Chemical Bonding

Chemical bond is an attractive force which keeps tow atoms or ions

together in a molecule.A molecule is formed if it is more stable and
has lower energy than the individual atoms. Normally only electrons in
the outermost shell of an atom are involved in bond formation and in
this process each atom attains a stable electronic configuration of
inert gas. Atoms may attain stable electronic configuration in three
different ways by losing or gaining electrons by sharing electrons. The
attractive forces which hold various constituents (atoms, ions etc) together in different
chemical species are called chemical bonds. Elements may be divided into three classes.

Electropositive elements, whose atoms give up one or more electrons easily, they have
low ionization potentials.

Electronegative elements, which can gain electrons. They have higher value of
electronegativity.

Elements which have little tendency to loose or gain electrons.

Three different types of bond may be formed depending on electropositive or electronegative

character of atoms involved.
Electropositive element + Electronegative element = Ionic bond (electrovalent bond)
Electronegative element + Electronegative element = Covalent bond
or less electro positive + Electronegative element = Covalent bond
Electropositive + Electropositive element = Metallic bond.

The Lewis Theory

The octet rule:- The Lewis theory gave the first explanation of a covalent bond in terms of
electrons that was generally accepted. If two electrons are shared between two atoms, this
constitutes a bond and binds the atoms together. For many light atoms, a stable arrangement
is attained when the atom is surrounded by eight electrons.
This octet can be made up from some electrons which are totally owned and some electrons
which are shared. Thus atoms continue to form bonds until they have made up an octet of
electrons. This is called the octet rule. The octet rule explains the observed valencies in a
large number of cases. There are exceptions to the octet rule; for example, hydrogen is stable
with only two electrons. Other exceptions are discussed later.Today, the conventional Lewis
structure representation of a pair of bonded electrons is by means of a dash (-) usually called
a bond. Lone pairs or non-bonded electrons are represented by dots. Some structures are
represented below:

It is therefore useful to remember some important categories of exceptions:

1.

Odd-electron species like NO, NO 2, O2 etc. Since it is impossible to distribute an odd

number of electrons into pairs, these species necessarily violate the octet rule.

2.

The Valence Bond theory handles such species rather clumsily (odd-electron bonds
etc.) the molecular orbital theory copes much better.

3.

Species in which the central atom `expands' its octet (so to speak) PCl 5, SF6, many
transition metal compounds etc.

4.

Electron -deficient species like BCl 3, BeCl2, AlCl3, B2H6 etc. in which the central atom has
fewer than eight electrons.

Ionic Bonding

Electrovalency

This type of valency involves transfer of electrons from one atom to

another, whereby each atom may attain octet in their outermost shell. The resulting ions that
are formed by gain or loss of electrons are held together by electrostatic force of attraction
due to opposite nature of their charges. The reaction between potassium and chlorine to form
potassium chloride is an example of this type of valency.

Here potassium has one electron excess of its octet and chlorine has one deficit of octet. So
potassium donates its electron to chlorine forming an ionic bond.

Here the oxygen accepts two electrons from calcium atom. It may be noted that ionic bond is
not a true bond as there is no proper overlap of orbitals.

Criteria for Ionic Bond Formation

One of the species must have electrons in excess of octet while the other should be deficit of
octet. Does this mean that all substance having surplus electron and species having deficient
electron would form ionic bond? The answer is obviously no. Now you should ask why? The
reasoning is that in an ionic bond one of the species is cation and the other is anion. To form a
cation from a neutral atom energy must be supplied to remove the electron and that energy is
called ionization energy. Now it is obvious that lower the ionization energy of the element the
easier it is to remove the electron. To form the anion, an electron adds up to a neutral atom
and in this process energy is released. This process is called electron affinity.
So for an ionic bond one of the species must have low ionization energy and the other should
have high electron affinity. Low ionization energy is mainly exhibited by the alkali and alkaline
earth metals and high electron affinity by the halogen and chalcogens. Therefore this group of
elements are predominant in the field of ionic bonding.

Energy Change During the Formation of

Ionic Bond

The formation of ionic bond can be consider to proceed in three steps

(a)
Formation
+
A(g) + I.E. A (g) + e

of

gaseous

The energy required for this step is called ionization energy (I.E)
(b) Formation of gaseous anions
X(g) + e X(g) + E.A
The energy released from this step is called electron affinity (E.A.)
(c) Packing of ions of opposite charges to form ionic solid
A+(g) + X(g) AX(s) + energy

cations

The energy released in this step is called lattice energy.

Now for stable ionic bonding the total energy released should be more than the
energy required.
From the above discussion we can develop the factors which favour formation of ionic bond
and also determine its strength. These factors have been discussed below:
(a) Ionization energy: In the formation of ionic bond a metal atom loses electron to form
cation. This process required energy equal to the ionization energy. Lesser the value of
ionization energy, greater is the tendency of the atom to form cation. For example, alkali
metals form cations quite easily because of the low values of ionization energies.
(b) Electron affinity: Electron affinity is the energy released when gaseous atom accepts
electron to form a negative ion. Thus, the value of electron affinity gives the tendency of an
atom to form anion. Now greater the value of electron affinity more is the tendency of an
atom to form anion. For example, halogens having highest electron affinities within their
respective periods to form ionic compounds with metals very easily.
(c) Lattice energy: Once the gaseous ions are formed, the ions of opposite charges come
close together and pack up three dimensionally in a definite geometric pattern to form ionic
crystal.
Since the packing of ions of opposite charges takes place as a result of attractive force
between them, the process is accompanied with the release of energy referred to as lattice
energy. Lattice energy may be defined as the amount of energy released when one mole of
ionic solid is formed by the close packing of gaseous ion.
In short, the conditions for the stable ionic bonding are:
(a) I.E. of cation forming atom should be low:
(b) E.A. of anion forming atom should be high;
(c) Lattice energy should be high.

Determination of Lattice Energy

The direct calculation of lattice enthalpy is quite difficult because the required data is often
not available. Therefore lattice enthalpy is determined indirectly by the use of the Born
Haber cycle. The cycle uses ionization enthalpies, electron gain enthalpies and other data for
the calculation of lattice enthalpies. The procedure is based on the Hesss law, which states
that the enthalpy of a reaction is the same, whether it takes place in a single step or in more
than one step. In order to understand it let us consider the energy changes during the
formation of sodium chloride from metallic sodium and chlorine gas. The net energy change
during the process is represented by H f.

