Chemical Bonding

Lecture Note
XI-B

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 Chemical Bond
Molecules of chemical substances are made of two or more atoms joined together by some force, acting
between them. This force which results from the interaction between the various atoms that go to form a stable
molecule, is referred to as a Chemical Bond.
A chemical bond is defined as a force that acts between two or more atoms to hold them together as a stable
molecule.
Types of chemical bond
Ionic or Electrovalent Bond
Covalent bond
Co-ordinate Covalent Bond
Metallic Bond
Valence Electrons
The electrons in the outer energy level of an atom are the ones that can take part in chemical bonding are
known as Valence Electron.
The electronic configuration of Na is 2, 8, 1 and that of Cl is 2, 8, 7. Thus sodium has one valence electron
and chlorine 7.
Bond pair and Lone pair of Electrons: The valence electrons actually involved in bond formation are called
bonding electrons or Bond Pair. The remaining valence electrons still available for bond formation are
referred to as non-bonding electrons or lone pair of electron.
Lewis Symbols of Elements:
A Lewis symbol of an element consists of an element’s symbol and surrounding dots to represent the
number of valence electrons. In this notation, the symbol of an element represents the nucleus plus the
inner normally filled levels (or shells) of the atom. For illustration, the symbol Na stands for the nucleus of
sodium atom plus 2, 8 electrons in the inner two levels.

Lewis dot formula for atoms of representative elements

The structural formulae of compounds built by union of Lewis symbols for the component atoms, are
referred to as Electron-dot formulas, or Electron-dot structures or Lewis structures
Electronic Theory of Valence or Valence Electron Theory
As Bohr put forward his model of the atom so electronic configuration of elements was known. G.N.
Lewis and W. Kossel, working independently, used this knowledge to explain ‘why atoms joined to
form molecules’.
They visualised that noble gas atoms had a stable electronic configuration, while atoms of all other
elements have unstable or incomplete electronic configuration. In 1916, they gave the electronic theory
of valence. It states that: In chemical bond formation, atoms interact by losing, gaining, or sharing

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 of electrons so as to acquire a stable noble gas configuration. Each noble gas, except helium, has a
valence shell of eight electrons
Atoms interact by electron-transfer (loss or gain) or electron-sharing, so as to achieve the stable
outer shell of eight electrons.
The tendency for atoms to have eight electrons in the outer shell is also known as the Octet Rule or
the Rule of Eight

Ionic Bond or Electrovalent Bond

This type of bond is established by transfer of an electron from one atom to another. Let us consider a
general case when an atom A has one electron in the valence shell and another atom B has seven electrons. A
has one electron in excess and B has one electron short than the stable octet. Therefore, A transfers an electron
to B and in this transaction both the atoms acquire a stable electron- octet. The resulting positive ion (cation)
and negative ion (anion) are held together by electrostatic attraction.

The electrostatic attraction between the cation (+) and anion (–) produced by electron-transfer constitutes an Ionic or
Electrovalent bond.

An ion is an atom or group of atoms which has acquired charge due to the loss or gain of one or more electrons.
When an atom gains an electron to form a negative ion (anion), it will increase in size. On the other hand,
when an atom loses an electron to give positive ion (cation), it will contract. The electron lost or gained is
always from the outermost shell.
Lattice Energy

When one mole of an ionic solid is formed from its constituent gaseous ions, the energy released is called
the lattice energy.

Lattice energy: - “The amount of energy released when one mole of an ionic compound is formed from its
cations and anions.”
Greater the lattice energy, greater the strength of ionic bond.
The value of lattice energy depends upon the following two factors:
a) Size of the ions: In order to have the greater force of attraction between the cations and anions their
size should be small as the force of attraction is inversely proportional to the square of the distance
between them.
b) Charge on Ions: Greater the charge on ions greater will be the force of attraction between them
and, therefore, greater will be the strength of the ionic bond.

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Born Haber’s Cycle: The energy included in the formation of an ionic compound from its constituent elements
may be considered as shown by the Born-Haber Cycle for the formation of one mole of Ionic Compound from
their respective Cation (M+) and Anion (X-)

The amount of heat liberated (i.e. H ) in the overall reaction is the heat of formation of ionic compound.
From the above
H = H (sub) + IE + H (diss) + EA + (-U)
H = Heat of formation H (Sub) = Heat of sublimation H (diss) = Dissociation energy
I E= Ionization Energy E A= Electron affinity U= lattice energy

H = -Ve
Heat of formation of ionic compound is Negative.
More the negative value of the heat of formation, greater would be the stability of the ionic
compound produced.
Condition for the formation of ionic compounds
Low ionization energy (IE) of the metal.
High electron affinity (EA) of the other element.
Higher lattice energy (U) of the resulting compound.
Formation of ionic Compounds
(I) Formation of sodium chloride:

(II) Formation of magnesium Fluoride:

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 Characteristics of Electrovalent Compounds
Solids at Room Temperature: On account of strong electrostatic forces between the opposite ions, these ions
are locked in their allotted positions in the crystal lattice. Since they lack the freedom of movement
characteristic of the liquid state, they are solids at room temperature
Hard and brittle: The crystals of ionic substances are hard and brittle. Their hardness is due to the strong
electrostatic forces which hold each ion in its allotted position.
These crystals are made of layers of (+) and (–) ions in alternate positions so that the opposite ions in the
various parallel layers lie over each other. When external force is applied to a layer of ions with respect to the
next, even a slight shift brings the like ions in front of each other. The (+) and (–) ions in the two layers thus
repel each other and fall apart. The crystal cleaves her

Ionic Compounds Exist as Crystals. The (+) and (–) ions attract each other with electrostatic force that
extends in all directions. This means that ions will be bonded to a number of oppositely charged ions around
them. Therefore, in solid state, single ionic molecules do not exist as such. Rather many (+) and (–) ions are
arranged systematically in an alternating cation-anion pattern called the crystal lattice. The crystal lattice of
NaCl is shown in Fig.

Melting and Boiling Point: Due to the powerful electrostatic force between the ions in a crystal of an
electrovalent compound considerable energy is needed to overcome these forces and break down the crystal
lattice. Hence such compounds possess high melting and boiling points.
Electrical Conductivity: When an electrovalent compound is, molten or dissolved in a solvent of high
dielectric constant e.g., water, the binding forces in the crystal lattice disappear and the component ions
become mobile. Under the influence of applied electrical field, the ions get charged and thus act as charge
carrier of the current. Hence their melts or solutions conduct electricity.

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Solubility:
Ionic compounds are soluble in polar solvents like water because of molecules of the polar solvent
interact strongly with the ions of the crystal and the solvation energy is sufficient to overcome the
attraction between the ions in the crystal lattice. Dissolution is also favored by the high dielectric
constant of the solvents such as water, since this weakens the interionic attractions in the resulting
solutions.

Non-polar solvents like benzene and carbon tetrachloride do not solvate the ions as their dielectric
constants are low. Ionic compounds are, therefore insoluble in non-polar solvents.
Ionic compounds like sulphate and phosphates of barium and strontium are insoluble in water
(because lattice energy is greater than hydration energy). This can be attributed to the high lattice
energies of these compounds due to polyvalent nature of both the cation and the anion. In these cases,
hydration of ions fails to liberate sufficient energy to offset the lattice energy.
Covalent Bond
The covalent bond is formed when two atoms achieve stability by the sharing of an electron pair. The
attractive force between atoms created by sharing of an electron-pair.
The compounds containing a covalent bond are called covalent compounds.
The shared pair is indicated by a dash (–) between the two bonded atoms. A shared pair of electrons
constitutes a Covalent bond or Electron-pair bond.
The arrangement of electrons in a covalent molecule is often shown by a Lewis structure in which only

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 valency shells (outer shells) are depicted. For sake of clarity, the electrons on different atoms are
denoted by dots and crosses.

(A) Formation of hydrogen Molecule:

(B) Formation of oxygen molecule

(C) Formation of Ammonia molecule:

(D) Formation of water molecule:

(E) Formation of methane Molecule:

(F) Formation of Carbon Dioxide:

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 Characteristics of Covalent Compounds
Gases, liquids or solids at room temperature: The covalent compounds are often gases, liquids or relatively
soft solids under ordinary conditions. This is so because of the weak intermolecular forces between the
molecules.
Low melting points and boiling points: Covalent compounds have generally low melting or boiling point.
The molecules are held together in the solid crystal lattice by weak forces. On application of heat, the
molecules are readily pulled out and these then acquire kinetic energy for free movement as in a liquid. For
the same reason, the liquid molecules are easily obtained in the gaseous form which explains low boiling
points of covalent liquids.
Neither hard nor brittle: While the ionic compounds are hard and brittle, covalent compounds are neither
hard nor brittle. There are weak forces holding the molecules in the solid crystal lattice. A molecular layer in
the crystal easily slips relative to other adjacent layers and there are no ‘forces of repulsion’ like those in ionic
compounds. Thus, the crystals are easily broken and there is no sharp cleavage between the layers on
application of external force.
Soluble in organic solvent: In general, covalent compounds dissolve readily in nonpolar organic solvents
(benzene, ether). The kinetic energy of the solvent molecules easily overcomes the weak intermolecular forces.
Covalent compounds are insoluble in water. Some of them (alcohols, amines) dissolve in water due to
hydrogen-bonding.
Exhibit Isomerism: Covalent bonds are rigid and directional; the atoms being held together by shared electron
pair and not by electrical lines of force. This affords opportunity for various spatial arrangements and covalent
compounds exhibit stereoisomerism.
Molecular reactions: The covalent compounds give reactions where the molecule as a whole undergoes a
change. Since there are no strong electrical forces to speed up the reaction between molecules, these reactions
are slow.
Conductivity: Covalent substances (whether of the “molecular lattice” or “giant molecule”type) do not
conduct electricity in the fused state since there are no free electrons or ions to carry the current. However,
substances like graphite which consists of separate layers conduct electricity because the electrons have a
passage in between the two flat layers.
Co Ordinate Covalent bond
In a normal covalent bond, each of the two bonded atoms contributes one electron to make the shared pair.
In some cases, a covalent bond is formed when both the electrons are supplied entirely by one atom. Such a
bond is called co-ordinate covalent or dative bond. It may be defined as: A special type of covalent bond in
which both electrons of the shared pair of electron is provided by one of the combing atoms (or ions). The
compounds containing a coordinate bond are called coordinate compounds.
If an atom A has an unshared pair of electrons (lone pair) and another atom B is short of two electrons than
the stable number, coordinate bond is formed. A donates the lone pair to B which accepts it. Thus both A and
B achieve the stable 2 or 8 electrons, the lone pair being held in common. The atom A which donates the
lone pair is called the donor, while B which accepts it the acceptor. The bond thus established is
indicated by an arrow pointing from A to B. Although the arrow head indicates the origin of the
electrons, once the coordinate bond is formed it is in no way different from an ordinary covalent bond.

