Ionic Bond 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.

When two atoms, one of which can lose one or more electrons to attain a noble gas configuration
and the other can receive these electrons and thereby acquire a noble gas configuration, they are
said to be bonded by an ionic bond. Since the loss and gain of electrons by atoms results in the
formation of ions, ionic bond is formed when two ions interact with each other and are thus held
together by electrostatic attraction. The formation of potassium chloride (KCl), is illustrated
below.
+
K (1s 2 2s 2 2p 6 3s 2 3p 6 4s1 ) loses
→ K (1s 2 2s 2 2p 6 3s 2 3p 6 )
1 electron

2 2 6
→ Cl− (1s 2 2s 2 2p6 3s 2 3p6 )
Cl (1s 2s 2p 3s 3p )  2 5 gains
1 electron (Ar configuration)

From the above illustrations, it is clear that the formation of an ionic compound is obviously
related to the ease of formation of the cations and anions from the neutral atoms which depends
on two main factors:

i) Ionization energy: Lower the value of ionization energy of an atom, greater will be the
ease of formation of the cation from it.

ii) Electron affinity: Higher the electron affinity of an atom, greater the ease of formation
of the anion from it.

Lattice Energy

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

Energetics of Formation of Ionic Substances: 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 sodium chloride from sodium and chlorine.

Na (s ) Sublimatio → Na (+g ) + e −
n → Na ( g ) 
+S +I

1 Dissociation Addition of e- −
Cl2(g) → Cl(g)  → Cl(g)
2 +1/ 2D* − EA
 + − Crystal formation
Na (g) + Cl(g) 
→ NaCl(S)
−U

Where S = heat of sublimation of sodium metal

I = ionization energy of sodium
D = heat of dissociation of molecular chlorine
EA = electron affinity of chlorine, and
U = lattice energy of sodium chloride

The amount of heat liberated in the overall reaction is the heat of formation of sodium chloride.
From the above

1
∆Hƒ = S + I + D – EA – U
2

The most important of these energy terms are I, EA and U, since these are considerably greater
than the remaining terms S and D.

More the negative value of the heat of formation, greater would be the stability of the ionic
compound produced. Thus on the basis of the above equation, formation of an ionic compound is
favoured by

a) low ionization energy (I) of the metal.

b) high electron affinity (EA) of the other element.
c) higher lattice energy (U) of the resulting compound.

Formation of Ions with Higher Charges: Formation of a cation with unit positive
charge is easy if the first ionization energy is low as in the case of alkali metals. Alkaline earth
metals ionizes in two successive steps.

Mg 
→ Mg+ + e–

Mg+ 
→ Mg2+ + e–

But energy needed to ionize alkaline earth metals are higher than alkali metals.

However, bipositive ions like Mg2+, Ca2+, Sr2+ and Ba2+ are quite common. Formation of a
tripositive ion like Al3+ requires much more energy (= 5138 kJ) which is not available ordinarily.
Successive ionization energies of aluminium are:

Al →
E1
Al + + e − E1 = 577kJ

Al + 
E2
→ Al 2 + + e − E2 = 1816kJ
 Al 2+ 
E3
→ Al3+ + e − E3 = 2745kJ

It is on this account that most of aluminium compounds are covalent. In solution, however,
aluminium is known to give hydrated ions [Al.6H2O]3+. This is possible because of the high heat
of hydration of Al3+. The energy liberated during hydration of ions is sufficient for ionization.

Similarly, anions with unit negative charge (e.g. Cl–1, Br–, I–) are very common. This is because
the electron affinity of these atoms is positive and quite high. Formation of anions carrying two
units of negative charge (e.g. S2–, O2–) is not so easy as their electron affinities are negative i.e.,
energy is needed to add second electron. Formation of anions carrying three units of negative
charge (e.g. N3–, P3–) is almost rare.

Characteristics of Electrovalent Compounds

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 molten forms or solutions
conduct electricity.

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
favoured 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 sulphates 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 (By Mutual Sharing of Electrons)

The covalent bond is formed when two atoms achieve stability by the sharing of an electron pair,
each contributing one electron to the electron pair.
The arrangement of electrons in a covalent molecule is often shown by a Lewis structure in
which only valency shells (outer shells) are depicted. For sake of clarity, the electrons on
different atoms are denoted by dots and crosses.

Polarity of Bonds: A covalent bond is set up by sharing of electrons between two atoms. It is
further classified as polar or non-polar depending upon the fact whether the electron pair is
shared unequally between the atoms or shared equally. For example, the covalent bonds in H2
and Cl2 are called non-polar as the electron pair is equally shared between the two atoms.

H H Cl Cl +δ −δ
Hydrogen molecule Chlorine molecule
(Both formed by equal sharing of H F
electrons between the atoms, i.e., by
non-polar bonds)
d

In the case of hydrogen fluoride the bond is polar as the electron pair is unequally shared.
Fluorine has a greater attraction for electrons or has higher electronegativity than hydrogen and
the shared pair of electrons is nearer to the fluorine atom than hydrogen atom. The hydrogen end
of the molecule, therefore, appears positive with respect to fluorine.

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 µ .

Magnitude of dipole moment | µ |= q × r

( charge in esu) ( Dis tan ce in Α )

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 = −18
= 2.998 × 10 29 D
10
 1
or 1D = = 3.336 × 10 −30 Cm
2,998 × 10 29
Dipole moment is a vector quantity and is often indicated by an arrow parallel to the line joining

the point of charge and pointing towards the negative end e.g., H − F .
Experimental dipole moment
% Ionic character of a covalent bond = × 100
Theoretical dipole moment assuming 100% ionic character

Illustration 1: 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
|µ| = qr = (1.602 × 10–19) (2.6 × 10–10) = 4.165 × 10–29 Cm
Actual dipole moment = 3.336 × 10–29 Cm

3.336 × 10 −29
∴ % of ionic bond = × 100 = 80.1%
4.165 × 10 −29
The bond is 80.1% ionic.

In general a polar bond is established between two atoms of different radii and different
electronegativities while positive centres (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:

i) 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.

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

For example, carbon dioxide, methane and carbon tetrachloride, being symmetrical molecules,
have zero dipole moments.

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
µ = 1.75d H

H Cl H
µ = 0D µ = 0D µ = 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.

We have seen that in a polar covalent bond between two atoms (say A and B), there is a partial
separation of charge. This bond is, therefore, said to have a partial ionic character. Greater the
difference of electronegativity between A and B, greater is the degree of ionic character (or
polarity measured by dipole moment of AB) of the bond. Pauling gave a fairly accurate rule by
which the nature of the bond can be predicted. According to this rule, “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”. For example, when
the electro negativity difference is 0.8, 1.2, 2.2 and 2.6, the corresponding partial ionic character
is 12%, 25%, 61% and 74% respectively.

Characteristics of Covalent Compounds

Melting Point and Boiling Point: In covalent compounds, except those consisting of
giant molecules, the molecules are less powerfully attracted to each other, as a result of which
their melting points and boiling points are relatively low compared to ionic compounds, e.g.,

SiCl 4 (b.p. = 33K) and NaCl (b.p. = 1713K)

(Covalent compound) (ionic compound)

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.

Solubility: The characteristic solubility of covalent compounds in non-polar solvents such as

benzene and carbon tetrachloride can be described to the similar covalent nature of the molecules
of solute and solvent (i.e., like dissolves like). Covalent compounds in solution react more slowly
as compared with the ionic compounds which react instantaneously in solution. The solubility of
covalent compounds is, however, very much dependent upon the size of the molecule. Thus
covalent substances having giant molecules are insoluble in virtually all solvents due to the big
size of the molecule unit.
 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.

