Chemical Bonding And

Molecular Structures
Kossel Lewis
Approach
 Kossel Lewis Approach To
Chemical Bonding
• In 1916, Kossel and Lewis were the
first to become independently
successful in giving a satisfactory
explanation about the formation
chemical bond in terms of electrons.
• They were the first to provide some
logical explanation of valence which
was based on the inertness of noble
gases.
 Lewis approach
• He pictured the atom in terms of a positively
charged ‘Kernel’ and the outer shell which could
accommodate a maximum of eight electrons.
• He assumed that these eight electrons occupy the
corners of a cube which surround the ‘Kernel’.
• Lewis postulated that atoms achieve the stable
octet when they are linked by chemical bonds.
• In sodium and chlorine, this can happen by transfer
of electron from sodium to chlorine.
• In case of other molecules like CL 2 the bond is
formed by sharing of a pair of electrons between
atoms.
 Lewis symbol
In formation of a molecule, only the
outer shell electron take part in
chemical combination and they
are called valence electrons.
The inner shells do not get involved
in the combination process.
G.N. Lewis, an American chemist
introduced simple notations to
represent valence shell electrons
in an atom and these are known
as Lewis symbols.
Lewis Dot Structures for elements known
at his time
 Significance of Lewis symbol

• The number of dots represent the

number of valence electrons.
• This number of valence electrons
help to calculate the common or
group valence of that element.
• The group valence of the element is
generally either equal to the number
of dots in Lewis symbol or 8 minus
the number of dots.
• Other important facts given by Kossel are-
• In periodic table, the highly electronegative
halogens and the highly electropositive alkali
metals are separated by 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 electron by
the respective atoms.
• The negative and positive ions thus formed attain
stable noble gas electronic configurations.
• The negative and positive ions are stabilized by
electrostatic attraction.
 Example
• Na  Na+ + e-
[Ne] 3s1 [Ne]

• Cl + e-  Cl-
[Ne} 3s2 3p5 [Ne] 3s2 3p6 or [Ar]

=> Na+ + Cl-  NaCl

 Octet rule

• According to electronic theory of

chemical bonding, atoms can
combine either by transfer of valence
electrons from one atom to another
or by sharing of valence in order to
have an octet in their valence shells.
this is known as octet rule.
 Covalent Bonding
Covalent bond is the sharing of the VALENCE
ELECTRONS
Recall: of each atom in a bond
Electrons are divided between
core and valence electrons.
ATOM core valence
Na 1s2 2s2 2p6 3s1 [Ne] 3s1
Br [Ar] 3d10 4s2 4p5 [Ar] 3d10 4s2 4p5

Br
Br
 Covalent bond
• The bond formed by atoms when they share
their valence electrons to gain octet is known
as covalent bond.
• When two atoms share one electron pair they
are said to be joined by a single covalent
bond.
• If two atoms share two pairs of electrons, the
covalent bond between them is called a
double bond.
• When combining atoms share three electron
pairs , a triple bond is formed.
Covalent bond diagrams