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 Some Example of Coordinate Compounds or ion
(A) Formation of Ammonium Ion:

(B) Formation of Ammonium Ion:

(C) Formation of Fluoroborate ion

(D) Addition compound of NH3 with BCl3:

(E) Formation of Sulphur dioxide and Sulphur trioxide:

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(F) Formation of Aluminium Trichloride (AlCl3), Ozone(O3), Carbon Monoxide(CO):
Aluminium atom has three valence electrons which it shares with three Cl atoms, forming three
covalent bonds. Thus, the Al atom acquires six electrons in its outer shell. Now Cl atom has three
lone pairs, one of which is donated to the Al atom of another molecule AlCl3. Thus, both Al atoms
achieve octet and stable Al2Cl6 results

[I]

[II]

[III]

Polarity of Bonds
In the H2 or Cl2 molecule, the two electrons constituting the covalent bond are equally shared by the
two identical nuclei. Due to even distribution of (+) and (–) charge, the two bonded atoms remain
electrically neutral. Such a bond is called nonpolar covalent bond. However, when two different
atoms are joined by a covalent bond as in HCl, the electron pair is not shared equally.

Due to a greater attraction of one nucleus (Cl) for the electrons, the shared pair is displaced towards
it. This makes one end of the bond partially positive ( +) and the other partially negative ( –).

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A covalent bond in which electrons are shared unequally and the bonded atoms acquire a partial positive
and negative charge, is called a polar covalent bond.
A molecule having partial positive and negative charge separated by a distance is commonly referred to as
a Dipole (two poles). The dipole of a bond is indicated by an arrow from positive to negative end with a
crossed tail as shown above in HCl molecule.
The greater the difference of electronegativity between two atoms, greater the polarity
The percentage ionic character of a bond can be calculated by using the equation

%age ionic character = 16 [XA – XB] + 3.5 [XA – XB]2 Here XA>XB

This equation is known as Hannay and Smith.

Example 1: Calculate the percentage ionic character of C–Cl bond in CCl4 if the electro negativities
of C and Cl are 3.5 and 3.0 respectively.
Solution: %age ionic character = 16 [XA – XB] +3.5 [XA + XB]2
Given XA =3.5andXB = 3.0
%age ionic character = 16 (3.5 – 3.0) + 3.5 (3.5 – 3.0)2 = 8.0 + 0.875
= 8.875%
Bond polarities affect both physical and chemical properties of compounds containing polar bond. The polarity
of a bond determines the kind of reaction that can take place at that bond and even affects the reactivity at
nearby bonds. The polarity of bonds can lead to polarity of molecules and affect melting point, boiling point
and solubility.

Dipole Moment:

It is vector quantity and is defined as the product of the magnitude of charge on any of the atom and the
distance between the atoms. It is represented by .

Magnitude of dipole moment | | q r

( charge in esu) ( Dis tan ce in )

Unit of Dipole Moment

The unit = 10–18 (esu) cm (D) is used in practice.

In SI units charge q is measured in coulombs (C) and the distance, r in metre, m

1C = 2.998 × 109 esu and 1 m = 102 cm

1 Cm = 2.998 × 109 × 102 = 2.998 × 1011 (esu) cm

Therefore in SI system, the unit of dipole moment is coulomb metre

2.998 1011
1 Cm = 2.998 10 29 D
10 18

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 1 30
or 1D 3.336 10 Cm
2,998 10 29
Experiment al dipole moment
% Ionic character of a covalent bond = 100
Theoretica l dipole moment assuming 100% ionic character
Example 2: The dipole moment of KCl is 3.336 × 10–29 Cm. The interatomic distance K+ and Cl– ion in KCl
is 260 pm. Calculate the dipole moments of KCl, if there were opposite charges of the fundamental unit
located at each nucleus. Calculate the percentage ionic character of KCl.

Solution: From the given data

q = 1.602 × 10–19C
r = 260 pm = 260 × 10–12 m = 2.6 × 10–10 m
Magnitude of dipole moment for 100% ionic character
| | = qr = (1.602 × 10–19) (2.6 × 10–10) = 4.165 × 10–29 Cm
Actual dipole moment = 3.336 × 10–29 Cm
29
3.336 10
% of ionic bond = 29
100 = 80.1%
4.165 10
The bond is 80.1% ionic.

In general, a polar bond is established between two atoms of different radii and different electronegativity
while positive centers (nuclei) of different magnitudes combine to share an electron pair. Greater the values
of the dipole moment, greater is the polarity of the bond.

The following points may be borne in mind regarding dipole moments:

In case a molecule contains two or more polar bonds, its dipole moment is obtained by the vectorial
addition of the dipole moments of the constituent bonds.
A symmetrical molecule is non-polar even though it contains polar bonds, As for example BF3 is
non polar while NH3 is polar

The dipole moment of NH3 is more than the dipole moment of NF3.

Carbon dioxide has no dipole moment ( = 0). This is possible only if the molecule has a linear structure and
the bond moments of the two C = O units cancel each other. On the other hand, SO2 has a dipole moment ( =
1.63). Evidently, here the individual dipole moments of the two S = 0 bonds are not cancelled. Thus, the
molecule has a bent structure. The vector addition of the bond moments of the two S = 0 units gives the net
dipole moment 1.63 D

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The dipole moment of ortho, meta and para:A para disubstituted benzene has zero dipole moment, while
that of the ortho isomer is higher than of meta isomer

Dipole moment of methyl chloride is a vectorial addition of dipole moments of three C – H bonds and one C
– Cl bond.

H Cl Cl

H F C C C

H H Cl Cl H H
1.75d
H Cl H
0D 0D 1.86D

Hydrogen Methane Carbon Methyl

fluoride tetrachloride chloride
Dipole moments of some molecules

Dipole moment gives valuable information about the structure of molecules. For example, carbon dioxide is
assigned a linear structure since its dipole moment is zero.
If the difference on the electronegativity scale between the two atoms is 1.9, the bond is 50% ionic in
character. When the difference is greater than 1.9, the bond is correspondingly more ionic
Fajan’s Rules
When two oppositely charged ions approach each other closely, the positively charged cation attracts the
outermost electrons of the anion and repel its positively charged nucleus. This results in the distortion or
polarization of the anion followed by some sharing of electrons between the two ions, i.e., the bond becomes
partly covalent in character.
Cation has polarizing power while anion has polarizability.
I. Charge on Either of the ions: As the charge on the cation increases, its tendency to polarize the
anion increases. This brings more and more covalent nature in the electrovalent compound.
Whereas with the increasing charge of anion, its ability to get polarized, by the cation, also increases.
For example, in the case of NaCl, MgCl2 and AlCl3 the polarization increases, thereby covalent
character becomes more and more as the charge on the cation increases.

Similarly, lead forms two chlorides PbCl2 and PbCl4 having charges +2 and +4 respectively. PbCl4
shows covalent nature. Similarly among NaCl, Na2S, Na3P, the charge of the anions are increasing,
therefore the increasing order of covalent character.

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 NaCl < Na2S < Na3P

II. Size of the cation: Polarization of the anion increases as the size of the cation decreases i.e., the
electrovalent compounds having smaller cations show more of the covalent nature. For example, in
the case of halides of alkaline earth metals, the covalent character decreases as we move down the
group. Hence melting point increases in the order of
BeCl2 < MgCl2 < CaCl2 < SrCl2 < BaCl2
III. Size of anion: The larger the size of the anion, more easily it will be polarized by the cation i.e., as
the size of the anion increases for a given cation, the covalent character increases. For example, in
the case of halides of calcium, the covalent character increases from F– anion to I– anion i.e.
CaF2 CaCl2 CaBr2 CaI2
increasing covalent character
Similarly, in case of trihalides of aluminium, the covalent character increases with increase in size
of halide anion i.e.
AlF3 AlCl3 AlBr3 AlI3
Covalent character increases as the
size of the halide ion increases
IV. Nature of the cation: Cations with 18 electrons (s2p6d10) in outermost shell polarize an anion more
strongly than cations of 8 electrons (s2p6) type. The d electrons of the 18-electron shell screen the
nuclear charge of the cation less effectively than the s and p electrons of the 18-electron shell. Hence
the 18-electron cations behave as if they had a greater charge. Copper (I) and Silver (I) halides are
more covalent in nature compared with the corresponding sodium and potassium halides although
charge on the ions is the same and the sizes of the corresponding ions are similar. This illustrates the
effect of 18-electron configuration of Cu+ (3s2, p6, d10) and Ag+ (4s2, p6, d10) ions.

Illustration 4: The decomposition temperature of Li2CO3 is less than that of Na2CO3. Explain.

Solution: As Li+ ion is smaller than Na+ ion, thus small cation (Li+) will favour more covalent
character in Li2CO3 and hence it has lower decomposition temperature than that of Na2CO3.

CLASS WORK:
SnCl2 is solid whereas SnCl4 is liquid, why?
Hydrogen Bonding

In 1920, Latimer and Rodebush introduced the idea of “hydrogen bond” to explain the nature of association
in liquid state of substance like water, hydrogen fluoride, ammonia, formic acid etc. In a hydrogen compound,
when hydrogen is bonded to highly electronegative atom (such as F, O, N) by a covalent bond, the electron
pair is attracted towards electronegative atom so strongly that a dipole results i.e., one end carries a positive
charge (H-end) and other end carries a negative charge (X-end).

