Class XI Chemistry

UNIT 4
CHEMICAL BONDING AND MOLECULAR
STRUCTURE
Topics:-
• Octet Rule
• Covalent Bond
• Limitations of Octet Rule
Chemical bond
• The attractive force which holds various constituents (atoms, ions, etc.) together
in different chemical species is called a chemical bond.
Valence electrons:-Electrons present in the outermost shell are known as valence
electrons
Lewis symbols:-Valence electrons of an atom are represented by dots around the
symbol of the element
Significance of Lewis Symbols
• 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
• Theory of chemical combination between atoms is known as electronic
theory of chemical bonding.
• It was developed by Kössel and Lewis in 1916. According to this,
• 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.
Covalent Bond
• Lewis postulated that atoms achieve the stable octet when they are
linked by chemical bonds.
• Langmuir introduced the term covalent bond.
• According to Lewis-Langmuir theory a covalent bond is formed by
sharing a pair of electron between two bonded atoms
 Single covalent bond
• If covalent bond is formed by sharing a pair of electron it is called a single
covalent bond and it is represented by a line between the two atoms

Double Bond:-
If two atoms share two pairs of
electrons

Triple Bond:-
If two atoms share three pairs of
electrons
• Multiple bonds- double and triple bonds
collectively known as multiple bonds
Limitations of the Octet Rule
1) The incomplete octet of the central atom:-
• This is especially the case with elements having less than four valence
electrons.
• Examples are LiCl, BeH2 and BCl3.

• Li, Be and B have 1,2 and 3 valence electrons only.

• Some other such compounds are AlCl3 and BF3.
Continue…
Limitations of the Octet Rule
2) Odd-electron molecules
• In molecules with an odd number of electrons like nitric oxide, NO and
nitrogen dioxide, NO 2, the octet rule is not satisfied for the N atoms
Continue…
Limitations of the Octet Rule
3) The expanded octet:-
• Elements in and beyond the third period of the periodic table have, apart
from 3s and 3p orbitals, 3d orbitals also available for bonding.
• 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.
sulphur also forms many
compounds in which the octet rule
is obeyed.
For example sulphur dichloride SCl 2
Continue…
Limitations of the Octet Rule
4) 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.,
5) This theory does not account for the shape of molecules.
6) It does not explain the relative stability of the molecules being totally silent
about the energy of a molecule.
 Class XI Chemistry
UNIT 4
CHEMICAL BONDING AND MOLECULAR
STRUCTURE
Topics:-
• Lewis dot structures
• Formal Charge
 Lewis dot structures
• The Lewis dot structures provide a picture of bonding in molecules and ions in terms of
the shared pairs of electrons and the octet rule
 Writing of Lewis dot structures
The Lewis dot structures can be written by adopting the following steps:
Step 1:- Count the total number of valence electrons. For anions, add one electron
for each negative charge and for cation subtract one electron for each positive charge.
Step 2:- Write skeletal structure (In general the least electronegative atom
occupies the central position)
Step 3:-Draw a single bond by one shared electron pair between bonded atoms.
Remaining electron pairs are either utilized for multiple bonding or remain as the
lone pairs. If necessary rearrange the electrons as multiple bonds or lone pairs
to complete the octet.
Problem 4.1 Write the Lewis dot structure of CO molecule.
Solution
• Step 1. Count the total number of valence electrons of carbon and oxygen atoms.
The valence electrons available are 4 + 6 =10.
• Step 2. The skeletal structure of CO is written as: C O
• Step 3. Draw a single bond (one shared electron pair) between C and O and
complete the octet on O, the remaining two electrons are the lone pair on C.

• This does not complete the octet on carbon and hence we have to resort to multiple
bonding (triple bond) between C and O atoms.
Formal Charge
• In case of polyatomic ions, the net charge is possessed by the ion as a
whole and not by a particular atom.
• It is, however, feasible to assign a formal charge on each atom.
• 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.
 Continue…
Formal Charge:- Consider the ozone molecule (O3).
The Lewis structure of O 3 may be drawn as

• 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.
 Class XI Chemistry
UNIT 4
CHEMICAL BONDING AND MOLECULAR
STRUCTURE
Topics:-
• Ionic Or Electrovalent Bond
• Lattice Enthalpy
 Ionic Or Electrovalent Bond
Kössel, drew attention to the following facts:
❖ In the periodic table, the highly electronegative halogens and the highly electropositive
alkali metals are separated by the noble gases;
❖ The formation of a negative ion from a halogen atom and a positive ion from an alkali
metal atom is associated with the gain and loss of an electron by the respective atoms;
❖ The negative and positive ions thus formed attain stable noble gas electronic
configurations. The noble gases (with the exception of helium which has a duplet of
electrons) have a particularly stable outer shell configuration of eight (octet) electrons,
ns2np 6.
❖ The negative and positive ions are stabilized by electrostatic attraction.
Continue…
Ionic Or Electrovalent Bond
• For example, the formation of NaCl
The bond formed, as a result of the
electrostatic attraction between the
positive and negative ions is termed
as the electrovalent bond.