For example: Born- Haber Cycle for Soidum Chloride

Solved Problem on Born- Haber Cycle

Calculate the lattice enthalpy of MgBr 2. Given that
Enthalpy of formation of MgBr2 = -524 kJ mol1
Some of first & second ionization enthalpy (IE 1 + IE2 ) = 148 kJ mol-1
Sublimation energy of Mg = +2187 kJ mol1
Vaporization energy of Br2(I) = +31kJ mol1
Dissociation energy of Br2(g) = +193kJ mol1

Electron gain enthalpy of Br(g) = -331 kJ mol 1

Solution: Hof = S + I.E. + Hvap + D + 2 E.A. + U
Or U = Hof (S + I.E. + Hvap + D + 2 E.A.)
Or U = -524 - [2187 - 148 + 31 + 193 + 2 (-331)]
= 524 1897 = 2421 kJ mol1

Characteristics of ionic compounds

The following are some of the general properties shown by these compounds
(i) Crystalline nature : These compounds are usually crystalline in nature with constituent
units as ions. Force of attraction between the ions is non-directional and extends in all
directions. Each ion is surrounded by a number of oppositely charged ions and this number is
called co-ordination number. Hence they form three dimensional solid aggregates. Since
electrostatic forces of attraction act in all directions, therefore, the ionic compounds do not
posses directional characteristic and hence do not show stereoisomerism.
(ii) Due to strong electrostatic attraction between these ions, the ionic compounds have high
melting and boiling points.
(iii) In solid state the ions are strongly attracted and hence are not free to move. Therefore, in
solid state, ionic compounds do not conduct electricity. However, in fused state or in aqueous
solution, the ions are free to move and hence conduct electricity.
(iv) Solubility : Ionic compounds are fairly soluble in polar solvents and insoluble in nonpolar solvents. This is because the polar solvents have high values of dielectric constant
which defined as the capacity of the solvent to weaken the force of attraction between the
electrical charges immersed in that solvent. This is why water, having high value of dielectric
constant, is one of the best solvents.
The solubility in polar solvents like water can also be explained by the dipole nature of water
where the oxygen of water is the negative and hydrogen being positive, water molecules pull
the ions of the ionic compound from the crystal lattice. These ions are then surrounded by
water dipoles with the oppositely charged ends directed towards them. These solvated ions
lead an independent existence and are thus dissolved in water. The electrovalent compound
dissolves in the solvent if the value of the salvation energy is higher than the lattice energy
of that compounds.
AB + Lattice energy A+ + B
These ions are surrounded by solvent molecules. This process is exothermic and is called
salvation.
A+ + x(solv.) [A(solv.)x]+ + energy

B + y(solv.) [B(solv.)y] + energy

The value of solvation energy depend on the relative size of the ions. Smaller the ions more is
the solvation. The non-polar solvents do not solvate ions and thus do not release energy due
to
which
they
do
not
dissolve
ionic
compounds.

(v) Ionic reactions: Ionic compound furnish ions in solutions. Chemical reactions are due to
the presence of these ions. For example
Na2SO4 2Na+ + SO42
BaCl2 Ba2+ + 2Cl

Covalent Bonding and Valence Bond Theory

Covalancy

This type of valency involves sharing of electrons between the concerned atoms to attain the
octet configuration with the sharing pair being contributed by both species equally. The atoms
are then held by this common pair of electrons acting as a bond, known as covalent bond. If
two atoms share more than one pair then multiple bonds are formed. Some examples of
covalent bonds are

Valence bond theory (VBT)

A covalent bond is formed by overlapping of valence shell atomic orbitals of the two atoms
having unpaired electron. As a result of overlapping, there is maximum electron density
between the bonding atoms and large part of bonding force arises due to electrostatic force of
attraction between accumulated electron cloud and two nuclei. Greater the overlapping of
atomic orbitals higher is the strength of chemical bond. The paired electron of valence shell
of an atom can take part in covalent bonding subject to availability of vacant orbitals of
slightly higher energy of the same main energy shell and availability of energy for unpairing
of paired electron and their shifting to vacant orbitals. This point explains the trivalency of
boron, tetravalency of carbon, pentavalency of phosphorous hexavalency of S and hepta
valency of Cl, Br, I.
Depending on type of overlapping atomic orbitals covalent bond can be classified into two
types
1. Sigma (s) 2. Pi (p) bond

Sigma and Pi Bonding

When two hydrogen atoms form a bond, their atomic orbitals overlap to produce a greater
density of electron cloud along the line connecting the two nuclei. In the simplified
representations of the formation of H 2O and NH3 molecules, the OH and NH bonds are also
formed in a similar manner, the bonding electron cloud having its maximum density on the
lines connecting the two nuclei. Such bonds are called sigma bonds (-bond).
A covalent bond established between two atoms having the maximum density of the electron
cloud along the line connecting the centre of the bonded atoms is called a -bond. A -bond
is thus said to possess a cylindrical symmetry along the internuclear axis.
Let us now consider the combination of two nitrogen atoms. Of the three singly occupied porbitals in each, only one p-orbital from each nitrogen (say, the p x may undergo head on
overlap to form a s-bond. The other two p-orbitals on each can no longer enter into a direct
overlap. But each p-orbital may undergo lateral overlap with the corresponding p-orbital on
the neighbour atom. Thus we have two additional overlaps, one by the two p y orbitals, and the
other by the two pz orbitals. These overlaps are different from the type of overlap in as-bond.
For each set of p-orbitals, the overlap results in accumulation of charge cloud on two sides of
the internuclear axis. The bonding electron cloud does no more posses an axial symmetry as
with the s-bond; instead, it possess a plane of symmetry. For the overlap of the p z atomic
orbital, the xy plane provides this plane of symmetry; for the overlap of the p yatomic orbitals,
the zx plane serves the purpose. Bonds arising out of such orientation of the bonding electron
cloud are designated as -bonds.
The bond formed by lateral overlap of two atomic orbitals having maximum overlapping on
both sides of the line connecting the centres of the atoms is called a -bond. A -bond
possess a plane of symmetry, often referred to as the nodal plane.