The electrostatic attraction between an H atom covalently bonded to a highly electronegative atom X and a
lone pair of electrons of X in another molecule, is called Hydrogen Bonding

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 Types of Hydrogen bond
Intermolecular hydrogen bonding: This type of bonding results between the positive and negative ends of
different molecules of the same or different substances.

i) Ammonia

ii) Water

iii) Acetic acid

Intramolecular hydrogen bonding: This type of bonding results between hydrogen and an electronegative
element both present in the same molecule. This type of bonding is generally present in organic compounds.
Examples are o-nitro-phenol, o-hydroxy benzoic acid, etc.
This type of hydrogen bonding is formed between the hydrogen atom and the electronegative atom present
within the same molecule. It results in the cyclisation of the molecule. Molecules exist as discrete units and
not in associated form. Hence intramolecular hydrogen bonding has no effect on physical properties like
melting point, boiling point, viscosity, surface tension, solubility etc. For example, intramolecular hydrogen
bonding exists in o-Nitro phenol, 2-Nitrobenzoic acid etc. as shown below:

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 Properties Explained by Hydrogen Bonding
(I) Abnormally high Boiling and Melting points
The compounds in which molecules are joined to one another by hydrogen bonds, have unusually
high boiling and melting points. this is because here relatively more energy is required to separate
the molecules as they enter the gaseous state or the liquid state.
The hydrides of fluorine (HF), oxygen (H2O) and nitrogen (NH3) have abnormally high boiling and
melting points compared to other hydrides of the same group which form no hydrogen bonds.
It will be noticed that there is a trend of decrease of boiling and melting points with decrease of
molecular weight from H2Te to H2S. but there is a sharp increase in case of water (H2O), although
it has the smallest molecular weight. The reason is that the molecules of water are ‘associated’ by
hydrogen bonds between them, while h2te, h2se and h2s exist as single molecules since they are
incapable of forming hydrogen bonds.

CHEMICAL BONDING - LEWIS THEORY 173

o H2 O
100

Melting
Boiling
points
points
Temperature C

H2Te
o

H2Se
o
H2O
0 H2S

H2Te

H2Se
H2 S
o
–100

0 60 120
Molecular weights
Figure 5.8
(II) High solubilityBoiling and melting
of Some point curves
Covalent of the hydrides of VIA group showing abrupt
Compounds
increase for water (H2O) although it has the lowest molecular weight.
The unexpectedly high solubility of some compounds containing O, N and F, such as NH3 and CH3OH in
(2) High solubilities of some covalent compounds
certain hydrogen Thecontaining
unexpectedlysolvents are due
high solubilities to hydrogen
of some bonding.O,For
compounds containing N andexample, ammonia
F, such as NH (NH3) and
3 and
CH3OH)
methanol (CH 3 OH in are
certain hydrogen
highly containing
soluble solvents
in water asare dueform
they to hydrogen bonding.
hydrogen For example, ammonia
bonds.
(NH3) and methanol (CH3OH) are highly soluble in water as they form hydrogen bonds.

H Hydrogen bond H Hydrogen bond

H N H O H C O H O

H H H H H
Ammonia Water Methanol Water

(3) Three dimensional crystal lattice

Strength of certain acids and
As already stated,bases can bonds
hydrogen be explained on the
are directional andbasis
prettyof hydrogen
strong to formbonding.
three dimensional
crystal lattice. For example, in an ice crystal the water molecules (H2O) are held together in a tetrahedral
(III) Three-dimensional crystal lattice
network and have the same crystal lattice as of diamond. This is so because the O atom in water has
As already stated, hydrogen
two covalent bonds and bonds aretwo
can form directional and These
hydrogen bonds. prettyarestrong to in
distributed form
spacethree-dimensional
like the four crystal
covalent bonds
lattice. For example, in an of ice
carbon. The tetrahedral
crystal the waterstructural
moleculesunits (H2O)
are linked to other
are heldunits throughinhydrogen
together a tetrahedral network
bonds as shown in Fig. 5.6.
and have the same crystal lattice as of diamond. This is so because the O atom in water has two covalent
Since there is enough empty space in its open lattice structure ice is lighter than water, while most
bonds and can form two hydrogen bonds. These are distributed in space like the four covalent bonds of
other solids are heavier than the liquid form.
carbon. The Water
tetrahedral structural units are linked to other units through hydrogen bonds. Since there is
as an Interesting Liquid
Water is very interesting solvent with unusual properties. It dissolves many ionic compounds
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and polar organic compounds. It has high heat of vaporisation, high heat of fusion, high specific heat
enough empty space in its open lattice structure ice is lighter than water, while most other solids are heavier
than the liquid form.

(IV) Maximum density of water at 277 K (4oC)

On melting ice, the hydrogen bonds break and water molecules occupy the vacant spaces. This results in
decrease in volume and increase in density (d = m/v). Hence density of water keeps on increasing when water
is heated. This continues up to 277 K (4oC). Above this temperature water molecules start moving away from
one another due to increase in kinetic energy. Due to this volume increases again and density starts decreasing.
This behaviour of water is shown in the fig. 5.9.

(V) Ice has less density than water. The explanation of this fact is as follows: In the crystal structure of ice, the
O-atom is surrounded by four H-atoms. Two H-atoms are linked to O-atom by covalent bonds as shown (by
normal covalent bond) and the remaining two H-atoms are linked to O-atom by two H-bonds shown by dotted
lines. Thus in ice every water molecule is associated with four other water molecules by H-bonding in a
tetrahedral fashion. Ice has an open cage like structure with a large empty space due to the existence of H-
bonds. As ice melts at 0°C, a number of H-bonds are broken down and the space between water molecules
decreases so that water molecules move closer together. The density of water increases, from 0° to 4°C, and
at 4°C it is maximum. Above 4°C the increase in kinetic energy of the molecules is sufficient to cause the
molecules to begin to disperse and the result is that the density decrease with increasing temperature.

H H

2.76 Å 1.80Å

-
H Open cage-like tetrahedral crystal structure
of ice. Circles indicate oxygen atoms.
0.96Å
0.96Å
Bonds represented by solid line are normal
covalent bonds while those represented by
water molecule dotted lines are hydrogen bonds.
H
H H

H H
H

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 Although HF forms stronger hydrogen bond than H2O, Hv of H2O is greater than that of HF why?
The Quantum Mechanical Model
At present, two quantum mechanical theories are used to describe covalent bond formation and the electronic
structure of molecules.
I- Valence Bond Theory II-Molecular Orbital Theory.
Valence Bond Theory

This theory was proposed by Linus Pauling, who was awarded the Noble Prize for Chemistry 1954.

Atoms with unpaired electrons tend to combine with other atoms which also have unpaired electrons. In this
way, the unpaired electrons are paired up, and the atoms involved, all attain a stable electronic arrangement.
This is usually a full shell of electrons (i.e. a noble gas configuration).
Two electrons shared between two atoms constitute a bond. The number of bonds formed by an atom is
usually the same as the number of unpaired electrons in the ground state, i.e. the lowest energy state.
However, in some cases the atom may form more bonds than this. This occurs by excitation of the atom
(i.e. providing it with energy) when electrons which were paired in the ground state are unpaired and
promoted into suitable empty orbitals. This increases the number of unpaired electrons, and hence it
increases number of bond which can be formed.

Heitler and London believed that electron cloud of the valence orbital on one atom ‘overlaps’ the electron
cloud of the other bonding atom to form a covalent linkage.

The theory of ‘maximum overlap’, affords an excellent interpretation of covalent bond formation. The
essential conditions for the overlap of electron waves of orbitals are:

I-The orbitals entering into combination must have only one electron or unpaired electron.i.e.the no of
covalent formed by an atom of an element is always equal to the no of unpaired electron.

II-The atoms with valence or bonding orbital (half-filled) should approach sufficiently close to one another
with the axis of their orbitals in proper alignment. i.e.

The strength of a covalent bond depends upon the extent of overlapping. Greater the overlapping
between the atomic orbitals stronger is the bond formed between the two atoms.
A stronger bond has, therefore, a shorter bond length.
Since the overlapping of atomic orbitals involves a release of energy, it must produce a stabilizing
effect on the system. The merger or overlapping of the atomic orbitals halts at a stage when the atomic
nuclei have come close enough to exercise a repulsive force on one another, which exactly balances
the force of merger. This equilibrium distance at which the two atomic nuclei are now held is called
the Bond length.

Formation of hydrogen Molecule

Energy Diagram of s-s overlap:

As the two atoms approach closer and closer for the overlap of half-filled 1s orbitals on them, the energy of
the system goes on decreasing till it registers a minimum. At this point the overlapping halts, since the positive
cores (nuclei) of the two atoms are apart by a certain equilibrium distance, the stabilizing effect of overlapping

| FIITJEE - DPS-MIS-DOHA, Q ATAR

is completely balanced by the repulsion between the positive nuclei. Beyond this point the energy of repulsion
predominates and there is a steep rise in the energy curve with a further decrease of internuclear distance.

Sigma and Pi Bonds ( and Bonds)

A covalent bond is formed by the overlapping of atomic orbitals. Covalent bonds formed are of two types
depending upon the way the orbitals overlap each other.

Sigma bond ( -bond): The bond formed by the overlapping of two half-filled atomic orbitals along their axis
is known as sigma bond. Bond is a strong bond because overlapping in it takes place to large extent. The
hybrid orbitals always from bond.

a) s – s overlapping

b) s – p overlapping

c) p – p overlapping

| FIITJEE - DPS-MIS-DOHA, Q ATAR

2. Pi bond ( bond): The bond formed by the lateral overlapping of half-filled atomic orbitals is known
as pi bond. The sidewise overlapping takes place to less extent. Therefore, bond formed is a weak
bond. bond overlapping takes place only at the sides of two lobes. A bond is formed when a
bond already exists between the combining atoms.