The electrovalence is equal to the

• Formation of CaF 2
number of unit charge(s) on the ion.
Thus, calcium is assigned a positive
electrovalence of two, while chlorine a
negative electrovalence of one.
Ionic Bonds: One Big Greedy
Thief Dog!
Continue…
Ionic Or Electrovalent Bond
❑ The formation of ionic compounds would depend upon:
❑ 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.

• 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.
• Lattice enthalpy plays a key role in the formation of ionic compounds
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.
• For example, the lattice enthalpy of NaCl is 788 kJ mol–1. This means that 788 kJ
of energy is required to separate one mole of solid NaCl into one mole of Na+ (g)
and one mole of Cl– (g) to an infinite distance. NaCl(s) → Na + (g) + Cl– (g)
• The solid crystal being three dimensional; it is not possible to calculate lattice
enthalpy directly from the interaction of forces of attraction and repulsion only. It is
determined indirectly using Born-Haber Cycle .
 Class XI Chemistry
UNIT 4
CHEMICAL BONDING AND MOLECULAR
STRUCTURE
Topics:-
• Bond Parameters-Bond Length, Bond Angle, Bond Enthalpy, Bond
Order
 Bond Parameters
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

• Each atom of the bonded pair contributes

to the bond length .
• In the case of a covalent bond, the
contribution from each atom is called the
covalent radius of that atom.
 Covalent radius and van der Waals radius

• The covalent radius is half of the distance

between two similar atoms joined by a
covalent bond in the same molecule.
• The van der Waals radius is half of the
distance between two similar atoms which
are not bonded
Continue…
Bond Parameters
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 which can be experimentally determined by
spectroscopic methods.
• It helps in determining the shape of molecule/complex ion.
• For example H–O–H bond angle in water is 104.5o
Continue…

Bond Parameters
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.

Larger the bond dissociation enthalpy,

Enthalpy of
stronger will be the bond in the
atomization
molecule .
Continue…

Bond Parameters
Bond Enthalpy
• In case of polyatomic molecules like water H 2O

• Two O-H bond have different values of bond enthalpy 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
Molecule No. of Shared Number of Bond Order
electron pairs covalent bonds
Hydrogen (H 2) One 1 1
Oxygen (O2) Two 2 2
Nitrogen (N2) Three 3 3
Carbon monoxide (CO) Three 3 3
 Class XI Chemistry
UNIT 4
CHEMICAL BONDING AND MOLECULAR
STRUCTURE
Topics:-
• Concept of Resonance
Resonance Structures
• A single Lewis structure of a molecule is not sufficient to describe its
experimentally determined parameters. For example, Ozone O3.