-Bond : When covalent bond is formed by overlapping of atomic orbitals along the same
axis it is called s - bond. Such type of bond is symmetrical about the line joining the two nuclei
e.g.

(a) s-s
overlapping

(b) s-p
overlapping

(c) p-p
overlapping

 - Bond: This type of bond is formed by the sidewise or lateral overlapping of two half filled
atomic orbitals.

|The strength of a bond depends upon the extent of overlapping of half-filled atomic orbitals.
The extent of overlapping is between two atoms is always greater when there is end to end
overlapping of orbitals than, when there is sidewise overlapping of oritals. Hence s-bond is
always stronger than p-bond.

The average distance between the nuclei of the two bonded atoms in a molecule is called
bond length and the energy required to break one mole of bonds of particular type in gaseous
state is called Bond energy or Bond strength. The same amount of energy is released in
formation of one mol of particular bond.
Limitation: VBT cannot explain the paramagnetic properties of B2,O2 etc.

Co-ordinate Covalency

A covalent bond results from the sharing of pair of electrons between two atoms where each
atom contributes one electron to the bond. It is also possible to have an electron pair bond
where both electrons originate from one atom and none from the other. Such bonds are
called coordinate bond or dative bonds. Since in coordinate bonds two electrons are shared by
two atoms, they differ from normal covalent-bond only in the way they are formed and once
formed they are identical to normal covalent bond.
It is represented as []
Atom/ion/molecule donating electron pair is called Donor or Lewis base. Atom / ion /
molecule accepting electron pair is called Acceptor or Lewis acid, [] points
donor to acceptor
NH4+, NH3 has three (N H) bond & one lone pair on N atom. In NH 4+ formation this lone pair
is donated to H+ (having no electron) NH3 + H+ NH4+

Properties of the coordinate compounds are intermediates of ionic and covalent

compounds.

Conditions for Formation of Covalent Bond

1.

The electronegativity deference between the two atoms should be less.

2.

The covalent bond is formed between the two non metals.

3.

Each combining atom must contribute at least one electron to the shared pair.

4.

The combining atoms should attain the noble gas configuration after bond formation.

Polar and non-polar covalent bonds

Covalent bonds can be classified into following two groups depending on the electronegativity
difference between the bonded atoms..
1.

Polar covalent bond.

2.

Nonpolar covalent bond.

Polar covalent bond is formed between two atoms which have large difference in
electronegativity. The electronegativity difference disturbs the distribution of shared pair of
electrons between the two atoms as the electron density would be more toward the element
which is more electronegative. This will develop partial positive charge on more
electronegative element and partial positive charge on less electronegative one. For example,
bond between H and F would be polar covalent bond.

Non-polar covalent bonds are formed between two like atoms

i.e. the atoms which have almost same electronegativity. Due to almost same
electronegativity, both atoms attract electron pair equally and no charge appears on any
atom, and the whole molecule becomes neutral. For example bond between two H atoms
would be non-polar.

Maximum Covalency

Elements which have vacant d-orbital can expand their octet by transferring electrons, which
arise after unpairing, to these vacant d-orbital e.g. in sulphur.

In excited state sulphur has six unpaired electrons and shows a valency of six e.g. in SF 6. Thus
an element can show a maximum covalency equal to its group number e.g. chlorine shows
maximum covalency of seven.

Dipole Moment

Difference in polarities of bonds is expressed on a numerical scale. The polarity of a molecule

is indicated in terms of dipole moment (). To measure dipole moment, a sample of the
substance is placed between two electrically charged plates. Polar molecules orient
themselves in the electric field causing the measured voltage between the plates to change.

The dipole moment is defined as the product of the distance separating charges of equal
magnitude and opposite sign, with the magnitude of the charge. The distance between the
positive and negative centres called the bond length.
Thus, = = electric charge bond length = q d
As q is in the order of 1010 esu and d is in the order of 108 cm, is the order of1018 esu cm.
Dipole moment is measured in Debye unit (D)
1D = 1018 es cm = 3.33 1030 coulomb metre
Note:
1.

2.

Generally as electronegativity difference increase in diatomic molecules, polarity of

bond between the atoms increases therefore value of dipole moment increases.
Dipole

moment

is

vector

quantity.

3.

A symmetrical molecule is non-polar even though it contains polar bonds. For

example, CO2, BF3, CCl4 etc. because summation of all bond moments present in the
molecules
cancel
each
other.

4.

Unsymmetrical non-linear polyatomic molecules have net value of dipole moment. For
example, H2O, CH3OH, NH3 etc.?

Calculation of Resultant Bond Moments

Let AB and AC are two polar bonds inclined at an angle their dipole moments are 1 and 2.

Resultant dipole moment may be calculated using vectorial method.

= 12 + 22 + 212 cos

when =

the

resultant

is

maximum R = 1 + 2

when, = 180, the resultant is minimum R = 1 2

For example, CO2 has got dipole moment of zero. The structure of CO2 is.This is a highly
symmetrical structure with a plane of symmetry passing through the carbon. The bond dipole
of CO is directed towards oxygen as it is the negative end. Here two equal dipoles acting in
opposite direction cancel each other and therefore the dipole moment is zero. Similarly dipole
moment of CCl4 is zero while that of CHCl 3 is non zero. . Explanation is again in geometry of
the molecules both CCl4 & CHCl3 have tetrahedral structure but CCl 4 is symmetrical while
CHCl3 is non-symmetrical.

Due to the symmetrical structure of CCl4 the resultant of bond dipoles comes out to be zero.
But in case of CHCl3 it is not possible as the presence of hydrogen introduces some
dissymmetry.

Bond Characteristics
1. Bond Length

The distance between the nuclei of two atoms bonded

together is termed as bond length or bond distance. It is expressed in angstrom () units or
picometer (pm).
[1 = 108 cm; 1 pm = 1012 m]
Bond length in ionic compound = rc+ + ra
Similarly, in a covalent compound, bond length is obtained by adding up the covalent (atomic)
radii of two bonded atoms.
Bond length in covalent compound (AB) = rA + rB
The factors such as resonance, electronegativity, hybridization, steric effects, etc., which
affect the radii of atoms, also apply to bond lengths.

Important features of bond length

1.