Orbital representation of some molecule

(i) Formation of F2 molecule-

Fluorine atom has electron configuration 1s2 2s2 2px2 2py2 2pz1. The unpaired electron in 2pz orbital of one
atom overlaps with similar orbital of other Fluorine atom along internuclear axis leading to the formation of
σ bond.
(ii) Formation of Oxygen Molecule

Oxygen (at. no. 8) atom has electronic configuration 1s2 2s2 2px2 2py1 2pz1. In the formation of O2 molecule
2pz orbital of one oxygen atom overlaps with the similar orbital of the other atom along internuclear axis
leading to the formation of a sigma (σ) bond. The other 2py orbital of one oxygen atom overlaps with the
similar orbital of another oxygen atom in sidewise manner forming a pi (π) bond. Thus an oxygen molecule
contains a double bond consisting of a sigma (σ) bond and a pi (π) bond.

| FIITJEE - DPS-MIS-DOHA, Q ATAR

(iii) Formation of Nitrogen Molecule

Nitrogen atom has three bonding electrons 2px1 2py1 2pz1 is its valence shell. These electrons are present in
three p-orbitals which are directed along three axes at right angles. When two N atoms approach each other,
2pz orbitals overlap in head-on manner to form a sigma (σ) bond, leaving two sets of parallel 2py and 2px
orbitals. Now the electron clouds in these orbitals interact to produce two pi (π) bonds by the sidewise
overlaps. Thus in N2 molecule two N atoms are bonded by a triple bond consisting of one sigma (σ) and two
pi (π) bonds. The orbital overlap in N2 molecule is shown in figure

Hybridization
It is the mathematically fabricated concept that is introduced to explain the geometry/shapes of the covalent
molecules of polyatomic ions containing covalent bonds.

Thus hybridization may precisely be defined as the phenomenon of mixing up (or merging) of orbitals of
an atom of nearly equal energy, giving rise to entirely new orbitals equal in number to the mixing orbitals
and having same energy contents and identical shapes

Rules of hybridization
For hybridization to occur, it is necessary for the atom to satisfy the following conditions:
1. Orbitals on a single atom only would undergo hybridization.
2. There should be very little difference of energy level between the orbitals mixing to form hybrid orbitals.
3. Number of hybrid orbitals generated is equal to the number of hybridizing orbitals.
4. The hybrid orbitals assume the direction of the dominating orbitals.
For example, if s and p orbitals are to hybridize, the s orbital having no directional character, does not
contribute towards the direction when p orbitals determine the directional character of the hybrid orbitals.
5. It is the orbitals that undergo hybridization and not the electrons.
For example, four orbitals of an oxygen atom (2s2, 2px2 , 2 py1 , 2 pz1 ) belonging to second level (i.e., 2s,|
2px, 2py, 2pz) can hybridize to give four hybrid orbitals, two of which have two electrons each (as before)
and the other two have one electron each.
6. The electron waves in hybrid orbitals repel each other and thus tend to be farthest apart.

| FIITJEE - DPS-MIS-DOHA, Q ATAR

 Types of hybridization

(A) sp-hybridization:

The mixing of an s and a p orbital only leads to two hybrid orbitals known as sp hybrid orbitals after the
name of an s and a p orbital involved in the process of hybridization. The process is called sp hybridization.
Each sp orbital has 50%, s-character and 50% p-character. Orbitals thus generated are the seat of electrons
which have a tendency to repel and be farther apart. In order to do so the new orbitals arrange themselves
along a line and are, therefore, often referred to as linear hybrid orbitals. This gives an angle of 180o
between the axes of the two orbitals. It is clear from Fig. that a sp orbital has two lobes (a character of p
orbital) one of which is farther than the corresponding s or p orbitals and also protrudes farther along the axis.
It is this bigger lobe that involves itself in the process of an overlap with orbitals of other atoms to form
bonds. It will be seen later on that the smaller lobes of hybrid orbitals are neglected while considering bond
formation.
(B) Sp2- hybridization:

| FIITJEE - DPS-MIS-DOHA, Q ATAR

 Ground State Excited State Hybridized state

Figure 6.15
Excited
Formation atom undergoing sp 2 hybridization leaves a pure 2p z orbital.
carbon molecule:
of Ethene
pz pz
H σ H σ
σ σ H H
σ
C σ
sp 2 C sp 2 C C
sp 2 sp 2
sp 2 sp 2
CHEMICAL BONDING – ORBITAL THEORY 209
σ σ H H
H predict about the H–N–H bond angles
can H is that they are 90º, the angle between the axes.
Ethene But this
(Ethylene)
is erroneous and does (a)
not agree with the experimental value(b)of 107º. The anomaly can (c)
be explained
satisfactorily
Figure 6.16
employing (a) the concept of hybrid orbitals and (b) the electron pair interactions.
Shape of ammonia molecule:
Orbital model of ethene molecule. (a) shows scheme of overlaps; (b) shows the bonds, sigma
bonds indicated by straight lines; and (c) shows ball-and-stick model of ethene (ethylene).
Lone pair Lone pair

Bond pair
N N N
H H H o H
107
H H
H H H Ammonia

Figure 6.19
When an Orbital
s and two p orbitals
overlaps mix up to
in the formation of hybridize, there result three new orbitals called sp2 hybrid
ammonia molecule.
orbitals (spoken as ‘sp two’). Each sp2 hybrid orbital has 33% s-character and 67% p-character. As
(a) sp3 Hybridization in ammonia molecule
the three orbitals undergoing hybridization lie in a plane, so do the new orbitals. They have to lie
It is assumed that the valence orbitals of the central N-atom undergo hybridization before
farthestaffecting
apart in overlaps
a plane with
which 1s can happen
orbitals if they are
of hydrogen. Whendirected at anofangle
the orbitals 120oenergy
the second to onelevel
another
of as shown
in Fig. ItN-atom
is for (2s
this 1
2, reason 1
2 p x , 2 pthat 1
y , 2 psp
2 hybridsporbitals
z ) undergo are alsofour
3 hybridization, called
new Trigonal result. the
hybrids,
hybrid orbitals One process
of being
referredthese
to aswill have twohybridization.
Trigonal electrons (like theThe
original
sp2atom) andorbitals
hybrid is non-bonding while
resemble inthe otherwith
shape threethat
haveof sp hybrid
one electron each and can form bonds by overlap. Now these hybrid orbitals are tetrahedrally
orbitalsdispersed
but are slightly fatterof
with an angle . 109.5º between them. After hybridization, let the 1s orbitals of three
H-atoms overlap to form three bonds (Fig. 6.21a). The tetrahedral angle 109.5º is quite near the
(C) Sp3 hybridization
experimental value 107º, and a difference of 2.5º can be explained by taking into consideration the
electron pair interactions.
CHEMICAL BONDING – ORBITAL THEORY 207
2p
Lone pair

H sp 3
Energy

H
Hybridization
sp 3 sp3 Hybrid orbitals
o
sp 3 sp 3 109.5
C2s C

H Isolated
H N atomH H N Atom in ammonia
sp 3
Figure 6.20
H H
sp 3 Hybridization of valence orbitals of N-atom. Methane
Figure 6.14
In ground
(b) state, the pair
Electron electronic
Shaperepulsion configuration
and formation of methane carbon is 1s2, 2s2, 2p2. It is proposed that from 2s orbital,
ofmolecule.
being quiteWe near
have inseen
energy to symmetrical
that the 2p orbitals,central
(b) sp2 Hybridization of Carbon
one electron
N-atom has mayin itsbevalence
promoted to thebond
shell, three vacant
pairs 2p z orbital thus
(bp),
each shared
obtaining the excited with one of the three H-atoms, and also a lone pair (lp) of electrons. The three bond pairs
Whenatom.
three outAt thisfourstage
of the valence the carbon
orbitals atomweundoubtedly
hybridize, has orbitals
have three sp2 hybrid four half-filled
lying in orbitals and
and one alone
plane
pair
and
may get arranged
inclined at an angle
tetrahedrally
of 120º. If 2s,
about
2p and
the
2p
central
orbitals
atom.
of the
The central
excited carbon
atom
atom
exercises
are
can form four bonds.
different In theThe
pulls on them. excited
lone lie
pairatom, all the four
x valence
y shell orbitals maypairsmix up to give four
hybridized, the new orbitals in is
theattracted more
xy plane while towards
the the N-atom
fourth pure 2pz orbitalthan
lies the bond
at right angles towhich
3 3
identicalbelongs
sp hybrid
to the
the orbitals.
H-atoms
hybridized andEach
orbitals withof
N-atom its these
jointly.
two four
lobes This sp orbital
is because
disposed above of possesses
andthe factthe
below one
thatplane electron
the lone
of and overlaps
pair orbitals.
hybrid belongs only with 1s
to the N-atom
Two and
such hence
carbon its
atoms electron
are involved
orbitals of four H atoms thus forming four equivalent cloud
in is
the more
formation concentrated
of alkenes near
(compounds the N-atom.
having The
double lone
bonds).
bonds in methane molecule. Due to the pair is,
In capable
therefore, the formation of ethenea two
of exerting carbon
greater atoms (inon
repulsion sp2a hybridization
bond pair than state) form one
a bond pairsigma bond by
can repel another
3
tetrahedral
bonddisposition
‘head-on’
pair. of three
overlap
As a result spof two
hybrid
bonds oforbitals,
sp2 orbitals the
contributed
ammonia orbital
one each
molecule are
areby theinclined
forced atoms. at
twoslightly The an angle
remaining
closer of
than intwo 109°
thesp
2
normal 28’. Thus all
the H– C– H angles
tetrahedral are equalTherefore
arrangement. to 109°each 28’ of the HNH bond angles is 107º rather than the anticipated
2p 2p 2p

Promotion sp2
Energy

of electron Hybridization
sp2 Hybrid
orbitals
2s 2s
| FIITJEE - DPS-MIS-DOHA, Q ATAR
Ground State Excited State Hybridized state
 to repel each other more strongly than do a lone pair and a bond pair, and of course, even more
strongly than two bond pairs. As a result, the two lone pairs of water force the two (O–H) bond pairs
closer together than the one lone pair in case of ammonia forces together the three (N–H) bond pair.
Thus the HOH angle is smaller (104.3º) than the HNH bond angles of 107º. In the light of the above
Formation of water
discussions we canmolecule:
explain the molecular geometry of PH3, PCl3, NF3, H2S, etc.