The magnitude of polarization depends upon following factors :

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.

NaCl < Na2S < Na3P

ii) Size of the cation: Polarisation 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
CaF < CaCl < CaBr < CaI
from F– anion to I– anion i.e.  
2

2

2

2 →
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.

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).

δ− δ+ δ− δ+
X H or X H

Electro-negative atom

If a number of such molecules are brought nearer to each other, the positive end of one molecule
and negative end of the other molecule will attract each other and weak electrostatic force will
develop. Thus, these molecules will associate together to form a cluster of molecules.

δ− δ+ δ− δ+ δ− δ+ δ− δ+ δ− δ+
X− H L X− H L X− H L X− H L X− H

The attractive force that binds hydrogen atom of one molecule with electronegative atom of the
other molecule of the same or different substance is known as hydrogen bond.

Hydrogen bonding is of two types:

a) Intermolecular hydrogen bonding: This type of bonding results between the

positive and negative ends of different molecules of the same or different substances.

Example
 i) Ammonia

δ+ δ+ δ+ δ+ δ+
H H H H H
+
δ− δ− δ− δ− δ− δ
N H N H N H N H N H

H H H H H
δ+ δ+ δ+ δ+ δ+

ii) Water
δ+ δ+ δ+ δ+
H H H H
δ− δ− δ− δ−
O H O H O H O H
iii) Acetic acid
O H O
H3C CH3
O H O
This type of hydrogen bonding increases the boiling point of the compound and also its
solubility in water. The increase in boiling point is due to association of several molecules
of the compound.
b) 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.
O - O -
H H
O O
N

O O
o-Nitrophenol o-Hydroxy benzoate ion

This type of bonding decreases the boiling point of the compound. The solubility of the
compound also decreases. Hence compound becomes more volatile.

Properties Explained by Hydrogen Bonding

a) Strength of certain acids and bases can be explained on the basis of hydrogen bonding.

b) Solubility: An organic substance is said to be insoluble in water if it does not form

hydrogen bonding with water. The organic compound like alkanes, alkenes, ethers, etc.,
are insoluble in water as they do not form hydrogen bonding with water, while alcohols
and acids are soluble because they readily form hydrogen bonds with water.
i) Melting and boiling points of hydrides of N, O and F. If the melting points
and boiling points of the hydrides of the elements of IVA, VA, VIA and VIIA groups
are plotted against the molecular weights of these hydrides, we shall get the plots as
shown in figure (a) and (b).

From these plots it may be seen that although in case of SbH3, AsH3, PH3 (VA group
elements hydrides), H2Te, H2Se, H2S (VI A group elements hydrides) and HI, HBr,
HCl (VIII group elements hydrides) there is a progressive decrease in their mp’s and
b.p’s with the decrease in their molecular weights, the mp’s and b.p’s of NH3, H2O
and HF hydrides suddenly increase with a further decrease of their molecular weights.
The sudden increase in mp’s and bp’s in these hydrides is due to the inter-molecular
H-bonding in between H and F in case of HF, in between H and O in case of H2O and
in between H and N in case of NH3 respectively. The existence of H-bonding in
these molecules gives polymerized molecules (NH3)n. Thus mp’s and bp’s of these
molecules are suddenly raised.

Having no power to form H-bonds, the simple carbon family hydrides (SnH4, GeH4,
SiH4 and CH4) show a decrease in their bp’s and mp’s with the decrease in their
molecular weights.
100 100
H2O

HF
Melting points (°C) increasing

H 2 Se
Boiling points (°C) increasing

H2O
VIA
0 0
H 2 Se H 2 Se SbH3
VIA NH 3 H2S VA
H 2 Se VIIIA VIIIA
HI
H2S HI
NH 3 VA HCl
HBr SbH3 HBr
HCl IVA
-100 HF -100 SnH4
PH 3 GeH4
AsH3
PH3 SnH4 SnH4
IVA
GeH4
CH4 SnH4 CH 4

-200 -200
Molecular weight increasing Molecular weight increasing
(a) (b)

ii) 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.
00.96Å
.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
 Coordinate Bond

It is a special type of covalent bond in which both the shared electrons are contributed by one
atom only. It may be defined as “a covalent bond in which both electrons of the shared pair
are contributed by one of the two atoms”. Such a bond is also called as dative bond. A
coordinate or a dative bond is established between two such atoms, one of which has a complete
octet and possesses a pair of valence electrons while the other is short of a pair of electrons.

xx xx
A + B xx A Bx or A B
xx xx x

This bond is represented by an arrow (→) pointing towards acceptor atom.

The atom which contributes electron pair is called the donor while the atom which accepts it is
called acceptor.

The compound consisting of the coordinate bond is termed coordinate compound. Some
examples of coordinate bond formation are given below:

i) Formation of ammonium ion: Hydrogen ion (H+) has no electrons and thus
accepts a lone pair donated by nitrogen.
H H
+
H N + H H N H

H H

ii) Formation of CO: Carbon has four valency electrons and oxygen has six. They
combine to form two double bond and a coordinate bond as to achieve their octet
completed.
xx
C + xxOxx C Oxx
Acceptor Donor

Characteristics of Coordinate Compounds: The properties of coordinate compounds

are intermediate between the properties of electrovalent compounds and covalent compounds.
The main properties are described below:

i) Melting and Boiling Points: Their melting and boiling points are higher than purely
covalent compounds and lower than ionic compounds.

ii) Solubility: These are sparingly soluble in polar solvents like water but readily soluble in
non-polar (organic) solvents.
iii) Conductivity: Like covalent compounds, these are also bad conductors of electricity.
The solutions or fused mass do not allow the passage of electricity.
 Valence Shell Electron Pair Repulsion (VSEPR) Theory
In 1957 Gillespie and Nyhom gave this theory to predict and explain molecular shapes and bond
angles more exactly. 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. A lone pair of electrons takes up more space round 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 angles between the atoms must be
decreased. The order of repulsion between lone pairs and bond pairs of electrons follows
the order as:
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 an 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 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 push 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 Number of Number of

Shape Bond angle
central 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 Cl
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
Cl Cl
contains five electron pairs: hence the structure is a trigonal
bipyramid. There are no lone pairs, so the structure is not P

distorted. However, a trigonal bipyramid is not a completely

Cl
regular structure, since some bond angels are 90° and others
120°. Symmetrical structures are usually more stable than
asymmetrical ones.
Cl
Note: Thus PCl5 is highly reactive, and in the solid state it Structure of PCl5 molecule
splits into [PCl4]+ and [PCl6]– ions, which have tetrahedral and
octahedral structures respectively.
Chlorine trifluoride ClF3: The chlorine atom is at the centre 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 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 F

is 1s22s22p63s23p6. All six of the outer electrons are used to F F
form bonds with the F atoms. Thus in SF6, the S has six
S
electron pairs in the outer shell: hence the structure is
F
octahedral. There are no lone pairs, so the structure is F

completely regular with bond angles of 90°.

F

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.

A covalent bond results from the pairing of electrons (one from each atom). The spins of the two
electrons must be opposite (antiparallel) because of the Pauli exclusion principle that no two
electrons in one atom can have all four quantum numbers the same.
1. In HF, H has a singly occupied s-orbital that overlaps with a singly filled 2p orbital on F.

