Chemical Bonding Class11th By

PS Sir IIT JEE /PMT Course

BY: LEARN FOR FREE

IN: CHEMISTRY

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:
 Odd-electron species like NO, NO2, O2 etc. Since it is impossible to
distribute an odd number of electrons into pairs, these species
necessarily violate the octet rule.

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

Species in which the central atom `expands' its octet (so to speak)
PCl5, SF6, many transition metal compounds etc.

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

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 of gaseous cations A(g) + I.E. A+ (g) + e

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
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 Hf.

For example: Born- Haber Cycle for Soidum Chloride

Solved Problem on Born- Haber Cycle

Calculate the lattice enthalpy of MgBr2. Given that

Enthalpy of formation of MgBr2 = -524 kJ mol1

Some of first & second ionization enthalpy (IE1 + 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 mol1

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 mol 1

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 non-polar 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

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 p-orbitals in each, only one p-orbital from each nitrogen
(say, the px 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
py orbitals, and the other by the two p z 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
NH4+ 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 SF6. 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. Generally as electronegativity difference increase in diatomic

molecules, polarity of bond between the atoms increases therefore
value of dipole moment increases.

2. Dipole moment is a 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 = 0 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 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
The bond length of the homonuclear diatomic molecules are twice
the covalent radii.

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)

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)

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

bond length.

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:

The magnitude of the bond energy depends on the type of bonding.

Most of the covalent bonds have energy between 50 to 100 kcal mol
1 (200-400 kJ mol1). Strength of sigma bond is more than that of a -
bond.

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)

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.

Resonance in the molecule affects the bond energy.

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.

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.

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

Bond energy increase in the following order:

s < p < sp < sp2 < sp3 C C > N N > O O (No lone

pair) (One lone pair) (Two lone pair)

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

sp2 120o BCl3

sp 180o BeCl2

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.

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 O3.
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 electron (or 2 or 3) The negative anion

"gains" the electron (or 2 or 3) The anion steals the electrons from the
cation.

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).
The mixing or merging of dissimilar orbitals of similar energies to form new
orbitals is known as hybridization and 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.

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 sp3 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 sp2 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.

hape Hybridisation
inear sp

rigonal planar sp2

etrahedral sp3

rigonal bipyramidal sp3d

ctahedral sp3d2

entagonal 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:- SF 4 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 Molecular geometry

1. NCl3 Total valence electrons = 26

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 : 16 F Be F

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 ar

be inter converted by simple rotation of molecule. The basic d
(C) is that in (B) the lone pair is present in the anti position wh
repulsion which is not possible in structure (C) where the lone
So in a octahedral structure the lone pairs must be placed at th
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
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 res

Requirement = 3 bonds

Hybrdisation = sp2

Shape: planar trigonal

In the structure one bond is a double bond and the other 2 are s
of the double bonds keeps changing in the figure. Since periph
isovalent, so contribution of the resonanting structures are equ
that none of the bonds are actually single or double. The actua

14. CO2 Total valence electrons:16 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 valence electrons : 34

Requirement: 4 bonds +1 lone pairs

Hybridization : sp3d

Shape: Distorted TBP (sea-saw geometry)

18. XeO3 Total valence electrons : 26

Requirement: 3 bonds + 1 lone pair

Hybridization: sp3

Shape: Pyramidal

19. XeOF4 Total valence electrons : 42

Requirement: 5 bonds + 1 lone pair

Hybridization: sp3d2

Shape: square pyramidal.

20. PF2Br3 Total valence electrons : 40

Requirements : 5 bonds

Hybridisation: sp3d

Shape : trigonal bipyramidal

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 = 360 o /Number of bond
pairs

Number
of Arrangement of Molecular
Examples
electron electrons geometry
pairs
B A B
2 BeCl2, HgCl2
Linear

3 BF3, AlCl3

= 120 = 120
 4 CH4, NH4+, SiF4

5 PCl5, PF5

6 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:

The shape of the molecule is determined by repulsions between all of

the electron pairs present in the valence shell.