Lone pair Lone pair

Bond pair

O O

H 104.3
o
H
H
Water
H
H H
(a) (b) (c)
Types of hybridization and spatial orientation of hybrid orbitals: The geometry and shapes of various
Figure 6.24
species on the basis of VSEPR theory along with hybrid state of central atom is given below in tabular form.
Tetrahedral model of water molecule showing two lone
pairs orbitals
Types of atomic on O-atom; (c) shows bp-bp, lp-bpOrientation
and lp-lp repulsions.
of
Hybridization Examples
used hybrid orbitals
1. 3d
one s + one p-orbital sp 3d
Linear BeF2 , BeCl 2 , C 2 H 2 , HgCl 2
2 Trigonal sp3d
2. one s + two p-orbitals sp
Promotion BF3 , C 2 H 4 , NO 3 , CO 32
3p 3p planar Hybridization
of electron 3
Energy

sp d Hybrid orbitals
3. one s + three p-orbitals sp 3 Tetrahedral CH 4 , CCl 4 , SiF4 , NH 4 , SO 24 , ClO4
Trigonal
4. one s + three p3s+ d sp 3 d 3s PF5 , PCl 5
bipyramidal
Ground State Excited State Hybridized State
5. one s + three p + two d sp 3 d 2 Octahedral SF5 , [CrF6 ]3 , IF5
Figure 6.25 Pentagonal
6. one s + three p+three d sp 3 d 3 IF7
Various states of Phosphorus atom with its orbitals undergoing sp3d hybridization.
Bipyramidal
Shape of Phosphorus pentachloride molecule, PCl5 Only in complexes like
7. One d + one s + two p dsp 2 Square planar
In PCl5 molecule, phosphorus is the central atom which has [ Ni(the ) 4 ) 2 , [PtCl
CNelectronic 2
configuration
4] etc.
2 2 6 2 3 0
1s , 2s , 2p , 3s , 3p , 3d . In the ground state, it has only three bonding orbitals in the valence
shell. One of the two 2s electrons uncouples itself and is promoted to the 3d orbital. The orbitals
Note: i) Orbitals
nowparticipating
hybridize ininaccordance
hybridization must
with sp3have only
d type assmall difference
follows. Three inoftheir energies.
these five bonding orbitals
ii) Both half-filled and completely filled orbitals can get involved in hybridization.
iii) The number of hybrid orbitals is equal to the number of orbitals participating in hybridization.
iv) Hybrid orbital form stronger bonds than pure atomic orbitals.
v) Same atom can assume different hybrid states under different situations.
vi) Hybrid orbitals form sigma bonds.

Method of predicting the Hybrid state of the central atom in covalent molecules of polyatomic ions:
The hybrid state of the central atom in similar covalent molecule or polyatomic ion can be predicted by using
the generalized formula as described below:
Simple Molecule Polyatomic Anion Polyatomic Cation
1 1 1
X [V G ] X [V G a ] X [ V G c]
2 2 2
In the above formulae,
V = Number of monovalent atoms or groups attached to the central atom
G = Number of outer shell electrons in ground state of the central atom
a = Magnitude of charge on anion
c = Magnitude of charge on Cation
Calculate the value of X and decide the hybrid state of central atom as follows:

| FIITJEE - DPS-MIS-DOHA, Q ATAR

 X 2 3 4 5 6 7
2 3 3 3 2
Hybrid state sp sp sp sp d sp d sp 3 d 3
PF5 COCl2 NH 4 ClO 4
1 1 1 1
X 2 [5 5] X 2 [2 4] X 2 [4 5 1] X 2 [0 7 1]
=5 =3 =4 =4
Hybrid state of P is Hybrid state of C is sp 2 Hybrid state of N is sp 3 Hybrid state of Cl is
sp 3 d sp 3
NO 3 IF5 CO 2 XeF4
1 1 1 1
X 2 [0 5 1] X 2 [5 7] X 2 [0 4] X 2 [ 4 8]
=3 =6 =2 =6
sp 2
sp d3 2 sp sp 3 d 2
PCl 6 PH3 SF3 SF4
1 1 1 1
X 2 [6 5 1] X 2 [3 5] X 2 [3 6 1] X 2 [4 6]
=6 =4 =4 =5
Hybrid state Hybrid state Hybrid state Hybrid state
sp 3 d 2 sp 3 sp 3 sp 3 d

Geometries of Molecules
So far we have depicted molecules by Lewis structures in the flat plane of paper. But all molecules containing
three or more atoms are three-dimensional. The shape of a particular molecule is determined by the specific
arrangement of atoms in it and the bond angles. Molecular shapes may be linear, bent (or angular), trigonal
planar, pyramidal or tetrahedral.
The shapes of molecules can be determined in the laboratory by modern methods such as X-ray and electron
diffraction techniques. Molecular shapes are important because they are helpful in the investigation of
molecular polarity, molecular symmetry or asymmetry. Physical and chemical properties of compounds
depend on these factors. VSEPR theory throws light on the three-dimensional shapes of molecules.
VSEPR Theory
The Lewis structure of a molecule tells us the number of pairs of electrons in the valence shell of the central
atom. These electron pairs are subject to electrostatic attractions between them. On this basis, R.G. Gillespie
(1970) proposed a theory called the Valence-Shell Electron Pair Repulsion or VSEPR (pronounced as
‘Vesper’) theory. It states that: The electron pairs (both lone pairs and shared pairs, surrounding the central
atom will be arranged in space as far apart as possible to minimise the electrostatic repulsion between them.

Let us consider the simplest case of an atom with two electron pairs. We wish to place the electron pairs on
the surface of a sphere such that they will be as far apart as possible so as to minimise repulsion between
them. The above figure illustrates it by showing some possible placements of the two electron pairs. The
arrangement in which the electron pair-central atom-electron pair angles is 180o, makes the electron pairs
farthest apart. This arrangement is called linear because the electron pairs and the central atom are in a
straight line.

| FIITJEE - DPS-MIS-DOHA, Q ATAR

VSEPR theory is simple but remarkably powerful model for predicting molecular geometries and bond
angles. While working out the shapes of molecules from this theory, it must be remembered:
The theory was developed extensively by Gillespie as the Valence Shell Electron Pair Repulsion (VSEPR)
theory. This may be summarized as:

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

2. Lone pair - lone pair repulsion > lone pair – bond pair repulsion > bond pair – bond pair repulsion.

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
a double bond.

Effect of Lone Pairs: Molecules with four electron pairs in their outer shell are based on a tetrahedron. In
CH4 there are four bonding pairs of electrons in the outer shell of the C atom, and the structure is a regular
tetrahedron with bond angle H – C – H of 109°28’. In NH3 and N atom has four electron pairs in the outer
shell, made up of three bond pairs and one lone pair. Because of the lone pair, the bond angle H – N – H is
reduced from the theoretical tetrahedral angle of 109°28’ to 107°28’. In H2O the O atom has four electron
pairs in the outer shell. The shape of the H2O molecule is based on a tetrahedron with two corners occupied
by bond pairs and the other two corners occupied by lone pairs. The presence of two lone pairs reduces the
bond angle further to 104°27’.

In a similar way, SF6 has six bond pairs in the outer shell and is a regular octahedron with bond angles of
exactly 90°. In BrF5, the Br also has six outer pairs of electrons, made up of five bond pairs and one lone pair.
The lone pair reduces the bond angles to 84°30’. Whilst it might be expected that two lone pairs would distort
the bond angles in an octahedral as in XeF4 but it is not so. Actual bond angle is 90°, reason being that the
lone pairs are trans to each other in the octahedron, and hence the atoms have a regular square planar
arrangement.

Molecules with five pairs of electrons are all based on a trigonal bipyramid. Lone pairs distort the structures
as before. The lone pairs always occupy the equatorial positions (in a triangle), rather than the axial positions
(up and down). Thus in I 3 ion, the central I atom has five electron pairs in the outer shell, made of two bond
pairs and three lone pairs. The lone pairs occupy all three equatorial positions and the three atoms occupy the

| FIITJEE - DPS-MIS-DOHA, Q ATAR

top, middle, and bottom positions in the trigonal bipyramid, thus giving a linear arrangement with a bond
angle of exactly 180°.

Effect of Electronegativity: NF3 and NH3 both have structures based on a tetrahedron with one corner
occupied by a lone pair. The high electronegativity of F pushes the bonding electrons further away from N
than in NH3. Hence the lone pair in NF3 causes a greater distortion from tetrahedral and gives a F – N –
F bond angle of 102°30’, compared with 107°48’ in NH3. The same effect is found in H2O (bond angle
104°27’) and F2O (bond angle 102°).

The effects of bonding and lone pairs on bond angles

Orbitals on central Number of Number of
Shape Bond angle
atom bond pairs lone pairs
BeCl2 2 Linear 2 0 180°
BF3 3 Plane triangle 3 0 120°
CH4 4 Tetrahedral 4 0 109°28
NH3 4 Pyramidal 3 1 107°48
NF3 4 Pyramidal 3 1 102°30
H2O 4 Bent (V-shape) 2 2 104°27
F2O 4 Bent (V-shape) 2 2 102°
PCl5 5 Trigonal bipyramid 5 0 120° and 90°
SF4 5 Trigonal bipyramid 4 1 101°36 and 86°33
ClF3 5 T-shape 3 2 87°40
XeF2 5 Linear 2 3 180°
SF6 6 Octahedral 6 0 90°
BrF5 6 Square pyramidal 5 1 84°30
XeF4 6 Square planar 4 2 90°

Some examples using the VSEPR Theory

Phosphorus pentachloride PCl5: Gaseous PCl5 is covalent. (The electronic structure P

is 1s22s22p63s23p3). All five outer electrons are used to form bonds to the five Cl
atoms. In the PCl5 molecule the valence shell of the P atom contains five electron
pairs: hence the structure is a trigonal bipyramid. There are no lone pairs, so the
structure is not distorted. However, a trigonal bipyramid is not a completely regular
structure, since some bond angels are 90° and others 120°. Symmetrical structures are
usually more stable than asymmetrical ones.