2. In H2O, the O atom has two singly filled 2p orbitals, each of which overlaps with a single
occupied s-orbital from two H atoms.

3. In NH3, there are three singly occupied p orbitals on N which overlap with s orbitals from
three H atoms.
4. In CH4, the C atom in its ground state has the electronic configuration 1s2, 2s2, 2p1x , 2p1y

and only has two unpaired electrons, and so can form only two bonds. If the C atom is
excited, then the 2s electrons may be unpaired, giving 1s2, 2s1, 2p1x , 2p1y , 2p1x . There are

now four unpaired electrons which overlap with singly occupied s orbitals on four H
atoms.
2p
2s 2px 2py 2pz
Electronic structure of
carbon atom - groun state

1s 2s 2p
Carbon atom - excited
state

Carbon atom having

gained four electrons
from H atoms in CH4
molecule. sp3 hybridisation

CH4 molecule uses its three p-orbitals px, py and pz, which are mutually at right angles to
each other, and the s orbital is spherically symmetrical. Hence they form tetrahedral
structure.

CH4 H – C – H = 109°28′

σ and π Bonds)
Sigma and Pi Bonds (σ

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.

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

a) s – s overlapping

Molecular axis

b) s – p overlapping

c) p – p overlapping
 head on
overlap
pz pz p-p overlap σ M.O.

2. Pi bond (π 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, π bond formed is a weak bond. π bond overlapping takes place only at the
sides of two lobes. A π bond is formed when a σ bond already exists between the
combining atoms.

p p p-p overlapping π M.O.

Example:
In A – B molecule the bond formed is σ bond.
σ
In A B, molecule there are one σ and one π bonds
π
σ
In A B, molecule there are one σ and two π bonds
π
Thus, all the single bonds are σ bonds. Double bond has one σ and one π bond. Triple bond has
one σ and two π bonds.

Hybridisation

It is the mathematically fabricated concept that is introduced to explain the geometry/shapes of

the covalent molecules of polyatomic ions containing covalent bonds.

It is a process of intermixing of atomic orbitals with small difference in energy and belonging to
the same atom, at the time of bonding so as to give another set of orbitals with equivalent shapes
and energies.

sp3 Hybridisation: In ground state, the electronic configuration of carbon is 1s2, 2s2, 2p2. It is
proposed that from 2s orbital, being quite near in energy to 2p orbitals, one electron may be
promoted to the vacant 2pz orbital thus obtaining the excited atom. At this stage the carbon atom
undoubtedly has four half-filled orbitals and can form four bonds. In the excited atom, all the
four valence shell orbitals may mix up to give four identical sp3 hybrid orbitals. Each of these
four sp3 orbital possesses one electron and overlaps with 1s orbitals of four H atoms thus forming
four equivalent bonds in methane molecule. Due to the tetrahedral disposition of sp3 hybrid
orbitals, the orbital are inclined at an angle of 109° 28’. Thus all the H– C– H angles are equal to
109° 28’

2p 2p
Promotion sp3
Energy

of an electron Hybridisation

2s 2s
Ground State Excited State Hybridised State

H
H

109.5°
C
H H
H H
H H

Shape and formation of methane molecule

sp2 Hybridisation: When three out of the four valence obritals of carbon atom in excited
state hybridize, we have three sp2 hybrid orbitals lying in a plane and inclined at an angle of 120°.
If 2s and 2p, orbitals of the excited carbon atom are hybridized, the new orbitals lie in the xy
plane while the fourth pure 2pz orbitals lies at right angles to the hybridized orbitals with its two
lobes disposed above and below the plane of hybrid orbitals. Two such carbon atoms are
involved in the formation of alkenes (compounds having double bonds). In the formation of
ethene two carbon atoms (in sp2 hybridization state) form one sigma bond by `head-on’ overlap
of two sp2 orbitals contributed one each by the two atoms. The remaining two sp2 orbitals of each
carbon form σ bonds with H atoms. The unhybridized 2p, orbitals of the two carbon atoms
undergo a side-wise overlap forming a π bond. Thus the carbon to carbon double bond in ethene
is made of one σ bond and one π bond. Since the energy of a π bond is less than that of a σ bond,
the two bonds constituting the ethene molecule are not identical in strength. The molecule is a
planar one.
Pure p-orbital

2p 2p
Promotion sp2
Energy

of an electron Hybridisation
sp2 hybrid
orbitals

2s 2s
Ground State Excited State
 pz pz
π π
H H H
H
σ σ σ
sp2 C C sp2 2
sp2 sp
σ H sp2 sp2 σ H H
π H

Orbital model of ethane molecule

Different types of hybridization depend upon the type of atomic orbitals which are used for
intermixing.

Types of hybridization and spatial orientation of hybrid orbitals: The geometry

and shapes of various species on the basis of VSEPR theory along with hybrid state of central
atom is given below in tabular form.

Orientation
Types of atomic
Hybridisation of hybrid Examples
orbitals used
orbitals

1. one s + one p-orbital sp Linear BeF2 , BeCl 2 , C 2 H 2 , HgCl 2

Trigonal
2. one s + two p-orbitals sp 2 BF3 , C 2 H 4 , NO 3− , CO 32−
planar

3. one s + three p-orbitals sp 3 Tetrahedral CH 4 , CCl 4 , SiF4 , NH +4 , SO 24 − , ClO −4

Trigonal
4. one s + three p + d sp 3 d PF5 , PCl 5
bipyramidal

5. one s + three p + two d sp 3 d 2 Octahedral SF5 , [CrF6 ]3− , IF5

Pentagonal
6. one s + three p+three d sp 3 d 3 IF7
Bipyramidal
Only in complexes like
2 Square
7. One d + one s + two p dsp
planar [ Ni (CN ) 4 ) 2 − , [ PtCl 4 ] 2 − etc.

Note: i) Orbitals participating in hybridization must have only small difference in their energies.
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 more 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 Poyatomic 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 :
X 2 3 4 5 6 7
Hybrid state sp
sp 2 sp 3 sp 3 d sp 3 d 2 sp 3 d 3

PF5 COCl 2 NH +4 ClO −4

X =12 [5 + 5] X =12 [ 2 + 4] X =12 [ 4 + 5 − 1] X =12 [0 + 7 + 1]

=5 =3 =4 =4
Hybrid state of P is Hybrid state of C is Hybrid state of N is Hybrid state of Cl is
sp 3 d sp 2 sp 3 sp 3

NO 3− IF5 CO 2 XeF4

X =12 [0 + 5 + 1] X =12 [5 + 7] X =12 [0 + 4] X =12 [ 4 + 8]

=3 =6 =2 =6
sp
sp 2 sp 3 d 2 sp 3 d 2

PH3 SF4
PCl 6− SF3+

X =12 [6 + 5 + 1] X =12 [3 + 5] X =12 [3 + 6 − 1] X =12 [ 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

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. Mulliken put forward a theory
known as Molecular Orbital Theory to explain above questions and many others. According to
this theory, as the electrons of an atom are present in various atomic orbitals, electrons of a
molecule are present in various molecular orbitals. 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 a molecular orbital, it is influenced by
two or more nuclei depending upon the number of atoms in the molecule. Thus, an atomic orbital
is monocentric while a molecular orbital is polycentric. The number of molecular orbitals formed
is equal to the number of combining atomic orbitals. When two atomic orbitals combine, two
molecular orbitals are formed. One is known as bonding molecular orbital (BMO) whereas other
is anti-bonding molecular orbital (ABMO). BMO has lower energy and hence greater stability
than the corresponding ABMO. First BMO are filled, then ABMO starts filling because BMO
has lower energy than that of ABMO.