H2O

NH3

CH4
 Lewis representation of simple
molecules(the Lewis structures)
• The Lewis dot structures provide a picture of
bonding in molecules and ions in terms of shared
pairs of electrons and the octet rule.
• The Lewis dot structures can be written by
adopting the following steps.
– 1)the total number of electrons required for
writing the structures are obtained by adding
the valence electrons of the combining atoms.
– 2) for anions, each negative charge would
mean addition of one electron. For cations,
each positive charge would result in
subtraction of one electron from the total
number of valence electrons.
– 3)one must know the chemical symbols
of the combining atoms and their
skeletal structures.
– 4)in general, the least electronegative
atom occupies the central position.
– 5)after accounting for shared pairs of
electrons for single bonds, the
remaining electron pairs are either
utilized for multiple bonding or remain
as lone pairs.
 Formal charge
• A formal charge (FC) is the charge
assigned to an atom in a molecule,
assuming that electrons in a chemical
bond are shared equally between atoms,
regardless of relative electro negativity.
• 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 Lewis
structure.
• Formal charge = (total no. of valence
electrons in the
free atom)-
(total no. of non
bonding electrons)-
(1/2(total no. of bonding
electrons)
• Formal charge on ‘1’ =6-2-1/2(6)=+1
• Formal charge on ‘2’ =6-4-1/2(4)=0
• Formal charge on ‘3’ =6-6-1/2(2)=-1
• Formal charges do not indicate real charge
separation within the molecule. These charges
help in keeping track of the valence electrons in
the molecule.
• 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 pure
covalent view of bonding in which electron pairs
are shared equally by neighboring atoms.
•
Limitations of the
It is not universal. There are
octet rule
exceptions to it.
1)the incomplete octet of
the central atom
In some compounds,
the number of electrons
surrounding the central
atom is less than eight.
Examples- LiCl, BeH2
and BCl3
2) Odd-electron molecule
in molecules with an odd number of
electrons like nitric oxide, NO and
nitrogen dioxide, the octet rule is not
satisfied for all atoms.
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 expanded
octet.
Examples-PF5, SF6, H2SO4
4) Octet rule is based on the chemical
inertness of noble gases. However,
some noble gases 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 the molecules.
6) It does not explain the relative
stability of the molecules being
totally silent about the energy of a
molecule.
Bond Parameters
 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
techniques etc.
Each atom of the bonded pair contribute
to the bond length.
• In case of a covalent bond, the
contribution from each atom is called
the covalent radius of that atom.
• The covalent radius is measured
approximately as the radius of an
atom’s core which is in contact with
the core of an adjacent atom in a
bonded situation.
• The van der Waals radius represents
the overall size of the atom which
includes its valence shell in a non
bonded situation.
• Bond angle

It is defined as the angle between the

orbitals containing bonding electron pairs
around the central atom in a molecule or
complex ion.
Bond angle is expressed in degree.
• 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 per mol.

Example-
The H-H bond enthalpy in hydrogen molecule is
435.8 kJ/mol.

H2 -------> H(g)+H(g) ΔaH=435.8 kJ/ mol

O2 (O=O) (g) ------> O(g)+O(g) ΔaH=498 kJ/mol

• The larger the bond dissociation enthalpy,
stronger will be the bond in the molecule.
HCl---H + Cl
• In case of polyatomic molecules, the
measurement of bond strength in the following
way-
let us take the example of H2O molecule.
H2O---H+OH; ΔaH1=502 kJ/mol
OH---H+O; ΔaH2=427 kJ/mol
In this case, the average bond enthalpy is taken.
average bond enthalpy=502+427=464.5 kJ/mol
2
 Bond order
• In Lewis description of covalent bond, the
bond order is given by the number of
bonds between the two atoms in a
molecule.
• For example, the bond order of h2 which
has a single shared pair of electrons is 1
• The bond order of O2 with 2 shared pairs of
electrons is 2
• The bond order of N2 with 3 shared pairs of
electron is 3.
• For N2, the bond order is 3 and its bond
enthalpy is 946 kJ/mol and it is one of the
highest for diatomic molecule.
• Isoelectronic molecules and ions have
identical bond orders.
example- N2 and CO have bond order 3.
A general correlation useful for understanding
the stabilities of molecules is that: with
increase in bond order, bond enthalpy
increases and bond length decreases.
Resonance
 Resonance structures
• A single Lewis structure may be inadequate
for representation of a molecule.
• According to the concept of resonance,
whenever a single Lewis structure cannot
describe a molecule accurately, a number
of structures with similar energy, position
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, O3 molecule
can be represented by
two structures as shown
in the figure.
• For O3 these two
structures constitute the
canonical structures or
resonance structures and
their hybrid shown by the
third figure represents
the structure of o3 more
accurately. this is called
resonance hybrid.
 • 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
– Resonance averages the bond
characteristics
Resonance Energyas a whole.
It is the difference between the actual bond
energy of the molecule and that of the most
stable of the resonating structures (having
least energy).
Polarity Of Bonds
Polarity of Bonds
The existence of a hundred percent ionic or covalent bond represents
an ideal situation. In reality no bond or a compound is either
completely covalent or ionic. Even in case of covalent bond
between two hydrogen atoms, there is some ionic character.
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 non polar covalent bond. Contrary to this in case
of a heteronuclear molecule like HF, the shared electron pair
between the two atoms gets displaced more towards fluorine
since the electronegativity of fluorine (Unit 3) is far greater than
that of hydrogen. The resultant covalent bond is a polar covalent
bond.
As a result of polarisation, the molecule possesses the dipole
moment (depicted below) which can be 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;’. Mathematically, it is expressed as follows :
Dipole moment (μ) = charge (Q) x distance of separation (r)
Dipole moment is usually expressed in Debye units (D).The
conversion factor is
1 D = 3.33564 x 10–-30 C m
where C is coulomb and m is meter.
• Further 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 :