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

(lp lp) > (lp bp) > (bp bp)

where lp-Lone pair; bp-bond pair

 The magnitude of repulsions between bonding pairs of electrons
depends on the electronegativity difference between the central atom
and the other atoms.

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

A brief summary of molecular shapes resulting from different

configurations of electrons pairs is presented below:

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

No.
Arrangemen
No. of of Shape
Molecul t of Example
Bondin lon (Geometr
e Type electrons s
g pairs e y)
pairs
pair

AB2E 2 1 Bent SO2, O3

Trigonal
AB3E 3 1 NH3
pyramidal

AB2E2 2 2 Bent H2O

See saw SF4

AB4E 4 1

AB3E2 3 2 T shaped CIF3

Square pyramidal BrF5

AB5E 5 1
 AB4E2 4 2 Square planar XeF4

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

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

Add to this, number of other atoms.

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

Call it total N

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

Shape of molecule or
Total N/2 Example
ion
2 Linear HgCl2/BeCl2

3 Triangular planar BF3

3 Angular SnCl2, NO2

4 Tetrahedral CH4, BF4-

4 Trigonal Pyramidal NH3, PCl3

4 Angular H2O

5 Trigonal bipyramidal PCl5, PF5

5 Irregular tetrahedral SF4, IF4+

5 T-shaped CIF3, BrF3

5 Linear XeF2, I3-

6 Octahedral SF6, PF6-

6 Square Pyramidal IF5

6 Square planar XeF4, ICI4

Introduction to 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).

Application of MOT to Homonuclear Diatomic Molecules

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

Arrangement : s 1s1

An unpaired electron always indicates that the molecule is

paramagnetic.

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

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.

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.

Total No. of Magnetic

Molecules/Ions
Electrons 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(5s25p2) 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:

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.

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.

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 -

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 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 mol1 or 8.442 kJ mol1 as compared to a covalent bond strength
50100 kcal mol1 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

State of the substance

Solubility of the substance

Boiling point

Acidity of different isomers

These can be evident from the following examples.

Example. H2O is a liquid at ordinary temperature while H 2S 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 H 2S 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 H2S molecule and therefore it is a gas.

Example.Ethyl alcohol (C2H5OH) has got a higher boiling point than

dimethyl ether (CH3-O-CH3) 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
| | |
C2 H 5 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.

Solved Problems of Chemical Bonding

Prob 1. Arrange the bonds in order of increasing ionic character in the
molecules:
LiF, K2O, N2, SO2 and ClF3
Solution: N2 < ClF3 < SO2 < K2O < LiF
Prob 2. Arrange the following in order of increasing ionic character:
C-H, F-H, Br-H, Na-I, K-F and Li-Cl
Solution: C-H < Br-H < F-H < Na-I < Li-Cl < K-F
Prob 3. Predict the shapes of the following ions
(a) BeF3- (b) BF4-
(c) IF4- (d) IBr2-
Solution:
(a) Triangular
(b) Tetrahedral
(c) Square planar
(d) Linear
Prob 4. Arrange the following in increasing order of stability O 2, O2+, O2-,
O22-
Solution: O22- < O2- < O2 < O2+
Calculate first the bond order which is as follows
O2 2, O2+ 2.5, O2- 1.5, O22- 1 & then arrange according to
increasing bond order.
Prob 5. Arrange the following:
(i) N2, O2, F2, Cl2 in increasing order of bond dissociation energy.
(ii) Increasing strength of hydrogen bonding (X H X):
O, S, F, Cl, N
Solution: (i) F2 < Cl2 < O2 < N2 (ii) Cl < S < N < O < F
Prob 6. Explain the following o - hydroxy benzaldehyde is liquid at room
temperature while p - hydroxy benzaldehyde is high melting solid.
Solution: There is intramolecular H bonding in o - hydroxy benzaldehyde
while intermolecular hydrogen bonding in p-hydroxy benzaldehyde

Prob 7. Explain why ClF2- is linear but ClF2+ is a bent molecular ion?
Solution: Chlorine atom lies in sp3d hybrid state. Three lone pairs are
oriented along the corners of triangular plane
Chlorine atom lies in sp3 hybrid state. Two lone pairs are oriented along
two corners of tetrahedral

Prob 8. AlF3 is ionic while AlCl3 is covalent.