The bond length of the homonuclear diatomic molecules are twice the covalent radii.

2.

The lengths of double bonds are less than the lengths of single bonds between the
same two atoms, and triple bonds are even shorter than double bonds.Single bond >
Double bond > Triple bond (decreasing bond length)

3.

Bond length decreases with increase in s-character since s-orbital is smaller than a p
orbital.
sp3 C H = 1.112:
sp2 C H = 1.103;
sp C H = 1.08;
(25% s-character as in alkanes) (33.3% s-character as in alkenes) (50% s-character as in
alkynes)

4.

Bond length of polar bond is smaller than the theoretical non-polar bond length.

2. Bond Energy or Bond Strength

Bond energy or bond strength is defined as the amount of energy required to break a bond in
molecule.

Important features of bond energy

1.

The magnitude of the bond energy depends on the type of bonding. Most of the
covalent bonds have energy between 50 to 100 kcal mol1 (200-400 kJ mol1). Strength of
sigma bond is more than that of a -bond.

2.

A double bond in a diatomic molecules has a higher bond energy than a single bond
and a triple bond has a higher bond energy than a double bond between the same
atoms. C C > C = C > C C (decreasing bond length)

3.

The magnitude of the bond energy depends on the size of the atoms forming the bond,
i.e. bond length. Shorter the bond length, higher is the bond energy.

4.

Resonance in the molecule affects the bond energy.

5.

The bond energy decreases with increase in number of lone pairs on the bonded atom.
This is due to electrostatic repulsion of lone pairs of electrons of the two bonded atoms.

6.

Homolytic and heterolytic fission involve different amounts of energies. Generally the
values are low for homolytic fission of the bond in comparison to heterolytic fission.

7.

Bond energy decreases down the group in case of similar molecules.

8.

Bond
s
CC

energy
<

increase
p

<
>

in

the

sp

following
<

NN

(No lone pair)

order:

sp <
2

>

sp3
OO

( One lone pair)

(Two lone pair)

3. Bond angles
Angle between two adjacent bonds at an atom in a molecule made up of three or more atoms
is known as the bond angle.

Bond angles mainly depend on the following three factors:

(i) Hybridization: Bond angle depends on the state of hybridization of the central atom

Hybridization

Bond angle

Example

sp3

109o28'

CH4

120o

BCl3

180o

BeCl2

sp2

sp

Generally s- character increase in the hybrid bond, the bond angle increases.
(ii) Lone pair repulsion: Bond angle is affected by the presence of lone pair of electrons at
the central atom. A lone pair of electrons at the central atom always tries to repel the shared
pair (bonded pair) of electrons. Due to this, the bonds are displaced slightly inside resulting in
a decrease of bond angle.
(iii) Electronegativity: If the electronegativity of the central atom decreases, bond angle
decreases.

4. Resonance
There may be many molecules and ions for which it is not possible to draw a single Lewis
structure. For example we can write two electronic structures of O 3.

In (A) the oxygen - oxygen bond on the left is a double bond and the oxygen-oxygen bond on
the right is a single bond. In B the situation is just opposite. Experiment shows however, that
the two bonds are identical. Therefore neither structure A nor B can be correct.
One of the bonding pairs in ozone is spread over the region of all the three atom rather than
associated with particular oxygen-oxygen bond. This delocalised bonding is a type of bonding
in which bonding pair of electrons is spread over a number of atoms rather than localised
between two.

Structures (A) and (B) are called resonating or canonical structures and C is the resonance
hybrid. This phenomenon is called resonance, a situation in which more than one plausible
structure can be written for a species.
Atoms gain or lose electrons to attain a more stable noble gas - like electron configuration
(octet rule). There are two ways in which atoms can share electrons to satisfy the octet rule:
Ionic Bonding - occurs when two or more ions combine to form an electrically-neutral
compound
The
positive
cation
"loses"
an
The
negative
anion
"gains"
the
The anion steals the electrons from the cation.

electron
electron

(or
(or

2
2

or
or

3)
3)

Covalent Bonding - occurs when two or more atoms combine to form an electrically-neutral
compound
The electrons are shared between the two atoms. Both atoms don't have charge in the
beginning and the compound remains with zero charge.
The chemical activity of an atom is determined by the number of electrons in its valence shell.
With the help of concept of chemical bonding one can define the structure of a compound and
is used in many industries for manufacturing products in which the true structure cannot be
written at all.
Some other examples
(i) CO32 ion

Example
(ii) Carbon-oxygen bond lengths in carboxylate ion are equal due to resonance.

(iii) Benzene

(iv) Vinyl Chloride

Difference in the energies of the canonical forms and resonance hybrid is called resonance
stabilization energy and provides stability to species.

Rules for Writing Resonating Structures

Only electrons (not atoms) may be shifted and they may be shifted only to adjacent atoms or
bond
positions.
The number of unpaired electrons should be same in all the canonical form.
The positive charge should reside as far as possible on less electronegative atom and
negative charge on more electronegative atom.
Like charge should not reside on adjacent atom
The larger the number of the resonating structures greater the stability of species. Greater
number of covalency adds to the stability of the molecule.
Example: Out of the following resonating structures for CO 2 molecule, which are important for
describing the bonding in the molecule and why?

Solution: Out of the structures listed above, the structure (III) is wrong since the number of
electron pairs on oxygen atoms are not permissible. Similarly, the structures (II) has very little
contribution towards the hybrid because one of the oxygen atoms (electronegative) is show to
have positive charge. Carbon dioxide is best represented by structures (I) and (IV).

Hybridization
The mixing or merging of dissimilar orbitals of similar energies to form new orbitals is known
as hybridizationand the new orbitals formed are known as hybrid orbitals.

Important characteristics of hybridization?

1.

Orbitals belonging to the same atom or ion having similar energies get hybridized.

2.

Number of hybrid orbitals is equal to the no. of orbitals taking part in hybridization.

3.

The hybrid orbitals are always equivalent in energy and shape.

4.

The hybrid orbitals form more stable bond than the pure atom orbital.

5.

The reason hybridization takes place is to produce equivalent orbitals which give
maximum symmetry.

6.

It is not known whether actually hybridization takes place or not. It is a concept which
explains the known behaviour of molecules.

7.