• The shift in electron density is symbolised by crossed

arrow ( ) above the Lewis structure to indicate the
direction of the shift.

• In 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. In such
case, the dipole moment of a molecule is the vector
sum of the dipole moments of various bonds. For
example in H2O molecule, which has a bent structure,
the two O-H bonds are oriented at an angle of 104.50.
Net dipole moment of 6.17 x 10–-30 C m (1D = 3.33564
x 10–-30 C m) is the resultant of the dipole moments of
two O-H bonds.

• Peter Debye, the Dutch chemist received Nobel prize in

1936 for his work on X-ray diffraction and dipole
moments. The magnitude of the dipole moment is given
• The dipole moment in case of BeF2 is
zero. This is because the two equal
bond dipoles point in opposite
directions and cancel the effect of
each other.
• In tetra-atomic molecule, for
example in BF3, the dipole moment is
zero although the B – F bonds are
oriented at an angle of 120° 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.
• In case of NH3 and NF3 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 x 10–3 the
orbital dipole due to lone pair is in the same
direction as the resultant dipole moment of
the N – H bonds, whereas in NF3the 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 NF3.
The partial covalent character of ionic bonds was
discussed by Fajan’s in terms of the following rules:
• 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,
typical of transition metals, is more polarising
than the one with a noble gas configuration,
ns2 np6, typical of alkali and alkaline earth metal
cations. The cation polarises the anion, pulling
the electronic charge toward itself and thereby
increasing the electronic charge between the
two. This is precisely what happens in a
covalent bond, i.e., build-up of electron charge
density between the nuclei. The polarising
power of the cation, the polarisability of the
anion and the extent of distortion (polarisation)
VSEPR Theory
 Valence Shell Electron
Pair Repulsion Theory
• Sidgwick and Powell in 1940, proposed a simple
theory based on the repulsive interactions of the
electron pairs in the valence shell of the atoms. It
was further developed and redefined by Nyholm
and Gillespie (1957).
• 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 minimise 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.
• 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)
• Nyholm and Gillespie (1957) refined the VSEPR
model by explaining the important difference
between the lone pairs and bonding pairs of
electrons. 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 result in deviations from
• 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.
• The VSEPR Theory is able to predict
geometry of a large number of molecules,
especially the compounds of p-block
elements accurately. It is also quite
successful in determining the geometry
quite-accurately even when the energy
difference between possible structures is
very small. The theoretical basis of the
VSEPR theory regarding the effects of
electron pair repulsions on molecular shapes
is not clear and continues to be a subject of
doubt and discussion.
• Shape (geometry) of Some Simple
Molecules/Ions with Central Ions having One
or more Lone Pairs of Electron(E).
• Shapes of Molecules containing Bond
Pair and Lone Pair
ORBITAL OVERLAP
CONCEPT
 ORBITAL OVERLAP
CONCEPT
• If orbitals of 2 atoms are mixed with each other partially during bond
formation, then the phenomenon is called as overlapping of orbitals.
• TYPES OF ORBITAL OVERLAPS:
• 1.Positive overlap: If the symmetry of both the atomic orbitals is
the same, then it is called as positive overlap i.e. if the symmetry of
the overlapping orbitals is either positive, or negative, then it is a
type of positive overlap.

• 2.Negative overlap: If the symmetry of the atomic orbitals is not

the same, i.e., one is positive and the other negative, then it is a
type of negative overlap.