• 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).
Continue…
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.
• Resonance is represented by a double headed arrow.
Problem 4.4:- Explain the structure of CO2 molecule.
Solution:-
• The experimentally determined carbon to oxygen bond length in CO2 is 115 pm.
• The lengths of a normal (C=O) and (C≡O) are 121 pm and 110 pm respectively.
• So a single Lewis structure cannot depict this position and it becomes necessary to
write more than one Lewis structures and to consider that the structure of CO2 is best
described as a hybrid of the canonical or resonance forms I, II and III.
 Continue…
Resonance Structures
• In general, it may be stated that
❖ Resonance stabilizes the molecule as the energy of the
resonance hybrid is less than the energy of any single
canonical structure; and,
❖ Resonance averages the bond characteristics as a whole.
Resonance Energy:-
• Energy difference between energy of the resonance hybrid and energy of the most
stable canonical structure is known as resonance energy
Continue…
Resonance Structures
Remember that :
❖ The canonical forms have no real existence.
❖ The molecule does not exist for a certain fraction of time in one canonical
form and for other fractions of time in other canonical forms.
❖ There is no equilibrium between the canonical .
❖ 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.
 Class XI Chemistry
UNIT 4
CHEMICAL BONDING AND MOLECULAR
STRUCTURE
Topics:-
• Polar covalent bond
• Dipole moment
• Covalent Character in Ionic Bond-Fajans Rule
Polarity of Bonds- Polar covalent bond
• When covalent bond is formed between two similar atoms, for example in H2, O2, Cl2,
N2 or F2, the shared pair of electrons is equally attracted by the two atoms. As a
result electron pair is situated exactly between the two identical nuclei. The bond so
formed is called nonpolar covalent bond.
• When covalent bond is formed between two atoms of different elements
(heteronuclear molecule) like HF, the shared electron pair between the two atoms
gets displaced more towards more electronegative atom (fluorine).The resultant
covalent bond is a polar covalent bond.
• As a result of polarisation, the molecule possesses the dipole moment
Covalent Bond, Polar covalent bond and Ionic
Bond
Dipole moment
• The product of the magnitude of the charge and the distance between the
centres of positive and negative charge is known as dipole moment.
• It is usually designated by a Greek letter ‘μ’ (Mu).
• Mathematically,
• 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.
Continue…
Dipole moment
• 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.
• But in chemistry presence of dipole moment is represented by the crossed
arrow put on Lewis structure of the molecule.
• The cross is on positive end and arrow head is on negative end.
• For example

This arrow symbolises the direction of the shift of

electron density in the molecule
 Dipole moment and geometry
• In case of polyatomic molecules the dipole moment depends
Bond dipole:-
not only on bond dipoles but also on the spatial arrangement
• Dipole moment of
of various bonds in the molecule.
individual bond
• In such case, the dipole moment of a molecule is the vector
sum of the dipole moments of various bonds.

• For example H2O molecule, bent , bond angle of 104.5o.

• Net dipole moment =1.85 D

• It is the resultant of the dipole moments of two O–H
bonds.
Continue…
Dipole moment and geometry
• The dipole moment in case of BeF 2 is zero.
• This is because the two equal bond dipoles point in opposite directions and cancel
the effect of each other.

• In BF3, the dipole moment is zero although the B – F bonds are oriented at an angle
of 120 o to one another, the three bond moments give a net sum of zero as the
resultant of any two is equal and opposite to the third.
 Dipole Moment in NH3 and NF3 molecule.
• Both have pyramidal shape with a lone pair of electrons on nitrogen atom.
• Dipole moment of NH 3 ( 4.90 × 10–30 C m) is greater than that of NF 3 (0.8 × 10–30 C m).

Fluorine is more electronegative than

nitrogen
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.
Covalent Character in Ionic Bond
• The cation polarises the anion, pulling the electronic charge toward itself and
thereby increasing the electronic charge between the two.
• In a covalent bond, electron charge density is in between the nuclei.
• Factors affecting the percent covalent character of the ionic bond:-
• The polarising power of the cation,
• the polarisability of the anion and
• the extent of distortion (polarisation) of anion
Continue…
Covalent Character in Ionic Bond
• Polarising power
• It is the extent to which a cation can polarise an anion.
• It is proportional to charge density.
• Charge density is the ratio of charge to volume.
• Polarising power α Charge density.
• More the charge density, greater is the polarising power for that cation.
• Polarisability
• It is the extent to which an anion can be polarised.
• It can also be called as the ease with which an ion can be polarised.
• Polarisation is the distortion of a spherically symmetric electron cloud to an unsymmetric cloud.
Fajans Rule
• The partial covalent character of ionic bonds was discussed by Fajans in terms of the
following rules:
• Size of the ion: 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 charge of Cation: The greater the charge on the cation, the greater the
covalent character of the ionic bond.
• Electronic Configuration: For cations of the same size and charge, the one, with
electronic configuration (n-1)d nnso, typical of transition metals, is more polarising
than the one with a noble gas configuration, ns2 np 6, typical of alkali and alkaline
earth metal cations.
 Class XI Chemistry
UNIT 4
CHEMICAL BONDING AND MOLECULAR
STRUCTURE
Topics:-
• The Valence Shell Electron Pair Repulsion (VSEPR) Theory
• Shapes of Molecules in which the central atom has no lone pair
 The Valence Shell Electron Pair Repulsion
(VSEPR) Theory
• This theory provides a simple procedure to predict the shapes of covalent
molecules.
• Proposed by:-Sidgwick and Powell in 1940,
• Based on the repulsive interactions of the electron pairs in the valence shell of the
atoms.
• Further developed and redefined by Nyholm and Gillespie (1957).
The main postulates of VSEPR theory:-
1) The shape of a molecule depends upon the number of valence shell electron
pairs (bonded or nonbonded) around the central atom.
2) Pairs of electrons in the valence shell repel one another since their electron
clouds are negatively charged.
Continue…
The main postulates of VSEPR theory:-
3) These pairs of electrons tend to occupy such positions in space that minimize
repulsion and thus maximise distance between them.
4) The valence shell is taken as a sphere with the electron pairs localising on the
spherical surface at maximum distance from one another.
5) 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.
6) 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:
• lp – lp > lp –bp > bp – bp lp= Lone pair
bp=Bond pair