The hybrid orbitals are directed in space in same preferred direction to have some
stable arrangement and giving suitable geometry to the molecule.

Refer the following video for hybridization

Depending upon the different combination of s and p orbitals, these types of
hybridization are known.
sp3 hybridization: In this case, one s and three p orbitals hybridise to form four sp 3 hybrid
orbitals. These four sp3 hybrid orbitals are oriented in a tetrahedral arrangement.

sp2 hybridization: In this case one s and two p orbitals mix together to form three sp 2 hybrid
orbitals and are oriented in a trigonal planar geometry.

The remaining p orbital if required form side ways overlapping with the other unhybridized p
orbital of other C atom and leads to formation of p2C = CH2 bond as in H
sp hybridization: In this case, one s and one p orbital mix together to form two sp hybrid
orbitals and are oriented in a linear shape.

The remaining two unhybridised p orbitals overlap with another unhybridised p orbital leading
to the formation of triple bond as in HC CH.

Shape

Hybridisation

Linear

sp

Trigonal planar

sp2

Tetrahedral

sp3

Trigonal bipyramidal

sp3d

Octahedral

sp3d2

Pentagonal bipyramidal

sp3d3

Rule for determination of total number of hybrid

orbitals

Detect the central atom along with the peripheral atoms.

Count the valence electrons of the central atom and the peripheral atoms.
Divide the above value by 8. Then the quotient gives the number of s bonds and
the remainder gives the non-bonded electrons. So number of lone pair = non bonded
electrons/2 .
The number of s bonds and the lone pair gives the total number of hybrid orbitals.
An Example Will Make This Method Clear:- SF4 Central atom S, Peripheral atom F
total number of valence electrons = 6 + (4 7) = 34
Now 34/8 = 4 2/8
Number of hybrid orbitals = 4 bonds + 1 lone pair)
So, five hybrid orbitals are necessary and hybridization mode is sp 3d and it is trigonal
bipyramidal (TBP).
Note:Whenever there are lone pairs in TBP geometry they should be placed in equatorial
position so that repulsion is minimum.

Compound and its

Hybridization

1. NCl3 Total valence electrons

= 26

Molecular geometry

Requirement = 3 bonds + 1
lone pair
Hybridization = sp3
Shape = pyramidal

2. BBr3 Total valence electron =

24
Requirement = 3 bonds
Hybridization = sp2
Shape = planar trigonal

3. SiCl4 Total valence electrons

= 32
Requirement = 4 bonds
Hybridization = sp3
Shape = Tetrahedral

4. CI4 Total valence electron =

32
Requirements = 4 bonds
Hybridization = sp3
Shape = Tetrahedral

5. SF6 Total valence electrons =

48
Requirement = 6 bonds
Hybridization = sp3d2
Shape = octahedral/square
bipyramidal

6. BeF2 Total valence electrons : F Be F

16
Requirement : 2 bonds
Hybridization : sp
Shape : Linear

7. ClF3 Total valence electrons :

28
Requirement: 3 bonds + 2
lone pairs
Hybridization : sp3d
Shape : T shaped

8. PF5 Total valence electrons :

40
Requirement : 5 bonds
Hybridization : sp3d
Shape : Trigonal bipyramidal
(TBP)

9. XeF4 Total valence electrons :

36
Requirement:4 bonds+ 2 lone
pairs
Hybridisation : sp3d
Shape : Square planar

Here three arrangements are possible out of which A and B are

same. A and B can be inter converted by simple rotation of
molecule. The basic difference of (B) and (C) is that in (B) the
lone pair is present in the anti position which minimizes the
repulsion which is not possible in structure (C) where the lone
pairs are adjacent. So in a octahedral structure the lone pairs
must be placed at the anti positions to minimize repulsion. So
both structure (A) and (B) are correct.

10. XeF2 Total valence electrons

: 22
Requirements : 2 bonds + 3
lone pairs
Hybridisation: sp3d
Shape : Linear

11. Total valence electrons : 32

Requirement : 4bonds
Hybridisation: sp3
Shape: tetrahedral
Here all the structures drawn are resonating structures with
O resonating with double bonded oxygen.

12. NO2 Total valence electron:

18
Requirement : 2 bonds + 1
lone pair

Hybridisation: sp2
Shape: angular

13. CO32 Total valence

electrons: 24

But C has 4 valence electrons of these 3 form s bonds \ the rest

will form a p bond.

Requirement = 3 bonds
Hybrdisation = sp2
Shape: planar trigonal
In the structure one bond is a double bond and the other 2 are
single. The position of the double bonds keeps changing in the
figure. Since peripheral atoms are isovalent, so contribution of
the resonanting structures are equal. Thus it is seen that none of
the bonds are actually single or double. The actual state is

14. CO2 Total

electrons:16

valence
O=C=O

Requirement: 2 bonds
Hybridisation: sp
Shape: linear

15. Total valence electrons = 32

Requirement= 4 bonds
Hybridisation: sp3
Shape: Tetrahedral

16. Total valence electron = 26

Requirement = 3 bond + 1
lone pair
Hybridization: sp3
Shape: pyramidal

17. XeO2F2 Total

electrons : 34
Requirement:
lone pairs

valence

4 bonds

+1

Hybridization : sp3d
Shape: Distorted TBP (sea-saw
geometry)

18. XeO3 Total valence electrons

: 26
Requirement:
lone pair

3 bonds

Hybridization: sp3
Shape: Pyramidal

19. XeOF4 Total

electrons : 42
Requirement:
lone pair

valence

5 bonds

Hybridization: sp3d2
Shape: square pyramidal.

20. PF2Br3 Total valence

electrons : 40
Requirements : 5 bonds
Hybridisation: sp3d
Shape : trigonal bipyramidal

Valence Shell Electron Pair Repulsion (VSPER)

Theory

Regular Geometry of Molecules

Geometry of the molecules in which the central atom has no lone pairs are regular and can be
predicted simply.
Bond ange of any molecule with regular geometry = 360o /Number of bond pairs

Number of
electron pairs

Arrangement of electrons

Molecular geometry

Examples
BeCl2, HgCl2

2
BAB
Linear

3
BF3, AlCl3

= 120

= 120

CH4, NH4+, SiF4

5
PCl5, PF5

SF6

Irregular Geometry of Molecules and VSPER Theory

Geometry of the molecules having lone pair of electrons can not be predicted simpley using
above mentioned method. The geometric arrangement of atoms in molecules and ions may
be predicted by means of the valence-shell electron-pair repulsion (VSEPR) theory. This type
includes molecules which may or may not obey the octet rule but have only single bonds.
Postulates of VSEPR theory:
1.