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

σ1s, σ*1s, σ2s, σ*2s, σ2px, [π2py = π2pz], [π*2py = π*2pz], σ*2px
For N2 and lower molecules
σ1s, σ*1s, σ2s, σ*2s, [π2py = π2pz], σ2px, [π*2py = π*2pz], σ*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
A positive bonding order suggest a stable molecule while a negative bond order or zero bond
order suggest an unstable molecule.

Magnetic Behaviour: 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.
Illustration 2 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 = σ1s2, σ*1s2, σ2s2, σ*2s2, σ2px2, π2py2, π2pz2, π*2py1 = π*2pz1
10 - 6
Bond order = = 2 , No. of unpaired electrons = 2
2
∴ paramagnetic
O2– = σ1s2, σ*1s2, σ2s2, σ*2s2, σ2px2, π2py2, π2pz2, π*2py2 = π*2pz1
10 - 5
Bond order = = 2.5 , No. of unpaired electrons = 1
2
∴ paramagnetic

O22– = σ1s2, σ*1s2, σ2s2, σ*2s2, σ2px2, π2py2, π2pz2, π*2py2 = π*2pz2
10 - 8
Bond order = = 1 , No. of unpaired electrons = 0
2
∴ diamagnetic
O2+ = σ1s2, σ*1s2, σ2s2, σ*2s2, σ2px2, π2py2, π2pz2, π*2py1 = π*2pz0
10 - 5
Bond order = = 2.5 , No. of unpaired electrons = 1
2
∴ paramagnetic

Now as the bond order decreases in the order O2+ > O2 > O2– > O22–

So, same will be the stability order of the above species because stability is
directionally proportional to bond order.

Note: Bond length is inversely proportional to bond order.

Solved Problems

OBJECTIVE

Problem 1: Which of the following compound (s) has/have sp2 hybridization of the central
atom:
(a) CO2 (b) SO2
(c) BF3 (d) N2O

1
Solution: (B) → CN = [6 + 0 − 0 + 0] = 3 sp2
2
1
(C) → CN = [3 + 3 − 0 + 0] = 3 sp2
2

Problem 2: The hybridization of atomic orbitals of nitrogen in NO +2 , NO3− and NH +4

are
(a) sp, sp3 and sp2 respectively (b) sp, sp2 and sp3 respectively
(c) sp2, sp and sp respectively (d) sp2, sp3 and sp respectively

Solution: (b) In NO +2 , valence electrons of Nitrogen = 5

n=5–1=4 (due to one + ve charge)

n
=2 ∴ Hybridization is sp
2
In NO 3− , n = 5 + 1 = 6 (due to one – ve chanrge)
n
=3 ∴ Hybridization is sp2
2
In NH +4

n=5+4–1 (Due to of four hydrogen atoms and one +ve charge)

n
=4
2

Problem 3: Molecular shapes of SF4, CF4 and XeF4 are

(a) the same, with 2, 0 and 1 lone pair of electrons, respectively
(b) the same, with 1, 1 and 1 lone pair of electrons, respectively
(c) different, with 0, 1 and 2 lone pair of electrons, respectively
(d) different with 1, 0 and 2 lone pair of electrons, respectively
Solution: (d)
Molecular shapes of SF4, CF4 and XeF4 are different with 1, 0, 2 lone pairs of
electrons, respectively.

Problem 4: Which of the following statements regarding ozone is not correct?

(a) the ozone molecule is angular in shape
(b) the ozone molecule is a resonance hybrid of the two structures
(c) The oxygen-oxygen bond length in ozone is identical with that of
molecular oxygen
(d) Ozone is used as germicide and disinfectant for the purification of air

Solution: (c) Because of resonance

Problem 5: The correct order of increasing acidity

(a) HOI < HOBr < HOCl (b) HOCl < HOBr < HOI
(b) HOBr < HOI < HOCl (d) HOCl < HOI < HOBr

Solution: (a) HOI < HOBr < HOCl

Problem 6: Which of the following statement is correct:

(a) when a molecule can best be represented as a series of resonance forms
each of these forms always contributes to the same degree in the hybrid.
(b) A node is a region of high electron density between the two atoms in a
covalent bond.
(c) For a carbon atom, the 2s and 2p orbitals are equal in energy
(d) When filling two or more orbitals of the same energy with electrons, the
single electron is filled into different orbital rather than pair up in the same
orbital

Solution: (d) Hund’s rule of maximum multiplicity.

Problem 7: In O2F2, which of the following statement is incorrect.

(a) O-F bond length in O2F2 is longer than O-F bond length in OF2
(b) The O.N. of oxygen in O2F2 is +1.
(c) The O–O bond length in O2F2 is shorter than O–O bond length in H2O2.
(d) None of these

Solution: (d)
+ +
F − O − O − F ↔ F O = O− F ↔ F − O = O F
Problem 8: Which of the following reaction cannot result into adduct formation ?
(a) BF3 + NH3 
→ Adduct (b) BCl3 + NH3 
→ Adduct

(c) H 3C − O − CH 3 + BCl3 → Adduct (d) H3Si − O − SiH3 + BCl3 

→ Adduct

Solution: In disilylether, there is p π − d π bonding and so disilyether cannot acts as Lewis

base. Hence, answer is (d).

Problem 9: The dipole moment of 1, 4- dimethoxybenzene is 1.730 D. This reveals that the
real structure of molecule may be written as
(a) (b) Η3C
H3 C O O CH3 Ο  Ο
CH3

Η3C  CH3
(c) Ο Ο (d) All of these

Solution: H3C
O O
CH3
In case of a & b, net dipole moment should be zero
There will be no net resultant vector and hence (C)

Problem 10: Which of the following set of molecules have almost same bond angle ?
(a) CH4, NH3, H2O (b) H2O, H2S and H2Se
(c) NH3, PH3, SbH3 (d) NF3, PF3 and AsF3

Solution: (d) The net result of the two opposing effects, greater non-bonding interatomic
distance and greater bond dipole charges produce a constant bond angle is NH3,
PF3 and AsF3.

Problem 11: Which homonuclear diatomic molecules of second period elements, besides
O2, should be paramagnetic ?
(a) Li2 (b) B2
(c) C2 (d) N2
Solution: B2 - σ1s2 σ1s*2 σ 22s σ*22s π12py π12pz

Hence B2 is paramagnetic
Hence (b)

Problem 12: Which of the following molecular orbital has two nodal planes ?
(a) 62s (b) π2 p y

(c) π*2 py (d) σ*2 px

Solution: (c)

Problem 13: Which of the following is increasing order of bond angle?

(a) CH3− < SiH3− < GeH3− (b) GeH3− < SiH3− < CH3−

(c) SiH3− < CH3− < GeH3− (d) SiH3− = GeH3− < CH3−

Solution: (b) As size of central atom increases the bond angle decreases

Problem 14: The phosphate of a metal has the formula MPO4. The formula of its nitrate
will be
(a) MNO3 (b) M2(NO3)2
(c) M(NO3)2 (d) M(NO3)3

Solution: (d) MPO4 the oxidations state of M is +3. Hence, the formula of nitrate is
M(NO3)3.