• 3.Zero overlap: If overlap of orbitals present in 2 different planes

takes place , then it is called as zero overlap. E.g.. Px overlaps with Py
(in real situation, overlapping does not takes place.)
 TYPES OF OVERLAPS
RESULTING IN SIGMA BOND
FORMATION
TYPES OF
OVERLAPS
RESULTING IN PI
BOND FORMATION

Due to lateral/sideways
overlap of P-P orbitals
present in the same
plane, Pi bond is
formed.
 COMPARISION
SIGMA
BONDS PI BONDS
• It is a strong bond. • It is a weak bond.
• Electron cloud is • Electron cloud is
symmetrical along the asymmetrical.
inter- nuclear axis.
• There can be free • Free rotation is not
rotations of atoms possible around this
around this bond. bond.
• These are less reactive. • These are more reactive.
• Shape of the molecule is • These bonds do not
determined by these affect the shape of the
bonds. molecule.
• Sigma bonds have • Pi bond always exists
independent existence. with a sigma bond.
 HYBRIDIZATION
The intermixing of different atomic orbitals of approximately equal
energy levels to produce hybrid orbitals before bond formation is
called as HYBRIDIZATION.
Here arrangement of hybrid orbitals are such that there is minimum
repulsion in between the hybrid orbitals.
No. of orbitals mixed=No. of hybrid orbitals produced.

DIFFERENT TYPES OF HYBRIDISATIONS:

Sp Hybridization
NO. of hybrid orbitals produced=2
Structure = LINEAR
Bond angle = 180 degree …..e.g. BeF₂
sp HYBRIDIDSATION
• SP2 Hybridization:
• No. of hybrid orbitals produced = 3
• Arrangement of these orbitals = TRIGONAL PLANAR
• Bond angle=120 degree……..ex. BF₃, etc.
• SP3 Hybridization:
• No. of hybrid orbitals = 4
• Arrangement= TETRAHEDRAL
• BOND ANGLE…..
• IN CH₄ = 109.28 degree
• IN NH₃ = 107.3 degree.
• Here, in methane, sigma bond is formed between H and C atom
due to overlapping of sp3 orbital of H atom with S orbital of H
atom.
• Structure of NH₃ – TRIANGULR PYRAMIDAL.
• SP2 • SP3
Hybridization Hybridization
• SP3d Hybridization:
• NO. of hybrid orbitals produced = 5
• Structure = TRIGONAL BIPYRAMIDAL
• BOND ANGLES:
• Equatorial = 120 degree.
• Axial = 90 degree.
• If lone pair of electron is present at central atom, its position is
always equatorial.Ex.PCl5
• Length of axial bonds is longer than that of equatorial bonds
because of minimum repulsion.
• IT may have different shapes according to no. of lone pairs it has:
• 1 lone pair – seesaw shape………e.g. SF₄
• 2 lone pairs – bent T shape………E.g. BrF₃
• 3 Lone pairs – Linear shape
• SP3d2 Hybridization:
• No. of hybrid orbitals produced = 6
• Arrangement = OCTAHEDRAL……e.g. SF₆ ( lone pairs = 0)
• Shape may be:
• Square pyramidal…..e.g. BrF₅ ( lone pairs = 1)
• Square planar…….e.g. XeF4₄ (lone pairs = 2)
• SP3d3 Hybridization:
• No. of hybrid orbitals = 7
• Arrangement = PENTAGONAL BIPYRAMIDAL
• BOND ANGLES:
• Axial with equatorial = 90 degree.
• Equatorial to equatorial = 72 degree.
• SP3d2 • Sp3d3
Hybridization Hybridization
 RULES REGARDING
HYBRIDIZATION
• Only orbitals of approximately same energy levels can take
part.
• No. of orbitals mixed = No. of hybrid orbitals produced.
• Most hybrid orbitals are similar but not always identical in
shape. They may differ from one another in their
orientation in space.
• The electron waves in hybrid orbitals repel each other and
this tend to the farthest apart.
• Hybrid orbitals can form only sigma bonds.
• Depending on the number and the nature of the orbitals
undergoing hybridization, various types of hybrid orbitals
directing towards the corners of specified geometrical
figures come into existence.
Molecular Orbital
Theory
MOT
• CONDITIONS FOR COMBINATION
OF ATOMIC ORBITALS
• For atomic orbitals to combine, resulting in
the formation of molecular orbitals , the
main conditions are :
• The combining atomic orbitals should have
almost the same energies. For example, in
the case of diatomic molecules, 1s-orbital of
one atom can combine with 1s-orbital of the
other atom, but 1s-orbital of one atom
cannot combine with 2s-orbital of the other
atom.
• The extent of overlap between the atomic
orbitals of the two atoms should be large.
• The combining atomic orbitals should have
the same symmetry about the molecular
axis. For example, 2Pxorbital of one atom
can combine with 2Px orbital of the other
atom but not with 2Pz orbital .
Designations of Molecular
Orbitals
Just as atomic orbitals are designated as s, p, d,
f etc molecular orbitals of diatomic molecules are
named σ (sigma) ,
π (pi) , δ (delta) etc.
MOLECULAR ORBITALS
The molecular orbitals which are cylindrically
symmetrical around inter-nuclear axis are
called σ - molecular orbitals. The molecular
orbital formed by the addition of 1s orbitals is
designated as σ 1s and the molecular orbital
formed by subtraction of 1s orbitals is designated
as σ * 1s . Similarly combination of 2s orbital
results in the formation of two
2 s - molecular orbitals designated as σ 2s
and σ * 2s
Orbital Diagram Of O 2 And O