The shape of the molecule is determined by repulsions between all of the electron pairs
present in the valence shell.

2.

A lone pair of electrons takes up more space around the central atom than a bond-pair,
since the lone pair is attracted to one nucleus whilst the bond pair is shared by two
nuclei. It follows that repulsion between two lone pairs is greater than repulsion between
a lone pair and a bond pair, which in turn is greater than the repulsion between two
bond pairs. Thus the presence of lone pairs on the central atom causes slight distortion
of the bond angles from the ideal shape. If the angle between a lone pair, the central
atom and a bond pair is increased, it follows that the actual bond angle between the
atoms
must
be
decreased.The
descending
order
of
repulsion
is

(lplp)
>
where lp-Lone pair; bp-bond pair

(lpbp)

>

(bpbp)

3.

The magnitude of repulsions between bonding pairs of electrons depends on the

electronegativity difference between the central atom and the other atoms.

4.

Double bonds cause more repulsion than single bonds and triple bonds cause more
repulsion than double bonds.

5.

A brief summary of molecular shapes resulting from different configurations of

electrons pairs is presented below:

6.

With very few exceptions, the predictions based on the VSEPR theory have been shown
to be correct.

Molecule
Type

No. of
Bonding
pairs

No. of
lone pair

Arrangement of
electrons pairs

Shape
(Geometry)

AB2E

Examples

SO2, O3

AB3E

Bent

Trigonal pyramidal NH3

AB2E2

H2O

See saw

SF4

AB4E

Bent

AB3E2

T shaped

CIF3

Square pyramidal

BrF5

Square planar

XeF4

AB5E

AB4E2

To find the shape of a molecule follow the steps given below:

1.

Identify the central atom and count the number of valence electrons.

2.

Add to this, number of other atoms.

3.

If it is an ion, add negative charges and subtract positive charges. Call it total N

4.

Divide N by 2 and compare the result with chart I and obtain the shape.

Total N/2

Shape of molecule or ion

Example

Linear

HgCl2/BeCl2

Triangular planar

BF3

Angular

SnCl2, NO2

Tetrahedral

CH4, BF4-

Trigonal Pyramidal

NH3, PCl3

Angular

H2O

Trigonal bipyramidal

PCl5, PF5

Irregular tetrahedral

SF4, IF4+

T-shaped

CIF3, BrF3

Linear

XeF2, I3-

Octahedral

SF6, PF6-

Square Pyramidal

IF5

Square planar

XeF4, ICI4

Molecular Orbital Theory

One of the most important theories developed is the wave-particle, duality of particles.
Electrons can be considered as particles and waves also. Based on this, it can be concluded
that electrons behaving as waves can interact with each other and the process is called
interference.
As in waves, two types of interferences are possible: (1) constructive and (2) Destructive.
In molecules the atomic orbitals of all the atoms are assumed to interfere with each other in
the form of waves and depending on the nature of interferences, two molecular orbitals result.
The one which results from constructive interference is called bonding molecular orbital and
the one which results from destructive interference is called anti-bonding molecular orbital.
Obviously anti-bonding MO is of higher energy than Bonding MO.
In Molecular Orbital Theory (MOT) the atoms in a molecule are supposed to loose their
individual control over the electrons. The nuclei of the bonded atoms are considered to be
present at equilibrium inter-nuclear positions. The orbitals where the probability of finding the
electrons is maximum are multicentred orbitals called molecular orbitals extending over two
or more nuclei.
In MOT the atomic orbitals loose their identity and the total number of electrons present are
placed in Mos according to increasing energy sequence (Auf Bau Principle) with due reference
to Paulis Exclusion Principle and Hunds Rule of Maximum Multiplicity.

As mentioned above, when a pair of atomic orbitals combine they give rise to a pair of
molecular orbitals, the bonding and the anti-bonding. The number of molecular orbitals
produced must always be equal to the number of atomic orbitals involved. Electron density is
increased for the bonding MOs in the inter-nuclear region but decreased for the anti-bonding
MOs, Shielding of the nuclei by increased electron density in bonding MOs reduces inter
nuclei repulsion and thus stabilizes the molecule whereas lower electron density even as
compared to the individual atom in anti-bonding MOs increases the repulsion and destabilizes
the system.
In simple homonuclear diatomic molecules the order of MO's based on increasing energy is :

For molecules including O2 and above, the order is

This order is true except B2, C2 & N2. If the molecule contains unpaired electrons in MOs it will
be paramagnetic but if all the electrons are paired up then the molecule will be diamagnetic.

Bond order

Bond order is a number which indicates the no. of bonds a molecule possesses and the
stability of the molecule in comparison to another. An integral value implies that so many
bonds exist in the molecule. Anything fractional indicates that the bond is intermediate.
Bond-order = 1/2 (no. of bonding electrons - No. of antibonding electrons).

1.

Application
Molecules

of

MOT

to

Homonuclear

Diatomic

H2+ molecule ion. Total no. of electrons = 1

Arrangement : s 1s1
An unpaired electron always indicates that the molecule is paramagnetic.

2.

H2 molecule, Total no. of electrons = 2

Arrangement : s 1s2
Paired electrons , so diamagnetic.

BO = 1/2 (2-0) = 1
Therefore No. of bonds = 1
3.

He2+ molecule ion, Total no. of electrons = 3,

Arrangement : s1s2, s* 1s1
Unpaired electron, so paramagnetic
BO = 1/2 (2-1) = 1/2
Bond existing by virtue of a single electron.

4.

He2 molecule. Total No. of electrons = 4,

Arrangement : s1s2, s* 1s2
Diamagnetic BO = 0
Molecule does not exist.

Example: Which diatomic molecule of second period besides O2 should be paramagnetic?

Solution:

As, paramagnetism arises due to unpaired electron. Therefore B 2is paramagnetic molecule.