Problem 15: Which of the following compound has electrovalent linkage

(a) CH3Cl (b) NaCl
(c) CH4 (d) Cl2

Solution: (b) Na is highly electropositive while Cl is highly electronegative so they will

form ionic bond.

Problem 16: Which one is the electron deficient compound

(a) ICl (b) NH3
(c) BCl3 (d) PCl3

Solution: (c) BCl3 is electron deficient compound because it has only 6 electrons after
forming bond.
Problem 17: Bond energy of covalent O – H bond in water is
(a) Greater than bond energy of H-bond
(b) Equal to bond energy of H – bond
(c) Less than bond energy of H – bond
(d) none of these

Solution: (a)

Problem 18: The interatomic distance in H2 and Cl2 molecules are 74 and 198 pm
respectively. The bond length of HCl is
(a) 272 pm (b) 136 pm
(c) 124 pm (d) 248 pm

Solution: (b) Middle length of H2 = 74 pm

Length of H = 74/2 = 37 pm
Middle length of Cl2 = 198 pm
Length of Cl = 198/2 = 99 pm
Bond length of HCl = Length of H + Length of Cl = 37 + 99 = 136 pm

Problem 19: Among the species : CO2, CH3COO−, CO, CO32-, HCHO which has the
weakest carbon –oxygen bond
(a) CO2 (b) CH3COO−
(c) CO (d) CO32−

Solution: (d) Among the give species. The bond dissociation energy of C – O bond is
minimum in case of CO32- by which C – O bond become more weaker in
CO32- or the bond order of CO32- (1.33) is minimum so the bond become
weaker.

Problem 20: Which of the following will show least dipole character
(a) Water (b) Ethanol
(c) Ethane (d) Ether
[Kurukshetra CEE 1998]
Solution: (c) due to its symmetrical structure.

Problem 21: The bond in the formation of fluorine molecule will be

(a) Due to s-s overlapping (b) due to s-p overlapping
(c) due to p-p overlapping (d) due to hybridization

Solution: (c) in fluorine molecule formation p –p orbitals take part in bond formation.
Problem 22: In which of following there exists a pπ - dπ bonding
(a) Diamond (b) Graphite
(c) Dimethyl amine (d) Trisilylamine

Solution: (d) We know that trisilylamine is sp2-hybridized therefore pπ-dπ bonding is

possible due to the availability of vacant d-orbitals with silicon.

Problem 23: In which of the following the central atom does not use sp3 hybrid orbitals in
its bonding
(a) BeF3− (b) OH3+
(c) NH2− (d) NF3
[MNR 1992]
− 3 2
Solution: (a) In BeF3 , Be is not sp - hybridised it is sp hybridized.

Problem 24: Which of the following has/have least dipole moment ?

CH3 CH3
(a) C
H H (b) CH3 – C ≡ C – CH3
CN

CH3 H
(d)
(c) C C
H CH3 CN

Solution: (b, c, d)
All the three has µ = 0

Problem 25: Which of the following molecules species has/have paramagnetic

characteristic
(a) O2 (b) O2−
(c) O22+ (d) O2+

Solution: (a, b, d)
Contains unpaired electrons.

Problem 26: Type of bonding (s) present in NH4Cl is/are

(a) ionic (b) covalent
(c) Coordinate (d) singlet.
Solution: (a, b, c)
H
N Cl
H H
H

Problem 27: Which of following statement (s) is/are true?

(a) HF is more polar than HBr
(b) CuCl is more covalent than NaCl
(c) HF is less polar than HBr.
(d) Chemical bond formation takes place when forces of attraction overcome
the forces of repulsion.

Solution: (a, b, d)

Problem 28: Match List – II with List – I.

List – I (Bond) List – II (Bond formed by)

i) C – H bond in ethylene a) sp3d2 – p overlap

ii) N – H bond in ammonia b) sp3d – p overlap

iii) Xe – F bond in XeF4 c) sp2 – s overlap

iv) Cl – F bond in ClF3 d) sp3 – s overlap

Solution: (i – c), (ii – d), (iii – a), (iv – b)

Write-up – I

Mixing of atomic orbitals is known as hybridization. When two or more atomic orbitals of
almost similar energies are mixed, equal numbers of new orbitals are formed. These new
orbitals are called hybrid orbitals and this phenomenon is known as hybridization. Whatever
be the number of hybrid orbitals, they orient themselves in such a way so that they are at their
maximum separation for minimum interelctronic repulsion for minimum energy and for
maximum stability. The geometries may be lineary equilateral triangular, tetrahedral,
triangular bipyramidal, octahedral etc.
If the central atom is surrounded by both lp’s and bp’s then not only shape differ from the
structure, but also bond angle departs from their standard value. The lone pair always occupy
such position which can give maximum stability. If all the positions are not equivalent, then
more electronegative substitutent prefers that orbitals which have high % of p-character and
 more electropositive substituent prefer orbital having high % of s-character. According to
VSEPR theory,
Lp – Lp repulsion > Lp − Bp repulsion > BP − BP repulsion.
Read the above paragraph carefully and answer the following questions.

1. When ammonia accepts a proton, the angle < HNH

(a) Remains same (b) Decreases
(c) Increases (d) Cannot be predicted

2. Which of the following is correct structure of XeF4 ?

F

:
F F :
:

(a) Xe (b) Xe
:

F F F
F F
F
:

F F : F
(c) Xe (d) Xe
:
F F :
F F

3. Which of the following is correct structure of P(CH3)2F2Cl ?

CH3 CH3
Cl CH3

(a) F P (b) F P
F F
CH3 Cl

F
Cl

(c) H3C P (d) None of these

CH3
F

4. Which of the following pair has different structure but same shape:
(a) [BrF3, PCl5] (b)  I3− , CS2 

(c) [BCl3, PCl3] (d)  BrF4+ , XeF4 

5. In BrF4+ molecule the hybridization of bromine atom is :

(a) sp3dxy (b) sp3dx2-y2

(c) sp3dz2 (d) all of them

Solutions : 1. (c) 2. (d) 3. (c) 4. (b) 5. (c)

1. In NH3, there is 3bp and one lp and so have bond angle less than 109028′. In
case of NH +4 ions, there are 4bp’s and hence bond angle is 109028′.

2. Lp’s will be at maximum possible separation hence (D)

3. In accordance with Bent’s rule

4. Both have linear structure

5. In strict sense
sp3d = s + px + py + pz dz2
Hence (C)

Write-up – II

Hybridization is the process of intermixing of atomic orbitals of same atom, having

almost similar energies, followed by redistribution of energies to form new orbitals. The
new orbitals formed are called hybrid orbitals. The no. of hybrid orbitals formed is
always equal to the no. of orbitals which get hybridized.

1. Hybridization on cental element in CO32 − and SO3 is

(a) sp2 (b) sp3

(c) sp3d (d) sp3d2

2. The shape of B F4− is

(a) square pyramidal (b) Tetrahedral

(c) Octahedral (d) none of these

Solution 1: (a) 2. (b)

SUBJECTIVE
Problem 1: Explain why 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

Problem 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.
Problem 3: Though Cs is most electropositive element in periodic table, Li has highest
oxidation potential why?

Solution: A metal ionizes in following way in gaseous state

M → M+(g) + 1e– ∆H = I.E. …(1)
But in water cation undergoes hydration
M+(g) + nH2O → [M(H2O)n]+ ∆H = hydration energy …(2)

I.E. has positive value but hydration energy has –ve value. For Cs, I.E. is less
than Li but for Li, hydration energy is more than Cs as Li+ has higher charge
density. The resultant of these two values is more –ve for Li rather than Cs.
Therefore in aqueous solution Li ionizes more than Cs.