Note: Thus PCl5 is highly reactive, and in the solid state it splits into [PCl4]+ and
[PCl6]– ions, which have tetrahedral and octahedral structures respectively.
Chlorine trifluoride ClF3: The chlorine atom is at the center of the molecule and determines its shape. The
electronic configuration of Cl is 1s22s22p63s23p5. Three electrons form bonds to F, and four electrons do not
take part in bonding. Thus in ClF3, the Cl atom has five electron pairs in the outer shell, hence the structure is
a trigonal bipyramid. There are three bond pairs and two lone pairs.

It was noted previously that a trigonal bipyramid is not a regular shape since the bond angles are not all the
same. It therefore follows that all the corners are not equivalent. Lone pair occupy two of the corners, and F

| FIITJEE - DPS-MIS-DOHA, Q ATAR

 atoms occupy the other three corners. Three different arrangements are theoretically possible, as shown in
figure below.

The most stable structure will be the one of lowest energy, that is the one with the minimum repulsion between
the five orbitals. The great repulsion occurs between two lone pairs. Lone pair bond pair repulsions are next
strongest, and bond pair-bond pair repulsions are weakest. Groups at 90° repel each other strongly, whilst
groups 120° apart repel each other much less.
F F

F F F F
Cl Cl Cl

F F

F
I II III
Chlorine trifluoride molecule

Structure I is the most symmetrical, but has six 90° repulsions between lone pairs and atoms. Structure II has
one 90° repulsion between two lone pairs, plus three 90° repulsions between lone pairs and atoms. These
factors indicate that structure III is the most probable. The observed bond angles are 80°40 , which is close to
the theoretical 90°. This confirms that the correct structure is III, and the slight distortion from 90° is caused
by the presence of the two lone pairs.

As a general rule, if lone pairs occur in a trigonal bipyramid they will be located in the equatorial position
(round the middle) rather than the axial positions (top and bottom), since this arrangement minimizes repulsive
forces.

Sulphur hexafluoride SF6: The electronic structure of S is 1s22s22p63s23p6. All

six of the outer electrons are used to form bonds with the F atoms. Thus in SF6,
the S has six electron pairs in the outer shell: hence the structure is octahedral.
There are no lone pairs, so the structure is completely regular with bond angles
of 90°.

214 6 PHYSICAL CHEMISTRY

Molecular Orbital Theory

Why He2 molecule does not exist and why O2 is paramagnetic? These questions cannot be explained by
valence bond theory. In 1932 F. Hund and R.S. Mullikan put forward a theory known as Molecular Orbital
Theory to explain above questions and many others.
According to this method, the molecular orbitals are formed by the linear combinatio
subtraction) oftheory,
According to this atomic orbitals
as the electronsofofthe constituent
an atom are presentatoms of atomic
in various the molecule. Let usofconside
orbitals, electrons a
molecule are present in various molecular orbitals.
case of H2 molecule consisting of two hydrogen atoms represented by HA and HB
orbitals of these atoms are represented by the wave functions and B.orbital, Whenitthese
Molecular orbitals are formed by the combination of atomic orbitals of comparable energy and proportional
symmetry. While an electron in atomic orbital is influenced by one nucleus, in aAmolecular is
at
each otherby there
influenced come
two or more twodepending
nuclei possibilities.
upon the number of atoms in the molecule.

(1) Molecular
A molecular orbitalbyistheformed
orbital is formed additionby the addition
of wave function of of wave
atomic functions
orbital known as ofbonding
atomic orbi
molecular orbital it can be represented by
represented by
(MO) = A + B
The M.O.
Molecular orbital formed
formed byissubtraction
called bonding
of wave molecular orbital.
function of atomic It lowers
orbital, known asthe energy and br
anti-bonding
molecular orbitals. It is represented by
stability in the system.
(2) Molecular orbital is formed by the subtraction of wave functions of atomic orb
| FIITJEE -
represented by DPS-MIS-DOHA, Q ATAR
 (2) energy
Molecular
is formed. Theexample,
For MO formed
state. It
orbital
when
has net
twois
is called 1sformed
antibonding
disruptive
by
orbitals combine
effect. That is
the
why
subtraction
moleculartwo
orbital.
new This
this MO
molecular
is termed
of
type of MO
wave
orbitals
as
arefunctions
corresponds to higher
formed.
antibonding
of atomic
One of
molecular
these pertains to the bonding molecular orbital with lower energy while the other corresponds to
represented
higher energyby
orbital, distinguished by attaching an asterisk (*) mark with the symbolic name of the molecular
as compared to both the atomic orbitals concerned in the process. Thus we find that
orbital. The molecular orbitals formed by the combination of 1s orbitals of two hydrogen atoms is
orbitals formed*from atomic
(MO) = A –
the number
shownofbelow
molecular
: orbitals is equal to the number of atomic orbitals
B
responsible for their formation and are of two types as shown below. (Fig. 6.30)
The MO formed is called antibonding molecular orbital. This type of MO cor
*(Is)
energy state. It has net disruptive effect. That is
Antibonding MOwhy this MO is termed as antib
* (Is)

orbital, distinguished by attaching an asterisk (*) mark with the symbolic name
orbital. The molecular orbitals formed by the combination of 1s orbitals of two h
shown below : (Is)

Figure 6.29
CHEMICAL BONDING – ORBITAL THEORY 215
Energy

Formation of molecular orbitals from two Is orbitals of hydrogen atoms.

RelativeTheEnergies of bondingeither
wave functions and
Is antibonding
have (+) orMOs (–) sign. The positive sign shown on Is 1s orbitals of
An atomic We have
orbital
hydrogen seen Atomic
above that
that when
is monocentric
atoms shows orbital
whileatomic
these orbitals
a molecular
orbitals combine,
orbital
are spherically an equivalent
is symmetrical
polycentric. The
and Atomic
number
number
their waveorbital
of new orbitals areorbitals
offunctions
molecular *
isassociated
formed formed.
is equalForwith +ve sign in all directions. In case of p-orbitals one lobe has +ve sign whileOne
to example,
the when
number oftwo 1s orbitals
combining combine
atomic two new
orbitals. molecular orbitals are formed. otherof has
these pertains
–ve sign. Thetooverlapping
the bondingofmolecular orbitaltakes
atomic orbitals with place
lowerifenergy whilesimilar
they have the other
signscorresponds to
on their lobes.
BMOhigher energyenergy
has lower as compared to both
and hence the atomic
greater orbitals
stability thanconcerned in the process.
the corresponding ABMO. Thus First
we find
BMO that are filled,
The probability density in bonding and antibonding molecular orbitals is given by the square of
then the
ABMO number of molecular
starts orbitalsBMO
filling because formedhasfrom atomic
lower orbitals
energy thanis equal
that to
ofthe number of atomic orbitals
ABMO.
the wave functions shown in the equations (i) and (ii) (Is) Bonding MO
responsible for their formation and are of two types as shown below. (Fig. 6.30)
2
Figure 6.30 σ (MO) = ( A + B)2
*(Is)
Energy level diagram for=bonding σ 2A + σ B2 and
+ 2σantibonding
Aσ B ... (iii)
Antibonding MO
molecular orbitals arising from Is atomic orbital. (
and σ *2
(MO) = ( A – B)
2
Molecular Orbitals from p-Atomic Orbitals
σ 2A + σ B2 – 2σ A σ B
Figure
Combination 6.29 is slightly= complicated.
of p-orbitals There being three types of 2p orbitals namely
... (iv)

2px, 2py andFrom

2p equation (iii) it is clear that probability density of bonding molecular orbital is greater than
directed along themolecular
cartesian co-ordinates x, y from and z respectively. By convention we
the sum of the probabilityof
Formation
z densities of isolatedorbitals
atoms by the factor 2two I.sThus
orbitals of hydrogen
the probability
Energy

assumedensity
that z-axis is the intermolecular axis. A B
of electrons in bonding MO is greater than that in either of atomic orbitals ( A2 or B2).
The wave
(1) Combination functions
From equation of 2p
(iv)z itatomic
is either
Atomic
Isorbitals
clear have (+)
that probability
orbital
orof antibonding
density (–) sign.MO The Is
is lesser
Atomic
positive sign shown
orbital than the sum of
hydrogenWhen atoms
probability
antibonding
shows
two 2pdensities
z orbitals
MO is less
that
ofonisolated
two atoms
than
these
atoms
that in
by orbitals
approach
a factoreach
either of atomic
are
2 A other spherically
along
B. Thus
orbitals
the the
(
probability
2 or
symmetrical
internuclear
densityaxis inand their w
they combine
of electrons
2). In a similar way, the
by the addition of electron wave. This results in the formation Aof bonding B (2pz) orbital while
associated
subtraction of electron waves give rise to antibonding molecular orbital * (2pz). It one
with
combination +ve
of two sign
2s orbitalsin all directions.
produces a bonding In
(2s) case
and of p-orbitals
antibonding * (2s) molecular lobe
orbitals.has
is represented as +ve sig
–vefollows
sign.: The overlapping of atomic orbitals takes place if they have similar sign
(Is) Bonding MO

Figure
Combination of 2p 6.30
z orbital
The probability density
Energy level inforbonding
diagram bonding andand antibonding molecular orbitals is give
antibonding
molecular orbitals arising from Is atomic orbital.
the wave functions shown in the equations (i) and (ii)
Molecular Orbitals from p-Atomic Orbitals
2pz 2pz
2 complicated. There being 2three types of 2p orbitals
(2pz )namely
MO
Combination of p-orbitals is slightly
(MO)σ =(
A x, y and
2px, 2py and 2pz directed along the cartesian co-ordinates + )
B z respectively. By convention we
assume that z-axis is the intermolecular axis.
2 2
(1) Combination of 2pz atomic orbitals A=σ B + σ + 2σ σ
A B
When two 2pz orbitals on two atoms approach each other along the internuclear axis they
*(2pcombine
*2
and (MO)σ =(
A –
by the addition of electron wave. This results in the formation 2 )
of bonding (2pz) orbitalz while
Borbital * (2p ). It Molecular
) MO
subtraction Atomic orbitals
of electron waves give rise to antibonding molecular z
orbitals
is represented as
follows : 2 2
Figure 6.31
Aσ (2pz ) Band
Combination of 2pz orbitals to form bonding
=σ
A B +σ – 2σ σ
From
antibonding σ*(2(iii)
equation it is clear
pz ) molecular that probability density of bonding
orbitals. molecular orb
the sum of the2p
probability
z 2p
densities of isolated atoms by (2the
z
p ) MOfactor 2 A B. Th z

density of electrons in bonding MO is greater than that in either of atomic orbital