M.O. of Some Diatomic Heteronuclei Molecules

The molecular orbitals of heteronuclei diatomic molecules should differ from those of
homonuclei species because of unequal contribution from the participating atomic orbitals.
Lets take the example of CO.
The M.O. energy level diagram for CO should be similar to that of the isoelectronic molecule
N2. But C & O differ much in electronegativity and so will their corresponding atomic orbitals.
But the actual MO for this species is very much complicated since it involves a hybridisation
approach between the orbital of oxygen and carbon.
HCl Molecule: Combination between the hydrogen 1s A.Os. and the chlorine 1s, 2s, 2p & 3s
orbitals can be ruled out because their energies are too low. The combination of H
1s1 and 3p1x gives both bonding and anti-bonding orbitals, and the 2 electrons occupy the
bonding M.O. leaving the anti-bonding MO empty.
NO Molecule: The M.O. of NO is also quite complicated due to energy difference of the atomic
orbitals of N and O.

As the M.O.s of the heteronuclei species are quite complicated, so we should concentrate in
knowing the bond order and the magnetic behaviour.

Molecules/Ions

Total No. of electrons

Magnetic behaviour

CO

14

Diamagnetic

NO

15

Paramagnetic

NO+

14

Diamagnetic

NO

16

Diamagnetic

CN

13

Paramagnetic

CN

14

Diamagnetic

Inert Pair Effect

Heavier p-block and d-block elements show two oxidation states. One is equal to group
number and second is group number minus two. For example Pb(5s 25p2) shows two OS, +II
and +IV. Here +II is more stable than +IV which arises after loss of all four valence electrons.
Reason given for more stability of +II O.S. that 5s 2 electrons are reluctant to participate in
chemical bonding because bond energy released after the bond formation is less than that
required to unpair these electrons (lead forms a weak covalent bond because of greater bond
length).
Example: Why does PbI4 not exist?
Solution: Pb(+IV) is less table than Pb(+II) due to inert pair effect and therefore Pb(+IV) is
reduced to Pb(+II) by I which changes to I2(I is a good reducing agent)

Covalent Character in Ionic Compounds

Fajan's Rule

Although atomic bond in a compound like M+X- is considered to be 100% ionic, actually it also
has some covalent character. An explanation for the partial covalent character of an ionic
bond has been given by Fajan. According to Fajan, if two oppositely charged ions are brought

together, the nature of the bond between them depends upon the effect of one ion on the
other.
When two oppositely charged ions (say A + and B- ) approach each other the positive ion
attracts electrons on the outermost shell of the anion and repels its positively charged
nucleus. This results in the distortion,deformation or polarization of the anion. If the
polarization is quite small, an ionic bond is formed, while if the degree of polarization is large,
a covalent bond results.
Thus the power of an ion (cation) to distort the other ion is known as its polarization
power and the tendency of the ion(anion) to get polarized by the other ion is known as
its polarisability. Greater the polarization power or polarisability of an ion, greater will be its
tendency to form a covalent bond.
The polarising power, or polarisability and hence formation of covalent bond is
favoured by the following factors:
1.

Small Positive Ion (Cation): Due to greater concentration of positive charge on a

small area, the smaller cation has high polarising power. This explains why LiCl is more
covalent than KCl.

2.

Large Negative Ion (Anion): The larger the anion, the greater is its polarisability, i.e.
susceptibility to get polarised. It is due to the fact that the outer electrons of a large
anion are loosely held and hence can be more easily pulled out by the cation. This
explains why iodides, among halides, are most covalent in nature.

3.

Large Charge on Either of the Two Ions: As the charge on the ion increases, the
electrostatic attraction of the cation for the outer electrons of the anion also increases,
with the result its ability for forming the covalent bond increases. Thus covalency
increases in the order : Na+ Cl-, Mg2+ (Cl2)2-, Al3+ (Cl3)3 -

4.

Electronic Configuration of the Cation : For the two ions of the same size and
charge, one with a pseudo noble gas configuration (i.e., 18 electrons in outer-most shell)
than a cation with noble gas configuration (i.e. 8 electrons in outermost shell) will be
more polarising. Thus copper (I) chloride is more covalent than sodium chloride
although Cu+ ion (0.96A) and Na+ ion (0.95A) have same size and charge.

The orbital overlapping involved in covalency reduces, the charge on each ion and so weakens
the electrovalent forces throughout the solid, as is evident from the melting point of lithium
halides.
LiF = 870C LiCl = 613C
LiBr = 547C LiI = 446C
From the above discussion, we find that greater the possibility of polarisation, lower is
the melting point and heat of sublimation and greater is the solubility in non-polar
solvents.

Example: The melting point of KCl is higher than that of AgCl though the crystal radii of
Ag+ and K+ ions are almost the same.
Solution : Now whenever any comparison is asked about the melting point of the
compounds which are fully ionic from the electron transfer concept it means that the
compound having lower melting point has got lesser amount of ionic character than the other
one. To analyse such a question first find out the difference between the 2 given compounds.
Here in both the compounds the anion is the same. So the deciding factor would be the
cation. Now if the anion is different, then the answer should be from the variation of the
anion. Now in the above example, the difference of the cation is their electronic configuration.
K+ = [Ar]; Ag+ = [Kr] 4d10. This is now a comparison between a noble gas core and pseudo
noble gas core, the analysis of which we have already done. So try to finish off this answer.