• lone pairs are localised on the central atom and 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.
 Molecules in which the central atom has no lone
pair

Geometry is regular-
• linear,
• trigonal planar,
• tetrahedral,
• Trigonal bipyramidal
and
• octahedral
Continue…
Molecules in which the central atom has no lone
pair
 Class XI Chemistry
UNIT 4
CHEMICAL BONDING AND MOLECULAR
STRUCTURE
Topics:-
• Shapes of Molecules in which the central atom has one or more
lone pairs- According to VSEPR Theory
 Molecules in which the central atom has one or more lone
pairs

Regular
Geometry -
• linear,
• trigonal planar,
• tetrahedral,
• Trigonal bipyramidal
• octahedral
Continue…
Molecules in which the central atom has one or more lone
pairs
Continue…
Molecules in which the central atom has one or more lone
pairs
 The Effect of Nonbonding Electrons

• Since electrons in a bond are attracted by two nuclei, they do not

repel as much as lone pairs.
• Therefore, the bond angle decreases as the number of lone pairs
increases
Some Specific Examples

• electron pairs of a multiple bond are treated as a

single super pair.
• lone pair- bond pair repulsion is much more as
compared to the bond pair-bond pair repulsion.
• So the angle is reduced to 119.5° from 120°.
Continue…
Some Specific Examples

• If bond angle is more than 100o, repulsive

interactions are not significant

• In (a) the lp is present at axial position so there are

three lp—bp repulsions at 90°.
• In(b) the lp is in an equatorial position, and there are
two lp—bp repulsions.
• Hence, arrangement (b) is more stable.
• The shape shown in (b) is described as a distorted
tetrahedron, a folded square or a see-saw.
Continue…
Some Specific Examples

• In (a) the lp are at equatorial position so

there are less lp-bp repulsions as compared
to others in which the lp are at axial
positions.
• So structure (a) is most stable. (T-shaped).
 Class XI Chemistry
UNIT 4
CHEMICAL BONDING AND MOLECULAR
STRUCTURE
Topics:-
• Valence bond theory(VBT)
Valence bond theory
• Introduced by Heitler and London (1927) and developed further by Pauling and others.
• based on the
• knowledge of atomic orbitals,
• Electronic configurations of elements ,
• The overlap criteria of atomic orbitals,
• The hybridization of atomic orbitals and the
• principles of variation and superposition
• A covalent bond is formed by the overlapping of atomic orbitals.
• Before overlapping atomic orbitals undergo hybridization.
• A bond is formed when attractive interactions balance the repulsive interactions and net energy
is lowered
Continue…
Valence bond theory
• consider the formation of hydrogen molecule
• Consider two hydrogen atoms A and B approaching each other having nuclei NA and
NB and electrons present in them are represented by eA and eB.
• Attractive forces arise between:
• nucleus of one atom and its own electron that is NA – e A and NB– eB.
• nucleus of one atom and electron of other atom i.e., NA– eB, NB– eA.
• Similarly repulsive forces arise between
• electrons of two atoms like eA – e B,
• nuclei of two atoms NA – N B.
 Continue…
consider the formation of hydrogen molecule
• Attractive forces tend to bring the two atoms close to each other
whereas repulsive forces tend to push them apart
 Continue…
consider the formation of hydrogen molecule
• Magnitude of new attractive force is more than the new repulsive forces.
• As a result, two atoms approach each other and potential energy decreases.
• Ultimately a stage is reached where the net force of attraction balances the force of
repulsion and system acquires minimum energy.
• At this stage two hydrogen atoms are said to be bonded together to form a stable
molecule having the bond length of 74 pm.
• Since the energy gets released when the bond is formed between two hydrogen atoms,
the hydrogen molecule is more stable than that of isolated hydrogen atoms.
• The energy so released is called as bond enthalpy
 When H – H distance = 74 pm,
Repulsion = Attraction
→ strongest bond
→ optimal overlap
74 pm
→ lowest energy
→ bond enthalpy -435.8 kJ
 At H – H distance > 74 pm,
Repulsion < Attraction
→ weaker bond
→ too little overlap
→ atoms come closer
74 pm

