1st year n0tes chemistry new

CHAPTER 6
CHEMICAL BONDING
TEXT BOOK EXERCISE
i.

Select the correct statement.

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Q.1.

An ionic compound A+B- is most likely to be formed when

the ionization energy of A is high and electron affinity of B is

low.
b.
the ionization energy of A is low and electron affinity of B is
high.
c.
both the ionization energy of A and electron affinity of B is
high.
d. both the ionization energy of A and electron affinity of B is low.

iii.
a.

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a.
b.
c.
d.

The number of bonds in nitrogen molecule is

one and one
one and two
three sigma only
two and one

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a.

Which of the following statements is not correct regarding bonding

molecular orbitals?

Bonding molecular orbitals possess less energy than atomic

orbitals from which they are formed.
b.
Bonding molecular orbitals have low electron density between
the two nuclei
c.
Every electron in the bonding molecular orbitals contributes to
the attraction between atoms.
d.
Bonding molecular orbitals are formed when the electron waves
Undergo constructive interference.
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1st year n0tes chemistry new

Which of the following molecules has zero dipole moment?

a.
d.

a.
Ans:
Q.2.
i.
ii.
iii.
iv.
v.

vi.
vii.

c.

H2O

b.

HBr

c.

HF

d.

HI

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HCl

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Which of the hydrogen halides has the highest percentage of ionic

character?

Which of the following species has unpaired electrons antibonding

molecular orbitals?

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vi.

CHCl3

b.
c.
B2
(i) b (ii) b (iii) b (iv) d (v) c (vi) b
Fill in the blanks.

d.

F2

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a.

b.

The tendency of atoms to attain maximum of ________ electrons

in the valence shell is called completion of octect.
The geometrical shape of SiCl4 and PCl3 can be explained on the
has of ________ and ________ hybridizations.
The VSEPR theory stands for ________.
For N2 molecule, the energy of (2p)x orbital is ________ than
(2py) orbital.
The paramagnetic property of 02 is well explained on the basis on
M.O theory in terms of the presence of _________ electrons in two
M.O orbitals.
The bond order of N2 is ________ while that of Ne2 is ________.
The values of dipole moment for CS2 is ________ while for SO2 is
________.

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v.

NH3
BF3

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iv.

(i) eight (ii) SP3, SP2 (iii) valence shell electron pair
repulsion (iv) greater (v) un-pairs electron (vi) tree, zero
(vii) zero, 1.61 D
Q.3. Classify the statements as true or false. Explain with reasons.
Ans:

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1st year n0tes chemistry new

viii.
ix.
x.
xi.
xii.

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iii.
iv.

The core of an atom is the atom minus its valence shell.

The molecules of nitrogen (N N) and acetylene (HC CH) are not
iso-electronic.
There are four coordinate covalent bonds in
ion.
A bond is stronger than bond and the electrons of bond are more
diffused than bond.
The bond energy of heteroatomic diatomic molecules increases
with the decrease in the electro negativities of the bonded atoms.
With increases in bond order, bond length decreases and bond
strength increases.
The first ionization energies of the elements rise steadily with
increasing atomic number from top to bottom is a group.
A double bond is stronger than a single bond and a triple bond is
weaker than a double bond.
The bonds formed between the elements having electro negativity
difference more than 1.7 are said to be covalent in nature.
The repulsive force between then two bonding pairs is less than
that between the two lone pairs.
The number of covalent bonds an atom can form is related to the
number of unpaired electrons it has.
The rules which govern the filling of electrons into the atomic
orbitals also govern the filling of electrons into the molecular
orbitals.

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i.
ii.

(i) true (ii) false (iii) false (iv) false (v) false (vi) true
(vii) false (viii) true (ix) false (x) false (xi) true (xii) true

Q.5.a. Define ionization energy and electron affinity. How these

qualities change in the periodic table. What factors are responsible
for their variation?

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b. Explain, what do you understand by the term electro

negativity? Discuss its variations in the periodic table. How does it
affect the bond strengths?
Ans:
a.
Ionization Energy
The minimum energy required to remove an electron from
gaseous atom to form positive ion is called ionization energy. The
process is called ionization. E.g.

The elements with low I.E are metals

The elements with high I.E are non-metals
The elements with intermediate I.E values are metalloids.