O2 O
DETERMINATION OF SHAPE
OF MOLECULES
1.Determine the number of electrons in the
molecule. We get the number of electrons per
atom from their atomic number on the periodic
table. (Remember to determine the total number
of electrons, not just the valence electrons.)
2.Fill the molecular orbitals from bottom to top
until all the electrons are added. Describe the
electrons with arrows. Put two arrows in each
molecular orbital, with the first arrow pointing up
and the second pointing down.
3. Orbitals of equal energy are half filled with
parallel spin before they begin to pair up.
 Stability of the molecule with
bond order.
Bond order = 1/2 (#e- in bonding MO's -
#e- in antibonding MO's)
We use bond orders to predict the
stability of molecules :-
• If the bond order for a molecule is equal to
zero, the molecule is unstable.
• A bond order of greater than zero suggests a
stable molecule.
• The higher the bond order is, the more
stable the bond.

We can use the molecular orbital diagram to

predict whether the molecule is paramagnetic
or diamagnetic. If all the electrons are paired,
the molecule is diamagnetic. If one or more
electrons are unpaired, the molecule is
 Examples
1. The molecular orbital diagram for a diatomic hydrogen molecule,
H2, is

• The bond order is 1. Bond Order = 1/2(2 - 0) = 1

• The bond order above zero suggests that H 2is stable.
• Because there are no unpaired electrons, H 2 is diamagnetic.

2. The molecular orbital diagram for a diatomic helium molecule,

He2, shows the following.

• The bond order is 0 for He2. Bond Order = 1/2(2 - 2) = 0

• The zero bond order for He2suggests that He2is unstable.
• If He2did form, it would be diamagnetic
3. The molecular orbital diagram for a diatomic oxygen
molecule, O2, is

• O2has a bond order of 2. Bond Order = 1/2(10 - 6) = 2

• The bond order of two suggests that the oxygen molecule
is stable.
• The two unpaired electrons show that O2is paramagnetic
BONDING IN HOMONUCLEAR
DIATOMIC MOLECULES

Diatomic molecules are molecules composed only

of two atoms, of either the same or different chemical
elements. The prefix di- is of Greek origin, meaning
two. Common diatomic molecules are hydrogen (H2),
nitrogen (N2), oxygen (O2), and carbon monoxide (CO).
Seven elements exist as homonuclear diatomic
molecules at room temperature: H2, N2, O2, F2, Cl2, Br2,
and I2. Many elements and chemical compounds aside
from these form diatomic molecules when
evaporated. The noble gases do not form diatomic
molecules: this can be explained using molecular
orbital theory (see molecular orbital diagram).
 H MOLECULE
2