> 74 pm
 At H – H distance < 74 pm,
Repulsion > Attraction
→ weaker bond
→ too much overlap
→ atoms get further apart
74 pm

< 74 pm
 Class XI Chemistry
UNIT 4
CHEMICAL BONDING AND MOLECULAR
STRUCTURE
Topics:-
• Overlapping of Atomic Orbitals
• Sigma and pi Bonds
Orbital Overlap Concept
• In the formation of hydrogen molecule, there is a minimum energy state when two
hydrogen atoms are so near that their atomic orbitals undergo partial
interpenetration.
• The partial merging of atomic orbitals is called overlapping of atomic orbitals
which results in the pairing of electrons.
• The extent of overlap decides the strength of a covalent bond.
• In general, greater the overlap the stronger is the bond formed between two
atoms.
• Therefore, according to orbital overlap concept, the formation of a covalent bond
between two atoms results by pairing of electrons present in the valence shell
having opposite spins.
 Overlapping of Atomic Orbitals
• When orbitals of two atoms come close
to form bond, their overlap may be
positive, negative or zero depending
upon the sign (phase) and direction of
orientation of amplitude of orbital wave
functionand
• Positive in space
negative sign on boundary surface
diagrams show the sign (phase) of orbital wave
function and are not related to charge.
• Orbitals forming bond should have same sign
(phase) and orientation in space.
• This is called positive overlap.
Overlapping of Atomic Orbitals

• A negative overlap results when two orbitals with different

phase overlap with each other.
• A zero overlap will results when orbitals do not overlap at all or
do not overlap effectively.
• A negative and zero overlap of orbitals does not result in bond
formation
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.
• In this the overlapping of orbitals takes place to a larger extent. Hence, it is
stronger
• It may be formed by s-s overlapping, s-p overlapping, p–p overlapping
• In this electron density is concentrated in between the nuclei of bonded atoms.
Continue…
(i) Sigma(σ) bond :
s-s overlapping : In this case, there is overlap of two half filled s-orbitals
along the internuclear axis
Continue…
(i) Sigma(σ) bond :
s-p overlapping: This type of overlap occurs between half filled s-orbitals
of one atom and half filled p-orbitals of another atom.
Continue…
(i) Sigma(σ) bond :
p–p overlapping : This type of overlap takes place between half filled p-
orbitals of the two approaching atoms.
(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.
• This bond is formed by sidewise or lateral overlapping of atomic orbitals.
• In this bond electron charged clouds is above and below the plane of the
participating atoms.
• Extent of overlapping is smaller so it is weaker.
Differences between Sigma and pi Bonds
 Class XI Chemistry
UNIT 4
CHEMICAL BONDING AND MOLECULAR
STRUCTURE
Topics:-
• HYBRIDISATION
Why?
 Salient features of hybridisation
• The number of hybrid orbitals is equal to the number of the atomic orbitals that get
hybridised.

• The hybridised orbitals are always equivalent in energy and shape.

• The hybrid orbitals are more effective in forming stable bonds than the pure atomic
orbitals.

• These hybrid orbitals are directed in space in some preferred direction to have minimum
repulsion between electron pairs and thus a stable arrangement. the type of
hybridisation indicates the geometry of the molecules
 Important conditions for hybridisation
• The orbitals present in the valence shell and penultimate shell of the atom are

hybridised.

• The orbitals undergoing hybridisation should have almost equal energy.

• Promotion of electron is not essential condition prior to hybridisation.