Percentage of Ionic Character

Every ionic compound having some percentage of covalent character according to Fajans
rule. The percentage of ionic character in a compound having some covalent character can be
calculated by the following equation.
The percent ionic character = Observed dipole moment/Calculated dipole moment
assuming 100% ionic bond 100
Example: Dipole moment of KCl is 3.336 1029 coulomb metre which indicates that it is
highly polar molecule. The interatomic distance between k + and Cl is 2.6 1010 m. Calculate
the dipole moment of KCl molecule if there were opposite charges of one fundamental unit
located at each nucleus. Calculate the percentage ionic character of KCl.
Solution: Dipole moment = e d coulomb metre
For KCl d = 2.6 1010 m
For complete separation of unit charge
e = 1.602 1019 C
Hence = 1.602 1019 2.6 1010 = 4.1652 1029 Cm
KCl = 3.336 1029 Cm
% ionic character of KCl = 3.3361029/4.1651029 = 80.09%
Example. Calculate the % of ionic character of a bond having length = 0.83 and 1.82 D as
its observed dipole moment.
Solution: Tocalculate considering 100% ionic bond
= 4.8 1010 0.83 108esu cm

= 4.8 0.83 1018 esu cm = 3.984 D

% ionic character = 1.82/3.984 100 = 45.68
The example given above is of a very familiar compound called HF. The % ionic character is
nearly 43.25%, so the % covalent character is (100 43.25) = 56.75%. But from the octet rule
HF should have been a purely covalent compound but actually it has some amount of ionic
character in it, which is due to the electronegativity difference of H and F. Similarly knowing
the bond length and observed dipole moment of HCl, the % ionic character can be known. It
was found that HCl has 17% ionic character. Thus it can be clearly seen that although we call
HCl and HF as covalent compounds but it has got appreciable amount of ionic character. So
from now onwards we should call a compound having more of ionic less of covalent and vice
versa rather than fully ionic or covalent.

Metallic and Hydrogen Bonding

Metallic Bonding

Metals are characterised by bright, lustre, high electrical and thermal conductivity,
malleability, ductility and high tensile strength. A metallic crystal consists of very large
number of atoms arranged in a regular pattern. Different model have been proposed to
explain the nature of metallic bonding two most important modules are as follows

The electron sea Model In this model a metal is assumed to consist of a lattice of positive ion
(or kernels) immersed in a sea of mobile valence electrons, which move freely within the
boundaries of a crystal. A positive kernel consists of the nucleus of the atom together with its
core on a kernel is, therefore, equal in magnitude to the total valence electronic charge per
atom. The free electrons shield the positively charged ion cores from mutual electrostatic
repulsive forces which they would otherwise exert upon one another. In a way these free
electrons act as glue to hold the ion cores together.
The forces that hold the atoms together in a metal as a result of the attraction between
positive ions and surrounding freely mobile electrons are known as metallic bonds.
Through the electron sea predated quantum mechanics it still satisfactorily explains certain
properties of the metals. The electrical and thermal conductivity of metals for example, can

be explained by the presence of mobile electrons in metals. On applying an electron field,

these mobile electrons conduct electricity throughout the metals from one end to other.
Similarly, if one part of metal is heated, the mobile electrons in the part of the metals acquire
a large amount of kinetic energy. Being free and mobile, these electrons move rapidly
throughout the metal and conduct heat to the other part of the metal.
On the whole this model is not satisfactory.

Hydrogen Bonding

An atom of hydrogen linked covalently to a strongly electronegative atom can establish an

extra weak attachment to another electronegative atom in the same or different molecules.
This attachment is called a hydrogen bond. To distinguish from a normal covalent bond, a
hydrogen bond is represented by a broken line eg X H Y where X & Y are two
electronegative atoms. The strength of hydrogen bond is quite low about 2-10 kcal mol 1 or
8.442 kJ mol1 as compared to a covalent bond strength 50100 kcal mol 1 or 209 419 kJ mol1

Conditions for Hydrogen Bonding:

Hydrogen should be linked to a highly electronegative element.
The size of the electronegative element must be small.
These two criteria are fulfilled by F, O, and N in the periodic table. Greater the
electronegativity and smaller the size, the stronger is the hydrogen bond which is evident
from the relative order of energies of hydrogen bonds.

Types of Hydrogen Bonding:

Intermolecular hydrogen bonding:This type of bonding takes place between two
molecules of the same or different types. For example,
H
H
H
|
|
|
OHOHOH
Intermolecular hydrogen bonding leads to molecular association in liquids like water etc. Thus
in water only a few percent of the water molecules appear not to be hydrogen bonded even at
90C. Breaking of those hydrogen bonds throughout the entire liquid requires appreciable
heat energy. This is indicated in the relatively higher boiling points of hydrogen bonded
liquids. Crystalline hydrogen fluoride consists of the polymer (HF) n. This has a zig-zag chain
structure
involving
H-bond.

Intramolecular hydrogen bonding: This type of bonding occurs between atoms of the
same molecule present on different sites. Intramolecular hydrogen bonding gives rise to a
closed ring structure for which the term chelation is sometimes used. Examples are
o-nitrophenol, salicylaldehyde.

Importance of Hydrogen Bonding in Biological Systems:

Hydrogen bonding plays a vital role in physiological systems. Proteins contain chains of amino
acids. The amino acid units are arranged in a spiral form somewhat like a stretched coil spring
(forming a helix). The N-H group of each amino acid unit and the fourth C=O group following it
along the chain, establishes the NH---O hydrogen bonds. These bonds are partly responsible
for the stability of the spiral structure. Double helix structure of DNA also consists of two
strands forming a double helix and are joined to each other through hydrogen bond.

Effect of Hydrogen Bonding

Hydrogen bonding has got a very pronounced effects on certain properties of the molecules.
They have got effects on
1.

State of the substance

2.

Solubility of the substance

3.

Boiling point

4.

Acidity of different isomers

These can be evident from the following examples.

Example. H2O is a liquid at ordinary temperature while H2S is a gas although both O and S
belong to the same group of the periodic table.
Solution: H2O is capable of forming intermolecular hydrogen bonds. This is possible due to
high electronegativity and small size of oxygen. Due to intermolecular H-bonding, molecular
association takes place. As a result the effective molecular weight increases and hence the
boiling point increases. So H2O is a liquid. But in H2S no hydrogen bonding is possible due to

large size and less electronegativity of S. So its boiling point is equal to that of an isolated H 2S
molecule and therefore it is a gas.
Example.Ethyl alcohol (C2H5OH) has got a higher boiling point than dimethyl ether (CH 3-OCH3) although the molecular weight of both are same.
Solution: Though ethyl alcohol and dimethyl ether have the same molecular weight but in
ethyl alcohol the hydrogen of the O-H groups forms intermolecular hydrogen bonding with the
OH group in another molecule. But in case of ether the hydrogen is linked to C is not so
electronegative to encourage the hydrogen to from hydrogen bonding.
HOHOHO
|
|
|
C2H5
C2H5
C2H5
Due to intermolecular H-bonding, ethyl alcohol remains in the associated form and therefore
boils at a higher temperature compared to dimethyl ether.