From equation (iv) it is clear that probability density of antibonding MO is less
*(2p ) MO
probability densities of isolated
Atomic orbitals
atoms by a factor 2 . Thus the probability den
A BMolecular orbitals
z

| FIITJEE - 2 2
antibondingFigure
MO 6.31is less than that in either of atomic orbitals (
A or B ). In a
DPS-MIS-DOHA, Q ATAR
Combination of 2px and 2pz orbital

Condition for overlapping of Atomic orbital

The energy of atomic orbitals should be comparable
The extent of overlap between the atomic orbitals should be to be a considerable extent.
The symmetry of the combining atomic orbitals should be the same.i.e. the atomic should have same
symmetry about the internuclear axis. For example, 2s orbital of one atom can combine with 2s or 2pz orbital of
another atom but not with the 2py or 2px orbital. In other word++ or – – interaction is allowed. It is made clear in the
following diagram

s-Orbital does not combine with 2py orbital s-Orbital combines with 2pz orbital as they have
because they do not have the same symmetry same symmetry about the internuclear axis.
about the internuclear axis.

Combination of s and px orbitals

Molecular orbitals like the atomic orbitals are filled in accordance with the Aufbau Principle obeying the
Pauli’s Principle and the Hund’s rule.

Order of energy of various molecular orbitals is as follows:

For O2 and higher molecules
1s, *1s, 2s, *2s, 2px, [ 2py = 2pz], [ *2py = *2pz], *2px

| FIITJEE - DPS-MIS-DOHA, Q ATAR

For N2 and lower molecules
1s, *1s, 2s, *2s, [ 2py = 2pz], 2px, [ *2py = *2pz], *2px

Bond order: It may be defined as the half the difference between the number of electrons present in the
bonding orbitals and the anti-bonding orbitals i.e.

No. of electrons in BMO - No. of electrons in ABMO

Bond order (B.O.) =
2
In general
A molecule is stable: when bonding electron is more than the antibonding electrons
A molecule is unstable: when number of bonding electron is less than the antibonding electron

Information given by the bond order:

Stability of molecule: A positive bonding order suggest a stable molecule while a negative bond order or
zero bond order suggest an unstable molecule.
Bond dissociation Energy: It depends upon the bond order. Greater the bond order greater is the bond
dissociation energy.
Bond Length: Bond order is inversely proportional to the bond length. Higher the bond order, smaller the
bond length. i.e. Bond length is inversely proportional to bond order.
Magnetic Behavior: If all the molecular orbitals in species are spin paired, the substance is diamagnetic.
However, if one or more molecular orbitals are singly occupied it is paramagnetic. CHEMICAL BONDING – ORBITAL THEORY 217
O2– = 1s2, *1s2, 2s2, *2s2, 2px2, 2py2, 2pz2,
* (2pz)
*2py2 = *2pz1
10 - 5
Bond order = 2.5 , No. of unpaired electrons =
2 σ* (2py ) σ*(2px)
1,paramagnetic
O22– = 1s2, *1s2, 2s2, *2s2, 2px2, 2py2, 2pz2,
*2py2 = *2pz2 2p σ (2py) σ (2px) 2p

10 - 8
Bond order = 1, No. of unpaired electrons
2
= 0, diamagnetic (2pz )
O2+ = 1s2, *1s2, 2s2, *2s2, 2px2, 2py2, 2pz2,
*2py1 = *2pz0
Energy

*(2s)
10 - 5
Bond order = 2.5 , No. of unpaired electrons
2 2s 2s
=1,paramagnetic
(2s)
Now as the bond order decreases in the order O2+ O2
O2– O22–So, same will be the stability order of the above
* (Is)
species because stability is directionally proportional to
bond order
Is Is

Atomic orbitals Atomic orbitals

(Is)
Molecular orbitals

Figure 6.33
Schematic energy level representation of molecular
orbitals for simple molecules of elements.

Conditions for the combination of Atomic Orbitals| FIITJEE - DPS-MIS-DOHA, Q ATAR

The atomic orbitals may combine when certain conditions are met with. For effective combinations
Molecular orbital Diagram for Hydrogen (H2) Molecule:

Molecular orbital configuration: - 1s2, *1s0,

Bond order: 2-0/2 = 1
Magnetic Behavior: Diamagnetic

Molecular orbital Diagram of He2 Molecule:

Molecular orbital configuration: - 1s2, *1s0,
Bond order: 2-0/2 = 1
Magnetic Behavior: Diamagnetic

Molecular orbital diagram of N2 Molecule: -

Molecular orbital configuration: - 1s2, *1s2, 2s2,
*2s2, [ 2py 2= 2pz 2], 2px2, [ *2py = *2pz], *2px
Bond order: 10-4/2 = 3
Magnetic Behavior: Diamagnetic

Molecular Orbital Diagram of Oxygen Molecule:

Molecular orbital configuration:- 1s2, *1s2, 2s2,
*2s2, 2px2, [ 2py2 = 2pz2], [ *2py1 = *2pz1], *2px
Bond order: 10-6/2 = 4/2 = 2
Magnetic Behavior: Paramagnetic
Molecular Orbital Diagram of Fluorine Molecule:
Molecular orbital configuration:- 1s2, *1s2, 2s2,
*2s2, 2px2, [ 2py2 = 2pz2], [ *2py2 = *2pz2], *2px
Bond order: 10-8/2 = 2/2 = 1
Magnetic Behavior: Diamagnetic
Molecular Orbital Diagram of Neon Molecule:
Molecular orbital configuration:- 1s2, *1s2, 2s2,
*2s2, 2px2, [ 2py2 = 2pz2], [ *2py2 = *2pz2],
*2px2
Bond order: 10-10/2 = 0/2 = this molecule will not exist.
Magnetic Behavior: Diamagnetic

| FIITJEE - DPS-MIS-DOHA, Q ATAR

 Molecular Orbital Diagram of NO Molecule:
Molecular orbital configuration:- 1s2, *1s2, 2s2,
*2s2, 2px2, [ 2py2 = 2pz2], [ *2py1 = *2pz], *2px0
Bond order: 10-5/2 = 2.5
Magnetic Behavior: Paramagnetic
Molecular Orbital Diagram of CO Molecule:
Molecular orbital configuration:- 1s2, *1s2, 2s2,
*2s2, 2px2, [ 2py2 = 2pz2], [ *2py0 = *2pz0],
*2px0
Bond order: 10-4/2 = 6/2= 3
Magnetic Behavior: Diamagnetic
Molecular Orbital Diagram of CN Molecule:
Molecular orbital configuration:- 1s2, *1s2, 2s2,
*2s2, 2px2, [ 2py2 = 2pz1], [ *2py0 = *2pz0],
*2px0
Bond order: 09-4/2 = 5/2 = 2.5
Magnetic Behavior: Paramagnetic

Properties of homonuclear diatomic molecule of the second period elements

Problem: Arrange the species O2, O2–, O22– and O2+ in the decreasing order of bond order and
stability and also indicate their magnetic properties.
Solution: The molecular orbital configuration of O2, O2–, O22– and O22+ are as follows:
O2 = 1s2, *1s2, 2s2, *2s2, 2px2, 2py2, 2pz2, *2py1 = *2pz1
10 - 6
Bond order = 2 , No. of unpaired electrons = 2 paramagnetic
2

| FIITJEE - DPS-MIS-DOHA, Q ATAR

CLASS WORK:
Arrange N2, N2+, N2– in the increasing order of stability
FORMAL CHARGE: - There are several ways to choose the more plausible of two structures, the one
way involves a concept called formal charge, which can be applied to any atom within a Lewis structure.
The formal charge for the atom in a molecule or ion is the charge calculated for that atom based on the
Lewis structure of the molecule or ion using the equation.
Formal charge of the atoms in the molecule or ion
Cf X Y Z /2
or Formal charge,
X Number of valence electrons in the free atom
Y Number of unshared electrons owned by the atom
Z Number of bonding electrons. The factor 1/2 divides the bonding electrons equally between the atoms
linked by the bond.
Ordinarily, the more likely Lewis structure is one is which
(i) the formal charges are close to zero as possible.
(ii) any negative formal charge is located on the most strongly electronegative atom.
Calculating the formal charges of various atoms in structures (i) and (ii) and applying the above rules
to decide which structure is preferred for methyl alcohol is a below:

H ‥ ‥
‥ H – C– O– H
H – C – O– H
‥ H H
H
(i) (ii)

For C: X 4, Y 0, Z 8 For C: X 4, Y 2, Z 6

8 6
Cf 4 0 0 Cf 4 2 1
2 2

O: X 6, Y 4, X 4 O: X 6, Y 2, Z 6

4 6
Cf 6 4 0 Cf 6 2 1
2 2

EveryH: X 1, Y 0, Z 2 Every H: X 1, Y 0, Z 2

2 2
Cf 1 0 0 Cf 1 0 0
2 2
In structure (i) carbon, oxygen and hydrogen atoms have formal charges of zero. In structure (ii), a
negative charge is assigned to carbon and a positive charge is assigned to oxygen which is very unlikely
because carbon is less electronegative than oxygen. Hence, structure (i) for methyl alcohol is preferred
over structure (ii).
The sum of the formal charges on the atoms in a molecule or ion always equal its net charge.

| FIITJEE - DPS-MIS-DOHA, Q ATAR

 RESONANCE

When a single Lewis structure fail to explain the all properties of a molecule or ion, then two or more than
two structures are written to explain the properties of given molecule. These structure known as resonating
structure or contributing structure and the phenomenon is known as resonance.