• It is not necessary that only half filled orbitals participate in hybridisation. In some
cases, even filled orbitals and empty orbitals of valence shell and penultimate shell
take part in hybridisation.
 Class XI Chemistry
UNIT 4
CHEMICAL BONDING AND MOLECULAR
STRUCTURE
Topics:-
• HYBRIDISATION-Involving s and p orbitals
• The molecule thus gets distorted and the
bond angle is reduced to 107° from
109.5°.
• The geometry is pyramidal
• The bond angle in this case is reduced to 104.5° from 109.5° Repulsion lp-lp > lp-bp
> bp-bp
• Water molecule has V-shape or angular geometry or bent shape.
 Class XI Chemistry
UNIT 4
CHEMICAL BONDING AND MOLECULAR
STRUCTURE
Topics:-
• Hybridisation of Carbon in Ethane, Ethene, Ethyne
Hybridisation in Ethane C2H6 molecule

• Each C is sp3 hybrid

• C-C bond , sp3-sp3 sigma bond .
• Each C-H sp3–s sigma bonds .
• In ethane C–C bond length is 154 pm and each
C–H bond length is 109 pm.
 Hybridisation in Ethene C2H4 molecule

• Each C is sp2 hybrid

• C-C bond , sp2-sp2 sigma
bond .
• Each C-H sp2–s sigma bonds .
 Continue…
Hybridisation in Ethene C2H4 molecule
• The unhybridised orbital (2p x or 2p y) of one
carbon atom overlaps sidewise with the
similar orbital of the other carbon atom to
form weak π bond, which consists of two
equal electron clouds distributed above and
below the plane of carbon and hydrogen
C=C bond length 134 pm.
atoms.
C–H bond length 108 pm.
H–C–H bond angle is
117.6°
H–C–C angle is 121°.
 Hybridisation in Ethyne C2H2 molecule

• Each of the two unhybridised

• Each C is sp hybrid
p orbitals of both the carbon
• C-C bond , sp-sp sigma
atoms overlaps sidewise to
bond .
form two π bonds between
• Each C-H sp –s sigma
the carbon atoms.
bonds .
 Continue…
Hybridisation in Ethyne C2H2 molecule

• The triple bond between the two carbon

atoms is made up of one sigma and two
pi bonds

C≡C bond length 120

pm.
C–H bond length 106
pm.
Summarization
 Class XI Chemistry
UNIT 4
CHEMICAL BONDING AND MOLECULAR
STRUCTURE
Topics:-
• Hybridisation of Elements involving d Orbitals
• Formation of PCl5 and SF6
Formation of PCl5 (sp3d hybridisation):

Five sp3d hybrid orbitals are directed

towards the five corners of a trigonal
bipyramidal
 Continue…
Formation of PCl5 (sp3d hybridisation):
• All the bond angles in trigonal bipyramidal geometry are
not equivalent.
• Three P–Cl bond lie in one plane and make an angle of
120° with each other; these bonds are termed as
equatorial bonds.
• The remaining two P–Cl bonds–one lying above and the
other lying below the equatorial plane, make an angle of
90°more
As the axial bond pairs suffer with repulsive
the [Link]
These bonds
fromare
thecalled axial bond
equatorial bonds.

pairs, therefore axial bonds are slightly longer and hence slightly weaker than the
equatorial bonds; which makes PCl5 molecule more reactive.
Formation of SF6 (sp3d2 hybridisation)

sp3d 2 hybrid orbitals are projected

towards the six corners of a regular
octahedron in SF6.
 Continue…
Formation of SF6 (sp3d2 hybridisation)

• These six sp3d 2 hybrid orbitals overlap with singly

occupied orbitals of fluorine atoms to form six S–F
sigma bonds.
• Thus SF 6 molecule has a regular octahedral geometry
 Class XI Chemistry
UNIT 4
CHEMICAL BONDING AND MOLECULAR
STRUCTURE
Topics:-
• Molecular Orbital Theory(MOT)
• Linear Combination of Atomic Orbitals (LCAO)
MOLECULAR ORBITAL THEORY
• Developed by F. Hund and R.S. Mulliken in 1932.
• The salient features of this theory are :
1) The electrons in a molecule are present in the various molecular orbitals.
2) The atomic orbitals of comparable energies and proper symmetry combine to
form molecular orbitals.
3) Molecular orbital is polycentric. The electron in a molecular orbital is influenced
by two or more nuclei depending upon the number of atoms in the molecule
Continue…
MOLECULAR ORBITAL THEORY
4) 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.
5) The bonding molecular orbital has lower energy and hence greater stability than the
corresponding antibonding molecular orbital.
6) The electron probability distribution around a group of nuclei in a molecule is given by a
molecular orbital.
7) 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
 Formation of Molecular Orbitals
Linear Combination of Atomic Orbitals (LCAO)
• This is an approximate method to obtain wave functions for molecular orbitals.
• Consider hydrogen molecule consisting of two atoms of hydrogen ,A and B.
• Each hydrogen atom in the ground state has one electron in 1s orbital.
• The atomic orbitals of these atoms may be represented by the wave functions ψA
and ψB.
• Mathematically, the formation of molecular orbitals may be described by the linear
combination of atomic orbitals that can take place by addition and by subtraction of
wave functions of individual atomic orbitals as shown :
Continue…
Linear Combination of Atomic Orbitals
(LCAO)
• The two molecular orbitals σ and σ* are formed
as :

