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.
Kossel – Lewis approach to chemical bonding
 Kossel and Lewis explained formation of chemical bond based on the inertness of noble gas.
 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 that occupy the corners of a
cube which surround the ‘Kernel’.
 Lewis introduced simple notations called Lewis symbols to represent valence electrons in an atom. The
number of dots around the symbol of the element represents the number of valence electrons.
 According to Kossel, in the periodic table, the highly electronegative halogens and the highly
electropositive alkali metals are separated by the noble gases.
 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.
 Langmuir introduced the term covalent bond that involves sharing of electron pairs between bond atoms.
 When two atoms share one electron pair they are said to be joined by a single covalent bond. Eg – Cl2,
CH4
 If two atoms share two pairs of electrons, the covalent bond between them is called a double bond. Eg –
O2, CO2
 When combining atoms share three electron pairs , a triple bond is formed. Eg – N2, C2H2
Octet Rule
Kossel and Lewis developed an important theory of chemical combination between atoms known as
electronic theory of chemical bonding/ octet rule.
The rule states that: 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.
Lewis dot structure
The Lewis dot structure can be written by adopting the following steps:
 The least electronegative atom occupies the central position in the molecule/ion.
 The total numbers of electrons required for writing the structures are obtained by adding the valence
electrons of the combining atoms. ( CH4 has 8 electrons)
 For anions, an electron is added for each negative charge and for cations an electron is subtracted for
each positive charge from the total number of valence electrons.
 Knowing the chemical symbol and having knowledge of the skeletal structure of the compound,
electrons are distributed as bonding pairs between the atoms in proportion to the total bonds.
 After accounting for the shared pairs of electrons for single bonds, the remaining electron pairs are
either utilized for multiple bonding or remain as lone pairs.
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.
 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
- ( ½ ) total number of bonding(s hared) electrons.
 Formal charges do not indicate real charge separation within the molecule.
 It helps in keeping track of the valence electrons in the molecule.
 It also helps 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.
Limitations of the Octet Rule
1. The incomplete octet of the central atom
In some compounds like LiCl, BeH2 and BCl3, the number of electrons surrounding the central atom is
less than eight.
2. 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.
3. The expanded octet
In compounds like PF5, SF6, H2SO4 there are more than eight valence electrons around the central atom.
4. Even though octet rule is based upon the chemical inertness of noble gases.
5. Some noble gases like xenon and krypton combine with oxygen and fluorine to form a number of
compounds like XeF2, KrF2, XeOF2 etc.,
6. This theory does not account for the shape of molecules.
7. It does not explain the relative stability of the molecules.
Ionic or Electrovalent bond
 The formation of ionic compounds primarily depends upon :
o The ease of formation of the positive and negative ions from the respective neutral atoms.
o The arrangement of the positive and negative ions in the solid,i.e.,the lattice of the crystalline
compound.
 ionic bonds will be formed more easily between elements with comparatively low ionization enthalpies
and elements with comparatively high negative value of electron gain enthalpy
 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.
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 Parameters
1. Bond Length
Bond length is defined as the equilibrium distance between the nuclei of two bonded atoms in a molecule.
2. 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 angle is expressed in degree. It helps in determining its shape.
3. 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. 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 .
For example in case of H2O molecule, the enthalpy needed to break the two O – H bonds are not the same
( 502 & 427 KJ/mol). The difference in enthalpy value shows that the second O – H bond undergoes some
change because of changed chemical environment.
Larger the bond dissociation enthalpy, stronger will be the bond in the molecule.
4. Bond Order
Bond Order is given by the number of bonds between the two atoms in a molecule. The bond order in
H2 ,O2, N2 is 1,2,3 respectively.
With increase in bond order, bond enthalpy increases and bond length decreases.
Isoelectronic molecules and ions have identical bond orders. For example, F2 and O22– have bond order 1.
N2, CO and NO+ have bond order 3.
Resonance
 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.
 For example, the ozone, O3 molecule can be equally represented by the structures I and II shown
below:

I II III
In both structures we have a O–O single bond and a O=O double bond. The normal O–O and O=O bond
lengths are 148 pm and 121 pm respectively. Experimentally determined oxygen-oxygen bond lengths in
the O3 molecule are same (128 pm). Thus the oxygen-oxygen bonds in the O3 molecule are intermediate
between a double and a single bond.
Structure I & II represents canonical structure or resonance structure of O3.structure III represents the
structure of O3 more accurately and is called resonance hybrid.
 Resonance is represented by a double headed arrow.
 Resonance stabilizes the molecule as the energy of the resonance hybrid is less than the energy of any
single canonical structure.
 The canonical forms have no real existence.
• The molecule as such has a single structure which is the resonance
hybrid of the canonical forms and which cannot as such be depicted by a single Lewis structure.
Note: (Refer class work for the examples )
Polarity of Bonds
Non polar covalent bond
In the case of homo nuclear molecules like Cl2, H2 etc the shared pair of electron is equally attracted by the
two bonded atoms. This type of bond is called non polar covalent bond.
Polar covalent bond (Ionic character of covalent bond)
 In the case of hetero nuclear molecules like HF, H2O etc, the shared pair of electron gets displaced more
towards fluorine since the electronegtaivity of fluorine is far greater than hydrogen. This results in the
polarization of the molecule (charge separation) due to which the molecule possesses dipole moment.
Dipole Moment
 It is defined as defined as the product of the magnitude of the charge and the distance between the
centres of positive and negative charge.
 It is usually designated by a Greek letter ‘μ’.
 Dipole moment (μ) = charge (Q) × distance of separation (r)
 Dipole moment is usually expressed in Debye units (D).
 1 D = 3.33564 × 10–30 C m where C is coulomb and m is meter.
 Dipole moment is a vector quantity.
 It is represented by a crossed arrow( )put on Lewis structure of the molecule.
 The cross is on positive end and arrow head is on negative end of the molecule.
 For example the dipole moment of HF may be represented as : HF
 The arrow symbolises the direction of the shift of electron density in the molecule.
 In the 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.
 The dipole moment of a molecule is the vector sum of the dipole moments of various bonds.
Note: (Refer class work for the examples )
Covalent character of ionic bond
 The covalent character of ionic bond is explained by Fajans in terms of Fajans rule. According to Fajans
rule:
 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)dnnso,(of transition metals) is more polarising than the
one with a noble gas configuration, ns2 np6(alkali and alkaline earth metal).
 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 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 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 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 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.
For the 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.
While the lone pairs are localised on the central atom, each bonded pair is shared between two atoms. As a
result, the lone pair electrons in a molecule occupy more space as compared to the bonding pairs of electrons.
This results in greater repulsion between lone pairs of electrons as compared to the lone pair - bond pair and
bond pair - bond pair repulsions. These repulsion effects results in deviation from the expected shape. 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)

Note: (Refer class work for the examples )

Valence Bond Theory (VBT)

Orbital overlap concept: When two atoms approach each other to form a bond, their atomic orbitals overlap.
i.e, The formation of a covalent bond involves the overlapping of half filled atomic orbitals. The orbitals
undergoing overlap must have electrons with opposite spin. The strength of a covalent bond depends upon the
extent of overlapping. The greater the overlapping, more is the energy released and stronger will be the covalent
bond.
Types of covalent bond: The covalent bonds can be classified into two different categories depending on the
type of overlapping. These are : i) Sigma covalent bond ii) Pi covalent bond.
Sigma covalent bond: This is formed by the axial overlapping of half filled atomic orbitals. The AO’s overlap
along the inter nuclear axis and involve end to end or head on overlap. The electron cloud formed as a result of
axial overlap is cylindrically symmetrical about the inter nuclear axis. Eg for this type are s-s, s-p, p-p overlap.
Pi covalent bond: This type of covalent bond is formed by the lateral or sidewise overlap of the AO’s. The
orbital overlap takes place in such a way that their axis are parallel to each other but perpendicular to the inter
nuclear axis. The pi bond consists of two charge clouds above and below the plane of atoms involved in the
bond formation.
Comparison between Sigma and Pi bond
Sigma bond Pi bond
Formed by the axial overlap of AO’s. Formed by the lateal overlap of AO’s.
Can be formed overlap of s-s, s-p, p-p orbitals. Involves overlap of p orbitals only.
The bond is stronger due to greater extent of The bond is weaker as overlapping occurs to a
overlap. smaller extent.
Free rotation of atoms around sigma bond Free rotation of atoms around pi bond not
possible. possible.
Can be present alone or along with a pi bond. Always present along with a sigma bond.
Are directional in nature. i.e, decides shape of Are non directional. They only modify
the molecule. dimensions of the molecule.
Hybridisation:It may be defined as the phenomenon of intermixing of AO’s of slightly different energies of the
atom to form new set of orbitals of equivalent energies and identical shape.