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ii.
iii.

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The ionization energy indicates the stability of an isolated atom.

Moreover ionization energy is an index to the metallic character.

Atomic radius or atomic size

Nuclear charge (Proton number) of atom
Shielding effect of inner electrons
Nature of orbital

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i.
ii.
iii.
iv.

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Factors Influencing Ionization Energies:

The I.E depends upon following factors

Higher Ionization Energies:

The energy required to remove an electron after the removal of
first electron is called second ionization energy. E.g.
The energy required to remove an electron after the removal of
second electron in called third ionization energy. E.g.
It is fact that 3rd I.E > 2nd I.E > 1st I.E

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The reason is that after the removal of one or more electrons, the
remaining electrons are held tightly by nuclear positive charge. Thus
further removal of electrons requires more energy.
Ionization Energy and Valency:
We can guess the valency of an element from gap between first,
second, third and higher I.E values. If there is big gap between first and
second I.E, then valency of element is one. Similarly if there is big gap
between second and third I.E, then valency of element is two. E.g.
valency of K is one.
Variation of I.E in Periodic Table:
(a)
I.E in a Group:
The ionization energy decreases from top to bottom of a group.
The reason is that new shells are added from top to bottom of group.
Thus valence electrons are at large distance from the nucleus. So force
of attraction between nucleus and outer electron decreases. Therefore I.E
decreases down the group.
(b)
I.E in a Period:
The I.E increases from left to right of a period. The reason is that
in a period nuclear charge increases one by one but no new shell is
added so atomic size decreases. Thus force of attraction between nucleus
and outer electron increases. Therefore I.E increases in a period.
Electron Affinity
The energy released when an electron is added to the partially
filled orbital of a gaseous atom to form negative ion is called electron
affinity. E.g.
Electron affinity is the measure of attraction between nucleus of
an atom and extra incoming electron.
Factors Influencing Electron Affinity:
Electron affinity depends upon following factors.
i.
ii.

Atomic radius
Nuclear charge
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1st year n0tes chemistry new

iii.
iv.

Shielding effect of inner electrons

Nature of orbital

i.

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In general electron affinity decreases with increase of atomic

radius. The reason is that by increasing distance between nucleus and
valence electrons, the force of attraction decreases. Hence E.A decreases
with increase of atomic radius.
Variation of E.A in Periodic Table:
E.A in a Group:

ii.

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When we go from top to bottom in a group the proton number

increases and new electronic shells are introduced. So atomic radius
increases. Thus force of attraction between nucleus and valence
electrons decreases. Hence E.A decrease from top to bottom in a group.
E.A in a Period:

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When we go from left to right in a period, the proton number

increases one by one but no new electronic shell is added. So atomic
radius decreases. Therefore force of attraction between nucleus and
valence electrons increases. Hence E.A increases from left to right in a
period.
Exceptional Cases:
The electron affinity of fluorine is less than that of chlorine. The
reason is that seven valence electrons of fluorine are present in 2s and 2p
sub shells. These sub shells have thick electronic cloud. This thick
electronic cloud repels the incoming electron. Hence E.A of fluorine is
less than that of chlorine.
Q.7.a. Explain qualitatively the valence bond theory. How does it
differ from molecular orbital theory?
b. How the bonding in the following molecules can be explained
with respect to valence bond theory? Cl2, O2, N2, HF, H2S.
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(a) Valence Bond Theory:
According to V.B theory molecule is formed by overlap of two
atomic orbitals. In the resulted molecule the atomic orbitals retain their
identity. The atomic orbitals are monocentric.
M.O. Theory:
According to M.O. theory a molecule is formed by linear
combination of atomic orbitals. Here atomic orbitals are buried into each
other and lose their identity. Moreover molecular orbitals are
Polycentric.
(b) Cl2:

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The Cl2 molecule has a sigma bond due to linear overlap of

partially filled orbitals.
O2 Molecule:

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O2 molecule has a double bond (one and one) for other

molecules.
Q.9. The molecules NF3, BF3 and CIF3 all have molecular formula
of the type XF3. But they have different structural formulas.
Keeping in view VSEPR theory sketch the shape of each molecule
and explain the origin of differing in shapes.
Ans:
(i)
In BF3, the central atom
boron contains three electron
pairs. All three pairs are
bonding. Thus shape of BF3 is
triangular planar. Each angle is
of 120o. It is shown in fig.
(ii)
In NF3, the
central
atom
Nitrogen contains
four
electrons
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pairs. Three are

bonding electrons
pairs and one is
lone
pair
of
electrons.
Thus
shape of
will be
tetrahedral.