INTRODUCTION
1.Two H atoms in their ground state
configuration come together and form a
single bond. The bond formation stabilizes
both atoms and, therefore, is lower in energy
than the atomic orbitals. This is also
observed in Valence Bond Theory, which
implies that each H atom in H2shares its
electron with one another, so that both can
achieve the stable configuration of He.
2.On top of that, MO Theory allows one to
compute the amount of energy released from
a bond formation and a distance between
two bonded atoms as well as predict the
magnetic property of a molecule (or a
substance). For H2, the bond strength is -432
kJ/Mol, and the bond length is 74 angstrom
(or 74 pm). H2 is a diamagnetic molecule
because the electrons paired up; therefore, it
is not attracted by a magnetic field.
 Bonding and Anti-bonding molecular orbitals in H2
1.Each H atom has a 1s atomic orbital. When two H atoms come to a
proper proximity, their 1s orbitals interact and produce two
molecular orbitals: a bonding MO and an anti-bonding MO.
2.If the electrons are in phase, they have a constructive interference.
This results in a bonding sigma MO (σ1s). This MO has an increased
probability of finding electrons in the bonding region.

Figure 2: Schematic representation of the bonding molecular orbital

σ(1s)
If the electrons are out of phase, they have a destructive
interference. This results in an anti-bonding sigma MO (σ* 1s). This MO
has a decreased probability of finding electrons in the bonding
region. (Valence Bond Theory does not explain this phenomenon.)

Figure 3:Schematic representation of antibonding molecular orbital

σ*(1s)
Note that there is a nodal plane in the anti-bonding
 Bond order in H 2

Bond order = 1/2 (#e- in bonding MO - #e- in

antibonding MO)
For H2, bond order = 1/2 (2-0) = 1, which means
H2 has only one bond. The antibonding orbital is
empty. Thus, H2 is a stable molecule.
Again, in the MO, there is no unpaired electron,
so H2 is diamagnetic
Hydrogen Bond
HYDROGEN BOND
In compounds of hydrogen with strongly
electronegative elements, such as fluorine,
oxygen and nitrogen, electron pair shared
between the two atoms lie far away from the
hydrogen atom. As a result, the hydrogen
atom becomes highly electropositive with
respect to the other atom. This phenomenon
of charge separation in the case of hydrogen
fluoride is represented as . Such a molecule
is said to be polar . The molecule behaves as
a dipole because one end carries a positive
charge and the other end a negative charge.
The electrostatic force of attraction between
such molecules should be very strong. This
is because the positive end of one
molecule is attracted by the negative end of
the other molecule . Thus, two or molecules
may associate together to form larger
cluster of molecules. This is illustrated below
for the association of several molecules of
• The cluster of HF molecules may be
described as (HF)n.
• It may be noted that hydrogen atom is
bonded to fluorine atom by a covalent bond
in one molecule and by electrostatic force or
by hydrogen bond to the fluorine atom in
the adjacent molecule . Hydrogen atom is
thus seen to act as a bridge between the
two fluorine atoms.
• The attractive force which binds the
atom of one molecule with an
electronegative atom (such as fluorine,
oxygen or nitrogen) of another
molecule, generally of the same
substance , is known as hydrogen
bond .
• The hydrogen bond is represented by a
dotted line. The solid lines represent the
original(covalent ) bond present in the
molecule.
• Chlorine, bromine and iodine are not as
highly electronegative as fluorine and
therefore, the shared pair of electrons in the
case of HCl , HBr and HI do not lie as far
away from hydrogen as in the case of HF.
The tendency to form hydrogen bond in
these cases is therefore less.
• Water molecule, because of its bent
structure, is also a dipole, oxygen end
carrying a negative charge and hydrogen
end carrying a positive charge. Hydrogen
bond taking place in this case as well, as
represented below:

• The cluster of water molecules may be

described as (H2O)n
• The nature of hydrogen bond
• The hydrogen bond is a class in itself. It
arises from electrostatic forces between
positive end (pole) of one molecule and the
negative end(pole) of the other molecule
generally of the same substance. The
strength of hydrogen bond has been has
been found to vary between 10 - 40
kJ mol−1 (i.e., 6.02 x 1023 bonds) while that of
a covalent bond has been found to be of the
order of 400 kJ mol−1 . Thus a hydrogen bond
is very much weaker than a covalent bond.
Consequently, the length of hydrogen bond
is bigger than the length of a covalent bond.
• In the case of hydrogen fluoride, for
instance, while the length of the covalent
bond between F and H atoms is 100 pm, the
length of hydrogen bond between F and H
atoms of neighbouring molecules is 155 pm.
• Types of hydrogen bonding
• Hydrogen bonding may be classified
into two types :
• Intermolecular hydrogen bonding
This type of hydrogen bonding involves
electrostatic forces of attraction between
hydrogen and electronegative element of
two different molecules of the substance.
Hydrogen bonding in molecules of HF, NH3 ,
H2O etc. are examples of intermolecular
hydrogen bonding.
• Intramolecular hydrogen
bonding
This type of bonding involves electrostatic
forces of attraction between hydrogen and
electronegative element both present in the
same molecule of the substance. Examples
o-nitrophenol and salicylaldehyde.