Features of hybridization:
The orbitals taking part in hybridization must have only a small difference of energy.The hybrid orbitals have
equivalent energies and identical shape. The number of hybrid orbitals will be equal to the number of AO’s
taking part in hybridization. Both half filled and completely filled orbitals of the valence shell can take part in
hybridization.The hybrid orbitals can form stronger bonds that the unhybridised orbitals as they undergo
effective overlap. The hybrid orbitals are directed in space in some preferred directions so as to have minimum
repulsion.Thus hybridization controls the geometry of molecule.
Types of hybridization:
There are different types of hybridization depending upon the type of orbitals involved in mixing.
sp3 hybridisation
This type involves mixing of one s and three p orbitals of the valence shell to form four sp3 hybrid orbitals of
equivalent energies and shape. The four sp3 hybrid orbitals are directed towards four corners of a tetrahedron
with the bond angle as 109o28’.
Eg: methane,ethane,NH3, H2O
sp2 hybridisation
This type involves mixing of one s and two p orbitals of the valence shell to form three sp2 hybrid orbitals of
equivalent energies and shape. The molecules undergoing this type of hybridization wil have trigonal planar
shape with 120o bond angle.
Eg: BF3, Ethene
sp hybridization
This type involves mixing of one s and one p orbital of the valence shell to form two sp hybrid orbitals of
equivalent energies and shape. The molecules undergoing this type of hybridization wil have linear shape with a
bond angle of 180o.
Eg: BeCl2, Ethyne.
sp3d hybridization
This type involves mixing of one s three p and one d orbital of the valence shell to form five sp3d hybrid orbitals
of equivalent energies and shape. The molecules undergoing this type of hybridization wil have
trigonalbipyramidal shape with a bond angle of 120obetween the three equatorial bonds lying in the same
plane.The two axial bonds in the vertical plane will make an angle of 90o with the equatorial bonds. Eg: PCl5
sp3d2 hybridization
This type involves mixing of one s three p and two d orbital of the valence shell to form six sp3d2 hybrid orbitals
of equivalent energies and shape. The molecules undergoing this type of hybridization wil have octahedral
shape with a bond angle of 90o.Eg: SF6.
Note: (Refer class work for the examples )

Molecular Orbital Theory (MOT)

Features: Refer text book
Formation of MO’s – LCAO method( Linear combination of AO’s)
MO’s are formed by the combination of AO’s of the bonded atoms. AO’s are represented by the wave
function,ψ obtained from the solutions of Schrodinger wave equation. But due to the complex nature of
Schrodinger wave equation it may not be easy to solve it for molecules. Hence an approximate method, LCAO
method is used to obtain the wave functions for MO’s.
Formation of molecular orbitals
According to LCAO method, the linear combination of atomic orbitals can take place by addition and by
subtraction of wave functions of atomic orbitals. 1.e, ΨMO = ΨA + ΨB.
These two types of combinations of AO’s gives rise to two MO’s .
MO obtained by the addition of wave functions is called bonding molecular orbital represented as ‘σ ‘and the
one obtained by subtraction is called antibonding molecular orbital represented as ‘σ *‘

Differences between BMO and ABMO

BMO ABMO
1. Formed by the addition of overlapping AO’s. Formed by the subtraction of the overlapping AO’s.

2. The lobes of the combining AO’s have same
sign.
3. It has greater electron density in the region
between the two nuclei of bonded atoms.
4. It possesses lower energy than the isolated AO’s.
The lobes of the combining AO’s have opposite
sign.
It has lesser electron density in the region between
the two nuclei of bonded atoms.
It possesses higher energy than the isolated AO’s.

Sigma and Pi MO’s

When the AO’s overlap head on along the inter nuclear axis, sigma MO is formed. When the AO’s overlap
laterally/sidewise, Pi MO is formed. By convention z axis is taken as the inter nuclear axis.

Differences between BMO and ABMO

Sigma MO Pi MO
1. Formed by the head to head overlap of the Is formed by the sidewise overlap of AO’s
AO’s along internuclear axis. perpendicular to the internuclear axis.
2. The orbital is symmetrical about internuclear The orbital is not symmetrical about the
axis. internuclear axis.
3. It leads to the formation of strong bond. It leads to the formation of a weak bond.
Combination of AO’s to form MO’s
 The important conditions for the effective combination of AO’s are :
 The combining AO’s should have same or nearly same energy.(is can combine with is but not
2s)
 The extent of overlapping between the AO’s should be large.
 The combining AO’s must have same symmetry about the axis.(2s can overlap with 2s or 2pz not
with 2px or 2py)
 The various BMO’s and ABMO’s formed by the overlap of 1s,2s,2p are as below:
AO’s BMO’s ABMO’s
1s σ1s σ*1s
2s σ2s σ*2s
2pz σ2pz σ*2pz
2px π2px π*2px
2py π2py π*2py
 The energy levels of these MO’s have been determined by spectroscopic methods. The order of
increasing energy of MO’s obtained by the combination of 1s,2s,2p orbitals of two atoms is:
σ1s, σ*1s, σ2s, σ*2s, σ2pz , π2px = π2py , π*2px= π*2py, σ*2pz---- for O2, F2
σ1s, σ*1s, σ2s, σ*2s, π2px = π2py , σ2pz, π*2px= π*2py, σ*2pz----- for diatomic molecules of second
period.
 The fiiling of MOs takes place in accordance with Aufbau principle, Pauli’s exclusion principle and
Hunds rule of maximum multiplicity.
Note: (Refer class work for the examples )