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(iii)
In ClF3, the
central
atom
Chlorine contains
five electron pairs.
Three pairs are
bonding and two
are lone pairs of
electrons.
Thus
according
to
VSEPR theory the
molecule ClF3 has
a
T-Shaped
structure.

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Q.10. The species

, NH3,
have bond angles of 105o, 107.5o and
109.5o respectively. Justify these values by drawing their structures.
Ans:
(i)
In
,
nitrogen
atom
forms two covalent
bonds with two
hydrogen
atoms.
Nitrogen has two
lone
pairs
of
electrons.
These
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lone
pairs
of
electrons
repel
each other. Thus
angle
decreases
from
o
o
109.5 to 105 .

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(ii)
In
,
nitrogen
forms
covalent
bonds
with
three
hydrogen
atoms.
There is one lone
pair of electrons on
nitrogen atom. The
lone
pair
of
electrons
on
nitrogen atom. The
lone
pair
of
electron
repels
bond
pairs
of
electrons.
Thus
angle
decreases
from 109.5o to
107o.

(iii)
In
,
nitrogen
forms
three
covalent
bonds and one
coordinate bond.
There is no lone
pair of electrons on
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nitrogen. So
ion
has
perfect
tetrahedral
structure. All bond
angles are equal to
109.5o.
a. Hybridization for PH3:
In PH3,
phosphorus shows
SP3 hybridization.
Four SP3 hybrid
orbitals
are
resulted. Three SP3
hybrid
orbitals
form -bonds with
1S orbital of three
H-atoms. In fourth
SP3 hybrid orbital
one lone pair of
electrons is present.
Due to repulsion
between lone pair
and bond pairs, the
angle
decreases
from 109.5o to
107o.
Geometry of CCl4:
In CCl4,
carbon shows SP3
hybridization. Four
SP3 hybrid orbitals
are formed. They
overlap with P-

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orbitals of four Clatoms. So structure

of CCl4 is perfect
tetrahedral. Each
angle is 109.5o.
Geometry of PCl3:
In PCl3,
phosphorus shows
SP3 hybridization.
Four SP3 hybrid
orbitals are formed.
They form three bonds with Porbitals of three
Chlorine atoms. In
the fourth SP3hybrid orbital a
lone
pair
of
electrons is present.
Due to lone pairbond pair repulsion
angle
decreases
from 109.5o to
107.5o
Geometry of H2S:
In H2S,
sulphur shows SP3
hybridization. Four
SP3-hybrid orbitals
are formed. Two
SP3
orbitals
overlap with 1S
orbtials of two H-

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Molecular Orbital Picture of Ne2:

The M.O picture of Ne2 (Neon molecule) is shown below. The
bond order =
= 0. Because bond order of Neon is zero. So Ne2

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(a)

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atoms.
In
the
remaining two SP3
orbitals, two lone
pairs of electrons
are present. Due to
lone pair-lone pair
repulsions, angle
decreases from
109.5o to 104.5o.
b. (i) When atoms are located at the corners of equilateral triangle,
then central atoms SP2-hybridization.
(ii) When atoms are located at the corners of regular tetrahedron,
then central atom shows SP3-hybridization.
(iii) When atoms are located at the corners of a triangular
bipyramide, then central atom shows SP3-hybridization.
Q.13.a Sketch the molecular orbital pictures of
(i) 2py and 2py
(ii) O2,
,
(iii) He2 and
Ne2

molecule does not exist.

