px1
2py° 2pz°.
➢ 3) Now sp hybridisation takes place at beryllium atom giving two sp hybrid orbitals. Each of them
with one unpaired electron forms a '𝜎' bond with one chlorine atom.
➢ 4) The overlapping is '𝜎'sp-p (Cl atom has the unpaired electron in 2pz orbital). In beryllium chloride
there are two '𝜎’ bonds.
➢ sp2 hybridisation : In this hybridisation one 's' and two 'p' atomic orbitals of the excited atom
combine to form three equivalent sp hybridised orbitals.
➢ This hybridisation is also known as trigonal hybridisation.
➢ In sp2 hybridisation each sp2 hybrid orbital has 33.33%’s’ nature and 66.66% 'p' nature.
➢ The shape of the molecule is trigonal with a bond angle 120°.
➢ E.g. : Boron trichloride molecule formation :
➢ 1) The electronic configuration of 'B' in the ground state
is 1s2 2s2 2px1 2py° 2pz°.
➢ 2) On excitation the configuration is 1s2 2s1 2px1 2py1 2pz°
now there are three half filled orbitals are available for
hybridisation.
➢ 3) Now sp2 hybridisation takes place at boron atom giving
three sp2 hybrid orbitals.
➢ Each of them with one unpaired electron forms a '𝜎' bond
with one chlorine atom. The overlapping is 𝜎sp2-p (Cl
atom has the unpaired electron in 2pz orbital). In boron
trichloride there are three '𝜎'bonds.
➢ sp3 hybridisation : In this hybridisation one ’s’ and three 'p' atomic orbitals of the excited atom
combine to form four equivalent sp 3 hybridised orbitals.
➢ This hybridisation is known as tetrahedral or tetragonal hybridisation.
➢ Each sp3 hybridised orbital possess 25%’s’ nature and 75% of 'p' nature. The shape of the molecule
is tetrahedral with a bond angle 109°28',
➢ e.g. : Formation of Methane molecule : -
➢ 1) The central atom of methane is
carbon.
➢ 2) The electronic configuration of
carbon in ground state is 1s2 2s2 2px1
2py1 2pz° and on excitation it is 1s2 2s1
2px1 2py1 2pz1. During excitation the 2s
pair splits and the electron jumps into
the adjacent vacant 2pz orbital.
➢ 3) The 1s2 2s1 2px1 2py1 2pz1 undergo sp3
hybridisation giving four equivalent sp3
hybridised orbitals.
➢ 4) Each sp3 hybrid orbital overlaps with
the 1s orbitals of hydrogen forming 𝜎sp3-
s bond.
➢ 5) In case of methane four 𝜎sp3-s bonds are formed. The bonds are directed towards the four corners
of a regular tetrahedron. The shape of methane molecule is tetrahedral with a bond angle 109°28'.
➢ sp3d hybridisation: - In this hybridisation one ’s’ and three 'p' and one ‘d’ atomic orbitals of the
excited atom combine to form five equivalent sp 3d hybridised orbitals.
➢ e.g.Formation of phosphorous pentachloride molecule : -

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 ➢ The ground state and the excited state outer electronic
configurations of phosphorus is (Z =15)
➢ Phosphorus undergoes sp3d - hybridisation by intermixing
of one s-orbital [3s], three p - orbitals [3px 3p 3pz] and one
d – orbital of [3dz2].
➢ These five hybrid orbitals overlap. The pz orbital of chlorine
atoms forming five 𝜎sp3d-pbonds.
➢ Out of these five P-Cl bonds three are equatorial and two P-
Cl bonds are axial bonds.
➢ There by PCl5 acquires the trigonal bipyramidal shape.
➢ The molecules contain two bond angles 90° and 120°.
➢ sp3d2 hybridisation: -
➢ In this hybridisation one s-orbital [3s], three p - orbitals [3px 3py 3pz] and two d – orbital of [3dz2,
3dx2-y2]. Orbitals of the excited atom combine to form six equivalent sp 3d2 hybrid orbitals.

