Chemical Bonding And Molecular

Structures

Dikki
Institute

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

Cl + e[Ne} 3s2 3p5

[Ne]

Cl-

[Ne] 3s2 3p6

or

=> Na+ + Cl-

[Ar]

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 of each atom in a bond

Recall: 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
Aformal charge(FC) is the charge

assigned to anatomin amolecule,

assuming thatelectronsin a chemical
bondare shared equally between atoms,
regardless of relativeelectro 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 octet rule

It is not universal. There are

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, Xray 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 atoms 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.
ExampleThe H-H bond enthalpy in hydrogen molecule is 435.8
kJ/mol.
H2 -------> H(g)+H(g)

aH=435.8 kJ/ mol

O2 (O=O) (g) ------> O(g)+O(g)

aH=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 waylet us take the example of H2O molecule.
H2O---H+OH; aH1=502 kJ/mol
OH---H+O; aH2=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 as
a whole.

Resonance Energy
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, N2or 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 ;. Mathematically, it
is expressed as follows :

 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 10-30C m (1D = 3.33564 x 10-30C
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 BeF2is

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 NH3and NF3molecule. 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 103the
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 Fajans 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)d nnso,
typical of transition metals, is more polarising
than the one with a noble gas configuration,
ns2np6, 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

 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 idealised shapes

 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.. P x 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
It is a strong bond.

Electron cloud is

SIGMA

PI

symmetrical along the

BONDS
BONDS
inter- nuclear axis.
It is a weak bond.
There can be free
Electron cloud is
rotations of atoms
asymmetrical.
around this bond.
These are less
Free rotation is not
reactive.
possible around this bond.
Shape of the molecule
is determined by these These are more reactive.
bonds. These bonds do not affect
the shape of the molecule.
Sigma bonds have
independent Pi bond always exists with
existence.
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. BeF

sp HYBRIDIDSATION

SP2 Hybridization:
No. of hybrid orbitals produced = 3
Arrangement of these orbitals = TRIGONAL PLANAR
Bond angle=120 degree..ex. BF, etc.

SP3 Hybridization:
No. of hybrid orbitals = 4
Arrangement= TETRAHEDRAL
BOND ANGLE..
IN CH = 109.28 degree
IN NH = 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 NH TRIANGULR PYRAMIDAL.

SP2
Hybridization

SP3
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 shapee.g. SF
2 lone pairs bent T shapeE.g. BrF
3 Lone pairs Linear shape

 SP3d2 Hybridization:
No. of hybrid orbitals produced = 6
Arrangement = OCTAHEDRALe.g. SF

( lone pairs = 0)

Shape may be:

Square pyramidal..e.g. BrF

( lone pairs = 1)

Square planar.e.g. XeF4

(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 Hybridization

Sp3d3 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 2Pxorbital of the other atom
but not with 2Pzorbital .

Designations of Molecular
Orbitals
Just as atomic orbitals are designated as s, p, d,
fetcmolecular orbitals of diatomic molecules are
named(sigma) ,
(pi) ,(delta)etc.

MOLECULAR ORBITALS
The molecular orbitals which are cylindrically
symmetrical around inter-nuclear axis are
called- molecular orbitals. The molecular
orbital formed by the addition of 1s orbitals is
designated as1s and the molecular orbital
formed by subtraction of 1s orbitals is designated
as* 1s . Similarly combination of 2s orbital
results in the formation of two
2 s - molecular orbitals designated as2s
and* 2s

Orbital Diagram Of O 2 And O

O2

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 H2is stable.
Because there are no unpaired electrons, H2 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 O 2is 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 H 2

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 ( 1s). This MO has an increased
probability of finding electrons in the bonding region.

Figure 2: Schematic representation of the bonding molecular orbital

(1s)
If the electrons are out of phase, they have a destructive interference.
This results in an anti-bonding sigma MO (* 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

*(1s)
Note that there is a nodal plane in the anti-bonding

Bond order in H2
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 bepolar. The molecule behaves as
a dipolebecause 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
becausethepositive end of one moleculeis
attracted by thenegative end of the other
molecule. Thus, two or molecules may
associate together to form larger cluster of
molecules. This is illustrated below for the

 The cluster of HF molecules may be

described as (HF)n.
It may be noted that hydrogen atom is

bonded to fluorine atom bya 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 abridgebetween 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
kJmol1(i.e.,6.02 x 1023bonds) while that of
a covalent bond has been found to be of the
order of 400 kJmol1. 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,
H2Oetc. are examples of intermolecular
hydrogen bonding.

Intramolecular hydrogen

bonding
This type of bonding involves electrostatic
forces of attraction between hydrogen and
electronegative elementboth present in the
same moleculeof 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
ofintramolecular 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 0C
and 4C. 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
opencage-like structure, as shown

 These holes are formed because the

hydrogen bonds holding the H2O molecules

in icearedirected 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 0C to 4C,
hydrogen bonds continue to be broken and
the molecules come closer and closer
together. This leads tocontraction.However,
there is some expansion of water also due to
rise in temperature as in other liquids. It
appears that up to 4C, the former effect
predominates and hence thevolume
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!!!