(b)
Hybrid Orbital of PCl3:
Phosphorous
shows
SP3
hybridization
in
PCl3. The four SP3
hybrid orbitals are
formed. Three form
bonds with P12

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orbitals of three
chlorine atoms. In
fourth SP3-hybrid
orbital lone pair of
electrons is present.
Hybrid Orbital of SF6:
In SF6,
sulphur
shows
2
6
d SP
hybridization. Six
d2SP6
hybrid
orbitals are formed.
They
all
six
overlap with Porbitals of sixfluorine atoms.
Hybrid Orbital of SiCl4:
In SiCl4,
silicon shows SP3
hybridization. Four
SP3 hybrid orbitals
are formed. They
overlap with four
P-orbitals of four
Chlorine atoms.
Hybrid Orbital of
:
In
,
Nitrogen
shows
SP3 hybridization.
Nitrogen
forms
three covalent bond
with three covalent
bond with three H-

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atoms and one
coordinate
bond
+
with H ion.

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Q.14.
b. How do you compare the bond strengths of
(i)
Polar and non-polar molecules, (ii) and bonds?
c. Calculate the bond energy of H-Br. The bond energy of H-H is
436 KJ mol-1 and that of Br-Br I s 193 KJ mol-1.
b.i.
A covalent bond between two alike atoms is called. e.g. Cl-Cl,
Br-Br. A covalent bond between two unlike atoms is called polar bond.
e.g.
,
. In a polar bond the shared pair of electrons is
slightly shifted towards more electro-negative (E.N) atom. So atoms
have partial positive and partial negative charges. Thus atoms are
attracted due to extra electrostatic (dipole-dipole) forces. Hence a polar
bond is stronger than a non-polar bond.
ii.
A bond formed by head to head or linear overlap of two partially
filled orbitals is called -bond. A bond formed by parallel overlap of two
partially filled P-orbitals is called -bond. In -bond, overlapping of
orbitals is symmetrical on the bond axis. In a -bond overlapping of
orbitals is spread above and below the bond axis. So -bond is stronger
than a -bond.
c.
Bond energy of
= 436 Kj mol-1
Bond energy of
per molecule =
= 7.24 10-22 Kj
Bond energy of 1atom of hydrogen =

= 3.62 10-22 Kj

= 193 Kj mol-1
per molecule =

= 3.20 10-22 Kj

Bond energy of
Bond energy of

Bond energy of 1atom of Bromine =

Bond energy of 1molecule of
5.22 10-22Kj
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= 1.60 10-22 Kj

= 3.62 10-22 + 1.60 10-22 =

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Bond length of HBr, r = 1.4 10-10m,

= 0.79D
-19
Unit positive charge, q = 1.6022 10 C
%ionic character = ?
= q r = 1.6022 10-19 1.4 10-10 = 2.24 10-29cm
=

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Bond energy of
per mole = 5.22 10-22 6.02 1023 = 314.2
Kj mol-1
Q.15.
b. The bond length of H-Br is 1.4 10-10m. Its observed dipole
moment is 0.79D. Find the percentage ionic character of the bond.
Unit positive charge = 1.6022 10-19 c and 1D = 3.336 10-30mc.

= 6.72 D

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%ionic character of H-Br =

= 11.7 %

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Q.16. PF3 is a polar molecular with dipole moment 1.02 D and thus
the P-F bond is polar. Si, is in proximity of P in the periodic table. It
is expected that Si-F bond would also be polar, but SiF4 has no
dipole moment. Explain it?
Ans: PF3 is a
Pyramidal
molecule like NH3.
All three P-F bonds
are polar. Their
polarity is not
cancelled. So PF3
has a net dipole
moment of 1.02D.
On other hand SiF4
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is
a
perfect
tetrahedral
molecule. All four
Si F bonds are
polar but their
polarity
is
cancelled
out.
Hence net dipole
moment of SiF4 is
zero.

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Q.17. Which of the following molecules will be polar or non-polar,

sketch the structures and Justify your answer.
(i) CCl4
(ii) SO3
(iii) SF4
(iv) NF3
(v)
PF5
(vi) SO2
(vii) SF6
(viii) IF7
Ans:
i.
CCl4:
The
CCl4
molecule
is
perfect
tetrahedral. All C Cl
bonds are polar. Their
polarities cancel each
other. Thus net dipole
moment is zero. So CCl4
is a non-polar molecule.
ii.

SO3:
The SO3 molecule
is plane triangular. All
bonds are polar but their
polarities cancel each
other. Thus net dipole
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1st year n0tes chemistry new

moment is zero. So SO3
is a non-polar.