Problem 4: 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 (µ) = e × d

µ 1.2 × 10 −18 esu.cm
∴ electronic charge = = −8
= 1.2 × 10–10 esu
d 1.0 × 10 cm

1.2 × 10 −10
∴ fraction of electronic charge = = 0.25
4.8 × 10 −10

Problem 5: 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 ?

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 π − pπ 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
Hybridization – sp3d
Shape – linear
F

Xe

Structure of XeF4

Hybridization sp 3 d 2
Shape – square planar
F F
Xe
F F

Problem 7: Anhydrous AlCl3 is covalent. From the data given below, predict
whether it would remain covalent or become ionic in aqueous solution
ΔH Hydration 3+
[Ionisation energy for Al = -5137 kJ mol–1, for Al =
ΔH Hydration
-4665 kJ mol–1, for Cl– = –381 kJ mol–1]

Solution: Total energy released during hydration of ions ( Al 3+ and 3 Cl − ) of

AlCl 3 = −4665 + ( −3 × 381) = -5808 kJ mole−1 . Since the energy released

during hydration is more (5808 kJ mole−1 ) than the ionization energy for Al

(5137 kJ mole−1 ), AlCl 3 would be ionic in aqueous solution.

Problem 8: Dipole moment of HX is 2.59 × 10–30 coulomb-metre. Bond length of

HX is 1.39Å. Calculate percentage ionic character of molecule.
Solution: dipole moment = q × d
µcal = q × 1.39 × 10–10 coulomb – metre
µcal = 1.6× 10–19 × 1.39 × 10–10
µ exp 2.59 × 10 −30
% age ionic character= × 100 = × 100 = 11.65%
µ cal 1.6 × 10 −19 × 1.36 × 10 −10
Problem 9: Calculate lattice energy of NaCl, from following data using Born-Haber’s
cycle.
Na (s ) ∆
H sub = +108.4 kJ mol -1
   → Na ( g )

I.E. = +495.8 kJ mol-1

E.A. = 348 kJ mol-1
1 ∆H D = 242 kJ mol-1
Cl 2 ( g )   → Cl ( g )
2

∆H f = −411.2kJ mol -1

Cl − (g ) Na + (g )
U
NaCl(s)

1
Solution: ∆Hf = ∆Hsub + ∆H D + IE + EA + U (using Hess' Law)
2
1
– 411.2 = 108.5 + × 242 + 495.8 – 348 + U
2
U = –788.4 kJ mol–1

Problem 10: 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.

Problem 11: The bond angle in F2O is less than that in H2O and also that in Cl2O. Give
reason for each in brief.

Solution: O O -
O
+

H H F F Cl Cl

Because of higher electronegativity of oxygen bond pairs of electron are close

to oxygen atom (central) in H2O molecule. In F2O molecule situation is just
the reverse (the F atom is more electronegative than O atom). So bp – bp
repulsion in H2O is more than that in F2O and hence there is relatively less
contraction in angle in H2O due to the presence of lone pairs.
In Cl2O molecule, one of the lone pair on oxygen atom is involved in pπ – dπ
bonding and hence the molecule is devoid of lp – lp repulsion.
Problem 12: Arrange the following in the increasing order of their
(a) CaCO3, BaCO3, MgCO3, BeCO3 (Thermal stability)
(b) CaMnO4, BaMnO4, Mg MnO4, Be MnO4 (Solubility in water)

Solution: (a) BeCO3 < MgCO3 < CaCO3 < BaCO3

(b) BaMnO4 < CaMnO4 < MgMnO4 < BeMnO4

Problem 13: a) Explain why H2O is a liquid while H2S is a gas at ordinary temperature?
b) Compare dipole moment of NH3 with that of NF3?
c) Arrange the following in increasing order of the property as mentioned in
the bracket (NH4+, SO2, CO2, [PCl4]+, [PCl6]– (energy of hybrid orbital of
the central atom)

Solution: a) Since there is hydrogen bonding in H2O while that is not present in H2S.
Due to hydrogen bonding H2O molecules come close to each other.

b) Both NH3 and NF3 show triangular Pyramidal geometry

N N

H F F
H F
H
The dipole moment produced due to lone pair of electrons on nitrogen and the
dipole moment due to N—F bond are acting in opposite direction, resulting in
the decrease of net dipole moment of the molecule. But in case of NH3, the
dipole moments are acting in same direction thereby increasing the net dipole
moment of the entire molecule will increases.
c) CO2 < SO2 < NH4+ < [PCl4]+ < [PCl6]–

Problem 14: The bond length of H – X molecule is 1.2Å and the dipole moment of the
molecule is 1.1D. Calculate % ionic character of the bond.

µobs
Solution: % ionic character = × 100
µionic

1.1 × 3.33 × 10−30 m.c.

= × 100
1.6 × 10−19 × 1.2 × 10−10 m.c.

= 1.90 × 10–1 × 100

= 19

Problem 15: B-F bond strength in BF3 is stronger than the same in BF4− , explain
Solution: Pπ - Pπ back bonding in BF3 gives some double bond character, which is
absent in BF4−

Problem 16: Compare the bond angle between:

(i) NH3 and NF3 (ii) H2Oand Cl2O

Solution: (i) NH3 > NF3 (ii) Cl2O > H2O

Problem 17: Draw the shape and mention the hybridization of central atom.
(a) ClF3O2 (b) XeO2F2
(c) IOCl4– (d) I3+
F
O
Solution: (a) O Cl

F F

Trigonal bipyramidal hybridization sp3d

Cl Cl
(b)
I
Cl Cl

square pyramidal hybridization sp3d2

(c) I

I I

V-shaped sp3 hybridisation

F
O

Xe

(d)
P
F Seasaw sp3d hybridized

Problem 18: Arrange the following in the increasing order of their

(a) CaCO3, BaCO3, MgCO3, BeCO3 (Thermal stability)
 (b) CaMnO4, BaMnO4, Mg MnO4, Be MnO4 (Solubility in water)
(c) NaCl, MgCl2, SiCl4, AlCl3 (ionic character)

Solution: (a) BeCO3 < MgCO3 < CaCO3 < BaCO3

(b) BaMnO4 < CaMnO4 < MgMnO4 < BeMnO4
(c) SiCl4 < AlCl3 < MgCl2 < NaCl

Problem 19: Assign the possible hybridization and shape of the following species
(a) SF4
(b) ClO3-

Solution: (a) sp3d ; sea-saw shaped

(b) sp3 ; Trigonal pyramidal

Problem 20: Arrange in increasing order of O – O bond length in the following

compounds O2, O2[AsF6], K[O2] using ground state configuration of

dioxygen in these compounds.

O2 σ 1s σ1s σ 2s σ 2s σ 2px .π2py π2pz π2py π2py π2pz

2 2 1 1
2 * 2 * 2 2 2 1 * *
Solution:

10 − 6
=2
B.O. = 2

O2 [AsF6] i.e. O +2 . The electron will be lost from π*2pz molecular orbital.