➢ Formation of SF6 molecule:-

➢ These six sp3d2 hybrid orbitals overlap six 2pz

orbitals of fluorine atoms to form six 𝜎sp3d2-p
bonds.
➢ The direction of the bonds gives an octahedral
shape to the molecule.
➢ The bond angle is 90° or 180° & 90°.

sp2 Hybridisation in C2H4:

➢ In ethylene two carbons undergo

sp2 hybridisation.
➢ One of sp2 hybrid orbital of
carbon overlaps with sp2 hybrid
orbital of another carbon atom to
form C–C sigma 𝜎sp2-sp2 bond.
➢ The two other sp2 hybrid orbitals
of each carbon overlap with‘s’
orbital of hydrogen atoms to form
C–H 𝜎sp2-s bonds.
➢ The unhybridised 2pz orbital of
one carbon atom overlap side
wisely with the similar 2pz orbital to form weak 𝜋 bond.
➢ The molecule as a whole is planar and the bond angle is 120°.
➢ sp Hybridisation in C2H2: -
➢ In acetylene two carbons undergo sp
hybridisation.
➢ One of sp hybrid orbital of carbon
overlaps with sp hybrid orbital of
another carbon atom to form C–C sigma
𝜎sp-sp bond.
➢ The two other sp hybrid orbitals of each
carbon overlap with‘s’ orbital of
hydrogen atoms to form C–H 𝜎sp-s
bonds.
➢ The unhybridised orbital of one carbon
atom overlap side wisely with the similar orbital to form two weak 𝜋 bond.

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 ➢ The molecule as a whole is linear and the bond angle is 180°.
➢ hybridisation of the molecules is calculated by given principle:
𝟏
➢ V = [no of electrons in valency shell of the atom + no of monovalent atoms – charge on cation +
𝟐
charge on anion].
Value of V 2 3 4 5 6
Hybridisation sp Sp2 Sp3 Sp3d Sp3d2

➢ 4.7 MOLECULAR ORBITAL THEORY

➢ Molecular orbital (MO) theory was developed by F. Hund and R.S. Mulliken in 1932.
➢ The salient features of this theory are :
➢ The electrons in a molecule are present in the various molecular orbitals as the electrons of atoms
are present in the various atomic orbitals.
➢ The atomic orbitals of comparable energies and proper symmetry combine to form molecular orbitals.
➢ While an electron in an atomic orbital is influenced by one nucleus, in a molecular orbital it is
influenced by two or more nuclei depending upon the number of atoms in the molecule thus an
atomic orbital is monocentric while a molecular orbital is polycentric.
➢ The number of molecular orbital formed is equal to the number of combining atomic orbitals. When
two atomic orbitals combine, two molecular orbitals are formed. One is known as bonding molecular
orbital while the other is called antibonding molecular orbital.
➢ The bonding molecular orbital has lower energy and hence greater stability than the corresponding
antibonding molecular orbital.
➢ Just as the electron probability distribution around a nucleus in an atom is given by an atomic
orbital, the electron probability distribution around a group of nuclei in a molecule is given by a
molecular orbital.
➢ The molecular orbitals like atomic orbitals are filled in accordance with the Aufbau principle obeying
the Pauli’s exclusion principle and the Hund’s rule.
➢ The molecular orbital energy diagram (MOED) of N 2 and O2 molecules: -
➢ MOED of N2
➢ Electronic configuration of nitrogen (Z=7) is 1s2 2s2 2p3.
➢ Since nitrogen atom has 7 electrons, the molecular orbital of
nitrogen molecule (N2) has 14 electrons which are distributed
like
10–4
➢ Bond order = = 3 therefore N≡N is present.
2
➢ Absence of unpaired electrons N 2 molecule has diamagnetic
nature.

➢ MOED of O2
➢ Electronic configuration of oxygen (Z=8) is 1s 2 2s2 2p4.
➢ Since oxygen atom has 8 electrons, the molecular orbital of
oxygen molecule (O2) has 16 electrons which are distributed
like
10–6
➢ Bond order = = 2 therefore O=O is present.
2
➢ Presence of two unpaired electrons in 𝜋 ∗2py1 and 𝜋 ∗2pz1
showed that O2 molecule has paramagnetic nature.
➢ Bond order of some important compounds:-