• The molecular orbital σ formed by the addition

of atomic orbitals is called the bonding
molecular orbital while
• the molecular orbital σ* formed by the
subtraction of atomic orbital is called
antibonding molecular orbital
 Bonding Molecular Orbital Anti-bonding Molecular Orbital
Formed by constructive interference of the electron Formed by destructive interference of the electron
waves of the combining atoms. waves of the combining atoms.

The electron density is located between the nuclei Most of the electron density is located away from
of the bonded atoms because of which the the space between the nuclei hence the repulsion
repulsion between the nuclei is very less between the nuclei is high.

Electrons placed in a bonding molecular orbital tend Electrons placed in the antibonding molecular
to hold the nuclei together and stabilise a molecule orbital destabilise the molecule.

Possesses lower energy than either of the Possesses higher energy than either of the
atomic orbitals that have combined to form it. atomic orbitals that have combined to form it.

It does not has nodal plane It has is a nodal plane

Conditions for the Combination of Atomic Orbitals
1. The combining atomic orbitals must have the same or nearly the same energy.
2. The combining atomic orbitals must have the same symmetry about the
molecular axis. By convention z-axis is taken as the molecular axis.
• For example, 2p z orbital of one atom can combine with 2p z orbital of the
other atom but not with the 2p x or 2p y orbitals because of their different
symmetries.
3. The combining atomic orbitals must overlap to the maximum extent. Greater
the extent of overlap, the greater will be the electron-density between the
nuclei of a molecular orbital.
 Class XI Chemistry
UNIT 4
CHEMICAL BONDING AND MOLECULAR
STRUCTURE
Topics:-
• Types of Molecular Orbitals
 Types of Molecular Orbitals
• Molecular orbitals of diatomic molecules are designated as σ (sigma), π
(pi), δ (delta), etc.
• The sigma (σ) molecular orbitals are symmetrical around the bond-axis
while pi (π ) molecular orbitals are not symmetrical.
 Continue…
Types of Molecular Orbitals
• For example, the linear combination of 1s orbitals centered on two nuclei
produces two molecular orbitals which are symmetrical around the bond-
axis.
• Such molecular orbitals are of the σ type and are designated as σ1s and
σ*1s
Continue…
Types of Molecular Orbitals
• If internuclear axis is taken to be in the z-direction, a linear
combination of 2p z- orbitals of two atoms also produces two sigma
molecular orbitals designated as σ2p z and σ*2p z.
Continue…
Types of Molecular Orbitals
• Molecular orbitals obtained from 2px and 2py orbitals are not symmetrical around the bond axis
because of the presence of positive lobes above and negative lobes below the molecular plane.
• Such molecular orbitals, are labelled as π and π* . (π 2px , π* 2px and π 2py , π* 2py)
• A π bonding MO has larger electron density above and below the inter -nuclear axis. The π*
antibonding MO has a node between the nuclei.
 Class XI Chemistry
UNIT 4
CHEMICAL BONDING AND MOLECULAR
STRUCTURE
Topics:-
• Energy Level Diagram for Molecular Orbitals
Energy Level Diagram for Molecular Orbitals
• 1s atomic orbitals on two atoms form two molecular orbitals designated as σ1s and
σ*1s.

• 2s and 2p atomic orbitals (eight atomic orbitals on two atoms) give rise to the

following eight molecular orbitals:

• The increasing order of energies of various molecular orbitals for O2 and F2 is :