10 − 5
B.O. = = 2.5
2
K[O2] i.e. O −2 the extra electron added will pair up π*2py electron.
10 − 7
B.O. = = 1.5
2
As bond order decreases, bond length increases so
Bond length order is as follows:
O2 [AsF6].< K[O2]
KVPY

1. A molecule with a trigonal pyramidal structure is (2007)

(A) H3 O+ (B) NH+4 (C) BF3 (D) CO23 −

2. The dipole moment of BeF2 is (2007)

(A) 1.5 D (B) 1.0 D (C) 0.0 D (D) 1.8 D

3. Among NH3, BCl3, Cl2 and N2 the compound that does not satisfy the octet rule is (2010)
(A) NH3 (B) BCl3 (C) Cl2 (D) N2

4. The diamagnetic species is (2014)

(A) NO (B) NO2 (C) O2 (D) CO2

Answer Key
1:A 2:C 3:B 4:D
Assignments

SECTION – I Single Choice Questions

LEVEL - I

1. In compound X all the bond angles around central atom are 109028’. Which one of the
following will X be
(a) Chloromethane (b) Carbon tetrachloride
(c) Iodoform (d) Chloroform

2. Which of the following structures is linear ?

(a) SO2 (b) CO2
(c) CO32 − (d) SO 24 −

3. Which bond is most polar ?

(a) Cl – F (b) Br – F
(c) I – F (d) F – F

4. Which of the following does not conduct electricity ?

(a) Molten NaOH (b) Molten KOH
(c) Solid NaCl (d) Aqueous NaCl

5. According to Fajan rules, the covalent character is most favoured in

(a) Small cation large anion (b) Small cation, small anion
(c) Large cation, large anion (d) Large cation, small anion.

6. The percentage of s-character in the hybrid orbitals sp, sp2 and sp3 follows the pattern
(a) sp3 > sp2 > sp (b) sp > sp2 > sp3
(c) sp = sp2 > sp3 (d) sp = sp2 = sp3

7. In allene structure, the three carbon atoms are joined by

(a) Three sigma bonds and three pi bonds (b) Two sigma bond and one pi bond
(c) Two sigma bonds and two pi bonds (d) Three pi bonds only.

8. Which of the following has a bond formed by sp-sp3 overlap ?

(a) CH3 – HC = CH – CH3 (b) CH3 – C ≡ C – H
(c) HC ≡ C – H (d) CH2 = CH – CH = CH2
9. The hybrid states of carbon in diamond, graphite and acetylene are respectively
(a) sp2, sp, sp3 (b) sp, sp2, sp3
(c) sp3, sp2, sp (d) sp2, sp3, sp
10. NH3 has higher boiling point than PH3 because
(a) NH3 has higher molecular mass
(b) NH3 undergoes umbrella inversion
(c) NH3 molecules form H-bonds with one another
(d) NH3 contains ionic bonds while PH3 does not

11. In which of the following molecule, all the atoms lie in one plane ?
(a) CH4 (b) BF3
(c) PF5 (d) NH3

12. The species having highest bond order is

(a) O2 (b) O −2

(c) O +2 (d) O 22 −

13. The bond angle around the central atom is maximum for
(a) H2O (b) H2Se
(c) H2S (d) H2Te

14. Which pair of elements among the following will form most stable ionic bond
(a) Na and Cl (b) Mg and F
(c) Li and F (d) Na and F

15. Which of the following best explain the fact that o-nitrophenol is more volatile than
p-nitrophenol ?
(a) Resonance (b) Hyper-conjugation
(c) Hydrogen bonding (d) Steric hindrance.

16. Carbon dioxide is isostructural with which of the following ?

(a) HgCl2 (b) H2O
(c) SnCl2 (d) NO −2

17. The ground state electronic configuration of N2 molecules is written as KK(σ2s)2 (σ*2s)2
(π2px)2 (π2py)2 (σ2pz)2. The bond order is
(a) 3 (b) 2
(c) 0 (d) 1

18. Which of the following species in paramagnetic ?

(a) CO2 (b) NO
(c) O 22 − (d) CN−
19. The bond order of NO molecule is
(a) 1.5 (b) 2.0
(c) 2.5 (d) 3.0

20. Combination of two AO’s lead to the formation of

(a) two MO’s (b) one MO
(c) three MO’s (d) four MO’s

LEVEL - II

1. AlCl3 is covalent while AlF3 is ionic. This can be justified on the basis of
(a) the valence-bond theory (b) Fajans’ rules
(c) the molecular-orbital theory (d) hydration energy

2. Polarization involves the distortion of the shape of an anion by an adjacently placed

cation. In this context, which of the following statements is correct ?
(a) Maximum polarization is brought about by a cation of high charge.
(b) Minimum polarization is brought about by a cation of low radius
(c) A large cation is likely to bring about a high degree of polarization
(d) The polarizing power of a cation is less than that of an anion.

3. Which of the following has been arranged in order of increasing covalent character?
(a) KCl < CaCl2 < AlCl3 < SnCl4 (b) SnCl4 < AlCl3 < CaCl2 < KCl
(c) AlCl3 < CaCl2 < KCl < SnCl4 (d) CaCl2 < SnCl4 < KCl < AlCl3

4. Orthonitrophenol is steam volatile but paranitrophenol is not because

(a) orthonitrophenol has intramolecular hydrogen bonding while paranitrophenol has
intermolecular hydrogen bonding.
(b) both ortho and paranitrophenol have intramolecular hydrogen bonding.
(c) orthonitrophenol has intermolecular hydrogen bonding and paranitrophenol has
intramolecular hydrogen bonding.
(d) Van der Waals forces are dominant in orthonitrophenol.

5. Which of the following have been arranged in increasing order of bond order as well as
bond dissociation energy ?

(a) O 2−2 < O 2− < O 2+ < O 2 (b) O −22 < O −2 < O 2 < O +2

(c) O 2 < O +2 < O 22 − < O −2 (d) O +2 < O 22− < O 2− < O 2

6. How many sigma and pi bonds are present in tetracyanoethylene ?

 (a) Nine σ and nine π (b) Five π and nine σ
(c) Nine σ and seven π (d) Eight σ and eight π

7. Which of the following diatomic molecules would be stabilized by the removal of an

electron?
(a) O2 (b) CN
(c) N2 (d) C2

8. The bond angle between two hybrid orbitals is 105°. The percentage s-character of hybrid
orbital is between
(a) 50 – 55% (b) 9 – 12%
(c) 22 – 23 % (d) 11 – 12%
9. Which type of bond is not present in HNO2 molecule?
(a) Covalent (b) Co-ordinate
(c) Ionic (d) Ionic as well as co-ordinate

10. KF combines with HF to form KHF2. The compound contains the species
(a) K+, F– and H+ (b) K+, F– and HF
+ –
(c) K and [HF2] (d) [KHF]+ and F2

SECTION – II More than one choice

1. Select correct orders for corresponding property as indicated in bracket for the following.
(a) NH3 > BiH3 > SbH3 > AsH3 > PH3 (Boiling point)
(b) H2O > H2Te > H2Se > H2S (Boiling point)
(c) NH3 > PH3 > AsH3 > SbH3 (Basic character)
(d) H2O < H2S < H2Se < H2Te (Acidic character)

2. Which one or more among the following involve(s) pπ - dπ bonding?

(a) (SiH3 )3 N (b) (CH3)3 N
(c) CCl3 (d) CF3

3. Which of the following orders are correct for property indicated in brackets
(a) NH3 > NF3 > BF3 (dipole moment)
(b) Cl > S > O > N (electron affinity)
(c) Si > Mg > Al > Na (first ionization enthalpy)
(d) HClO4 > HBrO4 > HIO4 (pKa values)

4. Which among the following are having sp3d hybridization of the central atom.
(a) XeF4 (b) XeO2F2
(c) ClO3− (d) BrF3
5. Which of the following statements are correct:
(a) The bond angle of NCl3 is greater than that of NH3.
(b) The bond angle in PH3 is greater than that of PF3.
(c) ClO3− and SO32 − are isostructural

(d) It is not necessary that in TBP structure the lone pairs always would occupy the
equatorial positions.