Species Bond order

CO2 2
N3–(azide ion) 2
O3 1.5
NO2– 1.5

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 CO3–2 1.33
NO3– 1.33
H2O2 1
SO4–2 1.5
HCO3– 1.5
PO4–3 1.25
SO3–2 1.33
➢ Hydrogen bond: -
➢ Hydrogen bond is a weak electrostatic bond formed between partially positive charged hydrogen atom
and an highly electronegative atom of the same molecule or another molecule.
➢ Hydrogen bond is formed when the Hydrogen is bonded to small, highly electronegative atoms like
F, O and N. A partial positive charge will be on hydrogen atom and partial negative charge on the
electronegative atom.
➢ The bond dissociation energy of hydrogen bond is 40 KJ/mole.
➢ Hydrogen bond is represented with dotted lines (--------).
➢ Hydrogen bond is stronger than Vander Waals' forces and weaker than covalent bond.
➢ Hydrogen bonding is of two types. (1) Intermolecular hydrogen bond and (2) Intramolecular hydrogen
bond.
➢ 1) Intermolecular hydrogen bond :
➢ If the hydrogen bond is formed between two polar molecules it is called intermolecular hydrogen
bond, i.e., the hydrogen bond is formed between hydrogen atom of one molecule and highly
electronegative atom of another molecule is known as intermolecular hydrogen bond.
➢ Example: - Water (H2O), HF, NH3, p-nitrophenol, CH3COOH, ethyl alcohol etc.
➢ Water molecule forms an associated molecule through intermolecular hydrogen bond. Due to
molecular association water possess high boiling point.

➢ 2) Intramolecular hydrogen bond : -

➢ If the hydrogen bond is formed within the molecule it is known as
Intramolecular hydrogen bond.
➢ Example:- o-nitrophenol, o-hydroxybenzaldehyde (salicyladehyde).

➢ Abnormal behaviour due to hydrogen bond : -

➢ The physical state of substance may alter. They have high melting and
boiling points.
➢ Ammonia has higher boiling point than HCl even though nitrogen and chlorine have same electro
negativity values (3.0). due to Ammonia forms an associated molecule through intermolecular
hydrogen bond.
➢ p - hydroxy benzaldehyde have higher boiling point than o- hydroxy benzaldehyde. This is due to
intermolecular hydrogen bonding in para isomer.
➢ Ethyl alcohol is highly soluble in water due to association and co-association through intermolecular
hydrogen bonding.
➢ Explain the formation of Coordinate Covalent bond with one example.
➢ Co-ordinate covalent bond (dative bond) is a special type of covalent bond.
➢ It is proposed by Sidgwick.
➢ It is formed by the sharing of electrons between two atoms in which both the electrons of the shared
electron pair are contributed by one atom and the other atom nearly participates in sharing.
➢ The bond is represented as (" ") an arrow starting from the donar atom and directed towards
the acceptor atom.
➢ Examples :

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 ➢ 1) Ammonia - Boron trifluoride H3N: BF3

➢ Ammonia combines with boron trifluoride to give ammonium boron trifluoride.

➢ In ammonia nitrogen has a complete octet and also it has a lone pair of electrons. In BF 3 the boron
atom has a total of six electrons after sharing with fluorine. Nitrogen donates the electron pair to
boron to form a co-ordinate covalent bond between ammonia and boron trifluoride.
➢ Properties of co-ordinate covalent bond :
➢ The bond do not ionise in water.
➢ The compounds are generally soluble in organic solvents and are sparingly soluble in water.
➢ These compounds exhibit space isomerism because the bond is rigid and directional.
➢ The bond is semi polar in nature - so their volatility lies in between covalent and ionic bonds.
➢ State Fajan’s rule
➢ For a given cation, covalent character increases with increase in size of the anion. KF is less covalent
compared to KI.
➢ For a given anion, covalent character increases with a decrease in size of the ation.
Ex- LiF is more covalent compared to KF
➢ Covalent character increases with increasing charge either on cation or on anion.
Ex- SnCl4 is more covalent compared to SnCl2
➢ Covalent character is higher for compounds with cations with pseudo noble gas electronic
configuration (n-1)dns0 compared to compounds with cation with noble gas electronic configuration
ns2np6 Ex- Cu+ polarises Cl– more strongly than Na+. Therefore CuCl is more covalent than NaCl.
➢ Note psudo noble gas electronic configuration is said to be after loss of one electron it’s configuration
becomes 18 electrons in valance shell.
➢ lonic nature of the bond increases with increase in the size of catión,
➢ e.g.: The ionic nature increases in the order Li+ < Na+ < K+ < Rb+ < Cs+
➢ The formation of ionic bond is favoured with the decrease of the size of anion,
e.g.: CaF2 is more ionic than Cal2.
➢ If the charge on cation (or) anion (or) both is less, then they can form ionic bonds.
e.g.: The ionic nature increases in the order AlCl3 < MgCl2, < NaCl Al+3 Mg+2 Na+
➢ The catión with inert gas configuration is more stable.
e.g.: Ca+2 is more stable than Zn+2 ion.
Element A Element B Nature of compound
formed
• Larger cation • Smaller anion Strong ionic bond
• Smaller size • Larger size Covalent bond
• Larger cation with low • Smaller cation with low Strong ionic bond
charge charge
• Smaller ion with higher • Larger ion with higher Covalent bond
charge charge

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