• For molecules such as B2, C2, N2, etc. the increasing order of energies is
 For B2, C2,
for O2 and F 2
N2
Electronic configuration of the molecule
• The distribution of electrons among various molecular orbitals is called the
electronic configuration of the molecule
Stability of Molecules:
• If Nb is the number of electrons occupying bonding orbitals and Na the number
occupying the antibonding orbitals, then
• (i) the molecule is stable if N b is greater than N a, and
• (ii) the molecule is unstable if N b is less than Na.
Bond order
• Bond order (b.o.) is defined as one half the difference between the number of
electrons present in the bonding and the antibonding orbitals i.e.,
Bond order (b.o.) = ½ (Nb–Na)
• Nb > Na Positive bond order means a stable molecule
• Nb< Na Negative bond order , unsatble molecule
• Nb = N a Zero bond order , unstable molecule.
• Integral bond order values of 1, 2 or 3 correspond to single, double or triple bonds
respectively
• The bond length decreases as bond order increases.
Magnetic nature
• If all the molecular orbitals in a molecule are doubly occupied, the
substance is diamagnetic (repelled by magnetic field). No unpaired electron
• However if one or more molecular orbitals are singly occupied it is
paramagnetic (attracted by magnetic field), e.g., O2molecule. Presence of
unpaired electron
 Class XI Chemistry
UNIT 4
CHEMICAL BONDING AND MOLECULAR
STRUCTURE
Topics:-
• Bonding In Some Homonuclear Diatomic Molecules as per
MOT
Hydrogen molecule (H2 )

electronic configuration of H2:- (σ1s)2

Magnetic property:- Diamagnetic ( no unpaired

electron)
 Helium molecule (He2 ):

• electronic configuration of He2:- (σ1s)2(σ*1s)2

• He2 molecule does not exist .

• Similarly, it can be shown that Be2 molecule also does not exist.
(σ1s)2 (σ*1s)2 (σ2s)2 (σ*2s)2 Bond order = 0
Lithium molecule (Li2 ):
• The electronic configuration of lithium is 1s2 2s1.
• There are six electrons in Li2.
• The electronic configuration of Li 2 molecule is
• Li2 : (σ1s)2 (σ*1s)2 (σ2s)2
• The above configuration is also written as KK( σ2s)2
where KK represents the closed K shell structure
(σ1s)2 (σ*1s)2.
• Li 2 Diamagnetic and stable.
• Li 2 molecules are known to exist in the vapour phase.
Carbon molecule (C2 ):
• The electronic configuration of carbon is 1s2 2s22p 2.
• There are twelve electrons in C2.
• The electronic configuration of C2 molecule is

Double bond in C2 consists

of both pi bonds because
of the
presence of four electrons
C2 diamagnetic, detected in vapour phase.
in two pi molecular orbitals.
Oxygen molecule (O2 ):
• The electronic configuration of oxygen atom is 1s2 2s22p 4. each atom 8
electrons
• There are 16 electrons in O2molecule..
• The electronic configuration of O 2 molecule is
 Oxygen molecule
(O2 ):
it contains two unpaired
electrons in p * 2p x and p * 2p y
molecular orbitals, therefore it is
paramagnetic
 Class XI Chemistry
UNIT 4
CHEMICAL BONDING AND MOLECULAR
STRUCTURE
Topics:-
• HYDROGEN BONDING
HYDROGEN BONDING
• Nitrogen, oxygen and fluorine are the highly electronegative elements.
• When they are attached to a hydrogen atom to form covalent bond, the electrons of the
covalent bond are shifted towards the more electronegative atom.
• This partially positively charged hydrogen atom of one molecule forms a bond with the
more electronegative atom of other molecule. This bond is known as hydrogen bond and is
weaker than the covalent bond.
• For example HF
• Hydrogen bond is represented by a dotted line (– – –) while a solid line represents the
covalent bond.
• Thus, hydrogen bond can be defined as the attractive force which binds hydrogen atom of
one molecule with the electronegative atom (F, O or N) of another molecule.
Cause of Formation of Hydrogen Bond
• An electrostatic force of attraction between hydrogen atom of one molecule and
electronegative atom of second molecule.
Conditions for the Formation of Hydrogen Bond
• (1) Hydrogen atom should be bonded to highly electronegative atom say F, O orN.
(2) The electronegative atoms should be small in size.
• For example in HF and HCl , H atom is bonded to more electronegative atom F
and Cl respectively but H-bond exist in HF not in HCl because size of Cl is larger
 Types of H-Bonds
There are two types of H-bonds
(i) Intermolecular hydrogen bond (ii) Intramolecular hydrogen bond
(1) Intermolecular hydrogen bond :
• It is formed between two different molecules of the same or different compounds.
• For example, H-bond in case of HF molecule, alcohol or water molecules, etc.
(2) Intramolecular hydrogen bond :
• It is formed when hydrogen atom is in between the two highly electronegative (F,
O, N) atoms present within the same molecule.
• For example, in o-nitrophenol the hydrogen is in between the two oxygen atoms.