6. Bond angle in PH3 is

(a) much less than NH3 (b) Much less than PF3
(c) slightly more than NH3 (d) much more than PF3

7. Which among the following are isostructural

(a) CO2, I3− (b) XeO2F2, SF4

(c) SO32 − , CO32 − (d) ClF3, XeF2

8. Stability of ions of Ge, Sn and Pb will be in the order

(a) Ge2+ < Sn2+ < Pb2+ (b) Ge 4+ > Sn 4+ > Pb 4+
(c) Sn4+ > Sn2+ (d) Pb2+ > Pb4+

9. Select the correct statements:

(a) the heat of hydration of the dipositive alkaline earth metals ions decrease with an
increase in their ionic size.
(b) hydration of alkali metal ions is less than that of IIA
(c) alkaline earth metal ions, because of their much larger charge to size ratio exert a
much stronger electrostatic attraction on the oxygen of water molecule surrounding
them.
(d) melting point of sodium halides follow order
NaF > NaCl > NaBr > NaI

10. The first element of groups 13-16 differ from rest of the elements. This is due to
(a) small size and high electronegativity
(b) inabilitiy to expand to the octet
(c) ability to form strong pπ - pπ multiple bonds
(d) Due to greater abundance

SECTION – III Comprehension Type Questions

 Write-up I

The shape of a molecule is determined by electron-pair repulsions in the valence shell. A

lone pair occupies larger space than a bond pair because it is not shared by two nuclei.
Thus the lone pair-lone pair repulsion is greater than the lone pair-bond pair repulsion,
which in trun is greater than the bond pair-bond pair repulsion. The presence of lone pairs
causes distortion of bond angles and hence a deviation from an ideal shape. The extent of
distortion depends upon the orientation of the lone pairs around the central atom. In a
trigonal bipyramid, the lone pairs occupy equatorial positions than the apical ones.
In ABn type molecules, as the electrongativity of A increases, the bond pairs come closer
and the repulsion between them increases. On the other hand, as electronegativity of B
increases, the bond pairs get farther and repulsion decreases.

1. Which of the following statements is true?

(a) F-N-F angle in NF3 is greater than H-N-H angle in NH3
(b) F-N-F angle in NF3 is smaller than H-N-H angle in NH3
(c) H-O-H angle in H2O is greater than H-N-H angle in NH3
(d) F-O-F angle in F2O is greater than H-O-H angle in H2O

2. Bond angle in which of the following molecules is the largest?

(a) PF3 (b) PCl3
(c) PBr3 (d) PI3

3. The shape of which of the following molecules will not be distorted?

(a) BrF3 (b) ClF3
(c) XeF4 (d) XeF6

4. Which of the following species will have the lone pair effects cancelled?
(a) ICl −2 (b) ClF3

(c) PCl3 (d) BrF5

Write-up II

The molecular orbital energy diagrams for homonuclear diatomic molecules are given
below. For systems containing up to 14 electrons:
For systems containing more than 14 electrons:
Electrons taken from both the atoms are filled from lower to higher energy molecular
orbitals (MO’s) following Hund’s rules.
The energy diagram of a heteronuculear diatomic molecule is similar. However, the
energies of the atomic orbitals (AO’s) of the atom having higher atomic number being
lower, the diagram will be unsymmetrical, but that will not make a difference in the
electron count.
 Bond order is given by half the difference in the number of electrons of the bonding (σ and
π) and anti-bonding (σ* and π*) molecular orbitals. For a bond to have been formed, the
bond order should be greater than zero. The greater the bond order, the shorter is the bond
distance and the greater is the bond dissociation energy. But if the bond order is the same
in two cases, the bond distance will be greater and the bond dissociation energy smaller in
the case which has more populated anti-bonding orbitals. The presence of unpaired
electron(s) in a molecular orbital will make the system paramagnetic.

5. Which of the following species is not expected to exist?

(a) He +2 (b) H +2

(c) Be2 (d) Be +2

6. Which among the following will have a triple bond order?

(a) CO (b) CN–
(c) NO+ (d) All of these

7. Which of the following orders is correct in respect of bond dissociation energy?

(a) N +2 > N −2 (b) O +2 > O −2

(c) NO + > NO (d) All of these

8. Which of the following species is expected to be paramagnetic?

(a) NO– (b) O −2

(c) O +2 (d) All of these

Write-up III

In the ionic bond, a cation tend to polarize the electron cloud of the anion by pulling
electron density towards itself. This causes development of covalent character in ionic
bond because the electron density gets localized in between the nuclei. The tendency of
cation to bring about the polarization of anion is expressed as its polarizing power. The
ability of ion to undergo polarization is called its polarisability. The polarizing power of
cation and polarisibality of anion are decided on the basis of Fajan rules as given below:
i) The smaller the cation, the higher is its polarizing power.
ii) Cations with pseudo noble gas configuration (ns2np6nd10) having relatively high
polarizing power than those with noble gas configuration (ns2np6).
iii) The larger the size of the anion, the higher is its polarisability.
9. Arrange the following species in increasing order of polarizing power?
Ag+, Tl+, Na+
 (a) Tl+ > Ag+ > Na+ (b) Tl+ > Na+ > Ag+
(c) Ag+ > Tl+ > Na+ (d) Na+ > Tl+ > Ag+

10. Among the following LiCl, BeCl2, BCl3, CCl4 which will have the lowest melting point and
the highest solubility
(a) CCl4, LiCl (b) LiCl, CCl4
(c) BeCl3, BCl3 (d) BCl3, BeCl2

11. The correct order of polarisibility is

I–, Br–, Cl–, F–
(a) I– > Br– > Cl– > F– (b) I– > Br– = Cl– > F–
(c) I– = Br– = Cl– > F– (d) I– = Br– < Cl– = F–

12. The ionic conductance of which of the following is the highest?

(a) Li+ (aq) (b) Na+ (aq)
(c) K+ (aq) (d) Cs+ (aq)

Answer to Assignments
SECTION - I

LEVEL - I

1. (b) 2. (b) 3. (c) 4. (c) 5.

(a) 6. (b) 7. (c) 8. (b) 9.
(c) 10. (c) 11. (b) 12. (c)
13. (a) 14. (d) 15. (c) 16. (a)
17. (a) 18. (b) 19. (c) 20. (a)

LEVEL - II

1. (b, d) 2. (a, b) 3. (a) 4. (a)

5. (b) 6. (a) 7. (a) 8. (c) 9.
(d) 10. (c)

SECTION – II
1. (b), (c), (d) 2. (a), (c) 3. (a), (b), (c)
4. (b), (d) 5. (a), (c) 6. (a), (b)
7. (a), (b) 8. (a), (c), (d) 9. (a), (b), (c), (d)
10. (a), (b), (c)

SECTION – III

1. (b) 2. (d) 3. (c) 4. (a)

5. (c) 6. (d) 7. (d) 8. (d)
9. (c) 10. (a) 11. (a) 12. (d)