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SF4:
The molecule SF4
is trigonal bi pyramidal.
All four S F bonds are
polar.
Their
bond
moments do not cancel
each other. Hence net
dipole moment of SF4 is
not zero. Therefore SF4 is
a polar molecule.

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iii.

NF3:
The molecule NF3
is trigonal pyramidal. All
four N F bonds are
polar.
Their
bond
moments do not cancel
each other. So net dipole
moment is not zero.
Hence NF3 is a polar
molecule.
v.

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iv.

PF5:
The molecule PF5
is trigonal bi pyramidal.
All P F bonds are polar.
Their bond moments
cancel each other. So net
dipole moment is zero.
Hence PF5 is a non polar
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molecule.

SF6:
The molecule SF6
is octahedral. All bond
moments cancel one
another. Thus net dipole
moment is zero. Hence
SF6 is a non-polar
molecule.
IF7:
The molecule IF7
is
Pentagonal
bi
pyramidal. All I-F bond
moments cancel each
other. So net dipole
moment is zero. Hence
IF7 is a non-polar.

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SO2:
The molecule SO2
is a angular V shaped.
Two bond moments do
not cancel each other.
Thus net dipole moment
is 1.6D. Hence SO2 is a
polar.

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Q.18. Classify the statements as true or false. Explain with reasons.

i.

Bond distance is the compromise distance between two atoms.

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iv.
v.
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iii.

The distinction between a coordinate covalent bond and a covalent

bond vanishes after bond formation in
, H3O+ and
.
The bond angles of H2O and NH3 are not 109.5o like that of CH4.
Although, 0-and N-atoms are sp3 hybridized.
are more diffused than
.
The abnormality of bond length and bond strength in HI is less
prominent than that of HCl.
Solid sodium chloride does not conduct electricity, but when
electric current is passed through molten sodium chloride or its
aqueous solution, Electrolysis takes place.
The melting points, boiling points, heat of vaporization and heats
of sublimations of electrovalent compounds are higher as
compared with those of covalent compounds.

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Ans.

When two atoms come close to make a bond, then their attraction
increases and P.E decreases. At a certain distance atomic attraction
is maximum and energy is minimum. It is compromise distance
between two atoms. Here bond formation takes place. It atoms
come further closer, then nuclear repulsions takes place and energy
of system increases. Here bond formation does not occur. Hence
bond distance is the compromise distance between two atoms.
In a covalent bond two atoms provide shared pair of electrons. In a
coordinate covalent bonds and one coordinate bond then there is no
difference between their bond length and bond energy. E.g. in
ion all four bonds are taken equally. It is the reason that distinction
between covalent and coordinate covalent bond vanishes after their
formation.
In NH3 and H2O there is SP3 hybridization like CH4. Four SP3
hybrid orbitals are formed. The angle between SP3 orbitals should
be 109.5o. But we know that NH3 has one lone pair and H2O has
two lone pairs of electrons. There is repulsion between lone pairs

ii.

iii.

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iv.

and bonding pairs of electrons. Due to lone pair-bond pair

repulsion the bond angles in NH3 and H2O are not 109.5o like CH4
which has no lone pair of electrons.
Sigma bond is formed by head to head (liner) overlap of two
partially filled orbitals. Here electron density is symmetrically
spread around the bond axis. The Pi-bond formed by parallel
overlap of two partially filled P-orbitals. Here electron density is
spread above and below the bond axis. It is the reason that
are
more diffused than
.
Chlorine has smaller size and higher electro negativity than Iodine.
Thus HCl has more polarity than HI. Due to this reason
abnormality of bond length and bond strength in HI is less
prominent than that of HCl.
In solid sodium chloride, the Na+ and Cl- ions have strong
electrostatic attractions. Thus they are tightly held and occupy
fixed positions. But in molten or solution form, ions become free
and move towards opposite electrodes. It is the reason that sold
NaCl does not conduct electricity but in molten or solution form
NaCl conducts electricity.

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In electrovalent compounds, the opposite ions have strong electrostatic

attractions. Thus they are tightly held and occupy fixed positions. It is
the reason that electrovalent compounds have high melting points,
boiling points, heat of vaporization and heat of sublimations as
compared with those of covalent compounds.

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