Solution: Since F is smaller in size, its polarisability is less and therefore it
is having more ionic character. Whereas Cl being large in size is having
more polarisability and hence more covalent character.
Prob 9. Write down the resonance structure of nitrous oxide

Solution:
Prob 10. Explain why BeH2 molecule has zero dipole moment although the
Be-H bonds are polar.
Solution: BeH2 is a linear molecule (H-Be-H) with bond angle equal to 180 o.
Although the Be-H bonds are polar on account of electronegativity
difference between Be and H atoms, the bond polarities cancel with each
other. The molecule has resultant dipole moment of zero.
Prob 11. Why the bond angle of H C H in methane (CH 4) is 109 28 while
H N H bond angle in NH 3 is 107 though both carbon and nitrogen are
sp3 hybridized
Solution: In CH4 there are 4 bond pair of electrons while in NH 3 are 3 bond
pair of electrons and 1 lone pair of electrons. Since bond pair bond pair
repulsion is less than lone pair bond pair repulsion, in NH 3 bond angle is
reduced from 10928 to 107.
Prob 12. Why bond angle in NH3 is 107 while in H2O it is 104.5?
Solution: In NH3, central nitrogen atom bears only one lone pair of
electrons whereas in H2O central oxygen atom bears two lone pair of
electrons.
Since the repulsion between lone pair-lone pair and lone pair bond pair is
more than that between bond pair-bond pair, the repulsion in H 2O is much
greater than that in NH3 which results in contraction of bond angle from
10928 to 104.5 in water while in NH 3 contraction is less i.e. from
10928 to 107.
If the electronegativity of the peripheral atoms is more, then the bond
angle will be less. For example if we consider NH 3 and NF3, F N F bond
angle will be lower than H N H bond angle. This is because in NF 3 the
bond pair is displaced more towards F and in NH 3 it is displaced more
towards N. So accordingly the b.p. b.p. interaction is less in NF 3 and more
in NH3.
Prob 13. The bond angle of H2O is 104 while that that of F2O is 102.
Solution:Both H2O and F2O have a lone pair of electrons. But fluorine being
highly electronegative, the bond pair of electrons are drawn more towards
F in F2O, whereas in H2O it is drawn towards O. So in F 2O the bond pairs
being displaced away from the central atom, has very little tendency to
open up the angle. But in H2O this opening up is more as the bond pair
electrons are closer to each other. So bond of F2O is less than H2O.

Prob 14. Predict the hybridization for the central atom in POCl 3, OSF4,
OIF5.
Solution:
Total No. of V.E. = 5+6+21/8 = 32/8 = 4
So, hybridization = sp3
OSF4 = 6+6+28/8 = 40/8 = 5
So, hybridization of s = dsp3
OIF5 = 6+7+35/8 = 48/8 = 6
So, hybridization of I = d2sp3
Prob 15. Out of the three molecules XeF 4, SF4 and SiF4 one which has
tetrahedral structures is
(A) All of three
(B) Only SiF4
(C) Both SF4 and XeF4
(D) Only SF4 and XeF4
Solution:
Hybridization of XeF4 = sp3d2, SF4 = sp3d, SiF4 = sp3
Hence (B) is correct.
Prob 16. Among the following compounds in which case central element
uses d-orbital to make bonds with attached atom
(A) BeF2 (B) XeF2 (C) SiF4 (D) BF3
Solution:
In XeF2. Xe atom has sp3d hybridisation. Hence (B) is correct.
Prob 17.
When NH3 is treated with HCl, state of hybridisation on central nitrogen
(A) Changes from sp3 to sp2
(B) Remains unchanged
(C) Changes from sp3 to sp3d
(D) Changes from sp3 to sp
Solution:
On NH4+ state of hybridisation on central nitrogen atom is sp 3 as in NH3.

Hence (B) is the correct answer.