Rules for selecting Canonical Forms or Mesomeric Forms:

(i) The relative position of all the atoms in each of the canonical forms must be the same. They should
differ only in the position of electrons.

(ii) The number of unpaired and paired electrons in each of the canonical forms must be same.

(iii) The contributing structures should not differ much in energy.

(iv) The contributing structures should be such that negative charge resides on more electronegative and
positive charge on the electropositive. Like charges should not reside on atoms choose together in the
canonical forms.

(v) As a result of resonance, the bond order changes in many molecules or ions

Bond order= total number of bonds between two atoms in all the structure /total no of resonating structure

2 1
e.g., (a) B.O. 1.5
2

O O O
C C C
(b) O O O O
O O

B. O=2+1+1/3=1.33

Many misconceptions are associated with resonance and the same need to be dispelled. It should always be
kept in mind that:

(i) The canonical forms have no real existence.

(ii) The molecule does not exist for certain fraction of time in one canonical form and for other fraction of
time in other canonical forms.

(iii) There is no equilibrium between the various canonical forms or the molecule is not a mixture of various
forms.

(iv) The molecule as such has a single definite structure which cannot be depicted by a Lewis structure.

More the resonance energy, more stable will be the molecule in comparison to canonical forms.

Characteristic Features of Resonance Hybrid

(i) The resonance hybrid is more stable than any one of the canonical forms, i.e., it has less energy.
(ii) In a resonance hybrid, the bond lengths are different from those in the canonical forms. The bond
lengths in a molecule become equal. For example, the carbon-carbon bond length in benzene is 1.39A0 as
against 1.54A0 for carbon-carbon single bond and 1.34A0 for carbon-carbon double bond.
(iii) The canonical forms do not have any real existence. They are only imaginary. The resonance hybrid
has only real existence.

| FIITJEE - DPS-MIS-DOHA, Q ATAR

Examples showing Resonance

(i) Nitric oxide molecule:

‥
N ＝O : N ＝O:
(ii) Nitrogen dioxide molecule:

N N N N

:O : O: :O :O : :O : O: :O :O :
‥ ‥ ‥ ‥ ‥ ‥
(iii) Carbonate ion:
O O O

C C C

O O O O O O
(iv) Ozone:
O O

O O O O
(vi) SO3molecule:
‥ ‥
S S
‥
:O: :O: :O: :O:
‥
(vii) SO3 molecule:

O O O

S S S

O O O O O O
(viii) NO3- ion:

O O O

N N N

O O O O O O

(ix) ClO4- ion

O O O O
O

Cl Cl Cl Cl Cl
O O O O O
O O O O O O O O O O

| FIITJEE - DPS-MIS-DOHA, Q ATAR

 Bonding Parameter
Covalent bonds are characterised by the following four parameters:
(1) Bond length (2) Bond energy or Bond strength (3) Bond angle
(4) Bond order
Bond length:
It is defined as the average distance between the centres of the nuclei of the two bonded atoms in a
molecule. It is usually expressed in angstrom units A0 or picometers (pm).
10 12
1 Å 10 m,1 pm 10 m
Bond length depends upon the following factors:
(a) Bond length increases with the increase in the size of atoms.
For example, bond length in H2 molecule is 74 pm, the bond length between C-H is 109 pm and the
bond length between C-Cl is 177 pm. This is due to the fact that carbon and chlorine atoms are
bigger in size in comparison to hydrogen.
(b) Bond length decreases with the multiplicity of bonds.
C C C＝C C–C
120 pm 134 pm 154 pm

(c) Bond length is affected by type of hybridization. Greater s -character decreases the bond length as
s -orbital is smaller in size.

sp C – H sp 2 C – H sp3 C – H
50% s -character 33.3% s -character 25% s -character
107 pm 110.3 pm 111.3 pm

Bond energy or Bond strength:

Bond energy or bond strength is defined as the amount of energy required to break a bond in a molecule.
Each bond has a characteristic value of this energy and is a measure of the strength of the bond. It is
generally observed that shorter the bond length, greater is the bond strength or bond energy of the bond.
in polyatomic molecules the term mean or average bond energy is used. It is evaluated by dividing the
total bond dissociation energy by the number of bonds broken.
1
H–O–H g H g O–H g ; H 502 kJ mol
1
O–H g O g H g ; H 427 kJ mol

502 427
Average bond energy of water
2
1
464.5 kJ mol
Factors affecting the bond energy:
(i) The magnitude of the bond energy depends on the type of bonding. Strength of a sigma bond is more
than that of a bond.
(ii) A double bond in a diatomic molecule 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
(iii) 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.
(iv) Resonance in the molecule affects the bond energy.
| FIITJEE - DPS-MIS-DOHA, Q ATAR
 (v) 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 on the two bonded atoms.
(vii) Bond energy decreases down the group in case of similar molecules.
(viii) Bond energy increases in the following order:
s p sp sp 2 sp3
Bond angle:
Angle between two adjacent bonds of an atom in a molecule made up of three or more atoms in known as
the bond angle.
Bond angle mainly depends on the following three factors:
Hybridization: Bond angle depends on the state of hybridization of the central atom.
Hybridization sp3 sp 2 sp
Bond angle 109 28 120 180
Example CH 4 BCl3 BeCl2
It is observed that as s -character increases 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. The bond angle
3
in NH3 is 107 A0and bond angle in H2O is 105A0 Inspite of the fact that N-atom and O-atom undergo sp
-hybridization.
‥ ‥
O: N
105 107

H
H H H H
Water molecule Ammonia molecule
(iii) Electronegativity: If the electronegativity of the central atom decreases, bond angle decreases.
In case the central atom remains the same, bond angle increases with decrease in the electronegativity of
the surrounding atoms.
(4) Bond order: The bond order is defined as the number of bonds or number of shared electron pairs
between two atoms in a molecule.
H – H or H : H Bond order 1

O＝O or O:: O Bond order 2

N N or N N Bond order 3

C O or C O Bond order 3

O2
Isoelectronic molecules or ions have same bond order. For example, F2 and 2 (18 electrons) have
bond order 1. N2 , CO and NO (14 electrons) have bond order 3.
It is observed that with increase in bond order, bond enthalpy increases and bond length decreases.

| FIITJEE - DPS-MIS-DOHA, Q ATAR

 Solved problems

Question -1: The bond angle of H2O is 104° while that of F2O is 102°.
Solution: Both H2O and F2O have a lone pair of electrons. But fluorine being highly electronegative, the bond
pair electrons are drawn more towards F in F2O. 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 bond pair electrons are
closer to each other. So bond angle of F2O is less than H2O.

H F
repulsion repulsion less
H F

Question 2: Explain why bond angle of NH3 is greater than NF3 while bond angle of PH3 is less than that
of PF3.
Solution: Both NH3 and NF3 are pyramidal in shape with one lone pair on N. However, F has higher
electronegativity than H, the electron pair is attracted more towards F in NF3 i.e. the bond pairs of electrons
are away from N or in other words distance between bond pairs ion is more. Hence repulsion between bond
pairs in NF3 is less than NH3. Hence the lone pair repels the bond pairs of NF3 more than it does in NH3. As
a result, the bond angle decreases to 102.4°. Whereas in NH3 it decreases to 107.3° only.

N N
H H F F
H F
107.3° 102.4°

PH3 and PF3 are also pyramidal in shape with one lone pair on P. But PF3 has greater bond angle than PH3
(opposite to NH3 and NF3). This is due to resonance in PF3, leading to partial double bond character as shown
below
P +
F F
F

As result repulsions between P – F bonds are large and hence the bond angle is large. There is no possibility
of formation of double bonds in PH3.

Question 3: A diatomic molecule has a dipole moment of 1.2D. If its bond distance is 1.0Å. What
fraction of an electronic charge exist on each atom?

Solution: Dipole moment for a diatomic molecule ( ) = e d

1.2 10 18 esu.cm
electronic charge = = = 1.2 10–10 esu
d 1.0 10 8 cm
10
1.2 10
fraction of electronic charge = 10
= 0.25
4.8 10

Problem 4: In trimethylamine, the nitrogen has a pyramidal geometry whereas in trisilylamine

N(SiH3)3, it has a planar geometry. What is the reason behind this ?

| FIITJEE - DPS-MIS-DOHA, Q ATAR

Solution: In N(CH 3 ) 3 , there is sp 3 hybridization at nitrogen but due to lone pair-bond pair repulsion,
shape become pyramidal.

N
Me Me
Me
In trisilyl amine, there is vacant d-orbital at silicon, hence formation of p p back
bonding takes place and geometry becomes planar.
SiH3 SiH3 SiH3

N N N
H3Si SiH3 H3Si SiH3 H3Si SiH3

Problem 6: Draw the molecular structures of XeF2 and XeF4, indicating the location of lone pair(s)
of electrons.

Solution:

Structure of XeF2 F
Hybridization – sp3d
Shape – linear Xe

F
Structure of XeF4
Hybridization sp 3 d 2 F F
Shape – square planar
Xe
F F

Problem 7: Dipole moment of HX is 2.59 10–30 coulomb-meter. Bond length of HX is 1.39Å.

Calculate percentage ionic character of molecule.
Solution: dipole moment = q d
cal = q 1.39 10–10 coulomb – meter cal = 1.6 10–19 1.39 10–10
exp 2.59 10 30
% age ionic character= 100 = 100 = 11.65%
cal 1.6 10 19 1.36 10 10

Problem 08: Why is that Lithium salts have a greater degree of covalent character than other halides
of the alkali metal.
Solution: The small size of Li+ gives it a large polarizing power, hence covalent nature of its
compound increases. It can be viewed in terms of Fajan’s rule, smaller the cation, larger
the anion, greater the charge density at the surface causes greater polarizing power of Li+.
Hence, greater the covalent nature.

| FIITJEE - DPS-MIS-DOHA, Q ATAR