• p-Nitrophenol , on account of large distance

between two groups , does not show any
intramolecular hydrogen bonding. On the
other hand, it shows the usual inter
molecular hydrogen bonding , as illustrated
below:
• As a result of intermolecular hydrogen
bonding, the para derivative undergoes
association, resulting in an increase in molar
mass and hence an increase in boiling point.
In ortho derivative, on account
of intramolecular hydrogen bonding , no
such association is possible. Consequently,
the ortho derivative is more volatile than the
para derivative. Thus, while ortho
nitrophenol is readily volatile in steam , para
nitrophenol is completely non-volatile. The
two derivatives can thus be separated from
each other by steam distillation.
• Some Unique Properties of
Water
• Density in solid state(ice) is less than that in
liquid state . This is some what unusual
because in most substances density in solid
is more than that in liquid state.
• Water contracts when heated between 0°C
and 4°C . This is again unusual because
most substances expand when heated in all
temperature ranges.
• Both these peculiar features are due to
hydrogen bonding, as discussed below :
• In ice, hydrogen bonding between
H2O molecules is more extensive
than in liquid water. A substance in
solid state has a definite structure
and the molecules are more rigidly
fixed relative to one another than
in the liquid state. In ice, the H2O
molecules are tetrahedrally
oriented with respect to one
another.At the same time , each
oxygen atom is surrounded
tetrahedrally by four hydrogen
atoms, two of these are bonded
covalently and the other two by
hydrogen bonds.The tetrahedral
open cage-like crystal structure of
ice. The central oxygen atom A is
surrounded tetrahedrally by the
oxygen atoms marked
1,2, 3 and 4.The hydrogen bonds
are weaker and therefore, longer
than covalent bonds. This
arrangement gives rise to an
open cage-like structure , as shown
• These holes are formed because the
hydrogen bonds holding the H2O molecules
in ice are directed in certain definite angles .
In liquid water such hydrogen bonds are
fewer in number. Therefore, as ice melts, a
large number of hydrogen bonds are broken.
The molecules, therefore, move into the
‘hole' or open spaces and come closer to
one another than they were in the solid
state. This results in a sharp increase in
density . The density of liquid water is,
therefore higher than that of ice.
• As liquid water is heated from 0°C to 4°C,
hydrogen bonds continue to be broken and
the molecules come closer and closer
together. This leads to contraction. However,
there is some expansion of water also due to
rise in temperature as in other liquids. It
appears that up to 4°C, the former effect
predominates and hence the volume
increases as the temperature rises.
• It can be easily realised that without
hydrogen bonding , water would
have existed as a gas like hydrogen
sulphide. In that case no life would
have been possible on this globe.
• Hydrogen bonding also exists in all
living organisms, whether of animal
or of vegetable kingdom. Thus, it
exists in various tissues, organs,
blood, skin and bones in animal life.
It plays an important role in
determining structure of proteins
which are so essential for life.
• Hydrogen bonding plays an important role in
making wood fibres more rigid and thus
makes it an article of great utility. The
cotton, silk or synthetic fibres owe their
rigidity and tensile strength to hydrogen
bonding. Thus hydrogen bonding is of vital
importance for our clothing as well. Most of
our food materials also consists of hydrogen
bonded molecules. Sugars and
carbohydrates , for example, have many -
OH groups. The oxygen of one such group in
one molecule is bonded with -OH group of
another molecule through hydrogen
bonding. Hydrogen bonding is thus a
phenomenon of great importance in every
day life.
Thank You!!!